From 5570e31dc11aff3e15d027ebda95138f1f906081 Mon Sep 17 00:00:00 2001
From: lzy <949777411@qq.com>
Date: Thu, 8 May 2025 11:50:00 +0800
Subject: [PATCH] first commit task2

---
 .../1-s2.0-S0040609020301334-main.json        |  127 +
 .../1-s2.0-S030094402400482X-main.json        |  132 +
 .../1-s2.0-S0927775719302274-main.json        |   77 +
 .../1-s2.0-S0927775719311537-main.json        |  102 +
 .../1-s2.0-S0960852424013415-main.json        |  107 +
 .../1-s2.0-S1385894722033654-main.json        |  117 +
 .../1-s2.0-S2468023024008459-main.json        |   77 +
 .../task2-chunks/10.1002@adfm.201903419.json  |  187 +
 .../task2-chunks/10.1002@advs.202000439.json  |   67 +
 .../10.1007@s11998-020-00338-z.json           |   72 +
 .../10.1016@j.porgcoat.2019.01.061.json       |   92 +
 .../task2-chunks/1980-kao soap-anti-fog.json  |  107 +
 task2/task2-chunks/2001-US-anti-fog.json      |  117 +
 task2/task2-chunks/2002-╚¤┴т-anti-fog.json    |  107 +
 task2/task2-chunks/2003-JP-anti-fog.json      |   57 +
 task2/task2-chunks/2011-DE-anti-fog.json      |   67 +
 task2/task2-chunks/2020-US-anti-fog.json      |  107 +
 task2/task2-chunks/2_UV╖└╬э╥║╩╣╙├╦╡├ў╩щ.json  |   27 +
 ...for high-performance anti-fog coating.json |  127 +
 task2/task2-chunks/AI╙├╙┌╙╨╗·-╛█║╧╬я║╧│╔.json |  132 +
 ...��╩ї╘┌╗п╣д╨╨╥╡╔ш╝╞╣д╫ў╓╨╡─╙ж╙├╒╣═√_╜к╥╦╛¤.json |  137 +
 .../ANTI-FOG    US10241237B2.json             |  397 +
 .../task2-chunks/ANTI-FOG  US10048408B2.json  |  252 +
 task2/task2-chunks/ANTI-FOG  US9346974B2.json |  122 +
 ...n Materials and Processes of Additive.json |  187 +
 ...lic Hydrophobic Polymer Heteronetwork.json |   82 +
 ...ymer additive manufacturing_ A review.json |  212 +
 ...rhydrophobic arrays and SiO2 coatings.json |   77 +
 .../CN102666753B╖└╬э═┐┴╧╫щ║╧╬я.json           |   47 +
 ...��─╖└╬э═┐▓у░№└и╦о╨╘╛█║╧╬я╖╓╔в╠хбв╜╗┴к╝┴║═╛█╗╖╤ї═щ.json |   47 +
 task2/task2-chunks/CN104926988B.json          |   52 +
 ...��э╝┴╫щ║╧╬я╝░╩╣╙├╕├╖└╬э╝┴╫щ║╧╬я╡─╖└╬э╨╘▓·╞╖.json |   42 +
 task2/task2-chunks/CN106977688A-neo-ssq.json  |   57 +
 ...03746B_╥╗╓╓╖└╬э═┐┴╧╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json |   47 +
 ...�╨°─═─ж▓┴╡─╫╧═т╣т╣╠╗п╖└╬э═┐┴╧╫щ║╧╬я╝░╞ф═┐▓у╡─╓╞▒╕.json |   47 +
 ...��╗╓╓╦л▓у╫╧═т╣т╣╠╗п─═─ж▓┴╖└╬э═┐▓у╝░╓╞▒╕.json |   47 +
 ...��е╟╫╦о╩ў╓мбв╥╗╓╓╕▀─═─е╬▐╚▄╝┴╖└╬э═┐┴╧╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json |   47 +
 ...╓╦о╨╘╗╖▒г─═─е╨═╙╨╗·╬▐╗·╘╙╗п╖└╬э═┐┴╧╝░╞ф╓╞▒╕.json |   47 +
 ...╗╓╓╖└╤г╣т╨═╙╨╗·╬▐╗·╘╙╗п╖└╬э═┐┴╧╝░╞ф╓╞▒╕.json |   57 +
 ...��╜╟╫╨╘╣▓╛█╬я╡─╖└╬э═┐▓у╫щ║╧╬я╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json |   47 +
 ...�-╚╚╦л╓╪╣╠╗п╬▐╚▄╝┴─═─е╖└╬э═┐┴╧╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json |   47 +
 ...�╒▒╛-╖└╬э═┐▓у╫щ║╧╬ябв╖└╬э═┐─д╝░╖└╬э╓╞╞╖.json |   52 +
 ...�┌ABS╗∙▓─╡─╣т╣╠╗п│м╟╫╦о═┐┴╧╫щ║╧╬я╝░╞ф═┐▓у╡─╓╞▒╕╖╜╖и.json |   57 +
 ...��╗╓╓╙├╙┌╖└╬э═┐▓у╡─╟╫╦о╩ў╓м╝░╞ф╓╞▒╕╖╜╖и.json |   47 +
 ...��╓╟╫╦о╨═╤Ї└ы╫╙╣т╣╠╗п╩ў╓м╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json |   57 +
 ...��╗╓╓╟╫╦о╨═╣т╣╠╗п╩ў╓м╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json |   57 +
 ...╣╠╗п╡═╛█╬ябв╞ф╓╞▒╕╖╜╖и╝░║м╙╨╕├╡═╛█╬я╡─╣т╣╠╗п═┐┴╧.json |   52 +
 ...9B_╥╗╓╓╖└╬э═┐┴╧╝░╞ф╓╞▒╕╖╜╖ибв╖└╬э═┐▓у.json |   52 +
 ...4B_╥╗╓╓╕▀╙▓╢╚─═─ж▓┴╖└╬э═┐┴╧╝░╓╞▒╕╖╜╖и.json |   47 +
 ...�╨╘╛█║╧╬я╝░╞ф╓╞▒╕╖╜╖ибв░№║м╞ф╡─│м╟╫╦о═┐┴╧.json |   52 +
 ...╗╞╘н╜║╜╙╓ж╣▓╛█╬я╟¤╙═╝┴╝░╞ф╓╞╖и║═╙ж╙├-╔ъ╟ы╣л┐к.json |   57 +
 ...080052429.5 - ╖└╬э═┐┴╧╫щ║╧╬я - ░█╠┌═°.json |   47 +
 ...│м╟╫╦о═╕├ў╖└╬э═┐▓у╡─╓╞▒╕╖╜╖и-╔ъ╟ы╣л┐к.json |   47 +
 ...�╗╟╦с╧╡╣▓╛█╬я║═░▒╗∙╩ў╓м╡─╟╫╦о╨╘▓─┴╧-╔ъ╟ы╣л┐к.json |   57 +
 ...╤╬╨═╟╫╦о╨╘╫╧═т╣т╣╠╗п╩ў╓м╡─╓╞▒╕╖╜╖и-╔ъ╟ы╣л┐к.json |   47 +
 ...�╟╫╦о╨╘╫╧═т╣т╣╠╗п╩ў╓м╡─╓╞▒╕╖╜╖и╝░╞ф╙ж╙├-╔ъ╟ы╣л┐к (1).json |   47 +
 ...�╦с╤╬╡─╛█▒√╧й╦сїе╦о╖╓╔в╠х╝░╞ф╓╞▒╕╖╜╖и╙ы╙ж╙├-╔ъ╟ы╣л┐к.json |   57 +
 ...��╓╓╦л╔·╜с╣╣╛█├╤╣ш╤ї═щ╝░╓╞▒╕╖╜╖и-╔ъ╟ы╣л┐к.json |   52 +
 ...473-╦о╨╘╖└╬э═┐┴╧╝░╞ф╓╞▒╕╖╜╖и-╔ъ╟ы╣л┐к.json |   52 +
 ...�э═┐┴╧╫щ║╧╬я╝░╖└╬э═┐─д╥╘╝░╖└╬э╬я╞╖-╔ъ╟ы╣л┐к.json |   52 +
 ...╙┌╣╠╗п╗╖╤ї╩ў╓м╡─╕─╜°╡─╣╠╗п┤▀╗п╝┴-╔ъ╟ы╣л┐к.json |   22 +
 .../ChemDFMг║╗п╤з┴ь╙Є╡─┤є╨═╙я╤╘╗∙┤б─г╨═.json  |  217 +
 task2/task2-chunks/Corkuna Introduction.json  |  217 +
 ...═┐┴╧╫щ║╧╬я╝░╩╣╙├╞ф═┐┴╧╫щ║╧╬я╡─╖└╬э╨╘═╕├ў╞м▓─.json |   52 +
 .../HDI╚¤╛█╠х╡─╙ж╙├US9676895B2.json           |  187 +
 ...�┐ю╙├╙┌╖╓┼ф╕║╘Ё╚╦║═╛█║╧╖┤╙ж╓╨SMILES╡─╬▓▓┐.json |   67 +
 ...sure-sensitive adhesive polymers-1989.json |   97 +
 ...raphene oxide coating for antifogging.json |   87 +
 ...perhydrophilic surfaces and materials.json |  137 +
 ...▒їе╖┤╙ж╓╨╢╘╤б╘ё╨╘╬┬╢╚бв┤▀╗п╣¤│╠║═╖┤╙ж╢╘╧є╡─╙░╧ь.json |   62 +
 task2/task2-chunks/PUA.json                   |   92 +
 ...tor pendanted on hydrophilic oligomer.json |  107 +
 ...og hard coatings on plastic substrate.json |   62 +
 .../RSC-terminated polysilicon.json           |  222 +
 task2/task2-chunks/Rheology_-_2015.json       |  202 +
 task2/task2-chunks/SDC-FSI CN109070134B.json  |   52 +
 .../SDC-FSI╖└╬э-CN109070134B.json             |   52 +
 ...╧│╔╛█║╧╬я╨щ─т┐т╡─╔·│╔╩╣╙├╗∙╙┌╣ц╘Є╡─╛█║╧╖┤╙ж.json |   72 +
 task2/task2-chunks/Solvents_-_2015.json       |  142 +
 ... ammonium salts for anti-fog coatings.json |   87 +
 ...sulfonic groups for anti-fog coatings.json |   92 +
 ...position and method of making thereof.json |  102 +
 task2/task2-chunks/US20030148113A1.json       |   42 +
 task2/task2-chunks/US20080076851A1.json       |   57 +
 task2/task2-chunks/US20220106497A1.json       |  187 +
 task2/task2-chunks/US8642180.json             |  267 +
 .../UV-curable anti-fog coatings.json         |   47 +
 ...rticle_AReviewOnProtectivePolymericCo.json |   87 +
 task2/task2-chunks/Zhao et al.json            |   12 +
 ...ating film grafted on glass substrate.json |   77 +
 task2/task2-chunks/adma.201807101.json        |   32 +
 .../adma202002710-sup-0001-suppmat.json       |   52 +
 task2/task2-chunks/admi.201801018.json        |   67 +
 .../advs3770-sup-0001-suppmat.json            |   37 +
 task2/task2-chunks/am3c17117_si_001.json      |   62 +
 task2/task2-chunks/am7b05286_si_001.json      |   17 +
 task2/task2-chunks/am9b09610_si_001.json      |   17 +
 task2/task2-chunks/am9b21871_si_001.json      |   22 +
 task2/task2-chunks/ao4c03563_si_001.json      |   12 +
 task2/task2-chunks/ap4c00912_si_001.json      |    7 +
 ...hylacrylamide-and-quaternary-ammonium.json |   72 +
 task2/task2-chunks/bai2020.json               |   72 +
 task2/task2-chunks/bayer2655-US6767958.json   |  167 +
 task2/task2-chunks/binder2014.json            |   27 +
 .../task2-chunks/biomimetics-07-00162-v2.json |   92 +
 task2/task2-chunks/c5ra21399a.json            |   92 +
 task2/task2-chunks/chang2012.json             |   62 +
 .../f4873e73d5de21b101f3e4875ca97069.json     |   97 +
 task2/task2-chunks/fuctional polymer.json     |  152 +
 .../task2-chunks/functionalized polymer.json  |  127 +
 task2/task2-chunks/gui2020.json               |   62 +
 ...esent-in-commercial-anti-fog-products.json |   92 +
 task2/task2-chunks/j.tribology.2022016.json   |  122 +
 task2/task2-chunks/lee2013.json               |  107 +
 ...tings-containing-poss-pdmaema-b-psbma.json |   52 +
 ...gs-with-rapid-self-healing-capability.json |   57 +
 ...sistant-long-lasting-antifog-coatings.json |   82 +
 ...achine-learning-a-polymer-perspective.json |  152 +
 ...-functionalized-polyhedral-oligomeric.json |   72 +
 task2/task2-chunks/olveira2015.json           |  147 +
 ...sable polyurethane-acrylate(PUA) mold.json |   67 +
 task2/task2-chunks/passaglia2018.json         |   52 +
 ...erial coatings by photopolymerization.json |  102 +
 task2/task2-chunks/s41467-020-14807-x.json    |   52 +
 task2/task2-chunks/s41524-023-01000-z.json    |  107 +
 task2/task2-chunks/s41529-024-00427-z.json    |   92 +
 ...al dual-cure coatings for antifogging.json |   97 +
 task2/task2-chunks/uchiyama2015.json          |   62 +
 ...r the design of anti-fogging surfaces.json |  187 +
 task2/task2-chunks/xu2012.json                |  142 +
 ...ransparency-long-term-antifogging-and.json |   72 +
 task2/task2-chunks/zhang2021.json             |  162 +
 ...fogging-antimicrobial-polymer-coating.json |   47 +
 ...��х╝░╡═╛█╬я╘┌╦▄╜║╗∙▓─╔╧╡─╕╜╫┼┴ж╙ы╗п╤з╜с╣╣╓о╝ф╣╪╧╡╡─╤╨╛┐.json |   72 +
 ...�╠╥л╗╘-╧╦╬м╦╪└ы╫╙╥║╠х╤Ї└ы╫╙╨═╤▄╔·╬я╖└╬э.json |  632 ++
 task2/task2-chunks/└н┬№.json                  |   72 +
 .../task2-chunks/└√╙├PubChem╜°╨╨╨щ─т╔╕╤б.json |  107 +
 ...�╙├╔ю╢╚╤з╧░╥¤╡╝╡─╥┼┤л╦у╖и╠╜╦ў▓─┴╧╔ш╝╞┐╒╝ф.json |  137 +
 .../task2-chunks/┤·▒э│╔╣√5-nanomaterials.json |   82 +
 ...�є╣ц─г╗п╤з╙я╤╘▒э╩╛▓╢╫╜╖╓╫╙╜с╣╣╙ы╨╘╓╩ zh.json |   77 +
 .../┤є╣ц─г╗п╤з╙я╤╘▒э╩╛▓╢╫╜╖╓╫╙╜с╣╣╙ы╨╘╓╩.json |   87 +
 ...��и╙├╨═╡╜╫и╝╥╨═г║╗п╤з┴ь╙Є┤є╨═╙я╤╘─г╨═╡─╫█╩Ў.json |  152 +
 ...�·╢р╧р┤▀╗п╝┴г║╗·╞ў...╓·┴ж▒э├ц╖┤╙ж╨╘╘д▓тги╙в╬─гй_┴ї╨╛╤╘.json |  122 +
 ...и╣¤╗·╞ў╤з╧░╘д▓т╛█╡ч╜т╓╩╢р▓у─д╡─═┐▓у║ё╢╚.json |   47 +
 ...��п╤з╠╪╨╘╔ш╝╞╫╘╫щ╫░╢■ы─╦о─¤╜║╝░╞ф╗·╞ў╤з╧░╤╨╛┐.json |   17 +
 task2/task2-chunks/═┐┴╧╚▄╝┴╡─╜щ╔▄.json        |   67 +
 .../task2-chunks/═┐┴╧╣д╥╒ги╡┌╦─░цгй╔╧▓с.json  | 5677 +++++++++++
 .../task2-chunks/═┐┴╧╣д╥╒ги╡┌╦─░цгй╧┬▓с.json  | 8647 +++++++++++++++++
 ...╗╖╛│╓╟─▄╖└╕п═┐▓уг║╜с╣╣╔ш╝╞╙ы╧ь╙ж╗·╓╞_╦я╙н╧ш.json |   77 +
 .../task2-chunks/╒│╨╘╞Ё╩╝▓у ═и╙├╦о─¤╜║AM.json |   52 +
 .../╒│╨╘╞Ё╩╝▓у ═и╙├╦о─¤╜║AM╕╜╝■.json          |   47 +
 task2/task2-chunks/╔ю╢╚╤з╧░╦о─¤╜║.json        |   92 +
 task2/task2-chunks/╔┘╤∙▒╛SI.json              |   17 +
 .../task2-chunks/╕┤╨╘╦о─¤╜║═┐┴╧ Sci. Adv.json |  122 +
 ...┴┐║╧│╔╖╓╬Ў║═╙┼╗п╙├╙┌╡░░╫╓╩╡▌╦═╡─┐╔╫в╔ф╦о─¤╜║.json |   52 +
 ...��у▓─┴╧╝░╞ф╖└╬█╩═╖┼╗ю╨╘╥╗╓╓╙├╙┌╘д▓т╨╘╓╩╡─╗п╤з╨┼╧в╤з╖╜╖и.json |   52 +
 .../╕▀╖╓╫╙▓─┴╧╗∙╥Є╫щ╤╨╛┐╜°╒╣_╙жь│╢∙.json      |  112 +
 ...█─й═┐┴╧╛▓╡ч┼ч═┐╡──¤╣╠╣¤│╠╖╓╬Ў╙ы▓╬╩¤╙┼╗п.json |  107 +
 ...�├ш╩Ў╖√╠ї╝■╤н╗╖╔ё╛н═°┬ч╡─┤╙═╖╖╓╫╙╔·│╔╓▒╜╙╥¤╡╝.json |   77 +
 ...�┌╗·╞ў╤з╧░╡─╥■╔э═┐┴╧╔ш╝╞╖╜╖и╙ы╤╨╛┐╜°╒╣_┴ї╨ё.json |   62 +
 ...�╚э╗·╞ў╚╦╓╨╩╡╧╓┤л╕╨╘╦╢п╣ж─▄╡─╚э▓─┴╧║═╫░╓├.json |  327 +
 ...��▓─┴╧╖в╧╓╡─╔·│╔╩╜╚╦╣д╓╟─▄ги╙в╬─гй_Jianjun Hu.json |   47 +
 task2/task2-chunks/╙═╦о╖╓└ыAFM.json           |   72 +
 .../╙╛╛╡╖└╬э╥й╦о╕─╔╞╩ф╚ы-20191028.json        |   27 +
 .../╚э╨╘║═╥║╠м╖╓╫╙▓─┴╧╡─╗·╞ў╤з╧░.json         |  102 +
 ...╨┬▓─┴╧╤╨╖вг║┬ї╧Є...╘д▓т╨╘╔ш╝╞б▒║═б░╛л╫╝┤┤╓╞б▒_╣∙╫╙╖╝.json |   32 +
 .../╚╦╣д╓╟─▄╕и╓·╔ш╝╞╣ж─▄╨╘║═┐╔│╓╨°╛█║╧╬я.json |  242 +
 .../╚╦╣д╓╟─▄╕и╓·╨┬╗п╤з╞╖╔ш╝╞╩╙╜╟.json         |   12 +
 ...▄╘┌╗п╤з╣д│╠╓╨╡─╙ж╙├бкбк┤┤╨┬╡─╨┬╞к╒┬ги╙в╬─гй_╚╬╞ф┴·.json |   12 +
 ...�д╓╟─▄╘┌╤к╥║╝▓▓б╒я┴╞╓╨╡─╙ж╙├╤╨╛┐╜°╒╣_╒┼└ё╟▒.json |   47 +
 ...��─▄╟¤╢п╡─╦о─¤╜║╔ш╝╞бв╙┼╗п╝░╞ф╘┌╔·╬я╥╜╤з╓╨╡─╙ж╙├.json |  107 +
 ...��╝╡─╔┘╤∙▒╛─ц╧Є╔ш╝╞╙├╙┌┐╣╥й╨╘╧╕╛·╡─╕▀├▄╢╚╛█║╧╬я─г─т╛█║╧╬я.json |  212 +
 ...��╫┼┴├╣╦╪═и╣¤╡ў┐╪╣╟...┐╫╝┘╠х╜ч├ц╣╟╒√║╧╡─╗·╓╞╤╨╛┐_└ю╫ц║╞.json | 1147 +++
 ...��─╨╘╢р├ц╠х╡═╛█▒╢░ы╣ш╤ї═щ╣╣╓■─═╦о╨╘╟╫╦о╖└╬э═┐▓у.json |   97 +
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+[
+    {
+        "id": 1,
+        "chunk": "# Sorption and permeation of water through Plasma Enhanced Chemical Vapour Deposited phosphonic acid-based membranes  \n\nArnaud Joël Kinfack Leogaa, Stéphanie Roualdèsa,⁎, Vincent Rouessaca, Nadège Follainb, Stéphane Maraisb  \n\na Institut Européen des Membranes, IEM UMR 5635, Univ Montpellier, ENSCM, CNRS, Montpellier, France b Normandie Univ, UNIRouen Normandie INSA Rouen CNRS PBS, Rouen 76000, France",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# A R T I C L E I N F O",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# A B S T R A C T  \n\nKeywords:   \nPhosphonic acid-based membrane   \nPlasma Enhanced Chemical Vapor Deposition   \nPlasma polymer   \nWater sorption   \nWater permeability  \n\nPhosphonic acid-based membranes were prepared by Plasma Enhanced Chemical Vapor Deposition (PECVD) with an input power of $100~\\mathrm{{w}}$ in a continuous or pulsed glow discharge. Comparing both kinds of plasma discharges makes appear that the pulsed configuration gives rise to PECVD materials with longer hydrocarbon chains and thus higher flexible polymer network which consequently present better sorption properties than those prepared from a continuous plasma discharge. Being more hydrophilic and richer in acidic functions than Nafion® 212, PECVD membranes (whatever the kind of plasma discharge, pulsed or continuous, during the deposition of films) present a better water sorption ability. Nevertheless, having a more highly cross-linked structure, they have a lower water diffusion/permeation capacity. Consequently PECVD membranes show singular water management properties which could be a great advantage for the final Proton-Exchange Membrane Electrolyte Cells and Proton-Exchange Membrane Fuel Cells applications.",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1. Introduction  \n\nIn the field of low-temperature electrolysis and fuel cells, Proton Exchange Membranes have attracted extensive attention in the recent years, due to their advantageous dual transport properties: protons transport to ensure internal conduction in the cells and gas barrier property to prevent fluids at both electrodes from interacting [1–4]. Most of the PEMECs (Proton-Exchange Membrane Electrolyte Cells) and PEMFCs (Proton-Exchange Membrane Fuel Cells) in the literature use sulfonic acid-based membranes notably Nafion® (by DuPont de Nemours) due to its several advantages such as excellent chemical, mechanical and thermal stabilities and high proton conductivity $(60{-}100\\ \\mathrm{mS.cm^{-1}})$ in the temperature range $30\\mathrm{-}80\\ ^{\\circ}\\mathrm{C}$ [5,6]. However, the dependence of Nafion® proton transport mechanism on water (due to its high acidic character) has motivated the research to develop alternative membranes being less water dependent such as imidazole [7,8] and phosphonic acid-based membranes [9–13]. Compared to imidazole, phosphonic acid-based groups are more amphoteric and possess a relatively high dielectric constant. The combination of these two properties leads to a high degree of auto-dissociation which favors the formation of a hydrogen-bonding network making the proton conductivity independent of relative humidity and temperature. Thus the proton transport through an anhydrous conduction mechanism known as the Grotthuss mechanism [14] is favored. Although phosphonic acidbased membranes are likely to operate in an anhydrous medium, the presence of water in these membranes remains an important factor facilitating proton transport and conditioning the maintenance of good performance of PEMECs and PEMFCs for a relatively long operating time [15,16].  \n\nAlthough the preparation of membranes containing phosphonic acid groups has enabled to improve the performance of electrolyte membranes in anhydrous conditions, these membranes still suffer from some limitations such as low mechanical stability and a poorly effective barrier effect on liquids and gases which strongly limit their competitiveness [17]. Therefore, the development of polymer electrolyte membranes that can efficiently conduct protons but block liquids and gases permeation has been envisaged by using Plasma Enhanced Chemical Vapor Deposition (PECVD) [18]. This dry-route synthesis method is considered as a promising way to prepare dense, uniform and mechanically resistant membranes [19,20]. It has been reported in the literature that electrolyte membranes prepared by PECVD exhibit superior properties, such as higher thermal and chemical stability, lower liquid and gas permeability and higher water retention (with a quite similar protons conduction level) when compared with classical polymer membranes, which provide them with great potential as membranes for PEMECs or PEMFCs applications [15,18]. However PECVD is a very complicated process in terms of synthesis mechanisms which are noticeably influenced by the plasma parameters in the preparation of membranes. Now synthesis mechanisms directly control the properties of the obtained membranes, in particular water sorption and permeation properties [21–23].  \n\nThis work is a sequel to a previous study by our group [15] which consisted in studying the influence of the plasma deposition conditions, especially the nature (continuous or pulsed) and the input power (in the range of $60-100\\mathrm{W})$ of the plasma discharge on the materials structural and proton conduction properties. The main objective of this paper is to investigate the water sorption and permeation properties of phosphonic acid-based membranes prepared at 100 W plasma input power (considered as the optimal plasma input power according to our previous study) in a continuous or pulsed discharge in comparison with those of the sulfonic acid-based membrane Nafion® 212 (as a commercial reference). Another objective of this study is to demonstrate the improvement of the membrane water sorption properties by using the pulsed plasma deposition configuration. The structural and physicochemical properties of the prepared phosphonic acid-based plasmapolymerized membranes were performed using different experimental methods, i.e. Scanning Electron Microscopy (SEM) for the membranes morphology and thickness, X-ray photoelectron spectroscopy (XPS) for the materials chemical composition and contact angle method for the membranes surface hydrophily/hydrophoby. In terms of transport properties, water sorption behavior of phosphonic acid-based plasmapolymerized membranes was investigated by ellipsometry coupled with water sorption and by Cahn microbalance; their water permeability was evaluated by diffusion measurements through a permeation cell.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2. Experimental section",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.1. Membranes preparation procedure  \n\nThe membranes preparation procedure is the same as that described in a previous paper by our group [15]. The PECVD device used was centrally composed of a $30\\mathrm{~L~}$ lab-scale capacitively coupled plasma reactor operating with a radio-frequency (RF) discharge at $13.56~\\mathrm{MHz}$ (manufactured by MECA2000). The precursor used was the dimethyl allylphosphonate ([757–54–0], SP-61–001, supplied by SPECIFIC POLYMERS) and the gas carrier was argon (purity $>99.999\\%$ , supplied by AIR LIQUIDE).  \n\nTwo different types of substrates were used to support phosphonic acid-based plasma-polymerized membranes: boron-doped p-type silicon wafer (100) (from Monsanto Electronic Materials, resistivity: 1–50 Ω.cm) for structural characterizations (SEM, XPS and ellipsometry) and Nafion® 212 (from Sigma-Aldrich) for SEM observations, contact angle investigation and water transport properties characterizations (sorption and permeation of water). Before each deposition process (continuous or pulsed), supports (silicon wafer and Nafion $\\mathfrak{G}$ 212) were $15\\mathrm{min}$ long plasma pre-treated (in a 100 W continuous plasma discharge), in order to clean the supports and improve plasma film adherence on them.  \n\nIn this study, the plasma discharge power was fixed at $100~\\mathrm{W}$ ; the only variable plasma parameters during deposition was the plasma discharge configuration (continuous or pulsed). The pulsed configuration consisted in performing the deposition by alternating $T_{o n}$ (time during which the plasma was on, equal to $5~\\mathrm{m}s\\mathrm{.}$ ) and $T_{o f f}$ (time during which the plasma was off, equal to $5\\mathrm{m}s\\mathrm{.}$ ). Pulse frequency was fixed at $100\\mathrm{Hz}$ . So the duty cycle $(D C)$ , defined by Eq. (1) was equal to 0.5, i.e. $50\\%$ . The $D C$ has been fixed at $50\\%$ , based on our previous paper [15] which was based on some references in the literature. As example, Z. Jiang et al. [22] has worked on the synthesis and optimization of proton exchange membranes prepared using a pulsed plasma enhanced chemical vapor deposition technique and has proved that a DC comprised between 0.1 to 0.5 could allow a softer fragmentation and thus, a better plasma polymerization, compared to higher DC values.  \n\n$$\nD C={\\frac{T_{o n}}{T_{o n}+T_{o f f}}}=T_{o n}X p u l s e f r e q u e n c y\n$$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.2. Morphological, structural and physico-chemical characterization techniques",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.2.1. SEM analysis  \n\nThe influence of the type of support on the PECVD membranes morphology and thickness (error $\\sim10\\%$ was investigated using a scanning electron microscope S-4800 Hitachi (using an operating voltage between 2 and $8~\\mathrm{kV},$ . Before the SEM analysis, the membranes deposited onto Nafion® 212 were immersed and broken in liquid nitrogen in order to have a neat cut of the samples cross-section. Before each observation, all the samples (deposits on silicon wafer or on Nafion® 212) were Pt-metalized by sputtering under vacuum in order to make the membrane surface electron conductive and so more easily observable.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.2.2. XPS analysis  \n\nThe chemical composition of the PECVD membranes deposited on silicon wafer was determined by XPS on an ESCALAB 250 from Thermo Electron (monochromatic source of Aluminium $1486.6\\ \\mathrm{eV}$ ; diameter of the analyzed surface: $400~{\\upmu\\mathrm{m}})$ . The background signal was removed using the Shirley method [24]. The surface atomic concentrations were determined from photoelectron peaks areas using the atomic sensitivity factors reported by Scofield [25]. Binding energies (BE) of all core levels were referred to the $C=C$ of C1s carbon at 284.4. eV.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.2.3. Contact angle method  \n\nThe contact angle method was performed to evaluate the surface wettability of the PECVD membranes deposited on Nafion® 212 (in comparison with the virgin Nafion® 212). The device used was a homemade equipment. The procedure consisted in depositing a drop of water of approximatively $6~\\upmu\\mathrm{L}$ on the surface of the analyzed sample. From the photo of the drop deposited on the material surface (taken 3 seconds after the drop deposition), the contact angle could be evaluated by averaging the contact angle (left and right) of 3 successive measures in order to determine the surface wettability of the analyzed membrane, using ImageJ utility with the drop shape analysis plugin.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 2.3. Water sorption and permeation characterization techniques",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# 2.3.1. Ellipsometry coupled with water sorption analysis  \n\nEllipsometry analysis was used to investigate the PECVD membranes behavior to the water sorption by using a Semilab GES5E spectroscopic ellipsometer (spectral range: 1.23–4.97 eV; Xenon lamp) completed with a lab-made set up for automatic adsorption-desorption with different intrusive vapor probes. Before each water sorption analysis, the sample (film deposited on silicon wafer) was vacuumed down to the limit pressure of $5\\ \\mathrm{Pa}$ (Alcatel Drytel 1025). Then, ultra-pure water (Milli- $Q^{\\circledast}$ purification system, Millipore) was introduced progressively in the analysis chamber by monitoring the ratio $P/P_{o}$ with $P$ being the water partial pressure and $P_{O}$ being the saturated vapor pressure of water at the analysis temperature. The thickness and refractive index (RI) on the full spectral range were simultaneously calculated from the ellipsometer data collected every $60~s$ in steady state, using the optical model Cauchy law.  \n\n2.3.2. Water sorption measurements by Cahn microbalance 2.3.2.1. Experimental procedure. Measurements of water vapor sorption through the PECVD membranes and Nafion® 212 were carried out using a Cahn D200 microbalance with electromagnetic compensation, DVS (Dynamic Vapor Sorption), supplied by Surface Measurement Systems (SMS, England) with a resolution of $0.1~\\upmu\\up g$ . This apparatus enables to measure the mass variation of a sample, following the adsorption or the desorption of a penetrant in vapor form, with a prescribed activity $a$ such that:  \n\n$$\na=\\frac{p}{p_{s a t}}\n$$  \n\nWith $P$ variable vapor pressure and $P_{s a t}$ saturated vapor pressure (of water in our case) at a controlled temperature $25^{\\circ}\\mathrm{C}$ in this work).  \n\nThe dry sample $\\mathrm{50~mg}$ for PECVD membranes and $5~\\mathrm{mg}$ for the Nafion® 212 membrane) was placed in the measuring nacelle within the thermoregulated chamber. Before each measurement, a conditioning step was carried out by imposing a sweep of dry nitrogen (Technical Nitrogen, Air Product) at a flow rate of $200~\\mathrm{cm}^{3}.\\mathrm{min}^{-1}$ to dry the sample and to remove all traces of humidity in the device. The mass of the sample after this step was recorded as the dry mass $M_{O}$ . Then a sequence of water vapor activity programmed from 0.05 to 0.95 was imposed on the sample. Each level of activity $a$ gave rise to a variation of the mass as a function of time until a sorption equilibrium was reached. For each water activity, the establishment of a sorption kinetic of the sample allowed to determine both the intrinsic diffusion coefficient (in head period of the transient regime) and the sorption equilibrium (in the second period of the kinetic, at the plateau). The so obtained sorption isotherm was read for physical interpretations of the mechanisms involved.  \n\n2.3.2.2. Theory and modeling. Depending on the nature and strength of the interactions between penetrant and substrate, the shape of a sorption isotherm varies. In literature, different models exist [26] to explain the behavior of small molecules interacting with a substrate. These models have been classified by Rogers [27]. Taking into account the shape of the isotherms obtained in this study and knowing the nature of the system penetrant/substrate, the representations of DualMode type and type BET II (Brunauer, Emmett, Teller) are relevant and described below.  \n\nThe dual-mode sorption mechanism results from a combination of the Henry and Langmuir type sorption isotherms. The shape of the isotherm (generally concave then linear) is characteristic of a double sorption model. It generally concerns glassy polymers and obeys the additivity law:  \n\n$$\nC=k_{H}.\\ a+{\\frac{A_{L}.\\ b_{L}.\\ a}{1+b_{L}.\\ a}}\n$$  \n\nWith $A_{L}$ the average concentration of Langmuir sites, $b_{L}$ the affinity constant of the penetrant molecules for these Langmuir sites, and $k_{H}$ the solubility coefficient also called Henry constant.  \n\nConcerning the Park model [28], it takes into account the formation of water aggregates in addition to the combination of the Langmuir and Henry type sorptions, or of the BET II type. This model is usually relevant in the case of water sorption in hydrophilic polymers or having polar functions or physical sites such as microvoids (as in glassy polymers). Park model can be mathematically described in the following form:  \n\n$$\nC=\\frac{A_{L}.\\:b_{L}.\\:a}{\\left(1+b_{L}\\times a\\right)}+k_{H}.\\:a+n.\\:K_{a}.\\:k_{H}^{n}.\\:a^{n}\n$$  \n\nWith $K_{a}$ the equilibrium constant for the aggregation reaction (formation of water clusters), $n$ the number of water molecules per aggregate and $k_{H}$ the Henry constant.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# 2.3.3. Water permeation measurements  \n\nFor water permeation measurements, the sample (PECVD film or Nafion® 212 membrane) was placed between two compartments of a permeation cell which was itself inserted in a thermostatically controlled enclosure at $25~^{\\circ}\\mathrm{C}$ (Fig. 1). The measurement was done in two steps. The preliminary step called \"purge\" consisted in drying the assembly (cell $^+$ film) with an inert and dry sweeping gas at a flow rate of  \n\n$560\\mathrm{ml.min^{-1}}$ (upstream: technical nitrogen, Air product; downstream: nitrogen beep, Air Product). Then a cooled mirror hygrometer (1311XR probe from General Eastern, USA) continuously measured the dew point temperature $T_{R}$ of sweeping gas in the downstream compartment as function of time. When the dew point temperature $T_{R}$ reached a constant value close to $-70~^{\\circ}\\mathrm{C}$ (corresponding to about $2.5~\\mathrm{ppmV}$ of water), the upstream nitrogen flow was then substituted by pure liquid water $\\ensuremath{\\mathrm{~\\boldmath~\\Omega~}}^{\\ }(18\\ \\ensuremath{\\mathrm{M}}\\Omega)$ . Due to the water concentration gradient established between both sides of the film, the water molecules could migrate through the film, from the upstream compartment to the downstream compartment where the flow of dry nitrogen could be charged in humidity; thus the mirror probe recorded the rise in dew point temperature $T_{R}$ as function of time. The flux (flux density) of water molecules having passed through the film $\\textit{J}(L,t)$ was determined by:  \n\n$$\nJ(L,\\ t)=\\frac{d.10^{-6}}{A}.\\ \\frac{x^{o u t}-x^{i n}}{R.\\ T}.p_{t}\n$$  \n\nWhere $d$ is the flow rate of sweeping gas the downstream compartment $(d=560\\mathrm{mL.min}^{-1})$ , $A$ is the active surface of the film $(A=2.5\\:\\mathrm{cm}^{2})$ , $R$ is the constant of the perfect gases $\\begin{array}{r l r}{(R}&{{}=}&{0.082}\\end{array}$ atm. $.\\mathrm{cm}^{3}.\\mathrm{K}^{-1}.\\mathrm{mmol}^{-1}\\ y$ , $p_{t}$ is the total pressure $(p_{t}=1$ atm). $x^{o u t}$ and $x^{i n}$ (ppmV) are respectively the water contents in the flushing gas at the inlet and outlet of the downstream compartment and are calculated as follows:  \n\n$$\nx=e^{\\left(-{\\frac{b}{T_{R}}}+c\\right)}\n$$  \n\nWhere $b$ and c $(b=6185.66\\mathrm{~K~}$ and $c=31.38)$ are empirical constants and valid for a dew point temperature range of $-70$ to $+20~^{\\circ}\\mathrm{C}$ [29].  \n\nThe permeability coefficient $P e$ is directly proportional to the flux of molecules passing through the film at the stationary state $J_{s t y}$ according to:  \n\n$$\nP e=\\frac{J_{s t\\cdot L}}{\\Delta a}\n$$  \n\nWith L the wet thickness and $\\Delta\\mathsf{a}$ the activity change defined as follows:  \n\n$$\n\\Delta a=a_{a m}-a_{a\\nu}\\approx1\n$$  \n\nWith $a_{a m}$ and $a_{a\\nu}\\mathbf{r}$ epresenting the water activities in the upstream and downstream compartments, respectively.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3. Results and discussions",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3.1. Morphology and thickness observations of PECVD membranes  \n\nFig. 2 shows a SEM cross-section view of a typical PECVD membrane deposited at 100 W plasma input power on silicon wafer (Fig. 2-a and c) and on Nafion® 212 (Fig. 2-b and d) for 1 hour deposition time. As already observed in a previous paper by our group [15], the PECVD coating on silicon wafer is dense, uniform, defect-free and very adherent on support (Fig. 2-a) and a slide detachment from the support is observed in the case of Fig. 2-c due to preparation of the sample only. Concerning the coating deposited on Nafion® 212 (Fig. 2-b), it can be noticed the presence of fractures and detachment of the film from the support probably due to the difference of mechanical properties between the film and the polymer support which certainly induces a decohesion of the bi-layered material during its preparation for SEM analysis (even if carried out by cryofracture in the liquid nitrogen). Only an inhomogeneity of the surface is displayed for the PECVD membrane prepared in continuous discharge (Fig. 2-d).  \n\nDespite the deposition time was the same $(1\\ \\mathrm{h})$ , the thicknesses of the films varied noticeably depending on the type of support. The thicknesses were respectively ${\\sim}1~\\upmu\\mathrm{m}$ for the membranes deposited on silicon wafer and ${\\sim}300~\\mathrm{nm}$ for the membranes deposited on Nafion® 212. This thickness disparity can be jutified by the surface state of the supports which is different from one support to another. This point will be examined in part 3.3.  \n\n![](images/78c1cd2365375e07edbfb767b792ec288f83b90c7325a5eeea83a0363e6c94ea.jpg)  \nFig. 1. Water permeation device.  \n\n![](images/a5a0f5de355ee34ffaecdce3fa1bc2d09748ba58ef3fd62dfaa1e3901f4d0f54.jpg)  \nFig. 2. PECVD membrane deposited at $100\\mathrm{W}$ with respectively a pulsed plasma discharge on (a) silicon wafer and (b) Nafion $\\mathfrak{P}$ 212 and a continuous discharge on (c) silicon wafer and (d) Nafion ${\\mathfrak{s}}$ 212.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 3.2. Chemical composition of PECVD membranes  \n\nIn order to investigate the chemical structure of PECVD membranes, XPS analyzes were performed. These analyzes were focused on the three chemical elements phosphorus, oxygen and carbon whose atomic percentages are presented in Table 1 for analyzed PECVD membranes and also for Nafion® 212 (from results extracted from the literature [30]). According to these results, PECVD membranes are supposed to be potentially more richer in acidic functions than Nafion® 212 assuming that a significant part of phosphorus elements corresponds to the phosphonic acid-based groups. Futhermore, the chemical composition gap between the two families of PECVD membranes (i.e. prepared with a continuous or pulsed plasma discharge) is related to the fragmentationrecombination mechanism of species during the deposition. Indeed, in the pulsed plasma discharge, the precursor containing hydrocarbon chains is less fragmented in the gaseous phase and thus the obtained material resulting from the combination of bigger fragments contains longer hydrocarbon chains and more carbon than the film prepared with the continuous plasma discharge. The consequence of PECVD materials containing more hydrocarbon chains is that they contain less phosphonated groups or phosphonic acid groups and thus less oxygen and phosphorus elements [15]. The chemical composition of the PECVD membranes can directly affect their physico-chemical properties such as their hydrophobic/hydrophilic nature characterized from contact angle measurements. It can be justified by the fact that, hydrophily/hydrophoby properties depend on the membrane surface state and thus on the presence of active functions on the surface of the membrane [31], which will be investigated in part 3.3.  \n\nTable 1 XPS atomic percentages of carbon, oxygen and phosphorous in PECVD membranes in comparison with chemical composition of Nafion ${\\mathfrak{G}}$ 212 in literature.   \n\n\n<html><body><table><tr><td>Membrane/at.%</td><td>C</td><td>F</td><td>0</td><td>S</td><td>P</td><td>- SO3H</td></tr><tr><td>Nafion°212 (from[30])</td><td>33.2</td><td>59.9</td><td>5.8</td><td>1.1</td><td>-</td><td>~ 1%</td></tr><tr><td>Membrane 1oo W - continuous plasma</td><td>38.2</td><td></td><td>43.5</td><td></td><td>18.3</td><td>-</td></tr><tr><td>Membrane 10o W - pulsed plasma [DC = 50%]</td><td>49.1</td><td>一</td><td>36.3</td><td>一</td><td>14.6</td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 3.3. Evaluation of the hydrophilic / hydrophobic character of PECVD membranes  \n\nBefore everything else, the contact angles of virgin supports (i.e. silicon wafer and Nafion $\\mathcal{\\underline{{\\boldsymbol{\\mathfrak{G}}}}}$ 212) were measured in order to determine their surface wettability (hydrophilic or hydrophobic nature). Table 2 presents the shape of the drop on the sample surface and the corresponding contact angle obtained for each support. For each sample, three contact angle measurements were realized, then all measured angles (six in total due to left and right sides for each drop) were averaged in order to obtain the corresponding mean contact angle $\\theta(^{\\circ})$ . As expected, Nafion® 212 (with a contact angle $\\theta>90^{\\circ}.$ presents a much more hydrophobic surface than silicon wafer $(\\theta~=~42~\\pm~2^{\\circ})$ , which explains why the growth rate of deposit on its surface is noticeably less than that on silicon wafer (as presented in part 3.1).  \n\nFig. 3 shows the mean contact angles $\\theta$ for the virgin supports (silicon wafer and Nafion® 212) already presented in Table 2 compared with the contact angles obtained for the PECVD membranes (prepared in both continuous and pulsed plasma discharges) deposited on silicon wafer. Thereby, the contact angle of the membrane prepared in pulsed conditions is lower than the contact angle of the material deposited in continuous conditions, which is also lower than that of the supports. Thus the pulsed discharge gives rise to more hydrophilic materials than the continuous one. This can be explained by the fact that the contact angle depends on the surface wettability, therefore on the roughness and the surface chemistry of the material [31]. Kale et al. [32] demonstrated that the use of a pulsed plasma discharge made it possible to obtain more hydrophilic tetraethylorthosilicate and hexamethyldisiloxane polymers than those obtained in continuous plasma discharge from the same precursors because of the lower density and more organic nature of the materials obtained in pulsed synthesis conditions. While Inagaki et al. [33] have shown that the surface properties are rather related to the surface chemistry of the materials (presence of active function on the surface of the membrane) when the plasma films are totally amorphous. In our case, there is clearly a competition between roughness and surface chemistry because although the film prepared in pulsed plasma deposition mode is less rich in active functions (i.e. phosphonated groups or phosphonic acid groups as mentioned in part 3.2) than that prepared in continuous plasma, it nevertheless has the most hydrophilic surface. Unfortunately the surface roughness was not evaluated in this study to confirm this hypothesis.  \n\n![](images/a8be053bc3ab4ed8ed1bf2eb58db8a11456156620155f3a567ae7d76f3020688.jpg)  \n\n![](images/f3e583cdb4de9719b5115b73101f8e7862a80623358a7f4b799a5de00fb3e82a.jpg)  \nFig. 3. Mean contact angles of both virgin supports and PECVD membranes deposited on silicon wafer.  \n\n![](images/839bf7acee73ed3edb74ae65632a82d7005ad68bf61b000eaf5440142e843c27.jpg)  \nFig. 4. Swelling rate change following water sorption in PECVD membranes.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# 3.4. Swelling rate change following water sorption of PECVD membranes  \n\nThe water sorption properties of PECVD membranes were foremost studied by ellipsometry coupled with water sorption. Fig. 4 shows the swelling rate change $(t{-}t_{O})/t_{O}$ of films as a function of water activity $P/$ $P_{O}$ . By increasing the water activity from 0 to 0.85, whatever the membrane is, the swelling rate change increases, i.e. to the amount of adsorbed water increases. This amount is less in the material prepared with the continuous plasma discharge. Despite the material prepared in the pulsed configuration presents the worst chemical composition in terms of concentration of active functions (in particular phosphonic acid groups), it shows the best ability to adsorb water. Indeed, the adsorption capacity of water is directly related to the length of the polymer chains. As already explained in the part 3.2, in pulsed plasma conditions, the resulted deposit contains longer hydrocarbon chains. Longer chains certainly induce higher flexibility of the polymer network and that allows a higher increase of the free volume as the water molecules penetrate the material.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 3.5. Water sorption isotherms of PECVD membranes and modeling  \n\nIn addition to the previous results displayed by ellipsometry coupled with water sorption, water vapor sorption measurements at $25^{\\circ}\\mathrm{C}$ were carried out using a sorption microbalance on PECVD membranes (deposited on silicon wafer) and compared to those performed on the plasma pre-treated Nafion $\\circledast$ 212 membrane and untreated Nafion $\\circledast$ 212 (as reference materials).  \n\nFig. 5 shows two successive sorption isotherms and an intermediate desorption isotherm with water vapor for both plasma pre-treated Nafion® 212 and untreated Nafion® 212. These isotherms represent the water mass gains, at the sorption equilibrium, as a function of the applied water activity. In both types of Nafion®, it can be seen that the desorption isotherms are slightly greater than the sorption isotherms, revealing a hysteresis conventionally encountered, and secondly that the second sorption isotherms are superimposed on the first sorption isotherms, indicating that there is no retention of sorbed water during the first sorption number one, and that the sorption-desorption mechanism is completely reversible. In the case of the sorption isotherms of the plasma pre-treated Nafion® 212, it is noted that there is no rise in water sorption isotherms at water activities above 0.7, probably due to the plasma pre-treatment carried out on the support Nafion® 212. The effect of the plasma pre-treatment most certainly leads to extreme surface cross-linking which results in the reduction of water uptake at high water activities. In fact, it is generally observed a strong rise in the water mass gain at the highest water activities, knowing that Nafion® is known to form water clusters with the famous Schroeder paradox between the vapor state and the liquid state of the water as it is the case for the untreated Nafion® 212. Then, the application of mathematical models to decouple the different contributions to water sorption of both plasma pre-treated Nafion® 212 and untreated Nafion® 212 as a function of water activity was implemented.  \n\n![](images/931f358d99d5b2577a46ef60c48b13b83f140e9fba78f6bacc63fc51b366b225.jpg)  \nFig. 5. Sorption isotherms for the plasma pre-treated Nafion® 212 and untreated Nafion® 212 according to the protocol: 1st rise in water activity $/$ desorption / 2nd rise in water activity and modeling of 1st sorption isotherms.  \n\nTable 3 Parameters obtained after modeling (1) by the Dual-Mode model of the first sorption curve (1st sorption isotherm) of the plasma pre-treated Nafion® 212 and (2) by the Park model of the first sorption curve (1st sorption isotherm) of the untreated Nafion® 212.   \n\n\n<html><body><table><tr><td></td><td>Nafion° 212 plasma pre-treated</td><td>Nafion° 212 untreated</td></tr><tr><td>AL</td><td>2.0</td><td>1.3</td></tr><tr><td>bL</td><td>51.3</td><td>233.8</td></tr><tr><td>KH</td><td>7.5</td><td>11.4</td></tr><tr><td>KH\".Ka.n</td><td></td><td>11.5</td></tr><tr><td>Ka</td><td></td><td>3.0 × 10-10</td></tr><tr><td>ｎ</td><td>一</td><td>9.1</td></tr></table></body></html>  \n\nIn the case of plasma pre-treated Nafion $\\circledast$ 212, Dual-Mode model comprising a Langmuir contribution ${\\frac{A_{L}b_{L}}{1+b_{L}}}a$ , for low water activities (less than 0.2), and a Henry contribution $K_{H}a,$ for higher activities, has been applied. The shape of the isotherm, concave then linear, is typically characteristic of this model with dual sorption mode [27]. Concretely, the Dual-Mode type isotherms correspond to a rapid saturation of the Langmuir sites before the dissolution of the penetrant in the matrix becomes preponderant [34]. After applying the Dual-Mode model equation on the first sorption curve (1st sorption isotherm), the modeling curve is perfectly superimposed on the experimental points, as shown in Fig. 5. The different parameters obtained from the modeling are summarized in Table 3.  \n\nIn the case of untreated Nafion® 212, it can be seen that the sorption curve obtained is comparable to those usually reported in the literature [35,36]. Indeed the shape of the sorption isotherm is sigmoidal; it is typical of sorption resulting from a complex combination of several modes of sorption, which can be mathematically described using the Park model [27]. In addition to take into account Langmuir's contribution to low water activities and Henry's contribution to intermediate activities, Park's model considers also a phenomenon of aggregation of the penetrant in the film with high water activities (here greater than 0.7). After applying the Park model equation on the sorption curve number one (1st sorption isotherm), the modeling curve is also perfectly superimposed on the experimental points, as showed in Fig. 5. Finally the different parameters obtained from the modeling are summarized in Table 3.  \n\nRegarding the experimental data and the modeling curves, it can be stated that the Dual-Mode model and the Park model are in perfect agreement with the experimental data and best describe respectively the experimental sorption isotherms of the plasma pre-treated Nafion® 212 and untreated Nafion® 212 in the entire range of water activity (from 0 to 0.95).  \n\nFig. 6 shows the sorption isotherms of PECVD membranes deposited on silicon wafer. Water sorption was performed on one side of the membrane because the deposit was in contact with water on only one side, the second face being in contact with the silicon wafer on which it was deposited. Because the deposits were characterized with their silicon support (mass significantly larger than the deposits themselves), the experimental values of mass gains are particularly low, less than $0.0010\\ ({\\mathrm{g/g)}}$ . Smoothed curves, for which water mass gains were recalculated by mathematical smoothing of experimental sorption kinetics, were added in Fig. 6. Since the mass gains are small, the difference between the measured values and the smoothed values is negligible. Moreover, the sorption isotherms, whether derived from experimental measurements or obtained by smoothing these measurements, have a similar and classic look of the sigmoidal type. The comparison of the isotherms according to the type of plasma discharge (continuous or pulsed) leads to believe that the membrane prepared in pulsed plasma discharge have a greater capacity to adsorb water than the one prepared in continuous plasma discharge, as previously observed by ellipsometry coupled with water sorption.  \n\n![](images/a86cf7faaf7224683aa9cef0daadc3a2186a1213c07662b544b7b48d5cc4a82a.jpg)  \nFig. 6. Sorption isotherms of PECVD membranes obtained from the measurement data (in $\\mathbf{g}/\\mathbf{g})$ , after mathematical smoothing (in $g/\\mathbf{g})$ and modeling by application of the equation of the Park model.  \n\nFrom a fundamental point of view, the application of mathematical models on the sorption isotherms of the PECVD deposits was carried out by applying the Park model because of the sigmoidal shape of the sorption isotherms. The convex form would indicate the water clustering in the film at water activities greater than 0.7. Indeed, Park model takes into account this hypothesis of aggregate formation resulting from penetrant-penetrant interactions stronger than the penetrant-substrate interactions. Because of their size, these water aggregates result in a restriction of the transport of the penetrant through the substrate (membrane), which generally induces a decrease in the diffusion coefficient. This model is found in the case of sorption of water in hydrophilic polymers or polymers with polar functions or with ionic groups such as polyelectrolyte [28].  \n\nAfter applying the Park model on the experimental sorption data, the different parameters from the modeling were obtained; they are summarized in Table 4. The lowest value of the constants pair $A_{L},~b_{L}$ (Langmuir contribution), obtained for the membrane prepared in the continuous plasma discharge, is characteristic of the reduction of surface solubility by water molecules. Indeed, the Langmuir sites correspond to the presence of specifically charged domains or micro-voids in which the water molecules can be sorbed. The decrease of the Langmuir $A_{L}$ and $b_{L}$ constants in the case of the membrane prepared in continuous plasma conditions is directly related to its less hydrophilic surface state and its less flexible polymer network compared with the membrane deposited in the pulsed plasma discharge. Thus the surface affinity with the water molecules is reduced when the deposit is made in continuous mode in comparison with that made in pulsed mode. Considering that the second mode of sorption is Henry contribution, which implies a random adsorption of water molecules, the $k_{H}$ constant (Henry's constant) is also affected by the continuous deposition mode. Indeed, the lower $k_{H}$ value in the case of deposition carried out in continuous mode is also justified by the accessibility of the water molecules inside the micro-cavities of the polymer matrix. As regards to the aggregation phenomenon that takes place in the core of the material and characterized by the constant $K_{a},$ we can observe that it is high in the case of the membrane prepared in continuous mode for the same reasons mentioned above, namely that the polymer membrane has less hydrophilic surface state and less polymer network flexibility and thus the accessibility of water in the bulk of the material is not facilitated. In fact these higher restrictions in the membrane prepared in continuous mode would lead to confinement effect which favors the water molecules to bond together and to form clusters. If the number of water molecules per aggregate $(n)$ seems to go in the same direction as the aggregation constant $K_{a},$ namely higher in the case of the membrane prepared in continuous mode, it is not surprising that the size of water clusters $(\\sim6$ molecules per aggregate) are rather similar for both plasma deposits modes which leads to comparable water sorption behaviors.  \n\nTable 4 Parameters obtained after modeling by Park model of smoothed sorption curves of PECVD membranes.   \n\n\n<html><body><table><tr><td>plasma</td><td>Membrane 1oo W - continuous</td><td>Membrane 10o W - pulsed plasma [DC =50%]</td></tr><tr><td>AL</td><td>0.000015</td><td>0.000022</td></tr><tr><td>bL</td><td>21.4</td><td>50.0</td></tr><tr><td>KH</td><td>0.000022</td><td>0.00015</td></tr><tr><td>kHn.Ka.n</td><td>0.00044</td><td>0.00051</td></tr><tr><td>Ka</td><td>6.46 × 1023</td><td>2.36×1017</td></tr><tr><td>n</td><td>6.0</td><td>5.6</td></tr></table></body></html>  \n\nBy observing the values of the constants $A_{L},\\ b_{L}$ (Langmuir contribution) and $k_{H}$ (Henry contribution) obtained for all types of material, namely plasma pre-treated Nafion® 212 and untreated Nafion® 212 (Table 3) and PECVD membranes (Table 4), it is observed that they are all much lower in the case of PECVD materials. This may lead to the conclusion that PECVD membranes have a lower water sorption capacity than Nafion® 212. However, for a better reliability of the comparisons between PECVD membranes and Nafion® 212, it is better to reason with the water uptakes of PECVD films without their support. Thus Fig. 7 shows the sorption isotherms as a function of water activity for the plasma pre-treated Nafion® 212 and untreated Nafion® 212 and PECVD membranes without support contribution. The support contribution was extracted by applying a factor of 1000 to the experimental sorption data, because after calculation, taking into account the mass density of the plasma films (from electronic densities measured in a previous work by our group [15]) and their estimated volume, the ratio deposit mass/(deposit $^+$ silicon wafer mass) was in the order of 1/1000. It should nevertheless be noted that water sorption was performed on only one side of the PECVD membranes (because their other side is in direct contact with the silicon wafer as a support) while it was performed on both sides of materials for the plasma pre-treated Nafion® 212 and untreated Nafion® 212. This should not change the sorption results as long as one or two faces are exposed to water, the water infiltrates quantitatively in the same way inside the microporosity until it is completely filled, but with more or less time depending on the thickness of the film. From a quantitative point of view, we found that  \n\n![](images/4348a4f1e88c48c52abd470a2cb4a960c39d3d65b132191b690746d16005b087.jpg)  \nFig. 7. Sorption isotherms of the plasma pre-treated Nafion® 212, untreated Nafion® 212 and PECVD membranes without support contribution.  \n\nPECVD membranes have higher water mass uptake (2 to 5 times higher at $a_{w}>0.7\\$ ) compared to Nafion $\\mathfrak{G}$ 212 (plasma pre-treated or untreated one). This is certainly related to the fact that the water sorption mechanism of polymer membranes is mainly governed by surface chemistry (presence of acid functions) [21]; the PECVD membranes are more hydrophilic and potentially richer in acidic functions than Nafion® 212 [30] as evidenced by the XPS analyzes. In addition, the water intake gap between the two families of PECVD membranes (i.e. continuous and pulsed discharge prepared deposits) is 1.6 to 4 times greater in the medium and high water activity ranges $(a_{w}>0.3)$ . As confirmation of the observations made previously, the PECVD membrane prepared in pulsed plasma discharge clearly have a greater capacity to adsorb water than the one prepared in continuous plasma discharge, despite its lower concentration of phosphonic acid functions. This is certainly due to its more flexible polymer network induced by its longer hydrocarbon chains and its more hydrophilic surface state as already mentioned.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# 3.6. Water permeability of PECVD membranes  \n\nFollowing the water sorption measurements, water permeation measurements were carried out at $25~^{\\circ}\\mathrm{C}$ by using a plane permeation cell, on PECVD membranes deposited on a plasma pre-treated Nafion® 212 and compared with virgin plasma pre-treated Nafion $\\circledast$ 212 and untreated Nafion $\\textcircled{\\mathfrak{P}}$ 212. Water permeation is a process that occurs in 3 steps: water sorption on the upstream side of the material, water diffusion through the material and water desorption on the downstream side of the material [37]. Fig. 8 shows the water permeability coefficients of all investigated materials calculated from the stationary permeation flux $(J_{s t})$ obtained from the permeation kinetic measurements. The calculation of permeabilities takes into account the thicknesses of plasma layers measured in dry conditions by SEM and corrected by the swelling rate (at $100\\%$ relative humidity) evaluated by ellipsometry. Thus, PECVD membranes have the following wet thicknesses: $234~\\mathrm{nm}$ for the film prepared in continuous plasma discharge, $348~\\mathrm{nm}$ for the film prepared in pulsed plasma discharge; and virgin plasma pre-treated Nafion® 212 and untreated Nafion® 212 have a wet thickness of $57\\upmu\\mathrm{m}$ (thickness measured with a sliding calipers). It can be seen in Fig. 8 that PECVD membranes have water permeabilities 10 to 30 times lower than that of virgin plasma pre-treated Nafion® 212 and untreated Nafion® 212. This is the consequence for a very low intrinsic diffusion capacity for the plasma deposits (directly related to their intrinsic highly crosslinked nature), which the good sorption capacity cannot counterbalance. These results are in good agreement with previous studies by Roualdès et al. [38] and Jiang et al. [39] on intrinsically sulfonic plasma membranes at least 10 times less permeable to methanol than Nafion® 117. Despite their intrinsic low diffusion ability, PECVD membranes are nonetheless competitive because of their small thickness. Concerning the permeabilities of Nafion $\\mathfrak{P}$ 212, we can say that the plasma pre-treatment has a small influence on the water transport probably due to the fact that plasma pre-treatment certainly leads to extreme surface cross-linking but doesn't affect the bulk of the Nafion® membrane which results in the rather close water permeabilities. The comparison of both families of PECVD membranes (i.e. continuous and pulsed discharge prepared deposits) shows a slight permeability increasing for the pulsed mode because of the structural differences previously mentioned such as: surface chemistry and polymer network flexibility.  \n\n![](images/b552c85a1d4d372209422f4d78b2d4aabef96f3bb0f88367862300ebfa5b80b9.jpg)  \nFig. 8. Water permeability of PECVD membranes, plasma pre-treated Nafion® 212 and untreated Nafion $\\circledast$ 212.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# 4. Conclusion  \n\nPhosphonic acid-based membranes with competitive sorption and permeation properties have been prepared in a RF-PECVD reactor by using a mixture of argon and precursor dimethyl allylphosphonate in the gaseous phase. Two different kind of supports have been used for the membranes preparation and characterization: silicon wafer (for SEM, XPS and ellipsometry analyses) and Nafion® 212 (for water contact angle, sorption and permeation investigations). The major interest of PECVD as the membranes preparation method comes from the fact it allows to obtain stable materials being dense, homogeneous, and strongly adherent on all types of support. Contact angle measurements revealed that phosphonic acid-based PECVD membranes are more hydrophilic than Nafion $\\mathcal{\\underline{{\\boldsymbol{\\mathfrak{G}}}}}$ 212 due to their higher concentration in acidic functions as proved by XPS analyzes. As a consequence of these differences of chemical nature, PECVD membranes present better water sorption properties (measured by ellipsometry or Cahn microbalance) than Nafion® 212. Comparing both kinds of PECVD membranes (prepared in both types of discharges), the PECVD membrane prepared in a pulsed plasma discharge presents the best sorption properties whereas it is less rich in acidic functions compared to the membrane deposited in a continuous plasma discharge. This may be due to the fact that the adsorption capacity of water in PECVD materials is partially controlled by the chain segment mobility which depends on the length of the polymer chains; now the pulsed plasma conditions enable deposits containing longer hydrocarbon chains and thus polymer chains with greater flexibility. Finally, as expected, permeability measurements have revealed that membranes prepared by PECVD (continuous or pulsed discharge prepared deposits) are 10 to 30 times less permeable to water than Nafion® 212 because of the very high diffusion resistance of the plasma deposits directly related to their intrinsic highly crosslinked nature compared to Nafion® 212. Presenting both higher water sorption ability and poorer water diffusion than Nafion®, PECVD membranes should show singular water management properties which could be a great advantage and a real interest for the final PEMEC and PEMFC applications.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 22,
+        "chunk": "# Declaration of Competing Interest  \n\nNone.",
+        "category": " References"
+    },
+    {
+        "id": 23,
+        "chunk": "# Acknowledgments  \n\nThe authors thank the University of Montpellier for PhD grant support. The authors also thank Didier Cot, Bertrand Rebiere (IEM Montpellier) for SEM analyses and Valérie Flaud (ICG Montpellier) for XPS analyses.",
+        "category": " References"
+    },
+    {
+        "id": 24,
+        "chunk": "# Supplementary materials  \n\nSupplementary material associated with this article can be found, in the online version, at doi:10.1016/j.tsf.2020.137918.",
+        "category": " References"
+    },
+    {
+        "id": 25,
+        "chunk": "# References  \n\n[1] K. Fujihara, T. Ohno, M. Matsumura, Splitting of water by electrochemical combination of two photocatalytic reactions on $\\mathrm{TiO}_{2}$ particles, J. Chem. Soc., Faraday Trans. 94 (1998) 3705–3709.   \n[2] J. Lin, P.-.H. Wu, R. Wycisk, P. Pintauro, PEM fuel cell properties of pre-stretched recast Nafion®, ECS Trans. 16 (2008) 1195–1204.   \n[3] K.O. Iwu, A. Galeckas, A.Y. Kuznetsov, T. Norby, Solid-state photoelectrochemical H2 generation with gaseous reactants, Electrochim. Acta 97 (2013) 320–325.   \n[4] K.O. Iwu, A. Galeckas, S. Diplas, F. Seland, A.Y. Kuznetsov, T. Norby, Effects of temperature, triazole and hot-pressing on the performance of TiO2 photoanode in a solid-state photoelectrochemical cell, Electrochim. Acta 115 (2014) 66–74.   \n[5] T.A. Zawodzinski, C. Derouin, S. Radzinski, R.J. Sherman, V.T. Smith, T.E. Springer, S. Gottesfeld, Water uptake by and transport through Nafion® 117 membranes, J. Electrochem. Soc. 140 (1993) 1041–1047.   \n[6] S.R. Samms, S. Wasmus, R.F. Savinell, Thermal stability of Nafion® in simulated fuel cell environments, J. Electrochem. Soc. 143 (1996) 1498–1504.   \n[7] S. M., R. T., N. A., K.K. D., M. J., About the choice of the protogenic group in PEM separator materials for intermediate temperature, low humidity operation: a critical comparison of sulfonic acid, phosphonic acid and imidazole functionalized model compounds, Fuel Cells 5 (2005) 355–365.   \n[8] S.J. Paddison, K.-.D. Kreuer, J. Maier, About the choice of the protogenic group in polymer electrolyte membranes: ab initio modelling of sulfonic acid, phosphonic acid, and imidazole functionalized alkanes, PCCP 8 (2006) 4530–4542.   \n[9] T. Sata, T. Yoshida, K. Matsusaki, Transport properties of phosphonic acid and sulfonic acid cation exchange membranes, J. Memb. Sci. 120 (1996) 101–110.   \n[10] S.V. Kotov, S.D. Pedersen, W. Qiu, Z.-.M. Qiu, D.J. Burton, Preparation of perfluorocarbon polymers containing phosphonic acid groups, J. Fluor. Chem. 82 (1997) 13–19.   \n[11] M. Yamabe, K. Akiyama, Y. Akatsuka, M. Kato, Novel phosphonated perfluorocarbon polymers, Eur. Polym. J. 36 (2000) 1035–1041.   \n[12] M. Yamada, I. Honma, Anhydrous proton conducting polymer electrolytes based on poly(vinylphosphonic acid)-heterocycle composite material, Polymer (Guildf) 46 (2005) 2986–2992.   \n[13] S.-.I. Lee, K.-.H. Yoon, M. Song, H. Peng, K.A. Page, C.L. Soles, D.Y. Yoon, Structure and properties of polymer electrolyte membranes containing phosphonic acids for anhydrous fuel cells, Chem. Mater. 24 (2012) 115–122.   \n[14] N. Agmon, The Grotthuss mechanism, Chem. Phys. Lett. 244 (1995) 456–462.   \n[15] A.J. Kinfack Leoga, L. Youssef, S. Roualdès, V. Rouessac, Phosphonic acid-based membranes as proton conductors prepared by a pulsed plasma enhanced chemical vapor deposition technique, Thin Solid Films 660 (2018) 506–515.   \n[16] K. Matsumoto, T. Higashihara, M. Ueda, Locally and densely sulfonated poly(ether sulfone)s as proton exchange membrane, Macromolecules 42 (2009) 1161–1166.   \n[17] T. Itoh, K. Hirai, M. Tamura, T. Uno, M. Kubo, Y. Aihara, Anhydrous proton-conducting electrolyte membranes based on hyperbranched polymer with phosphonic acid groups for high-temperature fuel cells, J. Power Sources 178 (2008) 627–633.   \n[18] J. Bassil, S. Roualdès, V. Flaud, J. Durand, Plasma-polymerized phosphonic acidbased membranes for fuel cell, J. Memb. Sci. 461 (2014) 1–9.   \n[19] A. Ennajdaoui, S. Roualdes, P. Brault, J. Durand, Membranes produced by plasma enhanced chemical vapor deposition technique for low temperature fuel cell applications, J. Power Sources 195 (2010) 232–238.   \n[20] A. Ennajdaoui, J. Larrieu, S. Roualdes, J. Durand, PECVD process for the preparation of proton conducting membranes for micro fuel cells. Impedance probe measurements and material characterizations, Eur. Phys. J. Appl. Phys. 42 (2008) 9–15.   \n[21] K. Fatyeyeva, C. Chappey, F. Poncin-Epaillard, D. Langevin, J.-.M. Valleton, S. Marais, Composite membranes based on Nafion® and plasma treated clay charges: elaboration and water sorption investigations, J. Memb. Sci. 369 (2011) 155–166.   \n[22] Z. Jiang, Z.-j. Jiang, Synthesis and optimization of proton exchange membranes by a pulsed plasma enhanced chemical vapor deposition technique, Int. J. Hydrogen Energy 37 (2012) 11276–11289.   \n[23] Z. Jiang, Z.-.J. Jiang, Plasma techniques for the fabrication of polymer electrolyte membranes for fuel cells, J. Memb. Sci. 456 (2014) 85–106.   \n[24] D.A. Shirley, High-resolution X-ray photoemission spectrum of the valence bands of gold, Phys. Rev. B 5 (1972) 4709–4714.   \n[25] J.H. Scofield, Hartree-Slater subshell photoionization cross-sections at 1254 and 1487 eV, J. Electron Spectros. Relat. Phenomena 8 (1976) 129–137.   \n[26] Eds, J.A. Barrie, J. Crank, G.S. Par (Eds.), Academic Press, London/ New York, 1968, pp. 259–313 Eds.   \n[27] C.E. Rogers, M.M. Labes, A. Weissberger (Eds.), Solubility and Diffusivity, Chap. 6 in: Physics and Chemistry of the Organic Solid State, Volume II, D. Fox, 6 Interscience Publishers, New York, 1965, pp. 509–635 EdsChap.   \n[28] G.S. Park, Transport principles-solution, diffusion and permeation in polymer membranes, NATO ASI Series, Series C Math. Phys. Sci. 181 (Synth. Membr.: Sci., Eng. Appl.) (1986) 57–107.   \n[29] D.E. Gray (Ed.), American Institute of Physics Handbook, Mc Graw-Hill, New York, 1989.   \n[30] Karren L. More, Juan Carlos Idrobo, Miaofang Chi, Kelly Perry, Dave Cullen, Harry Meyer, Shawn Reeves, Oak Ridge National Laboratory Oak Ridge, DOE Annual Merit Review, TN, 2011.   \n[31] Y. Bogdanova, V. Dolzhikova, D. Tsvetkova, I. Karzov, A. Alent’ev, Contact angles as indicators of the polymer surface structure, J. Struct. Chem. 52 (2011) 1187–1194.   \n[32] K.H. Kale, S.S. Palaskar, Structural studies of plasma polymers obtained in pulsed dielectric barrier discharge of TEOS and HMDSO on nylon 66 fabrics, J. Text. Inst. 103 (2012) 1088–1098.   \n[33] N. Inagaki, S. Kondo, T. Murakami, J. Appl. Polymer Sci., 29 (1984) 3595–3605.   \n[34] N. Follain, S. Roualdes, S. Marais, J. Frugier, M. Reinholdt, J. Durand, Water transport properties of plasma-modified commercial anion-exchange membrane for solid alkaline fuel cells, J. Phys. Chem. C 116 (2012) 8510–8522.   \n[35] M. Legras, Y. Hirata, Q.T. Nguyen, D. Langevin, M. Métayer, Sorption and diffusion behaviors of water in Nation 117 membranes with different counter ions, Desalination 147 (2002) 351–357.   \n[36] K. Fatyeyeva, C. Chappey, F. Poncin-Epaillard, D. Langevin, J.-.M. Valleton, S. Marais, Composite membranes based on Nafion® and plasma treated clay charges: elaboration and water sorption investigations, J. Memb. Sci. 369 (2011) 155–166.   \n[37] A.L. Rangel-Cárdenas, G.J.M. Koper, Transport in proton exchange membranes for fuel cell applications—a systematic non-equilibrium approach, Materials (Basel) 10 (2017) 576.   \n[38] S. Roualdes, I. Topala, H. Mahdjoub, V. Rouessac, P. Sistat, J. Durand, J. Power Sources 158 (2006) 1270–1281.   \n[39] Z. Jiang, Z.j. Jiang, X. Yu, Y. Meng, Preparation of proton exchange membranes by a plasma polymerization method and application in direct methanol fuel cells (DMFCs), Plasma Processes Polym. 7 (2010) 382–389.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# High and long-lasting antifogging performance of silane based hydrophilic polymer coating  \n\nQian Liu , Jianbing Cui , Tatsuo Kaneko , Weifu Dong , Mingqing Chen , Jing Luo , Dongjian Shi  \n\nThe Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, Jiangsu 214122, China",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# A R T I C L E I N F O",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# A B S T R A C T  \n\nKeywords: Interfacial interaction Strong adhesion Continuous antifogging Composite coating  \n\nThe inevitable presence of fog causes a loss of light transmission in optical materials and leads to many unacceptable and serious consequences. A promising strategy for avoiding fog is to modulate the wettability of the material surface and further change the formed way of droplets. Although many works achieved high antifogging coatings, they are lack of the long-lasting antifogging at varied conditions. In this work, a high adhesion strength and persistent antifogging capability hydrophilic coating is obtained by utilizing silane coupling agents containing double bonds such as triethoxyvinylsilane (A151) and 3-(trimethoxysilyl)propyl methacrylate (KH570) with 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and then compositing with poly(vinyl alcohol) (PVA). The coating composed of A151 has a relatively uniform and flat surface structure, due to weaker hydrolysis ability of A151 promoted the smooth condensation speed, compared to KH570. Thanks to the hydrophilic and hydrophobic balance properties of the A151-modulated coating network, the resultant coating exhibits good antifogging performance in the range of $0~^{\\circ}\\mathbf{C}$ to $90\\ {^\\circ}\\mathrm{C},$ , which keeps a light transmission of about $85~\\%$ . Surprisingly, the coating shows excellent adhesion $(350{-}700\\mathrm{kPa})$ to the substrate, which is significantly better than other conventional hydrophilic antifogging coatings, and the hydrophilic and hydrophobic modulation capability and the enhanced interfacial adhesion of A151 segments provide the basis of the coating for long-lasting antifogging, which would open up a new way of durable hydrophilic antifogging coatings.",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1. Introduction  \n\nOptical materials are wide used in a large number of visualization areas, including endoscopy [1,2], spectacle lenses [3–5], house decoration materials [6–8], windscreens [9], etc., to provide aesthetics, good observability and protection. Thus, the optical materials are required to have good optical performance in a variety of environments and operations. However, the changes in environmental parameters [10–12], or fluctuation in the temperature of the optical material [13,14], can lead to fogging on their surfaces, causing liquid droplets to block transmission of vision and reduce light transmission. The presence of fog may affect the professional judgement of doctors [15,16], shorten the visibility of eyeglasses as well as windscreens [17–19], hinder photosynthesis in plants [20], reduce the efficiency of photovoltaic conversion [21], and affect the visual evaluation and acceptance of food [22,23]. Therefore, it is an urgent necessity for development of effective antifogging strategies.  \n\nAntifogging coatings are considered to be the most promising approach to prevent fogging and significantly improve the light transmission of a substrate by eliminating visible light scattering. As a result, many researches have been devoted to creating transparent and antifogging surfaces. The main antifogging methods can be divided into active and passive antifogging. In active antifogging, the condensation of water droplets on the surface can be inhibited or even prevented by adjusting environmental parameters such as temperature, relative humidity, or air flow rate by additional wires or sensors [24–27]. In contrast, the passive antifogging utilizes surface-wetting properties, especially superhydrophobicity or superhydrophilicity, which are directly regulated by the material structures. The antifogging of the superhydrophobic surfaces is achieved by the extremely low surface energy leading to low friction coefficients between water droplets and the material surface as well as facilitating droplet migration [28]. On the other hand, hydrophilic surfaces allow droplets to diffuse rapidly into a continuous film [29,30], allowing incident light to transmit without being scattered and maintaining clarity, thereby preventing the formation of surface fog and inhibiting droplet growth to the critical size [31,32]. This process effectively avoids the pseudo-fog period, achieving efficient antifogging. Currently, some researches have used $\\mathbf{O}_{2}$ plasma etching to form nano-rough structure on the surface [33], by employed hydrophilic polymers (PEG) as hydrophilic active sites [34], or added surfactants (such as Polysorbate, Span 20 or Span 80) to achieve the purpose of antifogging [35]. Some researchers have also used the amphoteric monomer sulfobetaine to enhance the hydrophilicity, which is more conducive to the antifogging [36], or use the hydrophilic and hydrophobic components of the modulation to obtain antifogging coatings with good water resistance [37]. However, most researches on the hydrophilic antifogging coatings generally focus on the structure fabrication and the surface properties of coatings, which are obtained via the forces between the coating and the substrate including hydrogen bonding, metal coordination, and $\\pi{-}\\pi$ conjugation [38]. These weak interactions resulted in poor adhesion and instability of the coating. Therefore, considering the important influence of the capability of interfacial interactions on antifogging coatings, the utilization of stable covalent bonds to achieve strong interactions between the coating and the substrate is of great research significance.  \n\nHerein, we fabricated long-term antifogging coatings on transparent silicate glass substrates by copolymerization of triethoxyvinylsilane (A151) and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and complexation of poly(vinyl alcohol) (PVA) to form a hydrophilic/hydrophobic polymer network (denoted as PVA/P(A151-co-AMPS)). Specifically, the introduction of hydrophobic A151 not only inhibits the excessive swelling of the hydrophilic network, but also forms stable covalent interactions with the substrate and enhance the adhesion ability of the coating with hydrolysis of A151. The coating provides strong interfacial interaction $(350\\mathrm{-}700~\\mathrm{kPa})$ while effectively avoiding fog formation, and maintains high fogging transmittance $(>85\\ \\ \\%)$ within a long period over a wide range of temperatures $(0{-}90^{\\circ}\\mathbf{C})$ , with adhesion and antifogging capabilities significantly superior to those of similar products. The obtained PVA/P(A151-co-AMPS) coating paves the way for further commercial applications.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2. Experimental section",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.1. Materials  \n\nPoly (vinyl alcohol) (PVA-1799, $98\\mathrm{-}99\\mathrm{~\\}\\%$ , triethoxyvinylsilane (A151, $97~\\%]$ , 3-methacryloxypropyltrimethoxysilane (KH570, $97~\\%)$ , and initiator ammonium persulfate (APS, $98.5~\\%$ ) were purchased from Macklin. 2-Acrylamide-2-methylpropane sulfonic acid (AMPS, $98\\ \\%$ was obtained from Aladdin. All the materials and reagents were used without further purification. Glass $2.0\\ \\mathrm{mm})$ ) was purchased from Sinopharm Chemical Reagent Co., Ltd.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.2. Preparation of antifogging coating  \n\nAntifogging coating was prepared by thermal polymerization. Typically, PVA $(10~\\mathrm{wt\\%})$ aqueous solution was prepared by dissolved $1.0{\\mathrm{g}}$ PVA in $10{\\mathrm{g}}$ distilled water and stirred for $^{2\\mathrm{h}}$ at $95^{\\circ}\\mathrm{C}$ . $5\\mathrm{wt\\%}$ AMPS was added the above PVA solution at $60\\ {}^{\\circ}{\\bf C},$ and silane coupling agent (A151, $2\\mathrm{wt\\%}$ and the initiator APS were added sequentially after AMPS dissolved, and the reaction was continued for $^{2\\mathrm{~h~}}$ at $60~^{\\circ}\\mathrm{C}$ . Finally, the polymer solution obtained was spread uniformly on the glass surface using drip coating to obtain a coating film. The layer was further dried at $50^{\\circ}\\mathrm{C}$ for $^{2\\mathrm{h}}$ to obtain a dried polymer layer (abbr. as PVA/P $\\mathtt{\\backslash A151_{n}}\\cdot$ coAMPS)), in which n was the amount of A151. The preparation of PVA/P $\\mathrm{(KH570_{n}}$ -co-AMPS) layer was same with that of PVA/ $\\mathrm{P(A151_{n^{-}}c o^{-}}$ AMPS), just by substituted A151 as KH570.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.3. Measurement of antifogging performance  \n\nThe antifogging property of the sample was detected by hot steam and cold-fog conditions. Specifically, for the hot steam test, the samples were placed above a water bath at a constant temperature $(90~^{\\circ}\\mathrm{C})$ for 1 min with a distance of $1\\mathrm{cm}$ between the sample and the water surface, and then moved under ambient conditions to take a photo immediately. In order to investigate the antifogging properties of the samples, the light transmittance in the wavelength range of $400{\\scriptstyle-700}\\ \\mathrm{nm}$ was collected using a UV–Vis spectrophotometer (Shimadzu Corporation, UV-3600 PLUS). To make a comprehensive evaluation and direct comparison, we also used a test of antifogging resistance under hot steam at different temperatures $(90~^{\\circ}\\mathrm{C},70~^{\\circ}\\mathrm{C},50~^{\\circ}\\mathrm{C},30~^{\\circ}\\mathrm{C})$ and under cold condition $(0\\ ^{\\circ}\\mathbf{C})$ . In addition, a test of antifogging resistance time was also carried out (1 min, 3 min, 5 min, 7 min, $10\\mathrm{min}$ , $20\\mathrm{min}$ , $30\\mathrm{min}\\dot{}$ ).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.4. Wettability test  \n\nThe wettability of the sample was characterized by water contact angle (WCA) at a WCA measuring instrument (OCA15EC, Germany). The WCA was monitored on the samples with $3\\upmu\\mathrm{L}$ of droplets, and the time-related contact angle was collected every $1~\\mathrm{min}$ over a $10\\ \\mathrm{min}$ period.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.5. Lap shear adhesion test  \n\nThe adhesive strength of PVA/P(A151-co-AMPS) or PVA/P(KH570- co-AMPS) on glass was investigated by shear lap test according to GB/ T 7124-2008. PVA/P(A151-co-AMPS) and PVA/P(KH570-co-AMPS)) were directly coated on the glass, with an area of $1000\\ \\mathrm{mm}^{2}$ . The adherends were pressed together at $50^{\\circ}\\mathrm{C}$ for $^{2\\mathrm{h}}$ before testing. The lap shear adhesion test was carried out on a testing machine with a pressuremeasuring element of $5~\\mathrm{kN}$ and pulled apart at a speed of $5\\ \\mathrm{mm/min}$ until failure. The adhesion strength was calculated by dividing the force at breakage by the overlap area.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 2.6. Abrasion resistance, ageing resistance and water resistance test  \n\nThe abrasion resistance of PVA/P(A151-co-AMPS) was measured by pushing and pulling a coated glass continuously up and down in quartz sand with a diameter of $500~{\\upmu\\mathrm{m}}$ . The ageing resistance test was performed by exposing the coated glass to UV light at $365~\\mathrm{{nm}}$ . For water resistance, the coated glass was immersed in deionized water and then tested for anti-fog after drying. In order to assess the adhesion of the coating to the substrate, the coating immersed in deionized water was dried and then subjected to a tape peel test, where the tape was applied to the coating and then peeled off by rolling it with a $_{100~g}$ weight, and the anti-fogging properties of the coating were immediately tested. The antifogging properties of the coatings were tested after each test by placing the coated glass $1\\mathrm{cm}$ above hot water at $50^{\\circ}\\mathrm{C}$ for $10\\mathrm{min}$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# 2.7. Characterization  \n\nThe chemical structures of the coating were characterized by the Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR, Nicolet iS50). ATR-FTIR spectra were collected in the wavenumber range of $4000{-}400\\mathrm{cm}^{-1}$ on an instrument assisted by ATR attachments. The surface morphology of the sample was observed by optical microscopy (VHX-1000C, Hong Kong). Elemental analysis was acquired from the energy dispersive spectroscopy (EDS) device attached to the SEM (S-4800, Japan). An atomic force microscope (AFM, MuLtimode 8) was employed to exam the surface roughness of the samples. The Parallel steel plates with a diameter of $20~\\mathrm{mm}$ was selected for rheological property tests.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3. Result and discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.1. Characterization of antifogging coatings  \n\nAs illustrated in Fig. 1, the antifogging coating was formed by casting the polymer solution on the substrate by the drip coating method and further curing at $50~^{\\circ}\\mathrm{C}_{:}$ , the thickness of the coating obtained was approximately $30~{\\upmu\\mathrm{m}}$ (Fig. S1a). During the curing process, a classical dehydration condensation reaction occurred among silane coupling agents and between silane coupling agents and glass, resulting in forming stable covalent bonds for enhancing the interfacial interaction between the coating and the substrate.  \n\n![](images/80a8492b31698799e03fb1757e090e0343fa781131095d7918b35f86745a69dc.jpg)  \nFig. 1. (a) Schematic preparation of the PVA/P(A151-co-AMPS) coating, and (b) the synthesis mechanism of P(A151-co-AMPS) coating.  \n\nChemical structures of PVA/P(A151-co-AMPS) and PVA/P(KH570- co-AMPS) were investigated by FTIR. As shown in Fig. 2a, the peaks at $1095~\\mathrm{cm}^{-1}$ and $3404~\\mathrm{cm}^{-1}$ corresponded to the stretching vibrations of $\\mathtt{C-O}$ and -OH on PVA. The absorption peaks at $1722~\\mathrm{{cm}^{-1}}$ , 1550 $\\mathsf{c m}^{-1}$ , and $1032\\mathrm{cm}^{-1}$ corresponded to the stretching vibrations of $\\scriptstyle\\mathtt{C=}0$ , ${\\tt N}\\mathrm{-H}$ , and S–O on AMPS. And the peak at $1093~\\mathrm{{cm}^{-1}}$ was the absorption peak of $s\\mathrm{i}{-}0$ in A151 and KH570, the appearance of these absorption peaks indicated the successful preparation of the coatings. As shown in Fig. 2b, the viscosity of the PVA/P(A151-co-AMPS) solution increased compared with the PVA/A151/AMPS solution, indicating the formation of P(A151-co-AMPS) network. The surface morphology of the PVA/P(A151-co-AMPS) coating was slightly different compared to the glass (Fig. S1b, c), and AFM show that the coating was differentiated from pure glass as far as roughness was concerned (Fig. 2e, f), and the morphology observation indicated the successful preparation of the coatings on the glass surface. EDS elemental mapping revealed that the polymer was uniformly coated on the surface of the glass (Fig. 2c, d), with the content of N, Si, and S elements of the coating being $71.0\\%$ , 2.2 $\\%$ , and $26.8~\\%$ , respectively (Fig. S2). Compared with PVA/P(A151-coAMPS), the surface morphology of PVA/P(KH570-co-AMPS) was rougher (Fig. S3a), and a small amount of KH570 agglomerated to form polymer particles in the Si elemental mapping (Fig. S3b). Since the hydrolysis of alkoxy group in KH570 was stronger than that of in A151, KH570 was more easily to polycondensation, and thus affected the surface morphology of the coating.  \n\n![](images/fef0e8579f372830b1a22622302ac8bbf98d0e0abbd6343bd8dc9b520de2b07b.jpg)  \nFig. 2. (a) FTIR spectra of PVA/P(A151-co-AMPS), A151, PVA/P(KH570-co-AMPS) and KH570. (b) Rheological characterization of PVA/P(A151-co-AMPS) and PVA/A151/AMPS solutions. Mapping images of (c) Si and (d) S elements. The AFM photo of (e) pure glass and (f) PVA/P(A151-co-AMPS) coating.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3.2. Antifogging property  \n\nThe antifogging properties was tested by hot steam. The coated glass and bare glass were exposed to hot water vapor ${\\bf\\langle-90^{\\circ}C}$ 1 cm above) for 60 s. The antifogging test photographs were taken immediately after the samples were moved over the letter paper, and the antifogging performance was evaluated by the average transmittance at $400{\\-}700\\ \\mathrm{nm}$ . The effect of PVA amounts on the antifogging coating was first investigated, as shown in Fig. S4a, 2b. The coatings with $5\\ \\mathrm{wt\\%}$ PVA affected the overall performance of the antifogging coating, although it had better light transmission, the coatings had almost lost the antifogging ability (Fig. S4b), and thus $5\\ \\mathrm{wt\\%}$ PVA was not desirable for the antifogging coating. Then, the antifogging properties of the coatings with $10~\\mathrm{wt\\%}$ PVA was detected in detail.  \n\nTo understand more intuitively the effect of the silane coupling agents on the properties of the coatings, light transmission of the coatings with different amounts of A151 and their optical photo images of antifogging properties (same color as the curve of light transmittance) were investigated and shown in Fig. 3. The glasses without and with various coatings were transparent and the letters underneath were clearly visible (Fig. 3a), and the best light transmission was achieved 80 $\\%$ for the coating with $2\\mathrm{wt\\%}$ of A151 before atomization. To investigate the antifogging performance of the coatings, the transmittance and photo images were taken after the samples were placed above hot water at $90^{\\circ}\\mathrm{C}$ for $1\\mathrm{min}$ (Fig. 3b). Without the protection of the antifogging coating, water vapor formed small droplets on the bare glass, causing refraction and reflection of light, leading to a significant reduction in transmittance. For the glass with coatings, only the coating with $2\\mathrm{wt\\%}$ of A151 had no fog layer and the light transmission was ${\\sim}85~\\%$ , while the coatings with other amounts of A151 $5\\mathrm{wt\\%}$ , $10\\mathrm{\\wt{\\%}}$ ) were visibly fogged. With the low amount of A151, the coating was able to rapidly absorb the surrounding water vapor, which quickly diffused to the surface, increasing the light transmission and achieving antifogging. In the case of a large amount of A151, a large amount of hydrolyzed A151 will self-condensing and exhibit phase separation, reducing the light transmission and the coating loses its antifogging properties. For the coating PVA/P(KH570-co-AMPS), the light transmittance was weaker than that of PVA/P(A151-co-AMPS) (Fig. 3a), even with low amount of KH570, and the PVA/P(KH570-co-AMPS) coating showed lower antifogging (Fig. 3b). The possible reason was that the stronger hydrolysis of KH570 than that of A151, resulting in KH570 chains condensed together and more obvious hydrophobic effect occurred under atomization conditions. The antifogging mechanism of the coating is shown in Fig. 3c. Large number of hydrophilic groups in PVA and AMPS improve the surface energy of the composite coating, so that the fog spread uniformly on the surface to form a hydration layer, leading a high transmittance. However, for the glass without hydrophilic coating or with high hydrophobic coating, the fog condensed on the surface, grew, and finally formed water droplets, leading to obvious refraction and reflection of light, reducing the light transmittance, and therefore showing low antifogging capability.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 3.3. Wettability of coatings  \n\nTo further explored the antifogging properties of the PVA/P(A151- co-AMPS) coatings, the wettability of the coating were evaluated. The photographs of the water contact angle as a function of time and the values are shown in Fig. S5 and Fig. 4. As shown in Fig. 4a, the initial WCA of the coated glass surfaces was about $70^{\\circ}-80^{\\circ}$ , twice of that of the pure glass. As the A151 amounts in PVA/P(A151-co-AMPS) increased, the more Si-OH groups were produced by hydrolysis of the silanoxy groups, which reduced the surface energy of the coatings to be more hydrophilic and affected the initial contact angle of PVA/P(A151-coAMPS). In addition, time-dependent WCA measurements were used to further investigate the change in wettability of the coatings (Fig. 4a, b). The WCA values of all the coatings steadily decreased by approximately $35^{\\circ}$ over a 600-s time interval, while the WCA values of the pure glass decreased by approximately $17^{\\circ}$ . The WCA values indicated that the coatings absorbed a portion of the water from the water droplets in addition to the evaporation of water from the surface. Due to its beneficial absorptive capacity, the initially condensed water was immediately absorbed by the coating, leaving a fog-free surface.  \n\n![](images/3a159cc1c38f8785cc04fd2ff0c5f2c6e56d81829a26d5419a8c5be5b9926047.jpg)  \nFig. 3. Light transmittance (a) and atomized transmittance (b) of different coatings. (c) Schematic diagram of coating antifogging mechanism.  \n\n![](images/14193322e02b9decee2d2f6b181f23831190c9ac2bfc1d614f1955736d8b0ea6.jpg)  \nFig. 4. Water contact angles of PVA/P(A151-co-AMPS) with different A151 amounts at $5\\mathrm{\\wt\\%}$ (a) and $10~\\mathrm{wt\\%}$ (b) PVA.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 3.4. The interface strength of the coating  \n\nTo illustrate the superiority of the silane coupling agent in enhancing the adhesion strength between the coating and the glass, a lap shear test was performed as shown in Fig. 5a and the adhesion strength were obtained in Fig. 5b. Compared with PVA and PVA/PAMPS, the $\\mathbf{PVA_{10}/P}$ $(\\mathsf{A}151_{\\mathrm{n}}$ -co-AMPS) increased the interfacial adhesion by approximately 2-fold, which was attributed to the covalent condensation between A151 and the glass. With the increasing of the silane coupling agent content (Fig. 5b), the adhesion strength could increase to $700~\\mathrm{kPa}$ at $10\\ \\mathrm{wt\\%}$ A151 addition. When the silane coupling agent was KH570, the adhesion of the coating to the glass was slightly higher than that of A151 (Fig. S6, S7), probably due to the higher hydrolysis rate of KH570 increased the adhesion between the coating and the glass per unit area, as seen by the EDS elemental mapping (Fig. S3b). The uneven distribution of KH570 and the chains clustered together, which in turn affected the overall surface morphology of the coating (Fig. S3a), and the excessive roughness seriously affected the light transmission and antifogging performance of the coating (Fig. 3).  \n\nThe superiority of A151 for enhancing the adhesion of antifogging coatings was strong interfacial bonds provided by the partial hydrolysis of siloxanes on A151 to form Si-O-Si bonds with the glass, and significantly improved the adhesion strength of the coatings. The adhesive strengths of the coatings on silicate glass were higher than most of commercial glues and higher-performance polymer adhesives in the literatures [39–48], especially, the strength of the $\\mathrm{PVA_{10}}/\\mathrm{P}(\\mathrm{A}151_{10^{-}}\\mathrm{c}_{0^{-}}$ AMPS) coating was highest than that of the previous reports (Fig. 5c).  \n\n![](images/9d7386cbaf2a91a3de1d87f21048eadc8661a96dc9a161fea2cba9ecb2f0f4ef.jpg)  \nFig. 5. (a) Schematic illustration of measurement of adhesive strength based on the lap-shear test. (b) The adhesion strength of PVA/P(A151-co-AMPS) under different A151 additions at $5\\mathrm{\\wt\\%}$ and $10~\\mathrm{wt\\%}$ PVA additions. (c) Comparison of adhesion strengths of the PVA/P(A151-co-AMPS) on the glass substrate to other polymer adhesives reported in the literature. The error bars represent the standard deviation, and sample numbers, $n=3$ .",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# 3.5. Abrasion resistance, ageing resistance and water resistance  \n\nThe silane coupling agent A151 played two roles in this antifogging coating: exhibiting cross-linking through dehydration condensation and enhancing the adhesion strength. Considering that the practical application of the coating, the coating $\\mathrm{(PVA_{10}/P(A151_{2}}$ -co-AMPS) as an example) was subjected to abrasion tests (Fig. 6a) and ageing tests (Fig. 6b). After prolonged abrasion tests (250 cycles) and 7 days of continuous exposure to a UV source with a wavelength of $365~\\mathrm{{nm}}$ , the coating retained its good light transmission and antifogging properties. After 250 abrasion tests, the surface of the coating showed slight scratches (Fig. S8) and increased roughness (Fig. S9), but the antifogging performance was not affected, and the coating showed robust mechanical strength. The water resistance of the coatings was assessed by performing an antifog test after the samples were immersed in water for different times and dried. As shown in Fig. 6c, even after being immersed in water for $4\\mathrm{h}$ , the light transmission of the coating in the anti-fog test was still higher than ${>}85\\%$ . Due to the condensation of the coating with the glass surface to formed Si-O-Si covalent bonds, the coating was firmly bonded to the glass, resulting in the long-lasting anti-fogging performance. Additionally, the adhesion strength between the coating and the glass after $^\\textrm{\\scriptsize1h}$ of water immersion was further tested by tape peeling to assess the water resistance of the coating. The tape was fully applied to the sample and then rolled back and forth several times with a $_{100\\mathrm{~g~}}$ weight to ensure a tight fit with the coating, and finally, the tape was peeled off at a constant speed. The stability of the coating was further investigated using cycles of peeling the tape (e.g. 0, 10, 20 and 30 times). The results were shown in Fig. 5d. After 30 times of peeling, the antifogging transmittance of the coating remained stable $(85~\\%)$ . In summary, the good durability of the coatings is mainly attributed to the fact that due to the covalent bonding of the coating with the glass and the composite of the coating with PVA.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 3.6. Antifogging durability  \n\nThe temperature resistance employing hot steam and cold fogging were also detected. In Fig. 7a, during the initial antifogging stage (the first $1\\mathrm{min}\\mathrm{.}$ ), a slight disparity was observed in the light transmission rate of the glass coated with antifogging coating under water vapor at different temperatures. This discrepancy was attributed to the direct influence of temperature on the kinetic energy of water molecules, consequently affecting the collision frequency between water molecules and the coating surface within a given time interval. As a result, the temperature influenced the interaction between the coating and water molecules, leading to some variability in the light transmittance of the initial antifogging coating. Nonetheless, the observed light transmittance exceeded $80~\\%$ in all cases. Thus, it was believed that a successful antifogging effect was achieved when the average transmittance of the coating surpassed $80\\%$ .  \n\nThe transmittance at wavelengths of $400{\\-}700\\ \\mathrm{nm}$ at different temperatures is shown in Fig. S10, and the relationship of transmittance and temperature is summarized in Fig. 7b. The transmittance of the PVA/P (A151-co-AMPS) coated glass increased slightly at temperatures equal to or lower than $50^{\\circ}\\mathrm{C}$ with prolonged the water vapor evaporation time. This phenomenon occurred as the water molecules in contact with the coating gradually spread out, compensating for the coating surface defects and avoiding the loss of light reflection and light refraction. At the same time, the coated glass exhibited high time-independent optical transmittance $(\\sim89~\\%)$ under this condition. Conversely, at higher temperatures $70^{\\circ}\\mathrm{C}$ and $90~^{\\circ}\\mathrm{C})$ , the Brownian motion of water molecules was more intense, and the optical transmittance of the coated glass was lower than $80\\%$ at $10\\mathrm{min}$ and $5\\mathrm{min}$ , respectively, which could be attributed to the excessive water accumulation and limitation of water absorption for the coating. Overall, these findings provided valuable insights into the temperature-dependent behavior of antifogging coating and the coating was effective in preventing the formation of fog on the glass over a wide temperature range $(30\\ ^{\\circ}\\mathbf{C}\\ {\\boldsymbol{\\cdot}}90\\ ^{\\circ}\\mathbf{C})$ under hot steam conditions. The reusability of the antifogging coatings with high optical transmittance is a great challenge and is critical for practical applications. The glass with the PVA/P(A151-co-AMPS) coating was tested at $50^{\\circ}\\mathrm{C}$ for $10\\mathrm{min}$ or $20\\mathrm{min}$ over 20 cycles. As shown in Fig. 7c, the light transmission of the coating still exceeded $85\\%$ , which indicated that the coating could withstand at hot steam and repeated use under high light transmission conditions.  \n\n![](images/c7f0dbeadfe10a49a3184c9ec508b220d385fdafd35563a8e60f3cc322d6c384.jpg)  \nFig. 6. (a) Sand abrasion cycles. Inset pictures show the abrasive process and antifogging test before and after abrasion treatment. (b) UV irradiation test at $365\\mathrm{nm}$ of UV light. Inset pictures show antifogging test before and after UV irradiation treatment. (c) Transmittance of $\\mathrm{PVA_{10}}/\\mathrm{P}(\\mathrm{A}151_{2}$ -co-AMPS) in the antifogging test by immersed the coated glass in deionized water for different times and then dried. (d) Transmittances of the coated glass in antifogging tests. Tape peel test of coated glass after $^\\textrm{\\scriptsize1h}$ of deionized water immersion.  \n\n![](images/2add382451593408b13e9795fde087a0d604a49d135b514b13caad5e1c75b275.jpg)  \nFig. 7. Thermal antifogging properties and reusability of PVA/P(A151-co-AMPS) coatings on glass. a) Average transmittance of the coated glass for the first minute at different temperatures. b) Variation of transmittance of coated glass with time under water vapor at different temperatures. c) Average transmittance of coated glass slides for repeated antifogging tests $\\ensuremath{\\mathrm{?0}}\\ensuremath{\\mathrm{min}}$ and $20~\\mathrm{{min}}$ ) at the water temperature of $50~^{\\circ}\\mathrm{C}$ The coating was dried (D) at $50~^{\\circ}\\mathrm{C}$ before and after each test.  \n\nIn addition, the cold antifogging performance of the PVA/P(A151- co-AMPS) coating was evaluated by refrigerating the coated glass slide at $0^{\\circ}\\mathsf{C}$ for 1 h and then exposing it to the ambient environment $(\\sim25^{\\circ}\\mathsf C,$ $55\\mathrm{-}60\\%$ RH). The light transmission of the bare glass was only about 15 $\\%$ (Fig. 8 aI), which seriously affected the visual performance. Whereas the coated glass was unaffected in the cold condition (Fig. 8b) and still maintained the same or even higher light transmission of around $85\\%$ (Fig. 8 aIV). Remarkably, after $7200\\ \\mathrm{min}$ of refrigeration (Fig. 8c), the coated glass was still able to keep its high light transmission of ${\\sim}85~\\%$ .  \n\nAdditionally, the coated glass showed excellent reusability (Fig. 8d) even after being refrigerated for $30\\mathrm{min}$ or $60\\ \\mathrm{min}$ .  \n\nThese results suggested that the coating demonstrated excellent cold antifogging properties under both high temperature and low temperature conditions, making it suitable for a wide range of practical applications.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# 4. Conclusions  \n\nIn summary, a hydrophilic antifogging coating with strong interfacial adhesion achieved long-lasting antifogging on the substrate. This coating was prepared based on the copolymerization of the hydrophobic monomer A151 and the hydrophilic monomer AMPS and then composited with PVA, resulting in an antifogging coating. Since the hydrolyzed A151 end-groups can form covalent bonds with the target surface, it showed excellent adhesion ability and avoids interfacial failure. Meanwhile, the polymerized A151 limited to some extent the excessive swelling of the coating under fogging conditions. As a result, PVA/P(A151-co-AMPS) coating maintained high light transmittance $(>85~\\%)$ under the ability of strong adhesion $(350-700~\\mathrm{kPa})$ ) for a long time $(>30\\mathrm{min}$ ) over a wide temperature range $(0{-}90^{\\circ}\\mathrm{C})$ , which had the advantages of strong adhesion ability, long antifogging time, high transparency, and reusability stability. In addition, it provides ideas for the development and design of functional antifogging coatings for the study of interfacial adhesion.  \n\n![](images/4c89b2c41b41d8fbaf4fa606ebfdb14834f05362a4cb5472d3b26fbb44d4d50b.jpg)  \nFig. 8. The cold antifogging performance of the PVA/P(A151-co-AMPS) coating. (a) Light transmittance of pure glass and coated glass before and after refrigeration at $0^{\\circ}\\mathrm{C}$ for $\\begin{array}{r}{1\\mathtt{h},}\\end{array}$ , and corresponding optical photographs (b). (c) The light transmittance of coated glass after different refrigeration times. (d) The light transmittance of the same coated glass before and after refrigeration changes with the number of refrigeration times at $0~^{\\circ}\\mathrm{C}$ .",
+        "category": " Conclusions"
+    },
+    {
+        "id": 21,
+        "chunk": "# CRediT authorship contribution statement  \n\nQian Liu: Writing – review & editing, Writing – original draft, Methodology, Investigation, Formal analysis, Data curation, Conceptualization. Jianbing Cui: Validation. Tatsuo Kaneko: Supervision, Conceptualization. Weifu Dong: Conceptualization. Mingqing Chen: Validation, Supervision, Funding acquisition, Conceptualization. Jing Luo: Validation, Supervision, Investigation. Dongjian Shi: Writing – review & editing, Validation, Supervision, Methodology, Investigation, Data curation, Conceptualization.",
+        "category": " Abstract"
+    },
+    {
+        "id": 22,
+        "chunk": "# Declaration of competing interest  \n\nThe authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 23,
+        "chunk": "# Data availability  \n\nData will be made available on request.",
+        "category": " References"
+    },
+    {
+        "id": 24,
+        "chunk": "# Acknowledgements  \n\nThis work was supported by the National Natural Science Foundation of China (52103165, 22103029), MOE & SAFEA for the 111 Project (B13025).",
+        "category": " References"
+    },
+    {
+        "id": 25,
+        "chunk": "# Appendix A. Supplementary data  \n\nSupplementary data to this article can be found online at https://doi. org/10.1016/j.porgcoat.2024.108690.",
+        "category": " References"
+    },
+    {
+        "id": 26,
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Kang, Coordinationdriven surface zwitteration for antibacterial and antifog applications, Langmuir 38 (4) (2022) 1550–1559, https://doi.org/10.1021/acs.langmuir.1c03009.   \n[39] X. Liu, Q. Zhang, L. Duan, G. Gao, Bioinspired nucleobase-driven nonswellable adhesive and tough gel with excellent underwater adhesion, ACS Appl. Mater. Interfaces 11 (6) (2019) 6644–6651, https://doi.org/10.1021/acsami.8b21686.   \n[40] G. Gao, F. Yang, F. Zhou, J. He, W. Lu, P. Xiao, H. Yan, C. Pan, T. Chen, Z.L. Wang, Bioinspired self-healing human–machine interactive touch pad with pressuresensitive adhesiveness on targeted substrates, Adv. Mater. 32 (50) (2020) 2004290, https://doi.org/10.1002/adma.202004290.   \n[41] D. Lee, H. Hwang, J.-S. Kim, J. Park, D. Youn, D. Kim, J. Hahn, M. Seo, H. Lee, VATA: a poly(vinyl alcohol)- and tannic acid-based nontoxic underwater adhesive, ACS Appl. Mater. Interfaces 12 (18) (2020) 20933–20941, https://doi.org/ 10.1021/acsami.0c02037.   \n[42] N. Han, Z. Xu, C. Cui, Y. Li, D. Zhang, M. Xiao, C. Fan, T. Wu, J. Yang, W. Liu, A Fe3 $^+$ -crosslinked pyrogallol-tethered gelatin adhesive hydrogel with antibacterial activity for wound healing, Biomater. Sci. 8 (11) (2020) 3164–3172, https://doi. org/10.1039/d0bm00188k.   \n[43] H. Fan, J. Wang, J.P. Gong, Barnacle cement proteins-inspired tough hydrogels with robust, long-lasting, and repeatable underwater adhesion, Adv. Funct. Mater. 31 (11) (2020) 2009334, https://doi.org/10.1002/adfm.202009334.   \n[44] D. Wang, J. Cui, M. Gan, Z. Xue, J. Wang, P. Liu, Y. Hu, Y. Pardo, S. Hamada, D. Yang, D. Luo, Transformation of biomass DNA into biodegradable materials from gels to plastics for reducing petrochemical consumption, J. Am. Chem. Soc. 142 (22) (2020) 10114–10124, https://doi.org/10.1021/jacs.0c02438.   \n[45] C. Cui, C. Fan, Y. Wu, M. Xiao, T. Wu, D. Zhang, X. Chen, B. Liu, Z. Xu, B. Qu, W. Liu, Water-triggered hyperbranched polymer universal adhesives: from strong underwater adhesion to rapid sealing hemostasis, Adv. Mater. 31 (49) (2019) 1905761, https://doi.org/10.1002/adma.201905761.   \n[46] L. Xu, S. Gao, Q. Guo, C. Wang, Y. Qiao, D. Qiu, A solvent-exchange strategy to regulate noncovalent interactions for strong and antiswelling hydrogels, Adv. Mater. 32 (52) (2020) 2004579, https://doi.org/10.1002/adma.202004579.   \n[47] D. Zhang, Z. Xu, H. Li, C. Fan, C. Cui, T. Wu, M. Xiao, Y. Yang, J. Yang, W. Liu, Fabrication of strong hydrogen-bonding induced coacervate adhesive hydrogels with antibacterial and hemostatic activities, Biomater. Sci. 8 (5) (2020) 1455–1463, https://doi.org/10.1039/c9bm02029b.   \n[48] Z. Yu, P. Wu, Underwater communication and optical camouflage Ionogels, Adv. Mater. 33 (24) (2021) 2008479, https://doi.org/10.1002/adma.202008479.",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Surface wettability and stability of chemically modified silicon, glass and polymeric surfaces via room temperature chemical vapor deposition  \n\nVania Silverioa,b,⁎, Patricia A.G. Cananea, Susana Cardosoa,b  \n\na INESC Microsystems and Nanotechnologies, INESC MN, 1000-029 Lisboa, Portugal b Department of Physics, Instituto Superior Tecnico, Universidade de Lisboa, 1040-001 Lisboa, Portugal",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# G R A P H I C A L A B S T R A C T  \n\nRoom temperature chemical vapor deposition was used to modify surface wettability of materials commonly used in the fabrication of microfluidic devices: rigid flat surfaces of silicon (Si), glass, SU-8 photoresist and PDMS (polydimethylsiloxane). The efficiency of surface coverage and consequently the efficiency and stability of surface wettability modification are seen to be highly dependent on the availability of –SiOH groups at the surface and the time of surface activation. Surface wettability after CVD modification was perceived to be governed by the wettable nature of the tail group deposited at the surface.  \n\n![](images/caf47779fc10d47d9d80f32c20fe284d6dd08c7349fd90967cc4aa0b66ef9a62.jpg)",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# A R T I C L E I N F O",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# A B S T R A C T  \n\nKeywords:   \nSurface wettability modification   \nRoom temperature chemical vapor deposition   \nMicrofluidics   \nMicrofabrication  \n\nWettability of surfaces used in microdevices, either on the fabrication of fluidic passages or integration of sensing and actuating elements can impact the flow. The easiness of fabrication may dictate the materials and processes to use, that can subsequently have their surface wettability spatially controlled. The work reports surface wettability modification (SWM) by room temperature chemical vapor deposition (CVD) with HMDS (hexamethyldisilazane) and FDTS (perfluorodecyltrichlorosilane) on flat surfaces of silicon (Si), glass, SU-8 photoresist and PDMS (polydimethylsiloxane). The effect of SWM has been evaluated by the measurement of contact angles (CA) of $6{\\upmu\\mathrm{L}}$ droplets of deionized water and phosphate-buffered saline buffer (PBS). Time of surface exposure and evolution of CA after modification have been investigated for each pair surface/fluid. The time of surface activation with HMDS or FDTS and the chemical affinity of these to the surface are seen to govern the efficiency of surface coverage and consequently the efficiency and stability of SWM. For both HMSD and FDTS SWM, hydrophilic surfaces (glass and Si) became more hydrophobic (CA rising from $20^{\\circ}$ up to ${\\bf\\tilde{\\Gamma}}^{70^{\\circ}}$ ) while SU-8 hydrophobic surfaces became more hydrophilic (CA decreasing from $120^{\\circ}$ down to $\\mathrm{\\tilde{\\tau}}_{100}\\mathrm{\\cdot}$ upon $30\\mathrm{min}$ activation. PDMS surfaces shows no relevant SWM after activation with HMDS nor with FDTS. SWM of Si surfaces has remained irreversible following CVD exposure (HMDS and FDTS) for at least $65\\mathrm{h}$ .",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# 1. Introduction  \n\nMicrofluidic devices have received much attention in the past years due to their competitive advantages, especially regarding their reduced sample and reagent consumption, analysis time and increased automation. To build and use microfluidic passages, the characteristics of the materials at hand must be considered: minimum/maximum operating temperature, resistance and conductivity, electroosmotic mobility which influences analyte affinity, surface energy that plays an important role in surface wettability, among others. PDMS (polydimethylsiloxane), silicon, glass and SU-8 photoresist are all widely used materials in the fabrication of microfluidic devices [1–3]. Therefore are now references when novel surfaces are addressed for microchannel fabrication.  \n\nMicrofabrication and usage of microfluidic devices are extremely dependent on forces at the surface. Hydrogen bonds and van der Waals forces are sufficient to promote unwanted adhesive joint between PDMS microfluidic structures and SU-8 masters, adding difficulty in device peeling. On the other hand, adhesion forces between polymers (usually materials of high surface energy) and glass or metallic foils (usually low surface energy materials) are very week and require additional chemical reactions of highly reactive functional groups at the interface to promote strong covalent chemical bonds [4]. Surface wettability modification (SWM) appears as a very useful tool to tune these materials surface energy [5–7] not only for adhesion purposes for example in microfabrication or microfluidics [8,9], but also for inhibition of nonspecific adsorption of analytes at the surface [10,11], anti-stiction surfaces [12] or self-cleaning surfaces or even enhanced capillary pumps [13].  \n\nSurface wettability modification techniques, can be achieved by gasphase processing, wet chemical methods or a combination of both (Table 1) [14]. Electrochemical anodization and electrospinning techniques are also used for SWM. Compared to the other SWM processes, described elsewhere [15–20], Chemical Vapor Deposition (CVD) is a fairly simple technique in which the deposition of vaporized molecules form a thin film when in contact with a surface [21,22]. CVD is very attractive also because the vapor molecules can conform to the geometry of the substrate at relatively high deposition rates only requiring rough to process vacuum regimes [23]. The small amounts of chemicals used and the ability of the vapor-phase not to transport impurities present in the liquid to the thin film layer make this technique extremely appealing [24,25].  \n\nSan Vicente and co-workers [26] studied the effect of HMDS (hexamethyldisilazane) on wettability of porous antireflective (AR) coatings for solar glass covers. The surfaces consisting of glass with antireflective coating, rich in residual silanol groups, were immersed in HMDS/ Hexane with varying concentrations $(0\\%$ to $100\\%$ HMDS), for a range of immersion times from 0 to $1400\\mathrm{min}$ , at room temperature. The authors intended to minimize the number of silanol groups present at the glass surface since these are very reactive. Silanol groups induce the adsorption of water vapor and contaminants under humidity conditions, specifically leading to deterioration of optical properties of these AR films. The authors could successfully increase an initial static contact angle (CA) of $25^{\\circ}$ to $105^{\\circ}$ after the treatment with $100\\%$ (pure) HMDS solutions and reaction times longer than $60\\mathrm{min}$ .  \n\nStiction forces can have negative impact on the fabrication and application of microelectromechanical systems (MEMS) and nanoelectromechanical systems (NEMS) as they compromise reliability, longterm stability, efficiency and durability of the devices. Zhuang et al studied surface anti-stiction coatings of self-assembled monolayers of several organosilane precursors including FDTS (perfluorodecyltrichlorosilane), grown in vapor phase on silicon surfaces [27]. The antistiction performance was evaluated by the $\\mathbf{CA},$ among others. In this study, the vapor-phase coating process was performed for process pressures down to 0.2 mbar and temperatures between $20^{\\circ}\\mathrm{C}$ and $300^{\\circ}\\mathrm{C}$ . The authors could obtain contact angles of $115^{\\circ}$ for modified silicon wafers, which are naturally hydrophilic. Other techniques have been pursued to control surface adhesion in numerous applications [28–30].  \n\nAs seen above depending on the final application the surface interfacial energy can be tuned to the desired surface wettability and the SWM determined. The wettability of a liquid to a solid surface is characterized by the measurement of contact angle (CA). The relation between contact angles and surface energy is given by the Young equation:  \n\n$$\n\\gamma_{\\mathrm{lv}}\\cos(\\Theta)=\\gamma_{\\mathrm{sv}}-\\gamma_{\\mathrm{sl}}\n$$  \n\nwhere θ is the contact angle, $\\upgamma_{\\mathrm{lv}}$ is the liquid-vapor interfacial energy, $\\upgamma_{\\mathrm{sv}}$ is the interfacial energy between solid surface and vapor and $\\upgamma_{\\mathrm{sl}}$ is the solid-liquid interfacial energy. Contact angles $\\theta\\:<\\:90^{\\circ}$ correspond to high surface energy or high wettability (hydrophylic, fluidofilic or lyophilic surface), while contact angles $\\theta>90^{\\circ}$ correspond to low surface energy or low wettability (hydrophobic, fluidofobic or lyophobic surface) [31].  \n\nThe need to use various materials in the fabrication of integrated microfluidic devices with sensing and actuating elements, several microfluidic structures, etc. directly impacts the microfabrication effectiveness. The static contact angle provides valuable information of surface wettability useful to estimate microfabrication efficiency to support functional multilayers [32–34]. Further information on the impact of surface chemical heterogeneity or macroscopic roughness can be accessed by the dynamic contact angle [35].  \n\nParticularly, in this work a room temperature gas-phase processing (Chemical Vapor Deposition, CVD) with HMDS and FDTS was used to modify the interfacial energy of different surface materials (PDMS, glass, SU-8 and silicon). The contact angle measured by sessile static drop method with DI water and PBS buffer solution allows the classification of the effects of surface wettability modification. Image J software with LBADSA (low-bond axisymmetric drop shape analysis) plugin, developed by Stalder and co-workers [36] as a tool to determine the CA from droplet images, was used to obtain the CA in this work. The approach is based on a first-order perturbation technique to analytically solve the Young-Laplace equation (Eq. 2) and provide the whole sessile drop contour and as a result, the contact angle.  \n\nTable 1 Examples of gas-phase and wet chemical surface wettability modification (SWM) techniques.   \n\n\n<html><body><table><tr><td>Gas-phase processing</td><td>Wet chemical methods</td></tr><tr><td>ultrasonic spray pyrolysis calcination</td><td>phase inversion</td></tr><tr><td>hydrothermal treatment</td><td>interfacial polymerization</td></tr><tr><td></td><td></td></tr><tr><td>ultraviolet irradiation</td><td>layer-by-layer deposition</td></tr><tr><td>microwave irradiation</td><td>sol-gel coatings</td></tr><tr><td>plasma oxidation</td><td>silanization</td></tr><tr><td>UV irradiation</td><td>dynamic modification with surfactants</td></tr><tr><td>chemical vapor deposition</td><td>protein adsorption</td></tr><tr><td>atomic layer deposition</td><td></td></tr><tr><td>sputter coating of metal compounds</td><td></td></tr></table></body></html>  \n\n$$\n\\Delta\\mathfrak{p}=\\gamma\\ \\nabla\\cdot\\boldsymbol{n}\n$$  \n\nThe Young-Laplace equation relates the interfacial tension $\\gamma$ between the two fluids and the pressure difference across the interface Δp in opposite direction to $n$ . Here n is a unit vector normal to the interface directed from the liquid drop to air.",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2. Experimental technique",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.1. Materials  \n\nRigid flat samples of glass microscope slides $(76\\times26\\times1\\mathrm{{mm}}$ thick, Normax), silicon pieces (single side polished Si, mechanical grade, $0.65\\mathrm{mm}$ thick, University Wafer), SU-8 2005 coatings $(5\\upmu\\mathrm{m}$ thickness, permanent epoxy negative photoresist, Microchem) and PDMS membranes (10:1, $0.5\\mathrm{mm}$ thickness, SYLGARD ${\\mathfrak{P}}$ 184 silicone elastomer, Dow Corning) were exposed to HMDS vapor (hexamethyldisilazane $\\mathrm{(HN[Si(CH_{3})_{3}]_{2}}$ , $161.40\\mathrm{g.mol}^{-1}$ , $96.0\\%$ , TCI) and FDTS vapor (perfluorodecyltrichlorosilane, $(\\mathrm{CF}_{3}(\\mathrm{CF}_{2})_{7}(\\mathrm{CH}_{2})_{2}[\\mathrm{SiCl}_{3}],$ $581.56g.\\mathrm{mol}^{-1}$ , $97.0\\%$ , Alfa Aesar) at room temperature. The investigation of SWM consist in measuring the contact angle of liquid drops of deionised (DI) water or water-based phosphate-buffered saline solution (PBS, $1\\times$ , $\\mathsf{p H7.4}$ ) in contact with the solid surface after CVD exposure",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.2. Surfaces preparation  \n\nsamples of glass and silicon have been washed with Alconox® anionic detergent for $3\\ensuremath{\\mathrm{h}}$ , rinsed with isopropanol $(>99.8\\%$ , Labchem) followed by DI water, and blow dried. PDMS membranes have been prepared by manually mixing 3 dimethyl siloxane and 184 silicone elastomer (cross linking agent) in 10:1 ratio, left for $^{\\textrm{1h}}$ on the vacuum desiccator (1-800-4Bel-Art, Bel-Art Products) to remove any bubble present in the mixture, and cured at $70^{\\circ}\\mathrm{C}$ for $^{\\textrm{1h}}$ (Memmert $\\mathrm{GmbH}+\\mathrm{Co}$ . KG 100–800 oven). SU-8 $20055{\\upmu\\mathrm{m}}$ thickness homogeneous coating has been defined by a 2-step spin coating on previously dehydrated silicon pieces (step 1: 500 rpm for 10 s at $100\\mathrm{rpm}.s^{-1}$ , step 2: $3056\\mathrm{rpm}$ for $30s$ at $300\\mathrm{rpm}.s^{-1}$ ; Modular spin coater ws-650- 23NPP, Laurell Technologies Inc.). After a soft baking step on a hot plate ( $95^{\\circ}\\mathrm{C}$ for $2\\mathrm{min}$ , SD160 hotplate, Stuart), the SU-8 2005 has been exposed UV light (17 $s,5.95\\mathrm{W.cm}^{-2}$ , UH-H 254, UV Light Technology LTD; black filter: $320{\\mathrm{-}}405{\\mathrm{nm}},$ ), followed by another soft bake step $95^{\\circ}\\mathrm{C}$ for $3\\mathrm{min}^{\\cdot}$ ) and finally left to cool to room temperature. All steps have been prepared inside a laminar flow hood (Faster-BSC-EN) to avoid surface contamination",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.3. Surface wettability modification process – CVD  \n\nThe chemical composition of the surface layer was varied by exposing the surface to a volume of $6{\\upmu\\mathrm{L}}$ HMDS or FDTS vapor on a vacuum desiccator (Bel-Art Products) for 2, 10, 20, 30 or $50\\mathrm{min}$ at ambient temperature $(22^{\\circ}\\mathrm{C})$ and pressure - $-0.78\\ \\pm\\ 0.09$ atm (R5 rotary vane vacuum pump, Busch) (Fig. 1a).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.4. Sessile static drop method  \n\nContact angle analysis (Fig. 1b) has been performed dispensing $6{\\upmu\\mathrm{L}}$ liquid drops of DI water or PBS solution on the surface with a controllable syringe pump (NE 4000, New Era) and $1\\mathrm{mL}$ syringe (CODAN) plus polyethylene tubbing BTPE-90 ${863.3\\upmu\\mathrm{m}}$ inner diameter, Instech Lab). CA measurements have also been performed in cleaned, non-exposed control sample surfaces referring to exposure time $0\\mathrm{min}$ . Images of each droplet on the surface (Fig. 1c) have been taken under ambient conditions within $5\\mathrm{min}$ after CVD exposure, unless otherwise stated. The effectiveness and stability of SWM over time has been evaluated through CA measurements over $65\\mathrm{h}$ after CVD. Droplet images have been recorded with a CMOS camera $(5.1\\upmu\\mathrm{m}$ pixel size, 12 Mpixel) coupling a macro lens with 0.33 maximum magnification. Each combination of experimental conditions (substrate – liquid – CVD fluid – exposure time, see Table 2) has been repeated three times. CA evaluation has been performed using Image $\\boldsymbol{\\mathrm{~J~}}$ software with LBADSA plugin.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3. Experimental results and discussion  \n\nThe properties of liquid water are strongly influenced by a variety of cohesive internal interactions in liquid water molecules: van der Waals forces, dipole interactions, hydrogen bonds and proton exchange. In wettable surfaces (hydrophilic surfaces), the forces associated with surface-liquid interaction are greater than the cohesive forces in water molecules and the liquid water spreads on the surface. If internal cohesive forces dominate over surface-liquid interaction forces, drops are formed on the surface [37].  \n\nSurface wettability modification has been characterized by measuring the contact angle of sessile drops of liquid in contact with rigid surfaces. The surfaces have been previously exposed to chemical treatment according to process parameters depicted in Table 2. Random contact angle errors have been determined with a precision of $\\pm\\:\\%$ pixel by assessing the CA using LBADSA plugin of one single image 20 consecutive times. From this evaluation an error of $\\pm\\:2^{\\circ}$ was obtained. In their study, Williams and co-authors found an error of $-1.1^{\\circ}$ using the same methodology [38].  \n\nResults depicted in Fig. 2 show HMDS chemistry is more effective for SWM of highly wettable surfaces $\\mathrm{(CA}<20^{\\circ}\\$ into moderately wettable surfaces $(\\mathrm{CA}^{\\sim}70^{\\circ})$ after $30\\mathrm{min}$ chemical exposure. CA on both silicon-containing surfaces (glass and silicon surfaces), initially hydrophilic $\\mathbf{\\tilde{C}A}\\cong17^{\\circ})$ , showed an increase after chemical exposure of the surface to HMDS, which indicates a decrease in surface interfacial energy. The surface coverage seems to reach a plateau after $30\\mathrm{min}$ of CVD exposure to HMDS as the CA reaches a plateau of $\\mathrm{CA}_{\\mathrm{glass,t}30}=65^{\\circ}$ and $\\mathrm{CA}_{\\mathrm{Si},\\mathrm{t}30}=73^{\\circ}$ whereupon preserved.  \n\nWhen in the presence of HMDS, the oxygen of hydroxyl groups $(-\\mathrm{OH})$ on water-free silicon-containing surfaces will chemically bond to Si atoms of HMDS molecule, accompanied by the release of ammonia $\\left(-\\mathrm{NH}_{3}\\right)$ (Fig. 3). Additionally to the hydrophobic nature of the trimethylsilyl tail group $(-\\mathrm{{Si}}({\\mathrm{CH}}_{3})_{3})$ , the surface interfacial energy is dependent on the extent of surface coverage, unreacted residual groups from the silane on the surface and distribution and orientation of these specific functional groups grafted on the surface [41].  \n\n![](images/ba3c81e0490554000eee3001942c6fa98f6bdc2788fd5c8a3f1134db2ca9cc94.jpg)  \nFig. 1. Experimental apparatus. a) CVD setup used to chemically modify surface wettability, b) contact angle measurement apparatus, c) example of image captured for CA analysis.  \n\nTable 2 Experimental conditions tested to determine the influence of process parameters in surface wettability modification (SWM).   \n\n\n<html><body><table><tr><td>Rigid surface</td><td>Liquid used in CA analysis</td><td>Fluid used for SWM CVD exposure time [min]</td><td></td></tr><tr><td>Glass slide</td><td>DI water</td><td>HMDS,</td><td>FDTS,</td></tr><tr><td>Silicon piece</td><td></td><td>0,2,10,20,30,50 min,</td><td>0,2,10,20,30,50 min,</td></tr><tr><td>PDMS membrane</td><td>PBS</td><td>p = -0.78 ± 0.09 atm,</td><td>p = -0.78 ± 0.09 atm,</td></tr><tr><td>SU-8 2005 coating</td><td></td><td>Tamb = 22 °℃</td><td>Tamb = 22 °℃</td></tr></table></body></html>  \n\nDI water and PBS drops on SU-8 surfaces, initially with CASU-8,w,t0 $=112^{\\circ}$ , showed a decrease in CA after activation with HMDS (variation from $120^{\\circ}$ to $100^{\\circ}.$ ) throughout the different activation times, reaching a plateau after $30\\mathrm{min}$ of activation. The decrease in CA is believed to originate from the reaction between epoxide groups present in SU-8 and secondary amines of HMDS (Fig. 4). The free electrons of the nucleophile atom from HMDS (in this case, the nitrogen) react with the methylene group $\\left(-\\mathsf{C H}_{2}\\right)$ of the epoxide to obtain a less hydrophobic hydroxyl group $(-\\mathrm{OH})$ on SU-8 surface [42].  \n\nThe additional hydrogen atoms in SU-8 surface after activation coming from the hydroxyl group $(-\\mathrm{OH})$ increases the number of hydrogen bonds and consequently the forces of interaction between the surface and the liquid drop, leading to a decrease in CA. However, the surface-liquid interaction forces are not sufficient to overcome the cohesive forces of bulk liquid water, hence the surface maintains its hydrophobic behaviour (CA $100^{\\circ}.$ [37].  \n\nZisman described the influence of hydrogen atoms on surface energy, by modifying fluorocarbon surfaces $\\left(\\mathrm{CF}_{3}\\right)$ with hydrogen atoms $(\\mathrm{CF}_{2}\\mathrm{H})$ [43]. The author observed increasing surface energy in the order: $\\mathrm{CF}_{3}<\\mathrm{CF}_{2}\\mathrm{H}<\\mathrm{CH}_{3}<\\mathrm{CH}_{2}$ . Here, the modification of one single atom of fluorine for an atom of hydrogen duplicated the surface energy, leading to higher surface wettability. Likewise, surface-liquid interaction forces on surfaces containing $-\\mathrm{CH}_{3}$ groups are expected to be weaker than those containing hydroxyl groups $(-\\mathrm{OH})$ or hydrogen atoms $(-\\mathrm{H})$ . PDMS is a polymer with exposed methyl $\\left(-\\mathsf{C H}_{3}\\right)$ groups whose reactiveness also depends on the adjacent substituents (Fig. 5). In the case of PDMS, these groups are very unreactive and the attack from the nucleophile atom of HDMS does not occur. Hence, the CA values measured on PDMS surfaces are seen not to significantly change after HDMS CVD exposure. Nonetheless, this strategy for SWM of PDMS surfaces can be pursued to prevent adhesion between the PDMS master and a PDMS mold, as example [12,45,46] or act as self-cleaning layers [47]. Overall, the variation of chemical composition at the surface enabled to modify the surface contact angle never exceeding $120^{\\circ}$ , well in accordance with Terpilowski and Goncharuk [48].  \n\nPerfluorodecyltrichlorosilane (FDTS) molecules, like HDMS molecules, form self-assembled monolayers (SAM) in which the Si from trichlorosilane functional groups $(\\mathrm{-}{\\mathrm{{SiCl}}_{3}})$ covalently bonds to oxide surfaces to release hydrochloric acid (HCl) (Fig. 6) [27]. The decrease on wetting behaviour of silicon and glass surfaces observed from the increase in CA from $20^{\\circ}$ to around $70^{\\circ}$ after FDTS activation in Fig. 7a  \n\n![](images/2b68755c2df4d59c45d9d04c7b96e2561dc8d271413a5f57d70540d86a48ca8e.jpg)  \nFig. 2. Contact angle of a) DI water droplets and b) PBS droplets on rigid surfaces of glass, silicon, SU-8 and PDMS after CVD using HMDS, c) examples of static contact angles obtained with $6{\\upmu\\mathrm{L}}$ sessile droplets of liquid water on glass, silicon, SU-8 2005 and PDMS surfaces.  \n\nV. Silverio, et al.  \n\n![](images/867c8985b56da53607272d4f432f89db634c40f4c99cfda4dcc9567843ac10d9.jpg)  \nFig. 3. Reaction between HMDS and a silicon-containing surface. –Si atoms in HMDS chemically bond to the oxygen of hydroxyl groups, accompanied by the release of ammonia. (adapted from [39]).  \n\n![](images/bf4336848b86067611cfa3dbd1190188da2b109483496656973dfb2182240c89.jpg)  \n\n![](images/e9a6718c658c68b6b123e751d6b3cb6d11384dd03d95201cb8d98764cd2ac7f3.jpg)  \nFig. 4. Reaction between HMDS secondary amine and the epoxide group of SU-8 photoresist. The nucleophile atom of HMDS (nitrogen) reacts with the methylene present in the epoxide group of SU-8, forming an hydroxyl group. (adapted from [40]).  \n\nfor water and Fig. 7b for PBS, is attributed to the heavily fluorinated hydrophobic tail group of the SAM at the surface. The surface coverage seems to be reached later for glass surfaces (saturation around $50\\mathrm{min}$ FDTS CVD exposure) when compared to silicon surfaces (saturation around $20\\mathrm{min}$ FDTS CVD exposure) probably due to the boron ions in the composition of glass, which reduce the reaction kinetics of FDTS with hydroxyl groups at the surface [49].  \n\nCA on modified PDMS surfaces showed a slight increase after $2\\mathrm{min}$ CVD exposure with FDTS while on SU-8 modified surfaces present a slight decrease. As seen before, the increase or decrease in surface hydrophobicity by changing the surface chemical composition is limited by the wettable nature of the new chemical groups on the surface. The polimerization step of SU-8 monomers after post-exposure bake opens the epoxide group of SU-8 forming an hydroxyl group at SU-8 surface (Fig. 8a), available to react with the Si from the triclorosilane group of FDTS (Fig. 8b) which may explain the slight decrease observed in CA.  \n\n![](images/90cf00d19d52c01beebcc2b9523de88b5ddf20dc6de724b561214ab0ee1feb38.jpg)  \nFig. 5. Molecular structure of PDMS. Here n is the number of monomer repetitions. (adapted from [44]).   \nFig. 6. Reaction between FDTS (a self-assembled monolayer reagent) and a silicon surface. (adapted from [50]).  \n\n![](images/9df31606799b0f44c566ed6d6db172cac151759f5116b0a80b40ffe904b74836.jpg)  \nFig. 7. Contact angle of $6{\\upmu\\mathrm{L}}$ liquid droplets of a) DI water and b) PBS onto glass, silicon, SU-8 and PDMS surfaces after CVD exposure with FDTS.  \n\n![](images/b10319d8dd09e52f2196406eccb7d015f02c08f2c3c0b8412683818d3a19eb11.jpg)  \nFig. 8. Polimerization of SU-8 monomers in post-exposure bake (adapted from [51]). b) Reaction between FDTS and the SU-8 photoresist after post-exposure bake. The Si from the triclorosilane group of FDTS reacts with the oxigen of SU-8 releasing HCl.  \n\n![](images/4623ee197a63983a07f86c543e4a5e6ef8093ac02b4ac201dfcd5288e65d834d.jpg)  \nFig. 9. Variation of CA between a silicon surface and droplets of DI water and PBS buffer, after $50\\mathrm{min}$ of CVD exposure with a) HMDS and b) FDTS. In both cases after $65\\mathrm{h}$ the CA remains around $70^{\\circ}$ , which indicates a prolonged effect of chemical activation. Contact angles of DI water on Si surfaces modified with c) HMDS and d) FDTS.  \n\nThe quantification of surface chemical composition and structure can be realised recurring to techniques such as XPS, ToF-SIMS, XRF, LDFTMS or OES [52,53]. Vandencasteele and co-authors [54] used XPS to correlate the surface modification of PTFE, PVDF and PVF with nitrogen and oxygen plasma with measurements of contact angle of water droplets onto the same materials. Contact angle was directly correlated with polymer defluorination, corroborated by XPS analysis. This analysis becomes even more important when multiple layers of different materials or alloys need to contact to fabricate the final device. As example, Jung et al. [55] used XPS to correlate the effectiveness of graphene adhesion between silicon dioxide and glass, by modified anodic bonding with measurements of contact angle. The results show the contact angles obtained are directly dependent of the density of C–O bonds. Analysis techniques such those presented above are powerful tools for process validation in the several stages of microfabrication.  \n\nThe stability of SWM is a crucial parameter to successfully implement surface modification strategies in the fabrication and usage of microfluidic devices. The effectiveness of SWM over time has been evaluated for a silicon surface after $50\\mathrm{min}$ activation with HMDS (Fig. 9a) and FDTS (Fig. 9b). The results presented in Fig. 9a for DI water $\\mathrm{CA}_{\\mathrm{Si,HMDS,H2O}}=63\\pm5^{\\circ})$ and PBS $\\mathrm{CA}_{\\mathrm{Si,HMDS,PBS}}=63\\pm4^{\\circ})$ on the silicon surface show negligible variation of CA over time after SWM with HDMS whereas FDTS modified surfaces (Fig. 9b) present slightly higher variation in CA measured $\\mathrm{CA_{Si,FDTS,H2O}}=72\\pm8^{\\circ}$ and $\\mathrm{CA_{Si,FDTS,PBS}}=73\\pm7^{\\circ}$ .  \n\n![](images/8dcfc06d3cda6ec076dcfa631db7c494d17e2745b6bd8eb90bad4ecd4041e15f.jpg)  \nFig. 10. Self-assembled monolayers (SAM) of FDTS in the presence of water vapor in the reaction chamber. The presence of water promotes the formation of compact SAM by means of strong oxygen bonds. (adapted from [57]).  \n\nThis slight variability in surface contact angle may be due to lowerquality FDTS SAM on the surface originated by the absence of water vapor inside the desiccator. Although Si–Cl groups are strongly reactive with silanol functional groups (–SiOH), it is unlikely that all three terminal chlorine atoms of the same FDTS molecule react with the irregularly located silanol groups on the Si surface. As so, the SAM contains molecules that may not be firmly attached to the surface resulting in low-coverage or low-quality coverage of the Si surface [56]. To work around this limitation, Zhuang and co-authors [27] used water vapor in the reaction chamber to promote SWM with FDTS (Fig. 10). A prior reaction of −OH groups in water and –SiCl3 groups in FDTS allowed obtaining a denser and more stable self-assembled monolayer. In fact, compared with other more expensive and complex surface modification techniques (see Table 1), the simple yet very reliable chemical modification strategy pursued in this work using HMDS or FDTS on silicon surfaces as showed consistency over long periods of time over $65\\mathrm{h}$ . Due to the simplicity of this approach and the small experimental scheme needed, it can be easily implemented in diverse research and industrial scenarios.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 4. Conclusions  \n\nIn this work, chemical modification of surfaces of silicon, glass, SU-8 photoresist and PDMS was tested to understand the effect of HMDS and FDTS on the surface wettability. The experiments showed that the efficiency and stability of surface coverage are highly dependent on the availability of $-s\\mathrm{iOH}$ groups at the surface. Surface wettability after CVD modification was perceived to be governed by the wettable nature of the tail group deposited at the surface.  \n\nCA measurements of drops of DI water and PBS buffer on the surfaces activated with HMDS shows that surface energy of hydrophilic surfaces (glass and silicon) decreased with the increment of activation time. In other words, CA increased with activation (CA variation from $20^{\\circ}$ at $\\mathbf{t}=0\\mathrm{min}$ to $60^{\\circ}/70^{\\circ}$ at $\\mathbf{t}\\geq30\\mathrm{min},$ , reaching a plateau after $30\\mathrm{min}$ of activation. SU-8 photoresist, which is a hydrophobic surface, showed a decrease in CA, reaching a plateau after $30\\mathrm{min}$ of activation.  \n\nFor SWM with FDTS, the results obtained are similar those obtained with HMDS: both glass and silicon showed an increase in CA (variation from $20^{\\circ}$ to $60^{\\circ}/75^{\\circ})$ . The highest CA measured for glass was between 30 and $50\\mathrm{min}$ of activation, while for silicon, the highest CA was measured between 20 and $30\\mathrm{min}$ of activation. SU-8 showed a slight decrease in CA after $2\\mathrm{min}$ of activation (variation from $120^{\\circ}$ to 98°).  \n\nPDMS shows no relevant variation after activation with HMDS nor with FDTS.  \n\nThe evaluation of SWM persistence after $50\\mathrm{min}$ chemical activation of the Si surface with HMDS and FDTS shows the bonds formed from the reaction between Si and HMDS is more stable than those between Si and FDTS. FDTS shows a high potential to decrease surface energy due to its heavily fluorinated tail group but the absence of water vapor in the experiments leads to low-quality SAM growth.  \n\nThis surface wettability modification approach is seen as a simple and cost-efficient method to effectively control wettability of surfaces also attractive for industrial environments.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 13,
+        "chunk": "# Conflicts of interest  \n\nThe authors have no competing interests to declare.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# Acknowledgements  \n\nINESC-MN acknowledges Fundação para a Ciência e a Tecnologia (FCT) funding through the Instituto de Nanociência e Nanotecnologia (IN) Associated Laboratory and projects POCI-01-0145-FEDER-016623 and PTDC/CTM-NAN/3146/2014, financed by FEDER (Quadro Portugal 2020) and FCT. This project has received funding from National Funds through FCT under the project PTDC-FIS-PLA-31055- 2017.",
+        "category": " Acknowledgements"
+    },
+    {
+        "id": 15,
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+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Highly efficient antifogging and frost-resisting acrylic coatings from onestep thermal curing  \n\nJie Zhaoa, Pengpeng Lua, Lingjie Songc,\\*, Limei Tiana, Weihua Mingb,\\*, Luquan Rena  \n\na Key Laboratory of Bionic Engineering, Ministry of Education, Jilin University, Changchun 130022, China b Department of Chemistry and Biochemistry, Georgia Southern University, P.O. Box 8064, Statesboro, GA 30460, USA c State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Changchun 130022, China",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# G R A P H I C A L A B S T R A C T  \n\nScheme: Preparation of multiple crosslinked coatings and mechanism of antifogging and anti-frost.  \n\n![](images/a0e1ee39fa62e861e73b92fa3d11810da068ae5ce11687f18a5d528e9e645a8c.jpg)",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# A R T I C L E I N F O",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# A B S T R A C T  \n\nKeywords:   \nAntifogging   \nFrost-resisting   \nCross-linking   \nAcrylic coating   \nLight transmittance  \n\nHerein, we report an acrylic coating with both antifogging and frost-resisting performances via a one-step thermally initiated crosslinking method. This work adopted a facile and easily controlled process to prepare cross-linked acrylic polymer coatings. Among those, 2-acrylamido-2-methyl propane sulfonic acid (AMPS) and methyl methacrylate (MMA) were used as the hydrophilic and hydrophobic monomers, respectively, to endow the coating with delicate hydrophilic-hydrophobic balance. Meanwhile, ethylene glycol dimethacrylate (EGDMA) and 3-trimethoxysilylpropyl methacrylate (TMSMA), as the cross-linkers, were applied to adjust the cross-linking density as well as to improve adhesion toward the substrate. The influences of the hydrophilichydrophobic balance and the cross-linking density on the antifogging/frost-resisting performances were explored. Moreover, the water absorption capacity of the coating was investigated by time-depended water contact angle changes to further examine the origin of the antifogging/frost-resisting performances. Due to its simplicity and scalable characteristics, we believe this type of coating may find broad applications where both antifogging and frost-resisting properties are required.",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# 1. Introduction  \n\nDeveloping a surface with robust antifogging/anti-frost performances under a variety of different challenges (e.g., temperature and humidity) has received great attentions and considerable works have been devoted [1–10]. Currently, most related works about antifogging coatings particularly focused on highly hydrophilic or superhydrophilic surfaces due to their ability to form a thin-film-like water layer from water condensation, which would significantly suppress light scattering and improve light transmission [11–24]. However, complicated procedures to fabricate surface texture or UV illumination for $\\mathrm{TiO}_{2}$ based coatings are generally required to obtain surface superhydrophilicity [25–28]. Moreover, these superhydrophilic surfaces may fail to resist frost formation since ice layer would inevitably form out of the thin water layer under freezing conditions. Recently, an alternative antifogging strategy has been successfully developed by integrating both hydrophobic and hydrophilic segments in one coating [29–32]. Different to the conventional highly hydrophobic or superhydrophilic surfaces, the coatings with hydrophobic and hydrophilic components demonstrate their antifogging performances by enabling water vapor to diffuse rapidly into the hydrophilic domains rather than nucleating drops of condensed water on the surface [33,34]. Meanwhile, the hydrophobic components endow the coating with high stability, avoiding the potential water solubility of the coating [35]. Consequently, antifogging property can be obtained on the surfaces even without high hydrophilic or superhydrophobic properties, such as the coatings with both perfluoroalkyl groups and poly(ethylene glycol) (PEG) segments [36,37], or the coatings with zwitter-wettability via layer-by-layer assembly containing PEG segments [29] or with a nanoscale thin hydrophobic capping layer in Chitosan/Nafion system [33]. We have recently developed a series of effective antifogging/frost-resisting coatings based on a semi-interpenetrating polymer network (SIPN) consisting of binary or ternary acrylic copolymers with both hydrophilic and hydrophobic segments and a cross-linked network [38]. Although these SIPN coatings exhibit reliable antifogging/frost-resisting performances under different harsh conditions, the prolonged reaction time and a 2-step procedure including copolymer preparation and SIPN coating preparation are needed.  \n\nHerein, we report a facile strategy for developing antifogging/frostresisting cross-linked acrylic coatings, via a one-step thermally initiated crosslinking reaction (Scheme 1). Among those, 2-acrylamido-2-methyl propane sulfonic acid (AMPS) and methyl methacrylate (MMA) were adopted as the hydrophilic and hydrophobic monomers, respectively, to endow the coating with delicate hydrophilic-hydrophobic balance. Meanwhile, ethylene glycol dimethacrylate (EGDMA) and 3-Trimethoxysilylpropyl methacrylate (TMSMA), as the cross-linkers, were applied to adjust the cross-linking density as well as coating adhesion. Both qualitative and quantitative fogging analyses were conducted. The influences of the hydrophilic-hydrophobic balance and the cross-linking density on the antifogging/frost-resisting performances were explored.",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2. Experimental section",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.1. Materials  \n\n2-Acrylamido-2-methyl propane sulfonic acid (AMPS, $99\\%$ ), ethylene glycol dimethacrylate (EGDMA, $99\\%$ , thermal initiator $^{2,2^{\\prime}}$ -azobis (2-methylpropionitrile) (AIBN, $98\\%$ ) and silane coupling agent 3-trimethoxysilylpropyl methacrylate (TMSMA) were obtained from Aldrich; methyl methacrylate (MMA) was purchased from Alfa; The solvent $N,N\\mathrm{.}$ -dimethylformamide (DMF) was obtained from Fisher and used as received.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.2. Coating preparation  \n\nGlass slides $(2.5\\times2.5\\mathrm{cm}^{2})$ were first sonicated in acetone for $30\\mathrm{min}$ , dried by argon flow, exposed to an air plasma cleaner (plasma cleaner PCE-6, Harrick Scientific) for 180 s to completely clean and activate the surfaces. A series of mixtures $_{(1.00g)}$ with varying AMPS/ MMA molar ratios (20/80, 40/60, 50/50, 60/40, 80/20), EGDMA contents $(0.1{-}2\\mathrm{wt\\%}$ relative to monomers), TMSMA $(0.1\\mathrm{wt\\%}$ relative to monomers), AIBN $(1~\\mathrm{wt\\%}~\\$ relative to monomers) and ${\\mathrm{NH}}_{3}{\\cdot}{\\mathrm{H}}_{2}{\\mathrm{O}}$ (1 wt $\\%$ relative to TMSMA) were dissolved in $10\\mathrm{ml}$ DMF, purged by argon, well mixed, and spin-coated on the plasma-treated glass slides at different rates (500, 1000, 1500 and $2000\\mathrm{rpm})$ for $4s$ The spun-coated films were heated in an oven at $80^{\\circ}\\mathrm{C}$ for $^{12\\mathrm{h}}$ to complete the copolymerization, and dried in a vacuum oven overnight $(80^{\\circ}\\mathrm{C})$ to remove any unreacted impurity. All resultant coatings under various processing conditions were labeled accordingly. For instance, a coating with the AMPS/MMA molar ratio of $60/40$ was labeled as C-60. The C-60 samples with varied EGDMA contents ranging from $0.1\\%$ to $2\\%$ were labeled as $\\mathbf{C}{\\cdot}60{-}0.1\\%$ , $\\mathbf{C}{\\cdot}60{-}0.5\\%$ $C{-}60{-}1\\%$ and $C_{-}60\\substack{-2\\%}$ , respectively. Except where specifically stated, otherwise the coatings with different molar ratios of AMPS/MMA (20/80, 40/60 and 80/20) with EGDMA content of $1\\%$ were simply labeled as C-20, C-40, C-60 and C-80, respectively.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.3. Fogging/frosting test  \n\nFogging/frosting tests were carried out, according to previous protocols [39]. Briefly, fogging test against hot water vapor was conducted by holding samples $5\\mathrm{cm}$ above a water bath $(80^{\\circ}\\mathrm{C})$ for different periods of time (15, 30, 45 and $60s\\mathrm{\\dot{}}$ with a control glass as reference. Frosting test was performed by putting samples in a freezer at ${\\boldsymbol{-20}}^{\\circ}{\\boldsymbol{\\mathrm{C}}}$ for $30\\mathrm{min}$ and photographs were taken after the samples were exposed to ambient conditions ( $20^{\\circ}\\mathrm{C}$ , $50\\%$ relative humidity) for 5 s. In addition, light transmission over $400{\\mathrm{-}}700{\\mathrm{nm}}$ was collected on a UV–vis spectrophotometer (Shanghai Spectrum Win-SP5.0) during fogging/frosting test.  \n\n![](images/15a0e7991ffb7479fc5b44780b934a3d662aa5acc7a79a5980e0b918fe2ac839.jpg)  \nScheme 1. Schematic illustration of the preparation of antifogging and frost-resisting crosslinked acrylic coating.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.4. Wettability  \n\nTo further explore the antifogging/frost-resisting mechanism of our coatings, time-dependent contact angle changes on all as-prepared coatings were monitored on a contact angle goniometer (KRÜSS DSA100) and the time-dependent contact angle was collected every 4 s over a 80-s period.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3. Results and discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3.1. Coating preparation  \n\nIn this work, antifogging/frost-resisting coatings were concisely prepared by the combination of hydrophilic AMPS and hydrophobic MMA with EGDMA and TMSMA as cross-linkers via thermal curing, hence averting the tedious multi-step coating preparation. The waterabsorbing ability of the coating can be tuned by adjusting the contents of AMPS and MMA, while the amount of EGDMA and TMSMA also plays an important role in mediating the balance between the waterswellability and the cross-linking density. It is worth mentioning that the TMSMA plays a dual role as the cross-linker in the acrylic coating and the adhesion enhancer between the coating and the glass substrate. The glass slides were treated by air plasma to generate active groups (e.g. hydroxyl groups), which not only promote the interfacial interaction with TMSMA but also facilitate the formation of a uniform coating. Coating thickness can be controlled by adjusting the spin-coating speed. The coating surface roughness (Rq) and thickness were verified by Atomic Force Microscope (AFM) on a commercial instrument (Bruker Co., Dimension Fast Scan Pro) in tapping mode. To evaluate the thickness of the coating, the samples were inscribed by a razor blade. The coating thickness of $\\sim500~\\pm~20\\mathrm{nm}$ $1000\\mathrm{rpm}$ , 4 s) (S-Fig. 2b) and Rq ${\\sim}0.826\\mathrm{nm}$ (S-Fig. 2a) were measured by AFM and calculated by NanoScope Analysis (version 1.40). Our previous studies have shown that the hydrophilic-hydrophobic balance in the SIPN coating plays a vital role in their antifogging/frost-resisting performances [34]; herein, we also varied the AMPS/MMA molar ratio (20/80, 40/60, 50/ 50, 60/40, and 80/20) to obtain the optimal antifogging/frost-resisting performances. Besides, the cross-linked density of coating also makes great influence on antifogging/frost-resisting performances, the coating with an extremely high cross-linked density would probably restrict the diffusion of water molecules into the coating layer, compromising its antifogging/frost-resisting capabilities. To simplify the experimental model, only the coatings with different EGDMA contents, ranging from 0.1 to $2\\mathrm{wt\\%}$ with respect to monomers, were prepared to identify the influence of the cross-linking density on antifogging/frost-resisting performances.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3.2. Frost-resisting performances  \n\nQuickly exposing subjects from cold conditions to warm and moist environment easily triggers serious surface fogging. In principle, when water vapor contacted with the cold surface, the fog layer appeared immediately, followed by the formation of a frost layer due to the extremely low surface temperature. Under these conditions, most of the superhydrophilic surfaces may fail to exert effective frost-resisting properties because the condensed thin water layer readily converts into an ice layer, which severely blocks light transmittance. Hence, to evaluate the antifogging properties, the frost-resisting tests of C-80, C60, C-40 and C-20 were conducted with a control glass as the reference. First, the frost-resisting performance was investigated by visually examining the sample appearance after it was taken out of a freezer $(-20^{\\circ}\\mathsf{C}$ for $30\\mathrm{min}\\mathrm{.}$ ) and exposed to ambient environment for 5 s $(-20^{\\circ}\\mathrm{C},\\sim45{-}50\\%$ relative humidity) (Fig. 1).  \n\nAs for the hydrophilic bare glass slide, a fog layer formed immediately on the surface when taken out of freezer, then gradually turned into a frost layer, which heavily blocked the light transmission and led to an extremely low clarity during the whole process (Fig. 1a). In stark contrast, the C-60 sample remained completely fog- and frostfree throughout the whole frosting test (Fig. 1c), due to the rapid waterabsorbing capability of the coating, which totally avoided the formation of either frost or fog layers on the surface. Reducing hydrophilic AMPS contents in coating reduced the efficiency of frost-resisting property (partial or complete frosting) as shown on C-20 and C-40 surfaces (Fig. 1b). The results indicated that a low AMPS content obviously decreased water-absorbing ability of the coating, largely reducing its frost-resisting capability. On the other side, although the C-80 with the highest AMPS content in our experiments exhibited much stronger water-absorbing capacity than other samples, the excessive absorbed water in coating might have led to the formation of large water domains, severely compromising the frost-resisting property of the coating as indicated by the low clarity of the coating (Fig. 1d). Herein, the hydrophilic-hydrophobic balance of the cross-linked coating plays a vital role in adjusting the water absorption capability, and the C-60 with the AMPS/MMA molar ratio of 60/40 was considered as the optimal sample to exhibit excellent frost-resisting property.  \n\nTo further evaluate the influence of cross-linking density of the coatings on its frost-resisting performances, the quantitative frosting tests of the C-20, C-40, C-60 and C-80,  \n\nand C-60 series coating with different EGDMA contents were conducted, by quantifying the light transmittance over the $400{\\-}700\\mathrm{nm}$ . Prior to frosting tests, all the samples (C-20, C-40, C-60 and C-80) demonstrated high light transmittance values more than $90\\%$ (Fig. 2a). Obvious differences in light transmittance were found after frosting treatment, the highest value (more than $90\\%$ ) was observed on the C60, followed by the C-40, C-80, and the C-20 exhibited the relatively lower light transmittance value of $\\sim55\\%$ (Fig. 2c), which were consistent with the results indicated in Fig. 1. As for the samples with different cross-linking density, all the samples $(\\mathbf{C}{-}60{-}0.1\\%$ , $\\mathbf{C}{\\cdot}60{-}0.5\\%$ $C_{-}60\\substack{-1\\%}$ and $C{-}60{-}2\\%\\dot{}$ showed relatively high light transmittance values $(90-91.5\\%)$ (Fig. 2b), which are comparable to that on the control glass slide, revealing that cross-linked density had little influence on the intrinsic light transmittance of the coatings. Obvious differences in light transmittance were found after the frosting test. The control glass showed low light transmission (below $25\\%$ , Fig. 2c), which was attributed to the severe frost-layer formation on the surface. Apparently, the EGDMA content in the coatings demonstrated a significant effect on their light transmittances. Among these, $\\mathbf{C}{\\cdot}60{-}0.1\\%$ and $\\mathbf{C}{\\cdot}60{-}0.5\\%$ maintained higher light transmittance values (above $90\\%$ ) than those of $C_{-}60\\substack{-1\\%}$ and $C_{-}60\\substack{-2\\%}$ , while the $C_{-}60\\cdot2\\%$ exhibited the lowest value of $83\\%$ (Fig. 4c). The high cross-linking density in the $C_{-}60\\cdot2\\%$ sample likely reduced the water swellability of the cross-linked network, leading to its reduced water-absorbing ability and compromised frostresisting performance.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.3. Antifogging performances  \n\nAs illustrated in Fig. 3, antifogging performances of C-60 and control glass were conducted by holding the samples $5\\mathrm{cm}$ above water bath $(80^{\\circ}\\mathrm{C})$ for different time intervals (15, 30, 45 and 60 s). For the control glass, a fog layer emerged on the glass surface immediately upon exposure to water vapor (Fig. 3a, left). Prolonging the exposure time from 15 to $60s$ made these situation even worse, larger fog droplets stemming from the vapor condensation gradually appeared on the film surface, finally leading to a completely non-transparent film. In contrast, remarkably different antifogging performances were observed on the C-60 coating. During the whole procedure, the C-60 showed completely fog-free surface, indicating the resultant coating with the optimal AMPS/MMA molar ratio of $60/40$ could thoroughly suppress surface fogging under a warm humid condition.  \n\nTo more accurately investigate the exact role of cross-linked density in antifogging behavior, the quantitative evaluation of the antifogging behaviors of C-60 samples with different cross-linker content (C-60-  \n\n![](images/638ea0eed3c8af607baeddb0394707188756b843a2167c7fc9d38510dc0b098b.jpg)  \nFig. 1. Photos of different glass slides: (a) control glass, (b) C-40, and (c) C-60, (d) C-80. first stored at $\\mathrm{-20^{\\circ}C}$ for $30\\mathrm{min}$ and then exposed to ambient lab conditions for 5 s.  \n\n![](images/0c85153ad936f3abdb86dc6df179cd502eb5698d2724129833dbe0bf7a6bbe99.jpg)  \nFig. 2. Light transmittance over $400{\\mathrm{-}}700{\\mathrm{nm}}$ of (a) as-prepared coatings with different ratios of hydrophilic/hydrophobic monomers of C20, C-40, C-60 and C-80, and (b) $\\mathbf{C}{\\cdot}60{\\cdot}0.1\\%$ , C$60–0.5\\%$ , $C{=}60{-}1\\%$ , $C{-}60{-}2\\%$ coatings. Light transmittance over $400{\\mathrm{-}}700{\\mathrm{nm}}$ following the frosting tests (first stored at $-20^{\\circ}\\mathrm{C}$ for $30\\mathrm{min}$ and then exposed to ambient lab conditions) for (c) coatings with different ratios of hydrophilic/hydrophobic monomers of C-20, C-40, C-60 and C-80 and (d) $\\mathbf{C}{\\cdot}60{-}0.1\\%$ , $\\mathbf{C}{\\cdot}60{-}0.5\\%$ , $C{=}60{-}1\\%$ , $C_{-}60{-}2\\%$ coatings.  \n\n![](images/b7f5aff140378947197ca524d3d98dffc88ad216ae05f5655b6d41c58de0b065.jpg)  \nFig. 3. Photo images of different samples: (left) control glass and (right) C-60 under different exposure time: (a) 15 s, (b) 30 s, (c) 45 s and (d) 60 s after exposure to water vapor $_{5\\mathrm{cm}}$ above an $80^{\\circ}\\mathrm{C}$ water bath) under ambient lab conditions.  \n\n$0.1\\%$ , $\\mathbf{C}{\\cdot}60{-}0.5\\%$ , $C_{-}60\\substack{-1\\%}$ and ${\\mathrm{C}}{\\cdot}60{-}2\\%\\dot{.}$ ) was also evaluated, as mentioned above (Fig. 4b). All samples were placed $5\\mathrm{cm}$ above a water bath $(80^{\\circ}\\mathrm{C})$ for $60s$ . After fogging test, all the C-60 coatings with different cross-linker contents maintained high clarity. Notice that although the samples of $\\mathbf{C}{\\cdot}60{-}0.1\\%$ and $\\mathbf{C}{\\cdot}60{-}0.5\\%$ exhibited higher light transmittance values than others due to their lower EGDMA contents (lower cross-linked density), both $C_{-}60\\substack{-1\\%}$ and $C_{-}60\\cdot2\\%$ also maintained relatively high transparency with the light transmittances above $89\\%$ . Compared to the frost-resisting results above, some differences could be revealed that cross-linked density had more effects on the frost-resisting capability than on the antifogging performance for the coating.  \n\nThe coating stability is an important characteristic that can guarantee its potential application in various field. To evaluate the coating stability, multiple-cycle antifogging tests are conducted on the coating of C-60 for 5 cycles. As shown in (S-Fig. 1), the C-60 demonstrated high light transmittance (above $90\\%$ ) during the whole fogging process. No obvious changes in the light transmittance was observed even after 5- cycle fogging treatment, revealing that the coating possessed stable antifogging performance.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3.4. Surface wettability  \n\nDifferent with a conventional superhydrophilic antifogging surface, the cross-linked coatings of C-20, C-40 and C-60 showed much greater initial water contact angles (CAs) of $50^{\\circ}$ , $48^{\\circ}$ , and $45^{\\circ}$ , respectively (Fig. 5a), which is consistent with the recent findings [34] that a coating surface can exhibit antifogging/frost-resisting behavior even without high hydrophilicity or superhydrophilicity. Time-dependent water CA measurement was performed to further investigate the origin of the antifogging/frost-resisting behaviors in our system. Within 80-s time interval, all samples showed steady decreases of CA values. Much larger decreases in CA were observed on the cross-linked coatings compared to that of control glass $(\\sim4^{\\circ}$ decrease of CA), indicating that some water has been imbibed by the coatings apart from water evaporation on surfaces. The higher AMPS contents in the coatings led to more significant decreases in CA values within the same contacting time interval (80 s), which can be attributed to the high water-absorbing ability of the hydrophilic AMPS moiety. As shown in Fig. 5b, more remarkable differences were found on the changes in the basal diameter of the water droplet as compared to the changes of CA value: $\\sim24\\%$ , $32\\%$ and $60\\%$ increases in the diameter values for the coatings of C-20, C-40 and C-60, much greater than on the control glass (nearly no change). These results further confirmed that the water vapor had diffused into the coating and led to the expansion of the basal diameter of the water droplet. Compared with the above-mentioned antifogging results, we may draw the conclusion that the suitable water absorption capacity guarantees the effective antifogging properties; however, excessive AMPS contents such as in the C-80 would incur excessive water absorption, leading to the formation of large water domains and the compromised frost-resisting capability. On the contrary, with too low AMPS contents the samples such as C-20 and C-40 would have limited the water-absorbing capacity, which would hinder their antifogging property.  \n\n![](images/e881c41a76494f166d5f48b1a26044b7de2dc4e1d10381d1ab297f558aa6d9a8.jpg)  \nFig. 4. Light transmittance at the normal incident angle for various samples: (a) as-prepared samples with different ratios of hydrophilic/hydrophobic monomers and (b) C-60 with various crosslinking densities, after 60 s exposure to warm water vapor by placing the sample $5\\mathrm{cm}$ above $80^{\\circ}\\mathrm{C}$ water bath at room temperature.  \n\n![](images/b14daf39bd58e0dcc33f9cc8b594623daf0c0b8500651792c9f4349131fd950c.jpg)  \nFig. 5. (a) Water contact angle evolution within 80 s for samples showing different wettability. (b) Basal diameter change of water droplet on film surface within 80 s as expressed as $\\Delta\\mathrm{D}/\\mathrm{D}_{\\mathrm{o}}$ , where $\\Delta\\mathbf{D}=\\mathbf{D}-\\mathbf{D_{o}}$ and $\\mathbf{D_{o}}$ is the basal diameter at $\\mathbf{t}=0\\:\\mathsf{s}$ . All the data were the average of three times recorded in $4s$ interval.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 4. Conclusions  \n\nIn summary, antifogging/frost-resisting cross-linked acrylic coatings with the hydrophilic AMPS and hydrophobic MMA as monomers as well as EGDMA and TMSMA as cross-linkers were developed, via a one-step thermally initiated crosslinking reaction. Different with our previous strategies by forming a SIPN coating based on random copolymer, this work adopted a facile and easily controlled process to prepare crosslinked acrylic polymer coatings. The antifogging properties were derived from the hydrophilic-hydrophobic balance with the optimal AMPS/MMA molar ratio at 60/40, as well as a moderate cross-linking density from EGDMA and TMSMA. The coating demonstrated excellent antifogging performances under both warm and cold moist conditions. Considering its versatility and simplicity, these coatings may be used in various antifogging/frost-resisting applications.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 17,
+        "chunk": "# Declaration of Competing Interest  \n\nThe authors declare no conflict of interest.",
+        "category": " References"
+    },
+    {
+        "id": 18,
+        "chunk": "# Acknowledgements  \n\nThis work is supported by the National Natural Science Foundation of China (No. U1601203, 51775232) and the Equipment pre-research fund (No. 61400040404), the Science and Technology Development Plan Project of Jilin Province (No. 20190201155JC) and the Fundamental Research Funds for the Central Universities (No. 17SS023, 61400040403).",
+        "category": " References"
+    },
+    {
+        "id": 19,
+        "chunk": "# Appendix A. Supplementary data  \n\nSupplementary material related to this article can be found, in the online version, at doi:https://doi.org/10.1016/j.colsurfa.2019.124160.",
+        "category": " References"
+    },
+    {
+        "id": 20,
+        "chunk": "# References  \n\n[1] J. Zhao, L. Song, W. Ming, Antifogging and Frost-Resisting Polymeric surfaces, Adv. Polymer Sci., Springer, Berlin Heidelberg, Berlin, Heidelberg, 2019, pp. 1–30, https://doi.org/10.1007/12_2017_42. [2] Z. Han, Z. Mu, B. Li, Z. Wang, J. Zhang, S. Niu, L. Ren, Active antifogging property of monolayer $\\mathrm{SiO}_{2}$ film with bioinspired multiscale hierarchical pagoda structures, ACS Nano 10 (2016) 8591–8602. [3] Y.J. Gu, H.Y. Liu, J.L. Yang, S.X. Zhou, Surface-engraved nanocomposite coatings featuring interlocked reflection-reducing, anti-fogging, and contamination-reducing performances, Prog. Org. Coat. 127 (2019) 366–374. [4] C. Feng, Z. Zhang, J. Li, Y. Qu, D. Xing, X. Gao, Z. Zhang, Y. Wen, Y. Ma, J. Ye, R. Sun, A bioinspired, highly transparent surface with dry-style antifogging, antifrosting, antifouling, and moisture self-cleaning properties, Macromol. Rapid Commun. 40 (2019) 1800708. [5] C. Li, X. Li, C. Tao, L. Ren, Y. Zhao, S. 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Yuan, Formation of zwitterionic coatings with an aqueous lubricating layer for antifogging/anti-icing applications, Prog. Org. Coat. 115 (2018) 56–64.   \n[31] S. Bai, X. Li, R. Zhang, C. Li, K. Zhu, P. Sun, Y. Zhao, L. Ren, X. Yuan, Enhancing antifogging/frost-resisting performances of amphiphilic coatings via cationic, zwitterionic or anionic polyelectrolytes, Chem. Eng. J. 357 (2019) 667–677.   \n[32] B. Yao, H. Zhao, L. Wang, Y. Liu, C. Zheng, H. Li, C. Sun, Synthesis of acrylate-based UV/thermal dual-cure coatings for antifogging, J. Coat. Technol. Res. 15 (2018) 149–158.   \n[33] H. Lee, J.B. Gilbert, F.E. Angile, R. Yang, D. Lee, M.F. Rubner, R.E. Cohen, Design and fabrication of Zwitter-wettable nanostructured films, ACS Appl. Mater. Interfaces 7 (2015) 1004–1011.   \n[34] J. Zhao, A. Meyer, L. Ma, W. Ming, Acrylic coatings with surprising antifogging and frost-resisting properties, Chem. Commun. 49 (2013) 11764–11766.   \n[35] J. Zhao, L. Ma, W. Millians, T. Wu, W. Ming, Dual-functional antifogging/antimicrobial polymer coating, ACS Appl. Mater. Interfaces 8 (2016) 8737–8742.   \n[36] J.A. Howarter, J.P. Youngblood, Self-cleaning and anti-Fog surfaces via stimuliresponsive polymer brushes, Adv. Mater. 19 (2007) 3838–3843.   \n[37] J.A. Howarter, J.P. Youngblood, Self-cleaning and next generation anti-fog surfaces and coatings, Macromol. Rapid. Commun. 29 (2008) 455–466.   \n[38] J. Zhao, A. Meyer, L. Ma, X. Wang, W. Ming, Terpolymer-based SIPN coating with excellent antifogging and frost-resisting propertie, RSC Adv. 5 (2015) 102560–102566.   \n[39] W. Wang, P. Lu, Y. Fan, L. Tian, S. Niu, J. Zhao, L. Ren, A facile antifogging/frostresistant coating with self-healing ability, Chem. Eng. J. 378 (2019) 122173–122179.",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Direct Growth of Bio-Graphene Using Modified-Chemical Vapor Deposition For Straight-Forward Characterization  \n\nM.D. Nurhafizah \\*, A.A. Azahar , N. Abdullah  \n\nSchool of Physics, Universiti Sains Malaysia, 11800 USM, Minden Penang, Malaysia",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# H I G H L I G H T S",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# G R A P H I C A L  A B S T R A C T  \n\nOil Palm Shell biomass conversion to Bio-Graphene via pyrolysis and CVD.   \n• Partial and total covers growing settings were evaluated on Bio-Graphene growth.   \n• Faster characterization through direct deposition of Bio-Graphene on a silicon wafer.   \nBetter closed growing settings facilitate the growth of high-quality BioGraphene.  \n\n![](images/9cc379e22ff8561303e1280f50bb496d576e6d65b8ab6286afbcc88e40f0ef12.jpg)",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# A R T I C L E  I N F O",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# A B S T R A C T  \n\nKeywords:   \nGraphene   \nAlumina Boat   \nPyrolysis   \nOil Palm Shell   \nBiochar  \n\nOil Palm Shell (OPS) is subjected to heating, resulting in gaseous compound release. These compounds are deposited on the substrate to produce Bio-Graphene. Through Chemical Vapor Deposition (CVD), the process is optimized by growing environment parameters during the production process. This process involves the controlled deposition of gaseous compounds onto a substrate under two different positions of the alumina boat (ABC-1 and ABC-2). Direct deposition on silicon wafers eliminated etching and transfer sequences, simplifying Bio-Graphene characterization. Field Emission Scanning Electron Microscope, Atomic Force Microscope, Raman Spectroscopy, X-ray diffraction, and I-V measurement were employed to characterize the Bio-Graphene. The findings revealed that the better-closed settings (ABC-2) facilitated the growth of high-quality Bio-Graphene with better crystallinity, detectable growth spurt, estimated few-layer thickness, larger growth area, and lower surface roughness. Optimizing the deposition environment at ABC-2 significantly enhances the quality and crystallinity of Bio-Graphene from OPS, paving the way for future applications.",
+        "category": " Abstract"
+    },
+    {
+        "id": 6,
+        "chunk": "# 1. Introduction  \n\nPalm oil production is a global economic venture that promotes the economic growth of many countries that could supply them. In 2015, global production of palm oil reached 63 million tons, with Indonesia contributing the highest percentage at $53\\%$ , it is followed by Malaysia at $33\\%$ and then by Thailand at $3\\%$ (Mahlia et al., 2019). Palm oil holds immense significance not only in meeting the global demand but also as a vital economic contributor to Southeast Asian (SEA) countries. Palm oil is obtained by planting, growing, and harvesting palm oil plants over hectares of palm oil plantation. The production of palm oil generates a substantial amount of biomass waste, including various types of branching waste, at every stage of the production process (Nabila et al., 2023). Thus, an issue arises when the industry generates a substantial amount of waste that possesses a significant impact on waste manage­ ment. One of the palm oil wastes is Oil Palm Shell (OPS) which is be­ tween the hard seed and flesh mesocarp of the palm oil fruit (Omar et al., 2018). Improper waste management can lead to air pollution, water pollution, visual pollution, and odor pollution that results in damage to the natural environment, including the loss of biodiversity and ecosystem.  \n\nOil palm shell produces solid amorphous carbon biochar, a complex mixture of organic compounds bio-oil, and gaseous compounds biogas while undergoing pyrolysis. The biogas produced from oil palm shells are composed of methane $\\mathrm{(CH}_{4}\\mathrm{)}$ , carbon dioxide $\\left(\\mathsf{C O}_{2}\\right)$ , and small amounts of other gases such as nitrogen $\\left(\\mathrm{N}_{2}\\right)$ and hydrogen $\\left(\\mathrm{H}_{2}\\right)$ (Maithel, 2009). Typically, biogas contains around $50\\mathrm{-}70~\\%$ methane and $30\\text{\\textperthousand}$ carbon dioxide (Xie et al., 2020), although the exact composition can vary depending on the specific conditions. Under the right conditions, the biogas can be subsided on a designated substrate to produce a deposition carbon layer known as Bio-Graphene.  \n\nThe Bio-Graphene growth during carbon deposition plays an important role in the fabrication process. Thus, optimizing the growing environments is crucial to obtaining appropriate deposition and exfoli­ ation. Alumina boat configuration is utilized to adjust the growth con­ ditions, allowing for the regulation of gaseous compound release and enhancing gas flow. When thermal pressure is issued on the OPS bio­ char, it releases certain gaseous compounds when interacting with the dissociative substrate surface will deposit carbon and produce pores within the deposited layer (Serykh & Agafonov, 2020). To achieve the formation of the carbon-based nanomaterial, it is necessary to subject the carbon layer to high temperatures. This can be accomplished by creating a high-temperature environment, which will promote the development of carbon deposition and exfoliation during the Chemical Vapor Deposition (CVD) process.  \n\nBiomass from oil palm waste has been used over the years as a pre­ cursor due to its abundance of carbon content potential to fabricate graphene and graphene-like material (Safian et al., 2021). This research aims to investigate OPS green biomass precursor usage in fabricating Bio-Graphene instead of relying on factory-manufactured graphite pre­ cursor. The OPS is pyrolyzed to produce rich-methane potential carbon precursor and Bio-Graphene is fabricated in two different controlled settings/alumina boat placement during the CVD process. The produced the carbon-based nanomaterial was characterized using various analytical techniques, including Field Emission Scanning Electron Mi­ croscopy, Atomic Force Microscopy, Raman Spectroscopy, X-ray diffraction, and I-V measurement. According to the results, the use of better-closed settings (ABC-2) led to the growth of high-quality BioGraphene with improved crystallinity, detectable growth spurt, esti­ mated few-layer thickness, larger growth area, and lower surface roughness.  \n\nThis study presents a novel and sustainable method for producing direct deposition Bio-Graphene using OPS biochar as the precursor material. The process involves subjecting OPS biochar to a heating process to release gaseous compounds that are then deposited onto a substrate using CVD. Due to the new and unique low-cost CVD technique incorporated in this research, detailed information on the growing environment—whether partial or total cover— is lacking, which is imperative for the synthesis process. This research focuses on mecha­ nistic insight into how different growing environments influence or restrict the CVD deposition process, distinguishing it from other CVD research. The future application of this research could be in the pro­ duction of cost-effective and sustainable carbon-based nanomaterial for various industrial applications Furthermore, this study opens an array of methane-to-carbon-based nanomaterial possibilities from biomass sources instead of relying solely on industrialized methane containers. This approach presents a more sustainable and environmentally friendly method of producing carbon-based nanomaterial.  \n\nThe issue of CVD graphene growth can be observed from the para­ digm of economic comparative analysis between traditional CVD and this research CVD. Tradition CVD often possesses a few characteristics aspect such as normal atmospheric pressure, gaseous exposure, chemical vapours, surface reaction/decomposition, and thin layer formation (Dobrzanski et al., 2013). Although this research borrowed various key aspects from traditional CVD, the gas source during gaseous exposure sequences has been changed. In usual case, expensive methane and other gases are employed in their pure form, directed towards the CVD chamber for graphene growth. To add context, pure methane is sold around the world averages at 1.1 USD/litre, according to Global Petrol Prices. CVD process cost can be significantly reduced by employing green precursor as their gas source. However, this in turn creates a drawback, where the small gaseous release from green precursor might not accommodate well towards a large chamber from traditional CVD. Thus, employing two distinct growing environments to properly accommodate green precursors can create an overall cost reduction in the operation.",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2. Materials and methods",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.1. Raw materials  \n\nThe raw materials for palm oil waste were obtained from United Oil Palm Industries Sdn. Bhd. in Nibong Tebal, Penang, Malaysia, consisting of palm oil waste, specifically Oil Palm Shell (OPS). OPS is collected fresh from the mill and to ensure its shelf life and quality, the palm oil waste was subsequently kept in a dark area to avoid spoilage and contamination from fungi and other microorganisms. Subsequently, palm oil waste requires multiple processes to prepare it as a precursor. The palm oil waste is grounded and screened to obtain uniform particle size, afterward dried in a Force Air Convention Oven (Venticell Oven) at $105^{\\circ}\\mathrm{C}$ for $24\\mathrm{~h~}$ to ensure moisture escaped from the palm oil waste. Now, OPS is ready to be used as a precursor for biochar production.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.2. Production of biochar  \n\nThe prepared OPS palm oil waste is utilized as a precursor to produce biochar. This process involved multiple steps to ensure the quality and integrity of the product. The process starts with placing $200~\\mathrm{g}$ of OPS stainless steel pyrolizer and subsequently initiating pyrolysis process. The pyrolization process takes place in a compact muffle furnace suit­ able for high-temperature pyrolysis. The compact muffle furnace tem­ perature is raised gradually to $400~^{\\circ}\\mathrm{C}$ and held for $^\\textrm{\\scriptsize1h}$ . The entire pyrolization process is monitored using $\\mathrm{~K~}$ -type thermocouple that is placed inside the pyrolizer to ensure temperature accuracy. Throughout the entire process, nitrogen gas $\\left(\\Nu_{2}\\right)$ is used to purge air from inside the pyrolizer at a rate of $500~\\mathrm{mL/min}$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.3. Preparation of zinc Chloride-Silicon wafer  \n\nThe preparation for the graphene growth template involved a few steps to ensure its readiness for subsequent graphene synthesis. The template is made from a silicon wafer disc that is cut to $_{1\\thinspace\\mathrm{cm}\\mathrm{x}1}$ cm using a diamond cutter. After the cutting process, each silicon wafer was cleaned and dried in the Force Air Convention Oven for $^\\textrm{\\scriptsize1h}$ . Subse­ quently, the production of $\\mathrm{ZnCl}_{2}$ solution with a molarity of $\\approx0.4\\mathrm{{M}}$ is produced. The $0.4\\mathrm{~M~ZnCl_{2}}$ solution produced is airbrushed onto the cleaned silicon wafer with $15\\ \\mathrm{cm}$ between the two. Finally, the silicon wafer silicon wafer coated with a layer of $\\mathrm{ZnCl}_{2}$ is dried in a Drying Oven (Drying Oven Memmert UNB-500) at $105^{\\circ}\\mathrm{C}$ for $^\\textrm{\\scriptsize1h}$ to produce $\\mathrm{ZnCl}_{2}$ - Silicon Wafer (ZnSw), ready to be used as graphene growth template for",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# CVD.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# 2.4. Chemical Vapor deposition Procedure  \n\nA tubular quartz tube with a length of $124\\mathrm{cm}$ , an internal diameter of $6.9\\mathrm{cm}$ , and an outer diameter of $7.5\\mathrm{cm}$ is placed in a Heating Furnace (Naber-Labortherm R70/9 Furnace). (ABC-1) The biochar produced and ZnSw is placed in an alumina boat with a length of $10.0\\mathrm{cm}_{\\mathrm{i}}$ , a height of $1.8\\mathrm{cm}$ , and a width of $4.0\\mathrm{cm}$ , then two different alumina boats with (i) a length of $5.0\\mathrm{cm}$ , a height of $2.0\\mathrm{cm}$ and width of $2.0\\mathrm{cm}$ and (ii) with a length of $5.0\\mathrm{cm}$ , a height of $0.5\\mathrm{cm}$ and width of $1.0\\mathrm{cm}$ is placed in a position to cover the biochar and ZnSw. The temperature of the furnace is raised to $900^{\\circ}\\mathrm{C}$ , the heating rate of $10\\mathrm{^{\\circ}C/m i n}$ , and the residence time of $35\\mathrm{min}$ . Nitrogen gas $\\left(\\Nu_{2}\\right)$ was used as an inert gas to purge air from inside the pyrolizer at $500\\mathrm{mL/min}$ ; the purging was continued from the start of the process until the pyrolizer is cooled down. (ABC-2) Continuing the experiment, different placement of alumina boat was done, as the biochar produced and ZnSw is placed in an alumina boat with a length of $9.0\\mathrm{cm}$ , a height of $1.5\\mathrm{cm}$ , and width of $1.0\\mathrm{cm}$ , then a similar-sized alumina boat was placed on top. The same heating pa­ rameters are done on ABC-2. In Fig. 1, two different configurations of the alumina boat, namely ABC-1 and ABC-2, are presented. After conducting the experiments, the resulting samples obtained from both boat con­ figurations were analyzed and compared.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3. Results and discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.1. Growth mechanism  \n\nThe growth mechanism occurs during the CVD process, whereas the action compromises multiple steps for Bio-Graphene deposition. The first is, the thermal breakdown of biochar and gaseous compound release (He et al., 2018). Thermal pressure at $900^{\\circ}\\mathrm{C}$ is applied to the alumina boat and biochar gains higher kinetic energy. The increase in kinetic energy results in the breakdown of biochar, resulting in various gaseous releases including methane $\\mathrm{(CH}_{4}\\mathrm{)}$ , carbon dioxide $\\left(\\mathrm{CO_{2}}\\right)$ , and other volatile gases (Abhijeet et al., 2019). The gaseous release that occurs during this step is due to carbon-containing bonds in the biochar decomposition.  \n\nThe second step involves methane decomposition into the carbon layer. $\\mathrm{CH}_{4}$ , which is the main gaseous compound produced from the previous step plays a vital role for carbon deposition. In the hightemperature CVD environment, $\\mathrm{CH}_{4}$ acquires sufficient energy to un­ dergo thermal decomposition into elements of carbon and hydrogen gas. The carbon in this case deposits itself onto the substrate forming a layer. On the other hand, hydrogen gaseous remains stagnant around the CVD environment growth for a while and subsequently flows out with the nitrogen-supplied gas. The carbon layer is an important part of the experiment to finalize the graphene growth.  \n\nDuring these two steps, another reaction happen which is the decomposition of zinc chloride $\\mathrm{(ZnCl_{2})}$ . This is the third step that simultaneously occur with the previous two mentioned steps. As the temperature increases within the CVD environment, beyond its boiling point the compound begins to decompose into zinc crystal and chloride gas. The chloride gas escapes the tubular furnace, while the zinc crystal deposits onto the silicon wafer. The zinc becomes an active part during the redox reaction that will occur subsequently.  \n\nIn the fourth step, $\\mathsf{C O}_{2}$ is procured in the second step, and zinc crystals obtained in the third step react with each other. This reaction is critical to the CVD process because it forms zinc oxide (ZnO) and carbon monoxide (CO). In this reaction, zinc crystal absorbs one oxygen molecule from $\\mathsf{C O}_{2},$ producing the compound $z_{\\mathrm{{nO}}}$ and gas by-product, CO (Lu et al., 2018). The $z_{\\mathrm{{nO}}}$ is responsible for converting the carbon layer produced during the first step into graphitic-nature carbon.  \n\nThis results in the last step which is porous activity. The carbon layer deposited in the first step interacts with $z_{\\mathrm{{nO}}}$ produced in the fourth step in order to create a porous layer, in turn graphitic-nature layer. The carbon element absorbs one oxygen from the $z_{\\mathrm{{nO}}}$ to produce zinc crystals and carbon monoxide. This zinc crystal can continue partici­ pating in further reactions, and the carbon monoxide escapes the tubular furnace as a gas. The continuous cycling of these reactions contributes to the formation of pores in the material.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3.2. Characterization of bio-graphene  \n\nField Emission Scanning Electron Microscopy (FESEM) was con­ ducted on the fabricated Bio-Graphene samples to observe their surface structure. In terms of morphology, FESEM was performed on the fabri­ cated carbon-based nanomaterial, labeled ABC-1 and ABC-2, based on their respective settings. ABC-1 exhibited an agglomeration of mostly bonded particles with some minor segregation and a round-to-oval pattern, while ABC-2 showed an uneven layered growth and partial exfoliation at the base. ABC-1 had a more planar surface compared to ABC-2, which had a higher carbon deposition.  \n\nThe FESEM can detect the presence of a carbon layer on the substrate after fabrication. Both samples exhibited the presence of carbon on the substrate, thus indicating the success of the novel fabrication process. Two types of Bio-Graphene were produced, labeled ABC-1 and ABC-2, based on their respective settings and alumina boat placement. The FESEM analysis of ABC-1 showed an agglomeration of mostly bonded particles, with some particles showing minor segregation and a roundto-oval pattern. The surface presents a relatively uniform and smooth texture, indicating a smooth morphological structure without significant agglomeration (Fig. 2(a)). In contrast, ABC-2 showed an uneven layered growth and higher carbon deposition. The ‘splotches’ graphene struc­ ture indicates the presence of a thicker carbon layer with a higher possibility of surface defects. ABC-2 overall morphology is less uniform than ABC-1, with a rougher exterior structure. Despite these differences, both ABC-1 and ABC-2 exhibited close-bonded carbon structure and layering in the FESEM analysis. Comparing the FESEM results obtained in this study to previous research that uses pure methane to fabricate graphene, shows similarities between them. Both products have planar characteristics with a tendency to agglomerate, forming a cohesive layer. Both products also show the trend of carbon deposition increment as the volume of methane increases (Selvakumar et al., 2016). It is speculated that ABC-2 has a higher chance of methane-to-substrate contact due to its configuration, which involves a total cover alumina boat.  \n\n![](images/af1bd090201fed749fa2310761762a33c83d9e401031b865431fae205adf62cb.jpg)  \nFig. 1. Placement of Alumina Boat for ABC-1 and ABC-2.  \n\n![](images/4efcd02e8bdc7cdfd30da54f934eabb19250766c5edb1af48948d34d6de0b479.jpg)  \nFig. 2. (a) FESEM image of ABC-1, (b) FESEM image of ABC-2, (c) AFM 3D Image for ABC-1 and (d) AFM 3D Image for ABC-2 ${\\bf{\\{n=1\\}}}$ samples each)  \n\nAtomic Force Microscopy (AFM) 3D imaging and root mean square (RMS) surface roughness were used to further observe the surface morphology of ABC-1 and ABC-2. According to the 3D images in Fig. 2 (c,d), ABC-1 had a more even surface for the Bio-Graphene compared to ABC-2, which displays a less planar surface. This is due to the higher chance of methane to substrate contact for ABC-2 which promotes better carbon deposition. Additionally, AFM shows that the surface roughness of ABC-1 was also found to be lower than that of ABC-2, as shown in Table 1. A lower surface roughness indicates a more uniform carbonbased nanomaterial layer (Salifairus et al., 2018). Previous studies have reported similar trends in AFM surface roughness of selected samples indicating that those with the lowest surface roughness values are more likely to have a planar structure of graphene (Mesˇkinis et al., 2022). According to mechanistic observation by FESEM and AFM, ABC  \n\nTable 1 AFM Surface Roughness and Thickness for ABC-1 and ABC2.   \n\n\n<html><body><table><tr><td>Sample</td><td>Surface Roughness (nm)</td></tr><tr><td>ABC-1</td><td>40.3</td></tr><tr><td>ABC-2</td><td>55.9</td></tr></table></body></html>  \n\n1 morphology indicates areas that could potentially be multi-layer graphene under smoother and more uniform surfaces but with higher roughness and significant peak formations. On the other hand, ABC-2 demonstrates graphene with a less pronounced layer, possessing a higher irregular surface (possible defect) but more evenly distributed surface morphology.  \n\nFor the internal structure of graphene, Raman is done on fabricated Bio-Graphene by observing the vibrational energy modes. Both samples possess the G, D, and 2D bands that arise from the graphitic structure and $\\mathsf{s p}^{2}$ layer of hybridization (Safian et al., 2021). The G band corre­ sponds to the $\\mathbf{E}_{2g}$ phonon of the $\\displaystyle\\mathsf{s p}^{2}$ carbon atom, while the D band corresponds to the breathing mode of k-point phonons of $\\mathbf{A}_{1g}$ symmetry at the vibration of the atom in planar termination of irregular graphite (Widiatmoko et al., 2019). ABC-2 has a higher and observable G and D band than ABC-1. ABC-2 having stronger signals than ABC-1 indicates that ABC-2 carbon-based nanomaterial has a smaller crystalline size (Nasir et al., 2019). G and D bands of ABC-1 were observed to be 1602 and $1334\\mathrm{cm}^{-1}$ , respectively in Fig. 3. Whereas the G band and D band of  \n\n![](images/88dc0d2266598c192e6f8658f07a31bc6ec3126eb15b775ecf04a2ecfd3b86e0.jpg)  \nFig. 3. Raman Graphical for ABC-1 and ABC-2 ( ${\\bf{\\dot{n}}}=1$ samples each).  \n\nABC-2 were observed to be 1583 and $1330\\mathrm{cm}^{-1}$ , respectively. Previous work employed CVD to create Bio-Graphene layers by using Palm Oil Waste as precursor biomass. The previous results showed similar MicroRaman mapping located around the same area as this paper’s result (Salifairus et al., 2016). The G and D band ratio intensity presents the quality of the carbon-based nanomaterial produced. As seen in Table 2, their ratio intensity is $\\mathrm{I_{G}}/\\mathrm{I_{D}}=1.2$ for ABC-1 and $\\mathrm{I_{G}/I_{D}}=0.7$ for ABC-2. ABC-2 possesses a lower ratio intensity than ABC-1 despite having higher and observable G and D bands. This indicates that ABC-2 has a lower degree of graphitization than ABC-1 (Amir Faiz et al., 2020). An additional ${\\bf D}^{\\prime}$ band peak can be seen at $1603\\mathrm{cm}^{-1}$ . Defectiveness within the structure causes the G band to broaden which creates a D’ band peak (Kaniyoor & Ramaprabhu, 2012). The RAMAN analysis results are further solidified when compared to FESEM results. During morpho­ logical observation, ABC-2 is suspected to possess a higher level of defect compared to ABC-1 due to its presence of a thicker carbon layer. This coincides with RAMAN analysis showing a more prominent D band (defect band) for ABC-2.  \n\n2D band is the secondary peak of D band. High 2D band is associated with single layer graphene and low 2D band is associated with multi­ layer graphene. As seen in Table 2, their ratio intensity is $\\mathrm{I_{2D}/I_{G}}=0.7$ for ABC-1 and $\\mathrm{I_{2D}/I_{G}}=0.6$ for ABC-2. The 2D and G band ratio intensity band indicates the number of layers within graphene structure. The $\\mathrm{I_{2D}/}$ $\\mathrm{I_{G}}$ value less than 1 indicates 3 or more-layer graphene (Castriota et al., 2019). However, in some cases of $\\mathrm{I_{2D}/I_{G}}$ values between 0.3 and 0.8, the graphene can be treated as 2–3 layers of graphene (Akhavan et al., 2014). The number of layers of Bio-Graphene indicates two to three graphene layers for ABC-1 and ABC-2. The result is an improvement from Robaiah Hj Mamat in 2018 which also uses palm oil waste to create graphene through CVD which $\\mathrm{I_{2D}/I_{G}}$ value was 0.3 (Mamat et al., 2018). ABC-1 and ABC-2 analyzed 2D bands that possessed shortcomings due to their peak position. Typical single-layer graphene is around $2700\\mathrm{cm}^{-1}$ while both samples (ABC-1, ABC-2) have shifted away from the value, indication strain, and defect. Although ABC-1 indicates lower defect and graphene layer, the peak prominence highly favours ABC-2 suggesting higher graphene deposition on the substrate. This, in turn, results in a higher product-to-raw-material ratio.  \n\nTable 2 Micro-Raman value of D, G and 2D for ABC-1 and ABC-2.   \n\n\n<html><body><table><tr><td>Sample</td><td>G-Band (cm-1)</td><td>D-Band (cm-1)</td><td>2D-Band (cm-1)</td><td>IG/ID</td><td>I2D/IG</td></tr><tr><td>ABC-1</td><td>1602</td><td>1334</td><td>2844</td><td>1.2</td><td>0.7</td></tr><tr><td>ABC-2</td><td>1583</td><td>1330</td><td>2656</td><td>0.7</td><td>0.6</td></tr></table></body></html>  \n\nFor the crystalline structure of graphene, XRD is done on fabricated Bio-Graphene by observing the peak position. ABC-1 and ABC-2 are done for XRD spectra in the range of 2θ from 10 to $60^{\\circ}$ as shown in Fig. 4. XRD results have high noise signal from low nucleation of the carbonbased nanomaterial on a silicon wafer and create difficulty in detect­ ing formation (Holder & Schaak, 2019). The best estimation was given due to the high noise. Moreover, it can be observed that there are no discernible peaks at $2\\uptheta=42.8^{\\circ}$ , which is associated with a graphene crystalline peak at (0 0 2). The possibility for this occurrence is due to: (i) high noise-to-signal ratio or (ii) short-range order in stacked BioGraphene layers (Stobinski et al., 2014).  \n\nFurthermore, both XRD diffraction peaks are quite low indicating Bio-Graphene produced has a structure between the crystalline and amorphous structures. The broadness of both samples suggests that there were more oxygen-containing groups on the edges of each layer (Yang et al., 2020). From the observed peak broadening, it is inferred that the stacking of the carbon-based nanomaterial is not well-ordered due to incomplete exfoliation (Lee et al., 2019). There is an indication of the crystalline peak at (0 0 2) with a diffraction peak at $2\\uptheta=21.48^{\\circ}$ for ABC-1 and $2\\uptheta=22.8^{\\circ}$ for ABC-2 as seen in Fig. 4. The prominent graphene peak around $2\\theta\\:=\\:25{-27^{\\circ}}$ is absent indicating amorphic structure diverting away from graphitic lattice structure. Broad peaks on both samples indicated that it is not highly crystalline likely to have defects, multi-layer structure, and disordered carbon structure. How­ ever, ABC-2 possessed a higher intensity than ABC-1, suggesting a more ordered carbon structure and higher graphene content. The XRD anal­ ysis results are further cemented when compared to FESEM and RAMAN results indicating that both samples indeed possessed levels of defect.  \n\nBy using Bragg’s Equation to the (0 0 2), intercellular spacing can be obtained. The intercellular spacing of ABC-1 and ABC-2 is $0.4~\\mathrm{{nm}}$ and $0.4~\\mathrm{{nm}}$ , respectively. On the other hand, by using Scherrer’s equation and the constant value 0.9 from the (0 0 2) reflection, the crystalline size for ABC-1 and ABC-2 is $2.4\\ \\mathrm{nm}$ and $2.0\\ \\mathrm{nm}$ , respectively as seen in Table 3 (Stobinski et al., 2014). Thus, ABC-2 has a smaller crystalline size than ABC-1.  \n\nThe IV measurement is conducted on ABC-1, ABC-2, and silicon wafers. Alumina adheres to the surface of ABC-1, ABC-2, and silicon wafers. For ABC-1 and ABC-2, alumina covered the Bio-Graphene deposited onto the silicon wafer. The results show the IV measurement of ABC-1 is $150\\Omega$ , while ABC-2 had a resistance of $112.5\\Omega$ . On the other hand, the silicon wafer has the highest resistance at $387.5\\Omega$ . As seen in  \n\n![](images/5a5554d39c10604d1c3b9be92980eb1348bda0c988b71f36dd98f78a41c1f5e0.jpg)  \nFig. 4. XRD for ABC-1 and ABC-2 $\\mathbf{\\tilde{n}}=1$ samples each).  \n\nTable 3 Structural parameters of ABC-1 and ABC-2 resulting from the XRD patterns.   \n\n\n<html><body><table><tr><td>Sample</td><td colspan=\"2\">Peak (002)</td><td></td><td></td><td></td></tr><tr><td></td><td>20 (deg)</td><td>FWHM (deg)</td><td>Crystalline Size (nm)</td><td>Intercellular Spacing (nm)</td><td>Graphene Layers Number</td></tr><tr><td>ABC-1</td><td>21.5</td><td>3.3</td><td>2.4</td><td>0.4</td><td>8</td></tr><tr><td>ABC-2</td><td>22.8</td><td>3.9</td><td>2.0</td><td>0.4</td><td>7</td></tr></table></body></html>  \n\n![](images/416903f9204a7ec22515e094d1cd1503213f9dfcb1cf0c0182dcc5c7ad28c0c8.jpg)  \nFig. 5. I-V Curve for Silicon Wafer, ABC-1 and ABC-2 ${\\bf{\\hat{n}}}=1$ samples each).  \n\nFig. 5, the slope is greater for the two carbon-based nanomaterials deposited onto the silicon wafer samples compared to the silicon wafer indicating a lower resistivity to the former. This is due to the presence of Bio-Graphene that improves on the electron pathway which is attributed to its conducting properties (Mulla et al., 2023). When calculating the resistivity and conductivity of ABC-1 and ABC-2, it shows that ABC-1 has a higher resistivity and lower conductivity than ABC-2. ABC-1 resistivity and conductivity are $280.4\\Omega\\mathrm{m}$ and $3.6\\times10^{-5}\\mathrm{S/cm}.$ respectively, while resistivity and conductivity are 127.1 Ωm and $7.9\\times10^{-5}\\ \\mathrm{S/cm}$ . The difference in resistance between ABC-1 and ABC-2 is related to the quality of the carbon-based nanomaterial on the silicon wafer. This correlates with better quality graphene having higher structural lattice ordering which significantly enhances the graphene pathway to be less resistive and conduct more electricity (Yildiz et al., 2021).  \n\nXPS provides a comprehensive analysis of chemical composition that provides a thorough insight into the entirety of the produced BioGraphene framework. The evaluation presents unique spectra peaks that correlate to individualized core-level electrons of the atom’s bind­ ing energy. This determines the specialized atomic elements of the carbon-based nanomaterial, in this case consisting of $\\mathbf{C}_{1s},$ $\\mathrm{O}_{1s}$ , $\\mathrm{Si}_{2s_{:}}$ , and $\\sin_{2\\mathrm{p}}$ situated at $\\sim285\\mathrm{eV}$ , ${\\sim}531\\mathrm{eV}$ , ${\\sim}155\\mathrm{eV}$ , and $\\sim104\\mathrm{eV}$ (Keyn et al., 2021). The presence of $\\mathrm{Si}_{2s}$ and $\\sin_{\\mathrm{{}}}\\operatorname{si}_{2{\\mathrm{{p}}}}$ in Fig. 6 is due to the silicon wafer substrate, securing the deposited carbon-based nanomaterial layer. $\\mathbf{C}_{1s}$ presence at $\\sim285\\ \\mathrm{eV}$ confirms carbon species layering on the silicon wafer during CVD that consists of $\\mathsf{s p}^{2}$ carbon atoms in a graphitic structure. The peak at \\~ 531 eV appeared due to oxygen. The overall XPS spectra managed to capture ABC-2 molecular makeup that further validated the fabrication process, utilizing an alumina boat for gaseous capture on a silicon wafer for carbon layering.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 4. Conclusion  \n\nBio-Graphene is synthesized from OPS biomass via pyrolysis and  \n\n![](images/d76f0ef630ad534d41a6672a4f206add7589cf4c493761f905a8e40b24dea403.jpg)  \nFig. 6. Full XPS graph of the ABC-2 $\\mathbf{\\tilde{n}}=1$ samples each).  \n\nCVD. This method involves applying gaseous compounds from pyro­ lyzed OPS biochar directly onto a silicon wafer using two alumina boat configurations: ABC-1 and ABC-2. By bypassing etching and transfer steps, the characterization of carbon-based nanomaterial becomes easier. ABC-2 offers better encapsulation of gaseous compounds, leading to improved carbon deposition, higher nucleation, well-ordered struc­ ture, reduced graphitic layers, enhanced crystallinity, and higher con­ ductivity. This research demonstrates the potential of biomass-derived biogas in synthesizing eco-friendly carbon-based nanomaterial. Such advancements could replace methane-based graphene, enabling affordable, sustainable, and environmentally friendly production methods.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 17,
+        "chunk": "# CRediT authorship contribution statement  \n\nM.D. Nurhafizah: Conceptualization, Supervision, Funding acqui­ sition, Writing – original draft, Writing – review & editing. A.A. Azahar: Investigation, Methodology, Writing – original draft. N. Abdullah: Su­ pervision, Data curation.",
+        "category": " Abstract"
+    },
+    {
+        "id": 18,
+        "chunk": "# Funding  \n\nThis work was supported by the Ministry of Higher Education Malaysia for Fundamental Research Grant Scheme (FRGS) with project code: FRGS/1/2019STG05/USM/02/7 and Research University Grant (RUI), Universiti Sains Malaysia with project code: 1001/PFIZIK/ 8011113.",
+        "category": " References"
+    },
+    {
+        "id": 19,
+        "chunk": "# Declaration of competing interest  \n\nThe authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 20,
+        "chunk": "# Acknowledgements  \n\nA special thanks to the Ministry of Higher Education Malaysia for the Fundamental Research Grant Scheme (FRGS) with project code: FRGS/ 1/2019STG05/USM/02/7 and Research University Grant (RUI), Uni­ versiti Sains Malaysia with project code:1001/PFIZIK/8011113 for the financial supports. The authors also want to express their gratitude to Energy Lab, School of Physics, Universiti Sains Malaysia for the statistics information provided.",
+        "category": " Acknowledgements"
+    },
+    {
+        "id": 21,
+        "chunk": "# References  \n\nAbhijeet, P., Swagathnath, G., et al., 2019. Prediction of pyrolytic product composition and yield for various grass biomass feedstocks. Biomass Convers. Biorefin. 2019 10:3 10, 3, 663–674.   \nAkhavan, O., Ghaderi, E., et al., 2014. Ultra-sensitive detection of leukemia by graphene. Nanoscale. 6 (24), 14810–14819.   \nAmir Faiz, M.S., Che Azurahanim, C.A., et al., 2020. Low cost and green approach in the reduction of graphene oxide (GO) using palm oil leaves extract for potential in industrial applications. Results Phys. 16, 102954.   \nCastriota, M., Politano, G.G., et al., 2019. Variable angle spectroscopic ellipsometry investigation of CVD-grown monolayer graphene. Appl. Surf. Sci. 467–468, 213–220.   \nDobrzanski, L., Pakula, D., Staszuk, M., 2013. chemical vapor deposition in manufacturing. Handbook of Manufacturing Engineering and Technology 1–41.   \nHe, X., Liu, Z., et al., 2018. Effects of pyrolysis temperature on the physicochemical properties of gas and biochar obtained from pyrolysis of crop residues. Energy 143, 746–756.   \nHolder, C.F., Schaak, R.E., 2019. Tutorial on powder X-ray diffraction for characterizing nanoscale materials. ACS Nano. 13 (7), 7359–7365.   \nKaniyoor, A., Ramaprabhu, S., 2012. A Raman spectroscopic investigation of graphite oxide derived graphene. AIP Adv. 2 (3), 032183.   \nKeyn, M., Adrian Krauss, T., et al., 2021. Enhancing electrical properties of carbon nanotubes thin films by silicon incorporation. IOP Conf Ser Mater Sci Eng 1206 (1), 012028.   \nLee, S.M., Park, Y.J., et al., 2019. Laser reduction of Zn-infiltrated multilayered graphene oxide as electrode materials for supercapacitors. ACS Appl. Nano. Mater. 2 (6), 3711–3717.   \nLu, Y., Han, B., et al., 2018. Efficient electrocatalytic reduction of CO2 to CO on an electrodeposited Zn porous network. Electrochem. Commun. 97, 87–90.   \nMahlia, T.M.I., Ismail, N., et al., 2019. Palm oil and its wastes as bioenergy sources: a comprehensive review. Environ. Sci. Pollut. Res. 26 (15), 14849–14866.   \nMaithel, S., 2009. Biomass Energy Resource Assessment Handbook Asian and Pacific Centre for Transfer of Technology Of the United Nations-Economic and Social Commission for Asia and the Pacific (ESCAP).   \nMamat, R.H., Hamzah, F., et al., 2018. Influence of volume variety of waste cooking palm oil as carbon source on graphene growth through double thermal chemical vapor deposition. IEEE International Conference on Semiconductor Electronics.   \nMeˇskinis, V.A., et al., 2022. The direct growth of planar and vertical graphene on Si(100) via microwave plasma chemical vapor deposition: synthesis conditions effects. RSC Adv. 12 (29), 18759–18772.   \nMulla, M.Y., Isacsson, P., et al., 2023. Bio-graphene sensors for monitoring moisture levels in wood and ambient environment. Global Chall. 7 (4), 2200235.   \nNabila, R., Hidayat, W., et al., 2023. Oil palm biomass in Indonesia: Thermochemical upgrading and its utilization. Renew. Sust. Energ. Rev. 176, 113193.   \nNasir, S., Hussein, M.Z., et al., 2019. Development of New Carbon-Based Electrode Material from Oil Palm Waste-Derived Reduced Graphene Oxide and Its Capacitive Performance Evaluation. J. Nanomater. 2019.   \nOmar, A.K.M., Tengku Norsalwani, T.L., et al., 2018. Implementation of the supercritical carbon dioxide technology in oil palm fresh fruits bunch sterilization: A review. Journal of CO2 Utilization. 25, 205–215.   \nSafian, M.T., Uddeen, U.K., et al., 2021. Synthesis and scalability of graphene and its derivatives: A journey towards sustainable and commercial material. J Clean Prod. 318, 128603.   \nSalifairus, M.J., Hamid, S.B.A., et al., 2016. The effect of synthesis time on graphene growth from palm oil as green carbon precursor. AIP Conf. Proc. 1733 (1), 020066.   \nSalifairus, M.J., Soga, T., et al., 2018. The synthesis of graphene at different deposition time from palm oil via thermal chemical vapor deposition. AIP Conf. Proc. 1963 (1), 020007.   \nSelvakumar, N., Vadivel, B., et al., 2016. Controlled growth of high-quality graphene using hot-filament chemical vapor deposition. Appl. Phys. A Mater. Sci. Process 122 (11), 1–11.   \nSerykh, A.I., Agafonov, Y.A., 2020. On the nature of active sites in alumina-supported zinc propane dehydrogenation catalysts. Mol. Catal. 493, 111055.   \nStobinski, L., Lesiak, B., et al., 2014. Graphene oxide and reduced graphene oxide studied by the XRD, TEM and electron spectroscopy methods. J Electron Spectros. Relat. Phenomena. 195, 145–154.   \nWidiatmoko, P., Sukmana, I.F., et al., 2019. Increasing yield of graphene synthesis from oil palm empty fruit bunch via two-stages pyrolysis. IOP Conf. Ser. Mater. Sci. Eng. 543 (1), 012032.   \nXie, L., Xu, J., et al., 2020. Biogas Upgrading Advances in Bioenergy 5, 309–344.   \nYang, Z., Sun, Y., et al., 2020. Interlayer spacing of multilayer graphene oxide: influences of oxygen-containing group density, thickness, temperature and strain. Appl. Surf. Sci. 529, 147075.   \nYildiz, G., Bolton-Warberg, M., et al., 2021. Graphene and graphene oxide for biosensing: general properties and the effects of graphene ripples. Acta Biomater. 131, 62–79.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# A robust and transparent hydrogel coating for sustainable antifogging with excellent self-cleaning and self-healing ability  \n\nXuanfei $\\mathtt{X u}^{\\mathrm{a}}$ , Tianxue Zhu a,b, Weiwei Zheng a, Caiyun Xian a, Jianying Huang a, Zhong Chen c, Weilong Cai a,d, Weiying Zhang a,d,\\*, Yuekun Lai a,d,\\*  \n\nCollege of Chemical Engineering, Fuzhou University, Fuzhou 350116, PR China   \nb China National Textile and Apparel Council Key Laboratory of Flexible Devices for Intelligent Textile and Apparel, Soochow University, Suzhou 215123, PR China   \nc School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore   \nd Qingyuan Innovation Laboratory, Quanzhou 362801, PR China",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# A R T I C L E  I N F O",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# A B S T R A C T  \n\nKeywords:   \nSelf-healing   \nTransparency   \nAntifogging   \nAntifouling   \nChemical durability  \n\nFilms with antifogging properties can be used in a wide range of fields, from manufacturing to agriculture, such as screens, camera lenses, and greenhouse films. In this study, a scraping technique was utilized to coat anti­ fogging films on polyethylene substrate by using a solution containing polyvinyl alcohol, sodium alginate, and glycerin with suspended titanium dioxide nanoparticles. The resulting hydrophilic coating has outstanding antifogging, self-healing, and anti-fouling qualities due to the polymer’s great hydration capacity. The coating also held up well during prolonged heat and ultraviolet exposure ( $40^{\\circ}\\mathrm{C}$ for 17 days and $_{192\\mathrm{h}}$ of $1.27\\mathrm{mW/cm^{2}}$ UV radiation). Furthermore, when exposed to $30~\\mathrm{g}$ sands impact from a height of 10 to $40\\ \\mathrm{cm}$ , 18 days outdoors and 1 h soaking in polar and non-polar solvents (absolute ethanol, isopropanol, n-hexane and n-hexadecane), the hydrophilicity and antifogging performance were well sustained. Different flexible/rigid substrates, such as PET, PC, PVC, and others, can be successfully coated with antifogging film by using such simple construction approach.",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1. Introduction  \n\nFogging in films have posed a significant obstacle to greenhouse horticulture, agricultural progress, and human life [1–2]. The formation of fog on greenhouse films may reduce the transmission of light, affecting plant photosynthesis. Furthermore, rot and breed bacteria readily thrive in the absence of appropriate light, resulting in a drastic reduction in agricultural productivity [3]. As a result, technologies or materials that can effectively prevent or reduce fogging on the agricul­ tural film surface are critical for realizing long-term sustainability and efficiency. When the temperature and humidity drop, a substantial amount of vapor in the air condenses and adheres to the surface of the substrate, forming fog. The substrate changes from transparent to opa­ que due to diffuse reflection and refraction induced by the condensed droplets [4–6].  \n\nSeveral approaches, including substrate surface heating to lessen the temperature difference, have been used to eliminate the effect of un­ desired fogging [7]. However, this technology has a disadvantage of consuming a lot of energy, which has limited its use on a big scale. There is an immediate need for a more efficient and environmentally friendly strategy. The alteration of material surface wettability has received a lot of attention [8–16]. For example, the superhydrophobic surface’s strong water-resistant properties have made it a promising contender for antifogging applications [17–25]. Jiang et al. used soft lithography to create superhydrophobic artificial compound eyes that can be used to build new antifogging coatings, inspired by mosquito compound eyes. The droplet might potentially remove polluting particles away from the surface, according to the coating’s self-cleaning characteristic. However, the superhydrophobic coating was typically inadequate in terms of robustness and process complexity, and it was also nontransparent [26].  \n\nTo solve these flaws, researchers focused their efforts on developing a super-hydrophilic film that spreads condensed droplets quickly, generating an aqueous layer with uniform thickness that allows light to pass through the substrate without scattering [27–35]. Manufacturing procedures like as dipping, knife coating, and spin coating, are frequently employed. For example, Kim et al. proposed a silica com­ posite Fe(III)-tannic acid nanocoating which underwent 5 cycles of acid and alkali, sodium percarbonate deposition for $150~\\mathrm{min}$ , and hot and cold treatment for $120\\ \\mathrm{min}$ each without structural damage, demon­ strating the durability of the coating [19]. Sun et al. developed an antifogging UV-curable coating based on raspberry-like particles and illustrated the incorporation of raspberry-like particles to significantly improve the hardness of the coating by pencil hardness test and scratch method experiments [36]. Liang et al. prepared self-healing and antifouling films with high transparency by a one pot method that can mend, severe scratches inflicted in harsh conditions. However, the modification of silicon nanoparticles was too complicated, and the coating’s mechanical qualities were insufficient to meet actual manufacturing requirements [37]. Yang et al. used the sol–gel process to make a series of $\\mathrm{Fe}^{3+}$ -doped $\\mathrm{TiO}_{2}$ films, which were then dip coated on the target substrate. The resulting sample had outstanding antifogging capabilities as well as long-lasting superhydrophilicity. However, the coatings lacked rapid self-healing ability, which make them unsuitable for long-term use [38]. Despite significant progress, difficulties like as complex production process, long-term durability against physical and chemical damage, universality for different substrates, remain unsolved.  \n\n![](images/047d2f3fd638431343ed1a08dc049454475d6fb1f537600fc156927811e87cfd.jpg)  \nScheme 1. Schematic illustration for manufacturing the antifogging PE film.  \n\n![](images/204a57385cfc8f6386d9d10d8a6fcf4056ac37eaab0c3e7ce74c52bd1dbecc83.jpg)  \nFig. 1. a) SEM photograph of the coated PE, the inset is the cross-sectional SEM image and the underwater oil contact angle of the coating. b) Corresponding mapping images of C, Na, O, and Ti elements. c) EDS spectrum and elements proportion of the PSTG coating. d) FTIR spectra of SA, PVA, $\\mathrm{TiO}_{2},$ and the as-prepared PSTG film.  \n\nHere, we present a simple approach to construct a high-transparency antifogging coating with polyvinyl alcohol (PVA), sodium alginate (SA), titanium dioxide $\\left(\\mathrm{TiO}_{2}\\right)$ , and glycerin (PSTG coating). The PSTG film exhibits a number of unique performances, including effective contam­ ination removal via self-cleaning, quick scratch healing, universality across a variety of surfaces, and outstanding antifogging capabilities. In addition, this film maintains its antifogging properties through a variety of harsh situations including prolonged lasting heat and ultraviolet treatment ( $40^{\\circ}\\mathrm{C}$ for 17 days and $_{192\\mathrm{h}}$ of $1.27\\mathrm{mW/cm^{2}}$ UV radiation), impact by $_{30\\mathrm{~g~}}$ of sands from a height of 10 to $40\\ \\mathrm{cm}$ , exposure to outdoor environments for 18 days, and $^{\\textrm{1h}}$ of soaking in polar and nonpolar solvents. The coating’s exceptional qualities have led to specula­ tion that it may be utilized in greenhouse films to prevent fog from affecting photosynthesis, as well as optically clear equipment such as windshields, periscopes, and display devices.  \n\n![](images/0f2e71f161f85d13cdeddad59bc2460b76ef075e0f89cf337998c2993bf00723.jpg)  \nFig. 2. a) Optical image of $20~\\upmu\\mathrm{L}$ methyl blue solution $(10\\mathrm{ppm})$ before and after the PSTG coating and PSG coating were exposed to $365\\mathrm{nm}$ ultraviolet light for 20 min. b) Antifogging performance of PSTG coating (top) and the water contact angles of coated PE in air (bottom). c) UV–Vis transmission spectra of the bare PE and the coated PE. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2. Experimental section",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.1. Materials and reagents  \n\nPVA and $\\mathrm{TiO}_{2}$ (anatase, hydrophilic $99.8\\%$ , $30\\ \\mathrm{nm}.$ ) were obtained from Aladdin. Hydrophilic anatase $\\mathrm{TiO}_{2}$ , anatase, particles, $99.8\\%$ in purity, with different sizes $20\\ \\mathrm{nm}$ , $40\\ \\mathrm{nm}$ , $60~\\mathrm{{nm}}$ , $100~\\mathrm{{nm}}.$ were pur­ chased from Macklin. SA, n-hexane, hexadecane, absolute ethanol, iso­ propanol and glycerin were purchased from Sinopharm Chemical Reagent Co., Ltd. All the materials and reagents were used without further purification. Humidifier and polyethylene film were purchased from local supermarkets.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.2. Methods  \n\nOrthogonal experimental design $\\mathrm{L}_{25}(5^{3})$ was selected to achieve the optimum antifogging effect and production capacity by investigating the mass concentration of raw materials. Three factors were chosen in the experiment to inspect the mass concentration of PVA (factor A), SA (factor B), and $\\mathrm{TiO}_{2}$ (factor C) (Table S1) [39]. The antifogging grade and light transmission were taken as the criteria to calculate the comprehensive score. Among them, the light transmittance is based on the blank film (average value of $400{\\mathrm{-}}720\\ \\mathrm{nm})$ ), and the light trans­ mittance of each group of samples is $0.5\\%$ higher than the blank, plus 1 point, and $0.5\\%$ lower than the blank, 1 point is deducted. The antifogging level is based on level 2, and each higher level will add 2 points, and the lower level will deduct 2 points. The experimental results of the 25 groups are listed in Table S2.  \n\nBased on these experimental results, the mass concentrations of PVA, SA and $\\mathrm{TiO}_{2}$ were chosen to be $2.78\\%$ , $0.83\\%$ and $0.025\\%$ , respectively, owing to their outstanding antifogging capacity and higher light transmittance.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.3. Preparation of the PSTG coating  \n\n$2.78\\mathrm{wt\\%}$ PVA, $0.83\\mathrm{wt\\%}$ SA were dissolved in $35\\mathrm{mL}$ distilled water/ glycerol solution (volume ratio of 6: 1) at $95~^{\\circ}\\mathrm{C}$ for $^{2\\mathrm{~h~}}$ to obtain a ho­ mogeneous and transparent solution, and $0.025\\mathrm{wt}\\%\\mathrm{TiO}_{2}$ particles were suspended in the solution. Here glycerol was used for enhancing the low temperature resistance of the coating, PVA and SA were used for increasing the low surface energy of the coating, $\\mathrm{TiO}_{2}$ was used for improving the aging resistance of the coating. PE membranes were treated with oxygen plasma (Yamato PM100, Japan) for $20~\\mathsf{s}$ to endow the surface with superhydrophilic ability. Subsequently, an appropriate amount of the obtained solution was scraped onto the PE substrate. Eventually, the coated PE was dried at $60~^{\\circ}\\mathrm{C}$ for $^{2\\mathrm{h}}$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.4. Characterization  \n\nThe contact angles (CAs) of the coatings were determined using a contact angle device (Dataphysics OCA25, Germany). The volume of droplets applied for static contact angle and sliding angle measurements is $4\\upmu\\mathrm{L}$ . An atomic force microscope (AFM, Agilent 5500) was employed to exam the surface roughness of the samples. The morphology of the coated PE and its thicknesses were obtained by field emission scanning electron microscope (FESEM, Hitachi S-4800). Elemental analysis was acquired from the energy dispersive spectroscopy (EDS) device attached to the FESEM. The chemical structures were characterized by Fourier transform infrared (FT-IR) (Thermo Fisher Scientific, USA) at a resolu­ tion of $4\\mathrm{cm}^{-1}$ in the range of $4000{-}500\\mathrm{cm}^{-1}$ . The light transmission of the coating was tested by a Persee TU-1900 UV–Vis spectrophotometer. Optical images of the coatings before and after the self-healing test were taken by an optical microscopy (DM2700P, Leica, Germany). The light source was provided by a Solar Power Meter (PerfectLight, PLMW2000). According to the GB/T31726-2015 standard test method, the antifogging level is divided into level 1 to 5. The antifogging per­ formance test is by placing the sample at $2{\\cdot}3\\ \\mathrm{cm}$ above heated water at $85~^{\\circ}\\mathrm{C}$ for $1\\mathrm{min}$ .  \n\n![](images/943730d16322bad0cc5d5840978babf622b1a8e814c97cdbc560ca898de8f5b9.jpg)  \nFig. 3. a) WCAs after continuous exposure to $365~\\mathrm{{nm}}$ UV irradiation for $^{192\\mathrm{~h~}}$ . Inset pictures show antifogging test surface of coated PE exposed to UV and un­ exposed. b) WCAs were tested under the coated PE was continuously heat treated in an oven $(80~^{\\circ}\\mathrm{C})$ . c) Schematic diagram of sand punching experiment. d) The antifogging grade index of the coating exposed to $_{30\\mathrm{~g~}}$ sands at different scouring heights. Inset image shows the antifogging test surfaces of PSTG film at different scouring heights. e) A plot showing the water contact angles the antifogging grade index of the PSTG coating after exposure to various solvents for 1 h. f) Cross-cut method to measure the adhesion of the film, before the tape was peeled off (top) and after the tape was peeled off (bottom). g) Antifogging test of blank and adherent coating after immersion in various solvents for 1 h. h) Antifogging test of blank and adherent coatings in various temperatures.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3. Results and discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3.1. Characterization of PSTG coatings  \n\nThe pre-cleaned bare PE was treated with $\\mathbf{O}_{2}$ plasma for 20 s to create it superhydrophilic, as illustrated in Scheme 1. The PSTG solution was uniformly applied on the substrate, using a knife coating method. Strong hydrogen bonds were generated between PVA, SA, $\\mathrm{TiO}_{2}$ , and glycerin during curing at $60~^{\\circ}\\mathrm{C},$ which improved adhesion between the coating and the substrate. Meanwhile, the large amounts of hydrophilic groups in SA and PVA may increase the composite coating’s surface energy.  \n\nThe surface morphology was observed using SEM (Fig. 1a). It can be discovered that $\\mathrm{TiO}_{2}$ was uniformly disseminated in the coating, with just a small quantity of $\\mathrm{TiO}_{2}$ appearing to be agglomerated. The thick­ ness of PSTG composite layer was about $500~\\mathrm{nm}$ . Moreover, the EDS element mapping revealed that the homogeneous solution was uni­ formly coated on PE film (Fig. 1b), with the content of C, Na, O and Ti element of the film being $63.05\\%$ , $34.12\\%$ , $2.54\\%$ , and $0.29\\%$ , respec­ tively (Fig. 1c). The chemical functional groups in PSTG were investi­ gated using FTIR spectroscopy. As shown in Fig. 1d, peaks at $1625\\mathrm{cm}^{-1}$ and $3435~\\mathrm{cm}^{-1}$ correspond to the stretching vibrations of $\\mathsf{C O O-},$ and –OH of SA [40]. Peaks at $1095~\\mathrm{cm}^{-1}$ and $3404~\\mathrm{cm}^{-1}$ correspond to the stretching vibration of C-O, and $-\\mathrm{OH}$ on PVA [41]. Bands at $3416~\\mathrm{cm}^{-1}$ (stretching vibration of –OH) and $672\\mathrm{cm}^{-1}$ (stretching vibration of Ti − O) were also seen in $\\mathrm{TiO}_{2}$ [38]. PSTG coating peaks of –OH, COO– and CO moved to lower wavenumber of $3288~\\mathrm{cm}^{-1}$ , $1413~\\mathrm{cm}^{-1}$ and 1030 $\\mathsf{c m}^{-1}$ , respectively. Moreover, the development of intramolecular or intermolecular hydrogen bonds reduces the chemical bond forces, resulting in a red shift in their vibrational frequencies. As a result, the chemical shifts of these peaks indicate that hydrogen-bonded crosslinking between PSTG coatings has formed [42].  \n\n![](images/bf7f6c3deadabf1fc1f57eac540ff117586c8d12686c67b96f49190bb54e0aa9.jpg)  \nFig. 4. a) Schematic illustration of the self-healing composite coating. b) SEM photographs of the PSTG coating before and after healing. c) UV–Vis transmission spectra of the bare PE and the coated PE after surgical knife cutting and healing. Inset photos show the coated PE after the cutting (left) and after healing (right).  \n\nThe antifogging performance of PSTG, PTG (PVA- $\\mathrm{\\cdotTiO_{2}}$ -glycerin), and STG (SA- $\\mathrm{TiO}_{2}$ -glycerin) were studied to better understand the role of PVA, SA, and $\\mathrm{TiO}_{2},$ as demonstrated by the optical images in Fig. S1a. The images were taken after the samples were placed above the hot water for $1\\mathrm{min}$ , and both the STG and PTG surfaces have a visible fog layer. PSTG, on the other hand, has excellent antifogging performance with no fog layer. In the early stage of antifogging, the cross-linked PSTG was able to absorb the surrounding water vapor quickly, allowing the water vapor to swiftly spread across the surface, and achieve the anti­ fogging performance.  \n\nTo test the role of $\\mathrm{TiO}_{2}$ , $20~\\ensuremath{\\upmu\\mathrm{L}}$ of methyl blue solution $(10\\mathrm{ppm})$ wa dropped onto the coating and then irradiated with $365~\\mathrm{{nm}}$ ultraviolet light $(1.27\\mathrm{\\mW/cm}^{2})$ for $20\\ \\mathrm{min}$ on two samples, PSTG and PSG (Fig. 2a). The color of the methyl blue solution on the PSTG was entirely deteriorated, whereas the color of methyl blue solution on the PSG remained unchanged, demonstrating that the $\\mathrm{TiO}_{2}$ might endow the composite coating with photocatalytic ability. Apart from that, three different sizes of $\\mathrm{TiO}_{2}$ was used in this experiment and all of them exhibited satisfactory photocatalytic performance, while having no negative impact on antifogging performance (Fig. S1b). The PSTG sur­ face had a water contact angle of $66.8^{\\circ}$ , and the coating had excellent antifogging properties (Fig. 2b). The PSTG coating was more transparent than the blank film (Fig. 2c), making it slightly antireflective. The increased light transmittance due to reduced surface scattering could be due to the coating’s substantially reduced surface roughness ( ${\\cdot}{\\sim}10\\ \\mathrm{nm}$ , Fig. S1c).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3.2. Mechanical property  \n\nContinuous exposure to the UV sources with a wavelength of ${365}\\mathrm{nm}$ and a radiation intensity of $1.27\\mathrm{mW/cm^{2}}$ was used to test the coating’s aging resistance. Even though there was a slight rise in water contact angles (WCAs) after $192\\mathrm{h}$ of UV illumination, which could be attributed to the addition of $\\mathrm{TiO}_{2}$ NPs that act as UV absorbers, the irradiated area had the same excellent antifogging efficacy as the control (Fig. 3a). In contrast, the contact angle of the PSG coating increased significantly and some areas of the coating lost their anti-fogging properties after $192\\mathrm{h}$ of irradiation (Fig. S2). Additionally, the sample was heated in an oven at $80^{\\circ}\\mathrm{C}$ for 17 days to test the hydrophilic coating’s thermal resilience. The coating’s WCAs remained essentially constant after a long heat treat­ ment, and the letters beneath the beaker were plainly visible, indicating excellent antifogging properties (Fig. 3b).  \n\n![](images/1f56a84808c055fbd866b69704e449fdaa5ca4101ec8ea8e667de24ab0090c13.jpg)  \nFig. 5. a) Schematic diagram of self-cleaning of PSTG coating. b) Optical photograph of soybean oil (dyed with oil red) separated from bare PE and coated PE. c) The underwater dynamic sliding angle of coated PE. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)  \n\n![](images/e6ea268c394ca57e3907ab57d86ecb5f06d954b6588967f05d4a6948051b4a03.jpg)  \nFig. 6. a) UV–Vis transmission spectra of the bare PE and the coated PE after freezing at $-23^{\\circ}\\mathrm{C}$ for $24\\mathrm{h}$ . b) The optical photographs of the coated PE and the bare PE after anti-frosting experiment and then exposed to ambient lab conditions for $3\\:s$ .  \n\nFor practical applications, the coating’s mechanical strength is essential. To test the sample’s mechanical stability, as illustrated in Fig. 3c, $\\mathbf{30~g}$ of sands was dropped from a height of 10, 20, 30, $40~\\mathrm{cm}$ respectively, to strike the PSTG coated film [43], and the antifogging level was measured. The film’s antifogging level of the film remained at level 1 even though the impact height increased to $40~\\mathrm{cm}$ (Fig. 3d). Furthermore, the sandpaper abrasion durability of PSTG coating explored. The antifogging performance showed by the insert picture was well maintained in most areas after 100 cycles under $25\\mathrm{{Pa}}$ , although the CAs increased with the increased number of cycles (Fig. S3). The film’s adhesion was further tested using the cross-hatch method, as per the ASTM D3359 standard. No visible debris was observed following the cutting and tape peeling, as shown in Fig. 3f, demonstrating outstanding bonding force between the coating and the substrate. It is also worth noting that the coating performed exceptionally well against fogging in hot water of various temperature (Fig. 3h).  \n\nIn addition, the PE coatings were immersed into several polar and non-polar solvents for 1 h to test the chemical stability of the coating, after which the antifogging grade and hydrophilicity were measured. It was observed that the solvents had no effect on antifogging performance or hydrophilicity, indicating exceptional chemical stability (Fig. 3e, g).  \n\n![](images/fe0e72853ba83ec2e5e80ef7a71f0b3367270e1b3c41459d24fe290d69bb52b1.jpg)  \nFig. 7. a) Schematic diagram of greenhouse film construction. b) Antifogging test blank and adherent coatings after exposure to outdoors for several days. c) WCAs of the coating placed outdoors, where the green area is sunny and the orange area is rainy. d) Schematic diagram of light intensity test. e) Light intensity of blank PE and coated-PE under different hot fogging times. f) The average transmittance of coated PE at different temperatures. g, h) Image of blank (left) and coated (right) greenhouse film after $^\\textrm{\\scriptsize1h}$ of $100^{\\circ}\\mathrm{C}$ hot fogging. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3.3. Self-healing property  \n\nIt is unavoidable that substantial damage to the functional coating occurs consequently, therefore the robust antifogging coating with good self-healing ability is critical for sustainable application. To our superise, the clearly visible scratches were obviously removed via 1 s of water immersing or $5\\mathrm{min}$ of solar light irradiating treatment, indicating the hydrogel coating with good self-healing ability (Fig. 4a, b). This is ascribed to the water molecules adsorbed in the hydrogel coating can interact with the hydroxyl or carboxyl groups of PVA and SA to dynamically restore the broken hydrogen bonds. Furthermore, the transmittance of the self-healed sample was tested to quantitatively analyze the self-healing performances. It was difficult to distinguish between the pristine and self-healed sample (Fig. 4c), which indicated the exceptional self-healing performance made it great potential for practical application. Additionally, a comparison of self-healing condi­ tions with previous work is shown in Table S3, the current work displays simpler conditions and faster self-healing. At the same time, it also shows high light transmittance and excellent anti-fogging performance.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.4. Antifouling property  \n\nHydrophilic surfaces are known to have a high surface energy, therefore low surface energy materials, such as various oils, can easily contaminate the surface. Hence, antifouling plays a vital role in a variety of actual applications. As illustrated in Fig. 5a, it is believed that if the water molecules adsorbed on the surface of the PSTG coating can swiftly create a layer of hydration film, the oil droplets will be unable to reach the substrate, providing antifouling via underwater superoleophobicity. When the sample was immersed in water, a soybean oil (dyed with oil red) droplet quickly rolled off the coated surface and floated on the water surface, leaving a clean surface whereas the bare PE was contaminated (Fig. 5b). The underwater oil contact angle on coated PE film was measured using a $4~{\\upmu\\mathrm{L}}$ oil drop (1,2-dichloroethane), which revealed that the oil CA was around $160^{\\circ}(\\mathrm{Fig.~}1\\mathbf{a})$ . Furthermore, the oil droplets easily slipped off the surface of the coating, when the sample stage was oriented to a deviation of $3.3^{\\circ}$ from the horizon, demon­ strating a remarkable superoleophobic effect (Fig. 5c).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3.5. Anti-freezing property  \n\nThe frost-resistance performance of PSTG coating at extreme cold circumstances was also evaluated in climate areas where typical func­ tional coatings may lose their performance due to low temperatures. The light transmittance variation of PE films with and without PSTG coating frozen at $-23^{\\circ}\\mathsf{C}$ for $24\\mathrm{h}$ were shown in Fig. 6a. The result showed that the transmittance of bare PE declined over time, whereas the modified PE increased light transmission to the same level as the control PE without defrosting. This inspiring result can be attributed to two aspects. First, the coating contains glycerin, which can form hydrogen bond with water and lower its freezing point. Second, PVA has a high capacity for absorbing water, reducing water vapor condensation. The visibility of two samples from $-23^{\\circ}\\mathsf{C}$ to room temperature for 3 s is shown in Fig. 6b. The vapor condensed instantaneously on the bare PE film, obstructing light transmission obstructing, but the coated PE remained good transparent.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 3.6. Versatility and durability  \n\nThe created coating can be applied on a variety of substrates. The coated film had no effect on the substrates’ transmittance, as seen in Fig. S4. The coated glass, PET, PC, and PVC all had a transmittance of at least $82\\%$ . By exposing the samples to hot water vapor at $85~^{\\circ}\\mathrm{C},$ , the antifogging efficacy of the coated substrate was also evaluated (Fig. S5). The substrate without coating fogged up rapidly, whereas the coated substrates did not fog up at all, as previously described.  \n\nIt is also necessary to evaluate the coating’s durability in order to achieve its practicality. The obtained sample was tested for durability by analyzing its water contact angles and antifogging performance in an outdoor environment for many days. The WCAs gradually increased after 18 days (Fig. 7c), but the antifogging level remained at level 1 as shown in Fig. 7b, owing to the adhering of pollutant with a lower relative surface energy. Besides, the antifogging activity can be sus­ tained for more than 5 months in ambient conditions (Fig. S6).  \n\nAs displayed in Fig. 7a, the rising water vapor wetted the greenhouse canopy layer, forming a water film. Any excess water can slide down the slope of the canopy wall to keep the antifogging properties of the PE film. To simulate an agricultural greenhouse, a 0.2 curvature shed with half of the area uncoated for comparison was made. It could be obvi­ ously seen that the blank film was clearly covered with dense water drops, while the coated PE still maintained great transparency (Fig. $^{7}{\\bf g},$ h). Because the ultimate purpose of making antifogging film was to reduce the light refraction while having no influence on photosynthesis, the intensity of light transmission before and after the spraying of water vapor was measured, as shown in Fig. 7d. The light intensity of the blank film reduced significantly, from $1.5\\ \\mathrm{kW/m^{2}}$ to $0.5\\ \\mathrm{kW/m^{2}}$ , while the processed sample showed minor reduction, demonstrating excellent applicability (Fig. 7e). Furthermore, the water vapor temperature is also an indicator to measure the shed film’s practical performance. At tem­ peratures below or above $60~^{\\circ}\\mathrm{C}$ , the coated PE retained a high optical transmittance (over $85\\%$ ) almost independent with time, implying an efficient resistance to fog formation across a wide temperature range, as shown in Fig. 7f.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 4. Conclusions  \n\nIn summary, we have effectively fabricated a multifunctional hy­ drophilic antifogging coating through a convenient, environmentalfriendly and energy-saving one-step technique. The PSTG coating not only had excellent heat resistance but also UV resistance due to the addition of $\\mathrm{TiO}_{2}\\mathrm{NP}s$ . After sand impingement at various heights and $^{\\textrm{1h}}$ of soaking in both polar and non-polar solvent, the coating showed satisfactory mechanical and chemical stability, and maintained a level 1 antifogging rating. After being frozen at $-23^{\\circ}\\mathsf{C}$ for $24\\mathrm{~h~}$ and placed under ambient conditions for 153 days. Surprisingly, the sample showed excellent weather resistance. Additionally, it also had a high rate of selfhealing and a good antifouling action. The novel approach also proved universality, opening up a new path for long-lasting agricultural anti­ fogging coatings with commercial potential.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 18,
+        "chunk": "# Declaration of Competing Interest  \n\nThe authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# Data availability  \n\nData will be made available on request.",
+        "category": " References"
+    },
+    {
+        "id": 20,
+        "chunk": "# Acknowledgements  \n\nThe authors thank Natural Science Funds for Distinguished Young Scholar of Fujian Province (2020 J06038), Natural Science Foundation of Fujian Province (2019 J01652, 2019 J01256), National Natural Sci­ ence Foundation of China (22075046, 51972063), and 111 Project (No. D17005).",
+        "category": " References"
+    },
+    {
+        "id": 21,
+        "chunk": "# Appendix A. Supplementary data  \n\nSupplementary data to this article can be found online at https://doi. org/10.1016/j.cej.2022.137879.",
+        "category": " References"
+    },
+    {
+        "id": 22,
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Chem. 22 (15) (2012) 7420–7426.   \n[36] G.Q. Sun, M.Y. Fan, L.L. Chen, J. Luo, R. Liu, Antifogging UV curable coatings based on hierarchical composite particles through electrostatic interactions, Colloid Surface. A 589 (2020), 124458.   \n[37] B. Liang, Z. Zhong, E. Jia, G. Zhang, Z. Su, Transparent and scratch-resistant antifogging coatings with rapid self-healing capability, ACS Appl. Mater. Interfaces 11 (33) (2019) 30300–30307.   \n[38] Y. Yang, T. Sun, F. Ma, L.-F. Huang, Z. Zeng, Superhydrophilic $\\mathrm{Fe}^{3+}$ doped TiO2 films with long-lasting antifogging performance, ACS Appl. Mater. Interfaces 13 (2) (2021) 3377–3386.   \n[39] Z. Lv, Y. Liang, M. Jia, J. Wang, X. Zhang, Analysis of factors affecting magnetic memory time of $\\mathrm{CaCO_{3}}$ solutions based on orthogonal experiment, Sensor Mater. 32 (4) (2020) 1339–1350.   \n[40] H. Ji, W. Wang, X. Li, X. Han, X. Zhang, J. Wang, C. Liu, L. Huang, W. Gao, Natural small molecules enabled efficient immunotherapy through supramolecular selfassembly in p53-mutated colorectal cancer, ACS Appl Mater. Interfaces 14 (2) (2022) 2464–2477.   \n[41] J.I. Daza Agudelo, M.R. Ramirez, E.R. Henquin, I. Rintoul, Modelling of swelling of PVA hydrogels considering non-ideal mixing behaviour of PVA and water, J. Mater. Chem. B 7 (25) (2019) 4049–4054.   \n[42] Z. Bai, K. Jia, C. Liu, L. Wang, G. Lin, Y. Huang, S. Liu, X. Liu, A solvent regulated hydrogen bond crosslinking strategy to prepare robust hydrogel paint for oil/water separation, Adv. Funct. Mater. 31 (49) (2021) e2104701.   \n[43] H. Liu, J. Huang, Z. Chen, G. Chen, K.-Q. Zhang, S.S. Al-Deyab, Y. Lai, Robust translucent superhydrophobic PDMS/PMMA film by facile one-step spray for selfcleaning and efficient emulsion separation, Chem. Eng. J. 330 (2017) 26–35.",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Anti-fogging properties of amphiphilic copolymer films deposited by chemical vapor deposition (CVD)  \n\nMelek Dinç Tuna a, Emine Sevgili Mercan b, Mehmet Gürsoy b,c, Mustafa Karaman b,c,\\*  \n\na Mechanical and Chemical Industry Inc., Ankara 06560, Turkey   \nb Department of Chemical Engineering, Konya Technical University, Konya 42030, Turkey   \nc Nanotechnology and Advanced Materials Development Application and Research Center, Konya Technical University, Konya 42030, Turkey",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# A R T I C L E  I N F O",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# A B S T R A C T  \n\nKeywords: Anti-fogging Amphiphilic Copolymer Thin film CVD  \n\nThis study demonstrates the deposition of an amphiphilic copolymer as an anti-fogging coating on the glass and mirror surfaces. For this purpose, copolymer films of 2,2,2,3,4,4,4,4 hexafluorobutyl acrylate (HFBA) with 2- (dimethylamino)ethyl methacrylate (DMAEMA) were synthesized using initiated chemical vapor deposition (iCVD). During the iCVD process by adjusting the flow rate ratio of the monomers, the amount of fluorinated moiety in the P(HFBA-DMAEMA) was systematically tuned, which was confirmed through FTIR and XPS ana­ lyses. According to the water contact angle measurements, coatings were shown to be more hydrophobic with increasing fraction of fluorine atoms in their structures. The P(HFBA-DMAEMA)-deposited surfaces showed outstanding and long-lasting anti-fogging performance while maintaining high optical transmissivity. Films were observed to be functional in terms of anti-fogging behavior even after 1-year from the initial coating process, which confirms the durability of the films.",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1. Introduction  \n\nGlasses and mirrors, widely used in a wide range of applications, are essential materials for everyday life. In the future, smart devices using glass and mirror are expected to become more widespread in both in­ dividual and industrial level. When the temperature of the surrounding air is equal to or lower than the dew point, fogging occurs on the surface of the materials. Water droplets accumulated on the surface cause the refraction and reflection of light [1]. This not only reduces the trans­ parency of glass and mirror, but also adversely affects the efficiency of the devices in which they are used. Therefore, it is very important to prevent surface fogging. Various strategies have been developed for this purpose. Changing ambient conditions (e.g. relative humidity and air flow), heating, and wiping material surfaces are among the most tradi­ tional strategies to prevent fogging [2]. These strategies often require infrastructure and complex equipment to be implemented effectively. Another anti-fogging strategy is coating material surfaces to change their wetting properties. It is possible to prevent fogging by transforming surfaces into hydrophobic or hydrophilic coatings. The purpose of the hydrophobic coating is to minimize the contact area of the fog droplets with the surface and to ensure that the droplets roll away from the surface [3]. In most cases, for this to be successful, the droplets need to reach a certain weight and/or the materials need to be inclined [4,5]. Moreover, hydrophobic coatings are not always sufficient for the sepa­ ration of water droplets from the surface, so superhydrophobic coatings are mostly needed [6,7]. Generally, superhydrophobic coatings contain nano- and micro-sized roughness’s, which may limit their use in some application areas. The purpose of hydrophilic coatings is to allow the fog to spread on the surface as a thin film instead of droplets. In this way, drop-sourced light scattering is prevented [8]. However, when the amount of condensation on the surface exceeds the capacity of the film, the overflowing water layer can cause various problems. They are also susceptible to organic pollutant contamination due to their high surface energy [9]. Neither hydrophilic nor hydrophobic coatings can perform excellent anti-fogging performance in all conditions due to the afore­ mentioned handicaps.  \n\nThe coatings having hydrophilic and hydrophobic properties at the same time are expected to exhibit effective fogging performance. While the hydrophilic parts allow water to spread on the surface, the hydro­ phobic parts prevent the coating from dissolving. Therefore, there has been a growing interest in the production of amphiphilic coatings to be used for anti-fogging purposes in recent years [10–13]. The techniques used to produce amphiphilic coatings can be classified under two main groups: wet and dry techniques. Atom transfer radical polymerization (ATRP), electrospinning, sol-gel, and reversible addition–fragmentation chain-transfer (RAFT) can be given as examples of wet techniques [14–17]. These techniques require time-consuming extra steps such as purification, heating, and washing. In addition, the use of aggressive and toxic solutions poses a threat to both living organisms and the envi­ ronment. Dry techniques eliminate the problems encountered in using wet techniques such as the consumption of toxic solutions and excess chemicals. The environmentally friendly initiated chemical vapor deposition (iCVD) process, as a dry technique, is a versatile technique in polymer production [18]. In iCVD process, monomers are not dissolved in any solution as in wet techniques, their vapors are fed directly into the reactor. Therefore, iCVD process eliminates the solvent related prob­ lems, including surface-tension-driven instability, microphase separa­ tion, post purification steps, and solvent disposal costs [19,20]. All these unique advantages make the iCVD process an ideal technique for the production of amphiphilic polymers. However, there are very few studies on the production of amphiphilic polymers using iCVD. In these studies, antifouling and antibiofouling performances of the films have been investigated [21–24]. In this study, for the first time, amphiphilic polymeric thin films were produced by copolymerization of 2,2,2,3,4,4, 4,4 hexafluorobutyl acrylate (HFBA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) monomers using iCVD technique. Copolymer films with different chemical compositions were produced by changing the flow rate ratios of the monomers. The anti-fogging properties of copolymer films coated on glass and mirror were investigated.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2. Materials and methods",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.1. Materials  \n\nThe monomers HFBA $(95~\\%)$ ), DMAEMA $(98~\\%)$ and the initiator di‑tert butyl peroxide (TBPO, $98\\%$ ) were acquired from Sigma–Aldrich. The precursors were utilized as received without any additional modi­ fication or post-purification procedures. Glass slide (ISOLABLaborgera¨te GmbH), mirror and silicon wafer (100, p-type) were used as substrates.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.2. iCVD of amphiphilic film  \n\nThe iCVD process for amphiphilic film coatings was conducted within a specially constructed stainless-steel chamber measuring $20\\mathrm{cm}$ in width, $30\\mathrm{cm}$ in length, and $5\\mathrm{cm}$ in height. The schematic drawing of the iCVD system used is given in Fig. 1a and a more detailed description of the system used in this study was given elsewhere [25]. The reaction scheme of HFBA and DMAEMA in iCVD in the presence of TBPO initiator is shown in Fig. 1b.  \n\nThe substrates were kept at a constant temperature during polymerization by placing them on the reactor floor with a heat exchanger on the backside, which was connected to a recirculating chiller (Thermo Neslab). The energy required for the polymerization was provided by a tungsten filament array (Alfa-Aesar, $99.95\\:\\%$ ) placed $22~\\mathrm{mm}$ above the reactor floor. The resistive heating of tungsten fila­ ment was achieved by using a variac. The temperature of the filament array was continuously monitored using a K type thermocouple (Omega) in contact with it. According to the temperature reading, the current passing through the filament was manually adjusted by variac to reach the desired filament temperature. The precursors were placed in individual stainless-steel jars and their vapors were fed in the reactor using needle valves (Swagelock). The temperatures of DMAEMA, HFBA and TBPO were kept constant at $55^{\\circ}\\mathrm{C},$ , $25~^{\\circ}\\mathrm{C}$ and $25^{\\circ}\\mathrm{C}_{:}$ , respectively, using a proportional-integral-derivative (PID) controlled heaters. Vac­ uum environment was created inside the reactor by a rotary vacuum pump (Edwards RV8). The pressure within the reactor was monitored using a capacitance-type manometer (MKS). To maintain the pressure at the desired level, a PID-controlled butterfly valve (MKS) was placed between the vacuum pump and the reactor. By adjusting the flow rate ratios of HFBA/DMAEMA, it was aimed to fabricate amphiphilic poly­ mers with different chemical compositions. The amphiphilic polymers were deposited using three different DMAEMA flow rates, while the flow rates of both TBPO and HFBA were kept constant at 1.0 sccm. Thin films were named as follows: AP1, AP2 and AP3. AP1, AP2 and AP3; which were produced with HFBA/DMAEMA flow rate ratio of 1/0.3, 1/0.7 and 1/1, respectively. Table 1 summarizes the details of the iCVD experi­ mental conditions.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.3. Characterization  \n\nThe film thickness was measured in-situ during the experiments using a laser interferometry, details of which are given elsewhere [26]. The ex-situ measurement of film thickness was conducted using a reflec­ tometer, comprising an Avaspec-ULS2048L spectrometer with an AvaLight-DH-S BAL light source. This was employed to verify the pre­ cision of interferometric thickness measurements. The experiments were repeated three-times and the film thicknesses were measured for each as-deposited films. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) analyses were used to reveal the chemical structures of the polymeric films. FTIR spectra were acquired with a resolution of $4~\\mathrm{cm}^{-1}$ using a FTIR spectrometer (Thermo Scien­ tific, Nicolet 380).  \n\nXPS analysis of the polymeric films was carried out by a Specs spectrometer (Specs EA 300) equipped with a monochromatized Al Kα X-ray source. A contact angle goniometer (Krüss Easy Drop) was employed to measure water contact angle values at room temperature using $4.0~\\upmu\\mathrm{l}$ of pure water $\\mathrm{(pH=}7.0\\AA)$ ). The topographical scans of polymeric films were revealed by atomic force microscopy (AFM) (Veeco MultiMode). Two different approaches were applied to test antifogging performances. In the first approach, the samples were placed 4 cm above a hot water bath at $100^{\\circ}\\mathrm{C}$ for $100\\ s.$ . The temperature and relative humidity of the environment were measured as $23.1\\pm1^{\\circ}\\mathrm{C}$ and $55\\pm2\\%$ , respectively. In the second approach, the samples were kept in the freezer part of a refrigerator (Arçelik1060T) for $120\\ s$ and then exposed to open air laboratory environment ${\\cdot}^{\\sim23^{\\circ}\\mathrm{C}}$ and $\\sim30~\\%$ hu­ midity). After the fogging test, a UV–vis spectrophotometer (Shanghai Spectrum Instruments Co., Ltd.) was employed to measure the optical transmission spectra of uncoated and coated glasses in the wavelength range from 400 to $700\\ \\mathrm{nm}$ . In addition, in order to investigate the durability of the anti-fogging properties of the thin films over time, the thin film coated samples were kept in the open air laboratory environ­ ment ( $\\cdot\\sim23^{\\circ}\\mathrm{C}$ and ${\\sim}30\\%$ humidity) for one year and then re-exposed to fog.  \n\n![](images/9c763cc63c9598818345af054d50ae53d8de50848882bcf96108664ef14b404f.jpg)  \nFig. 1. (a) Schematic illustration of iCVD process, (b) iCVD copolymerization reaction of HFBA and DMAEMA.  \n\nTable 1 iCVD experimental conditions for amphiphilic thin film depositions.   \n\n\n<html><body><table><tr><td>Amphiphilic thin films</td><td colspan=\"3\">Flow rate (sccm)</td><td>Reactor pressure (mTorr)</td><td>Filament temperature( °C)</td><td>Substrate temperature (℃)</td></tr><tr><td></td><td>HFBA</td><td>DMAEMA</td><td>TBPO</td><td></td><td></td><td></td></tr><tr><td>AP1</td><td>1.0</td><td>0.3</td><td>1.0</td><td>600</td><td>245</td><td>25</td></tr><tr><td>AP2</td><td>1.0</td><td>0.7</td><td>1.0</td><td>600</td><td>245</td><td>25</td></tr><tr><td>AP3</td><td>1.0</td><td>1.0</td><td>1.0</td><td>600</td><td>245</td><td>25</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 3. Results and discussion  \n\nThe deposition rate was calculated as the film thickness divided by the deposition time. Excellent agreement was observed between the film thicknesses measured by interferometer and reflectometer. All iCVD films parameters were kept constant except the DMAEMA flow rates in the fabrication of AP1, AP2 and AP3 thin films. In the AP1 film, where the DMAEMA flow rate $(0.3\\ s c c m)$ was the lowest, the deposition rate was too low to be recorded. When the DMAEMA flow rate increased from 0.3 to 0.7 (AP2), the deposition rate was found to be $27.0\\pm1.3$ $\\mathrm{{nm/min}}$ . When the DMAEMA flow rate was further increased to 1 (AP3), the deposition rate also increased, and reached $35.0\\pm1.8\\mathrm{nm/min}$ . The possible reason for the lower deposition rate of AP2 than that of AP3 may be the higher amount of HFBA in the reactor. The presence of $\\mathrm{CF}_{2}$ and bulky $\\mathrm{CF}_{3}$ groups may have caused a steric effect, resulting in a decrease in the deposition rate [27].  \n\nThe FTIR spectra of AP2 and AP3 films are shown in Fig. 2 in comparison with the spectra of HFBA and DMAEMA monomers. All FTIR spectra were baseline corrected, and thickness normalized. The peak intensities of all spectra were normalized to the observed $\\scriptstyle{\\mathsf{C}}=0$ stretch­ ing at $1760\\mathrm{cm}^{-1}$ in HFBA and DMAEMA monomers [28]. The spectrum of HFBA monomer and copolymers show the following major peak as­ signments: $1288~\\mathrm{cm}^{-1}$ ( ${\\mathrm{-}}\\mathrm{CF}_{2}$ vibration), $962~\\mathrm{cm}^{-1}$ (-CF Vibration) and $892~\\mathrm{cm}^{-1}$ (symmetric ${\\mathrm{-CF}}_{3}$ stretching) [29]. Similarly, the peak at 2840 $\\mathsf{c m}^{-1}$ resulting from the C-H stretching vibration of $\\mathrm{{N}}(\\mathrm{{CH}}_{3})_{2}$ group observed in DMAEMA monomer was also observed in the copolymers [30,31]. These results confirm the presence of functional groups in both monomers in the copolymers. The narrow and distinct peaks in the spectra of the copolymers indicate a high retention of functional groups. Another important point to be noted about the FTIR spectra is that the $\\scriptstyle\\mathbf{C}=\\mathbf{C}$ stretching band observed at the $1635\\mathrm{cm}^{-1}$ peak in both monomers was not observed in the copolymers. The absence of $\\mathtt{C=C}$ double bond in copolymers indicates that the polymerization proceeds through the $\\scriptstyle\\mathbf{C}=\\mathbf{C}$ double bond. In radical polymerization processes performed by wet techniques, additional purification procedures are needed to remove monomer residues. According to FTIR analysis, the absence of any entrained monomer in the copolymers indicates that pure copolymers can be produced by iCVD method without the need for any additional purification process.  \n\n![](images/152ef4fb13b417fda857898d72262344eba7e835c90c0cd083fc2512b21a4230.jpg)  \nFig. 2. FTIR spectra of HFBA, DMAEMA, AP2, and AP3.  \n\nThe compositions of the as-deposited copolymer films were found from the FTIR spectra using the Beer Lambert equation, assuming that the $\\scriptstyle\\mathbf{C}=0$ bond oscillator coefficient is the same in the HFBA and DMAEMA components [32,33]. Eq. (1) was used to calculate the HFBA mole fraction $(f_{\\mathrm{HFBA}})$ in the copolymer film:  \n\n$$\nf_{H F B A}=1-\\left(\\frac{\\mathsf{A}_{C=O}}{\\mathsf{A}_{N(C H_{3})_{2}}}\\right)_{D M A E M A}\\left(\\frac{\\mathsf{A}_{N(C H_{3})_{2}}}{\\mathsf{A}_{C=O}}\\right)_{P(H F B A-D M A E M A)}\n$$  \n\nwhere, $\\scriptstyle\\mathbf{A}_{C=O}$ and $\\mathsf{A}_{N(C H3)2}$ are the area under the $\\scriptstyle\\mathbf{C}=0$ and $\\mathrm{{N}}(\\mathrm{{CH}}_{3})_{2}$ absorption peaks, respectively. HFBA content in AP2 and AP3 was found to be $^{41,3\\ \\%}$ and $33,1\\ \\%$ , respectively. In order to observe this differ­ ence, XPS analysis of the copolymers was performed. The XPS survey scans of AP2 and AP3 are shown in Fig. 3. As expected, only C, O, N and F atoms were detected in both copolymers. It was found that the amount of nitrogen was higher and the amount of fluorine was lower in AP3 film, where the DMAEMA/HFBA monomer flow rate ratio was higher compared to AP2 film.  \n\nIn addition, the chemical bonding of the copolymer films was investigated by high-resolution XPS analysis. High-resolution C1s, O1s, and N1s spectra of AP2 and AP3 films are shown in Fig. 4a–f. The binding energy values in the spectrum of each atom were matched to the experimental data using a curve fitting method. C1s, O1s, and N1s spectra of both thin films can be curve-fitted into eight, two and one peak components, respectively. Observed binding energies in the spectra are given with attributed groups and their theoretical values in Table 2.  \n\nCompared to the spectrum of AP2 (Fig. 4a), the area ratio of the $\\mathrm{CH_{2}\\mathrm{-}C^{\\ast}\\mathrm{-}H F}$ peak in the spectrum of AP3 (Fig. 4b) was lower, while the area ratio of the ${\\bf C}{\\cdot}{\\bf N}^{*}$ peak was higher. Considering the monomer flow rates, the observed difference of both peaks is as expected and in agreement with XPS atomic percentage calculations. Two oxygen moi­ eties present in HFBA and DMAEMA monomer structures were detected in nearly the same positions in both copolymers (Fig. 4c and d) [22,24]. Similarly, nitrogen moiety, which is found only in the structure of DMAEMA monomer, was detected in nearly the same position in both  \n\n![](images/69922b0bd12676e95f9680b4d4667118ad6af2ddae24a3b5272161a12e02f128.jpg)  \nFig. 3. XPS survey spectra of (a) AP2 and (b) AP3.  \n\n![](images/a03524ce4ea2504336ee67c94c67cc9f5f1dc1c7556265c0519471d6a7890034.jpg)  \nFig. 4. High-resolution XPS spectra of C1s for (a) AP2 and (b) AP3; O1s for (c) AP2 and (d) AP3; N1s for (e) AP2 and (f) AP3.  \n\ncopolymers (Fig. 4e and f).  \n\nOne of the desirable properties for anti-fogging coatings is the high homogeneity of the coverage. In order to investigate the homogeneity of the thin films, both copolymers were coated on $5\\cos{\\mathrm{x}}5\\mathrm{cm}$ mirrors with a thickness of $200\\mathrm{nm}$ . The mirrors were divided into 25 different areas, each of which is $1\\mathrm{cm}$ wide and $1\\mathrm{cm}$ long, for contact angle measure­ ments. The measured contact angles for AP2 and AP3 coated mirror surfaces are shown in Fig. 5a and Fig. 5c, respectively. The average contact angle measurements of AP2 and AP3 coated mirrors were calculated as 34.3 and 28.5, respectively. AP2, which has more fluorine atoms in its structure, showed more hydrophobic behavior. Contact angle measurements of both coated mirrors measured at different points were found to be close to each other. The standard deviation values of the contact angle measurements for AP2 and AP3 were 2.6 and 0.8, respectively. These values indicate that both films are homogeneously coated. The results are not surprising, because the CVD method is known for producing very smooth polymeric thin films [34,35]. AFM analysis was conducted to reveal the surface roughness and surface morphology of both copolymer films coated silicon wafers.  \n\nThe AFM images of AP2 and AP3 coated silicon wafers in dimension of $2\\upmu\\mathrm{m}\\times2\\upmu\\mathrm{m}$ are presented in Fig. 5b and Fig. 5d, respectively. The AFM image of both films was observed to be very smooth without any defects and 3D structures. The root mean square roughness values of AP2 and AP3 thin films were measured as $0.256\\ \\mathrm{nm}$ and $0.569\\ \\mathrm{nm}$ , respectively. The AFM images and roughness values of the films confirm that the films were smoothly coated.  \n\nAnother important point related to AFM and contact angle results is the inverse relationship between roughness values and contact angle values. This observation is in agreement with previous studies of hy­ drophilic films produced by PECVD method in the literature [36]. This relationship can be explained by Wenzel model as given in Eq. (2) [37].  \n\nTable 2 High-resolution XPS scan data of AP2 and AP3.   \n\n\n<html><body><table><tr><td colspan=\"2\"></td><td>AP2</td><td>AP3</td><td>Theoretical</td></tr><tr><td>Core level</td><td>Origin</td><td>Binding energy (eV)</td><td>Binding energy (eV)</td><td>Binding energy (eV)</td></tr><tr><td>C 1s</td><td>-C*-C/C-H</td><td>284.6</td><td>284.8</td><td>285.0</td></tr><tr><td></td><td>-C*H-CO-</td><td>285.2</td><td>285.3</td><td>285.5</td></tr><tr><td></td><td>-C*-N</td><td>285.6</td><td>285.7</td><td>285.9</td></tr><tr><td></td><td>-0-C*-H2</td><td>286.5</td><td>286.7</td><td>286.9</td></tr><tr><td></td><td>CH2-CF2-C*-</td><td>287.0</td><td>287.3</td><td>287.9</td></tr><tr><td></td><td>HF-</td><td>289.1</td><td>289.0</td><td>289.2</td></tr><tr><td></td><td>-C*=0-</td><td>291.0</td><td>291.2</td><td>290.9</td></tr><tr><td></td><td>-C*F2</td><td>293.3</td><td>293.5</td><td>293.9</td></tr><tr><td>01s</td><td>-C*F3</td><td></td><td></td><td></td></tr><tr><td></td><td>-C=0*</td><td>531.8</td><td>531.6</td><td>532.4</td></tr><tr><td></td><td>-0*-C</td><td>533.2</td><td>533.0</td><td>533.6</td></tr><tr><td>N1s</td><td>-C-N</td><td>399.0</td><td>399.1</td><td>399.4</td></tr></table></body></html>  \n\n$$\n\\mathrm{cos}\\theta{=}\\mathrm{R_{f}c o s}\\theta_{0}\n$$  \n\nwhere, θ and $\\theta_{0}$ represent the contact angle of a rough surface and flat surface, respectively. ${\\bf R}_{\\mathrm{f}}$ represents the surface roughness factor, defined as the ratio of surface actual area to the geometric surface. For completely smooth surfaces ${\\bf R}_{\\mathrm{f}}$ value should be equal to 1, while for rough surfaces it should be greater than 1. Since $\\theta_{0}$ value of hydrophilic surfaces is less than $90^{\\circ}$ , the contact angle value is expected to decrease with increasing roughness in hydrophilic surfaces. Although the corre­ lation between contact angle results and surface roughness is consistent with the Wenzel model, it should be noted that the roughness values are less than $1\\ \\mathrm{nm}$ . Therefore, it can be postulated that surface chemistry (the amount of fluorinated moieties) has more influence on the wetta­ bility of the surfaces in this study than surface roughness.  \n\nSince there is no significant difference between the chemical and morphological properties of AP2 and AP3 copolymers to affect their anti-fogging performance, the anti-fogging properties of the AP3 thin film which has a higher deposition rate were tested. Anti-fogging coat­ ings applied to optically transmissive or reflective material surfaces must be optically transparent. The UV–vis transmission spectra of the $200~\\mathrm{{nm}}$ thick AP3 film coated glass slide are shown in Fig. 6a in com­ parison with the uncoated glass slide. There is no significant difference between both spectra, indicating that the thin film does not cause any optical loss or absorption in the visible region. In addition, UV–vis transmission spectra of both glass slides were taken immediately after exposure to intense hot water vapor. As can be seen in Fig. 6b, a sharp decrease in the spectrum of the uncoated glass slide was observed due to the effect of the fog formed on the surface. On the other hand, no sig­ nificant difference was observed in the spectra of the glass slide coated with AP3 film before and after exposure to fog, confirming that no fog formed on the surface Fig. 6c shows photographs of uncoated and AP3 film coated glasses exposed to intense hot water vapor. Fig. 6d shows photographs of uncoated and AP3 film-coated mirrors removed from the freezer to room temperature. It is clearly observed that AP3 thin films show successful anti-fogging performance on different surfaces in both conditions. To investigate the long-time durability of the anti-fogging property of the as-deposited thin film produced in this study, the ascoated mirrors were kept in open air laboratory conditions for one year and contact angle measurements were carried out at various time intervals. For the mirror surface coated with AP3 film the contact angle values were found to vary between 27 and 30˚. In addition, no perfor­ mance decrease was observed when the anti-fogging property of the 1- year-old samples was retested. These results show the high durability of the films.  \n\n![](images/2b142c70e0e4cb9bd784a8968dd821f7134bce9328b8a5400696c1cb63922227.jpg)  \nFig. 5. Water contact angle measurements on (a) AP2 and (c) AP3 coated mirros from different locations; AFM images of (b) AP2 and (d) AP3 coated silicon wafers.  \n\n![](images/7e1defda58d49c8b29a118a90837dbb57a2728c47c089bab796fe78a8bd59d23.jpg)  \nFig. 6. UV−vis transmittance spectra of uncoated and AP3 coated glasses before (a) and (b) after fogging tests. Digital photographs of (c) uncoated and AP3 coated glasses, (d) uncoated and AP3 coated mirrors after fogging test.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 4. Conclusion  \n\nP(HFBA-DEAEMA) copolymer thin films were successfully synthe­ sized by iCVD. The iCVD method allowed the fraction of HFBA and DEAEMA incorporation to be systematically varied. All of the asdeposited copolymers were found to exhibit excellent optical trans­ parencies and anti-fogging properties at all monomer fractions studied. According to the water contact angle measurements, coatings were shown to be more hydrophobic with increasing fraction of fluorine atoms in their structures. The as-deposited surfaces showed excellent and long-lasting anti-fogging performance without any significant loss in their optical transparencies. Films were observed to be functional in terms of anti-fogging behavior even after 1-year from the initial coating process, which confirms the durability of the films. This work has shown that anti-fogging coatings can easily be produced via solventless and environmentally friendly iCVD technique on the surfaces of different materials, which can be used in real-world applications. Although very large-area and geometrically complex surfaces may possess some limi­ tations regarding coating uniformities, such limitations can be overcome by carrying out optimization studies at large-scale vacuum deposition systems.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 11,
+        "chunk": "# CRediT authorship contribution statement  \n\nMelek Dinç Tuna: Writing – original draft, Methodology, Data curation, Conceptualization. Emine Sevgili Mercan: Methodology, Data curation. Mehmet Gürsoy: Writing – original draft, Methodology. Mustafa Karaman: Writing – review & editing, Writing – original draft, Supervision, Funding acquisition, Conceptualization.",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# Declaration of competing interest  \n\nThe authors declare that they have no known competing financial  \n\ninterests or personal relationships that could have appeared to influence the work reported in this paper.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 13,
+        "chunk": "# Data availability  \n\nData will be made available on request.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 14,
+        "chunk": "# Acknowledgments  \n\nThis study was supported by the Konya Technical University Scien­ tific Research Foundation with a project number of 201016003 and by the Scientific and Technological Research Council of Turkey (TÜB˙ITAK) with a Grant No. of 119M227.",
+        "category": " Acknowledgments"
+    },
+    {
+        "id": 15,
+        "chunk": "# References  \n\n[1] Z. Han, X. Feng, Z. Guo, S. Niu, L. Ren, Flourishing bioinspired antifogging materials with superwettability: progresses and challenges, J. Adv. Mater. 30 (2018) 1704652.   \n[2] I.R. Dur´an, G. Laroche, Water drop-surface interactions as the basis for the design of anti-fogging surfaces: theory, practice, and applications trends, Adv. Colloid Interface 263 (2019) 68–94.   \n[3] M. Karaman, M. Gürsoy, F. Aykül, Z. Tosun, M.D. Kars, H.B. Yildiz, Hydrophobic coating of surfaces by plasma polymerization in an RF plasma reactor with an outer planar electrode: synthesis, characterization and biocompatibility, Plasma Sci. Technol. 19 (2017) 085503.   \n[4] I.F. Wahab, B. Abd Razak, S.W. Teck, T.T. Azmi, M. Ibrahim, Fundamentals of antifogging strategies, coating techniques and properties of inorganic materials; a compre-hensive review, J. Mater. Res. Technol. 23 (2023) 687–741.   \n[5] M. Gürsoy, All-dry patterning method to fabricate hydrophilic/hydrophobic surface for fog harvesting, Colloid Polym. Sci. 298 (2020) 969–976.   \n[6] M. Gürsoy, B. Kocadayıo˘gulları, Environmentally friendly approach for the plasma surface modification of fabrics for improved fog harvesting performance, Fibers Polym. 24 (2023) 3557–3567.   \n[7] M. Shahid, S. Maiti, R.V. Adivarekar, S. Liu, Biomaterial based fabrication of superhydrophobic textiles – A review, Mater. Today Chem. 24 (2022) 100940.   \n[8] I.R. Duran, G. Laroche, Current trends, challenges, and perspectives of anti-fogging technology: surface and material design, fabrication strategies, and beyond, Prog. Mater. Sci. 99 (2019) 106–186.   \n[9] H. Lee, M.L. Alcaraz, M.F. Rubner, R.E. Cohen, Zwitter-wettability and antifogging coatings with frost-resisting capabilities, ACS Nano 7 (2013) 2172–2185.   \n[10] X. Gong, H. Yu, L. Wang, J. Hu, L. Wang, C. Li, Tailoring amphiphilic polymeric coating with durable antifogging performance, Prog. Org. Coat. 179 (2023) 107523.   \n[11] S.H. Lee, M. Kang, H. Jang, S. Kondaveeti, K. Sun, S. Kim, H.H. Park, H.E. Jeong, Bifunctional amphiphilic nanospikes with antifogging and antibiofouling properties, ACS Appl. Mater. Interfaces 14 (2022) 39478–39488.   \n[12] C. Li, X. Li, C. Tao, L. Ren, Y. Zhao, S. Bai, X. Yuan, Amphiphilic antifogging/antiicing coatings containing POSS-PDMAEMA-b-PSBMA, ACS Appl. Mater. Interfaces 9 (2017) 22959–22969.   \n[13] C. Zhao, X. Yuan, S. Bai, P. Sun, Y. Zhao, K. Zhu, L. Ren, X. Li, Antifogging and antibacterial properties of amphiphilic coatings based on zwitterionic copolymers, Sci. China Technol. Sci. 64 (2021) 817–826.   \n[14] E. Fujita, K. Kaneko, T. Oshima, D. Fujioka, K. Kaneko, K. Fuchigami, T. Hanasaki, Synthesis of amphiphilic triblock copolymers by ATRP and coalescence suppression effect in suspension polymerization, J. Chem. Eng. Jpn. 56 (2023) 2276424.   \n[15] L. Gao, Y. Tang, C. Wang, L. Yao, J. Zhang, R. Gao, X. Tang, T. Chong, H. Zhang, Highly-efficient amphiphilic magnetic nanocomposites based on a simple sol-gel modification for adsorption of phthalate esters, J. Colloid Interface Sci. 552 (2019) 142–152.   \n[16] S. Samanta, S. Sarkar, N.K. Singha, Multifunctional layer-by-layer coating based on a new amphiphilic block copolymer via RAFT-mediated polymerization-induced self-assembly process, ACS Appl. Mater. Interfaces 15 (20) (2023) 24812–24826.   \n[17] C. Zhu, D. Chang, X. Wang, D. Chai, L. Chen, A. Dong, G. Gao, Novel antibacterial fibers of amphiphilic N-halamine polymer prepared by electrospinning, Polym. Adv. Technol. 30 (2019) 1386–1393.   \n[18] K.K. Gleason, Designing organic and hybrid surfaces and devices with initiated chemical vapor deposition (iCVD), Adv. Mater. 36 (8) (2023) 2306665.   \n[19] Y. Cheng, A. Khlyustova, P. Chen, R. Yang, Kinetics of all-dry free radical polymerization under nanoconfinement, Macromolecules 53 (2020) 10699–10710.   \n[20] A. Khlyustova, M. Kirsch, R. Yang, Amphiphilic copolymer thin films with short fluoroalkyl side chains for antibiofilm properties at the solid–liquid–air interface, ACS Sustain. Chem. Eng. 10 (2022) 15699–15713.   \n[21] C.A. Amadei, R. Yang, M. Chiesa, K.K. Gleason, S. Santos, Revealing amphiphilic nanodomains of anti-biofouling polymer coatings, ACS Appl. Mater. Interfaces 6 (2014) 4705–4712.   \n[22] D. Briggs, G. Beamson, XPS studies of the oxygen 1s and 2s levels in a wide range of functional polymers, Anal. Chem. 65 (1993) 1517–1523.   \n[23] R. Yang, E. Goktekin, M. Wang, K.K. Gleason, Molecular fouling resistance of zwitterionic and amphiphilic initiated chemically vapor-deposited (iCVD) thin films, J. Biomater. Sci. 25 (2014) 1687–1702.   \n[24] J.B. You, K.I. Min, B. Lee, D.P. Kim, S.G. Im, A doubly cross-linked nano-adhesive for the reliable sealing of flexible microfluidic devices, Lab Chip 13 (2013) 1266–1272.   \n[25] E. Sevgili, M. Karaman, Initiated chemical vapor deposition of poly(Hydroxypropyl methacrylate) thin films, Thin Solid Films 687 (2019) 137446.   \n[26] M. Gürsoy, T. Uçar, Z. Tosun, M. Karaman, Initiation of 2-hydroxyethyl methacrylate polymerization by tert-butyl peroxide in a planar PECVD system, Plasma Process. Polym. 13 (2016) 438–446.   \n[27] K.A. Wood, C. Cypcar, L. Hedhli, Predicting the exterior durability of new fluoropolymer coatings, J. Fluor. Chem. 104 (2000) 63–71.   \n[28] D. Lin-Vien, N.B. Colthup, W.G. Fateley, J.G. Grasselli, The Handbook of Infrared and Raman characteristic Frequencies of Organic Molecules, Academic Press, San Diego, 1991.   \n[29] M. Gürsoy, M. Karaman, Hydrophobic coating of expanded perlite particles by plasma polymerization, Chem. Eng. J. 284 (2016) 343–350.   \n[30] A. Angelini, C. Fodor, W. Yave, L. Leva, A. Car, W. Meier, pH-Triggered membrane in pervaporation process, ACS Omega 3 (2018) 18950–18957.   \n[31] N.S. Okten, C.C. Canakci, N. Orakdogen, Hertzian elasticity and triggered swelling kinetics of poly(amino ester)-based gel beads with controlled hydrophilicity and functionality: a mild and convenient synthesis via dropwise freezing into cryogenic liquid, Eur. Polym. J. 114 (2019) 176–188.   \n[32] F. Sarıipek, M. Karaman, Initiated CVD of tertiary amine-containing glycidyl methacrylate copolymer thin films for low temperature aqueous chemical functionalization, Chem. Vap. Depos. 20 (10-11-12) (2014) 373–379.   \n[33] Y. Mao, K. Gleason, Vapor-deposited fluorinated glycidyl copolymer thin films with low surface energy and improved mechanical properties, Macromolecules 39 (11) (2006) 3895–3900.   \n[34] D. Abessolo Ondo, F.o. Loyer, F. Werner, R. Leturcq, P.J. Dale, N.D. Boscher, Atmospheric-pressure synthesis of atomically smooth, conformal, and ultrathin low-k polymer insulating layers by plasma-initiated chemical vapor deposition, ACS Appl. Polym. Mater. 1 (2019) 3304–3312.   \n[35] Y. Zhao, N. Huo, S. Ye, W.E. Tenhaeff, Elastic broadband antireflection coatings for flexible optics using multi-layered polymer thin films, J. Mater. Chem. C 11 (2023) 4005–4016.   \n[36] M. Gürsoy, M. Karaman, Effect of substrate temperature on initiated plasma enhanced chemical vapor deposition of PHEMA thin films, Phys. Status Solidi C 12 (2015) 1006–1010.   \n[37] R.N. Wenzel, Surface roughness and contact angle, J. Phys. Chem. 53 (1949) 1466–1467.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Recent Developments in Stability and Passivation Techniques of Phosphorene toward Next-Generation Device Applications  \n\nDavid K. Sang, Huide Wang, Zhinan Guo,\\* Ni Xie, and Han Zhang\\*  \n\nPhosphorene as a rising star is a monolayer or few-layer form of black phosphorus (BP), which is used as a 2D material, in addition to graphene. This monoelemental 2D material has gained considerable attention in the fields of electronics, optoelectronics, and biomedicine due to its extraordinary physical properties. However, as both theoretical and experimental works show, the intrinsic instability of phosphorene under ambient conditions is a major challenge in practical applications. Various theoretical and experimental researches regarding the mechanism of the degradation and passivation strategies are proposed and reported to overcome the problem of the ambient instability of phosphorene. These strategies have enabled researchers to conduct fundamental studies on phosphorene’s extraordinary properties. Here, not only an extensive summary of these passivation strategies but also an overview of the fabrication methods, challenges, and suitable applications of phosphorene are provided.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1. Introduction  \n\nIn recent years, 2D layered materials (2DLMs) have made enormous progress through research after the discovery of graphene.[1] Graphene, as the first 2D material, was a major advance in science and technology because of its novel intrinsic physical properties, for example, thermal transport, electronic transport, and mechanical properties.[2] Since the exploration of graphene, researchers have discovered a series of 2D layered crystals, one of which is phosphorene. As a novel 2D material, phosphorene has been the focus of intense studies in recent years because of its excellent carrier mobility and high on/off ratio, tunable direct bandgap, and anisotropy in plane. Based on the bandgap value, phosphorene can be placed in between graphene and the 2D transitional metal dichalcogenides (2D-TMDs) in the hierarchy of 2D materials. Graphene  \n\nis gapless,[3] and the 2D TMDs only have direct bandgap at the monolayer level,[4] while phosphorene has emerged as the star because it shows direct bandgap in bulk, and mono- and few-layer forms,[5] with layer-dependent bandgap.[6] Phosphorus is abundant in the earth’s crust making up $0.1\\%^{\\left[7\\right]}$ as monoelement P, and it also exists in various allotropes,[8] i.e., black phosphorus (BP), red phosphorus (RP), white phosphorus A7 phases, and violet phosphorus. BP is energetically stable among the phosphorus allotropes and possesses an orthorhombic structure with high density.[9] The breakthrough in phosphorene exfoliation[10] elicited intense research[11] due to phosphorene’s fascinating properties, such as layer-dependent bandgap,[6a,12] high carrier mobility with pronounced high hole mobility, and anisotropy between elec  \ntrons and holes in the armchair and zigzag directions,[5a,13] and   \nphonon and optical responses anisotropy.[14] The electronic   \nband structures[15] of mono- and few-layer phosphorenes calcu  \nlated via density function theory (DFT) are shown in Figure 1b.   \nThe structures are for 1L, 2L, and 3L. The band structures[16]   \nshow that they can be manipulated by varying the layer thick  \nness where the gaps are ${\\approx}0.3\\ \\mathrm{eV}$ (bulk) and $2.0\\mathrm{eV}$ (monolayer),   \nas shown in Figure 1c. Bandgap is a significant characteristic   \nof the material, as it plays a crucial role in influencing the   \nelectrical, optical, and thermoelectric properties. The interplay   \nin the bandgaps is due to the strong out-of-plane quantum   \nconfinement and interlayer interactions. The bandgap range   \nin phosphorene covers the necessary technological spectral   \nrange, i.e., from the visible to mid-infrared. The tunability of   \nthe bandgap can offer unique interactions with photons and   \npolarized light,[17] where the direct optical transition occurs   \nand the strong in-plane anisotropy in phosphorene is seen. In   \naddition, the strong layer thickness-dependent electronic prop  \nerties of phosphorene offer a competitive edge over other 2D   \nmaterials.[18] Moreover, these extraordinary properties make   \nphosphorene admirable and attractive as a potential 2D-layered   \nmaterial for applications in various fields, such as in energy   \nstorage,[19] optoelectronic devices,[7,20] and field effect transis  \ntors (FETs).[10] Over the last few years, the number of studies on phosphorene  \n\nhas risen exponentially; however, the degradation of phosphorene under ambient conditions has largely limited its practical use and the actualization of its striking physical properties.[21] Therefore, innovative techniques for protecting phosphorene from degradation are much needed. The main cause of phosphorene degradation is its high reactivity with oxygen upon exposure to ambient conditions to form phosphate.[10b] Recently, substantial work has been conducted in search of effective and efficient protective modification methods of the exfoliated phosphorene with the sole aim of stabilizing exfoliated phosphorene, to make use of its intrinsic properties without interference from impurities.  \n\nAmong the 2D layered materials, phosphorene suffers the most severe degradation; its nanoflakes degrade in a few hours after exfoliation, making it very difficult to handle in open air,[22] and the multilayer form degrades after a few days.[10b] Stabilization mechanisms involved in the passivation techniques are very good factors to consider in establishing the chemistry behind the process of stabilization. In addition, gaining insight into and solving the problem of the chemistry of degradation in phosphorene is a fundamental question that needs both theoretical and experimental analyses, and we thank the various research groups who have tried to unveil this kind of information. Therefore, in this review, we will illustrate the current state of phosphorene stabilization techniques, as shown in Figure 2.  \n\nIn this review, we discuss the current state of the recent developments in phosphorene’s passivation techniques. In addition to the physical means of stabilizing BP, chemical methods and the most recently emerged chemical interaction methods are also reviewed in detail. Fabrication techniques are very crucial because they influence what the phosphorene flakes will look like at the end of the production process, thus dictating their susceptibility to oxidation; therefore, fabrication techniques will be discussed briefly. Stable phosphorene has been found to be suitable for application in various fields, such as electronics, optoelectronics, energy storage and conversion, and biomedicine, and therefore will be highlighted in the last section of this review. Finally, we will give conclusions on the status and perspectives of the stability of phosphorene, with an emphasis on passivation techniques.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2. Fundamental Basic Structure, Properties, and Importance of BP",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2.1. Basic Structure  \n\nThe preparation of BP involves the subjection of white phosphorus allotrope which is a precursor to high temperature and pressure.[9a,23] To understand the origin of BP structure is important to get the insight of white phosphorus which described by the molecular formula ${\\mathrm{P}}_{4}$ . The atoms in the white phosphorus form a tetrahedron with six single bonds of which the P atom consists of three covalent bonding with surrounding atoms. From the valence shell electron pair repulsion theory, shows that each P atom has a single lone pair of electrons and the three bonds which leads to the formation of $\\displaystyle\\mathrm{sp}^{3}$ hybridization of 3s and 3p atomic orbitals. In the $\\displaystyle\\mathbf{sp}^{3}$ hybridization, the bonds and lone pair of $\\mathrm{\\DeltaP}$ atom form an angle of $109.5^{\\circ}$ and because of the molecular structure of $\\mathrm{P_{4}}$ where angles between the bonds are $60^{\\circ}$ , which are small, hence induce some structural strain and this result in the instability seen in white phosphorus.[24] Turning to BP, obtained from white phosphorus, the  \n\n![](images/cee6866a89113fb1ffd4241875392899942f4ceb2bcf75f429fa23b76e900f23.jpg)  \n\nDavid K. Sang received his masters degree in Chemical Engineering and Technology in 2016, from Beijing University of Chemical Technology, China. In 2019, he obtained his Ph.D. degree from Shenzhen University under the mentorship of Prof. Han Zhang in the Shenzhen Engineering Laboratory of Phosphorene  \n\nand Optoelectronics, International Collaborative Laboratory of 2D Materials (ICL-2D) for Optoelectronics Science and Technology. His current research interests focus on 2D semiconductor materials’ design and simulations for optoelectronic and thermoelectric applications.  \n\n![](images/de53c200afcc19088cb08b755dfb247b8c0a46ad0686289226c0d0a765da7f79.jpg)  \n\nZhinan Guo obtained his Ph.D. degree from Jilin University in 2014. Now he is an Associate Professor in the Institute of Microscale Optoelectronics (IMO) and a Deputy Director of the Shenzhen Engineering Laboratory of Phosphorene and Optoelectronics in Shenzhen University. His current research interest is light–2D materials interactions and 2D material–based optoelectronics devices.  \n\nHan Zhang is currently a Director of the Shenzhen Engineering Laboratory of Phosphorene and Optoelectronics, Shenzhen University. His current research focus is the photo­ nics of low-dimensional materials and devices.  \n\n![](images/47f45673629fcf0392e0195dc6ccaacdf378f0058d531be9abfcf978b0ec953e.jpg)  \n\nthree bonds out of six bonds in $\\mathrm{\\DeltaP_{4}}$ have broken leaving three bonds with flattened ${\\mathrm{P}}_{4}$ with large angles; hence, no appreciable high-energy strained bonds make the BP most stable allotrope of the phosphorus element.[25] The flattened ${\\mathrm{P}}_{4}$ forms the basic building block of phosphorene and it forms a layer via linkage to two atoms from other blocks. The formed layer is not flat but is a puckered honeycomb lattice structure (orthorhombic) as shown in Figure 1a. The basic unit of phosphorene retained the $\\mathsf{s p}^{3}$ hybridization character of BP, and this shows that the orbitals contain s and p states.  \n\n![](images/000a2d2f4c62b51cb597ccf2a870b473a1de28d4b2be68a2d9b323fe724ecdfa.jpg)  \nFigure 1.  a) Side view of 3 layer phosphorene with armchair and zigzag orientations. b) Electronic band structures of few-layer phosphorene systems extracted from HSE06 hybrid functional calculations. c) Bandgap as a function of layer number extracted from different functions. Note that the direct bandgap character is maintained for all thickness up to 5L. Reproduced with permission.[15] Copyright 2015, American Chemical Society.  \n\nIn 2014, phosphorene was successfully exfoliated through sticky-tape techniques[5b] similar to how the graphene was obtained. Its fundamental structure belong to the Cmca space group number 64.[9c] The exfoliated phosphorene exhibited layered structure like other layered 2D materials with an interlayer distances of ${\\approx}3.11$ Å.[26] The layered phosphorene consists of a single element P. The $\\mathrm{\\DeltaP}$ atoms form 2D orthorhombic closed-packed layers and thus give the phosphorene crystal orthorhombic structure with two subatomic layers composed of strong in-plane covalent bonding and weak out plane bound by van der Waals (vdW) interactions. The lattice geometry constants of single layer phosphorene are $a=4.58\\mathrm{~\\AA~}$ and $b=3.32\\mathring\\mathrm{A}$ . In general, these unique fundamental structural characteristics of phosphorene play a critical role in the origin of its instability.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2.2. Chemical Properties  \n\nPhosphorene reacts with ambient species, i.e., water and oxygen are very significant because they influence fundamental properties, for examples, electronic structure in relation to air stability, transport charges, and wettability. Phosphorene is very reactive in air because of lone pair of electrons in $\\mathrm{\\DeltaP}$ atoms. The phosphorene surface’ reaction with air is enhanced by the presence of light forming $\\mathrm{P}_{x}\\mathrm{O}_{\\gamma}$ oxide. The oxide further reacts with moisture present in the ambient environment to form phosphoric acid. The visible light and oxygen $(\\mathrm{O}_{2})$ are the main contributing factors to the phosphorene degradation and, therefore, the reaction can be hampered by limiting either light or oxygen. In recent findings, phosphorene nanoparticles were established to be stable in the de-aerated aqueous dispersions for weeks.[27] In addition, phosphorene is prone to degradation because the effective surface is more exposed than in bulk BP, where the oxidized surface can be prevented by the oxide from further degradation,[28] and this makes the bulk BP more stable in ambient environment.  \n\n![](images/53c977fb432a2f5e3cd950194b011ab4df83c45798ecf0f8d7fd58d49fd1c51c.jpg)  \nFigure 2.  Chart of various passivation techniques for black phosphorus.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.3. Physical Properties  \n\nPhosphorene exhibits semiconducting behavior with considerable intrinsic physical anisotropy properties emanating from its unique structure as compared to graphene.[24,29] Phosphorene has aroused great research interests due to its layer-dependent bandgap and high mobility, which offer it distinct advantages over other 2D materials in electronic and optoelectronic appli cations.[5a,7,15,30] What especially exciting is the phosphorene’s nanosecond spin lifetime at room temperature (RT), which was theoretically predicted in $2016^{31}$ and experimentally confirmed in 2017.[32] Such long spin lifetimes afford BP new opportunities in spin-based electronics (such as spin diodes, spin transistors, and spintronics devices)[33] and which would significantly widen the application scope. Moreover, due to light, phosphorus (P) atoms in phosphorene can lead to a low spin–orbital coupling where the magnetoresistances in the phosphorene device can manifest and tune by gate voltage to optimal range for injection and detection of spin-polarized holes, thus making phosphorene suitable for spin transport devices.[33c]  \n\nPhosphorene is a direct allowed transition which falls between $0~\\mathrm{eV}$ for graphene and $2.0\\ \\mathrm{eV}$ for TMDs.[18,34] Varying the thickness of phosphorene leads to different energy values, which tend to change electronics and associated properties which are depended on the layer thickness. Optical absorption range of phosphorene covers near-infrared and mid-infrared, and this is a key feature of phosphorene as a potential material for photovoltaic cells, photocatalysis, thermoelectric, and thermal imaging[35] In addition, optical responses such as nonlinear saturable absorption, Kerr nonlinear, and ultrafast carrier dynamics can be manipulated in phosphorene via varying lateral size, which are essential in the design of phosphorenebased electronics and optoelectronics devices.[36]  \n\nMoreover, phosphorene crystal structure presents noticeable anisotropic properties unlike TMDs where physical properties are almost isotropic. Critical analysis of mechanical properties depicts a strong anisotropy along zigzag and armchair directions. Through first principles calculation, Jiang and Park studied the Young’s modulus and examined the variations in values from zigzag and armchair directions.[37] The determined Young’s moduli of monolayer in the zigzag and armchair directions are 56.3 and $21.9\\ \\mathrm{N}\\ \\mathrm{m}^{-1}$ , respectively. The magnitude of Young’s modulus in the zigzag direction was approximately twice the value along the armchair direction. Qin et  al. calculated the thermal conductivities in both directions (zigzag and armchair) and found out that in both zigzag and armchair directions, thermal conductivities were 30.15 and 13.65 W $\\mathrm{m}^{-1}\\ \\mathrm{K}^{-1}$ , respectively.[38] Zhang et  al. performed molecular dynamic simulation on a large single layer of phosphorene and demonstrated thermal conductivities along zigzag and armchair directions to be 42.553 and $9.891~\\mathrm{{W}~m^{-1}~K^{-1}}$ , respectively.[39]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.4. Importance of Phosphorene  \n\nAmong the families of 2D and layered materials, phosphorene is the most celebrated and regarded as a rising star beyond graphene, due to the iconic intrinsic tunable direct bandgap at monolayer, and few-layer forms, with high charge transport in the order of $\\approx10^{5}\\ \\mathrm{cm}^{2}\\ \\mathrm{V}^{-1}\\ \\mathrm{s}^{-1}$ , on/off current ratio of ${\\approx}10^{5}$ and unique in-plane anisotropic structure.[10a,40] Also, phosphorene exhibits p-type character with weak layer interaction, making it possible to be fabricated to a single layer number.[5b] Phosphorene shows an outstanding electronic structure, which influences its ability to absorb the light with energy greater than the gap energy without intrinsic resistance as compared to other vdW solids with indirect allowed transitions, where extra phonon must be absorbed to compensate for the difference momentum; hence, photon absorption process is inefficient. Due to the tunable optical absorption via doping with vacancy or appropriate elements, application of external electric field, functionalization via chemical or surface co-ordinate and stress–strain engineering, all these have shown to modulate the optical responses within the UV–IR regimes. In addition, phosphorene has been demonstrated to be a potential material with applications in 2D-LEDs, solar cells, lasers, optical switches, transparent displays, sensors, and photodetectors.[41]",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 3. Challenges Facing Phosphorene",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 3.1. Air Instability  \n\nPhosphorene has attracted great deal of interest because of its excellent electronic transport and high-performance tunable electronic band structure, which are suitable for design of electrical and optoelectronic devices;[42] however, due to instability, a oxidative process has made it difficult for practical actualization in the field of electronics and optoelectronics.[42] It has been established that few-layer phosphorene undergoes photo­ degradation within $^{2\\mathrm{h}}$ , hampering its accurate characterization procedure due to defects caused by the surface and edge degradation during the preparation process. Therefore, achieving stability in phosphorene demands a well-researched passivation techniques.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3.2. Mass Production  \n\nLarge production of phosphorene is more advantage for industrial purposes and commerce. The fundamental factor in meeting the demand phosphorene material is the production rate. Therefore, upscaling the production of monolayer or few-layer phosphorene still faces major challenges.[15] The mechanical exfoliation method is known to produce the bestquality samples, but the production scale is low and this will not meet the industrial demand. Even though, pulsed laser deposi$\\mathrm{tion}^{[43]}$ and liquid-phase exfoliation[44] can produce appreciable large samples, the quality is low and needs further modification to meet the standard for applications. Phosphorene fabrication poses a huge challenge to the researchers because the growth of bulk BP demands high pressure and temperature which are not attainable in the ordinary crystal growth approach[45] and phosphorene made via the bottom-up approach where the controllable synthesis of single- and multilayers are hard to attained. The method that can meet both the large samples’ production and good quality standard is considered in fabrication of phosphorene. Desirable techniques for phosphorene production should be simple, scalable, and cost effective, for feasible industrial purposes, maximum production, and good returns. Consequently, mass production of phosphorene with environmentally stability is quite difficult, though it is extremely important for industrial applications, and this challenge needs a synergy approach to ensure large production of phosphorene with air stable.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 4. Fabrication Techniques for Phosphorene  \n\nResearch on bulk BP dates back to 1914, where the first successful synthesis of black phosphorus was done via roasting white phosphorus in the furnace under high temperature and pressure[9a] and was found to be the most thermodynamically stable allotrope of phosphorus. Few studies then highlighted the use of BP because of difficulties in the fabrication process and the conditions needed, i.e., high pressure and temperature, and it received very low attraction. About 100 years later, BP was rediscovered, where isolation of monolayer (phosphorene) was successfully done via sticky tape by two different groups[5b,10a] Production of phosphorene is very critical and it demands reliable methods which yield high-quality phosphorene. Up to date, there are two approaches applied in phosphorene synthesis, which are bottom-up approaches (growth method) and top-down approaches (dissection method).[46] The bottom-up approach is based on wet chemistry like wet-chemical method and chemical vapor-deposition (CVD) epitaxial process, while top-down approaches are purely exfoliation of either monolayers through breakage of interlayer interaction through mechanical or chemical processes. In recent years, electrochemical exfoliation of BP is shown to be a new and effective method to obtain few-layer phosphorene.[47] Based on the current publications, it is shown that top-down methods are the most studied approaches48 and have raised prospects for the synthesis of 2D materials which can be used in various applications.",
+        "category": " Introduction"
+    },
+    {
+        "id": 12,
+        "chunk": "# 4.1. Liquid-Phase Exfoliation  \n\nLiquid phase exfoliation (LPE) is the preparation of nanoparticles from bulk-layered materials through electrostatic separation in aqueous solvent and matching surface energy in the organic solvent system.[49] LPE has been demonstrated as a potential method with a possibility of upscaling to obtained phosphorene nanosheets’ dispersal in solution.[50] This method has several strategies such as ion intercalation/exchange and sonication-assisted exfoliation[51] as shown in Figure  3. Shapter et  al.[52] recently developed an efficient production of phosphorene nanosheets through shear stress for a short processing time, and production of atomically thin phosphorene was achieved. Xu et al.[53] developed a scalable shear exfoliation of high-quality phosphorene nanoflakes by using simple means like a high-speed shear mixer or even a household kitchen blender, making this method relatively cheap and scalable to industrial applications. Guo et  al.[54] carried out a simple and cost-effective LPE experiment to produce phosphorene with excellent water stability, controllable size, and layer number as well as high yield by using basic $N\\mathrm{.}$ -methly-2-pyrrolidone (NMP) as the solvent. This approach proved that LPE is relatively very cheap and can produce phosphorene with desirable thicknesses.  \n\nMoreover, phosphorene with high quality has been produced through sonication of the liquid exfoliation method,[55] and the procedure was as follows: bulk black phosphorus crystal is sonicated in NMP solvent $(5~\\mathrm{mg}~\\mathrm{mL^{-1}}$ ) at $820~\\mathrm{\\textperthousand}$ and the frequency was set to $37\\mathrm{kHz}$ and powered for $24\\mathrm{h}$ under $30\\%$ power, and bath temperature was maintained below $30~^{\\circ}\\mathrm{C}$ using a watercooling coil, throughout the sonication process. Then, centrifugation of the final turbid was done to extract large flakes leaving the pale yellow/brown color dispersion of phospherene unchanged.  \n\nBased on the demand of ultrathin phosphorene for various applications in electronic and optoelectronic, quality is considered and is determined by the sonication of solvents. Yasaei and his group exfoliate few-layer phosphorene from bulk BP using various organic solvents with the range of $(2.98\\mathrm{-}9.3\\ \\mathrm{MPa}^{1/2})$ polarity and (21.7–42.78 dyne $\\mathrm{cm^{-1}}$ ) surface tension. Finally, aprotic and solvent with polarity were found to be the best solvents to exfoliate phosphorene from bulk BP after sonication for a period of $^{6\\mathrm{~h~}}$ at $130\\mathrm{~W~}$ for $0.2~\\mathrm{mg}/10~\\mathrm{mL}$ solvent.[44] Therefore, The advantages of LPE technology are low cost, high efficiency, and simple operation. In addition, the sample prepared by this method has good stability in NMP and some other solvents. However, the disadvantage of this method is that the quality and size of the sample are not good enough.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 4.2. Plasma-Assisted Fabrication  \n\nThe production of monolayer and few-layer of 2D materials via this method has been demonstrated to be faster and effective, and sizes are controllable.[10b,56] Lu et  al. demonstrated this strategy approach using few-layer phosphorene by placing on $\\mathrm{SiO}_{2}/\\mathrm{Si}$ substrate and pre-treatment with optimized conditioned plasma to produced monolayer phosphorene through etching[56b] as shown in Figure  4a. The advantage of the plasma-assisted method is that the thickness of the sample can be artificially controlled. Furthermore, the method can be used to remove the oxide layer on the surface of the sample. Its disadvantage is that the speed and precision of etching process are difficult to be controlled accurately.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 4.3. Pulse Laser Deposition  \n\nPulse laser deposition (PLD) is one of the physical bottomup synthesis methods, which involves physical deposition of vapor on nonmetallic substrate.[57] It is commonly used to grow the complex oxide thin films and has been demonstrated as the best alternative method for the CVD method, unlike the extreme conditions of pressure and temperature in the preparation of black phosphorus allotrope.[7] PLD exploits the gas segment attained after raising the temperature, and the formation of thin film sheets on cooling or via chemical reaction.[58] A defective BP crystal with a size ranging from several nanometers to tens of nanometers was successful developed on substrates through PLD by utilizing bulk BP as the precursor.[59] Recently, $\\mathtt{X u}$ et  al. synthesized amorphous ultrathin phosphorene with a highly disordered structure arrangement film of $4\\ \\mathrm{nm}$ via deposing red phosphorus on a flexible polyester substrate, and the red phosphorus transformed into BP nanosheet in multi-anvil cell under high pressure[45] where they fabricated an amorphous ultrathin BP on graphene/Cu or $\\mathrm{SiO}_{2}/\\mathrm{Si}$ substrates via the PLD method as shown in Figure  5. The setup framework was as follows: a distance of $4\\ \\mathrm{cm}$ from the BP and substrate was set, and the chamber was evacuated to around $1.5\\times10^{-7}$ Torr before the PLD deposition. The microenvironment around the substrate was maintained at $150~^{\\circ}\\mathrm{C}$ , and the BP deposit (target) was evaporated through KrF pulse laser at $248~\\mathrm{nm}$ wavelength with a $5~\\mathrm{Hz}$ cycle. Throughout the PLD process, BP and the substrate were rotated simultaneously so as to achieve uniform film growth. Finally, the as-prepared amorphous ultrathin disordered BP film was cooled down to room temperature in a high vacuum chamber followed by characterization. Largescale film and favorable low-processing temperature are of great importance in device applications. It is anticipated that PLD-grown phosphorene will attract great attention from scientists and technologists. In this method, layers can be controlled by regulating the laser ablation exposure time, hence produce ultrathin 2D materials at low temperature and pressure, while the demerit of this method is the need of strict preparation conditions.  \n\n![](images/43a10a84afb1a152b27a432823f948de8e73b978081b48b4efc2aa035ac55c39.jpg)  \nFigure 3.  Schematic descriptions of the main liquid exfoliation mechanisms. a) Ion intercalation: ions (yellow spheres) are intercalated between the layers in the liquid environment, swelling the crystal and weakening the interlayer attractions. Then, the agitation (like shear, ultrasonication, or thermal) can completely delaminate the layers, resulting in the exfoliated dispersion. b) Ion exchange: some layered compounds contain ions in between the layers in order to balance charge on the layers. Th (red spheres) can be chan ged with other ions with larger size (yellow spheres) in a liquid environment. As shown above, the agitation results inan exfoliated dis sisted exfoliation: the layered crystal is sonicated in a solvent, resulting into exfoliation and nanosheet format wh solvents (those with appropriate urface energy) the exfoliated nanosheets are stabilized against reaggregation. While in “bad” solvents, reaggregation and sedimentation will occur. Note that solvents molecules are not shown in this figure.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# 4.4. Chemical Vapor Deposition  \n\nThis method is one of the bottom-up synthesis approaches of nanomaterials and has been known to produce high-quality 2D materials, for example, graphene and TMDs.[60] More effort has been put up in the production of phosphorene in large scale in order to compete fairly with other 2D materials such as graphene and TMDs in the emerging fields.[61] Also, growing a single crystal of phosphorene for the purpose of studying its anisotropic properties in large scale is a priority in the design of production technique.[62] Smith and his group grew phosphorene film of $>3~\\upmu\\mathrm{m}^{2}$ and lateral size of approximately four layers[63] using a set as shown in Figure  6. In addition, the preparation of wafer scale on metal substrate and epitaxial growth on isolating substrate[64] have enabled the fabrication of device-based graphene in large scale. However, this method has not yet been fully explored in the production of highquality phosphorene as in the aforementioned 2D materials.  \n\n![](images/8aac7d39ab408b3a3b7eee8bc6410f3be6dfb762ad5144359a15399da7ba1816.jpg)  \nFigure 4.  a) Diagram showing the plasma etching process on the surface of BP nanosheet. b–d) Flake optical images at different storage durations. $\\mathsf{e{-}g})$ BP thickness at different regions, BP thickness as a function of duration exposed to plasma treatment, and Raman spectra as a function of thickness, respectively. Reproduced with permission.[56b] Copyright 2015, American Chemical Society.  \n\nThe advantage of this technology is that it is expected to realize the industrial production of phosphorene with large size. However, the method needs further refinement by optimizing the processing conditions. Furthermore, this method is not yet fully explored in phosphorene production.  \n\n![](images/e945c7613f0ac43f06770c2e3e424ac5c13caab3b51cf65346de1cf7b723576a.jpg)  \nFigure 5.  a) Schematic setup of pulse laser deposition (PLD) for production of ultrathin BP. (b) Energy dispersion X-ray (EDX) spectrum of a-BP film grown on $\\mathsf{S i O}_{2}/\\mathsf{S i}$ . c) Raman spectra of a-BP films deposited under different temperatures on the PLD. Reproduced with permission.[45] Copyright 2014, IOP Publishing.  \n\n![](images/fb863e11fb509a9c5479e275b3fba45468f53703d89ebc085c1bc4b193c450e5.jpg)  \nFigure 6.  a) Schematic production of BP film via the chemical vapor deposition method. b) Scanning electron microscopy (SEM) image of thin substrate black phosphorus (SBP) sample on the substrate. c) Thin film of SBP with an area of $0.35\\upmu\\mathrm{m}^{2}$ , inset: height profile of SBP thin film showing a thickness of ${\\approx}4$ layers $(3.4~\\mathsf{n m})$ . Reproduced with permission.[63] Copyright 2015, IOP Publishing.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 4.5. Wet Chemical Method  \n\nThis method is one of the bottom-up approaches for preparing 2D materials,[65] and it comprises solvothermal, hydrothermal, template synthesis, and self-assembly of particles. Previous studies showed that this method has been applied in the production of graphene and TMDs.[66] Fan et al. carried out hydrothermal synthesis of functionalized phosphate carbon, which consists of composite carbon with porous support material via a model of hydrothermal approach, preceded by heat treatment,[67] as demonstrated in Figure 7. It was reported recently that synthesis of phosphorene via this method was achieved.[68] The advantages of this method are low production cost and high quality of samples while its limitation is that it is difficult to control thickness, large size, and large-scale production of the sample.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 17,
+        "chunk": "# 4.6. Mechanical Cleavage  \n\nThe Nobel Prize award for physics in 2010 was as a result of breakthrough in micromechanical cleavage of high-ordered pyrolytic graphite (HOPG) in 2004.[1,69] From this noble success, the idea has been extended to other layered materials. Effectiveness and quality production of few-layer materials make the mechanical method receive much attention in fabrication of 2D materials.[25,70] BP is layered material and its layers are held together in out of plane by weak vdW interactions which make it easy to obtained monolayer and few-layer phosphorene via the mechanical exfoliation. The mechanism process for this method is simplest, because it involves the application of adhesive scotch tape to the pellets of bulk BP and pressed with the standard force, as demonstrated in Figure 8. Exertion of standard force for several times leads to the production of thinner phosphorene. Through this method, control of exfoliated phosphorene layer with high quality is possible, and it enables the study of physical properties in phosphorene without inaccuracy from the edge and surface defects. However, this technique is time-consuming and labor intensive. Moreover, this technique is the best choice for phosphorene devices’ fabrication with high quality, but it cannot be produced on a large scale and hence confined to be used for laboratory research.  \n\n![](images/5cd9f2a0588caab719fea936bc1188aba5f549224b3879a2bc4a0a7e83168f70.jpg)  \nFigure 7.  Schematic illustration of wet chemical approach. a) Wet chemicalproduction process via chemical solvothermal reaction. b) Holey phosphorus-based composite nanosheet. The morphology evolution of the bulk red phosphorus at high-temperature solvothermal reaction at c) $2h$ , d) $12\\mathsf{h}$ , and e) $24\\ h$ , respectively. f) Illustration of the formation of the holey phosphorus composite nanosheets. g) Sublimation of the bulk red phosphorus. h) Formation of the phosphorus nanodomain in ethanol solution (ethanol/phosphorus vapor on the top) at the initial stage. i) Formation of phosphorus nanosheets in the ethanol (near supercritical fluid) via bottom-up assembly. j) Final product in the enthanol solution. Reproduced with permission.[68] Copyright 2016, Wiley-VCH.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# 5. Ambient Instability and Improving the Stability of Phosphorene",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 5.1. The Mechanism of Ambient Instability  \n\nEven though bulk BP is supreme in terms of stability but phosphorene is unstable in humid air and light,[71] and this has been the limiting factor for its full actualization in practical applications. It has been reported widely that a bare phosphorene possesses a strong affinity for water and oxygen molecules in the presence of photoenergy (light), and this has hindered the utilization of phosphorene in electronics and optoelectronic devices. Also, the degradation process is a factor of layer thickness and this has been confirmed by van der Zant et  al.,[10b] that flake thickness (from bulk to a limit of single layer) exhibits insightful trends in degradation rate. The origin of instability emanates from the structural nature of phosphorene where the energy gap is an aspect, which plays an important role in instigating the photo-oxidation process. Each atom is covalently bonded $(\\mathsf{P}{\\mathrm{-}}\\mathsf{P})$ with a lone pair of electron resonating within the bonds, hence exposing bonds prone to attack, thus instigates the process of phosphorene degradations.[72]  \n\nThe chemical instability of phosphorene is influenced by the lone pair of electrons in phosphorus atoms, and this has demonstrated the limited ambient stability of phosphorene. The photoenergy hastens the degradation process of phosphorene to form $\\mathrm{P}_{x}\\mathrm{O}_{\\gamma}$ on the surface, and the limiting step in oxidation rate is influenced by the oxygen concentration, energy gap, and light intensity. Further exposure will lead to the formation of phosphoric acid. This has been demonstrated in the recent experiment[73] where phosphorene was found to be steady under de-aerated solutions for several days, and this shows that water and phosphorene surface interact weakly. Moreover, oxidized surface can effectively control the phosphorene inner layer from degrading[74] and this support the fact that bulk BP is stable in ambient conditions.  \n\nRecently, Wang and co-workers discovered theoretically that the BP degradation process involves three steps: first, the formation of unstable oxide within visible illumination; second, detachment of unstable oxide; third, separation of unstable oxide under water activity.[75] The covalent bond $_{(\\mathrm{P-O-P})}$ on the surface of BP plays an important role in stabilization of BP structure, and this shows that the superficial layer formed after the full process of oxidation is a protective cover for preventing further degradation.  \n\n![](images/dca7e382d839b4e40fa7817ff69eabd4a1f497a63bed0acfd4ece65f2b0a25b6.jpg)  \nFigure 8.  Mechanical exfoliation procedures of obtaining few-layer phosphorene from bulk BP by using adhesive scotch tape.  \n\nFew-layer phosphorene fabricated via mechanical exfoliation is prone to degradation in ambient environment due to the presence of humid air as investigated by Neto and coworkers[76] and Hersam and co-workers,[77] respectively, and this demonstrated that oxygen, water, and photon energy (light) are needed concurrently for the degradation process to take place on the surface of phosphorene. Edges of phosphorene flakes are also prone to degradation because of the edge-induced mechanism, which is instigated by moisture and the presence of impurity traces at the edges of the flake, and high affinity of moist air by dangling bonds on the edges leads to high degradation rate.[78] Moreover, poor coating at the edge of phosphorene contributes to high rate of degradation. Also, the internal key factors such as thickness and lateral dimensions influence the environmental instability of phosphorene[25] Earlier reports indicated that phosphorene degradation in ambient conditions is strongly due to moisture and hydrophilicity nature of the phosphorene.[10b,79] The degradation process is not well understood, and the systematic investigations of degradation process have been done by employing spectroscopic instruments such as atomic force microscopy (AFM), polarized Raman, and transmission electron microscope (TEM) combined with high-angle annular dark field (ADF) and hyperspectral electron energy loss spectroscopy[80] to fully comprehend the principles behind this phenomenon. Free water, air, and photolight are the main variable elements behind the phosphorene degradation process, which was confirmed by Wang et al.[81] through DFT and ab initio molecular simulations; thus, it provides an insightful information on how $\\mathrm{O}_{2}$ and water interact on the surface of phosphorene. They demonstrated through their findings that oxygen extemporaneously detaches on phosphorene surface at room temperature, while, on the other hand, water–pristine BP interaction is not strong. However, some reported controversial observation that phosphorene –water reaction is feasible without the presence of oxygen,[82] and this negates the earlier report that phosphorene–water reaction is not feasible without the presence of oxygen. Walia and his group confirmed that moisture alone does not cause degradation on the freshly exfoliated phosphorene,[83] and this confirms that the three essential variable elements needed to jump-start the degradation process are all interdependent and their trading-off is a subject of intense study. Other than water, oxygen, and light, temperature is also believed to influence the phosphorene degradation to an extent. The light-induced chemical reactions on phosphorene surface and edge are demonstrated in the following  \n\n$$\n\\mathrm{monolayer}\\left(\\mathrm{few-layerBP}\\right)+h\\nu\\rightarrow\\mathrm{BP^{\\ast}}\n$$  \n\n$$\n\\mathrm{BP^{*}}+\\mathrm{O}_{2}\\rightarrow\\mathrm{O}_{2}^{*-}+\\mathrm{BP}+h\\nu\\rightarrow\\mathrm{PO}_{x}\n$$  \n\nIn Equation  (1), the incident visible light with phonon energy surpasses the electronic bandgap of phosphorene, thus generates excitons, which leads to photoinduction of electron and hole pairs in phosphorene. In Equation  (2), the adsorbed oxygen molecules trap the photogenerated electrons to produce the intermediate superoxide anions $(\\mathsf{O}_{2}^{\\bullet\\bullet})$ . The excess $\\mathbf{O}_{2}^{\\bullet}$ and photogenerated holes further induce the oxidation of phosphorene and phosphorus oxide species $(\\mathrm{PO}_{x})$ are formed. Effects of photo-oxidation on phosphorene fabricated devices are enormous and limit its full implementation. The outcome of photo-oxidation is that the insulating layer of oxide enhances the surface protection from further corrosion, and also the layer formed increases the Ohmic resistance.[5a] Ambient dilapidation on phosphorene also yields significant physical changes, thus causes increase in surface roughness, triggering impediment in carrier mobility.[84] Severe degradation changes phosphorene’s intrinsic electronic properties which can alter the threshold voltage of phosphorene-based transistors, thus reducing its optimum performance via lowering $I_{\\mathrm{on}}/I_{\\mathrm{off}}$ ratio on carrier transport.[77]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# 5.2. Ways of Improving the Stability  \n\nThe freshly exfoliated layers of phosphorene are prone to the oxidation process, which began immediately upon exposure to favorable conditions for the process to take to place on the exposed surface.[10b] The presence of moist air, light, and the phosphorene flakes’ surface or edge are the fundamental variable parameters needed for the formation of $\\mathrm{PO}_{x}$ .[80] Ambient degradation limits the performance of phosphorenefabricated devices; thus, stabilizing phosphorene is crucial to its applications. Chemical stability of phosphorene needs to be well studied before selecting the field to be applied. The quality of phosphorene layer reduces against the size, and the degradation severity depends on the layer thickness because of the quantum-confinement effects.[79b,80] This is because reducing layer thickness enlarges the gap, hence, drift energy gap to higher energies and shift the valence band maximum (VBM) and conduction band minimum (CBM) to align with the one of oxygen.[75] Despite the fact that phosphorene is less reactive as compared to other elemental 2D materials like silicene, and can be studied under the normal conditions for a certain duration of time, and prolonging the handling time has been a topic of concern. Enhancing the stability will enable phosphorene to be a potential material suitable for electronic and optoelectronic applications. This observation has prompted several researches towards understanding the chemistry behind the degradation process and possible passivation techniques. Passivation strategies with effective protective layers and coating with other inactive layered materials have proved to be very effective methods to protect the phosphorene surface from degradation.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# 5.2.1. Encapsulations  \n\nEncapsulation is a physical method of passivation where the phosphorene layer(s) is covered with appropriate material before exposing to air–water–light condition, devoid of other substances like chemical supports as shown in Figure 9a. This method has been confirmed to be noncovalent functionalization using different capping layers such as $\\mathsf{A l O}_{x},$ $\\mathrm{SiO}_{2}$ , and polymers to enhance the air stability of phosphorene.[77,85] High charge carrier mobility exhibited by phosphorene semiconductor has made it to have a potential to replace silicone in the making of very fast response nanodevices that consume less energy. However, rapid oxidation has limited this ability to substitute the silicone. Successful physical passivation and enhancement of electrical properties of phosphorene via encapsulation with $\\mathrm{Al}_{2}\\mathrm{O}_{3}$ layers have been reported.[86] Ozyilmaz and co-workers demonstrated phosphorene surface protection by employing the graphene sheet and hexagonal boron nitride to sandwich the phosphorene, where the encapsulated phosphorene showed enhanced electron mobility, thus exhibiting a balanced n-type and p-type transconductance behavior.[87] h-BN exhibits smooth surface free of dangling bonds and low roughness, compared to $\\mathrm{SiO}_{2}^{88}$ and atomically good material for encapsulating the phosphorene as demonstrated by Doganov et al.,[89] thus, enhanced the phosphorene stability. Atomic layer deposition over layers has been shown to deprive the defects caused by surface reaction, hence boosting the on–off current ratio to ${\\approx}10^{3}$ and carrier transport to ${\\approx}100~\\mathrm{cm}^{2}~\\mathrm{V}^{-1}~\\mathrm{s}^{-1}$ for several days.[77] Combination of dielectric materials with polymer can be a synergy approach to prolong the ambient stability of phosphorene, where Kim et  al. established that the double-layer capping strategy stabilized the ultrathin film phosphorene in a transistor for an infinite period of time,[78] and thus overcoming a significant material challenge for applied research and development. Recently, Lau and co-workers demonstrated that capping phosphorene with polymer improves the stability, durability, and regulates the Schottky barriers between phosphorene surface and metal. Furthermore, this strategy is nondestructive and effective technique to achieve double strategy.[90] ${\\mathbb{W}}{\\mathbb{u}}$ et  al.[91] recently demonstrated a very simple and effective encapsulation method by using $\\mathrm{SnO}_{2}$ film to limit the action of water vapor and $\\mathrm{O}_{2}$ in air from eroding the phosphorene surface. In this approach, tin oxide film was formed via electron-beam evaporation of a tin film and, subsequently, exposed to natural oxidation in air. The fabricated back-gate FETs from the passivated phosphorene exhibit a typical p-type character and maintained a constant hole mobility of ${\\approx}200\\ c m^{2}\\ \\mathrm{V}^{-1}\\ \\mathrm{s}^{-1}$ and a high $I_{\\mathrm{on}}/I_{\\mathrm{off}}$ ratio of ${\\approx}10^{4}$ for over 15 days, as shown in Figure $^{9\\mathrm{c},\\mathrm{d}}$ respectively. The advantage of this method is that it can keep the stability of ultrathin phosphorene films for a long time, and their properties are basically unaffected while the disadvantage is that this method cannot fundamentally solve the problem of instability of phosphorene.  \n\n![](images/ca25441ce864baa7d2cf971bf12eea245c34863f89c1c522e4b60480a7ed6291.jpg)  \nFigure 9.  Structure, electrical characteristics, and ambient performance of BP–FETs with and without $\\mathsf{S n O}_{2}$ passivation: a) Schematic of BP–FET with $\\mathsf{S n O}_{2}$ passivation. b) Transfer curves of the passivated BP–FET at different time, i.e., as fabricated, $\\mathsf{l o h}$ and 15 days, $V_{\\mathrm{ds}}=-0.7$ V. c) Hole mobility (pea field-effect miobility at $V_{\\mathrm{ds}}=-0.1~\\mathrm{V})$ ). d) $I_{\\mathrm{on}}/I_{\\mathrm{off}}$ ratio with change with time exposed in air. Reproduced with permission.[91] Copyright 2019, Elsevier.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# 5.2.2. Surface Functionalization  \n\nDue to the atomically thin nature of phosphorene, chemical doping based on surface modification with adlayer provides a strong and nonvolatile doping strategy on phosphorene with a very simple way of device fabrication. Chemical doping of phosphorene’s FETs has been carried out with metal oxides $\\ensuremath{\\left(\\mathrm{Cs}_{2}\\mathrm{CO}_{3}\\right.}$ and $\\mathsf{M o O}_{3})$ ,[92] where FET’s performance was recorded. Considering the orientations and the chemistry of the lone pairs existing on phosphorene surface, functional group reacts with the lone pair to form the PX bonds and further functionalized via suitable substitution reactions, thus ensuring that the formed surface is not prone to oxygen attack. The covalent functionalization in phosphorene via aryl diazonium proved to limit the chemical reaction, hence reduces the severity caused by the photo-oxidation process (carbon–phosphorus bond formation) in phosphorene-fabricated devices for even 3 weeks upon exposure to ambient conditions.[42] The covalent and noncovalent functionalization[42,93] strategies via coating with polymer films have proved to be very effective in improving phosphorene stability. Hirsch and co-workers[94] recently reported unprecedented top-down strategy for thinning BP flakes at will by controlling the oxidation process and removing the oxidized phosphorus species such as phosphoric acid by utilizing water solvent, and this oxidative process can be terminated via noncovalent functionalization with perylenediimide chromophores resulting into prevention of the photo-oxidation process on the surface of phosphorene flakes which they demonstrated via femtosecond transient spectroscopy, and the electronic properties of the flakes were not compromised.[102] Many organic compounds have been used not only to modulate the transport but also to enhance protection from ambient degradation.[95] Lei et  al.[96] demonstrated adsorption of Ca, Sr, Ba, Cs, La, and Cl on the surface of monolayer BP and the results showed CBM shift below $\\mathrm{O}_{2}/\\mathrm{O}\\overline{{2}}$ redox potential; thus, it prohibits the oxidation to take place and, hence, enhances the ambient stability of few-layer phosphorene.  \n\nMetal-ion modification has been confirmed by Guo et  al.[97] as one of the effective strategies for surface functionalization, which enhances the stability of BP. They have demonstrated that silver ion $(\\mathrm{Ag^{+}})$ adsorbed into phosphorene surface by conjugating $\\pi$ -bonds to yield a ${\\mathrm{Ag}}^{+}$ -modified BP $(\\mathrm{BP_{Ag(+)}})$ can limit the lone pair of electrons from $\\mathrm{\\DeltaP}$ atoms by interacting with oxygen from ambient environment, which leads to a stable phosphorene. The mechanism behind the interaction between ${\\mathrm{Ag}}^{+}$ and BP sheet is that the lone pair of electrons on the phosphorene surface are evenly distributed forming conjugated $\\pi$ -bonds, thus providing a platform for the ${\\mathrm{Ag}}^{+}$ to strongly bond on it through the cation– $\\pi$ interaction, preventing the oxygen from reacting with the lone pair of electrons of the $\\mathrm{\\DeltaP}$ atoms, as shown in Figure  10a. To check on the ${\\mathrm{Ag}}^{+}$ -modified BP, the AFM test was carried out and found that $\\mathsf{B P}_{(\\mathrm{Ag}+)}$ sheet was stable for 5 days as shown in Figure 10d.  \n\nCovalent functionalization has been demonstrated by Ryder et  al. that it protects the phosphorene from degradation, thus stabilizes and improves the FET characteristics.[42] Also, decorated exfoliated phosphorene with nickel nanoparticles (Ni/phosphorene) exhibits enhanced stability compared with pristine phosphorene when both are kept under ambient conditions in the dark.[98] Also, covalent functionalization of 2D materials via chemical modification schemes not only manipulates the chemical,[99] optical,[100] and electronic[101] properties, but also enhances the stability as seen in stable $\\mathsf{P{\\mathrm{-}}C}$ bonds evolution across phosphorene–graphite,[102] and this provides the carbon-chemical-based passivation strategy suitable for stabilization of phosphorene surface. The fabricated polydoamine (PDA)-modified nanosheets were reported to show an improved stability as compared to bared phosphorene nanosheets,[103] and the coated phosphorene nanosheets with PDA also exhibited an enhanced stability.[104] Both encapsulation and surface coordination have proved to be effective strategies, synergy for enhancing the phosphorene stability, as recently demonstrated by Zhang et  al.,[105] by designing a new janus nanoparticle based on BP quantum dots and tetrahydraxyanthraquinonemetal–organic particles to concurrently demonstrate an improved microenvironment stability of phosphorene and at the same time boost the photocatalytic action for applications in the treatment of cancerous cells. Therefore, the sandwich BP quantum dots (QDs) in janus particles isolate the water and air and trap the lone pair of electrons in BP resulting in improved BPQDs’ ambient stability.  \n\nThis method starts from the source of the instability of phosphorene and stabilizes the phosphorene by functionalizing the surface of phosphorene and binding the lone pair of electrons on the surface of phosphorene. Although the present research results cannot stabilize phosphorene for infinite time, this idea is expected to be the fundamental method to solve the stability problem of phosphorene.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# 5.2.3. Liquid-Phase Surface Passivation  \n\nThe phosphorene degradation poses a big challenge, and remedy to this drawback in liquid-exfoliated phosphorene is surface modification via liquid-phase surface passivation. This method has been utilized in preventing degradation of phosphorene.[42,93,106] To achieve this, appropriate conductive polymer[107] and ionic liquid (ILs)[108] are needed. Recently, phosphorene suspension prepared from different ILs was confirmed to exhibit air stability for 1 month,[108] and also, surface coating with ILs proved to be an effective suppressor of the oxidation process in mechanically exfoliated phosphorene nanoflakes.[25,109] Zhang et al.[110] showed stabilization of phosphorene via a single-step ionic liquid–assisted exfoliation process and synchronous fluorination step whereby the fluorinated phosphorene exhibited enhanced air stability during 7 days of air exposure. Polymer ionic liquid (PIL) has been proved to be an effective approach in surface passivation of few-layer BP,[111] where the polymer ionic liquid–modified phosphorene showed enhance stability which goes for up to 100 days, with little degradations observed on the phosphorene surface. Besides stabilizing the few-layer phosphorene, PIL-modified phosphorene provides dependable flexible contact across the phosphorene and nanodevice constituents. Walia et  al.[109] used imidazolium-based ionic liquids to suppress the reactive oxygen species, which is responsible for phosphorene degradation, and this demonstrated that phosphorene remained stable for over 13 weeks without alteration of its key electronic properties. Recently, Fan et  al.[112] demonstrated the phosphorene modification via the wet chemistry approach where thinning and surface protection of phosphorene was achieved. Combination of two electron-deficient reagents and triphenyl carbernium tetrafluorobor was applied for thinning, while 2,2,6,6-tetramethyl piperidyl-N-oxyl was used for enhancing the stability for up to 4 months through surface coordination. Deoxygenated water has been used to prolong the photocatalytic activity of exfoliated few layers of phosphorene for 15 days,[113] and this has given insights into the chemistry of phosphorene degradation.  \n\n![](images/891abb95291a2317820559626c9e862e6a8070c4cf293129585b26584f0f1bc1.jpg)  \nFigure 10.  a) Schematic illustration of ${\\sf A g}^{+}$ adsorption on BP. b) ${\\mathsf{B P}}_{\\mathsf{A g(+)}}$ in three different views. c–e) AFM images of pristine BP sheet exposed to air for c) 1 day, d) 3 days, and e) 5 days. f–h) AFM images of ${\\mathsf{B P}}_{\\mathsf{A g(+)}}$ sheet exposed to air for f) 1 day, g) 3 days, and h) 5 days. Reproduced with permission.[97] Copyright 2017, Wiley-VCH.  \n\nPolymers have been used to stabilize the exfoliated phosphorene and recognized as an excellent material for layer intercalation in nanoparticles,[114] forming heterostructures with enhanced performance optimal for optoelectronic, sensors and nonlinear optics.[115] Polymer coating, like poly(methyl methacrylate) (PMMA), not only preserves mechanically exfoliated phosphorene flakes but also improves its stability.[116] Moreover, polymers play a significant role in semiconductors,[117] detection platforms in biomedical field,[118] pseudocapacitors,[119] and lasers.[120] Passagalia et  al.[85a] demonstrated polymerbased phosphorene hybrid material in situ radical polymerization, which has been proved to be an effective tool to obtain stabilized phosphorene flakes, and this is a breakthrough in preventing the intrinsic instability of exfoliated phosphorene, where the moisture and air are eliminated. The advantage of this method is that the phosphorene can be stabilized for a long time, but the operation is complicated, and the controllability needs to be further improved.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# 5.2.4. Doping  \n\nDoping phosphorene with tellurium improves its stability, making it one of the strategies for stabilizing the phosphorene as was demonstrated recently.[121] The Te atom will induce the reduction of CBM of phosphorene to a position which is not aligned to $\\mathrm{O}_{2}$ oxidation energy. The phosphorene flakes were exposed to ambient environment for 1 month and no degradation was noted, exhibiting that doping with appropriate dopant enhances the stability of phosphorene. Theoretical investigation via density functional theory has shown that doping phosphorene with organic molecules adsorbed on the surface noncovalently reduces the bandgap,[122] limiting from attaining the oxidation energy of $\\mathrm{O}_{2}$ .  \n\nRecently, the surface-electron withdrawing and donating strategy has been reported to suppress the agent causing instability in phosphorene.[123] Ruan and co-workers[124] reported that electron doping on BPQDs exhibits prolonged stable phosphorene nanoflakes for up to 6 months, and this enables further studies on the prepared phosphorene materials for a long time without any change in electrical properties. Neto and co-workers[125] showed electron doping in ultrathin phosphorene via Cu adatoms where threshold voltage was lowered without degrading the transport properties of the Cu-doped phosphorene. Zhang and co-workers[126] demonstrated a nonvolatile complementary metal-oxide-semiconductor (COMS) is well matched and very stable in the n-type doping method of few-layer phosphorene where the induced effect from K-center of silicon nitride, of which electron(n) doping exhibits air-stable transport properties for over a month. Recently, Liu et  al.[127] demonstrated sulfur doping to be effective method where they modeled phosphorene–FET doped with sulfur which exhibited robust and stable with an on–off current ratio of ${\\approx}1000$ lasting for a period of 21 days. Li et  al.[128] carried out DFT calculations on doped monolayer phosphorene, and found that the bi-doping with sulfur, silicon, and aluminum is more favorable stable than single doping. Uniform and highly crystalline Se-doped phosphorene has been reported to exhibit an enhanced electronic transport of ${\\approx}561~\\mathrm{cm}^{2}~\\mathrm{V}^{-1}~\\mathrm{s}^{-1}$ at ordinary conditions,[129] demonstrating that even crystal is free of surface defects, which is one of the predisposing factor in phosphorene degradations. The advantage of this method is that the obtained samples are stable for a long time while the disadvantage is that it is difficult to operate, and some properties of phosphorene will inevitably be affected.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 25,
+        "chunk": "# 6. Applications of BP with Enhanced Stability  \n\nPhosphorene exhibits attractive properties suitable for applications in next-generation devices,[130] especially the physical features such as mobility and optical properties which offer the phosphorene material the advantage over other 2D materials. However, obtaining a stable mono- and few-layer will make these wonderful phosphorene features’ useful for practical utilization. The semiconducting nature associated with phosphorene nanoparticle offers opportunity for practical use in electronics and optoelectronics.[131–133] Research on phosphorene attracts great $\\mathrm{deal}^{[24]}$ of attention owing to numerous fascinating properties, of which a number of them are layered dependent. For example, phosphorene shows high carrier mobility $(\\mu)$ with remarkably high hole mobility and high anisotropy between holes and electrons along $x$ and $\\gamma$ directions,[5b,10a] anisotropic optical response,[6a] and phonon anisotropy.[14] Phosphorene also shows its potential and important applications in spin-related or spintronics devices. Avsar et  al.[32] performed an experiment and discovered that a spin valve based on ultrathin $(\\approx5\\ \\mathrm{nm})$ 1 phosphorene spin channel exhibited a fundamental spin property that supports the electrical spin injection, transport procession, and detection up to room temperature. The essential spin–orbit and spin-relaxation properties of phosphorene exhibit an interesting interplay of large anisotropy for in-plane and out-of-plane spin orientations.[31] The capability of tuning the source–drain contact resistances in the phosphorene-based devices by gate voltage to an optimal range for injection and detection of spin-polarized hole enables phosphorene to be a potential candidate for efficient nanoelectronic and spintronic devices.[33c] Absorption of metals such as V/Mn/Fe on phosphorene can enhance and manipulate the local magnetic moment with large exchange-splitting and spin-flip energies which are of great advantage for the spintronic applications.[33a] The ambient degradation-induced spin paramagnetism in phosphorene can be tuned by changing one of the ambient factors such as ambient temperature, humidity, and light intensity.[21] Moreover, BP possesses thickness-dependent bandgap,[6a,134] and all these characteristics make phosphorene the most preferred nanomaterial for consideration in the following application thematic areas.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 26,
+        "chunk": "# 6.1. Energy Storage",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 27,
+        "chunk": "# 6.1.1. Lithium-Ion Battery  \n\nLithium-ion batteries (LIBs) play an important role in human civilization since it is a portable power source, hence, making the availability of energy source very convenience. Also, rechargeable lithium ions have stable cycling performance,[135] high storage capacity,[135c,136] and high energy density.[137] The setup of lithium-ion battery consists of anode, cathode, a separator, and an electrolyte. Anode and cathode act as the host of lithium ion with a separator membrane to prevent short-circuit and the electrolyte is the source of lithium ions.  \n\nPhosphorene possesses structures suitable for application in lithium-ion batteries which can replace graphene in the near future. Formation of $\\mathrm{Li}_{n}\\mathrm{P}_{m}$ via insertion reaction exhibited better electrochemical activity, which is attributed to the stable formed structure exhibiting excellent anode performance. Electrochemical mechanism processes during discharge and charge[138] in BP are as follows  \n\nDischarge: $\\mathrm{BP}\\rightarrow\\mathrm{Li}_{n}\\mathrm{P}\\rightarrow\\mathrm{LiP}\\rightarrow\\mathrm{Li}_{2}\\mathrm{P}\\rightarrow\\mathrm{Li}_{3}\\mathrm{P}$  \n\nThe lithium-ion battery’s performance is always determined by the nature of electrodes used. Recently, great performance from cathode electrode was achieved and gained recognition,[139] and focus now is on search for suitable anode. Graphite is the proposed material due to the good electroconductivity, low cost, and plenty in abundance,[140] and has attracted a lot of attention as the appropriate anode material, but it delivers an energy density of ${\\approx}200$ W $\\mathrm{~h~kg^{-1}~}$ , but still too low to meet the growing demand for high-energy storage nanosystems. Other materials explored for anode are Ge,[141] $\\mathrm{sn}$ ,[142] Si,[143] and $\\mathrm{SnO}_{2}$ .[144] Yet, phosphorene is the most celebrated elemental 2D material with potential characteristics suitable for anode in LIB, due to small barrier energy of diffusion $\\scriptstyle(\\approx0.08\\ \\mathrm{eV})$ and improved theoretical specific capacity $(2596\\mathrm{mA}$ h $\\mathrm{g}^{-1})^{[145]}$ which are based on the $\\mathrm{Li}_{3}\\mathrm{P}$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 28,
+        "chunk": "# 6.1.2. Lithium–Sulfur Battery  \n\nResearches focusing on Li–S battery have been carried out because of growing demand for high-energy storage systems. Li–S battery has been investigated and found to have great the theoretical energy density of about $2597~\\mathrm{\\textperthousand}$ h $\\mathrm{kg^{-1}}$ . However, Li–S battery’s application in actual practical is yet to achieved,[146] due to the following limitations. First, weak ionic and S conductivities which can result into overpotential and underused of active and participating species. Second, irreversible loss of active species, due to termination of intermediary polysulfides, leads to short cycle life. Third, large volumetric variation in S cathode electrode during charging and discharging cycle leads to loss of contact between conductive species and the current collector. Alleviating some of these limitations has been demonstrated through configuration of electrode composite and architecture in order to enhance electronic conductivity, thus impeding the polysulfide termination through chemically and physically immobilizing the S species. With extraordinary physical and chemical properties of phosphorene, it offers a competitive advantage as anode for Li–S ion battery because of its nature to trap and co-ordinate covalently,[147] high surface-to-volume ratio, and high carrier mobility,[148] appreciably low diffusion energy barrier toward $\\mathrm{Li^{+,149}}$ All these excellent properties make phosphorene a prospective candidate for electrode (anode) material in the Li–S battery. Moreover, for lithium-ion battery, phosphorene/red phosphorus shows enhanced discharging and charging of about 2449 and $491\\mathrm{\\mA}$ h $\\mathbf{g}^{-1}$ in 100 complete cycles,[150] showing that hybrid improves the performance of Li-ion battery.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 29,
+        "chunk": "# 6.1.3. Magnesium-Ion Battery  \n\nReusable Mg-ion battery (MIB) has gained a lot of interest over the last few years due to its enhanced electrochemical capacity of bivalent $\\mathbf{M}\\mathbf{g}$ ion,[151] which has yielded an improved volumetric capability $(3868\\mathrm{mAh}\\mathrm{g}^{-1})$ ) compared to KIBs $(609\\mathrm{\\mAh\\g^{-1})}$ and thus stands out to be feasible for practical due to its high safety characteristics, high gravimetric $(2205\\mathrm{~A~h~kg^{-1}})$ , low standard electrode potential $(\\mathrm{Mg}^{2}+2\\mathrm{e}^{-}\\rightarrow\\mathrm{Mg})$ , and readily available material.[152] Moreover, $\\mathrm{{Mg}}$ electrodeposition does not either form the dendrites or a thick complex solid electrolyte interphase which is a concern to safety of rechargeable batteries. Despite these outstanding characteristics, there are underlying setbacks which need to be address, i.e., anode–electrolyte incompatibility, small window for electrolytes, deficiency of high voltage/cathode capacity, and very low rate of diffusion of $\\mathbf{M}\\mathbf{g}$ ions around the anode due to polarization of the bivalent cation.[153] Another limiting factor is associated with polar electrolyte which tends to hinder the migration of $\\mathbf{\\mathrm{Mg}}$ ions and electrons, and therefore, with the emergence of phosphorene, work has been done theoretically, and the report indicates that loading energy, specific capacity, and diffusion barrier of $\\mathbf{M}\\mathbf{g}$ ion on phosphorene are $0.99\\mathrm{eV}$ along the zigzag direction $,865\\mathrm{\\mA}\\mathrm{h}\\mathrm{g}^{-1}$ and $0.833\\mathrm{~V},$ respectively,[154] The formation of stable $\\mathrm{Mg}_{0.5}\\mathrm{P}$ at $11\\%$ variation in capacity could offer covalent framework (COF) to enhance the $\\mathrm{Mg^{2+}}$ diffusion rate as an anode host,155 and these could make the phosphorene as the ideal anode for a magnesium-ion battery.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 30,
+        "chunk": "# 6.1.4. Supercapacitors  \n\nPhosphorene has a puckered honeycomb structure with weakly bonded layers of $\\mathrm{\\DeltaP}$ atoms in the out of plane through vdW interactions and has emerged as a material with potentials suitable for application in energy storage. These properties enable the phosphorene to have fast ion diffusivity, good electrical conductivity, and dynamic stability, hence presenting the phosphorene as a potential material for supercapacitors.[10b,156] Flexible solid-state supercapacitor is reported to have shown a good volumetric capacitance of $\\approx17.78\\ensuremath{\\mathrm{~F~}}\\ensuremath{\\mathrm{cm}}^{-3}$ $(59.3\\mathrm{~F~g}^{-1})$ at $0.1\\mathrm{~V~}\\mathrm{s}^{-1}$ and unprecedented capacitance rate with constant $1.43\\ \\mathrm{F\\cm^{-3}}$ $(4.8\\mathrm{~F~g^{-1}})$ of volumetric capacitance at $10\\mathrm{V}\\mathrm{s}^{-1}$ .[106] Phosphorene maintained high mechanical stability even after a long period (30 000 charging–discharging cycles). Recently, a mask-assisted interdigital electrode pattern was developed by the use of layer-by-layer stacking of phosphorene nanosheets and electrochemically exfoliated graphene nanosheets (GNs) in IL electrolyte.[157] Micro-supercapacitors offered an excellent electrochemical performance of around $9.8~\\mathrm{mF~cm^{-2}}$ and a volumetric capacitance of $\\approx37.5\\ \\mathrm{F\\cm^{-3}}$ at $5~\\mathrm{mV}~\\mathrm{s}^{-1}$ and operates at $94\\%$ of their original capacitance. The performance of micro-supercapacitors is ascribed to the strong combination of phosphorene–GNs which offers large space for ionic storage and high mobility routes. Also, another supercapacitor which consists of 2D single-walled carbon nanotube (SWCNT) electrodes and ion gel was reported to have exhibited an excellent device performance where it only declines in its performance at $30\\%$ strain.[158] Chen et  al.[150] reported a phosphorene–RP composite with a large value of ${\\approx}60.1\\mathrm{~F~g^{-1}}$ and long cycling self-life with a capacity retention of ${\\approx}83.3\\%$ in 2000 cycles, demonstrating that phosphorene is suitable for application in supercapacitor. Monolayer or few-layer phosphorenes stand out to be the best material for solid-state based-stretchable supercapacitor for energy storage devices which may found utilization in paper like mobile phone (touch screen), electronic newspaper, power dressing, and flexible and wearable computers.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 31,
+        "chunk": "# 6.2. Field Effect Transistors  \n\nA significant component in electronic field is FET, and thus it plays a great role in revolutionizing the electronics. The physical features of the FET are the three terminals which have semiconducting channel electrodes in-between the terminalsource and terminal-drain. The quantity of charges between the source and the drain terminals can be regulated through application of gate voltage. Gate voltage causes a transverse electric field which will either deplete (off state) or enhance (on state), where the ratio is $(l_{\\mathrm{on}}/l_{\\mathrm{off}})>10^{4}$ .  \n\nSince the discovery of graphene, the continuous improvement on FET is based on the stability of the material in question, and the intrinsic electronic structure and associated electronic properties have the topic of intense research. Lack of bandgap in graphene has made it difficult to be implemented in the logic transistors, because it needs large $l_{\\mathrm{on}}/l_{\\mathrm{off}}$ ratio, and presence of optimum energy gap. Despite graphene exhibiting a transport mobility of ${\\approx}20~000~\\mathrm{cm}^{2}~\\mathrm{V}^{-1}~\\mathrm{s}^{-1}$ at room-temperature, however, its ability to attained ballistic transport limits in FETs is unbearable.[159] The tunable bandgap and high carrier mobility characteristic exhibited by phosphorene offer a hunting ground for an excellent FET as depicted in Figure 11.  \n\nGuo et  al.[97] demonstrated that FET fabricated from a passivated BP with ${\\mathrm{Ag}}^{+}$ metal ion exhibited enhanced electronic transport properties, where the prototype ${\\mathrm{Ag}}^{+}$ -modified BP FET as shown in Figure  11a, showed an improved hole mobility from 796 to $1666\\ c m^{2}\\mathrm{V}^{-1}\\mathrm{s}^{-1}$ and $I_{\\mathrm{on}}/I_{\\mathrm{off}}$ ratio from $5.9\\times10^{4}$ to $2.6\\times10^{6}$ as shown in Figure 11d; this clearly demonstrates that ${\\mathrm{Ag}}^{+}$ played an important role in enhancing ambient stability of BP–FET without changing the electronic intrinsic properties of BP as confirmed in Figure  11b. Also, they performed the room-temperature switching modes of ${\\mathrm{Ag}}^{+}$ -modified BP–FET before and after $\\mathbf{A}\\mathbf{g}\\mathbf{+}$ modification as presented in Figure  11c, and established that the initial ambipolar transport character of BP tends to change to p-type carrier as concentration of ${\\mathrm{Ag}}^{+}$ gradually increases on the BP surface, and this is demonstrated by the fact that ${\\mathrm{Ag}}^{+}$ modification enhances the initial hole carriers by lowering the off-state resulting into high $I_{\\mathrm{on}}/I_{\\mathrm{off}}$ ratio. In addition, they perform a comparative test to established the effect of other metal ions like $\\mathrm{Fe}^{3+}$ , $\\mathrm{Mg^{2+}}$ , and $\\mathrm{Hg}^{2+}$ on BP stability and FET performance. All the three metal ions are formed, $\\mathrm{BP}_{\\mathrm{Fe}(3+)}$ , $\\mathrm{BP_{Mg(2+)}},$ and ${\\mathrm{BP}}_{\\mathrm{Hg}(2+)}$ , due to favorable energy of formations. Also the metal ion-BP modification was established to be stable. Their FET performance improved after metal ions modification because the three metal ions act as an electron-deficient medium in the BP–FETs. Among the three metal ions, only the $\\mathrm{Fe}^{3+}$ exhibits a change in ambipolar transport to character after $^{2\\mathrm{~h~}}$ of modification to p-type, because of more cations of $\\mathrm{Fe}^{3+}$ . However, the ${\\mathrm{Ag}}^{+}$ modification provides the best BP stability and FET performance.  \n\nThe phosphorene-based FET has been fabricated on polyimide substrates sandwich between bi-layers of ${\\mathrm{Al}}_{2}{\\mathrm{O}}_{3}$ . Compared to TMD transistors,[160] phosphorene-based FET exhibited a higher carrier mobility of ${\\approx}310~\\mathrm{cm}^{2}~\\mathrm{V}^{-1}~\\mathrm{s}^{-1}.$ ,[161] which is much larger, fivefold the one shown by TMD. Single-layer $\\mathbf{MoS}_{2}$ exhibits a robust large bandgap of $2.84\\ \\mathrm{eV},$ an $l_{\\mathrm{on}}/l_{\\mathrm{off}}$ ratio of $10^{8}$ , and a low carrier mobility of $200\\ c m^{2}\\ \\mathrm{V}^{-1}\\ \\mathrm{s}^{-1}$ ,[162] and these have made it not suitable for fast nanoelectronics. For high performance, phosphorene transistors are suitable because of their sizeable and tunable bandgap with high hole mobility at room temperature.[10a] It is anticipated that phosphorene stands out to be appropriate material to bridge the gap in $I_{\\mathrm{on}}/I_{\\mathrm{off}}$ and mobility among the graphene and TMDs.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 32,
+        "chunk": "# 6.3. Biomedicine  \n\nPhosphorene possesses environmental benign properties with low lethal, and these are some of the reasons behind its widely applications in the field of biomedicine.[163] First, clinical trials on biocompatibility and cytotoxicity of phosphorene nanoparticles have been investigated and found to be biocompatible and nontoxic[25,164] under physiological conditions. Phosphorene decomposed into nonlethal phosphite, phosphate and other $\\mathrm{P}_{x}\\mathrm{O}_{\\gamma}$ species.[75] With these two fundamental properties, i.e., low cytotoxicity and good biocompatibility pave way for utilizing phosphorene nanoparticles in biomedicine field.[164] Recently, Song et  al. fabricated transient FET using few-layer phosphorene and found that its performance is comparable to channel’s material for transient devices. Also the biodegradability was tested via cytotoxicity assay and confirmed that the rate at which the phosphorene dissolves was within $36\\mathrm{~h~}$ and therefore, phosphorene-based transient FETs provide a viable platform toward human-implantable electronics nanodevices.[165] The large surface area-to-volume ratio of phosphorene nanoparticles has offered a platform for drug delivery with high drug loading efficiency. The drug-delivery system (DDS) using phosphorene nanoparticles as a biodegradable drug delivery system has been demonstrated to be an excellent therapeutic system because of its high surface-tovolume ratio and low toxicity to microenvironments. Recently, Zhang and co-workers demonstrated the near-infrared light induced decomposition of BP hydrogel for accurate release of drugs in tumor tissue to eradicate subcutaneous cancers without inflicting pain to the patient.[166] Zhang and coworkers[167] prepared BPQDs with excellent biocompati­bility and low cytoxicity even at high concentration as $5\\ \\mathrm{\\mg\\mL^{-1}}$ and re-engineered via coating with polyelectrolyte polymer to offer a nanoplatform for drug delivery. Photodynamic therapy (PDT) is also a strategy for managing the cancer disease. For PDT to occur, three factors are needed, i.e., light source, tissue oxygen, and photosensitizer, and the combination of these produces toxic substance, which kills the diseased cells with less injuries to the patient.[168] The PDT cycle process encompasses the transmission of light energy from the photosensitizer to oxygen molecules found in the tissue to generate reactive oxygen species (ROS), and the ROS induces toxicity to the cellular.[169] Ultrathin phosphorene has been found to be an excellent photosensitizer with large quantum yield, thus enhances the ROS evolution rate[170] and is very versatile in the PDT application.  \n\n![](images/dda1cd6207266f51899b834252cd6ff44327e663d35db5e7cf1a1af41152e96c.jpg)  \nFigure 11.  a) AFM image (top) and schematic of a BP–FET device on silicon substrate with a $300{\\mathsf{n m}}{\\mathsf{S i O}}_{2}$ . b) Raman spectra of a BP sheet before and after ${\\sf A}{\\sf g}^{+}$ modification. c) Current to gate voltage curve obtained from the BP–FET at room temperature after ${\\mathsf{A}}{\\mathsf{g}}^{+}$ modification for 0, 0.5, 1, and $2\\ h$ . d) Hole mobility and $I_{\\mathrm{on}}/I_{\\mathrm{off}}$ ratio of the FET device as a function of ${\\mathsf{A}}{\\mathsf{g}}^{+}$ modification time. Reproduced with permission.[97] Copyright 2017, Wiley-VCH.  \n\nPhotothermal therapy (PTT) has also gained a lot of attraction in treatment of cancer because of minimal invasion, hence, less pain infliction to the patient. The mechanism process of the PTT is triggered by the absorbed light energy, where the photothermal agent transforms the light to heat, leading to thermal ablation to the cancerous cells[171] as illustrated in Figure  12a. Phosphorene nanostructures possess high extinction coefficient, excellent photothermal conversion efficiency, good biocompatibility, and photostability,[172b] making it a promising material for PPT. The combination of PDT and PTT forms a good synergy for cancer therapy, as demonstrated in Figure  12b. The phosphorene nanoparticles have good interaction with infrared light to generate ROS under $660~\\mathrm{nm}$ wavelength for PDT and heat generation under $808\\ \\mathrm{nm}$ laser irradiation for PTT.[173] Combining these two methods gives a powerful double cancer therapy for maximum eradication of cancerous cells.  \n\n![](images/f50727f38a8c452242e13d7b2ab29956dece35bdf34b910aee590b7a15c520db.jpg)  \nFigure 12.  a) The photothermal therapy (PTT). Reproduced with permission.[166] Copyright 2018, PNAS Early Edition. b) The combination of PDT and PTT form a good synergy for cancer therapy. Reproduced with permission.[172a] Copyright 2017, Wiley-VCH.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 33,
+        "chunk": "# 6.4. Photocatalyst for Water Splitting  \n\nThe exploration of sustainable renewable source of energy has been an important research topic over the last decade.[174] Because of this, development of novel technology regarding the capture of sunlight as a natural source of energy and utilized to benefit the human being has been received well by the researchers, where low-dimensional materials have been utilized in the fabrication of solar devices. The proper use of sunlight supplement in the fossil source energy thus meets the energy demand in the society. Employing a semiconductor for concurrent solar light absorption and transformation in the photocatalytic water splitting reaction is of great concern in the renewable energy field.[175] Efficient water splitting into hydrogen has attracted great attention in the research community with a view of setting a new industrial photosynthetic process which proved to be a clean source of energy.[176] Photocatalysis from semiconducting materials is projected to make a significant contribution in enabling both the energy transformation in hydrogen evolution and valued chemical feedstock upon interacting with photon energy. Through photon absorption by semiconductor material, evolution of effective charge generation is experienced and for effective transfer of charge pairs needs appropriate bandgap of photocatalyst and, therefore, band structure of photocatalytic material is very important. Phosphorene-based photocatalytic technology for splitting of water into oxygen and hydrogen phase has been on the rise,[177] and this is a suitable technology for mitigating emission. Phosphorene exhibits extraordinary charge carrier migration characteristic, which is faster hence facilitates charge separations, and fulfills the requirements of the photocatalyst for hydrogen evolution. The bandgap features of BP such as tunable bandgap have demonstrated well that it is suitable for water splitting since it absorbed light up to even near-infrared region and the carrier migration is very excellent as compare to existing 2D materials such as $\\mathbf{MoS}_{2}$ , graphene, and $\\mathrm{g}–\\mathrm{C}_{3}\\mathrm{N}_{4,}{}^{178}$ as shown in Figure  13. Adjustable bandgap and strong broadband optical absorption in phosphorene are highly considered as the sole characteristics useful for photocatalyst.[177b]  \n\nThe photocatalytic cycle for water splitting composed of three stages: 1) semiconducting materials get excited when light is illuminated on it to produce electron and hole pairs in the CBM and VBM, respectively; 2) photogenerated electron migrates from bulk to edge surface of the semiconductor to reduce protons to $\\mathrm{H}_{2}$ ; and 3) the holes facilitates the oxidation half-reaction.[179] Under normal conditions, splitting of one molecule of water $\\mathrm{(H}_{2}\\mathrm{O})$ into $\\mathrm{H}_{2}$ and $\\mathrm{O}_{2}$ needs the standard Gibbs free energy $(\\Delta G\\approx237\\mathrm{\\kJ\\mol^{-1}}$ $(1.23\\ \\mathrm{eV})$ . Appropriate selection of photocatalyst is governed by their bandgap energy $(E_{\\mathrm{g}}>1.23\\ \\mathrm{eV})$ ) values with the suitable CBM edge energy ( $[E_{\\mathrm{cbm}}$ and VBM edge energy $(E_{\\mathrm{vbm}})$ matching with the electrochemical potentials of $E^{\\circ}$ $\\left(\\mathrm{H}^{+}/\\mathrm{H}_{2}\\right)$ and $E^{\\circ}(\\mathrm{O}_{2}/\\mathrm{H}_{2}\\mathrm{O})$ .  \n\nHigh hole mobility, tunable bandgap, and strong optical absorption have made phosphorene the most preferred material for water splitting.[10a,180] The high carrier mobility and anisotropy help in the separation of photogenerated carriers while the tunable bandgap supports the wide absorption spectrum. The determining factor of a photocatalyst semiconductor is the position of VB edge and the band CB edge, and therefore, the inherent band edge position determined the probability of phosphorene as the photocathode for hydrogen evolution reaction (HER). Edge modification is another method for attaining full water splitting in phosphorene by pseudohalogen.[181] Yang and co-workers computed the bandgap edge positions on the phosphorene nanoribbon (PNR) via edge passivation using nitrile cyanate functional groups. The bandgap edge values in the zigzag edge-modified PNRs exhibit an abrupt decrease as compare to those in armchair orientations due to their variant edge-shaped structure. The trend shows that the edge-modified bandgap value decreases with the increase in width of nanoribbons.  \n\n![](images/682b01eee2d584bbab93ceac8fa71f9f6ada5e4418067c1955c12b7f40893d72.jpg)  \nFigure 13.  Schematic illustration of band edge positions of $\\mathsf{T i O}_{2},\\mathsf{g}{\\cdot}\\mathsf{C}_{3}\\mathsf{N}_{4}$ , ${\\mathsf{M o S}}_{2}$ , and phosphorene as photocatalysts for water splitting. The reduction potential of $\\mathsf{H}^{+}/\\mathsf{H}_{2}$ and the oxidation potential of $\\mathsf{O}_{2}/\\mathsf{H}_{2}\\mathsf{O}$ are shown by dotted red and blue lines, respectively. The positions of CBM and VBM band edges are shown by solid lines and their redox potential are shown against each edges, respectively. The bandgap energy of each semiconductor is shown by the black arrows and all the energy levels are referenced to the vacuum level, set to be zero. Reproduced with permission.[178] Copyright 2017, American Chemical Society.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 34,
+        "chunk": "# 7. Conclusion and Perspectives  \n\nBP, beyond graphene, is the most celebrated layered material, not only because of its inherent exceptional physical properties but also due to its peculiar chemical properties, and it has found a special interest from the materials scientists who have carried out prototype applications in the electronics, optoelectronics, energy storage, energy conversion, and biomedical fields. BP is regarded as a rising star, but not the brightest star, in condensed matter physics, only because of the limitations due to its degradation behavior, and overcoming these problems will place BP at the top of the hierarchical order of 2D materials. Stabilization of phosphorene still represents a challenging task, and the search for effective and efficient passivation techniques raises questions of fundamental interest and importance. In this review, we focused on recent progress on ineffective passivation techniques that render phosphorene more stable, and some of the phosphorene stabilization approaches have been summarized in detail along with developments in the implementation of the stabilized phosphorene in real-life situations. The ambient instability of phosphorene is almost solved, although some new methods are still needed to further improve its stability and to attain the real commercialization of phosphorene-based devices. This review might assist researchers in understanding the chemistry behind phosphorene degradation, in identifying the best strategy or synergistic approach to mitigate phosphorene degradation, and in the long run, in obtaining long-term solution to the instability of phosphorene in air. Therefore, obtaining a stable monolayer or few-layer phosphorene in ambient conditions is likely to bring revolutionary change in the landscape of the electronics, optoelectronics, energy conversion, and biomedical fields, and thus offers improvements in human civilization. Understanding the chemistry behind the phosphorene degradation is very significant toward the appropriate design of excellent passivation techniques to obtain long-term stability of phosphorene, for full implementation in practical applications.  \n\nThe goal of this paper was to review the recent research developments on passivation techniques of phosphorene as a rising star-layered material. There is a great hope that core advances in passivation techniques for phosphorene will be attained in the near future, which will mitigate the disadvantages of BP nanoparticles. Much work still needs to be performed to understand the chemistry behind phosphorene degradation, such as the design of preparation methods that will not cause defects to the phosphorene surface and edges and the development of production methods that are environmentally friendly, cost effective, and efficient enough to meet the anticipated industrial demand. Breakthroughs in these aspects will make phosphorene a full-fledged star 2D material with impeccable properties.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 35,
+        "chunk": "# Acknowledgements  \n\nD.K.S. and H.W. contributed equally to this work. Financial supports from the National Natural Science Foundation of China (Grant Nos. 61605131, 61435010, and 61875138), Natural Science Foundation of Guangdong Province for Distinguished Young Scholars (2018B030306038), and Science and Technology Innovation Commission of Shenzhen (Grant Nos. JCYJ20180507182047316, KQJSCX20180328095501798, KQTD2015032416270385, and JCYJ20150625103619275) are gratefully acknowledged.",
+        "category": " References"
+    },
+    {
+        "id": 36,
+        "chunk": "# Conflict of Interest  \n\nThe authors declare no conflict of interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 37,
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+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Photochemical Activity of Black Phosphorus for Near-Infrared Light Controlled In Situ Biomineralization  \n\nJundong Shao, Changshun Ruan, Hanhan Xie, Paul K. Chu, and Xue-Feng Yu\\*  \n\nThe photochemical activity of black phosphorus (BP) in near-infrared (NIR) light controlled in situ biomineralization is investigated. Owing to the excellent NIR absorption, irradiation with NIR light not only promotes degradation of BP into $\\mathsf{P O}_{4}{}^{3-}$ , but also enhances the chemical activity to accelerate the reaction between $\\mathsf{P O}_{4}{}^{3-}$ and $\\mathsf{C a}^{2+}$ and promote in situ biomineralization. Mineralization of hydrogels is demonstrated by the preparation of BP incorporated hydrogel $B P@$ Hydrogel) which delivers greatly improved biomineralization performance under NIR illumination. The biomineralization process which can be controlled by modulating the light irradiation time and location has a high potential in controlling the mechanical properties and osteoinductive ability in tissue engineering. This study also provides insights into the degradation, photochemical activity, and new biological/biomedical applications of BP.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1. Introduction  \n\nAs a new and emerging 2D semiconductor containing a single element of phosphorus, black phosphorus (BP) has been shown to have superior physical properties and great potential in  \n\nThe ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/advs.202000439  \n\n$\\textcircled{5}2020$ The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.  \n\nDOI: 10.1002/advs.202000439 a myriad of applications including optoelectronics, catalysis, energy, and biomedicine.[1–8] Particularly, few-layer BP sheets also called phosphorene have excellent optical properties, such as the layer-dependent bandgap, broad optical absorption range spanning the near-infrared (NIR) region, as well as high photothermal and photodynamic efficiency[9–13] Moreover, owing to the good biocompatibility and biodegradability, BP sheets have captured extensive attention in biomedical applications, such as optical therapies, drug/gene delivery, bioimaging, and sensing.[14–22] However, in spite of the excellent properties, BP sheets degrade rapidly in the presence of oxygen and/or water and degradation is accelerated by light irradiation[23–26] thus hindering many potential applications.[27–29] However, the degradable nature of BP sheets can be exploited to boost the chemical activity. Typically, degradation of BP in the presence of water produces phosphate $(\\mathrm{PO_{4}}^{3-})$ ,[30–32] which is a vital constituent in bone mineralization, phospholipids in membranes, nucleotides that provide energy and found in DNA and RNA, and phosphorylated intermediates in cellular signaling. Phosphate thus plays a critical role in skeletal development, mineral metabolism, and cellular functions in the human body.[33–35] Although the degradation-induced chemical activity of BP sheets and concomitant photoresponsivity are very interesting, there have been few systematic investigations and the related phenomena are not well understood.  \n\nHerein, the chemical and photochemical activity of BP is studied systematically and the potential use in NIR-light controlled in situ biomineralization is investigated. $\\mathrm{PO_{4}}^{3-}$ combines with calcium $(\\mathsf{C a}^{2+})$ in the physiological environment to form the calcium phosphate (CAP) biomineral found in bone, teeth, and tendons.[36–38] In fact, the phosphorus-driven and calciumextracted biomineralization processes have immense potential in many applications, such as particle reinforcement of biomaterials, biomimetic materials, and tissue engineering.[39–41] Typically, biomineralization is implemented to adjust the mechanical properties of hydrogels via particle reinforcement of calcium phosphate nanostructures and can also be applied in vivo to generate implants with tunable mechanical properties.[42–44] In addition, biomineralization plays a crucial role in the growth of hard tissues, such as teeth and bone and also the initiation of bone regeneration.[40] Generally, biomineralization begins with a precipitation reaction from different ions (such as ${\\mathsf{C a}}^{2+}$ , $\\mathrm{CO_{3}}^{2-}$ , and $\\mathrm{PO_{4}}^{3-}$ ) followed by nucleation, growth, and self-organization of the mineral crystals, which is controlled by matrix macromolecules in the living organisms.[45] The biomineralization process usually proceeds spontaneously in organisms and it is difficult to control the process artificially in situ in the body.  \n\n![](images/3b46b93f4b892f8ec0e291fad10fcf2918a5750230ba614f5f4f6da87595bccc.jpg)  \ncheme 1. Schematic illustration of the NIR photochemical activity of BP to control the biomineralization of hydrogel in s  \n\nOur results demonstrate that BP enables controllable in situ formation of $\\mathrm{PO_{4}}^{3-}$ for the biomineralization of hydrogels (Scheme 1). Owing to the excellent NIR absorption properties of BP sheets, irradiation with NIR light not only promotes degradation of BP into $\\mathrm{PO_{4}}^{3-}$ but also enhances the chemical activity to accelerate the reaction between $\\mathrm{PO_{4}}^{3-}$ and ${\\mathsf{C a}}^{2+}$ to promote in situ biomineralization. This process is demonstrated by the mineralization of hydrogels to improve the mechanical properties and in vivo biomineralization induction ability. Furthermore, owing to the high tissue penetration ability and excellent controllability in space and time of NIR light, the NIR light-induced photochemical activity of BP provides an efficient way to spatially tune the mineralization behavior by modulating the irradiation time and location.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2. Results and Discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2.1. Synthesis and Characterization of BP Sheets  \n\nThe BP sheets are synthesized by a modified liquid exfoliation technique reported by our group previously.[16] The scanning electron microscopy (SEM) image in Figure 1a reveals a uniform morphology with an average lateral size of $389.6\\pm119.6$ nm (inset in Figure 1a) according to the statistical analysis of 200 BP sheets. The transmission electron microscopy (TEM) image in Figure 1b and high-resolution TEM (HR-TEM) image in Figure 1c discloses lattice fringes of $0.27{\\mathrm{nm}}$ matching that of the monolayered BP structure. The atomic force microscopy (AFM) image in Figure 1d shows the topographic morphology of the BP sheets and the thickness is determined by the cross-sectional analysis (inset in Figure 1d). A 2D sheet-like morphology with a flat and smooth surface is clearly observed and the average thickness of the BP sheets is $27.1\\pm9.3\\mathrm{nm}$ . Raman spectrum in Figure S1 (Supporting Information) reveals three prominent Raman peaks at 355.4, 430.8, and $459.3~\\mathrm{cm}^{-1}$ , which can be assigned to one out-of-plane phonon mode $\\mathrm{(A^{1}_{\\ g})}$ and two in-plane modes $(\\mathrm{B}_{2\\mathrm{g}}$ and $\\mathsf{A}_{\\mathrm{~g~}}^{2}\\big)$ , respectively.[16] To evaluate the NIR photothermal performance, 20 ppm BP sheets dispersed in aqueous solution was exposed to an NIR laser $\\scriptstyle(808\\ n m$ , $1.0\\mathrm{~W~cm}^{-2}$ ) for $10~\\mathrm{min}$ . As shown in Figure S2 (Supporting Information), the solution temperature increases by $26.1^{\\circ}\\mathrm{C}$ after irradiation, while the temperature of water increases by only $2.4~^{\\circ}\\mathrm{C}$ , indicating the excellent photothermal performance of BP sheets.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2.2. The Degradation Process of BP Sheets  \n\nThe degradation properties of BP sheets are studied. As shown in Figure 2a, when a big BP sheet is exposed to nearly $100\\%$ relative humidity air at room temperature for 2 days, small topographic protrusions (hereafter termed “bubbles”) emerge from the surface and both the density and size of the bubbles increase with time as a result of structural or chemical changes.[46] When the BP sheet in the same environment is exposed to $808~\\mathrm{nm}$ light $\\cdot1.0\\mathrm{~W~cm}^{-2}$ , $10~\\mathrm{min}$ ) three times daily, their surface becomes rougher compared to that without light irradiation for the same exposure time (Figure 2a) suggesting that the chemical activity of BP increases with NIR light illumination.  \n\n![](images/61959b96cb0ae6f9872df488a665eed8bd6c73255e1cedb74f013de1909dfa4b.jpg)  \nFigure 1. Characterization of BP sheets: a) SEM image and statistical size analysis (inset). b) TEM image. c) HR-TEM image. d) AFM images and cross-sectional analysis (inset) of BP sheets.  \n\nTo further evaluate the degradation process, the aqueous dispersions containing the same amount of BP sheets $(20\\mathrm{ppm})$ are exposed to air for 8 days without or with NIR light irradiation $(1.0\\mathrm{W}\\mathrm{cm}^{-2}$ , $10\\mathrm{min}$ , three times daily). The absorption spectra and variation of the absorption ratios $(A/A_{0})$ at $808~\\mathrm{nm}$ in Figure S3 (Supporting Information); and Figure 2b shows that the BP sheets with NIR light irradiation show faster degradation as demonstrated by the faster decline of the absorbance intensity compared to that without NIR light irradiation. The corresponding photographs in the inset of Figure 2b show that the color of these two dispersions becomes lighter and the dispersion with NIR light irradiation shows more severe color deterioration than that without irradiation after 2, 4, 6, and 8 days. The amount of residual BP and the concentration of P ions in the solution are determined by inductively-coupled plasma atomic emission spectroscopy (ICP-AES) (Figure 2c). The BP sheets under NIR light irradiation degrades nearly $30\\%$ faster than without NIR light irradiation after 8 days and the trend of the absorbance intensity is similar.  \n\nSince degradation of BP is caused by the reaction with oxygen and water to form oxidized phosphorus species $(\\mathrm{P}_{x}\\mathrm{O}_{\\gamma})$ followed by the subsequent reaction of $\\mathrm{P}_{x}\\mathrm{O}_{\\gamma}$ to $\\mathrm{PO_{4}}^{3-}$ ions,[30] Xray photoelectron spectroscopy (XPS) is employed to determine the chemical states of the BP sheets without/with NIR light irradiation during degradation. As shown in the $\\mathrm{~P~}2\\mathrm{p}$ spectra in Figure 2d, the two peaks at 129.5 and $130.5\\ \\mathrm{eV}$ verify the original state of BP and that at $134.0\\mathrm{eV}$ is associated with $\\mathrm{P}_{x}\\mathrm{O}_{\\gamma}$ .[47–50] After NIR light irradiation, the $\\mathrm{P}_{x}\\mathrm{O}_{\\gamma}$ peak increases more than that without NIR light irradiation, indicating more serious oxidization of BP sheets under NIR illumination. The concentration of $\\mathrm{PO_{4}}^{3-}$ after degradation is determined with the phosphate assay kit and the trend is similar to that disclosed by XPS that the BP sheets with NIR light irradiation produce more $\\mathrm{PO_{4}}^{3-}$ in the supernatant (Figure S4, Supporting Information). The results indicate the enhanced photochemical activity of BP by NIR illumination accelerates degradation and $\\mathrm{PO_{4}}^{3-}$ a production that can facilitate biomineralization.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.3. In Situ Biomineralization of BP Sheets  \n\nThe in situ biomineralization properties of BP sheets are determined in a simulated physiological environment by dispersing them in a simulated body fluid (SBF) and shaking at $37^{\\circ}\\mathrm{C}$ . SBF is a suitable medium to study the biomineralization performance of BP sheets in vitro.[51] Compared to BP quantum dots $(\\approx5~\\mathrm{nm})$ and BP bulks (over $10~\\upmu\\mathrm{m}$ ), BP sheets exhibit proper degradation rate in SBF, which is more suitable for long-term biomineralization (Figure S5, Supporting Information). After 2, 4, 6, and 8 days, the BP sheets are removed from the SBF and washed gently with distilled water and vacuum dried. The SEM images in Figure 3a show the surface morphology evolution of the BP sheets during biomineralization. Compared to the BP sheets on day 0 with smooth surface morphology, new nanoparticles emerge the surface of the BP sheets after 2 days and the number of nanoparticles increases with biomineralization time. The nanoparticles are wrapped on the surface of BP sheets to prevent further corrosion and degradation is slowed so that it serves as a long-term biomineralization initiator. Since phosphorus-driven and calcium-extracted biomineralization processes usually begins with precipitation reaction from ${\\mathrm{Ca}}^{2+}$ , $\\mathrm{PO_{4}}^{3-}$ , and $\\mathrm{H}_{2}\\mathrm{O}$ , followed with nucleation, growth, and self-organization of mineral crystals, such in situ biomineralization of BP may begin with the degradation of BP into $\\mathrm{PO_{4}}^{3-}$ and then extract ${\\mathsf{C a}}^{2+}$ from SBF followed with above chemical reaction and eventually formed CAP.[52,53]  \n\n![](images/1a743f2832f8870413b8751180cf2641894e2273aaf0f48522c8457860219de1.jpg)  \nFigure 2. Degradation process of BP sheets without/with NIR laser irradiation: a) Photographs of a BP sheet without/with NIR light irradiation in moist air for 0, 2, 4, 6, and 8 days. b) Variation of the absorption ratios $(A/A_{0})$ at $808{\\mathsf{n m}}$ and corresponding photographs of BP sheets in the solution without/with NIR laser irradiation for 0, 2, 4, 6, and 8 days. c) Quantitative analysis of the residual P and P ions in the solution of the BP sheets without/with NIR laser irradiation after storing in water for different periods of time. d) $\\mathsf{P2p}\\mathsf{X P S}$ spectra of BP sheets after storing in water for different periods of time.  \n\nThe biomineralization behavior of BP sheets under intermittent NIR illumination is assessed. As shown in Figure 3b, the nanoparticles on the BP sheets after NIR light irradiation show faster nucleation and growth than those without NIR light irradiation. After 8 days, the nanoparticles grow in quantity and size in comparison with those without NIR light irradiation and form a densely packed layer on the surface. Hence, the NIR photochemical activity of BP sheets promotes in situ biomineralization because under NIR illumination, faster enrichment of $\\mathrm{PO_{4}}^{3-}$ in local regions accelerates extraction of calcium ions from SBF and the heat generated by the photothermal effect of BP sheets also promotes nucleation and growth of the mineral crystals to accelerate biomineralization.[21]  \n\n![](images/1ec5b6dba7d1a3cf988c1b1c60424f2e39ff19b41e5dfc2bfe489586e2bbdc49.jpg)  \nFigure 3. Characterization of BP sheets after biomineralization: SEM images of BP sheets a) without and b) with NIR light irradiation after biomineralization in SBF for different periods of time. c) EDS elemental maps and d) XPS spectra of BP sheets after biomineralization in SBF for 8 days.  \n\nThe chemical composition of the nanoparticles is determined by energy dispersive X-ray spectrometry (EDS) (Figure 3c). The distribution of O and Ca are similar to that of $\\mathrm{\\DeltaP}$ indicating efficient degradation and biomineralization. XPS is employed to determine the chemical states of the BP sheets before (Figure S6, Supporting Information) and after (Figure 3d) biomineralization. The peaks at 129.5 and $130.5\\mathrm{eV}$ assigned to P drop significantly, while the peak at $134.0\\ \\mathrm{eV}$ due to $\\mathrm{P}_{x}\\mathrm{O}_{\\gamma}$ increases and peaks at 347.0 and $350.5\\mathrm{eV}$ related to ${\\mathrm{Ca}}^{2+}$ appear,[53] providing additional evidence about the degradation and in situ biomineralization process on BP sheets in SBF. The P, O, and Ca concentrations after immersion for 0, 2, 4, 6, and 8 days without/with NIR light irradiation are determined by EDS (Figure S7, Supporting Information). The concentration of Ca increases gradually with time for both groups and the increase is faster with NIR light irradiation.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.4. Controlled Biomineralization of BP@Hydrogel  \n\nThe biomineralization performance is crucial to tissue engineering especially scaffolds for cartilage and bone repair since hardened and stiffened scaffolds are necessary to provide structural support to tissues during bone regeneration.[54] Based on the unique and excellent in situ biomineralization performance and NIR photochemical activity of BP sheets, NIR light controlled biomineralization of BP incorporated hydrogel (BP $@$ Hydrogel) is demonstrated in vitro. The BP incorporated hydrogel (BP $@$ Hydrogel) is prepared using a $4\\%\\ \\mathrm{w/v}$ agarose aqueous solution containing $50\\ \\mathrm{ppm\\BP}$ sheets at $60~^{\\circ}\\mathrm{C}$ and it is then cooled rapidly to $4^{\\circ}\\mathrm{C}$ to form the hydrogel. The photographs of the hydrogels in Figure 4a reveal that the BP sheets are distributed uniformly over the agarose hydrogel and the addition of BP sheets does not destroy the structure of the agarose hydrogel.  \n\nThe pure hydrogel, BP $@$ Hydrogel, and $\\mathtt{B P@}$ Hydrogel with NIR light irradiation are incubated in SBF for further biomineralization at $37^{\\circ}\\mathrm{C}$ for up to 8 days. At the predetermined time intervals (0, 2, 4, 6, and 8 days), the mechanical properties of the hydrogels are determined by a dynamic mechanical analyzer. Figure S8 (Supporting Information) presents the stress versus strain curves after 8 days. The curves of the pure hydrogel and $\\mathtt{B P}\\ @$ Hydrogel without NIR light irradiation display a sigmoid shape characteristic of elastomeric materials with a low modulus and large deformation before fracture, whereas that of $\\mathtt{B P@}$ Hydrogel with NIR light irradiation shows a much higher slope and bigger stress at the breaking point. The corresponding compressive strength (Figure 4b) and Young’s modulus (Figure 4c) of the hydrogels at the predetermined time intervals (0, 2, 4, 6, and 8 days) are calculated from the stress–strain curves. Compared to the pure hydrogel with unobvious changes in mechanical properties during the biomineralization process, $\\mathtt{B P@}$ Hydrogel exhibits a relatively significant mechanical enhancement, indicating that BP sheets promote in situ biomineralization of hydrogels by providing phosphorus and nucleation sites. $\\mathtt{B P}\\ @$ Hydrogel with NIR light irradiation has a higher compressive strength of $1350\\mathrm{KPa}$ and Young’s modulus of $220\\ \\mathrm{KPa}$ after 8 days and they are almost 5 times larger than those of the pure hydrogel confirming that NIR illumination accelerates biomineralization of $\\mathtt{B P}\\ @$ Hydrogel. Since biominerals generally possess superior mechanical properties than the synthetic pure crystals,[55] $\\mathtt{B P@}$ Hydrogel after biomineralization possess better mechanical properties (Figure S9, Supporting Information) than the sample with the same amount of CAP nanoparticles (BP&CAP $@$ Hydrogel) due to homogeneous intermixing and combination of organic and inorganic components.  \n\n![](images/bf1652dd7b3072e997d3bcdf7ca98427df3ef4a0fbd0fecfc31378c83d4f61ca.jpg)  \nFigure 4. Controlled biomineralization of hydrogels arising from the NIR photochemical activity of BP: a) Photographs of hydrogels before biomineralization. b) Compressive strength and c) Young’s modulus of hydrogels after biomineralization at the predetermined time intervals (0, 2, 4, 6, and 8 days). d) SEM images of the internal morphology of hydrogels after 8 days. e) Quantitative analysis of P and Ca in hydrogels after biomineralization. f) Photographs of bone-shaped hydrogels after controlled in situ biomineralization for 0, 2, 4, 6, and 8 days with insets showing the corresponding SEM images with and without light irradiation after 8 days.  \n\nThe appearance of the hydrogels before and after biomineralization is visualized after vacuum freeze-drying (Figure S10, Supporting Information). The hydrogels show slight swelling without structural collapse during biomineralization indicating good mechanical properties. Compared to that without NIR light irradiation, BP@Hydrogel with NIR light irradiation shows a lighter color during biomineralization due to faster degradation and biomineralization. The internal morphology of these hydrogels is observed by SEM and the images after 8 days are depicted in Figure 4d. All the hydrogels have a similar porous structure further confirming no obvious structural damage during biomineralization. Compared to the pure hydrogel with few mineral particles on the wall of the inner pores, a large number of tiny mineral particles are evenly distributed on the inner pore wall of $\\mathtt{B P}\\ @$ Hydrogel without or with NIR illumination, indicating that the in situ biomineralization take place homogeneously on the hydrogel. In addition, more mineral particles with a dense arrangement are observed from the inner pore wall and form a mineral layer on the surface of $\\mathtt{B P@}$ Hydrogel after NIR light irradiation. The mineral particles have a spherical structure of about $300\\ \\mathrm{nm}$ in diameter. EDS reveals the presence of phosphorus, oxygen, and calcium (Figure S11, Supporting Information) and ICP-AES (Figure 4e) confirms the results.  \n\nBone-shape scaffolds are produced using the hydrogels (Figure 4f; and Figure S12, Supporting Information) by 3D printing to further investigate the controlled biomineralization process in situ. Similar spontaneous degradation and biomineralization process of $\\mathtt{B P@}$ Hydrogel can be observed. Interestingly, the upper left part of the bone-shape BP@Hydrogel scaffold under light irradiation by adjusting the light spot size and illumination position shows more extensive biomineralization than the upper right part without light irradiation (Figure S13, Supporting Information; and insets of Figure 4f). The results demonstrate that the NIR light-induced photochemical activity of BP sheets can be modulated by changing the irradiation time and location. This is particularly attractive because of the high tissue penetration ability and excellent controllability in space and time of NIR light.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 3. Conclusions  \n\nIn conclusion, the photochemical activity of BP sheets arising from the formation of $\\mathrm{PO_{4}}^{3-}$ during NIR light-controlled biomineralization in situ is systematically investigated and demonstrated. Owing to the excellent NIR absorption, BP sheets under NIR illumination exhibit much faster degradation both in moist air and solution. The chemical activity of BP sheets is enhanced by NIR light irradiation. The BP sheets not only can provide a phosphorus source and nucleation sites, but also accelerate the reaction between $\\mathrm{PO_{4}}^{3-}$ and $\\mathrm{Ca^{2+}}$ to promote biomineralization. The BP sheets with excellent photochemical activity are applied to controlled biomineralization of hydrogels in situ and by modulating the irradiation time and location of the NIR light, the mechanical properties and biomineralization ability can be tailored. NIR light-controlled biomineralization has immense clinical potential especially tissue engineering and the photochemical activity of BP bodes well for many other biological and biomedical applications.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 9,
+        "chunk": "# 4. Experimental Section  \n\nMaterials: The BP crystals were purchased from Mophos and stored in a dark Ar glovebox and N-methyl-2-pyrrolidone (NMP, $99.5\\%$ , anhydrous) was obtained from Aladdin Reagents. The SBF with an inorganic salt composition similar to human blood plasma was obtained from Qingdao Jisskang Biotechnology. Agarose was purchased from Fisher Scientific. All the chemicals used in this study were analytical reagent grade and used without further purification.  \n\nSynthesis of BP Flakes, BP Sheets, and $B P@$ Hydrogel: The micro-sized BP flakes were prepared by mechanical exfoliation from the bulk crystal using scotch tape and transferred to a $\\mathsf{S i}/\\mathsf{S i O}_{2}$ wafer. The BP sheets were prepared by a modified liquid exfoliation technique. Briefly, the BP crystals were dispersed in NMP with an initial concentration of $1\\mathrm{\\mg\\mL^{-1}}$ and ground to fine powders. The dispersion was sonicated in an ice bath for $\\mathsf{\\Delta}\\mathsf{70~h}$ using a power of $300\\mathrm{\\:}\\forall\\$ and centrifuged at 4000 rpm for $\\mathsf{10}\\mathsf{m i n}$ . The supernatant containing the BP sheets was decanted gently and centrifuged for another 10 min at 7000 rpm. The precipitate was collected and resuspended for subsequent experiments. A certain amount of agarose powders $(4~\\mathrm{wt\\%})$ was dispersed in deionized water under mechanical stirring at $90^{\\circ}\\mathsf{C}$ for 30 min and stored in a $4~^{\\circ}\\mathsf{C}$ refrigerator for $30\\mathrm{\\min}$ to obtain the agarose hydrogels. $\\mathsf{B P@}$ Hydrogel was prepared by mixing the agarose solution with BP sheets (20 ppm) by the procedures mentioned above. ${\\mathsf{B P\\&C A P}}({\\widehat{\\boldsymbol{\\varrho}}})$ Hydrogel was obtained by dispersing $2{\\mathsf{m g}}{\\mathsf{C A P}}$ nanoparticles ( ${\\approx}200\\mathsf{n m}$ in diameter) into the $\\mathsf{B P@}$ Hydrogel solution and then prepared by the same method as described above. The bone-shape hydrogels were fabricated by 3D printing using the sequential strand deposition method on a bioplotter pneumatic dispensing system (Bioscaffolder 3.1, GeSiM, Grosserkmannsdorf, Germany).  \n\nCharacterization: The SEM images were obtained on the fieldemission SEM (NOVA NANOSEM430, FEI, Netherlands) at $5{-}70~\\mathsf{k V}$ after gold coating for $\\boldsymbol{120\\ s}$ (EM-SCD500, Leica, Germany). EDS was conducted on the Oxford INCA 300 equipped on the SEM. The TEM images were acquired on the JEOL JEM-2010 transmission electron microscope at an acceleration voltage of $200\\ensuremath{\\mathrm{\\kV}}$ and AFM was performed on an MFP3D-S AFM (Asylum Research, USA) using the tapping mode in air. Raman scattering was conducted on a Horiba Jobin-Yvon LabRam HR-VIS high-resolution confocal Raman microscope equipped with the $633\\ \\mathsf{n m}$ laser as the excitation source. The UV–vis–NIR absorption spectra were acquired on a Lambda25 spectrophotometer (PerkinElmer) with QS-grade quartz cuvettes at room temperature. The concentration was determined by inductively-coupled plasma atomic emission spectroscopy (ICP-OES, 7000DV, PerkinElmer). XPS was carried out on the Thermo Fisher ESCALAB 250Xi XPS with an Al ${\\sf K}_{\\alpha}$ X-ray source. The XPS peaks were calibrated by the standard C 1 s peak at 284.8 eV according to the Thermo Scientific XPS Knowledge Base. The mechanical properties of these hydrogels ( $8\\:\\mathsf{m m}$ in diameter and $4\\:\\mathsf{m m}$ in height) were evaluated through a uniaxial compression test on a WDW-05 electromechanical tester (Time Group Inc., China). The modulus was obtained by the initial (straight line) linear slope of the stress–strain curve and the compressive strength was defined as the stress at the end of the linear portion of the stress–strain curve.  \n\nNIR Laser Irradiation: NIR laser irradiation was performed with a fibercoupled continuous semiconductor diode laser ( $\\cdot808\\ n m$ , KS-810F-8000, Kai Site Electronic Technology Co., Ltd. Shaanxi, China) at a power density of $\\mathsf{l}.0\\mathsf{W}\\mathsf{c m}^{-2}$ for $\\mathsf{10}\\mathsf{m i n}$ , three times daily.  \n\nNIR Laser-Induced Heat Conversion: A fiber-coupled continuous semiconductor diode laser $808{\\mathsf{n m}}$ , KS-810F-8000, Kai Site Electronic Technology Co., Ltd. Shaanxi, China) was employed in the experiments. 1 mL of the sample in a $\\mathsf{1c m}$ path length quartz cuvette was irradiated with the laser at a power density of 1 W $c m^{-2}$ for $\\mathsf{10}\\mathsf{m i n}$ . The laser spot was adjusted to cover the entire surface of the sample. Real-time thermal imaging was performed and the maximum temperature was recorded by the Fluke Ti27 infrared thermal imaging camera (USA).  \n\nDegradation Performance: The freshly prepared micro-sized BP flakes were stored in air at nearly $100\\%$ relative humidity at room temperature for different time durations and the evolution without/with NIR laser irradiation was observed by optical microscopy after exposure to moist air for 0, 2, 4, 6, and 8 days. For the degradation of BP sheets, BP sheets dispersed in water (1 mL for each, $20\\mathsf{p p m})$ were kept in closed sample vials, maintained in a horizontal shaker at $37^{\\circ}\\mathsf C$ . Then the solutions were exposed to an NIR laser with a wavelength of $808~\\mathsf{n m}$ at a power density of $\\mathsf{\\dot{l}}.0\\mathsf{W}\\mathsf{c m}^{-2}$ for 10 min each time for sufficient heating, naturally cool in the shaker, and then repeated three times daily for 0, 2, 4, 6, and 8 days. The concentration of phosphate anions in the supernatant was determined by the QuantiChrom Phosphate Assay Kit (BioAssay Systems) following the manufacturer’s instruction.  \n\nIn Situ Biomineralization of $B P$ Sheets and $B P@$ Hydrogel: The biomineralization process was carried out in the SBF solution containing similar ion concentrations as the human blood plasma. The BP sheets and $\\mathsf{B P@}$ Hydrogel without/with NIR laser irradiation were immersed in SBF for up to 8 days with fixed at intervals at $37^{\\circ}\\mathsf{C}$ in an incubator. After biomineralization for 0, 2, 4, 6, and 8 days, the samples were taken out, washed twice with deionized water, and vacuum freeze-dried.  \n\nStatistical Analysis: All the data were presented as means $\\pm$ standard deviation (SD). In order to test the significance of the observed differences between the study groups, analysis by variance (ANOVA) statistics was applied and a value of $P<0.05$ was considered to be statistically significant.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# Supporting Information  \n\nSupporting Information is available from the Wiley Online Library or from the author.",
+        "category": " References"
+    },
+    {
+        "id": 11,
+        "chunk": "# Acknowledgements  \n\nThe authors acknowledge financial support from the Guangdong Special Support Program (No. 2017TX04C096), Key Research Program of Frontier Sciences, CAS (No. QYZDB-SSW-SLH034), Leading Talents of Guangdong Province Program (No. 00201520), National Natural Science Foundation of China (No. 51702352), and Hong Kong Research Grants Council (RGC) General Research Funds (GRF) (CityU 11205617).",
+        "category": " Acknowledgements"
+    },
+    {
+        "id": 12,
+        "chunk": "# Conflict of Interest  \n\nThe authors declare no conflict of interest.",
+        "category": " References"
+    },
+    {
+        "id": 13,
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+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Hydrophilic nano-SiO /PVA-based coating with durable antifogging properties  \n\nGuoqiang Wu, Yuling Yang, Yongtong Lei, Dapeng Fu, Yuchao Li, Yanhu Zhan, Jinming Zhen, Mouyong Teng  \n\n$\\circleddash$ American Coatings Association 2020  \n\nAbstract Hydrophilic $\\mathrm{SiO}_{2}/$ poly(vinyl alcohol) (PVA) coating prepared by solution blended method showed high light transmittance and durable antifogging performance. The effects of $\\mathrm{SiO}_{2}$ content and $\\mathrm{p}\\mathrm{\\bar{H}}$ value of $\\mathrm{SiO}_{2}$ suspension on the morphology and properties of hydrophilic coating were studied by Fourier transform infrared spectroscopy, scanning electron microscopy, atomic force microscopy, contact angle test, ultraviolet visible light spectrophotometer, and antifogging test. Results showed that the PVA had good compatibility with nano- $\\mathrm{SiO}_{2}$ because of the formation of $S_{\\mathrm{i-O-C}}$ chemical bond at the interface between nano- $S\\mathrm{i}0_{2}$ and PVA. When prepared at $\\mathrm{pH}=7$ , $\\mathrm{SiO}_{2}/\\mathrm{PV}\\mathrm{A}$ coatings $\\mathbf{\\dot{SiO}}_{2}/\\mathbf{PVA}$ mass ratio of 0.8) were hydrophilic, with a water contact angle of $22.9^{\\circ}$ , and exhibited papilla-like surface features $(\\mathbf{RMS}=7.6~\\mathrm{nm}$ ). Polyethylene (PE) samples coated with this $\\mathrm{SiO}_{2}/\\mathrm{PV}\\mathrm{A}$ film exhibited a light transmittance of up to $90\\%$ , between 560 and $700~\\mathrm{nm}$ , and remained fog-free for more than 1 month after exposure to water at $60^{\\circ}\\mathrm{C}$ (QB/T 4475-2013 standard). Water-resisting and wear-resisting tests revealed that antifogging coatings demonstrated excellent mechanical properties.  \n\nKeywords Hydrophilic coating, Papilla-like structures, High transmittance, Durable antifogging",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# Introduction  \n\nFogging occurs when water molecules condense as discrete droplets with diameters larger than $190~\\mathrm{nm}$ or half of the shortest wavelength $\\left(380\\ \\mathrm{nm}\\right)$ of visible light.1 This phenomenon is harmful to optical materials and analytical and medical instruments, such as eyeglasses,2 goggles, solar cells,3 face shields, binoculars, microscopes,4 and laparoscopes.5 Fogging is also common in agricultural greenhouses where a polymer film, such as polyethylene (PE), is used as a barrier to protect growing plants.6 The occurrence of fogging results in a number of side effects, including poor film clarity and reduced light transmittance. Several research groups have developed polymer films with antifogging performance by depositing hydrophilic coatings.7–12 An efficient way to prevent fog is to increase the surface energy that can form a hydrophilic surface for polymer films. Water drops lying on a (super)hydrophilic surface spread across it to form a transparent and continuous thin film of water. The resulting layer of water allows for the incident light to pass through it without being scattered, thus attaining the antifogging effect.13–16  \n\nSo far, two main strategies have been explored to produce antifogging coatings with water-attracting characteristics. The first strategy uses inorganic nanoparticles to create one or more layers of micron-/nanometer-scale roughness on the surface of the substrate. Various types of nanoparticles are available for the creation of surface roughness, such as $\\mathrm{TiO}_{2}$ ,8 $\\mathbf{SiO}_{2,\\dots,\\dots}^{\\phantom{-}17-19}$ faujasitic nanozeolites,20 $Z_{\\mathrm{{nO},\\l}}{}^{21}$ $\\mathbf{Z}\\mathbf{r}\\mathbf{O}_{2}$ , or ${\\bf W}{\\bf O}_{3}$ .22,23 Saxena et al.17 deposited a dendritic pattern of $\\mathrm{TiO}_{2}$ and $\\mathrm{SiO}_{2}$ on the transparent glass surface by the template method. The patterns of only $\\mathrm{SiO}_{2}$ and $\\mathrm{TiO}_{2}$ nanoparticles are attained on the glass surface after calcining the template at $450^{\\circ}\\mathrm{C}$ The surface of the glass showed superhydrophilic and antifogging performance. Chen et al.18 fabricated a multifunctional $\\mathrm{SiO}_{2}$ coating via a low-cost one-step chemical vapor deposition method. In particular, the 10-h-deposited silica nanoparticles’ thin coating surface showed the best hydrophilicity, transparency, antifogging, and self-cleaning properties. The second strategy to prepare antifogging coatings consists of depositing polymers or monomers containing hydrophilic functionalities, such as – OH or –COOH groups. For example, hydrophilic coatings have been achieved by depositing acrylic resin,24,25 silicone,26 poly(vinyl alcohol) (PVA),12,27–29 poly(vinyl acetate), poly(ethylene glycol),30 cellulose ester or cellulose ether,11,31 and poly(vinylpyrrolidone) (PVP).32 Lee et al.28 obtained a hydrophilic coating by hydrogen-bonding-assisted layer-by-layer assembly using PVA and poly(acrylic acid) (PAA) with excellent antifogging and frostresistant properties. Nuraje et al.2 prepared a hydrophilic surface with carboxymethyl cellulose and oligomeric chitosan on polycarbonate and glass samples, The results show that the anti-fog property is related to intermolecular hydrogen bonding and surface water film. The above-mentioned hydrophilic coatings showed excellent antifogging property; however, the fabrication steps were tedious and complex, usually requiring multistep, expensive fabrication techniques.  \n\nPVA is a water-soluble polymer having the properties of good compactness, high crystallinity, strong adhesion, nontoxicity, being odorless and harmless to the human body, and good affinity for water molecules.12,16 The PVA molecule contains a large amount of hydroxyl groups and is highly hydrophilic. The addition of nano- $\\mathrm{\\cdot}\\mathrm{\\dot{SiO}}_{2}$ into PVA can improve the network structure, enhance the mechanical properties of the film, and improve its thermal stability and water resistance.33 Tong et al.34 prepared the noncharged $\\mathrm{PVA}/\\mathrm{SiO}_{2}$ hybrid films through sol–gel process for alkali recovery. The hybrid films can be potentially used to separate $\\mathrm{\\DeltaNaOH/Na_{2}W O_{4}}$ solution. Liu et al.35 reported the $\\mathrm{PVA}/\\mathrm{SiO}_{2}$ hybrid coatings via ‘‘one-step’’ hydrolysis and co-condensation, with the ability to separate oil/water immiscible mixture from highly acidic, alkaline, and salty environment. In this study, we fabricated hydrophilic nano- $\\mathrm{SiO}_{2}/$ PVA coating by solution blending method and deposited the surface on PE film by dip coating technique for the first time. The structure of hydrophilic coating was observed by SEM, AFM, and FTIR. The hydrophilic property was studied by water contact angle test. The transmittances of the coated PE were investigated. Furthermore, the antifogging property of the coated PE was also studied by the self-made antifog-measuring instrument and the mechanical properties (water-resisting and wear-resisting property) of the hydrophilic coating were also tested.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# Experimental",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# Materials  \n\nCorona-treated PE films with $0.1\\mathrm{mm}$ thickness were obtained from Shandong Dongda Plastic Industry $\\scriptstyle{\\mathrm{Co}}$ ., Ltd. Haq et al.36 reported that corona discharge treatment can significantly improve the wettability of the PE surface so that the hydrophilic coatings prepared in this study are expected to spread across it evenly. Poly(vinyl alcohol) (PVA, $\\bar{M}_{\\mathrm{n}}=70{,}000{-}$ 90,000, $99\\%$ hydrolyzed) was purchased from Sinopec Chongqing SVM Chemical $\\scriptstyle{\\mathrm{Co}}$ , Ltd. The colloidal silica nanoparticles Ludox N2010 $(20~\\mathrm{wt\\%}$ $\\mathrm{SiO}_{2}$ suspension, average particle size of $12\\ \\mathrm{nm}$ , and $\\mathrm{pH}$ value of 7) and Ludox SS3010 ( $(30~\\mathrm{wt\\%}$ $\\mathrm{SiO}_{2}$ suspension, average particle size of $8\\ \\mathrm{nm}$ , and $\\mathrm{pH}$ value of 10) were obtained from Shandong Peak-Tech New Material $\\mathrm{Co}$ ., Ltd. The fluorocarbon surfactant (FA-6812) was supplied by Horizon Admixtures $\\scriptstyle{\\mathrm{Co}}$ , Ltd. Deionized water was exclusively used in all aqueous solutions and rinsing procedures.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# Preparation  \n\nHydrophilic coating was deposited on PE substrates by one-step dip coating followed by solution blending method. Solution blending process is a simple and convenient method, which can be applied to fabricate various thin films.9,37,38 A brief description follows. First, PVA solution $(5~\\mathrm{wt\\%}$ in water) was mixed with Ludox (N2010, SS3010) via mechanical stirring for $^{1\\mathrm{~h~}}$ . The aforementioned solution was then diluted with deionized water followed by the addition of fluorocarbon surfactant in one thousandth to the solution in order to reduce the surface tension. Then, the PE film was immersed in the hybrid solution for $5\\mathrm{\\textbf{s}}$ Finally, the PE film was thermal-treated for $5\\mathrm{{min}}$ at $80^{\\circ}\\mathrm{C}$ to evaporate solvent. Three $\\mathrm{SiO}_{2}/\\mathrm{PV}\\mathrm{A}$ ratios and two $\\mathrm{pH}$ values were used in this work to prepare hydrophilic coatings. The assembly of hydrophilic coating is designated as (Y$\\mathbf{PV}\\mathbf{A})_{\\mathbf{x}}$ , in which x and Y represent the mass ratio of $\\mathrm{SiO}_{2}$ to PVA and the kind of Ludox, respectively. For example, $(\\mathrm{N}2010–\\mathrm{PV}\\mathrm{A})_{0.8}$ means that the mass ratio of Ludox N2010 to PVA is 0.8. Table 1 lists the mass ratios of $\\mathrm{SiO}_{2}$ to PVA in the antifogging coatings.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# Characterization  \n\nThe surface morphologies of the deposited coatings were examined by field emission scanning electron microscopy (FE-SEM) on a German Zeiss scanning electron microscope. Water contact angles on deposited coatings were measured at room temperature on a JC2000 contact angle measuring instrument (Shanghai Zhongchen Digital Technique Apparatus Co., Ltd). Water droplets of $2.0~\\upmu\\mathrm{L}$ were dropped carefully onto the thin-film surfaces. At least three positions were tested in order to get the average value. Atomic force microscopic (AFM) images of the deposited coatings were captured with a SPA-300HV environment controlled scanning probe microscope (Japan Seiko). The scanning frequency was $0.8\\mathrm{Hz}$ . The scanning size was $1.5~{\\upmu\\mathrm{m}}\\times1.5~{\\upmu\\mathrm{m}}$ . At least three positions were tested in order to get the average value. Transmission spectra in the wavelength range of $300{\\mathrm{-}}900\\ \\mathrm{nm}$ were recorded using a UV-3600 spectrophotometer (Shimadzu, Japan). The hybrid solution particle size and its distribution were determined with a laser particle analyzer (90Plus S/N) from Brookhaven (America). FTIR spectra of samples dispersed in KBr pellets were obtained by Nicolet IR-100 spectrometer in a spectra range of $400{\\-}4000~\\mathrm{cm}^{-1}$ . The antifogging performance of the coated PE films was tested according to the protocol defined in the QB/T 4475-2013 standard using a laboratory-made device (Fig. 1).39 The PE film was placed on the round opening (diameter of $115~\\mathrm{mm}$ ) of the instrument. The water was kept at ${}60^{\\circ}\\mathrm{C}$ in the instrument while observing and recording the surface antifogging performance of the PE film. Freeze tests were performed by placing the two PE films in the freezer at $20^{\\circ}\\mathrm{C}$ for $20~\\mathrm{min}$ . PE films were removed and then placed in the humid laboratory air. Vapor condensed on the PE film surface was observed and photographed. Reliability of the antifogging performance of the coated PE films was tested by rubbing, using a soaked sponge rotating at 50 cycles per minute for up to 20 cycles and by exposure to a continuous water scouring for $12\\mathrm{~h~}$ .  \n\n<html><body><table><tr><td>Table1: Chemical antifogging layer (SiO2/PVA in mass ratio) Sample code</td><td>species for Ludox N2010 (pH = 7)</td><td>preparing LudoxSS3010</td><td>the PVA</td></tr><tr><td></td><td></td><td>(pH = 10)</td><td>(5%)</td></tr><tr><td>PVA (N2010-PVA)0.4</td><td>0 0.4</td><td>0 0</td><td>1 1</td></tr><tr><td>(N2010-PVA)0.8</td><td>0.8</td><td>0</td><td>1</td></tr><tr><td>(N2010-PVA)2</td><td>2</td><td>0</td><td>1</td></tr><tr><td>(SS3010-PVA)0.4</td><td>0</td><td>0.4</td><td>1</td></tr><tr><td>(SS3010-PVA)0.8</td><td>0</td><td>0.8</td><td>1</td></tr><tr><td>(SS3010-PVA)2</td><td>0</td><td>2</td><td>1</td></tr><tr><td>Ludox N2010</td><td>1</td><td>0</td><td>0</td></tr><tr><td></td><td></td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# Results and discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# Chemical composition  \n\nFigure 2 illustrates the particle size distributions of the nanocomposite solution. The average diameter of neutral Lodox N2010 was $18.7\\ \\mathrm{nm}$ , while that of the $(\\mathrm{N}2010–\\mathrm{PV}\\mathrm{A})_{0.4}$ composite solution was $73.5~\\mathrm{nm}$ . Such increase in the average diameter may be attributed to the encapsulation of PVA chains. As the $(\\mathrm{SiO}_{2}/\\mathrm{PV}\\mathrm{A})$ 1 mass ratio increased to 2, the average diameter of the $(\\mathrm{N}2010–\\mathrm{PV}\\mathbf{A})_{2}$ decreased to $49.7~\\mathrm{nm}$ . This is due to the fact that PVA molecule chains can crosslink with the nano- $\\mathrm{.}\\mathrm{SiO}_{2}$ to form much denser particles.33 The average diameter of alkaline Lodox SS3010 is about $16.3\\ \\mathrm{{nm}}$ , while the diameter of $(\\mathrm{SS3010–PVA})_{0.8}$ is $68.6\\ \\mathrm{nm}$ . The neutral and alkaline Lodox showed a similar pattern with no significant difference in the solution.  \n\n![](images/a46b27f80ec8a804d6ca1420eba9da178839a338e7f788535694c292a1d6e5bf.jpg)  \nFig. 1: Diagram of fog test  \n\n![](images/33e8d84cf51198aa6efb201afade98bcdec28472856f103805d5ac6760e594a1.jpg)  \nFig. 2: Particle size and distribution of nano- $S i O_{2}/P V A$ composite solution. (a) $(\\S\\S\\3010\\mathrm{-}\\mathsf{P V A})_{0.8}$ , (b) (N2010- $\\mathsf{P V}\\mathsf{A})_{0.4},$ , (c) $(\\mathsf{N}2010\\mathsf{-P V}\\mathsf{A})_{0.8},$ (d) $(\\mathsf{N}2010\\mathsf{-P V}\\mathsf{A})_{2}$ , (e) Ludox N2010, (f) Ludox SS3010  \n\nIn order to understand the interaction between the PVA and $\\mathrm{SiO}_{2}$ , the hybrid materials were analyzed by Fourier transform infrared (FTIR) spectroscopy. Figure 3 shows the FTIR spectra of PVA, $\\mathrm{SiO}_{2}$ coating, and $\\mathrm{SiO}_{2}/\\mathrm{PV}\\mathrm{A}$ coating (summarized in Table 2). The characteristic peak found around $3436~\\mathrm{cm}^{-1}$ is associated with stretching vibrations of $-\\mathrm{OH}$ , which decreased with the increase in silica content, indicating the presence of a hydrogen bond.40 The absorption peaks at 2920 and $2\\mathrm{{\\dot{8}58}}\\mathrm{{\\dot{cm}}}^{-1}$ correspond to the $\\mathrm{CH}_{3}$ asymmetric stretching and $\\mathrm{CH}_{2}$ asymmetric stretching vibrations. The peaks at $1382~\\mathrm{cm}^{-\\mathrm{f}}$ are associated with $\\mathrm{CH}_{2}$ wagging vibrations. And the peaks at 1163 and $1071~\\mathrm{cm}^{=1}$ are related to $\\mathrm{C-O}$ bond and $\\scriptstyle{\\mathrm{C-C}}$ group. The characteristic stretching vibration peak intensities of $\\mathrm{Si-O{-}S i}$ group, located at $1102~\\mathrm{{cm}^{-1}}$ and $797~\\mathrm{cm}^{-1}$ , increased gradually with the increase in $\\mathrm{SiO}_{2}$ mass fraction. The peak at $1000~\\mathrm{cm}^{-1}$ represents $\\mathrm{Si-O-C}$ vibration modes due to the overlapping vibrations of $\\mathrm{C-O}$ and $\\mathrm{Si-O}$ bonds.33,41 A similar trend was also observed by Xu et al.,42 who reported the condensation of silanol groups with the $-\\mathrm{O}\\bar{\\mathrm{H}}$ on the PVA molecule chain to form $\\mathrm{Si-O{-}(P V A){-}O{-}S i}$ crosslinks or ‘‘bridges’’. Because a lot of silanol groups had been condensed with the hydroxyls on PVA chain to form Si–O–C linkage, the vibrating intensity of Si–O–Si, Si– OH, and $\\mathrm{\\Gamma_{O-H}}$ bonds was largely weakened.  \n\n![](images/80fce4dbbab62b9b11a9e8bfd4a8067480b22c430b50a7855b1f73b75b1ff203.jpg)  \nFig. 3: Fourier transform infrared spectra of nano- $\\bullet\\mathrm{i}0_{2}/$ PVA hydrophilic coatings. (a) PVA, (b) $(\\mathsf{N}2010\\mathsf{-P V}\\mathsf{A})_{0.4},$ , (c) $(\\mathsf{N}2010\\mathrm{-}\\mathsf{P}\\mathsf{V}\\mathsf{A})_{0.8}$ , (d) $(\\mathsf{N}\\mathsf{2}\\mathbf{0}\\mathsf{1}\\mathbf{0}\\mathsf{\\mathrm{-}P}\\mathsf{V}\\mathsf{A})_{\\mathsf{2}},$ (e) Ludox N2010, (f) $(\\mathsf{S S3010-P V A})_{0.8}$  \n\nTable 2: Assignments of FTIR absorption bands of films   \nPeaks for films $(\\mathsf{c m}^{-1})$ )   \n\n\n<html><body><table><tr><td>PVA</td><td>SiO2/PVA</td><td colspan=\"2\">SiO2</td></tr><tr><td>3436</td><td>3436</td><td>3436</td><td>Stretching of OH</td></tr><tr><td>2920</td><td>2920</td><td>一</td><td>Asymmetric stretching of CH3</td></tr><tr><td>2858</td><td>2858</td><td>一</td><td>Asymmetric stretching of CH2</td></tr><tr><td>1382</td><td>1382</td><td>、</td><td>CH2 wagging</td></tr><tr><td>1163</td><td>1159</td><td>一</td><td>C-O stretching</td></tr><tr><td>1071</td><td>1075</td><td>1</td><td>Stretching of C-C and bending of OH</td></tr><tr><td></td><td>一</td><td>1102</td><td>Si-O-Si</td></tr><tr><td>950</td><td>950</td><td></td><td> O-H bending out-of-plane</td></tr><tr><td>858</td><td>858</td><td>一</td><td>C-C stretching</td></tr><tr><td></td><td></td><td>797</td><td>Si-O-Si</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# Surface morphology  \n\nThe SEM images of PVA, PVA/ $\\mathrm{\\SiO}_{2}$ , and $\\mathrm{SiO}_{2}$ composite coatings are displayed in Fig. 4. From Fig. 4a, it is seen that the PVA coating is smoothly coated on the PE film. For $(\\mathrm{N}2010–\\mathrm{PV}\\mathrm{A})_{0.4}^{-}$ , the surface of PE film is coated by silica nanoparticles with a diameter of $18\\pm5~\\mathrm{{nm}}$ , as shown in Fig. 4b. When the $\\mathrm{SiO}_{2}$ concentrations increase from $(\\mathrm{N}2010–\\mathrm{PV}\\mathrm{A})_{0.4}$ to $(\\mathrm{N}2010–\\mathrm{PV}\\mathrm{A})_{0.8}$ , the size of silica has no change, but the dispersion of $\\mathrm{SiO}_{2}$ particles is more uniform on the surface (Fig. 4c). In Fig. 4e, $\\mathrm{SiO}_{2}$ nanoparticles are evenly dispersed on the surface of PE film. The particles on the surface of PE film become denser with the increase in the content of neutral $\\mathrm{SiO}_{2}$ nanoparticles. However, it is found that the alkaline $\\mathrm{SiO}_{2}$ and PVA of surface structures are different from those of neutral ones and the alkaline $\\mathrm{SiO}_{2}$ nanoparticles are easily aggregated into particles with a particle size of $500\\ \\mathrm{{\\dot{n}m}}$ and dispersed on the surface unevenly (Figs. 4 f–4h).  \n\nAFM was employed to disclose the surface morphology and the roughness of the coating surfaces. Figure 5 shows the AFM images of the $\\mathbf{\\bar{SiO}}_{2}/\\mathbf{PV}\\mathbf{A}$ coating surfaces with various $\\mathrm{SiO}_{2}$ concentrations and $\\mathrm{pH}$ values. As shown in Fig. 5a, the surface of PVA coating is flat with an average roughness of $4.4~\\mathrm{nm}$ . When the $\\mathrm{SiO}_{2}$ concentrations increase from (N2010- $\\mathrm{PVA})_{0.4}$ to $(\\mathrm{N}2010–\\mathrm{PV}\\mathrm{A})_{0.8}$ , the topographic diagrams of the two samples are similar (Figs. 5b and 5c), which agree well with the results of SEM images. The two surfaces exhibit an average roughness of $6.3~\\mathrm{{nm}}$ and $7.6~\\mathrm{nm}$ , respectively. In contrast, the average roughness of $(\\mathrm{N}2010\\mathrm{-}\\mathrm{PV}\\mathbf{A})_{2}$ decreases to $1.6\\ \\mathrm{nm}$ as shown in Fig. 5d. The $\\mathrm{SiO}_{2}$ nanoparticles accumulate layer by layer, generating holes in the surface due to the high content of $\\mathrm{SiO}_{2}$ . Figure 5e shows that the Ludox N2010 coating is in fact very smooth and dense, and many thin cracks can be noted. The roughness of $\\mathrm{SiO}_{2}$ nanoparticle coating is tested to be only $1.4~\\mathrm{nm}$ . In Fig. 5f, the nano- $\\mathrm{SiO}_{2}$ particles condense into large particles around $500\\ \\mathrm{nm}$ and the roughness reaches $8.6\\ \\mathrm{nm}$ .  \n\n![](images/1d2d16a72e12817c7a2e2fdc2419f3f91e60049fded7928e43d1221470d8bbae.jpg)  \nFig. 4: SEM images of PE film surface with nano- $\\mathsf{s i o}_{2}/\\mathsf{P}\\mathsf{V}\\mathsf{A}$ hydrophilic coatings. (a) PVA, (b) $(\\mathsf{N}2010\\mathsf{-P}\\mathsf{V}\\mathsf{A})_{0.4},$ (c) (N2010- $\\mathsf{P V}\\mathsf{A})_{0.8},$ , (d) $(\\mathsf{N}2010\\mathsf{-P V}\\mathsf{A})_{2}.$ , (e) Ludox N2010, (f) (SS3010-PVA)0.4, (g) (SS3010-PVA)0.8, (h) (SS3010-PVA)2  \n\nThe structural construction of natural plants and animals’ organs has provided inspiration for the wettability film designed and manufactured by humans.43,44 For example, the leaf of the lotus plant, the eyes of peacock, a nymphalid butterfly, and the fly compound eye have a well-arrayed papillae structure. In real life, there are plenty of ordered papillae arrays, which may greatly enhance the stability and wettability of various objects when coated.15 As shown in Figs. 4 and 5, the PVA coating has no obvious structure on the surface of the PE film (Supporting Information 1 shows the 3D AFM image of different specimens). With the addition of $\\mathrm{SiO}_{2}$ (Figs. 4, 5b, and 4 and 5c), the coatings $(\\mathrm{N}2010–\\mathrm{PV}\\mathrm{A})_{0.4}$ and $(\\mathrm{N}2010–\\mathrm{PV}\\mathrm{A})_{0.8}$ exhibit papilla-like nanostructures on the surface of the PE film and the coating $(\\mathrm{N}2010{\\mathrm{-}}\\mathrm{PV}\\mathrm{A})_{0.8}$ has a more regular papilla-like nanostructure on the surface of the PE film. With further increase in $\\mathrm{SiO}_{2}$ content (Figs. 4 and 5d), the voids of the coating (N2010- $\\mathrm{PVA})_{2}$ on the surface of the PE film are gradually filled and the coating $(\\mathrm{N}2010{\\mathrm{-}}\\mathrm{PV}\\mathrm{A})_{2}$ on the surface roughness is reduced from $7.6\\ \\mathrm{nm}$ [the coating (N2010- $\\mathrm{PVA})_{0.8}]$ to $1.6\\ \\mathrm{nm}$ . In Fig. 5e, the coating of $\\mathrm{SiO}_{2}$ only Ludox N2010 exhibits the minimal nanostructure on the surface of the PE film. The alkaline (SS3010- $\\mathrm{PVA})_{0.8}$ coating exhibits a convex cell structure on the surface of the PE film with the largest voids between adjacent convex cell structures (Fig. 5f). It is known that $\\mathrm{SiO}_{2}$ content and $\\mathrm{pH}$ have important influence on surface morphology.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# Surface wettability  \n\nEarly theoretical reports by Wenzel45 and Cassie and Baxter46 as well as other studies14,18 suggest that it is possible to significantly change water wettability on a surface by introducing roughness at the right length scale. Wenzel’s roughness equation concludes that roughened surfaces will have a large area of contact between surface and droplet.  \n\n$$\n\\cos\\theta^{*}=r\\cos\\theta\n$$  \n\n![](images/002f49958a9fc4a04ab06c89253f9e88c73b0fc5968998e487b3aafab6e55028.jpg)  \nFig. 5: AFM image of PE film surface with nano- $\\mathsf{S i O}_{2}/\\mathsf{P V}\\mathsf{A}$ hydrophilic coatings. (a) PVA, (b) $(\\mathsf{N}2010\\mathsf{-P V}\\mathsf{A})_{0.4},$ (c) (N2010- $\\mathsf{P V}\\mathsf{A})_{0.8}$ , (d) $(\\mathsf{N}2010\\mathsf{-P V}\\mathsf{A})_{2}$ , (e) Ludox N2010, (f) (SS3010-PVA)0.8  \n\nwhere $\\theta^{*}$ is the contact angle on the rough surface, $\\theta$ is the equilibrium contact angle on flat smooth surface, and $r$ is the roughness factor defined as the ratio of the actual surface area of surface to the projected area. From equation (1), for a hydrophilic surface (contact angle $\\mathit{\\Theta}<\\bar{9}0^{\\circ}$ ), the roughness will magnify the hydrophilicity and promote spreading of the droplet, whereas for a hydrophobic surface (contact angle $>$ $90^{\\circ}.$ ), the roughness will magnify the hydrophobicity and retard spreading of the droplet.  \n\nThe surface wettability of composite coatings is controlled by chemical composition and morphology of composite surface. Higher hydrophilicity of a coating can be reflected by lower contact angle of water on the surface.47 To examine the hydrophilicity of the composite coating surface, water contact angle measurements were carried out, which are shown in Fig. 6. For the blank PE film, the water droplet does not spread, and the contact angle is $99.5^{\\circ}\\$ (Fig. 6a). In contrast, the PE thin film after being corona treated can improve the surface energy. From Young’s equation [equation (2)], we know that the contact angle of PE thin film surface will decrease with the increase in surface tension:  \n\n$$\n\\cos\\theta=\\frac{\\gamma_{S V}-\\gamma_{S L}}{\\gamma_{L V}}\n$$  \n\nwhere $\\theta$ is the contact angle, $\\gamma_{S V}$ is the solid–gas interfacial tension, $\\gamma_{S L}$ is the solid–liquid interfacial tension, and $\\gamma_{S V}$ is the gas–liquid surface tension. The measured water contact angle decreases from $99.5^{\\circ}\\$ to $66.0^{\\circ}$ (from hydrophobic to hydrophilic, in Fig. 6b). The water droplets spread promptly out on PE film surfaces with PVA, $(\\mathrm{N}201{\\bar{0}}{\\mathrm{-}}\\mathrm{PV}{\\bar{\\mathrm{A}}})_{0.4{\\sim}2}$ , and neutral Ludox N2010 coatings (Fig. 6c, d, e, f, and g). The water contact angles change to $28.8^{\\circ}$ , $20.2^{\\circ}$ , $22.9^{\\circ}$ , $23.4^{\\circ}$ , and $23.8^{\\circ}$ at $\\mathrm{~1~s~}$ , respectively. It is found that the water contact angles of the neutral $\\mathrm{SiO}_{2}/\\mathrm{PV}\\mathrm{A}$ composite coatings are less than those of the pure $\\mathrm{SiO}_{2}$ or PVA coating, which indicates that the structure and morphology generated by the combination of $\\mathrm{SiO}_{2}$ and PVA play a positive role in wettability. In contrast, the water contact angle on PE film with alkaline coatings exhibits the highest of all coatings at $35.5^{\\circ}$ , $29.9^{\\circ}$ and $39.0^{\\circ}$ (Fig. 6h, j, and k). Therefore, the nanoscale morphology on the surface plays a key role in spreading the water droplets.48  \n\n![](images/26a52c8dd50f2a8c1b948a654dbc822ce22acfe80015ea9412de269865ebb5d6.jpg)  \nFig. 6: Water contact angle on PE film surface with nano$\\mathsf{S i O}_{2}/\\mathsf{P}\\mathsf{V}\\mathsf{A}$ hydrophilic coatings. (a) PE film, (b) PE film (after corona modification), (c) PVA, (d) $(\\mathsf{N}2010\\mathsf{-P}\\mathsf{V}\\mathsf{A})_{0.4},$ (e) (N2010-PVA) 0.8, (f) $(N2010\\mathrm{-}\\mathsf{P V}\\mathsf{A})_{2}$ , (g) Ludox N2010, (h) $(\\S\\S\\3010\\ –\\mathsf{P V A})_{0.4},$ (i) (SS3010-PVA)0.8, (j) (SS3010-PVA)2",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# The fogging test and optical properties  \n\nIt is well known that the moisture condenses to a continuous thin film on hydrophilic or superhydrophilic surfaces, whose water contact angle is less than $4{\\bar{0}}^{\\circ}$ , in order to avoid fogging.14 As discussed above, the transparent and hydrophilic $\\mathrm{SiO}_{2}/\\mathrm{PV}\\mathrm{A}$ coating on PE film surface with a water contact angle of approximately $25^{\\circ}$ was obtained. The PE film with $\\mathrm{SiO}_{2}/\\mathrm{PV}\\mathrm{A}$ coatings was found to exhibit an excellent antifogging behavior, as shown in Fig. 7a and c. Because of the good hydrophilicity of the PE film surface containing $\\mathrm{SiO}_{2}/\\mathrm{PV}\\mathrm{A}$ coatings, it shows antifogging performance in a short time. However, the PE film surface with $\\mathrm{SiO}_{2}/\\mathrm{PV}\\mathrm{A}$ coatings shows poor antifogging property after $168\\mathrm{~h~}$ (Fig. 7d). Fogging appeared on the surface of PE film containing (SS3010-PVA) coating. PVA is gradually dissolved under the action of water vapor, resulting in the poor antifogging property of PE film surface with PVA coatings after $1\\bar{6}8\\mathrm{~h~}$ (Fig. 7d). After $720\\mathrm{{h}}$ , the photographs of PE film with $\\mathrm{SiO}_{2}/\\mathrm{PV}\\mathrm{A}$ coatings are shown in Fig. 7b. Fogging also occurs on the PE film surface with coatings of $(\\mathrm{N}2010{-}\\mathrm{PV}\\mathrm{A})_{0.4}$ and Ludox N2010 as shown in Fig. 7b. The coating containing silica only gradually falls off under the scour of water film for a long time, resulting in poor antifogging performance. The $(\\mathrm{N}2010–\\mathrm{PV}\\mathrm{A})_{0.4}$ coating shows a slightly worse antifogging performance than $(\\mathrm{N}2010–\\mathrm{PV}\\mathbf{\\bar{A}})_{0.8,\\ 2}$ coatings because it has a low nano$\\mathrm{SiO}_{2}$ content and the interaction force is small with that of PVA. The composite coating tends to swell and slide on the surface of PE film under moisture. When the distance between nano- $\\mathrm{SiO}_{2}$ particles in the surface coating of PE film is larger than $190~\\mathrm{{nm}}$ or half the shortest wavelength $(380~\\mathrm{nm})$ ) of visible light, large droplets are easily formed without the effect of nanostructures, so the antifogging performance will begin to deteriorate.1 Such phenomenon is also verified in the $(\\mathrm{SS3010–PVA})_{0.8}$ coating because it has convex cell papillae structure with the biggest air voids. In Fig. 7b, the (N2010-PVA)0.8, $_2$ coatings have chemical (formation chemical bond of silicon oxycarbon) and physical interactions (PVA molecular chain is irregular and wound around nano- $\\mathrm{SiO}_{2}$ ) in PE film surface, which finally lead to the stable and durable antifogging performance. A more aggressive fogging test was performed by placing the PE thin films into the freezer at $20^{\\circ}\\mathrm{C}$ for about $20~\\mathrm{min}$ and then moving them into humid laboratory air. As seen in Fig. 8, the blank PE films are fully fogged, whereas the PE film with $(\\mathrm{N}2010–\\mathrm{PV}\\mathrm{A})_{0.8}$ coating remains fog free. As a special material with more hydroxy groups, silica and PVA have been used to achieve the antifogging properties. In the research, the $\\mathrm{SiO}_{2}/\\mathrm{PV}\\mathrm{A}$ coating surfaces are designed to form a special nanostructure, which is similar to the structure of fly compound eye (Supporting Information 2). The hydroxyl group in PVA condenses with the hydroxyl group of silica to form a gel. The gel acts as a crosslinking point in the hydrophilic coating, improving the water resistance of the PVA film. The corona modification can cause pits and oxygen-containing groups on the surface of the PE film.36,49 The thermal expansion coefficient of the PE film and nano- $\\mathrm{SiO}_{2}$ is different during the drying process, which causes the large particles of nano- $\\mathrm{\\dot{\\mathbf{SiO}_{2}}}$ to be anchored like nails on the surface of the PE film. The PVA film containing hydroxyl group exists next to the large particles of $\\mathrm{SiO}_{2}$ . The nano- $\\mathrm{SiO}_{2}$ particles play the role of nails in this case. The PVA film is nailed to the PE surface. This special structure makes the water flow easily on the surface and also reduces the scour effect of the water to the $\\mathrm{SiO}_{2}$ particles. The special nanostructure of $\\mathrm{SiO}_{2}/\\mathrm{PV}\\mathrm{A}$ composite plays an important role in improving the stability of antifogging coatings.  \n\nThe transmission spectra $(350-670~\\mathrm{nm})$ ) of $\\mathrm{SiO}_{2}/$ PVA-coated PE films are shown in Fig. 9. Clearly, in Fig. 9, the biggest transmittance of all samples reaches more than $90\\%$ in the visible light range $(400-670~\\mathrm{nm})$ . The transmittance of the coatings PVA, (N2010- $\\mathrm{PVA})_{0.4}$ , $(\\mathrm{N}2010–\\mathrm{PV}\\mathrm{A})_{0.8}$ , $(\\mathrm{N}2010{\\mathrm{-}}\\bar{\\mathrm{P}}\\mathrm{V}\\mathrm{A})_{2}$ , and Ludox N2010 shows a trend of decreasing first and then increasing with the addition of silica, which has a negative correlation with the roughness of the surface of the coatings. The coatings $\\mathbf{\\bar{(N2010-PVA)}_{0.8}}$ and (SS3010-PVA) $_{0.8}$ have large roughness (7.6 and $8.6\\ \\mathrm{nm}$ ), and the transmittance of the surfaces is lowered. In Fig. 9, the disadvantage is that the $(\\mathrm{N}2010{-}\\mathrm{PV}\\mathrm{A})_{0.8}$ hydrophilic coating with good antifogging performance slightly decreases the light transmittance of the PE film, but the biggest transmittance still exceeds $90\\%$ $(350-670~\\mathrm{nm}$ ).  \n\n![](images/14e31784b1d5c0dd5c0db12add2c9b7e1f43c2d2e97b82f6a4df09d3c1c9119e.jpg)  \nFig. 7: Fogging test image on PE film surface with nano-SiO2/PVA hydrophilic coatings (a) nano-SiO2/PVA $(\\mathsf{p H}=7)$ after 0.5 h, (b) nano-SiO2/PVA ( $\\left[\\mathsf{p H}=7\\right)$ after $720\\ h$ , (c) nano-SiO2/PVA $\\left[\\mathsf{p}\\mathsf{H}=\\mathsf{10}\\right]$ after $\\pmb{0.5}\\hbar$ , (d) nano-SiO $\\mathsf{\\pmb{\\mathscr{2}}}^{\\prime}\\mathsf{P}\\mathsf{V}\\mathsf{A}$ $\\left\\langle\\mathsf{p}\\mathsf{H}=1\\mathsf{0}\\right\\rangle$ ) after 168 h  \n\n![](images/0ef80da9493017f975390b64025b64c253bc0c61b5d03ba0947ed2def3d7c1ee.jpg)  \nFig. 8: Freeze tests. Fogging response being removed from 2 $\\mathsf{\\pmb{20}}^{\\circ}\\mathsf{\\pmb{C}}$ freezer to humid laboratory environment. (a) PE film uncoated, (b) PE film with $(\\mathsf{N2010-P V A})_{0.8}$ coating",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# The mechanical properties  \n\nFor the purpose of actual application, the mechanical properties (water-resisting and wear-resisting property) of $\\mathrm{SiO}_{2}/\\mathrm{PV}\\mathrm{A}$ hydrophilic coating must be considered. It was preliminarily assessed by the impact of a water scour. In this study, the water flowed out for $12\\mathrm{~h~}$ on $(\\mathrm{N}2010–\\mathrm{PV}\\mathrm{A})_{0.8}$ coating surface. When water drop was in contact with the hydrophilic coating, it immediately spread out on the surface (Supporting Information 3). These water scour tests were repeated three times. After the water flushing test of the coating, the properties of the coating were analyzed (Fig. 10a). The SEM image showed that nano- $\\mathrm{SiO}_{2}$ was still present on the surface of PE films. The contact angle on the surface of PE film increased from $22.9^{\\circ}$ to $44.2^{\\circ}$ , it still remained hydrophilicity. Subsequently, the thin film was washed for up to 20 cycles using a sponge at a speed of 50 cycles per minute. If the hydrophilic coating was not washed off, it was believed to have good washability and could endure practical washing. After washing, the SEM image of PE thin film became smooth (Fig. 10b), and it also maintained a low water contact angle $(37.8^{\\circ})$ and good antifogging property. Therefore, the current hydrophilic coating showed good mechanical properties.  \n\n![](images/d96aae71e89eca181f062efdf8f50282c0db3e24b9dcdccd81d1c50418092ce7.jpg)  \nFig. 9: Transmission spectra of PE film with nano- $\\bullet\\mathrm{i}0_{2}/$ PVA hydrophilic coatings. (a) Blank PE film, (b) PVA, (c) $(\\mathsf{N}2010\\mathrm{-}\\mathsf{P}\\mathsf{V}\\mathsf{A})_{0.4}$ , (d) $(\\mathsf{N}2010{\\circ}\\mathsf{P}\\mathsf{V}\\mathsf{A})_{0.8}$ , (e) $(N2010\\ –\\mathsf{P V A})_{2}$ , (f) Ludox N2010, (g) $(\\Im\\Im3010\\mathrm{-}\\mathsf{P V A})_{0.8}$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# Conclusions  \n\nIn summary, the hydrophilic coating of $\\mathrm{SiO}_{2}/\\mathrm{PV}\\mathrm{A}$ with high light transmittance and durable antifogging properties was prepared by solution blending method with simple and low-cost one-step dipping technique. The influence of different $\\mathrm{SiO}_{2}$ contents and $\\mathrm{\\pH}$ on the hydrophilic coating was discussed. Dynamic laser particle and Fourier transform infrared spectra data showed that the $\\mathrm{SiO}_{2}$ particles interacted with PVA molecular chain by forming a small amount of $_{\\mathrm{Si-O-C}}$ chemical bonds. The chemical structure can improve the strength and water resistance of the hydrophilic coating. SEM and AFM images of PE film containing $(\\mathrm{N}201\\bar{0}{\\cdot}\\mathrm{PV}\\mathrm{A})_{0.8}$ coating showed that $\\mathrm{SiO}_{2}$ nanoparticles were dispersed in PVA with good compatibility, forming a uniform papilla-like structure. The large roughness $(7.6~\\mathrm{nm})$ had a magnifying effect on the hydrophilicity of the coating, which decreased the contact angle from $99.5^{\\circ}\\$ to $22.9^{\\circ}$ . The maximum transmittance of the PE film with SiO2/PVA coatings between 560 and $700~\\mathrm{nm}$ was over $90\\%$ . The antifogging time was more than 1 month under $60^{\\circ}\\mathrm{C}$ by QB/T 4475-2013 standard. The water-resisting and wearresisting property tests showed that the current hydrophilic coating showed good mechanical properties. The current approach was facile, effective, and low cost, and had applications in the fields of eyeglasses, mirrors, face shields, camera lens, greenhouse claddings, and medical instruments.  \n\n![](images/817cb5005a9de8dd7dff610bf9dd2cc18aeb7df50b893b36f8887df0dc4afe1a.jpg)  \nFig. 10: SEM images of PE film (N2010-PVA)0.8 coating (a) after 12-h water scour test, (b) after 20-cycle wear test. Insert shows a water contact angle image and fogging test image on corresponding PE film surface  \n\nAcknowledgments This work was supported by the Natural Science Foundation of Shandong Province (Grant Numbers ZR2019MB053; ZR2017MEM001; and R2019MEE018)",
+        "category": " Conclusions"
+    },
+    {
+        "id": 14,
+        "chunk": "# References  \n\n1. Sun, Z, Liao, T, Liu, K, et al., ‘‘Fly-Eye Inspired Superhydrophobic Anti-Fogging Inorganic Nanostructures.’’ Small, 10 (15) 3001–3006 (2014)   \n2. Nuraje, N, Asmatulu, R, Cohen, RE, et al., ‘‘Durable Antifog Films from Layer-by-Layer Molecularly Blended Hydrophilic Polysaccharides.’’ Langmuir, 27 (2) 782–791 (2011)   \n3. Lu, X, Wang, Z, Yang, X, et al., ‘‘Antifogging and Antireflective Silica Film and its Application on Solar Modules.’’ Surf. Coat. Technol., 206 (6) 1490–1494 (2011)   \n4. Hlavay, J, Gullbault, G, ‘‘Applications of the Piezoelectric Crystal Detector in Analytical Chemistry.’’ Anal. Chem., 49 1890–1898 (1977)   \n5. Bessell, JR, Flemming, E, Kunert, W, et al., ‘‘Maintenance of Clear Vision During Laparoscopic Surgery.’’ Minim. Invasive Ther. Allied Technol., 5 (5) 450–455 (1996)   \n6. 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Cao, L, Hao, H, Dutta, PK, ‘‘Fabrication of High-Performance Antifogging and Antireflective Coatings Using Faujasitic Nanozeolites.’’ Microporous Mesoporous Mater., 263 62–70 (2018)   \n21. Liu, H, Feng, L, Zhai, J, et al., ‘‘Reversible Wettability of a Chemical Vapor Deposition Prepared ZnO Film Between Superhydrophobicity and Superhydrophilicity.’’ Langmuir, 20 (14) 5659–5661 (2004)   \n22. Yang, F, Wang, P, Yang, X, et al., ‘‘Antifogging and Antifrosting Coatings by Dip-Layer-by-Layer Self-assembly of Just Triple-Layer Oppositely Charged Nanoparticles.’’ Thin Solid Films, 634 85–95 (2017)   \n23. Miyauchi, M, Shibuya, M, Zhao, Z, et al., ‘‘Surface Wetting Behavior of a ${\\bf W}{\\bf O}_{3}$ Electrode Under Light-Irradiated or Potential-Controlled Conditions.’’ J. Phys. Chem. C, 113 (24) 10642–10646 (2009)   \n24. Hu, J, Wu, S, Lou, B, ‘‘Research on Preparation of Transparent Hydrophilic Antifogging Acrylate Resin.’’ Mater. Sci. Forum, 704 92–101 (2012)   \n25. 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Zhao, J, Ma, L, Millians, W, et al., ‘‘Dual-Functional Antifogging/Antimicrobial Polymer Coating.’’ ACS Appl. Mater. Interfaces, 8 (13) 8737–8742 (2016)   \n31. Shibraen, MHMA, Yagoub, H, Zhang, X, et al., ‘‘Antifogging and Anti-frosting Behaviors of Layer-by-Layer Assembled Cellulose Derivative Thin Film.’’ Appl. Surf. Sci., 370 1–5 (2016)   \n32. Grube, S, Siegmann, K, Hirayama, M, ‘‘A Moisture-Absorbing and Abrasion-Resistant Transparent Coating on Polystyrene.’’ J. Coat. Technol. Res., 12 (4) 669–680 (2015)   \n33. Pirzada, T, Arvidson, SA, Saquing, CD, et al., ‘‘Hybrid Silica-PVA Nanofibers via Sol-Gel Electrospinning.’’ Langmuir, 28 (13) 5834–5844 (2012)   \n34. Tong, B, Cheng, C, Khan, MI, et al., ‘‘Double Cross-Linking PVA- $\\cdot\\mathrm{SiO}_{2}$ Hybrid Membranes for Alkali Recovery.’’ Sep. Purif. Technol., 174 203–211 (2017)   \n35. Liu, H, Yu, H, Yuan, X, et al., ‘‘Amino-Functionalized Mesoporous $\\mathrm{PVA}/\\mathrm{SiO}_{2}$ Hybrids Coated Membrane for Simultaneous Removal of Oils and Water-Soluble Contaminants From Emulsion.’’ Chem. Eng. J., 374 1394–1402 (2019)   \n36. Haq, AU, Boyd, A, Acheson, J, et al., ‘‘Corona DischargeInduced Functional Surfaces of Polycarbonate and Cyclic Olefins Substrates.’’ Surf. Coat. Technol., 362 185–190 (2019)   \n37. Topc¸u Kaya, AS, Cengiz, U, ‘‘Fabrication and Application of Superhydrophilic Antifog Surface by Sol-Gel Method.’’ Prog. Org. Coat., 126 75–82 (2019)   \n38. Ye, L, Zhang, Y, Song, C, et al., ‘‘A Simple Sol-Gel Method to Prepare Superhydrophilic Silica Coatings.’’ Mater. Lett., 188 316–318 (2017)   \n39. QB/T 4475-2013. ‘‘Long Term Anti-Drip Polyethylene Greenhouse Film with Coating.’’ S, 41602-2013   \n40. Liao, W, Teng, H, Qu, J, et al., ‘‘Fabrication of Chemically Bonded Polyacrylate/Silica Hybrid Films with High Silicon Contents by the Sol–Gel Method.’’ Prog. Org. Coat., 71 (4) 376–383 (2011)   \n41. Venckatesh, R, Balachandaran, K, Sivaraj, R, ‘‘Synthesis and Characterization of Nano $\\mathrm{TiO}_{2}{\\cdot}\\mathrm{SiO}_{2}$ : PVA Composite—A Novel Route.’’ Int. Nano Lett., 2 (1) 1–5 (2012)   \n42. Xu, Y, Li, Z, Fan, W, et al., ‘‘Density Fluctuation in SilicaPVA Hybrid Gels Determined by Small-Angle X-ray Scattering.’’ Appl. Surf. Sci., 225 (1) 116–123 (2004)   \n43. Iva´n, R, Gae´ tan, L, ‘‘Water Drop-Surface Interactions as the Basis for the Design of Anti-fogging Surfaces-Theory, Practice, and Applications Trends.’’ Adv. Colloid Interface Sci., 263 68–94 (2019)   \n44. Si, Y, Dong, Z, Jiang, L, ‘‘Bioinspired Designs of Superhydrophobic and Superhydrophilic Materials.’’ ACS Cent. Sci., 4 (9) 1102–1112 (2018)   \n45. Wenzel, RN, ‘‘Resistance of Solid Surfaces to Wetting by Water.’’ Ind. Eng. Chem., 28 (8) 988–994 (1936)   \n46. Cassie, A, Baxter, S, ‘‘Wettability of Porous Surfaces.’’ Trans. Faraday Soc., 40 546–551 (1944)   \n47. Liao, W, Huang, X, Ye, L, et al., ‘‘Synthesis of Composite Latexes of Polyhedral Oligomericsilsesquioxane and Fluorine Containing Poly(styrene-acrylate) by Emulsion Copolymerization.’’ J. Appl. Polym. Sci., 133 (21) 933 (2016)   \n48. Feng, C, Zhang, Z, Li, J, et al., ‘‘A Bioinspired, Highly Transparent Surface with Dry-Style Antifogging, Antifrosting, Antifouling, and Moisture Self-Cleaning Properties.’’ Macromol. Rapid Commun., 40 (6) 1800708 (2019)   \n49. Kalapat, N, Amornsakchai, T, ‘‘Surface Modification of Biaxially Oriented Polypropylene (BOPP) Film Using Acrylic Acid-Corona Treatment: Part I. Properties and Characterization of Treated Films.’’ Surf. Coat. Technol., 207 594–601 (2012)  \n\nPublisher’s Note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Review",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Research progress of UV-curable polyurethane acrylate-based hardening coatings  \n\nJunchao $\\mathtt{F u}^{\\mathrm{a}}$ , Li Wanga,⁎, Haojie $\\mathrm{Yu^{a,*}}$ , Muhammad Haroona, Fazal Haqa, Wenlei $s\\mathrm{{hi}^{\\mathrm{{b}}}}$ , Bin Wub, Libo Wangc  \n\na State Key Laboratory of Chemical Engineering, College of Chemical and Biochemical Engineering, Zhejiang University, Hangzhou 310027, China b Suzhou Taihu Electric Advanced Material Ltd., Fenhu New & Hi-Tech Industrial Development Zone, Wujiang 215200, China c Ningbo Haoxin YURON New Material Co., Ltd., NO. 7, Dajiang North Road, Jiangkou Sub District, Fenghua 315514, China",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# A R T I C L E I N F O",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# A B S T R A C T  \n\nKeywords:   \nUV-curable   \nPolyurethane acrylate Hardening coatings  \n\nWith the development of society, plastics play a significant role in daily supplies owing to their advantages. Whereas, insufficient scratch resistance and vulnerable plastic surfaces result in the constraint of their range of application fields, for instance, electronic products. Hence, it is a highly desirable objective of researchers to investigate hardening coatings for protecting plastic surfaces, by selecting polyurethane acrylate (PUA) as filmforming materials attributing to their adjustable features. This article reveals components of PUA and principles for its hardening modification, and summaries various methods of hardening modification of PUA-based coatings, such as improving the crosslinking density, strengthening hydrogen bonding, incorporating rigid groups into molecular structure, introducing inorganic nanoparticles into resin matrix and transferring linear PUA into hyperbranched analogs. Moreover, optimal strategies for the preparation of PUA-based hardening films from above five tactics are discussed.",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# 1. Introduction  \n\nPlastic is an indispensable material in the industry to produce daily supplies and high-tech products for specific applications owing to its lightweight, easy process and low cost, such as optical glasses, electronic product shells or protective films of precision instruments and so on. However, as optical resins and instrument housings, the insufficient mechanical strength of plastic results in the constraint of their range of application fields, because poor scratch resistance causes soft plastic surfaces which can be easily damaged [1–3].  \n\nUp to now, there exist many methods to improve the hardness of plastic which can be divided into three groups. One is an additive modification, in which hardening additives are added to plastics. The commonly used hardening additives are rigid inorganic fillers (kaolin or silica hydrated etc.) and fibers. However, these additives have significantly increased the surface roughness of plastic products, which brings bad influence to plastic. Second is blocking or grafting at the molecular level, which can be operated by incorporating polar groups or rigid groups into molecular chains of plastic to increase the crystallinity or rigidity of plastic, respectively. The hardness of plastic can be enhanced, possibly while the other mechanical properties will be affected, such as the considerable decrease in toughness. Third is hardening modification of plastic surface, which means that only the hardness of surface is promoted, and the internal hardness of products does not change. The examples are coating, plating and surface treatment. The coating has lower cost, easier process and slighter influences on the other performances of plastic than the above hardening modifications. So, it is an urgent need to extend the application domain of hardening coatings with high mechanical properties in plastic products.  \n\nCurrently, considerable efforts have been made to investigate highperformance UV-curable coatings through changing materials or operational parameters [4–6]. Compared with thermal curing, UV-curing technology is noted as 5E, which stands for Efficiency, Energy saving, Enabling, Economical, and Environmental friendly [7–12]. Generally, UV-curing systems mainly consist of three basic components: a monoor multifunctional acrylate monomer, an acrylate prepolymer, and a photo-initiator. Until now, diverse sorts of additives are constantly employed in such systems [13,14].  \n\nAs the one of most popular resin, PUA has attracted much attention in UV-curable coatings attributing to its excellent flexibility, prominent adhesion on substrates and a variety of adjustable features. [15] Significant results can be acquired when it is applied in coatings for metals, mobile phones, and other electronic products. However, the density and content of photosensitive groups of the existing photo-curable resins are not abundant, and have influence on the film performance. For example, the hardness of coating films is poor and UV-curing speed is slow which limits its practical applications in some fields [16,17]. Therefore, improving these performances of PUA is priority.  \n\nIn this review paper, the components of PUA and principles for hardening modification of PUA-based coatings is revealed in the first part. Afterward, the second part will be devoted to review diverse methods of its hardening modification. Eventually, a discussion about the optimal approaches for the preparation of PUA hardening coatings will be drawn.",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2. Compositions of PUA and principles for hardening modification of PUA-based coatings  \n\nPUA is an important category of photo-curable crosslinking resins, and is also widely employed in protective coatings. It is based on polyurethane, and then the double bond of acrylates is introduced into the molecular chain terminal of polyurethane, eventually, oligomers are used to initiate double-crosslinking reaction under the action of photoinitiators [18].",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.1. Compositions of PUA  \n\nPUA comprises a significant category of polymeric materials whose properties can be tailored by regulating its compositions, the ratio of polyurethane/polyacrylate or -NCO/−OH, and the structure of raw materials [19–22]. The molecular structure of PUA mainly consists of urethane segments, the main chain of polyols or polyamines, and acrylate hydroxyalkyl ester segments (Fig. 1). The curing characteristics are determined by the acrylates located in the segments, and the structure and composition of the resin backbone mostly affect the properties of products.  \n\nGenerally, researchers frequently employ diisocyanates containing toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI) as the urethane segments, including ethylene diamine (EDA) or ethane glycol (EG) etc. as chain extenders (Table 1) [18]. Attributing to the fact that diisocyanates possess different molecular structures, bringing diverse features for segments, we can acquire the properties of coatings what we want through varying the category or content of diisocyanates. For example, selecting HMDI and MDI for improving mechanical properties of resins owing to the cyclic structure or benzene rings they have, or choosing HDI to receive flexible coatings because of the exiting long-chain alkane, or using IPDI to control the reaction process which can design the chemical structure of compounds ascribing it to the different reactivity of two isocyanate groups of IPDI at low temperature. For the parts of main chain of polyols or polyamines, investigators usually employ polyethylene glycols (PEG), polytetrahydrofuran (PTMEG), poly (caprolactone glycol) (PCL), or polycarbonate diols (PCDL) etc. as flexible chain extenders whose terminals contain many hydroxyl or amino groups (Table 1) which can react with diissocynates by semi-adduct reaction. For the acrylate segments, we constantly choose hydroxyethyl acrylate (HEA) as end-capper to obtain unsaturated bonds. Nevertheless, in order to get compounds containing high functionality, raise the hardness or mechanical properties of coatings after curing, sometimes, we are more willing to introduce trimethylolpropane diallyl ether(TMPDE) or pentaerythritol triacrylate (PETA) containing lots of unsaturated bonds into system which are used as end-capping reagent (Table 1).  \n\nWhereas, in order to follow new policies of sustainable chemistry development, academic and industrial researchers have to seek for some greener resources or processes to replace hazardous chemicals and rigorous reaction conditions [23]. The greener raw materials can be divided into two groups. One is the preparation of non-isocyanate polyurethane (NIPU) by transurethanization polycondensation (Fig. 2), such as the reaction between cyclic carbonate and diamine, representing one of the most promising surrogates to the traditional route for synthesizing polyurethanes [24–28]. Another is discovery of renewable resources, for instance, vegetable oils, which are the most promising sustainable building blocks that can efficiently substitute for fossil-feedstock-derived polyester and polyether polyols [29]. Vegetable oils are triglycerides mainly consisting of saturated and unsaturated fatty acids, such as soybean oil [30], castor oil [31] or jatropha oil [32] and so on. The relationships between structure-property and resulting polyurethanes dramatically depend on the kind of triglyceride used [33], the category of diisocyanates and the degree of cross-linking28].  \n\nIn another aspect, some researchers add several reactive diluents into UV-curing systems (Table 1), such as tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA) or pentaerythritol tetraacrylate (PETTA), not only to decrease the viscosity of curing system, but also to increase the crosslinking density of coating films after cured owning to its plentiful double carbon bonds. For the reason that PUA occupies so many adjustable characteristics which combines the advantages of both acrylic and polyurethane resins, it has high reactivity, excellent flexibility, adhesion, low temperature resistance, abrasion resistance, chemical resistance and elasticity.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.2. Principles for hardening modification  \n\nFor the past few years, a large number of researchers have made much effort to modify the hardness of PUA coatings, some of which show excellent results. [11,12] We can receive the conclusion, whether from strategies they have used or the PUA molecular structure (Fig. 1), existing four techniques to elaborate hardening modification.  \n\nFrom Fig. 1, we can see that PUA can be divided into three sections, section a contains double bond functional groups, which are mainly used for photo-curing crosslinking, section b includes urethane bonds, which forms the hard segments, and section c comprises with weak or no other intermolecular forces, forming the soft segments. Sequentially, some tactics will be utilized. We can select section a to improve the hardness of PUA, promoting its functionality (unsaturated bonds), thereby increasing the crosslinking density to achieve more compact network structures [34], or incorporating some chain extenders that can form more hydrogen bonds into section b or section c reinforcing hydrogen bonding, accordingly strengthening the micro-phase separation or producing mixed phases between hard and soft segments, respectively, and then increasing the hardness [35], or introducing rigid groups (containing cyclic groups) for section c which can promote the hardness of soft segment owing to its rigidity [36]. Certainly, adding some inorganic fillers into the resin, such as nano- $s\\mathrm{iO}_{2}$ or $z_{\\mathrm{{nO}}}$ and so on, can also endow the considerable result of hardness for composite films. [10] The inorganic nanoparticles have capabilities to remarkably improve physical properties of polymers due to the strong interaction between particles and polymer interface caused by nanometer effect and its high specific area. The above strategies can not only be employed alone but also be united, to achieve the best outcomes.  \n\n![](images/fde373c0c2e43d1d2215f732ad74ba994287e5fbc5ffaafb8a14c107031fdea3.jpg)  \nFig. 1. General chemical structure of PUA.  \n\n![](images/69bc1fcc67aee22316961b19f266dbdeeb050647c625e68d78bfeae95e7c121c.jpg)  \nFig. 2. Overview of synthetic routes to polyurethanes. [23] Copyright 2015. Reproduced with permission from American Chemical Society [23]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 3. Strategies of hardening modification of PUA  \n\nFrom the mechanisms of hardened modification for PUA, we can get that there are five methods to enhance the hardness of coating films, which include improving the crosslinking density, strengthening the effect of hydrogen bonding, introducing rigid groups or adding inorganic nanoparticles into matrix to augment the rigidity of films and transferring linear PUA into hyperbranched PUA.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3.1. Improving the crosslinking density  \n\nTheoretically speaking, there are two ways to reinforce the crosslinking density. One is forming multi-functional groups (carbon double bonds) and another is the introduction of silicone coupling agent. Silanol groups produced by the silicone coupling agent will react with each other to form siloxane bonds (Si-O-Si), consequently forming stable Si-O-Si siloxane networks [37]. The crosslinking result of silane coupling agents enhances the hardness and abrasion resistance of coatings.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3.1.1. Polyfunctionality modification  \n\nAs a rule, the modification of double bonds content exists two strategies. One is adding reactive diluents [38] and another is promoting functionality of oligomers [39].  \n\nFor the reactive diluent, Xia et al. [40] synthesized a cluster of UVcurable polyurethane mixed components including (Nethylperfluorooctylsulfonamido) methyl acrylate (EFCSA) and pentaerythritol tetra (3-mercaptopropionate) (PETMP, a reactive oligomer). Subsequently, EFCSA and PETMP reacted with (2-hydroxyethyl acrylate)-terminated polyurethane resin to fabricate coatings (Fig. 3a). With increasing contents of PETMP, the pencil hardness was raised from 2B to HB due to the promotional crosslinking density of coatings caused by the increasing of thiol groups. Meanwhile, one point should be emphasized that this study introduced thiol-ene click reactions into crosslinking system to form polyurethane coatings, offering some benefits like high curing rate, low energy consumption [41] and enhanced mechanical properties due to its high reactivity for emerging highly dense networks. Li et al. [42] used PETA as end-capper and PETTA as reactive diluents to form PETA/PETTA composite system, including many unsaturated double bonds, subsequently enhancing the crosslinking density of films (Fig. 3c). The results revealed that dense network structures were formed by introducing PETTA with higher reactivity into the polyurethane molecule after cured and pencil hardness was improved from 2H to 3H. And the best consequence of mechanical properties was acquired when nearly $35\\mathrm{wt.\\%}$ PETTA was added (Fig. 4d). It was found that if the weight ratio of PETTA was tremendous, it might bring something worse effects to films owing to its high reactivity, which can take the shape of compact networks sharply, and then restrict the diffusion and motion of PETTA or radicals out of networks. In consequence, it brought a reduction of the crosslinking density because of premature termination of polymerization that was caused by partially unreacted double bonds trapped in the polymeric networks [15]. On the same method, Xu et al. [43] introduced tripropylene glycol diacrylate (TPGDA) as a multifunctional acrylate molecule reactive diluents into resins (Fig. 3b) that can form the preferable crosslinking structure, and then raise the coating hardness due to two unsaturated double bond $\\mathbf{\\tilde{\\Sigma}}.\\mathbf{C}=\\mathbf{CH}_{2})$ ) and shorter soft chains of TPGDA. As a whole, we can conclude that reactive diluents play an important role in the film hardness attributing to their high functionality.  \n\n![](images/b4f305dd9a76f73621e253bdd0dc16cd6cbbccedbdd4edebb16b37e03a8e3a56.jpg)  \nFig. 3. a) Preparation process of HFTPU. [40] b) Reaction mechanism of UV-WPUA based on PETA/PETTA [42]. c) The formation of UV-WPUA coating film [43].Copyright 2013. Copyright 2014. Reproduced with permission from John Wiley and Sons [42]. Reproduced with permission from John Wiley and Sons [43].  \n\n![](images/99d4c5deca0cf58a83f8e79afbe2ede692ad07edc47acb7cc962610373d3d1c8.jpg)  \nFig. 4. a) Synthesis process of UV-WPUA emulsion and b) Tensile properties of UV-WPUA. [45] c) Synthesis of fluorinated/methacrylated soybean oil [48]. d) Tensile properties of UV-WPUA [42]. Copyright 2014. Reproduced with permission from Elsevier [45]. Copyright 2009. Reproduced with permission from Elsevier [48]. Copyright 2014. Reproduced with permission from John Wiley and Sons [42].  \n\nFor the functionality of oligomers, Yuan et al. [44] developed a series of PUA oligomers terminated with multiple unsaturated bonds by using PETA as an end-capping reagent. Poly (propylene oxide) and PETA have significant effects to furnish more double bonds, which can increase the content of multi-functional groups. The results demonstrated that the functionality and content of oligomers (PETA content) of PU prepolymer have a huge impact on the film hardness, raising from 4H to 6H when PETA was added. Li et al. [45] introduced both castor oil (CO) and end-capper of PETA into waterborne polyurethane (WPU) molecules to obtain UV-WPUA oligomers containing multiple unsaturated double bonds and polar groups attributing to the high functionality and existing ester groups of CO (Fig. 4a), and the excellent mechanical properties was obtained. Simultaneously, researchers found that when the additive amount of CO was more than $6.86\\%$ , tensile strength received a sharp reduction (Fig. 4b). The excessive crosslinking results in some negative effects in the molecular level, such as molecular chains hardly moved freely and the mechanical strength decreased. Nevertheless, owing to its good advantages, castor oil and its derivatives have been considerably employed in polyurethane coatings field. [39,46,47] In another article, Kahraman et al. [48] used epoxidized soybean oil and methacrylic acid to synthesize methacrylated soybean oil terminated with multiple double bond, and then introduced it into PUA resins to get the harden coating (Fig. 4c). The result exhibited that the modification of film hardness was great, which can be supposed to the modified soybean oil acting as a cross-linking agent, because its polyfunctionality will raise the crosslinking behavior, afterward developing a tight network structure. Coincidentally, Li et al. [30] disclosed the similar consequence that acrylated epoxidized soybean oil (AESO) can increase the crosslinking density and form network structures during the curing process. The reason can be attributed to the fact that AESO contains two types of functional groups: one is hydroxyl groups which can covalently bond by reacting with other reactive groups or form hydrogen bonds to strengthen the effect of intermolecular chains, and the another is double carbon bonds that can be UV-cured.  \n\nObviously, the increment of double bonds content of curing systems or oligomers can make the chemical crosslinking density raise as well, so that the crosslinking network structures of components are more compact, reducing the free space for chain motion. Subsequently, the overall hardness and abrasion resistance of film is enhanced. With aggrandizing functionalities of compounds, however, the viscosity of system remarkably ascend which is not conducive to the leveling of coatings, resulting in insignificant increase in hardness. As a result, the lower viscosity of the system could promote a full crossing-linking reaction to form a denser crossing-linking structure by its leveling of films and motion of free chains [44].  \n\n![](images/b6ceeea9a83e74413a1237f639e8fafbcd6b42f8bfdf96e4c3bc595f21042385.jpg)  \nFig. 5. Schematic diagram of PDMS-based polyurethane acrylate oligomers. [52] Copyright 2011. Reproduced with permission from Elsevier [52]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3.1.2. Siloxanes and silane coupling agents modification  \n\nNumerous researchers have certified that preparing harder films only with siloxanes and silane coupling agents through sol-gel technique can be done successfully [49], which can even raise the pencil hardness of coatings from 2B to 5H [50]. It can be attributed to the formation of stable Si-O-Si siloxane networks [51]. The most studied and applied silicon-containing acrylate monomers are silane coupling agents containing only one silicon atom, such as $\\upgamma$ -methacryloxypropyltrimethoxysilane (MPTMS), trimethylsilyl methacrylate (TMSM) and so on. $\\upgamma$ -Methacryloxypropyltris (trimethylsiloxy) silane containing several silicon atoms is also a commonly used monomer.  \n\nFor the modification of PUA coatings, hydroxy-terminated polydimethylsiloxane (PDMS) was introduced into the soft segments of PUA dispersions by Hwang et al. to reinforce the thermal and surface property (Fig. 5) [52]. From the results, they revealed that the curing rate and conversion of unsaturated bonds were diverse when end-cappers containing different functionality were added. For the conversion of unsaturated bonds, PDMS with mono-functional methacrylate obtained a little increment, but PDMS with high functionality reduced slightly. The reason could be supposed to that the former can be attributed to chain flexibility of PDMS, and the latter may be influenced more by the steric hindrance caused by PDMS. Furthermore, coatings with PDMS, especially including tri-acrylate end-capping, showed high initial modulus and excellent tensile strength and got a sharp reduction of elongation at break due to the polyfunctionality of tri-acrylate endcapping. Park et al. [37] investigated the effect of silane coupling agents in coatings, and introduced acrylic monomer and vinyltrimethoxysilane (VTMS) to acquire the UV-curable polyurethane acrylates (Fig. 6a). The consequences exhibited that as the amount of VTMS augmented, the storage modulus/hardness of the UV-cured coating enhanced significantly and the tensile strength/glass transition temperature raised slightly (Fig. 6b and c), whereas, the elongation at break decreased sharply owing to the occurrence of rigidity by the stable and dense Si-O-Si network structures. Wang et al. [36] adopted  \n\nMPTMS (KH-570) as the silane coupling agent and then found that the introduction of KH-570 can form a more compact spatial structure by increasing crosslinking density, afterwards improving the tensile strength of the latex films properly while keeping other performances well.  \n\nFor silane coupling agents, they can condense by themselves to form the structure of polyhedral oligomeric silsesquioxane (POSS), which can obtain the nanometer effect and excellent mechanical properties. Octavinyl-POSS was incorporated into UV-curing PUA matrixes by Kim et al. [53] to prepare hybrid nanocomposite films with distinctive thermal and mechanical properties. The PUA was consisted of poly (tetramethylene glycol), IPDI and HEA. Researchers found that the Shore A hardness (Hardness value measured by Shore hardness tester) of coating raised from 70 to 85 by adding and increasing POSS content in hybrid coatings. Addition of silicones to the matrix made films harder which can be ascribed to the increment of the cross-linking density as well as the reinforcing effect produced by the multi-functionality and rigidity of octavinyl-POSS. In another research, the silane coupling agent was utilized for the modification of interfacial compatibility. Kim et al. [54] gained the UV-curable PUA based hybrid materials, and MPTMS as a silane coupling agent was incorporated into the matrix to promote interfacial attraction between main organic part and inorganic silicate in the curing system, to receive a high degree of cross-linking and compact organic-inorganic network structure. By adjusting the adding quantity of MPTMS, morphological variation was obtained in Fig. 7. From the figure, we can see that with increasing the additive amount of the silane coupling agent MPTMS, the dispersion of silica particles was remarkably improved, eventually the stable and homogeneous morphology can be observed. Furthermore, this phenomenon delivered a significant information that raising interaction between organic and inorganic phases can substantially suppress the tendency of agglomeration among nano-inorganic particles and bring the silane coupling agent into full play.  \n\nFrom the above discussions, some conclusions can be made that the addition of siloxanes and silane coupling agents reinforce the crosslinking density of the system to form a dense network structure owning to its compact and stable siloxane networks generated from silanol groups, to acquire the effect of improving coatings hardness. Whereas, siloxanes are easily crosslinked together and then make clusters, which brings inferior effects to coatings, such as the low increase in hardness and high reduction of elongation at break after cured [55]. So, in order to receive excellent results of modification, we should control the number of siloxanes in a moderated range.  \n\n![](images/646cd109986830ce5c5445e4efd164e07fa4cfdd4fe5739c16471413a45acb4d.jpg)  \nFig. 6. a) Synthetic route of UV-curable PUAs. b) The storage modulus and c) Stress-strain curves of UV-cured coatings (FPUA $6/0$ , FPUA $_{6/3}$ , FPUA $6/6$ and FPUA 6/ 9). [37] Copyright 2015. Reproduced with permission from Springer Nature [37].  \n\n![](images/66aee6f7485de02b919463fd0b94329d16cdf435304977a48af2e686880a94e3.jpg)  \nFig. 7. SEM images of acrylate $\\mathrm{\\Delta}^{\\prime}\\mathrm{SiO}_{2}$ hybrids without MPTMS, a) $\\mathrm{TEOS}=0.01\\mathrm{mol}$ , b) $0.03\\mathrm{mol}$ , and hybrids with addition of MPTMS, c) $\\mathrm{TEOS}=0.01\\mathrm{mol}$ , d) $0.03\\mathrm{mol}$ . [54] Copyright 2010. Reproduced with permission from Springer Nature [54].  \n\n![](images/cea78c79ee44d5e6902d995339e84f8b797920de3a239572485add264c8a9b2f.jpg)  \nFig. 8. a) Preparation of soybean-oil-based WPU dispersions. b) The relation between glass-transition temperature $(T_{g})$ of the SPU coatings and the hydroxyl number of the MSOL. c) Stress-strain curves for MSOLs-based SPU films with different hydroxyl numbers. [29] Copyright 2008. Reproduced with permission from American Chemical Society [29].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3.2. Strengthening hydrogen bonding  \n\nPUA contains thermodynamically incompatible hard segment and soft segment units. The hydrogen bonding generated between hard segments form physical crosslinking among polymer molecular chains which have a significant effect on physical properties of polymers, and are easy to produce mixed phases, giving the material excellent overall performance [29,56].  \n\nLu et al. [29] incorporated a derivative of soybean oil (MSLO) into prepolymers to prepare a cluster of vegetable-oil-based WPU dispersions, among them, hydroxyl groups of MSLO ranged from $2.4\\mathrm{up}$ to 4.0 (Fig. 8a). Certainly, MSLO can play the role of UV-cured functional groups owing to its unsaturated double bonds as well. In addition, the experimental results disclosed that hydroxyl functionalities of the MSOLs had significant effects in controlling mechanical properties of coatings. With increasing the $-\\mathrm{OH}$ number in MSOL, the $T_{g}$ value and mechanical properties were strengthened due to the higher physical cross-linking in the soft segment provided by hydrogen bonding (Fig. 8b and c). Jofre-Reche et al. [57] modified the abrasion resistance and hardness of PU with polycarbonate diol (PCD) and polytetramethylene glycol diol (PTMEG). The results revealed that PUPTMEG possessed poor abrasion resistance, while the hardness and wear resistance of PU-PCD and PU- $50\\%$ $\\mathrm{PCD}+50\\%$ PTMEG were significantly improved, almost up to 60 Shore A hardness, which attributed to stronger interactions of the carbonate groups in soft segments that were able to create hydrogen bonds with urethane groups of hard segments, producing a higher miscibility of the hard and soft domains and then reinforcing mechanical properties. Definitely, we should note that the role played by hydrogen bonds is mainly augmenting the abrasion resistance of coatings, which makes resins tough owing to its role of buffers, conversely, restricting the improvement of the hardness of films.  \n\nAnother approach is not the modification of oligomers but blending. Zhang et al. [35] successfully acquired a new type of waterborne PUPA ester emulsion through a physical blend between polyurethane emulsion (PU) and polyacrylic ester emulsion (PA). The film properties of  \n\n![](images/500a8f3ab9e167f8ae48d9f86505a1d28bbd23bb578fb1d1b41c3cfa652ba660.jpg)  \nFig. 9. a) Formation of the PUPA polymer particles. [35] b) The different patterns of $\\scriptstyle{\\mathsf{C}}=0$ in polyurethane: (a) free carbonyls, (b) disordered H-bonded carbonyls, (c) ordered H-bonded carbonyls. c) XRD graphs of the WPU and WFPU coatings [59]. Copyright 2013. Reproduced with permission from Springer Nature [35]. Copyright 2017. Reproduced with permission from Elsevier [59].  \n\nPUPA coating was characterized and exhibited reasonable hardness, improving the stability of the PUPA coating by the hydrogen bonding between $\\boldsymbol{\\mathrm{N-H}}$ of PU and $\\scriptstyle0=\\mathbf{C}$ of PA [58]. The forming mechanism of hydrogen bonding between PU and PA was represented and shown in Fig. 9a. From the above researches, it is worth noting that the introduction of more hydrogen bonds into soft segments can increase the interaction between hard and soft segments to enhance mixed phases, and then endow coatings with favorable properties. The method strengthens hydrogen bonding between hard and hard segments to raise micro-phase separation, whereas, also can work pretty well to increase the hardness of films. As an instance, Yang et al. [59] developed a series of novel waterborne fluorinated polyurethane and acquired the conclusion that the increment of H-bonded carbonyl groups in hard domains has a significant effect on crystallization, bringing the increase of crystalline in hard domains (Fig. 9b), which was contributed to raising the hardness of films. All samples showed a strong peak at $2\\Theta=19^{\\circ}$ (Fig. 9c), demonstrating that micro-phase separation between the soft and hard segment was generated to endow coatings with excellent properties because of the crystallinity in the hard domains. This enhancement can be related to the restricted movement of polymer chains caused by the larger degree of hydrogen bonding between the hard and hard segments [29,60]. However, the large degree of micro-phases separation will lead to uneven film surface because of its crystallization on the surface.  \n\nAlthough the hydrogen bonding improves the mechanical properties of materials, its enhancement in hardness is limited, because it mainly improves the abrasion resistance of coatings. The reason can be attributed to taking the shape of buffers by hydrogen bonding, which will absorb impact energy when subjected to force. At the same time, the hydrogen bonds in coatings break at relatively high temperatures, whose thermal stability is relatively poor.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.3. Incorporation of rigid groups  \n\nResearches have shown that rigid groups give the PUA a very high hardness improvement, for example, bisphenol A epoxy resin itself contains benzene rings, whose hardness after curing is very considerable [36]. In contrast, it was demonstrated that the addition of compounds containing tough chains into epoxy resins or PUA coatings will decrease coating hardness and increase damping properties [61]. Rigid groups that can be introduced into PUA include benzene rings or sixmembered heterocyclic rings, especially six-membered heterocyclic rings that can form large $\\uppi$ bonds, such as triazine groups, which not only provide considerable rigidity, but also endow coatings with antiyellowing.  \n\nShi et al. [62] introduced melamine into PUA matrix to get phasechange heat-storage UV-PUA coatings by microencapsulated technology, where melamine-formaldehyde shell and paraffin core were synthesized to form phase change materials. Certainly, the melamine possesses triazine group that can take the shape of large $\\uppi$ bonds. Attributing to dense crosslinking density and rigidity of melamine-formaldehyde, the mechanical properties of films were enhanced [63]. Besides, Pathak et al. [64] selected hexamethoxymethylmelamine (HMMM) as a crosslinking agent, which was incorporated into resin system to prepare films, getting the conclusion that triazine groups of HMMM play a significant role in strengthening mechanical properties of coatings owing to its rigidity. In another study, Mishra et al. [65] synthesized a new intermediate through the reaction between epoxy resin and dimer fatty acid, which called dimer acid modified epoxy (DME) polyol containing both hydroxyl and epoxy groups (Fig. 10a), and then prepared UV-curable polyurethane by adding trimethylolpropane tris(3-mercaptopropionate) as a cross-linking agent. Evaluation of cured samples showed that with incresing the amount of thiol ratio, the significant improvement in storage modulus (Fig. 10b) and hardness can be observed. Furthermore, the high hardness value of coatings can be attributed to the rigidity of DME, which contains rigid phenyl groups.  \n\n![](images/4a73499aced67259f34b0b643e47f9808912903c97eeef98673f9a0d9cd64c90.jpg)  \nFig. 10. a) Synthetic route of DME. b) Storage modulus of cured films. [65] c) Chemical structures of hard/soft monomers containing acrylic groups [66]. Copyright 2017. Reproduced with permission from Springer Nature [65]. Copyright 2017. Reproduced with permission from Elsevier [66].  \n\nIn addition, Yong et al. [66] selected different ratios of hard/soft monomers containing acrylic groups as an adjusting mean to prepare a series of WPUA hybrid emulsions (Fig. 10c). The research disclosed the relationship between mechanical properties and amounts of acrylic monomers. Comparing to the WPU film, the hardness of WPUA coatings increased remarkably owing to the introduction of acrylic monomers, which is due to the reason that the increment of the weight ratio of hard monomers can endow films with rigidity and excellent mechanical properties by considerable phenyl skeleton structures of acrylic monomers. Certainly, they also discovered that each film possessed two $T_{g}$ values, indicating that the phase separation phenomenon existed due to the appearance of hydrogen bonding between hard and hard segments. Hence, they can form buffers by breaking hydrogen bonds when subjected to force, giving coatings toughness. Moreover, Beniah et al. [56] used 1,4-diaminobutane, isophorone diamine, methylene bis(cyclohexyl amine), and bis(aminomethyl) norbornane as chain extenders to investigate the influence between polyhydroxyurethane (PHU) structure and properties of PHUs (Fig. 11a), eventually demonstrating that structure and content of chain extenders played an important role in the properties of PHUs (Fig. 11b and c). The most remarkable improvement in mechanical properties of the resulting PHUs can be obtained when the norbornane-based chain extender was applied owing to the norbornane ring acting as an effective physical cross-linking point since no crystalline structure or hydrogen bonding was observed in their elastomers. This inference was the same as what Jiao et al. [67] got, who synthesized UV-curable PUA oligomers modified with cycloaliphatic epoxide resin.  \n\nOne conclusion we should note is that it is a capital idea to introduce rigid groups into PUA which will significantly improve the hardness of coatings. Whereas, the introduction of benzene rings may result in yellowing of coatings, as benzene ring can be easily oxidized into quinones. In consequence, we should avoid employing materials contained benzene rings to synthesize PUA resins when the appearance of films is a priority.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3.4. Introduction of inorganic nanoparticles  \n\nInorganic nanoparticles can provide excellent mechanical properties for organic/inorganic composites because nano-inorganic fillers are not only small in size but also large in specific surface area. As a result, there exists a strong interaction between particles and polymer interface, which significantly improves physical properties of polymers [68,69].  \n\nGenerally, nano-inorganic fillers that can be introduced into the PUA matrix include silica [70], carbon nitride [17], calcium carbonate [71], alumina [72] and zinc oxide [73] and so on. Lv et al. [16] acquired some waterborne UV-curable $\\mathrm{PUA}/\\mathrm{SiO}_{2}$ nanocomposites via traditional sol-gel method, in which KH-570 was used as the coupling agent of inorganic phases and organic phases, making sure $\\mathrm{{siO}}_{2}$ had good dispersion in the PUA matrix and then incorporated modified- $s\\mathrm{i}0_{2}$ into the ends of the PUA main chains by radical polymerization. Comparing to the physical blending method, from results, it was easier to obtain a uniform emulsion by the sol-gel technique owning to $\\mathrm{{siO}}_{2}$ nanoparticles showing a tendency to aggregate together without any KH-570 added (Fig. 12), which can bring some good effects in practical production applications. At that, comparing with neat PUA, the pencil hardness of $\\mathrm{{PUA}}/{\\mathrm{{SiO}}_{2}}$ coatings enhanced from the HB up to 4H when 6 wt. $\\%$ of silica was added. Certainly, Kim et al. [73] and Xu et al. [74] both also obtained similar consequences by introducing ZnO (Fig. 13a and b) and $\\mathsf{C a C O}_{3}$ (Fig. 13c) into PUA matrix, respectively, in which KH-570 was used as the coupling agent to modify inorganic fillers. Afterward, Liu et al. [75] revealed the relationship between pencil hardness and modified inorganic fillers. As expected, increasing modified fillers loading resulted in apparent improvement of pencil hardness, raising from HB to 2H with $2\\mathrm{wt.\\%}$ filler content. Nevertheless, the pencil hardness occurred a reduction from 2H to H when high filler content was added, which may be caused by the occurrence of inorganic particles aggregation (Fig. 14). As a result, appropriate dispersion of the modified fillers is crucial to take advantage of nanoscale reinforcement and to acquire desired physical and mechanical properties of composites films.  \n\nIn another research, Liao et al. [17] prepared a suite of UV-curable waterborne Wsi-PUA- $\\mathrm{.C_{3}N_{4}}$ composites including vinyl hydroxyl silicone oil and different contents of $\\mathrm{C}_{3}\\mathrm{N}_{4}$ without any couple agents. The results showed that the dispersion of $\\mathrm{C}_{3}\\mathrm{N}_{4}$ particles in composite films were homogeneous when the additive contents of $\\mathrm{C}_{3}\\mathrm{N}_{4}$ were low, endowing composite films with the excellent mechanical property. Nevertheless, agglomerates could be found at higher $\\mathrm{C}_{3}\\mathrm{N}_{4}$ content, which can be supposed to the fact that the high concentration induced phase separation (Fig. 15). Certainly, the pencil hardness of films could increase from 2H to 4H when the content of $\\mathrm{C}_{3}\\mathrm{N}_{4}$ was low. Nam et al. [71] investigated the effect of inorganic nanoparticles $\\mathsf{C a C O}_{3}$ in the UVcurable PUA coating and revealed that the performance of organic/ inorganic nanocomposite film was intensively linked with organicallymodified colloidal $\\mathsf{C a C O}_{3}$ nanoparticles. This was because the weak interfacial interaction between organic phases and inorganic interfaces could be disconnected when the amount of additive $\\mathsf{C a C O}_{3}$ was high, resulting in discontinuity of bond matrix, which gave rise to the disastrous fault of the nanocomposite films. Hence, in order to get highperformance UV-curable PUA nanocomposites coatings, inorganic nanoparticles homogeneously dispersed in organic matrix is crucial.  \n\n![](images/2bc4facc701bc220b8107d411dc5859b0a3a7242226b8aa633b4ea7250b0b555.jpg)  \nFig. 11. a) Synthetic route of PHUs. b) Stress-strain curves of PHUs chain extended with $50\\mathrm{wt.\\%}$ hard-segment content and c) Norbornane diamine at several har segment contents. [56] Copyright 2017. Reproduced with permission from John Wiley and Sons [56].  \n\nAbove of all, something we can discover is that, although PUAs modified with inorganic fillers can raise the hardness of coatings significantly, inorganic nanoparticles may be poorly dispersed due to miserable dispersibility of the high inorganic fillers content in the organic phase, resulting in unfortunate performance enhancement [76]. Therefore, in order to avoid this negative effect, the amount of inorganic filler should be controlled in the appropriate range, because the appropriate dispersion of the nanofillers is crucial to take advantage of nanoscale reinforcement and to obtain desired physical and mechanical properties of nanocomposites [75]. Of course, it must be mentioned that introducing inorganic fillers into the resin matrix will roughen the surface of coatings.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 3.5. Hyperbranched modification  \n\nHyperbranched polymers have advantages of high solubility and reactivity, low solution viscosity and melt viscosity, which are widely used in coatings [77–79]. Modifying PUA with hyperbranched structure not only improve the functionality but also can reduce the viscosity of system, contributing to the dispersion of materials within matrix [80–83]. Some researchers have demonstrated that introducing dendritic hyperbranched PUA into curing system will augment the crosslinking density [84,85] and will form the highly compact structure of films owing to its high functionality.  \n\nJana et al. [86] acquired the hyperbranched core (Fig. 16a) through esterification of pentaerythritol (PE), 2, 2-bis (methylol) propionic acid (DMPA) and trimethylolpropane (TMP), whose branching can be controlled with a varying amount of DMPA as chain extender, and then can form the alkyd polyurethane resin by employing phthalic anhydride and benzoic acid as end-cappers, both containing phenyl groups. The research revealed that with increasing the branching in the hyperbranched core, the pendulum hardness of coatings was reinforced by the introduction of rigid groups of end-cappers. However, the increment of the extent of branching in polyurethane structure lost the orientation or structural regularity of alkyd polyurethane chain, resulting in decreasing the glass transition temperature. In another research, a cluster of hyperbranched polyurethane acrylate (F-HBPUA) with diverse hydroxyl numbers and flexible chains was successfully developed by Xiang et al. [87] (Fig. 16b), and then the effect of generation number and flexible chain on the performances of resin and film was investigated. The results indicated that with increasing generation numbers and chain lengths, the increment of the viscosity was occurred, whereas hardness decreases from F to HB owing to its flexibility which increases with longer soft chains. Certainly, the number of polar groups (nitrogen and oxygen) was raised with the increment of the degree of branching and soft chain length, which strengthened the intermolecular interaction and then endowed good mechanical properties to films. [88,89] Apart from that, Jeong et al. [90] also investigated the effect of degree of HBPUA’s branching on performance, obtaining the result that with increasing the branching from 8 to 16, the hardness of HBPUA coatings enhanced slightly, exhibiting that the effect was not significant. The reason for this phenomenon will be discussed below. Absolutely, one thing for synthesizing oligomers we should be aware is that HBPUA can provoke rapid gelation of the mixed solution in a brief period during preparation owing to its high reactivity. In order to prevent this issue from occurring, sometimes, the reaction was carried out with excess polymerization inhibitors or solvent [31].  \n\n![](images/caa9fd18331bc8a935915710d583716f886ed2ebe8e13cca61a24bd4f5670c9e.jpg)  \nFig. 12. TEM micrographs of PUA and PUA $\\mathrm{\\SiO}_{2}$ hybrid particles: (a) pure PUA, (b) PUA with $4\\mathrm{wt.\\%}$ unmodified $\\mathrm{{SiO}}_{2},$ (c) PUA with $4\\mathrm{wt.\\%}$ modified $\\mathrm{SiO}_{2}$ and (d) PUA with $6\\mathrm{wt.\\%}$ modified $\\mathrm{{SiO}}_{2}$ [16]. Copyright 2015. Reproduced with permission from Royal Society of Chemistry [16].  \n\n![](images/e4288ff7a01ae4da684f8873ef046bd3f1667ea280232bede47f3918bff4fd29.jpg)  \nFig. 13. a) Reaction mechanism of KH-570 with $z_{\\mathrm{{nO}}}$ surface hydroxyl groups. b) The relationship between hardness and modulus values of PUA/ZnO nanocomposite films and ZnO content. [73] c) Brief mechanism of hydrolysis of KH-570 and surface modification of inorganic carbonate [74]. Copyright 2012. Reproduced with permission from Elsevier [73]. Copyright 2018. Reproduced with permission from Springer Nature [74].  \n\n![](images/1ba46e6d4c180fe3a05b5a2841af8a8d1df3a6154f5d8c2d1dfdebf2efc3db04.jpg)  \nFig. 14. SEM micrographs of cross-section of the UV-curable nanocomposite coatings (coated PC) containing a, b $2\\mathrm{wt.\\%}$ and d, e 5 wt. $\\%$ $\\mathrm{TiO}_{2}$ $\\scriptstyle\\phantom{+}_{2}-S\\mathrm{iO}_{2}/\\mathbf{P}$ (MMA-coPMPM), and surface of the UV-curable nanocomposite coatings (coated PC) c 2 wt.% and f 5 wt. $\\%$ $\\mathrm{TiO}_{2}$ - $\\mathrm{SiO}_{2}$ /P(MMA-co-PMPM). [75] Copyright 2018. Reproduced with permission from Springer Nature [75].  \n\nFrom the above research, what we can conclude is that hyperbranched modification both improves functionality and reduces system viscosity, resulting to coatings leveling [91–93]. Nevertheless, singlecomponent hyperbranched polymers have low crosslink density and acquire miserable results after curing. The reason is that although functionalities of polymers are considerable, each of functional groups can be cross-linked together after curing is impossible due to the spherical shape of polymers, which results in a low crosslink density [94–97]. Whereas, if researchers employ it as an additive, especially as an additive of low-functionality PUA, its advantages can be fully exerted, and properties of PUA can be improved well [98].  \n\nZhang et al. [99] chose toluene diisocyanate (TDI) as the main part of PUA matrix. Bifunctional PUA was first prepared by the reaction between polyethylene glycol, hydroxyethyl acrylate and TDI. Subsequently, hyperbranched HBPUA was synthesized via trimethylolpropane as the core of the dendritic polymer, which was used as additives and then introduced into PUA matrix to acquire coatings (Fig. 17a). The results showed that with an increase in HBPUA content, the hardness of coatings improved from 6H to 9H, simultaneously the abrasion resistance and storage modulus also raised markedly (Fig. 17c). Definitely, the cured film with about $10\\mathrm{wt.}\\%$ HBPUA displayed strongly raised tensile strength while the elongation at break received a little reduction. However, the elongation at break was reduced by about $30\\%$ when $20\\mathrm{wt.}\\%$ HBPUA was added, indicating a significant decline in toughness (Fig. 17b). Some researches also disclosed the similar issue that although the rigidity of coatings was reinforced with the increase of crosslink density, the remarkable decrease in elongation at break values resulted in the restrained toughness [31]. And so, it’s a crucial issue that how to keep the toughness constant or decrease slightly while increase the hardness of coatings. One is selecting chain extenders or long soft segments that can generate more hydrogen bonds to promote micro-phases separation or mixed phases [100], which can play a role of the buffer when coatings subjected to force, obtaining the effect of toughness [101]. But for the former, it will lead to uneven coating surface owning to its crystallinity, which is bad for films as the smooth appearance of them is a priority. Another is increasing the content of flexible chain extenders in soft segments, so that PUA chains can easily move, and thus improve the toughness of films. But beyond that, Xiang et al. [87] also certified that as the soft chains increased, the dendritic arms became more flexible, the cured films were more flexible, accordingly. Although the toughening effect can be acquired, the film hardness descended [102]. So, we can receive that only moderate addition of soft chains can keep hardness and toughness both well.  \n\n![](images/b359c529ab1effc66a59036c860f480aab00c5e60d4874bc4f18aeb1b19f6e00.jpg)  \nFig. 15. TEM micrographs of ultra-thin sections taken from the coating samples filled with: a) $0.25\\mathrm{wt.\\%}$ , b) $0.5\\mathrm{wt.}\\%,$ , c) 1.0 wt. $\\%$ and d) $2.0\\mathrm{wt.\\%}$ $\\mathsf{g}\\mathrm{-}\\mathsf{C}_{3}\\mathsf{N}_{4}$ particle [17] Copyright 2015. Reproduced with permission from Elsevier [17].  \n\nGiving a similar example, Zou et al. [103] designed hyperbranched polyurethane (HBPU) by reacting IPDI and poly (tetrahydrofuran), which brought flexible segments for HBPU resin, sequentially generating more hydrogen bonds among molecular chains. HBPU and the linear analog polyurethane (LPU) were used as tougheners in the diglycidyl ether of bisphenol A (DGEBA)/amine system, respectively. This research revealed that the average crosslinking density, comparing with DGEBA/LPU films, DGEBA/HBPU samples were higher attributing to high functionality of HBPU. Furthermore, though adding HBPU raised the crosslink density, the HBPU introduced into matrix enhanced the flexibility of the network structure as well (Fig. 18). It should be noted that the enhancement in toughness is associated with micro-phase separation structures which prevent the crack to freely develop and absorb the impact energy. Apart from that, the stronger interface interaction in the DGEBA/HBPU films promotes the stress transfer when films subjected to force, which is caused by the generation of hydrogen bonding that formed the buffer upon loading.  \n\n![](images/eb8e19a04b94a1fe50d2fc5c2b167d3d5065d1b06e0cb0a9616338ac15c265a6.jpg)  \nFig. 16. a) Scheme of the synthesis of the hyperbranched core. [86] b) Schematic representation for the preparation of F-HBPUA [87]. Copyright 2017. Reproduced with permission from John Wiley and Sons [86]. Copyright 2017. Reproduced with permission from Elsevier [87].  \n\n![](images/79fc80b8b7dfd8b3256ee7493e343c1385d2fc7d40d0466b21bba88e1ceaf933.jpg)  \nFig. 17. a) Synthetic process of PUA/HBPUA UV-curable coatings. b) Stress-strain curves of the cured films. c) Storage modulus (E′) graphs of UV-curable coatings as a function of temperature. [99] Copyright 2016. Reproduced with permission from Royal Society of Chemistry [99].  \n\n![](images/27900aa5eb45069edb84782a067391aeaaf8912ca7992517092ffad1c2f52c05.jpg)  \nFig. 18. The influence of modifier content on the a) impact strength and b) flexural strength. c) Schematic illustration of separate particles in the DGEBA/HBPU films. [103] Copyright 2016. Reproduced with permission from Royal Society of Chemistry [103].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 4. Conclusion  \n\nIn summary, five types of strategies are used for hardening modification of PUA, such as the improvement of the crosslinking density of system, the enhancement in the effect of hydrogen bonding, the incorporation of rigid groups at molecular level, the introduction of inorganic fillers and hyperbranched modification, which have their own advantages and disadvantages. Of these, hyperbranched polyurethane acrylate is optimal because it not only provides polyfunctionality (increasing the cross-linking density), but also reduces system viscosity and contributes to the dispersion of compositions. Although the effect of single hyperbranched polymer on film formation is not very good, its advantages can be maximized when it employs as an additive to coatings. Next one is followed by the introduction of rigid groups owning to their pronounced effect on the hardness of coatings. The material containing rigid groups should be a benzene-free substance which can prevent coatings from yellowing. Furthermore, in order to maximize the increment of hardness, this material will be introduced into the hyperbranched polymer by the formation of hyperbranched nuclei. For the polyfunctional modification, it is a distinct method that using vegetable oils as hyperbranched polyols which can increase the functionality of PUA by epoxidation and ring-opening reaction. In addition, it can be a sustainable route to solve the problem of environment and depletion of the world crude oil stock due to their green and abundant resources, such as palm oil [104] and olive oil [105]. Certainly, siloxanes and silane coupling agents, or inorganic fillers can be introduced into PUA coatings to enhance the hardness of films significantly when the contents of those materials are moderate, which is economical for industrial manufacture. In another expect, we can endow hardening coatings with excellent toughness by the introduction of flexible aliphatic chain or others that can form remarkable hydrogen bonds, accordingly generating physical cross-linking buffers, eventually absorbing impact energy or strengthening stress transfer in the intermolecular chains.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 18,
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Yang, Synthesis, mechanical properties and iron surface conservation behavior of UV-curable waterborne polyurethane-acrylate coating modified with inorganic carbonate, Polym. Bull. (2018), https://doi.org/10.1007/s00289-018-2294-1. [75] F. Liu, G. Liu, Enhancement of UV-aging resistance of UV-curable polyurethane acrylate coatings via incorporation of hindered amine light stabilizers-functionalized $\\mathrm{TiO}_{2}–\\mathrm{SiO}_{2}$ nanoparticles, J. Polym. Res. 25 (2018) 59. [76] S. Zhang, Z. Chen, M. Guo, H. Bai, X. Liu, Synthesis and characterization of waterborne UV-curable polyurethane modified with side-chain triethoxysilane and colloidal silica, Colloids Surf. A Physicochem. Eng. Asp. 468 (2015) 1–9. [77] C. Rim, D.Y. Son, Facile and efficient synthesis of star-shaped oligomers from a triazine core, Tetrahedron Lett. 50 (2009) 4161–4163. [78] W. Han, B. Lin, H. Yang, X. Zhang, Synthesis of novel poly(ester amine) dendrimers by Michael addition and acrylate esterification, Des. Monomers Polym. 16 (2013) 67–71. [79] W. Han, Application of thiol-ene “click” chemistry to preparation of hyperbranched polyurethane acrylate oligomers containing carboxyl groups, J. Photopolym. Sci. Technol. 28 (2015) 419–427. [80] G. Li, S. Jiang, Y. Gao, X. Liu, F. Sun, Synthesis and property of water-soluble hyperbranched photosensitive polysiloxane urethane acrylate, Ind. Eng. Chem. Res. 52 (2013) 2220–2227. [81] W. Han, B. Lin, H. Yang, X. Zhang, Synthesis of UV-curable hyperbranched polyurethane (meth)acrylate oligomers via thiol-ene “click” chemistry, J. Appl. Polym. Sci. 128 (2013) 4261–4270. [82] W. Han, Synthesis and properties of networking waterborne polyurethane/silica nanocomposites by addition of poly(ester amine) dendrimer, Polym. Compos. 34 (2013) 156–163. [83] W. Han, Synthesis and characterization of hyperbranched waterborne polyurethane/Ag nanoparticle composites, Polym. Compos. 39 (2016) 1967–1977. [84] J. Cui, Synthesis of UV-cured hyperbranched polyurethane acrylate coatings and its corrosion resistance revealed by electrochemistry, Int. J. Electrochem. Sci. 11 (2016) 3727–3737. [85] S. Pilla, R.R. Gaddam, R. Narayan, K.V.S.N. Raju, Nitrogen rich hyperbranched polyurethane-carbon nanohorn composite: Implications on the development of multifunctional coatings, Polym. Compos. 39 (2016) E772–E779. [86] T. Jana, T. Koley, T.K. Dhar, Effect of branching in hyperbranched alkyd on the performance of alkyd polyurethane coating, J. Appl. Polym. Sci. 135 (2018) 45835. [87] H. Xiang, X. Wang, L. Xi, H. Dong, P. Hong, J. Su, Y. Cui, X. Liu, Effect of soft chain length and generation number on properties of flexible hyperbranched polyurethane acrylate and its UV-cured film, Prog. Org. Coat. 114 (2018) 216–222. [88] A.K. Mishra, R. Narayan, K.V.S.N. Raju, T.M. Aminabhavi, Hyperbranched polyurethane (HBPU)-urea and HBPU-imide coatings: Effect of chain extender and NCO/OH ratio on their properties, Prog. Org. Coat. 74 (2012) 134–141. [89] G. Xu, Y. Zhao, W. Shi, Properties and morphologies of UV-cured epoxy acrylate blend films containing hyperbranched polyurethane acrylate/hyperbranched polyester, J. Polym. Sci. Part B: Polym. Phys. 43 (2005) 3159–3170. [90] H.J. Jeong, B.K. Kim, Shape memory hyperbranched polyurethanes via thiol-ene click chemistry, React. Funct. Polym. 116 (2017) 92–100. [91] R. Liu, X. Zhang, S. Gao, X. Liu, Z. Wang, J. Yan, Bio-based epoxy-anhydride thermosets from six-armed linoleic acid-derived epoxy resin, RSC Adv. 6 (2016) 52549–52555. [92] W. Han, B. Lin, H. Yang, X. Zhang, Synthesis and properties of UV-curable hyperbranched polyurethane acrylate oligomers containing carboxyl groups, Polym. Bull. 68 (2012) 1009–1022. [93] J. Zhi, Y. He, M. Xiao, J. Nie, Preparation and properties of dual-cure polyurethane acrylate, Prog. Org. Coat. 66 (2009) 35–39. [94] F. Bao, W. Shi, Synthesis and properties of hyperbranched polyurethane acrylate used for UV-curing coatings, Prog. Org. Coat. 68 (2010) 334–339. [95] W. Han, B. Lin, Y. Zhou, J. Song, Synthesis and properties of UV-curable hyperbranched polyurethane acrylate oligomers containing photoinitiator, Polym. Bull. 68 (2012) 729–743. [96] M. Keramatinia, F. Najafi, M.R. Saeb, Synthesis and viscoelastic properties of  \n\nacrylated hyperbranched polyamidoamine UV-curable coatings with variable microstructures, Prog. Org. Coat. 113 (2017) 151–159.   \n[97] Y. Wang, X. Jiang, C. Zhang, X. Jing, Y. Liu, Synthesis of epoxide functionalized hyperbranched polyurethane and its blending with benzoxazine: Cure kinetics and thermal properties, Polym. Bull. 74 (2017) 4209–4222.   \n[98] H. Xiang, X. Wang, G. Lin, L. Xi, Y. Yang, D. Lei, H. Dong, J. Su, Y. Cui, X. Liu, Preparation, characterization and application of UV-curable flexible hyperbranched polyurethane acrylate, Polymers 9 (2017) 552. [99] Q. Zhang, C. Huang, H. Wang, M. Hu, H. Li, X. Liu, UV-curable coating crosslinked by a novel hyperbranched polyurethane acrylate with excellent mechanical properties and hardness, RSC Adv. 6 (2016) 107942–107950.   \n[100] J. Wang, H. Zhang, Y. Miao, L. Qiao, X. Wang, F. Wang, Microphase separation idea to toughen $\\mathrm{CO}_{2}$ -based waterborne polyurethane, Polymer 138 (2018) 211–217.   \n[101] Z. Jiao, Q. Yang, X. Wang, C. Wang, UV-curable hyperbranched urethane acrylate oligomers modified with different fatty acids, Polym. Bull. 74 (2017) 5049–5063.   \n[102] Y. Zhang, A. Asif, W. Shi, Highly branched polyurethane acrylates and their waterborne UV curing coating, Prog. Org. Coat. 71 (2011) 295–301.   \n[103] Z. Zou, X. Liu, Y. Wu, B. Tang, M. Chen, X. Zhao, Hyperbranched polyurethane as a highly efficient toughener in epoxy thermosets with reaction-induced microphase separation, RSC Adv. 6 (2016) 18060–18070.   \n[104] P.K.S. Pillai, M.C. Floros, S.S. Narine, Elastomers from renewable metathesized palm oil polyols, ACS Sustain. Chem. Eng. 5 (2017) 5793–5799.   \n[105] C. Zhang, S.A. Madbouly, M.R. Kessler, Biobased polyurethanes prepared from different vegetable oils, ACS Appl. Mater. Interfaces 7 (2015) 1226–1233.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# [54]   DURABLE ANTI-FOGGING COMPOSITION  \n\n[75]  Inventors: Katsuhiko Deguchi, Sakura; Junryo Mino, Kamagaya; Kaoru Tsujii, Sakura, all of Japan   \n[73] Assignee: Kao Soap Co., Ltd., Tokyo, Japan   \n[21] Appl. No.: 845,973   \n[22] Filed: Oct. 27, 1977   \n[30] Foreign Application Priority Data Nov. 8, 1976 [JP] Japan 51-134514   \n[51] Int. CI.2 C09K 3/18   \n[52] U.S. Cl. 106/13; 260/29.6 B; 260/29.6 SQ; 260/29.6 MQ; 260/29.6 MN   \n[58] Field of Search 106/13   \n[56] References Cited",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# U.S. PATENT DOCUMENTS  \n\n2,716,068 8/1955 Fain et al. 106/13 3,696,043 10/1972 Labrage et al. 106/13 3,856,534 12/1974 Fletcher et al. 106/13 Primary Examiner—J. Ziegler Attorney, Agent, or Firm---Blanchard, Flynn, Thiel, Boutell & Tanis  \n\n[57]",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# ABSTRACT  \n\nA durable anti-fogging agent composition comprises at least one sulfonic acid type amphoteric surface active agent represented by the following general formula (I):  \n\n$$\n\\underset{\\underset{\\mathbf{R}_{3}}{\\parallel}}{\\boldsymbol{\\mathbb{R}}_{1}}\\underset{\\underset{\\mathbf{R}_{3}}{\\parallel}}{\\boldsymbol{\\mathbb{Q}}_{\\mathbf{N}-\\mathbf{R}_{4}-\\mathbf{SO}_{3}}}\\Theta^{\\mathrm{~.~}}\n$$  \n\nwherein $\\mathbb{R}_{1},$ ${\\bf R}_{2}$ and ${\\bf R}_{3}$ each stand for an alkyl, hydroxyalkyl or benzyl group, the sum of carbon atoms of the groups ${\\bf R}_{1}$ ${\\tt R}_{2}$ and ${\\bf R}_{3}$ is in the range of 16 to 38 and one of the groups ${\\bf R}_{1}$ ${\\tt R}_{2}$ and $\\mathbb{R}_{3}$ is an alkyl or hydroxyalkyl group having at least 14 carbon atoms, and $\\mathtt{R}_{4}$ stands for an alkylene or hydroxyalkylene group having 2 to 4 carbon atoms,  \n\nand at least one member selected from inorganic salts and acetates represented by the general formulae MeSCN, $\\mathbf{MeNO}_{3}$ MeX and $\\mathbf{MeOOCCH_{3}}$ in which Me is a cation selected from Na, K, Li, $\\mathbf{NH}_{4}$ $\\scriptstyle{\\frac{1}{2}}\\mathbf{C}\\mathbf{a}$ and $\\scriptstyle{\\frac{1}{2}}\\mathbf{M}\\mathbf{g}$ and $\\mathbf{x}$ is a halogen ion.",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# 6 Claims, No Drawings",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# DURABLE ANTI-FOGGING COMPOSITION",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# BACKGROUNDOFTHEINVENTION",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 1. Field of the Invention  \n\nThe present invention relates to a composition providing a high and durable anti-fogging effect on the surfaces of glass, plastics and polymeric films.",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2. Description of Prior Arts  \n\nIn general, the surfaces of glass, plastics and polymeric films readily become foggy with the condensation of water vapor, and the transparency disappears or uneven reflection is caused on the surfaces. This phenomenon of fogging causes various troubles. For exam- 1: ple, fogging on front, side or rear glass windows of an automobile or on spectacles results in great inconvenience and sometimes causes an accident endangering life. Further, when show-windows become foggy, no intended exhibiting effect can be attained, and when a 2l polymeric film or glass of an agricultural green house or a dormer or other window of an oridinary house becomes foggy, transmission of light is inhibited and the growth of plants is checked or their health is injured.  \n\nAnti-fogging agents comprising anionic surface ac- 2 tive agents, silicone type surface active agents or tricresyl phosphates have heretofore been used as agents for preventing fogging. However, none of the known anti-fogging agents have a sufficient durability of the anti-fogging effect. In order to attain the anti-fogging effect, it is necessary to increase the free energy on the surface and render the surface easily wettable with water. For attaining this purpose, a surface active agent is generally coated on the surface. However, the surface active agent is readily separated from the coated surface 3 when wetted with water and the intended anti-fogging effect cannot be attained.",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# SUMMARY OF THEINVENTION  \n\nThe present invention provides an anti-fogging agent composition having a good durable anti-fogging effect, which is adsorbed on the surface very effectively and is not readily separated from the surface.  \n\nIn accordance with the present invention, there is provided an anti-fogging agent composition comprising as indispensable components 0.05 to $30\\%$ by weight of at least one sulfonic acid type amphoteric surface active agent represented by the following general formula (I):  \n\nerably Cl, Br or I. The balance of the composition is generally water.  \n\nThis anti-fogging agent may further comprise as a third component 0.01 to $30\\%$ by weight of a nonionic surface active agent having an HLB value of 12 to 15 or 0.005 to $10\\%$ by weight of a water-soluble polymer composed of a maleic anhydridevinyl monomer copolymer.  \n\nThe sulfonic acid type amphoteric surface acitve 10 agent represented by the general formula (I), which is used in the present invention, may be prepared by reaction an $\\pmb{\\alpha}$ -hydroxyalkyldialkylamine derived from a tertiary alkylamine or $^{\\alpha,\\beta}$ -alkylene epoxide with an alkane sultone or by reacting the $\\pmb{\\alpha}$ -hydroxyalkyldialkylamine with benzyl chloride or epichlorohydrin and sulfating the resulting product.  \n\nThis first component is incorporated in the anti-fogging agent in an amount of 0.05 to $30\\%$ by weight, preferably 0.1 to $10\\%$ by weight.  \n\nAn inorganic salt or acetate is used as the second component in the present invention, and this second component is selected from inorganic salts and acetates represented hy the above-mentioned general formulae, for example, NaSCN, $N a N O_{3}$ , KCl, LiBr, $\\boldsymbol{\\widetilde{\\mathbf{NH}_{4}}\\mathbf{Cl}}.$ ,KI, $\\mathbf{MgCl}_{2}.$ $\\mathbf{CaCl}_{2}$ and $\\mathbf{CH_{3}C O O N a}$ . The second component is incorporated in the anti-fogging agent in an amount of 0.01 to $20\\%$ by weight, preferably 0.1 to $10\\%$ by weight.  \n\n30 The most characteristic feature of the present invention is that the anti-fogging agent composition has an excellent anti-fogging effect, which can be maintained for a long time. More specifically, the present invention is based on the finding that although the sulfonic acid   \n35 type amphoteric surface active agent repesented by the general formula (I) has a very low water solubility and in general, it cannot be used as it is, if a specific inor- ganic salt or acetate is used as the second component in combination with this hardly water-soluble surface ac  \n40 tive agent, the solubility is drastically enhanced by interactions between the two components and the adsorption on the surface is remarkably improved. Further, when the anti-fogging agent is once adsorbed into the surface, it is prevented from falling out from the surface   \n$\\pmb{45}$ for a long time because of the: low solubility thereof. Accordingly, an excellent anti-fogging effect can be manifested for a long time. In general, it is well known that surface active agents readily exhibit a so-called salting-out phenomenon, that is, the solubility is drasti  \n50 cally reduced in the presence of a salt. According to the present invention, it has been found that sulfonic acid type amphoteric surface active agents such as represented by the above general formula (I) exhibit a socalled salting-in phenomenon, that is, the solubility is   \n55 remarkably enhanced even in the presence of a salt, as observed in case of proteins. This salting-in phenomenon is peculiar because it has not been known in case of surface active agents. This salting-in phenomenon gives excellent dissolving, adsorbing and anti-fogging effects   \n60 to the first component of the present invention. The inorganic salt or acetate acts as a kind of salt, giving charges to the sulfonic acid type amphoteric surface active agent, and it not only exerts a dissolution-promoting effect, but also manifests an anti-fogging effect   \n65 synergistically with the sulfonic acid type amphoteric surface active agent. In other words, the inorganic salt or acetate as the second component has an interaction with the ionic portion of the sulfonic acid type ampho  \n\n$$\n\\underset{\\underset{\\mathrm{R3}}{\\uparrow}}{\\mathbb{R}}1\\underset{\\underset{\\mathrm{R3}}{\\uparrow}}{\\mathbb{R}}-\\underset{\\mathrm{R}_{4}-\\underset{\\mathrm{S}(3_{3}\\ominus)}{\\uparrow}}{\\mathbb{S}}\n$$  \n\nwherein $\\mathbf{R}_{1},$ ${\\bf R}_{2}$ and ${\\bf R}_{3}$ each stand for an alkyl, hydroxyalkyl or benzyl group, the sum of carbon atoms of the groups $\\mathbf{R}_{1},\\mathbf{R}_{2}$ and $\\pmb{\\mathrm{R}}_{3}$ is in the range of 16 to 38 and one of the groups $\\pmb{\\mathrm{R}}_{1}$ . ${\\tt R}_{2}$ and ${\\bf R}_{3}$ is an alkyl or hydroxyalkyl group having at least 14 carbon atoms, and $\\pmb{\\mathrm{R}_{4}}$ stands for an alkylene or hydroxyalkylene group having 2 to 4 carbon atoms,  \n\nand 0.01 to $20\\%$ by weight of at least one member selected from inorganic salts and acetates represented by the general formulae MeSCN, ${\\bf M e N O}_{3},$ ， MeX and $\\mathbf{MeOOCCH_{3}}$ in which Me is a cation selected from $\\mathbf{Na},$ $\\mathbf{x},$ Li, $\\mathbf{NH_{4}}$ $\\pmb{\\mathrm{\\hat{c}}}\\mathbf{a}$ and $\\pmb{\\mathrm{i}}\\mathbf{M}\\mathbf{g}$ and $\\mathbf{x}$ is a halogen ion, pref",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 4,214,908",
+        "category": " References"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3",
+        "category": " Introduction"
+    },
+    {
+        "id": 12,
+        "chunk": "# #  \n\nteric surface active agent and as a result, the adsorption and the anti-fogging effect are synergistically improved.  \n\nAs the nonionic surface active agent having an HLB value of 12 to 15, that is used as the third component in the present invention, those represented by the following general formuia (11):  \n\n$$\n\\mathtt{R O(C H_{2}C H_{2}O)}_{n^{\\sharp}}\n$$  \n\nwherein R stands for an alkyl group having 10 to 16 1C carbon atoms, an alkenyl group having 14 to 18 carbon atoms or an octyiphenyl or nonyiphenyi group, and n is the number of moles of added ethylene oxide, which should be determined so that the HLB value may be in the range of 12 to 15,  \n\nare preferred. The nonionic surface active agent is incorporated in an amount of 0.01 to $30\\%$ by weight, preferably 0.1 to $10\\%$ by weight.  \n\nAs the water-soluble polymer composed of a maleic anhydride-vinyi monomer copolymer, that is used as 20 the third component, there can be mentioned, for example, a maleic anhydride-acetalized vinyl alcohol copolymer, a maleic anhydride-vinyl alcohol copolymer, a maleic anhydride-ethylene copolymer, a maleic anhydride-styrene copolymer, a partially saponified product 25 thereof, a maleic anhydride-methyl vinyl ether copolymer, a partially saponified product thereof, a maleic anhydride-diisobutylene copolymer and a partially saponified product thereof. It is preferred that the average degree of polymerization of the water-soluble polymer 30 be in the range of 500 to 1500. This water-soluble polymer is incorporated in an amount of 0.005 to $10\\%$ by weight, preferably 0.01 to $5\\%$ by weight. By incorporation of such third components the anti-fogging effect is enhanced, and moreover, the low temperature stability 35 of the composition can be remarkably improved.  \n\nIn order to improve the low temperature stability, it is preferred that up to $30\\%$ by weight of an alcohol having two or three carbon atoms, such as ethanol and propanol, be incorporated in the anti-fogging agent composition of the present invention. p Further, the anti-fogging agent composition of the present invention may be impregnated into paper, cloth, nonwoven fabric or the like and it may be used in the form of an anti-fogging paper or cloth.  \n\nThe present invention will now be described in deta I reference to the following Examples.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# EXAMPLE 1  \n\nAn anti-fogging agent having the following composition was prepared:  \n\n<html><body><table><tr><td>Amphoteric surface active agent</td><td>1.0% by weight</td></tr><tr><td>(Table 1) Inorganic salt (Table 1)</td><td>1.0% by weight</td></tr><tr><td>Ethanol</td><td>10.0% by weight</td></tr><tr><td>Deionized water</td><td>balance</td></tr></table></body></html>  \n\nThe durability of the anti-fogging agent having the i5 above composition was tested according to the following method to obtain results shown in Table 1.  \n\n(I) The outer wall of a clean glass beaker was dipped in the anti-fogging agent having the above composition, and it was dried with air.   \n(II) Cold water (maintained at $0^{\\circ}\\mathbb{C}.$ ) was poured into the beaker and after 10 minutes, the fogginess on the outer wall of the beaker was examined with the naked eye.   \n(III) Cold water in the beaker was thrown away, and the outer wall of the beaker was dried with air again.   \n(IV) After drying, cold water was poured into the beaker again and the outer wall of the beaker was examined again.   \n(V) The above operations (I) to (IV) were repeated until no anti-fogging effect was observed. In Table 1, the durability of the anti-fogging effect is expressed in terms of the number of cycles of repetition of the above operations conducted until no anti-fogging   \n35 effect was observed. Accordingly, a larger value indicates a higher durability of the anti-fogging effect. From the results shown in Table 1, it wili readily be understood that an especially good effect can be attained by the combined use of a sulfonic acid type am  \n40 photeric surface active agent and an inorganic salt. In Table l, “control\" means a composition in which a typical anionic surface active agent, sodium dodecyl sulfate $(\\mathbb{C}_{12}\\mathbb{H}_{25}\\mathbf{O}\\mathbb{S}\\mathbf{O}_{3}\\mathbb{N}\\mathbf{a})$ ， was incorporated in an amount of $2.0\\%$ by weight instead of the inorganic salt.   \n45 When an amphoteric surface active agent was used alone, the durability of the anti-fogging effect was l or lower.  \n\nTable 1   \n\n\n<html><body><table><tr><td>Amphoteric Surface Active Agent</td><td>Inorganic Salt</td><td>Durability of Anti-Fogging Effect (number of cycles)</td></tr><tr><td>Comparison</td><td></td><td></td></tr><tr><td>control</td><td></td><td>1</td></tr><tr><td>C18H37(CH3)2N+-O-</td><td>NaSCN</td><td>3</td></tr><tr><td>C18H37NH+(CH2)2COO-</td><td></td><td>3</td></tr><tr><td>C18H37(CH3)2N+(CH2)COO--</td><td></td><td>3</td></tr><tr><td>Present Invention</td><td></td><td></td></tr><tr><td>C18H37(CH3)2N+(CH2)2SO3-</td><td></td><td>6</td></tr><tr><td>C18H37(OH)(CH3)N+(CH)3SO3--</td><td></td><td>9</td></tr><tr><td></td><td></td><td>8</td></tr><tr><td>C14H29(CH2 )(CH3)N+(CH2)3SO -</td><td></td><td></td></tr><tr><td>C14H29(CH3)21  (CH2)3SD3-</td><td></td><td>6</td></tr><tr><td>C18H37(CH3)2(CH2)SO</td><td></td><td>10</td></tr><tr><td></td><td>NaNO</td><td>8</td></tr><tr><td></td><td>NaCl</td><td>7</td></tr><tr><td></td><td>NazSO4</td><td>6</td></tr><tr><td></td><td>CaCl2</td><td>8</td></tr><tr><td></td><td>Mg(NO3)2</td><td>9</td></tr></table></body></html>  \n\nTable l-continued   \n\n\n<html><body><table><tr><td>Amphoteric Surface Active Agent</td><td>Inorganic Salt</td><td>Durability of Anti-Fogging Effect (number of cycies)</td></tr><tr><td></td><td>NaOOCCH3</td><td>6</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 14,
+        "chunk": "# EXAMPLE 2  \n\nThe durability of the anti-fogging effect and the low 10 temperature stability were examined in composition formed by further incorporating a nonionic surface  \n\namined with the naked eye. The low temperature stability was evaluated according to the following scale:  \n\n$\\circledcirc$ : not changed $\\bigcirc$ : slightly turbid $\\Delta$ ： considerably turbid X: precipitates formed.  \n\n![](images/d4ebdaf22fc3582ed48918e3f0900be0cf53d343c8496902201c88084fe55e6a.jpg)  \n\nactive agent into the composition illustrated in Example 1. Results obtained when $\\mathbf{C}_{18}\\mathbf{H}_{37}(\\mathbf{C}\\mathbf{H}_{3})_{2}\\mathbf{N}+(\\mathbf{C}\\mathbf{H}_{2})_{3}\\mathbf{S}\\mathbf{O}_{3}3\\mathbf{i}$ was used as the amphoteric surface active agent and NaSCN was used as the inorganic salt are shown in Table 2. The recipe of the 4: anti-fogging agent composition tested is as follows:  \n\n<html><body><table><tr><td>C18H37(CH3)2N+(CH)3SO3- NaSCN</td><td>1.0% by weight</td></tr><tr><td>Nonionic surface active agent</td><td>1.0% by weight 0.5% by weight</td></tr><tr><td>(Table 2) Ethanol</td><td>10.0% by weight</td></tr><tr><td>Deionized water</td><td>balance</td></tr><tr><td></td><td></td></tr></table></body></html>  \n\nIn Table 2, “control\" means a composition having the 55 same recipe as described above except that the nonionic surface active agent was not added.  \n\nTable 2   \n\n\n<html><body><table><tr><td rowspan=\"5\">50 55</td><td>C18H37(CH3)2N+(CH2)3SO3-</td><td>1.0% by weight</td></tr><tr><td>NaSCN</td><td>1.0% by weight 0.01% by weight</td></tr><tr><td>Water-soluble polymer (Table 3)</td><td></td></tr><tr><td>Ethanol</td><td>10.0% by weight</td></tr><tr><td>Deionized water</td><td>balance</td></tr></table></body></html>  \n\nFrom the results shown in Table 2, it is apparent that a nonionic surface active agent having an HLB value of 12 to 15 is very effective for improving the durability of 6( the anti-fogging effect and the low temperature stability in the above anti-fogging agent composition.  \n\nThe durability of. the anti-fogging effect was evaluated according to the same method as described in Example 1. The iow temperature stability was evaluated in 6 the following manner.  \n\nThe test composition was allowed to stand at $-5^{\\circ}\\mathbf{C}$ · for one week and the state of the composition was ex",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# EXAMPLE3  \n\nThe durability of the anti-fogging effect and the low temperature stability were examined in compositions formed by incorporating a water-soluble polymer instead of the nonionic surface active agent in the composition illustrated in Example 2. Obtained results are shown in Table 3. The recipe of the composition tested is as follows:  \n\nThe durability of the anti-fogging effect and the low temperature stability were evaluated according to the same methods as adopted in Example 2.  \n\nIn Table 3, \"control\" means a composition in which the water-soluble polymer was not added, and “P\" means an average degree of polymerization in the water-soluble polymer.  \n\nFrom the results shown in Table 3, it is apparent that if a maleic anhydride copolymer is incorporated, the durability of the anti-fogging effect and the low temperature stability can be remarkably improved in the antifogging agent composition.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 7  \n\nTable 3   \n\n\n<html><body><table><tr><td>Water-Soluble Polymer</td><td>Durability of Anti-Fogging Effect (number of cycles)</td><td>Low Temperature Stability</td></tr><tr><td>Comparison</td><td></td><td></td></tr><tr><td>control polyvinyl alcohol (saponification degree 85% P=500)</td><td>10 6</td><td>A X</td></tr><tr><td>polyvinyl alcohol (saponification degree 90% P--600) polyacrylic acid (P=850)</td><td>6</td><td>X</td></tr><tr><td>sodium polyacrylate (P-500)</td><td>5 6</td><td>A X</td></tr><tr><td>sodium polyacrylate (P=800)</td><td>5</td><td>△</td></tr><tr><td>polyethylene glycol (P=400) polyethyiene glycol (P=900)</td><td>5</td><td>X X</td></tr><tr><td>Present Invention</td><td>6</td><td></td></tr><tr><td>maleic anhydride-methyl vinyl ether copolymer (P=1000)</td><td></td><td></td></tr><tr><td></td><td>12</td><td>00</td></tr><tr><td>maleic anhydride-ethyl vinyl ether copolymer (P=900)</td><td>12</td><td></td></tr><tr><td>maieic anhydride-diisobutylenecopolymer (P=1200)</td><td></td><td></td></tr><tr><td>maleic anhydride-styrene copolymer (P=800)</td><td>13</td><td></td></tr><tr><td>maleic anhydride-vinyl alcohol copolymer (P=1500)</td><td>12 11</td><td>A</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# EXAMPLE4  \n\nA soft cloth was impregnated with an anti-fogging agent composition having the following recipe:  \n\n![](images/c1b0ac97a6c019bd321159d0318d48f5b3dc87567d5c699d8d29fb4b2a9fd7cf.jpg)  \n\nThe impregnated cloth was dried and the outer wall of a clean glass beaker was rubbed sufficiently with this 35 cloth.Then, the durability of the anti-fogging effect was evaluated according to the method described in Example 1 to obtain results shown in Table 4. As will be apparent from the results shown in Table 4, the cloth has an anti-fogging effect even when it is used 20 times. 40  \n\n14 carbon atoms, and R4 is alkylene or hydroxyalkylene having2 to 4 carbon atoms; 0.01 to $20\\%$ by weight of at least one member selected from the group consisting of inorganic salts and acetates having the formulae MeSCN, MeNO3, MeX and   \n25 MeOOCCH3 in which Me is a cation selected from the group consisting of Na, K, Li, $\\mathbb{N H}_{4},$ $\\mathtt{j}\\mathtt{C a}$ and ${\\bf\\Gamma}_{2}^{3}\\bf{M}g$ and X is halogen; up to 30% by weight of alkanol having 2 or 3 carbon atoms; and the balance is water. 2. A durable anti-fogging composition as set forth in   \n30 claim 1, which comprises 0.1 to i0% by weight of said sulfonic acid type amphoteric surface active agent and 0.1 to 10% by weight of said inorganic salt or acetate. 3. A durable anti-fogging composition as set forth in claim 1, wherein said inorganic salt is NaSCN, NaNO3   \n35 or $\\mathbf{Mg(NO_{3})_{2}}$ 4.A durable anti-fogging composition consisting essentially of 0.05 to 30% by weight of at least one sulfonic acid type amphoteric surface active agent having the formula (I):  \n\nTable 4   \n\n\n<html><body><table><tr><td colspan=\"2\">Durability of Anti-Fogging Effect of Anti-Fogging Cloth</td><td rowspan=\"5\">45 50</td></tr><tr><td>Frequency (times) of Use of Anti-Fogging Cloth</td><td>Effect (number of cycles) Durability of Anti-Fogging</td></tr><tr><td></td><td>6</td></tr><tr><td>15</td><td>4</td></tr><tr><td>10</td><td>3</td></tr><tr><td>520</td><td>２１</td></tr><tr><td></td><td></td></tr></table></body></html>  \n\nWhat is claimed is:  \n\n1. A durable anti-fogging composition consisting essentially of 0.05 to 30% by weight of at least one sulfonic acid type amphoteric surface active agent hav- 5 ing the formula (I):  \n\n$$\n\\underset{\\overset{.}{\\mathrm{R}}_{1}\\overset{.}{\\mathrm{\\mathbb{Q}}}_{\\mathrm{N}}^{\\overset{}{\\|}}-\\mathrm{\\mathbb{R}}_{4}-{\\mathrm{S}}\\mathrm{\\mathbf{O}}_{3}\\ominus}{\\overset{}{\\|}}\n$$  \n\nwherein R1, R2 and R3 each is alkyl, hydroxyalkyl or benzyl, the sum of the number of carbon atoms of R1, R2 and R3 is in the range of from 16 to 38 and one of R1, R2 and R3 is alkyl or hydroxyalkyl having at least  \n\n$$\n\\underset{\\underset{\\mathrm{R}_{3}}{\\mathrm{R}_{1}}\\underset{\\mathrm{R}_{3}}{\\mathrm{\\oplus}}}{\\mathrm{R}_{1}\\underset{\\mathrm{R}_{3}}{\\mathrm{\\oplus}}}{\\mathrm{R}_{2}}\n$$  \n\nwherein $\\mathbb{R}_{1},\\mathbb{R}_{2}$ and ${\\bf R}_{3}$ each is alkyl, hydroxyalkyl or benzyl, the sum of the number of carbon atoms of R1, ${\\tt R}_{2}$ and $\\mathbb{R}_{3}$ is in the range of from 16 to 38 and one of R1, ${\\bf R}_{2}$ and $\\mathbf{R}_{3}$ is an alkyl or hydroxyalkyl having at least 14 carbon atoms, and R4 is alkylene or hydroxyalkylene having 2 to 4 carbon atoms;  \n\n0.01 to 20% by weight of at least one member selected from the group consisting of inorganic salts and acetates having the formulae MeSCN, MeNO3, MeX and MeOOCCH3 in which Me is a cation selected from the group consisting of $\\ \\mathbb{N}\\mathfrak{a},\\ \\mathbb{K},$ Li, $\\mathrm{\\DeltaNH_{4}},$ $\\scriptstyle{\\mathtt{k C a}}$ and $\\bf\\Pi_{2}M g$ and X is halogen; up to 30% by weight of alkanol having 2 or 3 carbon atoms; and the balance is water.  \n\n5. A durable anti-fogging composition as set forth in 0 claim 4 wherein said nonionic surface active agent has the formula (11):  \n\n$$\n\\mathbf{RO}(\\mathbf{CH}_{2}\\mathbf{CH}_{2}\\mathbf{O})_{n}\\mathbf{H}\n$$  \n\nwherein R is alkyl having 10 to 16 carbon atoms, alkenyl having 14 to 18 carbon atoms, octylphenyl or",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# 4,214,908",
+        "category": " References"
+    },
+    {
+        "id": 19,
+        "chunk": "# 9",
+        "category": " Introduction"
+    },
+    {
+        "id": 20,
+        "chunk": "# 10  \n\nnonylphenyl, and n is the number of moles of added ethylene oxide and is selected so that the HLB value is in the range of 12 to 15.  \n\n6. A durable anti-fogging composition as set forth in claim 4 which comprises from 0.1 to 10% by weight of 5 said sulfonic acid type amphoteric surface active agent, from 0.1 to 10% by weight of said inorganic salt or acetate, and from 0.1 to 10% by weight of said nonionic surface active agent.  \n\n15  \n\n25  \n\n30  \n\n35  \n\n40  \n\n45  \n\n50  \n\n55  \n\n60",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 21,
+        "chunk": "# U NITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION  \n\nPATENT NO. : 4 214 908   \nDATED : July 29, 1980   \nINVENTOR(S) : Katsuhiko DEGUCHI, JunryO MINO and Kaoru TSUJII  \n\nIt is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  \n\nColumn 8, line 57; after \"halogen;\" insert ---0.01 to $30\\%$ by weight of a nonionic surface active agent having an HLB value of l2 to l5;---.  \n\nSigned.and Sealed this Twenty-eighth Day of October 1980  \n\n[SEAL]  \n\nAttest:  \n\nSIDNEY A. DIAMOND  \n\nAttesting Officer  \n\nCommissioner of Patents and Trademarks",
+        "category": " References"
+    }
+]
\ No newline at end of file
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new file mode 100644
index 0000000..981e13c
--- /dev/null
+++ b/task2/task2-chunks/2001-US-anti-fog.json
@@ -0,0 +1,117 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (12） United States Patent Yamamoto et al.",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# References Cited",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54) ANTI-FOGGING COATING MATERIAL, ANTI-FOGGING COATING FILM AND ANTI-FOGGING ARTICLE  \n\n(75） Inventors: Tohru Yamamoto; Shigeo Yoshida; Hatsumi Ikari, all of Shiga-ken; Keiji Ikemori, Yokohama; Keiji Ohtaka, Yokohama; Hideo Ukuda, Yokohama, all of (JP)  \n\n（\\*） Notice: This patent issued on a continued prosecution application filed under 37 CFR 1.53(d), and is subject to the twenty year patent term provisions of 35 U.S.C. 154(a)(2).  \n\n(10) Patent No.: US 6,306,932 B1   \n(45) Date of Patent: \\*Oct. 23, 2001  \n\nSubject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days.  \n\n(73） Assignees: Canon Kabushiki Kaisha, Tokyo (JP); Nakato Laboratory, Inc., Shiga-Ken (JP)",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# FOREIGNPATENTDOCUMENTS  \n\n0 716051A2 \\* 6/1996 (EP).   \n0871046A1 10/1998 (EP).   \n8-231944 9/1996 (JP).",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# OTHERPUBLICATIONS  \n\nPatent Abstracts of Japan, vol. 017, No. 406 (C-1090), Jul.   \n22,1993.   \nPatent Abstracts of Japan, vol. 012, No. 501 (C-556), Dec.   \n27,1988.   \nPatent Abstracts of Japan, vol. 011, No. 012 (P-535), Jan.   \n13,1987.   \nPatent Abstracts of Japan, vol. 013, No. 227 (C-600), May 25,1989.   \nPatent Abstracts of Japan, vol. 013, No. 223 (M-829), May 24,1989.   \nPatent Abstracts of Japan, vol. 016, No. 437 (C-0984), Sep.   \n11,1992.   \nPatent Abstracts of Japan, vol.1997, No. 01, Jan.31, 1997.   \nPatent Abstracts of Japan, vol.1998, No. 01, Jan.30, 1998.  \n\n\\* cited by examiner  \n\n(21) Appl. No.: 09/140,409 (22) Filed: Aug.26, 1998 (30) Foreign Application Priority Data  \n\nAug.27,1997 (JP) 9-230530  \n\n(51) Int. Cl.7 C08J 3/00; C08K 29/04; C08K 5/07; C08L 29/04; C09K 3/18 (52) U.S. Cl. 523/169; 522/8; 522/33;   \n524/359; 524/394; 524/401; 524/503 (58) Field of Search 523/169; 522/8,   \n522/33; 524/359,394,401,503  \n\nPrimary Examiner—Patrick D.Niland (74) Attorney, Agent, or Firm—Fitzpatrick, Cella, Harper & Scinto",
+        "category": " References"
+    },
+    {
+        "id": 6,
+        "chunk": "# ABSTRACT  \n\nDisclosed herein is an anti-fogging coating material comprising at least one selected from the group consisting of an inorganic alkoxide, a hydrolysate of the inorganic alkoxide and a polycondensate of the hydrolysate of the inorganic alkoxide, a polyacrylic, and polyvinyl alcohol.",
+        "category": " Abstract"
+    },
+    {
+        "id": 7,
+        "chunk": "# 14 Claims, No Drawings",
+        "category": " References"
+    },
+    {
+        "id": 8,
+        "chunk": "# 1 ANTI-FOGGING COATING MATERIAL, ANTI-FOGGING COATING FILM AND ANTI-FOGGING ARTICLE  \n\nBACKGROUNDOFTHEINVENTION",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 1.Field of the Invention  \n\nThe present invention relates to an anti-fogging coating material which is capable of imparting hydrophilicity and the function of absorbing water to the surfaces of substrates, such as optical lenses, spectacles and window glass of vehicles, which require anti-fogging properties and the prevention of dew condensation, and the surfaces of films for bubble-jet printers, and forming a water-insoluble film having a high surface hardness, an anti-fogging coating film formed out of the anti-fogging coating material, and an anti-fogging article on which the anti-fogging coating film has been formed.",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2. Related Background Art  \n\nThe reason why substrates such as glass and plastics fog up is that moisture in the air adheres thereto in the form of fine waterdrops because their surface temperatures are lowered to a dew point or lower, and so light is irregularly reflected on the surfaces of the substrates. Accordingly, it is considered that the occurrence of fogging can be prevented by preventing the formation of waterdrops on the surfaces of the substrates. As such anti-fogging methods, for example, four factors of (A) adjustment of wetting; (B) impartment of water-absorbing properties; (C) impartment of water repellency; and (D) adjustment of humidity by heating have been considered.  \n\nWith respect to the factor (A), anti-fogging sprays and the like are on the market for the purpose of adjusting wetting, namely, making a contact angle between a substrate and a waterdrop small.However, such a spray uses a surfactant or the like, so that the durability of its effect is not good.  \n\nWith respect to the factor (B), the water-absorbing properties is an effect brought about by a coating film of a hydrophilic polymer, and the durability of the effect is somewhat good when compared with the anti-fogging spray. However, a substrate to the surface of which the waterabsorbing properties have been imparted by such a coating film fogs up when exceeding the water absorption capacity of the coating film, and the surface begins to dissolve.  \n\nWith respect to the factor (C), the water repellency is imparted by applying a water-repellent compound to a substrate. When the water-repellent compound is applied to, in particular, the inside surface of a vinyl plastic hothouse, fine waterdrops on the surface come into contact each other and fall as bigger waterdrops, whereby anti-fogging properties can be developed. However, fine waterdrops may adhere to the surface in some cases, resulting in the occurrence of fogging.  \n\nWith respect to the factor (D), the adjustment of humidity by heating can achieve an anti-fogging effect on lenses of copying machines, rear windshields for automobiles and high-grade dressing tables. Since a power source is required, however, its application fields are limited.  \n\nFurther, the films formed out of an anti-fogging coating composition comprising an organic polymer containing a surfactant have been developed. This anti-fogging coating composition is so designed that the film formed is made hydrophilic by polyether polyol in the presence of the surfactant to absorb moisture, and wetting is adjusted by the surfactant contained when the moisture exceeds the critical point of water absorption of this film, thereby retaining good transparency. Since the surfactant is easily dissolved in water and dissolved out, however, the anti-fogging properties and strength of the film are markedly lowered.  \n\n15  \n\nJapanese Patent Application Laid-Open No. 8-231944   \n5 discloses that the drawbacks involved in the conventional methods are improved by using polyalkylene oxide and a polyacrylic as organic polymers, and making use of a three-dimensional structure formed by the hydrolysis and polycondensation reaction of an inorganic alkoxide.   \n10 However, a problem arises after immersion in water for a long period of time and upon use at a low temperature, and so there is a tendency not to sufficiently develop its performance.",
+        "category": " Introduction"
+    },
+    {
+        "id": 11,
+        "chunk": "# SUMMARY OF THE INVENTION  \n\nThe present invention has been made to solve the abovedescribed drawbacks involved in the prior art, and its object is to provide a coating material for providing a anti-fogging coating film which is hydrophilic and water-insoluble and has high water absorbing power and excellent surface hardness, and in particular, an anti-fogging coating material for enhancing surface precision in the coating and light transmission properties of optical lenses and the like.  \n\nAnother object of the present invention is to provide an anti-fogging coating film formed out of the coating material described above and an anti-fogging article on which the anti-fogging coating film has been formed.  \n\nThe above objects can be achieved by the present invention described below.  \n\nThe present invention provides an anti-fogging coating material comprising at least one selected from the group consisting of an inorganic alkoxide, a hydrolysate of the inorganic alkoxide and a polycondensate of the hydrolysate of the inorganic alkoxide, a polyacrylic, and polyvinyl alcohol.  \n\nThe present invention provides an anti-fogging coating film formed by using, as a main component, a composition obtained by the polycondensation reaction of a hydrolysate of an inorganic alkoxide in the presence of a polyacrylic and polyvinyl alcohol.  \n\nThe present invention provides an anti-fogging coating film formed by using, as a main component, a composition obtained by the polycondensation reaction of a hydrolysate of an inorganic alkoxide in the presence of a polyacrylic, polyvinyl alcohol and hydrosilicofluoric acid.  \n\nThe present invention provides an anti-fogging coating film formed by using, as a main component, a composition obtained by the polycondensation reaction of a hydrolysate of an inorganic alkoxide in the presence of a polyacrylic, polyvinyl alcohol, hydrosilicofluoric acid and a silane coupling agent having an epoxy group.  \n\nThe present invention yet further provides an anti-fogging coating film formed by using, as a main component, a composition obtained by the polycondensation reaction of a hydrolysate of an inorganic alkoxide in the presence of a polyacrylic, polyvinyl alcohol and a specific benzophenone compound.  \n\nThe present invention yet still further provides an antifogging article obtained by providing any one of the aforementioned anti-fogging coating films on the surface of a substrate.  \n\nThe anti-fogging coating films obtained by using the anti-fogging coating material according to the present invention combine excellent anti-fogging properties with high insolubility, abrasion resistance and weather resistance",
+        "category": " Introduction"
+    },
+    {
+        "id": 12,
+        "chunk": "# US 6,306,932 B1  \n\nwhich are required of anti-fogging coating films. Such a phenomenon that the anti-fogging properties is developed on the anti-fogging coating films according to the present invention is considered to be as follows. The polyacrylic and polyvinyl alcohol are generally soluble in water or an alcoholic solvent. However, the polyacrylic and polyvinyl alcohol contained in the anti-fogging coating films according to the present invention do not dissolve out even when the films are immersed in water or the alcoholic solvent. The reason is considered to be due to the fact that when a hydrolysate of an inorganic alkoxide undergoes the polycondensation reaction, it also reacts with the coexisting polyacrylic and polyvinyl alcohol to form a complex polymer having an inorganic moiety derived from the inorganic alkoxide and an organic moiety having hydrophilic groups derived from the polyacrylic and polyvinyl alcohol. Further, the hydrophilic groups of the complex polymer effectively orient, whereby moisture or water from the outside can be absorbed greatly and quickly.  \n\nThe hydrolysis of the inorganic alkoxide and the polycondensation reaction subsequent thereto are called a sol-gel processing reaction such that an inorganic alkoxide is subjected to hydrolysis and polycondensation reaction in its solution to convert the solution into sol in which fine particles of an inorganic oxide or inorganic hydroxide are dissolved, and the reaction is further allowed to proceed to form gel. In the present invention, a film has been formed with the anti-fogging coating material obtained by conducting this reaction in the presence of the polyacrylic and polyvinyl alcohol, thereby obtaining an anti-fogging coating film having excellent anti-fogging properties.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# DETAILEDDESCRIPTION OF THE PREFERRED EMBODIMENTS  \n\nThe inorganic alkoxide used in the present invention is at least one of compounds represented by the formulae  \n\n$$\n\\mathbf{M}(\\mathrm{OR})_{n}(\\mathrm{X})_{\\alpha-n}\n$$  \n\nwherein $\\mathbf{M}$ is an element selected from the group consisting of Si,Al, Ti, Zr, Ca, Fe, V, Sn, Li, Be, B and P, R is an alkyl group, X is an alkyl group, an alkyl group having a functional group or halogen, a is a valence of M, and n is an integer of from 1 to a.  \n\nAmong the compounds represented by the formula (I), the compounds in which n equals a, namely, the compounds in which only alkoxyl groups are bonded to $\\mathbf{M}$ ，are commonly used.  \n\nWhen M is Si, a is 4. Such an alkoxide is represented by $\\mathrm{Si(OR^{1})_{4}}$ ，wherein ${\\mathrm{R}}^{1}$ is preferably an alkyl group having 1 to 4 carbon atoms (hereinafter referred to as a lower alkyl group). Examples of such alkoxysilanes include $\\mathrm{Si}(\\mathrm{OCH}_{3}\\bar{)}_{4}$ and $\\mathrm{Si}(\\mathrm{OC}_{2}\\mathrm{H}_{5})_{4}$  \n\nWhen M is Al, a is 3. Such an alkoxide is represented by $\\mathrm{\\bfA}(\\mathrm{\\bfOR}^{2})_{3}$ ，wherein ${\\mathrm{R}}^{2}$ is preferably a lower alkyl group. Examples of such aluminum alkoxides include $\\operatorname{Al}(\\operatorname{OCH}_{3})_{3}$ $\\mathrm{Al}(\\mathrm{OC}_{2}\\mathrm{H}_{5})_{3}$ ， $\\mathrm{\\bfAl(O-n-C_{3}H_{7})}_{3}$ ， $\\mathrm{\\bfAl(O-iso-C_{3}H_{7})_{3}}$ and $\\mathrm{\\bfAl(OC_{4}H_{9})}_{3}$ . The aluminum alkoxides may be used either singly or in any combination thereof. Such aluminum alkoxides are generally used in combination with the alkoxysilane. The use of the aluminum alkoxide enhances the light transmission properties and heat resistance of the resulting anti-fogging coating film. The amount of the aluminum alkoxide used is preferably within a range of from 1 to 10 parts by weight per 100 parts by weight of the alkoxysilane.  \n\nWhen $\\mathbf{M}$ is $\\mathrm{Ti}$ , a is 4. Such an alkoxide is represented by $\\mathrm{Ti}(\\mathrm{OR}^{3})_{4}$ ，wherein $\\mathbb{R}^{3}$ is preferably a lower alkyl group.  \n\nExamples of such titanium alkoxides include $\\mathrm{Ti}(\\mathrm{OCH}_{3})_{4}$ $\\mathrm{Ti}(\\mathrm{OC}_{2}\\mathrm{H}_{5})_{4}$ ， $\\mathrm{Ti}(\\mathrm{O}{\\cdot}\\mathrm{n}{\\cdot}\\mathrm{C}_{3}\\mathrm{H}_{7})_{4}$ ， $\\mathrm{Ti}(\\mathrm{O-iso-C}_{3}\\mathrm{H}_{7})_{4}$ and $\\mathrm{Ti}(\\mathrm{OC}_{4}\\mathrm{H}_{9})_{4}$ . The titanium alkoxides may be used either singly or in any combination thereof. Such titanium alkoxides are generally used in combination with the alkoxysilane. The use of the titanium alkoxide enhances the ultraviolet light resistance of the resulting anti-fogging coating film, and markedly improves the heat resistance of a substrate. The amount of the titanium alkoxide used is preferably within a range of from 0.1 to 3 parts by weight per 100 parts by weight of the alkoxysilane.  \n\nWhen M is $Z_{\\mathrm{{I}}}$ a is 4. Such an alkoxide is represented by $\\mathrm{Zr(OR^{4})_{4}}$ ，wherein $\\mathrm{R}^{4}$ is preferably a lower alkyl group. Examples of such zirconium alkoxides include $\\mathrm{Zr}(\\mathrm{OCH}_{3})_{4}$ ，   \n.5 $\\mathrm{Zr}(\\mathrm{OC}_{2}\\mathrm{H}_{5})_{4}$ 。 $\\mathrm{Zr(O–iso-C}_{3}\\mathrm{H}_{7})_{4}$ ， $\\mathrm{Zr(O\\mathrm{-}t\\mathrm{-}C_{4}H_{9})_{4}}$ and Ti(O-n$\\mathrm{C_{4}H_{9}})_{4}$ . The zirconium alkoxides may be used either singly or in any combination thereof. Such zirconium alkoxides are generally used in combination with the alkoxysilane. The use of the zirconium alkoxide enhances the toughness and   \n:0 heat resistance of the resulting anti-fogging coating film. The amount of the zirconium alkoxide used is preferably within a range of from 0.5 to 5 parts by weight per 100 parts by weight of the alkoxysilane.  \n\nExamples of the alkoxides other than the above alkoxides include $\\mathrm{Ca}(\\mathrm{OC}_{2}\\mathrm{H}_{5})_{2}$ ， $\\mathrm{Fe}(\\mathrm{OC}_{2}\\mathrm{H}_{5})_{3}$ ， $\\mathrm{V}(\\mathrm{O-iso-C}_{3}\\mathrm{H}_{7})4$ ， $\\mathrm{{Sn}(O\\mathrm{-}}$ $\\mathrm{t-C_{4}H_{9})_{4}}$ ， $\\mathrm{Li}(\\mathrm{OC}_{2}\\mathrm{H}_{5})$ ， $\\mathrm{Be}(\\mathrm{OC}_{2}\\mathrm{H}_{5})_{2}$ ， $\\mathrm{B}(\\mathrm{OC}_{2}\\mathrm{H}_{5})3$ ， $\\mathrm{P}(\\mathrm{OC}_{2}\\mathrm{H}_{5})_{2}$ and $\\mathrm{P}(\\mathrm{OCH}_{3})_{3}$  \n\nAmong the alkoxides represented by the formula (I), the compounds in which n is a-1 or smaller, namely, the com  \n0 pounds in which group(s) $\\mathbf{\\boldsymbol{X}}$ other than alkoxyl groups are bonded to $\\mathbf{M}$ ,include, for example, compounds in which X tother is halogen such as Cl or Br. The compounds in which X is halogen is hydrolyzed in the same way as in a alkoxyl group to form an OH group as described below, and so a   \n5 polycondensation reaction takes place. X may be an alkyl group or an alkyl group having a functional group. The number of carbon atoms in this alkyl group is generally within a range of from 1 to 15. Such a group is not hydrolyzed, but remains as an organic moiety in the result  \n0 ing polymer. Examples of the functional group include carboxyl, carbonyl, amino, vinyl and epoxy groups. Such a group is preferred in that anti-fogging properties are enhanced as described below.  \n\nExamples of the compounds of the formula (I) having X includevinyltrichlorosilane， vinyltrimethoxysilane, vinyltriethoxysilane， $\\upgamma$ -methacryloxypropyltrimethoxysilane， $\\upgamma-\\up g1$ ycidoxypropyltrimethoxysilane, $\\upgamma\\cdot$ -aminopropyltrimethoxysilane.  \n\nExamples of the polyacrylic used in the present invention 50 include polyacrylic acid, polymethacrylic acid, and methyl and ethyl esters thereof. The methyl and ethyl esters of polyacrylic acid and polymethacrylic acid are preferably saponified products each having a saponification degree of 10 to $30\\mathrm{\\mol}\\mathrm{\\}\\%$ [namely, (the number of moles of the 55 saponified ester group) $\\times100_{I}$ (the number of moles of the saponified ester group $^+$ the number of moles of the unsaponified ester group)]. The amount of the polyacrylic used is preferably within a range of from 1 to 5 parts by weight (solid content) per 100 parts by weight of the anti-fogging 50 coating material.  \n\nThe polyvinyl alcohol used in the present invention are incompletely saponified products having a saponification degree of preferably 65 to $85\\mathrm{mol}\\%$ [namely, (the number of moles of the hydroxyl group) $\\times100_{/}$ (the number of moles of the acetyl group $^+$ the number of moles of the hydroxyl group)], more preferably 75 to $82\\mathrm{mol}\\%$ . The amount of the polyvinyl alcohol used is preferably within a range of from",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 14,
+        "chunk": "# 6  \n\n1 to 10 parts by weight (solid content) per 100 parts by weight of the anti-fogging coating material.  \n\nIn the anti-fogging coating material according to the present invention, it is preferred that hydrosilicofluoric acid be further used. The amount of hydrosilicofluoric acid used is preferably within a range of from 0.005 to 0.5 parts by weight per 100 parts by weight of the anti-fogging coating material.  \n\nIn the anti-fogging coating material according to the present invention, it is preferred that a silane coupling agent having an epoxy group be further used. The silane coupling agent is preferably $\\upgamma$ -glycidoxypropyltrimethoxysilane.The amount of the coupling agent used is preferably within a range of from 0.05 to 10 parts by weight per 100 parts by weight of the anti-fogging coating material.  \n\nThe present applicant proposed in Japanese Patent Application Ser. No. 9-206102 corresponding to U.S. patent application Ser. No. 09/119,404 that a benzophenone compound,which acts as both ultraviolet absorbent and group scavenger, is added for the purpose of enhancing the weather resistance of the resulting anti-fogging coating film. It has been confirmed that the addition of this benzophenone compound is also effective in the present invention. The benzophenone compound is represented by the general formula  \n\n![](images/a78da0646c7c75146944ec77564f7321aab101d64c3156518ee85eb12a7818d1.jpg)  \n\nwherein $\\mathbf{X}_{1}$ to $\\mathbf{X}_{10}$ ,which may be the same or different from one another, are each a group selected from the group consisting of hydrogen, a hydroxyl group, a sulfonic acid group, a carboxyl group, an acyl group, an ester group, an ether group, hydrocarbon groups, alkoxyl groups having 1 to 6 carbon atoms, an amino group, hydroxyalkyl groups and hydroxyalkoxyl groups, with the proviso that at least one of $\\mathbf{X}_{1}$ to $\\mathbf{X}_{10}$ is a group selected from a hydroxyl group and a sulfonic acid group.  \n\nAs a catalyst preferably used in the present invention, may be named an acid catalyst. The acid catalyst is used in the hydrolysis of the inorganic alkoxide.Accordingly, the inorganic alkoxide is hydrolyzed and polycondensed in some degree in advance to become a polymer (which may be an oligomer having a relatively low molecular weight) having OH groups.  \n\nAs the acid catalyst, may be used a mineral acid such as hydrochloric acid, sulfuric acid or nitric acid.An anhydride of the mineral acid, for example, hydrogen chloride gas may be used. In addition, organic acids and anhydrides thereof may be used. They are exemplified by the following: tartaric acid,phthalic acid， maleic acid，dodecylsuccinic acid, hexahydrophthalic acid, methylnadic acid, pyromellitic acid,benzophenonetetracarboxylic acid， dichlorosuccinic acid, chlorendic acid, phthalic anhydride, dodecylsuccinic anhydride， hexahydrophthalic anhydride， methylnadic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, dichlorosuccinic anhydride and chlorendic anhydride. These acid catalysts are used in an amount of preferably from 0.01 to 0.5 parts by weight, more preferably from 0.015 to 0.3 parts by weight per 100 parts by weight of the alkoxide.  \n\nFurther, the organic acid derived from the saponified moiety of the polyacrylic ester functions as a catalyst for hydrolysis and polycondensation reaction of the alkoxide, preferably the alkoxide and $\\upgamma$ -glycidoxypropyltrimethoxysilane.  \n\nExamples of an organic solvent preferably used in the anti-fogging coating material according to the present invention include solvents having good compatibility with water, such as methyl alcohol, ethyl alcohol, isopropyl alcohol and ）butyl alcohol. It is more preferred that the organic solvent be used together with water. The amount of the organic solvent used is preferably within a range of from 100 to 5,000 parts by weight per 100 parts by weight of the anti-fogging coating material.  \n\n15 The anti-fogging coating films according to the present invention can be formed via the steps of applying to the surface of a substrate a reaction solution containing at least one of an inorganic alkoxide, a hydrolysate of the inorganic alkoxide and a low molecular weight polycondensate of the   \n20 hydrolysate, a polyacrylic, polyvinyl alcohol and preferably a catalyst for accelerating the polycondensation reaction of the hydrolysate to form a coating film on the substrate surface and subjecting the coating film thus formed to heat-treatment. The term “containing at least one of an   \n25 inorganic alkoxide, a hydrolysate of the inorganic alkoxide and a low molecular weight polycondensate of the hydrolysate\" means any one of the following four cases. (1) An inorganic alkoxide is used for the preparation of the reaction solution, and the hydrolyzing reaction thereof is   \n30 effected after the preparation of the reaction solution. (2) A hydrolysate obtained by subjecting an inorganic alkoxide to a hydrolyzing reaction in advance is used for the preparation of the reaction solution. (3)A low molecular weight polycondensate obtained by   \n35 partially polycondensing a hydrolysate of an inorganic alkoxide in advance is used for the preparation of the reaction solution. (4) At least two of an inorganic alkoxide, a hydrolysate thereof and a low molecular weight polycondensate of the   \n40 hydrolysate are used for the preparation of the reaction solution.  \n\nSince the anti-fogging coating films according to the present invention are obtained by a sol-gel reaction in the presence of the polyacrylic and polyvinyl alcohol, the principal compositions of the coating films are considered to comprise a polycondensate obtained by deprotonating the OH group(s) of the hydrolysate of the inorganic alkoxide and consequently initiating a polycondensation reaction; the above-described complex polymer obtained by a crosslinking reaction between the OH groups contained in the polycondensate, and the polyacrylic, polyvinyl alcohol and the like; a reaction product of the hydrolysate of the inorganic alkoxide with the polyacrylic, polyvinyl alcohol and the like; and a reaction product of three reactants of the polycondensate, the hydrolysate, and the polyacrylic, polyvinyl alcohol and the like.  \n\nThe substrates used in the present invention include lenses, optical parallel plates, mirrors, prisms, glass and plastics.  \n\n60 The anti-fogging article according to the present invention is formed, for example, in the following manner. The individual components of the anti-fogging coating material are first mixed with each other to prepare a transparent coating fluid. This coating fluid is then applied to at least one   \n65 side of a substrate and dried under heating at preferably $80^{\\circ}$ C. or higher, more preferably at a temperature ranging from $120^{\\circ}\\mathrm{C}$ .to $200^{\\circ}\\mathrm{C}$ , thereby obtaining the anti-fogging article  \n\naccording to the present invention. If need be, the coating fluid may be applied repeatedly several times, followed by the heat treatment.  \n\nThe thickness of the coating film is preferably within a range of from $0.01\\mu\\mathrm{m}$ to $10\\mu\\mathrm m$ in the case where it is used 5 for optical lenses. When the coating fluid is applied to window glass and the like, the thickness of the coating film is preferably within a range of from $1.0\\mu\\mathrm{m}$ to $10.0\\mu\\mathrm{m}$ .The thickness of the coating film may be suitably adjusted by applying the coating fluid thick or thin, or changing the 10 number of times of the application. With the anti-fogging article thus obtained, imparts anti-fogging properties and dew condensation-preventing properties are imparted to the surface of the substrate. The anti-fogging coating film formed is insoluble in water and organic solvents and has a 15 high surface hardness.  \n\nWhen the anti-fogging coating material according to the present invention is applied to a substrate, dried and then heat-treated, the condensation reaction and crosslinking reaction among the above-described reactions are allowed to 2( proceed to form a complex polymer having a threedimensional structure. This polymer is a polymer having an inorganic moiety and an organic moiety. Since the complex polymer has an insoluble skeleton of the inorganic moiety, an anti-fogging coating film formed by this polymer is 2: insoluble in water and organic solvents and has a high surface hardness. This polymer further has hydrophilic groups derived from the polyacrylic ester and polyvinyl alcohol of the organic moiety, and such hydrophilic portions exist on the surface of the coating film formed. Therefore, 3( moisture or water is adsorbed on such a portion.  \n\nThe present invention will be described below more specifically by the following examples.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# EXAMPLE1  \n\n40  \n\nA coating fluid was prepared in accordance with the formulation shown in Table 1 by adding a $10\\%$ (by weight; the same shall apply hereinafter) aqueous solution of polyvinyl alcohol (average polymerization degree: 2,000, saponification degree: about $82\\mathrm{\\mol}\\mathrm{\\}\\%$ toa $2.5\\%$ watermethanol solution of a $20\\mathrm{\\mol}$ $\\%$ -saponified product of polymethyl acrylate [a saponified product obtained by adding methanol to a $25\\%$ aqueous solution of polyacrylic acid (average molecular weight: 150,000), stirring the resulting mixture at ordinary temperature $(25^{\\circ}\\mathrm{~C.})$ for 30 minutes to produce polymethyl acrylate, adding sodium hydroxide (caustic soda) to the polymethyl acrylate thus obtained so as to give a saponification degree of $20\\%$ and then stirring the resulting mixture for additional 30 minutes to saponify the methyl ester], stirring the resulting mixture at ordinary temperature $(25^{\\circ}\\mathrm{C})$ for 10 minutes, adding to the mixture a solution of $\\upgamma$ -glycidoxypropyl-trimethoxysilane, a solution of a hydrolysate of aluminum isopropoxide (a solution obtained by hydrolyzing aluminum isopropoxide using an acid catalyst in ethanol; $5\\%$ by weight in terms of $\\mathrm{Al}_{2}\\mathrm{O}_{3}.$ j and a $0.47\\%$ methanol solution of hydrosilicofluoric acid prepared in advance, and then stirring the resulting mixture at ordinary temperature $(25^{\\circ}\\mathrm{C}.)$ for 15 minutes.  \n\nThe coating fluid thus obtained was colorless and transparent.A glass sheet was dip coated with the coating fluid at a lifting rate of $50\\ \\mathrm{mm/min}$ by using a dip coating device. The coated glass sheet was heated and dried at $150^{\\circ}\\mathrm{~C~}$ .for 10 minutes, thereby obtaining a colorless, transparent coating film having a uniform thickness (thickness of the coating film: $3.0\\ \\mu\\mathrm{m})$ . The coated glass sheet was placed in a refrigerator (about $0^{\\circ}\\mathrm{C}.$ ) for 5 minutes and then left standing in an atmosphere of $25^{\\circ}$ C. and $81\\%$ RH. As a result, no occurrence of fogging was observed on the coated surface of the glass sheet.  \n\nTABLE1   \n\n\n<html><body><table><tr><td></td><td>(parts by weight)</td></tr><tr><td>20 mol %-Saponified product of polymethyl acrylate (solution in water-methanol)</td><td>59.50</td></tr><tr><td>10% Aqueous solution of polyvinyl alcohol (saponification degree: about 82 mol %)</td><td>37.50</td></tr><tr><td>-Glycidoxypropyltrimethoxysilane Ethanol solution of aluminum isopropoxide</td><td>0.14</td></tr><tr><td>(containing 5% by weight of AlO3)</td><td>0.28</td></tr><tr><td>0.47% Methanol solution of</td><td>2.58</td></tr><tr><td>hydrosilicofluoric acid</td><td></td></tr><tr><td>Total</td><td>100.00</td></tr></table></body></html>  \n\nThe surface of the coated glass sheet was wiped repeatedly 50 times with lens cleaning paper (Dusper, trade name; product of OZU CO., LTD., Tokyo) impregnated with water under a load of $300\\ \\mathrm{g}$ . As a result, no peeling of the coating film occurred, and its surface was not damaged by the wiping.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 16,
+        "chunk": "# COMPARATIVEEXAMPLE1  \n\nA test was made in the same manner as in Example 1 except that no coating film was applied to the glass sheet. As a result, fogging immediately occurred on the surface of the glass sheet, and was not removed until 5 minutes later.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# COMPARATIVEEXAMPLE2  \n\nA coating fluid prepared in the same manner as in Example 1 except that the $10\\%$ aqueous solution of polyvinyl alcohol was not added, was used to prepare a coated 35 glass sheet in the same manner as in Example 1. The surface of the coated glass sheet was tested for separation of coating film in the same manner as in Example 1. As a result, separation of the coating film occurred at the time the surface had been wiped repeatedly 5 times.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# EXAMPLE 2  \n\nA coated glass sheet was prepared in the same manner as in Example 1 except that hydrosilicofluoric acid used in Example 1 was not added. The anti-fogging effect of this   \n45 glass sheet was the same as in Example 1.When the surface of the coated glass sheet was wiped repeatedly with lens cleaning paper in the same manner as in Example 1,no peeling of the coating film occurred even after the surface was wiped repeatedly about 25 times. However, it was   \n50 observed that the surface was somewhat damaged by the wiping.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# EXAMPLE 3  \n\nA coating fluid was prepared in accordance with the   \n55 formulation shown in Table 2 by adding methanol and a $10\\%$ aqueous solution of polyvinyl alcohol (average polymerization degree: 2,Ooo; saponification degree: about $82\\mathrm{mol}\\%$ j to a $25\\%$ aqueous solution of polyacrylic acid (average molecular weight: 150,O00), stirring the resulting mixture at   \n60 ordinary temperature $(25^{\\circ}\\mathrm{C})$ for 10 minutes, adding to the mixture a solution of $\\upgamma$ -glycidoxypropyltrimethoxysilane，a solution of a hydrolysate of aluminum isopropoxide (a solution obtained by hydrolyzing aluminum isopropoxide using an acid catalyst in ethanol; $5\\%$ by weight in terms of   \n65 $\\mathbf{Al}_{2}\\mathbf{O}_{3},$ and a $0.47\\%$ methanol solution of hydrosilicofluoric acid prepared in advance, and then stirring the resulting mixture at ordinary temperature $(25^{\\circ}\\mathrm{~C~})$ for 15 minutes.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 20,
+        "chunk": "# 9  \n\nThe coating fluid thus obtained was colorless and transparent. This coating fluid was applied to a glass sheet and dried in the same manner as in Example 1, thereby obtaining a colorless, transparent coating film having a uniform thickness (thickness of the coating film: $3.0\\mu\\mathrm{{\\bar{m}}}{\\cdot}$ ，  \n\nThe coated glass sheet thus obtained was tested in the same manner as in Example 1. As a result, neither fog nor frost occurred on the coated surface of the glass sheet.  \n\nTABLE 2   \n\n\n<html><body><table><tr><td></td><td>(parts by weight)</td></tr><tr><td>25% Aqueous solution of polyacrylic acid</td><td>6.00</td></tr><tr><td>Methanol 10% Aqueous solution of polyvinyl alcohol</td><td>53.50 37.50</td></tr><tr><td>(saponification degree: about 82 mol %) -Glycidoxypropyltrimethoxysilane</td><td></td></tr><tr><td>Ethanol solution of aluminum isopropoxide</td><td>0.14 0.28</td></tr><tr><td>(containing 5% by weight of AlO3) 0.47% Methanol solution of</td><td>2.58</td></tr><tr><td>hydrosilicofluoric acid</td><td></td></tr><tr><td>Total</td><td>100.00</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# EXAMPLE4  \n\nA $10\\%$ methanol solution of $^{2,2^{\\prime},4,4^{\\prime}}$ -tetrahydroxybenzophenone as an ultraviolet light absorber and a $10\\%$ methanol solution of bis-[N-formyl-(2,2,6,6-tetramethyl-4- piperidyl)imino]hexamethylene as a supplementary ultraviolet light absorber, both prepared in advance were added to a coating fluid prepared in the same manner as in Example 1 in accordance with the formulation shown in Table 3. The mixture was stirred at ordinary temperature $(25^{\\circ}\\mathrm{C})$ for 15 minutes. The coating fluid thus obtained had a yellow color. This coating fluid was applied to a glass sheet and dried in the same manner as in Example 1. The coating film (thickness of the coating film: ${3.0\\ \\mu\\mathrm{m}},$ ）thus obtained was colorless and transparent. The coated glass sheet thus obtained was tested in the same manner as in Example 1.As a result, neither fog nor frost occurred on the coated surface of the glass sheet.  \n\nThe coated glass sheet was exposed for 20o hours to ultraviolet light $(250\\ \\mathrm{nm},4\\ \\mathrm{kW})$ from a distance of about 24 cm. Then, the coated glass sheet was subjected to the same test on anti-fogging properties as described above. As a result, neither fog nor frost occurred on the coated surface of the glass sheet, and besides, the surface did not undergo changes such as cracking and separation.  \n\nTABLE 3   \n\n\n<html><body><table><tr><td></td><td>(parts by weight)</td></tr><tr><td>20 mol %-Saponified product of polymethylacrylate (solution in water-methanol)</td><td>58.58</td></tr><tr><td>10% Aqueous solution of polyvinyl alcohol (saponification degree: about 82 mol %)</td><td>36.92</td></tr><tr><td>-Glycidoxypropyltrimethoxysilane</td><td>0.14</td></tr><tr><td>Ethanol solution of aluminum isopropoxide (containing 5% by weight of Al2O3)</td><td>0.27</td></tr><tr><td>0.47% Methanol solution of hydrosilicofluoric acid</td><td>2.54</td></tr><tr><td>10% Methanol solution of ultraviolet light absorber</td><td>1.03</td></tr><tr><td>10% Methanol solution of supplementary</td><td>0.52</td></tr><tr><td>ultraviolet light absorber Total</td><td>100.00</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 22,
+        "chunk": "# EXAMPLE5  \n\nA coating fluid was prepared in accordance with a formulation shown in Table 4, and a coated glass sheet was prepared in the same manner as in Example 1.  \n\nThe anti-fogging effect of this glass sheet was the same as in Example 1.When the surface of the coated glass sheet was wiped repeatedly with lens cleaning paper in the same manner as in Example 1,no peeling of the coating film occurred even after the surface was wiped repeatedly 30 times.Partial peeling of the coating film was observed at the time the surface had been wiped repeatedly about 40 times.  \n\nTABLE 4   \n\n\n<html><body><table><tr><td></td><td>(parts by weight)</td></tr><tr><td>20 mol %-Saponified product of polymethyl acrylate (solution in water-methanol)</td><td>59.58</td></tr><tr><td>10% Aqueous solution of polyvinyl alcohol (saponification degree: about 82 mol %)</td><td>37.55</td></tr><tr><td>Ethanol solution of aluminum isopropoxide (containing 5% by weight of AlO3)</td><td>0.28</td></tr><tr><td>0.47% Methanol solution of</td><td>2.59</td></tr><tr><td>hydrosilicofluoric acid Total</td><td>100.00</td></tr></table></body></html>  \n\nWhile the present Invention has been described with respect to what is presently considered to be the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. To the contrary, the invention is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.  \n\nWhat is claimed is:  \n\n1. An anti-fogging coating material comprising a solution which comprises: i) at least one composition selected from the group consisting of an inorganic alkoxide, a hydrolysate of the inorganic alkoxide and a polycondensate of the hydrolysate of the inorganic alkoxide; ii) a polyacrylic; and iii) polyvinyl alcohol. 2. The anti-fogging coating material according to claim 1, wherein the inorganic alkoxide is at least one of compounds represented by the formulae  \n\n$$\n\\mathbf{M}(\\mathrm{OR})_{n}(\\mathrm{X})_{a-n}\n$$  \n\n45 wherein $\\mathbf{M}$ is an element selected from the group consisting of Si,Al, Ti, Zr, Ca, Fe, V, Sn, Li, Be, B and P, R is an alkyl group, $\\mathbf{X}$ is an alkyl group, an alkyl group having a functional group or halogen, a is a valence of $\\mathbf{M}$ ，and $\\mathfrak{n}$ is an integer of from 1 to a.   \n50 3. The anti-fogging coating material according to claim 1, wherein the inorganic alkoxide is at least one selected from the group consisting of $\\mathrm{Si}(\\mathrm{OC}_{2}\\mathrm{H}_{5})_{4},\\mathrm{Al}(\\mathrm{O-i}\\mathrm{so-C}_{3}\\mathrm{H}_{7})_{3}$ . $\\mathrm{Ti(O\\mathrm{-}}$ iso- ${\\cdot}{\\mathrm{C}}_{3}\\mathrm{H}_{7}{\\rangle}_{4}$ ， $\\mathrm{Zr(O\\mathrm{-}t\\mathrm{-}C_{4}H_{9})_{4}}$ ， $\\mathrm{Zr(O{-}n{-}C_{4}H_{9})_{4}},$ $\\mathrm{Ca}(\\mathrm{OC}_{2}\\mathrm{H}_{5})_{2}$ ， $\\mathrm{Fe(OC}_{2}\\mathrm{H}_{5})_{3}$ ， $\\mathrm{V}(\\mathrm{O-iso-}\\mathrm{C}_{3}\\mathrm{H}_{7})_{4}$ ， $\\mathrm{Sn(O\\mathrm{-}t\\mathrm{-}C_{4}H_{9})_{4}}$ ， $\\mathrm{Li}(\\mathrm{OC}_{2}\\mathrm{H}_{5})$ ，   \n55 $\\mathrm{Be}(\\mathrm{OC}_{2}\\mathrm{H}_{5})_{2}$ 。 $\\mathrm{B}(\\mathrm{OC}_{2}\\mathrm{H}_{5})_{3}$ ， $\\mathrm{P}(\\mathrm{OC}_{2}\\mathrm{H}_{5})_{2}$ and $\\mathrm{P}(\\mathrm{OCH}_{3})_{3}$ · 4. The anti-fogging coating material according to claim 1, wherein hydrosilicofluoric acid is further used as a formulation ingredient. 5. The anti-fogging coating material according to claim 1,   \n60 wherein a silane coupling agent having an epoxy group is further used as a formulation ingredient. 6. The anti-fogging coating material according to claim 5, wherein the epoxy group is a glycidoxy group. 7. The anti-fogging coating material according to claim 1,   \n65 wherein hydrosilicofluoric acid and a silane coupling agent having an epoxy group are further used as formulation ingredients.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# 11  \n\n8. The anti-fogging coating material according to claim 1, wherein the polyacrylic is at least one selected from the group consisting of polyacrylic acid, polymethacrylic acid, polyacrylic esters and polymethacrylic esters.  \n\n9. The anti-fogging coating material according to claim 1, wherein a saponification degree of polyvinyl alcohol is 65 to $85\\mathrm{~mol~}\\%$  \n\n10. The anti-fogging coating material according to claim 1,wherein a benzophenone compound represented by the following formula is further used as a formulation ingredient:  \n\nthe presence of a polyacrylic, polyvinyl alcohol and hydrosilicofluoric acid.  \n\n13. An anti-fogging coating film formed by using, as a main component, a composition obtained by a polycondensation reaction of a hydrolysate of an inorganic alkoxide in the presence of a polyacrylic, polyvinyl alcohol, hydrosilicofluoric acid and a silane coupling agent having an epoxy group.  \n\n14. An anti-fogging coating film formed by using, as a main component, a composition obtained by a polycondensation reaction of a hydrolysate of an inorganic alkoxide in the presence of a polyacrylic, polyvinyl alcohol and a benzophenone compound represented by the formula  \n\n15  \n\n![](images/d74e74bbcef7adec0cadac3e6b5ff836dbc187cfcb61dfbb8b1bdbcf3cc6664e.jpg)  \n\nwherein $\\mathbf{X}_{1}$ to $\\mathbf{X}_{10}$ , which may be the same or different from one another, are each a group selected from the group consisting of hydrogen, a hydroxyl group,a sulfonic acid group, a carboxyl group, an acyl group, an ester group, an ether group, hydrocarbon groups, alkoxyl groups having 1 to 6 carbon atoms, an amino group, hydroxyalkyl groups and hydroxyalkoxyl groups, with the proviso that at least one of $\\mathbf{X}_{1}$ to $\\mathbf{X}_{10}$ is a group selected from the group consisting of a hydroxyl group and a sulfonic acid group.  \n\n11. An anti-fogging coating film formed by using, as a main component, a composition obtained by a polycondensation reaction of a hydrolysate of an inorganic alkoxide in the presence of a polyacrylic and polyvinyl alcohol.  \n\n12. An anti-fogging coating film formed by using, as a main component, a composition obtained by a polycondensation reaction of a hydrolysate of an inorganic alkoxide in wherein $\\mathbf{X}_{1}$ to $\\mathbf{X}_{10}$ ,which may be the same or different from one another, are each a group selected from the group consisting of hydrogen, a hydroxyl group, a sulfonic acid group, a carboxyl group, an acyl group, an ester group, an ether group, hydrocarbon groups, alkoxyl groups having 1 to 6 carbon atoms, an amino group, hydroxyalkyl groups and hydroxyalkoxyl groups, with the proviso that at least one of $\\mathbf{X}_{1}$ to $\\mathbf{X}_{10}$ is a group selected from the group consisting of a hydroxyl group and a sulfonic acid group.  \n\n![](images/0c1a646541d64595753ad3fdd718f7afc09fdfb8d7f37f9442b1993bfa330c00.jpg)",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# (12) United States Patent Heberger et al.",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (54) ANTI-FOG COATING AND COATED FILM  \n\n(75) Inventors: John M.Heberger; Robin M. Donald, both of Greer; Jan C. Westermeier, Taylors; F. Gene Funderburk, Taylors; John G. Rollins, Taylors, all of SC (US)  \n\n(73） Assignee: Mitsubishi Polyester Film, LLC, Greer, SC (US)  \n\n（\\*）Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days.  \n\n(21) Appl. No.: 09/466,377  \n\n(22) Filed: Dec.17,1999   \n(51) Int. Cl.7 B32B 27/06; B32B 27/08; B32B 27/18; B32B 27/36   \n(52) U.S. Cl. 428/215; 428/480; 428/482; 428/213; 428/216; 106/13; 528/293; 528/294; 528/295; 528/302; 528/308; 528/308.6; 528/308.7; 427/384; 427/385.5; 427/393.5   \n(58) Field of Search 428/480, 482, 428/212,213,215,216; 528/302,308, 308.6, 308.7,293, 294, 295; 106/13",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# References Cited",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# U.S.PATENTDOCUMENTS  \n\n4,467,073 A 8/1984 Creasy   \n4,816,333 A 3/1989 Lange et al.   \n4,847,324 A 7/1989 Creasy   \n4,944,294 A 7/1990 Borek, Jr.   \n4,987,182 A 1/1991 Creasy   \n5,020,533A 6/1991 Hubbard et al.   \n5,334,457 A \\* 8/1994 Wada et al. 428/480   \n5,496,647 A 3/1996 Krejci et al.   \n5,512,211 A 4/1996 McSwigan et al.   \n(10) Patent No.: US 6,455,142 B1   \n(45) Date of Patent: Sep. 24, 2002   \n5,545,713A 8/1996 Krejci et al.   \n5,562,997 A 10/1996 Krejci et al.   \n5,585,186 A 12/1996 Scholz et al.   \n5,607,777 A 3/1997 Krejci et al.   \n5,723,175 A 3/1998 Scholz et al.   \n5,753,373 A 5/1998 Scholz et al.   \n5,759,696 A $*$ 6/1998 Alers 428/431   \n5,873,931 A 2/1999 Scholz et al.   \n5,997,621 A 12/1999 Scholz et al.   \n6,228,499 B1 $*$ 5/2001 Nakauchi et al. 428/412",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# FOREIGNPATENTDOCUMENTS  \n\n<html><body><table><tr><td>EP</td><td>0 896 229 A2</td></tr><tr><td>EP</td><td>0 899315 A2 3/1999 6/1997</td></tr><tr><td>JP</td><td>97/170325</td></tr><tr><td>JP</td><td>97/202803 7/1997</td></tr><tr><td>JP</td><td>97/206102 7/1997</td></tr><tr><td>JP</td><td>97/260373 9/1997</td></tr><tr><td>JP</td><td>97/279012 10/1997</td></tr><tr><td>WO</td><td>WO95US15648 11/1995</td></tr><tr><td>WO</td><td>WO95/32237 11/1995</td></tr><tr><td>WO</td><td>WO 96/18918 6/1996</td></tr></table></body></html>",
+        "category": " References"
+    },
+    {
+        "id": 6,
+        "chunk": "# OTHER PUBLICATIONS  \n\nAerosol OT-NV product data sheet.  \n\n\\* cited by examiner  \n\nPrimary Examiner—Vivian Chen",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# ABSTRACT  \n\nThe present invention provides a coated polymer film having an essentially streak-free coated surface that resists the formation of fog. The film includes a self-supporting polymer film layer, and an anti-fog coating on the film layer. The anti-fog coating, which can also be applied to alternate substrates, consisting essentially of a copolyester binder and an anionic surfactant, wherein the surfactant contains less than about 0.5 weight percent of a fluorosurfactant. A slip agent can also be included in the anti-fog coating.",
+        "category": " Abstract"
+    },
+    {
+        "id": 8,
+        "chunk": "# 36 Claims, No Drawings",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# 1",
+        "category": ", but it seems that the text segment you mentioned is missing. Please provide the text segment, and I will be happy to analyze it and classify it according to the categories you've provided."
+    },
+    {
+        "id": 10,
+        "chunk": "# ANTI-FOG COATING AND COATED FILM  \n\nBACKGROUNDOFTHEINVENTION",
+        "category": " Introduction"
+    },
+    {
+        "id": 11,
+        "chunk": "# 1.Field of the Invention  \n\nThe present invention relates generally to a method for creating a fog resistant product, typically a polymer film, by means of coating the product with an anti-fog coating. The anti-fog coating is also disclosed.",
+        "category": " Introduction"
+    },
+    {
+        "id": 12,
+        "chunk": "# 2. Description of Related Art  \n\nAnti-fog coatings are desirable for many applications, such as facemasks and other types of face protection, eyewear such as goggles and glasses, car windshields, windows, bathroom mirrors, see-through packaging materials for moist foods and the like. Disposable and replaceable liners for eyewear such as welding goggles, ski goggles and the like, or for other surfaces subject to fogging, such as windows, are also a desired end use. In many of these applications, it is important that the coating be substantially transparent. However, prior art anti-fog coatings have suffered from numerous limitations, including high cost, need for frequent re-application, inadequate transparency and limited anti-fog properties. There is a need for anti-fog coatings that address one or more of these problems. There is similarly a need for anti-fog coatings that are suitable for use on disposable items such as single-use facemasks.A need also exists for anti-fog coatings that are adapted for application to polymer film substrates. In addition, prior art anti-fog coatings are typically applied off-line. This is a less efficient and more costly alternative. Coatings adapted for in-line application are also desirable.",
+        "category": " Introduction"
+    },
+    {
+        "id": 13,
+        "chunk": "# BRIEFSUMMARYOFTHEINVENTION  \n\nAccordingly, it is an object of the present invention to provide an anti-fog coating suitable for application to a base polymer film.  \n\nIt is a further object of the present invention to provide a base polymer film with an anti-fog coating on one or both sides.  \n\nIt is another object of the present invention to provide an anti-fog coating that is substantially free of streaks and smears, particularly when applied to a base polymer film.  \n\nIt is yet another object of the present invention to provide an anti-fog coating that is substantially transparent.  \n\nThe present invention has accomplished these objectives by providing in a preferred embodiment a coated polymer film having an essentially streak-free coated surface that resists the formation of fog. The film includes a selfsupporting polymer film layer, and an anti-fog coating on the film layer. The anti-fog coating, which can also be applied to alternate substrates, includes a binder and a surfactant, where the surfactant preferably includes a fluorosurfactant at less than about 0.5 weight percent.",
+        "category": " Abstract"
+    },
+    {
+        "id": 14,
+        "chunk": "# DETAILED DESCRIPTION OF THE INVENTION  \n\nThe present inventors have surprisingly found that excellent anti-fog properties are provided by a coating that includes a copolyester binder and specific surfactants. The selection of binder and surfactants, and the specific amounts used of the preferred fluorosurfactant, have been found to be critical to the optimal anti-fog results achieved by various coatings of this invention.  \n\nThe anti-fog coating of the present invention preferably includes a binder to anchor the anti-fog coating to the base polymer film. Polymeric binders have proven to be most effective. One preferred binder is a water soluble copolyester. Preferably, the water soluble copolyester includes a  \n\ncopolyester as disclosed in U.S. Pat. No. 4,493,872 to Funderburk et al., the disclosure of which is incorporated herein by reference in its entirety. This copolyester is disclosed as the condensation product of the following   \nC maderfogi sulfonate group attached to a dicarboxylic aromatic nucleus and an alkylene glycol with about 2 to about 11 carbon atoms. Optionally, an aliphatic dicarboxylic acid of the formula $\\mathrm{\\bar{HOOC}(\\bar{C H}_{2})-}_{n}\\mathrm{\\bar{COOH}}$ ,where n is about 1 to about   \n10 11, can also be employed as a monomer therein.An optimal copolyester is made up of about $90~\\mathrm{mol}$ percent isophthalic acid，about $10~\\mathrm{\\mo{\\bar{l}}}$ percent of the sodium salt of 5-sulfoisophthalic acid and about $100\\mathrm{mol}$ percent ethylene glycol. It is important to note, however, that the preferred per  \n15 centage of sulfomonomer, isophthalic acid and aliphatic dicarboxylic acid employed is somewhat broader in the context of the present invention than in the Funderburk et al. patent. For example, in the context of the present invention, isophthalic acid is preferably about 50 to about $98\\mathrm{\\mol}$   \n20 percent, aliphatic dicarboxylic acid is preferably about 0 to about $50~\\mathrm{mol}$ percent, and the sulfomonomer is preferably about 2 to about $20\\mathrm{mol}$ percent. In addition, the sulfomonomer group of the present invention is not limited to an alkali metal sulfonate group. Any sulfomonomer in which a sulfonate group is attached to a dicarboxylic nucleus is pre  \n25 ferred for use herein. In fact, any water soluble copolyester that functions to bind the coating to the surface of the base polymer film, either alone or synergistically in combination with other components, is preferred for use in the anti-fog coating of the present invention.  \n\n30 It is believed that films coated with an anti-fog film containing this binder would possess the improved adhesion to inks and metals that have been previously disclosed in conjunction with this class of compounds.  \n\nAnother preferred water-soluble copolyester binder is a   \n351 polymer having a Chemical Abstract Name of 1,3- benzenedicarboxylic acid, 5-sulfo-, 1,3-dimethyl ester, sodium salt, polymer with dimethyl $^{1,4-}$ benzenedicarboxylate, 1,2-ethanediol and 2, $2\"$ -oxybis [ethanol]. The molecular formula of this polymer is $\\mathrm{\\bar{(C_{10}H_{10}O_{7}S.C_{10}H_{10}O_{4}}}$ .1 $\\mathrm{C}_{4}\\mathrm{H}_{10}\\mathrm{O}_{3}.\\mathrm{C}_{2}\\mathrm{H}_{6}\\mathrm{O}_{2}.\\mathrm{\\hat{N}a}\\big)_{x}$ . This   \n40 copolyester is commercially available as AJ2oA polymer from Palmetto Chemicals, Greenville, South Carolina, and contains an antimony catalyst. A similar polymer commercially available from the same company as AJ30 polymer is also preferred for use herein, but it contains a titanium   \n45 catalyst. It is believed that the antimony catalyst of the AJ20A polymer is preferable because it minimizes the yellowness of reclaimed scrap film. The reclaim (no excessive yellowing or deterioration in physical properties when coated film scrap is mixed with fresh polymer and   \n50 reextruded) and recycling characteristics of coated polymer film are important.The ability to reuse scrap film, instead of disposing of it, reduces material and waste disposal costs and minimizes unnecessary waste. Without intending to be bound by theory, it is believed   \n55 that water soluble and water dispersible binders are preferred for use in the present invention because this water sensitivity contributes to the positive antifog performance, particularly in combination with anionic surfactants. It is postulated that the surfactant induces wet out of the water droplets on the film surface, preventing fog, and the water   \n60 sensitive binder absorbs the water, conducting it away from the surface. Water-based binders are also preferred for health and safety reasons, due the elimination or reduction of potentially hazardous solvents.In addition, is it believed that the preferred coating layers of the present invention are   \n65 substantially amorphous, non-crystalline layers. They are preferably hydrophilic, water-wicking or water-dispersing layers.  \n\nBinders containing water-dispersing agents are preferred for use in the present invention. Agents having a sulfonated component are particularly useful. Such water-dispersing agents include 5-sulfoisophthalic acid (also known as 5-SIPA), or its 1,3-dimethyl ester sodium salt. Alternate sulfomonomers disclosed in U.S. Pat. No. 5,496,647 to Krejci et al., the disclosure of which is incorporated herein by reference, are also preferred for use herein.  \n\nThe binder is preferably present at about 1 to about 30 percent by weight of the coating solution, and in an alternate preferred embodiment, it is present at about 1 to about 6 percent by weight of the coating solution.  \n\nIt is also preferred that the anti-fog coating of the present invention include a surfactant or mixture of surfactants. In one preferred embodiment, the anti-fog coating contains an anionic surfactant. The anionic surfactant results in a high wetting tension on the surface of the dried coating, and the high wetting tension prevents the formation of minute water droplets—fog—on the film surface. The anionic surfactant further enhances the wet-out of the water to maintain a clear, non-fogged surface.A preferred anionic surfactant for use in the anti-fog coatings of the present invention is sodium dodecyl benzenesulfonate. This surfactant is commercially available as Rhodacal LDS-10 surfactant from Rhone Poulenc. In an alternate preferred embodiment, a fluorosurfactant is included in the anti-fog coating of the present invention. Preferably, this fluorosurfactant contains fluoroaliphatic oxyethylenes of carbon chain lengths of about 4 to about 8, and it can also include polyethylene glycol. Such a flurosurfactant is commercially available from 3M as Fluorad FC-17oC surfactant. The fluorosurfactant, among other things, serves to minimize streaking of the coating. This effect is shown clearly when the coating is applied to a polymer film surface. This is particularly important for anti-fog coatings that are applied to clear films for applications such as window films and face shields, where visibility should not be limited by streaks or smears. The fluorosurfactant works optimally in combination with the anionic surfactant because it minimizes or eliminates the coating streaks that can be caused by the anionic surfactant.  \n\nAlternate surfactants that are preferred for use in the present invention include sodium lauryl sulfate, an anionic 4 surfactant commercially available as Sipon UB, and a sulfosuccinate blend, an anionic surfactant commercially available as Aerosol OTNV. While this blend is proprietary, it is indicated to be covered by U.S. Pat. No. 5,512,211, the disclosure of which is incorporated herein by reference.A 4 similar surfactant, Aerosol TO, is also commercially available from Cytec Industries, and is a sodium dioctyl sulfosuccinate. The anionic surfactant sodium 2-ethylhexyl sulfate,commercially available as Rhodapon BOS, is also preferred for use herein. 5  \n\nThe surfactant component is preferably present at about 0.4 to about 2.O weight percent of the anti-fog coating composition. Higher levels can be used, however they typically result in an increase in haze,which is undesirable for many applications. In an alternate preferred embodiment, the surfactant component makes up about O.8 to about 1.5 weight percent of the coating. It has been surprisingly found that the fluorosurfactant provides optimal results when present at no more than about O.5 weight percent of the coating. A range of about 0.0o1 to about 0.5 weight percent is preferred, with a range of about 0.01 to about 0.10 being alternately preferred. In an alternate embodiment, the preferred content is about O.05 weight percent fluorosurfactant of the coating. At significantly higher amounts of fluorosurfactant, the anti-fog properties of the coating and coated film show markedly lower performance.  \n\nThe ingredients of the anti-fog coating are preferably formulated as a dispersion in water or a water-containing solvent. Alternatively, alcohols or other suitable organic solvents can be employed, alone or in combination with water. The solids level is preferably up to about 50 weight percent, alternatively about O.01 to about 30 weight percent, more preferably about 1 to about 6 weight percent.  \n\nIn addition, a slip agent is preferably incorporated into the anti-fog coating of the present invention. The slip agent is believed to enhance the ability of the coated film to wind smoothly during the manufacturing process. The slip agent   \n10 is preferably inorganic. More preferably, the slip agent includes colloidal $\\mathrm{SiO}_{2}$ ，most preferably the product commercially available as Nalco $1060\\textcircled{\\mathrm{B}}$ colloidal $\\bar{\\mathrm{SiO}}_{2}$ from the Nalco Chemical Company. Other slip agents that are preferred for use in the present invention include silica in one or more of its various morphological forms, including those l5 commercially available as Syloid $\\textsuperscript{\\textregistered}$ silica or Rapidup $\\textsuperscript{\\textregistered}$ silica, although due to their larger particle size, they are less preferred for uses in which clarity and low haze are needed. Moreover, a combination of two or more of the foregoing slip agents is also preferred for use. The slip agent is   \n20 preferably present at about 0.25 to about 2 weight percent of the anti-fog coating. In an alternate preferred embodiment, the slip agent is present at about O.3 to about 1.0 weight percent, or in a third preferred embodiment at about 0.5 weight percent.  \n\nConventional additives that are known in the art can be included in the anti-fog coatings of the present invention. For example, pigments, other colorants, stabilizers, antistatic agents, adhesion promoters, antioxidants, delusterants, fillers, plasticizers and the like can be included in the anti-fog coatings of the present invention.  \n\nThe preferred solids level of the anti-fog coating, as it is applied to the base polymer film, is a level sufficient to yield a final dry coating thickness within the range of about 0.02 microns to about O.1 microns, alternatively about 0.03 microns to about O.o5 microns. In addition, the anti-fog coating of the present invention is suitable for application at much higher levels, and for extrusion or coextrusion as a separate self-supporting web.  \n\nThe coating compositions of the present invention can be formulated by simply combining the desired coating components.Agitation may be used to insure an even dispersion or solution.  \n\nBase Film  \n\nFor many preferred uses of the coating and method of the present invention, a polymer film substrate is most useful. It provides a lightweight, substantially transparent, inexpensive, disposable or recyclable substrate that accommodates many of the end uses of fog resistant materials.In addition, the coated polymer film can also easily be laminated by heat bonding or by adhesives to various other substrates.  \n\nThe anti-fog coatings and coating methods of the present invention are applicable to any polymeric film capable of acting as a substrate for an anti-fog coating.For example, the present invention is applicable to polymeric films such as   \n55 those made from polyamides exemplified by nylon; polyolefins such as polypropylene and polyethylene; polyester such as polyethylene terephthalate; polyacetal; polycarbonate; and the like. The invention is particularly applicable to polyester, most preferably polyethylene terephthalate, polyethylene naphthalate or polybutylene terephthalate. The   \n50 present invention is also applicable to polymeric films including copolyesters such as polyethylene terephthalate isophthalate.A preferred process for forming a base film is set forth in U.S.Pat.No. 5,350,601 to Culbertson et al., incorporated herein by reference. Generally, any polyester   \n55 film based on a polymer resulting from polycondensation of a glycol or diol with a dicarboxylic acid (or its ester equivalents) such as terephthalic acid, isophthalic acid,  \n\nsebacic acid, malonic, adipic, azelaic, glutaric, suberic, succinic acids and the like, of mixtures of two or more of the foregoing, are_ preferred for use in the present invention. Suitable glycols include ethylene glycol, diethylene glycol, polyethylene glycol, and polyols such as butanediol and the like. Mixtures of two or more of the foregoing are also suitable.  \n\nAny of the above base polymer films can contain conventional additives such as antioxidants, delusterants, pigments, fillers such as silica, calcium carbonate, kaolin, titanium dioxide, antistatic agents and the like, or mixtures thereof, all of which are well known in the art.  \n\nIn addition, the base polymer film may be a polymer laminate. Such laminates include polymer-polymer laminates like polyester-polyolefin or polyester-adhesivepolyolefin, polymer-metallic laminates such as polyesteraluminum, or polymer-paper or polymer-adhesive-paper laminates. Coated polymer films or film laminates can also be used. Primer coatings used to enhance wet-out or coating adhesion are preferred examples of such coatings.  \n\nThe films may be produced by any well known technique in the art. For example, polyester is typically melted and extruded as an amorphous sheet onto a polished revolving casting drum to form a cast sheet of the polymer. The sheet is quickly cooled and then stretch oriented in one or more directions to impart strength and toughness to the film. The sheet is typically stretched from about two to about four times the original cast sheet dimension, in one or both directions. Biaxial orientation is most preferred, with monoaxial orientation being less preferred. Generally, stretching occurs in a temperature range from about the second order transition temperature of the polymer to below the temperature at which the polymer softens and melts. Where necessary, the film is heat treated after stretching to “lockin” the properties by further crystallizing the film. The crystallization imparts stability and good tensile properties to the film. Such heat treatment for polyester film is generally conducted at about $190^{\\circ}\\mathrm{~C~}$ .to about $240^{\\circ}\\mathrm{~C~}$  \n\nAs discussed above,the coatings and methods of reducing fog of the present invention are not limited to use on polymer film bases. Alternate substrates such as metals, glass, polymeric articles and the like can be coated according to the teachings of the present invention. Furthermore, it is envisioned that polymer films coated with the coatings of the present invention can also be applied to other surfaces, including irregular surfaces, to provide anti-fog properties to those surfaces. The film may be heat bonded or adhered to the surface, or can be mechanically attached via fasteners, clips and the like.  \n\nCoating Methods  \n\nIn-line coating of the base polymer layer, in which the coatings are applied during the film manufacturing process and before it is heat-set, is the preferred method for use of s the coatings disclosed herein. Typically, the base polymer film is coated after corona treatment and prior to the stretch orientation of the film as described in British Pat. No. 1,411,564, or coated between drawing steps (when biaxially oriented film is produced) as taught byU.S. Pat. No. 4,571,363, or coated post-draw as taught by U.S. Pat. No. 3,322,553.  \n\nIn addition to in-line coating, one or more of the coatings of the present invention may be off-line coated (after manu  \n\nfacturing and heat setting the film), preferably after conventional surface modification of the polymeric substrate has occurred. Thus, the coating and method of the present invention are also intended for use where, for example,the   \n5 base polymer film is produced and later coated off-line with one or more coatings of the present invention. Alternatively, one or more coatings can be applied in-line,with the remainder being applied off-line.Conventional off-line coating processes include roll coating, reverse roll coating,   \n.0 gravure roll coating, reverse gravure roll coating, brush coating, wire-wound rod (Meyer rod) coating, spray coating, air knife coating, meniscus coating or dipping. While surface modification of the base polymer film prior to coating is not required, it has been found that better results   \n15 are obtained if the surface or surfaces of the base polymer film are modified before application of the coatings of the present invention. Conventional surface modification techniques include corona treatment, which is the most common and most preferred procedure for modifying the surface of   \n20 the polymer base film to enhance coating adhesion. The corona treatment or other surface modification should be suficient to permit wetting out of the coating. Corona treatment of about 1.0 watt per square foot per minute is typically sufficient to achieve the desired results. In addition,   \n25 primer or other intermediate layers can optionally be used between the polymer film and the anti-fog coating  \n\nIn light of the foregoing, a preferred method of controlling fog formation on polymer film is provided herein. Preferably, one or both faces of a base polymer film are coated with an anti-fog coating of the present invention. Optionally, if only one face is coated with the anti-fog coating of the present invention, this coating can occur before, after or at the same time the opposite face of the base polymer film is coated with an alternate coating. The antifog coating is preferably not overcoated with another coating. Such a top coating could limit the ability of the anti-fog coating to prevent fog.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# EXAMPLES  \n\nThe following Examples demonstrate various aspects of certain preferred embodiments of the present invention, and are not to be construed as limitations thereof. The formulations of the individual samples are shown in the charts below. In each example,the listed coating samples were formulated and coated in-line on biaxially oriented polyester film. Specifically, heat set PET film was coated in-line between draw steps on biaxially oriented polyester film with the following sample coatings. As in all of the following examples, anti-fog performance was tested by placing a sheet of the coated film, coated side down, over a warm air humidifier such as a “Holmes Air Pure Mist\" humidifier at a distance of approximately 3 to 6 inches for a period of approximately 2 seconds. The sheets were observed for fogging, with a score of 1 being completely obscured by fog and 5 being fog-free. The wetting tension of the film surface is measured using the Victor Contact Angle System of AST Products, Billerica, Mass.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 16,
+        "chunk": "# EXAMPLESERIESA  \n\n<html><body><table><tr><td>Ex.</td><td>Coating Formulation</td><td>Anti-fog</td><td>Wetting Tension (dynes/cm)</td></tr><tr><td></td><td>A-1 12.5% AJ-30 + 0.5% Nalco 1060</td><td>１</td><td>51.00</td></tr><tr><td>A-2</td><td>13.5% AJ-30 + 0.5% Nalco 1060</td><td>1</td><td>52.16</td></tr></table></body></html>  \n\n-continued   \n\n\n<html><body><table><tr><td>Ex.</td><td>CoatingFormulation</td><td>Anti-fog</td><td>Wetting Tension (dynes/cm)</td></tr><tr><td>A-3</td><td>12.8% AJ-30 + 0.5% Nalco 1060 + 0.7% Cymel 303</td><td>1</td><td>51.56</td></tr><tr><td></td><td>A-4 14.5% AJ-30 + 0.5% Nalco 1060</td><td>1</td><td>52.31</td></tr><tr><td></td><td>A-5 12.5% AJ-30 + 0.5% Nalco 1060 + 1% LDS-10</td><td>5</td><td>69.97</td></tr><tr><td></td><td>A-6 12.5% AJ-30 + 0.5% Nalco 1060 + 1% LDS-10</td><td>5</td><td>69.71</td></tr><tr><td></td><td>A-7 12.5% AJ-30 + 0.5% Nalco 1060 + 1% FC-170C</td><td>3.5</td><td>48.25</td></tr><tr><td>A-8</td><td>12.5% AJ-30 + 0.5%Nalco 1060 + 1% Airvol107 PVOH</td><td>2</td><td>54.25</td></tr></table></body></html>\n\nCymel 303 is a melamine hardener/crosslinker Airvol 107 PVOH is polyvinyl alcohol.  \n\nThe first series of examples demonstrate the improved 15 performance provided by the LDS-10 surfactant.As seen in examples A-5 and A-6, the combination of copolyester and this anionic surfactant provide surprisingly superior anti-fog performance. The presence of crosslinkers and polyvinyl alcohol (A-3 and A-8) do not give rise to such performance. Example A-7 demonstrates that the fluorosurfactant alone  \n\nExample Series B  \n\nThe potential negative effect of Cymel 303 crosslinker melamine hardener and more than $0.1\\%$ FC 170C is supported by the following examples, in which levels of AJ-30 copolymer, LDS-10 surfactant, Nalco 1060 silica, and FC-170C fluorosurfactant are varied:  \n\n<html><body><table><tr><td>Ex.</td><td>Coating Formulation</td><td>Anti-fog (fresh/ aged)</td><td>Wetting Tension (dynes/cm)</td></tr><tr><td>B-1</td><td>25% AJ-30 + 1% LDS-10 + 0.5% Nalco 1060</td><td>5/5</td><td>68.50</td></tr><tr><td>B-2</td><td>25%AJ-30 +1% LDS-10 + 0.5% Nalco 1060</td><td>5/5</td><td>66.70</td></tr><tr><td>B-3</td><td>25%AJ-30+1%LDS-10 + 0.5%Nalco 1060</td><td>-/3</td><td>69.02</td></tr><tr><td>B-4</td><td>22.5% AJ-30 + 1%LDS-10 + 0.5% Nalco 1060</td><td>5/5</td><td>69.17</td></tr><tr><td>B-5</td><td>22.5%AJ-30+1%LDS-10 + 0.5%Nalco 1060</td><td>5/4</td><td>70.18</td></tr><tr><td>B-6</td><td>22.5%AJ-30 +1%LDS-10 + 0.5%Nalco1060</td><td>5/5</td><td>69.95</td></tr><tr><td>B-7</td><td>20%AJ-30 +1%LDS-10 + 0.5% Nalco 1060</td><td>4/3</td><td>65.44</td></tr><tr><td>B-8</td><td>20% AJ-30 + 1% LDS-10 + 0.5% Nalco 1060</td><td>4/5</td><td>66.07</td></tr><tr><td>B-9</td><td>20%AJ-30 +1% LDS-10 + 0.5% Nalco 1060</td><td>4/4</td><td>65.13</td></tr><tr><td></td><td>B-10 22.5% AJ-30 +1%LDS-10 + 0.1%FC-170C + 0.5%</td><td>4.5/5</td><td>66.75</td></tr><tr><td></td><td>Nalco 1060 B-11 22.5% AJ-30 + 1%LDS-10 + 0.25%FC-170C + 0.5% Nalco 1060</td><td>3/5</td><td>69.22</td></tr><tr><td></td><td>B-12 22.5% AJ-30 + 1%LDS-10 + 0.5%FC-170C + 0.5% Nalco 1060</td><td>1/5</td><td>68.977</td></tr><tr><td></td><td>B-1322.5%AJ-30+1%LDS-10+ 0.25%FC-170C+2.2% Cymel 303 + 0.5% Nalco 1060</td><td>1/2</td><td>58.10</td></tr><tr><td></td><td>B-14 22.5% AJ-30 + 1%LDS-10 + 0.25% FC-170C + 1.1%</td><td>1/3</td><td>63.68</td></tr><tr><td></td><td>Cymel 303 + 0.5% Nalco 1060 B-15 22.5% AJ-30 +1%LDS-10 + 0.25%FC-170C + 0.5%</td><td>3/5</td><td>64.92</td></tr><tr><td></td><td>Cymel303 + 0.5%Nalco 1060 B-16 10% M + 1% LDS-10 +0.5% Nalco 1060</td><td>4/3</td><td>70.71</td></tr><tr><td></td><td>B-17 10%M+ 1%LDS-10 + 0.25%FC-170C + 0.5%</td><td>1/4.5</td><td>70.73</td></tr><tr><td></td><td>Nalco 1060 B-18 10% M +1%LDS-10 + .25%FC-170C + 1%</td><td>1/4.5</td><td>66.91</td></tr><tr><td></td><td>Cymel 303 + 0.5% Nalco 1060 B-19 10% M + 1% LDS-10 + 0.25 FC-170C + 0.5%</td><td>3/4.5</td><td>68.78</td></tr><tr><td></td><td>Cymel 303 + 0.5% Nalco 1060</td><td></td><td></td></tr><tr><td></td><td>B-20 10% M + 1% LDS-10 + 0.25 FC-170C + 0.25% Cymel 303 + 0.5% Nalco 1060</td><td>3/4.5</td><td>69.93</td></tr></table></body></html>\n\n$\\mathbf{M}=\\mathbf{a}$ copolyester of 10 mol percent sodium salt of 5-sulfoisophthalic acid, 90 mol percent isophthalic acid and 100 mol percent ethylene glycol Fresh $\\mathbf{\\tau}=$ day of manufacture Aged $=22$ days after manufacture  \n\nprovides acceptable but not excellent anti-fog properties, suggesting a synergistic effect of the fluorosurfactant with surfactants such as LDS-10. These data also support a direct correlation between wetting tension and anti-fog performance. It is further shown that a wetting tension of about 60 dynes/cm or greater (optionally to about 72 dynes/cm or more) is preferred herein.As will be shown in the following examples, wetting tension of greater than 65 dynes/cm is alternately preferred, with wetting tension of greater than 69 being an additional preferred embodiment.  \n\nThis Example demonstrates the ameliorative effect of short-term aging on some compositions according to the present invention (B-11 and following, except B-16). In addition, it suggests that at fluorosurfactant levels of 0.5 or greater (B-12), or when crosslinkers are added (B-13 through B-15 and B-18 through B-20) anti-fog performance is diminished, particularly for fresh film.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# Example Series C  \n\nThese examples reinforce the conclusion that the use of greater than $1\\%$ LDS-1O surfactant gives rise to improved performance:  \n\n<html><body><table><tr><td>Ex.</td><td>Coating Formulation</td><td>Anti-fog (fresh/ aged)</td><td>Wetting Tension (dynes/cm)</td></tr><tr><td>C-1</td><td>15%AJ-30 + 1%LDS-10 + 0.5%Nalco 1060</td><td>5/5</td><td>70.38</td></tr><tr><td>C-2</td><td>25%AJ-30 +1% LDS-10 + 0.5%Nalco 1060</td><td>5/5</td><td>70.09</td></tr><tr><td>C-3</td><td>15% AJ-30 + 2%LDS-10 + 0.5% Nalco 1060</td><td>5/5</td><td>70.71</td></tr><tr><td>C-4</td><td>25% AJ-30 + 2%LDS-10 + 0.5% Nalco 1060</td><td>5/5</td><td>70.04</td></tr><tr><td>C-5</td><td>15% AJ-30 + 1% LDS-10 + 1% Nalco 1060</td><td>5/5</td><td>70.35</td></tr><tr><td>C-6</td><td>25%AJ-30 +1%LDS-10 + 1%Nalco 1060</td><td>5/5</td><td>68.28</td></tr><tr><td>C-7</td><td>15% AJ-30 + 2%LDS-10 + 1% Nalco 1060</td><td>5/5</td><td>69.76</td></tr><tr><td>C-8</td><td>25% AJ-30 + 2% LDS-10 + 1% Nalco 1060</td><td>5/5</td><td>70.28</td></tr><tr><td>C-9</td><td>25% AJ-30 + 2% LDS-10 + 0.1% Nalco 1060</td><td>5/5</td><td>70.14</td></tr><tr><td></td><td>C-10 7.5% AJ-30 + 0.5% LDS-10 + 0.5% Nalco 1060</td><td>1/3</td><td>67.25</td></tr><tr><td></td><td>C-11 15% AJ-30 + 0.5% LDS-10 + 0.5% Nalco 1060</td><td>3/4.5</td><td>65.47</td></tr><tr><td></td><td>C-12 7.5% AJ-30 +1%LDS-10 + 0.5%Nalco 1060</td><td>5/4</td><td>69.54</td></tr><tr><td></td><td>C-13 15% M-30 + 1% LDS-10 + 0.5% Nalco 1060</td><td>5/5</td><td>69.70</td></tr><tr><td></td><td>C-14 7.5% AJ-30 + 0.5%LDS-10 + 1%Nalco 1060</td><td>1/3</td><td>64.03</td></tr><tr><td></td><td>C-15 15% AJ-30 + 0.5% LDS-10 + 1% Nalco 1060</td><td>1/3</td><td>64.31</td></tr><tr><td></td><td>C-167.5% AJ-30 + 1%LDS-10 +1%Nalco 1060</td><td>5/5</td><td>70.53</td></tr><tr><td></td><td>C-17 15% AJ-30 + 1% LDS-10 + 1% Nalco 1060</td><td></td><td>64.47</td></tr><tr><td></td><td>C-18 15% AJ-30 + 1% LDS-10 + 1%Nalco 1060</td><td>5/5</td><td>68.66</td></tr><tr><td></td><td>C-19 15% AJ-30 + 1% LDS-10 + 0.5% Nalco 1060 +</td><td>5/4.5</td><td>68.74</td></tr><tr><td></td><td>0.01%FC-170C C-20 15% AJ-30 + 1% LDS-10 +0.5% Nalco 1060 +</td><td>5/5</td><td>68.82</td></tr><tr><td></td><td>0.02%FC-170C C-21 15% AJ-30 + 1% LDS-10 + 0.5% Nalco 1060 +</td><td>5/5</td><td>68.04</td></tr><tr><td></td><td>0.05%FC-170C C-22 15% AJ-30 + 1% LDS-10 + 0.5% Nalco 1060 + 0.1%FC-170C</td><td>5/5</td><td>67.56</td></tr></table></body></html>  \n\nThe optimal results, with high anti-fog performance, are achieved with films having higher levels of surfactant, namely 2 weight percent of total composition. Notably, too, these results are achieved with a lower relative copolyester content of about 15 percent. These examples (notably C-10, C-14 and C-1 5, in comparison with surrounding examples)  \n\ni0 suggest that low levels of copolyester (approximately $7.5\\%$ and $15\\%$ ）in combination with low levels of LDS-10 surfactant $(0.5\\%)$ give rise to poorer results.  \n\nExample Series D  \n\n<html><body><table><tr><td>Ex. CoatingFormulation</td><td></td><td>Anti-fog</td><td>Tension (dynes/cm) Wetting</td><td>Total Haze (%)</td><td>Trans- mission (%)</td></tr><tr><td>D-1</td><td>1% AJ-30 + 1% LDS-10 + 0.05% FC-170C + 0.5%</td><td>4</td><td>65.95</td><td>0.68</td><td>89.6</td></tr><tr><td>D-2</td><td>Nalco 1060 2% AJ-30 + 1% LDS-10 + 0.05% FC-170C + 0.5%</td><td>4</td><td>69.30</td><td>0.62</td><td>89.8</td></tr><tr><td>D-3</td><td>Nalco 1060 3% AJ-30 + 1% LDS-10 + 0.05% FC-170C + 0.5%</td><td>3</td><td>68.94</td><td>0.65</td><td>90.5</td></tr><tr><td>D-4</td><td>Nalco 1060 4% AJ-30 + 1% LDS-10 + 0.05%FC-170C + 0.5%</td><td>4.5</td><td>69.77</td><td>0.75</td><td>90.6</td></tr><tr><td>D-5</td><td>Nalco 1060 5% AJ-30 + 1% LDS-10 + 0.05%FC-170C + 0.5%</td><td>4.5</td><td>69.43</td><td>0.80</td><td>90.8</td></tr><tr><td>D-6</td><td>Nalco 1060 6% AJ-30 + 1% LDS-10 + 0.05% FC-170C + 0.5%</td><td>5</td><td>69.51</td><td>0.97</td><td>90.7</td></tr><tr><td>D-7</td><td>Nalco 1060 7%AJ-30 +1%LDS-10 + 0.05%FC-170C+ 0.5%</td><td>5</td><td>69.65</td><td>0.80</td><td>91.2</td></tr><tr><td>D-8</td><td>Nalco 1060 8%AJ-30+ 1%LDS-10+ 0.05%FC-170C + 0.5%</td><td>5</td><td>67.81</td><td>0.82</td><td>91.0</td></tr><tr><td>D-9</td><td>Nalco 1060 9% AJ-30 + 1%LDS-10 + 0.05%FC-170C + 0.5%</td><td>5</td><td>69.65</td><td>0.84</td><td>91.1</td></tr><tr><td></td><td>Nalco 1060 D-10 10% AJ-30 + 1% LDS-10 + 0.05% FC-170C + 0.5%</td><td>4.5</td><td>69.59</td><td>0.81</td><td>91.4</td></tr><tr><td></td><td>Nalco 1060 D-11 1% AJ-20A + 1% LDS-10 + 0.05% FC-170C + 0.5% Nalco 1060</td><td>4</td><td>69.94</td><td>0.70</td><td>90.1</td></tr><tr><td></td><td>D-12 2% AJ-20A + 1% LDS-10 + 0.05% FC-170C +</td><td>3.5</td><td>69.48</td><td>0.74</td><td>90.2</td></tr><tr><td></td><td>0.5%Nalco1060 D-13 3% AJ-20A + 1% LDS-10 + 0.05% FC-170C +</td><td>4</td><td>69.94</td><td>0.86</td><td>90.3</td></tr><tr><td></td><td>0.5%Nalco1060 D-14 4% AJ-20A + 1% LDS-10 + 0.05% FC-170C + 0.5%Nalco1060</td><td>5</td><td>69.64</td><td>0.92</td><td>90.5</td></tr><tr><td></td><td>D-15 5% AJ-20A + 1% LDS-10 + 0.05% FC-170C + 0.5%Nalco1060</td><td>5</td><td>69.74</td><td>0.82</td><td>91.2</td></tr></table></body></html>  \n\n-continued   \n\n\n<html><body><table><tr><td></td><td>Ex. Coating Formulation</td><td>Anti-fog</td><td>Wetting Tension (dynes/cm)</td><td>Total Haze (%)</td><td>Trans- mission (%)</td></tr><tr><td></td><td>D-16 6% AJ-20A + 1% LDS-10 + 0.05% FC-170C + 0.5%Nalco1060</td><td>５</td><td>69.96</td><td>1.50</td><td>91.2</td></tr><tr><td></td><td>D-17 7% AJ-20A + 1% LDS-10 + 0.05% FC-170C + 0.5% Nalco 1060</td><td>５</td><td>69.67</td><td>0.78</td><td>91.4</td></tr><tr><td></td><td>D-18 8% AJ-20A + 1% LDS-10 + 0.05% FC-170C + 0.5%Nalco1060</td><td>５</td><td>69.41</td><td>0.75</td><td>91.0</td></tr><tr><td></td><td>D-19 9% AJ-20A + 1% LDS-10 + 0.05% FC-170C + 0.5%Nalco1060</td><td>5</td><td>70.30</td><td>0.66</td><td>91.8</td></tr><tr><td></td><td>D-20 10% AJ-20A + 1% LDS-10 + 0.05% FC-170C + 0.5%Nalco1060</td><td>5</td><td>69.17</td><td>0.75</td><td>91.5</td></tr></table></body></html>  \n\nThese results establish that even relatively low levels of copolyester binder give acceptable anti-fog performance in combination with low levels of surfactants, but that even better performance is achieved at higher levels of copolyester binder.  \n\nTotal haze is a preferred method of measuring the clarity of a polyester film, which can determine its suitability for such films as antifog faceshield film. Haze is measured based on ASTM Method D1003-61, Procedure A,“Haze and  \n\nLuminous Transmittance of Transparent Plastics\", using a BYK Gardner “Haze Gard Plus” instrument. The AJ-20A provides minimum haze at higher concentrations,whereas the AJ-30 provides minimum haze at lower concentrations.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# Example Series E  \n\nThese examples establish that two different preferred copolyester binders perform better at higher levels of LDS10 surfactant.  \n\n<html><body><table><tr><td>Ex. Coating Formulation</td><td></td><td>Anti- fog</td><td>Wetting Tension (dynes/cm)</td><td>Total Haze (%)</td><td>Trans- mission (%)</td></tr><tr><td>E-1</td><td>6% AJ-20A + 0.5% LDS-10 + 0.05% FC-170C +</td><td>2</td><td>66.14</td><td>0.87</td><td>90.3</td></tr><tr><td>E-2</td><td>0.5% Nalco 1060 6% AJ-20A + 0.75% LDS-10 + 0.05% FC-170C +</td><td>4</td><td>69.99</td><td>1.08</td><td>90.2</td></tr><tr><td>E-3</td><td>0.5% Nalco 1060 6% AJ-20A + 1% LDS-10 + 0.05% FC-170C +</td><td>5</td><td>68.82</td><td>1.21</td><td>90.4</td></tr><tr><td>E-4</td><td>0.5% Nalco 1060 6% AJ-20A + 1.25% LDS-10 + 0.05% FC-170C +</td><td>5</td><td>70.34</td><td>1.14</td><td>90.3</td></tr><tr><td>E-5</td><td>0.5%Nalco 1060 6%AJ-20A+ 1.5%LDS-10+ 0.05%FC-170C +</td><td>5</td><td>68.98</td><td>1.34</td><td>90.7</td></tr><tr><td>E-6</td><td>0.5% Nalco 1060 6% AJ-20A + 2% LDS-10 + 0.05% FC-170C +</td><td>5</td><td>69.24</td><td>1.62</td><td>90.4</td></tr><tr><td>E-7</td><td>0.5% Nalco 1060 6%AJ-20A +1%LDS-10+ 0.05%FC-170C + 0.03%Cymel 303+ 0.5%Nalco 1060</td><td>5</td><td>70.10</td><td>0.91</td><td>91.2</td></tr><tr><td>E-8</td><td>6% AJ-20A + 1% LDS-10 + 0.05% FC-170C + 0.03% Cymel 303+ 0.5% Nalco 1060</td><td>5</td><td>70.32</td><td>1.08</td><td>91.0</td></tr><tr><td>E-9</td><td>6%AJ-20A+ 1%LDS-10 + 0.05%FC-170C +</td><td>5</td><td>70.14</td><td>1.02</td><td>90.3</td></tr><tr><td></td><td>0.03% Cymel 303 + 0.5% Nalco 1060 E-10 6% M + 0.5% LDS-10 + 0.05% FC-170C +</td><td>1</td><td>66.13</td><td>0.59</td><td>90.7</td></tr><tr><td></td><td>0.5% Nalco 1060 E-11 6% M + 0.75%LDS-10 + 0.05% FC-170C +</td><td>3</td><td>70.68</td><td>0.72</td><td>91.3</td></tr><tr><td></td><td>0.5%Nalco1060 E-12 6% M + 0.5% LDS-10 + 0.05% FC-170C +</td><td>4</td><td>70.96</td><td>0.74</td><td>91.3</td></tr><tr><td></td><td>0.5%Nalco1060 E-13 6% M + 1.25%LDS-10 + 0.05%FC-170C +</td><td>5</td><td>71.18</td><td>082</td><td>91.2</td></tr><tr><td></td><td>0.5% Nalco 1060 E-14 6%M+1.5%LDS-10 + 0.05%FC-170C +</td><td>5</td><td>70.87</td><td>0.88</td><td>91.0</td></tr><tr><td></td><td>0.5% Nalco 1060 E-15 6%M+2%LDS-10 +0.05%FC-170C + 0.5% Nalco 1060</td><td>5</td><td>70.77</td><td>0.99</td><td>91.2</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 13  \n\nCoatings containing less than $0.75\\%$ ， specifically $0.5\\%$ LDS-10, show poor anti-fog performance. Even at $0.75\\%$ LDS-1O surfactant, the resulting anti-fog effects are not complete. In this case, at optimized coating formulations, the presence of the Cymel 303 crosslinker did not adversely affect performance (see E-7 through E-9) and its presence is believed to provide greater permanence to the coating. Total haze increases generally for each system as the level of LDS-10 surfactant increases.  \n\nExample Series F  \n\n<html><body><table><tr><td></td><td>Ex. Coating Formulation</td><td>Anti- fog</td><td>Wetting Tension (dynes/cm)</td><td>Total Haze (%)</td><td>Trans- mission (%)</td></tr><tr><td>F-1</td><td>6% AJ-20A + 1% Rhodacal LDS-10 + 0.05% FC-170C + 0.5%Nalco 1060</td><td>5</td><td>70.07</td><td>1.38</td><td>90.7</td></tr><tr><td></td><td>F-2 6% AJ-20A + 1.5% Rhodacal LDS-10 + 0.05% FC-170C + 0.5% Nalco 1060</td><td>5</td><td>70.86</td><td>1.47</td><td>90.8</td></tr><tr><td></td><td>F-3 6% AJ-20A + 1% Sipon UB + 0.05% FC-170C +</td><td>5</td><td>70.59</td><td>0.74</td><td>90.0</td></tr><tr><td></td><td>0.5%Nalco 1060 F-4 6% AJ-20A + 1.5% Sipon UB + 0.05% FC-170C +</td><td>5</td><td>71.29</td><td>0.97</td><td>90.6</td></tr><tr><td></td><td>0.5%Nalco 1060 F-5 6% AJ-20A + 1% Aer0sol OTNV + 0.05% FC-170C + 0.5%Nalco 1060</td><td>5</td><td>71.07</td><td>0.75</td><td>90.5</td></tr><tr><td></td><td>F-6 6% AJ-20A + 1.5% Aer0sol OTNV + 0.05% FC-170C + 0.5% Nalco 1060</td><td>5</td><td>69.78</td><td>1.45</td><td>90.6</td></tr><tr><td></td><td>F-7 6% M + 1% Rhodacal LDS-10 + 0.05% FC-170C + 0.5%Nalco 1060</td><td>5</td><td>70.60</td><td>0.94</td><td>89.6</td></tr><tr><td></td><td>F-8 6% AJ-20A + 1.5% Rhodacal LDS-10 + 0.05% FC-170C + 0.5%Nalco 1060</td><td>5</td><td>70.64</td><td>1.23</td><td>90.0</td></tr><tr><td></td><td>F-9 6% M + 1% Sipon UB + 0.05% FC-170C + 0.5%Nalco 1060</td><td>5</td><td>70.92</td><td>1.01</td><td>90.1</td></tr><tr><td></td><td>F-10 6% M + 1.5% Sipon UB + 0.05% FC-170C + 0.5%Nalco 1060</td><td>5</td><td>70.70</td><td>1.29</td><td>90.4</td></tr><tr><td></td><td>F-11 6% M + 1% Aer0sol OTNV+ 0.05% FC-170C + 0.5%Nalco 1060</td><td>5</td><td>70.97</td><td>0.93</td><td>90.0</td></tr><tr><td></td><td>F-12 6% M+ 1.5% Aer0sol OTNV + 0.05% FC-170C + 0.5%Nalco 1060</td><td>5</td><td>70.64</td><td>1.33</td><td>90.1</td></tr></table></body></html>  \n\nThe foregoing preferred compositions show that optimal results can be achieved with varying levels and varying 40 components according to the present invention. It is noted that haze rises to a degree when the level of surfactant is raised.  \n\nExample Series G  \n\n<html><body><table><tr><td></td><td>Ex.CoatingFormulation</td><td>Anti- fog</td><td>Tension (dynes/cm) Wetting</td><td>Total Haze (%)</td><td>Trans- mission (%)</td></tr><tr><td></td><td>G-1 4% AJ-20A + 0.48% Aer0sol OTNV + 0.05% FC-170C + 0.5% Nalco 1060</td><td>3</td><td>67.91</td><td>0.77</td><td>90.7</td></tr><tr><td></td><td>G-2 4% AJ-20A + 0.72% Aer0sol OTNV + 0.05% FC-170C + 0.5%Nalco1060</td><td>5</td><td>70.35</td><td>0.80</td><td>90.3</td></tr><tr><td></td><td>G-3 4% AJ-20A + 0.96% Aer0sol OTNV + 0.05% FC-170C + 0.5% Nalco 1060</td><td>5</td><td>70.88</td><td>0.89</td><td>90.3</td></tr><tr><td></td><td>G-4 4% AJ-20A + 1.2% Aer0sol OTNV+ 0.05% FC-170C + 0.5% Nalco 1060</td><td>5</td><td>70.55</td><td>0.84</td><td>90.3</td></tr><tr><td></td><td>G-5 6% AJ-20A + 0.48% Aer0s0l OTNV + 0.05% FC-170C + 0.5%Nalco1060</td><td>4</td><td>69.75</td><td>0.69</td><td>90.6</td></tr><tr><td></td><td>G-6 6% AJ-20A + 0.72% Aer0sol OTNV+ 0.05% FC-170C + 0.5%Nalco 1060</td><td>5</td><td>70.73</td><td>0.67</td><td>90.7</td></tr><tr><td></td><td>G-7 6% AJ-20A + 0.96% Aer0s0l OTNV + 0.05% FC-170C + 0.5%Nalco 1060</td><td>5</td><td>71.16</td><td>0.65</td><td>90.3</td></tr><tr><td></td><td>G-8 6% AJ-20A + 1.2% Aer0sol OTNV+ 0.05% FC-170C + 05%Nalco 1060</td><td>5</td><td>70.88</td><td>0.75</td><td>91.2</td></tr></table></body></html>  \n\nAerosol OTNV provides excellent antifog performance and excellent clarity. Total haze is low throughout the ranges shown.  \n\nExample Series H  \n\ntains less than about O.5 weight percent of a fluorosurfactant, and wherein said coating has a wetting tension of greater than about 60 dynes/cm.  \n\n2. The coated polymer film of claim 1, wherein said anti-fog coating is transparent.  \n\n<html><body><table><tr><td>Ex.</td><td>Coating Formulation</td><td>Anti- fog</td><td>Wetting Tension (dynes/cm)</td><td>Total Haze (%)</td><td>Trans- mission (%)</td></tr><tr><td>H-1</td><td>2% AJ-20A + 0.4% Aer0s0l OTNV + 0.05% FC-170C + 0.5% Nalco 1060</td><td>4</td><td>69.38</td><td>0.49</td><td>90.9</td></tr><tr><td>H-2</td><td>2% AJ-20A + 0.6% Aerosol OTNV + 0.05% FC-170C +</td><td>5</td><td>69.51</td><td>0.60</td><td>89.9</td></tr><tr><td></td><td>0.5% Nalco 1060 H-3 2% AJ-20A + 0.8% Aerosol OTNV + 0.05% FC-170C +</td><td>5</td><td>69.67</td><td>0.56</td><td>90.1</td></tr><tr><td>H-4</td><td>0.5% Nalco 1060 2% AJ-20A + 1% Aer0sol OTNV + 0.05% FC-170C +</td><td>5</td><td>70.57</td><td>0.68</td><td>90.4</td></tr><tr><td>H-5</td><td>0.5%Nalco 1060 3% AJ-20A + 0.4% Aer0sol OTNV + 0.05% FC-170C +</td><td>4</td><td>66.51</td><td>0.73</td><td>90.2</td></tr><tr><td></td><td>0.5% Nalco 1060 H-6 3% AJ-20A + 0.6% Aer0sol OTNV + 0.05% FC-170C +</td><td>4</td><td>70.56</td><td>0.77</td><td>90.3</td></tr><tr><td>H-7</td><td>0.5% Nalco 1060 3% AJ-20A +0.8% Aer0sol OTNV + 0.05% FC-170C +</td><td>5</td><td>70.61</td><td>0.83</td><td>89.8</td></tr><tr><td>H-8</td><td>0.5% Nalco 1060 3% AJ-20A + 1% Aerosol OTNV + 0.05% FC-170C +</td><td>5</td><td>69.83</td><td>0.94</td><td>90.4</td></tr><tr><td>H-9</td><td>0.5%Nalco1060 4% AJ-20A + 0.4% Aer0sol OTNV + 0.05% FC-170C +</td><td>4</td><td>66.57</td><td>0.82</td><td>90.6</td></tr><tr><td></td><td>0.5% Nalco 1060 H-10 4% M-20A + 0.6% Aer0sol OTNV + 0.05% FC-170C +</td><td>5</td><td>70.04</td><td>0.83</td><td>90.2</td></tr><tr><td></td><td>0.5%Nalco 1060 H-11 4% AJ-20A + 0.8% Aer0sol OTNV + 0.05% FC-170C +</td><td>5</td><td>70.39</td><td>0.89</td><td>90.3</td></tr><tr><td></td><td>0.5% Nalco 1060 H-12 4% AJ-20A + 1% Aer0sol OTNV + 0.05% FC-170C +</td><td>5</td><td>70.82</td><td>0.86</td><td>91.0</td></tr><tr><td></td><td>0.5% Nalco 1060 H-13 2% AJ-20A + 0.4% Sip0n UB + 0.05% FC-170C +</td><td>2</td><td>55.39</td><td>0.63</td><td>90.7</td></tr><tr><td></td><td>0.5% Nalco 1060 H-14 2% AJ-20A + 0.6% Sipon UB + 0.05% FC-170C +</td><td>3</td><td>62.86</td><td>0.66</td><td>90.7</td></tr><tr><td></td><td>0.5% Nalco 1060 H-15 2% AJ-20A + 0.8% Sipon UB + 0.05% FC-170C +</td><td>4</td><td>66.76</td><td>0.66</td><td>90.7</td></tr><tr><td></td><td>0.5%Nalco 1060 H-16 2% AJ-20A + 1% Sipon UB + 0.05% FC-170C +</td><td>4</td><td>67.67</td><td>0.71</td><td>91.1</td></tr><tr><td></td><td>0.5% Nalco 1060 H-17 3% AJ-20A + 0.4% Sipon UB + 0.05% FC-170C +</td><td>2</td><td>54.57</td><td>0.66</td><td>90.6</td></tr><tr><td></td><td>0.5% Nalco 1060 H-18 3% AJ-20A + 0.6% Sipon UB + 0.05% FC-170C +</td><td>3</td><td>61.96</td><td>0.71</td><td>91.0</td></tr><tr><td></td><td>0.5% Nalco 1060 H-19 3% AJ-20A + 0.8% Sipon UB + 0.05% FC-170C +</td><td>4</td><td>66.85</td><td>0.78</td><td>90.7</td></tr><tr><td></td><td>0.5% Nalco 1060 H-20 3% AJ-20A + 1% Sipon UB + 0.05% FC-170C +</td><td>4</td><td>66.82</td><td>0.76</td><td>91.3</td></tr><tr><td></td><td>0.5% Nalco 1060 H-21 4% AJ-20A + 0.4% Sipon UB + 0.05% FC-170C +</td><td>2</td><td>55.87</td><td>0.69</td><td>90.8</td></tr><tr><td></td><td>0.5% Nalco 1060 H-22 4% AJ-20A + 0.6% Sipon UB + 0.05% FC-170C +</td><td>3</td><td>61.79</td><td>0.87</td><td>90.8</td></tr><tr><td></td><td>0.5% Nalco 1060 H-23 4% AJ-20A + 0.8% Sip0n UB + 0.05% FC-170C +</td><td>4</td><td>68.32</td><td>0.70</td><td>91.0</td></tr></table></body></html>\n\n50  \n\nThese data suggest that Sipon UB surfactant is preferably used at a somewhat higher level than Aerosol OTNV surfactant, with roughly $0.8\\%$ and $0.4\\%$ preferred minimums, respectively.  \n\nThe present invention having been thus described with particular reference to the preferred forms and embodiments thereof, it will be obvious to one of ordinary skill in the art that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.  \n\nWhat is claimed is:  \n\n1.A coated polymer film having a coated surface that resists the formation of fog, said film comprising a self-supporting polymer film layer, and an anti-fog coating on said film layer, said anti-fog coating consisting essentially of a hydrophilic copolyester binder and a surfactant, wherein said surfactant con  \n\n3. The coated polymer film of claim 1, wherein said film is transparent.  \n\n4. The coated polymer film of claim 1, wherein an intermediate coating or layer is interposed between said anti-fog coating and said film layer.  \n\n5. The coated polymer film of claim 1, wherein said fluorosurfactant comprises fluoroaliphatic oxyethylenes of carbon chain lengths of about 4 to about 8 and polyethylene glycol.  \n\n6. The coated polymer film of claim 1, wherein said 60 binder comprises a water-soluble copolyester comprising, 1,3-benzenedicarboxylic acid, 5-sulfo-, 1,3-dimethyl ester sodium salt, polymer and dimethyl 1,4- benzenedicarboxylate, 1,2-ethanediol and $^{2,2^{\\prime}}$ -oxybis (ethanol).  \n\n7.The coated polymer film of claim 1, wherein said binder comprises a water-soluble copolyester comprising about 50 to about $98~\\mathrm{mol}$ percent isophthalic acid, about 2",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# 17",
+        "category": " Introduction"
+    },
+    {
+        "id": 21,
+        "chunk": "# 18  \n\nto about $20\\mathrm{\\mol}$ percent of at least one sulfomonomer containing a sulfonate group attached to a dicarboxylic nucleus, and about $100\\mathrm{mol}$ percent of at least one copolymerizable glycol having from about 2 to about 11 carbon atoms.  \n\n8. The polymer film of claim 1, wherein said polymer comprises polyester. 9.The polymer film of claim 1, wherein said binder is present at about 1 to about 30 weight percent of said anti-fog coating. 10. The polymer film of claim 1, wherein said binder is 1C present at about 1 to about 6 weight percent of said anti-fog coating. 11. The polymer film of claim 1, wherein said binder comprises a sulfomonomer. 12. The polymer film of claim 11, wherein said sul- 15 fomonomer comprises 5-sulfoisophthalic acid. 13. The polymer film of claim 1, wherein said fluorosurfactant is present at about 0.02 to about 0.5 weight percent of said anti-fog coating. 14. The coated polymer film of claim 1,wherein said 2( surfactant is present at about 0.4 to about 2.0 weight percent of said anti-fog coating. 15. The coated polymer film of claim 1,wherein said surfactant comprises an anionic surfactant. 16. The coated polymer film of claim 1,wherein said $25$ surfactant comprises sodium dodecyl benzenesulfonate. 17. The coated polymer film of claim 1, wherein said surfactant includles comprises sodium lauryl sulfate. 18. The coated polymer film of claim 1,wherein said surfactant comprises a sulfosuccinate. 19.Thecoated polymer film of claim 1,wherein said 3 surfactant comprises sodium 2-ethylhexylsulfate. 20. The polymer film of claim 1, further comprising a slip agent. 21.The polymer film of claim 20, wherein said slip agent comprises at least one silica. 35 22. The polymer film of claim 20, wherein said slip agent comprises colloidal $\\mathrm{SiO}_{2}$ 23. The polymer film of claim 20, wherein said slip agent is present at about 0.25 to about 2 weight percent of said anti-fog coating. 4C 24. The polymer film of claim 20, wherein said slip agent is present at about O.3 to about 1 weight percent of said anti-fog coating. 25. The polymer film of claim 1, wherein said anti-fog coating has a solids level of about 0.01 to about 30 weight percent.  \n\n26. The polymer film of claim 1, wherein said anti-fog coating has a coating thickness of about 0.o2 microns to about 0.1 microns.   \n27. The polymer film of claim 1, wherein said anti-fog coating has a coating thickness of about 0.o3 microns to about 0.05 microns.   \n28. The polymer film of claim 1, wherein said coating has a wetting tension of greater than about 65 dynes/cm.   \n29. The polymer film of claim 1, wherein said coating has a wetting tension of greater than about 69 dynes/cm.   \n30. The coated polymer film of claim 1, wherein said anti-fog coating contains no crosslinkers.   \n31. The coated polymer film of claim 1, wherein said anti-fog coating contains no more than about 0.5 weight percent crosslinker.   \n32. A process for controlling the formation of fog on a surface, said process comprising: a) coating said surface with an anti-fog coating consisting essentially of a water-soluble hydrophilic copolyester binder and a surfactant, wherein said surfactant contains less than about O.5 weight percent of a fluorosurfactant, and wherein said coating has a wetting tension of greater than about 60 dynes/cm.   \n33. The process of claim 32, wherein said coating is coated on a polymer film surface.   \n34. The process of claim 32, wherein said coating of said surface is accomplished by in-line coating.   \n35. A coated polymer film having a coated surface that resists the formation of fog, said film comprising a self-supporting polymer film layer, and an anti-fog coating layer on said film layer, said anti-fog coating consisting essentially of a hydrophilic copolyester binder and a surfactant, wherein said surfactant contains less than about O.5 weight percent of a fluorosurfactant, and wherein said coating is fog-free after 2 seconds exposure to a warm air humidifier at a distance of 3-6 inches.   \n36.A process for controlling the formation of fog on a surface, said process comprising: a) coating said surface with an anti-fog coating layer consisting essentially of a hydrophilic copolyester binder and a surfactant, wherein said surfactant contains less than about O.5 weight percent of a fluorosurfactant, and wherein said coating is fog-free after 2 seconds exposure to a warm air humidifier at a distance of 3-6 inches.",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/2003-JP-anti-fog.json b/task2/task2-chunks/2003-JP-anti-fog.json
new file mode 100644
index 0000000..2e14737
--- /dev/null
+++ b/task2/task2-chunks/2003-JP-anti-fog.json
@@ -0,0 +1,57 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19) United States (12) Patent Application Publication (1o) Pub. No.: US 2003/0218885 A1 Ishizaki (43) Pub. Date: Nov. 27, 2003",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (54) ANTI-FOGGING STRUCTURE FOR HEADLIGHT LAMPS",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# Publication Classification  \n\n(75) Inventor: Masaru Ishizaki, Shioya-gun (JP)  \n\n(51) Int. C1.7 B60Q 1/00   \n(52) U.S. Cl. 362/547; 362/294  \n\nCorrespondence Address: RANKIN, HILL,PORTER & CLARK,LLP 700HUNTINGTONBUILDING 925 EUCLID AVENUE, SUITE 700 CLEVELAND, OH 44115-1405 (US)",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# ABSTRACT  \n\n(73） Assignee: Honda Giken Kogyo Kabushiki Kaisha, Tokyo (JP)  \n\n(21) Appl. No.: 10/440,926  \n\nConforming with the differing conditions in which the left and right headlight lamps are placed, an anti-fogging structure for headlight lamps is proposed wherein variation in the anti-fogging performance on the left and right does not occur by providing differing structures for the breathing mechanisms in the left and right headlight lamps. In an anti-fogging mechanism for headlight lamps 5L and 5R provided on the left and right of the radiator fan at the front of the body of a vehicle, different structures are provided for the breathing holes that enable circulation of air into and out of the lamp housings 51L and 51R of the left and right headlight lamps 5L and 5R.  \n\n(22) Filed: May 19, 2003 (30) Foreign Application Priority Data  \n\nMay 24,2002 (JP) 2002-151276  \n\n![](images/c9368220015f035196dc49299201575d7d8f62191c90b533e84089cb238fb7c8.jpg)",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# FIG. 1  \n\n![](images/08c351d46824e6540e6992d741cceb9f84cb2f6e584b8d62a1ffb213968172e4.jpg)  \n\n![](images/6ee13234c10750781b04df60e6d690cc3e0599a139302542781dd0e3b5142ac5.jpg)  \nFIG.2",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# FIG.3  \n\n![](images/c2b90fe6d6fa94fe49ad9d6bd596c2eabe1cea53696c80d482bf8c1864343338.jpg)  \n\n![](images/865c6ed72a499b728708029f1eb7354505d29c2dcc5257c9a263bf43a54c3151.jpg)  \n\n![](images/b03c38eaf0c865b99c04ee394ffdf1e9ee9b3a334c114f981ea807c991746713.jpg)  \nRACS  \n\n![](images/b412af0a9c146d9f4c2151c88c23f307e5125335e1fff7cec9c46c2111673bf1.jpg)  \n\n![](images/f9ed5e2ec3b6ecf93fa1ddf72b3544bc425dbf7c9f2438655086e5bb056b87c6.jpg)  \n\n![](images/6d72e269ab0e1f209bb536da5a4ad1a27c466b930623a7dcae91ef50aab2e36b.jpg)  \n\n![](images/25f1fb5bc3a0dfbb9a5f0a06a1771b5c4c748e89bdd7a552ba0200f2af327465.jpg)  \n\nPatent Application Publication Nov.27, 2003 Sheet 9 of 10 US 2003/0218885 A1  \n\nFIG.10  \n\n![](images/fb20c80513c019a40dd6714dddb6c9cc8372d40618c2ef636cbfae95d655dab9.jpg)  \n\n![](images/ec60ab3eb36b1abafa6acdda2f691c9627cf98dbe13b4a335418d7c0db924d08.jpg)  \nAATAET  \n\n$$\n\\begin{array}{r}{\\underbrace{\\underline{{\\underline{{\\sigma}}}}}_{\\mathrm{[~L~]}}}\\\\ {\\qquad\\underbrace{\\overline{{\\underline{{\\sigma}}}}}_{\\mathrm{[~L~]}}}\\end{array}\n$$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# ANTI-FOGGING STRUCTURE FOR HEADLIGHTLAMPS  \n\nBACKGROUND OF THE INVENTION  \n\n[0001]1. Field of the Invention  \n\n[0002]  The prevent invention relates to an anti-fogging structure for a headlight lamp.",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# [0003]   2. Description of the Related Art  \n\n[0004]  An anti-fogging structure for the headlight lamps of a vehicle or the like, as disclosed, for example, in Japanese Unexamined Patent Application, First Publication, No. 2001-10403, draws air inside the headlight lamp from an intake opening and discharges it from a discharge opening. In addition, Japanese Unexamined Patent Application, First Publication, No.Hei 11-86614, discloses a structure in which the air in a headlight lamp housing is smoothly discharged to the outside from an air hole by preventing circulation of air in the headlight lamp housing.  \n\n[0005] However, in the conventional anti-fogging structure for a headlight lamp described above, because the conditions in which the left and right headlight lamps are placed are subtly different, there is the problem that a difference in the performance of the condensation on the left and right headlight lamps occurs.  \n\n[0006]   For example, in a normal vehicle having a radiator fan that rotates in a predetermined direction, a bias occurs in the pressure conditions where the left and right headlight lamps are placed, and in addition, in a vehicle having a structure wherein the engine,which is a source of heat,is disposed offset to either the left or right, a bias occurs in the temperature conditions in which the left and right headlight lamps are placed, and there is the problem that this causes an unevenness in the anti-fogging performance of the left and right headlight lamps.  \n\n[0007] Thus, this invention provides uses a structure in which the unevenness in the anti-fogging performance of the left and right headlight lamps is eliminated and the antifogging performance is improved by using a structure in which the breathing mechanism of the left and right headlight lamps differ in conformity to the differing conditions in which the left and right headlight lamps are placed.",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# SUMMARY OF THE INVENTION  \n\n[0008] In order to solve the above-described problems, a first aspect of the present invention is an anti-fogging structure for headlight lamps (for example, the headlight lamps 5L and 5R in the embodiments) provided to the left and right of the radiator fan (for example, the radiator fan 6 in the embodiments) on the front of the body (for example, the body 1 in the embodiments) of a vehicle,wherein a breathing mechanism (for example, the breathing holes 10, 11, and 12, and the water-repelling filter 13) that makes possible the circulation of air into and out of the lamp housing (for example, the lamp housings 51L and 51R in the embodiments) is structured differently on the left and right headlight lamps.  \n\n[0009] By using this type of structure, it becomes possible to use a structure wherein, taking into consideration the flow of air generated by the radiator fan, the air in the lamp housing can be easily discharged, while the air flows into the lamp housing with difficulty.  \n\n[0010] In a second aspect of the invention, the above breathing mechanism comprises breathing holes (for example, the breathing holes 10 and 12 in the embodiments) formed in the back walls (for example, the back walls 52L and 52R in the embodiments) of the lamp housing, and the breathing holes (for example, the breathing holes 10S and 12S in the embodiments) of the headlight lamps (for example the headlight lamp 5L in the embodiments) on the side where the pressure inside the lamp housing is negative due to the rotation of the radiator fan are set to have an aperture area smaller than the breathing holes (for example, the breathing holes 10B and 12B in the embodiments) of the headlight lamps (for example, the headlight lamp 5R in the embodiments) on the side where the pressure inside the lamp housing is positive due to the rotation of the radiator fan.  \n\n[0011] By using this type of structure, it becomes possible to suppress the inflow of external air as much as possible at the headlight lamp housing having a negative pressure inside, and promote the discharge of internal air as much as possible at the headlight lamp housing having a positive pressure inside.  \n\n[0012] In a third aspect of the present invention, the above breathing mechanism comprises breathing holes formed in the back walls of the headlight lamp housing, and the number of breathing holes in the headlight lamp on the side where the lamp housing has a positive pressure inside due to the rotation of the radiator fan is greater than the number of breathing holes of the headlight lamp housing on the side where the lamp housing has a negative pressure inside due to the rotation of the radiator fan.  \n\n[0013]  By using this type of structure, it becomes possible to promote the discharge of air from the headlight lamp housing having a positive pressure inside and to suppress the inflow of air into the headlight lamp housing having a negative pressure inside.  \n\n[0014] In a fourth aspect of the present invention, the above breathing mechanism comprises breathing holes formed in the back wall of the lamp housing, and in the case that an air flow is generated due to the rotation of the radiator fan, each of the breathing holes in the headlight lamp housing (for example, the breathing holes 10B and 11B in the embodiments) is formed downstream of this airflow.  \n\n[0015] By forming this type of structure, it becomes possible to discharge the air inside each of the headlight lamp housings such that the air is evacuated from the air holes that open downstream of the low-pressure air flow.  \n\n[0016]  In a fifth aspect of the present invention, the above breathing mechanism comprises breathing holes (for example, the breathing holes 10B and 12B in the embodiments) formed in the back wall of the lamp housing and filters (for example the water-repelling filters 13 and $\\mathbf{13^{\\prime}}$ in the embodiments) that cover them, wherein the filter (for example, the water-repelling filter 13' in the embodiments) of the headlight lamp housing on the side where the pressure inside the headlight lamp housing is positive due to the rotation of the radiator fan has a density that is lower than the filter (for example,the water-repelling filter 13 in the embodiments) of the headlight lamp housing on the side where the pressure inside the headlight lamp housing is negative due to the rotation of the radiator fan.  \n\n[0017]   By using this type of structure, it becomes possible to promote as much as possible the discharge of internal air in the headlight lamp housing having a positive pressure inside and suppress as much as possible the inflow of external air at the headlight lamp housing having a negative pressure inside.  \n\n[0018]  A sixth aspect of the present invention is an antifogging structure for headlight lamps provided on the left and right of the front part of the body of a vehicle having an engine (for example, the engine E in the embodiments) in an engine compartment that is disposed offset either to the left or right, wherein the breathing mechanisms that enables circulation of air into and out of the lamp housing are made different for the left and right headlight lamp housings.  \n\n[0019]   By using this type of structure, considering that the air closer to the engine contains higher content of moisture, it becomes possible to make it difficult for the air to stagnate in the headlight lamp housing on the side near the engine in comparison to the headlight lamp housing on the side distant from the engine.  \n\n[0020] In a seventh aspect of the invention, the breathing mechanism described above comprises breathing holes, and the breathing holes (for example, the breathing holes 10B and 12B in the embodiments) on the side near the engine are set so that their aperture area is larger than the breathing holes (for example, the breathing holes 10S and 12S in the embodiments) in the headlight lamp housing on the side distant from the engine.  \n\n[0021] By using this type of structure, the high-temperature and high-moist air near the engine can be discharged easily from the breathing holes having a large aperture area even when such air flows into the lamp housing.  \n\n[0022] In an eighth aspect of the present invention, the above breathing mechanism comprises breathing holes, and the number of breathing holes in the headlight lamp housing on the side near the engine is greater than the number of breathing holes in the headlight lamp housing on the side distant from the engine.  \n\n[0023] By having this type of structure, it becomes possible for the high-temperature air that that is near the engine and includes much water to be discharged easily from the many breathing holes even when it flows into the lamp housing.  \n\n[0024]In a ninth aspect of the invention, the above breathing mechanism comprises breathing holes formed in the back wall of the lamp housing and a filter that covers them, and the filter of the headlight lamp housing on the side near the engine has a lower density than the filter of the headlight lamp housing on the side distant from the engine.  \n\n[0025] By having this type of structure, it becomes possible for the high-temperature air that that is near the engine and includes much moisture to be discharged easily by passing though the low-density filter that has little resistance.",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# BRIEFDESCRIPTIONOFTHEDRAWINGS  \n\n[0026] FIG.1 is a perspective view drawing of the vehicle of the first embodiment.  \n\n[0027] FIG.2 is a partial plane view showing the inside of the engine compartment in the first embodiment.  \n\n[0028]  FIG. 3 is a frontal explanatory drawing showing the state of the disposition of the headlight lamps and the radiator in the first embodiment.   \n[0029]  FIG. 4 is an enlarged back view of the left headlight lamp housing in the first embodiment.   \n[0030] FIGS. 5A and 5B are back views of the left and right headlight lamp housings in the first embodiment. [0031]FIG.6 is a back view of the left and right headlight lamp housings in the second embodiment.   \n[0032]  FIG. 7 is a back view of the left and right headlight lamp housings in the third embodiment.   \n[0033]  FIG.8 is a back view of the left and right headlight lamp housings in the fourth embodiment.   \n[0034] FIG. 9 is a perspective view showing the installation state of the water-repelling filter in the fourth embodiment.   \n[0035] FIG.10 is a partial frontal view showing the inside of the engine compartment in the fifth embodiment.   \n[0036]FIGS.11A and 11B are back views of the left and right headlight lamp housings in the fifth embodiment.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# DESCRIPTIONOFTHEPREFERRED EMBODIMENTS  \n\n[0037] Below, embodiments of the invention will be explained with reference to the attached figures. FIG.1 through FIG. 5 illustrates the first embodiment of the invention.  \n\n[0038] As shown in FIG. 1 through FIG. 3, in the front part of the body 1 of a vehicle, a radiator 4 is disposed on the engine compartment 3 side of the front grill 2, and the respective headlight lamps 5L and 5R are provided on both left and right sides of the radiator 4. On the back side of the radiator 4, a radiator fan 6 and an electrical fan 7 for an air-conditioning system are provided. Moreover, L denotes left and R denotes right (and similarly below).  \n\n[0039] As shown in FIG. 2 and FIG. 3, in the present embodiment, the radiator fan 6 rotates counterclockwise when viewed from the front of the body 1, and, in cooperation with the electrical fan 7 that similarly rotates counterclockwise, produces a flow of air indicated by the arrow towards the headlight lamp 5R on the right side by passing through the front of the radiator 4 from the headlight lamp 5L on the left side.Moreover, E denotes the engine disposed to the side.  \n\n[0040] Therefore, due to the radiator fan 6 being interposed therebetween, the headlight lamp 5L on the left side positioned upstream of the air flow and the headlight lamp 5R on the right side positioned downstream of the airflow are placed under differing pressure conditions.  \n\n[0041]  The headlight lamps 5L and 5R comprise transparent lenses 50L and 50R and the lamp housings 51L and 51R, and have built-in a light (not illustrated), and the back walls 52L and 52R of the lamp housings 51L and 51R face engine compartment 3.  \n\n[0042]The brackets 53 and 54 (refer to FIG. 4) of the lamp housings 51L and 51R are fixed to the body panel 8, and thereby the headlight lamps 5L and 5R are mounted on the body 1.  \n\n[0043] Next, the arrangement of the headlight lamps 5L and 5R will be explained using as an example the headlight lamp 5L on the left side shown in FIG. 4. In the back wall 52L of the lamp housing 51L, a breathing mechanism for preventing fogging of the headlight lamp 5L is provided that allows circulation of air into and out of the lamp housing 51L. In addition, this breathing mechanism has a structure that differs from that of the headlight lamp 5R on the right side.  \n\n[0044]  Specifically, the breathing mechanism comprises breathing holes 10, 11, and 12 provided in the back wall 52L of the lamp housing 51L. These breathing holes 10, 11, and 12 are formed as follows: one (breathing hole 10) if formed below the outside portion of the vehicle in the transverse direction (below, referred to simply as the “outer portion\"); one (breathing hole 11) is formed below the inner portion of the vehicle in the transverse direction (below, simply referred to as the “inner portion\"); and one (breathing hole 12) is formed above the light bulb disposition location at the center portion in the vertical direction of the center portion of the vehicle (below, simply referred to as the “center portion\") in the transverse direction of the headlight lamp 5L. Arch shaped roof parts $\\mathbf{10}a$ and ${\\bf11}a_{} $ and a circular arc-shaped roof part ${\\bf1}2a{\\bf\\Phi}$ are respectively formed above the breathing holes 10, 11, and 12. The penetration of raindrops or car wash water from above into the breathing holes is prevented by these roof parts 10a, 1la, and $_{12a}$  \n\n[0045] Here,in the outer portion, respectively large sized and small sized breathing holes 10B and 10S are selected and can be formed by being pressed open after a molding step. The breathing holes 12B and 12S respectively having a large size and a small size can be formed in the center portion, and similarly the breathing holes 11B and 11S respectively having a large size and a small size can be formed in the inner portion. Moreover, as shown in FIG.4, as is shown by the hatching, in the outer portion, the small sized breathing hole 10S is selected; in the inner portion, as is shown by the hatching, the small sized breathing hole 12S is similarly selected; and at the inner portion, the breathing hole 11 is not formed. Here, the breathing holes (correctly referred to as the “breathing hole formation positions\") that are not selected are shown by a dashed line.  \n\n[0046] Next, the structure of the breathing holes in the headlight lamps 5L and 5R in this first embodiment will be explained with reference to FIG. 5.Moreover, the flow of the air is shown in the figure by the arrow. In addition, the large, small, and unselected breathing hole formation positions are denoted by reference numerals (for example,“11\") that group the large hole, the small hole, and the unselected hole together (similarly in the following embodiments).  \n\n[0047]   As shown in FIG. 5, breathing holes 10 and 12 are formed in the respective outer portion and the center portion the headlight lamp 5L on the left side and the headlight lamp 5R on the right side. Moreover, breathing hole 11 is not formed in either of the headlight lamps 5L or 5R, but depending on the state of the vehicle, that is, depending on the pressure on the back wall of the lamp housing, breathing holes 10 and 12 can be used instead of the breathing hole 11. In addition, as shown in FIG.3, each of the breathing holes 10 and 12 in the headlight lamp 5L on the left side with a lamp housing 51L, which has a negative pressure inside due to the rotation of the radiator fan 6 and the electric fan 7, has an aperture area set so as to be smaller than each of the breathing holes 10 and 12 of the headlight lamp 5R on the right side with a lamp housing 51R having a positive pressure inside due to the rotation of the radiator fan 6 and the electric fan 7, and thereby the structures of both are different.  \n\n[0048] Concretely, the breathing holes 10S and 12S having a small size are formed in the headlight lamp 5L on the left side and the breathing holes 10B and 12B having a large size are formed in the headlight lamp 5R on the right side. Moreover, the parts where the breathing holes 10 and 12 are opened are shown in the figure by the hatching, and the parts where they are not opened are shown by the dashed line (similarly in the following embodiments).  \n\n[0049]  Specifically, when the inside of the leadlight 5L on the left side has a negative pressure due to a negative pressure being established by the rotation of the radiator fan 6 and the electric fan 7, the high humidity air in the engine compartment 3 is drawn into the lamp housing 51L of the headlight lamp 5L on the left side, and there is the possibility that fogging will occur.  \n\n[0050]  To the extent that the amount of air drawn in from the engine compartment 3 is reduced, fog does not occur. Thus, the diameter of the breathing holes 10S and 12S of the outer portion and the center portion of the headlight lamp 5L on the left side is made smaller than the respective diameters of those in the headlight lamp 5R on the right side, the aperture area of each of the breathing holes 10S and 12S of the headlight lamp 5L on the left side, which has a negative pressure and is easily fogged, is made small, and this contributes to making fogging difficult to a degree that is identical to that of the headlight lamp 5R on the right side.  \n\n[0051] In addition, contrariwise, at the headlight lamp 5R on the right side, the aperture area of the breathing holes 10B and 12B is larger than the that of the headlight lamp 5L on the left side, but because the headlight lamp 5R on the right side is placed under a positive pressure due to the counterclockwise rotation of the electric fan 7, the air inside is discharged into the engine compartment 3 from each of the breathing holes 10B and 12B that have a larger aperture area than that of the headlight lamp 5L on the left side, and thereby the anti-fogging performance is increased.  \n\n[0052] Therefore, according to this embodiment, the inflow of external air is suppressed as much as possible at the headlight lamp 5L on the left side, which has a negative pressure inside, and the discharge of internal air is promoted as much as possible at the headlight lamp 5R on the right side,which has a positive pressure inside. Thereby, the unevenness in the anti-fogging performance in the left and right headlight lamps 5L and 5R, which originates in the direction of the rotation of the radiator ran 6 and the electric fan 7, is adjusted by changing the aperture area of the breathing holes 10 and 12, the anti-fogging performance is increased, and the uniformity of the illumination characteristics on the left and right can be maintained.  \n\n[0053] Next, aided by FIG. 1 and FIG. 3,a second embodiment of the present invention will be explained with reference to FIG. 6. Moreover, parts that are identical to those in the first embodiment will be explained denoted by identical numbers.  \n\n[0054]  In this embodiment, the number of the breathing holes formed in the back walls 52L and 52R of the lamp housings 51L and 51R of the respective headlight lamps 5L and 5R is different. Concretely, three breathing holes 10, 11, and 12 are formed in the headlight lamp 5R on the right side, whose lamp housing 51R has a positive pressure due to the rotation of the radiator fan 6 and the electric fan 7, and two breathing holes 10 and 12 are formed in the headlight lamp 5L on the left side, whose lamp housing 51L has a negative pressure due to the rotation of the radiator fan 6 and the electric fan 7. That is, the number of breathing holes in the headlight lamp 5R on the right side is greater than the number of breathing holes in the headlight lamp 5L on the left side. Moreover, the breathing holes 10, 11, and 12 use the large breathing holes 10B, 11B, and 12B having the same size.  \n\n[0055]The breathing holes 10 and 12 are formed in the inner portion and the center portion of the headlight lamp 5L on the left side identically to the first embodiment, on the right side the breathing holes 10 and 12 are added to the outer portion and center portion in the headlight lamp 5R, and the breathing hole 11 is formed in the inner portion.  \n\n[0056]Thereby, the amount of air that is discharged from the headlight lamp 5R on the right side,whose inside has a positive pressure due to the rotation of the radiator fan 6 and the electric fan 7, is increased, the discharge of moist air is promoted, and the inflow of air into the headlight lamp 5L on the left side, whose inside has negative pressure, can be suppressed by making the number of breathing holes lower than the headlight lamp 5R on the right side, is decreased. Thus, the unevenness in the anti-fogging performance in the left and right headlight lamps 5L and 5R, which originates in the direction of the rotation of the radiator ran 6 and the electric fan 7, is adjusted by changing the number of the breathing holes, the anti-fogging performance is increased, and the uniformity of the illumination characteristics on the left and right can be maintained.  \n\n[0057] Moreover, because this embodiment focuses on the number of breathing holes, an example was explained wherein each of the breathing holes 10, 11, and 12 is formed as the breathing holes 10B, 11B and 12B having identical large sizes, but it is also possible to make the breathing holes 10 and 12 on the headlight lamp 5L side have the small-sided breathing holes 10S and 12S.  \n\n[0058]Next, aided by FIG.1 and FIG.3, a third embodiment of the present invention will be explained with reference to FIG.7. Here, parts with are identical to those in the first embodiment will be explained denoted by identical numbers. Moreover, the arrow in the figure indicates the flow of the air.  \n\n[0059]  In this embodiment, when the airflow indicated by the arrow in FIG.2 occurs due to the rotation of the radiator fan 6 and the electric fan 7, the breathing holes in each of the headlight lamps 5L and 5R are formed downstream of this airflow.  \n\n[0060] Concretely, in FIG. 7, the flow of the air occurs from the left to the right, but the further downstream of the flow, the pressure becomes progressively lower than it is upstream. This means that the headlight lamp 5R on the right side is placed under a lower pressure than the headlight lamp 5L on the left side, and at the same time, at each of the headlight lamps 5L and 5R, it means that the pressure on the right side is lower than the pressure on the left side.  \n\nSpecifically, at the headlight lamp 5R on the right side, in the transverse direction of the vehicle the pressure at the outer side is lower than the pressure at the center side, and at the headlight lamp 5L on the left side, the pressure at center side in the transverse direction of the vehicle is lower than the pressure at the inner side. Focusing on this factor, in this embodiment, the breathing hole 1lB is formed in the inner portion of the headlight lamp 5L on the left side, and the breathing hole 1oB is formed in the inner portion of the headlight lamp 5R on the right side. That is, the formation positions of the breathing holes at the left and right headlight lamps 5L and 5R are varied.  \n\n[0061] Therefore, the air inside each of the headlight lamps 5L and 5R can be discharged by being drawn out from each of the breathing holes 11B and 10B that open downstream of the airflow having low pressure, and thus the unevenness in the anti-fogging performance in the left and right headlight lamps 5L and 5R,which originates in the direction of the rotation of the radiator ran 6 and the electric fan 7, is adjusted by discharging air inside both the lamp housings 51L and 51R, the anti-fogging performance is increased, and the uniformity of the illumination characteristics on the left and right can be maintained.  \n\n[0062] Next, aided by FIG. 1 and FIG. 3, a fourth embodiment of the present invention will be explained with reference to FIG. 8 and FIG. 9. Here, parts with are identical to those in the first embodiment will be explained denoted by identical numbers.Moreover, the arrow in the figure indicates the flow of the air.  \n\n[0063] In this embodiment, a breathing mechanism is formed comprising the breathing holes 10 and 12 formed in the back walls 52L and 52R of the lamp housings 51L and 51R and the water-repellant filters 13 and $\\mathbf{13^{\\prime}}$ that cover them. The water-repellant filter 13 prevents penetration of water but allows the passage of air, and the higher its density, the more difficult it is for air to pass through. Moreover, sponge can be used instead of a water-repellant filter.  \n\n[0064]  As shown in FIG. 9, a rubber filter mounting part 131 is installed under the arch-shaped roof parts 10a and $_{12a}$ formed in the back walls 52L and 52R of the lamp housings 51L and 51R and extends in a pipe-form to a position that is accommodated in these roof parts 10a and $_{12a}$ Under the filter mounting part 131, water falls by being guided downward, and the roof-shaped water guide 132 is installed to prevent water from splashing up from below.  \n\n[0065]   In addition, at the filter mounting parts 131, breathing holes 10 and 12 are formed that communicate with the inside of the lamp housings 51L and 51R by passing through the center portion, and the water-repellant filters 13 and 13' are installed in the filter mounting part 131. Moreover, in the following explanation, an example is explained using the water-repellant filter 13 in the headlight lamp 5L on the left side, and the explanation of the water-repellant filter $\\mathbf{13^{\\prime}}$ in the headlight lamp 5R on the right side having an identical structure will be omitted. In addition, the opening diameter of the breathing holes 10 and 12 can be either the aperture diameter of the large breathing holes 10B and 12B or the aperture diameter of the small breathing holes 1oS and 12S.  \n\n[0066]   The water-repellant filters 13 are cap-shaped members comprising a tubular portion 14 that is mounted by being inserted into the filter insertion part 131 and a filter body 15, and four separate projections 142 are formed on the periphery of the tubular portion 14.  \n\n[0067]  In addition, a synthetic resin stopping cap 143 having a tubular shape with a bottom that covers the same is installed on the water-repellant filter 13, and when the stopping cap 143 is installed in the water-repellant filter 13, the air flow path between the two is maintained by these projections 142. At the position corresponding to the filter body 15 of the stopping cap 143, spacer projections 144 are formed at 3 locations along the peripheral direction, a space between the stopping cap 143 and the filter body 15 during installation is maintained, and can communicate with the air flow path formed by the projections 142.  \n\n[0068]  Here, the structure of each of the headlight lamps 5L and 5R is identical on the point of installing the waterrepellant filters 13 and 13' on the breathing holes 10 and 12 at the outside position and the center position, but the density of the water-repellant filters 13 and 13' varies between the headlight lamp 5L on the left side and the headlight lamp 5R on the right side, and the water-repellant filter 13' of the headlight lamp 5R on the right side placed under positive pressure due to the rotation of the electric fan 7 has a lower density than the water-repellant filter 13 of the headlight lamp 5L on the left side that has been placed under a negative pressure due to the rotation of the electric fan 7.  \n\n[0069] Therefore, at the headlight lamp 5R on the right side having a positive pressure inside, the discharge of interior air is promoted because the density of the waterrepellant filter 13' is low, and at the headlight lamp 5L on the left side having a negative pressure inside, the flow of outside air can be suppressed because the density of the water-repellant filter 13 is higher than that of the headlight lamp 5L on the left side. Therefore, while the unevenness in the anti-fogging performance in the left and right headlight lamps 5L and 5R that originates in the direction of the rotation of the electric fan 7 is adjusted by changing the density of the water-repellant filters, the anti-fogging performance is increased, and the illumination performance that is even on the left and right can be maintained. Moreover, both breathing holes 12 can be opened and water-repellant filters 13 and 13' provided there as well.  \n\n[0070] Next, aided by FIG. 1 to FIG. 3, a fifth embodiment of the invention will be explained with reference to FIG.10 and FIG.11. Moreover, parts identical to those of the first embodiment will be explained using identical reference numerals.As shown in FIG.10, this embodiment is structured so that the radiator fan 6 and the electric fan 7 rotate in mutually different directions.  \n\n[0071] Therefore, unlike FIG. 2, no bias in the pressure occurs in the environment in which each of the headlight lamps are placed that originates an air flow that is biased due to the radiator fan 6 and the electric fan 7, but because the engine E in the engine compartment 3 is disposed in a position offset to the right in the compartment, the temperature conditions where each of the headlight lamps 5L and 5R are placed are different.  \n\n[0072] Specifically, considering that there is much incorporated moisture because the temperature of the air in the vicinity increases as it gets closer to the engine E,the structure is such that, in comparison to the headlight lamp 5L on the side distant from the engine E, the breathing operation of the headlight lamp 5R on the side close to the engine E can be carried out smoothly.  \n\n[0073] Concretely, as shown in FIG. 11, because each of the breathing holes 10 and 12 of the headlight lamp 5R on the right side close to the engine E is set so as to have a larger aperture area than each of the breathing holes 10 and 12 of the headlight lamp 5L on the left side distant from the engine E, breathing holes 10S and 12S having a small size are formed in the headlight lamp 5L on the left side and breathing holes 10B and 12B having a large size are formed in the headlight lamp 5R on the right side. Note that breathing hole 12 is not opened. Therefore, the headlight lamps 5L and 5R have a structure that is substantially identical to that shown in FIG.5.  \n\n[0074]That is, because the headlight lamp 5R on the right side is positioned near the engine E under high temperature conditions, there is the possibility that there is much moisture incorporated in the air. Thus, the large sized breathing holes 10B and 12B are structured such that even if air is drawn into the engine compartment 3, it can be immediately discharged and the breathing operation can be carried out smoothly, and can thereby contribute to the anti-fogging performance to the same degree as the headlight lamp 5L on the left side.  \n\n[0075] Therefore, according to this embodiment, even if air having a high humidity flows into the headlight lamp 5R on the right side near the engine E that is more disadvantageous in terms of condensation, it can easily be discharged making it difficult for air to stagnate. Thus, the unevenness in anti-fogging performance between the left and right headlight lamps 5L and 5R originating in the offset disposition of the engine E can be adjusted by providing a structure in which the breathing mechanisms on the left and right are different, the antifogging performance can be increased, and the evenness of the illumination performance on the left and right can be maintained.  \n\n[0076] Here,in the fifth embodiment described above, the breathing action was carried out smoothly by focusing on the size of the breathing holes and making the aperture area of the headlight lamp 5R on the right side, which is close to the engine E, large. However, as shown in FIG.6 for the second embodiment, it is also possible to provide three breathing holes 10, 11, 12 in the headlight lamp 5R on the right side, which is near the engine E, provide two breathing holes 10 and 12 in the headlight lamp 5L on the left side, which is distant from the engine E, and increase the number of breathing holes in the headlight lamp 5R on the right side, which is close to the engine E.  \n\n[0077] In the case of this type of structure, because it is possible to discharge easily the high temperature air close to the engine E that includes much moisture from the many breathing holes 10, 11, and 12, it is possible to eliminate the unevenness in the anti-fogging performance in the headlight lamps 5L and 5R on the left and right that is caused by the offset disposition of the engine E.  \n\n[0078] In addition, as shown in FIG. 8 for the fourth embodiment, the breathing mechanism is formed by breathing holes 10 and 12 of the filter mounting part 131 formed in the back walls 52L and 52R of the lamp housings 51L and 51R and water-repellant filters 13 and 13' that cover the same. It is also possible to use a water-repellant filter $\\mathbf{13^{\\prime}}$ of the headlight lamp 5R on the right side near the engine E that has a lower density than the water-repellant filter 13 of the headlight lamp 5L on the left side distant from the engine E.  \n\n[0079] In the case of this type of structure, because the high temperature air near the engine E that includes much moisture can pass through the low density water-repellant filter $\\mathbf{13^{\\prime}}$ that has low resistance and thereby be easily discharged, it is possible to eliminate the unevenness in the anti-fogging performance in the headlight lamps 5L and 5R on the left and right that originates in the offset disposition of the engine E.  \n\n[0080] Moreover, in the above-described embodiments of the invention, the case in which the engine is placed towards the side was explained. However, it is possible to apply the invention in the case wherein the engine is placed in the center part in the transverse direction. In this case, if the influence of the heat originating in the other auxiliary devices is ignored, the heat bias due to the heat of the engine is identical at the left and right headlight lamps, and thus the only influence on the left and right headlight lamps is the unbalanced pressure due to the radiator fan and the like. Therefore, in this case, the breathing mechanism can be set taking into consideration this unbalance in the pressure due to the radiator fan.  \n\n[0081] In addition, in the first through fourth embodiments, the breathing mechanisms are structured differently in the left and right headlights taking into consideration only the bias in pressure applied to each of the headlight lamps due to the radiator fan, but as shown in FIG. 2,the unevenness in the anti-fogging performance of the left and right headlight lamps can be even further reduced by taking into consideration the disposition of the engine, which is offset to the right side, the size of the breathing holes, which make up the breathing mechanism, the number of locations, and finer adjustment of the density of the water-repellant filters.  \n\n[0082] In addition, although each of the embodiments was explained focusing on the size and number of the breathing holes, it is possible to apply various structures for more reliably preventing the penetration of air containing much moisture into the headlight lamps. For example, the discharge of air in the headlight lamps can be made smooth by setting the direction of the breathing holes to conform to the flow of the air, or, focusing on the fact that within the engine compartment the temperature is high in the upper portion, air holes can be formed as far as possible on the bottom side where the temperature is low.  \n\n[0083] In addition, the structure of a combination of a radiator fan and an electric fan was explained, but a structure can also be applied in which only a radiator fan is disposed.  \n\n[0084]  In addition, the shape and the number of breathing holes are only one example, and are not limited by the embodiments described above.  \n\n[0085] As described above, according to a first aspect of the invention, by taking into consideration the flow of the air produced by the radiator fan, it is possible to use a structure in which the air in the lamp housing can be easily discharged and the air flows into the lamp housing with difficulty. Thereby, the effects can be obtained that the unevenness in the anti-fogging performance produced in the left and right headlight lamps can be adjusted by structuring the breathing mechanisms on the left and right differently, the anti-fogging performance can be increased, and the evenness of the illumination performance on the left and right can be maintained.  \n\n[0086] According to a second aspect of the invention, the inflow of external air can be suppressed as much a possible in the headlight lamp having a negative pressure inside and the discharge of internal air in the headlight lamp having a positive pressure inside can be promoted as much as possible. Thereby, the effect is obtained that the variation in the anti-fogging performance in the left and right headlight lamps originating in the direction of the rotation of the radiator fan can be adjusted by varying the aperture area of the breathing holes, the anti-fogging performance can be increased, and the evenness of the illumination performance on the left and right can be maintained.  \n\n[0087] According to a third aspect of the invention, the discharge of air from inside the headlight lamp having a negative pressure inside is promoted and the inflow of air into the headlight lamp having a negative pressure inside is suppressed. Thereby, the effects are obtained that the variation in the anti-fogging performance in the left and right headlight lamps that originates in the direction of the rotation of the radiator fan is adjusted by varying the number of breathing holes, the anti-fogging performance can be increased, and the evenness of the illumination performance on the left and right can be maintained.  \n\n[0088] According to a fourth aspect of the invention, it becomes possible to discharge the air in each of the headlight lamps such that it is drawn out from the breathing holes opened downstream of the airflow having a low pressure. Thereby, the effects are obtained that the variation in the anti-fogging performance in the left and right headlight lamps originating in the direction of the rotation of the radiator fan can be adjusted by discharging the air inside both headlight lamps, the anti-fogging performance can be increased, and the evenness of the illumination performance on the left and right can be maintained.  \n\n[0089] According to a fifth aspect of the invention, the discharge of internal air in the headlight lamp having a positive pressure inside can be promoted as much as possible and the inflow of external air can be suppressed as much a possible in the headlight lamp having a negative pressure inside. Thereby, the effect is obtained that the variation in the anti-fogging performance in the left and right headlight lamps originating in the direction of the rotation of the radiator fan can be adjusted by varying the density of the filters, the anti-fogging performance can be increased, and the evenness of the illumination performance on the left and right can be maintained.  \n\n[0090]   According to a sixth aspect of the invention, taking into consideration that the closer to the engine the greater the moisture included in the air, it is possible to make it difficult for the air in the headlight lamps on the side close to the engine difficult to stagnate in comparison to the headlight lamp on the side distant from the engine. Thereby, the effect is obtained that the variation in the anti-fogging performance in the left and right headlight lamps caused by the direction of the rotation of the radiator fan can be adjusted by structuring the breathing mechanisms on the left and right differently, the anti-fogging performance can be increased, and the evenness of the illumination performance on the left and right can be maintained.  \n\n[0091] According to a seventh aspect of the invention, even if high temperature air that includes much moisture close to the engine flows into the lamp housing, it can be discharged easily from the breathing holes having a large aperture area. Thereby, the variation in the anti-fogging performance in the left and right headlight lamps that originates in the offset disposition of the engine can be adjusted by forming the aperture area of the breathing mechanisms on the left and right differently, the anti-fogging performance can be increased, and the evenness of the illumination performance on the left and right can be maintained.  \n\n[0092] According to an eighth aspect of the invention, even if the high temperature air that includes much moisture near the engine flows into the lamp housing, it is possible to discharge it easily from the many breathing holes by passing through a low density filter having a low resistance. Thereby, the variation in the anti-fogging performance in the left and right headlight lamps that originates in the offset disposition of the engine can be adjusted by providing differing numbers of breathing holes on the left and right, the anti-fogging performance can be increased, and the evenness of the illumination performance on the left and right can be maintained.  \n\n[0093]  According to a ninth aspect of the invention, even if the high temperature air that includes much moisture near the engine flows into the lamp housing,it is possible to discharge it easily from the many breathing holes by passing through a low density filter having a low resistance. Thereby, the variation in the anti-fogging performance in the left and right headlight lamps that originates in the offset disposition of the engine can be adjusted by providing filters on the left and right that have differing densities, the anti-fogging performance can be increased, and the evenness of the illumination performance on the left and right can be maintained.  \n\nWhat is claimed is:  \n\n1. An anti-fogging structure for headlight lamps provided on the left and right of the radiator fan at the front of the body of a vehicle, wherein each headlight lamp comprises a headlight lamp housing for housing each headlight lamp; and  \n\na breathing mechanism that enables circulation of air into and out of the lamp housing is made different for the left and right headlight lamps housings.  \n\n2.An anti-fogging structure for headlight lamps according to claim 1 wherein said breathing mechanism comprises breathing holes formed in the back wals of the lamp housings, and the breathing holes of the headlight lamp housings on the left or right side of the vehicle where the pressure inside the lamp housing is negative due to the rotation of the radiator fan are set so that their aperture areas are smaller than those of the breathing holes of the headlight lamp housing on the side where the pressure inside the lamp housing is positive due to the rotation of the radiator fan.  \n\n3.An anti-fogging structure for headlight lamps according to claim 1 wherein said breathing mechanism comprises breathing holes formed in the back walls of the headlight lamp housing, and the number of breathing holes of the headlight lamp housing on the side where the pressure inside the lamp housing is positive due to the rotation of the radiator fan is greater than the number of breathing holes of the headlight lamp housing on the side where the pressure inside the lamp housing is negative due to the rotation of the radiator fan.  \n\n4. An anti-fogging structure according to claim 1 wherein said breathing mechanism comprises breathing holes formed in the back wall of the lamp housing, and in the case that an air flow is generated due to the rotation of the radiator fan, each of the breathing holes in the headlight lamp housing is formed downstream of said airflow.  \n\n5. An anti-fogging structure according to claim 1 wherein said breathing mechanism comprises breathing holes formed in the back wall of the lamp housing and filters that cover the breathing holes and the filter for the headlight lamp housing on the side where the pressure inside the headlight lamp housing is positive due to the rotation of the radiator fan has a density that is lower than the filter for the headlight lamp housing on the side where the pressure inside the headlight lamp is negative due to the rotation of the radiator fan.  \n\n6. An anti-fogging structure for headlight lamps provided on the left and right at the front part of the body of a vehicle having an engine in an engine compartment that is disposed offset either to the left or right, and the breathing mechanisms that enables circulation of air into and out of the lamp housing are structured differently in the left and right headlight lamps.  \n\n7. An anti-fogging structure for headlight lamps according to claim 6 wherein said breathing mechanism comprises breathing holes, and the breathing holes for the headlight lamp housing on the side near the engine have an aperture area set larger than the breathing holes in the headlight lamp housing on the side distant from the engine.  \n\n8.An anti-fogging structure for headlight lamps according to claim 6 wherein said breathing mechanism comprises breathing holes, and the number of breathing holes in the headlight lamp on the side near the engine is greater than the number of breathing holes in the headlight lamp on the side distant from the engine.  \n\n9.An anti-fogging structure for headlight lamps according to claim 6 wherein said breathing mechanism comprises breathing holes formed in the back wall of the lamp housing and a filter that covers them, and the filters in the headlight lamp on the side near the engine have a lower density than the filters in the headlight lamp on the side distant from the engine.",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/2011-DE-anti-fog.json b/task2/task2-chunks/2011-DE-anti-fog.json
new file mode 100644
index 0000000..c9c77f7
--- /dev/null
+++ b/task2/task2-chunks/2011-DE-anti-fog.json
@@ -0,0 +1,67 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19) United States (12) Patent Application Publication Daute et al.",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (10) Pub. No.: US 2011/0124785 A1 (43) Pub. Date: May 26, 2011",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54) ANTI-FOGGING AGENT BASED ON POLYGLYCEROL ANDNATURAL OILS  \n\n(30) Foreign Application Priority Data  \n\nJun.2,2008 (DE) 10 2008 026 263.3  \n\n(76) Inventors: Peter Daute, Beverstedt (DE); Martin Schafer, Stubben (DE)",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# Publication Classification  \n\n(21) Appl. No.: 12/995,249  \n\n(51) Int. Cl. C08K 11/00 (2006.01) (52) U.S. CI. 524/315;252/182.12  \n\n(22) PCT Filed: Jun. 2,2009",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# ABSTRACT  \n\n(86) PCT No.: PCT/EP2009/056742 $\\S371$ (c)(1), (2), (4) Date: Jan. 27, 2011  \n\nThe invention provides an anti-fogging agent comprising an ester product and at least one further anti-fogging agent. The invention also relates to shaped articles and polymer compositions comprising such anti-fogging agents, and the preparation and use thereof.",
+        "category": " Abstract"
+    },
+    {
+        "id": 6,
+        "chunk": "# ANTI-FOGGINGAGENTBASEDON POLYGLYCEROL ANDNATURAL OILS  \n\n[0001] The invention generally provides ester products, and the use thereof as anti-fogging agents, anti-fogging agents and processes for the preparation thereof. The invention also relates to shaped articles and polymer compositions comprising such anti-fogging agents, and the preparation and use thereof.  \n\n[0002] During the processing of plastics, anti-fogging agents are often added to these. These then serve to prevent the condensation of water and the formation of drops of water on the surface of the plastics. Such additives are often employed in the production of transparent packaging's and films. Without anti-fogging agents, a deposit forms on the inside, especially on transparent packaging films, as a result of which the contents of the packaging are scarcely or no longer detectable, as can be seen from Plastics Additives Handbook, 5th edition, Hanser Verlag,p. 609-626. The prevention of deposits is also of importance in other uses, for example spectacles, windows or visors of helmets as threedimensional forms. Generally, internal anti-fogging agents are incorporated into the plastic and therefore become part of the plastic and therefore also of the three-dimensional form containing this plastic, while external anti-fogging agents are applied externally to the plastic and therefore become part of the plastic as a surface layer and therefore also of the threedimensional form comprising this.  \n\n[0003] DE 10 2004 038 980 A1 discloses anti-fogging agents for plastics which are obtainable by transesterification of natural oils with polyethylene glycol.  \n\n[0004] U.S. Pat. No. 3,759,856 provides stabilizers for plastics, such as PVC, based on partial glycerol esters of monocarboxylic acids. The esters impart to the plastics antifogging properties and antistatic properties. The esters are obtained by reaction of polyglycerol with fatty acids or with fatty acid mixtures, for which either no catalyst or an acid catalyst is employed.  \n\n[0005] U.S. Pat. No. 5,302,327 discloses a process for the production of thermoplastic layers with anti-fogging properties by means of corona discharge. Polyglycerol esters or sorbitan esters of fatty acids are employed as anti-fogging agents. Monoesters are preferably employed. By way of example, the product Glycolube AFA-1 from Lonza Inc.is employed.  \n\n[0006] Generally, one object lies in overcoming the disadvantages emerging from the prior art. Furthermore, the known agents often do not have optimum properties with respect to the prevention of the formation of drops. There is therefore a continuous need to improve the known anti-fogging agents and to simplify the preparation processes. Since large quantities of anti-fogging agents are employed worldwide, a more efficient preparation process and an easier availability of the raw materials would be of significance.  \n\n[0007]   In particular, processes for the preparation of antifogging agents which can be carried out by a simple method and manner with few process steps are to be provided. Overall, the preparation of anti-fogging agents is to be facilitated and the availability of the raw materials improved. At the same time, the anti-fogging agents according to the invention should have good anti-fogging properties. The invention is based in particular on the object of achieving anti-fogging properties which are at least equivalent to those of known agents, or even of improving these. In this context, under moisture conditions the formation of drops on the plastics should take place as early as possible and a clear film should form from these as rapidly as possible. An improved packed product is thus also to be provided.  \n\n[0008]  A contribution towards achieving at least one of the above objects is made by a process, an ester product, an anti-fogging agent, a polymer composition, a shaped article and the use thereof according to the particular classifying claims, the sub-claims in each case dependent thereon relating to preferred embodiments.  \n\n[0009]  The invention provides an anti-fogging agent comprising  \n\n[0010] a) an ester product obtainable by a process comprising as process steps: [0011]  S1) provision of a reaction mixture comprising as reaction components [0012] Sla) a polyglycerol comprising at least two glycerol units; [0013]  S1b) an oil based on a natural oil; [0014]  S2) reaction of the reaction mixture by a transesterification in the presence ofa basic catalyst to give the ester product;   \n[0015] b) at least one further anti-fogging agent chosen from the group consisting of a polyethylene glycol ether, a partial glyceride or a polyethylene glycol ester or a mixture of at least two of these.  \n\n[0016]In view ofthe basic catalyzed transesterification, the process differs from known processes for the preparation of anti-fogging agents, in which the anti-fogging agents are obtained by an esterification of fatty acids.  \n\n[0017] According to the invention, both individual pure esters and ester mixtures with two and more individual esters which differ from one another are understood as the ester product. Preferably, the ester product comprises a particular polyglycerol partial ester to the extent of at least 20 wt. $\\%$ preferably to the extent of at least 30 wt. $\\%$ and particularly preferably to the extent of at least 60 wt. $\\%$ ,in each casebased on the ester product. In some cases, the particular one polyglycerol partial ester is found up to a maximum of 80 or 90 wt. $\\%$ , in each case based on the ester product.  \n\n[0018]  Basic is preferably understood as meaning that the reaction mixture employed for the transesterification has a pH in a range of from 7 to 14, preferably from 8 to 14 and particularly preferably 9 to 13.  \n\n[0019] Furthermore, in one embodiment of the process according to the invention, the reaction mixture comprises the reaction components Sla and S1b to the extent of at least 50 wt. $\\%$ ，preferably to the extent of at least 75 wt. $\\%$ and particularly preferably to the extent of at least 90 wt. $\\%$ in each case based on the total weight of the reaction mixture. In a particularly preferred embodiment, the reaction mixture comprises 10 to 95 wt. $\\%$ of the oil, particularly preferably between 20 to 90 wt. $\\%$ of the oil. In a further preferred embodiment, the reaction mixture comprises 5 to 90 wt. $\\%$ of polyglycerol, particularly preferably 10 to 50 wt. $\\%$ ofpolyglycerol or between 15 and 40 wt. $\\%$ of polyglycerol. Preferably, the content of basic catalyst is less than 1 wt. $\\%$ particularly preferably less than O.1 wt. $\\%$ . Particularly preferably, the content of the basic catalyst in the reaction mixture is between O.1 and $10~\\mathrm{ppm}$ . In a further preferred embodiment, the content of the further alcohol with at least two hydroxyl groups is between O and 20 wt. $\\%$ ，particularly preferably between O.1 and 10 wt. $\\%$ . Furthermore, in a further embodiment of the present invention the reaction mixture likewise comprises polyglycols, in particular polyethylene glycol or polypropylene glycol.  \n\n[0020]  A process which is preferred according to the invention is that wherein the process is carried out in a reaction mixture which contains the following reaction components:  \n\n[0021]  at least 5, preferably at least 10 and particularly preferably at least 15 wt. $\\%$ of oil;   \n[0022] from 5 to 95, preferably from 10 to 90 and particularly preferably from 5 to 85 wt. $\\%$ of polyglycerol;   \n[0023] from 0.0001 to 1, preferably from 0.001 to 0.5 and particularly preferably from 0.oo1 to 0.1 wt. $\\%$ of basic catalyst;   \n[0024]from O to 40 wt. $\\%$ ， preferably from O to 30 and particularly preferably from O to 20 wt. $\\%$ of a further alcohol with at least two hydroxyl groups;   \n[0025]from O to 20, preferably from O to 10 and particularly preferably from O to 5 wt. $\\%$ of additives such as impurities,which differ from the above reaction components,  \n\nwherein the sum of all the percentages by weight of the reaction components is 100.  \n\n[0026] Fatty acids are conventionally obtained chemically by isolation from fats or oils and by chemical synthesis. The process according to the invention has the advantage that the transesterification can be carried out directly starting from oils and polyglycerols. The process is thereby simplified and the availability of the raw materials is improved. Surprisingly, such ester products also show very good anti-fogging properties.  \n\n[0027]  A process which is preferred according to the invention is that in which the esterification is carried out in a one-pot process. In a one-pot process, the oil, the polyglycerol and the basic catalyst are mixed and then reacted, preferably in the same reactor.In contrast to a two- or multi-stage process in which the oil is first cleaved into fatty acid and glycerol and esterification is then carried out, according to the invention the oil or the oils are present with a content of free fatty acids of less than 30 wt. $\\%$ , preferably less than 15 wt. $\\%$ and particularly preferably less than 5 wt. $\\%$ ，in each case based on the oil, before the start of the transesterification.  \n\n[0028]  The basic catalysts which can be employed according to the invention preferably have a pH, determined in water at $25^{\\circ}\\mathrm{C}.$ , of more than 7, preferably more than 8, particularly preferably more than 10 and moreover preferably more than 12.All the catalysts which are known to the person skilled in the art and seem suitable for the transesterification according to the invention are possible in principle. In a preferred embodiment of the invention, the basic catalyst is chosen from the group consisting of alkali metal hydroxide, alkaline earth metal hydroxide or hydroxides of main group II of the periodic table of the elements, in each case including their hydrates, or a mixture of at least two of these. Particularly preferred catalysts are sodium hydroxide, potassium hydroxide, lithium hydroxide or a mixture of at least two of these as alkali metal hydroxides, and magnesium hydroxide, calcium hydroxide or a mixture of two of these as an alkaline earth metal hydroxide, aluminum hydroxide or boron hydroxide or both as hydroxides of main group III and mixtures of at least two of these.Lithium hydroxide is particularly preferred, in particular the monohydrate of lithium hydroxide.  \n\n[0029] It is furthermore preferable according to the invention for the transesterification to be carried out under at least two pressures which differ from one another. It is preferable here for a first pressure prevailing during the transesterification to be greater than, preferably at least 10 mbar, particularly preferably at least 100 mbar, moreover preferably at least 200 mbar and furthermore preferably at least 250 mbar greater than an at least one further pressure which likewise prevails during the transesterification. In the process according to the invention, it is furthermore preferable for the at least one further pressure to be in a range of from 100 to 500 mbar, preferably from 150 to 450 mbar and particularly preferably from 250 to 350 mbar. It is furthermore preferable according to the invention for the first pressure and the at least one further pressure to follow one another with a time difference of at least $5\\mathrm{min}$ ， preferably at least $15\\mathrm{min}$ and particularly preferably in a range of from 30 to $90~\\mathrm{min}$ .  \n\n[0030] It is furthermore preferable according to the invention for the reaction to be carried out at a temperature at which a transesterification takes place, which is often above $40^{\\circ}\\mathrm{C}$ Generally, it is to be noted that the transesterification temperature is chosen such that the ester product is not discolored by too high an exposure to heat. It is preferable here to carry out the transesterification in a range of from 100 to $350^{\\circ}\\mathrm{C}.$ ， preferably from 150 to $300^{\\circ}~\\mathrm{C}$ 、 and particularly preferably from 200 to $270^{\\circ}\\mathrm{~C~}$ . It is furthermore preferable for the transition from the first to the at least one further pressure to take place at least at a temperature above $40^{\\circ}\\mathrm{C}.$ , and preferably at the abovementioned temperatures according to the invention. Thus, according to the invention it is furthermore preferable to carry out the transesterification over a reaction period of from $10\\mathrm{min}$ to $10\\mathrm{h}$ , preferably from 0.5 to $^{7\\mathrm{h}}$ and particularly preferably from 1 to $6\\mathrm{{h}}$ . In the present case, the start of the reaction period is regarded as being when the transesterification starts to a noticeable extent, such as is the case, for example, at a temperature above $40^{\\circ}\\mathrm{C}$  \n\n[0031] According to the invention, the oil used is a natural oil, which can also be chemically modified. The term “oil\" describes mixtures of esters of glycerol. Natural oils essentially consist of glycerol esters of aliphatic monocarboxylic acids, the so-called fatty acids. These have chain lengths of from 6 to $22\\mathrm{C}$ atoms. The esters are also called triglycerides. “Oils\" in the context of the invention are present if these are liquid above $40^{\\circ}$ C. Natural oils from different biological sources vary with respect to the nature and the distribution of the amounts of the fatty acids they contain. Natural oils according to the invention can be of either plant or animal origin. The natural oils according to the invention also include synthetically prepared oils which have a chemical structure the same as that of the natural oils. The use of natural oils with a content of triglycerides of greater than 50, preferably greater than 75 and particularly preferably greater than 90 wt. $\\%$ , in each case based on the oil, is preferred according to the invention.  \n\n[0032] In a preferred embodiment of the invention, the content of C18 fatty acids in the total fatty acids which are esterified with the one glycerol of the oil is in a range of from 30 to 95, preferably 50 to 95 and particularly preferably from 75 to 95 and moreover preferably from 80 to 95 wt. $\\%$ , in each case based on the oil. In a further embodiment, the content of unsaturated fatty acids in the glycerides is greater than 10, preferably greater than 30, in particular greater than 60 and particularly preferably greater than 70 wt. $\\%$ ，in each case based on the oil.  \n\n[0033]  In a preferred embodiment ofthe invention, the oil is chosen from the group consisting of rape oil, castor oil, hydrogenated castor oil, sunflower oil, palm oil, tallow oil, hydrogenated tallow oil, coconut oil, groundnut oil and soya oil or a mixture of at least two of these, rape oil being particularly preferred. Sunflower oil is prepared from the seeds of the sunflower and comprises approximately 35 to $95\\%$ of C18 fatty acids. The content of unsaturated fatty acids is approximately between 20 and $75\\%$ . Castor oil is obtained from the seeds of the castor oil bush by cold pressing and comprises the glyceride of ricinoleic acid to the extent of about80 to $85\\%$ . Rape oil is also called rapeseed oil and is obtained from the seeds of rape by pressing. The oil comprises about $63\\%$ of oleic acid and $20\\%$ of linoleic acid.Soya oil is obtained from soya beans by pressing, optionally followed by extraction of hydrocarbons, and comprises chiefly C18 fatty acids, which are predominantly unsaturated. Palm oil is obtained from the fruit pulp ofpalm fruits and comprises a high content of linoleic acid.  \n\n[0034]In the context of the invention, “chemically modified\" means that the oil obtained from biological sources is subjected to a treatment which essentially does not influence the ester bonds and changes the chemical consistency of the oil.A chemical after-treatment process on natural oils which is preferred according to the invention is hardening, in which the carbon-carbon double and triple bonds contained in some fatty acid chains are converted into single bonds. The oils according to the invention can also be mixed with additives. Mixtures which comprise more than $50\\%$ ， preferably more than $75\\%$ or $90\\%$ of natural oil are also regarded as natural oil in the context of the invention.  \n\n[0035] In the context of the invention,“polyglycerol\" represents ethers from two or more glycerol molecules. In the context of the invention, the term polyglycerol therefore also includes diglycerol. The term polyglycerol also describes ether mixtures which have a particular distribution of dimers, trimers, tetramers etc. from glycerol, depending on their preparation process and subsequent separation steps. Numerous processes for the preparation of polyglycerols are known in the prior art, for example in U.S.Pat.No.3,968,169. Solvay Chemicals International offers a diglycerol and a polyglycerol under the brand names “Solvay Diglycerol\" and “Solvay Polyglycerol- $3^{\\circ}$ Polyglycerols serve industrially as starting substances for the preparation of cosmetics, as emulsifiers for industrial use and as additives for foodstuffs.  \n\n[0036] In a preferred embodiment of the invention, the polyglycerol has an average number of from 1.5 to 5 glycerol units per molecule.An average number of from 2 to 4 glycerol units per molecule is particularly preferred. Generally, it is particularly preferable for the polyglycerol to comprise more than 70 wt. $\\%$ , preferably more than 80 wt. $\\%$ and particularly preferably more than 85 wt. $\\%$ ,in each case based on the polyglycerol, of di-, tri- and tetraglycerol. In a particularly preferred embodiment of the invention, a mixture which comprises more than 30, particularly preferably more than $40\\%$ of triglycerol is used as the polyglycerol. The use of a mixture which comprises less than $10\\%$ of monoglycerol, 20 to $40\\%$ of diglycerol, 25 to $50\\%$ of triglycerol and 10 to $30\\%$ of tetraglycerol and less than $20\\%$ of polyglycerols of 5 glycerol sub-units or more is particularly preferred. This corresponds to the distribution of glycerols in the product“Solvay Polyglycerol-3\", the use of which is particularly preferred.  \n\n[0037] A process in which the transesterification is carried out in the presence of at least one further alcohol which differs from the polyglycerol is preferred according to the invention. In a preferred embodiment of the invention, the further alcohol comprises at least two, preferably 2 to 50, particularly preferably 2 to 40 and furthermore preferably 2 to 20 hydroxyl groups. In a preferred embodiment of the invention, the further alcohol is chosen from the group consisting of glycerol, sorbitol, pentaerythritol and trimethylolpropane or alkoxylates thereof, polyethylene glycol, preferably with 2 to 200 ethylene oxide recurring units, polypropylene glycol, preferably with 2 to 200 ethylene oxide recurring units, or mixtures of at least two of these, glycerol, sorbitol or polyethylene glycol being preferred.  \n\n[0038] The invention also provides an ester product which is obtainable by a process according to the invention.  \n\n[0039] An ester product with atleast one, preferably each of the following properties is preferred according to the invention:  \n\n[0040]Pl a viscosity in a range of from 1.5 to 6,000, preferably from 5 to 4,oo0 and particularly preferably from 10 to $3,000\\mathrm{mPas}$ D   \n[0041] P2 a density of between 0.8 and 1.4, preferably from 0.85 to 1.35 and particularly preferably from 0.85 to $1.3\\:\\mathrm{g}/\\mathrm{cm}^{3}$ ，  \n\n[0042]  The invention also provides an anti-fogging agent which comprises an ester product according to the invention, preferably in an amount in a range of from 10 to 99.9 and preferably from 15 to 95 wt. $\\%$ , in each case based on the anti-fogging agent.An anti-fogging agent for use as an internal anti-fogging agent is particularly preferred.  \n\n[0043] An anti-fogging agent composition comprising at least one further anti-fogging agent is preferred according to the invention. This means that it comprises a further substance which improves the anti-fogging action of the agent and which is not an ester product according to the invention from the transesterification of a natural oil with a polyglycerol. In a preferred embodiment of the invention, the further anti-fogging agent is a polyethylene glycol ether, a partial glyceride or apolyethylene glycol ester or a mixture of at least two of these.A polyethylene glycol oleate, in particular polyethylene glycol sorbitan monooleate, is particularly preferred. The further anti-fogging agent or a mixture of further anti-fogging agents is preferably employed in a ratio of from 1:10 to 10:1 to the ester product according to the invention. Particularly preferably, the ratio is between 1:2 and 2:1.  \n\n[0044] The invention also provides a polymer composition comprising an ester product or anti-fogging agent according to the invention or both and at least one polymer. In principle, any polymer which can be melted is possible. This includes, in particular, linear polymers and branched polymers, which are in each case called, generally, thermoplastics. The polymers which the polymer composition comprises according to the invention can be obtained by any processes known to the person skilled in the art for the preparation of thermoplastics, such as polycondensation, poly-ring opening, polyaddition, metal-catalyzed, anionic, cationic and free radical polymerization. In a preferred embodiment of the invention, the polymer is chosen from the group consisting of polyvinyl chloride，polypropylene， polyethylene,polyethylene/ polypropylene copolymers, polyethylene terephthalate, polylactate, polycarbonate, copolymers or polyester and mixtures of at least two of these. Copolymers which can be used are also those which comprise as a monomer unit one of the sub-units described above and have been copolymerized with a monomer unit which is not mentioned here.  \n\n[0045] In a preferred embodiment of the invention, the polymer composition comprises 0.01 to $10\\mathrm{wt.\\%}$ ,preferably  \n\n0.05 to 7 wt. $\\%$ and particularly preferably 0.1 to 5 wt. $\\%$ ,in each case based on the polymer composition, of the ester product.  \n\n[0046] In a preferred embodiment of the invention, the polymer composition comprises 10 to 99.95, preferably 50 to 99 and particularly preferably 60 to 95 wt. $\\%$ , in each case based on the polymer composition, of the polymer or polymers.  \n\n[0047] In further embodiments of the invention, the polymer composition or the anti-fogging agent comprises further additives chosen from the group consisting of stabilizers, lubricants, plasticizers, antiblocking agents, further anti-fogging agents, antistatics, flameproofing agents, dyestuffs, pigments, blowing agents, fillers, fats, oils and solvents or a mixture of at least two of these.  \n\n[0048]Stabilizers keep plastics, such as PVC, from decomposing or changing chemically at high temperatures, and improve resistance to weathering. For example, compounds based on lead, calcium, zinc, barium and tin are employed.  \n\n[0049]   Lubricants serve to facilitate processing of PVC by reducing the friction between the PVC chains and reducing the adhesion of the PVC melt to the wall. Lubricants which are frequently used are metal soaps, such as lead and calcium stearates and laurates, which simultaneously act as a costabilizer.  \n\n[0050] Plasticizers impart suppleness and flexibility to the plastic. Many plasticizers belong to the group of phthalates (DEHP, DINP and DIDP), and of adipates and citrates.  \n\n[0051]  Antiblocking agents are additives which prevent or reduce the sticking (\"blocking\") of coated surfaces to one another or to substrates (e.g. during stacking or packing) Depending on the drying time in air, degree of drying, layer thickness, pressure or temperature under a certain loading, suitable release agents must be chosen, these as a rule being added to the coating substance and arriving at the surface during the drying phase. Paraffin, polyethylene wax, wax esters, silicone oils, stearates, modified silicas and talc, for example, are used for this.  \n\n[0052] Fillers, for example mineral fillers, such as chalk and talc, increase the strength and improve the insulating action.  \n\n[0053] Colored pigments, such as titanium oxide, which is also suitable for contact with foodstuffs, cosmetics and medicaments, serve as dyestuffs and pigments.  \n\n[0054] Water or organic solvents, such as alcohols, can be employed as solvents.  \n\n[0055] A polymer composition which comprises the following composition components is preferred according to the invention:  \n\n[0056]  at least 10, preferably at least 15 and particularly preferably at least 20 wt. $\\%$ of a polymer;   \n[0057] from 0.05 to 20, preferably 0.1 to 10 and particularly preferably 1 to 8 wt. $\\%$ of the ester product;   \n[0058]from O to 10, preferably 0.1 to 10 and particularly preferably 1 to 8 wt. $\\%$ of further anti-fogging agents;   \n[0059] from O to 75, preferably 5 to 70 and particularly preferably 10 to 65 wt. $\\%$ of   \n[0060] additives which differ from the above composition components;  \n\nwherein, in each case based on the polymer composition, the sum of all the percentages by weight is 100.  \n\n[0061] In a preferred embodiment of the invention, the polymer composition is a thermoplastic polymer composition. Thermoplastic polymer compositions are reversibly deformable from a certain temperature range. In further embodiments of the invention, the polymer composition is a non-crosslinked, crosslinkable polymer composition, for example for the preparation of elastomers.  \n\n[0062]   The invention also provides the use of an ester product according to the invention as an anti-fogging agent, preferably as an internal anti-fogging agent. Internal anti-fogging agents are incorporated into polymer compositions before these are processed to shaped articles.  \n\n[0063] The invention also provides a process for the production of a shaped article, wherein a polymer composition according to the invention is processed to the shaped article. A “shaped article\" in the context of the invention is a polymer composition which has been processed to a three-dimensional form. In this context, this can be a shaped article obtainable by thermal forming. Such shaped articles are obtained, for example, by processing thermoplastics by known processes.However, the shaped article can also be a crosslinked or vulcanized shaped article. Such shaped articles are obtained, for example, during processing of elastomers. The shaped article according to the invention has anti-fogging properties which are achieved due to the distribution of the anti-fogging agent in the shaped article and therefore also on the surface thereof.  \n\n[0064] The present invention also provides a shaped article comprising a polymer composition according to the invention or produced from a polymer composition according to the invention.  \n\n[0065] In a preferred embodiment of the invention, the shaped article is constructed in the form of a film, an outer facing, a transparent molding, a window, a visor or spectacle lens. Particularly preferably, the shaped articles serve as packaging materials, in particular in the form of films, outer facings and transparent moldings. Such packaging materials with anti-fogging properties are used for packaging of foodstuffs or other products with a moisture content. In such packaging materials, the anti-fogging properties alleviate or prevent fogging of the packaging materials from the inside. In further embodiments of the inventions, such as outer facings, windows, visors or spectacle lenses, the formation of drops and of accumulations ofmoisture on the outside and/or inside is prevented. The shaped articles according to the invention are particularly preferably transparent or at least transmit a proportion of light.  \n\n[0066] The thermoplastic polymer compositions according to the invention can be reacted generally by known processes to give the shaped articles according to the invention. In this context, the polymer formulations can first be worked up by known methods, for example by incorporation of additives or by conversion of the polymer composition into a suitable form, such as granules, powders, pastes or solutions. In this context, the polymer compositions are optionally mechanically treated, that is to say dispersed, kneaded or granulated. The processing to shaped articles is carried out, for example, by injection molding or extrusion. The moldings are optionally reworked, that is to say formed, cut, treated on the surface or welded. Curable polymer compositions are cured after pressing or forming to give moldings.  \n\n[0067]  The invention also provides a process for use for the production of a shaped article, comprising the process steps:  \n\n[0068] I) provision of the thermoplastic composition comprising an ester product according to the invention or an anti-fogging agent according to the invention or both;  \n\n[0069] II) heating of the thermoplastic composition to the glass transition temperature of the thermoplastic polymer or to a temperature above the glass transition temperature of the thermoplastic polymer;  \n\n[0070]  III) production of a shaped article from the heated thermoplastic composition prepared in process step II). [0071] In step I) of the process according to the invention for the production of a shaped article, a thermoplastic composition according to the invention is first provided, this provision preferably being carried out by a process according to the first variant of the process according to the invention.  \n\n[0072] In process step II), the thermoplastic composition is then heated to the glass transition temperature of the thermoplastic polymer or to a temperature above the glass transition temperature of the thermoplastic polymer. In this connection, it is in turn preferable for the heating of the thermoplastic composition to be carried out to a temperature in a range of from 5 degrees below the glass transition temperature $(\\mathrm{T}_{g})$ to $100^{\\circ}\\mathrm{C}$ . above the glass transition temperature of the thermoplastic polymer employed, particularly preferably to a temperature in a range of from 1 degree below the glass transition temperature $(\\mathrm{T}_{g})$ to $50^{\\circ}\\mathrm{C}.$ above the glass transition temperature of the thermoplastic polymer employed and most preferably to a temperature in a range of from 1 degree above the glass transition temperature $(\\mathrm{T}_{g})$ to $20^{\\circ}\\mathrm{~C~}$ . above the glass transition temperature of the thermoplastic polymer employed, here also, however, the upper limit of the temperature range being essentially limited by the decomposition temperature of the thermoplastic polymer employed.  \n\n[0073]  In principle, process steps I) and II) can be carried out simultaneously or in succession. It is appropriate to carry out process steps I) and II) simultaneously, for example, if the thermoplastic composition is prepared by means of a melt mixing process. Where appropriate, it may be advantageous here to convert the composition prepared by the melt mixing process directly into a shaped article. It is appropriate to carry out process steps I) and II) successively, for example, if the thermoplastic composition is prepared by means of a dry mixing process or if the thermoplastic composition is indeed prepared by means of a melt mixing process, but is not subjected to the formation of a shaped article directly after the preparation, but rather is first cooled according to process step V).  \n\n[0074]  In process step II) of the process according to the invention for the production of a shaped article, a shaped article is produced from the heated thermoplastic composition prepared in process step II). Possible processes for the production of a shaped article are, in particular, injection molding， extrusion molding， compression molding, layer molding, laminating molding, blow molding, vacuum molding and transfer molding, injection molding being particularly preferred.  \n\n[0075] In a preferred embodiment of the invention, in a further process step IV) at least a part region of the shaped article obtained in process step II) is reduced in its mass cross-section compared with process step III).  \n\n[0076] The invention also provides a process for the production of a packed product, comprising as process steps the provision of a product and a shaped article according to the invention and at least partial surrounding of the product with the shaped article.  \n\n[0077] Furthermore, in an embodiment of the process according to the invention for the production ofa thermoplastic shaped article, in at least one further process step IV) at least a part region ofthe shaped article obtained in process II) serves as a shaped article blank and is reduced in its mass cross-section by comparison. The mass cross-section is the cross-section of a region of the shaped article made solidly from the thermoplastic molding composition according to the invention. For example, in containers or vessels, the mass cross-section is the thickness of a wall of these containers or vessels. In the case of shaped articles which are rather threador strand-like in construction, the mass cross-section is the thickness of these threads or strands. In the case of rather planar structures, such as sheets, layers, webs, films or foils, the mass cross-section is the thickness of these planar structures.For the reduction in the mass cross-section, in principle all the methods known to the person skilled in the art and suitable for this are possible. These include, for example, stretching in one or two directions, drawing in one or two directions, centrifugation or blowing, each of which are preferably carried out at elevated temperatures at which the thermoplastic composition according to the invention is so soft or even liquid that stretching, drawing,centrifugation or blowing can be carried out. The part region in which the reduction in cross-section is effected preferably makes up at least $50\\%$ and particularly preferably at least $80\\%$ of the shaped article obtained in step II). Stretching or drawing are generally carried out if a fiber is to be obtained from the shaped article obtained in step II). For the production of films, on the one hand drawing or stretching in one or more dimensions can be carried out. Thus, the web running out of an extruder can be drawn on to a roll at a higher speed compared with the exit speed from the extruder. On the other hand, if a container or vessel is to be obtained, apart from stretching, drawing and centrifugation, blowing is chiefly carried out in step IV). In this, the reduction in mass cross-section is effected by applying a gas pressure. The gas pressure is generally chosen such that the thermoplastic composition, which is usually heated at least to the glass transition temperature, of the shaped article obtained in step III) can be extended. The extending is as a rule limited by using a mould having the final shape of the shaped article. It is furthermore possible for two or more of process steps I) to IV) to be supplemented by further process steps and/or to at least overlap in time. This applies in particular to process steps III) and IV).  \n\n[0078]  A contribution towards achieving at least one of the abovementioned objects is furthermore made by a process for the production of a packed product, comprising as process steps:  \n\n[0079]  a) provision of a product and a shaped article, in particular a film, the shaped article being obtainable by the process described above;  \n\n[0080]  b) at least partial surrounding of the product with the shaped article.  \n\n[0081]  The product provided in process step a) is preferably a pharmaceutical, a body care composition or a foodstuff. The at least partial surrounding of the product can be carried out, for example, by the process described in DE-A-103 56 769. [0082] The objects on which the invention is based are achieved by the ester product according to the invention, the process for its preparation and the use as an anti-fogging agent. The transesterification process renders possible the preparation of an effective and active anti-fogging agent directly from natural oils. Natural oils are available in large quantities and inexpensively as a raw material. It is therefore not necessary to use the comparatively expensive pure faty acids and mixtures thereof. In a process on a large industrial scale, such as the preparation of anti-fogging agents, this simplification means a significant saving in costs. Furthermore, it has been found, surprisingly, that in the preparation of anti-fogging agents directly starting from natural oils, very good anti-fogging properties are achieved. The plastics treated according to the invention show comparatively low clouding. In tests, the accumulation of drops on the film takes place only at a high humidity after relatively long times. The clearing of the films after the formation of drops takes place comparatively rapidly. The preparation process according to the invention and the properties of plastics treated according to the invention are explained in the following embodiment examples.",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# Test Methods:  \n\n[0083]  If not stated in detail in the following, the parameters described in this text are determined in accordance with the particular best suitable DIN specifications. Should no suitable DIN specification be available, the ISO specification which is most suitable is resorted to. Unless stated otherwise, all the properties are determined at $25^{\\circ}\\mathrm{C}$  \n\n[0084] The density is determined with a pyknometer, or 51550.  \n\n1. Color number  \n\n[0085] The color number is determined in accordance with ISO 15305 by the Lovibond method (Lov.)  \n\n2.Acid number  \n\n[0086] The acid number is determined in accordance with DIN ENISO 3682.  \n\n3. Saponification number  \n\n[0087]  The saponification number is determined in accordance with DIN EN ISO 3681.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 4. Hot fogging test  \n\n[0088]  The hot fogging test simulates the anti-fogging properties of films which are used for packagings which are filled with hot or warm foodstuffs which are then stored in the closed state.For this, a $250\\mathrm{ml}$ glass beaker is filled with 200 ml of distilled water, and the glass is covered with a sample of the film to be tested and positioned in a bath temperaturecontrolled at $60^{\\circ}\\mathrm{C}$ . The intervals of time in which a change in the film becomes visible are then recorded over a period of $600\\mathrm{s}$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 5. Cold fogging test  \n\n[0089]  This test simulates the anti-fogging properties of films which are used as packaging material for foodstuffs which are stored in the refrigerator. For this, a $250~\\mathrm{ml}$ glass beaker is filled with $200\\mathrm{ml}$ of distilled water, and the glass is covered with a sample of the film to be tested and placed in a temperature-regulatable chamber temperature-controlled at $8^{\\circ}\\mathrm{~C~}$ . The intervals of time in which a change in the film becomes visible are then recorded over a period of $600\\mathrm{{s}}$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 6.Density  \n\n[0090] The density is determined in accordance with DIN 51757V4.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 7. Viscosity  \n\n[0091]  The viscosity is determined in accordance with DIN 1342 P1, 2.  \n\n8.Surface tension   \n[0092] The surface tension is determined in accordance withDIN 53914.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# EMBODIMENTEXAMPLES  \n\nExample 1 菜籽油 Transesterification of Rape Oil with Polyglycerol- $3\\equiv$ 聚甘油 [0093] $255.6\\mathrm{g}$ of rape oil, $74.4\\mathrm{g}$ of Polyglycerol-3 (Solvay Chemicals） and $_{0.03\\mathrm{~g~}}$ of $\\mathrm{LiOH^{*}H}_{2}\\mathrm{O}$ were initially introduced into a glass flask and heated to $235^{\\circ}\\mathrm{C}.$ , while stirring. After $^\\textrm{\\scriptsize1h}$ ，a vacuum of 300 mbar was applied, and after a reaction time of 2 h the mixture was cooled. The product is a bright yellow liquid with the following properties:  \n\nColor1\"Lov.yellow $_{\\mathrm{\\Omega}}=1.6$ Lov. red=0.5, acid number $=0.10~\\mathrm{{mg}}$ of $\\mathrm{\\KOH/g}$ ,saponification number=146皂化值 mg of $\\operatorname{KOH}/\\operatorname{g},$ index $(20^{\\circ}\\mathrm{C}.){=}1.4772$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# Examples 2 and 3  \n\nProduction of the Test Specimens  \n\n[0094]  \n\n<html><body><table><tr><td></td><td colspan=\"2\">Example:</td></tr><tr><td></td><td>E2</td><td>E3</td></tr><tr><td>PVCEVIPOL SH 7020</td><td>100</td><td>100</td></tr><tr><td>DOAPLASTOMOL</td><td>37</td><td>37</td></tr><tr><td>EDENOL D 81</td><td>13</td><td>13</td></tr><tr><td>STABIOLVCZ2222</td><td>0.8</td><td>0.8</td></tr><tr><td>LOXIOL G10 V</td><td>1.6</td><td></td></tr><tr><td>DISPONIL SMO 120SPEZ.</td><td>0.8</td><td></td></tr><tr><td>LOXIOLP 1508</td><td>0.1</td><td>0.1</td></tr><tr><td>LOXIOL G 20</td><td>0.1</td><td>0.1</td></tr><tr><td>Product of Example 1</td><td>一</td><td>2.4</td></tr></table></body></html>  \n\n[0095] The components were mixed together and the mixture was rolled on a laboratory roll mill at $185^{\\circ}\\mathrm{C}$ .for $5\\mathrm{min}$ The rolled sheets were investigated by the“hot fogging test” at $60^{\\circ}\\mathrm{C}$  \n\nHot Fogging Test, $60^{\\circ}\\mathrm{C}.$ ·：  \n\n[0096]  \n\n[0097]   \n\n\n<html><body><table><tr><td>Sample</td><td>Clouding on the film after s</td><td>Formation of drops after s</td><td>Clear film after s</td></tr><tr><td>E2</td><td>immediate</td><td>60</td><td>300</td></tr><tr><td>E3</td><td>immediate</td><td>45</td><td>210</td></tr></table></body></html>\n\nE2 is prior art and E3 is according to the invention.  \n\nExamples 4 to 9  \n\n<html><body><table><tr><td>Example:</td><td>E4</td><td>E5</td><td>E6</td><td>E7</td><td>E8</td><td>E9</td></tr><tr><td>PVC EVIPOL SH 7020</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td></tr><tr><td>DOAPLASTOMOL</td><td>7</td><td>7</td><td>7</td><td>7</td><td>7</td><td>7</td></tr></table></body></html>  \n\n-continued   \n\n\n<html><body><table><tr><td>Example:</td><td>E4</td><td>E5</td><td>E6</td><td>E7</td><td>E8</td><td>E9</td></tr><tr><td>EDENOL D81</td><td>15</td><td>15</td><td>15</td><td>15</td><td>15</td><td>15</td></tr><tr><td>EDENOL 1215</td><td>15</td><td>15</td><td>15</td><td>15</td><td>15</td><td>15</td></tr><tr><td>STABIOLVCZ 2222</td><td>0.8</td><td>0.8</td><td>0.8</td><td>0.8</td><td>0.8</td><td>0.8</td></tr><tr><td>LOXIOL G 71S</td><td>0.2</td><td>0.2</td><td>0.2</td><td>0.2</td><td>0.2</td><td>0.2</td></tr><tr><td>LOXIOL G10V</td><td>1.5</td><td></td><td></td><td>1.6</td><td></td><td>一</td></tr><tr><td>DISPONIL SMO 120</td><td>1.5</td><td></td><td>1.2</td><td></td><td></td><td></td></tr><tr><td>SPEZ. DISPONIL SML 20</td><td></td><td></td><td></td><td>0.8</td><td></td><td>0.8</td></tr><tr><td>Product of Example 1</td><td></td><td>3.0</td><td>1.2</td><td></td><td>2.4</td><td>1.6</td></tr></table></body></html>  \n\n[0098] The components of Examples E4-E6 were mixed together and the mixture was rolled on a laboratory roll mill from Berstorff Maschinenfabrik at $185^{\\circ}\\mathrm{~C~}$ .for min. The rolled sheets were investigated by the“cold fogging test” at $25^{\\circ}\\mathrm{C}\\mathrm{/8^{\\circ}C}$  \n\n[0099]  \n\nCold Fogging Test, $25^{\\circ}\\mathrm{C}$ . Water Temperature $/8^{\\circ}\\mathrm{C}.$ Ambient Temperature   \n\n\n<html><body><table><tr><td>Sample</td><td>Clouding on the film after s</td><td>Formation of drops after s</td><td>Clear film after s</td></tr><tr><td>E4</td><td>immediate</td><td>>600</td><td>一</td></tr><tr><td>E5</td><td>immediate</td><td>60</td><td>360</td></tr><tr><td>E6</td><td>immediate</td><td><<60</td><td>60</td></tr></table></body></html>\n\nE4 is prior art and E5 and E6 are according to the invention.  \n\n-continued   \n\n\n<html><body><table><tr><td>Trade name</td><td>Manufacturer</td><td>Constituent/function</td></tr><tr><td>DOA PLASTOMOL</td><td>BASFES</td><td>plasticizer</td></tr><tr><td>EDENOL D 81</td><td>Cognis Oleochemicals epoxidized soya oil GmbH</td><td></td></tr><tr><td>STABIOLVCZ2222</td><td>Reagens GmbH</td><td>Ca/Zn stabilizer</td></tr><tr><td>LOXIOLG10V</td><td>Cognis Oleochemicals glycerol monooleate GmbH</td><td></td></tr><tr><td>DISPONIL SMO 120 SPEZ.</td><td>Cognis GmbH</td><td>PEG sorbitan monooleate</td></tr><tr><td>DISPONIL SML 20</td><td>Cognis GmbH</td><td>PEG sorbitan monolaurate</td></tr><tr><td>LOXIOLP 1508</td><td>Cognis Oleochemicals lubricant GmbH</td><td></td></tr><tr><td>LOXIOLG 20</td><td>Cognis Oleochemicals lubricant GmbH</td><td></td></tr><tr><td>Edenol 1215</td><td>GmbH</td><td>Cognis Oleochemicals polymer plasticizer</td></tr><tr><td>Loxiol G 71S</td><td>Cognis Oleochemicals release agent GmbH</td><td></td></tr></table></body></html>  \n\n[0100] The components of Examples E7-E9 were mixed together and the mixture was rolled on a laboratory roll mill from Berstorff Maschinenfabrik at $185^{\\circ}\\mathrm{~C~}$ .for $5~\\mathrm{min}$ .The rolled sheets were investigated by the“hot fogging test\" at $60^{\\circ}$ C.  \n\nHot Fogging Test, $60^{\\circ}\\mathrm{C}$ ·  \n\n[0101]   \n\n\n<html><body><table><tr><td>Sample</td><td>Clouding on the film after s</td><td>Clear film after s</td></tr><tr><td>E7</td><td>immediate</td><td>>300</td></tr><tr><td>E8</td><td>immediate</td><td>>360</td></tr><tr><td>E9</td><td>immediate</td><td>60</td></tr></table></body></html>\n\nE9 is according to the invention.  \n\nRaw Materials: [0102]   \nNote: Cognis Oleochemicals GmbH has recently changed its name to Emery Oleochemicals GmbH.   \n\n\n<html><body><table><tr><td>Trade name</td><td>Manufacturer</td><td>Constituent/function</td></tr><tr><td>PVC EVIPOL SH 7020</td><td>Ineos GmbH</td><td>PVC</td></tr></table></body></html>  \n\n1. An anti-fogging agent, comprising a) an ester product obtainable by a process comprising as process steps: S1) provision of a reaction mixture comprising as reaction components Sla) a polyglycerol comprising at least two glycerol units; S1b) an oil based on a natural oil; S2) reaction of the reaction mixture by a transesterification in the presence of a basic catalyst to give the ester product; b) at least one further anti-fogging agent chosen from the group consisting of a polyethylene glycol ether, a partial glyceride or a polyethylene glycol ester or a mixture of at least two of these. 2. The anti-fogging agent according to claim 1, wherein the transesterification is carried out as a one-pot process.  \n\n3. The anti-fogging agent according to claim 1 wherein the basic catalyst is chosen from the group consisting of alkali metal hydroxide, alkaline earth metal hydroxide or hydroxides of main group III or a mixture of at least two of these.  \n\n4. The anti-fogging agent according to claim 1 wherein the oil is chosen from the group consisting of rape oil, castor oil, hydrogenated castor oil, sunflower oil, palm oil, soya oil, tallow oil, hydrogenated tallow oil, coconut oil and groundnut oil or a mixture of at least two of these.  \n\n5. The anti-fogging agent according to claim 1 wherein the polyglycerol has an average number of from 1.5 to 5 glycerol units per molecule.  \n\n6. The anti-fogging agent according to claim 1 wherein the transesterification is carried out in the presence of at least one further alcohol.  \n\n7. The anti-fogging agent according to claim 6, wherein the further alcohol comprises at least two hydroxyl groups.  \n\n8. The anti-fogging agent according to claim 6 wherein the further alcohol is chosen from the group consisting of glycerol, sorbitol, pentaerythritol, trimethylolpropane or alkoxylates thereof, polyethylene glycol and polypropylene glycol.  \n\n9. The anti-fogging agent according to claim 1 wherein the process is carried out in a reaction mixture which contains the following reaction components:  \n\nat least about 10 wt. $\\%$ of oil, from about 5 to about 90 wt $\\%$ of polyglycerol, from about 0.0001 to about 1 wt $\\%$ of basic catalyst,  \n\nfrom O to about 40 wt. $\\%$ of a further alcohol with at least two hydroxyl groups, from O to about 20 wt. $\\%$ of additives which differ from the above reaction components, in each case based on the reaction mixture, wherein the sum of the percentages of the reaction components is 100. 10. The anti-fogging agent according to claim 1 with at least one of the following properties: Pl a viscosity in a range offrom about 1.5 to about 15 mPas P2 a density in a range of from about 0.8 to about 0.95 $\\mathrm{{g}}/\\mathrm{{cm}}^{3}$ . 11.A polymer composition comprising an ester product, an anti-fogging agent of claim 1 and at least one polymer. 12. The polymer composition according to claim 11, wherein the polymer is chosen from the group consisting of polyvinyl chloride, polypropylene, polyethylene, polyethylene/polypropylene copolymers, polyethylene terephthalate, polylactate, polycarbonate, polyesters and mixtures of these. 13. The polymer composition according to claim 11 comprising from about 0.05 to about 10 wt. $\\%$ of the ester product. 14.The polymer composition according to claim 11, which comprises the following components: at least about $10\\mathrm{wt}$ $\\%$ of a polymer, from about 0.05 to about $20\\mathrm{wt}\\%$ of the ester product, from O to about $10\\mathrm{wt}\\%$ of further anti-fogging agent, from O to about $75\\mathrm{wt\\\\%}$ of additives. 15. The polymer composition according to claim 11, wherein the composition is a thermoplastic polymer composition.  \n\n16.A process for the production of a shaped article,   \nwherein a polymer composition according to claim 11 is   \nprocessed to give the shaped article. 17.A shaped article comprising a polymer composition   \naccording to claim 11. 18.The shaped article according to claim 17 in the form of   \na film, an outer facing, a transparent moulding, a window, a   \nvisor or spectacle lens. 19.A process for the production of a thermoplastic shaped   \narticle, comprising the process steps: I) provision of the anti-fogging agent according to claim 1; I) heating of the thermoplastic composition to the glass transition temperature of the thermoplastic polymer or to a temperature above the glass transition temperature of the thermoplastic polymer; and II) production of a shaped article from the heated thermoplastic composition prepared in process step II). 20.The process according to claim 19, wherein in a further   \nprocess step IV) at least a part region of the shaped article   \nobtained in process step II) is reduced in its mass cross  \nsection compared with process step III). 21.A process for the production of a packed product,   \ncomprising as process steps: a) provision of a product and of a shaped article according to claim 17 or of a mixture of at least two of these as a pack shaped article; b) at least partial surrounding of the product with the pack shaped article.",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# (2) United States Patent Yahiaoui et al.",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (54） ANTI-FOG, ANTI-GLARE FACEMASKS  \n\n(71） Applicant: O&M Halyard, Inc., Mechanicsville,VA (US)  \n\n(72） Inventors: Ali Yahiaoui, Roswell GA (US); Anthony Stephen Spencer, Woodstock, GA (US)  \n\n(73） Assignee: O&M Haylard, Inc., Mechanicsville,VA (US)  \n\n（\\*） Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 525 days.  \n\n(21) Appl. No.: 15/524,404   \n(22) PCT Filed: Nov. 13, 2014   \n(86) PCT No.: PCT/US2014/065410 $\\S\\ S71$ (c)(1), (2) Date: May 4, 2017   \n(87) PCT Pub.No.: WO2016/076869 PCT Pub. Date: May 19, 2016",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# Prior Publication Data  \n\nUS 2017/0318877A1 Nov. 9,2017 (51) Int. Cl. G02B 26/00 (2006.01) G02B26/02 (2006.01) A41D13/11 (2006.01) C09D 1/00 (2006.01) G02B 27/00 (2006.01) G02B1/18 (2015.01) C09D 101/02 (2006.01) G02B 1/11 (2015.01)  \n\n(52) U.S. Cl. CPC A41D13/1184 (2013.01); A41D 13/11 (2013.01); C09D 1/00 (2013.01); C09D  \n\n(10) Patent No.: US 10.827,788 B2   \n(45) Date of Patent: Nov. 10, 2020   \n101/02 (2013.01); G02B 1/11 (2013.01); G02B   \n1/18 (2015.01); G02B 27/0006 (2013.01)  \n\n(58) Field of Classification Search CPC. G02B 1/18; G02B 1/105; G02B 1/11; G02B 1/111; G02B 27/0006 USPC 359/290-292,295,296,298 See application file for complete search history.",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# References Cited",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# U.S.PATENTDOCUMENTS  \n\n3,888,246 A 6/1975 Lauer   \n3,890,966 A 6/1975 Aspelin et al.   \n4,419,993A 12/1983 Petersen   \n4,635,628 A 1/1987 Hubbard et al.   \n5,585,186 A 12/1996 Scholz et al.   \n5,723,175 A 3/1998 Scholz et al.   \n(Continued)",
+        "category": " References"
+    },
+    {
+        "id": 6,
+        "chunk": "# FOREIGNPATENTDOCUMENTS  \n\nWO WO 2013/127054 A1 9/2013  \n\nOTHERPUBLICATIONS  \n\nInternational Search Report for PCT/US2014/065410, dated Jul.14, 2015,7 pages.  \n\nPrimary Examiner—Brandi N Thomas (74) Attorney, Agent, or Firm —DOority & Manning, P.A.",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# ABSTRACT  \n\nA coating composition that is incorporated into a facemask to reduce fogging and glare is provided. For example, in one embodiment, the facemask contains a shield or visor formed from a transparent substrate having at least one surface applied with the coating composition of the present disclosure. The coating composition contains a large amount of nanoparticles, desirably greater than 10 wt $\\%$ ·",
+        "category": " Abstract"
+    },
+    {
+        "id": 8,
+        "chunk": "# 10 Claims, 1 Drawing Sheet  \n\n![](images/0587972f32d85520179388f3ebb9b4ec0b81c4d7f3724b1292b5608a56bcee13.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# References Cited",
+        "category": " References"
+    },
+    {
+        "id": 10,
+        "chunk": "# U.S.PATENTDOCUMENTS  \n\n5,753,373A 5/1998 Scholz et al. 5,804,612 A 9/1998 Song et al. 5,813,398 A 9/1998 Baird et al. 5,873.,931A 2/1999 Scholz et al. 5,997,621 A 12/1999 Scholz et al. 6,040,053A 3/2000 Scholz et al. 6,217,176 B1 4/2001 Maekawa 6,455,142 B1 9/2002 Heberger et al. 6,945,656B2 9/2005 Takahashi et al. 7,703,456 B2 \\* 4/2010 Yahiaoui A41D13/1184 128/206.19   \n2007/0142595 A1\\* 6/2007 Hashiba C08F 212/08 526/348   \n2013/0065039 A1\\* 3/2013 Tada et al. C08K3/04 428/220  \n\n\\* cited by examiner  \n\n![](images/0ee652f0044aee4431d226e506d29a946ba0d8925d124b2520ce0ae01a1cd337.jpg)",
+        "category": " References"
+    },
+    {
+        "id": 11,
+        "chunk": "# US 10,827,788 B2",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# 1 ANTI-FOG, ANTI-GLAREFACEMASKS  \n\nRELATEDAPPLICATIONS  \n\nThis application is a national phase of and claims priority : to PCT/US2014/065410, filed Nov. 13, 2014,the contents of which are incorporated herein by reference.",
+        "category": " References"
+    },
+    {
+        "id": 13,
+        "chunk": "# BACKGROUND  \n\nThe use of protective facemasks has become standard for many health care and other related activities. The primary objective of the facemasks is to filter harmful materials from the inhaled and exhaled air. However, medical facemasks may also be used to protect the wearer from liquid insults. As such, these masks may include an attached clear plastic visor to protect the eyes from liquid splashes. Alternatively, a stand-alone clear face shield may also be worn in conjunction with the filtering mask.  \n\nOne continuing problem attendant with the use of face 20 shields or protective facemasks with attached visors in both medical and industrial applications is fogging of the visor or shield. The warm, moist air exhaled by the wearer will condense on relatively cool surfaces that are in close proximity to the nose or mouth of the user. Condensate droplets 25 will fog or cloud eye glasses, face masks and other protective shields, along with oculars for scientific equipment, such as endoscopes and microscopes. This fogging or clouding results when a high concentration of moisture vapor contained within the protective mask passes through or 30 around the facemask and condenses on a cooler eyeglass in the proximity of the mask. Various techniques have been proposed to solve the problem of fogging, such as described in U.S. Pat. Nos. 4,635,628; 4,419,993; 3,890,966; and 3,888,246.  \n\nNevertheless, many of these solutions fail to solve the problem of glare. Glare is an undesirable specular reflection of light from a surface upon which the light is incident. For instance, personnel working in clean rooms and medical personnel performing lengthy, complex surgical procedures often report eye strain and eye fatigue from such reflections and glare after wearing a facemask for extended periods of time. Eye fatigue from glare is particularly noticeable when using precision scientific equipment, such as microscopes and endoscopes, while wearing a facemask or other protective equipment to protect and/or shield the wearer's face. Many commercial transparent films (e.g., polyester) used to form transparent visors or shields are coated with a thin finish; however, the impact of the finish on optical properties is negligible.  \n\nVarious techniques have thus been suggested to reduce both fogging and glare in facemasks. For example, U.S. Pat. No. 5,813,398 to Baird, et al. describes a facemask having a filter body with a layer of fluid impervious film disposed over an upper portion of the facemask to block air exhaled by the wearer through the filter body from fogging eyeglasses and/or an eye piece.A layer of non-woven material is preferably placed over the fluid impervious film layer to substantially reduce and/or eliminate any glare from the fluid impervious film layer. In addition, U.S. Pat. No. 5,585,186 to Scholz,et al.; U.S. Pat. No. 5,723,175 to Scholz, et al.; U.S. Pat. No. 5,753,373 to Scholz.et al.; U.S. Pat. No. 5,873,931 to Scholz, et al.; U.S. Pat. No. 5,997,621 to Scholz, et al.; and U.S. Pat. No. 6,040,053 to Scholz, et al. generally describe coating compositions that rely on a solid particles of porous inorganic metal oxide network to impart anti-reflection properties, and very specific surfactants to impart anti-fogging properties. Unfortunately, such techniques for reducing fogging and glare in facemasks still have limitations. For example, the use of one coating ingredient for anti-reflection (e.g., porous inorganic metal oxides) and another for anti-fogging (e.g., surfactants) is overly complex and expensive. Other issues with surfactant/ solid particle dispersions relate to formulation instability over time, which can negatively affect optical properties of the product. U.S. Pat. No. 7,703,456 to Yahiaoui et al. generally describes a coating composition for a facemask that is about 50 to 250 nanometers thick and that consists essentially of particular organic polymers with a water soluble cellulosic ether derivative making up at least $90\\%$ of the organic polymer. U.S. Pat. No. 7,703,456 teaches that nanoparticles may be present in the composition at a concentration of less than $10\\mathrm{\\wt\\\\%}$  \n\nCurrently, there is a need for an improved technique for simultaneously eliminating the deleterious effects of fogging and reducing glare on facemasks.",
+        "category": " Introduction"
+    },
+    {
+        "id": 14,
+        "chunk": "# SUMMARY  \n\nIn accordance with one embodiment of the present disclosure, a facemask is disclosed that comprises a substrate, such as a transparent polyester visor or shield. A coating is present on at least one surface of the substrate that consists essentially of greater than 10 wt $\\%$ nanoparticles.  \n\nOther features and aspects of the present disclosure are discussed in greater detail below.",
+        "category": " Abstract"
+    },
+    {
+        "id": 15,
+        "chunk": "# BRIEFDESCRIPTIONOFTHEDRAWINGS  \n\nFIG.1 is a schematic illustration of a facemask that may be formed in accordance with one embodiment of the 5 present disclosure.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# DETAILEDDESCRIPTION  \n\nReference now will be made in detail to various embodi  \n40 ments of the disclosure, one or more examples of which are set forth below. Each example is provided by way of explanation of the disclosure, not limitation. In fact, it will be apparent to those skilled in the art that various modifications and variations may be made in the present disclosure   \n45 without departing from the scope or spirit of the disclosure. For instance, features illustrated or described as part of one embodiment, may be used on another embodiment to yield a still further embodiment. Thus, it is intended that the present disclosure covers such modifications and variations   \n50 as come within the scope of the appended claims and their equivalents.  \n\nIn general, the present disclosure is directed to a facemask that contains the dried residue of an aqueously applied coating composition for reducing fogging and glare. For example, in one embodiment, the facemask contains a shield or visor 30 that is utilized in conjunction with a filter body. Alternatively, the facemask may be a stand-alone shield or visor 30.Regardless, the shield or visor may be formed from a transparent substrate, desirably polyester, having at least one surface applied with the coating composition of the present disclosure.  \n\nThe transparent substrate to which the coating composition of the present disclosure is applied may be formed from a variety of different materials.Examples of such materials include, but are not limited to, polyesters, such as polyethylene terephthalate or polybutylene terephthalate; polycarbonates; allyldiglycolcarbonates; polyacrylates, such as",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 17,
+        "chunk": "# 3  \n\npolymethylmethacrylate;polystyrenes；polysulfones; polyethersulfone; cellulose acetate butyrate; glass; combinations thereof; and so forth. In one particular embodiment, the transparent substrate is formed from polyester (PET). The transparent substrate may be in the form of a film, sheet, panel or pane of material, and may be formed by any well-known process, such as blowing, casting, extrusion, injection molding, and so forth. It is desirable that, prior to applying the aqueous coating composition or formulation, the PET film is first oxidized via corona or plasma glow discharge at a watt density of 2 to 10 watt/((ft²/min)/side). The glow discharge enables PET to be more receptive to subsequent coating with the aqueous formulation and also allows for good uniformity throughout the PET film.  \n\nTypical PET film reflects back incident light by about   \n$8\\mathrm{-}11\\%$ and is sufficient to cause eye strain/fatigue. To   \nminimize glare, two conditions must simultaneously be met: Refractive Index: must follow a root square relationship with respect to the refractive index of PET filmFormulations containing particles, surfactant and a binder have been developed that meet this requirement. Coating thickness: A thickness of about $140~\\mathrm{nm}$ or $\\%$ the wavelength of the green color centered at $550~\\mathrm{nm}$ is desired to eliminate the green color from reflected light via destructive interference, yielding a light purple hue on the PET visor. The human eye is most sensitive to the green color and eliminating the green from the reflected visible light will cause less eye fatigue/strain and thus should be preferred by physicians and hospital workers. However, the coating thickness can be lower than $140\\mathrm{nm}$ if a specific hue is preferred. For example, a thickness between 85 and $110~\\mathrm{{nm}}$ will yield a more pronounced darker blue/darker hue. The more desired thickness is in the 90 to $105~\\mathrm{{nm}}$ range.  \n\nPET is relatively hydrophobic and water droplets sus- 3: pended in air during exhalation will bead up on PET and will therefore scatter visible light causing the PET film to fog up and hinder vision. Providing anti-fog properties requires a hydrophilic coating that can prevent water droplets from beading up, desirably resulting in a droplet contact angle of 4( less than 20 degrees on the PET. Fogging was evaluated by directly breathing onto the film held approximately one inch $(2.5~\\mathrm{cm})$ from the mouth. Fogging was determined subjectively to be excellent if no fogging was observed. All examples (except the control） had excellent (instant) fog 4: dissipation. The control sample fogged persistently.  \n\nThe coating composition of the present disclosure includes one or more water-soluble organic polymers. The water-soluble organic polymer may be utilized as the principal component of the coating composition to simultaneously reduce both fogging and glare. To minimize glare, the water-soluble organic polymer may be selected to have a nominal refractive index approximately equal to the square root of the refractive index of the transparent substrate.In some embodiments of this disclosure, the water-soluble organic polymer of the coating may have an average index of refraction of 1.0 to 1.7, in some embodiments from 1.2 to 1.5.  \n\nAny of a variety of water-soluble organic polymers capable of achieving the desired characteristics of transparency, reduced fogging, and reduced glare may be utilized in the present disclosure. One exemplary water-soluble organic polymer is Bermocoll $\\mathrm{E}230\\mathrm{FQ}$ ，which is ethyl hydroxyethyl cellulose commercially available from Akzo Nobel of Stamford, Conn. It is desirable that the cellulose be present in the aqueous composition in an amount of between O.1 and 0.5 weight percent (wt $\\%$ ),more desirably about $0.2\\mathrm{\\wt\\\\%}$  \n\nAlso present in the composition is a nanoparticle, desirably Nalco 2326 particles, which are colloidal silica particles commercially available from Nalco Co. of Naperville, Ill. The nanoparticles should be present in an amount between 5 and $20\\mathrm{wt\\\\%}$ ，more desirably about 15 wt $\\%$ .Nalco 2326 is available as a silica sol with mean particle size of 5 nanometers, $\\mathsf{p H}10.5$ ，and solid content $15\\%$ by weight.  \n\nAnother ingredient of the composition is a surfactant that decreases surface tension of water at low concentrations thus I allowing a more uniform coating of actives on the PET film. One example of such a low molecular weight silicone glycol surfactant is Masil $\\textsuperscript{\\textregistered}$ SF-19, available from Emerald Performance Materials of Cheyenne, Wyo. The surfactant is desirably present in the composition at a concentration of between about 0.05 and $0.15\\mathrm{wt}\\%$ ，more desirably about 0.1 wt $\\%$ . Another example is Surfactant 10G, $50\\%$ ,a glycidol ether, and is available from Arch Chemicals, Inc., Norwalk, Conn. Other surfactants that may be used may be an alkyl polyglycoside such as Standapol 215UP made by BASF, or Stantex $\\textsuperscript{\\textregistered}$ H 215UP from Pulcra Chemical and Lutensol $\\textsuperscript{\\textregistered}$ A65N, also from BASF. A small amount of alcohol (e.g. Isopropyl alcohol or methanol available from Sigma Aldrich) can also be used to help wet out the PET film.  \n\nThe coating composition is formed as an aqueous solution. This solution may contain, for instance, at least about 75 wt $\\%$ water, preferably de-ionized (DI) water, in some embodiments at least about 90 wt $\\%$ water, and in some embodiments, at least about 96 wt $\\%$ water.  \n\nThe aqueous solution may be applied to the transparent substrate using any conventional technique, such as bar, roll, knife, curtain, print (e.g., rotogravure), spray, slot-die, or dip-coating techniques. When applying the coating composition to multiple surfaces, each surface may be coated sequentially or simultaneously.  \n\nAs discussed above, the PET film may be oxidized prior to coating using corona discharge, ozone, plasma, or flame treatment methods. This helps to ensure uniform coating and wetting of the transparent substrate. In some embodiments, the transparent substrate may also be applied with a pretreatment to facilitate uniform application of the coating composition thereto. For instance, in one embodiment, a primer is applied to the transparent substrate, such as polyvinylidene chloride (PVDC) or polyvinyl chloride (PVC). Typically, the primer does not have a substantial effect on the optical properties of the transparent substrate.  \n\nThe average thickness of the resulting coating may be selected to minimize glare. Specifically, it is known that a single-layer optical coating having a thickness equal to $\\%$ the wavelength of incident light will result in reflections ） from the air-coating boundary and coating-substrate boundary that are 180 degrees out of phase with each other, thereby causing destructive interference and reducing total reflectance. Thus, because the wavelength of visible incident light ranges from approximately 200 to 10o0 nanometers, 5 the average thickness of the coating of the present disclosure typically ranges from about 50 to 250 nanometers. In addition, because 550 nanometers is the center of the wavelength range at which the human eye displays a peak photo-optic response, the coating thickness is desirably ）between about 90 and about 140 nanometers. It should be understood, however, that the coating of the present disclosure is not limited to a single layer, but may also contain multiple layers. For example, it is readily understood by those skilled in the art that two layers may be utilized, with 5 each layer being optimized in refractive index and thickness to minimize reflection of different wavelengths of light, thus further enhancing the anti-glare properties over a wider spectrum of light. In addition, while the average coating thickness is desirably uniform, the actual coating thickness may vary considerably from one particular point on the coating to another. Such variations in thickness, when correlated over a visibly distinct region, may actually be beneficial by contributing to the broadband anti-reflective properties of the coating.  \n\nThe coating composition of the present disclosure may be applied to one or both surfaces of the transparent of the substrate. When used in a facemask, the coating is generally present on at least the surface of the transparent substrate that faces the wearer. In addition, the coating may cover an entire surface of the transparent substrate, or may only cover a portion of the surface, such as a portion immediately adjacent to the eyes in a face shield. The coated substrate may be dried to remove water from the coating. For example, the coated substrate may be dried in an oven at a temperature of from about 20 degree C.to about 150 degrees C.,in some embodiments from about 50 degrees C.to about 120 degrees C., and in some embodiments, from about 100 degrees C. to about 110 degrees C. Once dried, the watersoluble organic polymers may constitute at least about 50 wt $\\%$ , in some embodiments at least about $75\\mathrm{wt}\\%$ and in some embodiments, at least about $90\\uppi\\%$ of the coating.  \n\nAs stated, the coating composition reduces fogging and glare when applied to a transparent substrate in the manner set forth. The anti-fogging property is exhibited by the tendency of the coating to resist the formation of water droplets that would otherwise significantly reduce transparency. Water vapor from, for example, human breathing, tends to condense on the coated substrate in the form of a thin uniform water film, rather than as water droplets. Such a uniform film does not significantly reduce the clarity or transparency of the substrate. Likewise, the reduction in glare is discernible through the light transmission and haze of the coated substrate. Light transmission through a coated substrate depends on the angle of incidence and the wavelength of light, and is determined using ASTM D1003 entitled “Haze and Luminous Transmittance of Transparent Plastics\". An increase in light transmission reveals a corresponding reduction in glare. In most embodiments of the present disclosure, the coated substrate exhibits an increase in transmission of normal incident light of greater than about $10\\%$ when compared to an uncoated substrate, at a wavelength of 550 nanometers.  \n\nIn addition, haze is a measurement of the wide angle scattering of light within a material.Haze may be measured with a BYK Gardner “Haze Gard Plus” instrument (BYKGardner USA, Columbia, Md.) using ASTM D 1003-61, procedure A, entitled “Haze and Luminous Transmittance of Transparent Plastics\", which is incorporated herein by reference in its entirety for all purposes. Haze is defined as the percentage of transmitted light, which in passing through the specimen, deviates from the incident beam by more than an average of 25 degrees. Haze is commonly referred to as the \"milkiness\" of a specimen, or its loss in contrast.A negative value for the difference in haze, expressed as the difference in the percentage of haze for the coated substrate and an uncoated substrate, signifies a reduction in haze. In most embodiments of the present disclosure, the difference in iaze is less than $0\\%$ , in some embodiments from about $-1\\%$ o about $-0.001\\%$ ,and in some embodiments, from abot $-0.5\\%$ to about $-0.01\\%$  \n\nAs stated, the coated transparent substrate of the present   \n5 disclosure is particularly useful in facemasks. One embodiment of such a facemask 20 is shown that includes a visor 30 attached to a filter body 32. The filter body 32 has a top edge 24 and a bottom edge 44, an exterior surface 46, and may have multiple pleats 34. The visor 30 is designed to   \n10 protect the eyes and other portions of the face of a wearer 22 from liquid spray or splash.A pair of ear loops 36 (only one of which is shown in FIG. 1) is also attached to respective opposite side edges 40 of the filter body 32 for use in securing the facemask 20 over the nose and mouth of the   \n15 wearer 22. If desired, surgical ties or headbands may also replace the ear loops 36.  \n\nIn one embodiment, the visor 30 is formed from a transparent substrate, such as described above, and is dimensioned to fit across the width of the filter body 32 and extend ）over the eyes of the wearer 22.The thickness of the visor 30 may vary so that it is stiff enough to prevent collapse, yet flexible enough to bend. In some embodiments, the thickness of the visor 30 is from about 0.001 to about 1 millimeter, in some embodiments from about 0.01 to about 0.5 i millimeters, and in some embodiments, from about 0.1 to about 0.2 millimeters.  \n\nThe present disclosure may be better understood with reference to the following examples.  \n\nTest Methods: The following test methods are utilized in the Examples.  \n\nCoating Thickness: The coating thickness was measured with using spectroscopic elipsometry or reflectometry analytical techniques. For Ellipsometry we utilized a RC2 DI model to measures the coating thickness and refractive index.Additionally,we also utilized a F2-RT instrument from Filmetrics. The F2-RT also measures coating thickness and refractive index, but can also measure other critical optical properties such a spectral transmittance, spectral reflectance and reflectance color.  \n\nHaze: Haze is a measurement of the wide angle scattering of light within a material. Haze was measured with a BYK Gardner “Haze Gard Plus” instrument (BYK-Gardner USA, Columbia, Md.) using ASTM D 1003-61, procedure A, entitled “Haze and Luminous Transmittance of Transparent Plastics.”",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# Table 1, Examples  \n\nThe ability to inhibit haze yet allow light transmittance   \ni0 with a coating composition of the present disclosure was demonstrated. Coating compositions were formed from water-soluble organic polymer Bermocoll E 23oFQ,which is ethyl hydroxyethyl cellulose commercially available from Akzo Nobel of Stamford, Conn. Nalco 2326 colloidal silica   \ni5 particles were also used as well as various surfactants as shown in Table 1. The balance was de-ionized water. The coating was applied to both sides of the film using a rotogravure process.  \n\nThe active percentage of the ingredients within each coating composition is set forth below in Table 1. Example 1 was a control without any coating.  \n\nTABLE1   \n\n\n<html><body><table><tr><td colspan=\"9\">Coating composition and optical properties of coated PET film</td></tr><tr><td></td><td colspan=\"6\">Composition (wt %)</td><td colspan=\"2\">Performance</td></tr><tr><td>Example</td><td>HO</td><td>Standapol 215UP</td><td>Lutensol A65 N</td><td>Stantex H 215 UP</td><td>Nalco 2326</td><td>Bermocoll E230FQ</td><td>% Light Transmission</td><td>% Haze</td></tr><tr><td>1 (Control PET Film)</td><td>0.00</td><td>0.00</td><td>0.00</td><td>0.00</td><td>0.00</td><td>0.00</td><td>90.00</td><td>0.50</td></tr><tr><td></td><td>85.24</td><td>0.85</td><td>0.00</td><td>0.00</td><td>24.85</td><td>0.06</td><td>97.50</td><td>0.43</td></tr><tr><td>2 3</td><td>85.24</td><td>0.85</td><td>0.00</td><td>0.00</td><td>23.85</td><td>0.06</td><td>97.40</td><td>0.51</td></tr><tr><td>4</td><td>84.69</td><td>0.00</td><td>0.10</td><td>0.00</td><td>15.01</td><td>0.20</td><td>98.50</td><td>0.50</td></tr><tr><td>5</td><td>85.39</td><td>0.00</td><td>0.00</td><td>0.64</td><td>13.88</td><td>0.10</td><td>96.80</td><td>0.50</td></tr></table></body></html>\n\nNote: Both sides of PET film were coated.  \n\nAs can be seen in Table 1, the compositions had very high amounts of nanoparticles and yet also had very high light transmittance values. The haze of each example (except barely by example 2) resulted in a delta haze (haze of coated substrate minus haze of the untreated control) that was less than zero.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# Table 2, Examples  \n\nTable 2 has additional examples at differing nanoparticle concentrations and using different surfactants as indicated in the Table. The balance was de-ionized water. The coating was applied to both sides of the film using a slot coating process to determine if the application process affected the light transmittance and haze.  \n\npolyester film was performed by either the rotogravure process or by slot coating, as indicated. Conditions for both rotogravure and slot die processes along with bath concen  \n20 tration and line speed can be tailored to deliver the desired coating thickness.A coating thickness was targeted so that the dried coated film yielded a blue/purple hue. Drying was carried out in a hot air convection oven at about 110 degrees C.for typically about 1 minute or until constant weight. The   \n25 coating solution is degassed to remove air bubbles in order to eliminate potential defects on the coated film. Coatings were applied sequentially, i.e., one side at a time, but a 1-step simultaneous dual side coating is also possible  \n\nAs indicated above, the coating composition of the present disclosure achieved improved light transmittance and reduced haze when applied to clear polyester film for use as  \n\nTABLE 2   \n\n\n<html><body><table><tr><td></td><td colspan=\"10\">Coating Composition and Optical properties of coated PET Film</td></tr><tr><td></td><td colspan=\"6\">Composition (Wt %)</td><td colspan=\"6\">Coating</td></tr><tr><td>Example</td><td>Bermocol E230FQ</td><td>10G</td><td>Surfactant MASIL</td><td>Nalco</td><td>Isopropyl alcohol</td><td>DI Water</td><td>Thickness</td><td colspan=\"2\">%LT AVG</td><td colspan=\"2\">%Haze1 AVG</td></tr><tr><td>1</td><td></td><td></td><td>SF-19</td><td>2326</td><td></td><td></td><td>(nm)</td><td></td><td>STD</td><td></td><td>STD</td></tr><tr><td>2</td><td>0.04%</td><td>0.1%</td><td>0.0%</td><td>7.1%</td><td>0</td><td>92.7%</td><td>103</td><td>99.17</td><td>0.12</td><td>0.44</td><td>0.01</td></tr><tr><td></td><td>0.04%</td><td>0.1%</td><td>0.0%</td><td>7.1%</td><td>0</td><td>92.7%</td><td>103</td><td>99.57</td><td>0.06</td><td>0.21</td><td>0.01</td></tr><tr><td>3 4</td><td>0.04%</td><td>0.1%</td><td>0.0%</td><td>7.1%</td><td></td><td>92.7%</td><td>98</td><td>99.63</td><td>0.06</td><td>0.22</td><td>0.02</td></tr><tr><td></td><td>0.04%</td><td>0.1%</td><td>0.0%</td><td>7.1%</td><td>0</td><td>92.7%</td><td>98</td><td>99.70</td><td>0.00</td><td>0.23</td><td>0.02</td></tr><tr><td>5</td><td>0.04%</td><td>0.1%</td><td>0.0%</td><td>7.1%</td><td>0</td><td>92.7%</td><td>98</td><td>98.77</td><td>0.06</td><td>0.46</td><td>0.01</td></tr><tr><td>6</td><td>0.04%</td><td>0.1%</td><td>0.0%</td><td>7.1%</td><td>0</td><td>92.7%</td><td>103</td><td>98.77</td><td>0.06</td><td>0.49</td><td>0.02</td></tr><tr><td>7</td><td>0.04%</td><td>0.1%</td><td>0.0%</td><td>7.1%</td><td>0</td><td>92.7%</td><td>103</td><td>98.53</td><td>0.06</td><td>0.51</td><td>0.03</td></tr><tr><td>8</td><td>0.04%</td><td>0.1%</td><td>0.0%</td><td>7.1%</td><td>0</td><td>92.7%</td><td>103</td><td>98.53</td><td>0.06</td><td>0.60</td><td>0.01</td></tr><tr><td>9</td><td>0.04%</td><td>0.1%</td><td>0.0%</td><td>7.1%</td><td>0</td><td>92.7%</td><td>103</td><td>98.67</td><td>0.06</td><td>0.53</td><td>0.01</td></tr><tr><td>10</td><td>0.04%</td><td>0.1%</td><td>0.0%</td><td>7.1%</td><td>0</td><td>92.7%</td><td>103</td><td>98.80</td><td>0.10</td><td>0.55</td><td>0.00</td></tr><tr><td>11</td><td>0.04%</td><td>0.1%</td><td>0.0%</td><td>7.1%</td><td>0</td><td>92.7%</td><td>103</td><td>98.90</td><td>0.10</td><td>0.54</td><td>0.01</td></tr><tr><td>12</td><td>0.044%</td><td>0.10%</td><td>0.0%</td><td>7.11%</td><td>0</td><td>92.7%</td><td>103</td><td>98.80</td><td>0.00</td><td>0.57</td><td>0.01</td></tr><tr><td>13</td><td>0.3%</td><td>0.0%</td><td>0.4%</td><td>23.2%</td><td>3.1%</td><td>73.0%</td><td>320</td><td>97.18</td><td>0.08</td><td>0.80</td><td>0.03</td></tr><tr><td>14</td><td>0.3%</td><td>0.0%</td><td>0.4%</td><td>23.2%</td><td>3.1%</td><td>73.0%</td><td>100</td><td>99.30</td><td>0.10</td><td>0.90</td><td>0.06</td></tr></table></body></html>\n\nlOptical properties measured via HazeGard Plus $\\circledast$ ASTM D1003-61  \n\nAs can be seen in Table 2, the compositions had very high amounts of nanoparticles and yet also had very high light transmittance values. The haze of most examples resulted in a delta haze (haze of control minus haze of the example) that was less than zero.  \n\nThe coating compositions of the Examples were applied to a clear polyester film obtained from E.I. duPont of Wilmington, Del. under the name“Melinex $\\textsuperscript{\\textregistered}$ $516^{\\prime\\prime}$ . To apply the coating, the ingredients of each composition were initially dispersed in deionized water. The resulting dispersion was thoroughly mixed at a temperature of less than 45 degrees C. (or ambient temperature). The mixing was performed until a clear solution was obtained. Coating of the a visor 30, in comparison to those taught in U.S. Pat.No. 7,703,456, which taught compositions with particles in an amount below 10 wt $\\%$  \n\nWhile the disclosure has been described in detail with respect to the specific embodiments thereof, it will be appreciated that those skilled in the art, upon attaining an understanding of the foregoing,may readily conceive of alterations to, variations of, and equivalents to these embodiments. Accordingly, the scope of the present disclosure should be assessed as that of the appended claims and any equivalents thereto.  \n\nWhat is claimed is:",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 20,
+        "chunk": "# 9",
+        "category": " Introduction"
+    },
+    {
+        "id": 21,
+        "chunk": "# 10  \n\n1.A facemask comprising a transparent substrate, wherein a dried residue of an aqueously applied coating is present on at least one surface of said substrate, the coating having a thickness of from about 50 to about 250 nanometers and consisting essentially of organic polymers, nanoparticles and a surfactant, wherein the nanoparticles are present in an amount greater than $15\\mathrm{wt\\%}$ ，and the substrate forms a visor or shield of the facemask that exhibits a transmission of normal incident light of greater than about $3\\%$ when compared to an uncoated substrate.  \n\n2.A facemask as defined in claim 1, wherein said substrate is a polyester film. 3.A facemask as defined in claim 1, wherein said coating comprises at least one organic polymer having an index of refraction of from 1.0 to 1.7. 4.A facemask as defined in claim 1, wherein said organic polymer is ethyl hydroxyethyl cellulose.  \n\n5.A facemask as defined in claim 1, wherein said coating comprises less than about $10\\mathrm{\\mt\\\\%}$ of surfactants. 6. A facemask as defined in claim 1, wherein said coating comprises less than about 1 wt $\\%$ of surfactants. 7.A facemask as defined in claim 1, wherein said coating further comprises antiblocking particles. 8.A facemask as defined in claim 1, wherein said coated substrate exhibits a transmission of normal incident light of greater than about $5\\%$ when compared to an uncoated substrate. 9.A facemask as defined in claim 1, wherein said coated substrate exhibits a transmission of normal incident light of greater than about $10\\%$ when compared to an uncoated substrate. 10.A facemask as defined in claim 1, wherein the haze of said coated substrate subtracted by the haze of an uncoated substrate is less than $0\\%$ +",
+        "category": " Results and discussion"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/2_UV╖└╬э╥║╩╣╙├╦╡├ў╩щ.json b/task2/task2-chunks/2_UV╖└╬э╥║╩╣╙├╦╡├ў╩щ.json
new file mode 100644
index 0000000..cdb10df
--- /dev/null
+++ b/task2/task2-chunks/2_UV╖└╬э╥║╩╣╙├╦╡├ў╩щ.json
@@ -0,0 +1,27 @@
+[
+    {
+        "id": 1,
+        "chunk": "# UV 防雾液产品说明",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# 一、产品简介  \n\nUV 防雾液是一款杂化高分子功能材料液体。本产品主体成分为UV 亲水树脂，在PC 塑料板上有着良好的附着并有着优异的防雾性。对人体无刺激，适应性强，施工性优异。",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 二、产品特点  \n\n硬化优异  \n持久防雾性强  \n良好的黏胶覆膜适应性  \n附着力佳",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# 三、施工参数  \n\n<html><body><table><tr><td>编号</td><td>项目</td><td>单位</td><td>参数</td><td>备注</td></tr><tr><td>1</td><td>开稀比例</td><td>/</td><td>0~30%</td><td></td></tr><tr><td>２</td><td>涂层厚度</td><td>μm</td><td>5-8</td><td></td></tr><tr><td>3</td><td>流平烘烤温度</td><td>℃</td><td>50~60</td><td></td></tr><tr><td>4</td><td>UV固化能量</td><td> J/cm²</td><td>480-550</td><td></td></tr></table></body></html>  \n\n本产品可以直接进行淋涂，根据需要进行适当稀释，稀释比例不得超过 $30\\%$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 四、存储和运输  \n\n1）运输过程中防止撞击和挤压，防止暴晒，按一般危险品运输。  \n2）密封储存于阴凉、干燥通风处，防潮防水，远离火源、热源。需要防潮。  \n3）最好存放请保存环境请低于 $30^{\\circ}\\mathrm{C}$ ，但不建议低于 $10^{\\circ}\\mathrm{C}$ 。保存环境的相对湿度低  \n于 $40\\%\\mathrm{RH}$ 为佳。  \n4）使用期限：6 个月。",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/A novel organic-inorganic zwitterionic acrylate polymer for high-performance anti-fog coating.json b/task2/task2-chunks/A novel organic-inorganic zwitterionic acrylate polymer for high-performance anti-fog coating.json
new file mode 100644
index 0000000..37eec96
--- /dev/null
+++ b/task2/task2-chunks/A novel organic-inorganic zwitterionic acrylate polymer for high-performance anti-fog coating.json	
@@ -0,0 +1,127 @@
+[
+    {
+        "id": 1,
+        "chunk": "# A novel organic-inorganic zwitterionic acrylate polymer for highperformance anti-fog coating  \n\nZiyang Zhenga, Yuping Liua,\\*, Li Wangb,\\*, Li $\\mathtt{Y u}^{\\mathrm{a}}$ , Yuan Cena, Tingting Zhua, Danmei $\\mathtt{Y u}^{\\mathrm{a}}$ , Changguo Chena  \n\na School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, 400044, China b Cccc-Aecom Eco-Environmental Corporation Limited., Beijing, China",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# A R T I C L E I N F O",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# A B S T R A C T  \n\nKeywords: Anti-fog coating Low temperature Zwitterionic salt Hydrophilicity  \n\nA novel organic-inorganic zwitterionic polymer was developed via free radical copolymerization using quaternary ammonium salt as hydrophilic monomer. The unique structure realizes the perfect compromise between the hydrophobicity and hydrophilicity. The chemical composition, the physical properties, the anti-fog characteristic and mechanism of the zwitterionic acrylate coating were investigated by FT-IR, UV-VIS spectrometry, XPS, AFM and water contact angle. After anti-fogging test under ultralow temperature at $\\mathrm{-40^{\\circ}C}$ , the resultant zwitterionic acrylate polymer displays high transparency of $91\\%$ significantly better than that of the bare PC board $21\\ \\%$ . AFM images and water contact angle test demonstrate that the hydrophilic (the soft) region is continuously distributed on the surface of SMA-H coating with smaller water contact angle of $10^{\\circ}$ , indicates better hydrophilicity and wettability. The organic-inorganic zwitterionic polymer endows the coating on polycarbonate (PC) substrate with excellent anti-fog/frost performance, good adhesion and stability (repeated use for 100 times) under wider temperature range $(-40\\sim80^{\\circ}\\mathrm{C})$ of applications.",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1. Introduction  \n\nPolycarbonate (PC) has been extensively used in our daily life due to its excellent transmittance and weather ability [1,2]. However, fogging frequently occurs on the surface of transparent material PC when the temperature of the surrounding solid surface falls below the dew point of contained-water vapor air at certain relative humidity. The undesirable phenomenon means water vapor condensing onto the solid surface under high or low temperature, such as windshield glass, mirror, goggle, cameras, sensors, windows, photovoltaic modules, endoscopes and so on [3,4]. The condensation gives rise to a series of inconvenient and detrimental problems, involving in blurred vision, light scattering, energy consumption and safety hazard during the usage process of transparent glass and plastics [5,6].One strategy to solve these problems is surface modification with hydrophilic anti-fog coating [7,8]. On the surface of hydrophilic anti-fog coating, the water droplets spread over the whole solid surface as a sheet-like water layer, favorable for light transmittance without scattering [9,10]. Generally speaking, the interfacial energy falls to a minimum value once the water droplets are condensed [11,12]. According to Young’s equation, the hydrophilicity of solid surface can be characterized by the contact angle between the three-phase interfaces [13,14]. The contact angles of the superhydrophilic and hydrophilic surfaces feature the range of $5^{\\circ}<\\theta<10^{\\circ}$ and $10^{\\circ}<\\theta<40{-}50^{\\circ}$ , respectively. Then, developing a stable hydrophilic coating with versatile functionalities and facile process is essential for its practical application in hydrophilic anti-fog coating.  \n\nMore recently, many efforts have been reported on synthesizing the hydrophilic coating with good transmittance and anti-fog performance [15,16]. Maechler et al. successfully assembled a multilayer transparent PVA hydrophilic anti-fog coating on a polycarbonate (PC), but its stability should be further improved to practical application [17]. Nuraje et al. produced good mechanical and durable, and long-lasting anti-fog coatings with polysaccharides [18]. Cebeci et al. prepared stably superhydrophilic films with silica nanoparticles and a polycation by the layer-by-layer method [19]. A special hydrophilic/hydrophobic bilayer material with tween-20 and dipentaethritol hexaacrylate was developed by Chang et al. [20]. Further, an effective UV curable hydrophilic acrylate polymers containing a sulfonic acid group was reported as an anti-fog coating by Yuan [4]. Valuably, the zwitterionic polymers raises a lot of concerns comparing to conventional polymers, due to their excellent anti-fog and anti-bacterial performance [21]. The positive and negative charged groups can strongly and stably bind with water molecules through the electrostatically induced hydration interaction [22]. And, the high water content of zwitterionic polymer-grafted surface prevents organic foulants from irreversible adsorption and conformational change [23]. For this reason, Ezzat et al. modified the superhydrophilic poly(methacryloxyethyl sulfobetaine) polymer brushes with the surface-initiated atom transfer radical polymerization [24]. Among these preparation methods, some shortcomings are existed: 1) Some fabrication process is more expensive, complicated and environmental unfriendly. 2) The anti-fogging temperature range is narrow and the anti-fogging/anti-frosting performance is not effective under the boundary condition(extremely cold at $-40^{\\circ}\\mathrm{C}$ , military project, space and so on). 3) The superhydrophilic/hydrophilic coatings possess a number of hydrophilic functionalities such as hydroxyl (OH), amino $\\left(\\mathrm{NH}_{2}\\right)$ , carboxyl(COOH), ester(COOR), amide(NHCOR) and sulfonic $\\left(\\mathrm{HSO}_{3}\\right)$ . These hydrophilic functionalities are prone to interact with considerable water molecules, leading to the instability and dissolution of hydrophilic coatings, especially zwitterionic polymer. Inspired by the reported literature [20], the combination of hydrophobicity and hydrophilicity for the zwitterionic polymer would effectively maintain the balance between the water absorption and water penetration, beneficial for increasing the anti-fogging performance [25].  \n\n![](images/58844d7cc38cecc1ff856dda20713fe171b55a91185200cc3712782d224999e6.jpg)  \nScheme 1. Synthetic route for hydrophilic monomer (D-GMA).  \n\nIn this work, we have developed, for the first time, a facile and inexpensive method to obtain the dual-functional anti-fogging/antifrosting coatings with organic-inorganic zwitterionic polymer, featuring excellent anti-fogging performance under ultralow temperature even at $\\angle40^{\\circ}\\mathrm{C},$ less than the usage temperature of the previously reported literatures at $-20^{\\circ}\\mathrm{C}$ [26–28]. The self-designed silicone modified acrylic zwitterionic polymer is copolymerized by acrylic monomers as acrylic macromolecular skeleton, sulfonic acid quaternary ammonium salt as hydrophilic monomer and the silane as a stabilization component. These functional groups endow the silicone modified acrylic coating with the properties of low water contact angle, high transparency, good mechanical properties, long-term persistence [23] and excellent anti-fogging/anti-frosting performance. This result indicates that the silicone modified acrylic resin hydrophilic coating (SMA-H) is a novel and promising organic-inorganic zwitterionic anti-fog coating.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2. Experimental",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.1. Materials  \n\nDiethanolamine(DEA, $99\\ \\%$ ), N,N-dimethylformamide(DMF, 99.5 $\\%,)$ , butylacrylate(BA, 99 ${\\%},$ ), $^{2,2^{\\prime}}$ -azobis(2-methylpropionitrile) (AIBN,99 $\\left.\\begin{array}{c c c}{{0\\check{}}}&{{}}&{{}}\\\\ {{}}&{{}}&{{}}\\end{array}\\right.$ ), tetrahydrofuran (THF, $99~\\%$ ) and methyl methacrylate (MMA, $99\\ \\mathrm{~\\%~}$ ) were purchased from Aladdin. Glycidylmethacrylate (GMA, $99~\\%$ ), hydroxyethyl methacrylate(HEMA, $99~\\%$ ), 3-methacryloxypropyltrimethoxysilane(KH-570, 98 $\\%$ ) and ethylene glycol monomethylether (EE, $99\\ \\%$ ) were purchased from Adamas. 2-acrylamide-2-methylpropanesulfonic acid(AMPS,99 $\\left.\\begin{array}{r l}{\\centering}&{{}\\overline{{9/_{0}}}\\right|\\overline{{9/_{0}}}\\Biggr.$ ) and iso-propyl alcohol(IPO, $99.5~\\%$ ) was purchased from Sigma-Aldrich. All the chemicals were used as received.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.2. Synthesis of 3-(bis(hydroxymethyl)amino)-2-hydroxypropyl methacrylate (D-GMA)  \n\nFirstly, small hydrophilic molecules of 3-(bis(hydroxymethyl) amino)-2-hydroxypropyl methacrylate (D-GMA) was synthesized with diethanolamine (DEA) and glycidylmethacrylate(GMA) in the molar ratio of 1:1 in tetrahydrofuran solvent. DEA and GMA reactants were mixed and stirred for $^{3\\mathrm{h}}$ at $60^{\\circ}\\mathrm{C}$ under refluxing condition until the mixed solution was transparent. The aqueous supernatant fraction was remained after repeatedly washing with $5\\mathrm{\\sim}7\\mathrm{ml}$ dichloromethane and water to remove the unreacted DEA and GMA. The D-GMA was further acquired via rotary evaporation to remove the residual water in aqueous supernatant fraction with a yield of $30\\ \\%$ . The detailed synthesis procedure is shown in Scheme 1.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.3. Synthetic silicone modified acrylic resin (SMA-H)  \n\nNext, five monomers including the hydrophilic D-GMA/sulfonic acid quaternary ammonium salt(AMPS)/hydroxyethyl methacrylate (HEMA), the acrylic methyl methacrylate (MMA)/butyl acrylate (BA), the importantly hydrophilic silicone(KH-570) were copolymerized to obtain the silicone modified acrylic resin hydrophilic polymer(SMA-H). The synthesis of silicone modified acrylic resin (SMA-H) was divided into two steps. Firstly, $10\\mathrm{ml}$ DMF was heated to $60^{\\circ}\\mathrm{C}$ in the $250\\mathrm{ml}$ three-neck flask, followed by slowly adding MMA, BA and KH-570 in the molar ratio of 3:1:2 in turns. The AIBN concentration was approximately $0.3\\ \\%$ . After reaction for $^{\\textrm{1h}}$ , the low molecular weight copolymer was obtained. Secondly, the as-synthesized low molecular weight copolymer was subsequently reacted with the hydrophilic monomers, HEMA, AMPS and D-GMA (molar ratio: 3:1:3) at $60^{\\circ}\\mathrm{C}$ for $^{4\\mathrm{h}}$ . The synthetic route of the hydrophilic polymer (SMA-H) is displayed in the Scheme 2.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.4. Preparation and curing process of anti-fog coating  \n\nFirstly, the silicone modified acrylic resin hydrophilic polymer (SMA-H), the solvent, hydrolysis catalyst and the leveling agent were configurated to form the mixture of the silicone modified acrylic resin hydrophilic coating. The solvent was composed of iso-propyl alcohol (IPO) and ethylene glycol monomethylether (EE) in the volume ratio of 1:1. The silicone modified acrylic resin hydrophilic polymer and the solvent in the volume ratio of 2:3 were stirred to gain a diluted solution. Then, the diluted solution was reacted with the acetic acid solution $\\mathrm{(pH}=4$ , mass fraction $0.04\\mathrm{~\\}\\%$ ) and BYK-300 leveling agent (mass fraction $0.1\\%\\mathrm{~}$ at $40^{\\circ}\\mathrm{C}$ for $0.5\\mathrm{h}$ to give the mixture of silicone modified acrylic resin hydrophilic coating.  \n\nSecondly, the hydrophilic polymer of SMA-H was grafted onto the pretreated PC board, followed by curing. After washing and drying, the PC board in the size of $5\\mathrm{cm}\\times5\\mathrm{cm}$ was immersed into a solution including PVB(Polyvinyl butyral)and ethanol (the mass fraction of PVB was between $0.05\\substack{-0.1\\ \\%}$ ) for $3\\mathrm{min}$ . Then, the surface-treated PC board was taken out and dried at $80^{\\circ}\\mathrm{C}$ for $10\\mathrm{min}$ . The silicone modified acrylic hydrophilic coating with $\\sim20\\upmu\\mathrm{m}$ thickness was deposited onto the pretreated PC board by a bar applicator at the heat treatment temperature of $110^{\\circ}\\mathrm{C}$ for $^{2\\mathrm{h}}$ .  \n\n![](images/8a20de48a56de4824f150cf790a6845656b419d11216ff102a496f240453b76d.jpg)  \nScheme 2. Synthetic route for the hydrophilic polymer (SMA-H).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.5. Measurements  \n\nFTIR spectra were collected on an AVANAR360 FTIR spectrophotometer using potassium bromide (KBr) disk sampling technique. Differential Scanning Calorimetry (DSC) was conducted by a NETZSCH DSC404 F3 analyzer at a heating rate of $10^{\\circ}\\mathrm{C/min}$ in $\\Nu_{2}$ atmosphere. The thermal stabilities of the polymers were investigated by thermogravimetric analysis (TGA) on a METTLER TOLEDO TGA/1600 L F thermo gravimetric analyzer in $\\Nu_{2}$ atmosphere with the heating rate of $10\\mathrm{^{\\circ}C/m i n}$ from room temperature to $600^{\\circ}\\mathrm{C}$ . X-ray photoelectron spectroscopy (XPS, Kratos Axis Ultra DLD) was monitored with Al Ka probe beam to analyze the chemical composition of the anti-fog coating. Atomic force microscopic (AFM) images were tested with Asylum Research Probe MFP-3D-BIO microscope to capture the surface morphology of the coating. The water contact angle was measured by XYCXIE XG-CAMB2-X water contact meter. The thickness of the coating was measured by the DualScope MP0R thickness gauge (Germany, Fisher). In addition, the adhesion of coating was evaluated according to Chinese National Standard GB/T9286-88 or ISO 2409 Standard [1].",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 2.6. Anti-fog and anti-frost tests  \n\nHigh-temperature anti-fog experiment was carried out by placing the samples above the beaker mouth filled with hot water $(80^{\\circ}\\mathrm{C})$ for 10 s (The distance between the sample and the water surface is $5\\mathrm{cm}$ ). In low temperature anti-fog/frost test, the samples were also put into a refrigerator at certain temperature for $30\\mathrm{min}$ , followed by taking out of refrigerator to ambient condition $20^{\\circ}\\mathrm{C}$ , $50\\%$ relative humidity) for 5 s and recording the surface morphology on PC board. To quantitatively evaluate the transparency of the as-prepared anti-fogging/anti-frosting coating, the light transmission measurement was immediately conducted after these samples were exposed to fogging/frosting environment by the 721 UV–Vis spectroscopy in the wavelength range of $380-780\\mathrm{nm}$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3. Results and discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3.1. Chemical composition  \n\nFig. 1(a) and (b) show the FTIR spectra of the hydrophilic monomer D-GMA and the hydrophilic polymer (SMA-H), respectively. As shown in Fig. 1(a), the IR spectrum of the reactant GMA has obviously characteristic absorption peaks at $850\\mathrm{cm}^{-1}$ and $910\\mathrm{cm}^{-1}$ , corresponding to the symmetric ring deformation and the symmetrical stretching vibration of epoxy function group, respectively [29]. In contrast, the absorption peaks at $850\\mathrm{cm}^{-1}$ and $910\\mathrm{cm}^{-1}$ disappear in the IR of DGMA, which indicates that the epoxy groups participate in the ring opening reaction. As for D-GMA, an distinct stretching vibration absorption peak at $1640\\mathrm{cm}^{-1}$ for $\\mathsf C=\\mathsf C$ [30] represents the successful preparation of the monomer D-GMA in Fig. 1(a). The IR spectrum of the silicone modified acrylic resin is also presented in Fig. 1(b). As can be seen in Fig. 1(b), the peak intensity at $1640\\mathrm{cm}^{-1}$ of SMA-H associated with the $\\mathsf{C}{=}\\mathsf{C}$ group is very weaker than that of GMA, demonstrating the successful copolymerization of all the monomers. As for SMA-H, the stretching vibration absorption bands at $1197\\mathrm{cm}^{-1}$ [31] and $1043\\mathrm{cm}^{-1}$ [32] are assigned to the organic sulfonate in Fig. 1(b). The absorption peak of the hydroxyl group at stretching vibration $3500\\mathrm{cm}^{-1}$ is also observed in the FTIR spectrum of the product SMA-H, as seen in Fig. 1(b). These hydrophilic groups comprising of the hydroxyl and the zwitterionic salt efficiently contribute to the increasing of the anti-fog/anti-frost properties for the silicone modified acrylic resin hydrophilic anti-fog coating. As expected in Scheme 2, the structure of SMA-H is further confirmed by the presence of carbonyl stretching vibration absorption peak at $1720\\mathrm{cm}^{-1}$ [32].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.2. Glass transition temperature  \n\nThe glass transition temperature characterizes the transition temperature of amorphous polymers from glassy to high elasticity. Fig. 2(a) displays the DSC curve of hydrophilic anti-fogging coating. From Fig. 2(a), the glass transition temperatures(Tg) of the anti-fogging coating is approximately $65^{\\circ}\\mathrm{C}$ . It means that the coating exhibits elasticity when the temperature is above $65^{\\circ}\\mathrm{C}_{\\mathrm{i}}$ while the hydrophilic anti-fogging coating shows the property of brittleness when the temperature is lower than $65^{\\circ}\\mathrm{C}$ . Thus, the operating temperature of hydrophilic anti-fogging coating should be controlled below $65^{\\circ}\\mathrm{C}$  \n\nFig. 2(b) gives the DTA-TGA curves of the silicone modified acrylic resin hydrophilic anti-fog coating. It can be apparently seen in Fig. 2(b) that the hydrophilic coating is very stable after curing when the temperature declines to $360^{\\circ}\\mathrm{C}$ . When the temperature is below $200^{\\circ}\\mathrm{C}$ , no significant mass loss implies the absence of solvent in the coating after curing at $110^{\\circ}\\mathrm{C}$ . This result shows the excellent heat stability of the hydrophilic coating. From DTA curve in Fig. 2(b), a strong endothermic peak at $\\sim65^{\\circ}\\mathrm{C}$ is attributed to the glass transition temperature and the other endothermic peak at $360^{\\circ}\\mathrm{C}$ represents the disintegration of silicone modified acrylic resin coating, similar to the previous report [33].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3.3. Anti-Fog properties  \n\nIn this work, the anti-fogging tests of the coating were evaluated at low temperature $(-20^{\\circ}\\mathrm{C},\\ -40^{\\circ}\\mathrm{C})$ and high temperature $(80^{\\circ}\\mathrm{C})$ . In high temperature anti-fog test, a SMA-H-coated PC board and the bare board were put on a cup of hot water $(80^{\\circ}\\mathrm{C})$ . In low temperature antifog test, the samples were put into a refrigerator for $30\\mathrm{min}$ and the surface appearance was recorded 5 s after removal to ambient temperature $20^{\\circ}\\mathrm{C}$ , $50\\%$ relative humidity).  \n\nFig. 3 shows the anti-fog test results of the surface-treated and the bare PC board at different temperatures. As for the bare PC board, the fogging phenomenon is immediately observed on the surface of the bare PC boards at low temperature $(-20,\\ -40^{\\circ}\\mathrm{C})$ and high temperature $(80^{\\circ}\\mathrm{C})$ in Fig. 3(a–c). It can be clearly observed in Fig. 3(a), a large amount of water droplets on the bare PC board blurs our vision and diminishes the transparency of the PC board. Nevertheless, the PC boards treated with silicone modified acrylic resin hydrophilic coating still retain a good transparency at −20, −40 and $80^{\\circ}\\mathrm{C}$ in Fig. 3(a–c). The school badge of Chongqing University is clearly visible through the PC boards covered with SMA-H coating. In comparison with the previous literatures [19,24–27,30,31], the as-prepared coating exhibits an excellent anti-fog performance at low temperature $-40^{\\circ}\\mathrm{C}$ . It is mainly due to successful reduction of the freezing point of the water by the quaternary ammonium salt groups in the polymer. The anti-fog results testify that the anti-fog coatings have good optical transparency with wider temperature range of applications.  \n\n![](images/16421f46cbeebf891119602c721eb828704a5a0da31e7d3621c067ab91c6bc16.jpg)  \nFig. 1. FTIR spectra of hydrophilic monomer (D-GMA) (a) and hydrophilic polymer (SMA-H) (b).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 3.4. Transparency  \n\nFig. 4(a) and (b) display the transmittance of the coated and bare PC board before and after fogging $(-40^{\\circ}\\mathrm{C})$ , respectively. As can be seen in Fig. 4a, the transmittance of the coated PC is slightly higher than that of the bare PC in the range of $380-780\\mathrm{nm}$ (91 vs. $89\\%$ ) before the antifog test. After the anti-fog test at $\\angle40^{\\circ}\\mathrm{C},$ the transmittance of the bare sample is decreased to $21\\ \\%$ owing to the surface fog formation, whereas the surface-treated PC board still shows high transmittance of $91\\%$ in Fig. 4(b), indicating an excellent anti-fog property of the asprepared hydrophilic coating. The main reason for this is that a certain amount of water molecules could interact with the hydrophilic coating as non-freezable bond water through hydrogen bonds and spread uniformly on the PC surface [34].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 3.5. Stability and adhesion  \n\nFig. 5 shows the stability test result of the as-prepared coating after multiple anti-fog tests at $-40^{\\circ}\\mathrm{C}$ . After every anti-fog test, the PC surface is slightly wiped and dried. It can be clearly seen from Fig. 5(a–c) that the as-prepared coating on PC board still shows a good anti-fog feature even after 100 times of anti-fog tests. After repeated tests, the coating still remains good anti-fog performance without scaling, dropping and cracking phenomenon. As also can be observed, the silicone modified acrylic resin hydrophilic coating is still transparent on the whole and has outstanding stability after 100 times of anti-fog tests. Additionally, the adhesion of the coating was measured after 100 times of anti-fog tests at $-40^{\\circ}\\mathrm{C}$ , according to Chinese Standard GB/T9286-88 of the cross-cut method. Fig. 5(d) shows the adhesion test result of the as-prepared coating after 100 times of anti-fog tests. As shown in Fig. 5(d), the coating maintains the intact surface and exhibits the best level of ISO 0 grade according to Chinese national standard GB/T9286- 88, indicating the high durability of the coating on the PC substrate in a certain extent. The pencil hardness of the as-prepared multiple anti-fog coating can reach up to 3H, higher than those of the conventional coatings on the market, such as UV coating(2 H), Epoxy primer(1 H) and so on. The good mechanical property of the as-prepared coating is attributed to the compromise between the Si-O-Si bond and hydrophilic functionalities, specially zwitterionic group. In brief, the silicone modified acrylic resin hydrophilic coating ensures the reliability and durability in consideration of color, transparency and adhesion performance.  \n\n![](images/bcef4b5d8c2c3f6285658499ff56424c6026152217383622c7722787002f5c7c.jpg)  \nFig. 2. (a) DSC curve of hydrophilic anti-fog coating; (b) DTA-TGA curves of the anti-fog coating heated from room temperature to $600^{\\circ}\\mathrm{C}$ at a heating rate of $10^{\\circ}\\mathrm{C}$ $/\\mathrm{min}$ in $\\mathbf{N}_{2}$ atmosphere.  \n\n![](images/9f3dd02e10e086ce8c9f5f3335ab3e924aa5ce3a37b2f2cac94990900234cb6d.jpg)  \nig. 3. Anti-fog test of the bare samples and surface-coated samples at (a) $-20^{\\circ}\\mathrm{C};$ $(\\boldsymbol{\\mathbf{b}})-40{}^{\\circ}\\boldsymbol{\\mathbf{C}};$ (c)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# 3.6. Analysis of the surface  \n\nThe excellent anti-fog/anti-frost performance and good stability of the cured SAM-H coating on PC board is expounded by means of X-ray photoelectron spectroscopy. Fig. 6(a) shows the XPS survey spectrum of the cured SAM-H coating. As expected, the cured SAM-H coating consists of C, N, O, S and Si elements in Fig. 6(a). Fig. 6(b)–(e) displays the high-resolution spectra of C1s, O1s, N1s, Si2p, respectively. As can be shown in Fig. 6(b), the C1s peak originates from the CeO (285.91 eV), $\\mathsf{C}{\\mathrm{-}}\\mathsf{H}$ $284.42\\mathrm{eV})$ , $\\scriptstyle{\\mathsf{C}}=0$ (288.47 eV), CeN $285.6\\mathsf{e V}$ [35] and C-Si $(283.4\\mathrm{eV})$ [36]. The O1s spectrum in Fig. 6(c) is composed of four peaks, which are located at $531.09\\mathrm{eV}$ , 531.53 eV, $531.83\\mathrm{eV}$ and $532.97\\mathrm{eV}$ . The O1s peak at 531.09 eV can be ascribed to the $_{\\mathsf{C}-\\mathsf{O}}$ bond according to the XPS handbook and the other three O1s peaks are attributed to $\\scriptstyle\\mathtt{C=}0$ (531.53 eV) [37], Si-O(531.83 eV) [38] and Si-O-Si (532.97 eV) [39], respectively. In Fig. 6(d), the N1s peak can be fitted with three individual peaks at $399.09\\mathrm{eV}$ , 401.1 eV and 401.86. eV, corresponding to the N- $(\\mathrm{CH}_{3})_{3}$ group of the reactant (AMPS), the $\\boldsymbol{\\mathrm{N-H}}$ and the ${{\\bf{C}}{\\bf{-}}{\\bf{N}}^{+}}$ group of the hydrophilic polymer(D-GMA) [37], respectively. As for $\\mathtt{s i2p}$ spectrum in Fig. 6(e), the Si2p peak situated at $102.14\\mathrm{eV}$ and $101.46\\mathrm{eV}$ can be assigned to two components of the $S\\mathrm{i}-\\mathsf{C O}_{3}$ [40] and Si- $(\\mathsf{C}_{2}\\mathsf{O}_{2})$ groups [39], respectively. These findings verify that the macromolecular network structure of the cured SMA-H coating on PC board is formed by the co-condensation reaction between the $S\\mathrm{i}{-}0\\mathrm{H}$ bonds of the anti-fog coating and the $_{\\mathrm{O-H}}$ bonds of the pretreated surface of PC board, whose the highly crosslinked backbone is Si-O-Si siloxane bonds. Fig.7 shows the schematic illustration of the SMA-H coating formed on the PC substrate, elucidating the mechanism of the chemical interaction between the SMA-H coating and the PC board. This illustration gives a good explanation to the enhanced stability of hydrophilic SMA-H coating by implementing the perfect compromise between the hydrophobicity and hydrophilicity.  \n\n![](images/dbb64c115e3b489ce05b3cea3ec40e0ca82c00900a97987106b3bf3d764a9044.jpg)  \nFig. 4. UV–vis spectra of the surface-coated and bare PC board (a) before and (b) after fogging $(-40^{\\circ}\\mathrm{C})$  \n\n![](images/aac7df4ecee316b5ee21c1f3c8075f3c97471e158632587365e9c87f4014dbce.jpg)  \nFig. 5. Stability test of the coating after multiple anti-fog tests: (a) 20 times; (b) 50 times; (c) 100 times.  \n\n![](images/3b9e4b7ac51d0ca38325d0c4655407cbdda1e7762f9d7462127b60804fca8de4.jpg)  \nFig. 6. XPS spectra of the cured SMA-H coating (a) Survey; (b) C1s; (c) O1s; (d) N1s and (e) Si2p.  \n\n![](images/a4d591269299f768dea32914fff324efe948fa053142fc009fc75b84134c94de.jpg)  \nFig. 7. Schematic illustration of the SMA-H coating formed on the PC substrate.  \n\n![](images/d667db37be53f1d789c4947c87ae673be6cad4c893f39d5fd7e4b52f84bfc560.jpg)  \nFig. 8. AFM topography (left) and phase (right) images of the cured anti-fog coating on PC board.  \n\n![](images/3c286c1a580bbfda458cad1898cdf9addc86ce6abe78a2626703bd4b9fbad494.jpg)  \nFig. 9. The water contact angle profile of the bare sample (a) and the coated sample (b).  \n\nAtomic force microscopy (AFM) was adopted to detect the physical properties and micromorphology of material in order to further clarify the anti-fog mechanism of the zwitterionic hydrophilic polymer. The topography (left) and phase (right) images of the cured SMA-H coating surface are given in Fig. 8 with tapping-mode AFM in air under ambient conditions. The high Rq roughness of the SMA-H coating from the topography images in Fig. 8(a, c) is $\\sim3.574\\mathrm{nm}$ , suggesting the porous/ rough properties of the SMA-H coating surface decreasing its optical reflection [41]. Fig. 8(b) and (d) show the phase images of SMA-H coating. In a typical AFM phase image of a micro-phase separated polyurethane, the lighter regions represent the hard phase, whereas the darker regions assign the soft phase [42]. In the light of the lighter and darker image, we can easily distinguish the hydrophilic (the soft) region from the hydrophobic (the hard) region on the surface of SMA-H coating. The yellow soft region in Fig. 8(b, d) is continuously distributed on the surface of SMA-H coating. The growing-condensed water droplets gradually adsorb and spread onto large areas of the hydrophilic region, accompanied by their decreased surface tension [20]. In Fig. 8(d), the area of the hydrophobic domains is only less than $100\\mathrm{nm}^{2}$ and the hydrophobic area is fully surrounded by the hydrophilic materials, which further explains why the coating has an outstanding anti-fogging performance.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 3.7. Assessment of the wetting behavior  \n\nTo further elaborate the anti-fog/anti-frost mechanism, the water contact angle was measured to evaluate the anti-fog performance in term of the wettability of coating surface. Fig. 9(a, b) show the water contact angle profiles of the bare sample and the coated sample, respectively. As can be displayed in Fig. 9(a) and (b), the water contact angles of the bare and surface-treated PC boards are $78^{\\circ}$ and ${\\sim}10^{\\circ}$ respectively. It is widely accepted that the solid surface is hydrophilic when the water contact angle is less than $90^{\\circ}$ , whereas the solid surface is hydrophobic when the water contact angle is greater than $90^{\\circ}$ [43]. The smaller the contact angle, the better the liquid's wettability of the solid. Wettability can characterize the degree of affinity between a liquid and a solid surface and the contact angle is the important parameter that quantifies the wettability. Upon balancing the interface tensions between the solid/vapor, solid/liquid, and liquid/vapor interface, water drops tend to minimize the total surface free energy while maintaining its volume [44]. The shape of liquid drops is typically spherical on the hydrophobic surface. Hence, the water drops on the bare PC board in Fig. 9(a) resembles sphere, which is very similar to the morphology of the hydrophobic surface [44]. In contrast, the water contact angle of the surface-coated sample is very small $(10^{\\circ})$ . The main reason for this is that the liquid drops spread over the hydrophilic surface to form a sheet-like layers in Fig. 9(b) with the synergistic effect of the $-\\mathrm{OH}$ groups and the zwitterionic of the SMA-H coating. As a result, the coated surface of the PC board remains optical transmittance even after the anti-fogging test under ultralow temperature at the $\\angle40^{\\circ}\\mathrm{C}$ . Simultaneously, the Si-O-Si groups provide a water-fast mesh structure and prevents the SMA-H coating from being dissolved in water.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# 4. Conclusion  \n\nIn this article, we fabricated a novel effective organic-inorganic zwitterionic acrylate anti-fog/frost coating via free radical copolymerization. The organic-inorganic zwitterionic acrylate coating consists of the hydroxyl groups, the sulfonic acid quaternary ammonium salt and silicon oxygen network structure confirmed by IR and XPS. The unique structure endows the polymer coated on polycarbonate (PC) substrate with excellent anti-fog performance and good stability (repeated use for 100 times) under wider temperature range $(-40\\sim80^{\\circ}\\mathrm{C})$ of applications. The glass transition temperatures(Tg) of the anti-fogging coating is about $65^{\\circ}\\mathrm{C}$ . After anti-fogging test under ultralow temperature at $\\angle40^{\\circ}\\mathrm{C},$ the light transmittance value of the grafted-coating on PC board still maintain $91\\%$ , significantly better than that of the bare PC board $21\\ \\%$ . AFM images demonstrate that the hydrophilic (the soft) region is continuously distributed on the surface of SMA-H coating. As for the coated PC board, the smaller water contact angle of $10^{\\circ}$ indicates better hydrophilicity and wettability. The as-prepared organic-inorganic zwitterionic acrylate anti-fog/frost coating will promote the extensive application of transparent polycarbonate (PC) material with a facile and low-cost preparation route.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 21,
+        "chunk": "# CRediT authorship contribution statement  \n\nZiyang Zheng: Investigation, Conceptualization, Methodology, Software, Data curation, Formal analysis, Writing - original draft. Yuping Liu: Funding acquisition, Investigation, Methodology, Formal analysis, Software, Writing - review & editing. Li Wang: Funding acquisition, Formal analysis, Visualization. Li Yu: Investigation, Data curation, Formal analysis. Yuan Cen: Software, Formal analysis, Validation. Tingting Zhu: Investigation, Formal analysis, Software. Danmei Yu: Resources, Supervision, Validation. Changguo Chen:  \n\nProject administration, Methodology, Supervision.",
+        "category": " Abstract"
+    },
+    {
+        "id": 22,
+        "chunk": "# Declaration of Competing Interest  \n\nThe authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 23,
+        "chunk": "# Acknowledgments  \n\nThis research was supported by the National Natural Science Foundation of China under Grant No. 21406021.",
+        "category": " References"
+    },
+    {
+        "id": 24,
+        "chunk": "# Appendix A. Supplementary data  \n\nSupplementary material related to this article can be found, in the online version, at doi:https://doi.org/10.1016/j.porgcoat.2020. 105578.",
+        "category": " References"
+    },
+    {
+        "id": 25,
+        "chunk": "# References  \n\n[1] R. Fateh, R. Dillert, D. Bahnemann, Preparation and characterization of transparent hydrophilic photocatalytic $\\mathrm{TiO_{2}/S i O_{2}}$ thin films on polycarbonate, Langmuir 29 (2013) 3730–3739. [2] A. Suligoj, O. Pliekhova, N. Vodisek, M. Mihelcic, A.K. Surca, R. Kunic, B. Subic, J. Starman, A. Ugovsek, U. Lavrencic Stangar, Field test of self-cleaning ZrModified- $\\mathrm{\\cdotTiO}_{2}$ - $\\mathrm{SiO}_{2}$ films on glass with a demonstration of their anti-fogging effect, Materials Basel (Basel) 12 (2019). [3] J.W. Hong, H.K. Cheon, S.H. Kim, K.H. Hwang, H.K. Kim, Synthesis and characterization of UV curable urethane acrylate oligomers containing ammonium salts for anti-fog coatings, Prog. Org. Coat. 110 (2017) 122–127. [4] Y. Yuan, R. Liu, C. Wang, J. Luo, X. Liu, Synthesis of UV-curable acrylate polymer containing sulfonic groups for anti-fog coatings, Prog. Org. Coat. 77 (2014) 785–789. [5] Z. Han, Z. Mu, Y. Wei, W. Li, S. Niu, J. Zhang, L. Ren, Biomimetic multifunctional surfaces inspired from animals, Adv. Colloid Interface Sci. 234 (2016) 27–50.   \n[6] J.B. Chemin, S. Bulou, K. Baba, C. Fontaine, T. Sindzingre, N.D. Boscher, P. Choquet, Transparent anti-fogging and self-cleaning $\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ thin films on polymer substrates using atmospheric plasma, Sci. Rep. 8 (2018) 9603. [7] R. Wang, K. Hashimoto, A. Fujishima, M. Chikuni, E. Kojima, A. Kitamura, M. Shimohigoshi, T. Watanabe, Light-induced amphiphilic surfaces, Nature 388 (1997) 431–432. [8] B. Lin, S. Zhou, Poly(ethylene glycol)-grafted silica nanoparticles for highly hydrophilic acrylic-based polyurethane coatings, Prog. Org. Coat. 106 (2017) 145–154.   \n[9] H. Lee, M.L. Alcaraz, M.F. Rubner, R.E. Cohen, Zwitter-wettability and antifogging coatings with frost-resisting capabilities, ACS Nano 7 (2013) 2172.   \n[10] P.S. Brown, O.D.L.A. Atkinson, J.P.S. Badyal, Ultrafast oleophobic–Hydrophilic switching surfaces for antifogging, self-cleaning, and oil–Water separation, ACS Appl. Mater. Interfaces 6 (2014) 7504.   \n[11] J.G. Kim, H.J. Choi, K.C. Park, R.E. Cohen, G.H. Mckinley, G. Barbastathis, Multifunctional inverted nanocone arrays for non‐wetting, self‐cleaning transparent surface with high mechanical robustness, Small 10 (2014) 2487–2494.   \n[12] Q. Xu, J. Li, J. Tian, J. Zhu, X. Gao, Energy-effective frost-free coatings based on superhydrophobic aligned nanocones, ACS Appl. Mater. Interfaces 6 (2014) 8976–8980.   \n[13] K.T. Huang, S.B. Yeh, C.J. Huang, Surface modification for superhydrophilicity and underwater superoleophobicity: applications in Antifog, underwater self-cleaning, and oil–water separation, ACS Appl. Mater. Interfaces 7 (2015) 21021.   \n[14] Y. Zhu, F. Zhang, D. Wang, X.F. Pei, W. Zhang, J. Jin, A novel zwitterionic polyelectrolyte grafted PVDF membrane for thoroughly separating oil from water with ultrahigh efficiency, J. Mater. Chem. A 1 (2013) 5758–5765.   \n[15] Z. Duan, Y. Zhu, P. Ren, J. Jia, S. Yang, G. Zhao, Y. Xie, J. Zhang, Non-UV activated superhydrophilicity of patterned Fe-doped $\\mathrm{TiO}_{2}$ film for anti-fogging and photocatalysis, Appl. Surf. Sci. 452 (2018) 165–173.   \n[16] L. Wang, J. Lu, M. Wang, B. Zhang, Y. Hou, G. Liu, W. Yang, J. Liu, Anti-fogging performances of liquid metal surface modified by ZnO nano-petals, J. Taiwan Inst. Chem. Eng. 95 (2019) 65–70.   \n[17] L. Maechler, C. Sarra-Bournet, P. Chevallier, N. Gherardi, G. Laroche, Anti-fog layer deposition onto polymer materials: a multi-step approach, Plasma Chem. Plasma Process. 31 (2011) 175–187.   \n[18] N. Nuraje, R. Asmatulu, R.E. Cohen, M.F. Rubner, Durable antifog films from layerby-layer molecularly blended hydrophilic polysaccharides, Langmuir 27 (2011) 782–791.   \n[19] F.C. Cebeci, Z. Wu, L. Zhai, R.E. Cohen, M.F. Rubner, Nanoporosity-driven superhydrophilicity: a means to create multifunctional antifogging coatings, Langmuir the Acs Journal of Surfaces & Colloids 22 (2006) 2856–2862.   \n[20] C.C. Chang, F.H. Huang, H.H. Chang, T.M. Don, C.C. Chen, L.P. Cheng, Preparation of water-resistant antifog hard coatings on plastic substrate, Langmuir the Acs Journal of Surfaces & Colloids 28 (2012) 17193.   \n[21] H. Guo, X. Tong, J. Zhang, W. Zhao, J. Zhang, C. Lin, Z. Lei, A multifunctional antifog, antibacterial, and self-cleaning surface coating based on poly(NVP-co-MA), Chem. Eng. J. (2018) S1385894718311008-.   \n[22] K. Ishihara, Why do phospholipid polymer reduce protein adsorption? J.biomed.mater.res 39 (1998).   \n[23] S. Chen, F. Yu, Q. Yu, Y. He, S. Jiang, Strong resistance of a thin crystalline layer of balanced charged groups to protein adsorption, Langmuir the Acs Journal of Surfaces & Colloids 22 (2006) 8186.   \n[24] M. Ezzat, C.J. Huang, Zwitterionic polymer brush coatings with excellent anti-fog and anti-frost properties, RSC Adv. 6 (2016) 61695–61702.   \n[25] M. Shahnooshi, A. Eshaghi, A.A. Aghaei, Transparent anti-fogging and anti-scratch SiO2/SiO2–TiO2 thin film on polycarbonate substrate, Mater. Res. Express 6 (2019) 086447.   \n[26] C. Tao, S. Bai, X. Li, C. Li, L. Ren, Y. Zhao, X. Yuan, Formation of zwitterionic coatings with an aqueous lubricating layer for antifogging/anti-icing applications, Prog. Org. Coat. 115 (2018) 56–64.   \n[27] M. Vatankhah-Varnosfaderani, X. Hu, Q. Li, H. Adelnia, M. Ina, S.S. Sheiko, Universal coatings based on zwitterionic-dopamine copolymer microgels, ACS Appl. Mater. Interfaces 10 (2018) 20869–20875.   \n[28] Q. Liu, J. Locklin, Transparent grafted zwitterionic copolymer coatings that exhibit both antifogging and self-cleaning properties, ACS Omega 3 (2018) 17743–17750.   \n[29] N.S. Nadiah, F.S. Omar, A. Numan, Y.K. Mahipal, S. Ramesh, K. Ramesh, Influence of acrylic acid on ethylene carbonate/dimethyl carbonate based liquid electrolyte and its supercapacitor application, Int. J. Hydrogen Energy 42 (2017).   \n[30] W. Lee, S. Furusaki, K. Saito, T. Sugo, Tailoring a brush-type interface favorable for capturing microbial cells, J. Colloid Interface Sci. 200 (1998) 66–73.   \n[31] M. Stach, Z. Kroneková, P. Kasák, J. Kollár, M. Pentrák, M. Mičušík, D.C. Jr, T.S. Nunney, I. Lacík, Polysulfobetaine films prepared by electrografting technique for reduction of biofouling on electroconductive surfaces, Appl. Surf. Sci. 257 (2011) 10795–10801.   \n[32] Z. Yang, D. Saeki, H. Matsuyama, Zwitterionic polymer modification of polyamide reverse-osmosis membranes via surface amination and atom transfer radical polymerization for anti-biofouling, J. Memb. Sci. (2018).   \n[33] Yuhang JIANG, Xuesong WANG, Linglan PIAO, Zhanchen Zuosen, Fabrication of new transparent and hydrophilic hybrid anti-fog coating from silane coupler modified by polyethylene glycols, Chem. Res. Chin. Univ. 33 (2017) 1–5.   \n[34] C.Q. Sun, Supersolidity of the undercoordinated and the hydrating water, Phys. Chem. Chem. Phys. 20 (2018) 30104–30119.   \n[35] W.J. Yang, K.G. Neoh, E.T. Kang, L.M. Teo, D. Rittschof, Stainless steel surfaces with thiol-terminated hyperbranched polymers for functionalization via thiol-based chemistry, Polym. Chem. 4 (2013) 3105–3115.   \n[36] P.W. Wang, J. Sulak, S. Bater, L.P. Zhang, J.H.C. Jr, X-ray photon and thermal effects on trimethylsilane covered Si(100) surfaces, Thin Solid Films 304 (1997) 160–165.   \n[37] E.J. Oh, R. Hempelmann, V. Nica, I. Radev, H. Natter, New catalyst supports prepared by surface modification of graphene- and carbon nanotube structures with nitrogen containing carbon coatings, J. Power Sources 341 (2017) 240–249.   \n[38] J.H. Lopes, E.M.B. Fonseca, I.O. Mazali, A. Magalhães, R. Landers, C.A. Bertran, Facile and innovative method for bioglass surface modification: optimization studies, Mater. Sci. Eng. C 72 (2017) 86–97.   \n[39] Y.T. Fang, T. Liu, Z.C. Zhang, X.N. Gao, Silica gel adsorbents doped with Al, Ti, and Co ions improved adsorption capacity, thermal stability and aging resistance, Renew. Energy 63 (2014) 755–761.   \n[40] J. Lewandowska-Łańcucka, M. Staszewska, M. Szuwarzyński, S. Zapotoczny, M. Kepczynski, Z. Olejniczak, B. Sulikowski, M. Nowakowska, Design and characterization of silicone micromaterials: a systematic study, Mater. Des. 146 (2018).   \n[41] K. Manabe, M. Matsuda, C. Nakamura, K. Takahashi, K.H. Kyung, S. Shiratori, Antireflective Antifibrinogen, Antifogging surfaces with biocompatible nano-ordered hierarchical texture fabricated by layer-by-layer self-assembly, Chem. Mater. 29 (2017).   \n[42] S. Hsu, C.M. Tang, H.J. Tseng, Gold nanoparticles induce surface morphological transformation in polyurethane and affect the cellular response, Biomacromolecules 9 (2008) 241.   \n[43] I.R. Durán, G. Laroche, Current trends, challenges, and perspectives of anti-fogging technology: surface and material design, fabrication strategies, and beyond, Prog. Mater. Sci. 99 (2019) 106–186.   \n[44] I.R. Duran, G. Laroche, Water drop-surface interactions as the basis for the design of anti-fogging surfaces: theory, practice, and applications trends, Adv. Colloid Interface Sci. 263 (2019) 68–94.",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# AI for organic and polymer synthesis  \n\nXin Hong1\\*, Qi Yang2\\*, Kuangbiao Liao3\\*, Jianfeng Pei4\\*, Mao Chen5\\*, Fanyang Mo6,8\\*, Hua Lu7\\*, Wen-Bin Zhang7,8\\*, Haisen Zhou7, Jiaxiao Chen4, Lebin ${\\mathrm{Su}}^{3}$ , Shuo-Qing Zhang Siyuan Liu2, Xu Huang9, Yi-Zhou Sun1, Yuxiang Wang7,8, Zexi Zhang5, Zhunzhun $\\mathrm{Yu}^{3}$ , Sanzhong Luo , Xue-Feng Fu & Shu-Li You  \n\n1Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou 310027, China; 2Center of Basic Molecular Science, Department of Chemistry, Tsinghua University, Beijing 100084, China; 3Guangzhou National Laboratory, Guangzhou 510005, China; 4Center for Quantitative Biology, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China; 5State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200433, China; 6School of Materials Science and Engineering, Peking University, Beijing 100871, China; $^{7}$ Beijing National Laboratory for Molecular Sciences, Center for Soft Matter Science and Engineering, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China; 8AI for Science (AI4S)-Preferred Program, Shenzhen Graduate School, Peking University, Shenzhen 518055, China; 9State Key Laboratory of Chemical Biology, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, China; 10Department of Chemical Sciences, National Natural Science Foundation of China, Beijing 100085, China; 11State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China  \n\nReceived March 20, 2024; accepted April 28, 2024; published online June 26, 2024  \n\nRecent years have witnessed the transformative impact from the integration of artificial intelligence with organic and polymer synthesis. This synergy offers innovative and intelligent solutions to a range of classic problems in synthetic chemistry. These exciting advancements include the prediction of molecular property, multi-step retrosynthetic pathway planning, elucidation of the structure-performance relationship of single-step transformation, establishment of the quantitative linkage between polymer structures and their functions, design and optimization of polymerization process, prediction of the structure and sequence of biological macromolecules, as well as automated and intelligent synthesis platforms. Chemists can now explore synthetic chemistry with unprecedented precision and efficiency, creating novel reactions, catalysts, and polymer materials under the datadriven paradigm. Despite these thrilling developments, the field of artificial intelligence (AI) synthetic chemistry is still in its infancy, facing challenges and limitations in terms of data openness, model interpretability, as well as software and hardware support. This review aims to provide an overview of the current progress, key challenges, and future development suggestions in the interdisciplinary field between AI and synthetic chemistry. It is hoped that this overview will offer readers a comprehensive understanding of this emerging field, inspiring and promoting further scientific research and development.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# organic synthesis, polymer synthesis, machine learning prediction, chemical database, automated synthesis",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# CONTENTS  \n\n1 Introduction 2462   \n2 Machine learning pipeline 2462   \n3 AI applications in organic synthesis 2465   \n3.1 Molecular property prediction 2465   \n3.2 Prediction and optimization of synthetic transfor  \nmation 2467   \n4 AI applications in polymer synthesis 2475   \n4.1 Structure-property relationship prediction of poly  \nmer 2475   \n4.2 Target-orientated design of polymer 2477   \n4.3 Design and optimization of polymer synthesis 2478   \n4.4 End-to-end prediction of polymerization 2479   \n4.5 AI Application in biological macromolecules 2481   \n5 Automated experimentation 2483   \n5.1 Automated synthesis 2483   \n5.2 Automated work-up, isolation and purification 2486   \n5.3 Integration of AI with robotic systems 2486   \n6 Challenges and perspective 2486   \n6.1 Data 2486   \n6.2 Encoding 2487   \n6.3 Model availability 2488   \n6.4 Automated experimentation 2488   \n7 Conclusions and outlook 2489",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1 Introduction  \n\nArtificial intelligence (AI) encompasses a broad set of technologies that simulate human intelligence, of which machine learning (ML) is a crucial subset. ML enables computer systems to learn from and interpret data without explicit programming, forming the core mechanism behind most AI applications. By observing and analyzing massive datasets, AI algorithms can identify patterns, classify information, and even make complex decisions. Particularly in the field of natural language processing (NLP), the development of AI has been transformative. Recent years have seen large language models (LLMs) [1–4], like ChatGPT [5], significantly contribute to this advancement, embodying the dream of artificial general intelligence. In the field of chemistry, LLMs also have exciting applications: research has shown that LLMs inherently possess a certain degree of chemical understanding [6]. Models like Coscientist, which can autonomously design, plan, and execute chemical research, illustrate how LLMs facilitate chemical research by automating literature analysis and experimental processes [7]. This AI wave continues to expand, driving technological advancements across a broad spectrum of domains; for example, the advent of AlphaGo has seen it defeat top human players in Go [8], and the emergence of AlphaFold [9] signals the inevitable embrace of the AI revolution in natural sciences. This paradigm shift brought about by AI is profoundly influencing the methods through which humanity tackles and resolves complex high-dimensional problems.  \n\nWithin the realm of synthetic chemistry, chemists are constantly faced with the challenges of complexity and multidimensionality. The inherent intricacy of these problems renders bottom-up theoretical deductions difficult, leading synthetic chemists to realize the potential of approaching these issues from the perspectives of data science and information science [10]. Whether in synthetic pathway planning [11–13] or exploring substituent effects [14], chemists have already widely applied data-driven methods. These methods, ranging from simple linear fitting to the development of complex expert systems, offered a powerful strategy for chemists to find solutions in the ocean of data, yielding fruitful advances in synthetic chemistry.  \n\nFrom the research journey of the substituent effect, we can appreciate the profound impact of data and intelligence on synthetic chemistry. The pioneering explorations of Ingold [15] and Robinson et al. [16] laid the foundation for concepts such as steric hindrance and electronic effects, now fundamental in organic chemistry textbooks. Hammett’s systematic and in-depth application of linear relationship to the study of substituent effects has made the Hammett equation a cornerstone for analyzing organic reaction mechanisms [17,18]. Later, the exciting advances from Sigman and others revealed the potential of multivariate linear free energy relationship (LFER) in propelling the understanding and design of modern synthetic transformations [19]. Today, the continuous expansion of synthetic chemistry databases and the advancement of AI algorithms have enabled chemists to make chemical accuracy-level predictions of molecular properties directly from topological structures. A notable example includes the application of the iBonD database [20] for $\\mathsf{p}K_{\\mathrm{a}}$ predictions, which matches the accuracy of quantum calculations while significantly enhancing efficiency by orders of magnitude [21]. These advancements have not only facilitated progress in organic synthesis, but also led to significant achievements in polymer synthesis and automated experimentation with important directions highlighted in Figure 1, signaling the dawn of a new era of intelligent synthesis. In this review, we focus not only on representative directions and outcomes of the intersection between artificial intelligence and synthetic chemistry, but also delve into the current challenges facing the field along with potential solutions. This list is by no means comprehensive, but it is our hope that through this review, readers will gain a clear and comprehensive perspective on the breadth and depth of AI applications in synthetic chemistry.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2 Machine learning pipeline  \n\nPrior to delving into specific research advancements, it is essential to elucidate the fundamentals of ML, especially as they pertain to applications within synthetic chemistry. ML techniques are categorized into three primary types: supervised learning, where the goal is to learn a function mapping inputs to outputs given labeled data; unsupervised learning, aimed at uncovering the hidden structure of unlabeled data; and reinforcement learning, focused on learning how to take actions to maximize some notion of cumulative reward through interaction with an environment. ML typically encompasses four critical stages: data collection, encoding, model training, and result analysis (Figure 2). Initially, the collection and organization of relevant data lay the groundwork for model construction. Subsequently, during the encoding phase, these data are transformed into a format interpretable by ML models. The model training stage then utilizes encoded data, allowing algorithms to identify patterns and relationships within the data. Finally, result analysis evaluates the predictive performance of the model as well as interprets the rationale behind the model predictions. These stages collectively form the foundation for applying ML in the realm of synthetic chemistry, promoting the intelligent solution of chemical problems.  \n\nThe primary sources of data in synthetic chemistry currently include public databases, high-throughput experimentation (HTE), computational simulations, and electronic laboratory notebooks (ELNs). These diverse data streams are vital for the success of ML modeling, offering extensive information on reactions, compounds, and properties. Table 1 lists exemplary open-access databases for organic and polymer synthesis. Public databases like Reaxys and Scifinder are indispensable for providing comprehensive chemical data, while HTE systems enable the efficient generation of large datasets through automated experiments, assessing thousands of reactions with minimal material and time. ELNs play a crucial role in documenting and sharing experimental details [22,23], although they present challenges related to data standardization, privacy, and variability. Together, these sources underpin the development of ML models in synthetic chemistry, leveraging the vast array of data to fuel innovations through computational analysis and experimental integration.  \n\nEncoding molecules and reactions into machine-readable formats are critical for ML modeling. The molecular encodings can be characterized by a hierarchy of complexity: zero-dimensional physicochemical properties like molecular weight and $\\mathrm{Log}P$ , one-dimensional string representations such as SMILES [38] and SELFIES [39] for encoding atomic types and connections, two-dimensional molecular fingerprints capturing molecular structures without stereochemical details, and three-dimensional descriptors that include stereochemistry and quantum chemical features for a comprehensive representation of molecular conformations. Additionally, graph-based learning methods offer advanced ways to depict molecules and reactions [40], addressing the complexity of chemical structures in multidimensional space. For polymers, the challenge of their stochastic nature is met with novel encoding strategies like BigSMILES [41] for sequence distributions and PolyGrammar [42] for hypergraph representations, alongside graph neural networks and Transformer-based language models to distinguish polymer sequences and topologies. These encoding strategies are essential for effectively processing and analyzing chemical data, enabling the advancement of ML applications in organic and polymer systems.  \n\n![](images/b2a502371d09d4b0c832c995ffc4d58f26e9f7bd53515f407782dc486f373d50.jpg)  \nFigure 1 Representative research directions of AI applications in organic and polymer synthesis (color online).  \n\n![](images/4d9d6362e8d9e6392209e31fdf2279597e071566817fa87cdef418c0fb670d1c.jpg)  \nFigure 2 Typical pipeline of machine learning modeling (color online).  \n\nTable 1 Overview of representative open access databases for organic and polymer synthesis   \n\n\n<html><body><table><tr><td>Database</td><td>Description</td><td>Database</td><td>Description</td></tr><tr><td>ChEBI [24]</td><td>Molecular entities of small chemical compounds.</td><td>IBonD [20]</td><td>Chemical database that covers heterolytic (pKa and homolytic bond dissociation energies (BDE).</td></tr><tr><td>ChEMBL[25]</td><td>Database of bioactive molecules with drug-like properties.</td><td>SDBS [26]</td><td>Spectra database system for organic compounds.</td></tr><tr><td>COD [27]</td><td>Crystal structure database of organic, inorganic, and metal-organic compounds.</td><td>SpectraBase [28]</td><td>Spectra database for organic, organometallic, and inorganic compounds.</td></tr><tr><td>NIST chemistry Webbook [29]</td><td>NIST standard reference database of chemical and physical property data.</td><td>UniChem [30]</td><td>Database of pointers between chemical structures and EMBL-EBI chemistry resources.</td></tr><tr><td>OSCAR [31]</td><td>Datasets of chemically and functionally diverse organocatalysts.</td><td>ZINC20 [32]</td><td>Database of commercially available compounds.</td></tr><tr><td>PubChem [33,34]</td><td>Collection of freely accessible chemical information.</td><td>ORD [35]</td><td>Open organic reaction database.</td></tr><tr><td>ChemSpider</td><td>Database of chemical information including molecular structures and properties.</td><td>PoLyInfo</td><td>Polymer database that covers properties, structures, processing methods, etc.</td></tr><tr><td>USPTO</td><td>Open data of United States patents.</td><td>MatWeb</td><td>Material property database that includes information on a wide range of materials and polymers.</td></tr><tr><td>Quantum-machine [36,37]</td><td>Quantum chemistry calculation database.</td><td>Synthesis Explorer</td><td>Curated collection of chemical reactions and synthesis pathways.</td></tr></table></body></html>  \n\nThe process of ML modeling involves utilizing algorithms to grasp patterns within data, thereby enabling predictions about unknown targets. This involves a spectrum of methodologies from classical ML, adept at handling linear relationships and structured data, to deep learning, known for its proficiency with large-scale and complex datasets. Classical models like linear, tree-based, and kernel-based methods offer solutions for simpler relationships, while deep learning’s layered architecture allows for the extraction of high-dimensional features. In addition, the modern ML process can be adaptive with active learning and transfer learning techniques. Active learning dynamically selects the most informative data points for labeling and training, effectively improving model performance with less data. Transfer learning leverages knowledge acquired from one domain to enhance model accuracy in another, significantly reducing the need for extensive labeled datasets in new applications. Selecting the right model and algorithm is crucial, depending on the data’s nature and the analytical task at hand. Typical evaluation methods include cross-validation and independent test sets, which are essential to ensure the model’s generalizability and effectiveness in real-world applications.  \n\nFor ML applications, result analysis and model interpretation are equally important [43,44], as merely relying on and executing each model prediction is insufficient and lacks comprehensiveness. In the analysis of ML predictions, one can leverage domain expertise to evaluate and contrast predictions against non-ML methodologies. Techniques such as sensitivity analysis and hypothesis testing further aid in assessing the accuracy and reliability of models, especially when predictions deviate from expected norms. Additionally, methods like dimensionality reduction and clustering are instrumental in deriving valuable insights from ML predictions, as demonstrated in Tim Cernak’s utilization of graph editing distance to analyze retrosynthesis routes designed by SYNTHIA [45]. The goal of model interpretation is to elucidate the decision-making process of complex, high-dimensional ML models, thereby extracting heuristic principles and knowledge pertinent to the domain. Crucial approaches include feature importance analysis, which pinpoints key influencing variables, and interpretability frameworks such as SHAP [46,47] and LIME [48,49], which facilitate the understanding of how models arrive at their decisions.",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 3 AI applications in organic synthesis  \n\nIn the realm of organic synthesis, data-driven methodologies are catalyzing solutions to a multitude of complex challenges, achieving substantial progress in recent years. These issues encompass a vast array of dimensions, from single molecule to intermolecular chemical reactions, and even multi-step transformations in total synthesis. The scope of research in this area is equally comprehensive, involving the prediction of molecular physicochemical properties, the evaluation of structure-activity relationships in organic transformations, and the optimization of reaction conditions. Facing these chemical challenges across diverse scenarios, researchers have applied and developed innovative AI technologies, with key directions highlighted in Figure 3. These successes demonstrate the immense potential of AI within the sphere of organic synthesis. In this section, the representative research advances are discussed to showcase the ability of AI technology in these application scenarios.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 3.1 Molecular property prediction  \n\nThe physicochemical properties of organic molecules dictate how they behave in chemical reactions and influence the evolution of organic transformations [50,51]. Therefore, the accurate comprehension and prediction of molecular properties serve as the backbone for the rationality of organic synthesis. As shown in Table 2, molecular properties can be classified into thermodynamic and kinetic parameters, with data sourced from both experiment and computation. Through the discussion of the highlighted ML studies, this section will elaborate on how ML enables quantitative thermodynamic and kinetic property predictions.  \n\n(1) Prediction of thermodynamic properties  \n\nThermodynamic properties are inherent characteristics of molecules in an equilibrium state that are used as fundamental parameters to assess the thermodynamics of chemical reactions. Traditional approaches for determining thermodynamic parameters entail both experimental methods and quantum chemical computations, which are accurate but also time- and resource-intensive [110,111]. However, since the thermodynamic property is dictated by the molecular structure, it presents a scenario that is well-suited for ML modeling and prediction. This high-dimensional mapping from molecular structure to thermodynamic property can be learned by data-driven approaches, which could lead to much more accurate and efficient thermodynamic parameter prediction than with conventional techniques. In recent years, significant breakthroughs have been seen in the prediction of various important thermodynamic parameters including $\\mathsf{p}K_{\\mathrm{a}}$ , BDE, and others.  \n\n$\\mathsf{p}K_{\\mathrm{a}}$ indicates the degree of proton dissociation from a molecule, which is important to understanding heterolytic $\\mathrm{\\DeltaX{-}H}$ bond cleavage energies [112–116] and plays a critical role in both chemical and medical sciences [57,114–116]. Although quantum mechanical computations have been extensively applied for $\\mathsf{p}K_{\\mathrm{a}}$ evaluation with high accuracy [54– 58], they also suffer from time- and resource-consuming limitations. To achieve the data-driven $\\mathsf{p}K_{\\mathrm{a}}$ prediction, classic ML methods [21,57–65] and graph convolutional neural networks (GCNs) based approaches [66,67] have made tremendous progress. Benefiting from the massive $\\mathsf{p}K_{\\mathrm{a}}$ values in the iBonD database, Luo et al. [21] have reported an NNbased ML model that can predict the overall $\\mathsf{p}K_{\\mathrm{a}}$ value of a given molecule (macro- $\\cdot\\mathsf{p}K_{\\mathrm{a}}^{\\cdot}$ ) with an MAE of $0.87\\mathrm{p}K_{\\mathrm{a}}$ units in various solvents [20]. For micro- $\\cdot\\mathsf{p}K_{\\mathrm{a}}$ of a specific $_\\mathrm{X-H}$ bond, Grzybowski et al. [66] achieved a mean absolute error (MAE) of $2.1~\\mathsf{p}K_{\\mathrm{a}}$ units using a GCN model with a DFTcalculated database, which enabled accurate $\\mathsf{p}K_{\\mathrm{a}}$ prediction of a wide range of $\\mathrm{C-H}$ acids. These strategies have also been extended to the $\\mathsf{p}K_{\\mathrm{a}}$ prediction in protein residues [117,118], which play a crucial role in regulating protein structures and their functions in biological processes.  \n\n![](images/f44d349a58d5f2b6036921ad798200d84c20a7086ae2b56f2baf76436ab78940.jpg)  \nFigure 3 Key directions of AI applications in organic synthesis (color online).  \n\nTable 2 Overview of representative molecular properties and models   \n\n\n<html><body><table><tr><td>Category</td><td> Property</td><td>Data source</td><td>Model</td></tr><tr><td rowspan=\"6\">Thermodynamics</td><td>pKa</td><td>Exp./cal.</td><td>Quantum mechanical calculations [52-56], traditional ML methods [21,57-65], GCN [19,66,67], etc.</td></tr><tr><td>BDE</td><td>Exp./cal.</td><td>Theoretical calculations [68-70], quantitative structure-activity rela- tionship (QSAR) [69-75], graph neural network (GNN)[76,77], spectrum-enhanced methods [78], and other ML methods [79-82].</td></tr><tr><td>Quantum chemical properties (HOMO, LUMO, U, H, G, etc.)</td><td>Cal.</td><td>SchNet [40], PhysNet [83], HMGNN [84], TensorNet [85], ChemRL- GEM [86], Uni-Mol [87], etc.</td></tr><tr><td>Physical chemistry-related properties</td><td>Exp./cal.</td><td>A variety of AI models based on datasets like ESOL [88], FreeSolv [89], Solv@TUM [90], Lipophilicity [91], etc.</td></tr><tr><td>Redox potential</td><td>Exp./cal.</td><td>HOMO/LUMO orbital energy [92], density functional theory (DFT)- calculated descriptors [93], etc.</td></tr><tr><td>Activation energies</td><td>Exp./cal.</td><td>MPNN [94] and hybrid reaction models [95]</td></tr><tr><td rowspan=\"4\">Kinetics</td><td>Rate constant</td><td>Exp.</td><td>Gaussian process regression [96]</td></tr><tr><td>nuclecphiliyt </td><td>Exp./cal.</td><td>Physac</td></tr><tr><td>Potential energy surface (PES)</td><td>Cal.</td><td>Neural networks [104,105], Deep Potential Net [106], CGnets [107],</td></tr><tr><td></td><td></td><td>SchNet[40], △-machine learned PES [108], stochastic surface walking method [109], etc.</td></tr></table></body></html>  \n\nBDE, which involves the homolysis of chemical bonds, reflects the intrinsic bond strength and is critical in a series of chemical transformations. One representative example is the metal-oxo complex-mediated $\\mathrm{C-H}$ activation [114], in which the C–H BDEs are closely related to reaction rates. Typically, BDEs could be determined using experimental methods [119] or theoretical calculations with an MAE of around 2 kcal/mol [68–70]. However, these methods, while precise, are costly and inefficient for large-scale analysis. Over the last two decades, early QSAR studies laid the groundwork for efficient and accurate approaches to evaluating BDEs [69–75]. More recent advancements leveraged highthroughput DFT calculations to generate larger BDE datasets with diverse bond types and advanced ML strategies like GNNs [76,77] and spectrum-enhanced strategies [78], offering high-accuracy BDE predictions [79–82]. It is noted that Paton et al. [81] have reported an appealing GNN model based on approximately $300\\mathrm{k}$ DFT-calculated BDEs, achieving accuracy with an MAE of $0.58\\mathrm{\\kcal/mol}$ when compared with DFT calculations.  \n\nIn addition to $\\mathsf{p}K_{\\mathrm{a}}$ and BDE, the ML modeling of a collection of quantum chemical properties (HOMO/LUMO energies, thermal values like U, H, G, etc.) of molecules has made significant progress thanks to the creation of the quantum machine (QM)-series database [36,37,120–122]. This large-scale database serves as a powerful data engine that stimulated the development of a series of novel AI frameworks for molecular prediction, including SchNet [40], PhysNet [83], HMGNN [84], TensorNet [85], ChemRLGEM [86], and Uni-Mol [87]. These models continued to push the state-of-the-art (SOTA) record of molecular property prediction in the QM-series database, achieving an accuracy comparable to DFT calculations. Aside from the synthetic interest, there has been a long-standing interest in predicting molecular properties that are important for drug and material design. Standard databases such as ESOL [88], FreeSolv [89], Solv $@$ TUM [90], and Lipophilicity [91] have been widely used in developing accurate predictive models to aid in the design and screening of drug-like molecules. Redox potential, on the other hand, is an important parameter in electrochemical behavior and has been modeled using a variety of molecular representations, including HOMO/ LUMO orbital energy [92] and DFT-calculated descriptors",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# [93]. (2) Prediction of kinetic properties  \n\nIn synthetic chemistry, kinetic properties are just as important as thermodynamic properties in determining the practical feasibility of reactions that are theoretically favorable. Their importance extends to critical aspects such as reaction yield, regioselectivity, and stereoselectivity, and they are essential in a variety of processes, including pharmacokinetics [123,124], dynamic kinetic resolution [125], and petroleum cracking [126]. However, the development of kinetic property prediction lags behind that of thermodynamic properties due to the intrinsic complexity and limited data availability [70,127,128].  \n\nReaction rate constants and activation energies are key kinetic properties worthy of ML modeling [129]. In 2020, Green et al. [94] utilized a message-passing neural network model with reaction fingerprints to predict activation energies, achieving an MAE of $1.7\\mathrm{kcal/mol}$ . Using transition state modeling, Buttar et al. [95] predicted the barrier of nucleophilic aromatic substitution processes with an MAE of $0.77\\mathrm{\\kcal/mol}$ . For rate constant prediction, Bowman and colleagues [96] employed Gaussian process regression for rate constant prediction for bimolecular chemical reactions. Greaves et al. [130] reported a multiple linear regression method to predict the rate constant of the reaction between benzyl bromide and pyridine with an $R^{2}$ of 0.92. However, the lack of a substantial rate constant database limits the scope and application of these ML models, highlighting an important subject for future research and data collection efforts.  \n\nAs fundamental concepts in polar chemistry, nucleophilicity $(N)$ and electrophilicity $(E)$ are quantified with rate constants in specific reactions. Particularly, Mayr et al. established the well-known Mayr equation to describe the nucleophilicity and electrophilicity of molecules [131] and then built a database for $N/E$ evaluation in chemical reactions [132]. Several ML modeling attempts have been made based on the empirically known $N/E$ values to forecast the $N/E$ value of novel reagents using physical, topological, or quantum chemical descriptors [97–102] or directly via the GNN model [103]. Recently, Luo et al. [97] developed a holistic model for predicting both $N(R^{2}{=}0.92,\\mathrm{MAE}=1.45)$ and $\\boldsymbol{R}^{2}\\:=\\:0.93$ , $\\mathrm{{MAE}}\\ =\\ 1.45)$ by integrating reactivity structural and physicochemical (rSPOC) descriptors, which was then used to predict the nucleophilicity of a variety of enamine intermediates and $\\mathrm{\\DeltaNAD(P)H}$ .  \n\n(3) Prediction of potential energy surface  \n\nUnlike the thermodynamic and kinetic properties, which are characterized by specific numerical values, ML modeling of potential energy surfaces (PESs) requires capturing the continuous relationship between nuclear coordinates and their corresponding energies. The precise prediction of PES is not only theoretically important but also has great practical significance. The AI potential model has received extensive attention in recent years [104,127,133–135], and it can help us understand and simulate molecular systems [136] and synthetic processes [137,138]. Behler and Parrinello made a seminal contribution to this field in 2007 when they used neural networks to create PES at remarkable speeds and efficiency [105]. This was followed by the introduction of Deep Potential Net in 2017 [106], which achieved quantum chemical precision in generating PESs. Further advancements include Schütt et al.’s use of SchNet for PES prediction and its application in molecular dynamics simulations of small molecules [40] as well as Clementi et al.’s development of CGnets for coarse-grained (CG) molecular modeling [107], extending it to encompass all-atom free energy surfaces in explicit solvation. In recent years, there has been a surge in exciting innovations, such as neural network-based full-dimensional PES constructions for chemical systems [104], $\\Delta$ -machine learned PES enhancing DFT-based PESs to near CCSD(T) accuracy [108], and the enrichment of the PES library with more comprehensive datasets for chemical systems [139]. These developments have paved the way for an increasing number of modern methods exploring PESs of chemical reactions [140]. One representative example of using PES to elaborate synthetic mechanisms is Liu’s study of the mechanism and selectivity of glucose pyrolysis [109]. Using the AI potential model developed by their stochastic surface walking method [141–145], this study detailed an amount of 6,407 elementary reactions and elucidated the mechanistic details and origins of site-selectivity for 5-hydroxymethylfurfural formation.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 3.2 Prediction and optimization of synthetic transformation  \n\nBecause of the massive possibilities of chemical bond cleavage and formation, synthetic transformation inherently poses a multiple-choice question with numerous possible products. Moreover, the issue of synthetic transformation prediction also involves predicting the quantitative outcomes of reactions (yield, selectivity, etc.) and strategizing the synthetic pathways for multistep transformations. These problems are highly amenable to data-driven solutions. In fact, even before the advent of modern artificial intelligence technology, the birth and growth of chemoinformatics encompassed the exploration of using data and programming to address these challenges. In recent years, with the accumulation of large-scale synthetic data and the development of advanced reaction modeling frameworks, this field has seen significant progress. On a range of reaction prediction scenarios, AI has demonstrated promising prospects, even offering judgments that surpass those of human chemists.  \n\n(1) Multistep retrosynthesis planning Computer-assisted synthetic planning (CASP), particularly the strategic planning of multi-step retrosynthesis, represents one of the oldest yet most vibrant challenges in AI synthetic chemistry [146]. The crux of the challenge in retrosynthesis planning lies in the construction of a coherent and reasonable multi-step synthetic network, followed by the execution of an efficient and rational search and scoring process within this network. Finally, the synthesis pathways must be regressed to the available building blocks, ensuring a practical and feasible approach to the synthesis design. To realize the multistep retrosynthesis, a series of innovative algorithm designs have been proposed in recent years. In this regard, Segler et al. [147,148] utilized the Monte Carlo Tree Search (MCTS) algorithm to devise synthetic routes for small organic molecules. Kishimoto et al. [149] introduced the DFPN-E method, integrating depth-first proof-number search (DFPN) with heuristic edge initialization, showcasing a time advantage over the MCTS algorithm with comparable success rates. Chen et al. [150] presented Retro\\*, a neuralbased $\\mathbf{A}^{*}$ -like algorithm, utilizing an AND-OR search tree and an optimal priority search strategy, offering a more efficient approach to searching reaction pathways. Xie et al. [151] presented a graph-based search algorithm called RetroGraph, further enhancing the performance of $\\mathbf{A}^{*}$ -like search algorithms to reduce molecular redundancy in treebased search methods. Kim et al. [152] introduced Retro\\*+, a self-improving framework training a single-step model to emulate successful trajectories, maximizing success rates and leveraging simulated experiences for model enhancement. Yu et al. [153] proposed GRASP, a goal-driven actorcritic method, utilized for seeking routes with specific predefined objectives, such as building block materials. Recently, Liu et al. [154] presented PDVN, a dual-value network planning, constructing two distinct value networks to predict synthesizability and cost, enhancing search success rates, optimizing model invocations, and aiding in identifying shorter synthetic routes.  \n\nWith the above algorithm advancements, reports on computer-aided multi-step route design in chemical synthesis are emerging. The Jensen group [155] employed ASKCOS for multi-step retrosynthetic route design of 15 drug molecules, including (S)-warfarin and safinamide, and validated the synthetic feasibility through a robotic flow chemistry platform. The Grzybowski team [12] demonstrated SYNTHIA’s powerful retrosynthetic design capabilities, passing the Turing test in which chemists cannot differentiate the AIdesigned and the human-designed synthetic routes for the studied compounds. A series of SYNTHIA-predicted routes for natural products are experimentally executed, including challenging targets of $(-)$ -Dauricine, Tacamonidine, and Lamellodysidine A (Figure 4a). It is worth noticing that Tacamonidine and Lamellodysidine A were synthesized for the first time. The Cernak research group [156] utilized SYNTHIA to study 12 potential anti-COVID-19 drugs, experimentally validating four predicted routes for umifenovir and one predicted route for bromhexine, highlighting that automated retrosynthetic predictions can rapidly identify alternative starting material supply chains for pharmaceuticals. Cernak and colleagues [45] further demonstrated that human chemists can harness the heuristic value of AI predictions to achieve out-of-box synthetic innovations. They group-employed SYNTHIA for the retrosynthetic route prediction of $(-)$ -stemoamide. Based on the myriad of SYNTHIA-predicted pathways, they proposed a concept of graph edit distance to quantify the synthetic impact of AIsuggested single-step transformations (Figure 4b). Through this, they were able to realize a remarkable 3-step synthesis of $(-)$ -stemoamide (Figure 4c). Interestingly, the AI tool for retrosynthesis analysis can also be applied in a reversed fashion to guide forward synthetic possibilities. The Grzybowski team [157] utilized the forward-synthesis Allchemy platform to generate a plethora of synthetic networks from approximately 200 commercially recovered waste chemicals. They selected numerous viable synthetic routes and experimentally validated several of them. The continuous reporting of computer-aided multi-step reaction planning, encompassing both algorithm development and experimental applications, underscores the growing significance of this field in the work of synthetic chemists.  \n\n(2) Reactivity prediction of single step transformation  \n\nFor molecular synthesis, although many reactions appear theoretically feasible, the reactions that can actually achieve uniformly high reactivity and selectivity are exceptionally rare [158–160]. More commonly, most reactions only achieve the desired efficiency and selectivity under a delicate combination of substrate, catalyst, and conditions. Therefore, accurate evaluation of the reactivity and selectivity of singlestep transformation is equally crucial for the successful design of molecular synthesis [161,162]. However, due to the vast molecular structural space and the multitude of controlling factors, there is no simple formulaic equation capable of quantitatively describing the universal laws of molecular synthesis. The QSAR of single-step transformation still remains one of the core challenges in AI synthesis [163–165]. Facing this challenge, traditional research has typically relied on experience-driven strategies: by summarizing the available data, synthetic chemists are able to derive a local structure-activity relationship for the specific target, which is then used for the rational design and improvement of synthetic transformation. However, this empirical approach lacks precision and predictive power, and conflicting rules can exist. This situation makes random selection and trial-and-error inevitable in designing and screening actual synthetic explorations.  \n\nRecently, data-driven approaches have brought a new perspective to solve the problem of single-step QSAR prediction [127,166–168]. Benefiting from advanced AI algorithms and rich chemical data, a series of studies have shown that ML models are able to accurately predict reaction yields and selectivities [169–175], even surpassing the judgment of experienced chemists in some cases [12,176]. More importantly, these models can assist chemists in efficiently screening new catalysts for target reactions [177–179], providing powerful AI tools for molecular synthesis. These studies revealed the remarkable potential of ML technology in synthetic chemistry, promising to accelerate the process from the development of synthetic methods to the discovery of functional molecules.  \n\n![](images/06d79cb50797a3627827e224d9dbceb96af6a1640b30109e8c39ab64afc29189.jpg)  \nFigure 4 Representative applications of SYNTHIA. (a) Highlighted complex organic molecules whose SYNTHIA’s predicted synthetic routes have been experimentally verified. (b) Calculation of the graph edit distance between two synthetic intermediates based on bond connections. Reproduced with permission from Ref. [45]. Copyright 2023, American Association for the Advancement of Science. (c) 3-step synthesis of $(-)$ -stemoamide inspired by SYNTHIA (color online).  \n\nFor the palladium-catalyzed Buchwald-Hartwig crosscoupling reactions, Doyle et al. [180] demonstrated the potential of ML in predicting reaction yields. Utilizing a highthroughput synthetic platform, they reliably evaluated the yields of 4,140 reactions comprising a diverse range of substrates, catalysts, additives, and bases (Figure 5a). Through quantum chemistry computations and customized scripts, a series of atomic, molecular, and vibrational descriptors were automatically generated. Employing a random forest regression algorithm, they achieved an $R^{2}$ of 0.92 and a root mean square error (RMSE) of $7.8\\%$ across a $70\\%$ (training) $130\\%$ (validation) data split. Furthermore, the trained ML model is able to predict the outcomes for unseen additives, showcasing the extrapolative predictive power of the established yield model. Interestingly, the model interpretation revealed that the descriptors of isoxazoles were crucial for yield predictions. Following this mechanistic hint, the authors subsequently discovered that the active isoxazoles were able to inhibit palladium’s catalytic activity through oxidative addition. This study, combining highthroughput experimentation with ML modeling, unveiled the attractive potential of data-driven research paradigm for reaction design and screening. It provides a powerful AI tool for evaluating the productivity of Buchwald-Hartwig crosscoupling reactions and enriches the understanding of the reaction mechanism.  \n\nBy merging automation and ML modeling, Liao and colleagues [181] achieved selective Pd-catalyzed functionalization of sterically hindered aromatic meta-C–H bonds. They employed a synergistic protocol combining photoinduced $\\mathrm{C}-$ H carboxylation, carboxy-directed Pd-catalyzed C–H functionalization, and microwave-assisted decarboxylation, using $\\mathrm{CO}_{2}$ as a traceless director for targeted meta C–H functionalization (Figure 5b). Through high-throughput experiments, they efficiently executed 1,032 reactions to explore a remarkable substrate scope, thereby providing comprehensive insights into the reaction’s synthetic potential. With this dataset in hand, they developed a yield prediction model using a message-passing neural network with pre-training from the USPTO dataset, which achieved an $R^{2}$ of 0.750 and an MAE of $7.2\\%$ in 5-fold cross-validation. In addition, this model is able to accurately predict the reaction outcome for unseen substrates, demonstrating significant advantages of high-throughput experimentation and MLassisted yield prediction in exploring novel synthetic reactions.  \n\n![](images/29d796c159a761999347fb8f4776e2b8bbd8762c0272285f6ee3c70074845413.jpg)  \nFigure 5 Selected ML yield prediction studies of organic transformation. (a) ML approach and performance of yield prediction of Pd-catalyzed BuchwaldHartwig cross-coupling reactions. (b) ML approach and performance of yield prediction of Pd-catalyzed functionalization of sterically hindered aromatic meta-C–H bonds (color online).  \n\nDiffering from the complete HTE dataset of chemical spaces, the synthetic exploration in real-world applications tends to be sparse and significantly more diverse in molecular selections. To investigate whether ML models could meet the challenge of predicting such scenarios, Wiest and colleagues [182] extracted and processed the data from AstraZeneca’s ELNs, creating a dataset for Buchwald-Hartwig reactions. This dataset included 781 reactions involving 340 aromatic halides, 260 amines, 24 ligands, 15 bases, and 15 solvents. Moreover, it contained a substantial number of lowyield or nonproductive reactions, with $39.9\\%$ yielding no product. This ELN dataset reflected the reality of synthetic transformation in pharmaceutical applications, presenting a significant challenge for ML modeling. The authors found that all attempted models, including the classic regression algorithms using RDKit features and more advanced YieldBERT [183] model, failed to provide meaningful predictions, with the best model achieving an $R^{2}$ of only 0.266. This finding, contrasting with the success of similar models on HTE datasets, indicated that ML models still need significant improvement in handling real-world synthetic scenarios and highlighted the need for caution in modeling with legacy yield data.  \n\nAlso targeting the challenge of biased distributions in literature data, Glorius et al. [184] noticed the importance of negative data in structure-activity relationship modeling. They found that, despite having up to 190,000 yield data from literature, models still struggled to achieve reliable predictions. Whether using traditional modeling methods or Yield-BERT [183] models, none could provide meaningful regression results, which is consistent with the above study from Wiest. By manipulating the data extraction and including additional random noise, the Glorius group attributed these poor modeling results primarily to the bias in literature data rather than the noise in experimental data. This bias stemmed from both selective sampling of reaction spaces in literature reports and a tendency to publish positive reaction outcomes. To address this issue, the authors proposed two strategies: purposefully conducting additional experiments to gather data on low-performing synthetic space, and data augmentation to help mitigate the issues caused by overly biased sampling. This work further revealed the importance of data distribution in synthetic chemistry modeling, highlighting the critical need for comprehensive, diversified, and fair evaluations and reporting in synthetic investigations.  \n\n(3) Selectivity prediction of single-step transformation  \n\nAs a key component of structure-performance relationships, selectivity is also a crucial target for ML predictions in synthetic chemistry [161,164,166,185,186]. To realize the data-driven prediction of asymmetric catalysis, the Denmark group [187] reported the successful ML application in BINOL phosphoric acid (BPA)-catalyzed asymmetric addition of imines (Figure 6a), demonstrating the advantages of AI in solving stereoselectivity problems. The authors introduced innovative designs in both data selection and ML modeling. For data selection, they proposed a concept called universal training set (UTS), employing the Kennard-Stone algorithm to select chemically representative substances within a space composed of steric and electronic descriptors. This selection method, independent of reaction and mechanistic understanding, is solely based on the physicochemical properties of studied molecules, thereby rendering the chosen BPA set broadly applicable for modeling of BPA-involved transformations. In addition, to accurately characterize the complex steric environment of BPA molecules, a novel stereochemical descriptor called “average steric occupancy”  \n\n(ASO) was developed. This descriptor is based on molecular occupancy at grid points within a cubic lattice: for each grid point, a value of 0 or 1 is assigned based on whether molecules occupy this position. The grid values were subsequently averaged across all conformers to generate the uniformed, high-dimensional ASO descriptor representing the steric environment of the molecule. Integrating these innovative designs, the authors attempted ML predictions of enantioselectivity on a dataset comprising 43 BPAs, 5 imines, and 5 thiols, totaling 1,075 reactions. The constructed neural network model precisely predicted the target enantioselectivity, with a mean absolute deviation (MAD) of about $0.15\\mathrm{\\kcal/mol}$ . Moreover, the model’s reliability was validated in several out-of-sample and out-of-range tasks, accurately predicting unseen catalysts and successfully differentiating superior ones. This work, with the innovative workflow and descriptor designs, provides a key reference for data-driven modeling of stereoselectivity, highlighting the potential of AI technology in addressing asymmetric challenges.  \n\nInterestingly, Sigman and colleagues [188] also explored the stereoselectivity prediction of BPA-catalyzed imine addition reactions from the perspective of multivariate linear regression using physical organic parameters (Figure 6b). They posited that by uncovering the common mechanistic features of all reaction components, a comprehensive understanding of the factors controlling the reactivity and selectivity could be achieved. With this comprehensive set of physical organic controlling factors and leveraging statistical modeling, predictions for different structural motifs within a single model became feasible. For the studied BPA catalysis, the authors systemically parameterized the involved reaction components and catalysts from a physical organic chemistry standpoint, leading to the compilation of 313 parameters expressing steric and electronic effects. Based on this, multivariate linear regressions were made on an enantioselectivity dataset of 367 reactions compiled from relevant literature. The linear model achieved the remarkable performance of $R^{2}$ close to 0.9. Notably, when applied to the exact same dataset published by Denmark [187], Sigman’s model also achieved excellent predictive performance, accurately identifying the selective catalysts. This highlights that the mechanism-based physical organic chemistry parameters can enable powerful QSAR prediction of focal datasets without the usage of sophisticated regression algorithms, which provides an alternative approach for quantitative predictions of stereoselectivity.  \n\n![](images/e8dfdbd7b49eee0b43d773f7deb055e6fb390190cf1effc89ce4cdb698cdf75f.jpg)  \nFigure 6 Selected ML enantioselectivity prediction studies of chiral phosphoric acid-catalyzed imine addition. (a) Data distribution, molecular descriptors with the design of ASO, and model performances. (b) Data distribution, physical organic descriptors, and the model performances using the multivariate linear regression approach (color online).  \n\nExciting advances in stereoselectivity prediction were also made for transition metal catalysis [165,189,190]. Focusing on the asymmetric hydrogenation of olefins [189], Hong and colleagues [191] reported a productive ML modeling study. Due to the highly sparse and biased nature of the selected datasets from literature, a novel modeling strategy called “hierarchical learning” was proposed to overcome the bias and achieve extrapolative prediction. The core idea is to view the structure-selectivity relationship as a superposition of a universal relationship and local perturbations. A base model representing the universal structure-activity relationship is learned through the representative data samplings, followed by training a delta model with the neighboring data close to the target reaction, thus learning the perturbations of the relationship. The superposition of layered models yields the final prediction, which can be considered as an approach to transfer learning. This transfer learning strategy achieved excellent prediction in the asymmetric hydrogenation of olefins, requiring only limited reaction data of the target alkene substrate for satisfying modeling. The collaboration between Hong and Ackermann further applied the hierarchical learning strategy to explore the holistic synthetic space of electrochemical Pd-catalyzed $\\mathrm{C-H}$ alkenylation (Figure 7a) [192], systematically studying the enantioselectivities of 846,720 reaction combinations, which demonstrated the appealing advantages of data-driven method in achieving the comprehensive knowledge of synthetic space. They also utilized this transfer learning protocol in virtual catalyst screening for asymmetric Co-catalyzed $\\mathrm{C-H}$ alkenylation, which successfully predicted and verified an intriguing chiral carboxylic acid with excellent enantioselectivity [193].  \n\nIn addition to enantioselectivity, ML modeling has also been applied to other categories of stereoselectivity [172,194,195]. One representative study is Grzybowski’s work [194] in Diels-Alder reaction (Figure 7b). Using physical organic descriptors, the authors successfully predicted the major regio-, site-, and diastereoisomers using ML modeling. They found that using physical organic descriptors, as opposed to naive molecular fingerprints, significantly improved the model performance. By capturing electronic effects with Hammett constants and steric properties with TSEI indices, the chemical descriptors combined with a random forest classifier achieved an excellent prediction accuracy for regio- $(93.6\\%)$ , site- $(91.3\\%)$ , and diastereoselectivities $(89.2\\%)$ . The authors further demonstrated that the prediction performance of the Hammett-TSEI-based random forest classifier received less effect by the dataset partitioning compared to other encodings, indicating that the physical organic descriptors can enable the model to learn the organic structure-performance relationship and accurately predict outcomes for compounds unseen during model training.  \n\nRegioselectivity prediction has also been realized using ML methods, as evidenced by a series of exciting advances in recent years [194,196–199]. The Hong group [197] has conducted ML studies on the regioselectivity of radical C–H functionalization of arenes (Figure 8a). Based on previous mechanistic understandings [200], they systematically computed the DFT barriers of the rate-determining step for a myriad of substrates, obtaining regioselectivity data for 9,438 reactions. They found that the physical organic descriptor, with only a few dozen dimensions, achieved satisfying regression results comparable to other typical higher-dimensional descriptors (smooth overlap of atomic positions (SOAP), atom-centered symmetry functions (ACSF), etc.). The trained random forest model accurately predicted the reaction sites with $94.2\\%$ accuracy and determined the degree of selectivity with $89.9\\%$ accuracy. Subsequently, the model’s predictions were compared with reported experimental results on complex polysubstituted aromatics. Despite being trained only on DFT data and not having been exposed to the experimental complex compounds, the model still performed with convincing accuracy. This work not only demonstrates that the DFT computation can provide a reliable data source for ML modeling of selectivity problems and can be directly applied to experimental prediction and verification, but emphasizes the importance of local physical organic descriptors of reaction sites in regioselectivity modeling.  \n\nJensen and colleagues [198] advanced the prediction modeling of regioselectivity for synthetic transformations, including aromatic $\\mathrm{C-H}$ functionalization and $\\operatorname{C-X}$ substitution. In their work, the implicit molecular representations derived from ML were combined with explicit quantum chemical properties (Figure 8b). The machine-learned molecular representation was realized by a GNN based on the Weisfeiler-Lehman network framework. Quantum chemical descriptors of organic molecules (atomic charges, Fukui indices, nuclear magnetic resonance (NMR) shielding constants, etc.) were calculated at the B3LYP/def2-SVP level using GFN2-xTB optimized structures. By combining these two types of molecular representations, they developed an ML model that accurately predicts the regioselectivity of the target reactions. To circumvent the time- and resource-consuming quantum chemical calculations, they demonstrated the appealing potential of combining multiple ML models. For this, they trained a directed message-passing neural network to predict QM properties of molecules, using these predictions instead of DFT-computed parameters as input for the selectivity model. This strategy provided an end-to-end model that can predict selectivity from SMILES within milliseconds. The evaluation showed that this fusion model achieved an accuracy of $89.7\\%$ for aromatic C–H functionalization reactions, $96.7\\%$ for aromatic $\\operatorname{C-X}$ substitution reactions, and $97.2\\%$ for other substitution reactions. This work illustrates the complementary nature of data-driven representation and quantum chemical parameters for molecular encoding, while also highlighting the potential of onthe-fly quantum chemical property prediction and derived reactivity/selectivity modeling in synthetic chemistry.  \n\n![](images/ac87c7f3cd9d462f7d9f678e71998ffa4730b314eeb3af97073449a69a255be3.jpg)  \nFigure 7 Selected ML stereoselectivity prediction studies of Pd-catalyzed $\\mathrm{C-H}$ alkenylation and Diels-Alder reaction. (a) Descriptor design, ML approach, and the model performances and predictions of the enantioselectivities of pallada-electrocatalyzed $\\mathrm{C-H}$ activation. (b) Descriptor design, ML approach, and the model performances of the regio-, site-, and diastereoselectivities of Diels-Alder reaction (color online).  \n\nHartwig and colleagues [201] successfully merged expert rules with data modeling to predict the regioselectivity of Ircatalyzed C–H borylation reactions (Figure 8c). They combined literature results with specifically sampled low-selectivity data and representative intermolecular competition experiments, forming a data set for regioselectivity training. In selectivity modeling, they combined computational chemistry, data-driven approaches, and expert experience. Starting with a rough estimation of reaction activation barriers using the xTB method, they combined it with a partial least squares (PLS) model to predict the regioselectivity. Considering the limited scope of modeling data, they further implemented an expert rule to express the influence of neighboring substituents. Combining model predictions with rule-based corrections, they provided a predictive model for evaluating borylation sites. This approach maximized the benefits of computation, modeling, and expert experience, resulting in a highly effective selectivity prediction model. The model’s predictions aligned well with experimental verification across various compounds, which was also compared with predictions from experienced human chemists, outperforming them in tests on a few showcase complex compounds. This study demonstrates the complementary nature of human expertise and ML modeling, showing how expert rules can enhance and improve the predictive capabilities of ML models.  \n\n![](images/57132dc74496cdeda3e12e97cbc9b42aa6416fe9d88441a0db1dee076224c264.jpg)  \nFigure 8 Selected ML regioselectivity prediction studies of organic transformation. (a) Descriptor design and ML performances of radical C–H functionalization of arenes. Reproduced with permission from Ref. [197]. Copyright 2020, John Wiley $\\&$ Sons. (b) Regioselectivity prediction model of aromatic C–H functionalization and $\\mathrm{C-}\\mathrm{X}$ substitution that combines the machine-learned representation by GNN and the calculated atomic descriptors. Reproduced with permission from Ref. [198]. Copyright 2021, Royal Society of Chemistry. (c) Regioselectivity prediction model of Ir-catalyzed $\\mathrm{C-H}$ borylation that combines the xTB calculation, the ML regression, and the expert rule for neighboring substituent influence (color online).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# (4) Reaction optimization  \n\nData-driven reaction optimization allows an effective strategy to accelerate the discovery and improvement of synthetic processes by providing actionable recommendations for reaction conditions. This is an optimization problem in a defined chemical space, which does not fall into the category of regression or classification, necessitating an iterative workflow with experimental testing for correct and complete predictions in the face of chemical nuances. Traditionally, reaction optimization relies on chemists’ knowledge and design of experiment (DoE) methods, which, though automatable, do not harness the statistical value of the accumulated data and demand significant experiment efforts. In addition, the efficacy of these models relies heavily on the quality of the training data. Beker et al. [202] argued that noise and bias in literature data could hinder the creation of models that surpass literature popularity trends, emphasizing the importance of high-quality training data.  \n\nIn 2018, the Aspuru-Guzik group [203] introduced Phoenics, an algorithm using Bayesian optimization for global optimization in chemical experimentation. Phoenics proposes new conditions based on previous observations, efficiently identifying optimal conditions and demonstrating applicability in complex case studies like the Oregonator, a nonlinear chemical reaction network. Sunoj and colleagues [204] developed an ML model for discovering catalysts in asymmetric hydrogenation, accurately predicting enantiomeric excess with an RMSE of $8.4\\pm1.8$ using molecular parameters from 368 substrate-catalyst combinations. The model successfully predicted out-of-sample data, indicating potential for catalyst discovery and substrate selection. In 2021, Doyle, Adams, and colleagues [176] reported a Bayesian reaction optimization framework integrating algorithms into daily lab practices. They applied Bayesian optimization to Mitsunobu and deoxyfluorination reactions, enabling more efficient synthesis of value-added compounds through data-driven experimental decisions. Wang and colleagues [205] used ML to accelerate $\\mathrm{{Cu}}$ catalyst discovery and optimization for $\\mathrm{CO}_{2}$ reduction, identifying critical features and facilitating catalyst design and validation. In addition, the ML-assisted reaction optimization extends to materials. Norquist et al. [206] used support vector machine (SVM) for an ML-assisted materials discovery from failed experiments. Cooper’s group [207] integrated robotic experimentation and high-throughput computation to explore high-activity linear polymers for hydrogen evolution photocatalysts. It is also demonstrated that the ML model can recommend new reactions and generate hypotheses about crystal formation, emphasizing its versatility beyond traditional organic synthesis.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 4 AI applications in polymer synthesis  \n\nAs key substances in the fields of molecular science and functional materials, the AI application in polymer synthesis has received wide interest and significant progress in recent years. Unlike small molecules with well-defined structures, polymers’ continuous molecular structure adds more possibilities in terms of structure and functionality. However, this also brings new challenges for data modeling. These challenges manifest both in how to represent the molecular structure of polymers in a data-driven format for ML models and in how to rationally establish quantitative relationships between the polymer synthesis process and the structure/ properties of the generated polymers. Furthermore, biomacromolecules like proteins and DNA are naturally programmable macromolecular machines. Addressing the synthesis of such biomacromolecules through data-driven solutions is not only a focal point of synthetic interest but also forms a key component in the field of bioinformatics. This section delves into the research on AI applications in polymer synthesis, with key directions highlighted in Figure 9. It aims to reveal the new opportunities AI brings to this field, as illustrated through discussions on representative works.",
+        "category": " Introduction"
+    },
+    {
+        "id": 12,
+        "chunk": "# 4.1 Structure-property relationship prediction of polymer  \n\nPolymers constitute a significant class of materials that are ubiquitous, with applications spanning from daily products, including plastics and rubbers, to cutting-edge high-tech products in electronics, photonics, and biomedicines [208]. The highly tunable functionality of polymers arises from their remarkable diversity at both microscales (e.g., chemical composition, atomic-level connectivity) and macroscales (e.g., crystallinity, phase separation) [209]. Nevertheless, the vast and complex chemical and morphological spaces hinder the discovery of novel polymeric materials for specific purposes.  \n\nMaterials science has witnessed transformative advancements through the integration of ML into polymer property prediction. ML techniques are able to leverage pre-existing experimental data and computational data from first-principles calculations or molecular dynamic simulations, establishing models for rapid and accurate predictions of the properties of new polymer materials [210]. The initial step in modeling the structure-property prediction of polymers involves defining their representation at atomic/molecular levels [211]. However, traditional text-based representations are labor-intensive, computationally demanding, and lack adaptability to diverse polymer classes. These drawbacks hinder the development of AI/ML pipelines for highthroughput applications. In parallel, it is also non-trivial to efficiently probe existing databases for further discoveries. Advanced ML frameworks provide promising prospects for bridging the gap by exploiting available data.  \n\nAs illustrated in Figure 10a, graph-based representations, which directly capture topological information of chemical structures, show favorability for property prediction tasks of polymers. Simine et al. [212] predicted ultraviolet-visible (UV-vis) spectroscopy of conjugated polymers directly from CG representations via a deep-learning model of long-shortterm memory recurrent neural network. The approach demonstrated the potential to investigate organic optoelectronics through computational experiments invoking CG representations. Wang and colleagues [213] utilized CG representations to construct a high-dimensional design space. Bayesian optimization process efficiently explored this continuous space, offering comprehensive insights into molecular-level relationships influencing the lithium conductivity of polymer electrolytes. More recently, Aldeghi et al. [214] introduced a graph representation of molecular ensembles that captured key features including monomer compositions and chain architectures, using a weighted directed message-passing neural network tailored for polymer property prediction. The platform established a database of over 40,000 possible copolymers via calculation of electron affinity and ionization potential and achieved superior accuracy than off-the-shelf material informatics methods.  \n\nThe Ramprasad group [209,215] constituted a userfriendly structure-property prediction platform named “Polymer Genome”. The informatics platform leveraged three hierarchical levels of fingerprints to capture features critical to describe a specific polymer property, which spanned from three-atom fragments, descriptors of the quantitative structure-property relationship type, to morphological descriptors such as the fraction of side-chain atoms (Figure 10b) [208]. Researchers utilized ML algorithms based on Gaussian process regression to generate prediction models that were implemented in the online platform “Polymer Genome”.  \n\nFingerprints as inputs for predictive models tend to attain the relatively best performance [216]. However, hierarchical handcrafted fingerprints, necessitating chemical intuition, consume an amount of time due to complicated computations for model training and inference. Recent advancements in NLP have established Transformer as a powerful AI framework for language modeling. SMILES strings, considered the “chemical language” of polymers, entitle Transformerbased models to the opportunity for application in polymer science. Xu and colleagues [217] introduced TransPolymer, a Transformer-based model benefitting from pretraining on a large unlabeled dataset. This model showcased the importance of chemical awareness in modeling polymer sequences, affording a robust tool for structural-property relationship exploration. Similarly, Kuenneth et al. [218] trained polyBERT on 100 million polymer SMILES strings of hypothetical polymers to function as a chemical linguist. Integrated into multitask deep neural networks, the fully machine-learned polyBERT fingerprints predicted polymer properties at unparalleled speed with unimpaired accuracy, surpassing the SOTA record of handcrafted Polymer Genome fingerprints (Figure 10c).  \n\n![](images/1cdd67c69c6eaa4040e72edb3d787794dccc33c2555643156d51bc3c9d919b32.jpg)  \nFigure 9 Key directions of AI applications in polymer synthesis (color online).  \n\n![](images/d05ab5439b8be0f3386f989be40f2b7bf8c55ff14cea36d52912ab1196e91c1b.jpg)  \nFigure 10 Illustration of (a) graph-based representations and (b) Transformer-based models favorable for structure-property relationship prediction of polymers (color online).  \n\nDeep-learning architectures have revolutionized structureproperty prediction of polymers by automatically learning expressive representations (Figure 11a). Rahman et al. [219] proposed a CNN-based framework that predicted the critical mechanical property, namely pullout force, of carbon nanotube-polymer interfaces. Park et al. [220] utilized GCNs for predicting the thermal and mechanical properties of polymers. They found that GCNs, especially when combined with neural network regression, could slightly outperform the widely used extended-connectivity circular fingerprint (ECFP) representation.  \n\n![](images/579d7c79d128d6678cd704fe4e0e89555747a2a8e694df1e5f4c7d064506612b.jpg)  \nFigure 11 Schematic representation of (a) deep-learning architectures and (b) transfer learning-based frameworks for polymer property prediction (color online).  \n\nIn addition to the structure-property relationship prediction, correlations between chemical, electronic, mechanical, and thermodynamic properties offer alternative avenues for effective property prediction models. Transfer learning leveraging models based on interrelated properties proves promising for predicting target properties even with minimal data (Figure 11b). The Yoshida group [221] developed XenonPy.MDL, a pretrained model library with over 140,000 models for diverse properties of organic small molecules, polymers, and inorganic materials. Their frameworks, exemplified by neural network models, demonstrated efficient property prediction for extremely small datasets. Through a multi-fidelity fusion strategy that addresses the limitation of experimental data in quantity and diversity, the Ramprasad group [222] trained the model on the low-fidelity but abundant data set employing group contribution methods to predict polymer crystallinity under high-fidelity accuracy. Later, the same group [223] advocated multi-task learning by exploiting intercorrelations between various property datasets, yielding efficient, scalable, and interpretable models for polymer property prediction.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 4.2 Target-orientated design of polymer  \n\nIn addition to the forward structure-property relationship prediction, it would be ideal to inverse design the desired polymer with target property. This concept of inverse design presents a novel paradigm, departing from the traditional Edisonian method, which accompanies time- and labor-intensive exploration reliant on human intuition with inherent biases and knowledge limitations. This approach enables generating polymers with superior functionality or properties by navigating the chemical space informed by data-driven strategies. Two avenues, high-throughput screening and advanced ML algorithms, are recognized as pivotal protocols to achieve the target-oriented polymer design (Figure 12).  \n\nIn the context of high-throughput screening, researchers should narrow the chemical space by defining the inputs of polymer fragments and adjoining rules based on their prior knowledge and chemical intuition, which would simultaneously ensure the validation of combining building blocks. For example, the Ramprasad group leveraged a polymer database derived from first principles, exploring the linear combination of 7 basic building blocks to recommend novel dielectric polymers [224]. In a similar manner, Afzal et al. [225] identified polyimides with exceptional refractive index values via high-throughput virtual screening, which could access a massive library of polyimide structures composed of 29 building blocks. However, integrating polymer fragments as inputs is prone to neglecting interaction between polymer chains and other influential factors in realistic production.  \n\nActive learning and the derived AI-driven space exploration have also been utilized in the search for polymer candidates. Bayesian optimization, a noise-tolerant and global optimization strategy free from assumptions of functional forms, has also been implemented in polymer design. The workflow utilized by Wu et al. [226] overcame the challenge of limited data by incorporating transfer learning coupled with BO process. The approach empowered attaining quantitative structure-property relationships for thermal conductivity, which provided candidates possessing comparable thermal conductivities to those of SOTA non-composite thermo-plastics. Kim et al. [227] employed the genetic algorithm process that mimics the natural selection, creating over 100 novel polymers with a high glass transition temperature $(T_{\\mathrm{g}})>500\\:\\mathrm{K}$ and bandgap $(E_{\\mathrm{g}})>6\\mathrm{eV}$ , which are suitable for dielectric materials for high-temperature capacitors. Moreover, researchers suggested that optimized GA parameters and the biased initial population with prior knowledge could significantly improve the GA scheme. Zhou et al. [228] demonstrated that a non-periodic and nonintuitive sequence of PE-PP copolymers, which was generated through the genetic algorithm, outperformed regular block copolymers in thermal conductivity. Atomistic molecular dynamics then performed the fitness evaluation of each candidate by measuring its thermal conductivity.  \n\n![](images/fdf6c6ae366c0285217b40deb0f75eff9e2e4b1c6b9ecd7466577727b3103692.jpg)  \nFigure 12 Schematic representation of high-throughput screening and advanced ML algorithms for target-oriented polymers (color online)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 4.3 Design and optimization of polymer synthesis  \n\nThe advent of synthetic plastics in the last century revolutionized the chemical industry and the world at large. Polymer materials are now ubiquitous in our daily lives. However, traditional polymer synthesis is a process fraught with trial and error. Polymerization condition optimizing and catalyst screening are time- and resource-consuming endeavors. Moreover, this trial-and-error approach generates a significant amount of chemical waste, posing environmental concerns.  \n\nOptimizing polymerization conditions is not a simple task with a singular focus. Chemists often need to balance parameters like chemical composition, molecular weight (MW), and dispersity $\\mathbf{\\eta}(\\mathcal{P})$ for superior material properties. This multi-parameter, multi-objective optimization is a monumental task, compounded by the complexity of high-dimensional data, which often hinders chemists from precisely attaining diverse polymer targets. From this perspective, the potential for implementing AI and ML in polymer synthesis is enormous. By employing advanced data analysis techniques and predictive models, AI can assist scientists in rapidly identifying optimal polymerization conditions and catalysts, thereby reducing the cycle of experiments and saving time significantly.  \n\nHowever, the application of AI in polymer synthesis has been slower compared with its usage in optimizing small molecule organic synthesis. A primary reason is the lack of sufficient high-quality data in polymer research. The scarcity of data stems from the complexity of the polymerization process: The multi-parametric conditions and intricate polymerization mechanisms make computational simulations challenging, rendering simulated data unavailable. Additionally, stringent and sensitive polymerization conditions lead to significant variability in outcomes between different batches. These issues of data limitation pose challenges for ML modeling of polymer synthesis. Therefore, one of the key tasks for data-driven modeling of polymer synthesis relies on the acquisition of large quantities of highquality, repeatable, and interpretable data that adhere to the FAIR (Findable, Accessible, Interoperable, and Reusable) principles [229].  \n\nOne way to obtain data is searching from handbooks or literature. However, inconsistent and sometimes even contradictory results across different publications are not uncommon. High-throughput computational simulations or virtual screening is another approach. However, this approach highly depends on the computational power and is still challenging to predict experimental outcomes in a quantitative manner, especially for polymer synthesis. Highthroughput experiment is a viable approach ensuring experimental consistency but relies on automation and is not suitable for experiments with long measurement times or complex material handling steps.  \n\nFlow chemistry is currently the primary choice in AI-assisted polymerization processes optimization for its ability of real-time monitoring, time-dependent data acquisition on polymer MW and monomer conversion. For example, Junkers and colleagues developed an automated flow synthesis platform for polymer synthesis, coupled with real-time monitoring using gel permeation chromatography (GPC) [230], NMR [231], and Fourier-transform infrared spectroscopy [232]. This platform enables rapid and efficient screening of reaction parameters, including residence time, monomer concentration, polymerization degree, reaction temperature, and monomer conversion rate. They used single-objective ML optimization algorithms to dynamically adjust reaction parameters, optimizing the reaction to precisely control MW or monomer conversion rate, leading to significantly reduced experimental cycles and development time. To achieve multi-objective closed-loop optimization of polymer synthesis, Warren and colleagues demonstrated an ML-assisted automated flow polymerization synthesis platform that can autonomously determine optimal polymerization reaction conditions toward predetermined polymer properties [233]. It features a computer-controlled flow reactor that autonomously polymerizes, using real-time NMR and GPC for polymer characterization. This platform utilizes the Thompson Sampling Efficient Multi-Objective Optimization (TSEMO) algorithm to optimize reversible addition– fragmentation chain transfer (RAFT) polymerization of different monomers, exploring the trade-off between $\\boldsymbol{\\mathcal{P}}$ and monomer conversion rate. Hartman and colleagues [234] also combined automated microfluidics with ML to explore the reaction space of olefin free radical polymerization catalysts, accelerating the discovery of optimal catalytic efficiency conditions.  \n\nIn analyzing the relationship between polymerization parameters and outcomes, Chen and colleagues [235] developed an ML-assisted systematic polymerization planning (SPP) platform for intelligent control of polymer MW and $\\boldsymbol{\\mathcal{P}}$ . They constructed an ML model to analyze and optimize the reversible deactivation free radical polymerization process, combining multivariate analysis to uncover complex interactions between polymerization conditions for optimal polymerization condition prediction (Figure 13). Wilson and colleagues [236] also employed active learning and Bayesian optimization algorithms to accelerate the optimization of electrochemical atom transfer free radical polymerization reactions, which significantly improved the experiment efficiency.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 4.4 End-to-end prediction of polymerization  \n\nOptimization of polymer conditions or catalysts for desired MW and $\\mathcal{P}$ , however, is often not the end of polymer synthesis in real-world practices. The ultimate goal of AIassisted polymer synthesis, as previously mentioned, is to identify targeted (multi-)functions from high dimensional, enormous chemical spaces, elucidate the hidden structurefunction relationships, and accelerate material design. Thus, many laboratories in recent years have been dedicated to the development of closed-loop high-throughput “designsynthesis-test-learn” toward end-to-end AI-assisted prediction from polymer synthesis to properties/functions. This approach, again, highly relies on robust high-throughput polymer synthesis platform amenable to automation and data digitalization for successive AI/ML.  \n\nThere are two primary strategies for high-throughput polymer synthesis, namely parallel copolymerization of various monomers and post-polymerization modifications. For the parallel copolymerization approach, the main challenges include: (1) polymerization reactions that are sensitive to moisture and/or air, increasing difficulties for automated liquid handling systems; (2) poor polymerization control, resulting in low repeatability and predictability; (3) limited flexibility in structural units, restricting monomer types and chemical space; (4) complex and inefficient posttreatment operations, difficult to pursue high throughput. To tackle these challenges, researchers have developed various water- and oxygen-resistant controlled free radical polymerization platforms, such as Enz-RAFT [237–240], oxygen-tolerant atom transfer radical polymerization (ATRP) [241], PET (photoinduced electron/energy transfer)-RAFT [242,243], and others [244–248], most of which overcome these issues and enable controlled high-throughput preparation of polymers. The second strategy is based on postpolymerization modification, which has been one of the primary methods for preparing high-throughput polymer libraries in recent years [249]. Efficient Huisgen cycloaddition [250], activated ester-amine coupling, thiol–ene reactions [251], and Michael addition are the most commonly used post-polymerization modification methods. The challenge with this strategy lies in the typically poor water solubility, instability, and difficulty in long-term storage of the precursor polymers.  \n\n![](images/848729b3ad7913388abf66c0356fe74fb865f2be7415dfa7e03a28201719e902.jpg)  \nFigure 13 An ML-assisted systematical polymerization planning (SPP) platform for polymer inverse design. Reproduced with permission from Ref. [235]. Copyright 2021, Science China Press (color online).  \n\nFor efficient discovery of polymers with certain functions, quick and convenient polymer purification methods are also needed in addition to high-throughput synthetic techniques. Gormley’s group [252] developed a gel filtration chromatography technique that rapidly and high-throughput purifies polymers, with over $95\\%$ removal of small molecule impurities and about $85\\%$ retention rate for 32 types of polymers. However, many polymer purification strategies (such as precipitation, extraction, and chromatographic separation) often depend on specific properties of the target polymers [253,254]. And due to the complexity of these processes, the purification step was sometimes skipped in some cases.  \n\nOnce a vast amount of structural and informational data were successfully generated through the high-throughput synthesis and characterization methods, the next key issue is how to effectively mine these data to guide new material design. Applying ML to identify key features from past data can guide studies on material structure-function relationships [255,256]. For instance, Reineke and colleagues [43,257] combined polymer design with parallel experimental workflows to discover efficient polymers for intracellular ribonucleoprotein (RNP) delivery. Utilizing interpretable ML, they computed SHAP (Shapley additive explanations) for nine polymorphic features, uncovering the structure-function relationship behind editing efficiency, cytotoxicity, and RNP uptake, providing guidelines for designing polymer libraries based on RNP delivery. Bao et al. [258] reported an MLassisted method that guides the design of full-color tunable emission trans-space charge transfer through-space charge transfer (TSCT) polymers. They synthesized 71 different chain length and type styrene polymers through ATRP, building Maximum Likelihood Expectation Multivariate Linear Regression (MLREM) and Bayesian Regularized Artificial Neural Network (BRANNLP) models to predict the photophysical properties of unknown TSCT polymers, exploring the relationship between structure and function. Olsen et al. [259] used high-throughput synthesis techniques to create a large library of 642 polyesters and polycarbonates, while developing a high-throughput clean area biodegradation test to assess the biodegradability of the polymers. They used ML models to interpret the structure-property relationships of polymer biodegradability. Knight and colleagues [260] designed and synthesized a series of polymers containing novel triphenylphosphine acrylamide monomers, using ML regression models to study the relationship between polymer properties and polymerization catalysis rates.  \n\nIn recent years, the ML-assisted closed-loop HTE has shown immense potential in the discovery of new materials [261–263] (Figure 14a). For example, Leibfarth and colleagues [264] combined ML with flow polymerization, enhancing the magnetic resonance signal strength of fluorinated polymers through only about 300 experiments and discovering previously unreported structure-effect relationships (Figure 14b). Gormley et al. [265], through a closed-loop high-throughput polymerization and active learning strategy, rapidly discovered polymers for neuroregeneration research that could protect proteins, as well as designed stable proteinase-active random copolymers [266] (Figure 14c). Lu and colleagues [267] established a high-throughput postpolymerization modification platform for selenium-containing polypeptides synthesis. By incorporating ML algorithms, they were able to efficiently explore the functional chemical space of 600 random copolymers for desired functions such as enzyme-like catalysis without much prior knowledge in four days (Figure 15). It is foreseeable that the deep integration of high-throughput technology and ML will have a significant impact on polymers and will aid in accelerating the discovery of materials in key areas.  \n\n![](images/d0e11146405a8f9be73b0fc041bc801bb0c11794ba32affb357c7604b8ae538f.jpg)  \nFigure 14 (a) An ML-assisted design-build-test-learn closed-loop pipeline for the evolution of polymers. (b) Active-learning-guided discovery of copolymer $^{19}\\mathrm{F}$ MRI agents. Reproduced with permission from Ref. [264]. Copyright 2021, American Chemical Society. (c) Closed-loop design-build-test-learn process for the design of polymer–protein hybrids. Reproduced with permission from Ref. [266]. Copyright 2022, John Wiley & Sons (color online).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 4.5 AI Application in biological macromolecules  \n\nAs mentioned previously, synthetic polymers are highly heterogeneous whose structural information is hard to encode. By contrast, biological macromolecules (such as nucleic acids and proteins) are highly programmable, which provides an exciting arena for AI application. All the details about their structures and functions are conveniently encoded in sequences and facilely manipulated by a set of biochemical tools. The structure-property relationship can thus be deduced from the mapping between sequence and function. Consequently, molecular engineering of biopolymers is usually accomplished with precise sequence variation. The astronomically large sequence space inevitably brings in unparalleled complexity and “the curse of dimensionality” in research and engineering. In view of the enormous biological data accumulated over the past decades (e.g., PDB, UniProt, UniClust, BFD), it is an ideal scenario for the use of AI. To date, the application of AI has already transformed many fields of bio-macromolecular research, particularly in protein sciences such as protein structure prediction, de novo protein design, and protein engineering.  \n\nProteins perform functions through their native structures. The Anfinsen’s dogma postulates that the native structure of one protein is determined only by the amino acid sequence as the thermodynamically most stable structure. The structure prediction thus composes the “protein folding problem”. Classically, this is accomplished by developing a reliable energy function and efficient conformational sampling protocol, as exemplified by the Rosetta software. The advent of AI-based methods pushed the structural modeling quality to approach that of experimental accuracy, resulting in a 1000- fold increase in structural data [268]. AlphaFold2 [9] and RoseTTAFold [269] learn evolutionary information from multiple sequence alignments. The use of protein language models such as ESMFold overcomes the limitation to generalize across protein families and facilitated atomic level prediction from single sequences [270]. While certain limitations remain, such as overpresentation of proteins in spite of missing features (cofactors, post-translational modifications, partners), insensitiveness to mutations, and incapability of generating dynamic ensembles, protein structure prediction seems a largely solved challenge. Predicting function from sequence using ML has also been demonstrated by assigning the enzyme commission (EC) number for a given sequence [271]. The availability of more structures further allows genome mining based on structures using tools like Foldseek [272]. These tools greatly expand our knowledge about proteins.  \n\n![](images/6ae0c08048e83d04d21c10cf312d4b91956d09276d8cf3fd001f356bda65c114.jpg)  \nFigure 15 (a) Closed-loop optimization of GPx activity of the heteropolypeptides via high throughput synthesis and machine learning. (b) Structure of the seven selected organohalides for heteropolypeptides library generation and aim of optimization. (c) $\\mathrm{GPx}$ -like activity of RHPs in each iteration via random searching (blue) or Bayesian optimization (red). (d) Data validation within a plate $(n=8)$ ) and between two different plates. RHPs with low (lanes 1–3) and high (lanes 4–7) GPx-like activities from the database ere selected for validation. The dots on the right and left side in each lane represent the results from different plates. The black central lines and error bars in each lan t the mean and s.d. The coloured line in each lane is the original activity of the RHP from the database.Reproduced with permission from Ref. [267]. Copyright 2023, Nature Publishing Group (color online).  \n\nThe “inverse folding problem” of protein design aims at finding amino acid sequences that fold selectively into a desired “target” structure. More broadly, de novo protein design focuses on generating structures new to our knowledge or accomplishing functions (e.g., binding, fluorescence, catalysis) new to the scaffold. Currently, there are mainly two approaches to design, namely, data-driven and physicsinspired. The former relies on sequence features that can be extracted and leveraged by various neural network-based generative models, such as UniRep [273], ProGen [274], ESM-1b [275], ProViz [276], ProtTrans [277], and ProteinBERT [278], for structure or sequence generation. The latter combines free energy calculation, binding affinity calculation, or conformational entropy estimation with sequence variation for de novo design toward a target structure/function. It includes force-field-based methods like Rosetta [279] and FoldX [280] and ML-based tools like ABACUS [281] and ProteinMPNN [282]. To evaluate the designability of a protein fold, a backbone centered energy function of neural network, SCUBA [283], was developed. When the target structure is partially/fully absent, hallucination protocols can be employed based on trDesign [284], RFdiffusion [285], and Chroma [286]. In addition, it is also possible to perform controllable generation of proteins directly at the sequence level. The convergence of these two complementary approaches has proven synergistic and powerful in achieving hard goals such as de novo enzyme design [287,288]. The problem of these methods is the relatively low success rate, which mandates labor-intensive screening of hundreds to thousands of designs for validation. This challenge may be ameliorated by high-throughput robotic automation. While some of the obtained structures can agree precisely with the design at the atomic level, it is often difficult to gain the desired function with high activity as designed, which necessitates further rounds of directed evolution.  \n\nDirected evolution comprises two steps: library generation and property screening. Traditionally, directed evolution takes an uphill hike on the protein fitness landscape by accumulating beneficial mutations over rounds of mutation/ screening. With high-throughput sequencing techniques and low-cost assay methods, the information about otherwise discarded suboptimal mutants can also be used to train ML models to capture the sequence-function relationship. When meaningful features are included in the representations, simple ML models such as linear regression or shallow neural network could work well, especially for those with highly correlated local mutations [289–292]. State-of-the-art protein language models can be pre-trained on sequences from all protein families and fine-tuned with multiple sequence alignments of homologues so as to be more taskspecific [275]. Notably, the limited number of experimental assays (often ${<}100\\mathrm{\\Omega}$ ) presents a considerable challenge for high-accuracy prediction using ML models. To cope with the “low-N” scenario or even enable high-accuracy zero-shot predictions, one could combine assay-labeled data and ML models trained under different contexts (e.g., probabilistic context, evolutionary context, structural-aware context) [293]. Such fitness predictors can navigate through the enormous fitness landscape by strategic virtual screening or by steered generative models [294]. To ensure broad landscape coverage with carefully chosen premium designs, one can use either a straightforward greedy algorithm or Beam search or Bayesian optimization to gain an acceptable trade-off between exploitation and exploration. It is not surprising to see that AI has already contributed considerably to directed evolution. But, protein complexity still demands heavy wetlab experiments for directed evolution.  \n\nTo reduce the workload of directed evolution, continuous evolution schemes such as PACE have been developed [295], which leads to the discovery of powerful molecular biology tools like RNA polymerases [296] and base editors [297]. However, as a platform, it relies on the cell survival for selection and can hardly be adapted to non-living circumstances. To meet the enormously diverse need of protein engineering, it is increasingly recognized that an integrated biofoundry platform combining core robotic instruments (like liquid handlers, thermocyclers, fragment analyzer, and colony pickers) and AI algorithms (for data analysis and decision making) would be indispensable to enable a closedloop in vitro continuous evolution [298] (Figure 16). The biochemical processes for making biological macromolecules are usually robust under mild conditions, which is ideal for implementing automation. For example, PlasmidMaker has been developed as an end-to-end pipeline for automated plasmid construction [299]; BioAutomata has been developed as a closed-loop system for microbial pathway engineering [300]. Although it remains nontrivial to adapt biofoundary to diverse assay methods, this system is highly promising in terms of high-quality data generation, acquisition, and analysis. They can be used to quickly evolve the ML model to be more and more powerful over time. The interactive interface can be in the form of an AI agent specialized in protein sciences which conveniently communicates with personnel in human language. Eventually, a paradigm shift in protein engineering is envisioned. It is only with Biofoundry that the need for speed in industry could be potentially met. Ready access to diverse enzymes shall bring yet another revolution to the synthesis of small molecules with time frame and cost superior to chemical methods.  \n\nThe above mainly focuses on protein as the model biological macromolecule. This is also where most literature works on. In principle, the work could be similarly done on RNA molecules. There are also works on using ML for structure prediction of RNA molecules [301–303]. Polysaccharides are an exception since they are not genetically encoded and highly heterogeneous. Hence, they behave more like synthetic polymers discussed in the previous section with collective materials properties as a functional output. Nevertheless, their chemical structures may be precisely manipulated by various enzymes like glycosynthase and glycosyl transferases, and their precise structures have great implications in cell signaling and are heavily involved in diverse biological pathways. Their synthesis and structural editing may be performed using biofoundary in a way similar to proteins [304]. Overall, AI has impacted and will continue to influence the engineering of biological macromolecules for diverse purposes, especially when aided with closed-loop automation (Figure 16).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 5 Automated experimentation  \n\nFor AI applications in synthetic chemistry, the generation of large-scale, high-quality chemical synthesis data is not only a crucial foundation for chemical modeling but also a vital knowledge source driving the innovation of synthetic chemistry itself. However, the approach of generating synthetic chemistry data has not undergone revolutionary changes over the past century. In current chemical experimentation, manual operations still dominate, which not only makes the synthetic exploration labor-intensive but also limits the efficiency of experiments and the reproducibility of synthesis data. The advent of autonomous synthesis platforms offers a novel strategy to address these issues. These platforms, by integrating advanced control technologies and robotic systems, are capable of precision control over the chemical synthesis process, thereby enhancing the efficiency of synthetic experiments, reducing labor input, and ensuring the accuracy and reproducibility of experimental results. Recent years have witnessed significant advancements in automated synthesis, separation, and even entire intelligent synthesis systems, providing a critical hardware engine for the paradigm shift in synthetic chemistry (Figure 17).",
+        "category": " Introduction"
+    },
+    {
+        "id": 18,
+        "chunk": "# 5.1 Automated synthesis  \n\nAutomation provides an avenue to transfer organic synthesis from a labor-intensive job to a machine-driven process [305]. The first concept of automated synthesis can be traced back to the 1960s when Merrifield and Stewart reported an automated system for solid-phase peptide synthesis [306,307]. Taking advantage of a similar strategy, DNA [308,309], RNA fragments [310], as well as polysaccharides [311] could be synthesized through an automated procedure today.  \n\nFor peptides and oligonucleotides, the synthetic protocol in their automated synthesizers is fundamentally the same for every individual molecule. In contrast, this is not the same case for general molecular synthesis. The synthesis instruments need to adjust the synthetic routes to holistic, interdependent, and multistep processes, which are mostly distinctive for each synthesis of small organic molecules. Given that automation in chemical research is rare and the commercially available systems were usually designed for specific purposes and only valid for repetitive work. In 1978, Legrand and Foucard [312] developed an automation kit for synthetic chemists. Ley’s group [313] devised a convenient and efficient prototype for evaporating, concentrating, and switching solvents in continuous flow processes and batch mode. In 2013, researchers from AbbVie Inc. developed an efficient compound-synthesis system with integrated components and automated sample-handling modules [314]. Tu et al. [315] later developed a fully automated synthesispurification station based on the SWAVE platform and inhouse developed robotics. Very recently, Ahmed’s group [316] developed a robot-assisted acoustofluidic end effector (RAEE) system consisting of a robotic arm and an acoustofluidic end effector (Figure 18a).  \n\n![](images/1dc1343dfc798ec61903f6f851ddd00ce7e121fa89d88de14353ab205d97de57.jpg)  \nFigure 16 Closed-loop, in vitro continuous directed evolution enabled by AI-assisted protein design and robotic automation (color online).  \n\n![](images/4f8819ec5d3f309f710f9ac5a6dcffc2ad9cb4fe061ddf6118779407eb822296.jpg)  \nFigure 17 Key research directions of automated experimentation (color online).  \n\nContinuous flow manufacture is widely embraced for synthesizing active pharmaceutical ingredients (APIs) and fine chemicals (Figure 18b) [317,318]. Automated platforms, such as ChemKonzert (Figure 18c) [319], enable solution-phase synthesis of diverse organic compounds. Pentelute’s lab introduced an automated flow-based system for rapid polypeptide synthesis [320]. Pfizer’s platform integrates nanomole-scale screening and micromole-scale synthesis, conducting over 1,500 experiments per $24\\mathrm{h}$ [321]. Li et al. [322,323] developed Tiny Tides, a fully automated fast-flow device, achieving on-demand customized antisense phosphorodiamidate morpholino oligomers (PMOs) and high-speed synthesis of PPNAs. This high-efficiency synthesizer serves as a training data source for effective ML models guiding efficient PNA sequence design [324].  \n\nIn 2019, Cronin et al. [325] developed an autonomous compiler and robotic laboratory platform, called Chemputer (Figure 18d), to synthesize organic compounds on the basis of standardized methods descriptions. Dömling’s group [326] employed I-DOT, a positive-pressure-based low-volume dispensing technology, for fully automated synthesis of over 1,000 iminopyrrolidine-2-carboxylic acid derivatives through Ugi-3-component reaction at the nanoscale. Williams, Kappe, and colleagues [327] designed an integrated multistep reaction and real-time analysis platform for controlled synthesis of mesalazine, achieving a throughput of $1.6\\ \\mathrm{g}$ per hour. In 2021, Kim’s group [328] developed a parallel flow synthesizer enabling multiplex synthesis and optimization of compound libraries, offering rapid screening and obtaining optimal conditions for various reactions in less than one hour from 96 different conditions. Gilmore and colleagues [329] introduced an automatic radial synthesizer featuring multiple continuous flow modules arranged around a central core, enabling stable and reproducible linear and convergent syntheses without manual reconfiguration. In 2022, Jensen et al. [330] developed a continuous stirred-tank reactor (CSTR) flow platform capable of handling solids and slurries during chemical transformations, enhancing the identification of optimized reaction conditions for manufacturing process development.  \n\nIsolation and purification in flow chemistry can follow an ideal process where reactants enter, and pure products exit continuously. George et al. [331] demonstrated continuous artemisinin synthesis in a supercritical $\\mathrm{CO}_{2}$ flow system. Multi-step reactions often require interruptions for work-ups and extractions before proceeding. Inline solid-phase extraction [332], gas-liquid, and liquid-liquid separation [333] technologies can incorporate most work-ups into a continuous process. Baranczak et al. [334] developed a fully automated platform for synthesis-purification-testing of small molecule libraries. Lee and Vilela et al. [335] reported an inline chromatographic purification automated flow synthesis platform, achieving $97\\%-99\\%$ purity in continuously isolating products.  \n\n![](images/03ade8e1591e270159c9896134f13d02438fcfca47b5db35bdbd5d9225e02b81.jpg)  \nFigure 18 Schematics of flow chemistry-based automatic synthesis platforms. (a) RAEE system. Reproduced with permission from Ref. [316]. Copyright 2022, Nature Publishing Group. (b) Flow manufacturing. Reproduced with permission from Ref. [317]. Copyright 2017, American Chemical Society. (c) ChemKonzert system. Reproduced with permission from Ref. [319]. Copyright 2010, Pharmaceutical Sociey of Japan. (d) Chemputer system. Reproduced with permission from Ref. [325]. Copyright 2019, American Association for the Advancement of Science (color online).  \n\nBurke’s automated Lego-like synthesis process utilized iterative peptide coupling for Suzuki-Miyaura $\\mathrm{C}(\\mathrm{sp}^{2})\\mathrm{-}\\mathrm{C}(\\mathrm{sp}^{2})$ bond formation [336], creating 14 diverse small molecule classes. The approach used $N$ -methyliminodiacetic acid (MIDA) as a building block, employing a “catch-and-release” purification protocol [337]. The strategy, while incompatible with stereospecific $\\bar{\\mathrm{C}}(\\mathrm{sp}^{3})\\mathrm{-}\\mathrm{C}(\\mathrm{sp}^{2})$ or $\\mathrm{C}(\\mathrm{sp}^{3})\\mathrm{-C}$ $(\\mathsf{s p}^{3})$ bond-forming reactions due to MIDA sensitivity, was recently improved with stable tetramethyl- $.N.$ -methyliminodiacetic acid (TIDA) boronates [338]. This advancement enabled the automated synthesis of $\\mathrm{C}(\\mathrm{sp}^{3})$ boronate building blocks and facilitated stereospecific $\\mathrm{C}(\\mathrm{sp}^{3}){\\mathrm{-C}}$ bond formation, broadening the scope of accessible molecules [339]. Jensen and collaborators [340] pioneered microfluidic automated platforms, such as droplet-based systems for efficient reaction screening and product isolation in small-scale medicinal chemistry. They optimized Pd-catalyzed $\\mathrm{C-N}$ coupling conditions [341] and developed an automated single-droplet screening platform for electroorganic process discovery [342,343]. In 2020, Kennedy and Stephenson et al. [344] reported an automated microfluidic platform to enable picomole scale synthesis. Recently, Jensen and Pidko et al. [345] reported a catalytic asymmetric hydrogenation of a sensitive $\\upbeta$ -amino-ketone substrate by means of an automated microfluidic platform. Debrouwer et al. [346] reported a dual catalysis cross-electrophile coupling using oscillatory plug flow photoreactors.  \n\nAdamo et al. [347] introduced a compact continuous manufacturing platform. Bode’s group [348] developed an automated capsule-based synthesis for $N_{\\mathbf{\\delta}}$ -heterocycles. Bode et al. [349] designed an iterative console assembling molecules from vast virtual libraries. Cronin et al. [350–352] utilized 3D printing for interconnected modules and a chemical to computer-automated design (ChemCAD) approach. They later created a portable platform for universal chemical synthesis using chemical markup language $(\\chi\\mathrm{DL})$ and 3D printing. These advancements signify a transformative shift towards efficient, digitized, and automated synthetic platforms [353].  \n\nVarious research groups have explored the concept of a “cloud lab” for remote operation of self-optimizing systems. In this regard, Poliakoff’s group [354] demonstrated a remote-operated system. Ley’s group [355] introduced Ley Lab in 2016, an Internet-based software allowing global monitoring and control of chemical reactions. Aspuru-Guzik and colleagues [356] developed ChemOS in 2018, a portable framework employing AI, sensors, and robotics for closedloop systems. Cronin’s Chemputer translated reported procedures into automatable steps using NLP and χDL [325,357]. Zhu’s materials acceleration operation system (MAOS) [358] in 2020 enabled intelligent robotics for material synthesis with AI-controlled quality assurance, accessible through VR-robot interaction. Cooper’s 2020 robo-chemist [359], driven by a Bayesian algorithm, autonomously conducted 688 reactions over eight days. Jiang’s AI-Chemist can autonomously extract literature and propose experimental plans from a cloud database [360]. In 2023, Gomes et al. [7] developed a system called Coscientist which is an artificial intelligence system driven by GPT-4 that autonomously designs, plans, and performs complex experiments.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 5.2 Automated work-up, isolation and purification  \n\nAutomated work-up, separation, and purification platforms are integral components of laboratory automation. In this regard, Ley et al. [361] has done significant contributions, whose works have been comprehensively reviewed by their own review. For instance, they have implemented machine vision automation for extraction operations [362], online solvent flash evaporation devices [313], optimized chromatographic separations [363], and automated filtration [364]. In terms of automating chemical laboratories and integrating ML and deep learning, the Cronin research group has achieved remarkable progress for automated automated synthesis machine [325,365]. Their system’s implementation relies on computer-controlled pumps. These pumps inject reactants into reaction flasks. Reaction work-up, including extraction, column chromatography, and rotary evaporation, is also integral to the system. These operations are achieved by transferring liquid reactants through a complex pipeline system using pumps. Spectroscopic detection methods, such as infrared spectroscopy and nuclear magnetic resonance spectroscopy, are also integrated. ML algorithms are employed to interpret these spectra, obtaining reaction information, which is then fed back into the system to achieve a closed-loop optimization.  \n\nIn chromatographic analysis and preparation, Kassel et al.’s PrepLCMS [366], a pioneering mass spectrometrybased system, automates the purification of substantial compound quantities. Koppitz et al.’s LC/MS-based system efficiently processes 100–200 compounds daily [367], ensuring high purity and yield. Ilg et al. [368] introduced a high-throughput high performance liquid chromatography/ mass spectrometry (HPLC/MS) platform, incorporating Covaris technology for sample preparation, automated aliquotation in fractionation, and a novel evaporation technique combining freeze-drying, enhancing purification efficiency. Recently, Mo et al. [369] developed an automated thin layer chromatography (TLC) platform for high-throughput data collection, subsequently using ML methods to predict the retardation factor (Rf) of compounds. The trained ML model can accurately predict the Rf value curves of organic compounds under different solvent combinations, providing general guidance for purification condition selection. Additionally, they have also developed a QGeoGNN-based model for predicting optimal HPLC separation conditions for chiral enantiomers, significantly reducing trial-and-error costs [370].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# 5.3 Integration of AI with robotic systems  \n\nDiscovering new reactions is unpredictable and laborious. Suboptimal initial conditions, especially in micro/nanoscale, may lead to overlooked trace products. In this regard, the integration of AI with robotic system can provide an effective strategy. However, it should be noted that applying ML to navigate new chemical space is underexplored due to the challenge of assessing reactivity in unknown reactions with unpredictable products compared with optimizing conditions for known target compounds [371,372]. Deconvolution algorithms, for instance, can help identify novel products [373,374]. Cronin’s group [365] demonstrated that a synthetic robot controlled by SVM algorithm significantly accelerated organic reaction discovery. The liquid-handling robot selected reactants from a pool, with real-time analytics monitoring reactions. ML built a chemical space model, recommending experiments and controlling the robot. The system outperformed manual processes, predicting the reactivity of 1,000 combinations with over $80\\%$ accuracy. Zahrt and colleagues [375] applied ML to guide electrochemical reaction discovery, developing a molecular representation for general models and successfully predicting new reactions’ competency. These studies showcase AIdriven chemical robots advancing reaction space exploration. Recently, research groups have also applied reinforcement learning for automated mechanism discovery, bypassing exhaustive screening [376,377]. An agent constructs efficient reaction pathways by selecting actions (elementary steps) with varying rewards. This approach holds promise for efficient reaction network exploration, requiring first-principles or semi-empirical evaluations.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# 6 Challenges and perspective  \n\nThe burgeoning field of AI in organic and polymer synthesis presents a transformative potential for scientific discovery. However, this promise is contingent on overcoming a series of challenges that currently impede its full realization. This section delves into these critical issues, offering a succinct yet comprehensive overview of the challenges faced by AI applications in synthetic chemistry as well as potential solutions.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# 6.1 Data  \n\nIn synthetic chemistry, particularly in organic and polymer synthesis, the role of data is foundational for the successful AI application [378]. The main challenges associated with data in this field include issues of quantity, quality, standardization, and accessibility [229,379,380]. Generating sufficient, high-quality data is a complex endeavor, limited by the intricate and time-consuming nature of chemical experiments. The quality of data, essential for the training and performance of AI models, is frequently compromised by variations in experimental conditions, disparate practices among researchers, and inherent biases, leading to significant inconsistencies [381–383]. These variations and the lack of detailed reaction conditions in public databases undermine the reliability of data for AI applications. Moreover, the absence of standardized data formats complicates the compatibility and comparability across different systems, hindering the efficient training of AI models and their application to varied tasks. Data accessibility is further challenged by legal, technical, and proprietary barriers that restrict the use of data, making it difficult for researchers to obtain and utilize the information needed for their work.  \n\nAddressing the limitations around data in synthetic chemistry necessitates a multifaceted approach that integrates the establishment of open data principles with advanced AI-assisted data management techniques. The adoption of FAIR principles—ensuring data is Findable, Accessible, Interoperable, and Reusable—is critical for improving data quality, standardization, and accessibility [384]. These principles support the creation of a standardized data management framework that facilitates the sharing and reuse of data across the scientific community. Additionally, leveraging AI for automated data extraction and processing offers a powerful solution to enhance the efficiency and accuracy of data collection [385,386]. This involves the use of advanced natural language processing and large language models for scraping, mining, and extracting valuable information from a plethora of sources including chemical literature, reaction databases, and experimental records. The key to harnessing these technologies lies in their ability to process and analyze vast amounts of data, translating them into actionable insights that can drive research forward. However, ensuring the reliability of the extracted data is crucial, necessitating careful validation and verification processes. Moreover, fostering an open data community, grounded in the principles of collaboration and shared resources, is essential for overcoming the barriers of data accessibility and standardization. Such a community would serve as a hub for aggregating, refining, and sharing data, thereby facilitating a more collaborative, efficient, and innovative research environment [35]. Together, these strategies offer a comprehensive blueprint for addressing the challenges posed by data limitations in synthetic chemistry, paving the way for enhanced AI applications and scientific discovery.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# 6.2 Encoding  \n\nFor the digital representation of synthetic chemistry, three core challenges are prominently identified: universality, interpretability, and the representation of the stochastic nature of polymer structures. The complexity and diversity of chemical data, spanning a wide spectrum from molecular structures to reaction conditions, necessitate distinct representation approaches for each type, complicating the quest for universality. The issue of diversity, encompassing various modalities such as texts, images, and tables, adds another layer of complexity in standardizing chemical information. Further complicating this pursuit is the fact that various laboratories and researchers often employ their customized methods for data recording and representation. These personalized approaches create significant hurdles in achieving a universal standard for chemical data across different formats and sources. The challenge of interpretability arises from the need to encode chemical insights in a way that is comprehensive to computational models and intelligible to human researchers. This includes difficulties in conveying complex chemical phenomena and the inherent tension in designing models that combine high accuracy with ease of understanding, emphasizing the trade-off where increased predictive performance often diminishes transparency. Additionally, accurately capturing the stochastic nature of polymers, characterized by their varied molecular weights and structural configurations, presents a unique challenge. The properties of polymers are heavily influenced by their molecular diversity, requiring nuanced and precise encoding strategies to capture the essential characteristics that dictate their behavior and functionality. These challenges collectively underscore the complexities of developing effective encoding systems in synthetic chemistry, aimed at bridging the gap between the intricate chemical phenomena and their computational representations.  \n\nAdvancing encoding techniques in synthetic chemistry can be approached from the following angles. Leveraging multimodal learning methods and large Transformer-based models such as ChemBERTa [387], MoLFormer [388], and ChemGPT [389] to integrate chemical data from diverse modalities including texts, images, and tables, could pave the way towards a unified representation system. This effort may also involve standardizing chemical information through the creation of universal datasets and the application of intelligent algorithms to address the challenges of non-standardization. On the interpretability front, enhancing models to combine high accuracy with ease of understanding is crucial. A representative example is the ASO descriptor designed by Denmark et al. [187], which finely depicts the three-dimensional structure of chiral molecules from the perspective of space filling. Additionally, symbolic regression represents a valuable method that could uncover relationships with clear analytical expressions, offering new ways to interpret complex chemical data [390]. For the representation of the stochastic nature of polymers, it requires models that can encapsulate the diversity in molecular weights and structural configurations. Specialized polymer representation models that consider dispersity and monomer sequence arrangements could more precisely predict polymer properties [214]. Exploring computational models for topological structures, such as branched polymers, might also improve the accuracy of property predictions and expand the models’ applicability. Through these strategies, the goal is to effectively bridge the gap between the complexity of chemical phenomena and their digital representation, facilitating AI applications for chemical understanding and innovation.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# 6.3 Model availability  \n\nIn synthetic chemistry, the field faces the challenge of model availability due to its diverse chemical dimensions and highly individualized application scenarios. Related AI researches often narrow the focus to specific synthetic targets, utilizing customized datasets of limited size. This specialized approach to developing and implementing AI models in synthetic chemistry is not yet fully mature. Although certain AI models demonstrate significant potential, the majority presented in research papers typically provide only a GitHub link with minimal annotations. This mode of sharing, while enabling the replication of research, lacks in offering userfriendly software, platforms, or sufficient documentation and user guides, rendering it difficult for chemists without computer science expertise to effectively utilize these models. Additionally, most model developments prioritize the verification of scientific hypotheses over the consideration of the models’ applicability from the users’ perspective. Even successful model implementations may not meet the specific needs of synthetic chemists for particular molecules or reactions. The efficiency and accessibility of the encoding process also pose notable challenges. Many of the current models require the use of specialized quantum chemistry software and significant computational resources, further complicating matters for experimental synthetic chemists. Thus, making AI technology conveniently and efficiently usable for experimental chemists is essential for the progress of AI in synthetic chemistry.  \n\nTo tackle the issue of availability, democratizing AI becomes a critical step towards technological advancement, essential for fostering scientific innovation of AI-assisted synthetic advancement. This democratization process aims to make AI tools, algorithms, and software more accessible and user-friendly for synthetic chemists, particularly those without a background in computer science. Developing AI software that aligns with the needs and experiences of chemists, moving away from complex code repositories to tools characterized by intuitive data input, clear result displays, and simple operation procedures, can significantly lower the barriers to AI application, thereby improving its impact in synthetic chemistry. Moreover, the transparency and chemical interpretability of AI tools are crucial; they should not only provide accurate predictions but also clearly explain their decision-making processes to users, building trust and promoting positive interactions between chemists and AI. In addition, allowing chemists to contribute to the AI modeling processes can lead to more meaningful predictions and ensure that AI-assisted experimental designs are closely aligned with real-world scenarios. The democratization of AI in synthetic chemistry is not just about making AI more accessible; it is about creating a more collaborative and innovative environment where AI and synthetic chemistry complement each other.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 25,
+        "chunk": "# 6.4 Automated experimentation  \n\nAutomated or semi-automated platforms, utilizing robotics and data-driven algorithms, present a solution to the bottleneck in chemical synthesis. While automation is well-established in routine tasks for pharmaceuticals, it often focuses on narrow, well-defined processes. Methodologies for chemical synthesis automation, optimization, and discovery, particularly in laboratory-based research and benchscale synthesis, face challenges from both hardware and software, as well as the high cost. For the hardware foundation, a critical issue is the integration of automated synthetic platforms into existing laboratory setups. This requires not only consideration of the physical space within synthesis labs but also the adaptability of the platform to seamlessly fit these environments. Moreover, the importance of userfriendly software interfaces and application programming interfaces (APIs) cannot be overstated. Chemists are in search of comprehensive solutions that encompass reaction monitoring, machine self-optimization, and AI/ML algorithms, all compatible with remote control capabilities. Currently, the software and APIs available fall short of supporting a fully self-driving laboratory, indicating a significant gap that needs to be bridged.  \n\nIn tackling the challenges faced by automated chemical synthesis, a focused approach on both hardware and software innovations is pivotal. For hardware, the introduction of customizable, modular systems like Opentrons’ laboratory robots for liquid handling showcases a significant step towards affordability and adaptability in automation. Their open-source robots (OT-1 and OT-2), priced as low as $\\$10,000$ , exemplify the move towards making sophisticated automated platforms more accessible to a broader audience, ensuring easy integration into existing lab setups without extensive modifications. On the software side, beyond democratizing AI, the incorporation of integrated AI management software holds the key to bridging the gap in automated chemical synthesis. Systems like those developed by Jensen and Jamison, utilizing MATLAB and LabVIEW, offer examples of how control systems can provide real-time monitoring and automated feedback optimization [391]. Such platforms demonstrate the potential for AI-based synthesis planning and ML algorithms to revolutionize synthesis routes, from hypothesis generation to molecule structure prediction. Together, these hardware and software advancements present a coherent strategy to overcome existing obstacles in automated chemical synthesis. By aligning the cost-effective, customizable hardware solutions with cuttingedge, integrated software platforms, the field is set to undergo a transformative shift towards more accessible, efficient, and innovative research methodologies, marking a significant leap in the application of automation technology within the chemical sciences.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 26,
+        "chunk": "# 7 Conclusions and outlook  \n\nIn summary, this review discusses the applications of AI in organic and polymer synthesis in recent years, investigating the benefits and potential of the data-driven research paradigm in addressing challenges of synthetic chemistry. In organic synthesis, AI applications have made significant breakthroughs at various levels ranging from molecules to reactions: (1) Predictions of molecular thermodynamic and kinetic properties have seen a quantum leap in efficiency without sacrificing accuracy. Chemists, empowered by ML models, can now swiftly and precisely assess crucial physicochemical parameters like $\\mathsf{p}K_{\\mathrm{a}}$ , BDE, and rate constants, offering valuable insights for molecular design in synthetic chemistry. (2) The capabilities of computer-assisted synthetic planning have undergone tremendous improvement, particularly for complex molecules. Emerging AI software can more rationally, diversely, and efficiently plan multi-step synthetic routes, even rivaling human chemist designs. (3) Data-driven prediction for yield and selectivity can help chemists identify superior catalysts or reagents, providing essential AI support for rational reaction design. In polymer synthesis, AI application has also shown remarkable outcomes: (1) ML methods can establish quantitative relationship between polymer structures and properties, achieving accurate predictions and even target-oriented polymer design; (2) AI can aid and guide the design and optimization of polymerization processes, achieving end-to-end control and linking polymerization conditions directly to the products’ functionalities; (3) AI application in biological macromolecules is equally thriving, predicting structures, designing functional sequences, and even autonomously performing closed-loop continuous directed evolution for proteins, RNA, and other macromolecules. Additionally, the advancement of automated experimentation paves the way for liberating synthetic chemists, significantly improving precision and efficiency in synthesis, work-up, isolation, and purification. This, coupled with AI’s brainpower, heralds the advent of intelligent synthesis laboratories. These exciting developments demonstrate AI’s substantial contribution to synthetic chemistry, signaling the dawn of an era of intelligent synthesis.  \n\nHowever, it is crucial to acknowledge that AI application in synthetic chemistry is still nascent, with challenges and limitations that cannot be overlooked. The quantity and quality of available open data in synthetic chemistry are far from satisfactory, lacking unbiased, large-scale datasets like ImageNet to support AI development. The digital representation of synthetic systems requires the improvements in standardization, interpretability, and applicability. Current molecular and reaction encodings lack standardized methods and deep chemical understanding, also posing challenges in encoding like the stochastic nature of polymer structures. The “black box” nature of existing AI models makes it difficult for chemists to comprehend the decision-making process, limiting the models’ capacity to provide chemical insights. Issues with model availability also hinder the model application in new synthetic systems. To overcome these challenges and truly promote the healthy, sustainable development of AI synthetic chemistry, the following actions are recommended. First, enhancing data sharing and model openness. Following the FAIR (findable, accessible, interoperable, and reusable) principles, chemists should reshape the open data community of synthetic chemistry with advanced large models, so as to foster broader collaboration and innovation. Second, democratize AI, making the cuttingedge achievements of AI chemistry accessible to experimental chemists for frontline synthetic design. Third, focusing on software and hardware upgrades and optimization to better integrate AI technology and experimental synthetic processes. This will enable automated synthesis platforms to enter everyday laboratories and significantly enhance the efficiency and accuracy of synthetic experiments. It requires the joint efforts of chemists, computer scientists, and engineers to accelerate the process of intelligentization in synthetic chemistry.  \n\nWith the continuous breakthroughs and development of ML and automation technologies, synthetic chemistry is undergoing a transformation from a traditional “manual” era to an “intelligent” era. In the near future, AI will play a vital role in every aspect of synthetic chemistry: (1) Molecular design. AI will use chemical databases and ML algorithms to design molecules with specific functions according to chemists’ needs. (2) Synthetic pathway planning. For a given target molecule, AI models can efficiently plan synthetic pathways and provide detailed experimental schemes. (3) Experimental execution: Integrated AI with automated synthesis platforms/robots will create intelligent synthesis laboratories capable of conducting experiments, providing real-time feedback, and automatically adjusting experimental plans for condition optimization until the target product is synthesized with high selectivity and yield. (4) Remote interaction: AI systems deployed in the cloud enable chemists to interact remotely at any time and place via mobile phones/computers. (5) The commercialization of general chemical databases, ML algorithms, and machine chemists will likely make AI and related automation technologies standard equipment in ordinary synthetic laboratories, greatly promoting the development of synthetic chemistry.  \n\nAcknowledgements This work was supported by the National Natural Science Foundation of China (22393890, You SL; 22393891 and 22031006, Luo S; 2203300, Pei J; 22371052, Chen M; 21991132, 21925102, 92056118, and 22331003, Zhang WB; 22331002 and 22125101, Lu H; 22071004, Mo F; 22393892 and 22071249, Liao K; 22122109 and 22271253, Hong X), the National Key R&D Program of China (2023YFF1205103, Pei J; 2020YFA0908100 and 2023YFF1204401, Zhang WB; 2022YFA1504301, Hong X), Zhejiang Provincial Natural Science Foundation of China (LDQ23B020002, Hong X), the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study (SNZJU-SIAS-006, Hong X), the CAS Youth Interdisciplinary Team (JCTD2021-11, Hong X), Shenzhen Medical Research Fund (B2302037, Zhang WB), Beijing National Laboratory for Molecular Sciences (BNLMSCXXM-202006, Zhang WB), the State Key Laboratory of Molecular Engineering of Polymers (Chen M), Haihe Laboratory of Sustainable Chemical Transformations and National Science & Technology Fundamental Resource Investigation Program of China (2023YFA1500008, Luo S).  \n\nConflict of interest The authors declare no conflict of interest.  \n\n1 Zhang S, Roller S, Goyal N, Artetxe M, Chen M, Chen S, Dewan C, Diab M, Li X, Lin XV, Mihaylov T, Ott M, Shleifer S, Shuster K, Simig D, Koura PS, Sridhar A, Wang T, Zettlemoyer L. 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+        "category": " Conclusions"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# AI技术在化工行业设计工作中的应用展望  \n\n姜宜君  \n\n（中海油石化工程有限公司，山东青岛 266101）  \n\n摘　要：随着人工智能（Artifi cial Intelligence, AI）技术的飞速发展，其在化工行业设计工作中的应用已经引起了广泛关注。AI 技术以其强大的自然语言处理能力、数据分析能力和逻辑推理能力，为化工行业设计带来了革命性的变化。首先解析了AI 技术具备数据分析、自然语言处理、知识融合、机器视觉能力，发现这些 AI 能力能够在化工设计领域发挥一定的价值。其次，深入探讨了 AI 技术在化工设计领域的知识管理、图纸管理、设计流程自动化等诸多核心设计过程的应用场景。化工设计场景在AI 的赋能下，不仅提高了设计效率，降低了成本，还实现了知识共享的愿景。然后，针对 $\\mathrm{AI^{+}}$ 化工设计应用场景，识别出目前 AI 在智能化设计、跨学科融合和人工智能伦理安全的风险与挑战。最后，对 AI 技术在化工行业设计中的未来发展进行了展望，预见其将实现更高级别的智能化、更广泛的应用领域以及更紧密的产业融合，并进一步推动化工行业设计的创新与发展。  \n\n关键词：AI 技术；人工智能；化工设计；智能设计；数字化中图分类号：TP29 文献标志码：A 文章编号 ：1003-6490（2025）01-0103-04",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# Application Prospect of AI Technology in Chemical Industry Design  \n\nJIANG Yijun  \n\nAbstract: With the rapid development of artificial intelligence technology, its application in the design work of the chemical industry has attracted extensive attention. With its powerful natural language processing capabilities, data analysis capabilities, and logical reasoning capabilities, AI technology has brought revolutionary changes to the design of the chemical industry. Firstly, this paper analyzes the capabilities of AI technology in data analysis, natural language processing, knowledge fusion, and machine vision, and finds that these AI capabilities can play a certain value in the field of chemical design. Secondly, this paper deeply discusses the application scenarios of AI technology in many core design processes in the field of chemical design, such as knowledge management, drawing management, and design process automation. With the empowerment of AI, the chemical design scenario not only improves design efficiency and reduces costs, but also realizes the vision of knowledge sharing. Then, for the application scenario of $\\mathrm{AI^{+}}$ chemical design, the current risks and challenges of AI in intelligent design, interdisciplinary integration and artificial intelligence ethical security are identified. Finally, the future development of AI technology in the design of the chemical industry is prospected, and it is foreseen that it will achieve a higher level of intelligence, a wider range of application fields and closer industrial integration, and further promote the innovation and development of design in the chemical industry.  \n\nKeywords: AI technology; artificial intelligence; chemical engineering design;intelligent design; digitization",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# 0 序言  \n\nAI 技术是一种让计算机具备人的学习、思考、推理和自主学习技术，旨在能够让计算机“以人的行为和思维方式”完成一系列工作或任务。2022年OpenAI 的 ChatGPT 横空出世，各行业、专业领域、业务场景不断探索出与 AI 融合的业务场景或商业模式，不断提升业务智能化的进程。同时，这些 AI 场景，也在反向促进AI 的发展。尽管业务搭上AI 的便车实现了更高效、智能的发展，但是，正由于 AI“能够以人的思维方式”工作，这也不由得引起人们对其安全性、可靠性、保密性等诸多方面的担忧。我们希望搭建安全可信的AI 应用场景，一方面，借助于 AI 在各行业、专业领域、各业务部门之间搭建更加高效的协同桥梁，降低因专业壁垒导致的技术鸿沟，另一方面，也应该提升 AI 的安全性，在共享业务系统和知识的过程中，避免数据泄露，并让 AI 基于化工基本伦理工作，减少上述忧虑。",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1 AI 技术及其在化工设计中的应用背景  \n\n化工设计行业专业性较高，并且设计过程复杂，因其在效率、成本、质量、安全等方面均有较高的要求，一直以来，针对这些问题并没有较好的解决方案。而AI 能够基于大数据，通过对数据的挖掘和自我学习，发现化工设计过程中隐藏的设计模式，帮助设计过程更加科学、高效，进而提出创新性的解决方案，在化工设计应用过程中可发挥巨大作用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 1.1 数据分析与优化功能  \n\n在化工设计中，AI 技术通过对行业设计数据和公司已交付工程进行数据机器学习和深度学习，挖掘出化工设计过程的设计规律和发展趋势，为化工设计人员提供高效的数据分析和优化能力，并对化工设计过程提供较完备的设计建议。同时，因机器学习算法具备自我学习和进化的能力，从而能够在不断对新产生设计数据的挖掘和学习过程中，根据正向的知识反馈，不断优化算法，提升数据分析的准确性，进而反馈质量和效率“双高”的设计建议。  \n\n在未来的设计过程中，设计人员可以借助于生成式AI，改变传统的设计模式：将“以人的经验为中心”的设计模式，转变为“用 AI 辅助”的设计模式。在新的设计模式下，设计人员可以将项目背景、设计规范以及设计要求以“提示词”的形式投喂给 AI，让AI 辅助生成初步的设计图纸。这些设计图纸，为设计人员提供比较丰富的设计灵感和参考思路，为基础设计阶段打下坚实的基础。进入详细设计阶段后，设计人员将基础设计阶段选型的设计图纸，结合进一步细化的设计需求和相关业务调度要求，以提示词的形式与 AI 进行交互，在经过多轮的交互后，得到既满足业务需求，又具有创新性的设计方案[3]。",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 1.2 自然语言处理与知识管理功能  \n\n自然语言处理（Nature Language Processing, NLP）技术因其能够理解并处理自然语言，所以在化工设计过程中，可以使用NLP 技术解析行业规范、化学文献、实验报告等文本数据，从中提取出对设计有价值的信息和知识，搭建具备 NLP 功能的知识管理能力，提升设计人员的知识检索效率。此外，NLP 能够将分散的设计系统、行业知识进行关联，形成独有专业的“知识图谱”，为化工设计工作者提供全方位的设计指引，避免因为遗漏设计规范和法规条例出现设计反复修改甚至设计事故。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 1.3 计算机视觉与专家系统  \n\n计算机视觉具有强大的监控和检测功能，在笔记识别、绘图识别、实物识别等领域有广泛的应用 [4]。通过图像和视频数据，实时监控生产过程、检测产品质量、设备状态等关键信息，及时发现并预警各个业务环节出现的问题和异常信息。例如，对于化工反应过程中颜色、气泡等显著特性的变化，机器视觉可以自动识别反应结果，帮助设计师及时调整工艺参数。现阶段某些可燃气体检测仪便是运用了机器视觉技术，达到了对气体泄漏的检测甚至提前预测的目的。  \n\n专家系统则集成了化工领域的专业知识和经验，能够模拟人类专家的思考过程，解决复杂的设计问题，为此，专家系统能够为设计师提供权威的决策支持和建议 [5]。在化工设计过程中，一方面，专家系统能够根据设计师人员的需求和约束条件，为其提供更加贴近项目实际场景的设计方案、材料选型和工艺参数等建议；另一方面，专家系统基于对历史数据和实时数据的分析，预测出生产过程中的潜在风险，并提供针对性的解决方案。当然，为了达到以上的应用效果，专家系统需要对海量的设计文件、行业经验、文献、规范等非结构化的“自然语言”文本不断迭代和学习，提升 AI 的自主推理和学习能力，保证专家系统具备“专家能力”。  \n\n化工设计可以借助于AI 相关的数据分析与优化、自然语言处理与知识管理、计算机视觉与专家系统等多种功能和应用场景，提高化工设计的效率和质量，挖掘更多的创新场景和发展机遇。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2 AI 技术在化工设计过程中的应用场景",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.1 AI+化工设计知识管理应用场景",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.1.1 自动化与智能化整合  \n\n在化工设计领域，利用机器学习技术的自动化搜索和智能分类能力，可极大地提高设计人员查找和整合规范文档的效率。利用深度学习和自然语言处理技术，机器学习模型能够自动从海量规范中提取关键特征，以向量的形式关联业务关键点，形成知识图谱的底层数据要素，构建高效的搜索索引，形成垂直领域的知识图谱，方便设计人员向 AI 发起基于专业提示词的对话。  \n\nAI 通过对提示词的解析，在专业知识库中完成快速、精准检索后，将结果组装后反馈给设计人员。此外，机器学习还能将设计领域与其他相关领域的知识图谱进行关联和融合，实现跨领域级知识的关联和检索，更好地为设计工作提供相关领域知识的智能推荐和业务指引。如针对工程师基于设计规范、专业背景和项目需求等特征，由 AI 提供跨领域融合的智能化解决方案，有效帮助工程师获取完备的设计规范，同时也能够促进设计行业的知识发现和业务创新。",
+        "category": " Introduction"
+    },
+    {
+        "id": 11,
+        "chunk": "# 2.1.2 预测性分析与可视化展示  \n\n机器学习不仅提供了高效的信息整合和检索能力，还具备对业务数据的可视化展示和预测性分析的能力。通过对历史数据和行业动态的分析，机器学习能够预测规范的发展趋势和潜在变化，帮助企业提前做好应对策略，以在新的发展阶段寻求发展机遇和应对挑战。同时，机器学习还能将规范信息以流程图、思维导图、热力图、数据流图等可视化的方式展示，帮助工程师更直观地理解规范内容，让工程师将设计过程聚焦在行业规范和风险特征较高的设计流程中，减少因对冗余信息的检索和排查而导致的沉没成本，提高信息的吸收和应用效率。此外，机器学习模型具有自我学习和持续进化的能力，随着数据的积累和模型的优化，其对设计要素的完备性和准确度将不断提升，这将有助于提升化工设计规范的整合能力与信息检索能力。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 2.2 $\\mathbf{A}\\mathbf{I}+$ 化工图纸绘制应用场景  \n\n将 AI 的视觉检测技术应用到化工设计过程中的图纸识别与分析、图纸错误检测、图纸标准化、图纸的三维建模与分析、图纸与模型的相互转换、设计参数优化、设计流程自动化等设计场景，有效提升图纸绘制的效率和准确性。",
+        "category": " Introduction"
+    },
+    {
+        "id": 13,
+        "chunk": "# 2.2.1 自动化图纸识别与分析  \n\n在化工设计中，图纸是设计师们表达设计意图、展示工艺流程的重要工具。传统的手工图纸因为是由设计人员识别与分析，以至于整个设计过程不仅耗时高，而且还容易出现遗漏项导致错误率居高不下。计算机视觉技术通过先进的图像识别和模式匹配算法，能够迅速而准确地识别图纸中如管道、阀门、泵等各类元素，并理解它们之间的相关性，形成集统计、合规性于一体的分析报告。这不仅加快了设计分析的速度，提高了分析的准确性，为后续的设计修改、优化和审阅提供了坚实的基础；而且结合了 AI 的风险识别能力，依托 AI 已经整合的设计规范、法律法规和最佳设计案例，AI 能够快速并有效地根据识别出的遗漏的设计要素和“非规范化设计要素”，帮助设计人员规避业务风险。",
+        "category": " Introduction"
+    },
+    {
+        "id": 14,
+        "chunk": "# 2.2.2 图纸错误检测  \n\n化工设计图纸中的错误可能会导致严重的后果，轻则损坏设备，重则导致生产事故，为此，图纸错误检测在设计过程中具有相当重要的分量。因此，如何及时发现图纸中的错误，并提供有效修改建议，变得尤其重要。计算机视觉技术能够开发出高效的图纸错误检测系统，能识别图纸中的潜在错误，如设备尺寸错误、连接错误等，并及时提醒设计师进行修正。这不仅减少了设计错误发生的概率，还提高了设计的可靠性和安全性。在人与 AI 交互的过程中，设计人员不断将修改的建议迭代到 AI 的认知能力库中，逐步完善 AI 的错误检测和错误修正能力，最终实现让 AI帮助设计人员完成图纸错误检测和修正的工作，达到提高设计效率的目的。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 2.2.3 图纸标准化  \n\n由于每一位设计人员参与的项目不同，设计习惯也因此有一定的差异，这便为图纸的标准化带来一定的挑战。图纸的标准化可以使项目风格统一、提高成品文件设计质量，更有效地实现信息共享。计算机视觉技术的应用便可以提供如检测设计文件图例是否正确、格式是否统一、数据是否完整等服务，极大地提高了标准化程度与检测的效率和准确率。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 16,
+        "chunk": "# 2.2.4 三维建模与可视化  \n\n三维建模在化工设计中已极为普遍，智慧工厂设计、数字化交付技术更是趋于成熟。计算机视觉技术甚至可以检查检修人员的巡检路线是否畅通，以便修改设计使得符合实际情况。这不仅有助于设计师更好地分析设计细节，还为后续的项目审查、优化等提供  \n\n了有力支持。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 2.2.5 设计流程自动化  \n\n传统的化工设计流程往往需要大量的人工输入、统计和检查工作，这往往会浪费大量的时间，并且会因为复杂度的提升而容易出错。通过自动识别图纸中的元器件、工艺流程等信息，并将其记录到设计软件中，视觉技术自动完成相关设计输入和统计相关的工作，在提高设计效率的同时，自动检查设计过程中存在的疏漏或风险，确保设计的准确性和可靠性。基于此，视觉技术有效代替设计人员的手工操作，帮助设计人员完成容易遗漏的差错检测，并结合 AI 的图例能力，可逐步实现流程的自动化设计，提升流程设计的自动化水平。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# 3 AI 技术在化工设计中面临的挑战与机遇",
+        "category": " Introduction"
+    },
+    {
+        "id": 19,
+        "chunk": "# 3.1 智能化设计  \n\n传统的化工设计过程往往依赖于人工经验和复杂的计算，而 AI 系统则能够凭借其强大的数据处理和分析能力，更深入地理解设计需求和市场趋势。通过机器学习、深度学习等算法，AI 系统可以自动完成部分如模拟实验、参数优化等设计工作，从而大大提高设计效率和质量。尽管 AI 算法能够根据大数据的统计规律自动生成设计方案，但往往因为 AI 使用类似的推理模型容易出现较常规和无差异化的解决方案，这难以匹配实际的业务需求，而对于设计人员的辅助设计来说，反而会将“利器”变为“累赘”。此外，AI 技术在处理复杂问题和非结构化任务时仍面临诸多挑战，其能力尚未达到人类工程师的综合决策水平。设计工程师在设计中能够综合考虑诸如环境、规范、业务需求、客户偏好、设计理念等诸多复杂和不可控的因素，而 AI 技术在这方面仍有待进一步发展和提升。  \n\n设计师可以借助于智能化设计，从繁琐的计算和模拟工作中脱离出来，从而更加专注于设计模式优化和创新。此外，AI 系统还可以根据市场反馈和消费者需求，快速调整设计方案，以满足不断变化的市场需求和发展趋势。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# 3.2 跨学科融合  \n\n化工设计是一个涉及化学、物理、机械等多个学科的复杂过程。传统的化工设计往往因为存在学科壁垒，导致各学科之间的知识和经验无法有效融合和共享，AI 技术的出现，为跨学科融合提供了新的方式。  \n\n在化工设计产品过程中，借助于AI 的信息整合能力，以“统一语言”的形式，输出让各专业领域相互理解的设计模式。因此，在化工设计过程中，AI 可以帮助各专业突破专业障碍，降低沟通难度，提升沟通和协作效率，从而促进化工产品设计的革新与开发。",
+        "category": " Introduction"
+    },
+    {
+        "id": 21,
+        "chunk": "# 3.3 人工智能伦理和安全的关注  \n\n尽管AI 技术在化工设计中具有丰富的应用场景，（下转第115页）  \n\n压缩机基础荷载较大，采用天然地基或地基处理不能满足设计要求，应采用桩基础。因压缩机厂房基础底部的拔力较大，需要桩能提供很大的抗拔力，所以本工程选用干作业灌注桩。以第 $\\textcircled{5}$ 层强风化岩为桩基持力层，计算得单桩竖向抗压承载力特征值为 $1~100\\mathrm{kN}$ 。需要注意的是，根据《动力机器基础设计标准》（GB50040—2020）第 3.3.1 条及 3.3.3 条，桩基承载力需要乘以动力折减系数，旋转式机器基础可取0.8。  \n\n采用PKPM 基础设计版块进行基础的设计，基础底板尺寸为 $15\\mathrm{m}\\times6.9\\mathrm{m}$ ，布置三行六列灌注桩。计算得最大桩基反力为 $550\\mathrm{kPa}$ ，平均桩基反力为 $514~\\mathrm{kPa}$ ，满足承载力要求。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# 2 结语  \n\n当动力机器基础的振动响应超过容许振动标准时，会造成动力机器机器振动过大，减少使用寿命，降低工作效率，被迫停止工作，造成设备附属管道和零部件损坏，会对操作人员舒适性造成不良影响，会对附属建筑结构造成损伤、破坏，甚至引发工程事故。因此进行动力机器基础的动力计算很有必要。通过工程计算实践证明，STAAD.Pro 非常适用于构架式压缩机基础的动力计算。其空间建模方便，计算模型合理，而且结果直接详细，为大型构架式动力机器的发展提供了便利的条件。  \n\n构架式压缩机基础设计是一项繁重而复杂的过程，不仅仅是为了避免经济损失，更是为了保证操作人员的人身安全。作为一个合格的设计人员，我们要对自己负责，也要对别人负责，做新时代的好青年。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 23,
+        "chunk": "# 参考文献  \n\n[1] 中华人民共和国工业和信息化部 . 石油化工压缩机基础设计规范 : SH/T 3091—2012[S]. 北京 : 中国石化出版社 , 2013.  \n[2] 中华人民共和国住房和城乡建设部 . 动力机器基础设计标准 : GB 50040—2020[S]. 北京 : 中国计划出版社 ,2021.",
+        "category": " References"
+    },
+    {
+        "id": 24,
+        "chunk": "# （上接第105页）  \n\n也能为化工设计过程带来便捷的设计体验，但因其具备“人的思维方式”，我们不得不面临AI带来的伦理和安全方面的诸多挑战。  \n\n人工智能伦理问题应优先考虑。随着 AI 系统在化工设计中的应用日益广泛，如何确保 AI 系统的道德合规性、避免潜在的伦理风险成为亟待解决的问题。我们需要制定相应的伦理规范和监管机制来确保 AI能够秉持化工伦理的基本准则来赋能化工各场景。  \n\n数据安全也是 $\\mathrm{AI^{+}}$ 化工场景的关键问题。在大数据时代，尽管设计师可以借助 AI 的学习成果，提高设计团队的协作效率，发现设计过程中的潜在风险，以便提前采取预防措施，但设计人员投喂给 AI 的资料，也必将成为 AI 的学习资料，这将很有可能出现数据泄露的风险，进而出现公司、行业和国家机密泄露的风险。所以，AI 在化工行业应用的过程中，如何保障数据安全将成为至关重要的环节。  \n\n综上，我们需要采取有效的技术手段和管理措施来防止数据泄露、非法获取和滥用等风险的发生。",
+        "category": " Introduction"
+    },
+    {
+        "id": 25,
+        "chunk": "# 4 结论  \n\nAI 技术在化工设计过程中具有广泛的应用前景，也面临着安全与伦理等诸多方面的挑战。通过提高设计效率和质量、降低设计风险、实现个性化定制设计、推动设计业务流程高效协同等多种场景的融合，AI技术将为化工设计带来新的变革。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 26,
+        "chunk": "# 参考文献  \n\n[1] 梁庆国. AI 人工智能技术应用于设计专业实践教学的跨界合作与创新模式研究 [J]. 现代职业教育 , 2024(4): 153-156.  \n[2] Huang J W. Digital engineering transformation withtrustworthy AI towards industry 4.0: emerging paradigmshifts[J]. ArXiv e-Prints, 2023: arXiv: 2301.00951.  \n[3] 黎锐垣. 工业设计的转变: 人工智能全流程应用[J]. 产业创新研究 , 2024(4): 38-40.  \n[4] 马明 , 贾楠 , 苏璐 . 工程图纸图像识别技术在数字化交付中的应用 [J]. 石油化工建设 , 2021, 43(6): 63-65.  \n[5] 李强 . 人工智能教育研究专家系统构建框架及实施 [J].天津市教科院学报 , 2020, 32(1): 42-48.",
+        "category": " References"
+    },
+    {
+        "id": 27,
+        "chunk": "# 版  权  声  明  \n\n录稿通知发出后，视为投稿人已阅读并理解我刊“投稿须知”等内容。例如，投稿人投稿时请勿“一稿多投”；根据国家著作权法，编辑部享有作品的汇编权和文字修改权等权力，所发表文章版权归编辑部所有。投稿人将作品交本刊刊载的同时也同意将其信息网络传播权授予我编辑部等等。本声明所说的信息网络传播权，包含相应的电子版本复制权。如发现已录用稿件有学术不端行为嫌疑的，编辑部有权将其从美国《化学文摘》、知网、万方、维普、超星等数据库平台撤稿。  \n\n《化工设计通讯》编辑部",
+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,397 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (12) United States Patent Jing et al.",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (54) ANTI-FOG COATING COMPRISING AQUEOUS POLYMERIC DISPERSION, CROSSLINKER AND SURFACTANT  \n\n(71） Applicant: 3M INNOVATIVE PROPERTIESCOMPANY, St. Paul, MN (US)  \n\n(72） Inventors: Naiyong Jing, Woodbury, MN (US); Yongshang Lu, Woodbury, MN (US); Dang Xie, Shanghai (CN); Zhigang Yu, Shanghai (CN); John L. Battiste, Northfield, MN (US); Alan L. Levin, Shrewsbury, MA (US); Caroline M. Ylitalo, Stillwater, MN (US); Mahfuza B. Ali, Mendota Heights, MN (US)  \n\n(73） Assignee: 3M Innovative Properties Company, St. Paul, MN (US)  \n\n（\\*） Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 686 days.  \n\n(21) Appl. No.: 14/361,107   \n(22) PCT Filed: Nov. 1, 2012   \n(86) PCT No.: PCT/US2012/062902 $\\S\\ S71$ (c)(1), (2) Date: May 28, 2014   \n(87) PCT Pub.No.: WO2013/089926 PCT Pub.Date: Jun.20, 2013  \n\n(65) Prior Publication Data US 2014/0335360 A1 Nov.13,2014",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# Related U.S. Application Data  \n\n(60） Provisional application No. 61/576,030, filed on Dec. 15,2011.  \n\n(51) Int. Cl. C09D5/16 (2006.01) G02B1/18 (2015.01) C03C 17/32 (2006.01) C09D 5/02 (2006.01) C08K 5/00 (2006.01) G02B 27/00 (2006.01) C03C 17/00 (2006.01)  \n\n(52) U.S. Cl. CPC G02B 1/18 (2015.01); C03C 17/009 (2013.01); C03C 17/32 (2013.01); C03C 17/322 (2013.01); C08K 5/0025 (2013.01); C09D 5/024 (2013.01); C09D 5/1687 (2013.01); G02B 27/0006 (2013.01); C03C 2217/75 (2013.01); Y10T 428/31507 (2015.04);Y10T 428/31551 (2015.04); Y10T 428/31855 (2015.04)  \n\n(58) Field of Classification Search CPC C09D 5/1687 See application file for complete search history.  \n\n(10) Patent No.: US 10,241,237 B2   \n(45) Date of Patent: Mar. 26,2019",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# References Cited",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# U.S. PATENT DOCUMENTS  \n\n2,803,552 A 8/1957 Stedman   \n3,022,178 A 2/1962 Park   \n3,425,976 A 2/1969 Adams   \n3,437,617A 4/1969 Bogle   \n3,484,157 A 12/1969 Crandon   \n3,488,215 A 1/1970 Shepherd   \n3,700,487 A 10/1972 Crandon   \n3,773,776 A 11/1973 Iler   \n3,821,136 A 6/1974 Hudgin   \n3,822,238 A 7/1974 Blair   \n3,865,619 A 2/1975 Pennewiss   \n3,895,155 A 7/1975 Shukuri   \n3,897,356 A 7/1975 Pociluyko   \n4,016,129 A 4/1977 Miyosawa   \n4,027,073 A 5/1977 Clark   \n4,064,308 A 12/1977 Laurin   \n4,108,819 A \\* 8/1978 Oyamada C08L63/00   \n156/330   \n4,126,595A 11/1978 Martorano et al.   \n4,127,682 A 11/1978 Laurin   \n4,211,823 A 7/1980 Suzuki   \n4,310,330 A \\* 1/1982 Funaki .B32B17/10339   \n8/506   \n4,467,073 A 8/1984 Creasy   \n(Continued)",
+        "category": " References"
+    },
+    {
+        "id": 6,
+        "chunk": "# FOREIGNPATENTDOCUMENTS  \n\nCN 1747906 3/2006 CN 101065456 10/2007 (Continued)",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# OTHERPUBLICATIONS  \n\nTriton X-405 Technical Data Sheet, Dow Chemical Company, 2009.\\*   \nPentaerythritol tris[3-(l-aziridinyl)propionate] Safety Data Sheet, Sigma-Aldrich Corporation, Nov. 14,2016.\\*   \nTamol 731A Technical Data Sheet, Dow Chemical Company, Mar. 2013.\\*   \nTrotoir, “Anti-fog/antistat eases processing problems\", Modern Plastics, Oct. 1988, 3 pgs.   \nHowarter, “Self-Cleaning and Next Generation Anti-Fog Surfaces and Coatings\", Macromolecular Rapid Communications, 2oo8, vol. 29, pp. 455-466.  \n\n(Continued)  \n\nPrimary Examiner—Michael F Pepitone (74) Attorney, Agent, or Firm —Adrian L. Pishko; Carolyn A. Fischer",
+        "category": " References"
+    },
+    {
+        "id": 8,
+        "chunk": "# ABSTRACT  \n\nAn anti-fog coating composition is described comprising an aqueous polymeric dispersion; a crosslinker, and a surfactant. The dried and cured coating composition does not exhibit fogging within 8 seconds after being soaked in $25^{\\circ}$ C.water for 1 hour. In favored embodiments, the dried and cured coating composition does not exhibit fogging within 60 seconds after being soaked in $50^{\\circ}\\mathrm{C}$ .water for 24 hours. Also described are articles comprising the dried and cured coating composition disposed on a substrate as well as a method a providing an anti-fog coating on a substrate.  \n\n18 Claims, No Drawings",
+        "category": " Abstract"
+    },
+    {
+        "id": 9,
+        "chunk": "# References Cited",
+        "category": " References"
+    },
+    {
+        "id": 10,
+        "chunk": "# U.S. PATENT DOCUMENTS  \n\n4,478,909 A 10/1984 Taniguchi 4,551,484 A 11/1985 Radisch 4,605,698 A \\* 8/1986 Briden C08K5/3412 524/559 4,609,688 A 9/1986 Radisch 4,745,152 A 5/1988 Fock 5,073,404 A 12/1991 Huang 5,075,133 A 12/1991 Hosono 5,116,442 A 5/1992 Daude 5,124,021 A 6/1992 Kaneyasu 5,134,021 A 7/1992 Hosono 5,262,475A 11/1993 Creasy 5,424,355A 6/1995 Uemae et al. 5,585,186 A 12/1996 Scholz 5,723,175 A 3/1998 Scholz 5,804,612 A 9/1998 Song 5,873,931 A 2/1999 Scholz 5,877,254 A 3/1999 La Casse 6,013,372 A 1/2000 Hayakawa 6,040,053 A 3/2000 Scholz 6,156,409 A 12/2000 Doushita 6,194,498 B1 2/2001 Anderson 6,420,020 B1 7/2002 Yamazaki 6,800,365 B2 10/2004 Yamazaki 7,008,979 B2 3/2006 Schottman 7,048,989 B2 5/2006 Watkins 7,261,843 B2 8/2007 Knox 7,838,110 B2 11/2010 Zhu 8,017,666 B2 9/2011 Bissinger 2003/0203991 A1\\* 10/2003 Schottman C08K3/22 523/334 2003/0205059 A1 11/2003 Roche 2004/0137155 A1 7/2004 Bernheim 2006/0063868 A1 3/2006 Janmaat 2006/0135649 A1 6/2006 Jedlicka et al. 2007/0286959 A1 12/2007 Palmer  \n\n2008/0160187 A1 7/2008 Murata et al.   \n2010/0009108 A1\\* 1/2010 Shih C08L 31/04   \n428/41.3   \n2010/0227945 A1 9/2010 Bissinger et al.   \n2010/0227969 A1 9/2010 Zhu",
+        "category": " References"
+    },
+    {
+        "id": 11,
+        "chunk": "# FOREIGN PATENT DOCUMENTS  \n\nCN 101602913 12/2009   \nCN 101591494 8/2011   \nEP 2062861 5/2009   \nJP 63-150369 6/1988   \nJP H10-25468 1/1998   \nWO WO 1993-23471 11/1993   \nWO WO 1996-18691 6/1996   \nWO WO 0231016 A1 \\* 4/2002 C08J 7/047   \nWO WO 2008-039228 4/2008   \nWO WO 2009-085680 7/2009   \nWO WO 2010-114700 10/2010   \nWO WO 2013-089927 6/2013",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# OTHERPUBLICATIONS  \n\nNie, “Superhydrophilic Anti-Fog Polyester Film by Oxygen Plasma Treatment\", Proceedings of the Nano/Micro Engineered and Molecular Systems, 4th IEEE International Conference, Jan. 2009, pp. 1017-1020.   \nChattopadhyay, “Structural engineering of polyurethane coatings for high performance applications\", Progress in Polymer Science, 2007,vol. 32,pp.352-418.   \nLu, “Durable Anti-fog Coatings form Waterborne Polyurethane Dispersions and Nanoparticles\", Performance Materials and Coating Group, 3M, 13pgs.   \nInternational Search Report for PCT International Application No. PCT/US2012/062902, dated Feb. 7, 2013, 3pgs.  \n\n\\* cited by examiner",
+        "category": " References"
+    },
+    {
+        "id": 13,
+        "chunk": "# 2",
+        "category": " Introduction"
+    },
+    {
+        "id": 14,
+        "chunk": "# 1 ANTI-FOG COATING COMPRISING AQUEOUS POLYMERIC DISPERSION, CROSSLINKER ANDSURFACTANT  \n\nCROSS REFERENCE TO RELATED APPLICATIONS  \n\nThis application is a national stage filing under 35 U.S.C. 371 of PCT/US2012/062902, filed Nov. 1, 2012, which claims priority to Provisional Application No. 61/576, 030, filed Dec. 15, 2011, the disclosure of which is incorporated by reference in its/their entirety herein.",
+        "category": " References"
+    },
+    {
+        "id": 15,
+        "chunk": "# BACKGROUND  \n\nAs described for example in U.S. Pat. No. 7,008,979; fog formation occurs under conditions of high humidity and high temperature or at interfacial boundaries where there is a large temperature and humidity difference. Coatings which reportedly reduce the tendency for surfaces to “fog up\" (i.e., anti-fogging coatings) have been suggested.  \n\nIn order to prevent this fogging, it is known to use various surface active agents to provide anti-fog properties to articles. For example, hydrophilic agents have been added to polyurethanes in order to impart anti-fog properties. Anti- : fog coating compositions for transparent surfaces which include a three-dimensional cross-linked polyurethane having a free surface active agent disposed within open domains in its cross-linked structure have been suggested. The coating compositions are prepared by reacting isocyanates with : polyfunctional polyols to obtain a polyurethane, and subsequently contacting the thus prepared polyurethane with a hydrophilic surface-active agent in order to diffuse molecules of the surface-active agent into the interior of the coating. (See for example U.S. Pat. Nos. 4,551,484 and : 4,609,688 to Radisch et al.)  \n\nThe surface-active agent, however, is not chemically reacted into the polyurethane, but is instead physically disposed within the polymeric structure.As such, the cured coating is susceptible to undesirable leaching and erosion of the surfactant, thereby decreasing the anti-fog properties of the coating composition.  \n\nIt has also been proposed to react surface active agents into a polyurethane coating composition in order to impart anti-fog properties to the coating composition. For example, the addition of sulfonated “resins” to polyurethanes in order to prepare coatings with various properties including antifog characteristics have been suggested. The resins are prepared from diols or diamines reacted with di-carboxylic acid esters, followed by sulfonation of double bonds or quarternization of amines. The resins are intended to increase the hydrophilic character and water absorption of the polyurethane coatings by reacting into the polyurethane backbone in an end-to-end fashion, rather than as pendent groups. Such resins which react in an end-to-end fashion, as opposed to remaining pendant at the end of the polyurethane chain, cannot provide for a clear delineation of hydrophilic and hydrophobic groups and in this respect do not behave as surfactants, i.e., they do not provide cooperation between distinct hydrophilic and hydrophobic portions to reduce interfacial tension.(See for example U.S. Pat. No.3,822,238 to Blair et al.)  \n\nPolyurethane compositions have also been suggested which are useful as coatings for transparent substrates with improved self-healing properties and prevention against formation of surface moisture. The polyurethane compositions are prepared from a reaction of an isocyanate with a polyol mixture including a difunctional sulfonated polyether polyol and a trifunctional polyol. Such a polyurethane composition incorporates only polyol combinations which impart hydrophilic character to the coating, and does not further incorporate into the composition a surfactant material. (See for example U.S. Pat. No. 4,754,152 to Fock et al.)  \n\nHowever, these compositions do not provide permanent fog resistance properties, i.e. fog resistant properties which last after repeated washings or extended soaking in water, nor are they effective for more than a few hours of use.  \n\nAdditionally, it is known to incorporate non-ionic surfactants containing reactive functional groups into polyurethanes prepared with polyvinylpyrrolidone as a hydrophilic agent. For example, anti-fog coating compositions incorporating an isocyanate prepolymer which is reacted with a polyvinylpyrrolidone polymer, the reaction product thereof being subsequently reacted with a non-ionic surfactant having reactive groups for reacting with the isocyanate, for instance, hydroxyl reactive groups are known. Polyvinylpyrrolidone polymers, however, while serving to increase the hydrophilicity of the polyurethane matrix and improve antifog properties, generally reduce the scratch-resistance, chemical resistance, water sensitivity, and durability of the cured polyurethane surface. Thus, although these compositions,when cured, have been known to provide anti-fog properties, their solvent sensitivity, flexibility and scratch resistance properties are less than desirable. (See for example U.S. Pat. No. 4,467,073 to Creasy).",
+        "category": " Introduction"
+    },
+    {
+        "id": 16,
+        "chunk": "# SUMMARY  \n\nAlthough various anti-fog coatings have been described, industry would find advantage in alternative compositions that can provide persistent long-lasting anti-fog properties.  \n\nIn one embodiment, an anti-fog coating composition is described comprising an aqueous polymeric dispersion; a crosslinker, and a surfactant; wherein the dried and cured coating composition does not exhibit fogging within 8 seconds after being soaked in $25^{\\circ}\\mathrm{~C~}$ .water for 1 hour. In favored embodiments, the dried and cured coating composition does not exhibit fogging within 60 seconds after being soaked in $50^{\\circ}\\mathrm{~C~}$ ：water for 24 hours.  \n\nAlso described are articles comprising the dried and cured coating composition disposed on a substrate as well as a method a providing an anti-fog coating on a substrate.",
+        "category": " Abstract"
+    },
+    {
+        "id": 17,
+        "chunk": "# DETAILEDDESCRIPTIONOFILLUSTRATIVE EMBODIMENTS  \n\nThe coating compositions described herein are suitable for imparting anti-fog characteristics. The coating composition comprises an aqueous polymeric dispersion, typically one that can be prepared as a latex, and more typically an alkaline $\\mathfrak{p H}$ stable latex. Favored polymeric dispersions include polyurethane polymer dispersions, acrylic polymer dispersions, and mixture thereof. Such polymers are typically thermoplastic.  \n\nThe term “polyurethane” includes any polymeric material that comprises polyurethane segments. The term “polyurethane segment\" refers to at least two urethane and/or urea groups that are connected by an organic group.  \n\nThe term“acrylic\" includes any polymer or copolymer of acrylic acid, methacrylic acid, ester of these acids or acrylonitrile.  \n\nThermoplastic polyurethane compositions are generally the reaction product of a diisocyanate with short-chain diols (also referred to as chain extenders) and diisocyantes with long-chained difunctional diols (known as polyols). Polyurethanes are characterized as having urethane groups, i.e. —NH— $\\mathrm{C}{=}0\\mathrm{\\Omega}$ O—that link the segments derived from the diisocyanate and diol. Such urethane group comprise a carbonyl group, i.e. a carbon atom double bonded to an oxygen atom, $\\scriptstyle{\\mathrm{C=O}}$  \n\nNon-limiting examples of long-chained polyols are polyether polyols, polyester polyols, acrylic polyols and mixtures of such polyols. Typically, polyester based thermoplastic urethanes are known for providing good abrasion and chemical resistance. The final resin consists of linear polymeric chains in block-structures. Such chains contain low polarity segments, referred to as “soft segments\", alternating with shorter, high polarity segments, referred to as \"hard segments\". Both types of segments are linked together by covalent links, forming random copolymers or blockcopolymers.  \n\nPolyester polyols are prepared by the polyesterification of an organic polycarboxylic acid or anhydride thereof with organic polyols and/or an epoxide. Usually, the polycarboxylic acids and polyols are aliphatic or aromatic dibasic acids and diols. The diols that are usually employed in making the polyester include, but are not limited to,acyclic alkylene glycols, such as ethylene glycol and neopentyl glycol, and cyclic glycols such as hydrogenated Bisphenol A, cyclohexanediol and cyclohexanedimethanol. Polyols of higher functionality can also be used. Non-limiting examples include trimethylolpropane and pentaerythritol, as well as higher molecular weight polyols such as those produced by oxyalkylating low molecular weight polyols.  \n\nThe acid component of the polyester consists primarily of monomeric carboxylic acids or anhydrides having 2 to 18 carbon atoms per molecule. Among the acids that can be used are phthalic acid, terephthalic acid, hexahydrophthalic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, glutaric acid, chlorendic acid, decanoic acid and dodecanoic acid. Higher polycarboxylic acids, such as trimellitic acid and tricarballylic acid, can also be used. Where acids are referred to above, it is understood that anhydrides of those acids that form anhydrides can be used in place of the acid. Also, lower alkyl esters of the acids such as dimethyl glutarate and dimethyl-terephthalate can be used.  \n\nIn addition to the polyester polyols, hydroxy-containing acrylic polymers or acrylic polyols can be used as the polyol component.  \n\nExamples of polyether polyols are polyalkylene ether polyols include those having the following general formula:  \n\nene-bis-(cyclohexyl isocyanate), isophorone diisocyanate and NCO-prepolymers, e.g., the reaction products of monomeric polyisocyanates, such as those mentioned above, with polyester or polyether polyols. Particularly desired are the isocyanurates from isophorone isocyanate and 1,6-hexamethylene diisocyanate, both of which are commercially available.  \n\nIn some embodiments, the polyurethane dispersion comprises a polyester backbone, a polycarbonate backbone, a polyester carbonate or a combination thereof. In other embodiments, the acrylic dispersion comprises an acrylic backbone, a hydroxyl-containing acrylic backbone, or a combination thereof. In yet other embodiments, the poly5 meric dispersion is a urethane-acrylic hybrid, or polycarbonate urethane/acrylic hybrid. In some embodiments, the polymers are described as having a polycarbonate or carbonate backbone. In such embodiments, the polymer comprises aliphatic or aromatic carbonate moieties, such as 0 bisphenol A carbonate moieties.  \n\nVarious processes have been developed for the preparation of waterborne or aqueous polymeric dispersions. In the preparation of aqueous polyurethane polymers, typically a medium molecular weight polymer (e.g. prepolymer) is 25 formed by the reaction of suitable diols or polyols with a molar excess of diisocyantes or polyisocyanates in the presence of an internal emulsifier. The internal emulsifier is typically a diol with an ionic group (carboxylate, sulfonates, or quaternary ammonium slat) or a non-ionic group, such as 30 polyethylene oxide. Aqueous polyurethane dispersion are typically one of three types, i.e. non-ionic, cationic, and anionic depending on the type of hydrophilic segments present in the polyurethane backbone. In the case of anionic 351 polyurethanes, dimethyol propionic acid (DMPA) is commonly incorporated into the polyurethane backbone due to its effectiveness for water dispersions in the subsequent neutralization reactions with triethylamine. The carboxylate ion of DMPA in the polymer is hydrophilic and serves an 40 anionic center as well an internal emulsifier.Carboxylic ions not only stabilize aqueous polyurethane dispersions, but also provide curing sites. Aqueous acrylic polymers are also typically prepared with an internal emulsifier and thus typically also comprise carboxylate ions to stabilize the 45 dispersion and provide curing sites.  \n\nThe (e.g. polyurethane and/or acrylic) polymer is generally dispersed in a liquid diluent to form a polymeric dispersion.“Liquid diluent\" refers to solvent that is volatile and removed after the coating is applied. In favored embodi  \n50 ments, the coating composition comprises predominantly water as the diluent with little or no organic solvents. In this embodiment, the concentration of organic solvent is typically less than 2, 1.5, $1\\ \\mathrm{wt}\\mathrm{-}\\%$ or $0.5\\mathrm{\\wt-\\%}$ of the coating composition. A polyurethane dispersion available from   \n55 Incorez, under the trade designation “W835 Series” are described as being co-solvent free grades of polyurethane dispersions.  \n\nwhere the substituent R is hydrogen or lower alkyl contain- 55 ing from 1 to 5 carbon atoms including mixed substituents, and n is typically from 2 to 6 and m is from 10 to 100 or even higher. Included are poly(oxytetramethylene)glycols, poly (oxyethylene)glycols, poly(oxy-1,2-propylene)glycols and the reaction products of ethylene glycol with a mixture of 6( 1,2-propylene oxide and ethylene oxide.  \n\nThe polyisocyanates that can be used include aromatic and aliphatic polyisocyanates with aliphatic polyisocyanates being more desirable because of their superior ultraviolet light stability and non-yellowing tendencies. Non-limiting examples of such polyisocyanates include monomeric polyisocyanates, such as toluene diisocyanate, and $^{4,4^{\\prime}}$ -methyl  \n\nThe (e.g. polyurethane and/or acrylic) polymer dispersed in an aqueous diluent are film-forming polymers. Suitable polymer latexes and methods for making them are widely known in the art, and many are commercially available.  \n\nTypically, the particles in the polymer latexes are substantially spherical in shape. The polymer core may comprise one or more water-insoluble polymers, although this is not a requirement. Useful polymer particle sizes include those typical of latexes and other dispersions or emulsions. Typical polymer particle sizes are in a range of from about",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# 5",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 6  \n\n0.01 micrometers to 100 micrometers, preferably in a range of from O.o1 to 0.2 micrometers, although this is not a requirement.  \n\nExamples of commercially available aqueous aliphatic polyurethane emulsions include NEOREZ R-960, NEOREZ R-967,NEOREZR-9036, andNEOREZR-9699 fromDSM NeoResins, Inc. of Wilmington, Mass.; aqueous anionic polyurethane dispersions available as ESSENTIAL CC4520,ESSENTIAL CC4560, ESSENTIAL R4100, and ESSENTIAL R4188 from Essential Industries, Inc. of Merton,Wis.; polyester polyurethane dispersions available as SANCURE 843,SANCURE 898,and SANCURE 12929 from Lubrizol, Inc. of Cleveland, Ohio; an aqueous aliphatic self-crosslinking polyurethane dispersion available as TURBOSET 2025 from Lubrizol, Inc.; polyurethanes dispersions available from Stahl USA, Peabody, Mass.under the trade designations“RU-077” and“RU- $075^{,}$ ·  \n\nSelf cross-linking polymer dispersion maybe used in the ink receptive layer. Such polymeric dispersions have self cross-linking function that is activated upon drying of the coating layer. The use of this type of dispersions may eliminate the need for incorporating crosslinking compounds into the coating composition. Examples of self cross-linking polymer dispersions include polyurethane dispersions available from Bayer Material Science, LLC of Pittsburgh, Pa. as “BAYHYDROL PR240” and from DSM Neoresins as“NEOREZ R-661\".  \n\nExamples of commercially available aqueous aliphatic acrylic emulsions include acrylic latexes available from Dow Coating Materials under the trade designations ROSHIELDTM and RHOPLEXTM such as“ROSHIELDTM 3188\"，“ROSHIELDTM3275”，“ROSHIELDTM1024” “ROSHIELDTM 636\",“RHOPLEXTM WL-96\",and “RHOPLEXTM CL- $104^{,}$ ; acrylic latexes available from Arkema Coating Resins under the trade designation “UCARTM\", such as “UCARTM LATEX $455'$ ,“UCARTM LATEX 443\", “UCARTM LATEX 451\", and “UCARTM LATEX $\\mathrm{DM}109^{\\circ}$ acrylic latexes available from Lubrizol Advanced Materials, Inc. under the trade designation HYCAR $\\textsuperscript{\\textregistered}$ ， such as \"HYCAR $\\textsuperscript{\\textregistered}$ $26349^{\\circ}$ ; “HYCAR $\\textsuperscript{\\textregistered}$ $26459^{\\circ}$ ; and acrylic latexes available from DSM NeoResins under the trade designation “NEOCRYL\",such as “NEOCRYL $\\mathrm{A}{-}640^{3}$ ，“NEOCRYL $\\mathrm{XK-}220^{\\circ}$ ，“NEOCRYL $\\mathrm{A-}1044^{\\cdots}$ ，“NEOCRYL XK-90\" “NEOCRLYL XK-96”and “NEOCRYL XK-95\".  \n\nDispersions of polyurethane polymers can be characterized by measuring the properties of a 50-100 micron thin film of the neat polyurethane formed from the dispersion (dried at $22^{\\mathrm{o}}\\mathrm{~C}./50\\%$ RH for 14 days). In some embodiments, the elongation of the thin film thus formed typically has an elongation at break ranging from about $500\\%$ to about $60\\%$ . In some embodiments, the tensile strength ranges from about 15 to $30\\mathrm{MPa}$ \\*  \n\nIn some embodiments, the acrylic dispersion comprises a polyacrylate backbone, a polycarbonate backbone, or a combination thereof.  \n\nA combination of polymeric polymers may be utilized in the (e.g. anti-fog） coating composition.For example, the polyurethane dispersion may comprise two or more polyurethane polymers having a different average molecular weight. Further, the composition may contain a different ( type of polymer in combination with a polyurethane, for example, as would be obtained by mixing an acrylic latex and a polyurethane latex. In one embodiment, the aqueous polyurethane dispersion comprises a mixture of “INCOREZ W835/140\"and“NEOREZR-961\".The inclusion of\"NEO-( REZ R-961” can improve the abrasion resistance. However, when the concentration of “NEOREZ R-961”exceeds a a weight ratio of about 1:2 (i.e. more than 1 part by weight “NEOREZ R-961” per 2 parts by weight“INCOREZ W835/ $140^{7})$ , the coating can become white after being soaked in water. In yet another example, a combination of a polyurethane polymer and an acrylic polymer is utilized or a hybrid polymer of both acrylic and polyurethane. An example of a commercially available acrylic urethane copolymer dispersion is available under the trade designation NEOPAC from DSM Neoresins.  \n\n0 The coating composition typically comprises one or more (e.g. polyurethane and/or acrylic) polymers in an amount totaling at least $40\\mathrm{wt}-\\%$ solids of the coating composition and typically no greater than $90\\ \\mathrm{wt-\\%}$ or $85\\mathrm{\\wt-\\%}$ or 80 wt- $\\%$ . In some embodiments, the coating composition com5 prises one or more polymers in an amount of at least 45 wt- $\\%$ or $50\\ \\mathrm{wt-\\%}$ ，  \n\nThe (e.g. anti-fog) coating compositions described herein comprise at least one surfactant. The term “surfactant\" as used herein describes molecules that reduce the surface tension of the coating composition and provide a coating that imparts“good” or “excellent” anti-fog properties to substrates or articles coated therewith, according to the test method described in the examples. Surfactant molecules generally include both hydrophilic (polar) and hydrophobic (non-polar) segments on the same molecule.  \n\nUseful surfactants of the present invention include ionic (e.g. anionic, cationic) non-ionic, as well as amphoteric surfactants. A surfactant can be classified by the presence of formally charged groups in its head. The head of an ionic   \n30 surfactant carries a net charge. An anionic surfactant has a negatively charged hydrophilic group, such as in the case of alkyl sulphates and alkyl ethoxylated sulfates. Cationic surfactants have a positively charged hydrophilic group, such as in the case of sodium salts and quaternary (e.g   \n35 ammonium) salts. A non-ionic surfactant has no charged groups in its head. Some illustrative surfactants are described in WO 2009/085680; incorporated herein by reference. For embodiments wherein the coating composition lacks   \n40 an acid or salt of a polyalkylene oxide as a hydrophilic component, the coating composition comprises a suficient amount of surfactant to render the coating composition an anti-fog composition. The surfactant concentration in the coating compositions is typically at least $0.5\\mathrm{wt}-\\%$ ,1wt- $\\%$ D   \n451.5 wt- $\\%$ ,or2 wt- $\\%$ percent of the coating composition. The surfactant concentration is typically no greater than $10\\mathrm{wt-}\\%$ of the coating composition.  \n\nIn some embodiments, the (e.g. anti-fog) coating composition comprises a non-ionic surfactant. Non-ionic surfac50 tants generally comprise an alkyl or alkenyl group having at least 6, or 8, or 10, or 12 carbon atoms. Such relatively long chain alkyl or alkylene group is commonly referred to as a \"fatty\" group. The number of carbon atoms can be greater than 18 carbon atoms provided the non-ionic surfactant is a 55 liquid at ambient temperature (e.g. $25^{\\circ}\\mathrm{C}.$ . In some embodiments, the alkyl or alkenyl group has no greater than 24 carbon atoms. In some favored embodiments, such alkyl group is unbranched. The alkyl or alkenyl group may optionally comprise substituents.  \n\nVarious classes of non-ionic surfactants are known including for example fatty alcohols, fatty acids, fatty amines, fatty amides, and derivatives thereof.  \n\nFatty alcohols typically have the general formula:",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 20,
+        "chunk": "# R—OH  \n\nwherein R is a (e.g. straight or branched chain) alkyl or alkenyl group, as previously described, optionally substituted in available positions by N, O, or S atoms. Various fatty alcohols are known including dodecyl alcohol, cetyl alcohol $\\mathrm{CH}_{3}(\\mathrm{CH}_{2})_{15}\\mathrm{OH}$ ， stearyl alcohol (also known as octadecyl alcohol or 1-octadecanol), and oleyl alcohol.  \n\nIn some embodiments, the non-ionic surfactant is a 5 derivative of a fatty alcohol. One favored derivative is a fatty alcohol, ester or derivative thereof comprising alkylene oxide repeat units such as ethylene oxide and/or propylene oxide repeat units. Such derivatives may also be referred to as a polyethoxylated and/or polypropoxylated fatty alcohols, 1( esters, or derivatives thereof. Polyethoxylated fatty alcohols have the general formula:  \n\n$$\n\\mathrm{R}{\\longrightarrow}(\\mathrm{OCH}_{2}\\mathrm{CH}_{2})_{n}\\mathrm{OH}\n$$  \n\nwherein R is a (e.g. straight or branched chain) alkyl or 1: alkenyl group, as previously described, optionally substituted in available positions by N, O, or S atoms. The number of ethylene oxide repeat units, “n\" can range from 2 to 20. In some embodiments, n is at least 3 or 4 and no greater than about 10 or 12. 2(  \n\nSurfactant comprising polyalkylene oxide repeat units, such as polyethoxylated fatty alcohols, can be a favored non-ionic surfactant of the coating composition.  \n\nIn some embodiments, one or more polyethoxylated fatty alcohols are the sole surfactant of the coating composition. In other embodiments, at least one polyethoxylated fatty alcohol is employed in combination with a second surfactant. The polyethoxylated fatty alcohol surfactant may be utilized in combination with a second surfactant at a weight ratio of about 1:1 or 2:1. In some embodiments, the second surfactant is a silicone surfactant, an ionic surfactant,or mixture thereof.  \n\nThe some embodiments, the coating composition comprises a non-ionic surfactant in combination with an ionic surfactant or silicone surfactant.  \n\nSilicone surfactants generally comprises a siloxane backbone with a various number of dimethyl siloxane units, typically end-capped with a trimethyl siloxane group at each end. The siloxane backbone is generally the hydrophobic group. The hydrophilic group can be ionic, zwitterionic, or non-ionic and are usually attached by a short alkyl chain to the siloxane backbone. One illustrative siloxane surfactant is a polyether modified siloxane, commercially available from Innovadex under the trade designation “BYK-346\".  \n\nVarious ionic surfactants are known. One illustrative ionic surfactant is a sodium alpha olefin sulfonate, commercially available from Stepan Company under the trade designation “A-18\". Another ionic surfactant is a polyoxyethylene alkylphenyl ether ammonium sulfate, commercially available from Dai-Ichi Kogyo Seiyaku., Ltd. of Japan under the trade designation “Hitenol BC $10^{\\circ}$  \n\nVarious non-ionic surfactants as previously described comprise a hydroxyl group. Anti-fog coatings have been previously described wherein a hydroxyl functional surfactant is utilized as a reactant during the formation of the polyurethane. (See for example U.S. Pat. No. 3,822,238) However, in the presently described anti-fog coating compositions a preformed (e.g. commercially available) polymer, provided as an aqueous dispersion is utilized as a component. The polymer of the dispersion is typically free of hydroxyl-reactive. Hence, when a hydroxyl functional surfactant is combined with such polyurethane dispersion, the surfactant does not react with the polyurethane due. In other words the surfactant is non-reactive with respect to the (e.g. polyurethane and/or acrylic) polymer.  \n\nThe anti-fog coating described herein may optionally comprise various hydrophilic additives.A hydrophilic additive is distinguished from a surfactant in that a hydrophilic additive lacks a hydrophobic group, a requisite group of a surfactant. In some embodiments, the coating compositions comprise a small concentration of a (e.g. non-reactive) hydrophilic additive, such as a polyethylene glycol (PEG) monomethyl ether, to enhance the anti-fog performance. In this embodiment, the concentration of the hydrophilic additive is typically at least $0.5~\\mathrm{wt-\\%}$ ,or1 wt- $\\%$ ,or $1.5~\\mathrm{wt-\\%}$ . or $2\\ \\mathrm{wt-\\%}$ and generally no greater than about $5\\mathrm{wt-\\%}$  \n\nIn another embodiment, the anti-fog coating comprises a hydrophilic additive that is non-reactive with respect to the polyurethane polymer, yet is reactive and thus can be crosslinked by the (e.g.aziridine) crosslinker. The concentration of such hydrophilic additive is typically at least 5 wt- $\\%$ ,6wt- $\\%$ ，7wt- $\\%$ ,8wt- $\\%$ ，9wt- $\\%$ or $10\\mathrm{wt}\\%$ of the solids of the coating composition. In some embodiments, the concentration of hydrophilic additive is at least $11\\mathrm{\\wt{-}}\\%$ ，12 wt- $\\%$ 。 $13\\mathrm{\\wt-\\%}$ D $14\\mathrm{wt}\\%$ ,or $15\\ \\mathrm{wt-\\%}$ . The concentration of such hydrophilic additive is typically no greater than about 35wt- $\\%$  \n\nOne example of a hydrophilic additive that can be crosslinked by the crosslinker is an acid or salt of a polyalkylene oxide. Such additive generally comprises a polyalkylene oxide backbone that comprises repeat units of the ethylene   \n25 oxide, propylene oxide, or a combination thereof. The number of ethylene oxide and propylene oxide repeat units may independently range from O to 100 with the proviso that the sum of ethylene oxide and propylene oxide repeat units range from about 10 to 10o. The polyalkylene oxide back  \n30 bone typically comprises more ethylene oxide repeat units than propylene oxide repeat units. In some embodiments, the ratio of ethylene oxide repeat units to propylene oxide repeat units is at least 2:1, or 3:1; or 4:1, or 5:1, or 6:1 or 7:1, or 8:1,or 9:1, or 10:1. The polyalkylene oxide backbone is   \n35 typically linear and divalent, terminating with an acid or salt group on each end. A divalent linking group is typicaly present between the polyalkylene oxide backbone and at least one or two terminal acid or salt groups. Depending on the starting compound and reactant(s), the linking group can   \n40 vary. In some embodiments, the additive is formed from a polyalkylene oxide amine (also referred to as a polyether amine) reacted with a succinic anhydride forming a diacid that is then reacted with an alkyl amine to convert the acid group to an ammonium salt group. In this embodiment, the   \n45 linking group between the polyalkylene oxide backbone and theterminal acid or salt groups may be $\\mathrm{-CH}_{2}\\mathrm{NHCOC}_{2}\\mathrm{H}_{4}-$ . However, other linking group would be present by use of other reaction schemes. The molecular weight of the linking group is generally relatively small so   \n50 as not to detract from the hydrophilic nature of the polyalkylene oxide backbone. In some embodiments, the molecular weight of the linking group is no greater than 100 g/mole. As the molecular weight of the polyalkylene oxide backbone increases, the molecular weight of the linking   \n55 group may also increase without detracting from the hydrophilic properties. However, the molecular weight of the linking group is typically no greater than about 20, 15 or $10\\%$ by weight of the total molecular weight of the hydrophilic additive (i.e. the molecular weight of the linking   \n60 groups divided by the total molecular weight multiplied by $100\\%$ ，  \n\nIn one embodiment, the hydrophilic additive comprises a divalent polyalkylene oxide backbone and terminal acid or salts groups, as may be represented by the following formula:  \n\n$$\n\\mathrm{R-L-}(\\mathrm{C}_{3}\\mathrm{H}_{6}\\mathrm{O})\\mathrm{-}(\\mathrm{C}_{2}\\mathrm{H}_{4}\\mathrm{O})_{y}\\mathrm{-L-R}\n$$  \n\nwherein is $\\mathrm{~R~}$ is a reactive group that is capable of (covalently) reacting with the (e.g. aziridine) crosslinker such as a carboxylic acid group or salt thereof,  \n\nL is a divalent linking,  \n\nand $\\mathbf{x}$ and y independently range from O to 100 with the proviso that the sum of $\\mathbf{x}{+}\\mathbf{y}$ ranges from about 5, 6, 7, 8, 9, or 10 to about 100.  \n\nThe linking group L can vary depending on the selection of reactants. For example, when a polyalkylene oxide diol is reacted with an isocyanate compound, Lmay be 10 —OCONH—. In another embodiment, when a polyalkylene oxide diamine is reacted with an isocyanate compound, L may be—NHCONH—. In yet another embodiment, when a polyalkylene oxide diol is reacted with an anhydride or carboxylic acid compound, L may be —( $\\mathrm{C}{=}0_{,}$ O—.L15 may also be an ester linkage when a polyalkylene oxide diacid is reacted with an alcohol compound. In yet another embodiment, L may be —CONH— by reaction of a polyalkylene oxide diacid or acrylic chloride with a primary or secondary amine.The amide linkage can also be made by the 20 reaction of a polyalkylene diamine with an anhydride or a carboxylic acid compound. In yet another embodiment, L may be—NR—by reaction of a polyalkylene oxide diamine with a halide compound or by reaction of a polyalkylene oxide dihalide with an amine compound. In yet another 25 embodiment, L can be —COS— by the reaction of a polyalkylene oxide diol with an acryl chloride thiol or thiol ester compound. Further, L may be — $\\mathrm{CS}_{2}$ — by reaction a polyalkylene oxide dithiol with a thiol or mercapto compound. In yet another embodiment, L may be —S— by 30 reaction of a polyalkylene oxide dithiol with a halide compound. In yet another embodiment, L may be —O— by a condensation reaction of polyalkylene oxide diol. In yet another embodiment, L may be—SCONH—by the reaction of a polyalkylene oxide dithiol with an isocyanate com- 35 pound or by reaction of a polyalkylene oxide diisocyanate with a thiol compound.  \n\nThe counter ions of the acid salts can be ammonium, as well as primary, secondary or tertiary alkyl ammoniums. The counter ions may also be inorganic metallic ions includ- 40 ing divalent zinc from zinc halides, nitrate, carbonate,or ammonium carbonate. Other inorganic metallic ions comprise Cu, Ti, and $Z\\mathrm{r}$  \n\nWithout intending to be bound by theory it is surmised that alkylene oxide repeat units of the acid or salt of 45 polyalkylene oxide can aid in preventing a surfactant, compatible with such hydrophilic segments (e.g. such as a non-ionic surfactant comprising alkylene oxide repeat units) from leaching out of the coating.  \n\nThe anti-fog coatings described herein comprise a cross- 5( linker. The crosslinker typically reacts with the (e.g. carboxylate) hydrophilic segments present in the polymer (eg. polyurethane and/or acrylic) backbone.Favored crosslinkers include multifunctional aziridine crosslinkers, typically comprising at least three terminal groups. 5  \n\nCarboxylic ion (e.g. carboxylate） containing aqueous polymeric dispersions and a multi-aziridine curing agent may be formulated as a curing polymeric dispersion. The curing mechanism can take place at ambient temperature during the drying process of when the pH value drops below 6. In some embodiments the crosslinker may also react with the (e.g. acid or salt of a polyalkylene oxide) hydrophilic additive, as just described.  \n\nThe concentration of (e.g. aziridine) crosslinker is typically at least 5 wt- $\\%$ solids of the coating composition. In some embodiments, a relatively high concentration of (e.g. aziridine) crosslinker is utilized. For example, the concentration of (e.g. aziridine) crosslinker is typically at least 10 or $15\\ \\mathrm{wt}\\mathrm{-}\\%$ of the solids of the coating composition. The concentration of (e.g. aziridine) crosslinker is typically no greater than 25 wt- $\\%$ ,or $24\\mathrm{wt-\\%}$ ,or $23\\ \\mathrm{wt-\\%}$ ,or22wt- $\\%$ D or 21 wt- $\\%$ or $20\\mathrm{\\wt-\\%}$  \n\nVarious multifunctional aziridine crosslinkers are known such as trimethylolpropane tri-[beta-(N-aziridinyl)-propionate, 2,2-bishydroxymethyl butanoltris[3-(1-aziridine) propionate], aziridine-2-methylol acrylate, aziridine-2-methylol methacrylate, N-(2-aziridinyl)methylacrylamide, N-(2- aziridinyl)methylmethacrylamide, 1-(aziridin-2-yl)-2-oxabut-3-ene, 4-(aziridin-2-yl)-but-l-ene, and 5-(aziridin-2- yl)-pent-l-ene. These particular aziridine crosslinkers are relatively hydrophobic crosslinkers.  \n\nParticularly for embodiments wherein the crosslinker is present at relatively high concentrations, it can be favored to utilize a hydrophilic aziridine crosslinker, rather than a hydrophobic crosslinker.A hydrophilic aziridine crosslinker may comprise alkylene oxide repeat units, such as ethylene oxide repeat units. The number of alkylene oxide (e.g ethylene oxide) repeats units is typically at least 2 or 3 and typically no greater than about 20. In some embodiments, the number of alkylene oxide (e.g. ethylene oxide) repeat units averages about 6, 7, 8, or 9. The use of a hydrophilic crosslinker is favored for embodiment wherein the composition is substantially free of or comprises a low concentration (no greater than 5 wt $\\%$ ) of hydrophilic additives.  \n\nAn aziridine crosslinker comprising ethylene oxide repeat units can be prepare by reacting an ethoxylated alkyl multi (meth)acrylate, such as ethoxylated (9) trimethyl propane triacrylate with an alkyl aziridine, such as 2-methylaziridine. Such aziridine crosslinker has the general formula:  \n\n![](images/0cc38584288d4d7cb0fca27a8a9bcf6c166c986a7a045434aaeb686a49bf7e92.jpg)  \n\nwherein R' is hydrogen, or a $\\mathrm{C_{1}{-}C_{4}}$ alkyl group; $\\mathrm{R}\"$ is hydrogen or methyl,  \n\nx, y, and $z$ are independently at least 1; and M is a divalent atom of divalent linking group.  \n\nIn some embodiments, the sum of $\\ x+y+z$ is at least 3, 4, 5, or 6. Further the sum of $\\mathbf{x}+\\mathbf{y}+\\mathbf{z}$ may be no greater than 20. In some embodiments, M is oxygen.  \n\nOther aziridine crosslinkers comprising alkylene oxide repeat units are described in U.S. Pat. No. 8,017,666; incorporated herein by reference.  \n\nWithout intending to be bound by theory it is surmised that alkylene oxide repeat units of the crosslinker aid in preventing a surfactant, compatible with such hydrophilic segments (e.g. such as a non-ionic surfactant comprising alkylene oxide repeat units) from leaching out of the coating.  \n\nIn some embodiments, one or more surfactants and a hydrophilic aziridine crosslinker are the primary or sole hydrophilic components of the coating composition.  \n\nIn other embodiments, the composition further comprises 5 an acid or salt of a polyalkylene oxide.  \n\nIn each of these embodiments, the coating composition may comprise less than 5 wt- $\\%$ or no other hydrophilic organic monomers, oligomer or polymers such as monomer or polymers derived from N-vinylpyrrolidone.  \n\nIn some embodiments, the anti-fog coating compositions are free of inorganic nanoparticles. Such dried and cured composition typically exhibits satisfactory abrasion resistance due to the selection of polyurethane and the relatively high concentration of crosslinker.  \n\nIn other embodiments, the coating composition comprises inorganic nanoparticles at a concentration of at least 0.5 wt- $\\%$ ,1wt- $\\%$ or2wt- $\\%$ and typically no greater than about $40\\ \\mathrm{wt-\\%}$ of the solids of the coating composition. In some embodiments, the concentration of inorganic nanoparticles is no greater than about $30\\mathrm{\\mt{-}}\\%$ or $20\\mathrm{\\wt-\\%}$ .In some embodiments, the linear abrasion is compromised, particularly with 200 or 300 cycles when the nanoparticle concentration is $15\\ \\mathrm{wt-\\%}$ or greater.  \n\n“Nanoparticles” are herein defined as nanometer-sized particles, preferably with an average particle size of no greater than 100, 75 or 50 nanometers (nm). In some embodiments, the average particle size of the inorganic nanoparticles is no greater than 40, or 30, or $20\\mathrm{nm}$ (prior to surface modification. The average particle size of the nanoparticles is at least $1\\ \\mathrm{nm}$ ，2 nm, or $3\\ \\mathrm{nm}$ ·  \n\nAs used herein,“particle size” and “particle diameter” have the same meaning and are used to refer to the largest dimension of a particle (or agglomerate thereof). In this context, “agglomeration” refers to a weak association between particles which may be held together by charge or polarity and can be broken down into smaller entities.  \n\nAverage particle size of the nanoparticles can be mea- 30 sured using transmission electron microscopy. In the practice of the present invention, particle size may be determined using any suitable technique. Particle size refers to the number average particle size and is measured using an instrument that uses transmission electron microscopy or 35 scanning electron microscopy. Another method to measure particle size is dynamic light scattering that measures weight average particle size. One example of such an instrument found to be suitable is the N4 PLUS SUB-MICRON PARTICLE ANALYZER available from Beckman Coulter Inc. 40 of Fullerton, Calif.  \n\nThe nanoparticles may be relatively uniform in size. Uniformly sized nanoparticles generally provide more reproducible results. Preferably, variability in the size of the nanoparticles is less than $25\\%$ of the mean particle size.  \n\nThe nanoparticles preferably have a surface area of at least $10\\mathrm{m}^{2}/\\dot{\\mathrm{g}}\\mathrm{ram}$ ，more preferably at least $20~\\mathrm{m}^{2}/\\mathrm{gram}$ ,and even more preferably at least $25\\mathrm{{m}}^{2},$ /gram. The nanoparticles preferably have a surface area of greater than $750\\mathrm{\\m}^{2}/\\mathrm{gram}$  \n\nNanoparticles of the present invention can be porous or nonporous. In some embodiments, the nanoparticles consist solely of only silica. Silica can be preferred nanoparticles, particularly silica nanoparticles derived from a silicate, such as an alkali metal silicate or ammonium silicate. Herein, “silica nanoparticles\" refer to nanoparticles that include only silica as well as to core-shell nanoparticles with a surface that includes silica. In other embodiments, the coating composition may comprise other inorganic oxides such as $\\mathrm{ZrO}_{2}$ ， colloidal zirconia, $\\mathrm{Al}_{2}\\mathrm{O}_{3}$ ， colloidal alumina, $\\mathrm{CeO}_{2}$ colloidal ceria, $\\mathrm{SnO}_{2}$ ,colloidal tin (stannic) oxide, and $\\mathrm{TiO}_{2}$ % colloidal titanium dioxide). Mixtures of such inorganic oxides can also be utilized.  \n\nThe unmodified nanoparticles are typically provided as a dispersion rather than as a powder. Preferred dispersion generally contain from $15\\ \\mathrm{wt}-\\%$ to $50\\ \\mathrm{wt-\\%}$ of colloidal particles dispersed in a fluid medium. Representative examples of suitable fluid media for the colloidal particles  \n\ninclude water, aqueous alcohol solutions, lower aliphatic alcohols, ethylene glycol, N,N-dimethylacetamide, formamide, or combinations thereof. The preferred fluid medium is aqueous, e.g., water and optionally one or more alcohols.   \n； Inorganic silica sols in aqueous media are well known in the art and available commercially. Silica sols in water or water-alcohol solutions are available commercially under such trade names as LUDOX (manufactured by E.I. duPont de Nemours and Co., Inc., Wilmington, Del.), NYACOL   \n0 (available from Nyacol Co.,Ashland, Mass.) or NALCO (manufactured by Nalco Chemical Co., Naperville, Ill.). Useful silica dispersions include “NALCO 1115” and \"DVSZNoo4\", both available from Nalco Chemical Company.  \n\n5 The inorganic nanoparticles typically comprise a surface treatment. Surface-treating the nano-sized particles can provide a stable dispersion in the polymeric resin. Preferably, the surface-treatment stabilizes the nanoparticles so that the particles will be well dispersed in the aqueous polyurethane :0 dispersion and results in a substantially homogeneous composition. Furthermore, the nanoparticles can be modified over at least a portion of its surface with a surface treatment agent so that the stabilized particle can copolymerize or react with the polyurethane or aziridine crosslinker during :5curing.  \n\nIn general a surface treatment agent has a first end that will attach to the particle surface (covalently, ionically or through strong physisorption) and a second end that imparts compatibility of the particle with the remainder of the coating composition and/or reacts with components of the coating composition during curing. Examples of surface treatment agents include alcohols, amines, carboxylic acids, sulfonic acids, phosphohonic acids, silanes and titanates. The preferred type of treatment agent is determined, in part, by the chemical nature of the metal oxide surface. Silanes are preferred for silica and other for siliceous fillers.  \n\nIn some embodiments the nanoparticles comprise a surface treatment comprising a water dispersible group. Waterdispersible groups are monovalent groups that are capable of providing hydrophilic characteristics to the nanoparticle surface, thereby reducing, and preferably preventing, excessive agglomeration and precipitation of the nanoparticles in an aqueous coating solution. Such surface treatment can be represented by the formula A-L-WD, wherein A are the surface-bonding groups (i.e. for bonding to the nanoparticle surface), WD represents the water-dispersible groups, and L represents an organic linker or a bond. Organic linkers L can be linear or branched alkylene, arylene, or a combination of alkylene and arylene groups, optionally including heteroatoms.  \n\nThe water-dispersible groups are hydrophilic or waterlike groups. They typically include, for example, nonionic groups, anionic groups, cationic groups, groups that are capable of forming an anionic group or cationic group when dispersed in water (e.g., salts or acids), or mixtures thereof.  \n\nExamples of nonionic water-dispersible groups include polyalkylene oxide (e.g. PEG) groups. One illustrative silane surface treatment for use with silica nanoparticles is a polyethylene oxide (PEG) silane, such as 2-[methoxy (polyethyleneoxy)propylltrimethoxysilane.Thesurface treatment may comprise other water dispersible groups, as well as epoxy silane surface treatments, such as described in WO2009/085680; incorporated herein by reference.  \n\nThe preferred amount of surface modifier can depend on several factors such particle size, particle type, modifier molecular weight, and modifier type. In general it is preferred that approximately a monolayer of modifier is",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 21,
+        "chunk": "# 13  \n\nattached to the surface of the particle. The attachment procedure or reaction conditions required also depend on the surface modifier used. For silanes it can be preferred to surface treat at elevated temperatures under acidic or basic conditions for approximately 1-24 hours.  \n\nThe level of coverage of the inorganic nanoparticles herein is reported in terms of the concentration of epoxy groups in the coating composition, assuming $100\\%$ of the amount of functional groups of the surface treatment would be covalently bonded to surface of the silica particles. In some embodiments, the inorganic nanoparticles comprise a surface treatment at $25\\%$ or $50\\%$ coverage.  \n\nCoating compositions can be supplied in liquid form (e.g., in a pourable form or sprayable form) or impregnated into an applicator substrate (e.g., forming an applicator pad or 1: wipe). Suitable applicator substrates can be in the form of a sponge，foam, woven, nonwoven, or knit material,for example. The term“nonwoven web” or“nonwoven fabric” refers to a web or fabric having a structure of individual fibers that are interlaid in an irregular manner. In contrast, 2 knit or woven fabrics have fibers that are interlaid in a regular manner.  \n\nThe liquid polyurethane coating compositions can be applied by conventional methods, including spraying, spin coating, brushing, dipping, flow coating, etc., but typically are applied by spin coating or spraying. The coating operation can be conducted either in a single stage or by a multiple stage coating procedure, as is well known in the art. The conditions adopted for curing the (e.g. aziridine) crosslinkers with the polyurethane polymer can vary. In some embodiments, the coating is thermally cured at a temperature from about 90 to $120^{\\circ}$ C. for about 20 minutes. Generally, lower temperatures require longer cure times. Infrared heating can be used to shorten the time until the coating can be handled.  \n\nThe dried and cured coating compositions described herein can exhibit high transparency, greater than $90\\%$ and thus are suitable for application to a variety of light transmissive substrates and articles. The haze of the dried and cured coating is typically less than 5, 4, 3, 2, 1 or $0.5\\%$ .The highly transparent compositions are typically substantially free of opacifiying pigments (i.e. less than 0.5 or 0.1 wt $\\%$ j The coating compositions can provide anti-fog properties to substrates coated and dried and cured thereon. Dried and cured coatings are considered to have“good'\" or“excellent” anti-fogging properties if a coated substrate resists the formation of small, condensed water droplets in sufficient density to significantly reduce the transparency of the coated substrate such that it cannot be adequately seen through, according to the test method described in the example.  \n\nIn some embodiments, the dried and cured coating compositions are sufficiently durable that such that good or excellent anti-fog characteristics are provided initially and after being soaked in $25^{\\circ}\\mathrm{~C~}$ .water for 1 hours. In other embodiments, the dried and cured coating compositions are sufficiently durable that they can provide good or excellent anti-fog characteristics after being soaked in or $50^{\\circ}\\mathrm{C}$ water for 24 hours or $65^{\\circ}\\mathrm{C}$ water for 120 hours.  \n\nIn some embodiments, the dried and cured coating compositions exhibited mechanical durability (i.e., the haze of the coatings increased only $1-7\\%$ haze change) after linear razor abrasion test and no scratches were observed after wiping the coatings with a paper towel for 100, 200, or 300 cycles.  \n\nThere are various articles that can benefit from an anti-fog 6 coating such as traffic signs,motor vehicle windows and particularly windshields, protective eyewear (e.g. goggles, face shields, helmets, etc.) and architectural glazings, as well as other decorative glass articles.  \n\nSubstrates to which the antifog coating composition can be applied are preferably transparent or translucent to visible light. If the coating composition is utilized for a different purpose, the substrate may alternatively be opaque such as in the case of stainless steel, polyvinyl chloride, and fiberboard. Substrates include both organic and inorganic materials. Exemplary substrates are made of polyester (e.g., polyethylene terephthalate (PET), polybutyleneterephthalate), polycarbonate (PC), allyldiglycolcarbonate, polyacrylates such as polymethylmethacrylate, polystyrene, polysulfone, polyethersulfone, cellulose acetate butyrate, glass, and the like, including blends and laminates thereof. Typically the substrate is in the form of a film, sheet, panel or pane of material and is part of an article. The substrate may be flat, curved or shaped. The article to be coated may be produced by blowing, casting, extrusion, or injection molding.  \n\nThe anti-fog coatings may be coated on both sides of the substrate.Alternatively, the coatings of the present invention may be coated on one side of the substrate. The opposite side of the substrate may be uncoated or coated with a wide variety of conventional antifogging compositions. Preferably, the coating surface should face the direction of higher humidity, e.g., on a face shield the side having the anti-fog coating should face the wearer.  \n\nObjects and advantages of this disclosure are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this disclosure.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 22,
+        "chunk": "# Test Descriptions 35 Test for Anti-Fogging Property  \n\nThe anti-fogging property of the coatings according to the invention was determined by placing coated substrates over a container of hot water (at a temperature of about $50\\mathrm{-}60^{\\circ}$ ） C.). If fogging was observed within 10 seconds, the coating was deemed to have“poor\" anti-fogging property. If fogging was observed within 10-60 seconds, the coating was deemed to have “good” anti-fogging property. If fogging was observed after 60 seconds, the coating was deemed to have ；“excelent\" anti-fogging property.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 23,
+        "chunk": "# Test for Measuring Transmission & Haze  \n\nTransmission and haze values disclosed herein were measured using a Haze-Gard Plus haze meter (available from BYK-Gardiner, Silver Springs, Md.) according to the procedure described in ASTM D1003.  \n\nTest for Durability of Coatings  \n\nThe adhesion of the anti-fog coatings and the (plastic) substrates was determined by cross-hatch/tape adhesion test. All of the coatings made according to the Examples of this invention passed the cross-hatch/tape adhesion test.  \n\nMechanical durability of the anti-fog coatings was determined by subjecting the coated substrates to linear abrasion test. The linear abrasion test was carried out by wiping the coatings with a paper towel for 100, 200 or 300 cycles under a constant force of about 1400 grams of force $(13.73~\\mathrm{N})$ _ Then the coatings were tested for haze and observed visually for the presence of scratches.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 24,
+        "chunk": "# Materials  \n\nThe following list of materials and their source is referred to throughout the Examples.  \n\n<html><body><table><tr><td>Mateial</td><td>Description</td></tr><tr><td>NALCO 1115</td><td>An aqueous (4 nm) colloidal silica dispersion obtained from Nalco Co., Naperville, IL under trade designation \"NALCO 1115”.</td></tr><tr><td>DVSZN004</td><td>An aqueous (42 nm) colloidal silica dispersion obtained from Nalco Co., Naperville, IL.</td></tr><tr><td>W835/140</td><td>Polyurethane dispersion having polycarbonate backbone, obtained from Incorez Co., Lancashire, England under trade designation “INCOREZ W835/140\".</td></tr><tr><td>W835/177</td><td>Polyurethane dispersion having polyester backbone, obtained from Incorez Co., Lancashire, England under trade designation “INCOREZ W835/170\".</td></tr><tr><td>W835/360</td><td>Polyurethane dispersion having polyester carbonate backbone,obtained from Incorez Co., Lancashire, England under trade designation “INCOREZ</td></tr><tr><td></td><td>W835/360\". Polyurethane dispersion, obtained from Royal DSM</td></tr><tr><td>R-960 R-961</td><td>N.V., Harleen, Netherlands under trade designation “R- 961\".</td></tr><tr><td>U9800</td><td>A solvent free aliphatic polyester polyurethane dispersion, obtained from Alberdingk Boley, Inc. Greensboro, NC under trade designation “ABERDINGK</td></tr><tr><td>EM 2382</td><td>U9800\" Ethoxylated (9) trimethylpropane triacrylate, obtained</td></tr><tr><td>SR502</td><td>from Eternal Chemical Co., Ethoxylated (9) trimethylpropane triacrylate, obtained from Sartomer Company, Exton, PA under trade</td></tr><tr><td>2-methylaziridine</td><td>designation“SR 502”. Obtained from Sigma Aldrich Chemical Company, St.</td></tr><tr><td></td><td>Louis, MO. 2-[Methoxy(polyethyleneoxy)propyl]Obtained from Gelest, Inc., Morrisville, PA.</td></tr><tr><td>trimethoxysilane ED-900</td><td>Polyetheramine, obtained from The Woodlands, TX</td></tr><tr><td>ED-2003</td><td>under trade designation “JEFFAMINE ED-900”.</td></tr><tr><td></td><td>Polyetheramine, obtained from The Woodlands, TX under trade designation “JEFFAMINE ED-2033\".</td></tr><tr><td>Poly(ethylene glycol) (200) monomethacrylate</td><td>Obtained from Sigma Aldrich Chemical Company, St. Louis, MO.</td></tr><tr><td>Succinic anhydride</td><td>Obtained from Alfa Aesar, Ward Hill, MA.</td></tr><tr><td>Triethylamine</td><td>Obtained from Sigma Aldrich Chemical Company, St. Louis, MO.</td></tr><tr><td>THF</td><td>Tetrahydrofuran, obtained from Sigma Aldrich Chemical Company, St. Louis, MO.</td></tr><tr><td>AL-2450</td><td>Alumina nanoparticle dispersion (50 wt %) obtained from Nanophase Technologies, Corp., Romeoville, IL,</td></tr><tr><td>BRIJ 30</td><td>under trade designation“NANO ARC AL-2450” Tetraethylene glycol dodecyl ether, obtained from Sigma</td></tr><tr><td>BYK-346</td><td>Aldrich Chemical Company, St. Louis, MO under trade designation“BRIJ 30”. Silicone surfactant, available from Innovadex under trade</td></tr><tr><td>A-18</td><td>designation“BYK-346\". Ionic Surfactant, obtained from Stepan Company,</td></tr><tr><td>BC-10</td><td>Northfield, IL under trade designation“POLYSTEP A-18\" Ionic Surfactant, avilable from Dai-Ichi Kogyo Seitaku,</td></tr><tr><td></td><td>Ltd. of Japan under trade designation “Hitenol BC-10”</td></tr><tr><td>PEG monomethyl ether</td><td>Poly(ethylene glycol) methyl ether (Mw = 550) is obtained from Sigma Aldrich Chemical Company, St.</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 25,
+        "chunk": "# EXAMPLES",
+        "category": "your request, please provide the text segment about hydrophilic polymers so that I can analyze it and classify it accordingly."
+    },
+    {
+        "id": 26,
+        "chunk": "# Preparative Examples 1-4  \n\nSynthesis of Nanoparticles Comprising PEG Silane Surface Treatment  \n\nFor each of Preparative Examples 1-3, silica nanoparticles modified with functional silanes were prepared by slowly 60 adding a desired amount of a functional silane to selected silica nanoparticle dispersion. The relative amounts of the silica nanoparticle dispersion to the functional silane were determined on the basis of equivalent surface coverage desired. The resulting dispersions were stirred for 4 hours at 65 room temperature and then heated up to $65^{\\circ}\\mathrm{C}$ .in an oven overnight. Table 1 below describes the silica nanoparticles,  \n\nfunctional silanes used and the percent coverage obtained for each of Preparative Examples 1-3. The resulting modified nanoparticle dispersions with different particle size and surface coverage were used as described in Examples described below.  \n\nTABLE1   \n\n\n<html><body><table><tr><td>Preparative Example</td><td>Nanoparticles</td><td>% Surface Coverage</td><td>Functional silane</td></tr><tr><td>1</td><td>NALCO 1115</td><td>0</td><td></td></tr><tr><td>2</td><td>DVSZN004</td><td>50</td><td>2-[Methoxy(polyeth- yleneoxy)propyl]</td></tr></table></body></html>  \n\n17 TABLE 1-continued   \n\n\n<html><body><table><tr><td>Preparative Example</td><td>Nanoparticles</td><td>% Surface Coverage</td><td>Functional silane</td></tr><tr><td>3</td><td>DVSZN004</td><td>100</td><td>2-[Methoxy(polyeth- yleneoxy)propyl]</td></tr><tr><td>4</td><td>DVSZN004</td><td>5</td><td>trimethoxysilane 2-[Methoxy(polyeth- yleneoxy)propyl] trimethoxysilane</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 27,
+        "chunk": "# Preparative Example 4",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 28,
+        "chunk": "# Synthesis of Multi-Functional Aziridine Crosslinkers PZ-2382 and PZ-502  \n\nTrifunctional aziridine crosslinkers, PZ-2382 and PZ-502. were prepared via a Michael addition of $\\begin{array}{l l}{\\mathrm{EM}}&{2382}\\end{array}$ $(\\mathrm{M}\\mathrm{W}{=}692$ ）orSR-502 $(\\mathrm{M}\\mathrm{W}{=}692)$ ）with 2-methylaziridine. Briefly, the 2-methylaziridine (9.1 grams, $0.1385~\\mathrm{mol}$ was",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 29,
+        "chunk": "# 18 Preparative Example 5  \n\nSynthesis of PEG-Based Ammonium Salts (900-DA and 2003-DA)  \n\nTo the succinic anhydride (10 grams) dissolved into THF at $50^{\\circ}\\mathrm{C},$ ,the ED-900 (50 grams) or ED-2003 (100 grams) was added. After 24 hours of reaction at $50^{\\circ}\\mathrm{C}.$ , the product   \n10 yellow viscous liquid or yellowish wax, respectively, was obtained after removal of THF under vacuum. The resulting PEG-based diacid was dissolved into water to obtain a $30\\%$ aqueous solution, to which 10 grams of triethylamine was   \n15 added and stirred at room temperature for 30 minutes to obtain PEG-based dicarboxylic acid ammonium salts with $30\\mathrm{\\wt\\\\%}$ solid.The resulting product was used in the salt form in the Examples that follow. The reaction scheme is shown below.  \n\n![](images/94c8780cf484a6692f6b5abfb867c438a78c167d5e341f8fc29f7be91a969652.jpg)  \n\nadded drop-wise to the EM 2382 or SR-502 (30 grams, 5( $0.0434\\mathrm{mol}$ ) at room temperature, then the resulting mixture was stirred for 1 hour at room temperature and then refluxed at $60^{\\circ}\\mathrm{~C~}$ .for 24 hours. Excessive methyl aziridine was removed under vacuum and finally a slight yellow liquid product was obtained and named PZ-2382 and PZ-502，5: respectively. The disappearance of the double bonds from 5.8 to 6.4 confirms that the reaction between acrylate group and NH in the methyl aziridine was completed successfully.  \n\nThe NMR spectra of the“EM-2382\"trifunctional acrylate was obtained using a modern ${500}\\mathrm{MHz}$ Avance III Bruker NMR obtained from Bruker BioSpin Corporation, Tucson, Ariz.According to analysis this acrylate contained 30 wt $\\%$ of the following surfactant:  \n\n$$\n\\mathrm{HO\\_fGH_{2}C H_{2}O]}n\\mathrm{-C_{12}H_{25}}\n$$  \n\nHence, the aziridine crosslinker prepared from “EM-2382” was calculated to contain $23\\ \\mathrm{wt-\\%}$ of such surfactant.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 30,
+        "chunk": "# 0 General Process for Forming Anti-Fog Coatings  \n\nThe components were mixed together and stirred for 20 minutes at room temperature. The resulting coating solutions with a solid content of about $30\\%$ were coated on polyester (PET), polycarbonate (PC) or glass substrates using a #15 Mayer bar or by dip coating. The resulting coatings were then cured at a temperature from $110{-}120^{\\circ}\\mathrm{C}$ for 20-30 minutes, to form coatings with the desired properties (i.e., clear and durable anti-fog coatings).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 31,
+        "chunk": "# Dip Coating Procedure  \n\nPlace clip with freshly prepared polycarbonate lens slide on metal bar of Velmax Unislide dip coater. Align slide so sides are perpendicular to lab bench top and bottom is parallel to lab bench top. Secure binder clips with tape. The ） substrates were immersed in coating solutions and were gradually pulled out at an appropriate pulling speed of about $1~\\mathrm{mm}/$ second.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 32,
+        "chunk": "# 19",
+        "category": " Introduction"
+    },
+    {
+        "id": 33,
+        "chunk": "# 20",
+        "category": " Introduction"
+    },
+    {
+        "id": 34,
+        "chunk": "# Example 1  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，79.7 grams) was mixed with 4.5 grams of PZ-2382 (neat) and 15.8 grams of water, and then stirred for 20 minutes until a homogenous dispersion was obtained. The solution $30\\mathrm{wt\\%}$ solids) was applied on a PC film with a #14 Mayer Bar and then cured at $110^{\\circ}\\mathrm{~C~}$ .for 20 minutes. The resulting coated PC film was tested for anti-fog performance as described above. The samples of Example 1 had “excellent” anti fogging properties (fogged after 65-70 seconds of exposure to $50^{\\circ}\\mathrm{~C~}$ . vapor) while having good light transmittance $(>90\\%)$ ·",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 35,
+        "chunk": "# Example 2  \n\n20  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，75.0 grams) was mixed with 6.0 grams of PZ-2382 (neat) and 9.0 grams of water, and then stirred for 2O minutes until a homogenous dispersion was obtained.The solution $30\\mathrm{wt\\%}$ solids) was applied on a PC film with a $\\#14$ Mayer Bar and then cured at $110^{\\circ}\\mathrm{~C~}$ .for 20 minutes. The resulting coated PC film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}~\\mathrm{C}$ ：vapor) and good light transmittance $(>90\\%)$ . After soaking in room temperature water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{C}.$ ,the coated PC film still exhibit “good\" anti-fog performance.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 36,
+        "chunk": "# Example 3  \n\n35  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，65.6 grams) was mixed with 9.0 grams of PZ-2382 (neat) and 25.37 grams of water, and then stirred for 20 minutes until a homogenous dispersion was obtained. The solution (30 wt $\\%$ solids) was applied on a PC film with a $\\#14$ Mayer Bar and then cured at $110^{\\circ}~\\mathrm{C}$ . for 20 minutes. The resulting coated PC film exhibited “excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ ：vapor) and good light transmittance $(>90\\%)$ . After soaking in room temperature water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{C}$ .water, the coated PC film still exhibit“good\" anti-fog performance.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 37,
+        "chunk": "# Example 4  \n\nThe polyurethane dispersion W835/177 (34 wt $\\%$ ，61.845 grams) was mixed with 9.0 grams of PZ-2382 (neat) and 29.2 grams of water, and then stirred for 20 minutes until a homogenous dispersion was obtained. The solution ( $30\\mathrm{wt\\%}$ solids) was applied on a PC film with a $\\#14$ Mayer Bar and then cured at $110^{\\circ}\\mathrm{~C~}$ . for 20 minutes. The resulting coated 50 PC film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}~\\mathrm{C}$ . vapor) and good light transmittance $(>90\\%)$ . After soaking in room temperature water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{~C~}$ .water, the coated PC film still exhibit“good\" anti-fog performance. 55",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 38,
+        "chunk": "# Example 5  \n\nThe polyurethane dispersion W835/360 (33 wt $\\%$ ，63.6 grams) was mixed with 9.0 grams of PZ-2382 (neat) and 27.4 grams of water, and then stirred for 20 minutes until a homogenous dispersion was obtained.The solution $30\\mathrm{wt\\%}$ solids) was applied on a PC film with a $\\#14$ Mayer Bar and then cured at $110^{\\circ}\\mathrm{~C~}$ . for 20 minutes. The resulting coated PC film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}~\\mathrm{C}$ ：vapor) and good light transmittance $(>90\\%)$ . After soaking in room temperature water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{~C~}$ .water, the coated PC film still exhibit“good” anti-fog performance.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 39,
+        "chunk": "# Example 6  \n\nThe polyurethane dispersion U9800 (34 wt $\\%$ ，61.8 grams) was mixed with 9.0 grams of PZ-2382 (neat) and 29.2 grams of water, and then stirred for 20 minutes until a   \n10 homogenous dispersion was obtained. The solution $30\\mathrm{wt\\%}$ solids) was applied on a PC film with a $\\#14$ Mayer Bar and then cured at $110^{\\circ}\\mathrm{~C~}$ .for 20 minutes. The resulting coated PC film exhibited“excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{~C~}$ . vapor) and good light   \n15transmittance $(>90\\%)$ . After soaking in room temperature water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{~C~}$ .water, the coated PC film still exhibit“good” anti-fog performance.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 40,
+        "chunk": "# Example 7  \n\nThe polyurethane dispersion R961 ( $34\\mathrm{wt}\\%$ ,61.8 grams) was mixed with 9.0 grams of PZ-2382 (neat) and 29.2 grams of water, and then stirred for 20 minutes until a homogenous   \n25 dispersion was obtained. The solution ( $30\\mathrm{wt\\%}$ solids) was applied on a PC film with a $\\#14$ Mayer Bar and then cured at $110^{\\circ}\\mathrm{~C~}$ . for 20 minutes. The resulting coated PC film exhibited“excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ 、vapor) and good light transmittance   \n30 $(>90\\%)$ . After soaking in room temperature water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{C}$ .water, the coated PC film still exhibit“good\" anti-fog performance.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 41,
+        "chunk": "# Example 8  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，74.1 grams) was mixed with 6.0 grams of PZ-502 (neat), $1.0~\\mathrm{g}$ BYK-346 and 18.9 grams of water, and then stirred for 20 minutes until a homogenous dispersion was obtained. The solution (30 wt $\\%$ solids) was applied on a PC film with a $\\#14$ Mayer Bar and then cured at $110^{\\circ}\\mathrm{C}$ .for 20 minutes.The resulting coated PC film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ . vapor) and good light transmittance $(>90\\%)$ . After soaking in room temperature water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{C}$ . water, the coated PC film still exhibit “good” anti-fog performance.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 42,
+        "chunk": "# Example 9  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，74.1 grams) was mixed with 6.0 grams of PZ-502 (neat), 1.0 gram BRIJ 30 and 18.9 grams of water, and then stirred for 20 minutes until a homogenous dispersion was obtained. The solution ( $30\\mathrm{wt\\%}$ solids) was applied on a PC film with a $\\#14$ Mayer Bar and then cured at $110^{\\circ}\\mathrm{~C~}$ .for 20 minutes. The resulting coated PC film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}$ C. vapor) and good light transmittance $(>90\\%)$ . After soaking in room temperature water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{C}$ . water, the coated PC film still exhibit“good' anti-fog performance.  \n\nTable 1 below summarizes the components and the relative amounts of each component in the resulting cured coatings (on PC films) of Examples 1-9 described above.  \n\nTABLE1   \n\n\n<html><body><table><tr><td></td><td colspan=\"5\">Type and wt.% Polyurethane</td><td colspan=\"2\">Type and wt.% Aziridine</td><td colspan=\"2\">Type and wt. % Surfactant</td></tr><tr><td>Example</td><td>W835/140</td><td>W835/177</td><td>W835/360</td><td>U9800</td><td>R961</td><td>PZ-2382*</td><td>PZ-502</td><td>BYK-346</td><td>BRIJ30</td></tr><tr><td>1</td><td>85</td><td></td><td></td><td></td><td></td><td>15</td><td></td><td></td><td></td></tr><tr><td>2</td><td>80</td><td></td><td></td><td></td><td></td><td>20</td><td></td><td></td><td></td></tr><tr><td>3</td><td>70</td><td></td><td></td><td></td><td></td><td>30</td><td></td><td></td><td></td></tr><tr><td>4</td><td></td><td>70</td><td></td><td></td><td></td><td>30</td><td></td><td></td><td></td></tr><tr><td>5</td><td></td><td></td><td>70</td><td></td><td></td><td>30</td><td></td><td></td><td></td></tr><tr><td>6</td><td></td><td></td><td></td><td>70</td><td></td><td>30</td><td></td><td></td><td></td></tr><tr><td>7</td><td></td><td></td><td></td><td></td><td>70</td><td>30</td><td></td><td></td><td></td></tr><tr><td>8</td><td>79</td><td></td><td></td><td></td><td></td><td></td><td>20</td><td>1</td><td></td></tr><tr><td>9</td><td>79</td><td></td><td></td><td></td><td></td><td></td><td>20</td><td></td><td>1</td></tr></table></body></html>\n\nPZ-2382 comprises $23\\%$ surfactant, as previously described. Therefore, $15\\mathrm{wt}\\mathrm{\\textperthousand}$ PZ-2382 = 3.5 wt-% of surfactant and $11.5\\mathrm{wt}\\%$ hydrophilic aziridine crosslinker 20 wt $\\%$ P $Z-2\\dot{3}82=4.6$ wt- $\\%$ of surfactant and 15.4 wt- $\\%$ hydrophilic aziridine crosslinker 30 wt $\\%$ 工 $\\mathcal{Z}\\mathcal{-}2382=6.9$ wt- $\\%$ of surfactant and $23.1~\\mathrm{wt}\\cdot\\%$ hydrophilic aziridine crosslinker",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 43,
+        "chunk": "# Example 10  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，75.02( grams) was mixed with 4.5 grams of PZ-2382 (neat), 5.0 grams PEG-modified DVSZN004 (Preparative Example 2, $50\\%$ coverage and $30\\mathrm{wt\\%}$ solid) and 15.5 grams water, and then stirred for 20 minutes until a homogenous dispersion was obtained. The solution (30 wt $\\%$ solids) was applied on 2: a PC film with a $\\#14$ Mayer Bar and then cured at $110^{\\circ}\\mathrm{~C~}$ \\* for 20 minutes. The resulting coated PC film exhibited “excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ . vapor) and good light transmittance $(>90)$ No scratching was observed after linear abrasion of more $30$ than 100 cycle using paper towel under 1400 grams of force. After soaking in room temperature water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{C}$ water, the coated PET film still exhibit \"good” anti-fog performance.  \n\nsame manner as Example 11A. The resulting coated PMMA film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{~C~}$ . vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{~C~}$ .water,the coated PET film still exhibit “good\" anti-fog performance.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 44,
+        "chunk": "# Example 11D  \n\nThe same coating composition as Example 1lA was applied to a glass substrate in the same manner as Example 11A. The resulting coated glass substrate exhibited “excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{~C~}$ . vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{~C~}$ 、water, the coated PET film still exhibit ；“good\" anti-fog performance.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 45,
+        "chunk": "# Example 11A  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ 75.0 grams) was mixed with 4.5 grams of PZ-2382 (neat), 5.0 grams PEG-modified DVSZN004 (Preparative Example 2, $50\\%$ coverage and $30\\mathrm{wt}\\%$ solid) and 15.5 grams water, and then stirred for 20 minutes until a homogenous dispersion was obtained. The solution ( $30\\mathrm{wt}\\%$ solids) was applied on a PC film with a $\\#14$ Mayer Bar and then cured at $\\mathrm{{110^{\\circ}C}}$ \\* for 20 minutes. The resulting coated PC film exhibited “excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ . vapor) and good light transmittance $(>90)$ No scratching was observed after linear abrasion of more than 100 cycle using paper towel under 1400 grams of force. After soaking in room temperature water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{C}$ water, the coated PET film still exhibit “good” anti-fog performance.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 46,
+        "chunk": "# Example 12  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，65.6   \n40 grams) was mixed with 7.5 grams of PZ-2382 (neat), 5.0 grams PEG-modified DVSZN004 (Preparative Example 2, $50\\%$ coverage and $30\\mathrm{\\wt\\\\%}$ ） and 21.9 grams of water, and then stirred for 2O minutes until a homogenous dispersion was obtained. The solution (30 wt $\\%$ solids) was applied on   \n45 a PC plate with a $\\#14$ Mayer Bar and then cured at $110^{\\circ}\\mathrm{~C~}$ for 20 minutes. The resulting coated PC plate exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ . vapor) and good light transmittance $(>90)$ · After soaking in room temperature water for 1 hour as well   \n50 as 24 hours at $50^{\\circ}\\mathrm{C}$ .water, the coated PET film still exhibit “good” anti-fog performance.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 47,
+        "chunk": "# Example 11B  \n\nThe same coating composition as Example 1lA was applied to a PET film in the same manner as Example 11A. The resulting coated PET film exhibited“excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{~C~}$ vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 1 hour as well as 24 hours at $50^{\\circ}$ C. water, the coated PET film still exhibit “good\" anti-fog performance.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 48,
+        "chunk": "# Example 11C  \n\nThe same coating composition as Example 1lA was applied to a polymethyl methacrylate (PMMA) film in the",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 49,
+        "chunk": "# Example 13  \n\n55 The polyurethane dispersion W835/140 (32 wt $\\%$ ，65.6 grams) was mixed with 7.5 grams of PZ-2382 (neat), 5.0 grams PEG-modified DVSZN004 (Preparative Example 3, $100\\%$ coverage and $30\\mathrm{wt}\\%$ )and 21.9 grams of water, and then stirred for 2O minutes until a homogenous dispersion   \n60 was obtained. The solution (30 wt $\\%$ solids) was applied on a PC film with a $\\#14$ Mayer Bar and then cured at $110^{\\circ}\\mathrm{~C~}$ \\* for 20 minutes. The resulting coated PC film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ vapor) and good light transmittance $(>90)$ ·   \n65 After soaking in room temperature water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{C}$ .water, the coated PET film still exhibit “good\" anti-fog performance.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 50,
+        "chunk": "# 23",
+        "category": " Introduction"
+    },
+    {
+        "id": 51,
+        "chunk": "# Example 14  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，65.6 grams) was mixed with 7.5 grams of PZ-2382 (neat),5.0 grams PEG-modified DVSZN004 (Preparative Example 2, $50\\%$ coverage and $30\\mathrm{\\wt\\\\%}$ ) and 21.9 grams of water, and then stirred for 20 minutes until a homogenous dispersion was obtained. Then, 0.6 gram of poly(ethylene glycol) (200) monomethacrylate was added to above dispersion under stirring until a homogenous dispersion was formed. The solution (30 wt $\\%$ solids) was applied on a PC film with a $\\#14$ Mayer Bar and then cured at $110^{\\circ}\\mathrm{C}$ .for 20 minutes.The resulting coated PC film exhibited “excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ . vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{C}$ . water, the coated PET film still exhibit “good\" anti-fog performance and durable.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 52,
+        "chunk": "# Example 15  \n\n25  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，65.6 grams) was mixed with 7.5 grams of PZ-2382 (neat),5.0 grams PEG-modified DVSZN004 (Preparative Example 2, $50\\%$ coverage and 30 wt $\\%$ ) and 21.9 grams of water, and then stirred for 20 minutes until a homogenous dispersion was obtained. Then, 1.0 gram of BYK-346 was added to above dispersion under stirring until a homogenous dispersion was formed. The solution (30 wt $\\%$ solids) was applied on a PC film with a $\\#14$ Mayer Bar and then cured at $110^{\\circ}$ C.for 20 minutes. The resulting coated PC film exhibited “excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ . vapor) and good light transmittance $(>90)$ \\* After soaking in room temperature water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{C}$ .water, the coated PET film still exhibit “good” anti-fog performance and durable.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 53,
+        "chunk": "# Example 16  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，65.64 grams) was mixed with 7.5 grams of PZ-2382 (neat), 5.0 grams PEG-based modified DVSZN004 (Preparative Example 2, $50\\%$ coverage and $30\\mathrm{wt}\\%$ ）and 21.9 grams of water, and then stirred for 20 minutes until a homogenous dispersion was obtained. Then, 1.0 gram of BRIJ 30 was 4 added to above dispersion under stirring until a homogenous dispersion was formed. The solution ( $30\\mathrm{\\wt\\\\%}$ solids)was applied on a PC film with a $\\#14$ Mayer Bar and then cured at $110^{\\circ}$ C. for 2O minutes. The resulting coated PC film exhibited “excellent” anti-fog performance(no fog 5 appeared when exposed to $50^{\\circ}~\\mathrm{C}$ . vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{~C~}$ .water, the coated PET film still exhibit“good” anti-fog performance and durable. 5",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 54,
+        "chunk": "# 24  \n\ntemperature water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{C}$ water, the coated PET film still exhibit “good\"” anti-fog performance and durable.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 55,
+        "chunk": "# Example 18  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ,8.43 grams) was mixed with 0.94 gram R-961 $(32\\%)$ , 1.15 grams of PZ-2382 (neat) and 2.5 grams PEG-based modified l0 DVSZNo04 (Preparative Example 2, $50\\%$ coverage and 10 wt $\\%$ ), and then stirred for 20 minutes until a homogenous dispersion was obtained. Then, 0.4 gram of A-18 and 0.2 gram BC-10 was respectively added to above dispersion under stirring until a homogenous dispersion was formed.   \n15The solutionwas applied ona PCfilmwitha #14 Mayer Bar and then cured at $110^{\\circ}~\\mathrm{C}$ 、for 20 minutes. The resulting coated PC film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ vapor) and good light transmittance $(>90)$ . After soaking in room temperature   \n20 water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{~C~}$ .water, the coated PC film still exhibit“good\" anti-fog performance and durable.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 56,
+        "chunk": "# Example 19  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，65.6 grams) was mixed with 6.0 grams of PZ-2382 (neat, prepared as described above in Preparative Example 21), 10.0 grams PEG-based modified DVSZN004 (Preparative Example 4, $5\\%$ coverage and $30\\mathrm{~wt~}\\%$ ） and 18.4 grams water, and then stirred for 20 minutes until a homogenous dispersion was obtained. The solution ( $30\\mathrm{wt}\\%$ solids)was applied on a PC film with a $\\#14$ Mayer Bar and then cured at $110^{\\circ}\\mathrm{~C~}$ 、for 20 minutes. The resulting coated PC film exhibited“excellent” anti-fogperformance(no fog appeared when exposed to $50^{\\circ}~\\mathrm{C}$ ： vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{~C~}$ .water, the coated PC film still exhibit “good” anti-fog performance.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 57,
+        "chunk": "# Example 20  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，56.3 grams) was mixed with 6.0 grams of PZ-2382 (neat), 20.0 grams PEG-based modified DVSZN004 (Preparative Example 4, $5\\%$ coverage and $30\\mathrm{\\textrm{wt}\\%}$ ）and 17.7grams water, and then stirred for 20 minutes until a homogenous dispersion was obtained.The solution ( $30\\mathrm{wt\\\\%}$ solids)was applied on a PC film with a $\\#14$ Mayer Bar and then cured at $110^{\\circ}\\mathrm{~C~}$ . for 20 minutes. The resulting coated PC film exhibited“excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}$ C.vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{~C~}$ .water,the ； coated PC film still exhibit “good\" anti-fog performance.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 58,
+        "chunk": "# Example 17  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，65.6 grams) was mixed with 7.5 grams of PZ-2382 (neat), 1.5 grams AL-2450 and 22.9 grams water, and then stirred for $20~\\mathrm{min}$ until a homogenous dispersion was obtained. The solution (30 wt $\\%$ solids) was applied on a PC film with a $\\#14$ Mayer Bar and then cured at $110^{\\circ}\\mathrm{C}$ .for 20 minutes.The resulting coated PC film exhibited “excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ vapor) and good light transmittance $(>90)$ . After soaking in room",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 59,
+        "chunk": "# Example 21  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，28.1 grams) was mixed with 6.0 grams of PZ-2382 (neat), 50.0 grams PEG-based modified DVSZN004 (Preparative Example 4, $5\\%$ coverage and $30\\mathrm{~wt~}\\%$ ）and 15.9 grams water, and then stirred for 20 minutes until a homogenous dispersion was obtained. The solution ( $30\\mathrm{wt\\%}$ solids)was applied on a PC film with a $\\#14$ Mayer Bar and then cured at $\\mathrm{{110^{o}~C}}$ . for 2O minutes. The resulting coated PC film exhibited“excellent\" anti-fog performance (no fog appeared",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 60,
+        "chunk": "# 25  \n\nwhen exposed to $50^{\\circ}\\mathrm{C}$ vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 1 hour as well as 24 hours at $50^{\\circ}\\mathrm{C}$ .water, the coated PC film still exhibit“good” anti-fog performance.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 61,
+        "chunk": "# 26 Example 24  \n\nTable 2 below summarizes the components and the relative amounts of each component in the resulting cured coatings on substrates of Examples 10-21 described above.  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，54.7 grams) was mixed with 35 grams of 900-DA (30 wt $\\%$ under stirring to form a homogenous dispersion, then 7.0 grams of PZ-2382 (neat) and 3 grams of water were added and stirred for $20~\\mathrm{min}$ until a homogenous dispersion was  \n\n<html><body><table><tr><td rowspan=\"3\">Example</td><td rowspan=\"3\">Type and Wt % Polyurethane</td><td rowspan=\"3\">Wt % Aziridine</td><td colspan=\"4\">Type and wt % Nanoparticles</td></tr><tr><td colspan=\"3\">Preparative Example</td><td>wt-% of Surfactant</td></tr><tr><td>PZ-2382* 1</td><td>2</td><td>3 AL-2450</td><td>or Additive</td></tr><tr><td>10</td><td>80</td><td>15</td><td>５</td><td></td><td></td><td></td></tr><tr><td>11A-D</td><td></td><td></td><td></td><td>５</td><td></td><td></td></tr><tr><td></td><td>80</td><td>15</td><td></td><td>5</td><td></td><td></td></tr><tr><td>12</td><td>70</td><td>25 25</td><td></td><td></td><td></td><td></td></tr><tr><td>13 14</td><td>70 68.6</td><td>24.5</td><td></td><td>4.9</td><td></td><td>2 mono</td></tr><tr><td>15</td><td>68</td><td>24.2</td><td></td><td>4.8</td><td></td><td>ether 3.2</td></tr><tr><td>16</td><td>68</td><td>24.2</td><td></td><td>4.8</td><td></td><td>BYK-346 3.2</td></tr><tr><td>17</td><td>72</td><td></td><td>25.6</td><td></td><td>2.4</td><td>BRIJ 30</td></tr><tr><td>18</td><td>54</td><td></td><td>23</td><td>５</td><td></td><td>8 A-18&4</td></tr><tr><td>19</td><td>70</td><td></td><td></td><td></td><td></td><td>BC-10</td></tr><tr><td>20</td><td>60</td><td>20 20</td><td></td><td>10 20</td><td></td><td></td></tr><tr><td>21</td><td>30</td><td>20</td><td></td><td>50</td><td></td><td></td></tr></table></body></html>\n\n\\*PZ-2382 comprises $23\\%$ surfactant, as previously described. Therefore,15 wt $\\%$ P $Z{\\cdot}2382=3.5~\\mathrm{wt}{\\cdot}\\%$ of surfactant and11.5wt $\\%$ hydrophilic aziridine crosslinker 25wt $\\%$ PZ- $2382=5.8\\$ wt- $\\%$ of surfactant and 19.2 wt- $\\%$ hydrophilic aziridine crosslinker 24.2 wt $\\%$ 1 $?Z-2382=5.6$ wt $\\%$ of surfactant and 18.6 wt- $\\%$ hydrophilic aziridine crosslinker 23 wt $\\%$ 1 $^{\\ }_{\\cdot}Z-2382=5.3$ wt- $\\%$ of surfactant and 17.7 wt- $\\%$ hydrophilic aziridine crosslinker  \n\n35",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 62,
+        "chunk": "# Example 22  \n\nThe polyurethane dispersion $\\mathrm{W}835/140$ (32 wt $\\%$ ，60.9 grams) was mixed with 15 grams of 900-DA (30 wt $\\%$ 价 prepared as described above in Preparative Example 5) under stirring to form a homogenous dispersion, then 6.0 grams of PZ-2382 (neat) and 18.1 grams of water were added and stirred for 20 min until a homogenous dispersion was obtained. The solution ( $30\\mathrm{wt}\\%$ solids) was applied on a PC plate by a Velmax Unislide dip coater and then cured at $11\\bar{0}^{\\circ}\\mathrm{~C~}$ . for 20 minutes. The resulting coated PC film exhibited“excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ vapor) and good light transmittance $(>90)$ .After soaking in room temperature water for 240 hours as well as 96 hours at $80^{\\circ}\\mathrm{C}$ .water or 120 hours at $65^{\\mathrm{{o}}}$ C., the coated PC plates still exhibit“excellent” anti-fog performance and very durable.  \n\nobtained. The solution ( $35\\mathrm{wt\\%}$ solids) was applied on a PC plate by a Velmax Unislide dip coater and then cured at $110^{\\circ}$ C.for 20 minutes. The resulting coated PC film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ . vapor) and good light transmittance $(>90)$ \\* After soaking in room temperature water for 24o hours as well as 96 hours at $80^{\\circ}\\mathrm{C}$ .water or 120 hours at $65^{\\circ}\\mathrm{C}.$ ，the coated PC plate still exhibit “excellent” anti-fog performance and very durable.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 63,
+        "chunk": "# Example 25",
+        "category": " Introduction"
+    },
+    {
+        "id": 64,
+        "chunk": "# Example 23  \n\nThe polyurethane dispersion $\\mathrm{W}835/140$ (32 wt $\\%$ ，60.2 grams) was mixed with 29.2 grams of 900-DA (30 wt $\\%$ j under stirring to form a homogenous dispersion, then 7.0 grams of PZ-2382 (neat) and 3.6 grams of water were added and stirred for $20~\\mathrm{{inin}}$ until a homogenous dispersion was obtained. The solution ( $35\\mathrm{wt\\%}$ solids) was applied on a PC plate by a Velmax Unislide dip coater and then cured at $110^{\\circ}$ C.for 20 minutes. The resulting coated PC film exhibited “excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ . vapor) and good light transmittance $(>90)$ After soaking in room temperature water for 240 hours as well as 96 hours at $80^{\\circ}\\mathrm{C}$ water or 120 hours at $65^{\\circ}\\mathrm{C}.$ ，the coated PET film still exhibit“excellent” anti-fog performance and very durable.  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，65.6 grams) was mixed with 23.3 grams of 900-DA (30 wt $\\%$ j   \n50 under stirring to form a homogenous dispersion, then 7.0 grams of PZ-2382 (neat), 1 gram BYK-346 and 3 grams of water were added and stirred for $20\\mathrm{min}$ until a homogenous dispersion was obtained. The solution $35\\mathrm{\\wt\\\\%}$ solids) was applied on a PC plate by a Velmax Unislide dip coater and   \n55 then cured at $110^{\\circ}\\mathrm{~C~}$ .for 20 minutes. The resulting coated PC film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}$ C. vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 240 hours as well as 96 hours at $80^{\\circ}\\mathrm{~C~}$ .water or   \n60 120 hours at $65^{\\circ}\\mathrm{C}.$ , the coated PC film still exhibit“excellent\" anti-fog performance and very durable. A glass plate and a PC lens were coated with the above coating solution by casting and dip coating methods followed by curing at $110^{\\circ}\\mathrm{C}$ for 20 minutes. The resulting coated glass plate and   \n65 PC lens had “excellent” anti-fog performance before and after 24 hours of soaking in room temperature water as well as hot water.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 65,
+        "chunk": "# 27 Example 26  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，54.7 grams) was mixed with 35.0 grams of 900-DA (30 wt $\\%$ ) under stirring to form a homogenous dispersion, then 7.0 grams of PZ-2382 (neat), 1 gram BYK-346 and 4 grams of water were added and stirred for $20\\mathrm{min}$ until a homogenous dispersion was obtained. The solution ( $35\\mathrm{\\wt\\\\%}$ solids) was applied on a PC plate with a #14 Mayer Bar and then cured at $\\mathrm{\\dot{1}10^{\\circ}}$ C. for 20 minutes. The resulting coated PC film exhibited“excellent”anti-fogperformance(nofog appeared when exposed to $50^{\\circ}\\mathrm{~C~}$ . vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 240 hours as well as 96 hours at $80^{\\circ}\\mathrm{~C~}$ .water or 120 hours at $65^{\\circ}\\mathrm{C}.$ , the coated PC film still exhibit “excellent” anti-fog performance and very durable. A glass plate and a PC lens were coated with the above coating solution by casting and dip coating methods followed by curing at $110^{\\circ}\\mathrm{C}$ for 20 minutes. The resulting coated glass plate and PC lens had “excellent” anti-fog performance before and after 24 hours of soaking in room temperature water as well as hot water.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 66,
+        "chunk": "# Example 27  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，56.325 grams) was mixed with 15.0 grams of 900-DA (30 wt $\\%$ j under stirring to form a homogenous dispersion, then 6.0 grams of PZ-2382 (neat), 5.0 grams PEG-modified DVSZN004 (Preparative Example 2, $50\\%$ coverage and 30 wt $\\%$ ) and 17.7 grams of water were added and stirred for 30 $20~\\mathrm{min}$ until a homogenous dispersion was obtained. The solution ( $30\\mathrm{\\wt\\\\%}$ solids) was applied on a PC plate by a Velmax Unislide dip coater and then cured at $110^{\\circ}\\mathrm{C}$ .for 20 minutes. The resulting coated PC film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}$ 35 C. vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 240 hours as well as 96 hours at $80^{\\circ}\\mathrm{~C~}$ .water or 120 hours at $65^{\\circ}\\mathrm{C}.$ ,the coated PC film still exhibit “excellent” anti-fog performance and very durable. A PC lens was coated with the above coating 4( solution by dip coating followed by curing at $110^{\\circ}\\mathrm{C}.$ for20 minutes. The resulting coated PC lens had “excellent\" anti-fog performance before and after 24 hours of soaking in room temperature water as well as hot water.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 67,
+        "chunk": "# Example 28  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，60.9 grams) was mixed with 15 grams of 2003-DA (30 wt $\\%$ j under stirring to form a homogenous dispersion, then 6.0 grams of PZ-2382 (neat) and 18.1 grams of water were added and stirred for $20\\mathrm{min}$ until a homogenous dispersion was obtained. The solution ( $30\\mathrm{wt\\\\%}$ solids) was applied on a PC plate by a Velmax Unislide dip coater and then cured at $110^{\\circ}$ C. for 20 minutes. The resulting coated PC film exhibited“excellent”anti-fogperformance(nofog appeared when exposed to $50^{\\circ}~\\mathrm{C}$ . vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 240 hours as well as 96 hours at $80^{\\circ}\\mathrm{~C~}$ .water or 120 hours at $65^{\\circ}\\mathrm{~C~}$ ，the coated PC plates still exhibit “excellent” anti-fog performance and very durable.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 68,
+        "chunk": "# Example 29",
+        "category": " Introduction"
+    },
+    {
+        "id": 69,
+        "chunk": "# 28  \n\ngrams of PZ-502 (neat) and 11.1 grams of water were added and stirred for $20~\\mathrm{min}$ until a homogenous dispersion was obtained. The solution $30\\mathrm{wt\\%}$ solids) was applied on a PC film with a #14 Mayer Bar and then cured at $110^{\\circ}\\mathrm{C}$ .for20 5minutes. The resulting coated PC film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}$ C. vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 240 hours as well as 96 hours at $80^{\\circ}\\mathrm{~C~}$ .water or 120 hours at $65^{\\circ}\\mathrm{C}.$ ，the coated PC film ， still exhibit “excellent” anti-fog performance and very durable.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 70,
+        "chunk": "# Example 30  \n\n15 The polyurethane dispersion W835/140 (32 wt $\\%$ ，60.9 grams) was mixed with 25 grams of 900-DA (30 wt $\\%$ j under stirring to form a homogenous dispersion, then 3.0 grams of PZ-502 (neat) and 11.1 grams of water were added and stirred for $20~\\mathrm{min}$ until a homogenous dispersion was   \n20 obtained. The solution ( $30\\mathrm{wt\\%}$ solids) was applied on a PC plate with a $\\#14$ Mayer Bar and then cured at $110^{\\circ}\\mathrm{C}$ .for20 minutes. The resulting coated PC film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}$ C.vapor) and good light transmittance $(>90)$ . After soaking   \n25i in room temperature water for 240 hours as well as 96 hours at $80^{\\circ}\\mathrm{~C~}$ .water or 120 hours at $65^{\\circ}\\mathrm{C}.$ ，the coated PC film still exhibit “excellent” anti-fog performance and very durable.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 71,
+        "chunk": "# Example 31  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，60.9 grams) was mixed with 25 grams of 900-DA (30 wt $\\%$ ) under stirring to form a homogenous dispersion, then 3.0 grams of XL-706 (neat) and 11.1 grams of water were added and stirred for 20 min until a homogenous dispersion was obtained. The solution ( $30\\mathrm{wt\\%}$ solids) was applied on a PC film with a $\\#14$ Mayer Bar and then cured at $110^{\\circ}\\mathrm{C}$ .for20 minutes. The resulting coated PC film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}$ C. vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 240 hours as well as 96 hours at $80^{\\circ}\\mathrm{~C~}$ .water or 120 hours at $65^{\\circ}\\mathrm{C}.$ ，the coated PC film still exhibit “excellent” anti-fog performance and very durable.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 72,
+        "chunk": "# Example 32  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，60.9 grams) was mixed with 25 grams of 900-DA (30 wt $\\%$ j under stirring to form a homogenous dispersion, then 3.0 grams of CX-100 (neat) and 11.1 grams of water were added and stirred for $20~\\mathrm{min}$ until a homogenous dispersion was obtained. The solution ( $30\\mathrm{wt\\%}$ solids) was applied on a PC 5 film with a #14 Mayer Bar and then cured at $110^{\\circ}\\mathrm{C}$ .for20 minutes. The resulting coated PC film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}$ C. vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 240 hours as well as 96 hours ）at $80^{\\circ}\\mathrm{~C~}$ . water or 120 hours at $65^{\\circ}\\mathrm{C}.$ , the coated PC film still exhibit “excellent” anti-fog performance and very durable.  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，60.965 grams) was mixed with 25 grams of 900-DA (30 wt $\\%$ j under stirring to form a homogenous dispersion, then 3.0",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 73,
+        "chunk": "# Example 33  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，54.7 grams) was mixed with 35.0 grams of 900-DA (30 wt $\\%$ j under stirring to form a homogenous dispersion, then 7.0 grams of PZ-2382 (neat), 1 gram BRIJ 30 and 4 grams of water were added and stirred for $20\\mathrm{min}$ until a homogenous dispersion was obtained. The solution (35 wt $\\%$ solids)was applied on a PC plate with a #14 Mayer Bar or by dipping coating and then cured at $110^{\\circ}\\mathrm{~C~}$ .for 20 minutes. The resulting coated PC film exhibited “excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 240 hours as well as 96 hours at $80^{\\circ}$ C.water or 120 hours at $65^{\\circ}\\mathrm{~C~}.$ ,the coated PC film still exhibit“excellent” anti-fog performance and very durable. A glass plate and a PC lens were coated with the above coating solution by casting and dip coating methods followed by curing at $110^{\\circ}\\mathrm{~C~}$ .for 20 minutes. The resulting coated glass plate and PC lens had “excellent” anti-fog performance before and after 24 hours of soaking in room temperature water as well as hot water.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 74,
+        "chunk": "# Example 34  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，65.6 grams) was mixed with 23.3 grams of 900-DA (30 wt $\\%$ j under stirring to form a homogenous dispersion, then 7.0 grams of PZ-2382 (neat), 1 gram BRIJ 30 and 3 grams of water were added and stirred for 20 min until a homogenous dispersion was obtained. The solution ( $35\\mathrm{wt\\\\%}$ solids)was applied on a PC plate with a #14 Mayer Bar or by dipping coating and then cured at $110^{\\circ}\\mathrm{~C~}$ .for 20 minutes.The resulting coated PC film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 240 hours as well as 96 hours at $80^{\\circ}$ C.water or 120 hours at $65^{\\circ}\\ \\mathrm{C}.$ ，the coated PC film still exhibit “excellent” anti-fog performance and very durable. A glass plate and a PC lens were coated with the above coating solution by casting and dip coating methods followed by curing at $110^{\\circ}~\\mathrm{C}$ . for 20 minutes. The resulting coated glass plate and PC lens had “excellent” anti-fog performance before and after 24 hours of soaking in room temperature water as well as hot water.  \n\nTable 3 below summarizes the components and the relative amounts of each component in the resulting cured coatings on substrates of Examples 22-34 described above.  \n\nTABLE3   \n\n\n<html><body><table><tr><td></td><td>Wt %</td><td colspan=\"2\">Type and Wt % Diacid Salt</td><td colspan=\"2\">Type and Wt %</td><td></td></tr><tr><td>Example</td><td>Polyurethane (W835/140)</td><td>900-DA</td><td>2003- DA</td><td>Aziridine PZ-2382*</td><td>BYK- 346</td><td>BRIJ 30</td></tr><tr><td>22</td><td>65</td><td>15</td><td></td><td>20</td><td></td><td></td></tr><tr><td>23</td><td>55</td><td>25</td><td></td><td>20</td><td></td><td></td></tr><tr><td>24</td><td>50</td><td>30</td><td></td><td>20</td><td></td><td></td></tr><tr><td>25</td><td>58.3</td><td>19.4</td><td></td><td>19.4</td><td>2.8</td><td></td></tr><tr><td>26</td><td>48.6</td><td>29.1</td><td></td><td>19.4</td><td>2.7</td><td></td></tr><tr><td>27**</td><td>60</td><td>15</td><td></td><td>20</td><td></td><td></td></tr><tr><td>28</td><td>65</td><td></td><td>15</td><td>20</td><td></td><td></td></tr></table></body></html>\n\n\\*PZ-2382 comprises $23\\%$ surfactant, as previously described. Therefore, $15\\ \\mathrm{\\mt}-\\%$ $\\mathrm{P}Z-2382=3.5$ wt- $\\%$ of surfactantand11.5wt $\\%$ hydrophilic aziridinecrosslinker $25\\mathrm{wt}-\\%$ $\\mathrm{P}Z-2382=5.8$ wt- $\\%$ of surfactant and19.2wt $\\%$ hydrophilic aziridine crosslinker 24.2 wt- $\\%$ PZ- $2382=5.6\\$ wt- $\\%$ of surfactant and $18.6~\\mathrm{wi}–\\%$ hydrophilic aziridine crosslinker 23wt- $\\%$ PZ $2382=5.3\\$ wt- $\\%$ of surfactant and 17.7 wt $\\%$ hydrophilic aziridine crosslinker \\*\\*Example 27 also contained $5\\mathrm{\\wt-\\%}$ of the silica nanoparticles of Prep 2.  \n\nAll the anti-fog coatings prepared from compositions of Table 3 exhibited excellent mechanical durability (i.e., the haze of the coatings increased only $1-7\\%$ haze change after",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 75,
+        "chunk": "# 30  \n\nlinear razor abrasion test and no scratches were observed after wiping the coatings with a paper towel for 30o cycles).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 76,
+        "chunk": "# Example 29  \n\nAn acrylic latex (40.5 wt $\\%$ ，43.5 grams), available from Dow Coating Materials under the trade designation “ROSHIELDTM 3188\", was mixed with 900-DA (30 wt $\\%$ D 30 grams) under stirring to form a homogenous dispersion.   \nl0 Then PZ-2382 (7.0 grams, neat) and 19.5 grams of water were added respectively and the resulting solution was stirred for $20~\\mathrm{min}$ .The final dispersion solution (35 wt $\\%$ solids) was thus obtained and subsequently applied on a PC film with a $\\#14$ Mayer. The resulting coating was cured at   \n15 $110^{\\circ}$ C. for 20 minutes. The resulting coated PC film exhibited“excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}$ C. vapor after 1 minute) and good optical properties with light transmittance up to $90\\%$ · Samples were subjected to both water soak test, one at room   \n20 temperature for 120 hours, and one at $65^{\\circ}\\mathrm{C}$ .120 hours. The soaked PC samples showed excellent water resistance and anti-fog properties remained.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 77,
+        "chunk": "# Example 30  \n\nA polyurethane/acrylic hybrid latex (40 wt $\\%$ ，43.5 grams), available from DSM NeoResins Company under the trade designation “NEOPAC R-9036” was mixed with 900-D (30 wt $\\%$ ，30.0 grams) under stirring to form a   \n30 homogenous dispersion. Then PZ-2382 (7.0 grams, neat), and 19.5 grams of water were added respectively and the resulting solution was stirred for $20\\mathrm{min}$ until a homogenous dispersion was obtained. The final dispersion solution (35 wt $\\%$ solids) was thus obtained and subsequently was applied   \n35 on a PC film with a $\\#14$ Mayer. The resulting coating was cured at $110^{\\circ}\\mathrm{C}.$ for 20 minutes.The resulting coated PC film exhibited“excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{~C~}$ .vapor after 1 minute) and good optical properties with light transmittance up to $90\\%$   \n40 Samples were subjected to both water soak tests, one at room temperature for 120 hours, and one at $65^{\\mathrm{{o}}}$ C.120 hours. The soaked PC samples showed excellent water resistance and anti-fog properties remained.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 78,
+        "chunk": "# Example 31  \n\nSilica nanoparticles comprising an epoxy silane surface treatment were prepare by combining Nalco 105O silica nanoparticles sol (180 grams, $10\\mathrm{\\mt\\\\%}$ ）with concentrated   \n50 $\\mathrm{H}_{2}\\mathrm{SO}_{4}$ to a $\\mathfrak{p H}$ value $:=2\\mathord{\\sim}3$ under stirring condition. Then $\\upgamma$ -Glycidoxypropyl-trimethoxysilane (1.31 grams, 50 mole $\\%$ coverage) was added to the acidified sol dispersion by drop wise. After addition, the solution was heated at $60^{\\circ}\\mathrm{C}$ · overnight. After reaction, the solution $\\mathfrak{p H}$ was adjusted to a   \n55 neutral condition by adding NaOH aqueous solution (5 wt $\\%$ ， A polyurethane dispersion (4.0 grams, $10\\mathrm{wt\\%}$ ),available from DSM NeoResins Company under the trade designation \"NeoResin $\\ensuremath{\\mathrm{R960^{\\circ}}}$ was mixed with a hydroxyl-containing   \n60 acrylic latex (2.0 grams, 10 wt $\\%$ ） obtained from Bayer Company under the trade designation “VPLS2058\". To the solution was sequentially added polyisocyanate, available from Bayer under the trade designation “Bayhdur $2665^{\\mathrm{,}\\mathrm{,}}$ (0.04 gram, neat), PZ-2382 (0.15 gram, neat) and epoxy   \n65 silane modified nanoparticles (50 mole $\\%$ coverage,2.0 grams, $10\\ \\mathrm{\\mt}\\ \\%$ . The final solution was stirred for 10 minutes. The final dispersion solution ( $35\\mathrm{\\wt\\\\%}$ solids)was",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 79,
+        "chunk": "# 32  \n\nthus obtained and subsequently applied on a PC film with a $\\#14$ Mayer. The resulting coating was cured at $110^{\\circ}\\mathrm{~C~}$ .for 20 minutes. The resulting coated PC film exhibited “excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ . vapor after 1 minute) and good optical properties with light transmittance up to $90\\%$ \\*  \n\nWhat is claimed is: 1. An anti-fog coating composition comprising an aqueous polymeric dispersion; a crosslinker; and at least 1 wt- $\\%$ of a surfactant; wherein the crosslinker is an aziridine crosslinker that is the reaction product of an ethoxylated alkyl multi (meth)acrylate and an alkyl aziridine, wherein the coating composition comprises at least $15\\ \\mathrm{wt}-\\%$ solids of aziridine crosslinker; wherein the dried and cured coating composition does not exhibit fogging within 8 seconds after being soaked in $25^{\\circ}\\mathrm{~C~}$ . water for 1 hour. 2. The anti-fog coating composition of claim 1 wherein the dried and cured coating composition comprises at least about 40 wt- $\\%$ of a carboxylate-containing polymer selected from a polyurethane polymer, an acrylic polymer, or a mixture thereof. 3. The anti-fog coating composition of claim 2 wherein the polymer comprises carbonate moieties. 4. The anti-fog coating composition of claim 2 wherein the surfactant is unreactive with respect to the polymer. 5. The anti-fog coating composition of claim 4 wherein the crosslinker comprises at least three terminal aziridine groups. 6. The anti-fog coating composition of claim 4 wherein the crosslinker has the general formula  \n\nwherein $\\mathbf{R^{\\prime}}$ is hydrogen, or a $\\mathrm{C_{1}{-}C_{4}}$ alky1 group; $\\mathrm{R}\"$ is hydrogen or methyl, $\\mathbf{x},\\mathbf{y}$ ，and z are independently at least 1; and $\\mathbf{M}$ i   \n$5$ the coating composition comprises at least $10\\mathrm{wt}\\%$ solids of aziridine crosslinker. 8. The anti-fog coating composition of claim 1 wherein   \n10 the surfactant is a nonionic surfactant. 9. The anti-fog coating composition of claim 8 wherein the surfactant comprises polyalkylene oxide repeat units. 10. The anti-fog coating composition of claim 7 wherein the surfactant further comprises a silicone surfactant, an   \n15 ionic surfactant, or a mixture thereof. 11. The anti-fog coating composition of claim 1 wherein the coating composition further comprises an acid or salt of a polyalkylene oxide. 12. The anti-fog coating composition of claim 1 wherein   \n20 the dried and cured coating comprises up to $40\\ \\mathrm{wt-\\%}$ of inorganic oxide nanoparticles. 13.The anti-fog coating composition of claim 12 wherein the inorganic oxide nanoparticles comprise silica, alumina,   \n25 or a mixture thereof. 14. The anti-fog coating composition of claim 13 wherein the nanoparticles comprise a silane surface treatment comprising a water dispersible group. 15. The anti-fog coating composition of claim 1 wherein   \n30 the dried and cured coating composition does not exhibit fogging within 60 seconds after being soaked in $50^{\\circ}\\mathrm{C}$ .water for 120 hours or $65^{\\circ}\\mathrm{~C~}$ water for 120 hours. 16. The anti-fog coating composition of claim 1 wherein the cured anti-fog coating has a transmission of at least $90\\%$   \n35 17. An article comprising a substrate and the dried and cured anti-fog coating of claim 1. 18.A method of providing an anti-fog coating on a surface of a substrate, the method comprising   \n40 providing an aqueous anti-fog coating composition according to claim 1; applying the coating composition to a substrate; and drying and curing the coating composition.  \n\n![](images/5b14bde7af01e80f4692cc380ab7a1f1b4df250595fa8e5a43489c483a269cfd.jpg)",
+        "category": " Results and discussion"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "(12) United States Patent Lu et al.",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (54) ANTI-FOG COATING COMPRISING AQUEOUS POLYMERIC DISPERSION, CROSSLINKER AND ACID OR SALT OF POLYALKYLENE OXIDE  \n\n(71） Applicant: 3M INNOVATIVE PROPERTIESCOMPANY, St. Paul, MN (US)  \n\n(72） Inventors: Yongshang Lu, Woodbury, MN (US); Naiyong Jing, Woodbury, MN (US); Dang Xie, Shanghai (CN); Zhigang Yu, Shanghai (CN); Caroline M. Ylitalo, Stillwater, MN (US); Mahfuza B. Ali, Mendota Heights, MN (US); Alexander J. Kugel, Woodbury, MN (US); Steven P. Swanson, Blaine, MN (US)  \n\n(73） Assignee: 3M Innovative Properties Company, St. Paul, MN (US)  \n\n（\\*）Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 6 days. This patent is subject to a terminal disclaimer.  \n\n(21) Appl. No.: 14/361,076   \n(22) PCT Filed: Nov. 1, 2012   \n(86) PCT No.: PCT/US2012/062903 $\\S\\ S71$ (c)(1), (2) Date: May 28, 2014   \n(87) PCT Pub. No.: WO2013/089927 PCT Pub. Date: Jun. 20, 2013",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# Prior Publication Data  \n\nUS 2015/0118501 A1 Apr.30, 2015",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# Related U.S. Application Data  \n\n(60） Provisional application No. 61/576,044, filed on Dec. 15,2011.  \n\n(51) Int. Cl. C09K3/18 (2006.01) C09D 133/00 (2006.01) C09D 175/04 (2006.01) C08K 5/06 (2006.01) G02B 1/18 (2015.01) C09D 5/02 (2006.01) C09D 5/16 (2006.01) C08K5/00 (2006.01) G02B 27/00 (2006.01) C03C 17/00 (2006.01) C03C 17/32 (2006.01)  \n\n(52) U.S. Cl. CPC G02B 1/18 (2015.01); C03C 17/007 (2013.01); C03C 17/322 (2013.01); C08K 5/0025 (2013.01); C08K 5/06 (2013.01); C09D 5/024 (2013.01); C09D 5/1687 (2013.01);  \n\n(10) Patent No.: US 10,048,408 B2   \n(45) Date of Patent: \\*Aug. 14, 2018  \n\nC09D 133/00 (2013.01); C09D 175/04 (2013.01); C09K 3/18 (2013.01); G02B 27/0006 (2013.01); C03C 2217/445 (2013.01); C03C 2217/478 (2013.01); Y10T 428/3158 (2015.04); Y10T428/3192 (2015.04); Y10T 428/31551 (2015.04); Y10T 428/31605 (2015.04); Y10T428/31699 (2015.04); Y10T 428/31935 (2015.04)  \n\n(58) Field of Classification Search CPC C03C 17/007; C03C 17/322; C03C 2217/445; C03C 2217/478; C08K 5/0025; C08K 5/06; C09D 133/00; C09D 175/04; C09D 5/04; C09D 5/1687; C09K 3/08; Y10T 428/31551; Y10T 428/3158; Y10T 428/31605;Y10T 428/31699; Y10T 428/3192; Y10T 428/31935 USPC 428/423.1,480, 482, 500; 523/169; 427/385.5 See application file for complete search history.",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# References Cited",
+        "category": " References"
+    },
+    {
+        "id": 6,
+        "chunk": "# U.S. PATENT DOCUMENTS  \n\n2,803,552 A 8/1957 Stedman   \n3,022,178 A 2/1962 Park   \n3,425,976 A 2/1969 Adams   \n3,437,617A 4/1969 Bogle   \n3,484,157 A 12/1969 Crandon   \n3,488,215 A 1/1970 Shepherd   \n3,700,487 A 10/1972 Crandon   \n(Continued)",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# FOREIGNPATENTDOCUMENTS  \n\nCN 1747906 3/2006 CN 101065456 10/2007 (Continued)",
+        "category": " References"
+    },
+    {
+        "id": 8,
+        "chunk": "# OTHERPUBLICATIONS  \n\nTrotoir, “Anti-fog/antistat eases processing problems\", Modern Plastics, Oct. 1988, 3 pgs.   \nHowarter, “Self-Cleaning and Next Generation Anti-Fog Surfaces and Coatings\", Macromolecular Rapid Communications, 2oo8, vol. 29, pp.455-466.   \nNie,“Superhydrophilic Anti-Fog Polyester Film by Oxygen Plasma Treatment\"， Proceedings of the Nano/Micro Engineered and Molecular Systems, 4th IEEE International Conference, Jan. 2009, pp. 1017-1020.   \nChattopadhyay, “Structural engineering of polyurethane coatings for high performance applications\", Progress in Polymer Science, 2007, vol. 32,pp.352-418.  \n\n(Continued)  \n\nPrimary Examiner— Thao T Tran (74) Attorney, Agent, or Firm — Adrian L. Pishko; Carolyn A. Fischer",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# ABSTRACT  \n\nCoating compositions are described comprising an aqueous polymeric dispersion; a crosslinker; and an acid or salt of a polyalkylene oxide. Also described are articles comprising the dried and cured coating composition disposed on a substrate as well as a method a providing an anti-fog coating on a substrate.",
+        "category": " Abstract"
+    },
+    {
+        "id": 10,
+        "chunk": "# 22 Claims, No Drawings",
+        "category": " References"
+    },
+    {
+        "id": 11,
+        "chunk": "# References Cited",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# U.S. PATENT DOCUMENTS  \n\n3,725,352 A \\* 4/1973 Koleske C08G 63/672   \n525/88   \n3,773,776 A 11/1973 Iler   \n3,821,136 A 6/1974 Hudgin   \n3,822,238 A 7/1974 Blair   \n3,865,619 A 2/1975 Pennewiss   \n3,895,155 A 7/1975 Shukuri   \n3,897,356 A 7/1975 Pociluyko   \n4,016,129 A 4/1977 Miyosawa   \n4,027,073 A 5/1977 Clark   \n4,064,308 A 12/1977 Laurin   \n4,126,595 A \\* 11/1978 Martorano C09D 133/00   \n428/418   \n4,127,682 A 11/1978 Laurin   \n4,211,823 A 7/1980 Suzuki   \n4,467,073 3A 8/1984 Creasy   \n4,478,909 A 10/1984 Taniguchi   \n4,551,484 A 11/1985 Radisch   \n4,563,307 A \\* 1/1986 Briden C08K 5/3412   \n526/263   \n4,605,698 A 8/1986 Briden   \n4,609,688 A 9/1986 Radisch   \n4,745,152 A 5/1988 Fock   \n4,876,302 A 本 10/1989 Noll C08G 18/0819   \n524/267   \n5,073,404 A 12/1991 Huang   \n5,075,133 A 12/1991 Hosono   \n5,116,442 A 5/1992 Daude   \n5,124,021 A 6/1992 Kaneyasu   \n5,134,021 A 7/1992 Hosono   \n5,262,475 A 11/1993 Creasy   \n5,424,355 A \\* 6/1995 Uemae et al. 524/507   \n5,585,186 A 12/1996 Scholz   \n5,695,851 A \\* 12/1997 Watanabe C09D 4/00   \n428/147   \n5,723,175 A 3/1998 Scholz   \n5,804,612 A 9/1998 Song   \n5,807,923 A \\* 9/1998 Sleegers. 524/757   \n5,821,294 A 10/1998 Perlinski 524/507   \n5,873,931 A 2/1999 Scholz   \n5,877,254 A 3/1999 La Casse   \n6,013,372 A 1/2000 Hayakawa   \n6,040,053 A 3/2000 Scholz   \n6,156,409 A 12/2000 Doushita   \n6,194,498 B1 2/2001 Anderson   \n6,420,020 B1 7/2002 Yamazaki   \n6,800,365 B2 10/2004 Yamazaki   \n7,008,979 B2 3/2006 Schottman   \n7,048,989 B2 5/2006 Watkins   \n7,261,843 B2 8/2007 Knox  \n\n7,838,110 B2 11/2010 Zhu 8,017,666 B2 9/2011 Bissinger   \n2003/0203991 A1 10/2003 Schottman   \n2003/0205059 A1 11/2003 Roche   \n2004/0022950 A1\\* 2/2004 Jung et al. 427/385.5   \n2004/0137155 A1 7/2004 Bernheim   \n2006/0063868 A1 3/2006 Janmaat   \n2006/0135649 A1 6/2006 Jedlicka et al.   \n2006/0204528 A1\\* 9/2006 Nolte B82Y30/00 424/401   \n2007/0155946 A1\\* 7/2007 Berti C08G63/64 528/272   \n2007/0286959 A1 12/2007 Palmer   \n2008/0017071 A1\\* 1/2008 Moebus C09D5/028 106/287.24   \n2008/0108743 A1\\* 5/2008 Tomizaki C08F 265/00 524/523   \n2008/0160187 A1 7/2008 Murata et al.   \n2010/0227969 A1 9/2010 Zhu   \n2011/0195263 A1\\* 8/2011 Malotky C08J3/05 428/480   \n2012/0101210 A1\\* 4/2012 Nennemann .. C08G 18/0828 524/507   \n2012/0305862 A1\\* 12/2012 Kasahara C08G18/807 252/519.33   \n2014/0335360 A1\\* 11/2014 Jing et al. 428/412",
+        "category": " References"
+    },
+    {
+        "id": 13,
+        "chunk": "# FOREIGNPATENTDOCUMENTS  \n\nCN 101602913 12/2009   \nCN 101591494 8/2011   \nEP 0238991 1A2\\* 9/1987 C08G 18/0819   \nEP 2062861 5/2009   \nJP 03275787 12/1991   \nJP 07-102188 4/1995   \nJP 10297081 11/1998   \nJP 2000515564 11/2000   \nWO WO 1993-23471 11/1993   \nWO WO 1996-18691 6/1996   \nWO WO 2008-039228 4/2008   \nWO WO 2009-085680 7/2009   \nWO WO 2010-114700 10/2010   \nWO WO 2013-089926 6/2013",
+        "category": " References"
+    },
+    {
+        "id": 14,
+        "chunk": "# OTHERPUBLICATIONS  \n\nLu,“Durable Anti-fog Coatings form Waterborne Polyurethane Dispersions and Nanoparticles\", Performance Materials and Coating Group, 3M, 13pgs. International Search Report for PCT International Application No. PCT/US2012/062903, dated Mar. 1, 2013, 3pgs.  \n\n\\* cited by examiner",
+        "category": " References"
+    },
+    {
+        "id": 15,
+        "chunk": "# 1 ANTI-FOG COATING COMPRISING AQUEOUS POLYMERIC DISPERSION, CROSSLINKERANDACIDORSALTOF POLYALKYLENE OXIDE  \n\nCROSSREFERENCETORELATED APPLICATIONS  \n\nThis application is a national stage filing under 35 U.S.C. 371 of PCT/US2012/062903，filed Nov. 1，2012，which claims priority to Provisional Application No. 61/576044, filed Dec. 15, 201l, the disclosure of which is incorporated by reference in its/their entirety herein.",
+        "category": " References"
+    },
+    {
+        "id": 16,
+        "chunk": "# BACKGROUND  \n\n15  \n\nAs described for example in U.S. Pat. No. 7,008,979; fog formation occurs under conditions of high humidity and high temperature or at interfacial boundaries where there is a large temperature and humidity difference. Coatings which reportedly reduce the tendency for surfaces to “fog up\" (i.e., anti-fogging coatings) have been suggested.  \n\nIn order to prevent this fogging, it is known to use various surface active agents to provide anti-fog properties to articles. For example, hydrophilic agents have been added to polyurethanes in order to impart anti-fog properties. Antifog coating compositions for transparent surfaces which include a three-dimensional cross-linked polyurethane having a free surface active agent disposed within open domains in its cross-linked structure have been suggested. The coating compositions are prepared by reacting isocyanates with polyfunctional polyols to obtain a polyurethane, and subsequently contacting the thus prepared polyurethane with a hydrophilic surface-active agent in order to diffuse molecules of the surface-active agent into the interior of the coating. (See for example U.S. Pat. Nos. 4,551,484 and 4,609,688 to Radisch et al.)  \n\nThe surface-active agent, however, is not chemically reacted into the polyurethane, but is instead physically disposed within the polymeric structure. As such, the cured coating is susceptible to undesirable leaching and erosion of the surfactant, thereby decreasing the anti-fog properties of the coating composition.  \n\nIt has also been proposed to react surface active agents into a polyurethane coating composition in order to impart 4 anti-fog properties to the coating composition. For example, the addition of sulfonated “resins\" to polyurethanes in order to prepare coatings with various properties including antifog characteristics have been suggested. The resins are prepared from diols or diamines reacted with di-carboxylic 5 acid esters, followed by sulfonation of double bonds or quarternization of amines. The resins are intended to increase the hydrophilic character and water absorption of the polyurethane coatings by reacting into the polyurethane backbone in an end-to-end fashion, rather than as pendent 5 groups. Such resins which react in an end-to-end fashion, as opposed to remaining pendant at the end of the polyurethane chain, cannot provide for a clear delineation of hydrophilic and hydrophobic groups and in this respect do not behave as surfactants, i.e., they do not provide cooperation between 6 distinct hydrophilic and hydrophobic portions to reduce interfacial tension.(See for example U.S. Pat. No.3,822,238 to Blair et al.)  \n\nPolyurethane compositions have also been suggested which are useful as coatings for transparent substrates with improved self-healing properties and prevention against formation of surface moisture. The polyurethane compositions are prepared from a reaction of an isocyanate with a polyol mixture including a difunctional sulfonated polyether polyol and a trifunctional polyol. Such a polyurethane composition incorporates only polyol combinations which impart hydrophilic character to the coating, and does not further incorporate into the composition a surfactant material. (See for example U.S.Pat.No. 4,754,152 to Fock et al.) However, these compositions do not provide permanent fog resistance properties, i.e. fog resistant properties which last after repeated washings or extended soaking in water, nor are they effective for more than a few hours of use.  \n\nAdditionally, it is known to incorporate non-ionic surfactants containing reactive functional groups into polyurethanes prepared with polyvinylpyrrolidone as a hydrophilic agent. For example, anti-fog coating compositions incorporating an isocyanate prepolymer which is reacted with a polyvinylpyrrolidone polymer, the reaction product thereof being subsequently reacted with a non-ionic surfactant hav0 ing reactive groups for reacting with the isocyanate, for instance, hydroxyl reactive groups are known. Polyvinylpyrrolidone polymers, however, while serving to increase the hydrophilicity of the polyurethane matrix and improve antifog properties, generally reduce the scratch-resistance, 5 chemical resistance, water sensitivity, and durability of the cured polyurethane surface. Thus, although these compositions, when cured, have been known to provide anti-fog properties, their solvent sensitivity, flexibility and scratch resistance properties are less than desirable. (See for 0 example U.S. Pat. No. 4,467,073 to Creasy)",
+        "category": " Introduction"
+    },
+    {
+        "id": 17,
+        "chunk": "# SUMMARY  \n\nAlthough various anti-fog coatings have been described, iindustry would find advantage in alternative compositions that can provide persistent long-lasting anti-fog properties.  \n\nIn one embodiment, a coating composition is described comprising an aqueous polymeric dispersion; a crosslinker; and an acid or salt of a polyalkylene oxide.  \n\nAlso described are articles comprising the dried and cured coating composition disposed on a substrate as well as a method a providing an anti-fog coating on a substrate.",
+        "category": " Abstract"
+    },
+    {
+        "id": 18,
+        "chunk": "# DETAILEDDESCRIPTIONOFILLUSTRATIVE EMBODIMENTS  \n\nThe coating compositions described herein are suitable for imparting anti-fog characteristics. The coating composition comprises an aqueous polymeric dispersion, typically one that can be prepared as a latex, and more typically an alkaline $\\mathfrak{p H}$ stable latex. Favored polymeric dispersions include polyurethane polymer dispersions, acrylic polymer dispersions, and mixture thereof. Such polymers are typically thermoplastic.  \n\nThe term“polyurethane\" includes any polymeric material that comprises polyurethane segments. The term “polyurethane segment\" refers to at least two urethane and/or urea groups that are connected by an organic group.  \n\nThe term“acrylic\" includes any polymer or copolymer of acrylic acid, methacrylic acid, ester of these acids or acrylonitrile.  \n\nThermoplastic polyurethane compositions are generally the reaction product of a diisocyanate with short-chain diols (also referred to as chain extenders) and diisocyantes with long-chained difunctional diols (known as polyols). Polyurethanes are characterized as having urethane groups, i.e. NH— $\\mathrm{{C}=}0$ —O—that link the segments derived from",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 19,
+        "chunk": "# 2  \n\nhe diisocyanate and diol. Such urethane group comprise :arbonyl group, i.e.a carbon atom double bonded to a ixygen atom, $\\mathrm{C=O}$ ·  \n\nNon-limiting examples of long-chained polyols are polyether polyols, polyester polyols, acrylic polyols and mixtures of such polyols. Typically, polyester based thermoplastic urethanes are known for providing good abrasion and chemical resistance. The final resin consists of linear polymeric chains in block-structures. Such chains contain low polarity segments, referred to as “soft segments\", alternating with shorter, high polarity segments, referred to as \"hard segments\". Both types of segments are linked together by covalent links, forming random copolymers or blockcopolymers.  \n\nPolyester polyols are prepared by the polyesterification of 15 an organic polycarboxylic acid or anhydride thereof with organic polyols and/or an epoxide. Usually, the polycarboxylic acids and polyols are aliphatic or aromatic dibasic acids and diols. The diols that are usually employed in making the polyester include, but are not limited to, acyclic alkylene 2C glycols, such as ethylene glycol and neopentyl glycol, and cyclic glycols such as hydrogenated Bisphenol A, cyclohexanediol and cyclohexanedimethanol. Polyols of higher functionality can also be used. Non-limiting examples include trimethylolpropane and pentaerythritol, as well as 25 higher molecular weight polyols such as those produced by oxyalkylating low molecular weight polyols.  \n\nThe acid component of the polyester consists primarily of monomeric carboxylic acids or anhydrides having 2 to 18 carbon atoms per molecule.Among the acids that can be used are phthalic acid, terephthalic acid, hexahydrophthalic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, glutaric acid, chlorendic acid, decanoic acid and dodecanoic acid. Higher polycarboxylic acids, such as trimellitic acid and tricarballylic acid, can also be used. Where acids are referred to above, it is understood that anhydrides of those acids that form anhydrides can be used in place of the acid. Also,lower alkyl esters of the acids such as dimethyl glutarate and dimethyl-terephthalate can be used.  \n\nIn addition to the polyester polyols, hydroxy-containing acrylic polymers or acrylic polyols can be used as the polyol component.  \n\nExamples of polyether polyols are polyalkylene ether polyols include those having the following general formula:  \n\nene-bis-(cyclohexyl isocyanate), isophorone diisocyanate and NCO-prepolymers, e.g., the reaction products of monomeric polyisocyanates, such as those mentioned above, with polyester or polyether polyols. Particularly desired are the isocyanurates from isophorone isocyanate and 1,6-hexamethylene diisocyanate, both of which are commercially available.  \n\nIn some embodiments, the polyurethane dispersion comprises a polyester backbone, a polycarbonate backbone, a polyester carbonate or a combination thereof. In other embodiments, the acrylic dispersion comprises an acrylic backbone, a hydroxyl-containing acrylic backbone, or a combination thereof. In yet other embodiments, the polymeric dispersion is a urethane-acrylic hybrid, or polycarbonate urethane/acrylic hybrid. In some embodiments, the polymers are described as having a polycarbonate or carbonate backbone. In such embodiments, the polymer comprises aliphatic or aromatic carbonate moieties, such as bisphenol A carbonate moieties.  \n\nVarious processes have been developed for the preparation of waterborne or aqueous polymeric dispersions. In the preparation of aqueous polyurethane polymers, typically a medium molecular weight polymer (e.g. prepolymer) is 25 formed by the reaction of suitable diols or polyols with a molar excess of diisocyantes or polyisocyanates in the presence of an internal emulsifier. The internal emulsifier is typically a diol with an ionic group (carboxylate, sulfonates, or quaternary ammonium slat) or a non-ionic group, such as 30 polyethylene oxide. Aqueous polyurethane dispersion are typically one of three types, i.e. non-ionic, cationic, and anionic depending on the type of hydrophilic segments present in the polyurethane backbone. In the case of anionic 35 polyurethanes,dimethyol propionic acid (DMPA)is commonly incorporated into the polyurethane backbone due to its effectiveness for water dispersions in the subsequent neutralization reactions with triethylamine. The carboxylate ion of DMPA in the polymer is hydrophilic and serves an 40 anionic center as well an internal emulsifier. Carboxylic ions not only stabilize aqueous polyurethane dispersions, but also provide curing sites. Aqueous acrylic polymers are also typically prepared with an internal emulsifier and thus typically also comprise carboxylate ions to stabilize the 45 dispersion and provide curing sites.  \n\n![](images/55bffe659718cdcf0aa6501a68ed6968d4f12b14b9bcf50c02852a21a9915b11.jpg)  \n\nwhere the substituent R is hydrogen or lower alkyl contain- 55 ing from 1 to 5 carbon atoms including mixed substituents, and n is typically from 2 to 6 and m is from 10 to 100 or even higher. Included are poly(oxytetramethylene)glycols, poly (oxyethylene)glycols, poly(oxy-1,2-propylene)glycols and the reaction products of ethylene glycol with a mixture of 6( 1,2-propylene oxide and ethylene oxide.  \n\nThe polyisocyanates that can be used include aromatic and aliphatic polyisocyanates with aliphatic polyisocyanates being more desirable because of their superior ultraviolet light stability and non-yellowing tendencies. Non-limiting examples of such polyisocyanates include monomeric polyisocyanates, such as toluene diisocyanate, and $^{4,4^{\\prime}}$ -methyl  \n\nThe (e.g. polyurethane and/or acrylic) polymer is generally dispersed in a liquid diluent to form a polymeric dispersion.“Liquid diluent\" refers to solvent that is volatile and removed after the coating is applied. In favored embodi  \n50 ments, the coating composition comprises predominantly water as the diluent with little or no organic solvents. In this embodiment, the concentration of organic solvent is typically less than 2, 1.5, $1\\ \\mathrm{wt}\\mathrm{-}\\%$ or $0.5\\mathrm{\\wt-\\%}$ of the coating composition. A polyurethane dispersion available from   \n55 Incorez, under the trade designation “W835 Series” are described as being co-solvent free grades of polyurethane dispersions.  \n\nThe (e.g. polyurethane and/or acrylic) polymer dispersed in an aqueous diluent are film-forming polymers. Suitable polymer latexes and methods for making them are widely known in the art, and many are commercially available.  \n\nTypically, the particles in the polymer latexes are substantially spherical in shape. The polymer core may comprise one or more water-insoluble polymers, although this is not a requirement. Useful polymer particle sizes include those typical of latexes and other dispersions or emulsions. Typical polymer particle sizes are in a range of from about",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 20,
+        "chunk": "# 6  \n\n0.01 micrometers to 100 micrometers, preferably in a range of from O.o1 to 0.2 micrometers, although this is not a requirement.  \n\nExamples of commercially available aqueous aliphatic polyurethane emulsions include NEOREZ R-960, NEOREZ 5 R-967,NEOREZR-9036, andNEOREZR-9699 fromDSM NeoResins, Inc. of Wilmington, MA; aqueous anionic polyurethane dispersions available as ESSENTIAL CC4520, ESSENTIAL CC4560, ESSENTIAL R4100, and ESSENTIAL R4188 from Essential Industries, Inc. of Merton, Wis.; 1( polyester polyurethane dispersions available as SANCURE 843, SANCURE 898, and SANCURE 12929 from Lubrizol, Inc.of Cleveland, Ohio; an aqueous aliphatic self-crosslinking polyurethane dispersion available as TURBOSET 2025 from Lubrizol, Inc.; polyurethane dispersions available as 1: “INCOREZ” from Incorez Co., Lancashire, England; and polyurethanes dispersions available from Stahl USA, Peabody, Mass. under the trade designations “RU-O77” and \"RU- $.075^{,3}$ ，  \n\nSelf cross-linking polymer dispersion maybe used in the 20 ink receptive layer. Such polymeric dispersions have self cross-linking function that is activated upon drying of the coating layer. The use of this type of dispersions may eliminate the need for incorporating crosslinking compounds into the coating composition. Examples of self 25 cross-linking polymer dispersions include polyurethane dispersions available from Bayer Material Science, LLC of Pittsburgh, Pa. as“BAYHYDROL PR240” and from DSM Neoresins as “NEOREZ R-661\".  \n\nExamples of commercially available aqueous aliphatic 3 acrylic emulsions include acrylic latexes available from Dow Coating Materials under the trade designations ROSHIELDTM and RHOPLEXTM such as“ROSHIELDTM 3188\"，“ROSHIELDTM $3275^{\\circ}$ ，“ROSHIELDTM $1024^{\\cdots}$ “ROSHIELDTM 636\",“RHOPLEXTM WL-96\", and“RHO- 3 PLEXTM CL- $104^{,}$ ; acrylic latexes available from Arkema Coating Resins under the trade designation “UCARTM\", such as “UCARTM LATEX $455'$ ,“ UCARTM LATEX 443\", \"UCARTMLATEX $451^{\\circ}$ ， and “UCARTM LATEX DM109\"; acrylic latexes available from Lubrizol Advanced Materials， 4 Inc. under the trade designation HYCAR $\\textsuperscript{\\textregistered}$ ，such as “HYCAR $\\textsuperscript{\\textregistered}$ $26349^{\\prime\\prime}$ ; \"HYCAR $\\textsuperscript{\\textregistered}$ $26459^{\\circ}$ ; and acrylic latexes available from DSM NeoResins under the trade designation “NEOCRYL”, such as “NEOCRYL $\\mathrm{A}{-}640^{3}$ ，“NEOCRYL $\\mathrm{XK-}220^{\\circ}$ ，“NEOCRYL A-1044\"，“NEOCRYL $\\mathrm{{XK-90}^{9}}$ ，4 “NEOCRLYL XK-96” and “NEOCRYL XK-95”.  \n\nDispersions of polyurethane polymers can be characterized by measuring the properties of a 50-100 micron thin film of the neat polyurethane formed from the dispersion (dried at $22^{\\circ}\\mathrm{C}/50\\%$ RH for 14 days). In some embodiments, the elongation of the thin film thus formed typically has an elongation at break ranging from about $50\\%$ to about $60\\%$ . In some embodiments, the tensile strength ranges from about 15 to $30\\mathrm{MPa}$  \n\nIn some embodiments, the acrylic dispersion comprises a polyacrylate backbone, a polycarbonate backbone, or a combination thereof.  \n\nA combination of polymeric polymers may be utilized in the (e.g. anti-fog） coating composition. For example, the polyurethane dispersion may comprise two or more polyurethane polymers having a different average molecular weight. Further, the composition may contain a different type of polymer in combination with a polyurethane, for example, as would be obtained by mixing an acrylic latex and a polyurethane latex. In one embodiment, the aqueous polyurethane dispersion comprises a mixture of “INCOREZ W835/140\" and“NEOREZ R-961\". The inclusion of\"NEO  \n\nREZ R-961\" can improve the abrasion resistance. However, when the concentration of “NEOREZ R-961” exceeds a a weight ratio of about 1:2 (i.e. more than 1 part by weight “NEOREZ R-961\" per 2 parts by weight“INCOREZ W835/ 140\"), the coating can become white after being soaked in water. In yet another example, a combination of a polyurethane polymer and an acrylic polymer is utilized or a hybrid polymer of both acrylic and polyurethane.An example of a commercially available acrylic urethane copolymer dispersion is available under the trade designation NEOPAC from DSM Neoresins.  \n\nThe coating composition typically comprises one or more (e.g. polyurethane and/or acrylic) polymers in an amount totaling at least $40\\mathrm{wt}\\%$ solids of the coating composition and typically no greater than $90\\ \\mathrm{wt-\\%}$ or $85\\ \\mathrm{wt-\\%}$ or 80 wt- $\\%$ . In some embodiments, the coating composition comprises one or more polymers in an amount of at least 45 wt- $\\%$ or $50\\%$  \n\nThe anti-fog coating comprises a hydrophilic additive that is non-reactive with respect to the polyurethane polymer, yet is reactive and thus can be crosslinked by the (e.g. aziridine) crosslinker. The concentration of such hydrophilic additive is typically at least 5 wt- $\\%$ ,6wt- $\\%$ ,7wt- $\\%$ 8wt- $\\%$ ,9wt- $\\%$ or 10 wt- $\\%$ of the solids of the coating composition. In some embodiments, the concentration of hydrophilic additive is at least11 wt- $\\%$ ，12wt- $\\%$ ，13wt- $\\%$ ，14wt- $\\%$ ,or15wt- $\\%$ .The concentration of such hydrophilic additive is typically no greater than about $40\\ \\mathrm{wt-\\%}$ or $35\\ \\mathrm{wt-\\%}$ ，  \n\nOne example of a hydrophilic additive that can be crosslinked by the crosslinker is an acid or salt of a polyalkylene oxide. Such additive generally comprises a polyalkylene oxide backbone that comprises repeat units of the ethylene oxide, propylene oxide, or a combination thereof. The   \n； number of ethylene oxide and propylene oxide repeat units may independently range from O to 100 with the proviso that the sum of ethylene oxide and propylene oxide repeat units range from about 10 to 100. The polyalkylene oxide backbone typically comprises more ethylene oxide repeat units   \n） than propylene oxide repeat units. In some embodiments, the ratio of ethylene oxide repeat units to propylene oxide repeat units is at least 2:1,or 3:1; or 4:1,or 5:1,or 6: 1 or 7:1,or 8:1,or 9:1,or 10:1. The polyalkylene oxide backbone is typically linear and divalent, terminating with an acid or salt   \n5 group on each end. A divalent linking group is typically present between the polyalkylene oxide backbone and the at least one or two terminal acid or salt groups. Depending on the starting compound and reactant(s), the linking group can vary. In some embodiment, the additive is formed from a   \npolyalkylene oxide amine (also referred to as a polyether amine) reacted with a succinic anhydride forming a diacid that is then reacted with an alkyl amine to convert the acid group to an ammonium salt group. In this embodiment, the linking group between the polyalkylene oxide backbone and   \n；theterminal acid or salt groups may be $\\mathrm{\\_CH_{2}N H C O C_{2}H_{4}-}$ -. However, other linking group would be present by use of other reaction schemes. The molecular weight of the linking group is generally relatively small so as not to detract from the hydrophilic nature of the poly  \n）alkylene oxide backbone. In some embodiments, the molecular weight of the linking group is no greater than 100 g/mole.As the molecular weight of the polyalkylene oxide backbone increases, the molecular weight of the linking group may also increase without detracting from the hydro  \n） philic properties. However, the molecular weight of the linking group is typically no greater than about 20, 15 or $10\\%$ by weight of the total molecular weight of the hydro  \n\nphilic additive (i.e. the molecular weight of the linking groups divided by the total molecular weight multiplied by $100\\%$ ，  \n\nIn one embodiment, the hydrophilic additive comprises a divalent polyalkylene oxide backbone and terminal acid or salts groups, as may be represented by the following formula:  \n\n$$\n\\mathrm{R-L}\\mathbf{-}(\\mathrm{C}_{3}\\mathrm{H}_{6}\\mathrm{O})_{x}(\\mathrm{C}_{2}\\mathrm{H}_{4}\\mathrm{O})_{y}\\mathbf{-}\\mathrm{L}\\mathbf{-}\\mathrm{R}\n$$  \n\nwherein is $\\mathrm{~R~}$ is a reactive group that is capable of (cova- 1( lently) reacting with the (e.g. aziridine) crosslinker such as a carboxylic acid group or salt thereof,  \n\n$\\mathrm{~L~}$ is a divalent linking,  \n\nand $\\mathbf{x}$ and y independently range from O to 10o with the proviso that the sum of $\\mathbf{x}{+}\\mathbf{y}$ ranges from about 5, 6, 7, 8, 1:  \n\n9, or 10 to about 100.  \n\nThe linking group L can vary depending on the selection of reactants. For example, when a polyalkylene oxide diol is reacted with an isocyanate compound, L may be OCONH—.  \n\nIn another embodiment, when a polyalkylene oxide diamine is reacted with an isocyanate compound, L may be -NHCONH—. In yet another embodiment, when a polyalkylene oxide diol is reacted with an anhydride or carboxylic acid compound, L may be —( $\\mathrm{C}{=}\\mathrm{O}_{,}$ O—.Lmay also 2: be an ester linkage when a polyalkylene oxide diacid is reacted with an alcohol compound. In yet another embodiment, L may be —CONH— by reaction of a polyalkylene oxide diacid or acrylic chloride with a primary or secondary amine. The amide linkage can also be made by the reaction 3( of a polyalkylene diamine with an anhydride or a carboxylic acid compound. In yet another embodiment, L may be —NR— by reaction of a polyalkylene oxide diamine with a halide compound or by reaction of a polyalkylene oxide dihalide with an amine compound. In yet another embodi- 3: ment, L can be —COS—by the reaction of a polyalkylene oxide diol with an acryl chloride thiol or thiol ester compound. Further, L may be — $\\mathrm{CS}_{2}$ - by reaction a polyalkylene oxide dithiol with a thiol or mercapto compound. In yet another embodiment, L may be —S— by reaction of a 4( polyalkylene oxide dithiol with a halide compound. In yet another embodiment, L may be —O— by a condensation reaction of polyalkylene oxide diol. In yet another embodiment, L may be —SCONH—by the reaction of a polyalkylene oxide dithiol with an isocyanate compound or by 4: reaction of a polyalkylene oxide diisocyanate with a thiol compound.  \n\nThe counter ions of the acid salts can be ammonium, as well as primary, secondary or tertiary alkyl ammoniums. The counter ions may also be inorganic metallic ions includ- 5 ing divalent zinc from zinc halides, nitrate, carbonate, or ammonium carbonate. Other inorganic metallic ions comprise Cu, Ti, and Zr.  \n\nWithout intending to be bound by theory it is surmised that alkylene oxide repeat units of the acid or salt of 5 polyalkylene oxide can aid in preventing a surfactant, compatible with such hydrophilic segments (e.g. such as a non-ionic surfactant comprising alkylene oxide repeat units) from leaching out of the coating.  \n\nThe anti-fog coatings described herein comprise a cross- 6( linker. The crosslinker typically reacts with the (e.g. carboxylate) hydrophilic segments present in the polymer (e.g. polyurethane and/or acrylic) backbone.Suitable crosslinkers typically comprises at least three terminal (e.g. carboxylate) reactive groups. 6:  \n\nCarboxylic ion (e.g. carboxylate） containing aqueous polymeric dispersions and a multi-aziridine curing agent may be formulated as a curing polymeric dispersion. The curing mechanism can take place at ambient temperature during the drying process of when the $\\mathfrak{p H}$ value drops below 6.In some embodiments the crosslinker may also react with the (e.g. diacid or salt of a polyalkylene oxide) hydrophilic additive, as just described.  \n\nFavored examples of crosslinkers include aziridine crosslinkers available under various trade designations, such as described in the examples; carbodiamide crosslinkers, such as those available from Nisshinbo Industries, Inc. Japan under the trade designation $^{\\bullet\\bullet}\\mathrm{V-}04^{\\circ\\bullet}$ ； and $\\mathfrak{p H}$ responsive carbonate crosslinkers, such as an ammonium zirconyl carbonate crosslinker available from Zirconium Chemicals, Flemington, NJ under the trade designation “Bacote $20^{\\circ}$  \n\nOther crosslinkers include cycloaliphatic epoxy crosslinkers,such as available from Dow Chemicals under the trade designation “ERL-4221\"; hydrophilic aliphatic polyisocyanate crosslinkers, such as available from Bayer Materials Science, Leverkusen under the trade designation “BH$305^{\\cdot,}$ ； and melamine crosslinkers such as those available Stahl USA under the trade designation XR-9174 and from CYTEC Surface Specialties, Inc., under the trade designation “CYMEL 327\".  \n\nMixtures of crosslinkers can also be utilized, particularly mixtures with (e.g. hydrophilic） aziridine crosslinkers.  \n\nThe concentration of crosslinker is typically at least 2, 3, 4,or $5\\mathrm{\\wt-\\%}$ solids of the coating composition. In some embodiments, a relatively high concentration of crosslinker is utilized. For example, the concentration of crosslinker is typically at least 10 or $15\\ \\mathrm{wt-\\%}$ of the solids of the coating composition. The concentration of crosslinker is typically no greater than 25 wt- $\\%$ ,or $24\\mathrm{wt}\\mathrm{-}\\%$ ,or23wt- $\\%$ ,or22wt- $\\%$ or 21wt- $\\%$ or $20\\mathrm{wt-\\%}$  \n\nVarious multifunctional aziridine crosslinkers are known such as trimethylolpropane tri-[beta-(N-aziridinyl)-propionate, 2,2-bishydroxymethyl butanoltris[3-(1-aziridine) propionate], aziridine-2-methylol acrylate, aziridine-2-methylol methacrylate, N-(2-aziridinyl)methylacrylamide, N-(2- aziridinyl)methylmethacrylamide, 1-(aziridin-2-yl)-2-oxabut-3-ene, 4-(aziridin-2-yl)-but-l-ene, and 5-(aziridin-2- yl)-pent-l-ene. These particular aziridine crosslinkers are relatively hydrophobic crosslinkers.  \n\nParticularly for embodiments wherein the crosslinker is present at relatively high concentrations, it can be favored to utilize a hydrophilic aziridine crosslinker, rather than a hydrophobic crosslinker. One favored class of hydrophilic aziridine crosslinkers comprise alkylene oxide repeat units, such as ethylene oxide repeat units. The number of alkylene oxide (e.g. ethylene oxide) repeats units is typically at least 2 or 3 and typically no greater than about 20. In some embodiments, the number of alkylene oxide (e.g. ethylene oxide) repeat units averages about 6, 7, 8, or 9. The use of a hydrophilic crosslinker is favored for embodiment wherein the composition is substantially free of or comprises a low concentration (no greater than 5 wt- $\\%$ )of hydrophilic additives.  \n\nAn aziridine crosslinker comprising ethylene oxide repeat units can be prepare by reacting an ethoxylated alkyl multi 5 (meth)acrylate, such as ethoxylated (9) trimethyl propane triacrylate with an alkyl aziridine, such as 2-methylaziridine. Such aziridine crosslinker has the general formula:  \n\n![](images/ac193645b5fadbf28ca92a5c3f760fe16524f388442d6651a58508e5b00fb50e.jpg)  \n\nwherein $\\mathrm{R^{\\prime}}$ is hydrogen, or a $\\mathrm{C_{1}{-}C_{4}}$ alkyl group; $\\mathrm{R}\"$ is hydrogen or methyl,  \n\nx, y, and $z$ are independently at least 1; and M is a divalent atom of divalent linking group.  \n\nIn some embodiments, the sum of $x+y+z$ is at least 3, 4, 5, or 6. Further the sum of $\\mathbf{x}+\\mathbf{y}+\\mathbf{z}$ may be no greater than 20. In some embodiments, M is oxygen.  \n\nOther aziridine crosslinkers comprising alkylene oxide repeat units are described in U.S. Pat. No. 8,017,666; incorporated herein by reference.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 21,
+        "chunk": "# 10  \n\nWithout intending to be bound by theory it is surmised that alkylene oxide repeat units of the crosslinker aid in preventing a surfactant, compatible with such hydrophilic segments (e.g. such as a non-ionic surfactant comprising alkylene oxide repeat units) from leaching out of the coating.  \n\n5  \n\nThe (e.g. anti-fog) coating compositions described herein may optionally comprise at least one surfactant. The term \"surfactant\" as used herein describes molecules that reduce the surface tension of the coating composition and provide a coating that imparts“good\" or“excellent\" anti-fog properties to substrates or articles coated therewith, according to the test method described in the examples. Surfactant molecules generally include both hydrophilic (polar) and hydrophobic (non-polar) segments on the same molecule.  \n\nUseful surfactants of the present invention include ionic (e.g. anionic, cationic) non-ionic, as well as amphoteric surfactants. A surfactant can be classified by the presence of 4 formally charged groups in its head. The head of an ionic surfactant carries a net charge. An anionic surfactant has a negatively charged hydrophilic group, such as in the case of alkyl sulphates and alkyl ethoxylated sulfates. Cationic surfactants have a positively charged hydrophilic group, 4 such as in the case of sodium salts and quaternary (e.g. ammonium) salts. A non-ionic surfactant has no charged groups in its head. Some illustrative surfactants are described in WO 2009/085680; incorporated herein by reference. 5  \n\nFatty alcohols typically have the general formula:  \n\nVarious classes of non-ionic surfactants are known includ ng for example fatty alcohols, fatty acids, fatty amines, fatt amides, and derivativesthereof.  \n\nFor embodiments that comprise a surfactant, the surfactant concentration in the coating compositions is typically at least $0.5~\\mathrm{wt-\\%}$ ,1 wt- $\\%$ $1.5~\\mathrm{wt-\\%}$ ,or $2\\mathrm{wt-\\%}$ percent of the coating composition. The surfactant concentration is typically no greater than $10\\ \\mathrm{wt}\\cdot\\%$ of the coating composition.  \n\nIn some embodiments, the (e.g. anti-fog) coating composition comprises a non-ionic surfactant. Non-ionic surfactants generally comprise an alkyl or alkenyl group having at least 6, or 8, or 10, or 12 carbon atoms. Such relatively long chain alkyl or alkylene group is commonly referred to as a \"fatty\" group. The number of carbon atoms can be greater than 18 carbon atoms provided the non-ionic surfactant is a liquid at ambient temperature (e.g. $25^{\\circ}\\mathrm{C}.$ ). In some embodiments, the alkyl or alkenyl group has no greater than 24 carbon atoms. In some favored embodiments, such alkyl group is unbranched. The alkyl or alkenyl group may optionally comprise substituents.  \n\nwherein R is a (e.g. straight or branched chain) alkyl or alkenyl group, as previously described, optionally_substituted in available positions by N, O, or S atoms. Various 10 fatty alcohols are known including dodecyl alcohol, cetyl alcohol $\\mathrm{CH}_{3}(\\mathrm{CH}_{2})_{15}\\mathrm{OH}$ ， stearyl alcohol (also known as octadecyl alcohol or 1-octadecanol), and oleyl alcohol.  \n\nIn some embodiments, the non-ionic surfactant is a derivative of a fatty alcohol. One favored derivative is a fatty 15 alcohol, ester or derivative thereof comprising alkylene oxide repeat units such as ethylene oxide and/or propylene oxide repeat units. Such derivatives may also be referred to as a polyethoxylated and/or polypropoxylated fatty alcohols, esters, or derivatives thereof. Polyethoxylated fatty alcohols 20 have the general formula:  \n\n$$\n\\mathrm{R}{\\longrightarrow}(\\mathrm{OCH}_{2}\\mathrm{CH}_{2})_{n}\\mathrm{OH}\n$$  \n\nwherein R is a (e.g. straight or branched chain) alkyl or alkenyl group, as previously described, optionally substi25 tuted in available positions by N, O, or S atoms. The number of ethylene oxide repeat units,“n” can range from 2 to 20. In some embodiments, n is at least 3 or 4 and no greater than about 10 or 12.  \n\nSurfactant comprising polyalkylene oxide repeat units, ） such as polyethoxylated fatty alcohols, can be a favored non-ionic surfactant of the coating composition.  \n\nIn some embodiments, one or more polyethoxylated fatty alcohols are the sole surfactant of the coating composition. In other embodiments, at least one polyethoxylated fatty 5 alcohol is employed in combination with a second surfactant. The polyethoxylated fatty alcohol surfactant may be utilized in combination with a second surfactant at a weight ratio of about 1:1 or 2:1. In some embodiments, the second surfactant is a silicone surfactant, an ionic surfactant, or 0 mixture thereof.  \n\nThe some embodiments, the coating composition comprises an ionic surfactant or silicone surfactant.  \n\nSilicone surfactants generally comprises a siloxane backbone with a various number of dimethyl siloxane units, typically end-capped with a trimethyl siloxane group at each end. The siloxane backbone is generally the hydrophobic group. The hydrophilic group can be ionic, zwitterionic, or non-ionic and are usually attached by a short alkyl chain to the siloxane backbone. One illustrative siloxane surfactant is a polyether modified siloxane, commercially available from Innovadex under the trade designation “BYK-346\".  \n\nVarious ionic surfactants are known. One illustrative ionic surfactant is a sodium alpha olefin sulfonate, commercially available from Stepan Company under the trade designation ；“A-18\".Another ionic surfactant is a polyoxyethylene alkylphenyl ether ammonium sulfate, commercially available from Dai-Ichi Kogyo Seiyaku., Ltd. of Japan under the trade designation “Hitenol BC $10^{\\circ}$ ，  \n\nVarious non-ionic surfactants as previously described comprise a hydroxyl group. Anti-fog coatings have been previously described wherein a hydroxyl functional surfactant is utilized as a reactant during the formation of the polyurethane. (See for example U.S. Pat. No. 3,822,238) However, in the presently described anti-fog coating compositions a preformed (e.g. commercially available) poly mer, provided as an aqueous dispersion is utilized as a component. The polymer of the dispersion is typically free of hydroxyl-reactive groups. Hence, when a hydroxyl functional surfactant is combined with such polyurethane dispersion, the surfactant does not react with the polyurethane due. In other words the surfactant is non-reactive with respect to the (e.g. polyurethane and/or acrylic) polymer.  \n\nThe anti-fog coating described herein may optionally comprise various hydrophilic additives.A hydrophilic additive is distinguished from a surfactant in that a hydrophilic additive lacks a hydrophobic group, a requisite group of a surfactant. In some embodiments, the coating compositions 1 comprise a small concentration of a (e.g. non-reactive) hydrophilic additive, such as a polyethylene glycol (PEG) monomethyl ether, to enhance the anti-fog performance. In this embodiment, the concentration of the hydrophilic additive is typically at least $0.5~\\mathrm{wt-\\%}$ ,or $1\\mathrm{wt}\\%$ ，or $1.5~\\mathrm{wt-\\%}$ ，1 or $2\\ \\mathrm{wt}\\mathrm{-}\\%$ and generally no greater than about $5\\mathrm{\\wt-\\%}$ \\*  \n\nIn some embodiments, an acid or salt of a polyalkylene oxide is the primary or sole hydrophilic component of the coating composition.  \n\nIn another embodiment, an acid or salt of a polyalkylene oxide and one or more surfactants is the primary or sole hydrophilic components of the coating composition.  \n\nIn another embodiment, an acid or salt of a polyalkylene oxide and a hydrophilic aziridine crosslinker are the primary or sole hydrophilic components of the coating composition.  \n\nIn another embodiment, the coating composition comprises an acid or salt of a polyalkylene oxide, one or more surfactants, and a hydrophilic aziridine crosslinker as the primary or sole hydrophilic components of the coating composition.  \n\nIn each of these embodiments, the coating composition may comprise less than $5\\ \\mathrm{wt-\\%}$ or no other hydrophilic organic monomers, oligomer or polymers such as monomer or polymers derived from N-vinylpyrrolidone.  \n\nIn some embodiments, the anti-fog coating compositions are free of inorganic nanoparticles. Such dried and cured composition typically exhibits satisfactory abrasion resistance due to the selection of polyurethane and the relatively high concentration of crosslinker.  \n\nIn other embodiments, the coating composition comprises inorganic nanoparticles at a concentration of at least 0.5 wt- $\\%$ ,1wt- $\\%$ ,or2wt- $\\%$ and typically no greater than about 40wt- $\\%$ of the solids of the coating composition. In some embodiments, the concentration of inorganic nanoparticles is no greater than about $30\\mathrm{\\mt{-}\\%}$ or $20\\mathrm{\\wt-\\%}$ .In some embodiments, the linear abrasion is compromised, particularly with 200 or 300 cycles when the nanoparticle concentration is $15\\ \\mathrm{wt-\\%}$ or greater.  \n\n“Nanoparticles” are herein defined as nanometer-sized particles, preferably with an average particle size of no greater than 100, 75 or 50 nanometers (nm). In some embodiments, the average particle size of the inorganic nanoparticles is no greater than 40, or 30, or $20\\mathrm{nm}$ (prior to surface modification. The average particle size of the nanoparticles is at least $1\\ \\mathrm{nm}$ ,2 nm, or $3\\ \\mathrm{nm}$  \n\nAs used herein, “particle size” and “particle diameter\" have the same meaning and are used to refer to the largest dimension of a particle (or agglomerate thereof). In this context, “agglomeration” refers to a weak association between particles which may be held together by charge or polarity and can be broken down into smaller entities.  \n\nAverage particle size of the nanoparticles can be measured using transmission electron microscopy. In the practice of the present invention, particle size may be determined using any suitable technique. Particle size refers to the number average particle size and is measured using an instrument that uses transmission electron microscopy or scanning electron microscopy. Another method to measure particle size is dynamic light scattering that measures weight average particle size. One example of such an instrument found to be suitable is the N4 PLUS SUB-MICRON PARTICLE ANALYZER available from Beckman Coulter Inc. of Fullerton, Calif.  \n\nThe nanoparticles may be relatively uniform in size. Uniformly sized nanoparticles generally provide more reproducible results.Preferably, variability in the size of the nanoparticles is less than $25\\%$ of the mean particle size.  \n\nThe nanoparticles preferably have a surface area of at least $10\\mathrm{m}^{2}/\\mathrm{gram}$ , more preferably at least $20\\mathrm{m}^{2}/\\mathrm{gram}$ ，and even more preferably at least $25\\mathrm{m}^{2}/\\mathrm{gram}$ . The nanoparticles preferably have a surface area of greater than $750~\\mathrm{m}^{2}/\\mathrm{gram}$  \n\nNanoparticles of the present invention can be porous or nonporous. In some embodiments, the nanoparticles consist solely of only silica. Silica can be preferred nanoparticles, particularly silica nanoparticles derived from a silicate, such as an alkali metal silicate or ammonium silicate. Herein, “silica nanoparticles\" refer to nanoparticles that include only silica as well as to core-shell nanoparticles with a surface that includes silica. In other embodiments, the coating composition may comprise other inorganic oxides such as $\\boldsymbol{Z}\\mathrm{rO}_{2}$ ， colloidal zirconia, $\\mathrm{Al}_{2}\\mathrm{O}_{3}$ , colloidal alumina, $\\mathrm{CeO}_{2}$ D colloidal ceria, $\\mathrm{SnO}_{2}$ ，colloidal tin (stannic) oxide, and $\\mathrm{TiO}_{2}$ colloidal titanium dioxide). Mixtures of such inorganic oxides can also be utilized.  \n\nThe unmodified nanoparticles are typically provided as a   \n30 dispersion rather than as a powder. Preferred dispersion generally contain from $15\\ \\mathrm{wt-\\%}$ to $50\\ \\mathrm{wt-\\%}$ of colloidal particles dispersed in a fluid medium. Representative examples of suitable fluid media for the colloidal particles include water, aqueous alcohol solutions, lower aliphatic   \n35 alcohols, ethylene glycol, N,N-dimethylacetamide, formamide, or combinations thereof. The preferred fluid medium is aqueous, e.g., water and optionally one or more alcohols. Inorganic silica sols in aqueous media are well known in the art and available commercially. Silica sols in water or   \n40 water-alcohol solutions are available commercially under such trade names as LUDOX (manufactured by E.I. duPont de Nemours and Co., Inc., Wilmington, Del.), NYACOL (available from Nyacol Co.,Ashland, Mass.) or NALCO (manufactured by Nalco Chemical Co., Naperville, Ill.).   \n45 Useful silica dispersions include “NALCO $1115^{\\cdots}$ and “DVSZNoo4\", both available from Nalco Chemical Company.  \n\nThe inorganic nanoparticles typically comprise a surface treatment. Surface-treating the nano-sized particles can provide a stable dispersion in the polymeric resin. Preferably, the surface-treatment stabilizes the nanoparticles so that the particles will be well dispersed in the aqueous polyurethane dispersion and results in a substantially homogeneous composition. Furthermore, the nanoparticles can be modified ； over at least a portion of its surface with a surface treatment agent so that the stabilized particle can copolymerize or react with the polyurethane or aziridine crosslinker during curing.  \n\nIn general a surface treatment agent has a first end that will attach to the particle surface (covalently, ionically or through strong physisorption) and a second end that imparts compatibility of the particle with the remainder of the coating composition and/or reacts with components of the coating composition during curing. Examples of surface treatment agents include alcohols, amines, carboxylic acids, sulfonic acids, phospohonic acids, silanes and titanates. The preferred type of treatment agent is determined, in part, by the chemical nature of the metal oxide surface. Silanes are preferred for silica and other for siliceous fillers.  \n\nIn some embodiments the nanoparticles comprise a surface treatment comprising a water dispersible group. Waterdispersible groups are monovalent groups that are capable of providing hydrophilic characteristics to the nanoparticle surface, thereby reducing, and preferably preventing, excessive agglomeration and precipitation of the nanoparticles in an aqueous coating solution. Such surface treatment can be represented by the formula A-L-WD, wherein A are the surface-bonding groups (i.e. for bonding to the nanoparticle surface), WD represents the water-dispersible groups, and L represents an organic linker or a bond. Organic linkers L can be linear or branched alkylene, arylene, or a combination of alkylene and arylene groups, optionally including heteroatoms.  \n\nThe water-dispersible groups are hydrophilic or waterlike groups. They typically include, for example, nonionic groups, anionic groups, cationic groups, groups that are capable of forming an anionic group or cationic group when dispersed in water (e.g., salts or acids), or mixtures thereof.  \n\nExamples of nonionic water-dispersible groups include polyalkylene oxide (e.g. PEG） groups. One illustrative silane surface treatment for use with silica nanoparticles is a polyethylene oxide (PEG) silane, such as 2-[methoxy (polyethyleneoxy)propyltrimethoxysilane.The surface treatment may comprise other water dispersible groups, as well as epoxy silane surface treatments, such as described in WO2009/085680; incorporated herein by reference.  \n\nThe required amount of surface modifier can depend on several factors such particle size, particle type, modifier molecular weight, and modifier type. In general it is preferred that approximately a monolayer of modifier is attached to the surface of the particle. The attachment procedure or reaction conditions required also depend on the surface modifier used. For silanes it can be preferred to surface treat at elevated temperatures under acidic or basic conditions for approximately 1-24 hours.  \n\nThe level of coverage of the inorganic nanoparticles herein is reported in terms of the concentration of epoxy groups in the coating composition, assuming $100\\%$ of the amount of functional groups of the surface treatment would be covalently bonded to surface of the silica particles. In some embodiments, the inorganic nanoparticles comprise a surface treatment at $25\\%$ or $50\\%$ coverage.  \n\nCoating compositions can be supplied in liquid form (e.g., in a pourable form or sprayable form) or impregnated into an applicator substrate (e.g.， forming an applicator pad or wipe). Suitable applicator substrates can be in the form of a sponge,foam， woven， nonwoven， or knit material， for example. The term“nonwoven web” or“nonwoven fabric” refers to a web or fabric having a structure of individual fibers that are interlaid in an irregular manner. In contrast, knit or woven fabrics have fibers that are interlaid in a regular manner.  \n\nThe liquid polyurethane coating compositions can be applied by conventional methods, including spraying, spin coating, brushing, dipping, flow coating, etc., but typically are applied by spin coating or spraying. The coating operation can be conducted either in a single stage or by a multiple stage coating procedure, as is well known in the art. The conditions adopted for curing the (e.g. aziridine) crosslinkers with the polyurethane polymer can vary. In some embodiments, the coating is thermally cured at a temperature from about 90 to $120^{\\circ}$ C. for about 2O minutes.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# 14  \n\nGenerally, lower temperatures require longer cure times. Infrared heating can be used to shorten the time until the coating can be handled.  \n\nThe dried and cured coating compositions described   \n5 herein can exhibit high transparency, greater than $90\\%$ and thus are suitable for application to a variety of light transmissive substrates and articles. The haze of the dried and cured coating is typically less than 5, 4, 3, 2, 1 or $0.5\\%$ .The highly transparent compositions are typically substantially   \n10 free of opacifiying pigments (i.e. less than 0.5 or $0.1~\\mathrm{wt-\\%}$ j The coating compositions can provide anti-fog properties to substrates coated and dried and cured thereon.Dried and cured coatings are considered to have“good\" or “excellent” anti-fogging properties if a coated substrate resists the   \n15 formation of small, condensed water droplets in sufficient density to significantly reduce the transparency of the coated substrate such that it cannot be adequately seen through, according to the test method described in the example. In some embodiments, the dried and cured coating com  \n20 positions are suficiently durable that such that good or excellent anti-fog characteristics are provided initially and after being soaked in $50^{\\circ}\\mathrm{~C~}$ .water for 24 hours. In other embodiments, the dried and cured coating compositions are suficiently durable that they can provide good or excellent   \n25 anti-fog characteristics after being soaked in $65^{\\circ}\\mathrm{C}$ water for 120 hours.  \n\nIn some embodiments, the dried and cured coating compositions exhibited mechanical durability (i.e., the haze of the coatings increased only $1-7\\%$ haze change) after linear 30 razor abrasion test and no scratches were observed after wiping the coatings with a paper towel for 100, 200, or 300 cycles.  \n\nThere are various articles that can benefit from an anti-fog coating such as traffic signs, motor vehicle windows and particularly windshields, protective eyewear (e.g. goggles, face shields, helmets, etc.) and architectural glazings, as well as other decorative glass articles.  \n\nSubstrates to which the antifog coating composition can be applied are preferably transparent or translucent to visible   \n40 light. If the coating composition is utilized for a different purpose, the substrate may alternatively be opaque such as in the case of stainless steel, polyvinyl chloride, and fiberboard. Substrates include both organic and inorganic materials. Exemplary substrates are made of polyester (e.g.,   \n45 polyethylene terephthalate (PET)， polybutyleneterephthalate), polycarbonate (PC), allyldiglycolcarbonate, polyacrylates such as polymethylmethacrylate, polystyrene, polysulfone, polyethersulfone, cellulose acetate butyrate, glass, and the like, including blends and laminates thereof. Typically   \n50 the substrate is in the form of a film, sheet, panel or pane of material and is part of an article. The substrate may be flat, curved or shaped. The article to be coated may be produced by blowing, casting, extrusion, or injection molding.  \n\nThe anti-fog coatings may be coated on both sides of the substrate. Alternatively, the coatings of the present invention may be coated on one side of the substrate. The opposite side of the substrate may be uncoated or coated with a wide variety of conventional antifogging compositions. Preferably, the coating surface should face the direction of higher humidity, e.g., on a face shield the side having the anti-fog coating should face the wearer.  \n\nThe inclusion of the coating described herein can reduce the contact angle of a coated (e.g. substrate) surface. The advancing contact angle with water may be reduced by $20\\%$ D $30\\%$ $40\\%$ D $50\\%$ D $60\\%$ D $70\\%$ or $80\\%$ as compared to the same substrate lacking such coating. For example, the contact angle of fiberboard can be reduced from $50^{\\circ}+$ to less than",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# 16  \n\n$25^{\\circ}$ or $20^{\\circ}$ . As another example, the advancing contact angle with water of stainless steel can be reduced from $85^{\\circ}+$ to less than $50^{\\mathrm{o}}$ ，or $40^{\\circ}$ ，or $20^{\\circ}$ . As yet another example, the advancing contact angle with water of polyvinylchloride can be reduced from $60^{\\circ}+$ to less than $30^{\\circ}$ ,or $25^{\\mathrm{{\\circ}}}$ ,or $20^{\\circ}$ .Thus, the presence of the coating described herein can reduce the advancing contact angle with water of a variety of substrates to less than $30^{\\circ}$ ,or $25^{\\circ}$ ,or $20^{\\circ}$ . Further, the receding contact angle with water (e.g. of fiberboard, stainless steel, and polyvinylchloride) can be reduced to $5^{\\circ}$ or less.  \n\nObjects and advantages of this disclosure are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this disclosure.  \n\nTest Descriptions Test for Anti-Fogging Property  \n\nThe anti-fogging property of the coatings according to the invention was determined by placing coated substrates over a container of hot water (at a temperature of about $50{-}60^{\\circ}$ C.). If fogging was observed within 10 seconds, the coating was deemed to have“poor\" anti-fogging property. If fogging was observed within 10-60 seconds, the coating was deemed to have “good” anti-fogging property. If fogging was observed after 60 seconds, the coating was deemed to have \"excellent\" anti-fogging property.  \n\nTest for Measuring Transmission & Haze  \n\nTransmission and haze values disclosed herein were measured using a Haze-Gard Plus haze meter (available from BYK-Gardiner, Silver Springs, MD) according to the procedure described in ASTM D1003.  \n\nTest for Durability of Coatings  \n\n10 The adhesion of the anti-fog coatings and the (plastic) substrates was determined by cross-hatch/tape adhesion test. All of the coatings made according to the Examples of this invention passed the cross-hatch/tape adhesion test.  \n\nMechanical durability of the anti-fog coatings was deter15 mined by subjecting the coated substrates to linear abrasion test. The linear abrasion test was carried out by wiping the coatings with a paper towel for 100, 200 or 300 cycles under a constant force of about 1400 grams of force $(13.73~\\mathrm{N})$ _” Then the coatings were tested for haze and observed visually 20 for the presence of scratches.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 24,
+        "chunk": "# Materials  \n\nThe following list of materials and their source is referred to throughout the examples.  \n\n<html><body><table><tr><td>Material</td><td>Description</td></tr><tr><td>NALCO 1115</td><td>An aqueous (4 nm) colloidal silica dispersion obtained from Nalco Co., Naperville, IL under trade designation</td></tr><tr><td>DVSZN004</td><td>\"NALCO 1115\". An aqueous (42 nm) colloidal silica dispersion obtainec from Nalco Co., Naperville, IL.</td></tr><tr><td>W835/140</td><td>Polyurethane dispersion having polycarbonate back- bone, obtained from Incorez Co., Lancashire, England under</td></tr><tr><td>EM 2382</td><td>trade designation “INCOREZ W835/140\". Ethoxylated (9) trimethylpropane triacrylate,obtained from Etermal Chemical Co.,</td></tr><tr><td>SR 502</td><td>Ethoxylated (9) trimethylpropane triacrylate, obtained from Sartomer Company, Exton, PA under trade</td></tr><tr><td>2-methylaziridine</td><td>designation “SR 502\". Obtained from Sigma Aldrich Chemical Company, St.</td></tr><tr><td>trimethoxysilane</td><td>Louis, MO. 2-[Methoxy(polyethyleneoxy)propyl] Obtained from Gelest, Inc., Morrisville, PA.</td></tr><tr><td>ED-900</td><td>Polyetheramine, obtained from The Woodlands, TX under trade designation “JEFFAMINE ED-900”.</td></tr><tr><td>ED-2003</td><td>Polyetheramine, obtained from The Woodlands, TX under trade designation “JEFFAMINE ED-2033\".</td></tr><tr><td>Poly(ethylene glycol) (200) monomethacrylate</td><td>Obtained from Sigma Aldrich Chemical Company, St. Louis, MO.</td></tr><tr><td>PZ-28</td><td>Propylene imine tri-functional aziridine, obtained from PolyAziridine, LLC, Medford, NJ under trade designation “PZ-28\".</td></tr><tr><td>PZ-33</td><td>Propylene imine tri-functional aziridine, obtained from PolyAziridine, LLC, Medford, NJ under trade designation“PZ-33”.</td></tr><tr><td>XL-706</td><td>VOC free, tri-functional aziridine crosslinker, obtained from Picassian Polymers, under trade designation “XL- 706\".</td></tr><tr><td>CX-100</td><td>Multi-functional aziridine crosslinker, obtained from Royal DSM N.V., Harleen, Netherlands under trade</td></tr><tr><td>Succinic anhydride</td><td>designation“CX-100\". Obtained from Alfa Aesar, Ward Hill, MA.</td></tr><tr><td>Bacote 20</td><td>Ammonium Zirconyl Carbonate, cross-linking agent, available from Zirconium Chemicals, Flemington, NJ</td></tr><tr><td>ERL-4221</td><td>Cycloaliphatic epoxy, cross-linking agent, available from</td></tr></table></body></html>  \n\n-continued   \n\n\n<html><body><table><tr><td>Material</td><td>Description</td></tr><tr><td>V-04</td><td>Carbodiamide, cross-linking agent, available from Nisshinbo Industries, Inc. Japan.</td></tr><tr><td>BH-305</td><td>Hydrophilic aliphatic polyisocyanate, cross-linking agent, available from Bayer Materials Science, Leverkusen, Germany</td></tr><tr><td>Triethylamine</td><td>Obtained from Sigma Aldrich Chemical Company, St. Louis, MO.</td></tr><tr><td>THF</td><td>Tetrahydrofuran, obtained from Sigma Aldrich Chemi- cal Company, St. Louis,MO.</td></tr><tr><td>AL-2450</td><td>Alumina nanoparticle dispersion (50 wt %) obtained from Nanophase Technologies, Corp., Romeoville, IL, under trade designation “NANO ARC AL-2450”</td></tr><tr><td>BRIJ 30</td><td>Tetraethylene glycol dodecyl ether, obtained from Sigma Aldrich Chemical Company, St. Louis, MO under trade</td></tr><tr><td>BYK-346</td><td>designation“BRIJ 30\". Silicone surfactant, available from Innovadex under trade</td></tr><tr><td>A-18</td><td>designation“BYK-346\". Ionic Surfactant, obtained from Stepan Company, Northfield, IL under trade designation “POLYSTEP A-</td></tr><tr><td>BC-10</td><td>18” Ionic Surfactant, available from Dai-Ichi Kogyo Seitaku,</td></tr><tr><td>PEG monomethyl ether</td><td>Ltd. of Japan under trade designation “Hitenol BC-10” Poly(ethylene glycol) methyl ether (Mw = 550) is obtained from Sigma Aldrich Chemical Company, St. Louis, MO.</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 25,
+        "chunk": "# EXAMPLES  \n\nSynthesis of Nanoparticles Comprising PEG Silane Surface Treatment:  \n\nFor each of Preparative Examples 1-3, silica nanoparticles modified with functional silanes were prepared by slowly adding a desired amount of a functional silane to selected silica nanoparticle dispersion. The relative amounts of the silica nanoparticle dispersion to the functional silane were determined on the basis of equivalent surface coverage desired. The resulting dispersions were stirred for 4hours at room temperature and then heated up to $65^{\\circ}\\mathrm{C}$ .in an oven overnight. Table 1 below describes the silica nanoparticles, functional silanes used and the percent coverage obtained for each of Preparative Examples 1-3. The resulting modified nanoparticle dispersions with different particle size and surface coverage were used as described in Examples described below.  \n\nremoved under vacuum and finally a slight yellow liquid product was obtained and named PZ-2382 and PZ-502, respectively. The disappearance of the double bonds from 5.8 to 6.4 confirms that the reaction between acrylate group and NH in the methyl aziridine was completed successfully  \n\nThe NMR spectra of the “EM-2382\" trifunctional acrylate was obtained using a modern ${500}\\ \\mathrm{MHz}$ Avance III Bruker NMR obtained from Bruker BioSpin Corporation, Tucson, Ariz. According to analysis this acrylate contained 30 wt $\\%$ of the following surfactant:  \n\n$$\n\\mathrm{HO}{-}[\\mathrm{CH}_{2}\\mathrm{CH}_{2}\\mathrm{O}]\\mathrm{n}{-}\\mathrm{C}_{12}\\mathrm{H}_{25}\n$$  \n\nHence, the aziridine crosslinker prepared from “EM-2382” was calculated to contain $23\\ \\mathrm{wt-\\%}$ of such surfactant.  \n\nTABLE1   \n\n\n<html><body><table><tr><td>Nanoparticles</td><td>% Surface Coverage</td><td>Functional silane</td></tr><tr><td>DVSZN004</td><td>50</td><td>2-[Methoxy(polyethyleneoxy)propyl] trimethoxysilane</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 26,
+        "chunk": "# Preparative Example 5  \n\nSynthesis of PEG-Based Ammonium Salts (900-DA and 2003-DA):",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 27,
+        "chunk": "# Preparative Example 4  \n\nSynthesis of Multi-Functional Aziridine Crosslinker:  \n\nTrifunctional aziridine crosslinkers, PZ-2382 and PZ-502， 6 were prepared via a Michael addition of EM 2382 $(\\mathrm{MW}{=}692$ ）orSR-502 $(\\mathrm{M}\\mathrm{W}{=}692)$ ）with 2-methylaziridine. Briefly, the 2-methylaziridine (9.1 grams, $0.1385~\\mathrm{mol}$ )was added drop-wise to the EM 2382 or SR-502 (30 grams, $0.0434\\mathrm{mol}$ ) at room temperature, then the resulting mixture 6 was stirred for 1 hour at room temperature and then refluxed at $60^{\\circ}$ C. for 24 hours. Excessive methyl aziridine was  \n\nTo the succinic anhydride (10 grams) dissolved into THF at $50^{\\circ}\\mathrm{C}.$ ,the ED-900 (50 grams) or ED-2003 (100 grams)   \n55was added. After 24 hours of reaction at 50° C.,the product yellow viscous liquid or yellowish wax， respectively, was obtained after removal of THF under vacuum. The resulting PEG-based diacid was dissolved into water to obtain a $30\\%$   \n50 aqueous solution, to which 1O grams of triethylamine was added and stirred at room temperature for 30 minutes to obtain PEG-based dicarboxylic acid ammonium salts with 30 wt $\\%$ solid. The resulting product was used in the salt   \n55 form in the Examples that follow. The reaction scheme is shown below.  \n\n![](images/f3f6ba18575f74993bd496ab85af399217a978ab46055ce97bb8a75edc407ead.jpg)  \n\nGeneral Process for Forming Anti-fog Coatings  \n\nThe components were mixed together and stirred for 20 minutes at room temperature. The resulting coating solutions with a solid content of about $30\\text{\\textperthousand}$ were coated on polyester (PET), polycarbonate (PC) or glass substrates using a $\\#15$ Mayer bar or by dip coating. The resulting coatings were then cured at a temperature from $110{-}120^{\\circ}\\mathrm{C}$ . for 20-30 minutes, to form coatings with the desired properties (i.e., clear and durable anti-fog coatings).  \n\nDip Coating Procedure  \n\nPlace clip with freshly prepared polycarbonate lens slide on metal bar of Velmax Unislide dip coater. Align slide so sides are perpendicular to lab bench top and bottom is parallel to lab bench top. Secure binder clips with tape. The substrates were immersed in coating solutions and were gradually pulled out at an appropriate pulling speed of about 1 mm/second.  \n\n40",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 28,
+        "chunk": "# Example 1  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，60.9 grams) was mixed with 15 grams of 900-DA (30 wt $\\%$ ” prepared as described above in Preparative Example 5) under stirring to form a homogenous dispersion, then 6.0 grams of PZ-2382 (neat, prepared as described above in Preparative Example 4) and 18.1 grams of water were added and stirred for $20~\\mathrm{min}$ until a homogenous dispersion was obtained. The solution ( $30\\mathrm{wt\\%}$ solids) was applied on a PC plate by a Velmax Unislide dip coater and then cured at $110^{\\circ}$ C. for 20 minutes. The resulting coated PC film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ . vapor) and good light transmittance $(>90)$ \\* After soaking in room temperature water for 240 hours as well as96hours at $80^{\\circ}\\mathrm{C}$ water or 120 hours at $65^{\\circ}\\mathrm{C}.$ ，the coated PC plates still exhibit “excellent” anti-fog performance and very durable.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 29,
+        "chunk": "# Example 2  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，60.26 grams) was mixed with 29.2 grams of 900-DA (30 wt $\\%$ prepared as described above in Preparative Example 5)  \n\n25  \n\nunder stirring to form a homogenous dispersion, then 7.0 grams of PZ-2382 (neat) and 3.6 grams of water were added and stirred for $20~\\mathrm{min}$ until a homogenous dispersion was obtained. The solution ( $35\\mathrm{wt\\%}$ solids) was applied on a PC   \n30 plate by a Velmax Unislide dip coater and then cured at $110^{\\circ}$ C.for 2O minutes. The resulting coated PC film exhibited “excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ . vapor) and good light transmittance $(>90)$ · After soaking in room temperature water for 240 hours as   \n35 well as 96 hours at $80^{\\circ}\\mathrm{C}$ . water or 120 hours at $65^{\\circ}\\mathrm{C}.$ , the coated PET film still exhibit“excellent” anti-fog performance and very durable.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 30,
+        "chunk": "# Example 3  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，54.7 grams) was mixed with 35 grams of 900-DA (30 wt $\\%$ D prepared as described above in Preparative Example 5) under stirring to form a homogenous dispersion, then 7.0 45 grams of PZ-2382 (neat) and 3 grams of water were added and stirred for $20~\\mathrm{min}$ until a homogenous dispersion was obtained. The solution ( $35\\mathrm{wt\\%}$ solids) was applied on a PC plate by a Velmax Unislide dip coater and then cured at $110^{\\circ}$ C. for 20 minutes. The resulting coated PC film exhibited 50“excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ 、vapor) and good light transmittance $(>90)$ \\* After soaking in room temperature water for 240 hours as well as 96 hours at $80^{\\circ}\\mathrm{C}$ .water or 120 hours at $65^{\\circ}\\mathrm{C}.$ ,the coated PC plate still exhibit “excellent” anti-fog perfor55 mance and very durable.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 31,
+        "chunk": "# Example 4  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，65.6 grams) was mixed with 23.3 grams of 900-DA (30 wt $\\%$ 中 prepared as described above in Preparative Example 5) under stirring to form a homogenous dispersion, then 7.0 grams of PZ-2382 (neat), 1 gram BYK-346 and 3 grams of water were added and stirred for $20\\mathrm{min}$ until a homogenous dispersion was obtained. The solution (35 wt $\\%$ solids)was applied on a PC plate by a Velmax Unislide dip coater and then cured at $110^{\\circ}\\mathrm{~C~}$ .for 20 minutes. The resulting coated",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 32,
+        "chunk": "#  \n\nPC film exhibited“excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}~\\mathrm{C}$ . vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 240 hours as well as 96 hours at $80^{\\circ}\\mathrm{~C~}$ water or 120 hours at $65^{\\circ}\\mathrm{C}$ , the coated PC film still exhibit “excellent” anti-fog performance and very durable.A glass plate and a PC lens were coated with the above coating solution by casting and dip coating methods followed by curing at $110^{\\circ}\\mathrm{C}$ . for 20 minutes. The resulting coated glass plate and PC lens had “excellent” anti-fog performance before and after 24 hours of soaking in room temperature water as well as hot water.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 33,
+        "chunk": "# Example 5  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，54.7 grams) was mixed with 35.0 grams of 900-DA (30 wt $\\%$ prepared as described above in Preparative Example 5) under stirring to form a homogenous dispersion, then 7.0 grams of PZ-2382 (neat), 1 gram BYK-346 and 4 grams of water were added and stirred for $20\\mathrm{min}$ until a homogenous dispersion was obtained. The solution ( $35\\mathrm{wt\\\\%}$ solids)was applied on a PC plate with a # 14 Mayer Bar and then cured at $110^{\\circ}$ C. for 2O minutes. The resulting coated PC film exhibited“excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ . vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 240 hours as well as 96 hours at $80^{\\circ}\\mathrm{C}$ . water or 120 hours at $65^{\\circ}$ C., the coated PC film still exhibit “excellent” anti-fog performance and very durable. A glass plate and a PC lens were coated with the above coating solution by casting and dip coating methods followed by curing at $110^{\\circ}\\mathrm{~C~}$ .for 20 minutes. The resulting coated glass plate and PC lens had “excellent” anti-fog performance before and after 24 hours of soaking in room temperature water as well as hot water.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 34,
+        "chunk": "# Example 6  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，56.3 grams) was mixed with 15.0 grams of 900-DA (30 wt $\\%$ ，4C prepared as described above in Preparative Example 5) under stirring to form a homogenous dispersion, then 6.0 grams of PZ-2382 (neat), 5.0 grams PEG-modified DVSZN004 (Preparative Example 2, $50\\%$ coverage and 30 wt $\\%$ ) and 17.7 grams of water were added and stirred for 45 $20~\\mathrm{min}$ until a homogenous dispersion was obtained. The solution (30 wt $\\%$ solids) was applied on a PC plate by a Velmax Unislide dip coater and then cured at $110^{\\circ}\\mathrm{C}$ .for 20 minutes. The resulting coated PC film exhibited “excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}$ 5C C. vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 240 hours as well as 96 hours at $80^{\\circ}\\mathrm{~C~}$ .water or 120 hours at $65^{\\circ}\\mathrm{C}.$ ,the coated PC film still exhibit “excellent” anti-fog performance and very durable. A PC lens was coated with the above coating 55 solution by dip coating followed by curing at $110^{\\circ}\\mathrm{C}$ .for 20 minutes. The resulting coated PC lens had “excellent\" anti-fog performance before and after 24 hours of soaking in room temperature water as well as hot water.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 35,
+        "chunk": "# Example 7  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，60.9 grams) was mixed with 15 grams of 2003-DA (30 wt $\\%$ prepared as described above in Preparative Example 5) under stirring to form a homogenous dispersion, then 6.0 grams of PZ-2382 (neat) and 18.1 grams of water were added and stirred for $20\\mathrm{min}$ until a homogenous dispersion was obtained. The solution $30\\mathrm{wt}\\%$ solids) was applied on a PC plate by a Velmax Unislide dip coater and then cured at $110^{\\circ}\\mathrm{~C~}$ . for 20 minutes. The resulting coated PC film exhibited“excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ ： vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 240 hours as well as 96 hours at $80^{\\circ}\\mathrm{C}$ .water or 120 hours at $65^{\\circ}$ C., the coated PC plates still exhibit“excellent\" anti-fog performance and very durable.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 36,
+        "chunk": "# Example 8  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，60.9 grams) was mixed with 25 grams of 900-DA (30 wt $\\%$ D   \n15 prepared as described above in Preparative Example 5) under stirring to form a homogenous dispersion, then 3.0 grams of PZ-28 (neat) and 11.1 grams of water were added and stirred for 20 min until a homogenous dispersion was obtained.The solution ( $30\\mathrm{wt\\%}$ solids) was applied on a PC   \n20 film with a # 14 Mayer Bar and then cured at $110^{\\circ}\\mathrm{C}$ .for20 minutes. The resulting coated PC film exhibited “excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}$ C. vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 240 hours as well as 96 hours   \n25 at $80^{\\circ}\\mathrm{~C~}$ water or 120 hours at $65^{\\circ}\\mathrm{C}.$ ，the coated PC film still_exhibit “excellent” anti-fog performance and very durable.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 37,
+        "chunk": "# Example 9  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，60.9 grams) was mixed with 25 grams of 900-DA (30 wt $\\%$ D prepared as described above in Preparative Example 5) under stirring to form a homogenous dispersion, then 3.0 grams of PZ-33 (neat) and 11.1 grams of water were added and stirred for 20 min until a homogenous dispersion was obtained. The solution ( $30\\mathrm{wt\\%}$ solids) was applied on a PC plate with a $\\#14$ Mayer Bar and then cured at $110^{\\circ}\\mathrm{~C~}$ . for 20 minutes. The resulting coated PC film exhibited “excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}$ C.vapor) and good light transmittance $(>90)$ .After soaking in room temperature water for 240 hours as well as 96 hours at $80^{\\circ}\\mathrm{C}$ .water or 120 hours at $65^{\\circ}\\mathrm{C}.$ ，the coated PC film still exhibit“excellent” anti-fog performance and very durable.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 38,
+        "chunk": "# Example 10  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，60.9 grams) was mixed with 25 grams of 900-DA (30 wt $\\%$ D ） prepared as described above in Preparative Example 5) under stirring to form a homogenous dispersion, then 3.0 grams of XL-706 (neat) and 11.1 grams of water were added and stirred for $20~\\mathrm{min}$ until a homogenous dispersion was obtained. The solution ( $30\\mathrm{wt\\%}$ solids) was applied on a PC 5film with a # 14 Mayer Bar and then cured at $110^{\\circ}\\mathrm{C}$ .for 20 minutes. The resulting coated PC film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}$ C. vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 240 hours as well as 96 hours ）at $80^{\\circ}\\mathrm{~C~}$ .water or 120 hours at $65^{\\circ}\\mathrm{C}.$ ，the coated PC film still exhibit “excellent” anti-fog performance and very durable.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 39,
+        "chunk": "# Example 11  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，60.9 grams) was mixed with 25 grams of 900-DA (30 wt $\\%$ D",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 40,
+        "chunk": "# 23  \n\nprepared as described above in Preparative Example 5) under stirring to form a homogenous dispersion, then 3.0 grams of CX-100 (neat) and 11.1 grams of water were added and stirred for $20~\\mathrm{min}$ until a homogenous dispersion was obtained. The solution ( $30\\mathrm{wt\\%}$ solids) was applied on a PC film with a # 14 Mayer Bar and then cured at $110^{\\circ}\\mathrm{C}.$ for20 minutes. The resulting coated PC film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}$ C. vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 240 hours as well as 96 hours at $80^{\\circ}\\mathrm{~C~}$ .water or 120 hours at $65^{\\circ}\\mathrm{C}.$ ,the coated PC film still exhibit “excellent” anti-fog performance and very durable.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 41,
+        "chunk": "# Example 12  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，54.7 grams) was mixed with 35.0 grams of 900-DA (30 wt $\\%$ prepared as described above in Preparative Example 5) under stirring to form a homogenous dispersion, then 7.0 grams of PZ-502 (neat), 1 gram BRIJ 30 and 4 grams of water were added and stirred for $20\\mathrm{min}$ until a homogenous dispersion was obtained. The solution ( $35\\mathrm{wt\\\\%}$ solids)was applied on a PC plate with a # 14 Mayer Bar or by dipping coating and then cured at $110^{\\circ}\\mathrm{~C~}$ .for 20 minutes. The resulting coated PC film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 240 hours as well as 96 hours at $80^{\\circ}$ C.water or 120 hours at $65^{\\circ}\\mathrm{~C~}.$ ,the coated PC film still exhibit “excellent” anti-fog performance and very durable. A glass plate and a PC lens were coated with the above coating solution by casting and dip coating methods followed by curing at $110^{\\circ}~\\mathrm{C}$ .for 20 minutes. The resulting coated glass plate and PC lens had “excellent” anti-fog performance before and after 24 hours of soaking in room temperature water as well as hot water.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 42,
+        "chunk": "# Example 13  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，65.6 grams) was mixed with 23.3 grams of 900-DA (30 wt $\\%$ prepared as described above in Preparative Example 5) under stirring to form a homogenous dispersion, then 7.0 grams of PZ-502 (neat), 1 gram BRIJ 30 and 3 grams of water were added and stirred for $20\\mathrm{min}$ until a homogenous dispersion was obtained. The solution ( $35\\mathrm{\\wt\\\\%}$ solids)was applied on a PC plate with a $\\#14$ Mayer Bar or by dipping coating and then cured at $110^{\\circ}\\mathrm{~C~}$ .for 20 minutes. The resulting coated PC film exhibited “excellent\" anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{C}$ vapor) and good light transmittance $(>90)$ . After soaking in room temperature water for 240 hours as well as 96 hours at $80^{\\circ}$ C.water or 120 hours at $65^{\\circ}\\mathrm{~C~}.$ ，the coated PC film still exhibit “excellent” anti-fog performance and very durable. A glass plate and a PC lens were coated with the above coating solution by casting and dip coating methods followed by curing at $110^{\\circ}~\\mathrm{C}.$ 、for 20 minutes. The resulting coated glass plate and PC lens had “excellent” anti-fog performance before and after 24 hours of soaking in room temperature water as well as hot water.  \n\nTable 3 below summarizes the components and the relative amounts of each component in the resulting cured coatings on substrates of Examples 1-13 described above.  \n\n24 TABLE 3   \n\n\n<html><body><table><tr><td></td><td></td><td>Wt % Polyurethane</td><td colspan=\"2\">Type and Wt % Diacid Salt</td><td>Type and Wt %</td><td></td><td></td></tr><tr><td></td><td>Example</td><td>(W835/140)</td><td>900-DA</td><td>2003- DA</td><td>Aziridine PZ-2382*</td><td>BYK- 346</td><td>BRIJ 30</td></tr><tr><td></td><td>1</td><td>65</td><td>15</td><td></td><td>20</td><td></td><td></td></tr><tr><td></td><td>2</td><td>55</td><td>25</td><td></td><td>20</td><td></td><td></td></tr><tr><td></td><td>3</td><td>50</td><td>30</td><td></td><td>20</td><td></td><td></td></tr><tr><td>0</td><td>4</td><td>58.3</td><td>19.4</td><td></td><td>19.4</td><td>2.8</td><td></td></tr><tr><td></td><td>5</td><td>48.6</td><td>29.1</td><td></td><td>19.4</td><td>2.7</td><td></td></tr><tr><td></td><td>6**</td><td>60</td><td>15</td><td></td><td>20</td><td></td><td></td></tr><tr><td></td><td>7</td><td>65</td><td></td><td>15</td><td>20</td><td></td><td></td></tr><tr><td></td><td>8</td><td>65</td><td>25</td><td></td><td>10</td><td></td><td></td></tr><tr><td>5</td><td>9</td><td>65</td><td>25</td><td></td><td>PZ-28 10</td><td></td><td></td></tr><tr><td></td><td>10</td><td>65</td><td>25</td><td></td><td>PZ-33 10</td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td>XL-706</td><td></td><td></td></tr><tr><td></td><td>11</td><td>65</td><td>25</td><td></td><td>10 CX-100</td><td></td><td></td></tr><tr><td>20</td><td>12</td><td>48.6</td><td>29.1</td><td></td><td>19.4 PZ-502</td><td></td><td>2.7</td></tr><tr><td></td><td>13</td><td>58.3</td><td>19.4</td><td></td><td>19.4 PZ-502</td><td></td><td>2.7</td></tr></table></body></html>\n\nPZ-2382 comprises $23\\%$ surfactant, as previously described. Therefore, 15 wt $\\%$ Z $\\therefore2382=3.5\\mathrm{wt}\\cdot\\%$ of surfactant and 11.5 wt $\\%$ hydrophilic aziridine crosslinker ′← $25\\mathrm{wt-}\\%\\mathrm{PZ-}2382=5.81$ t $\\%$ of surfactant and $19.2\\mathrm{wt}\\%$ hydrophilic aziridine crosslinker $24.2\\ \\mathrm{wt}\\cdot\\%$ $P Z{=}2382\\ =\\ 5.6\\ \\mathrm{wt}{=}\\%$ of surfactant and $18.6~\\mathrm{wt}\\cdot\\%$ hydrophilic aziridine crosslinker 23 $:\\mathrm{wt-\\%}\\mathrm{PZ}.2382=5.3$ wt- $.\\%$ of surfactant and 17.7 wt- $\\%$ hydrophilic aziridine crosslinker \\*\\*Example 6 also contained 5 wt- $\\%$ of the silica nanoparticles comprising a PEG silane surface treatment, as previously described.  \n\nAll the anti-fog coatings prepared from compositions of Table 3 exhibited excellent mechanical durability (i.e., the haze of the coatings increased only $1-7\\%$ haze change after linear razor abrasion test and no scratches were observed after wiping the coatings with a paper towel for 30o cycles).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 43,
+        "chunk": "# Example 14  \n\nAn acrylic latex (40.5 wt $\\%$ ，43.5 grams), available from   \n$40$ Dow Coating  Materials under the trade designation “ROSHIELDTM 3188\", was mixed with 900-DA prepared as described in the Example 22 (30 wt $\\%$ ，30 grams) under stirring to form a homogenous dispersion. Then PZ-2382 (7.0 grams, neat) and 19.5 grams of water were added   \n45 respectively and the resulting solution was stirred for 20 min. The final dispersion solution ( $35\\mathrm{wt\\\\%}$ solids) was thus obtained and subsequently applied on a PC film with a $\\#14$ Mayer. The resulting coating was cured at $110^{\\circ}~\\mathrm{C}$ .for20 minutes. The resulting coated PC film exhibited “excellent”   \n50 anti-fog performance (no fog appeared when exposed to $50^{\\circ}$ C.vapor after 1 minute) and good optical properties with light transmittance up to $90\\%$ . Samples were subjected to both water soak tests, one at room temperature for 120 hours, and one at $65^{\\circ}\\mathrm{C}$ .120 hours. The soaked PC samples   \n55 showed excellent water resistance and anti-fog properties remained.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 44,
+        "chunk": "# Example 15  \n\n60 A polyurethane/acrylic hybrid latex (40 wt $\\%$ ，43.5 grams), available from DSM NeoResins Company under the trade designation “NEOPAC R-9036” was mixed with 900- DA prepared as described in Example 22 (30 wt $\\%$ ，30.0 grams) under stirring to form a homogenous dispersion.   \n65 Then PZ-2382 (7.0 grams, neat), and 19.5 grams of water were added respectively and the resulting solution was stirred for $20\\ \\mathrm{\\min}$ until a homogenous dispersion was",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 45,
+        "chunk": "# 25  \n\nobtained. The final dispersion solution (35 wt $\\%$ solids) was thus obtained and subsequently was applied on a PC film with a $\\#14$ Mayer. The resulting coating was cured at $110^{\\circ}$ C. for 20 minutes. The resulting coated PC film exhibited “excellent” anti-fog performance (no fog appeared when exposed to $50^{\\circ}\\mathrm{~C~}$ . vapor after 1 minute) and good optical properties with light transmittance up to $90\\%$ . Samples were subjected to both water soak tests, one at room temperature for 120 hours, and one at $65^{\\circ}\\mathrm{C}$ .120 hours. The soaked PC samples showed excellent water resistance and anti-fog properties remained.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 46,
+        "chunk": "# Examples 16-20  \n\nA polyurethane dispersion blend was formed by combining the polyurethane dispersion W835/140 (32 wt $\\%$ ，94.38 grams) with 900-DA prepared as described in Example 22 (30 wt $\\%$ ，61.17 grams). The mixture was stirred for 15 minutes to form a homogenous dispersion. To it was added 1.75 grams of BYK-346 with stirring. The mixture was stirred for 15 additional minutes to make a homogenous dispersion.  \n\nThe crosslinker (type and amount shown in the table below) was combined with 0.4 grams of water, and 9 grams of the polyurethane blend to make the anti-fog coating composition.  \n\nExamples 16-20 were coated onto PC film as described earlier using Meyer bar $\\#15$ The coatings were cured at $120^{\\circ}\\mathrm{~C~}$ .for 20 minutes.  \n\n<html><body><table><tr><td>Example</td><td>Cross- linker (1) Type</td><td>Cross- linker (1) amount</td><td>Cross- linker (2) Type</td><td>Cross- linker (2) amount</td></tr><tr><td>Example 16</td><td>PZ-2382</td><td>0.77 grams</td><td>Bacote 20</td><td>0.1 grams</td></tr><tr><td>Example 17</td><td>Bacote 20</td><td>0.3 grams</td><td>none</td><td></td></tr><tr><td>Example 18</td><td>PZ-2382</td><td>0.7 grams</td><td>ERL 4221</td><td>0.1 grams</td></tr><tr><td>Example 19</td><td>PZ-2382</td><td>0.7 grams</td><td>BH-305</td><td>0.1 grams</td></tr><tr><td>Example 20</td><td>V-04</td><td>0.8 grams</td><td>none</td><td></td></tr></table></body></html>  \n\nAnti-fog properties were evaluated after soaking in $50^{\\circ}\\mathrm{~C~}$ water for 24 hours. Examples 16-20 exhibited good anti-fog properties and excellent light transmission.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 47,
+        "chunk": "# Example 21  \n\nThe polyurethane dispersion $\\mathrm{W}835/140$ (32 wt $\\%$ ，32.8 grams) was mixed with 11.5 grams of 900-DA (30 wt $\\%$ j under stirring to form a homogenous dispersion, then 3.0 grams of PZ-502 (neat), $\\mathbf{0.75\\g}$ Jeecol LA-7 $(\\mathrm{C}_{12}\\mathrm{E}0_{7}$ from Jeen International Co.) and $1.0\\mathrm{g}$ BYK-346 were added and stirred for 20 minutes until a homogenous dispersion was obtained. The solution was casted on the substrates, such as stainless steel, PVC, and fiberboard then cured at room temperature.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 48,
+        "chunk": "# Example 22  \n\nThe polyurethane dispersion W835/140 (32 wt $\\%$ ，32.8 grams) was mixed with 11.5 grams of 900-DA (30 wt $\\%$ j under stirring to form a homogenous dispersion, then 1.0 grams of Bacote 20 ( $20\\%$ by weight in water), $0.75\\mathrm{g}$ Jeecol LA-7 $\\mathrm{\\C_{12}E0}_{7}$ from Jeen International Co.） and $1.0\\mathrm{g}$ BYK346 were added and stirred for 20 minutes until a homogenous dispersion was obtained. The solution was casted on the substrates, such as stainless steel, PVC, and fiberboard then cured at room temperature.  \n\nContact angle measurements with water were obtained from the resulting coated and uncoated substrates using a VCA Optima goniometer (AST products, INC). The results are reported in the following table.  \n\n<html><body><table><tr><td colspan=\"5\">Contact Angle Analysis (Degrees)</td></tr><tr><td>Sample</td><td>Advancing</td><td>St.Dev.</td><td>Receding</td><td>St. Dev.</td></tr><tr><td>10 Fiberboard Control Fiberboard w/</td><td>54.3</td><td>11.7</td><td>20.4</td><td>3.0</td></tr><tr><td>Example 21 Coating</td><td>16.8</td><td>1.5</td><td>#</td><td></td></tr><tr><td>Fiberboard w/ Example 22 Coating</td><td>15.6</td><td>0.9</td><td>3</td><td></td></tr><tr><td>Stainless Steel Control</td><td>89.4</td><td>2.7</td><td>35.5</td><td>2.4</td></tr><tr><td>15 Stainless Steel w/ Example 21 Coating</td><td>19.6</td><td>0.3</td><td>3</td><td></td></tr><tr><td>Stainless Steel w/ Example 22 Coating</td><td>16.1</td><td>1.1</td><td><3</td><td></td></tr><tr><td>PVC Control</td><td>68.3</td><td>8.9</td><td>25.6</td><td>2.0</td></tr><tr><td>PVC w/Example 21 Coating</td><td>19.0</td><td>0.4</td><td>#</td><td></td></tr><tr><td>PVC w/Example 22 Coating</td><td>16.7</td><td>0.1</td><td></td><td></td></tr></table></body></html>  \n\nWhat is claimed is:  \n\n1. A coating composition comprising an aqueous polymeric dispersion;  \n\na crosslinker comprising an aziridine crosslinker; and a polyalkylene oxide backbone terminating with an acid or salt group on each end, wherein the polyalkylene oxide backbone comprises a copolymer of polyethylene oxide and polypropylene oxide, and wherein the polyalkylene oxide backbone is linked to the acid or salt group on each end by a divalent linking group, the divalent linking group selected from:  \n\n$\\mathrm{-CH}_{2}\\mathrm{NHCOC}_{2}\\mathrm{H}_{4}-$ ，—NHCONH—，— $\\mathrm{C}{=}\\mathrm{O})$ o-CONH—，—COS—， $-\\mathrm{CS}_{2}$ ，—S—，—O—，and—SCONH—.  \n\n2. The coating composition of claim 1 wherein the aqueous polymeric dispersion comprises a carboxylate-containing polymer selected from a polyurethane polymer, an acrylic polymer, or a mixture thereof, and wherein the carboxylate-containing polymer is present in the dried and cured coating composition in an amount of at least about 40 wt $\\%$  \n\n3. The coating composition of claim 2 wherein the poly mer comprises carbonate moieties.  \n\n45 4. The coating composition of claim 1 wherein the poly alkylene oxide comprises 10 to 100 repeat units selected from ethylene oxide and propylene oxide.  \n\n5. The coating composition of claim 4 wherein the ratio of ethylene oxide repeat units to propylene oxide repeat units . is at least 2:1.  \n\n6. The coating composition of claim 1 wherein the crosslinker further comprises a $\\mathfrak{p H}$ sensitive carbonate crosslinker, a carbodiimide crosslinker, or a mixture thereof.  \n\n7. The coating composition of claim 1 wherein the aziri55 dine crosslinker comprises alkylene oxide repeat units.  \n\n8. The coating composition of claim 1 wherein the coating composition comprises at least 10 wt $\\%$ solids of aziridine crosslinker.  \n\n9. The coating composition of claim 1 wherein the coating ） composition further comprises a surfactant.  \n\n10. The coating composition of claim 9 wherein the surfactant is a nonionic surfactant.  \n\n11. The coating composition of claim 10 wherein the surfactant comprises polyalkylene oxide repeat units.  \n\n12. The coating composition of claim 9 wherein the coating composition comprises a silicone surfactant, an ionic surfactant, or a mixture thereof.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 49,
+        "chunk": "# 27  \n\n13.The coating composition of claim 1 wherein the dried   \nand cured coating comprises inorganic oxide nanoparticles. 14. The coating composition of claim 13 wherein the   \ninorganic oxide nanoparticles comprise silica nanoparticles. 15. The coating composition of claim 14 wherein the 5   \nnanoparticles comprise a silane surface treatment compris  \ning a water dispersible group. 16. The coating composition of claim 1 wherein the dried   \nand cured coating composition does not exhibit fogging   \nwithin 60 seconds after being soaked in $50^{\\circ}\\mathrm{C}$ .water for 24 10   \nhours. 17. The coating composition of claim 1 wherein the dried   \nand cured coating composition does not exhibit fogging   \nwithin 60 seconds after being soaked in $50^{\\circ}\\mathrm{C}$ .water for 24   \nhours or $65^{\\circ}\\mathrm{C}$ .water for 120 hours. 15 18.The coating composition of claim 1 wherein the cured   \ncoating has a light transmission of at least $90\\%$ \\* 19.An article comprising a substrate and the dried and   \ncured coating of claim 1. 20.The article of claim 19 wherein the substrate is light 20   \ntransmissive or opaque. 21. The article of claim 20 wherein the substrate is   \nstainless steel, fiberboard, or polyvinylchloride. 22.A method of providing an anti-fog coating on a surface   \nof a substrate, the method comprising 25 providing the coating composition according to claim 1; applying the coating composition to a substrate; and drying and curing the coating composition.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 50,
+        "chunk": "# UNITEDSTATESPATENTANDTRADEMARKOFFICE CERTIFICATE OF CORRECTION  \n\nPATENT NO. : 10,048,408 B2 APPLICATION NO. : 14/361076 DATED : August 14, 2018 INVENTOR(S) : YongshangLu  \n\nIt iscertifiedthaterrappearsintheaboveidentifiedpatentandthatsaidLettersPatentisherebyorrectedasshownbelow:  \n\nIn the Specification  \n\nColumn 5, Line 33, delete “RHOPLEXTM\" and insert -- RHOPLEXTM, --, therefor.  \n\nColumn 8, Line 43, delete “-but-l-ene,\" and insert -- -but-l-ene, --, therefor.  \n\nColumn 25, Line 50, delete “ $\\mathrm{\\dot{(}C_{12}E0\\gamma^{3}}$ and insert -- $(\\mathrm{C}_{12}\\mathrm{EO}_{7}\\cdots$ , therefor. Line 63, delete “ $(\\mathrm{C}_{12}\\mathrm{E}0_{7}^{\\ \\mathrm{3}\\mathrm{3}}$ and insert -- ( $\\mathrm{C}_{12}\\mathrm{EO}_{7}$ --, therefor.  \n\nIn the Claims  \n\nColumn 26, Line 42, in Claim 2, delete “wt $\\%^{9\\%^{9}}$ and insert -- wt- $\\%$ --, therefor. Line 57, in Claim 8, delete “wt $\\%^{9\\%^{9}}$ and insert -- wt- $\\%$ --, therefor.  \n\nSigned and Sealed this Ninth Day of October, 2018  \n\n![](images/04503a12294cdfe1b724bd9dd559ba181b2e83cb9326fc86934e6c9640af2c8d.jpg)  \n\nAndrei Iancu Director of the United StatesPatentand Trademark Office",
+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,122 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (12) United States Patent Majumdar et al.",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (54) FLEXIBLE VISOR HAVING ANTI-FOGGING PROPERTIES AND ANTI-FOGGING COATING COMPOSITIONS  \n\n(71） Applicant: SAINT-GOBAIN PERFORMANCEPLASTICS CORPORATION, Solon,OH (US)  \n\n(72） Inventors: Debasis Majumdar, Manchester, NH (US); Ryan C.Hirschey, Nashua, NH (US); John P. Russo, Hudson, NH (US); Gerard T. Buss, Bedford, NH (US)  \n\n(73） Assignee: SAINT-GOBAIN PERFORMANCEPLASTICS CORPORATION, Solon,OH (US)  \n\n（\\*） Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days.  \n\n(21)Appl.No.: 14/314,241 (22) Filed: Jun.25,2014 (65) Prior Publication Data  \n\nUS 2014/0377566 A1 Dec.25,2014",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# Related U.S. Application Data  \n\n(60） Provisional application No. 61/839,299,filed on Jun. 25,2013.  \n\n(51) Int. Cl. C09K 3/18 (2006.01) C09D7/12 (2006.01) C09D 167/00 (2006.01) C09D 175/04 (2006.01) B32B33/00 (2006.01) B32B27/08 (2006.01)  \n\n52) U.S. Cl. CPC C09D 175/04 (2013.01);B32B 27/08 (2013.01);B32B33/00 (2013.01);B32B 2250/05 (2013.01); B32B 2250/24 (2013.01);  \n\n(10) Patent No.: US 9,346,974 B2   \n(45) Date of Patent: May 24, 2016  \n\nB32B 2250/246 (2013.01);B32B 2255/10 (2013.01); B32B 2255/26 (2013.01); B32B   \n2307/412 (2013.01); B32B 2551/00 (2013.01);   \nC09D 167/00 (2013.01); C09K 3/18 (2013.01); Y10T 428/3158 (2015.04)  \n\n(58)Field of Classification Search None See application file for complete search history.",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# References Cited",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# U.S.PATENTDOCUMENTS  \n\n4,775,658 A 10/1988 Matsuda et al.   \n5,846,650 A \\* 12/1998 Ko G02B1/105 296/84.1   \n5,877,254A 3/1999 La Casse et al. (Continued)",
+        "category": " References"
+    },
+    {
+        "id": 6,
+        "chunk": "# OTHERPUBLICATIONS  \n\nThe International Search Report and the Written Opinion received from the International Searching Authority (ISA/KR) for InternationalApplication No.PCT/US2014-044024,dated Oct.20,2014,12 pages.  \n\n(Continued)  \n\nPrimary Examiner—Ramsey Zacharia  \n(74） Attorney, Agent, or Firm—Abel Law Group, LLP;Thomas Osborn",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# ABSTRACT  \n\nThe present disclosure is directed to transparent composites having anti-fogging properties and anti-fog coating compositions for providing anti-fogging properties. The anti-fogging layers can contain an adhesive polymer, a hard polymer, and a hydrophilic polymer, wherein the adhesive polymer, hard polymer, and hydrophilic polymers are different. In further embodiments, composites are described including a substrate layer; a first adhesive layer; a first transparent layer; a second adhesive layer; a second transparent layer; and an anti-fog layer.  \n\n19 Claims, 1 Drawing Sheet  \n\n<html><body><table><tr><td>20</td></tr><tr><td>50</td></tr></table></body></html>",
+        "category": " Abstract"
+    },
+    {
+        "id": 8,
+        "chunk": "# References Cited",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# U.S.PATENTDOCUMENTS  \n\n2003/0203991 A1 10/2003 Schottman et al.   \n2005/0153106 A1\\* 7/2005 Lansberry B32B17/10   \n428/195.1   \n2006/0078718 A1 4/2006 Konrad et al.   \n2009/0246513 A1 10/2009 Laroche et al.   \n2012/0049401 A1 3/2012 Schneider et al.   \n2012/0308828 A1 12/2012 Iwazumi et al.",
+        "category": " References"
+    },
+    {
+        "id": 10,
+        "chunk": "# OTHERPUBLICATIONS  \n\nLUDOX Colldodal Silica, Grace Materials Technologies, 2012 (Brochure), W.R. Grace & Co.-Conn, see p. 6.  \n\n\\* cited by examiner",
+        "category": " References"
+    },
+    {
+        "id": 11,
+        "chunk": "# U.S. Patent  \n\nMay 24, 2016  \n\n<html><body><table><tr><td></td><td>20</td></tr><tr><td></td><td>50</td></tr></table></body></html>  \n\n10  \n\nFIG.1  \n\n100  \n\nFIG.2   \n\n\n<html><body><table><tr><td>200</td></tr><tr><td>210</td></tr><tr><td>220</td></tr><tr><td>230</td></tr><tr><td>240</td></tr><tr><td>250</td></tr></table></body></html>",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# 2",
+        "category": " Introduction"
+    },
+    {
+        "id": 13,
+        "chunk": "# 1FLEXIBLEVISORHAVINGANTI-FOGGINGPROPERTIESANDANTI-FOGGINGCOATING COMPOSITIONS  \n\nCROSS-REFERENCETORELATED APPLICATION  \n\nThis application claims priority under 35 U.S.C. \\$119(e) to U.S. Provisional Application°No. 61/839,299 entitled “FLEXIBLEVISOR HAVING ANTI-FOGGING PROPERTIES AND ANTI-FOGGING COATING COMPOSITIONS,” by Majumdar et al., filed Jun. 25, 2013, and is hereby incorporated by reference in its entirety.",
+        "category": " References"
+    },
+    {
+        "id": 14,
+        "chunk": "# FIELD OF THE DISCLOSURE  \n\nThe present disclosure relates to visors having anti-fogging properties and anti-fogging coating compositions, and more particularly to, visors having anti-fogging properties and antifogging coating compositions using a combination of different polymers.",
+        "category": " Introduction"
+    },
+    {
+        "id": 15,
+        "chunk": "# RELATED ART  \n\nAnti-fogging compositions and visors containing anti-fogging compositions are known in the art. For example, polyurethane coating compositions having hydrophilic properties have been used to provide anti-fogging effects. However, hydrophilic polyurethanes are often soft and tacky, leading to undesirable sticking of the anti-fogging coating layer to various surfaces. Such tackiness can cause delamination of the coated layer from the substrate during coating, assembly or actual use of a flexible composite visor. Moreover, characteristics such as transparency, haze, hardness, scratch resistance are traditionally negatively affected when attempting to improve the drawbacks of using solely hydrophilic polyurethanes.  \n\nAccordingly, new visor composites exhibiting anti-fogging properties which do not delaminate and have good hardness with excellent transparency are still needed.",
+        "category": " Introduction"
+    },
+    {
+        "id": 16,
+        "chunk": "# BRIEFDESCRIPTION OF THE DRAWINGS  \n\nEmbodiments are illustrated by way of example and are not limited in the accompanying figures.  \n\nFIG.1 includes a cross-section illustration of a composite visor according to one embodiment of the present disclosure.  \n\nFIG.2 includes a cross-section illustration of a composite visor according to another embodiment of the present disclosure.  \n\nSkilled artisans appreciate that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale.For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help to improve understanding of embodiments of the invention.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# DETAILEDDESCRIPTION  \n\nThe following description in combination with the figures is provided to assist in understanding the teachings disclosed herein. The following discussion will focus on specific implementations and embodiments of the teachings. This focus is provided to assist in describing the teachings and should not be interpreted as a limitation on the scope or applicability of the teachings. However, other embodiments can be used based on the teachings as disclosed in this application.  \n\nThe terms“comprises,\"“comprising,\"\"includes,\"\"including,”“has,”“having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a method, article, or apparatus that comprises a list of features is not necessarily limited only to those features but may include other features not expressly listed or inherent to such method, article, or apparatus. Further, unless expressly stated to the contrary, “or” refers to an inclusive-or and not to an exclusive-or.For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).  \n\nAlso, the use of “a\" or “an” is employed to describe ele  \n.0 ments and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one, at least one, or the singular as also including the plural, or vice versa, unless it is clear that it is meant otherwise. For example,   \n5 when a single item is described herein, more than one item may be used in place of a single item. Similarly, where more than one item is described herein, a single item may be substituted for that more than one item.  \n\nUnless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The materials, methods, and examples are illustrative only and not intended to be limiting. To the extent not described herein, many details regarding specific materials and processing acts are conventional and may be found in textbooks and other sources within the transparent, anti-fogging composite arts.  \n\nThe following disclosure describes anti-fogging compositions and composites having anti-fogging compositions, where the anti-fogging composition comprises a novel com  \n30 bination of at least three different polymers which the current inventors have surprisingly discovered result in synergistic improvement in characteristics including anti-fogging, mechanical strength, adhesion, and transparency. The composites can particularly be useful for applications including visors, windows, and the like. The concepts are better under  \n35 stood in view of the embodiments described below that illustrate and do not limit the scope of the present invention. One embodiment of the present disclosure is directed to a composite 10 which includes a substrate layer 20 and an anti-fog layer 50 as illustrated in FIG.1. The anti-fog layer 50   \n40 can be disposed directly adjacent the substrate layer 20.In other embodiments, as will be discussed in more detail below, the composite can contain additional intervening layers between the substrate layer 20 and the anti-fog layer 50, and further layers above or below the substrate layer 20 and anti  \n45 fog layer 50. Generally, the anti-fog layer 50 will be an external layer of the composite and exposed to an environment. In certain embodiments, the anti-fog layer will be disposed in the composite such that it is adapted to face a human user.For example, one form of the composite, as discussed in more detail below, is a visor construct, and the anti-fog layer   \n50 may be disposed within the layering of the composite such that it is adapted to face the user. One particular example of a composite having additional layers is illustrated in FIG. 2. The composite 100 can contain a substrate layer 200; a first adhesive layer 210; a first trans  \n55 parent layer 220; a second adhesive layer 230; a second transparent layer 240; and an anti-fog layer 250. Each of the aforementioned layers can directly contact each other in the arrangement as shown in FIG. 2. Additionally, in other embodiments, further layers can be disposed in between the layers illustrated in FIG. 2. As discussed above, traditionally,   \n60 the anti-fog layer in the context of visor constructs, can be adapted to face a user when in use. As such, in particular embodiments, the anti-fog layer 250 can be directly adjacent to and contacting the second transparent layer 240. Other particular embodiments of the present disclosure are directed   \n65to anti-fog coating compositions. Such anti-fog coating compositions can contain a cross-linkable network of polymers comprising an adhesive polymer, a hard polymer, and a  \n\nhydrophilic polymer, wherein the adhesive polymer, hard polymer, and hydrophilic polymer are different.  \n\nExamples and characteristics of certain layers of the composite and constituents of the anti-fog layer will now be described. It is to be understood that any description of the anti-fog coating layer also applies to the anti-fog coating compositions.  \n\nThe substrate layer can be a multitude of different materials, including, for example, transparent plastics, glass, metals or ceramics. In a preferred embodiment, the substrate is flexible.For example, a flexible substrate, is a substrate which can be repeatedly bent or flexed without breaking. In certain embodiments, the substrate can include flexible plastic materials such as polyester including polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyester ionomer, amorphous polyester such as amorphous glycol modified PET (PETG), polyethersulfone (PES), polycarbonate (PC), polysulfone, a phenolic resin, an epoxy resin, polyetherester, polyetheramide, cellulose nitrate, cellulose acetate, such as cellulose triacetate (TAC), poly(vinyl acetate), polystyrene, polyolefins including polyolefin ionomers, polyamide, polyurethanes, polythiourethanes, polyacrylonitrile, poly(methyl (x-methacrylates), an aliphatic or cyclic polyolefin, polyarylate (PAR), polyetherimide (PEI), polyethersulphone (PES), polyimide (PI), poly(ether ether ketone) (PEEK), poly(ether ketone) (PEK), and poly(methyl methacrylate) and various acrylate/methacrylate copolymers (PMMA), polyvinyl chloride (PVC), various fluoropolymers, various silicone based polymers, voided polymers including polymeric foam, microvoided polymers and microporous materials, fabric, or any combinations thereof. In particular embodiments, polyolefins may include high density polyethylene (HDPE), low density polyethylene (LDPE), and polypropylene, including oriented polypropylene (OPP). Cyclic polyolefins may include poly(bis(cyclopentadiene)). Examples  include Artong made by Japan Synthetic Rubber Co., Tokyo, Japan; Zeanor T made by Zeon Chemicals L.P., Tokyo Japan; and Topas $\\textsuperscript{\\textregistered}$ made by Celanese A. G., Kronberg Germany. Arton is a poly(bis(cyclopentadiene)) condensate that is a film of a polymer.  \n\nIn further particular embodiments, polyesters may include those which are derived from the condensation of aromatic, cycloaliphatic, and aliphatic diols with aliphatic, aromatic 4 and cycloaliphatic dicarboxylic acids and may be cycloaliphatic, aliphatic or aromatic polyesters.Examples of particular cycloaliphatic, aliphatic and aromatic polyesters include poly(ethylene terephthalate), poly(cyclohexlenedimethylene), terephthalate)poly(ethylene dodecate), poly(buty- 4 lene terephthalate), poly(ethylene naphthalate), poly(ethylene(2,7-naphthalate)), poly(methaphenylene isophthalate), poly(glycolic acid), poly(ethylene succinate), poly(ethylene adipate), poly(ethylene sebacate), poly(decamethylene azelate), poly(ethylene sebacate), poly(decamethylene adipate), poly(decamethylene sebacate), poly(dimethylpropiolac- 5i tone), poly(para-hydroxybenzoate) (Ekonol), poly(ethylene oxybenzoate) (A-tell), poly(ethylene isophthalate), poly(tetramethylene terephthalate, poly(hexamethylene terephthalate), poly(decamethylene terephthalate), poly(1,4-cyclohexane dimethylene terephthalate) (trans), poly(ethylene 1,5- 5. naphthalate), poly(ethylene 2,6-naphthalate), poly(1,4- cyclohexylene dimethylene terephthalate), (Kodel) (cis), and poly(l,4-cyclohexylene dimethylene terephthalate (Kodel) (trans). In particular embodiments, the polyester compounds can be polyester compounds prepared from the condensation 6 of a diol and an aromatic dicarboxylic acid. Illustrative of such aromatic carboxylic acids are terephthalic acid, isophthalic acid and an $\\mathbf{\\alpha}_{\\mathrm{~d~}}$ -phthalic acid, 1,3-napthalenedicarboxylic acid, 1,4 napthalenedicarboxylic acid, 2,6-napthalenedicarboxylic acid, 2,7-napthalenedicarboxylic acid, 4,4'- diphenyldicarboxylic acid, $^{4,4^{\\prime}}$ -diphenysulfphone- 6: dicarboxylic acid, 1,1,3-trimethyl-5-carboxy-3-(pcarboxyphenyl)-idane, diphenyl ether $^{4,4^{\\dag}}$ -dicarboxylic acid, bis-p(carboxy-phenyl)methane, and the like. In even more particular embodiments, the aforementioned aromatic dicarboxylic acids can include those based on a benzene ring (such as terephthalic acid, isophthalic acid, orthophthalic acid). Amongst these acid precursors, terephthalic acid is a particular acid precursor.  \n\nThe fluoropolymers can include polytetrafluoroethylene (PTFE), perfluoroalkoxy polymer (PFA), fluorinated ethylene-propylene (FEP), copolymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride (THV), copoly  \n10 mers of hexafluoropropylene (HFP) and vinylidene fluoride (VDF or VF2), terpolymers of tetrafluoroethylene (TFE), vinylidene fluoride(VDF) and hexafluoropropylene (HFP) as well as perfluoromethylvinylether (PMVE) containing specialties, polyethylenetetrafluoroethylene (ETFE)， polyvi  \n15 nylidene fluoride (PVDF), polyvinylfluoride (PVF), polyethylenechlorotrifluoroethylene (ECTFE), polychlorotrifluoroethylene (PCTFE), poly(ethylene tetrafluoroethylene)fluoropolymer (PETFE), and combinations thereof.Fluoropolymers, in particular, are very difficult sub  \n20 strates on which to adhere any layer, particularly an antifogging layer without risks of delamination. One particular advantage of certain embodiments of the composites described herein is the excellent adherability or bondability of the fluoropolymer layer. This feature is also described in terms of its ability to not delaminate.   \n25 In certain embodiments, the polyvinyl chloride material can be derived from the polymerization of the monomer vinyl chloride by any suitable techniques such as suspension polymerization, emulsion polymerization or bulk polymerization. The polyvinyl chloride material may include chlorinated   \n30 polyvinyl chloride with increased chlorine content. For desired physical and chemical properties and ease of processability the polyvinyl chloride material may comprise addenda such as heat stabilizers, UV stabilizers, lubricants, plasticizers, processing aids, impact modifiers, thermal modifiers, fillers, flame retardants, biocides, blowing agents and smoke   \n35 suppressors, and, optionally pigments.  \n\nIn very particular embodiments, the substrate materials can include polyvinyl chloride; polyesters such as PET, PEN, PETG, polyester ionomers; polycarbonates; fluoropolymers such as ETFE, PFA, FEP, PVDF, THV and PVF; polyolefins such as PE and PP; polyurethanes; cellulose acetates; and glass.  \n\nIn certain embodiments, when used, the flexible plastic substrate can be reinforced with a hard coating. Typically, the hard coating is an acrylic coating. Such a hard coating typically has a thickness of from 1 to 15 microns, such as from 2 to 4 microns and can be provided by free radical polymerization, initiated either thermally or by ultraviolet radiation, of an appropriate polymerizable material. Depending on the substrate, different hard coatings can be used. When the substrate is polyester or Arton, a particularly useful hard coating is the coating known as “Lintec.” Lintec contains UV cured polyester acrylate and colloidal silica. When deposited on Arton, it has a surface composition of 35 atom $\\%$ C,45 atom $\\%$ O, and 20 atom $\\%$ Si, excluding hydrogen. Another particularly useful hard coating is the acrylic coating sold under the trademark “Terrapin\" by Tekra Corporation, New Berlin, Wis.  \n\nReferring again to FIG. 2, certain embodiments can include additional polymer layers in the composite other than the substrate layer. In such embodiments, the composite can contain an adhesive layer, such as between any of the polymer layers.  \n\nIn certain embodiments, the adhesive layer can include one or more of a water soluble polymer, a hydrophilic colloid or a water insoluble polymer, latex or dispersion. In particular embodiments, the adhesive layer can contain a polymer or interpolymer prepared from ethylenically unsaturated monomers such as styrene, styrene derivatives, acrylic acid or methacrylic acid and their derivatives, olefins, (meth)acrylonitriles, itaconic acid and its derivatives, maleic acid and its derivatives, vinyl halides, vinyl acetate,vinylidene halides, epoxies, urethanes,imines, polyesters, fluoropolymers,or combinations thereof.  \n\nParticularly suitable fluoropolymers can include polytetrafluoroethylene (PTFE), perfluoroalkoxy polymer (PFA), fluorinated ethylene-propylene (FEP), copolymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride (THV), polyethylenetetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polyvinylfluoride (PVF), polyethylenechlorotrifluoroethylene (ECTFE),polychlorotrifluoroethylene (PCTFE), and combinations thereof.  \n\nIn particular embodiments, the adhesive layer can be prepared from an aqueous dispersion of condensation polymers such as, for example, polyurethanes and polyesters.  \n\nIt is also useful to describe the constituents of the adhesive layer in terms of its glass transition temperature. In particular embodiments, the adhesive layer can include a polymer having a glass transition temperature $(\\mathrm{T}_{g})$ of no greater than 60 degrees Celsius, no greater than 20 degrees Celsius, no greater than 10 degrees Celsius, and even no greater than 0 degrees Celsius. These glass transition temperatures ensure sufficient flow of the adhesive layer during lamination.  \n\nAnother way to describe the adhesive layer is through a quantification of its adhesive effect through a peel strength test. The peel strength can be measured according to ASTM D1876. In certain embodiments, the first adhesive layer, the second adhesive layer, or combinations thereof can have peel strength of at least about 2 pounds per linear inch (PLI), at least about 3 PLI, at least about 4 PLI, or even at least about 5 PLI between adjoining sheets. In particular, the adjoining sheets can be those described herein such as the substrate layer, the first transparent layer, the second transparent layer, or combinations thereof.  \n\nThe adhesive layer can have a thickness of at least 0.1 micrometers, at least 0.5 micrometers, or even at least 1 micrometer. The adhesive layer can have a thickness of no greater than 100 micrometers, no greater than 50 micrometer, no greater than 10 micrometers, or even no greater than 8 micrometers. Moreover, the adhesive layer can have a thickness in a range of any of the maximum and minimum values described above, such as about O.1 micrometers to about 100 micrometers, about 0.5 micrometers to about 50 micrometers, or even about 1 micrometer to about 10 micrometers.  \n\nAs discussed above, the composite can contain additional layers other than the substrate layer, such as a first transparent layer and a second transparent layer. The first transparent layer and/or the second transparent layer can be a multitude of different materials, including those described for the substrate layer. In certain embodiments, the first transparent layer and the second transparent layer can contain the same material. In other embodiments, the first transparent layer and the second transparent layer can be different. In particular embodiments, the first and/or second transparent layers can contain a polymer. However, it is to be understood that the first and/or second transparent layers can be include glass, ceramic, metals or any other suitable material for any reason. For example, the first and second transparent layers can be any of the materials described above for the substrate layer.  \n\nThe first transparent layer and/or the second transparent layer can include, for example, transparent plastics such as those described herein above as the substrate layer. In particular embodiments, the first transparent layer and/or the second transparent layer is the same as described for the substrate layer herein above.Most preferred materials for the first transparent layer and/or the second transparent layer include polyvinyl chloride; polyesters such as PET, PEN, PETG, polyester ionomers; polycarbonates; fluoropolymers such as ETFE, PFA, FEP, THV; polyolefins such as PE and PP; cellulose acetates; and glass.  \n\nThe substrate layer and/or the first transparent layer and/or the second transparent layer can be produced by any means known in the art such as, extrusion, coextrusion, molding, blow molding, orientation, lamination, casting, calendaring, coating, thermo-forming, and the like. In a preferred embodiment the substrate layer and/or the first transparent layer and/or the second transparent layer can contain a free standing sheet.  \n\nThe substrate layer and/or the first transparent layer and/or the second transparent layer can comprise any additives such as charge control agents, conductive particles or polymers, crosslinking agents or hardeners, soluble and/or solid particle dyes, anti-foggants, inorganic or organic fillers, dispersants, lubricants, plasticizers, antioxidants, voiding agents, colorants or tints, roughening agent, slip agent, UV absorbers, refractive index matching material, release agents, flame retardants, and others well-known in the art.  \n\n15 In particular embodiments, the substrate layer and/or the first transparent layer and/or the second transparent layer, and particularly the fluoropolymer layer, can have any number of primers or surface treatment to improve coatability and/or adhesion. Such primers can include acrylics, polyurethanes,   \n20 polyesters, vinylidene halides, polyolefines, epoxies, silanes and the like. Surface treatments can include flame, plasma and corona discharge treatment, ultraviolet radiation treatment, ozone treatment, electron beam treatment, chemical treatment and the like. A particularly useful surface treatment preferred for fluo  \n25 ropolymer surface is the C-treatment, which refers to_a method for modifying the surface by corona treatment in the presence of a solvent gas such as acetone.Not to be limited by theory, the method has been found to provide strong interlayer adhesion between a modified fluoropolymer and a non   \n30 fluoropolymer interface (or a second modified fluoropolymer).C-treatment has been described in U.S.Pat.No. 6,726, 979 and references therein, the teachings of which are incorporated herein in their entirety for all purposes.  \n\nThe anti-fog layer can contain one or more polymers. In certain embodiments, the anti-fog layer can contain can contain at least two different polymers, at least three different polymers, or even at least four different polymers. In a preferred embodiment, the antifog layer contains a crosslinked network of the different polymers.  \n\nIt is helpful to describe the polymers within the anti-fog layer in terms of certain material properties. In particular embodiments the anti-fog layer can contain a hydrophilic polymer, an adhesive polymer, and a hard polymer in which each polymer is different.  \n\nThe hydrophilic polymer of the anti-fog layer can include, for example, a polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate, polyvinylpyrrolidone, polyethylene oxide, polyacrylamide, polyester, polyurethane, cellulose acetate, hydroxyethyl cellulose, hydroxymethyl cellulose or gelatin or blends or copolymers thereof. The hydrophilic polymer can be a polymer having a backbone and hydrophilic segments covalently bonded to the backbone.  \n\nThe hydrophilic segments can include alkylene oxides lactones, lactams, silanes, acrylamides, alcohols, gelatin, or combinations thereof. In particular embodiments, the hydrophilic segments include alkylene oxides, lactones, lactams, or combinations thereof.  \n\nThe hydrophilic segments can have a molecular weight of at least about 100, at least about 500, or even at least about 1000.Further, the hydrophilic segments can have a molecular weight of no greater than about 10oo00, no greater than about 50000, or even no greater than about 10oo0. Moreover, the hydrophilic segments can have a molecular weight in a range of any of the maximum and minimum values described above, such as, about 100 to about 100o00, about 500 to about 50000, or even about 10o0 to about 10000.  \n\nThe hydrophilic segments can be at least about $1\\mathrm{wt}\\%$ ,at 65 least about $10\\mathrm{wt}\\%$ , or even at least about $25\\mathrm{wt\\%}$ by weight ofthe hydrophilic polymer.Further, the hydrophilic segments can be no greater than about $95\\mathrm{wt\\%}$ , no greater than about 75 wt $\\%$ ， or even no greater than about $50\\mathrm{wt\\%}$ . Moreover, the hydrophilic segments can contain a weight percentage of the hydrophilic polymer in a range of any of the maximum and minimum values described above, such as, about 1 wt $\\%$ to about $95\\mathrm{wt}\\%$ ,about $10\\mathrm{wt}\\%$ to about $75\\mathrm{wt\\%}$ ,or even about 25wt $\\%$ to about $50\\mathrm{wt\\%}$  \n\nThe hydrophilic polymer can be present in the anti-fog layer in an amount of no greater than about 99.9 wt $\\%$ ，no greater than about $90\\mathrm{wt}\\%$ , no greater than about $80\\mathrm{wt}\\%$ ,or even no greater than about 70 wt $\\%$ based on the total dry weight of the anti-fog layer. In further embodiments, the hydrophilic polymer can be present in the anti-fog layer in an amount of at least about $0.0\\bar{1}\\mathrm{wt\\%}$ ，at least about $10\\mathrm{{wt}\\%}$ ,at least about $20\\mathrm{wt\\%}$ ，or even atleast about 25 wt $\\%$ basedon the total dry weight of the anti-fog layer.Moreover, the hydrophilic polymer can be present in the anti-fog layer in an amount in a range of any of the maximum and minimum values described above, such as about $0.01\\mathrm{wt}\\%$ to about 99.9 $w t\\%$ about $10\\mathrm{wt}\\%$ to about $90\\mathrm{wt}\\%$ ,about $20\\mathrm{wt\\%}$ to about $80\\mathrm{wt\\%}$ ,or even about $25\\mathrm{wt\\%}$ to about $75\\mathrm{wt\\%}$ based on the total dry weight of the anti-fog layer.  \n\nFurther, in certain embodiments, the hydrophilic polymer can be the primary polymer in the anti-fog layer. For example, the hydrophilic polymer can be present in the anti-fog layer in an amount greater than the adhesive polymer, hard polymer, or a combination thereof.  \n\nThe adhesive polymer can include one or more of a water soluble polymer, a hydrophilic colloid or a water insoluble polymer, latex or dispersion. In particular embodiments, the adhesive polymer can be a polymer or interpolymer prepared from ethylenically unsaturated monomers such as styrene, styrene derivatives, acrylic acid or methacrylic acid and their derivatives, olefins, (meth)acrylonitriles, itaconic acid and its derivatives, maleic acid and its derivatives, vinyl halides, vinyl acetate, vinylidene halides, epoxies, urethanes, imines, polyesters, fluoropolymers, or combinations thereof.  \n\nParticularly suitable fluoropolymers can include polytetrafluoroethylene (PTFE), perfluoroalkoxy polymer (PFA), fluorinated ethylene-propylene (FEP), copolymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride (THV), polyethylenetetrafluoroethylene (ETFE), polyvinylidene fluoride(PVDF), polyvinylfluoride (PVF), polyethylenechlorotrifluoroethylene (ECTFE), polychlorotrifluoroethylene (PCTFE), and combinations thereof.  \n\nIn particular embodiments, the adhesive polymer can be prepared from an aqueous dispersion of condensation polymers such as, for example, polyurethanes and polyesters.  \n\nIt is also useful to describe the adhesive polymer in terms of its glass transition temperature. In particular embodiments, the adhesive polymer can have a glass transition temperature $(\\mathrm{T}_{g})$ of no greater than 60 degrees Celsius, no greater than 20 degrees Celsius, no greater than 1O degrees Celsius, and even no greater than O degrees Celsius. These glass transition temperatures ensure sufficient flow of the polymer during lami- 5 nation.  \n\nAnother way to describe the adhesive polymer is through a quantification of its adhesive effect through a peel strength test. The peel strength is measured according to ASTM D1876. In certain embodiments, the adhesive polymer can have a peel strength of at least about 2 pounds per linear inch (PLI), at least about 3 PLI, at least about 4 PLI, or even at least about 5 PLI between adjoining sheets.  \n\nIn certain embodiments, the adhesive polymer can be present in the anti-fog layer in an amount of no greater than about $90\\mathrm{wt}\\%$ , no greater than about $80\\mathrm{wt\\%}$ , no greater than about $70\\mathrm{wt}\\%$ ,or even no greater than about 60 wt $\\%$ based on the total dry weight of the anti-fog layer. In further embodiments, the adhesive polymer can be present in an amount of at least about $0.1\\mathrm{wt}\\%$ ，at least about $10\\mathrm{wt\\%}$ ，atleast about 20 wt $\\%$ ，or even at least about $25\\mathrm{\\wt\\\\%}$ based on the total dry weight of the anti-fog layer. Moreover, the adhesive polymer can be present in the anti-fog layer in an amount in a range of any of the maximum and minimum values described above, such as about 0.1 wt $\\%$ to about $90\\mathrm{\\wt\\\\%}$ ，about $10\\mathrm{\\mt\\%}$ to about $80\\mathrm{wt\\%}$ about $20\\mathrm{wt\\%}$ to about $70\\mathrm{wt\\%}$ ,or even about $25\\mathrm{wt\\%}$ to about $60\\mathrm{wt\\%}$ based on the total dry weight of the anti-fog layer.  \n\nIn further embodiments, the anti-fog layer can further include a hard polymer. The hard polymer can provide mechanical strength to the anti-fog layer and also aid in improving the scratch resistance of the anti-fog layer.  \n\nIn certain embodiments, the hard polymer can include a 10 water soluble polymer, a hydrophilic colloid or a water insoluble polymer, latex or dispersion. In particular embodiments, the hard polymer can be a polymer or interpolymer prepared from ethylenically unsaturated monomers such as styrene, styrene derivatives, acrylic acid or methacrylic acid 15 and their derivatives, olefins, (meth)acrylonitriles, itaconic acid and its derivatives, maleic acid and its derivatives, vinyl halides, vinyl acetate, vinylidene halides, epoxies, urethanes, imines, polyesters, fluoropolymers, or combinations thereof. Particularly suitable fluoropolymers can include polytet20 rafluoroethylene (PTFE), perfluoroalkoxy polymer (PFA), fluorinated ethylene-propylene (FEP), copolymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride (THV), polyethylenetetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polyvinylfluoride (PVF), polyethylenechlorotrifluoroethylene (ECTFE),polychlorot25 rifluoroethylene (PCTFE), and combinations thereof.  \n\nIn certain further embodiments, the hard polymer can include an aqueous dispersion of condensation polymers such as polyurethanes and polyesters.  \n\nIt is also useful to describe the hard polymer in terms of its hardness. Hardness can be quantified using a pencil hardness test, measured according to ASTM D3363. In the embodiments described herein, the hard polymer can have a pencil hardness of at least about H, at least about 2H, at least about 3H as measured according to ASTMD3363.Further, the hard polymer can have a pencil hardness of no greater than about 9H, no greater than about 8H, no greater than about 7H, no greater than about 6H, or even no greater than about 5H as measured according to ASTM D3363.Moreover, the hard polymer can have a pencil hardness in a range of any of the maximum and minimum values described above, such as, from about H to about 9H, from about 2H to about 8H, or even from about 3H to about 7H as measured according to ASTM D3363.  \n\nAnother useful property to describe the hard polymer is its $100\\%$ modulus. In particular embodiments, the hard polymer   \n$45$ can have a $100\\%$ modulus of at least about 20o0 psi, at least about 3000 psi, or even at least about 3500 psi as measured according to ASTM D412. In further embodiments, the hard polymer can have a $100\\%$ modulus of no greater than about 15000 psi, no greater than about 10oo0 psi, or even no greater than about 7500 psi as measured according to ASTM D412.   \n50 Moreover, the hard polymer can have a $100\\%$ modulus in a range of any of the maximum and minimum values described above, such as, from about 2000 psi to about 15000 psi, from about $3000{\\mathrm{psi}}$ to about 10000 psi, or even from about 3500 psi to about 7500 psi as measure according to ASTM D412.   \n55 Still yet another useful characteristic to describe the hard polymer is its tensile strength. In particular embodiments, the hard polymer can have a tensile strength of at least about 3000 psi, at least about 4000 psi, or even at least about 5000 psi as measured according to ASTM D412. In further embodiments, the hard polymer can have a tensile strength of no greater than   \n60 about 15000 psi, no greater than about 1000 psi, or even no greater than about 7500 psi as measured according to ASTM D412.Moreover, the hard polymer can have a tensile strength in a range of any of the maximum and minimum values described above, such as, from about 30o0 psi to about 15000   \n65 psi, from about 4000 psi to about 10000 psi, or even from about 5000 psi to about 7500 psi as measured according to ASTM D412.  \n\nStill yet another useful characteristic to describe the hard polymer is its $\\%$ elongation at break. In particular embodiments, the hard polymer can have a $\\%$ elongation at break of at least $100\\%$ at break, at least about $200\\%$ at break, or even at least about $300\\%$ at break as measured according to ASTM D412. In further embodiments, the hard polymer can have a $\\%$ elongation at break of no greater than $100\\%$ elongation at break, no greater than $700\\%$ elongation at break, or even no greater than $500\\%$ elongation at break as measured according to ASTM D412. Moreover, the hard polymer can have $\\%$ elongation at break in a range of any of the maximum and minimum values described above, such as from about $100\\%$ to about $100\\%$ ，from about $200\\%$ to about $700\\%$ ，or even from about $300\\%$ to about $500\\%$ elongation at break as measured according to ASTM D412  \n\nIn certain embodiments, the hard polymer can be present in the anti-fog layer in an amount of no greater than about 90 wt $\\%$ , no greater than about $80\\mathrm{wt}\\%$ , no greater than about 70 wt $\\%$ ，or even no greater than about $60\\%$ based on the total dry weight of the anti-fog layer. In further embodiments, the hard polymer can be present in an amount of at least about 0.1 wt $\\%$ , at least about $10\\mathrm{wt\\%}$ , at least about $20\\mathrm{wt\\%}$ ，or even at least about 25 wt $\\%$ based on the total dry weight of the anti-fog layer. Moreover, the hard polymer can be present in the anti-fog layer in an amount in a range of any of the maximum and minimum values described above, such as about 0.1 wt $\\%$ to about 90 wt $\\%$ ，about $10\\mathrm{wt}\\%$ to about 80 $w t\\%$ ,about $20\\mathrm{wt\\%}$ to about $70\\mathrm{wt}\\%$ ,or even about $25\\mathrm{wt\\%}$ to about $60\\mathrm{wt\\%}$ based on the total dry weight of the anti-fog layer.  \n\nIn very particular embodiments, the anti-fog coating composition and the anti-fog layer can further include one more anti-blocking agents. In particular embodiments, the antiblocking agents can include colloidal inorganic particles, such as a colloidal silica and/or a surfactant.  \n\nIn certain embodiments, the colloidal silica compound can contain a nanoparticle. Further, in certain embodiments, the colloidal silica compound can be generally transparent. Particular examples of a suitable colloidal silica can include Ludox AM, which is commercially available from WR Grace Co.  \n\nWhen used, the colloidal silica can be present in the antifog coating composition or the anti-fog layer in an amount of at least about 1 wt. $\\%$ ,at least about 3 wt. $\\%$ ，or even at least about 7 wt. $\\%$ ，based on the total weight of the anti-fog coating composition or the anti-fog layer. In further embodiments, the colloidal silica can be present in the anti-fog coating composition or the anti-fog layer in an amount of no greater than about 50 wt. $\\%$ no greater than about 40 wt. $\\%$ 。 no greater than about 30 wt. $\\%$ ,or even no greater than about 20wt. $\\%$ . In still further embodiments, the colloidal silica can be present in the anti-fog coating composition or the anti-fog layer in an amount in a range of any of the minimum and maximum values provided above, such as in a range of from about 1 wt. $\\%$ to about 50 wt. $\\%$ about 3 wt. $\\%$ to about $40\\mathrm{wt}$ · $\\%$ ,or even about 7 wt. $\\%$ to about 30 wt. $\\%$ \\*  \n\nRegarding the surfactant, it particular embodiments, the surfactant can include a fluorinated surfactant. Furthermore, in certain embodiments, the surfactant can include an anionic surfactant. In very particular embodiments, the surfactant can include a fluorinated anionic surfactant. Suitable examples of fluorinated anionic surfactant can include Capstone FS-61 available from DuPontTM.  \n\nIn certain embodiments the surfactant can be present in the anti-fog coating composition or the anti-fog layer in an amount of at least about O.005 wt. $\\%$ ,atleast about 0.01 wt. $\\%$ or even at least about 0.03 wt. $\\%$ , based on the total weight of the anti-fog coating composition or the anti-fog layer. In further embodiments, the surfactant can be present in the anti-fog coating composition or the anti-fog layer in an amount of no greater than about 15 wt. $\\%$ ， no greater than about 10 wt. $\\%$ , no greater than about 8 wt. $\\%$ ，or even no greater than about 2 wt. $\\%$ . In still further embodiments, the surfactant can be present in the anti-fog coating composition or the anti-fog layer in an amount in a range of any of the minimum and maximum values provided above, such as in a range of from about 0.005 wt. $\\%$ to about 15 wt. $\\%$ ,about 0.01 wt. $\\%$ to about 10 wt. $\\%$ , or even about 0.03 wt. $\\%$ to about 8 wt. $\\%$  \n\nA particular advantage of certain embodiments of the present disclosure is the unexpected discovery that the antiblocking agents described above were able to significantly   \n10 reduce the blocking (also commonly referred to as stickiness or tackiness) of the anti-fog coating layer. Such anti-blocking effects are particularly desirable when the composite structure containing the anti-fog layer is folded such that two surfaces containing the anti-fog layer touch, such as in pack  \n15 aged personal protective equipment. In the absence of the anti-blocking agents described above, such situations could result in the two surfaces sticking together and damaging the anti-fog layer when separated, and particularly when the composite structure is stored at an elevated temperature,   \n20 above room temperature. As shown in more detail in the examples below, it was unexpectedly discovered that the antiblocking agents described above served to significantly reduce blocking. Accordingly, in certain particular embodiments of the present disclosure, an anti-fog layer and/or an anti-fog coating composition can contain a hydrophilic poly  \n25 mer and an anti-blocking agent comprising colloidal silica and/or an anionic fluorinated surfactant. Thus it is to be understood that in certain embodiments, the hard polymer and/or the adhesive polymer can be optional.  \n\nIn forming the anti-fog layer or the first and the second adhesive layer, the composition can be solventborne or waterborne.For environmental reasons waterborne compositions are preferred. By waterborne it is meant that the coating medium comprises at least $50\\%$ by weight of water.  \n\nThe coating composition(s) or the coated layer(s) can include any number of additives for a variety of different reason. These additives can include surfactants, defoamers or coating aids, charge control agents, conductive particles or polymers, thickeners or viscosity modifiers, coalescing aids, crosslinking agents or hardeners, soluble and/or solid particle dyes, anti-foggants, inorganic or organic fillers, matte beads, inorganic or polymeric particles, adhesion promoting agents, bite solvents or chemical etchants, lubricants, plasticizers, antioxidants, voiding agents, colorants or tints, roughening agent, slip agent, UV absorbers, refractive index matching material, flame retardant and others well-known in the art.  \n\n45 In a particular embodiment the coated layer can be crosslinked by the use of a suitable cross linking agent such as melamine resins, glycoluril formaldehyde resins, polycarboxylic acids and anhydrides, polyamines, polyimines, epihalohydrins, epoxides, diepoxides, dialdehydes, diols, carboxylic acid halide, ketenes, polyaziridines, isocyanates, 50 carbodiimides, metal carbonates and combinations thereof. Alternatively, the coated layer can be crosslinked by suitable use of radiation such as UV or visible light, electron beam, plasma or corona.  \n\nThe anti-fog layer or the first and the second adhesive   \n55 layers can be formed by any method known in the art. Particular methods include coating from a suitable coating composition by any well-known coating method such as rod coating, knife coating, air knife coating, gravure coating, dip coating, slot-die coating, roller coating,knife over roller coat  \n60 ing,spray coating, and the like. Other techniques may include inkjet printing, flexographic printing, screen printing, calendaring, lamination, hot melt extrusion, and the like. Alternatively, the layer(s) can be transferred to a receiver member from a donor member by the application of heat and/or pressure.  \n\nAn important characteristic of the anti-fog layer of the invention for its desirable application in a visor is its high transparency to visible light, as indicated by its $\\mathrm{{high\\%}}$ visible light transmission $(\\%\\mathrm{VLT})$ _ $\\%\\mathrm{VLT}$ is the intensity ratio of the transmitted light to incident light passing through a layer and can be determined by measuring the optical density of the layer using a densitometer (such as an X-rite densitometer) as described in U.S. Pat.No. 7,410,825 or directly by an instrument such as BYK Gardner Haze-Gard Plus. The antifog layer of the invention has $a\\%$ VLT of at least $40\\%$ ，preferably at least $50\\%$ , more preferably at least $60\\%$ , most preferably at least $70\\%$ or even at least $90\\%$ as measured according to either a densitometer or a BYK Gardner Haze-Gard Plus.  \n\nMoreover, the transparent composite, as a whole including all layers integral to the composite can have a high $\\%$ VLT.In particular embodiments, the transparent composite can have a $\\%\\mathrm{VLT}$ of at least $30\\%$ ,atleast $40\\%$ ,atleast $50\\%$ ,atleast $60\\%$ or even at least $80\\%$  \n\nFurther, the anti-fog layer can have good adhesion to an adjacent layer as measured according to the Scotch Tape test. The Scotch Tape test is described in more detail below in the Examples section.A particular advantage of the present disclosure is that the composites according to the embodiments described herein have good adhesion to the underlying layer. Traditional anti-fog layers suffer from the ability to adhere to underlying substrates, particularly without negatively effecting either the transparency or anti-fogging effects of the antifog layer.  \n\nStill further, the anti-fog layer can be non-tacky as deter- 25 mined by folding the layer over itself, separating the layer, and observing if the layer stuck to itself. This tackiness characteristic is described in more detail below. A particular advantage of the present disclosure is that the composites according to the embodiments described herein have good 30 JV adhesion to the underlying layer without being tacky in the layer exposed to the environment. Traditional anti-fog layers suffer from the ability to adhere to underlying substrates while also being non-tacky on the opposite surface.  \n\nMoreover, the anti-fog layer can pass a steam bath test. The steam bath test measures the ability of the anti-fog layer to withstand repeated humid environments without deterioration of the anti-fogging effects.A particular advantage of the present disclosure is that the composites according to the embodiments described herein can withstand repeated washing and repeated exposure to humid environments without deterioration of the anti-fogging effects, particularly in a waterborne anti-fog coating composition.  \n\nStill further, it is a particular advantage of the present disclosure that the composites described herein do not delaminate during flexing. This attribute can be quantified by a flexing operation in a Gelbo tester for 2000 cycles. In the embodiments_described herein, the composites cannot delaminate after 2O00 cycles in a Gelbo tester. Traditional composites suffer from delamination when tailoring the composite to have desired anti-fogging effects, transparency, tackiness, and combinations thereof.  \n\nThe transparent composite of the invention as described herein above may comprise any number of additional functional layers for any purpose. These functional layers may include antistatic layer, primers, adhesion promoting layer, flame retardant layer, barrier layer, breathable layer, conveyance layer, sealable layer, abrasion or scratch resistant layer, hard coat, release layer, slip layer, antireflection layer, refractive index matching layer, UV protective layer, tint layer, tamper-resistant layer, and the like.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# EXAMPLES  \n\nEmbodiments of the disclosure are illustrated with the following Examples, which are illustrative, and do not limit the scope of the present disclosure. The polymeric substrates or layers used in these examples include (1) polyvinyl chloride (PVC) sheets and (2) C-treated fluorinated ethylene propylene (FEP) copolymer sheets.  \n\nThe constituents used for various layers of the Examples of the invention as well as Comparative samples comprised of the following commercially available materials:  \n\na. Neorez R 962l, a waterborne aliphatic polyurethane dispersion supplied by DSM Neoresins;   \nb. Neorez R 9330, a waterborne aliphatic polyurethane dispersion supplied by DSM Neoresins;   \nc. Neorez R 9679, a waterborne aliphatic polyurethane dispersion supplied by DSM Neoresins;   \nd. Neorez R6oo, a waterborne aliphatic polyurethane dispersion supplied by DSM Neoresins;   \ne. Bondthane UD-410, a waterborne aliphatic polyurethane dispersion supplied by BPI;   \nf. Cymel 303LF, a hexamethoxymethylmelamine compound supplied by Cytech Industries; and   \ng. Zonyl FSO, an ethoxylated nonionic fluorosurfactant supplied by Dupont.   \nh. Ludox AM, a colloidal silica dispersion supplied by WR Grace   \ni. Capstone FS-61, a fluorinated anionic surfactant supplied by Dupont   \nAdhesive Layer",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 19,
+        "chunk": "# Example 1",
+        "category": " Introduction"
+    },
+    {
+        "id": 20,
+        "chunk": "# Two Layer Composite  \n\nCoating compositions for the adhesive layer described in Table 1A, were coated at various thickness on to C-treated FEP substrates and dried at 93 degrees Celsius for 1O minutes. Subsequently, each of the adhesive coated FEP sheet was   \n351 laminated to a PVC sheet such that the adhesive layer is between the FEP and the PVC sheet Lamination was done either at a foot press at 40 psi at 121 degrees Celsius or with a hand roller at room temperature (RT). Some ofthe compos  \n40 ites thus prepared were additionally cured at 107 degrees Celsius for various time periods. The peel strength between the FEP sheet and the PVC sheet was determined as pounds per linear inch (PLI) in an Instron following ASTM D1876.   \n45 The various composite structures, processing details and the corresponding peel strength values are listed in table 1B.  \n\nTABLE1A   \n\n\n<html><body><table><tr><td rowspan=\"3\">50</td><td></td><td>Neorez R9621</td><td>Neorez R9330</td><td>Neorez R9679</td><td>Neorez</td><td>Cymel 303</td><td>water</td><td>Zonyl FSO</td></tr><tr><td>Sample # Adhesive</td><td>gms 65.8</td><td>gms</td><td>gms</td><td>R600</td><td>gms</td><td>gms 34.2</td><td>gms</td></tr><tr><td></td><td>1 Adhesive</td><td>59.2</td><td></td><td></td><td></td><td>2.5</td><td>38.3</td><td>１</td></tr><tr><td>55</td><td>2 Adhesive</td><td>52.6</td><td></td><td></td><td></td><td>5.0</td><td>42.4</td><td>１ 1</td></tr><tr><td>3</td><td>Adhesive</td><td></td><td>62.5</td><td></td><td></td><td></td><td>37.5</td><td>１</td></tr><tr><td>4</td><td>Adhesive</td><td></td><td>56.3</td><td></td><td></td><td>2.5</td><td>41.2</td><td>1</td></tr><tr><td>60</td><td>5 Adhesive</td><td></td><td>50.0</td><td></td><td></td><td>5.0</td><td>45.0</td><td>1</td></tr><tr><td>6</td><td>Adhesive</td><td></td><td></td><td>67.6</td><td></td><td></td><td>32.4</td><td>１</td></tr><tr><td></td><td>7 Adhesive</td><td></td><td></td><td></td><td>75.8</td><td></td><td>24.2</td><td>１</td></tr><tr><td>65</td><td>8</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n13 TABLE1B   \n\n\n<html><body><table><tr><td>Composite</td><td>Adhesive Sample</td><td>Adhesive thickness micrometers</td><td>Lamination</td><td>Additional Curing</td><td>Peel strength PLI</td></tr><tr><td>Composite 1</td><td>Adhesive 1</td><td>2</td><td>Roller (RT)</td><td>20 min</td><td>6.7</td></tr><tr><td>Composite 2</td><td>Adhesive 2</td><td>2</td><td>Roller (RT)</td><td>20 min</td><td>5.6</td></tr><tr><td>Composite 3</td><td>Adhesive 3</td><td>2</td><td>Roller (RT)</td><td>20 min</td><td>5.3</td></tr><tr><td>Composite 4</td><td>Adhesive 1</td><td>2</td><td>Foot press; 15 sec</td><td>一</td><td>4.3</td></tr><tr><td>Composite 5</td><td>Adhesive 4</td><td>2</td><td>Roller (RT)</td><td>2 min</td><td>2.4</td></tr><tr><td>Composite 6</td><td>Adhesive 4</td><td>2</td><td>Roller (RT)</td><td>3 min</td><td>2.6</td></tr><tr><td>Composite 7</td><td>Adhesive 4</td><td>2</td><td>Roller (RT)</td><td>5 min</td><td>3.2</td></tr><tr><td>Composite 8</td><td>Adhesive 4</td><td>2</td><td>Roller (RT)</td><td>20 min</td><td>5.2</td></tr><tr><td>Composite 9</td><td>Adhesive 4</td><td>6</td><td>Roller (RT)</td><td>2 min</td><td>3.6</td></tr><tr><td>Composite 10</td><td>Adhesive 4</td><td>6</td><td>Roller (RT)</td><td>3 min</td><td>3.6</td></tr><tr><td>Composite 11</td><td>Adhesive 4</td><td>6</td><td>Roller (RT)</td><td>5 min</td><td>3.5</td></tr><tr><td>Composite 12</td><td>Adhesive 5</td><td>2</td><td>Roller (RT)</td><td>20 min</td><td>5.4</td></tr><tr><td>Composite 13</td><td>Adhesive 6</td><td>2</td><td>Roller (RT)</td><td>20 min</td><td>5.4</td></tr><tr><td>Composite 14</td><td>Adhesive 7</td><td>2</td><td>Roller (RT)</td><td>2 min</td><td>0</td></tr><tr><td>Composite 15</td><td>Adhesive 7</td><td>2</td><td>Roller (RT)</td><td>3 min</td><td>0</td></tr><tr><td>Composite 16</td><td>Adhesive 7</td><td>2</td><td>Roller (RT)</td><td>5 min</td><td>0</td></tr><tr><td>Composite 17</td><td>Adhesive 7</td><td>2</td><td>Roller (RT)</td><td>20 min</td><td>0</td></tr><tr><td>Composite 18</td><td>Adhesive 8</td><td>2</td><td>Roller (RT)</td><td>2 min</td><td>0.5</td></tr><tr><td>Composite 19</td><td>Adhesive 8</td><td>2</td><td>Roller (RT)</td><td>3 min</td><td>0.7</td></tr><tr><td>Composite 20</td><td>Adhesive 8</td><td>2</td><td>Roller (RT)</td><td>5 min</td><td>0.6</td></tr></table></body></html>  \n\nAs illustrated above Adhesive combinations Adhesive 1 through Adhesive 6 resulted in peel strength value at least 2 PLI.  \n\nFurthermore, each composite utilizing Adhesive 1 through Adhesive 6 was bent, folded and flexed and did not delaminate. On the other hand, composites produced with Adhesive 7 through Adhesive 8 provided little to no adhesion. In fact, an integral composite that can be bent, folded or flexed without delamination could not be created using Adhesives 7 through Adhesive 8.  \n\nTABLE 2-continued   \n\n\n<html><body><table><tr><td>Sample No.</td><td>Composite Structure</td><td>Thickness of Adhesive Layer</td><td>Delaminated</td></tr><tr><td>Composite B2</td><td>PVC/Adhesive 4/FEP/ Adhesive 4/PVC</td><td>8 micrometers</td><td>No</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 21,
+        "chunk": "# Example 2  \n\n35  \n\nExample 3  \n\nThree Layer Composite Based on Adhesive 4",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# Anti-Fog Layer  \n\nTwo FEP sheets, which have been C-treated on both sides, were each coated on both sides with Adhesive 4 as outlined in Table A1 and dried at 93 degrees Celsius for 10 minutes.Each adhesive coated FEP sheet was laminated between two PVC sheets with a hand roller at room temperature (RT), followed by 5 minutes of curing at 107 degrees Celsius, to create the  \n\nAnti-fog coating compositions as described in Table 3 below were coated on Composites B1 and B2 over the surface of one of the PVC layers. Further, the anti-fog coating composition was applied directly to a stand-alone C-treated FEP sheet.  \n\nTABLE3   \n\n\n<html><body><table><tr><td>Coating</td><td>Bondthane UD410 gms</td><td>Neorez R9330 gms</td><td>Neorez R9679 gms</td><td>Cymel 303 gms</td><td>Ludox AM gms</td><td>water gms</td><td>Zonyl FSO gms</td><td>Capstone FS-61 gms</td></tr><tr><td>Anti-fog 1</td><td>48.6</td><td>17</td><td>27.6</td><td>5</td><td></td><td>1.8</td><td>1</td><td></td></tr><tr><td>Anti-fog 2</td><td>48.6</td><td>17</td><td>27.6</td><td>一</td><td></td><td>6.8</td><td>1</td><td></td></tr><tr><td>Anti-fog 3</td><td>71.4</td><td>一</td><td></td><td></td><td></td><td>28.6</td><td>1</td><td></td></tr><tr><td>Anti-fog 4</td><td>57.1</td><td>6.2</td><td>6.8</td><td></td><td></td><td>29.9</td><td>1</td><td></td></tr><tr><td>Anti-fog 5</td><td>35.7</td><td>6.2</td><td>27</td><td>3.8</td><td></td><td>27.3</td><td>1</td><td></td></tr><tr><td>Anti-fog 6</td><td>43.7</td><td>15.3</td><td>24.8</td><td>一</td><td>11.3</td><td>4.8</td><td>一</td><td>0.1</td></tr></table></body></html>  \n\nfollowing composites outlined in Table 2 below.Further, each composite was subjected to flexing in a Gelbo apparatus for 2000 cycles and checked for delamination.  \n\nTABLE2   \n\n\n<html><body><table><tr><td>Sample No.</td><td>Composite Structure</td><td>Thickness of Adhesive Layer</td><td>Delaminated</td></tr><tr><td>Composite B1</td><td>PVC/Adhesive 4/FEP/ Adhesive 4/PVC</td><td>2 micrometers</td><td>No</td></tr></table></body></html>  \n\nPerformance Tests Transparency  \n\nThe samples described above having an anti-fog layer 60 coated thereon was evaluated for $\\%$ VLT. Samples with $\\%$ VLT of at least $50\\%$ was considered“high” and otherwise \"low.”  \n\nAdhesion—  \n\nSamples with anti-fog layer were evaluated for adhesion of 65 the anti-fog layer to the immediately preceding layer with Scotch tape. Any removal of material was deemed“poor\" whereas no removal was deemed “good\"",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 23,
+        "chunk": "# 15  \n\nTackiness—  \n\nSamples with anti-fog layer were evaluated for tackiness by folding the layer over itself and separating it. If the layer stuck to itself it was considered “tacky.\" Otherwise, it was considered “non-tacky.\"  \n\nAnti-Fog Capability  \n\nSamples of anti-fog layer were exposed to a steam bath with water temperature at 80 degrees Celsius for 15 second and evaluated for anti-fogging characteristics. The steamed sample was subsequently washed with a clean rag in soap and warm water and dried. After drying the sample was exposed to steam again in the aforesaid manner. The cycle of exposure to steam followed by washing was continued for 15 times, and the sample was checked for any removal of material or loss of anti-fogging characteristics. The anti-fog layers of the invention “passed'\" this test without showing any removal of material or loss of anti-fogging characteristics during or at the end of the cycles.  \n\nDelamination—  \n\nThe anti-fog coated composite was subjected to flexing in a Gelbo tester for 20o0 cycles and evaluated for delamination. The sample is considered to have “passed\" the test, if there was no delamination detected in any of the layers.  \n\nThe test results are summarized below in Table 2B.  \n\nItem 4.The transparent composite according to any one of the preceding items, wherein the adhesive polymer comprises a polymer having a Tg of less than about 45 degrees Celsius; wherein the hard polymer comprises a polymer having a pencil hardness of at least H as measured according to ASTM D3363; and wherein the hydrophilic polymer comprises a polymer having a backbone and hydrophilic segments covalently bonded to the backbone.  \n\nItem 5. The transparent composite or coating composition according to any one of the preceding items, wherein the anti-fog layer or anti-fog coating composition comprises a hydrophilic polymer.  \n\nItem 6. The transparent composite or coating composition according to item 4, wherein the hydrophilic polymer comprises a hydrophilic polyurethane.  \n\nItem 7. The transparent composite or coating composition according to any one of items 5 to 6, wherein the hydrophilic polymer comprises a polymer having a polyurethane backbone and hydrophilic segments covalently bonded to the polyurethane backbone.  \n\nItem 8. The transparent composite or coating composition according to item 7, wherein the hydrophilic segments comprise alkylene oxides, lactones, lactams, silanes, acrylamides, alcohols, gelatin, or combinations thereof.  \n\nTABLE2B   \n\n\n<html><body><table><tr><td></td><td>Anti-fog # Coating</td><td>Composite</td><td>Transparency</td><td>adhesion</td><td>tackiness</td><td>Steam/ clean cycle</td><td>Gelbo</td></tr><tr><td></td><td>1  Anti-fog 1</td><td>Composite B1 (PVC surface)</td><td>high</td><td>good</td><td>Non-tacky passed</td><td></td><td>passed</td></tr><tr><td></td><td></td><td>2 Anti-fog 1 FEP sheet</td><td>high</td><td>good</td><td>Non-tacky passed</td><td></td><td>passed</td></tr><tr><td></td><td>3 Anti-fog 2</td><td>Composite B2 (PVC surface)</td><td>high</td><td>good</td><td>Non-tacky</td><td></td><td>passed</td></tr><tr><td></td><td>4Anti-fog 3</td><td>Composite1 (PVC surface)</td><td>high</td><td></td><td>tacky</td><td></td><td></td></tr><tr><td>5</td><td>Anti-fog 4</td><td>Composite 1 (PVC surface)</td><td>high</td><td></td><td>tacky</td><td></td><td></td></tr><tr><td>6</td><td>Anti-fog 5</td><td>Composite 1 (PVC surface)</td><td>high</td><td>poor</td><td></td><td></td><td></td></tr><tr><td></td><td>7 Anti-fog 6</td><td>Composite B2 (PVC surface)</td><td>high</td><td>good</td><td>Non-tacky passed</td><td></td><td></td></tr></table></body></html>  \n\n40  \n\nAs shown above, Samples 1-3 and 7 resulted in composite visors exhibiting high transparency, good adhesion, nontacky surface, good flexibility, good washability and maintain good anti-fog performance. On the other hand, samples 4-6 provided poor adhesion or a tacky surface, and deemed undesirable for visor applications.  \n\nMany different aspects and embodiments are possible. Some of those aspects and embodiments are described below. After reading this specification, skilled artisans will appreciate that those aspects and embodiments are only illustrative and do not limit the scope of the present invention.Embodiments may be in accordance with any one or more of the items as listed below.  \n\nItem 1.A transparent composite comprising: a substrate layer; and an anti-fog layer, wherein the anti-fog layer comprises an adhesive polymer, a hard polymer, and a hydrophilic polymer, wherein the adhesive polymer, hard polymer, and hydrophilic polymers are different.  \n\nItem 2.A transparent composite comprising: a substrate layer; a first adhesive layer; a first transparent layer; a second adhesive layer; a second transparent layer; and an anti-fog layer comprising an adhesive polymer, a hard polymer, and a hydrophilic polymer, wherein the adhesive polymer, hard polymer, and hydrophilic polymer are different.  \n\nItem 3. An anti-fog coating composition comprising an adhesive polymer, a hard polymer, and a hydrophilic polymer, wherein the adhesive polymer, hard polymer, and hydrophilic polymer are different.  \n\nItem 9. The transparent composite or coating composition according to any one of items 7 to 8, wherein the hydrophilic segments comprise alkylene oxides, lactones, lactams, or combinations thereof.  \n\nItem 10. The transparent composite or coating composition according to any one of items 7 to 9, wherein the hydrophilic segments have a molecular weight of at least about 100, at least about 500, or even at least about 1000.  \n\nItem 11. The transparent composite or coating composition according to any one ofitems 7 to 10, wherein the hydrophilic segments comprise at least about $1\\mathrm{wt\\%}$ , at least about 10 wt $\\%$ ，or even at least about $25\\mathrm{wt\\%}$ by weight of the hydrophilic polymer.  \n\nItem 12. The transparent composite or coating composition according to any one ofitems 5 to 11, wherein the hydrophilic ； polymer is present in the anti-fog layer in an amount of no greater than about $99.9\\mathrm{wt\\\\%}$ , no greater than about $90\\mathrm{wt\\%}$ D no greater than about $80\\mathrm{wt}\\%$ ， or even no greater than about $70\\mathrm{\\bar{w}t\\%}$ based on the total dry weight of the anti-fog layer or coating composition.  \n\nItem 13. The transparent composite or coating composition according to any one ofitems 5 to 12, wherein the hydrophilic polymer is present in the anti-fog layer in an amount of at least about 0.01 wt $\\%$ ，at least about $10\\mathrm{\\textperthousand}$ ，at least about 20 wt $\\%$ ,or even at least about $25\\mathrm{wt\\%}$ based on the total dry weight of the anti-fog layer or coating composition.  \n\nItem 14.The transparent composite or coating composition according to any one of items 5 to 13, wherein the hydrophilic polymer is present in the anti-fog layer in an amount within a range of about $0.01\\mathrm{wt}\\%$ to about $99.9\\mathrm{wt}\\%$ ，about $10\\mathrm{wt}\\%$ to about $90\\mathrm{wt}\\%$ ，about20 wt $\\%$ to about $80\\mathrm{wt\\\\%}$ ，or even about $25\\mathrm{wt\\%}$ to about $75\\mathrm{wt\\%}$ based on the total dry weight of the anti-fog layer or coating composition.  \n\nItem 15.The transparent composite according to any one of the preceding items, wherein the anti-fog layer or anti-fog coating composition comprises a hard polymer.  \n\nItem 16. The transparent composite or coating composition according to item 15, wherein the hard polymer comprises a polymer or interpolymer prepared from ethylenically unsaturated monomers comprising styrene, styrene derivatives, acrylic acid or its derivate, methacrylic acid or its derivate, olefins, (meth)acrylonitriles, itaconic acid and its derivatives, maleic acid and its derivatives, vinyl halides, vinylidene halides, fluoropolymers, or combinations thereof.  \n\nItem 17. The transparent composite or coating composition according to any one of items 15 to 16, wherein the hard polymer comprises a polymer prepared from an aqueous dispersion of condensation polymers.  \n\nItem 18.The transparent composite or coating composition according to any one of items 15 to 17,wherein the hard polymer comprises a polyurethane, a polyester, or combinations thereof.  \n\nItem 19. The transparent composite according to any one of items 15 to 18, wherein the hard polymer comprises a polymer prepared from a polyurethane dispersion, a polyester dispersion, or combinations thereof.  \n\nItem 20. The transparent composite or coating composition according to any one of items 15 to 19, wherein the hard polymer has a pencil hardness of at least about H, at least about 2H, at least about 3H as measured according to ASTM D3363.  \n\nItem 21.The transparent composite or coating composition according to any one of items 15 to 20, wherein the hard polymer has a $100\\%$ modulus of at least about 2000 psi, at least about 3000 psi, or even at least about 3500 psi as measured according to ASTM D412.  \n\nItem 22. The transparent composite or coating composition according to any one of the items 15 to 21, wherein the hard polymer has a $100\\%$ modulus of no greater than about 15000 psi, no greater than about 10oo0 psi, or even no greater than about 7500 psi as measured according to ASTM D412.  \n\nItem 23.The transparent composite or coating composition according to any one of items 15 to 22,wherein the hard polymer has a tensile strength of at least about 3000 psi, at least about 4000 psi, or even at least about 5000 psi as measured according to ASTM D412.  \n\nItem 24. The transparent composite or coating composition according to any one of items 15 to 23,wherein the hard polymer has a tensile strength of no greater than about 15000 psi as measured according to ASTM D412.  \n\nItem 25.The transparent composite or coating composition according to any one of items 15 to 24,wherein the hard polymer is present in the anti-fog layer in an amount of no greater than about $90\\mathrm{wt}\\%$ ,no greater than about $80\\mathrm{wt\\%}$ ,no greater than about $70\\mathrm{wt}\\%$ ，or even no greater than about 60 wt $\\%$ based on the total dry weight of the anti-fog layer or coating composition.  \n\nItem 26. The transparent composite or coating composition according to any one of items 15 to 25,wherein the hard polymer is present in an amount of at least about $0.1\\mathrm{wt}\\%$ ,at least about $10\\mathrm{\\wt\\\\%}$ ，at least about $20\\mathrm{wt}\\%$ ，or even at least about $25\\mathrm{\\wt\\\\%}$ based on the total dry weight of the anti-fog layer or coating composition.  \n\nItem 27. The transparent composite or coating composition according to any one of the items 15 to 26, wherein the hard polymer is present in an amount within a range of about 0.1 wt $\\%$ to about 90 wt $\\%$ ，about10 wt $\\%$ to about $80\\mathrm{wt\\%}$ ，about $20\\mathrm{wt\\%}$ to about $70\\mathrm{wt\\%}$ ,or even about $25\\mathrm{wt\\%}$ to about 60 wt $\\%$ based on the total dry weight of the anti-fog layer or coating composition.  \n\nItem 28. The transparent composite or coating composition according to any one of the preceding items, wherein the anti-fog layer or coating composition comprises an adhesive polymer.  \n\nItem 29.The transparent composite or coating composition according to item 28, wherein the adhesive polymer comprises a polyester or a polyurethane.  \n\nItem 30. The transparent composite or coating composition according to any one items 28 to 29, wherein the adhesive polymer comprises an aliphatic, non-ionic polyurethane.  \n\nItem 31. The transparent composite or coating composition according to any one of items 28 to 30, wherein the adhesive polymeris present in an amount of no greater than about 90 wt $\\%$ , no greater than about $80\\mathrm{wt\\%}$ , no greater than about 70 wt $\\%$ ，or even no greater than about $60\\mathrm{wt\\%}$ based on the total dry weight of the anti-fog layer or coating composition.  \n\nItem 32. The transparent composite or coating composition according to any one of items 28 to 31,wherein adhesive polymer is present in an amount of at least about $0.1\\mathrm{wt}\\%$ ,at least about $10\\mathrm{\\wt\\\\%}$ ，at least about $20\\mathrm{wt\\%}$ ,or even at least about 25 wt $\\%$ based on the total dry weight of the anti-fog layer or coating composition.  \n\nItem 33. The transparent composite or coating composition according to any one of items 28 to 32,wherein the adhesive polymer is present in an amount within a range of about 0.1 wt to about $90\\mathrm{wt\\\\%}$ ，about $10\\mathrm{wt\\%}$ to about 80 wt $\\%$ ，about $20\\mathrm{wt\\%}$ to about $70\\mathrm{wt}\\%$ ,or even about $25\\mathrm{wt\\%}$ to about 60 wt $\\%$ based on the total dry weight of the anti-fog layer or coating composition.  \n\nItem 34. The transparent composite or coating composition   \n$30$ according to any one of items 28 to 33, wherein the adhesive polymer comprises a polymer or interpolymer prepared from ethylenically unsaturated monomers selected from the group consisting of styrene, styrene derivatives, acrylic acid or its derivate, methacrylic acid or its derivate, olefins, (meth)acrylonitriles, itaconic acid and its derivatives, maleic acid and its   \n35 derivatives, vinyl halides, vinylidene halides, fluoropolymers, and combinations thereof.  \n\nItem 35. The transparent composite or coating composition according to any one of items 28 to 34, wherein the adhesive polymer comprises a polymer or interpolymer prepared from 40 a fluoropolymer, and wherein the fluoropolymer is selected from the group consisting of PTFE, FPA, FEP, THV, ETFE, PVDF, and combinations thereof.  \n\nItem 36. The transparent composite or coating composition according to any one of items 28 to 35, wherein the adhesive polymer comprises a polymer prepared from an aqueous dispersion of condensation polymers.  \n\nItem 37.The transparent composite or coating composition according to any one of items 28 to 36, wherein the adhesive polymer comprises a polymer prepared from a polyurethane or polyester dispersion.  \n\nItem 38.The transparent composite or coating composition according to any one of the preceding items, wherein the anti-fog layer or coating composition further comprises a crosslinker.  \n\nItem 39.The transparent composite or coating composition 55 according to any one of the preceding items, wherein the anti-fog layer or coating composition further comprises a cross-linked network of polymers comprising a hard polymer, a hydrophilic polymer, and an adhesive polymer.  \n\nItem 40. The transparent composite or coating composition according to any one of the preceding items,wherein the anti-fog layer or coating composition further comprises an additive selected from the group consisting of surfactants, defoamers, coating aids, charge control agents, conductive particles, conductive polymers, thickeners, viscosity modifiers, coalescing aids, soluble and/or solid particle dyes, antifoggants, inorganic or organic fillers, matte beads, inorganic or polymeric particles, adhesion promoting agents, bite solvents, chemical etchants, lubricants, plasticizers, antioxilants, voiding agents, colorants, tints, roughening agents, sli igents, UV absorbers, refractive index matching material md combinations thereof.  \n\nItem 41. The transparent composite according to any one of the preceding items, further comprising a first transparent layer disposed adjacent the substrate layer.  \n\nItem 42. The transparent composite according to item 41, wherein the first transparentlayer comprises a fluoropolymer.  \n\nItem 43. The transparent composite according to any one of items 41 to 42, wherein the first transparent layer comprises a C-treated fluoropolymer.  \n\nItem 44. The transparent composite according to any one of items 41 to 43, further comprising a second transparent layer disposed adjacent the first transparent layer.  \n\nItem 45. The transparent composite according to item 44, wherein the second transparent layer comprises a fluoropolymer or polyvinyl chloride, or polyester, or polycarbonate, or cellulose acetate, or polyolefin.  \n\nItem 46. The transparent composite according to any one of items 44 to 45, wherein the second transparent layer comprises a C-treated fluoropolymer.  \n\nItem 47. The transparent composite according to any one of items 41 to 46, wherein the first transparent layer and the second transparent layer comprise the same polymer material.  \n\nItem 48. The transparent composite according to any one of the preceding items, wherein the transparent composite comprises a first adhesive layer disposed between the first transparent layer and the substrate layer; and a second adhesive layer disposed between the second transparent layer and the first transparent layer.  \n\nItem 49. The transparent composite according to item 48, 3( wherein the first adhesive layer, or the second adhesive layer comprises a polyurethane polymer.  \n\nItem 50. The transparent composite according to any one of items 48 to 49, wherein the first adhesive layer, or the second adhesive layer comprise a cured, crosslinked waterborne aliphatic polyurethane dispersion.  \n\n35  \n\nItem 51.The transparent composite according to any one of items 48 to 50, wherein the first adhesive layer, or the second adhesive layer comprise the same adhesive polymer as in the anti-fog layer.  \n\nItem 52.The transparent composite according to any one of items 48 to 51, wherein the first adhesive layer, or the second adhesive layer comprise a water soluble polymer, a hydrophilic colloid or a water insoluble polymer in the form of a latex or a dispersion.  \n\nItem 53. The transparent composite according to any one of $_{45}$ items 48 to 52, wherein the first adhesive layer, or the second adhesive layer comprise polymers and interpolymers prepared from ethylenically unsaturated monomers such as styrene, styrene derivatives, acrylic acid or its derivate, methacrylic acid or its derivate, olefins, (meth)acrylonitriles, itaconic acid and its derivatives, maleic acid and its deriva- 5 tives, vinyl halides, vinylidene halides, or fluoropolymers.  \n\nItem 54. The transparent composite according to any one of items 48 to 53, wherein the first adhesive layer, or the second adhesive layer comprise a polymer prepared from an aqueous dispersion of condensation polymers.  \n\nItem 55.The transparent composite according to any one of items 48 to 54, wherein the first adhesive layer, or the second adhesive layer comprise a polymer prepared from a polyurethane or polyester dispersion.  \n\nItem 56. The transparent composite according to any one of items 48 to 55, the first adhesive layer, or the second adhesive layer comprise a polymer having a glass transition temperature $\\left(\\mathrm{Tg}\\right)$ of no greater than 45 degrees Celsius, no greater than 20 degrees Celsius, no greater than 10 degrees Celsius, or even no greater than O degrees Celsius.  \n\nItem 57. The transparent composite according to any one of 6 the preceding items, wherein the composite comprises a substrate layer.  \n\nItem 58. The transparent composite according to any one of the preceding items, wherein the composite comprises a freestanding transparent substrate layer.  \n\nItem 59. The transparent composite according to any one of the preceding items, wherein the composite comprises a substrate layer comprising a polyvinyl chloride, a polyester, a fluoropolymer, a polycarbonate, or a polyolefin.  \n\nItem 60. The transparent composite according to any one of the preceding items, wherein a peel strength between the first transparent layer and substrate layer is at least about 2 pounds per linear inch (PLI), at least about 3 PLI, at least about 4 PLI, or even at least about 5 PLI as measured according to ASTM D1876.  \n\nItem 61. The transparent composite according to any one of the preceding items, wherein a peel strength between the second transparent layer and the first transparent layer is at least about 2 pounds per linear inch (PLI), at least about 3 PLI, at least about 4 PLI, or even at least about 5 PLI as measured according to ASTM D1876.  \n\nItem 62.The transparent composite according to any one of   \n0 the preceding items, wherein a bond between the outer layer and layer comprising a fluoropolymer has a bond strength of at least about 2 pounds per linear inch (PLI), at least about 3 PLI, at least about 4 PLI, or even at least about 5 PLI as measured according to ASTM D1876; and wherein a bond   \n5 between the layer comprising a fluoropolymer and the layer comprising a polymer has a bond strength of at least about 2 pounds per linear inch (PLI), at least about 3 PLI, at least about 4 PLI, or even at least about 5 PLI as measured according to ASTM D1876.  \n\nItem 63. The transparent composite according to any one of the preceding items, wherein the anti-fog layer has good adhesion to an adjacent layer as measured according to the Scotch Tape test.  \n\nItem 64. The transparent composite according to any one of the preceding items, wherein the anti-fog layer is non-tacky as determined by folding the layer over itself, separating the layer, and observing if the layer stuck to itself.  \n\nItem 65.The transparent composite according to any one of the preceding items, wherein the anti-fog layer passes a steam bath test.  \n\nItem 66. The transparent composite according to any one of the preceding items, wherein the composite does not delaminate as determined by flexing in a Gelbo tester for 2000 cycles.  \n\nItem 67.The transparent composite according to any one of the preceding items, wherein the anti-fog layer has $\\%$ VLTof at least $50\\%$ ，or atleast $70\\%$ ，or even at least $90\\%$ .  \n\nItem 68.A transparent composite comprising an anti-fog layer, wherein the anti-fog layer comprises a hydrophilic polymer and an anti-blocking agent comprising colloidal silica and/or an anionic fluorinated surfactant.  \n\nItem 69. An anti-fog coating composition comprising a hydrophilic polymer and an anti-blocking agent comprising colloidal silica and/or an anionic fluorinated surfactant.  \n\nItem 70. The transparent composite or coating composition according to any one of the preceding items, wherein the anti-fog coating composition and/or layer comprises an antiblocking agent.  \n\nItem 71.The transparent composite or coating composition according to any one of the preceding items, wherein the anti-fog coating composition and/or layer comprises an antiblocking agent comprising colloidal inorganic particles.  \n\nItem 72. The transparent composite or coating composition according to any one of the preceding items,wherein the anti-fog coating composition and/or layer comprises an antiblocking agent comprising colloidal silica.  \n\nItem 73. The transparent composite or coating composition according to any one of the preceding items,wherein the anti-fog coating composition and/or layer comprises an antiblocking agent comprising a fluorinated surfactant.  \n\nItem 74.The transparent composite or coating composition according to any one of the preceding items, wherein the anti-fog coating composition and/or layer comprises an antiblocking agent comprising an anionic fluorinated surfactant.  \n\nItem 75. The transparent composite or coating composition according to any one of the preceding items, wherein the anti-fog coating composition and/or layer comprises an antiblocking agent comprising a colloidal silica present in the anti-fog coating composition or the anti-fog layer in an amount of at least about 1 wt. $\\%$ , at least about 3 wt. $\\%$ ,oreven at least about 7 wt. $\\%$ , based on the total weight of the anti-fog coating composition or the anti-fog layer.  \n\nItem 76.The transparent composite or coating composition according to any one of the preceding items, wherein the anti-fog coating composition and/or layer comprises an antiblocking agent comprising a colloidal silica present in the anti-fog coating composition or the anti-fog layer in an amount of no greater than about 50 wt. $\\%$ ，no greater than about 40 wt. $\\%$ , no greater than about 30 wt. $\\%$ ，or even no greater than about 20 wt. $\\%$ ·  \n\nItem 77.The transparent composite or coating composition according to any one of the preceding items, wherein the anti-fog coating composition and/or layer comprises an antiblocking agent comprising a colloidal silica present in the anti-fog coating composition or the anti-fog layer in an amount in a range of from about 1 wt. $\\%$ to about 50 wt. $\\%$ . about 3 wt. $\\%$ to about 40 wt. $\\%$ ,or even about 7 wt. $\\%$ to about 30 wt. $\\%$ ，  \n\nItem 78. The transparent composite or coating composition according to any one of the preceding items, wherein the anti-fog coating composition and/or layer comprises an antiblocking agent comprising a fluorinated anionic surfactant present in the anti-fog coating composition or the anti-fog layer in an amount of at least about 0.o05 wt. $\\%$ ,at least about 0.01 wt. $\\%$ , or even at least about 0.03 wt. $\\%$ , based on the total weight of the anti-fog coating composition or the anti-fog layer.  \n\nItem 79. The transparent composite or coating composition according to any one of the preceding items, wherein the anti-fog coating composition and/or layer comprises an antiblocking agent comprising a fluorinated anionic surfactant present in the anti-fog coating composition or the anti-fog layer in an amount of no greater than about 15 wt. $\\%$ no greater than about 10 wt. $\\%$ , no greater than about 8 wt. $\\%$ ,or even no greater than about 2 wt. $\\%$ .  \n\nItem 80. The transparent composite or coating composition according to any one of the preceding items, wherein the anti-fog coating composition and/or layer comprises an antiblocking agent comprising a fluorinated anionic surfactant present in the anti-fog coating composition or the anti-fog layer in an amount in a range of from about 0.o05 wt. $\\%$ to about 15 wt. $\\%$ ,about 0.01 wt. $\\%$ to about 10 wt. $\\%$ ，or even about 0.03 wt. $\\%$ to about 8 wt. $\\%$  \n\nNote that not all of the activities described above in the general description or the examples are required, that a portion of a specific activity may not be required, and that one or more further activities may be performed in addition to those described.Still further, the order in which activities are listed is not necessarily the order in which they are performed.  \n\nBenefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, the benefits, advantages, solutions to problems, and any feature(s) that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential feature of any or all the claims.  \n\nThe specification and illustrations of the embodiments described herein are intended to provide a general understanding of the structure of the various embodiments. The specification and illustrations are not intended to serve as an exhaustive and comprehensive description of all of the elements and features of apparatus and systems that use the  \n\nstructures or methods described herein. Separate embodiments may also be provided in combination in a single embodiment, and conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. Further, reference to values stated in ranges includes each and every value within that range.Many other embodiments may be apparent to skilled artisans only after reading this specification. Other embodiments may be used and derived from the 0 disclosure, such that a structural substitution, logical substitution, or another change may be made without departing from the scope of the disclosure.Accordingly, the disclosure is to be regarded as illustrative rather than restrictive.  \n\nWhat is claimed is:  \n\n1.An anti-fog coating composition comprising an adhesive polymer, a hard polymer, and a hydrophilic polymer, wherein the adhesive polymer, hard polymer, and hydrophilic polymer are different, and the hard polymer has an elongation at break of at least $100\\%$ as measured according to ASTM D412, and a pencil hardness of at least 2H as measured according to ASTM D3363.  \n\n2. The anti-fog coating composition according to claim 1, wherein the adhesive polymer comprises a polymer having a Tg of less than about 45 degrees Celsius; and wherein the hydrophilic polymer comprises a polymer having a backbone and hydrophilic segments covalently bonded to the backbone.  \n\n3. The anti-fog coating composition according to claim 1,   \nwherein the hydrophilic polymer comprises a polymer having   \na polyurethane backbone and hydrophilic segments   \ncovalently bonded to the polyurethane backbone wherein the   \nhydrophilic segments comprise_alkylene oxides, lactones,   \nlactams, or combinations thereof. 4. The anti-fog coating composition according to claim 1,   \nwherein: the hydrophilic polymer is present in the anti-fog coating composition in an amount within a range of about 10 wt $\\%$ to about $90\\mathrm{wt}\\%$ based on the total dry weight of the anti-fog coating composition; the hard polymer is present in the anti-fog coating composition in an amount within a range of about 10 wt $\\%$ to about 80 wt $\\%$ based on the total dry weight of the anti-fog coating composition; and the adhesive polymer is present in the anti-fog coating composition in an amount within a range of about 10 wt $\\%$ to about $80\\mathrm{wt\\%}$ based on the total dry weight of the anti-fog coating composition. 5. The anti-fog coating composition according to claim 1,   \nwherein the hard polymer comprises a polymer or interpoly  \nmer prepared from ethylenically unsaturated monomers com  \nprising styrene, styrene derivatives, acrylic acid or its derivate, methacrylic acid or its derivate, olefins, (meth)   \nacrylonitriles, itaconic acid and its derivatives, maleic acid   \nand its derivatives, vinyl halides, vinylidene halides, fluo  \nropolymers, or combinations thereof. 6. The anti-fog coating composition according to claim 1,   \nwherein the adhesive polymer comprises a polyester or a   \npolyurethane. 7. The anti-fog coating composition according to claim 1,   \nwherein the anti-fog coating composition further comprises a   \ncrosslinker. 8.A transparent composite comprising: a substrate layer; and an anti-fog layer, wherein the anti-fog layer comprises an adhesive polymer, a hard polymer, and a hydrophilic polymer, wherein the adhesive polymer, hard polymer, and hydrophilic polymers are different, and the hard polymer has an elongation at break of at least $100\\%$ as measured according to ASTM D412, and a pencil hardness of at least 2H as measured according to ASTM D3363.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 24,
+        "chunk": "# 23  \n\n9. The transparent composite according to claim 8, wherein the transparent composite further comprises:  \n\na first adhesive layer; a first transparent layer; a second adhesive layer; and a second transparent layer. 10. The transparent composite according to claim 8,   \nwherein the transparent composite is in the form of personal   \nprotective equipment. 11. The transparent composite according to claim 9,   \nwherein a peel strength between the first transparent layer and   \nsubstrate layer is at least about 2 pounds per linear inch (PLI)   \nas measured according to ASTM D1876. 12. The transparent composite according to claim 8,   \nwherein the anti-fog layer is non-tacky as determined by   \nfolding the layer over itself, separating the layer, and observ  \ning if the layer stuck to itself. 13. The transparent composite according to claim 8,   \nwherein the anti-fog layer comprises an anti-blocking agent comprising acolloidal silica present in the anti-fog layer ina range of from about 3 wt. $\\%$ to about 40 wt. $\\%$ based on the total weight of the anti-fog layer; and/or wherein the anti-fog layer comprises an anti-blocking agent comprising a fluorinated anionic surfactant present in the anti-fog layer in an amount in a range of from about 0.01 wt. $\\%$ to about 10 wt. $\\%$ based on the total weight of the anti-fog layer.  \n\n14. The transparent composite according to claim 8, wherein the adhesive polymer comprises a polymer having a Tg of less than about 45 degrees Celsius; and wherein the hydrophilic polymer comprises a polymer having a backbone and hydrophilic segments covalently bonded to the backbone.  \n\n15. The transparent composite according to claim 8,   \nwherein: the hydrophilic polymer is present in the anti-fog layer in an amount within a range of about 10 wt $\\%$ to about 90 wt $\\%$ based on the total dry weight of the anti-fog layer; the hard polymer is present in the anti-fog layer in an amount within a range of about $10\\mathrm{wt}\\%$ to about 80 wt $\\%$ based on the total dry weight of the anti-fog layer; and the adhesive polymer is present in the anti-fog layer in an amount within a range of about $10\\mathrm{wt\\%}$ to about 80 wt $\\%$ based on the total dry weight of the anti-fog layer. 16. The transparent composite according to claim 8,   \nwherein the hydrophilic polymer comprises a polymer having   \na polyurethane backbone and hydrophilic segments   \ncovalently bonded to the polyurethane backbone wherein the   \nhydrophilic segments comprise alkylene oxides, lactones,   \nlactams, or combinations thereof. 17. The transparent composite according to claim 8,   \nwherein the hard polymer comprises a polymer or interpoly  \nmer prepared from ethylenically unsaturated monomers com  \nprising styrene, styrene derivatives, acrylic acid or its deri  \nvate, methacrylic acid or its derivate, olefins, (meth)   \nacrylonitriles, itaconic acid and its derivatives, maleic acid   \nand its derivatives, vinyl halides, vinylidene halides, fluo  \nropolymers, or combinations thereof. 18. The transparent composite according to claim 8,   \nwherein the adhesive polymer comprises a polyester or a   \npolyurethane. 19. The transparent composite according to claim 8,   \nwherein the anti-fog layer further comprises a crosslinker.",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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+++ b/task2/task2-chunks/Advanced Materials - 2024 - Ng - Progress and Opportunities for Machine Learning in Materials and Processes of Additive.json	
@@ -0,0 +1,187 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Progress and Opportunities for Machine Learning in Materials and Processes of Additive Manufacturing  \n\nWei Long Ng,\\* Guo Liang Goh, Guo Dong Goh, Jyi Sheuan Jason Ten, and Wai Yee Yeong\\*  \n\nIn recent years, there has been widespread adoption of machine learning (ML) technologies to unravel intricate relationships among diverse parameters in various additive manufacturing (AM) techniques. These ML models excel at recognizing complex patterns from extensive, well-curated datasets, thereby unveiling latent knowledge crucial for informed decision-making during the AM process. The collaborative synergy between ML and AM holds the potential to revolutionize the design and production of AM-printed parts. This review delves into the challenges and opportunities emerging at the intersection of these two dynamic fields. It provides a comprehensive analysis of the publication landscape for ML-related research in the field of AM, explores common ML applications in AM research (such as quality control, process optimization, design optimization, microstructure analysis, and material formulation), and concludes by presenting an outlook that underscores the utilization of advanced ML models, the development of emerging sensors, and ML applications in emerging AM-related fields. Notably, ML has garnered increased attention in AM due to its superior performance across various AM-related applications. It is envisioned that the integration of ML into AM processes will significantly enhance 3D printing capabilities across diverse AM-related research areas.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1. Introduction  \n\nIn recent years, the growing interest in machine learning (ML) has been driven by a convergence of technological advancements, data availability, community collaborations, and its practical applications in various domains. ML, a subset of artificial intelligence, empowers systems to learn from data, recognize patterns, and make intelligent decisions.[1] There are four types of ML algorithms (Table 1): supervised learning,[2] unsupervised learning,[3] semi-supervised learning[4] and reinforcement learning.[5] Supervised learning learns from a labeled dataset (input-output pairs) and creates a mapping between the input data and the corresponding output, allowing the algorithm to make predictions when presented with new data. Although supervised learning requires a lot of human effort and domain knowledge to label the data and define the goal, it can produce accurate predictions with repeated training iterations with large relevant dataset, and has found applications in various industries such as sports[6] and robotics.[7] In contrast, unsupervised learning is trained on a dataset without labeled output. It aims to find patterns or relationships within the large and complex data without human intervention. Semi-supervised learning is an ML algorithm that combines the elements of both supervised and unsupervised learning; it is trained on a dataset that contains both labeled and unlabeled data to improve the model performance. It makes efficient use of available data and reduces the reliance on costly labeled data to achieve good performance. Lastly, reinforcement learning focuses on regimented learning processes, whereby the algorithm undergoes a trial-and-error process based on the provided set of actions, parameters, and end values to achieve the best possible result.  \n\nAdditive manufacturing (AM), often known as 3D printing, has revolutionized the field of manufacturing by enabling the fabrication of customized, complex 3D structures in a layer-bylayer manner. It can be categorized into seven main groups based on ISO/ASTM 52900:2021: 1) binder jetting, 2) directed energy deposition, 3) material extrusion, 4) material jetting, 5) powder bed fusion, 6) sheet lamination, and 7) vat photopolymerization. When applied to AM, ML opens new avenues for enhancing the entire manufacturing process, from material formulation, design optimization, and process optimization to quality control. The synergy between ML and AM has the potential to revolutionize the way AM-printed parts are designed or produced. By harnessing the vast amount of generated data, ML algorithms can unlock deeper insights into AM processes such as optimizing designs, predicting material properties, or even improving production quality (Figure 1).  \n\nTable 1. Different classifications of ML techniques.   \n\n\n<html><body><table><tr><td>Category</td><td>Techniques</td></tr><tr><td>Supervised Learning</td><td>Linear Regression</td></tr><tr><td></td><td>Logistic Regression</td></tr><tr><td></td><td>Support Vector Machine</td></tr><tr><td></td><td>Decision Trees (e.g., Classification and</td></tr><tr><td></td><td>Regression Tree) Random Forest</td></tr><tr><td></td><td>Gradient Boosted Trees (e.g., XGBoost, LightGBM, CatBoost)</td></tr><tr><td></td><td>Neural Networks (e.g., DNN, RNN, U-Net,</td></tr><tr><td></td><td>RandLA-Net, LSTM) K-Nearest Neighbours (K-NN)</td></tr><tr><td></td><td>Gaussian Process Modelling</td></tr><tr><td></td><td>Ensemble learning (e.g.,Adaboost, Bayes</td></tr><tr><td></td><td>optimal classifier, bagging, stacking)</td></tr><tr><td>Unsupervised Learning</td><td>K-means Clustering</td></tr><tr><td></td><td>Hierarchical Clustering</td></tr><tr><td></td><td>Principal Component Analysis (PCA)</td></tr><tr><td></td><td>Independent Component Analysis (ICA)</td></tr><tr><td></td><td>Autoencoders (e.g.,variational autoencoder)</td></tr><tr><td></td><td>Gaussian Mixture Models</td></tr><tr><td>Semi-supervised Learning</td><td>Self-training</td></tr><tr><td></td><td>Multi-view Training</td></tr><tr><td></td><td>Generative Adversarial Networks (GANs)</td></tr><tr><td></td><td>Domain Adversarial Neural Network</td></tr><tr><td>Reinforcement Learning</td><td>Q-learning</td></tr><tr><td></td><td>Deep Q Networks (DQN)</td></tr><tr><td></td><td>Monte Carlo Methods</td></tr><tr><td></td><td>Policy Gradient Methods</td></tr><tr><td></td><td>Actor-Critic</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2. Publication Landscape for ML in AM  \n\nAn analysis of the publication landscape was conducted to determine the influence of ML on different 3D printing techniques using the following set of keywords on Web of Science (“machine learning” $+\\ {}^{\\mathrm{~\\tiny~4~}}3\\mathrm{D}$ printing/additive manufacturing” $^+$ “printing technique”). As there are many variants of 3D printing technique under each ASTM classification, numerous keywords for each printing technique were used: 1) binder jetting—binder jetting, multi-jet fusion; 2) directed energy deposition—directed energy deposition, wire arc additive manufacturing; 3) material extrusion—extrusion, fused deposition modeling, fused filament fabrication, direct ink writing; 4) material jetting—jetting, inkjet, microvalve; 5) powder bed fusion—powder bed fusion, selective laser sintering, selective laser melting, electron beam melting, laser powder bed fusion; 6) sheet lamination—sheet lamination; and 7) vat photopolymerization—vat photopolymerization, stereolithography, digital light processing (DLP), and continuous liquid interface production. As shown in Figure 2a, a total of 528 ML-related AM publications were published over the last 10 years and the adoption of ML for each 3D printing technique varies— powder bed fusion (225 publications) $>$ material extrusion (135 publications) $>$ material jetting (80 publications) $>$ directed energy deposition (59 publications) $>$ vat photopolymerization (20 publications) $>$ binder jetting (8 publications) $>$ sheet lamination (1 publication). The ML-related AM research has grown substantially over the last ten years; it has increased significantly from one publication in the year 2013 to 213 publications in the year 2022 (Figure 2b).  \n\nAs ML is prevalently used in AM processes, further analysis was conducted on Web of Science to determine some common ML applications in AM research using the following set of keywords (“machine learning” $+\\ensuremath{}^{\\mathrm{*}}3\\ensuremath{\\mathrm{D}}$ printing/additive manufacturing” $+$ “application”). The top five most common ML applications in AM research over the last 10 years include 1) Quality control (301 publications), 2) Process optimization (222 publications), 3) Design optimization (183 publications), 4) Microstructure analysis (45 publications), and 5) Material formulation (14 publications) (Figure 2c). These ML applications are applied in various key AM-related research areas such as aerospace and defense, bioprinting, construction printing, drug printing, electronics printing, and marine and offshore and unmanned aerial vehicles (Figure 2d). A more in-depth discussion of these five common ML applications and their specific roles in different key AMrelated research areas will be presented in subsequent sections.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# 3. Common ML Applications in AM Research  \n\nOver the years, ML has attracted increasing attention in AM due to its superior performance in different applications such as quality control, process optimization, design optimization, microstructure analysis, and material formulation. In-depth discussion on the common ML applications will be categorized based on their AM technique to provide a comprehensive overview of how machine learning can be applied to each specific AM technique, thereby highlighting the unique challenges and solutions that each method presents.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 3.1. Quality Control  \n\nQuality control plays a crucial role in enhancing the efficiency and reliability of additive manufacturing processes. Many studies have explored the application of ML algorithms and sensor data analysis to achieve real-time process monitoring and quality assurance. Signals from in situ sensors are used to train ML models to monitor the stability of the process and detect defects within successful builds. Different ML techniques (supervised, unsupervised, semi-supervised, and reinforcement learning) have been used for quality control in AM; the choice of ML approach for quality control is dependent on the nature of the data and the objectives of the quality control system. Supervised learning is most used ML technique for quality control in AM and most of the studies demonstrated high prediction accuracies $>90\\%$ . Although it is well-suited for quality control with labeled historical data from both good and defective products/processes, it may not be useful for the detection of novel defects or anomalies not seen in the training data. Figure 3 provides a summary of the techniques involved and applications of ML in quality control and more discussion on the different types of ML used in quality control will be provided in the subsequent sections.  \n\n![](images/bbb4953cd3e360d7f7011a42c79ded52481970a0d6f7e2883e5984c18e03abd7.jpg)  \ntypes—supervised, unsupervised, semi-supervised, and reinforcement learning—while introducing the emerging transformer model for ML applications. On the right, various AM techniques are detailed. The central part of the figure illustrates the potential benefits that ML can offer to AM and the bottom part showcases practical applications across a wide range of industries, from aerospace and defense to electronics, and food, underscoring the extensive impact of integrating ML with advanced manufacturing methods. Reproduced with permission.[53,76,115,176] Copyright 22 Mar 2024, Elsevier.  \n\n![](images/b7d59caa22485ea140b020b1d071fb71681f1057160770599f879226aeefbc18.jpg)  \nFigure 2. a) Number of ML-related additive manufacturing publications over the past 10 years. b) Detailed annual breakdown of the number of publications for each printing technique from years 2013 to 2022. c) Detailed annual breakdown of the number of publications for different ML applications in AM from years 2013 to 2022. d) Detailed annual breakdown of the number of publications on ML applications in various key AM research areas from years 2013 to 2022.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 3.1.1. Powder Bed Fusion  \n\nIt is common to observe high porosity, balling, incomplete fusion, and spattering during the AM process. These defects arise from factors such as process instability and poor material interactions. Such defects are detrimental to the quality of printed parts, leading to compromised mechanical strength, surface roughness, inaccurate geometries, and potential delamination. It is important to address these defects to ensure the reliability and performance of AM-fabricated components across industries.[8]  \n\n![](images/9494de93ad1fbdb1bae57342c0d447478089600d01f1fb6e5d196a31e9c233fd.jpg)  \nFigure 3. Graphical overview summarizing the diverse applications of ML in quality control across various AM processes.  \n\nTo monitor the process stability, a study used data from the supplied EOS M290 powder bed images to predict anomalies during the powder spreading process (Figure 4).[9] The powder-based materials included Ti6Al4V, AlSi10g, IN718, SS316L, SS17-4, and bronze. The images were first filtered using 37 different 2D image processing filters, and the filter responses were stored in vectors for each pixel. The response vectors were then grouped into 100 groups using a standard k-means unsupervised clustering algorithm. The mean response vector for each group was then stored as visual words in a dictionary. Then, the pixel at each training image patch was matched to the closest visual word, and the histogram for the occurrence frequency of each word in the patch was calculated and termed “fingerprints”. The rationale was that training images with similar powder-spreading anomalies would result in similar “fingerprints”. During the method execution, the powder bed image was divided into different patches and the “fingerprint” from each patch was then calculated. The quality of a patch was determined by matching its “fingerprint” to a database of 2402 “fingerprints”. These “fingerprints” were manually labeled under six conditions: anomalyfree: 1040 “fingerprints”, recoater hopping: 264 “fingerprints”, recoater streaking: 228 “fingerprints”, debris: 187 “fingerprints”, super-elevation: 314 “fingerprints”, part failure: 264 “fingerprints”, incomplete spreading: 105 “fingerprints”. The top three matches from this database were then used to assess the patch’s quality. The algorithm managed to classify the powder spreading based on the six conditions with precision ranging from $65.0\\%$ to $98.9\\%$  \n\n![](images/3edb327fafa0c8064fc3b8e68401904cf324b1b386f8b963437bced715b543cd.jpg)  \nFigure 4. Flow chart of ML process to detect anomaly in laser powder bed fusion. Reproduced with permission.[9] Copyright 2018, Elsevie  \n\nFor defect detection in laser powder bed fusion (LPBF) builds, various sensor technologies were used in conjunction with ML techniques. These technologies included visible light cameras, infrared cameras, high-speed cameras, photodiodes, and acoustic sensors. There were also efforts that combined multiple sensor technologies for ML training. Using a high-resolution 36.3- megapixel digital single-lens reflex (DSLR) camera, images of each layer were taken before and after LPBF laser scanning to predict the locations of voids.[10] Multiple images were taken under different lighting conditions for each build layer and were combined using an ensemble classification. It was possible to combine data from multiple sensors through the ensemble technique instead of only using data from a single sensor under different conditions. The ground truths were obtained from X-ray computed tomography (CT) convolved with a Gaussian filter and labeled using support vector machine (SVM) binary classifiers before being manually checked by a certified non-destruction inspection inspector. The ensemble method improved the accuracy of prediction from $65\\%$ to $85\\%$ for single sensor image input to $85\\%$ for multiple images.  \n\nA four-phase (sliding, convolutional neural networks (CNN), smoothing, and compensation) modeling approach was developed for online surface measurement in additive manufacturing.[11] This approach utilized a window-based data reformulation technique and CNN to predict 3D surface data directly from 2D images without the need for time-consuming triangulation computations. The method proved to be highly accurate, with an average relative prediction error mostly lower than $10\\%$ . Its computational efficiency and ability to acquire data layer-wise in real-time made it suitable for online quality monitoring and control in additive manufacturing processes.  \n\nIn-process monitoring using infrared cameras followed by ML for data analysis was performed using the original equipment manufacturer and customized hardware.[12] The EOSTATE Exposure OT captured a long exposure image at ${\\approx}900\\ \\mathrm{nm}$ of the laser scanning over one whole layer. Both groups changed the process parameters to create the training dataset. The unsupervised Kmeans clustering was used to enlarge the manually labeled training dataset followed by $\\mathrm{\\Deltak}$ -nearest neighbors (K-NN) supervised learning to identify anomalies (drifts) in the images.[12a] These anomalies were then shown to have a correlation with high porosity occurrence in X-ray CT scans of the actual samples. Random forest-bagged tree ensemble labeled with X-ray CT data are used (Figure 5) and the use of multiple consecutive layers improved the prediction accuracy. The interpretability of the random forest (RF) model showed that the lack of fusion defects prediction was dependent on the adjacent layers while keyhole defects prediction was heavily dependent on the $10^{\\mathrm{th}}$ subsequent layer. The model could determine the average density of a small area measuring $1\\mathrm{mm}\\times1\\mathrm{mm}$ .  \n\nAn infrared thermographic camera was integrated to an SLM 280 LPBF system to capture short videos of delamination, splatters, and defect-less processes that were then converted to image frames to train a CNN.[13] The training dataset was augmented by rotating the image, flipping the images, and random image noise and blur. Delamination and splatter defects were detected at an average accuracy of $96.8\\%$ .  \n\nHigh-speed cameras with frame rates above $1000~\\mathrm{Hz}$ in the visible and infrared range were also used as inputs for ML models. A short wavelength infrared high-speed camera was used to capture the thermal history of the part and train a customized CNN for the identification of defect locations within the part.[14]  \n\n![](images/4a1907f3c768e56c42ec45d9483a3709e6838329b279e05d484b79b19893accb.jpg)  \nFigure 5. Workflow of training the ML model using labeled X-ray CT data. Initially, a compilation of through-process data encompassing Computer-Aided Design (CAD), processing parameters, real-time online monitoring data captured via Optical Tomography (OT) images, and subsequent post-processing characterization data derived from X-ray Computed Tomography (CT) was performed. Subsequently, an ML model was developed to glean valuable insights into the mechanisms underlying defect generation. The adeptly trained ML model is proficient in accurately forecasting porosity occurrences within individual layers, leveraging the composite data from multiple layers of OT information. Reproduced with permission.[12b] 2022, Elsevier.  \n\nMelt-pool and time-dependent attributes were extracted from the thermal images for groups of pixels and a threshold was set for a binary outcome of pore and non-pore groups. The data was labeled in comparison to X-ray CT data with details from their previous work[15] and a 1D CNN model was trained using Bayesian Optimization. It was found that a group of pixels representing a volume of $700\\times700\\times50~\\upmu\\mathrm{m}$ produced the best prediction accuracy for keyhole porosities above $0.1\\%$ in volume and decreasing the volume size reduced the prediction accuracy. A highspeed visible light camera at $6{,}400~\\mathrm{Hz}$ was used to capture melt pool images.[16] The feature extraction, classification, and subsequent unsupervised ML model training were similar to another work for build failure detection and modifications were made to achieve a scale-invariant representation of the melt pool morphology.[9] The “fingerprints” that were identified for five outcomes include desirable, under-melting, keyhole porosity, severe keyhole porosity, and balling. Two infrared (IR) high-speed cameras at 700 and ${950}\\mathrm{nm}$ wavelengths respectively were used to take images of melt pools at $100~\\mathrm{kHz}$ (Figure 6).[17] Multiple feature types from the raw sensor data and calculated thermal field were extracted to train various ML models ranging from KNN, SVM, to CNN. The algorithms were used to 1) detect out-offocus laser and 2) porosity level and were able to achieve a true positive rate of $90\\%$ . The computationally light ML models produced subpar results when trained on single feature types but generated on-par results with the deep learning models when trained on inputs from the multiple feature types (melt pool morphology, spatter characteristics, and melt pool temperature features).  \n\nOne of the challenges for training ML models with high-speed camera data was the difficulty in volumetrically matching the ground truth data typically obtained by X-ray CT. Synchrotron Xray imaging was used to obtain real-time defect formation data for comparison with the in situ visible and NIR imaging above $50~\\mathrm{kHz}$ instead of measuring the defects after the process.[18] The frequency response of the intensity of the high-speed camera images was grouped into wavelets shorter than 1 ms for training a deep neural network model to identify pore and non-pore events. Simulation models were then used to provide further insights into the pore formation mechanism. The developed simulation model was then used to generate data to train a deep learning model for a high-speed camera integrated into a commercial LPBF system SLM 280. Accuracies up to $87\\%$ were obtained for identifying the pores.  \n\nDue to the limited penetration depth of visible and IR waves in metals, the signals obtained from electromagnetic emissions of these wavelengths typically only capture signals from the surface of the metal during the process. Besides using synchrotron X-ray to penetrate the metal, others have captured acoustic emissions to potentially detect process signals originating from below the metal surface. A microphone was secured $25{-}30~\\mathrm{cm}$ on top of the build plate to sample acoustic emissions at $100~\\mathrm{kHz}$ .[19] Features from the signal were extracted based on three primary groups: time-series statistics, frequency domain characteristics, and oscillatory modes via an ensemble empirical mode decomposition technique. An SVM was then trained based on X-ray radiograph ground truths for signal windows of $1{-}15\\ \\mathrm{ms}$ . A window of $7.5~\\mathrm{ms}$ showed the best accuracy of $97\\%$ in predicting keyhole pore and keyhole-free scan lengths that corresponded to the window. A sensor measuring a wideband of $100{-}900~\\mathrm{kHz}$ at the center bottom of a circular build plate was used to detect acoustic emissions from coupons separated radially from the sensor.[20] The noise from the acoustic signal was first removed and three methods were explored: $\\mathrm{k\\Omega}$ -means, principal component analysis, and a general deep learning. Kmeans clustering achieved a $90\\%$ prediction rate when paired with a deep learning classifier, cracks were detected using principal component analysis and lastly the general deep learning model (trained on raw H13 signals) demonstrated good adaptability for prediction when tested on SS316L data. A 1D CNN model accurately detected the spattering event in the LPBF process up to $85\\%$ (Figure 7a).[21] Conversely, acoustic emission from the powder bed fusion process was used to predict possible defect formation within the printed parts (Figure 7b).[22] The developed model was able to predict different types of defects (lack of fusion pores, conduction mode, and keyhole pores) within different materials (316L stainless steel, bronze $\\scriptstyle(\\mathrm{CuSn8})$ , and Inconel 718) with an accuracy of ${\\approx}93\\%$ . It was challenging to collect the acoustic emissions as the signal passed through the previously melted layers and the build plate to reach the sensor. Another study collected the acoustic signals via an optoacoustic fiber Bragg grating with sampling rates up to $10~\\mathrm{MHz}$ .[23] Reinforcement learning was used to recognize acoustic emissions from three classes of material: poor quality, medium quality, and high quality, and achieved detection accuracies above $74\\%$ . A monitoring strategy for LPBF process was developed using a hybrid deep learning (DL) model that combined CNN and long–short-term memory (LSTM) (Figure 8).[24] The proposed model achieved high prediction accuracy ranging from $95.9\\%$ to $100\\%$ in classifying lack of fusion, conduction mode, and keyhole across various time scales, based on data from a heterogeneous time-synced sensing system. The study emphasized the importance of back reflection and structure-borne acoustic emission sensors in the decision-making process. Although the model demonstrated high accuracy, further validation is necessary for complex geometries and scanning paths, other types of defects, and optimization of hardware and data collection pipeline, and the inclusion of physics-based inference from the trained models.  \n\n![](images/79e755e99fd0d8197e67560ec4538b15613ba8f4cfb18ceff5cfbfb91f4615ef.jpg)  \nFigure 6. Diagram illustrating the diverse physics-derived attributes extracted from various sensing methods, which are then used to train the CNN architecture. A visual depiction of the efficacy of various models in classifying a) the size of the laser spot and b) the kind of porosity, measured using the F1-score. RRC stands for ridge regression classifier, NLR denotes nonlinear logistic regression classifier, SVM represents support vector machine classifier, and CNN signifies convolutional neural network classifier. Adapted with permission.[17] 2022, Elsevier.  \n\n![](images/54a13c5de91719a6eee41f59164607cc323de407ae69cd7e0071335ff6c43097.jpg)  \nFigure 7. a) Schematic showing the ID-CNN model that is used for detecting spattering event using acoustic signal. Reproduced with permission.[21] 2021, MDPI. b) Schematic showing the flowchart of model that is used for detecting various types of defects using acoustic signal. Reproduced with permission.[22] 2022, Taylor & Francis.  \n\nThe previous studies were either based on derived or raw data taken from one sensor type. There were also efforts to use ML for multiple sensor types to achieve improved defect detection rates. Sensor data from the optical layer images, process multispectral emission, and the vector scan path of the laser were combined (Figure 9).[25] The combined sensor data input was trained against X-ray CT ground truths in a CNN model to classify volumes of $940~{\\upmu\\mathrm{m}}\\times940~{\\upmu\\mathrm{m}}\\times660~{\\upmu\\mathrm{m}}$ into flaw and nominal build regions. The training accuracy was $97.3\\%$ when trained solely on multi-spectral emissions but decreased to $88.7\\%$ for the test dataset. Similarly, the training accuracy was $97.0\\%$ when trained on all data modalities but decreased to $91.9\\%$ for the test dataset.  \n\n![](images/c02a2c9cc70763cd8b88b61dfe746c4062dff3cb7d9e1c38aa5333a343c03f18.jpg)  \nFigure 8. Overview of the variable time scale monitoring of LPBF using a hybrid DL model. The proposed DL model can operate over variable time scales for LPBF monitoring. A hybrid DL architecture combining CNN and LSTM was introduced. Heterogeneous signals, including optical and acoustic emissions from the process zone, were used to train the DL model. The DL model demonstrated accurate classification of lack of fusion, conduction, and keyhole regimes within time scales ranging from 0.5 to $4m s$ . Adapted with permission.[24] 2022, Elsevier.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 3.1.2. Material Extrusion  \n\nMaterial extrusion, a prevalent additive manufacturing technique, is prone to specific defects that impact the quality of printed parts. Common defects include layer misalignment caused by inaccurate deposition, voids stemming from incomplete material fusion, inconsistent extrusion leading to irregular wall thickness, and delamination due to weak adhesion between layers. These defects are dependent on factors like improper temperature control, inadequate material flow, and incorrect print settings. These undesirable defects compromise the structural integrity, mechanical strength, and dimensional accuracy of printed parts, making defect mitigation essential for producing reliable and functional components.  \n\nTo improve print quality and consistency of fused filament fabrication (FFF) processes, an innovative approach to quality assurance in additive manufacturing processes was implemented by leveraging environmental data and ML.[26] Various environmental parameters (temperature, humidity, air pressure, and gas particles) were recorded and analyzed during fused deposition modeling (FDM) processes and different ML algorithms (multilayer perceptron (MLP), 1D CNN, RNN, LSTM, Inception Time, XceptionTime, and eXplainable CNN for multivariate time series classification (XCM)) were employed for classification. The XceptionTime architecture was found to be the most effective, achieving a minimum accuracy of $95\\%$ with both small and large datasets. This ML algorithm provided faster and cheaper quality assurance compared to traditional optical 3D scan methods.  \n\nNozzle clogging is also a common issue when dealing with fiber-reinforced polymers. Nozzle clogging is usually undetected by the printer and would cause an eventual print failure. A multihead encoder-decoder temporal convolutional network (MH-EDTCN) algorithm utilized time-series data from collaborative sensors to detect nozzle clogging.[27] This algorithm outperformed other ML approaches including SVM, LSTM, LSTM autoencoder, and a simple CNN to achieve a remarkable $97.2\\%$ accuracy in identifying nozzle clogging. Further improvements to the algorithm were also recommended and the addition of appropriate sensors addressed the printing malfunctions caused by the viscoelastic behavior of polymer materials. Although prediction of nozzle clogging can be performed using ML approaches, it is challenging to predict the quality of extruded materials from the nozzle. To solve that, image-based anomaly detection techniques were developed to realize real-time monitoring and correction. Image classification model[28] and object detection models[29] were used to predict under-extrusion and over-extrusion phenomena during the FDM process and accuracies of $98.0\\%$ and $89.8\\%$ were achieved respectively. The system outperformed human response times in detecting and correcting defects. The framework proposed can be extended to other 3D printing technologies for fabricating high-performance materials in challenging environments without human intervention.  \n\n![](images/5ad789b6a4fafa669a973e48a0e97971675a39fc605f81772dffec480bb65ed0.jpg)  \nFigure 9. A Convolutional Neural Network (CNN) design for defect identification uses 3D image slices from M different sensor types. This network is structured with two convolutional phases followed by a dense layer comprising one hidden layer. The model’s output predictions are produced through a softmax classification layer. Bar chart showing sensor fusion performing better than the individual layer-wise optical layer images, process multi-spectral emission, and the vector scan path of the laser. Reproduced with permission.[25] 2022, Elsevier.  \n\nA study was performed to diagnose faults and identify causes, particularly regarding the drift of process parameters. A deep adversarial learning system that utilized captured upper-layer images during the manufacturing process was proposed.[30] It employed a conditional generative adversarial network (CGAN) to address data imbalance and a domain adversarial neural network (DANN) to handle domain-shifting problems caused by drifting process parameters. The experimental validation demonstrated the effectiveness and accuracy $(91.01\\%)$ of the proposed method. Although many approaches have been developed to provide automated monitoring, current automated methods cannot be universally applied to various components, materials, and printing systems. A study focused on generalizing the 3D printing defects and correcting errors in material extrusion additive manufacturing (Figure 10).[31] A multi-head neural network trained on a large and diverse dataset $(\\approx1.2$ million images) was developed to identify deviations from optimal printing parameters. The system allowed for real-time error detection and rapid correction across different printing scenarios. The trained network achieved an overall accuracy of $84.3\\%$ in classifying the flow rate, lateral speed, Z offset and hot end temperature and demonstrated the effectiveness of gradient-based visual explanations for understanding network decisions. The methodology offered a cost-effective and scalable solution that can be easily integrated into existing printers and workflows, leading to improved quality and reliability of end-use products (Figure 11).  \n\nDefect detection is critical for large-scale printing due to the high cost involved, especially so in building and construction. A study has demonstrated automated layer defect detection in construction 3D printing using deep CNN.[32] The system comprised a deep CNN model that took images as input and distinguished concrete layers from surrounding objects via semantic pixel-wise segmentation. Data augmentation techniques generated 1 million images for training, tuning, and testing the CNN model. Furthermore, a defect detection module was developed to detect deformations in the printed concrete layers using the images output by the CNN model. The evaluation results showed a high level of accuracy and F1 score $(>90\\%)$ in differentiating concrete and non-concrete pixels, while the defect detection module achieved a total accuracy of $97.5\\%$ and a miss rate of less than $6\\%$ for printed layers with and without defects. A similar study with fewer images resulted in poorer performance of $80\\%$ mean average precision.[33] These studies demonstrated the potential of computer vision and deep learning techniques for automated inspection and quality monitoring in construction 3D printing.  \n\nIn construction printing, the bigger size (cm-scale) of the extrudate allowed the utilization of 3D scanners for detecting deformations in printed structures.[34] This was unlike smaller-scale polymer printing (in mm scale) where the precision of 3D cameras imposed limitations on this capability. A study evaluated the performance of a monocular camera, LiDAR, and LiDAR-camera in terms of point cloud density and 3D map reconstruction for defect detection. The results showed that the RGB-L camera outperformed the other sensors in all scenarios, with an error below $4\\%$ when using K-means clustering at a distance of $0.5\\mathrm{m}$ .  \n\n![](images/f5e901cee0c788cbbaf40b9cac0751029717a1798d27eb10d212eabbabe2b598.jpg)  \nFigure 10. a) The feedback pipeline consists of six key steps that facilitate the online updating of parameters based on image data obtained during the extrusion process. b) The provided table presents the values for $\\theta_{\\sf m o d e}$ (mode threshold), L (sequence length), $I_{\\min}$ (interpolation minimum), $\\mathsf{A}^{+}$ (maximum increase), and $\\mathsf{A}^{-}$ (maximum decrease) for each printing parameter, along with the corresponding possible levels of update amounts. c) A simple example is presented to illustrate the geometric structure of a single layer and the subdivision of the toolpath into smaller segments of equal length. This subdivision, using $\\mathsf{1\\ m m}$ segments, enables swift correction and reduces the response time in the feedback process. Reproduced with permission.[31] 2022, Nature Portfolio.  \n\nHowever, the execution time of the algorithm was currently too high for real-time applications. It was suggested that future work can focus on validating the system by analyzing concrete printed areas, incorporating color information to better identify points belonging to each printed layer, and developing the more advanced algorithm in $\\mathrm{C/C^{++}}$ to reduce computational cost and enable real-time applications.  \n\nA novel methodology for real-time quality assurance in 3Dprinted electronics using U-Net was presented.[35] An FFF printer equipped with an extruder was used for conductive paste dispensing, pick-and-place unit, and dual cameras. The cameras captured images during the printing process and a trained neural network was used to distinguish the conductive wires from the plastic substrate. The method was used to identify common printing flaws such as connection breaks, shorts, and inaccuracies in wire width, comparing the actual output with the intended Gcode instructions with an overall accuracy of $96.6\\%$ . The results facilitated high-resolution documentation and provided data to improve the printing process. This innovation enabled the detection of errors and can be potentially used for automated flaw rectification, paving the way for more reliable and autonomous 3D-printed electronics production.  \n\nIn situ monitoring is commonly implemented during the bioprinting process to improve the dimensional accuracies of 3Dbioprinted tissue constructs. The error (missing or excess material) within each printed layer is compounded with increasing layers and it would lead to poor dimensional accuracies for large 3Dbioprinted tissue constructs, which typically require a long printing time and involve high material cost. The CNN-based classifiers are typically utilized for defection detection in most manufacturing processes; they can be implemented to monitor and improve the printing outcome in 3D bioprinting processes using computer vision. The captured images can be labeled as “underextrusion”, “good-quality” and “over-extrusion” images for training. A DL model can be used to optimize the printing parameters iteratively and adaptively using a real-time in situ monitoring and correction system. An ad hoc optimized CNN and a mathematical model were used to perform in-process and parameter optimization of the extrusion-based bioprinting process.[36] The dataset was constructed by capturing videos of multi-layered scaffolds fabricated using the extrusion bioprinting process; the inputs include type of extrusion system (pneumatic or mechanical), type of material, layer thickness, and infill density while the output is based on extrusion multiplier (which represents the ratio of printing resolution to nozzle diameter). The printing quality can be optimized by tuning the printing parameters through a series of consecutive prints in a feedback loop manner using the CNN model. The results showed an accuracy of $94.3\\%$ for overall printing; acceptable printing has a precision of $87.2\\%$ and recall of $96.5\\%$ , over-extrusion has a precision of $98.3\\%$ and recall of  \n\n![](images/4c3d5d921bb086bf172db877095815dce0e316dc2bd8cdaaf44da661baa7dbd3.jpg)  \nFigure 11. a) The multi-head neural network allows for quick correction of errors caused by manual intervention in a single parameter. It has been trained on a particular printer and PLA feedstock. The correction procedure is used on a hidden $0.4~\\mathsf{m m}$ nozzle that was not part of the training set of data. b) The control pipeline shows that multiple incorrect parameters for thermoplastic polymers that were not seen during the training phase can be simultaneously optimized online. This demonstrates the system’s adaptability to a variety of feedstocks with various material characteristics, colors, and initial conditions. c) The system uses self-learned relationships between parameters to make rrective predictions, much like human operators do. By decreasing the Z offset value and/or increasing the material flow rate, for example, a high Z offset can corrected. d) The system successfully fixes numerous wrong printing parameters that were added during a print job. The only difference between the two identical rooks printed under the same circumstances was how the correction process was used. e) Prints started with the wrong parameter combinations ar successfully handled by the system. The same conditions were used to print a set of six spanners, demonstrating the system’s capacity to correct mistakes and produce the desired results. Reproduced with permission.[31] 2022, Nature Portfolio.  \n\n$94.5\\%$ and lastly under-extrusion has a precision of $97.6\\%$ and recall of $92.2\\%$ .  \n\nThese research efforts collectively demonstrate the growing potential of ML and computer vision in automating quality inspection and monitoring in a material extrusion process. By addressing the limitations of manual inspection methods, these advanced solutions offer enhanced accuracy, efficiency, and the potential for real-time applications. Further developments in dataset size, sensor technology, and algorithm optimization hold promise for broader adoption and improved quality control in the field of AM.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 3.1.3. Material Jetting  \n\nA technique for in-process monitoring of droplet properties during liquid metal jetting AM was developed using an in-process millimeter wave (MW) sensor and ML.[37] The MW sensor provided a real-time monitoring solution that circumvented the computing requirements of high-speed image sensors by producing efficient time series data to anticipate droplet size, velocity, and shape. An MLP-based non-linear autoregressive model was trained to predict droplet size and velocity with a statistical fidelity exceeding $90\\%$ , outperforming traditional statistical models. Furthermore, a supervised ML model was trained to classify droplet shapes using spectral frequencies from the MW sensor data, achieving an F1-score of over $95\\%$ . This approach presented a practical and computationally efficient solution for quality control in liquid metal jetting AM. It was even suggested that future research should aim to develop and use ML models for the prediction of defect formation and build failures and contribute to improved part quality and higher manufacturing efficiency.  \n\nA novel in situ monitoring method employing vision-based techniques was introduced to observe droplet formation in inkjet printing.[38] A drop watcher camera was implemented to capture video sequences of droplet properties which include size, velocity, aspect ratio, and the existence of satellite droplets under various voltage and frequency combinations. The influence of these parameters on distinct droplet modes (namely normal, satellite, and no-droplet) was analyzed through computer vision, and a backpropagation neural network (BPNN) was constructed to categorize the droplet modes based on these properties with a high degree of classification accuracy at $90\\%$ . This method offered a sturdy framework for real-time quality inspection during inkjet printing, which can potentially facilitate process enhancement and predictive analysis. The work laid the foundation for the future development of a digital twin model for inkjet printing and other related electronic printing technologies.  \n\n![](images/d8196111fa6ceb3fbb5d2cc2b04efc50acedbc6fa94736659b18238757ddc521.jpg)  \nFigure 12. Illustration of the process for detecting irregular powder feeding. a) Deposition head featuring four side nozzles and a central camera for monitoring the melt pool region, b) Training and validation of the model using image datasets representing both regular and irregular conditions, and c) Real-time application of the pre-trained model for immediate inference. Reproduced with permission.[43] 2022, Elsevier.  \n\nAnother study proposed the adoption of predictive models and nonlinear autoregressive neural networks with external input (NARX) for quality assurance and process control in AM for electronics. The challenges of using 3D printing in electronics manufacturing were highlighted and modeling techniques such as finite element analysis (FEA) and data-driven ML can be applied for predicting product performance, quality, and reliability.[39] A novel model-based approach for inkjet printing process is demonstrated using state-space models derived from measured process data.[40] This approach helped to anticipate process trends and associated product quality characteristics over large prediction horizons, even in the case of moderately non-linear dynamics of the 3D printing process. Both studies emphasized the importance of proactive, model-based assessment over conventional post-manufacture techniques to mitigate common reliability and quality risks associated with AM. These advancements have significant potential in enhancing the acceptance of 3D printing technology in the electronics industry, while ensuring improved and more robust process performance.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 3.1.4. Directed Energy Deposition (DED)  \n\nThe occurrence of defects is common in the DED process; these defects include balling, lack of fusion, porosity, warping, and waviness. The defects are caused by improper laser parameters, material interactions, and heat accumulation. These issues compromise the structural integrity, surface finish, and dimensional accuracy of the manufactured parts, highlighting the importance of meticulous parameter control and realtime monitoring in DED processes for achieving high-quality components.  \n\nAn infrared camera coaxial to the laser beam was used to train a deep CNN to identify process stability at four categories: normal laser power, low laser power, low scanning speed, and high scanning speed with accuracies above $80\\%$ [41] Another study analyzed process parameters to predict the melt pool temperatures via extreme gradient boosting ensemble learning and LSTM neural networks.[42] The melt pool temperatures were trained on infrared camera measurements and the coefficient of determination between the prediction and actual measured temperatures was higher than $51\\%$ in all cases tested. Another study used coaxial camera images to determine abnormal powder supply in DED due to issues such as restricted powder flow (Figure 12).[43] A few ML models were trained and the accuracies were above $55.1\\%$ , $69.8\\%$ , $70.6\\%$ , and $95.9\\%$ for K-NN, decision tress (DT), RF, and CNN, respectively. Furthermore, an in situ monitoring system was developed for DED process.[44] The monitoring system consisted of a hyperspectral camera for melt pool width and temperature control, a coaxial camera for melt pool data, and a laser scanning system for material height measurement. Independent tuning of the process parameters was challenging due to the highly interconnected process parameters that significantly influenced the deposited geometry and material properties. Hence, ML-based optimization is helpful in finding the optimal controller output for the in situ process monitoring system.  \n\nBeyond process stability, neural network-based ML such as RandLA-Net with in situ sensors were used to detect defects within the DED built parts. Geometrical defects were classified based on a laser line scanner trained on a DL model to classify surfaces into normal, convex, and concave at accuracies of $91.3\\%$ .[45] A similar study used data from a laser profiler to first cluster the points via an unsupervised ML model followed by supervised learning to classify the clusters into no defect, bulging, dents, and wavy surfaces.[46] For the supervised learning, a few ML models were explored, and K-NN achieved the highest accuracy of $93.2\\%$ . Another work combined optical emission spectrometer and CCD camera images through Kronecker product of graphs as inputs into an SVM model.[47] The model was trained against X-ray CT data to classify the layers into three categories: low, medium, and high severity. The combination of input from the two sensors via a Kronecker product improved the statistical fidelity score from $35\\%$ to $75\\%$ . A microphone with a sampling rate of $44.1\\ \\mathrm{kHz}$ was used to gather acoustic emissions from the DED.[48] A deep learning model that consisted of a fully connected regression deep neural network (F-DNN) and a redundant convolutional encoder-decoder network (R-CED) was trained to remove the signal noise from the machine motion, inert gas motion, and powder supply based on the ground truth signal that was equalized, filtered and processed using audiobased algorithms.[48a] The acoustic signal was first denoised by audio-based signal processing algorithms, followed by extraction of time and frequency features to construct a sequence of MelFrequency Cepstral Coefficients (MFCC).[48b] These coefficients were used as inputs to train a CNN model and compared against simpler ML models such as RF, SVM, gradient boosting, and KNN with a subset of the audio signal features used as inputs. The MFCC CNN model produced the highest accuracies above $89\\%$ at predicting defect free, cracks, and keyhole pores in the built part (Table 2).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3.2. Process Optimization  \n\nProcess optimization plays a crucial role in maximizing the efficiency and reliability of AM processes. With the complexity and intricacy involved in AM, fine-tuning the printing parameters, and optimizing the process parameters are essential for achieving consistent and desirable results. One of the major challenges in process optimization for 3D metal printing is the intricate interplay of numerous variables, including laser power, scanning speed, layer thickness, and powder characteristics. The optimal combination of these parameters is dependent on the specific metal alloy, part geometry, and desired mechanical properties. This is where ML is important in process optimization for metal printing. ML algorithms can analyze large amounts of data from previous printing runs, identifying patterns and relationships between process parameters and part quality. By learning from these patterns, ML models can predict the optimal process parameters for a given set of conditions, thereby reducing the need for trial and error, and minimizing material waste. In general, ML can be implemented in metal printing to predict printability of a material under specific set of process parameters, to optimize the toolpath to decrease the residual stress, and to predict the thermal gradient for process optimization purposes.  \n\nSupervised learning is commonly used for process optimization in AM; it is suitable for process optimization when historical data with well-defined input-output pairs are available, but it may not adapt well to dynamic processes. Figure 13 provides an overview of ML applications in optimizing processes across diverse AM processes, along with various objectives related to process optimization. The choice of ML approach is often dependent on the specific process optimization problem, the availability of data (labeled or unlabelled), and the level of complexity involved and more discussion will be provided in the subsequent sections.  \n\n![](images/0f9edb5b7ca81eacdf8acbb2b0a5720387f09f6d74db3040eff828f7629dc65a.jpg)  \nFigure 13. Graphical overview of ML applications in optimizing processes across diverse AM processes, along with various objectives related to process optimization.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3.2.1. Powder Bed Fusion  \n\nThe quality of LPBF-fabricated parts is heavily influenced by process parameters, but existing methods for determining the parameter window are time-consuming and subjective. A supervised ML method was implemented to optimize the LPBF process in additive manufacturing (Figure 14).[53] An ML approach was proposed to detect and track defects and predict material printability in LPBF. It classified printed tracks into five groups based on surface characteristics and developed a datadriven model using BPNN. The model utilized the classification results as target output and four quantitative indicators calculated from surface morphology as input variables. The proposed method significantly improved the efficiency of parameter window search, enabling defect-free printing and excellent part performance. The integration of a 3D microscope for in situ measurement further enhanced its applicability in unmanned factories. Overall, the work highlighted the importance of ML in optimizing the LPBF process, offering an intelligent solution for parameter determination and paving the way for more efficient and automated manufacturing processes.  \n\nThe primary object of another study was to determine the optimal laser tool path by minimizing the average thermal gradient. The study showcased the capability of accurately predicting optimal laser paths using a DL model, which was trained on 33000 physics-based simulation results that contain “good” labels (lowtemperature gradient) and “bad” labels (high-temperature gradient) in a 1:1 ratio, despite limitations in training data and binary information.[54] Notably, the DL simulation, implemented with a CNN, significantly outperformed brute force simulations in terms of speed. This work underscored DL’s potential in tool path optimization within AM, highlighting its ability to comprehend tool path patterns and reconstruct comprehensive path performances. Furthermore, the research illustrated the feasibility of applying a physics-based DL approach to other AM techniques, providing lower simulation costs while maintaining accuracy. Thus, a trade-off between computational expenses and accuracy was identified, emphasizing the importance of striking an optimal balance for future investigations in this domain. It is crucial to note that, despite the DL’s model’s substantial speed advantage over traditional brute force simulation methods, this does not imply that the predictions are flawless and devoid of the need for further refinement. The model’s success lies in its rapid narrowing identification of a singular perfect solution. The model’s predictions serve as a highly informed starting point, and subsequent optimizations can be applied using additional criteria or constraints not fully captured by the training data. This iterative refinement process is essential for tailoring the model’s output to the specific nuances. It is important to note that while the DL model significantly outperforms traditional brute force simulation methods in processing speed, this does not imply that the predictions are flawless and devoid of the need for further refinement. The model’s success lies in its rapid narrowing down of potential tool paths to a subset likely to include the optimal path, rather than guaranteeing the identification of a singular, perfect solution. The model’s predictions serve as a highly informed starting point, and subsequent optimizations can be applied using additional criteria or constraints not fully captured by the training data. This iterative refinement process is essential for tailoring the model’s output to the specific nuances of any given LPBF task. Additionally, the well-known challenge of ML models not precisely adhering to hard constraints is addressed. In the context of LPBF tool path optimization, this limitation necessitates the integration of supplementary optimization algorithms or constraint-satisfaction techniques post-prediction. These steps ensure that the final tool paths not only approximate the model’s predictions but also align with the physical and operational constraints of the LPBF process.  \n\n(Continued)   \nTable 2. ML for quality control in AM.   \n\n\n<html><body><table><tr><td>Research target</td><td>Fabrication process</td><td>ML technique</td><td>Sample size</td><td>Inputs</td><td>Outputs</td><td>Performance</td><td>Refs.</td></tr><tr><td>Process stability: anomalies in powder spreading</td><td>PBF</td><td>Unsupervised: K-means unsupervised clustering followed by labelling based on expert knowledge of the powder spreading defects</td><td>2402 image patches</td><td>Powder bed images</td><td>Powder spreading quality: anomaly-free, recoater hopping, recoater streaking, debris,</td><td>Able to classify the powder spreading with precision ranging from 65 to</td><td>[9] </td></tr><tr><td>Defect prediction: location of voids</td><td>PBF</td><td>Supervised: Ensemble classification</td><td>840 samples of DSLR voxels</td><td>Build layer images taken with DSLR camera at eight different</td><td>spreading Binary quality of a group of voxels as a</td><td>Prediction accuracy: 85%</td><td>[10]</td></tr><tr><td>Layer-wise Surface morphology measurement</td><td>PBF</td><td>Supervised: CNN</td><td>70 000 samples</td><td>lighting conditions 300 × 300-pixel images</td><td> Surface morphology</td><td>Average relative prediction error lower than 10%</td><td>[11]</td></tr><tr><td>Defect prediction through labelling of anomalous in situ data</td><td>PBF</td><td>Unsupervised: K-means clustering to enlarge the manually labelled training dataset k-nearest neighbours supervised learning to identify</td><td>200</td><td>Long exposure IR camera images (OEM EOSTATE Exposure OT)</td><td>Labelling of in situ IR camera images as either normal or anomalous</td><td>Accuracy close to 100%</td><td>[12a] </td></tr><tr><td>Defect prediction through average porosity in a local volume</td><td>PBF</td><td>anomalies Supervised: Random forest bagged tree ensemble.</td><td>100 000 to 1 000 000</td><td>Long exposure IR camera images (OEM EOSTATE Exposure OT)</td><td>Average porosity of a local volume</td><td>Accuracy greater than 90%</td><td>[12b]</td></tr><tr><td>Defect prediction of delamination and splatters</td><td>PBF</td><td>Supervised: Convolutional neural networks</td><td>4314 RGB color images converted into 18 short video sequences</td><td>Infrared thermographic camera images</td><td>Delamination, splatter, or defect-less</td><td>Average accuracy of 96.8%.</td><td>[13] </td></tr><tr><td>Defect prediction of porosities within a volume</td><td>PBF</td><td>Supervised: 1D CNN model was trained using Bayesian Optimization</td><td>Up to 836426 samples</td><td>Short wavelength infrared high-speed camera images</td><td>Binary outcome of pore and non-pore in local volume</td><td>Best prediction accuracy for keyhole porosities above 0.1%</td><td>[14]</td></tr><tr><td>Defect prediction of baling,. under-melting, keyholes, porosity, spatter</td><td>PBF</td><td>Supervised: Feature extraction using Scale Invariant Feature Transforms followed by Bag-of-Words unsupervised ML then labelling by experts</td><td>24385</td><td>High speed visible light camera images</td><td>Prediction of melt pool outcome into 5 types of desirables conditions, balling,</td><td>Accuracy close to 85.1%</td><td>[16] </td></tr></table></body></html>  \n\n(Continued)   \nTable 2. (Continued)   \n\n\n<html><body><table><tr><td> Research target</td><td>Fabrication process</td><td>ML technique</td><td>Sample size</td><td>Inputs</td><td>Outputs</td><td>Performance</td><td>Refs.</td></tr><tr><td>Process stability in predicting laser focus</td><td>PBF</td><td>Supervised: Various ML models ranging from k-nearest neighbours, support vector machines, to</td><td>18 000 data points of 9 classes (162 000 input</td><td>Two IR high speed cameras at 700 and 950 nm wavelengths</td><td>Prediction of laser focus 4-class porosity: severe lack of fusion, lack of fusion, optimal,</td><td>False positive rate: 0.1-0.001%; true positive rate:~90%</td><td>[17]</td></tr><tr><td>Defect prediction in identifying pore locations</td><td>PBF</td><td>Supervised: Deep neural network</td><td>Varies with each configuration up to ≈500 videos</td><td>Visible and NIR high speed camera images</td><td>Prediction of keyhole defect formation</td><td>Prediction accuracies up to 87% were achieved</td><td>[18]</td></tr><tr><td>Defect prediction of keyhole pore location</td><td>PBF</td><td>Supervised: Support vector machine</td><td>1176 time series segments</td><td>Acoustic emissions captured via a microphone fixed 25 - 30 cm on top of the build plate</td><td>Prediction of keyhole or keyhole-free formation within a time window</td><td>Best accuracy of 97%</td><td>[19]</td></tr><tr><td>Quality prediction of produced coupon</td><td>PBF</td><td>Unsupervised and Supervised: K-means clustering Deep learning convolutional neural network</td><td>22 263 data points</td><td>Acoustic emissions captured by a wideband sensor at the center bottom of</td><td>Part quality (minimum defects or cracks only or porosities)</td><td>90% prediction rate</td><td>[20]</td></tr><tr><td>Anomaly detection</td><td>PBF</td><td>Supervised: 1D-CNN, 2D-CNN, RNN, LSTM, Gated Recurrent Unit (GRU) Supervised:</td><td>1809 samples</td><td>Sampling rate: 51.2 kHz 512 acoustic signal data points ML: 23-time domain</td><td>Spattering event</td><td>Highest classification confidence of models is 85.08% Classification accuracy</td><td>[21]</td></tr><tr><td></td><td></td><td>: Logistic Regression (LR), Random Forest (RF), and SVM and CNN</td><td></td><td>features, 18 frequency domain features, and 263 time-frequency dhaira fe atcoastic signal with windows of 5 ms, which is a time-series signal</td><td>regimes (lack of fusion pores, conduction mode and keyhole pores)</td><td>of ~93%</td><td></td></tr><tr><td>Quality prediction of produced coupon</td><td>PBF</td><td>Reinforcement learning</td><td>180 spectrograms</td><td>data points. Optoacoustic fiber Bragg grating Four sensors were split</td><td>Part quality (poor, medium, high)</td><td>Prediction accuracies above 74%</td><td>[23] </td></tr><tr><td>Defect detection</td><td>PBF</td><td>Supervised: CNN-LSTM</td><td>>15000</td><td>into four different running windows (wl,w2, w3,and w4), whose time duration is 0.83,1.65,2.5, and</td><td>Lack of Fusion (LoF), conduction mode, and keyhole across various time scales</td><td>95.9% to 100%</td><td>[24] </td></tr><tr><td>Defect detection</td><td>PBF</td><td>Supervised: CNN</td><td>4004</td><td>3.30 ms,respectively. Layer-wise imagery, multi-spectral emissions, and laser scan vector data</td><td>\"flaw\" and “no flaw\"</td><td>93.9% and 98.9%</td><td>[25] </td></tr></table></body></html>  \n\nTable 2. (Continued)   \n\n\n<html><body><table><tr><td> Research target</td><td>Fabrication process</td><td>ML technique</td><td>Sample size</td><td>Inputs</td><td>Outputs</td><td>Performance</td><td>Refs.</td></tr><tr><td>Defect detection</td><td>Material extrusion (FFF)</td><td>Supervised: MLP, 1D CNN, RNN LSTM, Inception time, XceptionTime, XCM</td><td>20 000 value pairs</td><td>Temperature, humidity, air pressure, gas particle resistance</td><td> Normal, defect</td><td>Accuracy: 95%</td><td>[26] </td></tr><tr><td>Anomaly detection</td><td>Material extrusion (FFF)</td><td>Supervised: multi-head encoder-decoder temporal convolutional network (MH-ED-TCN)</td><td>328 470</td><td>Humidity, temperature, acoustic sensor</td><td>Normal, anomaly</td><td>Accuracy obtained was 97%</td><td>[27]</td></tr><tr><td>Defect detection</td><td>Material extrusion (FFF)</td><td>Supervised: CNN-pre-trained ResNet 50</td><td>120000</td><td>224 × 224-pixel images</td><td>Over-extrusion, good quality, Under-extrusion</td><td>98% accuracy</td><td>[28]</td></tr><tr><td> Defect detection</td><td>Material extrusion (FFF)</td><td>Supervised: CNN-yolov4</td><td>>8000</td><td> 512 × 512-pixel images</td><td>Over-extrusion, good quality, Under-extrusion</td><td>89.8%</td><td>[29]</td></tr><tr><td>Fault diagnosis</td><td>Material extrusion (FFF)</td><td>Semi-supervised: conditional generative adversarial network (CGAN), and domain adversarial neural network (DANN)</td><td>13 025 images (3.5% for normal images, 16% each for other classes)</td><td>128 × 128-pixel images</td><td>standard (STD), low nozzle flow rate (Low NFR), high nozzle flow rate (High NFR), low flling speed (Low FS),high flling sped (High FS),low liquefier temperature (Low LT), and high liquefier temperature</td><td>Accuracy for DANN_CGAN is the highest (91.01%)</td><td>[30] </td></tr><tr><td>and rapid correction</td><td>Material extrusion (FFF)</td><td>Multi-head deep residual attention network with a single backbone and four output heads, one for each parameter</td><td>946 283</td><td>320 × 320 RGB image</td><td>Good, low, high (for flow rate,lateral speed, Z offset, and</td><td>Overall accuracy: 84.3%</td><td>[31]</td></tr><tr><td>Detect deformations in the printed concrete layers</td><td>Material extrusion</td><td>Supervised: CNN model Line and edge detections Thresholding line angles</td><td>1 M images</td><td>RGB image from camera</td><td>Cropped concrete layers</td><td>Fl scores for detect and non-detect are 82% and 98.05%</td><td>[32]</td></tr><tr><td>Detect crack on concrete surface</td><td>Material extrusion</td><td>Supervised: Mobile Net-SSD</td><td>20 000+ images</td><td>300 × 300-pixel images</td><td>cracks</td><td>80% mean average precision</td><td>[33]</td></tr><tr><td>Detect deformations on printed concrete structures</td><td>Material extrusion</td><td>Unsupervised: Principal component analysis and clustering methods (K-means and spectral cluster)</td><td>-</td><td>3D point clouds</td><td>Circle radius estimation Deformation detection</td><td>inaccuracy of 0.3%</td><td>[34]</td></tr></table></body></html>  \n\n(Continued)   \nTable 2. (Continued)   \n\n\n<html><body><table><tr><td>Research target</td><td>Fabrication process</td><td>ML technique</td><td>Sample size</td><td>Inputs</td><td>Outputs</td><td>Performance</td><td>Refs.</td></tr><tr><td> In situ monitoring</td><td>Material extrusion</td><td>Supervised: Image segmentation using U-net neural network</td><td>20 000 images</td><td>512 ×512-pixel image input</td><td>512 ×512-pixel image output</td><td>The pixels in the segmentized output have an accuracy of</td><td>[35] </td></tr><tr><td>Optimization of printing outcome</td><td>Material extrusion</td><td>Supervised: ad hoc optimized convolutional neural network (CNN) and mathematical model</td><td>128</td><td>Printing set-up, material type, layer height, infll density</td><td> Extrusion multiplier</td><td>96.6%, The results showed an accuracy of 94.3% for overall printing.</td><td>[36]</td></tr><tr><td> In-process monitoring</td><td>Material jetting (Inkjet printing)</td><td>Supervised: Multilayer perceptron-based non-linear autoregression (MLP-NARX) model</td><td>A total of 345 droplets were used</td><td>20 data points before and after each local minimum a</td><td>Droplet size, velocity, and morphology</td><td>Achieve >95% accuracy for droplet morphology classification</td><td>[37]</td></tr><tr><td>In situ droplet monitoring</td><td> Material jetting</td><td>Support vector machine Supervised: Back propagation neural network</td><td>N.A.</td><td>Droplet size, velocity, aspect ratio,</td><td>Normal dispensing, non-dispensing, and</td><td>Accuracy: 90%</td><td>[38]</td></tr><tr><td>In-line process control</td><td> Materia jetting</td><td> State-space modeling</td><td>N.A.</td><td>presence of satellites Nozzle temperature</td><td>satellite modes Film thickness</td><td> Accuracy metric of</td><td>[39]</td></tr><tr><td> In-line monitoring</td><td>(Inkjet printing) Material jetting (Inkjet printing)</td><td>Supervised: nonlinear autoregressive neural network with external input</td><td>150 past datapoints</td><td>Thickness of printed line</td><td>Thickness of printed line</td><td></td><td>[40]</td></tr><tr><td>Process stability of laser power and scan speed</td><td>DED</td><td>(NARX) Supervised: Deep convolutional neural network</td><td> 21l images</td><td>Coaxial infrared camera</td><td>Four process conditions: normal, low laser power, low</td><td>Prediction accuracies above 80%</td><td>[41]</td></tr><tr><td>Process stabilty by prediction of melt pool temperature</td><td>DED</td><td>Supervised: Extreme gradient boosting ensemble Long short-term memory neural networks</td><td>70 112 data points</td><td>Laser power, scan speed,layer index, time index, average</td><td>scanning speed Melt pool temperature</td><td>R² values above 0.51</td><td>[42]</td></tr><tr><td>Process stability relating to the condition of the powder nozzles</td><td>DED</td><td>Supervised: K-nearest neighbours Decision tree Random forest</td><td>80 000 images</td><td>Coaxial camera</td><td>Condition of nozzles (i) normal case, (ii) #1 nozzle clogged, (ii) #2 nozzleclogged, (iv) #3 nozzle clogged, and (v) #4</td><td>Accuracy of 95.9% for CNN model</td><td>[43]</td></tr><tr><td> Realtime monitoring</td><td>DED</td><td>Supervised: Artificial Neural Network</td><td></td><td>Laser power (P), powder mass flow (m) and scanning speed (s)</td><td>nozzle clogged Close-loop feedback</td><td></td><td>[44]</td></tr></table></body></html>  \n\nTable 2. (Continued)   \n\n\n<html><body><table><tr><td>Research target</td><td>Fabrication process</td><td>ML technique</td><td>Sample size</td><td>Inputs</td><td>Outputs</td><td>Performance</td><td>Refs.</td></tr><tr><td>Surface geometrical quality classification</td><td>DED</td><td>Supervised: RandLA-Net</td><td>247 samples with ~10 000 points per sample</td><td>Laser line scanner</td><td>Surface conditions: normal, convex, concave</td><td>Prediction accuracies above 91.3%</td><td>[45]</td></tr><tr><td>Surface geometrical quality classification</td><td>DED</td><td>Clustering via unsupervised ML model followed by several supervised learning models: Support Vector Machine, K-Nearest Neighbours, Gaussian Process, Decision</td><td>73 samples</td><td>Laser profiler</td><td>Surface conditions: no defect, bulging, dented, and wavy.</td><td>Highest accuracy of 93.2%.</td><td>[46]</td></tr><tr><td>Quality of each layer</td><td>DED</td><td>Random Forest, and AdaBoost Supervised: Support Vector Machine</td><td>400 layers</td><td>Optical emission spectrometer and CCD camera images</td><td>Quality of the layer: low severity, medium</td><td>Fidelity score from 35% to 75%</td><td>[47]</td></tr><tr><td>Defect prediction (defect free, cracks, or keyhole pores) in local area of part </td><td>DED</td><td>Supervised: Random forest, support vector machine, gradient boosting, and k-nearest, convolutional neural network</td><td>1300 signal samples</td><td>Acoustic emissions gathered using a microphone</td><td>severity, high severity Acoustic signal with removed noise Prediction of defect free, cracks, or keyhole pores within</td><td>Highest accuracies above 89%.</td><td>[48]</td></tr><tr><td>Predict surface roughness</td><td>PBF</td><td>Supervised: The roughness prediction models are developed using linear regression, polynomial regression, support vector regression (SVR), Gaussian process regression</td><td>59</td><td>The image texture features such as the contrast from the GLCM method, and the second moment from the</td><td>Surface roughness parameters</td><td>R² value of more than 0.9</td><td>[49]</td></tr><tr><td>Defect inspection (ST and Inconel)</td><td>PBF</td><td>networks (ANNs) Supervised: Neural Learning Based Blind Source Separation (NLBSS) and Spatial-Temporal Sparse Dictionary Learning (STSDL)</td><td></td><td>Thermogram sequence</td><td>Defect detection</td><td>F-score of 0.96 for large detects, 0.57 for small defects</td><td>[50]</td></tr><tr><td>Detect detection</td><td>PBF</td><td>Supervised: Image classification via U-net</td><td>Nil</td><td>1280 × 1024</td><td>Prediction classes: Holes, Spattering, Vertical defects, Horizontal defects,</td><td>Accuracy >90% for most tested features.</td><td>[51]</td></tr><tr><td>Pore size prediction</td><td>PBF</td><td>Supervised: Dynamic time warping and k-Nearest Neighbor classifiers</td><td></td><td>Time-series temperature</td><td>and Incandescence. Pore size</td><td>Classification accuracies of 92% to 94% are achievable</td><td>[52]</td></tr></table></body></html>  \n\n![](images/b6f947ae61e362657f18b7b962ff5dd11bea2891227d40d87497d1615da10047.jpg)  \nFigure 14. Illustration showing the different types of line morphology created by powder bed fusion using different process parameters and the use of ML to classify and predict the printability of the parts. Reproduced with permission.[53] 2020, MDPI.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3.2.2. Material Extrusion  \n\nMultiple process parameters such as the nozzle and bed temperatures, raster angle, layer thickness, nozzle size, and print speed are known to affect the quality of the printed parts during material extrusion. The high dimensionality of the dataset warrants the use of ML techniques to identify the most optimum process parameters.  \n\nA data-driven ML platform using MLP and CNN models was developed to predict optimized parameters for the FFF process.[55] Spatial features were first extracted using CNN and were then transferred to the MLP model together with other process parameters such as extrusion width, layer height, print speed, infill, area, and volume. The approach enabled quick and accurate predictions of decisive parameters such as time, weight, and length, even with fuzzy input information. It did not require consideration of the shape, size, and material of the printed object and can perform the process automatically. The proposed ML approach has several advantages, including better stability and clearer rules compared to previous research, fast estimation of printer parameters in approximately one second, and applicability to various types of 3D printing materials and domains like construction, medical, and architecture. In a different study, a datadriven predictive model for the FDM process was created using a variety of ML algorithms.[56] The model predicted dimensional deviations between the printed model and the original one by fusing temperature and vibration data from various sensors with process parameters. In terms of parts dimensional accuracy prediction, the residual attention neural network model performed better than other ML models such as 1D CNN and LSTM networks. However, more advancements are required to consider environmental factors from the outside, develop an online feedback system for real-time prediction, and create a comprehensive digital twin system for AM.  \n\nBayesian optimization was used in a recent work to accelerate the printability optimization for extrusion-based bioprinting.[57] The input variables for bioink compositions consist of 3-gelatin methacryloyl (GelMA) concentrations and 3 GelMA/hyaluronic acid methacrylate, whereas the input variables for printer parameters include bioink reservoir temperature, extrusion pressure, print-head speed, and platform temperature. A scoring system was then implemented to assess the filament morphology during extrusion and pore architecture on layer stacking. The study has shown that the Bayesian optimization algorithm can be used to analyze the optimal printer parameters and accelerate the extrusion bioprinting experimentation process in comparison to the traditional trial and error approach.[57] Another work utilized Uniform Design (UD) technique to select 12 experiment data points based on three parameters four-level data space $\\mathrm{U}_{12}(\\mathrm{P}_{3}{}^{4})^{[58]}$ and SVM algorithm to generate a process map that identified optimal printing parameters to fabricate high-quality printed parts using Pluronic F127 bioink with a high probability $0f>75\\%$ .[59] It provided a simple tool to improve the printability of extrusion-based bioprinting process based on width index with minimum dataset using inputs such as printing temperature, material composition, and path height.  \n\nAn interesting study used optimized ML models to predict material printability for FDM-printed pharmaceutical products.[60] A total of 318 materials and 1594 formulations obtained from online literature and in-house formulations were used as dataset for this study; three different ML techniques (ANN, SVM, and RF) were used and a 75:25 split was used for training and testing. RF emerged as the best ML model for predicting all targeted variables (filament mechanical characteristics, extrusion temperature, printing temperature, and printability) with the highest accuracy. Another work compared the optimization of 3D printing properties for assistive devices using traditional ANN and deep neural networks (DNN).[61] The DNN outperformed the traditional ANN approach, offering improved calculation speed, higher print quality, and decreased errors. It highlighted the effectiveness of DL-based optimization in 3D printing processes.  \n\nAnother study proposed the use of both open-loop and closedloop ML models to monitor the effects of processing parameters on the quality of 3D-printed parts.[62] The open-loop approach utilized multiple ML classification algorithms such as deep neural network (DNN), support vector machine (SVM), decision tree (DT), random forest (RF), and logistic regression (LR) to determine the relationship between processing parameters and printed lines’ quality (large space, little space, good connection, little material flow, large material flow). A closed-loop system is constructed based on this relationship using a fuzzy inference system that generates optimized processing parameters. The ML-based closed-loop system improved the quality of printed parts and enabled a self-adjusting 3D printing process by effectively monitoring and optimizing processing parameters. More research could be conducted to include additional processing parameters and conducting real-time closed-loop 3D printing experiments.  \n\nIn larger-scale construction printing, printing parameters such as pumping, extrusion, and printing speeds, nozzle diameter, and standoff height have a direct impact on the printing process and the final mechanical properties of the concrete structures. It is a daunting task to identify the optimal printing process due to the large number of variables involved. One approach to address this challenge is through nozzle shape optimization. A predictive modeling approach using ANN was proposed to directly control the geometry of concrete printing extrudate by optimizing nozzle shapes.[63] Thirteen different nozzle shapes were predetermined and used in the experiments, with their corresponding extrudate geometries analyzed using MATLAB. The ANN model was then developed to correlate nozzle and extrudate shapes, and a nozzle-extrudate database was formed for analyzing the optimal nozzle shape for specific target extrudate shapes. The results showed a noticeable improvement in surface finish quality without additional post-finishing effort, offering flexibility for various printing structures with different outersurface shapes. The proposed approach has the potential to improve surface finish quality in concrete printing, as it directly controls extrudate geometry without the need to reduce nozzle size.  \n\nResearchers are making significant advancements in process optimization for 3D printing by exploring nozzle shape optimization, predictive modelling for mechanical properties, and AIbased control systems. These approaches offer potential for enhanced surface finish quality, improved mechanical properties, and better control over the printing process, paving the way for further innovation and application of 3D printing in various industries.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3.2.3. Material Jetting  \n\nThere are many variants of jetting-based printing techniques which include inkjet printing, aerosol jet printing, electrohydrodynamic jet printing, acoustic printing, laser-induced forward transfer printing, etc., that facilitate drop-on-demand highresolution printing. Each of these printing techniques are designed differently and they have their unique sets of process parameters that can be controlled to adjust the print quality. Typically, these print parameters are adjusted such that a printed pattern with well-defined edges is obtained. However, most printing processes have multiple process parameters that make it difficult to identify the most optimum print settings for the best print condition. Thus, many on-going research works are looking at applying ML to simplify process optimization.  \n\nA multi-objective optimization design method for drop-ondemand printing parameters through fully connected neural networks (FCNNs) was proposed; a hybrid multi-subgradient descent bundle with an adaptive learning rate algorithm was used for multi-objective optimization due to its rigorous convergence theorems; it can be used to optimize printing of droplets with smaller diameter, faster droplet speed with absence of satellite droplets using inputs such as applied voltage, viscosity, surface tension and nozzle diameter.[64] Another study used ensemble learning approach and its base learners (RF, least absolute shrinkage and selection operator (LASSO), extreme gradient boosting, and SVR) to predict the droplet velocity and volume using inputs such as polymer concentration, excitation voltage, dwell time, and rise time in inkjet-based bioprinting process; the experimental results showed extreme gradient boosting has highest predictive accuracy ( $'R^{2}=0.977$ , $\\mathrm{RE}=0.044$ , and $\\mathrm{RMSE}=0.240\\$ in accordance with the studied operating conditions.[65]  \n\nAnother study utilized ML models to optimize the electrohydrodynamic jet printing of graphene-based biosensors.[66] Supervised ML models, trained on key printing parameters such as nozzle speed, ink flow rate, and voltage, could predict the conductivity of printed circuits in real time. The RF and K-NN $(\\mathbf{k}~=~10)$ models delivered the highest prediction accuracy of about $83\\%$ . The integration of ML aimed to streamline the manufacturing process, ensure resource efficiency, and produce devices with controlled electrical properties. Overall, the study emphasized the significant potential of ML in enhancing the manufacturing processes in the electronics industry.  \n\nML models were used to predict ink-jetting behavior in the inkjet printing process based on 11 distinct ink and printer parameters.[67] Notably, small ensembles of DT such as boosted DTs and RF demonstrated superior predictive power for drop velocity and radius, with an RMSE of $0.39\\ \\mathrm{m}\\mathrm{s}^{-1}$ and $2.21~\\upmu\\mathrm{m}$ , respectively. Furthermore, a neural network model was constructed to categorize drop behavior into three categories: stable “single drop”, “multiple drops”, or “no ejection” and achieved an accuracy of $91.94\\%$ . The models were validated using an untried graphene oxide ink, which was not included in the training dataset. This innovative ML approach could accurately predict ink jetting behavior and eliminate the need for costly, timeconsuming, and material-intensive jetting experiments. Overall, the research demonstrated that ML can significantly enhance the efficiency of inkjet printing, highlighting its potential for accelerating the development of new functional ink materials for printed electronics.  \n\nAn innovative combination of a microfluidics-driven multiscale 3D printer with ML was implemented to enhance the precision of the freeform generation of active electronics.[68] A new printing and ML workflow was developed to modulate ink composition in real time and classify complex internal features. This was achieved by using an SVM-guided classification model for automated, in situ pattern classification. The ML model showed a balanced accuracy of $81.96\\%$ in classifying the internal textures of the evaporative-driven printed droplets. The developed ML-integrated printing system facilitated autonomous optimization of printing parameters and robust adaptation to unanticipated disturbances. This represented a significant step towards automated process parameter control for the 3D printing of electronics.  \n\nAnother study applied RSM to investigate the interplay between aerosol jet printing parameters and the intense pulsed light (IPL) sintering process for silver nanoparticle film in printed electronics applications.[69] The correlation between print passes and sintering distance on surface morphology and sheet resistance was investigated to elucidate the complex relationships among the different parameters (Figure 15). A hybrid multi-objective optimization approach, including a modified central composite design (CCD) and non-dominated sorting genetic algorithm (GA), was applied to systematically manage these conflicting responses. The use of ML allowed for the identification of optimal windows for the IPL sintering process, resulting in films with low sheet resistance and low surface roughness. Compared to conventional trial-and-error methods, this optimization approach was found to be more efficient and systematic. This work lays a foundation for future optimization of IPL sintering parameters for various nanoparticle-based films and multi-layered electronics fabrication.  \n\n![](images/486de980392d48d22ed54ea710cc09f3f847f5081ebe5e1aa2895384b260dad8.jpg)  \nFigure 15. Schematic showing the workflow for a multi-objective optimization using RSM for optimizing the electrical conductivity and surface roughnes in the IPL sintering process. Reproduced with permission.[69] 2022, AccScience Publishing.  \n\nVarious ML methods such as RSM, GA, and transfer learning were used to optimize the process parameters of the aerosol jet printing process and understand the complexity between their interactions.[70] The results showed that the Gaussian process regression performed better than the other ML models such as Kmean clustering and SVM in terms of prediction of the classification of printed features such as the line width, edge roughness, and film thickness. It is possible to use a very small dataset for the same prediction using transfer learning techniques such as feature representation, instance transfer, and model-based transfer. The feature representation technique outperformed the other methods as it resulted in smaller error in the prediction. Overall, the ML works for aerosol jet printing present a framework that can be effectively transferred and applied in other printing techniques.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.2.4. Directed Energy Deposition (DED)  \n\nBesides toolpath optimization for LPBF processes, ML is often applied in other metal printing such as DED and gas-metal arc welding-AM to predict the spatial and temporal thermal fields to inform the designers of the producibility and the potential risk for cracks of the parts.[71] A study utilized a novel approach for discretizing the deposition process of gas-metal arc welding-AM process to enhance the adaptability and flexibility of numerical simulation in analyzing thermal aspects of the material deposition process (Figure 16).[71a] A unique data structure was used to obtain deposition state data from numerical simulation results. The data was then utilized to train a recurrent neural network and deep neural network (RNN-DNN), and one convolutional neural network (CNN) specifically designed for identifying correlations between deposition stages and their corresponding thermal fields. The validation results demonstrated that the developed method achieved a prediction accuracy exceeding $94\\%$ compared to numerical simulation results. Interestingly, the time required for a single prediction process was reduced to the millisecond level. Another study also RNN-DNN for thermal analysis in laser-aided AM (LAAM).[71b] A thermal field prediction numerical model was used to generate a comprehensive training dataset, the developed RNN-DNN model successfully correlated laser scanning patterns with their corresponding thermal history distributions. The high prediction accuracy of over $95\\%$ compared to finite element models highlighted the significance of ML in improving efficiency and decision-making in LAAM processes.  \n\n![](images/5b31fc5c32e739029a65287054d00023f1d33eec73055bfd8a8ef2302974d9a7.jpg)  \nFigure 16. Illustration showing the use of RNN-DNN and CNN model to predict the temperature field of the 3D printing process. Reproduced with permission.[71a] 2021, Elsevier.  \n\nThis advancement enables rapid evaluation of different scanning patterns within minutes, leading to potential cost savings and enhanced manufacturing outcomes. Furthermore, the integration of ML techniques paves the way for future research on multi-layered 3D deposition processes, expanding the understanding of complex geometries and optimizing deposition strategies for desired material properties. Overall, these studies underscore the importance of ML in revolutionizing thermal analysis in metal printing and accelerating its adoption in diverse industries.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3.2.5. Vat Photopolymerization  \n\nA recent work has demonstrated the use of NN to learn printing parameters for DLP process from a 3D-printed simulator to offset the cell-induced light scattering effect.[72] Single-layer trial prints were obtained from different sample masks and used to train the algorithm; a print simulator was used to generate a huge amount of new training data, which greatly reduced the required training samples by more than tenfold. The printed samples and the generated samples were then used to train the neural network which calculates the appropriate masks that compensate the cell scattering effect. The NN approach in the study is composed of two U-Net-like NNs—slave NN and master NN. The network architecture of the master NN is composed of 14 convolution or deconvolution layers with batch normalization, ReLU, and Tanh activation function, as well as U-net style skip connections. The slave NN learned the transformation of the physical 3D printer and provided gradient information to support the training of the master NN, while the master NN learned the inverse transformation of the 3D printer. This allowed the master NN to suggest a deformed mask for any given target structure and print it out under highly scattering condition. Furthermore, the algorithm enabled the use of a small sample size (as small as 32) for training data to generate grayscale masks that can print fine-detailed structures surpassing the traditional manual tuning method with identical masks.  \n\nContinuous liquid interface production (CLIP) is an advanced vat photopolymerization technique that uses an oxygenpermeable “dead zone” between the fabricated part and transparent window to continually cure the resin. There is an optimal range of printing speeds to achieve successful print for each defined geometry; a combination of physical modeling and ML approaches was used in a recent work to identify the optimum speed and appropriate speed range for continuous printing.[73] A synthetic dataset was first generated in the absence of an available experimental dataset to identify the significant factors using the design of experiments (DOE) for successful prints. The predicted results for the successful prints were then screened and collected as new experimental dataset that were subsequently used for training. Various ML algorithms such as conventional techniques (DT, naive Bayes, K-NN, and SVM), ensemble approaches (RF, gradient boost, and Ada boost), and DNN (Siamese networks) were evaluated and compared; Siamese Networks demonstrated superior performance (average training accuracy of $90.17\\%$ and testing accuracy of $88.42\\%$ ) as critical information was extracted from the mathematical models-generated synthetic dataset (Table 3).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 3.3. Design Optimization  \n\nThe rapid evolution of 3D printing technologies has paved the way for innovative approaches in the design and fabrication of materials and structures. Amidst the plethora of techniques that have emerged to enhance the additive manufacturing process, the integration of ML stands out as a game-changer. Particularly in the realm of design and topology optimization, ML offers capabilities that have the potential to redefine the paradigms of 3D printing. Design and topology optimization traditionally involve intricate processes, where the objective is to derive the best material distribution within a given space, considering specific boundary conditions and loads. The challenge here is the vast solution space, which becomes computationally intensive and time-consuming to navigate. This is where ML comes into play. With its ability to analyze massive datasets, recognize patterns, and make predictions, ML can provide insights and solutions at a pace and precision that are often beyond traditional computational methods. Moreover, the iterative nature of design optimization aligns seamlessly with ML models. These models can be trained on a myriad of design variations, learning from each iteration, and subsequently suggesting optimal design strategies that not only meet but often surpass human-driven solutions. Furthermore, the incorporation of ML allows for real-time feedback during the design phase, which can be instrumental in making swift, informed decisions. In the context of AM, the choice of ML approach is dependent on the stage of design process. Supervised learning might be useful for the prediction of material properties at the early design stage, while reinforcement learning could be employed for fine-tuning and optimizing the design of 3D-printed parts. Most of the design optimization problems are multi-objective with conflicting design goals. Hence, a combination of approaches, like multi-objective optimization algorithms might be applied to determine the optimal solutions. Figure 17 provides a summary of the application of ML for design optimization for various AM-related applications and more discussion on the use of different ML techniques for design optimization in AM will be provided in the subsequent sections.  \n\n![](images/71dd067cae372ac39f0c284056ddcbceb7dcd11f928fdd00abdd7e333ed4dbf4.jpg)  \nFigure 17. Graphical overview illustrating the utilization of ML for optimizing designs in the context of AM-related applications.  \n\nA novel approach for constructing AM design rules was introduced using ML and knowledge graphs (Figure 18).[75] The framework extracted knowledge on predictive manufacturability from data, stored both existing and newfound AM knowledge in an ontology-based knowledge graph and applied reasoning to derive data-driven prescriptive AM design rules. The methodology enhanced the automated and autonomous construction and improvement of AM design rules, supporting AI-related decisionmaking in additive manufacturability analysis and (re-)design for AM. By providing shareable AM design rule knowledge with the AM community, this work promotes collaboration and facilitates advancements in the field.  \n\nAn optimization framework that utilized variational autoencoder (VAEs) was proposed to design composite mechanical metamaterials (Figure 19).[76] The focus was on controlling macroscopic elastic moduli and designing optimal representative volume element. The approach employed a variational autoencoder to learn a reduced representation of representative volume element configurations, enabling Bayesian optimization for multi-material design problems. Bayesian optimization can be used to construct a probabilistic surrogate model for the objective function and query the next data point. This ML-based framework eliminated the need for subjective trial-and-error design decisions. Experimental validation using multi-material 3D-printed samples demonstrated good agreement between the optimized values by the ML model and the experimental counterparts.  \n\nA method utilizing StyleGAN was employed to design architected materials inspired by nature, specifically focusing on the generative formulation of original unit cell designs inspired by leaf microstructures.[77] By employing unsupervised learning, this approach facilitates the exploration of a latent space for pioneering material design, overcoming the limitations associated with labelled data. This methodology proves particularly pertinent to 3D printing workflows, where it can guide the development of materials and structures by translating natural language inputs or human design iterations into optimized 3D models. This process showcases the potential of integrating advanced ML techniques to augment material design and manufacturing processes, thereby enhancing the efficiency and responsiveness of intricate design workflows to human inputs.  \n\nTable 3. ML for process optimization in AM.   \n\n\n<html><body><table><tr><td>Predict printability (% nano-TiB2 reinforced AlSi10Mg composite)</td><td>PBF (SLM)</td><td>Supervised: Backpropagation-based neural network model</td><td>2048</td><td>9 parameter combinations of laser power and scan speed</td><td>2 prediction classes (Good and bad printability)</td><td>A predictive approach for selective laser melting was developed, which makes use ofa ML algorithm capable of recognizing faulty tracks and</td><td>[53] </td></tr><tr><td>Toolpath optimization</td><td>PBF (SLS)</td><td>Supervised: Linear regression modeland CNN</td><td>33 000</td><td>Laser toolpath</td><td>Good or bad classification based on median temperature gradient</td><td>intelligently anticipating printable parameters It was noted that the linear model was notcapableofaccurately discerning the true optimal laser path pattern. Furthermore,when employing a Convolutional Neural Network (CNN), the Deep Learning simulation proved</td><td>[54]</td></tr><tr><td>Print information estimation</td><td>Material extrusion (FFF)</td><td>Supervised: MLP and CNN</td><td>24640</td><td>Extrusion width, layer height, print speed, infll percentage, volume area</td><td>Time, length, and weight</td><td>to be significantly faster compared to a brute force simulation. The proposed model does not need to consider the shape ofthe object but can perform the process automatically</td><td>[55] </td></tr><tr><td>Predict dimensional deviations</td><td>Material extrusion (FFF)</td><td>Supervised: random forest (RF),extreme gradient boosting (XGB), linear regression (LR), gradient boost (GB), light gradient boosting machine (LGBM),decision tree (DT), Ridge, Lasso, AdaBoost, and three deep learning algorithm</td><td>N.A.</td><td>Temperature and vibration data from multiple sensors (thermocouples, infrared thermometers, and accelerometers)</td><td>Dimensional deviations</td><td>without external factors Deep learning algorithms often outperform traditional machine learning techniques, even with limited datasets. (R²:0.9113) When tested on a dataset consisting only of process parameters and extruder vibrations,the Residual Attention model demonstrated strong resilience</td><td>[56]</td></tr></table></body></html>  \n\n(Continued)   \nTable 3. (Continued)   \n\n\n<html><body><table><tr><td>Research target</td><td>Fabrication process</td><td>ML technique</td><td>Sample size</td><td>Inputs</td><td>Outputs</td><td>Major findings</td><td>Refs.</td></tr><tr><td>rintability optimization</td><td>Material extrusion</td><td>Supervised: Bayesian optimization framework</td><td>N.A.</td><td>Ink composition, reservoir temperature, extrusion pressure, print-head</td><td>Score system for filament morphology</td><td>It can be used to analyze the optimal printer parameters and accelerate the extrusion bioprinting experimentation process in comparison to the</td><td>[57]</td></tr><tr><td>Dptimization of printing outcome</td><td>Material extrusion</td><td>Supervised: Support Vector Machine (SVM)</td><td>12</td><td>Printing temperature, material composition, path height</td><td>Width index</td><td>traditional trial and error approach Another work utilized Uniform Design (UD) technique to select 12 experiment data points based on three parameters four level data space U12(P34)[58] and Support Vector Machine algorithm to generate a process map that identified optimal</td><td>[59] </td></tr><tr><td>rintability optimization</td><td>Material extrusion (Hot melt extrusion)</td><td>Supervised: Artificial neural networks, support vector machines and random forests</td><td>1594 samples</td><td>Material type, glass transition temperature, melting temperature,</td><td>Filament mechanical characteristics,extrusion temperature, printing</td><td>75% Random forest emerged as the best ML model for predicting all targeted variables (filament mechanical characteristics, extrusion temperature, printing temperature and printability)</td><td>[60]</td></tr><tr><td>parameters</td><td></td><td>Supervised: ANN, DNN</td><td></td><td>Maximum tensile force, Type of part, Dimensions of part</td><td>Material, layer height, thicknesses (Top, Bottom Shell), fill density, print speed Temperatures (bed, lst and 2nd nozzles)</td><td>with the highest accuracy. Compared with the results from the traditional ANN approach, optimization based on DL decreased the calculating speed by up to 1.5 times with the same print quality, increased quality (both learning: 0.9577 and testing: 0.972l), decreased MSE (0.001), and a set of printing parameters not previously determined</td><td>[61] </td></tr><tr><td>closed-loop feedback control</td><td></td><td>Multi-lnput-Multi-Output 400 labeled data (MIMO) Fuzzy logic-based control algorithm</td><td></td><td>print states</td><td>Error and change in error of Filament extrusion speed, Layer height, Line Distance, Print speed</td><td>by trial and error was also identified. Five supervised ML algorithms- deep neural network (DNN),support vector machine (SVM), decision tree (DT), random forest (RF), and logistic regression (LR)- are used for classification.The resulting models are used to decide the status of printed</td><td>[62] </td></tr></table></body></html>  \n\nTable 3. (Continued)   \n\n\n<html><body><table><tr><td>Research target</td><td>Fabrication process</td><td>ML technique</td><td>Sample size</td><td>Inputs</td><td>Outputs</td><td>Major findings</td><td>Refs.</td></tr><tr><td>Predicting cross section of extrudate (concrete)</td><td>Material extrusion</td><td>Supervised: ANN</td><td>101 extrudate cross-sectional samples were generated</td><td>Shape ofthe nozzle outlet and flow rate</td><td>Shape of the extrudate cross-section</td><td>The ML-based proposed approach improves the surface quality of three structures with varying curvatures by adjusting the nozzle geometry to match the desired extrudate shape for</td><td>[63]</td></tr><tr><td>Optimizing Droplet Formation</td><td>Material jetting (lnkjet printing)</td><td>Supervised: Fully connected NNs (FCNNs)</td><td>N.A.</td><td>Applied voltage, viscosity, surface tension and nozzle diameter</td><td>Droplet diameter, droplet speed, satellite droplets</td><td>each structure. It can be used to optimize droplet printing and propose an optimal range of bio-inkpropertiesforbest printing outcome based on nozzle diameter.</td><td>[64]</td></tr><tr><td>Droplet Prediction</td><td>Material jetting (linkjet printing)</td><td>Supervised: Ensemble (random forest, LASSO,extreme gradient boosting, support vector</td><td>243 data points</td><td>Polymer concentration, excitation voltage, dwell time, rise time</td><td>Droplet velocity, droplet volume</td><td>The experimental results showed extreme [65] gradient boosting has highest predictive accuracy (R² = 0.977, RE= 0.044 and RMSE = 0.240) in accordance with the studied operating</td><td></td></tr><tr><td>Prediction of electrical conductivity</td><td>Material jetting (Electrohydrodynamic- jet)</td><td>Supervised: Random forest, Logistic regression, K-NN</td><td>A set of 240 samples</td><td>Nozzle speed, voltage between the print head and the substrate, and the flow rate</td><td>Conductivity of electrodes</td><td>conditions Random forest and K-NN (k = 10) models resulted in the highest accuracy (about 83%) in estimating the conductivity of graphene electrodes</td><td>[66] </td></tr><tr><td>Prediction of jetting window</td><td>Material jetting (Inkjet printing)</td><td>Supervised: 14 regressive models (linear regression, Bayes ridge, RANSAC, Decision tree, gradient boosting etc.) and deep neural network</td><td></td><td>1l features (frequency, rise time,fall time, dwell time, echo time,voltage, echo voltage,viscosity, surface tension, density, nozzle diameter)</td><td>Droplet jetting velocity, droplet radius, jettability prediction, jetting window prediction</td><td>Ensembles of DTs (GB and RF) were applied to predict the drop velocity and radius of 14 materials.The observed RMSE was 0.39 m s-1 and 2.12 μm respectively. The mean absolute percentage error is 3.87%. A neural network model was built to classify jetting category with 91.94% accuracy.</td><td>[67]</td></tr><tr><td>Tuning of colloidal ink composition and optimization of printing parameters</td><td>Material jetting (Microfluidic mixer-based printing)</td><td>Supervised: Support vector machine, random forest</td><td>N.A.</td><td> Feature maps</td><td>Deposition patterns</td><td>SVM model has achieved a balanced accuracy of 81.96% in classifying the internal textures of the evaporation-driven printed droplets.</td><td>[68]</td></tr><tr><td>Multi-objective optimization</td><td>Material jetting (Aerosol jet printing)</td><td>Supervised: Response surface method (RSM), genetic algorithm</td><td>105 samples</td><td>Sintering distance, print layers</td><td>Electrical resistivity, surface Response Surface Models (RSMs) were roughness</td><td>developed, and their associated statistical uncertainties were integrated with the NSGA-lll algorithm to effectively optimize the printing</td><td>[69]</td></tr></table></body></html>  \n\nTable 3. (Continued)   \n\n\n<html><body><table><tr><td></td><td>Material jetting (Aerosol jet printing)</td><td>Supervised: Response surface method (RSM), genetic algorithm</td><td>100 data points</td><td>Sheath gas flow rate, carrier gas flow rate, print speed</td><td>Edge roughness, film thickness</td><td>The RSMs were employed to determine the optimal operating window in the 2D space,considering the trade-off between printed line features and print speed using the desirability function approach. The derived RSMs and corresponding statistical uncertainties were jointly utilized with the NSGA-II</td><td>[70a] </td></tr><tr><td></td><td>Material jetting (Aerosol jet printing)</td><td>Supervised: Noisy (input Gaussian process (NIGP))</td><td>25 samples</td><td>Sheath gas flow rate, carrier Line width, edge gas flow rate, print speed</td><td>roughness,thickness</td><td>three-dimensional (3D) design space. Developed multi-objective optimization framework to optimize the overall printed line quality for customized line width printing using smalldata set and prediction uncertainty. Latin hyper sampling was combined with a noisy input Gaussian process</td><td>[70b] </td></tr><tr><td>ediction of features using transfer learning</td><td>Material jetting (Aerosol jet printing)</td><td>Supervised: Transfer learning (instance transfer, feature representation), model-based transfer</td><td></td><td>SheathgafowatecarrerLinewithege gas flow rate, print speed</td><td>roughness,thickness</td><td>It was found that Feature representation transfer generally produce much lower errors in the prediction of line width, line thickness and edge roughness. The errors are found to be 5% or smaller.</td><td>[70c]</td></tr><tr><td></td><td>int qualityoptimizationMaterialjetting (Aerosol jet printing)</td><td>Unsupervised and Supervised: K-means clustering, SVM, GPR, genetic algorithm</td><td>N.A.</td><td>Sheath gas flow rate, carrier gas flow rate</td><td>Edge roughness, thickness, overspray</td><td>the quality of Additive Jet Printing (AJP) by investigating the connection between the morphology of deposited droplets and the characteristics of printed lines. The approach employed Gaussian process regression to establish a process model for the geometrical properties of droplets.The deposited droplet morphology was</td><td>A ML method was introduced to optimize [70d]</td></tr></table></body></html>  \n\nTable 3. (Continued)   \n\n\n<html><body><table><tr><td>Research target</td><td>Fabrication process</td><td>ML technique</td><td>Sample size</td><td>Inputs</td><td>Outputs</td><td>Major findings</td><td>Refs.</td></tr><tr><td>Temperature field prediction</td><td>DED (Gas metal arc welding)</td><td>Supervised: Recurrent neural network and deep neural network (RNN-DNN) parts, and one convolutional neural</td><td></td><td>Spatial coordinates, material properties, and process parameters.</td><td>Thermal field, Temperature evolution</td><td>To detect the association between the deposition stage and its related thermal field, a physics-based ML approach based on an ensemble learning model was constructed. The time cost of a single prediction step</td><td>[71a,b]</td></tr><tr><td>Print quality optimization</td><td>Vat photo-polymerization (Digital light processing)</td><td>network Supervised: NN consisting of 2 U-Net-like NNs (master NN and slave NN)</td><td>24 samples</td><td>Grayscale maskimage M of Binary image P of the same The U-net like NNs enabled the use of size 512 ×512 size</td><td></td><td>Accuracy of 94% small sample size (as small as 32) for training data to generate grayscale masks that can print fine-detailed structures surpassing the traditional manual tuning method with identical</td><td>[72]</td></tr><tr><td>Print speed optimization</td><td>Vat photo-polymerization (Continuous liquid interface production)</td><td>Siamese networks</td><td>N.A.</td><td>Manufacturing speed, resin  Printing success/failure viscosity, part radius, PDMS thickness, surface type, curing time per layer, total curing time</td><td></td><td>Siamese Networks worked the best among all the investigated models (average training accuracy of 90.17% and testing accuracy of 88.42%) as it can effectively extract useful information from the mathematical</td><td>[73]</td></tr><tr><td>the aero-pendulum extruder (concrete)</td><td></td><td>Deep Reinforcement Learning: (twin-delayed deep deterministic policy gradient)</td><td></td><td>Critic network: environment states and agent's actions Actor network: environment states</td><td>Trajectory of the toolpath Critic network: Expectation of the long-term reward Actor network: actions that maximize the long-term reward</td><td>A better performance in terms of process[74] duration</td><td></td></tr></table></body></html>  \n\n![](images/b99137174244038ef39016e857295ebb0ee07f774eb32d595d7302fae6da7649.jpg)  \nFigure 18. Schematic diagram of a framework that utilized ML and knowledge graphs to formalize unstructured AM guidelines into structured knowledge. The framework comprised four key components: a priori knowledge structuration, transformation of AM data into AM knowledge, transformation of AM knowledge into design for AM ontology, and rule transformation. By employing this approach, the framework facilitated automated and autonomous construction and enhancement of AM design rules by leveraging both existing knowledge and data-driven insights. Reproduced with permission.[75] 2021, Elsevier.  \n\nA technique was developed to reverse engineer composite material parts using imaging methods and ML (Figure 20).[78] The approach captured the geometry of the parts and reconstructed the 3D printing tool path by examining the microstructure. The study utilized glass fiber reinforced acrylonitrile butadiene styrene filaments for 3D printing specimens, which were then reverse-engineered using micro-computed tomography $(\\upmu\\mathrm{{CT})}$ scans and scanning electron microscopy (SEM) images. The tool-path information was extracted by identifying fiber orientation in each layer using an RNN with LSTM architecture. The results showed high accuracy in predicting printing orientation (error of $0.5^{\\circ}1$ and achieved high dimensional accuracy in the reverse-engineered models. The research demonstrated the potential to reverse engineer high-quality replicas of composite parts by leveraging the capabilities used for designing highperformance composites.  \n\n![](images/34b7101652e71fdebfa5f689d54692033bbee848161086280ad86679d87b14c2.jpg)  \nStep1:BuildinglmageDatabase   \nStep 2: Training a VAE   \nFigure 19. The metamaterial optimization framework involved three main steps. In Step 1, samples were drawn from a random process to create an artificial database of representative volume element images, each consisting of $28\\times28$ pixels. Step 2 involved training a variational autoencoder to generate realistic output samples. By flipping the $28\\times28$ images twice, larger $56\\times56$ RVE images were obtained, which preserve symmetry. Finally, in Step 3, the framework employed Bayesian optimization to achieve the optimal design of a representative volume element that met the specified macroscopic elastic moduli requirements. Adapted with permission.[76] 2020, Elsevier.  \n\n![](images/442bb0d5112d38ec3311e49c8e97cbc4a3defcf95a99bb45fb724b0d571a7186.jpg)  \nFigure 20. The implementation of a reverse engineering method using both $\\upmu\\mathsf{C T}$ scan and SEM images of the model. The tool-path details are extracted by employing an RNN with LSTM architecture, which identifies the fiber orientation within each layer. This approach enabled the reconstruction of the model’s toolpath based on the available imaging data. Reproduced with permission.[78] 2020, Elsevier.  \n\nResearchers are advancing the field by integrating ML into AM processes for automating customization, optimizing parameters, improving part quality, and facilitating design rule development. These advancements enable efficient and cost-effective production, while also promoting collaboration and innovation within different research groups.  \n\nAn optimization method for complex mechanical structures was demonstrated by combining the RSM and multi-objective genetic algorithm (MOGA).[79] After conducting experimental modal analysis and FEA on the inkjet printer, the method identified weak points and performance aspects of the structure. The central composite design (CCD) method was deployed to select sample points for numerical simulations and the initial secondorder RSM, which focused on the printer’s first-order natural frequency, weight, and maximum deformation of the inkjet head, was established. The approximation optimization of the RSM was then carried out using MOGA, resulting in a Pareto optimal solution set. The method demonstrated increased computational efficiency compared to conventional optimization methods and was good for multi-objective optimization of complex structures printed by the inkjet printer. The optimized solution increased the printer’s first-order natural frequency by $36.3\\%$ , reduced the maximum deformation of the inkjet head by $33\\%$ , and lowered the printer’s weight by $19.5\\%$ . There was a trade-off between computing costs and accuracy, hence it is necessary to discover the optimal balance for future research.  \n\nThe synergy of ML with design and topology optimization for 3D printing holds the promise of pushing boundaries, that allows creating efficient and sustainable designs for specific applications. As we delve deeper into this intersection, we will explore the mechanisms through which ML augments the design process, addresses the challenges, and opens the horizons in the dynamic world of 3D printing (Table 4).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 3.4. Microstructure Analysis  \n\nThe microstructure of metal printed parts is critical for determining their mechanical, thermal, and functional properties. However, there are several challenges in characterizing the microstructure in AM parts. The AM process introduces unique complexities such as rapid solidification and cooling rates, which results in distinct microstructural features compared to conventional manufacturing methods. Moreover, spatial variations within a single part and the need for non-destructive evaluation further complicate microstructural analysis. To address these challenges, advanced imaging techniques such as electron backscatter diffraction (EBSD), X-ray CT, and high-resolution microscopy have emerged as powerful tools for microstructural characterization in metal printing. These techniques enable the visualization and quantification of grain morphology, crystallographic orientations, and defects. However, analyzing the vast amounts of data obtained from these techniques requires sophisticated data analysis methods. This is where ML and DL algorithms come into play, offering automated approaches to extract meaningful microstructural descriptors and establish quantitative relationships between processing parameters and microstructure variations.  \n\n(Continued)   \nTable 4. ML for design optimization in AM.   \n\n\n<html><body><table><tr><td>Research type</td><td>Research target</td><td>Fabrication process</td><td>ML technique</td><td>Sample size</td><td>Inputs</td><td>Outputs</td><td>Major findings</td><td>Refs.</td></tr><tr><td>Design optimization</td><td>ML and KG based design rule construction for AM</td><td></td><td>Supervised: Classification and regression tree CART</td><td>N.A.</td><td>Prior knowledge and surface roughness measurement data from a LPBF build</td><td>Design rule for overhang features</td><td>Data-Knowledge-Design Rule (DKDR) framework, which comprises of a prior knowledge structuration, AM knowledge to-DfAMOnt transformation, AM data-to-AM knowledge transformation, and Rule</td><td>[75]</td></tr><tr><td>Design optimization</td><td>Automatic design of composite mechanical</td><td></td><td>Unsupervised: Variational autoencoder (VAEs)</td><td>200</td><td>28 ×28 image pattern (representative volume</td><td>Elastic moduli</td><td>and KG. Bayesian optimization was used to get the necessary elastic moduli.</td><td>[76]</td></tr><tr><td>Design optimization</td><td>Toolpath reconstruction Material extrusion using imaging</td><td>(FFF)</td><td>Supervised: Recurrent neural network with LSTM</td><td>(70:30)</td><td>78373 images CT-scan images</td><td>Direction of fiber</td><td>The original models were reverse engineered with just a 0.33% discrepancy in dimensional correctness.</td><td>[78]</td></tr><tr><td>Design optimization</td><td>Design optimization</td><td>Material jetting (Inkjet printing)</td><td>Supervised: RSM Multi-objective genetic algorithm</td><td>N.A.</td><td>8 parameters as design variables for optimization</td><td>Natural frequency, maximum deformation weight</td><td>The optimal solution proposed in this study demonstrates a significant improvement in the first-order natural frequency of the inkjet printer, resulting in a remarkable 36.3% increase. This enhancement effectively mitigates the resonance region caused by the excitation of the servo motor. Additionally, the maximum deformation of the inkjet head is reduced by 33%,leading to enhanced stability and performance.Furthermore, the weight</td><td>[79]</td></tr><tr><td>Design optimization</td><td>Crack prediction</td><td>PBF</td><td>Supervised: High-fidelity surrogate model based on an Attention-based U-Net architecture</td><td>540</td><td>3D geometries</td><td>index</td><td>resulting in a more lightweight and compact design. Maximum shear strain Maximum Shear Strain Index (MSSl) as a dependable index for crack formation, it demonstrated how a deep convolutional neural network equipped with an attention-based 3D U-Net architecture could be trained as a trustworthy surrogate of the time-consuming construction process simulation,</td><td>[80] </td></tr></table></body></html>  \n\nTable 4. (Continued)   \n\n\n<html><body><table><tr><td>Research type</td><td>Research target</td><td>Fabrication process</td><td>ML technique</td><td>Sample size</td><td>Inputs</td><td>Outputs</td><td> Major findings</td></tr><tr><td rowspan=\"3\">Design optimization</td><td rowspan=\"3\">Composite layer design Material jetting for tissue-mimicking</td><td>(Inkjet</td><td>Supervised: ANN and GE</td><td>(with 72</td><td>hardness,base shore</td><td>216 specimens Infilltype,coating shore Shore hardness and compressive</td><td>By 3.5%, the ML technology surpasses the surface response method.</td></tr><tr><td>anatomical models Printing)</td><td></td><td>combina- tions of</td><td>hardness, height, coating & base</td><td>modulus</td><td>Material characteristics ranging from 20A to 65A may be simulated using the multi-layer model.</td></tr><tr><td></td><td></td><td>design parameters)</td><td>thickness</td><td></td><td></td></tr></table></body></html>  \n\nThe choice of ML approach for microstructure analysis in AM is dependent on the specific objectives and the nature of the microstructure data. Microstructure analysis in AM involves examining the internal structure of 3D-printed parts to understand their properties and quality. Supervised learning is suitable when there is labeled microstructure data with corresponding information about the specific microstructure characteristics or properties, while unsupervised learning is suitable for discovering patterns, clusters, or anomalies in microstructure data without having pre-defined labels. A combination of supervised and unsupervised techniques may be beneficial for microstructure analysis in AM; the initial use of unsupervised learning to discover patterns in the data, followed using supervised learning to predict specific microstructure based on those patterns. More discussion on the use of different ML techniques for microstructure analysis in AM will be provided in the subsequent sections.  \n\nOptimization of AM processes can be performed by leveraging ML models to correlate processing parameters with specific microstructural characteristics. A DL framework for the quantitative analysis of microstructural variations in metals fabricated through additive friction stir deposition technique was developed to predict the grain size, grain orientation, and grain boundary morphology.[82] Microstructural descriptors were extracted by utilizing EBSD patterns and were used to represent the differences in microstructures under different processing conditions. A regeneration neural network was employed to predict new microstructures within the reduced representation domain. The framework was validated using samples produced through additive friction stir deposition, known for equiaxed microstructures. The study addressed challenges in high-dimensional data processing and the identification of principal microstructure descriptors that aligned with specific problem goals. The results demonstrated the effectiveness of the framework in capturing salient changes within microstructures and accurately regenerating them. The physical insights in microstructure descriptors obtained through mapping the regenerated microstructures provided valuable understanding. The study establishes a foundation for quantifying processing-microstructure linkages in metal AM and holds promise for applications in materials science, including heterogeneous material design and optimization. Figure 21 provides a summary of the applications of ML in AM for the prediction of various microstructure-related properties.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# 3.4.1. Powder Bed Fusion  \n\nDetermining the mechanical properties of 3D-printed metal parts is crucial for ensuring their reliability, functionality, and safety. However, there are unique challenges in determining the mechanical properties of 3D-printed metal parts. The microstructure and defects in the printed material can significantly affect its properties, making it essential to consider factors like porosity, grain structure, and residual stresses. Furthermore, the complex geometry and layer-by-layer fabrication process of 3D printing make it difficult to perform standardized testing. ML techniques offer a promising solution to address the associated challenges. By analyzing diverse datasets, ML algorithms can predict mechanical properties based on geometrical and microstructural features, reducing the need for extensive experimental testing. These algorithms can also identify correlations between printing parameters and mechanical properties, optimizing the printing process. ML aids in defect detection and classification, enhancing quality control and it enables more efficient and effective characterization of 3D-printed metal parts by leveraging the power of AI.  \n\n![](images/06cd5b77967c753ffd9b9c39048390590591992d86966152deec4d892b53c1fa.jpg)  \nFigure 21. Graphical overview depicting the applications of ML in the field of AM for predicting various properties related to microstructure.  \n\nVarious ML techniques such as NN,[83] gradient boosting regression,[84] SVM,[85] and $\\mathrm{GA}^{[86]}$ have been utilized for predicting the mechanical property of 3D-printed metal parts with a good coefficient of determination $(R^{2}\\colon0.84\\ –0.98)$ . The mechanical properties that were explored include the ultimate tensile strength, the maximum elongation, the fatigue life, and the microhardness of the 3D-printed metal parts. The inputs were dependent on the type of mechanical properties (static or dynamic). Inputs for static mechanical properties include process parameters, parts and build orientations, surface roughness, relative density, and crystal orientation, while the inputs for dynamic mechanical properties include stress, build orientation, defect size and depth, and loading conditions.  \n\nFor most cases, the mechanical properties of 3D-printed materials are assessed at the specimen level, employing a range of standardized testing methodologies to ensure consistency, reliability, and comparability of results. The American Society for Testing and Materials (ASTM) provides several standards that are widely adopted in evaluating the mechanical properties of materials produced by additive manufacturing processes. These standards help in defining the procedures for preparing specimens, conducting tests, and interpreting the results for materials such as metals, polymers, and composites. ASTM F2971- 13,[87] ASTM E8/E8M,[88] and ASTM E9[89] are some notable ASTM standards used in the testing of 3D-printed materials. Utilizing these ASTM standards in testing 3D-printed materials ensures that the mechanical properties are measured accurately and consistently, facilitating the comparison of data across different studies and applications. It also helps in validating the performance of 3D-printed parts against traditional manufacturing methods, aiding in the broader acceptance and adoption of additive manufacturing technologies. These standards guide the testing of uniformly prepared specimens that are assumed to represent the material’s overall characteristics. The results, such as tensile strength, elongation, compressive strength, and flexural modulus, are considered to reflect the average or bulk properties of the material across the entire specimen. This assumption is valid under the premise that the specimen is homogeneous, and the material properties are uniform throughout the specimen. In 3D printing, however, the layer-bylayer manufacturing process and the potential variability in microstructure across different regions of a part may challenge this assumption.  \n\nThe repeatability of LPBF-printed metal parts was investigated using ML models (Figure 22a).[90] The mechanical properties of the printed metal parts (standard deviation of yield strength, tensile strength, and maximum elongation) were used to quantify the repeatability. The study showed that the DT method was the most efficient method to classify and predict the quality of the part, achieving an F1 score of $95\\%$ . While most ML models are trained with homogenized properties, derived from standardized testing of uniform specimens, their application extends beyond simple predictions to encompass the complex and varied nature of arbitrary 3D-printed parts. This potential is rooted in the ability of these models to analyze and predict based on diverse inputs, offering a nuanced understanding of material behavior. For instance, the ML models can be trained on a dataset that captures a wide range of mechanical properties, geometries, materials, and print parameters, allowing the model to recognize patterns and correlations that apply across different printing scenarios. By extracting detailed features of an arbitrary part, including its geometry, material composition, and print settings, ML models could potentially predict its localised mechanical properties so that designers can rapidly iterate on designs by incorporating predictive insights into mechanical properties, effectively tailoring parts to specific performance criteria.  \n\nThe adaptation of new printers requires a lot of effort due to the high variability of 3D printers in determining the optimal process window to fabricate AM parts with good mechanical strength. The main challenge involves the collection of a large dataset which can be time consuming and costly. Notably, this can be solved using ML models to predict the performance of the printed parts that are fabricated by a new printer using a small dataset via a transfer learning technique. The published data of LPBF Ti-6Al-4 V parts was used for the model training to predict process parameters for different hardness-porosity property combinations (Figure 22b).[86] The challenges of predicting processproperty relationship include 1) adopting a new printer model from the same manufacturer, 2. adopting a printer from different manufacturers but with similar technology, and 3) adopting a printer from a new manufacturer with different technology. Bayesian optimization models were found to be effective in modeling process-property relations and outperformed other models. The framework demonstrated the feasibility of crossmachine knowledge transfer and multi-property optimization experiments. The work highlights that data mining-assisted ML efforts can accelerate the development and optimization of metal 3D printing processes, emphasizing the need for standardized reporting of data and the creation of a comprehensive metals AM database.  \n\n![](images/c860c62833db0f5521f195e3e9987f727f946490d2f0c19691ad11a2986363b5.jpg)  \nFigure 22. a) Schematic showing the workflow of ML technique for predicting the mechanical property of 3D-printed metal parts. Reproduced with permission.[90] 2021, Elsevier. b) Schematic showing the workflow for training an ML model for predicting the performance of the 3D-printed parts from a new printer. Reproduced with permission.[86] 2021, Elsevier.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 3.4.2. Material Extrusion  \n\nA study demonstrated prediction of mechanical properties in 3D FDM-printed parts. This was addressed by developing a data-driven predictive model using LSTM networks for FDM processes.[91] The model took into account the layer-by-layer printing process and related cyclic layer thermal history to improve accuracy and reliability. Layer-wise activities were captured using sensors (IR sensor, thermocouple, and accelerometer) and their data were incorporated into the LSTM network. The LSTMbased predictive model outperformed traditional ML techniques such as support vector regression (SVR) and RF by $9.8\\%$ and $24.3\\%$ respectively. Key findings of the study included significant improvements in prediction performance by incorporating in-process sensing data, high relevance of infrared sensor and accelerometer data for tensile strength prediction, and substantial contributions of process parameters to tensile strength prediction. The LSTM model demonstrated the effectiveness of sequential layer-by-layer modeling of the FDM process, paving the way for improved microstructure analysis in AM applications.  \n\nTo address the issue of poor part strength in extrusion-based additive manufacturing processes, another study developed an ANN model to predict the tensile strength of 3D-printed parts.[92] The ANN model considered various input variables such as layer thickness, orientation, raster angle, nozzle temperature, bed temperature, room temperature, air gap, and barrel temperature and showed higher accuracy and lower errors compared to existing response surface methodology (RSM) models with rootmean-square-error (RMSE) values for ANN and RSM models at 0.49 and 0.90, respectively. This approach offers significant improvement in predicting part strength, enabling better optimization of manufacturing process conditions and cost-effective additive manufacturing. Another study utilized RF and ANN (known for their ability to capture nonlinearity) to predict the dynamic strength of 3D-printed continuous ramie fiber reinforced biocomposites (CRFRC) under various conditions (varying layer thicknesses, hatch spacings, and strain rates).[93] The ANN model outperformed RF in prediction accuracy $5\\%$ error compared to $9\\%$ error) and provided insights into the importance of different factors. ML proved advantageous in accurately predicting CRFRC’s dynamic strength, optimizing printing parameters, and understanding the influence of microstructural characteristics on composite performance.  \n\nA comparative analysis of selected ML algorithms (ANN, SVM, and RF) was performed for construction printing to evaluate the interlayer bonding in layered cementitious composites using non-destructive testing and measurements.[94] The objective was to simplify the mathematical models by reducing the number of input parameters, making it more practical for implementation in real-world scenarios. The study concluded that ANN yielded the most accurate results in predicting interlayer bond strength, yielding a linear correlation coefficient $R^{2}$ of 0.883 and RMSE of 0.341 MPa. The ANN model was trained using data from various mixtures and it effectively predicted the interlayer bond strength and determined the optimal printing parameters for obtaining strong interlayer bonding.  \n\nML models were used to classify 3D-printed boron-based geopolymer samples based on their compressive strength.[95] Supervised ML algorithms such as recursive-partitioning functions rpart and ctree, were used to build separate classification models. The models were compared in terms of simplicity and cumulative accuracy. The rpart function demonstrated slightly better performance, with a cumulative accuracy of $70\\%$ as compared to the ctree function’s $63\\%$ accuracy. Furthermore, the rpart function required fewer parameters for prediction. The study highlighted the importance of the slag content and the ratio of boron ions in determining the compressive strength of samples. The application of machine learning significantly reduces the error in predicting compressive strength, demonstrating its potential for developing a guide or standard for classifying 3D-printed boronbased geopolymer samples based on compressive strength.  \n\nAnother study proposed a hybrid approach combining the multi-objective grasshopper optimization algorithm (MOGOA) and ANN to predict the compressive strength of 3D-printed concrete.[96] The MOGOA was used to optimize the architecture of the ANN model, considering the number of hidden layers and neurons in each layer. The results showed that the hybrid MOGOA-ANN model achieved accurate predictions (mean absolute percentage error (MAPE) of $92\\%$ ) of the compressive strength, even with simplified neural network architectures. This approach can reduce computational complexity and enable faster predictions in the material design process (Table 5).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# 3.5. Material Formulation  \n\nMaterial formulation is a pivotal process in achieving desired properties for various applications. Two key considerations in this endeavor are processability and the targeted end-use properties. Achieving this balance can be intricate due to the multifaceted nature of material behavior and the interplay between different parameters. Processability entails ensuring that the material can be effectively and reliably processed into the desired form. On the other hand, tailoring materials to exhibit specific properties such as mechanical strength, thermal conductivity, or electrical resistivity is crucial for meeting the demands of diverse applications. However, this pursuit is often a delicate balancing act. Enhancing one aspect may inadvertently impact another. For instance, increasing mechanical strength might result in reduced flexibility. Moreover, this trade-off is complicated by the multitude of factors at play, including chemical composition, processing conditions, and material microstructure. This is where ML steps in as a powerful tool. By ingesting and analyzing vast datasets encompassing various material compositions and their corresponding properties, ML algorithms can identify complex relationships and patterns that might elude traditional analysis. This enables the formulation of predictive models that guide the selection of optimal material compositions to achieve desired properties, while also considering processability constraints.  \n\n![](images/1be5a015174149dd1d9939e653789e55c7e1a51bda9376596bc2880f6973d4e9.jpg)  \nFigure 23. A graphical overview summarizing the applications of ML in material formulation for AM.  \n\nThe choice of ML approach for material formulation in AM is dependent on the specific goals and challenges associated with the material development process in AM. Material formulation in AM involves designing and optimizing the materials with desired properties for 3D printing. Supervised learning is suitable when there is labeled data that associates material compositions with specific material properties or performance metrics, while unsupervised learning is suitable for discovering patterns, clusters, or similarities among materials or their properties without pre-defined labels. A combination of supervised and unsupervised techniques may be beneficial for material formulation in AM; the initial use of unsupervised learning to discover complex relationship in the data followed by using supervised learning to build predictive models for specific material properties. More discussion on the use of different ML techniques for material formulation in AM will be provided in the subsequent sections (Figure 23).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# 3.5.1. Powder Bed Fusion  \n\nAlloy selection profoundly influences the entire AM process, spanning from the initial energy-source-material interactions to the final component characteristics. The degree to which lasers are reflected or absorbed by a powder bed is contingent upon the powder’s makeup.[100] Both the internal and external granular densities of the feedstock contribute significantly to the density of the end products.[101] Moreover, the thermal properties of the selected alloy partially dictate the conduction pathways in the molten state.[102] Variations in solidification rates among alloys can result in significantly diverse post-manufacture microstructures.[103] Certain AM-related challenges, such as the evaporation of elemental constituents due to intense thermal changes, can be attributed to material composition. This can affect the stoichiometry of the melt pools and ultimately the quality of the finished product.[104] Furthermore, some research has probed the influence of feedstock attributes, like particle size distribution and shape, on process outcomes.[100b,105] Yet, the exact effects remain to be fully elucidated.  \n\nDatabases offering a myriad of alloy attributes serve as indispensable tools in the realm of materials science. Notably, the International Crystal Structure Database (ICSD) hosts crystallographic structures of countless materials, while the Linus Pauling files extend from atomic specifics, such as radii and electron valence, to more advanced crystallographic information.[106] Contemporary platforms like Aflow[107] and the Materials Project[108] empower users with sophisticated search functionalities across diverse alloy datasets. The efficacy of data mining in advancing AM alloy development has been underscored by several studies. A study employed this method to optimize the chemistry of aluminum alloys for enhanced processing during LPBF.[102] The printed Al alloys historically faced challenges such as limited grain nucleation, resulting in the coalescence of expansive grains and concomitant intergranular stresses, predisposing the material to hot-cracking. To mitigate this, a study sought potential grain inoculant compounds, generated via chemical reactions during LPBF, which could refine grain properties. A notable solution emerged when silicon and carbon reactions birthed SiC particles, promoting more uniform grain nucleation. However, the lattice disparities between certain compounds and the aluminum alloy could induce substantial stresses at their interface, perpetuating cracking issues. Consequently, the focus shifted to identifying inoculants with lattice parameters aligning with the primary aluminum alloy. Through the deployment of a search algorithm probing around 4500 potential nucleants, hydrogen-stabilized Zr emerged as the optimal candidate.  \n\nTable 5. ML for microstructure analysis in AM.   \n\n\n<html><body><table><tr><td>Research target</td><td>Fabrication process</td><td>ML technique</td><td>Sample size</td><td>Inputs</td><td>Outputs</td><td> Performance</td><td>Refs.</td></tr><tr><td>Predict microstructure</td><td>Additive friction stir deposition</td><td>Supervised: convolutional neural network (VGG16)</td><td>Nil</td><td>EBSD scans</td><td>Grain size, grain orientation, and grain boundary morphology</td><td>Near 100% accuracy</td><td>[82] </td></tr><tr><td>Predict mechanical property</td><td>PBF</td><td>Supervised: a custom 3D convolutional neural network (CNN) based</td><td>7680</td><td>Crystal orientation as input (with or without auxiliary input features)</td><td>Mechanical properties</td><td>R2 value of 0.84 and a root mean square error (RMSE) value of 16.57 MPa.</td><td>[83a]</td></tr><tr><td>Prediction of fatigue life</td><td>PBF</td><td>on VGGNet Supervised: Backpropagation neural network</td><td>32800 data points</td><td>Stress, build orientation, defect size, defect depth, defect distance to</td><td>Fatigue life</td><td>R2 value of greater than 0.98</td><td>[83b] </td></tr><tr><td>Mechanical property prediction</td><td>PBF</td><td>Supervised: Gradient boosting regression</td><td>3000</td><td>surface Surface roughness and void position, number density</td><td> Mechanical property</td><td>R² value of greater than 0.98</td><td>[84]</td></tr><tr><td>Fatigue life</td><td>PBF</td><td>Supervised: ANN, random forest, Support vector machine</td><td></td><td>and size Process parameters, fatigue loading conditions</td><td>Fatigue life</td><td>R2 value of greater than 0.95 for random forest and SVM</td><td>[85] </td></tr><tr><td>Transfer learning for property prediction</td><td>PBF</td><td>Supervised: Multi-Objective Genetic Algorithm (MOGA)</td><td>Data from 120 manuscripts</td><td>Laser power, scan speed, energy density, hatch spacing,layer thickness, powder size</td><td>Relative density, microhardness,</td><td>Overall prediction accuracy of 88%</td><td>[86] </td></tr><tr><td>Repeatability of printed parts</td><td>PBF</td><td>Supervised: Tree-based models</td><td>167</td><td>Production parameters such as build mass, height and time, part volume, sample locations and temperature parameters.</td><td>Static mechanical properties such as yield strength, tensile strength, and maximum elongation.</td><td>F1 score > 0.95</td><td>[90] </td></tr><tr><td>Tensile strength prediction</td><td>Material extrusion (FFF)</td><td>Supervised: LSTM</td><td></td><td>Material property, extruder temp, printing speed, layer height</td><td>Tensile strength</td><td>With an RMSE of roughly 2%, the developed LSTM model outperforms previous ML models in predicting the tensile strength of 3D-printed parts.</td><td>[91] </td></tr></table></body></html>  \n\n(Continued)   \nTable 5. (Continued)   \n\n\n<html><body><table><tr><td>Research target</td><td>Fabrication process</td><td>ML technique</td><td>Sample size</td><td>Inputs</td><td>Outputs</td><td>Performance</td><td>Refs.</td></tr><tr><td>Part strength prediction</td><td>Material extrusion (FFF)</td><td>Supervised: ANN, RSM</td><td>120 (70:15:15)</td><td>Layer thickness, orientation, raster angle, raster width, air gap</td><td>Tensile strength</td><td>Pellet based printing: The RMSE for the ANN results are lower in most of the cases, which shows the adequacy of this model, but ANN is not suitable for less data, while</td><td>[92] </td></tr><tr><td>Dynamic tensile strength prediction</td><td>Material extrusion (FF)</td><td>Supervised: Random forest, ANN</td><td>108 (81:27)</td><td>Hatching spacing, layer thickness, strain rate</td><td> Tensile strength </td><td>to predict the strength. The workflow combines dual-resolution Robotic Scanning, Neural Network prediction and printing of PETG plastic. This integrated approach offers the advantage of responding</td><td>[93]</td></tr><tr><td>Interlayer bond strength prediction (concrete)</td><td>Material extrusion</td><td>Supervised: ANN, SVM, RF</td><td></td><td>Parameters of concrete surface repair cover thickness: 10-point height, core height, reduced peak height, average mobility, overlay thickness, frequency of the sound wave reflection from the bottom</td><td></td><td>customization. ANN provided the most accurate assessment of the interlayer bonding pull-off adhesion of layered concrete, with an average relative error of 10.13 percent.</td><td>[94]</td></tr><tr><td>Compressive Strength prediction (concrete)</td><td>Material extrusion</td><td>Supervised: The conditional inference trees (ctree) and recursive partitioning (rpart) methods</td><td></td><td>Weight percentages of the fly ash and Ground granulated blast-furnace slag (GGBFS) (%S), as well as the ratios of boron ions</td><td>Compressive strength</td><td>Ctree function has a 100% positive predictive value, while rpart has a positive predictive value of up to 81%.</td><td>[95]</td></tr></table></body></html>  \n\nTable 5. (Continued)   \n\n\n<html><body><table><tr><td>Research target</td><td>Fabrication process</td><td>ML technique</td><td>Sample size</td><td>Inputs</td><td>Outputs</td><td> Performance</td><td>Refs.</td></tr><tr><td>Compressive strength prediction (concrete)</td><td>Material extrusion</td><td>Supervised: Multi-objective Grasshopper Optimization algorithm's</td><td>N.A.</td><td>Water-cement ratio (W/C),amount of coarse aggregate (CA), amount of fine aggregate (FA), amount of</td><td>Compressive strength</td><td>Accuracy of ANNMOGOA-1 is about 92%</td><td>[96]</td></tr><tr><td>Surrogate model to predict peak and maximum displacement of beam of cellular</td><td>Material extrusion</td><td>Supervised: ANN</td><td>1800</td><td>Number of TPMS layers and volume fraction</td><td>Peak load Maximum displacement</td><td>The maximum deviations of 2.5% and 3.5% for peak loads and maximum midpoint displacements</td><td>[97]</td></tr><tr><td>design (concrete) Predicting the auxetic behavior of cementitious cellular composite (concrete)</td><td>Material extrusion</td><td>Supervised: perceptron-based neural network (NN) Shapley additive explanations (SHAP)</td><td>850 combinations FEA simulation results</td><td>Design parameters: aspect ratio, length of the major axis, number of voids along the X- and Y- directions</td><td>Poisson's ratio</td><td>R²> 0.99 and MSE <0.0004</td><td>[98]</td></tr><tr><td>Crack prediction of air-void structure (concrete)</td><td>Material extrusion</td><td>Supervised: U-net CNN</td><td>193989 (95:5)</td><td>2D microstructure image containing pores (32 by 32 pixels)</td><td>Crack patterns</td><td>CNN model predictions show excellent agreement with lattice numerical analyses, with an Intersection over Union (loU) of 0.85 for crack pattern prediction and an R² value of 0.75 for stress-crack width curve prediction.</td><td>[99] </td></tr></table></body></html>  \n\nThe challenges of data mining from existing literature include missing values from isolated studies of individual parameters or properties. A database linking process parameters and material properties in SLM-fabricated Ti6Al4V alloys was developed.[109] Various data imputation methods such as K-NN, multivariate imputation by chained equations, and graph imputation neural network (GINN) were explored to fill missing data. The K-NN model excelled in process parameters, whereas GINN model excelled in material properties. The imputation quality was enhanced by using the median of the values from the three models, and a self-organizing map provided visualization of the relationships between process parameters and material properties.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# 3.5.2. Material Extrusion  \n\nOne key area of focus in material formulation for material extrusion technique is the rheological properties of the extrudate to ensure good flowability and extrudability. A study was conducted to investigate the effects of various admixtures on the rheological properties of cement paste for 3D printing applications.[110] An empirical formula was proposed to analyze the relationship between dynamic yield stress and mini-slump. ANN model was used to predict dynamic yield stress and mini slump based on admixture proportions. The model was validated by simulating new mixes, and the results demonstrated a high level of effectiveness in predicting the correlation between mini-slump and dynamic yield stress. This work opens avenues for future research to consider the time factor in ANN models for predicting printability over time.  \n\nA novel ML algorithm called gene expression programming (GEP) was used to develop mathematical models that predict the rheological properties of concrete such as yield stress and plastic viscosity.[111] A comprehensive database was built using previous experimental results and the significant input parameters that influence concrete rheology (cement, sand, water, small and medium-sized coarse gravels, and superplasticizer) were identified. The GEP models, which use simple arithmetic expressions to describe the relationships between the input parameters and the rheological properties, exhibited a strong correlation with experimental data ( $R^{2}$ of 0.998 for yield stress and $R^{2}$ of 0.978 for plastic viscosity). The models demonstrated high efficiency and predictability, with performance index factors indicating their accuracy. Various statistical parameters and external validation checks further confirmed the precision and generalization capacity of the GEP models in predicting the rheological properties of fresh concrete.  \n\nAnother study focused on predicting the static yield stress $(\\tau\\mathsf{S}_{n})$ of blended cement pastes containing supplementary cementitious materials (SCMs) using ML models.[112] A dataset from previous experimental work was collected and eight input parameters, including SCM properties, cement reactivity, mixture design parameters, and resting time were identified. A comparison of different ML models (MLP, RF, and SVR) was conducted and the MLP model demonstrated the highest accuracy with low RMSE and high coefficient of determination $\\scriptstyle(R^{2})$ . The study revealed that $\\tau\\mathsf{S}_{n}$ was primarily influenced by the amount of pseudo-contact points, while the amount of cement replacement by SCM had the least effect by analyzing the importance of different input parameters using Shapley-value and permutation feature importance analysis. These ML models show promise in improving mix design for innovative concrete technologies that require better workability control such as concrete printing or self-consolidating concrete.  \n\nApart from the rheological properties, ML has also been used to predict the optimal composition of additives for the feedstock material. A study investigated the 3D-printing of polylactic acid (PLA) composites reinforced with chopped long carbon fiber using an FDM printer.[113] The study employed gaussian process modeling, an ML technique suitable for small dataset, to predict the optimal carbon fiber content for the composites The model predicted the best mechanical performance at $6.7~\\mathrm{wt}.\\%$ carbon fiber, closely aligning with the experimental result of $5\\mathrm{wt.\\%}$ carbon fiber. The use of ML demonstrated its advantages in accurately predicting material properties and optimizing composite performance, potentially saving time and resources in the manufacturing process.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# 3.5.3. Material Jetting  \n\nMaterial design plays a crucial role in 3D printing of electronics, as it directly influences printability and the final properties of the printed traces (conducting, semi-conducting, or insulating). Additives such as surfactants or binders are typically added to the functional materials to ensure good printability of the functional inks. The proportion of different solvents is important in determining the printability and the final deposition pattern for certain inks. Important factors such as particle loading, and particle size can influence the printability and final electrical property of the printed structures. It can be a daunting task in identifying the optimal parameters and ratios for the materials. Therefore, researchers are increasingly turning to ML techniques to predict the performance of the final printed electrical circuits and components, streamlining the process, and improving overall outcomes.  \n\nA study introduced a strategy that leveraged ML models to guide the 3D printing process of Cu anode scaffolds directly onto solid-state NASICON-type $\\mathrm{Li_{1+x}A l_{x}}^{3+}\\mathrm{M}_{2-x}^{4+}(\\mathrm{PO}_{4})_{3}$ (LATP)  \n\n![](images/3f841a414200cfc592ec616a14a8dd178adc00167f96d04bc4402a88cb7a8cac.jpg)  \nFigure 24. Illustration showing the ink formulation optimization using RSM to improve the electrical resistivity and line quality. Reproduced with permission.[115] 2023, Nature Portfolio.  \n\nelectrolytes, thereby addressing obstacles associated with lithium batteries.[114] A sequential learning method based on mixture design was employed to refine the formulation of the printing ink, the rheological parameters, and the operational conditions of the 3D printing process. The method streamlined experimental work by systematically enhancing the design variables through a sequence of experiments, resulting in a sturdy methodology for ink characterization. The printed hierarchical scaffold and copper oxide (CuO) interlayer substantially decreased overpotential in comparison to unadorned lithium anodes, which was achieved by improving interfacial contact to mitigate the formation of lithium dendrites and inhibit side reactions. In summary, the research introduced a novel methodology for swiftly exploring anode geometries and 3D printable inks for lithium batteries, exploiting both experimental design and machine learning techniques.  \n\nA hybrid multi-objective optimization technique was used to identify the best functional ink composition for aerosol jet printing technology and obtain low electrical resistivity and good printed line quality (Figure 24).[115] The suggested method systematically examined the causal relationship between several ink components (ethanol, nanoparticle silver ink, and carbon nanotube (CNT) ink) and printing outcomes. Two RSM were created based on the analysis of variance; a non-dominated sorting genetic algorithm III (NSGA-III) was then merged with these models to provide a more reliable optimization in the 3D mixture design space. This data-driven methodology extended the process of creating materials with multi-component and multi-property in aerosol jet printing technology, resulting in higher electrical performance and broader applications in the field of printed electronics (Table 6).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# 4. Outlook",
+        "category": " Conclusions"
+    },
+    {
+        "id": 25,
+        "chunk": "# 4.1. Advanced ML Models  \n\nLarge Language Models (LLMs) are revolutionizing the ML landscape, showcasing broad applicability across domains due to their profound understanding of language and context. These advanced AI systems are designed to comprehend, generate, and interact with human language at scale, excelling in tasks like writing, translating, summarizing, and question-answering. Fuelled by DL techniques and the transformer architecture, exemplified by OpenAI’s GPT series, LLMs process and generate coherent, contextually relevant text. “MechGPT”, developed by Buehler’s group, exemplifies their prowess in modeling mechanics and materials, showcasing the model’s proficiency in knowledge retrieval, hypothesis generation, and bridging disparate areas for understanding and predicting material behavior and failure mechanisms.[116]  \n\nRecent efforts have also focused on enhancing the efficiency of in-context learning for LLMs through active learning strategies, specifically targeting the optimization of demonstration selection for few-shot learning tasks.[117] By employing methods such as uncertainty sampling, diversity sampling, and similarity-based selection, the study identifies the most informative examples that significantly improve LLM performance. The principles from this research can be adapted to 3D printing in several ways – 1. optimizing printing parameters through active learning to enhance the quality of 3D-printed objects while minimizing resource use, 2. accelerating the design iteration process through active learning to facilitate rapid prototyping of models based on feedback and predicted outcomes, 3. developing new printable materials through active learning to prioritize the exploration of material compositions to yield novel properties and expedite innovation in material science within the 3D printing domain.  \n\nTable 6. ML for material formulation in AM.   \n\n\n<html><body><table><tr><td>Research target</td><td>Fabrication process</td><td>ML technique</td><td>Sample size</td><td>Inputs</td><td>Outputs</td><td>Major findings</td><td>Refs.</td></tr><tr><td>Rheological properties prediction (concrete)</td><td>Material extrusion</td><td>Supervised: ANN</td><td>16</td><td>Dosage of high efficiency water reducing agent, hydrated calcium silicate, nano-clay, viscosity-modified</td><td>Dynamic yield stress, mini slump</td><td>The suggested model can precisely forecast the dynamic yield stress and mini-slump of 3D-printed cementitious materials using a variety of admixtures of different kinds and</td><td>[110]</td></tr><tr><td>Rheological parameters prediction (concrete)</td><td>Material extrusion</td><td>Supervised: Gene expression programming (GEP)</td><td>137 data sets of yield stress and 142 for plastic</td><td>Percentages of Cement, water, sand, small coarse gravel, medium coarse gravel, and super plasticizer</td><td>Yield stress and plastic viscosity</td><td>For yield stress and plastic viscosity, the mathematical models based on GEP demonstrated greater efficiency with significant correlation factors R2 of 0.978 and 0.998,respectively, with the experimental data</td><td>[111]</td></tr><tr><td>Yield stress evolution prediction (concrete)</td><td>Material extrusion</td><td>Supervised: ANN, Random Forest, SVR</td><td>280 data points (75:25)</td><td>SCM properties (i.e.,particle number density (NPSD), specific surface area (SSAPSD), surface potential (), and hydraulicity (SCMR)),cement reactivity (CR), main mixture parameters, and resting</td><td></td><td>The best model to predict rSO was MLP, which had an average RMSE of 20.97 Pa and an R2 of 98.4%.</td><td></td></tr><tr><td>Mechanical properties prediction</td><td>Material extrusion</td><td>Supervised: Gaussian Process Modeling</td><td></td><td>Composition of CF/PLA</td><td>Tensile strength, tensile modulus, elongation at break, flexural strength, flexural modulus, hardness</td><td>It can accurately gauge uncertainty metrics and offer a distribution for the predicted value.</td><td>[113]</td></tr><tr><td> ink formulation</td><td>Material extrusion (Direct ink writing - pneumatic)</td><td>Supervised: Mixture design RSM,sequential learning</td><td>N.A.</td><td>Solid loading, binder humectant</td><td>Herschel-Bulkley shear thinning index, dynamic yield stress, static yield stress, ink stiffness G' LVR,</td><td>Successfully identified the optimal range of ink formulation, referred to as the printable window, within which the desired printing results were achieved.The optimal rheological parameters for the selected ink deviated from the initial projections and previousfindings reported in theliterature</td><td>[114]</td></tr><tr><td>ink composition</td><td>Material jetting (Aerosol jet printing)</td><td>Supervised: Mixture design RSM, non-dominated sorting GA</td><td>13 data points</td><td>Ink composition of silver, CNT, and ethanol</td><td>Resistivity, line quality</td><td>Investigated the causal relationship between various ink components, namely nanoparticle silver ink,CNTs ink, and ethanol, and their corresponding effects on the printing outcomes. To optimize the composition of functional ink to achieve desirable characteristics,specifically low electrical resistivity, and high quality of printed lines.</td><td>[115]</td></tr></table></body></html>  \n\nMoreover, LLMs, with their vast knowledge base, prove valuable in troubleshooting 3D printing issues by offering languagebased solutions. They can understand descriptions of issues encountered during the 3D printing process and provide relevant solutions or suggestions for parameter adjustments. Their capacity to learn from diverse data sources enables them to offer guidance on a wide range of problems, from hardware malfunctions to software glitches and material issues, making them valuable tools for both novice and experienced users seeking to optimize their 3D printing workflows. For instance, ChatGPT was explored to optimize the G-code generation process in AM, particularly focusing on fused filament fabrication (FFF) with thermoplastic polyurethane (TPU) as the feedstock.[118] It assesses ChatGPT’s capabilities in addressing common 3D printing challenges such as warping, bed detachment, and stringing by optimizing printing parameters. The study demonstrates ChatGPT’s effectiveness in generating optimized G-code, leading to improved print quality and material savings. It highlights the potential of integrating AI tools like ChatGPT in additive manufacturing to enhance efficiency, reduce trial and error, and accelerate innovation in material science.  \n\nIncorporating generative AI into design workflows holds promise for transforming 3D modeling and printing. This vision entails a collaborative experience where designers articulate ideas in natural language, and AI translates them into tangible 3D models. The iterative cycle of feedback and refinement between human designers and AI could significantly accelerate the design process, allowing for rapid prototyping and optimization, thereby blurring the lines between imagination and materialization in the realm of 3D printing. A method was proposed for generating 3D architected materials from natural language inputs using a combination of a vector quantized generative adversarial network (VQGAN) and contrastive language-image pretraining (CLIP) neural networks.[119] This approach translates natural language descriptions into 2D images, which are then converted into 3D models for printing, applying both to materials with varying rigidity and to molecular dynamics modeling of nano-architectures. This innovative method allows for the direct materialization of concepts derived from language, offering new pathways for complex design workflows in 3D printing by leveraging human-readable inputs to drive the creation and optimization of 3D models and materials. Despite their capabilities, these models face challenges such as bias, interpretability, and adaptability in novel situations.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 26,
+        "chunk": "# 4.2. Advanced Sensors  \n\nVarious sensors, ranging from image-based to sensor signalbased types, are utilized to monitor and detect defects in AM, providing comprehensive insights into the processes.[120] Image-based sensors, capturing visual and sequential images through cameras, offer a detailed representation of the printing process.[121]Sensor signal-based techniques, including acoustic emission with fibre Bragg grating (FBG) sensors,[122] optical emission with multispectral sensors[123] and X-ray computed tomography,[124] and infrared signal-based sensors like pyrometers[125] and high-speed infrared cameras, focus on different aspects of monitoring. Notably, multi-sensor signal integration, combining accelerometers, acoustic emission sensors, and optical emission spectrometers with CCD cameras, enhances simultaneous monitoring.[126] Employing ML models alongside the various existing sensors aids in detecting macroscale or mesoscale defects. However, a trade-off exists between the speed of processing 1D data and higher information density for 2D or 3D data, posing a challenge in balancing processing speed and information richness in AM defect detection strategies.  \n\nIn the dynamic realm of AM, the integration of advanced sensor technology with ML models presents a transformative opportunity to push the boundaries of innovation. Looking ahead, the adoption of three-dimensional data acquisition, particularly using stereoscopic cameras, emerges as a significant advancement over traditional two-dimensional imaging methods.[127] These cameras capture the manufacturing process in three dimensions, unlocking a previously inaccessible depth of data. This enhancement allows ML algorithms to predict the quality and performance of the final product more precisely, shifting from a flat perspective to a comprehensive, volumetric analysis that could revolutionize quality assessment practices. Expanding the data spectrum for ML models, the incorporation of advanced measuring techniques such as scanning electron microscopy (SEM),[128] surface roughness measurement,[129] and in situ computed tomography (CT) scans provide abundant information on both microand macro-scales.[130] SEM offers insights into microstructural integrity crucial for predicting mechanical properties, surface roughness serves as a direct quality metric, and CT scanning non-destructively verifies internal structure and dimensional accuracy. The convergence of these diverse data streams holds the potential to create a comprehensive dataset for ML models, capable of transforming process optimization, and real-time quality control in AM.  \n\nThe concept of data fusion is particularly promising in this context, holding the potential to establish robust, predictive ML models providing comprehensive insights into the AM process. By amalgamating data from various sources, such as stereoscopic images, SEM analyses, surface topology, and CT scans, a more nuanced view of the printing process emerges. ML models can be trained on datasets reflecting the complexity of AM, enabling more accurate predictions and the ability to proactively identify and address potential failures. Furthermore, the use of augmented and virtual reality (AR/VR) technologies can potentially enhance this advanced sensory ecosystem, offering an immersive interface for design and decision-making.[131] When integrated with ML, AR/VR creates a virtual testing ground for refining designs and simulating manufacturing outcomes, pre-empting potential issues and optimizing parameters for optimal results.[132] Informed by both virtual simulations and real-time sensory data, ML models guide users through the design-to-production journey, suggesting modifications that enhance the end product’s functionality and design fidelity.  \n\nThe integration of these technologies into AM not only elevates the precision and reliability of the manufacturing process but also represents a stride toward a fully integrated, intelligent manufacturing system. These advancements signal the potential for a new era of “smart” AM, where machines evolve beyond tools of creation to become design partners capable of learning, adapting, and optimizing in real-time, ensuring the delivery of products meeting the highest standards of quality and performance.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 27,
+        "chunk": "# 4.3. ML Applications in Emerging AM-Related Fields  \n\nIn the vibrant landscape of AM, 3D printing has taken center stage, metamorphosing various industries by offering unprecedented customization, precision, and efficiency. As this transformative technology continues to evolve, the integration of machine learning emerges as a compelling frontier, promising to amplify the capabilities of 3D printing across diverse AM-related research areas. In this section, the unique applications of ML in various fields such as metal printing, polymer printing, bioprinting, construction printing, drug printing, and electronic printing will be discussed.",
+        "category": " Introduction"
+    },
+    {
+        "id": 28,
+        "chunk": "# 4.3.1. Bioprinting  \n\nOver the years, the widespread adoption of 3D bioprinting technologies (including extrusion-based,[133] jetting-based,[134] vat photopolymerization-based)[135] in tissue engineering, regenerative medicine, and biomedical applications can be attributed to its remarkable ability to accurately deposit multiple types of living cells and bio-inks at pre-defined positions. This capability facilitates the fabrication of biomimetic 3D tissue-engineered constructs.[136] The pivotal functional units in 3D bioprinted tissue constructs are the living cells, and ML proves to be a potent tool for unraveling the complexities of cellular behavior. It achieves this by handling large datasets, identifying patterns, and making predictions at various stages of the bioprinting process (Figure 25).  \n\nCell expansion is a crucial step in the bioprinting process to attain sufficient and well-characterized cell populations for the development of functional and viable tissue constructs. A study implemented an innovative ML approach, employing just-in-time learning to calibrate Raman spectroscopic models. This enabled real-time predictions of critical cell culture performance parameters for optimal cell growth.[137] ML has also been applied to differentiate healthy from apoptotic cells based on cell size and granularity information.[138] Flow cytometry-based analysis of cell size and granularity, combined with ML, offers an automated, reliable, and stain-free classification of healthy and apoptotic cells. ML plays a pivotal role in optimizing cell proliferation and selecting healthy cells for the fabrication of 3D biomimetic tissue constructs.  \n\nNumerous publications discuss the use of ML for optimizing printability in bioprinting[36,139] and a comprehensive understanding of the influence of printing parameters is essential to enhance the viability of the printed cells. Various factors such as shear stress, nozzle size in extrusion-based bioprinting,[140] shear stress, droplet impact velocity, droplet volume and polymer concentration in jetting-based bioprinting[141] and the wavelength and intensity of light, exposure time, type and concentration of photo-initiators and presence of unreacted free radicals in vat photopolymerization-based bioprinting[142] significantly affect the cell viability post-printing. Recent studies have demonstrated the use of ML approaches to predict cell viability during the bioprinting processes with high accuracies.[143] Various parameters were evaluated in the extrusion-based bioprinting system[143a] and vat photo-polymerization bioprinting,[143b] and the live-dead assays provided the dataset for ML training to predict cell viability post-printing. Additionally, a recent study demonstrated the ability to predict the number of printed cells in inkjet-based bioprinting based on the droplet velocity profile captured using a high-speed camera.[144] The ability to precisely predict the number of printed cells is important for fabrication of 3D tissue constructs in a scalable and reproducible manner.  \n\nFinally, the tissue maturation process plays a vital role in cell proliferation and differentiation over time, ultimately resulting in 3D tissues/organs with some degree of functionality. This intricate process involves critical biochemical cues that regulate cellular behavior within 3D-bioprinted tissue constructs. Biomechanical conditioning, including mechanical conditioning,[145] electromechanical stimulation,[146] macromolecules,[147] air-liquid interface cultivation,[148] or short-term hypoxic conditions,[149] has been explored to expedite the maturation of 3D-bioprinted constructs into vascularized, functional tissues. ML approaches have been applied to assess the differentiation potential of cells using morphological-based prediction by measuring geneexpression profiles and various biomarkers of undifferentiated cells.[150] Furthermore, a recent study utilized mineral apposition rate and mineralizing surface area as input loading parameters in a DL model to predict and accelerate loading-induced osteogenesis during the bone remodeling process.[151] The interplay between advanced ML models with detailed biological parameters promises to revolutionize the ability to predict and influence tissue maturation, marking a significant stride toward the realization of functional, bioprinted tissues.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 29,
+        "chunk": "# 4.3.2. Bioelectronics  \n\nThe convergence of bioprinting and electronics printing in bioelectronics printing marks a revolutionary development, ushering in a new era of advancements in healthcare and related domains.[152] This technology fundamentally revolves around creating a platform that combines biomaterials with electronic components, paving the way for a spectrum of devices, from portable benchtop platforms to wearable or implantable platforms. These devices seamlessly interact with biological systems, holding transformative potential in areas such as regenerative medicine, neural interfaces, biosensors, and in-vitro diagnostic tools for medical assessments and drug testing. The advent of 3D multi-material printing technology has enabled the fusion of diverse materials, spanning biomaterials to functional electronic inks. This synergy provides unparalleled integration, design flexibility, and functionalities that traditional platforms struggle to achieve. Nevertheless, bioelectronics printing encounters challenges, including the development of biocompatible conductive inks (demanding meticulous selection and optimization of conductive biomaterials) and maintaining high cell viability during printing (requiring careful selection of techniques and precise calibration of parameters). Effectively addressing these challenges involves navigating a complex optimization problem, balancing factors such as electronic material conductivity, platform printability, biocompatibility, and cell survival rates. A recent demonstration showcased the potential application of ML in bioelectronics printing (Figure 26).[153] ML emerges as a powerful tool, assisting researchers in identifying patterns among various parameters and guiding decision-making to optimize performance in bioelectronics platforms.[154]  \n\n![](images/900b7482509a73cc24202ecadbf08933b9a6fdbd994988122966621320681309.jpg)  \nFigure 25. An overview of ML application in typical bioprinting processes. ML can be used to a) generate high-resolution images, b) perform image segmentation, c) control cell quality, d) optimize printing parameters, e) monitor and correct bioprinting process, f) optimize co-culture medium, and g) optimize external stimuli for tissue conditioning process. Reproduced with permission.[136a] 2020, Taylor $\\&$ Francis.  \n\n![](images/c4bd27408751693274500db717e3a9e64dccce101b4704efe8c74b66f6194278.jpg)  \nFigure 26. A) Schematic illustration of the material extrusion-based 3D printing that features highly customizable inks based on versatile materials to construct all main building blocks of the wearable electronic $({\\mathsf e}^{3})$ -skin with multimodal sensing and powe ment capabilities. B) Schematic illustration of material extrusion edu 2D and 3D architectur . Top right inset, typical rheological properties of printable inks; bottom, optical images of as printed 2D and 3D MXene rchitect s. ${\\sf G}_{0}$ , storag modulus ${\\sf G}_{00}$ dulus. Scale bars, $2\\mathsf{m m}$ . C) A machine learning framework for multimodal $\\mathtt{e}^{3}$ skin. Figu win the 3D- printed valuation using e3-skin for realtime health surveillance and ML- Multiplexed multim odal physiolo of a subject after consuming an alcoholic beverage with differ fl ask deviation in reaction time (RT) and commis $(\\%)$ fo M) The actual performance versus ML-predicted RT-H (J) and g SHAP decision plot explaining ho model arrives at final task performance outcome of RT-H (K) and Error-V ). Reproduced with permission.[153] 2023, American Association for the Advancement of Science.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 30,
+        "chunk": "# 4.3.3. Construction  \n\nML finds application in diverse facets of construction printing, including architectural design, structural analysis, structural health monitoring, and durability.[155] In the realm of architectural design, ML plays a pivotal role in generating both 2D and 3D innovative layouts. ML models excel in classifying architectural styles and recognizing building components from drawings. A recent study showcased the utilization of the House-GAN model, demonstrating its capacity to explore new designs by learning from existing data, generating diverse house layouts based on input sketches.[156] Additionally, techniques such as semantic segmentation and CNNs are employed to analyze architectural drawings, identify space usage, and simulate interior layouts.[157]  \n\nIn the domain of structural analysis, ML algorithms are instrumental in predicting structural behavior (such as seismic response, buckling, and fatigue analysis). Neural networks are employed to predict material properties and assess structural components, contributing to the safety and stability evaluation of existing structures.[158] Furthermore, ML, coupled with vibrationbased data, facilitates the detection, localization, and quantification of damage in steel beams.[159] Notably, ML can also be applied to structural health monitoring for 3D-printed buildings, evaluating the condition of structures over time, detecting defects, deterioration, and potential failures.[160] ML algorithms analyzed sensor data from strain gauges and accelerometers to predict structural health, identify anomalies, and provide recommendations for maintenance or repairs.[161] Durability assessment, considering factors like material properties, environmental exposure, and load-bearing capacity, benefits from ML by predicting the lifespan of structures and optimizing their design for longevity.  \n\nDespite notable progress, challenges such as data quality, model interpretability, and real-world implementation necessitate careful consideration. The ongoing evolution of ML is poised to have a profound impact on the construction industry, reshaping the entire lifecycle of structures from conceptual design to operational maintenance. ML-driven innovations are ushering in a revolution in construction, facilitating the creation of safer, more efficient, and sustainable built environments.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 31,
+        "chunk": "# 4.3.4. Drug  \n\nTo date, 3D printing technology has garnered increasing attention within the pharmaceutical sector, revolutionizing drug manufacturing. One of the key advantages of drug printing lies in its ability to facilitate production in small batches, offering unprecedented flexibility in customized dosages, geometries, dimensions, and controllable drug release profiles. This breakthrough in manufacturing capability leads to the on-demand fabrication of personalized medicines. Remarkably, drug printing finds applications across the entire spectrum of the drug development process, ranging from preclinical drug development and human clinical trials to the actual intake of medicines.[162]  \n\nNumerous studies have reported the use of ML to optimize the printing parameters in the drug printing process.[163] Notably, an intriguing application of ML involves predicting the drug dissolution behavior of 3D-printed medicine based on the drug’s composition. Several studies have demonstrated the capability to predict drug dissolution profiles by considering various input parameters, including material composition, glass transition temperature, melting temperature, molecular weight, infill pattern, density, and surface area-to-volume ratio.[164] This predictive modeling proves invaluable in understanding how different factors influence the release of drugs over time, contributing to more informed and efficient drug development processes.  \n\nFurthermore, another captivating application is the optimization of loading efficiency for 3D-printed drugs through the utilization of ML models and advanced Design of Experiments (DOE) techniques.[165] By leveraging ML algorithms and systematic experimentation, researchers can fine-tune the parameters influencing loading efficiency, ensuring that the maximum amount of drug is effectively incorporated into the 3D-printed structure. The marriage of 3D drug printing and ML models holds immense promise for the future of pharmaceutical research and development, paving the way for more personalized and efficient drug therapies.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 32,
+        "chunk": "# 4.3.5. Electronics  \n\n3D-printed electronics have emerged as a ground-breaking frontier in AM, introducing novel opportunities for integrating circuits, sensors, and devices directly within printed structures.[166] ML plays a dual role in this domain: 1) optimizing the printing processes and detecting anomalies during fabrication, 2) processing data collected from the 3D-printed sensors. These printed sensors, enhanced by ML algorithms, can exhibit adaptive behaviors, dynamically responding to their environment and ensuring optimal performance in end-use applications. The synergy between 3D printing and ML thus presents a unique avenue for creating intelligent electronics that are both fabricated and functionally enhanced by advanced computational techniques.  \n\nThe advances in additive nanomanufacturing of flexible wearable electronics have been presented, showcasing the potential of printed bioelectronic systems for portable healthcare, humanmachine interfaces, and advanced wearable technologies.[167] Aerosol jet printing was used to fabricate soft electromyography (EMG) electrodes for recording signals from the skin and CNN was applied for pose-prediction. The results achieved over $97\\%$ accuracy in classifying six muscle activities, enabling realtime, wireless control of external machines. In another work, a graphene-based electrode was fabricated, and a similar ML technique was applied for pose prediction (Figure 22). It demonstrated about $99\\%$ accuracy in detecting seven classes of finger motions, facilitating wireless control of a robotic hand. Both studies emphasize the reliability, mechanical flexibility, and highfidelity recording capabilities of the printed bioelectronic systems. The integration of ML algorithms enhances classification accuracy and ensures precise control and continuous monitoring in wearable devices. These quantitative findings validate the feasibility and effectiveness of these technologies in revolutionizing healthcare and human performance.  \n\nA novel wearable biosensing system that used surface EMG and hyperdimensional computing for real-time hand gesture recognition was demonstrated.[168] The device comprised of a screen-printed, conformal electrode array and custom-designed application-specific integrated circuit and it incorporated adaptive learning and inference capabilities within the sensor. It classified 13 hand gestures with $97.12\\%$ accuracy and maintained high accuracy $(92.87\\%)$ even when expanded to 21 gestures. The device facilitated real-time updates of its ML models to adapt to changes such as different arm positions or sensor replacement, recovering accuracy by $9.5\\%$ without needing additional external computation. The system offers potential advancements in human-machine interface applications, allowing fast initial training and on-the-fly adaptation, and future work could consider additional situational contexts and gesture transitions, potentially improving classification performance. The low-cost, low-complexity design could also be adapted for other physiological signal processing applications, like electrocardiography or electroencephalography (Figure 27).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 33,
+        "chunk": "# 4.3.6. Food  \n\nIn recent years, the global food industry has been at the forefront of a transformative paradigm shift, responding to pressing challenges such as environmental sustainability, animal welfare, and the escalating demand for protein-rich diets. This shift has given rise to the innovative concept of 3D cultivated meat, often referred to as lab-grown or cell-based meat. This cuttingedge approach to meat production is currently in its infancy, with researchers working intensively to surmount technical, cost, and regulatory hurdles. The ultimate goal is to provide a sustainable and ethical alternative to conventional meat production, addressing the growing concerns associated with traditional practices.[169]  \n\nNotably, the incorporation of ML offers a myriad of advantages to produce 3D-printed cultivated meat. These advantages span from the meticulous fabrication of 3D meat-like structures to the precise regulation of food texture and the customization of nutritional profiles, ushering in a new era of precision and customization.[170] Recent studies have already demonstrated the use of ML in various aspects of 3D-printed cultivated meat, showing its potential for optimization and enhancement. These applications range from the optimization of culture medium formulation,[171] to the prediction and regulation of food flavor,[172] and even quality control measures.[173] A pivotal stage in cultivated meat production lies in cell production within bioreactors, and ML is proving to be a valuable tool for real-time adjustments. Parameters such as temperature, pH, oxygen levels, and nutrient circulation can be dynamically optimized through ML, facilitating optimal cell growth. A recent study showcased the application of ML to sustainably optimize serum-free media development, identifying the optimal combination of media ingredients that strike a balance between yield, environmental impact, and cost for cultivated meat production.[171a]  \n\nFurthermore, ML also plays a pivotal role in various facets of 3D-cultivated meat production. ML contributes to the development, optimization, and scale-up of the entire process. By analyzing data on different cell types, ML can identify the most suitable type of cells for cultured meat production based on factors such as growth rate, nutrient requirements, and flavor profile to achieve the best-quality cultured meat products.[174] In essence, ML proves to be an invaluable tool in the development of 3Dprinted cultivated meat, aiding researchers in overcoming challenges related to cell selection, bioreactor control, product quality, and nutritional requirements. The role of ML has become increasingly pivotal in shaping the future of sustainable and ethical meat production.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 34,
+        "chunk": "# 5. Concluding Remarks  \n\nThe integration of ML in AM processes has attracted increasing attention due to its superior performance for various AM-related applications; the ML models can recognize complex patterns from large, curated datasets and elucidate the complex relationships among different parameters to improve decision-making during the AM process. Some common ML applications in AM research include quality control, process optimization, design optimization, microstructure analysis, and material formulation. The implementation of ML in AM helps to enhance the efficiency and reliability of AM processes. Quality control involves the collection of signals from in situ sensors to train ML models for monitoring process stability and detecting defects within printed layers. Process optimization relies on large datasets from previous printing runs for the prediction of optimal process parameters under a given set of conditions. The incorporation of ML in design optimization enables training on a myriad of design variations, learning from previous iterations, and providing real-time feedback during the design phase. Advanced imaging techniques were used to collect vast amounts of data which can be processed and extracted easily using ML algorithms to decipher the relationships between the processing parameters and microstructure variations. ML algorithms can be used to guide the selection of optimal material compositions to achieve desired properties within the processability constraints. Furthermore, ML applications in emerging AM-related fields such as bioprinting, bioelectronics, construction printing, drug printing, electronics printing, and food printing were highlighted.  \n\nIn AM, even seemingly straightforward calibration can be subject to a multitude of variable factors, including environmental conditions, equipment wear and tear, and batch-to-batch material inconsistencies. ML, particularly adaptive algorithms, can continuously learn from new data to adjust for these variations, thereby maintaining and even improving the calibration over time without manual re-calibration. The AM landscape is rapidly evolving, with the development of new materials and complex geometries that present high-dimensional challenges suitable for advanced ML techniques. In these scenarios, ML can be integral not just for calibration, but for optimizing printing strategies for novel materials, predicting mechanical properties of printed objects, and enabling real-time quality control for intricate structures that are beyond the capabilities of traditional manufacturing processes.  \n\nWhile current DL research indeed focuses on complex domains such as image and language processing, the principles and models developed in these domains can be adapted to the high-dimensional aspects of AM. For example, CNNs, primarily used for image data, can be repurposed to analyze topological features of printed layers, and recurrent neural networks can model time-series data from the printing process to predict and compensate for potential defects. The intersection of AM with highdimensional data becomes evident in the pursuit of customizable manufacturing, such as for medical implants or aerospace components, where bespoke designs are the norms. Here, ML can navigate the vast design space to optimize for specific performance criteria, considering individualized constraints and objectives. The application of ML in AM is not limited to simple calibration problems but extends to tackling the intrinsic complexity and evolving challenges of the field. The potential for ML to contribute to AM is vast and varied, and we anticipate further integration of advanced ML techniques as the technology and materials of AM continue to advance.  \n\n![](images/89495e3e829ff3fbea99914424039352d7f33933f4879aabb9679af324f8798b.jpg)  \nFigure 27. Schematics showing the application of ML to process the output signals from the printed electrodes and sensors. Reproduced with permission.[167b] 2020, Nature Portfolio.  \n\nLastly, establishing a unified data community could serve as a catalyst for overcoming current bottlenecks in ML-driven 3D printing research. By ensuring that data and insights are freely shared, researchers can build on each other’s work, accelerating the path from experimental prototypes to practical applications. Additive Manufacturing Materials Database (AMMD) is an initiative that fosters data sharing and collaboration within the AM community.[175] The AMMD enables users to browse and search for specific datasets, facilitating easy access to a wealth of information regarding AM materials and processes. For users who have data but lack a framework to structure it, AMMD provides a data schema and a tool called “Curate Data” to assist in organizing their information according to standardized practices. The database is built upon the National Institute of Standards and Technology’s Material Data Curation System (MDCS), utilizing a structure defined by NIST’s AM schema. This suggests a robust, standards-driven approach to data curation in the field of additive manufacturing. Nonetheless, currently available databases consist primarily of data extracted from powder bed fusion process and more effort from the AM community to contribute to the development of the database. We strongly believe that ML is an indispensable tool in realizing the full potential of AM, paving the way for unprecedented innovation and efficiency in AM processes. The integration of ML in AM processes would significantly enhance its efficiency and reliability and amplify the 3D printing capabilities across various AM-related research areas.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 35,
+        "chunk": "# Acknowledgements  \n\n$\\forall.L.\\mathsf{N g}$ would like to acknowledge support from the NTU Presidential Postdoctoral Fellowship. W.Y.Yeong would like to acknowledge the support of the National Research Foundation for NRF Investigatorship Award No.: NRF-NRFI07-2021-0007. Part of this research was supported by $A^{\\because}S T A R$ under its RIE2015 JCO Career Development Award (Grant No 202D800024).",
+        "category": " Acknowledgements"
+    },
+    {
+        "id": 36,
+        "chunk": "# Conflict of Interest  \n\nThe authors declare no conflict of interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 37,
+        "chunk": "# Keywords  \n\nadditive manufacturing, bioelectronics, bioprinting, construction, cultivated meat, drug, machine learning  \n\nReceived: September 26, 2023   \nRevised: March 1, 2024   \nPublished online: March 28, 2024  \n\nG. Rätsch), Springer, Berlin, Heidelberg 2004; b) T. Hastie, R. Tibshirani, J. Friedman, in The Elements of Statistical Learning: Data Mining, Inference, and Prediction, (Eds: T. Hastie, R. Tibshirani, J. Friedman), Springer, New York 2009. [4] J. E. Van Engelen, H. H. Hoos, Machine Learning 2020, 109, 373. [5] a) K. Arulkumaran, M. P. Deisenroth, M. Brundage, A. A. Bharath, IEEE Signal Process Mag 2017, 34, 26; b) M. A. Wiering, M. Van Otterlo, Adapt., Learn., Optimiz. 2012, 12, 729; c) L. P. Kaelbling, M. L. Littman, A. W. Moore, J. Artif. Intell. Res. 1996, 4, 237. [6] G. L. Goh, G. D. Goh, J. W. Pan, P. S. P. Teng, P. W. Kong, Sensors 2023, 23, 9759. [7] G. L. Goh, X. Huang, W. Toh, Z. Li, S. Lee, W. Y. Yeong, B. S. Han, T. Y. Ng, Int. J. AI Mater. Design 2024, 1, 2328. [8] J. Zhang, C. Yin, Y. Xu, S. L. Sing, Int. J. AI Mater. Design 2024, 1, 2301. [9] L. Scime, J. Beuth, Addit. Manuf. 2018, 19, 114. [10] C. Gobert, E. W. Reutzel, J. Petrich, A. R. Nassar, S. Phoha, Addit. Manuf. 2018, 21, 517. [11] C. Liu, R. R. Wang, I. Ho, Z. J. Kong, C. Williams, S. Babu, C. Joslin, J. Intell. Manuf. 2023, 34, 2673. [12] a) P. Yadav, V. K. Singh, T. Joffre, O. Rigo, C. Arvieu, E. Le Guen, E. Lacoste, Adv. Eng. Mater. 2020, 22, 2000660; b) S. Feng, Z. Chen, B. Bircher, Z. Ji, L. Nyborg, S. Bigot, Mater. Des. 2022, 222, 111115. [13] H. Baumgartl, J. Tomas, R. Buettner, M. Merkel, Progress Additive Manuf. 2020, 5, 277. [14] S. Oster, P. P. Breese, A. Ulbricht, G. Mohr, S. J. Altenburg, J. Intell. Manuf. 2023. [15] S. Oster, T. Fritsch, A. Ulbricht, G. Mohr, G. Bruno, C. Maierhofer, S. J. Altenburg, Metals 2022, 12, 947. [16] L. Scime, J. Beuth, Addit. Manuf. 2019, 25, 151. [17] A. Gaikwad, R. J. Williams, H. de Winton, B. D. 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Florencia, J. of Alloys and Comp. 2016, 660, 461.  \n\n![](images/2e3e3513e6080d146a56f420b81bf4aca745bea4d3f7ef33af9c1f97319033e5.jpg)  \n\nWei Long Ng is a NTU Presidential Postdoctoral Fellow at the Singapore Centre for 3D Printing (SC3DP), Nanyang Technological University (NTU), Singapore. He received his Ph.D. degree from School of Aerospace & Mechanical Engineering, Nanyang Technological University under the A\\*STAR Graduate Scholarship. Dr. Ng served as a Research Assistant Professor at the HP-NTU Digital Manufacturing Corporate Lab, Singapore from 2020 to 2022. His expertise lies in the intersection of additive manufacturing and machine learning, where he fabricates 3D biomimetic constructs using novel bioprinting strategies for applications ranging from tissue engineering to the emerging field of cultivated meat production.  \n\n![](images/50cdb657c09fa6188c190da5bc68c2db1abb314c47db468449b0efd5e2d2caf6.jpg)  \n\nGuo Liang Goh is a Research Fellow at the School of Mechanical and Aerospace Engineering, Nanyang Technological University, Singapore. He obtained his Ph.D. degree in Mechanical Engineering from the Nanyang Technological University. He specializes in the innovative fields of 3D printing, additive manufacturing, 3D-printed electronics and machine learning. His expertise spans wearables, soft robotics, bioelectronics and more. He has led numerous research projects, secured substantial funding, and contributed to pioneering advancements in sensor technology, UAVs, and sports technology.  \n\n![](images/22fc2109805cf87fa144c75c3aae5aba6cb8a791923b1417bb29e7526e11c98a.jpg)  \n\nGuo Dong Goh is a scientist at Singapore Institute of Manufacturing Technology (SIMTech). He obtained his Ph.D. degree in Mechanical Engineering from the Nanyang Technological University. His research interests include using additive manufacturing process to create multifunctional polymer parts and applying machine learning techniques to advance the field of 3D printing in terms of design and quality. He has led numerous research projects, secured substantial funding, and contributed to pioneering advancements in fracture mechanics in 3D printing composites, UAVs, and sports technology.  \n\n![](images/527b6929c8bc2f7dfec8951d9078b1ea5473c3b2ac60eb36e840adedb2dd9d41.jpg)  \n\nJyi Sheuan Jason Ten is currently the Deputy Group Manager of the Additive Technology Innovation Group within the Additive Manufacturing Division at the Singapore Institute of Manufacturing Technology. He received a Ph.D. degree in lasers for manufacturing from the University of Cambridge in 2018. Dr. Ten’s research interests are in additive manufacturing: including in-process monitoring for defect detection and quality assurance, sustainability of powder within re-use cycles with correlation to part properties, fine feature part production, multi-material laser powder bed fusion, materials for additive manufacturing, and machine learning in AM.  \n\n![](images/d60c9485ab82fb1ba65b25d32ea56c6841029db7966d780a71658b0d7705cc69.jpg)  \n\nWai Yee Yeong is a Professor and Chair of School of Mechanical & Aerospace Engineering, Nanyang Technological University (NTU). She joined NTU since 2013 and was promoted to Full Professor in 2022. She is currently serving as a Program Director at HP-NTU Digital Manufacturing Corporate Lab, Editor-in-Chief of International Journal of AI for Materials and Design (IJAMD) and Associate Editor for Virtual and Physical Prototyping and International Journal of Bioprinting. Her current research interest focuses on the convergence of 3D printing and machine learning, particularly in the realms of printing multi-functional structures, printed electronics, and bio-electronic platforms.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Effective Antifogging Coating from Hydrophilic/Hydrophobic Polymer Heteronetwork  \n\nJunhe Shi, Liju Xu, and Dong Qiu\\*  \n\nFogging on optical devices may severely impair vision, resulting in unacceptable adverse consequences. Hydrophilic coatings can prevent surface fogging by instantly facilitating pseudo-film water condensation but suffer from short antifogging duration due to water film thickening with further condensation. Here, an innovative strategy is reported to achieve longer antifogging duration via thickening the robust bonded hydrophilic/hydrophobic polymer heteronetwork coating to enhance its water absorption capacity. The combination of strong interfacial adhesion and hydrophilic/hydrophobic heteronetwork structure is key to this approach, which avoids interfacial failure and swelling-induced wrinkles under typical fogging conditions. The developed antifogging coating exhibits prolonged antifogging durations over a wide temperature range for repetitious usages. Eyeglasses coated with this coating successfully maintained fog-free vision in two typical scenarios. Besides, the coating recipes developed in this study also have potential as underwater glues as they demonstrate strong adhesions to both glass and polymer substrates in wet conditions.",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1. Introduction  \n\nOptical devices are prone to fogging (formation of tiny water droplets that distract the optical transmittance) when their surface temperature is approaching or below the dew point of the surrounding atmosphere, leading to substantially performance detriments or even disastrous consequences in health and safety.[1–5] For instances, fog formed on the camera lens makes images blurred and distorted;[6] drivers’ vision may be impaired by fog on the vehicle windscreen or rearview mirrors, which is one of the main causes for traffic accidents.[7] In addition, fog on optical sensors or instruments often reduces the precision of spectrographs.[8] Therefore, effective antifogging strategies for optical devices are highly demanded.  \n\nAntifogging coating is regarded as the most promising approach to avoid fog formation on optical devices, whereas the antifogging coating is mainly divided into two classes in terms of wettability: hydrophobic and hydrophilic. The hydrophobic coating works by reducing adhesion and enhancing repellence of water droplets to substrates.[9–12] As water droplets are consistently removed by gravity from the surface, hydrophobic coating is advantageous in long-term effectiveness. However, water droplets can only be removed once they have grown above a critical size, i.e., $10~{\\upmu\\mathrm{m}}$ ,[13,14] therefore, an induction antifogging period is inevitable for hydrophobic coating, which, although may be very short, is still unacceptable for many circumstances. In the case of hydrophilic antifogging coating, condensed water spreads into a pseudo-film shape immediately to avoid fogging,[15–18] thus it does not have the problem of induction antifogging period as the hydrophobic coating does. However, once the water film on surface grows to a certain thickness, it becomes mobile, which often results in image distortion.[19] Therefore, hydrophilic antifogging coating suffers from short-term effectiveness.  \n\nA methodology to avoid forming thick water film on hydrophilic coating will make this antifogging method both prompt and durable, till the temperature difference between surface and vapor becomes so small that further condensation is suppressed. Hydrophilic coating of polymer network can absorb water through volume swollen, therefore, increasing coating thickness may enhance its water absorption capability and prolong the antifogging duration.[19–21] However, thick hydrophilic polymer coating raises the following primary challenges:[22–25] (i) maintaining high optical transmittance; (ii) avoiding wrinkles and creases in repeated drying-swelling cycles; (iii) preventing peeling and cracking under fogging conditions. The principles and procedures for adhesion and microstructure regulation of hydrophilic polymer networks will have to be addressed before they can be used as effective antifogging coatings in practice.  \n\nHerein, we achieve long-term antifogging performance on transparent substrates made of both silicate glass and polymethyl methacrylate (PMMA), by strongly bonded coating of a hydrophilic/hydrophobic polymer heteronetwork composed of hydrophilic poly(vinyl alcohol) (PVA) and hydrophobic poly 3-(trimethoxysilyl) propyl methacrylate (PTPM), denoted as PVA/PTPM HN thereafter. Concretely, the antifogging duration is remarkably extended through increasing the thickness of the PVA/PTPM HN coating to enhance its water absorption capacity. To provide robust adhesion, the PVA/PTPM HN is coupled with the surfaces through either covalent bonding[26] or topological entanglements.[27,28] Meanwhile, the hydrophobic PTPM in heteronetwork restrains the over-swelling of hydrophilic PVA network,[29,30] thus preventing wrinkle formation. The resultant coated slides can effectively avoid fog formation and maintain high transmittances $(>85\\%)$ in high humidity environments over a wide temperature range $(20{-}100^{\\circ}\\mathbf{C})$ for as long as $30\\mathrm{min}$ , one of the best among its peers.[31–34] Furthermore, we demonstrate the excellent antifogging effect of PVA/PTPM HN coating on eyeglasses, paving the way for such a technology to commercial applications. As the lack of adhesion and over-swelling are two wellknown deficiencies of hydrogels,[35,36] the progress made in this study also enables hydrogels to be used in many other fields,[37–40] for example, under water adhesives.  \n\n![](images/163908c114e0d5dae774384199f3382c4e4a7cf3019fc8bb4acd1d5b396e463f.jpg)  \nFigure 1. Design of the thick hydrophilic/hydrophobic polymer heteronetwork coating for effective antifogging performance. a) Weak adhesion of hydrophilic polymer network coating results in interfacial failure along with breakages and wrinkles with increasing thickness. b) Swelling induces creases on the surface of strongly bonded hydrophilic polymer network coating with increasing thickness. c) Robust anchorage of hydrophilic/hydrophobic polymer heteronetwork coating avoids both interfacial failure and creases at larger thickness. The antifogging duration is prolonged by higher water absorption in the thick hydrophilic/hydrophobic polymer heteronetwork coating. d) Antifogging behavior of a pristine glass slide (uncoated) and the one coated with PVA/PTPM HN (coated) in hot water vapor $(60~^{\\circ}\\mathrm{C})$ for 10, 60, and $300\\mathrm{~s~}$ . The coated glass slide remained clear until $300\\mathrm{~s~}$ , while the uncoated one became blurred even at $\\boldsymbol{{\\mathsf{10}}\\mathsf{s}}$ .",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2. Results and Discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2.1. Design of Thick Hydrophilic/Hydrophobic Polymer Heteronetwork Coating for Effective Antifogging Performance  \n\nWe proposed a general strategy to achieve long-term antifogging performance via thickening the robust bonded hydrophilic/hydrophobic polymer heteronetwork coatings. The hydrophilic polymer coatings are well known to have antifogging performance by swiftly spreading and absorbing condensed water.[8,41] However, these hydrophilic coatings can only immobilize limited amount of water, and a mobile water film is quickly formed afterward. Increasing the thickness of hydrophilic coatings may delay the formation of mobile water film to a time point, at which the surface is sufficiently warmed up and no more condensed water is generated, thus to achieve effective long-term antifogging performance. Nevertheless, the issues arisen with thicker coating have to be addressed before hand.  \n\nWeak bonding of coating on surface often leads to interfacial failure along with breakages and wrinkles at increased thickness (Figure 1a). Although increasing bonding strength can effectively avoid interfacial failure, the inevitable inhomogeneity in polymer network is amplified during the swelling of thicker network, i.e., forming wrinkles or creases (Figure 1b),[42,43] which either blur the vision or distort the image. We therefore propose to use thick hydrophilic/hydrophobic polymer heteronetwork coating with strong interfacial bonding for persistent antifogging performance. The hydrophobic moiety in the heteronetwork inhibits the formation of large-scale inhomogeneity by preventing any local over-swelling of hydrophilic polymer segments, thus, to maintain long-term antifogging performance (Figure 1c). The obtained glass slide coated with a $100\\upmu\\mathrm{m}$ thick PVA/PTPM HN showed persistent antifogging ability, remaining clear for at least $300\\mathrm{~s~}$ over a $60~^{\\circ}\\mathrm{C}$ water bath, while the uncoated one became blurred even at $10\\mathrm{{s}}$ (Figure 1d).  \n\n![](images/5deab32a3f487cdd4a8d48073039dd6f91dcb8d1c9a3d244a7bf1bfcb392cc52.jpg)  \nFigure 2. Antifogging performance of PVA/PTPM HN coating and the mechanism of its long-term effectiveness. a) Illustration of coating PVA/PTPM HN on silicate glass via a two-step method involving photopolymerization and solvent exchange. b) The average transmittance of PVA-WI, PVA-SI, and PVA/PTPM HN coated glass slides with varyin oating thickness over time when exposed to hot water vapo $(60~^{\\circ}\\mathrm{C})$ . c) Optical photographs of the surface of $100\\upmu\\mathrm{m}$ thick PVA-WI, PVA-SI, and PVA/PTPM HN coatings after exposed to hot vapor $(60~^{\\circ}\\mathrm{C})$ for 5 (left), 20 (middle), and $20~\\mathrm{min}$ (right), respectively. d) Antifogging duratio of PVA-WI, PVA-SI, and PVA/PTPM HN coatings with varying thickne ) The optical microscope images of the mixtures of TPM/PVA in DMSO water (water route) dyed with Suda sho wing the homogeneous dissolution of TPM in DMSO while phase g optica l images. f) Schematic illustration of measurement of adhesive strength based on the la adhe on strength of PVA/PTPM HN on glass and PMMA substrates. h) Comparison of adhesion strengths of the wet adhe on glass and PMMA substrates to other polymer adhesives reported in the literature (point) and commercial 3M adhesives (colored area). The error bars represent standard deviation; sample size $n=3$ .",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2.2. Construction of robust PVA/PTPM HN Antifogging Coating  \n\nOur method to construct the hydrophilic/hydrophobic polymer heteronetwork antifogging coating is based on a two-step approach involving the sequential processes of photopolymerization and solvent exchange (Figure 2a). We first dissolved the hydrophilic PVA and hydrophobic 3-(Trimethoxysilyl) propyl methacrylate (TPM) monomer in a cosolvent dimethyl sulfoxide (DMSO). PVA was chosen as the hydrophilic moiety because it has abundant hydrophilic hydroxyl groups to facilitate the quick spreading and sucking of condensed water (Figure S1, Supporting Information). TPM was photopolymerized in situ to form hydrophobic PTPM initiated by $365~\\mathrm{nm}$ ultraviolet, confirmed by the disappearance of $\\scriptstyle{\\mathrm{C}}={\\mathrm{C}}$ double bond $(1635~\\mathrm{cm}^{-1}$ ) in Fourier transform infrared spectroscopy (FTIR, Figure S2, Supporting Information) and the increase in viscosity (Figure S3, Supporting Information). The mass ratio of PVA/PTPM in the antifogging coating was set as $7/1$ to achieve both high transmittance and strong adhesion at increased thickness (Figure S4, Supporting Information). Upon displacing DMSO with water, interpolymer hydrogen bonding was restored to form hydrophilic PVA network.[44] At the same time, the siloxane moieties on PTPM hydrolyzed then condensed to form hydrophobic PTPM network interpenetrating with the hydrophilic PVA network. Notably, this hydrophobic PTPM network offers dual functions: providing strong interfacial bonding by forming siloxane bonds with glass[26,45] and preventing the local over-swelling of hydrophilic PVA network,[46–48] thus avoiding interfacial failure and creases of coating.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.3. Antifogging Performance of PVA/PTPM HN Coating  \n\nAs a proof-of-concept, PVA/PTPM HN at various thickness (25, 100, and $200~{\\upmu\\mathrm{m}}$ ) were coated on glasses using the procedures proposed in Figure 2a. Other two control c were used for comparison: the PVA coating by drying aqueous PVA solution on the glass slide at $25~^{\\circ}\\mathrm{C}$ for $24\\mathrm{~h~}$ , representing the hydrophilic coating with weak interfacial bonding (named as PVA-WI); and covalently anchored PVA coating on the glass slide pre-modified with epoxide groups, under otherwise identical conditions, representing the hydrophilic coating with strong interfacial bonding (named as PVA-SI, Figure S5, Supporting Information). The average transmittance between 400 and $800\\mathrm{nm}$ wavelength (obtained by Equation S1, Supporting Information) is used to assess their antifogging performance (Figure S6, Supporting Information).  \n\nAs shown in Figure 2b and Figure S7 (Supporting Information), despite of the increase in PVA-WI coating thickness from 25 to $200~{\\upmu\\mathrm{m}}$ , sharp reduction of optical transmittance was still observed after only $5~\\mathrm{min}$ , accompanied with interfacial breakages and wrinkles in the coating (Figure 2c, left). With the enhancement of interfacial bonding (PVA-SI coating), although coating breakages were avoided, surface creases were still evident (Figure 2c, middle), leading to the decrease in light transmittance at only slightly prolonged durations (Figure 2b). In contrast, with the aid of hydrophobic moieties (PVA/PTPM HN), neither interfacial breakages nor creases were observed under otherwise the same conditions (Figure 2c, right), consequently, the decrease in average transmittance was remarkably delayed upon increasing the thickness (Figure 2b), maintaining a clear vision for as long as $20\\mathrm{min}$ . Herein, we take an average transmittance higher than $85\\%$ as a successful antifogging effect. As summarized in Figure 2d, the antifogging duration of PVA/PTPM HN coatings increased remarkably, from 5 to 30 min when increasing their thickness from 25 to $200~{\\upmu\\mathrm{m}}$ , which was attributed to the enhanced water absorption capacity (Figure S8, Supporting Information), while that of other two control samples, PVA-WI and PVA-SI coatings, showed no obvious enhancement, manifesting the rationality of our strategy for antifogging coating design. This prolonged antifogging duration may enable the warm-up of substrates by environment, thus eventually avoid fog formation in practice.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.4. Structural and Mechanical Characteristics of PVA/PTPM HN Antifogging Coating  \n\nThe role of DMSO is nontrivial; it enables a well mixing of PVA and TPM, therefore guarantees the formation of a homogeneous and interlaced hydrophilic/hydrophobic polymer heteronetwork structure, essential for good optical transparency (Figure 2e; Figure S9, Supporting Information). By contrast, phase separation of TPM was observed in water and an opaque gel was obtained after polymerization of TPM through water route (Figure S10, Supporting Information). Consequently, the PVA/PTPM (DMSO route) coated glass slides remained transparent at $200\\upmu\\mathrm{m}$ thickness (transmittance higher than $85\\%$ ), while the PVA/PTPM (water route) coated ones became blurred even at $25~{\\upmu\\mathrm{m}}$ thickness (transmittance less than $85\\%$ ), as shown in Figure S11 in the Supporting Information.  \n\nPTPM forms covalent bonding with glass surface through the condensation with silanol groups, which remarkably increases the adhesive strength of PVA/PTPM HN coatings. The lap-shear test (Figure 2f) revealed a rather strong adhesion of two glass slides glued by PVA/PTPM HN coating, i.e., $\\approx1171\\pm147\\mathrm{~KPa}$ at dry state and $\\approx1153\\pm58\\mathrm{{\\KPa}}$ at wet state (Figure $2\\mathrm{g}i$ Figure S12, Supporting Information), enabling a lift of a $5~\\mathrm{kg}$ hydrothermal reactor both in air and water with an overlap area of $25\\:\\mathrm{mm}\\times25\\:\\mathrm{mm}$ (Figure S13, Supporting Information). Microscopically, the PVA/PTPM HN coating exhibited a mixed failure mode on glass slides (Figure S14, Supporting Information), manifesting its robust adhesive feature. In addition, the measured interfacial toughness of the developed PVA/PTPM HN coating on glass substrate by peeling test is over $350\\mathrm{~J~m}^{-2}$ (Figure S15, Supporting Information), also manifesting its robust adhesive ability. On the other hand, for polymeric substrates without surface hydroxyl groups, strong bonding of PVA/PTPM HN coating can also be realized via topological entanglements, benefited from the good swelling capability of DMSO to most polymers, again highlighting the advantage of DMSO route. Taking the most common optical polymer, PMMA, as an example, this topological entanglement is achieved by partial swelling of surface with TPM/DMSO solution followed by subsequent photopolymerization (Figure S16, Supporting Information). As expected, strong adhesive strength $(914\\pm80\\mathrm{{KPa}}$ at dry state and ${\\approx}987\\pm178$ KPa at wet state) on PMMA substrates was also obtained (Figure $2\\mathrm{g};$ Figure S12, Supporting Information). On the contrary, in the absence of covalent bonds and/or topological entanglements, PVA adhesion strength was much lower, i.e., ${\\approx}359\\pm60$ KPa for glass and ${\\approx}52\\pm16$ KPa for PMMA (Figure S17, Supporting Information). Indeed, the wet-contact adhesive strengths of the PVA/PTPM NH coatings on both silicate glass and PMMA were much higher than many commercial glues and high-performance polymeric adhesives in literatures (Figure 2h).[39,44,49–57] Even for two surfaces of dissimilar materials, this PVA/PTPM NH could still glue them. For examples, the wet-contact adhesive strengths between glass slides to steel, aluminum and PMMA slides were found to be ${\\approx}1091\\pm$ 159, ${\\approx}1082\\pm128$ , and ${\\approx}839\\pm83~\\mathrm{KPa}$ , respectively (Figure S18, Supporting Information). Therefore, this strategy developed for antifogging coating also sheds light on the design of universal strong adhesives for materials ranging from glass through metal to polymer, both in air and under water.  \n\nIt is worth noting that PVA/PTPM HN coating on PMMA substrate also possessed an effective antifogging performance, with the antifogging duration of ${\\approx}30$ min at a thickness of $200~{\\upmu\\mathrm{m}}$ (Figure S19, Supporting Information). On the contrary, the antifogging duration of PVA-WI coatings on PMMA (prepared following the same procedure as PVA-WI coating on glass slides) was only ${\\approx}10$ min under otherwise the same conditions (Figure S19, Supporting Information). In addition, the PVA/PTPM HN coating still maintained high transparency (above $85\\%$ ) both at dry and wet states even after a $5\\mathrm{~N~}$ load of dynamic scratching, attributed to its high hardness (Figures S20 and S21, Supporting  \n\n![](images/550df571d0a411fe79d6338fafb27392a26ce37dd5ef10cc8cbe5e329854f8c9.jpg)  \nFigure 3. Temperature tolerance and reusability of the PVA/PTMP HN antifogging coating on glass slides. a) The average transmittance of the PVA/PTPM HN coated glass slides at different temperatures. b) Antifogging duration of PVA/PTPM HN coatings over a wide temperature range. c) The volume and mass swelling ratio of PVA/PTPM HN coating during cyclic drying-swelling test, where D and W denote the dry and wet state, respectively. d) The average transmittance of PVA/PTPM HN coated glass with a coating thickness of $100\\ \\upmu\\mathrm{m}$ through repeated antifogging tests on a $60~^{\\circ}\\mathrm{C}$ water bath, indicating its excellent reusability. e) The optical photographs of dry-state (top) and wet-state (bottom) of PVA/PTPM HN coated glass slides after 7 cycles of antifogging tests, showing a clear vision over the same picture. The error bars represent standard deviation; sample size $n=3$ .  \n\nInformation). Thus, the combination of homogeneous hydrophilic/hydrophobic heteronetwork structure and strong adhesion and scratching resistance in PVA/PTPM HN coatings endues them with the potential of universal antifogging coatings on diverse optical materials.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.5. Temperature Tolerance and Reusability of the PVA/PTPM HN Antifogging Coating  \n\nWater vapor temperature has a profound effect on antifogging performance due to the altered condensation speed and size of the condensed water droplets. To further investigate the temperature impact, optical transmittance of PVA/PTPM HN coated glass slides with the coating thickness of $100~{\\upmu\\mathrm{m}}$ was measured over time at different temperatures (Figure S22, Supporting Information). As shown in Figure 3a, these coated glass slides maintained a high optical transmittance (over $85\\%$ almost independent with time at temperatures below or at $40~^{\\circ}\\mathrm{C}$ . At higher temperatures, reduction in optical transmittance was observed after an initial plateau and became lower than $85\\%$ at ${\\approx}20$ and ${\\approx}10$ min for 60 and $80~^{\\circ}\\mathrm{C}$ , respectively, probably due to the formation of excess water layer beyond its water absorption limit.[19] Surprisingly, the decrease in optical transmittance was suppressed at $100~^{\\circ}\\mathrm{C}$ , probably due to the approaching of water-vapor phase equilibrium point.[58] Overall, as summarized in Figure 3b, the PVA/PTPM HN coating can effectively prevent fog formation on glass slides over a wide temperature range $(20-$ $100^{\\circ}\\mathrm{C})$ .  \n\nReusability is a key challenge faced by existing antifogging approaches but essential for practical applications, as the coating will have to endure repeated swelling–drying cycles. We explored the reusability of PVA/PTPM HN coating through repeated antifogging tests. In the initial swelling process, the equilibrium mass and volume swelling ratios of PVA/PTPM HN coating can reach $86\\pm11\\%$ and $133\\pm17\\%$ within $30~\\mathrm{min}$ (Figure S23,  \n\nSupporting Information). After seven cycles of drying-swelling tests, they maintained fairly steady levels comparable to the original ones, i.e., $\\approx130\\%$ and $\\approx80\\%$ , respectively (Figure 3c), ensuring the long-term and repetitious antifogging performance. In addition, the PVA/PTPM HN coating on glass slides demonstrated robust adhesion and remained smooth after immersed in water for up to 3 d (Figure S24, left, Supporting Information). In contrast, the PVA-WI coating showed interfacial failure and wrinkled surface upon swelling in water, severely deteriorating the optical transparency (Figure S24, right, Supporting Information). Attributed to the strong interfacial adhesion and hydrophilic/hydrophobic heteronetwork structure, the PVA/PTPM HN coating on glass slides remained highly transparent (optical transmittance over $88\\%$ ) during seven cycles of fogging tests (Figure 3d,e), manifesting its long-term antifogging performance.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.6. Pseudo-Service Performance Evaluation of PVA/PTPM HN Antifogging Coating  \n\nFog formed on optical devices, such as eyeglasses, may severely impair people’s vision. Therefore, effective antifogging method is highly important. Owing to the outstanding antifogging performance of the PVA/PTPM HN coating, it can be readily used to endow eyeglasses with antifogging effect. The PVA/PTPM HN can be firmly coated on silicate-based eyeglasses which are rich in surface silanol groups without sacrificing their inherent optical transparency. The antifogging performance of the coated eyeglasses was tested in two typical scenarios, where fog is prone to generate. In one case, a person simultaneously wore a pair of eyeglasses and a mask at room temperature (Figure 4a–c). Fog easily formed on the uncoated lens (Figure 4b,c, left) due to the abundant water vapor from breathing, while the coated lens (Figure 4b,c, right) remained highly transparent. In the other case, a person wearing a pair of eyeglasses entered a warm room $(25^{\\circ}\\mathrm{C})$ from cold outdoors $(-15^{\\circ}\\mathrm{C})$ (Figure 4d–f). In this situation, the uncoated lens (Figure 4e,f, left) became opaque immediately. Notably, the coated one (Figure 4e,f, right) remained clear, manifesting the remarkable antifogging performance of PVA/PTPM HN coating. In addition, the coating is also much easier to clean once fouled by oily pollutants, such as annoying fingerprints (Figure S25, Supporting Information), which is highly valued for realworld applications.  \n\n![](images/dcaa7a1d832fe5456310445c29a41878ba28868c2011022807e3b5833c837197.jpg)  \nFigure 4. Antifogging eyeglasses using the PVA/PTPM HN coating. a) The schematic route of fogging on eyeglasses when wearing a mask. b,c) Th antifogging test of eyeglasses when wearing a mask. d) The schematic illustration of fogging on eyeglasses when entering warm indoors from cold outdoors. e,f) The antifogging test of eyeglasses when entering indoors $(25^{\\circ}\\mathrm{C})$ from cold outdoors $(-75^{\\circ}\\mathrm{C})$ .",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3. Conclusion  \n\nIn summary, a highly adhesive hydrophilic/hydrophobic polymer heteronetwork thick coating is proposed to achieve effective antifogging performance. Under this concept, PVA/PTPM HN coatings are developed, starting from their solution in DMSO and finally crosslinked by photopolymerization and solvent exchange. These coatings displayed superior strong interfacial adhesion resulted from the formation of covalent bonds and/or topological entanglements with the targeted surfaces to avoid interfacial failure. Meanwhile, this hydrophilic/hydrophobic polymer heteronetwork restrains the formation of swelling-induced wrinkles under typical fogging conditions. At increasing thickness, these coatings showed prolonged antifogging performance, when exposed to water vapor in a wide temperature range $(20-$ $100~^{\\circ}\\mathrm{C})$ . Therefore, this PVA/PTPM HN antifogging coating offers advantages over existing antifogging materials, including longer antifogging duration, high transparency and stability over repeated usages. As a proof-of-concept, the PVA/PTPM HN coating demonstrated highly effective antifogging performance on the eyeglasses. We anticipate that the reported method and material are generally applicable for the rational design of highperformance antifogging coatings towards commercial applications. Besides, the strategy developed for antifogging coating also sheds light on the design of universal strong adhesives for materials ranging from glass through metal to polymer, both in air and under water.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 11,
+        "chunk": "# 4. Experimental Section  \n\nPreparation of PVA/PTPM HN Coating: The two-step method involving photopolymerization and solvent exchange was adopted to prepare the PVA/PTPM HN coating. Typically, PVA with the mass of $3.6\\ \\gtreqqless$ was dissolved in $75~\\mathsf{m L}$ DMSO and stirred for $2\\ h$ at $95~^{\\circ}\\mathrm{C}$ . A mixture of TPM $(0.5~\\mathsf{m L})$ and DMPA ( $\\cdot75{\\mathsf{m g}})$ was added to the above solution, followed by stirring for $20~\\mathrm{min}$ in dark. After defoaming, the resultant solution was spread onto the glass slides to produce a uniform liquid layer with different thickness (25, 100, $200\\upmu\\mathrm{m})$ using a wet film coater, followed by UV irradiation ( $365\\ \\mathsf{n m}$ wavelength, $0.8\\dot{\\mathsf{W}}\\mathsf{c m}^{-2}$ ) for $\\rceil\\boldsymbol{\\mathsf{h}}$ and solvent exchange in water for another $0.5\\mathsf{h}$ . To obtained dry PVA/PTPM HN coated substrates, the samples were dried at $25~^{\\circ}\\mathrm{C}$ for $24\\ h$ .  \n\nStatistical Analysis: When average value is referred, it is based on 3 parallel tests and presented in the form of mean $\\pm S\\mathsf{D}$ . In the corresponding figures, error bars reflect the values of SDs.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# Supporting Information  \n\nSupporting Information is available from the Wiley Online Library or from the author.",
+        "category": " References"
+    },
+    {
+        "id": 13,
+        "chunk": "# Acknowledgements  \n\nJ.S. and L.X. contributed equally to this work. This work was supported by the National Basic Research Program (Grant 2017YFC1103300), National Natural Science Foundation of China (Grant 51773209). J.S., L.X., and D.Q. conceived and performed the experiments, undertook the data analysis and wrote the manuscript.",
+        "category": " References"
+    },
+    {
+        "id": 14,
+        "chunk": "# Conflict of Interest  \n\nThe authors declare no conflict of interest.",
+        "category": " References"
+    },
+    {
+        "id": 15,
+        "chunk": "# Data Availability Statement  \n\nThe data that support the findings of this study are available from the corresponding author upon reasonable request.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# Keywords  \n\nadhesive, antifogging, coating, hydrophilic/hydrophobic heteronetwork  \n\nReceived: January 25, 2022 Revised: February 21, 2022 Published online:  \n\n[1] I. R. Duran, G. Laroche, Adv. Colloid Interface Sci. 2019, 263, 68. [2] B. J. Briscoe, K. P. Galvin, Sol. Energy 1991, 46, 191.   \n[3] R. N. Leach, F. Stevens, S. C. Langford, J. T. Dickinson, Langmuir 2006, 22, 8864.   \n[4] X. Chen, J. Wu, R. Ma, M. Hua, N. Koratkar, S. Yao, Z. Wang, Adv. Funct. Mater. 2011, 21, 4617.   \n[5] C. H. Chen, Q. Cai, C. Tsai, C. L. Chen, G. Xiong, Y. Yu, Z. Ren, Appl. Phys. Lett. 2007, 90, 71.   \n[6] J. Zhao, L. Ma, W. Millians, T. Wu, W. Ming, ACS Appl. Mater. Interfaces 2016, 8, 8737.   \n[7] M. San-Juan, O. Martin, B. J. Mirones, P. De Tiedra, Appl. Therm. Eng. 2016, 104, 479. [8] J. Zhao, A. Meyer, L. Ma, W. Ming, Chem. Commun. 2013, 49, 11764.   \n[9] V. Zorba, X. Chen, S. S. Mao, Appl. Phys. Lett. 2010, 96, 093702.   \n[10] P. Brown, O. Atkinson, J. 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+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Application of machine learning in polymer additive manufacturing: A review  \n\nTahamina Nasrin1 | Farhad Pourkamali-Anaraki² | Amy M. Peterson $\\mathbf{1}_{\\mathbb{O}}$  \n\n'Department of Plastics Engineering, University of Massachusetts Lowell, Lowell, Massachusetts, USA ²Department of Mathematical and Statistical Sciences, University of Colorado Denver, Denver, Colorado, USA",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Correspondence  \n\nAmy M.Peterson, Department of Plastics Engineering, University of Massachusetts Lowell, Lowell, MA, USA. Email: amy_peterson@uml.edu",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# Abstract  \n\nAdditive manufacturing (AM) is a revolutionary technology that enables production of intricate structures while minimizing material waste. However, its full potential has yet to be realized due to technical challenges such as the dependence of part quality on numerous process parameters, the vast number of design options, and the occurrence of defects. These complications may be magnified by the use of polymers and polymer composites due to their complex molecular structures, batch-to-batch variations, and changes in final part properties caused by small alterations in process settings and environmental conditions. Machine learning (ML), a branch of artificial inteligence, offers approaches to tackle these challenges and significantly reduce the experimental and computational time and expense. This review provides a comprehen sive analysis of existing research on integrating ML techniques into polymer AM. It highlights the challenges involved in adopting ML in polymer AM, proposes potential solutions, and identifies areas for future research.",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# KEYWORDS  \n\nin-situ monitoring, machine learning, polymer additive manufacturing, process optimization, property prediction",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# 1 INTRODUCTION  \n\nAdditive manufacturing(AM) involves fabricating three dimensional objects, often in a layer-by-layer manner, from computer-aided design (CAD) models. Over the past few decades, AM has transformed from a technology primarily used for prototyping into a robust tool capable of producing functional end-use parts.l One of the key advantages of AM over traditional subtractive manufacturing methods is its ability to manufacture complex geometries that would be challenging or impossible to achieve using conventional processes.² Furthermore,  \n\nAM typically results in less material waste than subtractive methods due to its minimal post-processing steps and near-net-shape output.² However, the widespread adoption of AM is still hindered by a number of obstacles, such as anisotropy of final part properties,4 limitations in dimensional accuracy and resolution,5 slow manufacturing speeds relative to mass production techniques,% and a limited selection of printable materials compared to conventional manufacturing.?  \n\nThe history of machine learning (ML) dates back to 1957. Inspired by the human nervous system, psycholo gist Frank Rosenblatt and his team created an alphabet letter-recognition machine. This device was dubbed the “perceptron” and is regarded as the basis for modern artificial neural networks. Although the concept of ML has been around for over half a century, it has only recently gained  significant popularity due to advancements in computing power, data storage capabilities, open-source software, and ML libraries such as TensorFlow,9 Scikit-Learn,10 PyTorch,1l and Keras.1² The fundamental operating principle of ML models entails learning from existing data to unveil patterns and relationships, which can then be used to make predictions or decisions about new and unseen cases.13 This process can handle various types of data, including numeric, categorical, text, image, audio, and video data.14 With advances in data acquisition techniques and data storage technologies, ML has attracted significant interest in a wide range of fields including AM.  \n\nAM techniques exhibit high levels of complexity due, in part, to an extensive number of process parameters.15-19 The microstructural and macrostructural properties of the printed parts are significantly influenced by these parameters. For instance, cure depth, irradiation time, and irradiation power are all crucial factors for dictating the final properties of vat photopolymerized parts. There are additional pre-printing and post-processing variables, too. Continuing the vat photopolymerization example, the printing process may be affected by resin moisture content. Additionally, the extent and conditions of post curing substantially affect the mechanical properties. Therefore, in order to ensure that the final part is of high quality, an in-depth understanding of the material-process-structure-property relationships is essential.  \n\nThe most straightforward approach for understanding material-process-structure-property relationships entails conducting physical experiments wherein a single parameter is altered while the remaining parameters are held constant, thereby enabling the observation of variations in the quality of the printed parts. However, this is not practical due to the sheer number of process parameters involved. Therefore, modeling approaches are frequently adopted. Mathematical modeling is one approach for understanding the AM process. However, it is challenging to develop these models because multiple processing parameters dictate resulting properties, and the relative importance of parameters changes across process steps and with different materials.20 Physics-based models can be used instead, but they require comprehensive domain expertise and substantial computational resources.2- ML techniques provide an alternative approach for constructing predictive models capable of simultaneously handling multiple process and material parameters. Additionally, ML techniques exhibit flexibility in their ability to learn from various data types. Therefore, ML techniques have been increasingly employed in AM, including property prediction, defect detection, quality control, material development, and design for AM.20-23  \n\nAM enables fabrication of parts using many classes of materials. Numerous reviews have concentrated on the application of ML to metal-based AM techniques, while few polymer AM aspects are covered.21-24 Polymer-based AM techniques present distinct challenges. For instance, the molecular structures of polymers exhibit greater complexity compared to metals due to the presence of varying chain lengths within the same material. Part consistency is, therefore, a challenge. In addition, thermal and environmental factors are more likely to alter the properties of polymers compared to metals. To achieve adequate predictive accuracy when implementing ML techniques in polymer AM, it is necessary to account for these nuances. This article provides an overview of the applications of ML techniques specifically for polymer AM. The article is structured as follows: Section 2 provides a brief overview of polymer-based AM techniques. In Section 3, the ML techniques used in polymer AM research are discussed. Section 4 explains the importance of ML techniques to polymer AM. Section 5 provides a comprehensive summary of the existing research that has applied ML to various polymer AM techniques. In Section 6, the challenges associated with the application of ML in polymer AM are discussed, along with types of opportunities in this area.",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2 | POLYMER ADDITIVE MANUFACTURING TECHNIQUES  \n\nAM techniques have gained considerable attention for their ability to fabricate parts with complex geometries and substantial reductions in material waste. In AM processes, three-dimensional (3D） objects are typically created in a layer-by-layer fashion, directed by a computer aided design （CAD） file. ASTM 52910 classifies according to seven types of additive manufacturing processes: material extrusion (ME), vat photopolymerization (VP), material jetting (MJ), binder jetting (BJ), powder bed fusion (PBF), direct energy deposition (DED), and sheet lamination (SL). The most common polymer-based AM techniques are ME, VP, and MJ. Polymer-based PBF requires powdered feedstocks, limiting material choice because few polymers are available in powder form with the required sintering window.25 BJ is another AM method that uses powdered materials. The powder can be metal, ceramic, or polymer and the powders are bound using a polymer binder.26 Figure 1 includes a summary of the categories and most common subcategories of polymer AM techniques.  \n\n![](images/ec623e901269d444e9f105d2d05cc20ae1f031412814abf3ab6579829cb7f8a4.jpg)  \nFIGURE1 Classification of polymer additive manufacturing techniques.  \n\nFor further information on the development and use of polymer materials in AM, readers are referred to the comprehensive review by Tan et al.27 The following sections include short overviews of polymer-based AM techniques.",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.1 Material extrusion (ME)  \n\nME involves dispensing materials selectively through a nozzle or orifice onto a build surface layer-by-layer to create a 3D structure. A wide range of polymer and polymer composites are used as feedstocks for ME. Fused fila ment fabrication (FFF), a prevalent form of ME, uses thermoplastic filaments. Initially, FFF was limited to a few polymers such as acrylonitrile butadiene styrene (ABS) and polylactic acid (PLA).28 However, the technique has evolved to allow for use of many engineered polymers and polymer composites and is capable of producing printed parts with enhanced mechanical,29 thermal,30 and/or electrical performance.31 Big area additive manufacturing (BAAM) is a large format ME method that uses thermoplastic pellets instead of filaments as its feedstock and is designed to fabricate large-scale structures.32 The working principle of BAAM and FFF are similar. However, BAAM retains heat longer than FFF, allowing for better interlayer bonding through diffusion and weld formation, but presents challenges such as material sagging or slumping due to their significant scale differences.33 Direct ink  writing(DIW） uses viscoelastic inks and can print a wide range of polymeric materials including thermoplastics, thermosets, elastomers, hydrogels, and polymer composites. Essentially, any material that has suitable rheological properties can be printed using DIW.34 A relatively new ME technology is ambient reactive extrusion (ARE), in which reactive thermosetting polymers that cure after deposition at room temperature are printed.35 ME applications have greatly advanced, evolving from solely rapid prototyping to producing durable and functional end-use-parts. These parts are found in fields including gaerospace,36 automotive,37 and biomedical sectors.38-40  \n\nThe properties of ME parts are influenced by part design and process parameters.41 For example, typical process parameters in FFF include extruder temperature, layer height, material extrusion rate, raster orientation, raster width, build orientation, and infill. With numerous parameters involved, optimization becomes time-consuming and resource-intensive. Additionally, processstructure-property correlations are often complex and nonlinear, further complicating the optimization process.42",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.2 | Vat photopolymerization (VP)  \n\nVP consists of selective curing of liquid photo-sensitive material using light/radiation. Light is projected onto the photopolymer, following a pattern defined by a CAD file. This process selectively cures the photopolymer, resulting in the formation of the final part.43 There are many variants of VP, which are categorized based on factors such as light source, speed and resolution, layering method, and build platform position. The two main VP methods are stereolithography (SLA） and digital light processing (DLP). Both techniques use UV light to cure the photo polymer in a layer-by-layer manner to fabricate the final part. The main distinction lies in the method of curing: DLP cures an entire layer simultaneously using digital micro-mirrors devices, while SLA cures pixel-by-pixel within a layer.16 Therefore, DLP offers faster print speed compared to SLA. Other VP techniques include twophoton polymerization (2PP), Volumetric AM, and continuous liquid interface production (CLIP). 2PP is capable of very high resolutions ( ${\\sim}100\\ \\mathrm{nm})$ and is best suited to very small structures.44 Volumetric AM and continuous liquid interface production (CLIP） are both layerless VP approaches.45,46 Comparative discussions of different VP techniques are presented in review articles by Zhang et al.47 and Rashid et al.16  \n\nVP is limited to photo-sensitive polymers. It finds application in the electrical and biomedical fields.16,48 VP is capable of printing a wide range of photopolymer and photopolymer suspensions with high resolution.47 Solid particle reinforcement in vat photopolymerization has gained significant interest due to its potential as an alternative to processes such as PBF or BJ.49-52 This approach involves incorporating metal or ceramic particles into the photopolymer, enabling improved structural and mechanical properties and fabrication of ceramic or metal green bodies.53-55 Typical material systems consist of acrylate or epoxy-based monomers, photoinitiators, diluents, light absorbers, and radical inhibitors.56-58 Low viscosity $(0.25\\mathrm{-}10\\ \\mathrm{Pa\\cdots})$ resins are recommended to avoid damaging printed features during the recoating process.59  \n\nThe structural and surface properties of VP parts are significantly influenced by factors including layer height build orientation, exposure time, and light source intensity.60-62 Resin properties,such as viscosity, reactivity, and photoinitiator concentration, also have great impact on the final part properties.63 Introducing solid particles into the formulation further complicates the rheological behavior.64 This can lead to increased viscosity,65 reduced cure depth due to scattering,66 inhomogeneous particle distribution due to sedimentation or creaming,67 which may cause print failures. Achieving defect-free parts requires adjusting both process and material parameters, which often relies on experimentally costly trial-and-error and/or  intuition-based methods.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.3 Material jetting (MJ)  \n\nMJ is a popular AM method known for its ability to print highly complex structures with multiple materials, offering high dimensional accuracy and low surface roughness. The process may use UV-curable inks in a manner similar to an inkjet printer. Wax can also be printed with the MJ process and is commonly used as a support material.68.69 Droplets of inks are ejected through multiple nozzles onto a substrate and, if necessary, subsequently cured using UV-light. Based on the droplet dispensing method, MJ processes can be classified as either continuous inkjet (CI） printing or droplet-on-demand (DoD) printing.7° It is important to note that commonly used commercially available photopolymer inks have poor mechanical and thermal properties.7l Therefore, MJ cannot be used to print structures for applications involving heavy loads.72 However, the technology is valuable in the realm of functionally graded materials, making it well-suited for sophisticated applications such as bioprinting73 and printed electronics.74,75 For further exploration of recent developments and advanced applications of MJ, readers are referred to review articles by Elkaseer et al.72 and Guilcan et al.71  \n\nMJ is an intricate process that requires careful optimization of process parameters to achieve high quality prints. The existing body of literature on process parameter optimization in the field of interest is limited. Bass et al. investigated the impact of part orientation on the MJ-produced parts, highlighting its significance in the printing process.76 Pugalendhi et al. explored the effect of MJ process parameters on the mechanical properties of the printed objects.77 Achieving high resolution printed structure requires precise control of ink droplet size as well as the droplet spread on the surface. Moreover, the optimization of curing strategies is also crucial, yet it has not been extensively explored. This aspect becomes more complicated for multi-material MJ process, as different materials may require different curing strategies.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.4 I Powder bed fusion (PBF)  \n\nPBF selectively fuses powdered material from a powder bed in a layer-by-layer manner, typically using thermal energy provided by a laser beam. Selective laser sintering (SLS) is a more common term for processing polymer powders. The key advantage of SLS is the design freedom attribued to not requiring any support structure.78,79 Custom designed automotive and aerospace parts as well as functional implants have been fabricated via SLS.80-82  \n\nAs compared to other polymer-based AM techniques, SLS has a limited range of available materials. The primary material used for SLS is polyamide 12 (PA12) due to its appropriate sintering window (between melting and crystallization） and free flowing behavior facilitated by highly spherical particles with precise particle size distributions (PSDs).25 Other commercially available polymers used in SLS include other polyamides, ABS, polyaryletherketones (PAEK), thermoplastic elastomers (TPE), polypropylene (PP), and polystyrene (PS). Numerous process parameters control the final part quality in SLS. Han et al. categorized SLS experimental parameters as either laser or build parameters while discussing the effects of these parameters on part property and quality.79 Similar to other AM processes, SLS optimization is complicated due to the high dimensionality of its parameter space.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 2.5 Binder jetting (BJ)  \n\nBJ is a powder-based AM technique in which a liquid binder is selectively dispensed onto a powder bed in the X-Y plane to create a two-dimensional (2D） pattern. These patterns are then repeated in the Z direction to construct a complete 3D structure of bonded powder par ticles, known as a“green\" structure. The green part can be used directly, sintered, or infiltrated with other materials.83 BJ is frequently used to fabricate sand molds and cores with complex geometries.84,85 The porous nature of the printed structures is particularly favorable because the pores may act as channels for gas transport and simple release of the molded part.85 Early works also showed the efficacy of BJ for fabricating drug delivery devices.86  \n\nThe key to BJ's success is its versatility with a variety of powdered materials, including metal, ceramic, and polymer. Metal and ceramic powders are commonly used.87,88 Research on polymer powders in BJ is limited because powder forms are not commonly used in the production of polymer structures.26 The choice of binder material is crucial because it directly influences print success and the properties of the final part. The binder needs to have sufficient wettability to the powder. Many polymeric materials have been used as binders, including polyvinyl alcohol (PvA),89,90 polyacrylicacid (PAA),% cellulose derivatives,91 and waxes.92  \n\nNumerous process and material parameters influence the dimensional precision and final properties of BJ parts. First and foremost, it is essential to maintain the powder bed density across all layers in order to produce parts with uniform properties. Uniformity in powder beds is crucial for consistent binder jetting quality, but variations can occur due to roller movement, leading to differences in green part density and shrinkage during debinding. 93 Fine powders, with micron and sub-micron dimensions, frequently aggregate.94 In addition, layer thickness, drying power level and drying time of the binder, and powder spreading speed affect printed part quality.95,96",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3 | MACHINELEARNING TECHNIQUECATEGORIESAND TASKSINPOLYMERADDITIVE MANUFACTURING  \n\nML is a sub-field of artificial intelligence (AI) that employs a data-based modeling approach to uncover patterns within a dataset.97 By extracting these patterns, ML algorithms can make predictions for previously unseen cases. AM techniques are complex, and the end part quality is influenced by numerous material and pro cessing parameters as discussed in Section 2. This complexity creates an opportunity for ML techniques to reduce the time and resources required to evaluate process-structure-property-performance relationships as compared to purely trial-and-error-based experiments, numerical, and analytical models. While ML has found extensive applications in metal AM, its use in polymerbased AM techniques is still emerging and will be discussed in detail in Section 5.98-104",
+        "category": " Introduction"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3.1 Machine learning tasks  \n\nML models can perform tasks such as regression, classification, clustering, and dimensionality reduction.Each of these types of tasks is described in greater detail below, including applications in AM.  \n\nRegression tasks focus on predicting numerical or quantitative outcomes. Therefore, the main objective of regression-based ML modeling is to minimize the difference (error) between the predicted and actual outputs, thereby finding accurate input-output relationships.105 Regression-based modeling approaches have been used to predict properties of AM structures, including compressvestrngthnileis rougness,12 and hardness.113 In theseexamples, process parameters were used as model inputs.  \n\nClassification tasks focus on generating decision boundaries between predefined classes based on patterns learned from the training data.l14 Classification-based modeling techniques have been extensively used in real-time/in situ monitoring of AM processes.115 In situ monitoring with classification techniques includes defect detection,16 process anomaly detection,1,i18 and product quality prediction.119 These tasks often involve training ML models with images.  \n\nClustering tasks involve grouping similar data points together based on their intrinsic properties.120 Clusteringbased ML techniques have been applied to in-situ monitoring of AM process for defect detection,12l failure mode detection,122 and process monitoring.123  \n\nLastly, dimensionality reduction entails reducing the number of input features, or data dimensionality, while preserving as much variance or information as possible.124 Polymer AM-related problems may have numerous input variables, but not all of them have the same level of impact on the parameter being investigated. Hence, dimensionality reduction techniques can be useful for enhancing the efficiency and interpretability of models by identifying the most important or relevant input features. These techniques have been used to investigate process parameter-property correlations42 and the selection of printed formulations.125",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.2| Categorization of machine learning techniques  \n\nThere are various ways to categorize ML techniques. In this review, we categorize ML techniques according to data supervision and model complexity for aiding further discussion of their applications in polymer AM.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3.2.1 Data supervision  \n\nUsing data supervision as the metric, ML models can be categorized as being supervised, unsupervised, or semi-supervised, as shown in Figure 2. Supervised ML techniques train models using labeled data.126 The term \"labeled\" means that the data points include known targets or outcomes. Supervised models are primarily used for regression and classification tasks. In contrast to supervised models, unsupervised models learn from unlabeled data without the guidance of predefined labels or outcomes.127 Unsupervised techniques discover  the hidden pattern in the dataset. They are popular for tasks such as data clustering and reducing dimensionality in the dataset.  \n\nSemi-supervised ML techniques use principles of both supervised and unsupervised approaches.128 Semisupervised models start with a dataset where a small number of data points are labeled, and a large portion is often unlabeled. The labeled data are first used to train the ML model. Then, the model learns iteratively from the unlabeled data. Based on interactions with labeled and unlabeled data, semi-supervised techniques can be categorized as active learning (AL), passive learning, or self-training. AL queries an external source, typically a human expert, for labeling the most informative data points.129 Passive learning, on the other hand, uses both labeled and unlabeled data without actively searching for new labels, while self-training uses its own predictions to label and iteratively retrain using unlabeled data.130 Semi-supervised approaches are typically used for regression and classification tasks. Semi-supervised approaches are used in AM when dealing with large design spaces, when labeling processes are impractical, or when experiments are costly.131",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 3.2.2 Model complexity  \n\nDepending on the complexity of the architecture, ML techniques can be classified as being either shallow or deep, as shown in Figure 3. In general, shallow ML models have simple architectures, whereas deep learning models have complex architectures that are capable of identifying complex data patterns. The ability to discern intricate and hierarchical patterns from data is a key distinction between shallow and deep models. A shallow model's input features are manually extracted, while deep models can automatically learn feature representations from raw input data.132 One additional distinction between shallow and deep learning models is the types of data they can process. Shallow models are typically limited to structured data such as tabular data. Deep learning models can handle both structured and unstructured data, including but not limited to tabular data, image data, time series or sequential data, text data, audio data, and video data.133  \n\n![](images/696bbe6e5e3fbf9540571927a8607e789b4999f14487b709a295a938fd1a51d6.jpg)  \nFIGURE 2 Classification of machine learning models based on data supervision approach.  \n\n![](images/37f995507d11086f23edc25dad94df36b8395f9f73a0dd1f18fa4f54c0f126a4.jpg)  \nFIGURE3 Classification of machine learning models based on model complexity.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# Shallow models  \n\nShallow models can be parametric or non-parametric. Parametric models are characterized by their strong assumptions regarding the relationship between input features and target variables or outcomes. These assumptions typically involve a fixed number of coefficients or weights. Consequently, the flexibility of parametric models in capturing complex patterns is limited. Nevertheless, these models exhibit simplicity and efficiency, especially when data availability is limited. Several parametric models commonly used in polymer AM include linear regression (LiR), multivariate linear regression (MLR), multiple regression analysis (MRA), ridge regres sion (RR), logistic regression (LoR), polynomial regression (PR), Naive Bayes (NB), and Gaussian mixture model (GMM).  \n\nLiR, MLR, MRA, RR, LoR, PR, and NB are supervised techniques, whereas GMM is unsupervised. However, they can all be adapted to semi-supervised techniques. Typically, adaptation involves iterative methods that use labeled data to infer labels for unlabeled data. The newly labeled data are then incorporated into the model's training process.  \n\nLiR, MLR, MRA, RR, and PR are commonly employed to conduct regression analysis.134 LiR, MLR, RR, and MRA model the relationship between input features and output variables in a linear manner. MLR and MRA are straightforward extensions of LiR, while RR and PR introduce additional complexity. The primary distinction among LiR,MLR,and MRA lies in the number of variables used. LiR uses a single independent variable (input) to make predictions about a corresponding dependent variable (output). MRA employs two or more independent variables in order to make predictions about a single dependent variable. MLR, in contrast, uses multiple independent variables to make predictions about multiple dependent variables. PR is an extension of LiR.However, PR incorpo rates higher-degree polynomial terms of the input features, allowing the model to capture more complex, non-linear relationships in the data that would be impossible to capture with linear models. RR, another extension of LiR, uses a regularization term to address multicollinearity (highly correlated input variables) and overfitting issues. RR can capture nonlinear inputoutput relationships by employing polynomial features and nonlinear transformations.  \n\nLoR and NB algorithms are classification techniques. LoR assumes a linear relationship between the input features and the logarithm of the output class's probabilities. It is frequently applied to continuous data. NB calculates class probabilities based on the distribution of input features within each class, under the assumption that all input features are independent. It is especially useful for categorical data.  \n\nGMM is a probabilistic technique employed for clustering tasks. Typically, it is used to model continuous data. GMM assumes that the data are derived from a mixture of several Gaussian distributions. Each distribution has its own mean,variance (or covariances in the case of multivariate distributions), and weight. These parameters are estimated using the expectationmaximization algorithm.  \n\nSupport vector methods are known for their versatility because they are capable of effectively handling both regression and classification tasks. These methods are especially suited for continuous or categorical data with high dimensionality. The designation “Support Vector Machine\" (SVM) denotes its use as a classification method, while “Support Vector Regression” (SVR) signifies its use in regression analysis. Support vector methods seek an optimal hyperplane that best separates (classification task) or fits (regression task) the data.  \n\nIn contrast to parametric models, non-parametric models do not assume a predefined mapping or distribution for a given problem, which makes them more flexible, adapting to the characteristics of the data. Common non-parametric techniques used in polymer AM research include decision trees (DT),135 K-nearest neighbors (KNN),136 K-means clustering (KMC),137 Gaussian process (GP),138 principal component analysis (PCA),139 and t-distributed stochastic neighbor embedding (t-SNE).125 KMC, PCA, and t-SNE are unsupervised ML techniques, while DT and KNN are supervised ML techniques. GP can be used in both supervised and unsupervised settings. Although all models mentioned can be used for semisupervised learning with proper adaptation, only KNN is inherently suited for this task.  \n\nDTs are algorithms that support both continuous and categorical data for classification and regression tasks. They are capable of capturing complex and nonlinear relationships, which is why they are widely used in for polymerAMIDstais edly based on input features until a termination criterion is met.Each split corresponds to a decision node and terminal nodes (leaves). Leaves represent predicted outputs, which may be class labels or continuous values. DTs are intuitive and resemble human decision-making. They are versatile and powerful tools that can be used effectively as base learners in ensemble learning algorithms (ELA), where the predictions of multiple models can be combined to improve the overall performance and robustness of final prediction. DT-based ensemble methods used in polymer AM and discussed in Section 5 include random forest (RF), extremely randomized trees (EXTr), AdaBoost (ADA), gradient boosting (GB), extreme gradient boosting (XGBoost), and light gradient boosting machine (LightGBM). Notably, while RF and EXTr are required to use DTs as the base learner, other ensemble techniques are not.  \n\nGPs are probabilistic modeling techniques that are used to model continuous data for regression (GPR） and classification (GPC) tasks. GPs assume that the underlying data-generating process is a Gaussian process, which provides a distribution over all possible functions.142 Therefore, when this distribution is used to make predictions for new data points, it can also provide a measure of the uncertainty associated with those predictions.  \n\nKMC and KNN share similarities in terms of handling data, as both use distance metrics. In addition, both methods are applied to continuous and categorical data. Despite similarities, their applications are distinct. KMC is used for clustering tasks, while KNN is used for classification and regression tasks. KMC uses unlabeled data to find patterns, whereas KNN uses labeled data to make predic tions. KNN bases its predictions on the majority class or average value of the K nearest training data points. In contrast, KMC divides the data into K clusters where the center of a cluster is the average of its data points.  \n\nPCA and t-SNE are two methods for reducing the dimensionality of a dataset while retaining as much information as possible.143 However, their approaches to the task vary. PCA uses linear transformations to project data onto a subspace with fewer dimensions. It seeks to preserve the global structure and variation of the dataset. t-SNE, on the other hand, models nonlinear relationships between data points by preserving local structure and relationships in a lower-dimensional space.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# Deep learning models  \n\nBased on architecture, input data type, and application, deep models can be categorized as multilayer perceptron (MLP), recurrent neural network (RNN), or convolutional neural network (CNN). These models are generally described as artificial neural networks (ANN). The architectures of each of these model types are shown in Figure 4.  \n\nANN models are capable of capturing highly complex and non-linear relationships between inputs and outputs.144,145 The models are inspired by the structure and functionality of the human brain. ANN models generally consist of three types of layers: an input layer, one or more hidden layers, and an output layer.146 Each layer is comprised of several nodes, also known as neurons. The information passes from one layer to another through the connections that link the neurons. Each connection in a neural network has a numerical parameter, known as its weight, representing the emphasis given to a partic ular input feature. These weights are iteratively updated by an optimization algorithm during the training process to improve prediction accuracy. The neurons also contain an additional parameter called bias, which allows the model to fit the data flexibly.147  \n\n![](images/f703122f12899bc2e7cdb769fb67e596e6de5e39870424379ff8ee4dd56d731d.jpg)  \nFIGURE 4Generalarchitectures ofdifferentdeeplearming models.(A)Multilayer perceptronfor predicting polymerAMprint properties;(B)RecurenturaletwrkforqualitycontolinpolymerAMprints;(C)Convolutionalnuraletworkfordefectdetectionin a polymer AM process.  \n\nMLPs are fully interconnected feedforward networks As shown in Figure 4A, every neuron in one layer is connected to every neuron in the following layer. MLP is well-suited for structured data such as tabular data. MLP is also capable of working with unstructured data that does not contain spatial or temporal structure, such as flattened images.  \n\nIn contrast to MLPs, which are completely feedforward networks, RNNs have connections that loop back on themselves, as shown in Figure 4B, allowing them to maintain a “memory\" of previous inputs in their internal state. RNNs are, therefore, ideally suited for sequential data with temporal structures. However, long sequences make it challenging for a network to transmit information from one end of the architecture to the other, resulting in unstable training. Long short-term memory (LSTM), a subtype of RNN, has a unique structure for remembering long sequences.148 The choice between standard RNN and LSTM depends on the sequence type of the dataset. Standard RNN is adequate when the output is dependent on the most recent elements in the sequence. On the other hand, LSTM may be considered for long-term dependencies, that is, when the output depends on elements that appeared in the sequence along timeago.149  \n\nCNNs are designed to process data with spatial structures, such as images. The arrangement of pixels in rows and columns, as well as the relative position of different colors and intensities, convey crucial information in an image. As depicted in Figure 4C, CNNs are composed of convolutional layers that apply convolutional filters (also known as kernels) to the input data, capturing local image features such as edges and textures to produce feature maps. After the convolutional layers, CNNs often incorporate pooling layers, which reduce the size and complexity of the feature maps to save computational time and energy.  \n\nANNs exhibit a high degree of customization. These tools have the potential to be modified to suit a diverse range of tasks. MLP, RNN, CNN have been widely employed for various tasks such as regression, classification, and dimensionality reduction.150-157 However, their application in clustering tasks is not as prevalent. Autoen coders (AE) are frequently employed in conjunction with MLP, RNN, and CNN to carry out tasks related to dimensionality reduction.158 The utilization of self-organizing maps (SOMs), a variant of ANN, is prevalent in the domain of clustering tasks.159 sOM is not classified within the overarching framework of deep learning methods due to the absence of multilayered architectures.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 3.3 | Performance metrics for machine learning models  \n\nVarious performance metrics are used to evaluate predic tive performance, modify hyperparameters, and make decisions regarding the selection of ML models. The selection of evaluation metrics is dependent upon the task being carried out. Some of these performance metrics will be introduced in this section to facilitate discussion in subsequent sections.  \n\nRoot mean squared error (RMsE),mean absolute error (MAE), coefficient of determination $(\\mathrm{R}^{2})$ ,and relative error (RE) are used to evaluate the performance of ML models for regression tasks. RMSE and MAE both quantify the disparity between predicted and observed values.However, RMSE is more sensitive than MAE to outliers.160 Low RMSE and MAE values signify performance excellence. ${\\mathrm{R}}^{2}$ values range from O to 1 and represent how well the model fits the dataset. A value closer to 1 represents a superior fit. RE is beneficial when the measured quantities vary greatly in magnitude. Similar to RMSE and MAE values, a low RE value denotes excellent predictive performance.  \n\nF1 score is commonly used as a classification performance metric. F1 score is used when class distributions are unbalanced. Similar to $R^{2}$ values, Fl scores range from O to 1, with values closer to 1 indicating a higher degree of accuracy when identifying a particular class (true positive or true negative).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# 4丨THENEEDFORMACHINE LEARNINGINPOLYMER ADDITIVE MANUFACTURING  \n\nDespite advances in polymer AM, several roadblocks continue to hinder its broader adoption. One major limitation is the relatively narrow range of available materials, particularly when compared to subtractive polymer manufacturing processes, which limits possible applica tions. Additionally, the success of polymer AM processes relies heavily on numerous process and material parameters, making optimization a complex and timeconsuming task. Compared to metals, polymers are less recyclable. Therefore, a key objective during the design phase is to minimize the use of support structures to reduce material waste; this often depends on trialand-error and/or simulations, both of which are time consuming.161 ML techniques are gradually being incorporated to help navigate these challenges. In this section, we discuss the potential of ML techniques to accelerate advances in polymer AM.  \n\nAs AM techniques have progressed from rapid proto typing methods to large scale manufacturing processes capable of creating functional end-use parts, there has been a significant increase in research focused on using a wider range of polymers and polymer composites. Over the past decade, these efforts have been aimed at broadening the application in sectors such as automotive, aerospace and biomedical industries.162 A common aspect of material discovery or screening materials for the AM techniques is that it requires a series of experiments and/or physics-based simulations in order to characterize and validate the choice. Hence, only a few among the vast array of available polymer materials have been employed in AM.  \n\nDue to continued progress in experimental and simulation-based approaches, numerous material databases, such as ChemSpider and MatWeb, now contain an enormous amount of material data for physical, mechanical, and chemical properties.163,164 However, the data are mostly unsorted and accompanied by a large amount of variance, making analysis challenging using only subject-matterexpertise. ML techniques can be used to extract meaningful structure-property correlation from these data, thereby providing recommendations for new materials for AM techniques that are likely to result in improved part quality. This approach can be useful for both the development of novel materials and screening of existing ones.  \n\nAM techniques, which involve many process parameters, are difficult to optimize for achieving desired part properties. Traditional full factorial design of experiments (DoE) is infeasible for exploring the design space due to high experimental cost. Advanced DoEs, such as Taguchi,i65 response surface methodology (RSM),166 and Latin hypercube sampling (LHS)l67 are useful in reducing the total number of experiments. However, these methods only consider the input design space, not the process parameter-property correlations that are crucial for optimization tasks. ML techniques, on the other hand, take into account input-output correlations and therefore have the potential to accelerate the optimization process. Theoretical models derived from fundamental principles are too complex to solve analytically when an array of material and process parameters is involved. Additionally, physics-based models may capture the behavior of the AM system accurately due to considering the under lying physics. However, they are computationally intensive and often time-consuming. ML can be combined with physics-based models to reduce the computational cost and streamline the optimization process.  \n\nWhile ML techniques can extract meaningful information from high-volume data, they can also be useful when it comes to exploring a high-dimensional parameter space, particularly in solving an optimization problem cost-effectively by guiding the sampling only from the promising regions, rather than sampling the entire space, such as AL. Lookman et al. provided a comprehensive guide to using AL in material science.168 The overall goal of AL is to find an accurate predictive model without needing to train with a large volume of data, which is typically required for supervised ML techniques, as the model can intelligently learn from most informative instances.  \n\nThe use of AM techniques to generate complex structures is widespread. For printing to be successful, complex designs require support structures. During the design optimization phase, one objective is to minimize the support structure in order to reduce post-processing steps. Topology optimization (TO) can be undertaken to generate an optimal design with reduced material while still ensuring substantial performance.169 However, TO often suffers from being computationally expensive and may recommend designs that are impractical to implement.17o,171 ML techniques have great potential to be synergistically applied with TO to attain good performance with reduced computational cost.For example, ANN techniques such as CNN-integrated TO were reported to be more efficient than traditional TO without compromising accuracy.172",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# 5 | APPLICATIONOF MACHINE LEARNING IN POLYMER ADDITIVE MANUFACTURING  \n\nThis section summarizes the application of ML techniques to various polymer AM-related tasks. The organization is as follows: 1. Section 5.l summarizes the literature that employed ML techniques in ME; 2. Section 5.2 summarizes the ML-related research in VP; 3. Section 5.3 summarizes the literature based on PBF; and 4. Section 5.4 summarizes the application of ML techniques in inkjet-based AM, including BJ and MJ. Common ML-related tasks for polymer AM include property prediction, process optimization, and in-situ monitoring. Figure 5 provides a comprehensive guide for employing ML techniques for the aforementioned tasks. The selection of ML techniques is primarily determined by the collected data type and dataset size. Small tabular and sensor-based datasets (manual pre-processing) are frequently analyzed with shallow models for property prediction and process optimization tasks. In these instances, the input features are used directly.However, when datasets are large and appropriate features must be extracted from the raw dataset, deep learning models, specifically MLPs, can be employed. CNNs are specially designed for processing image-based data and are primarily used for in-situ monitoring, although process parameter optimization tasks have been performed in certain scenarios.173-176 For in-situ monitoring and process parameter optimization, RNNs are commonly used to process spatiotemporal data, such as data collected from recorded videos. Nevertheless, image segmentation tasks for processing video data are handled uniquely by convolutional layers, which is why RNNs are frequently combined with CNNs. Notably, sequence-based data can be processed by RNNs for any task.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# 5.1 | Machine learning for material extrusion  \n\nAmong all ME-based AM techniques, FFF has made the most extensive use of ML. This is likely due to the wide use of FFF. Additionally, FFF feedstock materials are commercially available and can be used as received. ML applications in DIW are relatively new.177-179 In this review, literature reporting the use of ML for ME are classified according to their broad motivation and are summarized in Table 1. The primary focus has been on predicting mechanical properties and surface quality of the printed parts, reducing experimental effort for process parameter optimization, and in-situ monitoring for online defect detection. ML has also been proven useful in detecting cyber security attacks and reducing the computational time and cost of physics-based simulations.  \n\n![](images/f76297d4395b08d6c2f84dc96167ae8aa2e2696b26ea3d7a40cd74fa90871bfa.jpg)  \nFIGURE5Aguide forapplying machinelearning techniques tocommon types of tasks assciated withpolymer additive manufacturing based on the type and amount of data available.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# 5.1.1 Predicting properties  \n\nThe mechanical and surface properties of ME-based printed parts largely depend on process and design parameters such as extrusion temperature, print bed temperature, print speed, infill density, infill pattern, raster orientation, and layer height. In order to optimize the performance and appearance of the printed parts, it is impractical to depend solely on trial-and-error based methods to tune the process and design parameters. Researchers have taken various ML-based approaches to reduce the experimental effort required to understand the correlations between process and/or design parameters and part properties. In the domain of predicting part properties, training datasets typically consist of empirical data from physical experiments. Data acquired from sensors such as thermocouples and accelerometers can also be used to train. Experiments are often conducted systematically based on advanced DoEs such as Taguchi, RSM, and LHS so that the defined design space is explored efficiently and the data points are informative toward the training process of the ML models.  \n\nShallow and deep learning models have been used for predicting mechanical properties of the ME-based printed parts. ANN models often yield higher predictive accuracy due to their capacity to capture complex non-linear process parameter-property relationships, which are common in AM. However, due to the high level of design freedom, ANN models are typically more complex and computationally expensive than shallow models. Sharma et al. compared the accuracy of shallow models such as RF, KNN, ADA, and DT with LSTM for predicting tensile and flexural strength of polydopamine (PDA)-coated poly(lactic acid)(PLA） bone plates fabricated with FFF.135 The authors investigated the effect of process parameters including infill density of the base PLA structure, immersion time of the PLA structure in a PDA solution, incubator shaking speed for the coating solution, and coating solution concentration. The ML models used an experimentally generated training dataset consisting of 100 data points, where the process parameters were considered as input features and corresponding tensile and flexural strengths were considered as outputs. The work reported a significant gain in prediction accuracy for the LSTM model compared to the traditional ML models. For example, predictive performance for tensile strength as $R^{2}$ for RF, KNN, ADA, and DT were 0.7425, 0.7217, 0.7191, and 0.695l, respectively,whereas $R^{2}$ for LSTM was 0.9242. However, training ANN models with limited data may result in overfitting due to lack of generalizability for unseen data points.196  \n\nSurface roughness is an important property since it greatly affects mechanical and optical properties of AM parts. Thus, multiple studies have investigated the surface roughness of ME parts. Surface roughness of printed parts depends on parameters such as layer thickness, raster orientation, print speed, print bed temperature, infill pattern, and infill density. Several experimental studies197 and analytical models19s,199 have been used to estimate surface roughness of AM parts. However, ML-based modeling methods present an alternative approach to roughness determination since they are computationally less demanding than numerical techniques such as finite element analysis (FEA） and are capable of reducing experimental effort.  \n\nTraining of ML models for predicting surface roughness of ME parts has been achieved with both sensor signals and experimental data acquired by varying multiple process parameters. Li et al. proposed a data-based hybrid modeling technique for FFF, where the training process takes place offline with temperature and vibration data from in-situ sensors while the prediction of the surface roughness takes place online.182 The authors used RF to select important features from the processed sensor data to reduce computational time and to avoid overfitting. The RF selected features were then fed into an ELA consisting of six ML models to develop a predictive model for surface roughness, which was later employed in online prediction. Based on RMSE and RE values, the authors reported that the overall predictive performance of the ensemble algorithm is higher than its base models. Nevertheless, the simpler constituent models, RR and SVR, had very close RMSE and RE values to the ELA, indicating the potential to bypass the computational complexity. It is worth noting that ELAs can be important for providing improved accuracy and better generalizability compared to the constituent models. However, they are often computationally intensive and somewhat less interpretable than the simpler models. Hence, the tradeoff between accuracy and interpretability must be considered carefully when ML techniques are being employed for property prediction in AM structures.  \n\n(teseentn   \nreneaeeeenereeeneereeeenereeeereeeieeee TT   \n\n\n<html><body><table><tr><td> Broad motivation</td><td colspan=\"3\">AM technique ML technique</td><td> Remarks</td><td>References</td></tr><tr><td rowspan=\"10\">Property prediction</td><td>FFF</td><td>RF, KNN, ADA, DT, and LSTM</td><td>Infill density, submersion time, shaker speed, and coating solution concentration</td><td> Predicting tensile and flexural strengths</td><td> Sharma et al.135</td></tr><tr><td>FFF</td><td>LiR, GPR, RR, and KNN</td><td>Extruder temperature and layer height</td><td>Predicting five critical tensile properties (Young's modulus, yield stress, yield strain, tensile stress,</td><td> Nasrin et al.129</td></tr><tr><td>FFF</td><td>LiR, DT, RF, and</td><td> Infill density, layer thickness, print orientation,</td><td>and tensile strain) Predicting hardness</td><td> Veeman et al.113</td></tr><tr><td>FFF</td><td>ADA RF</td><td>and raster orientation Infill pattern, infill density, and the number of sprayed layers</td><td>Predicting ultimate flexural strength, fracture flexural strength, strain at peak and strain at</td><td> Ranjan et al.180</td></tr><tr><td>FFF</td><td> MLP</td><td>Bed temperature, printing speed, layer thickness, and orientation angle</td><td>break Predicting surface roughness</td><td>Malleswari et al.181</td></tr><tr><td>FFF</td><td>ELA</td><td>Build plate temperature and vibrations, extruder temperature and vibration, and temperature of</td><td>Predicting surface roughness</td><td>Li et al.182</td></tr><tr><td>FFF</td><td>KMC, LiR, and MLP</td><td>the deposited material Layer thickness, fan speed, and infill density</td><td>Predicting surface roughness</td><td>Si et al.183</td></tr><tr><td>FFF</td><td> MLP</td><td>Extruder temperature, infill percentage, and layer thickness</td><td>Predicting toughness, part thickness, and production cost</td><td> Meiabadi et al.184</td></tr><tr><td>FFF</td><td>MLP</td><td>Printing speed, extrusion temperature, infill density, extruded filament thickness, extrusion orientation</td><td>Predicting tensile strength</td><td> Silva et al.185</td></tr><tr><td>Process parameter FFF optimization</td><td>CNN and RF</td><td>Material extrusion rates and extrusion temperatures</td><td>Correlate the process parameters with the quality of printed parts (surface roughness, hardness,</td><td> Butt et al.173</td></tr><tr><td rowspan=\"5\"></td><td>FFF</td><td>CNNs</td><td> Infill type, density, material, wallthickness, layer</td><td>and tensile strength) Predicting optimal input parameters for user defined mechanical properties</td><td> Ratnavel et al.174</td></tr><tr><td>FFF</td><td> LiR and PR</td><td>Layer height, printing speed and printing bed temperature for the coating layer</td><td>Finding most influential coating layer print parameter for ultimate shingle-lap shear</td><td> Belei et al.186</td></tr><tr><td>FFF</td><td> GPR</td><td>Tensile testing and surface imaging data</td><td>strength Optimizing print parameters to achieve superior surface quality</td><td> Liu et al.187</td></tr><tr><td>FFF</td><td>RF, SVM, LoR,</td><td>Formulation data from literatures</td><td> Predicting processng parameters and printability</td><td>Castro et al.136</td></tr><tr><td></td><td> KNN, and MLP</td><td></td><td>for additively manufactured drugs based on literature-mined formulations</td><td></td></tr></table></body></html>  \n\n(panunuon) TTRE   \n\n\n<html><body><table><tr><td>Broad motivation</td><td> technique</td><td>ML technique</td><td>Model inputs</td><td>Remarks</td><td> References</td></tr><tr><td></td><td> FFF</td><td>GP</td><td>Temperature history from heat transfer analysis</td><td>Optimizing print parameters for reducing geometrical inaccuracy</td><td>Nath et al.138</td></tr><tr><td></td><td> FFF</td><td> SOM</td><td> Laser scanning data from the surface of test parts</td><td>Understanding correlations between process parameters and geometric accuracy</td><td>Khanzadeh et al.188</td></tr><tr><td></td><td> DIW</td><td>PCA and SVM</td><td>Pivotal lines (areas providing mechanical support) and transition points (areas not bearing stress after printing)</td><td>Optimizing print parameters for newly developed ink </td><td> Zhu et al.139</td></tr><tr><td></td><td> DIW</td><td>KMC, SVM, GPR</td><td> Sheath gas flow rate andcarrergas flowrate</td><td>Improving the quality of aerosol jet printing by optimizing the deposited droplet morphology</td><td> Zhang et al.137</td></tr><tr><td>In-situ monitoring for anomaly/defect detection</td><td>FFF</td><td>CNN</td><td>Image data from printhead</td><td>On-site monitoring system for detecting defects (under-extrusion and over-extrusion) and make corrections in real-time</td><td>Goh et al.189</td></tr><tr><td></td><td>FFF</td><td>RNN and ADA</td><td> Sensor signal from side channel</td><td>Sensor-based anomaly detection during unintended process/product alterations caused by cyber-security attacks</td><td>Shi et al.190</td></tr><tr><td></td><td>FFF</td><td> SVM, NBC, and DT</td><td>Combined feature vector of acoustic emission and point cloud data</td><td>Real-time monitoring based on acoustic emission and laser technology for monitoring warpage defect</td><td>Xu et al.118</td></tr><tr><td></td><td>FFF</td><td>RNN</td><td> Simulation results from digital twin</td><td>Automated clogging detection by predicting extrusion rate, extrudate temperature, and</td><td> Rossi et al.191</td></tr><tr><td></td><td>FFF</td><td> SVM and CNN</td><td>Digital imaging</td><td>compression force acting on the filament Detecting anomalies at the topographic level</td><td> Rossi et al.192</td></tr><tr><td></td><td>FFF</td><td>SVM, KNN, and CNN</td><td>Image data from 3D laser scanning</td><td>Laser-based process monitoring system for assuring print quality</td><td>Lyu et al.193</td></tr><tr><td></td><td>FFF</td><td>MLP</td><td>Thermal data from a physics-based model</td><td>Surrogate modeling replicating thermal profile simulation</td><td> Roy et al.194</td></tr><tr><td></td><td>FFF</td><td>PCA, SVM, and CNN</td><td> Image data from video recording during printing</td><td> Automated classification of print quality during</td><td>Narayanan et al.195</td></tr></table></body></html>  \n\nSurface roughness has been more commonly predicted based on process parameters such as layer thickness, infill density, raster orientation, and print speed.181183Asthedatasetisoftenexperimentally acquired, researchers leverage advanced statistical DoE techniques to reduce the number of total experiments. For example, Malleswari et al. used Taguchi method, which was useful to reduce experimental time and cost for generating the dataset by using orthogonal arrays. S.181 In this work, the authors explored the effect of four processing factors on surface roughness: print bed temperature, printing speed, layer thickness, and raster orientation. Each processing factor included three levels, which would require conducting a total of 81 experiments with full factorial DoE. The Taguchi method helped to reduce the required experiments by three-fold. The acquired data was informative toward the training process evidenced by $R^{2}$ values of 0.993 and 0.994 for RSM and MLP, respectively.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# 5.1.2 | Process parameter optimization  \n\nML techniques have been proved to be useful to optimize process parameters to obtain superior qualities in the printed parts. For example, dimensional inaccuracies are a common problem in AM parts. ML techniques have been used to tune process parameters to reduce dimensional inaccuracies.i38,188 Khanzadeh et al. reported that geometric deviations are correlated with extruder temperature and infill percentage. Thus, these parameters can be optimized to attain higher geometric accuracy.188 This work used a large dataset consisting of laser-scanned coordinates of the parts printed at varying extruder temperature and infill percentage. In order to measure the geometric deviations, the laser scanned coordinates were compared to the original CAD design of the part. The geometric deviations were then clustered using SOM based on their similarity in shape deviations, both in direction and magnitude. The clusters were then ranked based on the severity of their geometric deviations. Upon analyzing the most critical clusters, the authors were able to adjust the extruder temperature and layer height to reduce the geometric inaccuracies.  \n\nML techniques have also been used for optimizing process parameters for obtaining superior surface quality173,17anddesidmecanicalpprtieshe overall goal is to reduce reliance on trial-and-error-based approaches to find the best parameter setting for the desired part quality. Liu et al. proposed a GP-based non parametric Bayesian framework for optimizing process parameters (extruder temperature, print speed, and layer thickness) for improving surface quality of graphene filled nanocomposite FFF parts.187 In this work, Bayesian optimization (BO） guided the search for the process parameters yielding the lowest surface roughness. GPR served as the surrogate model and was initially trained with just four data points, establishing a prior distribution. The model was then iteratively refined with new data points corresponding to the acquisition function maximum value, updating the prior to form a posterior distribution. The optimization process was terminated after only the fifth iteration because the predicted surface roughness for the recommended process parameter settings converged with the experimental value.  \n\nML-based techniques have been used to optimize printing parameters for reducing defects in printed parts.139 The modeling approach taken in this study used data from in-situ imaging. A camera was attached to the printing nozzle to record the printing process in realtime. Nine videos were recorded with different layer thicknesses and nozzle speeds. The videos were converted into individual frames, which were then fed to PCA to reduce dimensionality and extract relevant features. After dimensionality reduction, SVM was used to classify the transformed data into two distinct categories: pivotal lines and transition points. The knowledge gained from PCA and SVM provided the foundation for the opti mization step, where the aim was to detect the processing parameters (layer thickness and nozzle speed) that produce the fewest defects. The model performance was assessed through a three-fold cross validation process, and it was found that slower nozzle speed and smaller layer thickness are beneficial for reducing print defects.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 25,
+        "chunk": "# 5.1.3 In-situ monitoring  \n\nIn-situ monitoring is largely applied in AM for defect and anomaly detection. Sensorsi18,190 and high-resolution cameras189195arecommonlyused todetectdefectsin real-time. Data acquired from sensor signals and processed images are often combined with ML techniques for predicting defects in the early stages of printing process. An example of using sensor signal-based ML for insitu monitoring was demonstrated by Xu et al.l18 They combined acoustic emission with laser scanning technology to develop a real-time monitoring system for detecting warpage in FFF parts. The acoustic emission sensors were placed along the print bed to capture platform vibrations during the printing process, while the warpage in each layer of the printed structure was quantified using point cloud data from laser scanning. The combined data were then used to train three ML algorithms: SVM, NB, and DT. It is worth noting that sensor signals consist of numerous features. In order to ensure good predictive accuracy, selecting the appropriate features is crucial. Xu et al. extracted voltage distribution information from the raw acoustic emission signal because it was highly correlated with structure warpage. Overall, DT outperformed the other two ML models for classifying the printed parts based on the amount of warpage.  \n\nFor in-situ monitoring involving image-based data, CNN models using different architectures are preferred.189,19195For instance,Gohet al.usedCNN with various“You Only Look Once\"(YOLO） architectures to analyze images captured during the printing process in order to detect print anomalies (over under-extrusion/ over-extrusion).189 Using YOLO-based architectures with CNN has the advantage of processing images in a single pass, which enables simultaneous detection of multiple objects.200,201  \n\nPhysics-based models can offer a comprehensive understanding of the printing process and can be useful for in-process monitoring. However, their in-process application is frequently hindered by high computational cost. ML models have been used as surrogates because they are more computationally efficient than physicsbased models. In this circumstance, ML-based surrogate models are built using data collected from physics-based models. They replace the computationally intensive models when they achieve sufficient accuracy. For example, Rossi et al.19l and Roy et al.194 used physics-based models to collect the initial data for training deep learning models, which were subsequently used for in-situ monitoring of the FFF process. Rossi et al. used an RNN model to simulate a complex extrusion process simulation. This model was then used to detect clogging events by analyzing the deviations between predicted and realtime values of extrusion rate, extrudate temperature, and filament compression force, as measured by various sensors during printing. Roy et al. used an MLP-based surrogate model to replicate the thermal profile of various geometries, allowing for inline monitoring of the FFF process.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 26,
+        "chunk": "# 5.2 | Machine learning for vat photopolymerization  \n\nVP techniques are widely favored due to their rapid print ing speeds and ability to achieve high resolutions. The use of ML techniques in VP has emerged more recently in comparison to ME. ML-based research in VP tends to fall into three distinct groups: material and process optimization, in-situ monitoring, and metamaterial design The optimization of material and process parameters through ML techniques focuses on minimizing the need for extensive experimentation. In-situ optimization aided by ML methods focuses on defect detection. Therefore, the primary workflows are examined within the context of VP techniques. ANN models have been the prevailing approach in research pertaining to VP. Table 2 presents a comprehensive overview of the literature relating to MLassisted VP. This table includes details such as the ML techniques employed in each study, the model inputs that reflect the source of training data, and the specific objectives of each work.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 27,
+        "chunk": "# 5.2.1 Process parameter optimization  \n\nFor VP, ML models are used to optimize different printing and material parameters such as light dosage, exposure time, printing speed, and material compositions for printing structures with desired properties. Existing research has used various types of image-based data, captured during printing process, totrain ML models.175agesofo of large quantities of data. ANN models tend to be more generalizable when trained with a large amount of data.2ll In addition, after determining a suitable architecture, ANN techniques can automatically extract important features from a large volume of data. As a result, many studies have used ANN techniques for optimizing the VP process. For example, Guan et al. used ANN to enhance the quality of celloaded bioprinting.176 They printed structures using digital masks and imaged those structures. A genetic algorithm was used to calibrate a mathematical 3D printer simulator using digital masks and images of the structures. This procedure aimed to replicate the effects of cell loading on light scattering during printing. 400o training data points (digital maskimage pairs) were produced using the calibrated simulator, which was not possible using only the printing process. The trained CNN model was then used to create a mask that accounted for light scattering consisting of a grayscale image that represented the light exposure dose for any given target structure. ML-optimized masks increased print fidelity for the highly scattering cellloaded material.  \n\nWhen the training dataset is small, shallow models are typically chosen to avoid overfitting and improve interpretability.212 For instance, Tagami et al. investigated the effect of light exposure time and material composition on drug release from VP-based poly(ethylene glycol) diacrylate (PEGDA) tablets with MRA and SVM trained on a dataset containing only 108 data points.203 In this study, six input features were analyzed, five of which were associated with material composition and one with the processing condition, specifically light exposure time. MRA with a sequential forced entry method elucidated which parameters significantly affected drug release. The results of the MRA analysis indicated that excluding the “light exposure time\" variable from the dataset improved the accuracy of drug release predictions. Later, the MRA analysis served as the foundation for the development of an SVM-based drug release kinetics model.  \n\nrreeeeaereeneeeerenerneereeeereareeaererenaeen AR   \n\n\n<html><body><table><tr><td> Broad motivation</td><td>AM technique</td><td> ML technique</td><td> Model inputs</td><td>Remarks</td><td> Reference</td></tr><tr><td rowspan=\"6\">Process-parameter optimization</td><td>SLA and DLP</td><td>CNN</td><td>High-resolution images of microneedle patches</td><td>Optimizing lithium phenyl (2,4,6-trimethylbenzoyl) phosphinate (LAP) concentration, water concentration, and exposure time for controlling needle morphology and</td><td>Bagde et a)</td></tr><tr><td>DLP</td><td>LSTM</td><td>Grayscale values of each element in finite element model</td><td>Optimizing grayscale distributions for obtaining varying deformations in printed structures</td><td>Zhao et al.</td></tr><tr><td>DLP</td><td>CNN</td><td>Digital mask image data and simulator generated structures</td><td>Optimizing grayscale value to compensate for scattering effect of cell-loaded bioink</td><td>Guan et al</td></tr><tr><td>DLP</td><td>MRA and SVM</td><td>Composition of ink and printing parameter (light exposure time during printing)</td><td>Investigating the effects of ink composition and printing conditions on drug release of printed tablets</td><td>Tagami et</td></tr><tr><td>CLIP</td><td>Shallow models (DT, NB, KNN, SVM), ELAs (RF, GB, ADA), and deep learning (MLP-based Siamese</td><td>Material properties, geometric and physical parameters, printing dynamics, surface texture and quality, hardware and setup</td><td>Optimizing printing speed</td><td>He et al.204</td></tr><tr><td>In-situ monitoring SLA and DLP</td><td>neural network) GPR</td><td>Thermistor data</td><td>Real-time failure detection and area prediction</td><td> Shan et al.</td></tr><tr><td></td><td>2PP</td><td>3D-CNN and CNN-LSTM</td><td>Image data from printing while light dosage varies</td><td>Identifying the optimal light dosage and part defect detection</td><td>Lee et al.20</td></tr><tr><td rowspan=\"5\"> Metamaterial design</td><td>SLA</td><td>MLP</td><td>Control points from Bezier curves</td><td>Designing novel beam elements with varying cross-sections</td><td>Lee et al.20</td></tr><tr><td>SLA</td><td>Variation AE (Combined with CNN and MLP)</td><td>Binary images of representative volume elements</td><td>Designing optimal representative volume elements with specified macroscopic elastic moduli</td><td>Xu et al.208</td></tr><tr><td>DLP</td><td>MLP</td><td>FEA simulation results for mechanical properties while varying the design aspects</td><td>Designing novel metamaterial with varying stiffness in three spatial directions</td><td>Fleisch et </td></tr><tr><td>SLA</td><td>MLP</td><td>Length and orientation angle</td><td>Optimizing the design of SLA-printed</td><td>Tak et al.21</td></tr><tr><td></td><td></td><td></td><td>W-band slotted waveguide array antenna</td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 28,
+        "chunk": "# 5.2.2 In-situ monitoring  \n\nIn-situ monitoring is frequently used in VP for monitoring unexpected process variations, which lead to thermal distortions, print failure, and other defects in printed parts. ML techniques have the capacity to predict print outcomes at the initial stages of the printing process. In bioprinting, where feedstock is expensive, this is particularly useful for reducing material waste. Camera systems are commonly used in in-situ monitoring of AM. Using video data captured during the printing process in twophoton lithography (TPL) printing, Lee et al. developed a spatiotemporal ML-based process for detecting part defects.206 The work entailed the creation of a comprehensive dataset consisting of raw videos from four sets of experiments: three with commercially available photoresists and one with a custom photoresist. Experiments included varying structures (cuboids and truncated cones), discretization (log-pile rectangular Cartesian grid and grid of concentric circles), scan paths, and experimental parameters such as discretization period in the X-Y plane, write speed, and laser power. Due to the spatiotemporal and high dimensional nature of the dataset, which is typical of video-extracted data, two different ANN models were trained: 1. 3D-CNN and 2. CNNLSTM. While 3D-CNN only captured the spatial relationship in three dimensions from the dataset, CNN-LSTM captured both spatial and temporal relationship due to its hybrid nature (CNN for feature extraction from images and LSTM for sequence prediction tasks). Consequently, CNN-LSTM had higher accuracy in defect detection $(\\sim95\\%)$ compared to 3D-CNN $(\\sim91\\%)$ .  \n\nThe printing mechanisms and optical systems used in VP techniques make it challenging to monitor printingrelated changes using traditional image-based analysis.205 Thermal cameras have been reported in some studies.213,214 However, the use of thermal cameras is constrained by their high cost and limited accuracy. To address these concerns, Shan et al. developed a compact intelligent vat system that monitors the printing process through the analysis of temperature data acquired from thermistors that are evenly distributed and affixed to the edges of the resin vat.205 The system was designed to monitor temperature fluctuations throughout the resin vat during printing and these fluctuations were used as indicators of the degree of polymerization occurring. The authors trained a GPR model with temperature data from thermistor to predict the printed area of each layer since the rise in temperature is related to photopolymerization. Subsequently, the trained model was used to predict potential feature defects that could arise throughout the printing procedure. The study found that the predictive model had low accuracy, which was attributed to overfitting resulting from the limited size of the training dataset. The choice of temperature fluctuations as an input feature, which may not be a good indicator of the degree of polymerization in VP, may also contribute to low predic tive accuracy.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 29,
+        "chunk": "# 5.2.3 Metamaterial design  \n\nMechanical metamaterials are comprised of periodic architectures capable of producing exceptional macroscale level properties such as auxetic behavior (negative Poisson's 。ratio),215 programmable mechanical response,216controlledbulkingbehavior,217shape morphing,218andacousticband gaps.219VPtechniques are useful for fabricating polymer-based metamaterials due to their capacity to offer high speed, good resolution and excellent surface quality.47 However, designing the lattice units for metamaterials based on past knowledge and intuition is insufficient for next generation designs. Furthermore, using FEA for exploring the large design space of possible lattice structures is computationally expensive. Hence, research has focused on applying ML techniques for creating new designs for lattice structures for metamaterials and optimization of the existing ones. In particular, ANNs have become important for metamaterial design because they can generate equivalent solutions to FEA, which is a crucial technique for determining the feasibility of structural designs, while reducing the computational time and cost by many orders of magnitude.  \n\nDesign optimization of lattice structures starts from the root, which is the beam element of the unit cells. A uniform cross-sectional area is typically assumed for the root, which limits the achievable strength-to-weight ratio. Moreover, the junction where the beam elements meet often suffers from lower strength compared to other regions. As a result, the lattice structures with a uniform beam element cross-section often fail to yield the desired performance without increasing the density of the lattice structure. To address this, Lee et al. introduced a workflow that integrates ANN with genetic optimization (GO)to enable more diverse and advanced selection of beam element shapes.207 An interesting aspect of this work is applying Bezier curves for generating the designs of beam elements. Bézier curves include control points that determine the curve's shape and orientation.220 A population of initial unit cell structures was generated by randomly modifying the control points of the beam elements and the initial designs underwent assessment for elastic modulus and strength using FEA. The GO step then chose the cell designs with superior performance and mixed their control points to generate new cell designs. After a significant amount of data (cell designs and their FEA-evaluated mechanical performances) was generated through the GO process, a dataset containing control points as input and mechanical performance as output was curated,which was used to train an MLP model. In order to verify the efficacy of the entire workflow and the resulting designs, a selection of the highest performing lattice structures (identified by MLP and subsequently confirmed by FEA) were manufactured using SLA and tested experimentally. The results of the experimental validation demonstrated that the lattice design optimized using ML exhibited superior performance compared to two benchmark models, namely the gradeddensity beam and the cylindrical beam.  \n\nComposite materials can achieve properties that would be impossible to achieve with a single base material. Designs of metamaterials based on composite materials present unique challenges due to the large design space, which includes a wide variety of possible configurations for the unit cells and fine-tuning structural properties through spatial material distribution. Thus, process automation necessitates the intervention of ML. Xue et al. proposed an ANN-based framework that incorporates multi-material-based unit cell design, also known as representative volume element (RVE).208 The materials consisted of a hard polyurethane-based material and a soft silicone-based material. The focus of the work was to control the elastic moduli of the cumulated lattice structure. A database was developed with combinations of artificially generated binary images. The authors used variation AE to generate potential design structures for RVE using the binary images from the database. The encoder architecture included a combination of convolutional and dense layers (fully connected) and the decoder architecture included a combination of deconvolutional and dense layers. The architecture leveraged CNN's spatial feature extraction and ML's data compression and reconstruction capabilities. The best RVE configuration that met the desired properties was determined with BO and the optimized designs were printed using SLA and subjected to tensile testing to ascertain the elastic moduli. The majority of experimental results were found to be consistent with computational predictions.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 30,
+        "chunk": "# 5.3 | Machine learning for powder bed fusion  \n\nPBF is a popular AM technique since it is capable of printing without a support structure. Polymer-based PBF is restricted by its limited material selection. In addition, the current quality control and in-situ optimization techniques heavily rely on human expertise, which hinders process automation. The complexity of existing physicsbased models for characterizing relationships between process parameters and part properties prevents their use in process optimization. To address these issues, current research employs ML techniques, as summarized in Table 3. Literature is classified in accordance with four broad motivations: 1. Material selection; 2. Quality control; 3. In-situ monitoring; and 4. Discrete outcome pre dictions. This section provides a brief discussion of ongoing research outlining the trends in ML for polymerbased PBF.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 31,
+        "chunk": "# 5.3.1 Material selection  \n\nIntrinsic properties such as particle size and shape, thermal properties, optical properties, rheological properties, and extrinsic properties such as powder flowability, bulk density, and tapped density are important when selecting polymer powders for SLS.231 Therefore, when introducing a new material, a series of characterization techniques are typically employed to determine its applicability for SLS printing, which is time consuming and requires extensive subject matter expertise. Moreover, printing withnew materialsincludes resource intensive trail-and-error to determine appropriate combinations of processing conditions to achieve successful prints. ML techniques have been used to reduce experimental effort by identifying correlations between the powder's intrinsic properties and its printability.125 Utilizing the power of ML techniques, a simple material-agnostic screening technique was also developed based on extrinsic properties to predict the suitability of new materials for SLS.221  \n\nIn order to identify printable formulations of a powdered pharmaceutical, Abdalla et al. developed a pipeline based on classification techniques that uses the data related to intrinsic properties of the formulations, such as differential  scanning calorimetry (DSC), Fourier-transformed infrared spectroscopy (FTIR), and x-ray diffraction (XRD) results.125 Raw data from each characterization technique were fed to an unsupervised ML model (PCA） for reducing dimensionality before applying the supervised models (RF, LR, SVM, GB, XGBoost, DT, MLP, KNN, and EXTr), thereby decreasing the reliance on human expertise for data analysis and decision making. The predictions from supervised models showed that FTIR spectra resulted in higher accuracy $(84.2\\%)$ than DsC thermograms $(80.1\\%)$ and XRD diffraction data $(81.3\\%)$ due to its higher capacity to handle the diversity and complexity of the formulations, especially when they contained amorphous polymers, which posed challenges for the other two methods. Moreover, combining all the characterization information led to even higher predictive accuracy $(88.9\\%)$ than the spectral data alone. In both cases, the best predictions were provided by RF, an ensemble model developed through combining multiple DTs.  \n\noepetedaeeneteeieareareeoreeneened SRAR   \n\n\n<html><body><table><tr><td>Broad motivation</td><td>AM technique</td><td> ML technique</td><td> Model inputs</td><td> Remarks</td><td> References</td></tr><tr><td>Material selection</td><td>SLS</td><td>LR, KNN, SVM, DT, MLP, EXTr, RF, GB, and XGBoost</td><td>Formulation composition and characterization data</td><td>Predicting printability of formulations using multi-modal data</td><td> Abdalla et al.125</td></tr><tr><td></td><td>SLS</td><td>SVM</td><td>Powder flowability and as-spread surface roughness</td><td>Developing a pre-screening method for SLS materials</td><td> Sassaman et al.221</td></tr><tr><td>Quality control</td><td> SLS </td><td>GPR</td><td>Surface diffusivity and interparticle distance</td><td>Analyzing the relationship between input parameters and the size of the neck region between particles</td><td> Batabyal et al.222</td></tr><tr><td></td><td> SLS</td><td>CNN</td><td>Data obtained from X-ray Computed Tomography (XCT)</td><td>Evaluation of DL vs. traditional methods on low-quality XCT scans</td><td> Bellens et al.223</td></tr><tr><td>Discrete outcome prediction</td><td>SLS</td><td>MLP</td><td>Binary image data from sliced CAD files</td><td>Predicting energy consumption using a knowledge distillation approach</td><td>Li et al.224</td></tr><tr><td></td><td>SLS</td><td>Genetic programming, SVR and MLP</td><td>Layer thickness,laser power, and feed rate</td><td> Predicting open porosity</td><td>Garg et al.225</td></tr><tr><td></td><td>SLS</td><td>Ensemble-based multi- gene genetic programming</td><td>Layer thickness,laser power, and laser scan speed</td><td>Predicting open porosity</td><td>Garg et al.226</td></tr><tr><td></td><td>SLS</td><td>MLP</td><td>Laser power, scan speed, scan spacing and layer thickness</td><td> Predicting density</td><td>Shen et al.227</td></tr><tr><td></td><td>SLS</td><td>MLP, DT, GB, and SVR</td><td> Part orientation</td><td> Predicting part dimension</td><td> Baturynska et al.141</td></tr><tr><td></td><td>SLS</td><td>MLP, SVM, and NB</td><td>Coordinates of the parts within the print volume and print parameters</td><td>Predicting surface roughness in the production planning phase</td><td> Kog et al.228</td></tr><tr><td> In-situ monitoring</td><td> SLS</td><td>CNN</td><td>Images of powder bed samples captured during printing process</td><td>Automatically classifying powder bed defects</td><td>Westphal et al.229</td></tr><tr><td></td><td> SLS</td><td>CNN</td><td> Thermal infrared recordings</td><td> In-situ quality control that detects</td><td> Klamert et al.230</td></tr></table></body></html>  \n\nSassman et al. used a classification algorithm to develop a material-agnostic screening method for SLS materials in an effort to accelerate the process of determining whether a particular powder (nylon) or powder mix (nylon mixed with various amounts of alumina and carbon fibers) would be suitable for a particular applications.21 This method used extrinsic properties, such as powder flowability information extracted from revolution powder analysis (RPA) and as-spread surface roughness, pertaining to the condition of the powder after it has been spread but prior to the SLS process. A SVM classifier was trained separately using RPA and asspread surface roughness data. The prediction results demonstrated that powder systems were correctly classified using RPA information $(93.1\\%)$ , but not surface roughness information $(62.5\\%)$ ， establishing the RPA process as a promising technique for pre-screening materials for the SLS process.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 32,
+        "chunk": "# 5.3.2 |Quality control  \n\nThe complex dynamics of the SLS process, influenced by numerous parameters, often result in final part quality variability.232 A significant challenge in SLS, as with other AM methods, is achieving consistent part quality. Computational modeling such as phase-field microstructure model222 as well as characterization tools such as x-ray computed tomography $\\left(\\mathrm{X-CT}\\right)^{223}$ have been combined with ML techniques for data processing and analysis to gain a better understanding of the critical parameters influencing SLS part quality.  \n\nSLS final part quality depends on factors such as particle size and shape,233 contact area between particles,234 and diffusion kinetics (grain boundary vs volume diffusion).235 Batabyal et al. investigated microstructure variation during sintering based on two parameters: 1. Surface diffusivity between two polymer particles (equal sized particles and unequal sized particles) and 2. Interparticle distance.222 The size of the neck that forms between two particles during sintering was selected as the response quantity of interest (QOI). Training data was obtained from a two-particle phase-field microstructure model simulation. GPR was used as a surrogate model to approximate the underlying relationships between the input features (surface diffusivity and interparticle distance) and QOI. Sensitivity analysis showed that neck size is more sensitive to changes in interparticle distance than surface diffusivity irrespective of the particle size. BO was used to optimize the input features using two acquisition functions: 1. Expected improvement and 2. Probability of improvement. The optimization results from both acquisition functions were in good agreement, validating the optimization approach. Thus, the MLbased framework served as a rapid predictive tool for capturing the complex behavior of the sintering process, paving the way for enhanced quality control.  \n\nIn order to assess the quality of SLS printed parts, numerous non-destructive characterization techniques have been shown to be useful. Such characterization techniques include XCT,236 micro computed tomography (micro-CT),237 eddy current testing,238 and acoustic emission.239 Multiple techniques are necessary to confidently determine the quality of printed parts,which requires time and expertise. ML techniques have been able to accelerate quality assessment.223 For example, Bellens et al. employed CNN using U-net and MultiResUnet architectures, which are particularly useful for image segmentation tasks.240,241 To compare the effciency of the CNN-based image segmentation with the traditional Otsu's global algorithm, several observations were made in terms of quality inspection such as porosity and defect detection. Traditional technique requires 1500-3000 pro jections for accurate segmentation, while CNN showed improved results with as few as 99-1572 projections, substantially reducing the acquisition time.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 33,
+        "chunk": "# 5.3.3 In-situ monitoring  \n\nCommon in-situ monitoring techniques applicable to polymer-based PBF include surface defect detection through image-based optical monitoring,242 temperature distribution monitoring using infrared thermography,243 and laser power monitoring to ensure uniform melting.244 Recent studies have centered on incorporating ML techniques into image-based in-situ monitoring for defect detection.29.230 CNNs are commonly used given their ability to handle image-based data.245,246 Westphal et al. reported a detection accuracy of up to $95.8\\%$ for defects using a VGGl6 CNN architecture trained with data extracted from powder bed images.229 Klamert et al. also reported a very high accuracy of $98.54\\%$ for detecting curling defects using the same architecture trained with thermal imaging data.230",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 34,
+        "chunk": "# 5.3.4 Discrete outcome prediction  \n\nSupervised learning has been used to predict discrete outcomes of SLS structures, such as energy consumption,224 porosity as a percentage of void content in printed structures26eity27atdims, face roughness.228 These are important quantities/ qualities to investigate in order to ensure precision and reliability, quality control, resource optimization, and the safety and functionality of a system.  \n\nExisting research has relied on MLP for discrete outcome predictions. The problems were framed as either regression or classification task. For example, Li et al. trained an MLP model with a teacher-student architec ture using layer-by-layer images of the printed structures to predict the energy consumption during the printing process.224 The correlations of the input and output features were transferred from a complex model (the \"Teacher\" model) to a simpler model (the “Student\" model), thereby reducing the model training time. More over, MLP was used to predict the part density based on scan speed, scan spacing, laser power, and layer thickness.227 MLP was also used for clasification, where it was used to predict surface roughness (set to a categorical output). In this example, MLP performed better than traditional classification methods such as SVM and NB when its hyperparameters were appropriately tuned.228 On the other hand, evolutionary algorithm-based approaches such as genetic programming and ensemblebased multi-gene genetic programming, outperformed MLP for predicting the open porosity of SLS parts.225,226",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 35,
+        "chunk": "# 5.4 | Machine learning for binder jetting and material jetting  \n\nBJ and MJ are two categories of AM that employ inkjet based material deposition techniques. Therefore, the exploration of ML applications within both BJ and MJ is discussed together. While there have been several reports of ML being used in BJ, particularly for porosity analysis, its application in MJ has been more limited. Conversely, ML techniques have been widely used for process parameter optimization, benefiting both BJ and MJ techniques Table 4 summarizes applications of ML in BJ and MJ, categorizing them into two main groups: one focusing on porosity analysis unique to the BJ process, and the other on process parameter optimization,relevant to both BJ and MJ processes.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 36,
+        "chunk": "# 5.4.1 Porosity analysis  \n\nNumerous studies have been conducted to address the issues associated with defect detection and quality control in BJ to ensure the consistency and reliability of end-use parts.249 Due to its direct effect on the final properties, porosity analysis is of particular interest for BJ.254 However, characterization techniques such as SEM and transmission electron microscopy (TEM) provide analysis of local pore morphologies that may not be representative of the entire structure. In addition, traditional image analysis software requires specific conditions and manual inputs, making the porosity analysis process timeconsuming and prone to error. XCT is a non-destructive characterization technique that offers global morphology analysis, but is constrained by its long acquisition time.255 ANNs have been used to reduce the acquisition time for morphological analysis for PBF.223 However, the pore morphology of BJ components is significantly different from that of PBF components (uniform vs. clustered pores), requiring a different analytical approach.254,256 Zhu et al. created a pore evolution pipeline unique to BJ by implementing a CNN-based fast tomography algorithm that efficiently analyzed 3D morphological images from XCT.247 Moreover, they were able to create a database containing the morphological characteristics of ${{10}^{5}}$ pores, which was useful for tracing changes in morphology of different types of pores throughout the various stages of BJ manufacturing. Clustering techniques such as PCA and GMM were employed to extract key morphological descriptors of these pores and classify them into four distinct morphological groups.  \n\nAnother approach was reported by Satterlee et al. for realizing the global morphologies of BJ parts from local cross-sectional analysis using image augmentation.248 Image augmentation is a data expanding technique, which is often used when training data is limited, and data acquisition is time-consuming.257 The study obtained 3966 images (27,294 pores) from 67 SEM images (4545 cross-sectional pores) through image augmentation using generative adversarial ANN. The authors reported that CNN performed poorly for porosity detection, which can be attributed to regional proposal algorithms related to reducing image areas for examining specific sections more closely. Therefore,a Faster R-CNN method and YOLOv5 were also investigated, which demonstrated good performance in porosity detection on the original dataset, with Fl scores of $84\\%$ and $77\\%$ ，respectively.However, YOLOv5 performed better than Faster R-CNN on the augmented dataset $88\\%$ VS. $75\\%$ ). In addition, YOLOv5 was observed to produce an F1 score of $85\\%$ for a test dataset comprised of SEM images from the literature.  \n\neeeereaereeenieeeree AARE   \n\n\n<html><body><table><tr><td>Broad motivation</td><td>AM technique</td><td> ML technique</td><td> Model inputs</td><td>Remarks</td><td> References</td></tr><tr><td rowspan=\"3\"> Porosity analysis</td><td>BJ</td><td>GMM</td><td> XCT images</td><td>Inspection pipeline for defect characterization</td><td>Zhu et al.247</td></tr><tr><td>BJ</td><td>CNN</td><td>Cross section images of post-processed part</td><td>Automated porosity detection with small dataset</td><td>Satterle et al.248</td></tr><tr><td>BJ</td><td> LighGBM</td><td>Scanning electron microscopy (SEM) and XCT images</td><td>Characterizing microstructure of green body through binder and porosity distribution</td><td>Ojea et al.249</td></tr><tr><td rowspan=\"5\">Process parameter optimization</td><td>BJ </td><td> MLP and KNN</td><td>Roller speed, binder level, binder drying time, and layer thickness</td><td>Optimizing input parameters to maximize density, minimize dimensional errors and surface roughness, and obtain defect-free green bodies</td><td> Onler et al.250</td></tr><tr><td>BJ </td><td>MLR and GPR</td><td>Recoat speed, oscillator speed, layer thickness, drying time, roller transverse speed, drying power, and binder saturation level</td><td>Optimizing input parameters for desired green body density</td><td> Jimenez et al.251</td></tr><tr><td>BJ </td><td>Aggregated ANN (MLP-based)</td><td>Layer thickness, delay time between spreading, and print orientation</td><td>Optimizing input parameters for desired compressive strength and porosity</td><td>Asadi-Eydivand et al.252</td></tr><tr><td> MJ</td><td>Drop radius and velocity Pertictiog GB and RF;. prediction: KNN and MLP</td><td>Machine-related configurations and material properties</td><td>Optimizing inkjet printing parameters fo able itigt iding ivel </td><td> Brishty et al.140</td></tr><tr><td> MJ</td><td>ANNs (MLP, CNN, and RNN)</td><td>Droplet evolution captured in both simulated and experimental videos</td><td>Predicting droplet behavior under difetnt mamial and ontrois</td><td> Segura et al.253</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 37,
+        "chunk": "# 5.4.2 / Process parameter optimization  \n\nSimilar to other AM techniques, numerous process parameters affect the quality of BJ parts.258 Shallow and ANN techniques have been used to understand the effects of process parameters such as roller speed, oscillator speed, recoating speed, binder saturation level, layer thickness, and print orientation on the green part and sintered part properties such as density, surface rough ness, and compressive strength.250-252 Optimal print settings for user-defined properties have been determined using Pareto front252 and genetic algorithm methods.250 For efficient exploration of the parameter space, print conditions for the initial dataset are typically determined by orthogonal array-based DoEs.250,251 However, full factorial DoE has been used with a small number of param eters with limited levels.252  \n\nMJ requires ensuring consistent droplet quality in order to print high-resolution parts.140 The effect of material and process parameters on droplet characteristics has been investigated using ML techniques. Brishty et al. modeled droplet velocity, radius, and jetting regime (single drop/multiple drop/no ejection) using traditional ML models such as ensembles of DTs (boosted DTs and RF), KNN, and DNN.140 Additionally, Segura et al. evaluated droplet morphology using different ANNs.253 Machine configurations such as dwell and echo voltage, dwell and echo time, and material properties such as density, surface tension, and viscosity were considered as model inputs for both works. Both frameworks aimed for greater adaptability beyond the materials they tested, ensuring the feasibility of analyzing new materials.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 38,
+        "chunk": "# 6 | CHALLENGES AND OPPORTUNITIES  \n\nIn reviewing the state of the art for applying ML to polymer AM, some common challenges emerge that limit model accuracy and/or broader adoption. These challenges can be related to materials, polymer AM processes, distributed manufacturing, or a combination of factors, which are discussed in more detail below.  \n\nPolymer materials are composed of large, often branching, molecules and are often formulated with many smaller molecule constituents to improve processing and performance. Subtle variations in composition and processing conditions can result in significant changes to a material's properties. In addition, polymer materials are highly sensitive to environmental factors like humidity and storage temperature. Therefore, the data collection procedure must be robust enough to capture intricate details of polymer behavior so that  \n\nML models can make accurate predictions for unseen cases.  \n\nAM processes are significantly slower than conventional polymer manufacturing techniques such as injection molding and extrusion, making it difficult to collect substantial amounts of experimental data. As a result, it is challenging to consider ML approaches that require large datasets for tasks such as process-parameter optimization and property prediction. To tackle the challenge, research aimed at improving model efficiency by developing techniques that decrease the reliance on large training datasets is being conducted.129,259 For example, AL aims to minimize experimental effort by iteratively exploring the design space to identify the most valuable data points for the model's training process168 Data augmentation is another technique that can be used to artificially enlarge a dataset, thereby reducing the effort for on-hand experimentation.Data augmentation techniques are particularly prevalent for image processing tasks such as defect detection and in-situ monitoring.29.260,261 Some techniques for enhancing image data include rotating images by a certain angle,262 adjusting the brightness or contrast of the image,263 translating the image in any direction,264 and injecting noise.265 Synthetic minority over-sampling techniques,266 and feature jittering267 are examples of augmentation techniques for tabular data. Notably, excessive reliance on data augmentation can result in overfitting to the augmented data. Therefore, it is essential to ensure that the augmented data represents accurate information in the context of the problem.  \n\nAs discussed in Section 2, polymer AM techniques have numerous parameters controlling the final part quality. While ML techniques can be useful in mapping the complex correlations between multiple process parameters and part properties, using raw data can lead to models capturing irrelevant noise rather than meaningful relationships, potentially resulting in overfitting Feature engineering, a data preprocessing technique, can be advantageous to tackle this challenge.268 The process includes selecting, transforming, or creating new features from the original dataset to enhance the performance of ML models. Feature engineering often involves utilizing domain knowledge to select more informative and relative signals from the raw data. For example, the raw data from XCT scans typically contains grayscale values corresponding to the densities of the voxels (3D pixels). Instead of relying solely on the raw intensity values, the data can be refined through segmentation, boundary extraction, and statistical analysis to derive quantifiable morphological descriptor of internal defects, enhancing the ability of the ML models to detect and classify defects based on their size and shape. Another example of feature engineering includes using dimensionality reduction techniques such as PCA and t-SNE.269 These techniques reduce the dimensionality of the dataset while retaining significant variance (PCA) or preserving local similarities (t-SNE), thereby making the data more manageable and interpretable for ML models.  \n\nCorrectly labeling data is an important task in the data collection phase for supervised learning. Analyzing the raw data and labeling them correctly is a timeconsuming process. The matter is further complicated by the dynamic nature of AM. For example, as AM processes evolve to accept more materials for manufacturing, the labeling criteria for the same task may shift. Transfer learning may be an approach to circumvent manual data labeling. In this process, a pre-trained model from a related system is used. The model is first fine-tuned with a small set of manually labeled data, which can be then used to label large dataset automatically. AL may also be used to reduce the effort for data labeling. While these methods can help automate data labeling, domainspecific insights are still required to ensure quality. Hence, a hybrid approach combining automatic labeling with expert review could be optimal.  \n\nAnother challenge involves cloud computing, which refers to a variety of services including data processing, analysis, and storage. Cloud computing is advantageous for AM, particularly in industrial settings, for design collaboration, scalable processing power for complex simulation and modeling, and data analysis. However, it presents significant difficulties for tasks involving realtime monitoring and control, such as in-situ monitoring, because sending data to the cloud system for processing and analysis takes time. Adopting ML models with simple architectures that can be implemented using local devices is a viable solution to the problem. Additionally, cloud computing is vulnerable to cybersecurity risks. Any variation in the input data can significantly mislead the model, leading to defective products and compromised structural integrity. Using robust end-to-end encryption and periodically  validating  input data by crossreferencing against benchmarks are recommended.  \n\nDespite these challenges, applications of ML for polymer AM continue to grow. This is due, in large part, to the incredible opportunities enabled by this combination of ML and AM, many of which are discussed in previous sections. Here, we highlight some particularly promising opportunities.  \n\nFeedstocks for polymer AM techniques are limited compared to traditional manufacturing techniques. ML can be a powerful tool in introducing new materials. ML has already been shown to effectively predict mechanical, thermal, and chemical properties, optimiz ing the process conditions, failure analysis, and defect detection in reduced time.20,2247 This indicates that ML techniques can also be useful in analyzing new formulations by predicting whether the materials would be suitable to a particular technique and application or not.  \n\nAM offers incredible design flexibility. ML offers the potential to accelerate design optimization for AM structures. ML models can be trained to generate design suggestions based on performance criteria, which may consequently reveal new design opportunities. MLenabled metamaterial designs are a relatively new area of study.207,27o,271 Proper adaptation of ML techniques will open the door to novel lattice structure designs with features such as wireless energy transfer,272 nonlinear optics,273 and acoustic properties.274 In addition, ML models that have been properly trained can analyze and predict the material distribution within a structure in order to increase its strength and reduce its weight. Lastly, ML allows for the modification of existing designs based on prerequisites without requiring a complete redesign.  \n\nCreating separate ML models for each material and printer on an industrial scale is time-consuming and resource intensive. Transfer learning emerges as a solution, permitting the transfer of knowledge from one task to another. This strategy typically entails utilizing limited training data to adapt a model originally developed for one material or printing system to work with a different but comparable system. Beyond just model adaptation, transfer learning also facilitates the transfer of pertinent data and insights, ensuring smooth integra tion across different systems. By actively sharing existing models and their associated data on platforms such as the Materials Data Facility and GitHub, researchers and developerscan expediteML advancementsin polymer AM.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 39,
+        "chunk": "# V CONCLUSIONS  \n\nThe article provides an overview of the use of ML in polymer AM. ML has been applied to a variety of tasks, and primarily for property prediction, process parameter optimization, and quality control via in-situ monitoring. ML has been used more frequently in FFF these printers are widely available and the feedstock requires minimal preparation prior to use. As ML is a data-driven modeling technique, the primary concern is the data source and data collection procedure. Existing studies have focused on training ML models with data collected with minimal experimental effort, while ensuring that the collected data is sufficiently informative to the ML models so that their predictions are reliable. ANNs were the most popular ML model due to their ability to learn from diverse data sources, including tabular, image, video, and sensor data. However, care should be taken when applying ANNs to polymer AM, as they require a large amount of data to achieve sufficient generalizability. Lastly, challenges, potential solutions, and future research opportunities were outlined in an effort to provide readers with research directions.  \n\nML offers unique research prospects for polymer AM in terms of adapting new materials, exploring new designs, accelerating defect detection, and ensuring quality control. The scope of research extends beyond the utilization of established ML methodologies, encompassing the creation of novel algorithms with the objective of expediting advancements in polymer AM. As a result, the appropriate integration of ML techniques will also facilitate the exploration of novel applications.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 40,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nAmy Peterson acknowledges the Department of Plastics Engineering and the Dandeneau Endowed Professorship.  \n\nORCID   \nAmy M. Peterson $\\textcircled{1}$ https://orcid.0rg/0000-0002-4612-   \n0062",
+        "category": " Acknowledgments"
+    },
+    {
+        "id": 41,
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+        "category": " References"
+    },
+    {
+        "id": 42,
+        "chunk": "# AUTHORBIOGRAPHIES  \n\n![](images/6cde9c3f60e921ddff70b9d0e9b0cf1fe78f7dbe046b56d1f3d98bd2171286aa.jpg)  \n\nTahamina Nasrin is a PhD candidate in the Department of Plastics Engineeringat University of Massachusetts Lowell, where she works under the supervision of Amy Peterson. Her research is focused on the application of machine learning techniques to multilayered polymer composites and investigating innovative approaches for additive manufacturing and multilayered packaging materials. She obtained her Bachelor of Science from the Department of Applied Chemistry and Chemical Engineering at the University of Dhaka, Bangladesh.  \n\n![](images/bacac322eb4af1e490e062e0af8929372ef2b6d229db358e82e4830e5d16fdc5.jpg)  \n\nFarhad Pourkamali-Anaraki is an Assistant Professor in the Department of Mathematical and Statistical Sciences at the University of Colorado Denver. Previously, he was an Assistant Professor of Computer Science at the University of Massachusetts Lowell (2018-2022)  \n\nand received his Ph.D. in Electrical Engineering from CU Boulder in 20l7. His main research interest revolves around transitioning machine learning models from controlled lab environments to realworld settings involving unpredictable and changing conditions, such as accelerating the design and discovery of new materials using cost-effective and uncertainty-aware machine learning models.  \n\nAmy M. Peterson is an Associate Professor and Dandeneau Endowed Professor of Plastics Engineering at University of Massachusetts Lowell with expertise in interfacial phenomena and additive manufacturing. Her research group studies processing-structure-property relationships in polymers and polymer composites, with a focus on interfacial phenomena in multilayered systems. She received her PhD in 2011 from Drexel University. She was an Alexander von Humboldt Postdoctoral Fellow while at the Max Planck Institute of Colloids and Interfaces 201l-2013 and was an Assistant Professor of Chemical Engineering at Worcester Polytechnic Institute 2013-2018.  \n\n![](images/89f0144aa31e664b54b8546852ac760e2fbc7f93721ca70dc5e73690dac805df.jpg)  \n\nHow to cite this article: T. Nasrin, F.Pourkamali-Anaraki, A. M.Peterson, J. Polym. Sci. 2024, 62(12),2639.https://doi.org/10.1002/pol. 20230649",
+        "category": " References"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/Bio-inspired antifogging PDMS coupled micro-pillared superhydrophobic arrays and SiO2 coatings.json b/task2/task2-chunks/Bio-inspired antifogging PDMS coupled micro-pillared superhydrophobic arrays and SiO2 coatings.json
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@@ -0,0 +1,77 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Bio-inspired antifogging PDMS coupled micropillared superhydrophobic arrays and $\\mathsf{S i O}_{2}$ coatings†  \n\nZhiwu Han, $\\textcircled{1}$ a Xiaoming Feng,a Zhibin Jiao,a Ze Wang,a Junqiu Zhang,ab Jie Zhao, a Shichao Niu $\\textcircled{1}$ \\*a and Luquan Rena  \n\nIn this work, inspired by some typical creatures from nature with superhydrophobic surfaces, a bio-inspired antifogging PDMS is designed and fabricated successfully using UV lithography and a template method. First, we fabricated an SU-8 layer with a bio-inspired micro-pillared array (MPA) using traditional UV lithography. Then, it was used as a template to fabricate a PDMS film (PF). After that, it was chemically modified with $\\mathsf{S i O}_{2}$ coatings. It was found that the PF coupled with sprayed $\\mathsf{S i O}_{2}$ coatings and a MPA have a higher water contact angle (CA) of $158^{\\circ}$ and a lower contact angle hysteresis (CAH) of less than $2^{\\circ}$ . Water drops can be separated from this bio-inspired PDMS surface within $86.8~\\mathsf{m s}$ More importantly, this film’s antifogging property is superior, with a recovery time of less than $\\begin{array}{r}{13\\ \\mathsf{s},}\\end{array}$ which is significantly superior to that of the flat PF and the PF with the MPA. Afterwards, FTIR was applied to analyse the surface chemistry features and suggested that the bio-inspired PF has extremely low surface tension. So, it can be confirmed that an excellent superhydrophobic antifogging property has been achieved on the surface of the PF. Meanwhile, the microscopic and macroscopic dynamic movement behaviour of the fog drops was further observed. Then, the underlying antifogging mechanism was also revealed. These properties mainly benefit from the coupling effect of intermolecular attraction of droplets, chemical compositions (nanometre roughness $\\mathsf{S i O}_{2})$ and the physical structures (MPA). The investigations offer a promising way to handily design and fabricate multiscale hierarchical structures on polymers and other materials. More importantly, these findings suggest great potential value for specific antifogging applications in display devices, transport, agricultural greenhouses, food packaging and solar products, especially in continuous harsh fogging conditions.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1. Introduction  \n\nFog formation and accumulation on the surfaces of equipment, such as eyeglasses, windshields, goggles, lenses and display devices in analytical and medical instruments, are known to cause serious economic and safety problems.1–3 The fundamental principle of antifogging materials is to regulate the interaction between water drops and the solid surface via surface chemical composition as well as the rough features’ size and geometry to ensure appropriate wettability.4,5 Antifogging surfaces with hydrophilic or even superhydrophilic wetting behaviour have drawn wide attention due to their ability to signicantly reduce light scattering by only allowing fog droplets to condensate in a lm-like form.6–9 However, under harsh fogging conditions, these surfaces may exhibit frost formation or excess and inhomogeneous water condensation, which would cause irreversible catastrophic results, such as ceasing the operation, impairing the efficiency or even paralyzing the entire system, especially when considering applications in aircras, wind turbines, high-voltage power transmission, telecommunications equipment and heat exchangers.1 Superhydrophobic-induced antifogging behaviour not only can improve the evaporation rate of fog because of its high CA to the tiny water droplets,10 but can also induce tiny condensed droplets to merge with each other easily and then shed from the surface. This prevents moisture or microscale fog droplets from nucleating on a surface and so that the surface remains dry.11–13  \n\nBio-inspired micro-/nanopatterned structures combined with a variety of material substrates can improve the water repellency performance, even leading to the enhancement of the antifogging ability.14–17 Compared with these materials, polymer materials have lots of peculiar attributes, such as low cost, good deformability and ease of fabrication and so they have broader application prospects.18,19 Polydimethylsiloxane (PDMS) is typical example of these materials.20,21 PDMS is inherently water repellent and one of the frequently-used surface modiers to create superhydrophobic surfaces.22 Introducing different surface textures such as microwell arrays,23 femtosecond parallel arrays24 or other 3D pattern dependent structures25 into PDMS surfaces can create some chemistry/ topography-combined superhydrophobic surfaces. However, a plausible issue has recently arisen. Superhydrophobicity is not the only criteria for generating high-performance antifogging or even anti-ice surfaces.26 Besides, most of the methods are not scalable for industrial level. In fact, PDMS microscale pillar arrays can achieve higher CAs over $150^{\\circ}$ without further coatings or treatment steps,27,28 but their antifogging ability is not obvious because of the good adhesion to droplets of PDMS itself. Some investigations on antifogging function involving PDMS have been reported, for example, the involved PDMS layer was treated with $\\mathbf{O}_{2}$ plasma to convert into highly porous silica lms,29 or as a “seed layer” by photochemical oxidation,30 the common purpose was to result in a superhydrophilic antifogging layer. In addition, Zheng and co-workers11 rst designed a composite micro/nanostructure surface using a polyvinylidene diuoride polymer as the substrate, showing excellent antifogging and icing-delay properties. Next they presented a series of surfaces combined with nanohairs and micropillar arrays using PDMS as a negative replica and then epoxy as the substrate, demonstrating the excellent anti-icing abilities of the surface.15 This provides the inspiration for our work as, to the best of our knowledge, the antifogging performance using PDMS directly as the substrate has rarely been characterized in detail.  \n\nHerein, we designed the surface asperities to take the form of a regular micro-pillared array (MPA) using a PDMS lm (PF) in combination with a silicon dioxide $\\left(\\mathrm{SiO}_{2}\\right)$ modication. In this fabrication, an SU-8 mold of negative well arrays was obtained using traditional UV lithography, then a so replication method was adopted to obtain a PF with a MPA as the substrate. Subsequent $\\mathrm{SiO}_{2}$ nanometer coatings were sprayed on the surface of the PF with the MPA. Depositing a layer of $\\mathrm{SiO}_{2}$ on the surface of the PF with the MPA using a spray coating technique makes PDMS with a superhydrophobic antifogging property. The dimensional uniformity and quality of the as-prepared PF was characterized with the help of eld emission scanning electronic microscopy (FESEM). Fourier transform infrared spectroscopy (FTIR) results indicated that both the functional groups of $\\mathbf{-CH}_{2}$ and $\\mathbf{-CH}_{3}$ existed on the surfaces of the bioinspired PF samples, which not only increases their hydrophobicity dramatically, but also decreases their water adhesion performance. So, the superhydrophobic antifogging performance of the bio-inspired PF is ensured. Meanwhile, a set of optimized models were generated to illustrate the fabrication process. Moreover, the nal antifogging behaviors were also revealed. The antifogging properties of the PF were characterized experimentally using a spray simulation system and an optical CA measuring device. The time-lapse transmittance measurements demonstrated that the as-prepared PF possessed a superior fogging recovery property because it can reach a plateau in far less time $(<13\\ s)$ . It also suggested a reliable optical performance in practical outdoor conditions. Furthermore, the dynamic antifogging behaviors of the PF coupled with $\\mathrm{SiO}_{2}$ coatings and the MPA were observed carefully, verifying that the MPA can get dry and the fog drops can drop from the asmodied PF. It was conrmed that PF coupled with sprayed $\\mathrm{SiO}_{2}$ coatings and the MPA possesses excellent superhydrophobicity and antifogging behaviors.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2. Results and discussion  \n\nIn this work, we designed a matrix of geometries made of periodic structures on a PDMS substrate. The overall process of preparation is shown in Fig. 1. Briey, a clean glass slide was spin-coated with a negative photoresist SU-8, the spinning speed determined the thickness of the SU-8 coating; a photomask containing the circle-shaped arrays was utilized in traditional UV lithography; the unexposed SU-8 was ushed off in the developer, leaving the circular micro-hole arrays standing on the glass slide; a mixture of the PDMS pre-polymer and curing agent in a $10:1$ mixture (by weight) was degassed using a vacuum chamber and carefully poured onto the SU-8 masters; aer curing at $80~^{\\circ}\\mathbf{C}$ for $^{\\textrm{1h}}$ , the PDMS sample was gently peeled from the mold; the commercial $\\mathrm{SiO}_{2}$ coating agent was sprayed on top of the as-prepared PDMS. As illustrated in Fig. 2a, the side length of the pillar $(L)$ is about $5~{\\upmu\\mathrm{m}}$ , the pitch between neighboring pillars $(P)$ is about $7.5~{\\upmu\\mathrm{m}}$ and the nominal height of the pillar $(H)$ is about $6\\upmu\\mathrm{m}$ . The quality and uniformity of the pillars were inspected using FESEM. The FESEM sample was titled at $45^{\\circ}$ to reveal the actual structures. Fig. 2b shows the PDMS coating has a negligible effect on the global structure of the MPA, though the individual micro-pillar was coated with nanoscale $\\mathrm{SiO}_{2}$ (Fig. 2c). The FESEM results indicate that the asprepared PF possessed a rough surface and contained many bumps.  \n\n![](images/44bf64beefa33b3ec1de19558a3a57209a9d1d9d7a8acb70981e6e056016f2ce.jpg)  \nFig. 1 The fabrication process of the bio-inspired PDMS coupled with sprayed $\\mathsf{S i O}_{2}$ coatings and the MPA. (a) A clean glass slide was spincoated with a negative photoresist SU-8. (b) A photomask containing the circle-shaped arrays was utilized during the process of UV lithography. (c) With the circular micro-hole arrays (CMHAs) standing on the glass slide, PDMS was carefully poured onto the SU-8 masters and then gently peeled from the mold. (d) The commercial $\\mathsf{S i O}_{2}$ coating agent was sprayed on top of the MPA surface.  \n\n![](images/f8cd8320ef84868f3af0d07e55d2925d9057acef171b3b7b0b853669ef7e16e1.jpg)  \nFig. 2 (a) The top view (left) and side view (right) of the MPA. This pattern was repeated periodically across the PDMS surface. (b) The FESEM image of the fabricated $\\mathsf{S i O}_{2}$ -sprayed MPA under low-magnification, demonstrating that the coated PDMS has a negligible effect on the global structure of the MPA. (c) The $\\mathsf{X}$ -ray diffraction (XRD) spectrum of the coating and high-magnification FESEM image shows the nanoscale $\\mathsf{S i O}_{2}$ (insert).  \n\nThe wettability properties of the at PF, PF with the MPA and PF coupled with sprayed $\\mathrm{SiO}_{2}$ coatings and the MPA were examined separately via an optical CA measuring device based on a sessile drop technique. An average of ve measurements on each sample is effective. Fig. 3 shows the water CA of the three PFs was linearly increased and the hydrophobicity of at PF and PF with the MPA was compared, exhibiting water CAs of $114^{\\circ}$ and $133^{\\circ}$ , respectively. The PF coupled with sprayed $\\mathrm{SiO}_{2}$ coatings and the MPA was found to be superhydrophobic, showing an average water CA of $158^{\\circ}$ . This indicated that the change in surface structure results from the MPA signicantly increasing the water CA, rendering the surface superhydrophobic. The superhydrophobic property was elucidated using the Cassie–Baxter model,31 suggesting that the microstructure on a low-surface-energy material signicantly improved the superhydrophobicity of the surface.  \n\n![](images/65a6c6516b4ddf78123f85830ee70e28153cd6372db6d8de56b4464cc68f6125.jpg)  \nFig. 3 CA and CAH measurements of three PF surfaces. The error bars denote standard deviations, which were obtained from distinct measurements on the three different PFs and at least at five different locations on each.  \n\nThe effective CA of the droplets can be regulated by the equation cos $\\theta_{\\mathrm{c}}=f_{\\mathrm{s}}$ cos $\\theta_{\\mathrm{{s}}}+f_{\\mathrm{{v}}}$ cos $\\theta_{\\mathrm{v}},$ where $\\theta_{\\mathrm{{s}}}$ and $\\theta_{\\mathrm{v}}$ are the CA of the liquid contacting with solid and vapor parts and $f_{s}$ and $f_{\\mathrm{v}}$ are the area fractions of the solid and vapor on the surface. If rough structures on a surface can generate entrapped air pockets, in such circumstance, $f_{\\mathrm{s}}+f_{\\mathrm{v}}=1$ and $\\theta_{\\mathrm{v}}=180^{\\circ}$ . $\\theta_{\\mathrm{c}}$ can be calculated by the following equation,  \n\n$$\n\\cos\\theta_{\\mathrm{c}}=f_{\\mathrm{s}}(\\cos\\theta_{\\mathrm{s}}+1)-1\n$$  \n\nIn addition, a superhydrophobic surface with low adhesion to droplets is a crucial index of antifogging materials. It is found that the water adhesion on both the at PF and the PF with the MPA was high. Therefore, our starting surface was hydrophobic with high adhesion. Amazingly, the PF coupled with sprayed $\\mathrm{SiO}_{2}$ coatings and the MPA had a low CAH of less than $2^{\\circ}$ . From a thermodynamic point of view, eliminating a liquid from its solid substrate requires the energy to overcome the adhesion.32 The basic relation between the work of adhesion and surface wettability is given by the Dupre–Yong equation,33  \n\n$$\nW_{\\mathrm{e}}=\\gamma_{\\mathrm{lv}}(1+\\cos\\theta_{\\mathrm{c}})\n$$  \n\nwhere $W_{\\mathrm{e}}$ is the work of adhesion at the equilibrium state and $\\gamma_{\\mathrm{lv}}$ is the surface tension of the liquid–vapor interfaces. At a large static CA, it requires a small amount of work to remove droplets. When the $\\mathrm{SiO}_{2}$ coatings were applied on the top of the MPA using the spraying technology, their morphology changed dramatically as shown in Fig. 2b. Specically, the pillars retained their microscale geometrical characteristics and also exhibited nanometer roughness due to the presence of the $\\mathrm{SiO}_{2}$ particles. Moreover, the increase in the CA of the $\\mathrm{SiO}_{2}$ -sprayed MPA was followed by a noticeable decrease in the water adhesion. Since the water drops roll off easily on the patterned surface, we can assume that the water drops stay on the top of the MPA without penetrating the gap between the neighboring pillars. Thus, by simply spraying $\\mathrm{SiO}_{2}$ on the PF with the MPA, we created “non-sticky” superhydrophobic surfaces (see ESI Video S1†). The very low water adhesion is due to the $\\mathrm{SiO}_{2}$ coatings in combination with the geometrical features of the rough surface, which further veried the superhydrophobic antifogging effect of both adding $\\mathrm{SiO}_{2}$ and the creation of the MPA on the PDMS surface. In summary, on one hand, a foundation of hydrophobic $\\mathrm{SiO}_{2}$ nanometer coatings can achieve the superhydrophobic PF chemically. On the other hand, the MPA further amplied the hydrophobic effect to realize the superhydrophobic effect ( $\\mathbf{\\tilde{CA}}=158^{\\circ}$ and $\\mathbf{CAH}=2^{\\circ}$ ) physically, which played a crucial role in achieving the antifogging property.  \n\nThe water droplet bounce behaviors on the as-prepared PF were recorded with the help of a high-speed video camera when a $15.6~\\upmu\\mathrm{L}$ water droplet was dropped from a height of $54.8~\\mathrm{mm}$ (see ESI Video $^{S2\\dagger}$ ). The dropping height was determined by the maximum height avoiding droplet fragmentation upon impact with the surface, ensuring maximum droplet momentum. This droplet volume ${\\mathit{\\Omega}}({\\approx}16\\ \\upmu\\mathrm{L})$ was found to be optimum as the droplet could be replicated easily and fell under its own weight when dropped from a 23 gauge dispensing tip. As shown in Fig. 4, the water droplet deformed quickly aer contact with the as-prepared PF. The initial impacting velocity of the droplet was $0.94~\\mathrm{ms}^{-1}$ . At $3.1\\mathrm{ms}$ , the spherical water droplet reached a disclike form. Then, the water drop began to bounce twice and nally completely separated from surface of the as-prepared PF within $86.8~\\mathrm{ms}$ , which further illustrates the excellent superhydrophobic and low adhesion properties.  \n\nFurthermore, since fogging results in a certain degree of transmittance loss, we quantied the response of the at PF, PF with the MPA and PF coupled with sprayed $\\mathrm{SiO}_{2}$ coatings and the MPA to fogging at regular intervals $\\left(T_{\\mathrm{t}}\\right)$ until the original transmittance $\\left(T_{\\mathrm{max}}\\right)$ was restored. In order to characterize the antifogging recovery property, the variation trends of the timelapse transmittance measurements of the three PFs were performed aer being sprayed by the generated fog. For this purpose, we built a spray simulation system to characterize their antifogging properties.34 The PF was xed by a clip which was adjusted to be perpendicular to the light beam. As shown in Fig. 5a, recovery from fogging was much faster for the PF coupled with sprayed $\\mathrm{SiO}_{2}$ coatings and the MPA, with $T_{\\mathrm{max}}/T_{t}$ reaching a plateau in far less time than the others. It was conrmed that the PF coupled with sprayed $\\mathrm{SiO}_{2}$ coating and the MPA possesses a superior ability for antifogging recovery, especially in wet and humid environments.35  \n\nIn order to clarify the reasons that the PF coupled with sprayed $\\mathrm{SiO}_{2}$ coating and the MPA possessed the superhydrophobic-antifogging function we investigated the chemical composition of the as-prepared PF surface. Fig. 5b shows the EDS spectra of the as-prepared PF and the results indicated that the fabricated PF is composed of three elements, carbon (C), silicon (Si) and oxygen (O). FTIR spectra of the commercial $\\mathrm{SiO}_{2}$ coating agent, the PF with the MPA and the PF coupled with sprayed $\\mathrm{SiO}_{2}$ coatings and the MPA were obtained. The FTIR spectrum of the commercial $\\mathrm{SiO}_{2}$ coating agent is shown in Fig. 5c. The peak at $810~\\mathrm{{cm}^{-1}}$ is due to Si–O–Si symmetric stretching, and the Si–O–Si asymmetric vibration is at $1082~\\mathrm{cm}^{-1}$ . The peaks at 1264 and $2960~\\mathrm{cm}^{-1}$ correspond to the symmetric bending vibration of $\\mathbf{Si-CH}_{3}$ and symmetric stretching vibration of $\\mathbf{Si-CH}_{3}$ , respectively. The peaks at 850 and $1405~\\mathrm{cm}^{-1}$ are due to the Si–C bending and $\\mathrm{si-C}$ stretching vibrations, respectively. The $\\mathbf{Si-CH}_{2}$ stretching band is at $2850~\\mathrm{cm}^{-1}$ and the peaks at 1389 and $1460~\\mathrm{cm}^{-1}$ are due to the bending vibration of $\\mathbf{Si-CH}_{2}$ .36 The FTIR spectrum of the PF with the MPA and the PF coupled with sprayed $\\mathrm{SiO}_{2}$ coatings and the MPA is shown in Fig. 5d. The peak at 1089 is attributed to the Si–O–Si stretching vibration. The peaks at around 1263 and $803~\\mathrm{cm}^{-1}$ are assigned to the Si–C groups. Other characteristic peaks in the spectrum are assigned to the –CH, $\\mathbf{-CH}_{2}$ and $\\mathbf{-CH}_{3}$ groups of the polymer backbone $2964~\\mathrm{cm}^{-1},$ $2904~\\mathrm{cm}^{-1}$ and $1415~\\mathrm{cm}^{-1}$ , respectively). It could be observed that the FTIR spectrum of the modied PF is consistent with the FTIR spectrum of the untreated PF.37 The above results not only suggest the commercial $\\mathrm{SiO}_{2}$ coating agent without any impurities, but also the as-prepared PF, was enriched with extreme superhydrophobicity and low adhesion, due to the hydrophobic functional groups $\\mathbf{\\bar{\\Pi}}_{\\mathbf{-CH}_{2}}$ and $\\begin{array}{r}{-\\mathbf{C}\\mathbf{H}_{3}\\overline{{.}}}\\end{array}$ ) of the $\\mathrm{SiO}_{2}$ coating.  \n\n![](images/2d98579cb46bc6571f826ef63e4df45bd68d5f59c29660a1fe5695cd28beb8f1.jpg)  \nFig. 4 Bounce dynamics of a water droplet impacting with the PF coupled with sprayed $\\mathsf{S i O}_{2}$ coatings and the MPA surface.  \n\nTo examine the antifogging property more intuitively, a 3D ultra-depth stereoscopic microscope was used to observe the micro-dynamic behaviour of fog drops on the PF coupled with sprayed $\\mathrm{SiO}_{2}$ coatings and the MPA surface (see ESI Video ${\\bf S}3\\dagger$ ). First, many individual fog drops with a spherical appearance were occurring on the top of the micropillars. As time went on, we found some tiny fog drops began to merge with each other and form new fog drops. As shown in Fig. 6, fog drops A–E were growing smoothly $(t=20~\\mathrm{s})$ ). Subsequently, fog drops B and C coalesced into larger fog drop F $\\left(t=30~\\mathrm{s}\\right)$ , fog drops D and E coalesced into larger fog drop H $\\left(t=45~s\\right)$ and fog drops A and F coalesced into larger droplet I $\\left(t=55s\\right)$ . Then, fog drops H and I merged with fog drop G and formed fog drop J $(t=90\\ s)$ . This indicated that the condensed fog drops can be in Cassie’s state. We theorised that a de-wetting transition phenomenon may occur on the surface,38 then the released surface energy can propel the fog drop jumping or self-removal from the surface.39,40 Furthermore, when this ying fog drop touched another constrained fog drop, a transition would again be stimulated. Due to the occurrence of the de-wetting transitions and the self-removal phenomenon, the MPA can get dry and the fog drops can drop from the PF by means of the low surface adhesion.  \n\nIn order to verify our hypothesis about antifogging behaviour on the PF coupled with sprayed $\\mathrm{SiO}_{2}$ coatings and the MPA surface, the macro-dynamic process of fog drop movement was recorded using a 3D ultra-depth stereoscopic microscope (see ESI Video ${\\bf S4\\dagger}$ ). As shown in Fig. 7a, the fog spray was applied to the surfaces, some tiny fog drops initially condensed on the surface and subsequently the fog drops became gradually larger. As time went on, we amazingly found the same phenomenon as Fig. 6, that some tiny fog drops began to merge with each other and form larger fog drops (see the same color circles from $t=90\\mathrm{~s~}$ to $t=196\\mathrm{~s~}$ ). In addition, when the fog drops grew to a certain size, the same phenomenon occurred as in ESI Video $^{85,\\dagger}$ that these fog drops began to roll off suddenly. It is interesting that this roll-off performance removed some circumjacent tiny fog drops, sweeping the surface clean and keeping the area dry (see purple circle at $t=236\\mathrm{~s~}$ ). This is consistent with our previous conjecture and demonstrated the excellent antifogging property of the as-prepared PF surface. To evaluate the antifogging ability of the PF coupled with sprayed $\\mathrm{SiO}_{2}$ coatings and the MPA surface, we estimated the percentage of dry areas versus time, as shown in Fig. 7b, at $\\sim50\\mathrm{~s~}$ , the percentage was lower, but the percentage increased suddenly aer ${\\sim}200\\ s$ , and the percentage was maintained at ${\\sim}83\\%$ from ${\\sim}250$ to 500 s on the whole. This demonstrated the superior antifogging property of the PF coupled with sprayed $\\mathrm{SiO}_{2}$ coatings and the MPA surface.  \n\n![](images/c03b997c672a1ffde7a9324141f6e1d151d1fa4923c148cff6d49c595196b91f.jpg)  \nFig. 5 (a) Antifogging of the three PFs is quantified by performing time-lapse transmittance measurements $(T_{\\mathrm{t}})$ to determine the required time to restore their original optical properties $(T_{\\mathrm{max}})$ . The PF coupled with sprayed $\\mathsf{S i O}_{2}$ coatings and the MPA shows a significantly faster recovery from fogging. (b) Energy-dispersive X-ray spectroscopy (EDS) spectra of the PF coupled sprayed $\\mathsf{S i O}_{2}$ coatings and the MPA. (c) FTIR spectra of the commercial $\\mathsf{S i O}_{2}$ coating agent. (d) FTIR spectra of the PF with the MPA (black) and the PF coupled with sprayed $\\mathsf{S i O}_{2}$ coatings and the MPA (purple).  \n\nIn order to further reveal the internal antifogging mechanism of the PF coupled with sprayed $\\mathrm{SiO}_{2}$ coating and the MPA, one possible reasonable explanation for these ndings was that the synergistic effect of the droplets intermolecular attraction, chemical compositions and the MPA was the key factor in realizing the superhydrophobic antifogging property. On one hand, the low surface energy methylated $\\mathbf{-CH}_{3}$ and $\\begin{array}{r}{-\\mathbf{C}\\mathbf{H}_{2}\\dot{\\mathbf{\\upmu}}_{.}}\\end{array}$ ) components resulted from the $\\mathrm{SiO}_{2}$ nanometer coatings, which further increased the PF surface hydrophobicity and dramatically decreased the PF surface adhesion to water droplets.  \n\nIndeed, the sliding angle for the water drops occurred for a CAH of less than $2^{\\circ}$ . Since the water drops rolled off easily on the PF surface, we can assume that the water drops stayed on the top of the MPA without penetrating the interpillar areas, and then induced tiny condensed droplets to merge with each other easily until shed from the surface. Moreover, the evaporation rate of fog drops was also improved.41 Physically, the fog drops would remain repulsive to the MPA due to the surface forces having sufficient magnitude to suspend liquid against the downward pull of gravity (or other body forces) (see ESI Videos S6 and ${\\bf57\\dagger}$ ). As a whole, the water molecules were affected by a repulsion force of the material itself $\\left(F_{1}\\right)$ intermolecular attraction $\\left(F_{2}\\right)$ , a repulsion force of micro-pillared arrays $\\left(F_{3}\\right)$ , surface tension $(\\sigma)$ and their own gravity $(G)$ (Fig. 8).  \n\nOn the other hand, it is a universal strategy to construct a superhydrophobic surface by creating surface roughness onto a low surface energy material. Interestingly, the $\\mathrm{SiO}_{2}$ -sprayed MPA played a signicant role in amplifying the PF’s intrinsic hydrophobicity, which dramatically increased the surface roughness. Specically, the pillars retained their microscale geometrical characteristics and also exhibited nanometer roughness due to the presence of the $\\mathrm{SiO}_{2}$ coating. The combination of the micro/nano-roughness as well as the wellknown water-repellent chemical properties of the PDMS made the patterned surfaces superhydrophobic. Previous researchers have reported that the relationships between CA and roughness ratio in two different wettability states were quantitatively described as the Wenzel model and the Cassie–Baxter model42 which indicated that the true CA of a at hydrophobic surface would be lower with the increase in surface asperities. The very low water adhesion was due to the inherent property of the $\\mathrm{SiO}_{2}$ coatings in combination with the geometrical features of the MPA. Apparently, it was the hierarchical amplication effect of $\\mathrm{SiO}_{2}$ -sprayed MPA that brought big rewards for the achievement of the superhydrophobic antifogging surface. In addition, with the increase in the hydrophobic specic surface that arose from the $\\mathrm{SiO}_{2}$ -sprayed MPA, the PF surface free energy was obviously reduced. According to energy minimization theory,43 once a droplet coalesces with the adjacent droplets, the released surface energy will overcome droplet adhesion, which may induce the fog drops from a Wenzel state to a Cassie–Baxter state,31 so that coalescing fog droplets can self-remove from PF surfaces. Consequently, the transmittance of the PF coupled with sprayed $\\mathrm{SiO}_{2}$ coatings and the MPA would recover to the initial state. These were exactly consistent with the results of the transmittance spectra.  \n\n![](images/99b8fff439d8cfbc7cff0302ec7a2c71ad29fc2ba7a24c7fa0eca2e6ad3903bd.jpg)  \nFig. 6 (a) Optical images show the micro-dynamic behaviour of the fog drops movement on the PF coupled with sprayed $\\mathsf{S i O}_{2}$ coatings and the MPA surface. From $t=0$ s to $t=90$ s, as the fog drops (A–E) grow larger gradually $(t=20\\ s)$ , they will merge with each other, fog drops B and C coalesce into larger fog drop F $\\left(t=30\\ s\\right)$ , fog drops D and E coalesce into larger fog drop H $(t=45s$ ) and fog drops A and F coalesce into larger droplet I $\\left(t=55s\\right)$ ). Then, fog drops H and I merge with fog drop G and form fog drop J $(t=90~\\mathsf{s})$ . (b) Time evolution of the diameter of an individual fog drop during the merge process (blue triangles). The inserts correspond to $t=20$ , 30, 45, 55 and $90~\\mathsf{s}.$ (c) Additional details are displayed with the assistance of schematic diagrams.  \n\n![](images/20014e7fd804776d288ecdcbfddf7ae84e4005677c7053f0e60db94fcf841c94.jpg)  \nFig. 7 (a) Optical images show the macro-dynamic process of the fog drops movement on the PF coupled with sprayed $\\mathsf{S i O}_{2}$ coatings and the MPA surface. From $t=90$ s to $t=236s$ , with water condensation, some tiny fog drops began to merge with each other and form larger fog drops (the same color circles from $t=90~\\mathrm{s}$ to $t=196\\ s)$ . As the fog drops reach a certain size, the fog drops begin to roll off suddenly and take away some surrounding tiny fog drops (purple circle at $t=236s\\mathrm{,}$ . (b) The percentage of dry areas versus time. At ${\\sim}50\\ s.$ , the percentage is lower, but the percentage increases suddenly after ${\\sim}200\\ s,$ and the percentage was maintained at $\\sim83\\%$ from ${\\sim}250$ to 500 s on the whole.  \n\n![](images/84f109070f5956c18f77d07ac71022937c4ea47de5e9315c600100d38911ded8.jpg)  \nFig. 8 The antifogging behaviors of the PF coupled with sprayed $\\mathsf{S i O}_{2}$ coating and the MPA. Here, $F_{1}$ is the repulsion force of the material itself, $F_{2}$ is the intermolecular attraction, $F_{3}$ is the repulsion force of the micro-pillared arrays, $\\sigma$ is surface tension and $G$ is gravity.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# 3. Conclusions  \n\nIn summary, an antifogging PDMS, inspired by some typical creatures from nature with superhydrophobic surfaces, was designed and fabricated successfully via traditional UV lithography combined with a so replication and subsequent spray coating technique. First, the dimensional uniformity and quality of the bio-inspired PF was characterized using FESEM. It was conrmed that this bio-inspired PF had a coupling surface structure integrated MPA and functionalized $\\mathrm{SiO}_{2}$ coating. FTIR results indicated that both the functional groups of $\\mathbf{-CH}_{2}$ and $\\mathbf{-CH}_{3}$ existed on the surfaces of the bio-inspired PF samples.  \n\nIt not only increased its hydrophobicity dramatically, but also decreased its water adhesion property, ensuring the PF surface achieved superhydrophobic antifogging performance. Meanwhile, a set of optimized models were generated to illustrate the fabrication process. Moreover, the nal antifogging behaviors were also revealed. The antifogging properties of PF coupled with sprayed $\\mathrm{SiO}_{2}$ coating and the MPA were characterized experimentally using a spray simulation system and optical CA measuring devices. The time-lapse transmittance measurements demonstrated that the bio-inspired PF also possessed superior fogging recovery property (less than 13 s). It conrmed the reliable optical performance of this advanced antifogging material in practical outdoor conditions. Furthermore, dynamic antifogging behaviors of the bio-inspired PF coupled with sprayed $\\mathrm{SiO}_{2}$ coatings and the MPA were also observed carefully. It can be conrmed that the bio-inspired PF possesses excellent superhydrophobicity and antifogging behaviours. It is anticipated that the ndings reported here provide direct guidance for the future design of superhydrophobic antifogging materials on polymers and other material substrates, and suggest great potential value for specic antifogging applications, such as solar cell panels and window buildings.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 5,
+        "chunk": "# 4. Experimental section",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 4.1 Materials and chemical reagents  \n\nAcetone, anhydrous ethanol and deionized water were purchased from commercial sources in the highest available purity. The negative photoresist SU-8 2005 and its developer were obtained from MicroChem Corp. Glass slides were used for the substrates. The elastomer PDMS Sylgard 184 was purchased from Dow Corning. The $\\mathrm{SiO}_{2}$ coating agent was purchased from Changzhou Nanocoatings Co., Ltd.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 4.2 Preparation of the CMHA  \n\nThe procedures were performed as follows: rst, glass slides (approximately $4\\times3~\\mathrm{cm}^{2}]$ were cleaned for $10~\\mathrm{\\min}$ . The substrate was dried at $200^{\\circ}\\mathrm{C}$ for $30\\mathrm{min}$ . Next, SU-8 photoresist was dispensed on a glass slide through a spin-coating program $\\mathrm{500~rpm}$ for $10~\\mathrm{s}$ and $3000~\\mathrm{rpm}$ for 30 s). The substrate was so baked on a level hotplate at $103^{\\circ}\\mathrm{C}$ for $6~\\mathrm{{min}}$ . In addition, the substrate was treated using traditional UV lithography and UV exposure (exposure energy at $158\\mathrm{~mJ~cm}^{-2}$ for 10 s) was performed perpendicularly to a photomask of circle-shaped array patterns. Then a post exposure bake step was carried out at $98~^{\\circ}\\mathbf{C}$ for $5~\\mathrm{{min}}$ to harden the SU-8 layer. The thickness of the resulting lm was approximately $6~{\\upmu\\mathrm{m}}$ . Finally, the substrate was immersed in the developer for $30\\mathrm{~s~}$ . The solution was agitated using a tweezer to obtain the uniform SU-8 CMHA on the glass substrate.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 4.3 Preparation of the micro-pillared array (MPA)  \n\nThe CMHA on the glass substrate was used as a master pattern. The procedures were performed as follows: rst, the prepolymer and the curing agent were mixed uniformly and stirred in a glass beaker to synthesize the PDMS. Second, the PDMS was poured over the photoresist layer gently and the assembly was moved into the vacuum chamber for $40~\\mathrm{{min}}$ to remove air bubbles, next it was heated in a drying oven at $80~^{\\circ}\\mathbf{C}$ for $^{1\\mathrm{~h~}}$ to completely cure the PDMS. Last, the solidied PDMS was peeled off from the glass substrate and the MPA was transferred to the PF.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 4.4 Preparation of the sprayed $\\mathbf{SiO}_{2}$ coatings on the MPA  \n\nA commercial $\\mathrm{SiO}_{2}$ coating agent was sprayed on top of the asprepared PDMS. A spray coating setup was used to deposit the particles. The distance between the sample and the nozzle head was approximately $15\\ \\mathrm{cm}$ . The samples were baked in a drying oven at $80~^{\\circ}\\mathbf{C}$ for $20\\ \\mathrm{\\min}$ . The spray coating and heating processes were performed twice.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 4.5 Characteristics of the prepared samples  \n\nThe uniformity and quality of the fabricated sample was inspected with the help of FESEM (JSM-6700F, JEOL) at an accelerating voltage of $2.0\\mathrm{kV}.$ . The static water CAs of the sample surfaces were estimated with an optical CA measuring device (OCA20 data physics, Germany). The advancing contact angles (ACAs) and receding contact angles (RCAs) were tested using a method in which the droplets were enlarged from 7 to $14\\upmu\\mathrm{L}$ to obtain ACAs and shrunk from 14 to $7~\\upmu\\mathrm{L}$ to obtain RCAs. The CAH was measured by inclining the sample until the droplet start rolling. An XRD sample was xed on the sample stage to keep it even. The commercial $\\mathrm{sio}_{2}$ coating agent was characterized using an X-ray diffractometer (Rigaku). The experiment data were collected from 15 to $60^{\\circ}$ . The compositions and distributions of the main elements in the PF coupled with sprayed $\\mathrm{SiO}_{2}$ coating and the MPA were measured using EDS (OXFORD X-MaxN 150). The chemical bonds of the samples were examined using FTIR spectroscopy (IRAffinity-1S). The transmittance spectra of the three PFs were obtained using a miniature ber-optic spectrometer (Ocean Optics USB 4000) and the light spot size of the incident beam was about $5\\mathrm{mm}$ in diameter. The spectrometer was carefully calibrated with STDWS, a standard white board certied by the National Institute of Metrology of China.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 4.6 Observation of fog drops condensation  \n\nThe samples were xed horizontally on the object stage. The spray of a humidier was used to generate condensed fog drops on the sample surface. Aer the surfaces were sprayed, the microscopic and macroscopic dynamic behaviour of the movement of the fog drops on the PF coupled with sprayed $\\mathrm{SiO}_{2}$ coating and the MPA surface were simultaneously observed using the 3D ultra-depth stereoscopic microscope (KEYENCE VHX-5000). The condensation experiments were repeated several times. The laboratory temperature was measured at $29^{\\circ}\\mathbf{C}$ with a relative humidity of $40\\%$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# 4.7 Spray simulation  \n\nThe spray simulation system includes a tungsten-halogen lamp (Ocean Optics LS-1-LL), optical ber, ultrasonic humidier (YADU YC-X100E), optical-collimated bracket, a spectrograph (Ocean Optics USB 4000) and a laptop computer.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# Conflicts of interest  \n\nThere are no conicts to declare.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 14,
+        "chunk": "# Acknowledgements  \n\nThis work was supported by the National Natural Science Foundation of China (No. 51325501, 51505183 and 51675220), JLU Science and Technology Innovative Research Team (No. 2017TD-04), Joint Construction Project of Jilin University and Jilin Province (No. SF2017-3-4), Graduate Innovation Fund of Jilin University (No. 2017010), Special Funding from China Postdoctoral Science Foundation (No. 2018T110246) and Outstanding Young Talent Fund of Jilin Province (No. 20170520095JH).",
+        "category": " Acknowledgements"
+    },
+    {
+        "id": 15,
+        "chunk": "# References  \n\n1 Q. Zhang, B. Jin, B. Wang, Y. Fu, X. Zhan and F. Chen, Ind. Eng. Chem. Res., 2017, 56, 2754–2763.  \n\n2 T. Zhang, Q. Yu, J. Wang and T. Wu, Ind. Eng. Chem. Res., 2018, 57, 4577–4584.   \n3 F. Wang and H. Liu, J. Phys. Chem. C, 2018, 122, 3434–3442.   \n4 Z. Han, X. Feng, Z. Guo, S. Niu and L. Ren, Adv. Mater., 2018, 30, 1704652.   \n5 T. Mouterde, G. Lehoucq, S. Xavier, A. Checco, C. T. Black, A. Rahman, T. Midavaine, C. Clanet and D. Qu´ere´, Nat. Mater., 2017, 16, 658–663.   \n6 J. Zhao, A. Meyer, L. Ma and W. Ming, Chem. Commun., 2013, 49, 11764–11766.   \n7 F. Xu, X. Li, Y. Li and J. Sun, ACS Appl. Mater. Interfaces, 2017, 9, 27955–27963.   \n8 F. Liu, J. Shen, W. Zhou, S. Zhang and L. Wan, RSC Adv., 2017, 7, 15992–15996.   \n9 Z. Bai, Y. Hu, S. Yan, W. Shan and C. Wei, RSC Adv., 2017, 7, 1966–1974.   \n10 Q. Shang and Y. Zhou, Ceram. Int., 2016, 42, 8706–8712.   \n11 M. Wen, L. Wang, M. Zhang, L. Jiang and Y. Zheng, ACS Appl. Mater. Interfaces, 2014, 6, 3963–3968.   \n12 R. Wen, S. Xu, D. Zhao, Y.-C. Lee, X. Ma and R. Yang, ACS Appl. Mater. Interfaces, 2017, 9, 44911–44921.   \n13 P. Zhang, Y. Maeda, F. Lv, Y. Takata and D. Orejon, ACS Appl. Mater. Interfaces, 2017, 9, 35391–35403.   \n14 M. He, Y. Ding, J. Chen and Y. Song, ACS Nano, 2016, 10, 9456–9462.   \n15 W. Shi, L. Wang, Z. Guo and Y. Zheng, Adv. Mater. Interfaces, 2015, 2, 1500352.   \n16 H. K. Raut, S. S. Dinachali, Y. C. Loke, R. Ganesan, K. K. Ansah-Antwi, A. Gora, E. H. Khoo, V. A. Ganesh, M. S. Saifullah and S. Ramakrishna, ACS Nano, 2015, 9, 1305–1314.   \n17 J. Lomga, P. Varshney, D. Nanda, M. Satapathy, S. Mohapatra and A. Kumar, J. Alloys Compd., 2017, 702, 161–170.   \n18 L. Ai, J. Zhang, X. Li, X. Zhang, Y. Lu and W. Song, ACS Appl. Mater. Interfaces, 2018, 10, 4993–4999.   \n19 S. Das, S. Kumar, S. K. Samal, S. Mohanty and S. K. Nayak, Ind. Eng. Chem. Res., 2018, 57, 2727–2745.   \n20 K. H. Oh, H. S. Kang, M. J. Choo, D. H. Jang, D. Lee, D. G. Lee, T. H. Kim, Y. T. Hong, J. K. Park and H. T. Kim, Adv. Mater., 2015, 27, 2974–2980.   \n21 I. Hwang, D. Choi, S. Lee, J. H. Seo, K.-H. Kim, I. Yoon and K. Seo, ACS Appl. Mater. Interfaces, 2017, 9, 21276–21282.   \n22 M. J. Nine, M. A. Cole, L. Johnson, D. N. Tran and D. Losic, ACS Appl. Mater. Interfaces, 2015, 7, 28482–28493.   \n23 J. Yong, F. Chen, Q. Yang, D. Zhang, H. Bian, G. Du, J. Si, X. Meng and X. Hou, Langmuir, 2013, 29, 3274–3279.   \n24 J. Yong, F. Chen, Q. Yang, D. Zhang, G. Du, J. Si, F. Yun and X. Hou, J. Phys. Chem. C, 2013, 117, 24907–24912.   \n25 J. Yong, Q. Yang, F. Chen, D. Zhang, G. Du, H. Bian, J. Si, F. Yun and X. Hou, Appl. Surf. Sci., 2014, 288, 579–583.   \n26 S. Kulinich, S. Farhadi, K. Nose and X. Du, Langmuir, 2010, 27, 25–29.   \n27 J. B. Lee, H. R. Gwon, S. H. Lee and M. Cho, Mater. Trans., 2010, 51, 1709–1711.   \n28 J. Yeo, M. J. Choi and D. S. Kim, J. Micromech. Microeng., 2010, 20, 025028.   \n29 D. M. Sim, M. J. Choi, Y. H. Hur, B. Nam, G. Chae, J. H. Park and Y. S. Jung, Adv. Opt. Mater., 2013, 1, 428–433.   \n30 S. S. Chae, K. H. Kim, J. H. Park, K. H. Lee, S. W. Han, J. Y. Oh, H. K. Baik and Y. S. Kim, Adv. Mater. Interfaces, 2016, 3, 1500725.   \n31 C. Lv, X. Zhang, F. Niu, F. He and P. Hao, Sci. Rep., 2017, 7, 42752.   \n32 Z. Pan, W. Zhang, A. Kowalski and B. Zhao, Langmuir, 2015, 31, 9901–9910.   \n33 A. J. Meuler, J. D. Smith, K. K. Varanasi, J. M. Mabry, G. H. McKinley and R. E. Cohen, ACS Appl. Mater. Interfaces, 2010, 2, 3100–3110.   \n34 Z. Han, Z. Mu, B. Li, Z. Wang, J. Zhang, S. Niu and L. Ren, ACS Nano, 2016, 10, 8591–8602.   \n35 X. Gao, X. Yan, X. Yao, L. Xu, K. Zhang, J. Zhang, B. Yang and L. Jiang, Adv. Mater., 2007, 19, 2213–2217.   \n36 X. Zou, C. Tao, K. Yang, F. Yang, H. Lv, L. Yan, H. Yan, Y. Li, Y. Xie and X. Yuan, Appl. Surf. Sci., 2018, 440, 700–711.   \n37 Z. Han, B. Li, Z. Mu, M. Yang, S. Niu, J. Zhang and L. Ren, Appl. Surf. Sci., 2015, 355, 290–297.   \n38 C. Lv, P. Hao, X. Zhang and F. He, ACS Nano, 2015, 9, 12311– 12319.   \n39 M. He, Q. Zhang, X. Zeng, D. Cui, J. Chen, H. Li, J. Wang and Y. Song, Adv. Mater., 2013, 25, 2291–2295.   \n40 M. Cao, D. Guo, C. Yu, K. Li, M. Liu and L. Jiang, ACS Appl. Mater. Interfaces, 2015, 8, 3615–3623.   \n41 G. McHale, S. Aqil, N. Shirtcliffe, M. Newton and H. Y. Erbil, Langmuir, 2005, 21, 11053–11060.   \n42 B. He, N. A. Patankar and J. Lee, Langmuir, 2003, 19, 4999– 5003.   \n43 R. Wen, Z. Lan, B. Peng, W. Xu, R. Yang and X. Ma, ACS Appl. Mater. Interfaces, 2017, 9, 13770–13777.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# (19)中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n![](images/0bffc018fdedcd442811e7ce17aae453331fa1de9a0208691a529be610cc5a91.jpg)  \n\n(21)申请号 201080052429.5  \n(22)申请日2010.12.21  \n(30)优先权数据2010-002817 2010.01.08 JP  \n\n(85)PCT国际申请进入国家阶段日2012.05.18  \n\n(86)PCT国际申请的申请数据PCT/JP2010/073020 2010.12.21(87)PCT国际申请的公布数据WO2011/083686 JA 2011.07.14(73)专利权人日油株式会社地址 日本东京  \n\n(72)发明人加纳崇光 益子真司 卷口琢郎 山田伦久  \n\n(74)专利代理机构北京路浩知识产权代理有限公司11002代理人谢顺星王朋飞  \n\n(51) Int.CI. C09D 133/24(2006.01) CO9D 7/12(2006.01) CO9D 133/06(2006.01) CO9D 139/00(2006.01) CO9D 141/00(2006.01) C09K 3/18(2006.01)",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (56)对比文件  \n\nJP 特开 2006-28335 A,2006.02.02, JP 特开平8-188682A,1996.07.23, JP 特开平8-269387A,1996.10.15,  \n\n审查员 冯雪",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# (54）发明名称  \n\n防雾涂料组合物",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# (57）摘要  \n\n本发明提供一种防雾涂料组合物，所述防雾涂料组合物即使在进行涂料涂饰及干燥时湿度高的情况下，也能够抑制雾浊现象，并且能够使其在低温且短时间的条件下加热固化，能够获得对基材的粘附性、耐热性及防雾性优异的涂膜。所述防雾涂料组合物含有共聚物(A)、胺类等碱性化合物(B)及阴离子表面活性剂等表面活性剂(C)。所述共聚物(A）由含有下述所示的单体(A1)、单体(A2）及单体(A3）的单体混合物形成。单体(A1)为具有N-羟甲基或 $\\mathrm{N-}$ 烷氧基羟甲基的乙烯基类单体，单体（A2）为具有磺酸基的乙烯基类单体，单体（A3）为（甲基）丙烯酸烷基酯类单体。  \n\n1.防雾涂料组合物，其特征在于，所述防雾涂料组合物含有共聚物(A)、碱性化合物(B)及表面活性剂(C)，所述共聚物(A）由含有下述所示的单体(A1)、单体(A2）及单体（A3)的单体混合物形成；  \n\n单体（A1）：具有 $\\mathrm{N^{-}}$ 羟甲基或 $\\mathrm{N^{-}}$ 烷氧基羟甲基的乙烯类单体；单体（A2）：具有磺酸基的乙烯类单体；单体（A3）：（甲基）丙烯酸烷基酯类单体；以单体（A1)、单体（A2）及单体（A3）的总量为100 质量份计，单体（A1）的含量为 $3\\sim$ 20质量份、单体（A2）的含量为 $3\\sim20$ 质量份、单体(A3)的含量为 $60\\sim94\\$ 质量份，以及单体（A1）及单体（A2）的总量为 $6\\sim40$ 质量份；相对于单体（A2）的磺酸基，碱性化合物（B）的含量为 $50\\sim95\\mathrm{mol}\\%$ ；所述碱性化合物 (B)为单乙醇胺、二乙醇胺、三乙醇胺、二甲氨基乙醇、二乙氨基乙醇或咪唑；以共聚物（A）为100质量份计，表面活性剂（C）的含量为 $0.5\\sim30$ 质量份；碱性化合物(B)在 $25\\mathrm{^\\circC}$ 水溶液中的碱解离常数为 $3\\sim14$ ·碱性化合物(B）的沸点为 $130\\sim1500^{\\circ}\\mathrm{C}$ 02.根据权利要求1所述的防雾涂料组合物，其特征在于，所述单体混合物还含有$\\mathrm{N,N^{-}}$ 二烷基（甲基）丙烯酰胺类单体（A4)，以单体（A3）及单体（A4）的总量为100质量份计，单体（A4）为 $5\\sim50$ 质量份。3.根据权利要求1所述的防雾涂料组合物，其特征在于，共聚物（A）具有单体（A1）的$\\mathrm{N^{-}}$ 羟甲基或 $\\mathrm{N-}$ 烷氧基羟甲基通过缩合反应形成的交联结构；单体(A2）具有中和了的磺酸基和未被中和的磺酸基，所述中和了的磺酸基提高共聚物(A)的亲水性，所述未被中和的磺酸基促进单体（A1）的所述缩合反应。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 防雾涂料组合物",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 技术领域  \n\n[0001］本发明涉及防雾涂料组合物，所述防雾涂料组合物形成于例如汽车前照灯等的基材上，即使在进行涂料涂饰及干燥时湿度高的情况下，也不会产生雾浊(blushing）等问题，能够使其在低温且短时间的条件下加热固化，用于给予对基材的粘附性、耐热性及防雾性优异的涂膜。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 背景技术  \n\n[0002]对于汽车的前照灯等车辆灯具，由于高湿度的空气进入灯室内，因外部气体或降雨等原因使镜片变凉，水分凝结到内侧面上，从而往往会出现结雾。其结果，降低了车灯的亮度，并且影响镜片的美观，从而存在给使用者带来不快的情况。为了防止这种镜片结雾，已知在结雾的部位涂布防雾涂料。  \n\n[0003]本申请人已经提出了如下所述的加热固化型防雾涂料组合物（参见专利文献1)。即，该加热固化型防雾涂料组合物含有嵌段共聚物或接枝共聚物，所述嵌段共聚物或接枝共聚物由亲水性聚合物部分与疏水性聚合物部分构成，所述亲水性聚合物部分由具有$\\mathrm{N^{-}}$ 羟甲基、 $\\mathrm{N-}$ 羟甲基醚基、羟基中的任一种交联官能团的单体、亲水性单体及（甲基）丙烯酸低级烷基酯形成，所述疏水性聚合物部分由具有磺酸基、羧基或磷酸基的乙烯基类单体及（甲基）丙烯酸低级烷基酯形成。根据该防雾涂料组合物，可形成在高温环境下能够维持优异的防雾性和粘附性的涂膜。  \n\n[0004] 现有技术文献  \n[0005] 专利文献  \n[0006] 专利文献1：特开平6-212146号公报（第2页、第3页、第14页～第17页）",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 发明内容  \n\n[0007] 本发明要解决的技术问题  \n\n[0008]但是，专利文献1中记载的防雾涂料组合物，为了使涂膜在 $80^{\\circ}\\mathrm{C}$ 的低温下加热固化，需要60分钟之久的时间。并且在涂饰防雾涂料组合物时环境的相对湿度(RH）高于$60\\%$ 的情况下，会发生因共聚物的疏水性聚合物部分而引起的雾浊现象，存在涂膜容易白化的问题。在此，雾浊现象是指进行涂料涂饰及干燥时的湿度高时（例如相对湿度在 $60\\%$ 以上)，在涂饰过程及干燥过程中，空气中的水分微粒冷凝在涂膜表面上，使树脂成分凝结、析出或涂膜表面产生凹凸，从而看起来涂膜白化的现象。  \n\n[0009］因此，本发明的目的在于，提供一种防雾涂料组合物，所述防雾涂料组合物即使在进行涂料涂饰及干燥时湿度高的情况下也能够抑制雾浊现象，并且能够使其在低温且短时间的条件下加热固化，能够获得对基材的粘附性、耐热性及防雾性优异的涂膜。  \n\n[0010] 解决技术问题的技术手段  \n\n[0011］为了实现上述目的，本发明的一个实施方式的防雾涂料组合物，其含有共聚物(A)、碱性化合物(B）及表面活性剂(C)，所述共聚物(A）由含有下述所示的单体(A1)、单体  \n\n(A2）及单体（A3）的单体混合物形成，  \n[0012]单体（A1）：具有 $\\mathrm{N^{-}}$ 羟甲基或 $\\mathrm{N^{-}}$ 烷氧基羟甲基（N-alkoxymethyl ol group）的乙烯基类单体；  \n[0013]单体（A2）：具有磺酸基（磺基、 $-\\mathrm{S0_{3}H})$ 的乙烯基类单体；  \n[0014] 单体（A3）：（甲基）丙烯酸烷基酯类单体。  \n[0015] 优选的是，以单体(A1)、单体(A2）及单体(A3）的总量为100质量份计，单体(A1)的含量为 $3\\sim20$ 质量份、单体（A2）的含量为 $3\\sim20$ 质量份、单体（A3）的含量为 $60\\sim94\\$ 质量份，以及单体（A  \n[0016］1）与单体（A2）的总量为 $6\\sim40$ 质量份；相对于单体（A2）的磺酸基，碱性化合物(B）的含量为 $50\\sim95\\mathrm{mol}\\%$ ；以共聚物（A）为100质量份计，表面活性剂（C）的含量为$0.5\\sim30$ 质量份。  \n[0017]所述单体混合物还含有 $\\ N,\\ N-$ 二烷基（甲基）丙烯酰胺类单体 (A4)，以单体 (A3)及单体（A4）的总量为100质量份计，单体（A4）优选为 $5\\sim50$ 质量份。  \n[0018] 碱性化合物(B）在 $25\\mathrm{^\\circC}$ 水溶液中的碱解离常数优选为 $3\\sim14$ 0  \n[0019] 碱性化合物(B）的沸点优选为 $130\\sim1500^{\\circ}\\mathrm{C}$ 0  \n[0020］在一个实例中，共聚物（A）具有单体（A1）的 $\\mathrm{N^{-}}$ 羟甲基或 $\\mathrm{N^{-}}$ 烷氧基羟甲基通过缩合反应形成的交联结构；单体（A2）具有中和了的磺酸基和未被中和的磺酸基，所述中和了的磺酸基提高共聚物(A)的亲水性及耐热性，所述未被中和的磺酸基促进单体(A1）的所述缩合反应。  \n[0021］发明效果  \n[0022] 根据本发明，能够发挥如下效果。  \n[0023]在第一发明的防雾涂料组合物中，基于形成共聚物的单体（A1）的性质，表现出了良好的固化性，基于单体（A2）的性质，表现出了在低温下对固化性的促进及对雾浊现象的抑制，基于单体（A3）的性质，表现出了对基材的良好的粘附性和耐热性。另外，基于碱性化合物(B)的性质，使单体(A2)的部分磺酸基被中和,提高了共聚物的亲水性，并提高了对雾浊现象的抑制效果，在此基础上还抑制了涂膜在高温环境下因磺酸基引起的氧化劣化，表现出了优异的耐热性。另外，通过表面活性剂(C)的表面活性作用，降低了附着在涂膜表面的水分的表面张力，通过形成水膜，表现出了良好的防雾性。  \n[0024]因此，防雾涂料组合物即使在进行涂料涂饰及干燥时湿度高的情况下，也能够抑制雾浊现象，并在低温且短时间的条件下具有优异的加热固化性，同时得到的涂膜能够发挥出对基材的优异的粘附性、耐热性及防雾性。  \n具体实施方式  \n而目休亡淫消木[0026] <防雾涂料组合物>  \n[0027] 本实施方式的防雾涂料组合物含有共聚物(A)、碱性化合物 (B）及表面活性剂(C)，所述共聚物（A）由含有下述所示的单体(A1)、单体（A2）及单体（A3）的单体混合物形成；  \n[0028] 单体（A1）：具有N-羟甲基（-NHCHOH）或N-烷氧基羟甲基（-NHCHzOR,但R为烷  \n\n基）的乙烯基类单体；  \n\n[0029] 单体（A2）：具有磺酸基（磺基、 $-\\mathrm{S0_{3}H})$ 的乙烯基类单体；  \n[0030] 单体（A3）：（甲基）丙烯酸烷基酯类单体。  \n\n[0031]该防雾涂料组合物适合用作例如前照灯等车辆灯具的防雾涂料。该防雾涂料组合物在高湿度环境下进行涂饰及干燥时，不会产生雾浊现象等问题，在低温且短时间的条件下具有优异的加热固化性。并且使防雾涂料组合物加热固化而得到的涂膜，对基材（也称为被涂饰物）的粘附性、耐热性及防雾性优异。  \n\n[0032] 下面，对防雾涂料组合物的构成要素依次进行说明。  \n\n[0033] ［共聚物(A)] [0034] ［单体（A1)]  \n\n[0035］首先，对形成共聚物的单体(A1)，即具有 $\\mathrm{N^{-}}$ 羟甲基或 $\\mathrm{N^{-}}$ 烷氧基羟甲基的乙烯基类单体进行说明。该单体(A1）为通过脱水缩合反应或脱醇缩合反应等缩合反应，使分子间交联，用来在共聚物中形成交联结构的乙烯基类单体。由于单体(A1）具有这种交联性官能团，通过对制备后的共聚物进行加热，能够在共聚物中形成交联结构。此外，使用酸催化剂来促进该缩合反应。  \n\n[0036]作为单体（A1）可以例举如 $\\mathrm{N^{-}}$ 羟甲基（甲基）丙烯酰胺、N-甲氧基羟甲基（甲基)丙烯酰胺、 $.\\mathrm{N-}$ 丁氧基羟甲基（甲基）丙烯酰胺等。可以使用其中的一种或两种以上作为单体(A1)。从防雾涂料组合物的保存稳定性优异、在低温下加热固化性优异的角度来看，在这些单体中尤其优选的单体（A1）为 $\\mathrm{N-}$ 羟甲基（甲基）丙烯酰胺。  \n\n[0037]在单体（A1)、(A2）及（A3）的总量100质量份中，单体（A1）的含量优选为 $3\\sim20$ 质量份，更优选为 $5\\sim15$ 质量份。单体（A1）的含量低于3质量份的情况下，会降低共聚物在低温下的固化性，使固化时间延长。另一方面，单体（A1）的含量高于20质量份的情况下,共聚物的交联密度变高，会降低涂膜的防雾性，并且，在高温环境下放置的情况下，交联反应会随时间进行，有可能导致进一步降低防雾性。  \n\n[0038] [单体 (A2)]  \n\n[0039］接下来,对单体(A2)，即具有磺酸基的乙烯基类单体进行说明。该单体(A2）具有作为酸催化剂的功能，用来在低温下促进上述单体(A1)的缩合反应；该单体(A2)还具有提高共聚物的亲水性、在高湿度环境下进行涂饰及干燥的情况下抑制雾浊现象、用来赋予良好的涂膜外观的功能。  \n\n[0040]作为单体（A2）可以例举如（甲基）丙烯酸 $-3-$ 磺基丙酯、（甲基）丙烯酸 $-2-$ 磺基乙酯、2-丙烯酰胺 $-2-$ 甲基丙磺酸、对苯乙烯磺酸、乙烯基磺酸、甲代烯丙基磺酸等。可以使用其中的一种或两种以上作为(A2)。  \n\n[0041］从与单体（A1）具有优异的共聚性的角度来看，在这些单体中优选的单体（A2）为（甲基）丙烯酸 $-3-$ 磺基丙酯及（甲基）丙烯酸 $-2-$ 磺基乙酯、 $2^{-}$ 丙烯酰胺 $-2-$ 甲基丙磺酸。  \n\n[0042]在单体（A1)、(A2）及（A3）的总量100质量份中，单体（A2）的含量优选为 $3\\sim20$ 质量份，更优选为 $5\\sim15$ 质量份。单体(A2）的含量低于3质量份的情况下，在单体(A1)的缩合反应中作为酸催化剂的效果不充分，降低共聚物在低温下的固化性，有固化时间延长的倾向。进一步地，因共聚物的亲水性不足，在高湿度环境下进行涂饰及干燥的情况下，有可能产生雾浊现象。另一方面，单体（A2)的含量高于20质量份的情况下，共聚物（A）的极性变得非常高，使得涂膜和基材之间的亲和性变低，结果存在涂膜的粘附性降低的倾向，在此基础上，因单体(A2）的磺酸基容易引起在高温环境下涂膜的氧化劣化，存在导致涂膜的耐热性降低的倾向。  \n\n[0043] [单体(A3)]  \n\n[0044］接下来，对作为单体(A3)的（甲基）丙烯酸烷基酯类单体进行说明。该单体（A3)为用于提高涂膜的耐热性，并且提高涂膜与基材之间的亲和性，从而给予良好的粘附性的成分。（甲基）丙烯酸烷基酯类单体是指（甲基）丙烯酸的直链、支链或环状的烷基酯。[0045]作为该单体(A3）可以例举如（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丙酯、（甲基）丙烯酸异丙酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸异丁酯、（甲基）丙烯酸叔丁酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸月桂酯、（甲基）丙烯酸十八烷基酯、（甲基）丙烯酸环己酯等。可以使用其中的一种或两种以上作为单体(A3)。[0046］优选的单体（A3）为（甲基）丙烯酸低级烷基酯类单体。（甲基）丙烯酸低级烷基酯类单体是指在（甲基）丙烯酸烷基酯类单体中，烷基酯的烷基碳原子数为 $1\\sim4$ 的物质。进一步优选的单体（A3）为烷基酯的烷基碳原子数为1或2的（甲基）丙烯酸低级烷基酯。在使用烷基酯的烷基碳原子数为5以上的（甲基）丙烯酸烷基酯类单体的情况下，会降低共聚物的亲水性，在高湿度环境下进行涂饰及干燥的情况下，存在容易产生雾浊现象的倾向。  \n\n[0047]在单体（A1)、(A2）及（A3）的总量100质量份中，单体（A3）的含量优选为 $60\\sim94\\$ 质量份，更优选为 $70\\sim90$ 质量份。单体(A3）的含量低于60质量份的情况下，单体(A1)及（A2）的比例增大，因此会降低涂膜与基材之间的粘附性。另一方面，单体(A3)的含量高于94质量份的情况下，单体（A1）及单体（A2）的比例降低，因此共聚物在低温下的固化性降低，存在固化时间延长的倾向。  \n\n[0048] ［其他乙烯基类单体]  \n\n[0049]作为用来形成共聚物的单体，除了上述单体（A1)、单体（A2）及单体(A3）之外，还可以使用其他乙烯基类单体。作为这些其他乙烯基类单体只要是能够和单体 (A1) $\\sim$ (A3)共聚，则没有特别限制。  \n\n[0050]］作为其他乙烯基类单体的具体例,可以例举如苯乙烯、乙烯基甲苯、α－甲基苯乙烯等芳香族乙烯基类单体；（甲氧基）聚乙二醇单（甲基）丙烯酸酯、（甲氧基）聚丙二醇单（甲基）丙烯酸酯、（乙氧基）聚乙二醇单（甲基）丙烯酸酯、（乙氧基)聚丙二醇单（甲基）丙烯酸酯等烷氧基烷二醇（甲基）丙烯酸酯类单体；（甲基）丙烯酸 $2^{-}$ 羟乙酯、（甲基）丙烯酸 $2^{-}$ 羟丙酯、（甲基）丙烯酸4-羟丁酯、（甲基）丙烯酸2-羟乙酯的－己内酯加成产物等的含羟基的乙烯基类单体；（甲基）丙烯酸、巴豆酸、马来酸、马来酸半酯等含羧基单体及其碱金属盐或铵盐；（甲基）丙烯酰胺、 $\\mathrm{N-}$ 甲基（甲基）丙烯酰胺、N，N-二甲基（甲基）丙烯酰胺、 $\\mathrm{N^{-}}$ 乙基（甲基）丙烯酰胺、 $\\mathrm{N},\\mathrm{N-}$ 二乙基（甲基）丙烯酰胺、 $\\mathrm{N^{-}}$ 正丙基（甲基）丙烯酰胺、 $.\\mathrm{N-}$ 异丙基（甲基）丙烯酰胺、 $\\mathrm{N-}$ 二甲氨基乙基（甲基）丙烯酰胺、 $.\\mathrm{N-}$ 二甲氨基丙基（甲基）丙烯酰胺、二丙酮（甲基）丙烯酰胺、N-（甲基）丙烯酰哌啶、（甲基）丙烯酰吗啉、 $\\mathrm{N^{-}}$ 乙烯基 $-2-$ 吡咯烷酮、 $2-$ 乙烯基吡啶等的含氮原子的乙烯基类单体等。可以使用其中的一种或两种以上作为其他乙烯基类单体。  \n\n[0051] [单体 (A4)]  \n\n[0052]从耐热性优异、亲水性高、对雾浊现象的抑制效果良好等方面来看，在其他乙烯基类单体中优选 $\\mathrm{N},\\mathrm{N-}$ 二甲基（甲基）丙烯酰胺、 $\\cdot\\mathrm{N},\\mathrm{N-}$ 二乙基（甲基）丙烯酰胺等 $\\mathrm{N},\\mathrm{N-}$ 二烷基（甲基）丙烯酰胺类单体（有时简称为单体(A4)）。可以使用一种或两种以上作为单体(A4)。在单体（A3）及单体（A4）的总量100质量份中，单体（A4）的含量优选为 $5\\sim50$ 质量份。  \n\n[0053]另外，从在对基材的粘附性及耐热性优异的同时，能够提高共聚物的亲水性，抑制雾浊现象的方面来看，进一步优选为将（甲基）丙烯酸低级烷基酯类单体（A3）与N，N-二烷基丙烯酰胺类单体(A4）进行组合使用。  \n\n[0054]］（甲基）丙烯酸低级烷基酯类单体与N，N-二烷基（甲基）丙烯酰胺类单体进行组合使用的情况下，在（甲基）丙烯酸低级烷基酯类单体（A3）与N，N-二烷基（甲基）丙烯酰胺类单体（A4）的总量100质量份中，（甲基）内烯酸低级烷基酯类单体（A3）的含量优选为 $50\\sim90\\$ 质量份，N, $\\mathrm{N^{-}}$ 二烷基（甲基）丙烯酰胺类单体（A4）的含量优选为余量范围。（甲基）丙烯酸低级烷基酯类单体（A3）小于50质量份的情况下，共聚物的亲水性显著提高，因此存在为了获得充分的交联度，固化时间延长的倾向。另一方面，（甲基）丙烯酸低级烷基酯类单体(A3)大于90质量份的情况下，提高共聚物亲水性的效果变低，存在对雾浊现象的抑制效果降低的倾向。  \n\n[0055] ［共聚物（A）的制备方法]  \n\n[0056]共聚物(A）是通过将含有上述单体（A1)、(A2)、(A3）及根据需要含有(A4）的单体混合物进行共聚而制得的。作为共聚物的结构可以是无规共聚物、交替共聚物、嵌段共聚物及接枝共聚物中的任意一种结构，但从能够提高防雾涂料组合物以防雾性为首的效果，同时能够容易地配制防雾涂料组合物的角度来看，优选无规共聚物。作为用来得到共聚物的聚合方法，可以使用自由基聚合法、阳离子聚合法、阴离子活性聚合法、阳离子活性聚合法等公知的各种聚合方法，但从工业生产性的容易度、产品性能多样化的方面考虑，尤其优选自由基聚合法。作为自由基聚合法，通常采用块状聚合法、悬浮聚合法、溶液聚合法、乳化聚合法等，但从聚合后能够将其直接用作涂料的角度来看，优选溶液聚合法。  \n\n[0057] 下面说明使用溶液聚合法进行制备的方法。  \n\n[0058]关于聚合溶剂，具有非常高的沸点的聚合溶剂，在涂膜的干燥、加热固化时，存在由于聚合溶剂残留使涂膜对基材的粘附性受损的情况，因此优选使用具有小于 $180^{\\circ}\\mathrm{C}$ 沸点的聚合溶剂。作为这样的聚合溶剂，例如可以使用甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、仲丁醇、叔丁醇、二丙酮醇等醇类溶剂;乙二醇单甲醚、乙二醇单乙醚、丙二醇单甲醚、丙二醇单乙醚、 $\\cdot3-$ 甲氧基 $^{-1-}$ 丁醇、 $\\:3-\\:$ 甲氧基 $-3-$ 甲基 $^{-1-}$ 丁醇等醇醚类溶剂;丙酮、甲乙酮、甲基异丁基酮、环己酮等酮类溶剂;四氢呋喃、二氧六环等醚类溶剂;乙酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸异丁酯、乙酸叔丁酯、乳酸甲酯、乳酸乙酯等酯类溶剂;苯、甲苯、二甲苯等芳香族类溶剂;甲酰胺、二甲基甲酰胺等胺类溶剂;水等。可以使用其中的一种或两种以上作为聚合溶剂。  \n\n[0059]在单体(A1)、(A2)、(A3）及根据需要加入的单体(A4）的总量与用于聚合反应的聚合溶剂的总量100质量份中，单体总量优选为50质量份以下。单体的比例超过50质量份的情况下，存在聚合发热变大，不易于工业制备的倾向。  \n\n[0060］作为自由基聚合引发剂,可以使用通常所使用的有机过氧化物、偶氮化合物。作为有机过氧化物，可以例举如过氧化苯甲酰、过氧化 $3,5,5-$ 三甲基己酰（3,5,5-trimethylhexanoyl peroxide)、过 氧化 $-2-$ 己酸叔丁酯(t-butylperoxy $^{-2}$ -hexanoate)、过氧化新戊酸叔丁酯（t-butyl peroxypivalate)、过氧化新戊酸叔己酯（t-hexyl peroxypivalate）等。作为偶氮化合物,可以例举如 $2,2^{\\prime}\\mathrm{~-~}$ 偶氮二异丁腈、 $2,2^{\\prime}\\mathrm{~-~}$ 偶氮双 $-2-$ 甲基丁晴等。在单体 (A1)、(A2)、(A3）及根据需要加入的单体(A4)的总量100质量份中，自由基聚合引发剂的添加量优选为 $0.01\\sim5$ 质量份。从边滴加到反应容器中边进行聚合反应会易于控制聚合发热的角度来看，优选自由基聚合引发剂。根据使用的自由基聚合引发剂的种类，可以对聚合温度进行适当调整，但在工业制备中优选为$30\\sim150\\mathrm{^{\\circ}C}$ ，更优选为 $40\\sim100^{\\circ}\\mathrm{C}$ 0  \n\n[0061] [碱性化合物 (B)]  \n\n[0062]下面，对碱性化合物(B)进行说明。该碱性化合物是用于中和上述单体(A2）的部分磺酸基的成分。由于单体(A2）的部分磺酸基被碱性化合物(B)中和，因此能够提高共聚物的亲水性，并能够提高对雾浊现象的抑制效果，在此基础上，还能够抑制涂膜在高温环境下因磺酸基引起的氧化劣化，能够提高耐热性。  \n\n[0063]作为碱性化合物 (B)，可以例举如氢氧化钠、氢氧化钙、氨、甲胺、二甲胺、三甲胺、乙胺、二乙胺、三乙胺、单乙醇胺、二乙醇胺、三乙醇胺、二甲氨基乙醇、二乙氨基乙醇、苯胺、α－萘胺、苄胺、吡啶、 $2,6-$ 二甲基吡啶、咪唑等。可以使用其中的一种或两种以上作为碱性化合物 (B)。  \n\n[0064]］此外，从加热固化涂膜时与磺酸基容易解离，难以阻碍磺酸基用作酸催化剂的作用的角度来看，碱性化合物 (B)在 $25\\mathrm{^\\circC}$ 水溶液中的碱解离常数（以下简称为pKb）优选为$3\\sim14$ ，更优选为 $4\\sim14$ 。作为这样的碱性化合物 (B)，可以例举如氨 $\\mathrm{(pKb=4.7)}$ 、甲胺$(\\mathrm{pKb}=3.5)$ 、二甲胺 $\\mathrm{(pKb=3.4)}$ 、三甲胺 $\\mathrm{(pKb=3.2)}$ 、乙胺 $(\\mathrm{pKb}=3.5)$ 、二乙胺 $\\mathrm{(pKb=}$ 3.4)、三乙胺 $\\mathrm{(pKb=3.2)}$ 、单乙醇胺 $\\mathrm{(pKb=4.5)}$ 、二乙醇胺 $\\mathrm{(pKb=5.1)}$ 、三乙醇胺（pKb$=6.2\\times$ 、二甲氨基乙醇 $\\mathrm{(pKb=4.1\\dot{}}$ )、二乙氨基乙醇 $\\mathrm{{(pKb=4.1)}}$ 、苯胺 $\\mathrm{(pKb=4.6)}$ )、α-萘胺 $(\\mathrm{pKb}=10.1)$ 、苄胺 $(\\mathrm{pKb}=4.6)$ 、吡啶 $\\mathrm{(pKb=8.8)}$ 、 $\\:2,6-\\:$ 二甲基吡啶 $\\mathrm{(pKb=8.0)}$ ）、咪唑 $(\\mathrm{pKb=7.1})$ 等。  \n\n[0065]从提高抑制涂膜在高温环境下因磺酸基引起的氧化劣化的效果的角度来看，碱性化合物(B）优选具有 $130\\sim1500^{\\circ}\\mathrm{C}$ 的沸点，在高温环境下挥发性低，更优选具有 $150\\sim$ $1500^{\\circ}\\mathrm{C}$ 的沸点。作为这样的碱性化合物 (B)，可以例举如氢氧化钠（沸点 $1390^{\\circ}\\mathrm{C}$ )、氢氧化钙（在熔点 $580^{\\circ}\\mathrm{C}$ 下分解）、单乙醇胺（沸点 $172\\mathrm{^\\circC}$ )、二乙醇胺（沸点 $217\\mathrm{^{\\circ}C}$ )、三乙醇胺（沸点$335\\mathrm{^\\circC}$ )、二甲氨基乙醇（沸点 $144^{\\circ}\\mathrm{C}$ )、二乙氨基乙醇（沸点 $163^{\\circ}\\mathrm{C}$ ）、苯胺（沸点 $184^{\\circ}\\mathrm{C}$ ）、α-萘胺（沸点 $301^{\\circ}\\mathrm{C}$ )、苄胺（沸点 $183^{\\circ}\\mathrm{C}$ ） $2,6-$ 二甲基吡啶（沸点 $\\mathrm{144^{\\circ}C}$ )、咪唑（沸点$256^{\\circ}\\mathrm{C}$ ）等。  \n\n[0066]作为碱性化合物 (B)，更优选为 $25\\mathrm{^\\circC}$ 水溶液中的 $\\mathrm{\\pKb}$ 为 $3\\sim14$ ，且沸点为 $130\\sim$ $1500^{\\circ}\\mathrm{C}$ 的化合物。作为这样的碱性化合物 (B)，可以例举如单乙醇胺、二乙醇胺、三乙醇胺、二甲氨基乙醇、二乙氨基乙醇、咪唑等。  \n\n[0067]作为碱性化合物 (B)，最优选为 $25\\mathrm{^\\circC}$ 水溶液中的 $\\mathrm{\\pKb}$ 为 $4\\sim14$ ，且沸点为 $150\\sim$ $1500^{\\circ}\\mathrm{C}$ 的化合物。作为这样的碱性化合物 (B)，可以例举如单乙醇胺、二乙醇胺、三乙醇胺、  \n\n二乙氨基乙醇、咪唑等。  \n\n[0068]为了使该碱性化合物(B)仅中和单体（A2）的部分磺酸基，由此使单体（A2）具有提高共聚物（A)的亲水性及耐热性的磺酸基和促进单体（A1）的缩合反应的未被中和的磺酸基，从而决定碱性化合物(B)的含量。在实施方式中，相对于单体(A2）的磺酸基，碱性化合物(B）的含量优选为 $50\\sim95\\mathrm{mol}\\%$ ，更优选为 $60\\sim90\\mathrm{mol}\\%$ 。碱性化合物(B）的含量小于 $50m o l\\%$ 的情况下，提高共聚物亲水性及耐热性的效果会变低。另一方面，碱性化合物(B）的含量大于 $95m o l\\%$ 的情况下，磺酸基作为酸催化剂的功能会降低，并且共聚物在低温下的固化性显著降低，因此不优选。  \n\n[0069]作为通过碱性化合物(B)对单体(A2）的磺酸基进行中和的方法，可以是在共聚物和溶剂的溶液中加入碱性化合物(B)的方法，也可以是在制备共聚物时，将碱性化合物(B)与单体一同加入的方法。在这些方法中，优选后者，这是因为通过单体(A2)被碱性化合物(B）中和,酸度降低，对聚合溶剂的溶解性良好，同时不易腐蚀反应容器。  \n\n[0070] ［表面活性剂（C)]  \n\n[0071]下面，对表面活性剂(C)进行说明。该表面活性剂(C)是用来使附着在涂膜表面的水分的表面张力降低，通过在涂膜表面形成水膜，从而提高防雾性的成分。作为表面活性剂(C)，可以使用现有公知的所有表面活性剂，可以例举如非离子表面活性剂、阴离子表面活性剂、阳离子表面活性剂及两性离子表面活性剂等。其中，从效果的持续性来看，优选为至少含有一种以上的阴离子表面活性剂。  \n\n[0072]作为非离子表面活性剂，例如可以使用聚氧乙烯月桂醇、聚氧乙烯月桂醚、聚氧乙烯油基醚等聚氧乙烯高级醇醚类;聚氧乙烯辛基苯酚、聚氧乙烯壬基苯酚等聚氧乙烯烷基芳基醚类;聚氧乙二醇单硬脂酸酯等聚氧乙烯酰基酯类;聚丙二醇环氧乙烯加成产物、聚氧乙烯山梨醇酐单月桂酸酯、聚氧乙烯山梨醇酐单硬脂酸酯等聚氧乙烯山梨醇酐脂肪酸酯类；烷基磷酸酯、聚氧乙烯烷基醚磷酸酯等磷酸酯类;糖脂类;纤维素醚类等。  \n\n[0073]作为阴离子表面活性剂,例如可以使用油酸钠、油酸钾等脂肪酸盐；月桂基硫酸钠、月桂基硫酸铵等高级醇硫酸酯类；十二烷基基苯磺酸钠、烷基萘磺酸钠等烷基苯磺酸盐及烷基萘磺酸盐;萘苯磺酸福尔马林缩合物、二烷基磺化琥珀酸盐、二烷基磷酸盐、聚氧乙烯烷基苯基醚硫酸钠等聚氧乙烯硫酸盐等。  \n\n[0074]作为阳离子表面活性剂，例如可以使用乙醇胺类；月桂胺醋酸盐、三乙醇胺单甲酸盐、硬质酰胺乙基二乙胺醋酸盐等胺盐；月桂基三甲基氯化铵、硬脂基三甲基氯化铵、二月桂基二甲基氯化铵、二硬脂基二甲基氯化铵、月桂基二甲基苄基氯化铵、硬脂基二甲基苄基氯化铵等季铵盐等。  \n\n[0075]作为两性离子表面活性剂，例如可以使用二甲基烷基月桂基甜菜碱、二甲基烷基硬脂基甜菜碱等脂肪酸型两性离子表面活性剂；二甲基烷基磺基甜菜碱等磺酸型两性离子表面活性剂;烷基甘氨酸等。  \n\n[0076]以上述共聚物为100 质量份，上述表面活性剂(C)的含量优选为 $0.5\\sim30$ 质量份，更优选为 $1\\sim20$ 质量份。表面活性剂(C）的含量不足0.5质量份的情况下，难以获得长期的涂膜防雾持续性。另一方面，超过30质量份的情况下，表现出涂膜的外观和粘附性降低，同时涂膜的耐水性降低的倾向。作为共聚物与表面活性剂(C)的混合方法，可以将共聚物溶于溶剂后，在其中加入表面活性剂(C)，或者可以在制备共聚物时，将表面活性剂(C）与  \n\n单体一同加入。  \n\n[0077] ［其他成分]  \n\n[0078]防雾涂料组合物的必须成分为共聚物(A)、碱性化合物(B）及表面活性剂(C)。在防雾涂料组合物中，作为其他成分，可以根据需要混配流平剂、抗氧化剂、紫外线吸收剂、光稳定剂、固化催化剂等常用的各种添加剂。这些其他成分，每种添加剂可以分别以常用的添加量进行混配。  \n\n[0079] ［防雾涂料组合物的制备]  \n\n[0080］防雾涂料组合物，其是将通过上述单体的共聚获得的共聚物溶液，以调节成适合涂饰的粘度作为目的，一般通过加入溶剂溶解、分散或稀释而制得。对于加入到共聚物溶液中的溶剂，具有非常高的沸点的溶剂,在涂膜的干燥、加热固化时，存在因溶剂的残留损害涂膜对基材的粘附性的情况，因此优选使用具有小于 $180^{\\circ}\\mathrm{C}$ 的沸点的聚合溶剂。  \n\n[0081］作为这样的溶剂可以例举如甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、仲丁醇、叔丁醇、二丙酮醇等醇类溶剂;乙二醇单甲醚、乙二醇单乙醚、丙二醇单甲醚、丙二醇单乙醚、3-甲氧基 $^{-1-}$ 丁醇、3-甲氧基 $-3-$ 甲基 $^{-1-}$ 丁醇等醇醚类溶剂;丙酮、甲乙酮、甲基异丁酮、环己酮等酮类溶剂;四氢呋喃、二氧六环等醚类溶剂;乙酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸异丁酯、乙酸叔丁酯、乳酸甲酯、乳酸乙酯等酯类溶剂;苯、甲苯、二甲苯等芳香族类溶剂；甲酰胺、二甲基甲酰胺等胺类溶剂;正己烷、环己烷、正庚烷、正辛烷、正癸烷等烃类溶剂;水等。可以使用其中的一种或两种以上作为溶剂。  \n\n[0082] ［涂饰物品］  \n\n[0083]对使用上述防雾涂料组合物形成的涂饰物品进行说明。该涂饰物品是将防雾涂料组合物涂布于作为基材的被涂饰物上，然后进行干燥，接着在 $60\\sim150\\mathrm{^{\\circ}C}$ 的温度下加入固化 $5\\sim60$ 分钟，从而在被涂饰物表面形成涂膜。  \n\n[0084]作为涂膜的具体形成方法，首先按照一般涂料中使用的涂饰方法，将防雾涂料组合物涂饰在被涂饰物上。此时，以提高防雾涂料组合物对被涂饰物的润湿性，及防止凹陷为目的，在涂饰前，优选去除被涂饰物表面附着的异物或进行脱脂、清洗。具体地，可以例举如通过高压空气或离子化空气进行除尘、通过洗涤剂水溶液或乙醇溶剂进行超声清洗、使用乙醇溶剂等进行擦拭、通过紫外线和臭氧进行清洗等。作为涂饰方法，适合采用浸渍法、流涂法、辊涂法、棒涂法、喷涂法等。  \n\n[0085］涂饰后，在 $20\\sim50^{\\circ}\\mathrm{C}$ 的温度下，使涂膜中含有的溶剂挥发干燥 $0.5\\sim5$ 分钟。然后在 $60\\sim150^{\\circ}\\mathrm{C}$ 的温度下加热固化 $5\\sim60$ 分钟，优选在 $70\\sim130\\mathrm{^{\\circ}C}$ 下加热固化 $10\\sim40$ 分钟，从而形成涂膜。此时，通过单体（A2）的磺酸基促进共聚物中含有的单体（A1）的 $\\mathrm{N^{-}}$ 羟甲基或 $\\mathrm{N^{-}}$ 烷氧基羟甲基的脱水缩合反应或脱醇缩合反应的进行，从而在共聚物中形成交联结构。但是，被涂饰物为合成树脂材料的情况下，需要将固化温度设定在合成树脂材料的热变形温度以下。  \n\n[0086]为了获得良好的防雾性和涂膜外观,通过防雾涂料组合物形成于被涂饰物上的涂膜厚度优选为 $0.5\\sim20\\:\\upmu\\mathrm{~m~}$ ，更优选为 $1\\sim10~\\upmu\\textrm{m}$ 。该厚度比 $0.5\\upmu\\mathrm{{m}}$ 薄的情况下，存在涂膜的防雾性变低的倾向，在超过 $20~\\upmu\\textrm{m}$ 的情况下，存在涂膜外观变差的倾向。  \n\n[0087]作为防雾涂料组合物所涂饰的被涂饰物，可以适当使用丙烯酸树脂、聚碳酸酯树脂、聚乙二醇对苯二甲酸酯树脂等透明树脂的薄膜、板材、成品及其加工品。作为该被涂饰物，尤其优选车辆灯具。作为车辆灯具，具体可以例举如前照灯、辅助前照灯、侧灯、牌照灯、尾灯、停车灯、刹车灯、倒车灯、方向指示灯、辅助方向指示灯、危险报警闪光灯等。  \n\n[0088] 《实施方式的效果概述>  \n\n[0089]（1）实施方式的防雾涂料组合物中，由单体（A1）的性质表现出良好的固化性，由单体（A2）的性质表现出在低温下对固化性的促进和对雾浊现象的抑制，由单体（A3）的性质表现出与基材良好的粘附性和耐热性。并且，由碱性化合物(B)的性质，表现出下述效果，单体（A2）的部分磺酸基被中和,提高共聚物的亲水性，并且提高了对雾浊现象的抑制效果，在此基础上，抑制了涂膜在高温环境下因磺酸基引起的的氧化劣化，表现出优异的耐热性。另外，由表面活性剂(C)的表面活性作用，降低了附着在涂膜表面的水分的表面张力，形成水膜，从而表现出良好的防雾性。  \n\n[0090]］因此，防雾涂料组合物即使在进行涂料的涂饰及干燥时湿度高的情况下，也能够抑制雾浊现象，并在低温且短时间条件下的加热固化性优异，同时制得的涂膜还能够发挥出对基材优异的粘附性、耐热性及防雾性。  \n\n[0091］（2）另外，将单体（A1)、单体（A2）及单体（A3）的总量以100 质量份计，单体（A1)的含量为 $3\\sim20$ 质量份、单体(A2）的含量为 $3\\sim20$ 质量份，以及单体（A3）的含量为 $60\\sim$ 94质量份，并且单体(A1）及单体(A2)的总量被设定为 $6\\sim40$ 质量份。因此,基于单体 (A1)的固化性，因基于单体(A2)的催化剂功能而得以提高，同时利用基于单体(A2)的亲水性能够抑制涂饰时产生雾浊现象。并且，单体(A3)的含量也非常充足，能够发挥涂膜的良好的耐热性和粘附性。  \n\n[0092]另外，相对于单体（A2）的磺酸基，碱性化合物(B）被设定为其 $50\\sim95\\mathrm{mol}\\%$ 。因此，能够提高共聚物的亲水性，从而能够充分抑制雾浊现象，同时能够充分维持该磺酸基的催化剂功能，在此基础上，还能够抑制涂膜在高温环境下因磺酸基引起的氧化劣化，提高耐热性。  \n\n[0093]并且，以共聚物（A）为100 质量份计，表面活性剂（C)被设定为 $0.5\\sim30$ 质量份。  \n因此，降低了附着在涂膜表面的水分的表面张力，能够对形成水膜发挥出充分的效果。  \n\n[0094]（3）单体混合物进一步含有N，N-二烷基（甲基）丙烯酰胺类单体（A4)，将单体(A3）及单体（A4）的总量以100质量份计，单体（A4）被设定为 $5\\sim50$ 质量份的情况下，能够进一步扩大对雾浊现象的抑制效果，同时还能够提高涂膜的耐热性。  \n\n[0095]（4）碱性化合物（B）在 $25\\mathrm{^\\circC}$ 水溶液中的碱解离常数pKb为 $3\\sim14$ ，从而在加热固化涂膜时，磺酸基与碱性化合物容易解离，能够充分发挥磺酸基作为酸催化剂的作用。  \n\n[0096]（5）碱性化合物（B）的沸点为 $130\\sim1500^{\\circ}\\mathrm{C}$ ，从而降低在高温环境下的挥发性，提高抑制涂膜在高温环境下因磺酸基引起的氧化劣化的效果持续性，能够进一步提高耐热性。  \n\n[0097] 实施例  \n\n3] 下面，例举实施例及比较例，进一步具体说明上述实施方式。  \n\n[0099] ［实施例1]  \n\n[0100]］在具有搅拌装置、氮气导入管及冷凝管的反应容器中加入下述化合物，边吹入氮气边加热至 $65^{\\circ}\\mathrm{C}$ 0  \n\n[0101] 作为聚合溶剂的 $240\\mathrm{g}$ 正丙醇（以下简称为NPA）；  \n\n[0102] 作为单体（A1）的 $10\\mathrm{g}\\ N-$ 羟甲基丙烯酰胺（以下简称为N-MAA）；[0103] 作为单体（A2）的 $10\\mathrm{{g}\\ 2-}$ 丙烯酰胺 $-2-$ 甲基丙磺酸（以下简称为AMPS）；[0104] 作为单体（A3）的 $60\\mathrm{g}$ 甲基丙烯酸甲酯（以下简称为MMA)、 $20\\mathrm{g}$ 丙烯酸正丁酯（以下简称为BA）；  \n\n:0105] 作为单体（A4）的 $20\\mathrm{g}\\ N,\\mathrm{N}-$ 二甲基丙烯酰胺（以下简称为DMAA）；  \n\n[0106]作为碱性化合物（B）的 $5.04\\mathrm{g}$ 三乙醇胺（参见表1,在 $25\\mathrm{^\\circC}$ 水溶液中的碱解离常数 $\\mathrm{pKb}=6.2$ ，沸点 $335^{\\circ}\\mathrm{C}$ )。  \n\n[0107]并且，碱性化合物（B)的量相当于作为单体（A2）的AMPS 的磺酸基的 $70m o l\\%$ 0参见下式。{AMPS加入量）÷AMPS的摩尔质量 $\\times70\\%$ · $100\\times$ {三乙醇胺的摩尔质量 $\\}=$ $10\\div207.4\\times70\\div100\\times149.2=5.04_{}$ 。  \n\n[0108]然后，将作为自由基聚合引发剂的 $\\mathrm{1g}$ 过氧化新戊酸叔己酯的烃稀释品（日油（株）制备的商品名：PERHEXYL（八一）PV）溶于 $40\\mathrm{gNPA}$ 中,将得到的溶液经3小时滴入到反应容器中。经过5小时的聚合后，将反应容液升温至 $80^{\\circ}\\mathrm{C}$ ，在该温度下聚合1小时，得到共聚物浓度为30质量 $\\%$ 的溶液。  \n\n[0109］在上述 $333.3\\mathrm{g}$ 共聚物溶液（作为共聚物为 $\\left|100\\mathrm{g}\\right\\rangle$ ）中加入266.7gNPA和 $400\\mathrm{g}$ 丙二醇单甲醚（以下简称为PGM)，使共聚物的浓度调节至10质量 $9\\%$ ，然后与作为表面活性剂(C）的 $10\\mathrm{{g}\\ 2\\mathrm{{-}}}$ 乙基己基磺化琥珀酸钠（日油（株）制备的商品名：Rapizol（匕一）$\\mathrm{A}{-}80$ （有效成分80质量 $\\%$ ))（换算为纯品为 $8\\mathrm{g}^{\\cdot}$ ）和作为流平剂的 $0.1\\mathrm{g}$ 聚醚改性聚二甲基硅氧烷（日本毕克化学公司（·）（株）制备的商品名:BYK333）进行混合，获得防雾涂料组合物。  \n\n[0110］关于该防雾涂料组合物，使用以下说明的防雾涂料组合物的评价方法进行评价，得到的结果如表2所示。  \n\n[0111] 表1  \n\n<html><body><table><tr><td rowspan=\"7\">[0112]</td><td colspan=\"3\"></td><td>在25℃水溶液中 的碱解离常数 (pKb)</td><td>沸点 (℃)</td><td>摩尔质量 (g/mol)</td></tr><tr><td rowspan=\"7\">碱性化合物</td><td rowspan=\"7\">B</td><td>三乙醇胺</td><td>6.2</td><td>335</td><td>149.2</td></tr><tr><td>咪唑</td><td>7.1</td><td>256</td><td>68.1</td></tr><tr><td>二甲氨基乙醇</td><td>4.1</td><td>144</td><td>89.1</td></tr><tr><td>吡啶</td><td>8.8</td><td>115</td><td>79.1</td></tr><tr><td>三乙胺</td><td>3.2</td><td>90</td><td>101.2</td></tr><tr><td>氢氧化钠</td><td>0.2</td><td>1390</td><td>40.0</td></tr></table></body></html>  \n\n<html><body><table><tr><td colspan=\"9\">表2</td></tr><tr><td colspan=\"3\"></td><td rowspan=\"19\">单位</td><td colspan=\"8\">实施例</td></tr><tr><td></td><td>A1</td><td></td><td></td><td>1</td><td>2 10</td><td>3 4 10</td><td>5 10</td><td>6 10</td><td>7 10</td><td>8 10</td></tr><tr><td rowspan=\"4\">形的聚物</td><td></td><td>N-MAA</td><td>(以单()(A)</td><td>10</td><td></td><td>10</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>AMS</td><td></td><td>102</td><td></td><td>20</td><td></td><td></td><td>02</td><td>62</td><td></td></tr><tr><td>##</td><td></td><td></td><td></td><td>2</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>A4</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td rowspan=\"6\">碱性 化合物</td><td rowspan=\"6\">B</td><td>DMAA 三乙醇胺</td><td rowspan=\"5\">摩尔% （相对于单体（A2）的磺酸基）</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td></tr><tr><td></td><td>70</td><td></td><td></td><td></td><td></td><td></td><td>50</td><td>95</td></tr><tr><td>咪唑</td><td></td><td>70</td><td></td><td></td><td></td><td></td><td></td><td>一</td></tr><tr><td>二甲氨基乙醇</td><td></td><td></td><td>70</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>吡啶</td><td></td><td></td><td></td><td>70</td><td></td><td></td><td></td><td></td></tr><tr><td>三乙胺</td><td></td><td>一</td><td></td><td></td><td>70</td><td></td><td></td><td></td><td></td></tr><tr><td>表面</td><td>C</td><td>氢氧化钠 RapizolA-80 （换算成纯品量）</td><td>质量份</td><td></td><td></td><td></td><td></td><td></td><td>70</td><td></td><td></td></tr><tr><td colspan=\"2\">活性剂 其他</td><td rowspan=\"4\"></td><td rowspan=\"4\">（以单体（A1）、（A2）、（A3）及 （A4）的总量为100计）</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td></tr><tr><td>BYK333</td><td>0.1</td><td>0.1</td><td>0.1</td><td>0.1</td><td>0.1</td><td>0.1</td><td>0.1</td><td>0.1</td></tr><tr><td>NPA</td><td></td><td></td><td></td><td>500</td><td></td><td></td><td>500</td><td>500</td></tr><tr><td></td><td>500</td><td>400</td><td>500</td><td></td><td>500</td><td>500</td><td></td><td></td></tr><tr><td rowspan=\"6\" colspan=\"2\">溶剂 评价结果</td><td>耐雾浊性</td><td></td><td>?</td><td>?</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>固化所需时间</td><td>10分钟</td><td>10分钟</td><td>10分钟</td><td>10分钟</td><td>20分钟</td><td>40分钟</td><td>10分钟</td><td></td><td>40分钟</td></tr><tr><td></td><td>粘附性（PC）</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>?</td><td></td></tr><tr><td></td><td>粘附性（PMMA）</td><td></td><td>##</td><td>#</td><td></td><td></td><td></td><td>##</td><td>##</td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>防雾性 耐热性</td><td>##</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n[0114] （1）耐雾浊性的评价[0115] 在设定为 $30^{\\circ}\\mathrm{C}\\ 、60\\sim90\\%$ RH任意相对湿度的环境下，用喷涂法将上述防雾涂料组合物涂饰在聚碳酸酯树脂板上，使固化后的涂膜厚度为 $2\\sim3~\\upmu\\textrm{m}$ ，涂饰后直接在同样环境下放置30分钟。然后在 $80^{\\circ}\\mathrm{C}$ 下加热固化10分钟，获得涂膜试验片。在 $60\\sim90\\%$ 范围内的各种相对湿度RH下，采用上述方法制备了涂膜试验片。用肉眼观察涂膜外观，确定没有看到白化等外观异常的最大相对湿度，按照下面四级进行评价。并且，如果评价为 $\\times$ ，则在应用上存在问题；如果是 $\\bigtriangleup$ ，则在应用上没有问题；如果是 $\\bigcirc$ ，则更优选，如果是 $\\circledcirc$ ，则非常优选。  \n\n[0116] $\\circledcirc$ :在相对湿度设定为 $90\\%$ 的环境下能够获得无色透明的涂膜。  \n[0117] $\\bigcirc$ ：相对湿度设定为 $80\\%$ 的环境下能够获得无色透明的涂膜。  \n[0118] $\\bigtriangleup$ ：相对湿度设定为 $70\\%$ 的环境下能够获得无色透明的涂膜。  \n[0119] $\\times$ ：相对湿度设定为 $60\\%$ 的环境下能够获得无色透明的涂膜。  \n[0120] (2）固化所需时间的评价  \n[0121] 用喷涂法将上述防雾涂料组合物涂饰在聚碳酸酯树脂板上，使固化后的涂膜厚度为 $2\\sim3~\\upmu\\textrm{m}$ ，在 $30^{\\circ}\\mathrm{C}$ 下干燥1分钟后，在 $80^{\\circ}\\mathrm{C}$ 下,于 $10\\sim90$ 分钟任意时间内实施加热固化，获得涂膜试验片。固化时间在10分钟、20分钟、40分钟、60分钟及最长为90分钟的范围内变化,将获得的涂膜在 $40^{\\circ}\\mathrm{C}$ 温水中浸渍240小时后，在室温下干燥1小时，用肉眼观察干燥后的涂膜外观并进行评价。上述温水浸渍后的涂膜外观与试验前没有发生变化的最小固化时间为固化所需时间。如果固化所需时间在40分钟之内，则在应用上没有问题；如果在20分钟之内，则为更优选；如果在10分钟之内，则为非常优选。  \n[0122］（3）涂膜性能的评价  \n[0123]用喷涂法将上述防雾涂料组合物涂饰在聚碳酸酯树脂板及丙烯酸树脂板上，使固化后的涂膜厚度为 $2\\sim3~\\upmu\\textrm{m}$ ，在 $30^{\\circ}\\mathrm{C}$ 下干燥1分钟后，在 $80^{\\circ}\\mathrm{C}$ 下，于上述固化所需时间的条件下进行加热固化，获得涂膜试验片。  \n[0124]（粘附性（PC))  \n[0125]将每个形成于上述聚碳酸酯树脂（PC）板上涂膜试验片，将涂膜切割成长1cm，宽1cm的区域，区域之间纵横分别间隔1mm,共制备100个格子。在每个格子表面压附玻璃纸，用肉眼观察急速剥离时的外观，按照下面四级进行评价。如果评价为 $\\times$ ，则在应用上存在问题；如果是，则在应用上没有问题；如果是O，则更优选；如果是 $\\circledcirc$ ，则非常优选。  \n[0126] $\\circledcirc$ ：完全没有发生剥离。  \n[0127] $\\bigcirc$ ：在切割的交叉点上，确认为有稍微剥离。  \n[0128] $\\bigtriangleup$ ：确认为一部分剥离。  \n[0129] $\\times$ :完全剥离。  \n[0130] （粘附性（PMMA)）  \n[0131] 除了将树脂板变更为丙烯酸树脂（PMMA）板之外，采用与上述粘附性（PC)同样的方法进行评价。  \n[0132] （防雾性）  \n[0133]将形成于上述聚碳酸酯树脂板或丙烯酸树脂板上的涂膜试验片设置在离保持为$80^{\\circ}\\mathrm{C}$ 的温水浴的距水面5cm的高度处，使试验片的涂膜面朝下，使从温水浴中产出的蒸汽连续照射在涂膜上，通过肉眼观察照射起10秒后有没有结雾，然后按照下面五级进行评价。如果评价为 $\\times$ 或 $\\times\\times$ ，则在应用上存在问题；如果是△，则在应用上没有问题；如果是$\\bigcirc$ ，则更优选；如果是 $\\circledcirc$ ，则非常优选。  \n[0134] $\\circledcirc$ ：完全不认为有结雾。  \n[0135] $\\bigcirc$ ：用蒸汽照射后，仅稍稍在瞬间出现结雾，之后不认为有结雾。  \n[0136] $\\bigtriangleup$ ：认为稍有结雾，或者不认为有结雾，但涂膜表面不光滑，粗糙。  \n[0137] $\\times$ ：明显认为由结雾。  \n[0138] $\\times\\times$ ：由于涂膜固化不足，在照射蒸汽后，涂膜马上白化。  \n[0139] （耐热性）  \n[0140] 将形成于上述聚碳酸酯树脂板上的涂膜试验片在 $120^{\\circ}\\mathrm{C}$ 气氛条件下，放置240小时后，在室温下冷却1小时。冷却后实施上述防雾性试验，进行了相同的评价。  \n[0141］［实施例 $2\\sim8]$   \n[0142］除了将碱性化合物(B）的种类和相对于单体（A2）的磺酸基的添加量按照表2所示进行变更之外，其余按照与实施例1相同的方法制备共聚物溶液，然后制备防雾涂料组合物，分别进行评价，结果如表2所示。并且，各实施例中使用的碱性化合物(B)的物理性质如表1所示。  \n[0143］［实施例 $9\\sim17_{-}^{-}$ 一  \n[0144]除了变更为表3所示的成分及其配比之外，其余按照与实施例1相同的方法制备共聚物溶液，然后制备防雾涂料组合物，分别进行评价，结果如表3所示。  \n\n<html><body><table><tr><td colspan=\"11\">表3</td></tr><tr><td colspan=\"4\">单位</td><td colspan=\"2\"></td><td colspan=\"2\">实施例</td><td colspan=\"4\"></td></tr><tr><td rowspan=\"6\">形成共</td><td>A1</td><td>N-MAA</td><td rowspan=\"6\">质量份 （以单体（A1）、（A2）及（A3）</td><td>9 3</td><td>10 20</td><td>11</td><td>12</td><td>13</td><td>14 20</td><td>15 10</td><td>16</td><td>17 10</td></tr><tr><td>A2</td><td>AMPS</td><td>12</td><td>10</td><td>12 3</td><td>10 20</td><td>3</td><td></td><td>10</td><td>10</td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>3</td><td>20</td><td></td><td>10</td><td>10</td></tr><tr><td>聚物的</td><td>MMA</td><td>65</td><td>60</td><td>65</td><td>60</td><td>70</td><td>60</td><td></td><td>60</td><td>60</td></tr><tr><td>A3</td><td>2-EHMA</td><td></td><td></td><td></td><td></td><td></td><td></td><td>60</td><td></td><td></td></tr><tr><td></td><td>BA</td><td>20</td><td>10</td><td>20</td><td>10</td><td>24</td><td></td><td>20</td><td>20</td><td>20</td></tr><tr><td>碱性</td><td>A4</td><td>DMAA 三乙醇胺</td><td>20</td><td>10</td><td>20</td><td>10</td><td>20</td><td>10</td><td>20</td><td>20</td><td>20</td></tr><tr><td>化合物</td><td>B</td><td>咪唑</td><td>70 （相对于单体（A2）的磺酸基）</td><td>90</td><td>70</td><td>. 90</td><td>70</td><td>90</td><td>80</td><td>70</td><td>70 一</td></tr><tr><td>面</td><td>C</td><td>(换</td><td>质量份 （以单体（A1）、(A2)、(A3）</td><td></td><td>8</td><td>8</td><td></td><td>8</td><td></td><td>0.5</td><td></td></tr><tr><td colspan=\"2\">其他</td><td rowspan=\"4\">及（A4）的总量为100计） 耐雾浊性</td><td rowspan=\"2\"></td><td>8</td><td>8</td><td></td><td></td><td></td><td>8</td><td>8</td><td></td><td>30</td></tr><tr><td>BYK333</td><td>0.1</td><td>0.1</td><td>0.1</td><td>0.1</td><td>0.1</td><td>0.1</td><td>0.1</td><td>0.1</td><td>0.1</td></tr><tr><td>溶剂</td><td>PPM</td><td>500</td><td>400</td><td>500</td><td>400</td><td>500</td><td>500</td><td>500</td><td>500</td><td>500</td></tr><tr><td colspan=\"2\"></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td rowspan=\"6\">评价结果</td><td colspan=\"3\"></td><td></td><td></td><td></td><td>#</td><td>△#</td><td></td><td></td><td></td></tr><tr><td></td><td>固化所需时间</td><td>20分钟</td><td>10分钟</td><td>20分钟</td><td>10分钟</td><td>40分钟</td><td>10分钟</td><td>10分钟</td><td>10分钟</td><td>10分钟</td></tr><tr><td></td><td>粘附性（PC）</td><td></td><td>###</td><td>##</td><td></td><td>##</td><td>A</td><td>#</td><td></td><td></td></tr><tr><td></td><td>粘附性（PMMA）</td><td></td><td>Q</td><td></td><td>A</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>防雾性</td><td></td><td></td><td></td><td></td><td>##</td><td></td><td></td><td>A</td><td></td></tr><tr><td></td><td>耐热性</td><td></td><td>△</td><td></td><td></td><td></td><td>△</td><td></td><td>△</td><td>#</td></tr></table></body></html>  \n\n[0145]  \n\n[0146] 并且，表2及表3中的简略标记表示的意思如下。[0147] N-MAA： $\\mathrm{N-}$ 羟甲基丙烯酰胺  \n\n[0148] AMPS: $2-$ 丙烯酰胺 $-2-$ 甲基丙磺酸 [0149] MMA：甲基丙烯酸甲酯 [50] 2-EHMA：甲基丙烯酸2-乙基己酯  \n\n[0151］BA：丙烯酸正丁酯  \n[0152] DMAA :N, $\\mathrm{N-}$ 二甲基丙烯酰胺  \n[0153] NPA：正丙醇  \n[0154] PGM：丙二醇单甲醚  \n[0155] 如表2所示，在实施例1、2的防雾涂料组合物中，碱性化合物(B)，其为上述pKb 分别为6.2、7.1,沸点分别为 $335^{\\circ}\\mathrm{C}\\cdot256^{\\circ}\\mathrm{C}$ 的三乙醇胺或咪唑，共聚物的组成及各成分的含量在更优选范围内。因此,实施例1、2的防雾涂料组合物具有非常优异的耐雾浊性，能够在低温且短时间的条件下进行加热固化，具有非常优异的涂膜性能。  \n[0156]实施例3的防雾涂料组合物中，碱性化合物（B）为 pKb 4.1、沸点 $144^{\\circ}\\mathrm{C}$ 的二乙氨基乙醇,碱性化合物 (B)的沸点比实施例1的情况还低，因此实施例3的防雾涂料组合物与实施例1相比，其耐热性略差。  \n[0157]实施例4中，碱性化合物（B）为pKb8.8、沸点 $115^{\\circ}\\mathrm{C}$ 的吡啶,碱性化合物(B)的沸点比实施例1的情况还低，因此实施例4与实施例1相比，耐热性差，但在应用上不存在问题。  \n[0158]实施例5中，碱性化合物（B）为pKb3.2、沸点 $90^{\\circ}\\mathrm{C}$ 的三乙醇胺,碱性化合物(B）的pKb比实施例1的情况稍低，因此实施例5与实施例1相比，固化所需时间稍微延长。并且，实施例5中碱性化合物(B)的沸点比实施例1的情况还低，因此与实施例1相比耐热性差，但在应用上不存在问题。  \n[0159]实施例6中，碱性化合物（B）为pKb0.2、沸点 $1390^{\\circ}\\mathrm{C}$ 的氢氧化钠,碱性化合物 (B)的 pKb 比实施例1的情况还低，因此实施例6与实施例1相比，固化所需时间延长,但在应用上不存在问题。  \n[0160]实施例7中，由于作为碱性化合物(B)的三乙醇胺的使用量为优选范围的下限值，因此实施例7与实施例1的情况相比，耐雾浊性略差，耐热性差，但在应用上不存在问题。[0161]实施例8中，由于作为碱性化合物(B)的三乙醇胺的使用量为优选范围的上限值，因此实施例8与实施例1的情况相比，固化所需时间延长，但在应用上不存在问题。[0162]如表3所示,实施例9中，单体（A1）的含量为优选范围的下限值，因此共聚物的固化性降低，固化所需时间稍微延长。  \n[0163]实施例10中，单体（A1）的含量为优选范围的上限值，因此共聚物的交联密度变高，涂膜的防雾性降低，并且耐热性降低，但在应用上不存在问题。  \n[0164]实施例11中，单体(A2)的含量为优选范围的下限值，因此可见共聚物的亲水性和固化性降低，耐雾浊性降低，固化所需时间稍微延长，但在应用上不存在问题。  \n[0165]实施例12中，单体（A2）的含量为优选范围的上限值，因此可见共聚物的极性变高,涂膜与基材间的亲和性降低，结果使粘附性降低，且耐热性降低，但在应用上不存在问题。  \n[0166］实施例13中，单体（A1）及单体（A2）的总量为优选范围的下限值，单体（A3）的含量为优选范围的上限值，因此可见共聚物的亲水性和固化性降低，耐雾浊性降低，固化所需  \n\n时间延长，但应用上不存在问题。  \n\n[0167］实施例14中，单体（A1）及单体（A2）的总量为优选范围的上限值，单体（A3）的含量为优选范围的下限值。因此可见共聚物的极性变高，涂膜与基材间的亲和性降低，结果使粘附性降低，防雾性降低，且共聚物的交联密度变高，涂膜的防雾性降低，并且耐热性降低，但在应用上不存在问题。  \n\n[0168]实施例15中，通过将实施例1中用作单体（A3）的MMA（烷基酯的烷基的碳原子数为1）替换为2-EHMA（烷基酯的烷基的碳原子数为8)，从而使共聚物的亲水性降低，耐雾浊性降低，但在应用上不存在问题。  \n\n[0169］实施例16中，表面活性剂（C)的含量为优选范围的下限值，因此与实施例1相比，形成水膜的能力降低，防雾性降低，但在应用上不存在问题。  \n\n[0170］实施例17中，表面活性剂（C)的含量为优选范围的上限值，因此与实施例1相比，粘附性降低，但在应用上不存在问题。",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# （19)中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n<html><body><table><tr><td>(21)申请号 201280062264.9 C·M·伊利塔罗M·B·阿里 A·J·库格尔S·P·斯旺森 (22)申请日2012.11.01 (74)专利代理机构北京市金杜律师事务所 (65)同一申请的已公布的文献号 11256 申请公布号 CN 104080861 A</td></tr></table></body></html>",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n包含水性聚合物分散体、交联剂和聚环氧烷的酸或盐的防雾涂料",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明描述了一种涂料组合物，所述涂料组合物包含水性聚合物分散体；交联剂;以及聚环氧烷的酸或盐。本发明还描述了包含设置在基底上的干燥并固化的涂料组合物的制品以及在基底上提供防雾涂料的方法。  \n\n1.一种涂料组合物，包含：水性聚合物分散体;交联剂，其中所述交联剂的浓度不大于所述涂料组合物的固体的25重量 $\\%$ ;和聚环氧烷的酸或盐，其中所述聚环氧烷的酸或盐的浓度不大于所述涂料组合物的固体  \n的40重量 $\\%$ o2.根据权利要求1所述的涂料组合物，其中干燥并固化的涂料组合物包含至少40重  \n量 $\\%$ 的含羧酸酯的聚合物，所述聚合物选自聚氨酯聚合物、丙烯酸聚合物、或它们的混合  \n物。3.根据权利要求2所述的涂料组合物，其中所述含羧酸酯的聚合物包含碳酸酯部分。4.根据权利要求1所述的涂料组合物，其中所述聚环氧烷包含10至100个重复单元，所  \n述重复单元选自环氧乙烷、环氧丙烷、或它们的组合。5.根据权利要求4所述的涂料组合物，其中所述聚环氧烷包含仅环氧乙烷重复单元或  \n其中环氧乙烷重复单元与环氧丙烷重复单元的比率为至少2:1的组合。6.根据权利要求1所述的涂料组合物，其中所述交联剂包含氮丙啶交联剂、pH敏感性碳  \n酸酯交联剂、碳二亚胺交联剂、或它们的混合物。7.根据权利要求6所述的涂料组合物，其中所述氮丙啶交联剂包含环氧烷重复单元。8.根据权利要求1所述的涂料组合物，其中所述交联剂是氮丙啶交联剂，所述氮丙啶交  \n联剂的浓度是所述涂料组合物的固体的至少10重量 $\\%$ 09.根据权利要求1所述的涂料组合物，其中所述涂料组合物还包含表面活性剂。10.根据权利要求9所述的涂料组合物，其中所述表面活性剂为非离子表面活性剂。11.根据权利要求10所述的涂料组合物，其中所述表面活性剂包含聚环氧烷重复单元。12.根据权利要求9所述的涂料组合物，其中所述涂料组合物包含有机硅表面活性剂、  \n离子表面活性剂、或它们的混合物。13.根据权利要求1所述的涂料组合物，其中干燥并固化的涂料组合物包含无机氧化物  \n纳米粒子。14.根据权利要求13所述的涂料组合物，其中所述无机氧化物纳米粒子包含二氧化硅  \n纳米粒子。15.根据权利要求14所述的涂料组合物，其中所述纳米粒子包含硅烷表面处理，所述硅  \n烷表面处理包含水分散性基团。16.根据权利要求1所述的涂料组合物，其中干燥并固化的涂料组合物在浸泡于 $50^{\\circ}\\mathrm{C}$ 的  \n水中24小时后在60秒内不表现出起雾。17.根据权利要求1所述的涂料组合物，其中干燥并固化的涂料组合物在浸泡于 $50^{\\circ}\\mathrm{C}$ 的  \n水中24小时或 $65\\mathrm{^\\circC}$ 的水中120小时后在60秒内不表现出起雾。18.根据权利要求1所述的涂料组合物，其中固化的涂料组合物具有至少 $90\\%$ 的透射  \n率。19.一种制品，包含基底以及干燥并固化的权利要求1-18中任一项的涂料组合物。20.根据权利要求19所述的制品，其中所述基底为透光的或不透明的。21.根据权利要求20所述的制品，其中所述基底为不锈钢、纤维板、或聚氯乙烯。22.一种在基底的表面上提供防雾涂料的方法，所述方法包括：  \n\n提供根据权利要求1-18中任一项的涂料组合物;将所述涂料组合物施涂到基底；以及干燥并固化所述涂料组合物。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 包含水性聚合物分散体、交联剂和聚环氧烷的酸或盐的防雾涂料",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 背景技术  \n\n[0001］如例如在美国专利No.7,008,979中所述，雾形成在高湿度和高温条件下或在存在大的温度和湿度差的界面边界处发生。已经提出据报告降低表面“起雾\"趋势的涂料(即防起雾涂料)。  \n\n[0002]为防止该起雾，已知的是使用各种表面活性剂以向制品提供防雾特性。例如,已将亲水性试剂添加到聚氨酯中以赋予防雾特性。已提出用于透明表面的防雾涂料组合物，这些防雾涂料组合物包含三维交联的聚氨酯，在其交联结构中的开放域内设有游离的表面活性剂。所述涂料组合物通过以下方法制备：使异氰酸酯与多官能多元醇反应以获得聚氨酯，并且随后使因而制得的聚氨酯与亲水性表面活性剂接触以便使表面活性剂的分子扩散到涂料的内部中。(参见例如授予Radisch等人的美国专利No.4,551,484和4,609,688)。  \n\n[0003]然而，表面活性剂并非通过化学反应进入聚氨酯，而是以物理方式设置在聚合物结构内。因此，固化的涂料易发生表面活性剂的不可取的浸出和腐蚀，从而减弱涂料组合物的防雾特性。  \n\n[0004]还已提议使表面活性剂反应进入聚氨酯涂料组合物中以便向涂料组合物赋予防雾特性。例如，已提出向聚氨酯添加磺化“树脂\"以便制备具有各种特性(包括防雾特征)的涂料。所述树脂通过二醇或二胺与二羧酸酯反应随后使双键磺化或使胺季化而制得。所述树脂旨在通过以首尾相连的方式反应进入聚氨酯主链而非作为侧基来提高聚氨酯涂料的亲水性特征和吸水性。以首尾相连的方式反应而非保持侧接在聚氨酯链的末端处的此类树脂不能提供亲水性基团与疏水性基团的明确划分，并且在该方面不作为表面活性剂发挥作用,即它们不提供不同亲水性部分与疏水性部分之间的合作以减小界面张力。(参见例如授予Blair等人的美国专利No.3,822,238)。  \n\n[0005]还已提出可用作透明基底的涂料的聚氨酯组合物，其具有改善的自行复原特性并防止形成表面水分。所述聚氨酯组合物由异氰酸酯与多元醇混合物(包含双官能磺化聚醚多元醇和三官能多元醇)的反应而制备。此类聚氨酯组合物仅掺入赋予涂料亲水性特征的多元醇组合，并且不进一步在组合物中掺入表面活性剂材料。(参见例如授予Fock等人的美国专利No.4,754,152)。  \n\n[0006]然而，这些组合物既不提供永久抗雾特性(即在反复洗涤或在水中长时间浸泡后维持的抗雾特性)，也不在使用超过几小时后有效。  \n\n[0007]另外，已知的是，向用作为亲水剂的聚乙烯吡咯烷酮制备的聚氨酯中掺入含有反应性官能团的非离子表面活性剂。例如，已知掺有异氰酸酯预聚物的防雾涂料组合物，该异氰酸酯预聚物与聚乙烯吡咯烷酮聚合物反应，其反应产物随后与具有与异氰酸酯反应的反应性基团(例如羟基反应性基团)的非离子表面活性剂反应。然而，聚乙烯吡咯烷酮聚合物尽管有助于增大聚氨酯基质的亲水性并改善防雾特性，但是一般降低固化的聚氨酯表面的耐刮性、耐化学品性、水敏感性和耐久性。因此，尽管已知这些组合物在固化时提供防雾特性，但是其溶剂敏感性、柔韧性和耐刮特性不够理想。(参见例如授予Creasy的美国专利  \n\nNo.4,467,073)。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 发明内容  \n\n[0008]尽管已描述了各种防雾涂料，但是工业上将发现可提供持续耐久防雾特性的替代性组合物的优点。  \n\n[0009]在一个实施例中，描述了一种涂料组合物，该涂料组合物包含水性聚合物分散体；交联剂;以及聚环氧烷的酸或盐。  \n[0010］还描述了包含设置在基底上的干燥并固化的涂料组合物的制品以及在基底上提供防雾涂料的方法。具体实施方式  \n[0011]本文所述的涂料组合物适于赋予防雾特征。该涂料组合物包含水性聚合物分散体，通常为可制备为胶乳的水性聚合物分散体，并且更典型为可制备为碱性pH稳定胶乳的水性聚合物分散体。有利的聚合物分散体包括聚氨酯聚合物分散体、丙烯酸聚合物分散体、以及它们的混合物。此类聚合物通常为热塑性的。  \n[0012]术语\"聚氨酯\"包括包含聚氨酯链段的任何聚合物材料。术语\"聚氨酯链段”是指通过有机基团连接的至少两个氨基甲酸酯和/或脲基团。  \n[0013]术语\"丙烯酸\"包括丙烯酸、甲基丙烯酸、这些酸的酯或丙烯腈的任何聚合物或共聚物。  \n[0014]热塑性聚氨酯组合物一般为二异氰酸酯与短链二醇 (也称为扩链剂)以及二异氰酸酯与长链双官能二醇(称为多元醇)的反应产物。聚氨酯的特征为具有连接衍生自二异氰酸酯和二醇的链段的氨基甲酸酯基团，即 $-\\mathrm{NH}-\\left(\\mathrm{C}=0\\right)-0-\\mathrm{{c}}$ 此类氨基甲酸酯基团包含基基团，即碳原子以双键键合到氧原子 $({\\mathsf{C}}{=}0)$ 。  \n[0015]长链多元醇的非限制性例子为聚醚多元醇、聚酯多元醇、丙烯酸多元醇以及此类多元醇的混合物。通常，基于聚酯的热塑性氨基甲酸酯因提供良好的耐磨性和耐化学品性而已知。最终的树脂由嵌段结构的线性聚合物链组成。此类链含有低极性链段(称为\"软链段\")，其与较短的、高极性链段(称为\"硬链段\")交替。两种类型的链段通过共价键连接在一起，从而形成无规共聚物或嵌段共聚物。  \n[0016]聚酯多元醇通过用有机多元醇和/或环氧化物使有机聚羧酸或其酸酐聚酯化而制备。通常，聚羧酸和多元醇为脂族或芳族二元酸和二醇。制备聚酯中通常采用的二醇包括但不限于无环亚烷基二醇(诸如乙二醇和新戊二醇)以及环状二醇(诸如氢化双酚A、环己二醇和环己烷二甲醇)。还可使用更高官能度的多元醇。非限制性例子包括三羟甲基丙烷和季戊四醇以及更高分子量的多元醇，诸如通过使低分子量多元醇氧烷基化而制备的那些。[0017]聚酯的酸组分主要由每分子具有2至18个碳原子的单体羧酸或酸酐组成。可使用的酸为邻苯二甲酸、对苯二甲酸、六氢邻苯二甲酸、己二酸、壬二酸、癸二酸、马来酸、戊二酸、氯菌酸、癸酸和十二烷酸。还可使用高级聚羧酸，诸如偏苯三酸和丙三羧酸。在上文提及酸时，应当理解，还可使用形成酸酐的那些酸的酸酐来替代酸。另外，可使用酸的低级烷基酯，诸如戊二酸二甲酯和对苯二甲酸二甲酯。  \n[0018]除聚酯多元醇外，还可使用含有羟基的丙烯酸聚合物或丙烯酸多元醇作为多元醇  \n\n组分。  \n\n聚醚多元醇的例子为聚亚烷基醚多元醇，包括具有以下通式的那些：  \n\n[0020]  \n\n[021］其中取代基R为氢或含有1至5个碳原子的低级烷基(包括混合的取代基)，并且n通常为2至6,并且m为10至100或甚至更高。包括的是聚(氧四亚甲基)二醇、聚(氧乙烯)二醇、聚 (氧-1,2-丙烯)二醇以及乙二醇与1,2-环氧丙烷和环氧乙烷混合物的反应产物。  \n\n[0022]可使用的聚异氰酸酯包括芳族和脂族聚异氰酸酯，其中脂族聚异氰酸酯由于其优异的紫外光稳定性和不发黄趋势而更理想。此类聚异氰酸酯的非限制性例子包括单体聚异氰酸酯，诸如甲苯二异氰酸酯和4,4'-亚甲基-双-(环己基异氰酸酯)、异佛乐酮二异氰酸酯;以及NCO预聚物，例如单体聚异氰酸酯(诸如上述那些)与聚酯或聚醚多元醇的反应产物。尤其理想的是得自异佛乐酮异氰酸酯和1,6-六亚甲基二异氰酸酯(两者均可商购获得)的异氰脲酸酯。  \n\n[0023]在一些实施例中，聚氨酯分散体包含聚酯主链、聚碳酸酯主链、聚酯碳酸酯、或它们的组合。在其它实施例中，丙烯酸分散体包含丙烯酸主链、含羟基的丙烯酸主链、或它们的组合。在其它实施例中，聚合物分散体为氨基甲酸酯-丙烯酸杂化物、或聚碳酸酯氨基甲酸酯/丙烯酸杂化物。在一些实施例中，将聚合物描述为具有聚碳酸酯或碳酸酯主链。在此类实施例中，聚合物包含脂族或芳族碳酸酯部分，诸如双酚A碳酸酯部分。  \n\n[0024]已开发多种方法来制备水基或水性聚合物分散体。在水性聚氨酯聚合物的制备中，通常通过合适的二醇或多元醇与摩尔过量的二异氰酸酯或聚异氰酸酯在内部乳化剂的存在下反应而形成中等分子量的聚合物(例如预聚物)。内部乳化剂通常为具有离子基团(羧酸盐、磺酸盐或季铵盐)或非离子基团的二醇，诸如聚环氧乙烷。根据聚氨酯主链中所存在的亲水性链段的类型，水性聚氨酯分散体通常为三种类型 (即非离子、阳离子和阴离子)之一。就阴离子聚氨酯而言，由于其在后续与三乙胺的中和反应中对于水分散体的效果，常常向聚氨酯主链中掺入二羟甲基丙酸(DMPA)。聚合物中DMPA的羧酸根离子为亲水的并用作阴离子中心以及内部乳化剂。羧基离子不仅使水性聚氨酯分散体稳定，而且提供固化位点。水性丙烯酸聚合物还通常用内部乳化剂制备，并且因此通常还包含羧酸根离子以稳定分散体并提供固化位点。  \n\n[0025]一般将(例如聚氨酯和/或丙烯酸)聚合物分散于液体稀释剂中以形成聚合物分散体。\"液体稀释剂”是指为挥发性的并在施加涂料后移除的溶剂。在有利的实施例中，涂料组合物主要包含水作为稀释剂，具有很少的有机溶剂或无有机溶剂。在该实施例中，有机溶剂的浓度通常小于涂料组合物的2重量 $\\%.1.5$ 重量 $\\%.1$ 重量 $\\%$ 或0.5重量 $\\%$ 。将可以商品名“W835Series\"购自Incorez的聚氨酯分散体称为无共溶剂级聚氨酯分散体。  \n\n[0026］分散于水性稀释剂中的(例如聚氨酯和/或丙烯酸)聚合物为成膜聚合物。合适的聚合物胶乳以及制备它们的方法是本领域中广泛已知的，并且许多可商购获得。  \n\n[027］通常，聚合物胶乳中的粒子的形状基本上为球形。聚合物核可包含一种或多种水不溶性聚合物，但这不是必要条件。可用的聚合物粒度包括胶乳和其它分散体或乳液的典型的那些。典型的聚合物粒度在约0.01微米至100微米的范围内，优选在0.01至0.2微米的  \n\n范围内，但这不是必要条件。  \n\n[0028]可商购获得的水性脂族聚氨酯乳液的例子包括得自美国马萨诸塞州威明顿帝斯曼利康树脂有限公司(DSM NeoResins,Inc.(Wilmington,MA)）的NEOREZ R-960、NEOREZ R-967、NEOREZ R-9036和NE0REZ R-9699;可以ESSENTIAL CC4520、ESSENTIAL CC4560、ESSENTIAL R4100和ESSENTIAL R4188购自威斯康辛州默顿的基础工业有限公司(Essential Industries,Inc．(Merton,WI)）的水性阴离子聚氨酯分散体；可以SANCURE843、SANCURE898和SANCURE12929购自俄亥俄州克利夫兰的路博润有限公司(Lubrizol,Inc.(Cleveland,0H)）的聚酯聚氨酯分散体;可以TURB0SET2025购自路博润有限公司(Lubrizol,Inc.)的水性脂族自交联聚氨酯分散体;可以“INCOREZ\"购自英国兰开夏郡的Incorez公司(Incorez Co.,Lancashire,England)的聚氨酯分散体;以及可以商品名“RU-077\"和\"RU-075\"购自马萨诸塞州皮博迪的斯塔尔美国公司(Stahl USA,Peabody,MA)的聚氨酯分散体。  \n\n[0029]自交联聚合物分散体可用于墨接受层中。此类聚合物分散体具有自交联功能，该功能在干燥涂层时激活。使用该类型的分散体可消除向涂料组合物中掺入交联化合物的需要。自交联聚合物分散体的例子包括可以\"BAYHYDROLPR240\"购自宾夕法尼亚州匹兹堡的拜耳材料科学有限公司(Bayer Material Science,LLC(Pittsburgh,PA)）以及以\"NEOREZR-661\"购自帝斯曼利康树脂有限公司(DSMNeoresins)的聚氨酯分散体。  \n\n[0030]］可商购获得的水性脂族丙烯酸乳液的例子包括可以商品名ROSHIELDTM和RHOPLEXTM购自陶氏涂料材料公司(Dow Coating Materials)的丙烯酸胶乳，诸如\"ROSHIELD $^\\mathrm{TM_{3188},*}$ 、“ROSHIELDTM3275”、“ROSHIELDM1024\"、“ROSHIELD $^\\mathrm{TM}636^{3,3}$ 、“RHOPLEXTMWL-96\"和\"RHOPLEXTMCL-104”；可以商品名“UCART\"购自阿科玛涂料树脂公司（ArkemaCoatingResins)的丙烯酸胶乳，诸如“UCARTMLATEX455”、“UCARTMLATEX443”、“UCARTMLATEX451\"和\"UCARTMLATEXDM109”；可以商品名HYCAR?购自路博润先进材料公司（LubrizolAdvanced Materials,Inc.）的丙烯酸胶乳,诸如“HYCAR?26349”、“HYCAR?$26459^{3}$ ；以及可以商品\"NEOCRYL\"购自帝斯曼利康树脂有限公司(DSM Neoresins)的丙烯酸胶乳，诸如\"NE0CRYL A-640”、\"NE0CRYL XK-220”、\"NEOCRYL A-1044”、\"NE0CRYL XK-90”、“NEOCRLYL XK-96\"和\"NEOCRYL XK-95”。  \n\n[0031]］聚氨酯聚合物的分散体可通过测量由分散体形成的净聚氨酯的50-100微米薄膜(在 $22\\%$ H下干燥14天)的特性来表征。在一些实施例中，由此形成的薄膜的伸长率通常具有范围为约 $500\\%$ 至约 $60\\%$ 的断裂伸长率。在一些实施例中，拉伸强度范围为约15至$\\mathrm{30MPa}$ 0  \n\n[0032]在一些实施例中，丙烯酸分散体包含聚丙烯酸酯主链、聚碳酸酯主链、或它们的组合。  \n\n[0033]聚合聚合物的组合可在(例如防雾)涂料组合物中利用。例如，聚氨酯分散体可包含两种或更多种具有不同平均分子量的聚氨酯聚合物。此外，组合物可包含不同类型的聚合物与聚氨酯的组合，例如通过混合丙烯酸胶乳与聚氨酯胶乳将获得。在一个实施例中，水性聚氨酯分散体包含“INCOREZW835/140\"与\"NE0REZR-961”的混合物。包含\"NEOREZ R-961\"可改善耐磨性。然而，当\"NE0REZR-961\"的浓度超过约1:2的重量比（即，每2重量份“INCOREZW835/140\"超过1重量份\"NE0REZR-961\")时，涂料在水中浸泡后可变白。在另一个实例中，利用聚氨酯聚合物与丙烯酸聚合物的组合或丙烯酸与聚氨酯两者的杂化聚合物。可商购获得的丙烯酸氨基甲酸酯共聚物分散体的例子可以商品名NEOPAC购自帝斯曼利康树脂有限公司(DSMNeoresins）。  \n\n[0034]涂料组合物通常包含总量为涂料组合物固体的至少40重量 $\\%$ 并且通常不大于90重量 $\\%$ 或85重量 $\\%$ 或80重量 $9\\%$ 的一种或多种 (例如聚氨酯和/或丙烯酸)聚合物。在一些实施例中，涂料组合物包含至少45重量 $\\%$ 或50重量 $\\%$ 的量的一种或多种聚合物。  \n\n[0035]防雾涂料包含不与聚氨酯聚合物反应，但为反应性的并因此可通过(例如氮丙啶)交联剂交联的亲水性添加剂。此类亲水性添加剂的浓度通常为涂料组合物固体的至少5重量 $\\%16$ 重量 $\\%$ 、7重量 $\\%\\cdot8$ 重量 $\\%9$ 重量 $\\%$ 或10重量 $\\%$ 。在一些实施例中，亲水性添加剂的浓度为至少11重量 $\\%.12$ 重量 $\\%.13$ 重量 $\\%.14$ 董量 $\\%$ 或15重量 $\\%$ 。此类亲水性添加剂的浓度通常不大于约40重量 $\\%$ 或35重量 $\\%$  \n\n[0036]］可通过交联剂交联的亲水性添加剂的一个例子为聚环氧烷的酸或盐。此类添加剂一般包含聚环氧烷主链，其包含环氧乙烷、环氧丙烷、或它们的组合的重复单元。环氧乙烷和环氧丙烷重复单元的数目可独立地在0至100范围内，前提条件是环氧乙烷和环氧丙烷重复单元的总数范围为约10至100。聚环氧烷主链通常包含比环氧丙烷重复单元更多的环氧乙烷重复单元。在一些实施例中，环氧乙烷重复单元与环氧丙烷重复单元的比率为至少2：1、或3:1、或4:1、或5:1、或6:1、或7:1、或8:1、或9:1或10:1。聚环氧烷主链通常为直链的并为二价的，在每个末端上用酸或盐基团封端。二价连接基团通常存在于聚环氧烷主链与至少一个或两个末端酸或盐基团之间。根据起始化合物和一种或多种反应物，连接基团可变化。在一些实施例中，添加剂由聚环氧烷胺 (也称为聚醚胺)与琥珀酸酐反应形成二酸，然后二酸与烷基胺反应以将酸基团转化为铵盐基团而形成。在该实施例中，聚环氧烷主链与末端酸或盐基团之间的连接基团可为 $\\mathrm{-CH_{2}N H C O C_{2}H_{4}-}_{\\mathrm{~}}$ 然而，通过使用其它反应方案将存在其它连接基团。连接基团的分子量一般相对小，以免降低聚环氧烷主链的亲水性质。在一些实施例中，连接基团的分子量不大于 $100\\mathrm{g/mol}$ 。随着聚环氧烷主链的分子量增加，连接基团的分子量也可增加而不降低亲水特性。然而，连接基团的分子量通常不大于亲水性添加剂的总分子量的约20重量 $\\%.15$ 重量 $\\%$ 或10重量 $\\%$ (即连接基团的分子量除以总分子量乘以$100\\%$ 。  \n\n[0037］在一个实施例中，亲水性添加剂包含二价聚环氧烷主链和末端酸或盐基团，如可由下式表示：  \n\n[0038] $\\mathrm{R-L-(C_{3}H_{6}0)_{\\Delta x}(C_{2}H_{4}0)_{\\Delta y}-L-R}$   \n[0039] 其中R为能够与 (例如氮丙啶)交联剂(共价)反应的反应性基团,诸如羧酸基团或其盐，  \n[0040] L为二价连接，  \n[0041] 并且x和y独立地在0至100的范围内，前提条件是 $\\mathbf{\\nabla}_{X^{+}\\mathrm{{y}}}$ 的总和范围为约5、6、7、8、9或10至约100。  \n[0042] 连接基团L可根据反应物的选择而变化。例如，当聚环氧烷二醇与异氰酸酯化合物反应时，L可为-OCONH-。  \n[0043] 在另一个实施例中，当聚环氧烷二胺与异氰酸酯化合物反应时，L可为-NHCONH-。  \n\n在另一个实施例中，当聚环氧烷二醇与酸酐或羧酸化合物反应时，L可为- $\\cdot(\\mathrm{C}=0)-0-$ 当聚环氧烷二酸与醇化合物反应时，L还可为酯键。在另一个实施例中，通过聚环氧烷二酸或丙烯酸氯化物与伯胺或仲胺的反应，L可为-CONH-。通过聚亚烷基二胺与酸酐或羧酸化合物的反应，还可制得酰胺键。在另一个实施例中，通过聚环氧烷二胺与卤化化合物的反应或通过聚环氧烷二卤化物与胺化合物的反应，L可为-NR-。在另一个实施例中，通过聚环氧烷二醇与丙烯酰氯硫醇或硫醇酯化合物的反应，L可为 $-\\mathrm{COS^{-}}$ 。另外，通过聚环氧烷二硫醇与硫醇或琉基化合物的反应，L可为 $-\\mathrm{CS2^{-}}$ 。在另一个实施例中，通过聚环氧烷二硫醇与卤化化合物的反应，L可为 $-\\mathrm{S}-$ 。在另一个实施例中，通过聚环氧烷二醇的缩合反应，L可为 $-0-$ 。在另一个实施例中，通过聚环氧烷二硫醇与异氰酸酯化合物的反应或通过聚环氧烷二异氰酸酯与硫醇化合物的反应，L可为-SCONH-。  \n\n[0044]］酸盐的抗衡离子可为铵以及伯烷基铵、仲烷基铵或叔烷基铵。抗衡离子还可为无机金属离子，包括得自卤化锌、硝酸锌、碳酸锌或碳酸铵锌的二价锌。其它无机金属离子包括Cu、Ti和Zr。  \n\n[0045]无意于受理论的束缚，据猜测，聚环氧烷的酸或盐的环氧烷重复单元可有助于防止与此类亲水性链段相容的表面活性剂(例如包含环氧烷重复单元的非离子表面活性剂)从涂料中浸出。  \n\n[0046]本文所述的防雾涂料包含交联剂。交联剂通常与聚合物(例如聚氨酯和/或丙烯酸)主链中所存在的 (例如羧酸酯)亲水性链段反应。合适的交联剂通常包含至少三个末端(例如羧酸酯)反应性基团。  \n\n[0047］可将含羧基离子(例如羧酸根)的水性聚合物分散体和多氮丙啶固化剂配制为固化聚合物分散体。固化机制可在环境温度下在干燥过程期间当pH值降到低于6时发生。在一些实施例中，交联剂还可与如刚才所述的(例如聚环氧烷的二酸或盐)亲水性添加剂反应。  \n\n[0048]交联剂的有利例子包括可以各种商品名获得的氮丙啶交联剂，诸如在以下例子中所述;碳二亚胺交联剂，诸如可以商品名\"V-04\"购自日本日清纺株式会社(NisshinboIndustries,Inc.Japan)的那些;以及pH响应性碳酸酯交联剂,诸如以商品名\"Bacote20\"购自新泽西州夫雷明顿的锆化学有限公司(Zirconium Chemicals,Flemington,NJ)的碳酸锆铵交联剂。  \n\n[0049]其它交联剂包括脂环族环氧树脂交联剂，诸如以商品名\"ERL-4221\"购自陶氏化学公司(Dow Chemicals)；亲水性脂族聚异氰酸酯交联剂，诸如以商品名\"BH-305\"购自勒沃库森的拜耳材料科学公司(Bayer Materials Science,Leverkusen）；以及三聚氰胺交联剂，诸如以商品名XR-9174购自斯塔尔美国公司(StahlUSA)以及以商品名\"CYMEL327\"购自氰特表面特种公司(CYTEC Surface Specialties,Inc.)的那些。  \n\n[0050] 还可利用交联剂的混合物，尤其是与(例如亲水性)氮丙啶交联剂的混合物。  \n\n[0051]交联剂的浓度通常为涂料组合物固体的至少2重量 $\\%.3$ 重量 $\\%,4$ 重量 $\\%$ 或5重量 $\\%$ 。在一些实施例中，利用相对高浓度的交联剂。例如，交联剂的浓度通常为涂料组合物固体的至少10重量 $\\%$ 或15重量 $\\%$ 。交联剂的浓度通常不大于25重量 $\\%$ 、或24重量 $\\%$ 、或23重量 $\\%$ 、或22重量 $\\%$ 、或21重量 $\\%$ 或20重量 $\\%$ 0  \n\n[0052]］已知各种多官能氮丙啶交联剂,诸如三羟甲基丙烷三[β-(N-氮丙啶基)-丙酸酯]、2,2-双羟基甲基丁醇三[3-(1-氮丙啶)丙酸酯]、氮丙啶 $-2-$ 羟甲基丙烯酸酯、氮丙啶 $-2-$ 羟甲基甲基丙烯酸酯、N- (2-氮丙啶基)甲基丙烯酰胺 $\\、\\mathrm{N-}$ (2-氮丙啶基)甲基甲基丙烯酰胺、 $1^{-}$ (氮丙啶 $-2-$ 基)-2-氧杂丁 $-3-$ 烯、4-(氮丙啶 $-2-$ 基)-丁-1-烯以及 $5-$ (氮丙啶 $-2-$ 基)-戊 $^{-1-}$ 烯。这些特定氮丙咬交联剂为相对疏水的交联剂。  \n\n[0053]尤其对于其中交联剂以相对高浓度存在的实施例,利用亲水性氮丙啶交联剂而非疏水性交联剂可为有利的。一类有利的亲水性氮丙啶交联剂包含环氧烷重复单元，诸如环氧乙烷重复单元。环氧烷(例如环氧乙烷)重复单元的数目为通常至少2或3并且通常不大于约20。在一些实施例中，环氧烷(例如环氧乙烷)重复单元的数目平均为约6、7、8或9。使用亲水性交联剂对于其中组合物基本上不含或包含低浓度(不大于5重量 $\\%$ )亲水性添加剂的实施例是有利的。  \n\n[0054]］包含环氧乙烷重复单元的氮丙啶交联剂可通过使乙氧基化烷基多 (甲基)丙烯酸酯(诸如乙氧基化 (9)三甲基丙烷三丙烯酸酯)与烷基氮丙啶 (诸如2-甲基氮丙啶)反应而制备。此类氮丙啶交联剂具有通式：  \n\n![](images/8b6ba220784db74134a4c38885db839d876a422983cbefb4c35dee6111f7f332.jpg)  \n\n[0056] 其中R为氢或 $\\mathrm{C_{1}-C_{4}}$ 烷基基团;[0057] R\"为氢或甲基，[0058] $\\mathrm{~X,y~}$ 和z独立地为至少1;并且[0059] M为二价连接基团的二价原子。  \n\n[0060]在一些实施例中， $\\mathrm{{x+y+z}}$ 的总和为至少3、4、5或6。此外， $\\mathrm{{x+y+z}}$ 的总和可不大于20。  \n在一些实施例中,M为氧。  \n\n[0061］其它包含环氧烷重复单元的氮丙啶交联剂在美国专利No.8,017,666中描述;所述专利以引用方式并入本文。  \n\n[0062]无意于受理论的束缚，据猜测，交联剂的环氧烷重复单元有助于防止与此类亲水性链段相容的表面活性剂(例如包含环氧烷重复单元的非离子表面活性剂)从涂料中浸出。[0063]本文所述的(例如防雾)涂料组合物可任选地包含至少一种表面活性剂。如本文所用的术语“表面活性剂\"描述了减小涂料组合物的表面张力并提供涂料的分子，该涂料根据实例中所述的测试方法赋予涂有该涂料的基底或制品“良好的\"或\"优异的\"防雾特性。表面活性剂分子一般在相同分子上包含亲水性 (极性)和疏水性 (非极性)链段两者。  \n\n[0064]］本发明的可用表面活性剂包括离子(例如阴离子、阳离子)、非离子以及两性表面活性剂。表面活性剂可根据在其头部中存在的形式上带电的基团来分类。离子表面活性剂的头部携带净电荷。阴离子表面活性剂具有带负电的亲水性基团，诸如就烷基硫酸盐和烷基乙氧基化硫酸盐而言。阳离子表面活性剂具有带正电的亲水性基团，诸如就钠盐和季(例如铵)盐而言。非离子表面活性剂在其头部中不具有带电基团。一些例证性表面活性剂在W02009/085680中描述；所述专利以引用方式并入本文。  \n\n[0065]对于包含表面活性剂的实施例，涂料组合物中的表面活性剂浓度通常为涂料组合物的至少0.5重量 $\\%.1$ 重量 $\\%.1.5$ 重量 $\\%$ 或2重量 $\\%$ 。表面活性剂浓度通常不大于涂料组合物的10重量 $\\%$ 。  \n\n[0066]在一些实施例中，(例如防雾)涂料组合物包含非离子表面活性剂。非离子表面活性剂一般包含具有至少6、或8、或10或12个碳原子的烷基或烯基基团。此类相对长链的烷基或亚烷基基团常常被称为\"脂肪\"基团。碳原子的数目可大于18个碳原子，前提条件是非离子表面活性剂在环境温度(例如 $25\\mathrm{{^\\circC}}$ )下为液体。在一些实施例中，烷基或烯基基团具有不大于24个碳原子。在一些有利的实施例中，此类烷基基团是非支化的。烷基或烯基基团可任选地包含取代基。  \n\n[0067］多种类别的非离子表面活性剂是已知的，包括例如脂肪醇、脂肪酸、脂肪胺、脂肪酰胺、以及它们的衍生物。  \n\n[0068] 脂肪醇通常具有通式：  \n\n[0069] R-OH  \n\n[0070]］其中R为如前所述的(如,直链或支链)烷基或烯基基团,其任选地在可用位置被N、0或S原子取代。多种脂肪醇是已知的，包括十二烷醇、鲸蜡醇CH3 (CHz) $_{15}0\\mathrm{H}$ 、硬脂醇(也称为十八烷醇或1-十八醇)和油醇。  \n\n[0071］在一些实施例中，非离子表面活性剂为脂肪醇的衍生物。一种有利的衍生物为包含环氧烷重复单元(诸如环氧乙烷和/或环氧丙烷重复单元)的脂肪醇、酯或它们的衍生物。此类衍生物也可称为多乙氧基化的和/或多丙氧基化的脂肪醇、酯或它们的衍生物。多乙氧基化脂肪醇具有通式：  \n\n[0072] $\\mathrm{R-(OCH_{2}C H_{2})_{\\ n}O H}$  \n\n[0073]其中R为如前所述的(如，直链或支链)烷基或烯基基团，其任选地在可用位置被N、0或S原子取代。环氧乙烷重复单元的数目\"n\"可在2至20范围内。在一些实施例中，n为至少3或4并且不大于约10或12。  \n\n[0074]］包含聚环氧烷重复单元的表面活性剂(诸如多乙氧基化脂肪醇)可为涂料组合物的有利非离子表面活性剂。  \n\n[0075]在一些实施例中，一种或多种多乙氧基化脂肪醇为涂料组合物的唯一表面活性剂。在其它实施例中，采用至少一种多乙氧基化脂肪醇与第二表面活性剂相结合。多乙氧基化脂肪醇表面活性剂可与第二表面活性剂以约1:1或2:1的重量比结合利用。在一些实施例中，第二表面活性剂为有机硅表面活性剂、离子表面活性剂、或它们的混合物。  \n\n[0076]在一些实施例中，涂料组合物包含离子表面活性剂或有机硅表面活性剂。  \n\n[0077]有机硅表面活性剂一般包含具有各种数目的二甲基硅氧烷单元的硅氧烷主链，通常在每个末端处用三甲基硅氧烷基团封端。硅氧烷主链一般为疏水性基团。亲水性基团可为离子、两性离子或非离子，并且通常由短烷基链附接到硅氧烷主链。一种示例性硅氧烷表面活性剂为聚醚改性的硅氧烷(可以商品名\"BYK-346\"从赢讯公司(Innovadex)商购获得)。[0078]已知各种离子表面活性剂。一种示例性离子表面活性剂为a烯烃磺酸钠(可以商品名\"A-18\"从斯泰潘公司(Stepan Company)商购获得。另一种离子表面活性剂为聚氧乙烯烷基苯基醚硫酸铵(可以商品名\"Hitenol BC10\"从日本第一工业制药株式会社(Dai-IchiKogyo Seiyaku.,Ltd.,Japan)商购获得。  \n\n[0079]如前所述的各种非离子表面活性剂包含羟基基团。先前已描述了防雾涂料，其中在形成聚氨酯期间利用羟基官能表面活性剂作为反应物。(参见例如US3,822,238)。然而，在当前描述的防雾涂料组合物中，利用作为水性分散体提供的预形成(例如可商购获得的)的聚合物作为组分。分散体的聚合物通常不含羟基反应性基团。因此，当将羟基官能表面活性剂与此类聚氨酯分散体组合时，表面活性剂不与聚氨酯直接反应。换句话讲，表面活性剂不与 (例如聚氨酯和/或丙烯酸)聚合物反应。  \n\n[0080]］本文所述的防雾涂料可任选地包含各种亲水性添加剂。亲水性添加剂与表面活性剂不同，因为亲水性添加剂缺乏疏水性基团，一种表面活性剂的必需基团。在一些实施例中，涂料组合物包含小浓度的 (例如非反应性)亲水性添加剂(诸如聚乙二醇(PEG)单甲基醚)以提高防雾特性。在该实施例中，亲水性添加剂的浓度通常为至少0.5重量 $\\%$ 、或1重量 $\\%$ 、或1.5重量 $\\%$ 或2重量 $\\%$ ，并且一般不大于约5重量 $\\%$ 0  \n\n[0081] 在一些实施例中，聚环氧烷的酸或盐为涂料组合物的主要或唯一亲水性组分。  \n\n[0082］在另一个实施例中，聚环氧烷的酸或盐以及一种或多种表面活性剂为涂料组合物的主要或唯一亲水性组分。  \n\n[0083]在另一个实施例中，聚环氧烷的酸或盐以及亲水性氮丙啶交联剂为涂料组合物的主要或唯一亲水性组分。  \n\n[0084]］在另一个实施例中，涂料组合物包含聚环氧烷的酸或盐、一种或多种表面活性剂以及亲水性氮丙啶交联剂作为涂料组合物的主要或唯一亲水性组分。  \n\n[0085]在这些实施例的每一个中，涂料组合物可包含少于5重量 $\\%$ 的或无其它亲水性有机单体、低聚物或聚合物(诸如衍生自N-乙烯基吡咯烷酮的单体或聚合物)。  \n\n[0086]在一些实施例中，防雾涂料组合物不含无机纳米粒子。此类干燥并固化的组合物由于聚氨酯的选择以及相对高浓度的交联剂而通常表现出令人满意的耐磨性。  \n\n[0087]在其它实施例中，涂料组合物包含浓度为涂料组合物固体的至少0.5重量 $\\%.1$ 重量 $\\%$ 或2重量 $\\%$ 并且通常不大于约40重量 $\\%$ 的无机纳米粒子。在一些实施例中，无机纳米粒子的浓度不大于约30重量 $\\%$ 或20重量 $\\%$ 。在一些实施例中，线性磨蚀受损，尤其在纳米粒子浓度为15重量 $\\%$ 或更大时进行200或300个循环。  \n\n[0088］“纳米粒子\"在本文中定义为纳米大小的粒子，优选具有不大于100纳米、75纳米或50纳米(nm)的平均粒度。在一些实施例中，无机纳米粒子的平均粒度不大于40nm或30nm或$20\\mathrm{{nm}}$ (表面改性之前)。纳米粒子的平均粒度为至少1nm、2nm或 $3\\mathrm{{nm}}$ 0  \n\n[0089］如本文所用，“粒度\"和\"粒径\"具有相同的含义并用于指粒子(或其凝聚物)的最大尺寸。在该背景下，“凝聚”是指可通过电荷或极性保持在一起并且可分解成更小实体的粒子之间的弱缔合。  \n\n[0090]纳米粒子的平均粒度可使用透射电子显微镜测量。在本发明的实践中，可使用任何合适的技术测定粒度。粒度是指数均粒度，并且利用使用透射电子显微镜或扫描电子显微镜的仪器进行测量。测量粒度的另一种方法为测量重均粒度的动态光散射。发现合适的此类仪器的一个例子为购自加利福尼亚州富勒顿的贝克曼库尔特公司(Beckman CoulterInc.(Fullerton,CA)）的N4PLUS SUB-MICRON PARTICLE ANALYZER(N4PLUS亚微米粒子分析  \n\n仪)。  \n\n[0091]］纳米粒子的大小可相对均一。均一大小的纳米粒子一般提供更加可再现的结果。优选地，纳米粒子的大小波动小于平均粒度的 $25\\%$ 0  \n\n[0092]纳米粒子优选具有至少 $\\mathrm{10m^{2}/g}$ ，更优选至少 $\\mathrm{20m^{2}/g}$ ，并且甚至更优选至少 $\\mathrm{25m^{2}/g}$ 的 表面积。纳米粒子优选具有大于 $750\\mathrm{m^{2}/g}$ 的表面积。  \n\n[0093]本发明的纳米粒子可为多孔的或无孔的。在一些实施例中，纳米粒子仅由二氧化硅组成。二氧化硅可为优选的纳米粒子，尤其是衍生自硅酸盐(诸如碱金属硅酸盐或硅酸铵)的二氧化硅纳米粒子。在本文中，“二氧化硅纳米粒子”是指包含仅二氧化硅的纳米粒子以及具有包含二氧化硅的表面的核-壳纳米粒子。在其它实施例中，涂料组合物可包含其它无机氧化物，诸如 $\\mathrm{|Zr0_{2}}$ 、胶态氧化锆、A1203、胶态氧化铝、 $\\mathrm{Ce0_{2}}$ 、胶态二氧化铈、 $\\mathrm{{SnO_{2}}}$ 、胶态氧化锡 (四价的)和Ti02、胶态二氧化钛。还可利用此类无机氧化物的混合物。  \n\n[0094]未改性的纳米粒子通常作为分散体而非粉末提供。优选的分散体一般含有15重量 $\\%$ 至50重量 $\\%$ 的分散于流体介质中的胶态粒子。用于胶态粒子的合适流体介质的代表性例子包括水、水性醇溶液、低级脂肪醇、乙二醇、N,N-二甲基乙酰胺、甲酰胺、或它们的组合。优选的流体介质是水性的，如水和任选地一种或多种醇。水性介质中的无机二氧化硅溶胶在本领域中是熟知的并且可商购获得。水或水-醇溶液中的二氧化硅溶胶可以商品名LUDOX（由特拉华州威尔明顿的杜邦公司(E.I.duPont de Nemours and Co.,Inc.,Wilmington,DE)制造）、NYACOL（购自马萨诸塞州阿什兰的亚科尔公司(NyacolCo.,Ashland,MA)）或NALCO(由伊利诺伊州内珀维尔的纳尔科化工公司(Nalco Chemical Co.,Naperville,IL)制造)商购获得。可用的二氧化硅分散体包括“NALCO1115\"和\"DVSZN004”，两者均购自纳尔科化工公司(Nalco Chemical Company）。  \n\n[0095]无机纳米粒子通常包含表面处理。表面处理纳米大小的粒子可在聚合物树脂中提供稳定的分散体。优选地，表面处理使纳米粒子稳定，使得粒子将充分分散于水性聚氨酯分散体中并产生基本上均匀的组合物。此外，纳米粒子可在其表面的至少一部分之上用表面处理剂改性，使得稳定的粒子可在固化期间与聚氨酯或氮丙啶交联剂共聚或反应。  \n\n[0096]一般来讲，表面处理剂具有将附接(共价地、离子地或通过强物理吸附)到粒子表面的第一末端以及赋予粒子与涂料组合物的其余部分的相容性和/或在固化期间与涂料组合物的组分反应的第二末端。表面处理剂的例子包括醇、胺、羧酸、磺酸、麟酸、硅烷和钛酸酯。处理剂的优选类型部分地由金属氧化物表面的化学性质确定。对于二氧化硅优选硅烷，并且对于硅质填料，优选其它表面处理剂。  \n\n[0097］在一些实施例中，纳米粒子包含含有水分散性基团的表面处理。水分散性基团为能够向纳米粒子表面提供亲水性特征从而减少并优选防止水性涂料溶液中的纳米粒子过度凝聚和沉淀的一价基团。此类表面处理可由式A-L-WD表示，其中A为表面键合基团(即用于键合到纳米粒子表面)，WD表示水分散性基团，并且L表示有机连接基或化学键。有机连接基L可为直链或支化的亚烷基、亚芳基或亚烷基和亚芳基基团的组合，任选地包含杂原子。  \n\n[0098］水分散性基团为亲水性或水样基团。它们通常包括(例如)非离子基团、阴离子基团、阳离子基团、在分散于水中时能够形成阴离子基团或阳离子基团的基团(例如盐或酸)、或它们的混合物。  \n\n[0099] 非离子水分散性基团的例子包括聚环氧烷(例如PEG)基团。与二氧化硅纳米粒子一起使用的一种例证性硅烷表面处理为聚环氧乙烷(PEG)硅烷,诸如2-[甲氧基(聚氧乙烯)丙基]三甲氧基硅烷。表面处理可包含其它水分散性基团以及环氧树脂硅烷表面处理，诸如在W02009/085680中描述；所述专利以引用方式并入本文。  \n\n[0100]表面改性剂的所需量可取决于若干因素，诸如粒度、粒子类型、改性剂分子量以及改性剂类型。一般来讲，优选将大约单层的改性剂附接到颗粒的表面。附接程序或所需的反应条件也取决于所用的表面改性剂。对于硅烷，在高温和酸性或碱性条件下表面处理大约1-24小时可为优选的。  \n\n[0101]本文无机纳米粒子的覆盖水平根据涂料组合物中环氧树脂基团的浓度报告，假定$100\\%$ 量的表面处理官能团将共价键合到二氧化硅粒子的表面。在一些实施例中，无机纳米粒子包含 $25\\%$ 或 $50\\%$ 覆盖的表面处理。  \n\n[0102]涂料组合物可以液体形式 (例如，可倾倒形式或可喷洒形式)供应或浸渍到施涂基底中 (例如形成施涂垫或擦拭物)。合适的施涂基底可为例如海绵、泡沫、织造物、非织造物或针织材料的形式。术语\"非织造网\"或\"非织造织物”是指具有以不规则方式插入的各个纤维的结构的网或织物。相比之下，针织或织造织物具有以规则方式插入的纤维。  \n\n[0103]液体聚氨酯涂料组合物可通过常规方法 (包括喷洒、旋涂、刷涂、浸渍、流涂等)施涂，但通常通过旋涂或喷洒施涂。如本领域中所熟知，涂覆操作可在单个阶段中或通过多阶段涂覆程序进行。用于固化(例如氮丙啶)交联剂与聚氨酯聚合物的条件可变化。在一些实施例中，将涂料在约 $90^{\\circ}\\mathrm{C}$ 至 $120^{\\circ}\\mathrm{C}$ 的温度下热固化约20分钟。一般来讲，更低的温度需要更长的固化时间。可使用红外加热来缩短直到可处理涂料的时间。  \n\n[0104]本文所述的干燥并固化的涂料组合物可表现出高透明度(大于 $90\\%$ )，并因此适于施涂到多种透光性基底和制品。干燥并固化的涂料的雾度通常小于 $5\\%.4\\%.3\\%.2\\%.1\\%$ 或 $0.5\\%$ 。高度透明的组合物通常基本上不含遮光颜料 (即，少于0.5重量 $\\%$ 或0.1重量 $\\%$ ）。  \n\n[0105]涂料组合物可向其上涂覆该组合物并干燥和固化的基底提供防雾特性。根据实例中所述的测试方法，如果涂覆的基底阻止形成密度足以显著降低涂覆基底的透明度使得其不能被充分看透的冷凝小水滴，则干燥并固化的涂料被视为具有“良好的\"或“优异的\"防起雾特性。  \n\n[0106]在一些实施例中，干燥并固化的涂料组合物足够耐久，使得在最初和在浸泡于50$\\mathrm{{^\\circC}}$ 的水中24小时后提供良好或优异的防雾特征。在其它实施例中，干燥并固化的涂料组合物足够耐久，使得它们在浸泡于 $65\\mathrm{^\\circC}$ 的水中120小时后可提供良好或优异的防雾特征。  \n\n[0107］在一些实施例中，干燥并固化的涂料组合物在线性剃刀磨蚀测试后表现出机械耐久性(即，涂料的雾度仅增加 $1-7\\%$ 的雾度变化)并且在用纸巾擦拭涂层100、200或300个循环后未观察到刮痕。  \n\n[0108]有多种制品可受益于防雾涂料，诸如交通标志、机动车辆窗户(并且尤其是挡风玻璃)、防护眼镜 (例如护目镜、面罩、头盔等)和建筑镶嵌玻璃以及其它装饰性玻璃制品。  \n\n[0109]可施涂防雾涂料组合物的基底优选对可见光透明或半透明。如果将涂料组合物用于不同的目的，则作为另外一种选择，基底可为不透明的，诸如就不锈钢、聚氯乙烯和纤维板而言。基底包括有机和无机材料两者。示例性基底由以下材料制得：聚酯(例如聚对苯二甲酸乙二醇酯 (PET)、聚对苯二甲酸丁二醇酯)、聚碳酸酯 (PC)、烯丙基二乙二醇碳酸酯、聚丙烯酸酯 (诸如聚甲基丙烯酸甲酯)、聚苯乙烯、聚矾、聚醚矾、乙酸丁酸纤维素、玻璃等，包括其共混物和层合物。通常，基底为材料的膜、薄片、面板或嵌板的形式并且为制品的一部分。基底可为平坦的、弯曲的、或成形的。待涂覆的基底可通过吹塑、浇注、挤出或注塑来制备。  \n\n[0110]防雾涂料可涂覆在基底的两侧上。作为另外一种选择，可将本发明的涂料涂覆于基底的一侧上。基底的相对侧可为未涂覆的或涂覆有多种常规的防雾组合物。优选地，涂料表面应面向更高湿度的方向，例如面罩上具有防雾涂料的一侧应面向穿着者。  \n\n[0111]包含本文所述的涂料可降低涂覆 (例如基底)表面的接触角。相比于缺乏此类涂料的相同基底，与水的前进接触角可降低 $:20\\%.30\\%.40\\%.50\\%.60\\%.70\\%$ 或 $80\\%$ 。例如，纤维板的接触角可从 $50^{\\circ}+$ 降低至小于 $25^{\\circ}$ 或 $20^{\\circ}$ 。作为另一个实例，不锈钢与水的前进接触角可从 $85^{\\circ}+$ 降低至小于 $50^{\\circ}$ 或 $40^{\\circ}$ 或 $20^{\\circ}$ 。作为另一个实例，聚氯乙烯与水的前进接触角可从${60}^{\\circ}+$ 降低至小于 $30^{\\circ}$ 或 $25^{\\circ}$ 或 $20^{\\circ}$ 。因此，本文所述涂料的存在可使多种基底与水的前进接触角降低至小于 $30^{\\circ}$ 或 $25^{\\circ}$ 或 $20^{\\circ}$ 。另外， (例如纤维板、不锈钢和聚氯乙烯)与水的后退接触角可降低至 $5^{\\circ}$ 或更小。  \n\n[0112]通过以下实例进一步例证本公开的目的和优点，但在这些实例中列举的具体材料及其量以及其它条件和细节不应理解为是对本公开的不当限制。  \n\n[0113] 测试描述 [0114] 防起雾特性的测试  \n\n[0115]根据本发明的涂料的防起雾特性通过将涂覆的基底置于热水(在约 $50–60^{\\circ}\\mathrm{C}$ 的温度下)的容器之上而确定。如果在10秒内观察到起雾，则认为涂料具有“较差的\"防起雾特性。如果在10-60秒内观察到起雾，则认为涂料具有“良好的\"防起雾特性。如果在60秒后观察到起雾，则认为涂料具有“优异的\"防起雾特性。  \n\n[0116] 测量透射率和雾度的测试  \n\n[0117］本文所公开的透射率和雾度值使用Haze-Gard Plus雾度计(购自马里兰州银泉的毕克-加德纳公司(BYK-Gardiner,Silver Springs,MD)）根据ASTM D1003中所述的程序测量。  \n\n[0118] 涂料的耐久性测试  \n\n[0119]防雾涂料与(塑性)基底的粘附力通过十字切割式/胶带粘附力测试而确定。根据本发明的实例制得的所有涂料均通过了十字切割式/胶带粘附力测试。  \n\n[0120]防雾涂料的机械耐久性通过使涂覆的基底经受线性磨蚀测试而确定。线性磨蚀测试通过在约1400克力(13.73N)的恒定力下用纸巾擦拭涂层100、200或300个循环而进行。然后，测试涂料的雾度并在视觉上观察刮痕的存在。  \n\n[0121] 材料[0122] 整个实例涉以及到以下材料列表及其来源。  \n\n[0123]   \n\n\n<html><body><table><tr><td>材料</td><td>说明</td></tr><tr><td>NALCO 1115</td><td>水性（4nm）胶态二氧化硅分散体，以商品名 “NALCO1115购自伊利诺伊州内珀维尔的纳尔 科公司(Nalco Co.,Naperville, IL)。</td></tr><tr><td>DVSZN004</td><td>水性（42nm）胶态二氧化硅分散体，购自伊利诺伊 州内珀维尔的纳尔科公司(NalcoCo.，Naperville， IL).</td></tr><tr><td>W835/140 EM2382</td><td>具有聚碳酸酯主链的聚氨酯分散体，以商品名 \"INCOREZW835/140购自英国兰开夏郡的 Incorez 公司(Incorez Co.,Lancashire,England). 乙氧基化(9)三甲基丙烷三丙烯酸酯，购自长兴 化学工业公司（EtemalChemicalCo.)。</td></tr><tr><td>SR 502 2-甲基氮丙啶</td><td>乙氧基化（9)三甲基丙烷三丙烯酸酯，以商品名 \"SR502”购自宾夕法尼亚州埃克斯顿的沙多玛公 司（Sartomer Company, Exton, PA)。 购自密苏里州圣路易斯的西格玛奥德里奇化学公</td></tr><tr><td>2-[甲氧基（聚氧乙烯） 丙基]三甲氧基硅烷</td><td>司(Sigma Aldrich Chemical Company, St. Louis, MO)。 购自宾夕法尼亚州莫里斯维尔的盖勒斯特有限公 司（Gelest,Inc.,Morrisville,PA)</td></tr><tr><td>ED-900</td><td>聚醚胺，以商品名“JEFFAMINEED-900购自德 克萨斯州的伍德兰公司(TheWoodlands,TX)。</td></tr><tr><td>ED-2003</td><td>聚醚胺，以商品名“JEFFAMINEED-2033购自德 克萨斯州的伍德兰公司（TheWoodlands,TX)。 购自密苏里州圣路易斯的西格玛奥德里奇化学公</td></tr><tr><td>聚（乙二醇）（200）单甲 基丙烯酸酯</td><td>司(Sigma Aldrich Chemical Company, St. Louis, MO).</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# [0124]  \n\n<html><body><table><tr><td>PZ-28</td><td>丙烯亚胺三官能氮丙啶，以商品名“PZ-28”购自 新泽西州梅德福的聚氮丙啶有限公司 (PolyAziridine,LLC,Medford,NJ)。</td></tr><tr><td>PZ-33</td><td>丙烯亚胺三官能氮丙啶，以商品名“PZ-33”购自 新泽西州梅德福的聚氮丙啶有限公司 (PolyAziridine,LLC,Medford,NJ)。</td></tr><tr><td>XL-706</td><td>不含VOC的三官能氮丙啶交联剂，以商品名 “XL-706\"购自Picassian聚合物公司（Picassian Polymers).</td></tr><tr><td>CX-100</td><td>多官能氮丙啶交联剂，以商品名“CX-100”购自荷 兰哈林的皇家帝斯曼集团（RoyalDSMN.V. Harleen,Netherlands)</td></tr><tr><td>琥珀酸酐</td><td>购自马萨诸塞州沃德山的阿法埃莎公司（Alfa Aesar,Ward Hill,MA)。</td></tr><tr><td>Bacote20</td><td>碳酸锆铵交联剂，购自新泽西州夫雷明顿的锆化 学有限公司(Zirconium Chemicals,Flemington, ND.</td></tr><tr><td>ERL-4221</td><td>脂环族环氧树脂交联剂，购自密歇根州米德兰的 陶氏化学公司（Dow Chemicals，Midland,MI)</td></tr><tr><td>V-04</td><td>碳二亚胺交联剂，购自日本日清纺株式会社 (Nisshinbo Industries,Inc. Japan).</td></tr><tr><td>BH-305</td><td>亲水性脂族聚异氰酸酯交联剂，购自德国勒沃库 森的拜耳材料科学公司（BayerMaterials Science, Leverkusen,Germany)</td></tr><tr><td>三乙胺</td><td>购自密苏里州圣路易斯的西格玛奥德里奇化学公 司（Sigma Aldrich Chemical Company, St. Louis, MO)。</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# [0125]  \n\n<html><body><table><tr><td>THF</td><td>四氢呋喃，购自密苏里州圣路易斯的西格玛奥德 里奇化学公司(Sigma Aldrich Chemical Company, St. Louis, MO).</td></tr><tr><td>AL-2450</td><td>氧化铝纳米粒子分散体（50重量%），以商品名 “NANOARCAL-2450购自伊利诺伊州罗密欧维 尔的纳米相技术公司(NanophaseTechnologies, Corp.,Romeoville, IL).</td></tr><tr><td>BRIJ30</td><td>四甘醇十二烷醚，以商品名“BRIJ30\"购自密苏里 州圣路易斯的西格玛奥德里奇化学公司（Sigma Aldrich Chemical Company, St. Louis, MO).</td></tr><tr><td>BYK-346</td><td>有机硅表面活性剂，可以商品名“BYK-346”购自 赢讯公司（Innovadex）。</td></tr><tr><td>A-18</td><td>离子表面活性剂，以商品名“POLYSTEPA-18”购 自伊利诺伊州诺斯菲尔德的斯泰潘公司（Stepan Company, Northfield, IL).</td></tr><tr><td>BC-10</td><td>离子表面活性剂，可以商品名“HitenolBC-10\"购 自日本第—工业制药株式会社(Dai-Ichi Kogyo Seitaku, Ltd., Japan)</td></tr><tr><td>PEG单甲醚</td><td>聚（乙二醇）甲醚（MW=550），购自密苏里州圣路 易斯的西格玛奥德里奇化学公司（SigmaAldrich Chemical Company, St. Louis, MO).</td></tr></table></body></html>  \n\n[0126] 实例[0127] 合成包含PEG硅烷表面处理的纳米粒子：  \n\n[0128]对于制备性实例1-3中的每一个，用官能硅烷改性的二氧化硅纳米粒子通过向所选的二氧化硅纳米粒子分散体中缓慢添加所需量的官能硅烷而制备。二氧化硅纳米粒子分散体与官能硅烷的相对量基于所需的等同表面覆盖而确定。在室温下将所得的分散体搅拌4小时，并且然后在烘箱中加热至至多 $65\\mathrm{^\\circC}$ 过夜。下表1描述了针对制备性实例1-3中的每一个的二氧化硅纳米粒子、所用的官能硅烷以及所得的覆盖百分比。如下文实例中所述，使用具有不同粒度和表面覆盖的所得改性纳米粒子分散体。  \n\n[0129] 表1  \n\n[0130]  \n\n<html><body><table><tr><td>纳米粒子</td><td>%表面覆盖</td><td>官能硅烷</td></tr><tr><td>DVSZN00450</td><td></td><td>2-[甲氧基（聚氧乙烯）丙基]三甲 氧基硅烷</td></tr></table></body></html>  \n\n[0131] 制备性实例4)132] 多官能氮丙啶交联剂的合成：  \n\n[0133]三官能氮丙啶交联剂PZ-2382和PZ-502经由EM2382( $\\mathrm{M}\\Psi=692,$ 或SR-502 $(\\mathrm{MW=692}^{\\cdot}$ )与2-甲基氮丙啶的迈克尔加成制备。简而言之，在室温下向EM2382或SR-502( $\\mathrm{30g}$ ，$0.0434\\mathrm{mol})$ 中逐滴添加2-甲基氮丙啶 $(9.1\\mathrm{g},0.1385\\mathrm{mol})$ ，然后在室温下将所得的混合物搅拌1小时，并且然后在 $60^{\\circ}\\mathrm{C}$ 下回流24小时。在真空下移除过量的甲基氮丙啶，并且最终获得浅黄色液体产物并分别称为PZ-2382和PZ-502。由5.8至6.4的双键消失证实了丙烯酸酯基团与甲基氮丙啶中的NH之间的反应成功地完成。  \n\n[0134]使用购自亚利桑那州图森布鲁克BioSpin公司(Bruker BioSpin Corporation,Tucson,AZ)的现代500MHz Avance III Bruker NMR获得“EM-2382\"三官能丙烯酸酯的NMR光谱。根据分析，该丙烯酸酯含有30重量 $\\%$ 的以下表面活性剂：  \n\n[0135] $\\mathrm{H0-\\left[CH_{2}C H_{2}O\\right]n-C_{12}H_{25}}$   \n[0136] 因此，由“EM-2382\"制备的氮丙啶交联剂经计算含有23重量 $\\%$ 的此类表面活性剂。[0137] 制备性实例5  \n[0138] 基于PEG的铵盐(900-DA和2003-DA)的合成：  \n\n[0139]在 $50^{\\circ}\\mathrm{C}$ 下，向溶解到THF中的琥珀酸酐 $({10}\\mathrm{g})$ 加入ED-900 $(50\\mathrm{g})$ 或ED-2003 $(100\\mathrm{g})$ 。在 $50^{\\circ}\\mathrm{C}$ 下反应24小时后，在真空下移除THF后，分别获得产物黄色粘稠液体或浅黄色蜡状物。将所得的基于PEG的二酸溶解到水中，以获得 $30\\%$ 的水性溶液，向其中添加10g的三乙胺并在室温下搅拌30分钟，以获得具有30重量 $\\%$ 固体的基于PEG的二羧酸铵盐。将所得的产物以盐形式用于后续实例中。反应方案示于下文。  \n\n![](images/72d22bd910026cfb4ed7909a01869053190aacef4198a486e923622981ada282.jpg)  \n\n[0141] 形成防雾涂料的一般过程  \n\n[0142]在室温下将组分混合在一起并搅拌20分钟。使用15号迈耶棒(Mayer bar)或通过浸涂将具有约 $30\\%$ 固含量的所得涂料溶液涂覆在聚酯 (PET)、聚碳酸酯 (PC)或玻璃基底上。然后将所得的涂料在 $110{-}120^{\\circ}\\mathrm{C}$ 的温度下固化20-30分钟，以形成具有所需特性的涂层  \n\n(即透明并耐久的防雾涂层)。  \n\n[0143] 浸涂程序  \n\n[0144]将具有新鲜制备的聚碳酸酯镜片滑座的夹子置于VelmaxUnislide浸涂机的金属棒上。对准滑座以使侧面垂直于实验工作台顶部并且底部平行于实验工作台顶部。用胶带固定长尾夹。将基底浸入涂料溶液中并以大约1毫米/秒的适当牵拉速度逐渐拉出。  \n\n[0145] 实例1  \n\n[0146]在搅拌下将聚氨酯分散体W835/140(32重量 $\\%,60.9\\mathrm{g})$ 与 $15\\mathrm{g}$ 的900-DA(30重量 $\\%$ ，如上所述在制备性实例5中制备)混合，以形成均质分散体，然后添加 $16.0\\mathrm{g}$ 的PZ-2382(净，如上所述在制备性实例4中制备)和18.1g的水并搅拌20分钟，直至获得均质分散体。通过VelmaxUnislide浸涂机将溶液(30重量 $\\%$ 的固体)施涂在PC板上，并且然后在 $110^{\\circ}\\mathrm{C}$ 下固化20分钟。所得涂覆的PC膜表现出“优异的\"防雾性能(在暴露于 $\\mathrm{50^{\\circ}C}$ 的蒸气时未出现雾)以及良好的透光率 $(>90)$ 。浸泡在室温水中240小时以及 $80^{\\circ}\\mathrm{C}$ 水中96小时或 $65\\mathrm{^\\circC}$ 水中120小时后，涂覆的PC板仍表现出“优异的\"防雾性能并且非常耐久。  \n\n[0147] 实例2  \n\n[0148]在搅拌下将聚氨酯分散体W835/140(32重量 $\\%,60.2\\mathrm{g})$ 与 $29.2\\mathrm{g}$ 的 $900{-}\\mathrm{DA}$ (30重量 $\\%$ ，如上所述在制备性实例5中制备)混合，以形成均质分散体，然后添加7.0g的PZ-2382(净)和3.6g的水并搅拌20分钟，直至获得均质分散体。通过VelmaxUnislide浸涂机将溶液(35重量 $\\%$ 的固体)施涂在PC板上，并且然后在 $110^{\\circ}\\mathrm{C}$ 下固化20分钟。所得涂覆的PC膜表现出“优异的\"防雾性能(在暴露于 $50^{\\circ}\\mathrm{C}$ 的蒸气时未出现雾)以及良好的透光率 $(>90)$ 。浸泡在室温水中240小时以及 $80^{\\circ}\\mathrm{C}$ 水中96小时或 $65^{\\circ}\\mathrm{C}$ 水中120小时后，涂覆的PET膜仍表现出“优异的\"防雾性能并且非常耐久。  \n\n[0149] 实例3  \n\n[0150]在搅拌下将聚氨酯分散体W835/140(32重量 $\\%$ ,54.7g)与35g的900-DA(30重量 $\\%$ ，如上所述在制备性实例5中制备)混合，以形成均质分散体，然后添加7.0g的PZ-2382(净)和3g的水并搅拌20分钟，直至获得均质分散体。通过Velmax Unislide浸涂机将溶液(35重量 $\\%$ 的固体)施涂在PC板上，并且然后在 $110^{\\circ}\\mathrm{C}$ 下固化20分钟。所得涂覆的PC膜表现出“优异的\"防雾性能(在暴露于 $\\mathrm{50^{\\circ}C}$ 的蒸气时未出现雾)以及良好的透光率 $(>90)$ 。浸泡在室温水中240小时以及 $80^{\\circ}\\mathrm{C}$ 水中96小时或 $65\\mathrm{^\\circC}$ 水中120小时后，涂覆的PC板仍表现出“优异的\"防雾性能并且非常耐久。  \n\n[0151] 实例4  \n\n[0152]在搅拌下将聚氨酯分散体W835/140(32重量 $\\%,65.6\\mathrm{g})$ 与 $23.3\\mathrm{g}$ 的900-DA(30重量 $\\%$ ，如上所述在制备性实例5中制备)混合，以形成均质分散体，然后添加7.0g的PZ-2382(净）、1g的BYK-346和3g的水并搅拌20分钟，直至获得均质分散体。通过VelmaxUnislide浸涂机将溶液(35重量 $\\%$ 的固体)施涂在PC板上，并且然后在 $110^{\\circ}\\mathrm{C}$ 下固化20分钟。所得涂覆的PC膜表现出“优异的\"防雾性能(在暴露于 $50^{\\circ}\\mathrm{C}$ 的蒸气时未出现雾)以及良好的透光率(>90)。浸泡在室温水中240小时以及 $80^{\\circ}\\mathrm{C}$ 水中96小时或 $65\\mathrm{^\\circC}$ 水中120小时后，涂覆的PC膜仍表现出“优异的\"防雾性能并且非常耐久。通过浇铸和浸涂方法用上述涂料溶液涂覆玻璃板和PC镜片，随后在 $110^{\\circ}\\mathrm{C}$ 下固化20分钟。浸泡于室温水以及热水中24小时之前和之后，所得涂覆的玻璃板和PC镜片具有“优异的\"防雾性能。  \n\n[0153] 实例5  \n\n[0154]在搅拌下将聚氨酯分散体W835/140(32重量 $\\%,54.7\\mathrm{g})$ 与35.0g的 $900{-}\\mathrm{DA}$ (30重量 $\\%$ ，如上所述在制备性实例5中制备)混合，以形成均质分散体，然后添加7.0g的PZ-2382(净)、1g的BYK-346和4g的水并搅拌20分钟，直至获得均质分散体。用14号迈耶棒将溶液(35重量 $\\%$ 的固体)施涂在PC板上，并且然后在 $110^{\\circ}\\mathrm{C}$ 下固化20分钟。所得涂覆的PC膜表现出“优异的\"防雾性能 (在暴露于 $\\mathrm{50^{\\circ}C}$ 的蒸气时未出现雾)以及良好的透光率 $(>90)$ 。浸泡在室温水中240小时以及 $80^{\\circ}\\mathrm{C}$ 水中96小时或 $65\\mathrm{^\\circC}$ 水中120小时后，涂覆的PC膜仍表现出“优异的\"防雾性能并且非常耐久。通过浇铸和浸涂方法用上述涂料溶液涂覆玻璃板和PC镜片，随后在110$\\mathcal{C}$ 下固化20分钟。浸泡于室温水以及热水中24小时之前和之后，所得涂覆的玻璃板和PC镜片具有“优异的\"防雾性能。  \n\n[0155] 实例6  \n\n[0156]在搅拌下将聚氨酯分散体W835/140(32重量 $\\%,56.38)$ 与15.0g的 $900{-}\\mathrm{DA}$ (30重量 $\\%$ ，如上所述在制备性实例5中制备)混合，以形成均质分散体，然后添加6.0g的PZ-2382（净）、5.0g的PEG改性的DVSZN004（制备性实例 $2,50\\%$ 的覆盖和30重量 $\\%$ )和17.7g的水并搅拌20分钟，直至获得均质分散体。通过VelmaxUnislide浸涂机将溶液(30重量 $\\%$ 的固体)施涂在PC板上，并且然后在 $110^{\\circ}\\mathrm{C}$ 下固化20分钟。所得涂覆的PC膜表现出“优异的\"防雾性能(在暴露于 $50^{\\circ}\\mathrm{C}$ 的蒸气时未出现雾)以及良好的透光率 $(>90)$ 。浸泡在室温水中240小时以及$80^{\\circ}\\mathrm{C}$ 水中96小时或 $65\\mathrm{^\\circC}$ 水中120小时后，涂覆的PC膜仍表现出“优异的\"防雾性能并且非常耐久。通过浸涂用上述涂料溶液涂覆PC镜片，随后在 $110^{\\circ}\\mathrm{C}$ 下固化20分钟。浸泡于室温水以及热水中24小时之前和之后，所得涂覆的PC镜片具有\"优异的\"防雾性能。  \n\n[0157] 实例7  \n\n[0158]在搅拌下将聚氨酯分散体 ${\\mathbb{W}}835/140$ (32重量 $\\%,60.9\\mathrm{g})$ 与 $15\\mathrm{g}$ 的2003-DA(30重量 $\\%$ ，如上所述在制备性实例5中制备)混合，以形成均质分散体，然后添加6.0g的PZ-2382(净)和18.lg的水并搅拌20分钟，直至获得均质分散体。通过VelmaxUnislide浸涂机将溶液(30重量 $\\%$ 的固体)施涂在PC板上，并且然后在 $110^{\\circ}\\mathrm{C}$ 下固化20分钟。所得涂覆的PC膜表现出“优异的\"防雾性能(在暴露于 $50^{\\circ}\\mathrm{C}$ 的蒸气时未出现雾)以及良好的透光率 $(>90)$ 。浸泡在室温水中240小时以及 $80^{\\circ}\\mathrm{C}$ 水中96小时或 $65\\mathrm{^\\circC}$ 水中120小时后，涂覆的PC板仍表现出“优异的\"防雾性能并且非常耐久。  \n\n[0159] 实例8  \n\n[0160]在搅拌下将聚氨酯分散体W835/140(32重量 $\\%,60.9\\mathrm{g})$ 与 $25\\mathrm{g}$ 的900-DA(30重量 $\\%$ ，如上所述在制备性实例5中制备)混合，以形成均质分散体，然后添加3.0g的PZ-28(净)和11.1g的水并搅拌20分钟，直至获得均质分散体。用14号迈耶棒将溶液(30重量 $\\%$ 的固体)施涂在PC膜上，并且然后在 $110^{\\circ}\\mathrm{C}$ 下固化20分钟。所得涂覆的PC膜表现出“优异的\"防雾性能(在暴露于 $50^{\\circ}\\mathrm{C}$ 的蒸气时未出现雾)以及良好的透光率 $(>90)$ 。浸泡在室温水中240小时以及$80^{\\circ}\\mathrm{C}$ 水中96小时或 $65\\mathrm{^\\circC}$ 水中120小时后，涂覆的PC膜仍表现出“优异的\"防雾性能并且非常耐久。  \n\n[0161] 实例9  \n\n[0162]在搅拌下将聚氨酯分散体W835/140(32重量 $\\%,60.9\\mathrm{g})$ 与 $25\\mathrm{g}$ 的900-DA(30重量 $9\\%$ ，如上所述在制备性实例5中制备)混合，以形成均质分散体，然后添加 $3.0\\mathrm{g}$ 的PZ-33(净)和  \n\n11.1g的水并搅拌20分钟，直至获得均质分散体。用14号迈耶棒将溶液(30重量 $\\%$ 的固体)施涂在PC板上，并且然后在 $110^{\\circ}\\mathrm{C}$ 下固化20分钟。所得涂覆的PC膜表现出“优异的\"防雾性能(在暴露于 $50^{\\circ}\\mathrm{C}$ 的蒸气时未出现雾)以及良好的透光率 $(>90)$ 。浸泡在室温水中240小时以及$80^{\\circ}\\mathrm{C}$ 水中96小时或 $65\\mathrm{^\\circC}$ 水中120小时后，涂覆的PC膜仍表现出“优异的\"防雾性能并且非常耐久。  \n\n[0163] 实例10  \n\n[0164]在搅拌下将聚氨酯分散体W835/140(32重量 $\\%,60.9\\mathrm{g})$ 与 $25\\mathrm{g}$ 的900-DA(30重量 $\\%$ ，如上所述在制备性实例5中制备)混合，以形成均质分散体，然后添加 $3.0\\mathrm{g}$ 的XL-706(净)和11.1g的水并搅拌20分钟，直至获得均质分散体。用14号迈耶棒将溶液(30重量 $\\%$ 的固体)施涂在PC膜上，并且然后在 $110^{\\circ}\\mathrm{C}$ 下固化20分钟。所得涂覆的PC膜表现出“优异的\"防雾性能(在暴露于 $50^{\\circ}\\mathrm{C}$ 的蒸气时未出现雾)以及良好的透光率 $(>90)$ 。浸泡在室温水中240小时以及$80^{\\circ}\\mathrm{C}$ 水中96小时或 $65\\mathrm{^\\circC}$ 水中120小时后，涂覆的PC膜仍表现出“优异的\"防雾性能并且非常耐久。  \n\n[0165] 实例11  \n\n[0166]在搅拌下将聚氨酯分散体W835/140(32重量 $\\%,60.9\\mathrm{g})$ 与 $25\\mathrm{g}$ 的900-DA(30重量 $\\%$ ，如上所述在制备性实例5中制备)混合，以形成均质分散体，然后添加3.0g的CX-100(净)和11.1g的水并搅拌20分钟，直至获得均质分散体。用14号迈耶棒将溶液(30重量 $\\%$ 的固体)施涂在PC膜上，并且然后在 $110^{\\circ}\\mathrm{C}$ 下固化20分钟。所得涂覆的PC膜表现出“优异的\"防雾性能(在暴露于 $50^{\\circ}\\mathrm{C}$ 的蒸气时未出现雾)以及良好的透光率 $(>90)$ 。浸泡在室温水中240小时以及$80^{\\circ}\\mathrm{C}$ 水中96小时或 $65\\mathrm{^\\circC}$ 水中120小时后，涂覆的PC膜仍表现出“优异的\"防雾性能并且非常耐久。  \n\n[0167] 实例12  \n\n[0168]在搅拌下将聚氨酯分散体W835/140(32重量 $\\%,54.7\\mathrm{g})$ 与35.0g的900-DA(30重量 $\\%$ ，如上所述在制备性实例5中制备)混合，以形成均质分散体，然后添加7.0g的PZ-502(净)、1g的BRIJ30和4g的水并搅拌20分钟，直至获得均质分散体。用14号迈耶棒或通过浸涂将溶液(35重量 $\\%$ 的固体)施涂在PC板上，并且然后在 $110^{\\circ}\\mathrm{C}$ 下固化20分钟。所得涂覆的PC膜表现出“优异的\"防雾性能(在暴露于 $50^{\\circ}\\mathrm{C}$ 的蒸气时未出现雾)以及良好的透光率 $(>90)$ 。浸泡在室温水中240小时以及 $80^{\\circ}\\mathrm{C}$ 水中96小时或 $65^{\\circ}\\mathrm{C}$ 水中120小时后，涂覆的PC膜仍表现出“优异的\"防雾性能并且非常耐久。通过浇铸和浸涂方法用上述涂料溶液涂覆玻璃板和PC镜片，随后在 $110^{\\circ}\\mathrm{C}$ 下固化20分钟。浸泡于室温水以及热水中24小时之前和之后，所得涂覆的玻璃板和PC镜片具有“优异的\"防雾性能。  \n\n[0169] 实例13  \n\n[0170]在搅拌下将聚氨酯分散体W835/140(32重量 $\\%,65.6\\mathrm{g})$ 与 $23.3\\mathrm{g}$ 的900-DA(30重量 $\\%$ ，如上所述在制备性实例5中制备)混合，以形成均质分散体，然后添加7.0g的PZ-502(净）、1g的BRIJ30和3g的水并搅拌20分钟，直至获得均质分散体。用14号迈耶棒或通过浸涂将溶液(35重量 $\\%$ 的固体)施涂在PC板上，并且然后在 $110^{\\circ}\\mathrm{C}$ 下固化20分钟。所得涂覆的PC膜表现出“优异的\"防雾性能(在暴露于 $50^{\\circ}\\mathrm{C}$ 的蒸气时未出现雾)以及良好的透光率 $(>90)$ 。浸泡在室温水中240小时以及 $80^{\\circ}\\mathrm{C}$ 水中96小时或 $65\\mathrm{^\\circC}$ 水中120小时后，涂覆的PC膜仍表现出“优异的\"防雾性能并且非常耐久。通过浇铸和浸涂方法用上述涂料溶液涂覆玻璃板和PC镜片，随后在 $110^{\\circ}\\mathrm{C}$ 下固化20分钟。浸泡于室温水以及热水中24小时之前和之后，所得涂覆的玻璃板和PC镜片具有“优异的\"防雾性能。  \n\n[0171] 下表3汇总了在上述实例1-13的基底上所得的固化涂料中的组分和各组分的相对量。  \n\n[0172] 表3 [0173]  \n\n<html><body><table><tr><td rowspan=\"2\">实 例酯</td><td rowspan=\"2\">(W835/140</td><td colspan=\"2\">重量%聚氨类型和重量% 二酸盐</td><td>类型和 重量% 氮丙啶</td><td colspan=\"2\"></td></tr><tr><td>900- DA</td><td>2003- DA</td><td>PZ- 2382*</td><td>BYK- 346</td><td>BRIJ 30</td></tr><tr><td>1</td><td>65</td><td>15</td><td></td><td>20</td><td></td><td></td></tr><tr><td>2</td><td>55</td><td>25</td><td></td><td>20</td><td></td><td></td></tr><tr><td>3</td><td>50</td><td>30</td><td></td><td>20</td><td></td><td></td></tr><tr><td>4</td><td>58.3</td><td>19.4</td><td></td><td>19.4</td><td>2.8</td><td></td></tr><tr><td>5</td><td>48.6</td><td>29.1</td><td></td><td>19.4</td><td>2.7</td><td></td></tr><tr><td>6**</td><td>60</td><td>15</td><td></td><td>20</td><td></td><td></td></tr><tr><td>7</td><td>65</td><td></td><td>15</td><td>20</td><td></td><td></td></tr><tr><td>8</td><td>65</td><td>25</td><td></td><td>10 PZ-28</td><td></td><td></td></tr></table></body></html>  \n\n[0174]  \n\n<html><body><table><tr><td></td><td>65</td><td>25</td><td></td><td>10 PZ-33</td><td></td><td></td></tr><tr><td>10</td><td>65</td><td>25</td><td></td><td>10 XL-706</td><td></td><td></td></tr><tr><td>11</td><td>65</td><td>25</td><td></td><td>10 CX-100</td><td></td><td></td></tr><tr><td>12</td><td>48.6</td><td>29.1</td><td></td><td>19.4 PZ-502</td><td></td><td>2.7</td></tr><tr><td>13</td><td>58.3</td><td>19.4</td><td></td><td>19.4 PZ-502</td><td></td><td>2.7</td></tr></table></body></html>  \n\n[0175] PZ-2382包含 $23\\%$ 的表面活性剂，如前所述。因此，  \n[0176] 15重量 $\\%$ 的 $\\mathrm{PZ}\\mathrm{-}2382\\mathrm{=}3.5$ 重量 $\\%$ 的表面活性剂和11.5重量 $\\%$ 的亲水性氮丙啶交联剂  \n[0177] 25重量 $\\%$ 的 $\\mathrm{PZ}\\mathrm{-}2382\\mathrm{=}5.8$ 重量 $\\%$ 的表面活性剂和19.2重量 $\\%$ 的亲水性氮丙啶交联剂  \n[0178] 24.2重量 $\\%$ 的 $\\mathrm{PZ}\\mathrm{-}2382\\mathrm{=}5.6$ 重量 $\\%$ 的表面活性剂和18.6重量 $\\%$ 的亲水性氮丙啶交联剂  \n[0179] 23重量 $\\%$ 的 $\\mathrm{PZ^{-2382=5.3}}$ 重量 $\\%$ 的表面活性剂和17.7重量 $\\%$ 的亲水性氮丙啶交联剂  \n[0180] \\*\\*实例6还含有5重量 $9\\%$ 的如前所述的包含PEG硅烷表面处理的二氧化硅纳米粒子。  \n\n[0181]由表3的组合物制备的所有防雾涂料均表现出优异的机械耐久性(即，在线性剃刀磨蚀测试后涂料的雾度仅增加 $1-7\\%$ 的雾度变化并且在用纸巾擦拭涂层300个循环后未观察到刮痕)。  \n\n[0182]实例14在搅拌下将丙烯酸胶乳(40.5重量 $\\%$ ,43.5g,可以商品名“ROSHIELDTM3188\"购自陶氏涂料材料公司(Dow Coating Materials)）与900-DA(如实例22中所述制备，30重量 $\\%,30\\mathrm{g})$ 混合，以形成均质分散体。然后分别添加PZ-2382 $(7.0\\mathrm{g}$ ,净)和19.5g的水，并将所得的溶液搅拌20分钟。由此获得最终分散溶液(35重量 $\\%$ 的固体)，并且随后用14号迈耶棒施涂在PC膜上。在 $110^{\\circ}\\mathrm{C}$ 下将所得的涂料固化20分钟。所得涂覆的PC膜表现出“优异的\"防雾性能 (在暴露于 $50^{\\circ}\\mathrm{C}$ 蒸气1分钟后未出现雾)以及良好的光学性质，其中透光率至多 $90\\%$ 。使样品经受两项水浸泡测试，一项在室温下120小时，并且一项在 $65\\mathrm{^\\circC}$ 下120小时。浸泡的PC样品显示优异的抗水性并保持防雾特性。  \n\n[0183]实例15在搅拌下将聚氨酯/丙烯酸混合胶乳(40重量 $\\%$ ,43.5g，可以商品名“NEOPACR-9036\"购自帝斯曼利康树脂有限公司(DSMNeoresins)）与 $900{-}\\mathrm{DA}$ (如实例22中所述制备，30重量 $\\%,30.0\\mathrm{g})$ 混合，以形成均质分散体。然后分别添加PZ-2382 $(7.0\\mathrm{g}$ ,净)和$19.5\\mathrm{g}$ 的水，并将所得的溶液搅拌20分钟直至获得均质分散体。由此获得最终分散溶液(35重量 $\\%$ 的固体)，并且随后用14号迈耶棒施涂在PC膜上。在 $110^{\\circ}\\mathrm{C}$ 下将所得的涂料固化20分钟。所得涂覆的PC膜表现出“优异的\"防雾性能(在暴露于 $50^{\\circ}\\mathrm{C}$ 蒸气1分钟后未出现雾)以及良好的光学性质(透光率至多 $90\\%$ )。使样品经受两项水浸泡测试，一项在室温下120小时，并且一项在 $65\\mathrm{^\\circC}$ 下120小时。浸泡的PC样品显示优异的抗水性并保持防雾特性。  \n\n[0184] 实例16-20  \n\n[0185]通过将聚氨酯分散体W835/140(32重量 $\\%,94.38\\mathrm{g})$ 与900-DA(如实例22中所述制备，30重量 $\\%,61.17\\mathrm{g})$ 组合而形成聚氨酯分散体共混物。将混合物搅拌15分钟，以形成均质分散体。在搅拌下向其加入1.75g的BYK-346。将混合物搅拌附加的15分钟，以制备均质分散体。  \n\n[0186]将交联剂(类型和量如下表所示)与0.4g的水和9g的聚氨酯共混物结合，以制备防雾涂料组合物。  \n\n[0187]使用15号迈耶棒将实例16-20涂覆到如早前所述的PC膜上。在 $120^{\\circ}\\mathrm{C}$ 下将涂料固化20分钟。  \n\n[0188]   \n\n\n<html><body><table><tr><td>实例</td><td>交联剂（1）类 型</td><td>交联剂（1) 量</td><td>交联剂(2)类交联剂(2）量 型</td><td></td></tr><tr><td>实例16</td><td>PZ-2382</td><td>0.77g</td><td>Bacote20</td><td>0.1g</td></tr><tr><td>实例17</td><td>Bacote20</td><td>0.3g</td><td>无</td><td></td></tr><tr><td>实例18</td><td>PZ-2382</td><td>0.7g</td><td>ERL4221</td><td>0.1g</td></tr><tr><td>实例19</td><td>PZ-2382</td><td>0.7g</td><td>BH-305</td><td>0.1g</td></tr><tr><td>实例20</td><td>V-04</td><td>0.8g</td><td>无</td><td></td></tr></table></body></html>  \n\n[0189]浸泡在 $50^{\\circ}\\mathrm{C}$ 的水中24小时后评估防雾特性。实例16-20表现出良好的防雾特性和优异的透光率。  \n\n[0190] 实例21  \n\n[0191]在搅拌下将聚氨酯分散体W835/140(32重量 $\\%,32.8\\mathrm{g})$ ）与11.5g的900-DA(30重量 $\\%$ ）混合，以形成均质分散体，然后添加3.0g的PZ-502(净)、0.75g的JeecolLA-7(得自Jeen国际公司(Jeen International Co.）的 $\\mathrm{C_{12}E0_{7}})$ 和 $1.0\\mathrm{g}$ 的BYK-346并搅拌20分钟直至获得均质分散体。将溶液浇铸在基底(诸如不锈钢、PVC和纤维板)上，然后在室温下固化。  \n\n[0192] 实例22  \n\n[0193]在搅拌下将聚氨酯分散体W835/140(32重量 $\\%,32.8\\mathrm{g}$ 与11.5g的 $900{-}\\mathrm{DA}$ (30重量 $\\%$ )混合，以形成均质分散体，然后添加1.0g的Bacote20(20重量 $\\%$ 的水溶液）、0.75g的Jeecol LA-7（得自Jeen国际公司（Jeen International Co.）的 $\\mathrm{C_{12}E0_{7}})$ 和 $1.0\\mathrm{g}$ 的BYK-346并搅拌20分钟直至获得均质分散体。将溶液浇铸在基底(诸如不锈钢、PVC和纤维板)上，然后在室温下固化。  \n\n[0194]使用VCA Optima测角计(AST产品公司(AST products,INC)）从所得涂覆和未涂覆 的基底获得与水的接触角测量值。结果报告于下表中。   \n[0195]  \n\n<html><body><table><tr><td colspan=\"5\">接触角分析（度）</td></tr><tr><td>样品</td><td>前进</td><td>标准偏 差</td><td colspan=\"2\">标准偏 后退 差</td></tr><tr><td>纤维板对照</td><td>54.3</td><td>11.7</td><td>20.4</td><td>3.0</td></tr><tr><td>具有实例21涂层的 纤维板</td><td>16.8</td><td>1.5</td><td><3</td><td></td></tr><tr><td>具有实例22涂层的 纤维板</td><td>15.6</td><td>0.9</td><td><3</td><td></td></tr><tr><td>不锈钢对照</td><td>89.4</td><td>2.7</td><td>35.5</td><td>2.4</td></tr><tr><td>具有实例21涂层的 不锈钢</td><td>19.6</td><td>0.3</td><td><3</td><td></td></tr><tr><td>具有实例22涂层的 不锈钢</td><td>16.1</td><td>1.1</td><td><3</td><td></td></tr><tr><td>PVC对照</td><td>68.3</td><td>8.9</td><td>25.6</td><td>2.0</td></tr><tr><td>具有实例21涂层的 PVC</td><td>19.0</td><td>0.4</td><td><3</td><td></td></tr><tr><td>具有实例22涂层的 PVC</td><td>16.7</td><td>0.1</td><td><3</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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new file mode 100644
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+++ b/task2/task2-chunks/CN104926988B.json
@@ -0,0 +1,52 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n(10)授权公告号CN104926988B (45)授权公告日2017.08.22  \n\n<html><body><table><tr><td>(21)申请号201410100625.5</td><td>C08F 226/06(2006.01)</td></tr><tr><td>(22)申请日2014.03.19</td><td>C09K 8/035(2006.01)</td></tr><tr><td>(65)同一申请的已公布的文献号</td><td>(56)对比文件</td></tr><tr><td>申请公布号CN104926988A</td><td>CN 1772778 A,2006.05.17,</td></tr><tr><td>（43)申请公布日2015.09.23</td><td>JP 2012025820 A,2012.02.09,</td></tr><tr><td></td><td>CN 101519473 A,2009.09.02,</td></tr><tr><td>(73)专利权人中国石油化工股份有限公司</td><td>CN 1240795 A,2000.01.12,</td></tr><tr><td>地址100728北京市朝阳区朝阳门北大街 22号</td><td>刘小军等.两性离子聚丙烯酰胺的合成.《精</td></tr><tr><td>专利权人中国石油化工股份有限公司抚顺</td><td>细石油化工进展》.2010，(第08期)，</td></tr><tr><td>石油化工研究院</td><td>桂张良等.含磺酸甜菜碱两性离子共聚物P (AM-co-VPPS)的合成及盐溶液性质.《高分子学</td></tr><tr><td>(72)发明人杨超鲁娇陈楠张志智</td><td>报》.2009,(第04期)，</td></tr><tr><td>尹泽群刘全杰</td><td>审查员 李青莲</td></tr></table></body></html>  \n\n(51)Int.Cl. C08F 220/56(2006.01) C08F 220/38(2006.01)",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n一种用于钻井液的两性离子共聚物的制备方法",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明提供一种用于钻井液的两性离子共聚物的制备方法，称取质量比为 $2{:}1{\\sim}9{:}1$ 的甲基丙烯酸二甲氨基乙酯和1，3-丙磺酸内酯，并向甲基丙烯酸二甲氨基乙酯中加入1，3-丙磺酸内酯，反应后经过滤、抽提、干燥制得DMAPS；按照比例分别称取DMAPS、AM和VPPS，加去溶剂溶解后转移至反应器，然后通入N2除氧反应，然后加入引发剂反应得到凝胶状固体，用丙酮沉淀得白色沉淀物；得到的沉淀物经干燥后粉碎，最终得两性离子共聚物。本发明方法得到的聚合物可耐温高达$180^{\\circ}\\mathrm{C}$ ，抗NaC1饱和、抗CaC12饱和，且随盐量的增加聚合物的降滤失量减小，同时还具有优越的页岩抑制性能。  \n\n1.一种用于钻井液的两性离子共聚物的制备方法，其特征在于：所述制备方法包括如下步骤：  \n\n(1)首先分别称取质量比为 $2\\colon1\\sim9\\colon1$ 的甲基丙烯酸二甲氨基乙酯和1,3-丙磺酸内酯，并向甲基丙烯酸二甲氨基乙酯中加入1,3-丙磺酸内酯，然后在 $10{\\sim}60^{\\circ}\\mathrm{C}$ 的温度下反应0.5${\\sim}4\\mathrm{h}$ ,最后经过滤、抽提、干燥制得甲基丙烯酰氧乙基-N， $\\mathrm{N^{-}}$ 二甲基丙磺酸盐;  \n\n(2)按照摩尔比为 $1:1.1{\\sim}1:1.3$ 分别称取4-乙烯基吡啶和1,3-丙磺酸内酯，然后称取有机溶剂和助剂,有机溶剂与4-乙烯基吡啶和1,3-丙磺酸内酯的总质量比为 $2\\colon1\\sim8\\colon1$ ,助剂与4-乙烯基吡啶、1,3-丙磺酸内酯和有机溶剂的总质量比为 $0.001{\\sim}0.01$ ，然后将有机溶剂平均分成三份，分别与4-乙烯基吡啶、1,3-丙磺酸内酯、助剂溶解混合，将得到的三种混合溶液依次加入反应器，在 $20^{\\circ}\\mathrm{C}\\sim90^{\\circ}\\mathrm{C}$ 条件下反应 $1\\sim10\\mathrm{h}$ ，然后经过滤、洗涤、干燥制得4-乙烯基吡啶丙磺酸内盐;(3)按照 $1.5{\\sim}3:6{\\sim}7:0.5{\\sim}1.5$ 的摩尔比分别称取步骤(1)的得到的甲基丙烯酰氧乙基-N， $\\mathrm{N^{-}}$ 二甲基丙磺酸盐、丙烯酰胺和步骤(2)得到的4-乙烯基吡啶丙磺酸盐，加入溶剂溶解后通入N除氧 $0.5\\sim1\\mathrm{h}$ ，同时升温至 $50{\\sim}70^{\\circ}\\mathrm{C}$ ，恒温 $5\\sim10\\mathrm{min}$ 后加入引发剂反应 $4\\mathrm{\\sim}6\\mathrm{h}$ ，反应后得到凝胶状固体，用丙酮沉淀得白色沉淀物；(4)将步骤(3)得到的沉淀物在 $100{\\sim}120^{\\circ}\\mathrm{C}$ 下干燥 $16\\sim24\\mathrm{h}$ 后粉碎，最终得两性离子共聚物。2.按照权利要求1所述的方法,其特征在于：步骤(1)中甲基丙烯酸二甲氨基乙酯和1，3-丙磺酸内酯的质量比为 $2.5{:}1{\\sim}8{:}1$ 03.按照权利要求1所述的方法，其特征在于：步骤(1)中1,3-丙磺酸内酯滴加到甲基丙烯酸二甲氨基乙酯中或者直接一次性加入到甲基丙烯酸二甲氨基乙酯中。4.按照权利要求1或3所述的方法,其特征在于：步骤(1)中1,3-丙磺酸内酯直接一次性加入到甲基丙烯酸二甲氨基乙酯中。5.按照权利要求3所述的方法，其特征在于：采用直接一次性加入时称取的甲基丙烯酸二甲氨基乙酯和1,3-丙磺酸内酯质量比为 $5.2{:}1{\\sim}7.8{:}1$ 06.按照权利要求3所述的方法，其特征在于：采用滴加方式时甲基丙烯酸二甲氨基乙酯和1，3-丙磺酸内酯质量比为 $2.5{:}1\\sim5{:}1$ o7.按照权利要求1所述的方法，其特征在于：步骤(1)的反应条件为在 $20{\\sim}55^{\\circ}\\mathrm{C}$ 的温度下反应 $\\mathrm{.1\\sim3h}$ 08.按照权利要求1所述的方法，其特征在于：步骤(1)中所述抽提溶剂选用甲醇或乙醇，抽提时间为 $1\\sim3\\mathrm{h}$ 09.按照权利要求1所述的方法，其特征在于：步骤(1)中所述干燥为在 $30{\\sim}50^{\\circ}\\mathrm{C}$ 下干燥$10\\mathrm{\\sim}20\\mathrm{h}$ 010.按照权利要求1所述的方法,其特征在于：步骤(2)中所述有机溶剂为苯、甲苯、乙酸乙酯、丙酮、环己酮、碳酸丙烯酯中的任一种。11.按照权利要求1所述的方法，其特征在于：步骤(2)中所述助剂为羟胺类化合物和硝基苯类化合物,其中羟胺类化合物为二甲基羟胺、二乙基羟胺、二丙基羟胺、异丙基羟胺、二丁基羟胺、甲基乙基羟胺中的任一种;硝基苯类化合物为1,2-二硝基苯、1,3-二硝基苯、1，$4^{-}.$ 二硝基苯、1,3,5-三硝基苯中的任一种。  \n\n12.按照权利要求1所述的方法，其特征在于：步骤(2)中所述洗涤操作为用步骤(2)中所述有机溶剂洗涤 $2{\\sim}5$ 次，步骤(2)中所述干燥为在 $40{\\sim}60^{\\circ}\\mathrm{C}$ 下干燥 $10\\mathrm{\\sim}20\\mathrm{h}$ 013.按照权利要求1所述的方法，其特征在于：步骤(3)中所述溶剂为去离子水或者盐水，所述盐水中加入的NaCl浓度为 $0{\\sim}0.5\\mathrm{mol/L}.$ O14.按照权利要求1所述的方法，其特征在于：步骤(3)中加入溶剂后单体总浓度为 $20\\%$ ${\\sim}40\\%$ 015.按照权利要求1所述的方法，其特征在于：步骤(3)中使用的引发剂为过硫酸钾、过硫酸钠、过硫酸铵中任一种。16.按照权利要求1所述的方法，其特征在于：所述引发剂用量占单体总质量 $0.5\\%\\sim$ $0.7\\%$ 0",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 一种用于钻井液的两性离子共聚物的制备方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001]］本发明涉及石油钻井过程中用于钻井液聚合物及其制备方法，特别是涉及一种钻井液用两性离子共聚物的制备方法。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002］钻井液用聚合物涉及的种类复杂繁多、功能各异，但其中的降滤失剂最为重要，是用量最大的聚合物处理剂。降滤失剂是用以保证钻井液性能稳定，减少有害液体侵入地层，以及保证井径规则、稳定井壁的重要钻井液处理剂。随着钻遇地层日趋复杂，以及特殊井、超深井和复杂井数量的增多，对钻井液降滤失剂提出了更高的要求，以满足耐盐性(NaCl浓度大于 $10\\%$ ,CaCl2浓度大于 $5\\%$ )和耐温性(温度高于 $\\mathrm{150^{\\circ}C)}$ 的新要求。糊化淀粉、羧甲基纤维素、褐煤等都是最早使用的钻井液降滤失剂。随着研究的不断深入以及钻遇地层的日趋复杂性，已有的天然及天然改性的降滤失剂已经不能满足钻井条件的需要，从而促进了人工合成聚合物类降滤失剂的研究与发展。  \n\n[0003］由于两性离子聚合物中既含有具有吸附和水化双重作用的阳离子基团，又含有大量的水化基团，可以在粘土颗粒周围形成致密的水化层，阻止和延缓水分子与粘土表面接触，起到防止粘土颗粒水化膨胀的作用;阳离子基团和阴离子基团在水中电离不受外加盐的影响，还有可能阻止酰胺基的水解，因此两性离子聚合物还具有耐温抗盐的优点，其研究和开发应用正逐步受到重视。杨小华采用MAOPS,AM和AA合成两性离子磺酸盐聚合物CPS-2000，在各种钻井液体系中均具有较强的降滤失、提黏切能力和抑制性作用，还具有较强的耐温和抗盐、抗钙能力。杨金荣以氧化还原体系为引发剂,采用水溶液聚合合成了两性离子四元共聚物：聚丙烯酰胺-二甲基二烯丙基氯化铵 $-2-$ 丙烯酰胺基-2-甲基丙磺酸钠-甲基丙烯酸(PADAM)，具有较强的降失水能力和抑制性、较好的耐盐性和耐温性。郑海洪以丙烯酰胺(AM)、2-丙烯酰胺-2-甲基丙磺酸(AMPS)、二甲基二烯丙基氯化铵(DMDAAC)和顺丁烯二酸酐(MA）为单体，采用水溶液聚合方法，以过硫酸铵/亚硫酸氢钠为引发剂合成了两性离子聚合物降滤失剂PA-1,热稳定性好，降滤失能力和抗温能力强。杨文以二甲基二烯丙基氯化铵(DMDAAC)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、马来酐(MA)、丙烯酰胺(AM）为单体，氧化还原体系为引发剂，利用水溶液聚合法合成了两性离子聚合物降滤失剂PMADA。贺爱民采用水溶液聚合方法合成的AEDMAC/AM/AA两性共聚物降滤失剂，具有良好的降滤失、防塌、保护油气层性能，抗温、抗盐性较好。中国专利CN2008100472416以丙烯酰胺2-丙烯酰胺基-2-甲基丙磺酸为单体，采用水溶液聚合合成了一种两性离子聚合物降滤失剂，抗温耐盐性较强。  \n\n[0004]但上述的两性离子聚合物的制备均是由阴、阳离子单体共聚得到。由于受阳离子单体聚合活性及竞聚率的限制，共聚物中阴离子含量要远大于阳离子含量，导致共聚物中正负电荷的数量不相等，达不到理想的“反聚电解质\"效应，聚合物抗盐抗钙性能有限。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0005]针对现有技术的不足，本发明提供一种用于钻井液的两性离子共聚物的制备方法。本发明方法得到的用于钻井液的两性离子共聚物可耐温高达 $180^{\\circ}\\mathrm{C}$ ，抗NaCl饱和、抗CaCl2饱和，且随盐量的增加聚合物的降滤失量减小，同时还具有优越的页岩抑制性能。  \n\n[0006] 本发明制备方法得到的两性离子共聚物的结构如下：  \n\n[0007]  \n\n![](images/ba9a384db3d634f768a6e17cd5cfc5ebdf51fe77b237b36078fc9511d1d9227a.jpg)  \n\n[0008] 本发明所述用于钻井液的两性离子共聚物的制备方法包括如下步骤：  \n\n[0009］(1)首先分别称取质量比为 $2\\colon1\\sim9\\colon1$ 的甲基丙烯酸二甲氨基乙酯和1,3-丙磺酸内酯，并向甲基丙烯酸二甲氨基乙酯中加入1,3-丙磺酸内酯，然后在 $10{\\sim}60^{\\circ}\\mathrm{C}$ 的温度下反应$0.5{\\sim}4\\mathrm{h}$ ，最后经过滤、抽提、干燥制得甲基丙烯酰氧乙基-N， $\\mathrm{N^{-}}$ 二甲基丙磺酸盐;  \n\n[0010](2)首先按照摩尔比为 $1:1.1\\sim1:1.3$ 分别称取4-乙烯基吡啶和1,3-丙磺酸内酯，然后称取有机溶剂和助剂，有机溶剂与4-乙烯基吡啶和1,3-丙磺酸内酯的总质量比为2:1${\\sim}8!\\$ ，助剂与4-乙烯基吡啶、1,3-丙磺酸内酯和有机溶剂的总质量比为 $0.001{\\sim}0.01$ ，然后将有机溶剂平均分成三份，分别与4-乙烯基吡啶、1,3-丙磺酸内酯、助剂溶解混合，将得到的三种混合溶液依次加入反应器，在 $20^{\\circ}\\mathrm{C}\\sim90^{\\circ}\\mathrm{C}$ 条件下反应 $1\\sim10\\mathrm{h}$ ,然后经过滤、洗涤、干燥制得4-乙烯基吡啶丙磺酸内盐;  \n\n[0011] (3)按照 $1.5{\\sim}3:6{\\sim}7:0.5{\\sim}1.5$ 的摩尔比分别称取步骤(1)的得到的甲基丙烯酰氧乙基-N， $\\mathrm{N^{-}}$ 二甲基丙磺酸盐、丙烯酰胺和步骤(2)得到的 $4^{-}$ 乙烯基吡啶丙磺酸盐，加入溶剂溶解后通入N2除氧 $0.5\\sim1\\mathrm{h}$ ，同时升温至 $50{\\sim}70^{\\circ}\\mathrm{C}$ ，恒温 $5\\sim10\\mathrm{min}$ 后加入引发剂反应4${\\sim}6\\mathrm{h}$ ，反应后得到凝胶状固体，用丙酮沉淀得白色沉淀物;  \n\n[0012](4)将步骤(3)得到的沉淀物在 $100{\\sim}120^{\\circ}\\mathrm{C}$ 下干燥 $16\\sim24\\mathrm{h}$ 后粉碎，最终得DMAPS-AM-VPPS两性离子共聚物。  \n\n[0013]本发明方法中，步骤(1)中甲基丙烯酸二甲氨基乙酯和1,3-丙磺酸内酯的质量比为 $2.5{:}1{\\sim}8{:}1$ 0  \n\n[0014]本发明方法中，步骤(1)中1,3-丙磺酸内酯滴加到甲基丙烯酸二甲氨基乙酯中或者直接一次性加入到甲基丙烯酸二甲氨基乙酯中，优选直接加入方式。采用直接一次性加入时称取的甲基丙烯酸二甲氨基乙酯和1,3-丙磺酸内酯质量比为 $5.2{:}1{\\sim}7.8{:}1$ 采用滴加方式时甲基丙烯酸二甲氨基乙酯和1,3-丙磺酸内酯质量比为 $2.5{:}1\\sim5{:}1$ ,滴加前可以将1，3-丙磺酸内酯加热熔化。  \n\n[0015] 本发明方法中，步骤(1)的反应条件为在 $20{\\sim}55^{\\circ}\\mathrm{C}$ 的温度下反应 $1\\sim3\\mathrm{h}$ 0[0016]本发明方法中，步骤(1)中抽提溶剂选用甲醇或乙醇，优选乙醇，抽提时间为 $1\\sim$ $\\mathrm{3h}$ 。所述干燥为在 $30{\\sim}50^{\\circ}\\mathrm{C}$ 条件下干燥 $10\\mathrm{\\sim}20\\mathrm{h}$ 0  \n\n[0017］本发明方法中，步骤(2)中所述有机溶剂为苯、甲苯、乙酸乙酯、丙酮、环己酮、碳酸丙烯酯中的任一种。  \n\n[0018]本发明方法中，步骤(2)中所述助剂为羟胺类化合物和硝基苯类化合物,其中羟胺类化合物为二甲基羟胺、二乙基羟胺、二丙基羟胺、异丙基羟胺、二丁基羟胺、甲基乙基羟胺中的任一种;硝基苯类化合物为1,2-二硝基苯、1,3-二硝基苯、1,4-二硝基苯、1,3,5-三硝基苯中的任一种。  \n\n[0019］本发明方法中，步骤(2)中所述过滤操作为将反应得到的产物转移至漏斗中过滤除去溶剂及未反应的原料，优选为使用布氏漏斗进行减压抽滤。  \n\n[0020]本发明方法中，步骤(2)中所述洗涤操作为用步骤(2)中所述有机溶剂洗涤 $2\\sim5$ 次。  \n\n[0021] 本发明方法中，步骤(2)中所述干燥为在 $40{\\sim}60^{\\circ}\\mathrm{C}$ 下干燥 $10\\mathrm{\\sim}20\\mathrm{h}$ 0[0022］本发明方法中，步骤(3)中所述溶剂为去离子水或者盐水，加入溶剂后单体总质量浓度为 $20\\%\\sim40\\%$ ，所述盐水中加入的NaCl浓度为 $0{\\sim}0.5\\mathrm{mol/L}$ 。  \n\n[0023］本发明方法中，步骤(3)中使用的引发剂为过硫酸钾、过硫酸钠、过硫酸铵中任一种;所述引发剂用量占单体总质量的 $0.5\\%{\\sim}0.7\\%$ 0  \n\n[0024] 与现有技术相比，本发明方法优点如下：  \n\n[0025](1)本发明方法将1,3-丙磺酸内酯加入到过量的甲基丙烯酸二甲氨基乙酯中，过量的甲基丙烯酸二甲氨基乙酯不仅可以作为原料参与反应，而且也能够起到溶剂的作用，避免了常规方法中使用有毒的丙酮为溶剂，是一种绿色的合成方法。  \n\n[0026］(2)本发明方法通过控制1,3-丙磺酸内酯和甲基丙烯酸二甲氨基的质量比及投料方式，解决了1,3-丙磺酸内酯和甲基丙烯酸二甲氨基按照常规方法直接进行反应时（一般为等摩尔比反应)，不能得到单体DMAPS的问题。  \n\n[0027］(3)本发明方法通过加入助剂,不仅使得合成得到的4-乙烯基吡啶丙磺酸内盐产品收率高，可达 $90\\%$ 以上，而且不需要经过重结晶步骤直接得到高纯度产品，产物为粉末状，产品纯度 $\\geqslant95\\%$ 。本发明方法具有反应时间短、操作简单，反应后反应器不挂胶，易于清洗维护，有利于工业化生产，适于工业应用。  \n\n[0028］（4)本发明方法制备的两性离子共聚物中，DMAPS和VPPS均为大分子聚合单体，其共聚得到的聚合物具有长支链及热稳定性高的环状共轭基团，在水溶液中由于它们的存在，增加了聚合物的空间位阻，增大了聚合物的流体力学体积，减少聚合物上酰胺基基团、酯基基团受温度影响断裂水解的趋势，从而提高了其耐温的性能，耐温可达 $180^{\\circ}\\mathrm{C}$ 0  \n\n[0029](5)本发明方法制备的两性离子共聚物属内盐型两性离子聚合物，与传统两性离子聚合物不同的是，其在淡水中分子间由于静电吸引力作用,表现为分子链蜷曲。而在高盐高钙溶液中，由于小分子盐的存在，屏蔽了分子间的缔合作用，将分子间的静电吸引力转变为静电排斥力，使得分子链更加舒展。它所表现出的明显“反聚电解质\"效应使聚合物的性能随盐量的增加逐渐增强。可抗NaCl饱和及CaCl2饱和，这是目前几乎所有的两性离子聚合物都不具备的抗盐抗钙性能。本发明方法得到的两性离子共聚物结构中还含有大量的季铵阳离子基团，使聚合物具有优越的页岩抑制性能。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 具体实施方式  \n\n[0030］下面结合实施例来具体说明本发明方法的作用和效果，但以下实施例不构成对本发明方案的限制。  \n\n[0031] 实施例1  \n\n[0032] 首先制备甲基丙烯酰氧乙基－N， $\\mathrm{N^{-}}$ 二甲基丙磺酸盐 (DMAPS)  \n\n[0033］称取 $630\\mathrm{g}$ 甲基丙烯酸二甲氨基乙酯(DM)放入反应器中，然后放入恒温水浴锅中，加热并开始搅拌。再称取 $^{122\\mathrm{g}\\mathrm{~1,3-}}$ 丙磺酸内酯(PS)，直接加入到DM中，反应温度为 $35\\mathrm{{^\\circC}}$ ，搅拌反应1.5h后得到DMAPS的粗产品。将DMAPS粗产品转移到大片滤纸中包裹住，放置于索式抽提器中，使用乙醇为溶剂抽提1h，抽提完毕后将滤纸包放在干燥箱中，在 $40^{\\circ}\\mathrm{C}$ 下干燥，最终得到纯净的DMAPS单体，产率为 $92.8\\%$ ，(产率为实际得到产物的质量与按化学计量比反应得到的理论产物质量的比值)。  \n\n[0034] 比较例1 (直接反应)  \n\n[0035］按照化学计量比DM:PS为1:1反应。称取157gDM倒入反应器中，然后放入恒温水浴锅中，加热并开始搅拌。再称取 $122\\mathrm{gPS}$ ，直接加入到DM中，反应温度为 $20\\mathrm{{^\\circC}}$ ，搅拌反应0.5h后得到大块聚合产物，已无DMAPS单体，产率为0。按照化学计量比反应时，反应中生产大量的热无法及时散去，温度瞬间急剧上升，导致原料DM和产物DMAPS都发生聚合。  \n\n[0036] 比较例2(常规方法，以丙酮为溶剂反应)  \n\n[0037]］称取 $170\\mathrm{gDM}$ 倒入反应器中，然后放入恒温水浴锅中，加热并开始搅拌。再称取$12\\mathrm{{2gPS}}$ 溶于 $1170\\mathrm{g}$ 丙酮，将混合溶液直接加入到DM中，反应温度为 $60^{\\circ}\\mathrm{C}$ ，搅拌反应4h后得到DMAPS的粗产品。将DMAPS粗产品转移到大片滤纸中包裹住，放置于索式抽提器中，使用乙醇为溶剂抽提2h，抽提完毕后将滤纸包放在干燥箱中，在 $35\\mathrm{{^\\circC}}$ 下干燥，最终得到纯净的DMAPS单体，产率为 $82.4\\%$ 0  \n\n[0038] 实施例2  \n\n[0039] 制备4-乙烯基吡啶丙磺酸内盐 (VPPS)  \n\n[0040]（1)分别称取105g的4-乙烯基吡啶(4-VP)、125g的1,3-丙磺酸内酯(PS)、500g的有机溶剂苯、0.75g的二乙基羟胺;  \n\n[0041］(2)将有机溶剂苯平均分成三份,分别与4-乙烯基吡啶、1,3-丙磺酸内酯、助剂二乙基羟胺溶解混合;  \n\n[0042](3)将得到的三种混合溶液依次加入反应器，在 $70\\mathrm{{^\\circC}}$ 下反应2h,然后经减压抽滤，然后使用苯洗涤 $2{\\sim}3$ 次，在 $50^{\\circ}\\mathrm{C}$ 下干燥15h，制得4-乙烯基吡啶丙磺酸内盐，经计算最终得到淡黄色固体粉末状产品 $2136\\mathrm{g}$ 0  \n\n[0043] 实施例3  \n\n[0044]分别称取 $50\\mathrm{gDMAPS}.60\\mathrm{gAM}$ 和 $40\\mathrm{gVPPS}$ ,加一定量去离子水溶解后转移至反应器，单体总浓度为 $35\\%$ 。通入N2除氧1h，同时升温至 $60^{\\circ}\\mathrm{C}$ ，保持30min后加入 $0.9\\mathrm{g}$ 过硫酸钾，反应6h后得到凝胶状固体，用丙酮沉淀得白色沉淀物。在 $110^{\\circ}\\mathrm{C}$ 下干燥24h后粉碎，最终得DMAPS/AM/VPPS两性离子共聚物。  \n\n[0045] 实施例4[0046] 分别称取120gDMAPS、60gAM、34gVPPS和 $\\mathrm{15gNaCl}$ ，加一定量去离子水溶解后转移至反应器，单体总浓度为 $30\\%$ 。通入N2除氧1h，同时升温至 $55\\mathrm{{^\\circC}}$ ，保持30min后加入 $1.4\\mathrm{g}$ 过硫酸钠，反应5h后得到凝胶状固体，用丙酮沉淀得白色沉淀物。在 $110^{\\circ}\\mathrm{C}$ 下干燥24h后粉碎，最终得DMAPS/AM/VPPS两性离子共聚物。  \n\n[0047] 比较例3  \n\n[0048]传统两性离子单体A,AMPS/AM/DMDAAC三元共聚物合成方法按文献《AM／AMPS/DMDAAC 共聚物合成及其降滤失性能研究》(王春华，2012年《山东化工》报道方法制备。  \n\n[0049] 比较例4  \n\n[0050］传统两性离子单体B,AMPS/AM/AA/阳离子单体四元共聚物合成方法按文献《抗高温抗海水降滤失剂的研究与性能评价》(王仲广，2010年《钻井液与完井液》报道方法制备。  \n\n[0051] 上述实施例及比较例使用含盐含钙的基浆评价降滤失性能，具体评价方法如下：  \n\n[0052]淡水基浆配制：在1000mL水中加入 $40\\mathrm{g}$ 钙膨润土和5g碳酸钠，高速搅拌20min，室温下放置养护24h，得到淡水基浆。  \n\n[0053］饱和盐水基浆：在 $1000\\mathrm{mL}$ 淡水基浆中加人 $36\\%\\mathrm{{NaCl}}$ ,高速搅拌20min,室温下养护24h，得到饱和盐水基浆。  \n\n[0054]抗盐性能评价方法：量取 $350\\mathrm{mL}$ 的淡水基浆,先加入一定量NaCl,高速搅拌5min，再加入 $1.5\\%$ 的两性离子共聚物，高速搅拌5min，常温养护24h后测中压滤失量。通过考察在淡水基浆中不断增加NaCl的量，测定降滤失量的变化。其中降滤失量越低越好。  \n\n[0055］抗钙性能评价方法：量取350mL的饱和盐水基浆，先加入一定量CaCl2，高速搅拌5min，再加入 $2.0\\%$ 的两性离子共聚物，高速搅拌5min，常温养护24h后测中压滤失量。在饱和盐水基浆中不断增加CaCl2的量，测定降滤失量的变化。  \n\n[0056] 表1不同两性离子聚合物抗盐性能对比表  \n\n[0057]  \n\n<html><body><table><tr><td rowspan=\"7\">057]</td><td>Naa加 谷</td><td>实美例3</td><td>3 实施例4德比较例3 A</td><td></td><td>比较例48</td></tr><tr><td></td><td>12</td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td>4</td><td></td><td>9</td><td>12</td><td>13</td></tr><tr><td>10</td><td>10</td><td>8.</td><td>19</td><td>15</td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td>20</td><td></td><td>，</td><td>25</td><td>18</td></tr><tr><td>30</td><td>7.5</td><td></td><td>36</td><td>20</td></tr></table></body></html>  \n\n[0058] 表2不同两性离子聚合物抗钙性能对比表  \n\n![](images/52fff79f5b51e1957db2fa04153d4a3701dfe74fea62e457ef060a49c2838304.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# [0060] 表3不同两性离子聚合物抗温性能对比表  \n\n[0061]   \n\n\n<html><body><table><tr><td>老化温度/℃</td><td>实施例3滤失量/mL</td><td>实施例4滤失量/mL</td><td>比较例3滤失量/mL</td><td>比较例4滤失量/mL</td></tr><tr><td>120</td><td>8</td><td>6</td><td>33</td><td>11</td></tr><tr><td>150</td><td>15</td><td>11</td><td>57</td><td>19</td></tr><tr><td>180</td><td>24</td><td>20</td><td>126</td><td>47</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,42 @@
+[
+    {
+        "id": 1,
+        "chunk": "# （19)中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n<html><body><table><tr><td>(21)申请号 201580044953.0</td><td>(51)Int.CI.</td></tr><tr><td>(22)申请日2015.09.08</td><td>CO9K 3/00(2006.01)</td></tr><tr><td>(65)同一申请的已公布的文献号</td><td>B32B 27/30(2006.01)</td></tr><tr><td>申请公布号CN 106574167A</td><td>B32B 27/40(2006.01)</td></tr><tr><td></td><td>CO9D 5/16(2006.01)</td></tr><tr><td>(43)申请公布日2017.04.19</td><td>CO9D 133/14(2006.01)</td></tr><tr><td>(30)优先权数据</td><td>CO9D 133/26(2006.01)</td></tr><tr><td>2014-192217 2014.09.22 JP</td><td>C09D 175/04(2006.01) C09K 3/18(2006.01)</td></tr><tr><td>(85)PCT国际申请进入国家阶段日</td><td></td></tr><tr><td>2017.02.21</td><td>(56)对比文件</td></tr><tr><td>(86)PCT国际申请的申请数据</td><td>US 5180760 A,1993.01.19, CN 1662466 A,2003.07.29,</td></tr><tr><td>PCT/JP2015/075382 2015.09.08</td><td>CN 101065456 A,2007.10.31,</td></tr><tr><td>(87)PCT国际申请的公布数据</td><td></td></tr><tr><td>WO2016/047430 JA 2016.03.31</td><td>CN 102666753 A,2012.09.12,</td></tr><tr><td></td><td>CN 103391875 A,2013.11.13,</td></tr><tr><td>(73)专利权人日油株式会社</td><td>JP 特开2008-150454 A,2008.07.03,</td></tr><tr><td>地址 日本东京都</td><td>JP 特开2012-7033 A,2012.01.12,</td></tr><tr><td>(72)发明人加纳崇光鹤冈大杉原靖</td><td>审查员霍艳丽</td></tr><tr><td>(74)专利代理机构北京路浩知识产权代理有限 公司11002</td><td></td></tr><tr><td>代理人张晶 谢顺星</td><td>权利要求书2页说明书23页</td></tr></table></body></html>",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n2)。  \n\n防雾剂组合物及使用该防雾剂组合物的防雾性产品",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明提供一种防雾性能的持久性优异的防雾剂组合物。该防雾剂组合物由共聚物(A)、多官能嵌段异氰酸酯化合物(B)和表面活性剂(C)组成。所述共聚物(A)由相对于100重量份的所述共聚物(A)为 $35{\\sim}90$ 重量份的单体（A-1） $.5\\sim60$ 重量份的单体(A-2） $5\\sim30$ 重量份的单体(A-3)构成。所述多官能嵌段异氰酸酯化合物(B)的异氰酸酯基含量NCO与所述共聚物(A)的羟基含量OH之比NCO/OH比为 $0.1{\\sim}1.5$ 的范围。相对于100重量份的所述共聚物(A)，所述表面活性剂(C)含有 $1.00{\\sim}10.0\\$ 重量份的阴离子表面活性剂(C-1)和 $0.01{\\sim}3.00$ 重量份的阳离子表面活性剂( $\\mathrm{C^{-}}$  \n\n1.一种防雾剂组合物,其由共聚物(A)、多官能嵌段异氰酸酯化合物(B)和表面活性剂(C)组成，  \n\n所述共聚物(A)由下列通式(1)或(2)所示单体(A-1)、下列通式(3)所示单体(A-2)和下列通式(4)或(5)所示单体(A-3)构成，  \n\n[化学式1]  \n\n![](images/9a3a770c27dac54f47f25e5d89e7ae5ffcb71daaacf719b2d81257b2d59a05cc.jpg)  \n\n通式(1)中， $\\mathrm{R}^{1}$ 为氢原子或甲基， $\\mathrm{R}^{2}$ 为碳原子数 $1{\\sim}4$ 的直链或枝化的烷基、 $\\mathrm{.-C\\left(CH_{3}\\right)}$ $\\mathrm{2CH_{2}C O C H_{3}}$ 、-C2H4N(CH3)2、或者 $\\mathrm{-C_{3}H_{6}N\\left(C H_{3}\\right)_{2},R^{3}.}$ 为氢原子或直链或枝化的碳原子数 $1{\\sim}4$ 的烷基，  \n\n[化学式2]  \n\n![](images/3ba2fa304aaceb92d5ee01ce96d022b3e3bba02c3229e548aa4f3b327bce0f47.jpg)  \n\n通式(2)中， $\\mathrm{R}^{4}$ 为氢原子或甲基，[化学式3]  \n\n![](images/5ee4c2ce9705fde9a416b40b57b400b2f477eda3fa20cc67c9bbe2c092a0d1a4.jpg)  \n\n通式(3)中， $\\mathrm{R}^{5}$ 为氢原子或甲基， $\\boldsymbol{\\mathrm{R}}^{6}$ 为碳原子数 $1{\\sim}16$ 的直链、枝化或环状的烷基，[化学式4]  \n\n![](images/cb116004de241a229c6c4ffc3d694811313d9058b6be408b7b4671e761a14de6.jpg)  \n\n通式(4)中， $\\mathrm{R}^{7}$ 为氢原子或甲基， $\\boldsymbol{\\mathrm{R}}^{8}$ 为碳原子数 $2{\\sim}4$ 的直链或枝化的亚烷基、或者-C2H4$\\left(\\mathrm{OCO}\\left(\\mathrm{CH_{2}}\\right){5}\\right){\\mathrm{n}}^{-},{\\mathrm{n}}{=}1{\\sim}5,$ [化学式5]  \n\n![](images/30cc462524b7c10b2b3edc62166d059561df8a905a878b6895a3a94909d2e13c.jpg)  \n\n通式(5)中， $\\boldsymbol{\\mathrm{R}}^{9}$ 为氢原子或甲基， $\\mathrm{R}^{10}$ 为碳原子数 $1{\\sim}4$ 的直链或枝化的亚烷基，  \n\n相对于共计100重量份的所述单体(A-1)、所述单体(A-2)及所述单体(A-3)，所述单体(A-1)为 $35{\\sim}90$ 重量份，所述单体(A-2)为 $5\\sim60$ 重量份，所述单体(A-3)为 $5\\sim30$ 重量份，  \n\n所述多官能嵌段异氰酸酯化合物(B)的异氰酸酯基含量NCO与所述共聚物(A)的羟基含量OH之比的NCO/OH比为 $0.1{\\sim}1.5$ 的范围，  \n\n相对于100重量份的所述共聚物(A)，所述表面活性剂(C)含有 $1.00\\sim10.0\\$ 重量份的阴离子表面活性剂 $(\\mathrm{C}\\mathrm{-}1)$ 和 $0.01{\\sim}3.00$ 重量份的阳离子表面活性剂(C-2)。  \n\n2.根据权利要求1所述的防雾剂组合物，其中，所述阴离子表面活性剂(C-1)为氟类表面活性剂。  \n\n3.一种防雾性产品，其具备基材和防雾膜，所述防雾膜为在所述基材上涂布根据权利要求1或2所述的防雾剂组合物被加热固化而形成。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 防雾剂组合物及使用该防雾剂组合物的防雾性产品",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001］本发明涉及具有优异防雾性能的防雾剂组合物及使用了该防雾剂组合物的防雾性产品。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002］汽车前灯等照明装置以如下方式构成：在光源前方配置有由玻璃或塑料等形成的透明部件，光源发出的光通过透明部件照射到外部。在这种照明装置中，例如，在透明部件的内侧起雾时，照射光的强度降低，同时可能有损照射光的美观。  \n\n[0003］专利文献1公开了可用于防止上述照明装置中的起雾的防雾剂组合物。该防雾剂组合物含有下列成分：  \n\n[0004] ·单体(A)：非交联性的水溶性乙烯基类单体  \n[0005] ·单体 (B)：非交联性的非水溶性乙烯基类单体  \n[0006] ·单体(C)：具有羟基的乙烯基类单体  \n[0007] ·具有异氰酸酯基的交联剂 (D)  \n[0008]·表面活性剂(E)  \n\n[0009］在专利文献1所述防雾剂组合物中，基于单体(A)的性质，可获得防雾性能，基于单体(B)的性质，可获得良好的贴附性和耐水性，利用表面活性剂(E)的功能，可获得良好的防雾性能。  \n\n[0010] 现有技术文献  \n[0011] 专利文献  \n[0012] 专利文献1：特开第2010-150351号公报",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0013]本发明要解决的技术问题  \n[0014]由专利文献1所述防雾剂组合物获得的防雾膜在用于在反复进行结露的环境中使用的汽车前灯等时，表面活性剂(E)慢慢流出。因此，使用了专利文献1所述防雾剂组合物的防雾性产品，随着使用其防雾性能 (水膜形成能力)可能会降低。  \n[0015]鉴于上述事实，本发明的目的在于提供防雾性能的持久性优异的防雾剂组合物及使用了该防雾剂组合物的防雾性产品。  \n[0016] 解决技术问题的技术手段  \n[0017] 为了达到上述目的，本发明的一个实施方式的防雾剂组合物由共聚物(A)、多官能嵌段异氰酸酯化合物 (B)和表面活性剂(C)组成。  \n[0018] 上述共聚物(A)由下列通式(1)或(2)所示单体(A-1)、下列通式(3)所示单体(A-2)和下列通式(4)或(5)所示单体(A-3)构成。  \n[0019] ［化学式1]  \n\n[0020]  \n\n![](images/4f5f264539c57b8dd32ef11e401a0d0c4cbbb71ecbf8c7446caf2a04e02b6740.jpg)  \n\n[0021](通式（1)中， $\\mathrm{R}^{1}$ 为氢原子或甲基， $\\mathrm{R}^{2}$ 为碳原子数 $1{\\sim}4$ 的直链或枝化的烷基、 $-\\mathrm{C}$ (CH3) $\\mathrm{2CH_{2}C O C H_{3}}$ 、-C2H4N(CH3)2、或者-C3H6N(CH3)2， $\\mathrm{R}^{3}$ 为氢原子或直链或枝化的碳原子数 $1{\\sim}4$ 的烷基。)  \n\n[0022] [化学式2]  \n\n[0023] \\*\\*·(2)  \n\n![](images/31a15c3a4a3fff15d00a092002e5d39f304266ac17d504e95968525a1b093aec.jpg)  \n\n[0024] (通式(2)中， $\\mathrm{R}^{4}$ 为氢原子或甲基。)[0025] [化学式3]  \n\n[0026]  \n\n![](images/eb67d76b1a02cc887627b2d3bd33b83319733ad735ece500d55684bd65795cb8.jpg)  \n\n[0027] (通式(3)中， $\\mathrm{R}^{5}$ 为氢原子或甲基， $\\boldsymbol{\\mathrm{R}}^{6}$ 为碳原子数 $1\\sim16$ 的直链、枝化或环状的烷基。)[0028] [化学式4]  \n\n[0029]  \n\n![](images/1a3faa1ba5e51bc2b9fc98bc9402fdb701d0da0cc4f797c449d3a826271b41ec.jpg)  \n\n[0030] (通式(4)中， $\\mathrm{R}^{7}$ 为氢原子或甲基， $\\mathrm{R}^{8}$ 为碳原子数 $2{\\sim}4$ 的直链或枝化的亚烷基、或者-  \n$\\mathrm{C_{2}H_{4}}\\left(\\mathrm{OCO}\\left(\\mathrm{CH_{2}}\\right){\\mathfrak{s}}\\right)_{\\mathfrak{n}}-\\left(\\mathrm{n}{=}1{\\ \\widetilde{-5}}\\right){\\mathfrak{o}}\\right)$   \n[0031] [化学式5]  \n\n![](images/09774eef864b5debdcf28219857f2d9eec5ef8d0149d149bd27ca7b0ebd80d52.jpg)  \n\n[0033] (通式(5)中， $\\mathrm{R}^{9}$ 为氢原子或甲基， $\\mathrm{R}^{10}$ 为碳原子数 $1{\\sim}4$ 的直链或枝化的亚烷基。)  \n\n[0034]相对于共计100重量份的上述单体(A-1)、上述单体(A-2)及上述单体(A-3)，上述单体 (A-1)为 $35{\\sim}90$ 重量份，上述单体(A-2)为 $5\\sim60$ 重量份，上述单体(A-3)为 $5\\sim30$ 重量份。  \n\n[0035]上述多官能嵌段异氰酸酯化合物(B)的异氰酸酯基含量(NCO)与上述共聚物(A)的 羟基含量(OH)之比NCO/OH为 $0.1{\\sim}1.5$ 的范围。  \n\n[0036]相对于100重量份的上述共聚物(A)，上述表面活性剂(C)含有 $1.00\\sim10.0\\$ 重量份的阴离子表面活性剂(C-1)和 $0.01{\\sim}3.00$ 重量份的阳离子表面活性剂(C-2)。  \n[0037]该构成通过阴离子表面活性剂(C-1)和阳离子表面活性剂(C-2)的并用，使得由结露等产生的水分所导致的表面活性剂的流出难以发生。因此，该防雾剂组合物难以随着使用而降低防雾性能(水膜形成能力)，保持了优异的防雾性能。  \n[0038] 上述阴离子表面活性剂(C-1)可以是氟类表面活性剂。  \n[0039] 通过该构成，可以更好的降低水的表面张力。  \n[0040] 本发明的一个实施方式的防雾性产品具备基材和防雾膜。  \n[0041] 上述防雾膜是由涂布于上述基材上的上述防雾剂组合物经加热固化而形成的。[0042] 通过该构成，壳获得由难以随着使用而降低防雾性能 (水膜形成能力)、保持优异防雾性能的防雾膜所形成的防雾性产品。  \n[0043] 发明效果  \n[0044] 可以提供防雾性能的持久性优异的防雾剂组合物及防雾性产品。具体实施方式  \n[0045]下面对本发明的实施方式进行说明。  \n[0046］本发明的一个实施方式涉及一项技术，该技术用于在例如汽车前灯等所使用的透明部件等、作为赋予防雾性能的对象的基材的表面上设置防雾膜。本实施方式的防雾膜是通过使作为多种材料的混合物的防雾剂组合物加热固化而形成。防雾剂组合物所含成分以可在加热固化后的防雾膜中有效获得防雾性能的持久性的方式决定。  \n[0047] [防雾剂组合物]  \n[0048] 本实施方式的防雾剂组合物具有共聚物(A)、多官能嵌段异氰酸酯化合物(B)和表面活性剂(C)。  \n[0049] (表面活性剂(C))  \n[0050] 在本实施方式的防雾剂组合物中，作为表面活性剂(C)，并用了阴离子表面活性剂(C-1)和阳离子表面活性剂(C-2)。在该构成中，阴离子表面活性剂(C-1)的阴离子和阳离子表面活性剂(C-2)的阳离子形成离子对。由此使得难以发生阴离子表面活性剂(C-1)和阳离子表面活性剂(C-2)由于结露等产生的水分所导致的流出。  \n[0051]因此，由本实施方式的防雾剂组合物获得的防雾膜通过阴离子表面活性剂(C-1)和阳离子表面活性剂(C-2)的作用，难以发生随着使用而产生的防雾性能(水膜形成能力)下降，保持了优异的防雾性能。  \n[0052］当阴离子表面活性剂(C-1)为含氟表面活性剂时，由于能够更好的降低由防雾剂组合物获得的防雾膜中的水的表面张力，从而可获得更高的防雾性能。  \n[0053]相对于100重量份的共聚物(A)，阴离子表面活性剂(C-1)的量优选在 $1.00{\\sim}10.00$ 重量份的范围内。若阴离子表面活性剂(C-1)的量不足1.00重量份，则防雾膜的防雾性能的持久性降低,同时耐热试验后的防雾性能降低。另一方面,若阴离子表面活性剂(C-1)的量超过10.00重量份，则防雾膜上的滴水痕迹容易变醒目。  \n[0054］相对于100重量份的共聚物(A)，阳离子表面活性剂(C-2)的量优选在 $0.01{\\sim}3.00$ 重量份的范围内。若阳离子表面活性剂(C-2)的量不足0.01重量份，则防雾膜的防雾性能的  \n\n持久性降低。另一方面,若阴离子表面活性剂(C-2)的量超过3.00重量份，则防雾膜上的滴水痕迹容易变醒目。  \n\n[0055] (共聚物(A))  \n\n[0056]共聚物(A)由单体(A-1)、单体(A-2)和单体(A-3)构成。单体(A-1)由下列通式(1)或(2)表示，单体(A-2)由下列通式(3)表示，单体(A-3)由下列通式(4)或(5)表示。  \n\n[0057] [化学式6]  \n\n[0058]  \n\n![](images/3d5b2c3c05f6127a1c3cc3f7f04b1d908e64dccd87b87761ffe58b785d33426e.jpg)  \n\n[0059]通式(1)中， $\\mathrm{R}^{1}$ 为氢原子或甲基， $\\mathrm{R}^{2}$ 为碳原子数 $1{\\sim}4$ 的直链或枝化的烷基、 $\\mathrm{-C\\left(CH_{3}\\right)}$ $\\mathrm{2CH_{2}C O C H_{3}}$ 、-C2H4N(CH3)2、或者-C3H6N(CH3)2， $\\mathrm{R}^{3}$ 为氢原子或直链或枝化的碳原子数 $1{\\sim}4$ 的烷基。  \n\n[0060] [化学式7]  \n\n[0061] (2)  \n\n![](images/526545d7bdd896927d9afea6bd0ff42386bb66bddfc2715f760e6844b7a32d9d.jpg)  \n\n[0062] 通式(2)中， $\\mathrm{R}^{4}$ 为氢原子或甲基。[0063] [化学式8]  \n\n[0064]  \n\n![](images/bf1c39c573d87e5904f4823a93b265e3a0faa8a1ed997d93f4018310a4f612eb.jpg)  \n\n[0065] 通式(3)中， $\\mathrm{R}^{5}$ 为氢原子或甲基， $\\boldsymbol{\\mathrm{R}}^{6}$ 为碳原子数 $1\\sim16$ 的直链、枝化或环状的烷基。[0066] [化学式9]  \n\n[0067]  \n\n![](images/6aadef63a061ffcc2a204edb3335ebb36b22076fd8c935b254660303b5290803.jpg)  \n\n[0068]通式(4)中， $\\boldsymbol{\\mathrm{R}}^{7}$ 为氢原子或甲基， $\\mathrm{R}^{8}$ 为碳原子数 $2{\\sim}4$ 的直链或枝化的亚烷基、或者-$\\mathrm{C_{2}H_{4}}\\left(\\mathrm{OCO}\\left(\\mathrm{CH_{2}}\\right)_{5}\\right)_{\\mathrm{n}^{-}}\\left(\\mathrm{n}{=}1{\\sim}5\\right)$ 。  \n\n[0069] [化学式10]  \n\n![](images/e4e5f8b6ddcc72080e86446eb2f248874461965c128837b4dfa546030ee6ef00.jpg)  \n\n[0071] 通式(5)中， $\\mathrm{R}^{9}$ 为氢原子或甲基， $\\mathrm{R}^{10}$ 为碳原子数 $1{\\sim}4$ 的直链或枝化的亚烷基。[0072] 当单体(A-1)为二烷基(甲基)丙烯酰胺时,由防雾剂组合物获得的防雾膜相对于基材的贴附性特别优异。  \n\n[0073］相对于共计100重量份的单体(A-1)、单体(A-2)及单体(A-3)，单体(A-1)的量优选在 $35{\\sim}90$ 重量份的范围内。若单体(A-1)的量不足35重量份，则防雾膜的防雾性能的持久性降低。另一方面，若单体(A-1)的量超过90重量份，则防雾膜上的滴水痕迹容易变醒目。  \n\n[0074]当单体(A-2)为碳原子数 $1\\sim16$ 的(甲基)丙烯酸酯时，由防雾剂组合物获得的防雾膜的耐热及耐湿试验后的防雾性能特别优异。当碳原子数大于16时，由防雾剂组合物获得的防雾膜的耐热及耐湿试验后的防雾性能降低。  \n\n[0075]相对于共计100重量份的单体(A-1)、单体(A-2)及单体(A-3)，单体(A-2)的量优选在 $5\\sim60$ 重量份的范围内。若单体(A-2)的量不足5重量份，则防雾膜上的滴水痕迹容易变醒目。另一方面,若单体(A-2)的量超过60重量份，则防雾膜的防雾性能的持久性降低。  \n\n[0076]当单体(A-3)为羟烷基 (甲基)丙烯酸酯或羟烷基(甲基)丙烯酰胺时，由防雾剂组合物获得的防雾膜的防雾性能的持久性特别优异。  \n\n[0077］相对于共计100重量份的单体(A-1)、单体(A-2)及单体(A-3)，单体(A-3)的量优选在 $5\\sim30$ 重量份的范围内。若单体(A-3)的量不足5重量份，则防雾膜的耐水性降低，同时防雾膜上的滴水痕迹容易变醒目。另一方面，若单体(A-3)的量超过30重量份，则防雾膜相对于基材的贴附性降低。  \n\n[0078] (多官能嵌段异氰酸酯化合物(B))  \n\n[0079］多官能嵌段异氰酸酯化合物(B)为丙二酸二乙酯嵌段异氰酸酯时，防雾剂组合物在不添加催化剂的情况下于低温( $\\mathrm{120^{\\circ}C}$ 左右)良好的发生固化。  \n\n[0080］将多官能嵌段异氰酸酯化合物(B)的异氰酸酯基含量设为\"NC0\"，将共聚物(A)的羟基含量设为 $^{\\mathfrak{s}}\\mathrm{0H}^{\\mathfrak{s}}$ ，用异氰酸酯基含量NCO除以共聚物(A)的羟基含量OH,由此得到的NCO/OH比优选在 $0.1{\\sim}1.5$ 的范围内。  \n\n[0081］若NCO/OH比不足0.1，则防雾膜的耐水性降低，同时防雾膜上的滴水痕迹容易变醒目。另一方面，若NC0/0H比超过1.5，则防雾膜的防雾性能的持久性降低。  \n\n[0082] [防雾性产品]  \n\n[0083］本实施方式的防雾性产品可通过在充当作为赋予防雾性能的对象的基材的物品的表面上涂布防雾剂组合物，使物品表面的防雾剂组合物被加热固化来制造。可适用于本实施方式的物品没有特别的限制。  \n\n[0084]但是，由于本实施方式的防雾性产品可获得防雾性能高的持久性，因而本实施方式可以更好的适用于在易发生结露的环境下使用的物品。作为这样的物品，例如可列举汽车前灯。  \n\n[0085] 实施例  \n\n0086] 1.防雾剂组合物的制作[0087] (1-1)共聚物 (A)的合成  \n\n[0088］使用装有温度计、搅拌装置、氮气导入管及冷却管的反应容器，对作为有机溶剂的213重量份的叔戊醇进行吹氮的同时，加热至 $80^{\\circ}\\mathrm{C}$ 。在此反应容器中，经时2小时滴加下列溶液(a)及溶液(b)。  \n\n[0089］·溶液(a)：混合有50重量份的N,N-二甲基丙烯酰胺(单体(A-1)）、35重量份的丙烯酸丁酯(单体(A-2)）及15重量份的2-羟基丙烯酸酯(单体(A-3))的溶液  \n\n[0090］·溶液(b)：在20重量份的叔戊醇中溶解有相当于0.5重量份的过氧化特戊酸叔己酯(自由基聚合引发剂)[日油(株)制，商品名:PerhexylPV(有效成分为70重量 $\\%$ 的溶液[0091］通过直接对滴加溶液(a)及溶液(b)后的反应容器中的溶液搅拌1小时,得到共聚物(A)的溶液。通过气相色谱法测得的共聚物(A)的进料单体的聚合转化率为 $100\\%$ 。此外，通过凝胶渗透色谱法测得的共聚物(A)的重均分子量为93,000。  \n[0092］此外，共聚物(A)的羟值按照如下所示的式子进行计算。  \n[0093] [羟值] $\\mathrm{(mgK0H/g)}$   \n[0094] $=[100.0\\$ 重量份的共聚物(A)中的单体(A-3)的重量份](g)/[单体(A-3)的摩尔重量) $]\\ (\\mathrm{g/mol)\\timesKOH\\left(mg\\right)}$   \n[0095] $=0.15\\mathrm{(g)/116.12\\mathrm{(g/mol)}\\times56100\\mathrm{(mgK0H)}}$   \n[0096] $=72.5(\\mathrm{mgK0H/g})$   \n[0097] (1-2)防雾剂组合物的制作 (在使用丙二酸嵌段异氰酸酯的情况下)  \n[0098]在作为相当于100重量份的共聚物(A)的、333重量份的固含量为 $30.0\\%$ 的聚合溶液中，添加100重量份的聚丙二醇单甲基醚、200重量份的双丙酮醇、100重量份的甲基异丁基酮和267重量份的正丁醇，将固含量调整为10.0重量 $\\%$ 0  \n[0099］作为多官能嵌段异氰酸酯化合物(B)，使用了NCO/OH比相当于1.0的、83.5重量份的六亚甲基二异氰酸酯的丙二酸嵌段异氰酸酯体[旭化成化学(株)制,商品名:DuranateMF-K60B(NCO浓度为6.5重量 $\\%$ )]。  \n[0100]作为阴离子表面活性剂(C-1)，使用了相当于5.0重量份的二(2-乙基已基)磺基琥珀酸钠[日油(株)制，商品名：RapisolA80(有效成分为80.0重量 $\\%$ )]。  \n[0101]作为阳离子表面活性剂(C-2)，使用了相当于0.01重量份的二癸基二甲基氯化铵[日油(株)制，商品名：Nissancation2DB500E(有效成分为50.0重量 $\\%$ ]。  \n[0102]作为流平剂,使用了0.01重量份的聚醚改性聚二甲基硅氧烷[BYK日本(株)制，商品名：BYK333]。  \n[0103]混合上述共聚物(A)、多官能嵌段异氰酸酯化合物(B)、阴离子表面活性剂(C-1)、阳离子表面活性剂(C-2)及流平剂,得到防雾剂组合物。  \n[0104] (1-3)防雾剂组合物的制作(在使用丙二酸嵌段异氰酸酯以外的情况下)  \n[0105]在作为相当于100重量份的共聚物(A)的、333重量份的固含量为 $30.0\\%$ 的聚合溶液中，添加100重量份的聚丙二醇单甲基醚、200重量份的双丙酮醇、100重量份的甲基异丁基酮和267重量份的正丁醇，将固含量调增为10.0重量 $\\%$   \n[0106］作为多官能嵌段异氰酸酯化合物(B)，使用了NCO/0H比相当于1.0的、51.7重量份的六亚甲基二异氰酸酯的二甲基吡唑嵌段异氰酸酯体[Sumika Bayer Urethane(株)制,商品名:Desmodur $3575/1$ (NCO浓度为10.5重量 $\\%$ ]。  \n[0107］作为阴离子表面活性剂(C-1)，使用了相当于5.0重量份的二(2-乙基已基)磺基琥珀酸钠[日油(株)制，商品名：RapisolA80(有效成分为80.0重量 $\\%$ )]。  \n[0108]作为阳离子表面活性剂(C-2)，使用了相当于3.0重量份的1-甲基 $\\cdot-1-$ 羟基乙基 $\\cdot-2-$  \n\n牛脂烷基-咪唑氯[日油(株)制,商品名：Nissancation AR-4(有效成分为35.0重量 $\\%$ )]。  \n\n[0109] 作为催化剂，使用了1.0重量份的二月桂酸二丁基锡。  \n\n[0110]作为流平剂,使用了0.01重量份的聚醚改性聚二甲基硅氧烷[BYK日本(株)制,商品名：BYK333]。  \n\n[0111]混合上述共聚物(A)、多官能嵌段异氰酸酯化合物(B)、阴离子表面活性剂(C-1)、阳离子表面活性剂(C-2)、催化剂及流平剂，得到防雾剂组合物。  \n\n[0112] 2.防雾膜的制作  \n\n[0113］作为形成防雾膜的基材，使用了聚碳酸酯树脂板。以使固化后的防雾膜的膜厚为5um的方式，利用喷涂法在聚碳酸酯树脂板上涂布防雾剂组合物。然后，通过将涂布有防雾剂组合物的聚碳酸酯树脂板在 $130^{\\circ}\\mathrm{C}$ 下保持30分钟，加热固化防雾剂组合物。由此得到具有防雾膜的防雾膜试验片。  \n\n[0114] 3.防雾膜的性能评价 [0115] (3-1)防雾性能 [0116] (a)持久性试验  \n\n[0117]通过在距离保持为 $80^{\\circ}\\mathrm{C}$ 的温水浴的水面2cm高的位置,以使防雾膜向下的方式设置防雾膜试验片，对防雾膜试验片的防雾膜进行来自于温水浴的蒸汽照射，然后使防雾膜试验片以直立状态在室温下干燥1小时。此操作重复50次后，按照下列4个等级，通过目视评价蒸汽照射10秒钟后有无雾气。  \n\n[0118] A：蒸汽照射后立即形成水膜，不生雾。  \n[0119] B：蒸汽照射后立刻观察到瞬间的雾气，但即刻形成水膜，雾气消失。  \n[0120] C:蒸汽照射后立刻观察到雾气，但不久即形成水膜，雾气消失。  \n[0121] D：蒸汽照射后没有形成完整的水膜，或者不形成水膜，观察到雾气。  \n\n[0122]另外，防雾膜试验片上所形成的防雾膜的评价只要在\"C\"以上，则在实际应用上没有问题，优选为\"B”，更优选为\"A”。  \n\n[0123] (b)蒸汽实验  \n\n[0124]通过在距离保持为 $80^{\\circ}\\mathrm{C}$ 的温水浴的水面2cm高的位置，以使防雾膜向下的方式设置防雾膜试验片，对防雾膜试验片的防雾膜进行来自于温水浴的蒸汽照射，按照下列4个等级，通过目视评价蒸汽照射10秒钟后有无雾气。  \n\n[0125] A：蒸汽照射后立即形成水膜，不生雾。  \n[0126] B：蒸汽照射后立刻观察到瞬间的雾气，但即刻形成水膜，雾气消失。  \n[0127] C：蒸汽照射后立刻观察到雾气，但不久即形成水膜，雾气消失。  \n[0128] D:蒸汽照射后立刻观察到雾气，没有形成水膜。  \n\n[0129]另外，防雾膜试验片上所形成的防雾膜的评价只要在\"C\"以上，则在实际应用上没有问题，优选为\"B”，更优选为 $\\mathrm{^{*}A}^{,*}$ o  \n\n[0130] (C)耐湿试验后的蒸汽试验  \n\n[0131]将防雾膜试验片在 $50\\%$ RH的条件下静置240小时，进一步在室温下静置1小时。然后，通过在距离保持为 $80^{\\circ}\\mathrm{C}$ 的温水浴的水面2cm高的位置，以使防雾膜向下的方式设置防雾膜试验片，对防雾膜试验片的防雾膜进行来自于温水浴的蒸汽照射，按照下列4个等级，通过目视评价蒸汽照射10秒钟后有无雾气。  \n\n[0132] A：蒸汽照射后立即形成水膜，不生雾。  \n\n[0133]B：蒸汽照射后立刻观察到瞬间的雾气，但即刻形成水膜,雾气消失。  \n[0134] C：蒸汽照射后立刻观察到雾气，但不久即形成水膜，雾气消失。  \n[0135] D:蒸汽照射后没有形成完整的水膜，或者不形成水膜，观察到雾气。  \n[0136] 另外，防雾膜试验片上所形成的防雾膜的评价只要在\"℃\"以上，则在实际应用上没有问题，优选为\"B”，更优选为\"A”。  \n[0137］(d)耐热试验后的蒸汽试验  \n[0138]将防雾膜试验片在 $120^{\\circ}\\mathrm{C}$ 的条件下静置240小时，进一步在室温下静置1小时。然后，通过在距离保持为 $80^{\\circ}\\mathrm{C}$ 的温水浴的水面2cm高的位置，以使防雾膜向下的方式设置防雾膜试验片，对防雾膜试验片的防雾膜进行来自于温水浴的蒸汽照射，按照下列4个等级，通过目视评价蒸汽照射10秒钟后有无雾气。  \n[0139］A：蒸汽照射后立即形成水膜,不生雾。  \n[0140] B:蒸汽照射后立刻观察到瞬间的雾气，但即刻形成水膜,雾气消失。  \n[0141] C：蒸汽照射后立刻观察到雾气，但不久即形成水膜，雾气消失。  \n[0142] D:蒸汽照射后没有形成完整的水膜，或者不形成水膜，观察到雾气。  \n[0143] 另外，防雾膜试验片上所形成的防雾膜的评价只要在\"C\"以上，则在实际应用上没有问题，优选为\"B”，更优选为\"A”。  \n[0144] (3-2)滴水痕迹  \n[0145］通过在距离保持为 $80^{\\circ}\\mathrm{C}$ 的温水浴的水面2cm高的位置，以使防雾膜向下的方式设置防雾膜试验片，对防雾膜试验片的防雾膜进行来自于温水浴的蒸汽照射，然后使防雾膜试验片以直立状态在室温下干燥1小时。按照下列4个等级，通过目视评价干燥后的防雾试验片上有无滴水痕迹。  \n[0146]A:滴水痕迹不醒目。  \n[0147] B:滴水痕迹基本不醒目。  \n[0148] C:滴水痕迹稍微醒目。  \n[0149] D:滴水痕迹醒目。  \n[0150] 另外，防雾膜试验片上所形成的防雾膜的评价只要在\"C\"以上，则在实际应用上没有问题，优选为\"B”，更优选为\"A”。  \n[0151] (3-3)贴附性  \n[0152]按照下列3个等级，以JIS K5600-5-6为标准，通过目视评价防雾膜试验片的防雾膜有无剥离。  \n[0153］A：完全未观察到剥离。  \n[0154] B:观察到部分剥离。  \n[0155] D:完全剥离。  \n[0156] 另外，防雾膜试验片上所形成的防雾膜的评价只要在\"B\"以上，则在实际应用上没有问题，更优选为\"A”。  \n[0157] (3-4)耐水性  \n[0158]将防雾膜试验片在 $40^{\\circ}\\mathrm{C}$ 的温水中静置240小时，进一步在室温下静置1小时。然后，按照下列4个等级，通过目视评价防雾膜试验片的防雾膜的外观。  \n[0159]A.外邓与试验前于变化  \n\n[0160] B:仅涂膜表面粗糙。  \n[0161] C：涂膜表面粗糙，或者略微观察到白化或污点。  \n[0162] D：涂膜部分或全部溶解，或者清楚观察到白化或污点。  \n[0163] 另外，防雾膜试验片上所形成的防雾膜的评价只要在\"C\"以上，则在实际应用上没有问题，优选为\"B”，更优选为\"A”。  \n[0164] 4.防雾膜的评价结果  \n[0165] (4-1)实施例 $1^{-1\\sim}1^{-9}$   \n[0166] 在实施例 $1-1\\sim1-9$ 中，主要对阴离子表面活性剂(C-1)及阳离子表面活性剂(C-2)的种类及用量进行了探讨。实施例 $1-1\\sim1-9$ 的防雾膜试验片均通过与上述相同的方法进行制作。表1示出了实施例 $1-1\\sim1-9$ 的防雾剂组合物的组成 (重量份)和由该防雾剂组合物形成防雾膜的防雾膜试验片的性能的评价结果。  \n\n![](images/ad898bf0a95309a0581ef9aadcde14a484932ae280b5f286d8b92688c8c3277b.jpg)  \n\n[0167]  \n\n[0168] 另外，关于表1中的各物质的简略表述如后所示。[0169] 如表1所示，在实施例 $1-1\\sim1-9$ 中，防雾膜的良好性能均得到确认。在实施例1-2的  \n\n防雾膜中，获得特别良好的性能。  \n\n[0170]由实施例 $1-1.1-4.1-5$ 的结果可知，阴离子表面活性剂(C-1)与阳离子表面活性剂(C-2)中的至少一种较少时，防雾膜的防雾性能的持久性有略微降低的倾向。  \n[0171]由实施例1-4的结果可知，阴离子表面活性剂(C-1)和阳离子表面活性剂(C-2)均较少时，防雾膜的防雾性能有略微降低的倾向。  \n[0172]由实施例1-1、1-4的结果可知,阳离子表面活性剂(C-2)较少时，防雾膜的耐湿试验后的防雾性能有略微降低的倾向。  \n[0173］由实施例 $1^{-1}\\cdot1^{-4}\\cdot1^{-5}\\cdot1^{-6}$ 的结果可知，阴离子表面活性剂(C-1)和阳离子表面活性剂(C-2)中的至少一种较少时，防雾膜的耐热试验后的防雾性能有略微降低的倾向。[0174] 由实施例 $1^{-3},1^{-6},1^{-7},1^{-8},1^{-9}$ 的结果可知，阴离子表面活性剂(C-1)和阳离子表面活性剂(C-2)中的至少一种较多时,防雾膜中的滴水痕迹有略微变醒目的倾向。  \n[0175] (4-2)实施例 $1{-}10{\\sim}1{-}21$   \n[0176］在实施例 $1{-}10{\\sim}1{-}21$ 中，主要对单体(A-1)、单体(A-2)及单体(A-3)的种类进行了探讨。实施例 $1{-}10{\\sim}1{-}21$ 的防雾膜试验片均通过与上述相同的方法进行制作。表2示出了实施例 $1{-}10{\\sim}1{-}21$ 的防雾剂组合物的组成 (重量份)和由该防雾剂组合物形成防雾膜的防雾膜试验片的性能的评价结果。[0178] 另外，关于表2中的各物质的省略表述如后所示。  \n[0179] 如表2所示，在实施例 $1{-}10{\\sim}1{-}21$ 中，防雾膜的良好性均能得到确认。  \n\n![](images/b228081a63768c232224c8c227cad106ce3cb44820d2b49d4a3e367467eb6a58.jpg)  \n\n[0180]］由实施例 $1\\mathrm{-}10,1\\mathrm{-}16,1\\mathrm{-}18,1\\mathrm{-}19$ 的结果可知,单体(A-1)为二烷基丙烯酰胺时、单体(A-2)为碳原子数6的丙烯酸酯时、以及单体(A-3)为甲基丙烯酸羟乙酯或羟乙基丙烯酰胺时，得到特别良好的性能。  \n\n[0181]由实施例1-20、1-21的结果可知,当单体(A-3)为长链、或者更长链的羟基丙烯酸酯时，防雾膜的防雾性能的持久性有略微降低的倾向。  \n\n[0182]由实施例1-17的结果可知，当单体(A-2)为碳原子数16的丙烯酸酯时，防雾膜的耐湿及耐热试验后的防雾性能有略微降低的倾向。  \n\n[0183]由实施例1-15的结果可知，当单体(A-2)为碳原子数1的丙烯酸酯时，防雾膜上的滴水痕迹有略微变醒目的倾向。  \n\n[0184]由实施例 $1^{-}11,1^{-}12,1^{-}13,1^{-}14,1^{-}21$ 的结果可知,单体(A-1)为单烷基丙烯酰胺、二丙酮丙烯酰胺、二甲氨基丙基丙烯酰胺、或者丙烯酰基吗啉时，以及单体(A-3)为长链的羟基丙烯酸酯时，防雾膜试验片的防雾膜的贴附性有略微降低的倾向。  \n\n[0185] (4-3)实施例 $1{-}22{\\sim}1{-}26$  \n\n[0186]在实施例 $1{-}22{\\sim}1{-}26$ 中，主要对单体(A-1)、单体(A-2)、单体(A-3)、以及多官能嵌段异氰酸酯化合物 (B)的量进行了探讨。实施例 $1{-}22{\\sim}1{-}26$ 的防雾膜试验片均通过与上述相同的方法进行制作。表3示出了实施例 $1{-}22{\\sim}1{-}26$ 的防雾剂组合物的组成 (重量份)和由该防雾剂组合物形成防雾膜的防雾膜试验片的性能的评价结果。  \n\n[0187] [表3]  \n\n[0188]  \n\n<html><body><table><tr><td colspan=\"4\" rowspan=\"2\"></td><td colspan=\"5\">实施例</td></tr><tr><td>1-22</td><td>1-23</td><td>1-24</td><td>1-25</td><td>1-26</td></tr><tr><td>防雾剂组合物</td><td></td><td>单体（A-1）</td><td>DMAA</td><td>90</td><td>35</td><td>50</td><td>50</td><td>50</td></tr><tr><td rowspan=\"3\">共聚物（A) [重量份]</td><td>单体（A-2）</td><td>BA(C4)</td><td>5</td><td>60</td><td>20</td><td>35</td><td>35</td></tr><tr><td>单体（A-3）</td><td>HEA</td><td>5</td><td>5</td><td>30</td><td>15</td><td>15</td></tr><tr><td colspan=\"2\">单体总量</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td></tr><tr><td rowspan=\"5\">多官能嵌段 B</td><td>丙二酸二乙 酯</td><td>羟值[mgKOH/g] Duranate</td><td>24.2</td><td>24.2</td><td>144.9</td><td>72.5</td><td>72.5</td></tr><tr><td>嵌段异氰酸 二甲基吡唑</td><td>MF-K60B</td><td>27.8</td><td></td><td>83.5</td><td>8.4</td><td>125.3</td></tr><tr><td>嵌段异氰酸 酯</td><td>Desmod/r</td><td></td><td>17.3</td><td></td><td></td><td></td></tr><tr><td colspan=\"2\">NCO/OH比 阴离子型 RapisolA80</td><td>1.0</td><td>1.0 5.0</td><td>0.5</td><td>0.1</td><td>1.5</td></tr><tr><td rowspan=\"5\">表面 活性剂（C） [重量份] (C2)</td><td colspan=\"2\">(C1）</td><td>5.0</td><td></td><td></td><td></td><td></td></tr><tr><td rowspan=\"4\">阳离子型</td><td>Persoft SK Nissan cation</td><td></td><td></td><td>5.0</td><td>5.0</td><td>5.0</td></tr><tr><td>2DB500E</td><td>0.5</td><td></td><td></td><td></td><td></td></tr><tr><td>Nissan cation BB</td><td></td><td></td><td>0.50</td><td>0.50</td><td>0.50</td></tr><tr><td>Nissan cation AR-4 Ftergent300</td><td></td><td>0.5</td><td></td><td></td><td></td></tr><tr><td>催化剂[重量 份]</td><td colspan=\"2\">二月桂酸二丁基锡</td><td></td><td>1.0</td><td></td><td></td><td></td></tr><tr><td rowspan=\"7\">性能</td><td rowspan=\"5\">防雾性</td><td>持久性试验</td><td>B</td><td>C</td><td>B</td><td>B</td><td>C</td></tr><tr><td>蒸汽试验</td><td>A</td><td>A</td><td>A</td><td>A</td><td>A</td></tr><tr><td>耐湿试验后的蒸汽 试验</td><td>A</td><td>A</td><td>A</td><td>A</td><td>A</td></tr><tr><td>耐热试验后的蒸汽 试验</td><td>A</td><td>A</td><td>A</td><td>A</td><td>A</td></tr><tr><td colspan=\"2\">滴水痕迹</td><td>C</td><td>B</td><td>A</td><td>C</td><td>A</td></tr><tr><td colspan=\"2\">贴附性</td><td>A</td><td>A</td><td>B</td><td>A</td><td>A</td></tr><tr><td>耐水性</td><td colspan=\"2\"></td><td>C</td><td>B</td><td>A</td><td>C</td><td>A</td></tr></table></body></html>  \n\n[0189] 另外，关于表3中的各物质的省略表述如后所示。  \n\n[0190] 如表3所示，在实施例 $1{-}22{\\sim}1{-}26$ 中，防雾膜的良好性能均得到确认。  \n\n[0191]由实施例1-23、1-26的结果可知，单体(A-2)较多、单体(A-1)及单体(A-3)较少时，以及多官能嵌段异氰酸酯化合物(B)较多时,防雾膜的防雾性能的持久性有略微降低的倾向。  \n\n[0192]由实施例1-22、1-23、1-25的结果可知,当单体(A-1)较多、单体(A-2)及单体(A-3)较少时，单体(A-2)较多、单体(A-1)及单体(A-3)较少时,以及多官能嵌段异氰酸酯(B)较少时，防雾膜上的滴水痕迹有略微变醒目的倾向。  \n\n[0193]由实施例1-24的结果可知，单体(A-3)较多时，防雾膜试验片的防雾膜的贴附性有略微降低的倾向。  \n\n[0194] 由实施例1-22、1-23、1-25的结果可知,单体(A-1)较多、单体(A-2)及单体(A-3)较少时，单体(A-2)较多、单体(A-1)及单体(A-3)较少时,以及多官能嵌段异氰酸酯(B)较少时，防雾膜的耐水性有略微降低的倾向。  \n\n[0195] (4-4)实施例 $2^{-1}{\\sim}2^{-9}$  \n\n[0196]在实施例 $2^{-1}\\sim2^{-9}$ 中，主要对使用了作为阴离子表面活性剂(C-1)的含氟表面活性剂时的阴离子表面活性剂 $(\\mathrm{C}\\mathrm{-}1)$ 及阳离子表面活性剂(C-2)的种类和量进行了探讨。实施例 $2-1\\sim2-9$ 的防雾膜试验片均通过与上述相同的方法进行制作。表4示出了实施例 $2^{-1\\sim2^{-}}$ 9的防雾剂组合物的组成(重量份)和由该防雾剂组合物形成防雾膜的防雾膜试验片的性能的评价结果。  \n\n![](images/a8d41582270e5ef18730cfed36b01920986e6ba8837258a41d5e14b6257bdf05.jpg)  \n\n[0197]  \n\n[0198] 另外，关于表4中的各物质的省略表述如后所示。[0199] 如表4所示，在实施例 $2^{-1\\sim2^{-9}}$ 中，防雾膜的良好性均能得到确认。在实施例2-2的  \n\n防雾膜中，获得特别良好的性能。  \n\n[0200］由实施例2-1、2-4、2-5的结果可知,阴离子表面活性剂(C-1)与阳离子表面活性剂(C-2)中的至少一种较少时，防雾膜的防雾性能的持久性有略微降低的倾向。  \n[0201］由实施例2-4的结果可知，阴离子表面活性剂(C-1)和阳离子表面活性剂(C-2)均较少时，防雾膜的防雾性能有略微降低的倾向。  \n[0202]由实施例2-1、2-4的结果可知，阳离子表面活性剂(C-2)较少时,防雾膜的耐湿试验后的防雾性能有略微降低的倾向。  \n[0203]由实施例 $2-1\\cdot2^{-}4\\cdot2^{-}5\\cdot2^{-}6$ 的结果可知,阴离子表面活性剂(C-1)和阳离子表面活性剂(C-2)中的至少一种较少时，防雾膜的耐热试验后的防雾性能有略微降低的倾向。[0204]由实施例 $2\\substack{-3,2\\substack{-6,2-7,2-8,2-9}}$ 的结果可知,阴离子表面活性剂(C-1)和阳离子表面活性剂(C-2)中的至少一种较多时,防雾膜中的滴水痕迹有略微变醒目的倾向。  \n[0205] (4-5)实施例 $2\\mathrm{-}10\\mathrm{\\sim}2\\mathrm{-}21$   \n[0206］在实施例 $2\\mathrm{-}10\\mathrm{\\sim}2\\mathrm{-}21$ 中，主要对使用了作为阴离子表面活性剂(C-1)的含氟表面活性剂时的单体(A-1)、单体(A-2)及单体(A-3)的种类进行了探讨。实施例 $2^{-}\\mathrm{{10}^{-}\\mathrm{{2-21}}}$ 的防雾膜试验片均通过与上述相同的方法进行制作。表5示出了实施例 $2\\mathrm{-}10\\mathrm{\\sim}2\\mathrm{-}21$ 的防雾剂组合物的组成(重量份)和由该防雾剂组合物形成防雾膜的防雾膜试验片的性能的评价结果。[0208] 另外，关于表5中的各物质的省略表述如后所示。  \n[0209] 如表5所示，在实施例 $2\\mathrm{-}10\\mathrm{\\sim}2\\mathrm{-}21$ 中，防雾膜的良好性能均得到确认。  \n\n![](images/45c98edfeb280eb831eea121d94671ea562da74d7975c1d2ed7a8d0eb5f9ae61.jpg)  \n\n[0210］由实施例 $2\\mathrm{-}10,2\\mathrm{-}16,2\\mathrm{-}18,2\\mathrm{-}19$ 的结果可知,单体(A-1)为二烷基丙烯酰胺时、单体(A-2)为碳原子数6的丙烯酸酯时、以及单体(A-3)为甲基丙烯酸羟乙酯或羟乙基丙烯酰胺时，防雾膜得到特别良好的性能。  \n\n[0211]由实施例2-20、2-21的结果可知，当单体(A-3)为长链、或者更长链的羟基丙烯酸酯时，防雾膜的防雾性能的持久性有略微降低的倾向。  \n\n[0212]由实施例2-17的结果可知，当单体(A-2)为碳原子数16的丙烯酸酯时，防雾膜的耐湿及耐热试验后的防雾性能有略微降低的倾向。  \n\n[0213]由实施例2-15的结果可知,当单体(A-2)为碳原子数1的丙烯酸酯时，防雾膜上的滴水痕迹有略微变醒目的倾向。  \n\n[0214]由实施例 $2\\substack{-11,2-12,2-13,2-14,2-21}$ 的结果可知,单体(A-1)为单烷基丙烯酰胺、二丙酮丙烯酰胺、二甲氨基丙基丙烯酰胺、或者丙烯酰吗啉时，以及单体(A-3)为更长链的羟基丙烯酸酯时，防雾膜试验片的防雾膜的贴附性有略微降低的倾向。  \n\n[0215] (4-6)实施例 $2^{-}22{\\sim}2^{-}26$  \n\n[0216]在实施例 $2^{-}22{\\sim}2^{-}26$ 中，主要对使用了作为阴离子表面活性剂(C-1)的含氟表面活性剂时的单体(A-1)、单体(A-2)、单体(A-3)、以及多官能嵌段异氰酸酯化合物(B)的量进行了探讨。实施例 $2^{-}22{\\sim}2^{-}26$ 的防雾膜试验片均通过与上述相同的方法进行制作。表6示出了实施例 $2^{-}22{\\sim}2^{-}26$ 的防雾剂组合物的组成(重量份)和由该防雾剂组合物形成防雾膜的防雾膜试验片的性能的评价结果。  \n\n[0217] [表6]  \n\n[0218]  \n\n<html><body><table><tr><td colspan=\"5\" rowspan=\"2\"></td><td colspan=\"5\">实施例</td></tr><tr><td>2-22</td><td>2-23</td><td>2-24</td><td>2-25</td><td></td><td>2-26</td></tr><tr><td rowspan=\"9\">防雾剂组合物</td><td rowspan=\"5\">共聚物（A） [重量份]</td><td>单体（A-1）</td><td colspan=\"2\">DMAA</td><td>90</td><td>35</td><td>50</td><td>50</td><td>50</td></tr><tr><td>单体（A-2）</td><td>BA(C4)</td><td></td><td>5</td><td>60</td><td>20</td><td>35</td><td>35</td></tr><tr><td>单体（A-3）</td><td colspan=\"2\">HEA</td><td>5</td><td>5</td><td>30</td><td>15</td><td>15</td></tr><tr><td colspan=\"3\">单体总量</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td></tr><tr><td colspan=\"3\">羟值[mgKOH/g]</td><td>24.2</td><td>24.2</td><td>144.9</td><td>72.5</td><td>72.5</td></tr><tr><td rowspan=\"5\">多能段 化合物（B) [重量份]</td><td>丙二酸二 乙酯 嵌段异氰</td><td colspan=\"2\">Duranate MF-K60B</td><td>27.8</td><td></td><td>83.5</td><td>8.4</td><td>125.3</td></tr><tr><td>酸酯 二甲基吡 唑 嵌段异氰</td><td colspan=\"2\">Desmodur BL3575/1</td><td></td><td>17.3</td><td></td><td></td><td></td></tr><tr><td>酸酯</td><td colspan=\"2\">NCO/OH比</td><td>1.0</td><td>1.0</td><td>0.5</td><td>0.1</td><td>1.5</td></tr><tr><td rowspan=\"2\">阴离子型 (C1)</td><td rowspan=\"2\">含氟型</td><td>Ftergent100</td><td></td><td>5.0</td><td></td><td>5.0</td><td>5.0</td></tr><tr><td colspan=\"2\">SurflonS211</td><td>5.0</td><td></td><td>5.0</td><td></td></tr><tr><td rowspan=\"4\">表面 活性剂（C） [重量份]</td><td rowspan=\"4\">阳离子型 (C2)</td><td colspan=\"2\"></td><td>0.5</td><td></td><td></td><td></td><td></td></tr><tr><td colspan=\"2\">Nissan cation 2DB500E Nissan cation BB</td><td></td><td></td><td>0.50</td><td>0.50</td><td></td></tr><tr><td colspan=\"2\">Nissan cation AR-4</td><td></td><td>0.5</td><td></td><td></td><td>0.50</td></tr><tr><td colspan=\"2\">Ftergent300</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>催化剂[重 量份]</td><td colspan=\"3\">二月桂酸二丁基锡</td><td></td><td>1.0.</td><td></td><td></td><td></td></tr><tr><td rowspan=\"7\">性能</td><td rowspan=\"4\">防雾性</td><td colspan=\"2\">持久性试验</td><td>A</td><td>B</td><td>A</td><td>A</td><td>B</td></tr><tr><td colspan=\"2\">蒸汽试验</td><td>A</td><td>A</td><td>A</td><td>A</td><td>A</td></tr><tr><td colspan=\"2\">耐湿试验后的蒸汽试验</td><td>A</td><td>A</td><td>A</td><td>A</td><td>A</td></tr><tr><td colspan=\"2\">耐热试验后的蒸汽试验</td><td>A</td><td>A</td><td>A</td><td>A</td><td>A</td></tr><tr><td colspan=\"2\">滴水痕迹</td><td>C</td><td>B</td><td>A</td><td>C</td><td>A</td></tr><tr><td colspan=\"2\">贴附性</td><td>A</td><td>A</td><td>B</td><td>A</td><td>A</td></tr><tr><td colspan=\"3\"></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td colspan=\"3\">耐水性</td><td>C</td><td>B</td><td>A</td><td>C</td><td>A</td></tr></table></body></html>  \n\n[0219] 另外，关于表6中的各物质的省略表述如后所示。  \n\n[0220] 如表6所示，在实施例 $2\\mathrm{-}22\\mathrm{\\sim}2\\mathrm{-}26$ 中，防雾膜的良好性均能得到确认。  \n\n[0221]由实施例2-23、2-26的结果可知,单体(A-2)较多、单体(A-1)及单体(A-3)较少时，以及多官能嵌段异氰酸酯化合物(B)较多时，防雾膜的防雾性能的持久性有略微降低的倾向。  \n\n[0222]由实施例2-22、2-23、2-25的结果可知，当单体(A-1)较多、单体(A-2)及单体(A-3)较少时，单体(A-2)较多、单体(A-1)及单体(A-3)较少时,以及多官能嵌段异氰酸酯(B)较少时，防雾膜上的滴水痕迹有略微变醒目的倾向。  \n\n[0223]由实施例2-24的结果可知，单体(A-3)较多时，防雾膜试验片的防雾膜的贴附性有略微降低的倾向。  \n\n[0224]由实施例2-22、2-23、2-25的结果可知，单体(A-1)较多、单体(A-2)及单体(A-3)较少时，单体(A-2)较多、单体(A-1)及单体(A-3)较少时，以及多官能嵌段异氰酸酯(B)较少时，防雾膜的耐水性有略微降低的倾向。  \n\n[0225] 5.比较例  \n\n[0226]表7示出了比较例 $1{\\sim}6$ 的防雾剂组合物的组成(重量份)和由该防雾剂组合物形成防雾膜的防雾膜试验片的性能的评价结果。比较例 $1{\\sim}6$ 的防雾膜试验片均通过与上述相同的方法进行制作。  \n\n[0227] [表7] [0228]  \n\n<html><body><table><tr><td rowspan=\"2\" colspan=\"3\"></td><td rowspan=\"2\"></td><td colspan=\"6\">比较例</td></tr><tr><td>1</td><td>2</td><td>3</td><td>4</td><td>5</td><td>6</td></tr><tr><td rowspan=\"8\">防雾剂组合物 酯</td><td rowspan=\"5\">共聚物 [重份]</td><td>单体 (A-1) 单体</td><td colspan=\"2\">DMAA</td><td>50</td><td>50</td><td>50</td><td>50</td><td>50</td><td>50</td></tr><tr><td>(A-2)</td><td colspan=\"2\">BA(C4)</td><td>35</td><td>35</td><td>35</td><td>35</td><td>35</td><td>35</td></tr><tr><td>单体</td><td colspan=\"2\">HEA</td><td>15</td><td>15</td><td>15</td><td>15</td><td>15</td><td>15</td></tr><tr><td colspan=\"3\">单体总量</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td></tr><tr><td colspan=\"3\">羟值[mgKOH/g]</td><td>72.5</td><td>72.5</td><td>72.5</td><td>72.5</td><td>72.5</td><td>72.5</td></tr><tr><td>多能 丙二酸二 异氰酸 嵌段异氰 酸酯 化合物</td><td colspan=\"3\">Duranate MF-K60B</td><td>83.5</td><td>83.5</td><td>83.5</td><td>83.5</td><td>83.5</td><td>83.5</td></tr><tr><td rowspan=\"4\">（B） [重量份] 表面 活性剂 (C)</td><td colspan=\"3\">NCO/OH比</td><td>1.0</td><td>1.0</td><td>1.0</td><td>1.0</td><td>1.0</td><td>1.0</td></tr><tr><td>阴离子型</td><td></td><td>RapisolA80</td><td>10.0</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>(C1) 阳离子型</td><td>含氟型</td><td>Surflon S211</td><td></td><td>10.0</td><td></td><td></td><td>10.0</td><td></td></tr><tr><td>(C2) 非离子型</td><td colspan=\"2\">Nissan cation BB Noigen EA-140</td><td></td><td></td><td>3.0</td><td></td><td></td><td>3.0</td></tr><tr><td rowspan=\"6\">性能</td><td rowspan=\"5\">(C-3 防雾性</td><td colspan=\"2\">持久性试验</td><td></td><td></td><td></td><td></td><td>10.0</td><td>10.0</td><td>10.0</td></tr><tr><td colspan=\"2\">蒸汽试验</td><td>D A</td><td>D</td><td>D</td><td></td><td>D B</td><td>D A</td><td>D</td></tr><tr><td colspan=\"2\">耐湿试验后的蒸汽试验</td><td>A</td><td>A A</td><td>B B</td><td></td><td>B</td><td>A</td><td>A A</td></tr><tr><td colspan=\"2\">耐热试验后的蒸汽试验</td><td>A</td><td>A</td><td>C</td><td></td><td>C</td><td>A</td><td>C</td></tr><tr><td colspan=\"2\">滴水痕迹</td><td>C</td><td>C</td><td>C</td><td></td><td>C</td><td>D</td><td>C</td></tr><tr><td colspan=\"2\">贴附性</td><td></td><td>A</td><td>A</td><td>A</td><td>A</td><td>A</td><td>A</td></tr><tr><td colspan=\"3\">耐水性</td><td>A</td><td>A</td><td>A</td><td></td><td>A</td><td>A</td><td>A</td></tr></table></body></html>  \n\n[0229] 另外，关于表7中的各物质的省略表述如后所示。  \n\n[0230］比较例1、2的防雾剂组合物与本发明的实施方式不同，不含有阳离子表面活性剂(C-2)。其结果为，在比较例1、2的防雾膜中，没有获得防雾性能的充分持久性。此外，在比较例1、2的防雾膜中，滴水痕迹变醒目。  \n\n[0231]比较例3的防雾剂组合物与本发明的实施方式不同，不含有阴离子表面活性剂 $(\\mathrm{C^{-}}$ 1)。其结果为，在比较例3的防雾膜中，没有获得防雾性能的充分持久性。此外，在比较例3的防雾膜中，耐热试验后的防雾性略低，滴水痕迹略为醒目。  \n\n[0232] 比较例4的防雾剂组合物与本发明的实施方式不同,使用非离子表面活性剂(C-3)  \n\n代替阴离子表面活性剂(C-1)及阳离子表面活性剂(C-2)。其结果为，在比较例4的防雾膜中，没有获得防雾性能的充分持久性。此外，在比较例4的防雾膜中，耐热试验后的防雾性略低，滴水痕迹略为醒目。  \n\n[0233]比较例5的防雾剂组合物与本发明的实施方式不同，使用非离子表面活性剂(C-3)代替阳离子表面活性剂(C-2)。其结果为,在比较例5的防雾膜中，没有获得防雾性能的充分持久性。此外，在比较例5的防雾膜中，滴水痕迹略为醒目。  \n\n[0234]比较例6的防雾剂组合物与本发明的实施方式不同，使用非离子表面活性剂(C-3)代替阴离子表面活性剂(C-1)。其结果为，在比较例6的防雾膜中，没有获得防雾性能的充分持久性。此外，在比较例6的防雾膜中，耐热试验后的防雾性略低，滴水痕迹略为醒目。[0235] 6.物质的省略表述  \n[0236] 在表 $1{\\sim}7$ 中使用的物质的省略表述所对应的名称整理如下。  \n[0237] (6-1)单体(A-1)  \n[0238] DMAA:N,N-二甲基丙烯酰胺  \n[0239] DEMA:N,N-二乙基甲基丙烯酰胺  \n[0240] IPAA:N-异丙基丙烯酰胺  \n[0241] DAAA：双丙酮丙烯酰胺  \n[0242] DMAPAA：二甲胺基丙基丙烯酰胺  \n[0243] ACMO:N-丙烯酰吗啉  \n[0244] (6-2)单体(A-2)  \n[0245] MMA:甲基丙烯酸甲酯  \n[0246] BA:丙烯酸正丁酯  \n[0247] CHA：丙烯酸环己酯  \n[0248] CA：十六烷基丙烯酸酯  \n[0249] (6-3)单体(A-3)  \n[0250] HEA:丙烯酸2-羟乙酯  \n[0251] HEMA:甲基丙烯酸2-羟乙酯  \n[0252] HEAA：羟乙基丙烯酰胺  \n[0253] PLACCELFA2D：丙烯酸2-羟乙酯的2mol己内酯加成物  \n[0254] PLACCELFA5：丙烯酸2-羟乙酯的5mol己内酯加成物  \n[0255] (6-4)多官能嵌段异氰酸酯化合物 (B)  \n[0256] DuranateMF-K60B：丙二酸嵌段异氰酸酯体[旭化成化学(株)制，商品名：Duranate MF-K60B]  \n[0257]  Desmodur $3575/1$ ：二甲基吡唑嵌段异氰酸酯[Sumika Bayer Urethane(株)制,商品名:Desmodur 3575/1]  \n[0258]Sumidur BL3175:甲基乙基酮嵌段异氰酸酯[Sumika Bayer Urethane(株)制,商品名:Sumidur BL3175]  \n[0259] (6-5)阴离子表面活性剂(C-1)  \n[0260] Ftergent 100:含氟磺酸盐  \n[0261] Surflon S211:含氟羧酸盐[0262] Rapiso A80：磺基琥珀酸二酯盐  \n[0263] SK:烷基磺酸盐  \n[0264] (6-6)阳离子表面活性剂(C-2)  \n[0265] Nissan cation 2DB500E：二烷基季铵盐  \n[0266] Nissan cation BB:单烷基季铵盐  \n[0267] Nissan cation AR-4:咪唑啉盐  \n[0268] Ftergent 300：含氟阳离子表面活性剂  \n[0269] (6-7)非离子表面活性剂(C-3)  \n[0270] Noigen EA-140:聚氧乙烯烷基苯基醚  \n[0271] [其他]  \n[0272] 以上对本发明的实施方式进行了说明，但本发明并不仅仅局限于上述实施方式，在不脱离本发明的主旨的范围内进行各种变更是理所当然的。",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/CN106977688A-neo-ssq.json b/task2/task2-chunks/CN106977688A-neo-ssq.json
new file mode 100644
index 0000000..01ab97c
--- /dev/null
+++ b/task2/task2-chunks/CN106977688A-neo-ssq.json
@@ -0,0 +1,57 @@
+[
+    {
+        "id": 1,
+        "chunk": "# （19)中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利申请  \n\nCO9D 7/12(2006.01)  \n\n(21)申请号201710183813.2  \n(22)申请日2017.03.24  \n(71)申请人武汉锯欧能源材料有限公司地址430205 湖北省武汉市东湖高新区高新大道666号C7栋511室  \n(72)发明人王执错王思哲陈志华  \n(74)专利代理机构湖北武汉永嘉专利代理有限公司42102代理人钟锋 张秋燕  \n(51)Int.CI.C08G 18/75(2006.01)CO8G 18/61(2006.01)C08G 18/04(2006.01)C08G 18/38(2006.01)C09D 175/14(2006.01)",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n一种有机-无机杂化高分子复合材料及其制备方法",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明公开了一种有机-无机杂化高分子复合材料，其主要组成成分包括：可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物、可聚合或可交联的单体或齐聚体、固化辅助剂和/或添加剂。本发明的将改进的溶胶-凝胶技术和聚氨酯合成化学相结合，在分子水平上，将无机部分和有机部分用共价键杂化在一起，形成有机-无机杂化的可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物，进而与可聚合或可交联的单体或齐聚体、固化辅助剂和/或添加剂经聚合和/或交联固化，得到有机-无机杂化高分子复合材料，合成步骤简单，稳定可控，并明显缩短反应时间，所得产品具有高光学透明性，高热稳定性，高机械强度，高耐候性等。  \n\n1.一种有机-无机杂化高分子复合材料，其特征在于它的主要组成成分包括：可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物、可聚合或可交联的单体或齐聚体、固化辅助剂和/或添加剂。  \n\n2.一种有机-无机杂化高分子复合材料，其特征在于它的主要组成成分按质量百分比计为：可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物 $5-90\\%$ 、可聚合或可交联的单体或齐聚体 $10-80\\%$ 、固化辅助剂和/或添加剂 $0-10\\%$ 0  \n\n3.根据权利要求1或2所述的一种有机-无机杂化高分子复合材料，其特征在于所述可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物通式为 $\\mathrm{R_{m}S i_{n}O_{a}(O H)_{b}X_{c}}$ ，其中， $\\mathrm{,m,n,a,b,c}$ 均表示原子或基团的个数，m，n为正整数，且n在2至100的范围内， $\\mathfrak{m}$ 在0至3n的范围内，b，c均为非负整数，且满足 $\\mathrm{b+c}{\\mathrm{<}}3\\mathrm{n}$ ,a为正实数，且 $\\mathrm{a}{=}2\\mathrm{n}{-}0.5\\mathrm{b}{-}0.5\\mathrm{c}{-}0.5\\mathrm{m}$ ;Si表示元素硅;0H表示羟基，X表示为可水解的功能团;R为有机基团，相同或者不同。  \n\n4.根据权利要求3所述的一种有机-无机杂化高分子复合材料，其特征在于所述R含有一种或几种非活性或活性功能团,所述非活性基团包括但不限于：烷基、苯基、碳氟基，所述活性功能团包括但不限于：丙烯酰氧基烷基或芳香基，甲基丙烯酰氧基烷基或芳香基，烯烃基，芳香烃烯基，炔烃基,环烯烃基，环炔烃基，链式脂肪族环氧烷基,环状脂肪族环氧烷基，硫醇基以及肉桂酸基。  \n\n5.根据权利要求4所述的一种有机-无机杂化高分子复合材料，其特征在于所述R中至少有一个含有一种或几种活性功能团;X为烷氧基或者卤原子。  \n\n6.根据权利要求1或2所述的一种有机-无机杂化高分子复合材料，其特征在于所述可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物的制备方法，主要步骤如下：  \n\n1)以有机硅烷和水作为反应物，进行水解和缩合反应，获得作为第一中间体；  \n\n2)选择或者制备第二中间体，所述第二中间体含有能与硅羟基进行封端反应的官能团，并同时具有可聚合或可交联活性有机官能团;  \n\n3)第二中间体对第一中间体进行硅羟基封端反应，生成可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物。  \n\n7.根据权利要求6所述的一种有机-无机杂化高分子复合材料，其特征在于所述第一中间体、第二中间体均为一种或者几种的混合物。  \n\n8.根据权利要求6所述的一种有机-无机杂化高分子复合材料，其特征在于所述有机硅烷的化学式表达为 $\\mathrm{R}_{\\mathrm{m}}\\mathrm{Si}\\mathrm{X}_{4-\\mathrm{m}}$ ，其中，R包括但不限于：非活性基团烷基、苯基、碳氟基，活性基团丙烯酰氧基烷基或芳香基，甲基丙烯酰氧基烷基或芳香基，烯烃基，芳香烃烯基，炔烃基，环烯烃基,环炔烃基,链式脂肪族环氧烷基,环状脂肪族环氧烷基，硫醇基以及肉桂酸基;X表示可水解的功能团;m不大于3的正整数；Si表示元素硅。  \n\n9.根据权利要求8所述的一种有机-无机杂化高分子复合材料，其特征在于所述有机硅烷包括但不局限于有机烷氧基硅烷、有机卤硅烷。  \n\n10.根据权利要求8所述的一种有机-无机杂化高分子复合材料，其特征在于所述水解和缩合反应中，有机硅烷的摩尔数的总和与水摩尔数的比值为 $1.0\\colon(1.0{\\sim}6.5)$ ;水解和缩合反应的时间范围为 $0{\\sim}7$ 天；温度范围为 $0{\\sim}200^{\\circ}\\mathrm{C}$ 0  \n\n11.根据权利要求8所述的一种有机-无机杂化高分子复合材料，其特征在于所述第一中间体是完全缩合的笼状硅倍半氧烷，以及多种未完全缩合硅倍半氧烷的混合物。  \n\n12.根据权利要求8所述的一种有机-无机杂化高分子复合材料，其特征在于所述第二中间体中能进行硅羟基封端反应的基团包括但不限于异氰酸酯基，酰卤基，硅卤基；所述可聚合或可交联活性有机官能团包括但不限于丙烯酰氧基烷基或芳香基，甲基丙烯酰氧基烷基或芳香基，烯烃基，芳香烃烯基，炔烃基，环烯烃基，环炔烃基，链式脂肪族环氧烷基，环状脂肪族环氧烷基，硫醇基以及肉桂酸基。  \n\n13.根据权利要求8所述的一种有机-无机杂化高分子复合材料，其特征在于所述第一中间体中的硅羟基和第二中间体中的异氰酸酯基的摩尔比在 $0.5\\sim1.5$ 之间，硅羟基封端反应的温度在 $60{\\sim}100^{\\circ}\\mathrm{C}$ 之间，封端反应的时间在 $2{\\sim}12$ 小时之间。  \n\n14.根据权利要求8所述的一种有机-无机杂化高分子复合材料，其特征在于所述可聚合或可交联的单体或齐聚体为一种或多种按任意比例的混合物;其中，可聚合或可交联的活性基团包括但不限于烯烃基、芳香烃烯基、炔烃基、环烯烃基、环炔烃基、肉桂酸基、链式脂肪族环氧烷基、环状脂肪族环氧烷基、巯基、丙烯酰氧基烷基或芳香基、甲基丙烯酰氧基烷基或芳香基中的一种或几种。  \n\n15.根据权利要求1或2所述的一种有机-无机杂化高分子复合材料，其特征在于所述固化辅助剂包括但不限于自由基光引发剂，阳离子光引发剂，热引发剂，固化剂，催化剂中的一种或几种。  \n\n16.根据权利要求15所述的一种有机-无机杂化高分子复合材料，其特征在于所述自由基光引发剂包括但不限于2-羟基 $-2-$ 甲基 $^{-1-}$ 苯基丙酮，1-羟基环己基苯基甲酮,2,4,6-三甲基苯甲酰基-二苯基氧化麟，2-甲基 $-2-$ (4-吗啉基)-1-[4-(甲硫基)苯基] $^{-1-}$ 丙酮，二苯甲酮,4-甲基二苯甲酮,4-(二甲氨基)-苯甲酸-(2-乙基)己酯;所述阳离子光引发剂包括但不限于重氮盐、二芳基碘盐、三芳基硫盐、烷基硫盐、铁芳烃盐、磺酰氧基酮及三芳基硅氧醚;所述热引发剂为有机过氧化物或偶氮类引发剂，包括但不限于过硫酸钾，过硫酸铵，过氧化环己酮、过氧化二苯甲酰、叔丁基过氧化氢、偶氮二异丁腈、偶氮二异庚腈;所述固化剂为胺类、酸类、酸酐类、酚类、醇类、硫醇类，包括但不限于二乙烯基三胺、芳香族多胺、双氰双胺、三氟化硼、乙二酸、邻苯二甲酸酐、对苯二酚、乙二醇、1,4-丁二硫醇;所述催化剂为胺类、麟类,包括但不限于选自正丙胺，三乙胺,N,N-二异丙基乙胺,4-二甲氨基吡啶，三苯基麟。  \n\n17.根据权利要求1或2所述的一种有机-无机杂化高分子复合材料，其特征在于所述添加剂包括但不限于阻聚剂、润湿剂、抗氧化剂、流平剂、消泡剂、流变改性剂、附着力增进剂。  \n\n18.根据权利要求17所述的一种有机-无机杂化高分子复合材料，其特征在于所述阻聚剂包括但不限于4-甲氧基苯酚、对苯二酚、对苯;所述润湿剂包括但不限于丙二醇、甘油;所述抗氧化剂包括但不限于2,6-二叔丁基对甲酚，丁基羟基茴香醚、叔丁基对苯二酚等。所述流平剂为聚二甲基硅氧烷，聚丙烯酸酯;所述消泡剂包括但不限于乳化硅油、高碳醇脂肪酸酯复合物、聚氧乙烯聚氧丙烯季戊四醇醚、聚氧乙烯聚氧丙醇胺醚、聚氧丙烯甘油醚和聚氧丙烯聚氧乙烯甘油醚、聚二甲基硅氧烷;所述流变改性剂包括但不限于气相二氧化硅、麻油衍生物;所述附着力增进剂包括但不限于硅烷偶联剂、钛酸酯偶联剂。  \n\n19.权利要求1或2所述的一种有机-无机杂化高分子复合材料的制备方法，其特征在于按配比，称取可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物、可聚合或可交联的单体或齐聚体、固化辅助剂和/或添加剂,然后相互溶解或混合均匀,经聚合和/或交联固化，得到  \n\n有机-无机杂化高分子复合材料。  \n\n20.权利要求19所述的一种有机-无机杂化高分子复合材料的制备方法，其特征在于所述固化的方式包括但不限于紫外线照射、电子束照射、加热。  \n\n21.包含权利要求1或2所述有机-无机杂化高分子复合材料的光学材料、介电材料、储能材料、光电子器件、功能涂料产品也在本发明的保护范围之内。",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# 一种有机-无机杂化高分子复合材料及其制备方法",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001]］本发明属于高分子复合材料领域，具体涉及一种有机-无机杂化高分子复合材料及其制备方法。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002]有机-无机杂化高分子材料是一种复合材料，通常在微观上即在纳米尺度或者在分子水平上，通过化学键键合而成。它和传统的复合材料有重大意义上的区别。传统的复合材料是在宏观上即微米到毫米，甚至在更大尺度上将有机和无机相物理性地混合而成。传统复合材料，甚至纳米复合材料和杂化高分子复合材料的最大区别在于，杂化高分子复合材料所具有的有些新性质(性能)，在原始其各自组成的无机相和有机相都不具有。  \n\n[0003]最近20多年来，有机-无机杂化高分子复合材料越来越强烈地引起了化学家，材料科学家以及工业界的兴趣。这些兴趣首先源自于材料学家们企图同时利用无机材料的优秀物理性能和有机材料加工简单的两种优势的愿望。而且，两种材料的化学键合，还可能产生一些新的，在原先无机和有机独自组份中都不具有的性能。相比较于传统的复合材料，甚至纳米复合材料，有机-无机杂化高分子复合材料具有如下明显优点：  \n\n[0004]1、无机(原子或分子)簇所具有的光学，电学，磁学或其他特别性质可以被引入有机高分子的机体内;2、一般无机态分子往往需要高温处理才能进行加工制作，相反，杂化高分子复合材料可以象一般处理高分子/聚合物那样在较低温度甚至常温下加工处理，甚至还可能像活性小分子或齐聚体那样，进行交联或聚合而形成更大分子;3、传统的复合材料是异相多相的混合体，甚至纳米复合材料，如果没有能做到很好的纳米无机颗粒的表面改性，也难避免异相光散射问题。与此极大的区别是，有机-无机杂化高分子材料是一种均相、透明物质，光散射现象可以完全避免。因此，极适于用作光学材料。  \n\n[0005]这种新型材料技术的创立与发展，为各种日新月异高科技应用发展所亟需的特种材料功能的开发，无论于理论设计，还是工业实践，都提供了一个巨大的可能。它的巨大潜力和应用的广泛性已经在再生新能源工业，化学催化工业，微电子工业，光电子工业，医学生物业，功能涂料等等逐步得到验证。要达到这些成就，无论是传统的纯无机材料技术的实践，还是纯有机材料技术的实践都证明，不是经济成本极高，就是几乎不可能;甚至近年来热议的纳米复合材料技术，也是困难重重，难以实际地产业化与工业化。  \n\n[0006］根据有机(相)部分和无机(相)部分可能的相互作用，可将有机-无机杂化材料分为两类：第一类为弱相互作用类,即范德华力(vanderWaals);氢键作用(hydrogenbonding)和弱电磁作用(weak electrostatic interactions);传统复合材料,甚至纳米复合材料，多是物理混合而成，就多属这一类。第二类为强相互作用类，即有机分子和无机分子以化学键相键合(covalentbonds)而形成杂化高分子复合材料，以及纳米无机颗粒的表面被改性，并赋予化学活性，同样通过化学键将无机颗粒和有机基体结合为一体，都属于这一类。  \n\n[0007]第一类材料,传统的基体-填料系统,也包括聚合物-纳米填料系统，或叫纳米复合材料系统，即，以聚合物为基体，以无机纳米颗粒，纳米纤维，纳米片等为填料的复合材料系统。这些纳米填料，例如纳米黏土,纳米二氧化硅(silica)等可以在很大程度上提高材料的物理和化学性能。纳米相的极高比表面(specific surface area)产生的巨大无机和有机相间的相互作用甚至可能给复合材料带来新的性能。遗憾的是，和传统的复合材料一样，这种纳米复合材料仍旧是一种多相异相的非均匀系统。无机相和有机相之间的不匹配性，常常是材料异相分离，造成自我凝聚或自我絮凝，分层，结块，最终失去功能而不能使用的主要原因。同时，不匹配性也常是造成不利于加工工艺的特殊材料流变行为的主要原因。在更特别的光学应用上，这种多相异相的非均匀材料常常造成光散射现象，使得材料浑浊，失去光学透明性，而完全不能使用。纳米材料科学家和化学家们提出了许多有价值的方法，对纳米颗粒 (纳米纤维，纳米片等)作表面修饰改性，虽然在实验室里取得不少进展，但在实际工业界的实施，仍旧是一个艰难而漫长的挑战。  \n\n[0008]溶胶-凝胶技术是迄今为止的最好的，从分子水平上，设计和制备有机-无机杂化高分子复合材料的方法。该技术最大的优点是，它可以直接以分子作为前驱体，将无机部分和有机部分分别以分子，常常是高分子的方式，通过化学键的方式键合在一起制备而成。在第一类复合材料中常见的，因异相不匹配而分离，不稳定，光散射现象都能被完全克服。  \n\n[0009］硅倍半氧烷(Silsesquioxane)：溶胶-凝胶法制备的一类最主要的产物就是硅氧化合物。硅氧化合物根据其硅原子上连结的氧原子的个数可以分为3类。其中研究较多且应用较成熟的主要是两类，一个是由(Si02)结构组成的无机陶瓷材料，另一个是由(R2Si0)结构组成的聚硅氧烷材料。而介于这两者之间的，是由 $\\mathrm{(RSiO_{3/2})}$ 单元构成的硅倍半氧烷。这一领域在最近二十年内发展迅速，是最典型的有机-无机杂化分子。  \n\n[0010]硅倍半氧烷中存在一个R基团，可以是氢原子或有机基团，按R取代基分类，可以将硅倍半氧烷分为非活性功能型和活性功能型两类。非活性功能型硅倍半氧烷：非活性功能型硅倍半氧烷的常见取代基有甲基、苯基、碳氟基等。这类硅倍半氧烷通常作为纳米粒子填料，与聚合物组成基质-填料体系，形成复合材料。在这种复合材料中，填料粒子起到增强聚合物的机械强度、耐高温、耐气候、抗老化、抗击穿等作用，对材料的理化性能都有很大的提升。活性功能型硅倍半氧烷：活性功能型硅倍半氧烷的常见取代基有乙烯基和烯丙基、(甲基)丙烯酸酯基、氨基取代烷基、环氧基取代烷基、脂环族环氧基、羧基等。这类硅倍半氧烷的特点是其有机取代基上具备活性反应位点，可以与有机化合物或生物分子进行反应，从而形成新的杂化分子或实现特殊的功能。由于这种特点，这类化合物除了具备非活性功能型硅倍半氧烷所能提供的应用价值，还会具备一些特殊的功能。例如含有乙烯基、烯丙基或(甲基)丙烯酸酯基的硅倍半氧烷可以进行自由基聚合反应，含有氨基的硅倍半氧烷具有很好的生物活性，含有环氧基或脂环族环氧基的硅倍半氧烷可以进行阳离子聚合反应，含有羧基的硅倍半氧烷则可以与羟基或一些碱性化合物反应。活性功能型硅倍半氧烷中引入了有机活性功能基团，可提供化学、生物活性位点，从而为材料提供更多的性能。  \n\n[0011]但是，要达到使用溶胶-凝胶技术制备有机-无机杂化高分子复合材料的产业化和工业化，长期阻碍这项技术产业化的三个实质性问题成为最大障碍，必须要克服和解决：  \n\n[0012]1、水解反应和几乎同时发生和进行的缩合反应的不可控问题;这两个反应几乎同时受到以下多重因素影响,包括：反应物的化学计量比，反应介质，催化剂的类型，反应过程温度的控制，前驱体反应物自身的化学活性以及其他反应条件等;  \n\n[0013]2、水解和缩合反应难以反应完全。而在最终产物中，未水解的烷氧基和未缩合的羟基会对产物的热稳定性和水解稳定性造成影响。  \n[0014]3、使用传统的溶胶-凝胶技术进行工业化生产制备有机-无机杂化高分子复合材料的产率低，耗时长耗能高。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0015]本发明所要解决的技术问题是针对上述现有技术存在的不足而提供一种有机-无机杂化高分子复合材料及其制备方法，将有机材料与无机材料的特性进行了组合，利用两者的优势进行互补或增强，具有高光学透明性，高热稳定性，高机械强度，高耐候性等。  \n\n[0016]本发明为解决上述提出的问题所采用的技术方案为：  \n[0017] 一种有机-无机杂化高分子复合材料，其主要组成成分包括：可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物、可聚合或可交联的单体或齐聚体、固化辅助剂和/或添加剂。[0018]按上述方案，所述有机-无机杂化高分子复合材料，主要组成成分按质量百分比计为：可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物 $5-90\\%$ 、可聚合或可交联的单体或齐聚体 $10-80\\%$ 、固化辅助剂和/或添加剂 $0-10\\%$ ；优选地，可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物 $10\\%$ 、可聚合或可交联的单体或齐聚体 $10\\text{\\textperthousand}$ 、固化辅助剂和/或添加剂 $0-10\\%$ 0  \n\n[0019]按上述方案，所述可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物通式为$\\mathrm{R_{m}S i_{n}O_{a}(O H)_{b}X_{c}}$ ，其中，m,n,a,b,c均表示原子或基团的个数， $\\mathtt{m},\\mathtt{n}$ 为正整数，且n大致在2至100的范围内，m在0至3n的范围内，b，c均为非负整数，且满足 $\\mathfrak{b}{+}\\mathfrak{c}{\\langle}3\\mathfrak{n}$ ,a为正实数，且 $\\mathrm{a}=2\\mathrm{n}^{-}$ $0.5\\mathrm{b}{-}0.5\\mathrm{c}{-}0.5\\mathrm{m};\\mathrm{Si}$ 表示元素硅;0H表示羟基，X表示为可水解的功能团。R为有机基团，可相同可不同，优选含有以下一种或几种非活性或活性功能团，这些功能团包括但不限于：烷基、苯基、碳氟基等非活性基团,丙烯酰氧基烷基或芳香基，甲基丙烯酰氧基烷基或芳香基，烯烃基，芳香烃烯基，炔烃基，环烯烃基，环炔烃基，链式脂肪族环氧烷基，环状脂肪族环氧烷基，硫醇基以及肉桂酸基等活性基团。更进一步，R中至少有一个含有一种或几种活性功能团;X优选烷氧基、卤原子等。  \n\n[0020]］按上述方案，所述可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物的制备方法，主要步骤如下：  \n\n[0021] 1)以有机硅烷和水作为反应物，进行水解和缩合反应，获得作为第一中间体;[0022] 2)选择或者制备第二中间体，所述第二中间体含有能与硅羟基进行封端反应的官能团，并同时具有可聚合或可交联活性有机官能团;  \n[0023]3)第二中间体对第一中间体进行硅羟基封端反应，生成可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物。  \n[0024]进一步地，所述第一中间体、第二中间体均为一种或者几种组分的混合物。[0025]进一步地，所述有机硅烷可以用化学式 $\\mathrm{R_{t}S i X_{4-t}}$ 表达，包括但不局限于有机烷氧基硅烷、有机卤硅烷等。其中，R可以是烷基、苯基、碳氟基等非活性基团，也可以是活性基团，例如，可聚合的或可交联的活性基团。这些活性基团包括但不限于丙烯酰氧基烷基或芳香基，甲基丙烯酰氧基烷基或芳香基，烯烃基，芳香烃烯基,炔烃基，环烯烃基,环炔烃基,链式脂肪族环氧烷基,环状脂肪族环氧烷基，硫醇基以及肉桂酸基等。X表示为可水解的功能团，  \n\n例如：烷氧基、卤原子等；t为0，1，2，或3;Si表示元素硅。  \n\n[0026]］进一步地，所述水解和缩合反应中，有机硅烷的摩尔数的总和与水摩尔数的比值为 $1.0\\colon(1.0{\\sim}6.5)$ ，优选 $1.0\\colon(1.0{\\sim}4.0)$ 。水解和缩合反应的时间范围为 $0{\\sim}7$ 天，优选 $0{\\sim}4$ 天;温度范围为 $0{\\sim}200^{\\circ}\\mathrm{C}$ ，优选 $20{\\sim}80^{\\circ}\\mathrm{C}$ 0  \n\n[0027］进一步地，所述第一中间体是完全缩合的笼状硅倍半氧烷，以及多种未完全缩合硅倍半氧烷的混合物。这些未完全缩合硅倍半氧烷包括：未完全缩合的笼状硅倍半氧烷，未完全缩合的梯状硅倍半氧烷，未完全缩合的环状硅倍半氧烷，以及其他不同缩合程度的硅倍半氧烷化合物的组合。在第一中间体里，除了完全缩合的笼状硅倍半氧烷外，所有未完全缩合的硅倍半氧烷化合物上都带有一个或多个硅羟基，这些硅羟基为下一步的硅羟基封端反应提供了化学活性位点。  \n\n[0028]进一步地，所述第二中间体中能进行硅羟基封端反应的基团包括但不限于异氰酸酯基，酰卤基，硅卤基。所述可聚合或可交联活性有机官能团包括但不限于丙烯酰氧基烷基或芳香基，甲基丙烯酰氧基烷基或芳香基，烯烃基，芳香烃烯基，炔烃基,环烯烃基,环炔烃基(cycloalkyne)，链式脂肪族环氧烷基,环状脂肪族环氧烷基,硫醇基以及肉桂酸基等。  \n\n[0029］进一步地，所述第一中间体中的硅羟基和第二中间体中的异氰酸酯基的摩尔比在$0.5{\\sim}1.5$ 之间，优选地在 $0.8\\sim1.2$ 之间，更优选地在 $0.99\\sim1.03\\$ 之间，硅羟基封端反应的温度在 $60{\\sim}100^{\\circ}\\mathrm{C}$ 之间，硅羟基封端反应的时间在 $2\\mathord{\\sim}12$ 小时之间。  \n\n[0030]按上述方案，所述可聚合或可交联的单体或齐聚体为一种或多种按任意比例的混合物。其中，可聚合或可交联的活性基团包括但不限于烯烃基、芳香烃烯基、炔烃基、环烯烃基、环炔烃基、肉桂酸基、链式脂肪族环氧烷基、环状脂肪族环氧烷基、琉基、丙烯酰氧基烷基或芳香基、甲基丙烯酰氧基烷基或芳香基等中的一种或几种。  \n\n[0031］按上述方案，所述固化辅助剂可分为自由基光引发剂，阳离子光引发剂，热引发剂，固化剂，催化剂等中的一种或几种。  \n\n[0032]按上述方案，所述自由基光引发剂为2-羟基 $-2-$ 甲基-1-苯基丙酮,1-羟基环已基苯基甲酮,2,4,6-三甲基苯甲酰基-二苯基氧化麟,2-甲基 $-2-$ (4-吗啉基)-1-[4- (甲硫基)苯基]-1-丙酮,二苯甲酮,4-甲基二苯甲酮,4-(二甲氨基)-苯甲酸-(2-乙基)己酯等。  \n\n[0033]按上述方案，所述阳离子光引发剂为重氮盐、二芳基碘盐、三芳基硫盐、烷基硫盐、铁芳烃盐、磺酰氧基酮及三芳基硅氧醚等。  \n\n[0034]按上述方案，所述热引发剂为有机过氧化物或偶氮类引发剂，如过硫酸钾，过硫酸铵，过氧化环己酮、过氧化二苯甲酰、叔丁基过氧化氢、偶氮二异丁腈、偶氮二异庚腈等。  \n\n[0035］按上述方案，所述固化剂为胺类、酸类、酸酐类、酚类、醇类、硫醇类等。如4,4'-二氨基二苯矾、二乙烯基三胺、芳香族多胺、双氰双胺、三氟化硼、乙二酸、邻苯二甲酸酐、对苯二酚、乙二醇、1,4-丁二硫醇等。  \n\n[0036]］按上述方案，所述催化剂为胺类、麟类等，如选自正丙胺，三乙胺，N,N-二异丙基乙胺,4-二甲氨基吡啶，三苯基麟等。  \n\n[0037]按上述方案，所述添加剂可分为阻聚剂、润湿剂、抗氧化剂、流平剂、消泡剂、流变改性剂、附着力增进剂等。所述阻聚剂为4-甲氧基苯酚、对苯二酚、对苯等。所述润湿剂为丙二醇、甘油等。所述抗氧化剂为2,6-二叔丁基对甲酚，丁基羟基茴香醚、叔丁基对苯二酚等。所述流平剂为聚二甲基硅氧烷，聚丙烯酸酯等。所述消泡剂为乳化硅油、高碳醇脂肪酸酯复合物、聚氧乙烯聚氧丙烯季戊四醇醚、聚氧乙烯聚氧丙醇胺醚、聚氧丙烯甘油醚和聚氧丙烯聚氧乙烯甘油醚、聚二甲基硅氧烷等。所述流变改性剂为气相二氧化硅、麻油衍生物等。所述附着力增进剂为硅烷偶联剂、钛酸酯偶联剂等。  \n\n[0038]本发明所述有机-无机杂化高分子复合材料的制备方法，主要步骤为：按配比，称取可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物、可聚合或可交联的单体或齐聚体、固化辅助剂和/或添加剂，然后相互溶解或混合均匀，经聚合和/或交联固化，得到有机-无机杂化高分子复合材料。  \n\n[0039]］按上述方案，所述固化的方式为紫外线照射、电子束照射、加热等。具体地，所述固化可以经紫外线照射，通过光引发自由基聚合或交联达到固化的目的;或者，所述固化可以经电子束照射，通过聚合或交联达到固化的目的；或者，所述固化可以经加热，通过自由基聚合和或开环聚合反应达到固化的目的。其中，在使用电子束照射聚合或交联时，所述组成成分中可以不含光引发剂。由于本发明所述有机-无机杂化高分子复合材料可以包含一种或多种不同的可聚合或可交联的单体或齐聚体，故固化方式的机理可能是一种或者是几种不同机理的组合。  \n\n[0040］包含本发明所述有机-无机杂化高分子复合材料的光学材料、介电材料、储能材料、光电子器件、功能涂料等产品也在本发明的保护范围之内。  \n\n[0041] 与现有技术相比，本发明的有益效果是：  \n\n[0042]1、本发明所述有机-无机杂化高分子复合材料，将有机材料与无机材料的特性进行了组合，利用两者的优势进行互补或增强，可以同时拥有无机材料的高光学透明性，高热稳定性，高机械强度，高耐候性等，以及有机材料的优良的可加工性，具有很好的工业化应用前景，可以广泛用于新能源，光电子器件，生物医药，功能涂料等多种高科技领域。  \n\n[0043]2、本发明所述有机-无机杂化高分子复合材料中，有机相和无机相通过化学键有力的结合在一起，有效的克服了长期困扰工业界的一个难题，即在传统的通过物理方式混合的有机-无机复合材料(包括纳米复合材料)中，由于异相不匹配性而造成的相分离的问题。  \n\n[0044]3、本发明将改进的溶胶-凝胶技术和聚氨酯合成化学相结合,解决了用溶胶-凝胶法制备有机-无机分子杂化材料走向大规模工业生产的根本问题，即水解缩合反应过程的不可控以及反应不完全导致产物不稳定等问题，提出了一种过程可控且产物稳定的制备途径，并具有反应时间较短的优点，同时，可以有选择的引入相同，或不同的新型官能团，提供了一条制备多功能分子杂化材料的新途径。通过该途径合成有机-无机杂化的可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物，进而与可聚合或可交联的单体或齐聚体、固化辅助剂和/或添加剂均匀混合，得到有机-无机杂化高分子复合材料，制备步骤简单，稳定可控，拓宽了发展新型功能材料的途径。",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 附图说明  \n\n[0045] 图1为产物MASSQ-1至MASSQ-5的光学透明性。   \n[0046] 图2为参比样品甲基丙烯酰氧基丙基笼型硅倍半氧烷(T8,T1o和T12的混合物)的基 质辅助激光解吸电离飞行时间质谱。质荷比范围为 $1100{\\sim}3000\\mathrm{{Da}}$ 。   \n[0047] 图3为样品MASSQ-1的基质辅助激光解吸电离飞行时间质谱。质荷比范围为 $650\\sim$  \n\n1600Da。  \n\n[0048] 图4为样品MASSQ-1的MALDI-TOF质谱测试结果中 $\\mathrm{T_{4}}$ (OH)4和 $\\mathrm{T}_{7}$ (OH)3对应的部分可能的分子结构。其中， $\\boldsymbol{\\mathrm{R}}^{1}$ 基团代表甲基丙烯酰氧基丙基基团。  \n[0049] 图5为样品MASSQ-1的电喷雾电离飞行时间质谱，质荷比范围为 $700{\\sim}3000\\mathrm{{Da}}$ 0[0050] 图6为红外吸收光谱测试结果;其中，测试样品为IPDI-HEA(a)和MASSQ-UA(c），以MASSQ-1(b)为参照。  \n[0051] 图7为样品IPDI-HEA的核磁共振氢谱图。  \n[0052] 图8为样品MASSQ-UA的核磁共振氢谱图。  \n[0053] 图9为样品MASSQ-UA的核磁共振硅谱谱图。  \n[0054] 图10为样品MASSQ-UA的基质辅助激光解吸电离飞行时间质谱，质荷比范围为800${\\sim}2000\\mathrm{{Da}}$ 0  \n[0055] 图11为样品MASSQ-UA的MALDI-TOF质谱测试结果中T7 (OH) $\\mathrm{2R^{2}}$ 对应的部分可能的分子结构，其中， $\\mathrm{R}^{1}$ 基团代表甲基丙烯酰氧基丙基基团。  \n[0056] 图12为样品IPDI-HEA的电喷雾电离飞行时间质谱，质荷比范围是 $0\\sim1000\\mathrm{{Da}}$ 0[0057] 图13为样品MASSQ-UA的电喷雾电离飞行时间质谱，质荷比范围是 $700{\\sim}3000\\mathrm{{Da}}$ 0[0058] 图14为产物MASSQ-UA以及对照样品MASSQ-1的实物照片以及紫外-可见吸收光谱。[0059] 图15为样品MASSQ-1和MASSQ-UA的(a)TGA和(b)DTG曲线。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 具体实施方式  \n\n[0060］为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明不仅仅局限于下面的实施例。  \n[0061］本发明中，可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物的制备过程中，主要步骤及有关化学方程式如下：  \n[0062] 按上述方案，所述可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物的制备方法，主要步骤如下：  \n[0063]第一步：以有机硅烷和水作为反应物，进行水解和缩合反应，所得产物(MASSQ)作为第一中间体;  \n\n[0064]  \n\n![](images/79f6a08d33f24feb8e95dfb521470e4e4a8f3349a19a4a45b7d5d5ecfd37a61f.jpg)  \n\n[0065]由于溶胶凝胶法中，水解和缩合反应通常难以进行完全，所以产物中可能会有含有极少量的未水解的甲氧基团和未缩合的硅羟基的组分。按照溶胶-凝胶化学界里现在已被广泛接受的表示方法，将硅倍半氧烷中一个硅原子连结一个有机基团或氢原子及三个氧原子的结构简写为T，于是产物 $\\mathrm{MASS4}$ 可以用通式 $\\mathrm{T_{n}}$ (OH) $\\mathbf{\\boldsymbol{x}}$ （OCH3）y表示，其中 $\\mathrm{{T}=}$ $\\mathrm{R}^{1}\\mathrm{Si}0_{[1.5-(x+y)/2\\mathrm{n}]}$ (此处， ${\\mathrm{R}}^{1}$ 代表甲基丙烯酰氧基丙基， $\\mathrm{n=2,3,4,5,6\\cdots\\cdots,x=0,1,2\\cdots\\cdots,y}$ 几乎为0)。由于空间位阻效应，极少量残存的未水解的甲氧基团反应活性极低，所以，其残存的甲氧基团个数，y，可以视为零。这样，产物MASSQ可以用简化的通式 $\\mathrm{{T}_{n}\\left(0H\\right)_{x}}$ 表示。同样，在反应方程式的产物结构式，含有甲氧基团的结构单元也被略去(详情请见实例中的结构分析)。注意，各单元的排列顺序不代表实际分布情况，实际情况应为随机排布。  \n\n[0066]］第二步:等摩尔的丙烯酸羟乙酯(HEA)与异佛尔酮二异氰酸酯(IPDI)发生加合反应,得到单异氰酸酯基的化合物异佛尔酮二异氰酸酯-丙烯酸羟乙酯(IPDI-HEA),即带有能和硅羟基反应的NCO基团以及可聚合的丙烯酸酯基团的第二中间体;  \n\n[0067]  \n\n![](images/bf50bb8043ddfd6e3db153bb5896eb8750cbced7f6617501854a6a65a36b44ad.jpg)  \n\n[0068]第三步：IPDI-HEA中的NCO基团与MASSQ中的硅羟基的加合反应，获得可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物(MASSQ-UA)。  \n\n[0069]  \n\n![](images/0c222a77084fee731899d3a6e1841b2b4484d2928d720cf999b9e87749e31b3b.jpg)  \n\n[0070]］其中，MASSQ和MASSQ-UA的结构式仅表示其结构的单元组成，结构式中各单元的连接顺序并不代表实际排序，实际情况应为随机排布。  \n\n[0071] 实施例1-2  \n\n[0072] 主要试剂及仪器：所用的化学试剂如无特别说明均为直接使用，主要试剂列于表1中，主要仪器设备列于表2中，其他未列试剂均为市售分析纯或化学纯的产品。[0073] 表1实验所用的主要化学试剂  \n\n[0074]   \n\n\n<html><body><table><tr><td>药品名称</td><td>规格</td><td>生产厂家</td></tr><tr><td>3-甲基丙烯酰氧基丙基二甲氧基硅烷 (MAPTMS)</td><td>98%</td><td>湖北武大有机硅新材料股份有限公司</td></tr><tr><td>无水乙醇</td><td>分析纯</td><td>国药集团化学试剂有限公司</td></tr><tr><td>浓盐酸</td><td>分析纯</td><td>国药集团化学试剂有限公司</td></tr><tr><td>甲基丙烯酰氧基丙基笼型硅倍半氧烷（T， T1o，T混合物）</td><td></td><td>Sigma-Aldrich 中国</td></tr><tr><td>氯仿</td><td>分析纯</td><td>国药集团化学试剂有限公司</td></tr><tr><td>氛代氯仿（含0.03%v/v四甲基硅烷）</td><td>99.8%</td><td>百灵威科技有限公司</td></tr><tr><td>乙晴</td><td>HPLC</td><td>Sigma-Aldrich中国</td></tr><tr><td>甲醇</td><td>HPLC</td><td>Sigma-Aldrich中国</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# [0075] 表2实验所用的主要仪器设备  \n\n[0076]   \n\n\n<html><body><table><tr><td>仪器名称</td><td>型号</td><td>生产厂家</td></tr><tr><td>艾科浦超纯水机</td><td>AFZ-0501-U</td><td>重庆颐洋企业发展有限公司</td></tr><tr><td>电子天平</td><td>BL-220H</td><td>日本岛津Shimadzu</td></tr><tr><td>旋转蒸发仪</td><td>RE-2000A</td><td>上海亚荣生化仪器厂</td></tr><tr><td>傅立叶变换红外光谱仪</td><td>NicoletiS10</td><td>赛默飞世尔科技公司</td></tr><tr><td>基质辅助激光解吸电离飞行时间质谱仪</td><td>Voyager-DE STR</td><td>美国应用生物系统公司</td></tr><tr><td>电喷雾电离飞行时间质谱仪</td><td>Q-TOF</td><td>德国布鲁克公司</td></tr><tr><td>核磁共振波谱仪</td><td>MercuryVX-300</td><td>美国瓦里安公司</td></tr><tr><td>核磁共振波谱仪</td><td>Inova 600</td><td>美国瓦里安公司</td></tr><tr><td>紫外-可见吸收光谱仪</td><td>TU-1901</td><td>北京普析通用仪器有限责任公司</td></tr><tr><td>旋转粘度计</td><td>LVDV-II+Pro</td><td>美国博勒飞工程实验室</td></tr><tr><td>循环恒温水槽</td><td>SYC</td><td>巩义市了华仪器有限责任公司</td></tr></table></body></html>  \n\n[0077] 实施例1  \n\n)078] 1、甲基丙烯酰氧基丙基硅倍半氧烷(MASSQ)，即第一中间体，合成步骤如下：  \n\n[0079]1)在一个100mL的三口烧瓶中，称取 $40.0\\mathrm{g}\\left(0.161\\mathrm{mol}\\right)3-$ 甲基丙烯酰氧基丙基三甲氧基硅烷(MAPTMS)，然后在三口烧瓶的三个瓶口上分别安装温度计、机械搅拌和恒压滴液漏斗；另外，在另一个50mL的烧杯中依次称取 $8.792\\mathrm{g}$ 的0.lmol/L的稀盐酸(水的物质的量为0.485mol)和 $14.8\\mathrm{g}$ 乙醇，用玻璃棒搅拌均匀，得无色的反应物溶液，然后转移至恒压滴液漏斗中；此时，水和MAPTMS的摩尔比为3:1;  \n\n[0080]2)在室温及机械搅拌的条件下，开始恒压滴液漏斗向MAPTMS中滴加反应物溶液，控制滴加速度使反应物溶液在30分钟内滴加完全;滴完后，迅速将恒压滴液漏斗换成回流冷凝管并保持机械搅拌，将反应混合物加热至 $60^{\\circ}\\mathrm{C}$ ，并在此温度下维持4小时，得无色溶液;[0081]］在该合成步骤中，将水与盐酸、乙醇的溶液滴入3-甲基丙烯酰氧基丙基三甲氧基硅烷(MAPTMS)中，发生水解反应，酸作催化剂。随着水解出现的硅羟基增多，缩合反应也同时发生。该步骤为一个明显的放热过程，为控制反应速率，防止局部反应过快，反应物需缓慢滴加。  \n\n[0082]3)将步骤2)所得无色溶液倒入一个100mL圆底烧瓶中，减压旋转蒸发，水浴加热至$80^{\\circ}\\mathrm{C}$ ，真空度达到 $0.095\\mathrm{MPa}$ ，并在此温度和压力下保持4个小时，从而将无色溶液中挥发性的醇类及水除去，最终得到无色透明的油状物，即为第一中间体甲基丙烯酰氧基丙基硅倍半氧烷(MASSQ)，标记为样品MASSQ-1。  \n\n[0083］2、基质辅助激光解吸电离飞行时间质谱对所制备的第一中间体，即甲基丙烯酰氧基丙基硅倍半氧烷(样品MASSQ-1)的结构表征  \n\n[0084]］基质辅助激光解吸电离飞行时间(MALDI TOF)质谱测试作为一种新兴的软电离质谱技术，具有灵敏度高，可测质量数大(可达30万)以及可提供分子离子峰信息的特点，近二十年以来一直是研究硅倍半氧烷结构的有效工具之一。在该技术中,影响测试结果的重要因素之一是样品的电离效果。在测试中，对多个制样条件进行了筛选：分别使用不同的基质，如芥子酸(SA)、a-氰基 $-4-$ 羟基肉桂酸(CHCA)和2，5-二羟基苯甲酸(DHB)；加银盐(三氟乙酸银)辅助;以及采用不同的样品浓度，如0.01mg/ml，1.0mg/ml和 $\\mathrm{10mg/ml}$ ,配制共结晶薄膜。通过不同的组合，最终获得较好的测试结果。  \n\n[0085] 1)参比样品笼型硅倍半氧烷的MALDITOF质谱的测试结果[0086]参比样品甲基丙烯酰氧基丙基笼型硅倍半氧烷( $\\mathrm{\\DeltaT8},\\mathrm{T10}$ 和 $\\mathrm{T_{12}}$ 的混合物)的MALDITOF质谱，见图2，主要有6组峰簇，相邻峰簇之间的间隔均在 $160{\\sim}200\\mathrm{{Da}}$ 以内。由于MALDI为软电离技术，一般不会造成分子裂解，故可假设这些信号均为分子离子峰，而相邻峰簇的间隔正好是一个T单元，即 $\\mathrm{(C_{7}H_{11}O_{2}S i0_{1.5})}$ $\\mathrm{(M_{w}=179.05D a)}$ 的摩尔质量，故可推测出，这些峰簇是一系列相差为一个结构单元的硅倍半氧烷的同系物;再根据质荷比进行推导，便得出了各主要信号峰所对应的组分的化学式，及其理论分子量和可能的分子简式，结果列于表3中。  \n\n[0087]在表3中，理论值与实测值的相对偏差均小于 $0.06\\%$ ，表明分析结果准确。在后面MASSQ-1的MALDITOF质谱以及电喷雾质谱的分析中亦同。  \n\n[0088]表3甲基丙烯酰氧基丙基笼型硅倍半氧烷 $(\\mathrm{n=8,10,12})$ 参比样品MALDI-TOF质谱测试结果的主要信号峰，对应的化学式，理论分子量以及可能的分子简式[0089]  \n\n<html><body><table><tr><td>实测质荷比（m/z）</td><td>符合的化学式</td><td>理论分子量</td><td>相对偏差（%）</td><td>分子简式</td></tr><tr><td>1455.17</td><td>（CHOSi）ONa</td><td>1455.35</td><td>-0.012</td><td>T8</td></tr><tr><td>1473.11</td><td>(CHOSi）O（OH）N a</td><td>1473.36</td><td>-0.017</td><td>T8(OH）2</td></tr><tr><td>1490.13</td><td>（CHOSi）O(OH）K</td><td>1489.34</td><td>0.053</td><td>Tg(OH）</td></tr><tr><td>1644.18</td><td>(CHOSi）O（OH)N</td><td>1643.40</td><td>0.047</td><td>T(OH)</td></tr><tr><td>1661.11</td><td>（CHOSi）O（OH）N</td><td>1661.41</td><td>-0.018</td><td>T(OH)</td></tr><tr><td>1814.15</td><td>（CHOSi）oO1sNa</td><td>1813.44</td><td>0.039</td><td>T10</td></tr><tr><td>1831.13</td><td>（CHnOSi）oO（OH）</td><td>1831.45</td><td>-0.017</td><td>T10(OH）</td></tr><tr><td>2019.16</td><td>Na （CHOSi）Os（OH）</td><td>2019.50</td><td>-0.017</td><td>T(OH)</td></tr><tr><td>2172.23</td><td>Na* （CHOSi）O8Na</td><td>2171.53</td><td>0.032</td><td></td></tr><tr><td>2377.52</td><td>(CHOSi）O18（OH） Na</td><td>2377.59</td><td>-0.003</td><td>T1(OH） T12</td></tr></table></body></html>\n\n[0090] a相对偏差 $\\c=$ [(实测质荷比-理论分子量)/理论分子量]x $100\\%$ 0[0091] 由参比样品的MALDITOF质谱的分析结果可知，该样品中确实含有T8， $\\mathrm{T}_{10}$ 和T12三种  \n\n组分，与已知的样品信息，以及参比样品的核磁氢谱、硅谱的测试结果均吻合。由此，再次验证了参比样品的组分信息，同时也确定了本发明中所采用的MALDI TOF质谱测试方法可行，测试结果准确，可对结构近似的未知样品MASSQ-1采用此方法测试。  \n\n[0092]另外，由于硅倍半氧烷属于低聚物，不同聚合度的分子之间，以及完全缩合与不完全缩合的分子之间，极性较相近，因此，难以将特定的某一个或某几个组分进行完全分离。表4的分析结果显示，参比样品中除了T8,T1o和T12，还有一些含有少量羟基的 $\\mathrm{T}_{8}\\mathrm{\\sim}\\mathrm{T}_{13}$ 组分，表明参比样品中确实含有杂质，这也与核磁硅谱的分析结果一致。  \n\n[0093] 2)实施例1产物MASSQ-1的MALDITOF质谱的测试结果[0094]］图3是产物MASSQ-1的MALDI TOF质谱，其中的主要信号峰可分为4组峰簇，且相邻的峰簇的间隔为 $160\\sim190\\mathrm{{Da}}$ 。与参比样品类似，这些峰簇说明产物MASSQ-1中含有一系列间隔为一个T结构单元的硅倍半氧烷的组分。由核磁氢谱和硅谱的分析结果可知，MASSQ-1中除了T单元，还含有部分羟基，以及极少量甲氧基和乙氧基，因此，可设其结构通式为 $\\mathrm{T}_{\\mathrm{n}}\\left(0\\mathrm{H}\\right)_{\\mathrm{\\scriptsize~x}}$ (OCH3) $\\mathbf{y}$ (OC2H5) z 。  \n\n[0095]为了有效的处理 $\\mathrm{MASS2-1}$ 中的质谱数据，以其质谱中最高的一个峰 $(\\mathrm{m/z}=$ 774.9315)的峰强度作为 $100\\%$ ,将峰强度大于或等于 $10\\%$ 的谱峰对应的质荷比数据全部收集，排除同位素峰后，根据其结构通式进行分析，得到各谱峰对应的组分的化学式，及其理论分子量和可能的分子简式，分析结果列于表4中。  \n\n[0096]］表4产物样品MASSQ-1的MALDI-TOF质谱测试结果的主要信号峰（相对峰强度大于或等于 $10\\%$ )，对应的化学式，理论分子量以及可能的分子简式  \n\n[0097]   \n\n\n<html><body><table><tr><td>实测质荷比 (m/z)</td><td>符合的化学式</td><td>理论质荷比 (m/z)</td><td>相对偏差（%）</td><td>分子简式</td></tr><tr><td>774.9315</td><td>(CHOSi）O（OH）Na</td><td>775.1912</td><td>-0.034</td><td>T4(OH)4</td></tr><tr><td>790.8459</td><td>（CHOSi）O(OH）K</td><td>791.1651</td><td>-0.040</td><td>T(OH）</td></tr><tr><td>802.9019</td><td>（CHOSi）O（OH）（OCH）Na</td><td>803.2225</td><td>-0.040</td><td>T（OH）(OCH）2</td></tr><tr><td>944.9262</td><td>(C-HOSi）O(OH）Na</td><td>945.2311</td><td>-0.032</td><td>T(OH）</td></tr><tr><td>1114.8239</td><td>(CHOSD）O（OH）Na</td><td>1115.2710</td><td>-0.040</td><td>T(OH）</td></tr><tr><td>1132.8382</td><td>(CHnOS）O(OH）Na</td><td>1133.2816</td><td>-0.039</td><td>T(OH)4</td></tr><tr><td>1302.8185</td><td>（CHOSi）O(OH）Na</td><td>1303.3215</td><td>-0.039</td><td>T(OH)</td></tr></table></body></html>  \n\n[0098] a相对偏差 $\\c=$ [(实测质荷比-理论分子量)/理论分子量] $\\mathrm{~x~}100\\%$ 0[0099］由表4的分析结果可知， $\\mathbb{M A S S}\\mathbb{Q}-1$ 中的主要组分是含有羟基的低聚硅倍半氧烷分子，其羟基的数量不超过4个，与参比样品类似，这表明虽然缩合反应进行的并不完全，但是未缩合的硅羟基数量得到了有效的控制。另外，产物MASSQ-1中还存在少量含甲氧基的组分，这是由于水解反应不完全造成的，与核磁氢谱的分析结果一致；而含乙氧基的组分则没有出现，这可能是因为其含量较少，相对信号强度低于 $10\\%$ ，所以没有收进解析范围。  \n\n[0100] 与有机环类化合物类似，在硅倍半氧烷的分子结构当中，硅氧环的个数可以按照等式  \n\n[0101] (1)进行计算：  \n\n[0102] 硅氧环的数量 $=\\left({\\mathrm{n}}{+}2{-}\\mathrm{x}{-}\\mathrm{y}{-}\\mathrm{z}\\right)/2$  \n\n[0103]］根据表4中的分子简式以及等式（1），可以对MASSQ-1中各组分的分子结构进行推导。以 $\\mathrm{T_{4}}$ (OH)4和T7(0H)3为例，其部分可能的结构式如图4所示。  \n\n[0104] 3、电喷雾电离飞行时间质谱对第一中间体，即甲基丙烯酰氧基丙基硅倍半氧烷  \n\n(样品MASSQ-1)的结构表征  \n\n[0105]电喷雾质谱是另一种研究表征硅倍半氧烷的分子结构的有效工具。电喷雾电离作为一种软电离技术，可以用于从有机小分子到生物蛋白大分子的广阔范围内的分子的电离。与MALDITOF质谱不同,电喷雾电离质谱不受基质干扰，离子化效率较高，且有可能产生带有多电荷的离子，从而提供丰富的分子质量与结构的信息。但这也意味着其质谱信息也相对更复杂，谱峰较多。  \n\n[0106]］鉴于硅倍半氧烷分子结构的复杂性，本发明中采用电喷雾电离质谱与MALDI TOF质谱共同对产物MASSQ-1进行表征，以获得尽可能多的结构信息，排除因单一技术的局限性而造成的缺失，从而全面的分析产物的组成及其结构。  \n\n[0107］图5是产物MASSQ-1的电喷雾质谱，与其MALDI TOF质谱类似，其信号峰主要集中在$750{\\sim}1550\\mathrm{D}\\varepsilon$ 的范围内，且可大致分为5组峰簇，峰簇的间隔为 $160\\sim200\\mathrm{{Da}}$ 。然而，电喷雾质谱中的信号峰明显比MALDITOF质谱中的信号峰多，为了获得有效的数据信息，以其最高的谱峰 $(\\mathrm{m/z}=1245.2720)$ 的峰强度为 $100\\%$ ，收集所有峰强度大于或等于 $20\\%$ 的谱峰对应的质荷比数据。采用与MALDITOF质谱相同的方法进行分析，得到各谱峰对应的阳离子，及其相符合的分子简式，分析结果列于表5中。  \n\n[0108]表5产物样品MASSQ-1的电喷雾质谱测试结果的主要信号峰(相对峰强度大于或等于 $20\\%$ )，对应阳离子及其相符合的分子简式  \n\n<html><body><table><tr><td>实测质荷比（m/z）</td><td>符合的分子简式</td><td>离子类型</td><td>理论质荷比（m/z）</td><td>相对偏差（%）</td></tr><tr><td>717.1613</td><td>T8</td><td>[M+2H]</td><td>717.1881</td><td>-0.004</td></tr><tr><td>731.1092</td><td>T(OH)(OCH）6</td><td>[M+Na+K]²</td><td>731.1998</td><td>-0.012</td></tr><tr><td>745.1850</td><td>T8(OH）</td><td>[M+H+K]²</td><td>745.1713</td><td>0.002</td></tr><tr><td>759.1223</td><td>T8(OCH）</td><td>[MIHK]²</td><td>759.1870</td><td>-0.009</td></tr><tr><td>775.1620</td><td>T(OH）4</td><td>[M+Na]</td><td>775.1912</td><td>-0.004</td></tr><tr><td>789.1774</td><td>T(OH)(OCH)</td><td>[M+Na]</td><td>789.2068</td><td>-0.004</td></tr><tr><td>803.1931</td><td>T（OH）(OCH）</td><td>[M+Na]</td><td>803.2225</td><td>-0.004</td></tr><tr><td>817.1806</td><td>T(OH)(OCH）3</td><td>[M+Na]</td><td>817.2381</td><td>-0.007</td></tr><tr><td>819.1647</td><td>T(OH）(OCH3）</td><td>[M+K]</td><td>819.1964</td><td>-0.004</td></tr><tr><td>831.2231</td><td>T(OCH)4</td><td>[M+Na]</td><td>831.2538</td><td>-0.004</td></tr><tr><td>833.1941</td><td>T（OH）(OCH）</td><td>[M+K]</td><td>833.2121</td><td>-0.002</td></tr><tr><td>847.1983</td><td>T(OCH3）4</td><td>[MIK]</td><td>847.2277</td><td>-0.003</td></tr><tr><td>887.1965</td><td>T（OH）(OCH）4</td><td>[M+Na+K]²</td><td>887.2241</td><td>-0.003</td></tr><tr><td>903.1715</td><td>T(OH）(OCH3）</td><td>[M+Na+K]²</td><td>903.2372</td><td>-0.007</td></tr><tr><td>945.1966</td><td>Ts(OH）</td><td>[M+Na]</td><td>945.2311</td><td>-0.004</td></tr><tr><td>961.1820 959.2113</td><td>T(OH）</td><td>[M+K]</td><td>961.2050</td><td>-0.002</td></tr><tr><td>959.2113</td><td>T（OH）（OCH）</td><td>[M+Na]</td><td>959.2467</td><td>-0.004</td></tr><tr><td>975.2114</td><td>T(OH)(OCH)</td><td>[M+2K]²</td><td>959.2076</td><td>0</td></tr><tr><td></td><td>T(OH）(OCH）</td><td>[MIK]</td><td>975.2207</td><td>-0.001</td></tr><tr><td>973.2275</td><td>T5(OH)(OCH）</td><td>[MINa]*</td><td>973.2624</td><td>-0.004</td></tr><tr><td>989.2056</td><td>T(OH)(OCH）</td><td>[M+K]</td><td>989.2363</td><td>-0.003</td></tr><tr><td>1003.2206</td><td>T(OCH)</td><td>[M+K]</td><td>1003.2520</td><td>-0.003</td></tr><tr><td>1031.1726</td><td>T(OCH）</td><td>[M+H+Na]²</td><td>1031.2783</td><td>-0.010</td></tr><tr><td>1075.2387</td><td>T6</td><td>[M+H]</td><td>1075.2785</td><td>-0.004</td></tr><tr><td>1089.2508</td><td>T(OH)(OCH3）</td><td>[M+Na+K]²+</td><td>1089.2903</td><td>-0.004</td></tr><tr><td>1103.2674</td><td>T1(OH）</td><td>[M+H+K]</td><td>1103.2617</td><td>0.001</td></tr><tr><td>1115.2300</td><td>T(OH）</td><td>[MINa]</td><td>1115.2710</td><td>-0.004</td></tr><tr><td>1129.2444</td><td>T1(OH)(OCH)</td><td>[M+2K]</td><td>1129.2475</td><td>0</td></tr><tr><td>1131.2150</td><td>T(OH)</td><td>[M+K]</td><td>1131.2450</td><td>-0.003</td></tr></table></body></html>  \n\n[0110]   \n\n\n<html><body><table><tr><td>1133.2330</td><td>T1(OH）(OCH）3</td><td>[M+H+K]²</td><td>1133.2905</td><td>-0.005</td></tr><tr><td>1143.2601 1143.2601</td><td>T(OCH32 T(OCH3）</td><td>[M+Na] [M+Na]</td><td>1143.3023 1143.3023</td><td>-0.004 -0.004</td></tr><tr><td>1147.2475</td><td>T(OH)s（OCH3）</td><td>[M12K]²</td><td>1147.2581</td><td>-0.001</td></tr><tr><td>1159.2384</td><td>T(OCH）</td><td>[M+K]</td><td>1159.2763</td><td>-0.003</td></tr><tr><td>1159.2384</td><td>T(OCH3）</td><td>[M+K]</td><td>1159.2763</td><td>-0.003</td></tr><tr><td>1161.2582</td><td>T1(OH）(OCH3）B</td><td>[M+2K]²+</td><td>1161.2737</td><td>-0.001</td></tr><tr><td>1175.2765</td><td>T12(OH)(OCH3）</td><td>[M+2K]²+</td><td>1175.2894</td><td>-0.001</td></tr><tr><td>1177.2532</td><td>T(OH）(OCH）</td><td>[M+K]</td><td>1177.2868</td><td>-0.003</td></tr><tr><td>1177.2532</td><td>T(OH）(OCH3）</td><td>[M+K]</td><td>1177.2868</td><td>-0.003</td></tr><tr><td>1189.2917</td><td>T3(OH）</td><td>[M+H+Na]²</td><td>1189.3000</td><td>-0.001</td></tr><tr><td>1191.2681</td><td>T(OH)</td><td>[M+2Na]²</td><td>1191.2857</td><td>-0.001</td></tr><tr><td>1203.2483</td><td>TB(OH)(OCH）</td><td>[M+H+Na]2</td><td>1203.3157</td><td>-0.006</td></tr><tr><td>1205.2625</td><td>T（OH）（OCH）</td><td>[M+H+Na]²</td><td>1205.3131</td><td>-0.004</td></tr><tr><td>1245.2720</td><td>TB(OH)(OCH3）4</td><td>[M+Na+K]</td><td>1245.3145</td><td>-0.003</td></tr><tr><td>1263.2743</td><td>T(OH)</td><td>[M+H]</td><td>1263.3290</td><td>-0.004</td></tr><tr><td>1285.2630</td><td>T(OH)</td><td>[MINa]</td><td>1285.3109</td><td>-0.004</td></tr><tr><td>1301.2480</td><td>T(OH)</td><td>[M+K]</td><td>1301.2849</td><td>-0.003</td></tr><tr><td>1303.2661</td><td>T(OH)</td><td>[M+Na]</td><td>1303.3215</td><td>-0.004</td></tr><tr><td>1317.2845</td><td>T14(OH)(OCH)</td><td>[M+2K]²</td><td>1317.2980</td><td>-0.001</td></tr><tr><td>1319.2649</td><td>T(OH）</td><td>[M+K]</td><td>1319.2954</td><td>-0.002</td></tr><tr><td>1331.3010</td><td>T14（OH）（OCH3）3</td><td>[M+2K]²+</td><td>1331.3136</td><td>-0.001</td></tr><tr><td>1347.2841</td><td>T(OH）（OCH）</td><td>[M+K]</td><td>1347.3267</td><td>-0.003</td></tr><tr><td>1433.3132</td><td>T8</td><td>[M+H]</td><td>1433.3689</td><td>-0.004</td></tr><tr><td>1473.3034</td><td>T(OH)</td><td>[M+Na]</td><td>1473.3614</td><td>-0.004</td></tr><tr><td>1489.2984</td><td>T(OH）</td><td>[M+K]</td><td>1489.3354</td><td>-0.002</td></tr><tr><td>1491.3048</td><td>T(OH）4</td><td>[M+Na]</td><td>1491.3720</td><td>-0.005</td></tr><tr><td>1507.3133</td><td>T8(OH）4</td><td>[M+K]</td><td>1507.3459</td><td>-0.002</td></tr><tr><td>1519.3359</td><td>T(OH）(OCH）2</td><td>[M+Na]</td><td>1519.4033</td><td>-0.004</td></tr><tr><td>1535.3280</td><td>T(OH）（OCH）</td><td>[MK]</td><td>1535.3772</td><td>-0.003</td></tr><tr><td>1537.3269</td><td>T(OH）（OCH3）</td><td>[M+Na]</td><td>1537.4139</td><td>-0.006</td></tr><tr><td>1603.3479</td><td>T(OH)(OCH）</td><td>[M+K1</td><td>1603.4246</td><td>-0.005</td></tr><tr><td>1621.3525</td><td>T(OH)</td><td>[M+H]</td><td>1621.4194</td><td>-0.004</td></tr><tr><td>1791.3915</td><td>T10</td><td>[M+H]</td><td>1791.4593</td><td>-0.004</td></tr></table></body></html>\n\n[0111]a相对偏差 $\\c=$ [(实测质荷比-理论分子量)/理论分子量]x $100\\%$ o  \n\n[0112］综合MALDI TOF和电喷雾质谱的两种分析结果可知，实施例1的产物MASSQ-1主要由四聚至十三聚的硅倍半氧烷组成，其中有一部分是完全缩合的笼型结构，如T6,T8,T1o，其余，且更多部分则是含有羟基或极少量的甲氧基的不完全反应的产物。  \n\n[0113] 实施例2  \n[0114] 水和3-甲基丙烯酰氧基丙基三甲氧基硅烷(MAPTMS)的化学计量比优选  \n[0115] 表6水和硅烷前体摩尔比  \n\n[0116]   \n\n\n<html><body><table><tr><td>产物编号</td><td>水和MAPTMS的摩尔比</td><td>0.1mol/L稀盐酸的质量（g）</td></tr><tr><td>MASSQ-1</td><td>3</td><td>8.792</td></tr><tr><td>MASSQ-2</td><td>15</td><td>43.97</td></tr><tr><td>MASSQ-3</td><td>30</td><td>87.92</td></tr><tr><td>MASSQ-4</td><td>60</td><td>175.9</td></tr><tr><td>MASSQ-5</td><td>90</td><td>263.8</td></tr></table></body></html>  \n\n[0117］本实施例与实施例1的不同之处在于：改变所加入的0.1mol/L的稀盐酸的量，从而调整水和MAPTMS的摩尔比，进而探讨不同的水和有机硅烷的摩尔比对第一中间体的影响，其他条件均相同。如表6所示，水和有机硅烷的摩尔比分别为3、15、30、60和90，并对产物依  \n\n次编号为MASSQ-1至MASSQ-5。  \n\n[0118]图1是所获产物MASSQ-1至MASSQ-5的样品照片，均为流体。其中，样品MASSQ-1和样品MASSQ-2从肉眼观察均为无色透明的流体，而从样品MASSQ-3开始，已出现轻微的浑浊，样品MASSQ-4和MASSQ-5则呈现出更严重的浑浊。由此可知：水与有机硅烷的摩尔比越大，反应速度过快，产物第一中间体越容易浑浊，从而明显影响溶胶凝胶法制备的硅倍半氧烷产物的光学性能，进而从而影响复合材料的潜在光学应用价值。尤其是，MASSQ-1不仅对可见光高度透明，而且无色，这是均相体系的特征之一。  \n\n[0119] 实施例3-4  \n\n[0120]实施例3-4所用主要试剂及仪器所用的化学试剂如无特别说明均为直接使用，主要试剂列于表7中，主要仪器设备列于表2中，其他未列试剂均为市售分析纯或化学纯的产品。  \n\n[0121] 表7本实验所用的主要化学试剂  \n\n[0122]  \n\n<html><body><table><tr><td>药品名称</td><td>规格</td><td>生产厂家</td></tr><tr><td>异佛尔酮二异氰酸酯（IPDI）</td><td>98%</td><td>Sigma-Aldrich中国</td></tr><tr><td>丙烯酸-2-羟基乙酯（HEA）</td><td>≥98%</td><td>上海笛柏化学品技术有限公司</td></tr><tr><td>二月桂酸二丁基锡（DBTDL）</td><td>95%</td><td>Sigma-Aldrich中国</td></tr><tr><td>4-甲氧基酚（MEHQ）</td><td>化学纯</td><td>Sigma-Aldrich中国</td></tr><tr><td>2.6-二叔」基-4-甲基苯酚（BHT）</td><td>化学纯</td><td>国药集团化学试剂有限公司</td></tr><tr><td>无水碳酸钠</td><td>分析纯</td><td>国药集团化学试剂有限公司</td></tr><tr><td>基橙</td><td>指示剂</td><td>国药集团化学试剂有限公司</td></tr><tr><td>溴酚蓝</td><td>指示剂</td><td>国药集团化学试剂有限公司</td></tr><tr><td>丙酮</td><td>分析纯</td><td>国药集团化学试剂有限公司</td></tr><tr><td>氯仿</td><td>分析纯</td><td>国药集团化学试剂有限公司</td></tr><tr><td>氛代氯仿（含0.03%v/v四甲基硅烷）</td><td>99.8%</td><td>百灵威科技有限公司</td></tr><tr><td>乙腈</td><td>HPLC</td><td>Sigma-Aldrich中国</td></tr><tr><td>甲醇</td><td>HPLC</td><td>Sigma-Aldrich中国</td></tr><tr><td>四氢呋喃</td><td>HPLC</td><td>美国Fishcr</td></tr><tr><td>1.6-已二醇二丙烯酸酯（HDODA）</td><td>工业级</td><td>南京金鹿化工有限公司</td></tr><tr><td>Irgacure184</td><td>光引发剂</td><td>德国巴斯夫BASF</td></tr></table></body></html>  \n\n[0123] 试剂预处理：  \n\n[0124] 1)HEA经过活化的4A分子筛除水；  \n[0125] 2)甲基橙指示液：称取0.1g甲基橙，用 $70\\mathrm{{^\\circC}}$ 的超纯水溶解，冷却后用超纯水稀释至$100\\mathrm{mL}$ ；  \n[0126] 3)溴酚蓝指示液：称取 $0.04\\mathrm{g}$ 溴酚蓝，用乙醇 $(95\\%)$ 溶解并稀释至 $\\boldsymbol{100}\\boldsymbol{\\mathrm{mL}}$ .  \n[0127] 4)无水碳酸钠基准物质：将无水碳酸钠在 $270{\\sim}300^{\\circ}\\mathrm{C}$ 的马弗炉中灼烧至恒重，制成工作基准试剂;  \n\n[0128]5)盐酸标准溶液 $\\left(0.1\\mathrm{mol/L}\\right)$ 的配制：称取 $9.9\\mathrm{g}$ 浓盐酸 $(37\\mathrm{wt}\\%)$ ，用超纯水溶解后移入1L容量瓶中，加超纯水稀释至刻度线，摇匀;以甲基橙指示液作为指示剂，用无水碳酸钠基准物质标定其浓度；  \n\n[0129]6)二正丁胺-丙酮溶液 $\\left(0.1\\mathrm{mol/L}\\right)$ 的配制：称取6.5g二正丁胺，用丙酮溶解后移入500mL的棕色容量瓶，加丙酮稀释至刻度线，摇匀，避光放置；  \n\n[0130] 表8本实验所用的主要仪器设备  \n\n[0131]   \n\n\n<html><body><table><tr><td>仪器名称</td><td>型号</td><td>生产厂家</td></tr><tr><td>艾科浦超纯水机</td><td>AFZ-0501-U</td><td>重庆颐洋企业发展有限公司</td></tr><tr><td>电子天平</td><td>BL-220H</td><td>日本岛津Shimadzu</td></tr><tr><td>傅立叶变换红外光谱仪</td><td>NicoletiS10</td><td>赛默飞世尔ThermoFisher科技公司</td></tr><tr><td>核磁共振波谱仪</td><td>Mercury VX-300</td><td>美国瓦里安Varian公司</td></tr><tr><td>核磁共振波谱仪</td><td>Inova 600</td><td>美国瓦里安Varian公司</td></tr><tr><td>基质辅助激光解吸电离飞行时间 质谱仪</td><td>Voyager-DE STR</td><td>美国应用生物系统AppliedBiosystems公 司</td></tr><tr><td>电喷雾电离飞行时间质谱仪</td><td>Q-TOF</td><td>德国布鲁克Blucker公司</td></tr><tr><td>紫外-可见吸收光谱仪</td><td>TU-1901</td><td>北京普析通用仪器有限责任公司</td></tr><tr><td>旋转粘度计</td><td>LVDV-II+Pro</td><td>美国博勒飞Brookfield工程实验室</td></tr><tr><td>循环恒温水槽</td><td>SYC</td><td>巩义市予华仪器有限责任公司</td></tr><tr><td>凝胶渗透色谱仪</td><td>Waters 2690D</td><td>美国沃特世Waters</td></tr><tr><td>激光光散射检测器</td><td>WyattDAWNEOS</td><td>美国怀雅特Wyall技术公司</td></tr><tr><td>热重分析仪</td><td>Setsys-16</td><td>法国塞塔拉姆Setaram仪器</td></tr></table></body></html>  \n\n[0132] 实施例3  \n\n[0133]异佛尔酮二异氰酸酯与丙烯酸-2-羟基乙酯的单加合物(IPDI-HEA)，即第二中间体，其合成过程如下：  \n\n[0134]1)在一个干净的 $50\\mathrm{mL}$ 的三口烧瓶中，依次称取 $22.23\\mathrm{g}$ (0.1000mol) IPDI和 $0.0342\\mathrm{g}$ $(0.100\\mathrm{wt}\\%)$ DBTDL，然后迅速在烧瓶的三个瓶口上分别安装温度计、机械搅拌器和接有干燥管的 $50\\mathrm{mL}$ 的恒压滴液漏斗;另外，依次称取 $0.0899\\mathrm{g}\\left(0.263\\mathrm{wt}\\%\\right)$ 的MEHQ,0.1798g$(0.526\\mathrm{wt}\\%)$ 的BHT和 $11.66\\mathrm{g}\\left(0.1004\\mathrm{mol}\\right)$ 的HEA，混合于一个烧杯中，用玻璃棒充分搅拌至MEHQ和BHT完全溶解，得无色或淡黄色的反应物溶液，转移至恒压滴液漏斗中；  \n\n[0135]2)在室温及机械搅拌的条件下，打开恒压滴液漏斗，向三口烧瓶中缓慢的滴加反应物(该反应剧烈放热，控制滴加速度以保持反应物的温度始终不超过 $70^{\\circ}\\mathrm{C}\\backslash$ ），滴加完全后继续在室温下搅拌1小时；然后，油浴加热，将所得反应混合物溶液温度升至 $70\\mathrm{{^\\circC}}$ ，并保持在此温度下继续搅拌2小时；  \n\n[0136]此时，通过二正丁胺反滴定法(下述)测定反应混合物的异氰酸酯基(NCO)的含量。通常测定值已达到IPDI和HEA的单加合物的NCO含量理论值 $(12.3\\%)$ ，且延长反应时间也不会再有明显的变化，从而得到无色或淡黄色的透明流体，标记为IPDI-HEA(等摩尔的HEA与IPDI发生加合反应，主要产物为含有一个NCO基团的单异氰酸酯基的化合物,IPDI-HEA)，用干燥的氮气保护，密封保存。  \n\n[0137] 实施例4  \n\n[0138]MASSQ的硅羟基封端反应得到硅倍半氧烷-聚氨酯的衍生物,即MASSQ-UA,其合成过程如下：  \n\n[0139]1)在一个干净的 $250\\mathrm{mL}$ 三口烧瓶中，依次称取 $25.88\\mathrm{g}\\left(19.2\\mathrm{wt}.\\%\\right)$ 的IPDI-HEA(实施例3的产物)与 $0.136\\mathrm{g}\\left(0.10\\mathrm{wt}.\\%\\right)$ 的DBTDL，然后在三个瓶口上分别安装温度计、机械搅拌和恒压滴液漏斗，室温下搅拌 $5\\sim10$ 分钟，使反应物混合均匀;  \n\n[0140]2)称取 $110.0\\mathrm{g}\\left(80.7\\mathrm{wt.}\\%\\right)\\mathrm{MASSQ–1}$ (实施例1的产物)，在室温及机械搅拌的条件下，控制在一定速率下加入IPDI-HEA中，使反应混合物的温度始终不超过 $70\\mathrm{{^\\circC}}$ ；待反应物加入完全后，继续室温搅拌1小时，然后升温至 $60^{\\circ}\\mathrm{C}$ ，恒温搅拌1小时，再升温至 $70^{\\circ}\\mathrm{C}$ ，继续恒温搅拌 $4{\\sim}5$ 小时。在恒温反应的过程中，每隔1小时取少量反应物样品，通过二正丁胺反滴定法测定反应混合物中的 $N C O\\%$ 含量，反应结束的标志为：反应物的 $N C O\\%$ 值处于0至 $0.3\\%$ 之间，且此前1小时 $\\prime0\\%$ 的变化量小于 $0.1\\%$ ，从而得到硅倍半氧烷-聚氨酯的衍生物，标记为MASSQ-UA。  \n\n[0141]对上述IPDI-HEA和MASSQ-1的化学计量的确定遵循如下原则：该反应是IPDI-HEA中的NCO基团与MASSQ-1中的硅羟基之间的反应，因为MASSQ-1中的硅羟基的含量难以定量确定，所以上述投料的比例必须通过预实验来确定。在反应过程中，根据反应混合物的$N C0\\%$ 值的变化来调控反应，若 $N C O\\%$ 值降低至0，则说明MASSQ-1中的硅羟基可能过量，含NCO基团的IPDI-HEA已经化学反应耗尽，此时需要补加一定量的IPDI-HEA，并继续在 $70\\mathrm{{^\\circC}}$ 反应；若 $N C0\\%$ 值大于 $0.3\\%$ ，且此前1小时变 $N C0\\%$ 值降低极慢，甚至无变化，不超过 $0.1\\%$ ，说明IPDI-HEA可能过量，MASSQ-1已反应完全，此时为了封住未反应的NCO基团，则补加一定量的含羟基的HEA，并继续在 $70\\mathrm{{^\\circC}}$ 反应，直至反应结束。  \n\n[0142]］IPDI-HEA中的NCO基团与MASSQ-1中的硅羟基的加合反应，利用二正丁胺反滴定法监测反应过程中NCO基团含量的变化。由于加入了稍过量的IPDI-HEA，当MASSQ-1中的硅羟基充分反应后，还会残余一些未反应的NCO基团，此时NCO值变化的斜率趋近于0。因为这些NCO基团仍有活性，当产物与空气接触时，NCO基团会与水蒸气反应，显著的增大产物的粘度，甚至有可能导致产物结块。此外，为了确保产物对健康和环境的安全性，必须控制最终产物中的NCO值足够低 $(>0.3\\%)$ 。根据NCO值和反应物的质量，可以计算出还需加入的HEA的量，从而刚好将NCO基团反应完全。  \n\n[0143]1、傅立叶变换红外吸收光谱对第二中间体、硅倍半氧烷-聚氨酯的衍生物MASSQ-UA的结构表征  \n\n[0144]实施例3所得第二中间体样品IPDI-HEA和实施例4所得产物MASSQ-UA的红外吸收光谱测试结果如图6所示。IPDI-HEA(图6a)在 $3354\\mathrm{cm}^{-1}$ 附近有一个宽吸收峰，是CO-NH中亚胺基的振动峰，在 $1530\\mathrm{cm}^{-1}$ 处的吸收峰则是CO-NH的特征峰，由这两个峰可以验证IPDI和HEA发生了反应，制得到了IPDI-HEA；而 $2266\\mathrm{cm}^{-1}$ 处的尖峰则是NCO基团的特征吸收峰，这与IPDI-HEA中还含有一个NCO基团的情况相符。  \n\n[0145]与IPDI-HEA对比,MASSQ-UA(图6c)在 $2266\\mathrm{cm}^{-1}$ 处的NCO特征峰几乎没有，或极弱，与实验情况相符，说明IPDI-HEA中的NCO基团已在反应中完全消耗；在 $3360\\mathrm{cm}^{-1}$ 处的胺基吸收峰较强，且在 $1530\\mathrm{cm}^{-1}$ 处出现了CO-NH的吸收峰，而在MASSQ-1(图6b)的谱图中没有出现此峰；同时，MASSQ-1中 $3467\\mathrm{cm}^{-1}$ 处的硅羟基峰较强，而在MASSQ-UA中此处羟基峰则明显减弱，且比 $3360\\mathrm{cm}^{-1}$ 的胺基峰弱，说明MASSQ-1中的大部分硅羟基在反应中已消耗。综上，可验证IPDI-HEA的NCO基团和MASSQ-1的硅羟基发生了反应，生成了CO-NH基团，即得到了加合产物MASSQ-UA。  \n\n[0146]虽然,MASSQ-UA中较弱的羟基峰表明其组分中还残留有未参与反应的硅羟基，但是，加入过量的含有NCO的IPDI-HEA的操作，很难使硅羟基峰继续降低。由此，也说明硅羟基的化学反应性极低，这被认为是原有的甲基丙烯酸酯基以及IPDI-HEA的引入带来的空间位阻效应造成。当然，略过量的NCO可以容易地通过添加含有羟基的HEA而被清除。  \n\n[0147] 2、核磁共振波谱对对第二中间体、硅倍半氧烷-聚氨酯的衍生物MASSQ-UA的结构表征  \n\n[0148] 1)产物IPDI-HEA的'H NMR结果分析  \n\n[0149]图7是实施例3所得第二中间体样品IPDI-HEA的 $^1\\mathrm{H}$ NMR谱图。各质子峰的归属为：6.471-6.413,5.879-5.845 (CH2 $\\circleddash$ ),6.190-6.098 $\\mathop{\\left(-\\mathrm{CH}=\\right)}$ ,4.335-4.304(-C0-CH2-CH2-0-），3.847-3.663(六元环上与N相连的-CH)，3.521-3.030(与一级NC0相连的 $\\mathrm{-CH_{2})}$ ， $1.866-$ 1.505(六元环中的 $\\mathrm{-CH_{2}-)}$ ， $1.251\\mathrm{-}1.030$ (与手性碳原子相连的-CH3)，0.950(与六元环相连的-CH3），7.281(溶剂中的CHCl3)，具体结构已在图中分别进行标注。 $^1\\mathrm{H}$ NMR同样可以验证了，IPDI与HEA已发生反应，并得到了预期的单加合产物IPDI-HEA。  \n\n[0150] 2)产物MASSQ-UA的 $^1\\mathrm{H}$ NMR结果分析  \n\n[0151]图8是实施例4所得产物MASSQ-UA的MASSQ-UA的 $^1\\mathrm{H}$ NMR谱图。其中,5.8-5.9,6.1-6.2,6.4-6.5ppm的质子峰可推导出丙烯酸酯结构，即IPDI-HEA的部分结构。而6.1,5.6，4.1,1.9,1.8和0.7ppm处的质子峰可推导出甲基丙烯酰氧基丙基结构，即MASSQ-1的部分结构。虽然不能直接证明IPDI-HEA与MASSQ-1发生了反应，但通过与IPDI-HEA和MASSQ-1的 $^1\\mathrm{H}$ NMR谱图对比，发现MASSQ-UA中包含了两者的结构。  \n\n[0152] 3)产物MASSQ-UA的 $^{29}\\mathrm{Si}$ NMR谱图分析[0153]图9是实施例4所得产物MASSQ-UA的的 $^{29}\\mathrm{Si}$ NMR谱图。MASSQ-UA的硅谱谱峰主要分布在三个区域内，分别是-45至 $-50\\mathrm{ppm}$ ， $-55$ 至-61ppm，以及-64至 $-70\\mathrm{ppm}$ ,而这三个区域的谱峰可以依次归属为端基硅T，线型硅T和体型硅T三种，在一定程度上表明了MASSQ-UA的硅氧骨架结构。  \n\n[0154]］3、基质辅助激光解吸电离飞行时间质谱对第二中间体、硅倍半氧烷-聚氨酯的衍生物MASSQ-UA的结构表征  \n\n[0155]由于实施例4所得产物MASSQ-UA的分子量较大，因此选择针对大分子的基质辅助激光解吸电离飞行时间(MALDITOF）质谱进行测量。图10是实施例4所得产物MASSQ-UA的MALDI TOF质谱结果。图中信号强度较大的四个峰簇，除m/z1171处的峰以外，其余三个峰簇的间隔为190和200，因为MALDITOF质谱的信号峰基本都是分子离子峰，所以说明这三组峰对应的分子之间分别相差一个T结构单元 $\\mathrm{(T=C_{7}H_{11}O_{2}S i0_{1.5},M_{w}=179.05D a)}$ 。根据质荷比及结构单元进行推导，可以得出各主要谱峰(相对峰强度大于或等于 $10\\%$ 对应的分子离子的化学式和结构简式，分析结果列于表9中。  \n\n[0156]表9产物样品MASSQ-UA的MALDI-TOF质谱测试结果的主要信号峰（相对峰强度大于或等于 $10\\%$ )，对应分子离子的化学式，理论分子量以及可能的分子简式[0157]  \n\n<html><body><table><tr><td>实测质荷比（m/z）</td><td>符合的组成a</td><td>理论质荷比（m/z）</td><td>相对偏差（%）</td></tr><tr><td>1171.1634</td><td>T（OCH）R²K</td><td>1171.3962</td><td>-0.020</td></tr><tr><td>1250.1408</td><td>T(OCH）K</td><td>1251.3600</td><td>-0.098</td></tr><tr><td>1440.2191</td><td>T(OH）（OCH）K</td><td>1439.4105</td><td>0.056</td></tr><tr><td>1640.2346</td><td>T(OH）R²Na</td><td>1639.6100</td><td>0.038</td></tr><tr><td>1641.2311</td><td>T（OI)R²Na</td><td>1641.5057</td><td>-0.017</td></tr></table></body></html>  \n\n[0158] a. $\\mathrm{R}^{2}$ 代表-OH与IPDI-HEA的加合物基团，见图3.1;b.相对偏差 $\\circleddash$ [(实测质荷比-理论分子量)/理论分子量]x $100\\%$ 0  \n\n[0159]由表9的推导结果分析，MASSQ-UA中包含带甲氧基或羟基的不完全水解/缩合的产物，但甲氧基的含量较少，且由于空间位阻效应，不表现化学活性，有部分组分是IPDI-HEA与硅羟基加合的产物。由于硅倍半氧烷的结构可能是笼型、梯型、无规或者半笼型等，为更清晰的表达MASSQ-UA的结构，这里以T7(OH) $\\mathrm{2R^{2}}$ (主产物， $\\mathrm{.m/z=1641.2311}$ ）为例，对MASSQ-UA中组分的结构进行推导，其部分可能的结构式如图11所示。  \n\n[0160］4、电喷雾电离飞行时间质谱对第二中间体、硅倍半氧烷-聚氨酯的衍生物MASSQ-UA的结构表征  \n\n[0161]］与MALDI TOF质谱一样，电喷雾质谱适用于大分子的测量。由于电离原理不同，通常电喷雾质谱的离子化效果更好，测量得到的样品信息更全面，但杂峰也更多，谱图的分析更困难。对于实施例4所得产物MASSQ-UA这样一个成分复杂的杂化材料，通过结合多种表征手段分析验证，以获得更准确的结果。因此，除了MALDITOF质谱，同时也进行了电喷雾质谱测试。另外，对IPDI-HEA也进行了电喷雾质谱测试，以验证其结构。  \n\n[0162] 1)样品IPDI-HEA的电喷雾质谱结果分析[0163]实施例3所得第二中间体样品IPDI-HEA的电喷雾质谱结果如图12所示。由于IPDI-HEA是单异氰酸酯化合物，其NCO基团在室温即可与羟基,氨基化合物发生反应。因此，空气中的水蒸气，测试用的溶剂均有可能与之反应生成副产物，而对质谱的结果产生影响。在我们所知的范围内，以往没有对IPDI-HEA进行质谱分析的研究。在本发明中，对新鲜的IPDI-HEA样品进行了快速的制样，并立即测试。仅选取质谱结果中，相对峰强度大于或等于 $20\\%$ 的信号峰进行结构分析，所得结果列于表10中。  \n\n[0164]表10样品IPDI-HEA的电喷雾质谱测试结果的主要信号峰(相对峰强度大于或等于$20\\%$ ，以及对应的离子，推导的分子结构。  \n\n[0165]   \n\n\n<html><body><table><tr><td>信号峰 (m/z)</td><td>推导的分子结构</td><td>离子类型</td><td>理论质荷比 (m/z)</td><td>相对偏差 (%)</td></tr><tr><td>313.1843</td><td></td><td>[M+H]</td><td>313.2122</td><td>-0.009</td></tr><tr><td>339.3028</td><td></td><td>[M+H]</td><td>339.1915</td><td>0.033</td></tr><tr><td>419.3319</td><td></td><td>[M+II]</td><td>419.3017</td><td>0.007</td></tr><tr><td>455.3152</td><td></td><td>[M+II]</td><td>455.2388</td><td>0.017</td></tr></table></body></html>  \n\n[0166]   \n\n\n<html><body><table><tr><td>477.2384</td><td></td><td>[M+Na]</td><td>477.2207</td><td>0.004</td></tr><tr><td>535.4782</td><td></td><td>[M+H]</td><td>535.3490</td><td>0.024</td></tr><tr><td>651.5578</td><td></td><td>M+HJ</td><td>651.3964</td><td>0.025</td></tr></table></body></html>  \n\n[0167]由以上质谱分析的结果表明，实施例3的目标化合物IPDI-HEA单加合物分子(313Da)已成功制得。在副产物当中，也有双加合物HEA-IPDI-HEA出现，说明反应里有该副产物生成;其余副产物则可能与测试中与水接触有关;再结合滴定结果-产物中NCO的实际含量为 $12.1\\%$ (接近理论值 $12.3\\%$ ），可证明产物的主要成分是IPDI-HEA单加合物。  \n\n[0168] 2)样品MASSQ-UA的电喷雾质谱结果分析[0169]图13是实施例4的产物MASSQ-UA的电喷雾质谱，其信号峰主要集中在 $750{\\sim}2000\\mathrm{{Da}}$ 的范围内。比MALDI TOF质谱相比，电喷雾质谱中的信号峰更多，为了获得有效的数据信息，仅收集所有相对峰强度大于或等于 $20\\%$ 的谱峰对应的质荷比数据。同样，按照MALDITOF质谱采用的方法进行分析，得到各谱峰对应的阳离子，及其相符合的分子简式，分析结果列于表11中。  \n\n[0170］表11产物样品MASSQ-UA的电喷雾质谱测试结果的主要信号峰(相对峰强度大于或等于 $20\\%$ )，对应阳离子及其相符合的分子简式  \n\n[0171]   \n\n\n<html><body><table><tr><td>信号峰 (m/z)</td><td>符合的分子简式a</td><td>离子类型</td><td>理论质荷比 (m/z)</td><td>相对偏差 (%)</td></tr><tr><td>717.3928</td><td>TR²2</td><td>[M+H+Na]²</td><td>717.2781</td><td>0.016</td></tr><tr><td>731.4901 752.5328</td><td>T(OH）（OCH）R²</td><td>[M+2H]²</td><td>731.3055</td><td>0.025</td></tr><tr><td></td><td>T（OCH）R²</td><td>[M+2H]²</td><td>752.3290</td><td>0.027</td></tr><tr><td>803.2037</td><td>T(OH）（OCH）</td><td>[M+Na]</td><td>803.2225</td><td>-0.002</td></tr><tr><td>817.2008</td><td>T(OH)(OCH）R²</td><td>[M+2H]²+</td><td>817.2733</td><td>-0.009</td></tr><tr><td>831.2366</td><td>TR²</td><td>[M+Na+K]2+</td><td>831.2291</td><td>0.001</td></tr><tr><td>847.5381</td><td>T(OHOCH）R²</td><td>[M+Na+K]²</td><td>847.2422</td><td>0.035</td></tr><tr><td>869.5190</td><td>T(OCH）R²</td><td>[M+2Na]²</td><td>869.2840</td><td>0.027</td></tr><tr><td>887.2107</td><td>T(OH)(OCH3）4</td><td>[M+Na+K]²+</td><td>887.2241</td><td>-0.002</td></tr><tr><td>903.1864</td><td>T(OH)(OCH3）s</td><td>[M+Na+K]²</td><td>903.2372</td><td>-0.006</td></tr><tr><td>973.2444</td><td>T10（OH）（OCH）4</td><td>[M+2Na]²</td><td>973.2624</td><td>-0.002</td></tr><tr><td>989.2220</td><td>T10(OH）（OCH）4</td><td>[M+2K]²+</td><td>989.2363</td><td>-0.001</td></tr><tr><td>1043.6937</td><td>T(OH)（OCH）R²</td><td>[M+2K]²</td><td>1043.2797</td><td>0.040</td></tr><tr><td>1075.2567</td><td>T</td><td>[M+2H]²</td><td>1075.2785</td><td>-0.002</td></tr><tr><td>1115.2483</td><td>T2(OH)4</td><td>[M+2Na]²</td><td>1115.2710</td><td>-0.002</td></tr><tr><td>1131.2372</td><td>T1(OH）4</td><td>[M+2K]²</td><td>1131.2450</td><td>-0.001</td></tr><tr><td>1143.2784</td><td>T1（OCH）4</td><td>[M+2Na]2</td><td>1143.3023</td><td>-0.002</td></tr><tr><td>1161.2740</td><td>T（OH）（OCH）</td><td>[M+2K]²</td><td>1161.2737</td><td>0</td></tr></table></body></html>  \n\n[0172]   \n\n\n<html><body><table><tr><td>1245.2929</td><td>T3(OH)(OCH3）4</td><td>[M+Na+K]²</td><td>1245.3145</td><td>-0.002</td></tr><tr><td>1285.2852</td><td>T(OH)</td><td>[M+Na]</td><td>1285.3109</td><td>-0.002</td></tr><tr><td>1303.2807</td><td>T(OH)</td><td>[M+Na]</td><td>1303.3215</td><td>-0.003</td></tr><tr><td>1347.3090</td><td>T(OH）(OCH）</td><td>[M+K]</td><td>1347.3267</td><td>-0.001</td></tr><tr><td>1433.3358</td><td>T8</td><td>[M+H]</td><td>1433.3689</td><td>-0.002</td></tr><tr><td>1519.3615</td><td>T8(OH）(OCH3）2</td><td>[M+Na]</td><td>1519.4033</td><td>-0.003%</td></tr><tr><td>1604.3786</td><td>T（OH）（OCH）R²</td><td>[M+2K]²+</td><td>1604.4859</td><td>-0.007%</td></tr></table></body></html>  \n\n[0173]a. $\\mathrm{R}^{2}$ 代表-OH与IPDI-HEA的加合物基团，见图3.1;b.相对偏差 $\\c=$ [(实测质荷比-理论分子量)/理论分子量]x $100\\%$ 0  \n\n[0174]综合MALDI TOF和电喷雾质谱的分析结果可知，实施例4所得产物MASSQ-UA主要由四聚至十三聚的硅倍半氧烷组成。其中，部分组分含有硅羟基与IPDI-HEA反应所得的加合结构，而其余则没有与IPDI-HEA发生反应;同时，在发生反应的组分中，也含有部分未反应的硅羟基。这些说明MASSQ-1中的硅羟基并不能完全与IPDI-HEA反应，这是由于硅原子上的甲基丙烯酰氧基丙基基团以及IPDI-HEA的体积均较大，因此存在空间位阻效应，导致即使在过量的IPDI-HEA中，部分硅羟基仍难以与其发生反应。由此可知：MASSQ-UA中剩余的硅羟基受到空间位阻的影响，不会发生缩合反应，因此不会对产物MASSQ-UA的稳定性造成影响。  \n\n.0175] 5、硅倍半氧烷-聚氨酯的衍生物MASSQ-UA的光学透明度-材料的性能分析[0176]将实施例4的产物MASSQ-UA与其原料MASSQ-1(即实施例1产物)作对比，分别观察其实物的表观透明度以及测试其紫外可见吸收光谱，如图14所示，可知：MASSQ-UA和MASSQ-1均为无色透明的流体，两者没有肉眼可辨的差异;紫外-可见吸收光谱显示：在可见光区即$400{-}800{\\mathrm{nm}}$ 的波长范围内，MASSQ-UA与MASSQ-1均没有吸收峰，且基线吸收均为0，说明两者对可见光都有很高的透明度，进一步表明，MASSQ-UA是一个均相体系。另外，在紫外光谱中，MASSQ-UA在314nm处，MASSQ-1在307nm处，各自有一个吸收峰，这是已知的丙烯酸酯或甲基丙烯酸酯中双键的吸收峰。  \n\n[0177] 6、硅倍半氧烷-聚氨酯的衍生物MASSQ-UA的热稳定性测试-材料的性能分析[0178]众所周知，硅倍半氧烷化合物有较高的耐高温性质，如图 $15,\\mathrm{MASSQ{-}1}$ (即实施例1产物)即硅倍半氧烷化合物的最大热分解温度为约 $415\\mathrm{^\\circC}$ 。图15中， $\\mathrm{MASSQ^{-1}}$ 和实施例4的产物MASSQ-UA的TGA测试结果清楚表明：在IPDI-HEA被键合在MASSQ-1后，不但没有降低材料的耐高温性能，反而将MASSQ-UA的最大热分解温度提高到了 $435\\mathrm{{^\\circC}}$ ，比MASSQ-1高了 $20^{\\circ}\\mathrm{C}$ 0  \n\n[0179] 实施例5  \n\n[0180]一种有机-无机杂化高分子复合材料，其主要组成成分包括： $15.0\\%$ 的MASSQ-UA(实施例4制备的可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物，官能度4-13)， $16.0\\%$ 的双季戊四醇六丙烯酸酯(DPHA，可聚合的单体)， $10\\%$ 的EA-80(江苏三木公司的6105-80，一种环氧改性丙烯酸型UV树脂，可聚合的齐聚体）， $16\\%$ 的Eb230（美国Cytec公司的EBECRYL230，一种聚氨酯丙烯酸酯，可聚合的齐聚体）， $15\\%$ 的1，6-己二醇二丙烯酸酯(HDDA，可聚合的单体）， $12\\%$ 的二缩三丙二醇二丙烯酸酯(TPGDA，可聚合的单体)， $5\\%$ 的三羟甲基丙烷三丙烯酸酯(TMPTA，可聚合的单体)， $2\\%$ 的甲基丙烯酰氧基丙基三甲氧基硅烷(Z6030，附着力促进剂）， $2\\%$ 的磷酸氢二(甲基丙烯酰氧乙基)酯(PM-2,附着力促进剂)， $2\\%$ 的1-羟基环己基苯基甲酮(Irgacurel84,光引发剂)， $4\\%$ 的 $2^{-}$ 羟基 $-2-$ 甲基 $^{-1-}$ 苯基 $-1-$ 丙酮(1173，光引发剂)， $1\\%$ 的三苯基氧化麟(TP0，光引发剂)。  \n\n[0181] 本实施例所述有机-无机杂化高分子复合材料的制备方法，具体步骤如下：  \n\n[0182]1)依次称取1g $\\mathrm{;\\TP0,2g}$ Irgacure 184,4g 1173,15g HDDA, $12\\mathrm{g}$ TPGDA,5g TMPTA,16gDPHA，室温高速搅拌10分钟，形成混合物A;  \n\n[0183] 2)将 $\\mathrm{2g}$ Z6030，2gPM-2加入混合物A中，室温高速搅拌2分钟，形成混合物B;[0184] 3)将 $10\\mathrm{g}$ EA-80，16gEb 230依次加入混合物B中，且每加入一个组分，都高速搅拌5分钟，得到混合物C。  \n\n[0185]4)将15g MASSQ-UA加入混合物D,高速搅拌分散10分钟,得到混合物D,静置8小时除去气泡(或60度加热30分钟)，得到有机-无机杂化高分子复合材料。  \n\n[0186]将本实施例制备的有机-无机杂化高分子复合材料用胶辊涂在经砂纸打磨的木板上，UV照射至完全固化，得到有机-无机杂化高分子复合材料涂层。  \n\n[0187] 对比例1  \n\n[0188]本对比例与实施例5的不同之处在于：将MASSQ-UA替换为Eb 1290（一种脂肪族聚氨酯丙烯酸酯)，其他条件不变。由实施例4可知:MASSQ-UA主要由四聚至十三聚的硅倍半氧烷组成，因此MASSQ-UA中含有4至13个可聚合的甲基丙烯酸酯基团。Eb1290是现有涂料产品常用的组分中官能度(官能度为6)最高的一种产品。通过对比实施例5和对比例1，可知：使用本发明中合成的有机-无机杂化的可聚合或可交联的硅倍半氧烷-聚氨酯MASSQ-UA制备的涂层比使用Eb1290制备的涂层，在性能上有所提高，具体体现在涂层的硬度、耐磨度、附着力、耐冲击性、耐擦伤能力、耐灼烧能力都有提高，且其他性能持平，详见表13。  \n\n[0189] 对比例2  \n\n[0190]本对比例与实施例5的不同之处在于：将MASSQ-UA替换为Eb 264（一种脂肪族聚氨酯丙烯酸酯，官能度2)，其他条件不变。Eb264是现有涂料产品中常用的一种增加涂料韧性、耐磨损性等性能的优良树脂产品。对比实施例5和对比例2可知：使用本发明中合成的有机-无机杂化的可聚合或可交联的硅倍半氧烷-聚氨酯MASSQ-UA制备的涂层比使用Eb264制备的涂层，在部分性能上有所提高，具体体现在涂层的耐污性、硬度、耐磨度、耐擦伤能力、耐灼烧能力都有提高，详见表13。  \n\n[0191] 对比例3  \n\n[0192]本对比例与实施例5的不同之处在于：将MASSQ-UA替换为纳米二氧化硅，其他条件不变。但发现所得涂料的粘度达到 $1.37\\mathrm{x10^{4}m P a\\ ^{\\bullet}\\ s}$ ，粘度太高，无法进行测试或涂膜工艺，且该涂料浑浊半透明，不能用于光学应用。由此可见，在涂料配制及使用过程中，本发明中合成的有机-无机杂化的可聚合或可交联的硅倍半氧烷-聚氨酯MASSQ-UA比纳米二氧化硅，在可加工性能以及透光性上更优。  \n\n[0193] 实施例6  \n\n[0194]为了比较MASSQ-UA与纳米二氧化硅的区别，重新配制一种有机-无机杂化高分子复合材料，其主要组成成分包括： $5.0\\%$ 的MASSQ-UA, $16.0\\%$ 的双DPHA， $20\\%$ 的 $6A-80,16\\%$ 的Eb $230,15\\%$ 的HDDA， $12\\%$ 的TPGDA， $5\\%$ 的TMPTA， $2\\%$ 的 $26030,2\\%$ 的PM-2, $2\\%$ 的Irgacure$184,4\\%$ 的 $1173,1\\%$ 的TPO。  \n\n[0195] 本实施例所述有机-无机杂化高分子复合材料的制备方法，具体步骤如下：[0196]1)依次称取 $\\mathrm{1g}$ $\\textsl{g}\\ \\mathrm{TP0,2g}$ Irgacure $^{184,4g}\\ 1173,15\\mathrm{g}$ HDDA， $12\\mathrm{g}$ TPGDA,5g TMPTA,$16\\mathrm{g}$ DPHA,室温高速搅拌10分钟，形成混合物A;  \n\n[0197] 2)将 $\\mathrm{2g}$ $\\mathrm{26030,2g}$ PM-2加入混合物A中，室温高速搅拌2分钟，形成混合物B;[0198]3)将 $20\\mathrm{g}$ EA-80，16g Eb 230依次加入混合物B中，且每加入一个组分，都高速搅拌5分钟，得到混合物C。  \n\n[0199]4)将5g MASSQ-UA加入混合物D,高速搅拌分散10分钟,得到混合物D,静置8小时除去气泡(或60度加热30分钟)，得到有机-无机杂化高分子复合材料。  \n\n[0200]将本实施例制备的有机-无机杂化高分子复合材料用胶辊涂在经砂纸打磨的木板上，UV照射至完全固化，得到有机-无机杂化高分子复合材料涂层。  \n\n[0201] 对比例4  \n\n[0202]本对比例与实施例5的不同之处在于：将MASSQ-UA替换为纳米二氧化硅，其他条件不变。纳米二氧化硅常被用来提高涂料的硬度耐擦伤能力等性能。对比实施例6和对比例4可知：使用本发明中合成的有机-无机杂化的可聚合或可交联的硅倍半氧烷-聚氨酯MASSQ-UA制备的涂料及涂层比使用纳米二氧化硅制备的涂料及涂层，在硬度上有所提高，耐擦伤能力持平，此外，涂料的粘度更低，涂层的表面光泽度、耐污性、附着力、耐碱性都有提高，详见表13。  \n\n[0203] 实施例5、6，对比例1、2、4所用的测试和评价方法见表12  \n\n[0204] 表12 [0205]  \n\n<html><body><table><tr><td>测试项目</td><td>测试及评价方法</td></tr><tr><td>光泽度</td><td>GB/T9754-2007</td></tr><tr><td>粘度</td><td>GB/T5561-94</td></tr><tr><td>固化能量</td><td>用能量计（UVPowerPuck）测试。</td></tr><tr><td>耐污性</td><td>用油性笔在表面画圈，然后滴5滴酒精在上面，等酒精自然挥发后用酒精棉球擦拭十净， 看是否有留下痕迹。评价方法按照GB/T1766-2008执行。</td></tr><tr><td>硬度</td><td>GB/T 6739-2006</td></tr><tr><td>耐磨度</td><td>GB/T1768-2006，使用砂纸为P180号。</td></tr><tr><td>附着力</td><td>GB/T 9286-1998</td></tr><tr><td>耐水性</td><td>GB/T4893.1-2005</td></tr><tr><td>耐酸性</td><td>同耐水性测试，试液为50g/L的CHCOOH，试验时间为2h，试验后放置1h后观察。评 价方法按照GB/T1766-2008执行。</td></tr><tr><td>耐碱性</td><td>同耐酸性测试，试液为50g/L的Na2CO3。评价方法按照GB/T1766-2008执行。</td></tr><tr><td>耐油性</td><td>同耐水性，试液为甲基硅油。评价方法按照GB/T1766-2008执行。</td></tr><tr><td>耐冲击性</td><td>用漆膜冲击器从一定高度冲击涂有漆膜的马口铁板，冲击部位形成一个凹洞，凹洞和未冲 击到的部位有一条界线，比较相同情况卜两种膜界线处的断裂情况。优：基本没有断裂； 良：有较少部分断裂；中：有一半左右断裂；差：大部分断裂。</td></tr><tr><td>耐擦伤能力</td><td>用1kg缺码压在钢丝球上擦拭200次（来回算1次），测量擦伤测试前后涂层的光泽度， 比较光泽度的保有率（保有率=测试后光泽度/测试前光泽度），优：保有率人于90%； 良：保有率在70-90%之间；中：保有率在50-70%之间；差：保有率小于50%。</td></tr><tr><td>耐灼烧能力</td><td>先把烟点燃后放在马口铁漆膜上，等它烧完后用酒精棉球擦净，观察留下的痕迹的色泽深 浅。优：完全没有痕迹；良：涂层完好，但有轻微黄褐色灼痕：中：涂层完好，但黄褐色 灼痕较深；差：涂层破损，发黑。</td></tr></table></body></html>  \n\n[0206] 实施例5、6，对比例1、2、4的有机-无机杂化高分子复合材料及相应的涂层性能列  \n\n于表13中。 [0207] 表13 [0208]  \n\n[0209]   \n\n\n<html><body><table><tr><td></td><td>实施例5</td><td>对比例1</td><td>对比例2</td><td>实施例6</td><td>对比例4</td></tr><tr><td>外观</td><td>无色透明液 体</td><td>无色透明液 体</td><td>无色透明液 体</td><td>无色透明液 体</td><td>灰色半透明 液体</td></tr><tr><td>粘度（25℃，mPa·s）</td><td>734</td><td>716</td><td>728</td><td>645</td><td>1198</td></tr><tr><td>固化能量（mJ/cm²）</td><td>528</td><td>496</td><td>653</td><td>498</td><td>569</td></tr><tr><td>表面光泽度</td><td>88</td><td>85</td><td>67</td><td>86</td><td>59</td></tr><tr><td>耐污性</td><td>0级（无变</td><td>0级</td><td>1-2级（残留</td><td>1-2级</td><td>3级（留下部</td></tr></table></body></html>  \n\n<html><body><table><tr><td></td><td>化）</td><td></td><td>轻微痕迹）</td><td></td><td>分痕迹）</td></tr><tr><td>硬度/</td><td>7-8</td><td>6-7</td><td>3-4</td><td>5-6</td><td>4-5</td></tr><tr><td>耐磨度/g</td><td>0.1046</td><td>0.1184</td><td>0.1359</td><td>0.1226</td><td>0.1257</td></tr><tr><td>附着力</td><td>1级</td><td>3级</td><td>0级</td><td>1级</td><td>2级</td></tr><tr><td>耐水性</td><td>0级（无变 化）</td><td>0级</td><td>0级</td><td>0级</td><td>0级</td></tr><tr><td>耐酸性</td><td>0级</td><td>0级</td><td>0级</td><td>0级</td><td>0级</td></tr><tr><td>耐碱性</td><td>0级</td><td>0级</td><td>0级</td><td>0级</td><td>2级（发白）</td></tr><tr><td>耐油性</td><td>0级</td><td>0级</td><td>0级</td><td>0级</td><td>0级</td></tr><tr><td>耐冲击性</td><td>良</td><td>中等</td><td>优</td><td>良</td><td>中等</td></tr><tr><td>耐擦伤能力 耐灼烧能力</td><td>优 优</td><td>良 良</td><td>中 中</td><td>良 良</td><td>良 良</td></tr></table></body></html>  \n\n[0210]以上所述仅是本发明的优选实施方式，应当指出，对于本领域的普通技术人员来说，在不脱离本发明创造构思的前提下，还可以做出若干改进和变换，这些都属于本发明的保护范围。  \n\n![](images/cd5716dc250571de286fa77040a14f155973813dedeab7b5c5b9ff50fe79ea3e.jpg)  \n图1  \n\n![](images/9b8e3e59c2ae76f45c1dc64c698d04797c44ee236bb18cc2c4782016bcc1d1f2.jpg)  \n图2  \n\n![](images/d5ce978088d127ffa28fca30a8539fecb1b6a2fe7106a9a78a624f0472ff17f7.jpg)  \n图3  \n\n![](images/113add2c602001cb545bcd36bd03c77df4ffd2c4b00dfa3ee3c2b292dfb368ce.jpg)  \n图4  \n\n![](images/afc54f837a1eb4f17d61fb477ec3784413bc054392f4a6f647c449c3987ba1b7.jpg)  \n图5  \n\n![](images/625e7e793d179d004b93d3640f40443d5af6bfa18c169aea7a4cf89e06df89a2.jpg)  \n图6  \n\n![](images/6db77c9ba4d87a177535f989180529201decbd3cbae986bc63b77ecc857ce28b.jpg)  \n图7  \n\n![](images/9545bd87ac432e72b1f2d35a27d32a90a029701fecb5b3ccd521316b24e34f1f.jpg)  \n图8  \n\n![](images/dd03464c60a28b0ff42df84f7df5626dd7e87c287ceb7226c930b2d00bf33251.jpg)  \n图9  \n\n![](images/4af1bd2550ad9d62f16ebb7fd487b4bd4408469e137cc0804dccbbcc48ec7e78.jpg)  \n图10  \n\n![](images/b529465e89e9b384085aeb35e61c35b96d31e84540e4600535c2275a23739153.jpg)  \n图11  \n\n![](images/2ef359e71139552caf1e4ab46633faf396cb3bb1515c40fe261f2f3817d410c0.jpg)  \n图12  \n\n![](images/a2d90875cf292868cda3aa5a289e3662a40de0eac24dc119b4c42a2d794874a1.jpg)  \n图13  \n\n![](images/b773cd6339676d204c5b965c7a5c0d62132020412e46c0d2ddfd7f367c32fd87.jpg)  \n图14  \n\n![](images/a545ce1847bd9f40d9790ed90ba040378a8e5cf37cf7f20a8c1f65c684591990.jpg)  \n图15",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,47 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n<html><body><table><tr><td>(21)申请号 202010239152.2</td><td>(51)Int.CI.</td></tr><tr><td>(22)申请日2020.03.31</td><td>C09D 175/04 (2006.01)</td></tr><tr><td>(65)同一申请的已公布的文献号</td><td>C09D 163/00 (2006.01)</td></tr><tr><td>申请公布号CN 111303746 A</td><td>C09D 7/62 (2018.01)</td></tr><tr><td></td><td>C09D 7/61 (2018.01)</td></tr><tr><td>(43)申请公布日 2020.06.19</td><td>C09D 7/63 (2018.01)</td></tr><tr><td>(73)专利权人武汉中科先进技术研究院有限公</td><td>C08J 7/054 (2020.01)</td></tr><tr><td>司</td><td>C03C 17/00 (2006.01)</td></tr><tr><td>地址430050湖北省武汉市武汉经济技术</td><td>C08L 67/02 (2006.01)</td></tr><tr><td>开发区206M地块华中电子商务产业园</td><td>审查员孔菲</td></tr><tr><td>A6栋1-6层</td><td></td></tr><tr><td>(72)发明人康翼鸿喻学锋程文杰杨新耕</td><td></td></tr><tr><td>(74)专利代理机构武汉知产时代知识产权代理</td><td></td></tr><tr><td>有限公司42238</td><td></td></tr><tr><td>代理人 郝明琴</td><td></td></tr></table></body></html>",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n一种防雾涂料及其制备方法和应用",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明公开了一种防雾涂料及其制备方法和应用。包括防雾涂料如下质量份数的原料： $1\\sim$ 20份金纳米粒子、 $1{\\sim}40$ 份亲水纳米颗粒、 $.10{\\sim}30$ 份有机粘合剂和 $40{\\sim}90$ 份溶剂；金纳米粒子是以聚甲基丙烯酸或聚甲基丙烯酸/聚苯乙烯共聚物为囊壁，将纳米金包裹起来形成的微胶囊；亲水纳米颗粒包括纳米二氧化钛和亲水型的纳米二氧化硅中的一种或两种；有机粘合剂中包含环氧基、氨基和羟基中的一种或多种。本发明制备的防雾涂料，在室温条件下，防雾涂料中的各组分不会发生化学反应，能够长时间储存，该防雾涂料形成的涂层，具备防雾效果好、耐水性好、表面硬度高、附着力强、透明度高和使用寿命长的优点。  \n\n1.一种防雾涂料，其特征在于，包括如下质量份数的原料： $1{\\sim}20$ 份金纳米粒子、 $.1\\sim40$ 份亲水纳米颗粒、 $.10{\\sim}30$ 份有机粘合剂和 $40{\\sim}90$ 份溶剂；所述金纳米粒子是以聚甲基丙烯酸或聚甲基丙烯酸/聚苯乙烯共聚物为囊壁，将纳米金包裹起来形成的微胶囊。  \n\n2.如权利要求1所述的一种防雾涂料，其特征在于，所述有机粘合剂包含环氧基、氨基和羟基中的基团中的一种或多种。  \n\n3.如权利要求1所述的一种防雾涂料，其特征在于，所述金纳米粒子的制备方法如下：  \n\nS1：甲基丙烯酸叔丁酯单体或甲基丙烯酸叔丁酯单体/苯乙烯与逆加成‑断裂链转移剂 在催化剂的作用下发生反应，生成末端含二硫酯键的聚甲基丙烯酸叔丁酯或末端含二硫酯 键的聚基丙烯酸叔丁酯/聚苯乙烯共聚物；  \n\nS2：将步骤S1制备得到的产物通过还原反应，制备为末端含硫醇基团的聚甲基丙烯酸或末端含硫醇基团的聚甲基丙烯酸/聚苯乙烯共聚物；  \n\nS3：再将HAuC1 和NaBH 放入将步骤S1制备得到的产物的水溶液中，HAuC1 被NaBH 聚还原为Au粒子，末端含硫醇基团的聚甲基丙烯酸或末端含硫醇基团的聚甲基丙烯酸/聚苯乙烯共聚物将Au粒子包裹，形成金纳米粒子。  \n\n4.如权利要求3所述的一种防雾涂料，其特征在于，所述步骤S1中的可逆加成‑断裂链转移剂包括2‑(甲氧基碳酰基)‑乙基双硫苯酯和\\或二硫代苯甲酸酯。  \n\n5.如权利要求1‑4任一项所述的一种防雾涂料，其特征在于，所述有机粘合剂包括聚氨酯、环氧树脂、丙烯酸酯、醇酸树脂、聚酯和聚酰胺中的一种或多种。  \n\n6.如权利要求5所述的一种防雾涂料，其特征在于，所述环氧树脂包括非离子型环氧树脂，所述非离子型环氧树脂为在双酚A型环氧树脂或双酚F型环氧树脂的侧链接枝上亲水的非离子型链段得到的聚合物，所述非离子型链段为 $\\mathrm{-NHCOOCH_{2}[C H_{2}^{-}O^{-}C H_{2}]n C H_{2}O O C N H^{-}},$ 。  \n\n7.如权利要求1所述的一种防雾涂料，其特征在于，所述溶剂包括水、乙醇和异丙醇中的一种或多种。  \n\n8.一种如权利要求1‑7任一项所述的防雾涂料的制备方法，其特征在于，将上述质量份数的所述亲水纳米颗粒、有机粘合剂和金纳米粒子依次加入上述质量份数的溶剂中，混合搅拌均匀后，即可得到所述防雾涂料。  \n\n9.一种如权利要求8所述的防雾涂料的应用，其特征在于，将所述防雾涂料涂覆在玻璃或塑料基材固化形成防雾涂层。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 一种防雾涂料及其制备方法和应用",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明涉及防雾涂料技术领域，尤其涉及一种防雾涂料及其制备方法和应用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 生活中存在大量与光学相关的物件或材料，例如：汽车玻璃、建筑物玻璃、广告牌、浴室镜、仪表仪盘、护目镜等。然而，在高湿度或者存在较大温差的地方，这些或透光或反光的光学表面上就会容易形成影响视线的雾。雾遮挡了人们的视线，不仅给工作生活带来不便，同时还存在极大的安全隐患。例如在雨季或者低温的冬季，当驾驶汽车时，车窗或后视镜表面容易形成雾。若不及时消除，会对驾驶员的视线受到影响，大大增加大车祸发生概率。因此，防雾技术的研究及应用逐步受到人们的重视。  \n\n[0003] 目前防雾的方法主要分为电热法和防雾功能涂层法，电热法是利用空调吹风或自带的加热功能加热光学材料表面，从而使光学材料表面处于干燥的状态，以此来防止结雾，确保能见度；电热法效果良好，但是实施成本较高，且需要额外的热源，不节能、不环保。  \n\n[0004] 防雾功能涂层法是通过涂覆具有防雾功能的涂料，于光学材料表面形成一层薄的涂层来进行防雾。目前按照防雾功能的不同，涂层可分为疏水型和亲水型两种；疏水型的防雾涂层还处在研究阶段，还没有大规模的产品问世，存在成本太高，防雾效果不好，工艺太复杂等难以解决的问题；现有技术中的亲水型的防雾涂料，是将亲水的表面活性剂直接涂覆或者将这类表面活性剂与其它的成膜基质混合后涂覆；其防雾原理是通过“溶出”作用，当光学材料表面存在水分子时，表面活性剂分子迁移到涂层表面，降低水的表面张力，水分子在光学材料表面迅速铺展形成透明水膜，避免以水珠的形式聚集在表面成雾；但是这种方法需要不断地“消耗”表面活性剂分子，因此这种防雾涂层存在使用寿命短的缺陷，使用寿命一般不超过3个月。  \n\n[0005] 通过提高涂层自身的表面能来实现水在表面的铺展，可以实现了水珠向水膜的转变。现有技术中使用亲水的无机纳米二氧化硅或二氧化钛作为防雾涂料，其中二氧化硅的表面羟基数量少，亲水性较差，单独使用不足以提供防雾性，需要搭配使用表面活性剂使用才能达到较好的防雾效果，存在使用寿命短、防雾效果不理想的缺点。二氧化钛表面在紫外光照射下可以产生非常活泼的自由基，引起表面由疏水向亲水的转变从而提高表面能，最终实现防雾功能；该表面能的转变过程是可逆的，一旦离开了紫外光，又会恢复低表面能的状态，防雾效果难以持续；现有技术中的防雾涂层中使用的亲水的有机聚合物存在表面硬度低、耐磨性不好的问题，涂层容易被刮伤从而影响防雾性能以及使用寿命；通过提高涂层的表面硬度及耐磨性，会牺牲自身的亲水性，从而造成涂层的防雾能力下降。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0006] 本发明的目的在于，针对现有技术的上述不足，提出一种防雾效果好、耐水性好、表面硬度高、透明度高以及使用寿命长的的防雾涂料及其制备方法。  \n\n[0007] 本发明的目的可以通过以下技术方案来实现：  \n\n[0008] 一种防雾涂料，包括如下质量份数的原料： $1{\\sim}20$ 份金纳米粒子、 $.1{\\sim}40$ 份亲水纳米颗粒、 $.10{\\sim}30$ 份有机粘合剂和 $40{\\sim}90$ 份溶剂。  \n\n[0009] 优选的，所述金纳米粒子是以聚甲基丙烯酸或聚甲基丙烯酸/聚苯乙烯共聚物为囊壁，将纳米金包裹起来形成的微胶囊。  \n\n[0010] 优选的，所述有机粘合剂包含环氧基、氨基和羟基中的基团中的一种或多种。  \n\n[0011] 优选的，所述金纳米粒子的制备方法如下：  \n\n[0012] S1：甲基丙烯酸叔丁酯单体或甲基丙烯酸叔丁酯单体/苯乙烯与逆加成‑断裂链转移剂在催化剂的作用下发生反应，生成末端含二硫酯键的聚甲基丙烯酸叔丁酯或末端含二硫酯键的聚基丙烯酸叔丁酯/聚苯乙烯共聚物；  \n\n[0013] S2：将步骤S1制备得到的产物通过还原反应，制备为末端含硫醇基团的聚甲基丙烯酸或末端含硫醇基团的聚甲基丙烯酸/聚苯乙烯共聚物；  \n\n[0014] S3：再将HAuC1 和NaBH 放入将步骤S1制备得到的产物的水溶液中，HAuC1 被 $\\mathrm{NaBH_{4}}$ 聚还原为Au粒子，末端含硫醇基团的聚甲基丙烯酸或末端含硫醇基团的聚甲基丙烯酸/聚苯乙烯共聚物将Au粒子包裹，形成金纳米粒子。  \n\n[0015] 优选的，所述步骤S1中的可逆加成‑断裂链转移剂包括2‑(甲氧基碳酰基)‑乙基双硫苯酯和\\或二硫代苯甲酸酯。  \n\n[0016] 优选的，所述有机粘合剂包括聚氨酯、环氧树脂、丙烯酸酯、醇酸树脂、聚酯和聚酰胺中的一种或多种。  \n\n[0017] 优选的，所述环氧树脂包括非离子型环氧树脂，所述非离子型环氧树脂为在双酚A型环氧树脂或双酚F型环氧树脂的侧链接枝上亲水的非离子型链段得到，所述非离子型链段为 $\\cdot\\mathrm{NHCOOCH_{2}}$ [CH2‑O‑CH2]nCH2OOCNH‑。  \n\n[0018] 优选的，所述溶剂包括水、乙醇和异丙醇中的一种或多种。  \n\n[0019] 一种如上所述的防雾涂料的制备方法，将上述质量份数的所述亲水纳米颗粒、有机粘合剂和金纳米粒子依次加入上述质量份数的溶剂中，混合搅拌均匀后，即可得到所述防雾涂料。  \n\n[0020] 一种如上所述的防雾涂料的应用，将所述防雾涂料涂覆在玻璃或塑料基材固化形成防雾涂层。  \n\n[0021] 本发明的一种防雾涂料包括金纳米粒子、亲水纳米颗粒、有机粘合剂和溶剂；金纳米粒子能够稳定分散在溶剂中，而且其中的纳米金之间不会发生团聚，有利于金纳米发挥稳定的防雾效果；有机粘合剂与金纳米粒子能够在一定温度下发生固化，保证了防雾涂料在所涂覆的材料表面形成的涂层具有良好的硬度，并且使得涂层与材料表面有很好的粘黏性，亲水纳米颗粒能够增强涂层的亲水性，有利于加快水在涂层表面的铺展，加快水滴的挥发，与金纳米粒子协同来进一步提高防雾性。  \n\n[0022] 金纳米粒子的囊壁包括聚甲基丙烯酸或聚甲基丙烯酸/聚苯乙烯共聚物，其囊壁中含有大量的羧基基团，由于纳米金被聚甲基丙烯酸或聚甲基丙烯酸/聚苯乙烯共聚物的囊壁包裹，当金纳米粒子溶解在溶剂中时，纳米金之间不会发生团聚，保证了纳米金在溶剂中的分散稳定性，进而使得纳米金在使用过程中发挥出优异的防雾性能。金纳米粒子的中的纳米金具有高活性，在可见光的照射下纳米金的能量被激发，引起涂层表面温度升高，温度升高会使得小液滴挥发，阻止了雾的形成；金纳米粒子的囊壁采用是聚甲基丙烯酸或聚甲基丙烯酸/聚苯乙烯共聚物，羧基之间的间距较小，由于位阻的效应，会存在一部分羧基不参与固化反应，由于羧基具有良好的亲水性，能够提高了涂层的表面张力，有利于水在涂层表面的铺展，进一步阻止了雾的形成。  \n\n[0023] 有机粘合剂中包含的环氧基、氨基和羟基与金纳米粒子的囊壁上的羧基基团在一定温度下发生交联固化，使得防雾涂料固化，提高防雾涂料在材料表面形成涂层的表面硬度。  \n\n[0024] 亲水纳米颗粒包括纳米二氧化钛和亲水型的纳米二氧化硅，其亲水性良好，有利于加快水在涂层表面的铺展，加快水滴的挥发，与金纳米粒子协同来进一步提高防雾性。  \n\n[0025] 金纳米粒子的制备原理如下：在偶氮二异丁腈的催化作用下，甲基丙烯酸叔丁酯单体或甲基丙烯酸叔丁酯单体和苯乙烯的混合物与逆加成‑断裂链转移剂发生反应，生成末端含二硫酯键的聚甲基丙烯酸叔丁酯或末端含二硫酯键的聚基丙烯酸叔丁酯/聚苯乙烯共聚物；然后向其中加入浓盐酸，发生还原反应，制备出末端含硫醇基团的聚甲基丙烯酸或末端含硫醇基团的聚甲基丙烯酸/聚苯乙烯共聚物；HAuC1 被NaBH 聚还原为Au粒子，由于硫醇基团与金的耦合作用强，末端含硫醇基团的聚甲基丙烯酸或末端含硫醇基团的聚甲基丙烯酸/聚苯乙烯共聚物将Au粒子包裹，形成金纳米粒子。本发明通过含羟基的亲水性聚合物和异氰酸酯，在双酚A型环氧树脂或双酚F型环氧树脂上嵌入非离子型链段 $\\mathrm{\\cdotNHCOOCH_{2}}$ [CH2‑O‑CH2] $\\mathrm{nCH_{2}00C N H^{-}}$ ，得到非离子型环氧树脂；由于非离子型链段具有亲水性，使得非离子型环氧树脂的水溶性增强，使得非离子型环氧树脂能更好的分散在水相中；并且非离子型环氧树脂溶解在水中呈中性，不会影响防雾涂料体系的pH值，使得防雾涂料体系的稳定性好。[0026] 本发明制备的防雾涂料，在室温条件下，其中的各组分不会发生化学反应，可以长时间储存，该防雾涂料能够在玻璃和塑料基材上形成涂层，涂层的防雾效果好、耐水性好、表面硬度高、附着力强、透明度高和使用寿命长的优点。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 具体实施方式  \n\n[0027] 以下是对本发明的技术方案作进一步的描述，但本发明并不限于这些实施例。[0028] 实施例1  \n[0029] 本发明的一种防雾涂料的制备方法，具体实施步骤包括如下：  \n[0030] 1 .将0.5份偶氮二异丁腈、2份2‑(甲氧基碳酰基)‑乙基双硫苯酯和70份甲基丙烯酸叔丁酯单体加入反应釜中，在氮气保护环境下，在 $70^{\\circ}\\mathrm{C}$ 温度下反应24h，然后冷却至 $5^{\\circ}\\mathrm{C}$ ，得到混合物A；  \n[0031] 2.将步骤1中的混合物A溶解在三氯甲烷中，向其中加入 $.5\\mathrm{{^circC}}$ 的乙醚，搅拌均匀，收集混合溶液中的固体沉淀得到沉淀物B，沉淀物B为末端含二硫酯键的聚甲基丙烯酸叔丁酯；  \n[0032] 3.将步骤2中得到的沉淀物B与200份1，4‑二氧六环和20份质量分数为 $37\\%$ 的浓盐酸混合，在 $85^{\\circ}\\mathrm{C}$ 温度下反应72h，得到混合液；旋蒸去除混合液中的1，4‑二氧六环，然后加入乙醚，搅拌均匀，收集混合液中的固体沉淀得到沉淀物C，沉淀物C为末端含硫醇基团的聚甲基丙烯酸；  \n[0033] 4.将步骤3得到的沉淀物C溶于水，配置成质量浓度为 $1\\%$ 的溶液，在其中加入10份$\\mathrm{HAuC1}_{4}$ ，搅拌6h后，再加入0.5份NaBH ，在室温下反应0.5h，收集混合液中的沉淀物，即获得  \n\n金纳米粒子。  \n\n[0034] 将15份聚乙二醇400和6份异佛尔酮二异氰酸酯加入反应釜中，在室温下反应$0.5\\mathrm{h}$ ，然后在 $40^{\\circ}\\mathrm{C}$ 温度下继续反应1h，再向其中加入35份环氧树脂E44，在 $80^{\\circ}\\mathrm{C}$ 温度下反应4h，整个反应过程保持搅拌，搅拌转速为 $200\\mathrm{rpm}$ ，得到非离子型环氧树脂。  \n\n[0035] 本实施例制备得到的金纳米粒子的颗粒平均直径为20纳米；按重量份数计，将1份纳米二氧化钛、10份非离子型环氧树脂和1份金纳米粒子依次加入40份水中，混合均匀，形成防雾涂料。  \n\n[0036] 在实际使用过程中，将防雾涂料涂覆在玻璃板上，在 $100^{\\circ}\\mathrm{C}$ 温度下固化2h，形成防雾涂层，对防雾涂层进行如下性能测试：按照GB/T  9286‑1998的规定测试防雾涂层的附着力，按照GB/T  6739‑1996中的规定测试防雾涂层的涂层硬度；按照GB/T  1733‑1993中的规定测试防雾涂层的耐水性；通过采用LS182太阳膜测试仪，以普通玻璃为基材，将涂料涂在玻璃上固化成膜，测试固化膜的自然光透过率，以0‑100数值给出，数值越大透明度越好，其中普通玻璃的透光率92‑95，测试结果记录在表1中。  \n\n[0037] 实施例2  \n\n[0038] 本实施例与实施例1中的步骤基本相同，不同之处在于，以重量份数计，步骤1中，偶氮二异丁腈为1份，2‑(甲氧基碳酰基)‑乙基双硫苯酯为3份，甲基丙烯酸叔丁酯单体为50份，苯乙烯为5份；反应温度为 $60^{\\circ}\\mathrm{C}$ ，反应时间为 $48\\mathrm{h}$ ；步骤2中，乙醚温度 $0^{\\circ}\\mathrm{C}$ ；步骤3中，1，4‑二氧六环为300份和浓盐酸为30份，反应温度为 $90^{\\circ}\\mathrm{C}$ ，反应时间为 $48\\mathrm{h}$ ；步骤4中，沉淀物C的质量浓度为 $3\\%$ ， $\\mathrm{HAuC1}_{4}$ 为15份， $\\mathrm{NaBH_{4}}$ 为1.5份，搅拌时间为8h后，反应时间为4h。  \n\n[0039] 将25份聚乙二醇1000和10份甲苯二异氰酸酯加入反应釜中，在室温下反应1h，然后在 $50^{\\circ}\\mathrm{C}$ 温度下继续反应2h，再向其中加入65份环氧树脂E51，在 $100^{\\circ}\\mathrm{C}$ 温度下反应6h，整个反应过程保持搅拌，搅拌转速为 $500\\mathrm{rpm}$ ，得到非离子型环氧树脂。  \n\n[0040] 本实施例制备得到的金纳米粒子的颗粒平均直径为50纳米；按重量份数计，将40份纳米二氧化钛、30份非离子型环氧树脂和20份金纳米粒子依次加入90份水中，混合均匀，形成防雾涂料。  \n\n[0041] 在实际使用过程中，将防雾涂料涂覆在玻璃板上，在 $150^{\\circ}\\mathrm{C}$ 温度下固化1h，形成防雾涂层，对防雾涂层按照实施例1中进行性能测试，将测试结果记录在表1中。  \n\n[0042] 实施例3  \n\n[0043] 本实施例与实施例1中的步骤基本相同，不同之处在于，以重量份数计，步骤1中，偶氮二异丁腈为0.7份，2‑(甲氧基碳酰基)‑乙基双硫苯酯为4份，甲基丙烯酸叔丁酯单体为80份，苯乙烯为10份，反应温度为 $65^{\\circ}\\mathrm{C}$ ，反应时间为 $36\\mathrm{h}$ ；步骤3中，1，4‑二氧六环为280份，浓盐酸为27份，反应温度为 $95\\mathrm{^\\circC}$ ，反应时间为 $\\mathrm{72h}$ ；步骤4中，沉淀物C的质量浓度为 $2\\%$ ， $\\mathrm{HAuC1}_{4}$ 为12份，NaBH 为1份，搅拌时间为7h后，反应时间为2h。  \n\n[0044] 将20份聚乙二醇单甲醚750和8份二苯基甲烷二异氰酸酯加入反应釜中，在室温下反应0.8h，然后在 $45\\mathrm{^\\circC}$ 温度下继续反应2h，再向其中加入50份环氧树脂E20，在 $90^{\\circ}\\mathrm{C}$ 温度下反应5h，整个反应过程保持搅拌，搅拌转速为 $400\\mathrm{rpm}$ ，得到非离子型环氧树脂。  \n\n[0045] 本实施例制备得到的金纳米粒子的颗粒平均直径为80纳米；按重量份数计，将20份亲水型的纳米二氧化硅、20份非离子型环氧树脂和10份金纳米粒子依次加入70份水中，混合均匀，形成防雾涂料。  \n\n[0046] 在实际使用过程中，将防雾涂料涂覆在玻璃板上，在 $120^{\\circ}\\mathrm{C}$ 温度下固化1h，形成防雾涂层，对防雾涂层按照实施例1中进行性能测试，将测试结果记录在表1中。  \n\n[0047] 实施例4  \n\n[0048] 本实施例与实施例1中的步骤基本相同，不同之处在于，以重量份数计，步骤1中，偶氮二异丁腈为0.9份，2‑(甲氧基碳酰基)‑乙基双硫苯酯为3.5份，甲基丙烯酸叔丁酯单体为90份；步骤3中，1，4‑二氧六环为240份，浓盐酸为22份，反应温度为 $90^{\\circ}\\mathrm{C}$ ，反应时间为 $60\\mathrm{h}$ ；步骤4中，沉淀物C的质量浓度为 $1.5\\%$ ，HAuC14为14份，NaBH4为1 .2份，搅拌时间为7 .5h后，反应时间为 $2.5\\mathrm{h}$ 。  \n\n[0049] 将18份聚乙二醇/聚丙二醇共聚物和7份液化MDI加入反应釜中，在室温下反应$0.6\\mathrm{h}$ ，然后在 $40^{\\circ}\\mathrm{C}$ 温度下继续反应1.5h，再向其中加入45份双酚F型环氧树脂，在 $95^{\\circ}\\mathrm{C}$ 温度下反应 $4.5\\mathrm{h}$ ，整个反应过程保持搅拌，搅拌转速为 $300\\mathrm{rpm}$ ，得到非离子型环氧树脂。  \n\n[0050] 本实施例制备得到的金纳米粒子的颗粒平均直径为65纳米；按重量份数计，将10份亲水型的纳米二氧化硅、15份非离子型环氧树脂和15份金纳米粒子依次加入80份水中，混合均匀，形成防雾涂料。  \n\n[0051] 实施例5  \n\n[0052] 本实施例与实施例4中的步骤基本相同，不同之处在于，在防雾涂料中加入四丁基溴化胺，将其涂覆在PET塑料板上，在 $25\\mathrm{{^\\circC}}$ 的温度下放置7d，四丁基溴化胺催化羧酸基团与环氧基团发生反应固化形成涂层。对防雾涂层按照实施例1中进行性能测试，将测试结果记录在表1中。其中PET塑料板的透光率在 $90{\\sim}95$ 。  \n\n[0053] 由表1可知，本发明实施例中的防雾涂料在玻璃或塑料表面形成的涂层，其防雾性能优异，表面硬度高达到 $5\\mathord{\\sim}6\\mathrm{H}$ ，涂层附着力达到最高等级0级，表明涂层与玻璃或塑料表面的粘附力非常强，使得涂层不易脱落，同时涂层的耐水性好，将涂料涂覆在玻璃或塑料表面形成涂层后，不影响玻璃或塑料的透光率，说明涂层的透光率。本发明的防雾涂料安全无毒，其形成的涂层防雾性能优异、硬度高、耐水性良好、与基材的粘接强度高，透光率高，使用寿命可长达3年。  \n\n[0054] 表1本发明实施例中防雾涂料形成的涂层的性能测试的结果表  \n\n[0055]  \n\n<html><body><table><tr><td></td><td>防雾等级</td><td>表面硬度</td><td>附着力</td><td>耐水性</td><td>透光率</td></tr><tr><td>实施例1</td><td>1级</td><td>5H</td><td>0级</td><td>通过</td><td>92</td></tr><tr><td>实施例2</td><td>1级</td><td>5H</td><td>0级</td><td>通过</td><td>95</td></tr><tr><td>实施例3</td><td>1级</td><td>6H</td><td>0级</td><td>通过</td><td>94</td></tr><tr><td>实施例4</td><td>1级</td><td>6H</td><td>0级</td><td>通过</td><td>93</td></tr><tr><td>实施例5</td><td>1级</td><td>6H</td><td>0级</td><td>通过</td><td>92</td></tr></table></body></html>\n\n[0056] 以上未涉及之处，适用于现有技术。  \n\n[0057] 虽然已经通过示例对本发明的一些特定实施例进行了详细说明，但是本领域的技术人员应该理解，以上示例仅是为了进行说明，而不是为了限制本发明的范围，本发明所属技术领域的技术人员可以对所描述的具体实施例来做出各种各样的修改或补充或采用类似的方式替代，但并不会偏离本发明的方向或者超越所附权利要求书所定义的范围。本领域的技术人员应该理解，凡是依据本发明的技术实质对以上实施方式所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围。",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,47 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n<html><body><table><tr><td>(21)申请号 202110751873.6</td><td>(51)Int.CI.</td></tr><tr><td>(22)申请日2021.07.02</td><td>CO9D 175/14 (2006.01)</td></tr><tr><td>(65)同一申请的已公布的文献号</td><td>C09D 163/10 (2006.01)</td></tr><tr><td>申请公布号CN113372807A</td><td>C09D 7/62 (2018.01)</td></tr><tr><td>(43)申请公布日2021.09.10</td><td>C09D 7/65 (2018.01)</td></tr><tr><td></td><td>审查员周苹</td></tr><tr><td>(73)专利权人武汉中科先进材料科技有限公司</td><td></td></tr><tr><td>地址 430000 湖北省武汉市武汉经济技术</td><td></td></tr><tr><td>开发区206M地块华中电子商务产业园</td><td></td></tr><tr><td>A6栋1-6层</td><td></td></tr><tr><td>(72)发明人康翼鸿喻学锋吴列程文杰 杨新耕</td><td></td></tr><tr><td></td><td></td></tr><tr><td>(74)专利代理机构武汉高得专利代理事务所</td><td></td></tr><tr><td>（普通合伙）42268</td><td></td></tr><tr><td>专利代理师姜璐</td><td></td></tr></table></body></html>",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n一种持续耐摩擦的紫外光固化防雾涂料组合物及其涂层的制备",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明的目的是提供一种持续耐摩擦的紫外光固化防雾涂料组合物及其制备方法。该涂料光固化后所得超亲水涂层，持续防雾性能出色，同时具有优异的耐磨擦性能，因此克服了市面上防雾涂料的一些弊端，长期在水中浸泡使用后(如泳镜)仍具有优异的防雾性能，持续防雾时间可达1‑2年，非常适合应用于具有防雾要求的领域，如泳镜、车灯、挡风玻璃、浴室镜、光学透镜材料等。  \n\n1.一种持续耐摩擦的紫外光固化防雾涂料组合物，包括如下重量份的组分：  \n\n表面活性剂3‑5份；  \n\n可光固化丙烯酸亲水树脂20‑38份；  \n可光固化丙烯酸疏水树脂20‑25份；  \n可光固化无机组分10‑15份；  \n两性离子聚合物树脂5‑10份；  \n可光固化疏水小分子10‑15份；  \n可光固化亲水小分子5‑10份；  \n\n流平剂1‑2份；  \n\n引发剂1‑5份；  \n\n所述组合物还包括溶剂，所述溶剂重量是其它组分总重量的0.3‑3倍；  \n\n所述可光固化无机组分包括带碳碳双键中空透明 $\\mathrm{Si0_{2}}$ 和/或 $\\mathrm{Ti0}_{2}$ 纳米颗粒；  \n\n所述中空透明SiO 和/或TiO 纳米颗粒制备方法包含两步：  \n\n第一步为合成中空透明 $\\mathrm{Si0_{2}}$ 和/或 $\\mathrm{Ti0}_{2}$ 纳米颗粒，在反应容器中加入TEOS和/或钛酸四丁酯，以及甲醇，缓慢滴加草酸溶液做催化剂，常温下搅拌，加入氨水和聚丙烯酸，反应得到的产物用无水乙醇离心洗涤，得中空透明 $\\mathrm{Si0_{2}}$ 和/或TiO 溶胶，将溶剂蒸干后可得中空透明$\\mathrm{Si0_{2}}$ 和/或TiO 纳米颗粒；  \n\n第二步为合成含双键的中空透明 $\\mathrm{Si0_{2}}$ 和/或 $\\mathrm{Ti}0_{2}$ 纳米颗粒，将上述中空透明SiO 和/或$\\mathrm{Ti}0_{2}$ 纳米颗粒分散于乙醇，加入硅烷偶联剂KH570，室温搅拌，无水乙醇离心洗涤。  \n\n2.根据权利要求1所述持续耐摩擦的紫外光固化防雾涂料组合物，其特征在于：所述表面活性剂为壬基酚聚氧乙烯醚、辛基酚聚氧乙烯醚或聚乙烯醇中的一种或多种。  \n\n3.根据权利要求1所述持续耐摩擦的紫外光固化防雾涂料组合物，其特征在于：所述可光固化丙烯酸亲水树脂为自制的侧链含有不饱和双键的丙烯酸酯，其主要骨架为聚氨酯丙烯酸酯，以亲水的脂肪醇聚氧乙烯醚(AEO)、二异氰酸酯、丙烯酸酯为单体聚合而成的低聚物。  \n\n4.根据权利要求3所述持续耐摩擦的紫外光固化防雾涂料组合物，其特征在于：所述可光固化丙烯酸亲水树脂的具体制备方法为：将二异氰酸酯和丙烯酸酯混合，溶剂为乙酸乙酯；在 $40-60^{\\circ}\\mathrm{C}$ 反应1‑2小时后加入脂肪醇聚氧乙烯醚(AEO)继续反应3‑4小时后制得；二异氰酸酯、丙烯酸酯及脂肪醇聚氧乙烯醚(AEO)三者投料摩尔比为1‑1.3：2‑2.4：2‑2.2。  \n\n5.根据权利要求1所述持续耐摩擦的紫外光固化防雾涂料组合物，其特征在于：所述可光固化丙烯酸疏水树脂为官能度高于 $\\geqslant4$ 的环氧丙烯酸树脂；所述可光固化丙烯酸疏水树脂为环氧树脂和丙烯酸酯为单体聚合而得。  \n\n6.根据权利要求5所述持续耐摩擦的紫外光固化防雾涂料组合物，其特征在于：可光固化丙烯酸疏水树脂的具体制备方法为：将上述环氧树脂和丙烯酸酯混合，另加入三乙胺做催化剂，溶剂为乙酸乙酯；在 $80-120^{\\circ}\\mathrm{C}$ 反应5‑8小时后制得；环氧树脂和丙烯酸酯二者投料摩尔比为1：2.2‑1：2.5。  \n\n7.一种如权利要求 $1{\\sim}6$ 任一项所述持续耐摩擦的紫外光固化防雾涂料组合物的制备方法，其特征在于：准确称取以下各组分，表面活性剂，可光固化丙烯酸亲水树脂，可光固化丙烯酸疏水树脂，可光固化无机组分，两性离子聚合物树脂，可光固化疏水小分子，可光固化亲水小分子；加入溶剂混合搅拌 $0.5\\AA^{}-1\\mathrm{h}$ ，再加入光引发剂和流平剂，混合后制得。  \n\n8.一种防雾涂层的制备，以玻璃、PC板、PMMA板或PET为板材，以喷涂、淋涂、滴涂、刮涂或滚涂方式涂覆权利要求 $1{\\sim}6$ 任一项所述持续耐摩擦的紫外光固化防雾涂料组合物，60$80^{\\circ}\\mathrm{C}$ 预烘 $2\\ifmmode-\\else\\textmu\\fi{}\\mathrm{3min}\\fi{}$ ，紫外LED灯光固化30‑60s，能量为 $500-1000\\mathrm{mJ/cm}^{2}$ 。  \n\n9.一种制品，包括板材和所述板材上的防雾涂层，其中所述防雾涂层通过固化权利要求1至6中任一项所述持续耐摩擦的紫外光固化防雾涂料组合物来获得。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 一种持续耐摩擦的紫外光固化防雾涂料组合物及其涂层的制备",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明属于光固化涂料领域，具体涉及一种紫外光固化的防雾涂料组合物。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 空气中的水蒸气在温度低于露点时，便会凝结成微小的液滴而成雾。这种不良的影响经常发生在窗户、浴室镜子、眼镜、游泳及潜水眼镜、挡风玻璃、光学仪器镜头、车灯、指示灯、农膜等这些与我们生活紧密相关的透明材料上。透明材料表面水滴雾化的结果，不仅透光率下降影响视觉，有时会产生危害，例如当雾滴凝结在如红外光学显微镜等精密分析仪器的透镜表面上时，其分析的准确性会降低。  \n\n[0003] 为了解决这些问题，通常会对材料表面进行疏水或亲水处理。疏水处理的方法并不常用，一方面疏水的材料价格较高，耐磨性差，同时难以达到防雾的效果。而有机亲水涂料本身价格较为便宜，也可通过一些改性来提高其耐水浸泡性、耐磨性。使用有机亲水涂层相比于疏水涂层处理方法不但施工方便，而且价格低廉。  \n\n[0004] 现在国内外主要集中在超亲水的研究，如涂层表面引入能形成氢键的基团如羧基、氨基、巯基、羟基，或是一些离子基团：羧酸根、磺酸根、铵根、磷酸根等，当引入这些基团或是离子时，涂层的表面达到超亲水的状态，水汽冷凝后在基材表面高度铺展，形成一层均匀的水膜，消除了微小水珠对光线的漫反射而达到防雾的目的。目前制备超亲水的途径主要是通过物理共混、化学表面修饰、化学键接法。目前市场上的防雾涂层持续防雾性能与耐磨性能无法平衡，使用一段时间后，防雾性能便下降明显。另外这些涂层在水的浸泡下水分子会持续渗透，对涂层进行破坏，难以持续防雾，因此，耐水浸泡与耐磨是防雾涂层亟待解决的两大问题。  \n\n[0005] 国内专利CN102795791A公开了一种耐磨超亲水增透涂层，该涂层通过反复沉积聚二烯丙基二甲基氯化铵和聚苯乙烯磺酸钠制备 $5\\sim20$ 层的双层结构，再通过反复沉积聚二烯丙基二甲基氯化铵和含有粒径为 $10{\\sim}40\\mathrm{nm}$ 的 $\\mathrm{Si0_{2}}$ 球形纳米粒子的悬浮液制备 $3{\\sim}8$ 层的双层结构，再通过 $100{\\sim}140^{\\circ}\\mathrm{C}$ 的水热处理和在 $600{\\sim}800^{\\circ}\\mathrm{C}$ 的马弗炉中淬火 $100{\\sim}300\\mathrm{s}$ 制得所需涂层。尽管该方法制得的涂层能够达到5H的高硬度且水接触角也很小，但步骤复杂，持续防雾性一般，能耗大，只是对性能有特殊高要求的用户合适。国内专利CN102086348A公开了一种聚氨酯固化丙烯酸酯树脂防雾涂料的制备方法，该涂料由亲水性丙烯酸树脂，封闭型聚醚异氰酸酯固化剂和催化剂二月桂酸二丁基锡组成。该涂层硬度大于2H，耐磨性能好，但持续防雾性能一般，固化过程需要时间较长，且需分段固化 $(50^{\\circ}\\mathrm{C}\\sim120^{\\circ}\\mathrm{C})$ )，工艺较为复杂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0006] 针对现有技术中的缺陷，本发明的目的是提供一种持续耐摩擦的紫外光固化防雾涂料组合物及其制备方法。该涂料光固化后所得超亲水涂层，持续防雾性能出色，同时具有优异的耐磨擦性能，因此克服了市面上防雾涂料的一些弊端，长期在水中浸泡使用后(如泳镜)仍具有优异的防雾性能，持续防雾时间可达1‑2年，非常适合应用于具有防雾要求的领域，如泳镜、车灯、挡风玻璃、浴室镜、光学透镜材料等。  \n\n[0007] 本发明的目的是通过以下技术方案实现的：  \n[0008] 本发明提供了一种紫外光固化防雾涂料组合物，所述组合物包括如的各组分：[0009] 表面活性剂3‑5份；  \n[0010] 可光固化丙烯酸亲水树脂(20‑38份)；  \n[0011] 可光固化丙烯酸疏水树脂(20‑25份)；  \n[0012] 可光固化无机组分(10‑15份)；  \n[0013] 两性离子聚合物树脂(5‑10份)；  \n[0014] 可光固化疏水小分子(10‑15份)；  \n[0015] 可光固化亲水小分子(5‑10份)；  \n[0016] 流平剂(1‑2份)；  \n[0017] 引发剂(3‑5份)；  \n[0018] 所述组合物还包括溶剂，所述溶剂重量是其它组分总重量的0.3‑3倍。  \n[0019] 所述表面活性剂为壬基酚聚氧乙烯醚，辛基酚聚氧乙烯醚，聚乙烯醇中的一种或多种。  \n\n[0020] 所述表面活性剂为组合物中的一种防雾组分，能加强涂层的防雾性能。  \n\n[0021] 所述可光固化丙烯酸亲水树脂为自制的侧链含有不饱和双键的丙烯酸酯(单官)，其主要骨架为聚氨酯丙烯酸酯，以亲水的脂肪醇聚氧乙烯醚(AEO)、二异氰酸酯、丙烯酸酯为单体聚合而成的低聚物。  \n\n[0022] 以下为所述可光固化丙烯酸亲水树脂的结构与制备过程反应式：  \n\n[0023]  \n\n![](images/72f37351cc477bb3fbad6557a9aab7da38ab09a788395baae797ab07cb4fcc90.jpg)  \n\n[0024] 其中 $\\mathrm{R}_{1},\\mathrm{R}_{2},$ $\\mathrm{R_{3}}$ 均为1‑18个碳原子组成的烷基链段。  \n\n[0025] 可光固化丙烯酸亲水树脂的具体制备方法为：将上述二异氰酸酯和丙烯酸酯混合，溶剂为乙酸乙酯。在 $40-60^{\\circ}\\mathrm{C}$ 反应1‑2小时后加入脂肪醇聚氧乙烯醚(AEO)继续反应3‑4小时后制得。二异氰酸酯、丙烯酸酯及脂肪醇聚氧乙烯醚(AEO)三者投料摩尔比约为1‑1.3：2‑2.4：2‑2.2。  \n\n[0026] 所述脂肪醇聚氧乙烯醚(AEO)为十二醇聚氧乙烯醚，十六醇聚氧乙烯醚，十八醇聚氧乙烯醚中的一种或多种。  \n\n[0027] 优选的，所述脂肪醇聚氧乙烯醚(AEO)的分子量在500‑2000之间[0028] 所述二异氰酸酯为异佛尔酮二异氰酸酯(IPDI) 、二环己基甲烷二异氰酸酯(HMDI)、六亚甲基二异氰酸酯(HDI)中的一种或多种。  \n\n[0029] 所述丙烯酸酯包含甲基丙烯酸羟乙酯(HEMA)、丙烯酸羟乙酯(HEA)、季戊四醇三丙烯酸酯(PETA)中的一种或多种。  \n\n[0030] 先加入丙烯酸酯反应后加入脂肪醇聚氧乙烯醚的目的在于为了使制备的可光固化丙烯酸亲水树脂引入更多的双键。  \n\n[0031] 所述可光固化亲水树脂为组合物中的一种防雾组分，能加强涂层的防雾性能，紫外(UV)  固化后能提高涂层机械性能和持续防雾性能。  \n\n[0032] 可光固化丙烯酸疏水树脂为官能度高于≥4的环氧丙烯酸树脂。  \n\n[0033] 所述可光固化丙烯酸疏水树脂为环氧树脂和丙烯酸酯为单体聚合而得。  \n\n[0034] 所述环氧树脂为双官环氧树脂，包括双酚A型环氧树脂，缩水甘油醚类环氧树脂中的一种或多种。  \n\n[0035] 所述丙烯酸酯为季戊四醇三丙烯酸酯(PETA)，季戊四醇二丙烯酸酯(PEDA)中的一种或多种。  \n\n[0036] 可光固化丙烯酸疏水树脂的具体制备方法为：将上述环氧树脂和丙烯酸酯混合，另加入三乙胺做催化剂，溶剂为乙酸乙酯。在 $80-120^{\\circ}\\mathrm{C}$ 反应5‑8小时后制得。环氧树脂和丙烯酸酯二者投料摩尔比约为1：2.2‑1：2.5。  \n\n[0037] 可光固化丙烯酸疏水树脂紫外固化后可提高涂层的机械性能，在基材上有良好的附着力。  \n\n[0038] 可光固化无机组分包括带碳碳双键中空透明 $\\mathrm{Si0_{2}}$ 和/或 $\\mathrm{Ti0}_{2}$ 纳米颗粒。  \n\n[0039] 所述中空透明SiO 和/或 $\\mathrm{Ti0}_{2}$ 纳米颗粒制备方法包含两步：  \n\n[0040] 第一步为合成中空透明 $\\mathrm{Si0_{2}}$ 和/或 $\\mathrm{Ti0}_{2}$ 纳米颗粒。具体方法为：在反应容器中加入TEOS  或钛酸四丁酯，以及甲醇，缓慢滴加草酸溶液做催化剂，在常温下搅拌30min。另取烧杯加入氨水和聚丙烯酸，等分5次加入反应容器中，每隔1h加入1次，总体反应时间大约为6h，将得到的产物用无水乙醇离心洗涤2遍，可得中空透明 $\\mathrm{Si0_{2}}$ 和 $\\mathrm{\\Ti0_{2}}$ 溶胶。将溶剂蒸干后可得中空透明 $\\mathrm{Si0_{2}/T i0_{2}}$ 纳米颗粒。  \n\n[0041] 第二步为含双键的中空透明 $\\mathrm{Si0_{2}/T i0_{2}}$ 纳米颗粒。具体方法为将上述中空透明$\\mathrm{Si0_{2}/T i0_{2}}$ 纳米颗粒分散于乙醇，加入硅烷偶联剂KH570，室温搅拌4‑6h，无水乙醇离心洗涤2遍。  \n\n[0042] 中空透明 $\\mathrm{Si0_{2}/T i0_{2}}$ 纳米颗粒是通过在 $\\mathrm{SiO_{2}/T i O_{2}}$ 溶胶中在包覆盐然后再将盐除去的方式制得，所得的 $\\mathrm{Si0_{2}/T i0_{2}}$ 纳米颗粒为空心颗粒，以此来减少光的散射从而达到透明的效果。  \n\n[0043] 本发明通过可光固化无机组分与可光固化有机组分杂化提高涂层强度。  \n\n[0044] 两性离子聚合物树脂是一类整体呈电中性，在同一单体侧链上同时含有阴、阳离子基团的高分子树脂。两性离子聚合物树脂是有很好的亲水性能，为组合物中的一种防雾组分，能加强涂层的防雾性能。  \n\n[0045] 本发明所述两性离子聚合物树脂的阳离子基团类型为季铵盐阳离子，阴离子基团类型主要有3种：磺酸根负离子、羧酸根负离子、磷酸根负离子。因此所述两性离子聚合物树脂包括以聚(甲基)丙烯酸酯为骨架的磺酸甜菜碱(SB)、羧酸甜菜碱(CB)和磷酰胆碱(PC)。  \n\n[0046] 本发明通过有机可光固化丙烯酸亲水树脂、有机光可固化丙烯酸疏水树脂与两性离子聚合物树脂形成交联的互穿网络，提高涂层硬度、机械强度，可锁住表面活性剂，延长防雾耐久时间。  \n\n[0047] 所述含可光固化疏水小分子包括1、6‑己二醇二丙烯酸酯(HDDA)，季戊四醇四丙烯酸酯(PETA4)，双季戊四醇六丙烯酸酯(DPHA)中的一种或多种。  \n\n[0048] 所述含可光固化疏水小分子在涂层光固化时可与光固化亲水、疏水树脂交联，提 高涂层在基材的附着力。  \n\n[0049] 所述含可光固化亲水小分子包括丙烯酸、衣康酸、丙烯酸羟乙酯中的一种或多种。[0050] 所述含可光固化亲水小分子在涂层光固化时可与光固化亲水、疏水树脂交联，提高涂层防雾能力。  \n\n[0051] 所述流平剂是能有效降低涂料表面张力，提高其流平性和均匀性的一类物质，能促使涂料在干燥成膜过程中形成一个平整、光滑、均匀的涂膜。  \n\n[0052] 所述流平剂为丙烯酸酯类流平剂，分子量在6000‑20000之间。  \n\n[0053] 所述光引发剂是一类能在紫外光区 $(250{\\sim}420\\mathrm{nm})$ 吸收一定波长的能量，产生自由基、阳离子等，从而引发单体聚合交联固化的化合物。  \n\n[0054] 所述光引发剂包括2‑羟基‑2‑甲基‑1‑苯基丙酮(1173)，1‑羟基环己基苯基甲酮(184)  ， 2,4,6‑三甲基苯甲酰基‑二苯基氧化膦(TPO)中的一种或多种。  \n\n[0055] 所述溶剂为乙酸乙酯、乙酸丁酯、异丙醇、乙醇中的一种或多种。  \n\n[0056] 本发明通过大量的实验尝试确定配方各组分的合适比例。若可光固化丙烯酸亲水树脂过高，亲水性光固化小分子过高，可光固化丙烯酸疏水树脂过低，  \n\n[0057] 所得最终光固化后所得涂膜亲水性太好，会导致最终涂膜耐水性差，持续防雾性差；可光固化丙烯酸亲水树脂过低，亲水性光固化小分子过低，可光固化丙烯酸疏水树脂过高，会导致最终涂膜亲水性太差，初始水接触角较大，没有防雾性。  \n\n[0058] 若光引发剂高于5份时，紫外光照下会产生大量自由基，导致所得涂料固化后形成的最终三维网络聚合物分子量低，导致涂膜较脆，附着力会变差，同时还会提高涂料成本；若光引发剂低于1份，紫外光照下会产生自由基不充分，导致残留没有光聚合的树脂和单体含量较多，引起最终涂膜表干不好，发粘，根本不能使用。  \n\n[0059] 溶剂的量高于其他组分总重量3倍时，涂料太稀，涂膜厚度太低，导致最终涂膜的硬度太低，耐磨变差。若溶剂的量低于其他组分总重量0.3倍时，涂料粘度太大，容易导致涂膜流平不好，涂膜厚度太厚，也会带来固化不完全问题。  \n\n[0060] 本发明所述紫外光固化防雾涂料的制备方法如下：准确称取各组分，将表面活性剂，可光固化丙烯酸亲水树脂，可光固化丙烯酸疏水树脂，可光固化无机组分，两性离子聚合物树脂，可光固化疏水小分子，可光固化亲水小分子；加入溶剂混合搅拌0.5‑1h，再加入光引发剂和流平剂，混合0.5h后制得。  \n\n[0061] 本发明所述紫外光固化防雾涂层制备方法为：将紫外光固化防雾组合物原液涂覆在板材上， $60-80^{\\circ}\\mathrm{C}$ 预烘 $2\\ifmmode-3\\else\\textmu\\fi{}\\mathrm{{min}}$ ，紫外LED灯光固化30‑60s，能量为 $500\\mathrm{-}1000\\mathrm{mJ/cm^{2}}$ ，涂覆方式为喷涂、淋涂、滴涂、刮涂或滚涂中的一种。  \n\n[0062] 本发明还提供一种制品，包括板材和所述板材表面上的防雾涂层，其中所述防雾涂层通过固化上述任一项的持续耐摩擦的紫外光固化防雾涂料组合物来获得。  \n\n[0063] 该涂层所选板材为玻璃、PC(聚碳酸酯)板、PMMA(聚甲基丙烯酸甲酯)板、PET(聚对苯二甲酸乙二醇酯)中的一种。  \n\n[0064] 本发明可将紫外光固化防雾组合物原液涂覆至浴室镜(玻璃)、泳镜(PC)、护目镜(PC)、车灯罩(PMMA)等生活用品中，其涂覆方式与板材一致。  \n\n[0065] 本发明制备的紫外光固化防雾涂层，通过水接触角测试与水浴锅熏蒸测试来检测涂层防雾性能。水浴锅熏蒸是常见的防雾性能测试方法，水蒸气在水浴锅中与基材上会有温差，未处理的基材容易起雾。  \n\n[0066] 本发明耐水性能测试方法为：将涂覆有紫外光固化防雾涂层的基材放置在水中浸泡 $72~\\mathrm{h}\\cdot90\\mathrm{h}$ 后进行防雾测试，防雾性能未衰减。  \n\n[0067] 本发明中紫外光固化防雾涂层耐磨性能通过耐磨擦试验机测试。  \n\n[0068] 所述紫外光固化防雾涂层进行高温加速老化试验，将测试样品放入至 $200^{\\circ}\\mathrm{C}$ 烘箱，测试  1000‑1500小时，测试老化前后涂层无明显脱落、剥离、起皱现象。  \n\n[0069] 所述紫外光固化防雾涂层进行耐盐腐蚀测试， $5\\%$ 氯化钠溶液浸泡500‑1000小时，老化前后涂层无明显脱落、剥离、起皱现象。  \n\n[0070] 所述紫外光固化防雾涂层耐消毒水浸泡测试，将样品浸泡于消毒水中200‑500小时，老化前后涂层无明显脱落、剥离、起皱现象。  \n\n[0071] 所述紫外光固化防雾涂层进行环境测试，将样品放置于露天环境1‑2年，老化前后涂层无明显脱落、剥离、起皱现象。  \n\n[0072] 本发明与现有技术相比，本发明具有如下的有益效果：  \n\n[0073] 1、本发明因采用亲水性优良的可光固化亲水树脂，配合高官的可光固化疏水树脂，可光固化疏水小分子，可光固化亲水小分子，光固化后形成亲水性和疏水性部分交联的网状结构。其中亲水部分具有优异的亲水性能，致使水滴在涂层上易铺展形成水膜而不会起雾。疏水部分在涂层中起到锚固点的作用，交联密度增加，保证涂层在遇到大量的水时不会因溶胀而溶解，既能保证持续防雾性能又可以提高耐磨性能。  \n\n[0074] 2、可光固化无机组分与可光固化有机组分杂化提高涂层强度。  \n\n[0075] 3、有机可光固化丙烯酸亲水树脂、有机光可固化丙烯酸疏水树脂与两性离子聚合物树脂形成交联的互穿网络，提高涂层硬度、机械强度，可锁住表面活性剂，延长防雾耐久时间。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 具体实施方式  \n\n[0076] 下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。  \n\n[0077] 实施例1  \n[0078] 可光固化丙烯酸亲水树脂A的制备  \n[0079] 将 $0.1\\mathrm{mol}$ 异佛尔酮二异氰酸酯(IPDI)和0.2mol丙烯酸羟乙酯(HEA)混合，溶剂为乙酸乙酯。在 $40^{\\circ}\\mathrm{C}$ 反应2小时后加入 $0.2\\mathrm{mol}$ 十二醇聚氧乙烯醚继续反应3小时后制得。  \n\n[0080] 实施例2  \n\n[0081] 可光固化丙烯酸亲水树脂B的制备  \n\n[0082] 将 $1.3\\mathrm{mol}$ 二环己基甲烷二异氰酸酯(HMDI)和2.4mol甲基丙烯酸羟乙酯(HEMA)  混合，溶剂为乙酸乙酯。在 $50^{\\circ}\\mathrm{C}$ 反应1小时后加入2.2mol十六醇聚氧乙烯醚继续反应4小时后制得。  \n\n[0083] 实施例3  \n[0084] 可光固化丙烯酸亲水树脂C的制备  \n[0085] 将1mol六亚甲基二异氰酸酯(HDI)和2.4mol季戊四醇三丙烯酸酯(PETA)，溶剂为乙酸乙酯。在 $60^{\\circ}\\mathrm{C}$ 反应2小时后加入 $2.2\\mathrm{mol}$ 十八醇聚氧乙烯醚继续反应4小时后制得。  \n[0086] 实施例4  \n[0087] 可光固化丙烯酸疏水树脂a的制备  \n[0088] 将1mol双酚A型环氧树脂和 $2.2\\mathrm{mol}$ 季戊四醇三丙烯酸酯(PETA)混合，另加入  \n\n0.01mol  三乙胺做催化剂，溶剂为乙酸乙酯。在 $80^{\\circ}\\mathrm{C}$ 反应5小时后制得。  \n\n[0089] 实施例5  \n[0090] 可光固化丙烯酸疏水树脂b的制备  \n[0091] 将1mol缩水甘油醚类环氧树脂和2.5mol季戊四醇二丙烯酸酯(PEDA)混合，另加入  \n\n$0.02\\mathrm{mol}$ 三乙胺做催化剂，溶剂为乙酸乙酯。在 $120^{\\circ}\\mathrm{C}$ 反应8小时后制得。  \n\n[0092] 实施例6  \n[0093] 含双键中空透明 $\\mathrm{Si0_{2}}$ 纳米颗粒的制备  \n[0094] 在反应容器中加入1mol的TEOS和 $30\\mathrm{ml}$ 甲醇，缓慢滴加0.1mol草酸溶液做催化剂，在常温下搅拌30min。另取烧杯加入3.5ml氨水和3.8ml聚丙烯酸，等分5次加入反应容器中，每隔1h加入1次，完全加入后室温反应30min，将得到的产物用无水乙醇离心洗涤2  遍，可得中空透明SiO 溶胶。将溶剂蒸干后可得中空透明 $\\mathrm{Si0}_{2}$ 纳米颗粒。  \n\n[0095] 将所得0 .1mol中空透明 $\\mathrm{Si0_{2}}$ 纳米颗粒分散于乙醇中，加入0 .3mol硅烷偶联剂KH570，室温搅拌4h，无水乙醇离心洗涤2遍得到。  \n\n[0096] 实施例7  \n\n[0097] 含双键中空透明 $\\mathrm{Ti}0_{2}$ 纳米颗粒的制备[0098] 在反应容器中加入 $1.2\\mathrm{mol}$ 的钛酸四乙酯和 $30\\mathrm{ml}$ 甲醇，缓慢滴加0.15mol草酸溶液做催化剂，在常温下搅拌30min。另取烧杯加入3.5ml氨水和3.8ml聚丙烯酸，等分5次加入反应容器中，每隔1h加入1次，完全加入后室温反应 $30\\mathrm{{min}}$ ，将得到的产物用无水乙醇离心洗涤2遍，可得中空透明TiO 溶胶。将溶剂蒸干后可得中空透明TiO 纳米颗粒。  \n\n[0099] 将所得0 .15mol中空透明TiO 纳米颗粒分散于乙醇中，加入0 .3mol硅烷偶联剂KH570，室温搅拌4h，无水乙醇离心洗涤2遍得到。  \n\n[0100] 实施例8  \n\n[0101] 紫外光固化防雾涂料组合物的制备  \n\n[0102] 本发明中涉及的紫外光固化防雾涂料组合物制备方法如下：准确称取各组分，将表面活性剂，可光固化丙烯酸亲水树脂，可光固化丙烯酸疏水树脂，可光固化无机组分，两性离子聚合物树脂，可光固化疏水小分子，可光固化亲水小分子；加入溶剂混合搅拌0 .5‑1h，再加入光引发剂和流平剂，混合0.5h后制得。  \n\n[0103] 紫外光固化防雾涂料组合物组分及含量如表1，本发明中，溶剂可为乙酸乙酯、乙酸丁酯、异丙醇、乙醇中的一种或多种，在本实施例中，均采用乙酸丁酯：异丙醇：乙醇 $=4$ ：3 ： 3(体积比)做溶剂，溶剂总重量是其它组分总重量的0.3‑3倍。  \n\n[0104] 表1：紫外光固化防雾涂料组合物组分及含量  \n\n<html><body><table><tr><td>配方 编号</td><td>表面活 性剂</td><td>可光固化 亲水 树脂</td><td>可光固化 疏水树脂</td><td>可光固 化无机 组分</td><td>两性 离子 聚合 物</td><td>可光固 化疏水 小分子</td><td>可光固 化亲水 小分子</td><td>流平 剂</td><td>引发剂</td></tr><tr><td>#1</td><td>壬基酚 聚氧乙 烯醚，3 份</td><td>可光固化 丙烯酸亲 水树脂A 38份</td><td>可光固化 丙烯酸疏 水树脂A 25份</td><td>含双键 中空 SiO 10份</td><td>磺酸 甜菜 碱，5 份</td><td>HDDA. 10份</td><td>丙烯酸 5份</td><td>丙烯 酸酯， 1份</td><td>1173，3 份</td></tr><tr><td>#2</td><td>辛基酚 聚氧乙 烯醚，4 份</td><td>可光固化 丙烯酸亲 水树脂B 20份</td><td>可光固化 丙烯酸疏 水树脂B 25份</td><td>含双键 中空 TiO 15份</td><td>羧酸 甜菜 碱，10 份</td><td>PETA4 10份</td><td>衣康酸 10份</td><td>丙烯 酸酯， 2份</td><td>184，4 份</td></tr><tr><td>#3</td><td>聚乙烯</td><td>可光固化</td><td>可光固化</td><td>含双键</td><td>磷酰</td><td>DPHA</td><td>丙烯酸</td><td>丙烯</td><td>TPO,5</td></tr></table></body></html>  \n\n[0105]  \n\n<html><body><table><tr><td>[0106]</td><td></td><td></td><td>水树脂C</td><td>水树脂A</td><td>SiO2</td><td>10份</td><td></td><td>10份</td><td>1份</td><td></td></tr><tr><td rowspan=\"3\"></td><td></td><td>聚氧乙 烯醚，3</td><td>水树脂A</td><td>水树脂B</td><td>TiO</td><td>碱，5</td><td></td><td></td><td>1份</td><td></td></tr><tr><td>聚氧乙</td><td>烯醚，4</td><td>水树脂A</td><td>水树脂A</td><td>SiO2</td><td>碱，10</td><td></td><td></td><td>2份</td><td></td></tr><tr><td></td><td>醇5份</td><td>水树脂B 24份</td><td>水树脂B 20份</td><td>TiO 10份</td><td>10份</td><td>15份</td><td>羟乙酯 10份</td><td>1份</td><td></td></tr></table></body></html>  \n\n[0107] 实施例9   \n[0108] 板材上紫外光固化防雾涂层的制备   \n[0109] 将实施例8所得紫外光固化防雾组合物配方#1至#6原液涂覆在板材上， $60-80^{\\circ}\\mathrm{C}$ 预 烘  2‑3min，紫外LED灯光固化30‑60s，能量为 $500-1000\\mathrm{mJ/cm^{2}}$ ，涂覆方式为喷涂、淋涂、滴  \n\n涂、刮涂或滚涂中的一种。本发明中的板材可为玻璃、PC(聚碳酸酯)板、PMMA(聚甲基丙烯酸甲酯)板、PET(聚对苯二甲酸乙二醇酯)中的一种。  \n\n[0110] 实施例10  \n[0111] 制品上紫外光固化防雾涂层的制备  \n[0112] 将实施例8所得紫外光固化防雾组合物配方#1至#6原液涂覆在浴室镜(玻璃)、泳镜  (PC)、护目镜(PC)、车灯罩(PMMA)等生活用品中，其涂覆方式与实施例9一致。  \n[0113] 实施例11  \n[0114] 实施例9‑10中防雾涂层的性能测试  \n[0115] 水接触角测试仪进行水接触角测试：水接触角在 $8^{-}18^{\\circ}$ °之间。  \n[0116] 水浴锅熏蒸测试来检测涂层防雾性能：将水浴锅中的水加热至 $65-70^{\\circ}\\mathrm{C}$ ，涂覆有防雾涂层的样品放置在水浴锅上方10cm处熏蒸10s，所有样品均无起雾现象。  \n[0117] 耐水性能测试：将涂覆有紫外光固化防雾涂层的样品放置在水中浸泡 $72\\mathrm{h}\\ensuremath{-}90\\mathrm{h}$ 后进行水浴锅熏蒸防雾测试，防雾性能未衰减。  \n[0118] 耐磨擦试验机测试耐磨性能：砝码为 $200\\mathrm{g}$ ，测试工具为羊毛毡，循环擦拭10000次涂层无明显脱落、剥离、起皱且防雾性能无衰减。  \n[0119] 高温加速老化试验：将测试样品放入至 $200^{\\circ}\\mathrm{C}$ 烘箱，测试1000‑1500小时，测试老化前后涂层无明显脱落、剥离、起皱现象。  \n[0120] 耐盐腐蚀测试： $5\\%$ 氯化钠溶液浸泡500‑1000小时，老化前后涂层无明显脱落、剥离、起皱现象。  \n[0121] 耐消毒水浸泡测试：将样品浸泡于消毒200‑500小时，老化前后涂层无明显脱落、剥离、起皱现象。  \n[0122] 环境测试：将样品放置于露天环境1‑2年，老化前后涂层无明显脱落、剥离、起皱现象。",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# (19)中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利申请  \n\n<html><body><table><tr><td>(21)申请号 202110751892.9</td><td>CO8L 23/12 (2006.01)</td></tr><tr><td>(22)申请日2021.07.02</td><td></td></tr><tr><td>(71)申请人武汉中科先进技术研究院有限公司</td><td></td></tr><tr><td>地址 430000 湖北省武汉市武汉经济技术</td><td></td></tr><tr><td>开发区206M地块华中电子商务产业园</td><td></td></tr><tr><td>A6栋1-6层</td><td></td></tr><tr><td>(72)发明人康翼鸿喻学锋吴列杨新耕</td><td></td></tr><tr><td>(51) Int.CI .</td><td></td></tr><tr><td>CO9D 163/10 (2006.01)</td><td></td></tr><tr><td>CO9D 171/02 (2006.01)</td><td></td></tr><tr><td>C08J 7/043 (2020.01)</td><td></td></tr><tr><td>C08J 7/046 (2020.01)</td><td></td></tr><tr><td>C08J 7/054 (2020.01)</td><td></td></tr><tr><td>C08L 33/12 (2006.01)</td><td></td></tr><tr><td>C08L 25/06 (2006.01)</td><td></td></tr><tr><td>C08L 23/06 (2006.01)</td><td>权利要求书2页 说明书6页</td></tr></table></body></html>",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n一种双层紫外光固化耐摩擦防雾涂层及制备",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明涉及一种双层紫外光固化亲水防雾涂层，其涂料是由原液A和原液B两部分组成，原液A为底涂液，在基材上通过光固化附着在非极性塑料基材上；原液B为面涂液，以原液A光固化后的涂层为基材进一步附着。利用本发明的制备方法制备得到涂层，在兼顾涂层防雾性能的同时可以保证涂层有很好的附着力和耐久性。  \n\n1.一种双层紫外光固化耐摩擦防雾涂层，其特征在于：涂料是由原液A和原液B两部分  \n组成，原液A为底涂液，在基材上通过光固化附着在非极性塑料基材上；原液B为面涂液，以  \n原液A光固化后的涂层为基材进一步附着；所述原液A的各组分及重量份如下：环氧丙烯酸酯树脂70‑80份，丙烯酸酯15‑25份，光引发剂3‑5份，溶剂0‑200份；所述原液B的各组分及含量如下：光固化亲水树脂60‑70份，光固化亲水小分子10‑20份，光固化亲水盐10‑20份，光引发剂3‑5份，溶剂0‑200份；所述非极性塑料基材为表面能较低的基材，包括PMMA、PS、PE、PP中的一种。2.根据权利要求1所述双层紫外光固化耐摩擦防雾涂层，其特征在于：所述环氧丙烯酸  \n酯树脂的制备方法为：将环氧丙烯酸酯与二元酸溶于乙酸乙酯中，四丁基溴化铵作为催化  \n剂，加热至 $80^{\\circ}\\mathrm{C}-120^{\\circ}\\mathrm{C}$ 反应6‑8h制得；环氧丙烯酸酯与二元酸的比例为1： $:1.1{\\sim}1{:}1.4\\$ ，所述  \n环氧丙烯酸酯包括双酚A环氧丙烯酸酯(E51)、甲基丙烯酸缩水甘油酯(GMA)中的一种或多  \n种，所述二元酸包括己二酸、丁二酸、衣康酸中的一种或多种。3.根据权利要求1所述双层紫外光固化耐摩擦防雾涂层，其特征在于：所述丙烯酸酯为  \n包括烷氧化丙烯酸苯氧酯(OEPA)、丙烯酸辛酯、丙烯酸葵酯、三羟甲基丙烷三丙烯酸酯  \n(TMPTA)中的一种或多种。4.根据权利要求1所述双层紫外光固化耐摩擦防雾涂层，其特征在于：所述光固化亲水  \n树脂包括聚乙二醇二丙烯酸酯(PEG400DA)、聚乙二醇二丙烯酸酯(PEG600DA)、聚乙二醇二  \n丙烯酸酯(PEG1000DA)中的一种或多种。5.根据权利要求1所述双层紫外光固化耐摩擦防雾涂层，其特征在于：所述光固化亲水  \n小分子包括丙烯酸、甲基丙烯酸、丙烯酸羟乙酯、三羟甲基丙烷三丙烯酸酯(TMPTA)中的一  \n种或多种。6.根据权利要求1所述双层紫外光固化耐摩擦防雾涂层，其特征在于：所述光固化亲水  \n盐包括烯丙氧基壬基酚丙醇聚氧乙烯醚硫酸铵(DNS‑86) ，2‑丙烯酰胺‑2‑甲基丙磺酸  \n(AMPS)中的一种或多种。7.根据权利要求1所述双层紫外光固化耐摩擦防雾涂层，其特征在于：所述光引发剂包  \n括2‑羟基‑2‑甲基‑1‑苯基丙酮(1173)，1‑羟基环己基苯基甲酮(184)，2,4 ,6‑三甲基苯甲酰  \n基‑二苯基氧化膦(TPO)，2‑甲基‑2‑(4‑吗啉基)‑1‑[4‑(甲硫基)苯基]‑1‑丙酮(907)，苯甲  \n酰甲酸甲酯(MBF)，二苯甲酮中的一种或多种；所述溶剂为乙醇、异丙醇、乙酸丁酯、乙酸乙  \n酯、乙酸丙酯、正丁醚中的一种或多种。8.根据权利要求1所述双层紫外光固化耐摩擦防雾涂层，其特征在于：原液A的制备方  \n法为：准确称取各组分，将环氧丙烯酸酯，丙烯酸酯，加入溶剂混合搅拌，再加入光引发剂，  \n\n混合后制得；原液B的制备方法为：准确称取各组分，将光固化亲水树脂，光固化亲水小分子，光固化亲水盐加入溶剂混合搅拌10‑20min，再加入光引发剂，混合0.5‑1h后制得。  \n\n9.根据权利要求1所述双层紫外光固化耐摩擦防雾涂层，其特征在于：原液A和原液B的涂覆方式均为喷涂、淋涂、滴涂、刮涂或滚涂中的一种。  \n\n10.一种双层紫外光固化耐摩擦防雾涂层的制备方法，利用权利要求1中所述原液A和原液B对板材进行涂覆，具体为：为将原液A涂覆在板材上， $60-80^{\\circ}\\mathrm{C}$ 预烘 $1-3\\mathrm{{min}}$ ，紫外LED灯光固化20‑30s，能量为 $400{-}800\\mathrm{mJ/cm^{2}}$ ；再为将原液B涂覆在板材上， $60\\mathrm{-}80^{\\circ}\\mathrm{C}$ 预烘 $1-3\\mathrm{{min}}$ ，紫外LED灯光固化60‑120s，能量为 $400{-}800\\mathrm{mJ/cm^{2}}$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 一种双层紫外光固化耐摩擦防雾涂层及制备",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明涉及一种双层紫外光固化耐摩擦防雾涂层的制备方法，属于高分子材料合成技术领域。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 透明玻璃和聚合物材料具有优异的光学性能，在日常生活中应用广泛。但是这些材料在实际使用时，由于环境改变产生温差变化，空气中的水蒸气很容易在这些材料表面凝结成水滴，产生雾气，导致其透明性和能见度急剧下降。起雾现象不但降低了材料本身的透明度,影响相关产品的使用,还会给设备的运行安全带来隐患。  \n[0003] 因此,如何防雾逐渐引起研究人员和产业届的关注。常见的防雾技术有自动擦拭、热力防雾、表面涂层等。其中,具有主动防雾性能的超亲水表面涂层技术在施工简便性、持续防护性及运行维护成本的经济性等方面具有独特优势,是最有发展潜力的防雾技术。[0004] 目前，在众多超亲水涂层的制备方法中，化学涂料涂覆具有操作简便，成本低，适合大规模生产等优点，因此最受瞩目。国内外学者目前也陆续报道了有机、无机和复合材料等涂料。由于化学涂料通常容易在高极性塑料基材上附着，目前的化学涂料所涂覆的基材多为极性塑料基材(PET等)。而日常生活中使用的聚甲基丙烯酸甲酯(PMMA)、聚苯乙烯(PS)、聚乙烯(PE)、聚丙烯(PP)等非极性塑料基材表面能较低，通常所涂覆的涂层附着力较差，造成使用寿命短。因此非极性塑料基材的超亲水防雾涂层是亟待开发的。  \n[0005] 紫外光固化涂料，或UV涂料，具有不含挥发性有机化合物(VOC)，对环境污染小，固化速度快，节省能源、固化产物性能好、适合于高速自动化生产等优点，因此具有广泛的应用。UV涂料在附着力方面存在着两大缺陷：一是UV涂料缺乏对底材的渗透力，二是在固化过程中UV树脂的应力大。因此UV涂料经常采用双层涂层的方法，UV附着力促进剂(底涂液)做基材表面预处理，而后涂覆面涂液。然而这一方法应用在超亲水涂层中存在一些问题，如底涂液和面涂液亲和力不够，导致面涂液不能很好地附着从而发挥作用，同时底涂液通常润湿性太好导致超亲水涂层容易发生水的渗透从而影响涂层使用寿命。这些问题的存在影响了双层紫外光固化涂层在防雾领域的应用。因此，开发高性能的双层紫外光固化亲水防雾涂层是十分有必要的。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0006] 针对现有技术的缺陷，本发明的目的是提供一种双层紫外光固化耐摩擦防雾涂层。该涂料有两部分组成，一个是底涂液，与基材很好地附着，另一个是面涂液，涂覆时先涂覆底涂液，再涂覆面涂液，两层涂层均通过紫外光固化后所得，本发明涂层防雾性能出色，同时在非极性塑料基材(PMMA、PS、PE、PP)上附着力为0级，同时耐磨擦性能良好，所述涂层使用1年仍具有防雾性能。因此克服了市面上防雾涂料的一些弊端，非常适合应用于具有防雾要求的非极性塑料基材。  \n\n[0007] 本发明的目的是通过以下技术方案实现的：  \n\n[0008] 本发明提供了一种双层紫外光固化耐摩擦防雾涂层，所述涂料原液是由原液A和原液B两部分组成。  \n\n[0009] 原液A为底涂液，在基材上通过光固化能附着在非极性塑料基材(PMMA)上，同时原液A光固化后的涂层能作为原液B的基材，使原液B的涂层很好地附着。  \n[0010] 所述非极性塑料基材为表面能较低的基材，包括PMMA、PS、PE、PP中的一种。[0011] 所述原液A的各组分及含量如下：  \n[0012] 环氧丙烯酸酯树脂70‑80份，  \n[0013] 丙烯酸酯15‑25份，  \n[0014] 光引发剂3‑5份，  \n[0015] 溶剂0‑200份；  \n[0016] 环氧丙烯酸酯树脂属于高附着力光固化树脂，容易咬噬基材，与基材有高结合力的树脂，具有低收缩性和低官能度。  \n[0017] 本发明中，环氧丙烯酸酯树脂分子量为5000‑20000。  \n[0018] 所述丙烯酸树脂的制备方法为，将环氧丙烯酸酯与二元酸溶于乙酸乙酯中，四丁基溴化铵作为催化剂，加热至 $80^{\\circ}\\mathrm{C}-120^{\\circ}\\mathrm{C}$ 反应6‑8h制得。  \n[0019] 其中，环氧丙烯酸酯与二元酸的比例为1：1.1‑1：1.4，所述环氧丙烯酸酯包括双酚A环氧丙烯酸酯(E51)、甲基丙烯酸缩水甘油酯(GMA)中的一种或多种，所述二元酸包括己二酸、丁二酸、衣康酸中的一种或多种。  \n[0020] 所述丙烯酸酯含双键、低表面张力、低收缩，能与丙烯酸树脂交联，包括烷氧化丙烯酸苯氧酯(OEPA)、丙烯酸辛酯、丙烯酸葵酯、三羟甲基丙烷三丙烯酸酯(TMPTA)中的一种或多种。  \n[0021] 所述光引发剂在紫外光的照射下可用于引发烯类、双烯类单体的自由基聚合反应，包含2‑羟基‑2‑甲基‑1‑苯基丙酮(1173)，1‑羟基环己基苯基甲酮(184)，2 ,4 ,6‑三甲基苯甲酰基‑二苯基氧化膦(TPO) ，2‑甲基‑2‑(4‑吗啉基)‑1‑[4‑(甲硫基)苯基]‑1‑丙酮(907)，苯甲酰甲酸甲酯(MBF)，二苯甲酮中的一种或多种；所述溶剂为乙醇、异丙醇、乙酸丁酯、乙酸乙酯、乙酸丙酯、正丁醚中的一种或多种。  \n[0022] 原液A的制备方法为：准确称取各组分，将环氧丙烯酸酯树脂，丙烯酸酯，加入溶剂混合搅拌，再加入光引发剂，混合后制得。  \n[0023] 原液A的涂覆方式为喷涂、淋涂、滴涂、刮涂或滚涂中的一种。  \n[0024] 原液A涂层的制备方法为将原液A涂覆在板材上， $60-80^{\\circ}\\mathrm{C}$ 预烘 $1-3\\mathrm{{min}}$ ，紫外LED灯光固化20‑30s，能量为 $400{-}800\\mathrm{mJ/cm^{2}}$ 。  \n[0025] 使用百格测试法测得原液A涂层的附着力为0级。  \n[0026] 所述原液B的各组分及含量如下：  \n[0027] 光固化亲水树脂60‑70份，  \n[0028] 光固化亲水小分子10‑20份，  \n[0029] 光固化亲水盐10‑20份，  \n[0030] 光引发剂3‑5份，  \n[0031] 溶剂0‑200份；  \n[0032] 所述光固化亲水树脂包括聚乙二醇二丙烯酸酯(PEG400DA)，聚乙二醇二丙烯酸酯  \n\n(PEG600DA)，聚乙二醇二丙烯酸酯(PEG1000DA)中的一种或多种。  \n\n[0033] 所述光固化亲水小分子包括丙烯酸、甲基丙烯酸、丙烯酸羟乙酯、三羟甲基丙烷三丙烯酸酯(TMPTA)中的一种或多种。  \n[0034] 所述光固化亲水盐包括烯丙氧基壬基酚丙醇聚氧乙烯醚硫酸铵(DNS‑86)，2‑丙烯酰胺‑2‑甲基丙磺酸(AMPS)中的一种或多种。  \n[0035] 所述光引发剂包括2‑羟基‑2‑甲基‑1‑苯基丙酮(1173)，1‑羟基环己基苯基甲酮(184)，2 ,4 ,6‑三甲基苯甲酰基‑二苯基氧化膦(TPO)，2‑甲基‑2‑(4‑吗啉基)‑1‑[4‑(甲硫基)苯基]‑1‑丙酮(907)，苯甲酰甲酸甲酯(MBF)，二苯甲酮中的一种或多种；  \n[0036] 所述溶剂为乙醇、异丙醇、乙酸丁酯、乙酸乙酯、乙酸丙酯、正丁醚中的一种或多种。  \n[0037] 原液B的制备方法为：准确称取各组分，将光固化亲水树脂，光固化亲水小分子，光固化亲水盐加入溶剂混合搅拌 $10-20\\mathrm{{min}}$ ，再加入光引发剂，混合0.5‑1h后制得。  \n[0038] 原液B的涂覆方式和原液A一样，为喷涂、淋涂、滴涂、刮涂或滚涂中的一种。[0039] 原液B涂层的制备方法为将原液B涂覆在板材上， $60-80^{\\circ}\\mathrm{C}$ 预烘 $1-3\\mathrm{{min}}$ ，紫外LED灯光固化60‑120s，能量为 $400{-}800\\mathrm{mJ/cm^{2}}$ 。  \n[0040] 使用百格测试法测得原液B涂层的附着力为0级。  \n[0041] 使用水接触角测试仪测得原液B涂层的水接触角为 $8-15^{\\circ}$ °。  \n[0042] 本发明涂层所选基材为聚甲基丙烯酸甲酯(PMMA)、聚苯乙烯(PS)、聚乙烯(PE)、聚丙烯(PP)。  \n[0043] 本发明制备的紫外光固化耐摩擦防雾涂层，通过水接触角测试与起雾测试来检测涂层防雾性能。  \n[0044] 本发明中紫外光固化耐摩擦防雾涂层耐磨性能通过耐磨擦试验机测试。  \n[0045] 所述紫外光固化耐摩擦防雾涂层进行高温加速老化试验，将测试样品放入至100$\\mathrm{{^\\circC}}$ 烘箱，测试1500‑2000小时，测试老化前后涂层无明显脱落、剥离、起皱现象。  \n[0046] 所述紫外光固化耐摩擦防雾涂层进行耐盐腐蚀测试， $5\\%$ 氯化钠溶液浸泡500‑800小时，老化前后涂层无明显脱落、剥离、起皱现象。  \n[0047] 所述紫外光固化耐摩擦防雾涂层进行耐高湿测试，将样品放在 $85\\%-95\\%$ 湿度的空气中2000‑3000小时，老化前后涂层无明显脱落、剥离、起皱现象。  \n[0048] 所述紫外光固化耐摩擦防雾涂层进行环境测试，将样品放置于露天环境0.5‑1年，老化前后涂层无明显脱落、剥离、起皱现象。  \n[0049] 本发明与现有技术相比，本发明具有如下的有益效果：  \n[0050] 1 .本发明因采用双层涂层，第一层涂层与基材能很好地附着，第二层有较好的防雾性能。因此能在兼顾涂层防雾性能的同时保证涂层有很好的附着力和耐久性。  \n[0051] 2.原液A是以环氧丙烯酸酯树脂以主要原料，在各种基材上有良好的附着力，同时能与原液B交联固化，使得双层涂层有良好的机械性能。  \n[0052] 3.原液B的主要成分为光固化亲水树脂、光固化亲水小分子、光固化亲水盐，三者可以互相交联，形成互穿网络结构，具有良好的机械性能，同时使得涂层表面富含丰富的亲水基团，使涂层防雾性能大大提升。  \n[0053] 4.与单层涂层相比，双层涂层更容易实现附着力与防雾性能的平衡  \n\n[0054] 5.与单层涂层相比，双层涂层具有更好的机械性能。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 具体实施方式  \n\n[0055] 下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。  \n\n[0056] 实施例1  \n\n[0057] 1.1制备环氧丙烯酸酯树脂：将1mol甲基丙烯酸缩水甘油酯(GMA)与1.1mol己二酸溶于乙酸乙酯中， $0.05\\mathrm{mol}$ 四丁基溴化铵作为催化剂，加热至 $80^{\\circ}\\mathrm{C}$ 反应6h制得。  \n\n[0058] 1.2制备原液A，各组分及重量份如下：  \n\n[0059] 一坏氧内烯酸酯树脂70份、0EPA作为内烯酸酯25份和1173作为元引发剂5份；溶剂米用乙酸丁酯：异丙醇：乙醇 $=4:3:3$ (体积比)，总重量是其它组分总重量的0.3倍  \n\n[0060] 准确称取上述组分，将环氧丙烯酸酯树脂和OEPA，加入溶剂混合搅拌10min，再加入光引发剂，混合0.5h后制得。  \n\n[0061] 1.3涂层A的制备  \n\n[0062] 将上述制备得到的原液A涂覆在板材上， $60^{\\circ}\\mathrm{C}$ 预烘2min，紫外LED灯光固化30s，能量为 $400\\mathrm{{mJ/cm}^{2}}$ 。  \n\n[0063] 采用ISO2409‑1992标准的百格测试法，测试涂层的附着力为0级。  \n\n[0064] 1.4制备原液B，各组分及重量份如下：  \n\n[0065] PEG400DA作为光固化亲水树脂60份、丙烯酸作为光固化亲水小分子20份、DNS86作为光固化亲水盐15份、1173作为光引发剂5份；溶剂采用乙酸丁酯：异丙醇：乙醇 $=4{:}3{:}3$ (体积比)，总重量是其它组分总重量的1倍。  \n\n[0066] 准确称取各组分，将PEG400DA，丙烯酸，DNS86加入溶剂混合搅拌10min，再加入1173，混合0.5h后制得。  \n\n[0067] 1.5涂层B的制备  \n\n[0068] 将上述制备得到的原液B涂覆在已涂覆原液A的板材上， $80^{\\circ}\\mathrm{C}$ 预烘1min，紫外LED灯光固化60s，能量为 $400\\mathrm{{mJ/cm}^{2}}$ 。  \n\n[0069] 采用ISO2409‑1992标准的百格测试法，测试涂层的附着力为0级。  \n\n[0070] 实施例2  \n\n[0071] 2.1制备环氧丙烯酸酯树脂：将1mol双酚A环氧丙烯酸酯(E51)与 $1.2\\mathrm{mol}$ 丁二酸溶于乙酸乙酯中， $0.05\\mathrm{mol}$ 四丁基溴化铵作为催化剂，加热至 $100^{\\circ}\\mathrm{C}$ 反应7h制得。  \n\n[0072] 2.2制备原液A，各组分及重量份如下：  \n\n[0073] 环氧丙烯酸酯树脂80份、丙烯酸辛酯作为丙烯酸酯17份和184作为光引发剂3份；  \n溶剂采用乙酸丁酯：异丙醇：乙醇 $=4:3:3$ (体积比)，总重量是其它组分总重量的1.5倍。  \n\n[0074] 准确称取上述组分，将环氧丙烯酸酯树脂和丙烯酸辛酯，加入溶剂混合搅拌10min，再加入光引发剂184，混合0.5h后制得。  \n\n[0075] 2.3涂层A的制备  \n\n[0076] 将上述制备得到的原液A涂覆在板材上， $80^{\\circ}\\mathrm{C}$ 预烘1min，紫外LED灯光固化25s，能  \n\n量为 $700\\mathrm{{mJ/cm}^{2}}$ 。  \n\n[0077] 采用ISO2409‑1992标准的百格测试法，测试涂层的附着力为0级。  \n\n[0078] 2.4制备原液B，各组分及重量份如下：  \n\n[0079] PEG600DA作为光固化亲水树脂70份、甲基丙烯酸作为光固化亲水小分子10份、AMPS作为光固化亲水盐17份、184作为光引发剂3份；溶剂采用乙酸丁酯：异丙醇：乙醇 $=4$ ：3：3(体积比)，总重量是其它组分总重量的3倍。  \n[0080] 准确称取各组分，将PEG600DA，甲基丙烯酸，DNS86加入溶剂混合搅拌20min，再加入184，混合1h后制得。  \n[0081] 2.5涂层B的制备  \n[0082] 将上述制备得到的原液B涂覆在已涂覆原液A的板材上， $60^{\\circ}\\mathrm{C}$ 预烘3min，紫外LED灯光固化100s，能量为 $800\\mathrm{mJ/cm}^{2}$ 。  \n[0083] 采用ISO2409‑1992标准的百格测试法，测试涂层的附着力为0级。  \n[0084] 实施例3  \n[0085] 3.1制备环氧丙烯酸酯树脂：将1mol甲基丙烯酸缩水甘油酯(GMA)与1.4mol衣康酸溶于乙酸乙酯中， $0.05\\mathrm{mol}$ 四丁基溴化铵作为催化剂，加热至 $120^{\\circ}\\mathrm{C}$ 反应8h制得。  \n[0086] 3.2制备原液A，各组分及重量份如下：  \n[0087] 环氧丙烯酸酯树脂75份、丙烯酸葵酯作为丙烯酸酯20份和二苯甲酮作为光引发剂5份；溶剂采用乙酸丁酯：异丙醇：乙醇 $=4:3:3$ (体积比)，总重量是其它组分总重量的2.8倍。  \n[0088] 准确称取上述组分，将环氧丙烯酸酯树脂和丙烯酸葵酯，加入溶剂混合搅拌10min，再加入二苯甲酮，混合0.5h后制得。  \n[0089] 3.3涂层A的制备  \n[0090] 将上述制备得到的原液A涂覆在板材上， $60^{\\circ}\\mathrm{C}$ 预烘3min，紫外LED灯光固化20s，能量为 $500\\mathrm{mJ/cm^{2}}$ 。  \n[0091] 采用ISO2409‑1992标准的百格测试法，测试涂层的附着力为0级。  \n[0092] 3.4制备原液B，各组分及重量份如下：  \n[0093] PEG1000DA作为光固化亲水树脂65份、丙烯酸羟乙酯作为光固化亲水小分子20份、DNS86作为光固化亲水盐10份、二苯甲酮作为光引发剂4份；溶剂采用乙酸丁酯：异丙醇：乙醇 $=4{:}3{:}3$ (体积比)，总重量是其它组分总重量的0.5倍。  \n[0094] 准确称取各组分，将PEG1000DA，丙烯酸羟乙酯，DNS86加入溶剂混合搅拌10min，再加入二苯甲酮，混合1h后制得。  \n[0095] 3.5涂层B的制备  \n[0096] 将上述制备得到的原液B涂覆在已涂覆原液A的板材上， $75\\mathrm{{^\\circC}}$ 预烘1 .5min，紫外LED灯光固化120s，能量为 $400\\mathrm{{mJ/cm}^{2}}$ 。  \n[0097] 采用ISO2409‑1992标准的百格测试法，测试涂层的附着力为0级。  \n[0098] 性能测试  \n[0099] 将实施例1‑3中所得的涂层通过水接触角测试仪进行水接触角测试，水接触角在$8^{-}18^{\\circ}$ °之间。  \n[0100] 将实施例1‑3中所得的防雾涂层通过水浴锅熏蒸测试来检测涂层防雾性能。将水浴锅中的水加热至 $65\\mathrm{-}70^{\\circ}\\mathrm{C}$ ，涂覆有防雾涂层的样品放置在水浴锅上方10cm处熏蒸10s，所有样品均无起雾现象。  \n[0101] 将实施例1‑3中所得的防雾涂层通过耐磨擦试验机测试耐磨性能。砝码为 $200\\mathrm{g}$ ，测试工具为羊毛毡，循环擦拭10000次涂层无明显脱落、剥离、起皱且防雾性能无衰减。[0102] 将实施例1‑3中所得的防雾涂层进行高温加速老化试验，将测试样品放入至 $100^{\\circ}\\mathrm{C}$ 烘箱，测试1500‑2000小时，测试老化前后涂层无明显脱落、剥离、起皱现象。  \n[0103] 将实施例1‑3中所得的防雾涂层进行耐盐腐蚀测试， $5\\%$ 氯化钠溶液浸泡500‑800小时，老化前后涂层无明显脱落、剥离、起皱现象。  \n[0104] 将实施例1‑3中所得的防雾涂层进行耐高湿测试，将样品放在 $85\\%-95\\%$ 湿度的空气中2000‑3000小时，老化前后涂层无明显脱落、剥离、起皱现象。  \n[0105] 将实施例1‑3中所得的防雾涂层进行环境测试，将样品放置于露天环境0.5‑1年，老化前后涂层无明显脱落、剥离、起皱现象。",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,47 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n<html><body><table><tr><td colspan=\"3\">(21)申请号 202111012076.2 (51)Int.Cl.</td></tr><tr><td colspan=\"2\">(22)申请日2021.08.31</td><td>C08G 18/12 (2006.01)</td></tr><tr><td colspan=\"2\">(65)同一申请的已公布的文献号</td><td>C08G 18/66 (2006.01)</td></tr><tr><td colspan=\"2\">申请公布号CN 113603850 A</td><td>C08G 18/48 (2006.01)</td></tr><tr><td colspan=\"2\"></td><td>C08G 18/67 (2006.01)</td></tr><tr><td colspan=\"2\">(43)申请公布日2021.11.05</td><td>C08G 18/61(2006.01)</td></tr><tr><td colspan=\"2\">(73)专利权人武汉中科先进材料科技有限公司</td><td>CO8G 18/32 (2006.01)</td></tr><tr><td colspan=\"2\">地址 430000 湖北省武汉市武汉经济技术</td><td>C09D 175/16 (2006.01)</td></tr><tr><td colspan=\"2\">开发区206M地块华中电子商务产业园</td><td>审查员 窦海方</td></tr><tr><td colspan=\"2\">A6栋1-6层</td><td></td></tr><tr><td colspan=\"2\">(72)发明人康翼鸿喻学锋程文杰杨新耕 吴列</td><td></td></tr><tr><td colspan=\"2\"></td><td></td></tr><tr><td colspan=\"2\">(74)专利代理机构武汉高得专利代理事务所</td><td></td></tr><tr><td colspan=\"2\">（普通合伙）42268 专利代理师姜璐</td><td></td></tr></table></body></html>",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n一种高耐磨亲水树脂、一种高耐磨无溶剂防雾涂料及其制备方法和应用",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明公开了一种高耐磨亲水树脂、一种高耐磨无溶剂防雾涂料及其制备方法和应用，该防雾涂料包括以下组份：所述高耐磨亲水树脂、疏水树脂、活性稀释剂、光引发剂和助剂；所述亲水树脂为本发明设计得到的可UV固化的亲水聚合物。本发明通过设计一种具有高耐磨的亲水性树脂，将其应用到防雾配方中得到高耐磨无溶剂防雾涂料，该涂料安全无毒，能够在多种类型的基材上成膜，在紫外光照射下可实现快速固化，与基材的粘接强度高，形成的涂层具有良好的透明度、耐磨性和耐化学品性，并具有优异的防雾性能。  \n\n1.一种高耐磨亲水树脂，其特征在于：先将高硬度单体与二乙醇胺按照摩尔比1：1‑1：8反应得到亲水改性的预聚体1，然后将含羟基的混合物与二异氰酸酯按照羟基(‑OH)与异氰酸酯(‑NCO)摩尔比1：1反应得到部分封端的预聚体2，最后将预聚体1和预聚体2按照摩尔比1：1‑1：24混合反应生成得到高耐磨亲水树脂；所述高硬度单体包括异氰脲酸三丙烯酸酯、双季戊四醇六丙烯酸酯、丙烯酰氧丙基笼型聚倍半硅氧烷、八环氧环己基乙基笼状聚倍半硅氧烷、缩水甘油醚氧丙基笼状聚倍半硅氧烷中的至少一种；所述含羟基的混合物由亲水表面活性剂和羟基丙烯酸酯单体按照1:1‑1:4的比例混合而成；所述亲水表面活性剂为非离子的具有聚氧乙烯片段的单羟基聚合物，单羟基聚合物包括分子量400‑1000的聚乙二醇单甲醚、壬基酚聚氧乙烯醚、辛基酚聚氧乙烯醚中的至少一种。  \n\n2.根据权利要求1所述的高耐磨亲水树脂，其特征在于：所述羟基丙烯酸酯单体包括甲基丙烯酸羟乙酯(HEMA)、丙烯酸羟乙酯(HEA)、丙烯酸羟丙酯(HPA)、4‑羟基丁基丙烯酸酯(4HBA)、季戊四醇三丙烯酸酯(PETA)中的至少一种。  \n\n3.根据权利要求1所述的高耐磨亲水树脂，其特征在于：所述二异氰酸酯包括异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、六亚甲基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(HMDI)、改性二苯基甲烷二异氰酸酯(液化MDI)中的至少一种。  \n\n4.一种高耐磨无溶剂防雾涂料，其特征在于，由以下质量份的组份制成：亲水树脂2050份，疏水树脂30‑70份，活性稀释剂单体5‑20份，光引发剂3‑5份，流平剂0.5‑1.0份；所述亲水树脂为权利要求 $1{\\sim}3$ 任一项所述高耐磨亲水性树脂；所述疏水树脂为至少六个官能度的聚氨酯丙烯酸酯，包括氰特EB1290、帝斯曼2421、帝斯曼242、长兴6145‑100、长兴6195‑100中的至少一种；所述活性稀释剂单体包括三羟甲基丙烷三丙烯酸酯(TMPTA)、乙氧基化三羟甲基丙烷三丙烯酸酯(ETPTA)、季戊四醇三丙烯酸酯(PETA)、双季戊四醇六丙烯酸酯(DPHA)、丙烯酰吗啉(ACMO)、聚乙二醇400二丙烯酸酯(PEG400DA)、聚乙二醇600二丙烯酸酯(PEG600DA)、聚乙二醇1000二丙烯酸酯(PEG1000DA)中的至少一种。  \n\n5.一种高耐磨无溶剂防雾涂料的制备方法，其特征在于，包括以下步骤：将20‑50份权利要求 $1{\\sim}3$ 任一项所述的高耐磨亲水树脂，30‑70份疏水树脂，5‑20份活性稀释剂单体，3‑5份光引发剂和0.5‑1.0份流平剂分散混合，即可得到所述防雾涂料。  \n\n6.根据权利要求5所述的高耐磨无溶剂防雾涂料的制备方法，其特征在于，  \n\n在容器内先加入所述活性稀释剂单体，在搅拌状态下依次加入光引发剂、亲水树脂、疏水树脂和流平剂并搅拌，得到高耐磨无溶剂防雾涂料。  \n\n7.一种根据权利要求4所述高耐磨无溶剂防雾涂料在制备防雾涂层中的应用。  \n\n8.一种防雾涂层，其特征在于，由以下方法制备得到：将根据权利要求4所述高耐磨无溶剂防雾涂料涂覆在基质上，经固化后形成所述防雾涂层。  \n\n9.根据权利要求8所述的防雾涂层，其特征在于，所述基质包括玻璃、塑料、金属。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 一种高耐磨亲水树脂、一种高耐磨无溶剂防雾涂料及其制备方法和应用",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明属于涂料技术领域，具体涉及一种高耐磨亲水树脂、一种高耐磨无溶剂防雾涂料及其制备方法和应用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 高透明材料是我们日常生活生产中不可缺少的材料，但其在使用过程中易出现结雾现象，造成材料表面的透光率降低，影响视线，给生活带来了诸多不便，甚至造成严重危害。近年来防雾技术逐步受到人们的重视，以亲水型防雾涂层的研发进展最快，已经形成了一系列先进的技术和相对成熟的产品，如光学透镜、汽车显示屏、护目镜、面罩、头盔面板等。亲水防雾涂料是一种功能性材料，它是以具有亲水基团的高分子材料为主要成分，配以相应比例的其他助剂和有机溶剂调配而成的具有防雾功能的化工产品，是现阶段防雾的最有效途径之一。  \n\n[0003] 为了提高防雾涂料的耐磨性，目前的防雾技术中，通常向防雾配方中添加“硬质”耐磨材料作为保护性涂层施涂来防止涂层的刮伤或者损坏。例如：CN106752623B合成了主链含硅烷偶联剂(MPS)、甲基丙烯酸缩水甘油酯(GMA)和磺酸基亲水单体(AMPS)的聚丙烯酸酯，采用正硅酸乙酯(TE0S)和三乙烯四胺作为固化剂，分别与主链硅氧烷基和环氧基团反应提升交联密度及耐磨性；CN101591494B使用氮丙啶交联剂与聚丙烯酸酯主链上的羧基反应提高交联度及涂层的耐磨性；但是以上体系需要混合后不久就施涂到基底如透明玻璃或者塑料基材上，凝胶时间短，使用不便。CN102086348B使用封闭型聚氨酯延长凝胶反应时间，但是制备方法复杂，解封闭反应难以完全进行，影响了涂层的性能。以上防雾配方中均添加有机溶剂充当分散介质来降低体系黏度，增强体系稳定性，利于流平，便于涂布工艺操作。但有机溶剂会对环境和生物体造成危害，不利于绿色可持续发展。综上，现有报道都难以得到无溶剂、耐磨性好、防雾性能优异的涂层。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0004] 为了解决上述背景技术中提出的技术问题，本发明的目的是提供一种高耐磨无溶剂防雾涂料，不含有机溶剂，涂布完毕后可直接UV固化，能够在多种类型的基材上成膜，在紫外光照射下可实现快速固化，与基材的粘接强度高，形成的涂层具有良好的透明度、耐磨性和耐化学品性，并具有优异的防雾性能。  \n\n[0005] 为了达到上述目的，本发明所采用的技术方案为：  \n\n[0006] 一方面，本发明提供一种高耐磨亲水性树脂，先将高硬度单体与二乙醇胺按照摩尔比1：1‑1：8反应得到亲水改性的预聚体1，然后将含羟基的混合物与二异氰酸酯按照羟基(‑OH)与异氰酸酯(‑NCO)摩尔比1：1反应得到部分封端的预聚体2，最后将预聚体1和预聚体2按照摩尔比1：1‑1：24混合反应而成。  \n\n[0007] 所述的高硬度单体包括异氰脲酸三丙烯酸酯、双季戊四醇六丙烯酸酯、丙烯酰氧丙基笼型聚倍半硅氧烷、八环氧环己基乙基笼状聚倍半硅氧烷、缩水甘油醚氧丙基笼状聚倍半硅氧烷中的至少一种；  \n\n[0008] 所述的含羟基的混合物由亲水表面活性剂和羟基丙烯酸酯单体按照1:1‑1:4的比例混合而成；  \n\n[0009] 所述亲水表面活性剂为非离子的具有聚氧乙烯片段的单羟基聚合物。  \n\n[0010] 进一步地，所述单羟基聚合物包括聚乙二醇单甲醚(分子量400‑1000)、壬基酚聚氧乙烯醚、辛基酚聚氧乙烯醚中的至少一种；  \n\n[0011] 优选地，所述羟基丙烯酸酯单体包括甲基丙烯酸羟乙酯(HEMA)、丙烯酸羟乙酯(HEA)、丙烯酸羟丙酯(HPA)、4‑羟基丁基丙烯酸酯(4HBA)、季戊四醇三丙烯酸酯(PETA)中的至少一种；  \n\n[0012] 优选地，所述二异氰酸酯包括异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、六亚甲基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(HMDI)、改性二苯基甲烷二异氰酸酯(液化MDI)中的至少一种；  \n\n[0013] 生成预聚体2的反应中还添加有催化剂、阻聚剂和抗氧剂，其中优选的催化剂为二月桂酸二丁基锡，阻聚剂为对羟基苯甲醚，抗氧剂为2,6‑二叔丁基‑4‑甲基苯酚。  \n\n[0014] 再一方面，本发明提供了一种高耐磨无溶剂防雾涂料，由以下质量份的组份制成：亲水树脂20‑50份，疏水树脂30‑70份，活性稀释剂单体5‑20份，光引发剂3‑5份，流平剂0.5‑1.0份；所述亲水树脂为上述所述的高耐磨的亲水性树脂；  \n\n[0015] 优选地，所述疏水树脂为至少六个官能度的聚氨酯丙烯酸酯，包括氰特EB1290、帝斯曼2421、帝斯曼242、长兴6145‑100、长兴6195‑100中的至少一种。  \n\n[0016] 优选地，所述活性稀释剂单体包括三羟甲基丙烷三丙烯酸酯(TMPTA)、乙氧基化三羟甲基丙烷三丙烯酸酯(ETPTA)、季戊四醇三丙烯酸酯(PETA)、双季戊四醇六丙烯酸酯(DPHA)、丙烯酰吗啉(ACMO)、聚乙二醇400二丙烯酸酯(PEG400DA)、聚乙二醇600二丙烯酸酯(PEG600DA)、聚乙二醇1000二丙烯酸酯(PEG1000DA)中的至少一种；  \n\n[0017] 优选地，所述光引发剂为夺氢型光引发剂；优选地，所述光引发剂包括光引发剂1173、TPO、BP、184、907中的至少一种。  \n\n[0018] 优选地，所述流平剂包括氟素润湿流平剂FSWET1010、含氟流平剂FS3100、聚醚硅氧烷流平剂TEGO410中的至少一种。  \n\n[0019] 无溶剂配方黏度控制主要在于活性稀释剂，合成的高耐磨亲水树脂黏度不高，是由于亲水树脂的合成采用的仅是简单的接枝反应，不涉及2‑2官能度缩合体系的扩链反应，树脂没有结构单元，就是几种反应原料的分子量相加之和。进一步地，亲水树脂中的链结构与活性稀释剂结构高度一致，更容易被活性稀释剂稀释。活性稀释剂除了起到稀释作用，还起到耐磨和亲水的作用，即本身活性稀释剂分两种，亲水型的和耐磨型的，亲水活性稀释剂起到提高亲水的作用，耐磨型起到提高耐磨的作用。列举的活性稀释剂中，三羟甲基丙烷三丙烯酸酯(TMPTA)、乙氧基化三羟甲基丙烷三丙烯酸酯(ETPTA)、季戊四醇三丙烯酸酯(PETA)、双季戊四醇六丙烯酸酯(DPHA)属于耐磨型；丙烯酰吗啉(ACMO)、聚乙二醇400二丙烯酸酯(PEG400DA) 、聚乙二醇600二丙烯酸酯(PEG600DA) 、聚乙二醇1000二丙烯酸酯(PEG1000DA)属于亲水型。  \n\n[0020] 上述所述的无溶剂高耐磨防雾涂料的制备方法，包括以下步骤：将20‑50份高耐磨亲水树脂，30‑70份疏水树脂，5‑20份活性稀释剂，3‑5份光引发剂和0.5‑1.0份流平剂分散混合，即可得到所述防雾涂料；  \n\n[0021] 优选地，具体包括以下步骤：在容器内加入所述活性稀释剂，在搅拌状态下依次加入光引发剂、亲水树脂、疏水树脂和流平剂并搅拌，得到所述防雾涂料。  \n\n[0022] 本发明再一方面提供了一种上述所述的防雾涂料在制备防雾涂层中的应用。  \n\n[0023] 本发明再一方面提供了一种防雾涂层，由以下方法制备得到：将上述所述的防雾涂料涂覆在基质上，经固化后形成所述防雾涂层；  \n\n[0024] 优选地，所述基质包括玻璃、塑料、金属，具体包括汽车玻璃，建筑物玻璃，广告牌，浴室镜及公共交通工具玻璃，铁板，铜板及铝合金板；  \n\n[0025] 优选地，所述涂覆的方法包括刮涂、滴涂、辊涂、淋涂、旋涂；  \n[0026] 优选地，所述固化的方法经200‑2000mJ紫外光固化。  \n\n[0027] 本发明从原料上选择耐磨的高硬度单体，其既具备高硬度，又具备高的官能度(官能度大于等于3)，利用二乙醇胺与双键或环氧基团的反应对其进行改性，使得高硬度单体每牺牲一个官能度，都新增两个羟基取而代之，形成亲水改性的预聚体1；最后使预聚体1的羟基和预聚体2的‑NCO发生接枝反应，最后形成耐磨的亲水树脂。通过调节含羟基的混合物中亲水表面活性剂和羟基丙烯酸酯单体的用量比，可以调整接枝到预聚体1上的双键和亲水链段的比例，提高官能度，该方法可以使最终形成耐磨的亲水树脂仍然保持高硬度单体的耐磨结构，又能够调节耐磨与亲水性的平衡，使之UV固化时同时具备优异的耐磨性和持续的亲水防雾性能。  \n\n[0028] 本发明的有益效果是：本发明设计了一种可UV固化的兼具防雾和耐磨功能的亲水聚合物，将其应用到防雾涂料配方中得到本申请保护的防雾涂料，防雾涂料不含溶剂，安全无毒，能够在多种类型的基材上成膜，在紫外光下可实现瞬时固化，可应用于连续工业化生产，形成的涂层与基材的粘接强度高，形成的涂层具有良好的透明度、高硬度、耐划伤性和耐化学品性，并具有优异的防雾效果、防雾持久性、良好的耐水性、低粘性。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 具体实施方式  \n\n[0029] 为了更好地理解本发明的内容，通过以下具体实施方式对本发明作进一步详细说明，应理解为，以下实施方式仅为对本发明的说明，不是对本发明内容的限制，任何对本发明内容未作实质性变更的技术方案仍落入本发明的保护范围。  \n\n[0030] 下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。  \n\n[0031] 实施例1  \n\n[0032] 一、高耐磨亲水树脂的制备：  \n\n[0033] (a) $100\\mathrm{mL}$ 的三口烧瓶中加入 $8.46\\mathrm{g}\\left(0.02\\mathrm{mol}\\right)$ 异氰脲酸三丙烯酸酯和 $4.2\\mathrm{g}$ $\\left(0.04\\mathrm{mol}\\right)$ 二乙醇胺，开启搅拌并升温至 $65^{\\circ}\\mathrm{C}$ 反应2h得到亲水改性的预聚体1；  \n\n[0034] (b)另取100mL的三口烧瓶，加入 $17.78\\mathrm{g}\\left(0.08\\mathrm{mol}\\right)$ 异佛尔酮二异氰酸酯和 $0.021\\mathrm{g}$ $(0.05\\mathrm{wt}\\%)$ 二月桂酸二丁基锡开启搅拌；另依次称取 $0.11\\mathrm{g}\\left(0.262\\mathrm{wt}\\%\\right)$ 对羟基苯甲醚，$0.22\\mathrm{g}\\left(0.525\\mathrm{wt\\%}\\right)2,6^{-}$ 二叔丁基‑4‑甲基苯酚以及 $24.0\\mathrm{g}\\left(0.04\\mathrm{mol}\\right)$ 聚乙二醇单甲醚600和$11.92\\mathrm{g}\\left(0.04\\mathrm{mol}\\right)$ 季戊四醇三丙烯酸酯(PETA)，充分混合至完全溶解，转移至恒压滴液漏斗中，在室温下缓慢滴加至上述三口烧瓶中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $60^{\\circ}\\mathrm{C}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值(通过盐酸二正丁胺法测定)，降温得到部分封端的预聚体2，干燥密封保存；二月桂酸二丁基锡DBTDL、对羟基苯甲醚MEHQ、2,6‑二叔丁基‑4‑甲基苯酚BHT都是常规选择，对性能没有影响，起到催化剂和阻聚剂的作用。  \n\n[0035] (c)将预聚体1和预聚体2混合，升温至 $70\\mathrm{{^\\circC}}$ 反应3h得到官能度为7的高耐磨的亲水性树脂。  \n\n[0036] 二、防雾涂料的制备：  \n\n[0037] (d)在高速分散机料筒容器内加入15份双季戊四醇六丙烯酸酯(DPHA)、4份聚乙二醇400二丙烯酸酯(PEG400DA)和5份光引发剂TPO，开动搅拌高速分散溶解后，依次加入45份高耐磨的亲水性树脂，30份疏水树脂帝斯曼2421，1份流平剂TEGO410搅拌均匀，得到所述防雾涂料。  \n\n[0038] 三、UV防雾涂层的制备：(e)UV防雾涂层的制备：将(d)中制备的防雾涂料用线棒均匀刮涂在PC板上，然后放在传送带式UV固化机上，经 $1000\\mathrm{mJ}$ 紫外光固化得防雾涂层。  \n\n[0039] 实施例2  \n\n[0040] 一、高耐磨亲水树脂的制备：  \n\n[0041] (a)250mL的三口烧瓶中加入 $.40.11\\mathrm{g}\\left(0.03\\mathrm{mol}\\right)$ 缩水甘油醚氧丙基笼状聚倍半硅氧烷和 $25.23\\mathrm{g}\\left(0.24\\mathrm{mol}\\right)$ 二乙醇胺，开启搅拌并升温至 $65^{\\circ}\\mathrm{C}$ 反应2h得到亲水改性的预聚体1；  \n\n[0042] (b)另取 $500\\mathrm{mL}$ 的三口烧瓶，加入 $125.92\\mathrm{g}\\left(0.48\\mathrm{mol}\\right)$ 二环己基甲烷二异氰酸酯和$0.13\\mathrm{g}\\left(0.05\\mathrm{wt}\\%\\right)$ 二月桂酸二丁基锡开启搅拌；另依次称取 $.0.695\\mathrm{g}\\left(0.262\\mathrm{wt}\\%\\right)$ 对羟基苯甲醚， $1.39\\mathrm{g}\\left(0.525\\mathrm{wt\\%}\\right)2,6\\mathrm{-}$ 二叔丁基‑4‑甲基苯酚以及 $64.6\\mathrm{g}\\left(0.1\\mathrm{mol}\\right)$ 辛基酚聚氧乙烯醚(OP‑10)、 $40\\mathrm{g}\\left(0.08\\mathrm{mol}\\right)$ 聚乙二醇单甲醚500和 $34.83\\mathrm{g}\\left(0.3\\mathrm{mol}\\right)$ 丙烯酸羟乙酯，充分混合至完全溶解，转移至恒压滴液漏斗中，在室温下缓慢滴加至上述三口烧瓶中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $70^{\\circ}\\mathrm{C}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值(通过盐酸二正丁胺法测定)，降温得到部分封端的预聚体2，干燥密封保存；二月桂酸二丁基锡DBTDL、对羟基苯甲醚MEHQ、2,6‑二叔丁基‑4‑甲基苯酚BHT都是常规选择，对性能没有影响，起到催化剂和阻聚剂的作用。  \n\n[0043] (c)将预聚体1和预聚体2混合，升温至 $80^{\\circ}\\mathrm{C}$ 反应3h得到官能度为10的高耐磨的亲水性树脂。  \n\n[0044] 二、防雾涂料的制备：(d)在高速分散机料筒容器内加入10份乙氧基化三羟甲基丙烷三丙烯酸酯(ETPTA)和4份光引发剂TPO，开动搅拌高速分散溶解后，依次加入60份高耐磨的亲水性树脂，25份疏水树脂长兴6195‑100，1份流平剂FS3100搅拌均匀，得到所述防雾涂料。  \n\n[0045] 三、UV防雾涂层的制备：(e)UV防雾涂层的制备：将(d)中制备的防雾涂料用辊涂机辊涂在PMMA板上，然后放在传送带式UV固化机上，经 $600\\mathrm{{mJ}}$ 紫外光固化得防雾涂层。  \n\n[0046] 实施例3  \n\n[0047] 一、高耐磨亲水树脂的制备：  \n\n[0048] (a)100mL的三口烧瓶中加入 $17.35\\mathrm{g}$ (0 .03mol)双季戊四醇六丙烯酸酯和 $9.46\\mathrm{g}$ $\\left(0.09\\mathrm{mol}\\right)$ 二乙醇胺，开启搅拌并升温至 $65^{\\circ}\\mathrm{C}$ 反应2h得到亲水改性的预聚体1；  \n\n[0049] (b)另取 $250\\mathrm{mL}$ 的三口烧瓶，加入 $40.01\\mathrm{g}\\left(0.18\\mathrm{mol}\\right)$ 异佛尔酮二异氰酸酯和 $0.055\\mathrm{g}$ $(0.05\\mathrm{wt}\\%)$ 二月桂酸二丁基锡开启搅拌；另依次称取 $0.29\\mathrm{g}\\left(0.262\\mathrm{wt}\\%\\right)$ 对羟基苯甲醚，$0.58\\mathrm{g}\\left(0.525\\mathrm{wt}\\%\\right)2,6^{-}$ 二叔丁基‑4‑甲基苯酚以及 $59.4\\mathrm{g}\\left(0.09\\mathrm{mol}\\right)$ 壬基酚聚氧乙烯醚(TX‑10)和 $11.71\\mathrm{g}\\left(0.09\\mathrm{mol}\\right)$ 丙烯酸羟丙酯，充分混合至完全溶解，转移至恒压滴液漏斗中，在室温下缓慢滴加至上述三口烧瓶中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $60^{\\circ}\\mathrm{C}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值(通过盐酸二正丁胺法测定)，降温得到部分封端的预聚体2，干燥密封保存；二月桂酸二丁基锡DBTDL、对羟基苯甲醚MEHQ、2,6‑二叔丁基‑4‑甲基苯酚BHT都是常规选择，对性能没有影响，起到催化剂和阻聚剂的作用。  \n\n[0050] (c)将预聚体1和预聚体2混合，升温至 $70\\mathrm{{^\\circC}}$ 反应3h得到官能度为6的高耐磨的亲水性树脂。  \n\n[0051] 二、防雾涂料的制备：(d)在高速分散机料筒容器内加入20份双季戊四醇六丙烯酸酯(DPHA)和4份光引发剂TPO，开动搅拌高速分散溶解后，依次加入50份高耐磨的亲水性树脂，25份疏水树脂长兴6195‑100，1份流平剂FSWET1010搅拌均匀，得到所述防雾涂料。  \n\n[0052] 三、UV防雾涂层的制备：(e)UV防雾涂层的制备：将(d)中制备的防雾涂料滴涂在PC板上，然后放在传送带式UV固化机上，经 $1000\\mathrm{mJ}$ 紫外光固化得防雾涂层。  \n\n[0053] 实施例4  \n\n[0054] 一、高耐磨亲水树脂的制备：  \n\n[0055] (a)100mL的三口烧瓶中加入 $.39.63\\mathrm{g}\\left(0.03\\mathrm{mol}\\right)$ 丙烯酰氧丙基笼型聚倍半硅氧烷和$15.77\\mathrm{g}\\left(0.15\\mathrm{mol}\\right)$ 二乙醇胺，开启搅拌并升温至 $65^{\\circ}\\mathrm{C}$ 反应2h得到亲水改性的预聚体1；  \n\n[0056] (b)另取 $500\\mathrm{mL}$ 的三口烧瓶，加入 $45.28\\mathrm{g}\\left(0.26\\mathrm{mol}\\right)$ 甲苯二异氰酸酯(TDI)和 $0.1\\mathrm{g}$ $(0.05\\mathrm{wt}\\%)$ 二月桂酸二丁基锡开启搅拌；另依次称取 $0.54\\mathrm{g}\\left(0.262\\mathrm{wt}\\%\\right)$ 对羟基苯甲醚，$1.08\\mathrm{g}\\left(0.525\\mathrm{wt\\%}\\right)2,6\\AA$ 二叔丁基‑4‑甲基苯酚以及 $150\\mathrm{g}\\left(0.2\\mathrm{mol}\\right)$ 聚乙二醇单甲醚750和$17.88\\mathrm{g}\\left(0.06\\mathrm{mol}\\right)$ 季戊四醇三丙烯酸酯(PETA)，充分混合至完全溶解，转移至恒压滴液漏斗中，在室温下缓慢滴加至上述三口烧瓶中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $60^{\\circ}\\mathrm{C}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值(通过盐酸二正丁胺法测定)，降温得到部分封端的预聚体2，干燥密封保存；二月桂酸二丁基锡DBTDL、对羟基苯甲醚MEHQ、2,6‑二叔丁基‑4‑甲基苯酚BHT都是常规选择，对性能没有影响，起到催化剂和阻聚剂的作用。  \n\n[0057] (c)将预聚体1和预聚体2混合，升温至 $70^{\\circ}\\mathrm{C}$ 反应3h得到官能度为9的高耐磨的亲水性树脂。  \n\n[0058] 二、防雾涂料的制备：  \n\n[0059] (d)在高速分散机料筒容器内加入10份三羟甲基丙烷三丙烯酸酯(TMPTA)和4份光引发剂TPO，开动搅拌高速分散溶解后，依次加入60份高耐磨的亲水性树脂，25份疏水树脂帝斯曼242，1份流平剂FS3100搅拌均匀，得到所述防雾涂料。  \n\n[0060] 三、UV防雾涂层的制备：(e)UV防雾涂层的制备：将(d)中制备的防雾涂料旋涂在玻璃板上，然后放在传送带式UV固化机上，经 $600\\mathrm{{mJ}}$ 紫外光固化得防雾涂层。  \n\n[0061] 实施例5性能测试[0062] 实施例1‑4所制得的防雾涂层的性能测试项目和方法如下表所示：  \n\n<html><body><table><tr><td>项目</td><td>方法</td></tr><tr><td>铅笔硬度 附着力</td><td>通过铅笔硬度仪按照GB/T6739-1996中的规定进行</td></tr><tr><td></td><td>采用百格法，交叉划格形成10X10的小方格。用3M-610压 敏胶带紧密粘附于涂层表面，然后沿90度方向快速撕去胶带， 观测格子边缘的破坏程度</td></tr><tr><td>烧杯防雾测试</td><td>涂层置于70℃热水上方标准高度，面向水蒸气高达3分钟。 如果测试中形成连续的水膜，则不会再起雾。如果测试中起 雾，记录从开始测试到出现雾的时间</td></tr><tr><td>初始防雾</td><td>防雾测试中3分钟不起雾，则通过</td></tr><tr><td>哈气测试</td><td>朝涂层哈气，观察起雾情况</td></tr><tr><td>室温水浸泡-防雾 0063] 测试(冷水测试）</td><td>样品在室温水中浸泡12小时，取出，干燥12小时，进行烧 杯防雾测试</td></tr><tr><td>沸水浸泡-防雾测 试 (沸水测试)</td><td>样品在沸水中煮1小时，取出，冷却干燥12小时，进行烧杯 防雾测试</td></tr><tr><td>酒精擦拭测试</td><td>样品分别用无水乙醇浸泡过的布擦拭10次，观察防雾是否出 现下降，不下降则通过</td></tr><tr><td>钢丝绒测试（耐 划伤)</td><td>#0000钢丝绒，200克压力，擦10圈。1-2个划痕为优；5-10 个擦痕为良；多于10个擦痕为差。</td></tr><tr><td>防雾持久性测试</td><td>对涂层做长期测试，每天测试防雾性能，记录出现防雾性能 下降时的天数</td></tr><tr><td>粘性测试</td><td>用棉花擦样品表面，不残留纤维为光滑，残留纤维越多说明 越粘</td></tr></table></body></html>  \n\n[0064] 实施例1‑4所制得的防雾涂层的性能测试结果如下表所示：  \n\n<html><body><table><tr><td></td><td></td><td>实施例1</td><td>实施例2</td><td>实施例3</td><td>实施例4</td></tr><tr><td>固化所 需能量</td><td></td><td>1000mJ</td><td>600mJ</td><td>1000mJ</td><td>600mJ</td></tr><tr><td>初始防雾</td><td>3min不起雾，则通过</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>哈气</td><td>不起雾则通过</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>冷水测试</td><td>观察开始测试到出现雾 的时间</td><td>>180s</td><td>>180s</td><td>>180s</td><td>>180s</td></tr><tr><td>沸水测试</td><td>观察开始测试到出现雾 的时间</td><td>>180s</td><td>>180s</td><td>>180s</td><td>>180s</td></tr><tr><td>酒精擦拭</td><td>化学品布擦拭</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>铅笔硬度</td><td>铅笔测试仪</td><td>3H</td><td>4H</td><td>4H</td><td>9H</td></tr><tr><td>耐划伤</td><td>钢丝绒测试，记划痕数</td><td>良</td><td>优</td><td>良</td><td>优</td></tr><tr><td>附着力</td><td>划格</td><td>0级</td><td>0级</td><td>0级</td><td>0级</td></tr><tr><td>防雾持久性</td><td></td><td>180d</td><td>120d</td><td>180d</td><td>120d</td></tr><tr><td>粘性测试</td><td></td><td>光滑</td><td>光滑</td><td>光滑</td><td>光滑</td></tr></table></body></html>  \n\n[0066] 综上，本发明创造性的利用高硬度单体与二乙醇胺按照摩尔比1：1‑1：8反应得到亲水改性的预聚体1，然后将含羟基的混合物与二异氰酸酯按照羟基(‑OH)与异氰酸酯(‑NCO)摩尔比1：1反应得到部分封端的预聚体2，最后将预聚体1和预聚体2按照摩尔比1：1‑1：24混合反应形成可耐钢丝绒擦拭的高耐磨亲水树脂，可以生成理论最高达到24‑F预聚体(F代表官能度，24‑F为24个官能度，官能度越大，硬度越高)，大幅提高了涂膜的硬度，与疏水树脂，活性稀释剂，光引发剂和流平剂分散混合，非常适合用于刮涂、滴涂、辊涂、淋涂、旋涂等工艺，由于不含有机溶剂，涂布完毕后可直接UV固化，能够在多种类型的基材上成膜，在紫外光照射下可实现快速固化，与基材的粘接强度高，形成的涂层具有良好的透明度、耐磨性和耐化学品性，并具有优异的防雾性能。",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,47 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n<html><body><table><tr><td>(21)申请号 202110814663.7</td><td>(51) Int.CI .</td></tr><tr><td>(22)申请日 2021.07.19</td><td>C09D 4/06 (2006.01)</td></tr><tr><td>(65)同一申请的已公布的文献号</td><td>CO9D 4/02 (2006.01)</td></tr><tr><td>申请公布号CN113637345A</td><td>CO9D 7/62 (2018.01)</td></tr><tr><td></td><td>CO9D 7/20 (2018.01)</td></tr><tr><td>(43)申请公布日2021.11.12</td><td>C08G 18/62 (2006.01)</td></tr><tr><td>(73)专利权人武汉中科先进材料科技有限公司</td><td>C08G 18/48 (2006.01)</td></tr><tr><td>地址430000 湖北省武汉市武汉经济技术</td><td>(56)对比文件</td></tr><tr><td>开发区206M地块华中电子商务产业园 A6栋1-6层</td><td>WO 2004076566 A1,2004.09.10</td></tr><tr><td></td><td>US 2021071031 A1,2021.03.11</td></tr><tr><td>(72)发明人康翼鸿喻学锋李金堆边式 杨新耕吴列程文杰</td><td>审查员冯宁</td></tr><tr><td>(74)专利代理机构武汉高得专利代理事务所</td><td></td></tr><tr><td></td><td></td></tr><tr><td>（普通合伙）42268</td><td></td></tr><tr><td>专利代理师 美</td><td></td></tr></table></body></html>",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n一种水性环保耐磨型有机无机杂化防雾涂料及其制备",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明涉及防雾涂料领域，具体涉及一种水性环保耐磨型有机无机杂化防雾涂料。本发明以水性聚氨酯‑丙烯酸树脂和修饰后的 $\\mathrm{Ti0_{2}/S i0_{2}}$ 杂化微球为主体，复配以活性稀释剂，聚丙烯酰胺，流平剂等；该方法制备的涂料以水和醇为复合溶剂，挥发性有机化合物(VOC)含量低，属于环境友好型涂料。本发明提供的防雾涂料通过UV光固化后，涂层的硬度高，耐浸泡性能好，同时兼具耐磨性能和持久的防雾性能，适用于具有防雾需求的领域，如护目镜、泳镜、车灯罩、浴室镜等。  \n\n1.一种水性环保耐磨型有机无机杂化防雾涂料的制备方法，其特征在于：所述水性环保耐磨型有机无机杂化防雾涂料按重量份包括如下组分：  \n\n水性聚氨酯丙烯酸树脂 $30{\\sim}50$ 份；  \n$\\mathrm{Ti0_{2}/S i0_{2}}$ 杂化微球 $15{\\sim}25$ 份；  \n活性稀释剂 $20{\\sim}30$ 份；  \n聚丙烯酰胺 $2{\\sim}5$ 份；  \n光引发剂 $3{\\sim}5$ 份；  \n流平剂 $0.5\\mathord{\\sim}1$ 份；  \n助剂 $0.5\\mathord{\\sim}1$ 份；  \n去离子水 $80{\\sim}100$ 份；  \n乙醇或异丙醇 $20{\\sim}40$ 份；  \n\n所述助剂为阻聚剂和抗氧剂；  \n\n制备方法包括以下步骤：将水性聚氨酯丙烯酸树脂、 $\\mathrm{.Ti0_{2}/S i0_{2}}$ 杂化微球、活性稀释剂、聚丙烯酰胺、光引发剂、流平剂、助剂、去离子水、乙醇或异丙醇依次加入到容器中进行混合，水浴超声分散，待溶液澄清后用机械搅拌进行二次分散；  \n\n所述 $\\mathrm{Ti0_{2}/S i0_{2}}$ 杂化微球的制备步骤如下：  \n\n（1） $\\mathrm{Ti0_{2}/S i0_{2}}$ 杂化微球的制备：钛酸四丁酯（TBT）/正硅酸四乙酯（TEOS）： $\\mathrm{H}_{2}0$ ：无水乙醇的质量比为 $1{\\sim}2:3{\\sim}8:3{\\sim}8$ ，其中TBT/TEOS摩尔比为 $0.98{\\sim}0.8\\$ ，pH值为 $2{\\sim}3.5$ ，搅拌速率为 $500\\sim$ $1000\\mathrm{rpm}$ ，反应温度为 $50{\\sim}80^{\\circ}\\mathrm{C}$ ，反应时间为 $3{\\sim}5\\mathrm{h}$ ；  \n\n（2）随后加入硅烷偶联剂KH‑570，继续进行搅拌， $3{\\sim}5{\\mathrm{h}}$ 后结束反应，调节pH值于 $6.8{\\sim}7.2$ 之间进行常温保存。  \n\n2.根据权利要求1所述水性环保耐磨型有机无机杂化防雾涂料的制备方法，其特征在于，所述水性聚氨酯丙烯酸树脂由三步反应制备得到：  \n\n第一步，聚丙烯酸酯（PAA）的制备：采用不同比例的甲基丙烯酸甲酯（MMA），丙烯酸（AA），苯乙烯 $\\mathrm{(St)}$ ），丙烯酸羟乙酯（HEA）作为单体，以及偶氮二异丁腈（AIBN）作为引发剂，在$60{\\sim}80^{\\circ}\\mathrm{C}$ 条件下反应 $8{\\sim}10$ 小时制得，其中偶氮二异丁腈（AIBN）的用量为单体总质量的 $0.5\\%\\sim$ $1.5\\%$ ；  \n\n第二步，聚氨酯树脂预聚体的制备：采用聚醚多元醇和异佛尔酮二异氰酸酯制得，其中二者官能团摩尔比为‑NCO：‑OH为2：1，聚醚多元醇的分子量为 $800{\\sim}2000$ ；  \n\n第三步，水性聚氨酯丙烯酸树脂的制备：将一定量的聚丙烯酸酯（PAA）加入到聚氨酯树脂预聚体中，在 $60{\\sim}80^{\\circ}\\mathrm{C}$ 条件下继续反应 $5\\mathord{\\sim}6\\mathrm{h}$ 制得。  \n\n3.根据权利要求1所述水性环保耐磨型有机无机杂化防雾涂料的制备方法，其特征在于，所述活性稀释剂包括丙烯酸，甲基丙烯酸，甲基丙烯酸羟乙酯，羟乙基丙烯酰胺，甲基丙烯酸缩水甘油酯，季戊四醇三丙烯酸酯中的一种或者几种。  \n\n4.根据权利要求1所述水性环保耐磨型有机无机杂化防雾涂料的制备方法，其特征在于，所述聚丙烯酰胺的分子量为 $200{\\sim}800$ 万。  \n\n5.根据权利要求1所述水性环保耐磨型有机无机杂化防雾涂料的制备方法，其特征在于，所述光引发剂为184D，MBF，TPO，1173D中的至少一种。  \n\n6.根据权利要求1所述水性环保耐磨型有机无机杂化防雾涂料的制备方法，其特征在于，所述流平剂为BYK‑333，BYK‑306，BYK‑3700，BYK‑358N，BYK‑3720中的至少一种。  \n\n7.根据权利要求 $1{\\sim}6$ 任一项所述制备方法制备得到的水性环保耐磨型有机无机杂化防雾涂料在防雾中的应用，其特征在于，将所述水性环保耐磨型有机无机杂化防雾涂料依次进行涂膜、预烘以及UV光固化。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 一种水性环保耐磨型有机无机杂化防雾涂料及其制备",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明涉及防雾涂料领域，具体涉及一种水性环保耐磨型有机无机杂化防雾涂料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 结雾是日常生活中常见的一种自然现象，原因是当温度达到或接近露点温度时，空气中的水蒸气便会凝结成微小的露珠形成雾层。透明材料表面的雾化现象，不仅可以导致透光率严重下降，有时候甚至还存在重大安全隐患，比如在农业塑料大棚或者太阳能电池板上结露时，严重影响光的透过率，从而影响到太阳能的吸收率，导致农作物减产或者太阳能电池板的发电率降低；当结雾发生在医用护目镜或者摩托车头盔上时会严重影响视野，存在重大的安全隐患。为了防止上述结雾现象的发生，人们采取了多种防雾措施，常见的有(1)加热法，通过加热来保持透明材料表面的温度高于露点，从而防止结雾，但该方法成本高，局限性强，不适合大范围内推广使用。(2)对材料表面进行亲水或疏水处理，疏水处理一般采用含硅、氟的高分子树脂，存在成膜困难，工艺复杂，成本昂贵，且在有大量水汽迅速冷凝在材料表面时仍会出现雾化现象，因此在生活中应用少；亲水处理能够提升整个材料表面的浸润性能，有利于小水珠在其表面的铺展，因此具有良好的防雾性能，但传统的亲水防雾涂层存在以下问题：a、一般采用酯类，醚类等挥发性溶剂，在成膜过程中一方面会产生较大的环境污染，另一方面会提高涂料的生产成本和涂膜的制备工艺成本；b、防雾层存在耐磨性能差，硬度低，耐浸泡性能差等问题。  \n\n[0003] 例如，中国专利CN105315735公开了一种光热双重固化的亲水防雾涂料。该涂料先经过热固化，再经过光固化，得到的防雾层具有良好的防雾持久性和耐磨性能，但其固化工艺复杂，同时该涂料的溶剂采用丙二醇丁醚，乙二醇丁醚，丙二醇甲醚醋酸酯，醇酯‑12，丙二醇苯醚，苯甲醇等，在制膜过程中造成环境的污染，资源的浪费；中国专利CN103980455A公开了一种以聚氨酯丙烯酸树脂为基体树脂的光固化防雾涂料，该涂料制得的防雾膜虽然具有良好的初始防雾效果和持久的防雾性能，但由于其是纯的高分子防雾膜，因此该防雾膜的硬度较低，耐磨性能较差；专利CN1321164C公开的亲水性高分子防雾涂料，其溶剂使用的是乙二醇单甲醚或者乙二醇单乙醚，该类溶剂不仅成本高，而且在使用过程中会造成空气的污染,其防雾膜表面的耐磨性能差，硬度低，限制了其使用范围。专利CN111607320A提供了一种水性聚氨酯‑硅溶胶复合防雾剂，其中的水性聚氨酯的主体链段为PEG，在实际成膜过程中在不同的基材上存在结合力弱以及光滑度不够的问题，亲水二氧化硅微球在使用过程中容易发生微孔堵塞和表面的双键没有调节导致交联度过高亲水性能下降等问题；专利CN201210419958 .5以纳米 $\\mathrm{Si0_{2}}$ 为芯材， $\\mathrm{Ti0}_{2}$ 为壳材，在实际制备过程中工艺较为复杂，且$\\mathrm{Si0_{2}}$ 被包覆之后实际的亲水效果将会极大下降。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0004] 针对现有技术的缺陷，本发明的目的在于提供一种水性环保耐磨性型有机无机杂化防雾涂料，该涂料在制备过程中直接以水和醇作为复合溶剂，能够有效降低溶剂挥发对环境造成的污染，降低涂料的生产成本。  \n\n[0005] 本发明的目的是通过以下技术方案实现的：  \n\n[0006] 本发明提供了一种水性环保耐磨性有机无机杂化防雾涂料，其包含重量份数计的如下组分：  \n\n水性聚氨酯-丙烯酸树脂 30\\~50份；$\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ 杂化微球 15\\~25份；活性稀释剂 20\\~30份；聚丙烯酰胺 2\\~5份；[0007] 光引发剂 3\\~5份；流平剂 $0.5{\\sim}1$ 份；助剂 $0.5\\mathord{\\sim}1$ 份；去离子水 80\\~100份；乙醇或异丙醇 20\\~40份[0008] 本发明还提供一种水性环保耐磨型有机无机杂化防雾涂料的制备方法，包括以下步骤：将水性聚氨酯丙烯酸树脂、 $\\mathrm{Ti0_{2}/S i0_{2}}$ 杂化微球、活性稀释剂、聚丙烯酰胺、光引发剂、流平剂、助剂、去离子水、乙醇或异丙醇依次加入到容器中进行混合，水浴超声分散，待溶液澄清后再二次分散。  \n\n[0009] 具体的，所述的水性聚氨酯‑丙烯酸树脂的水性聚氨酯丙烯酸树脂由三步反应制备得到：  \n\n[0010] 第一步，聚丙烯酸酯(PAA)的制备，采用不同比例的单体(MMA，AA，St，HEA)以及引发剂偶氮二异丁腈(AIBN)，在 $60{\\sim}80^{\\circ}\\mathrm{C}$ 条件下反应 $8\\sim10$ 小时制得，其中AIBN的用量为单体总质量的 $0.5\\%\\sim1.5\\%$ ；  \n\n[0011] 第二步，聚氨酯树脂预聚体(PUA)的制备，采用聚醚多元醇和异佛尔酮二异氰酸酯制得，其中二者官能团摩尔比为(‑NCO：‑OH为2：1)，聚多元醚的分子量为 $1800{\\sim}2000$ ；  \n\n[0012] 第三步水性聚氨酯丙烯酸树脂，将一定量的PAA加入到PUA中，在 $60{\\sim}80^{\\circ}\\mathrm{C}$ 条件下继续反应 $5\\mathord{\\sim}6\\mathrm{h}$ 制得。  \n\n[0013] 具体的， $\\mathrm{Ti0_{2}/S i0_{2}}$ 杂化微球的制备步骤如下：(1)TBT/TEOS：H2O：Et‑OH(无水乙醇)的质量比为 $1{\\sim}2:3{\\sim}8:3{\\sim}8$ ，其中TBT/TEOS摩尔比为 $10.98{\\sim}0.8,\\mathrm{{g}}$ pH值为 $2{\\sim}3.5$ ，搅拌速率为 $500{\\sim}1000\\mathrm{rpm}$ ，反应温度为 $50{\\sim}80^{\\circ}\\mathrm{C}$ ，反应时间为 $3\\sim5\\mathrm{h}$ ；(2)随后加入KH‑570、KH‑560、HEA或者MTMS中的一种或者几种，继续进行搅拌， $3\\sim5\\mathrm{h}$ 后结束反应，调节pH值于 $6.8{\\sim}7.2$ 之间进行常温保存。  \n\n[0014] 优选地，上述pH值是通过加入醋酸，柠檬酸，丙烯酸，氢氧化钠或者氢氧化钾等进行调节。  \n\n[0015] 优选地， $\\mathrm{Ti0_{2}/S i0_{2}}$ 杂化微球的粒径是小于 $800\\mathrm{nm}$ ，修饰 $\\mathrm{Ti0_{2}/S i0_{2}}$ 杂化微球的目的是为了将其稳定的固定在防雾膜当中，引入 $\\mathrm{Ti0_{2}/S i0_{2}}$ 杂化微球的目的是为了增加光固化防雾膜的硬度以及耐磨性能，同时可以增加防雾膜在玻璃表面的附着力。  \n\n[0016] 优选地，活性稀释剂包括丙烯酸，甲基丙烯酸，甲基丙烯酸羟乙酯，羟乙基丙烯酰胺，甲基丙烯酸缩水甘油酯，季戊四醇三丙烯酸酯中的一种或者几种，其中引入高官活性稀释剂有利于提升固化膜的交联密度，可以进一步提升防雾膜的硬度、耐磨性能和耐浸泡性能。  \n\n[0017] 优选地，聚丙烯酰胺的分子量为 $200{\\sim}800$ 万，引入丙烯酰胺的目的是为了提升防雾膜的防雾性能，通过调节涂料的粘度来提升涂料的成膜性能。  \n\n[0018] 优选地，光引发剂为184D，MBF，TPO，1173D中的至少一种，采用不同波段的光引发剂进行复合的目的是为了进一步提升防雾涂料的固化效率，减少固化时间，提升固化膜的交联密度。  \n\n[0019] 优选地，流平剂为BYK‑333，BYK‑306，BYK‑3700，BYK‑358N，BYK‑3720中的至少一种。  \n\n[0020] 优选地，助剂为阻聚剂和抗氧剂，加入助剂有利于提升防雾涂料的储存稳定性。  \n\n[0021] 优选地，水性环保耐磨型有机无机杂化防雾涂料的溶剂为水和乙醇或者异丙醇的复配溶剂，其中乙醇或者异丙醇的加入，有利于预烘过程中水的挥发。  \n\n[0022] 本发明还提供上述水性环保耐磨型有机无机杂化防雾涂料的在防雾种的应用，将所述水性环保耐磨型有机无机杂化防雾涂料依次进行涂膜、预烘以及UV光固化。其中预烘温度为 $75{\\sim}85^{\\circ}\\mathrm{C}$ ，预烘时间为 $5\\sim15\\mathrm{{min}}$ ，固化能量为 $40000{\\sim}6000\\mathrm{mJ/cm^{2}},$ 。  \n\n[0023] 本发明与现有技术相比，本发明具有如下的有益效果：  \n\n[0024] 1)该水性涂料中水性聚氨酯丙烯酸树脂中引入MMA和 $\\mathrm{St}$ ，其主要目的为了增强该防雾涂料在PMMA、PS等基材表面的附着力。  \n\n[0025] 2)纯的 $\\mathrm{Si0_{2}}$ 微球在遇到油类等难挥发物质时容易发生微孔堵塞造成防雾性能下降；纯的TiO2微球在没有光照的情况下将失去亲水性达不到防雾效果，但由于其具有自清洁的特点，因此采用 $\\mathrm{Ti0_{2}/S i0_{2}}$ 杂化微球可以将两者的优点结合到一起，到达最接的亲水防雾性能。  \n\n[0026] 3) $\\mathrm{Ti0_{2}/S i0_{2}}$ 杂化微球的修饰过程中采用不含 $\\scriptstyle{\\mathrm{C}}={\\mathrm{}}$ C双键硅烷偶联剂，其主要作用是用于硅溶胶表面官能度的调节，其中修饰后的微球表面具有碳碳双键，其粒径在小于$800\\mathrm{nm}$ ，因为其参与光固化反应，因此将被均匀的固定在了防雾膜中，一方面赋予了防雾膜较好的良好的耐磨性，另一方面与玻璃接近的极性，因此该固化膜在玻璃表面同样具有良好的附着力。其中高官水性聚氨酯‑丙烯酸树脂的引入，加上小分子活性稀释剂的作用，大大增加了防雾固化膜的交联密度，从而增强了防雾膜表面的整体耐摩擦性能，交联密度的提升在防雾膜浸泡过程中阻止了水分子对防雾膜的侵蚀，进一步增强了防雾膜的耐浸泡性能。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 具体实施方式  \n\n[0027] 下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。  \n\n<html><body><table><tr><td>[0028]</td><td colspan=\"2\">实施例1</td></tr><tr><td>[0029]</td><td colspan=\"2\">一种水性环保耐磨型有机无机杂化涂料，包括如下重量份数原料：</td></tr><tr><td rowspan=\"3\">[0030]</td><td>水性聚氨酯-丙烯酸树脂</td><td>35份；</td></tr><tr><td>TiO/SiO杂化微球</td><td>15份；</td></tr><tr><td>丙烯酸羟乙酯</td><td>20份；</td></tr><tr><td rowspan=\"5\">[0031]</td><td>聚丙烯酰胺（300万分子量）</td><td>2.5份；</td></tr><tr><td>光引发剂TPO</td><td>5份；</td></tr><tr><td>引发剂BYK-3720</td><td>0.5份；</td></tr><tr><td>抗氧剂1010，阻聚剂701</td><td>0.5份；</td></tr><tr><td>去离子水</td><td>80份；</td></tr><tr><td></td><td>乙醇</td><td>20份</td></tr></table></body></html>  \n\n[0032] 涂料的配制方法：将上述原料依次加入 $200\\mathrm{ml}$ 的烧杯中，在 $50^{\\circ}\\mathrm{C}$ 水浴中超声15min，待溶液澄清后继续用机械搅拌进行二次分散，待分散均匀后转移到棕色遮光瓶中进行储存。  \n\n[0033] 防雾膜的涂布方面，将200ul的防雾原液滴在 $5\\times5\\times2\\mathrm{mm}$ 的亚克力板上，采用线棒进行刮涂均匀，静置2min后放入 $80^{\\circ}\\mathrm{C}$ 的烘箱预烘5min，随后进行UV光固化，固化能量为$40000\\mathrm{{mJ/cm}^{2}}$ 。  \n\n[0034] 实施例2  \n[0035] 一种水性环保耐磨型有机无机杂化涂料，包括如下重量份数原料：水性聚氨酯-丙烯酸树脂 45份；$\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ 杂化微球 20份；甲基丙烯酸缩水甘油酯 25份；聚丙烯酰胺（分子量400万） 3份；  \n[0036] 光引发剂1173D 6份；流平剂BYK-306 0.5份；抗氧剂1010，阻聚剂对羟基苯甲醚 0.5份；去离子水 80份；异丙醇 20份  \n\n[0037] 涂料的配制方法：将上述原料依次加入 $200\\mathrm{ml}$ 的烧杯中，在 $50^{\\circ}\\mathrm{C}$ 水浴中超声15min，待溶液澄清后继续用机械搅拌进行二次分散，待分散均匀后转移到棕色遮光瓶中进行储存。  \n\n[0038] 防雾膜的涂布方面，将 $200\\mathrm{ul}$ 的防雾原液滴在 $5\\times5\\times2\\mathrm{mm}$ 的亚克力板上，采用线棒进行刮涂均匀，静置2min后放入 $80^{\\circ}\\mathrm{C}$ 的烘箱预烘5min，随后进行UV光固化，固化能量为$40000\\mathrm{{mJ/cm}^{2}}$ 。  \n\n[0039] 实施例3  \n\n一种水性环保耐磨型有机无机杂化涂料，包括如下重量份数原料：  \n\n水性聚氨酯-丙烯酸树脂 55份；$\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ 杂化微球 30份；甲基丙烯酸 25份；聚丙烯酰胺（分子量700万） 2.5份；[0041] 光引发剂184D 8份；流平剂BYK-3700 0.5份；抗氧剂1010，阻聚剂701 0.5份；去离子水 80份；乙醇 20份[0042] 涂料的配制方法：将上述原料依次加入 $200\\mathrm{ml}$ 的烧杯中，在 $50^{\\circ}\\mathrm{C}$ 水浴中超声15min，待溶液澄清后继续用机械搅拌进行二次分散，待分散均匀后转移到棕色遮光瓶中进行储存。  \n\n[0043] 防雾膜的涂布方面，将 $200\\mathrm{ul}$ 的防雾原液滴在 $5\\times5\\times2\\mathrm{mm}$ 的亚克力板上，采用线棒进行刮涂均匀，静置2min后放入 $80^{\\circ}\\mathrm{C}$ 的烘箱预烘5min，随后进行UV光固化，固化能量为$40000\\mathrm{{mJ/cm}^{2}}$ 。  \n\n[0044] 对比实施例4  \n\n[0045] 一种水性环保耐磨型有机无机杂化涂料，包括如下重量份数原料：  \n\n$\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ 杂化微球 30份；甲基丙烯酸 25份；聚丙烯酰胺（分子量700万） 2.5份；光引发剂184D 8份；[0046]流平剂BYK-3700 0.5份；抗氧剂1010，阻聚剂701 0.5份；去离子水 50份；乙醇 20份[0047] 涂料的配制方法：将上述原料依次加入 $200\\mathrm{ml}$ 的烧杯中，在 $50^{\\circ}\\mathrm{C}$ 水浴中超声15min，待溶液澄清后继续用机械搅拌进行二次分散，待分散均匀后转移到棕色遮光瓶中进行储存。  \n\n[0048] 防雾膜的涂布方面，将 $200\\mathrm{ul}$ 的防雾原液滴在 $5\\times5\\times2\\mathrm{mm}$ 的亚克力板上，采用线棒进行刮涂均匀，静置2min后放入 $80^{\\circ}\\mathrm{C}$ 的烘箱预烘5min，随后进行UV光固化，固化能量为$40000\\mathrm{{mJ/cm}^{2}}$ 。  \n\n[0049] 对比实施例5  \n\n[0050] 一种水性环保耐磨型有机无机杂化涂料，包括如下重量份数原料：  \n\n水性聚氨酯-丙烯酸树脂 55份；甲基丙烯酸 25份；聚丙烯酰胺（分子量700万） 2.5份；光引发剂184D 8份；[0051]流平剂BYK-3700 0.5份；抗氧剂1010，阻聚剂701 0.5份；去离子水 80份；乙醇 20份  \n\n[0052] 涂料的配制方法：将上述原料依次加入 $200\\mathrm{ml}$ 的烧杯中，在 $50^{\\circ}\\mathrm{C}$ 水浴中超声15min，待溶液澄清后继续用机械搅拌进行二次分散，待分散均匀后转移到棕色遮光瓶中进行储存。  \n[0053] 防雾膜的涂布方面，将 $200\\mathrm{ul}$ 的防雾原液滴在 $5\\times5\\times2\\mathrm{mm}$ 的亚克力板上，采用线棒进行刮涂均匀，静置2min后放入 $80^{\\circ}\\mathrm{C}$ 的烘箱预烘5min，随后进行UV光固化，固化能量为$40000\\mathrm{{mJ/cm}^{2}}$ 。  \n[0054] 性能测试：  \n[0055] 对实施例 $1\\sim3$ 进行涂膜性能测试，测试初始防雾性能，浸泡后防雾性能，水接触角，硬度，附着力，耐磨性能。  \n[0056] 具体性能测试项目及对应方法如下：  \n[0057] 一、防雾性能测试：  \n[0058] 将防雾片置于 $65^{\\circ}\\mathrm{C}$ 的水浴锅上方，距离液面5cm的距离，熏蒸30s，拍照观察防雾的防雾性能。  \n[0059] 防雾性能判断标准：A级，均匀水膜；B级，小于 $50\\%$ 的面积有不均匀水膜；C级，大于$50\\%$ 的面积有不均匀水膜；D级，小于 $50\\%$ 的面积有结露；E级，大于 $50\\%$ 的面积有结露；F级，小于 $50\\%$ 的面积有结雾，G级，大于 $50\\%$ 的面积有结雾。  \n[0060] 二、水接触角测试：  \n[0061] 在固化膜表面滴2.5uL的超纯水，在室温下采用接触角测量仪进行测试。  \n[0062] 三、硬度测试：  \n[0063] 参照国家标准GB/T6739《漆膜硬度铅笔测定法》  \n[0064] 四、附着力测试：  \n[0065] 采用白格法，用3M不干胶带对样品附着力进行测试；  \n[0066] 估评方法：  \n[0067] 0级‑划线边缘光滑，在划线的边缘及交叉点处均无漆膜脱落；  \n[0068] 1级‑在划线的交叉点处有小片漆膜脱落，但脱落面积小于 $5\\%$ ；  \n[0069] 2级‑在划线的边缘及交叉点处有小片漆膜脱落，但脱落面积在 $5\\sim15\\%$ 之间；[0070] 3级‑在划线的边缘及交叉点处有成片漆膜脱落，但脱落面积在 $15\\sim35\\%$ 之间；[0071] 4级‑在划线的边缘及交叉点处有成片漆膜脱落，但脱落面积在 $35\\sim65\\%$ 之间；  \n\n5级‑在划线的边缘及交叉点处有成片漆膜脱落，但脱落面积大于 $65\\%$ 。  \n\n五、耐磨性能测试  \n\n[0072] [0073] [0074] [0075] [0076]  \n\n使用0000#钢丝绒， $200\\mathrm{g}$ 砝码，摩擦200次，记录表面划痕数。  \n\n测试结果：  \n\n<html><body><table><tr><td></td><td>防雾</td><td>水接触角</td><td>硬度</td><td>附着力</td><td>耐磨</td></tr><tr><td>实施例1</td><td>A级</td><td>6.996°</td><td>2H</td><td>0级</td><td>5条</td></tr><tr><td>实施例2</td><td>A级</td><td>10.213°</td><td>3H</td><td>0级</td><td>0条</td></tr><tr><td>实施例3</td><td>A级</td><td>10.194°</td><td>3H</td><td>0级</td><td>0条</td></tr><tr><td>对比实施例4</td><td>D级</td><td>30.415°</td><td>B</td><td>5级</td><td>50条</td></tr><tr><td>对比实施例5</td><td>D级</td><td>35.173°</td><td>B</td><td>0级</td><td>80条</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,57 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n<html><body><table><tr><td>(21)申请号 202111011269.6 (51) Int.CI .</td></tr><tr><td>C09D 175/14 (2006.01) (22)申请日2021.08.31</td></tr><tr><td>C09D 7/62 (2018.01)</td></tr><tr><td>(65)同一申请的已公布的文献号 C08F 212/08 (2006.01)</td></tr><tr><td>申请公布号CN113667393A C08F 220/06 (2006.01)</td></tr><tr><td>(43)申请公布日2021.11.19 C08F 220/14 (2006.01)</td></tr><tr><td>C08F 220/56 (2006.01) (73)专利权人武汉中科先进材料科技有限公司</td></tr><tr><td>C08J 7/054 (2020.01) 地址430000 湖北省武汉市武汉经济技术</td></tr><tr><td>开发区206M地块华中电子商务产业园 C08L 33/12 (2006.01)</td></tr><tr><td>A6栋1-6层 (56)对比文件</td></tr><tr><td>(72)发明人康翼鸿喻学锋李金堆边式 CN 111574899 A,2020.08.25</td></tr><tr><td>杨新耕杨帆吴列程文杰 CN 111303465 A,2020.06.19</td></tr><tr><td>US 2007247713 A1,2007.10.25</td></tr><tr><td>(74)专利代理机构武汉高得专利代理事务所 审查员冯宁</td></tr><tr><td>（普通合伙）42268 专利代理师 姜璐</td></tr></table></body></html>  \n\n权利要求书2页 说明书7页",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n一种防眩光型有机无机杂化防雾涂料及其制备",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明涉及光学涂料领域，具体涉及一种防眩光型有机无机杂化防雾涂料。本发明以水性聚氨酯‑丙烯酸树脂为防雾主体，以 $\\mathrm{Ti02@Si02}$ 杂化/PS或者TiO2@SiO2杂化/PMMA微球为防眩光主体，复配以小分子活性稀释剂，成膜助剂，光引发剂，流平剂等；该方法制备的涂料以醇类为溶剂，采用UV光固化工艺进行成膜制备，成膜效率高，能耗小。本发明提供的防眩光型有机无机杂化防雾涂层光学性能优异，在防雾的同时兼具防眩光性能，特别适用于具有防雾和防眩光的需求领域，如护目镜、汽车前挡风玻璃，防护面罩、头盔面罩，显示屏等。  \n\n1.一种防眩光型有机无机杂化防雾涂料的制备方法，其特征在于：该防雾涂料包括按重量份计的如下成分：  \n\n水性聚氨酯丙烯酸树脂 $35\\mathrm{{\\sim}}60$ 份；  \n$\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化/PS微球或 $\\mathrm{TiO}_{2}@\\mathrm{Si}0_{2}$ 杂化/PMMA微球 $15{\\sim}25$ 份；  \n活性稀释剂 $20{\\sim}30$ 份；  \n光引发剂 $3{\\sim}5$ 份；  \n流平剂 $0.1{\\sim}2$ 份；  \n助剂 $1{\\sim}2$ 份；  \n乙醇或异丙醇 $40{\\sim}60$ 份；  \n\n所述助剂为阻聚剂和抗氧剂；  \n\n制备方法采用如下步骤：将水性聚氨酯丙烯酸树脂、 $\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化/PS微球或 $\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化/PMMA微球、活性稀释剂、光引发剂、流平剂、助剂、以及乙醇或异丙醇依次加入到容器中进行混合，水浴超声分散，待溶液澄清后再二次分散；  \n\n所述T $\\mathrm{i0_{2}}@\\mathrm{Si}0_{2}$ 杂化/PS微球或 $\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化/PMMA微球采用原位聚合法制备得到：  \n\n1)钛酸四丁酯(TBT)/正硅酸乙酯(TEOS)： $\\mathrm{H}_{2}0$ ：无水乙醇的质量比为 $1{\\sim}2{:}3{\\sim}8{:}3{\\sim}8$ ，其中TBT/TEOS摩尔比为0  . $98{\\sim}0$ .8，pH值为 $2{\\sim}3$ .5，搅拌速率为 $2000{\\sim}3000\\mathrm{rpm}$ ，反应温度为 $50{\\sim}80^{\\circ}\\mathrm{C}$ ，反应时间为 $3\\mathrm{\\sim}5\\mathrm{h}$ ，得到 $\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化纳米微球；  \n\n2)采用表面活性剂十二烷基苯磺酸钠(SDBS)、十二烷基磺酸钠(SDS)或十六烷基三甲基溴化铵(CTAB)对 $\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化纳米微球进行预乳化；  \n\n3)边搅拌边滴加反应单体、丙烯酸及其衍生物和催化剂过硫酸铵的混合物，其中反应单体为苯乙烯或甲基丙烯酸甲酯中的一种，反应单体与丙烯酸及其衍生物的物质的量比为$8\\sim12:1$ ；  \n\n4)滴加完后在 $60{\\sim}80^{\\circ}\\mathrm{C}$ 下继续反应 $\\mathrm{1\\sim2h}$ 后结束反应，得到 $\\mathrm{Ti0_{2}}\\ @\\mathrm{Si}0_{2}$ 杂化/PS微球或$\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化/PMMA微球；所述丙烯酸及其衍生物为丙烯酸或甲基丙烯酸或丙烯酰胺中的至少一种。  \n\n2.根据权利要求1所述防眩光型有机无机杂化防雾涂料的制备方法制得的防雾涂料，其特征在于，包括如下成分：  \n\n水性聚氨酯丙烯酸树脂 $35\\mathrm{\\sim}60$ 份；  \n$\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化/PS微球或 $\\mathrm{TiO}_{2}@\\mathrm{Si}0_{2}$ 杂化/PMMA微球 $15{\\sim}25$ 份；  \n活性稀释剂 $20{\\sim}30$ 份；  \n光引发剂 $3{\\sim}5$ 份；  \n流平剂 $0.1{\\sim}2$ 份；  \n助剂 $1{\\sim}2$ 份；  \n乙醇或异丙醇 $40{\\sim}60$ 份。  \n\n3.根据权利要求2所述的防雾涂料，其特征在于：所述活性稀释剂包括丙烯酸、甲基丙烯酸、甲基丙烯酸羟乙酯、羟乙基丙烯酰胺、甲基丙烯酸缩水甘油酯或季戊四醇三丙烯酸酯中的至少一种。  \n\n4.根据权利要求2所述防雾涂料，其特征在于：所述光引发剂为184D，MBF，TPO或1173D中的至少一种。  \n\n5.根据权利要求2所述防雾涂料，其特征在于：所述流平剂为BYK‑333，BYK‑306，BYK‑3700，BYK‑358N或BYK‑3720中的至少一种。  \n\n6.根据权利要求 $2{\\sim}5$ 任一项所述的防雾涂料，其特征在于：所述 $\\Gamma\\mathrm{i}0_{2}@\\mathrm{Si}0_{2}$ 杂化/PS微球或 $\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化/PMMA微球的核为 $\\mathsf{I T i O}_{2}@\\mathsf{S i O}_{2}$ 杂化纳米微球， $\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化纳米微球的粒径在 $20{\\sim}50\\mathrm{nm}$ ，采用苯乙烯 $\\mathrm{(St)}$ 或甲基丙烯酸甲酯(MMA)包覆后，得到的 $\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化/PS微球或 $\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化/PMMA微球的粒径在 $80{\\sim}200\\mathrm{nm}$ 。  \n\n7.根据权利要求 $2{\\sim}6$ 任一项所述防雾涂料在防雾中的应用，其特征在于，将所述防雾涂料依次进行涂膜、预烘以及UV光固化。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 一种防眩光型有机无机杂化防雾涂料及其制备",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明涉及防雾涂料领域，具体涉及一种防眩光型有机无机杂化防雾涂料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 眩光是一种由于眼前光线映射到眼睛里，在视觉上产生眩晕感，导致观察者瞬时或者永久视力下降或者观察者的视觉产生不适的现象。眩光在我们的日常生活中经常出现，例如：日光，室内照明，汽车灯，显示屏等。在生活中眩光往往给我们的生活带来诸多不便，例如室内照明灯引起的眩光让我们的眼睛疲劳产生不适，轻者影响工作效率，时间久了会造成近视甚至是丧失视觉功能；当显示屏幕产生眩光我们无法清楚的看到其呈现的画面，直接影响观看效果。  \n\n[0003] 结雾是日常生活中常见的一种自然现象，原因是当温度达到或接近露点温度时，空气中的水蒸气便会凝结成微小的露珠形成雾层。透明材料表面的雾化现象，导致透光率严重下降，有时候甚至还存在重大安全隐患，比如当结雾发生在医用护目镜或者摩托车头盔上时会严重影响视野，存在重大的安全隐患。  \n\n[0004] 目前市场上常见的防眩光涂层或者防雾涂层都在单独使用，或者采用防眩光防雾贴膜的技术，无法满足高透光要求下的既需要防雾又需要防眩光的使用环境。  \n\n[0005] 例如，专利201920104316.3公开的一防雾防眩光膜。该膜包括PET层、硬化防护层以及亲水防雾层，存在结构复杂，膜层较厚影响透光效果等问题。  \n\n[0006] 例如，专利201410222093.2公开了一种以聚氨酯丙烯酸树脂为基体树脂的光固化防雾涂料，该涂料制得的防雾膜虽然具有良好的初始防雾效果和持久的防雾性能，但不具备防眩光效果。  \n\n[0007] 例如，专利CN104177951A公开了采用用聚苯乙烯或者聚甲基丙烯酸甲酯来包覆纳米 $\\mathrm{Si0}_{2}$ 、纳米 $\\mathrm{Ti0}_{2}$ 、纳米 $\\mathrm{CaC0_{3}}$ 等来制备防眩光纳米的方法，该方法制备的纳米微球虽然具有良好的防眩光效果，但在微球与水性涂料复合时存在分散不均或者分层等问题，会严重影响膜层的透光效果。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0008] 针对现有技术的缺陷，本发明的目的在于提供一种防眩光型有机无机杂化防雾涂料，该涂料制备的涂层在具有防雾效果的同时兼具防眩光；采用一次性UV固化成膜技术，成膜工艺简单，膜厚度可控，透光率高。  \n[0009] 针对现有技术中的缺陷，本发明的目的是提供一种防眩光型有机无机杂化防雾涂料。  \n[0010] 本发明是通过以下技术方案实现的：  \n[0011] 本发明提供了一种防眩光型有机无机杂化防雾涂料，其包含重量份数计的如下组分：  \n\n水性聚氨酯丙烯酸树脂 35\\~60份；  \n\n$\\mathrm{TiO}_{2}@\\mathrm{SiO}_{2}$ 杂化/PS微球或 $\\mathrm{TiO}_{2}@\\mathrm{SiO}_{2}$ 杂化/PMMA微球 15\\~25份；活性稀释剂 20\\~30份；[0012] 光引发剂 3\\~5份；  \n流平剂 0.1\\~2份；助剂 1\\~2份；  \n乙醇或异丙醇 40\\~60份[0013] 优选地，所述的水性聚氨酯‑丙烯酸树脂的官能度为6官、8官或者10官。  \n[0014] 优选地， $\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化/PS微球采用原位聚合法制备得到，具体如下：  \n[0015] 1)钛酸四丁酯(TBT)/正硅酸乙酯(TEOS)： $H_{2}0:\\mathrm{Et-OH}$ (无水乙醇)的质量比为 $1{\\sim}2$ ：$3{\\sim}8{:}3{\\sim}8$ ，其中TBT/TEOS摩尔比为 $0.98{\\sim}0.8$ ，pH值为 $2{\\sim}3.5$ ，搅拌速率为 $2000{\\sim}3000\\mathrm{rpm}$ ，反应温度为 $50{\\sim}80^{\\circ}\\mathrm{C}$ ，反应时间为 $3\\mathrm{\\sim}5\\mathrm{h}$ ，得到 $\\Gamma\\mathrm{i}0_{2}@\\mathrm{Si}0_{2}$ 杂化纳米微球；  \n[0016] 2)采用表面活性剂十二烷基苯磺酸钠(SDBS)、十二烷基磺酸钠(SDS)或十六烷基三甲基溴化铵(CTAB)对T $\\mathrm{i0_{2}}@\\mathrm{Si0_{2}}$ 杂化纳米微球进行预乳化；  \n[0017] 3)边搅拌边滴加反应单体苯乙烯、丙烯酸及其衍生物和引发剂过硫酸铵的混合物，其中苯乙烯与丙烯酸及其衍生物质量比为 $8\\sim12:1$ ；  \n[0018] 4)滴加完后在 $60{\\sim}80^{\\circ}\\mathrm{C}$ 下继续反应 $\\mathrm{1\\sim2h}$ 后结束反应，得到 $\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化/PS微球；  \n[0019] 所述丙烯酸及其衍生物为丙烯酸或甲基丙烯酸或丙烯酰胺中的至少一种。[0020] 类似的， $\\mathrm{Ti0_{2}}\\ @\\mathrm{Si}0_{2}$ 杂化/PMMA微球采用原位聚合法制备得到，具体如下：  \n[0021] 1)钛酸四丁酯(TBT)/正硅酸乙酯(TEOS)： $H_{2}0:\\mathrm{Et-OH}$ (无水乙醇)的质量比为 $1{\\sim}2$ ：$3{\\sim}8{:}3{\\sim}8$ ，其中TBT/TEOS摩尔比为 $0.98{\\sim}0.8,\\mathrm{p}$ H值为 $2{\\sim}3.5$ ，搅拌速率为 $2000{\\sim}3000\\mathrm{rpm}$ ，反应温度为 $50{\\sim}80^{\\circ}\\mathrm{C}$ ，反应时间为 $3\\mathrm{\\sim}5\\mathrm{h}$ ，得到 $\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化纳米微球；  \n[0022] 2)采用表面活性剂十二烷基苯磺酸钠(SDBS)、十二烷基磺酸钠(SDS)或十六烷基三甲基溴化铵(CTAB)对 $\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化纳米微球进行预乳化；  \n[0023] 3)边搅拌边滴加反应单体甲基丙烯酸甲酯、丙烯酸及其衍生物和引发剂过硫酸铵的混合物，其中甲基丙烯酸甲酯与丙烯酸及其衍生物质量比为 $\\phantom{-}8\\sim12:1$ ；  \n[0024] 4)滴加完后在 $60{\\sim}80^{\\circ}\\mathrm{C}$ 下继续反应 $\\mathrm{1\\sim2h}$ 后结束反应，得到 $\\Gamma\\mathrm{i}0_{2}@\\mathrm{Si}0_{2}$ 杂化/PS微球；  \n[0025] 所述丙烯酸及其衍生物为丙烯酸或甲基丙烯酸或丙烯酰胺中的至少一种。[0026] 优选地，上述 $\\mathrm{Ti0_{2}}\\ @\\mathrm{Si}0_{2}$ 杂化纳米微球的粒径在 $20{\\sim}50\\mathrm{nm}$ ，修饰后的 $\\mathrm{Ti0_{2}}\\ @\\mathrm{Si}0_{2}$ 杂化/PS微球或 $\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化/PMMA微球粒径在 $80{\\sim}200\\mathrm{nm}$ 。  \n[0027] 优选地，活性稀释剂包括丙烯酸，甲基丙烯酸，甲基丙烯酸羟乙酯，羟乙基丙烯酰胺，甲基丙烯酸缩水甘油酯或季戊四醇三丙烯酸酯中的至少一种，其中引入高官活性稀释剂有利于提升固化膜的交联密度，可以进一步提升防雾膜的硬度、耐磨性能和耐浸泡性能。[0028] 优选地，光引发剂为184D，MBF，TPO或1173D中的至少一种，采用不同波段的光引发  \n\n剂进行复合的目的是为了进一步提升防雾涂料的固化效率，缩短固化时间，提高防雾膜的交联密度。  \n\n[0029] 优选地，流平剂为BYK‑333，BYK‑306，BYK‑3700，BYK‑358N或BYK‑3720中的至少一种。  \n\n[0030] 优选地，助剂为阻聚剂和抗氧剂，加入助剂有利于提升防雾涂料的储存稳定性。  \n\n[0031] 优选地，防眩光型有机无机杂化防雾涂料的溶剂为乙醇或者异丙醇，其中乙醇或者异丙醇的加入，有利于缩短预烘时间。  \n\n[0032] 优选地，所述防雾膜的制备方法包括：涂膜、预烘以及UV光固化，其中预烘温度为$75{\\sim}85^{\\circ}\\mathrm{C}$ ，预烘时间为 $5\\sim15\\mathrm{{min}}$ ，固化能量为 $40000{\\sim}6000\\mathrm{mJ/cm}^{2}$ 。  \n\n[0033] 本发明与现有技术相比，本发明具有如下的有益效果：  \n\n[0034] 1)采用PMMA/PS包覆后的 $\\mathrm{Ti0_{2}}@\\mathrm{Si}0_{2}$ 杂化一方面有助于提升该纳米微球的光学性能，提升防雾固化膜的防眩光性能，另一方面可以提升固化膜在PMMA/PC/PS等基材表面的附着力。  \n\n[0035] 2)在采用MMA或者St包覆 $\\mathrm{TiO}_{2}@\\mathrm{Si}0_{2}$ 杂化纳米微球时，在MMA或者St单体加入了丙烯酸(AA)、甲基丙烯酸(MAA)、丙烯酰胺(AM)中的至少一种；其作用是在 $\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化/PS或者$\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化/PMMA纳米微球表面引入羧基或者氨基来增强纳米微球的亲水防雾性能以及与亲水树脂之间的相容性，且纳米微球的粒径小于 $200\\mathrm{nm}$ ，可以分布在防雾层的各个层面，其中分布在表面的微球在具有防眩光的同时可以进一步提升防雾层的亲水性能。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 具体实施方式  \n\n[0036] 下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。  \n\n[0037] 实施例1制备 $\\mathrm{TiO}_{2}@\\mathrm{Si}0_{2}$ 杂化/PS微球[0038] 先准备 $\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化纳米微球，步骤如下：  \n\n[0039] 1)TBT/TEOS： $\\mathrm{{H}}_{2}\\mathrm{{0}}$ ：Et‑OH(无水乙醇)的质量比为1：3：3，其中TBT/TEOS摩尔比为0.98，pH值为2，搅拌速率为 $2000\\mathrm{rpm}$ ，反应温度为 $50^{\\circ}\\mathrm{C}$ ，反应时间为 $3\\mathord{\\sim}5\\mathrm{h}$ ；  \n\n[0040] 再以 $\\mathrm{Ti0_{2}}@\\mathrm{Si}0_{2}$ 杂化纳米微球为核，用St在核表面进行修饰，原位聚合包覆形成PS的壳，得到 $\\Gamma\\mathrm{i}0_{2}@\\mathrm{Si}0_{2}$ 杂化/PS微球。具体如下：  \n\n[0041] 2)采用表面活性剂 $5\\%$ 的十二烷基苯磺酸钠(SDBS)对 $\\mathrm{Ti0_{2}/S i0_{2}}$ 杂化纳米微球进行预乳化；  \n\n[0042] 3)边搅拌边滴加反应单体苯乙烯、丙烯酸和占总质量 $2\\%$ 的催化剂过硫酸铵的混合物，其中甲基丙烯酸甲酯与丙烯酸物质的量比为8：1；  \n\n[0043] 4)滴加完后在 $60^{\\circ}\\mathrm{C}$ 下继续反应2h后结束反应，得到 $\\mathrm{Ti0_{2}/S i0_{2}}$ 杂化/PS纳米微球；[0044] 实施例2制备 $\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化/PMMA微球  \n\n[0045] 先准备 $\\cdot\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化纳米微球，步骤如下：  \n\n[0046] 1)TBT/TEOS： $\\mathrm{{H}}_{2}0$ ：Et‑OH(无水乙醇)的质量比为2：3：8，其中TBT/TEOS摩尔比为0.85，pH值为2.5，搅拌速率为 $2500\\mathrm{rpm}$ ，反应温度为 $70\\mathrm{{^\\circC}}$ ，反应时间为4h。  \n\n[0047] 再以 $\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化纳米微球为核，用MMA在核表面进行修饰，原位聚合包覆形成  \nPMMA的壳，得到 $\\mathrm{Ti0_{2}}\\ @\\mathrm{Si}0_{2}$ 杂化/PMMA微球。具体如下：  \n[0048] 2)采用表面活性剂 $3\\%$ 的十六烷基三甲基溴化铵(CTAB)对 $\\mathrm{TiO}_{2}@\\mathrm{Si}0_{2}$ 杂化纳米微球  \n进行预乳化；  \n[0049] 3)边搅拌边滴加反应单体甲基丙烯酸甲酯、丙烯酰胺和引发剂过硫酸铵的混合  \n物，其中甲基丙烯酸甲酯与丙烯酰胺物质的量比为12：1；  \n[0050] 4)滴加完后在 $80^{\\circ}\\mathrm{C}$ 下继续反应1.5h后结束反应，得到 $\\mathrm{TiO}_{2}@\\mathrm{Si}0_{2}$ 杂化/PMMA纳米微  \n球。  \n[0051] 实施例3‑7均为制备涂料的方法，其中6‑7为对比例。  \n[0052] 实施例3  \n[0053] 一种防眩光型有机无机杂化涂料，包括如下重量份数原料：水性聚氨酯丙烯酸树脂 35份；$\\mathrm{TiO}_{2}@\\mathrm{SiO}_{2}$ 杂化/PS微球 15份；季戊四醇三丙烯酸酯 20份；  \n[0054] 光引发剂TPO 4份；流平剂BYK-306 2份；抗氧剂1010，阻聚剂701 1份；异丙醇 45份  \n\n[0055] 涂料的配制方法：将上述原料依次加入 $200\\mathrm{ml}$ 的烧杯中，在 $50^{\\circ}\\mathrm{C}$ 水浴中超声15min，待溶液澄清后继续用机械搅拌进行二次分散，待分散均匀后转移到棕色遮光瓶中进行储存。  \n\n[0056] 防雾膜的涂布方面，将 $200\\mathrm{ul}$ 的防雾原液滴在 $5\\times5\\times2\\mathrm{mm}$ 的亚克力板上，采用线棒进行刮涂均匀，静置2分钟后放入 $80^{\\circ}\\mathrm{C}$ 的烘箱预烘5min，随后进行UV光固化，固化能量为$40000\\mathrm{{mJ/cm}^{2}}$ 。  \n\n[0057] 实施例4  \n[0058] 一种防眩光型有机无机杂化涂料，包括如下重量份数原料：水性聚氨酯-丙烯酸树脂 45份；$\\mathrm{TiO}_{2}@\\mathrm{SiO}_{2}$ 杂化/PS微球 20份；甲基丙烯酸 30份；  \n[0059]光引发剂184D 5份；流平剂BYK-3720 0.1份；抗氧剂1010，阻聚剂701 1.5份；  \n[0060] 异丙醇 50份  \n[0061] 涂料的配制方法：将上述原料依次加入 $200\\mathrm{ml}$ 的烧杯中，在 $50^{\\circ}\\mathrm{C}$ 水浴中超声15min，  \n\n待溶液澄清后继续用机械搅拌进行二次分散，待分散均匀后转移到棕色遮光瓶中进行储存。  \n\n[0062] 防雾膜的涂布方面，将 $200\\mathrm{ul}$ 的防雾原液滴在 $5\\times5\\times2\\mathrm{mm}$ 的亚克力板上，采用线棒进行刮涂均匀，静置2分钟后放入 $80^{\\circ}\\mathrm{C}$ 的烘箱预烘5min，随后进行UV光固化，固化能量为$40000\\mathrm{{mJ/cm}^{2}}$ 。  \n\n[0063] 实施例5  \n[0064] 一种防眩光型有机无机杂化涂料，包括如下重量份数原料：水性聚氨酯丙烯酸树脂 60份；$\\mathrm{TiO}_{2}@\\mathrm{SiO}_{2}$ 杂化/PMMA微球 25份；丙烯酸羟乙酯 25份；  \n[0065] 光引发剂1173D 5份；流平剂BYK-3700 0.1份；抗氧剂1010，阻聚剂701 2份；异丙醇 60份  \n[0066] 实施例6  \n[0067] 一种防眩光型有机无机杂化涂料，包括如下重量份数原料：水性聚氨酯丙烯酸树脂 25份；丙烯酸羟乙酯 25份；光引发剂1173D 5份；  \n[0068]流平剂BYK-3700 0.1份；抗氧剂1010，阻聚剂701 2份；异丙醇 60份  \n[0069] 实施例7  \n[0070] 一种防眩光型有机无机杂化涂料，包括如下重量份数原料：$\\mathrm{TiO}_{2}@\\mathrm{SiO}_{2}$ 杂化/PMMA微球 60份；  \n[0071]丙烯酸羟乙酯 25份；光引发剂1173D 5份；流平剂BYK-3700 0.1份；  \n[0072]抗氧剂1010，阻聚剂701 2份；异丙醇 60份  \n[0073] 涂料的配制方法：将上述原料依次加入200ml的烧杯中，在 $50^{\\circ}\\mathrm{C}$ 水浴中超声15min，  \n\n待溶液澄清后继续用机械搅拌进行二次分散，待分散均匀后转移到棕色遮光瓶中进行储  \n\n存。  \n\n[0074] 防雾膜的涂布方面，将 $200\\mathrm{ul}$ 的防雾原液滴在 $5\\times5\\times2\\mathrm{mm}$ 的亚克力板上，采用线棒进行刮涂均匀，静置2分钟后放入 $80^{\\circ}\\mathrm{C}$ 的烘箱预烘5min，随后进行UV光固化，固化能量为$40000\\mathrm{{mJ/cm}^{2}}$ 。  \n\n[0075] 性能测试：  \n\n[0076] 对实施例 $3{\\sim}7$ 进行涂膜性能测试，测试初始防雾性能，浸泡后防雾性能，水接触角，硬度，附着力，耐磨性能。  \n\n[0077] 具体性能测试项目及对应方法如下：  \n\n[0078] 一、防雾性能测试：  \n\n[0079] 将防雾片置于 $65^{\\circ}\\mathrm{C}$ 的水浴锅上方，距离液面5cm的距离，熏蒸30s，拍照观察防雾的 防雾性能。  \n\n[0080] 防雾性能判断标准：A级，均匀水膜；B级，小于 $50\\%$ 的面积有不均匀水膜；C级，大于$50\\%$ 的面积有不均匀水膜；D级，小于 $50\\%$ 的面积有结露；E级，大于 $50\\%$ 的面积有结露；F级，小于 $50\\%$ 的面积有结雾，G级，大于 $50\\%$ 的面积有结雾。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# [0081] 二、水接触角测试：  \n\n在固化膜表面滴2.5uL的超纯水，在室温下采用接触角测量仪进行测试。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 三、硬度测试：  \n\n[0084] 参照国家标准GB/T6739《漆膜硬度铅笔测定法》  \n\n[0085] 四、附着力测试：  \n\n[0086] 采用白格法，用3M不干胶带对样品附着力进行测试；  \n\n[0087] 估评方法：  \n\n0级‑划线边缘光滑，在划线的边缘及交叉点处均无漆膜脱落；  \n\n1级‑在划线的交叉点处有小片漆膜脱落，但脱落面积小于 $5\\%$  \n\n2级‑在划线的边缘及交叉点处有小片漆膜脱落，但脱落面积在 $5\\sim15\\%$ 之间；  \n\n1] 3级‑在划线的边缘及交叉点处有成片漆膜脱落，但脱落面积在 $15\\sim35\\%$ 之间；  \n\n4级‑在划线的边缘及交叉点处有成片漆膜脱落，但脱落面积在 $35\\sim65\\%$ 之间；  \n\n5级‑在划线的边缘及交叉点处有成片漆膜脱落，但脱落面积大于 $65\\%$ 。  \n\n[0094] 五、透光率及雾度  \n\n采用彩谱雾度仪进行测量，按照GB/T2410‑80标准执行：  \n\n[0096] 六、光泽度  \n\n采用德国BYK公司光泽仪测定，以 $20^{\\circ}$ °， ${60}^{\\circ}$ °和 $85^{\\circ}$ °的角度测定相对的反射率来判断[0100] 如上表所示，在单独使用水性聚氨酯丙烯酸树脂时，固化膜的防雾性能和附着力较好，但硬度低，不存在防眩光性能；在单独使用 $\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化/PMMA或者 $\\mathrm{Ti0_{2}}\\ @\\mathrm{Si}0_{2}$ 杂化/PS微球时，固化膜虽然硬度较高，但防雾性能以及附着力、防眩光性能较弱；而在 $\\Gamma\\mathrm{i}0_{2}@\\mathrm{Si}0_{2}$ 杂化/PMMA或者 $\\mathrm{Ti0}_{2}@\\mathrm{Si}0_{2}$ 杂化/PS微球添加到最适范围时，固化膜的在防雾性能，硬度，附着力和防眩光性能方面均有了明显的改进。  \n\n表1实施例3‑7的性能参数比较  \n\n\n<html><body><table><tr><td></td><td>防雾性能</td><td>水接触角</td><td>附着力</td><td>硬度</td><td>透光度</td><td>雾度</td><td>光泽度</td></tr><tr><td>实施例3</td><td>A级</td><td>8.891°</td><td>0级</td><td>H</td><td>88.8</td><td>0.68</td><td>84</td></tr><tr><td>实施例4</td><td>A级</td><td>9.566°</td><td>0级</td><td>H</td><td>88.7</td><td>0.54</td><td>82</td></tr><tr><td>实施例5</td><td>A级</td><td>9.330°</td><td>0级</td><td>2H</td><td>88.5</td><td>0.92</td><td>79</td></tr><tr><td>实施例6</td><td>A级</td><td>8.451°</td><td>0级</td><td>2B</td><td>90.6</td><td>0.45</td><td>85</td></tr><tr><td>实施例7</td><td>D级</td><td>48.891°</td><td>5级</td><td>3H</td><td>78.5</td><td>0.98</td><td>45</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,47 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n<html><body><table><tr><td>(21)申请号202111336319.8</td><td>C09D 7/63 (2018.01)</td></tr><tr><td>(22)申请日 2021.11.11</td><td>C09D 7/47 (2018.01)</td></tr><tr><td>(65)同一申请的已公布的文献号</td><td>C08F 226/10 (2006.01)</td></tr><tr><td>申请公布号CN113930121A</td><td>C08F 220/14 (2006.01)</td></tr><tr><td></td><td>C08F 220/20 (2006.01)</td></tr><tr><td>(43)申请公布日2022.01.14</td><td>C08F 220/54 (2006.01)</td></tr><tr><td>(73)专利权人唐波</td><td>C08F 220/58 (2006.01)</td></tr><tr><td>地址402760 重庆市璧山区金科中央公园 E9栋30-6</td><td>审查员鲁慧</td></tr><tr><td>(72)发明人唐波</td><td></td></tr><tr><td></td><td></td></tr><tr><td>(74)专利代理机构重庆华科专利事务所50123 专利代理师 李勇康海燕</td><td></td></tr><tr><td></td><td></td></tr><tr><td>(51) Int.CI .</td><td></td></tr><tr><td>CO9D 139/06 (2006.01)</td><td></td></tr><tr><td>CO9D 133/12 (2006.01)</td><td></td></tr><tr><td>C09D 161/32 (2006.01)</td><td>权利要求书3页说明书8页</td></tr></table></body></html>",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n基于两亲性共聚物的防雾涂层组合物及其制备方法和应用",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明公开了一种基于两亲性共聚物的防雾涂层组合物及其制备方法和应用，包括两亲性共聚物、交联剂、表面活性剂、流平剂、碱性化合物和溶剂；所述两亲性共聚物由如下组分制得：单体 $\\mathrm{\\cdot}\\mathrm{A}_{1}$ ：作为主要的亲水性单体成分；单体 $\\mathbf{\\cdotA}_{2}$ ：具有羟基官能团的乙烯基类单体；单体 $\\mathrm{.A_{3}}$ ：作为疏水性单体成分；单体 $\\mathrm{A}_{4}$ ：具有亲水性官能团的乙烯基类单体；单体 ${\\bf\\cdot}\\hat{\\bf{A}}_{5}$ ：具有磺酸基团的乙烯基类单体，磺酸基团与碱性化合物反应形成盐，未与碱性化合物结合的磺酸基团催化含有羟基官能团的两亲性共聚物与交联剂发生交联反应，形成交联的空间结构。其涂覆基材固化成膜后，防雾膜中不含水溶性小分子，解决目前防雾技术产生留痕和发彩问题，并且综合性能满足使用要求。  \n\n1.一种基于两亲性共聚物的防雾涂层组合物，其特征在于：包括两亲性共聚物、交联剂、表面活性剂、流平剂、碱性化合物和溶剂；  \n\n所述两亲性共聚物包括如下组分：  \n\n单体A ：N‑乙烯基‑2‑吡咯烷酮，作为主要的亲水性单体成分；  \n\n单体 $\\mathbf{\\cdotA}_{2}$ ：具有羟基官能团的乙烯基类单体；  \n\n单体 ${\\bf\\cdot A}_{3}$ ：具有烷基链官能团、氰基官能团、苯环官能团、环戊烷官能团、环己烷官能团、乙烯酯官能团的乙烯类单体，作为疏水性单体成分，有效调节两亲性共聚物的疏水性，增加两亲性共聚物与基材的吸附力；  \n\n单体 $\\mathrm{.A_{4}}$ ：具有亲水性官能团的乙烯基类单体，作为亲水性的辅助调节单体，有效调节两亲性共聚物的亲水性，改善防雾性；  \n\n单体 ${\\bf\\cdot}\\hat{\\bf{h}}_{5}$ ：具有磺酸基团的乙烯基类单体，磺酸基团与碱性化合物反应形成盐，改善防雾性；未与碱性化合物结合的磺酸基团催化含有羟基官能团的单体 $\\mathbf{\\cdotA}_{2}$ 与交联剂发生交联反应，形成交联的空间结构；  \n\n所述两亲性共聚物按重量百分比计包括： $20{\\sim}50\\%$ 的单体 $\\mathbf{\\cdotA}_{1}$ 、 $4{\\sim}25\\%$ 的单体 $\\mathrm{A}_{2}\\cdot15{\\sim}50\\%$ 的单体 $\\mathrm{\\cdotA_{3}\\cdot4{\\sim}18\\%}$ 的单体 $\\mathrm{.A_{4}}$ $\\mathrm{i}_{4}\\cdot0.1{\\sim}5\\%$ 的单体 $\\mathrm{\\cdotA_{5}}$ ；  \n\n所述两亲性共聚物的数均分子量为 $4000{\\sim}120000$ ；  \n\n所述两亲性共聚物的典型结构式的示意图为：  \n\n![](images/245973afdd52663d393f43494cb74ff51b206607cd02af5199f9763c8af52aba.jpg)  \n\n其中， $\\mathrm{a},\\mathrm{b},\\mathrm{c},\\mathrm{d},\\mathrm{e}$ 分别代表各单体 $\\mathrm{.A}_{1}$ 、单体 $\\mathbf{\\cdotA}_{2}$ 、单体 $\\mathrm{.A_{3}}$ 、单体 $\\mathrm{.A_{4}}$ 、单体 $\\mathrm{\\cdotA}_{5}$ 的聚合度；  \n\n其中，单体 $\\mathrm{.A_{2}}$ 除了以上结构式示意图中含有羟基的丙烯酸酯类烯烃单体以外，还能够为$\\mathrm{CH_{2}}\\mathrm{=CHCH_{2}O H}$ $\\mathrm{\\DeltaH_{2}O H,C H_{2}=C H C H_{2}C H_{2}O H,C H_{3}C H=C H C H_{2}O H,C H_{2}=C\\left(C H_{3}\\right)C H_{2}O H,C H_{2}=C H C H_{2}C H_{2}C H_{2}O H,}$ 、 $\\mathrm{CH_{2}}\\mathrm{=}$ $\\mathrm{CHCH_{2}C H_{2}C H_{2}C H_{2}O H}$ $\\mathrm{,CH_{2}O H\\cdot C H_{2}=C H C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}O H\\cdot C H_{2}=C H C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}O H\\cdot C H_{2}=2^{2}C H_{2}C H_{2}C H_{2}\\cdot C H_{2}C H_{2}O H\\cdot C H_{2}=2^{2}H_{2}O H\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}\\cdot C H_{2}$ $\\mathrm{CHCH_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}O H\\cdot C H_{2}}=\\mathrm{CHCH_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}O H}$ 或为相同分子式的同分异构体；  \n\n单体 $\\mathrm{A}_{3}$ 除了以上结构示意图中含有烷基官能团的丙烯酸酯类单体外，还能够为 $\\mathrm{CH_{2}=}$ $\\mathrm{CH}_{2}$ 、 $\\mathrm{CH_{2}{=}C H C H_{3}}$ 、 $\\mathrm{CH_{2}{=}C H C H_{2}C H_{3}}$ 、 $\\mathrm{CH_{2}{=}C H C H_{2}C H_{2}C H_{3}}$ 或含有双键的同分异构体、 $\\mathrm{CH_{2}=}$ $\\mathrm{CHCH_{2}C H_{2}C H_{2}C H_{3}}$ 或含有双键的同分异构体、 $\\mathrm{.CH_{2}{=}C H C H_{2}C H_{2}C H_{2}C H_{2}C H_{3}}$ 或含有双键的同分异构体、 $\\mathrm{CH_{2}}\\mathrm{=CHCH_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{3}}$ 或含有双键的同分异构体、 $\\mathrm{.CH_{2}{=}C H C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{3}}$ 或含有双键的同分异构体、 $\\mathrm{,CH_{2}=C H C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{3}}$ 或含有双键的同分异构体、 $\\mathrm{CH_{2}=C H C N}$ 或含有氰基官能团的同类乙烯基单体、 ${\\mathrm{CH}}_{2}{=}{\\mathrm{CHAr}}$ 或含有苯环官能团的同类乙烯基单体、乙烯基环戊烷或含有环戊烷官能团的同类乙烯基单体、乙烯基环己烷或含有环己烷官能团的同类乙烯基单体、醋酸乙烯酯、丙酸乙烯酯或含有乙烯酯官能团的同类乙烯基单体；  \n\n单体 $\\mathrm{\\cdotA_{4}}$ 除了以上结构示意图中含有丙烯酰胺官能团的乙烯基单体以外，还能够为 $\\mathrm{CH_{2}=}$ CHCOOH、 $\\mathrm{CH_{2}}\\mathrm{=CHCH_{2}}($ COOH、HOOCCH=CHCOOH或含有羧基的同类乙烯基单体；  \n\n其中 $\\mathrm{,R_{1}\\mathcal{H}H_{s}C H_{3}\\mathrm{,}C H_{2}C H_{3}\\mathrm{,}C H_{2}C H_{2}C H_{3}\\mathrm{,}C H(C H_{3})_{2}\\mathrm{,}C H_{2}C H_{2}C H_{2}C H_{3}\\mathrm{,}C H_{3}C H(C H_{2}C H_{3}\\mathrm{,}C H_{2}C H_{3})}$ 中的至少一种； $\\mathsf{R}_{2}$ $\\mathrm{\\Delta\\Psi_{J}C H_{2}O H_{\\mathrm{{-}}C H_{2}}C H_{\\mathrm{{-}}}O H\\mathrm{{_{\\mathrm{{-}}C H0H C H_{\\mathrm{{3}}}\\cdot C H_{\\mathrm{{2}}C H_{\\mathrm{{2}}}O H\\mathrm{{-}C H_{\\mathrm{{2}}C H0H C H_{\\mathrm{{3}}}\\cdot C H0H C H_{\\mathrm{{2}}}C H_{\\mathrm{{3}}}\\cdot C H\\left(C H_{\\mathrm{{3}}}\\right)C H_{\\mathrm{{2}}O H}}}}}}}}}$ 、HOC $\\mathrm{(CH_{3^{\\prime}}}$ $)_{_{2}},\\mathrm{cH_{2}C H_{2}C H_{2}C H_{2}O H},\\mathrm{CH_{2}C H_{2}C H0H C H_{3}},\\mathrm{CH_{2}C H0H C H_{2}C H_{3}},\\mathrm{CHOHCH_{2}C H_{2}C H_{3}},\\mathrm{CHOHCH_{3}C H(C H_{3})C H_{2}C H_{2}O H},$ C $\\mathrm{\\Delta^{CH}_{3}\\mathrm{'}_{2}C H_{2}O H\\mathrm{,}C H(C H_{2}C H_{3})^{\\mathrm{~CH}}\\mathrm{,}}^{\\mathrm{0C~(CH_{3})^{\\mathrm{~CH}}\\mathrm{,}H O C~(C H_{3})^{\\mathrm{~CH}}\\mathrm{,}C H_{2}C H_{3}\\mathrm{,}C H_{2}C H_{2}C H_{2}C H_{2}O H\\mathrm{,}C H_{2}C H_{2}C H_{2}C H0H}}$ 、$\\mathrm{CH_{2}C H_{2}C H0H C H_{2}C H_{3}}\\cdot\\mathrm{CH_{2}C H0H C H_{2}C H_{2}C H_{3}}$ $\\mathrm{\\Delta\\cdotCH_{2}C H0H C H_{2}C H_{2}C H_{3}\\cdot C H0H C H_{2}C H_{2}C H_{2}C H_{3}\\cdot C H_{3}C H C H_{2}C H_{2}C H_{2}O H}\\sqrt{C_{2}}H_{2}O$ 、$\\mathrm{I_{3}C H C H_{2}C H_{3}},C H_{3}\\mathrm{,\\PhiCHCH_{3},O H C H_{2}C H_{3},C H_{3}C\\left(O H\\right)C H_{2}C H_{3}},C H_{3}\\mathrm{,\\PhiCH_{3}C H C H C H_{2}C H_{3}},C H_{3}\\mathrm{,\\PhiCH_{2}O H C H C H_{2}C H_{3}}.$ 、CH3CH2C $\\mathrm{HCH_{2}C H_{2}O H}\\cdot C H_{3}C H_{2}C\\left(0H\\right)C H_{2}C H_{3}\\mathrm{,CHOHCH_{2}C H\\left(C H_{3}\\right)_{2}\\cdot C H_{2}C H O H C H\\left(C H_{3}\\right)_{2}\\cdot C H_{2}C H_{2}C\\left(C H_{3}\\right)_{2}O H}\\cdot$ CH $\\mathrm{_{2}C H_{2}C H(C H_{3})C H_{2}O H.C H_{2}C(C H_{3})_{2}C H_{2}O H.C H O H C(C H_{3})_{3}.C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}O H}.$ 、中的至少一种； $\\mathrm{R_{3}}$ 为 $\\mathrm{H.cH_{3}.c H_{2}c H_{3}.c H_{2}C H_{2}C H_{3}.c H(C H_{3})_{2}.c H_{2}C H_{2}C H_{2}C H_{3}.c H_{3}C H C H_{2}C H_{3}.c\\left(C H_{3}\\right)_{3}\\mathrm{\\Delta^{+}H_{2}C H_{3}.c H(C H_{3})_{2}}}$ 的至少一种； $\\mathrm{R_{4}}$ 为$\\mathrm{CH}_{3}$ $\\mathrm{I_{3}\\cdot C H_{2}C H_{3}\\cdot C H_{2}C H_{2}C H_{3}\\cdot C H(C H_{3})_{2}\\cdot C H_{2}C H_{2}C H_{2}C H_{3}\\cdot C H_{3}C H C H_{2}C H_{3}\\cdot C(C H_{3})_{3}\\cdot C H_{2}C H_{2}C H_{2}C H_{2}C H_{3}}$ 、CH$\\mathrm{(CH_{3})C H_{2}C H_{2}C H_{3}}$ $\\mathrm{CH_{2}C H_{2}C H_{3}}\\cdot\\mathrm{CH(CH_{2}C H_{3})_{2}}\\circ\\mathrm{C(CH_{3})_{2}C H_{2}C H_{3}}\\circ\\mathrm{CH_{2}C(C H_{3})_{3}}\\circ\\mathrm{CH_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{3}}\\mathrm{CH_{3}}\\oplus\\mathrm{H_{2}}\\oplus\\mathrm{CJ}\\cdot\\mathrm{H_{2}C H_{3}}\\mathrm{CH_{2}C H_{3}}\\mathrm{CH_{2}C H_{3}}\\mathrm{CH_{2}C H_{3}}\\mathrm{CH_{2}}\\mathrm{CH_{3}}\\mathrm{CH_{2}}\\mathrm{CH_{3}}\\mathrm{CH_{2}}\\mathrm{CH_{3}}\\mathrm{CH_{2}}\\mathrm{CH_{3}}\\mathrm{CH_{2}}\\mathrm{CH_{3}}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{3}}\\mathrm{CH_{2}}\\mathrm{CH_{3}}\\mathrm{CH_{2}}\\mathrm{CH_{3}}\\mathrm{CH_{2}}\\mathrm{CH_{3}}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{3}}\\mathrm{CH_{2}}\\mathrm{CH_{3}}\\mathrm{CH_{2}}\\mathrm{CH_{3}}\\mathrm{CH_{2}}\\mathrm{CH_{3}}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{3}}\\mathrm{CH_{2}}\\mathrm{CH_{3}}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{2}\\mathrm{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{CH_{2}}\\mathrm{CH_{2}}\\mathrm{CH_{CH_{2}}\\mathrm{CH_{CH_{2}}\\mathrm\\mathrm{CH}\\mathrm{CH_{CH_{CH_{2}}}\\mathrm\\mathrm{CH}\\mathrm{CH_{CH_}\\mathrm{CH}\\mathrm{CH_{CH_}}\\mathrm{CH}\\mathrm{CH_}\\mathrm{C H $ 种；$\\mathrm{R}_{5}$ 为 $\\mathrm{H,cH_{3},c H_{2}C H_{3},c H_{2}C H_{2}C H_{3},c H(C H_{3})_{2},c H_{2}C H_{2}C H_{2}C H_{3},c H_{3}C H C H_{2}C H_{3},c(C H_{3})_{3}C H_{2}C H_{3},c H_{2}C H_{3},c H_{3}=0,0,0,0,0.1}$ 中的至少一种； ${\\mathrm{R}}_{6}$ 为H、 $\\mathrm{.CH_{3}.C H_{2}C H_{3}.C H_{3}C H C H_{3}}$ 中的至少一种； $\\mathrm{R}_{7}$ 为H、 $\\mathrm{\\cdotCH_{3}\\cdot C H_{2}C H_{3}\\cdot C H_{3}C H C H_{3}}$ 中的至少一种； $\\mathrm{R}_{8}$ 为H、$\\mathrm{CH_{3}}\\cdot\\mathrm{CH_{2}C H_{3}}\\cdot\\mathrm{CH_{2}C H_{2}C H_{3}}\\cdot\\mathrm{CH(CH_{3})}_{2}\\cdot\\mathrm{CH_{2}C H_{2}C H_{2}C H_{3}}\\cdot\\mathrm{CH_{3}C H C H_{2}C H_{3}}\\cdot\\mathrm{C\\left(CH_{3}\\right)}$ 3中的至少一种； $\\mathrm{R_{9}}$ 为OH、$0^{-}\\mathrm{\\DeltaN^{+}H_{2}}\\left(C H_{2}C H_{3}\\right)_{2}\\mathrm{\\Delta_{2}\\mathrm{\\Delta0^{-}M^{+}H\\left(C H_{2}C H_{3}\\right)_{3}\\mathrm{\\Delta_{3}\\mathrm{\\Delta0^{-}N^{+}H\\left(C H_{2}C H_{2}0H\\right)_{3}\\mathrm{\\Delta_{3}\\mathrm{\\Delta0^{-}N a^{+}\\mathrm{\\Delta_{3}\\mathrm{\\Delta0^{-}K^{+}\\left[\\Omega_{2}\\right]}}}}}}}}}$ 以及吡啶盐、氨基吡啶盐中的至少一种； $\\mathrm{R}_{10}$ 为O和NH中的至少一种； $\\mathrm{R}_{11}$ 为H、 $\\mathrm{CH}_{3}$ 和 $\\mathrm{CH_{2}C H_{3}}$ 中的至少一种； $\\mathrm{R}_{12}$ 为H、 $\\mathrm{CH_{3}}$ 和 $\\mathrm{CH_{2}C H_{3}}$ 中的至少一种。  \n\n2.根据权利要求1所述的基于两亲性共聚物的防雾涂层组合物，其特征在于：以100重量份的两亲性共聚物为基准，交联剂的含量为 $5\\mathrm{\\sim}50$ 重量份，表面活性剂的含量为 $0.5{\\sim}15$ 重量份，流平剂的含量为 $0.1{\\sim}2$ 重量份，碱性化合物的含量为相对于两亲性共聚物的单体 $\\mathrm{.A_{5}}$ 的$20{\\sim}99\\mathrm{mol}\\%$ 。  \n\n3.根据权利要求1或2所述的基于两亲性共聚物的防雾涂层组合物，其特征在于：单体 $\\mathbf{\\cdotA}_{2}$ 为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯醇、丁烯醇、戊烯醇、己烯醇、庚烯醇、辛烯醇、壬烯醇、癸烯醇中的至少一种；  \n\n单体 $\\mathrm{\\ddot{A}_{3}}$ 为丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯、乙烯、丙烯、丁烯、戊烯、己烯、庚烯、辛烯、壬烯、癸烯、丙烯腈、苯乙烯、乙烯基环戊烷、乙烯基环己烷、醋酸乙烯酯、丙酸乙烯酯中的至少一种；  \n\n单体A 为丙烯酰胺、甲基丙烯酰胺、N‑甲基丙烯酰胺、N‑甲基甲基丙烯酰胺、N‑乙基丙烯酰胺、 $.{\\mathrm{N}}^{-}$ 乙基甲基丙烯酰胺、N‑异丙基丙烯酰胺、N‑异丙基甲基丙烯酰胺、N,N‑二甲基丙烯酰胺、N,N‑二甲基甲基丙烯酰胺、N,N‑二乙基丙烯酰胺、N,N‑二乙基甲基丙烯酰胺、丙烯酸、甲基丙烯酸、丁烯酸、顺丁烯二酸中的至少一种；  \n\n单体 $\\mathrm{.A_{5}}$ 为丙烯酸‑3‑磺基丙酯、甲基丙烯酸‑3‑磺基丙酯、丙烯酸‑2‑磺基乙酯、甲基丙烯酸‑2‑磺基乙酯、2‑丙烯酰胺‑2‑甲基丙磺酸、甲基丙烯酰胺‑2‑甲基丙磺酸中的至少一种。  \n\n4.根据权利要求1或2所述的基于两亲性共聚物的防雾涂层组合物，其特征在于：所述交联剂为三聚氰胺‑甲醛树脂、苯代三聚氰胺‑甲醛树脂、烷基代三聚氰胺‑甲醛树脂、尿素‑甲醛树脂、六甲氧基甲基三聚氰胺树脂、六丁氧基甲基三聚氰胺树脂中的至少一种；  \n\n所述表面活性剂为全氟乙基乙基醇、全氟丙基乙基醇、全氟丁基乙基醇、全氟己基乙基醇、全氟辛基乙基醇、全氟乙基乙基醇聚氧乙烯醚、全氟乙基乙基醇聚醚、全氟丙基乙基醇聚氧乙烯醚、全氟丙基乙基醇聚醚、全氟丁基乙基醇聚氧乙烯醚、全氟丁基乙基醇聚醚、全氟己基乙基醇聚氧乙烯醚、全氟己基乙基醇聚醚、全氟辛基乙基醇聚氧乙烯醚、全氟辛基乙基醇聚醚中的至少一种；  \n\n所述流平剂为含有羟基官能团的硅氧烷、聚醚改性硅氧烷中的至少一种；  \n\n所述碱性化合物为二乙胺、三乙胺、三乙醇胺、氢氧化钠、氢氧化钾、吡啶、4‑氨基吡啶中的至少一种；  \n\n所述溶剂为醇类溶剂、醚类溶剂、酮类溶剂、酯类溶剂、芳香族类溶剂、胺类溶剂、烃类溶剂、水中的至少一种。  \n\n5.一种基于两亲性共聚物的防雾涂层组合物的制备方法，其特征在于：按照权利要求1${\\sim}4$ 任一项所述的基于两亲性共聚物的防雾涂层组合物组分进行备料，将单体 $\\mathbf{\\cdotA}_{1}$ 、单体 $\\mathbf{\\cdotA}_{2}$ 、单体 $\\mathrm{{A}_{3}}$ 、单体 $\\mathrm{.A_{4}}$ 、单体 $\\mathrm{.A}_{5}$ 、引发剂、碱性化合物加入到溶剂中，在温度为 $50{\\sim}95^{\\circ}\\mathrm{C}$ 的条件下反应 $3\\sim$ 24h得到两亲性共聚物；单体 $\\mathrm{.}\\mathrm{\\textmu}_{1}$ 、单体 $\\mathbf{\\cdotA}_{2}$ 、单体 ${\\bf\\cdot A}_{3}$ 、单体 $\\mathrm{.A_{4}}$ 、单体 $\\mathrm{\\cdotA_{5}}$ 、引发剂组成的混合物的重量为溶剂重量的 $20\\small{\\sim}60\\%$ ，所述引发剂为有机过氧化物或偶氮化合物；  \n\n将交联剂、表面活性剂、流平剂、溶剂加入到上述制得的两亲性共聚物中，在室温条件下搅拌混合，制得基于两亲性共聚物的防雾涂层组合物。  \n\n6.权利要求 $1{\\sim}4$ 任一项所述的基于两亲性共聚物的防雾涂层组合物或权利要求5所述制备方法制得的基于两亲性共聚物的防雾涂层组合物在车灯、车膜、玻璃、头盔、护目镜、眼镜或透镜设备中的应用。  \n\n7.根据权利要求6所述的防雾涂层组合物的应用，其特征在于：将基于两亲性共聚物的防雾涂层组合物通过喷涂或淋涂工艺涂附在基材表面，加热固化，固化温度为 $60{\\sim}120^{\\circ}\\mathrm{C}$ ，固化时间为 $10{\\sim}60\\mathrm{min}$ ，在基材表面得到厚度为 $1{\\sim}30\\upmu\\mathrm{m}$ 的防雾涂层。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 基于两亲性共聚物的防雾涂层组合物及其制备方法和应用",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明涉及防雾技术领域，具体涉及基于两亲性共聚物的防雾涂层组合物及其制备方法和应用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 汽车前大灯、汽车尾灯、汽车前挡玻璃、汽车中控屏、玻璃、护目镜、眼镜、头盔、水表等，由于在温度和湿度的差异条件下，温度较高和湿度较大一面的空气中水汽凝结在塑料或玻璃等表面，形成流动性较差的小水珠，使得塑料和玻璃表面产生雾气。这些形成雾气的小水珠使光线发生反射、散射和衍射等，使得透明塑料或玻璃变得模糊，从而给使用者带来不愉快。  \n\n[0003] 对此，有很多技术针对以上防雾问题进行了改进，其中主要的方法是高分子防雾涂层涂覆法。但是，目前的高分子防雾涂层涂覆法，由于高分子防雾涂层中含有可溶于水的小分子，比如阴离子型表面活性剂、阳离子型表面活性剂等，往往会在防雾后产生流痕和发彩现象，并且存在硬度低、防雾效果难以持久、涂覆成膜性差、耐水性差、耐热老化差等问题。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0004] 本发明的目的是提供一种基于两亲性共聚物的防雾涂层组合物及其制备方法和应用，其涂覆基材固化成膜后，防雾膜中不含水溶性小分子，解决目前防雾技术产生留痕和发彩问题，并且综合性能满足使用要求。  \n[0005] 本发明所述的基于两亲性共聚物的防雾涂层组合物，包括两亲性共聚物、交联剂、表面活性剂、流平剂、碱性化合物和溶剂；  \n[0006] 所述两亲性共聚物由如下组分制得：  \n[0007] 单体 $\\mathrm{.}\\mathrm{\\textmu}_{1}$ ：N‑乙烯基‑2‑吡咯烷酮，作为主要的亲水性单体成分；  \n[0008] 单体 $\\mathrm{{A}_{2}}$ ：具有羟基官能团的乙烯基类单体；  \n[0009] 单体 $\\mathrm{A}_{3}$ ：具有烷基链官能团、氰基官能团、苯环官能团、环戊烷官能团、环己烷官能团、乙烯酯官能团的乙烯类单体，作为疏水性单体成分；  \n[0010] 单体 $\\mathrm{\\A_{4}}$ ：具有亲水性官能团的乙烯基类单体；  \n[0011] 单体 $\\mathrm{\\cdotA_{5}}$ ：具有磺酸基团的乙烯基类单体，磺酸基团与碱性化合物反应形成盐，未与碱性化合物结合的磺酸基团催化含有羟基官能团的两亲性共聚物与交联剂发生交联反应，形成交联的空间结构。  \n[0012] 进一步，所述两亲性共聚物的数均分子量为 $4000{\\sim}120000$ ；  \n[0013] 所述两亲性共聚物的典型结构式的示意图为：  \n\n![](images/d3240982ea53697bcd68b322316729cb899516f103c8d1e62523b05d36420a4f.jpg)  \n\n[0014]  \n\n[0015] 其中， $\\mathrm{a},\\mathrm{b},\\mathrm{c},\\mathrm{d},\\mathrm{e}$ 分别代表各单体 $\\mathbf{\\cdotA}_{1}$ 、单体 $\\mathbf{\\cdotA}_{2}$ 、单体 ${\\bf\\cdot A}_{3}$ 、单体 $\\mathrm{.A_{4}}$ 、单体 $\\mathrm{\\cdotA_{5}}$ 的聚合度；  \n\n[0016] 其中，单体 $\\mathbf{\\cdotA}_{2}$ 除了以上结构式示意图中含有羟基的丙烯酸酯类烯烃单体以外，还能够为 $\\mathrm{CH_{2}}=\\mathrm{CHCH_{2}O H}\\setminus\\mathrm{CH_{2}}=\\mathrm{CHCH_{2}C H_{2}O H}\\setminus\\mathrm{CH_{3}C H}=\\mathrm{CHCH_{2}O H}\\setminus\\mathrm{CH_{2}}=\\mathrm{C\\left(CH_{3}\\right)C H_{2}O H}\\setminus\\mathrm{CH_{2}}=\\mathrm{CH_{2}O H}\\setminus\\mathrm{CH_{2}}$ C H C H 2 $\\mathrm{^{3H}_{2}C H_{2}O H_{\\mathrm{\\cdot}}C H_{2}}=C H C H_{2}C H_{2}C H_{2}C H_{2}O H\\cdot C H_{2}=C H C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}O H\\cdot C H_{2}=2C H C H_{2}C H_{2}\\cdot C H_{2}=2C H C H_{2}\\cdot C H_{2}\\cdot C H_{2}=2^{2}\\cdot C H_{2}C H_{2}\\cdot C H_{2}=2^{2}\\cdot C H_{2}\\cdot C H_{2}.$ $\\mathrm{\\DeltaCHCH_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}O H_{\\Delta}C H_{2}}=\\mathrm{CHCH_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}O H},$ $\\mathrm{C}\\mathrm{H}_{2}=$ $\\mathrm{CHCH_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}O H}$ H或为相同分子式的同分异构体；  \n\n[0017] 单体 ${\\bf\\cdot A}_{3}$ 除了以上结构示意图中含有烷基官能团的丙烯酸酯类单体以外，还能够为$\\mathrm{CH_{2}}=\\mathrm{CH_{2}}\\circ\\mathrm{CH_{2}}=\\mathrm{CHCH_{3}}\\circ\\mathrm{CH_{2}}=\\mathrm{CHCH_{2}C H_{3}}\\circ\\mathrm{CH_{2}}=\\mathrm{CHCH_{2}C H_{2}C H_{3}}$ 或含有双键的同分异构体、 $\\mathrm{CH_{2}=}$ $\\mathrm{CHCH_{2}C H_{2}C H_{2}C H_{3}}$ 或含有双键的同分异构体、 $\\mathrm{.CH_{2}{=}C H C H_{2}C H_{2}C H_{2}C H_{2}C H_{3}}$ 或含有双键的同分异构体、 $\\mathrm{CH_{2}}{=}\\mathrm{CHCH_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{3}}$ 或含有双键的同分异构体、 $\\mathrm{.CH_{2}{=}C H C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{3}}$ 或含有双键的同分异构体、 $\\mathrm{.CH_{2}{=}C H C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{3}}$ 或含有双键的同分异构体、 $\\mathrm{CH_{2}=}$ CHCN或含有氰基官能团的同类乙烯基单体、 ${\\mathrm{.CH_{2}{=}C H A r}}$ 或含有苯环官能团的同类乙烯基单体、乙烯基环戊烷或含有环戊烷官能团的同类乙烯基单体、乙烯基环己烷或含有环己烷官能团的同类乙烯基单体、醋酸乙烯酯、丙酸乙烯酯或含有乙烯酯官能团的同类乙烯基单体；[0018] 单体 $\\mathrm{A}_{4}$ 除了以上结构示意图中含有丙烯酰胺官能团的乙烯基单体以外，还能够为$\\mathrm{CH_{2}}\\mathrm{=CHCOOH\\cdotCH_{2}}\\mathrm{=CHCH_{2}C O O H\\cdot H O O C C H}\\mathrm{=CHCO0H}\\mathrm{\\cdot}$ 或含有羧基的同类乙烯基单体；[0019] $\\mathrm{R_{1}^{\\mathrm{\\#}}\\mathrm{\\mathcal{H}H_{\\mathrm{\\cdot}}C H_{\\mathrm{\\cdot}}C H_{\\mathrm{2}}C H_{\\mathrm{\\cdot}}C H_{\\mathrm{\\cdot}}C H_{\\mathrm{\\cdot}}C H_{\\mathrm{\\cdot}}C H(C H_{\\mathrm{3}})\\mathrm{\\Omega_{2}\\cdot C H_{\\mathrm{2}}C H_{\\mathrm{\\cdot}}C H_{\\mathrm{\\cdot}}C H_{\\mathrm{3}}\\cdot C H(C H_{\\mathrm{\\cdot}}C H_{\\mathrm{\\cdot}}C H_{\\mathrm{\\cdot}}C H(C H_{\\mathrm{3}})\\mathrm{\\Omega_{3}\\cdot}}}}$ 中的至少一 $\\mathrm{\\overline{{\\cdot}}\\mathrm{\\overline{{\\cdot}}\\mathrm{\\overline{{\\mathrm{H}}}\\mathrm{\\mathrm{i}}\\mathrm{\\mathrm{i}}_{2}\\mathrm{\\cdot}\\mathrm{R}_{2}\\mathrm{\\overline{{\\jmath}}\\mathrm{C}\\mathrm{H}_{2}\\mathrm{O}\\mathrm{H}\\mathrm{\\cdot}C H_{2}\\mathrm{C}H_{2}O H\\mathrm{\\cdot}C H\\mathrm{OHCH}_{3}\\mathrm{\\cdot}C H_{2}C H_{2}C H_{2}O H\\mathrm{\\cdot}C H_{2}C H0H C H_{3}\\mathrm{\\cdot}C H0H C H_{2}C H_{3}\\mathrm{\\cdot}C H(C H_{3})C H0H\\mathrm{\\cdot}C H0H}}}}$ $\\mathrm{CH}\\left(\\mathrm{CH}_{3}\\right)\\mathrm{CH}_{2}0\\mathrm{H}.$ 、HO $\\mathrm{{C\\left({CH_{3}}\\right)_{2},C H_{2}C H_{2}C H_{2}C H_{2}O H,C H_{2}C H_{2}C H0H C H_{3},C H_{2}C H0H C H_{2}C H_{3},C H0H C H_{2}C H_{3}C H_{3}C H(C H_{3})C H_{2}C H0H}}$ H2OH、C $\\mathrm{\\Delta^{\\prime}C H_{3}\\mathrm{)_{2}C H_{2}O H},C H(C H_{2}C H_{3})C H_{2}O H,H O C(C H_{3})C H_{2}C H_{3},C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}O H,C H_{2}C H_{2}C H_{2}C H_{2}C H0H}$ 、$\\mathrm{I_{2}C H_{2}C H0H C H_{2}C H_{3}\\cdot C H_{2}C H0H C H_{2}C H_{2}C H_{3}\\cdot C H0H C H_{2}C H_{2}C H_{2}C H_{3}\\cdot C H_{3}C H C H_{2}C H_{2}C H_{2}C H}$ 2OH 、C $\\begin{array}{r}{\\mathrm{I_{3}C H C H_{2}C H_{2}O H C H_{3}}\\mathrm{,\\CH_{3}C H C H_{2}O H C H_{2}C H_{3}\\mathrm{,\\CH_{3}C\\left(O H\\right)C H_{2}C H_{3}C H_{3}\\mathrm{,\\CH_{2}O H C H C H_{2}C H_{3}\\mathrm{,\\CH_{3}C H_{3}C H_{3}C H_{3}\\mathrm{,\\CH_{2}O H C H C H_{2}C H_{3}\\mathrm{,\\CH_{3}C H_{3}C H_{3}C H_{3}\\mathrm{,\\CH_{3}C H_{3}C H_{3}C H_{3}\\mathrm{,\\CH_{3}C H_{3}C H_{3}C H_{3}\\mathrm{,\\CH_{3}C H_{3}C H_{3}C H_{3}\\mathrm{,\\CH_{3}C H_{3}C H_{3}\\mathrm{,\\CH_{3}C H_{3}C H_{3}\\mathrm{,\\CH_{3}C H_{3}C H_{3}\\mathrm{,\\CH_{3}C H_{3}C H_{3}\\mathrm{,\\CH_{3}C H_{3}\\mathrm{,\\CH_{3}C H_{3}C H_{3}\\mathrm{,\\CH_{3}C H_{3}\\mathrm{,\\CH_{3}C H_{3}\\mathrm{.\\CH_{3}\\mathrm{,\\CH_{3}C H_{3}\\mathrm{,\\CH_{3}\\mathrm{.\\CH_{3}\\mathrm{.\\CH_{3}\\mathrm{.\\CH_{3}\\mathrm{.\\CH_{3}\\mathrm{.\\CH_{3}\\mathrm{.\\CH_{3}\\mathrm}\\mathrm{.}}}}}}}}}}}}}}}}}}}}}}}\\end{array}$ 、CH3C $\\mathrm{I_{2}C H C H_{2}C H_{2}O H_{\\mathrm{{r}}}C H_{\\mathrm{{3}}}C H_{\\mathrm{{2}}}C\\left(0H\\right)C H_{\\mathrm{{2}}}C H_{\\mathrm{{3}}},C H O H C H_{\\mathrm{{2}}}C H\\left(C H_{\\mathrm{{3}}}\\right)_{\\mathrm{{2}}},C H_{\\mathrm{{2}}}C H O H C H\\left(C H_{\\mathrm{{3}}}\\right)_{\\mathrm{{2}}},C H_{\\mathrm{{2}}}C H_{\\mathrm{{2}}}C\\left(C H_{\\mathrm{{3}}}\\right)_{\\mathrm{{2}}}0}$ H、CH $_{2}\\mathrm{CH_{2}C H(C H_{3})C H_{2}O H_{\\mathrm{\\cdot}}C H_{2}C\\left(C H_{3}\\right)_{2}C H_{2}O H_{\\mathrm{\\cdot}}C H O H C\\left(C H_{3}\\right)_{3}\\mathrm{\\cdot}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}O H}$ 、中的至少一种； $\\mathrm{R_{3}}$ 为 $\\mathrm{H.cH_{3}.c H_{2}c H_{3}.c H_{2}C H_{2}C H_{3}.c H(C H_{3})_{2}\\cdot C H_{2}C H_{2}C H_{2}C H_{3}\\cdot C H_{3}C H C H_{2}C H_{3}\\cdot C\\left(C H_{3}\\right)_{3}\\cdot\\mathrm{H(CH_{2})_{2}}}$ 的至少一种； $\\mathrm{R_{4}}$ 为$\\mathrm{CH}_{3}$ $\\mathrm{|\\Omega_{3}\\cdot C H_{2}C H_{3}\\cdot C H_{2}C H_{2}C H_{3}\\cdot C H(C H_{3})_{2}\\cdot C H_{2}C H_{2}C H_{2}C H_{3}\\cdot C H_{3}C H C H_{2}C H_{3}\\cdot C\\left(C H_{3}\\right)_{3}\\cdot C H_{2}C H_{2}C H_{2}C H_{2}C H_{3}}}$ H3、CH$\\begin{array}{r}{\\mathrm{(CH_{3})C H_{2}C H_{2}C H_{3}\\cdot C H(C H_{2}C H_{3})_{2}\\cdot C(C H_{3})_{2}C H_{2}C H_{3}\\cdot C H_{2}C(C H_{3})_{3}\\cdot C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{3}\\uparrow\\downarrow\\uparrow\\downarrow\\uparrow\\downarrow}}\\end{array}$ 少一种；$\\mathrm{R}_{5}$ 为 $\\mathrm{I\\cdotCH_{3}\\cdot C H_{2}C H_{3}\\cdot C H_{2}C H_{2}C H_{3}\\cdot C H(C H_{3})_{2}\\cdot C H_{2}C H_{2}C H_{2}C H_{3}\\cdot C H_{3}C H C H_{2}C H_{3}\\cdot C\\left(C H_{3}\\right)_{3}!}$ 中的至少一种； ${\\mathrm{R}}_{6}$ 为H、 $\\mathrm{.CH_{3}.C H_{2}C H_{3}.C H_{3}C H C H_{3}}$ 中的至少一种； $\\mathrm{R}_{7}$ $\\mathrm{\\hbar\\mathrm{\\cdot}H_{\\mathrm{H},\\mathrm{CH_{3}\\mathrm{\\cdot}C H_{2}C H_{3}\\mathrm{\\cdot}C H_{3}}}C H C H_{3}}$ 中的至少一种； $\\mathrm{R}_{8}$ 为H、$\\mathrm{CH_{3}}\\cdot\\mathrm{CH_{2}C H_{3}}\\cdot\\mathrm{CH_{2}C H_{2}C H_{3}}\\cdot\\mathrm{CH(CH_{3})}_{2}\\cdot\\mathrm{CH_{2}C H_{2}C H_{2}C H_{3}}\\cdot\\mathrm{CH_{3}C H C H_{2}C H_{3}}\\cdot\\mathrm{C(CH_{3})}_{3}\\cdot\\mathrm{RH(CH_{2})}\\cdot\\mathrm{CH_{2}C H_{3}}$ 中的至少一种； $\\mathrm{R_{9}}$ 为OH、$0^{-}\\mathrm{\\DeltaN^{+}H_{2}(C H_{2}C H_{3})_{2}\\circ O^{-}N^{+}H(C H_{2}C H_{3})_{3}\\circ O^{-}N^{+}H(C H_{2}C H_{2}O H)_{3}\\circ O^{-}N a^{+}\\cdot O^{-}K^{+}|\\Sigma\\}}.$ 及吡啶盐、氨基吡啶盐中的至少一种； $\\mathrm{R}_{10}$ 为O和NH中的至少一种； $\\mathrm{R}_{11}$ 为H、 $\\mathrm{CH_{3}}$ 和 $\\mathrm{CH_{2}C H_{3}}$ 中的至少一种； $\\mathrm{R_{12}\\mathrm{\\partial\\times\\mathrm{JH}\\mathrm{,CH_{3}}}}$ 和 $\\mathrm{CH_{2}C H_{3}}$ 中的至少一种。  \n\n[0020] 进一步，所述两亲性共聚物按重量百分比计包括： $3\\sim50\\%$ 的单体 $\\mathrm{A_{1}}\\cdot4{\\sim}25\\%$ 的单体 $\\mathrm{A_{2}}\\cdot10{\\sim}60\\%$ 的单体 $\\mathrm{.A_{3}}$ $\\phantom{+}_{3}{\\cdot}4{\\sim}40\\%$ 的单体 $\\mathrm{.A_{4}}$ $.0.1{\\sim}20\\%$ 的单体 $\\mathrm{\\cdotA_{5}}$ 。  \n\n[0021] 进一步，所述两亲性共聚物按重量百分比计包括： $5\\sim45\\%$ 的单体 $\\mathrm{A_{1}}\\cdot7\\sim20\\%$ 的单体 $\\mathrm{.A_{2}}$ $12\\cdot15\\sim50\\%$ 的单体 $\\mathrm{.A_{3}}$ 、 $6sim35\\%$ 的单体 $\\mathrm{.A_{4}}$ $.0.5\\sim18\\%$ 的单体 $\\mathrm{\\cdotA}_{5}$ 。  \n\n[0022] 进一步，以100重量份的两亲性共聚物为基准，交联剂的含量为 $5\\sim50$ 重量份，表面活性剂的含量为 $0.5{\\sim}15$ 重量份，流平剂的含量为 $0.1{\\sim}2$ 重量份，碱性化合物的含量为相对于两亲性共聚物的单体 $\\mathrm{.A}_{5}$ 的 $20\\mathrm{\\sim}99\\mathrm{mol}\\%$ ，溶剂的含量为 $100{\\sim}700$ 重量份。  \n\n[0023] 进一步，单体 $\\mathbf{\\cdotA}_{2}$ 为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯醇、丁烯醇、戊烯醇、己烯醇、庚烯醇、辛烯醇、壬烯醇、癸烯醇中的至少一种；  \n\n[0024] 单体 $\\mathrm{.A_{3}}$ 为丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯、乙烯、丙烯、丁烯、戊烯、己烯、庚烯、辛烯、壬烯、癸烯、丙烯腈、苯乙烯、乙烯基环戊烷、乙烯基环己烷、醋酸乙烯酯、丙酸乙烯酯中的至少一种；  \n\n[0025] 单体 $\\mathrm{\\cdotA_{4}}$ 为丙烯酰胺、甲基丙烯酰胺、N‑甲基丙烯酰胺、N‑甲基甲基丙烯酰胺、N‑乙基丙烯酰胺、N‑乙基甲基丙烯酰胺、N‑异丙基丙烯酰胺、N‑异丙基甲基丙烯酰胺、N,N‑二甲基丙烯酰胺、N,N‑二甲基甲基丙烯酰胺、N,N‑二乙基丙烯酰胺、N,N‑二乙基甲基丙烯酰胺、丙烯酸、甲基丙烯酸、丁烯酸、顺丁烯二酸中的至少一种；  \n\n[0026] 单体 $\\mathrm{.A_{5}}$ 为丙烯酸‑3‑磺基丙酯、甲基丙烯酸‑3‑磺基丙酯、丙烯酸‑2‑磺基乙酯、甲基丙烯酸‑2‑磺基乙酯、2‑丙烯酰胺‑2‑甲基丙磺酸、甲基丙烯酰胺‑2‑甲基丙磺酸中的至少一种。  \n\n[0027] 进一步，所述交联剂为三聚氰胺‑甲醛树脂、苯代三聚氰胺‑甲醛树脂、烷基代三聚氰胺‑甲醛树脂、尿素‑甲醛树脂、六甲氧基甲基三聚氰胺树脂、六丁氧基甲基三聚氰胺树脂中的至少一种；所述表面活性剂为全氟乙基乙基醇、全氟丙基乙基醇、全氟丁基乙基醇、全氟己基乙基醇、全氟辛基乙基醇、全氟乙基乙基醇聚氧乙烯醚、全氟乙基乙基醇聚醚、全氟丙基乙基醇聚氧乙烯醚、全氟丙基乙基醇聚醚、全氟丁基乙基醇聚氧乙烯醚、全氟丁基乙基醇聚醚、全氟己基乙基醇聚氧乙烯醚、全氟己基乙基醇聚醚、全氟辛基乙基醇聚氧乙烯醚、全氟辛基乙基醇聚醚中的至少一种；所述流平剂为含有羟基官能团的硅氧烷、聚醚改性硅氧烷中的至少一种；所述碱性化合物为二乙胺、三乙胺、三乙醇胺、氢氧化钠、氢氧化钾、吡啶、4‑氨基吡啶中的至少一种；所述溶剂为醇类溶剂、醚类溶剂、酮类溶剂、酯类溶剂、芳香族类溶剂、胺类溶剂、烃类溶剂、水中的至少一种。  \n\n[0028] 进一步，所述醇类溶剂为甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、仲丁醇、叔丁醇或二丙酮醇；所述醇醚类溶剂为乙二醇单甲醚、乙二醇单乙醚、丙二醇单甲醚、丙二醇单乙醚；所述酮类溶剂为丙酮、甲乙酮、甲基异丁酮或环己酮；所述醚类溶剂为四氢吠喃或二氧六环；所述酯类溶剂为乙酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸异丁酯、乙酸叔丁酯、丙酸甲酯或丙酸乙酯；所述芳香族类溶剂为苯、甲苯或二甲苯；所述胺类溶剂为甲酰胺或二甲基甲酰胺；所述烃类溶剂为正己烷、环己烷、正庚烷、正辛烷或正癸烷。  \n\n[0029] 一种基于两亲性共聚物的防雾涂层组合物的制备方法，按照上述的基于两亲性共聚物的防雾涂层组合物组分进行备料，将单体 $\\mathbf{\\cdotA}_{1}$ 、单体 $\\mathbf{\\cdotA}_{2}$ 、单体 ${\\bf\\cdot A}_{3}$ 、单体 $\\mathrm{.A_{4}}$ 、单体 $\\mathrm{\\cdotA}_{5}$ 、引发剂、碱性化合物加入到溶剂中，在温度为 $50{\\sim}95^{\\circ}\\mathrm{C}$ 的条件下反应 $3\\mathord{\\sim}24\\mathrm{h}$ 得到两亲性共聚物；单体$\\mathrm{A}_{1}$ 、单体 $\\mathrm{\\cdot}\\mathrm{A}_{2}$ 、单体 $\\mathbf{\\cdotA}_{3}$ 、单体 $\\mathrm{.A_{4}}$ 、单体 $\\mathrm{.A_{5}}$ 、引发剂组成的混合物的重量为溶剂重量的 $20\\sim60\\%$ ，所述引发剂为有机过氧化物或偶氮化合物；将交联剂、表面活性剂、流平剂加入到制得的两亲性共聚物中，在室温条件下搅拌混合，制得基于两亲性共聚物的防雾涂层组合物。  \n\n[0030] 所述两亲性共聚物是通过单体 $\\mathrm{\\AA}_{1}$ 、单体 $\\mathrm{\\cdotA_{2}}$ 、单体 ${\\bf\\nabla}\\cdot\\hat{\\bf{A}}_{3}$ 、单体 $\\mathrm{\\A_{4}}$ 、单体 $\\mathrm{\\cdotA}_{5}$ 混合物进行共聚而制备，其可以是无规共聚物、嵌段共聚物、交替共聚物、接枝共聚物、星型共聚物中的任意一种结构，但能够提高防雾涂层的防雾性、粘附性以及相容性，优选无规共聚物和嵌段共聚物的分子链结构。所述两亲性共聚物可以采用现有公知比较成熟的聚合物方法，优选自由基聚合法中的溶液聚合法。  \n\n[0031] 由于在涂膜干燥、加热时，溶剂残留使涂膜对基材的粘附性有很大影响，因此优选沸点不高于 $250^{\\circ}\\mathrm{C}$ 以及对基材腐蚀能力差的溶剂体系。关于自由基聚合物的引发剂，可采用通用的有机过氧化物、偶氮化合物。  \n\n[0032] 上述的基于两亲性共聚物的防雾涂层组合物或上述制备方法制得的基于两亲性共聚物的防雾涂层组合物在车灯、车膜、玻璃、头盔、护目镜、眼镜或透镜设备中的应用。  \n\n[0033] 进一步，将基于两亲性共聚物的防雾涂层组合物通过喷涂或淋涂工艺涂附在基材表面，加热固化，固化温度为 $60{\\sim}120^{\\circ}\\mathrm{C}$ ，固化时间为 $10{\\sim}60\\mathrm{min}$ ，在基材表面得到厚度为 $1\\sim$ $30\\upmu\\mathrm{m}$ 的防雾涂层。作为涂层基材，可以选用聚丙烯酸树脂、聚碳酸酯树脂、聚甲基丙烯酸甲酯树脂、聚对苯二甲酸乙二醇酯树脂、聚对二苯二甲酸丁二醇酯、聚酰亚胺等透明薄膜、板材、及其加工品。  \n\n[0034] 本发明与现有技术相比具有如下有益效果。  \n\n[0035] 1、本发明所述两亲性共聚物由单体 $\\mathbf{\\cdotA}_{1}$ 、单体 $\\mathrm{\\cdotA_{2}}$ 、单体 ${\\bf\\cdot A}_{3}$ 、单体 $\\mathrm{\\cdotA_{4}}$ 、单体 $\\mathrm{.A}_{5}$ 制得，所述单体A 为N‑乙烯基‑2‑吡咯烷酮，能够调节两亲性共聚物的亲水性，同时使得加热固化后的防雾膜具有优异的硬度和耐刮擦性。所述单体 $\\mathrm{\\cdotA_{2}}$ 为具有羟基官能团的乙烯基类单体，羟基官能团具有化学反应活性，在单体 $\\mathrm{\\cdotA}_{5}$ 的磺酸基团催化下与交联剂发生交联反应，形成具有三维网络结构的防雾膜，使得防雾膜具有良好的防雾性和耐水性。所述单体 ${\\bf\\cdot A}_{3}$ 为具有烷基链的丙烯酸酯类单体，能够有效调节两亲性共聚物的疏水性，同时增加了两亲性共聚物与基材的吸附力。所述 $\\mathrm{A}_{4}$ 为具有亲水性官能团的乙烯基类单体，能够有效调节两亲性共聚物的亲水性，改善了防雾膜的防雾性。所述单体 $\\mathrm{.A_{5}}$ 为具有磺酸基团的乙烯基类单体，一方面能够催化单体 $\\mathrm{.A_{2}}$ 中的羟基与交联剂发生交联反应，另一方面能够与碱性化合物反应形成盐，以改善防雾膜的亲水性，从而改善了防雾性。  \n\n[0036] 2、本发明限定了两亲性共聚物中各个单体的含量，按重量百分比计，单体 $\\mathbf{\\cdotA}_{1}$ 的含量为 $3\\sim50\\%$ ，优选地单体 $\\mathbf{\\cdotA}_{1}$ 的含量为 $5\\sim45\\%$ ，若单体 $\\mathrm{.}\\mathrm{A}_{1}$ 含量较多时，会增加防雾膜脆性以及降低防雾性。当 $\\mathrm{A}_{1}$ 含量较少时，会降低防雾膜的硬度，影响防雾膜的耐刮擦性；  \n\n[0037] 单体 $\\mathbf{\\cdotA}_{2}$ 的含量为 $4\\sim25\\%$ ，优选地单体 $\\boldsymbol{\\mathrm{A}}_{2}$ 的含量为 $7\\sim20\\%$ ，当单体 $\\mathbf{\\cdotA}_{2}$ 的含量低于$4\\%$ 时，会降低共聚物的固化效果，当单体 $\\mathrm{.A_{2}}$ 的含量高于 $25\\%$ 时，聚合物体系的交联密度增大，降低了防雾膜的防雾性；  \n\n[0038] 单体 $\\boldsymbol{\\cdot}\\mathrm{A}_{3}$ 的含量为 $10\\sim60\\%$ ，优选地单体 ${\\bf\\cdot A}_{3}$ 的含量为 $15\\sim50\\%$ ，当单体 $\\mathbf{\\cdotA}_{3}$ 的含量低于$10\\%$ 时，共聚物体系较为亲水，防雾膜与基材的粘附性较差。当单体 $\\mathrm{.A_{3}}$ 的含量高于 $60\\%$ 时，共聚物体系较为疏水，防雾膜与基材的粘附性变好，但防雾性变差；  \n\n[0039] 单体 $\\mathrm{.A_{4}}$ 的含量为 $4\\sim40\\%$ ，优选地单体 $\\mathrm{\\A_{4}}$ 的含量为 $6sim35\\%$ ，当单体 $\\mathrm{.A_{4}}$ 的含量低于$4\\%$ ，防雾膜的防雾性变差。当单体 $\\mathrm{.A_{4}}$ 的含量高于 $40\\%$ 时，防雾膜与基材的粘附力变差；  \n\n[0040] 单体 $\\mathrm{.A}_{5}$ 的含量为 $0.1\\sim20\\%$ 。优选地单体 $\\mathrm{\\cdotA}_{5}$ 的含量为 $0.5\\sim18\\%$ ，当单体 $\\mathrm{\\cdotA_{5}}$ 含量低于$0.1\\%$ 时，整个两亲性共聚物防雾涂层体系的固化效果差，防雾性变差。当单体 $\\mathrm{\\cdotA_{5}}$ 含量高于$20\\%$ 上，其在聚合物过程中容易被氧化，影响后期两亲性共聚物防雾涂层在固化过程中的催化效果。  \n\n[0041] 3、本发明限定了基于两亲性共聚物的防雾涂层组合物中各个组分的含量，以100重量份的两亲性共聚物为基准，交联剂的含量为 $5\\sim50$ 重量份，优选地交联剂的含量为 $10\\sim$ 40重量份，交联剂与两亲性共聚物在加热条件下发生交联反应，形成三维网络结构的防雾膜，当交联剂的含量低于5重量份或高于50重量份时，基于两亲性共聚物构成的防雾涂层体系的固化效果不好，防雾效果较差。  \n\n[0042] 4、本发明以100重量份的两亲性共聚物为基准，限定了表面活性剂的含量为 $0.5\\sim$ 15重量份，优选地表面活性剂的含量为 $0.8{\\sim}14$ 重量份，表面活性剂降低了防雾膜的表面能，使得防雾膜在起雾过程中形成的小水珠能够形成均匀的水膜。所述表面活性剂为表面活性剂为全氟乙基乙基醇、全氟丙基乙基醇、全氟丁基乙基醇、全氟己基乙基醇、全氟辛基乙基醇、全氟烷基乙基醇、全氟乙基乙基醇聚氧乙烯醚、全氟乙基乙基醇聚醚、全氟丙基乙基醇聚氧乙烯醚、全氟丙基乙基醇聚醚、全氟丁基乙基醇聚氧乙烯醚、全氟丁基乙基醇聚醚、全氟己基乙基醇聚氧乙烯醚、全氟己基乙基醇聚醚、全氟辛基乙基醇聚氧乙烯醚、全氟辛基乙基醇聚醚、全氟烷基乙基醇聚氧乙烯醚、全氟烷基乙基醇聚醚中的至少一种，进而表面活性剂中的羟基能够与交联剂反应接在防雾涂层主树脂中，使得防雾膜的防雾效果更持久。当表面活性剂的含量低于0.5重量份或高于15重量份时，其防雾涂层组合物膜固化后的防雾效果都较差，表面形成很多小水珠，不能形成大面积的均匀水膜。  \n\n[0043] 5、本发明以100重量份的两亲性共聚物为基准，限定了流平剂的含量为 $0.1{\\sim}2$ 重量份，优选地流平剂的含量为 $0.5\\sim1.5$ 重量份，流平剂能够与交联剂反应接枝在防雾涂层主树脂中，在防雾过程中不被水份带出，防止其产生流痕等不良现象。同时使得防雾涂层在涂覆成膜和加热固化过程中，改善其成膜性，利于在基材表面形成防雾膜。当流平剂含量低于0.1重量份时，导致防雾涂层组合物的成膜性较差，容易收缩和起皱。当流平剂含量高于2重量份时，导致形成的防雾膜的防雾性较差。  \n\n[0044] 6、本发明限定了碱性化合物的含量为相对于两亲性共聚物的单体 $\\mathrm{A}_{5}$ 的 $20\\sim$ $99\\%$ ，即以两亲性共聚物的单体 $\\mathrm{.A}_{5}$ 为100摩尔份，碱性化合物的含量为 $20{\\sim}99$ 摩尔份，当碱性化合物的含量低于20摩尔份时，涂覆形成的防雾膜的防雾性较差且耐热老化性较差。当碱性化合物的含量高于99摩尔份时，涂覆膜的固化效果较差，形成的膜耐水性较差。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 具体实施方式  \n\n[0045] 下面结合具体实施例对本发明作详细说明。[0046] 实施例一，一种基于两亲性共聚物的防雾涂层组合物，包括两亲性共聚物、交联剂、表面活性剂、流平剂、碱性化合物和溶剂，其制备方法包括如下步骤：[0047] 步骤一，两亲性共聚物的制备，向500mL玻璃三口烧瓶反应容器中加入作为溶剂的$100\\mathrm{g}$ 异丙醇、作为单体A 的 $30\\mathrm{g}$ 的N‑乙烯基‑2‑吡咯烷酮、作为单体 $\\mathrm{\\cdotA_{2}}$ 的 $20\\mathrm{g}$ 丙烯酸羟乙酯、作为单体 ${\\bf\\cdot A}_{3}$ 的 $30\\mathrm{g}$ 甲基丙烯酸甲酯，作为单体 $\\mathrm{\\cdotA_{4}}$ 的18g的N , ${\\mathrm{N}}^{-}$ 二甲基丙烯酸胺，作为单体 $\\mathrm{\\cdotA_{5}}$ 的1g的2‑丙烯酰胺‑2‑甲基丙磺酸、作为碱性化合物的 $0.2\\mathrm{g}$ 吡啶，吡啶的含量为相对于两亲性共聚物的单体 $\\mathrm{.A}_{5}$ 的 $50\\mathrm{mol}\\%$ ，在磁力搅拌下升温加热至 $55^{\\circ}\\mathrm{C}$ ，然后将作为溶液自由基聚合引发剂的 $\\mathrm{1g}$ 偶氮二异丁腈加入三口瓶反应器中，将水浴锅温度升高至 $75\\mathrm{{^\\circC}}$ 继续反应10小时，得到 $200.2\\mathrm{g}$ 质量浓度为 $50\\%$ 的两亲性共聚物溶液。  \n\n[0048] 步骤二，在上述 $200.2\\mathrm{g}$ 的两亲性共聚物溶液中加入 $300\\mathrm{g}$ 异丙醇和 $300\\mathrm{g}$ 丙酮，将两亲性共聚物溶液的质量浓度调节至 $12.5\\%$ 。然后将作为交联剂的33.7g六甲氧基甲基三聚氰胺树脂、作为表面活性剂的 $6\\mathrm{g}$ 全氟己基乙基醇、作为流平剂的0.5g聚醚改性聚二甲基硅氧烷加入到质量浓度为 $12.5\\%$ 的两亲性共聚物溶液中，搅拌混合均匀，得到基于两亲性共聚物的防雾涂层组合物。  \n\n[0049] 异丙醇以下简称为IPA，丙酮以下简称为AC，N‑乙烯基‑2吡咯烷酮以下简称为NVP，丙烯酸羟乙酯以下简称为HEA，甲基丙烯酸甲酯以下简称为MMA，N,N‑二甲基丙烯酸胺以下简称DMAA，2‑丙烯酰胺‑2‑甲基丙磺酸以下简称为AMPS，吡啶以下简称为Py，偶氮二异丁腈以下简称为AIBN，六甲氧基甲基三聚氰胺树脂以下简称为HMMM，全氟己基乙基醇以下简称为TEOH‑6，聚醚改性聚二甲基硅氧烷以下简称为PEPS。  \n\n[0050] 按照表1中所述组分含量制得实施例二至实施例九的基于两亲性共聚物的防雾涂 层组合物，分别对实施例一至实施例九的产物进行性能评价。  \n\n[0051] 1、成膜性的评价：用喷涂法将实施例一至实施例九制得的防雾涂层组合物涂覆在材质为聚碳酸酯的透明基材上，防雾涂层在自然表干过程和固化过程中膜表面流平效果很好，不产生褶皱、纹路、流挂和边缘收缩等现象，则判断成膜性优异。  \n\n[0052] 2、防雾浊性的评价：在室温 $25\\mathrm{{^\\circC}}$ 、湿度为 $70\\sim100\\%$ 的环境下，用喷涂法将实施例一至实施例九制得的防雾涂层组合物涂覆在材质为聚碳酸酯的透明基材上，使固化后的涂膜厚度为 $1\\sim4\\upmu\\mathrm{m}$ 。涂覆后的防雾膜放置环境中20分钟，然后在对应温度和时间下进行固化反应。在 $100\\%$ 的相对湿度环境中，用肉眼观察涂膜外观，确定没有发白等外观异常现象，则判断防雾浊性优异。  \n\n[0053] 3、防雾性的评价：将制得的防雾涂层涂覆在聚碳酸酯实验片并在对应温度和时间条件下固化后，将涂膜实验片设置在离温度为 $80^{\\circ}\\mathrm{C}$ 的温水液面的5cm高度处，且涂膜面朝下，通过肉眼观察10分钟内没有结雾，则判断防雾性优异。  \n\n[0054] 4、粘附力的评价：将涂覆由防雾涂层的聚碳酸酯的实验片，利用挂格器将涂膜切割成1x1cm2的方格，然后在格子表面压附3M胶带，观察方格玻璃的情况，如果方格玻璃上呈方格的涂膜没有脱落，则判断粘附力性能优异。  \n\n[0055] 5、耐热性的评价：将涂覆有防雾涂层的聚碳酸酯的实验片在温度为 $120^{\\circ}\\mathrm{C}$ 的条件下放置240小时。冷却后实施上述防雾性试验，进行相同评价。如果防雾性能优化、且没有出现发白、无纺布无法擦掉防雾膜，则判断耐热性优异。  \n\n[0056] 6、耐水性的评价：将上述涂覆防雾涂层的聚碳酸酯的实验片，在温度为 $40^{\\circ}\\mathrm{C}$ 的水中浸泡240小时，然后室温下存放1小时。如果外观无发白、乳化、流痕、起皮等现象，且防雾性和粘附力性能优异，则判断耐水性能优异。  \n\n[0057] 7、硬度评价：按GB/T  6739‑2006标准对防雾涂层进行硬度测试，如果硬度达到1H则判断硬度性能优异。  \n\n[0058] 8、流痕评价：将防雾涂层涂覆在聚碳酸酯实验片并在对应温度和时间条件下固化后，将涂膜实验片设置在离温度为 $80^{\\circ}\\mathrm{C}$ 的温水液面的5cm高度处，且涂膜面朝下，并将实验片进行10分钟蒸汽实验。然后，将实验片倾斜 $30^{\\circ}$ °放置在室温环境中自然干燥。如肉眼观察无水流和水珠干燥后的痕迹，则判断该防雾涂层不产生流痕的性能优异。  \n\n[0059] 所述喷涂法具体为：将基于两亲性共聚物的防雾涂层组合物通过喷涂或淋涂工艺涂附在基材表面，加热固化，固化温度为 $60{\\sim}120^{\\circ}\\mathrm{C}$ ，固化时间为 $10{\\sim}60\\mathrm{min}$ ，在基材表面得到厚度为 $1\\sim30\\upmu\\mathrm{m}$ 的防雾涂层。作为涂层基材，可以选用聚丙烯酸树脂、聚碳酸酯树脂、聚甲基丙烯酸甲酯树脂、聚对苯二甲酸乙二醇酯树脂、聚对二苯二甲酸丁二醇酯、聚酰亚胺等透明薄膜、板材、及其加工品。  \n\n[0060] 表1实施例一至实施例九的组分含量及性能评价结果  \n\n[0061]  \n\n<html><body><table><tr><td colspan=\"2\">原料名称</td><td>单 位</td><td>实施 例一</td><td>实施 例二</td><td>实施 例三</td><td>实施 例四</td><td>实施 例五</td><td>实施 例六</td><td>实施 例七</td><td>实施 例八</td><td>实施 例九</td></tr><tr><td>单体A</td><td>NVP</td><td>g</td><td>30</td><td>30</td><td>20</td><td>40</td><td>40</td><td>30</td><td>30</td><td>30</td><td>30</td></tr><tr><td>单体A2</td><td>HEA</td><td>g</td><td>20</td><td>20</td><td>20</td><td>10</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td></tr><tr><td>单体A3</td><td>MMA</td><td>g</td><td>30</td><td>30</td><td>40</td><td>30</td><td>30</td><td>40</td><td>28</td><td>28</td><td>30</td></tr><tr><td>单体A4</td><td>DMAA</td><td>g</td><td>18</td><td>18</td><td>18</td><td>18</td><td>8</td><td>8</td><td>16</td><td>18</td><td>18</td></tr><tr><td>单体A5</td><td>AMPS</td><td>g</td><td>1</td><td>1</td><td>1</td><td>1</td><td>1</td><td>1</td><td>5</td><td>1</td><td>1</td></tr><tr><td>引发剂</td><td>AIBN</td><td>g</td><td>1</td><td>1</td><td>1</td><td>1</td><td>1</td><td>1</td><td>1</td><td>3</td><td>1</td></tr><tr><td>交联剂</td><td>HMMM</td><td>g</td><td>33.7</td><td>33.7</td><td>33.7</td><td>33.7</td><td>33.7</td><td>33.7</td><td>33.7</td><td>33.7</td><td>33.7</td></tr><tr><td>表面活 性剂</td><td>TEOH-6</td><td>g</td><td>6</td><td>6</td><td>6</td><td>６</td><td>6</td><td>6</td><td>6</td><td>6</td><td>12</td></tr><tr><td>流平剂</td><td>PEPS</td><td>g</td><td>0.5</td><td>0.5</td><td>0.5</td><td>0.5</td><td>0.5</td><td>0.5</td><td>0.5</td><td>0.5</td><td>0.5</td></tr><tr><td>碱性化 合物</td><td>Py</td><td>g</td><td>0.2</td><td>0.4</td><td>0.2</td><td>0.2</td><td>0.2</td><td>0.2</td><td>1</td><td>0.2</td><td>0.2</td></tr><tr><td rowspan=\"2\">溶剂</td><td>IPA</td><td>g</td><td>400</td><td>400</td><td>400</td><td>400</td><td>400</td><td>400</td><td>400</td><td>400</td><td>400</td></tr><tr><td>AC</td><td>g</td><td>300</td><td>300</td><td>300</td><td>300</td><td>300</td><td>300</td><td>300</td><td>300</td><td>300</td></tr><tr><td rowspan=\"12\">评价结</td><td colspan=\"2\">固化时间（分 钟)</td><td>25</td><td>30</td><td>25</td><td>25</td><td>25</td><td>25</td><td>15</td><td>25</td><td>25</td></tr><tr><td colspan=\"2\">固化温度（C）</td><td>90</td><td>100</td><td>90</td><td>90</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td colspan=\"2\">成膜性</td><td>·</td><td></td><td>·</td><td>·</td><td>90</td><td>90</td><td>90</td><td>90</td><td>90</td></tr><tr><td colspan=\"2\"></td><td></td><td>·</td><td></td><td></td><td></td><td>·</td><td>·</td><td></td><td>·</td></tr><tr><td colspan=\"2\">防雾浊性</td><td></td><td></td><td></td><td></td><td>：。</td><td></td><td></td><td></td><td></td></tr><tr><td colspan=\"2\">粘附力</td><td>·</td><td>。</td><td>·</td><td></td><td></td><td></td><td></td><td>·</td><td></td></tr><tr><td colspan=\"2\">耐热性</td><td>·</td><td>·</td><td>·</td><td></td><td></td><td>·</td><td>·</td><td></td><td>·</td></tr><tr><td colspan=\"3\">耐水性</td><td></td><td>·</td><td>·</td><td>· ·</td><td>· ·</td><td></td><td></td><td>·</td></tr><tr><td colspan=\"3\"></td><td>·</td><td>·</td><td></td><td></td><td></td><td>·</td><td>·</td><td></td></tr><tr><td colspan=\"3\">硬度 流痕</td><td></td><td>。</td><td>· V</td><td>· ·</td><td>· ·</td><td>· ·</td><td>·</td><td>· ·</td></tr></table></body></html>  \n\n[0062] 其中， $\\bullet$ 表示性能优异； $\\bigcirc$ 表示满足应用要求； $\\bigtriangledown$ 表示不能满足应用要求。  \n\n[0063] 由表1可知，在实施例一所述的基于两亲性共聚物的防雾涂层组合物中，两亲性共聚物各个单体的含量在优选范围内，因此防雾涂层具有非常优异的涂膜性能，在温度为90$\\mathrm{{^\\circC}}$ 的条件下固化25min，得到的防雾膜具有优异的防雾浊性、防雾性、粘附力、耐热性、耐水性、硬度以及不产生流痕。  \n\n[0064] 实施例二所述的基于两亲性共聚物的防雾涂层组合物相比于实施例一，防雾涂层组合物中作为碱性化合物的吡啶为 $0.4\\mathrm{g}$ ，使得防雾涂层组合物需要在 $100^{\\circ}\\mathrm{C}$ 条件下固化30分钟，且其固化程度不充分，使得防雾膜在粘附力、耐水性、硬度和流痕方面的性能降低，但仍能够满足应用要求。  \n\n[0065] 实施例三所述的基于两亲性共聚物的防雾涂层组合物相比于实施例一，两亲性共聚物中作为单体 $\\mathrm{\\cdotA_{3}}$ 的MMA用量增加 $10\\mathrm{g}$ ，作为单体 $\\mathrm{\\ddot{A}_{1}}$ 的NVP的用量减少 $10\\mathrm{g}$ ，使得两亲性共聚物体系更加疏水，使得得到的防雾膜的防雾浊性变差，但满足要求；防雾性变差，且不能满足应用。  \n\n[0066] 实施例四所述的基于两亲性共聚物的防雾涂层组合物相比于实施例一，两亲性共聚物中作为单体 $\\mathrm{\\cdotA_{1}}$ 的NVP的用量增加 $10\\mathrm{g}$ ，作为单体 $\\mathrm{\\cdotA_{2}}$ 的HEA的用量减少 $10\\mathrm{g}$ ，使得两亲性共聚物体系更加亲水，交联度降低。实施例四中防雾膜的粘附力和耐水性变差，但满足要求；防雾过程产生流痕，且不能满足应用。  \n\n[0067] 实施例五所述的基于两亲性共聚物的防雾涂层组合物相比于实施例一，两亲性共聚物中作为单体 $\\mathrm{\\cdotA_{1}}$ 的NVP的增加 $10\\mathrm{g}$ ，作为单体 $\\mathrm{\\cdotA_{4}}$ 的DMAA用量减少 $10\\mathrm{g}$ ，使得两亲性共聚物体系变得更疏水。实施例五中防雾膜的成膜性和防雾性变差，但满足应用要求。  \n\n[0068] 实施例六所述的基于两亲性共聚物的防雾涂层组合物相比于实施例一，两亲性共聚物中作为单体 $\\mathrm{\\cdotA_{3}}$ 的MMA用量增加 $10\\mathrm{g}$ ，作为单体 $\\mathrm{.A_{4}}$ 的DMAA用量减少 $10\\mathrm{g}$ ，使得两亲性共聚物体系变得更疏水。实施例六中防雾膜的防雾浊性变差，但满足要求；防雾性变差，且不能满足应用要求。  \n\n[0069] 实施例七所述的基于两亲性共聚物的防雾涂层组合物相比于实施例一，防雾涂层组合物中作为单体 $\\boldsymbol{\\cdot}\\mathrm{A}_{3}$ 的MMA用量减少 $\\mathrm{2g}$ ，作为单体 $\\mathrm{.A_{4}}$ 的DMAA用量减少 $2\\mathrm{g}$ ，作为单体 $\\mathrm{.A_{5}}$ 的AMPS用量增加 $4\\mathrm{g}$ ，作为碱性化合物的Py用量增加 $0.8\\mathrm{g}$ ，使共聚物体系的亲疏水性无很大改变，但增加了磺酸根的量。由于磺酸根在高温条件下分解变质，使得实施例七中防雾膜的耐热老化性变差，但满足应用要求。  \n\n[0070] 实施例八所述的基于两亲性共聚物的防雾涂层组合物相比于实施例一，防雾涂层组合物中作为引发剂的AIBN用量增加 $\\mathrm{2g}$ ，使得共聚物的分子量分布更宽、且平均数均分子量变小。实施例八中防雾膜的成膜性变差，但满足应用要求；防雾过程产生轻微流痕，但满足应用要求。  \n\n[0071] 实施例九所述的基于两亲性共聚物的防雾涂层组合物相比于实施例一，防雾涂层组合物中作为表面活性剂的TEOH‑6用量增加 $6\\mathrm{g}$ ，增加防雾膜表面的疏水性，使得实施例九中防雾膜的防雾性变差，但满足应用要求。  \n\n[0072] 以上所述仅为本发明的优选实施例及比较例，并不用于限制本发明。对于相关领域的科研技术人员来说，本发明可以有多重更改和变化。凡在本发明的思想和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围内。",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# (19)国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n(21)申请号 202111651551 .0  \n(22)申请日 2021 .12.31  \n(65)同一申请的已公布的文献号申请公布号 CN 114213963 A  \n(43)申请公布日 2022.03.22  \n(73)专利权人 武汉中科先进材料科技有限公司地址 430000 湖北省武汉市武汉经济技术开发区201M地块华人汇和科技园（华中智谷）一期F10栋研发楼1-2层  \n(72)发明人 康翼鸿　喻学锋　程文杰　吴列杨帆  \n(74)专利代理机构 武汉高得专利代理事务所(普通合伙) 42268专利代理师 姜璐",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n一种光-热双重固化无溶剂耐磨防雾涂料及其制备方法和应用",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明公开了一种光‑热双重固化无溶剂耐磨防雾涂料及其制备方法和应用，该防雾涂料包括以下组份：光‑热双固化树脂、稀释单体、固化剂和光引发剂；所述的双固化树脂为本发明设计得到的超支化亲水树脂，既可以UV固化，又可以热固化，将其应用到防雾配方中得到高耐磨无溶剂防雾涂料，该涂料安全无毒，在紫外光照射下先形成基础光固化，然后自然放置能够较快实现深层次热固化，形成的涂膜在各种基材上均具有良好的附着力、透明度、耐磨性和耐化学品性，并具有优异持久的防雾性能。  \n\n(51)Int.Cl.C09D 175/14(2006.01)C09D 171/02(2006.01)  \n\n(56)对比文件CN 101602913 A,2009.12.16  \n\n审查员 廖晓凤  \n\n1.一种光‑热双重固化无溶剂耐磨防雾涂料，其特征在于，由以下质量份的组份制成：光‑热双固化树脂30‑70份、稀释单体20‑40份、固化剂5‑15份、光引发剂3‑5份和流平剂0.5‑1.0份；其中，所述光‑热双固化树脂由二异氰酸酯与醇1反应得到预聚体1，再与醇2反应得到超支化树脂，将羟基丙烯酸酯单体与二异氰酸酯反应得到部分封端的预聚体2，最后将超支化树脂与预聚体2混合反应，得到光‑热双固化树脂；所述固化剂为热固型异氰酸酯固化剂，能够与光‑热双固化树脂中的羟基发生交联反应，从而实现深层次固化，包括脂肪族聚异氰酸酯固化剂Desmodur  N100、N75、N3200、N3390、N3400、N3600及Desmodur  Z4470，以及芳香族聚异氰酸酯固化剂Desmodur  44V20L、HL和IL1451中的至少一种；所述醇1为小分子多元醇，醇2为二元醇；或者所述醇1为二元醇，醇2为小分子多元醇；所述小分子多元醇包括甘油、三羟甲基丙烷、三羟甲基乙烷中的至少一种；所述二元醇为1,6‑己二醇或1,4‑丁二醇中的任一种与聚乙二醇400或聚乙二醇600中的任一种的混合。  \n\n2.根据权利要求1所述防雾涂料，其特征在于：所述稀释单体包括三羟甲基丙烷三丙烯酸酯(TMPTA)、乙氧基化三羟甲基丙烷三丙烯酸酯(ETPTA)、季戊四醇三丙烯酸酯(PETA)、双季戊四醇六丙烯酸酯(DPHA)、丙烯酰吗啉(ACMO)、聚乙二醇400二丙烯酸酯(PEG400DA)、聚乙二醇600二丙烯酸酯(PEG600DA)、聚乙二醇1000二丙烯酸酯(PEG1000DA)中的一种或至少两种的组合。  \n\n3.根据权利要求 $1{\\sim}2$ 任一项所述防雾涂料，其特征在于：所述光引发剂为夺氢型水性光引发剂，包括光引发剂1173、TPO、BP、184、907中的一种或至少两种的组合。  \n\n4.根据权利要求 $1{\\sim}2$ 任一项所述防雾涂料，其特征在于：所述流平剂包括氟素润湿流平剂FSWET1010、含氟流平剂FS3100、聚醚硅氧烷流平剂TEGO410的一种或至少两种的组合。  \n\n5.一种光‑热双重固化无溶剂耐磨防雾涂料的制备方法，其特征在于，包含如下质量份的组分：光‑热双固化树脂30‑70份、稀释单体20‑40份、固化剂5‑15份、光引发剂3‑5份，流平剂0.5‑1.0份；包括以下步骤：在容器内加入所述稀释单体，在搅拌状态下依次加入光引发剂、光‑热双固化树脂并搅拌溶解，再依次加入流平剂并搅拌，加入固化剂并搅拌均匀即得所述防雾涂料；其中，所述光‑热双固化树脂由二异氰酸酯与醇1反应得到预聚体1，再与醇2反应得到超支化树脂，将羟基丙烯酸酯单体与二异氰酸酯反应得到部分封端的预聚体2，最后将超支化树脂与预聚体2混合反应，得到光‑热双固化树脂；所述固化剂为热固型异氰酸酯固化剂，能够与光‑热双固化树脂中的羟基发生交联反应，从而实现深层次固化，包括脂肪族聚异氰酸酯固化剂Desmodur  N100、N75、N3200、N3390、N3400、N3600及DesmodurZ4470，以及芳香族聚异氰酸酯固化剂Desmodur  44V20L、HL和IL1451中的至少一种；所述醇1为小分子多元醇，醇2为二元醇；或者所述醇1为二元醇，醇2为小分子多元醇；所述小分子多元醇包括甘油、三羟甲基丙烷、三羟甲基乙烷中的至少一种；所述二元醇为1,6‑己二醇或1,4‑丁二醇中的任一种与聚乙二醇400或聚乙二醇600中的任一种的混合。  \n\n6.一种光‑热双重固化无溶剂耐磨防雾涂料在防雾涂层上的应用，其特征在于，将权利要求 $1{\\sim}4$ 任一项所述防雾涂料或权利要求5所述制备方法制得的防雾涂料涂覆在基质上，经固化后形成所述防雾涂层；所述基质包括玻璃、塑料、金属。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 一种光‑热双重固化无溶剂耐磨防雾涂料及其制备方法和应用",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明属于涂料技术领域，具体涉及一种防雾涂料及其制备方法和应用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 近年来防雾技术逐步受到人们的重视，以亲水型防雾涂层的研发进展最快，已经形成了一系列先进的技术和相对成熟的产品。亲水防雾涂料是一种功能性材料，它是以具有亲水基团的高分子材料为主要成分，配以相应比例的稀释剂和其他助剂调配而成的具有防雾功能的化工产品，能够获得比防雾喷剂更持久的防雾效果，是现阶段防雾的最有效途径之一。  \n\n[0003] 按照固化方式不同，有热固化型防雾涂料和UV(紫外线)光固化型防雾涂料。虽然热固化型防雾涂料可以提供良好的耐磨性，但它们需要长固化时间和高能量消耗以便溶剂蒸发，生产效率低。而UV(紫外线)光固化型防雾涂料的透光率一般要比热固化防雾涂料高，在紫外光下能够实现瞬间固化，非常适合连续工业化生产，但它们的耐磨性通常低于热固化涂料。  \n\n[0004] 为克服以上问题，不少研究者提出了光‑热双重固化的方式，将光固化的便捷性与热固化良好的耐磨性结合在一起，发挥各自的优点。CN105315735采用先热固化，再光固化的方式，得到防雾性能优异和耐磨性好的防雾涂料，但体系需要超过100oC高温固化才能实现所述的性能。CN112391112采用光‑热双重固化，同时引入亲水无机纳米粒子来提高防雾和耐磨性。但是同样需要高温固化工艺，能耗高，且需引入大量有机溶剂实现纳米粒子的分散。现有报道都难以得到无溶剂、低能耗、耐磨性好、防雾性能优异的室温固化涂层。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0005] 本发明的目的是针对现有技术的不足，本发明提供一种光‑热双固化树脂，该树脂为一种超支化结构，表面既含有双键可供光固化，又含有羟基可进行热固化，同时含有亲水链段提供防雾性能，涂布完毕后无需加热烘烤，在常温下即可完成光固化和热固化，适用于多种基材，特别是不耐高温的塑料表面。  \n\n[0006] 为实现上述目的，本发明采用的技术方案如下：  \n\n[0007] 首先，本发明提供一种光‑热双重固化无溶剂耐磨防雾涂料，由以下质量份的组份制成：光‑热双固化树脂30‑70份、稀释单体20‑40份、固化剂5‑15份、光引发剂3‑5份和流平剂0.5‑1 .0份。  \n\n[0008] 具体的，所述光‑热双固化树脂由二异氰酸酯与醇1反应得到预聚体1，再与醇2反应得到超支化树脂，将羟基丙烯酸酯单体与二异氰酸酯反应得到部分封端的预聚体2，最后将超支化树脂与预聚体2混合反应，得到光‑热双固化树脂。  \n\n[0009] 在某些实施例中，所述醇1为小分子多元醇，醇2为二元醇。  \n[0010] 在某些实施例中，所述醇1为二元醇，醇2为小分子多元醇。  \n\n[0011] 优选地，所述二异氰酸酯包括异佛尔酮二异氰酸酯（IPDI）、甲苯二异氰酸酯（TDI）、六亚甲基二异氰酸酯（HDI）、二环己基甲烷二异氰酸酯（HMDI）、改性二苯基甲烷二异氰酸酯（液化MDI）中的一种或至少两种的组合；  \n\n[0012] 所述的二元醇包括1 ,3‑丙二醇、1 ,4‑丁二醇、1 ,2‑戊二醇、1 ,6‑己二醇、聚乙二醇（分子量200‑1000）中的至少一种；  \n\n[0013] 所述的小分子多元醇包括季戊四醇、甘油、三羟甲基丙烷、三羟甲基乙烷中的至少一种；  \n\n[0014] 所述羟基丙烯酸酯单体包括甲基丙烯酸羟乙酯(HEMA)、丙烯酸羟乙酯(HEA)、丙烯酸羟丙酯(HPA)、4‑羟基丁基丙烯酸酯(4HBA)、季戊四醇三丙烯酸酯(PETA)中的至少一种。  \n\n[0015] 再一方面，本发明提供了一种防雾涂料，由以下质量份的组份制成：光‑热双固化树脂30‑70份、稀释单体20‑40份、固化剂5‑15份、光引发剂3‑5份，流平剂0.5‑1.0份；所述亲水树脂为上述所述的高耐磨的亲水性树脂；  \n\n[0016] 优选地，所述稀释单体包括三羟甲基丙烷三丙烯酸酯（TMPTA）、乙氧基化三羟甲基丙烷三丙烯酸酯（ETPTA）、季戊四醇三丙烯酸酯（PETA）、双季戊四醇六丙烯酸酯（DPHA）、丙烯酰吗啉（ACMO）、聚乙二醇400二丙烯酸酯（PEG400DA）、聚乙二醇600二丙烯酸酯（PEG600DA）、聚乙二醇1000二丙烯酸酯（PEG1000DA）中的一种或至少两种的组合；  \n\n[0017] 优选地，所述固化剂为热固型异氰酸酯固化剂，能够与光‑热双固化树脂中的羟基发生交联反应，从而实现深层次固化。优选地，包括脂肪族聚异氰酸酯固化剂DesmodurN100、N75、N3200、N3390、N3400、N3600及Desmodur  Z4470；以及芳香族聚异氰酸酯固化剂Desmodur  44V20L、HL和IL1451中的至少一种；  \n\n[0018] 优选地，所述光引发剂为夺氢型水性光引发剂；优选地，所述光引发剂包括光引发剂1173、TPO、BP、184、907中的一种或至少两种的组合。  \n\n[0019] 优选地，所述流平剂包括氟素润湿流平剂FSWET1010、含氟流平剂FS3100、聚醚硅氧烷流平剂TEGO410。  \n\n[0020] 上述所述的光‑热双重固化无溶剂耐磨防雾涂料的制备方法，包括以下步骤：将光‑热双固化树脂30‑70份、稀释单体20‑40份、固化剂5‑15份、光引发剂3‑5份，流平剂0.5‑1.0份分散混合，即可得到所述防雾涂料；  \n\n[0021] 优选地，具体包括以下步骤：在容器内加入所述活性稀释剂，在搅拌状态下依次加入光引发剂、光‑热双固化树脂并搅拌溶解，流平剂并搅拌，固化剂并搅拌均匀即得所述防雾涂料。  \n\n[0022] 本发明再一方面提供了一种上述所述的防雾涂料在制备防雾涂层中的应用。  \n\n[0023] 本发明再一方面提供了一种防雾涂层，由以下方法制备得到：将上述所述的防雾涂料涂覆在基质上，经固化后形成所述防雾涂层；即上述防雾涂料在防雾涂层上的应用。  \n\n[0024] 优选地，所述基质包括玻璃、塑料、金属，具体包括汽车玻璃，建筑物玻璃，广告牌，浴室镜及公共交通工具玻璃，铁板，铜板及铝合金板；  \n\n[0025] 优选地，所述涂覆的方法包括刮涂、滴涂、辊涂、淋涂、旋涂；  \n\n[0026] 优选地，所述固化的方法先经200‑2000mJ紫外光固化，然后在室温条件下放置37d即可。  \n\n[0027] 与现有技术相比，本发明具有如下突出效果：  \n\n[0028] 本发明设计了一种具有光‑热双重固化功能的亲水性聚合物，即一种光‑热双固化树脂，表面既含有双键可供光固化，又含有羟基可进行热固化，其亲水链段能持久发挥防雾功能，它具有的超支化结构使分子链不易缠结，黏度较小，溶解性好。将其应用到防雾涂料配方中得到本申请保护的防雾涂料，防雾涂料不含溶剂，安全无毒，能够在多种类型的基材上成膜，涂布完毕后无需加热烘烤，适用于多种基材，特别是不耐高温的塑料表面；在紫外光照射下,  涂料中所含的碳碳双键被光引发剂捕捉，激发形成自由基，自由基相互结合形成基础光固化涂层，接着涂料中含有的‑OH与异氰酸酯固化剂中的‑NCO在室温下发生交联反应，室温自然放置就能够较快实现深层次热固化；这种高度交联形成的涂层与基材的粘接强度高，形成的涂层具有良好的透明度、高硬度、耐划伤性和耐化学品性，并具有优异的防雾效果、防雾持久性、良好的耐水性、低粘性。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 具体实施方式  \n\n[0029] 下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。  \n\n[0030] 制备光‑热双固化树脂的过程中还额外添加了二月桂酸二丁基锡DBTDL、对羟基苯甲醚MEHQ、2,6‑二叔丁基‑4‑甲基苯酚BHT，此为常规选择，对性能没有影响，起到催化剂和阻聚剂的作用。  \n\n[0031] 实施例1  防雾涂层的制备  \n\n[0032] （a）光‑热双固化树脂的制备： $250\\mathrm{mL}$ 的三口烧瓶中加入 $44.46\\mathrm{g}$ (0 .2mol)  异佛尔酮二异氰酸酯和 $0.09\\mathrm{g}$ (0.1wt%)  二月桂酸二丁基锡开启搅拌；另称取 $2.36\\mathrm{g}$ $\\left(0.02\\mathrm{mol}\\right)$ )$^{1,6^{-}}$ 己二醇和 $32.0\\mathrm{g}$ (0.08mol)  聚乙二醇400，充分混合至完全溶解，转移至恒压滴液漏斗中，在室温下缓慢滴加至上述三口烧瓶中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $70^{\\circ}\\mathrm{C}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值（通过盐酸二正丁胺法测定），得到亲水改性的预聚体1，然后加入 $26.83\\mathrm{g}$ (0 .2mol)  三羟甲基丙烷继续反应直至异氰酸酯基(‑NCO)的含量为零，得到超支化树脂；  \n\n[0033] 另取250mL三口烧瓶，向其加入11 .11g  (0 .05mol)  异佛尔酮二异氰酸酯和 $0.016\\mathrm{g}$ $(0.1\\mathrm{wt\\%})$ 二月桂酸二丁基锡开启搅拌；另依次称取 $0.044\\mathrm{g}$ $(0.262\\mathrm{wt}\\%)$ )  对羟基苯甲醚，$0.088\\mathrm{g}$ $(0.525\\mathrm{wt\\%})$ 2,6‑二叔丁基‑4‑甲基苯酚以及 $5.8\\mathrm{g}$ $\\left(0.05\\mathrm{mol}\\right)$ )  丙烯酸羟乙酯，充分混合至完全溶解，转移至恒压滴液漏斗中，在室温下缓慢滴加至上述三口烧瓶中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $70\\mathrm{{^\\circC}}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值（通过盐酸二正丁胺法测定)，降温得到预聚体2，加入上述超支化树脂继续反应直至异氰酸酯基(‑NCO)的含量为零，得到光‑热双固化树脂，干燥密封保存。  \n\n[0034] （b）防雾涂料的制备：将50份光‑热双固化树脂、24份聚乙二醇600二丙烯酸酯（PEG600DA）、10份三羟甲基丙烷三丙烯酸酯（TMPTA）、10份固化剂Desmodur  N3390、1份流平剂FSWET1010、5份光引发剂TPO加入分散料筒内高速分散30min，得到均匀透明的防雾涂料。[0035] （c）防雾涂层的制备：将（b）中制备的防雾涂料用线棒均匀的涂在干净的PET膜上，然后放在传送带式UV固化机上，经800mJ紫外光固化后，在室温条件下放置7d即得防雾涂层。  \n\n[0036] 实施例2  防雾涂层的制备  \n\n[0037] （a）光‑热双固化树脂的制备：250mL的三口烧瓶中加入 $34.83\\mathrm{g}$ (0 .2mol)  甲苯二异氰酸酯和 $0.08\\mathrm{g}$ $(0.1\\mathrm{wt\\%})$ 二月桂酸二丁基锡开启搅拌；另称取 $2.7\\mathrm{g}$ $\\left(0.03\\mathrm{mol}\\right),$ )  1 ,4‑丁二醇和 $42.0\\mathrm{g}$ $\\left(0.07\\mathrm{mol}\\right)^{\\cdot}$ )  聚乙二醇600，充分混合至完全溶解，转移至恒压滴液漏斗中，在室温下缓慢滴加至上述三口烧瓶中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $70^{\\circ}\\mathrm{C}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值（通过盐酸二正丁胺法测定），得到亲水改性的预聚体1，然后加入 $27.6\\mathrm{g}$ (0 .3mol)  甘油继续反应直至异氰酸酯基(‑NCO)的含量为零，得到超支化树脂；  \n\n[0038] 另取250mL三口烧瓶，向其加入11 .11g $\\left(0.05\\mathrm{mol}\\right)^{\\cdot}$ )  异佛尔酮二异氰酸酯和 $0.026\\mathrm{g}$ $(0.1\\mathrm{wt\\%})$ 二月桂酸二丁基锡开启搅拌；另依次称取 $0.068\\mathrm{g}$ $(0.262\\mathrm{wt}\\%)$ 对羟基苯甲醚，$0.136\\mathrm{g}$ $(0.525\\mathrm{wt\\%})$ 2,6‑二叔丁基‑4‑甲基苯酚以及 $14.9\\mathrm{g}$ $\\left(0.05\\mathrm{mol}\\right)$ )  季戊四醇三丙烯酸酯，充分混合至完全溶解，转移至恒压滴液漏斗中，在室温下缓慢滴加至上述三口烧瓶中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $70^{\\circ}\\mathrm{C}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值（通过盐酸二正丁胺法测定)，降温得到预聚体2，加入上述超支化树脂继续反应直至异氰酸酯基(‑NCO)的含量为零，得到光‑热双固化树脂，干燥密封保存；  \n\n[0039] （b）防雾涂料的制备：将60份光‑热双固化树脂、14份季戊四醇三丙烯酸酯（PETA）、10份丙烯酰吗啉（ACMO）、10份固化剂Desmodur  N75、1份流平剂FS3100、5份光引发剂1173加入分散料筒内高速分散30min，得到均匀透明的防雾涂料。  \n\n[0040] （c）防雾涂层的制备：将（b）中制备的防雾涂料用线棒均匀的涂在干净的PC板上，然后放在传送带式UV固化机上，经800mJ紫外光固化后，在室温条件下放置7d即得防雾涂层。  \n\n[0041] 实施例3  防雾涂层的制备  \n\n[0042] （a）光‑热双固化树脂的制备：250mL的三口烧瓶中加入 $34.83\\mathrm{g}$ (0 .2mol)  甲苯二异氰酸酯和 $0.08\\mathrm{g}\\quad(0.1\\mathrm{w}\\mathrm{t}\\%)$ 二月桂酸二丁基锡开启搅拌；另用 $100\\mathrm{g}$ 甲苯和 $100\\mathrm{g}$ 异丙醇将$13.4\\mathrm{g}\\left(0.1\\mathrm{mol}\\right)$ 三羟甲基丙烷混合溶解，充分混合至完全溶解，转移至恒压滴液漏斗中，在室温下缓慢滴加至上述三口烧瓶中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $70^{\\circ}\\mathrm{C}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值（通过盐酸二正丁胺法测定），得到亲水改性的预聚体1；然后加入 $.2.7\\mathrm{g}\\left(0.03\\mathrm{mol}\\right)1,4\\AA$ 丁二醇和$60.0\\mathrm{g}\\left(0.1\\mathrm{mol}\\right)$ 聚乙二醇600，继续反应直至异氰酸酯基(‑NCO)的含量为零，得到超支化树脂；  \n\n[0043] 另取250mL三口烧瓶，向其加入 $6.72\\mathrm{g}$ $\\left(0.04\\mathrm{mol}\\right),$ )  六亚甲基二异氰酸酯和 $0.012\\mathrm{g}$ $(0.1\\mathrm{w}\\mathrm{t}\\%)$ 二月桂酸二丁基锡开启搅拌；另依次称取 $0.03\\mathrm{g}$ $(0.262\\mathrm{wt}\\%)$ )  对羟基苯甲醚，$0.06\\mathrm{g}$ (0 .525wt%)  2,6‑二叔丁基‑4‑甲基苯酚以及 $5.2\\mathrm{g}$ $\\left(0.04\\mathrm{mol}\\right),$ )  丙烯酸羟丙酯(HPA)，充分混合至完全溶解，转移至恒压滴液漏斗中，在室温下缓慢滴加至上述三口烧瓶中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $70^{\\circ}\\mathrm{C}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值（通过盐酸二正丁胺法测定)，降温得到预聚体  \n\n2；加入上述超支化树脂继续反应直至异氰酸酯基(‑NCO)的含量为零，得到光‑热双固化树脂，减压蒸馏脱除溶剂，干燥密封保存。  \n\n[0044] （b）防雾涂料的制备：将60份光‑热双固化树脂、26份聚乙二醇400二丙烯酸酯（PEG400DA）、8份固化剂Desmodur  N100、1份流平剂FS3100、3份光引发剂TPO，2份光引发剂184，加入分散料筒内高速分散30min，得到均匀透明的防雾涂料。  \n\n[0045] （c）防雾涂层的制备：将（b）中制备的防雾涂料用线棒均匀的涂在干净的玻璃上，$80^{\\circ}\\mathrm{C}$ 烘箱预干燥2min，然后放在传送带式UV固化机上，经800mJ紫外光固化后，在室温条件下放置7d即得防雾涂层。  \n\n[0046] 实施例4  防雾涂层的制备  \n\n[0047] （a）光‑热双固化树脂的制备：250mL的三口烧瓶中加入 $44.46\\mathrm{g}$ (0 .2mol)  异佛尔酮二异氰酸酯和 $0.09\\mathrm{g}$ $(0.1\\mathrm{wt\\%})$ 二月桂酸二丁基锡开启搅拌；另用 $100\\mathrm{g}$ 无水乙醇和 $100\\mathrm{g}$ 异丙醇将 $12.0\\mathrm{g}\\left(0.1\\mathrm{mol}\\right)$ 三羟甲基乙烷混合溶解，充分混合至完全溶解，转移至恒压滴液漏斗中，在室温下缓慢滴加至上述三口烧瓶中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $70\\mathrm{{^\\circC}}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值（通过盐酸二正丁胺法测定），得到亲水改性的预聚体1；然后加入 $.2.36\\mathrm{g}\\left(0.02\\mathrm{mol}\\right)1,6\\cdot$ 己二醇和 $48.0\\mathrm{g}\\left(0.12\\mathrm{mol}\\right)$ ）聚乙二醇400，继续反应直至异氰酸酯基(‑NCO)的含量为零，得到超支化树脂；  \n\n[0048] 另取 $250\\mathrm{mL}$ 三口烧瓶，向其加入 $22.2\\mathrm{g}$ (0 .1mol)  异佛尔酮二异氰酸酯和 $0.036\\mathrm{g}$ $(0.1\\mathrm{wt\\%})$ 二月桂酸二丁基锡开启搅拌；另依次称取 $0.094\\mathrm{g}$ $(0.262\\mathrm{wt}\\%)$ 对羟基苯甲醚，$0.188\\mathrm{g}$ $(0.525\\mathrm{wt\\%})$ 2,6‑二叔丁基‑4‑甲基苯酚以及 $14.4\\mathrm{g}$ (0 .1mol)  4‑羟基丁基丙烯酸酯(4HBA)，充分混合至完全溶解，转移至恒压滴液漏斗中，在室温下缓慢滴加至上述三口烧瓶中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $70^{\\circ}\\mathrm{C}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值（通过盐酸二正丁胺法测定)，降温得到预聚体2；加入上述超支化树脂继续反应直至异氰酸酯基(‑NCO)的含量为零，得到光‑热双固化树脂，减压蒸馏脱除溶剂，干燥密封保存。  \n\n[0049] （b）防雾涂料的制备：将50份光‑热双固化树脂、24份聚乙二醇400二丙烯酸酯（PEG600DA）、10份双季戊四醇六丙烯酸酯（DPHA）、10份固化剂Desmodur  N3390、1份流平剂FSWET1010、5份光引发剂TPO加入分散料筒内高速分散30min，得到均匀透明的防雾涂料。  \n\n[0050] （c）防雾涂层的制备：将（b）中制备的防雾涂料用线棒均匀的涂在干净的PMMA板上，然后放在传送带式UV固化机上，经800mJ紫外光固化后，在室温条件下放置7d即得防雾涂层。  \n\n[0051] 实施例5  性能测试[0052] 实施例1‑4所制得的防雾涂层的性能测试项目和方法如下表所示：  \n\n<html><body><table><tr><td>项目</td><td>方法</td></tr><tr><td>铅笔硬度</td><td>通过铅笔硬度仪按照GB/T6739-1996 中的规定进行</td></tr><tr><td>附着力</td><td>采用百格法，交叉划格形成10X10的小 方格。用3M-610压敏胶带紧密粘附于 涂层表面，然后沿90度方向快速撕去 胶带，观测格子边缘的破坏程度</td></tr><tr><td>烧杯防雾测试 初始防雾</td><td>涂层置于50C热水上方标准高度，面向 水蒸气高达3分钟。如果测试中形成连 续的水膜，则不会再起雾。如果测试中 起雾，记录从开始测试到出现雾的时间</td></tr><tr><td>哈气测试</td><td>防雾测试中3分钟不起雾，则通过 朝涂层哈气，观察起雾情况</td></tr><tr><td>室温水浸泡-防雾测试（冷水测试）</td><td>样品在室温水中浸泡1小时，取出，干 燥12小时，进行烧杯防雾测试</td></tr><tr><td>沸水浸泡-防雾测试（沸水测试）</td><td>样品在沸水中煮1小时，取出，冷却干 燥12小时，进行烧杯防雾测试</td></tr><tr><td>初始雾度</td><td>采用透光率/雾度测定仪按照GB/T 2410-2008进行测试，小于10%不会被 目测观察到</td></tr><tr><td>落沙-雾度测试 化学品擦拭测试（耐化学品）</td><td>观察落沙试验后，雾度升高值 样品分别用在甲基乙基酮和异丙醇中</td></tr><tr><td>钢丝绒测试（耐划伤）</td><td>浸泡过的布擦拭，观察是否出现异常 #0000钢丝绒，100克压力，擦10圈。</td></tr><tr><td>防雾持久性测试</td><td>1-2个划痕为非常好；3-5个擦痕为好； 多于5个擦痕为差。 对涂层做长期测试，每天测试防雾性</td></tr><tr><td></td><td>能，记录出现防雾性能下降时的天数</td></tr><tr><td>粘性测试</td><td>用棉花擦样品表面，不残留纤维为光 滑，残留纤维越多说明越粘</td></tr></table></body></html>\n\n[0053] 实施例1‑4所制得的防雾涂层的性能测试结果如下表所示：  \n\n<html><body><table><tr><td>性能项目</td><td>测试方法</td><td>实施 例1</td><td>实施 例2</td><td>实施 例3</td><td>实施 例4</td></tr><tr><td>固化所 需能量</td><td></td><td>800mJ</td><td>800mJ</td><td>800mJ</td><td>800mJ</td></tr><tr><td>涂层厚度</td><td>m</td><td>5.2</td><td>6.2</td><td>5.4</td><td>6.8</td></tr><tr><td>初始雾度</td><td></td><td>0.2%</td><td>0.1%</td><td>0.1%</td><td>0.1%</td></tr><tr><td>落沙雾度</td><td>观察落沙测试后，雾度升 高值</td><td>2.9%</td><td>3.0%</td><td>3.4%</td><td>3.1%</td></tr><tr><td>初始防雾</td><td>3min不起雾，则通过</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>哈气</td><td>不起雾则通过</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>冷水测试</td><td>观察开始测试到出现雾 的时间</td><td>>180s</td><td>>180s</td><td>>180s</td><td>>180s</td></tr><tr><td>沸水测试</td><td>观察开始测试到出现雾 的时间</td><td>>180s</td><td>>180s</td><td>>180s</td><td>>180s</td></tr><tr><td>耐化学品</td><td>化学品布擦拭</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>铅笔硬度</td><td>铅笔测试仪</td><td>3H</td><td>3H</td><td>4H</td><td>4H</td></tr><tr><td>耐划伤</td><td>钢丝绒测试，记划痕数</td><td>3</td><td>4</td><td>2</td><td>１</td></tr><tr><td>附着力</td><td>划格</td><td>0级</td><td>0级</td><td>0级</td><td>0级</td></tr><tr><td>防雾持久性</td><td></td><td>266d</td><td>274d</td><td>274d</td><td>266d</td></tr><tr><td>粘性测试</td><td></td><td>光滑</td><td>光滑</td><td>光滑</td><td>光滑</td></tr></table></body></html>  \n\n[0055] 综上，本发明创造性的利用二异氰酸酯，二元醇混合物和小分子多元醇合成了亲水的超支化树脂，然后向超支化树脂表面引入功能双键，同时保留一部分羟基，使它具有光‑热双重固化功能，其亲水链段能持久发挥防雾功能，它具有的超支化结构使分子链不易缠结，黏度较小，溶解性好。将其应用到防雾涂料配方中得到本申请保护的防雾涂料，防雾涂料不含溶剂，安全无毒，能够在多种类型的基材上成膜，在紫外光下可实现瞬时固化，可应用于连续工业化生产，形成的涂层与基材的粘接强度高，形成的涂层具有良好的透明度、高硬度、耐划伤性和耐化学品性，并具有优异的防雾效果、防雾持久性、良好的耐水性、低粘性。",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# (19)国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利申请  \n\n(10)申请公布号 CN 114829509 A(43)申请公布日 2022.07.29  \n\n(21)申请号 202080088410.X  \n(22)申请日 2020.12.24  \n(30)优先权数据2020-003244 2020.01 .10 JP2020-102957 2020.06.15 JP  \n\n(85)PCT国际申请进入国家阶段日2022.06.17  \n\n(86)PCT国际申请的申请数据PCT/JP2020/048372 2020.12.24(87)PCT国际申请的公布数据WO2021/140931 JA 2021 .07 .15(71)申请人 株式会社尼欧斯地址 日本兵库县  \n\n(72)发明人 竹井工贵 重松遥 西井健太郎  \n\n(74)专利代理机构 北京律盟知识产权代理有限责任公司 11287专利代理师 范海云  \n(51)Int.Cl.C09D 1/0 (2006.01)B32B 9/0 (2006.01)C09K 3/0 (2006.01)C09K 3/18(2006.01)C09D 7/61(2006.01)C09D 7/63(2006.01)",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n防雾涂料组合物及防雾涂膜以及防雾物品",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明提供一种含有长条状胶体氧化硅、及球状胶体氧化硅的防雾涂料组合物。本发明的目的在于提供一种能够形成即使水蒸气附着也不会变白的防雾涂膜的防雾涂料组合物、以及能够几乎不引起流水痕等外观变化且长期发挥防雾效果的防雾涂膜。  \n\n![](images/801ed21bbab298b2816eea42300361a7ec44c18a76117adc61d2104cdd7913cc.jpg)  \n\n1.一种防雾涂料组合物，其含有长条状胶体氧化硅、及球状胶体氧化硅。  \n2.根据权利要求1所述的防雾涂料组合物，其中该长条状胶体氧化硅与该球状胶体氧化硅的固体成分重量比为 $10:10\\sim40:10$ 。  \n3.根据权利要求1或2所述的防雾涂料组合物，其中该长条状胶体氧化硅是酸性长条状胶体氧化硅与碱性长条状胶体氧化硅的混合物，该球状胶体氧化硅是碱性球状胶体氧化硅、酸性球状胶体氧化硅、或它们的混合物。  \n4.根据权利要求1至3中任一项所述的防雾涂料组合物，其还包含表面活性剂。  \n5.根据权利要求1至4中任一项所述的防雾涂料组合物，其还包含有机溶剂。  \n6.一种防雾涂膜，其包含长条状氧化硅、及球状氧化硅，且所述防雾涂膜是在相邻的该长条状氧化硅之间的空隙内埋设该球状氧化硅而成的。  \n7.根据权利要求6所述的防雾涂膜，其中该长条状氧化硅包含酸性长条状氧化硅及碱性长条状氧化硅，该球状氧化硅包含碱性球状氧化硅、酸性球状氧化硅、或它们的混合物。  \n8.一种防雾物品，其包含基材、及根据权利要求6或7所述的防雾涂膜。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 防雾涂料组合物及防雾涂膜以及防雾物品",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明涉及一种防雾涂料组合物及使用其制作而成的防雾涂膜以及防雾物品。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 汽车的前照灯等照明装置主要包含光源及配置在光源前方的由玻璃或塑料等所形成的透明部件。并且，光源所发出的光透过透明部件而照射至照明装置的外部及周边部。这种照明装置有时会在透明部件的内侧(光源侧)产生雾，可能导致照射光的强度降低而产生安全性问题。另外，透过已产生雾的透明部件所照射的光的光量较少，在美观方面也可能成为问题。  \n\n[0003] 在日本专利特开2016‑169287号公报中提出了一种防雾剂组合物，其包含共聚物(A)、多官能性封端异氰酸酯化合物(B)及表面活性剂(C)。日本专利特开2016‑169287号公报的防雾剂组合物是利用一直以来广为人知的防雾机制，应用了防雾剂组合物的防雾涂膜中存在的表面活性剂(C)使附着于基材上的防雾涂膜上的水的表面张力降低，瞬间形成平滑的水膜，防止光的漫反射，由此防止雾。另一方面，在日本专利特开2005‑126647号公报中提出了一种防雾剂，其包含水性介质、项链状胶体氧化硅、硅烷衍生物及表面活性剂。在日本专利特开2005‑126647号公报中，使用了分散于水性介质中时pH值为 $8\\sim11$ (即碱性)的项链状胶体氧化硅。日本专利特开2005‑126647号公报的防雾剂通过使形成有涂膜的基材的表面被胶体氧化硅覆盖来发挥防雾效果。进而，日本专利特开2019‑19253号公报提出了一种防雾涂料组合物，其含有酸性长条状胶体氧化硅及pH值调节用长条状胶体氧化硅，不会引起流水痕等外观变化且长期发挥防雾效果。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0004] [发明要解决的问题]  \n\n[0005] 如果在由日本专利特开2016‑169287号公报中所提出的包含表面活性剂作为主成分的防雾剂组合物所形成的防雾涂膜上形成水膜，那么可能导致该表面活性剂溶出至水中，局部地发生表面活性剂与水一起流走的情况。如果这种部位进行干燥，那么可能在防雾物品上残留流水痕。另外，如果像日本专利特开2005‑126647号公报那样，使用在水性介质中呈现强碱性的胶体氧化硅作为防雾剂，虽然原因并不确定，但可能导致以下情况，即，曾覆盖基材的胶体氧化硅与水一起流走，在防雾物品上残留流水痕。日本专利特开2019‑19253号公报的防雾涂料组合物虽然能够形成外观变化较少的有效的防雾涂膜，但存在以下情况，即，水蒸气附着于日本专利特开2019‑19253号公报的防雾涂膜上，在其干燥的过程中，发现涂膜变白的现象。涂膜变白是暂时的，只要涂膜完全干燥，变白就会消失。然而，要将该防雾涂膜用于汽车前照灯、或交通信号灯等这种最重视安全性的制品中，比较困难。[0006] 因此，本发明的目的在于提供一种能够形成即使水蒸气附着也不会变白的防雾涂膜的防雾涂料组合物、以及能够几乎不引起流水痕等外观变化且长期发挥防雾效果的防雾涂膜。  \n\n[0007] [解决问题的技术手段]  \n\n[0008] 本发明的实施方式中的防雾涂料组合物的特征在于含有长条状胶体氧化硅、及球状胶体氧化硅。  \n\n[0009] 本发明的另一实施方式是一种防雾涂膜，其包含长条状氧化硅、及球状氧化硅，且所述防雾涂膜是在相邻的该长条状氧化硅之间的空隙内埋设该球状氧化硅而成的。  \n\n[0010] 本发明的又一实施方式是一种防雾物品，其包含基材、及本发明的另一实施方式的防雾涂膜。  \n\n[0011] [发明的效果]  \n\n[0012] 使用本发明的防雾涂料组合物所形成的防雾涂膜可瞬间形成平滑的水膜而防止光的漫反射，防雾性能优异。本发明的防雾涂膜不易产生干燥后的流水痕等外观变化。另外，本发明的防雾涂膜几乎看不到伴随水蒸气的附着而产生的变白现象，可始终维持透明的外观。利用本发明的防雾涂料组合物的防雾物品(例如照明装置)不易产生外观变化，可长期地维持稳定的光量。",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 附图说明  \n\n[0013] 图1是表示在基材的表面配置有长条状氧化硅的涂膜的状态的示意图。[0014] 图2是表示实施方式的防雾涂膜形成在基材表面的状态的示意图，所述实施方式的防雾涂膜是在相邻的长条状氧化硅之间的空隙内埋设球状氧化硅而成的。[0015] 图3是表示水覆盖在实施方式的防雾涂膜上并形成了水膜的状态的示意图。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 具体实施方式  \n\n[0016] 以下对本发明的实施方式进行说明。本发明的一实施方式是一种防雾涂料组合物，其含有长条状胶体氧化硅、及球状胶体氧化硅。  \n\n[0017] 在本实施方式中，防雾涂料组合物是指能够在玻璃或塑料等基材上形成涂膜，不易因水蒸气的水滴而产生雾的组合物。在由基材隔开的两空间存在温度差的情况下，高温侧的湿气在基材表面上冷凝，形成水滴。该水滴引起光的漫反射而产生雾。作为防止在基材上形成水滴的机制，已知有使附着于基材表面的水分瞬间成为水膜的机制、及瞬间吸收附着于基材表面的水分的机制。本实施方式的防雾涂料组合物形成防雾涂膜，所述防雾涂膜使附着于基材表面的水分瞬间成为水膜，防止形成水滴，由此防止基材的雾。  \n\n[0018] 本实施方式的防雾涂料组合物包含长条状胶体氧化硅。所谓胶体氧化硅是指二氧化硅(氧化硅、 $\\mathrm{Si0_{2})}$ 或其水合物的胶体溶液(或分散液)。根据分散介质的性质而有水系胶体氧化硅、及有机溶剂系有机氧化硅溶胶，但实施方式中尤其适宜使用的氧化硅为胶体氧化硅。形成胶体氧化硅的球状氧化硅的一次粒径通常为 $10{\\sim}300\\mathrm{nm}$ 左右，其可能进行凝集等而形成更大的二次粒子。本实施方式中适宜使用的胶体氧化硅为长条状胶体氧化硅。长条状胶体氧化硅是指氧化硅的一次粒子彼此几十个或几万个进行共价键结并形成绳状、筒状或棒状等较长形状而成的长条状氧化硅的胶体溶液(或分散液)。关于作为这种长条状氧化硅的胶体溶液(或分散液)的胶体氧化硅，已知有链状胶体氧化硅或珍珠项链状胶体氧化硅。长条状胶体氧化硅因为能够在基材的表面上扩散吸附，形成覆膜，所以可优选地用作防雾涂膜组合物的成分。此外，关于将水作为分散介质并分散有氧化硅的胶体氧化硅，根据氧化硅的表面状态的不同，而存在酸性、中性、碱性胶体氧化硅。作为本实施方式中适宜使用的长条状胶体氧化硅，可列举表现 $\\mathrm{pH1}\\sim3$ 的强酸性的酸性长条状胶体氧化硅、表现 $\\mathrm{pH}4{\\sim}9$ 的弱酸性～中性～弱碱性的中性长条状胶体氧化硅、表现 $\\mathrm{pH}10{\\sim}14\\$ 的碱性长条状胶体氧化硅，它们可以单独使用，也可以混合使用。此外，在混合多种胶体氧化硅进行使用的情况下，优选以所混合的胶体氧化硅的pH值成为中性～弱碱性 $\\mathrm{(pH7\\sim10}$ 左右)的方式进行混合。适宜用作本实施方式的一成分的长条状胶体氧化硅是由表现 $\\mathrm{pH1}\\sim3$ 的强酸性的酸性长条状胶体氧化硅、与碱性胶体氧化硅混合所得的长条状胶体氧化硅混合物。作为可用于实施方式中的长条状胶体氧化硅，可列举ST‑OUP、ST‑UP、ST‑PS‑S、ST‑PS‑M、ST‑PS‑SO、ST‑PS‑MO(均为日产化学(股))等市售品。  \n\n[0019] 在将由酸性长条状胶体氧化硅、及碱性长条状胶体氧化硅混合所得的长条状胶体氧化硅混合物用于实施方式的防雾涂料组合物中时，碱性长条状胶体氧化硅是用于提高先前所说明的酸性长条状胶体氧化硅的pH值而调整至弱酸性～弱碱性。酸性长条状胶体氧化硅可在分散介质蒸发形成后形成涂膜，有效地形成水膜而发挥防雾效果，因此优选使用。但是，如果胶体氧化硅的酸性过强，那么防雾涂料组合物的性状不稳定，可能难以处理。另外，强酸性的防雾涂料组合物可能会腐蚀要涂布的基材(例如金属基材或指定的塑料基材等)，也存在根据所应用的基材而无法使用的情况。因此，混合碱性长条状胶体氧化硅来适当地调节长条状胶体氧化硅整体的pH值。此外，也可以使用无机碱或有机碱等各种碱性化合物来调节pH值，但优选使用使pH值的调节变得相对简便的碱性长条状胶体氧化硅。  \n\n[0020] 酸性长条状胶体氧化硅与碱性长条状胶体氧化硅优选以胶体氧化硅混合物的pH值成为中性 $\\sim$ 弱碱性 $\\mathrm{(pH7\\sim10}$ 左右)的方式进行混合。为了使胶体氧化硅混合物的pH值成为中性～弱碱性，可按照酸性长条状胶体氧化硅与碱性长条状胶体氧化硅的固体成分重量比成为 $2.5{:}10{\\sim}90{:}10$ 的方式进行混合。固体成分重量比是指各胶体氧化硅中固体成分实质上所占的重量的比率。此外，如上所述，酸性长条状胶体氧化硅与碱性长条状胶体氧化硅尤其优选按照混合物的pH值成为中性 $\\sim$ 弱碱性 $(\\mathrm{pH}7\\sim10\\$ 左右)的方式进行混合，但也可以通过进而混合下述球状胶体氧化硅来调节pH值。  \n\n[0021] 实施方式的防雾涂料组合物还包含球状胶体氧化硅。与所述长条状胶体氧化硅同样地，球状胶体氧化硅也为二氧化硅(氧化硅、 $\\mathrm{Si0_{2})}$ )或其水合物的胶体溶液(或分散液)。氧化硅的一次粒径通常为 $10{\\sim}300\\mathrm{nm}$ 左右，其可能进行凝集等而形成更大的二次粒子，但实施方式中所使用的球状胶体氧化硅的大小优选为最大为 $100\\mathrm{nm}$ 左右。球状胶体氧化硅在水中具有大致球形粒子形状。此外，如上所述，关于将水作为分散介质并分散有氧化硅的胶体氧化硅，根据氧化硅的表面状态的不同，而存在酸性、中性、碱性胶体氧化硅。作为本实施方式中适宜使用的球状胶体氧化硅，可列举表现 $\\mathrm{pH1}\\sim3$ 的强酸性的酸性球状胶体氧化硅、表现$\\mathrm{pH}4{\\sim}9$ 的弱酸性～中性～弱碱性的中性球状胶体氧化硅、表现 $\\mathrm{pH10}{\\sim}14\\$ 的碱性球状胶体氧化硅，它们可以单独使用，也可以混合使用。在实施方式中，尤其优选使用碱性球状胶体氧化硅、酸性胶体氧化硅、或碱性胶体氧化硅与酸性胶体氧化硅的混合物作为球状胶体氧化硅。球状胶体氧化硅优选为按照将所述长条状胶体氧化硅混合物的pH值调节为弱酸性～弱碱性的方式使用。含有长条状胶体氧化硅及球状胶体氧化硅的实施方式的防雾涂料组合物能够形成不易发生干燥变白的防雾涂膜。此外，尤其优选按照以下方式进行混合，即，长条状胶体氧化硅与球状胶体氧化硅的固体成分重量比为 $10{:}10\\{\\sim}40{:}10$ ，优选为 $15{:}10\\sim30$ ∶  \n\n10，进而优选为 $20{\\mathrel{:}}10{\\sim}25{\\mathrel{:}}10\\$ 。以这种比率调配而成的防雾涂料组合物尤其在造膜性方面优异，可获得在涂膜的表面未发现破裂或收缩等的均质的涂膜。作为可用于实施方式中的球状胶体氧化硅，可列举ST‑N、ST‑NXS、ST‑S、ST‑XS、ST‑O、ST‑OXS(均为日产化学(股))等市售品。此外，所述长条状胶体氧化硅与球状胶体氧化硅可按照以下方式以任意组合进行混合，即，实施方式的防雾涂料组合物的pH值成为不会对供涂布防雾涂料组合物的基材产生影响的范围(通常为弱酸性 $\\sim$ 弱碱性的范围)。例如，除了将酸性长条状胶体氧化硅及碱性长条状胶体氧化硅及碱性球状胶体氧化硅加以混合而使用以外，还可以碱性长条状胶体氧化硅与酸性球状胶体氧化硅的组合、酸性长条状胶体氧化硅与碱性球状胶体氧化硅的组合、酸性长条状胶体氧化硅及碱性长条状胶体氧化硅及酸性球状胶体氧化硅的组合、酸性长条状胶体氧化硅及碱性长条状胶体氧化硅及碱性球状胶体氧化硅及酸性球状胶体氧化硅的组合、中性长条状胶体氧化硅及酸性球状胶体氧化硅的组合、碱性长条状胶体氧化硅及中性球状胶体氧化硅的组合、或者碱性长条状胶体氧化硅及酸性球状胶体氧化硅及碱性球状胶体氧化硅的组合等所有组合进行混合。  \n\n[0022] 实施方式的防雾涂料组合物可还包含表面活性剂。在实施方式的防雾涂料组合物中，表面活性剂用于辅助各胶体氧化硅在基材表面上的扩散，而使涂布作业变得容易。作为表面活性剂，可使用阴离子性表面活性剂、阳离子性表面活性剂、非离子性表面活性剂、两性表面活性剂中的任一种，可使用它们中的一种或两种以上。作为阴离子性表面活性剂，可列举：油酸钠、油酸钾等脂肪酸盐、月桂基硫酸钠、月桂基硫酸铵等高级醇硫酸酯类、十二烷基苯磺酸钠、烷基萘磺酸钠等烷基苯磺酸盐及烷基萘磺酸盐、萘磺酸福马林缩合物、二烷基磺基琥珀酸盐、二烷基磷酸盐、聚氧乙烯烷基苯醚硫酸钠等聚氧乙烯硫酸盐、含有全氟烷基的磺酸盐型、含有全氟烷基的羧酸盐型、含有全氟烯基的磺酸盐型、含有全氟烯基的羧酸盐型等阴离子性氟系表面活性剂类。作为阳离子性表面活性剂，例如可列举：乙醇胺类、月桂基胺乙酸酯、三乙醇胺单甲酸盐、硬脂酰胺乙基二乙胺乙酸盐等胺盐、月桂基三甲基氯化铵、硬脂基三甲基氯化铵、二月桂基二甲基氯化铵、二硬脂基二甲基氯化铵、月桂基二甲基苄基氯化铵、硬脂基二甲基苄基氯化铵等季铵盐、含有全氟烷基或全氟烯基的季铵盐型等阳离子性氟系表面活性剂类。  \n\n[0023] 作为非离子性表面活性剂，例如可列举：聚氧乙烯月桂醇、聚氧乙烯月桂醚、聚氧乙烯油醚等聚氧乙烯高级醇醚类、聚氧乙烯辛基苯酚、聚氧乙烯壬基苯酚等聚氧乙烯烷基芳基醚类、聚氧乙烯乙二醇单硬脂酸酯等聚氧乙烯酰基酯类、聚丙二醇环氧乙烷加成物、聚氧乙烯山梨醇酐单月桂酸酯、聚氧乙烯山梨醇酐单硬脂酸酯等聚氧乙烯山梨醇酐脂肪酸酯类、烷基磷酸酯、聚氧乙烯烷基醚磷酸酯等磷酸酯类、糖酯类、纤维素醚、聚醚改性硅酮油等硅酮类、含有全氟烷基的环氧乙烷加成物型、含有全氟烷基的氧化胺、含有全氟烷基的低聚物型、含有全氟烯基的环氧乙烷加成物型、含有全氟烯基的氧化胺、含有全氟烯基的低聚物型等非离子性氟系表面活性剂类。作为两性表面活性剂，可列举：月桂基三甲基氯化铵、二月桂基二甲基氯化铵、二硬脂基二甲基氯化铵、月桂基二甲基苄基氯化铵等季铵盐、二甲基烷基月桂基甜菜碱、二甲基烷基硬脂基甜菜碱等脂肪酸型两性表面活性剂、二甲基烷基磺基甜菜碱等磺酸型两性表面活性剂、烷基甘氨酸、含有全氟烷基或全氟烯基的甜菜碱型两性氟系表面活性剂类等。可优选地使用所述表面活性剂中的任一种作为本实施方式的表面活性剂。表面活性剂优选为相对于防雾涂料组合物100重量份而含有 $0.01{\\sim}0.30$ 重量份左  \n\n右。  \n\n[0024] 进而，实施方式的防雾涂料组合物可含有有机溶剂。可将实施方式的防雾涂料组合物的主成分即以水作为分散介质的胶体氧化硅混合物单独涂布于基材表面上而形成防雾涂膜。但是，如果其中还包含有机溶剂，那么形成涂膜时的水的干燥得到促进，因此可在物品表面上更早一步形成防雾涂膜。实施方式中可使用的有机溶剂是与水具有相容性、或在指定的范围内与水进行混合的有机溶剂。作为这种有机溶剂，例如可列举：醇类(甲醇、乙醇、丙醇、乙二醇等)、醚类(二甲氧基乙烷、四氢呋喃、二恶烷、丙二醇单甲醚等)、酮类(丙酮、甲基乙基酮等)、酰胺类(二甲基甲酰胺等)、或二甲基亚砜(DMSO)、乙腈、硝基甲烷、三乙胺。有机溶剂优选为相对于防雾涂料组合物100重量份而含有 $10{\\sim}80$ 重量份左右。  \n\n[0025] 本实施方式的适宜的防雾涂料组合物可如下制造，即，首先准备长条状胶体氧化硅、及球状胶体氧化硅，接着视需要与表面活性剂及有机溶剂进行混合。长条状胶体氧化硅与球状胶体氧化硅是以特定的固体成分比率分散在作为分散介质的水中，可按照长条状胶体氧化硅与球状胶体氧化硅的固体成分重量比成为 $10{:}10\\mathrm{\\sim}40{:}10.$ 、优选为 $15:10\\sim30:10.$ 、进而优选为 $20{:}10{\\sim}25{:}10$ 的方式进行混合。如果相对于球状胶体氧化硅而长条状胶体氧化硅的比率过多，那么在下述干燥变白试验中容易发生变白，容易发生外观不良。如果相对于球状胶体氧化硅而长条状胶体氧化硅的比率过少，那么容易引起造膜不良。通过适当地调配长条状胶体氧化硅与球状氧化硅的比率，可获得造膜性优异的防雾涂膜组合物，由此可形成均质且防雾性较高的防雾涂膜。实施方式的防雾涂料组合物可除了这些成分以外还适当地调配通常包含在涂料组合物中的添加剂(例如染料、颜料、增塑剂、分散剂、防腐剂、消光剂、抗静电剂、阻燃剂)。  \n\n[0026] 可将由长条状胶体氧化硅、球状胶体氧化硅及视需要而定的表面活性剂、有机溶剂适当调配而成的实施方式的防雾涂料组合物涂布在基材表面。可列举玻璃、塑料、金属等作为基材，但实施方式的防雾涂料组合物可尤其适宜地涂布在透明塑料上。关于防雾涂料组合物在基材表面上的涂布，可通过刮刀法、棒式涂布法、浸渍法、空气喷涂法、滚筒刷法、辊式涂布机法等以往的涂布方法来适当地进行。可对所涂布的防雾涂料组合物进行加热而形成防雾涂膜。关于防雾涂料组合物的加热，只要加热至足够使水及含有情况下的有机溶剂蒸发的温度即可。虽然也取决于所使用的有机溶剂的种类，但通常加热至 $80{\\sim}150^{\\circ}\\mathrm{C}$ 、优选为 $100{\\sim}150^{\\circ}\\mathrm{C}$ 左右，由此可使水及有机溶剂蒸发。关于防雾涂料组合物涂布物的加热，除了利用燃烧器或烘箱等加热装置进行加热以外，还可以通过利用干燥机等的热风进行的加热方法来进行。当如此将实施方式的防雾涂料组合物涂布在基材上，通过加热使水或有机溶剂干燥时，在基材表面上扩散的长条状胶体氧化硅成为长条状氧化硅，球状胶体氧化硅成为球状氧化硅而形成覆膜。通过如此将实施方式的防雾涂料组合物应用于物品，可形成防雾涂膜，获得防雾物品。  \n\n[0027] 本发明的另一实施方式是一种防雾涂膜，其包含长条状氧化硅、及球状氧化硅。实施方式的防雾涂膜的特征在于，在相邻的长条状氧化硅之间存在空隙，且在该空隙内埋设有球状氧化硅。使用附图在以下说明实施方式的防雾涂料组合物含有长条状胶体氧化硅混合物及球状胶体氧化硅的技术性有意义点。此外，防雾涂膜的结构、及变白防止机制的理论并不拘泥于以下内容。  \n\n[0028] 图1是表示由仅含长条状胶体氧化硅的防雾涂料组合物(常规产品)所形成的防雾涂膜的状态的附图。图1中，1表示基材；2表示长条状氧化硅；4表示空隙；5表示防雾涂膜(常规产品)。在图1的防雾涂膜5中，绘制成下述形态，即，较长形状(例如筒状、棒状、绳状)的长条状氧化硅2以其长度方向大体一致的状态配置，但在实际的防雾涂膜5中，长条状氧化硅2未必规则性地配置。在图1中，具有相对刚性且较长的结构的长条状氧化硅2配置在基材1上，到处都存在空隙4。空隙4的大小通常具有几百纳米～几微米左右的大小。当水蒸气与图1中所示的防雾涂膜5接触时，在防雾涂膜5上形成水膜，且水蒸气渗透至空隙4的内部。在水干燥的过程中，防雾涂膜5的表面上所形成的水膜会迅速干燥，但进入至空隙4内的水的干燥会稍微延迟。认为在该残留有水的部分，光进行散射而进行漫反射，防雾涂膜发生变白。[0029] 另一方面，图2是表示由含有长条状胶体氧化硅、及球状胶体氧化硅的防雾涂料组合物(本发明的实施方式)所形成的防雾涂膜的状态的附图。图2中，1为基材；2为长条状氧化硅；3为球状氧化硅；5为防雾涂膜。在图2的防雾涂膜5中，绘制成下述形态，即，较长形状(例如筒状、棒状、绳状)的长条状氧化硅2以其长度方向大体一致的状态配置，但在实际的防雾涂膜5中，长条状氧化硅2未必规则性地配置。在图2中，具有相对刚性且较长的结构的长条状氧化硅2配置在基材1上，在相邻的长条状氧化硅之间随处可能存在的空隙(具有几百纳米～几微米左右的大小)内埋设有比空隙大小更小的(几纳米～几十纳米的)球状氧化硅3。认为虽然球状氧化硅3并非以完全填埋空隙的方式配置，但如图2所示，是以大体上使空隙消失的方式配置。当水蒸气与图2中所示的防雾涂膜5接触时，在防雾涂膜5上形成水膜，但图2的防雾涂膜5无空隙，或者即使有也是极小的，所以水蒸气不易渗透至防雾涂膜5的内部。认为在水干燥的过程中，防雾涂膜5的表面上所形成的水膜迅速干燥，且几乎没有水渗透至防雾涂膜内部成为可能引起光漫反射的点，所以未发现变白。  \n\n[0030] 图3是表示本发明的实施方式即由含有长条状胶体氧化硅、及球状胶体氧化硅的防雾涂料组合物(本发明的实施方式)所形成的防雾涂膜、与水蒸气接触而在防雾涂膜表面上形成了水膜的状态的附图。图3中，1为基材；2为长条状氧化硅；3为球状氧化硅；5为防雾涂膜；6为水；7为水可能渗透的范围。在图3的防雾涂膜5中，仅在防雾涂膜5的上部分绘制出配置有长条状氧化硅2及球状氧化硅3的状态，在下部分无该绘图，但在该下部分，与上部分同样地形成有长条状氧化硅2及球状氧化硅3的配置。当水蒸气与图3中所示的防雾涂膜5接触时，在防雾涂膜5上形成水膜(水6)。图3的防雾涂膜5中并无空隙，或者即使有也是极小的，所以水蒸气不易渗透至防雾涂膜5的内部。因此，防雾涂膜5中水所渗透的范围最大仅为7所表示的箭头的范围，水无法到达防雾涂膜5的深处。然后，认为在水干燥的过程中，防雾涂膜5的表面上所形成的水膜(水6)迅速干燥，几乎没有水渗透至防雾涂膜5的内部成为可能引起光散射的点，所以未发现防雾涂膜5变白。  \n\n[0031] 如上所说明，实施方式的防雾涂膜中，在相邻的长条状氧化硅所形成的空隙内埋设有球状氧化硅，所以即使防雾涂膜与水蒸气接触，水也不易渗透至防雾涂膜内部。防雾涂膜表面上所形成的水膜立即干燥，在防雾涂膜内部也不易残留水，所以能够防止由光的散射引起的漫反射。因此，实施方式的防雾涂膜不易变白。此外，实施方式的防雾涂膜中，所配置的长条状氧化硅可包含酸性长条状氧化硅及碱性长条状氧化硅，在相邻的长条状氧化硅之间的空隙内所埋设的球状氧化硅可包含碱性球状氧化硅、酸性球状氧化硅、或碱性球状氧化硅与酸性球状氧化硅的混合物。在该实施方式中，酸性长条状氧化硅是指分散于水中时表现酸性的长条状氧化硅。另外，碱性长条状氧化硅是指分散于水中时表现碱性的长条状氧化硅。进而，碱性球状氧化硅是指分散于水中时表现碱性的球状氧化硅。另外，酸性球状氧化硅是指分散于水中时表现酸性的球状氧化硅。  \n\n[0032] 可将本实施方式的防雾涂料组合物应用于基材来形成防雾涂膜。并且，可获得基材具有防雾涂膜的实施方式的防雾物品。作为实施方式的防雾物品，例如可列举：照明装置、前照灯、窗、透镜、透镜盖、监视器、监视器盖等。实施方式的防雾物品具有优异的防雾性能，不会引起流水痕的形成等外观变化。另外，即使水蒸气与实施方式的防雾物品接触，也不会变白，或者很难变白。  \n\n[0033] [实施例][0034] (1)防雾涂料组合物的制作  \n\n[0035] 将酸性长条状胶体氧化硅(ST‑OUP[固体成分 $15\\%$ ，水分散液]，日产化学(股))48.93重量份、碱性长条状胶体氧化硅(ST‑UP[固体成分 $20\\%$ ，水分散液]，日产化学(股))12.23重量份、碱性球状胶体氧化硅(ST‑N[固体成分 $20\\%$ ，水分散液]，日产化学(股))10.49重量份、碱性球状胶体氧化硅(ST‑NXS[固体成分 $15\\%$ ，水分散液]，日产化学(股))13.98重量份、表面活性剂(FTERGENT  150，氟系阴离子系表面活性剂，NEOS(股))0.03重量份、及有机溶剂(丙二醇单甲醚，日本乳化剂(股))14.34重量份加以混合而制作防雾涂料组合物(实施例1)。分别变更酸性长条状胶体氧化硅、碱性长条状胶体氧化硅、两种碱性球状胶体氧化硅ST‑N及ST‑NXS、两种酸性球状胶体氧化硅ST‑O及ST‑OXS、表面活性剂、有机溶剂的调配比率来制作实施例 $2{\\sim}8$ 的防雾涂料组合物。同样地，制作比较例1、2的防雾涂料组合物。将各防雾涂料组合物的成分构成示于表1及表2。  \n\n<html><body><table><tr><td colspan=\"3\">涂膜的评价（实施例）</td><td colspan=\"8\"></td></tr><tr><td colspan=\"3\"></td><td>1</td><td>2</td><td>3</td><td>实施例 4</td><td>5</td><td>6</td><td>7</td><td>8</td></tr><tr><td colspan=\"3\">长条状氧化硅/球状氧化硅 固体成分重量比</td><td>7/3(23.3/10)</td><td>7/3(23.3/10)</td><td>7/3(23.3/10)</td><td>6/4(15/10)</td><td>7/3(23.3/10)</td><td>7/3(23.3/10)</td><td>8/2(40/10)</td><td>5/5(10/10)</td></tr><tr><td colspan=\"3\">组合物</td><td>48.93</td><td>51.08</td><td>46.96</td><td>44.76</td><td>45.15</td><td>51.08</td><td>57.12</td><td>38.15</td></tr><tr><td rowspan=\"12\">防雾涂料</td><td>长条状胶体 氧化硅</td><td>ST-OUP ST-UP</td><td>12.23</td><td>12.77</td><td>11.74</td><td>11.19</td><td>11.29</td><td>12.77</td><td>14.28</td><td>9.54</td></tr><tr><td>碱性球状胶</td><td>ST-N</td><td>10.49</td><td>21.89</td><td></td><td>29.84</td><td></td><td>10.94</td><td>14.28</td><td>38.15</td></tr><tr><td>体氧化硅</td><td>ST-NXS</td><td>13.98</td><td></td><td>26.84</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>酸性球状胶</td><td>ST-O</td><td></td><td></td><td></td><td></td><td>9.67</td><td>10.94</td><td></td><td></td></tr><tr><td>体氧化硅</td><td>ST-OXS</td><td></td><td></td><td></td><td></td><td>19.35</td><td></td><td></td><td></td></tr><tr><td>表面活性剂</td><td>FT-150</td><td>0.03</td><td>0.04</td><td>0.03</td><td>0.04</td><td>0.03</td><td>0.04</td><td>0.04</td><td></td></tr><tr><td>溶剂</td><td>PGM</td><td>14.34</td><td>14.22</td><td>14.43</td><td>14.17</td><td>14.51</td><td>14.23</td><td>14.28</td><td>0.04</td></tr><tr><td></td><td>合计</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>14.12 100</td></tr><tr><td rowspan=\"4\">评价</td><td colspan=\"2\">造膜性</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td><td>不良</td></tr><tr><td colspan=\"2\">防雾性</td><td>无雾</td><td>无雾</td><td>无雾</td><td>无雾</td><td>无雾</td><td>无雾</td><td>无雾</td><td>无雾</td></tr><tr><td colspan=\"2\">流水痕</td><td>无流挂</td><td>无流挂</td><td>无流挂</td><td>无流挂</td><td>无流挂</td><td>无流挂</td><td>无流挂</td><td>无流挂</td></tr><tr><td colspan=\"2\">干燥变白</td><td>未变白</td><td>未变白</td><td>未变白</td><td>未变白</td><td>未变白</td><td>未变白</td><td>略微变白</td><td>未变白</td></tr></table></body></html>  \n\n[0037] [表2][0038] [表2]防雾涂料组合物的组成及防雾涂膜的评价(比较例)  \n\n<html><body><table><tr><td rowspan=\"2\" colspan=\"3\">长条状氧化硅/球状氧化硅</td><td>比较例</td></tr><tr><td>1</td></tr><tr><td rowspan=\"7\">防雾涂料 39] 组合物 (重量份)</td><td colspan=\"2\">固体成分重量比</td><td>10/0</td></tr><tr><td rowspan=\"2\">长条状胶体氧化硅</td><td>ST-OUP ST-UP</td><td>68.47 17.12</td></tr><tr><td>ST-N</td><td></td></tr><tr><td rowspan=\"2\">碱性球状胶体氧化硅</td><td>ST-NXS</td><td></td></tr><tr><td>ST-O</td><td></td></tr><tr><td rowspan=\"2\">酸性球状胶体氧化硅 表面活性剂</td><td>ST-OXS</td><td></td></tr><tr><td>FT-150</td><td>0.03</td></tr><tr><td>溶剂</td><td>PGM</td><td>14.38</td></tr><tr><td rowspan=\"5\">评价</td><td colspan=\"2\">合计</td><td>100</td></tr><tr><td colspan=\"2\">造膜性</td><td>良好</td></tr><tr><td colspan=\"2\">防雾性</td><td>无雾</td></tr><tr><td colspan=\"2\">流水痕</td><td>无流挂</td></tr><tr><td colspan=\"2\">干燥变白</td><td>变白</td></tr></table></body></html>  \n\n[0040] 此外，表中的缩写的含义如下所述：  \n\n[0041] $\\operatorname{ST}\\mathrm{-}0\\mathrm{UP}$ ：日产化学(股)商品名，BET(Brunauer‑Emmett‑Teller，布厄特)法平均一次粒径 $12\\mathrm{nm}$ 的酸性氧化硅(长条状)的水分散液，固体成分 $15\\%$   \n[0042] ST‑UP：日产化学(股)商品名，BET法平均一次粒径 $12\\mathrm{nm}$ 的碱性氧化硅(长条状)的水分散液，固体成分 $20\\%$   \n[0043] ST‑N：日产化学(股)商品名，BET法平均一次粒径 $12\\mathrm{{nm}}$ 的碱性氧化硅的水分散液(球状)，固体成分 $20\\%$   \n[0044] ST‑NXS：日产化学(股)商品名，西尔斯法平均一次粒径5nm的碱性氧化硅(球状)的水分散液，固体成分 $15\\%$   \n[0045] ST‑O：日产化学(股)商品名，BET法平均一次粒径12nm的酸性氧化硅(球状)的水分散液，固体成分 $20\\%$   \n[0046] ST‑OXS：日产化学(股)商品名，西尔斯法平均一次粒径5nm的酸性氧化硅(球状)的水分散液，固体成分 $10\\%$   \n[0047] FT‑150：NEOS(股)商品名，阴离子系表面活性剂  \n[0048] PGM：丙二醇单甲醚  \n[0049] 表中的“长条状氧化硅/球状氧化硅(固体成分重量比)”是指仅将涂料组合物中所使用的长条状胶体氧化硅(混合物)、及球状胶体氧化硅(混合物)的固体成分的重量(即长条状氧化硅(混合物)及球状氧化硅(混合物)的重量)加以比较，计算它们的比而获得的值。例如，实施例1的防雾涂料组合物包含酸性长条状胶体氧化硅ST‑OUP的固体成分7.34重量份、碱性长条状胶体氧化硅ST‑UP的固体成分2.45重量份、碱性球状胶体氧化硅的固体成分ST‑N2.10重量份、碱性球状胶体氧化硅ST‑NXS的固体成分2.10重量份，所以长条状氧化硅混合物与球状氧化硅混合物的固体成分的重量比为7/3(23.3/10)。对于其它实施例及比较例，也同样地计算“长条状氧化硅/球状氧化硅(固体成分重量比)”的值。  \n\n[0050] (2)防雾涂膜的制作  \n\n[0051] 在聚碳酸酯树脂板基材上涂布各防雾涂料组合物。涂布是通过棒式涂布法进行的，以由防雾涂料组合物形成后的防雾涂膜的厚度成为1μm等方式进行调整。将涂布有防雾涂料组合物的基材放入至 $110^{\\circ}\\mathrm{C}$ 的烘箱内，历时15分钟使水及有机溶剂蒸发而形成防雾涂膜。由此获得各防雾涂膜试验片。  \n\n[0052] (3)防雾涂膜组合物的造膜性的评价[0053] 通过目视来观察防雾涂膜试验片的表面。当可获得均质涂膜时记为“良好”，当可获得虽然均质但发现少许破裂或收缩等的涂膜时记为“及格”，当在表面发现大量破裂或收缩等而无法获得均质涂膜时记为“不及格”。  \n\n[0054] (4)涂膜的防雾性的评价  \n\n[0055] 在比 $60^{\\circ}\\mathrm{C}$ 热水浴的水面高1cm的位置处，将防雾涂膜试验片以涂膜朝下的方式进行配置，使涂膜面向来自热水浴的蒸气。经过1分钟后，通过目视来观察涂膜上是否形成有雾。当涂膜表面未产生雾时记为“无雾”，当涂膜表面产生雾时记为“有雾”。  \n\n[0056] (5)涂膜的外观变化的评价  \n\n[0057] 对所述涂膜的防雾性进行评价后，在垂直竖立放置防雾涂膜试验片的状态下维持30分钟并使其干燥。然后，通过目视来观察在防雾涂膜试验片上是否形成有流水痕。当未发现流水痕时记为“无流挂”，当虽然确认到流水痕但极少时记为“流挂少许”，当清晰地发现流水痕时记为“有流挂”。  \n\n[0058] (6)防雾涂膜的干燥变白的评价  \n\n[0059] 从距离防雾涂膜表面3厘米以内的距离起吹送呼气，通过目视来观察防雾涂膜的外观的变化。在将呼气吹送到防雾涂膜表面的瞬间，呼气中所含的水蒸气覆盖防雾涂膜。在其干燥的过程中，观察防雾涂膜是否看起来较白。当防雾涂膜进行干燥的过程中未发现变白时记为“未变白”，当虽然确认到变白但极少时记为“略微变白”，当清晰地发现变白时记为“变白”。  \n\n[0060] 关于调配有酸性长条状胶体氧化硅及碱性长条状胶体氧化硅及碱性球状胶体氧化硅的实施例 $1{\\sim}4$ 的防雾涂料组合物，都可以形成无破裂或收缩等的防雾涂膜。由这些实施例所形成的防雾涂膜具有优异的防雾性。另外，即使防雾涂膜与水接触也不产生流水痕，在吹送呼气而进行干燥的过程中也未发现变白的现象。  \n\n[0061] 另一方面，关于调配有酸性长条状胶体氧化硅及碱性长条状胶体氧化硅及酸性球状胶体氧化硅的实施例 $5{\\sim}6$ 的防雾涂料组合物，也可以形成无破裂或收缩等的防雾涂膜。由这些实施例所形成的防雾涂膜具有优异的防雾性。另外，即使防雾涂膜与水接触，也不产生流水痕，在吹送呼气而进行干燥的过程中也未发现变白的现象。  \n\n[0062] 实施例7的防雾涂料组合物是将酸性长条状胶体氧化硅及碱性长条状胶体氧化硅及碱性球状胶体氧化硅，以长条状氧化硅与球状氧化硅的固体成分重量比成为40∶10的方式进行调配而获得的。本实施例的防雾涂料组合物可以形成无破裂或收缩等的防雾涂膜。另外，即使防雾涂膜与水接触，也未产生流水痕。当向本实施例的防雾涂膜吹送呼气而进行干燥时，虽然少许但确认到了变白。  \n\n[0063] 实施例8的防雾涂料组合物是将酸性长条状胶体氧化硅及碱性长条状胶体氧化硅及碱性球状胶体氧化硅，以长条状氧化硅与球状氧化硅的固体成分重量比成为10∶10的方式进行调配而获得的。利用本实施例的防雾涂料组合物所形成的防雾涂膜具有防雾性，在对其吹送呼气而进行干燥的过程中未发现变白的现象。但是，本实施例的防雾涂料组合物的造膜性稍有缺陷，当防雾涂膜与水接触时，确认到少许流水痕。  \n\n[0064] 根据这些实施例的结果可知，利用含有长条状胶体氧化硅及球状胶体氧化硅的防雾涂料组合物所获得的防雾涂膜的防雾性较高，几乎未发现防雾涂膜的干燥变白。通过适当地改变长条状胶体氧化硅与球状胶体氧化硅的固体成分重量比，可提高防雾涂料组合物的造膜性，或防止在所获得的防雾涂膜形成流水痕。  \n\n[0065] 关于由仅调配长条状胶体氧化硅而未含有球状胶体氧化硅的比较例1的防雾涂料组合物所形成的涂膜，造膜性、防雾性、及涂膜的外观变化试验的评价都优异。然而，在吹送呼气后的干燥过程中发现明显变白。关于由不含长条状胶体氧化硅而仅调配有球状胶体氧化硅的比较例2的防雾涂料组合物所形成的涂膜，在涂膜表面发生破裂，作为涂膜未成立。因此，未进行涂膜的防雾性、流水痕、及干燥变白性的评价。  \n\n[0066] [符号说明]  \n[0067] 1  基材  \n[0068] 2  长条状氧化硅  \n[0069] 3  球状氧化硅  \n[0070] 4  空隙  \n[0071] 5  防雾涂膜  \n[0072] 6  水  \n[0073] 7  水可能渗透的范围。  \n\n![](images/d7f07c3257580768ab8add3ac2faf3092376c6b6ff8d2c76fef5bf83dc334254.jpg)  \n图1  \n\n![](images/f790ba61ae63ead576fa02c8f924c6ae71831d5a5668852df5843116f5490c60.jpg)  \n图2  \n\n![](images/144be122931f947b9d296a8823778800b8cb9474d7b3e545c555dc916b10ea11.jpg)  \n图3",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,57 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n<html><body><table><tr><td>(21)申请号 202210573076.8 (51) Int.CI.</td></tr><tr><td>C08G 65/332 (2006.01) (22)申请日2022.05.23</td></tr><tr><td>C08G 65/28 (2006.01)</td></tr><tr><td>(65)同一申请的已公布的文献号 C07C 69/54 (2006.01)</td></tr><tr><td>申请公布号CN 114957645 A C07C 67/08 (2006.01)</td></tr><tr><td>(43)申请公布日2022.08.30 C08J 7/056 (2020.01)</td></tr><tr><td>CO8L 55/02 (2006.01) (73)专利权人武汉中科先进材料科技有限公司</td></tr><tr><td>地址 430000 湖北省武汉市经济技术开发 (56)对比文件</td></tr><tr><td>区201M地块华人汇和科技园(华中智 CN 103193953 A,2013.07.10</td></tr><tr><td>谷)一期F10研发楼1-2层 CN 105859584 A,2016.08.17</td></tr><tr><td>专利权人中国科学院深圳先进技术研究院 CN 107405430 A,2017.11.28</td></tr><tr><td>CN 113372807 A,2021.09.10</td></tr><tr><td>(72)发明人康翼鸿喻学锋吴列潘昊 CN 113416473 A,2021.09.21 程文杰　杨帆　甄亚枝</td></tr><tr><td>JP 2013079323 A,2013.05.02</td></tr><tr><td>(74)专利代理机构武汉高得专利代理事务所 审查员 孟帅 （普通合伙）42268</td></tr><tr><td>专利代理师 姜璐 权利要求书2页 说明书6页 附图1页</td></tr></table></body></html>",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n一种用于ABS基材的光固化超亲水涂料组合物及其涂层的制备方法",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明提供一种用于ABS基材的耐候性光固化超亲水涂层，所制备的超亲水涂层光固化速度快，效率高，能耗小，超亲水涂层水接触角小于${10}^{\\circ}$ °，防雾持久性比较好，可长时间耐水浸泡不脱落，稳定性强。本发明具体还涉及一种光固化单体及其制备方法，该光固化单体骨架为乙氧化三羟甲基丙烷三丙烯酸酯，分子链段中包含 $10\\sim15$ 个聚乙二醇单元，该光固化单体搭配光固化低聚物，通过对表面张力，ABS基材的渗透溶胀、官能度等方面增强涂层在ABS基材的附着力。另外，光固化单体、光固化低聚物与两性离子聚合物树脂形成交联的互穿网络，提高涂层硬度、机械强度，可锁住表面活性剂，延长防雾耐久时间。  \n\n![](images/ac5e1bef8f1674d8c3489aa6aa050714d3862486819e35442005822da9fc2169.jpg)  \n\n1.一种光固化单体，其特征在于：骨架为乙氧化三羟甲基丙烷三丙烯酸酯，分子链段中包含 $10\\sim15$ 个聚乙二醇单元，具有以下结构：  \n\n![](images/7df1b5a327ff62e4ad4c217a837737244acc949c0d33bcc8bf760e5cc65676d1.jpg)  \n\n其中 $\\mathrm{m}+\\mathrm{n}+\\mathrm{I}=10\\sim15$ 。  \n\n2.一种光固化单体的制备方法，其特征在于包括以下步骤：1)三羟甲基丙烷在强碱作用下与环氧丙烷开环加成， $80\\sim120^{\\circ}\\mathrm{C}$ 下反应 $3\\sim6\\mathrm{h}$ ，三羟基  \n甲基丙烷与环氧丙烷的摩尔比为 $1{:}3\\sim1{:}7$ ；2)将步骤1)的产物与丙烯酸在 $60\\sim80^{\\circ}\\mathrm{C}$ 下进行酯化反应 $3\\sim6\\mathrm{h}$ 得到，对甲苯磺酸作为  \n催化剂，二者摩尔比为 $1:1\\sim1:1.5$ ，得到含聚乙二醇链段的乙氧化三羟甲基丙烷三丙烯酸  \n酯。3.一种光固化超亲水涂料组合物，其特征在于，为全亲水体系，包括如下重量份的组  \n分：一种如权利要求1所述的光固化单体 $25\\sim45$ 份；表面活性剂 $3\\sim5$ 份；光固化低聚物 $33\\sim48$ 份；光固化两性离子单体 $10\\sim15$ 份；活性稀释剂单体 $5\\sim10$ 份；流平剂 $1\\sim2$ 份；光引发剂 $3\\sim5$ 份；所述组合物还包括溶剂，所述溶剂重量是其它组分总重量的0.5‑3倍；所述光固化低聚  \n物为聚乙二醇丙烯酸酯、聚氨酯丙烯酸酯中的一种或两种的组合；所述光固化两性离子单  \n体包括2‑丙烯酰胺‑2‑甲基丙磺酸(AMPS)、烯丙氧基壬基酚丙醇聚氧乙烯醚硫酸铵(DNS  \n86)中的一种或两种的组合。4.根据权利要求3所述光固化超亲水涂料组合物，其特征在于，所述表面活性剂为非离  \n子氟表面活性剂FS3100、FS30、FS31、FS34、FS1700中的一种或多种。5.根据权利要求3所述光固化超亲水涂料组合物，其特征在于，所述活性稀释剂单体包  \n括丙烯酸、衣康酸、丙烯酸羟乙酯(HEA)中的一种或多种；所述流平剂为丙烯酸酯类流平剂，  \n分子量在6000‑20000之间。6.根据权利要求3所述光固化超亲水涂料组合物，其特征在于，所述光引发剂包括2‑羟  \n基‑2‑甲基‑1‑苯基丙酮(1173)，1‑羟基环己基苯基甲酮(184)，2,4,6‑三甲基苯甲酰基‑二  \n苯基氧化膦(TPO)中的一种或多种；所述溶剂包括乙酸乙酯、乙酸丁酯、乙醇、异丙醇中的一  \n种或多种。7.一种用于ABS基材的光固化超亲水涂层的制备方法，其特征在于，将如权利要求 $3\\sim6$  \n\n任一项所述光固化超亲水涂料组合物涂覆在ABS基材上， $60\\mathrm{-}80^{\\circ}\\mathrm{C}$ 预烘 $2\\ifmmode-\\else-\\else\\textmu\\fi{}\\mathrm{3min}$ ，紫外LED灯光  \n\n固化30‑60s，能量为 $500\\mathrm{-}1000\\mathrm{mJ/cm^{2}}$ 。  \n\n8.根据权利要求7所述用于ABS基材的光固化超亲水涂层的制备方法，其特征在于，所述涂覆方式为喷涂、淋涂、滴涂、刮涂或滚涂中的一种。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 一种用于ABS基材的光固化超亲水涂料组合物及其涂层的制备方法",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明属于高分子材料技术领域，具体地说，涉及一种用于ABS基材的耐候性光固化超亲水涂层及制备。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] ABS塑料是丙烯腈(A)、丁二烯(B)、苯乙烯(S)三种单体的三元共聚物，三种单体相对含量可任意变化，制成各种树脂。ABS塑料兼有三种组元的共同性能，A使其耐化学腐蚀、耐热，并有一定的表面硬度，B使其具有高弹性和韧性，S使其具有热塑性塑料的加工成型特性。因此ABS塑料是一种原料易得、综合性能良好、价格便宜、用途广泛的“坚韧、质硬、刚性”材料。ABS塑料在机械、电气、纺织、汽车、飞机、轮船等制造工业及化工中获得了广泛的应用。  \n\n[0003] 超亲水涂层是指水落在该材料表面，水滴接触角小于10度，从外观上看即水在该材料表面不会形成水滴而是水膜，另外，超亲水涂层跟水的亲和力远大于跟灰尘以及其他脏污的亲和力，因此超亲水涂层在防雾、自清洁、导流、减阻等领域具有广泛应用。  \n\n[0004] 由于超亲水涂层的组分多为亲水材料，ABS疏水组分多，极性低，因此与亲水材料相容性差，导致附着力低，从而导致超亲水涂层容易脱落，耐候性差，专利CN  106048610  A提供了一种等离子体处理ABS表面实现亲水涂层的方法。相比热固化涂层，光固化涂层的优点的是固化速度快，固化温度低；缺点是固化程度不足导致涂层性能不够。另外，超亲水涂层通常难以做到耐候性(耐摩擦、耐水浸泡)等功能。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0005] 本发明的目的是针对现有技术的不足，提供一种用于ABS基材的耐候性光固化超亲水涂层。可实现高附着力、高耐磨、耐水泡、耐腐蚀等的功能。  \n\n[0006] 为实现上述目的，本发明采用的技术方案如下：  \n\n[0007] 本发明首先提供一种光固化单体，所述光固化单体的结构如(I)所示，骨架为乙氧化三羟甲基丙烷三丙烯酸酯，分子链段中包含 $10\\sim15$ 个聚乙二醇单元，其中 $\\mathrm{m}\\mathrm{+n+I}=10\\sim$ 15。  \n\n[0008]  \n\n![](images/1fada34838346a15717d4ab41364f2eded463f20706d53ef03b552c7486670d3.jpg)  \n\n[0009] 同时，本发明提供上述光固化单体的制备方法，具体如下：  \n[0010] 1)三羟甲基丙烷在强碱作用下与环氧丙烷开环加成， $80\\sim120^{\\circ}\\mathrm{C}$ 下反应 $3\\sim6\\mathrm{h}$ ，三羟基甲基丙烷与环氧丙烷的摩尔比为 $1{:}3\\sim1{:}7$ ；  \n\n[0011] 2)将步骤1)的产物与丙烯酸在 $60\\sim80^{\\circ}\\mathrm{C}$ 下进行酯化反应 $3\\sim6\\mathrm{h}$ ，对甲苯磺酸作为催化剂，二者摩尔比为1 $:1\\sim1:1.5$ ，得到含聚乙二醇链段的乙氧化三羟甲基丙烷三丙烯酸酯。  \n\n[0012] 所述光固化单体表面张力低，对基材润湿性好；对于ABS基材有较强的渗透溶胀能力，固化交联后可在基材与涂层之间形成一层很薄的互穿网络结构，从而增强附着力。同时所述光固化单体的官能度为2，官能度低，交联密度低，体积收缩小，附着力较好。光固化单体同时含有醚键和酯键，能促进附着。  \n\n[0013] 本发明还涉及一种在ABS基材附着力优异的光固化低聚物，包括聚乙二醇丙烯酸酯、聚氨酯丙烯酸酯中的一种或两种组合；  \n\n[0014] 所述聚乙二醇丙烯酸酯的制备方法为将聚乙二醇600/400/1000(PEG  600/400/1000)与丙烯酸或丙烯酸衍生物在酸的作用下成酯；  \n\n[0015] 所述聚氨酯丙烯酸酯的制备方法为二异氰酸酯和三羟甲基丙烯酸酯扩链反应制备；  \n\n[0016] 本发明还涉及一种光固化低聚物A，其结构如(Ⅱ)所示，命名为聚氧乙烯醚异氰脲酸丙烯酸酯。  \n\n![](images/a800d790705903483cd91b7dad1c886f6f272c310444e7a51bf7c30c57f4d044.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# (Ⅱ）  \n\n[0018] 所述光固化低聚物A的制备方法具体如下：  \n\n[0019] 1)聚醚胺(ED2003)与三(2‑羟乙基)异氰脲酸三丙烯酸酯(THEICTA)在 $60-80^{\\circ}\\mathrm{C}$ 下进行加成反应，二者摩尔比为1：2；  \n\n[0020] 2)羟乙基丙烯酸酯(HEA)与异佛尔酮二异氰酸酯(IPDI)在 $30-50^{\\circ}\\mathrm{C}$ 下反应 $0.5\\sim$ 1h，二者摩尔比为1：1；  \n\n[0021] 3)将步骤1)和步骤2)所得产物在 $30-50^{\\circ}\\mathrm{C}$ 下进行聚合反应，反应 $0.5\\sim1\\mathrm{h}$ 。  \n\n[0022] 所述光固化低聚物A表面张力低，对基材润湿性好；对于ABS基材有较强的渗透溶胀能力，固化交联后可在基材与涂层之间形成一层很薄的互穿网络结构，从而增强附着力。同时所述光固化低聚物A含有多种官能团，能提高其在ABS上的附着力。  \n\n[0023] 按照GB/T  9286‑1998进行光固化单体及光固化低聚物的附着力测试，0级代表最好，5级代表最差，具体方法为将光固化单体/光固化低聚物与光引发剂TPO以质量比24：1混合，UV灯下固化30s，测试附着力，结果附着力均为0级。  \n\n[0024] 本发明还提供一种光固化超亲水涂料组合物，为全亲水体系，包括如下重量份的组分：  \n\n[0025] 如前所述的光固化单体 $25\\sim45$ 份；  \n[0026] 表面活性剂 $3\\sim5$ 份；[0030] 流平剂 $1\\sim2$ 份；  \n[0031] 光引发剂 $3\\sim5$ 份；  \n[0032] 所述组合物还包括溶剂，所述溶剂重量是其它组分总重量的0.5‑3倍。  \n[0033] 所述表面活性剂为非离子氟表面活性剂FS3100；  \n[0034] 光固化低聚物为聚乙二醇丙烯酸酯、聚氨酯丙烯酸酯中的一种或两种组合，或如前所述的光固化低聚物A聚氧乙烯醚异氰脲酸丙烯酸酯；  \n[0035] 光固化两性离子单体包括2‑丙烯酰胺‑2‑甲基丙磺酸(AMPS)、烯丙氧基壬基酚丙醇聚氧乙烯醚硫酸铵(DNS  86)中的一种或两种组合；  \n[0036] 所述活性稀释剂单体包括丙烯酸、衣康酸、丙烯酸羟乙酯(HEA)中的一种或多种；[0037] 所述流平剂是能有效降低涂料表面张力，提高其流平性和均匀性的一类物质，能促使涂料在干燥成膜过程中形成一个平整、光滑、均匀的涂膜；  \n[0038] 所述流平剂为丙烯酸酯类流平剂，分子量在6000‑20000之间；  \n[0039] 所述光引发剂是一类能在紫外光区 $(250\\sim420\\mathrm{nm})$ 吸收一定波长的能量，产生自由基、阳离子等，从而引发单体聚合交联固化的化合物；所述光引发剂包括2‑羟基‑2‑甲基‑1‑苯基丙酮(1173)，1‑羟基环己基苯基甲酮(184)，2 ,4 ,6‑三甲基苯甲酰基‑二苯基氧化膦(TPO)中的一种或多种。  \n[0040] 所述溶剂包括乙酸乙酯、乙酸丁酯、乙醇、异丙醇中的一种或多种。  \n[0041] 本发明还包括上述光固化超亲水涂料组合物在用于ABS基材上包括防雾、自清洁、自润滑、减阻中的应用。  \n[0042] 本发明还提供一种用于ABS基材的光固化超亲水涂层的的制备方法，具体为：将光固化超亲水涂料组合物涂覆在ABS基材上， $60-80^{\\circ}\\mathrm{C}$ 预烘2‑3min，紫外LED灯光固化30‑60s，能量为 $500\\mathrm{-}1000\\mathrm{mJ/cm}^{2}$ 。  \n[0043] 具体的，其涂覆方式为喷涂、淋涂、滴涂、刮涂或滚涂中的一种。  \n[0044] 本发明通过水接触角测试仪测试光固化超亲水涂层的水接触角为 $3^{-8^{\\circ}}$ °。  \n[0045] 本发明通过水浴锅熏蒸测试来检测涂层防雾性能。水浴锅熏蒸是常见的防雾性能测试方法，水蒸气在水浴锅中与基材上会有温差，未处理的基材容易起雾。涂覆本发明超亲水涂层的ABS基材放置在 $60^{\\circ}\\mathrm{C}$ 水浴锅水面上方10cm持续熏蒸15min无起雾现象。  \n[0046] 根据GB/T9780‑2005测试超亲水涂层自然暴晒6个月的沾污率测试结果，与未涂覆超亲水涂层的ABS基材相比，耐沾污性改善比率达到 $50\\text{\\textperthousand}$ 。  \n[0047] 本发明耐水性能测试方法为：将涂覆有光固化超亲水涂层的ABS基材放置在水中浸泡 $72\\sim90\\mathrm{h}$ 后进行防雾测试，防雾性能未衰减。  \n[0048] 本发明中光固化超亲水涂层耐磨性能通过耐磨擦试验机测试。所述光固化超亲水涂层进行高温加速老化试验，将测试样品放入至 $200^{\\circ}\\mathrm{C}$ 烘箱，测试1000‑1500小时，测试老化前后涂层无明显脱落、剥离、起皱现象，水接触角也未有明显变化。  \n[0049] 所述紫外光固化超亲水涂层进行耐盐腐蚀测试， $5\\%$ 氯化钠溶液浸泡500‑1000小时，老化前后涂层无明显脱落、剥离、起皱现象。所述紫外光固化防雾涂层耐消毒水浸泡测  \n\n试，将样品浸泡于消毒水中200‑700小时，老化前后涂层无明显脱落、剥离、起皱现象，接触角也未有明显变化。  \n\n[0050] 所述紫外光固化超亲水涂层进行环境测试，将样品放置于露天环境 $1\\sim2$ 年，老化前后涂层无明显脱落、剥离、起皱现象，水接触角也未有明显变化。  \n\n[0051] 本发明与现有技术相比，本发明具有如下的有益效果：  \n\n[0052] 1、针对ABS基材难以附着的特点，设计合成了新型的高ABS附着力的光固化单体，搭配光固化低聚物，通过对表面张力，ABS基材的渗透溶胀、官能度设计从而增强涂层在ABS基材的附着力。同时光固化单体与光固化低聚物含有多种基团增强附着力。  \n\n[0053] 2、光固化单体、光固化低聚物与两性离子聚合物树脂形成交联的互穿网络，提高涂层硬度、机械强度，可锁住表面活性剂，延长防雾耐久时间。  \n\n[0054] 3、所制备的超亲水涂层光固化速度快，效率高，能耗小，超亲水涂层水接触角小于${10}^{\\circ}$ °，防雾持久性比较好，可长时间耐水浸泡不脱落，稳定性强。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 附图说明  \n\n[0055] 图1为实施例6所得涂层#6的水接触角图。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 具体实施方式  \n\n[0056] 下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。  \n\n[0057] 实施例1光固化单体的制备1  \n\n[0058] 在150ml反应瓶中投入1mol三羟甲基丙烷与3mol环氧丙烷，加入0 .05mol  NaOH，80$\\mathrm{{^\\circC}}$ 下反应3h后加入1mol丙烯酸以及0.01mol对甲苯磺酸， $60^{\\circ}\\mathrm{C}$ 下反应3h。  \n\n[0059] 实施例2光固化单体的制备2  \n\n[0060] 在150ml反应瓶中投入1mol三羟甲基丙烷与7mol环氧丙烷，加入0 .03mol  NaOH，$120^{\\circ}\\mathrm{C}$ 下反应6h后加入1.5mol丙烯酸以及0.01mol对甲苯磺酸， $80^{\\circ}\\mathrm{C}$ 下反应6h。  \n\n[0061] 实施例3光固化单体的制备3  \n\n[0062] 在 $150\\mathrm{ml}$ 反应瓶中投入1mol三羟甲基丙烷与5mol环氧丙烷，加入0 .04mol  NaOH，$120^{\\circ}\\mathrm{C}$ 下反应5h后加入1.5mol丙烯酸以及0.01mol对甲苯磺酸， $70^{\\circ}\\mathrm{C}$ 下反应5h。  \n\n[0063] 实施例4光固化低聚物A的制备1  \n\n[0064] 将1mol聚醚胺(ED2003)与2mol三(2‑羟乙基)异氰脲酸三丙烯酸酯(THEICTA)在60$\\mathrm{{^\\circC}}$ 下反应4h，将1mol羟乙基丙烯酸酯(HEA)与1mol异佛尔酮二异氰酸酯(IPDI)在 $30^{\\circ}\\mathrm{C}$ 下反应0.5h，将两步反应所得产物在 $30^{\\circ}\\mathrm{C}$ 下反应0.5h得到光固化低聚物A。  \n\n[0065] 实施例5光固化低聚物A的制备2  \n\n[0066] 将1mol聚醚胺(ED2003)与2mol三(2‑羟乙基)异氰脲酸三丙烯酸酯(THEICTA)在80$\\mathrm{{^\\circC}}$ 下反应4h，将1mol羟乙基丙烯酸酯(HEA)与1mol异佛尔酮二异氰酸酯(IPDI)在 $50^{\\circ}\\mathrm{C}$ 下反应1h，将两步反应所得产物在 $50^{\\circ}\\mathrm{C}$ 下反应1h得到光固化低聚物A。  \n\n[0067] 实施例6光固化低聚物(聚乙二醇丙烯酸酯)的制备[0068] 将聚乙二醇 $600/400/1000$ (PEG  600/400/1000)与丙烯酸或丙烯酸衍生物进行反应，投料比为 $1{:}1.5\\sim1.5{:}1$ ，在酸的催化下 $60\\sim80^{\\circ}\\mathrm{C}$ 反应 $6\\sim8\\mathrm{h}$ ；  \n\n[0069] 实施例7光固化低聚物(聚氨酯丙烯酸酯)的制备[0070] 将异佛尔酮二异氰酸酯和三羟甲基丙烯酸酯投入反应瓶中，投料摩尔比为1：1 .5$\\sim1{:}2$ ，在 $40\\sim60^{\\circ}\\mathrm{C}$ 下反应4小时；  \n\n[0071] 实施例8紫外光固化防雾涂料组合物的制备[0072] 本发明中涉及的光固化超亲水涂料组合物制备方法如下：准确称取各组分，将表面活性剂，光固化单体，光固化低聚物，光固化两性离子单体，活性稀释剂单体，加入溶剂混合搅拌 $0.5\\sim1\\mathrm{h}$ ，再加入光引发剂和流平剂，混合0.5h后制得。光固化超亲水涂料组合物组分及含量如表1，本发明中，溶剂可为乙酸乙酯、乙酸丁酯、异丙醇、乙醇中的一种或多种，在本实施例中，均采用乙酸丁酯：异丙醇：乙醇 $=4:3:3$ (体积比)做溶剂，溶剂总重量是其它组分总重量的0.3‑3倍。  \n\n[0073] 表1：光固化超亲水涂料组合物组分及含量  \n\n[0074]  \n\n<html><body><table><tr><td>配方</td><td>表面活性剂</td><td>光固化 单体</td><td>光固化低聚物</td><td>光固化两性离 子单体</td><td>活性稀释剂 单体</td><td>流平剂</td><td>光引发剂</td><td></td></tr><tr><td>编号 #1</td><td>FS31003份</td><td>45份</td><td>聚乙二醇丙烯酸酯10份</td><td>AMPS33份</td><td>丙烯酸5份</td><td>1份</td><td>184</td><td>3份</td></tr><tr><td>#2</td><td>FS30 3份</td><td>30份</td><td>聚乙二醇丙烯酸酯10份</td><td>AMPS48份</td><td>丙烯酸5份</td><td>1份</td><td>184</td><td>3份</td></tr><tr><td>#3</td><td>FS31 4份</td><td>25份</td><td>聚氨酯丙烯酸酯13份</td><td>AMPS45份</td><td>衣康酸8份</td><td>1份</td><td>1173</td><td>4份</td></tr><tr><td>#4</td><td>FS34 4份</td><td>25份</td><td>聚氨酯丙烯酸酯13份</td><td>DNS8644份</td><td>衣康酸8份</td><td>2份</td><td>1173</td><td>4份</td></tr><tr><td>#5</td><td>FS17005份</td><td>30份</td><td>光固化低聚物A聚氧乙烯醚 异氰脲酸丙烯酸酯15份</td><td>DNS8633份</td><td>HEA 10份</td><td>2份</td><td>TPO</td><td>5份</td></tr><tr><td>#6</td><td>FS31005份</td><td>25份</td><td>光固化低聚物A聚氧乙烯醚 异氰尿酸丙烯酸酯15份</td><td>DNS8638份</td><td>HEA 10份</td><td>2份</td><td></td><td>TPO5份</td></tr></table></body></html>  \n\n[0075] 实施例9ABS基材上光固化超亲水涂层的制备[0076] 将实施例8所得光固化超亲水涂料组合物配方#1至#6原液涂覆在ABS板材上，60$80^{\\circ}\\mathrm{C}$ 预烘 $2-3\\mathrm{{min}}$ ，紫外LED灯光固化30‑60s，能量为 $500-1000\\mathrm{mJ/cm}^{2}$ ，涂覆方式为喷涂、淋涂、滴涂、刮涂或滚涂中的一种。  \n\n[0077] 实施例10超亲水涂层的性能测试  \n\n[0078] 将实施例9中制备得到的光固化超亲水涂层，即光固化超亲水涂料组合物配方#1至#6进行测试，结果如表2所示：  \n\n[0079] 表2光固化超亲水涂层性能测试  \n\n<html><body><table><tr><td>测试项目 配方</td><td>水接 触角</td><td>耐水 性能</td><td>耐摩擦性能</td><td>高温加速老化 试验</td><td>耐盐腐蚀测试</td><td>耐消毒水浸泡</td></tr><tr><td>#1</td><td>8°</td><td>浸泡72h 仍防雾</td><td>200g羊毛毡， 5000次后仍防雾</td><td>200°℃1000h 仍防雾</td><td>氯化钠溶液浸泡 500小时仍防雾</td><td>消毒水浸泡 200小时仍防雾</td></tr><tr><td>#2</td><td>6°</td><td>浸泡78h 仍防雾</td><td>200g羊毛毡， 6000次后仍防雾</td><td>200℃1100h 仍防雾</td><td>氯化钠溶液浸泡 600小时仍防雾</td><td>消毒水浸泡 300小时仍防雾</td></tr><tr><td>#3</td><td>4°</td><td>浸泡84h 仍防雾</td><td>200g羊毛毡， 7000次后仍防雾</td><td>200℃1200h 仍防雾</td><td>氯化钠溶液浸泡 700小时仍防雾</td><td>消毒水浸泡 400小时仍防雾</td></tr><tr><td>#4</td><td>7°</td><td>浸泡90h 仍防雾</td><td>200g羊毛毡， 8000次后仍防雾</td><td>200℃1300h 仍防雾</td><td>氯化钠溶液浸泡 800小时仍防雾</td><td>消毒水浸泡 500小时仍防雾</td></tr><tr><td>#5</td><td>5°</td><td>浸泡92h 仍防雾</td><td>200g羊毛毡， 9000次后仍防雾</td><td>200C1400h 仍防雾</td><td>氯化钠溶液浸泡 900小时仍防雾</td><td>消毒水浸泡 600小时仍防雾</td></tr><tr><td>#6</td><td>3°</td><td>浸泡96h 仍防雾</td><td>200g羊毛毡， 10000次后仍防雾</td><td>200℃1500h 仍防雾</td><td>氯化钠溶液浸泡 1000小时仍防雾</td><td>消毒水浸泡 700小时仍防雾</td></tr></table></body></html>  \n\n![](images/873e65beeff6d89fb7c61fb41d910d53e927ed1d2bf9810e6c65a6f80c011680.jpg)  \n图1",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# (19)国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n(10)授权公告号 CN 115028830 B(45)授权公告日 2023.12.22  \n\n<html><body><table><tr><td>(21)申请号202210502326.9 (56)对比文件</td></tr><tr><td>(22)申请日 2022.05.10 CN 106750235 A,2017.05.31</td></tr><tr><td>US 2010227127 A1,2010.09.09</td></tr><tr><td>(65)同一申请的已公布的文献号 CN 104357030 A,2015.02.18</td></tr><tr><td>申请公布号CN 115028830 A CN 106574099 A,2017.04.19</td></tr><tr><td>(43)申请公布日 2022.09.09 CN 106800621 A,2017.06.06</td></tr><tr><td>(73)专利权人 武汉中科先进材料科技有限公司 CN 106867376 A,2017.06.20</td></tr><tr><td>地址 430000 湖北省武汉市经济技术开发 CN 110054730 A,2019.07.26</td></tr><tr><td>CN 112920414 A,2021.06.08 区201M地块华人汇和科技园(华中智</td></tr><tr><td>CN 113416473 A,2021.09.21 谷)一期F10研发楼1-2层</td></tr><tr><td>CN 113993637 A,2022.01.28 (72)发明人 康翼鸿喻学锋甄亚枝何睿</td></tr><tr><td>CN 114163577 A,2022.03.11 杨帆</td></tr><tr><td>CN 114989348 A,2022.09.02</td></tr><tr><td>(74)专利代理机构武汉高得专利代理事务所 李豹.磺酸盐型双阴离子乳化剂的合成及其</td></tr><tr><td>（普通合伙）42268 在水性环氧树脂制备中的应用.《中国优秀硕士</td></tr><tr><td>专利代理师 杨如增 论文期刊数据库工程科技I辑》.2015，全文. Naz，Asima.Polymer membranes for</td></tr><tr><td>(51) Int.CI. biofouling mitigation: a review.《POLYMER-</td></tr><tr><td>C08G 65/334(2006.01)</td></tr><tr><td>PLASTICS TECHNOLOGY AND MATERIALS》.2019, C08G 65/332 (2006.01)</td></tr><tr><td>第58卷(第17期)，1829-1854. C09D 171/02 (2006.01)</td></tr><tr><td>CO9D 7/20 (2018.01) 审查员 董志瑞</td></tr></table></body></html>  \n\n权利要求书1页  说明书5页",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n一种用于防雾涂层的亲水树脂及其制备方法",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明公开一种用于防雾涂层的亲水树脂及其制备方法，在亲水性二元聚醚胺的两端通过两步迈克尔加成反应接枝了磺酸盐结构和丙烯酸酯结构，设计使用丙烯酰吗啉和/或N ,N‑二甲基丙烯酰胺溶解2‑丙烯酰胺基‑2‑甲基丙磺酸(AMPS)，既可以作为溶剂溶解AMPS，又因为带有活泼的碳碳双键可作为光固化或迈克尔加成反应的单体，不会使目标产物在超亲水涂层制备的应用上受限；由于在聚醚胺上接枝了比非离子聚乙二醇(EO)链段更为亲水的磺酸盐结构，减少聚乙二醇(EO)链段的使用量，增强固化后防雾涂层硬度的同时不影响附着力，最终制备得到的亲水树脂应用于防雾涂层中，防雾效果好，指摸无痕，具有良好的附着力和硬度。  \n\n1.一种用于防雾涂层的亲水树脂，其特征在于，具有以下结构式：  \n\n![](images/571aa2d15aa93efc4e3f0532bf009bb6536ef74fafceca168ea5968875102e33.jpg)  \n(I)  \n\n其中，x ,y ,z值根据选用的市售聚醚胺的牌号而变化，所述市售聚醚胺为ED2003、ED900、ED600中的一种或两种的混合物； $\\mathrm{R}_{1}$ 和R 为不同基团，选自以下结构A、B或C，其中R 或$\\mathrm{R_{2}}$ 为结构A； $\\mathrm{R_{3}}\\mathrm{\\#\\mathbb{H}R_{4}}$ 为多官能丙烯酸酯单体与伯胺或仲胺进行迈克尔加成反应后形成的连接N原子的乙基羰基以外的结构；  \n\n![](images/d1efaee015ca131d4dc465e84035564aa91b4caca8703438fdba7b999879d95d.jpg)  \n\n其中， $\\mathrm{R}_{5},\\mathrm{R}_{6},\\mathrm{R}_{7}$ 选自碳原子数小于等于6的烷烃基或烷羟基，且 $\\mathrm{R}_{5},\\mathrm{R}_{6},\\mathrm{R}_{7}$ 不能为氢原子。2.根据权利要求1所述用于防雾涂层的亲水树脂的制备方法，其特征在于，包括以下步  \n骤：1)2‑丙烯酰胺基‑2‑甲基丙磺酸溶解于带有活泼双键的液态单体中，再用有机叔胺进  \n行中和得到中间产物1；2)称取直链亲水聚醚胺加入到步骤1)得到的中间产物1中， $40-80^{\\circ}\\mathrm{C}$ 下反应 $2\\sim8\\mathrm{h}$ ，得到  \n中间产物2；3)称取多官能丙烯酸酯单体加入到步骤2)得到的中间产物2中， $40-80^{\\circ}\\mathrm{C}$ 下反应 $2\\sim8\\mathrm{h}$ ，  \n得到用于防雾涂层的亲水树脂；所述带有活泼双键的液态单体为丙烯酰吗啉、N,N‑二甲基丙烯酰胺或两者的混合物；所述聚醚胺为ED2003、ED900、ED600中的一种或两种的混合物。3.根据权利要求2所述用于防雾涂层的亲水树脂的制备方法，其特征在于：所述步骤1)  \n中2‑丙烯酰胺基‑2‑甲基丙磺酸，带有活泼双键的液态单体以及有机叔胺的摩尔比为1：1：  \n1。4.根据权利要求2所述用于防雾涂层的亲水树脂的制备方法，其特征在于：所述步骤2)  \n中聚醚胺和中间产物1的摩尔比为 $1:1\\sim1:3$ 。5.根据权利要求2所述用于防雾涂层的亲水树脂的制备方法，其特征在于：所述步骤2)  \n中反应温度为 $40^{\\circ}\\mathrm{C}$ ，反应时长为 $6\\sim8\\mathrm{h}$ 。6.根据权利要求2所述用于防雾涂层的亲水树脂的制备方法，其特征在于：所述步骤3)  \n中多官能丙烯酸酯单体和中间产物2的摩尔比为 $1:1\\sim1:3$ 。7.根据权利要求2所述用于防雾涂层的亲水树脂的制备方法，其特征在于：所述步骤3)  \n中反应温度为 $80^{\\circ}\\mathrm{C}$ ,反应时长为 $6\\sim8\\mathrm{h}$ 。8.一种如权利要求1所述亲水树脂在防雾涂层中应用。",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# 一种用于防雾涂层的亲水树脂及其制备方法",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明属于高分子材料合成技术领域，具体涉及一种用于防雾涂层的亲水树脂及其制备方法。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 具有防雾功能的超亲水涂层的制备，需要使用亲水单体和亲水聚合物，但是，现有的亲水单体因为分子量小，官能度低(只有一个或两个活性双键)，导致超亲水涂层的交联度小，涂层强度和各项功能均较易被破坏；而市售的亲水聚合物往往又亲水性不足，导致超亲水涂层的防雾性能迅速衰退。  \n\n[0003] 现有的防雾涂料，一般由亲水树脂和单体、附着力树脂和单体、表面助剂以及溶剂构成，亲水树脂和单体一般包括PEG(EO)n  DA( $\\mathrm{\\dot{n}}\\geqslant4$ ，n为整数)，乙氧化双酚A(EO)n二丙烯酸酯( $\\mathrm{\\acute{n}\\geqslant4}$ ，n为整数)，三羟甲基丙烷(EO)n三丙烯酸酯 $(\\mathrm{n}\\geqslant10$ ，n为整数)，丙烯酰吗啉(ACMO)，N,N‑二甲基丙烯酰胺等，附着力树脂和单体包括DSMAgiSynTM  2421，1,6‑己二醇二丙烯酸酯(HDDA)等，表面助剂主要是起流平和润湿的作用，如果以上组分混合后黏度较大，会使用单组份溶剂或混合溶剂进行稀释。  \n\n[0004] 上述组分中起防雾作用的主要功能基团为长的聚乙二醇(EO)链段，但是，EO链段却会引起附着力的迅速下降，导致涂层水洗或者在水中浸泡一段时间后气泡或脱落，并且长的聚乙二醇(EO)链段为软链段，易导致涂层硬度低，手摸或者用纸巾轻拭后容易留下指纹或者划痕。  \n\n[0005] 本发明要解决的技术问题是提供一种低聚物亲水树脂，以实现防雾功能衰退速度较慢或永久性防雾的超亲水涂层的制备。该树脂能够应用在PC\\PMMA\\PET等塑料基材上，实现良好乃至优秀的附着力以及耐水煮性。  \n\n[0006] 中国专利CN106867376A公开了一种多官能度亲水性紫外光固化树脂的制备方法及其应用，通过迈克尔加成接枝甲氧基聚乙二醇丙烯酸酯。但该专利合成的树脂完全依靠EO链段提供亲水性，大量使用会影响涂层的附着力以及硬度。CN106750235A公开一种季铵盐型亲水性紫外光固化树脂的制备方法，将以化学键固定在光固化后形成的交联网络上的季铵盐结构，应用到防雾涂料中，可以保证涂膜具有优异的初始及持续防雾性能。但该专利使用的季铵盐为 $80\\%$ 的丙烯酰氧乙基三甲基氯化铵水溶液，合成的光固化树脂中含有的水分难以去除，不能应用在含有大量不溶于水的有机物或者含有硅氧烷链段的体系中。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0007] 本发明的目的是针对现有技术的不足，本发明提供一种用于防雾涂层的亲水树脂，该树脂具有EO链段和磺酸盐，亲水性更强，能替代常规的亲水低聚物，从而降低EO链段对附着力和耐水煮性的负面影响。为实现上述目的，本发明采用的技术方案如下：  \n\n[0008] 首先本发明提供一种用于防雾涂层的亲水树脂，具有以下结构式：  \n\n[0009]  \n\n![](images/199d953c12455dd407eba8a329a12e04b20c84406b1a903cd40e4c98e76346a4.jpg)  \n\n[0010] 其中，x,y ,z值根据选用的市售聚醚胺的牌号而变化；R1和R2选自以下结构 $\\mathtt{A}\\sim\\mathtt{C}$ ；R3和R4为丙烯酸酯与伯胺或仲胺进行迈克尔加成反应后形成的连接N原子的乙基羰基以外的结构；  \n\n[0011]  \n\n![](images/dac1a61b1e8d5f53203f12d365a79469cf6ae62e3929bf58628fc7578ab4430e.jpg)  \n\n[0012] 其中，R5,R6,R7选自碳原子数小于等于6的烷烃基或烷羟基，且R5,R6,R7不能为氢原子。  \n\n[0013] 本发明其次提供一种用于防雾涂层的亲水树脂的制备方法，包括以下步骤：  \n\n[0014] 1)2‑丙烯酰胺基‑2‑甲基丙磺酸溶解于带有活泼双键的液态单体中，再用有机叔胺进行中和得到中间产物1；  \n\n[0015] 2)称取直链亲水聚醚胺加入到步骤1)得到的中间产物1中， $40-80^{\\circ}\\mathrm{C}$ ，反应 $2\\sim8\\mathrm{h}$ ，得到中间产物2；  \n\n[0016] 3)称取多官能单体加入到步骤2)得到的中间产物2中， $40-80^{\\circ}\\mathrm{C}$ 反应 $2\\sim8\\mathrm{h}$ ，得到用于防雾涂层的亲水树脂。  \n\n[0017] 具体的，所述带有活泼双键的液态单体为丙烯酰吗啉、N,N‑二甲基丙烯酰胺或两者的混合物。  \n\n[0018] 具体的，所述聚醚胺为ED2003、ED900、ED600中的一种或两种的混合物。  \n\n[0019] 优选的，步骤1)中2‑丙烯酰胺基‑2‑甲基丙磺酸、带有活泼双键的液态单体以及有机叔胺的摩尔比为1：1：1。  \n\n[0020] 具体的，所述步骤2)中聚醚胺和中间产物1的摩尔比为 $2\\colon1\\sim1:2$ 。  \n[0021] 优选的，所述步骤2)中反应温度为 $40^{\\circ}\\mathrm{C}$ ，反应时长为 $6\\sim8\\mathrm{h}$ 。  \n[0022] 具体的，所述步骤3)中多官能单体和中间产物2的摩尔比为 $1\\colon1\\sim1\\colon2$ 。  \n[0023] 优选的，所述步骤3)中反应温度为 $80^{\\circ}\\mathrm{C}$ ，反应时长为 $6\\sim8\\mathrm{h}$ 。  \n[0024] 本发明还提供上述用于防雾涂层的亲水树脂的应用。  \n\n[0025] 与现有技术相比，本发明具有如下突出效果：  \n\n[0026] 1)本发明在亲水性二元聚醚胺的两端通过两步迈克尔加成反应分别接枝磺酸盐结构和多个(大于等于2)丙烯酸酯基，设计使用丙烯酰吗啉和/或N,N‑二甲基丙烯酰胺溶解2‑丙烯酰胺基‑2‑甲基丙磺酸(AMPS)，并和小分子叔胺中和成盐，形成含有磺酸盐的中间产物1，先一步利用小分子叔胺中和AMPS成盐是为了防止AMPS与聚醚胺的端胺同时发生酸碱中和反应和迈克尔加成反应，导致凝胶。  \n\n[0027] 2)本发明在聚醚胺上接枝了比非离子聚乙二醇(EO)链段更为亲水的磺酸盐结构，减少聚乙二醇(EO)链段的使用量，增强固化后防雾涂层硬度的同时，因为磺酸盐结构在整个涂层结构中占比较少，不会影响附着力进而导致涂层水洗或者在水中浸泡一段时间后起泡或脱落。  \n\n[0028] 3)将2‑丙烯酰胺基‑2‑甲基丙磺酸(AMPS)溶解于等摩尔的丙烯酰吗啉(ACMO)和/或N,N‑二甲基丙烯酰胺等带有活泼双键的液态单体中，ACMO和/或N,N‑二甲基丙烯酰胺既可以作为溶剂溶解AMPS，又因为带有活泼的碳碳双键可作为光固化或迈克尔加成反应单体，不会使目标产物在超亲水涂层制备的应用上受限。  \n\n[0029] 4)AMPS的常用溶剂为水和DMF，AMPS溶于水后容易在水中自聚，且水作为溶剂，很难应用于含有大量不溶于水的有机物或者水的存在会影响储存稳定性的体系中，例如含有硅氧烷链段的体系；DMF沸点高，挥发困难，且有毒，在很多场景中应用受限。  \n\n[0030] 5)由本发明提供的亲水树脂制备得到的防雾涂层，防雾效果好，指摸无痕，具有良好的附着力和硬度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 具体实施方式  \n\n[0031] 下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。  \n\n[0032] 实施例1用于防雾的亲水树脂的制备[0033] 1)2‑丙烯酰胺基‑2‑甲基丙磺酸(AMPS)溶解于等摩尔的丙烯酰吗啉(ACMO)中，并用等摩尔量的三乙胺中和，得到中间产物1；  \n\n[0034] 2)选用直链亲水聚醚胺ED2003，按照摩尔比为聚醚胺：中间产物 $1=1$ ：2的比例投料，在 $40^{\\circ}\\mathrm{C}$ 下反应8h，得到中间产物2；  \n\n[0035] 3)中间产物2再与1，6‑己二醇二丙烯酸酯(HDDA)、季戊四醇三丙烯酸酯(PETA)、聚乙二醇200二丙烯酸酯(PEG200DA)三种的混合物，按照摩尔比为中间产物2：多官能单体 $\\c=$ 1：2的比例投料，在 $80^{\\circ}\\mathrm{C}$ 下反应8h，得到用于防雾的亲水树脂。  \n\n[0036] 实施例2用于防雾的亲水树脂的制备  \n\n[0037] 1)2‑丙烯酰胺基‑2‑甲基丙磺酸(AMPS)溶解于等摩尔的N,N‑二甲基丙烯酰胺中，并用等摩尔量的三乙胺中和，得到中间产物1；  \n\n[0038] 2)选用直链亲水聚醚胺ED900和ED600，按照摩尔比为聚醚胺：中间产物 $1=1$ ：2的比例投料，在 $40^{\\circ}\\mathrm{C}$ 下反应8h，得到中间产物2；  \n\n[0039] 3)中间产物2再与季戊四醇三丙烯酸酯(PETA)，按照摩尔比为中间产物2：PETA $\\c=$ 1：1.5的比例投料，在 $80^{\\circ}\\mathrm{C}$ 下反应8h，得到用于防雾的亲水树脂。  \n\n[0040] 实施例3用于防雾的亲水树脂的制备[0041] 1)2‑丙烯酰胺基‑2‑甲基丙磺酸(AMPS)溶解于等摩尔的丙烯酰吗啉(ACMO)和N ,N‑二甲基丙烯酰胺的混合物(ACMO和N,N‑二甲基丙烯酰胺的摩尔比为1：2)中，并用等摩尔量的三乙胺中和，得到中间产物1；  \n\n[0042] 2)选用直链亲水聚醚胺ED900和ED600，按照摩尔比为聚醚胺：中间产物 $1=1$ ：2的比例投料，在 $40^{\\circ}\\mathrm{C}$ 下反应8h，得到中间产物2；  \n\n[0043] 3)中间产物2再与季戊四醇三丙烯酸酯(PETA)，按照摩尔比为中间产物2：PETA $\\c=$ 1：1.5的比例投料，在 $80^{\\circ}\\mathrm{C}$ 下反应8h，得到用于防雾的亲水树脂。  \n\n[0044] 实施例4用于防雾的亲水树脂的制备[0045] 1)2‑丙烯酰胺基‑2‑甲基丙磺酸(AMPS)溶解于等摩尔的丙烯酰吗啉(ACMO)和N ,N‑二甲基丙烯酰胺的混合物(ACMO和N,N‑二甲基丙烯酰胺的摩尔比为1：2)中，并用等摩尔量的三乙胺中和，得到中间产物1；  \n\n[0046] 2)选用直链亲水聚醚胺ED900和ED600，按照摩尔比为聚醚胺：中间产物 $1=1$ ：1的比例投料，在 $40^{\\circ}\\mathrm{C}$ 下反应8h，得到中间产物2；  \n\n[0047] 3)中间产物2再与季戊四醇三丙烯酸酯(PETA)，按照摩尔比为中间产物2：PETA $\\c=$ 1：3的比例投料，在 $80^{\\circ}\\mathrm{C}$ 下反应8h，得到用于防雾的亲水树脂。  \n\n[0048] 实施例5亲水树脂在防雾涂层的应用[0049] 按重量份计将15份实施例1中得到的亲水树脂，15份DSM  AgiSynTM  2421，10份HDDA，10份ACMO，0 .5份Tego  wet  270，2份引发剂TPO，0 .5份引发剂184和47份乙醇加入分散料筒内高速分散30min，制备得到防雾涂料。  \n\n[0050] 将上述防雾涂料用线棒均匀的涂在洁净的PC塑料基材上， $80^{\\circ}\\mathrm{C}$ 烘箱预干燥2min，然后放在传送带式UV固化机上，经10000mJ的汞灯光固化后，即得防雾涂层。  \n\n[0051] 实施例6亲水树脂在防雾涂层的应用[0052] 按重量份计将10份实施例1中得到的亲水树脂，10份DSM  AgiSynTM  2421，10份HDDA，20份PEG600DA，0 .1份Tego  wet  500，2 .5份引发剂1173D和47 .4份乙醇加入分散料筒内高速分散30min，制备得到防雾涂料。  \n\n[0053] 将上述防雾涂料用线棒均匀的涂在洁净的PMMA塑料基材上， $80^{\\circ}\\mathrm{C}$ 烘箱预干燥2min，然后放在传送带式UV固化机上，经20000mJ的LED紫外光固化后，即得防雾涂层。  \n\n[0054] 实施例7亲水树脂在防雾涂层的应用[0055] 按重量份计将20份实施例1中得到的亲水树脂，10份DSM  AgiSynTM  2421，10份HDDA，10份TMPTA15EODA，0 .05份Tego  wet  270，2份引发剂TPO，0 .5份引发剂184和47 .45份乙醇加入分散料筒内高速分散30min，制备得到防雾涂料。  \n\n[0056] 将上述防雾涂料用线棒均匀的涂在干净的PET塑料材料上， $80^{\\circ}\\mathrm{C}$ 烘箱预干燥2min，然后放在传送带式UV固化机上，经20000mJ的LED紫外光固化后，即得防雾涂层。  \n\n[0057] 性能测试[0058] 实施例5‑7所制得的防雾涂层的性能测试项目和测试结果如下表所示：  \n\n<html><body><table><tr><td rowspan=\"6\">[0059]</td><td>项目</td><td>实施例5</td><td>实施例6</td><td>实施例7</td></tr><tr><td>涂层表观</td><td>平滑，指摸无痕</td><td>平滑，指摸有轻微痕 迹</td><td>平滑，指摸无痕</td></tr><tr><td>涂层铅笔硬度</td><td>H</td><td>HB</td><td>H</td></tr><tr><td>80℃热水水面上方 5cm处初始防雾效 果</td><td>肉眼观察，视野清晰， 不受影响</td><td>肉眼观察，视野清晰， 不受影响</td><td>肉眼观察，视野清晰， 不受影响</td></tr><tr><td>泡100ppm次氯酸1h 后是否脱皮</td><td>肉眼观察，视野清晰， 不受影响</td><td>肉眼观察，视野清晰， 不受影响</td><td>肉眼观察，视野清晰， 不受影响</td></tr><tr><td>泡100ppm次氯酸1h 后防雾效果</td><td>肉眼观察，视野清晰， 不受影响</td><td>肉眼观察，视野清晰， 不受影响</td><td>肉眼观察，视野清晰， 不受影响</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,57 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n(10)授权公告号 CN 115044008 B(45)授权公告日 2024.01.05  \n\n(21)申请号 202210614799.8  \n(22)申请日 2022.06.01  \n(65)同一申请的已公布的文献号申请公布号 CN 115044008 A  \n(43)申请公布日 2022.09.13  \n(73)专利权人 武汉中科先进材料科技有限公司地址 430000 湖北省武汉市经济技术开发区201M地块华人汇和科技园（华中智谷）一期F10研发楼1-2层  \n(72)发明人 康翼鸿　喻学锋　程文杰　何睿吴列　甄亚枝　杨帆  \n(74)专利代理机构 武汉高得专利代理事务所(普通合伙) 42268专利代理师 杨如增",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n一种亲水型阳离子光固化树脂及其制备方法和应用",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明属于高分子合成技术领域，具体涉及一种亲水型阳离子光固化树脂及其制备方法。将二元聚醚胺与聚乙二醇二丙烯酸酯在室温下进行迈克尔加成反应，得到丙烯酸酯基封端的亲水聚合物中间体1，然后与氨基磺酸盐继续进行迈克尔加成反应得到中间体2；另将二异氰酸酯与带羟基的氧杂环丁烷反应形成半封端预聚体；将所述亲水聚合物中间体2与半封端的预聚体反应，得到所述的亲水型阳离子光固化树脂。该树脂可进行阳离子光固化反应，收缩率低，附着力优异，光固化过程不发生氧阻聚，固化反应程度更高，具备超亲水性，并且能够耐消毒液以及乙醇浸泡。  \n\n权利要求书2页 说明书8页",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# 审查员 范洁  \n\n衣晓庆等，.“超支化聚醚胺杂化水凝胶的制备及其吸附行为研究”.《化工新型材料》.2018,第46卷(第3期) ,178-182.  \n\n(51)Int.Cl. C08G 18/50(2006.01) C08G 18/28(2006.01) C09D 175/08(2006.01)",
+        "category": " References"
+    },
+    {
+        "id": 6,
+        "chunk": "# (56)对比文件  \n\nCN 114085353 A,2022.02.25   \nWO 2012130762 A1 ,2012.10.04   \nUS 2008305349 A1 ,2008.12.11   \nUS 2010015450 A1 ,2010.01 .21   \nCN 110423435 A,2019.11 .08   \nWO 2006115547 A2,2006.11 .02  \n\n1.一种亲水型阳离子光固化树脂，其特征在于，该树脂具有全亲水主链和全疏水侧链，由二元聚醚胺与聚乙二醇二丙烯酸酯反应生成的聚合物中间体为主链结构单元，二异氰酸酯与带羟基的氧杂环丁烷反应得到的化合物链段为疏水侧链，主链两端的丙烯酸酯基进行氨基磺酸盐封端得到。  \n\n2.一种如权利要求1所述亲水型阳离子光固化树脂的制备方法，其特征在于，包括以下  \n步骤：1)二异氰酸酯与带羟基的氧杂环丁烷反应得到端NCO的半封端预聚体，其中二异氰酸  \n酯的异氰酸酯基(‑NCO)和氧杂环丁烷的羟基(‑OH)的摩尔比2:1；2)二元聚醚胺与聚乙二醇二丙烯酸酯在室温下进行迈克尔加成反应，得到丙烯酸酯基  \n封端的亲水聚合物中间体1，其中二元聚醚胺与聚乙二醇二丙烯酸酯的摩尔比为1:2‑4:5；3)氨基磺酸盐与中间体1中的丙烯酸酯基在室温下进行迈克尔加成反应得到中间体2，  \n其中氨基磺酸盐与中间体1的摩尔比为2:1，氨基磺酸盐事先用去离子水配置成溶液，质量  \n分数为 $50\\%-80\\%$ ；4)将步骤1中端NCO的半封端预聚体和中间体2按照异氰酸酯基(‑NCO)与仲胺(‑NH‑)摩  \n尔比1:1反应得到亲水型阳离子光固化树脂。3.根据权利要求2所述亲水型阳离子光固化树脂的制备方法，其特征在于：所述二异氰  \n酸酯包括异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、六亚甲基二异氰酸酯(HDI)、  \n二环己基甲烷二异氰酸酯(HMDI)、改性二苯基甲烷二异氰酸酯(液化MDI)中的一种或至少  \n两种的组合；所述带羟基的氧杂环丁烷包括3‑羟甲基氧杂环丁烷、3‑甲基‑3‑羟甲基氧杂环  \n丁烷、3‑乙基‑3‑羟甲基氧杂环丁烷中的至少一种。4.根据权利要求2所述亲水型阳离子光固化树脂的制备方法，其特征在于：所述二元聚  \n醚胺包括D230、D400、D2000、ED600、ED900和ED2003中的至少一种；所述聚乙二醇二丙烯酸  \n酯包括PEG200DA、PEG400DA、PEG600DA、PEG750DA和PEG1000DA中的至少一种。5.根据权利要求2所述亲水型阳离子光固化树脂的制备方法，其特征在于：所述氨基磺  \n酸盐包括乙二胺基乙磺酸钠，乙二胺基丙磺酸钠，氨基苯磺酸钠和牛磺酸钠中的至少一种。6.根据权利要求2所述亲水型阳离子光固化树脂的制备方法，其特征在于，步骤1)中先  \n将二异氰酸酯和二月桂酸二丁基锡加入反应釜中开启搅拌混合均匀；再将氧杂环丁烷加至  \n恒压滴液槽中，室温下缓慢滴加至上述反应釜中，滴完继续室温反应30min后，升温至60‑70  \n$\\mathrm{{^\\circC}}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值，得到半封端预聚体。7.根据权利要求2所述亲水型阳离子光固化树脂的制备方法，其特征在于，步骤2)将二  \n元聚醚胺加入反应釜中维持室温搅拌，将聚乙二醇二丙烯酸酯转移至恒压滴液槽中，缓慢  \n滴加至上述反应釜中，滴完维持室温继续反应2‑4h得到丙烯酸酯基封端的亲水聚合物中间  \n体1。8.根据权利要求6所述亲水型阳离子光固化树脂的制备方法，其特征在于，步骤3)用去  \n离子水将氨基磺酸盐溶解均匀后转移至恒压滴液槽中，室温条件下缓慢滴加至上述反应釜  \n中，滴完维持室温继续反应2‑3h后，升温至 $40-50^{\\circ}\\mathrm{C}$ 反应2h得到中间体2。9.根据权利要求2所述亲水型阳离子光固化树脂的制备方法，其特征在于，步骤4)将半  \n封端预聚体转移到中间体2的恒压滴液槽中，冰水浴条件下缓慢滴加至中间体2中，滴完继  \n续反应30min后，升温至室温反应直至混合物的异氰酸酯基(‑NCO)的含量为零，得到亲水型  \n\n阳离子光固化树脂，避光保存。  \n\n10.一种如权利要求1所述亲水型阳离子光固化树脂在超亲水涂层中的应用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 一种亲水型阳离子光固化树脂及其制备方法和应用",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 技术领域  \n\n[0001] 本发明属于高分子合成技术领域，一种亲水型阳离子光固化树脂及其制备方法。",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 背景技术  \n\n[0002] 超亲水表面与水具有很强的相互作用力，将水滴滴在上面能够在较短时间内完全铺展开，使接触角等于或接近于 $\\cdot0^{\\circ}$ °，在自清洁，导流，防污，生物耗材等众多领域均有着十分广阔的应用前景，是当前研究的热点之一。实现超亲水的方法为化学改性法(如等离子体处理)或者表面涂层法，但是这两种制备方法都存在一些问题，化学改性法需要采用昂贵的仪器设备或复杂的工艺流程，易受外界条件(光，热，氧等)的影响，应用领域仍有待于发展。表面涂层法最早依赖于亲水表面活性剂来提供亲水性能，耐用性较差，遇水容易失效，逐渐被亲水树脂替代。按照固化方式不同，有热固化型亲水树脂和UV(紫外线)光固化型亲水树脂。虽然热固化型亲水树脂可以提供良好的耐磨性，但它们需要长固化时间和高能量消耗以便溶剂蒸发，生产效率低。UV(紫外线)光固化型亲水树脂通常为自由基型，以碳碳双键作为活性基团，在紫外光下能够实现瞬间固化，非常适合连续工业化生产，但是固化过程容易产生氧阻聚，反应程度受限，需增大引发剂的用量来弥补，它们的性能通常低于热固化涂料。  \n\n[0003] 不少研究者提出了阳离子光固化的方式。阳离子光固化树脂具有固化速度快，体积收缩小，附着力高，没有氧阻聚，固化反应不易终止的特点，固化反应程度高，兼具光固化的便捷性与热固化的高反应性，成为UV固化领域的研究热点。但是阳离子光固化树脂仍处于研究阶段，商业化的产品很少，具有优异机械性能和持久亲水性能的阳离子光固化树脂更是鲜有报道。  \n\n[0004] 另外，超亲水涂层的现有技术中，树脂的亲疏水结构混杂，还存在亲水防雾持续性不佳，使用寿命不长，附着力差。",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# 发明内容  \n\n[0005] 本发明的目的是针对现有技术的不足，本发明提供一种亲水型阳离子光固化树脂，该树脂具有全亲水主链和全疏水侧链，疏水侧链含有脲基和氨基甲酸酯基团，具有优异的亲水性能，机械性能和耐溶剂性能，氧杂环丁烷可进行阳离子光固化反应，不产生氧阻聚，固化反应程度更高。  \n\n[0006] 为实现上述目的，本发明采用的技术方案如下：  \n\n[0007] 本发明首先提供一种亲水型阳离子光固化树脂，该树脂具有全亲水主链和全疏水侧链，由二元聚醚胺与聚乙二醇二丙烯酸酯反应生成的聚合物中间体为主链结构单元，二异氰酸酯与带羟基的氧杂环丁烷反应得到的化合物链段为疏水侧链，主链两端的丙烯酸酯基进行氨基磺酸盐封端得到。  \n\n[0008] 本发明其二提供上述亲水型阳离子光固化树脂的制备方法，包括以下步骤：  \n\n[0009] 1)二异氰酸酯与带羟基的氧杂环丁烷反应得到端NCO的半封端预聚体，其中二异氰酸酯的异氰酸酯基(‑NCO)和氧杂环丁烷的羟基(‑OH)的摩尔比2:1；  \n\n[0010] 2)二元聚醚胺与聚乙二醇二丙烯酸酯在室温下进行迈克尔加成反应，得到丙烯酸酯基封端的亲水聚合物中间体1，其中二元聚醚胺与聚乙二醇二丙烯酸酯的摩尔比为1:24:5；  \n\n[0011] 3)氨基磺酸盐与中间体1中的丙烯酸酯基在室温下进行迈克尔加成反应得到中间体2，其中氨基磺酸盐与中间体1的摩尔比为2:1，氨基磺酸盐事先用去离子水配置成溶液，质量分数为 $50\\%-80\\%$ ；  \n[0012] 4)将步骤1中端NCO的半封端预聚体和中间体2按照异氰酸酯基(‑NCO)与仲胺(‑NH‑)摩尔比1:1反应得到亲水型阳离子光固化树脂。  \n[0013] 优选地，所述二异氰酸酯包括异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、六亚甲基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(HMDI)、改性二苯基甲烷二异氰酸酯(液化MDI)中的一种或至少两种的组合；  \n[0014] 所述的氧杂环丁烷包括3‑羟甲基氧杂环丁烷、3‑甲基‑3‑羟甲基氧杂环丁烷、3‑乙基‑3‑羟甲基氧杂环丁烷中的至少一种。  \n[0015] 优选地，所述的二元聚醚胺包括D230、D400、D2000、ED600、ED900和ED2003中的至少一种；  \n[0016] 所述聚乙二醇二丙烯酸酯包括PEG200DA、PEG400DA、PEG600DA、PEG750DA和PEG1000DA中的至少一种。  \n[0017] 优选地，所述氨基磺酸盐包括乙二胺基乙磺酸钠，乙二胺基丙磺酸钠，氨基苯磺酸钠和牛磺酸钠中的至少一种。  \n[0018] 本技术方案制备亲水型阳离子光固化树脂的过程中还额外添加了二月桂酸二丁基锡(DBTDL)作为催化剂；催化剂占树脂质量的 $0.01\\%-0.05\\%$ 。  \n[0019] 上述亲水型阳离子光固化树脂的制备方法中，具体的，步骤1)中先将二异氰酸酯和二月桂酸二丁基锡加入反应釜中开启搅拌混合均匀；再将氧杂环丁烷加至恒压滴液槽中，室温下缓慢滴加至上述反应釜中，滴完继续室温反应30min后，升温至 $60-70^{\\circ}\\mathrm{C}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值，得到半封端的预聚体。  \n[0020] 具体的，步骤2)将二元聚醚胺加入反应釜中维持室温搅拌，将聚乙二醇二丙烯酸酯转移至恒压滴液槽中，缓慢滴加至上述反应釜中，滴完维持室温继续反应2‑4h得到丙烯酸酯基封端的亲水聚合物中间体1。  \n[0021] 具体的，步骤3)用去离子水将氨基磺酸盐溶解均匀后转移至恒压滴液槽中，室温条件下缓慢滴加至上述反应釜中，滴完维持室温继续反应2‑3h后，升温至 $40-50^{\\circ}\\mathrm{C}$ 反应2h得到中间体2。  \n[0022] 具体的，步骤4)将预聚体1转移到中间体2的恒压滴液槽中，冰水浴条件下缓慢滴加至中间体2中，滴完继续反应30min后，升温至室温反应直至混合物的异氰酸酯基(‑NCO)的含量为零，得到亲水型阳离子光固化树脂，避光保存。  \n[0023] 本发明其三提供上述亲水型阳离子光固化树脂在超亲水涂层中的应用。  \n[0024] 该亲水型阳离子光固化树脂与阳离子光引发剂，用30um线棒均匀的涂在干净的PC板上，60度烘烤3min，然后放在传送带式UV固化机上，经800mJ紫外光固化后，制得超亲水涂层。  \n[0025] 另外，上述亲水型阳离子光固化树脂也可以与其它阳离子树脂或单体复配，制备  \n\n防雾涂料组合物，并添加 $5\\%$ 的阳离子光引发剂，用30um线棒均匀的涂在干净的PC板上，60度烘烤3min，然后放在传送带式UV固化机上，经800mJ紫外光固化后，在室温条件下放置7d测试性能。  \n\n[0026] 其它的阳离子树脂包括所述主体树脂是脂环族环氧树脂，主要是含有两个环氧基团的饱和脂环结构，具体是带环氧环己基的羧酸酯和缩水甘油醚的结构，如：陶氏化学的UVR‑6110(3，4‑环氧环己基甲基，3，4_环氧环己基碳酸酯)、UVR‑6103(3，4‑环氧环己基甲基，3，4‑环氧环己基甲酯)、UVR‑6105(3，4‑环氧环己基甲基，3，4‑环氧环己基甲酸酯)、UVR‑6128(双(3,4‑环氧环己基)甲基己二酸酯)，江苏泰特尔公司的TTA11(1,2‑环氧‑4‑乙烯基环己烷)、TTA15(3,4‑环氧环己基甲基甲基丙烯酸酯)、TTA16(3,4‑环氧环己基甲基丙烯酸酯)、TTA500(三缩水甘油基对氨基苯酚)等；  \n\n[0027] 所述活性单体是乙烯基醚类单体，该单体是阳离子型活性稀释单体，如羟丁基乙烯基醚(HBVE)、三乙二醇二乙烯基醚(DVE‑3)、1，4‑环己基二甲醇二乙烯基醚(CHVE)、丁基乙烯基醚(BVE)等。  \n\n[0028] 与现有技术相比，本发明具有如下突出效果：  \n\n[0029] 1)本发明设计了一种亲水型阳离子光固化树脂，将亲水二元聚醚胺中的伯胺与聚乙二醇二丙烯酸酯中的丙烯酸酯基进行迈克尔加成反应形成聚合物中间体1，中间体1中保留仲胺和端基丙烯酸酯，接着将丙烯酸酯基和氨基磺酸盐中的伯胺再次进行迈克尔加成反应，形成由阴‑非两性亲水基团组成的全亲水中间体2，然后将中间体2作为主链，利用仲胺与端NCO预聚体反应形成疏水侧链，该全亲水主链和全疏水侧链能够形成一种类“爪型”的表面活性剂结构，并与阴‑非两性亲水基团协同发挥持久亲水性能，水接触角长期维持在${10}^{\\circ}$ °以内。  \n\n[0030] 2)疏水侧链含有脲基和氨基甲酸酯基团，具有优异的机械性能和耐溶剂性能，氧杂环丁烷可参与阳离子光固化反应，以阳离子活性种的形式参与开环固化，相比于自由基固化，难以发生链终止反应，固化时的收缩率低，对基材有很好的附着力，光固化过程不产生氧阻聚，固化反应程度更高，并且能够耐消毒液以及乙醇浸泡。氧杂环丁烷能够进行阳离子光固化反应，以阳离子活性种的形式参与开环固化反应，不同于自由基容易发生链终止反应，因此固化时的收缩率低，对基材有很好的附着力，光固化过程不产生氧阻聚，固化反应程度高，具有优异的机械性能，能够耐消毒液以及有机溶剂浸泡。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 具体实施方式  \n\n[0031] 下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。  \n\n[0032] 制备亲水型阳离子光固化树脂的过程中还额外添加了二月桂酸二丁基锡DBTDL，此为常规选择，对性能没有影响，起到催化剂的作用。  \n\n[0033] 实施例1  \n\n[0034] 步骤1) 向反应釜a 中加入 $444.6\\mathrm{g}\\left(2.0\\mathrm{mol}\\right)$ 异佛尔酮二异氰酸酯和 $0.06\\mathrm{g}$ $(0.01\\mathrm{wt\\%})\\$ )二月桂酸二丁基锡开启搅拌；将 $204.2\\mathrm{g}\\left(2.0\\mathrm{mol}\\right)3\\cdot$ ‑甲基‑3‑羟甲基氧杂环丁烷加入恒压滴液槽中，在室温下缓慢滴加至上述反应釜中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $70\\mathrm{{^\\circC}}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值(通过盐酸二正丁胺法测定)，得到半封端的预聚体；  \n\n[0035] 步骤2)向反应釜b中加入 $.450\\mathrm{g}\\left(0.5\\mathrm{mol}\\right)$ 聚醚胺ED900开启搅拌，将 $381\\mathrm{g}$ (0 .75mol)PEG400DA加入恒压滴液槽中，室温条件下缓慢滴加至上述反应釜中，滴完维持室温继续反应2h得到丙烯酸酯基封端的亲水聚合物中间体1，其中二元聚醚胺与聚乙二醇二丙烯酸酯的摩尔比为2:3；  \n\n[0036] 步骤3)用 $70\\mathrm{g}$ 去离子水将 $95.0\\mathrm{g}\\left(0.5\\mathrm{mol}\\right)$ 乙二胺基乙磺酸钠溶解均匀后转移至恒压滴液槽中，室温条件下缓慢滴加至反应釜b中，滴完维持室温继续反应2h后，升温至 $50^{\\circ}\\mathrm{C}$ 反应2h得到中间体2；  \n\n[0037] 步骤4)将步骤1中的预聚体转移到反应釜b的恒压滴液槽中，冰水浴条件下缓慢滴加至反应釜b中，滴完继续室温反应30min后，升至室温反应直至混合物的异氰酸酯基(‑NCO)的含量为零，得到亲水型阳离子光固化树脂，避光保存。  \n\n[0038] 实施例2  \n\n[0039] 步骤1) 向反应釜a 中加入 $.336.3\\mathrm{g}\\left(2.0\\mathrm{mol}\\right)$ 六亚甲基二异氰酸酯和 $0.06\\mathrm{g}$ $(0.01\\mathrm{wt\\%})$ )二月桂酸二丁基锡开启搅拌；将 $232.3\\mathrm{g}\\left(2.0\\mathrm{mol}\\right)3\\cdot$ 乙基‑3‑羟甲基氧杂环丁烷加入恒压滴液槽中，在室温下缓慢滴加至上述反应釜中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $70\\mathrm{{^\\circC}}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值(通过盐酸二正丁胺法测定)，得到半封端的预聚体；  \n\n[0040] 步骤2)向反应釜b中加入 $\\、800\\mathrm{g}\\left(0\\mathrm{~.~}4\\mathrm{mol}\\right)$ 聚醚胺ED2003开启搅拌，将 $566.4\\mathrm{g}$ (0.8mol)PEG600DA加入恒压滴液槽中，室温条件下缓慢滴加至上述反应釜中，滴完维持室温继续反应3h得到丙烯酸酯基封端的亲水聚合物中间体1，其中二元聚醚胺与聚乙二醇二丙烯酸酯的摩尔比为1:2；  \n\n[0041] 步骤3)用 $120\\mathrm{g}$ 去离子水将 $76.0\\mathrm{g}\\left(0.4\\mathrm{mol}\\right)$ 乙二胺基乙磺酸钠和 $58.8\\mathrm{g}\\left(0.4\\mathrm{mol}\\right)$ 牛磺酸钠溶解均匀后转移至恒压滴液槽中，室温条件下缓慢滴加至反应釜b中，滴完维持室温继续反应2h后，升温至 $50^{\\circ}\\mathrm{C}$ 反应2h得到中间体2；  \n\n[0042] 步骤4)将步骤1中的预聚体转移到反应釜b的恒压滴液槽中，冰水浴条件下缓慢滴加至反应釜b中，滴完继续室温反应30min后，升至室温反应直至混合物的异氰酸酯基(‑NCO)的含量为零，得到亲水型阳离子光固化树脂，避光保存。  \n\n[0043] 实施例3  \n\n[0044] 步骤1)向反应釜a中加入 $\\setminus314.78\\:(1.2\\mathrm{{mol})}$ 二环己基甲烷二异氰酸酯和 $0.04\\mathrm{g}$ $(0.01\\mathrm{wt\\%})$ )二月桂酸二丁基锡开启搅拌；将 $122.5\\mathrm{g}\\left(1.2\\mathrm{mol}\\right)3\\ensuremath{\\mathrm{\\Omega}}$ 甲基‑3‑羟甲基氧杂环丁烷加入恒压滴液槽中，在室温下缓慢滴加至上述反应釜中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $70\\mathrm{{^\\circC}}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值(通过盐酸二正丁胺法测定)，得到半封端的预聚体；  \n\n[0045] 步骤2)向反应釜b中加入 $.92\\mathrm{g}\\left(0.4\\mathrm{mol}\\right)$ 聚醚胺D230开启搅拌，将101 .6g(0 .2mol)PEG400DA和443 .2g(0 .4mol)PEG1000DA加入恒压滴液槽中，室温条件下缓慢滴加至上述反应釜中，滴完维持室温继续反应4h得到丙烯酸酯基封端的亲水聚合物中间体1，其中二元聚醚胺与聚乙二醇二丙烯酸酯的摩尔比为2:3；  \n\n[0046] 步骤3)用 $90\\mathrm{g}$ 去离子水将 $92.5\\mathrm{g}\\left(0.4\\mathrm{mol}\\right)$ 氨基苯磺酸钠溶解均匀后转移至恒压滴液槽中，室温条件下缓慢滴加至反应釜b中，滴完维持室温继续反应3h后，升温至 $40^{\\circ}\\mathrm{C}$ 反应2h得到中间体2；  \n\n[0047] 步骤4)将步骤1中的预聚体转移到反应釜b的恒压滴液槽中，冰水浴条件下缓慢滴加至反应釜b中，滴完继续室温反应30min后，升至室温反应直至混合物的异氰酸酯基(‑NCO)的含量为零，得到亲水型阳离子光固化树脂，避光保存。  \n\n[0048] 实施例4  \n\n[0049] 步骤1) 向反应釜a 中加入 $336.3\\mathrm{g}\\left(2.0\\mathrm{mol}\\right)$ 六亚甲基二异氰酸酯和 $0.05\\mathrm{g}$ $(0.01\\mathrm{wt\\%})$ 二月桂酸二丁基锡开启搅拌；将 $176.2\\mathrm{g}(2.0\\mathrm{mol})3\\cdot$ ‑羟甲基氧杂环丁烷加入恒压滴液槽中，在室温下缓慢滴加至上述反应釜中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $65^{\\circ}\\mathrm{C}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值(通过盐酸二正丁胺法测定)，得到半封端的预聚体；  \n\n[0050] 步骤2)向反应釜b中加入 $.360\\mathrm{g}\\left(0.6\\mathrm{mol}\\right)$ 聚醚胺ED600开启搅拌，将 $566.4\\mathrm{g}\\left(0.8\\mathrm{mol}\\right)$ PEG600DA加入恒压滴液槽中，室温条件下缓慢滴加至上述反应釜中，滴完维持室温继续反应3h得到丙烯酸酯基封端的亲水聚合物中间体1，其中二元聚醚胺与聚乙二醇二丙烯酸酯的摩尔比为3:4；  \n\n[0051] 步骤3)用 $60\\mathrm{g}$ 去离子水将 $76\\mathrm{g}\\left(0.4\\mathrm{mol}\\right)$ 乙二胺基乙磺酸钠溶解均匀后转移至恒压滴液槽中，室温条件下缓慢滴加至反应釜b中，滴完维持室温继续反应3h后，升温至 $40^{\\circ}\\mathrm{C}$ 反应2h得到中间体2；  \n\n[0052] 步骤4)将步骤1中的预聚体转移到反应釜b的恒压滴液槽中，冰水浴条件下缓慢滴加至反应釜b中，滴完继续室温反应30min后，升至室温反应直至混合物的异氰酸酯基(‑NCO)的含量为零，得到亲水型阳离子光固化树脂，避光保存。  \n\n[0053] 实施例5  \n\n[0054] 将实施例1所制得的亲水型阳离子光固化树脂添加 $5\\%$ 的阳离子光引发剂，用30um线棒均匀的涂在干净的PET膜上，60度烘烤3min，然后放在传送带式UV固化机上，经800mJ紫外光固化后，得到超亲水涂层。  \n\n[0055] 将实施例1所制得的亲水型阳离子光固化树脂与UVR‑6110、DVE‑3复配制备防雾涂料组合物，其中按质量份亲水型阳离子光固化树脂60份，UVR‑611020份、DVE‑320份，再添加$5\\%$ 的阳离子光引发剂，用30um线棒均匀的涂在干净的PC板上，60度烘烤3min，然后放在传送带式UV固化机上，经800mJ紫外光固化后，得到超亲水涂层。  \n\n[0056] 实施例6  \n\n[0057] 将实施例2所制得的亲水型阳离子光固化树脂添加 $5\\%$ 的阳离子光引发剂，用30um线棒均匀的涂在干净的PET膜上，60度烘烤3min，然后放在传送带式UV固化机上，经 $800\\mathrm{mJ}$ 紫外光固化后，得到超亲水涂层。  \n\n[0058] 将实施例2所制得的亲水型阳离子光固化树脂与UVR‑6110、DVE‑3复配制备防雾涂料组合物，其中按质量份亲水型阳离子光固化树脂60份，UVR‑611020份、DVE‑320份，再添加$5\\%$ 的阳离子光引发剂，用30um线棒均匀的涂在干净的PC板上，60度烘烤3min，然后放在传送带式UV固化机上，经800mJ紫外光固化后，得到超亲水涂层。  \n\n[0059] 实施例7  \n\n[0060] 将实施例3所制得的亲水型阳离子光固化树脂添加 $5\\%$ 的阳离子光引发剂，用30um线棒均匀的涂在干净的PET膜上，60度烘烤3min，然后放在传送带式UV固化机上，经 $800\\mathrm{mJ}$ 紫外光固化后，得到超亲水涂层。  \n\n[0061] 将实施例3所制得的亲水型阳离子光固化树脂与UVR‑6110、DVE‑3复配制备防雾涂料组合物，其中按质量份亲水型阳离子光固化树脂60份，UVR‑611020份、DVE‑320份，再添加$5\\%$ 的阳离子光引发剂，用30um线棒均匀的涂在干净的PC板上，60度烘烤3min，然后放在传送带式UV固化机上，经800mJ紫外光固化后，得到超亲水涂层。  \n\n[0062] 实施例8  \n\n[0063] 将实施例4所制得的亲水型阳离子光固化树脂添加 $5\\%$ 的阳离子光引发剂，用30um线棒均匀的涂在干净的PET膜上，60度烘烤3min，然后放在传送带式UV固化机上，经800mJ紫外光固化后，得到超亲水涂层。  \n\n[0064] 将实施例4所制得的亲水型阳离子光固化树脂与UVR‑6110、DVE‑3复配制备防雾涂料组合物，其中按质量份亲水型阳离子光固化树脂60份，UVR‑611020份、DVE‑320份，再添加$5\\%$ 的阳离子光引发剂，用30um线棒均匀的涂在干净的PC板上，60度烘烤3min，然后放在传送带式UV固化机上，经800mJ紫外光固化后，得到超亲水涂层。  \n\n[0065] 性能测试  \n\n[0066] 对上述实施例1‑4，实施例5‑8制得的超亲水涂层在室温条件下放置7d后分别按照表1和表3中的测试项目和方法进行性能的测试，结果如表2和表4所示。  \n\n[0067] 表1实施例1‑4所制得的超亲水涂层的性能测试项目和方法  \n\n[0068] [0069] [0073] [0074] [0076]  \n\n<html><body><table><tr><td>项目</td><td>方法</td></tr><tr><td>铅笔硬度</td><td>通过铅笔硬度仪按照GB/T6739-1996中的规定进行</td></tr><tr><td>附着力</td><td>采用百格法，交叉划格形成10×10的小方格。用3M-610压敏胶 带紧密粘附于涂层表面，然后沿90度方向快速撕去胶带，观测 格子边缘的破坏程度</td></tr><tr><td>初始水接触角</td><td>用便携式接触角测量仪SDP-260测试10ul水量下接触角的大小</td></tr><tr><td>耐酒精擦拭</td><td>样品用75%酒精打湿的布在200g力下，来回擦拭10次，观察接</td></tr></table></body></html>  \n\n<html><body><table><tr><td></td><td>触角的变化</td></tr><tr><td>耐乙醇浸泡</td><td>样品浸泡在95%的乙醇中1h，观察接触角的变化</td></tr><tr><td>耐消毒水浸泡</td><td>样品浸泡在100ppm的84消毒水中1h，观察接触角的变化</td></tr><tr><td>耐磨测试（耐划 伤)</td><td>用水打湿羊毛毡，500克压力，1cm×1cm磨头，擦500来回。无 划痕为非常好；不超过5个擦痕为好；多于5个擦痕为差。</td></tr><tr><td>持久性测试</td><td>对涂层做长期测试，每天测试接触角，记录出现接触角大于30 度时的天数</td></tr><tr><td>粘性测试</td><td>用棉花擦样品表面，不残留纤维为光滑，残留纤维越多说明越粘</td></tr></table></body></html>  \n\n[0070] 表2实施例1‑4所制得的超亲水涂层的性能测试结果  \n\n\n<html><body><table><tr><td>测试性能</td><td>测试方式和标准</td><td>实施例1</td><td>实施例2</td><td>实施例3</td><td>实施例4</td></tr><tr><td>涂层厚度</td><td>um</td><td>5.9</td><td>6.4</td><td>5.6</td><td>6.8</td></tr><tr><td>初始水接触角()</td><td></td><td>7</td><td>5</td><td>10</td><td>8</td></tr><tr><td>酒精擦拭(°)</td><td></td><td>12</td><td>10</td><td>14</td><td>12</td></tr><tr><td>乙醇浸泡</td><td></td><td>18</td><td>16</td><td>18</td><td>15</td></tr><tr><td>消毒水浸泡</td><td></td><td>10</td><td>8</td><td>12</td><td>12</td></tr><tr><td>铅笔硬度</td><td>铅笔测试仪</td><td>2H</td><td>2H</td><td>2H</td><td>2H</td></tr><tr><td>耐划伤</td><td></td><td>2</td><td>2</td><td>1</td><td>1</td></tr><tr><td>附着力</td><td>划格</td><td>0级</td><td>0级</td><td>0级</td><td>0级</td></tr><tr><td>粘性测试</td><td></td><td>光滑</td><td>光滑</td><td>光滑</td><td>光滑</td></tr><tr><td>持久性测试</td><td></td><td>>365d</td><td>>365d</td><td>>365d</td><td>>365d</td></tr></table></body></html>\n\n[0072] 表3实施例5‑8所制得的超亲水涂层的性能测试项目和方法  \n\n<html><body><table><tr><td>项目</td><td>方法</td></tr><tr><td>铅笔硬度</td><td>通过铅笔硬度仪按照GB/T6739-1996中的规定进行</td></tr><tr><td>附着力</td><td>采用百格法，交叉划格形成10×10的小方格。用3M-610压敏 胶带紧密粘附于涂层表面，然后沿90度方向快速撕去胶带，观 测格子边缘的破坏程度</td></tr><tr><td>初始防雾</td><td>在70度水浴锅上方3cm处观察30s，是否出现起雾现象</td></tr><tr><td>耐酒精擦拭</td><td>样品用75%酒精打湿的布在200g力下，来回擦拭10次，观察 防雾的变化</td></tr></table></body></html>  \n\n<html><body><table><tr><td>耐乙醇浸泡</td><td>样品浸泡在95%的乙醇中10min，观察防雾的变化</td></tr><tr><td>耐消毒水浸泡</td><td>样品浸泡在100ppm的84消毒水中1h，观察防雾的变化</td></tr><tr><td>耐磨测试（耐划伤）</td><td>用水打湿羊毛毡，500克压力，1cm×1cm磨头，擦500来回。 无划痕为非常好；不超过5个擦痕为好；多于5个擦痕为差。</td></tr><tr><td>持久性测试</td><td>涂层做长期测试，每天测试防雾性能，记录出现起雾时的天数</td></tr><tr><td>粘性测试</td><td>用棉花擦样品表面，不残留纤维为光滑，残留纤维越多说明越粘</td></tr></table></body></html>\n\n[0075] 表4实施例5‑8所制得的超亲水涂层的性能测试结果  \n\n<html><body><table><tr><td>测试性能</td><td>测试方式和标准</td><td>实施例5</td><td>实施例6</td><td>实施例7</td><td>实施例8</td></tr><tr><td>涂层厚度</td><td>um</td><td>5.9</td><td>6.4</td><td>5.6</td><td>6.8</td></tr><tr><td>初始防雾</td><td></td><td>无雾</td><td>无雾</td><td>无雾</td><td>无雾</td></tr><tr><td>酒精擦拭防雾</td><td></td><td>无雾</td><td>无雾</td><td>无雾</td><td>无雾</td></tr><tr><td>乙醇浸泡防雾</td><td></td><td>18</td><td>16</td><td>5-8s轻微 起雾，之 后无雾</td><td>15</td></tr><tr><td>消毒水浸泡防雾</td><td></td><td>无雾</td><td>无雾</td><td>无雾</td><td>无雾</td></tr><tr><td>铅笔硬度</td><td>铅笔测试仪</td><td>2H</td><td>2H</td><td>2H</td><td>2H</td></tr><tr><td>耐划伤</td><td></td><td>1</td><td>1</td><td>1</td><td>2</td></tr><tr><td>附着力</td><td>划格</td><td>0级</td><td>0级</td><td>0级</td><td>0级</td></tr><tr><td>粘性测试</td><td></td><td>光滑</td><td>光滑</td><td>光滑</td><td>光滑</td></tr><tr><td>持久性测试</td><td></td><td>190d</td><td>195d</td><td>175d</td><td>200d</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# (19)国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n(21)申请号 202210614794 .5  \n(22)申请日 2022.06.01  \n(65)同一申请的已公布的文献号申请公布号 CN 115044012 A  \n(43)申请公布日 2022.09.13  \n(73)专利权人 武汉中科先进材料科技有限公司地址 430000 湖北省武汉市经济技术开发区201M地块华人汇和科技园（华中智谷）一期F10研发楼1-2层  \n(72)发明人 康翼鸿　喻学锋　程文杰　何睿吴列　甄亚枝　杨帆  \n(74)专利代理机构 武汉高得专利代理事务所(普通合伙) 42268专利代理师 杨如增  \n\n(51)Int.Cl. C08G 18/67(2006.01)",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n一种亲水型光固化树脂及其制备方法和应用",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明属于高分子合成技术领域，具体涉及一种亲水型光固化树脂及其制备方法。将二元聚醚胺与聚乙二醇二丙烯酸酯在室温下进行迈克尔加成反应，得到丙烯酸酯基封端的亲水聚合物中间体1，然后与氨基磺酸盐继续进行迈克尔加成反应得到中间体2；另将二异氰酸酯与羟基丙烯酸酯反应形成半封端预聚体；将所述亲水聚合物中间体2与半封端的预聚体反应，得到所述的亲水型光固化树脂。该树脂经自由基光固化反应形成的超亲水涂层，具备优异的附着力和耐磨性，能够耐水擦拭500次以上以及耐盐水浸泡。  \n\n(10)授权公告号 CN 115044012 B(45)授权公告日 2023.12.12  \n\nC08G 18/63(2006.01) C08G 18/50(2006.01) C09D 175/14(2006.01)",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# (56)对比文件  \n\nCN 111393832 A,2020.07 .10 CN 112048051 A,2020.12.08 CN 113817433 A,2021 .12.21 JP H08176504 A,1996.07 .09 US 2008305349 A1 ,2008.12.11 US 6187897 B1 ,2001 .02.13 WO 2021110621 A1 ,2021 .06.10 Dania Alyounes 等.Development Of Polymeric Micro/Nanostructures For Gene Delivery .《Mater. Res . Soc. Symp. Proc.》 .2011 ,第1019卷1-8.",
+        "category": " References"
+    },
+    {
+        "id": 6,
+        "chunk": "# 审查员 廖杨  \n\n权利要求书1页 说明书8页  \n\n1.一种亲水型光固化树脂，其特征在于，该树脂具有全亲水主链和全疏水侧链，由二元聚醚胺与聚乙二醇二丙烯酸酯反应生成的聚合物中间体为主链结构单元，二异氰酸酯与羟基丙烯酸酯反应得到的化合物链段为疏水侧链，主链两端的丙烯酸酯基进行氨基磺酸盐封端得到。  \n\n2.一种如权利要求1所述亲水型光固化树脂的制备方法，其特征在于，包括以下步骤：  \n\n1)二异氰酸酯与羟基丙烯酸酯反应得到端NCO的半封端预聚体，其中二异氰酸酯的异氰酸酯基(‑NCO)和丙烯酸酯的羟基(‑OH)的摩尔比2:1；  \n\n2)二元聚醚胺与聚乙二醇二丙烯酸酯在室温下进行迈克尔加成反应，得到丙烯酸酯基封端的亲水聚合物中间体1，其中二元聚醚胺与聚乙二醇二丙烯酸酯的摩尔比为1:2‑4:5；  \n\n3)氨基磺酸盐与中间体1中的丙烯酸酯基在室温下进行迈克尔加成反应得到中间体2，其中氨基磺酸盐与中间体1的摩尔比为2:1，氨基磺酸盐事先用去离子水配置成溶液，质量分数为 $50\\%-80\\%$ ；  \n\n4)将步骤1中端NCO的半封端预聚体和中间体2按照异氰酸酯基(‑NCO)与仲胺(‑NH‑)摩尔比1:1反应得到亲水型光固化树脂。  \n\n3.根据权利要求2所述亲水型光固化树脂的制备方法，其特征在于：所述二异氰酸酯包括异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、六亚甲基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(HMDI)、改性二苯基甲烷二异氰酸酯(液化MDI)中的一种或至少两种的组合；所述羟基丙烯酸酯包括丙烯酸羟乙酯、丙烯酸羟丙酯、4‑羟基丁基丙烯酸酯、季戊四醇三丙烯酸酯中的至少一种。  \n\n4.根据权利要求2所述亲水型光固化树脂的制备方法，其特征在于：所述二元聚醚胺包括D230、D400、D2000、ED600、ED900和ED2003中的至少一种；所述聚乙二醇二丙烯酸酯包括PEG200DA、PEG400DA、PEG600DA、PEG750DA和PEG1000DA中的至少一种。  \n\n5.根据权利要求2所述亲水型光固化树脂的制备方法，其特征在于：所述氨基磺酸盐包括乙二胺基乙磺酸钠，乙二胺基丙磺酸钠，氨基苯磺酸钠和牛磺酸钠中的至少一种。  \n\n6.根据权利要求2所述亲水型光固化树脂的制备方法，其特征在于，步骤1)中先将二异氰酸酯和二月桂酸二丁基锡加入反应釜中开启搅拌混合均匀；再将羟基丙烯酸酯加至恒压滴液槽中，室温下缓慢滴加至上述反应釜中，滴完继续室温反应30min后，升温至 $60-70^{\\circ}\\mathrm{C}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值，得到半封端预聚体。  \n\n7.根据权利要求2所述亲水型光固化树脂的制备方法，其特征在于，步骤2)将二元聚醚胺加入反应釜中维持室温搅拌，将聚乙二醇二丙烯酸酯转移至恒压滴液槽中，缓慢滴加至上述反应釜中，滴完维持室温继续反应2‑4h得到丙烯酸酯基封端的亲水聚合物中间体1。  \n\n8.根据权利要求6所述亲水型光固化树脂的制备方法，其特征在于，步骤3)用去离子水将氨基磺酸盐溶解均匀后转移至恒压滴液槽中，室温条件下缓慢滴加至上述反应釜中，滴完维持室温继续反应2‑3h后，升温至 $40-50^{\\circ}\\mathrm{C}$ 反应2h得到中间体2。  \n\n9.根据权利要求2所述亲水型光固化树脂的制备方法，其特征在于，步骤4)将半封端预聚体转移到中间体2的恒压滴液槽中，冰水浴条件下缓慢滴加至中间体2中，滴完继续反应30min后，升温至室温反应直至混合物的异氰酸酯基(‑NCO)的含量为零，得到亲水型光固化树脂，避光保存。  \n\n10.一种如权利要求1所述亲水型光固化树脂在超亲水涂层中的应用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 一种亲水型光固化树脂及其制备方法和应用",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 技术领域  \n\n[0001] 本发明属于高分子合成技术领域，一种亲水型光固化树脂及其制备方法。",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 背景技术  \n\n[0002] 超亲水表面与水具有很强的相互作用力，将水滴滴在上面能够在较短时间内完全铺展开，使接触角等于或接近于 $\\cdot0^{\\circ}$ °，在自清洁，导流，防污，生物耗材等众多领域均有着十分广阔的应用前景，是当前研究的热点之一。实现超亲水的方法为化学改性法(如等离子体处理)或者表面涂层法，但是这两种制备方法都存在一些问题，化学改性法需要采用昂贵的仪器设备或复杂的工艺流程，易受外界条件(光,热,氧等)的影响，应用领域仍有待于发展。表面涂层法最早依赖于亲水表面活性剂来提供亲水性能，耐用性较差，遇水容易失效，逐渐被亲水树脂替代。按照固化方式不同，有热固化型亲水树脂和UV(紫外线)光固化型亲水树脂。虽然热固化型亲水树脂可以提供良好的耐磨性，但它们需要长固化时间和高能量消耗以便溶剂蒸发，生产效率低。  \n\n[0003] UV(紫外线)光固化型亲水树脂在紫外光下能够实现瞬间固化，非常适合连续工业化生产，但是亲水基团中往往夹杂着疏水基团，形成的涂层亲水持续性不佳，在频繁水擦和溶剂浸泡下很容易失效。目前耐水擦、耐浸泡的光固化树脂商业化的产品很少，同时具有优异机械性能和持久亲水性能的更是鲜有报道。",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# 发明内容  \n\n[0004] 本发明的目的是针对现有技术的不足，本发明提供一种亲水型光固化树脂，该树脂具有全亲水主链和全疏水侧链，疏水侧链含有脲基和氨基甲酸酯基团，具有优异的机械性能和耐溶剂性能，丙烯酸酯基团可进行光固化反应。为实现上述目的，本发明采用的技术方案如下：  \n\n[0005] 本发明首先提供一种亲水型光固化树脂，该树脂具有全亲水主链和全疏水侧链，由二元聚醚胺与聚乙二醇二丙烯酸酯反应生成的聚合物中间体为主链结构单元，二异氰酸酯与羟基丙烯酸酯反应得到的化合物链段为疏水侧链，主链两端的丙烯酸酯基进行氨基磺酸盐封端得到。  \n\n[0006] 本发明其二提供上述亲水型光固化树脂的制备方法，包括以下步骤：  \n\n[0007] 1)二异氰酸酯与羟基丙烯酸酯反应得到端NCO的半封端预聚体，其中二异氰酸酯的异氰酸酯基(‑NCO)和丙烯酸酯的羟基(‑OH)的摩尔比2:1；  \n\n[0008] 2)二元聚醚胺与聚乙二醇二丙烯酸酯在室温下进行迈克尔加成反应，得到丙烯酸酯基封端的亲水聚合物中间体1，其中二元聚醚胺与聚乙二醇二丙烯酸酯的摩尔比为1:24:5；  \n\n[0009] 3)氨基磺酸盐与中间体1中的丙烯酸酯基在室温下进行迈克尔加成反应得到中间体2，其中氨基磺酸盐与中间体1的摩尔比为2:1，氨基磺酸盐事先用去离子水配置成溶液，质量分数为 $50\\%-80\\%$ ；  \n\n[0010] 4)将步骤1中端NCO的半封端预聚体和中间体2按照异氰酸酯基(‑NCO)与仲胺(‑NH‑)摩尔比1:1反应得到亲水型光固化树脂。  \n\n[0011] 优选地，所述二异氰酸酯包括异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、六亚甲基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(HMDI)、改性二苯基甲烷二异氰酸酯(液化MDI)中的一种或至少两种的组合；  \n\n[0012] 所述羟基丙烯酸酯包括丙烯酸羟乙酯、丙烯酸羟丙酯、4‑羟基丁基丙烯酸酯、季戊四醇三丙烯酸酯中的至少一种。  \n\n[0013] 优选地，所述的二元聚醚胺包括D230、D400、D2000、ED600、ED900和ED2003中的至少一种；  \n\n[0014] 所述聚乙二醇二丙烯酸酯包括PEG200DA、PEG400DA、PEG600DA、PEG750DA和PEG1000DA中的至少一种。  \n\n[0015] 优选地，所述氨基磺酸盐包括乙二胺基乙磺酸钠，乙二胺基丙磺酸钠，氨基苯磺酸钠和牛磺酸钠中的至少一种。  \n\n[0016] 本技术方案制备亲水型光固化树脂的过程中还额外添加了二月桂酸二丁基锡(DBTDL)作为催化剂；催化剂占树脂质量的 $0.01\\%-0.05\\%$ 。  \n\n[0017] 上述亲水型光固化树脂的制备方法中，具体的，步骤1)中先将二异氰酸酯和二月桂酸二丁基锡加入反应釜中开启搅拌混合均匀；再将羟基丙烯酸酯加至恒压滴液槽中，室温下缓慢滴加至上述反应釜中，滴完继续室温反应30min后，升温至 $60-70^{\\circ}\\mathrm{C}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值，得到半封端的预聚体。  \n\n[0018] 具体的，步骤2)将二元聚醚胺加入反应釜中维持室温搅拌，将聚乙二醇二丙烯酸酯转移至恒压滴液槽中，缓慢滴加至上述反应釜中，滴完维持室温继续反应2‑4h得到丙烯酸酯基封端的亲水聚合物中间体1。  \n\n[0019] 具体的，步骤3)用去离子水将氨基磺酸盐溶解均匀后转移至恒压滴液槽中，室温条件下缓慢滴加至上述反应釜中，滴完维持室温继续反应2‑3h后，升温至 $40-50^{\\circ}\\mathrm{C}$ 反应2h得到中间体2。  \n\n[0020] 具体的，步骤4)将预聚体1转移到中间体2的恒压滴液槽中，冰水浴条件下缓慢滴加至中间体2中，滴完继续反应30min后，升温至室温反应直至混合物的异氰酸酯基(‑NCO)的含量为零，得到亲水型光固化树脂，避光保存。  \n\n[0021] 本发明其三提供上述亲水型光固化树脂在超亲水涂层中的应用。  \n\n[0022] 该亲水型光固化树脂与光引发剂，用30um线棒均匀的涂在干净的PC板上，60度烘烤3min，然后放在传送带式UV固化机上，经800mJ紫外光固化后，制得超亲水涂层。  \n\n[0023] 另外，上述亲水型光固化树脂也可以与其它树脂或单体复配，制备防雾涂料组合物，并添加 $5\\%$ 的光引发剂，用30um线棒均匀的涂在干净的PC板上，60度烘烤3min，然后放在传送带式UV固化机上，经 $800\\mathrm{mJ}$ 紫外光固化后，在室温条件下放置7d测试性能。  \n\n[0024] 其它的树脂包括所述主体树脂是带双键的聚氨酯丙烯酸酯，或环氧丙烯酸酯，如：长兴化学的6145‑100、6195‑100、DR‑U317、DR‑U319，DR‑U050M1、帝斯曼的Agisyn2421、Agisyn230A2、Agisyn271等；  \n\n[0025] 所述活性单体是丙烯酸酯类单体，该单体是型活性稀释单体，包括三羟甲基丙烷三丙烯酸酯(TMPTA)、乙氧基化三羟甲基丙烷三丙烯酸酯(ETPTA)、季戊四醇三丙烯酸酯(PETA)、双季戊四醇六丙烯酸酯(DPHA)、丙烯酰吗啉(ACMO)、聚乙二醇400二丙烯酸酯(PEG400DA)、聚乙二醇600二丙烯酸酯(PEG600DA)、聚乙二醇1000二丙烯酸酯(PEG1000DA)中的一种或至少两种的组合等。  \n\n[0026] 与现有技术相比，本发明具有如下突出效果：  \n\n[0027] 1)本发明设计了一种亲水型光固化树脂，将亲水二元聚醚胺中的伯胺与聚乙二醇二丙烯酸酯中的丙烯酸酯基进行迈克尔加成反应形成聚合物中间体1，中间体1中保留仲胺和端基丙烯酸酯，接着将丙烯酸酯基和氨基磺酸盐中的伯胺再次进行迈克尔加成反应，形成由阴‑非两性亲水基团组成的全亲水中间体2，然后将中间体2作为主链，利用仲胺与端NCO预聚体反应形成疏水侧链，该全亲水主链和全疏水侧链能够形成一种类“爪型”的表面活性剂结构，并与阴‑非两性亲水基团协同发挥持久亲水性能，水接触角长期维持在 ${10}^{\\circ}$ °以内。  \n\n[0028] 2)疏水侧链含有脲基和氨基甲酸酯基团，具有优异的机械性能和耐溶剂性能，丙烯酸酯基团可参与光固化反应，具备优异的附着力和耐磨性，能够耐水擦拭500次以上以及耐盐水浸泡。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 具体实施方式  \n\n[0029] 下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。  \n\n[0030] 制备亲水型光固化树脂的过程中还额外添加了二月桂酸二丁基锡DBTDL，此为常规选择，对性能没有影响，起到催化剂的作用。  \n\n[0031] 实施例1  \n\n[0032] 步骤1) 向反应釜a 中加入 $.444.6\\mathrm{g}\\left(2.0\\mathrm{mol}\\right)$ 异佛尔酮二异氰酸酯和 $0.06\\mathrm{g}$ $(0.01\\mathrm{wt\\%})$ )二月桂酸二丁基锡开启搅拌；将 $232.2\\mathrm{g}\\left(2.0\\mathrm{mol}\\right)$ 丙烯酸羟乙酯加入恒压滴液槽中，在室温下缓慢滴加至上述反应釜中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $70^{\\circ}\\mathrm{C}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值(通过盐酸二正丁胺法测定)，得到半封端的预聚体；  \n\n[0033] 步骤2)向反应釜b中加入 $.450\\mathrm{g}\\left(0.5\\mathrm{mol}\\right)$ 聚醚胺ED900开启搅拌，将 $381\\mathrm{g}\\left(0.75\\mathrm{mol}\\right)$ PEG400DA加入恒压滴液槽中，室温条件下缓慢滴加至上述反应釜中，滴完维持室温继续反应2h得到丙烯酸酯基封端的亲水聚合物中间体1，其中二元聚醚胺与聚乙二醇二丙烯酸酯的摩尔比为2:3；  \n\n[0034] 步骤3)用 $70\\mathrm{g}$ 去离子水将 $95.0\\mathrm{g}\\left(0.5\\mathrm{mol}\\right)$ 乙二胺基乙磺酸钠溶解均匀后转移至恒压滴液槽中，室温条件下缓慢滴加至反应釜b中，滴完维持室温继续反应2h后，升温至 $50^{\\circ}\\mathrm{C}$ 反应2h得到中间体2；  \n\n[0035] 步骤4)将步骤1中的预聚体转移到反应釜b的恒压滴液槽中，冰水浴条件下缓慢滴加至反应釜b中，滴完继续室温反应30min后，升至室温反应直至混合物的异氰酸酯基(‑NCO)的含量为零，得到亲水型光固化树脂，避光保存。  \n\n[0036] 实施例2  \n\n[0037] 步骤1) 向反应釜a 中加入 $336\\dots3\\mathrm{g}\\left(2\\dots0\\mathrm{mol}\\right)$ 六亚甲基二异氰酸酯和 $0.06\\mathrm{g}$ (0.01wt％)二月桂酸二丁基锡开启搅拌；将 $260.2\\mathrm{g}\\left(2.0\\mathrm{mol}\\right)$ 丙烯酸羟丙酯加入恒压滴液槽中，在室温下缓慢滴加至上述反应釜中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $70^{\\circ}\\mathrm{C}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值(通过盐酸二正丁胺法测定)，得到半封端的预聚体；  \n\n[0038] 步骤2)向反应釜b中加入 $800\\mathrm{g}\\left(0.4\\mathrm{mol}\\right)$ 聚醚胺ED2003开启搅拌，将 $566.4\\mathrm{g}$ (0.8mol)PEG600DA加入恒压滴液槽中，室温条件下缓慢滴加至上述反应釜中，滴完维持室温继续反应3h得到丙烯酸酯基封端的亲水聚合物中间体1，其中二元聚醚胺与聚乙二醇二丙烯酸酯的摩尔比为1:2；  \n\n[0039] 步骤3)用 $120\\mathrm{g}$ 去离子水将 $76.0\\mathrm{g}\\left(0.4\\mathrm{mol}\\right)$ )乙二胺基乙磺酸钠和 $58.8\\mathrm{g}\\left(0.4\\mathrm{mol}\\right)$ 牛磺酸钠溶解均匀后转移至恒压滴液槽中，室温条件下缓慢滴加至反应釜b中，滴完维持室温继续反应2h后，升温至 $50^{\\circ}\\mathrm{C}$ 反应2h得到中间体2；  \n\n[0040] 步骤4)将步骤1中的预聚体转移到反应釜b的恒压滴液槽中，冰水浴条件下缓慢滴加至反应釜b中，滴完继续室温反应30min后，升至室温反应直至混合物的异氰酸酯基(‑NCO)的含量为零，得到亲水型光固化树脂，避光保存。  \n\n[0041] 实施例3  \n\n[0042] 步骤1)向反应釜a中加入 $\\setminus314.78\\left(1.2\\mathrm{{mol}}\\right)$ 二环己基甲烷二异氰酸酯和 $0.04\\mathrm{g}$ $(0.01\\mathrm{wt\\%})$ 二月桂酸二丁基锡开启搅拌；将 $173.0\\mathrm{g}\\left(1.2\\mathrm{mol}\\right)4\\cdot$ ‑丙烯酸羟丁酯加入恒压滴液槽中，在室温下缓慢滴加至上述反应釜中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $70\\mathrm{{^\\circC}}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值(通过盐酸二正丁胺法测定)，得到半封端的预聚体；  \n\n[0043] 步骤2)向反应釜b中加入 $\\mathrm{.92g\\left(0.4mol\\right)}$ 聚醚胺D230开启搅拌，将101 .6g(0 .2mol)PEG400DA和 $443.2\\mathrm{g}\\left(0.4\\mathrm{mol}\\right)$ )PEG1000DA加入恒压滴液槽中，室温条件下缓慢滴加至上述反应釜中，滴完维持室温继续反应4h得到丙烯酸酯基封端的亲水聚合物中间体1，其中二元聚醚胺与聚乙二醇二丙烯酸酯的摩尔比为2:3；  \n\n[0044] 步骤3)用 $90\\mathrm{g}$ 去离子水将 $92.5\\mathrm{g}\\left(0.4\\mathrm{mol}\\right)$ 氨基苯磺酸钠溶解均匀后转移至恒压滴液槽中，室温条件下缓慢滴加至反应釜b中，滴完维持室温继续反应3h后，升温至 $40^{\\circ}\\mathrm{C}$ 反应2h得到中间体2；  \n\n[0045] 步骤4)将步骤1中的预聚体转移到反应釜b的恒压滴液槽中，冰水浴条件下缓慢滴加至反应釜b中，滴完继续室温反应30min后，升至室温反应直至混合物的异氰酸酯基(‑NCO)的含量为零，得到亲水型光固化树脂，避光保存。  \n\n[0046] 实施例4  \n\n[0047] 步骤1) 向反应釜a 中加入 $336.3\\mathrm{g}\\left(2.0\\mathrm{mol}\\right)$ 六亚甲基二异氰酸酯和 $0.05\\mathrm{g}$ $(0.01\\mathrm{wt\\%})$ )二月桂酸二丁基锡开启搅拌；将 $232.2\\mathrm{g}\\left(2.0\\mathrm{mol}\\right)$ 丙烯酸羟乙酯加入恒压滴液槽中，在室温下缓慢滴加至上述反应釜中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $65^{\\circ}\\mathrm{C}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值(通过盐酸二正丁胺法测定)，得到半封端的预聚体；  \n\n[0048] 步骤2)向反应釜b中加入 $360\\mathrm{g}\\left(0.6\\mathrm{mol}\\right)$ )聚醚胺ED600开启搅拌，将566 .4g(0 .8mol)PEG600DA加入恒压滴液槽中，室温条件下缓慢滴加至上述反应釜中，滴完维持室温继续反应3h得到丙烯酸酯基封端的亲水聚合物中间体1，其中二元聚醚胺与聚乙二醇二丙烯酸酯的摩尔比为3:4；  \n\n[0049] 步骤3)用 $60\\mathrm{g}$ 去离子水将 $76\\mathrm{g}\\left(0.4\\mathrm{mol}\\right)$ 乙二胺基乙磺酸钠溶解均匀后转移至恒压滴液槽中，室温条件下缓慢滴加至反应釜b中，滴完维持室温继续反应3h后，升温至 $40^{\\circ}\\mathrm{C}$ 反应2h得到中间体2；  \n\n[0050] 步骤4)将步骤1中的预聚体转移到反应釜b的恒压滴液槽中，冰水浴条件下缓慢滴加至反应釜b中，滴完继续室温反应30min后，升至室温反应直至混合物的异氰酸酯基(‑NCO)的含量为零，得到亲水型光固化树脂，避光保存。  \n\n[0051] 实施例5  \n\n[0052] 将实施例1所制得的亲水型光固化树脂添加 $5\\%$ 的光引发剂1173，用30um线棒均匀的涂在干净的PET膜上，60度烘烤3min，然后放在传送带式UV固化机上，经800mJ紫外光固化后，得到超亲水涂层。  \n\n[0053] 将实施例1所制得的亲水型光固化树脂与TMPTA、PEG600DA复配制备防雾涂料组合物，其中按质量份亲水型光固化树脂60份，TMPTA  20份、PEG600DA20份，再添加 $5\\%$ 的光引发剂1173，用30um线棒均匀的涂在干净的PC板上，60度烘烤3min，然后放在传送带式UV固化机上，经800mJ紫外光固化后，得到超亲水涂层。  \n\n[0054] 实施例6  \n\n[0055] 将实施例2所制得的亲水型光固化树脂添加 $5\\%$ 的光引发剂1173，用30um线棒均匀的涂在干净的PET膜上，60度烘烤3min，然后放在传送带式UV固化机上，经 $800\\mathrm{mJ}$ 紫外光固化后，得到超亲水涂层。  \n\n[0056] 将实施例2所制得的亲水型光固化树脂与TMPTA、PEG600DA复配制备防雾涂料组合物，其中按质量份亲水型光固化树脂60份，TMPTA  20份、PEG600DA20份，再添加 $5\\%$ 的光引发剂1173，用30um线棒均匀的涂在干净的PC板上，60度烘烤3min，然后放在传送带式UV固化机上，经800mJ紫外光固化后，得到超亲水涂层。  \n\n[0057] 实施例7  \n\n[0058] 将实施例3所制得的亲水型光固化树脂添加 $5\\%$ 的光引发剂1173，用30um线棒均匀的涂在干净的PET膜上，60度烘烤3min，然后放在传送带式UV固化机上，经 $800\\mathrm{mJ}$ 紫外光固化后，得到超亲水涂层。  \n\n[0059] 将实施例3所制得的亲水型光固化树脂与TMPTA、PEG600DA复配制备防雾涂料组合物，其中按质量份亲水型光固化树脂60份，TMPTA  20份、PEG600DA20份，再添加 $5\\%$ 的光引发剂1173，用30um线棒均匀的涂在干净的PC板上，60度烘烤3min，然后放在传送带式UV固化机上，经800mJ紫外光固化后，得到超亲水涂层。  \n\n[0060] 实施例8  \n\n[0061] 将实施例4所制得的亲水型光固化树脂添加 $5\\%$ 的光引发剂1173，用30um线棒均匀的涂在干净的PET膜上，60度烘烤3min，然后放在传送带式UV固化机上，经 $800\\mathrm{mJ}$ 紫外光固化后，得到超亲水涂层。  \n\n[0062] 将实施例4所制得的亲水型光固化树脂与TMPTA、PEG600DA复配制备防雾涂料组合物，其中按质量份亲水型光固化树脂60份，TMPTA  20份、PEG600DA20份，再添加 $5\\%$ 的光引发剂1173，用30um线棒均匀的涂在干净的PC板上，60度烘烤3min，然后放在传送带式UV固化机  \n\n上，经800mJ紫外光固化后，得到超亲水涂层。  \n\n[0063] 性能测试  \n\n[0064] 对上述实施例1‑4，实施例5‑8制得的超亲水涂层在室温条件下放置7d后分别按照表1和表3中的测试项目和方法进行性能的测试，结果如表2和表4所示。  \n\n[0065] 表1实施例1‑4所制得的超亲水涂层的性能测试项目和方法  \n\n[0066] [0067]  \n\n<html><body><table><tr><td>项目</td><td>方法</td></tr><tr><td>铅笔硬度</td><td>通过铅笔硬度仪按照GB/T6739-1996中的规定进行</td></tr><tr><td>附着力</td><td>采用百格法，交叉划格形成10×10的小方格。用3M-610压敏 胶带紧密粘附于涂层表面，然后沿90度方向快速撕去胶带，观 测格子边缘的破坏程度</td></tr><tr><td>初始水接触角</td><td>用便携式接触角测量仪SDP-260测试10ul水量下接触角的大小</td></tr><tr><td>耐水擦拭</td><td>样品用水打湿的无纺布在1kg力下，来回擦拭500次，观察接触</td></tr></table></body></html>  \n\n<html><body><table><tr><td></td><td>角的变化</td></tr><tr><td>耐盐水浸泡</td><td>样品浸泡在5.0%的氯化钠溶液中1h，观察接触角的变化</td></tr><tr><td>耐磨测试(耐划伤)</td><td>用羊毛毡，500克压力，lcm×1cm磨头，擦500来回，记录明 显的划痕个数。</td></tr><tr><td>持久性测试</td><td>对涂层做长期测试，每天测试接触角，记录出现接触角大于30 度时的天数</td></tr><tr><td>粘性测试</td><td>用棉花擦样品表面，不残留纤维为光滑，残留纤维越多说明越粘</td></tr></table></body></html>  \n\n[0068] 表2实施例1‑4所制得的超亲水涂层的性能测试结果  \n\n<html><body><table><tr><td>测试性能</td><td>测试方式和标准</td><td>实施例1</td><td>实施例2</td><td>实施例3</td><td>实施例4</td></tr><tr><td>涂层厚度</td><td>um</td><td>7.8</td><td>9.4</td><td>8.5</td><td>10.9</td></tr><tr><td>初始水接触角(°)</td><td></td><td>8</td><td>12</td><td>14</td><td>10</td></tr><tr><td>耐水擦拭(°)</td><td></td><td>10</td><td>14</td><td>14</td><td>12</td></tr><tr><td>盐水浸泡</td><td></td><td>20</td><td>21</td><td>25</td><td>19</td></tr><tr><td>铅笔硬度</td><td>铅笔测试仪</td><td>1H</td><td>1H</td><td>2H</td><td>1H</td></tr><tr><td>耐划伤</td><td></td><td>５</td><td>7</td><td>4</td><td>5</td></tr><tr><td>附着力</td><td>划格</td><td>0级</td><td>0级</td><td>0级</td><td>0级</td></tr><tr><td>粘性测试</td><td></td><td>光滑</td><td>光滑</td><td>光滑</td><td>光滑</td></tr><tr><td>持久性测试</td><td></td><td>>365d</td><td>>365d</td><td>>365d</td><td>>365d</td></tr></table></body></html>\n\n[0070] 表3实施例5‑8所制得的超亲水涂层的性能测试项目和方法  \n\n[0071] [0074] [0075]  \n\n<html><body><table><tr><td>项目</td><td>方法</td></tr><tr><td>铅笔硬度</td><td>通过铅笔硬度仪按照GB/T6739-1996中的规定进行</td></tr><tr><td>附着力</td><td>采用百格法，交叉划格形成10X10的小方格。用3M-610压敏胶带 紧密粘附于涂层表面，然后沿90度方向快速撕去胶带，观测格子边 缘的破坏程度</td></tr><tr><td>初始防雾测试</td><td>涂层置于60℃C热水上方3cm高度，面向水蒸气高达15分钟。如果 不起雾则通过。如果测试中起雾，记录从开始测试到出现雾的时间</td></tr><tr><td>哈气测试</td><td>朝涂层哈气，观察起雾情况</td></tr></table></body></html>  \n\n<html><body><table><tr><td rowspan=\"7\">[0072]</td><td>雾测试（冷水测</td><td>试</td></tr><tr><td></td><td>沸水浸泡-防雾 样品在沸水中煮1小时，取出，冷却干燥12小时，进行烧杯防雾测 测试(沸水测试) 试</td><td></td></tr><tr><td>落沙-雾度测试</td><td></td><td>不会被目测观察到</td></tr><tr><td>耐水擦测试</td><td></td><td>观察落沙试验后，雾度升高值</td></tr><tr><td rowspan=\"5\">耐磨测试（耐划 伤) 防雾持久性测试</td><td></td><td>样品用水打湿的无纺布在1kg力下，来回擦拭500次，观察雾度的</td></tr><tr><td></td><td>用羊毛毡，500克压力，1cm×1cm磨头，擦500来回，记录明显的 划痕个数。</td></tr><tr><td></td><td>对涂层做长期测试，每天测试防雾性能，记录出现防雾性能下降时 的天数</td></tr><tr><td>粘性测试</td><td>用棉花擦样品表面，不残留纤维为光滑，残留纤维越多说明越粘</td></tr></table></body></html>\n\n[0073] 表4实施例5‑8所制得的防雾涂层的性能测试结果  \n\n<html><body><table><tr><td></td><td></td><td>实施例5</td><td>实施例6</td><td>实施例 7</td><td>实施例 8</td></tr><tr><td>固化所需能量</td><td></td><td>800mJ</td><td>800mJ</td><td>800mJ</td><td>800mJ</td></tr><tr><td>涂层厚度</td><td>um</td><td>8.4</td><td>8.2</td><td>7.4</td><td>7.8</td></tr><tr><td>初始雾度</td><td></td><td>0.1%</td><td>0.1%</td><td>0.2%</td><td>0.1%</td></tr><tr><td>落沙-雾度</td><td>观察落沙测试后，雾度 升高值</td><td>2.3%</td><td>2.0%</td><td>2.4%</td><td>2.6%</td></tr><tr><td>初始防雾</td><td>15min不起雾，则通过</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>哈气</td><td>不起雾则通过</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>冷水测试</td><td>观察开始测试到出现雾 的时间</td><td>>180s</td><td>>180s</td><td>>180s</td><td>>180s</td></tr><tr><td>沸水测试</td><td>观察开始测试到出现雾 的时间</td><td>>180s</td><td>>180s</td><td>>180s</td><td>>180s</td></tr></table></body></html>  \n\n<html><body><table><tr><td>耐水擦</td><td></td><td>2.5%</td><td>2.8%</td><td>3.0%</td><td>3.4%</td></tr><tr><td>铅笔硬度</td><td>铅笔测试仪</td><td>2H</td><td>2H</td><td>3H</td><td>2H</td></tr><tr><td>耐划伤</td><td>记划痕数</td><td>1</td><td>2</td><td>1</td><td>1</td></tr><tr><td>附着力</td><td>划格</td><td>0级</td><td>0级</td><td>0级</td><td>0级</td></tr><tr><td>防雾持久性</td><td></td><td>293d</td><td>274d</td><td>266d</td><td>266d</td></tr><tr><td>粘性测试</td><td></td><td>光滑</td><td>光滑</td><td>光滑</td><td>光滑</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,52 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n(21)申请号 202210559327 .7(22)申请日 2022.05.23(65)同一申请的已公布的文献号申请公布号 CN 115521452 A(43)申请公布日 2022.12.27(73)专利权人 武汉中科先进材料科技有限公司地址 430000 湖北省武汉市经济技术开发区201M地块华人汇和科技园（华中智谷）一期F10研发楼1-2层  \n\n(72)发明人 康翼鸿 喻学锋 吴列　杨帆程文杰　甄亚枝  \n\n(74)专利代理机构 武汉高得专利代理事务所(普通合伙) 42268专利代理师 陈挥秀",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n一种光固化低聚物、其制备方法及含有该低聚物的光固化涂料  \n\n(51)Int.Cl. C08G 65/3 3(2006.01) C09D 171/02(2006.01)  \n\n(56)对比文件 CN 102762657 A,2012.10.31 CN 107057555 A,2017 .08.18 US 5907023 A,1999.05.25 JP 2014218621 A,2014 .11 .20 CN 112048051 A,2020.12.08 CN 113943529 A,2022.01 .18  \n\n审查员 贺勇",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明属于高分子材料技术领域，具体地说，涉及一种光固化低聚物、其制备方法及含有该低聚物的光固化涂料。该种光固化低聚物结构为以脲基基团为交联点、聚氧乙烯醚为主链段的脲基丙烯酸酯。低聚物具有低黏度、高速固化、有特殊功能等优点，针对部分基材难以附着的特点，在PMMA、聚砜、聚苯乙烯上均有较好的附着力，可应用在难附着基材的防雾、防污、减阻、润湿等领域。  \n\n![](images/6e8de00a30d5e60fda0c9109c944ab464d5fca64007e54e3b49f67bd5c7bd504.jpg)  \n\n1.一种光固化低聚物，其特征在于，具有以下结构：  \n\n![](images/19b37398a4f902bb159ae6b29016706db8ea6b57decc98f8d0db3bcdd2b2acaf.jpg)  \n\n其中， $\\mathrm{y}\\approx39$ ， $\\mathrm{X^{+}Z}{\\approx}6$ 。  \n\n2.权利要求1所述的光固化低聚物的制备方法，其特征在于，包括以下步骤：  \n\n(1)聚醚胺与三(2‑羟乙基)异氰脲酸三丙烯酸酯在 $60-80^{\\circ}\\mathrm{C}$ 下进行加成反应，得到异氰尿酸聚醚胺丙烯酸酯；(2)羟乙基丙烯酸酯与异佛尔酮二异氰酸酯在 $30-50^{\\circ}\\mathrm{C}$ 下反应0.5‑1h，得到脲基丙烯酸酯；(3)将步骤(1)和步骤(2)所得产物在 $30-50^{\\circ}\\mathrm{C}$ 下进行聚合反应，反应0.5‑1h，即得到所述光固化低聚物，命名为异氰尿酸聚氧乙烯醚丙烯酸酯。3.根据权利要求2所述光固化低聚物的制备方法，其特征在于，所述步骤(1)中聚醚胺与三(2‑羟乙基)异氰脲酸三丙烯酸酯的摩尔比为1：2。4.根据权利要求2所述光固化低聚物的制备方法，其特征在于，所述步骤(2)中羟乙基丙烯酸酯与异佛尔酮二异氰酸酯的摩尔比为1：1。5.根据权利要求2所述光固化低聚物的制备方法，其特征在于，所述步骤(1)和步骤(2)所得产物的摩尔比为1：1。6.一种光固化涂料，包含权利要求1所述光固化低聚物、丙烯酸酯单体、光引发剂、助剂和溶剂。7.根据权利要求6所述光固化涂料，其特征在于：光引发剂为2‑羟基‑2‑甲基‑1‑苯基丙酮，1‑羟基环己基苯基甲酮，2,4,6‑三甲基苯甲酰基‑二苯基氧化膦中的一种或多种。8.根据权利要求6所述光固化涂料，其特征在于：助剂为流平剂、消泡剂、增稠剂、分散剂、润湿剂中的一种或多种。9.根据权利要求6所述光固化涂料，其特征在于：溶剂为乙醇、异丙醇、乙酸乙酯、乙酸丁酯、丙二醇甲醚中的一种或多种。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 一种光固化低聚物、其制备方法及含有该低聚物的光固化涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明属于高分子材料技术领域，具体地说，涉及一种光固化低聚物、其制备方法及含有该低聚物的光固化涂料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 紫外光固化涂料技术是指一种表面处理技术，该技术通过光引发剂或者光敏剂，经紫外光辐照产生自由基而引发活性单体、低聚物或树脂发生聚合反应。近年来，人们对环保的要求越来越高，溶剂型涂料因为挥发性有机物(VOC)的排放受到越来越严格的限制，以紫外光固化涂料(UVCC)、水性涂料、高固体分涂料和粉末涂料为代表的绿色环保型涂料成为人们关注和研究的热点。与其它几类涂料相比，UVCC具有固化速度快、固化温度低、环保节能、涂层性能优异，可用于塑料、纸张和木材等热敏性底材的涂布等优势。  \n\n[0003] 低聚物是UV固化涂料最重要的组分，它决定了固化膜的物理机械性能，如硬度、柔韧性、强度、耐磨性、附着力等，也影响光固化速度。目前的低聚物通常是聚乙二醇丙烯酸酯等附着力低的物质或聚氨酯丙烯酸酯等亲水性差的物质，难以保持附着力与亲水性的平衡。  \n\n[0004] 目前常见的光固化低聚物包括环氧丙烯酸酯、聚氨酯丙烯酸酯、聚酯丙烯酸酯等，具有黏度低、固化速度快等优点，但是低聚物往往没有丰富的基团，附着力差。高聚后链段较软，机械强度差。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0005] 本发明的目的是针对现有技术的不足，提供附着力优异的一种光固化低聚物、其制备方法及含有该低聚物的光固化涂料。可实现高附着力、高耐磨、耐水泡、耐腐蚀等的功能。  \n\n[0006] 为实现上述目的，本发明首先提供一种光固化低聚物，如(Ⅰ)所示，结构为以脲基基团为交联点、聚氧乙烯醚为主链段的脲基丙烯酸酯，可命名为异氰尿酸聚氧乙烯醚丙烯酸酯；  \n\n[0007] 所述光固化低聚物表面张力低，对基材润湿性好；对于PMMA、聚砜、聚苯乙烯等塑料基材有较强的渗透溶胀能力，固化交联后可在基材与涂层之间形成一层很薄的互穿网络结构，从而增强附着力，同时所述光固化低聚物含有多种官能团，能提高附着力。  \n\n[0008] 按照GB/T  9286‑1998进行光固化低聚物的附着力测试，0级代表最好，5级代表最差，具体方法为将光固化低聚物与光引发剂TPO以质量比24：1混合，UV灯下固化30s，测试附着力，结果附着力均为0级。  \n\n![](images/bee5c359c35da8804c61c742b58fd10e75a608184841451128f28bc8f2ea306d.jpg)  \n（I)  \n\n[0010] 本发明还提供一种光固化低聚物的制备方法，具体如下：  \n\n[0011] (1)聚醚胺(ED2003)与三(2‑羟乙基)异氰脲酸三丙烯酸酯(THEICTA)在 $60-80^{\\circ}\\mathrm{C}$ 下进行加成反应，得到聚氧乙烯醚异氰尿酸丙烯酸酯；  \n[0012] (2)羟乙基丙烯酸酯(HEA)与异佛尔酮二异氰酸酯(IPDI)在 $30-50^{\\circ}\\mathrm{C}$ 下反应0 .5‑1h，得到脲基丙烯酸酯；  \n[0013] (3)将步骤(1)和步骤(2)所得产物在 $30-50^{\\circ}\\mathrm{C}$ 下进行聚合反应，反应0.5‑1h，即得到所述光固化低聚物。  \n[0014] 具体的，所述步骤(1)中聚醚胺与三(2‑羟乙基)异氰脲酸三丙烯酸酯的摩尔比为1：2。  \n[0015] 具体的，所述步骤(2)中羟乙基丙烯酸酯与异佛尔酮二异氰酸酯的摩尔比为1：1。[0016] 具体的，所述步骤(1)和步骤(2)所得产物的摩尔比为1：1。  \n[0017] 本发明还提供一种光固化涂料，包含上述光固化低聚物 $50\\sim70\\$ 份、丙烯酸酯单体$10\\sim20$ 份、光引发剂 $2\\sim5$ 份、助剂 $1\\sim2$ 份、溶剂 $14\\sim27$ 份。  \n[0018] 具体的，丙烯酸酯单体为1,6己二醇二丙烯酸酯(HDDA)、三羟甲基丙烷三丙烯酸酯(TMPTA)、二丙二醇二丙烯酸酯(DPGDA)中的一种或多种。  \n[0019] 具体的，光引发剂为2‑羟基‑2‑甲基‑1‑苯基丙酮(1173)，1‑羟基环己基苯基甲酮(184)，2,4,6‑三甲基苯甲酰基‑二苯基氧化膦(TPO)中的一种或多种。  \n[0020] 具体的，助剂为流平剂、消泡剂、增稠剂、分散剂、润湿剂中的一种或多种。  \n[0021] 具体的，溶剂为乙醇、异丙醇、乙酸乙酯、乙酸丁酯、丙二醇甲醚中的一种或多种。[0022]  \n\n本发明与现有技术相比，本发明具有如下的有益效果：  \n\n[0023] 1、低聚物具有低黏度、高速固化、有特殊功能等优点，光固化配方的基体树脂，构成固化产品的基本骨架，即固化后产品的基本性能(硬度、柔韧性、附着力、光学性能、耐老化等)主要由低聚物树脂决定。针对部分基材难以附着的特点，设计合成了新型的高PMMA、聚砜、聚苯乙烯附着力的光固化低聚物，通过对表面张力，基材的渗透溶胀、官能度设计从而增强涂层在基材的附着力，同时光固化低聚物含有多种基团增强附着力。可应用在难附着基材的防雾、防污、减阻、润湿等领域。  \n\n[0024] 2、本发明的光固化低聚物结合其他光固化单体可以形成交联的互穿网络，提高涂层硬度、机械强度，可锁住表面活性剂，延长防雾耐久时间。",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 附图说明  \n\n[0025] 图1实施例1所得可光固化低聚物B1H  NMR谱图；   \n[0026] 图2实施例1所得可光固化低聚物B  FTIR谱图。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 具体实施方式  \n\n[0027] 下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。  \n\n[0028] 实施例1光固化低聚物的制备1  \n\n[0029] 将1mol聚醚胺(ED2003)与2mol三(2‑羟乙基)异氰脲酸三丙烯酸酯(THEICTA)在60℃下反应4h，将1mol羟乙基丙烯酸酯(HEA)与1mol异佛尔酮二异氰酸酯(IPDI)在 $30^{\\circ}\\mathrm{C}$ 下反应0.5h，将两步反应所得产物在 $30^{\\circ}\\mathrm{C}$ 下反应0.5h得到光固化低聚物B。  \n\n[0030] 实施例2光固化低聚物的制备2  \n\n[0031] 将1mol聚醚胺(ED2003)与2mol三(2‑羟乙基)异氰脲酸三丙烯酸酯(THEICTA)在80℃下反应4h，将1mol羟乙基丙烯酸酯(HEA)与1mol异佛尔酮二异氰酸酯(IPDI)在 $50^{\\circ}\\mathrm{C}$ 下反应1h，将两步反应所得产物在 $50^{\\circ}\\mathrm{C}$ 下反应1h得到光固化低聚物B。  \n\n[0032] 实施例3光固化低聚物的制备3  \n\n[0033] 将1mol聚醚胺(ED2003)与2mol三(2‑羟乙基)异氰脲酸三丙烯酸酯(THEICTA)在70$\\mathrm{{^\\circC}}$ 下反应4h，将1mol羟乙基丙烯酸酯(HEA)与1mol异佛尔酮二异氰酸酯(IPDI)在 $50^{\\circ}\\mathrm{C}$ 下反应1h，将两步反应所得产物在 $40^{\\circ}\\mathrm{C}$ 下反应1h得到光固化低聚物B。  \n\n[0034] 实施例3光固化低聚物的测试结果  \n\n[0035] 以氘代氯仿为溶剂，将实施例1制备的可光固化低聚物B溶解，在布鲁克400MHz核磁共振NMR波谱仪测试1H  NMR，如图2所示。其在5.5‑6.5ppm之间的峰为 $\\mathrm{CH2=}$ CH‑的特征峰，4.2ppm左右的峰为O‑CH2‑CH2‑O链段的特征峰，分子式中所有的氢的峰都能与谱图中的峰相对应，鉴定结构为可光固化低聚物B。  \n\n[0036] 将实施例1制备的可光固化低聚物B测试红外光谱(FITR)，其谱图如图2所示。上述结构谱图中丙烯酸酯、脲基、聚乙二醇链段峰都在谱图中呈现，红外谱图与可光固化低聚物B结构相符。  \n\n[0037] 实施例4光固化低聚物的应用及效果[0038] 本发明将实施例1所得50份低聚物与20份丙烯酸酯单体HDDA、3份光引发剂1173、2份流平剂与消泡剂、25份乙醇、乙酸乙酯混合溶剂进行复配，可制备紫外光固化防雾涂料组合物，该涂料可在聚砜塑料基材上制备超亲水涂层。该涂层具有良好的防雾、防污、减阻、润湿等效果，且涂层附着力好、不易脱落、硬度高、耐久性好。  \n\n[0039] 实施例5光固化低聚物的应用及效果[0040] 本发明将实施例2所得60份低聚物与10份丙烯酸酯单体TMPTA、2份光引发剂184、1份增稠剂与分散剂、27份异丙醇、乙酸丁酯混合溶剂等进行复配，可制备紫外光固化防雾涂料组合物，该涂料可在PMMA塑料基材上制备超亲水涂层。该涂层具有良好的防雾、防污、减阻、润湿等效果，且涂层附着力好、不易脱落、硬度高、耐久性好。  \n\n[0041] 实施例6光固化低聚物的应用及效果[0042] 本发明将实施例3所得70份低聚物与常规的10份丙烯酸酯单体DPGDA、5份光引发剂TPO、1份润湿剂、14份丙二醇甲醚溶剂进行复配，可制备紫外光固化防雾涂料组合物，该涂料可在聚苯乙烯塑料基材上制备超亲水涂层。该涂层具有良好的防雾、防污、减阻、润湿等效果，且涂层附着力好、不易脱落、硬度高、耐久性好。  \n\n![](images/2462384ba31b1e95a9c34813aa91df6a63e55f5c81993d6b6b31c81e69bfe9ee.jpg)  \n图1  \n\n![](images/f93a8561d6689ce30cd816e07d79999510d644b2b444fecdf7be0082b20ff6d8.jpg)  \n图2",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,52 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n<html><body><table><tr><td>(21)申请号 202211452417.2 (51) Int.CI .</td></tr><tr><td>(22)申请日2022.11.21 CO9D 171/00 (2006.01)</td></tr><tr><td>C09D 175/04(2006.01)</td></tr><tr><td>(65)同一申请的已公布的文献号 C09K 3/18 (2006.01)</td></tr><tr><td>申请公布号CN 116023849 A C08J 7/054 (2020.01)</td></tr><tr><td>(43)申请公布日2023.04.28 C08L 69/00 (2006.01)</td></tr><tr><td>(73)专利权人武汉中科先进材料科技有限公司 (56)对比文件</td></tr><tr><td>地址430000 湖北省武汉市经济技术开发 CN 115044008A,2022.09.13</td></tr><tr><td>区201M地块华人汇和科技园（华中智 CN 106867376 A,2017.06.20</td></tr><tr><td>谷)一期F10研发楼1-2层 审查员卢玉</td></tr><tr><td>(72)发明人康翼鸿喻学锋甄亚枝程文杰</td></tr><tr><td>何睿吴列杨帆</td></tr><tr><td>(74)专利代理机构武汉高得专利代理事务所</td></tr><tr><td>（普通合伙）42268</td></tr><tr><td>专利代理师陈挥秀</td></tr></table></body></html>",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n一种防雾涂料及其制备方法、防雾涂层",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本申请涉及高分子材料技术领域，特别涉及一种防雾涂料及其制备方法、防雾涂层。本申请提供的防雾涂料的制备方法包括：将多元醇A和二异氰酸酯混合，加入溶剂，加热反应，得到亲水聚合物，向亲水聚合物中加入多元醇B混合均匀，得到亲水组分A；将聚醚胺与甲基丙烯酰胺类化合物混合进行加成反应，得到含有多个活泼N‑异丁氧基和/或N‑正丁氧基的亲水组分B；将亲水组分A和亲水组分B混合，即得到防雾涂料。本申请提供的防雾涂料的固化时间为 $10{\\sim}20$ 分钟，可有效提升产能并保证涂层制备的良品率。  \n\n![](images/f9daf867b158c64ebe081d5a83f9c6a33aae7c967c71595feab6fac37cd0802a.jpg)  \n\n1.一种防雾涂料的制备方法，其特征在于，包括以下步骤：  \n\n将多元醇A和二异氰酸酯混合，加入溶剂，加热反应，得到亲水聚合物，向亲水聚合物中加入多元醇B混合均匀，得到亲水组分A；所述多元醇A选用异山梨醇、吐温20、吐温60、吐温80、甘油、甘油聚醚‑18、甘油聚醚‑26中的任一种或多种的混合；所述多元醇B选用吐温20、吐温60、吐温80、甘油、甘油聚醚‑18、甘油聚醚‑26中的任一种或两种的混合；  \n\n将聚醚胺与甲基丙烯酰胺类化合物混合进行加成反应，得到含有多个活泼N‑异丁氧基和/或N‑正丁氧基的亲水组分B；所述甲基丙烯酰胺类化合物选用N‑(异丁氧基)甲基丙烯酰胺或N‑(正丁氧基)甲基丙烯酰胺中的任一种或两种的混合；  \n\n将亲水组分A和亲水组分B混合，即得到防雾涂料；所述亲水组分A中的羟基与亲水组分B中的N‑异丁氧基和/或N‑正丁氧基的摩尔比为 $1.2{\\sim}1.5{:}1$ ；其中，亲水组分A中的羟基含量为亲水聚合物中的羟基含量和多元醇B中的羟基含量的总和。  \n\n2.根据权利要求1所述的防雾涂料的制备方法，其特征在于，所述二异氰酸酯选用六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、1 ,4‑环己烷二异氰酸酯中的任一种或两种的混合。  \n\n3.根据权利要求1所述的防雾涂料的制备方法，其特征在于，所述聚醚胺选用聚醚胺D230、聚醚胺ED600、聚醚胺ED900、聚醚胺ED2003中的任一种或多种的混合。  \n\n4.根据权利要求1所述的防雾涂料的制备方法，其特征在于，聚醚胺与甲基丙烯酰胺类化合物的加成反应过程中还加入阻聚剂。  \n\n5.根据权利要求1所述的防雾涂料的制备方法，其特征在于，多元醇A与二异氰酸酯的摩尔比为2:1；聚醚胺与甲基丙烯酰胺类化合物的摩尔比为1：4。  \n\n6.一种防雾涂料，其特征在于，利用权利要求1‑5任一项所述的制备方法制得。  \n\n7.一种防雾涂层，其特征在于，由权利要求1‑5任一项所述的制备方法制得的防雾涂料或权利要求6所述的防雾涂料在基材上加热固化 $10{\\sim}20\\mathrm{min}$ 得到。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 一种防雾涂料及其制备方法、防雾涂层",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本申请涉及高分子材料技术领域，特别涉及一种防雾涂料及其制备方法、防雾涂层。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 防雾涂料是一种以涂层形式表现的能防止雾气凝结的涂层，具有精度高、涂覆率大、经济性好的优点。制备防雾涂料的原料一般由具有交联官能团的亲水聚合物和固化剂构成，亲水聚合物的分子量较大，分子链上的官能团的活性较低，需要在 $100{\\sim}120^{\\circ}\\mathrm{C}$ 的高温条件固化 $1{\\sim}2\\mathrm{h}$ 。而大部分塑料基材的热变形温度都较低，例如PC塑料的热变形温度为135$\\mathrm{{^\\circC}}$ ，亚克力的热变形温度为 $65{\\sim}95^{\\circ}\\mathrm{C}$ ，长时间的烘烤很容易导致塑料基材产生形变，降低涂层制备的良品率。另外，现有的热固性防雾涂料的固化剂一般不具备防雾性，加入量低于标准则涂层性能严重受损，高于标准则防雾性能快速下降。  \n\n[0003] 基于以上分析，提供一种能够提高固化效率的防雾涂料的原料组合十分重要。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0004] 本申请实施例提供一种防雾涂料的制备方法，以解决相关技术中现有的防雾涂料固化时间长的问题。  \n[0005] 第一方面，本申请实施例提供了一种防雾涂料的制备方法，包括以下步骤：[0006] 步骤S101，将多元醇A和二异氰酸酯混合，加入溶剂，加热反应，得到亲水聚合物，待亲水聚合物的温度降至小于 $40^{\\circ}\\mathrm{C}$ 后，向亲水聚合物中加入多元醇B混合均匀，得到亲水组分A；  \n[0007] 步骤S102，将聚醚胺与甲基丙烯酰胺类化合物混合进行加成反应，得到含有多个活泼N‑异丁氧基和/或N‑正丁氧基的亲水组分B；  \n[0008] 步骤S103，将亲水组分A和亲水组分B混合，即得到防雾涂料。  \n[0009] 一些实施例中，多元醇A与二异氰酸酯的摩尔比为2:1。  \n[0010] 一些实施例中，聚醚胺与甲基丙烯酰胺类化合物的摩尔比为1:4。  \n[0011] 一些实施例中，所述多元醇A选用异山梨醇、吐温20、吐温60、吐温80、甘油、甘油聚醚‑18、甘油聚醚‑26中的任一种或多种的混合。  \n[0012] 一些实施例中，所述二异氰酸酯选用六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、1 ,4‑环己烷二异氰酸酯中的任一种或两种的混合。  \n[0013] 一些实施例中，所述多元醇B选用吐温20、吐温60、吐温80、甘油、甘油聚醚‑18、甘油聚醚‑26中的任一种或两种的混合。  \n[0014] 一些实施例中，所述甲基丙烯酰胺类化合物选用N‑(异丁氧基)甲基丙烯酰胺或N‑(正丁氧基)甲基丙烯酰胺中的任一种或两种的混合。  \n[0015] 一些实施例中，所述聚醚胺选用聚醚胺D230、聚醚胺ED600、聚醚胺ED900、聚醚胺  \n\nED2003中的任一种或多种的混合。  \n\n[0016] 一些实施例中，所述溶剂选用二丙酮醇。  \n\n[0017] 一些实施例中，步骤S102中，聚醚胺与甲基丙烯酰胺类化合物的加成反应过程中还加入阻聚剂。  \n\n[0018] 一些优选实施例中，所述阻聚剂选用4‑甲氧基苯酚。  \n\n[0019] 一些实施例中，所述亲水组分A中的羟基与亲水组分B中的N‑异丁氧基和/或N‑正丁氧基的摩尔比为 $1.2{\\sim}1.5{:}1$ ；其中，亲水组分A中的羟基含量为亲水聚合物中的羟基含量和多元醇B中的羟基含量的总和。  \n\n[0020] 第二方面，本申请提供了利用上述制备方法制得的防雾涂料。  \n\n[0021] 第三方面，本申请还提供了一种防雾涂层，所述防雾涂层由上述防雾涂料在基材上加热固化 $10{\\sim}20\\mathrm{min}$ 得到。  \n\n[0022] 一些实施例中，所述基材选用聚碳酸酯PC、有机玻璃PMMA、聚对苯二甲酸乙二酯PET、聚砜等塑料基材。  \n\n[0023] 本申请的多元醇A选用异山梨醇时，异山梨醇与二异氰酸酯反应得到亲水聚合物的反应表达式为：  \n\n![](images/948439be741feac4dc326a8cf2bc4a74db888ce38ecc166a31fc1437770b2a80.jpg)  \n\n[0025] 式中，R为六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、1,4‑环己烷二异氰酸酯中一种或两种的残基。  \n\n[0026] 本申请中聚醚胺与N‑(异丁氧基)甲基丙烯酰胺反应得到亲水组分B的反应表达式为：  \n\n[0027]  \n\n![](images/bdc6e2c4054e245adc51955f52264cbea7e75ce128aa45790bcb313de8d4318b.jpg)  \n\n[0028] 式中， $\\mathrm{R}_{1}$ 为n个聚乙二醇链段和m个聚丙二醇链段组成的亲水长链，n、m为整数。  \n\n[0029] 本申请通过分子设计使亲水组分A和亲水组分B同时具有亲水性，在施工时能扩大两组分之间的配比窗口，提高了操作的简便性。  \n\n[0030] 本申请的防雾涂料使用的亲水组分B含有亲水长链，能够实现长效防雾，其固化形成的涂层可以应用在PC\\PMMA\\PET\\聚砜等塑料基材上，以及泳镜、汽车防雾灯等领域。  \n\n[0031] 本申请提供的技术方案带来的有益效果包括：  \n\n[0032] 1.本申请提供的防雾涂料的亲水组分B中含有多个活泼的N‑异丁氧基或N‑正丁氧基，能够与亲水组分A中的羟基(来源于亲水聚合物和多元醇B)实现 $120^{\\circ}\\mathrm{C}*(10{\\sim}20)\\mathrm{min}$ 的条件下交联固化，解决了长时间高温烘烤下塑料基材产生形变的问题，提高了固化效率，有效提升了产能并保证涂层制备的良品率；  \n\n[0033] 2.本申请的防雾涂料固化后形成的防雾涂层防雾性能优异，试验表明 $80^{\\circ}\\mathrm{C}$ 水蒸气熏蒸或长时间酸泡条件下防雾效果均不受影响。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 附图说明  \n\n[0034] 为了更清楚地说明本申请实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。  \n\n[0035] 图1为本申请实施例提供的防雾涂料的制备方法的流程示意图。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 具体实施方式  \n\n[0036] 为使本申请实施例的目的、技术方案和优点更加清楚，下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本申请的一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本申请保护的范围。[0037] 本申请实施例提供了一种防雾涂料的制备方法，其能解决相关技术中现有的防雾涂料固化时间长的问题。  \n\n[0038] 图1是本申请提供的防雾涂料的制备方法的流程示意图，参考图1，该防雾涂料的制备方法包括以下步骤：  \n\n[0039] 步骤S101，将多元醇A和二异氰酸酯按照摩尔比2:1混合，加入二丙酮醇，于 $80{\\sim}85$ $\\mathrm{{^\\circC}}$ 反应 $4\\mathrm{\\sim}8\\mathrm{h}$ 至NCO完全被消耗，得到亲水聚合物，待亲水聚合物的温度降至小于 $40^{\\circ}\\mathrm{C}$ 后，向亲水聚合物中加入多元醇B混合均匀，得到亲水组分A；  \n\n[0040] 步骤S102，将聚醚胺与甲基丙烯酰胺类化合物按照摩尔比1:4混合，在 $30{\\sim}80^{\\circ}\\mathrm{C}$ 下进行迈克尔加成反应 $2\\mathrm{\\sim}8\\mathrm{h}$ ，得到含有多个活泼N‑异丁氧基和/或N‑正丁氧基的亲水组分B；[0041] 步骤S103，将亲水组分A和亲水组分B混合，即得到防雾涂料；亲水组分A中的羟基与亲水组分B中的丁氧基的摩尔比为 $1.2{\\sim}1.5{:}1$ 。  \n\n[0042] 下面结合实施例对本申请提供的防雾涂料及其制备方法进行详细说明。  \n\n[0043] 下面结合实施例对本申请提供的防雾涂料进行详细说明。  \n\n[0044] 实施例1：  \n\n45] 实施例1提供了一种防雾涂料的制备方法，包括以下步骤：  \n\n[0046] (1)称取292 .28g异山梨醇和 $115.12\\mathrm{g}$ 二丙酮醇，在室温下搅拌溶解后，边搅拌边加入 $.168.19\\mathrm{g}$ 六亚甲基二异氰酸酯，然后升温至 $80{\\sim}85^{\\circ}\\mathrm{C}$ ，反应4h至NCO完全消耗，得到亲水聚合物；待亲水聚合物的温度降至小于 $40^{\\circ}\\mathrm{C}$ 后，称取614g吐温20和46.05g甘油与亲水聚合物混合均匀，得到亲水组分A；  \n\n[0047] (2)称取 $628.84\\mathrm{g}\\mathrm{N}^{-}$ (异丁氧基)甲基丙烯酰胺，再称取 $900\\mathrm{g}$ ED900，加入3g  4‑甲氧基苯酚，在 $60^{\\circ}\\mathrm{C}$ 下反应4h，再升温至 $80^{\\circ}\\mathrm{C}$ 反应6h，得到亲水组分B；  \n\n[0048] (3)称取 $40\\mathrm{g}$ 亲水组分A与 $50\\mathrm{g}$ 亲水组分B混合搅拌均匀，并加入醋酸丁酯稀释至方便涂布的黏度，即得到防雾涂料。  \n\n[0049] 将上述制得的防雾涂料均匀涂布在 $5\\mathrm{cm}\\times5\\mathrm{cm}$ 的PC板上，置于 $120^{\\circ}\\mathrm{C}$ 烘箱中烘烤10min后取出，均匀附着在板面上的涂层即为防雾涂层。  \n\n[0050] 实施例2：  \n\n[0051] 实施例2提供了一种防雾涂料的制备方法，包括以下步骤：  \n\n[0052] (1)称取2440g吐温 $^{-20}$ 和 $115.12\\mathrm{g}$ 二丙酮醇，在室温下搅拌溶解后，边搅拌边加入$168.19\\mathrm{g}$ 六亚甲基二异氰酸酯，然后升温至 $80{\\sim}85^{\\circ}\\mathrm{C}$ ，反应4h至NCO完全消耗，得到亲水聚合物；待亲水聚合物的温度降至小于 $40^{\\circ}\\mathrm{C}$ 后，称取 $655\\mathrm{g}$ 吐温80和 $46.05\\mathrm{g}$ 甘油与亲水聚合物混合均匀，得到亲水组分A；  \n\n[0053] (2)称取 $628.84\\mathrm{g}\\mathrm{N}\\cdot$ (正丁氧基)甲基丙烯酰胺，再称取 $900\\mathrm{g}$ ED900，加入 $3\\mathrm{g}$ 4‑甲氧基苯酚，在 $60^{\\circ}\\mathrm{C}$ 下反应4h，再升温至 $80^{\\circ}\\mathrm{C}$ 反应6h，得到亲水组分B；  \n\n[0054] (3)称取 $100\\mathrm{g}$ 亲水组分A与50g亲水组分B混合搅拌均匀，并加入醋酸丁酯稀释至方便涂布的黏度，即得到防雾涂料。  \n\n[0055] 将上述制得的防雾涂料均匀涂布在 $5\\mathrm{cm}\\times5\\mathrm{cm}$ 的PC板上，置于 $120^{\\circ}\\mathrm{C}$ 烘箱中烘烤15min后取出，均匀附着在板面上的涂层即为防雾涂层。  \n\n[0056] 实施例3：  \n\n[0057] 实施例3提供了一种防雾涂料的制备方法，包括以下步骤：  \n\n[0058] (1)称取292 .28g异山梨醇和 $115.12\\mathrm{g}$ 二丙酮醇，在室温下搅拌溶解后，边搅拌边加入222.28g异佛尔酮二异氰酸酯，然后升温至 $80{\\sim}85^{\\circ}\\mathrm{C}$ ，反应4h至NCO完全消耗，即得到亲水聚合物；待亲水聚合物的温度降至小于 $40^{\\circ}\\mathrm{C}$ 后，称取 $610\\mathrm{g}$ 甘油聚醚‑26与亲水聚合物混合均匀，即得到亲水组分A；  \n\n[0059] (2)称取 $628.84\\mathrm{g}$ N‑(异丁氧基)甲基丙烯酰胺，再称取 $600\\mathrm{g}$ ED600，加入 $3\\mathrm{g}$ 4‑甲氧基苯酚，在 $50^{\\circ}\\mathrm{C}$ 下反应4h，再升温至 $80^{\\circ}\\mathrm{C}$ 反应6h，即得到亲水组分B；  \n\n[0060] (3)称取 $40\\mathrm{g}$ 亲水组分A与 $25\\mathrm{g}$ 亲水组分B混合搅拌均匀，并加入醋酸丁酯稀释至方便涂布的黏度，即得到防雾涂料。  \n\n[0061] 将上述制得的防雾涂料均匀涂布在 $5\\mathrm{cm}\\times5\\mathrm{cm}$ 的PC板上，置于 $120^{\\circ}\\mathrm{C}$ 烘箱中烘烤20min后取出，均匀附着在板面上的涂层即为防雾涂层。  \n\n[0062] 对实施例 $1\\sim$ 实施例3的防雾涂层进行性能测试，结果见表1。  \n\n[0063] 表1：实施例 $1\\sim$ 实施例3的防雾涂层的性能测试结果  \n\n[0064]  \n\n<html><body><table><tr><td>项目</td><td>实施例1</td><td>实施例2</td><td>实施例3</td></tr><tr><td>涂层表观</td><td>平滑，指摸无痕</td><td>平滑，指摸有轻微痕迹</td><td>平滑，指摸无痕</td></tr><tr><td>涂层铅笔硬度</td><td>HB~H</td><td>B</td><td>2H</td></tr><tr><td>80℃热水水面上方5cm处</td><td>肉眼观察：视野清晰，</td><td>肉眼观察：视野清晰，</td><td>肉眼观察：视野清</td></tr><tr><td>初始防雾效果 泡100ppm次氯酸1h后是</td><td>不受影响 手扣不脱皮</td><td>不受影响 手扣脱皮</td><td>晰，不受影响 手扣不脱皮</td></tr><tr><td>否脱皮 泡100ppm次氯酸1h后防</td><td>肉眼观察：视野清晰，</td><td></td><td></td></tr><tr><td>雾效果</td><td>不受影响</td><td>肉眼观察：视野清晰， 不受影响</td><td>肉眼观察：视野清 晰，不受影响</td></tr></table></body></html>  \n\n[0065] 在本说明书的描述中，参考术语“一个实施例/方式”、“一些实施例/方式”、“示例”、“具体示例”或“一些示例”等的描述意指结合该实施例/方式或示例描述的具体特征、结构、材料或者特点包含于本申请的至少一个实施例/方式或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例/方式或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例/方式或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例/方式或示例以及不同实施例/方式或示例的特征进行结合和组合。  \n\n[0066] 需要说明的是，在本申请中，诸如“第一”和“第二”等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来，而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。在没有更多限制的情况下，由语句“包括一个……”限定的要素，并不排除在包括所述要素的过程、方法、物品或者设备中还存在另外的相同要素。在本申请中，“多个”的含义是至少两个，例如两个、三个等，除非另有明确具体的规定。  \n\n[0067] 以上所述仅是本申请的具体实施方式，使本领域技术人员能够理解或实现本申请。对这些实施例的多种修改对本领域的技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本申请的精神或范围的情况下，在其它实施例中实现。因此，本申请将不会被限制于本文所示的这些实施例，而是要符合与本文所申请的原理和新颖特点相一致的最宽的范围。  \n\n![](images/67ddf0de5cd1d8d37e2c8d09ed3199bf5be6b7819bc2ce9bd63b0b7b610b5e92.jpg)  \n图1",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# (19)国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n<html><body><table><tr><td>(21)申请号202211456880.4</td><td>C09D 183/16 (2006.01)</td></tr><tr><td>(22)申请日 2022.11.21</td><td>(56)对比文件</td></tr><tr><td>(65)同一申请的已公布的文献号</td><td>CN 104673090 A,2015.06.03</td></tr><tr><td>申请公布号CN 116023854 A</td><td>CN 113603850 A,2021.11.05</td></tr><tr><td>(43)申请公布日2023.04.28</td><td>CN 114752302 A,2022.07.15</td></tr><tr><td>(73)专利权人 武汉中科先进材料科技有限公司</td><td>CN 114761496 A,2022.07.15</td></tr><tr><td>地址430000 湖北省武汉市武汉经济技术</td><td>审查员赵丹</td></tr><tr><td>开发芙蓉路1号华中智谷F10栋1-2层</td><td></td></tr><tr><td>(72)发明人康翼鸿喻学锋程文杰何睿</td><td></td></tr><tr><td>杨帆吴列甄亚枝</td><td></td></tr><tr><td>(74)专利代理机构武汉高得专利代理事务所</td><td></td></tr><tr><td>（普通合伙）42268</td><td></td></tr><tr><td>专利代理师陈挥秀</td><td></td></tr><tr><td></td><td></td></tr></table></body></html>  \n\n(51)Int.Cl. C09D 183/04(2006.01)",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n一种高硬度耐摩擦防雾涂料及制备方法",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明提供一种高硬度耐摩擦防雾涂料，组分包括亲水环状聚硅氧烷、聚硅氮烷、固化剂、流平剂、溶剂。该涂料以亲水改性的聚硅氧烷为主体，聚硅氧烷具有刚性环状结构，表面既含有亲水基团发挥亲水防雾作用，又含有环氧基团可与固化剂交联固化，环氧基团开环后形成的羟基又可以参与聚硅氮烷的交联固化，形成聚硅氧烷和聚硅氮烷的互穿网络结构，这种刚性的以无机结构为主的致密网络，赋予防雾涂层高硬度和高耐摩擦性，对玻璃和塑料基材的附着力强，并且在常温下即可完成固化过程。  \n\n1.一种高硬度耐摩擦防雾涂料，其特征在于，包括以下质量份的组份：亲水环状聚硅氧烷50‑80份、聚硅氮烷20‑50份、固化剂5‑20份、流平剂0 .1‑1 .0份、溶剂100‑500份；所述的亲水环状聚硅氧烷由以下方式制备：由二乙醇胺与环状聚硅氧烷按照摩尔比1∶1‑4∶1反应得到预聚体1；由二异氰酸酯和单羟基封端的聚氧乙烯醚按照摩尔比1∶1反应得到半封端预聚体2；将所述预聚体1再与所述预聚体2按照摩尔比1∶3‑1∶12反应得到所述亲水环状聚硅氧烷；所述环状聚硅氧烷为缩水甘油醚氧丙基环四硅氧烷、缩水甘油醚氧丙基笼状聚倍半硅氧烷、八环氧环己基乙基笼状聚倍半硅氧中的至少一种；所述固化剂包括二乙烯三胺、三乙烯四胺、二乙氨基丙胺、聚醚胺D230、聚醚胺D400、聚醚胺ED600中的至少一种；所述溶剂包括乙酸乙酯、乙酸丁酯、正丁醚、环己酮中的一种或多种的组合。  \n\n2.根据权利要求1所述的高硬度耐摩擦防雾涂料，其特征在于：所述聚硅氮烷包括全氢聚硅氮烷，有机聚硅氮烷的任意一种。  \n\n3.根据权利要求2所述的高硬度耐摩擦防雾涂料，其特征在于：所述有机聚硅氮烷的侧链或端基由一个或多个乙烯基，甲基，苯基，环氧基组成。  \n\n4.根据权利要求1所述的高硬度耐摩擦防雾涂料，其特征在于：所述流平剂包括氟素润湿流平剂FSWET1010、含氟流平剂FS3100、聚醚硅氧烷流平剂TEGO410中的至少一种。  \n\n5.一种权利要求1‑4任一项所述的高硬度耐摩擦防雾涂料的制备方法，其特征在于，包括以下步骤：  \n\n步骤一，按质量份称取亲水环状聚硅氧烷、聚硅氮烷、固化剂、流平剂、溶剂；  \n\n步骤二，在容器中加入溶剂，然后在搅拌状态下依次加入亲水环状聚硅氧烷、聚硅氮烷、流平剂和固化剂混合均匀即得所述防雾涂料。  \n\n6.根据权利要求5所述的高硬度耐摩擦防雾涂料的制备方法，其特征在于：所述的二异氰酸酯包括异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯中的一种或多种的组合；所述的单羟基封端的聚氧乙烯醚包括聚乙二醇单甲醚200，聚乙二醇单甲醚350，聚乙二醇单甲醚500，聚乙二醇单甲醚750，聚乙二醇单甲醚1000中的一种或多种的组合。  \n\n7.一种高硬度耐摩擦防雾涂料在防雾涂层上的应用，其特征在于，将权利要求1‑4任一项所述防雾涂料或根据权利要求5‑6任一项所述方法制备的防雾涂料涂覆在基质上，经固化后形成所述防雾涂层；所述基质包括玻璃和塑料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 一种高硬度耐摩擦防雾涂料及制备方法",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明属于涂料技术领域，具体涉及一种防雾涂料及其制备方法和应用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 透明玻璃和聚合物材料具有优异的光学性能，在日常生活中应用广泛。但是这些材料在实际使用时，由于环境改变产生温差变化，空气中的水蒸气很容易在这些材料表面凝结成水滴，产生雾气，导致其透明性和能见度急剧下降。起雾现象不但降低了材料本身的透明度,影响相关产品的使用,还会给设备的运行安全带来隐患。  \n[0003] 因此,如何防雾逐渐引起研究人员和产业届的关注。常见的防雾技术有自动擦拭、热力防雾、表面涂层等。其中,具有主动防雾性能的超亲水表面涂层技术在施工简便性、持续防护性及运行维护成本的经济性等方面具有独特优势,是最有发展潜力的防雾技术。[0004] 目前，在众多超亲水涂层的制备方法中，化学涂料涂覆具有操作简便，成本低，适合大规模生产等优点，因此最受瞩目。由于具有防雾功能的化学涂料通常为有机聚合物，容易在塑料基材上附着，但难以在玻璃基材上附着，固化后形成的涂层硬度普遍较低，不耐摩擦，造成使用寿命短。无机聚硅氧烷聚合物的硬度高，耐磨性优异，近年来备受瞩目。虽然国内外学者也陆续报道了有机无机杂化防雾涂料，但有机物的含量仍占主体地位，难以根本解决防雾涂料硬度和耐磨差的问题。因此，开发以无机组分为主的高硬度耐摩擦的防雾涂料是十分有必要的。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0005] 本发明的目的是针对现有技术的不足，本发明提供一种高硬度耐摩擦防雾涂料，该涂料以亲水改性的聚硅氧烷为主体，聚硅氧烷具有刚性环状结构，表面既含有亲水基团发挥亲水防雾作用，又含有环氧基团可与固化剂交联固化，环氧基团开环后形成的羟基又可以参与聚硅氮烷的交联固化，形成聚硅氧烷和聚硅氮烷的互穿网络结构，这种刚性的以无机结构为主的致密网络，赋予防雾涂层高硬度和高耐摩擦性，对玻璃和塑料基材的附着力强，并且在常温下即可完成固化过程。  \n\n[0006] 为实现上述目的，本发明采用的技术方案如下：  \n\n[0007] 首先，本发明提供一种高硬度耐摩擦防雾涂料，包括以下质量份的组份：亲水环状聚硅氧烷50‑80份、聚硅氮烷20‑50份、固化剂5‑20份、流平剂0.1‑1 .0份、溶剂100‑500份。  \n\n[0008] 优选的，所述环状聚硅氧烷端基含环氧基团，能够与氨基进行开环反应。  \n\n[0009] 优选的，所述环状聚硅氧烷为缩水甘油醚氧丙基环四硅氧烷、缩水甘油醚氧丙基笼状聚倍半硅氧烷、八环氧环己基乙基笼状聚倍半硅氧中的至少一种。  \n\n[0010] 所述有机聚硅氮烷(OPSZ)的侧链或端基由一个或多个乙烯基，甲基，苯基，环氧基 等基团组成。  \n\n[0011] 优选的，所述聚硅氮烷包括全氢聚硅氮烷(PHPS)，有机聚硅氮烷(OPSZ)的任意一种。  \n\n[0012] 优选的，所述固化剂为热固型环氧固化剂，能够与亲水环状聚硅氧烷中的环氧基发生交联反应，从而实现交联固化；优选的，包括二乙烯三胺、三乙烯四胺、二乙氨基丙胺、聚醚胺(D230)、聚醚胺(D400)、聚醚胺(ED600)中的至少一种。  \n\n[0013] 优选的，所述流平剂包括氟素润湿流平剂(FSWET1010)、含氟流平剂(FS3100)、聚醚硅氧烷流平剂(TEGO410)中的至少一种。  \n\n[0014] 优选的，所述溶剂包括乙酸乙酯、乙酸丁酯、正丁醚、环己酮中的一种或多种的组合。  \n\n015] 一种高硬度耐摩擦防雾涂料的制备方法，其特征在于，包括以下步骤：  \n\n[0016] 步骤一，按质量组分称取亲水环状聚硅氧烷、聚硅氮烷、固化剂、流平剂、溶剂；  \n\n[0017] 步骤二，在容器中加入溶剂，然后在搅拌状态下依次加入亲水环状聚硅氧烷、聚硅氮烷、流平剂和固化剂混合均匀即得所述防雾涂料。  \n\n[0018] 优选的，步骤一中所述的亲水环状聚硅氧烷由以下方式制备：由二乙醇胺与环状聚硅氧烷按照摩尔比1:1‑4:1反应得到预聚体1；由二异氰酸酯和单羟基封端的聚氧乙烯醚按照摩尔比1:1反应得到半封端预聚体2；将所述预聚体1再与所述预聚体2按照摩尔比1:31:12反应得到所述亲水环状聚硅氧烷。  \n\n[0019] 优选的，所述的二异氰酸酯包括异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、六亚甲基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(HMDI)中的一种或多种的组合；所述的单羟基封端的聚氧乙烯醚包括聚乙二醇单甲醚200，聚乙二醇单甲醚350，聚乙二醇单甲醚500，聚乙二醇单甲醚750，聚乙二醇单甲醚1000中的一种或多种的组合。  \n\n[0020] 本发明再一方面提供了一种上述所述的防雾涂料在制备防雾涂层中的应用。  \n\n[0021] 本发明再一方面提供了一种防雾涂层，由以下方法制备得到：将上述所述的防雾涂料涂覆在基质上，经固化后形成所述防雾涂层；即上述防雾涂料在防雾涂层上的应用。  \n\n[0022] 优选地，所述基质包括玻璃、塑料，具体包括汽车玻璃，建筑物玻璃，广告牌，浴室镜及公共交通工具玻璃；  \n\n[0023] 优选地，所述涂覆的方法包括刮涂、滴涂、辊涂、淋涂、旋涂；  \n\n[0024] 优选地，所述固化的方法是加热固化，或在室温条件下放置3‑7d即可。  \n\n[0025] 与现有技术相比，本发明具有如下突出效果：  \n\n[0026] 本发明设计了一种亲水改性的聚硅氧烷，防雾涂料以亲水改性的聚硅氧烷为主体，该聚硅氧烷具有刚性环状结构，表面既含有亲水基团发挥亲水防雾作用，又含有环氧基团可与固化剂交联固化，环氧基团开环后形成的羟基又可以参与聚硅氮烷的交联固化，形成聚硅氧烷和聚硅氮烷的互穿网络结构，这种刚性的以无机结构为主的致密网络，赋予防雾涂层高硬度和高耐摩擦性，对玻璃和塑料基材的附着力强，并且在常温下即可完成固化过程。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 具体实施方式  \n\n[0027] 下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。  \n\n[0028] 制备亲水环状聚硅氧烷的过程中还可额外添加二月桂酸二丁基锡DBTDL，此为常规选择，对性能没有影响，起到催化剂的作用。  \n\n[0029] 实施例1防雾涂层的制备  \n\n[0030] (a)亲水环状聚硅氧烷的制备： $250\\mathrm{mL}$ 的三口烧瓶中加入 $.69.7\\mathrm{g}\\left(0.1\\mathrm{mol}\\right)$ 缩水甘油醚氧丙基环四硅氧烷开启搅拌；另称取 $21.0\\mathrm{g}\\left(0.2\\mathrm{mol}\\right)$ 二乙醇胺加至上述三口烧瓶中，80度反应3h后，测得PH值呈中性，得到预聚体1；  \n\n[0031] 另取 $1000\\mathrm{mL}$ 三口烧瓶，向其加入 $\\mathrm{133.3g\\left(0.6mol\\right)}$ 异佛尔酮二异氰酸酯和 $0.2\\mathrm{g}$ $(0.05\\mathrm{wt}\\%)$ 二月桂酸二丁基锡开启搅拌；另取 $300.0\\mathrm{g}\\left(0.6\\mathrm{mol}\\right)$ 聚乙二醇单甲醚500，充分混合至完全溶解，转移至恒压滴液漏斗中，在室温下缓慢滴加至上述三口烧瓶中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $70^{\\circ}\\mathrm{C}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值(通过盐酸二正丁胺法测定)，得到预聚体2，加入预聚体1继续反应直至异氰酸酯基(‑NCO)的含量为零，得到亲水环状聚硅氧烷，降温干燥密封保存。  \n\n[0032] (b)防雾涂料的制备：取乙酸乙酯200份、正丁醚100份加入分散容器，边搅拌边加入亲水环状聚硅氧烷60份、全氢聚硅氮烷25份、聚醚胺ED60015份、流平剂FSWET10100.1份，高速分散10min，得到均匀透明的防雾涂料。  \n\n[0033] (c)防雾涂层的制备：将(b)中制备的防雾涂料用线棒均匀的涂在干净的玻璃上，在80度烘烤2h即得防雾涂层。  \n\n[0034] 实施例2防雾涂层的制备  \n\n[0035] (a)亲水环状聚硅氧烷的制备：250mL的三口烧瓶中加入 $.133.7\\mathrm{g}\\left(0.1\\mathrm{mol}\\right)$ 缩水甘油醚氧丙基笼状聚倍半硅氧烷开启搅拌；另称取 $31.5\\mathrm{g}\\left(0.3\\mathrm{mol}\\right)$ 二乙醇胺加至上述三口烧瓶中，80度反应3h后，测得PH值呈中性，得到预聚体1；  \n\n[0036] 另取 $1000\\mathrm{mL}$ 三口烧瓶，向其加入 $200.1\\mathrm{g}\\left(0.9\\mathrm{mol}\\right)$ 异佛尔酮二异氰酸酯和 $0.4\\mathrm{g}$ $(0.05\\mathrm{wt}\\%)$ 二月桂酸二丁基锡开启搅拌；另取 $675.0\\mathrm{g}\\left(0.9\\mathrm{mol}\\right)$ 聚乙二醇单甲醚750，充分混合至完全溶解，转移至恒压滴液漏斗中，在室温下缓慢滴加至上述三口烧瓶中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $70^{\\circ}\\mathrm{C}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值(通过盐酸二正丁胺法测定)，得到预聚体2，加入预聚体1继续反应直至异氰酸酯基(‑NCO)的含量为零，得到亲水环状聚硅氧烷，降温干燥密封保存。  \n\n[0037] (b)防雾涂料的制备：将亲水环状聚硅氧烷50份、全氢聚硅氮烷40份、二乙烯三胺10份、流平剂TEGO4100.1份、乙酸乙酯100份，正丁醚200份加入分散料筒内高速分散10min，得到均匀透明的防雾涂料。  \n\n[0038] (c)防雾涂层的制备：将(b)中制备的防雾涂料旋涂在干净的PC板上，然后放在室 温条件下放置7d即得防雾涂层。  \n\n[0039] 实施例3防雾涂层的制备  \n\n[0040] (a)亲水环状聚硅氧烷的制备：250mL的三口烧瓶中加入141 .8g(0 .1mol)八环氧环己基乙基笼状聚倍半硅氧开启搅拌；另称取 $21.0\\mathrm{g}\\left(0.2\\mathrm{mol}\\right)$ 二乙醇胺加至上述三口烧瓶中，80度反应3h后，测得PH值呈中性，得到预聚体1；  \n\n[0041] 另取 $1000\\mathrm{mL}$ 三口烧瓶，向其加入 $100.8\\mathrm{g}\\left(0.6\\mathrm{mol}\\right)$ 六亚甲基二异氰酸酯和 $0.15\\mathrm{g}$ $(0.05\\mathrm{wt}\\%)$ 二月桂酸二丁基锡开启搅拌；另取 $210.0\\mathrm{g}\\left(0.6\\mathrm{mol}\\right)$ 聚乙二醇单甲醚350，充分混合至完全溶解，转移至恒压滴液漏斗中，在室温下缓慢滴加至上述三口烧瓶中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $70^{\\circ}\\mathrm{C}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值(通过盐酸二正丁胺法测定)，得到预聚体2，加入预聚体1继续反应直至异氰酸酯基(‑NCO)的含量为零，得到亲水环状聚硅氧烷，降温干燥密封保存。  \n\n[0042] (b)防雾涂料的制备：将亲水环状聚硅氧烷50份、有机聚硅氮烷35份、三乙烯四胺15份、流平剂FS31000.5份、乙酸丁酯100份，正丁醚200份加入分散料筒内高速分散10min，得到均匀透明的防雾涂料。  \n\n[0043] (c)防雾涂层的制备：将(b)中制备的防雾涂料淋涂在干净的玻璃上， $80^{\\circ}\\mathrm{C}$ 烘烤 $\\mathrm{2h}$ 即得防雾涂层。  \n\n[0044] 实施例4防雾涂层的制备  \n\n[0045] (a)亲水环状聚硅氧烷的制备： $250\\mathrm{mL}$ 的三口烧瓶中加入141 .8g(0 .1mol)八环氧环己基乙基笼状聚倍半硅氧开启搅拌；另称取 $31.5\\mathrm{g}\\left(0.3\\mathrm{mol}\\right)$ 二乙醇胺加至上述三口烧瓶中，80度反应3h后，测得PH值呈中性，得到预聚体1；  \n\n[0046] 另取 $1000\\mathrm{mL}$ 三口烧瓶，向其加入 $156.7\\mathrm{g}\\left(0.9\\mathrm{mol}\\right)$ 甲苯二异氰酸酯和 $0.15\\mathrm{g}$ $(0.05\\mathrm{wt}\\%)$ 二月桂酸二丁基锡开启搅拌；另取 $315.0\\mathrm{g}\\left(0.9\\mathrm{mol}\\right)$ 聚乙二醇单甲醚350，充分混合至完全溶解，转移至恒压滴液漏斗中，在室温下缓慢滴加至上述三口烧瓶中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 $70\\mathrm{{^\\circC}}$ 反应直至混合物的异氰酸酯基(‑NCO)的含量达到理论值(通过盐酸二正丁胺法测定)，得到预聚体2，加入预聚体1继续反应直至异氰酸酯基(‑NCO)的含量为零，得到亲水环状聚硅氧烷，降温干燥密封保存。  \n\n[0047] (b)防雾涂料的制备：将将亲水环状聚硅氧烷60份、有机聚硅氮烷30份、聚醚胺D23010份、流平剂FS31000 .5份、环己酮100份，正丁醚200份加入分散料筒内高速分散10min，得到均匀透明的防雾涂料。  \n\n[0048] (c)防雾涂层的制备：将(b)中制备的防雾涂料滴涂在干净的PMMA板上， $80^{\\circ}\\mathrm{C}$ 烘烤2h即得防雾涂层。  \n[0049] 实施例5性能测试  \n[0050] 实施例1‑4所制得的防雾涂层的性能测试项目和方法如下表所示：  \n\n<html><body><table><tr><td>项目</td><td>方法</td></tr><tr><td>铅笔硬度</td><td>通过铅笔硬度仪按照GB/T6739-1996 中的规定进行</td></tr><tr><td>附着力</td><td>采用百格法，交叉划格形成10X10的小 方格。用3M-610压敏胶带紧密粘附于 涂层表面，然后沿90度方向快速撕去 胶带，观测格子边缘的破坏程度</td></tr><tr><td>烧杯防雾测试</td><td>涂层置于50℃热水上方标准高度，面向 水蒸气高达3分钟。如果测试中形成连 续的水膜，则不会再起雾。如果测试中 起雾，记录从开始测试到出现雾的时间</td></tr><tr><td>初始防雾</td><td>防雾测试中3分钟不起雾，则通过</td></tr><tr><td>哈气测试</td><td>朝涂层哈气，观察起雾情况</td></tr><tr><td>室温水浸泡-防雾测试（冷水测试）</td><td>样品在室温水中浸泡1小时，取出，干 燥12小时，进行烧杯防雾测试</td></tr><tr><td>沸水浸泡-防雾测试 (沸水测试)</td><td>样品在沸水中煮1小时，取出，冷却干 燥12小时，进行烧杯防雾测试</td></tr><tr><td>初始雾度</td><td>采用透光率/雾度测定仪按照GB/T 2410-2008进行测试，小于1.0%不会被 目测观察到</td></tr><tr><td>落沙-雾度测试</td><td>观察落沙试验后，雾度升高值</td></tr><tr><td>化学品擦拭测试（耐化学品）</td><td>样品分别用在甲基乙基酮和异丙醇中 浸泡过的布擦拭，观察是否出现异常</td></tr><tr><td>钢丝绒测试 (耐划伤）</td><td>#0000钢丝绒，500克压力，擦50个来 回。1-2个划痕为非常好；3-5个擦痕为 好；多于5个擦痕为差。</td></tr><tr><td>粘性测试</td><td>用棉花擦样品表面，不残留纤维为光 滑，残留纤维越多说明越粘</td></tr></table></body></html>  \n\n[0051]  \n\n[0052] 实施例1‑4所制得的防雾涂层的性能测试结果如下表所示：  \n\n<html><body><table><tr><td rowspan=\"13\">0053]</td><td></td><td></td><td>实施 例1</td><td>实施 例2</td><td>实施 例3</td><td>实施 例4</td></tr><tr><td>初始雾度</td><td></td><td>0.2%</td><td>0.1%</td><td>0.1%</td><td>0.1%</td></tr><tr><td>落沙-雾度</td><td>观察落沙测试后，雾度升 高值</td><td>2.8%</td><td>2.0%</td><td>2.4%</td><td>2.1%</td></tr><tr><td>初始防雾</td><td>3min不起雾，则通过</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>哈气</td><td>不起雾则通过</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>冷水测试</td><td>观察开始测试到出现雾 的时间</td><td>>180s</td><td>>180s</td><td>>180s</td><td>>180s</td></tr><tr><td>沸水测试</td><td>观察开始测试到出现雾 的时间</td><td>>180s</td><td>>180s</td><td>>180s</td><td>>180s</td></tr><tr><td>耐化学品</td><td>化学品布擦拭</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>铅笔硬度</td><td>铅笔测试仪</td><td>6H</td><td>5H</td><td>7H</td><td>7H</td></tr><tr><td>耐划伤</td><td>钢丝绒测试，记划痕数</td><td>1</td><td>2</td><td>0</td><td>1</td></tr><tr><td>附着力</td><td>划格</td><td>0级</td><td>0级</td><td>0级</td><td>0级</td></tr><tr><td>粘性测试</td><td></td><td>光滑</td><td>光滑</td><td>光滑</td><td>光滑</td></tr></table></body></html>  \n\n[0054] 综上，本发明创造性的利用二乙醇胺，环状聚硅氧烷和亲水异氰酸酯预聚体合成了亲水的环状聚硅氧烷，该聚硅氧烷具有刚性环状结构，表面既含有亲水基团发挥亲水防雾作用，又含有环氧基团可与固化剂交联固化，环氧基团开环后形成的羟基又可以参与聚硅氮烷的交联固化，形成聚硅氧烷和聚硅氮烷的互穿网络结构，这种刚性的以无机结构为主的致密网络，赋予防雾涂层高硬度和高耐摩擦性，对玻璃和塑料基材的附着力强，并且在常温下即可完成固化过程。",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,52 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n<html><body><table><tr><td>(21)申请号 202310044231.1 (56)对比文件</td></tr><tr><td>(22)申请日 2023.01.29 CN 104610873 A,2015.05.13</td></tr><tr><td>CN 105694045 A,2016.06.22</td></tr><tr><td>(65)同一申请的已公布的文献号 CN 108659471 A,2018.10.16</td></tr><tr><td>申请公布号CN 116554477A CN 111961206 A,2020.11.20</td></tr><tr><td>(43)申请公布日2023.08.08 CN 113372814 A,2021.09.10</td></tr><tr><td>CN 113880534 A,2022.01.04 (73)专利权人武汉中科先进材料科技有限公司</td></tr><tr><td>地址 430000 湖北省武汉市经济技术开发 US 2016083526 A1,2016.03.24</td></tr><tr><td>区201M地块华人汇和科技园(华中智 US 2021189173 A1,2021.06.24</td></tr><tr><td>WO 2015076632 A1,2015.05.28 谷)一期F10研发楼1-2层</td></tr><tr><td>WO 2018117974 A1,2018.06.28 (72)发明人康翼鸿喻学锋谢雨晴吴列 WO 2022160983 A1,2022.08.04</td></tr><tr><td>肖中伟‧程文杰　杨帆 Liu DD，et al.Responsive Hybrid</td></tr><tr><td>(74)专利代理机构 武汉高得专利代理事务所 Microcapsules by the One-Step Interfacial</td></tr><tr><td>（普通合伙）42268 Thiol- Ene</td></tr><tr><td>专利代理师 姜璐 Photopolymerization.Langmuir.2013,第29卷</td></tr><tr><td>(51)Int.CI . 5307-5314.</td></tr><tr><td>C08G 77/38 (2006.01) 吴城锋;朱卫彪;何瑾馨;董霞.聚醚改性多</td></tr><tr><td>面体低聚倍半硅氧烷构筑耐水性亲水防雾涂层.</td></tr><tr><td>C08G 77/392 (2006.01) 表面技术.2020，(第08期)，133-141.</td></tr><tr><td>C09D 183/08 (2006.01)</td></tr><tr><td>CO9D 5/08 (2006.01) 审查员 李娟</td></tr></table></body></html>  \n\n权利要求书1页 说明书7页 附图1页",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\nPOSS改性聚合物及其制备方法、包含其的超亲水涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本申请涉及高分子材料技术领域，特别涉及一种POSS改性聚合物及其制备方法、包含其的超亲水涂料。本申请提供的POSS改性聚合物的制备方法包括以下步骤：将巯基丙酸与八环氧环己基乙基笼状聚倍半硅氧烷混合，加入第一催化剂进行加热反应，得到中间体；向中间体中加入乙氧  \n化三羟甲基丙烷三丙烯酸酯和第二催化剂在室  \n申温方请便下提，进其供行结的点构P击O中S反S含改应有性，醚即聚键得合、到物酯P键制OS备、S环改过氧性程基聚简等合单多物，种涂。官本装能团，增强了对ABS基材的附着力，附着力测试等级为0级。  \n\n![](images/ce8b55e0d8969d893a17a15ec45f5c92b9602bd7859728da02a365b488a4c0bd.jpg)  \n\n1.一种POSS改性聚合物的制备方法，其特征在于，包括以下步骤：  \n\n将巯基丙酸与八环氧环己基乙基笼状聚倍半硅氧烷混合，加入第一催化剂进行加热反应，得到中间体；  \n\n向中间体中加入乙氧化三羟甲基丙烷三丙烯酸酯和第二催化剂在室温下进行点击反应，即得到POSS改性聚合物；  \n\n其中，八环氧环己基乙基笼状聚倍半硅氧烷与巯基丙酸的摩尔比为1：2～1：8；乙氧化三羟甲基丙烷三丙烯酸酯与中间体的摩尔比为 $1:1\\sim1:3$ 。  \n\n2.根据权利要求1所述的POSS改性聚合物的制备方法，其特征在于，所述第一催化剂选用三乙胺，所述第二催化剂选用碳酸钠。  \n\n3.根据权利要求1‑2任一项所述制备方法制得的POSS改性聚合物，其特征在于，所述POSS改性聚合物的结构式如式(Ⅰ)所示：  \n\n![](images/a24e4ba1d2ad5f69957fcf4a28017777c0c6856a588b3e1663cfdc3dfcca14d7.jpg)  \n\n式(Ⅰ)中， $\\mathrm{m}+\\mathrm{n}+1=3\\sim20$ 。  \n\n4.一种超亲水涂料，其特征在于，包括以下质量份的原料：POSS改性聚合物 $33\\sim48$ 份，表面活性剂 $3\\sim5$ 份，光固化单体 $25\\sim45$ 份，光固化两性离子单体 $10\\sim15$ 份，活性稀释剂单体$5\\sim10$ 份，流平剂 $1\\sim2$ 份，光引发剂 $3\\sim5$ 份；所述POSS改性聚合物由权利要求1‑2任一项制备方法制得。  \n\n5.根据权利要求4所述的超亲水涂料，其特征在于，所述表面活性剂选用非离子氟表面活性剂；所述流平剂选用丙烯酸酯类流平剂。  \n\n6.根据权利要求4所述的超亲水涂料，其特征在于，所述光固化单体选用乙氧化双酚A二丙烯酸酯、乙二醇二甲基丙烯酸酯中的一种或两种的混合。  \n\n7.根据权利要求4所述的超亲水涂料，其特征在于，所述光固化两性离子单体选用2‑丙烯酰胺‑2‑甲基丙磺酸、烯丙氧基壬基酚丙醇聚氧乙烯醚硫酸铵中的一种或两种的混合。  \n\n8.根据权利要求4所述的超亲水涂料，其特征在于，所述活性稀释剂单体选用丙烯酸、衣康酸、丙烯酸羟乙酯中的一种或多种的混合；所述光引发剂选用2‑羟基‑2‑甲基‑1‑苯基丙酮、1‑羟基环己基苯基甲酮、2,4,6‑三甲基苯甲酰基‑二苯基氧化膦中的一种或多种的混合。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# POSS改性聚合物及其制备方法、包含其的超亲水涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本申请涉及高分子材料技术领域，特别涉及一种POSS改性聚合物及其制备方法、包含其的超亲水涂料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] ABS材料是丙烯腈、1，3‑丁二烯、苯乙烯三种单体的接枝共聚物，具有原料易得、综合性能良好、价格便宜、用途广泛的优点，在机械、电气、纺织、汽车、飞机、轮船等制造工业及化工中应用广泛。为了增强ABS基材表面装饰，通常会在其表面涂覆涂料，超亲水涂层表面光滑润泽，将超亲水涂层涂覆在ABS基材上，能够实现防雾，提高基材性能。  \n\n[0003] 现有超亲水涂层的原料大部分为亲水材料，而ABS基材疏水组分多、极性低，二者相容性差，导致涂层附着力低，从而使涂层容易脱落，耐候性差。专利CN105176371B公开了一种紫外光固化涂料及制备方法和超亲水透明防雾涂层及制备方法，具体公开了利用表面接枝有烯键和磺酸基的改性硅溶胶、UV树脂低聚物、活性稀释剂、表面活性剂和光引发剂等成分制备得到紫外光固化涂料，该涂料制得的涂层具有长效超亲水性能和优良的防雾性能，但是该方法的原料为纳米二氧化硅，无机纳米粒子制备过程复杂，涂装工艺难度大，导致应用环境有限。  \n\n[0004] 基于以上分析，提供一种制备简便、能够增强超亲水涂层在ABS基材上的附着力的有机化合物十分重要。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0005] 本申请实施例提供一种POSS改性聚合物，以解决相关技术中ABS基材与超亲水涂层相容性差的问题。  \n[0006] 第一方面，本申请提供了一种POSS改性聚合物的制备方法，包括以下步骤：[0007] 将巯基丙酸与八环氧环己基乙基笼状聚倍半硅氧烷混合，加入第一催化剂进行加热反应，得到中间体；  \n[0008] 向中间体中加入乙氧化三羟甲基丙烷三丙烯酸酯和第二催化剂在室温下进行点击反应，即得到POSS改性聚合物。  \n[0009] 一些实施例中，所述第一催化剂选用三乙胺。  \n[0010] 一些实施例中，加热反应的温度为 $95\\sim110^{\\circ}\\mathrm{C}$ ，反应时间为 $3\\sim6\\mathrm{h}$ 。  \n[0011] 一些实施例中，八环氧环己基乙基笼状聚倍半硅氧烷与巯基丙酸的摩尔比为1：2$\\sim1{:}8$ 。  \n[0012] 一些实施例中，所述第二催化剂选用碳酸钠。  \n[0013] 一些实施例中，乙氧化三羟甲基丙烷三丙烯酸酯与中间体的摩尔比为 $1:1\\sim1:3$ 。[0014] 第二方面，本申请提供了一种利用上述制备方法制得的POSS改性聚合物，该POSS改性聚合物的骨架为Poss改性过的乙氧化丙烯酸酯单体，分子链段中包含 $3\\sim20$ 个聚乙二醇单元，其结构式如式(Ⅰ)所示：  \n\n[0015] 式(Ⅰ)：  \n\n![](images/f390c149aa19cdab7e454005f424960873df12e28cf7d56cd8107ce256881ad9.jpg)  \n\n[0016]  \n\n![](images/0df3888adb66d92ef7beb029642cadc03047f5fd966fa476c3ddb93f82a6ced3.jpg)  \n\n[0017] 式(Ⅰ)中， $\\mathrm{m+n+1}{=}3\\sim20\\mathrm{_{o}P0S S}$ 改性聚合物中，环氧基团提供附着作用，poss基团提供硬度，SH基团提供固化。  \n\n[0018] 第三方面，本申请提供了一种超亲水涂料，按质量份计，包括以下原料：POSS改性聚合物 $30\\sim48$ 份，表面活性剂 $3\\sim8$ 份，光固化单体 $20\\sim45$ 份，光固化两性离子单体 $10\\sim20$ 份，活性稀释剂单体 $3\\sim10$ 份，流平剂 $1\\sim3$ 份，光引发剂 $3\\sim6$ 份。  \n\n[0019] 一些实施例中，所述超亲水涂料包括以下质量份的原料：POSS改性聚合物 $33\\sim48$ 份，表面活性剂 $3\\sim5$ 份，光固化单体 $25\\sim45$ 份，光固化两性离子单体 $10\\sim15$ 份，活性稀释剂单体 $5\\sim10$ 份，流平剂 $1\\sim2$ 份，光引发剂 $3\\sim5$ 份。  \n\n[0020] 一些实施例中，所述超亲水涂料的原料还包括溶剂，溶剂的使用量为其它组分总重量的 $1\\sim3$ 倍。  \n\n[0021] 一些实施例中，所述溶剂选用乙酸乙酯、乙酸丁酯、乙醇、异丙醇中的一种或多种的混合。  \n\n[0022] 一些实施例中，所述表面活性剂选用非离子氟表面活性剂。  \n\n[0023] 一些实施例中，所述光固化单体选用乙氧化双酚A二丙烯酸酯、乙二醇二甲基丙烯酸酯中的一种或两种的混合。  \n\n[0024] 一些实施例中，所述光固化两性离子单体选用2‑丙烯酰胺‑2‑甲基丙磺酸(AMPS)、烯丙氧基壬基酚丙醇聚氧乙烯醚硫酸铵(DNS‑86)中的一种或两种的混合。  \n\n[0025] 一些实施例中，所述活性稀释剂单体选用丙烯酸、衣康酸、丙烯酸羟乙酯(HEA)中的一种或多种的混合。  \n\n[0026] 一些实施例中，所述流平剂选用丙烯酸酯类流平剂，分子量在6000‑20000之间。流平剂能有效降低涂料表面张力，提高其流平性和均匀性，能促使涂料在干燥成膜过程中形成一个平整、光滑、均匀的涂膜。  \n\n[0027] 一些实施例中，所述光引发剂选用2‑羟基‑2‑甲基‑1‑苯基丙酮(1173)、1‑羟基环己基苯基甲酮(184)、2,4,6‑三甲基苯甲酰基‑二苯基氧化膦(TPO)中的一种或多种的混合。光引发剂能在紫外光区 $(250\\sim420\\mathrm{nm})$ )吸收一定波长的能量，产生自由基、阳离子等，从而引发单体聚合交联固化。  \n\n[0028] 第四方面，本申请还提供了一种用于ABS基材的超亲水涂层的制备方法，具体为：  \n\n将上述超亲水涂料涂覆在ABS基材上， $60-80^{\\circ}\\mathrm{C}$ 预烘2‑3min，紫外LED灯光固化30‑60s，能量为 $500\\mathrm{-}1000\\mathrm{mJ/cm^{2}}$ 。  \n\n[0029] 一些实施例中，超亲水涂料的涂覆方式为喷涂、淋涂、滴涂、刮涂或滚涂中的一种。  \n\n[0030] 利用本申请的超亲水涂料获得的超亲水涂层的性能数据为：(1)通过水接触角测试仪测试超亲水涂层的水接触角为 $5^{-9^{\\circ}}$ °；(2)通过水浴锅熏蒸测试检测涂层防雾性能，涂覆本申请超亲水涂层的ABS基材放置在 $60^{\\circ}\\mathrm{C}$ 水浴锅水面上方10cm持续熏蒸15min无起雾现象；(3)根据GB/T9780‑2005测试超亲水涂层自然暴晒6个月的沾污率测试结果，与未涂覆超亲水涂层的ABS基材相比，耐沾污性改善比率达到 $50\\text{\\textperthousand}$ ；(4)将涂覆有超亲水涂层的ABS基材放置在水中浸泡 $48\\sim78\\mathrm{h}$ 后进行防雾测试，防雾性能未衰减；(5)对超亲水涂层进行耐酸腐蚀测试，次氯酸溶液浸泡100‑600小时，老化前后涂层无明显脱落、剥离、起皱现象，接触角也未有明显变化；(6)对超亲水涂层进行环境测试，将样品放置于露天环境 $1\\sim2$ 月，老化前后涂层无明显脱落、剥离、起皱现象，水接触角也未有明显变化；(7)对超亲水涂层进行硬度测试，铅笔硬度为1H‑3H。  \n\n[0031] 现有通过向树脂中添加交联剂或疏水组分的方式虽然会提高涂层的耐水性，但是交联剂或疏水组分的加入会影响涂层的亲水性，亲水性与耐水性相矛盾，本申请利用POSS改性聚合物实现提高涂层附着力、耐水泡时间、耐腐蚀性能和硬度。本申请提供的POSS改性聚合物具有优异的附着力，具体表现为：(1)POSS改性聚合物表面张力低，润湿性好，对ABS基材有较强的渗透溶胀能力，固化交联后可在基材与涂层之间形成一层很薄的互穿网络结构，从而增强附着力；(2)POSS改性聚合物官能度为 $2\\sim8$ ，官能度低，交联密度低，体积收缩小，附着力较好；(3)POSS改性聚合物同时含有醚基和酯基，促进涂料在基材表面的附着。  \n\n[0032] 本申请提供的POSS改性聚合物能够延长涂层的防雾耐久时间和耐水浸泡时间：水蒸气冷凝形成的水滴在涂层表面的突起间扩散，在涂层表面形成一层水膜，具有疏水性的POSS调节水在涂层中的扩散，突起表面的POSS能促使水向涂层内部及周围扩散，突起内部的POSS阻止水向涂层内部扩散，水仅能向周围扩散至突起间隙，促进水膜的形成，水膜形成后，后续冷凝的水滴在涂层表面迅速铺展，从而延长防雾耐久时间和耐水浸泡的时间。  \n\n[0033] 按照GB/T  9286‑1998进行POSS改性聚合物的附着力测试，0级代表最好，5级代表最差，具体方法为将POSS改性聚合物与光引发剂TPO以质量比25：1混合，UV灯下固化30s，测试附着力，结果均为0级。  \n\n[0034] 本申请提供的技术方案带来的有益效果包括：  \n\n[0035] 1、本申请提供的POSS改性聚合物制备过程简单，涂装方便，其结构中含有醚键、酯键、环氧基等多种官能团，增强了对ABS基材的附着力，附着力测试等级为0级；  \n\n[0036] 2、本申请提供的超亲水涂料为全亲水体系，原料中光固化单体、POSS改性聚合物与光固化两性离子单体形成交联的互穿网络，有效提高了涂层的硬度、机械强度，可锁住表面活性剂；  \n\n[0037] 3、利用本申请提供的超亲水涂料制备的超亲水涂层光固化速度快，效率高，能耗小；利用POSS与环氧乙烷(EO)的亲水性，使水在亲水粗糙表面会发生hemi‑wicking现象从而水在该亲水粗糙表面扩散，表观接触角进一步降低，直至形成水膜，超亲水涂层水接触角为 $5\\sim9^{\\circ}$ °，防雾持久性好，可长时间耐水浸泡不脱落，稳定性强。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 附图说明  \n\n[0038] 为了更清楚地说明本申请实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。  \n\n[0039] 图1为本申请实施例1制得的POSS改性聚合物的透射电子显微镜图。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 具体实施方式  \n\n[0040] 为使本申请实施例的目的、技术方案和优点更加清楚，下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本申请的一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本申请保护的范围。  \n\n[0041] 本申请实施例提供了一种POSS改性聚合物，其能解决相关技术中ABS基材与超亲水涂层相容性差的问题。  \n\n[0042] 本申请实施例提供了一种POSS改性聚合物的制备方法，包括以下步骤：  \n\n[0043] 步骤S101，将巯基丙酸与八环氧环己基乙基笼状聚倍半硅氧烷混合，加入三乙胺在 $95\\sim110^{\\circ}\\mathrm{C}$ 的条件下反应 $3\\sim6\\mathrm{h}$ ，得到中间体；八环氧环己基乙基笼状聚倍半硅氧烷与巯基丙酸的摩尔比为 $1{:}2\\sim1{:}8$ ；  \n\n[0044] 步骤S102，向中间体中加入乙氧化三羟甲基丙烷三丙烯酸酯和碳酸钠在室温下进行点击反应，即得到POSS改性聚合物；乙氧化三羟甲基丙烷三丙烯酸酯与中间体的摩尔比为 $1{:}1\\sim1{:}3$ 。  \n\n[0045] 上述制得的POSS改性聚合物的结构式如式(Ⅰ)所示：[0046] 式(Ⅰ)：  \n\n![](images/7becd8c231f55fdade02316b6f0c4e095f6e421212d06c94d059191bdcf0a3f7.jpg)  \n\n[0047]  \n\n![](images/d087a12a2a73f9bbdc7d44f326f7b8b77dbd5250feecbb03835b98f17d1c4864.jpg)  \n\n[0048] 式(Ⅰ)中， $\\mathrm{m}+\\mathrm{n}+1=3\\sim20$ 。  \n\n[0049] 下面结合实施例对本申请提供的POSS改性聚合物及其制备方法、包含其的超亲水涂料进行详细说明。  \n\n[0050] 以下实施例中，制备超亲水涂料过程使用的溶剂为乙酸乙酯、异丙醇、乙醇按照体积比4：3：3混合构成的溶液，溶剂的加入量为其他组分总重量的0.3‑3倍。  \n\n[0051] 实施例1：  \n\n[0052] (1)制备POSS改性聚合物：在 $150\\mathrm{ml}$ 反应瓶中投入1mol八环氧环己基乙基笼状聚倍半硅氧烷与2mol巯基丙酸，加入0.05mol三乙胺， $100^{\\circ}\\mathrm{C}$ 下反应3h后，得到中间体，向1mol中间体中滴加0.4mol乙氧化三羟甲基丙烷三丙烯酸酯，加入碳酸钠，室温下反应1h，得到POSS改性聚合物；  \n\n[0053] (2)制备超亲水涂料：按质量份计，称取FS3100  3份，乙二醇二甲基丙烯酸酯45份，制得的POSS改性聚合物33份，AMPS10份，丙烯酸5份，加入溶剂混合搅拌 $0.5\\sim1\\mathrm{h}$ ，再加入光引发剂184  3份和丙烯酸酯类流平剂1份，混合0.5h，得到超亲水涂料；  \n\n[0054] (3)制备超亲水涂层：将超亲水涂料喷涂在ABS板材上， $60-80^{\\circ}\\mathrm{C}$ 预烘2‑3min，紫外 LED灯光固化30‑60s，能量为 $500-1000\\mathrm{mJ/cm}^{2}$ ，获得超亲水涂层。  \n\n[0055] 实施例1制得的POSS改性聚合物的透射电子显微镜图见图1。从图中可以看出POSS改性聚合物形貌为规则球形，粒径在 $700-800\\mathrm{nm}$ 之间。  \n\n[0056] 实施例2：  \n\n[0057] (1)制备POSS改性聚合物：在150ml反应瓶中投入1mol八环氧环己基乙基笼状聚倍半硅氧烷与4mol巯基丙酸，加入0.05mol三乙胺， $100^{\\circ}\\mathrm{C}$ 下反应4h后，得到中间体，向0.48mol中间体中滴加0.4mol乙氧化三羟甲基丙烷三丙烯酸酯，并加入碳酸钠，室温下反应1h，得到POSS改性聚合物；  \n\n[0058] (2)制备超亲水涂料：按质量份计，称取FS30  3份，乙二醇二甲基丙烯酸酯30份，制得的POSS改性聚合物48份，AMPS10份，丙烯酸5份，加入溶剂混合搅拌 $0.5\\sim1\\mathrm{h}$ ，再加入光引发剂184  3份和丙烯酸酯类流平剂1份，混合0.5h，得到超亲水涂料；  \n\n[0059] (3)制备超亲水涂层：将超亲水涂料刮涂在ABS板材上， $60-80^{\\circ}\\mathrm{C}$ 预烘2‑3min，紫外 LED灯光固化30‑60s，能量为 $500\\mathrm{-}1000\\mathrm{mJ/cm}^{2}$ ，获得超亲水涂层。  \n\n[0060] 实施例3：  \n\n[0061] (1)制备POSS改性聚合物：在 $150\\mathrm{ml}$ 反应瓶中投入1mol八环氧环己基乙基笼状聚倍半硅氧烷与6mol巯基丙酸，加入0.05mol三乙胺， $100^{\\circ}\\mathrm{C}$ 下反应5h后，得到中间体，向0.6mol中间体中滴加0.4mol乙氧化三羟甲基丙烷三丙烯酸酯，并加入碳酸钠，室温下反应1h，即得到POSS改性聚合物；  \n\n[0062] (2)制备超亲水涂料：按质量份计，称取FS31  4份，乙氧化双酚A二丙烯酸酯25份，制得的POSS改性聚合物45份，AMPS13份，衣康酸8份，加入溶剂混合搅拌 $0.5\\sim1\\mathrm{h}$ ，再加入光引发剂1173  4份和丙烯酸酯类流平剂1份，混合0.5h，得到超亲水涂料；  \n\n[0063] (3)制备超亲水涂层：将超亲水涂料滴涂在ABS板材上， $60-80^{\\circ}\\mathrm{C}$ 预烘2‑3min，紫外 LED灯光固化30‑60s，能量为 $500-1000\\mathrm{mJ/cm}^{2}$ ，获得超亲水涂层。  \n\n[0064] 实施例4：  \n\n[0065] (1)制备POSS改性聚合物：在 $150\\mathrm{ml}$ 反应瓶中投入1mol八环氧环己基乙基笼状聚倍半硅氧烷与8mol巯基丙酸，加入0.05mol三乙胺， $110^{\\circ}\\mathrm{C}$ 下反应5h后，得到中间体，向 $0.72\\mathrm{mol}$ 中间体中滴加0.4mol乙氧化三羟甲基丙烷三丙烯酸酯，并加入碳酸钠，室温下反应1h，即得到POSS改性聚合物；  \n\n[0066] (2)制备超亲水涂料：按质量份计，称取FS34  4份，乙氧化双酚A二丙烯酸酯25份，制得的POSS改性聚合物44份，DNS  86  13份，衣康酸8份，加入溶剂混合搅拌 $0.5\\sim1\\mathrm{h}$ ，再加入光引发剂1173  4份和丙烯酸酯类流平剂2份，混合0.5h，得到超亲水涂料；  \n\n[0067] (3)制备超亲水涂层：将超亲水涂料喷涂在ABS板材上， $60-80^{\\circ}\\mathrm{C}$ 预烘 $2\\ifmmode-\\else-\\else\\textmu\\fi{}\\mathrm{3min}$ ，紫外 LED灯光固化30‑60s，能量为 $500-1000\\mathrm{mJ/cm^{2}}$ ，获得超亲水涂层。  \n\n[0068] 实施例5：  \n\n[0069] (1)制备POSS改性聚合物：在 $150\\mathrm{ml}$ 反应瓶中投入1mol八环氧环己基乙基笼状聚倍半硅氧烷与6mol巯基丙酸，加入0.05mol三乙胺， $100^{\\circ}\\mathrm{C}$ 下反应5h后，得到中间体，向0.8mol中间体中滴加0.4mol乙氧化三羟甲基丙烷三丙烯酸酯，并加入碳酸钠，室温下反应1h，即得到POSS改性聚合物；  \n\n[0070] (2)制备超亲水涂料：按质量份计，称取FS1700  5份，乙氧化双酚A二丙烯酸酯30份，制得的POSS改性聚合物33份，DNS  86  15份，HEA  10份，加入溶剂混合搅拌 $0.5\\sim1\\mathrm{h}$ ，再加入光引发剂TPO  5份和丙烯酸酯类流平剂2份，混合0.5h，得到超亲水涂料；  \n\n[0071] (3)制备超亲水涂层：将超亲水涂料滚涂在ABS板材上， $60-80^{\\circ}\\mathrm{C}$ 预烘2‑3min，紫外 LED灯光固化30‑60s，能量为 $500-1000\\mathrm{mJ/cm}^{2}$ ，获得超亲水涂层。  \n\n[0072] 实施例6：  \n\n[0073] (1)制备POSS改性聚合物：在 $150\\mathrm{ml}$ 反应瓶中投入1mol八环氧环己基乙基笼状聚倍半硅氧烷与2mol巯基丙酸，加入0.05mol三乙胺， $105^{\\circ}\\mathrm{C}$ 下反应3h后，得到中间体，向 $0.88\\mathrm{mol}$ 中间体中滴加0 .4mol乙氧化三羟甲基丙烷三丙烯酸酯，加入碳酸钠，室温下反应1h，得到POSS改性聚合物；  \n\n[0074] (2)制备超亲水涂料：按质量份计，称取FS3100  5份，乙氧化双酚A二丙烯酸酯25份，制得的POSS改性聚合物38份，DNS  86  15份，HEA  10份，加入溶剂混合搅拌 $0.5\\sim1\\mathrm{h}$ ，再加入光引发剂TPO  5份和丙烯酸酯类流平剂2份，混合0.5h，得到超亲水涂料；  \n\n[0075] (3)制备超亲水涂层：将超亲水涂料喷涂在ABS板材上， $60-80^{\\circ}\\mathrm{C}$ 预烘2‑3min，紫外 LED灯光固化30‑60s，能量为 $500\\mathrm{-}1000\\mathrm{mJ/cm}^{2}$ ，获得超亲水涂层。  \n\n[0076] 上述实施例1‑实施例6中各原料的质量份见表1。  \n\n[0077] 表1：实施例1‑实施例6中各原料的质量份  \n\n<html><body><table><tr><td>实施 例</td><td>表面活性剂</td><td>POSS改 性聚合</td><td>光固化单体</td><td>光固化两性 离子单体</td><td>活性稀释剂 单体</td><td>流平 剂</td><td>光引发剂</td></tr><tr><td>1</td><td>FS31003份</td><td>物 33份</td><td>乙二醇二甲基丙烯酸酯45份</td><td>AMPS10份</td><td>丙烯酸5份</td><td>1份</td><td>1843份</td></tr><tr><td>2</td><td>FS303份</td><td>48份</td><td>乙二醇二甲基丙烯酸酯30份</td><td>AMPS10份</td><td>丙烯酸5份</td><td>1份</td><td>1843份</td></tr><tr><td>3</td><td>FS31 4份</td><td>45份</td><td>乙氧化双酚A二丙烯酸酯25份</td><td>AMPS13份</td><td>衣康酸8份</td><td>1份</td><td>1173 4份</td></tr><tr><td>4</td><td>FS344份</td><td>44份</td><td>乙氧化双酚A二丙烯酸酯25份</td><td>DNS8613份</td><td>衣康酸8份</td><td>2份</td><td>1173 4份</td></tr><tr><td>5</td><td>FS17005份</td><td>33份</td><td>乙氧化双酚A二丙烯酸酯30份</td><td>DNS8615份</td><td>HEA10份</td><td>2份</td><td>TPO 5份</td></tr><tr><td>6</td><td>FS31005份</td><td>38份</td><td>乙氧化双酚A二丙烯酸酯25份</td><td>DNS8615份</td><td>HEA 10份</td><td>2份</td><td>TPO 5份</td></tr></table></body></html>  \n\n[0078]  \n\n对实施例1‑实施例6获得的超亲水涂层进行性能测试，结果见表2。  \n\n表2：超亲水涂层的性能测试结果  \n\n\n<html><body><table><tr><td>项目 实施例</td><td>水接 触角</td><td>耐水性能</td><td>耐摩擦性能</td><td>高温加速老化 试验</td><td>耐酸腐蚀测试</td><td>硬度测试</td></tr><tr><td>1</td><td>9°</td><td>浸泡48h 仍防雾</td><td>200g羊毛毡， 2000次后仍防雾</td><td>100℃800h 仍防雾</td><td>次氯酸溶液浸泡 100小时仍防雾</td><td>铅笔硬度3H</td></tr></table></body></html>  \n\n[0081] [0082]  \n\n<html><body><table><tr><td>2</td><td>5°</td><td>浸泡54h 仍防雾</td><td>200g羊毛毡， 3000次后仍防雾</td><td>100℃1000h 仍防雾</td><td>次氯酸溶液浸泡 200小时仍防雾</td><td>铅笔硬度1H</td></tr><tr><td>3</td><td>8°</td><td>浸泡62h 仍防雾</td><td>200g羊毛毡， 4000次后仍防雾</td><td>100℃1200h 仍防雾</td><td>次氯酸溶液浸泡 300小时仍防雾</td><td>铅笔硬度3H</td></tr><tr><td>4</td><td>5°</td><td>浸泡72h 仍防雾</td><td>200g羊毛毡， 5000次后仍防雾</td><td>100℃1200h 仍防雾</td><td>次氯酸溶液浸泡 400小时仍防雾</td><td>铅笔硬度1H</td></tr><tr><td>5</td><td>6°</td><td>浸泡74h 仍防雾</td><td>200g羊毛毡， 6000次后仍防雾</td><td>100℃1400h 仍防雾</td><td>次氯酸溶液浸泡 500小时仍防雾</td><td>铅笔硬度2H</td></tr><tr><td>6</td><td>7°</td><td>浸泡78h 仍防雾</td><td>200g羊毛毡， 7000次后仍防雾</td><td>100℃1600h 仍防雾</td><td>次氯酸溶液浸泡 600小时仍防雾</td><td>铅笔硬度2H</td></tr></table></body></html>  \n\n[0083] 从表2的数据可以看出，利用本申请的超亲水涂料获得的超亲水涂层的水接触角为 $5\\sim9^{\\circ}$ °，表现出优异的防雾性能和耐腐蚀性能，耐水浸泡时间长。  \n\n[0084] 在本说明书的描述中，参考术语“一个实施例/方式”、“一些实施例/方式”、“示例”、“具体示例”或“一些示例”等的描述意指结合该实施例/方式或示例描述的具体特征、结构、材料或者特点包含于本申请的至少一个实施例/方式或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例/方式或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例/方式或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例/方式或示例以及不同实施例/方式或示例的特征进行结合和组合。  \n\n[0085] 需要说明的是，在本申请中，诸如“第一”和“第二”等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来，而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。在没有更多限制的情况下，由语句“包括一个……”限定的要素，并不排除在包括所述要素的过程、方法、物品或者设备中还存在另外的相同要素。在本申请中，“多个”的含义是至少两个，例如两个、三个等，除非另有明确具体的规定。  \n\n[0086] 以上所述仅是本申请的具体实施方式，使本领域技术人员能够理解或实现本申请。对这些实施例的多种修改对本领域的技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本申请的精神或范围的情况下，在其它实施例中实现。因此，本申请将不会被限制于本文所示的这些实施例，而是要符合与本文所申请的原理和新颖特点相一致的最宽的范围。  \n\n![](images/6474b32995ac20856d3d9130d580777f1321572d03a1c27bcb8c8d70c0c7835a.jpg)  \n图1",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,57 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利申请  \n\nE21B43/2 (2006.01)  \n\n(21)申请号 200910236651.X  \n(22)申请日 2009.10.27  \n(71)申请人 中国石油化工股份有限公司地址 100728 北京市朝阳区朝阳门北大街22 号申请人 中国石油化工股份有限公司北京化工研究院  \n(72)发明人 杜凯  李勇  伊卓 刘晓光林蔚然  计文希  魏小林  祝纶宇赵方园  \n(74)专利代理机构 北京思创毕升专利事务所11218代理人 韦庆文  \n(51)Int.Cl.C09K8/58 (2006.01)C08F251/0 (2006.01)",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54) 发明名称  \n\n一种黄原胶接枝共聚物驱油剂及其制法和应用",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57) 摘要  \n\n本发明提供一种黄原胶接枝共聚物驱油剂及其制备方法和用途，通过分子设计，将丙烯酰胺 (AM)、2- 丙烯酰胺基 $-2-$ 甲基丙磺酸 (AMPS)、$\\mathrm{N^{-}}$ 乙烯基吡咯烷酮 (NVP) 或 $\\ N,\\ N-$ 二甲基丙烯酰胺 (DMAM) 中的至少两种接枝共聚合到黄原胶大分子上，这种共聚型侧链的引入可以大大提高黄原胶大分子的黏弹性、耐热及生物稳定性，同时可作为三次采油驱油剂使用，溶解速度明显提高且在盐水中不易产生凝胶。在高温高盐油藏使用时，驱油效果提高。  \n\n1. 一种黄原胶接枝共聚物驱油剂，其特征是：  \n\n其结构式如(1) 式所示：  \n\n![](images/3f710a0794a69385d0960bb2ba705b7cdd45c34e75a60bcc433293fd6dad94dc.jpg)  \n\n在 (1) 式中 ：  \n\nn 值为所选用的黄原胶大分子上的重复单元数，所选用的黄原胶大分子的相对分子质量为 200 万 $\\sim600$ 万，n 值的范围相应确定。  \n\n[X] 为下列中的至少两种形成的重复单元：丙烯酰胺 (AM)、2- 丙烯酰胺基 $-2-$ 甲基丙磺酸 (AMPS)、 $\\mathrm{N^{-}}$ 乙烯基吡咯烷酮(NVP) 和 $\\mathrm{N},\\mathrm{N-}$ 二甲基丙烯酰胺(DMAM) ；  \n\ny 为接枝共聚单体的聚合度，为大于0 的整数。  \n\n2. 一种根据权利要求1 所述的黄原胶接枝共聚物驱油剂，其特征是：  \n\n在(1) 式中，[X] 为所述的AM 与所述的AMPS 形成的重复单元，其中AMPS 为第一单体AM 为第二单体，AM 单元在接枝链上占摩尔比例为不小于 $5\\%$ 且不大于 $95\\%$ 。  \n\n3. 一种根据权利要求1 所述的黄原胶接枝共聚物驱油剂，其特征是：  \n\n在(1) 式中，[X] 为AM 与NVP 形成的重复单元，其中NVP 为第一单体，AM 为第二单体，AM 单元在接枝链上占摩尔比例为不小于 $5\\%$ 且不大于 $95\\%$ 。  \n\n4. 一种根据权利要求1 所述的黄原胶接枝共聚物驱油剂，其特征是：  \n\n在 (1) 式中，[X] 为 AMPS 与 DMAM 形成的重复单元，其中 DMAM 为第一单体，AMPS 为第二单体，AMPS 单元在接枝链上占摩尔比例为不小于 $5\\%$ 且不大于 $95\\%$ 。  \n\n5. 一种根据权利要求1 所述的黄原胶接枝共聚物驱油剂，其特征是：  \n\n在 (1) 式中，[X] 为 AM、AMPS 与 DMAM 形成的重复单元，其中 DMAM 为第一单体，AMPS 为第二单体，AM 为第三单体，AM、AMPS 单元在接枝链上占摩尔比例均不小于 $10\\%$ 且不大于 $90\\%$ 。  \n\n6. 一种权利要求1 的黄原胶接枝共聚物驱油剂的制备方法，其特征是：  \n\n按质量份数，原料配方为：  \n\n黄原胶 100 份，总的单体 $200\\sim3000$ 份，硝酸铈铵 $0.1\\sim10$ 份，过硫酸盐 $0.1\\sim100$ 份，亚硫酸氢钠 $0.1\\sim300$ 份，去离子水 $300\\sim30000$ 份；  \n\n所述的单体为下列中的至少两种：丙烯酰胺 $(\\mathrm{AM})\\cdot2^{-}$ 丙烯酰胺基 $-2-$ 甲基丙磺酸(AMPS)、 $\\mathrm{N^{-}}$ 乙烯基吡咯烷酮(NVP) 和 $\\mathrm{N},\\mathrm{N}^{-}$ 二甲基丙烯酰胺 (DMAM) ；  \n\n所述的过硫酸盐为下列中的至少一种：过硫酸铵和过硫酸钾；优选过硫酸铵。  \n\n包括以下步骤：  \n\n第1 步，将100 份黄原胶在反应容器中完全溶解于前述配方份数的去离子水中，通入高纯氮气鼓泡除氧；  \n\n第2 步，将所述单体中的反应活性低的一种或两种 $10\\sim1500$ 份加入到反应容器中，搅拌至完全溶解；  \n\n第 3 步，向反应容器中继续通入高纯氮气鼓泡除氧20 分钟以上；  \n\n第4 步，在氮气保护下，向反应容器中加入前述配方份数的硝酸铈铵，在 $20^{\\circ}\\mathrm{C}\\sim70^{\\circ}\\mathrm{C}$ 下反应 $5\\sim15$ 分钟；  \n\n第 5 步，在氮气保护下，向反应容器中加入前述配方份数的过硫酸盐，前述配方份数的亚硫酸氢钠，将所述单体中反应活性高的另一种单体 $190\\sim2990$ 份配成水溶液，在 0.5 小时内以均匀速率加到反应容器中，在 $20^{\\circ}\\mathrm{C}\\sim70^{\\circ}\\mathrm{C}$ 下反应 $2\\sim6$ 小时；得到产物；  \n\n第6 步，将上步产物用过量丙酮沉淀， $50^{\\circ}\\mathrm{C}$ 下完全干燥，得到接枝共聚粗产物；  \n\n第7 步，将粗产物用体积比为 $80:20$ 的甲醇- 水混合溶剂在索氏提取器中萃取12 小时，抽提剩余物用蒸馏水反复洗涤，得到接枝共聚物，进行干燥，得到权利要求1 至5 之一的产品。  \n\n7. 一种根据权利要求6 所述的制备方法，其特征是：  \n在原料配方中，总的单体 $200\\sim1500$ 份。  \n8. 一种根据权利要求6 所述的制备方法，其特征是：  \n在原料配方中，硝酸铈铵 $1\\sim5$ 份。  \n9. 一种根据权利要求6 所述的制备方法，其特征是：  \n在原料配方中，过硫酸盐 $1\\sim50$ 份。  \n10. 一种根据权利要求6 所述的制备方法，其特征是：  \n在原料配方中，亚硫酸氢钠 $1\\sim100$ 份。  \n11. 一种根据权利要求6 所述的制备方法，其特征是：  \n在原料配方中，去离子水 $5000\\sim15000$ 份。  \n12. 一种根据权利要求6 至11 之一所述的制备方法，其特征是：在第2 步中，加入的单体为AMPS ；  \n在第5 步中，加入的为单体AM 的水溶液。  \n13. 一种根据权利要求6 至11 之一所述的制备方法，其特征是：在第2 步中，加入的单体为NVP ；  \n在第5 步中，加入的为单体AM 的水溶液。14. 一种根据权利要求6 至11 之一所述的制备方法，其特征是：  \n在第2 步中，加入的单体为DMAM ；  \n在第5 步中，加入的为单体AMPS 的水溶液。  \n15. 一种根据权利要求6 至11 之一所述的制备方法，其特征是：  \n在第2 步中，加入的单体为AMPS 与DMAM ；  \n优选，在第5 步中，加入的为单体AM 的水溶液。  \n16. 权利要求1 至5 之一的黄原胶接枝共聚物驱油剂在三次采油中的应用。",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# 一种黄原胶接枝共聚物驱油剂及其制法和应用",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明涉及三次采油领域水溶性聚合物，具体涉及一种黄原胶接枝共聚物驱油剂及其制备方法和用途。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 在国内油田已普遍进入高含水开发期的今天，以高分子量部分水解聚丙烯酰胺(HPAM) 为主要代表的聚合物驱提高原油采收率技术已经日见成效，且在低温、低盐的一、二类油藏中得到广泛使用。但针对三类油藏中高温、高盐的地层条件特点，高分子量部分水解聚丙烯酰胺 (HPAM) 存在耐盐性差、易水解、易降解、与钙、镁等二价金属离子络合易生成沉淀等问题，使其在三类油藏中的实际驱油效率大幅度下降。  \n\n[0003] 目前针对三类地层条件的油藏资源 ( 地层温度 $70\\sim95^{\\circ}\\mathrm{C}$ ，地层矿化度 $10000\\sim$ 30000mg/L)，全世界范围内仍没有成熟的、工业化、商品化的聚合物驱油剂产品问世。为了解决上述问题、提高三类油藏采收率，研发适应高温、高盐地层条件的驱油剂已经成为工业界、学术界研发的重点领域。  \n\n[0004] 黄原胶 (Xanthan gum，XG) 是由 $\\mathrm{D^{-}}$ 葡萄糖、 $\\mathrm{D^{-}}$ 甘露糖、 $\\mathrm{D^{-}}$ 葡萄糖醛酸、乙酰基、丙酮酸组成的高分子酸性杂多糖，是集增稠、悬浮、乳化、稳定作用于一体，性能较为优越的生物胶。与HPAM 相比，黄原胶作为驱油剂使用具有以下优点：其溶液在高温、高矿化度条件下仍具有相对较高的黏度值；抗机械剪切能力强；溶液不易被储层岩石吸附等。  \n\n[0005] 对于高温高盐的三类油藏条件下，虽然黄原胶较 HPAM 具有较明显的优势，但仍无法完全满足三类油藏的要求，主要由于黄原胶存在以下缺点： $\\textcircled{1}$ 黄原胶溶液耐生物降解能力差，容易造成溶液黏度损失； $\\textcircled{2}$ 耐热稳定性差，在高温高盐的条件下易发生降解； $\\textcircled{3}$ 提高原油采收率程度不明显。  \n\n[0006] 通过对黄原胶进行接枝共聚改性，将丙烯酰胺及带有耐温抗盐性能的单体接枝到黄原胶上，在保持黄原胶原有耐温耐盐优异性能的同时可以提高其黏弹性、耐热及生物稳定性。  \n\n[0007] 对比文献 1( 黄原胶与丙烯酰胺接枝共聚反应的研究，应用化工，2007，36(12) ：1163) 公开了一种黄原胶 $-\\mathrm{g}-$ 丙烯酰胺接枝共聚物 $(\\mathrm{XG-g-AM})$ 的制备方法：在 $250\\mathrm{mL}$ 三口烧瓶中，加入1g 黄原胶和 $100\\mathrm{mL}$ 蒸馏水，放置过夜，充分搅拌使黄原胶完全溶解。将三口烧瓶放在恒温水浴锅中，在反应温度下搅拌并通氮气保护，加入一定量的过硫酸铵和丙烯酰胺，反应至预定时间后，中止反应，冷却。将产物用过量丙酮沉淀， $50^{\\circ}\\mathrm{C}$ 下完全干燥，得到接枝共聚粗产物。将粗产品用体积比为 $80:20$ 的甲醇- 水混合溶剂在索氏提取器中萃取 $\\mathrm{12h}$ 以上，以除去PAM 均聚物，抽提剩余物用蒸馏水反复洗涤，得到 $\\operatorname{XG-g-AM}$ 接枝共聚物。  \n\n[0008] 对比文献2(Synthesis and Study of Metal Ion Sorption Capacity of XanthanGum-g-2-Acrylamido $^{-2}$ -Methyl-1-Propane Sulphonic Acid，J Appl Polym Sci，2007，104 ：470)公开了一种黄原胶 $-\\mathrm{g}-$ (2-丙烯酰胺基 $-2-$ 甲基丙磺酸)接枝共聚物 $({\\mathrm{XG-g-AMPS}})$ )的制备方法：在三口烧瓶中，加入定量的黄原胶蒸馏水，使黄原胶完全溶解，加入一定量的硫脲、AMPS 和硫酸溶液，通氮气除氧，30 分钟后加入定量的溴酸钾溶液引发聚合，反应至预定时间后，中止反应，冷却。将产物用过量丙酮沉淀，得到接枝共聚粗产物。将粗产品用甲醇- 水混合溶剂洗去均聚物，得到 ${\\tt X G}{-}\\mathrm{g}{-}{\\tt A M P S}$ 接枝共聚物。  \n\n[0009] 与黄原胶相比，对比文献报道的 $\\mathrm{XG-g-AM\\setminus\\mathrm{XG-g-AMPS}}$ 耐温性及生物稳定性有了一定程度的改善，但仍无法作为三次采油驱油剂使用，主要由于： $\\operatorname{XG-g-AM}$ 溶解速度太慢、滤过比高，不符合油田现场作业的要求；而 $\\mathrm{{XG-g-AMPS}}$ 接枝率低，注入到地层中易沉积，无法起到驱油作用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0010] 本发明要解决的技术问题是：  \n\n[0011] 针对现有技术的不足，本发明的目的是提供一种耐温抗盐型黄原胶接枝共聚物驱油剂，提高黄原胶驱油剂的黏弹性、耐热及生物稳定性，在高温高盐油藏使用时，驱油效果提高。  \n\n[0012] 本发明的产品技术方案是：  \n[0013] 一种黄原胶接枝共聚物驱油剂，其结构式如(1) 式所示：  \n[0014]  \n\n![](images/d0d12433b2804fae74f4866e5e0fbcdd29018e482df1a6ef49e91a05fc13fcfb.jpg)  \n(1)  \n\n[0015] 式中黄原胶重复单元可缩写为XG。  \n\n[0016] 在 (1) 式中 ：  \n\n[0017] n 值为所选用的黄原胶大分子上的重复单元数，所选用的黄原胶大分子的相对分子质量为200 万 $\\sim600$ 万，n 值的范围相应确定。  \n\n[0018] [X] 为下列中的至少两种形成的重复单元：丙烯酰胺 (AM)、 $\\cdot2\\textdegree$ 丙烯酰胺基 $-2-$ 甲基丙磺酸 (AMPS)、 $\\mathrm{N^{-}}$ 乙烯基吡咯烷酮(NVP) 和 $\\mathrm{N},\\mathrm{N-}$ 二甲基丙烯酰胺 (DMAM) ；  \n\n[0019] y 为接枝共聚单体的聚合度，为大于0 的整数。  \n\n[0020] 对 (1) 式进一步限定，得到不同优选产品：  \n\n[0021] 产品 1，[X] 为所述的 AM 与所述的 AMPS 形成的重复单元，其中 AMPS 为第一单体，AM 为第二单体，AM 单元在接枝链上占摩尔比例为不小于 $5\\%$ 且不大于 $95\\%$ ；  \n\n[0022] 产品 2，[X] 为 AM 与 NVP 形成的重复单元，其中 NVP 为第一单体，AM 为第二单体，AM 单元在接枝链上占摩尔比例为不小于 $5\\%$ 且不大于 $95\\%$ ；  \n\n[0023] 产品 3，[X] 为 AMPS 与 DMAM 形成的重复单元，其中 DMAM 为第一单体，AMPS 为第二单体，AMPS 单元在接枝链上占摩尔比例为不小于 $5\\%$ 且不大于 $95\\%$ ；  \n\n[0024] 产品 4，[X] 为 AM、AMPS 与 DMAM 形成的重复单元，其中 DMAM 为第一单体，AMPS 为第二单体，AM 为第三单体，AM、AMPS 单元在接枝链上占摩尔比例均不小于 $10\\%$ 且不大于 $90\\%$ ；[0025] 本发明的制备方法技术方案是：  \n\n[0026] 按质量份数，原料配方为：  \n\n[0027] 黄原胶 100 份，总的单体 $200\\sim3000$ 份，硝酸铈铵 $0.1\\sim10$ 份，过硫酸盐 $0.1\\sim$ 100 份，亚硫酸氢钠 $0.1\\sim300$ 份，去离子水 $300\\sim30000$ 份。  \n\n[0028] 优选 ：总的单体 $200\\sim1500$ 份，硝酸铈铵 $1\\sim5$ 份，过硫酸盐 $1\\sim50$ 份，亚硫酸氢钠 $1\\sim100$ 份，去离子水 $5000\\sim15000$ 份。  \n\n[0029] 所述的单体为下列中的至少两种：丙烯酰胺 (AM)、 $\\cdot2\\textdegree$ 丙烯酰胺基 $-2-$ 甲基丙磺酸(AMPS)、 $\\mathrm{N^{-}}$ 乙烯基吡咯烷酮(NVP) 和 $\\mathrm{N},\\mathrm{N-}$ 二甲基丙烯酰胺 (DMAM) ；  \n\n[0030] 所述的过硫酸盐为下列中的至少一种：过硫酸铵和过硫酸钾；优选过硫酸铵。  \n\n[0031] 包括以下步骤：  \n\n[0032] 第1 步，将100 份黄原胶在反应容器中完全溶解于 $300\\sim30000$ 份去离子水中，通入高纯氮气鼓泡除氧；  \n\n[0033] 第 2 步，将所述单体中的反应活性低的一种或两种 $10\\sim1500$ 份加入到反应容器中，搅拌至完全溶解；  \n\n[0034] 对于制备产品1，此步加入的单体为AMPS ；  \n\n[0035] 对于制备产品2，此步加入的单体为NVP ；  \n\n[0036] 对于制备产品3，此步加入的单体为DMAM ；  \n\n[0037] 对于制备产品4，此步加入的单体为AMPS 与DMAM ；  \n\n[0038] 第 3 步，向反应容器中继续通入高纯氮气鼓泡除氧20 分钟以上；  \n\n[0039] 第 4 步，在氮气保护下，向反应容器中加入 $0.1\\sim10$ 份硝酸铈铵，在 $20^{\\circ}\\mathrm{C}\\sim70^{\\circ}\\mathrm{C}$ 下反应 $5\\sim15$ 分钟；  \n\n[0040] 第5 步，在氮气保护下，向反应容器中加入 $0.1\\sim1000$ 份过硫酸盐， $0.1\\sim3000$ 份亚硫酸氢钠，将所述单体中反应活性高的另一种单体 $190\\sim2990$ 份配成水溶液，在 0.5 小时内以均匀速率加到反应容器中，在 $20^{\\circ}\\mathrm{C}\\sim70^{\\circ}\\mathrm{C}$ 下反应 $2\\sim6$ 小时；得到产物；  \n\n[0041] 对于制备产品1，此步加入的为单体AM 的水溶液；  \n[0042] 对于制备产品2，此步加入的为单体AM 的水溶液；  \n[0043] 对于制备产品3，此步加入的为单体AMPS 的水溶液；  \n\n[0044] 对于制备产品4，此步加入的为单体AM 的水溶液；  \n\n[0045] 第 6 步，将上步产物用过量丙酮沉淀， $50^{\\circ}\\mathrm{C}$ 下完全干燥，得到接枝共聚粗产物；[0046] 第 7 步，将粗产物用体积比为 $80:20$ 的甲醇 - 水混合溶剂在索氏提取器中萃取12 小时，抽提剩余物用蒸馏水反复洗涤，得到接枝共聚物，进行干燥，得到产品。  \n\n[0047] 干燥，粉碎采用本领域公知的常规技术。  \n\n[0048] 本发明的黄原胶接枝共聚物驱油剂产品可以在三次采油领域中应用。  \n\n[0049] 通过分子设计，将丙烯酰胺(AM)、2- 丙烯酰胺基 $-2-$ 甲基丙磺酸 (AMPS)、 $\\mathrm{N^{-}}$ 乙烯基吡咯烷酮(NVP) 或N，N- 二甲基丙烯酰胺(DMAM) 中的至少两种接枝共聚合到黄原胶大分子上，这种共聚型侧链的引入可以大大提高黄原胶大分子的黏弹性、耐热及生物稳定性，同时可作为三次采油驱油剂使用，溶解速度明显提高且在盐水不易产生凝胶。同时室内模拟驱油实验结果表明本专利发明的黄原胶改性产品可以明显提高高温高盐油藏的采收率。具有采收率提高、综合性能优异、开发性价比高的特点，对于三类油藏的开采具有重要价值。  \n\n[0050] 已有文献中均未见上述共聚结构黄原胶改性产品的报道，主要由于利用现有技术使上述共聚单体中的至少两种进行黄原胶共聚合改性时，接枝共聚反应的接枝率、接枝效率低；同时上述共聚单体中的至少两种进行黄原胶共聚合改性时存在竞聚率上的较大差异，难于制备侧链平均组成和序列分布均一的黄原胶改性产品。  \n\n[0051] 本发明在氧化 - 还原复合引发剂的作用下，通过复合引发剂引发接枝聚合，得到接枝率、接枝效率及转化率都很高的新型耐温抗盐黄原胶接枝共聚物。第一段由硝酸铈铵引发，通过 ${\\mathrm{Ce}}^{4+}$ 离子与黄原胶生成络合物，再引发黄原胶生成自由基，继而与单体发生接枝聚合反应；第二段由过硫酸盐 / 亚硫酸盐引发，通过氧化还原反应生成硫酸盐游离基，进一步提高接枝反应的接枝率和接枝效率。  \n\n[0052] 与现有技术相比，本发明在分子设计、制备方法及应用上具有如下优点和效果：  \n\n[0053] $\\textcircled{1}$ 耐温抗盐型侧链的引入大大提高黄原胶大分子耐热及生物稳定性，耐温抗盐型单体的引入使黄原胶接枝共聚物在高温高盐的条件下具有很高的黏度及黏度保留率；  \n\n[0054] $\\textcircled{2}$ 水溶性长侧链的引入极大改善了黄原胶大分子的黏弹性，作为驱油剂使用，可以提高驱油过程中的驱替效率。  \n\n[0055] $\\textcircled{3}$ 制备方法上，复合引发剂存在协同作用，保证了耐温抗盐型长支链的生成，与使用单一引发剂的对比例相比，接枝共聚反应的接枝率、接枝效率明显的提高。采用先加活性较低单体，再滴加活性较高单体的两段聚合法，一定程度上了规避了由于共聚单体竞聚率上较大差异造成的影响，易于制备侧链平均组成和序列分布均一的黄原胶改性产品。  \n\n[0056] $\\textcircled{4}$ 将上述耐温抗盐型黄原胶接枝共聚物应用于三次采油驱油剂使用，室内模拟驱油实验结果表明驱油效果明显，能够显著提高原油的采收率。  \n\n[0057] 本发明的有益效果：  \n\n[0058] 本发明在复合引发剂的协同作用下，通过两步引发接枝聚合，得到接枝率、接枝效率都较高的带有长侧链的新型耐温抗盐黄原胶接枝共聚物。应用于三次采油驱油剂使用，显著提高了原油的采收率。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 附图说明  \n\n[0059] 图 1 是黄原胶的IR 谱图。  \n\n[0060] 图 2 是实施例1 得到 $\\mathrm{XG^{-}g^{-}}\\left(\\mathrm{AM\\mathrm{-}c o^{-}A M P S}\\right)$ 的 IR 谱图。  \n[0061] 图 3 是黄原胶的SEM 图片。  \n[0062] 图 4 是实施例1 得到 $\\mathrm{XG^{-}g^{-}}\\left(\\mathrm{AM\\mathrm{-}c o^{-}A M P S}\\right)$ 的 SEM 图片。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 具体实施方式  \n\n[0063] 按下列公式计算接枝率(G)、接枝效率(GE) ：  \n[0064] $\\ddot{\\mathbf{G}}=\\frac{\\mathbb{W}_{2}}{\\mathbb{W}_{0}}\\times100\\%$   \n[0065] $\\mathrm{E}=\\frac{\\mathrm{W_{3}}}{\\mathrm{W_{3}}+\\mathrm{W_{2}}}\\times100\\%$  \n\n[0066] 式中， ${\\mathbb N}_{0},{\\mathbb N}_{1},{\\mathbb N}_{2}$ 分别为黄原胶的质量(g)、接枝共聚物质量(g)、均聚物的重量 $\\mathrm{(g)}$ 。  \n\n[0067] 黄原胶接枝共聚物的结构确立与分析采用红外光谱法 (IR)，测试仪器为Perkin-Elmer system 2000 型傅里叶红外光谱仪，扫描范围为 $4000\\sim400\\mathrm{{cm}^{-1}}$ ，使用 $\\mathrm{KBr}$ 研磨压片制样。  \n\n[0068] 溶液表观黏度在指定测试温度下用 Brookfield 黏度计测定，选用 0 号转子，剪切速率 $\\boldsymbol{7.34s^{-1}}$ 。  \n\n[0069] 实施例1 本发明的耐温抗盐黄原胶接枝共聚物制备[0070] 室温下，在 $250\\mathrm{mL}$ 三口烧瓶中，加入 1g 黄原胶和 $100\\mathrm{g}$ 蒸馏水，充分搅拌使黄原胶完全溶解，通入高纯氮气鼓泡除氧。将 $6.43\\mathrm{g}$ 的 $2^{-}$ 丙烯酰胺基 $-2-$ 甲基丙磺酸 (AMPS) 加入到反应容器中，搅拌至完全溶解；向反应容器中继续通入高纯氮气鼓泡除氧 20 分钟以上。将三口烧瓶放在 $55^{\\circ}\\mathrm{C}$ 恒温水浴锅中，在氮气保护下，加入 $0.02\\mathrm{g}$ 硝酸铈铵， $55^{\\circ}\\mathrm{C}$ 下反应5 分钟后，加入 $0.2\\mathrm{g}$ 过硫酸铵， $0.6\\mathrm{g}$ 亚硫酸氢钠，将 $\\mathrm{2g}$ 丙烯酰胺 (AM) 配成 $50\\%$ 的水溶液缓慢滴加入到反应容器中， $55^{\\circ}\\mathrm{C}$ 下反应 3 小时，将产物用过量丙酮沉淀， $50^{\\circ}\\mathrm{C}$ 下完全干燥，得到接枝共聚粗产物。将粗产品用体积比为 $80:20$ 的甲醇- 水混合溶剂在索氏提取器中萃取12 小时以上，以除去均聚物，抽提剩余物用蒸馏水反复洗涤，得到接枝共聚物，在 $50^{\\circ}\\mathrm{C}$ 下完全干燥，称重，得到黄原胶接枝共聚物 $\\mathrm{XG^{-}g^{-}}\\left(\\mathrm{AM\\mathrm{-}c o^{-}A M P S}\\right)$ 。将产物进行IR 测试，结果见图2 所示，并与图1 所示黄原胶IR 结果进行对比。  \n\n[0071] 由两图对比可见，黄原胶在 $3450\\mathrm{cm}^{-1}$ 处出现强而宽的 O-H 伸缩振动吸收峰；在 $1615\\mathrm{cm}^{-1}$ 和 $1476\\mathrm{cm}^{-1}$ 处出现 $\\mathrm{COO^{-}}$ 对称及非对称伸缩振动吸收峰；另外在 $1417\\mathrm{cm}^{-1}$ 和$1023\\mathrm{cm}^{-1}$ 处分别出现 C-H 弯曲振动吸收峰和 O-H 弯曲振动吸收峰。接枝共聚物在 $1660\\mathrm{cm}^{-1}$ 和 $1635\\mathrm{cm}^{-1}$ 处分别出现归属于酰胺基的酰胺I 带吸收峰( $\\mathrm{\\dot{C}}=0$ 伸缩振动) 和酰胺II 带吸收峰(N-H 弯曲振动)，在 $1430\\mathrm{cm}^{-1}$ 处出现C-N 的伸缩振动吸收峰； $3422\\mathrm{{cm}^{-1}}$ 处 O-H 伸缩振动吸收峰与 N-H 伸缩振动吸收峰叠加；在 $1040\\mathrm{cm}^{-1}$ 处出现 O-S 的伸缩振动吸收峰；在 $601\\mathrm{cm}^{-1}$ 处出现 C-S 的伸缩振动吸收峰。由此证明了 ${\\tt A M P S-c o-A M}$ 长链已接枝到黄原胶上。产物的结构见结构式(11)。  \n\n[0072]  \n\n[0073] 式中g 表示接枝，co 表示共聚，下同。  \n\n[0074] 在提取液中添加少量对苯二酚，减压蒸馏，除去甲醇，将剩余浓缩液倾入过量甲醇中，产生的沉淀即为副产品均聚物。  \n\n[0075] 将黄原胶与黄原胶接枝共聚物 $\\mathrm{XG^{-}g^{-}}\\left(\\mathrm{AM\\mathrm{-}c o^{-}A M P S}\\right)$ 的表面形貌进行 SEM 观察，分别如图 3、图 4 所示。 $\\mathrm{XG^{-}g^{-}\\left(A M\\mathrm{-}c o^{-}A M P S\\right)}$ 形貌较改性前黄原胶有了较大程度的改变，间接证明了接枝反应的发生。  \n\n[0076] 对比例1 用单一引发剂硝酸铈铵制备黄原胶接枝丙烯酰胺[0077] 室温下，在 $250\\mathrm{mL}$ 三口烧瓶中，加入 1g 黄原胶和 $100\\mathrm{g}$ 蒸馏水，充分搅拌使黄原胶完全溶解，通入高纯氮气鼓泡除氧。将 $4\\mathrm{g}$ 丙烯酰胺加入到反应容器中，搅拌至完全溶解；向反应容器中继续通入高纯氮气鼓泡除氧20 分钟以上。将三口烧瓶放在 $55^{\\circ}\\mathrm{C}$ 恒温水浴锅中，在氮气保护下，加入 $0.02\\mathrm{g}$ 硝酸铈铵， $55\\mathrm{{^\\circC}}$ 下反应3 小时，将产物用过量丙酮沉淀， $50^{\\circ}\\mathrm{C}$ 下完全干燥，得到接枝共聚粗产物。将粗产品用体积比为 $80:20$ 的甲醇 - 水混合溶剂在索氏提取器中萃取12 小时以上，以除去PAM 均聚物，抽提剩余物用蒸馏水反复洗涤，得到接枝共聚物，于 $50^{\\circ}\\mathrm{C}$ 下完全干燥，称重。在提取液中添加少量对苯二酚，减压蒸馏，除去甲醇，将剩余浓缩液倾入过量甲醇中，产生的沉淀即为PAM 均聚物。  \n\n[0078] 对比例2 用单一引发剂过硫酸铵、亚硫酸氢钠制备黄原胶接枝丙烯酰胺[0079] 室温下，在 $250\\mathrm{mL}$ 三口烧瓶中，加入 $\\mathrm{1g}$ 黄原胶和 $100\\mathrm{g}$ 蒸馏水，充分搅拌使黄原胶完全溶解，通入高纯氮气鼓泡除氧。将 $4\\mathrm{g}$ 丙烯酰胺加入到反应容器中，搅拌至完全溶解；向反应容器中继续通入高纯氮气鼓泡除氧20 分钟以上。将三口烧瓶放在 $55^{\\circ}\\mathrm{C}$ 恒温水浴锅中，在氮气保护下，加入 $0.2\\mathrm{g}$ 过硫酸铵， $0.6\\mathrm{g}$ 亚硫酸氢钠， $55\\mathrm{{^\\circC}}$ 反应3 小时，将产物用过量丙酮沉淀， $50^{\\circ}\\mathrm{C}$ 下完全干燥，得到接枝共聚粗产物。将粗产品用体积比为 $80:20$ 的甲醇- 水混合溶剂在索氏提取器中萃取 12 小时以上，以除去 PAM 均聚物，抽提剩余物用蒸馏水反复洗涤，得到接枝共聚物，于 $50^{\\circ}\\mathrm{C}$ 下完全干燥，称重。在提取液中添加少量对苯二酚，减压蒸馏，除去甲醇，将剩余浓缩液倾入过量甲醇中，产生的沉淀即为PAM 均聚物。  \n\n[0080] 实施例2 本发明的耐温抗盐黄原胶接枝共聚物制备[0081] 室温下，在 $250\\mathrm{mL}$ 三口烧瓶中，加入 1g 黄原胶和 $100\\mathrm{g}$ 蒸馏水，充分搅拌使黄原胶完全溶解，通入高纯氮气鼓泡除氧。将 $3.44\\mathrm{g}\\mathrm{N}^{-}$ 乙烯基吡咯烷酮(NVP) 加入到反应容器中，搅拌至完全溶解；向反应容器中继续通入高纯氮气鼓泡除氧20 分钟以上。将三口烧瓶放在$55^{\\circ}\\mathrm{C}$ 恒温水浴锅中，在氮气保护下，加入 $0.02\\mathrm{g}$ 硝酸铈铵， $55\\mathrm{{^\\circC}}$ 下反应 5 分钟后，加入 $0.2\\mathrm{g}$ 过硫酸铵，0.6g 亚硫酸氢钠，将 $\\mathrm{2g}$ 丙烯酰胺 (AM) 配成 $50\\%$ 的水溶液缓慢滴加入到反应容器中， $55^{\\circ}\\mathrm{C}$ 下反应 3 小时，将产物用过量丙酮沉淀， $50^{\\circ}\\mathrm{C}$ 下完全干燥，得到接枝共聚粗产物。  \n\n将粗产品用体积比为 $80:20$ 的甲醇- 水混合溶剂在索氏提取器中萃取12 小时以上，以除去均聚物，抽提剩余物用蒸馏水反复洗涤，得到接枝共聚物，于 $50^{\\circ}\\mathrm{C}$ 下完全干燥，称重，得到黄原胶接枝共聚物 $\\mathrm{XG-g-(AM-co-NVP)}$ 。将产物进行IR 测试，并与黄原胶IR 结果进行对比。接枝共聚物在 $1660\\mathrm{cm}^{-1}$ 和 $1635\\mathrm{cm}^{-1}$ 处分别出现归属于酰胺基的酰胺 I 带吸收峰 ( $\\mathrm{\\DeltaC=0}$ 伸缩振动) 和酰胺II 带吸收峰(N-H 弯曲振动)，在 $1430\\mathrm{cm}^{-1}$ 处出现C-N 的伸缩振动吸收峰；$3422\\mathrm{cm}^{-1}$ 处O-H 伸缩振动吸收峰与N-H 伸缩振动吸收峰叠加；在 $1399\\mathrm{cm}^{-1}$ 处出现专属于NVP结构单元C-N 的伸缩振动吸收峰。由此证明了 $_{\\mathrm{NVP-co-AM}}$ 长链已接枝到黄原胶上。产物的结构见结构式(12)。  \n\n[0082]  \n\n![](images/8fead7ee88a84eb6c11db8215ecbb94f3ba2826ce249081a7442e87c7027cea0.jpg)  \n(12)  \n\n[0083] 在提取液中添加少量对苯二酚，减压蒸馏，除去甲醇，将剩余浓缩液倾入过量甲醇中，产生的沉淀即为均聚物。  \n\n[0084] 实施例3 本发明的耐温抗盐黄原胶接枝共聚物制备[0085] 室温下，在 $250\\mathrm{mL}$ 三口烧瓶中，加入 $\\mathrm{1g}$ 黄原胶和 $100\\mathrm{g}$ 蒸馏水，充分搅拌使黄原胶完全溶解，通入高纯氮气鼓泡除氧。将 $2.79\\mathrm{g}$ 的 N， $\\mathrm{N^{-}}$ 二甲基丙烯酰胺加入到反应容器中，搅拌至完全溶解；向反应容器中继续通入高纯氮气鼓泡除氧20 分钟以上。将三口烧瓶放在$55^{\\circ}\\mathrm{C}$ 恒温水浴锅中，在氮气保护下，加入 $0.02\\mathrm{g}$ 硝酸铈铵， $55^{\\circ}\\mathrm{C}$ 下反应 5 分钟后，加入 $0.2\\mathrm{g}$ 过硫酸铵， $0.6\\mathrm{g}$ 亚硫酸氢钠，将 $5.83\\mathrm{g}$ AMPS 配成 $50\\%$ 的水溶液缓慢滴加入到反应容器中，$55^{\\circ}\\mathrm{C}$ 下反应 3 小时，将产物用过量丙酮沉淀， $50^{\\circ}\\mathrm{C}$ 下完全干燥，得到接枝共聚粗产物。将粗产品用体积比为 $80:20$ 的甲醇- 水混合溶剂在索氏提取器中萃取12 小时以上，以除去均聚物，抽提剩余物用蒸馏水反复洗涤，得到接枝共聚物，于 $50^{\\circ}\\mathrm{C}$ 下完全干燥，称重，得到黄原胶接枝共聚物 $\\mathrm{XG-g-(DMAM-co-AMPS)}$ 。将产物进行IR 测试，并与黄原胶IR 结果进行对比。枝共聚物在 $1660\\mathrm{cm}^{-1}$ 和 $1635\\mathrm{cm}^{-1}$ 处分别出现归属于酰胺基的酰胺 I 带吸收峰 ( $\\mathrm{\\dot{C}}=0$ 伸缩振动 ) 和酰胺 II 带吸收峰 (N-H 弯曲振动 )，在 $1430\\mathrm{cm}^{-1}$ 处出现 C-N 的伸缩振动吸收峰；$3422\\mathrm{{cm}^{-1}}$ 处 O-H 伸缩振动吸收峰与 N-H 伸缩振动吸收峰叠加；在 $1040\\mathrm{cm}^{-1}$ 处出现 O-S 的伸缩振动吸收峰；在 $601\\mathrm{cm}^{-1}$ 处出现 C-S 的伸缩振动吸收峰； $3422\\mathrm{{cm}^{-1}}$ 处 O-H 伸缩振动吸收峰与N-H 伸缩振动吸收峰叠加； $2936\\mathrm{cm}^{-1}$ 出现 $\\mathrm{-CH_{3}}$ 吸收峰， $1356\\mathrm{cm}^{-1}$ 和 $1401\\mathrm{cm}^{-1}$ 出现典型的甲基对称弯曲振动吸收峰，由此证明了AMPS-co-DMAM 长链已接枝到黄原胶上。产物的结构见结构式 (13)。  \n\n[0086]  \n\n[0087] 在提取液中添加少量对苯二酚，减压蒸馏，除去甲醇，将剩余浓缩液倾入过量甲醇中，产生的沉淀即为均聚物。  \n\n[0088] 实施例4 本发明的耐温抗盐黄原胶接枝共聚物制备[0089] 室温下，在 $250\\mathrm{mL}$ 三口烧瓶中，加入 $\\mathrm{1g}$ 黄原胶和 $100\\mathrm{g}$ 蒸馏水，充分搅拌使黄原胶完全溶解，通入高纯氮气鼓泡除氧。将2.91g的 $2^{-}$ 丙烯酰胺基 $-2-$ 甲基丙磺酸和 $1.39\\mathrm{g}$ 的N，$\\mathrm{N^{-}}$ 二甲基丙烯酰胺加入到反应容器中，搅拌至完全溶解；向反应容器中继续通入高纯氮气鼓泡除氧20分钟以上。将三口烧瓶放在 $55^{\\circ}\\mathrm{C}$ 恒温水浴锅中，在氮气保护下，加入 $0.02\\mathrm{g}$ 硝酸铈铵， $55^{\\circ}\\mathrm{C}$ 下反应5分钟后，加入 $0.2\\mathrm{g}$ 过硫酸铵，0.6g亚硫酸氢钠，将1g丙烯酰胺(AM)配成$50\\%$ 的水溶液缓慢滴加入到反应容器中， $55\\mathrm{{^\\circC}}$ 下反应 3 小时，将产物用过量丙酮沉淀， $50^{\\circ}\\mathrm{C}$ 下完全干燥，得到接枝共聚粗产物。将粗产品用体积比为 $80:20$ 的甲醇- 水混合溶剂在索氏提取器中萃取 12 小时以上，以除去均聚物，抽提剩余物用蒸馏水反复洗涤，得到接枝共聚物，于 $50^{\\circ}\\mathrm{C}$ 下完全干燥，称重，得到黄原胶接枝共聚物 $\\mathrm{XG-g-(DMAM-co-AMPS-co-AM)}$ 。将产物进行 IR 测试，并与黄原胶 IR 结果进行对比。接枝共聚物在 $1675\\mathrm{cm}^{-1}$ 和 $1655\\mathrm{cm}^{-1}$ 出现分别归属于 AM 和 AMPS 单元酰胺基的酰胺 I 带吸收峰 ( $\\mathrm{\\DeltaC=0}$ 伸缩振动 )， $1635\\mathrm{cm}^{-1}$ 处酰胺II 带吸收峰 (N-H 弯曲振动 )，在 $1430\\mathrm{cm}^{-1}$ 处出现 C-N 的伸缩振动吸收峰； $3422\\mathrm{{cm}^{-1}}$ 处 O-H伸缩振动吸收峰与 N-H 伸缩振动吸收峰叠加；在 $1040\\mathrm{cm}^{-1}$ 处出现 O-S 的伸缩振动吸收峰；在 $601\\mathrm{cm}^{-1}$ 处出现C-S 的伸缩振动吸收峰； $3422\\mathrm{{cm}^{-1}}$ 处O-H 伸缩振动吸收峰与N-H 伸缩振动吸收峰叠加； $2936\\mathrm{cm}^{-1}$ 出现 $\\mathrm{-CH_{3}}$ 吸收峰， $1356\\mathrm{{cm}^{-1}}$ 和 $1401\\mathrm{cm}^{-1}$ 出现典型的甲基对称弯曲振动吸收峰。由此证明了 $\\mathrm{DMAM-co-AMPS-co-AM}$ 长链已接枝到黄原胶上。产物的结构见结构式(14)。  \n\n[0090]  \n\n[0091] 在提取液中添加少量对苯二酚，减压蒸馏，除去甲醇，将剩余浓缩液倾入过量甲醇  \n\n中，产生的沉淀即为均聚物。  \n\n[0092] 测试例  \n\n[0093] 实施例 $1\\sim4$ 样品的接枝率、接枝效率如表1 所示。对比例 $1\\sim2$ 样品的接枝率、接枝效率如表2 所示。  \n\n[0094] 将实施例中的样品溶于矿化度为 $33000\\mathrm{mg/L}$ 的盐水中，配成浓度为 $1500\\mathrm{mg/L}$ 的清澈透明黏稠液体，在 $25^{\\circ}\\mathrm{C}\\cdot85^{\\circ}\\mathrm{C}$ 测试溶液表观黏度，数据如表3 所示。  \n\n[0095] 表 1 本发明的黄原胶接枝共聚物驱油剂的性能[0096]  \n\n<html><body><table><tr><td>实施例</td><td>１</td><td>2</td><td>3</td><td>４</td></tr><tr><td>接枝率 (%)</td><td>200.1</td><td>155.4</td><td>190.7</td><td>170.2</td></tr><tr><td>接枝效率(%)</td><td>95.2</td><td>89.5</td><td>86.5</td><td>84.4</td></tr></table></body></html>  \n\n[0097] 表 2 对比例中黄原胶接枝共聚物驱油剂的性能 [0098]  \n\n<html><body><table><tr><td>对比例</td><td>1</td><td>2</td></tr><tr><td>接枝率(%)</td><td>104.1</td><td>125.5</td></tr><tr><td>接枝效率(%）</td><td>50.2</td><td>78.5</td></tr></table></body></html>  \n\n[0099] 表 3 实施例样品溶液表观黏度随温度变化值  \n\n[0100]  \n\n<html><body><table><tr><td>实施例</td><td>1</td><td>2</td><td>3</td><td>4</td><td>未改性黄原胶</td></tr><tr><td>25℃表观黏度</td><td>80.8</td><td>85.9</td><td>80.8</td><td>89.8</td><td>68.49</td></tr><tr><td>85℃表观黏度 (mPa·s)</td><td>40.5</td><td>38.7</td><td>41.8</td><td>50.9</td><td>22.60</td></tr></table></body></html>  \n\n[0101] 应用例：  \n\n[0102] 对实施例 1 样品进行取油剂性能研究和室内模拟驱油实验，并与未接枝改性的黄原胶进行对。所用的人造岩心孔隙度～ $30\\%$ 、渗透率 $\\sim2.0\\upmu\\mathrm{\\m}^{2}$ ，含 $90\\%\\ \\mathrm{Si0_{2}.10\\%\\ N a_{2}O}.$ 。[0103] 模拟油样为混合油，其组成为，胜利油田原油∶中性煤油 $\\mathit{\\Theta}=1:0.9$ 。[0104] 实验用水分别为胜利油田底层水和注入水，其组成见表4。[0105] 表 4 胜利油田地层水和注入水中各种离子的含量 $(\\mathrm{mg/L})$  \n\n<html><body><table><tr><td>水样</td><td>Ca2+</td><td>Mg2+</td><td>Na++K+</td><td>Cl\"</td><td>S042-</td><td>HCO3</td></tr><tr><td>地层水</td><td>612</td><td>302</td><td>13732</td><td>16373</td><td>64</td><td>1398</td></tr><tr><td>注入水</td><td>220</td><td>30</td><td>4537</td><td>3885</td><td>119</td><td>783</td></tr></table></body></html>  \n\n[0107] 驱油剂的溶解性能  \n\n[0108] 实施例 1 样品在 $105^{\\circ}\\mathrm{C}$ 干燥90min 后固含量为 $91.5\\%$ 。称取 $\\mathrm{1g}$ 在 $400\\mathrm{r/min}$ 搅拌下溶于 $1000\\mathrm{ml}$ 蒸馏水中，连续搅拌 90min 后放置过夜，用孔径 $5\\upmu\\textrm{m}$ 的滤膜过滤，将滤出物连同滤膜在 $105^{\\circ}\\mathrm{C}$ 下干燥90min 后称量，测得水不溶物含量为 $0.12\\%$ 。驱油剂溶液均一、无不溶解的颗粒。相同测试条件下黄原胶水不溶物含量为 $0.29\\%$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# [0109] 驱油剂溶液的注入性  \n\n[0110] 将岩心抽空并饱和地层水，在 $80^{\\circ}\\mathrm{C}$ 下注入实施例 1 样品溶液，注入压力大体上随注入速度的增加线性增大，注入过程中未发现压力突变现象，实验测得浓度 $1000\\mathrm{mg/L}$ 的实施例 1 样品溶液的筛网系数为 18.4，过滤因子为 1.02，这表明该驱油剂具有良好的注入能力。  \n\n[0111] 驱油剂溶液黏度与采收率的关系  \n\n[0112] 以 $0.2\\mathrm{ml/min}$ 的流量将注入水泵入在 $80^{\\circ}\\mathrm{C}$ 下已建立束缚水的人造岩心，至岩心流出液含水 $98\\%$ ，计算水驱采收率 Rw。再注入 0.3PV 不同黏度 ( 即不同浓度 ) 的驱油剂溶液，用注入水驱至流出液含水 $98\\%$ ，计算驱油剂溶液的采收率 $\\mathrm{{Rp}}$ 及采收率提高值 $\\Delta\\mathrm{R}=$ $(\\mathrm{Rp-Rw})$ 。结果如表5、表6 所示。随驱油剂溶液黏度的增加，采收率提高值 $\\Delta\\mathrm{R}$ 增大。采收率明显优于纯黄原胶驱油剂，见表6。  \n\n[0113] 表 5 实施例1 样品溶液表观黏度与采收率的关系[0114]  \n\n\n<html><body><table><tr><td>序 号</td><td>溶液浓度 (mg/L)</td><td>溶液黏度 (mPaS)</td><td>Rw (%)</td><td>Rp (%)</td><td>△R (%)</td></tr><tr><td>1</td><td>500</td><td>43.1</td><td>55.86</td><td>65.10</td><td>9.24</td></tr><tr><td>２</td><td>1000</td><td>65.3</td><td>68.63</td><td>80.13</td><td>11.50</td></tr><tr><td>３</td><td>1500</td><td>80.8</td><td>61.44</td><td>79.31</td><td>17.87</td></tr></table></body></html>  \n\n[0115] 表 6 未改性黄原胶样品溶液表观黏度与采收率的关系[0116]  \n\n<html><body><table><tr><td>序 号</td><td>溶液浓度 (mg/L)</td><td>溶液黏度 (mPaS)</td><td>Rw (%)</td><td>Rp (%)</td><td>△R (%)</td></tr><tr><td>１</td><td>500</td><td>9.4</td><td>55.86</td><td>60.56</td><td>4.7</td></tr><tr><td>２</td><td>1000</td><td>29.3</td><td>68.63</td><td>73.83</td><td>5.20</td></tr><tr><td>3</td><td>1500</td><td>68.49</td><td>61.44</td><td>72.31</td><td>10.87</td></tr></table></body></html>  \n\n[0117] 驱油剂在不同注水期的驱油效果  \n\n[0118] 针对胜利油田的具体情况，在 $80^{\\circ}\\mathrm{C}$ 下考察了不同注水期驱油剂的驱替效果。将长$30\\mathrm{cm}$ 、内径 2.3cm 的石英砂充填有机玻璃长管岩心抽空，饱和地层水，用模拟油 ( 混合油 )建立束缚水后用注入水驱替，当流出液含水率达到 $90\\%\\sim99\\%$ 范围的某一值后计算相应水驱采收率 Rw，转注 0.3PV 浓度 $1500\\mathrm{mg/l}$ 的驱油剂溶液，用注入水驱至流出液含水 $98\\%$ ，计算注驱油剂的采收率提高值 $\\Delta\\mathrm{R}$ 。表7 给出了在不同流出液含水率时转注驱油剂获得的  \n\n采收率提高值。  \n\n[0119] 表 7 不同含水期转注实施例1 样品溶液的采收率提高值 $\\Delta\\mathrm{R}$ [0121] 表 8 不同含水期转注黄原胶样品溶液的采收率提高值 $\\Delta\\mathrm{R}$  \n\n<html><body><table><tr><td>含水率(%)</td><td>90.91</td><td>93.23</td><td>96.00</td><td>98.60</td></tr><tr><td>△R(% )</td><td>23.66</td><td>21.53</td><td>20.72</td><td>16.48</td></tr></table></body></html>  \n\n[0122]  \n\n<html><body><table><tr><td>含水率(%)</td><td>90.91</td><td>93.23</td><td>96.00</td><td>98.60</td></tr><tr><td>△R(%)</td><td>13.44</td><td>13.58</td><td>10.52</td><td>9.00</td></tr></table></body></html>  \n\n![](images/b5ed68164f7624c260259d4a4e8ea7169573c08e8687fbc31e51e464751642fb.jpg)  \n图 1  \n\n![](images/168d70bf46f3dcc1d98525d54edd315dc2aa337ebbf0db1d8e7437c065198b22.jpg)  \n图 2  \n\n![](images/b3664c9b0b9a67d4b7eab1bfa95203595f735eb4f0f592ecfc954bfc77e087ae.jpg)  \n图 3  \n\n![](images/782731c2859a5284952cf392bf78ae4f9e813e71941d34e347717d102f251906.jpg)  \n图 4",
+        "category": " Results and discussion"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# （19）中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# （12）发明专利申请  \n\n（10）申请公布号CN102666753A（43）申请公布日2012.09.12  \n\n<html><body><table><tr><td>（21）申请号201080052429.5</td><td>(51)Int.CI.</td></tr><tr><td>(22）申请日2010.12.21</td><td>CO9D133/24(2006.01)</td></tr><tr><td>(30）优先权数据</td><td>CO9D7/12(2006.01)</td></tr><tr><td>2010-0028172010.01.08JP</td><td>CO9D133/06(2006.01)</td></tr><tr><td></td><td>CO9D139/00(2006.01)</td></tr><tr><td>（85）PCT申请进入国家阶段日</td><td>CO9D141/00(2006.01)</td></tr><tr><td>2012.05.18</td><td>CO9K3/18(2006.01)</td></tr><tr><td>(86）PCT申请的申请数据</td><td></td></tr><tr><td>PCT/JP2010/0730202010.12.21</td><td></td></tr><tr><td>(87）PCT申请的公布数据</td><td></td></tr><tr><td>WO2011/083686JA2011.07.14</td><td></td></tr><tr><td>(71）申请人日油株式会社</td><td></td></tr><tr><td>地址日本东京 (72)发明人加纳崇光益子真司卷口琢郎</td><td></td></tr><tr><td>山田伦久</td><td></td></tr><tr><td>(74）专利代理机构北京路浩知识产权代理有限</td><td></td></tr><tr><td>公司11002</td><td>权利要求书1页说明书16页</td></tr><tr><td>代理人谢顺星王朋飞</td><td>按照条约第19条修改的权利要求书1页</td></tr></table></body></html>",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# （54）发明名称  \n\n防雾涂料组合物",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# （57）摘要  \n\n本发明提供一种防雾涂料组合物，所述防雾涂料组合物即使在进行涂料涂饰及干燥时湿度高的情况下，也能够抑制雾浊现象，并且能够使其在低温且短时间的条件下加热固化，能够获得对基材的粘附性、耐热性及防雾性优异的涂膜。所述防雾涂料组合物含有共聚物（A）、胺类等碱性化合物（B）及阴离子表面活性剂等表面活性剂（C）。所述共聚物（A）由含有下述所示的单体（A1）、单体（A2）及单体（A3）的单体混合物形成。单体（A1）为具有N-羟甲基或N-烷氧基羟甲基的乙烯基类单体，单体（A2）为具有磺酸基的乙烯基类单体，单体（A3）为（甲基）丙烯酸烷基酯类单体。  \n\n1.防雾涂料组合物，其特征在于，所述防雾涂料组合物含有共聚物(A)、碱性化合物(B）及表面活性剂（C)，所述共聚物（A）由含有下述所示的单体（A1）、单体（A2）及单体（A3）的单体混合物形成；单体（A1）：具有 $\\mathrm{N-}$ 羟甲基或 $\\mathrm{N^{-}}$ 烷氧基羟甲基的乙烯基类单体；单体（A2）：具有磺酸基的乙烯基类单体；单体（A3）：（甲基）丙烯酸烷基酯类单体。2.根据权利要求1所述的防雾涂料组合物，其特征在于，以单体（A1)、单体（A2）及单体（A3）的总量为100质量份计，单体（A1）的含量为 $3\\sim20$ 质量份、单体（A2）的含量为$3\\sim20$ 质量份、单体（A3）的含量为 $60\\sim94\\$ 质量份，以及单体（A1）及单体（A2）的总量为$6\\sim40$ 质量份；相对于单体（A2）的磺酸基，碱性化合物（B）的含量为 $50\\sim95\\mathrm{mol}\\%$ ；以共聚物（A）为100质量份计，表面活性剂（C）的含量为 $0.5\\sim30$ 质量份。3.根据权利要求1或2所述的防雾涂料组合物，其特征在于，所述单体混合物还含有N,N-二烷基（甲基）丙烯酰胺类单体（A4)，以单体（A3）及单体（A4）的总量为100质量份计，单体（A4）为 $5\\sim50$ 质量份。4.根据权利要求1至3中任意一项所述的防雾涂料组合物，其特征在于，碱性化合物(B)在 $25^{\\circ}\\mathrm{C}$ 水溶液中的碱解离常数为 $3\\sim14$ 。5.根据权利要求1至4中任意一项所述的防雾涂料组合物，其特征在于，碱性化合物(B）的沸点为 $130\\sim1500^{\\circ}\\mathrm{C}$ 。6.根据权利要求1所述的防雾涂料组合物，其特征在于，共聚物（A）具有单体（A1）的$N-$ 羟甲基或 $N-$ 烷氧基羟甲基通过缩合反应形成的交联结构；单体（A2）具有中和了的磺酸基和未被中和的磺酸基，所述中和了的磺酸基提高共聚物（A）的亲水性，所述未被中和的磺酸基促进单体（A1）的所述缩合反应。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 防雾涂料组合物",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001]本发明涉及防雾涂料组合物，所述防雾涂料组合物形成于例如汽车前照灯等的基材上，即使在进行涂料涂饰及干燥时湿度高的情况下，也不会产生雾浊（blushing）等问题，能够使其在低温且短时间的条件下加热固化，用于给予对基材的粘附性、耐热性及防雾性优异的涂膜。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002]对于汽车的前照灯等车辆灯具，由于高湿度的空气进入灯室内，因外部气体或降雨等原因使镜片变凉，水分凝结到内侧面上，从而往往会出现结雾。其结果，降低了车灯的亮度，并且影响镜片的美观，从而存在给使用者带来不快的情况。为了防止这种镜片结雾，已知在结雾的部位涂布防雾涂料。  \n\n[0003]本申请人已经提出了如下所述的加热固化型防雾涂料组合物（参见专利文献1)。即，该加热固化型防雾涂料组合物含有嵌段共聚物或接枝共聚物，所述嵌段共聚物或接枝共聚物由亲水性聚合物部分与疏水性聚合物部分构成，所述亲水性聚合物部分由具有N-羟甲基、N-羟甲基醚基、羟基中的任一种交联官能团的单体、亲水性单体及（甲基）丙烯酸低级烷基酯形成，所述疏水性聚合物部分由具有磺酸基、羧基或磷酸基的乙烯基类单体及（甲基）丙烯酸低级烷基酯形成。根据该防雾涂料组合物，可形成在高温环境下能够维持优异的防雾性和粘附性的涂膜。  \n\n[0004] 现有技术文献  \n\n[0005] 专利文献[0006] 专利文献1：特开平6-212146号公报（第2页、第3页、第14页 $\\sim$ 第17页）",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0007] 本发明要解决的技术问题  \n\n[0008]但是，专利文献1中记载的防雾涂料组合物，为了使涂膜在 $80^{\\circ}\\mathrm{C}$ 的低温下加热固化，需要60分钟之久的时间。并且在涂饰防雾涂料组合物时环境的相对湿度（RH）高于$60\\%$ 的情况下，会发生因共聚物的疏水性聚合物部分而引起的雾浊现象，存在涂膜容易白化的问题。在此，雾浊现象是指进行涂料涂饰及干燥时的湿度高时（例如相对湿度在 $60\\%$ 以上），在涂饰过程及干燥过程中，空气中的水分微粒冷凝在涂膜表面上，使树脂成分凝结、析出或涂膜表面产生凹凸，从而看起来涂膜白化的现象。  \n\n[0009]因此，本发明的目的在于，提供一种防雾涂料组合物，所述防雾涂料组合物即使在进行涂料涂饰及干燥时湿度高的情况下也能够抑制雾浊现象，并且能够使其在低温且短时间的条件下加热固化，能够获得对基材的粘附性、耐热性及防雾性优异的涂膜。  \n\n[0010] 解决技术问题的技术手段  \n\n[0011]为了实现上述目的，本发明的一个实施方式的防雾涂料组合物，其含有共聚物（A)、碱性化合物（B）及表面活性剂（C），所述共聚物（A）由含有下述所示的单体（A1）、单体  \n\n(AZ）及单体（A3）的单体混合物形成，  \n\n[0012]单体（A1）：具有 $\\mathrm{N-}$ 羟甲基或 $N-$ 烷氧基羟甲基（N-alkoxymethylolgroup）的乙烯基类单体；  \n[0013] 单体（A2）：具有磺酸基（磺基、 $-\\mathrm{S}0_{3}\\mathrm{H})$ 的乙烯基类单体；  \n[0014] 单体（A3）：（甲基）丙烯酸烷基酯类单体。  \n[0015] 优选的是，以单体（A1）、单体（A2）及单体（A3）的总量为100质量份计，单体（A1）的含量为 $3\\sim20$ 质量份、单体（A2）的含量为 $3\\sim20$ 质量份、单体（A3）的含量为 $60\\sim94\\$ 质量份，以及单体（A  \n[0016]1）与单体（A2）的总量为 $6\\sim40$ 质量份；相对于单体（A2）的磺酸基，碱性化合物（B）的含量为 $50\\sim95\\mathrm{mol}\\%$ ；以共聚物（A）为100质量份计，表面活性剂（C）的含量为$0.5\\sim30$ 质量份。  \n[0017] 所述单体混合物还含有N，N-二烷基（甲基）丙烯酰胺类单体(A4)，以单体（A3)及单体（A4）的总量为100质量份计，单体（A4）优选为 $5\\sim50$ 质量份。  \n[0018] 碱性化合物（B）在 $25\\mathrm{^\\circC}$ 水溶液中的碱解离常数优选为 $3\\sim14$ 0  \n[0019] 碱性化合物（B）的沸点优选为 $130\\sim1500^{\\circ}\\mathrm{C}$ 。  \n[0020]在一个实例中，共聚物（A）具有单体（A1）的 $\\mathrm{N^{-}}$ 羟甲基或 $N-$ 烷氧基羟甲基通过缩合反应形成的交联结构；单体（A2）具有中和了的磺酸基和未被中和的磺酸基，所述中和了的磺酸基提高共聚物（A）的亲水性及耐热性，所述未被中和的磺酸基促进单体（A1）的所述缩合反应。  \n[0021] 发明效果  \n[0022] 根据本发明，能够发挥如下效果。  \n[0023]在第一发明的防雾涂料组合物中，基于形成共聚物的单体（A1）的性质，表现出了良好的固化性，基于单体（A2）的性质，表现出了在低温下对固化性的促进及对雾浊现象的抑制，基于单体（A3）的性质，表现出了对基材的良好的粘附性和耐热性。另外，基于碱性化合物(B)的性质，使单体（A2）的部分磺酸基被中和，提高了共聚物的亲水性，并提高了对雾浊现象的抑制效果，在此基础上还抑制了涂膜在高温环境下因磺酸基引起的氧化劣化，表现出了优异的耐热性。另外，通过表面活性剂（C）的表面活性作用，降低了附着在涂膜表面的水分的表面张力，通过形成水膜，表现出了良好的防雾性。  \n[0024]因此，防雾涂料组合物即使在进行涂料涂饰及干燥时湿度高的情况下，也能够抑制雾浊现象，并在低温且短时间的条件下具有优异的加热固化性，同时得到的涂膜能够发挥出对基材的优异的粘附性、耐热性及防雾性。",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 具体实施方式  \n\n[0025] 下面通过具体实施方式详细说明本发明。  \n[0026] <防雾涂料组合物>  \n[0027] 本实施方式的防雾涂料组合物含有共聚物（A)、碱性化合物（B）及表面活性剂(C)，所述共聚物（A）由含有下述所示的单体（A1）、单体（A2）及单体（A3）的单体混合物形成；  \n[0028]单体（A1）：具有N-羟甲基（-NHCHOH）或N-烷氧基羟甲基（-NHCHOR，但R为烷  \n\n基）的乙烯基类单体；  \n\n[0029] 单体（A2）：具有磺酸基（磺基、 $-\\mathrm{S}0_{3}\\mathrm{H})$ 的乙烯基类单体；  \n[0030] 单体（A3）：（甲基）丙烯酸烷基酯类单体。  \n\n[0031]该防雾涂料组合物适合用作例如前照灯等车辆灯具的防雾涂料。该防雾涂料组合物在高湿度环境下进行涂饰及干燥时，不会产生雾浊现象等问题，在低温且短时间的条件下具有优异的加热固化性。并且使防雾涂料组合物加热固化而得到的涂膜，对基材（也称为被涂饰物）的粘附性、耐热性及防雾性优异。  \n\n[0032] 下面，对防雾涂料组合物的构成要素依次进行说明。  \n\n[0033] [共聚物（A)][0034] [单体（A1）]  \n\n[0035]首先，对形成共聚物的单体(A1)，即具有N-羟甲基或 $\\mathrm{N-}$ 烷氧基羟甲基的乙烯基类单体进行说明。该单体（A1）为通过脱水缩合反应或脱醇缩合反应等缩合反应，使分子间交联，用来在共聚物中形成交联结构的乙烯基类单体。由于单体（A1）具有这种交联性官能团，通过对制备后的共聚物进行加热，能够在共聚物中形成交联结构。此外，使用酸催化剂来促进该缩合反应。  \n\n[0036]作为单体(A1）可以例举如N-羟甲基（甲基）丙烯酰胺、N-甲氧基羟甲基（甲基）丙烯酰胺、N-丁氧基羟甲基（甲基）丙烯酰胺等。可以使用其中的一种或两种以上作为单体(A1)。从防雾涂料组合物的保存稳定性优异、在低温下加热固化性优异的角度来看，在这些单体中尤其优选的单体（A1）为N-羟甲基（甲基）丙烯酰胺。  \n\n[0037]在单体（A1）、（A2）及（A3）的总量100质量份中，单体（A1）的含量优选为 $3\\sim20$ 质量份，更优选为 $5\\sim15$ 质量份。单体（A1）的含量低于3质量份的情况下，会降低共聚物在低温下的固化性，使固化时间延长。另一方面，单体（A1）的含量高于20质量份的情况下，共聚物的交联密度变高，会降低涂膜的防雾性，并且，在高温环境下放置的情况下，交联反应会随时间进行，有可能导致进一步降低防雾性。  \n\n[0038] [单体（A2)]  \n\n[0039]接下来，对单体(A2)，即具有磺酸基的乙烯基类单体进行说明。该单体(A2）具有作为酸催化剂的功能，用来在低温下促进上述单体（A1）的缩合反应；该单体（A2)还具有提高共聚物的亲水性、在高湿度环境下进行涂饰及干燥的情况下抑制雾浊现象、用来赋予良好的涂膜外观的功能。  \n\n[0040]作为单体（A2）可以例举如（甲基）丙烯酸 $-3-$ 磺基丙酯、（甲基）丙烯酸 $-2-$ 磺基乙酯、2-丙烯酰胺-2-甲基丙磺酸、对苯乙烯磺酸、乙烯基磺酸、甲代烯丙基磺酸等。可以使用其中的一种或两种以上作为(A2)。  \n\n[0041]从与单体（A1）具有优异的共聚性的角度来看，在这些单体中优选的单体（A2）为（甲基）丙烯酸 $-3-$ 磺基丙酯及（甲基）丙烯酸 $-2-$ 磺基乙酯、2-丙烯酰胺 $-2-$ 甲基丙磺酸。  \n\n[0042]在单体（A1）、（A2）及（A3）的总量100质量份中，单体（A2）的含量优选为 $3\\sim20$ 质量份，更优选为 $5\\sim15$ 质量份。单体（A2）的含量低于3质量份的情况下，在单体（A1）的缩合反应中作为酸催化剂的效果不充分，降低共聚物在低温下的固化性，有固化时间延长的倾向。进一步地，因共聚物的亲水性不足，在高湿度环境下进行涂饰及干燥的情况下，有可能产生雾浊现象。另一方面，单体（A2）的含量高于20质量份的情况下，共聚物（A）的极性变得非常高，使得涂膜和基材之间的亲和性变低，结果存在涂膜的粘附性降低的倾向，在此基础上，因单体（A2）的磺酸基容易引起在高温环境下涂膜的氧化劣化，存在导致涂膜的耐热性降低的倾向。  \n\n[0043] [单体（A3）]  \n\n[0044]接下来，对作为单体（A3）的（甲基）丙烯酸烷基酯类单体进行说明。该单体（A3）为用于提高涂膜的耐热性，并且提高涂膜与基材之间的亲和性，从而给予良好的粘附性的成分。（甲基）丙烯酸烷基酯类单体是指（甲基）丙烯酸的直链、支链或环状的烷基酯。[0045]作为该单体（A3）可以例举如（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丙酯、（甲基）丙烯酸异丙酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸异丁酯、（甲基）丙烯酸叔丁酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸月桂酯、（甲基）丙烯酸十八烷基酯、（甲基）丙烯酸环己酯等。可以使用其中的一种或两种以上作为单体（A3）。[0046]优选的单体（A3）为（甲基）丙烯酸低级烷基酯类单体。（甲基）丙烯酸低级烷基酯类单体是指在（甲基）丙烯酸烷基酯类单体中，烷基酯的烷基碳原子数为 $1\\sim4$ 的物质。进一步优选的单体（A3）为烷基酯的烷基碳原子数为1或2的（甲基）丙烯酸低级烷基酯。在使用烷基酯的烷基碳原子数为5以上的（甲基）丙烯酸烷基酯类单体的情况下，会降低共聚物的亲水性，在高湿度环境下进行涂饰及干燥的情况下，存在容易产生雾浊现象的倾向。  \n\n[0047]在单体（A1）、（A2）及（A3）的总量100质量份中，单体（A3）的含量优选为 $60\\sim94\\$ 质量份，更优选为 $70\\sim90$ 质量份。单体（A3）的含量低于60质量份的情况下，单体（A1）及(A2）的比例增大，因此会降低涂膜与基材之间的粘附性。另一方面，单体（A3）的含量高于94质量份的情况下，单体（A1）及单体（A2）的比例降低，因此共聚物在低温下的固化性降低，存在固化时间延长的倾向。  \n\n[0048] [其他乙烯基类单体]  \n\n[0049]作为用来形成共聚物的单体，除了上述单体（A1)、单体（A2）及单体（A3)之外，还可以使用其他乙烯基类单体。作为这些其他乙烯基类单体只要是能够和单体(A1) $\\sim$ (A3)共聚，则没有特别限制。  \n\n[0050]作为其他乙烯基类单体的具体例，可以例举如苯乙烯、乙烯基甲苯、α-甲基苯乙烯等芳香族乙烯基类单体；（甲氧基）聚乙二醇单（甲基）丙烯酸酯、（甲氧基）聚丙二醇单（甲基）丙烯酸酯、（乙氧基）聚乙二醇单（甲基）丙烯酸酯、（乙氧基）聚丙二醇单（甲基）丙烯酸酯等烷氧基烷二醇（甲基）丙烯酸酯类单体；（甲基）丙烯酸2-羟乙酯、（甲基）丙烯酸2-羟丙酯、（甲基）丙烯酸4-羟丁酯、（甲基）丙烯酸2-羟乙酯的&-己内酯加成产物等的含羟基的乙烯基类单体；（甲基）丙烯酸、巴豆酸、马来酸、马来酸半酯等含羧基单体及其碱金属盐或铵盐；（甲基）丙烯酰胺、 $N-$ 甲基（甲基）丙烯酰胺、N，N-二甲基（甲基）丙烯酰胺、N-乙基（甲基）丙烯酰胺、N， $\\mathrm{N^{-}}$ 二乙基（甲基）丙烯酰胺、N-正丙基（甲基）丙烯酰胺、N-异丙基（甲基）丙烯酰胺、 $.\\mathrm{N-}$ 二甲氨基乙基（甲基）丙烯酰胺、N-二甲氨基丙基（甲基）丙烯酰胺、二丙酮（甲基）丙烯酰胺、N-（甲基）丙烯酰哌啶、（甲基）丙烯酰吗啉、 $\\mathrm{N-}$ 乙烯基 $-2-$ 吡咯烷酮、2-乙烯基吡啶等的含氮原子的乙烯基类单体等。可以使用其中的一种或两种以上作为其他乙烯基类单体。  \n\n[0051] [单体（A4)]  \n\n[0052]从耐热性优异、亲水性高、对雾浊现象的抑制效果良好等方面来看，在其他乙烯基类单体中优选N，N-二甲基（甲基）丙烯酰胺、N，N-二乙基（甲基）丙烯酰胺等N，N-二烷基（甲基）丙烯酰胺类单体（有时简称为单体（A4)）。可以使用一种或两种以上作为单体(A4)。在单体（A3）及单体（A4）的总量100质量份中，单体（A4）的含量优选为 $5\\sim50$ 质量份。  \n\n[0053]另外，从在对基材的粘附性及耐热性优异的同时，能够提高共聚物的亲水性，抑制雾浊现象的方面来看，进一步优选为将（甲基）丙烯酸低级烷基酯类单体（A3）与N，N-二烷基丙烯酰胺类单体（A4）进行组合使用。  \n\n[0054]（甲基）丙烯酸低级烷基酯类单体与N，N-二烷基（甲基）丙烯酰胺类单体进行组合使用的情况下，在（甲基）丙烯酸低级烷基酯类单体（A3）与N，N-二烷基（甲基）丙烯酰胺类单体（A4）的总量100质量份中，（甲基）丙烯酸低级烷基酯类单体（A3）的含量优选为 $50\\sim90\\$ 质量份，N， $N-$ 二烷基（甲基）丙烯酰胺类单体（A4）的含量优选为余量范围。（甲基）丙烯酸低级烷基酯类单体（A3）小于50质量份的情况下，共聚物的亲水性显著提高，因此存在为了获得充分的交联度，固化时间延长的倾向。另一方面，（甲基）丙烯酸低级烷基酯类单体（A3）大于90质量份的情况下，提高共聚物亲水性的效果变低，存在对雾浊现象的抑制效果降低的倾向。  \n\n[0055] [共聚物（A）的制备方法]  \n\n[0056]共聚物（A）是通过将含有上述单体（A1）、（A2)、(A3）及根据需要含有（A4）的单体混合物进行共聚而制得的。作为共聚物的结构可以是无规共聚物、交替共聚物、嵌段共聚物及接枝共聚物中的任意一种结构，但从能够提高防雾涂料组合物以防雾性为首的效果，同时能够容易地配制防雾涂料组合物的角度来看，优选无规共聚物。作为用来得到共聚物的聚合方法，可以使用自由基聚合法、阳离子聚合法、阴离子活性聚合法、阳离子活性聚合法等公知的各种聚合方法，但从工业生产性的容易度、产品性能多样化的方面考虑，尤其优选自由基聚合法。作为自由基聚合法，通常采用块状聚合法、悬浮聚合法、溶液聚合法、乳化聚合法等，但从聚合后能够将其直接用作涂料的角度来看，优选溶液聚合法。  \n\n[0057] 下面说明使用溶液聚合法进行制备的方法。  \n\n[0058]关于聚合溶剂，具有非常高的沸点的聚合溶剂，在涂膜的干燥、加热固化时，存在由于聚合溶剂残留使涂膜对基材的粘附性受损的情况，因此优选使用具有小于 $180^{\\circ}\\mathrm{C}$ 沸点的聚合溶剂。作为这样的聚合溶剂，例如可以使用甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、仲丁醇、叔丁醇、二丙酮醇等醇类溶剂；乙二醇单甲醚、乙二醇单乙醚、丙二醇单甲醚、丙二醇单乙醚、3-甲氧基-1-丁醇、3-甲氧基-3-甲基-1-丁醇等醇醚类溶剂；丙酮、甲乙酮、甲基异丁基酮、环己酮等酮类溶剂；四氢呋喃、二氧六环等醚类溶剂；乙酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸异丁酯、乙酸叔丁酯、乳酸甲酯、乳酸乙酯等酯类溶剂；苯、甲苯、二甲苯等芳香族类溶剂；甲酰胺、二甲基甲酰胺等胺类溶剂；水等。可以使用其中的一种或两种以上作为聚合溶剂。  \n\n[0059]在单体（A1）、(A2)、(A3）及根据需要加入的单体（A4）的总量与用于聚合反应的聚合溶剂的总量100质量份中，单体总量优选为50质量份以下。单体的比例超过50质量份的情况下，存在聚合发热变大，不易于工业制备的倾向。  \n\n[0060]作为自由基聚合引发剂，可以使用通常所使用的有机过氧化物、偶氮化合物。作为有机过氧化物，可以例举如过氧化苯甲酰、过氧化 $3,5,5-$ 三甲基己酰（3，5，5-trimethylhexanoylperoxide)、过氧化 $-2-$ 己酸叔丁酯（t-butylperoxy $^{-2}$ -hexanoate)、过氧化新戊酸叔丁酯（t-butylperoxypivalate）、过氧化新戊酸叔己酯（t-hexylperoxypivalate）等。作为偶氮化合物，可以例举如 $2,2^{\\prime}\\mathrm{~-~}$ 偶氮二异丁睛、2，2’-偶氮双 $-2-$ 甲基丁晴等。在单体(A1)、(A2)、(A3）及根据需要加入的单体（A4)的总量100质量份中，自由基聚合引发剂的添加量优选为 $0.01\\sim5$ 质量份。从边滴加到反应容器中边进行聚合反应会易于控制聚合发热的角度来看，优选自由基聚合引发剂。根据使用的自由基聚合引发剂的种类，可以对聚合温度进行适当调整，但在工业制备中优选为$30\\sim150^{\\circ}\\mathrm{C}$ ，更优选为 $40\\sim100^{\\circ}\\mathrm{C}$ o  \n\n[0061] [碱性化合物（B）]  \n\n[0062]下面，对碱性化合物（B）进行说明。该碱性化合物是用于中和上述单体（A2）的部分磺酸基的成分。由于单体(A2）的部分磺酸基被碱性化合物(B）中和，因此能够提高共聚物的亲水性，并能够提高对雾浊现象的抑制效果，在此基础上，还能够抑制涂膜在高温环境下因磺酸基引起的氧化劣化，能够提高耐热性。  \n\n[0063]作为碱性化合物(B)，可以例举如氢氧化钠、氢氧化钙、氨、甲胺、二甲胺、三甲胺、乙胺、二乙胺、三乙胺、单乙醇胺、二乙醇胺、三乙醇胺、二甲氨基乙醇、二乙氨基乙醇、苯胺、a-萘胺、苄胺、吡啶、 $2,6-$ 二甲基吡啶、咪唑等。可以使用其中的一种或两种以上作为碱性化合物（B）。  \n\n[0064]此外，从加热固化涂膜时与磺酸基容易解离，难以阻碍磺酸基用作酸催化剂的作用的角度来看，碱性化合物（B）在 $25\\mathrm{{^\\circC}}$ 水溶液中的碱解离常数（以下简称为pKb）优选为$3\\sim14$ ，更优选为 $4\\sim14$ 。作为这样的碱性化合物(B)，可以例举如氨 $\\mathrm{(pKb=4.7)}$ 、甲胺${\\mathrm{(pKb=3.5)}}$ 、二甲胺 $\\mathrm{(pKb=3.4)}$ 、三甲胺 $\\mathrm{(pKb=3.2)}$ 、乙胺 $\\mathrm{(pKb=3.5)}$ 、二乙胺 $(\\mathrm{pKb}=$ 3.4)、三乙胺 $\\mathrm{(pKb=3.2)}$ 、单乙醇胺 $\\mathrm{(pKb=4.5)}$ 、二乙醇胺 $\\mathrm{(pKb=5.1)}$ 、三乙醇胺（pKb$=6.2^{\\cdot}$ 、二甲氨基乙醇 $\\mathrm{{(pKb=4.1)}}$ 、二乙氨基乙醇 $\\mathrm{{(pKb=4.1)}}$ 、苯胺 $\\mathrm{(pKb=4.6)}$ 、a-萘胺 $(\\mathrm{pKb}=10.1)$ 、苄胺 $\\mathrm{{(pKb=4.6)}}$ 、吡啶 $(\\mathrm{pKb}=8.8\\$ 、 $2,6-$ 二甲基吡啶 $\\mathrm{{(pKb=8.0)}}$ 、咪唑 $\\mathrm{(pKb=7.1)}$ 等。  \n\n[0065]从提高抑制涂膜在高温环境下因磺酸基引起的氧化劣化的效果的角度来看，碱性化合物（B）优选具有 $130\\sim1500^{\\circ}\\mathrm{C}$ 的沸点，在高温环境下挥发性低，更优选具有 $150\\sim$ $1500^{\\circ}\\mathrm{C}$ 的沸点。作为这样的碱性化合物(B)，可以例举如氢氧化钠（沸点 $1390^{\\circ}\\mathrm{C}$ ）、氢氧化钙（在熔点 $580^{\\circ}\\mathrm{C}$ 下分解）、单乙醇胺（沸点 $172^{\\circ}\\mathrm{C}$ ）、二乙醇胺（沸点 $217^{\\circ}C$ ）、三乙醇胺（沸点$335^{\\circ}\\mathrm{C}$ ）、二甲氨基乙醇（沸点 $144^{\\circ}\\mathrm{C}$ ）、二乙氨基乙醇（沸点 $163^{\\circ}\\mathrm{C}$ ）、苯胺（沸点 $184^{\\circ}\\mathrm{C}$ ）、a-萘胺（沸点 $301^{\\circ}\\mathrm{C}$ ）、苄胺（沸点 $183^{\\circ}\\mathrm{C}$ ） $\\cdot2,6-$ 二甲基吡啶（沸点 $144^{\\circ}\\mathrm{C}$ ）、咪唑（沸点$256^{\\circ}\\mathrm{C}$ ）等。  \n\n[0066]作为碱性化合物(B)，更优选为 $25^{\\circ}\\mathrm{C}$ 水溶液中的pKb为 $3\\sim14$ ，且沸点为 $130\\sim$ $1500^{\\circ}\\mathrm{C}$ 的化合物。作为这样的碱性化合物(B)，可以例举如单乙醇胺、二乙醇胺、三乙醇胺、二甲氨基乙醇、二乙氨基乙醇、咪唑等。  \n\n[0067]作为碱性化合物(B)，最优选为 $25^{\\circ}\\mathrm{C}$ 水溶液中的pKb为 $4\\sim14$ ，且沸点为 $150\\sim$ $1500^{\\circ}\\mathrm{C}$ 的化合物。作为这样的碱性化合物(B)，可以例举如单乙醇胺、二乙醇胺、三乙醇胺、  \n\n二乙氨基乙醇、咪唑等。  \n\n[0068]为了使该碱性化合物（B）仅中和单体（A2）的部分磺酸基，由此使单体（A2）具有提高共聚物（A)的亲水性及耐热性的磺酸基和促进单体（A1）的缩合反应的未被中和的磺酸基，从而决定碱性化合物（B）的含量。在实施方式中，相对于单体（A2）的磺酸基，碱性化合物（B）的含量优选为 $50\\sim95\\mathrm{mol}\\%$ ，更优选为 $60\\sim90\\mathrm{mol}\\%$ 。碱性化合物（B）的含量小于 $50\\%$ 的情况下，提高共聚物亲水性及耐热性的效果会变低。另一方面，碱性化合物(B）的含量大于 $95m o l\\%$ 的情况下，磺酸基作为酸催化剂的功能会降低，并且共聚物在低温下的固化性显著降低，因此不优选。  \n\n[0069]作为通过碱性化合物(B)对单体(A2）的磺酸基进行中和的方法，可以是在共聚物和溶剂的溶液中加入碱性化合物(B）的方法，也可以是在制备共聚物时，将碱性化合物（B)与单体一同加入的方法。在这些方法中，优选后者，这是因为通过单体（A2）被碱性化合物(B）中和，酸度降低，对聚合溶剂的溶解性良好，同时不易腐蚀反应容器。  \n\n[0070] [表面活性剂（C）]  \n\n[0071]下面，对表面活性剂(C)进行说明。该表面活性剂(C）是用来使附着在涂膜表面的水分的表面张力降低，通过在涂膜表面形成水膜，从而提高防雾性的成分。作为表面活性剂(C)，可以使用现有公知的所有表面活性剂，可以例举如非离子表面活性剂、阴离子表面活性剂、阳离子表面活性剂及两性离子表面活性剂等。其中，从效果的持续性来看，优选为至少含有一种以上的阴离子表面活性剂。  \n\n[0072]作为非离子表面活性剂，例如可以使用聚氧乙烯月桂醇、聚氧乙烯月桂醚、聚氧乙烯油基醚等聚氧乙烯高级醇醚类；聚氧乙烯辛基苯酚、聚氧乙烯壬基苯酚等聚氧乙烯烷基芳基醚类；聚氧乙二醇单硬脂酸酯等聚氧乙烯酰基酯类；聚丙二醇环氧乙烯加成产物、聚氧乙烯山梨醇酐单月桂酸酯、聚氧乙烯山梨醇酐单硬脂酸酯等聚氧乙烯山梨醇酐脂肪酸酯类；烷基磷酸酯、聚氧乙烯烷基醚磷酸酯等磷酸酯类；糖脂类；纤维素醚类等。  \n\n[0073]作为阴离子表面活性剂，例如可以使用油酸钠、油酸钾等脂肪酸盐；月桂基硫酸钠、月桂基硫酸铵等高级醇硫酸酯类；十二烷基基苯磺酸钠、烷基萘磺酸钠等烷基苯磺酸盐及烷基萘磺酸盐；萘苯磺酸福尔马林缩合物、二烷基磺化琥珀酸盐、二烷基磷酸盐、聚氧乙烯烷基苯基醚硫酸钠等聚氧乙烯硫酸盐等。  \n\n[0074]作为阳离子表面活性剂，例如可以使用乙醇胺类；月桂胺醋酸盐、三乙醇胺单甲酸盐、硬质酰胺乙基二乙胺醋酸盐等胺盐；月桂基三甲基氯化铵、硬脂基三甲基氯化铵、二月桂基二甲基氯化铵、二硬脂基二甲基氯化铵、月桂基二甲基苄基氯化铵、硬脂基二甲基苄基氯化铵等季铵盐等。  \n\n[0075]作为两性离子表面活性剂，例如可以使用二甲基烷基月桂基甜菜碱、二甲基烷基硬脂基甜菜碱等脂肪酸型两性离子表面活性剂；二甲基烷基磺基甜菜碱等磺酸型两性离子表面活性剂；烷基甘氨酸等。  \n\n[0076]以上述共聚物为100质量份，上述表面活性剂（C）的含量优选为 $0.5\\sim30$ 质量份，更优选为 $1\\sim20$ 质量份。表面活性剂（C）的含量不足0.5质量份的情况下，难以获得长期的涂膜防雾持续性。另一方面，超过30质量份的情况下，表现出涂膜的外观和粘附性降低，同时涂膜的耐水性降低的倾向。作为共聚物与表面活性剂（C）的混合方法，可以将共聚物溶于溶剂后，在其中加入表面活性剂（C)，或者可以在制备共聚物时，将表面活性剂（C）与  \n\n单体一同加入。  \n\n[0077] [其他成分]  \n\n[0078]防雾涂料组合物的必须成分为共聚物(A)、碱性化合物(B）及表面活性剂(C)。在防雾涂料组合物中，作为其他成分，可以根据需要混配流平剂、抗氧化剂、紫外线吸收剂、光稳定剂、固化催化剂等常用的各种添加剂。这些其他成分，每种添加剂可以分别以常用的添加量进行混配。  \n\n[0079] [防雾涂料组合物的制备]  \n\n[0080]防雾涂料组合物，其是将通过上述单体的共聚获得的共聚物溶液，以调节成适合涂饰的粘度作为目的，一般通过加入溶剂溶解、分散或稀释而制得。对于加入到共聚物溶液中的溶剂，具有非常高的沸点的溶剂，在涂膜的干燥、加热固化时，存在因溶剂的残留损害涂膜对基材的粘附性的情况，因此优选使用具有小于 $180^{\\circ}\\mathrm{C}$ 的沸点的聚合溶剂。  \n\n[0081］作为这样的溶剂可以例举如甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、仲丁醇、叔丁醇、二丙酮醇等醇类溶剂；乙二醇单甲醚、乙二醇单乙醚、丙二醇单甲醚、丙二醇单乙醚、3-甲氧基-1-丁醇、3-甲氧基-3-甲基-1-丁醇等醇醚类溶剂；丙酮、甲乙酮、甲基异丁酮、环己酮等酮类溶剂；四氢呋喃、二氧六环等醚类溶剂；乙酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸异丁酯、乙酸叔丁酯、乳酸甲酯、乳酸乙酯等酯类溶剂；苯、甲苯、二甲苯等芳香族类溶剂；甲酰胺、二甲基甲酰胺等胺类溶剂；正己烷、环己烷、正庚烷、正辛烷、正癸烷等烃类溶剂；水等。可以使用其中的一种或两种以上作为溶剂。  \n\n[0082] [涂饰物品]  \n\n[0083]对使用上述防雾涂料组合物形成的涂饰物品进行说明。该涂饰物品是将防雾涂料组合物涂布于作为基材的被涂饰物上，然后进行干燥，接着在 $60\\sim150^{\\circ}\\mathrm{C}$ 的温度下加入固化 $5\\sim60$ 分钟，从而在被涂饰物表面形成涂膜。  \n\n[0084]作为涂膜的具体形成方法，首先按照一般涂料中使用的涂饰方法，将防雾涂料组合物涂饰在被涂饰物上。此时，以提高防雾涂料组合物对被涂饰物的润湿性，及防止凹陷为目的，在涂饰前，优选去除被涂饰物表面附着的异物或进行脱脂、清洗。具体地，可以例举如通过高压空气或离子化空气进行除尘、通过洗涤剂水溶液或乙醇溶剂进行超声清洗、使用乙醇溶剂等进行擦拭、通过紫外线和臭氧进行清洗等。作为涂饰方法，适合采用浸渍法、流涂法、辊涂法、棒涂法、喷涂法等。  \n\n[0085]涂饰后，在 $20\\sim50^{\\circ}\\mathrm{C}$ 的温度下，使涂膜中含有的溶剂挥发干燥 $0.5\\sim5$ 分钟。然后在 $60\\sim150^{\\circ}\\mathrm{C}$ 的温度下加热固化 $5\\sim60$ 分钟，优选在 $70\\sim130^{\\circ}\\mathrm{C}$ 下加热固化 $10\\sim40$ 分钟，从而形成涂膜。此时，通过单体（A2）的磺酸基促进共聚物中含有的单体（A1）的 $N-$ 羟甲基或 $\\mathrm{N-}$ 烷氧基羟甲基的脱水缩合反应或脱醇缩合反应的进行，从而在共聚物中形成交联结构。但是，被涂饰物为合成树脂材料的情况下，需要将固化温度设定在合成树脂材料的热变形温度以下。  \n\n[0086]为了获得良好的防雾性和涂膜外观，通过防雾涂料组合物形成于被涂饰物上的涂膜厚度优选为 $0.5\\sim20\\upmu\\textrm{m}$ ，更优选为 $1\\sim10\\upmu\\textrm{m}$ 。该厚度比 $0.5\\upmu\\mathrm{~m~}$ 薄的情况下，存在涂膜的防雾性变低的倾向，在超过 $20\\upmu\\mathrm{~m~}$ 的情况下，存在涂膜外观变差的倾向。  \n\n[0087]作为防雾涂料组合物所涂饰的被涂饰物，可以适当使用丙烯酸树脂、聚碳酸酯树脂、聚乙二醇对苯二甲酸酯树脂等透明树脂的薄膜、板材、成品及其加工品。作为该被涂饰物，尤其优选车辆灯具。作为车辆灯具，具体可以例举如前照灯、辅助前照灯、侧灯、牌照灯、尾灯、停车灯、刹车灯、倒车灯、方向指示灯、辅助方向指示灯、危险报警闪光灯等。  \n\n[0088] <实施方式的效果概述>  \n\n[0089]（1）实施方式的防雾涂料组合物中，由单体（A1）的性质表现出良好的固化性，由单体（A2）的性质表现出在低温下对固化性的促进和对雾浊现象的抑制，由单体（A3）的性质表现出与基材良好的粘附性和耐热性。并且，由碱性化合物(B)的性质，表现出下述效果，单体（A2）的部分磺酸基被中和，提高共聚物的亲水性，并且提高了对雾浊现象的抑制效果，在此基础上，抑制了涂膜在高温环境下因磺酸基引起的的氧化劣化，表现出优异的耐热性。另外，由表面活性剂（C）的表面活性作用，降低了附着在涂膜表面的水分的表面张力，形成水膜，从而表现出良好的防雾性。  \n\n[0090]因此，防雾涂料组合物即使在进行涂料的涂饰及干燥时湿度高的情况下，也能够抑制雾浊现象，并在低温且短时间条件下的加热固化性优异，同时制得的涂膜还能够发挥出对基材优异的粘附性、耐热性及防雾性。  \n\n[0091]（2）另外，将单体（A1）、单体（A2）及单体（A3）的总量以100质量份计，单体（A1)的含量为 $3\\sim20$ 质量份、单体（A2）的含量为 $3\\sim20$ 质量份，以及单体（A3）的含量为 $60\\sim$ 94质量份，并且单体（A1）及单体（A2）的总量被设定为 $6\\sim40$ 质量份。因此，基于单体（A1）的固化性，因基于单体（A2）的催化剂功能而得以提高，同时利用基于单体（A2）的亲水性能够抑制涂饰时产生雾浊现象。并且，单体（A3)的含量也非常充足，能够发挥涂膜的良好的耐热性和粘附性。  \n\n[0092]另外，相对于单体（A2）的磺酸基，碱性化合物（B）被设定为其 $50\\sim95\\mathrm{mol}\\%$ 。因此，能够提高共聚物的亲水性，从而能够充分抑制雾浊现象，同时能够充分维持该磺酸基的催化剂功能，在此基础上，还能够抑制涂膜在高温环境下因磺酸基引起的氧化劣化，提高耐热性。  \n\n[0093]并且，以共聚物(A）为100质量份计，表面活性剂（C）被设定为 $0.5\\sim30$ 质量份。  \n因此，降低了附着在涂膜表面的水分的表面张力，能够对形成水膜发挥出充分的效果。  \n\n[0094]（3）单体混合物进一步含有N， $\\mathrm{N-}$ 二烷基（甲基）丙烯酰胺类单体(A4)，将单体(A3）及单体（A4）的总量以100质量份计，单体（A4）被设定为 $5\\sim50$ 质量份的情况下，能够进一步扩大对雾浊现象的抑制效果，同时还能够提高涂膜的耐热性。  \n\n[0095]（4）碱性化合物（B）在 $25\\mathrm{^\\circC}$ 水溶液中的碱解离常数pKb为 $3\\sim14$ ，从而在加热固化涂膜时，磺酸基与碱性化合物容易解离，能够充分发挥磺酸基作为酸催化剂的作用。  \n\n[0096]（5）碱性化合物(B)的沸点为 $130\\sim1500^{\\circ}\\mathrm{C}$ ，从而降低在高温环境下的挥发性，提高抑制涂膜在高温环境下因磺酸基引起的氧化劣化的效果持续性，能够进一步提高耐热性。  \n\n[0097] 实施例  \n\n[0098] 下面，例举实施例及比较例，进一步具体说明上述实施方式。  \n\n[0099] [实施例1]  \n\n[0100]在具有搅拌装置、氮气导入管及冷凝管的反应容器中加入下述化合物，边吹入氮气边加热至 $65^{\\circ}\\mathrm{C}$ 。  \n\n[0101] 作为聚合溶剂的 $240\\mathrm{g}$ 正丙醇（以下简称为NPA）；  \n\n[0102] 作为单体（A1）的 $10\\mathrm{g}\\ N-$ 羟甲基丙烯酰胺（以下简称为N-MAA）；  \n\n0103]作为单体（A2）的 $10\\mathrm{{g}\\ 2-}$ 丙烯酰胺 $-2-$ 甲基丙磺酸（以下简称为AMPS）；  \n\n[0104]作为单体（A3）的 $60\\mathrm{g}$ 甲基丙烯酸甲酯（以下简称为MMA)、 $20\\mathrm{g}$ 丙烯酸正丁酯（以下简称为BA）；  \n\n[0105] 作为单体（A4）的 $20\\mathrm{g}\\ N,\\mathrm{N}-$ 二甲基丙烯酰胺（以下简称为DMAA）；  \n\n[0106]作为碱性化合物(B)的 $5.04\\mathrm{g}$ 三乙醇胺（参见表1，在 $25^{\\circ}\\mathrm{C}$ 水溶液中的碱解离常数 $\\mathrm{pKb}=6.2$ 沸点 $335^{\\circ}\\mathrm{C}$ ）。  \n\n[0107]并且，碱性化合物（B）的量相当于作为单体（A2）的AMPS的磺酸基的 $70m o l\\%$ 。参见下式。{AMPS加入量）÷AMPS的摩尔质量 $\\times70\\%$ ÷ $100\\times$ {三乙醇胺的摩尔质量】 $\\mathbf{\\Sigma}=$ $10\\div207.4\\times70\\div100\\times149.2=5.04$ 。  \n\n[0108]然后，将作为自由基聚合引发剂的1g过氧化新戊酸叔己酯的烃稀释品（日油（株）制备的商品名：PERHEXYL（ $\\therefore\\therefore\\Rightarrow\\ast\\Rightarrow\\ast(\\ast)\\vert\\boldsymbol{\\mathrm{PV}})$ 溶于 $40\\mathrm{gNPA}$ 中，将得到的溶液经3小时滴入到反应容器中。经过5小时的聚合后，将反应容液升温至 $80^{\\circ}\\mathrm{C}$ ，在该温度下聚合1小时，得到共聚物浓度为30质量 $\\%$ 的溶液。  \n\n[0109]在上述 $333.3\\mathrm{g}$ 共聚物溶液（作为共聚物为 $100\\mathrm{g})$ 中加入266.7gNPA和 $400\\mathrm{g}$ 丙二醇单甲醚（以下简称为PGM)，使共聚物的浓度调节至10质量 $\\%$ ，然后与作为表面活性剂(C）的 $10\\mathrm{{g}\\ 2\\mathrm{{-}}}$ 乙基己基磺化琥珀酸钠（日油（株）制备的商品名：Rapizol（一）A-80（有效成分80质量 $\\%$ ))（换算为纯品为 $8\\mathrm{g}$ ）和作为流平剂的0.1g聚醚改性聚二甲基硅氧烷（日本毕克化学公司（·）（株）制备的商品名：BYK333）进行混合，获得防雾涂料组合物。  \n\n[0110]关于该防雾涂料组合物，使用以下说明的防雾涂料组合物的评价方法进行评价，得到的结果如表2所示。  \n\n[0111] 表1  \n\n<html><body><table><tr><td rowspan=\"3\">[0112]</td><td colspan=\"3\"></td><td>在25C水溶液中 的碱解离常数 (pKb)</td><td>沸点 (℃)</td><td>摩尔质量 (g/mol)</td></tr><tr><td rowspan=\"7\">碱性化合物</td><td rowspan=\"6\">B</td><td>三乙醇胺</td><td>6.2</td><td>335</td><td>149.2</td></tr><tr><td>咪唑</td><td>7.1</td><td>256</td><td>68.1</td></tr><tr><td>二甲氨基乙醇</td><td>4.1</td><td>144</td><td>89.1</td></tr><tr><td>吡啶</td><td>8.8</td><td>115</td><td>79.1</td></tr><tr><td>三乙胺</td><td>3.2</td><td>90</td><td>101.2</td></tr><tr><td>氢氧化钠</td><td>0.2</td><td>1390</td><td>40.0</td></tr></table></body></html>  \n\n<html><body><table><tr><td colspan=\"9\">表2</td></tr><tr><td colspan=\"3\"></td><td rowspan=\"19\">单位</td><td colspan=\"8\">实施例</td></tr><tr><td rowspan=\"4\"></td><td rowspan=\"2\">A1</td><td>N-MAA</td><td>质量份</td><td>1</td><td>2</td><td>3 4</td><td>5</td><td>6</td><td>7</td><td>8</td></tr><tr><td></td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td></tr><tr><td rowspan=\"2\">形成共聚物 A2</td><td>AMPS</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td></tr><tr><td>A3 MMA</td><td></td><td>2</td><td>6020</td><td></td><td>0020</td><td>020</td><td>020</td><td>020</td></tr><tr><td>的单体</td><td>A4</td><td>(以单体量为）、(A2)及（A3）的 DMAA</td><td>020</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td rowspan=\"6\">碱性 化合物</td><td>B</td><td rowspan=\"6\"></td><td rowspan=\"6\">摩尔% （相对于单体（A2）的磺酸基）</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td></tr><tr><td>三乙醇胺</td><td>70</td><td>一</td><td>一</td><td></td><td>一</td><td>一</td><td>50</td><td>95</td></tr><tr><td>咪唑</td><td>一</td><td>70</td><td>一</td><td>一</td><td>一</td><td></td><td></td><td></td></tr><tr><td>二甲氨基乙醇</td><td>一</td><td>一</td><td>70</td><td>一</td><td>一</td><td>一</td><td>一</td><td>一</td></tr><tr><td>吡啶</td><td>一</td><td>一</td><td>一</td><td>70</td><td>一</td><td>一</td><td>一</td><td>一</td></tr><tr><td>三乙胺 氢氧化钠</td><td>一</td><td>三</td><td></td><td></td><td>70</td><td></td><td>一</td><td>一</td></tr><tr><td>表面</td><td></td><td>RapizolA-80 （换算成纯品量）</td><td></td><td>一</td><td>8</td><td></td><td>一</td><td>70</td><td></td><td>+</td></tr><tr><td colspan=\"2\">活性剂 C 其他</td><td rowspan=\"4\">质量份 （A4）的总量为100计）</td><td rowspan=\"4\">（以单体（A1）、（A2）、（A3）及</td><td>8</td><td>8</td><td></td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td></tr><tr><td>BYK333</td><td>0.1</td><td>0.1</td><td>0.1</td><td>0.1</td><td>0.1</td><td>0.1</td><td>0.1</td><td>0.1</td></tr><tr><td>NPA</td><td>500</td><td>500</td><td>500</td><td>500</td><td>500</td><td>500</td><td>500</td><td>500</td></tr><tr><td>PGM</td><td>400</td><td>400</td><td>400</td><td>400</td><td>400</td><td>400</td><td>400</td><td>400</td></tr><tr><td rowspan=\"5\" colspan=\"2\">评价结果</td><td colspan=\"2\">耐雾浊性</td><td></td><td>#</td><td></td><td></td><td></td><td></td><td>###</td><td></td></tr><tr><td>固化所需时间</td><td colspan=\"2\"></td><td>10分钟</td><td>10分钟</td><td>10分钟 10分钟</td><td>20分钟</td><td></td><td>40分钟</td><td>10分钟</td><td>40分钟</td></tr><tr><td>粘附性（PC）</td><td colspan=\"2\"></td><td></td><td></td><td>#</td><td></td><td>#</td><td></td><td></td><td></td></tr><tr><td>粘附性（PMMA）</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>耐热性</td><td colspan=\"2\">防雾性</td><td></td><td></td><td></td><td>#</td><td># △#</td><td></td><td>△</td><td></td></tr></table></body></html>  \n\n[0113]  \n\n[0114] （1）耐雾浊性的评价[0115] 在设定为 $30^{\\circ}\\mathrm{C}\\:.60\\sim90\\%$ RH任意相对湿度的环境下，用喷涂法将上述防雾涂料组合物涂饰在聚碳酸酯树脂板上，使固化后的涂膜厚度为 $2\\sim3\\upmu\\mathrm{~m~}$ ，涂饰后直接在同样环境下放置30分钟。然后在 $80^{\\circ}\\mathrm{C}$ 下加热固化10分钟，获得涂膜试验片。在 $60\\sim90\\%$ 范围内的各种相对湿度RH下，采用上述方法制备了涂膜试验片。用肉眼观察涂膜外观，确定没有看到白化等外观异常的最大相对湿度，按照下面四级进行评价。并且，如果评价为 $x$ ，则在应用上存在问题；如果是 $\\bigtriangleup$ ，则在应用上没有问题；如果是 $0$ ，则更优选，如果是 $\\circledcirc$ ，则非常优选。  \n\n[0116] $\\textcircled{9}$ ：在相对湿度设定为 $90\\%$ 的环境下能够获得无色透明的涂膜。  \n[0117] $0$ ：相对湿度设定为 $80\\%$ 的环境下能够获得无色透明的涂膜。  \n[0118] $\\bigtriangleup$ ：相对湿度设定为 $70\\%$ 的环境下能够获得无色透明的涂膜。  \n[0119] $x$ ：相对湿度设定为 $60\\%$ 的环境下能够获得无色透明的涂膜。  \n[0120] (2)固化所需时间的评价  \n[0121]用喷涂法将上述防雾涂料组合物涂饰在聚碳酸酯树脂板上，使固化后的涂膜厚度为 $2\\sim3\\upmu\\mathrm{~m~}$ ，在 $30^{\\circ}\\mathrm{C}$ 下干燥1分钟后，在 $80^{\\circ}\\mathrm{C}$ 下，于 $10\\sim90$ 分钟任意时间内实施加热固化，获得涂膜试验片。固化时间在10分钟、20分钟、40分钟、60分钟及最长为90分钟的范围内变化，将获得的涂膜在 $40^{\\circ}\\mathrm{C}$ 温水中浸渍240小时后，在室温下干燥1小时，用肉眼观察干燥后的涂膜外观并进行评价。上述温水浸渍后的涂膜外观与试验前没有发生变化的最小固化时间为固化所需时间。如果固化所需时间在40分钟之内，则在应用上没有问题；如果在20分钟之内，则为更优选；如果在10分钟之内，则为非常优选。  \n[0122]（3）涂膜性能的评价  \n[0123]用喷涂法将上述防雾涂料组合物涂饰在聚碳酸酯树脂板及丙烯酸树脂板上，使固化后的涂膜厚度为 $2\\sim3\\upmu\\mathrm{~m~}$ ，在 $30^{\\circ}\\mathrm{C}$ 下干燥1分钟后，在 $80^{\\circ}\\mathrm{C}$ 下，于上述固化所需时间的条件下进行加热固化，获得涂膜试验片。  \n[0124]（粘附性（PC)）  \n[0125]将每个形成于上述聚碳酸酯树脂(PC）板上涂膜试验片，将涂膜切割成长1cm，宽1cm的区域，区域之间纵横分别间隔 $\\mathrm{1mm}$ ，共制备100个格子。在每个格子表面压附玻璃纸，用肉眼观察急速剥离时的外观，按照下面四级进行评价。如果评价为 $x$ ，则在应用上存在问题；如果是 $\\bigtriangleup$ ，则在应用上没有问题；如果是O，则更优选；如果是 $\\textcircled{9}$ ，则非常优选。  \n[0126] $\\textcircled{9}$ ：完全没有发生剥离。  \n[0127] $0$ ：在切割的交叉点上，确认为有稍微剥离。  \n[0128] $\\bigtriangleup$ ：确认为一部分剥离。  \n[0129] $x$ ：完全剥离。  \n[0130] （粘附性（PMMA））  \n[0131] 除了将树脂板变更为丙烯酸树脂（PMMA）板之外，采用与上述粘附性（PC）同样的方法进行评价。  \n[0132] （防雾性）  \n[0133]将形成于上述聚碳酸酯树脂板或丙烯酸树脂板上的涂膜试验片设置在离保持为$80^{\\circ}\\mathrm{C}$ 的温水浴的距水面5cm的高度处，使试验片的涂膜面朝下，使从温水浴中产出的蒸汽连续照射在涂膜上，通过肉眼观察照射起10秒后有没有结雾，然后按照下面五级进行评价。如果评价为 $x$ 或 $x\\times$ ，则在应用上存在问题；如果是 $\\bigtriangleup$ ，则在应用上没有问题；如果是$0$ ，则更优选；如果是 $\\circledcirc$ ，则非常优选。  \n[0134] $\\textcircled{9}$ ：完全不认为有结雾。  \n[0135] $0$ ：用蒸汽照射后，仅稍稍在瞬间出现结雾，之后不认为有结雾。  \n[0136] $\\bigtriangleup$ ：认为稍有结雾，或者不认为有结雾，但涂膜表面不光滑，粗糙。  \n[0137] $x$ ：明显认为由结雾。  \n[0138] $x\\times$ ：由于涂膜固化不足，在照射蒸汽后，涂膜马上白化。  \n[0139] （耐热性）  \n[0140] 将形成于上述聚碳酸酯树脂板上的涂膜试验片在 $120^{\\circ}\\mathrm{C}$ 气氛条件下，放置240小时后，在室温下冷却1小时。冷却后实施上述防雾性试验，进行了相同的评价。  \n[0141] [实施例 $2\\sim8\\bar{.}$ 1  \n[0142] 除了将碱性化合物(B)的种类和相对于单体(A2）的磺酸基的添加量按照表2所示进行变更之外，其余按照与实施例1相同的方法制备共聚物溶液，然后制备防雾涂料组合物，分别进行评价，结果如表2所示。并且，各实施例中使用的碱性化合物（B）的物理性质如表1所示。  \n[0143] [实施例 $9\\sim17.$ 1  \n[0144]除了变更为表3所示的成分及其配比之外，其余按照与实施例1相同的方法制备  \n\n共聚物溶液，然后制备防雾涂料组合物，分别进行评价，结果如表3所示。  \n\n[0145]  \n\n<html><body><table><tr><td colspan=\"11\">表3</td></tr><tr><td colspan=\"4\"></td><td colspan=\"7\">实施例</td></tr><tr><td rowspan=\"6\">形成共</td><td>A1</td><td></td><td>单位 质量份</td><td>9</td><td>10</td><td>11</td><td>12</td><td>13</td><td>14</td><td>15 16</td><td>17</td></tr><tr><td>A2</td><td>N-MAA</td><td rowspan=\"6\">(以单体△1（A2）及（A3) 摩尔%</td><td>3 12</td><td>20</td><td>12</td><td>10</td><td>3</td><td>20</td><td>10</td><td>10</td><td>10</td></tr><tr><td></td><td>AMPS</td><td></td><td>10</td><td>3</td><td>20</td><td>3</td><td>20</td><td>10</td><td>10</td><td>10</td></tr><tr><td>聚物的</td><td>MMMA</td><td>##</td><td></td><td></td><td></td><td>20</td><td></td><td>###</td><td>6</td><td>6</td></tr><tr><td>A3</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>BA</td><td>20</td><td>10</td><td>20</td><td>10</td><td>24</td><td>一</td><td>20</td><td>20</td><td>20</td></tr><tr><td></td><td>A4</td><td>DMAA</td><td>20</td><td>10</td><td>20</td><td>10</td><td>20</td><td>10</td><td>20</td><td>20</td><td>20</td></tr><tr><td>碱性 化合物</td><td>B</td><td>三乙醇胺 咪唑</td><td>70 （相对于单体（A2）的磺酸基） 一</td><td>90</td><td>一 70</td><td>一 90</td><td>70 一</td><td>90</td><td>一</td><td>70 一</td><td>70</td></tr><tr><td>表面</td><td>C</td><td>RapizolA-80</td><td></td><td></td><td>8</td><td>8</td><td>8</td><td>一</td><td>80 8</td><td></td><td>一</td></tr><tr><td rowspan=\"2\">活性剂 其他</td><td></td><td>（换算成纯品的量）</td><td rowspan=\"2\">质量份 （以单体（A1）、(A2)、（A3) 及（A4）的总量为100计）</td><td>8</td><td></td><td></td><td></td><td></td><td>8</td><td>0.5</td><td>30</td></tr><tr><td>BYK333 NPA</td><td>0.1 500</td><td>0.1 500</td><td>0.1 500</td><td>0.1 500</td><td>0.1 500</td><td>0.1 500</td><td>0.1 500</td><td>0.1</td><td>0.1</td></tr><tr><td rowspan=\"5\">溶剂</td><td rowspan=\"2\"></td><td>PGM</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>500</td><td>500</td></tr><tr><td>耐雾浊性</td><td>400</td><td>400</td><td>400</td><td>400</td><td>400</td><td>400</td><td>400</td><td>400</td><td>400</td></tr><tr><td></td><td>固化所需时间</td><td></td><td></td><td></td><td>10分钟</td><td>△ 40分钟</td><td>10分钟</td><td>#</td><td>##</td><td></td></tr><tr><td></td><td>粘附性（PC）</td><td>20分钟</td><td>10分钟</td><td>20分钟</td><td></td><td></td><td></td><td>10分钟</td><td>10分钟</td><td>10分钟</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>##</td><td></td><td></td><td></td></tr><tr><td>评价结果</td><td colspan=\"2\">粘附性（PMMA）</td><td></td><td></td><td></td><td></td><td></td><td>###</td><td></td><td></td><td>##</td></tr><tr><td></td><td colspan=\"2\">防雾性 耐热性</td><td>#</td><td>###</td><td></td><td>△</td><td></td><td>#</td><td></td><td>#</td><td></td></tr></table></body></html>  \n\n[0146] 并且，表2及表3中的简略标记表示的意思如下。[0147] N-MAA：N-羟甲基丙烯酰胺  \n\n[0148] AMPS:2-丙烯酰胺 $-2-$ 甲基丙磺酸  \n[0149] MMA：甲基丙烯酸甲酯  \n[0150] 2-EHMA：甲基丙烯酸2-乙基己酯  \n[0151] BA：丙烯酸正丁酯  \n[0152] DMAA:N, $N-$ 二甲基丙烯酰胺  \n[0153] NPA：正丙醇  \n[0154] PGM：丙二醇单甲醚  \n[0155] 如表2所示，在实施例1、2的防雾涂料组合物中，碱性化合物(B)，其为上述pKb分别为6.2、7.1，沸点分别为 $335^{\\circ}\\mathrm{C},256^{\\circ}\\mathrm{C}$ 的三乙醇胺或咪唑，共聚物的组成及各成分的含量在更优选范围内。因此，实施例1、2的防雾涂料组合物具有非常优异的耐雾浊性，能够在低温且短时间的条件下进行加热固化，具有非常优异的涂膜性能。  \n[0156]实施例3的防雾涂料组合物中，碱性化合物（B）为pKb4.1、沸点 $144^{\\circ}\\mathrm{C}$ 的二乙氨基乙醇，碱性化合物(B)的沸点比实施例1的情况还低，因此实施例3的防雾涂料组合物与实施例1相比，其耐热性略差。  \n[0157]实施例4中，碱性化合物（B）为pKb8.8、沸点 $115^{\\circ}\\mathrm{C}$ 的吡啶，碱性化合物（B）的沸点比实施例1的情况还低，因此实施例4与实施例1相比，耐热性差，但在应用上不存在问题。  \n[0158]实施例5中，碱性化合物（B）为pKb3.2、沸点 $90^{\\circ}\\mathrm{C}$ 的三乙醇胺，碱性化合物(B）的pKb比实施例1的情况稍低，因此实施例5与实施例1相比，固化所需时间稍微延长。并且，实施例5中碱性化合物(B)的沸点比实施例1的情况还低，因此与实施例1相比耐热性差，但在应用上不存在问题。  \n[0159]实施例6中，碱性化合物（B）为 $\\mathrm{\\pKb{0}}.\\ 2.$ 沸点 $1390^{\\circ}\\mathrm{C}$ 的氢氧化钠，碱性化合物(B)的pKb比实施例1的情况还低，因此实施例6与实施例1相比，固化所需时间延长，但在应用上不存在问题。  \n[0160]实施例7中，由于作为碱性化合物(B）的三乙醇胺的使用量为优选范围的下限值，因此实施例7与实施例1的情况相比，耐雾浊性略差，耐热性差，但在应用上不存在问题。[0161]实施例8中，由于作为碱性化合物（B）的三乙醇胺的使用量为优选范围的上限值，因此实施例8与实施例1的情况相比，固化所需时间延长，但在应用上不存在问题。[0162]如表3所示，实施例9中，单体（A1）的含量为优选范围的下限值，因此共聚物的固化性降低，固化所需时间稍微延长。  \n[0163]实施例10中，单体（A1）的含量为优选范围的上限值，因此共聚物的交联密度变高，涂膜的防雾性降低，并且耐热性降低，但在应用上不存在问题。  \n[0164]实施例11中，单体（A2）的含量为优选范围的下限值，因此可见共聚物的亲水性和固化性降低，耐雾浊性降低，固化所需时间稍微延长，但在应用上不存在问题。  \n[0165]实施例12中，单体（A2）的含量为优选范围的上限值，因此可见共聚物的极性变高，涂膜与基材间的亲和性降低，结果使粘附性降低，且耐热性降低，但在应用上不存在问题。  \n[0166]实施例13中，单体（A1）及单体（A2)的总量为优选范围的下限值，单体（A3）的含  \n\n量为优选范围的上限值，因此可见共聚物的亲水性和固化性降低，耐雾浊性降低，固化所需  \n\n时间延长，但应用上不存在问题。  \n\n[0167]实施例14中，单体（A1）及单体（A2）的总量为优选范围的上限值，单体（A3）的含量为优选范围的下限值。因此可见共聚物的极性变高，涂膜与基材间的亲和性降低，结果使粘附性降低，防雾性降低，且共聚物的交联密度变高，涂膜的防雾性降低，并且耐热性降低，但在应用上不存在问题。  \n\n[0168]实施例15中，通过将实施例1中用作单体（A3）的MMA（烷基酯的烷基的碳原子数为1）替换为2-EHMA（烷基酯的烷基的碳原子数为8)，从而使共聚物的亲水性降低，耐雾浊性降低，但在应用上不存在问题。  \n\n[0169]实施例16中，表面活性剂(C)的含量为优选范围的下限值，因此与实施例1相比，形成水膜的能力降低，防雾性降低，但在应用上不存在问题。  \n\n[0170]实施例17中，表面活性剂(C）的含量为优选范围的上限值，因此与实施例 $^1$ 相比，粘附性降低，但在应用上不存在问题。  \n\n1.防雾涂料组合物，其特征在于，所述防雾涂料组合物含有共聚物(A)、碱性化合物(B）及表面活性剂(C)，所述共聚物（A）由含有下述所示的单体（A1）、单体(A2）及单体（A3)的单体混合物形成；  \n\n单体（A1）：具有 $\\mathrm{N-}$ 羟甲基或 $\\mathrm{N^{-}}$ 烷氧基羟甲基的乙烯类单体；单体（A2）：具有磺酸基的乙烯类单体；单体（A3）：（甲基）丙烯酸烷基酯类单体；以单体（A1）、单体（A2）及单体（A3）的总量为100质量份计，单体（A1）的含量为 $3\\sim$ 20质量份、单体（A2）的含量为 $3\\sim20$ 质量份、单体（A3）的含量为 $60\\sim94\\$ 质量份，以及单体（A1）及单体（A2）的总量为 $6\\sim40$ 质量份；相对于单体（A2）的磺酸基，碱性化合物（B）的含量为 $50\\sim95\\mathrm{mol}\\%$ ，以共聚物（A）为100质量份计，表面活性剂（C）的含量为 $0.5\\sim30$ 质量份。2.根据权利要求1所述的防雾涂料组合物，其特征在于，所述单体混合物还含有N，$\\mathrm{N-}$ 二烷基（甲基）丙烯酰胺类单体（A4)，以单体（A3）及单体（A4）的总量为100质量份计，单体（A4）为 $5\\sim50$ 质量份。3.根据权利要求1或2所述的防雾涂料组合物，其特征在于，碱性化合物（B）在 $25\\mathrm{^\\circC}$ 水溶液中的碱解离常数为 $3\\sim14$ 。4.根据权利要求1至3中任意一项所述的防雾涂料组合物，其特征在于，碱性化合物(B）的沸点为 $130\\sim1500^{\\circ}\\mathrm{C}$ 。5.根据权利要求1所述的防雾涂料组合物，其特征在于，共聚物（A）具有单体（A1）的$N-$ 羟甲基或 $N-$ 烷氧基羟甲基通过缩合反应形成的交联结构；单体（A2）具有中和了的磺酸基和未被中和的磺酸基，所述中和了的磺酸基提高共聚物（A）的亲水性，所述未被中和的磺酸基促进单体（A1）的所述缩合反应。",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,47 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利申请  \n\nC08G18/67(2006.01)C08G18/48(2006.01)  \n\n(21)申请号 201410852633.5  \n(22)申请日 2014.12.31  \n(71)申请人 三棵树涂料股份有限公司地址 351100 福建省莆田市荔城区荔园北大道 518 号  \n(72)发明人 洪杰  詹俊英 林金斌  王艳方江海  林伟  \n(74)专利代理机构 福州市众韬专利代理事务所( 普通合伙 ) 35220代理人 陈智雄  黄秀婷  \n(51)Int.Cl.C09D151/08(2006.01)C09D157/12(2006.01)C08F283/0(2006.01)C08F20/18(2006.01)C08F22/20(2006.01)C08F29/06(2006.01)C08F2/48(2006.01)",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54) 发明名称  \n\n超亲水透明防雾涂层的制备方法",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57) 摘要  \n\n本发明涉及一种超亲水透明防雾涂层的制备方法，本发明是通过丙烯酸羟酯与二异氰酸酯反应形成预聚体，再经聚山梨酯乳化剂进行亲水改性，改性后的预聚体经 UV 辐射固化形成超亲水涂层，涂层对水的接触角为 $3^{\\circ}$ °，硬度高达 2H，防雾性能优异，透光率 $91\\%$ ，可以达到透明面板的防雾要求，并具有一定的耐水性，综合性能优异。这种超亲水透明抗雾涂层制备工艺简单，具有很强的工业化能力与应用前景。  \n\n![](images/4c21ea22d78a49c64bef4cc849d95566a6ca83bff53c40d7d5869dd1f47b2488.jpg)  \n\n1.一种超亲水透明防雾涂层的制备方法，其特征在于，它包含以下步骤：  \n\n(1)、制备聚氨酯预聚体：  \n\n将二异氰酸单体、丙烯酸羟酯和有机溶剂 A 加入反应容器中，其中二异氰酸单体与丙烯酸羟酯的摩尔比为 $0.7{:}1{-}1{:}1$ ，丙烯酸羟酯与有机溶剂 A 的摩尔比为 $3{:}7{-}1:1$ ，然后加入二月桂酸二丁基锡作为催化剂，催化剂的用量为二异氰酸单体质量的 $0.1\\%$ ，将以上的混合物在 $50–70^{\\circ}\\mathrm{C}$ 反应 $2\\mathrm{-}4\\mathrm{h}$ ，得到聚氨酯预聚体；  \n\n(2)、制备聚山梨酯改性的超亲水预聚体：  \n\n将聚山梨酯用有机溶剂 B 溶解并添加到上述制备的聚氨酯预聚体中，其中，在聚山梨酯与有机溶剂B 的混合溶解液中，聚山梨酯的质量浓度为 $50\\text{\\textperthousand}$ ，聚山梨酯与二异氰酸的单体的摩尔比0.5:1-1:1，将以上混合物在 $50–70^{\\circ}\\mathrm{C}$ 反应2-4h, 得到聚山梨酯改性的超亲水预聚体；  \n\n(3)、制备超亲水透明抗雾涂层：  \n\n将上述制备的聚山梨酯改性的超亲水预聚体与活性稀释剂、光引发剂均匀混合；光引发剂为聚山梨酯改性的超亲水预聚体质量的 $1-2\\%$ ，混合均匀后涂覆在基材上烘干，经紫外线辐射交联固化5-10s，即得到超亲水透明抗雾涂层；  \n\n所述有机溶剂 A 为酯类或是碳原子数为 3-10 的酮、醚、醇、烷烃中的一种；有机溶剂 B为酯类或是碳原子数为3-10 的酮、醚、醇、烷烃中的一种。  \n\n2.根据权利要求 1 所述的超亲水透明防雾涂层的制备方法，其特征在于：所述有机溶剂A 和有机溶剂B 均为乙酸乙酯。  \n\n3.根据权利要求 1 所述的超亲水透明防雾涂层的制备方法，其特征在于：所述二异氰酸单体为 $1,6-$ 己二异氰酸酯、异佛尔酮二异氰酸酯、4，4，- 二环己基甲基二异氰酸酯或者苯二亚甲基二异氰酸酯中的一种。  \n\n4.根据权利要求 1 所述的超亲水透明防雾涂层的制备方法，其特征在于：所述丙烯酸羟酯为甲基丙烯酸羟甲酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯或者甲基丙烯酸羟丁酯中的一种。  \n\n5.根据权利要求 1 所述的超亲水透明防雾涂层的制备方法，其特征在于：所述聚山梨酯为聚山梨酯20、聚山梨酯40、聚山梨酯60 或者聚山梨酯80 中的一种。  \n\n6.根据权利要求 1 所述的超亲水透明防雾涂层的制备方法，其特征在于：所述活性稀释剂为丙烯酸酯类。  \n\n7.根据权利要求 6 所述的超亲水透明防雾涂层的制备方法，其特征在于：所述丙烯酸酯类为丙烯酸异冰片酯、二缩三羟基丙烷四丙烯酸酯、二缩三羟基丙烷四丙烯酸酯或者甲氧基聚乙二醇单丙烯酸中的一种。  \n\n8.根据权利要求 7 所述的超亲水透明防雾涂层的制备方法，其特征在于：所述活性稀释剂为甲氧基聚乙二醇单丙烯酸。  \n\n9.根据权利要求 1 所述的超亲水透明防雾涂层的制备方法，其特征在于：所述光引发剂为 $2^{-}$ 羟基 $-2-$ 甲基 $^{-1-}$ 苯基丙酮、 $1^{-}$ 羟基环己基苯基甲酮、 $\\cdot2\\textdegree$ 甲基 $-2-(4-$ 吗啉基 ) $-1-[4-$ ( 甲硫基) 苯基 $]-1-$ 丙酮或者双甲基氮- 对氧氮环丁酮中的一种。  \n\n10.根据权利要求9 所述的超亲水透明防雾涂层的制备方法，其特征在于：所述光引发剂为 $1^{-}$ 羟基环己基苯基甲酮。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 超亲水透明防雾涂层的制备方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明涉及一种防雾涂层，特别涉及一种超亲水透明防雾涂层的制备方法。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 玻璃、塑料等透明的材料是人们日常的生活不可或缺的材料，但是当其相互隔开的两侧出现一定的温差，温度低的表面水分的饱和蒸汽压低于周围环境的蒸汽压，水汽就在物体表面上聚集形成微小的水珠，这些水珠对光线形成漫反射，降低这些材料的透光率，给人们带来诸多不便。比如眼镜表面的雾化使人的视界模糊；汽车挡风玻璃的雾化给交通事故带来大量的隐患；对于太阳能装置，雾化现象可严重降低对太阳光的利用率；对于一些光谱仪器，雾化可以影响仪器的精密度。因此这些玻璃、塑料等透明的材料的防雾研究尤为重要。  \n\n[0003] 由雾化产生的机理可以得到防雾技术和防雾途径。目前，防雾的途径主要有两种：(1) 热力学的角度，使水蒸气雾化产生的小露珠在极短的时间挥发为水蒸气；(2) 材料的结构机理，改变基材表面的化学成分以及基材的微结构，从而改变材料表面的润湿状态。对于第一种途径，是采用热力学原理，通过升温使基材的表面温度始终高于水汽的露点。在实际运用中，如飞机、火车的除霜玻璃、平板液晶显示器、太阳能电池、红外辐射反射镜就是采用这些原理来达到防雾的目的，但存在造价昂贵，浪费能源，并且有一定的使用限制。对于第二种原理，改变基材表面的润湿性质，目前的途径有两种：超疏水和超亲水。超疏水的机理是水汽在超疏水的涂层上冷凝，形成的小水珠不能附着在基材上而是形成水滴因自身的重力而滚落达到防雾的功能 (Jeong H-J.,Kim D-K.,Lee S-B et al.Preparationof water-repellent glass by sol-gel process using perfluoroalkysilane andtetraethoxysilane[J].J Colloid Interface.Sci.2001,235,130-134)。超疏水涂层防雾的功效还令人满意，但目前没有大量推广主要是由于：超疏水选用低表面能的F、Si 聚合物、单体的价格昂贵、合成工艺繁琐；其次由于是低表面能与基材的附着力较低，机械性能差。现在国内外主要集中在超亲水的研究，如涂层表面引入能形成氢键的基团羧基、氨基、巯基、羟基，或是一些离子基团：羧酸根、磺酸根、铵基、磷酸根等，当引入这些基团或是离子时，涂层的表面达到超亲水的状态，水汽冷凝后在基材表面高度铺展，形成一层均匀的水膜，消除了微小水珠对光线的漫反射而达到防雾的目的。目前制备超亲水的途径主要是通过物理共混、化学表面修饰、化学键接法。对于物理共混，主要是将亲水的试剂与聚合物通过物理共混，将亲水试剂引入基材表面，方法简便易行，但是涂膜清洗时容易脱落，耐水性差，使用周期短 (Plasman V.,Caulier T.,Boulos N.Polyglycerol esters demonstratesuperior antifogging properties for films.Plast.Addit.Compd.2005,7,30-33) ；基材表面修饰法，可以提高涂层与基底的结合力和表面的亲水性，但是由于亲水基团的存在使涂层柔软，不耐机械摩擦，而且涂层柔软，不耐摩擦 (Howarter J-A.,Youngblood J-P.Self-cleaning and anti-fog surfaces via stimuli-responsive polymer brushes.Adv.Mater.2007,19,3838-3843) ；对于化学键接法，通过化学合成的方式引入亲水官能团，但由于在涂层中引入亲水基团，但要考虑涂层的耐水性，可通过适度交联提高涂层的综合性能。  \n\n发明内容  \n[0004] 本发明的目的是为了克服现有技术中的不足之处，提供一种超亲水透明防雾涂层的制备方法，本发明制备的超亲水透明防雾涂层不仅可在玻璃、塑料等制品表面施工以达到防雾的功效，而且透光率高、耐水性好。  \n[0005] 本发明是这样实现的：一种超亲水透明防雾涂层的制备方法，它包含以下步骤：[0006] (1)、制备聚氨酯预聚体 ：  \n[0007] 将二异氰酸单体、丙烯酸羟酯和有机溶剂 A 加入反应容器中，其中二异氰酸单体与丙烯酸羟酯的摩尔比为 $0.7{:}1{-}1{:}1$ ，丙烯酸羟酯与有机溶剂 A 的摩尔比为 3:7-1 ：1，然后加入二月桂酸二丁基锡作为催化剂，催化剂的用量为二异氰酸单体质量的 $0.1\\%$ ，将以上的混合物在 $50–70^{\\circ}\\mathrm{C}$ 反应2-4h，得到聚氨酯预聚体；  \n[0008] (2)、制备聚山梨酯改性的超亲水预聚体：  \n[0009] 将聚山梨酯用有机溶剂 B 溶解并添加到上述制备的聚氨酯预聚体中，其中，在聚山梨酯与有机溶剂B 的混合溶解液中，聚山梨酯的质量浓度为 $50\\%$ ，聚山梨酯与二异氰酸的单体的摩尔比0.5:1-1:1，将以上混合物在 $50–70^{\\circ}\\mathrm{C}$ 反应 $2\\mathrm{-}4\\mathrm{h}$ , 得到聚山梨酯改性的超亲水预聚体 ；  \n[0010] (3)、制备超亲水透明抗雾涂层：  \n[0011] 将上述制备的聚山梨酯改性的超亲水预聚体与活性稀释剂、光引发剂均匀混合；光引发剂为聚山梨酯改性的超亲水预聚体质量的 $1-2\\%$ ，添加适量的活性稀释剂以保证体系的粘度在 $25\\mathrm{^\\circC}$ 下测试为 $3000{-}6000{\\mathrm{cps}}$ ；混合均匀后涂覆在基材上烘干，经紫外线辐射交联固化5-10s，即得到超亲水透明抗雾涂层；  \n[0012] 所述有机溶剂 A 为酯类或是碳原子数为 3-10 的酮、醚、醇、烷烃中的一种；有机溶剂B 为酯类或是碳原子数为3-10 的酮、醚、醇、烷烃中的一种。  \n[0013] 进一步优化方案为 ：所述二异氰酸单体为 $1,6-$ 己二异氰酸酯 (HDI)、异佛尔酮二异氰酸酯 (IPDI)、4，4，- 二环己基甲基二异氰酸酯 (HMDI) 或者苯二亚甲基二异氰酸酯(XDI) 中的一种。  \n[0014] 进一步优化方案为：所述丙烯酸羟酯为甲基丙烯酸羟甲酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯或者甲基丙烯酸羟丁酯中的一种。  \n[0015] 进一步优化方案为：所述聚山梨酯为聚山梨酯 20、聚山梨酯 40、聚山梨酯 60 或者聚山梨酯80 中的一种。  \n[0016] 进一步优化方案为：所述活性稀释剂为丙烯酸酯类。如单官能团和双官能团以及多官能团的丙烯酸酯酯类：丙烯酸酯类为丙烯酸异冰片酯、二缩三羟基丙烷四丙烯酸酯、二缩三羟基丙烷四丙烯酸酯或者甲氧基聚乙二醇单丙烯酸中的一种。  \n[0017] 进一步优化方案为：所述光引发剂为 $2^{-}$ 羟基 $-2-$ 甲基 $^{-1-}$ 苯基丙酮 (1173)、1- 羟基环己基苯基甲酮(184) $\\cdot2^{-}$ 甲基 $-2-(4-$ 吗啉基 )-1-[4-( 甲硫基 ) 苯基 $]-1-$ 丙酮 (907)或者双甲基氮 - 对氧氮环丁酮(369) 中的一种。  \n[0018] 本发明优选乙酸乙酯作为有机溶剂A 与有机溶剂 $\\mathrm{~B~}$ 。优选苯二亚甲基二异氰酸酯(XDI) 作为二异氰酸酯单体来制备聚氨酯预聚体。优选聚山梨酯20 作为亲水改性剂来制备超亲水预聚体。优选甲基丙烯酸羟乙酯作为丙烯酸羟酯单体来制备聚氨酯预聚体。优选甲氧基聚乙二醇单丙烯酸作为活性稀释剂。优选 $1^{-}$ 羟基环己基苯基甲酮(184) 为光引发剂。[0019] 本发明制备的超亲水透明防雾涂层的制备方法具有如下优点：采用本发明所述制备方法制备的超亲水透明防雾涂层不仅可在玻璃、塑料等制品表面施工以达到防雾的功效，而且涂层对水的接触角为 $3^{\\circ}$ ，透光率高达 $91\\%$ ，硬度为2H，在 $25\\mathrm{^\\circC}$ 自来水中浸泡4 天，涂层无剥落、无气泡，耐水性好。  \n[0020] 本发明以丙烯酸羟酯与而异氰酸酯反应形成聚氨酯预聚体，聚氨酯具有耐磨、较高的附着力、耐一定的化学腐蚀，而选用世界公认安全的乳化剂聚山梨酯进行改性形成超亲水预聚体，引入大量的亲水基团 $-0\\mathrm{H}$ 。改性后的预聚体与活性稀释剂、光引发剂均匀混合后，经UV( 紫外线) 辐射固化提高涂层的机械性能以及耐水性，操作简便，生产周期短，可以在玻璃、塑料等制品表面是施工，具有较广的运用前景。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 附图说明  \n\n[0021] 下面参照附图结合实施例对本发明作进一步的说明。  \n[0022] 图 1 是本发明超亲水透明防雾涂层的聚山梨酯改性的超亲水预聚体的制备方程式。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 具体实施方式  \n\n[0023] 下面结合具体实施例来对本发明进行详细的说明。  \n[0024] ( 一 ) 具体实施方式如下：  \n[0025] 一种超亲水透明防雾涂层的制备方法，它包含以下步骤：  \n[0026] (1)、制备聚氨酯预聚体：  \n[0027] 将二异氰酸单体、丙烯酸羟酯和有机溶剂 A 加入反应容器中，其中二异氰酸单体与丙烯酸羟酯的摩尔比为 $0.7{:}1{-}1{:}1$ ，丙烯酸羟酯与有机溶剂 A 的摩尔比为 $3{:}7{-}1:1$ ，然后加入二月桂酸二丁基锡作为催化剂，催化剂的用量为二异氰酸单体质量的 $0.1\\%$ ，将以上的混合物在 $50\\mathrm{-}70^{\\circ}\\mathrm{C}$ 反应2-4h，得到聚氨酯预聚体；  \n[0028] (2)、制备聚山梨酯改性的超亲水预聚体：  \n[0029] 将聚山梨酯用有机溶剂 B 溶解并添加到上述制备的聚氨酯预聚体中，其中，在聚山梨酯与有机溶剂B 的混合溶解液中，聚山梨酯的质量浓度为 $50\\%$ ，聚山梨酯与二异氰酸的单体的摩尔比0.5:1-1:1，将以上混合物在 $50\\mathrm{-}70^{\\circ}\\mathrm{C}$ 反应2-4h, 得到聚山梨酯改性的超亲水预聚体 ；  \n[0030] (3)、制备超亲水透明抗雾涂层：  \n[0031] 将上述制备的聚山梨酯改性的超亲水预聚体与活性稀释剂、光引发剂均匀混合；光引发剂为聚山梨酯改性的超亲水预聚体质量的 $1-2\\%$ ，添加适量的活性稀释剂以保证体系的粘度在 $25\\mathrm{^\\circC}$ 下测试为 $3000{-}6000{\\mathrm{cps}}$ ；混合均匀后涂覆在基材上烘干，经紫外线辐射交联固化 $5\\mathrm{-}10\\mathrm{s}$ ，即得到超亲水透明抗雾涂层。  \n[0032] 本发明优选乙酸乙酯作为有机溶剂A 与有机溶剂B。优选苯二亚甲基二异氰酸酯(XDI) 作为二异氰酸酯单体来制备聚氨酯预聚体。优选聚山梨酯20 作为亲水改性剂来制备  \n\n超亲水预聚体。优选甲基丙烯酸羟乙酯作为丙烯酸羟酯单体来制备聚氨酯预聚体。优选甲氧基聚乙二醇单丙烯酸作为活性稀释剂。优选 $1^{-}$ 羟基环己基苯基甲酮(184) 为光引发剂。  \n\n[0033] ( 二 ) 实施例如下：  \n\n[0034] 实施例1 ：一种超亲水透明防雾涂层的制备方法，它包含以下步骤：  \n\n[0035] (1)、制备聚氨酯预聚体：  \n\n[0036] 在 $250\\mathrm{ml}$ 的四口瓶中，将4，4，- 二环己基甲基二异氰酸酯单体与甲基丙烯酸羟甲酯混入有机溶剂乙二醇甲醚当中，其中4，4，- 二环己基甲基二异氰酸酯单体与甲基丙烯酸羟甲酯的摩尔比例为0.7:1，然后加入催化剂二月桂酸二丁基锡，二月桂酸二丁基锡的用量为甲基丙烯酸羟甲酯质量的 $0.1\\%$ ，甲基丙烯酸羟甲酯与有机溶剂乙二醇甲醚的摩尔比为3:7，将以上的混合物在 $60^{\\circ}\\mathrm{C}$ 反应 $\\mathrm{2h}$ ，得到聚氨酯预聚体；  \n\n[0037] (2)、制备聚山梨酯改性的超亲水预聚体：  \n\n[0038] 将聚山梨酯 80 用有机溶剂乙二醇甲醚溶解并添加到上述制备的聚氨酯预聚体中，其中聚山梨酯80 在有机溶剂乙二醇甲醚中的质量浓度为 $50\\%$ ，聚山梨酯80 与4，4，- 二环己基甲基二异氰酸酯单体的摩尔比 0.5:1，将以上混合物在 $60^{\\circ}\\mathrm{C}$ 反应 $\\mathrm{2h}$ ，得到聚山梨酯改性的超亲水预聚体；  \n\n[0039] (3)、制备超亲水透明抗雾涂层：  \n\n[0040] 将上述制备的聚山梨酯改性的超亲水预聚体与活性稀释剂丙烯酸异冰片酯、光引发剂 $2^{-}$ 羟基 $-2-$ 甲基 $^{-1-}$ 苯基丙酮均匀混合后，光引发剂 $2^{-}$ 羟基 $-2-$ 甲基 $^{-1-}$ 苯基丙酮为聚山梨酯改性的超亲水预聚体质量的 $1\\%$ ，添加适量的活性稀释剂，调节体系在 $25^{\\circ}\\mathrm{C}$ 的粘度为3000cps，涂覆在基材上后烘干，经 $\\mathrm{JV}\\left(500\\mathrm{mJ/cm2}\\right)$ 辐射交联固化 $10\\mathrm{s}$ ，即得到超亲水透明抗雾涂层。  \n\n[0041] 经过测试，该涂层对水的接触角为 $5^{\\circ}$ ，透光率为 $88\\%$ ，硬度为 2H，在 $25\\mathrm{^\\circC}$ 自来水中浸泡4 天，涂层无剥落、无气泡，具有一定的耐水性。  \n\n[0042] 实施例2 ：一种超亲水透明防雾涂层的制备方法，它包含以下步骤：  \n\n[0043] (1)、制备聚氨酯预聚体：  \n\n[0044] 在 $250\\mathrm{ml}$ 的四口瓶中，将 $1,6-$ 己二异氰酸酯单体与甲基丙烯酸羟丁酯混入有机溶剂环己烷当中，其中 $1,6-$ 己二异氰酸酯单体与甲基丙烯酸羟丁酯的摩尔比例为 0.8:1，然后加入催化剂二月桂酸二丁基锡，二月桂酸二丁基锡的用量为甲基丙烯酸羟丁酯质量的$0.5\\%$ ，甲基丙烯酸羟丁酯与有机溶剂环己烷的摩尔比为 4:6，将以上的混合物在 $50^{\\circ}\\mathrm{C}$ 反应$3\\mathrm{h}$ ，得到聚氨酯预聚体；  \n\n[0045] (2)、制备聚山梨酯改性的超亲水预聚体：  \n\n[0046] 将聚山梨酯 40 用有机溶剂丙酮溶解并添加到上述的聚氨酯预聚体中，其中聚山梨酯在溶剂丙酮中的质量浓度为 $60\\%$ ，聚山梨酯 40 与 $1,6-$ 己二异氰酸酯单体的摩尔比1:1，将以上混合物在 $50^{\\circ}\\mathrm{C}$ 反应3h，得到聚山梨酯改性的超亲水预聚体；  \n\n[0047] (3)、制备超亲水透明抗雾涂层：  \n\n[0048] 将上述制备的聚山梨酯改性的超亲水预聚体与活性稀释剂双季戊四醇六丙烯酸酯、光引发剂双甲基氮- 对氧氮环丁酮均匀混合后，光引发剂双甲基氮- 对氧氮环丁酮为聚山梨酯改性的超亲水预聚体质量的 $1.2\\%$ ，添加适量的活性稀释剂，调节体系在 $25^{\\circ}\\mathrm{C}$ 的粘度为 4000cps，涂覆在基材上后烘干，经 $\\mathrm{UV}\\left(500\\mathrm{mJ/cm2}\\right)$ 辐射交联固化 5s，即得到超亲水透  \n\n明抗雾涂层。  \n\n[0049] 经过测试，该涂层对水的接触角为 $4^{\\circ}$ ，透光率为 $89\\%$ ，硬度为 2H，在 $25\\mathrm{^\\circC}$ 自来水中浸泡3 天，涂层无剥落、无气泡，具有一定的耐水性。  \n\n[0050] 实施例3 ：一种超亲水透明防雾涂层的制备方法，它包含以下步骤：  \n\n[0051] (1)、制备聚氨酯预聚体：  \n\n[0052] 在 $250\\mathrm{ml}$ 的四口瓶中，将异佛尔酮二异氰酸酯单体与甲基丙烯酸羟丙酯混入有机溶剂乙醇当中，其中异佛尔酮二异氰酸酯单体与甲基丙烯酸羟丙酯的摩尔比例为 0.9:1，然后加入催化剂二月桂酸二丁基锡，二月桂酸二丁基锡的用量为甲基丙烯酸羟丙酯质量的$0.8\\%$ ，甲基丙烯酸羟丙酯与有机溶剂乙醇的摩尔比为 9:11，将以上的混合物在 $70^{\\circ}\\mathrm{C}$ 反应$\\mathrm{4h}$ ，得到聚氨酯预聚体；  \n\n[0053] (2)、制备聚山梨酯改性的超亲水预聚体：  \n\n[0054] 将聚山梨酯 60 用有机溶剂乙醇溶解并添加到上述的聚氨酯预聚体中，其中聚山梨酯在溶剂乙醇中的质量浓度为 $70\\%$ ，聚山梨酯 60 与异佛尔酮二异氰酸酯单体的摩尔比1:1，将以上混合物在 $70^{\\circ}\\mathrm{C}$ 反应4h，得到聚山梨酯改性的超亲水预聚体；  \n\n[0055] (3)、制备超亲水透明抗雾涂层：  \n\n[0056] 将上述制备的聚山梨酯改性的超亲水预聚体与活性稀释剂二缩三羟基丙烷四丙烯酸酯、光引发剂 $2^{-}$ 甲基 $-2-(4-$ 吗啉基) $-1-[4-$ ( 甲硫基) 苯基 $]-1-$ 丙酮均匀混合后，光引发剂 $2^{-}$ 甲基 $-2-(4-$ 吗啉基) $-1-[4-$ ( 甲硫基) 苯基 $]-1-$ 丙酮为聚山梨酯改性的超亲水预聚体质量的 $1.6\\%$ ，添加适量的活性稀释剂，调节体系在 $25\\mathrm{^\\circC}$ 的粘度为 5000cps，涂覆在基材上后烘干，经UV(500mJ/cm2) 辐射交联固化7s，即得到超亲水透明抗雾涂层。  \n\n[0057] 经过测试，该涂层对水的接触角为 $5^{\\circ}$ ，透光率为 $90\\%$ ，硬度为 1H，在 $25\\mathrm{^\\circC}$ 自来水中浸泡3 天，涂层无剥落、无气泡，具有一定的耐水性。  \n\n[0058] 实施例4 ：一种超亲水透明防雾涂层的制备方法，它包含以下步骤：  \n\n[0059] (1)、制备聚氨酯预聚体：  \n\n[0060] 在 $250\\mathrm{ml}$ 的四口瓶中，将苯二亚甲基二异氰酸酯单体与甲基丙烯酸羟乙酯混入有机溶剂乙酸乙酯当中，其中苯二亚甲基二异氰酸酯单体与甲基丙烯酸羟乙酯的摩尔比例为1:1，然后加入催化剂二月桂酸二丁基锡，二月桂酸二丁基锡的用量为甲基丙烯酸羟酯质量的 $1\\%$ ，甲基丙烯酸羟乙酯与有机溶剂乙酸乙酯的摩尔比为1:1，将以上的混合物在 $70^{\\circ}\\mathrm{C}$ 反应2.5h，得到聚氨酯预聚体；  \n\n[0061] (2)、制备聚山梨酯改性的超亲水预聚体：  \n\n[0062] 将聚山梨酯 20 用有机溶剂乙酸乙酯溶解并添加到上述的聚氨酯预聚体中，其中聚山梨酯在溶剂乙酸乙酯中的质量浓度为 $80\\%$ ，聚山梨酯 20 与苯二亚甲基二异氰酸酯单体的摩尔比 0.6:1，将以上混合物在 $70^{\\circ}\\mathrm{C}$ 反应2.5h，得到聚山梨酯改性的超亲水预聚体；  \n\n[0063] (3)、制备超亲水透明抗雾涂层：  \n\n[0064] 将上述制备的聚山梨酯改性的超亲水预聚体与活性稀释剂甲氧基聚乙二醇单丙烯酸、光引发剂1- 羟基环己基苯基甲酮均匀混合后，光引发剂 $1^{-}$ 羟基环己基苯基甲酮为聚山梨酯改性的超亲水预聚体质量的 $2\\%$ ，添加适量的活性稀释剂，调节体系在 $25\\mathrm{^\\circC}$ 的粘度为 6000cps，涂覆在基材上后烘干，经 UV $\\mathrm{(500mJ/cm2)}$ 辐射交联固化 6s，即得到超亲水透明抗雾涂层。  \n\n[0065] 经过测试，该涂层对水的接触角为 $3^{\\circ}$ ，透光率为 $91\\%$ ，硬度为 2H，在 $25\\mathrm{^\\circC}$ 自来水中浸泡4 天，涂层无剥落、无气泡，具有一定的耐水性。  \n\n[0066] 由上述的实施例的测试结果可知：本发明制备的超亲水透明防雾涂层不仅可在玻璃、塑料等制品表面施工以达到防雾的功效，而且透光率高达 $91\\%$ 、耐水性好，在水中浸泡4 天涂层无开裂、无起泡。本发明制得的超亲水防雾涂层的接触角按常规方法测定。[0067] 上述具体实施方式只是对本发明的技术方案进行详细解释，本发明并不只仅仅局限于上述实施例，凡是依据本发明原理的任何改进或替换，均应在本发明的保护范围之内。  \n\n![](images/b05981c252ee692ed567afd3c72756aeb1ee58c871f3588b45a3179e233e0929.jpg)  \n图 1",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,57 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利申请  \n\n(21)申请号 201580040385 .7  \n(22)申请日 2015 .07 .28  \n(30)优先权数据2014-156146 2014 .07 .31 JP  \n\n(85)PCT国际申请进入国家阶段日2017 .01 .22  \n\n(86)PCT国际申请的申请数据PCT/JP2015/071331 2015 .07 .28(87)PCT国际申请的公布数据WO2016/017619 JA 2016.02.04(71)申请人 三井化学株式会社地址 日本东京都  \n\n(72)发明人 冈崎光树  \n\n(74)专利代理机构 北京市金杜律师事务所11256代理人 杨宏军  \n(51)Int.Cl .C08L 57/10(2006.01)B32B 27/42(2006.01)C08F 2 0/0(2006.01)C08K 3/0 (2006.01)C08L 61/20(2006.01)",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n包含磺酸系共聚物和氨基树脂的亲水性材料",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明提供下述固化物(例如，由该固化物形成的膜)、可得到该固化物的组合物，所述固化物的亲水性、耐磨性的均衡性优异，即使进行水洗也可维持高亲水性，而且即使进行长期保存或加热，污染物也不易附着(或容易脱除)并可维持亲水性。将包含共聚物(i)和氨基树脂(ii)的组合物固化，从而制作固化物，所述共聚物(i)包含由特定的化学式表示的结构单元。  \n\n![](images/cc2c11d4a785f3e843f1661d49273e90554a6b778f9f27c354660eb90ea4ef34.jpg)  \n\n1.一种固化物，其是由下述组合物得到的，所述组合物包含：  \n\n共聚物(i)，所述共聚物(i)包含下述通式(1)、(2)及(3)所示的结构单元；和氨基树脂(ii)，  \n\n![](images/be3678358fc2c766538ebbce500135d8773c4413c54faadfb5f5b3d772190b21.jpg)  \n\n所述式(1)、(2)及(3)中，a、b及c表示相对于a、b及c的总结构单元数100 $(\\mathrm{a+b+c}=100)$ 的各结构单元比，  \n\n$\\mathrm{A}^{1}$ 表示单键、碳原子数为 $1\\sim10$ 的2价的烃基、下述式(1-1)所示的基团或下述式(1-2)所示的基团，  \n\n$\\mathrm{A}^{2}$ 表示单键、碳原子数为 $1\\sim10$ 的2价的烃基、下述式(2-1)所示的基团或下述式(2-2)所示的基团，  \n\n$\\mathrm{A}^{3}$ 表示单键、碳原子数为 $1\\sim10$ 的2价的烃基、下述式(3-1)所示的基团或下述式(3-2)所示的基团，  \n\n${\\mathrm{R}}^{1}$ 、R2及 $\\mathrm{R^{3}}$ 各自独立地表示氢原子或甲基，$\\mathrm{R^{4}}$ 表示氢原子、甲基、乙基、丙基或丁基， $\\mathrm{R^{4}}$ 彼此可相同或不同，$\\mathrm{R}^{10}$ 表示氢原子、甲基、乙基、丙基、丁基、甲氧基、乙氧基、丙氧基或丁氧基  \n\nM表示氢原子、碱金属离子、1/2价的碱土金属离子、铵离子或胺离子；  \n\n下述式(1-1)、(1-2)、(2-1)、(2-2)、(3-1)及(3-2)中，n及n2各自独立地为 $1{\\sim}10$ 的整数，$\\mathrm{n}_{1}$ 为 $0\\sim10$ 的整数，m为 $1{\\sim}6$ 的整数， $\\mathfrak{m}_{1}$ 为 $0{\\sim}6$ 的整数，l为 $0{\\sim}4$ 的整数， $\\mathrm{R}^{5}$ 及 $\\mathrm{R}^{6}$ 各自独立地表示氢原子或甲基， $\\star$ 表示与 $\\mathrm{S0_{3}M}$ 键合侧的端部， $\\star\\star$ 表示与环氧基键合侧的端部， $\\star\\star\\star$ 表示与Si原子键合侧的端部，  \n\n![](images/71bcfcf2cce7aeaaf385963d1b237e1066dedd3881f46826e2ee0ab925cbf04d.jpg)  \n\n2.如权利要求1所述的固化物，其是由共聚物(i)为包含下述通式(4)、(5)及(6)所示的结构单元的共聚物(i3-1)的所述组合物得到的，  \n\n![](images/c8d7e835106296cd81df38d71bd82027a06fbfd262ccf94504f46d4136890c22.jpg)  \n\n所述式(4)、(5)及(6)中，a、b及c表示各结构单元相对于a、b及c的总结构单元数100( $\\mathrm{{\\dot{a}+}}$ $\\mathrm{b}{+}\\mathrm{c}=100)$ )的结构单元比，  \n\nn为 $1{\\sim}10$ 的整数， $\\mathrm{n}_{1}$ 为 $0{\\sim}10$ 的整数，  \n$\\mathrm{R^{1}}\\cdot\\mathrm{R^{2}}\\cdot\\mathrm{R^{3}}\\cdot\\mathrm{R^{5}}$ 及 $\\mathrm{R}^{6}$ 各自独立地表示氢原子或甲基，  \n$\\mathrm{R^{4}}$ 表示氢原子、甲基、乙基、丙基或丁基， $\\mathrm{R^{4}}$ 彼此可相同或不同，  \n$\\mathrm{R}^{10}$ 表示氢原子、甲基、乙基、丙基、丁基、甲氧基、乙氧基、丙氧基或丁氧基，M表示氢原子、碱金属离子、1/2价的碱土金属离子、铵离子或胺离子。  \n\n3.如权利要求1或2所述的固化物，其是由共聚物(i)的利用凝胶渗透色谱(GPC)测得的以标准聚甲基丙烯酸甲酯换算的重均分子量为 $500{\\sim}3,000,000$ 的所述组合物得到的。  \n\n4.如权利要求 $1{\\sim}3$ 中任一项所述的固化物，其是由氨基树脂(ii)为下述通式(7)所示的氨基树脂(ii1)的所述组合物得到的，  \n\n![](images/d86108d53a6cf162298741553760b886dab2b16b18f1799e6a5a06a1a74a0fcd.jpg)  \n\n所述式(7)中， $\\mathrm{R}^{30}$ 表示氢原子、碳原子数为 $1\\sim10$ 的烷基、羟基甲基或碳原子数为 $1\\sim10$ 的烷氧基甲基， $\\mathrm{R}^{40}$ 表示羟基、氢原子、碳原子数为 $1\\sim10$ 的烷基或碳原子数为 $1\\sim10$ 的烷氧基，q190为 $1{\\sim}90$ 的整数，MC表示下述通式 $(8)\\sim(10)$ 中任一者所示的母核， $\\sharp2$ 是与下述通式(8) $\\sim(10)$ 中的#1键合的化学键，#1和#2的数目相同，  \n\n下述式(8)中， $\\mathbf{q}_{030}$ 为 $0\\sim30$ 的整数，q030彼此可相同或不同， $\\mathrm{R}^{30}$ 及 $\\mathrm{R}^{40}$ 与式(7)中的定义相同，  \n\n下述式(9)中， $\\mathbf{q}_{050}$ 为 $0\\sim50$ 的整数，X表示氧原子或硫原子， $\\mathrm{R}^{30}$ 及 $\\mathrm{R}^{40}$ 与式(7)中的定义相同，  \n\n下述式(10)中，q050为 $0\\sim50$ 的整数，  \n\n![](images/1bc4f5f2faaf682bd6913e6b1f39830a30240a3be11eeddecb8418612940e4c9.jpg)  \n\n5.如权利要求 $1{\\sim}4$ 中任一项所述的固化物，其是由共聚物(i)与所述氨基树脂(ii)的重量比(i)/(ii)在 $99/1{\\sim}1/99$ 的范围内的所述组合物得到的。  \n\n6.如权利要求 $1\\sim5$ 中任一项所述的固化物，其是由还包含无机粒子(iii)的所述组合物得到的。  \n\n7.如权利要求6所述的固化物，其是由包含 $5{\\sim}98$ 重量份共聚物(i)、 $1\\sim70$ 重量份氨基树脂(ii)及 $1{\\sim}90$ 重量份无机粒子(iii)的所述组合物得到的，其中，将共聚物(i)、氨基树脂(ii)及无机粒子(iii)的总重量设为100重量份。  \n\n8.一种膜(Z1)，其是由权利要求 $1{\\sim}7$ 中任一项所述的固化物形成的，所述膜(Z1)的厚度为 $0.01{\\sim}300\\upmu\\mathrm{m}$ 。  \n\n9.一种层叠体，其具有至少一层权利要求8所述的膜(Z1)。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 包含磺酸系共聚物和氨基树脂的亲水性材料",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明涉及具有防雾性、防污性及防静电性、并且耐磨性及耐气候性优异的亲水性固化物(例如，由该固化物形成的膜)、以及该固化物的用途。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 近年来，针对在塑料表面、玻璃表面等基材表面产生的起雾、污垢进行改善的要求日趋强烈。  \n\n[0003] 作为解决起雾问题的方法，提出了向丙烯酸系低聚物中添加反应性表面活性剂的防雾涂料，认为由该防雾涂料得到的固化物(例如，由该固化物形成的膜)的亲水性和吸水性提高(非专利文献1)。另外，作为解决污垢问题的方法，例如，具有自清洁性(防污染性)的防污染材料受到关注，所述防污染材料使表面的亲水性提高，通过降雨或洒水等使附着在外壁等上的污垢(外界气体中的疏水性物质等)上浮而有效地将其除去(非专利文献2、3)。[0004] 作为用于解决上述“起雾”及“污垢”的课题的方案，本发明的发明人们提出了使阴离子性亲水基团向表面倾斜(集中化)的固化物(例如，单层膜)(专利文献1)。通过该发明得到的固化物(例如，膜)透明且亲水性高，防雾性、防污性、防静电性、速干性(附着水的除去速度快)、及耐药品性优异，并且，硬且擦伤性也优异。然而，通过本发明的发明人们的研究发现，在耐磨性及耐气候性方面存在改善的余地。  \n\n[0005] 通常，作为提高基材表面的耐气候性及耐磨性的方法，已知在基材表面上涂覆无机化合物的方法。作为代表例，可举出利用溶胶凝胶反应而将烷氧基硅烷应用于眼镜透镜的硬涂层的方法(非专利文献4)。  \n\n[0006] 利用烷氧基硅烷形成的硬涂层由于结构致密，所以非常硬，其磨耗性与玻璃相仿，但另一方面，该硬涂层存在容易破裂、染色困难、容易起雾、污垢容易附着而且容易固着等这样的课题。  \n\n[0007] 作为解决这些课题的方法，以往提出了多种方案。例如，作为赋予染色性及韧性的方法，提出了以下方法：向羟基硅烷中配合三聚氰胺树脂和具有环氧基的硅化合物的方法(专利文献2)、向羟基硅烷中配合环氧化合物和铝络合物的方法(专利文献3)、向羟基硅烷中配合具有羟基的丙烯酸系聚合物的方法(专利文献4)。  \n\n[0008] 作为赋予防雾性的方法，提出了向烷氧基硅烷中配合苯乙烯磺酸系聚合物的方法(专利文献5)。  \n\n[0009] 此外，作为钢板涂装用水分散性树脂组合物，已知有向下述共聚物树脂(A)中配合锆化合物(B)和硅烷偶联剂(C)而成的组合物，所述共聚物树脂(A)是将具有环氧基的聚合性不饱和单体、具有磺酸基等酸基的聚合性不饱和单体、具有羟基的聚合性不饱和单体、和具有水解性甲硅烷基的聚合性不饱和单体以相对于单体总量分别为 $0.1{\\sim}10\\mathrm{wt}\\%$ 的使用量范围进行乳液聚合而得到的(专利文献6)。  \n\n[0010] 同样地，作为金属表面用水分散性树脂处理剂，已知有向下述核壳型树脂(A)中配合锆化合物(B)和硅烷偶联剂(C)而成的处理剂，所述核壳型树脂(A)是将不含有环氧基、酸基及羟基的聚合性不饱和单体、具有环氧基的聚合性不饱和单体、具有磺酸基等酸基的聚合性不饱和单体、具有羟基的聚合性不饱和单体、具有水解性甲硅烷基的聚合性不饱和单体、和具有特定结构的环状脲基的聚合性不饱和单体以相对于单体总量分别为 $0.1{\\sim}5\\mathrm{wt}\\%$ 的使用量的范围进行乳液聚合而得到的(专利文献7)。  \n\n[0011] 进而，还已知有如下方法：使具有磺酸基及烷氧基甲硅烷基的共聚物与烷氧基硅烷反应从而获得由高亲水性的固化物形成的膜(专利文献8)。另外，本发明的发明人们之前也提出了如下方法：使具有磺酸基及环氧基的共聚物与烷氧基硅烷反应从而获得由高亲水性的固化物形成的膜(专利文献9)。  \n\n[0012] 现有技术文献  \n[0013] 专利文献  \n[0014] 专利文献1：国际公开第2007/064003号  \n[0015] 专利文献2：日本特开昭56-22365号公报  \n[0016] 专利文献3：日本特开昭61-166824号公报  \n[0017] 专利文献4：日本特开平06-166847号公报  \n[0018] 专利文献5：日本特开平11-021512号公报  \n[0019] 专利文献6：日本特开2006-342221号公报  \n[0020] 专利文献7：日本特开2006-089589号公报  \n[0021] 专利文献8：日本特开2009-062463号公报  \n[0022] 专利文献9：国际公开第2013/054877号  \n[0023] 非专利文献  \n[0024] 非专利文献1：东亚合成研究年报，TREND1999年2月号， $39{\\sim}44$ 页  \n[0025] 非专利文献2：高分子，44(5)，307页，1995年  \n[0026] 非专利文献3：未来材料，2(1)，36-41页，2002年  \n[0027] 非专利文献4：塑料透镜的技术和应用，165-166页，CMC出版，2003年6月30日发行",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0028] 发明所要解决的课题  \n\n[0029] 上述专利文献5中记载的方案是亲水性容易提高的方案，但存在聚合物容易从膜脱离，由于水洗而导致亲水性容易降低的倾向(膜厚越小，该倾向越显著)，并存在在实际要求防雾性及防污性(利用雨水等的自清洁性)的情况下难以耐用这样的课题。[0030] 上述专利文献8及9中记载的方案也是亲水性容易提高的理想方案，但经本发明的发明人们的研究而判明了存在下述这样的课题：若在室温下长时间保存或加热，则大气中的污染物容易附着，而且附着的污染物难以脱除。本发明的目的在于提供下述固化物(例如，由该固化物形成的膜)、可得到该固化物的组合物，所述固化物的亲水性、耐磨性的均衡性优异，即使进行水洗也可维持高亲水性，而且即使进行长期保存或加热，污染物也不易附着(或容易脱除)并可维持亲水性。  \n\n[0031] 用于解决课题的手段  \n\n[0032] 本发明的发明人们查明了被用作共聚成分的烷氧基硅烷(含羟基硅烷)是大气中的污染物变得容易附着且难以脱除的主要原因，并且，为了发现可得到在克服该课题的同  \n\n时还兼具与使用烷氧基硅烷(含羟基硅烷)的情况相比为同等程度以上的亲水性、硬度及耐磨性的固化物、例如由该固化物形成的膜的组合物而反复进行了研究。  \n[0033] 即，发现了若使用包含下述共聚物(i)和氨基树脂(ii)的组合物，则通过将该组合物固化而得到的固化物(例如，由该固化物形成的膜)的亲水性、硬度、耐磨性的均衡性优异，还可抑制由水及污染物等导致的亲水性的降低，所述共聚物(i)在分子内至少具有磺酸基和环氧基、磺酸基和烷氧基甲硅烷基、或磺酸基和环氧基和烷氧基甲硅烷基。  \n[0034] 本发明涉及以下的 $[1]\\sim[9]$ 。  \n[0035] [1]一种固化物，其是由下述组合物得到的，所述组合物包含：  \n[0036] 共聚物(i)，所述共聚物(i)包含下述通式(1)、(2)及(3)所示的结构单元；和[0037] 氨基树脂(ii)。  \n\n![](images/014cd9ce8c7c148ef110efb1d43487138dd5ac53eb141ffa3f8a3eddd5a6f10b.jpg)  \n\n[0038]  \n\n![](images/e612477cceaace038211a545f115bdd14496271c96650edf4ae7217aab8fbeb9.jpg)  \n\n[0039] (上述式(1)、(2)及(3)中， $\\mathrm{a},\\mathrm{b}$ 及c表示相对于a、b及c的总结构单元数100 $(a+b+c=$ 100)的各结构单元比，  \n[0040] A1表示单键、碳原子数为 $1\\sim10$ 的2价的烃基、下述式(1-1)所示的基团或下述式(1-2)所示的基团，  \n[0041] A2表示单键、碳原子数为 $1\\sim10$ 的2价的烃基、下述式(2-1)所示的基团或下述式(2-2)所示的基团，  \n[0042] A3表示单键、碳原子数为 $1\\sim10$ 的2价的烃基、下述式(3-1)所示的基团或下述式(3-2)所示的基团，  \n[0043] $\\mathrm{R}^{1}\\cdot\\mathrm{R}^{2}$ 及R3各自独立地表示氢原子或甲基，  \n[0044] $\\mathrm{R^{4}}$ 表示氢原子、甲基、乙基、丙基或丁基， $\\mathrm{R^{4}}$ 彼此可相同或不同，  \n[0045] $\\mathrm{R}^{10}$ 表示氢原子、甲基、乙基、丙基、丁基、甲氧基、乙氧基、丙氧基或丁氧基，[0046] M表示氢原子、碱金属离子、 $1/2$ 价的碱土金属离子、铵离子或胺离子；  \n[0047] 下述式(1-1)、(1-2)、(2-1)、(2-2)、(3-1)及(3-2)中， $\\mathfrak{n}$ 及n2各自独立地为 $1{\\sim}10$ 的整数， $\\mathrm{n}_{1}$ 为 $0{\\sim}10$ 的整数， $\\mathfrak{m}$ 为 $1{\\sim}6$ 的整数， $\\mathfrak{m}_{1}$ 为 $0{\\sim}6$ 的整数，1为 $0{\\sim}4$ 的整数， $\\mathrm{R}^{5}$ 及R6各自独立  \n\n地表示氢原子或甲基， $\\star$ 表示与 $\\mathrm{S0_{3}M}$ 键合侧的端部， $\\star\\star$ 表示与环氧基键合侧的端  \n\n部， $\\bigstar\\bigstar\\bigstar$ 表示与Si原子键合侧的端部。)[0048]  \n\n![](images/d380ac891753812bd0fb7fc8441963239f2db9a07f0c809e1cf960744b1eefbd.jpg)  \n\n[0049] [2]如[1]所述的固化物，其是由共聚物(i)为包含下述通式(4)、(5)及(6)所示的结构单元的共聚物(i3-1)的上述组合物得到的。  \n\n![](images/d23a562a77421fbf59e7adb80a5e2e1dd29c8461e469fbe3889c0edf4c8417a3.jpg)  \n\n[0051] (上述式(4)、(5)及(6)中，a、b及c表示各结构单元相对于a、b及c的总结构单元数100( $\\displaystyle{\\mathrm{^{\\prime}a+b+c=100}}\\gamma$ )的结构单元比，  \n[0052] n为 $1{\\sim}10$ 的整数， $\\mathrm{n}_{1}$ 为 $0{\\sim}10$ 的整数，  \n[0053] $\\mathrm{R^{1}}\\cdot\\mathrm{R^{2}}\\cdot\\mathrm{R^{3}}\\cdot\\mathrm{R^{5}}$ 及R6各自独立地表示氢原子或甲基，  \n[0054] $\\mathrm{R^{4}}$ 表示氢原子、甲基、乙基、丙基或丁基， $\\mathrm{R^{4}}$ 彼此可相同或不同，  \n[0055] $\\mathrm{R}^{10}$ 表示氢原子、甲基、乙基、丙基、丁基、甲氧基、乙氧基、丙氧基或丁氧基，[0056] M表示氢原子、碱金属离子、1/2价的碱土金属离子、铵离子或胺离子。)  \n[0057] [3]如 $[1]\\sim[2]$ 中任一项所述的固化物，其是由共聚物(i)的利用凝胶渗透色谱(GPC)测得的以标准聚甲基丙烯酸甲酯换算的重均分子量为 $500{\\sim}3,000,000$ 的上述组合物得到的。  \n\n[0058] 如[1]或[2]所述的固化物，其是由上述共聚物(i)的利用GPC测得的重均分子量为$500{\\sim}3,000,000$ 的组合物得到的。  \n\n[0059] [4]如 $[1]\\sim[3]$ 中任一项所述的固化物，其是由氨基树脂(ii)为下述通式(7)所示的氨基树脂(ii1)的上述组合物得到的。  \n\n![](images/e384220d6c9657945b3352d7f5b4a03665e68235bb7e754c2b46a813cc6b8503.jpg)  \n\n[0061] (上述式(7)中， $\\mathrm{R}^{30}$ 表示氢原子、碳原子数为 $1{\\sim}10$ 的烷基、羟基甲基或碳原子数为1${\\sim}10$ 的烷氧基甲基， $\\mathrm{R}^{40}$ 表示羟基、氢原子、碳原子数为 $1{\\sim}10$ 的烷基或碳原子数为 $1{\\sim}10$ 的烷氧基，q190为 $1{\\sim}90$ 的整数，MC表示下述通式 $(8)\\sim(10)$ 中任一者所示的母核，#2为与下述通式 $(8)\\sim(10)$ 中的#1键合的化学键，#1和#2的数目相同；  \n[0062] 下述式(8)中，q030为 $0{\\sim}30$ 的整数， $\\mathbf{q}_{030}$ 彼此可相同或不同， $\\mathrm{R}^{30}$ 及 $\\mathrm{R}^{40}$ 与式(7)中的定义相同，  \n[0063] 下述式(9)中， $\\mathbf{q}_{050}$ 为 $0\\sim50$ 的整数，X表示氧原子或硫原子， $\\mathrm{R}^{30}$ 及 $\\mathrm{R}^{40}$ 与式(7)中的定义相同，  \n\n[0064] 下述式(10)中，q050为 $0\\sim50$ 的整数。)  \n\n[0065] [0066]  \n\n![](images/ff6e4bd81b07fb1724a520c9196330921f6c10aa35efcca0cbb1c08fe6c1a035.jpg)  \n\n![](images/7ea177f110db32be1534f75395fac7b76a750b7330f2fb6c7c767f8344bcc324.jpg)  \n\n[0067] [5]如 $[1]\\sim[4]$ 中任一项所述的固化物，其是由共聚物(i)与上述氨基树脂(ii)的重量比(i)/(ii)在 $99/1\\sim1/99$ 的范围内的上述组合物得到的。  \n\n[0068] [6]如[1] $\\sim$ [5]中任一项所述的固化物，其是由还包含无机粒子(iii)的上述组合  \n\n物得到的。  \n\n[0069] [7]如[6]所述的固化物，其是由包含 $5{\\sim}98$ 重量份共聚物(i)、 $\\cdot1{\\sim}70$ 重量份氨基树脂(ii)及 $1{\\sim}90$ 重量份无机粒子(iii)(其中，将共聚物(i)、氨基树脂(ii)及无机粒子(iii)的总重量设为100重量份)的上述组合物得到的。  \n\n[0070] [8]一种膜(Z1)，其是由 $[1]\\sim[7]$ 中任一项所述的固化物形成的，所述膜(Z1)的厚度为 $0.01{\\sim}300\\upmu\\mathrm{m}$ 。  \n\n[0071] [9]一种层叠体，其具有至少一层[8]所述的膜(Z1)。  \n\n[0072] 发明的效果  \n\n[0073] 对于通过本发明得到的固化物、由该固化物形成的膜而言，亲水性、硬度及耐磨性的均衡性优异，还可抑制由水及污染物等导致的亲水性的降低。对于本发明中得到的膜而言，通过层叠于基材等，从而还能够以层叠体的形式使用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 附图说明  \n\n[0074] [图1]是表示下述式(1’)所示的化合物中的M(抗衡阳离子，counter  cation)为钠、钾时的热稳定性的DSC图。  \n[0075] [图2]是表示测定实施例中得到的样品的倾斜度时的、样品的切割方法及磺酸浓度测定部位的示意图。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 具体实施方式  \n\n[0076] 在本发明的用于形成固化物的组合物中，含有共聚物(i)。该共聚物(i)的特征在于包含(1)、(2)及(3)所示的结构单元。  \n\n[0077]  \n\n![](images/1b8298070c7d27c00fe63c7402d2309d433d7fab0be06755b547cdb8da4ae59c.jpg)  \n\n[0078] 上述式(1)、(2)及(3)中， $\\mathrm{a},\\mathrm{b}$ 及c表示各结构单元相对于a、b及c的总结构单元数100( $\\displaystyle{a+b+c=100}$ )的结构单元比。  \n[0079] 上述式(1)、(2)及(3)中， $\\mathrm{R}^{1}\\cdot\\mathrm{R}^{2}$ 及 $\\mathrm{R}^{3}$ 各自独立地表示氢原子或甲基， $\\mathrm{R^{4}}$ 表示氢原子、甲基、乙基、丙基或丁基， $\\mathrm{R^{4}}$ 彼此可相同或不同， $\\mathrm{R}^{10}$ 表示氢原子、甲基、乙基、丙基、丁基、甲氧基、乙氧基、丙氧基或丁氧基。  \n[0080] 上述式(1)、(2)及(3)中，M表示氢原子、碱金属离子、1/2价的碱土金属离子、铵离子或胺离子。  \n\n[0081] 上述式(1)、(2)及(3)中， $\\mathrm{A}^{1}$ 表示单键、碳原子数为 $1\\sim10$ 的2价的烃基、下述式 $(1^{-}$ 1)所示的基团或下述式(1-2)所示的基团， $\\mathrm{A}^{2}$ 表示单键、碳原子数为 $1\\sim10$ 的2价的烃基、下述式(2-1)所示的基团或下述式(2-2)所示的基团， $\\mathrm{A}^{3}$ 表示单键、碳原子数为 $1{\\sim}10$ 的2价的烃基、下述式(3-1)所示的基团或下述式(3-2)所示的基团。  \n\n[0082]  \n\n![](images/ae6c9c8533f8be428329c8806ee76acd789f70ddb469fe9903abff4d1e8fc0ec.jpg)  \n\n[0083] 上述式(1-1)、(2-1)、(2-2)、(3-1)及(3-2)中，n为 $1\\sim10$ 的整数，m为 $1{\\sim}6$ 的整数。上述式(1-2)中， $\\mathrm{n}_{1}$ 为 $0{\\sim}10$ 的整数。上述式(2-1)中， $\\mathrm{n}_{2}$ 为 $1\\sim10$ 的整数， $\\mathfrak{m}_{1}$ 为 $0{\\sim}6$ 的整数。上述式(2-2)及(3-2)中，1为 $0{\\sim}4$ 的整数。  \n\n[0084] 上述式(1-2)中， $\\mathrm{R}^{5}$ 及 $\\mathrm{R}^{6}$ 各自独立地表示氢原子或甲基。  \n\n[0085] 上述式 (1-1)及(1-2)中 ， $\\star$ 表示与 $\\mathrm{S0_{3}M}$ 键合侧的端部，上述式(2-1)及(2-2)中， $\\star\\star$ 表示与环氧基键合侧的端部，上述式(3-1)及(3-2)中， $\\star\\star\\star$ 表示与Si原子键合侧的端部。  \n\n[0086] 共聚物(i)由于包含上述结构单元而显示亲水性及交联反应性，由含有共聚物(i)的组合物，可制造亲水性、耐磨性的均衡性优异、因水而导致的亲水性的降低少、并且耐气候性也优异的固化物，例如，由该固化物形成的膜。  \n\n[0087] 作为上述式(1)的 $\\mathrm{A}^{1}$ ，优选为单键、亚甲基、亚苯基、上述式(1-1)所示的基团及上述式(1-2)所示的基团，更优选为上述式(1-2)所示的基团。  \n\n[0088] 上述式(1)的 $\\mathrm{A}^{1}$ 为式(1-2)所示的基团时，上述式(1)所示的结构单元成为下述式(4)所示的结构单元。  \n\n[0089]  \n\n![](images/dc70062958ef0e91195496811c4c1ccb686f2f84abd7fb42130c8b778775d816.jpg)  \n\n[0090] 需要说明的是，上述式(4)中的a、 $\\mathsf{R}^{1}$ 及M的定义与上述式(1)中的定义相同， $\\mathrm{R}^{5}\\cdot\\mathrm{R}^{6}$ 及n1的定义与上述式(1-2)中的定义相同。  \n\n[0091] 上述式(1)及(4)的M为氢原子、碱金属离子、1/2价的碱土金属离子、铵离子或胺离子，但考虑到得到的共聚物(i)的操作性时，优选 $\\mathrm{S0_{3}M}$ 不是游离酸的形态，因此，这些M中，优选碱金属离子、1/2价的碱土金属离子、铵离子及胺离子。  \n\n[0092] 作为上述碱金属离子，优选为钠离子、钾离子、铷离子。作为上述碱土金属离子，优选为钙离子、镁离子。作为上述铵离子，优选为四氢铵离子 $\\mathrm{(NH_{4}^{+})}$ )。作为上述胺离子，优选为三氢-甲基胺离子、三氢-乙基胺离子、三氢-丙基胺离子、三氢-异丙基胺离子、三氢-丁基胺离子、三氢-环己基胺离子、三氢-苄基胺离子、二氢-二甲基胺离子、氢-三乙基胺离子、三氢-乙醇胺离子、二氢-二乙醇胺离子、氢-三乙醇胺离子。  \n\n[0093] 作为上述式(2)的 $\\mathrm{A}^{2}$ ，优选为上述式(2-1)所示的基团及上述式(2-2)所示的基团，更优选为上述式(2-1)所示的基团。  \n\n[0094] 上述式(2)的 $\\mathrm{A}^{2}$ 为式(2-1)所示的基团时，上述式(2)所示的结构单元成为下述式(5A)所示的结构单元。  \n\n[0095]  \n\n![](images/c3da5443eb2c41bd006682a18d544c35ee90d542a779fa8f490c0301c028cb80.jpg)  \n\n[0096] 上述式(5A)中的b及R2的定义与上述式(2)中的定义相同，n、n2及m1的定义与上述式(2-1)中的定义相同。  \n\n[0097] 上述式(5A)所示的结构单元中，m1为0的下述式(5)所示的结构单元是一种优选方式。  \n\n[0098]  \n\n![](images/45272d0436ac7f5536ef27b9e24689459d0f8bc33d8cd0595319883d1470e554.jpg)  \n\n[0099] 需要说明的是，上述式(5)中的b及 $\\mathrm{R}^{2}$ 的定义与上述式(2)中的定义相同，n的定义与上述式(2-1)中的定义相同。  \n[0100] 作为上述式(3)的 $\\mathrm{A}^{3}$ ，优选为单键、亚甲基、亚苯基及上述式(3-1)所示的基团，更优选为上述式(3-1)所示的基团。  \n[0101] 上述式(3)的 $\\mathrm{A}^{3}$ 为式(3-1)所示的基团时，上述式(3)所示的结构单元优选成为下述式(6)所示的结构单元。  \n\n[0102]  \n\n![](images/1ef26cb777a9d4bb989600e0adfff9ed6430e5a6063209ae436fcd7bedce4ace.jpg)  \n\n[0103] 需要说明的是，上述式(6)中的 $\\mathrm{c\\cdotR^{3}\\cdot R^{4}}$ 及 $\\mathrm{R}^{10}$ 的定义与上述式(3)中的定义相同， $\\mathfrak{n}$ 的定义与上述式(3-1)中的定义相同。  \n\n[0104] 上述共聚物(i)为包含上述式(1)、(2)及(3)所示的结构单元的共聚物(以下也称为共聚物(i3))， $\\mathrm{a+b+c=100}$ ，通常a＝ $99.8{\\sim}0.1,\\mathrm{b}{=}0.1{\\sim}99.8,\\mathrm{c}{=}0.1{\\sim}99.8$ ，优选 $\\mathrm{a}=50$ $\\sim99.8,\\mathrm{b}=0.1\\mathrm{\\sim}25.\\mathrm{c}=0.1\\mathrm{\\sim}25$ ，更优选 $\\mathrm{a}{=}72{\\sim}98.\\mathrm{b}{=}1{\\sim}14.\\mathrm{c}{=}1{\\sim}14. $ 。  \n\n[0105] 当想要提高上述共聚物(i)的亲水性时，提高具有含磺酸基团的式(1)所示的结构单元的比a即可。然而，若过度提高式(1)所示的结构单元的比a，则具有有助于交联反应的基团的式(2)所示的结构单元及(3)的结构单元的比相对降低，由含有共聚物(i)的组合物形成的固化物(例如，由该固化物形成的膜)的交联密度降低，等等，因此，存在韧性、耐磨性、耐药品性等降低的倾向，有时不理想。  \n\n[0106] 另外，上述共聚物(i)中，在包含较多的(3)所示的结构单元的共聚物的情况下，硬度、耐磨性等存在提高的倾向，但亲水性存在容易降低的倾向。因此，对于要求高亲水性的用途而言，作为上述共聚物(i)，存在优选共聚物(i3)的倾向。  \n\n[0107] 为了将上述式(1)所示的结构单元导入共聚物(i)中，例如，将下述单体混合物聚合即可，所述单体混合物包含与式(1)所示的结构单元对应的具有含有碳-碳双键的聚合性官能团及 $\\mathrm{S03M}$ 基的化合物。同样地，为了将上述式(2)所示的结构单元导入共聚物(i)中，将下述单体混合物聚合即可，所述单体混合物包含与式(2)所示的结构单元对应的具有含有碳-碳双键的聚合性官能团及环氧基的化合物；为了将上述式(3)所示的结构单元导入共聚物(i)中，将下述单体混合物聚合即可，所述单体混合物包含与式(3)所示的结构单元对应的具有含有碳-碳双键的聚合性官能团及烷氧基甲硅烷基的化合物。  \n\n[0108] 因此，上述共聚物(i)中可包含的结构单元(1)、(2)及(3)的比a、b及c可通过在聚合制造上述共聚物(i)时的单体混合物中所含的与式(1)所示的结构单元对应的单体、与式(2)所示的结构单元对应的单体、及与式(3)所示的结构单元对应的单体的投料比等来控制。  \n\n[0109] 作为与式(1)所示的结构单元对应的具有含有碳-碳双键的聚合性官能团及 $\\mathrm{S0_{3}M}$ 基的化合物，可举出下述通式(1’)所示的化合物。  \n\n[0110]  \n\n![](images/478178aa260b707c4285597d62c1c60eeb071f9df9d1590e725bd0bfd6d9d260.jpg)  \n\n[0111] 上述式 $(1^{\\prime})$ 中， $\\mathrm{R}^{1}\\cdot\\mathrm{A}^{1}$ 及M的定义及优选方式与上述式(1)相同。  \n\n[0112] 上述式 $(1^{\\prime})$ 所示的化合物中，较优选具有乙烯基的磺酸系化合物、具有烯丙基的磺酸系化合物、具有异丙烯基的磺酸系化合物、具有苯乙烯基的磺酸系化合物、具有丙烯酰氧基或甲基丙烯酰氧基(以下，有时将丙烯酰氧基及甲基丙烯酰氧基统称地记载为(甲基)丙烯酰氧基。另外，有时将丙烯酰基及甲基丙烯酰基统称地记载为(甲基)丙烯酰基。)的磺酸系化合物、及具有丙烯酰胺基或甲基丙烯酰胺基(以下，有时将丙烯酰胺及甲基丙烯酰胺统称地记载为(甲基)丙烯酰胺。)的磺酸系化合物。  \n\n[0113] 作为具有乙烯基的磺酸系化合物，优选为乙烯基磺酸及它们的碱金属盐、铵盐，例如乙烯基磺酸锂等。  \n\n[0114] 作为具有烯丙基的磺酸化合物，优选为烯丙基磺酸、烯丙基磺酸钠、烯丙基磺酸钾等。  \n\n[0115] 作为具有异丙烯基的磺酸系化合物，优选为异丙烯基磺酸、4-异丙烯基苯-1-磺酸钠、3-异丙烯基苯-1-磺酸钠、2-异丙烯基苯-1-磺酸钠、4-异丙烯基苯-1-磺酸钾等。  \n\n[0116] 作为具有苯乙烯基的磺酸系化合物，优选为4-苯乙烯磺酸、2-苯乙烯磺酸及它们的碱金属盐、碱土金属盐、铵盐，例如4-苯乙烯磺酸锂等。  \n\n[0117] 作为具有(甲基)丙烯酰氧基的磺酸系化合物，优选为(甲基)丙烯酸甲磺酸酯 (sulfomethyl(meth)acrylate)的碱金属盐、(甲基)丙烯酸甲磺酸酯的碱土金属盐，例如 (甲基)丙烯酸甲磺酸酯钠盐等。  \n\n[0118] 作为具有(甲基)丙烯酰胺基的磺酸系化合物，优选为下述式(4’)所示的化合物。  \n\n[0119]  \n\n![](images/aef1dfcb404e2cc259bb1a46532c1c92fa7f55fe0eec49bf07c9fc3602c9b812.jpg)  \n\n[0120] 上述式 $(4^{\\prime})$ 中的 $\\mathrm{R^{1}\\cdot R^{5}\\cdot R^{6}}$ 、M及n1的定义及优选方式与上述式(4)相同。  \n\n[0121] 作为上述式 $(4^{\\prime})$ 所示的化合物，可举出 $1^{-}$ (甲基)丙烯酰胺基-甲磺酸、1-(甲基)丙烯酰胺基-甲磺酸钾、2-(甲基)丙烯酰胺基-乙磺酸、 $2^{-}$ (甲基)丙烯酰胺基-乙磺酸钠、2-(甲基)丙烯酰胺基-丙磺酸、 $2^{-}$ (甲基)丙烯酰胺基-丙磺酸钾、2-(甲基)丙烯酰胺基 $-2-$ 甲基-丙磺酸((甲基)丙烯酰胺基-叔丁基磺酸)、 $2^{-}$ (甲基)丙烯酰胺基 $^{-2-}$ 甲基-丙磺酸钠盐、2-(甲基)丙烯酰胺基 $-2-$ 甲基-丙磺酸钾盐、2-(甲基)丙烯酰胺基 $^{-2-}$ 甲基-丙磺酸铷盐、2-(甲基)丙烯酰胺基 $^{-2-}$ 甲基-丙磺酸钙盐、2-(甲基)丙烯酰胺基 $-2-$ 甲基-丙磺酸镁盐、2-(甲基)丙烯酰胺基 $-2-$ 甲基-丙基磺酸铵盐、3-(甲基)丙烯酰胺基-丙磺酸钾盐等具有(甲基)丙烯酰胺基(acryloylamide)的磺酸化合物等。  \n\n[0122] 上述化合物(1’)中，优选具有(甲基)丙烯酰胺基的磺酸系化合物，更优选上述式$(4^{\\prime})$ 所示的化合物，进一步优选2-(甲基)丙烯酰胺基 $^{-2-}$ 甲基-丙基磺酸((甲基)丙烯酰胺基-叔丁基磺酸)、2-(甲基)丙烯酰胺基 $^{-2-}$ 甲基-丙基磺酸((甲基)丙烯酰胺基-叔丁基磺酸)碱金属盐、2-(甲基)丙烯酰胺基 $^{-2-}$ 甲基-丙基磺酸((甲基)丙烯酰胺基-叔丁基磺酸)碱土金属盐、2-(甲基)丙烯酰胺基 $-2-$ 甲基-丙基磺酸((甲基)丙烯酰胺基-叔丁基磺酸)铵盐、2-(甲基)丙烯酰胺基 $-2-$ 甲基-丙基磺酸((甲基)丙烯酰胺基-叔丁基磺酸)胺盐，最优选2-(甲基)丙烯酰胺基 $-2-$ 甲基-丙基磺酸((甲基)丙烯酰胺基-叔丁基磺酸)碱金属盐。  \n\n[0123] 以下，对通式(1’)所示的化合物中M优选为氢原子以外的碱金属离子、1/2价的碱土金属离子、铵离子及胺离子的理由进行说明。  \n\n[0124] 在磺酸未被中和的情况下(M为氢原子的情况下)，在聚合反应中，有时磺酸基与后述的具有环氧基的化合物(典型的是下述通式(2’)所示的化合物)中包含的环氧基反应，发生凝胶化。关于该环氧基与磺酸基的反应，将示意性的反应式记载如下。  \n\n[0125]  \n\n![](images/72288ab0a5fa472ec94df8b4d7cff68317ff8c8b17a931dda89bcb416b38318d.jpg)  \n\n[0126] 为了抑制上述反应从而得到高纯度的共聚物(i)，优选利用抗衡阳离子中和磺酸基，抑制磺酸基与环氧基的反应(同样地，将示意性的反应式记载如下)。  \n\n[0127]  \n\n![](images/eb98995664ffb0783f164b8d5d5b10d9bdb52c2cb8fb1a6e978972a7099a5bc1.jpg)  \n反应抑制  \n\n[0128] 进而，在作为抗衡阳离子的碱金属离子、碱土金属离子、铵离子及胺离子中，倾向于优选存在反应抑制力和稳定性高的倾向的碱金属离子。碱金属中，优选钠或钾，更优选钾。其理由虽不明确，但抗衡阳离子为钾时与为钠时相比，存在热稳定性高的情况。作为参考，将上述具有含有碳-碳双键的聚合性官能团及含磺酸基团的化合物中的代表性化合物的热稳定性比较数据(DSC图)记载于图1。  \n\n[0129] 作为与式(2)所示的结构单元对应的具有含有碳-碳双键的聚合性官能团及环氧基的化合物，可举出下述通式(2’)所示的化合物。  \n\n[0130]  \n\n![](images/0895ae4ad1580da2a00cf5a0e7053a3d7b74836d0c0f1f4c7a06ada0e0538275.jpg)  \n\n[0131] 上述式 $(2^{\\prime})$ 中， $\\mathrm{R}^{2}$ 及 $\\mathrm{A}^{2}$ 的定义及优选方式与上述式(2)相同。  \n\n[0132] 上述式 $(2^{\\prime})$ 所示的化合物中，较优选具有乙烯基的环氧化合物、具有乙烯基醚基的环氧化合物、具有烯丙基醚基的环氧化合物、具有异丙烯基醚基的环氧化合物、具有苯乙烯基的环氧化合物、具有(甲基)丙烯酰氧基的环氧化合物。  \n\n[0133] 作为具有乙烯基的环氧化合物，优选为乙烯基-环己烯单氧化物(vinyl-cyclohexene  monoxide)、丁二烯-单氧化物(butadiene-monoxide)、戊二烯-单氧化物(pentadiene-monoxide)、己二烯-单氧化物(hexadiene-monoxide)等。  \n\n[0134] 作为具有乙烯基醚基的环氧化合物，优选为乙烯基缩水甘油基醚、丁二醇-二乙烯基醚单氧化物、环己烷二甲醇-二乙烯基醚单氧化物、4-缩水甘油基氧基甲基-1-乙烯基氧基甲基-环己烷、二乙二醇-二乙烯基醚单氧化物、三丙二醇-二乙烯基醚单氧化物、4-乙烯基氧基-1-缩水甘油基氧基-丁烷等。  \n\n[0135] 作为具有烯丙基醚基的环氧化合物，优选为烯丙基-缩水甘油基醚、烯丙基-环氧基醚、丁二醇-二烯丙基醚单氧化物、环己烷二甲醇-二烯丙基醚单氧化物、4-缩水甘油基氧基甲基-1-烯丙基氧基甲基-环己烷、二乙二醇-二烯丙基醚单氧化物、三丙二醇-二烯丙基醚单氧化物、4-烯丙基氧基-1-缩水甘油基氧基-丁烷等。  \n\n[0136] 作为具有异丙烯基醚基的环氧化合物，优选为异丙烯基缩水甘油基醚、异丙烯基环氧基醚、丁二醇-二异丙烯基醚单氧化物、环己烷二甲醇-二异丙烯基醚单氧化物、4-缩水甘油基氧基甲基-1-异丙烯基氧基甲基-环己烷、二乙二醇-二异丙烯基醚单氧化物、三丙二醇-二异丙烯基醚单氧化物、4-异丙烯基氧基-1-缩水甘油基氧基-丁烷、4-异丙烯基-1-缩水甘油基氧基-苯等。  \n\n[0137] 作为具有苯乙烯基的环氧化合物，优选为二乙烯基苯-单氧化物、4-缩水甘油基氧基-苯乙烯、3-缩水甘油基氧基-苯乙烯、2-缩水甘油基氧基-苯乙烯、4-环氧基氧基-苯乙烯、苯乙烯基羧酸环氧基酯(styryl  carboxylic  acid  epoxy  ester)、苯乙烯基羧酸缩水甘油基酯(styryl  carboxylic  acid  glycidyl  ester)等。  \n\n[0138] 作为具有(甲基)丙烯酰氧基的环氧化合物，优选为下述式(5’)所示的化合物。  \n\n[0139]  \n\n![](images/e9c90305a9e1bc96c0d354aa0a38b2875685486560b60df7daa38c9e0d35a2cf.jpg)  \n\n[0140] 上述式 $(5^{\\prime})$ 中， $\\mathrm{R}^{2}$ 及n的定义与上述式(5)中的定义相同。  \n\n[0141] 作为上述式(5’)所示的化合物，例如，可举出(甲基)丙烯酸缩水甘油基酯、(甲基)丙烯酸环氧基酯、(甲基)丙烯酸2-缩水甘油基氧基-乙基酯、(甲基)丙烯酸3-缩水甘油基氧基-丙基酯、(甲基)丙烯酸4-缩水甘油基氧基-丁基酯、(甲基)丙烯酸6-缩水甘油基氧基-己基酯、(甲基)丙烯酸5-缩水甘油基氧基 $\\cdot3-$ 氧杂戊基酯、(甲基)丙烯酸3-缩水甘油基氧基-2-羟基-丙基酯、(甲基)丙烯酸2，3-双(缩水甘油基氧基)-丙基酯、三羟甲基丙烷-二缩水甘油基醚-(甲基)丙烯酸酯、{4-缩水甘油基氧基苯基}-{ $(4^{-}$ (甲基)丙烯酰氧基 $\\cdot-3-$ 羟基-1-氧杂丁基)苯基}-2，2-丙烷、(甲基)丙烯酸7-缩水甘油基氧基 $^{-6,6-}$ 二甲基-2-羟基 $\\cdot^{-4^{-}}$ 氧杂庚基酯等。  \n\n[0142] 上述式 $(2^{\\prime})$ 所示的化合物中，优选具有(甲基)丙烯酰氧基的环氧化合物、具有烯丙基醚基的环氧化合物、具有苯乙烯基的环氧化合物，更优选(甲基)丙烯酸缩水甘油基酯、(甲基)丙烯酸4-缩水甘油基氧基-丁基酯、烯丙基缩水甘油基醚、4-缩水甘油基氧基苯乙烯。  \n\n[0143] 作为与式(3)所示的结构单元对应的具有含有碳-碳双键的聚合性官能团及烷氧基甲硅烷基的化合物，可举出下述通式 $(3^{\\prime})$ 所示的化合物。  \n\n[0144]  \n\n![](images/0c098c7cf648e026d0f8a6fdadaed7f897e8d608a7143503c432950380c94b80.jpg)  \n\n[0145] 上述式 $(3^{\\prime})$ 中， $\\mathrm{R^{3}}\\mathrm{\\cdot}\\mathrm{R^{4}}\\mathrm{\\cdot}\\mathrm{R^{10}}$ 及 $\\mathrm{A}^{3}$ 的定义及优选方式与上述式(3)相同。  \n\n[0146] 上述式 $(3^{\\prime})$ 所示的化合物中，较优选具有乙烯基的烷氧基甲硅烷基化合物、具有乙烯基醚基的烷氧基甲硅烷基化合物、具有烯丙基的烷氧基甲硅烷基化合物、具有异丙烯基的烷氧基甲硅烷基化合物、具有烯丙基醚基的烷氧基甲硅烷基化合物、具有异丙烯基醚基的烷氧基甲硅烷基化合物、具有苯乙烯基的烷氧基甲硅烷基化合物、具有(甲基)丙烯酰氧基的烷氧基甲硅烷基化合物。  \n\n[0147] 作为具有乙烯基的烷氧基甲硅烷基化合物，优选为乙烯基-三甲氧基硅烷、乙烯基-三乙氧基硅烷、乙烯基-三丙氧基硅烷、乙烯基-三异丙氧基硅烷、乙烯基-三丁氧基硅烷、乙烯基-甲基二甲氧基硅烷、乙烯基-苯基二甲氧基硅烷、乙烯基-乙基二乙氧基硅烷、乙烯基-二乙基单乙氧基硅烷、乙烯基-二甲基单丁氧基硅烷等。  \n\n[0148] 作为具有乙烯基醚基的烷氧基甲硅烷基化合物，优选为乙烯基氧基-乙基三甲氧基硅烷、乙烯基氧基-丙基三甲氧基硅烷等。  \n\n[0149] 作为具有烯丙基的烷氧基甲硅烷基化合物，优选为烯丙基三甲氧基硅烷、烯丙基三乙氧基硅烷、烯丙基三丙氧基硅烷、烯丙基三异丙氧基硅烷、烯丙基三丁氧基硅烷、异丙烯基三乙氧基硅烷、烯丙基甲基二甲氧基硅烷、烯丙基苯基二甲氧基硅烷、烯丙基乙基二乙氧基硅烷、烯丙基二乙基单乙氧基硅烷、烯丙基二甲基单丁氧基硅烷等。  \n\n[0150] 作为具有烯丙基醚基的烷氧基甲硅烷基化合物，优选为烯丙基氧基-乙基三甲氧基硅烷、烯丙基氧基-丙基三甲氧基硅烷、烯丙基氧基-丙基三乙氧基硅烷等。  \n\n[0151] 作为具有异丙烯基的烷氧基甲硅烷基化合物，优选为4-异丙烯基 $-1-$ 三甲氧基甲硅烷基-苯、4-异丙烯基-1-三乙氧基甲硅烷基-苯等。  \n\n[0152] 作为具有异丙烯基醚基的烷氧基甲硅烷基化合物，优选为异丙烯基氧基-丙基三甲氧基硅烷、异丙烯基氧基-丙基三乙氧基硅烷等。  \n\n[0153] 作为具有苯乙烯基的烷氧基甲硅烷基化合物，优选为苯乙烯基-三甲氧基硅烷、苯乙烯基-三乙氧基硅烷、苯乙烯基-三丁氧基硅烷、苯乙烯基-甲基二甲氧基硅烷等。  \n\n[0154] 作为具有(甲基)丙烯酰氧基的烷氧基甲硅烷基化合物，优选为下述式 $(6^{\\prime})$ 所示的化合物。  \n\n[0155]  \n\n![](images/247f6c9449b7454c74bf03d3dd9f644470379c2db5212357d315cf8517d19394.jpg)  \n\n[0156] 上述式 $\\left(6^{\\prime}\\right)$ 中的 $\\mathrm{R^{3}}\\mathrm{\\cdot}\\mathrm{R^{4}}\\mathrm{\\cdot}\\mathrm{R^{10}}$ 及n的定义与上述式(6)中的定义相同。  \n\n[0157] 作为上述式 $(6^{\\circ})$ 所示的化合物，例如，可举出(甲基)丙烯酰氧基-乙基三甲氧基硅烷、(甲基)丙烯酰氧基-丙基-三甲氧基硅烷、(甲基)丙烯酰氧基-丁基-三甲氧基硅烷、(甲基)丙烯酰氧基-己基-三甲氧基硅烷、(甲基)丙烯酰氧基-癸基-三甲氧基硅烷、(甲基)丙烯酰氧基-丙基-三乙氧基硅烷、(甲基)丙烯酰氧基-丙基-三丙氧基硅烷、(甲基)丙烯酰氧基-丙基-三丁氧基硅烷、(甲基)丙烯酰氧基-丙基-甲基二甲氧基硅烷、(甲基)丙烯酰氧基-丙基-乙基二乙氧基硅烷等。  \n\n[0158] 上述式(3’)所示的化合物中，优选具有乙烯基的烷氧基甲硅烷基化合物、具有苯乙烯基的烷氧基甲硅烷基化合物及具有(甲基)丙烯酰氧基的烷氧基甲硅烷基化合物，更优选乙烯基-三甲氧基硅烷、乙烯基-三乙氧基硅烷、苯乙烯基-三甲氧基硅烷、苯乙烯基-三乙氧基硅烷、(甲基)丙烯酰氧基-丙基-三甲氧基硅烷、(甲基)丙烯酰氧基-丙基-三乙氧基硅烷。  \n\n[0159] 上述共聚物(i)中，也可包含除了通式 $(1)\\sim(3)$ 所示的结构单元以外的其他的结构单元。  \n\n[0160] 其他的结构单元例如可通过以下方式得到：向包含上述 $(1^{\\prime})\\sim(3^{\\prime})$ 所示的化合物的单体混合物中，进一步添加与其他的结构单元对应的化合物，进行聚合。  \n\n[0161] 作为与其他的结构单元对应的化合物，例如，可举出丙烯酸、甲基丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸四氢糠酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸三溴苯酯、(甲基)丙烯酸羟基乙酯、(甲基)丙烯酸磷酸乙酯、(甲基)丙烯酸四甲基哌啶酯、(甲基)丙烯酸全氟辛基乙酯、(甲基)丙烯酸硫代缩水甘油基酯、苯乙烯、丙烯腈、二乙烯基苯、(甲基)丙烯酸烯丙酯等。需要说明的是，当使用二乙烯基苯及(甲基)丙烯酸烯丙基酯时，优选以共聚物(i)不发生凝胶化的程度少量使用。  \n\n[0162] 式(1)、(2)及(3)所示的结构单元的总结构单元数 $\\left({\\mathrm{a+b+c}}\\right)$ 与上述其他的结构单元数(d)之比(摩尔比) $\\left({\\mathrm{a+b+c}}\\right)$ /d通常为 $100/0{\\sim}30/70$ ，更优选为 $100/0{\\sim}50/50$ ，进一步优选为 $100/0{\\sim}60/40$ 的范围。另外，当使用上述其他的结构单元(d)时，上述摩尔比 $\\left(\\mathrm{a+b+c}\\right)$ )/d通常为 $99.9/0.1{\\sim}30/70$ 的范围，更优选为 $99/1{\\sim}50/50$ 的范围，进一步优选为 $95/5{\\sim}60/40$ 的范围。需要说明的是，有时也优选 $\\displaystyle\\bigl(a+b+c\\bigr)$ )/d为70/30以上，更优选为80/20以上。  \n\n[0163] 另外，式(1)、(2)及(3)所示的结构单元的总重量 $\\left(\\mathbb{W}\\mathrm{a}{+}\\mathbb{W}\\mathrm{b}{+}\\mathbb{W}\\mathrm{c}\\right)$ 与上述其他的结构单元的重量(Wd)之比(质量比) $(W a+W b+W c)$ )/Wd优选为 $100/0{\\sim}30/70$ 的范围，更优选为 $100/0\\sim$ 50/50的范围，进一步优选为 $100/0{\\sim}60/40$ 的范围。  \n\n[0164] 本发明中使用的共聚物(i)典型地可通过在聚合引发剂的存在下将下述单体混合物进行溶液聚合而得到，所述单体混合物含有式 $(1^{\\prime})$ 所示的化合物、式 $(2^{\\prime})$ 所示的化合物、式 $(3^{\\prime})$ 所示的化合物及根据需要含有的与其他的结构单元对应的化合物。对于上述共聚物(i)的结合形式没有特别限制，优选使用自由基聚合引发剂、通过自由基聚合而制造的共聚物(i)。此时，可认为共聚物(i)的结合形式成为无规共聚物的结合形式。  \n\n[0165] 本发明中使用的共聚物(i)的重复结构单元数及分子量主要可通过溶剂的种类、化合物(单体)浓度、聚合引发剂量及反应温度等来控制。  \n\n[0166] 上述共聚物(i)的重复结构单元数通常为 $1{\\sim}10$ ,000的范围，优选为 $3\\sim3,000$ 的范 围，进一步优选为 $30{\\sim}1$ ,500的范围。  \n\n[0167] 上述共聚物(i)的利用GPC测得的以标准聚甲基丙烯酸甲酯换算的重均分子量(Mw)通常为 $500{\\sim}3,000,000$ 的范围，但从耐久性及溶解性方面考虑，优选为 $1000{\\sim}1$ ,000 ,000，进一步优选为10, $000{\\sim}500,000$ 。  \n\n[0168] 另外，本发明中使用的共聚物(i)的重均分子量(Mw)与数均分子量(Mn)之比即分子量分布Mw/Mn通常为 $1{\\sim}10$ ，优选为 $1{\\sim}6$ ，更优选为 $1{\\sim}4$ 。通过使Mw/Mn在上述范围内，从而存在以下倾向：共聚物(i)或含有共聚物(i)的组合物在溶剂中的溶解性或分散性优异，通过将该组合物固化而得到的固化物、例如由该固化物形成的膜的透明性或平滑性等优异。  \n\n[0169] 作为上述聚合引发剂，优选为自由基聚合引发剂。  \n\n[0170] 作为自由基聚合引发剂，例如，可举出偶氮化合物(偶氮系自由基聚合引发剂)、有机过氧化物等。作为偶氮化合物，例如，可例示偶氮二异丁腈(AIBN)，作为有机过氧化物，可例示酮过氧化物类、二酰基过氧化物类(过氧化苯甲酰等)、氢过氧化物类、二烷基过氧化物类、过氧缩酮类、过酸烷基酯(alkyl  perester)类、过碳酸酯类等。它们之中，优选有机过氧化物，特别优选过氧化 $-2-$ 乙基己酸叔丁酯等过酸烷基酯类等自由基聚合引发剂。  \n\n[0171] 对于这些聚合引发剂的添加量而言，相对于式 $(1^{\\prime})$ 所示的化合物、式 $(2^{\\prime})$ 所示的化合物、式 $(3^{\\prime})$ 所示的化合物、及根据需要含有的与其他的结构单元对应的化合物的总重量，大致为 $0.01\\sim10\\mathrm{wt}\\%$ 的范围，优选为 $0.1{\\sim}5\\mathrm{wt}\\%$ 的范围，进一步优选为 $0.2{\\sim}3\\mathrm{wt}\\%$ 的范围。  \n\n[0172] 作为聚合溶剂，只要是不发生抑制聚合反应等不良情况的溶剂即可，没有特别限制，倾向于优选对式 $(1^{\\prime})$ 所示的化合物、式(2’)所示的化合物、式 $(3^{\\prime})$ 所示的化合物及根据需要含有的与其他的结构单元对应的化合物的溶解性高的高极性溶剂。  \n\n[0173] 作为这样的聚合溶剂，例如，可举出甲醇、乙醇、异丙醇(IPA)、 $.1-$ 丙醇 $\\cdot1^{-}$ 丁醇、 $\\cdot1^{-}$ 戊醇、异戊醇、1-己醇、1-辛醇、环己醇、苯甲醇、乙二醇、丙二醇、乙二醇单甲基醚(2-甲氧基乙醇)、丙二醇单甲基醚(1-甲氧基 $^{-2-}$ 丙醇)等醇类，乙腈、环丁砜、二甲基亚砜、N，N-二甲基甲酰胺(DMF)、N，N-二甲基乙酰胺(DMAc)、 $\\cdot\\mathrm{N},\\mathrm{N-}$ 二甲基咪唑啉酮(DMI)等非质子性极性溶剂，水及它们的混合物等。  \n\n[0174] 聚合温度主要可通过自由基聚合引发剂的10小时半衰期温度来设定，大致为室温${\\sim}200^{\\circ}\\mathrm{C}$ 的范围，优选为 $30{\\sim}120^{\\circ}\\mathrm{C}$ 的范围，更优选为 $40{\\sim}100^{\\circ}\\mathrm{C}$ 的范围。  \n\n[0175] 进一步地，以下说明本发明中使用的共聚物(i)的理想性质及高级结构。  \n\n[0176] 对于上述共聚物(i)而言，有时以要求高透明性的用途的固化物、膜及层叠体的形式使用，因此，优选透明性增高的非晶性的聚合物(结晶度低，无法测定 $\\mathrm{Tm}$ (熔点)或熔化热小。相当于非晶质聚合物或隐晶质聚合物。)。  \n\n[0177] 这样的透明性高的共聚物(i)例如可通过使式 $(1)\\sim(3)$ 的各结构单元比为所期望的范围来制作。  \n\n[0178] 另一方面，当形成核·壳结构体等高级结构时，这些核·壳结构体通常容易形成微米尺寸的大粒子，即使能形成纳米尺寸的小粒子，也会存在以下倾向：由于凝集等而发生二次粒子化，结果形成大的微米尺寸的粒子集合体。例如，对于这些微米尺寸的核·壳结构体而言，由于粒子尺寸大于光的1/4波长(约 $100\\mathrm{nm})$ ，所以光发生散射，透明性降低，因此，无法用于要求高透明性的用途。  \n\n[0179] 即，对于本发明中使用的共聚物(i)而言，优选不形成核壳等高级结构。另外，通常，由2种聚合物或聚合物原料等形成的上述的核壳结构体存在可观测到2个Tg(玻璃化转变温度)的倾向。  \n\n[0180] 这样的不形成高级结构的共聚物(i)例如可通过将形成各结构单元的化合物(单体)溶解于溶剂中进行聚合(溶液聚合)来制作。  \n\n[0181] 这样地形成的共聚物(i)通常为具有大量含磺酸基团的高分子量体，具有仅溶解于水的性质的情况也较多。因此，此时如果不大量使用水作为聚合溶剂，则随着聚合反应的进行，共聚物会逐渐从聚合溶液中析出。  \n\n[0182] 因此，在聚合反应结束后，仅通过过滤并进行干燥即可得到目标共聚物。  \n\n[0183] 另一方面，在为共聚物不易从聚合溶液中析出的含磺酸基团数目少的共聚物的情况下，可通过以下方法得到目标共聚物：放入到不良溶剂中使其析出；或利用蒸发器等蒸馏除去溶剂后，向残渣中添加不良溶剂并混合搅拌，进行过滤并将得到的滤饼干燥的方法。  \n\n[0184] 本发明的共聚物(i)主要通过与后述的氨基树脂(ii)的交联反应进行固化而成为本发明的固化物，由于共聚物(i)含有选自环氧基及烷氧基甲硅烷基中的至少一种基团，所以有时共聚物(i)彼此也发生交联反应而形成本发明的固化物的一部分骨架。环氧基及烷氧基甲硅烷基的反应通常通过加热而被促进。需要说明的是，作为加热以外的促进反应方法，例如，可举出照射微波(放射线的一种)的方法等。  \n\n[0185] 对于通过各基团而发生的反应，以下举出具有代表性的(a)、(b)及(c)的共聚物为例来进行详细说明。  \n\n[0186]  \n\n![](images/9ab5368b126dd7b45a59adc0649aab39bcd8723dda3c1e8bde696f679a532f4b.jpg)  \n\n[0187] <环氧基之间的反应>  \n\n[0188] 环氧基之间的反应由通式(11)表示，优选进行加热而使其反应。加热温度大致为$30{\\sim}250^{\\circ}\\mathrm{C}$ 的范围，优选为 $30{\\sim}200^{\\circ}\\mathrm{C}$ 的范围，进一步优选为 $30{\\sim}150^{\\circ}\\mathrm{C}$ 的范围。该环氧基之间的反应存在以下倾向：通过存在以酸等阳离子及碱等阴离子为代表的催化剂，可加速反应。  \n\n[0189] <环氧基与烷氧基甲硅烷基的反应>[0190] 环氧基与烷氧基甲硅烷基的反应由通式(12)及通式(14)表示。  \n\n[0191] 一般情况下，环氧基与烷氧基甲硅烷基难以直接反应，通常在烷氧基甲硅烷基水解而成的硅烷醇基与环氧基之间发生反应。对于环氧基与烷氧基甲硅烷基的反应而言，也优选进行加热而使其反应。加热温度大致为 $30{\\sim}300^{\\circ}\\mathrm{C}$ 的范围，优选为 $50{\\sim}250^{\\circ}\\mathrm{C}$ 的范围，进一步优选为 $100{\\sim}200^{\\circ}\\mathrm{C}$ 的范围。  \n\n[0192] 烷氧基甲硅烷基的水解反应及环氧基与硅烷醇基的反应存在以下倾向：通过存在以酸等阳离子及碱等阴离子为代表的催化剂，可加速反应。在如上所述地使用催化剂的情况下，也优选进行加热而使其反应。加热温度大致为 $30{\\sim}250^{\\circ}\\mathrm{C}$ 的范围，优选为 $30{\\sim}200^{\\circ}\\mathrm{C}$ 的范围，进一步优选为 $30{\\sim}180^{\\circ}\\mathrm{C}$ 的范围。  \n\n[0193] <烷氧基甲硅烷基之间的反应>  \n\n[0194] 烷氧基甲硅烷基之间的反应式由通式(13)表示，优选进行加热而使其反应。加热温度大致为 $30{\\sim}250^{\\circ}\\mathrm{C}$ 的范围，优选为 $30{\\sim}200^{\\circ}\\mathrm{C}$ 的范围，进一步优选为 $30{\\sim}180^{\\circ}\\mathrm{C}$ 的范围。[0195] 另外，烷氧基甲硅烷基在水分的作用下较容易被水解，被转化为硅烷醇基。该硅烷醇基的反应性高，硅烷醇基之间的反应比烷氧基甲硅烷基之间的反应更容易发生。因此，烷氧基甲硅烷基之间的反应，通常以在水分作用下被水解而得到的硅烷醇基之间的反应、硅烷醇基与烷氧基甲硅烷基的反应的形式进行。该硅烷醇基之间的反应、及硅烷醇基与烷氧基甲硅烷基的反应优选进行加热来进行。加热温度大致为 $30{\\sim}200^{\\circ}\\mathrm{C}$ 的范围，优选为 $30\\sim$ $180^{\\circ}\\mathrm{C}$ 的范围，进一步优选为 $30{\\sim}150^{\\circ}\\mathrm{C}$ 的范围。  \n\n[0196] 烷氧基甲硅烷基之间的反应、烷氧基甲硅烷基的水解反应、及烷氧基甲硅烷基与硅烷醇基的反应、及硅烷醇基之间的反应存在以下倾向：通过存在以酸等阳离子、碱等阴离子、烷氧基钛及氧化锡等金属化合物为代表的催化剂，可加速反应。  \n\n[0197] 本发明的固化物(例如，膜)可通过将共聚物(i)与氨基树脂(ii)的组合物固化而 得到。  \n\n[0198] 典型地，也可以通过使分子内具有磺酸基和环氧基和烷氧基甲硅烷基的共聚物(上述通式 $(10^{3})$ )与作为代表性的氨基树脂的三聚氰胺树脂(下述通式(15))进行反应(例如，通过下述通式 $(16)\\sim(19)$ 所示的羟基甲基或烷氧基甲基的缩聚反应进行的交联)而进行固化，形成固化物、例如膜。这些与羟基甲基或烷氧基甲基的缩聚反应通常通过加热而进行。需要说明的是，作为加热以外的固化方法，例如，可举出照射微波(放射线的一种)而进行固化的方法等。  \n\n[0199] 对于通过各基团而发生的反应，以下举例进行详细说明。  \n\n[0200]  \n\n![](images/e60a0814949d8627486268966f82d522bbba2aa74cafc933a0483a242e3e505c.jpg)  \n\n[0201] <羟基甲基与环氧基的反应>  \n\n[0202] 羟基甲基与环氧基的反应由通式(16)表示。本反应进行缓慢，存在以下倾向：若添加阿仑尼乌斯酸或路易斯酸性的化合物等作为催化剂，则该反应被促进。反应温度大致为$30{\\sim}300^{\\circ}\\mathrm{C}$ 的范围，优选为 $50{\\sim}250^{\\circ}\\mathrm{C}$ 的范围，进一步优选为 $80{\\sim}180^{\\circ}\\mathrm{C}$ 的范围。  \n[0203] <烷氧基甲基与环氧基的反应>  \n[0204] 烷氧基甲基与环氧基的反应由通式(17)表示，但由于存在比上述羟基甲基与环氧基的反应(16)更难进行的倾向，所以通常与仲羟基发生缩合反应，所述仲羟基是环氧基与硅烷醇基等活性氢基团进行开环反应而生成的。该烷氧基甲基与仲羟基的反应也与通式(16)的反应同样地缓慢，存在以下倾向：若添加阿仑尼乌斯酸或路易斯酸性的化合物等作为催化剂，则该反应被促进。反应温度大致为 $30{\\sim}300^{\\circ}\\mathrm{C}$ 的范围，优选为 $50{\\sim}250^{\\circ}\\mathrm{C}$ 的范围，进一步优选为 $80{\\sim}180^{\\circ}\\mathrm{C}$ 的范围。  \n\n[0205] <羟基甲基与硅烷醇基的反应>  \n\n[0206] 羟基甲基与硅烷醇基(其是来源于共聚物(i)的烷氧基甲硅烷基水解而生成的)的反应由通式(17)表示。本反应存在比通式(17)所示的与仲醇的反应更快的倾向。为了提高反应速度，有时也添加阿仑尼乌斯酸或路易斯酸性的化合物等作为催化剂。反应温度大致为 $20{\\sim}300^{\\circ}\\mathrm{C}$ 的范围，优选为 $40{\\sim}250^{\\circ}\\mathrm{C}$ 的范围，进一步优选为 $80{\\sim}180^{\\circ}\\mathrm{C}$ 的范围。  \n\n[0207] <烷氧基甲基与硅烷醇基的反应>  \n\n[0208] 烷氧基甲基与硅烷醇基(其是来源于共聚物(i)的烷氧基甲硅烷基水解而生成的)的反应由通式(19)表示。本反应也与通式(18)所示的反应同样地，存在比通式(17)所示的与仲醇的反应更快的倾向。为了提高反应速度，有时也添加阿仑尼乌斯酸或路易斯酸性的化合物等作为催化剂。反应温度大致为 $20{\\sim}300^{\\circ}\\mathrm{C}$ 的范围，优选为 $40{\\sim}250^{\\circ}\\mathrm{C}$ 的范围，进一步优选为 $80{\\sim}180^{\\circ}\\mathrm{C}$ 的范围。  \n\n[0209] 本发明中使用的氨基树脂(ii)，是通过含有氨基的化合物与甲醛的缩聚而制造的树脂，例如，可举出与三聚氰胺缩聚而成的三聚氰胺树脂、与尿素缩聚而成的尿素(脲)树脂、及与苯胺缩聚而成的苯胺树脂等。进而，这些氨基树脂还包含烷基化氨基树脂，所述烷基化氨基树脂是将甲醛反应生成的羟基中的一部分或全部用烷氧基进行取代而得到的。  \n\n[0210] 作为上述氨基树脂(ii)，优选为下述通式(7)所示的氨基树脂(ii1)。  \n\n[0212] 上述式(7)中， $\\mathrm{R}^{30}$ 表示氢原子、碳原子数为 $1\\sim10$ 的烷基、羟基甲基、或碳原子数为1${\\sim}10$ 的烷氧基甲基， $\\mathrm{R}^{40}$ 表示羟基、氢原子、碳原子数为 $1{\\sim}10$ 的烷基或碳原子数为 $1{\\sim}10$ 的烷氧基， $\\mathrm{\\q_{190}}$ 为 $1{\\sim}90$ 的整数，MC表示下述通式 $(8)\\sim(10)$ 中任一者所示的母核，#2为与下述通式 $(8)\\sim(10)$ 中的#1键合的化学键，#1与#2的数目相同。  \n\n[0213] 下述式(8)中， $\\mathbf{q}_{030}$ 为 $0{\\sim}30$ 的整数， $\\mathbf{q}_{030}$ 彼此可相同或不同， $\\mathrm{R}^{30}$ 及 $\\mathrm{R}^{40}$ 与式(7)中的定义相同。  \n\n[0214] 下述式(9)中， $\\mathbf{\\boldsymbol{q}}_{050}$ 为 $0\\sim50$ 的整数，X表示氧原子或硫原子， $\\mathrm{R}^{30}$ 及 $\\mathrm{R}^{40}$ 与式(7)中的定义相同。  \n\n[0215] 下述式(10)中， $\\mathbf{\\boldsymbol{q}}_{050}$ 为 $0\\sim50$ 的整数。  \n\n[0216] 下述式(8)中，作为 $\\mathrm{R}^{30}$ ，优选为烷氧基甲基及羟甲基，作为 $\\mathrm{R}^{40}$ ，优选为碳原子数为1${\\sim}10$ 的烷氧基，作为q030，优选为 $0{\\sim}10$ 的整数。下述式(9)中，作为 $\\ensuremath{\\mathbb{R}}^{30}$ ，优选为烷氧基甲基及羟甲基，作为 $\\mathrm{R}^{40}$ ，优选为碳原子数为 $1{\\sim}10$ 的烷氧基，作为 $\\mathrm{\\dot{~}q}050$ ，优选为 $1\\sim10$ 的整数。下述式(10)中，作为q050，优选为 $1{\\sim}10$ 的整数。  \n\n[0217]  \n\n![](images/e6e0c78bbbf24744e4a7a2764413ad777d849b747c72126fc3684a353c14f6d4.jpg)  \n\n[0218] 作为上述三聚氰胺树脂，例如，可举出氢化三聚氰胺树脂、甲基化三聚氰胺树脂、乙基化三聚氰胺树脂、正丙基化三聚氰胺树脂、异丙基化三聚氰胺树脂、正丁基化三聚氰胺树脂、异丁基化三聚氰胺树脂、正己基化三聚氰胺树脂、正辛基化三聚氰胺树脂、正癸基化三聚氰胺树脂、正十二烷基化三聚氰胺树脂等。  \n\n[0219] 作为代表性的尿素(脲)树脂，例如，可举出氢化尿素(脲)树脂、甲基化尿素(脲)树脂、乙基化尿素(脲)树脂、正丙基化尿素(脲)树脂、异丙基化尿素(脲)树脂、正丁基化尿素(脲)树脂、异丁基化尿素(脲)树脂、正己基化尿素(脲)树脂、正辛基化尿素(脲)树脂、正癸基化尿素(脲)树脂、正十二烷基化尿素(脲)树脂等。  \n\n[0220] 作为上述苯胺树脂，例如，可举出氢化苯胺树脂、甲基化苯胺树脂、乙基化苯胺树脂、正丙基化苯胺树脂、异丙基化苯胺树脂、正丁基化苯胺树脂、异丁基化苯胺树脂、正己基化苯胺树脂、正辛基化苯胺树脂、正癸基化苯胺树脂、正十二烷基化苯胺树脂等。  \n\n[0221] 本发明中使用的组合物包含的共聚物(i)与氨基树脂(ii)的重量比(i)/(ii)大致为 ${|99/1\\sim1/99}$ 的范围，优选为 $95/5{\\sim}5/95$ 的范围，更优选为 $90/10{\\sim}10/90$ 的范围。  \n\n[0222] 成为本发明的固化物(例如，由该固化物形成的膜)的组合物中，除共聚物(i)与氨基树脂(ii)以外，还可以在不损害本发明的效果的范围内包含其他的成分。  \n\n[0223] 例如，为了使通过本发明得到的固化物更硬、使作为亲水性基团的磺酸基在该固化物的表面进一步集中化(倾斜化)等，可以使上述组合物中含有无机粒子(iii)。作为这样的无机粒子(iii)，例如，可举出银粒子、铜粒子、氧化铜粒子、二氧化硅粒子、中空二氧化硅粒子、氧化铝粒子、氧化铁粒子、氧化钴粒子、二氧化锆粒子、二氧化钛粒子、氧化锑粒子等，其中优选为二氧化硅粒子、中空二氧化硅粒子、二氧化锆粒子、二氧化钛粒子，更优选为二氧化硅粒子、二氧化锆粒子、二氧化钛粒子。这些无机粒子也包含出于使分散性良好的目的而用具有烷基或(甲基)丙烯酰基的有机基团等对表面进行了修饰的无机粒子。进而，作为这些无机粒子(iii)，从确保透明性的观点考虑，倾向于优选直径为纳米尺寸的无机粒子，倾向于更优选上述例示的无机粒子中的粒径为纳米尺寸的无机纳米粒子(二氧化硅纳米粒子、二氧化锆纳米粒子、二氧化钛纳米粒子等)。  \n\n[0224] 在包含共聚物(i)及氨基树脂(ii)的上述组合物中含有无机粒子(iii)的情况下，在该组合物中，相对于共聚物(i)、氨基树脂(ii)及无机粒子(iii)的总重量100重量份，优选包含 $5{\\sim}98$ 重量份共聚物(i)、 $1{\\sim}70$ 重量份氨基树脂(ii)及 $1{\\sim}90$ 重量份无机粒子(iii)，更优选包含 $10{\\sim}70$ 重量份共聚物(i)、 $5{\\sim}40$ 重量份氨基树脂(ii)及 $25\\sim75$ 重量份无机粒子(iii)，进一步优选包含 $20\\sim60$ 重量份共聚物(i)、 $10{\\sim}30$ 重量份氨基树脂(ii)及 $30{\\sim}70$ 重量份无机粒子(iii)。  \n\n[0225] 另外，可以使上述组合物中包含共聚物(i)以外的具有环氧基的化合物、具有羟基的化合物、具有巯基的化合物、具有羧基的化合物、具有氨基的化合物、酸酐等反应性化合物。  \n\n[0226] 这些反应性化合物与共聚物(i)所具有的环氧基之间可发生的反应的一些例子示于下述通式(20)。另外，这些反应性化合物与共聚物(i)所具有的烷氧基甲硅烷基之间可发生的反应的一些例子示于下述通式(21)。  \n\n![](images/7e1526d4260b33472eb29966e994513de06c40f09bf20320183200b821076b69.jpg)  \n\n![](images/0554d69c9eb8196e4b7df3b1e09b2461bd4e9a625ec4ab10e51dda1c9d68fedf.jpg)  \n\n[0229] 当使用共聚物(i)以外的具有环氧基的化合物作为上述反应性化合物时，在上述式(20)的反应(与共聚物(i)的环氧基的反应)中，主要发生反应路线(F)中的反应，在上述式(21)的反应(与共聚物(i)的烷氧基甲硅烷基的反应)中，主要发生反应路线(A’)中的反应，发生固化。  \n\n[0230] 作为共聚物(i)以外的具有环氧基的化合物，优选在分子内具有2个以上环氧基的多元环氧化合物。作为多元环氧化合物，例如，可举出双酚A双(缩水甘油基醚)、双酚F双(缩水甘油基醚)、氢化双酚A双(缩水甘油基醚)、N，N’，N”-三缩水甘油基-异氰脲酸酯、异氰脲酸酯系多缩水甘油基醚(日产化学TEPIC-PAS  B22，TEPIC-PAS  B26)、苯酚线性酚醛树脂型多缩水甘油基醚(phenol  novolac  polyglycidyl  ether)(DIC公司N-730，三菱化学152)、1，1，2，2-四(4-缩水甘油基氧基-苯基)乙烷、N，N，N’，N’-四缩水甘油基-二氨基二苯基甲烷、三羟甲基丙烷-三缩水甘油基醚、新戊二醇二缩水甘油基醚、丁二醇二缩水甘油基醚、聚乙二醇二缩水甘油基醚(三菱化学YDE205)、环己烷二甲酸二缩水甘油基酯、邻苯二甲酸二缩水甘油基酯、3，4-环氧环己基甲基 $-3^{\\ast}$ ’，4’-环氧环己烷羧酸酯、二环癸烷系多缩水甘油基醚(DIC公司EPICLON  HP-7200L，EPICLON  HP-7200H)等。  \n\n[0231] 当使用具有羟基的化合物作为上述反应性化合物时，在上述式(20)的反应(与共聚物(i)的环氧基的反应)中，主要发生反应路线(B)中的反应，在上述式(21)的反应(与共聚物(i)的烷氧基甲硅烷基的反应)中，主要发生反应路线(G)中的反应，发生固化。  \n\n[0232] 作为上述具有羟基的化合物，优选具有2个以上羟基的多元羟基化合物。作为多元羟基化合物，例如，可举出乙二醇、二乙二醇、1，2-丙二醇、甘油、三羟甲基丙烷、季戊四醇、二季戊四醇、苯二甲醇、间苯二酚、双酚A、苯酚甲醛树脂(三井化学)、三聚氰胺与甲醛的缩合反应物、三聚氰胺与甲醛与低级醇的缩合反应物、尿素与甲醛的缩合反应物、尿素与甲醛与低级醇的缩合反应物等。作为具有羟基的化合物，还可使用三聚氰胺与低级醇的缩合反应物、尿素与低级醇的缩合反应物等。它们容易在水分的作用下发生水解而产生羟基，因此，可作为本发明的具有羟基的化合物使用。  \n\n[0233] 当使用具有巯基的化合物作为上述反应性化合物时，在上述式(20)的反应(与共聚物(i)的环氧基的反应)中，主要发生反应路线(C)中的反应，在上述式(21)的反应(与共聚物(i)的烷氧基甲硅烷基的反应)中，主要发生反应路线(H)中的反应，发生固化。  \n\n[0234] 作为上述具有巯基的化合物，优选具有2个以上巯基的多元巯基化合物。作为多元巯基化合物，例如，可举出甘油二巯基乙酸酯等。另外，国际公开第2014/168122号小册子第[0120]段中例示的多元巯基化合物也可用作上述多元巯基化合物。  \n\n[0235] 当使用具有羧基的化合物作为上述反应性化合物时，在上述式(20)的反应(与共聚物(i)的环氧基的反应)中，主要发生反应路线(D)中的反应，在上述式(21)的反应(与共聚物(i)的烷氧基甲硅烷基的反应)中，主要发生反应路线(I)中的反应，发生固化。  \n\n[0236] 作为上述具有羧基的化合物，优选具有2个以上羧基的多元羧基化合物。作为多元羧基化合物，例如，可举出马来酸等。另外，国际公开第2014/168122号小册子第[0122]段中例示的多元羧基化合物也可用作上述多元羧基化合物。  \n\n[0237] 当使用具有氨基的化合物作为上述反应性化合物时，在上述式(20)的反应(与共聚物(i)的环氧基的反应)中，主要发生反应路线(E)中的反应，在上述式(21)的反应(与共聚物(j)的烷氧基甲硅烷基的反应)中，主要发生反应路线(I)中的反应，发生固化。  \n\n[0238] 作为上述具有氨基的化合物，优选具有2个以上氨基的多元氨基化合物。作为多元氨基化合物，例如，可举出苯二胺等。另外，国际公开第2014/168122号小册子第[0124]段中例示的多元氨基化合物也可用作上述多元氨基化合物。  \n\n[0239] 当使用酸酐作为上述反应性化合物时，在上述式(20)的反应(与共聚物(i)的环氧基的反应)中，主要发生反应路线(G)中的反应，在上述式(21)的反应(与共聚物(j)的烷氧基甲硅烷基的反应)中，主要发生反应路线(L)中的反应，发生固化。  \n\n[0240] 作为上述酸酐，例如，可举出马来酸酐、琥珀酸酐等。另外，国际公开第2014/168122号小册子第[0126]段中例示的酸酐也可用作上述酸酐。  \n\n[0241] 为了提高本发明的组合物的固化速度等，可以使用酸催化剂、碱催化剂等。  \n\n[0242] 作为上述酸催化剂，例如，可举出盐酸、硫酸等。另外，国际公开第2014/168122号小册子第[0139]段中例示的酸催化剂也可用作上述酸催化剂，另外可将该段落中例示的碱催化剂用作上述碱催化剂。  \n\n[0243] 对于上述酸催化剂或碱催化剂的添加量而言，相对于共聚物(i)与氨基树脂(ii)的总计，优选为 $0.1{\\sim}20$ 重量 $\\%$ 的范围，更优选为 $0.2{\\sim}10$ 重量 $\\%$ 的范围，更优选为 $0.3{\\sim}5$ 重量 $\\%$ 的范围。  \n\n[0244] 为了改良通过将包含共聚物(i)和氨基树脂(ii)的组合物固化而得到的本发明的固化物(典型的是由该固化物形成的膜)的物性，也可向上述组合物中添加添加剂或改性剂等。作为添加剂或改性剂，例如，可举出紫外线吸收剂、HALS(受阻胺系光稳定剂)、抗氧化剂、自由基捕捉剂、无机粒子以外的填充材料、颜料、颜色修正剂、高折射率化剂、香料、表面活性剂、消泡剂、均化剂、防下垂材料、其他改性剂等。  \n\n[0245] 上述紫外线吸收剂及HALS主要是为了进一步提高耐气候性等而添加的。上述抗氧化剂及自由基捕捉剂主要是为了提高耐热性或防止劣化等而添加的。上述填充材料主要是为了提高磨耗性或赋予韧性等而添加的。作为无机粒子以外的填充材料，例如，可使用国际公开第2014/168122号小册子第[0180]段中例示的填充材料。另外，为了该段落中记载的目的等，可以使用颜料及染料、颜色修正剂、高折射率化剂、香料等，可以使用作为这些添加剂而例示的物质。  \n\n[0246] 为了形成本发明优选使用的磺酸浓度倾斜的固化物(典型的是由该固化物形成的膜，倾斜度 $\\mathrm{Sa/Da}{\\geqslant}1.1)$ )，上述表面活性剂的添加与极性溶剂的选择使用同样有效。  \n\n[0247] 作为优选使用的表面活性剂，例如，可使用国际公开第2014/168122号小册子第[0181]段中例示的表面活性剂。  \n\n[0248] 在这些表面活性剂中，倾向于优选十二烷基硫酸钠、二硬脂基磺基琥珀酸钠、二烷基磺基琥珀酸钠(花王PELEX  TR，PELEX  OT-P)、山梨糖醇酐硬脂酸酯、十二烷基甜菜碱。  \n\n[0249] 上述的消泡剂、均化剂及防下垂材料主要是为了改良涂布性、赋予表面平滑性、以及提高固化物(例如，由该固化物形成的膜)的外观等而添加的。  \n\n[0250] 作为上述消泡剂，例如，可使用国际公开第2014/168122号小册子第[0182]段中例示的消泡剂。  \n\n[0251] 作为上述均化剂，例如，可使用国际公开第2014/168122号小册子第[0183]段中例示的均化剂。  \n\n[0252] 作为上述防下垂材料，例如，可使用国际公开第2014/168122号小册子第[0184]段中例示的防下垂材料。  \n\n[0253] 作为上述其他改性剂，例如，可举出聚丙烯酸酯、聚甲基丙烯酸酯等。  \n\n[0254] 成为本发明的固化物的组合物中，可以包含共聚物(i)以外的水解性硅化合物及其水解产物，例如，烷氧基硅烷、卤化硅烷及羟基硅烷等。但是，当组合物中包含这样的水解性硅化合物及其水解产物时，存在得到的固化物(例如，由该固化物形成的膜)容易吸附大气中的污染物、并且难以脱除的情况，从而变得容易被污染。因此，在以长时间内维持亲水性为课题的情况下，有时优选不积极地添加这些水解性硅化合物及其水解产物。  \n\n[0255] 在通过将上述组合物固化而得到的固化物(典型的是由该固化物形成的膜)中，存在下述情况：来源于共聚物(i)的含磺酸基团的浓度以从该固化物内部朝向固化物的外表面方向逐渐升高的方式集中化(倾斜)。而且，根据该倾斜的程度，可推测固化物表面的亲水性变高。  \n\n[0256] 形成该倾斜结构的主要原理是：“在使预先添加的极性溶剂蒸发时，使具有含磺酸基团的亲水性的共聚物(i)伴随着极性溶剂的蒸发，而在表面上集中化并固化”；及“添加表面活性剂，伴随着表面活性剂向表面的移动，而在表面上集中化并固化”。  \n\n[0257] 当在基材上形成由组合物形成的固化物层(例如，膜)时，在将位于与基材为相反方向的外表面处的磺酸浓度设为Sa、将同基材接触的界面与外表面的中间地点处的磺酸浓度设为Da时，具有含磺酸基团的本发明的共聚物(i)的倾斜度由磺酸的浓度比(Sa/Da)表示。即，磺酸的浓度比(Sa/Da)大表示大量的磺酸集中于固化物层的外表面。这意味着磺酸的浓度比(Sa/Da)越大，固化物层表面的亲水性越高，从将本发明的固化物(典型的是由该固化物形成的膜)作为亲水性材料(典型的是亲水膜)使用的方面来看更有利。此处，关于上述Da，“同基材接触的界面与外表面的中间地点”通常是指朝向同基材接触的界面、距离外表面的深度为膜厚的1/2的地点(本说明书中，也将该地点称为“膜厚1/2的地点”。)。需要说明的是，在Sa及Da的说明中，语句“磺酸”及“磺酸浓度”分别是指 $^{6}{-}\\mathrm{S03M}$ 基”及 $^{6}{-}\\mathrm{S03M}$ 基的浓度”。  \n\n[0258] 通过将本发明的组合物固化而得到的固化物(典型的是由该固化物形成的膜)的倾斜度{磺酸的浓度比(Sa/Da)}通常为 $1.01{\\sim}1000$ 的范围，优选为 $1.1{\\sim}100$ 的范围，进一步优选为 $1.2{\\sim}60$ 的范围。另外，倾斜度的下限值更优选为1.1以上。当倾斜度大于1000时，存在以下倾向：氨基树脂(ii)的羟基甲基(烷氧基甲硅烷基)与高亲水性的共聚物(i)的反应(向氧甲基氨基键的网络的并入)容易变得不完全，韧性、透明性及耐久性(亲水持续性)降低。  \n\n[0259] 在基材上将本发明的组合物固化而形成的由固化物形成的膜的膜厚，不受特别限制，大致为 $0.0001{\\sim}3000{\\upmu\\mathrm{m}}$ 的范围，优选为 $0.01{\\sim}300\\upmu\\mathrm{m}$ 的范围，进一步优选为 $0.1\\sim30\\upmu\\mathrm{m}$ 的范围。  \n\n[0260] 本发明中，磺酸浓度倾斜的上述固化物(典型的是上述膜)显示更高的亲水性。虽然磺酸浓度未倾斜的固化物(例如倾斜度 $\\mathrm{Sa/Da}=1,$ )也显示高亲水性，但比磺酸浓度倾斜的情况低。此外，为了用磺酸浓度未倾斜的固化物(例如倾斜度 $\\mathrm{Sa/Da}=1,$ )得到与磺酸浓度倾斜的情况为同等程度的亲水性，需要更多的亲水性的共聚物(i)。因此，在为磺酸浓度倾斜的固化物(典型的是由该固化物形成的膜)的情况下，具有高亲水性，并且，形成氧甲基氨基键的交联密度高的状态，能够提高硬度、擦伤性、耐磨性及耐久性(亲水维持性)等。  \n\n[0261] 认为当通过将本发明的组合物固化而得到的固化物(典型的是由该固化物形成的膜)中其 $-\\mathrm{S03M}$ 基的浓度存在倾斜时，得到的固化物的亲水性(水接触角等)与硬度的均衡性更优异。  \n\n[0262] 在包含共聚物(i)及可与该共聚物(i)反应的氨基树脂(ii)的组合物中，通常含有共聚物(i)、氨基树脂(ii)、无机粒子、催化剂、及将它们均匀溶解或分散的溶剂。  \n\n[0263] 作为上述溶剂，只要能将上述各成分均匀溶解或分散即可，可以是任何溶剂。需要说明的是，所述溶剂可以单独使用1种，也可混合使用2种以上。  \n\n[0264] 在通过将本发明的组合物固化而得到的固化物(典型的是由该固化物形成的膜)中想要使亲水性的共聚物(i)在厚度方向上倾斜(使磺酸在固化物的表面集中化)时，优选使用1种以上的SP值(溶解度参数σ)高的高极性的溶剂、更具体而言SP值(溶解度参数σ)为至少9.3以上的溶剂。  \n\n[0265] 当想要使用SP值小于9.3的溶剂形成磺酸浓度倾斜的固化物时，优选并用该溶剂和SP值为9.3以上的溶剂，并且该溶剂的沸点比SP值为9.3以上的溶剂低(蒸发速度快)。  \n\n[0266] 需要说明的是，本发明中，溶剂的SP值(溶解度参数σ) $\\mathrm{(cal/cm^{3})^{1/2}}$ 是通过以下(1)$\\sim(5)$ 的计算式计算得到的值。  \n\n[0267] (1)每1mol的蒸发潜热 $\\mathrm{Hb{=}21\\times(273{+}T b)}$ [单位：cal/mol]，Tb：溶剂的沸点 $\\mathrm{(^{\\circ}C)}$ [0268] (2) $25\\mathrm{^\\circC}$ 下的每1mol的蒸发潜热 ${\\mathrm{H25}}={\\mathrm{Hb}}\\times\\left\\{1+0.175\\times\\left({\\mathrm{Tb}}{-}25\\right)/100\\right\\}$ [单位：cal/  \n\nmol]，Tb：溶剂的沸点 $\\mathrm{(^{\\circ}C)}$  \n\n[0269] (3)分子间键能 $_\\mathrm{E=H25-596}$ [单位：cal/mol][0270] (4)每 $\\mathrm{{1m1}(c m^{3})}$ 溶剂的分子间键能 $\\mathtt{E1}{=}\\mathtt{E}\\times\\mathtt{D}/\\mathtt{M w}$ [单位： $\\mathrm{cal/cm^{3}]}$ ，D：密度 $(\\mathrm{g/cm^{3}})$ ，  \n\nMw：溶剂的分子量  \n\n[0271] (5)SP值：溶解度参数 $\\upsigma=\\left(\\mathrm{E1}\\right)^{1/2}$ [单位： $\\left(\\mathrm{cal/cm^{3}}\\right){}^{1/2}]$ [0272] 通过使用这样的SP值(溶解度参数σ) $\\mathrm{(cal/cm^{3})^{1/2}}$ 为9.3以上的溶剂，与来源于共聚物(i)的亲水性的含磺酸基团具有一定的相互作用，因此，当将该混合物涂布于基材并从该混合物中除去溶剂时，具有亲水性的含磺酸基团的共聚物(i)随同溶剂移动至涂布的混合物的与外界气体接触的表面，亲水性的含磺酸基团在该表面上浓缩，形成亲水性的含磺酸基团在本发明中得到的固化物(典型的是膜)的外表面集中的倾斜结构。  \n\n[0273] 另一方面，若溶解度参数 $\\mathrm{{J}\\left(c a l/c m^{3}\\right)^{1/2}}$ 小于9.3，则上述那样的相互作用变弱，因此，不能充分地形成上述的倾斜结构。从更容易形成该倾斜结构的观点考虑，上述溶解度参数σ $\\left(\\mathrm{cal/cm^{3}}\\right){}^{1/2}$ 优选为9.3以上，更优选为10以上，进一步优选为11以上。  \n\n[0274] 另外，本发明主要通过加热来进行固化，因此，通常对应于加热条件(温度、时间、催化剂、固化材料、风量等)，使溶剂蒸发，形成倾斜结构并进行固定化(固化)。因此，从在形成上述倾斜结构的同时进行固化这方面考虑，在上述溶剂中，还存在对应于固化温度以沸点(蒸发速度)为基准进行选择的倾向。具体而言，优选沸点为 $30{\\sim}300^{\\circ}\\mathrm{C}$ 的溶剂，更优选沸点为 $40{\\sim}250^{\\circ}\\mathrm{C}$ 的溶剂，进一步优选沸点为 $50{\\sim}210^{\\circ}\\mathrm{C}$ 的溶剂。需要说明的是，在含有2种以上溶剂的混合溶剂的情况下，这些混合溶剂中含有的沸点最高的溶剂的沸点在上述范围内即可。  \n\n[0275] 作为可用作上述溶剂的溶解度参数σ $\\mathrm{(cal/cm^{3})}$ 1/2为9.3以上并且沸点为 $50\\sim210$ $\\mathrm{{^\\circC}}$ 的溶剂，例如，可举出分类为醇、酮、羧酸、羧酸酯、醚、酰胺、腈及水等的溶剂。关于该溶剂的具体例，例如，可举出国际公开第2014/168122号小册子第[0167]段中记载的溶剂。  \n\n[0276] 这些溶剂中，优选溶解度参数σ最高的 $\\lbrace21.4(\\mathrm{cal/cm^{3}})^{1/2}\\rbrace$ 水及醇。醇中，倾向于优选甲醇、乙醇、1-丙醇、2-甲氧基乙醇(EGM)、2-乙氧基乙醇 $\\cdot2^{-}$ 甲氧基丙醇(PGM)、1-丁醇、1-戊醇、2-甲基 $^{-1-}$ 丁醇、1-戊醇等伯醇。这些醇可以单独使用，也优选与水混合而使用。  \n\n[0277] 溶剂中含有的溶解度参数σ $\\mathrm{(cal/cm^{3}}$ )1/2为9.3以上的上述溶剂可以单独使用1种，或者也可混合使用2种以上。  \n\n[0278] 另外，当上述溶剂为含有2种以上溶剂的混合溶剂时，至少其中1种满足上述溶解度参数的条件即可。其原因在于，混合溶剂中含有的该1种溶剂的溶解度参数满足上述条件时，来源于共聚物(i)的亲水性的含磺酸基团与该1种溶剂具有一定的相互作用，因此，当将该混合物涂布于基材并从该混合物中除去溶剂时，具有亲水性的含磺酸基团的共聚物(i)随同该1种溶剂移动至涂布的混合物的与外界气体接触的表面，这一点并未改变，作为其结果，亲水性的含磺酸基团在表面被浓缩。  \n\n[0279] 当为含有2种以上溶剂的混合溶剂时，存在以下倾向：沸点最高的溶剂容易对倾斜结构的形成造成影响。因此，混合溶剂中含有的沸点最高的溶剂的溶解度参数 $\\mathrm{{J}\\left(c a l/c m^{3}\\right.}$ )1/2优选为9.3以上。  \n\n[0280] 即使是溶解度参数为9.3以上的溶剂彼此的混合溶剂，也最好尽量使用溶解度参数高(高极性)的溶剂。此外，高沸点侧的溶剂的溶解度参数 $\\mathrm{{\\bar{\\Delta}}(c a l/c m^{3})}$ 1/2高于低沸点侧的溶剂时，容易形成磺酸浓度向表面倾斜的固化物，因而优选。  \n\n[0281] 对于含有2种以上溶剂的混合溶剂的混合比而言，溶解度参数最高的溶剂/除此之外的溶剂的重量比优选为 $99.9/0.1{\\sim}1/99\\$ ，更优选为 $99/1\\sim10/90$ ，进一步优选为 $98/2\\sim$  \n\n30/70的范围。  \n\n[0282] 但是，在为水与水以外的溶剂的混合溶剂的情况下，当水以外的溶剂为与水分离的那样的低极性溶剂、或水的添加量多、或混合与水相比蒸发速度快至必要以上的(低沸点)溶剂时，存在如下情况：在溶剂去除工序中，已涂布的本发明的组合物容易成为水滴状，由于流平性降低等而导致无法获得透明且具有平滑表面的固化物(典型的是由该固化物形成的膜)。因此，在选择与水的混合溶剂时，首先，通过使用易于与水亲和的高极性的溶剂而使本发明的组合物形成均匀溶液或均匀分散液是重要的。另外，为了得到透明且具有平滑表面的固化物(典型的是由该固化物形成的膜)，水/水以外的溶剂的重量比较优选为80/20${\\sim}1/99$ ，更优选为 $70/30{\\sim}5/95$ ，进一步优选为 $60/40{\\sim}10/90$ 。  \n\n[0283] 作为选择与水混合的、水以外的溶剂的种类的方法，可举出选择溶解度参数σ$\\mathrm{(cal/cm^{3})^{1/2}}$ 为9.3以上的高极性溶剂的方法，此外还可举出基于溶剂去除工序中的实测温度下的蒸发速度比(相对于水的蒸发速度)R进行选择的方法。具体而言，优选溶剂去除工序中的实测温度下的相对于水的蒸发速度比 $\\mathrm{R}{=}0.1{\\sim}2.0$ 的范围的溶剂，更优选蒸发速度比R$=0.2{\\sim}1.8$ 的范围的溶剂，进一步优选蒸发速度比 $\\mathrm{R}{=}0.3{\\sim}1.5$ 的范围的溶剂。  \n\n[0284] 需要说明的是，本发明中，蒸发速度比R可通过以下的简易计算式 $\\mathrm{(A)\\sim(B)}$ 来计算。  \n\n[0285] (A) $\\c=$ 溶剂去除温度下的饱和蒸气压 $(\\mathrm{\\mmHg{\\ell}})\\times\\sqrt{\\phantom{+}}$ （分子量）  \n\n[0286] (B)相对于水的蒸发速度比R $\\circeq$ 水以外的溶剂的蒸发速度/水的蒸发速度[0287] 例如， $50^{\\circ}\\mathrm{C}$ 下的水的蒸发速度计算为92.6，在 $50^{\\circ}\\mathrm{C}$ 下进行溶剂去除时的代表性的溶剂的蒸发速度比R大致可如下计算。  \n\n[0288] 例如，甲醇 $=4.3$ 、乙醇 $=2.4$ 、IPA( $\\cdot2\\cdot$ 丙醇) $=1.8.1\\-$ 丙醇 $=1.0.1\\-$ 丁醇 $=0.4$ 、EGM(甲氧基乙醇) $=0.4$ 、EGE(乙氧基乙醇) $=0.3$ 。  \n\n[0289] 另一方面，作为本发明的其他方案，可举出以下的固化物(典型的是由该固化物形成的膜)，该固化物(典型的是由该固化物形成的膜)形成于基材上，且具有 $-\\mathrm{S03M}$ 基(M表示氢原子、碱金属、碱土金属、或铵离子。)、和N-CH2-O结构，该固化物的外表面处的 $\\mathrm{S03M}$ 基浓度(Sa)、与同基材接触的界面与上述外表面的中间地点处的 $\\mathrm{S0_{3}M}$ 基浓度(Da)之比 $\\mathrm{(Sa/Da)}$ )为2${\\sim}1000$ 。  \n\n[0290] 本发明的上述固化物(例如，由该固化物形成的膜)的倾斜度{磺酸的浓度比(Sa/Da)}通常为 $1.01{\\sim}1000$ 的范围，优选为 $1.1{\\sim}100$ 的范围，更优选为 $1.2{\\sim}60$ 的范围，在所有情况下均更优选下限值为1.1以上。  \n\n[0291] 另外，本发明的上述固化物具有亲水性，并且具有 $\\mathrm{\\DeltaN-CH_{2}-0}$ 结构，因此硬度、耐磨性、耐气候性等也优异。  \n\n[0292] 通过使如上所述地得到的包含共聚物(i)及氨基树脂(ii)的组合物固化，可形成本发明的固化物，例如由该固化物形成的膜。需要说明的是，本发明中，所谓固化，有时是指例如从上述组合物中除去溶剂时，典型地，在溶剂中的溶解性降低或丧失。当本发明中使用的包含共聚物(i)及氨基树脂(ii)的组合物被固化时，典型的是，在固化物中形成以氧甲基氨基键为主的网络(交联结构)，该氧甲基氨基键是通过使该组合物中含有的基团(典型的是环氧基、烷氧基甲硅烷基、羟基甲基)进行反应而形成的。  \n\n[0293] 这样的固化例如优选通过加热来进行。加热温度大致为 $30{\\sim}300^{\\circ}\\mathrm{C}$ 的范围，优选为  \n\n$40{\\sim}200^{\\circ}\\mathrm{C}$ 的范围，更优选为 $50{\\sim}180^{\\circ}\\mathrm{C}$ 的范围。加热时间通常为0.02小时 ${\\sim}200$ 小时的范围，优选为0.1小时 ${\\sim}8.0$ 小时，更优选为0.3小时 ${\\sim}4.0$ 小时。  \n\n[0294] 另外，固化也可通过加热以外的方法进行。例如，可举出向包含共聚物(i)及氨基树脂(ii)的组合物照射作为一种放射线的微波(代表例：频率2.45GHz，波长 $=12.2\\mathrm{cm})$ )而使其固化的方法。  \n\n[0295] 例如，向上述组合物中，添加已知的多官能(甲基)丙烯酸酯、已知的多官能环氧化合物、或已知的多官能乙烯基化合物等，进一步根据需要添加UV自由基聚合引发剂、或UV阳离子聚合引发剂等，照射作为一种放射线的紫外线(UV)，由此可进行固化。  \n\n[0296] 需要说明的是，在进行放射线照射的情况下，从在固化物中可靠地形成以氧甲基氨基键为主的网络的观点等考虑，将加热和放射线照射组合而进行固化是一种优选方式。  \n\n[0297] 在使用放射线进行固化的情况下，作为放射线，可使用波长区域为 $0.0001{\\sim}800\\mathrm{nm}$ 范围的能量线。上述放射线被分类为α射线、β射线、 $\\gamma$ 射线、X射线、电子束、紫外线、可见光、微波等，可根据上述共聚物(i)、氨基树脂(ii)的组成等适当选择使用。在这些放射线中，优选紫外线，紫外线的输出峰优选为 $200{\\sim}450\\mathrm{nm}$ 的范围，更优选为 $210{\\sim}445\\mathrm{nm}$ 的范围，进一步优选为 $220{\\sim}430\\mathrm{nm}$ 的范围，特别优选为 $230{\\sim}400\\mathrm{nm}$ 的范围。在使用上述输出峰的范围的紫外线的情况下，固化时的变黄及热变形等不良情况少，并且，在添加紫外线吸收剂的情况下，也可在较短时间内完成固化。另外，作为紫外线灯的种类，与通常的有电极UV(紫外线)灯相比，优选红外线少且照度高的无电极UV(紫外线)灯。此外，在向包含共聚物(i)及氨基树脂(ii)的上述组合物中添加紫外线吸收剂或HALS的情况下，倾向于优选使用在输出特性方面在 $240{\\sim}270\\mathrm{nm}$ 具有峰强度的紫外线灯。  \n\n[0298] 将包含共聚物(i)及氨基树脂(ii)的组合物固化时的气氛可以是氮等非活性气体气氛，优选为大气气氛。另外，关于气氛的湿度，由于在高湿度下固化物的表面容易变得不均匀，所以优选尽可能低的湿度，优选大致为 $20\\sim70\\%$ RH的范围，更优选为 $30\\sim60\\%$ RH的范围，进一步优选为 $40\\sim60\\%$ RH的范围。  \n\n[0299] 作为固化物的一例的膜，是厚度大于 $100\\mathrm{nm}\\left(0.\\mathrm{1\\upmum}\\right)$ 的膜(Z1)。具有这样的厚度的膜的耐磨性及耐久性优异，因此，可优选用作建筑物及运输机器(车辆、船舶、航空器)的内外装饰被膜、家电及电气化产品的内外装饰被膜、以及它们中使用的备品·部件等的被膜。尤其是，对于要求耐气候性的户外涂装用途等有用。  \n\n[0300] 若以厚度大于 $100\\mathrm{nm}\\left(0.1\\upmu\\mathrm{m}\\right)$ 的厚膜的形式被覆作为上述固化物的一例的膜，则能够不怎么受到基材的影响而形成高硬度的表面(通常，被覆于柔软基材上的膜容易受到基材的影响而受损伤)。利用该高硬度的表面被覆膜，不仅不易受损伤，而且即使假设由于预想以上的应力等而使表面受到一定程度地刨削，在大部分情况下膜都会残留，因此存在容易维持膜的性能(即，耐久性提高。)的倾向。  \n\n[0301] 上述膜(Z1)例如可通过将包含共聚物(i)及氨基树脂(ii)的上述组合物涂布于后述的基材并将其固化而制作。  \n\n[0302] 作为将上述组合物涂布于基材的方法，例如，可举出刷毛涂布法、喷涂法、线棒法、棒涂法、刮刀法、辊涂法、旋涂法、浸涂法、其他已知的涂覆方法。  \n\n[0303] 对于涂布量而言，以使膜(Z1)的厚度为所期望的范围的方式进行设定即可。  \n\n[0304] 在不需要硬度的情况下，上述膜(Z1)的厚度大于0.001μm(1nm)且为 $0.1\\upmu\\mathrm{m}\\left(100\\mathrm{nm}\\right)$  \n\n以下，在需要硬度的情况下，大致大于 $0.1\\upmu\\mathrm{m}\\left(100\\mathrm{nm}\\right)$ 且为 $500\\upmu\\mathrm{m}$ 以下，优选大于0.1μm且为$100\\upmu\\mathrm{m}$ 以下，更优选为 $1\\sim50\\upmu\\mathrm{m}$ 。  \n\n[0305] 例如，若为户外的涂装用途，则存在膜(Z1)的厚度变得较厚的倾向，大致为大于$0.1\\upmu\\mathrm{m}\\left(100\\mathrm{nm}\\right)$ 且为 $500\\upmu\\mathrm{m}$ 以下的范围，优选为1μm以上且为 $200\\upmu\\mathrm{m}$ 以下的范围，进一步优选为$3\\upmu\\mathrm{m}$ 以上且为 $100\\upmu\\mathrm{m}$ 以下的范围。  \n\n[0306] 另外，通过如上所述地将包含共聚物(i)及氨基树脂(ii)的上述组合物涂布于基材等上并进行固化，从而制作具有至少一层由膜(Z1)形成的层(Z1)、和基材的层叠体，也能够以此状态直接使用所得的层叠体。  \n\n[0307] 作为形成上述基材的材料，例如，可举出PMMA、聚碳酸酯(PC)、PET、ABS、三乙酰纤维素(TAC)、聚氯乙烯(polyvinyl  chloride)、聚乙烯(PE)、聚丙烯(PP)、聚乳酸(PLA)、聚(硫)氨酯树脂、聚(硫)脲树脂、及(硫代)环氧树脂等有机材料；玻璃、铁、不锈钢、铝、镍、锌、金、银、铜、金属氧化物、陶瓷、水泥、石板、大理石或花岗岩、灰浆等无机材料；将玻璃纤维、碳酸钙等无机材料与不饱和聚酯树脂等有机材料进行复合化而成的SMC(片状成型料，sheet  molding  compound)等复合材料等。  \n\n[0308] 由这样的有机材料、无机材料、复合材料分别形成的有机基材、无机基材、复合基材也可直接使用，还可进行各种表面处理后使用。通过进行表面处理，例如，可提高上述基材与由膜(Z)形成的层的密合性。作为这样的进行了表面处理的基材，例如，可举出对基材表面进行了镀金属的基材、利用磷酸锌水溶液等化学药品对基材表面进行了化学处理的基材、进行了电晕处理的基材、进行了等离子体处理的基材、进行了辉光放电处理的基材、进行了火焰处理的基材、进行了ITRO处理的基材、进行了底漆处理的基材、进行了底涂处理的基材、进行了锚涂处理的基材等。  \n\n[0309] 作为上述底漆处理、底涂处理、或锚涂处理中使用的涂覆剂，例如，可使用将聚酯系树脂、聚酰胺系树脂、聚氨酯系树脂、环氧树脂、酚醛树脂、(甲基)丙烯酸系树脂、聚乙酸乙烯酯系树脂、聚乙烯及聚丙烯等聚烯烃系树脂或其共聚物或者改性树脂、纤维素系树脂等树脂作为漆料(vehicle)的主成分的涂覆剂。上述涂覆剂可以是溶剂型涂覆剂、水性型涂覆剂中的任一种。  \n\n[0310] 这些涂覆剂中，优选硅烷偶联剂系涂覆剂、硅烷偶联剂与填充材料的混合系涂覆剂、改性聚烯烃系涂覆剂、乙基乙烯醇系涂覆剂、聚乙烯亚胺系涂覆剂、聚丁二烯系涂覆剂、聚氨酯系涂覆剂；聚酯系聚氨酯乳液涂覆剂、聚氯乙烯乳液涂覆剂、聚氨酯丙烯酸乳液涂覆剂(urethane  acrylic  emulsion  coating  agent)、硅丙烯酸乳液涂覆剂、乙酸乙烯酯丙烯酸乳液涂覆剂、丙烯酸乳液涂覆剂；  \n\n[0311] 苯乙烯-丁二烯共聚物胶乳涂覆剂、丙烯腈-丁二烯共聚物胶乳涂覆剂、甲基丙烯 酸甲酯-丁二烯共聚物胶乳涂覆剂、氯丁二烯胶乳涂覆剂、聚丁二烯胶乳的橡胶系胶乳涂覆 剂、聚丙烯酸酯胶乳涂覆剂、聚偏二氯乙烯胶乳涂覆剂、聚丁二烯胶乳涂覆剂、或者由这些 胶乳涂覆剂中含有的树脂的羧酸改性物胶乳或分散液形成的涂覆剂。  \n\n[0312] 这些涂覆剂例如可利用凹版印刷涂布法、逆转辊涂布法、刮刀涂布法、吻式涂布法等进行涂布，在基材上的涂布量在干燥状态下通常为 $0.005\\mathrm{g}/\\mathrm{m}^{2}{\\sim}5\\mathrm{g}/\\mathrm{m}^{2}$ 。  \n\n[0313] 这些涂覆剂中，更优选硅烷偶联剂系涂覆剂、硅烷偶联剂与上述填充材料的混合系涂覆剂、及以商品名称“TakelacTM”及“TakenateTM”(均为三井化学制)为代表的聚氨酯系  \n\n涂覆剂。  \n\n[0314] 上述硅烷偶联剂系涂覆剂、及硅烷偶联剂与上述填充材料的混合系涂覆剂具有以下特征：该涂覆剂中含有硅烷偶联剂。作为涂覆剂中含有的代表性的硅烷偶联剂，例如，可举出乙烯基三氯硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、2-(3，4-环氧环己基)乙基三甲氧基硅烷、3-缩水甘油基氧基丙基三甲氧基硅烷、3-缩水甘油基氧基丙基三乙氧基硅烷、3-缩水甘油基氧基丙基-甲基-二甲氧基硅烷、 $4^{-}$ 苯乙烯基三甲氧基硅烷、(甲基)丙烯酰氧基丙基-甲基-二甲氧基硅烷、(甲基)丙烯酰氧基丙基-三甲氧基硅烷、(甲基)丙烯酰氧基丙基-三乙氧基硅烷、 $.\\mathrm{N-}$ (2-氨基乙基) $-3-$ 氨基丙基-三甲氧基硅烷、 $\\mathrm{N^{-}}$ (2-氨基乙基) $-3-$ 氨基丙基-甲基-二甲氧基硅烷、N-(2-氨基乙基)-3-氨基丙基-三乙氧基硅烷、3-氨基丙基-三甲氧基硅烷、3-氨基丙基-三乙氧基硅烷、 $\\l_{3-}$ 三乙氧基甲硅烷基-N-(1，3-亚丁基)丙基胺、N-苯基-3-氨基丙基-三甲氧基硅烷、3-脲基丙基-三乙氧基硅烷、3-氯丙基三甲氧基硅烷、3-巯基丙基-三甲氧基硅烷、3-巯基丙基-甲基-二甲氧基硅烷、双(三乙氧基甲硅烷基丙基)四硫醚、双(三甲氧基甲硅烷基丙基)胺、双(三乙氧基甲硅烷基丙基)胺、N，N’-双(三甲氧基甲硅烷基丙基)乙二胺、N，N’-双(三乙氧基甲硅烷基丙基)乙二胺、N，N’，N”-三(三甲氧基甲硅烷基丙基)-异氰脲酸酯、3-异氰酸酯基丙基三甲氧基硅烷、3-异氰酸酯基丙基三乙氧基硅烷等。  \n\n[0315] 上述硅烷偶联剂中，较优选具有环氧基、巯基、或氨基的硅烷偶联剂，更优选具有氨基的硅烷偶联剂，进一步地，最优选双(三甲氧基甲硅烷基丙基)胺、双(三乙氧基甲硅烷基丙基)胺、N，N’-双(三甲氧基甲硅烷基丙基)乙二胺、N，N’-双(三乙氧基甲硅烷基丙基)乙二胺。  \n\n[0316] 上述聚氨酯系的涂覆剂是指，在该涂覆剂中含有的树脂的主链或者侧链具有氨基甲酸酯键的涂覆剂。聚氨酯系涂覆剂是含有聚氨酯的涂覆剂，所述聚氨酯是使例如聚酯多元醇、聚醚多元醇或丙烯酸多元醇等多元醇与异氰酸酯化合物反应而得到的。  \n\n[0317] 这些聚氨酯系涂覆剂中，将缩合系聚酯多元醇、内酯系聚酯多元醇等聚酯多元醇与甲苯二异氰酸酯、1，6-己二异氰酸酯、异佛尔酮二异氰酸酯、降冰片烷二异氰酸甲酯(norbornane  diisocyanatomethyl)、苯二甲撑二异氰酸酯等异氰酸酯化合物混合而得到的聚氨酯系涂覆剂的密合性优异，因而优选。  \n\n[0318] 对于将多元醇化合物和异氰酸酯化合物混合的方法没有特别限制。而且对配合比也没有特别限制，但在异氰酸酯化合物过少时，有时引起固化不良，因此，以当量换算，多元醇化合物的OH基和异氰酸酯化合物的NCO基优选为 $2/1{\\sim}1/40$ 的范围。此外，也可向上述的多元醇化合物和上述的异氰酸酯化合物中添加已知的硅烷偶联剂。  \n\n[0319] 上述底漆处理、底涂处理、或锚涂处理中使用的涂覆剂的膜厚可根据用途等任意确定。例如，在涂覆于常常要求防反射性的光学系基材的情况下，大致为 $0.0001\\upmu\\mathrm{m}\\left(0.1\\mathrm{nm}\\right)$ ${\\sim}0.1\\upmu\\mathrm{m}\\left(100\\mathrm{nm}\\right)$ 的范围，更优选为 $0.001\\mathrm{{km}(1n m)}\\sim0.05\\mathrm{{\\mum}(50n m)}$ 的范围。例如，在涂覆于光学系基材以外的基材的情况下，大致为 $0.1{\\sim}400\\upmu\\mathrm{m}$ 的范围，更优选为 $0.5\\sim200\\upmu\\mathrm{m}$ 的范围，进一步优选为 $1\\sim100\\upmu\\mathrm{m}$ 的范围。  \n\n[0320] 另外，上述表面处理可以出于除了提高密合性之外的目的、例如出于赋予防反射性的目的而进行，作为进行了这样的表面处理的基材，可举出在表面形成有微细的凹凸的抛光基材(grazed  substrate)等。此外，也可使用在这些基材的表面上涂布涂料而形成了  \n\n涂膜的涂装基材。  \n\n[0321] 上述基材可以以1层单独作为基材使用，也可以以将选自有机基材、无机基材、及复合基材中的多种基材层叠而成的层压基材的形式进行使用。  \n\n[0322] 另外，作为以透镜、眼镜、照相机、显示装置(显示器)、投影装置等为代表的光学物品及光学装置中使用的光学系基材，例如也可使用由上述有机材料、无机材料、混合材料中具有透明性的材料形成的透明性基材。  \n\n[0323] 在具有上述基材和层(Z1)的层叠体中，可以设置各种功能层。  \n\n[0324] 作为这样的功能层，例如，可举出硬涂层、防反射(AR)层等。  \n\n[0325] 作为上述硬涂层，例如，可举出由丙烯酸系材料形成的层、由二氧化硅材料形成的层等。  \n\n[0326] 作为上述防反射层，可举出由低折射率材料形成的层、交替层叠由低折射率材料形成的层和由高折射率材料形成的层而成的多层型防反射层等。  \n\n[0327] 上述功能层可以设置于基材与层(Z1)的外侧，也可设置于基材与层(Z1)之间，例如基材上。例如，对于硬涂层、防反射层而言，设置于基材层与层(Z1)之间，例如设置于基材上，这是一种优选方式。  \n\n[0328] 另外，本发明的层叠体可以具有多个上述功能层。  \n\n[0329] 通常，当以光学用途使用该层叠体时，需要高透明性的情况很多。在这种情况下，倾向于优选尽可能地使层叠体的各层变薄。上述功能层可利用已知的方法设置于层叠体中。  \n\n[0330] 另外，在制作上述层叠体时，以与由本发明的膜(Z1)形成的层(Z1)接触的层为以SiO2为主成分的层的方式进行层叠是一种优选方式。通过像这样进行层叠，存在可得到层(Z1)的粘接性优异的层叠体的倾向。  \n\n[0331] 尤其是在具有光学系基材和层(Z1)的层叠体的情况下，对于防雾性的要求高，因此，对于共聚物(i)的式(1)所示的结构单元a、式(2)所示的结构单元b、及式(3)所示的结构单元c的比率而言，式(1)所示的结构单元a多时，可得到高亲水性，因而优选。具体而言，优选的是，式(1)所示的结构单元a为 $99.0{\\sim}60.0\\$ 的范围，式(2)所示的结构单元b为 $0.5{\\sim}20.0$ 的范围，式(3)所示的结构单元c为 $0.5{\\sim}20.0$ 的范围；更优选的是，a为 $98.0{\\sim}70.0\\$ 的范围，b为 $1.0{\\sim}15.0\\$ 的范围，c为 $1.0{\\sim}15.0\\$ 的范围。  \n\n[0332] 另外，对于共聚物(i)的重量与氨基树脂(ii)的换算重量之比(i)/(ii)而言，基于与上述相同的理由，倾向于优选共聚物(i)的比率高的情况。以重量比计，优选 $99/1{\\sim}40/60$ 的范围，更优选 $95/5{\\sim}60/40$ 的范围。  \n\n[0333] 对于上述层叠体而言，例如上述膜(Z1)为防雾被膜、防污被膜、或防静电被膜时，例如可得到用防雾被膜、防污被膜或防静电被膜被覆基材而成的层叠体。  \n\n[0334] 例如，在基材为膜的情况下，在未形成本发明的膜的面上，也可设置后述的粘合层，此外，也可在粘合层的表面上设置剥离膜。若在基材膜的另一面上预先层叠粘合层，则可将具有本发明的膜的层叠膜作为防雾膜及防污膜，容易地贴合于玻璃、浴室等的镜子、显示器、电视机等的显示材料表面、招牌、广告、指示牌等指示牌、铁道、道路等的标识、建筑物的外壁、窗玻璃等。  \n\n[0335] 对于层叠体等的粘合层中使用的粘合剂没有特别限制，可使用已知的粘合剂。作为粘合剂，例如，可举出丙烯酸系粘合剂、橡胶系粘合剂、乙烯基醚聚合物系粘合剂、及聚硅氧烷粘合剂等。粘合层的厚度通常为 $2\\sim50\\upmu\\mathrm{m}$ 的范围，优选为 $5\\sim30\\upmu\\mathrm{m}$ 的范围。  \n\n[0336] 另外，对于本发明的膜(Z1)及层叠有该膜的层叠体而言，可以用被覆材料预先被覆膜的与外界气体接触的表面。对于被被覆材料被覆的膜及具有该膜的层叠体而言，可防止在进行输送、保存、陈列等时，膜受损伤或被污染。  \n\n[0337] 对于上述被覆材料，例如，当如上所述地涂布包含共聚物(i)及氨基树脂(ii)的组合物并进行加热或照射红外线时，为了保护表面免受大气中的垃圾及污染物的影响，也可以保持将上述被覆材料密合于涂布物的状态加热或照射红外线而使其固化，以在基材等上层叠本发明的膜和被覆材料的状态制成产品。通过如上所述地进行，可得到防止了对膜的损伤、污染等的层叠体。  \n\n[0338] 作为优选用作上述被覆材料(典型的是膜)的材料，例如，可举出聚乙烯醇(PVA)、乙烯·乙烯醇共聚物等乙烯醇系聚合物、聚丙烯酰胺、聚异丙基丙烯酰胺、聚丙烯腈、聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)、聚对苯二甲酸乙二醇酯(PET)、聚苯乙烯(PS)、双轴拉伸聚丙烯(OPP)等。  \n\n[0339] 对于本发明的层叠体而言，通过对基材的形状进行设计等，可制成各种形态的层叠体。通过本发明得到的膜(Z1)及层叠体可以以膜、片材、带等形态使用。需要说明的是，上述膜(Z1)也可作为底漆层使用。  \n\n[0340] 此外，对于包含共聚物(i)及氨基树脂(ii)的组合物，通过使其在各种形状的铸模内固化，也可以作为具有各种形状的固化物例如膜、成型体等而得到。  \n\n[0341] 通过本发明得到的膜(Z1)的亲水性、耐久性、耐磨性、及耐气候性优异，具有高防雾性、防污性、防静电性、速干性(水的蒸发)。  \n\n[0342] 通过本发明得到的膜(Z1)的水接触角通常为 $30^{\\circ}$ °以下，优选为 $20^{\\circ}$ °以下，更优选为${10}^{\\circ}$ °以下。水接触角为上述上限值以下的膜的亲水性高，容易与水亲和(浸润)，是优异的亲水性材料。  \n\n[0343] 对于通过将包含共聚物(i)及氨基树脂(ii)的组合物固化而得到的本发明的固化物、例如由该固化物形成的膜(Z1)而言，优选地，期望为以下状态：浸渍于 $25\\mathrm{^\\circC}$ 的水中进行10分钟超声波处理前后的水接触角的变化通常为 $20^{\\circ}$ °以内，优选为 ${10}^{\\circ}$ °以内，进一步优选为$5^{\\circ}$ °以内。如果是该状态，则对于为水溶性或非常容易与水亲和的本发明中使用的包含共聚物(i)及氨基树脂(ii)的组合物而言，该组合物中含有的基团的反应充分进行而网络化或固定化，由此成为不容易在水中溶解的状态(经充分固化的状态)。这样的特性的固化物可如上所述地通过加热等将组合物固化来制作。  \n\n[0344] 因此，通过本发明得到的膜(Z1)例如对于防雾材料、防雾被膜(以下也称为防雾涂层)、防污材料、防污被膜或自清洁涂层、防静电材料、速干性材料或速干性涂层、及防静电被膜或防灰尘附着涂层等是有用的。  \n\n[0345] 例如，在将本发明的膜作为防雾涂层使用时，水滴可在膜表面上铺展而形成水膜，因而防雾效果优异，另外，在作为自清洁涂层使用时，水进入到污垢与涂覆面之间，可使污垢浮起而将其除去，因而防污效果优异。另外，本发明的膜的防静电性优异，对于防静电材料、及防静电被膜或防灰尘附着涂层等也是有用的。  \n\n[0346] 通过本发明得到的层叠体的亲水性及耐久性也优异，作为防雾材料、防污材料、防静电材料等是有用的。例如，通过将上述本发明的膜层叠在由透明树脂、玻璃等透明材料形成的基材上而得到的层叠体可作为透明性、亲水性、防雾性、防污性、以及防静电性、速干性、防结露性、耐气候性、耐磨性优异的层叠体使用。  \n\n[0347] 因此，通过将本发明的组合物固化而得到的固化物、由该固化物形成的膜及层叠体可用于多种用途：主体、机轮、外部装饰品、及内部装饰品等以汽车、船舶、航空器为代表的运输设备用物品；外壁品、内壁品、地板、家具、浴室用物品、洗脸化妆室用物品、水槽、换气扇、炉灶周边构件等厨房用物品、厕所用物品、配管用物品等建筑用物品及住宅用物品；设置于高速公路等的隔音板等建设用物品；衣服及布及纤维等衣料用构件；窗、镜、光学膜、光盘、隐形眼镜、护目镜、反射膜、及反射板、眼镜、太阳镜、照相机、透镜、防反射膜、显示装置(触控面板、扁平面板、电子纸等显示装置)、投影装置、及遮蔽物等光学物品或光学装置；假牙等牙科材料；灯用物品及光照用物品等照明用物品；冷却及热交换用的叶片等产业用物品；电气化产品用物品、配线用物品等电气·电子产品用物品；喷墨记录版、印刷·印字用底漆层等印刷用物品；化妆品容器等日用品用物品等。  \n\n[0348] 实施例  \n[0349] 以下，通过实施例等进一步详细地说明本发明，但本发明并不仅限于这些实施例。[0350] 本发明中，如下所述地进行共聚物(i)的结构评价。  \n[0351] <共聚物的组成比>  \n[0352] 通过 $^{13}\\mathrm{C-NMR}$ 分析具有含磺酸基团的单元(1)、具有环氧基的单元(2)、及具有三烷氧基甲硅烷基的单元(3)的单元比 $\\left(1\\right)/\\left(2\\right)/\\left(3\\right)$ 。将测定条件记载如下。  \n[0353] (测定条件)  \n[0354] \\*装置：Bruker  BioSpin制AVANCEIII  cryo $-500$ 型核磁共振装置  \n[0355] \\*测定核： $^{13}\\mathrm{C}\\left(125\\mathrm{MHz}\\right)$   \n[0356] \\*测定模式：单脉冲质子宽带去耦  \n[0357] \\*脉冲宽度： $45^{\\circ}\\left(5.0\\right.$ 微秒)  \n[0358] \\*点数：64K  \n[0359] \\*测定范围： $-25{\\sim}225\\mathrm{ppm}$   \n[0360] \\*累积次数：1000次  \n[0361] \\*测定溶剂： $\\mathrm{D}_{2}0$   \n[0362] \\*测定温度：室温  \n[0363] \\*试样浓度： $40\\mathrm{{mg}/0.6m l\\mathrm{{-}\\mathrm{{D}_{2}0}}}$   \n[0364] (单元比 $\\left(1\\right)/\\left(2\\right)/\\left(3\\right)$ 的解析)  \n[0365] 通过下述式(200)的f碳的峰 $(57\\sim59\\mathrm{ppm}$ 附近)、下述式(300)的k碳的峰 $(51\\sim$ $52\\mathrm{ppm}$ 附近)、及下述式(400)的t碳的峰 $(4\\mathrm{\\sim}6\\mathrm{ppm}$ 附近)的积分强度比算出。  \n[0366] 即，单元比 $\\left(1\\right)/\\left(2\\right)/\\left(3\\right)=\\mathrm{f}$ 碳峰的积分强度/k碳峰的积分强度/t碳峰的积分强度。[0368] <重均分子量(Mw)、分子量分布(Mw/Mn)>  \n[0369] 通过GPC分析Mw(重均分子量)、及重均分子量(Mw)与数均分子量(Mn)之比即分子量分布Mw/Mn。将测定条件记载如下。  \n[0370] (测定条件)  \n[0371] \\*装置：日本分光(株)GPC-900  \n[0372] \\*柱：昭和电工(株)Shodex  Asahipac“GF-7M  HQ”，Φ7 .5mm×300mm  \n[0373] \\*测定温度： $40^{\\circ}\\mathrm{C}$   \n[0374] \\*洗脱液：水/甲醇 $\\mathrm{\\langleNaHP0_{4}/N a H P0_{4}\\bullet2H_{2}0{=}850.0/150.0/2.7/7.3}$ (重量比)[0375] \\*流速：0.5ml/min.  \n[0376] \\*分子量校正：利用分子量已知的聚甲基丙烯酸甲酯进行。  \n[0377] 需要说明的是，本发明中，如下所述地进行涂覆膜的物性评价。  \n[0378] <外观>  \n[0379] 通过目视确认得到的涂覆膜的透明性。  \n[0380] <水接触角的测定>  \n[0381] 使用协和界面科学公司制的水接触角测定装置CA-V型，针对1个样品测定3处，将这些值的平均值作为水接触角的值。  \n[0382] <雾度的测定>  \n[0383] 使用日本电色工业公司制的雾度计NDH2000，针对1个样品测定4处，将这些值的平均值作为雾度的值。  \n[0384] $\\mathrm{\\Omega^{\\angle120^{\\circ}C}}$ 加热污垢附着试验>  \n[0385] 于 $120^{\\circ}\\mathrm{C}$ 热风干燥机中保持12小时，冷却至室温后，在流水下用Bemcot(旭化成)擦洗表面，用气枪进行干燥，作为评价用样品。评价通过测定试验前后的水接触角而进行，水接触角的上升幅度(差距(gap))越大，判定污染越严重。  \n[0386] <铅笔硬度>  \n[0387] 按照JIS  K5600-5-4：刮擦硬度(铅笔法)进行试验。  \n[0388] <防雾性的评价>  \n[0389] 将未由于呼气而起雾的情况记为 $\\bigcirc$ ，将略微起雾的情况记为△，将起雾的情况记为 $\\times$ 。  \n[0390] <防污性的评价>  \n[0391] 使用ZEBRA(株)制的油性记号笔“Mckee极细”(黑，型号MO-120-MC-BK)做标记，在  \n\n![](images/5e6f78f35223f94eb4c1ab857af6b7398bbcc71a63a8fe8c6486254c4c7b048f.jpg)  \n\n其上滴下水滴并放置30秒钟，用纸巾拭去。将标记被拭去的情况记为 $\\bigcirc$ ，将略微残留的情况记为△，将未被拭去而残留的情况记为 $\\times$ 。  \n\n[0392] <密合性试验>  \n[0393] 按照JIS  K5600-5-6(附着性-交叉切割法(adhesion-cross-cut  method))进行试验。需要说明的是，对于评价而言，将25格换算为100格，用未剥离的(密合的)格数表示。[0394] <Taber磨耗试验(JIS  K  7204)>  \n[0395] 针对试验前的样品，利用上述方法进行雾度的测定。之后，按照JIS  K  7204，利用以下的条件进行Taber磨耗试验，针对Taber磨耗试验后的样品也进行雾度的测定。雾度的上升幅度越大，判定耐磨性越低(越容易磨耗)。  \n[0396] (Taber磨耗试验条件)  \n[0397] 测定仪器：旋转式磨耗试验机，(株)东洋精机制作所  \n[0398] 磨耗轮：C180  OXF  \n[0399] 负荷： $500\\mathrm{g}\\left(250\\mathrm{g}+250\\mathrm{g}\\right)\\times2$   \n[0400] <倾斜度的测定>  \n[0401] 如图2所示的试样制备那样，斜着切割在基材10上形成涂覆层20而成的样品，使用飞行时间型2次离子质谱仪(TOF-SIMS)，测定外表面处的磺酸浓度(Sa)、和同基材10接触的界面与上述外表面的中间地点处的磺酸浓度(Da)，从该值求出由同外界气体接触的膜的外表面、与膜的内表面与外表面的中间地点的磺酸浓度比表示的倾斜度(Sa/Da)。此处，在本发明的层叠体中，涂覆层20为本发明的膜。  \n[0402] (分析装置和测定条件)  \n[0403] TOF-SIMS：ION·TOF公司制TOF-SIMS  5  \n[0404] 1次离子： $\\mathrm{{Bi_{3}}^{2+}}$ (加速电压 $25\\mathrm{{kV})}$   \n[0405] 测定面积： $300{\\sim}340\\upmu\\mathrm{m}^{2}$ ；测定中使用电荷补偿用电子枪  \n[0406] 试样制备等  \n[0407] 如图2所示那样，沿着切削方向30对在基材10的表面上设置有涂覆层20的样品进行精密倾斜切削，然后切出 $10\\mathrm{mm}\\times10\\mathrm{mm}$ 左右的大小，将筛网(mesh)抵接于测定面，固定于样品架，在与外界气体接触的涂覆层表面40及作为膜内部的涂覆层内部50(膜厚1/2的地点、与基材10接触的涂覆层的内表面)，使用飞行时间型2次离子质谱仪(TOF-SIMS)测定磺酸浓度。  \n[0408] 评价  \n[0409] 利用以下的计算式进行评价。需要说明的是，各测定点的离子浓度使用相对强度(相对于全部检测离子)。  \n[0410] 倾斜度Sa/Da(磺酸浓度比，倾斜度) $\\c=$ 涂覆层表面40处的磺酸浓度/涂覆层20的膜厚1/2的地点处的磺酸浓度  \n[0411] <膜厚的测定>  \n[0412] (测定装置及条件)  \n[0413] 装置：场发射透射电子显微镜(FE-TEM)：JEM-2200FS(日本电子制)  \n[0414] 加速电压： $200\\mathrm{kV}$   \n[0415] FIB(Focused  Ion  Beam  System，聚焦离子束系统)加工装置：SMI2050(Seiko  \n\nInstruments公司制)  \n\n[0416] 试样制备等  \n\n[0417] 在将试样的凸面中央部切出后，在试样最表面进行Pt涂覆及碳蒸镀。通过FIB加工将其制成薄膜，制成测定样品。用场发射透射电子显微镜(FE-TEM)观察测定样品，测定膜厚。  \n\n[0418] [合成例1]<共聚物90/5/5CH140212的制造>[0419] 将在减压下进行了脱气的483 .3g甲醇装入反应烧瓶中，一边搅拌一边缓缓添加$28.0\\mathrm{g}\\left(0.424\\right.$ 摩尔)纯度 $85w t\\%$ 的KOH小片并使其完全溶解。接下来，分批装入 $89.9\\mathrm{g}\\left(0.424\\right.$ 摩尔)丙烯酰胺基-叔丁基磺酸(以下简称为ATBS。)，进行中和 $\\mathrm{(pH=7.2)}$ ，制作含有丙烯酰胺基-叔丁基磺酸钾盐(以下简称为ATBS-K。)的中和混合物。  \n\n[0420] 接下来，分别制备 $7.54\\mathrm{g}\\left(0.0530\\right.$ 摩尔)甲基丙烯酸缩水甘油酯(以下简称为GMA。)、$15.40\\mathrm{g}\\left(0.0530\\right.$ 摩尔)甲基丙烯酰氧基丙基三乙氧基硅烷(以下简称为KBE-503。)和 $22.8\\mathrm{g}$ 甲醇的混合液、及1.15g作为聚合引发剂的过氧化 $2^{-}$ 乙基己酸叔丁酯(以下简称为过丁基 $-0.$ 。)和11.5g甲醇的混合液。分别地将它们经2小时分批装入对得到的中和混合物进行加热回流(内温 $66^{\\circ}\\mathrm{C})$ )的反应烧瓶中，每次三分之一，装入结束后，进一步在加热回流及搅拌条件下进行8小时聚合。  \n\n[0421] 冷却至室温后，过滤结晶析出的共聚物，用 $300\\mathrm{ml}$ 甲醇将得到的滤饼洗涤2次后，将取出的滤饼在减压下(低于 $100\\mathrm{mmHg})$ )、在 $50^{\\circ}\\mathrm{C}$ 的条件下充分干燥，直至不发生重量变化，得到 $86.0\\mathrm{g}$ 白色的共聚物(收率 $67\\%$ )。  \n\n[0422] 对得到的共聚物进行GPC分析，结果是重均分子量 $\\mathrm{Mw}=108,000.$ 、分子量分布Mw/Mn$=3.4$ 。另外，进行 $^{13}\\mathrm{C-NMR}$ 分析，结果是共聚物的结构单元比率ATBS-K单元/GMA单元/KBE-503单元 $=90/5/5$ 。需要说明的是，未检测出环氧基开环而得到的单元。结果示于表1。  \n\n[0423]  \n\n![](images/df86a2c21cef74b1abc5c9759fe6de6f31c146d5c6ff50a127813d40bf99447f.jpg)  \n\n[0424] [合成例2]<共聚物91/9/0  CH140225的制造>[0425] 将 $7.54\\mathrm{g}\\left(0.0530\\right.$ 摩尔)GMA及 $15.40\\mathrm{g}$ (0 .0530摩尔)KBE-503变更为仅5 . $48\\mathrm{g}$ (0 .0386摩尔)GMA，除此之外，与合成例1同样地进行共聚物的制作，其结果是，得到 $108.8\\mathrm{g}$ 白色的共聚物(收率 $97\\%$ )。对得到的共聚物进行GPC分析，结果是重均分子量 $\\mathrm{Mw}{=}90\\mathrm{,000}$ 、分子量分布 $\\mathrm{Mw/Mn{=}3.1}$ 。另外，进行 $^{13}\\mathrm{C-NMR}$ 分析，结果是共聚物的结构单元比率ATBS-K单元/GMA单元/KBE-503单元 $=91/9/0$ 。需要说明的是，未检测出环氧基开环而得到的单元。结果示于表1。  \n\n[0426] [合成例3]<共聚物90/0/10  CH140206的制造>[0427] 将 $7.54\\mathrm{g}\\left(0.0530\\right.$ 摩尔)GMA及15 .40g(0 .0530摩尔)KBE-503变更为 $30.8\\mathrm{g}\\left(0.1061\\right.$ 摩尔)KBE-503，除此之外，与合成例1同样地进行共聚物的制作，其结果是，得到 $84.7\\mathrm{g}$ 白色的共聚物(收率 $62\\%$ )。对得到的共聚物进行GPC分析，结果是重均分子量 $\\mathtt{M w}=76,000$ 、分子量分布 $\\mathrm{Mw/Mn}{=}2.7$ 。另外，进行 $^{13}\\mathrm{C-NMR}$ 分析，结果是共聚物的结构单元比率ATBS-K单元/GMA单元/KBE-503单元 $=90/0/10$ 。结果示于表1。  \n\n[0428] [表1] [0429] 聚合物的结构 [0430]  \n\n<html><body><table><tr><td rowspan=\"2\">NO.</td><td rowspan=\"2\">外观</td><td rowspan=\"2\">Mw</td><td rowspan=\"2\">Mw/Mn</td><td colspan=\"3\">单元比（摩尔比）</td><td rowspan=\"2\">备注</td></tr><tr><td>ATBS-K</td><td>GMA</td><td>KBE- 503</td></tr><tr><td>合成例1</td><td>白色固体</td><td>108,000</td><td>3.4</td><td>90</td><td>5</td><td>5</td><td>CH140212</td></tr><tr><td>合成例2</td><td>白色固体</td><td>90,000</td><td>3.1</td><td>91</td><td>9</td><td></td><td>CH140225</td></tr><tr><td>合成例3</td><td>白色固体</td><td>76,000</td><td>2.7</td><td>90</td><td></td><td>10</td><td>CH140206</td></tr></table></body></html>  \n\n[0431]  \n\n![](images/9da242b36319a897ff330389746ced344844f13c18e756cb8662377e7d985f12.jpg)  \n\n[0432] 合成例1的共聚物CH130820  Mw＝108,000  \n\n[0433]  \n\n![](images/f8580dad3830f479fd6b47a5fedead5174a3fc1f0b668931be828b8ebf2a7a7c.jpg)  \n\n[0434] 合成例2的共聚物 $\\mathrm{CH1}40225~\\mathrm{Mw}{=}90,000$  \n\n[0435]  \n\n![](images/636b6c9720962284f855ffd9d85e95fe7ca9b705b40b3f1398b747206f57027e.jpg)  \n\n[0436] 合成例3的共聚物CH140206  Mw＝76,000  \n[0437] [实施例1]  \n[0438] <配方1涂覆溶液1的制备>  \n[0439] 按照下述表2的混合顺序混合各成分，最后通过平均孔径为0.5μm的过滤器从而制备涂覆溶液1。  \n[0440] [表2]  \n[0441] 配方1涂覆溶液1的配合",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# [0442]  \n\n<html><body><table><tr><td>混合 品名 顺序</td><td></td><td>配合 (g)</td><td>3种成分与表面活 性剂的重量比 （作为100%）</td><td>备注</td></tr><tr><td>1</td><td>合成例1的共聚物</td><td>3.2</td><td>50</td><td></td></tr><tr><td>2</td><td>水</td><td>11.9</td><td></td><td></td></tr><tr><td>3</td><td>EG:乙二醇</td><td>11.9</td><td></td><td></td></tr><tr><td>4</td><td>EGM:2-甲氧基乙醇</td><td>59.4</td><td></td><td></td></tr><tr><td>5</td><td>30wt%甲醇二氧化硅溶胶 （日产化学）</td><td>6.4</td><td>30</td><td></td></tr><tr><td>6</td><td>60wt%*甲基化三聚氰胺树脂 水溶液</td><td>2.1</td><td>20</td><td></td></tr><tr><td>7</td><td>5wt%乙烯基磺酸水溶液</td><td>5.0</td><td></td><td>催化剂</td></tr><tr><td>8</td><td>10wt%DS-Na水-EGM溶液</td><td>0.05</td><td>0.08</td><td>表面活性剂</td></tr><tr><td>总计</td><td></td><td>99.95</td><td>固态成分6.6wt%</td><td></td></tr></table></body></html>  \n\n[0443]  \n\n![](images/caff3224303a14abd17f503aad18bbc16af9cbb42c165744b76ec5226ce69375.jpg)  \n\n[0444] (底漆组合物的制备)  \n\n[0445] 在搅拌条件下，向0.5g作为硅烷偶联剂的双(三甲氧基甲硅烷基丙基)胺(以下简称为 $\\mathrm{KBM-666P_{\\circ}}$ )中，混合94.5g的2-甲氧基乙醇(以下简称为EGM。)、及 $5.0\\mathrm{g}$ 水，制备固态成分 $0.5\\mathrm{wt}\\%$ 的底漆用组合物。  \n\n[0446] (底漆层的形成)  \n\n[0447] 将作为基材的已充分洗净的玻璃板(表面的水接触角小于 $8^{\\circ}$ °)设置于旋涂机(MIKASA  SPINCOATER  1H-DX2)上，一边以 $500\\mathrm{rpm}$ 的旋转速度使其旋转，一边滴加制备的底漆用组合物(固态成分 $0.5\\mathrm{wt}\\%)$ )，滴加5秒后使旋转速度上升至 $4000\\mathrm{rpm}$ ，进而在该转速下使基材旋转10秒钟，将底漆用组合物均匀地涂布在基材表面上。将得到的涂布基材于 $50^{\\circ}\\mathrm{C}$ 的烘箱中预先干燥1分钟后，于 $120^{\\circ}\\mathrm{C}$ 的烘箱中加热1小时，在基材上得到厚度为 $5\\mathrm{nm}$ 的由硅烷偶联剂形成的底漆处理基板。  \n\n[0448] (涂覆膜的形成)  \n\n[0449] 用棒涂机#30在上述底漆处理基材的底漆层上涂布上述涂覆液1，于 $50^{\\circ}\\mathrm{C}$ 的烘箱中预先干燥1分钟后，于 $120^{\\circ}\\mathrm{C}$ 加热2小时，在底漆层上形成厚度为 $3\\upmu\\mathrm{m}$ 的涂覆膜。  \n\n[0450] 通过上述工序，得到在基材(玻璃板)上形成有底漆层及涂覆膜(两者总计的厚度为 $3.005\\upmu\\mathrm{m})$ 的层叠体。将该层叠体冷却至室温，在流水下用Bemcot  M-3  II(Asahi  KaseiFibers  Corporation制)擦洗涂覆膜后，用气枪对膜表面进行干燥，之后按照上述的方法进行涂覆膜的物性评价(外观、 $120^{\\circ}\\mathrm{C}$ 加热污垢附着试验、铅笔硬度、防雾性、防污性、密合性、Taber磨耗性)。结果示于表3。  \n\n[0451] [参考例1]  \n\n[0452] 将合成例1的共聚物变更为合成例2的共聚物，除此之外，与实施例1同样地进行涂覆溶液1的制备、底漆组合物的制备、底漆层的形成、涂覆膜的形成，得到在基材(玻璃板)上形成有底漆层及涂覆膜的层叠体。按照上述的方法，与实施例1同样地对得到的涂覆膜进行物性评价。结果示于表3。  \n\n[0453] [实施例2]  \n\n[0454] 将聚碳酸酯板(以下简称为PC板。)作为形成底漆层的基材，除此之外，与实施例1同样地进行涂覆溶液1的制备、底漆组合物的制备、底漆层的形成、涂覆膜的形成，得到在基材(PC板)上形成有底漆层及涂覆膜的层叠体。按照上述的方法，与实施例1同样地对得到的涂覆膜进行物性评价。结果示于表3。  \n\n[0455] [参考例2]  \n\n[0456] 将PC板作为形成底漆层的基材，除此之外，与实施例2同样地进行涂覆溶液1的制备、底漆组合物的制备、底漆层的形成、涂覆膜的形成，得到在基材(PC板)上形成有底漆层及涂覆膜的层叠体。按照上述的方法，与实施例1同样地对得到的涂覆膜进行物性评价。结果示于表3。  \n\n[0457] [比较例1] [0458] (CH110901聚合物的制造)  \n\n[0459] 将在减压下进行了脱气的535 .5g甲醇装入反应烧瓶中，一边搅拌一边缓缓添加$23.6\\mathrm{g}$ (0 .357摩尔)纯度 $85w t\\%$ 的KOH小片并使其完全溶解。接下来，分批装入75.7g(0.357摩尔)ATBS，进行中和 $\\mathrm{(pH=7.5)}$ ，制作含有ATBS-K的中和混合物。  \n\n[0460] 接下来，将该中和混合物加热回流(内温 $63^{\\circ}\\mathrm{C}$ )，装入 $5.14\\mathrm{g}$ (0 .036摩尔)GMA与0.13g作为聚合引发剂的过丁基 $-0$ 的混合液，在加热回流下混合搅拌4.5小时，进行聚合。  \n\n[0461] 冷却至室温后，将结晶析出的聚合物滤出，用甲醇将得到的滤饼洗涤后，将取出的滤饼在减压下(低于 $100\\mathrm{mmHg})$ 、在 $50^{\\circ}\\mathrm{C}$ 的条件下干燥，直至不发生重量变化，得到 $88.8\\mathrm{g}$ 白色的共聚聚合物“CH110901”(收率 $94\\%$ )。  \n\n[0462] 对得到的共聚物进行GPC分析，结果是重均分子量 $\\mathrm{Mw}{=}163,000,\\mathrm{Mw/Mn}{=}3.4$ 。另外，进行 $^{13}\\mathrm{C-NMR}$ 分析，结果是共聚物的结构单元比率ATBS-K单元/GMA单元 $=87/13$ 。需要说明的是，未检测出环氧基开环而得到的单元。  \n\n[0463] (涂覆用组合物1的制备)  \n\n[0464] 在 $5.8\\mathrm{g}$ 制得的共聚物(CH110901聚合物)中混合 $40\\mathrm{g}$ 水而制作溶液后，在搅拌条件下，在该溶液中混合 $35\\mathrm{g}$ 的 $2^{-}$ 甲氧基乙醇(以下简称为EGM。)、20.1g四乙氧基硅烷(以下简称为TEOS。)、及 $6\\mathrm{g}$ 的 $5w t\\%$ 硫酸水溶液。使得到的混合液通过平均孔径为0.5μm的过滤器，得到固态成分(共聚物及以SiO2换算的TEOS的总量)固态成分 $11w t\\%$ 的无色透明的涂覆用组合物1 $(106.9\\mathrm{g})$ 。该组合物中的聚合物/TEOS(以SiO2换算)重量比为50/50。  \n\n[0465] (涂布试验)  \n\n[0466] 将涂覆溶液1的用棒涂机#30向基材的涂布变更为上述涂覆用组合物1的用棒涂机#18向基材的涂布，除此之外，与实施例1同样地进行底漆组合物的制备、底漆层的形成、涂覆膜的形成，得到在基材(玻璃板)上形成有底漆层及涂覆膜的层叠体。按照上述的方法，与实施例1同样地对得到的涂覆膜进行物性评价。结果示于表3。  \n\n[0467] [0468]  \n\n<html><body><table><tr><td rowspan=\"2\">No.</td><td rowspan=\"2\">共聚物 种类</td><td rowspan=\"2\">基材</td><td rowspan=\"2\">外观</td><td colspan=\"2\">水接触角 (°）</td><td colspan=\"2\">雾度 (%)</td><td rowspan=\"2\">铅笔 硬度</td><td rowspan=\"2\">防雾性</td><td rowspan=\"2\">防污性</td><td rowspan=\"2\">密合性</td><td colspan=\"2\">Taber磨耗性 （雾度）</td><td rowspan=\"2\">备注</td></tr><tr><td>加热前</td><td>120℃ x12h</td><td>加热前 120℃</td><td></td><td>试验前旋转50</td><td>次后</td></tr><tr><td>实施例1</td><td>合成例1 90/5/5</td><td>玻璃</td><td>透明</td><td>9</td><td>11</td><td>0.2</td><td>x12h 0.2</td><td>3H</td><td></td><td></td><td>100/100</td><td>0.1</td><td>19.1</td><td></td></tr><tr><td>参考例1</td><td>合成例2 91/9/0</td><td>玻璃</td><td>透明</td><td>7</td><td>9</td><td>0.2</td><td>0.3</td><td>3H</td><td></td><td></td><td>100/100</td><td>0.5</td><td>18.6</td><td></td></tr><tr><td>实施例2</td><td>合成例1 90/5/5</td><td>PC</td><td>透明</td><td>6</td><td>8</td><td>0.2</td><td>0.9</td><td>B</td><td></td><td></td><td>100/100</td><td></td><td></td><td></td></tr><tr><td>参考例2</td><td>合成例2 91/9/0</td><td>PC</td><td>透明</td><td>6</td><td>8</td><td>0.4</td><td>1.3</td><td>2B</td><td></td><td></td><td>100/100</td><td></td><td></td><td></td></tr><tr><td></td><td>比较例1CH110901 87/13/0</td><td>玻璃</td><td>透明</td><td>4</td><td>36</td><td>0.2</td><td>0.3</td><td></td><td></td><td></td><td>100/100</td><td>0.3</td><td>25.4</td><td>配合 TEOS</td></tr></table></body></html>  \n\n![](images/0be84234c9c9317130efe0754a976859d15bba4853d6fc33ec4c280ddbc342f5.jpg)  \n\n[0469] 比较例1的共聚物CH110901  Mw＝163,000  \n\n[0470] [实施例3]  \n\n[0471] 按照下述表4(配方2)的混合顺序混合各成分，最后通过平均孔径为 $0.5\\upmu\\mathrm{m}$ 的过滤器而制备涂覆溶液2。  \n\n[0472] 将涂覆溶液1变更为涂覆溶液2，除此之外，进行底漆组合物的制备、底漆层的形成、涂覆膜的形成，得到在基材(玻璃板)上形成有底漆层及涂覆膜的层叠体。按照上述的方法对得到的涂覆膜进行物性评价(外观、水接触角、雾度、防污性、密合性、铅笔硬度、Taber磨耗性)。结果示于表5。另外，利用TOF-SIMS测定上述涂覆膜的倾斜度。结果示于表6。  \n\n[0473] [表4]  \n\n[0474] 配方2涂覆溶液2的配合  \n\n[0475]  \n\n<html><body><table><tr><td>混合 顺序</td><td>品名</td><td>配合 (g)</td><td>3种成分与表面活 性剂的重量比 （作为100%）</td><td>备注</td></tr><tr><td>1</td><td>合成例1的共聚物</td><td>1.2</td><td>20</td><td></td></tr><tr><td>2</td><td>水</td><td>11.5</td><td></td><td></td></tr><tr><td>3</td><td>EG:乙二醇</td><td>11.5</td><td></td><td></td></tr><tr><td>4</td><td>EGM:2-甲氧基乙醇</td><td>57.6</td><td></td><td></td></tr><tr><td>5</td><td>30wt%甲醇二氧化硅溶胶 （日产化学）</td><td>10.2</td><td>50</td><td></td></tr><tr><td>6</td><td>60wt%*甲基化三聚氰胺树脂 水溶液</td><td>3.1</td><td>30</td><td></td></tr><tr><td>7</td><td>5wt%乙烯基磺酸水溶液</td><td>4.8</td><td></td><td>催化剂</td></tr><tr><td>8</td><td>10wt%DS-Na水-EGM溶液</td><td>0.05</td><td>0.08</td><td>表面活性剂</td></tr><tr><td>总计</td><td></td><td>99.95</td><td>固态成分6.4wt%</td><td></td></tr></table></body></html>  \n\n[0476] [参考例3]  \n\n[0477] 将合成例1的共聚物变更为合成例2的共聚物，除此之外，与实施例3同样地进行涂覆溶液2的制备、底漆组合物的制备、底漆层的形成、涂覆膜的形成，得到在基材(玻璃板)上形成有底漆层及涂覆膜的层叠体。按照上述的方法，与实施例3同样地对得到的涂覆膜进行物性评价。结果示于表5。  \n\n[0478] [参考例4]  \n\n[0479] 将合成例1的共聚物变更为合成例3的共聚物，将10wt％DS-Na水-EGM溶液(表面活性剂)的添加量从0.05g变更为 $0.5\\mathrm{g}$ (变更为10倍)，除此之外，与实施例3同样地进行涂覆溶液2的制备、底漆组合物的制备、底漆层的形成、涂覆膜的形成，得到在基材(玻璃板)上形成有底漆层及涂覆膜的层叠体。按照上述的方法，与实施例3同样地对得到的涂覆膜进行物性评价。结果示于表5。  \n\n[0480] [比较例2] [0481] (涂覆用组合物2的制备)  \n\n[0482] 在2 .3g比较例1中制造的共聚物(CH110901聚合物)中混合 $30\\mathrm{g}$ 水而制作溶液后，在搅拌条件下，在该溶液中混合 $35\\mathrm{g}$ 的EGM、32 .1g的TEOS、及 $6\\mathrm{g}$ 的 $5w t\\%$ 硫酸水溶液。使得到的混合液通过平均孔径为 $0.5\\upmu\\mathrm{m}$ 的过滤器，得到固态成分(共聚物及以SiO2换算的TEOS的总量)固态成分11wt $\\%$ 的无色透明的涂覆用组合物2(105.4g)。该组合物中的聚合物/TEOS(以SiO2换算)重量比为20/80。  \n\n[0483] (涂布试验)  \n\n[0484] 将涂覆溶液2的用棒涂机#30向基材的涂布变更为上述涂覆用组合物2的用棒涂机#18向基材的涂布，除此之外，与实施例5同样地进行底漆组合物的制备、底漆层的形成、涂覆膜的形成，得到在基材(玻璃板)上形成有底漆层及涂覆膜的层叠体。按照上述的方法，与实施例5同样地对得到的涂覆膜进行物性评价。结果示于表5。  \n\n[0485]  \n\n肉   \n\n\n<html><body><table><tr><td rowspan=\"2\">No.</td><td rowspan=\"2\">共聚物 种类</td><td rowspan=\"2\">基材</td><td rowspan=\"2\">外观</td><td rowspan=\"2\">水接触角 (°)</td><td rowspan=\"2\">雾度 (%)</td><td rowspan=\"2\">防污性</td><td rowspan=\"2\">密合性</td><td rowspan=\"2\">铅笔硬度</td><td colspan=\"2\">Taber磨耗性（雾度）</td><td rowspan=\"2\">备注</td></tr><tr><td>试验前</td><td></td></tr><tr><td>实施例3</td><td>合成例1 90/5/5</td><td>玻璃</td><td>透明</td><td>14</td><td>0.2</td><td></td><td>100/100</td><td>6H</td><td>0.2</td><td>5.3</td><td></td></tr><tr><td>参考例3</td><td>合成例2 91/9/0</td><td>玻璃</td><td>透明</td><td>5</td><td>0.3</td><td></td><td>100/100</td><td>6H</td><td>0.3</td><td>5.3</td><td></td></tr><tr><td>参考例4</td><td>合成例3 90/0/10</td><td>玻璃</td><td>透明</td><td>16</td><td>1.9</td><td></td><td>100/100</td><td>一</td><td>一</td><td>1</td><td></td></tr><tr><td>比较例2</td><td>CH110901 87/13/0</td><td>玻璃</td><td>透明</td><td>14</td><td>0.2</td><td></td><td>100/100</td><td></td><td>0.2</td><td>7.1</td><td>配合 TEOS</td></tr></table></body></html>  \n\n[0486] [表6][0487] 实施例3的膜厚方向的分析  \n\n<html><body><table><tr><td rowspan=\"4\">[0488]</td><td></td><td>*表面浓度 Sa</td><td>**膜内部浓度 Da</td><td>倾斜度 Sa/Da</td></tr><tr><td>1磺酸成分</td><td>9.7E-02</td><td>8.6E-02</td><td>1.13</td></tr><tr><td>2)三聚氰胺树脂成分</td><td>9.9E-02</td><td>11.0E-02</td><td>0.90</td></tr><tr><td>3）二氧化硅粒子成分</td><td>0.66E-02</td><td>2.1E-02</td><td>0.31</td></tr></table></body></html>  \n\n[0489] \\*由TOF-SIMS分析得到的亲水性膜表面离子强度  \n[0490] \\*\\*由TOF-SIMS分析得到的亲水性膜的膜厚1/2的地点内部的离子强度  \n[0491] 1)TOF-SIMS磺酸 $\\left(\\mathrm{S0_{3}}^{-}\\right)$ )强度  \n[0492] 2)TOF-SIMS氨基 $\\left(\\mathrm{{C_{2}}\\mathrm{{N_{3}}^{-}}}\\right)$ 强度  \n[0493] 3)TOF-SIMS二氧化硅粒子 $(\\mathrm{Si}^{+})$ 强度  \n[0494] [合成例4]<共聚物 $\\boldsymbol{|94/3/3}$ AFM0110的制造>  \n\n[0495] 将在减压下进行了脱气的756 .6g甲醇装入反应烧瓶中，一边搅拌一边缓缓添加50 .46g(0 .7645摩尔)纯度 $85w t\\%$ 的KOH小片并使其完全溶解。接下来，分批装入 $162.0\\mathrm{g}$ (0.7645摩尔)丙烯酰胺基-叔丁基磺酸(以下简称为ATBS。)，进行中和 $\\mathrm{(pH=7.6)}$ )，制作含有ATBS-K的中和混合物。  \n\n[0496] 接下来，分别制备 $3.47\\mathrm{g}\\left(0.0244\\right.$ 摩尔) $\\mathrm{GMA}\\setminus7.09\\mathrm{g}\\left(0.0244\\right.$ 摩尔)KBE-503和 $10.0\\mathrm{g}$ 甲醇的混合液、及0.53g作为聚合引发剂的过丁基 $-0$ 和 $5.0\\mathrm{g}$ 甲醇的混合液。分别地将它们经2小时分批装入对得到的中和混合物进行加热回流(内温 $66^{\\circ}\\mathrm{C}\\cdot$ )的反应烧瓶中，每次三分之一，装入结束后，进一步在加热回流及搅拌条件下进行5小时聚合。  \n\n[0497] 冷却至室温后，过滤结晶析出的共聚物，用 $300\\mathrm{ml}$ 甲醇将得到的滤饼洗涤2次后，将取出的滤饼在减压下(低于 $100\\mathrm{mmHg})$ )、在 $50^{\\circ}\\mathrm{C}$ 的条件下充分干燥，直至不发生重量变化，得到 $198.0\\mathrm{g}$ 白色的共聚物(收率 $97\\%$ )。  \n\n[0498] 对得到的共聚物进行GPC分析，结果是重均分子量 $\\mathrm{Mw}=105,000$ 、分子量分布Mw/Mn$=4.1$ 。另外，进行 $^{13}\\mathrm{C-NMR}$ 分析，结果是共聚物的结构单元比率ATBS-K单元/GMA单元/KBE-503单元 $=94/3/3$ 。需要说明的是，未检测出环氧基开环而得到的单元。结果示于表7。  \n\n[0499] [合成例5]<共聚物71/17/12  CH131218的制造>[0500] 将在减压下进行了脱气的 $322.5\\mathrm{g}$ 甲醇和同样地进行了脱气的 $118.6\\mathrm{g}$ 乙醇装入反应烧瓶中，一边搅拌一边缓缓添加 $15.00\\mathrm{g}$ (0 .2273摩尔)纯度 $85w t\\%$ 的KOH小片并使其完全溶解。接下来，分批装入 $48.16\\mathrm{g}\\left(0.2273\\right.$ 摩尔)丙烯酰胺基-叔丁基磺酸(以下简称为ATBS。)，进行中和 $\\mathrm{(pH=7.4)}$ ，制作含有ATBS-K的中和混合物。  \n\n[0501] 接下来，分别制备 $16.15\\mathrm{g}$ (0 .1136摩尔) $\\mathrm{GMA,33.00g}$ (0 .1136摩尔)KBE-503和进行了脱气的 $22.8\\mathrm{g}$ 乙醇的混合液、及 $0.98\\mathrm{g}$ 作为聚合引发剂的过丁基 $_{-0}$ 和进行了脱气的9.8g乙醇的混合液。分别地将它们经2小时分批装入对得到的中和混合物进行加热回流(内温67${}^{\\circ}\\mathrm{C})$ )的反应烧瓶中，每次三分之一，装入结束后，进一步在加热回流及搅拌条件下进行8小时聚合。  \n\n[0502] 冷却至室温后，过滤结晶析出的共聚物，用 $500\\mathrm{ml}$ 甲醇洗涤得到的滤饼后，将取出的滤饼在减压下(低于 $100\\mathrm{mmHg})$ )、在 $50^{\\circ}\\mathrm{C}$ 的条件下充分干燥，直至不发生重量变化，得到$53.3\\mathrm{g}$ 白色的共聚物(收率 $50\\%$ )。  \n\n[0503] 对得到的共聚物进行GPC分析，结果是重均分子量 $\\mathrm{Mw=38,000}.$ 、分子量分布Mw/Mn$=3.9$ 。另外，进行 $^{13}\\mathrm{C-NMR}$ 分析，结果是共聚物的结构单元比率ATBS-K单元/GMA单元/KBE-503单元 $=71/17/12$ 。需要说明的是，未检测出环氧基开环而得到的单元。结果示于表7。  \n\n[0504] [合成例6]<共聚物66/20/14  CH131216的制造>[0505] 将在减压下进行了脱气的 $347.9\\mathrm{g}$ 甲醇和同样地进行了脱气的 $173.9\\mathrm{g}$ 乙醇装入反应烧瓶中，一边搅拌一边缓缓添加 $15.00\\mathrm{g}$ (0 .2273摩尔)纯度 $85w t\\%$ 的KOH小片并使其完全溶解。接下来，分批装入 $48.40\\mathrm{g}\\left(0.2284\\right.$ 摩尔)丙烯酰胺基-叔丁基磺酸(以下简称为ATBS。)，进行中和 $\\mathrm{(pH=7.4)}$ ，制作含有ATBS-K的中和混合物。  \n\n[0506] 接下来，分别制备 $24.23\\mathrm{g}$ (0 .1705摩尔)GMA、49 .50g(0 .1705摩尔)KBE-503和进行了脱气的 $2.0\\mathrm{g}$ 乙醇的混合液、及1.23g作为聚合引发剂的过丁基-O和进行了脱气的12.3g乙醇的混合液。分别地将它们经2小时分批装入对得到的中和混合物进行加热回流(内温67${}^{\\circ}\\mathrm{C})$ )的反应烧瓶中，每次三分之一，装入结束后，进一步在加热回流及搅拌条件下进行8小时聚合。  \n\n[0507] 冷却至室温后，过滤结晶析出的共聚物，用 $500\\mathrm{ml}$ 甲醇洗涤得到的滤饼后，将取出的滤饼在减压下(低于 $100\\mathrm{mmHg},$ )、在 $50^{\\circ}\\mathrm{C}$ 的条件下充分干燥，直至不发生重量变化，得到$53.2\\mathrm{g}$ 白色的共聚物(收率 $41\\%$ )。  \n\n[0508] 对得到的共聚物进行GPC分析，结果是重均分子量 $\\mathrm{Mw}{=}38\\mathrm{,000}$ 、分子量分布Mw/Mn$=2.7$ 。另外，进行 $^{13}\\mathrm{C-NMR}$ 分析，结果是共聚物的结构单元比率ATBS-K单元/GMA单元/KBE-503单元 $=66/20/14$ 。需要说明的是，未检测出环氧基开环而得到的单元。结果示于表7。  \n\n[0509] [表7] [0510] 聚合物的结构 [0511]  \n\n<html><body><table><tr><td rowspan=\"2\">NO.</td><td rowspan=\"2\">外观</td><td rowspan=\"2\">Mw</td><td rowspan=\"2\">Mw/Mn</td><td colspan=\"3\">单元比</td><td rowspan=\"2\">备注</td></tr><tr><td>ATBS-K</td><td>GMA</td><td>KBE- 503</td></tr><tr><td>合成例4</td><td>白色固体</td><td>105,000</td><td>4.1</td><td>94</td><td>3</td><td>3</td><td>AFM0110</td></tr><tr><td>合成例1</td><td>白色固体</td><td>108,000</td><td>3.4</td><td>85</td><td>8</td><td>7</td><td>CH140212</td></tr><tr><td>合成例5</td><td>白色固体</td><td>78,000</td><td>3.9</td><td>71</td><td>17</td><td>12</td><td>CH131218</td></tr><tr><td>合成例6</td><td>白色固体</td><td>38,000</td><td>2.7</td><td>66</td><td>20</td><td>14</td><td>CH131216</td></tr></table></body></html>  \n\n[0512] [实施例4、参考例 $5\\mathord{\\sim}6]$  \n\n[0513] 将合成例1的共聚物变更为下述表8的共聚物种类项中记载的共聚物，除此之外，与实施例1同样地进行涂覆溶液1的制备、底漆组合物的制备、底漆层的形成、涂覆膜的形成，得到在基材(玻璃板)上形成有底漆层及涂覆膜的层叠体。按照上述的方法对得到的涂覆膜进行物性评价(外观、 $120^{\\circ}\\mathrm{C}$ 加热污垢附着试验、铅笔硬度、防雾性、防污性、密合性)。结果示于表8。需要说明的是，表8中再次示出实施例1的结果。  \n\n[0514] [实施例5、参考例 $7{\\sim}8]$  \n\n[0515] 将合成例1的共聚物变更为下述表8的共聚物种类项中记载的共聚物，除此之外，与实施例2同样地进行涂覆溶液1的制备、底漆组合物的制备、底漆层的形成、涂覆膜的形成，得到在基材(PC板)上形成有底漆层及涂覆膜的层叠体。按照上述方法对得到的涂覆膜进行物性评价(外观、 $120^{\\circ}\\mathrm{C}$ 加热污垢附着试验、铅笔硬度、防雾性、防污性、密合性)。结果示于表8。需要说明的是，表8中再次示出实施例2的结果。  \n\n<html><body><table><tr><td rowspan=\"2\">No.</td><td rowspan=\"2\">共聚物 种类</td><td rowspan=\"2\">基材</td><td rowspan=\"2\">外观</td><td colspan=\"2\">水接触角</td><td colspan=\"2\">雾度</td><td rowspan=\"2\">铅笔硬度</td><td rowspan=\"2\">防雾性</td><td rowspan=\"2\">防污性</td><td rowspan=\"2\">密合性</td></tr><tr><td>加热前</td><td>120℃ x12h</td><td>加热前</td><td>120℃ x12h</td></tr><tr><td>实施例4</td><td>合成例4 94/3/3</td><td>玻璃</td><td>透明</td><td>8</td><td>12</td><td>0.2</td><td>0.3</td><td>2H</td><td></td><td></td><td>100/100</td></tr><tr><td>实施例1</td><td>合成例1 90/5/5</td><td>玻璃</td><td>透明</td><td>9</td><td>11</td><td>0.2</td><td>0.2</td><td>3H</td><td></td><td></td><td>100/100</td></tr><tr><td>参考例5</td><td>合成例5 71/17/12</td><td>玻璃</td><td>透明</td><td>66</td><td>73</td><td>0.2</td><td>0.2</td><td>6H</td><td>X</td><td>△</td><td>100/100</td></tr><tr><td>参考例6</td><td>合成例6 66/20/14</td><td>玻璃</td><td>透明</td><td>70</td><td>73</td><td>0.2</td><td>0.2</td><td>7H</td><td>X</td><td>△</td><td>100/100</td></tr><tr><td>实施例5</td><td>合成例4 94/3/3</td><td>PC</td><td>透明</td><td>6</td><td>7</td><td>0.2</td><td>0.9</td><td>2B</td><td></td><td></td><td>100/100</td></tr><tr><td>实施例2</td><td>合成例1 90/5/5</td><td>PC</td><td>透明</td><td>6</td><td>8</td><td>0.2</td><td>0.9</td><td>B</td><td></td><td></td><td>100/100</td></tr><tr><td>参考例7</td><td>合成例5 71/17/12</td><td>PC</td><td>透明</td><td>52</td><td>57</td><td>0.2</td><td>0.4</td><td>B</td><td>X</td><td>X</td><td>100/100</td></tr><tr><td>参考例8</td><td>合成例6 66/20/14</td><td>PC</td><td>透明</td><td>60</td><td>67</td><td>0.2</td><td>0.3</td><td>HB</td><td>X</td><td>X</td><td>100/100</td></tr></table></body></html>  \n\n[0517] [合成例7]<共聚物 $86/5/9$ CH130115的制造>[0518] 将在减压下进行了脱气的 $1150.0\\mathrm{g}$ 甲醇装入反应烧瓶中，一边搅拌一边缓缓添加$28.0\\mathrm{g}\\left(0.424\\right.$ 摩尔)纯度 $85w t\\%$ 的KOH小片并使其完全溶解。接下来，分批装入89.9g(0.424摩尔)ATBS，进行中和 $\\mathrm{(pH=7.3)}$ ，制作含有ATBS-K的中和混合物。  \n\n[0519] 接下来，分别制备 $3.77\\mathrm{g}\\left(0.0265\\right.$ 摩尔) $\\mathrm{\\Delta\\vec{\\mathrm{{zMA}}},23.10g\\ }$ (0 .0795摩尔)KBE-503和3 .1g甲醇的混合液、及 $3.44\\mathrm{g}$ 作为聚合引发剂的过丁基 $-0$ 和11.5g甲醇的混合液。分别地将它们经2小时分批装入对得到的中和混合物进行加热回流(内温 $66^{\\circ}\\mathrm{C}\\dot{}$ )的反应烧瓶中，每次三分之一，装入结束后，进一步在加热回流及搅拌条件下进行8小时聚合。  \n\n[0520] 冷却至室温后，过滤结晶析出的共聚物，用 $700\\mathrm{ml}$ 甲醇洗涤得到的滤饼后，将取出的滤饼在减压下(低于 $100\\mathrm{mmHg},$ )、在 $50^{\\circ}\\mathrm{C}$ 的条件下充分干燥，直至不发生重量变化，得到$69.2\\mathrm{g}$ 白色的共聚物(收率 $52\\%$ )。  \n\n[0521] 对得到的共聚物进行GPC分析，结果是重均分子量 $\\mathrm{Mw}=68,000.$ 、分子量分布Mw/Mn$=2.5$ 。另外，进行 $^{13}\\mathrm{C-NMR}$ 分析，结果是共聚物的结构单元比率ATBS-K单元/GMA单元/KBE-503单元 $=86/5/9$ 。需要说明的是，未检测出环氧基开环而得到的单元。结果示于表9。  \n\n[0522] [合成例8]<共聚物 $82/14/4$ CH130117的制造>[0523] 除了变更为 $11.31\\mathrm{g}\\left(0.0795\\right.$ 摩尔)GMA、7 .7g(0 .0265摩尔)KBE-503之外，与合成例7同样地进行共聚物的制作，其结果是，得到 $92.2\\mathrm{g}$ 白色的共聚物(收率 $73\\%$ )。对得到的共聚物进行GPC分析，结果是重均分子量 $\\operatorname{Mw}=71,000.$ 、分子量分布 $\\mathrm{Mw/Mn}{=}2.5$ 。另外，进行 $^{13}\\mathrm{C-MMR}$ 分析，结果是共聚物的结构单元比率ATBS-K单元/GMA单元/KBE-503单元 $=82/14/4$ 。需要说明的是，未检测出环氧基开环而得到的单元。结果示于表9。  \n\n[0524] [表9] [0525]  \n\n<html><body><table><tr><td rowspan=\"2\">NO.</td><td rowspan=\"2\">外观</td><td rowspan=\"2\">Mw</td><td rowspan=\"2\">Mw/Mn</td><td colspan=\"3\">单元比（摩尔比）</td><td rowspan=\"2\">备注</td></tr><tr><td>ATBS-K</td><td>GMA</td><td>KBE-503</td></tr><tr><td>合成例7</td><td>白色固体</td><td>68,000</td><td>2.5</td><td>86</td><td>5</td><td>9</td><td>CH130115</td></tr><tr><td>合成例1</td><td>白色固体</td><td>108,000</td><td>3.4</td><td>90</td><td>5</td><td>5</td><td>CH140212</td></tr><tr><td>合成例8</td><td>白色固体</td><td>71,000</td><td>2.5</td><td>82</td><td>14</td><td>4</td><td>CH130117</td></tr></table></body></html>  \n\n[0526] [实施例6、7]  \n\n[0527] 将合成例1的共聚物变更为下述表10的共聚物种类项中记载的共聚物，除此之外，与实施例1同样地进行涂覆溶液1的制备、底漆组合物的制备、底漆层的形成、涂覆膜的形成，得到在基材(玻璃板)上形成有底漆层及涂覆膜的层叠体。按照上述的方法对得到的涂覆膜进行物性评价(外观、 $120^{\\circ}\\mathrm{C}$ 加热污垢附着试验、铅笔硬度、防雾性、防污性)。结果示于表10。需要说明的是，表10中再次示出实施例1的结果。  \n\n[0528] [实施例8、9]  \n\n[0529] 将合成例1的共聚物变更为下述表10的共聚物种类项中记载的共聚物，除此之外，与实施例3同样地进行涂覆溶液2的制备、底漆组合物的制备、底漆层的形成、涂覆膜的形成，得到在基材(玻璃板)上形成有底漆层及涂覆膜的层叠体。按照上述的方法对得到的涂覆膜进行物性评价(外观、 $120^{\\circ}\\mathrm{C}$ 加热污垢附着试验、铅笔硬度、防雾性、防污性)。结果示于表10。需要说明的是，表10中再次示出实施例3的结果。  \n\n<html><body><table><tr><td rowspan=\"2\">No.</td><td rowspan=\"2\">共聚物 种类</td><td rowspan=\"2\">外观</td><td colspan=\"2\">水接触角 (°)</td><td colspan=\"2\">雾度 (%)</td><td rowspan=\"2\">铅笔硬度</td><td rowspan=\"2\">防雾性</td><td rowspan=\"2\">防污性</td><td rowspan=\"2\">涂覆溶液 种类</td></tr><tr><td>加热前</td><td>120℃</td><td>加热前</td><td>120C</td></tr><tr><td>实施例6</td><td>合成例7 86/5/9</td><td>透明</td><td>9</td><td>x12h 9</td><td>0.1</td><td>×12h 0.1</td><td>3H</td><td></td><td></td><td>配方1 涂覆溶液1</td></tr><tr><td>实施例1</td><td>合成例1 90/5/5</td><td>透明</td><td>9</td><td>11</td><td>0.2</td><td>0.2</td><td>3H</td><td></td><td></td><td>同上</td></tr><tr><td>实施例7</td><td>合成例8 82/14/4</td><td>透明</td><td>9</td><td>10</td><td>0.3</td><td>0.3</td><td>3H</td><td>O</td><td></td><td>同上</td></tr><tr><td>实施例8</td><td>合成例7 86/5/9</td><td>透明</td><td>14</td><td>12</td><td>0.2</td><td>0.2</td><td>5H</td><td>△</td><td></td><td>配方2 涂覆溶液2</td></tr><tr><td>实施例3</td><td>合成例1 90/5/5</td><td>透明</td><td>14</td><td>10</td><td>0.2</td><td>0.3</td><td>6H</td><td>△</td><td>O</td><td>同上</td></tr><tr><td>实施例9</td><td>合成例8 82/14/4</td><td>透明</td><td>20</td><td>18</td><td>0.4</td><td>0.6</td><td>6H</td><td>△</td><td>O</td><td>同上</td></tr></table></body></html>\n\n[0531] [合成例9]<共聚物 $95/5/0$ CH120217的制造>  \n\n[0532] 将在减压下进行了脱气的 $780.0\\mathrm{g}$ 甲醇装入反应烧瓶中，一边搅拌一边缓缓添加$46.26\\mathrm{g}\\left(0.7009\\right.$ 摩尔)纯度 $85w t\\%$ 的KOH小片并使其完全溶解。分批装入 $.150.0\\mathrm{g}\\left(0.7078\\right.$ 摩尔)ATBS，进行中和 $(\\mathrm{pH}=7.7)$ ，制作含有ATBS-K的中和混合物。  \n\n[0533] 接下来，分别制备 $3.43\\mathrm{g}\\left(0.0236\\right.$ 摩尔)GMA和2.0g甲醇的混合液、及 $0.24\\mathrm{g}$ 作为聚合引发剂的过丁基 $-0$ 和 $2.4\\mathrm{g}$ 甲醇的混合液。分别地将它们经2小时分批装入对得到的中和混合物进行加热回流(内温 $68^{\\circ}\\mathrm{C})$ )的反应烧瓶中，每次三分之一，装入结束后，进一步在加热回流及搅拌条件下进行6小时聚合。  \n\n[0534] 冷却至室温后，过滤结晶析出的共聚物，用 $400\\mathrm{ml}$ 甲醇将得到的滤饼洗涤2次后，将取出的滤饼在减压下(低于 $100\\mathrm{mmHg})$ )、在 $50^{\\circ}\\mathrm{C}$ 的条件下充分干燥，直至不发生重量变化，得到174.7g白色的共聚物(收率 $97\\%$ )。  \n\n[0535] 对得到的共聚物进行GPC分析，结果是重均分子量 $\\mathrm{Mw}=107,000.$ 、分子量分布Mw/Mn$=3.0$ 。另外，进行 $^{13}\\mathrm{C-NMR}$ 分析，结果是共聚物的结构单元比率ATBS-K单元/GMA单元/KBE-503单元 $=95/5/0$ 。需要说明的是，未检测出环氧基开环而得到的单元。结果示于表11。  \n\n[0536] [合成例10]<共聚物59/41/0  CH140312的制造>[0537] 将在减压下进行了脱气的 $215.0\\mathrm{g}$ 甲醇和进行了脱气的 $215.0\\mathrm{g}$ 乙醇装入反应烧瓶中，一边搅拌一边缓缓添加 $20.0\\mathrm{{g}\\ (0.303}$ 摩尔)纯度 $85w t\\%$ 的KOH小片并使其完全溶解。分批装入 $.64.2\\mathrm{g}\\left(0.303\\right.$ 摩尔)ATBS，进行中和 $\\mathrm{(pH=7.4)}$ ，制作含有ATBS-K的中和混合物。  \n\n[0538] 接下来，分别制备 $23.2\\mathrm{g}\\left(0.163\\right.$ 摩尔)GMA、0.15g作为聚合引发剂的过丁基-O、和进行了脱气的 $46.7\\mathrm{g}$ 乙醇的混合液。分别地将它们经2小时分批装入对得到的中和混合物进行加热回流(内温 $68^{\\circ}\\mathrm{C}$ )的反应烧瓶中，每次三分之一，装入结束后，进一步在加热回流及搅拌条件下进行10小时聚合。  \n\n[0539] 冷却至室温后，过滤结晶析出的共聚物，用 $300\\mathrm{ml}$ 甲醇将得到的滤饼洗涤2次后，将取出的滤饼在减压下(低于 $100\\mathrm{mmHg})$ 、在 $50^{\\circ}\\mathrm{C}$ 的条件下充分干燥，直至不发生重量变化，得到 $95.2\\mathrm{g}$ 白色的共聚物(收率 $96\\%$ )。  \n\n[0540] 对得到的共聚物进行GPC分析，结果是重均分子量 $\\mathrm{Mw}=120000.$ 、分子量分布Mw/Mn$=4.3$ 。另外，进行 $^{13}\\mathrm{C-NMR}$ 分析，结果是共聚物的结构单元比率ATBS-K单元/GMA单元/KBE-503单元 $=59/41/0$ 。需要说明的是，未检测出环氧基开环而得到的单元。结果示于表11。  \n\n[0541] [表11] [0542] 聚合物的结构 [0543]  \n\n<html><body><table><tr><td rowspan=\"2\">NO.</td><td rowspan=\"2\">共聚物</td><td rowspan=\"2\">外观</td><td rowspan=\"2\">Mw</td><td rowspan=\"2\">Mw/Mn</td><td colspan=\"3\">单元比（摩尔比）</td></tr><tr><td>ATBS-K</td><td>GMA</td><td>KBE -503</td></tr><tr><td>合成例9</td><td>CH120217</td><td>白色固体</td><td>107,000</td><td>3.0</td><td>95</td><td>5</td><td></td></tr><tr><td>合成例2</td><td>CH140225</td><td>白色固体</td><td>90,000</td><td>3.1</td><td>91</td><td>9</td><td></td></tr><tr><td>合成例10</td><td>CH140312</td><td>白色固体</td><td>120,000</td><td>4.3</td><td>59</td><td>41</td><td></td></tr></table></body></html>\n\n[0544] [参考例9、10]  \n\n[0545] 将合成例1的共聚物变更为下述表12的共聚物种类项中记载的共聚物，除此之外，与实施例1同样地进行涂覆溶液1的制备、底漆组合物的制备、底漆层的形成、涂覆膜的形成，得到在基材(玻璃板)上形成有底漆层及涂覆膜的层叠体。按照上述方法对得到的涂覆膜进行物性评价(外观、 $120^{\\circ}\\mathrm{C}$ 加热污垢附着试验、铅笔硬度、防雾性、防污性)。结果示于表12。需要说明的是，表12中再次示出参考例1的结果。  \n\n[0546] [参考例11、12]  \n\n[0547] 将合成例1的共聚物变更为下述表12的共聚物种类项中记载的共聚物，除此之外，与实施例3同样地进行涂覆溶液2的制备、底漆组合物的制备、底漆层的形成、涂覆膜的形成，得到在基材(玻璃板)上形成有底漆层及涂覆膜的层叠体。按照上述的方法对得到的涂覆膜进行物性评价(外观、 $120^{\\circ}\\mathrm{C}$ 加热污垢附着试验、铅笔硬度、防雾性、防污性)。结果示于表12。需要说明的是，表12中再次示出参考例3的结果。  \n\n[0548]  \n\n<html><body><table><tr><td rowspan=\"2\">No.</td><td rowspan=\"2\">共聚物 种类</td><td rowspan=\"2\">外观</td><td colspan=\"2\">水接触角 (°）</td><td colspan=\"2\">雾度 （%）</td><td rowspan=\"2\">铅笔硬度</td><td rowspan=\"2\">防雾性</td><td rowspan=\"2\">防污性</td><td rowspan=\"2\">涂覆溶液 种类</td></tr><tr><td>加热前</td><td>120C x12h</td><td>加热前</td><td>120C x12h</td></tr><tr><td>参考例9</td><td>合成例9 95/5/0</td><td>透明</td><td>5</td><td>5</td><td>0.3</td><td>0.3</td><td>3H</td><td></td><td></td><td>配方1 涂覆溶液1</td></tr><tr><td>参考例1</td><td>合成例2 91/9/0</td><td>透明</td><td>7</td><td>9</td><td>0.2</td><td>0.3</td><td>3H</td><td></td><td></td><td>同上</td></tr><tr><td>参考例10</td><td>合成例10 59/41/0</td><td>透明</td><td>10</td><td>11</td><td>0.3</td><td>0.3</td><td>3H</td><td></td><td></td><td>同上</td></tr><tr><td>参考例11</td><td>合成例9 95/5/0</td><td>透明</td><td>5</td><td>8</td><td>0.3</td><td>0.4</td><td>6H</td><td></td><td></td><td>配方2 涂覆溶液2</td></tr><tr><td>参考例3</td><td>合成例2 91/9/0</td><td>透明</td><td>5</td><td>5</td><td>0.3</td><td>0.4</td><td>6H</td><td></td><td></td><td>同上</td></tr><tr><td>参考例12</td><td>合成例10 59/41/0</td><td>透明</td><td>22</td><td>28</td><td>0.2</td><td>0.2</td><td>6H</td><td>△</td><td></td><td>同上</td></tr></table></body></html>  \n\n[0549] [实施例 $10\\mathrm{\\sim}16]$  \n\n[0550] 将涂覆溶液1中含有的DS-Na(表面活性剂)的添加量变更为表13中记载的量，除此之外，与实施例1同样地进行涂覆溶液1的制备、底漆组合物的制备、底漆层的形成、涂覆膜的形成，得到在基材(玻璃板)上形成有底漆层及涂覆膜的层叠体。对得到的涂覆膜进行物性评价(外观、 $120^{\\circ}\\mathrm{C}$ 加热污垢附着试验、铅笔硬度、防雾性、防污性)。结果示于表13。  \n\n[0551]  \n\n<html><body><table><tr><td rowspan=\"2\">No.</td><td rowspan=\"2\">DS-Na添加量 （倍/实施例1）</td><td rowspan=\"2\">基材</td><td rowspan=\"2\">外观</td><td colspan=\"2\">水接触角 (°)</td><td colspan=\"2\">雾度 (%)</td><td rowspan=\"2\">铅笔硬度</td><td rowspan=\"2\">防雾性</td><td rowspan=\"2\">防污性</td><td rowspan=\"2\">共聚物 种类</td></tr><tr><td>加热前</td><td>120℃</td><td>加热前</td><td>120C</td></tr><tr><td>实施例10</td><td>无添加</td><td>玻璃</td><td>透明</td><td>30</td><td>x12h 47</td><td>0.1</td><td>x12h 0.1</td><td>3H</td><td>X</td><td>△</td><td>合成例1</td></tr><tr><td>实施例11</td><td>0.5倍</td><td>玻璃</td><td>透明</td><td>16</td><td>19</td><td>0.1</td><td>0.2</td><td>3H</td><td>△</td><td></td><td>合成例1</td></tr><tr><td>实施例1</td><td>1倍</td><td>玻璃</td><td>透明</td><td>9</td><td>11</td><td>0.2</td><td>0.2</td><td>3H</td><td></td><td></td><td>合成例1</td></tr><tr><td>实施例12</td><td>2倍</td><td>玻璃</td><td>透明</td><td>9</td><td>10</td><td>0.2</td><td>0.3</td><td>3H</td><td></td><td></td><td>合成例1</td></tr><tr><td>实施例13</td><td>3倍</td><td>玻璃</td><td>透明</td><td>7</td><td>8</td><td>0.2</td><td>0.8</td><td>2H</td><td></td><td></td><td>合成例1</td></tr><tr><td>实施例14</td><td>5倍</td><td>玻璃</td><td>透明</td><td>4</td><td>7</td><td>0.3</td><td>2.2</td><td>2H</td><td></td><td></td><td>合成例1</td></tr><tr><td>实施例15</td><td>7倍</td><td>玻璃</td><td>透明</td><td><4</td><td>9</td><td>0.4</td><td>3.5</td><td>2H</td><td></td><td></td><td>合成例1</td></tr><tr><td>实施例16</td><td>10倍</td><td>玻璃</td><td>透明</td><td>12</td><td>13</td><td>0.9</td><td>5.1</td><td>2H</td><td></td><td></td><td>合成例1</td></tr></table></body></html>  \n\n[0552] [实施例 $17{\\sim}42]$  \n\n[0553] 将涂覆溶液1中含有的合成例1的共聚物的量、 $30\\%$ 甲醇二氧化硅溶胶的量、及$60\\%$ 甲基化三聚氰胺树脂水溶液的量变更为表14及15中记载的量，除此之外，与实施例1同样地进行涂覆溶液1的制备、底漆组合物的制备、底漆层的形成、涂覆膜的形成，得到在基材(玻璃板)上形成有底漆层及涂覆膜的层叠体。对得到的涂覆膜进行物性评价(外观、120$\\mathrm{{^\\circC}}$ 加热污垢附着试验、铅笔硬度、防污性)。结果示于表14及15。  \n\n<html><body><table><tr><td rowspan=\"2\">No.</td><td rowspan=\"2\">(g)</td><td rowspan=\"2\">共聚物30%二氧化硅溶胶 (g)</td><td rowspan=\"2\">60%三聚氰胺树脂 (g)</td><td rowspan=\"2\">聚合物/二氧化硅/ 三聚氰胺树脂 重量比</td><td colspan=\"2\">水接触角（°）</td><td colspan=\"2\">雾度（%）</td><td rowspan=\"2\">铅笔硬度</td><td rowspan=\"2\">防污性</td></tr><tr><td>加热前</td><td>120℃ x12h</td><td>加热前</td><td>120℃ x12h</td></tr><tr><td>实施例17</td><td>0.52</td><td>0.21</td><td>0.11</td><td>80/10/10</td><td>10</td><td>10</td><td>0.1</td><td>0.2</td><td>2H</td><td></td></tr><tr><td>实施例18</td><td>0.38</td><td>0.00</td><td>0.43</td><td>60/0/40</td><td>57</td><td>41</td><td>0.1</td><td>0.3</td><td></td><td></td></tr><tr><td>实施例19</td><td>0.38</td><td>0.43</td><td>0.21</td><td>60/20/20</td><td>9</td><td>7</td><td>0.2</td><td>0.4</td><td>2H</td><td></td></tr><tr><td>实施例20</td><td>0.38</td><td>0.64</td><td>0.11</td><td>60/30/10</td><td>8</td><td>10</td><td>0.1</td><td>0.1</td><td>2H</td><td></td></tr><tr><td>实施例21</td><td>0.32</td><td>0.00</td><td>0.53</td><td>50/0/50</td><td>55</td><td>52</td><td>0.2</td><td>0.3</td><td></td><td>X</td></tr><tr><td>实施例22</td><td>0.32</td><td>0.43</td><td>0.32</td><td>50/20/30</td><td>32</td><td>35</td><td>0.1</td><td>0.2</td><td></td><td>##</td></tr><tr><td>实施例23</td><td>0.32</td><td>0.64</td><td>0.21</td><td>50/30/20</td><td>8</td><td>11</td><td>0.1</td><td>0.2</td><td>3H</td><td></td></tr><tr><td>实施例24</td><td>0.32</td><td>0.85</td><td>0.11</td><td>50/40/10</td><td>8</td><td>9</td><td>0.1</td><td>0.2</td><td>H</td><td></td></tr><tr><td>实施例25</td><td>0.26</td><td>0.00</td><td>0.64</td><td>40/0/60</td><td>44</td><td>45</td><td>3.4</td><td>3.8</td><td></td><td>X</td></tr><tr><td>实施例26</td><td>0.26</td><td>0.43</td><td>0.43</td><td>40/20/40</td><td>47</td><td>55</td><td>0.2</td><td>0.1</td><td></td><td>X</td></tr><tr><td>实施例27</td><td>0.26</td><td>0.64</td><td>0.32</td><td>40/30/30</td><td>42</td><td>42</td><td>0.1</td><td>0.2</td><td></td><td></td></tr><tr><td>实施例28</td><td>0.26</td><td>0.85</td><td>0.21</td><td>40/40/20</td><td>7</td><td>8</td><td>0.1</td><td>0.2</td><td>3H</td><td></td></tr><tr><td>实施例29</td><td>0.26</td><td>1.06</td><td>0.11</td><td>40/50/10</td><td>8</td><td>11</td><td>0.2</td><td>0.2</td><td></td><td></td></tr><tr><td>实施例30</td><td>0.19</td><td>0.00</td><td>0.75</td><td>30/0/70</td><td>38</td><td>34</td><td>3.0</td><td>2.8</td><td></td><td>。</td></tr><tr><td>实施例31</td><td>0.19</td><td>0.43</td><td>0.53</td><td>30/20/50</td><td>27</td><td>30</td><td>0.6</td><td>0.4</td><td>6H</td><td></td></tr><tr><td>实施例32</td><td>0.19</td><td>0.85</td><td>0.32</td><td>30/40/30</td><td>9</td><td>10</td><td>0.1</td><td>0.1</td><td>6H</td><td></td></tr></table></body></html>  \n\n[0555]  \n\n<html><body><table><tr><td rowspan=\"2\">No.</td><td rowspan=\"2\">共聚物 (g)</td><td rowspan=\"2\">30%二氧化硅溶胶 (g)</td><td rowspan=\"2\">60%三聚氰胺树脂 (g)</td><td rowspan=\"2\">聚合物/二氧化硅/三 聚氰胺树脂重量比</td><td colspan=\"2\">水接触角 (）</td><td colspan=\"2\">雾度 (%)</td><td rowspan=\"2\">铅笔硬度</td><td rowspan=\"2\">防污性</td></tr><tr><td>加热前</td><td>120℃</td><td>加热前</td><td>120℃</td></tr><tr><td>实施例33</td><td>0.19</td><td>1.06</td><td>0.21</td><td>30/50/20</td><td>10</td><td>x12h 10</td><td>0.2</td><td>x12h 0.2</td><td>7H</td><td></td></tr><tr><td>实施例34</td><td>0.19</td><td>1.28</td><td>0.11</td><td>30/60/10</td><td>18</td><td>18</td><td>0.2</td><td>0.6</td><td></td><td></td></tr><tr><td>实施例35</td><td>0.13</td><td>0.00</td><td>0.85</td><td>20/0/80</td><td>53</td><td>51</td><td>4.1</td><td>6.3</td><td></td><td>##</td></tr><tr><td>实施例36</td><td>0.13</td><td>0.43</td><td>0.64</td><td>20/20/60</td><td>40</td><td>37</td><td>0.3</td><td>2.1</td><td>一</td><td>△#</td></tr><tr><td>实施例37</td><td>0.13</td><td>1.06</td><td>0.32</td><td>20/50/30</td><td>18</td><td>20</td><td>0.1</td><td>0.1</td><td>6H</td><td></td></tr><tr><td>实施例38</td><td>0.13</td><td>1.28</td><td>0.21</td><td>20/60/20</td><td>13</td><td>15</td><td>0.5</td><td>1.0</td><td>8H</td><td></td></tr><tr><td>实施例39</td><td>0.13</td><td>1.49</td><td>0.11</td><td>20/70/10</td><td>11</td><td>11</td><td>0.2</td><td>1.9</td><td>7H</td><td></td></tr><tr><td>实施例40</td><td>0.06</td><td>0.43</td><td>0.75</td><td>10/20/70</td><td>50</td><td>55</td><td>0.2</td><td>0.3</td><td></td><td>△#</td></tr><tr><td>实施例41</td><td>0.06</td><td>1.07</td><td>0.43</td><td>10/50/40</td><td>42</td><td>40</td><td>0.2</td><td>0.1</td><td></td><td>△#</td></tr><tr><td>实施例42</td><td>0.06</td><td>1.49</td><td>0.21</td><td>10/70/20</td><td>21</td><td>17</td><td>0.2</td><td>0.2</td><td></td><td></td></tr></table></body></html>  \n\n[0556] [合成例11]<甲基化苯胺树脂的制造方法>[0557] 向反应烧瓶中投入 $94.0\\mathrm{g}$ (1 .0摩尔)苯胺和 $160\\mathrm{g}$ 甲醇，在水浴下，一边搅拌内容物一边滴加 $109.6\\mathrm{g}\\left(1.0\\right.$ 摩尔) $35\\mathrm{wt}\\%$ 盐酸，接下来，装入 $178.4\\mathrm{g}$ (2 .2摩尔) $37\\mathrm{wt}\\%$ 甲醛水溶液后，在回流(内温 $67^{\\circ}\\mathrm{C})$ )下使其反应5小时。  \n\n[0558] 反应结束后，将得到的反应液冷却至室温后，在水浴下，于 $30^{\\circ}\\mathrm{C}$ 以下的内温下滴加$189.0\\mathrm{g}\\left(1.05\\right.$ 摩尔) $30\\%$ 甲醇钠(甲醇溶液)，中和反应液。  \n\n[0559] 过滤析出的共聚物(甲基化苯胺树脂)，用 $1000\\mathrm{ml}$ 甲醇洗涤滤饼后，于减压下(低于$\\mathrm{100mmHg)}$ ，在 $25{\\sim}30^{\\circ}\\mathrm{C}$ 的条件下充分干燥(2天)，直至不发生重量变化，得到110g橙色的共聚物。  \n\n[0560] 对得到的共聚物(甲基化苯胺树脂)进行GPC分析，结果是重均分子量 $\\mathrm{Mw}{=}800$ 。  \n\n[0561] [实施例43、44]  \n\n[0562] 将涂覆溶液1中含有的甲基化三聚氰胺树脂变更为表16中记载的氨基树脂(实施例43：甲基化尿素树脂，实施例44：甲基化苯胺树脂)，除此之外，与实施例1同样地进行涂覆溶液1的制备、底漆组合物的制备、底漆层的形成、涂覆膜的形成，得到在基材(玻璃板)上形成有底漆层及涂覆膜的层叠体。对得到的涂覆膜进行物性评价(外观、 $120^{\\circ}\\mathrm{C}$ 加热污垢附着试验、铅笔硬度、防雾性、防污性、密合性)。结果示于表16。需要说明的是，下述表16中再次示出实施例1的结果。  \n\n<html><body><table><tr><td rowspan=\"2\">No.</td><td rowspan=\"2\">氨基树脂种类</td><td rowspan=\"2\"></td><td rowspan=\"2\">基材外观</td><td colspan=\"2\">水接触角</td><td colspan=\"2\">雾度</td><td rowspan=\"2\">铅笔硬度</td><td rowspan=\"2\">防雾性</td><td rowspan=\"2\">防污性</td><td rowspan=\"2\">密合性</td></tr><tr><td>加热前</td><td>120℃ x12h</td><td>加热前</td><td>120℃ x12h</td></tr><tr><td>实施例1</td><td>甲基化三聚氰胺树脂</td><td>玻璃</td><td>透明</td><td>9</td><td>11</td><td>0.2</td><td>0.2</td><td>3H</td><td></td><td></td><td>100/100</td></tr><tr><td>实施例43</td><td>甲基化尿素树脂</td><td></td><td>玻璃透明</td><td>6</td><td>7</td><td>0.3</td><td>0.4</td><td>3H</td><td></td><td></td><td>100/100</td></tr><tr><td>实施例44</td><td>甲基化苯胺树脂</td><td></td><td>玻璃透明</td><td>26</td><td>33</td><td>0.2</td><td>0.4</td><td>3H</td><td></td><td></td><td>100/100</td></tr></table></body></html>  \n\n[0564]  \n\n![](images/2c1022c83e3b0df5352147461dda060e9f9656f48e36ab27eb1bc998bfacbcd8.jpg)  \n甲基化尿素树脂  \n\n![](images/d4797dd5c38dc3844153c26416dcc0c3be1147423d43f5de7f395a715dcb3e0b.jpg)  \n甲基化苯胺树脂  \n\n[0565] [合成例12]<共聚物SPA  CH130219的制造>[0566] 向反应烧瓶中装入 $52.43\\mathrm{g}$ (0 .2425摩尔)丙烯酸 $3-$ 磺酸丙酯·钠盐(以下简称为SPA-Na。)、 $2.43\\mathrm{g}$ (0 .0121摩尔)丙烯酸4-缩水甘油基氧基-丁基酯(以下简称为GOBA。)、$2.84\\mathrm{g}\\left(0.0121\\right.$ 摩尔) $3-$ 丙烯酰氧基 $-$ 丙基三甲氧基硅烷(以下简称为KBM-5103。)、及在减压下进行了脱气的 $488.9\\mathrm{g}$ 甲醇，制作混合液。  \n\n[0567] 接下来，在搅拌条件下，在将该混合液加热回流(内温 $65^{\\circ}\\mathrm{C}\\dot{}.$ )的状态下，装入 $0.12\\mathrm{g}$ 过丁基 $_{:-0}$ 和 $1.2\\mathrm{g}$ 甲醇的混合液，然后，进一步在加热回流及搅拌条件下进行4小时聚合。  \n\n[0568] 然后，利用旋转蒸发器对得到的聚合溶液进行减压浓缩，向得到的残渣中加入$400\\mathrm{g}$ 异丙醇和 $400\\mathrm{g}$ 环己烷，剧烈混合。  \n\n[0569] 将析出的聚合物滤出，用乙醇洗涤得到的滤饼后，将取出的滤饼在减压下(低于$\\mathrm{100mmHg)}$ 、在 $50^{\\circ}\\mathrm{C}$ 的条件下充分干燥，直至不发生重量变化，得到52.5g白色的共聚物(收率$91\\%$ )。  \n\n[0570] 对得到的共聚物进行GPC分析，结果是重均分子量 $\\cdot\\mathrm{Mw}{=}96,000\\mathrm{,}\\mathrm{Mw/Mn}{=}3.9$ 。另外，进行 $^{13}\\mathrm{C-NMR}$ 分析，结果是共聚物的结构单元比率SPA-Na单元/GOBA单元/KBM-5103单元 $\\c=$ $91/5/4$ 。需要说明的是，未检测出环氧基开环而得到的单元。  \n\n[0571] [实施例45]  \n\n[0572] 将合成例1的共聚物变更为合成例12的共聚物，除此之外，与实施例1同样地进行涂覆溶液1的制备、底漆组合物的制备、底漆层的形成、涂覆膜的形成，得到在基材(玻璃板)上形成有底漆层及涂覆膜的层叠体。对得到的涂覆膜进行物性评价(外观、 $120^{\\circ}\\mathrm{C}$ 加热污垢附着试验、铅笔硬度、防雾性、防污性、密合性)。结果示于表17。  \n\n<html><body><table><tr><td rowspan=\"2\">No.</td><td rowspan=\"2\">共聚物 种类</td><td rowspan=\"2\">基材</td><td rowspan=\"2\">外观</td><td colspan=\"2\">水接触角</td><td colspan=\"2\">雾度</td><td rowspan=\"2\"></td><td rowspan=\"2\">铅笔硬度防雾性</td><td rowspan=\"2\">防污性</td><td rowspan=\"2\">密合性</td></tr><tr><td>加热前</td><td>120℃ ×12h</td><td>加热前</td><td>120C ×12h</td></tr><tr><td>实施例45</td><td>合成例12 (91/5/4)</td><td>玻璃</td><td>透明</td><td>9</td><td>13</td><td>0.2</td><td>0.3</td><td>2H</td><td></td><td></td><td>100/100</td></tr></table></body></html>  \n\n![](images/3a3d144553332fe0e2155ab7150e7e75dce3f56e5ff646dbf7163e93631ee72c.jpg)  \n\n[0576] 合成例12的共聚物(共聚聚合物) $\\mathtt{M w}{=}96,000$ 。  \n\n![](images/25d0e438f49082062483bd4564966d389fccf66354e1dc3f34136a4c28b329cc.jpg)  \n图1  \n\n![](images/ab10360c2a086aa6e130f09c77f1ad1ca9e250a8ba7b2f8a6d84e08cb063fe77.jpg)  \n图2",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# (19)中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利申请  \n\n(21)申请号 201710055059.4  \n(22)申请日 2017 .01 .24  \n(71)申请人 上海维凯光电新材料有限公司地址 201111 上海市闵行区昆阳路2055号申请人 上海乘鹰新材料有限公司  \n(72)发明人 虞明东　王艳梅  \n(74)专利代理机构 上海汉声知识产权代理有限公司 31236代理人 郭国中  \n\n(51)Int.Cl . C08G 65/0 (2006.01) C09D 171/0(2006.01)",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n季铵盐型亲水性紫外光固化树脂的制备方法",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明提供了一种季铵盐型亲水性紫外光固化树脂的制备方法，其包括如下步骤：将二元聚醚胺与丙烯酰氧乙基三甲基氯化铵在室温下进行迈克尔加成反应，得到双末端仲氨基化合物中间体；将所述双末端仲氨基化合物中间体与多官能度丙烯酸酯在 $40{\\sim}45^{\\circ}\\mathrm{C}$ 下进行迈克尔加成反应，得到所述季铵盐型亲水性紫外光固化树脂。本发明的优点在于：1、季铵盐型亲水性紫外光固化树脂制备简单，在较低温度下，短时间内通过两步迈克尔加成反应即可以制得；2、该季铵盐型亲水性紫外光固化树脂因为具有以化学键固定在光固化后形成的交联网络上的季铵盐结构，应用到防雾涂料中，可以保证涂膜具有优异的初始及持续防雾性能。  \n\n1.一种季铵盐型亲水性紫外光固化树脂的制备方法，其特征在于，包括如下步骤：  \n\n将二元聚醚胺与丙烯酰氧乙基三甲基氯化铵在室温下进行迈克尔加成反应，得到双末端仲氨基化合物中间体；  \n\n将所述双末端仲氨基化合物中间体与多官能度丙烯酸酯在 $40{\\sim}45^{\\circ}\\mathrm{C}$ 下进行迈克尔加成反应，得到所述季铵盐型亲水性紫外光固化树脂。  \n\n2.如权利要求1所述的季铵盐型亲水性紫外光固化树脂的制备方法，其特征在于，所述二元聚醚胺与丙烯酰氧乙基三甲基氯化铵的摩尔比为1:2。  \n\n3.如权利要求1或2所述的季铵盐型亲水性紫外光固化树脂的制备方法，其特征在于，所述二元聚醚胺选自D-230、D-400、D-2000、ED-600、ED-900和ED-2003中的至少一种。  \n\n4.如权利要求1所述的季铵盐型亲水性紫外光固化树脂的制备方法，其特征在于，所述多官能度丙烯酸酯为官能度不小于4的丙烯酸酯单体。  \n\n5.如权利要求4所述的季铵盐型亲水性紫外光固化树脂的制备方法，其特征在于，所述丙烯酸酯单体为含有乙氧基单元的多官单体。  \n\n6.如权利要求5所述的季铵盐型亲水性紫外光固化树脂的制备方法，其特征在于，所述含有乙氧基单元的多官单体中，乙氧基单元的数量不小于20个。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 季铵盐型亲水性紫外光固化树脂的制备方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明涉及一种季铵盐型亲水性紫外光固化树脂的制备方法，属于高分子材料合成技术领域。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 空气中的水蒸气在温度低于露点时，便会凝结成微小的液滴而成雾。这种不良的影响经常发生在窗户、浴室镜子、眼镜、游泳及潜水眼镜、挡风玻璃、光学仪器镜头、太阳能电池透光板、车灯、指示灯、农膜等这些与我们生活紧密相关的透明材料上。透明材料表面水滴雾化的结果，不仅透光率下降影响视觉，有时会产生危害，例如当雾滴凝结在如红外光学显微镜等精密分析仪器的透镜表面上时，其分析的准确性会降低。而当雾滴凝结在太阳能电池透光板上时，致使太阳能吸收效率降低，从而不利于太阳能电池设备充分发挥应有的作用。  \n\n[0003] 为了解决这些问题，一般会对材料表面进行超疏水或超亲水处理。超疏水常用全氟树脂类，一方面价格较高，另一方面该类树脂一般较软，耐磨性差，同时其疏水特性也导致其表面容易吸附油污和灰尘，反而达不到要求的效果。而有机亲水涂料本身价格较为便宜，也可通过一些改性来提高其耐磨性。使用有机亲水涂层相比于疏水涂层处理方法不但施工方便，而且价格低廉。  \n\n[0004] 现在国内外主要集中在超亲水的研究，如涂层表面引入能形成氢键的基团如羧基、氨基、巯基、羟基；一些离子基团：羧酸根、磺酸根、铵根、磷酸根等；或是引入亲水性的乙氧基单元，当引入一定数量的这些基团或是离子时，涂层的表面可以达到超亲水的状态，水汽冷凝后在基材表面高度铺展，形成一层均匀的水膜，消除了微小水珠对光线的漫反射而达到防雾的目的。目前制备超亲水的途径主要是通过物理共混、化学表面修饰、化学键接法。  \n\n[0005] 中国专利CN  104053731A公开了一种热固性防雾涂料，该涂料组合物包含聚氨酯分散体、改性氮丙啶固化剂、亲水性二氧化硅纳米粒子、表面活性剂。这是一种热固性水性涂料，需要在 $110^{\\circ}\\mathrm{C}$ 以上加热20分钟以上才能发生固化，形成交联网络。虽然防雾性能较好，但是能耗高而且这里起到亲水防雾性能的成分其实主要是表面活性剂，而它根本不参与固化反应，只是被交联网络物理固定而已，在高湿度的情况下，容易流失而影响持续防雾性能。另外，亲水性二氧化硅纳米粒子还需要采用带有亲水性基团的硅烷偶联剂来进行纳米二氧化硅分散体表面处理得到，工艺比较复杂。而且亲水性硅烷偶联剂价格比较贵，而且种类稀少。因此制造成本会提高。  \n\n[0006] 中国专利CN102911582A公开了一种紫外光固化防雾涂料。该涂料的主体亲水性树脂是由可聚合非离子表面活性剂烯丙氧基壬基苯氧基丙醇聚氧乙烯醚、丙烯酸酯及丙烯酸经自由基聚合得到侧链含有羧基的聚丙烯酸酯，然后侧链羧基进行开环甲基丙烯酸缩水甘油酯的环氧基而得到侧链含有双键的光固化亲水性聚丙烯酸酯。但是，烯丙氧基单体的聚合活性比丙烯酸酯类单体的聚合活性低很多，因此会残留大量的未反应烯丙氧基壬基苯氧基丙醇聚氧乙烯醚。残留的烯丙氧基壬基苯氧基丙醇聚氧乙烯醚在涂料中尽管也会发生光聚合反应，但是其聚合活性较低，因此还是会有部分残留在涂层内，没有参与固化反应形成交联网络，只是被交联网络物理固定而已，在高湿度的情况下，容易流失而影响持续防雾性能。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0007] 针对现有技术中的缺陷，本发明的目的是提供一种季铵盐型亲水性紫外光固化树脂，将其应用于紫外光固化防雾涂料配方中，经紫外光固化后，涂膜不但初期亲水性好，并且耐水性好，具有持久的防雾性能，涂膜硬度高、耐擦拭性好，非常适合应用于具有防雾性能要求高的领域，如车灯、挡风玻璃、浴室镜、光学透镜材料等。  \n\n[0008] 本发明是通过以下技术方案实现的：  \n\n[0009] 本发明提供一种季铵盐型亲水性紫外光固化树脂的制备方法，其包括如下步骤：[0010] 将二元聚醚胺与丙烯酰氧乙基三甲基氯化铵在室温下进行迈克尔加成反应，得到双末端仲氨基化合物中间体；  \n\n[0011] 将所述双末端仲氨基化合物中间体与多官能度丙烯酸酯在 $40{\\sim}45^{\\circ}\\mathrm{C}$ 下进行迈克尔加成反应，得到所述季铵盐型亲水性紫外光固化树脂。  \n\n[0012] 作为优选方案，所述二元聚醚胺与丙烯酰氧乙基三甲基氯化铵的摩尔比为1:2。  \n\n[0013] 作为优选方案，所述二元聚醚胺选自D-230、D-400、D-2000、ED-600、ED-900和ED-2003中的至少一种。  \n\n[0014] 作为优选方案，所述多官能度丙烯酸酯为官能度不小于4的丙烯酸酯单体。若采用官能度小于4的丙烯酸酯单体，则制备的光固化树脂的官能度低，耐水性会降低，持续防雾性能差，另外耐磨性也会相应降低。作为优选方案，所述丙烯酸酯单体为含有乙氧基单元的多官单体。  \n\n[0015] 作为优选方案，所述含有乙氧基单元的多官单体中，乙氧基单元的数量不小于20个。所述乙氧基单元少于20个时，会导致多官能度亲水性紫外光固化树脂亲水性太差，防雾性能差。  \n\n[0016] 采用本发明方法制备的季铵盐型亲水性紫外光固化树脂的亲水程度可以由合成原料来控制，例如二元聚醚胺的分子量大，即乙氧基或异丙氧基数越多，亲水性越大；多官能度丙烯酸酯中乙氧基单元数越多，亲水性越大。对于多官能度丙烯酸酯，在同样乙氧基单元数的情况下，官能度越大，亲水性越小。因此，采用该季铵盐型亲水性紫外光固化树脂作为主体树脂用于光固化防雾涂料体系中，由于引入大量的亲水性部分，涂膜具有优异的亲水性能，可以使空气中的水汽凝结在其表面形成水膜而不是水滴，具有很好的初始防雾性能。另一方面，由于多官能度结构，可以与涂料体系中的其它紫外光固化树脂或单体，经紫外光固化后形成交联网络结构，亲水性部分不是以物理方式固定在交联网络上，而是以化学键固定在交联网络上，不会引起水或水蒸气使涂膜泡掉，所以涂膜持续亲水性好，体现出具有持续防雾性能。  \n\n[0017] 与现有技术相比，本发明具有如下的有益效果：  \n\n[0018] 1、季铵盐型亲水性紫外光固化树脂制备简单，在较低温度下，短时间内通过两步迈克尔加成反应即可以制得；  \n\n[0019] 2、该季铵盐型亲水性紫外光固化树脂因为具有以化学键固定在光固化后形成的交联网络上的季铵盐结构，应用到防雾涂料中，可以保证涂膜具有优异的初始及持续防雾性能；  \n\n[0020] 3、该季铵盐型亲水性紫外光固化树脂的亲水程度可以按照需求随意控制，要满足一些领域的超亲水性需要时，可以选择乙氧基或异丙氧基数目多的二元聚醚胺和乙氧基数多的官能度稍低的多官能度丙烯酸酯，要满足具有优异耐水性，即保证初始防雾性，还兼具有优异持续防雾性能好的领域需求时，可以通过使用官能度高的多官能度丙烯酸酯来达到；  \n\n[0021] 4、采用本发明的季铵盐型亲水性紫外光固化树脂用于紫外光固化防雾涂料配方中，经紫外光固化后，涂膜初期亲水性好，同时具有很好的耐水性，反映在防雾性能上就是不但初始防雾性能好，而且具有持久的防雾性能。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 具体实施方式  \n\n[0022] 下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。  \n\n[0023] 本发明的铵盐型亲水性紫外光固化树脂的制备方法如下：[0024] 由于市售原材料限制，多官丙烯酸酯只采用以下四种：[0025] 3官：乙氧基三羟甲基丙烷三丙烯酸酯(EO35mol)，其中的乙氧基数量为35；[0026] 4官：乙氧基季戊四醇四丙烯酸酯(EO15mol)，其中的乙氧基数量为15；[0027] 4官：乙氧基季戊四醇四丙烯酸酯(EO35mol)，其中的乙氧基数量为35；[0028] 4官：乙氧基季戊四醇四丙烯酸酯 $\\mathrm{(E0120mol)}$ )，其中的乙氧基数量为120；[0029] 6官：乙氧基双季戊四醇六丙烯酸酯(EO96mol)，其中的乙氧基数量为96。  \n\n[0030] 实施例1  \n\n[0031] 本实施例涉及一种季铵盐型亲水性紫外光固化树脂的制备方法，具体包括如下步骤：  \n\n[0032] 在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(70克)，阻聚剂对羟基苯甲醚(0 .14克)，聚醚胺D400(2.30克，5mmol)和 $80\\%$ 丙烯酰氧乙基三甲基氯化铵水溶液(24 .2克，10mmol)，室温反应1 .5小时，FT-IR检测不到 $810\\mathrm{cm}^{-1}$ 处双键的吸收峰，第一步反应结束。然后加入乙氧基双季戊四醇六丙烯酸酯(EO96mol)(48.02克，10mmol)，升温至 $45\\mathrm{^\\circC}$ 反应3小时，FT-IR检测不到 $3400{-}3300{\\mathrm{cm}}^{-1}$ 处仲胺的吸收峰，结束反应，得到浅黄色透明液体。然后用正己烷进行沉淀，再经 $50^{\\circ}\\mathrm{C}$ 真空干燥12小时得到官能度为10的季铵盐型亲水性紫外光固化树脂。  \n\n[0033] 实施例2  \n\n[0034] 本实施例涉及一种季铵盐型亲水性紫外光固化树脂的制备方法，具体包括如下步骤：  \n\n[0035] 在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(78克)，阻聚剂对羟基苯甲醚(0 .16克)，聚醚胺D400(2.30克，5mmol)和 $80\\%$ 丙烯酰氧乙基三甲基氯化铵水溶液(24 .2克，10mmol)，室温反应1 .5小时，FT-IR检测不到 $810\\mathrm{cm}^{-1}$ 处双键的吸收峰，第一步反应结束。然后加入乙氧基季戊四醇四丙烯酸酯 $\\mathrm{(E0120mol)}$ )(56 .32克，10mmol)，升温至 $45\\mathrm{^\\circC}$ 反应3小时，FT-IR检测不到 $3400{-}3300{\\mathrm{cm}}^{-1}$ 处仲胺的吸收峰，结束反应，得到浅黄色透明液体。然后用正己烷进行沉淀，再经 $50^{\\circ}\\mathrm{C}$ 真空干燥12小时得到官能度为6的季铵盐型亲水性紫外光固化树脂。  \n\n[0036] 实施例3  \n\n[0037] 本实施例涉及一种季铵盐型亲水性紫外光固化树脂的制备方法，具体包括如下步骤：  \n\n[0038] 在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(70克)，阻聚剂对羟基苯甲醚(0 .14克)，聚醚胺ED-600(2.64克，5mmol)和 $80\\%$ 丙烯酰氧乙基三甲基氯化铵水溶液(24 .2克，10mmol)，室温反应1 .5小时，FT-IR检测不到 $810\\mathrm{cm}^{-1}$ 处双键的吸收峰，第一步反应结束。然后加入乙氧基双季戊四醇六丙烯酸酯(EO96mol)(48.02克，10mmol)，升温至 $45\\mathrm{^\\circC}$ 反应3小时，FT-IR检测不到 $3400{-}3300{\\mathrm{cm}}^{-1}$ 处仲胺的吸收峰，结束反应，得到浅黄色透明液体，然后用正己烷进行沉淀，再经 $50^{\\circ}\\mathrm{C}$ 真空干燥12小时得到官能度为10的季铵盐型亲水性紫外光固化树脂。  \n\n[0039] 实施例4  \n\n[0040] 本实施例涉及一种季铵盐型亲水性紫外光固化树脂的制备方法，具体包括如下步骤：  \n\n[0041] 在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(76克)，阻聚剂对羟基苯甲醚(0 .17克)，聚醚胺ED-900(10 .0克，10mmol)和 $80\\%$ 丙烯酰氧乙基三甲基氯化铵水溶液(48.4克，20mmol)，室温反应1.5小时，FT-IR检测不到 $810\\mathrm{cm}^{-1}$ 处双键的吸收峰，第一步反应结束。然后加入乙氧基季戊四醇四丙烯酸酯 $\\left(\\mathrm{E035mol}\\right)$ )(37 .8克，20mmol)，升温至 $45\\mathrm{^\\circC}$ 反应3小时，FT-IR检测不到 $3400{\\sim}3300\\mathrm{cm}^{-1}$ 处仲胺的吸收峰，结束反应，得到浅黄色透明液体，然后用正己烷进行沉淀，再经 $50^{\\circ}\\mathrm{C}$ 真空干燥12小时得到官能度为6的季铵盐型亲水性紫外光固化树脂。  \n\n[0042] 实施例5  \n\n[0043] 本实施例涉及一种季铵盐型亲水性紫外光固化树脂的制备方法，具体包括如下步骤：  \n\n[0044] 在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(75克)，阻聚剂对羟基苯甲醚(0 .17克)，聚醚胺ED-900(5 .0克，5mmol)和 $80\\%$ 丙烯酰氧乙基三甲基氯化铵水溶液(24 .2克，10mmol)，室温反应1 .5小时，FT-IR检测不到 $810\\mathrm{cm}^{-1}$ 处双键的吸收峰，第一步反应结束。然后加入乙氧基季戊四醇四丙烯酸酯 $\\mathrm{(E0120mol)}$ )(56 .32克，10mmol)，升温至 $45\\mathrm{^\\circC}$ 反应3小时，FT-IR检测不到 $3400{-}3300{\\mathrm{cm}}^{-1}$ 处仲胺的吸收峰，结束反应，得到浅黄色透明液体，然后用正己烷进行沉淀，再经 $50^{\\circ}\\mathrm{C}$ 真空干燥12小时得到官能度为6的季铵盐型亲水性紫外光固化树脂。  \n\n[0045] 对比例1  \n\n[0046] 在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(72克)，阻聚剂对羟基苯甲醚(0 .14克)，己二胺(0 .58克，5mmol)和 $80\\%$ 丙烯酰氧乙基三甲基氯化铵水溶液(24 .2克，10mmol)，室温反应1 .5小时，FT-IR检测不到 $810\\mathrm{cm}^{-1}$ 处双键的吸收峰，第一步反应结束。然后加入乙氧基双季戊四醇六丙烯酸酯(EO96mol)(48.02克，10mmol) ,升温至45$\\mathrm{{^\\circC}}$ 反应3小时，FT-IR检测不到 $3400{-}3300{\\mathrm{cm}}^{-1}$ 处仲胺的吸收峰，结束反应，得到浅黄色透明液体，然后用正己烷进行沉淀，再经 $50^{\\circ}\\mathrm{C}$ 真空干燥12小时得到官能度为10的季铵盐型亲水性紫外光固化树脂。  \n\n[0047] 对比例2  \n\n[0048] 在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(62克)，阻聚剂对羟基苯甲醚(0.12克)，聚醚胺D400(4.6克，5mmol)和丙烯酸二甲氨基乙酯(14.22克，10mmol)，室温反应1 .5小时，FT-IR检测不到 $810\\mathrm{cm}^{-1}$ 处双键的吸收峰，第一步反应结束。然后加入乙氧基季戊四醇四丙烯酸酯 $\\left(\\mathrm{E0120mol}\\right)$ )(56 .32克，10mmol)，升温至 $45\\mathrm{^\\circC}$ 反应3小时，FT-IR检测不到 $3400{-}3300{\\mathrm{cm}}^{-1}$ 处仲胺的吸收峰，结束反应，得到浅黄色透明液体，然后用正己烷进行沉淀，再经 $50^{\\circ}\\mathrm{C}$ 真空干燥12小时得到官能度为6的亲水性紫外光固化树脂。  \n\n[0049] 对比例3  \n\n[0050] 在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(60克)，阻聚剂对羟基苯甲醚(0 .14克)，聚醚胺ED-900(10 .0克，10mmol)和 $80\\%$ 丙烯酰氧乙基三甲基氯化铵水溶液(48 .4克，20mmol)，室温反应1 .5小时，FT-IR检测不到 $810\\mathrm{cm}^{-1}$ 处双键的吸收峰，第一步反应结束。然后加入乙氧基季戊四醇四丙烯酸酯 $\\left(\\mathrm{E015mol}\\right)$ )(20 .24克，20mmol)，升温至 $45\\mathrm{^\\circC}$ 反应3小时，FT-IR检测不到 $3400{-}3300{\\mathrm{cm}}^{-1}$ 处仲胺的吸收峰，结束反应，得到浅黄色透明液体，然后用正己烷进行沉淀，再经 $50^{\\circ}\\mathrm{C}$ 真空干燥12小时得到官能度为6的亲水性紫外光固化树脂。  \n\n[0051] 对比例4  \n\n[0052] 在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(75克)，阻聚剂对羟基苯甲醚(0 .17克)，聚醚胺ED-900(10 .0克，10mmol)和 $80\\%$ 丙烯酰氧乙基三甲基氯化铵水溶液(48 .4克，20mmol)，室温反应1 .5小时，FT-IR检测不到 $810\\mathrm{cm}^{-1}$ 处双键的吸收峰，第一步反应结束。然后加入乙氧基三羟甲基丙烷三丙烯酸酯 $\\left(\\mathrm{E035mol}\\right)$ ) (36 .72克，20mmol)，升温至 $45\\mathrm{^\\circC}$ 反应3小时，FT-IR检测不到 $3400{-}3300{\\mathrm{cm}}^{-1}$ 处仲胺的吸收峰，结束反应，得到浅黄色透明液体，然后用正己烷进行沉淀，再经 $50^{\\circ}\\mathrm{C}$ 真空干燥12小时得到官能度为4的亲水性紫外光固化树脂。  \n\n[0053] 性能测试  \n\n[0054] 对所实施例 $1{\\sim}5$ 及对比例 $1{\\sim}4$ 制备的季铵盐型亲水性紫外光固化树脂，分别配成列于表1中的应用实施例 $1\\sim5$ 及应用对比例 $1{\\sim}4$ 的紫外光固化防雾涂料后，以PET作为基材，将应用实施例和应用对比例制备的涂料用10号线棒涂布在其表面，放入 $60^{\\circ}\\mathrm{C}$ 烘箱1min，之后经过紫外光固化，能量为 $500\\mathrm{mJ/cm^{2}}$ 。  \n\n[0055] 分别对应用实施例 $1\\sim5$ 及应用对比例 $1{\\sim}4$ 制得的涂层进行性能检测，测定涂层的附着力、铅笔硬度、耐磨性、初期水接触角和持续水接触角及防雾性能。具体结果列于表1中。  \n\n[0056] 具体性能检测项目及对应的方法如下：  \n\n[0057] 一、附着力  \n\n[0058] 采用百格法，用3M不干胶带对样张附着力进行测试。  \n\n[0059] 评估方法：  \n\n[0060] 5B－划线边缘光滑，在划线的边缘及交叉点处均无涂层脱落；  \n[0061] 4B－在划线的交叉点处有小片的涂层脱落，并且脱落总面积小于 $5\\%$ ；  \n[0062] 3B－在划线的边缘及交叉点处有小片的涂层脱落，并且脱落总面积在 $5\\sim15\\%$ 之间；  \n[0063] 2B－在划线的边缘及交叉点处有成片的涂层脱落，并且脱落总面积在 $15\\sim35\\%$ 之间；  \n[0064] 1B－在划线的边缘及交叉点处有成片的涂层脱落，并且脱落总面积在 $35\\sim65\\%$ 之间；  \n[0065] 0B－在划线的边缘及交叉点处有成片的涂层脱落，并且脱落总面积大于 $65\\%$ 。[0066] 二、铅笔硬度  \n[0067] 参照国家标准GB/T6739《漆膜硬度铅笔测定法》。  \n[0068] 三、耐磨性能  \n[0069] 使用0000#钢丝绒， $300\\mathrm{g}$ 力，一个来回记为一次，记录表面出现刮花的次数。[0070] 评估方法：经过一定次数的摩擦后，观察涂层是否有刮痕，记录无刮痕时所能耐受的最多摩擦次数。  \n[0071] 四、初期亲水角  \n[0072] 在固化好的试样表面滴4μL去离子水，在 $20{\\sim}25^{\\circ}\\mathrm{C}$ 范围内用接触角测试仪测定。[0073] 五、持续亲水角  \n[0074] 将固化好的试样放入去离子水中浸泡24h，晾干后用接触角测量仪测定。  \n[0075] 六：防雾性：把表面温度为25度的测试板水平置于 $80^{\\circ}\\mathrm{C}$ 的水面上方10cm处，观察样板起雾的时间。  \n[0076] X  1秒内起雾、  \n[0077] $\\Delta:10$ 秒后起雾、  \n[0078] $\\bigcirc$ ：30秒后起雾、  \n[0079] $\\textcircled{9}$ ：不起雾。  \n[0080] 表1  \n\n<html><body><table><tr><td rowspan=\"2\">原料</td><td rowspan=\"2\">化学名</td><td colspan=\"5\">应用实施例（重量份数)</td><td colspan=\"4\">应用对比例 （重量份数）</td></tr><tr><td>1</td><td>2</td><td>3</td><td>４</td><td>５</td><td>１</td><td>２</td><td>3</td><td>4</td></tr><tr><td>亲水性光 固化树脂 疏水性光</td><td>多官丙 烯酸树 脂 10官聚</td><td>60</td><td>60</td><td>60</td><td>60</td><td>60</td><td>60</td><td>60</td><td>60</td><td>60</td></tr><tr><td>[0081]</td><td>氨酯丙 烯酸酯 固化树脂 （长兴 6195) 三羟甲</td><td></td><td></td><td></td><td></td><td>25</td><td></td><td></td><td></td><td></td></tr><tr><td rowspan=\"2\"></td><td>疏水性单 体</td><td>基丙烷 三丙烯 酸酯</td><td></td><td></td><td></td><td>5</td><td></td><td></td><td></td><td></td></tr><tr><td>甲基丙 亲水性光 烯酸羟 固化单体 丙基磺 酸钠</td><td></td><td></td><td></td><td></td><td>5</td><td></td><td></td><td></td><td></td></tr><tr><td rowspan=\"2\">光引发剂</td><td>184</td><td></td><td></td><td></td><td></td><td>3</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>TPO</td><td></td><td></td><td></td><td></td><td>2</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>溶剂</td><td></td><td>乙酸乙</td><td></td><td></td><td></td><td>100</td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td rowspan=\"3\"></td><td>酯</td><td colspan=\"8\"></td></tr><tr><td>乙酸丁 酯</td><td colspan=\"8\">150</td></tr><tr><td>异丙醇</td><td colspan=\"8\">50</td></tr><tr><td>阻聚剂</td><td>对羟基 苯甲醚</td><td colspan=\"8\">0.05</td></tr><tr><td rowspan=\"6\">性能测试</td><td>附着</td><td>5B</td><td>5B</td><td>5B</td><td>5B</td><td>5B</td><td>5B</td><td>5B</td><td>5B</td><td>5B</td></tr><tr><td>铅笔硬 度</td><td>2H</td><td>2H</td><td>2H</td><td>2H</td><td>2H</td><td>2H</td><td>2H</td><td>2H</td><td>H</td></tr><tr><td>耐磨</td><td>46</td><td>42</td><td>45</td><td>49</td><td>41</td><td>56</td><td>49</td><td>53</td><td>33</td></tr><tr><td>防雾性</td><td></td><td></td><td></td><td></td><td></td><td>X</td><td>X</td><td>X</td><td>O</td></tr><tr><td>初期水 接触角</td><td>9. 3</td><td>< 5</td><td>8. 3</td><td>9. 5</td><td>< 5</td><td>51. 6</td><td>45.1</td><td>28.5</td><td><5</td></tr><tr><td>持续水 接触角</td><td>28 .9</td><td>27 .6</td><td>29 .8</td><td>33 .1</td><td>31 .5</td><td>一</td><td>一</td><td>51.6</td><td>46.2</td></tr></table></body></html>  \n\n[0083] 由表1可以看出，应用实施例 $1\\sim5$ 具有较好的防雾性能。初始水接触角均低于10度，24小时浸泡后的水接触角均低于35度，防雾性能优良，同时耐磨性也好。  \n\n[0084] 应用对比例1与应用实施例1相比,由于所用季铵盐型亲水性紫光固化树脂合成时,采用己二胺来代替聚醚胺D400，所得最终季铵盐型亲水性紫外光固化树脂的亲水性比较差，因此用在防雾涂料配方中，虽然涂层耐磨性有较大提高，但是导致涂层的亲水性差，因而不具备防雾性能。  \n\n[0085] 应用对比例2与应用实施例2相比，由于所用亲水性紫外光固化树脂合成时，第一步反应时，采用丙烯酰氧乙基三甲基氯化铵的前驱体-丙烯酸二甲氨基乙酯来代替它时，所得亲水性紫外光固化树脂只是非离子型的，不含季铵盐，其亲水性比较差，因此用在防雾涂料配方中，涂层的亲水性差，不具备防雾性能。  \n\n[0086] 应用对比例3与应用实施例4相比，由于所用季铵盐型亲水性紫外光固化树脂合成时，采用乙氧基季戊四醇四丙烯酸酯(EO15mol)，所得最终季铵盐型亲水性紫外光固化树脂的亲水性比较差，因此用在防雾涂料配方中，虽然涂层耐磨性稍有提高，但是导致涂层的亲水性差，因而不具备防雾性能。  \n\n[0087] 应用对比例4与应用实施例4相比，由于所用季铵盐亲水性紫外光固化树脂合成时，采用乙氧基三羟甲基丙烷三丙烯酸酯(EO35mol) ,得到四官能度季铵盐型亲水性紫外光固化树脂。因最终树脂官能度较低，亲水性太好，导致最终涂层由于水溶胀而使亲水部分网络从基材表面脱离，导致涂层中疏水部分占大多数，而使亲水性大大降低。同时涂层的耐磨和硬度也显著降低。  \n\n[0088] 以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# (19)中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利申请  \n\nC08G 81/0 (2006.01)  \n\n(21)申请号 201710055097 .X  \n(22)申请日 2017 .01 .24  \n(71)申请人 上海乘鹰新材料有限公司地址 201512 上海市金山区金山大道5099号申请人 上海维凯光电新材料有限公司  \n(72)发明人 虞明东　王艳梅  \n(74)专利代理机构 上海汉声知识产权代理有限公司 31236代理人 郭国中  \n(51)Int.Cl .C09D 171/02(2006.01)C09D 187/0(2006.01)C08G 65/3 2(2006.01)C08G 65/3 3(2006.01)",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n多官能度亲水性紫外光固化树脂的制备方法及其应用",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明提供了一种多官能度亲水性紫外光固化树脂的制备方法及其应用，所述制备方法采用两步迈克尔加成法，具体为采用二元聚醚胺与两倍当量的甲氧基聚乙二醇丙烯酸酯经迈克尔加成反应得到双末端仲氨基化合物中间体；然后该中间体再与两倍当量的多官能度丙烯酸酯进行迈克尔加成反应即得光固化树脂。本发明制得的光固化树脂应用于紫外光防雾涂料配方中，经紫外光固化后，涂膜不但初期亲水性好，并且耐水性好，具有持久的防雾性能，涂膜硬度高、耐擦拭性好。非常适合用于具有防雾性能要求高的领域，如车灯、挡风玻璃、浴室镜、光学透镜材料等。  \n\n1.一种多官能度亲水性紫外光固化树脂的制备方法，其特征在于，所述方法包括以下步骤：  \n\n室温条件下，将二元聚醚胺与两倍当量的甲氧基聚乙二醇丙烯酸酯在乙醇溶剂中进行迈克尔加成反应1-2小时，得到双末端仲氨基化合物中间体；  \n\n所述双末端仲氨基化合物中间体再与两倍当量的多官能度丙烯酸酯在 $40–45^{\\circ}\\mathrm{C}$ 条件下，进行迈克尔加成反应2-3小时，即得到多官能度亲水性紫外光固化树脂。  \n\n2.根据权利要求1所述的多官能度亲水性紫外光固化树脂的制备方法，其特征在于，所述二元聚醚胺包括亨斯迈公司生产的D-230、D-400、D-2000、D4000、ED-600、ED-900、ED-2003中的一种。  \n\n3.根据权利要求2所述的多官能度亲水性紫外光固化树脂的制备方法，其特征在于，所述二元聚醚胺为D-400、ED-600、ED-900、ED-2003中的一种。  \n\n4.根据权利要求1所述的多官能度亲水性紫外光固化树脂的制备方法，其特征在于，所述甲氧基聚乙二醇丙烯酸酯中的聚乙二醇单元的分子量不小于400。  \n\n5.根据权利要求1所述的多官能度亲水性紫外光固化树脂的制备方法，其特征在于，所述甲氧基聚乙二醇丙烯酸酯中的聚乙二醇单元的分子量不小于600。  \n\n6.根据权利要求1所述的多官能度亲水性紫外光固化树脂的制备方法，其特征在于，所述多官能度丙烯酸酯为官能度不小于4的丙烯酸酯单体。  \n\n7.根据权利要求6所述的多官能度亲水性紫外光固化树脂的制备方法，其特征在于，所述多官能度丙烯酸酯中含有乙氧基单元，所述乙氧基单元的数量为不小于20个。  \n\n8.根据权利要求7所述的多官能度亲水性紫外光固化树脂的制备方法，其特征在于，所述乙氧基单元的数量不少于30个。  \n\n9.根据权利要求1所述的多官能度亲水性紫外光固化树脂的制备方法，其特征在于，所述方法得到的多官能度亲水性紫外光固化树脂的官能度不小于4。  \n\n10.一种根据权利要求1所述方法制备的多官能度亲水性紫外光固化树脂在防雾涂料中的应用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 多官能度亲水性紫外光固化树脂的制备方法及其应用",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明属于高分子合成技术领域，具体涉及一种多官能度亲水性紫外光固化树脂的制备方法及其应用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 空气中的水蒸气在温度低于露点时，便会凝结成微小的液滴而成雾。这种不良的影响经常发生在窗户、浴室镜子、眼镜、游泳及潜水眼镜、挡风玻璃、光学仪器镜头、太阳能电池透光板、车灯、指示灯、农膜等这些与我们生活紧密相关的透明材料上。透明材料表面水滴雾化的结果，不仅透光率下降影响视觉，有时会产生危害，例如当雾滴凝结在如红外光学显微镜等精密分析仪器的透镜表面上时，其分析的准确性会降低。而当雾滴凝结在太阳能电池透光板上时，致使太阳能吸收效率降低，从而不利于太阳能电池设备充分发挥应有的作用。  \n\n[0003] 为了解决这些问题，一般会对材料表面进行疏水或亲水处理。疏水常用全氟树脂类，一方面价格较高，另一方面该类树脂一般较软，耐磨性差，同时其疏水特性也导致其表面容易吸附油污和灰尘，反而达不到要求的效果。而有机亲水涂料本身价格较为便宜，也可通过一些改性来提高其耐磨性。使用有机亲水涂层相比于疏水涂层处理方法不但施工方便，而且价格低廉。  \n\n[0004] 现在国内外主要集中在超亲水的研究，如涂层表面引入能形成氢键的基团如羧基、氨基、巯基、羟基，或是一些离子基团：羧酸根、磺酸根、铵根、磷酸根等，当引入这些基团或是离子时，涂层的表面达到超亲水的状态，水汽冷凝后在基材表面高度铺展，形成一层均匀的水膜，消除了微小水珠对光线的漫反射而达到防雾的目的。目前制备超亲水的途径主要是通过物理共混、化学表面修饰、化学键接法。目前市场上的防雾涂层一般都是初始防雾性能较好，但使用一段时间后，防雾性能便下降明显，即持续防雾性能差。  \n\n[0005] 中国专利CN  104053731A公开了一种热固性防雾涂料，该涂料组合物包含聚氨酯分散体、改性氮丙啶固化剂、亲水性二氧化硅纳米粒子、表面活性剂。这是一种热固性水性涂料，需要在110度以上加热20分钟以上才能发生固化，形成交联网络。虽然防雾性能较好，但是能耗高而且这里起到亲水防雾性能的成分其实主要是表面活性剂，而它根本不参与固化反应，只是被交联网络物理固定而已，在高湿度的情况下，容易流失而影响持续防雾性能。另外，亲水性二氧化硅纳米粒子还需要采用带有亲水性基团的硅烷偶联剂来进行纳米二氧化硅分散体表面处理得到，工艺比较复杂。而且亲水性硅烷偶联剂价格比较贵，而且种类稀少。因此制造成本会提高。  \n\n[0006] 中国专利CN102911582A公开了一种紫外光固化防雾涂料。该涂料的主体亲水性树脂是由可聚合非离子表面活性剂烯丙氧基壬基苯氧基丙醇聚氧乙烯醚、丙烯酸酯及丙烯酸经自由基聚合得到侧链含有羧基的聚丙烯酸酯，然后侧链羧基进行开环甲基丙烯酸缩水甘油酯的环氧基而得到侧链含有双键的光固化亲水性聚丙烯酸酯。但是，烯丙氧基单体的聚合活性比丙烯酸酯类单体的聚合活性低很多，因此会残留大量的未反应烯丙氧基壬基苯氧基丙醇聚氧乙烯醚。残留的烯丙氧基壬基苯氧基丙醇聚氧乙烯醚在涂料中尽管也会发生光聚合反应，但是其聚合活性较低，因此还是会有部分残留在涂层内，没有参与固化反应形成交联网络，只是被交联网络物理固定而已，在高湿度的情况下，容易流失而影响持续防雾性能。  \n\n[0007] 市面上的防雾涂料大多数存在持续防雾效果一般。持续防雾性好就要求涂膜的耐磨性好，但耐磨性好又与初始防雾性能好是彼此矛盾的。因此，为解决这一矛盾，急需开发亲水且耐磨性优的防雾涂料,这样才能保证涂层兼具好的初始防雾和持续防雾性能。而要满足这样的要求，开发防雾涂料的主体成分-亲水且耐磨性好的亲水性树脂是非常有必要的。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0008] 针对现有技术中的缺陷，本发明的目的是提供一种多官能度亲水性紫外光固化树脂的制备方法及其应用，所制备的树脂用于紫外光防雾涂料配方中，经紫外光固化后，涂膜不但初期亲水性好，并且耐水性好，具有持久的防雾性能，涂膜硬度高、耐擦拭性好，非常适合应用于具有防雾性能要求高的领域，如车灯、挡风玻璃、浴室镜、光学透镜材料等。  \n\n[0009] 本发明的目的是通过以下技术方案实现的：  \n\n[0010] 本发明提供了一种多官能度亲水性紫外光固化树脂的制备方法，所述方法包括以下步骤：  \n\n[0011] 室温条件下，将二元聚醚胺与两倍当量的甲氧基聚乙二醇丙烯酸酯在乙醇溶剂中进行迈克尔加成反应1-2小时，得到双末端仲氨基化合物中间体；  \n\n[0012] 所述双末端仲氨基化合物中间体再与两倍当量的多官能度丙烯酸酯在 $40–45^{\\circ}\\mathrm{C}$ 条件下，进行迈克尔加成反应2-3小时，即得到多官能度亲水性紫外光固化树脂。  \n\n[0013] 优选地，所述二元聚醚胺包括亨斯迈公司生产的D-230、D-400、D-2000、D4000、ED-600、ED-900、ED-2003中的一种。  \n\n[0014] 优选地，所述二元聚醚胺为D-400、ED-600、ED-900、ED-2003中的一种。  \n\n[0015] 优选地，所述甲氧基聚乙二醇丙烯酸酯中的聚乙二醇单元的分子量不小于400。若甲氧基聚乙二醇丙烯酸酯中的聚乙二醇单元的分子量小于400，则会导致多官能度亲水性紫外光固化树脂亲水性太差，防雾性能差。  \n\n[0016] 优选地，所述甲氧基聚乙二醇丙烯酸酯中的聚乙二醇单元的分子量不小于600。  \n\n[0017] 优选地，所述多官能度丙烯酸酯为官能度不小于4的丙烯酸酯单体。若采用官能度小于4的丙烯酸酯单体，则制备的光固化树脂的官能度低，耐水性会降低，持续防雾性能差，另外耐磨性也会相应降低。  \n\n[0018] 优选地，所述多官能度丙烯酸酯中含有乙氧基单元，所述乙氧基单元的数量为不小于20个。所述乙氧基单元少于20个时，会导致多官能度亲水性紫外光固化树脂亲水性太差，防雾性能差。  \n\n[0019] 优选地，所述乙氧基单元的数量不少于30个。  \n\n[0020] 优选地，所述方法得到的多官能度亲水性紫外光固化树脂的官能度不小于4。  \n\n[0021] 本发明还提供了一种根据所述方法制备的多官能度亲水性紫外光固化树脂在防雾涂料中的应用。  \n\n[0022] 采用上述方法制备的多官能度亲水性紫外光固化树脂的亲水程度可以由合成原料来控制，例如二元聚醚胺的分子量大，即乙氧基或异丙氧基数越多，亲水性越大；甲氧基聚乙二醇丙烯酸酯结构中聚乙二醇单元的分子量越高，亲水性越大；多官能度丙烯酸酯中乙氧基单元数越多，亲水性越大。对于多官能度丙烯酸酯，在同样乙氧基单元数的情况下，官能度越大，亲水性越小。因此，采用该多官能度亲水性紫外光固化树脂作为主体树脂用于光固化防雾涂料体系中，由于引入大量的亲水性部分，涂膜具有优异的亲水性能，可以使空气中的水汽凝结在其表面形成水膜而不是水滴，具有很好的初始防雾性能。另一方面，由于多官能度结构，可以与涂料体系中的其它紫外光固化树脂或单体，经紫外官方固化后形成交联网络结构，亲水性部分不是以物理方式固定在交联网络上，而是以化学键固定在交联网络上，不会引起水或水蒸气使涂膜泡掉，所以涂膜持续亲水性好，体现出具有持续防雾性能。  \n\n[0023] 现有技术相比，本发明具有如下的有益效果：  \n\n[0024] 1、本发明采用的多官能度亲水性紫外光固化树脂的制备方法简单，在较低温度下，短时间内通过两步迈克尔加成反应即可以制得，而且不用后处理，可以直接使用。[0025] 2、本发明的多官光固化亲水性紫外光固化树脂的亲水程度可以按照需求随意控制。要满足一些领域的超亲水性需要时，可以选择乙氧基或异丙氧基数目多的二元聚醚胺和聚乙二醇单元分子量大的甲氧基聚乙二醇丙烯酸酯，以及乙氧基数多、官能度稍低的多官能度丙烯酸酯。要满足具有优异耐磨性，即保证初始防雾性，还兼具有优异持续防雾性能好的领域需求时，可以通过使用官能度高的多官能度丙烯酸酯来达到。[0026] 3、采用本发明的多官能度亲水性紫外光固化树脂用于光固化防雾涂料配方中，经紫外光固化后，涂膜初期亲水性好，具有优异的耐磨性能，因此具有很好的耐水性。反映在防雾性能上就是不但初期防雾性能好，而且具有持久的防雾性能。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 具体实施方式  \n\n[0027] 下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。  \n\n[0028] 本实施例和对比例的多官能度光固化亲水性树脂的制备中采用的原料如下：[0029] 由于市售原材料限制，甲氧基聚乙二醇丙烯酸酯只采用以下四种：[0030] 甲氧基甲氧基聚乙二醇(400)丙烯酸酯，甲氧基甲氧基聚乙二醇(600)丙烯酸酯，甲氧基聚乙二醇(1000)丙烯酸酯和甲氧基聚乙二醇(2000)丙烯酸酯。  \n\n[0031] 乙氧基多官丙烯酸酯采用以下五种：  \n\n[0032] 3官：乙氧基三羟甲基丙烷三丙烯酸酯 $\\left(\\mathrm{E035mol}\\right)$ )，其中的乙氧基数量为35；  \n[0033] 4官：乙氧基季戊四醇四丙烯酸酯(EO15mol)，其中的乙氧基数量为15；  \n[0034] 4官：乙氧基季戊四醇四丙烯酸酯(EO35mol)，其中的乙氧基数量为35；  \n[0035] 4官：乙氧基季戊四醇四丙烯酸酯 $\\mathrm{(E0120mol)}$ )，其中的乙氧基数量为120；  \n[0036] 6官：乙氧基双季戊四醇六丙烯酸酯(EO96mol)，其中的乙氧基数量为96。  \n[0037] 实施例1  \n\n[0038] 本实施例提供了一种多官能度亲水性紫外光固化树脂的制备方法，具体步骤如下：在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(61克)，阻聚剂对羟基苯甲醚(0 .18克)，聚醚胺D-400(2 .30克，5mmol)和甲氧基聚乙二醇(1000)丙烯酸酯(10.54克，10mmol)，室温反应1 .5小时，FT-IR检测不到 $810\\mathrm{cm}^{-1}$ 处双键的吸收峰，第一步反应结束。然后加入乙氧基双季戊四醇六丙烯酸酯(EO96mol)(48.02克，10mmol) ,升温至45度反应3小时，FT-IR检测不到 $3400{-}3300{\\mathrm{cm}}^{-1}$ 处仲胺的吸收峰，结束反应，得到浅黄色透明液体，为 $50\\%$ 固含量的10官亲水性紫外光固化树脂。  \n\n[0039] 实施例2  \n\n[0040] 本实施例提供了一种多官能度亲水性紫外光固化树脂的制备方法，具体步骤如下：在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(69克)，阻聚剂对羟基苯甲醚(0 .21克)，聚醚胺D400(2 .30克，5mmol)和甲氧基聚乙二醇(1000)丙烯酸酯(10.54克，10mmol)，室温反应1 .5小时，FT-IR检测不到 $810\\mathrm{cm}^{-1}$ 处双键的吸收峰，第一步反应结束。然后加入乙氧基季戊四醇四丙烯酸酯 $\\mathrm{(E0120mol)}$ )(56 .32克，10mmol) ,升温至45度反应3小时，FT-IR检测不到 $3400{-}3300{\\mathrm{cm}}^{-1}$ 处仲胺的吸收峰，结束反应，得到浅黄色透明液体，为 $50\\%$ 固含量的6官亲水性紫外光固化树脂。  \n\n[0041] 实施例3  \n\n[0042] 本实施例提供了一种多官能度亲水性紫外光固化树脂的制备方法，具体步骤如下：在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(61克)，阻聚剂对羟基苯甲醚(0 .18克)，聚醚胺ED-600(2.64克，5mmol)和甲氧基聚乙二醇(1000)丙烯酸酯(10.54克，10mmol)，室温反应1 .5小时，FT-IR检测不到 $810\\mathrm{cm}^{-1}$ 处双键的吸收峰，第一步反应结束。然后加入乙氧基双季戊四醇六丙烯酸酯(EO96mol)(48.02克，10mmol) ,升温至45度反应3小时，FT-IR检测不到 $3400{-}3300{\\mathrm{cm}}^{-1}$ 处仲胺的吸收峰，结束反应，得到浅黄色透明液体，为 $50\\%$ 固含量的10官亲水性紫外光固化树脂。  \n\n[0043] 实施例4  \n\n[0044] 本实施例提供了一种多官能度亲水性紫外光固化树脂的制备方法，具体步骤如下：在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(45克)，阻聚剂对羟基苯甲醚(0 .14克)，聚醚胺ED-900(5 .0克，5mmol)和甲氧基聚乙二醇(2000)丙烯酸酯(20.96克，10mmol)，室温反应1 .5小时，FT-IR检测不到 $810\\mathrm{cm}^{-1}$ 处双键的吸收峰，第一步反应结束。然后加入乙氧基季戊四醇四丙烯酸酯 $\\left(\\mathrm{E035mol}\\right)$ )(18.92克，10mmol) ,升温至45度反应3小时，FT-IR检测不到 $3400{-}3300{\\mathrm{cm}}^{-1}$ 处仲胺的吸收峰，结束反应，得到浅黄色透明液体，为$50\\%$ 固含量的6官亲水性紫外光固化树脂。  \n\n[0045] 实施例5  \n\n[0046] 本实施例提供了一种多官能度亲水性紫外光固化树脂的制备方法，具体步骤如下：在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(82克)，阻聚剂对羟基苯甲醚(0 .25克)，聚醚胺ED-2003(23 .0克，10mmol)和甲氧基聚乙二醇(1000)丙烯酸酯(21 .08克，20mmol)，室温反应1 .5小时，FT-IR检测不到 $810\\mathrm{cm}^{-1}$ 处双键的吸收峰，第一步反应结束。然后加入乙氧基季戊四醇四丙烯酸酯(EO35mol)(37.84克，20mmol) ,升温至45度反应3小时，FT-IR检测不到 $3400{-}3300{\\mathrm{cm}}^{-1}$ 处仲胺的吸收峰，结束反应，得到浅黄色透明液体，为 $50\\%$ 固含量的6官亲水性紫外光固化树脂。  \n\n[0047] 实施例6  \n\n[0048] 本实施例提供了一种多官能度亲水性紫外光固化树脂的制备方法，具体步骤如下：在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(67克)，阻聚剂对羟基苯甲醚(0 .14克)，聚醚胺ED-900(5 .0克，5mmol)和甲氧基聚乙二醇(600)丙烯酸酯(6 .16克，10mmol)，室温反应1 .5小时，FT-IR检测不到 $810\\mathrm{cm}^{-1}$ 处双键的吸收峰，第一步反应结束。然后加入乙氧基季戊四醇四丙烯酸酯(EO120mol)(56 .32克，10mmol) ,升温至45度反应3小时，FT-IR检测不到 $3400{-}3300{\\mathrm{cm}}^{-1}$ 处仲胺的吸收峰，结束反应，得到浅黄色透明液体，为 $50\\%$ 固含量的6官亲水性紫外光固化树脂。  \n\n[0049] 对比例1  \n\n[0050] 本对比例提供了一种多官能度亲水性紫外光固化树脂的制备方法，具体步骤如下：在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(59克)，阻聚剂对羟基苯甲醚(0 .18克)，己二胺(0 .58克，5mmol)和甲氧基聚乙二醇(1000)丙烯酸酯(10 .54克，10mmol)，室温反应1 .5小时，FT-IR检测不到 $810\\mathrm{cm}^{-1}$ 处双键的吸收峰，第一步反应结束。然后加入乙氧基双季戊四醇六丙烯酸酯(EO96mol)(48.02克，10mmol) ,升温至45度反应3小时，FT-IR检测不到 $3400{-}3300{\\mathrm{cm}}^{-1}$ 处仲胺的吸收峰，结束反应，得到浅黄色透明液体，为 $50\\%$ 固含量的10官亲水性紫外光固化树脂。  \n\n[0051] 对比例2  \n\n[0052] 本对比例提供了一种多官能度亲水性紫外光固化树脂的制备方法，具体步骤如下：在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(60克)，阻聚剂对羟基苯甲醚(0 .18克)，聚醚胺D400(2.30克，5mmol)和丙烯酸丁酯(1 .28克，10mmol)，室温反应1.5小时，FT-IR检测不到 $810\\mathrm{cm}^{-1}$ 处双键的吸收峰，第一步反应结束。然后加入乙氧基季戊四醇四丙烯酸酯(EO120mol)(56 .32克，10mmol) ,升温至45度反应3小时，FT-IR检测不到$3400{-}3300{\\mathrm{cm}}^{-1}$ 处仲胺的吸收峰，结束反应，得到浅黄色透明液体，为 $50\\%$ 固含量的6官亲水性紫外光固化树脂。  \n\n[0053] 对比例3  \n\n[0054] 本对比例提供了一种多官能度亲水性紫外光固化树脂的制备方法，具体步骤如下：在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(72克)，阻聚剂对羟基苯甲醚(0 .22克)，聚醚胺ED-900(10 .0克，10mmol)和甲氧基聚乙二醇(2000)丙烯酸酯(41 .92克，20mmol)，室温反应1 .5小时，FT-IR检测不到 $810\\mathrm{cm}^{-1}$ 处双键的吸收峰，第一步反应结束。然后加入乙氧基季戊四醇四丙烯酸酯(EO15mol)(20.24克，20mmol) ,升温至45度反应3小时，FT-IR检测不到 $3400{-}3300{\\mathrm{cm}}^{-1}$ 处仲胺的吸收峰，结束反应，得到浅黄色透明液体，为 $50\\%$ 固含量的6官亲水性紫外光固化树脂。  \n\n[0055] 对比例4  \n\n[0056] 本对比例提供了一种多官能度亲水性紫外光固化树脂的制备方法，具体步骤如下：在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(56克)，阻聚剂对羟基苯甲醚(0 .15克)，聚醚胺ED-900(10 .0克，10mmol)和甲氧基聚乙二醇(2000)丙烯酸酯(9 .08克，20mmol)，室温反应1 .5小时，FT-IR检测不到 $810\\mathrm{cm}^{-1}$ 处双键的吸收峰，第一步反应结束。然后加入乙氧基三羟甲基丙烷三丙烯酸酯 $\\left(\\mathrm{E035mol}\\right)$ )(36 .72克，20mmol) ,升温至45度反应3小时，FT-IR检测不到 $3400{-}3300{\\mathrm{cm}}^{-1}$ 处仲胺的吸收峰，结束反应，得到浅黄色透明液体，为 $50\\%$ 固含量的4官亲水性紫外光固化树脂。  \n\n[0057] 性能测试  \n\n[0058] 对所合成例 $1{\\sim}6$ 及对比合成例 $1{\\sim}4$ 制备的多官能度亲水性紫外光固化树脂，分别配成列于表1中的应用实施例1-6及应用对比例1-4的紫外光固化防雾涂料后，以PET作为基材，将实施例和对比例制备的涂料( $30\\%$ 固含)用10号线棒涂布在其表面，放入 $60^{\\circ}\\mathrm{C}$ 烘箱1min，之后经过紫外固化，能量为 $500\\mathrm{mJ/cm^{2}}$ 。  \n\n[0059] 分别对应用实施例 $1{\\sim}6$ 以及应用对比例 $1{\\sim}4$ 制得的涂层进行性能检测，测定涂层的附着力、铅笔硬度、耐磨性、初期水接触角和持续水接触角及防雾性能。具体结果列于表1中。  \n\n[0060] 具体性能检测项目及对应的方法如下：  \n[0061] 一、附着力  \n[0062] 采用百格法，用3M不干胶带对样张附着力进行测试。  \n[0063] 评估方法：  \n[0064] 5B－划线边缘光滑，在划线的边缘及交叉点处均无涂层脱落；  \n[0065] 4B－在划线的交叉点处有小片的涂层脱落，并且脱落总面积小于 $5\\%$ ；  \n[0066] 3B－在划线的边缘及交叉点处有小片的涂层脱落，并且脱落总面积在 $5\\sim15\\%$ 之间；  \n[0067] 2B－在划线的边缘及交叉点处有成片的涂层脱落，并且脱落总面积在 $15\\sim35\\%$ 之间；  \n[0068] 1B－在划线的边缘及交叉点处有成片的涂层脱落，并且脱落总面积在 $35\\sim65\\%$ 之间；  \n[0069] 0B－在划线的边缘及交叉点处有成片的涂层脱落，并且脱落总面积大于 $65\\%$ 。[0070] 二、铅笔硬度  \n[0071] 参照国家标准GB/T6739《漆膜硬度铅笔测定法》。  \n[0072] 三、耐磨性能  \n[0073] 使用0000#钢丝绒， $300\\mathrm{g}$ 力，一个来回记为一次，记录表面出现刮花的次数。[0074] 评估方法：经过一定次数的摩擦后，观察涂层是否有刮痕，记录无刮痕时所能耐受的最多摩擦次数。  \n[0075] 四、初期亲水角  \n[0076] 在固化好的试样表面滴4μL去离子水，在 $20{\\sim}25^{\\circ}\\mathrm{C}$ 范围内用接触角测试仪测定。[0077] 五、持续亲水角  \n[0078] 将固化好的试样放入去离子水中浸泡 $24\\mathrm{h}$ ，晾干后用接触角测量仪测定。  \n[0079] 六：防雾性：把表面温度为25度的测试板水平置于 $80^{\\circ}\\mathrm{C}$ 的水面上方10cm处，观察样板起雾的时间。  \n[0080] X：1秒内起雾  \n[0081] $\\Delta$ ：10秒后起雾  \n[0082] $\\bigcirc:30$ 秒后起雾  \n\n[0083] $\\textcircled{9}$ ：不起雾 [0084] 表1  \n\n<html><body><table><tr><td rowspan=\"2\">原料</td><td rowspan=\"2\">化学名</td><td colspan=\"6\">应用实施例（重量份数）</td><td colspan=\"3\">应用对比例（重量份</td></tr><tr><td>1</td><td>2 3</td><td>4</td><td>5</td><td>6</td><td>1</td><td>数) 2</td><td>3</td><td>4</td></tr><tr><td>多官 能度 亲水 性光 固化 树脂</td><td>多官丙烯 酸树脂</td><td>60</td><td>60 60</td><td>60</td><td>60</td><td>60</td><td>60</td><td>60</td><td>60</td><td>60</td><td></td></tr><tr><td>疏水 性光 固化 树脂</td><td>10官聚氨 酯丙烯酸 酯（长兴 6195)</td><td colspan=\"10\">25</td></tr><tr><td>疏水 性单 体</td><td>三羟甲基 丙烷三丙 烯酸酯</td><td colspan=\"10\">5</td></tr><tr><td>亲水 性光 固化 单体</td><td>甲基丙烯 酸</td><td colspan=\"10\">5</td></tr><tr><td rowspan=\"2\">光引 发剂</td><td>184</td><td colspan=\"7\">3</td><td></td><td colspan=\"2\"></td></tr><tr><td>TPO</td><td colspan=\"7\">2</td><td colspan=\"3\"></td></tr><tr><td rowspan=\"3\">溶剂</td><td>乙酸乙酯</td><td colspan=\"10\">100</td></tr><tr><td>乙酸丁酯</td><td colspan=\"10\">150</td></tr><tr><td>乙醇 对羟基苯</td><td colspan=\"10\">50</td></tr><tr><td colspan=\"2\">阻聚 剂</td><td colspan=\"10\">0.05</td></tr><tr><td rowspan=\"6\">性能 测试</td><td>甲醚 附着</td><td>5B</td><td>5B</td><td>5B</td><td>5B</td><td>5B</td><td>5B</td><td>5B</td><td>5B</td><td>5B</td><td>5B</td></tr><tr><td>铅笔硬度</td><td>2H</td><td>2H</td><td>2H</td><td>2H</td><td>2H</td><td>2H</td><td>2H</td><td>2H</td><td>2H</td><td>H</td></tr><tr><td>耐磨</td><td>49</td><td>48</td><td>46</td><td>52</td><td>48</td><td>52</td><td>51</td><td>53</td><td>55</td><td>38</td></tr><tr><td>防雾性</td><td></td><td></td><td></td><td></td><td></td><td></td><td>X</td><td>X</td><td>X</td><td>△</td></tr><tr><td>初期水接 触角</td><td>8.1</td><td>6.8</td><td>7.3</td><td>9.5</td><td>7.9</td><td>8.9</td><td>41.</td><td>51. 3</td><td>45. 2</td><td><5</td></tr><tr><td>持续水接</td><td>28.</td><td>31. 29.</td><td>33.</td><td>30.2</td><td>29.</td><td>6 一</td><td>一</td><td></td><td>47.</td><td></td></tr></table></body></html>  \n\n[0086] 由表1的性能测试结果可以看出，应用实施例 $1{\\sim}6$ 具有较好的防雾性能。初始水接触角均低于10度，24小时浸泡后的水接触角均低于35度，防雾性能优良，同时耐磨性也好。[0087] 应用对比例1与应用实施例1相比,由于所用亲水性多官能度紫光固化树脂合成时,采用己二胺来代替聚醚胺D400,所得最终多官能度紫外光固化树脂的亲水性比较差，因此用在防雾涂料配方中，虽然涂层耐磨性有很大提高，但是导致涂层的亲水性差，因而不具备防雾性能。  \n\n[0088] 应用对比例2与应用实施例2相比,由于所用亲水性多官能度紫外光固化树脂合成时,第一步反应时，采用丙烯酸丁酯来代替甲氧基聚乙二醇(1000)丙烯酸酯,所得最终多官能度紫外光固化树脂的亲水性比较差，因此用在防雾涂料配方中，虽然涂层耐磨性稍有提高，但是导致涂层的亲水性差，因而不具备防雾性能。  \n\n[0089] 应用对比例3与应用实施例4相比,由于所用亲水性多官能度紫外光固化树脂合成时,采用含乙氧基数量比较少的乙氧基季戊四醇四丙烯酸酯(EO15mol)来代替含乙氧基数量较多的乙氧基季戊四醇四丙烯酸酯 $\\left(\\mathrm{E035mol}\\right)$ ) ,所得最终多官能度紫外光固化树脂的亲水性比较差，因此用在防雾涂料配方中，虽然涂层耐磨性稍有提高，但是导致涂层的亲水性差，因而不具备防雾性能。  \n\n[0090] 应用对比例4与应用实施例4相比,由于所用亲水性多官能度紫外光固化树脂合成时,采用乙氧基三羟甲基丙烷三丙烯酸酯 $\\left(\\mathrm{E035mol}\\right)$ 来代替乙氧基季戊四醇四丙烯酸酯$\\left(\\mathrm{E035mol}\\right)$ ) ,得到四官能度紫外光固化树脂。因最终树脂官能度较低，亲水性太好，导致最终涂层由于水溶胀而使亲水部分网络从基材表面脱离，导致涂层中疏水部分占大多数，而使亲水性大大降低。同时涂层的耐磨和硬度也显著降低。  \n\n[0091] 应当指出，以上实施例仅用于说明本发明，而并不用于限制本发明的保护范围。对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进，这些改进也应视为本发明的保护范围。",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/CN201810154740-╥╗╓╓║м╗╟╦с╤╬╡─╛█▒√╧й╦сїе╦о╖╓╔в╠х╝░╞ф╓╞▒╕╖╜╖и╙ы╙ж╙├-╔ъ╟ы╣л┐к.json b/task2/task2-chunks/CN201810154740-╥╗╓╓║м╗╟╦с╤╬╡─╛█▒√╧й╦сїе╦о╖╓╔в╠х╝░╞ф╓╞▒╕╖╜╖и╙ы╙ж╙├-╔ъ╟ы╣л┐к.json
new file mode 100644
index 0000000..41289bb
--- /dev/null
+++ b/task2/task2-chunks/CN201810154740-╥╗╓╓║м╗╟╦с╤╬╡─╛█▒√╧й╦сїе╦о╖╓╔в╠х╝░╞ф╓╞▒╕╖╜╖и╙ы╙ж╙├-╔ъ╟ы╣л┐к.json
@@ -0,0 +1,57 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利申请  \n\n<html><body><table><tr><td>(21)申请号201810154740.9</td><td>C08J 3/07(2006.01)</td></tr><tr><td>(22)申请日 2018.02.23</td><td>C09D 175/04(2006.01)</td></tr><tr><td>(71)申请人 华南理工大学</td><td>C08F 228/02(2006.01)</td></tr><tr><td></td><td>C08F 283/06(2006.01)</td></tr><tr><td>地址 510640广东省广州市天河区五山路 381号</td><td>C08F 222/02(2006.01)</td></tr><tr><td></td><td>CO8L 33/14(2006.01)</td></tr><tr><td>(72)发明人瞿金清廖珊珊</td><td>C08L 33/24(2006.01)</td></tr><tr><td>(74)专利代理机构广州市华学知识产权代理有</td><td>C08L 51/08(2006.01)</td></tr><tr><td>限公司44245 代理人向玉芳</td><td></td></tr><tr><td>(51)Int.CI.</td><td></td></tr><tr><td>C08F 220/14(2006.01)</td><td></td></tr><tr><td>C08F 220/18(2006.01)</td><td></td></tr><tr><td>C08F 220/06(2006.01)</td><td></td></tr><tr><td>C08F 220/20(2006.01)</td><td></td></tr><tr><td>C08F 220/58(2006.01)</td><td></td></tr></table></body></html>",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n一种含磺酸盐的聚丙烯酸酯水分散体及其制备方法与应用",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明公开了一种含磺酸盐的聚丙烯酸酯水分散体及其制备方法与应用，该方法为先将所有丙烯酸单体与链转移剂混合制备混合液I，将乙烯基磺酸盐单体、引发剂与有机溶剂溶解配制成混合液II，向反应釜内加入 $10-30\\%$ 混合物I和$10\\text{\\textperthousand}$ 混合物II，搅拌升温至 $80{-}95^{\\circ}\\mathrm{C}$ 反应，加入剩余混合物I和混合液II，保温、中和与乳化得到含磺酸盐的聚丙烯酸酯水分散体；将该水分散体与水性固化剂混配制膜，其干燥漆膜的水接触角低于 ${40}^{\\circ}$ °，光泽度大于 $98^{\\circ}$ °，硬度达2H，亲水性强、耐水性好、光泽度高、硬度高及附着力好，可用于塑料镜片、汽车挡风玻璃等的涂装保护，具有透明度高、防雾及易清洁作用。  \n\n![](images/e53a5d9bbe785a063fed5bc7762d4c578eb3a42f77192afb28b761e93e496fdd.jpg)  \n\n1.一种含磺酸盐的聚丙烯酸酯水分散体的制备方法，其特征在于包括以下步骤：  \n\n(1)含磺酸盐的聚丙烯酸酯的制备：将所有丙烯酸单体与链转移剂混合制备混合液I，将乙烯基磺酸盐单体、引发剂与有机溶剂溶解配制成混合液II，向反应釜内加入 $10-30\\%$ 混合物I和 $10\\text{\\textperthousand}$ 混合物II，搅拌升温至 $80{-}95^{\\circ}\\mathrm{C}$ 反应 $30{-}60\\mathrm{{min}}$ ，将剩余混合物I和混合液II分别在4-6h内加入到反应釜中，然后保温 $0.5\\mathrm{-2h}$ ，降温至 $40–70^{\\circ}\\mathrm{C}$ 以下，加入中和剂中和，得到含磺酸盐的聚丙烯酸酯；  \n\n(2)水分散体的制备：加入所述含磺酸盐的聚丙烯酸酯质量的1-3倍水乳化至固体含量为 $20\\%$ ，得到含磺酸盐的聚丙烯酸酯水分散体；  \n\n所述丙烯酸单体由甲基丙烯酸烷基酯、丙烯酸烷基酯、含羟基丙烯酸单体和含羧酸的丙烯酸单体组成；  \n\n所述的甲基丙烯酸烷基酯为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯和甲基丙烯酸异冰片酯中的一种或多种；  \n\n所述丙烯酸烷基酯为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯和丙烯酸异辛酯中的一种或者多种；  \n\n所述的含羟基丙烯酸单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯和甲基丙烯酸羟丙酯中的一种或多种；  \n\n所述的含羧酸的丙烯酸单体为丙烯酸、甲基丙烯酸、衣康酸和顺酐中的一种或多种；  \n\n所述乙烯基磺酸盐单体为 $2^{-}$ 丙烯酰胺基 $^{-2-}$ 甲基丙磺酸、乙烯基磺酸钠、2-丙烯酰胺基-2-甲基丙磺酸钠和烯丙氧基脂肪醇氧乙烯醚硫酸铵中的一种或多种；  \n\n所述引发剂为偶氮类引发剂；  \n\n所述链转移剂为巯基乙醇、巯基丙酸、十二烷基硫醇和巯基丙醇中的一种或2种以上混合物。  \n\n2.根据权利要求1所述的含磺酸盐的聚丙烯酸酯水分散体的制备方法，其特征在于，以质量百分比计，所述含磺酸盐的聚丙烯酸酯的原料配方组成为：甲基丙烯酸烷基酯 $26-$ $34\\%$ ，丙烯酸烷基酯 $22\\%$ ，含羟基丙烯酸单体 $11.5\\text{\\textperthousand}$ ，含羧酸的丙烯酸单体 $1-2\\%$ ，乙烯基磺酸盐单体 $3-8\\%$ ，引发剂 $0.8–1.5\\%$ ，链转移剂 $0.6\\%$ ，中和剂 $1.5\\%$ ，余量为有机溶剂。  \n\n3.根据权利要求1所述的含磺酸盐的聚丙烯酸酯水分散体的制备方法，其特征在于，所述偶氮类引发剂为偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯、偶氮二异丁脒盐酸盐，偶氮二异丁咪唑啉盐酸盐和偶氮异丁氰基甲酰胺中的一种或2种以上混合物。  \n\n4.根据权利要求1所述的含磺酸盐的聚丙烯酸酯水分散体的制备方法，其特征在于，所述的中和剂为三乙胺、N，N-二甲基乙醇胺和2-氨基-2-甲基丙醇中的一种或两种以上混合物。  \n\n5.根据权利要求1所述的含磺酸盐的聚丙烯酸酯水分散体的制备方法，其特征在于，所述的有机溶剂为N，N-二甲基甲酰胺、丙酮、丁酮、丙二醇甲醚醋酸酯和乙酸乙酯中的一种或者两者混合物。  \n\n6.一种含磺酸盐的聚丙烯酸酯水分散体，其特征在于，其由权利要求1-5任一项所述的制备方法制得，所述含磺酸盐的聚丙烯酸酯水分散体平均粒径 $50\\mathrm{-}300\\mathrm{nm}$ ， $25^{\\circ}\\mathrm{C}$ 下粘度为500-5000cp；固含量为 $20\\%$ 。  \n\n7.权利要求6所述的含磺酸盐的聚丙烯酸酯水分散体在塑料用亲水涂料中的应用，其特征在于，将所述含磺酸盐的聚丙烯酸酯水分散体加入到搅拌釜中，加入消泡剂和润湿剂，分散10-30分钟，过滤出料，得含磺酸盐的聚丙烯酸酯水分散体涂料；  \n\n施工时，水性多异氰酸酯固化剂按照NCO/OH摩尔比为1 .0-1 .8加入到含磺酸盐的聚丙烯酸酯水分散体涂料中，搅拌5-8分钟，得到水性双组份聚氨酯涂料。  \n\n8.根据权利要求7所述的含磺酸盐的聚丙烯酸酯水分散体在塑料用亲水涂料中的应用，其特征在于，所述的水性多异氰酸酯固化剂为拜尔公司的亲水改性六亚甲基二异氰酸酯(HDI)Bayhydur  3100、Bayhydur  XP  2655、Bayhydur  304、Bayhydur  XP  2547、DesmodurDA-L中的一种或多种。  \n\n9.根据权利要求7所述的含磺酸盐的聚丙烯酸酯水分散体在塑料用亲水涂料中的应用，其特征在于，所述的消泡剂为TEGO公司的聚醚硅氧烷共聚物消泡剂TEGO-800、TEGO-805、TEGO-815、TEGO-825和BYK公司的改性聚硅氧烷共聚体溶液BYK-019、BYK-020的一种或多种；消泡剂的用量为含磺酸盐的聚丙烯酸酯水分散体质量的 $0.2\\%$ 。  \n\n所述的润湿剂为TEGO公司的聚醚硅氧烷共聚物TEGO-245、非离子有机表面活性剂TEGO-500和BYK公司的聚醚改性聚硅氧烷溶液BYK-346的一种或多种；润湿剂的用量为含磺酸盐的聚丙烯酸酯水分散体质量的 $0.4\\%$ 。  \n\n10.根据权利要求7所述的含磺酸盐的聚丙烯酸酯水分散体在塑料用亲水涂料中的应用，其特征在于，所述的水性双组份聚氨酯涂料形成的涂膜与水的接触角低于 ${40}^{\\circ}$ °，测试入射角 ${60}^{\\circ}$ °的光泽度大于 $98^{\\circ}$ °，硬度达2H。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 一种含磺酸盐的聚丙烯酸酯水分散体及其制备方法与应用",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明涉及一种聚丙烯酸酯水分散体，特别涉及一种含磺酸盐的聚丙烯酸酯水分散体及其制备方法与在塑料用亲水涂料中的应用，属于精细化工合成领域。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 随着生活水平的不断提高，提高透明材料如塑料镜片、汽车挡风玻璃等的防雾性能，减少因雾化而带来的不便成为了普遍需求，亲水涂料作为突出的防雾材料越发引起重视。亲水性防雾涂料通过改善基材表面的润湿性，使水滴可以快速均匀铺展在基材表面，降低基材表面的静态水接触角；当某表面与水分的接触角小于 ${40}^{\\circ}$ °时，一般会被认为具有亲水性防雾能力；接触角在此范围内，虽然仍存在冷凝作用，但表面依然可保持光学透明。  \n\n[0003] 亲水性防雾材料主要包括亲水性表面活性剂、无机亲水防雾材料、有机/无机杂合型亲水防雾涂料、有机聚合物亲水防雾涂料；其中亲水性表面活性剂虽然成本低，但组分为小分子而使得其使用寿命短，不耐擦拭；无机亲水防雾材料常常需要高温固化，固化温度在$150^{\\circ}\\mathrm{C}$ 以上，不适用于塑料基材；有机/无机杂合型亲水涂料贮存稳定性和透明性难以达到要求。有机聚合物亲水防雾涂料具有明显的优势，其防雾效果好，亲水性能由极性亲水基团如羟基、羧基等提供；目前有机亲水涂料仍存在涂膜亲水但不耐水，亲水性保持时间不长，多数涂膜需要高温 $(100^{\\circ}\\mathrm{C})$ 以上固化，难以在塑料表面应用。  \n\n[0004] 中国发明专利申请201410429192.8公开了一种水性丙烯酸防雾涂料及其制备方法，该防雾涂料由对基材有优异附着力的底层涂料和亲水性的面层涂料组成，底漆和面漆皆为聚丙烯酸酯乳液，二层涂料虽能提高涂膜的附着力，但涂膜层透明性下降，而且二层涂膜增加施工成本；中国发明专利申请201410087145.X公开了一种超亲水有机硅涂料的制备方法，该方法需要高温 $\\left(120^{\\circ}\\mathrm{C}\\right)$ 固化，不适用于透明塑料表面。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0005] 本发明目的之一是克服现有技术存在的问题，提供一种含磺酸盐的聚丙烯酸酯水分散体及其制备方法；所制得的含磺酸盐聚丙烯酸酯水分散体制备的涂膜具有透明度高、光泽度高、亲水性佳、耐水性好、涂膜亲水保持时间长等优点。  \n\n[0006] 本发明的目的之二是提供上述含磺酸盐的聚丙烯酸酯水分散体在塑料用亲水涂料中应用。  \n\n[0007] 为了实现以上目的，本发明采用以下技术方案：  \n\n[0008] 一种含磺酸盐的聚丙烯酸酯水分散体的制备方法，包括以下步骤：  \n\n[0009] (1)含磺酸盐的聚丙烯酸酯的制备：将所有丙烯酸单体与链转移剂混合制备混合液I，将乙烯基磺酸盐单体、引发剂与有机溶剂溶解配制成混合液II，向反应釜内加入 $10^{-}$ $30\\%$ 混合物I和 $10\\text{\\textperthousand}$ 混合物II，搅拌升温至 $80{-}95^{\\circ}\\mathrm{C}$ 反应 $30{-}60\\mathrm{{min}}$ ，将剩余混合物I和混合液II分别在 $4{\\mathrm{-}}6\\mathrm{h}$ 内加入到反应釜中，然后保温 $0.5\\mathrm{-2h}$ ，降温至 $40–70^{\\circ}\\mathrm{C}$ 以下，加入中和剂中和，得到含磺酸盐的聚丙烯酸酯；  \n\n[0010] (2)水分散体的制备：加入所述含磺酸盐的聚丙烯酸酯质量的1-3倍水乳化至固体含量为 $20\\%$ ，得到含磺酸盐的聚丙烯酸酯水分散体；  \n\n[0011] 所述丙烯酸单体由甲基丙烯酸烷基酯、丙烯酸烷基酯、含羟基丙烯酸单体和含羧酸的丙烯酸单体组成；  \n\n[0012] 所述的甲基丙烯酸烷基酯为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯和甲基丙烯酸异冰片酯中的一种或多种；  \n\n[0013] 所述丙烯酸烷基酯为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯和丙烯酸异辛酯中的一种或者多种；  \n\n[0014] 所述的含羟基丙烯酸单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯和甲基丙烯酸羟丙酯中的一种或多种；  \n\n[0015] 所述的含羧酸的丙烯酸单体为丙烯酸、甲基丙烯酸、衣康酸和顺酐中的一种或多种；  \n\n[0016] 所述乙烯基磺酸盐单体为2-丙烯酰胺基 $-2-$ 甲基丙磺酸、乙烯基磺酸钠、2-丙烯酰胺基 $-2-$ 甲基丙磺酸钠和烯丙氧基脂肪醇氧乙烯醚硫酸铵中的一种或多种；  \n\n[0017] 所述引发剂为偶氮类引发剂；  \n\n[0018] 所述链转移剂为巯基乙醇、巯基丙酸、十二烷基硫醇和巯基丙醇中的一种或2种以上混合物。  \n\n[0019] 为进一步实现本发明目的，优选地，以质量百分比计，所述含磺酸盐的聚丙烯酸酯的原料配方组成为：甲基丙烯酸烷基酯 $26\\%-34\\%$ ，丙烯酸烷基酯 $22\\%$ ，含羟基丙烯酸单体$11.5\\text{\\textperthousand}$ ，含羧酸的丙烯酸单体 $1-2\\%$ ，乙烯基磺酸盐单体 $3-8\\%$ ，引发剂 $0.8–1.5\\%$ ，链转移剂 $0.6\\%$ ，中和剂 $1.5\\%1.5\\%$ ，余量为有机溶剂。  \n\n[0020] 优选地，所述偶氮类引发剂为偶氮二异丁腈(AIBN)、偶氮二异庚腈(ABVN)、偶氮二异丁酸二甲酯(V601，AIBME)、偶氮二异丁脒盐酸盐(AIBA) ，偶氮二异丁咪唑啉盐酸盐(AIBI)和偶氮异丁氰基甲酰胺(V30)中的一种或2种以上混合物。  \n\n[0021] 优选地，所述的中和剂为三乙胺、N，N-二甲基乙醇胺、2-氨基 $^{-2-}$ 甲基丙醇中的一种或两种以上混合物。  \n\n[0022] 优选地，所述的有机溶剂为 $\\mathrm{\\DeltaN,N-}$ 二甲基甲酰胺、丙酮、丁酮、丙二醇甲醚醋酸酯和乙酸乙酯中的一种或者两者混合物。  \n\n[0023] 一种含磺酸盐的聚丙烯酸酯水分散体，由上述的制备方法制得，所述含磺酸盐的聚丙烯酸酯水分散体平均粒径 $50\\mathrm{-}300\\mathrm{nm}$ ， $25\\mathrm{{^\\circC}}$ 下粘度为 $500{-}5000{\\mathrm{cp}}$ ；固含量为 $20\\%$ 。  \n\n[0024] 所述的含磺酸盐的聚丙烯酸酯水分散体在塑料用亲水涂料中的应用：将所述含磺酸盐的聚丙烯酸酯水分散体加入到搅拌釜中，加入消泡剂和润湿剂，分散10-30分钟，过滤出料，得含磺酸盐的聚丙烯酸酯水分散体涂料；  \n\n[0025] 施工时，水性多异氰酸酯固化剂按照NCO/OH摩尔比为1 .0-1 .8加入到含磺酸盐的聚丙烯酸酯水分散体涂料中，搅拌5-8分钟，得到水性双组份聚氨酯涂料。  \n\n[0026] 优选地，所述的水性多异氰酸酯固化剂为拜尔公司的亲水改性六亚甲基二异氰酸酯(HDI)Bayhydur  3100、Bayhydur  XP  2655、Bayhydur  304、Bayhydur  XP  2547、DesmodurDA-L中的一种或多种。  \n\n[0027] 优选地，所述的消泡剂为TEGO公司的聚醚硅氧烷共聚物消泡剂TEGO-800、TEGO-  \n\n805、TEGO-815、TEGO-825和BYK公司的改性聚硅氧烷共聚体溶液BYK-019、BYK-020的一种或多种；消泡剂的用量为含磺酸盐的聚丙烯酸酯水分散体质量的 $0.2\\%$ 。  \n[0028] 所述的润湿剂为TEGO公司的聚醚硅氧烷共聚物TEGO-245、非离子有机表面活性剂TEGO-500和BYK公司的聚醚改性聚硅氧烷溶液BYK-346的一种或多种；润湿剂的用量为含磺酸盐的聚丙烯酸酯水分散体质量的 $0.4\\%$ 。  \n[0029] 优选地，所述的水性双组份聚氨酯涂料形成的涂膜与水的接触角低于 ${\\cdot40}^{\\circ}$ °，光泽度$(60^{\\circ})$ 大于 $98^{\\circ}$ °，硬度达2H。且耐水性好、附着力好，可用于塑料镜片、汽车挡风玻璃等的涂装保护，具有透明度高、防雾及易清洁作用。  \n[0030] 本发明的技术原理如下：  \n[0031] (1)本发明亲水防雾性能的实现：通过自由基溶液聚合制备含磺酸基的聚丙烯酸酯，中和形成磺酸盐和羧酸盐，其中磺酸盐作为强亲水基团，不仅能作为内乳化剂使丙烯酸聚合物易分散在水中形成丙烯酸聚合物水分散体，而且该分散体固化形成涂膜后，涂膜中含有的磺酸盐赋予涂膜有极好的亲水性，使得涂膜与水的接触角小于 ${40}^{\\circ}$ °，从而实现涂料亲水防雾性能。相比羧酸盐聚合物涂膜亲水性不及磺酸盐。  \n[0032] (2)涂膜亲水和耐水性平衡问题：本发明制备的含磺酸盐的聚丙烯酸酯水分散体含有大量的羟基，能在常温下与水性聚氨酯固化剂的NCO基反应，形成三维交联网络结构，赋予涂膜优异的耐水性和耐醇性。通过调控丙烯酸聚合物的玻璃化转变温度、羟基含量、乙烯基磺酸盐的添加量等来调控涂膜的交联密度、亲水性和涂膜物理机械性能。  \n[0033] 相对于现有技术，本发明具有如下优点：  \n[0034] (1)本发明制备的含磺酸盐的聚丙烯酸酯水分散体，亲水基团为磺酸盐，其亲水能力强于羧酸盐和亲水非离子，能赋予涂膜优异的亲水性。  \n[0035] (2)本发明亲水涂料能在室温下固化，具有优异的耐水性，可用于塑料涂料，克服高温固化耗能和UV固化需要特殊固化设备的缺点；  \n[0036] (3)本发明制备的是水性涂料，贮存稳定，所含VOC低，具有绿色环保的优点。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 附图说明  \n\n[0037] 图1为实施例1塑料用亲水涂料的红外光谱图。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 具体实施方式  \n\n[0038] 为了更好地理解本发明，下面结合附图和实施例对发明做进一步的描述，需要说明的是，基于本发明实施例所作的非创造性改动，都属于本发明保护的范围。  \n[0039] 实施例中，塑料用亲水涂料的涂膜性能可用以下方法表征：干燥时间按GB/T1728-1979(1989)测定；铅笔硬度按GB/T  6739-2006测定；涂膜附着力按GB/T  9286-1998测定；涂膜耐水性按GB/T  5209-1985采用室温浸泡法测定；涂膜光泽按GB/T  9754-2007采用${60}^{\\circ}$ °角WGG60-E4型光泽计测定；树脂黏度粘度按GB/T  21059-2007使用NDJ-1型旋转粘度计测定；接触角按GB/T30693-2014测定；贮存稳定性按HG/T2454-2006测定。  \n[0040] 实施例1  \n[0041] 含磺酸盐的聚丙烯酸酯水分散体的制备  \n[0042] (1)以质量份计，一种含磺酸盐的聚丙烯酸酯的原料配方组分如下表1：  \n\n<html><body><table><tr><td colspan=\"2\">[0043] 表1 溶剂：</td></tr><tr><td colspan=\"2\"></td></tr><tr><td>N，N-二甲基甲酰胺</td><td>20份</td></tr><tr><td>[0044] 丙酮</td><td>5份</td></tr><tr><td>丙烯酸单体：</td><td></td></tr><tr><td>甲基丙烯酸甲酯</td><td>26份</td></tr><tr><td>丙烯酸丁酯</td><td>22份</td></tr><tr><td>丙烯酸</td><td>1.0份</td></tr><tr><td>甲基丙烯酸羟乙酯</td><td>15份</td></tr><tr><td>2-丙烯酰胺-2-甲基丙磺酸</td><td>6.0份</td></tr><tr><td>[0045] 引发剂：偶氮二异丁晴</td><td>0.8份</td></tr><tr><td>中和剂：2-氨基-2-甲基丙醇</td><td>3.6份</td></tr><tr><td>链转移剂：琉基乙醇</td><td>0.6份</td></tr><tr><td>总计：</td><td>100份</td></tr></table></body></html>  \n\n[0046] (2)含磺酸盐的聚丙烯酸酯的制备：按上述配方将相应质量份甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸羟乙酯、丙烯酸、链转移剂巯基乙醇混合制备混合液I；按上述配方将相应质量份2-丙烯酰胺 $-2-$ 甲基丙磺酸、引发剂偶氮二异丁腈加入至N， $\\mathrm{N^{-}}$ 二甲基甲酰胺和丙酮溶剂中，搅拌至完全溶解制备混合液II；向反应釜中加入 $10\\%$ 质量的混合液I和 $10\\%$ 质量的混合液II，搅拌，升温至 $80^{\\circ}\\mathrm{C}$ 保温 $30\\mathrm{{min}}$ ，而后控制剩余混合液I和II在6h内滴加完成，保温2h，降温至 $40^{\\circ}\\mathrm{C}$ 加入3.6份的2-氨基 $-2-$ 甲基丙醇中和，得到含磺酸盐的聚丙烯酸酯；[0047] (3)水分散体的制备：加入上述含磺酸盐的聚丙烯酸酯质量的1.5倍的去离子水乳化，得到含磺酸盐的聚丙烯酸酯水分散体；外观：乳白、半透明；固含量： $35\\%$ ；平均粒径：$50\\mathrm{nm}$ ；粘度 $(25^{\\circ}\\mathrm{C})$ 为1000CP；  \n\n[0048] (4)塑料用亲水涂料的配制：以质量份计，原料组成情况如下表2： [0049] 表2  \n\n<html><body><table><tr><td></td><td>上述含磺酸盐的聚丙烯酸酯水分散体</td><td>66份</td></tr><tr><td rowspan=\"3\">50]</td><td>固化剂Bayhydur 3100</td><td>34份</td></tr><tr><td>润湿剂TEGO-245</td><td>0.5份</td></tr><tr><td>消泡剂TEGO-800</td><td>0.2份</td></tr></table></body></html>  \n\n[0051] 按上述配方将相应质量份含磺酸盐的聚丙烯酸酯水分散体、消泡剂TEGO-800、润湿剂TEGO-245加入到搅拌釜中，分散10分钟，过滤出料。水性多异氰酸酯固化剂Bayhydur3100按照NCO/OH摩尔比为1.8加入到上述含磺酸盐的聚丙烯酸酯水分散体配制的涂料中，搅拌5分钟，静置消泡，用刷涂的方法在ABS基材上施工，常温下固化干燥7天，进行相应的涂膜性能测定。  \n\n[0052] 表3   \n\n\n<html><body><table><tr><td rowspan=\"7\">[0053]</td><td>检测项目</td><td>本实施例涂料</td><td>检测方法</td></tr><tr><td>表干时间/min</td><td>60</td><td>GB/T 1728-1979(1989)</td></tr><tr><td>实干时间/h</td><td>12</td><td>GB/T 1728-1979(1989)</td></tr><tr><td>光泽度(60°)</td><td>99</td><td>GB/T 9754-2007</td></tr><tr><td>铅笔硬度</td><td>H</td><td>GB/T6739-2006</td></tr><tr><td>附着力/级 (划格法)</td><td>1</td><td>GB/T6739-2006</td></tr><tr><td>耐水性</td><td>无异常</td><td>GB/T 5209-1985</td></tr><tr><td>接触角/°</td><td>37</td><td>GB/T30693-2014</td></tr><tr><td>透明性(目测法)</td><td>好</td><td>GB/T1721-79(1989)</td></tr><tr><td>贮存稳定性</td><td>无异常</td><td>HG/T2454-2006</td></tr></table></body></html>  \n\n[0054] 上表3说明本发明的含磺酸盐聚丙烯酸酯水分散体与水性固化剂复配制膜在较快的干燥速度情况下大大提高了涂层的亲水性，同时具有良好的附着力、硬度、耐水性等机械性能。附图1为所制备的塑料用亲水涂料，图中在 $1640\\mathrm{cm}^{-1}.810\\mathrm{cm}^{-1}$ 处不存在吸收峰，证明-C$=\\mathrm{C^{-}}$ 及 $\\mathrm{H-C=}$ 的消失，所有单体在共聚期间已经反应； $1470\\mathrm{cm}^{-1}$ 处的吸收峰的存在证明聚合物中磺基的引入；在 $1180\\mathrm{cm}^{-1}$ 处存在较明显的吸收峰，证明磺酸盐的生成。  \n\n[0055] 本发明通过自由基溶液聚合制备含磺酸基的聚丙烯酸酯，中和形成磺酸盐和羧酸盐，其中磺酸盐作为强亲水基团，不仅能作为内乳化剂使丙烯酸聚合物易分散在水中形成丙烯酸聚合物水分散体，而且该分散体固化形成涂膜后，涂膜中含有的磺酸盐赋予涂膜有极好的亲水性，使得涂膜与水的接触角小于 ${40}^{\\circ}$ °，从而实现涂料亲水防雾性能。相比纯羧酸盐聚合物涂膜，本发明亲水性更好、耐水性更强。本发明亲水涂料能在室温下固化，可用于塑料涂料，克服高温固化耗能和UV固化需要特殊固化设备的缺点；本发明制备的是水性涂料，贮存稳定，所含VOC低，具有绿色环保的优点。  \n\n[0056] 实施例2  \n\n含磺酸盐的聚丙烯酸酯水分散体的制备(1)以质量份计，一种含磺酸盐的聚丙烯酸酯的原料配方组分如下表4：表4  \n\n[0060]  \n\n溶剂：  \nN，N-二甲基甲酰胺 20份  \n丙烯酸单体：  \n\n<html><body><table><tr><td></td><td>甲基丙烯酸乙酯</td><td>34份</td></tr><tr><td></td><td>丙烯酸乙酯</td><td>27份</td></tr><tr><td></td><td>甲基丙烯酸</td><td>1.0份</td></tr><tr><td>[0061]</td><td>丙烯酸羟乙酯</td><td>11.5份</td></tr><tr><td></td><td>乙烯基磺酸钠</td><td>3份</td></tr><tr><td></td><td>引发剂：偶氮二异庚晴</td><td>1.0份</td></tr><tr><td></td><td>中和剂：三乙胺</td><td>1.5份</td></tr><tr><td></td><td>链转移剂：硫基丙酸</td><td>1.0份</td></tr><tr><td>总计：</td><td></td><td>100份</td></tr></table></body></html>  \n\n[0062] (2)含磺酸盐的聚丙烯酸酯的制备：按上述配方将相应质量份甲基丙烯酸乙酯、丙烯酸乙酯、丙烯酸羟乙酯、甲基丙烯酸、链转移剂巯基丙酸混合制备混合液I；按上述配方将相应质量份乙烯基磺酸钠、引发剂偶氮二异庚腈加入至N，N-二甲基甲酰胺溶剂中，搅拌至完全溶解制备混合液II；向反应釜中加入 $30\\%$ 质量的混合液I和 $20\\%$ 质量的混合液II，搅拌，升温至 $95^{\\circ}\\mathrm{C}$ 保温60min，而后控制剩余混合液I和II在4h内滴加完成，保温0.5h，降温至$70^{\\circ}\\mathrm{C}$ 加入1.5份的三乙胺中和，得到含磺酸盐的聚丙烯酸酯；  \n\n[0063] (3)水分散体的制备：加入上述含磺酸盐的聚丙烯酸酯质量的1.0倍的去离子水乳化，得到含磺酸盐的聚丙烯酸酯水分散体；外观：乳白、半透明；固含量： $40\\%$ ；平均粒径：$88\\mathrm{nm}$ ；粘度 $(25^{\\circ}\\mathrm{C})$ 为500CP；  \n\n[0064] (4)塑料用亲水涂料的配制：以质量份计，原料组成情况如下表5： [0065] 表5  \n\n[0066]  \n\n<html><body><table><tr><td>上述含磺酸盐的聚丙烯酸酯水分散体 83份</td></tr><tr><td>固化剂BayhydurXP2655 17份</td></tr><tr><td>润湿剂TEGO-500 0.5份</td></tr><tr><td></td></tr><tr><td>消泡剂TEGO-805 0.4份</td></tr></table></body></html>  \n\n[0067] 按上述配方将相应质量份含磺酸盐的聚丙烯酸酯水分散体、消泡剂TEGO-805、润湿剂TEGO-500加入到搅拌釜中，分散20分钟，过滤出料。水性多异氰酸酯固化剂BayhydurXP  2655按照NCO/OH摩尔比为1.0加入到上述含磺酸盐的聚丙烯酸酯水分散体配制的涂料中，搅拌8分钟，静置消泡，用刷涂的方法在ABS基材上施工，常温下固化干燥7天，进行相应的涂膜性能测定。  \n\n[0068] 表6  \n\n<html><body><table><tr><td rowspan=\"7\">[0069]</td><td>检测项目</td><td>本实施例涂料</td><td>检测方法</td></tr><tr><td>表干时间/min</td><td>45</td><td>GB/T 1728-1979(1989)</td></tr><tr><td>实干时间/h</td><td>13</td><td>GB/T 1728-1979(1989)</td></tr><tr><td>光泽度(60°)</td><td>99</td><td>GB/T9754-2007</td></tr><tr><td>铅笔硬度</td><td>2H</td><td>GB/T6739-2006</td></tr><tr><td>附着力/级 (划格法)</td><td>１</td><td>GB/T 6739-2006</td></tr><tr><td>耐水性</td><td>无异常</td><td>GB/T5209-1985</td></tr><tr><td>接触角/°</td><td>25</td><td>GB/T30693-2014</td></tr><tr><td>透明性 (目测法)</td><td>好</td><td>GB/T1721-79(1989)</td></tr><tr><td>贮存稳定性</td><td>无异常</td><td>HG/T2454-2006</td></tr></table></body></html>  \n\n实施例3  \n含磺酸盐的聚丙烯酸酯水分散体的制备  \n(1)以质量份计，一种含磺酸盐的聚丙烯酸酯的原料配方组分如下表7：  \n表7  \n\n<html><body><table><tr><td colspan=\"2\">溶剂：</td><td rowspan=\"5\">20份</td></tr><tr><td></td><td>丙二醇甲醚醋酸酯</td></tr><tr><td>丙烯酸单体：</td><td></td></tr><tr><td>甲基丙烯酸异冰片酯</td><td>28.5份</td></tr><tr><td>丙烯酸甲酯</td><td>22份</td></tr><tr><td rowspan=\"8\">[0074]</td><td>丙烯酸</td><td>1.0份</td></tr><tr><td>甲基丙烯酸</td><td>1.0份</td></tr><tr><td>丙烯酸羟丙酯</td><td>14份</td></tr><tr><td>2-丙烯酰胺基-2-甲基丙磺酸钠</td><td>8份</td></tr><tr><td>引发剂：偶氮二异丁酸二甲酯</td><td>1.5份</td></tr><tr><td>中和剂：N，N-二甲基乙醇胺</td><td>2.5份</td></tr><tr><td>链转移剂：十二烷基硫醇</td><td>1.5份</td></tr><tr><td>总计：</td><td>100份</td></tr></table></body></html>\n\n[0075] (2)含磺酸盐的聚丙烯酸酯的制备：按上述配方将相应质量份甲基丙烯酸异冰片 酯、丙烯酸甲酯、丙烯酸羟丙酯、丙烯酸、甲基丙烯酸、链转移剂十二烷基硫醇混合制备混合 液I；按上述配方将相应质量份2-丙烯酰胺基-2-甲基丙磺酸钠、引发剂偶氮二异丁酸二甲  \n\n酯加入至丙二醇甲醚醋酸酯溶剂中，搅拌至完全溶解制备混合液II；向反应釜中加入 $20\\%$ 质量的混合液I和 $15\\%$ 质量的混合液II，搅拌，升温至 $85^{\\circ}\\mathrm{C}$ 保温45min，而后控制剩余混合液I和II在5h内滴加完成，保温1h，降温至 $55^{\\circ}\\mathrm{C}$ 加入2.5份的N， $\\mathrm{N^{-}}$ 二甲基乙醇胺中和得到含磺酸盐的聚丙烯酸酯；  \n\n[0076] (3)水分散体的制备：加入上述含磺酸盐的聚丙烯酸酯质量的1.7倍的去离子水乳化，得到含磺酸盐的聚丙烯酸酯水分散体；外观：乳白、半透明；固含量： $30\\%$ ；平均粒径：$300\\mathrm{nm}$ ；粘度 $(25^{\\circ}\\mathrm{C})$ 为2000CP；  \n\n[0077] (4)塑料用亲水涂料的配制：以质量份计，原料组成情况如下表8： [0078] 表8  \n\n[0079]  \n\n<html><body><table><tr><td>上述含磺酸盐的聚丙烯酸酯水分散体</td><td>73份</td></tr><tr><td>固化剂Bayhydur 304</td><td>27份</td></tr><tr><td>润湿剂BYK-346</td><td>0.5份</td></tr><tr><td>消泡剂TEGO-815</td><td>0.2份</td></tr></table></body></html>  \n\n[0080] 按上述配方将相应质量份含磺酸盐的聚丙烯酸酯水分散体、消泡剂TEGO-815、润湿剂BYK-346加入到搅拌釜中，分散30分钟，过滤出料。水性多异氰酸酯固化剂Bayhydur304按照NCO/OH摩尔比为1.5加入到上述含磺酸盐的聚丙烯酸酯水分散体配制的涂料中，搅拌6分钟，静置消泡，用刷涂的方法在ABS基材上施工，常温下固化干燥7天，进行相应的涂膜性能测定。  \n\n[0081] 表9  \n\n<html><body><table><tr><td rowspan=\"7\">[0082]</td><td>检测项目</td><td>本实施例涂料</td><td>检测方法</td></tr><tr><td>表干时间/min</td><td>50</td><td>GB/T 1728-1979(1989)</td></tr><tr><td>实干时间/h</td><td>12</td><td>GB/T 1728-1979(1989)</td></tr><tr><td>光泽度(60°)</td><td>99</td><td>GB/T 9754-2007</td></tr><tr><td>铅笔硬度</td><td>2H</td><td>GB/T 6739-2006</td></tr><tr><td>附着力/级 (划格法)</td><td>1</td><td>GB/T 6739-2006</td></tr><tr><td>耐水性</td><td>无异常</td><td>GB/T 5209-1985</td></tr><tr><td>接触角/°</td><td>30</td><td>GB/T 30693-2014</td></tr><tr><td>透明性 (目测法)</td><td>好</td><td>GB/T1721-79(1989)</td></tr><tr><td>[0083] 贮存稳定性</td><td>无异常</td><td>HG/T2454-2006</td></tr></table></body></html>  \n\n[0084] 实施例4  \n[0085] 含磺酸盐的聚丙烯酸酯水分散体的制备  \n[0086] (1)以质量份计，一种含磺酸盐的聚丙烯酸酯的原料配方组分如下表10：  \n[0087] 表10  \n\n<html><body><table><tr><td>溶剂： 乙酸乙酯 丙烯酸单体： 甲基丙烯酸丁酯</td></tr></table></body></html>  \n\n[0089] (2)含磺酸盐的聚丙烯酸酯的制备：按上述配方将相应质量份甲基丙烯酸丁酯、丙烯酸异辛酯、甲基丙烯酸羟丙酯、丙烯酸、链转移剂巯基丙醇混合制备混合液I；按上述配方将相应质量份烯丙氧基脂肪醇氧乙烯醚硫酸铵、引发剂偶氮二异丁脒盐酸盐加入至乙酸乙酯溶剂中，搅拌至完全溶解制备混合液II；向反应釜中加入 $20\\%$ 质量的混合液I和 $20\\%$ 质量的混合液II，搅拌，升温至 $90^{\\circ}\\mathrm{C}$ 保温45min，而后控制剩余混合液I和II在5h内滴加完成，保温1.5h，降温至 $60^{\\circ}\\mathrm{C}$ 加入2份的N，N-二甲基乙醇胺中和，得到含磺酸盐的聚丙烯酸酯；  \n\n[0090] (3)水分散体的制备：加入上述含磺酸盐的聚丙烯酸酯质量的3.0倍的去离子水乳化，得到含磺酸盐的聚丙烯酸酯水分散体；外观：乳白、半透明；固含量： $20\\%$ ；平均粒径：$250\\mathrm{nm}$ ；粘度 $(25^{\\circ}\\mathrm{C})$ 为3000CP；  \n\n[0091] (4)塑料用亲水涂料的配制：以质量份计，原料组成情况如下表11：[0092] 表11  \n\n[0093]  \n\n<html><body><table><tr><td>上述含磺酸盐的聚丙烯酸酯水分散体</td><td>82份</td></tr><tr><td>固化剂BayhydurXP2547</td><td>18份</td></tr><tr><td>润湿剂TEGO-245</td><td>0.3份</td></tr><tr><td>润湿剂TEGO-500</td><td>0.3份</td></tr><tr><td>消泡剂TEGO-825</td><td>0.2份</td></tr></table></body></html>  \n\n[0094] 按上述配方将相应质量份含磺酸盐的聚丙烯酸酯水分散体、消泡剂TEGO-825、润湿剂TEGO-245和TEGO-500加入到搅拌釜中，分散25分钟，过滤出料。水性多异氰酸酯固化剂Bayhydur  XP  2547按照NCO/OH摩尔比为1 .2加入到上述含磺酸盐的聚丙烯酸酯水分散体配制的涂料中，搅拌7分钟，静置消泡，用刷涂的方法在ABS基材上施工，常温下固化干燥7天，  \n\n进行相应的涂膜性能测定。  \n\n[0095] 表12  \n\n<html><body><table><tr><td rowspan=\"7\">[0096]</td><td>检测项目</td><td>本实施例涂料</td><td>检测方法</td></tr><tr><td>表干时间/min</td><td>60</td><td>GB/T 1728-1979(1989)</td></tr><tr><td>实干时间/h</td><td>14</td><td>GB/T 1728-1979(1989)</td></tr><tr><td>光泽度(60°)</td><td>99</td><td>GB/T9754-2007</td></tr><tr><td>铅笔硬度</td><td>H</td><td>GB/T 6739-2006</td></tr><tr><td>附着力/级 (划格法)</td><td>1</td><td>GB/T6739-2006</td></tr><tr><td>耐水性</td><td>无异常</td><td>GB/T5209-1985</td></tr><tr><td>接触角/°</td><td>28</td><td>GB/T30693-2014</td></tr><tr><td>透明性 (目测法)</td><td>好</td><td>GB/T1721-79(1989)</td></tr><tr><td>贮存稳定性</td><td>无异常</td><td>HG/T2454-2006</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 实施例5  \n\n[0097] [0098] [0099] [0100]  \n\n含磺酸盐的聚丙烯酸酯水分散体的制备(1)以质量份计，一种含磺酸盐的聚丙烯酸酯的原料配方组分如下表13：表13  \n\n[0101]  \n\n溶剂：  \n丙酮 25份  \n丙烯酸单体：  \n\n<html><body><table><tr><td rowspan=\"14\">[0102]</td><td>甲基丙烯酸丁酯</td><td>15份</td></tr><tr><td>甲基丙烯酸甲酯</td><td>15份</td></tr><tr><td>丙烯酸异辛酯</td><td>25份</td></tr><tr><td>衣康酸</td><td>1.0份</td></tr><tr><td>甲基丙烯酸羟丙酯</td><td>11.5份</td></tr><tr><td>烯丙氧基脂肪醇氧乙烯醚硫酸铵</td><td>4份</td></tr><tr><td>引发剂：偶氮二异丁胱盐酸盐</td><td>1.0份</td></tr><tr><td>中和剂：三乙胺</td><td>1.5份</td></tr><tr><td>链转移剂：</td><td></td></tr><tr><td>十二烷基硫醇</td><td>0.5份</td></tr><tr><td>硫基丙醇</td><td>0.5份</td></tr><tr><td>总计：</td><td>100份</td></tr></table></body></html>  \n\n[0103] (2)含磺酸盐的聚丙烯酸酯的制备：按上述配方将相应质量份甲基丙烯酸丁酯、甲基丙烯酸甲酯、丙烯酸异辛酯、甲基丙烯酸羟丙酯、衣康酸、链转移剂巯基丙醇和十二烷基硫醇混合制备混合液I；按上述配方将相应质量份烯丙氧基脂肪醇氧乙烯醚硫酸铵、引发剂偶氮二异丁脒盐酸盐加入至丙酮溶剂中，搅拌至完全溶解制备混合液II；向反应釜中加入$10\\%$ 质量的混合液I和 $20\\%$ 质量的混合液II，搅拌，升温至 $90^{\\circ}\\mathrm{C}$ 保温60min，而后控制剩余混合液I和II在4h内滴加完成，保温1.5h，降温至 $50^{\\circ}\\mathrm{C}$ 加入1.5份的三乙胺中和，得到含磺酸盐的聚丙烯酸酯；  \n\n[0104] (3)水分散体的制备：加入上述含磺酸盐的聚丙烯酸酯质量的1.3倍的去离子水乳化，得到含磺酸盐的聚丙烯酸酯水分散体；外观：乳白、半透明；固含量： $35\\%$ ；平均粒径：$176\\mathrm{{nm}}$ ；粘度 $(\\mathrm{25^{\\circ}C)}$ 为5000CP；  \n\n[0105] (4)塑料用亲水涂料的配制：以质量份计，原料组成情况如下表14： [0106] 表14  \n\n[0107]  \n\n<html><body><table><tr><td></td><td>上述含磺酸盐的聚丙烯酸酯水分散体 80份</td></tr><tr><td>固化剂BayhydurXP2547</td><td>11份</td></tr><tr><td>107] 固化剂Bayhydur3100</td><td>9份</td></tr><tr><td>润湿剂TEGO-245</td><td>0.5份</td></tr><tr><td>消泡剂BYK-019</td><td>0.2份</td></tr></table></body></html>  \n\n[0108] 按上述配方将相应质量份含磺酸盐的聚丙烯酸酯水分散体、消泡剂BYK-019、润湿剂TEGO-245加入到搅拌釜中，分散15分钟，过滤出料。水性多异氰酸酯固化剂Bayhydur  XP2547、Bayhydur3100混合物按照NCO/OH摩尔比为1.4加入到上述含磺酸盐的聚丙烯酸酯水分散体配制的涂料中，搅拌5分钟，静置消泡，用刷涂的方法在ABS基材上施工，常温下固化  \n\n干燥7天，进行相应的涂膜性能测定。 [0109] 表15  \n\n<html><body><table><tr><td>检测项目</td><td>本实施例涂料</td><td>检测方法</td></tr><tr><td>表干时间/min</td><td>40</td><td>GB/T 1728-1979(1989)</td></tr><tr><td>实干时间/h</td><td>12</td><td>GB/T 1728-1979(1989)</td></tr><tr><td>光泽度(60°)</td><td>99</td><td>GB/T9754-2007</td></tr><tr><td>铅笔硬度</td><td>H</td><td>GB/T6739-2006</td></tr><tr><td>附着力/级 (划格法)</td><td>1</td><td>GB/T6739-2006</td></tr><tr><td>耐水性</td><td>无异常</td><td>GB/T5209-1985</td></tr><tr><td>接触角/°</td><td>23</td><td>GB/T30693-2014</td></tr><tr><td>透明性（目测法）</td><td>好</td><td>GB/T1721-79(1989)</td></tr><tr><td>贮存稳定性</td><td>无异常</td><td>HG/T2454-2006</td></tr></table></body></html>  \n\n[0115]  \n\n实施例6  \n含磺酸盐的聚丙烯酸酯水分散体的制备  \n(1)以质量份计，一种含磺酸盐的聚丙烯酸酯的原料配方组分如下表16：  \n表16  \n\n<html><body><table><tr><td>溶剂：</td></tr><tr><td>丁酮 25份</td></tr><tr><td>丙烯酸单体：</td></tr><tr><td>甲基丙烯酸丁酯 27份</td></tr><tr><td>丙烯酸乙酯 13份</td></tr><tr><td>丙烯酸异辛酯 12份</td></tr><tr><td>顺酐 1.0份 甲基丙烯酸羟丙酯 6份</td></tr><tr><td>丙烯酸羟乙酯 7份</td></tr></table></body></html>  \n\n<html><body><table><tr><td colspan=\"2\">烯丙氧基脂肪醇氧乙烯醚硫酸铵</td><td>3.0份</td></tr><tr><td rowspan=\"6\">[0116]</td><td>乙烯基磺酸钠</td><td>2.5份</td></tr><tr><td>引发剂： 偶氮异丁氰基甲酰胺</td><td>1.0份</td></tr><tr><td>中和剂：</td><td></td></tr><tr><td>2-氨基-2-甲基丙醇</td><td>0.75份</td></tr><tr><td>N，N-二甲基乙醇胺</td><td>0.75份</td></tr><tr><td>链转移剂：十二烷基硫醇</td><td>1.0份</td></tr><tr><td>总计：</td><td></td><td>100份</td></tr></table></body></html>  \n\n[0117] (2)含磺酸盐的聚丙烯酸酯的制备：按上述配方将相应质量份甲基丙烯酸丁酯、丙烯酸乙酯、丙烯酸异辛酯、甲基丙烯酸羟丙酯、丙烯酸羟乙酯、顺酐、链转移剂十二烷基硫醇混合制备混合液I；按上述配方将相应质量份乙烯基磺酸钠、烯丙氧基脂肪醇氧乙烯醚硫酸铵、引发剂偶氮异丁氰基甲酰胺加入至丁酮溶剂中，搅拌至完全溶解制备混合液II；向反应釜中加入 $30\\%$ 质量的混合液I和 $20\\%$ 质量的混合液II，搅拌，升温至 $90^{\\circ}\\mathrm{C}$ 保温60min，而后控制剩余混合液I和II在5h内滴加完成，保温1.5h，降温至 $60^{\\circ}\\mathrm{C}$ 加入1.5份的 $\\mathrm{N,N^{-}}$ 二甲基乙醇胺、2-氨基 $\\cdot-2-$ 甲基丙醇混合物中和，得到含磺酸盐的聚丙烯酸酯；  \n\n[0118] (3)水分散体的制备：加入上述含磺酸盐的聚丙烯酸酯质量的1.5倍的去离子水乳化，得到含磺酸盐的聚丙烯酸酯水分散体；外观：乳白、半透明；固含量： $30\\%$ ；平均粒径：$240\\mathrm{nm}$ ；粘度 $(25^{\\circ}\\mathrm{C})$ 为1800CP；  \n\n[0119] (4)塑料用亲水涂料的配制：以质量份计，原料组成情况如下表17： [0120] 表17  \n\n[0121]  \n\n<html><body><table><tr><td>上述含磺酸盐的聚丙烯酸酯水分散体</td><td>76份</td></tr><tr><td>固化剂Bayhydur3100</td><td>24份</td></tr><tr><td>润湿剂TEGO-500</td><td>0.4份</td></tr><tr><td>消泡剂BYK-020</td><td>0.3份</td></tr></table></body></html>  \n\n[0122] 按上述配方将相应质量份含磺酸盐的聚丙烯酸酯水分散体、消泡剂BYK-020、润湿剂TEGO-500加入到搅拌釜中，分散20分钟，过滤出料。水性多异氰酸酯固化剂Bayhydur3100按照NCO/OH摩尔比为1.7加入到上述含磺酸盐的聚丙烯酸酯水分散体配制的涂料中，搅拌8分钟，静置消泡，用刷涂的方法在ABS基材上施工，常温下固化干燥7天，进行相应的涂膜性能测定。  \n\n[0123] 表18  \n\n<html><body><table><tr><td rowspan=\"11\">[0124]</td><td>检测项目</td><td>本实施例涂料</td><td>检测方法</td></tr><tr><td>表干时间/min</td><td>60</td><td>GB/T 1728-1979(1989)</td></tr><tr><td>实干时间/h</td><td>13</td><td>GB/T 1728-1979(1989)</td></tr><tr><td>光泽度(60°)</td><td>98</td><td>GB/T9754-2007</td></tr><tr><td>铅笔硬度</td><td>2H</td><td>GB/T6739-2006</td></tr><tr><td>附着力/级 (划格法)</td><td>1</td><td>GB/T 6739-2006</td></tr><tr><td>耐水性</td><td>无异常</td><td>GB/T 5209-1985</td></tr><tr><td>接触角/°</td><td>32</td><td>GB/T30693-2014</td></tr><tr><td>透明性 (目测法)</td><td>好</td><td>GB/T1721-79(1989)</td></tr><tr><td>贮存稳定性</td><td>无异常</td><td>HG/T2454-2006</td></tr></table></body></html>  \n\n[0125] 实施例7  \n[0126] 含磺酸盐的聚丙烯酸酯水分散体的制备  \n[0127] (1)以质量份计，一种含磺酸盐的聚丙烯酸酯的原料配方组分如下表19：  \n[0128] 表19  \n\n<html><body><table><tr><td>溶剂：</td></tr><tr><td>乙酸乙酯 20份</td></tr><tr><td>丙酮 5份</td></tr><tr><td>丙烯酸单体： 甲基丙烯酸甲酯 26份</td></tr><tr><td>丙烯酸丁酯 22份</td></tr><tr><td>丙烯酸 2.0份</td></tr><tr><td>甲基丙烯酸羟乙酯 11.5份</td></tr><tr><td>2-丙烯酰胺基-2-甲基丙磺酸 4.0份</td></tr><tr><td>乙烯基磺酸钠 1.4份</td></tr><tr><td>引发剂： 1.0份</td></tr><tr><td>偶氮二异丁咪唑啉盐酸盐 0.7份</td></tr><tr><td>偶氮异丁氰基甲酰胺 0.8份</td></tr></table></body></html>  \n\n<html><body><table><tr><td></td><td>中和剂： 2-氨基-2-甲基丙醇</td><td>4.5份</td></tr><tr><td>[0130]</td><td>链转移剂：琉基乙醇</td><td>1.1份</td></tr><tr><td></td><td>总计：</td><td>100份</td></tr></table></body></html>  \n\n[0131] (2)含磺酸盐的聚丙烯酸酯的制备：按上述配方将相应质量份甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸羟乙酯、丙烯酸、链转移剂巯基乙醇混合制备混合液I；按上述配方将相应质量份将 $2^{-}$ 丙烯酰胺基 $^{-2-}$ 甲基丙磺酸、乙烯基磺酸钠、引发剂偶氮二异丁咪唑啉盐酸盐、偶氮异丁氰基甲酰胺加入至乙酸乙酯和丙酮溶剂中，搅拌至完全溶解制备混合液II；向反应釜中加入 $20\\%$ 质量的混合液I和 $20\\%$ 质量的混合液II，搅拌，升温至 $95^{\\circ}\\mathrm{C}$ 保温50min，而后控制剩余混合液I和II在5h内滴加完成，保温 $\\mathrm{2h}$ ，降温至 $70\\mathrm{{^\\circC}}$ 加入4.5份的 $2^{-}$ 氨基 $-2-$ 甲基丙醇中和，得到含磺酸盐的聚丙烯酸酯；  \n\n[0132] (3)水分散体的制备：加入上述含磺酸盐的聚丙烯酸酯质量的1.0倍的去离子水乳化，得到含磺酸盐的聚丙烯酸酯水分散体；外观：乳白、半透明；固含量： $37.5\\%$ ；平均粒径：$90\\mathrm{nm}$ ；粘度 $(25^{\\circ}\\mathrm{C})$ 为1600CP；  \n\n[0133] (4)塑料用亲水涂料的配制：以质量份计，原料组成情况如下表20： [0134] 表20  \n\n[0135]  \n\n<html><body><table><tr><td>上述含磺酸盐的聚丙烯酸酯水分散体</td><td>82份</td></tr><tr><td>固化剂DesmodurDA-L</td><td>18份</td></tr><tr><td>润湿剂TEGO-245</td><td>0.5份</td></tr><tr><td>消泡剂BYK-019</td><td>0.15份</td></tr><tr><td>消泡剂BYK-020</td><td>0.15份</td></tr></table></body></html>  \n\n[0136] 按上述配方将相应质量份含磺酸盐的聚丙烯酸酯水分散体、消泡剂BYK-019和BYK-020、润湿剂TEGO-245加入到搅拌釜中，分散10分钟，过滤出料。水性多异氰酸酯固化剂Desmodur  DA-L按照NCO/OH摩尔比为1.3加入到上述含磺酸盐的聚丙烯酸酯水分散体配制的涂料中，搅拌8分钟，静置消泡，用刷涂的方法在ABS基材上施工，常温下固化干燥7天，进行相应的涂膜性能测定。  \n\n[0137] 表21  \n\n[0138]  \n\n<html><body><table><tr><td>检测项目</td><td>本实施例涂料</td><td>检测方法</td></tr><tr><td>表干时间/min</td><td>50</td><td>GB/T 1728-1979(1989)</td></tr><tr><td>实干时间/h</td><td>14</td><td>GB/T 1728-1979(1989)</td></tr></table></body></html>  \n\n<html><body><table><tr><td rowspan=\"7\">[0139]</td><td>光泽度(60°)</td><td>99</td><td>GB/T 9754-2007</td></tr><tr><td>铅笔硬度</td><td>2H</td><td>GB/T 6739-2006</td></tr><tr><td>附着力/级 (划格法)</td><td>1</td><td>GB/T 6739-2006</td></tr><tr><td>耐水性</td><td>无异常</td><td>GB/T 5209-1985</td></tr><tr><td>接触角/°</td><td>20</td><td>GB/T30693-2014</td></tr><tr><td>透明性(目测法)</td><td>好</td><td>GB/T1721-79(1989)</td></tr><tr><td>贮存稳定性</td><td>无异常</td><td>HG/T2454-2006</td></tr></table></body></html>  \n\n[0140] 本发明制备的塑料用亲水涂料具有反应条件温和、制备工艺简单、低VOC排放的特点，所制备涂膜具有亲水性强、光泽度高、耐水性好、硬度高等特点。[0141] 本发明不受上述实施例约束，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的替代方式，都包含在本发明的保护范围之内。  \n\n![](images/19a2d0a03fb75ddacb94ab7668b79c42a4c47e8fc0af1736b5cd360c81a93f43.jpg)  \n图1",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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new file mode 100644
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@@ -0,0 +1,52 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利申请  \n\n(21)申请号 201910237001 .0  \n(22)申请日 2019.03 .27  \n(71)申请人 浙江润禾有机硅新材料有限公司地址 313200 浙江省湖州市德清经济开发区长虹东街  \n(72)发明人 严明亮 廖乐新 许振浩 陆思琪房小平  \n(74)专利代理机构 杭州恒翌专利代理事务所(特殊普通合伙) 33298代理人 王从友  \n(51)Int.Cl .C07F 7/08(2006.01)C09D 7/65(2018.01)C08G 65/3 6(2006.01)",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n一种双生结构聚醚硅氧烷及制备方法",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明涉及有机硅表面活性剂领域，有涉及一种双生结构聚醚硅氧烷及制备方法。本发明双生结构聚醚硅氧烷含有多个疏水链接，两个亲水链接，一个柔性桥链接基；其 $0.1\\%$ 水溶液表面张力为 $20{-}30\\mathrm{mN/m}$ ；具有消泡抑泡效果，耐水解性好且能保持长时间润湿性。本发明产品作为水性涂料润湿流平剂，兼有优异的消抑泡效果，并在碱性条件下耐水解。  \n\n![](images/b58753f3bfa1b3c7b4ae6791c3640ed00f8197bd42cf81dabaaaf58ea7556c31.jpg)  \n\n1.一种双生结构聚醚硅氧烷，结构如下：  \n\n![](images/3ffd42843fcc261a5927244153d796caa92b380f1f16b6e86fa280c437bbecb8.jpg)  \n\n其中， $\\mathbb{R}^{1}$ 是氢，烷基或芳基； $\\mathrm{R}^{2}$ 是氢和烷基中的一种或多种； $\\mathrm{R}^{3}$ 是氢，烷基和酰基中的一种或多种； $\\mathrm{R^{4}}$ 是氢，烷基和芳基中的一种或多种， $\\mathrm{R}^{5}$ 是烷基或芳基； $\\scriptstyle0\\leqslant\\mathrm{a}\\leqslant10;0\\leqslant\\mathrm{m}\\leqslant50;0\\leqslant\\mathrm{n}$ $\\leqslant30$ 。  \n\n2.根据权利要求1所述的一种双生结构聚醚硅氧烷，其特征在于， $\\mathrm{R}^{1}$ 是烷基。  \n\n3.根据权利要求1所述的一种双生结构聚醚硅氧烷，其特征在于，至少一个 $\\cdot\\mathrm{R}^{2}$ 是烷基  。  \n\n4.根据权利要求1所述的一种双生结构聚醚硅氧烷，其特征在于， $\\mathrm{R}^{3}$ 是为氢。  \n\n5.根据权利要求1所述的一种双生结构聚醚硅氧烷，其特征在于， $\\mathrm{R^{4}}$ 是甲基和乙基中的一种或多种， $\\mathrm{R}^{5}$ 是甲基或乙基。  \n\n6.根据权利要求1所述的一种双生结构聚醚硅氧烷，其特征在于  ， $1{\\leqslant}\\mathrm{a}{\\leqslant}2,0{\\leqslant}\\mathrm{m}{\\leqslant}30$ ，$0\\leqslant\\mathrm{{n}}\\leqslant30$ ，且 $\\boldsymbol{\\mathrm{n}}\\langle\\boldsymbol{\\mathrm{m}}$ 。  \n\n7.一种制备权利要求 $1{\\sim}6$ 任意一项权利要求所述的聚醚硅氧烷的制备方法，该方法包括以下的步骤：将化合物A与化合物B混合搅拌均匀，通惰性气体保护，升温至 $50{-}100^{\\circ}\\mathrm{C}$ ,加入催化剂，在 $100^{\\circ}\\mathrm{C}-140^{\\circ}\\mathrm{C}$ 反应 $2\\mathrm{-}8\\mathrm{h}$ ，在真空有惰性气体保护条件下，脱除低分子即得所述双生结构聚醚硅氧烷；  \n\n所述的化合物A的结构式如下：  \n\n![](images/47fd8bd49be118b7433e9657a6edd4b75bd90a125242c0680623b9bf76aee004.jpg)  \n\n所述的化合物B的结构式如下：  \n\n![](images/06694f20fbaba6faebf2de8b3fdd1fd11706acc17d29b7b25fdd42097895d4d6.jpg)  \n\n8.根据权利要求7所述的方法，其特征在于，所述的化合物B与化合物A的摩尔比例为$0.8\\mathrm{-}1.5\\colon1$ ，优选为1.2；加入催化剂温度 $50\\mathrm{-}100^{\\circ}\\mathrm{C}$ ，优选为 $60\\mathrm{-}80^{\\circ}\\mathrm{C}$ ；反应温度为 $100{-}150^{\\circ}\\mathrm{C}$ ，优选为 $110{-}140^{\\circ}\\mathrm{C}$ ；反应时间为 $2^{-}8\\mathrm{h}$ ，优选为 $4{\\mathrm{-}}6\\mathrm{h}$ 。  \n\n9.根据权利要求7所述的方法，其特征在于，所述催化剂为铂、铑、钯或它们的化合物，催化剂用量为 $5{-}300\\mathrm{ppm}$ ,优选为10-200ppm。  \n\n10.根据权利要求7所述的方法，其特征在于，所述惰性气体为氮气。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 一种双生结构聚醚硅氧烷及制备方法",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明涉及有机硅表面活性剂领域，有涉及一种双生结构聚醚硅氧烷及制备方法。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 有机硅表面活性剂主要是以聚二甲基硅氧烷为主链，在其侧链或末端含有一个或多个极性基团而构成的一类表面活性剂。从20世60年代，已经开始用于工业领域，大规模使用于20世纪80年代，这类表面活性剂具有独特的优点。有机硅表面活性剂特别是聚醚改性三硅氧烷，其甲基以独特的“伞型”结构，吸附于空气与水相邻界面上，可使表面张力降至$20\\mathrm{mN/m}$ 左右。聚醚改性三硅氧烷不仅能降低油水界面的界面张力，同时还能在疏水表面润湿扩展，这一能力称为“超级润湿性”或“超级铺展性”。但是聚醚改性三硅氧烷表面活性剂如：迈图高新材料CoatOSil  77和道康宁公司OFX-5211等产品，在碱性(PH>8)条件下，分子进一步缩合生成更高分子量的聚醚硅氧烷，导致表面张力上升，润湿作用降低，作为水性涂料润湿剂，在动态施工过程中出现大量泡沫，影响施工效率，长时间过后，施工底材出现缩孔、火山口效应等不良现象，影响了产品的使用效果。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0003] 为了解决上述的技术问题，本发明第一个目的是提供了一种双生结构聚醚硅氧烷，该聚醚硅氧烷具有消泡抑泡效果，耐水解性好且能保持长时间润湿性。本发明另一个目的是提供上述双生结构聚醚硅氧烷的制备方法。  \n\n[0004] 为了实现上述第一个目的，本发明采用了以下的技术方案：  \n\n一种双生结构聚醚硅氧烷，结构如下：  \n\n![](images/1e87fe5c9af86d8c41581a0235b1503320e1a33fdc1b943ee668492cffcd54db.jpg)  \n\n其中，  \n\n$\\mathrm{R}^{1}$ 是氢，烷基或芳基； $\\mathrm{R}^{2}$ 是氢和烷基中的一种或多种； $\\mathrm{R}^{3}$ 是氢，烷基和酰基中的一种或多种； $\\mathrm{R^{4}}$ 是氢，烷基和芳基中的一种或多种， $\\mathrm{R}^{5}$ 是烷基或芳基； $\\mathtt{0{\\le}a{\\le}10,0{\\le}m{\\le}50,0{\\le}n{\\le}30}$ 。  \n\n[0005] 作为优选， $\\mathbb{R}^{1}$ 是烷基。  \n[0006] 作为优选，至少一个 $\\cdot{\\mathrm{R}}^{2}$ 是烷基。  \n[0007] 作为优选， $\\mathrm{R}^{3}$ 是为氢。  \n[0008] 作为优选， $\\mathrm{R^{4}}$ 是甲基和乙基中的一种或多种， $\\mathrm{R}^{5}$ 是甲基或乙基。  \n[0009] 作为优选， $1\\leqslant\\mathsf{a}\\leqslant2,0\\leqslant\\mathsf{m}\\leqslant30,0\\leqslant\\mathsf{n}\\leqslant30$ ，且 $\\mathrm{n}{\\left<}{\\mathrm{m}}\\right.$ 。  \n[0010] 为了实现上述第二个目的，本发明采用了以下的技术方案：  \n\n一种制备所述的聚醚硅氧烷的制备方法，该方法包括以下的步骤：将化合物A与化合物B混合搅拌均匀，通惰性气体保护，升温至 $50{-}100^{\\circ}\\mathrm{C}$ ,加入催化剂，在 $100^{\\circ}\\mathrm{C}-140^{\\circ}\\mathrm{C}$ 反应 $2\\mathrm{-}8\\mathrm{h}$ ，在真空有惰性气体保护条件下，脱除低分子即得所述双生结构聚醚硅氧烷；  \n\n所述的化合物A的结构式如下：  \n\n![](images/7ceb8b53a67175bcc2ccbdace64d1010364d0367be8e96f82950c21f5a66977e.jpg)  \n\n所述的化合物B的结构式如下：  \n\n![](images/fdb39b0d58eddcbd6292b0b989f7dda8ffe4d2b48e5bc5131d4bdd73dcafb471.jpg)  \n\n[0011] 作为进一步改进，所述的化合物B与化合物A的摩尔比例为0.8-1.5:1，优选为1.2；加入催化剂温度 $50\\mathrm{-}100^{\\circ}\\mathrm{C}$ ，优选为 $60{-}80^{\\circ}\\mathrm{C}$ ；反应温度为 $100{-}150^{\\circ}\\mathrm{C}$ ，优选为 $110{-}140^{\\circ}\\mathrm{C}$ ；反应时间为 $2\\mathrm{-}8\\mathrm{h}$ ，优选为 $4{\\mathrm{-}}6\\mathrm{h}$ 。  \n\n[0012] 作为进一步改进，所述催化剂为铂、铑、钯或它们的化合物，催化剂用量为 $5-$ $300\\mathrm{{ppm}}$ ,优选为10-200ppm。  \n\n[0013] 作为进一步改进，所述惰性气体为氮气。  \n\n[0014] 本发明由于采用了上述的技术方案，该双生结构聚醚硅氧烷含有多个疏水链接，两个亲水链接，一个柔性桥链接基；其 $0.1\\%$ 水溶液表面张力为 $20{-}30\\mathrm{mN/m}$ ；具有消泡抑泡效果，耐水解性好且能保持长时间润湿性。本发明产品作为水性和油性涂料润湿流平剂，兼有优异的消抑泡效果，并在碱性条件下耐水解。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 附图说明  \n\n[0015] 图1为实施例1的红外光谱图。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 具体实施方式  \n\n[0016] 下面对本发明的事实作具体说明，但实施例不是对本发明保护范围的限制。[0017] 实施例1  \n\n在装有电动搅拌器、温度计的250ml干燥三口瓶中，分别加入46克七甲基三硅氧烷、100克2,4,7,9-四甲基-5-癸炔-4,7-二醇四乙氧基醚搅拌均匀，通N2，然后升温，当温度升至60$\\mathrm{{^\\circC}}$ ，加入氯铂酸催化剂0.2克（铂添加量相当于总物料量的10PPM），继续升温至 $110^{\\circ}\\mathrm{C}$ ，反应4h，在N2保护下，抽真空脱除低组分，即得一种浅黄色液体RA。  \n\n[0018] 实施例  2  \n\n在装有电动搅拌器、温度计的250ml干燥三口瓶中，分别加入28克七甲基三硅氧烷、100克2,4,7,9-四甲基-5-癸炔-4,7-二醇十乙氧基醚搅拌均匀，通N2，然后升温，当温度升至70$\\mathrm{{^\\circC}}$ ，加入氯铂酸催化剂0.88克（铂添加量相当于总物料量的50PPM），继续升温至 $120^{\\circ}\\mathrm{C}$ ，反应5h，在N2保护下，抽真空脱除低组分，即得一种深黄色液体RB。  \n\n[0019] 实施例3  \n\n在装有电动搅拌器、温度计的250ml干燥三口瓶中，分别加入43克七甲基三硅氧烷、100克2 ,5 ,8 ,11-四甲基 $\\cdot-6-$ 十二碳炔-5,8-二醇四乙氧基醚搅拌均匀，通N2，然后升温，当温度升至 $80^{\\circ}\\mathrm{C}$ ，加入氯铂酸催化剂1.38克（铂添加量相当于总物料量的70PPM），继续升温至130$\\mathrm{{^\\circC}}$ ，反应6h，在N2保护下，抽真空脱除低组分，即得一种棕色液体RC。  \n\n[0020] 实施例4  \n\n在装有电动搅拌器、温度计的250ml干燥三口瓶中，分别加入34克七甲基三硅氧烷、100克2 ,4 ,7 ,9-四甲基 $\\cdot-5-$ 癸炔-4,7-二醇六乙氧基一丙氧基醚搅拌均匀，通N2，然后升温，当温度升至 $80^{\\circ}\\mathrm{C}$ ，加入氯铂酸催化剂0 .37克（铂添加量相当于总物料量的20PPM），继续升温至$130^{\\circ}\\mathrm{C}$ ，反应5h，在N2保护下，抽真空脱除低组分，即得一种浅黄色液体RD。  \n\n[0021] 实施例5  \n\n在装有电动搅拌器、温度计的 $250\\mathrm{ml}$ 干燥三口瓶中，分别加入14克七甲基三硅氧烷、100克2 ,4 ,7 ,9-四甲基 $\\cdot-5-$ 癸炔-4,7-二醇三十乙氧基醚搅拌均匀，通N2，然后升温，当温度升至$70^{\\circ}\\mathrm{C}$ ，加入氯铂酸催化剂0.79克（铂添加量相当于总物料量的50PPM），继续升温至 $120^{\\circ}\\mathrm{C}$ ，反应4h，在N2保护下，抽真空脱除低组分，即得一种深黄色液体RE。  \n\n[0022] 分别对其进行物化参数测试，结果如下：  \n\n<html><body><table><tr><td colspan=\"7\">实施例物化参数表</td></tr><tr><td>编号</td><td>0.1%水溶液 外观</td><td>0.1%水溶液起泡 高度（mm）</td><td>0.1%水溶液25°℃下表 面张力（mN/m）</td><td colspan=\"3\">0.1%水溶液（PH=9-10）25°℃ 下表面张力（mH/m）</td></tr><tr><td>RA</td><td>部分分散</td><td></td><td>21.8</td><td>1周 22.4</td><td>4周 22.6</td><td>8周 22.4</td></tr><tr><td>RB</td><td>均一分散液</td><td>0.5</td><td>23.0</td><td>22.8</td><td>23.1</td><td>23.0</td></tr><tr><td>RC</td><td>部分分散</td><td></td><td>21.4</td><td>21.5</td><td>21.4</td><td>21.6</td></tr><tr><td>RD</td><td>均一分散液</td><td></td><td>23.6</td><td>23.5</td><td>23.6</td><td>23.7</td></tr><tr><td>RE</td><td>均一分散液</td><td>2</td><td>25.3</td><td>25.6</td><td>25.5</td><td>25.8</td></tr><tr><td>市售聚醚 改性三硅 氧烷表面</td><td>均相</td><td>10</td><td>20.5</td><td>35.4</td><td></td><td></td></tr></table></body></html>  \n\n注： $\\textcircled{1}0.1\\%$ 实施例产物水溶液外观均一性：浑浊、不漂油。[0023] $\\textcircled{2}$ 起泡高度是用 $100\\mathrm{ml}$ 具塞量筒，装 $20\\mathrm{ml}0.1\\%$ 实施例产物水溶液，上下振荡20次，测得泡沫高度。[0024] $\\textcircled{3}0.1\\%$ 实施例产物水溶液在全自动表面张力仪上测出的表面张力，单位 $\\mathrm{mN/m}$ 。[0025] $\\textcircled{4}$ 碱性条件下耐水解性测试： $0.1\\%$ 实施例产物水溶液 $(\\mathrm{PH}{=}9{-}10)$ ），表面张力在1周、4周、8周的对比测试。[0026] 从上表可以看出，本发明RB  、 RD和RE所制得的双生结构聚醚硅氧烷作为水性和油性涂料润湿剂，比市售聚醚改性三硅氧烷表面活性剂拥有更好的消泡抑泡性，耐水解性。而RA和RC所制得的双生结构聚醚硅氧烷作为油性涂料润湿剂。[0027] 以上为对本发明实施例的描述，通过对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的。本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施列，而是要符合与本文所公开的原理和新颖点相一致的最宽的范围。  \n\n![](images/f64f79d89816b9e9aaa79def7222b6f432d879eb51d47ab9eb2cd322967b9e59.jpg)  \n图1",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,52 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利申请  \n\n<html><body><table><tr><td>(21)申请号202011067473.5</td><td>CO9D 7/65 (2018.01)</td></tr><tr><td>(22)申请日2020.10.06</td><td rowspan=\"2\">CO9D 5/08 (2006.01)</td></tr><tr><td rowspan=\"2\">(71)申请人青岛羚智涂料科技有限责任公司</td></tr><tr><td>C08G 77/46 (2006.01)</td></tr><tr><td>地址266000 山东省青岛市青岛市前湾保</td><td></td></tr><tr><td>税港区上海路20号二号楼二层222室</td><td></td></tr><tr><td>研发中心</td><td></td></tr><tr><td>(72)发明人 李跃平</td><td></td></tr><tr><td></td><td></td></tr><tr><td>(74)专利代理机构潍坊诺诚智汇知识产权代理</td><td></td></tr><tr><td>事务所（普通合伙）37309 代理人 李海英</td><td></td></tr><tr><td></td><td></td></tr><tr><td>(51) Int.CI .</td><td></td></tr><tr><td>C09D 175/04 (2006.01)</td><td></td></tr><tr><td>CO9D 133/04 (2006.01)</td><td></td></tr><tr><td>C09D 163/00 (2006.01)</td><td></td></tr><tr><td>CO9D 183/12 (2006.01)</td><td></td></tr></table></body></html>",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n水性防雾涂料及其制备方法",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明涉及一种性能优异的水性防雾涂料，包括水性树脂乳液 $80-100\\mathrm{g}$ ，交联剂 $10-30\\mathrm{g}$ ，防雾改性剂 $10-30\\mathrm{g}$ ，其特征在于：防雾改性剂是一种星型结构的有机硅氧烷化合物。在该星型结构中，笼型聚倍半硅氧烷类化合物作为核心，并在其表面接枝有含有环氧丙烷链和环氧乙烷链的聚醚，既能够充分利用其作为纳米粒子化合物的物理特性，具有优异的机械强度、耐刮擦性，为水性涂料具有持久的防雾性能提供保证，又能够充分利用聚醚基团的低表面能、亲水性和润湿性，以及星型结构的支链，增强水性涂料的防雾性能。  \n\n1.一种水性防雾涂料，包括水性树脂乳液 $80{-}100\\mathrm{g}$ ，交联剂 $10{-}30\\mathrm{g}$ ，防雾改性剂 $10{-}30\\mathrm{g}$ ，其特征在于：防雾改性剂是一种星型结构的有机硅氧烷化合物，通过式（1）所示的八乙烯基聚倍半硅氧烷与式（2）所示的含有环氧丙烷链和环氧乙烷链的聚醚进行加成反应制备得到；  \n\n其中，式（1）为：  \n\n![](images/10f98009fb0bf6c87d11f49e96b585677a97f02c3d44c591dc32c259e68ec669.jpg)  \n\n式（2）为：  \n\nCH3$C H_{3}$ -CHCH-O-（CH-CH-O）m-（CH-CH-O）-CH3其中，m为3-15，优选为5-10，n为3-20，优选为5-15；反应式为：  \n\n![](images/b4a30608f695e52e5503a39f6a2699afdb95da7e641ca2d4805078b19020b2df.jpg)  \n\n![](images/79605e7587954998d9c1956c07ae95f9e8de1427fdb9c9658a4cd1f00a52fbc8.jpg)  \n\n$C H_{3}$ 其中，X为-CH-CH-CH-CH-CH-O-（CH-CH-O)-（CH-CH-O）-CH  \n\n2.如权利要求1所述的一种水性防雾涂料，其特征在于：所述加成反应在溶剂中进行，所述溶剂选自苯、甲苯、乙二醇单丁醚、乙酸乙酯、四氢呋喃中的一种或多种。3.如权利要求1所述的一种水性涂料防雾改性剂，其特征在于：所述催化剂选自铂、镍、金等催化剂，优选为氯铂酸。4.如权利要求3所述的一种水性防雾涂料，其特征在于：所述催化剂的用量为式（1）所示的八乙烯基聚倍半硅氧烷的 $1-3\\mathrm{wt\\%}$ 。  \n\n5.如权利要求1所述的一种水性防雾涂料，其特征在于：参与反应的式（1）所示的八乙烯基聚倍半硅氧烷与式（2）所示的含有环氧丙烷链和环氧乙烷链的聚醚的摩尔比 $1:(8^{-}$ 10），反应温度为 $60{-}100^{\\circ}\\mathrm{C}$ ，反应时间为 $3\\mathrm{-}6\\mathrm{h}$ 。  \n\n6.如权利要求1所述的一种水性防雾涂料，其特征在于：所述水性树脂乳液选自水性聚氨酯乳液、水性丙烯酸树脂乳液、水性环氧树脂乳液中的一种。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 水性防雾涂料及其制备方法",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明属于水性涂料领域，具体涉及水性防雾涂料及其制备方法。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 雾气是日常生活中的常见现象。由于在一些界面材料的两侧存在明显的温度差，如玻璃、塑料等，界面材料的温度通常与低温侧的温度更接近，使得温度较高一侧的空气中的水蒸气在接触到温度较低的基材时，会在其表面凝结形成流动性很差的小液滴，即产生雾气。在一些特定环境中，雾气的存在会产生很多不利影响。例如，汽车的挡风玻璃上产生了雾气，会影响驾驶员的驾驶，增加造成交通事故的风险；又如，塑料大棚的塑料薄膜上产生了雾气，会折射阳光，对大棚内的农作物的生长造成影响。因此，有必要对在这些环境中使用的透明基材进行防雾改性。  \n\n[0003] 涂覆水性防雾涂料是常用的防雾改性方法。其中，最常用的水性防雾涂料是亲水性丙烯酸酯或其共聚物，利用树脂涂层对涂层表面凝结的水分的吸收作用，起到防雾作用。然而，亲水性的丙烯酸酯或其共聚物虽然具有防雾作用，但是，其表面强度、表面耐刮擦性能、表面耐腐蚀性能等通常不够理想，特别是对于应用在透明窗口材料表面的涂覆透明防雾水性涂料，如汽车挡风玻璃表面，塑料大棚的塑料薄膜表面等，要求其不仅具备优良的防雾性能，同时其还需保持良好的表面强度、表面耐刮擦性能、表面耐腐蚀性能等。因此，本发明旨在提供一种性能优异的水性防雾涂料，不仅具有优良的防雾性能，同时，还具有良好的表面强度、表面耐刮擦性能、表面耐腐蚀性能。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0004] 本发明要解决的技术问题在于，确保优良的防雾性能的同时，改善现有的水性防雾涂料的表面强度、表面耐刮擦性、表面耐腐蚀性。  \n\n[0005] 因此，本发明的发明人提供了一种水性防雾涂料，包括水性树脂乳液 $80{-}100\\mathrm{g}$ ，交联剂 $10{-}30\\mathrm{g}$ ，防雾改性剂 $10{-}30\\mathrm{g}$ ，其特征在于：防雾改性剂是一种星型结构的有机硅氧烷化合物，该星型结构的有机硅氧烷化合物通过式（1）所示的八乙烯基聚倍半硅氧烷与式（2）所示的含有环氧丙烷链和环氧乙烷链的聚醚通过加成反应制备得到。所得到的星型结构的有机硅氧烷化合物的中心为一聚倍半硅氧烷结构，在该中的四面八方均匀分布有八个含有环氧丙烷链和环氧乙烷链的聚醚支链。  \n\n[0006] 式（1）为：  \n\n![](images/ec9df63cd28b9b95b30466279587fd94c05ca43887c9a88a1dbc4440a52c3bc0.jpg)  \n\n式（2）为：  \n\nCH3CH-CH-CH-O-（CH-CH-O）m-（CH-CH-O）-CH’其中，m为3-15，优选为5-10，n为3-20，优选为5-15；反应式为：  \n\n![](images/932657ea2713729f930df8a5ff59a2b6b9f6572d84f6b5dbca106af18c20d0ea.jpg)  \n\nCH3其中，X为-CH-CH-CH-CH-CH-O-(CH-CH-O）-（CH-CHO）-CH[0007] 其中，水性树脂乳液选自水性聚氨酯乳液、水性丙烯酸树脂乳液，水性环氧树脂乳液中的一种。  \n\n![](images/4618078e2d9ba9d522fe7859170535e058de4f288d2ec3b3f414a16b79b4d89b.jpg)  \n\n[0008] 进一步地，上述加成反应在溶剂中，所述溶剂选自苯、甲苯、乙二醇单丁醚、乙酸乙酯、四氢呋喃中的一种或多种。  \n\n[0009] 进一步地，所述催化剂选自铂、镍、金等催化剂，优选为氯铂酸。催化剂的用量为式（1）所示的八乙烯基聚倍半硅氧烷的 $1-3\\mathrm{wt\\%}$ 。  \n\n[0010] 进一步地，为了确保获得星型结构的有机硅氧烷化合物，参与反应的式（1）所示的八乙烯基聚倍半硅氧烷与式（2）所示的含有环氧丙烷链和环氧乙烷链的聚醚的摩尔比1:（8-10），反应温度为 $60{-}100^{\\circ}\\mathrm{C}$ ，反应时间为 $3\\mathrm{-}6\\mathrm{h}$ 。  \n\n[0011] 本发明的水性防雾涂料中，添加了本发明人研发的防雾改性剂可以确保涂料膜层具有优良的防雾性能，同时，还具有良好的表面强度、表面耐刮擦性能、表面耐腐蚀性能。在本发明人研发的防雾改性剂中，以八乙烯基聚倍半硅氧烷作为星型结构的核心，可以充分利用笼型聚倍半硅氧烷特殊的物理性质。笼型聚倍半硅氧烷由大量的Si-O键交替连接的硅氧骨架而形成的无机内核，三维尺寸在 $1{-}3\\mathrm{nm}$ 之间，是典型的纳米粒子化合物，是亲水性的，同时又是防水性的，还具有优异的综合性能，在机械强度、耐刮擦（或者摩擦）性、耐腐蚀性等方面尤为突出。可以明显改善水性涂料的表面强度、表面耐刮擦性能、表面耐腐蚀性能。[0012] 同时，本发明人考虑到聚倍半硅氧烷类化合物与水性涂料的润湿性较差，亲水、防雾性能不足，对八乙烯基聚倍半硅氧烷的八个乙烯基进行加成反应，将具有低表面能、亲水性和润湿性的聚醚基团接枝到聚倍半硅氧烷上，改善其与水性涂料的浸润性，并增强水性涂料的防雾性能。同时，由于八乙烯基聚倍半硅氧烷的八个乙烯基均匀分布在聚倍半硅氧烷核心结构的四面八方，使得最终的防雾改性剂为星型结构，该星型结构为涂料的亲水、吸水提供微观物理结构空间，增强了水性涂料的防雾性能。  \n\n[0013]",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 具体实施方式  \n\n[0014] 本发明的水性防雾涂料具有优异的防雾特性，同时，还可以明显改善水性涂料的表面强度、表面耐刮擦性能、表面耐腐蚀性能。为了更好地对本发明的水性防雾涂料的性能进行详细的阐述和比较，下面将结合一些本发明较佳的实例进行说明。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# [0015] 实施例1  \n\n一种水性防雾涂料，包括水性树脂乳液 $100\\mathrm{g}$ ，交联剂 $20\\mathrm{g}$ ，防雾改性剂 $20\\mathrm{g}$ 。  \n\n[0016] 其中，防雾改性剂的制备方法为：  \n\n取式（1）所示的八乙烯基聚倍半硅氧烷1mol，式（2）所示的含有环氧丙烷链和环氧乙烷链的聚醚8mol，分别溶解在溶剂甲苯中配制成1mol/L的八乙烯基聚倍半硅氧烷的溶液和8mol/L的聚醚溶液，在1L的八乙烯基聚倍半硅氧烷的溶液中加入 $\\mathrm{12g}$ 氯铂酸，然后将其与1L的上述聚醚溶液混合，搅拌，并在 $90^{\\circ}\\mathrm{C}$ 下加成反应4h，得到防雾改性剂。  \n\n[0017] 式（1）为：  \n\n![](images/75279c4aa1bcc61257056a1a75a50dda7566684b58f2dac321ddd7d483d42411.jpg)  \n\n式（2）为：  \n\n其中，m为5，n为10。  \n\n[0018] 其中，水性树脂乳液为水性聚氨酯乳液。  \n\n[0019] 对比例1  \n\n与实施例1类似，对比的区别在于：防雾改性剂的制备中，式（2）所示的含有环氧丙烷链和环氧乙烷链的聚醚的用量为4mol。所使用的式（1）和式（2）两种物质完全相同，催化剂及其用量、反应的温度和时间也完全相同，得到防雾改性剂。  \n\n实施例2  \n\n一种水性防雾涂料，包括水性树脂乳液 $80\\mathrm{g}$ ，交联剂 $30\\mathrm{g}$ ，防雾改性剂 $20\\mathrm{g}$ 。[0020] 其中，防雾改性剂的制备方法为：  \n\n取式（1）所示的八乙烯基聚倍半硅氧烷1mol，式（2）所示的含有环氧丙烷链和环氧乙烷链的聚醚9mol，分别溶解在溶剂甲苯中配制成1mol/L的八乙烯基聚倍半硅氧烷的溶液和9mol/L的聚醚溶液，在1L的八乙烯基聚倍半硅氧烷的溶液中加入8g氯铂酸，然后将其与1L的上述聚醚溶液混合，搅拌，并在 $80^{\\circ}\\mathrm{C}$ 下加成反应5h，得到防雾改性剂。  \n\n[0021] 式（2）为：  \n\n其中，m为8，n为8。  \n\n[0022] 其中，水性树脂乳液为水性丙烯酸树脂乳液。  \n\n[0023] 对比例2  \n\n与实施例2类似，对比的区别在于：防雾改性剂的制备中，用式（3） $\\mathrm{SH_{3}{-}0{-}\\left[S i\\ (C H_{3})\\ _{2}{-}\\right.}$ $\\mathrm{0]_{p}-[S i H C H_{3}-0]_{q}-S H_{3}},$ 所示的聚硅氧烷替换了式（1）所示的八乙烯基聚倍半硅氧烷，其中p为6，q为8；用式（4）所示的含有环氧丙烷链和环氧乙烷链的聚醚替换了式（2）所示的聚醚；  \n\n式（4）为：  \n\nCH，其中，m也为8，n也为8。  \n\n[0024] 催化剂及其用量、反应的温度和时间也完全相同，得到防雾改性剂。[0025] 实施例3  \n\n一种水性防雾涂料，包括水性树脂乳液 $90\\mathrm{g}$ ，交联剂 $20\\mathrm{g}$ ，防雾改性剂 $30\\mathrm{g}$ 。[0026] 其中，防雾改性剂的制备方法为：  \n\n取式（1）所示的八乙烯基聚倍半硅氧烷 $1\\mathrm{mol}$ ，式（2）所示的含有环氧丙烷链和环氧乙烷链的聚醚10mol，分别溶解在溶剂甲苯中配制成1mol/L的八乙烯基聚倍半硅氧烷的溶液和9mol/L的聚醚溶液，在1L的八乙烯基聚倍半硅氧烷的溶液中加入16g氯铂酸，然后将其与1L的上述聚醚溶液混合，搅拌，并在 $100^{\\circ}\\mathrm{C}$ 下加成反应3h，得到防雾改性剂。  \n\n[0027] 式（2）为：  \n\n$$\nC H_{3}-C H_{2}-C H_{2^{-}}O-(C H_{2^{-}}C H_{2^{-}}O)_{m^{-}}(C H_{2}-C H_{2^{-}}O)_{n^{-}}C H_{3}^{\\prime}\n$$  \n\n其中，m为6，n为12。  \n\n[0028] 其中，水性树脂乳液为水性环氧树脂乳液。  \n\n[0029] 对比例3  \n\n与实施例3类似，区别在于直接以式（2）所示的含有环氧丙烷链和环氧乙烷链的聚醚作为防雾改性剂进行对比。  \n\n[0030] 为了比较各个实施例和对比例中的水性防雾涂料的防雾性能、表面强度、表面耐刮擦性能、表面耐腐蚀性能等，分别将实施例1-3和对比例1-3的水性防雾涂料涂覆到玻璃表面，干燥固化，得到相应的防雾涂料膜层，并对其进行性能测试。[0031] 其中，防雾性能通过观察涂料膜层在 $80^{\\circ}\\mathrm{C}$ 的水面上方的起雾时间进行判断；硬度参照GB/T  6739-2006，使用QHQ-A型铅笔硬度计测定涂料膜层的铅笔硬度；耐刮擦性通过观察涂料膜层经过针织物3000次刮擦后的防雾性能进行判断，结果如下表。  \n\n<html><body><table><tr><td></td><td>防雾效果</td><td>硬度</td><td>耐刮擦性</td></tr><tr><td>实施例1</td><td>20分钟内不起雾</td><td>3H</td><td>20分钟内不起雾</td></tr><tr><td>对比例1</td><td>10分钟内不起雾</td><td>3H</td><td>10分钟内不起雾</td></tr><tr><td>实施例2</td><td>20分钟内不起雾</td><td>3H</td><td>20分钟内不起雾</td></tr><tr><td>对比例2</td><td>15分钟内不起雾</td><td>2H</td><td>10分钟内不起雾</td></tr><tr><td>实施例3</td><td>20分钟内不起雾</td><td>3H</td><td>20分钟内不起雾</td></tr><tr><td>对比例3</td><td>15分钟内不起雾</td><td>1H</td><td>1分钟内不起雾</td></tr></table></body></html>  \n\n[0032] 通过实施例1和对比例1的对比可以发现，在防雾改性剂中，需要在聚倍半硅氧烷类化合物表面接枝足够多的聚醚基团，才能够得到完全的星型结构的有机硅氧烷化合物，才能够确保足够优异的防雾性能。通过实施例2和对比例2的对比可以发现，在防雾改性剂中，笼型聚倍半硅氧烷类化合物作为核心，能够充分利用其作为纳米粒子化合物的物理特性，具有优异的机械强度、耐刮擦性，可以确保水性涂料具有持久的防雾性能。通过实施例3和对比例3的对比进一步证实了在防雾改性剂中笼型聚倍半硅氧烷类化合物作为核心的优势。  \n\n[0033] 以上实施例仅仅是本发明的一部分内容，在不脱离本发明的基本构思的前提下，所作出的简单变形或改进均属于本发明的保护范围。",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,52 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利申请  \n\n(10)申请公布号 CN 114867793 A(43)申请公布日 2022.08.05  \n\n(21)申请号 202180007560.8  \n(22)申请日 2021 .01 .06  \n(30)优先权数据2020-003245 2020.01 .10 JP  \n\n(85)PCT国际申请进入国家阶段日2022.06.17  \n\n(86)PCT国际申请的申请数据PCT/JP2021/000200 2021 .01 .06(87)PCT国际申请的公布数据WO2021/141044 JA 2021 .07 .15(71)申请人 株式会社尼欧斯地址 日本兵库县  \n\n(72)发明人 竹井工贵 重松遥 西井健太郎小野真司 内贵英人  \n\n(74)专利代理机构 北京律盟知识产权代理有限责任公司 11287专利代理师 范海云  \n(51)Int.Cl.C09D 1/0 (2006.01)C09D 7/20(2006.01)C09D 7/61(2006.01)C09D 7/63(2006.01)B32B 7/023(2006.01)",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n防雾涂料组合物及防雾涂膜以及防雾物品",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n本发明的目的在于提供一种能够形成下述防雾涂膜的防雾涂料组合物，所述防雾涂膜不会引起流水痕等外观变化，牢固地密接于包含塑料基材的多种基材表面上，且长期发挥防雾效果。本发明提供一种防雾涂料组合物，其含有：长条状胶体氧化硅；及硅烷衍生物化合物混合物，其至少包含分子内具有聚乙二醇链的硅烷衍生物化合物及分子内具有环氧基的硅烷衍生物化合物。  \n\n![](images/57a7e45dfe361911b44fd4ecce384ae6fcbce8cd6b845a4d69381875b20edf9e.jpg)  \n\n1.一种防雾涂料组合物，其含有：  \n\n长条状胶体氧化硅；及  \n\n硅烷衍生物化合物混合物，其至少包含分子内具有聚乙二醇链的硅烷衍生物化合物及分子内具有环氧基的硅烷衍生物化合物。  \n\n2.根据权利要求1所述的防雾涂料组合物，其中该分子内具有聚乙二醇链的硅烷衍生物化合物在分子内还具有酰基或氨基甲酸酯基。  \n\n3.根据权利要求1或2所述的防雾涂料组合物，其中相对于该长条状胶体氧化硅的固体成分100重量份，该硅烷衍生物化合物混合物的含量以固体成分计为0.1重量份以上10.0重量份以下。  \n\n4.根据权利要求1至3中任一项所述的防雾涂料组合物，其还包含球状胶体氧化硅。  \n\n5.根据权利要求4所述的防雾涂料组合物，其中该长条状胶体氧化硅与该球状胶体氧化硅的固体成分重量比为 $12:10\\sim35:10$ 。  \n\n6.根据权利要求4或5所述的防雾涂料组合物，其中相对于该长条状胶体氧化硅与该球状胶体氧化硅的固体成分合计量100重量份，该硅烷衍生物化合物混合物的含量以固体成分计为0.1重量份以上10.0重量份以下。  \n\n7.根据权利要求4至6中任一项所述的防雾涂料组合物，其中该长条状胶体氧化硅是酸性长条状胶体氧化硅与碱性长条状胶体氧化硅的混合物，该球状胶体氧化硅是碱性球状胶体氧化硅。  \n\n8.根据权利要求1至7中任一项所述的防雾涂料组合物，其还包含表面活性剂。  \n\n9.根据权利要求1至8中任一项所述的防雾涂料组合物，其还包含有机溶剂。  \n\n10.一种防雾涂膜，其包含长条状氧化硅与硅烷衍生物化合物的反应物，且该长条状氧化硅与该硅烷衍生物化合物键结在一起。  \n\n11.根据权利要求10所述的防雾涂膜，其还包含球状氧化硅，且  \n\n在相邻的长条状氧化硅之间的空隙内埋设有该球状氧化硅，该长条状氧化硅以及该球状氧化硅与该硅烷衍生物化合物键结在一起。  \n\n12.根据权利要求11所述的防雾涂膜，其中该长条状氧化硅包含酸性长条状氧化硅及碱性长条状氧化硅，该球状氧化硅包含碱性球状氧化硅。  \n\n13.根据权利要求10至12中任一项所述的防雾涂膜，其中该硅烷衍生物化合物至少包含分子内具有聚乙二醇链的硅烷衍生物化合物、及分子内具有环氧基的硅烷衍生物化合物。  \n\n14.一种防雾物品，其包含基材、及根据权利要求10至13中任一项所述的防雾涂膜。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 防雾涂料组合物及防雾涂膜以及防雾物品",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明涉及一种防雾涂料组合物及使用其制作而成的防雾涂膜以及防雾物品。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 汽车的前照灯等照明装置主要包含光源及配置在光源前方的由玻璃或塑料等所形成的透明部件。并且，光源所发出的光透过透明部件而照射至照明装置的外部及周边部。这种照明装置有时会在透明部件的内侧(光源侧)产生雾，可能导致照射光的强度降低而产生安全性问题。另外，透过已产生雾的透明部件所照射的光的光量较少，在美观方面也可能成为问题。  \n\n[0003] 在日本专利特开2016‑169287号公报中提出了一种防雾剂组合物，其包含共聚物(A)、多官能性封端异氰酸酯化合物(B)及表面活性剂(C)。日本专利特开2016‑169287号公报的防雾剂组合物是利用一直以来广为人知的防雾机制，应用了防雾剂组合物的防雾涂膜中存在的表面活性剂(C)使附着于基材上的防雾涂膜上的水的表面张力降低，瞬间形成平滑的水膜，防止光的漫反射，由此防止雾。另一方面，在日本专利特开2005‑126647号公报中提出了一种防雾剂，其包含水性介质、项链状胶体氧化硅、硅烷衍生物及表面活性剂。在日本专利特开2005‑126647号公报中，使用了分散于水性介质中时pH值为 $8\\sim11$ (即碱性)的项链状胶体氧化硅。日本专利特开2005‑126647号公报的防雾剂通过使形成有涂膜的基材的表面被胶体氧化硅覆盖来发挥防雾效果。在日本专利第5804996号公报中提出了一种有机基材用防雾防污剂，其含有甲醇及/或乙醇、及异丙醇、正丙醇或二醇醚、及有机氧化硅溶胶、及四氢呋喃、以及硼酸。在日本专利特开2019‑19253号公报中提出了一种防雾涂料组合物，其包含长条状胶体氧化硅、及硅烷衍生物，所述防雾涂料组合物可提供一种不会引起流水痕等外观变化而在包含塑料基材的多种基材表面上形成稳定的防雾涂膜，且长期发挥防雾效果的防雾涂料组合物。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0004] [发明要解决的问题]  \n\n[0005] 如果在由日本专利特开2016‑169287号公报中所提出的包含表面活性剂作为主成分的防雾剂组合物所形成的防雾涂膜上形成水膜，那么可能导致该表面活性剂溶出至水中，局部地发生表面活性剂与水一起流走的情况。如果这种部位进行干燥，那么可能在防雾物品上残留流水痕。另外，关于由像日本专利特开2005‑126647号公报那样重视与塑料基材的密接性而使用了硅烷衍生物的防雾剂所形成的涂膜，因硅烷衍生物的影响，可能会使长期防雾性受损。关于包含日本专利第5804996号公报中所使用的有机氧化硅溶胶的防雾剂，其所形成的涂膜的亲水性较低，有不易表现防雾性的情况。关于由日本专利特开2019‑19253号公报的防雾涂料组合物所形成的防雾涂膜，不易引起流水痕等外观变化，防雾效果也较高，但由于为了提高与塑料基材的密接性而使用的硅烷衍生物的影响，可能难以维持长期的防雾效果。另外，日本专利特开2019‑19253号公报的防雾涂膜存在以下情况，即，在  \n\n高温时，与基材的密接性降低。  \n\n[0006] 本发明的目的在于提供一种能够形成下述防雾涂膜的防雾涂料组合物，所述防雾涂膜不会引起流水痕等外观变化，牢固地密接于包含塑料基材的多种基材表面上，且长期发挥防雾效果。  \n\n[0007] [解决问题的技术手段]  \n\n[0008] 本发明的实施方式中的防雾涂料组合物的特征在于含有：长条状胶体氧化硅；及硅烷衍生物化合物混合物，其至少包含分子内具有聚乙二醇链的硅烷衍生物化合物及分子内具有环氧基的硅烷衍生物化合物。  \n\n[0009] 本发明的另一实施方式是一种防雾涂膜，其特征在于包含长条状氧化硅与硅烷衍生物化合物的反应物，且长条状氧化硅与硅烷衍生物化合物键结在一起。  \n\n[0010] 本发明的又一实施方式是一种防雾物品，其包含基材、及防雾涂膜。  \n\n[0011] [发明效果]  \n\n[0012] 使用本发明的防雾涂料组合物所形成的防雾涂膜可瞬间形成平滑的水膜而防止光的漫反射，防雾性能优异。本发明的防雾涂膜不易产生干燥后的流水痕等外观变化。本发明的防雾涂膜牢固地接着于塑料等基材上，密接性较高。进而，利用本发明的防雾涂料组合物的防雾物品(例如照明装置)不易产生外观变化，可长期维持稳定的光量。",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 附图说明  \n\n[0013] 图1是表示下述防雾涂膜的状态的示意图，所述防雾涂膜是在基材的表面键结有长条状氧化硅，并且在此处键结有分子内具有聚乙二醇链的硅烷衍生物化合物、及分子内具有环氧基的硅烷衍生物化合物。  \n\n[0014] 图2是表示下述防雾涂膜的状态的示意图，所述防雾涂膜是在相邻的长条状氧化硅之间的空隙内埋设有球状氧化硅，且在此处键结有分子内具有聚乙二醇链的硅烷衍生物化合物、及分子内具有环氧基的硅烷衍生物化合物。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 具体实施方式  \n\n[0015] 以下对本发明的实施方式进行说明。本发明的一实施方式是一种防雾涂料组合物，其含有长条状胶体氧化硅；及硅烷衍生物化合物混合物，其至少包含分子内具有聚乙二醇链的硅烷衍生物化合物、及分子内具有环氧基的硅烷衍生物化合物。  \n\n[0016] 在本实施方式中，防雾涂料组合物是指能够在玻璃或塑料等基材上形成涂膜，不易因水蒸气的水滴而产生雾的组合物。在由基材隔开的两空间存在温度差的情况下，高温侧的湿气在基材表面上冷凝，形成水滴。该水滴引起光的漫反射而产生雾。作为防止在基材上形成水滴的机制，已知有使附着于基材表面的水分瞬间成为水膜的机制、及瞬间吸收附着于基材表面的水分的机制。本实施方式的防雾涂料组合物形成防雾涂膜，所述防雾涂膜使附着于基材表面的水分瞬间成为水膜，防止形成水滴，由此防止基材的雾。  \n\n[0017] 本实施方式的防雾涂料组合物包含长条状胶体氧化硅。所谓胶体氧化硅是指二氧化硅(氧化硅、 $\\mathrm{Si0_{2})}$ 或其水合物的胶体溶液。根据使氧化硅分散的分散介质的性质，而有水系胶体氧化硅、及有机溶剂系有机氧化硅溶胶，但实施方式中尤其适宜使用的氧化硅为胶体氧化硅。形成胶体氧化硅的球状氧化硅的一次粒径通常为 $5\\sim300\\mathrm{nm}$ 左右，其可能进行凝集等而形成更大的二次粒子。本实施方式中适宜使用的胶体氧化硅为长条状胶体氧化硅。长条状胶体氧化硅是指氧化硅的一次粒子彼此进行共价键结并形成较长的绳状而获得长条状氧化硅，使该长条状氧化硅分散于水中而成的长条状氧化硅的胶体溶液。作为这种长条状胶体氧化硅，已知有链状胶体氧化硅或珍珠项链状胶体氧化硅。长条状胶体氧化硅因为能够在基材的表面上扩散吸附，形成覆膜，所以可优选地用作防雾涂料组合物的成分。此外，关于将水作为分散介质的胶体氧化硅，存在酸性、中性及碱性胶体氧化硅。作为本实施方式中适宜使用的胶体氧化硅，可列举分散于水中而表现 $\\mathrm{pH1}{\\sim}3$ 的强酸性的酸性长条状胶体氧化硅、表现 $\\mathrm{pH}4{\\sim}9$ 的弱酸性 $\\sim$ 中性～弱碱性的长条状胶体氧化硅、表现 $\\mathrm{\\pH10{\\sim}14}$ 的碱性长条状胶体氧化硅，它们可以单独使用，也可以混合使用。此外，在混合多种胶体氧化硅进行使用的情况下，优选以所混合的胶体氧化硅的pH值成为中性～弱碱性 $\\mathrm{(pH7\\sim10}$ 左右)的方式进行混合。作为可用于实施方式中的长条状胶体氧化硅，可列举：ST‑OUP、ST‑UP、ST‑PS‑S、ST‑PS‑M、ST‑PS‑SO、ST‑PS‑MO(均为日产化学工业(股))等市售品。此外，可按照实施方式的防雾涂料组合物的pH值成为不会对供涂布防雾涂料组合物的基材产生影响的范围(通常为弱酸性～弱碱性的范围)的方式，以任意组合混合长条状胶体氧化硅而使用。除了酸性长条状胶体氧化硅与碱性长条状胶体氧化硅的组合、碱性长条状胶体氧化硅与酸性长条状胶体氧化硅的组合以外，也可以单独使用中性长条状胶体氧化硅。  \n\n[0018] 实施方式的防雾涂料组合物还包含硅烷衍生物化合物混合物。硅烷衍生物化合物混合物优选为至少包含以下通式1‑1所表示的分子内具有聚乙二醇链的硅烷衍生物化合物、及以下通式2所表示的分子内具有环氧基的硅烷衍生物化合物：  \n\n[0019] [化1]  \n\n[0020]  \n\n$$\n\\mathsf{R_{2}{\\mathsf{O}}\\mathrm{-}\\mathop{S i}_{2}\\mathop{\\left(\\mathrm{R_{2}\\mathop{H_{2}}}+\\mathrm{CH_{2}}+\\right)_{n}}\\left\\{\\begin{array}{l l}{\\mathrm{OR_{1}}}\\\\ {\\mathrm{OR_{2}O}}\\end{array}\\right.\\qquad\\mathrm{(1\\cdot1)}\n$$  \n\n[0021] (式中， $\\mathsf{R}_{1}\\bullet\\mathsf{R}_{2}$ 及 $\\mathrm{R}_{3}$ 彼此相同或不同，且为碳数 $1{\\sim}3$ 的烷基， $\\mathrm{R_{4}}$ 为氢原子或碳数 $1{\\sim}3$ 的烷基， $\\mathfrak{n}$ 为 $1{\\sim}5$ 的整数， $\\mathfrak{m}$ 为 $1{\\sim}20$ 、优选为 $4{\\sim}20$ 、进而优选为 $4\\mathrm{\\sim}15$ 的整数)[0022] [化2]  \n\n[0023]  \n\n![](images/5b9a3c108e65098b94896c67717f041bc2d27c38bf516bed678ffd61cad9a58d.jpg)  \n\n[0024] (式中， $\\mathrm{R}_{5}{\\ 、}\\mathrm{R}_{6}$ 、及 $\\mathrm{R}_{7}$ 彼此相同或不同，且为碳数 $1{\\sim}3$ 的烷基，p为 $1{\\sim}5$ 的整数，X为环氧基或缩水甘油基)。  \n\n[0025] 分子内具有聚乙二醇链的硅烷衍生物化合物也可为像以下通式1‑2所表示的分子内具有聚乙二醇链及酰基的硅烷衍生物化合物：  \n\n[0026] [化3]  \n\n[0027]  \n\n![](images/f11eda4b8b24a1c7d0f6dfe6c8eaeb3a793adef445e446fd6a3b701017030101.jpg)  \n\n[0028] (式中 ， $\\mathrm{R}_{11}{\\setminus}\\mathrm{R}_{12}{\\setminus}\\mathrm{R}_{13}$ 及 $\\mathrm{R}_{14}$ 彼此相同或不同，且为碳数 $1\\sim3$ 的烷基，A选自由 $^-0\\cdot^{-}$ $\\mathrm{NHCO0-\\Phi_{\\mathrm{e}}-O C O^{-}\\Phi_{\\mathrm{e}}-C O O^{-}\\Phi_{\\mathrm{e}}-O C H_{\\mathrm{2}}C H\\left(O H\\right)C H_{\\mathrm{2}}O^{-}\\cdot\\mathrm{\\Phi_{\\mathrm{e}}-O C H_{\\mathrm{2}}C H_{\\mathrm{2}}C H\\left(O H\\right)O^{-}\\Phi_{\\mathrm{e}}-S^{-}\\cdot\\mathrm{\\Phi_{\\mathrm{e}}-S C O^{-}\\cdot\\Phi_{\\mathrm{e}}-O C H_{\\mathrm{2}}C H^{-}}}}$ 及‑COS‑所组成的群中， $\\boldsymbol{\\mathrm{n}}_{1}$ 为 $1{\\sim}5$ 的整数， $\\mathfrak{m}_{1}$ 为 $1{\\sim}20$ 、优选为 $4{\\sim}20$ 、进而优选为 $4\\mathord{\\sim}15$ 的整数)。通式(1‑2)所表示的硅烷衍生物化合物中，式中A的最优选的基团为 $-0-$ 。  \n\n[0029] 分子内具有聚乙二醇链的硅烷衍生物化合物也可为以下通式1‑3所表示的硅烷衍生物化合物：  \n\n[0030] [化4]  \n\n[0031]  \n\n$$\n\\mathsf{R}_{22}\\mathsf{O}-\\sideset{}{'}{\\mathsf{S i}}+\\mathsf{C H}_{2}\\underset{\\mathtt{n}_{2}}{\\to}\\big\\{\\big\\langle\\mathsf{I H}_{2}\\mathsf{C H}_{2}\\mathsf{O}-\\big\\rangle_{\\mathtt{m}_{2}}\\mathsf{R}_{24}\\qquad(1\\cdot3)\n$$  \n\n[0032] (式中， $\\mathsf{R}_{21}\\mathsf{\\Omega}\\cdot\\mathsf{R}_{22}$ 及 $\\mathrm{R_{23}}$ 彼此相同或不同，且为碳数 $1{\\sim}3$ 的烷基， $\\mathrm{R}_{24}$ 为氢原子或碳数 $1\\sim$ 3的烷基，B选自由 $\\begin{array}{r}{-\\mathbb{M}\\mathrm{HCO}0-\\ 、-0{\\mathbb C}0-\\ 、-{\\mathbb C}00-\\ 、-0{\\mathbb C}\\mathrm{H}_{2}\\mathrm{CH}\\left(0\\mathrm{H}\\right){\\mathbb C}\\mathrm{H}_{2}0-\\ 、-0{\\mathbb C}\\mathrm{H}_{2}{\\mathbb C}\\mathrm{H}_{2}{\\mathrm C}\\mathrm{H}\\left(0\\mathrm{H}\\right)0-\\ 、-{\\mathbb S}-\\pounds_{\\circ}-{\\mathrm C}0-\\big\\|\\mathrm{H}\\big(0\\mathrm{H}\\big)\\big(0-\\sqrt{\\bigcirc}\\bigtriangleup\\big\\big)\\big(0-\\sqrt{\\bigcirc}\\bigtriangleup\\big)\\big(0\\mathrm{H}\\big)\\big(0-\\sqrt{\\bigcirc}\\bigtriangleup\\big)\\big(0\\mathrm{H}\\big)\\big(0-\\sqrt{\\bigcirc}\\bigtriangleup\\big).}\\end{array}$ 及‑COS‑所组成的群中， $\\boldsymbol{\\mathrm{n}}_{2}$ 为 $1\\sim5$ 的整数， $\\mathfrak{m}_{2}$ 为 $1{\\sim}20$ 、优选为 $4{\\sim}20$ 、进而优选为 $4\\sim15$ 的整数)。通式(1‑3)所表示的硅烷衍生物化合物中，式中B的最优选的基团为‑NHCOO‑(氨基甲酸酯基)。  \n\n[0033] 式(1‑1)所表示的硅烷衍生物化合物具有能够与长条状氧化硅进行反应的烷氧基(即 $\\phantom{+}{-0\\mathrm{R_{1}}\\phantom{-}}\\phantom{+}\\bigl-0\\mathrm{R_{2}}$ 及 ${\\displaystyle-0\\mathrm{R_{3}}}$ 基团)、及包含与水的亲和性较高的聚乙二醇链的亲水基 $\\mathrm{\\left(-0CH_{2}C H_{2}-\\right)}$ )。在实施方式中，式(1‑1)所表示的硅烷衍生物化合物具有能够与长条状氧化硅进行反应的取代基及亲水基，由此能够使该硅烷衍生物化合物键结于长条状氧化硅，且对防雾涂料组合物所形成的防雾涂膜赋予亲水性。作为用于实施方式中的式(1‑1)所表示的硅烷衍生物化合物，可列举：甲氧基PEG‑10丙基三甲氧基硅烷、乙氧基PEG‑10丙基三甲氧基硅烷等聚乙二醇改性烷氧基硅烷。作为分子内具有聚乙二醇链的硅烷衍生物化合物，可使用Dynasylan4148、Dynasylan4150(均为Evonik  Japan(股))、甲氧基PEG‑10丙基三甲氧基硅烷(PG系列)(AZMAX(股))等市售品。另外，除此以外还可以使用2‑[羟基(聚亚乙氧基)乙基]三甲氧基硅烷、2‑[羟基(聚亚乙氧基)丙基]三甲氧基硅烷、2‑[羟基(聚亚乙氧基)丁基]三甲氧基硅烷、2‑[烷氧基(聚亚乙氧基)乙基]三甲氧基硅烷、2‑[烷氧基(聚亚乙氧基)丙基]三甲氧基硅烷、2‑[烷氧基(聚亚乙氧基)丁基]三甲氧基硅烷等。  \n\n[0034] 式(1‑2)所表示的硅烷衍生物化合物具有能够与长条状氧化硅进行反应的烷氧基(即 $\\boldsymbol{\\mathbf{\\rho}}-0\\mathrm{R}_{11}\\boldsymbol{\\mathbf{\\rho}}\\boldsymbol{\\mathbf{\\rho}}\\cdot\\boldsymbol{\\mathbf{\\rho}}^{-}0\\mathrm{R}_{12}$ 及 $-0\\mathrm{R}_{13}$ 基团) 、及包含与水的亲和性较高的聚乙二醇链的亲水基(‑$\\mathrm{0CH_{2}C H_{2}^{-}\\right)}$ )。在实施方式中，式(1‑2)所表示的硅烷衍生物化合物具有能够与长条状氧化硅进行反应的取代基及亲水基，由此可使该硅烷衍生物化合物键结于长条状氧化硅，且可对防雾涂料组合物所形成的防雾涂膜赋予亲水性。作为用于实施方式中的式(1‑2)所表示的硅烷衍生物化合物，可列举：2‑[乙酰氧基(聚亚乙氧基)丙基]三乙氧基硅烷、2‑[乙酰氧基(聚亚乙氧基)乙基]三甲氧基硅烷、2‑[乙酰氧基(聚亚乙氧基)丙基]三甲氧基硅烷、2‑[乙酰氧基(聚亚乙氧基)丁基]三甲氧基硅烷等。作为分子内具有聚乙二醇链及酰基的硅烷衍生物化合物，可使用2‑[乙酰氧基(聚亚乙氧基)丙基]三乙氧基硅烷(Gelest  Inc.)等市售品。  \n\n[0035] 式(1‑3)所表示的硅烷衍生物化合物具有能够与长条状氧化硅进行反应的烷氧基(即 $\\boldsymbol{\\mathbf{\\ell}}-0\\mathrm{R}_{21}\\boldsymbol{\\mathbf{\\ell}}\\cdot\\boldsymbol{\\mathbf{\\ell}}^{-}0\\mathrm{R}_{22}$ 及 $-\\ O\\mathrm{R}_{23}$ 基团) 、及包含与水的亲和性较高的聚乙二醇链的亲水基(‑$\\mathrm{OCH_{2}C H_{2}^{-}}\\overline{{\\prime}}$ )。在实施方式中，式(1‑3)所表示的硅烷衍生物化合物具有能够与长条状氧化硅进行反应的取代基及亲水基，由此可使该硅烷衍生物化合物键结于长条状氧化硅，且可对防雾涂料组合物所形成的防雾涂膜赋予亲水性。作为用于实施方式中的式(1‑3)所表示的硅烷衍生物化合物，可列举：[3‑(三甲氧基硅基)丙基]氨基甲酸2‑羟基(聚亚乙氧基)乙酯、[3‑(三乙氧基硅基)丙基]氨基甲酸2‑羟基(聚亚乙氧基)乙酯、[3‑(三甲氧基硅基)丙基]氨基甲酸2‑烷氧基(聚亚乙氧基)乙酯、[3‑(三乙氧基硅基)丙基]氨基甲酸2‑烷氧基(聚亚乙氧基)乙酯、[4‑(三甲氧基硅基)丁酸]2‑烷氧基(聚亚乙氧基)乙酯等。用于实施方式中的式(1‑3)所表示的硅烷衍生物化合物中，最优选为分子内具有聚乙二醇链及氨基甲酸酯基的硅烷衍生物化合物。分子内具有聚乙二醇链及氨基甲酸酯基的硅烷衍生物化合物可以通过以下方式合成，即，使异氰酸基丙基三甲氧基硅烷或异氰酸基丙基三乙氧基硅烷等具有异氰酸基的烷氧基硅烷化合物、与聚乙二醇进行反应而合成所述硅烷衍生物化合物。此外，在本说明书中，有时将式(1‑3)所表示的硅烷衍生物化合物中可尤其适宜地用于实施方式中的分子内具有聚乙二醇链及氨基甲酸酯基的硅烷衍生物化合物称为“氨基甲酸酯硅烷”。另外，有时将式(1‑1)、式(1‑2)、式(1‑3)分别所表示的硅烷衍生物化合物统一称为“分子内具有聚乙二醇链的硅烷衍生物化合物”。  \n\n[0036] 式(2)所表示的硅烷衍生物化合物具有能够与长条状氧化硅进行反应的烷氧基(即 ${\\cdot0\\mathrm{R}_{5},-0\\mathrm{R}_{6}}$ 及 ${\\displaystyle-0\\mathrm{R}_{7}}$ 基团)、及X(即环氧基或缩水甘油基)。在实施方式中，式(2)所表示的硅烷衍生物化合物具有能够与长条状氧化硅进行反应的取代基，由此该硅烷衍生物化合物能够使长条状氧化硅之间交联。作为用于实施方式中的式(2)所表示的硅烷衍生物化合物，可列举：3‑缩水甘油氧基丙基三乙氧基硅烷、3‑缩水甘油氧基丙基三甲氧基硅烷、3‑缩水甘油氧基丙基甲基二甲氧基硅烷、3‑缩水甘油氧基丙基甲基二乙氧基硅烷等含环氧基的硅烷衍生物化合物。作为分子内具有环氧基的硅烷衍生物化合物，可使用DynasylanGLYEO(EvonikJapan(股))、KBM402、KBM403、KBE402、KBE403(均为信越化学工业(股))等市售品。这样，硅烷衍生物化合物能够与长条状氧化硅进行反应而键结，使长条状氧化硅之间交联，提高防雾涂膜的强度，且对防雾涂膜赋予亲水性。  \n\n[0037] 硅烷衍生物化合物混合物优选为相对于长条状胶体氧化硅的固体成分100重量份，其含量以固体成分计为0.1重量份以上10.0重量份以下。长条状胶体氧化硅如上所述将水作为分散介质，所以相对于分散于水中的实际固体成分的重量来决定硅烷衍生物化合物的调配量。如果相对于长条状胶体氧化硅的固体成分100重量份，硅烷衍生物化合物的调配量以固体成分计未达0.1重量份，那么可能导致将防雾涂料组合物涂布于基材时的润湿性变差，进而可能导致所形成的涂膜的强度降低，而涂膜的耐久性欠佳。另一方面，如果相对于长条状胶体氧化硅的固体成分100重量份，硅烷衍生物化合物的调配量以固体成分计超过10.0重量份，那么存在由防雾涂料组合物所形成的防雾涂膜的防雾性变低的顾虑。如上所述，硅烷衍生物化合物是用来与防雾涂料组合物的构成成分即胶体氧化硅中所含的氧化硅进行反应而形成良好的氧化硅覆膜的，所以只要调配与氧化硅的一部分进行反应的量的硅烷衍生物化合物即可。  \n\n[0038] 实施方式的防雾涂料组合物可还包含球状胶体氧化硅。与所述长条状胶体氧化硅同样地，球状胶体氧化硅也为二氧化硅(氧化硅、 $\\mathrm{Si0_{2})}$ 或其水合物的胶体溶液。球状胶体氧化硅在水中具有大致球形粒子形状。此外，如上所述，关于将水作为分散介质的胶体氧化硅，存在酸性、中性、碱性胶体氧化硅。作为本实施方式中适宜使用的球状胶体氧化硅，可列举分散于水中而表现 $\\mathrm{\\pH1{\\sim}3}$ 的强酸性的酸性球状胶体氧化硅、表现 $\\mathrm{pH}4{\\sim}9$ 的弱酸性～中性～弱碱性的中性球状胶体氧化硅、表示p $\\mathrm{110}{\\sim}14$ 的碱性球状胶体氧化硅，它们可单独使用，也可以混合使用。在实施方式中，优选使用碱性球状胶体氧化硅作为球状胶体氧化硅，将所述长条状胶体氧化硅混合物的pH值调节为弱酸性～弱碱性。优选按照以下方式进行混合，即，长条状胶体氧化硅与球状胶体氧化硅的固体成分重量比成为 $12:10\\sim35:10$ ，优选为15：$10{\\sim}30:10$ 。作为可用于实施方式中的球状胶体氧化硅，可列举：ST‑N、ST‑NXS、ST‑S、ST‑XS、$\\mathrm{ST-0.ST-0XS}$ (均为日产化学工业(股))等市售品。此外，也可以按照实施方式的防雾涂料组合物的pH值成为不会对供涂布防雾涂料组合物的基材产生影响的范围(通常为弱酸性～弱碱性的范围)的方式，以任意组合混合所述长条状胶体氧化硅与球状胶体氧化硅。例如，除了将酸性长条状胶体氧化硅及碱性长条状胶体氧化硅及碱性球状胶体氧化硅加以混合而使用以外，还可以碱性长条状胶体氧化硅与酸性球状胶体氧化硅的组合、酸性长条状胶体氧化硅与碱性球状胶体氧化硅的组合、中性长条状胶体氧化硅与酸性球状胶体氧化硅的组合、碱性长条状胶体氧化硅与中性球状胶体氧化硅的组合、或者碱性长条状胶体氧化硅及酸性球状胶体氧化硅及碱性球状胶体氧化硅的组合等所有组合进行混合。  \n\n[0039] 实施方式中，在并用长条状胶体氧化硅与球状胶体氧化硅的情况下，非常优选为长条状胶体氧化硅为酸性长条状胶体氧化硅与碱性长条状胶体氧化硅的混合物，且球状胶体氧化硅为碱性球状胶体氧化硅。可适当地调配这些胶体氧化硅，将胶体氧化硅混合物的pH值调节为弱酸性～弱碱性。在并用长条状胶体氧化硅与球状胶体氧化硅的情况下，优选为相对于长条状胶体氧化硅与球状胶体氧化硅的固体成分合计量100重量份，硅烷衍生物化合物混合物的含量以固体成分计为0.1重量份以上10.0重量份以下。长条状胶体氧化硅及球状胶体氧化硅如上所述将水作为分散介质，所以相对于分散于水中的实际固体成分的重量来决定硅烷衍生物化合物的调配量。如果相对于长条状胶体氧化硅与球状胶体氧化硅的固体成分合计量100重量份，硅烷衍生物化合物的调配量以固体成分计未达0.1重量份，那么可能导致将防雾涂料组合物涂布于基材时的润湿性变差，进而可能导致所形成的涂膜的强度降低，而涂膜的耐久性欠佳。另一方面，如果相对于长条状胶体氧化硅与球状胶体氧化硅的固体成分合计量100重量份，硅烷衍生物化合物的调配量以固体成分计超过10.0重量份，那么存在由防雾涂料组合物所形成的防雾涂膜的防雾性变低的顾虑。如上所述，硅烷衍生物化合物是用来与防雾涂料组合物的构成成分即胶体氧化硅中所含的氧化硅进行反应而形成良好的氧化硅覆膜的，所以只要调配与氧化硅的一部分进行反应的量的硅烷衍生物化合物即可。  \n\n[0040] 实施方式的防雾涂料组合物可还包含表面活性剂。在实施方式的防雾涂料组合物中，表面活性剂用于辅助各胶体氧化硅在基材表面上的扩散，而使涂布作业变得容易。作为表面活性剂，可使用阴离子性表面活性剂、阳离子性表面活性剂、非离子性表面活性剂、两性表面活性剂中的任一种，可使用它们中的一种或两种以上。作为阴离子性表面活性剂，可列举：油酸钠、油酸钾等脂肪酸盐、月桂基硫酸钠、月桂基硫酸铵等高级醇硫酸酯类、十二烷基苯磺酸钠、烷基萘磺酸钠等烷基苯磺酸盐及烷基萘磺酸盐、萘磺酸福马林缩合物、二烷基磺基琥珀酸盐、二烷基磷酸盐、聚氧乙烯烷基苯醚硫酸钠等聚氧乙烯硫酸盐、含有全氟烷基的磺酸盐型、含有全氟烷基的羧酸盐型、含有全氟烯基的磺酸盐型、含有全氟烯基的羧酸盐型等阴离子性氟系表面活性剂类。作为阳离子性表面活性剂，例如可列举：乙醇胺类、月桂基胺乙酸酯、三乙醇胺单甲酸盐、硬脂酰胺乙基二乙胺乙酸盐等胺盐、月桂基三甲基氯化铵、硬脂基三甲基氯化铵、二月桂基二甲基氯化铵、二硬脂基二甲基氯化铵、月桂基二甲基苄基氯化铵、硬脂基二甲基苄基氯化铵等季铵盐、含有全氟烷基或全氟烯基的季铵盐型等阳离子性氟系表面活性剂类。  \n\n[0041] 作为非离子性表面活性剂，例如可列举：聚氧乙烯月桂醇、聚氧乙烯月桂醚、聚氧乙烯油醚等聚氧乙烯高级醇醚类、聚氧乙烯辛基苯酚、聚氧乙烯壬基苯酚等聚氧乙烯烷基芳基醚类、聚氧乙烯乙二醇单硬脂酸酯等聚氧乙烯酰基酯类、聚丙二醇环氧乙烷加成物、聚氧乙烯山梨醇酐单月桂酸酯、聚氧乙烯山梨醇酐单硬脂酸酯等聚氧乙烯山梨醇酐脂肪酸酯类、烷基磷酸酯、聚氧乙烯烷基醚磷酸酯等磷酸酯类、糖酯类、纤维素醚、聚醚改性硅酮油等硅酮类、含有全氟烷基的环氧乙烷加成物型、含有全氟烷基的氧化胺、含有全氟烷基的低聚物型、含有全氟烯基的环氧乙烷加成物型、含有全氟烯基的氧化胺、含有全氟烯基的低聚物型等非离子性氟系表面活性剂类。作为两性表面活性剂，可列举：月桂基三甲基氯化铵、二月桂基二甲基氯化铵、二硬脂基二甲基氯化铵、月桂基二甲基苄基氯化铵等季铵盐、二甲基烷基月桂基甜菜碱、二甲基烷基硬脂基甜菜碱等脂肪酸型两性表面活性剂、二甲基烷基磺基甜菜碱等磺酸型两性表面活性剂、烷基甘氨酸、含有全氟烷基或全氟烯基的甜菜碱型两性氟系表面活性剂类等。可优选地使用所述表面活性剂中的任一种作为本实施方式的表面活性剂。表面活性剂优选为相对于防雾涂料组合物100重量份而含有 $0.01\\sim1$ 重量份左右。[0042] 进而，实施方式的防雾涂料组合物可含有有机溶剂。仅凭实施方式的防雾涂料组合物的主成分即以水作为分散介质的胶体氧化硅与硅烷衍生物化合物的混合物，也可涂布于基材表面上而形成防雾涂膜，但是，如果还包含有机溶剂，那么水的干燥得到促进，因此可更早一步形成防雾涂膜。实施方式中可使用的有机溶剂是与水具有相容性、或在某一范围内与水进行混合的有机溶剂。作为这种有机溶剂，例如可列举醇类(甲醇、乙醇、丙醇、异丙醇、乙二醇、丙二醇、二丙酮醇等)、醚类(二甲氧基乙烷、四氢呋喃、二恶烷、丙二醇单甲醚、乙二醇单甲醚、乙二醇单乙醚、乙二醇单丙醚、乙二醇单丁醚、乙二醇叔丁醚、乙二醇苯醚、二乙二醇单甲醚、二乙二醇单丁醚、二乙二醇单丁醚、三乙二醇单丁醚、二丙二醇单甲醚等)、酮类(丙酮、甲基乙基酮等)、酰胺类(二甲基甲酰胺等)、二甲基亚砜(DMSO)、乙腈、硝基甲烷、三乙胺，它们可混合使用。有机溶剂优选为相对于防雾涂料组合物100重量份而含有1${\\sim}80$ 重量份左右。尤其优选为在有机溶剂中少量混合能够使塑料基材的表面稍微溶解的溶剂(二丙酮醇等)。二丙酮醇会使塑料基材的表面稍微溶解，扩大塑料基材的表面积，因此防雾涂料组合物能够进入至塑料基材的内部。由此，由防雾涂料组合物所形成的防雾涂膜牢固地密接于塑料基材的表面。在基于这种目的而将二丙酮醇混合到有机溶剂中时，较理想为相对于防雾涂料组合物100重量份将二丙酮醇混合 $1\\sim7\\%$ 、优选为 $1\\sim5\\%$ 。如果过多地混合二丙酮醇，那么针对塑料基材的润湿性降低，无法形成适当的防雾涂膜。因此，优选为以防雾涂料组合物稍微进入至塑料基材的表面附近的程度，使用少量的二丙酮醇。  \n\n[0043] 本实施方式的适宜的防雾涂料组合物可通过以下方式制造，即，首先准备长条状胶体氧化硅、及硅烷衍生物化合物混合物，接着视需要与球状胶体氧化硅、表面活性剂及有机溶剂进行混合。长条状胶体氧化硅是以特定的固体成分比率分散在作为分散介质的水中，所以可按照相对于该固体成分100重量份，硅烷衍生物的重量成为0.1重量份以上10重量份以下的方式进行计算而混合。实施方式的防雾涂料组合物可除了这些成分以外还适当地调配通常包含在涂料组合物中的添加剂(例如染料、颜料、增塑剂、分散剂、防腐剂、消光剂、抗静电剂、阻燃剂)。  \n\n[0044] 可将由长条状胶体氧化硅、硅烷衍生物化合物混合物、及视需要而定的球状胶体氧化硅、表面活性剂及有机溶剂适当调配而成的实施方式的防雾涂料组合物涂布在基材表面。可列举玻璃、塑料、金属等作为基材，但实施方式的防雾涂料组合物可尤其适宜地涂布在透明塑料上。关于防雾涂料组合物在基材表面上的涂布，可通过刮刀法、棒式涂布法、浸渍法、空气喷涂法、滚筒刷法、辊式涂布机法等以往的涂布方法来适当地进行。可对所涂布的防雾涂料组合物进行加热而形成防雾涂膜。关于防雾涂料组合物的加热，只要加热至足够使氧化硅与硅烷衍生物进行反应，且使水(及含有情况下的有机溶剂)蒸发的温度即可。虽然也取决于所使用的有机溶剂的种类，但通常加热至 $80{\\sim}150^{\\circ}\\mathrm{C}$ 、优选为 $100{\\sim}150^{\\circ}\\mathrm{C}$ 左右，由此可使反应顺利地进行，且使水及有机溶剂蒸发。关于防雾涂料组合物涂布物的加热，除了利用燃烧器或烘箱等加热装置进行加热以外，还可以通过利用干燥机等的热风进行的加热方法来进行。当如此将实施方式的防雾涂料组合物涂布于基材，通过加热使水或有机溶剂干燥时，在基材表面上扩散的长条状胶体氧化硅(及视情况而定的球状胶体氧化硅)成为长条状氧化硅(视情况而定的球状胶体氧化硅)，形成覆膜。另一方面，硅烷衍生物化合物与这些氧化硅键结，使氧化硅之间交联，形成牢固的高级结构。通过如此将实施方式的防雾涂料组合物应用于物品，可形成防雾涂膜，获得防雾物品。  \n\n[0045] 本发明的另一实施方式是一种防雾涂膜，其包含长条状氧化硅、与硅烷衍生物化合物的反应物。实施方式的防雾涂膜的特征在于，长条状氧化硅与硅烷衍生物化合物键结在一起。在实施方式的防雾涂膜中，硅烷衍生物化合物优选为下述硅烷衍生物化合物混合物，该硅烷衍生物化合物混合物至少包含分子内具有聚乙二醇链的硅烷衍生物化合物及分子内具有环氧基的硅烷衍生物化合物。使用附图在以下说明实施方式的防雾涂料组合物含有长条状胶体氧化硅及硅烷衍生物化合物混合物的技术性有意义点。此外，防雾涂膜的结构、及密接性表现机制的理论并不拘泥于以下内容。  \n\n[0046] 图1是表示由实施方式的含有长条状胶体氧化硅及硅烷衍生物化合物混合物的防雾涂料组合物(本发明的一实施方式)所形成的防雾涂膜的状态的附图。图1中，1表示基材；2表示长条状氧化硅；3表示源自分子内具有聚乙二醇链的硅烷衍生物化合物的基团；4表示源自分子内具有环氧基的硅烷衍生物化合物的基团；6表示防雾涂膜。在图1的防雾涂膜6中，绘制成下述形态，即，较长形状(例如筒状、棒状、绳状)的长条状氧化硅2以其长度方向大体一致的状态配置，但在实际的防雾涂膜6中，长条状氧化硅2未必规则性地配置。在图1中，具有相对刚性且较长的结构的长条状氧化硅2配置在基材1上，此处键结有分子内具有聚乙二醇链的硅烷衍生物化合物。另一方面，长条状氧化硅2上键结有分子内具有环氧基的硅烷衍生物化合物，使长条状氧化硅2之间交联在一起。分子内具有环氧基的硅烷衍生物化合物根据情况使基材1与长条状氧化硅2之间交联在一起。当水蒸气与图1中所示的防雾涂膜6接触时，因为在防雾涂膜6中存在基团3，所述基团3源自分子内具有作为亲水基的聚乙二醇链的硅烷衍生物化合物，所以立即在防雾涂膜6上形成水膜。另一方面，因为源自分子内具有环氧基的硅烷衍生物化合物的基团4使长条状氧化硅2之间、或基材1与长条状氧化硅2之间交联在一起，所以形成有高级结构的防雾涂膜6牢固地密接在基材1上。  \n\n[0047] 另一方面，图2是表示由含有长条状胶体氧化硅、硅烷衍生物化合物混合物、以及球状胶体氧化硅的防雾涂料组合物(本发明的另一实施方式)所形成的防雾涂膜的状态的附图。图2中，1为基材；2为长条状氧化硅；3为源自分子内具有聚乙二醇链的硅烷衍生物化合物的基团；4为源自分子内具有环氧基的硅烷衍生物化合物的基团；5为球状氧化硅；6为防雾涂膜。在图2的防雾涂膜6中，绘制成下述形态，即，较长形状(例如筒状、棒状、绳状)的长条状氧化硅2以其长度方向大体一致的状态配置，但在实际的防雾涂膜6中，长条状氧化硅2未必规则性地配置。在图2中，具有相对刚性且较长的结构的长条状氧化硅2被配置在基材1上，在相邻的长条状氧化硅2之间随处可能存在的空隙(通常具有几百纳米～几微米左右的大小)内埋设有比空隙大小更小的(几纳米～几十纳米的)球状氧化硅5。认为虽然球状氧化硅5并非以完全填埋空隙的方式配置，但如图2所示，是以大体上使空隙消失的方式配置。在长条状氧化硅2及球状氧化硅5上键结有分子内具有聚乙二醇链的硅烷衍生物化合物。另一方面，在长条状氧化硅2及球状氧化硅5上键结有分子内具有环氧基的硅烷衍生物化合物，使长条状氧化硅2之间、长条状氧化硅2与球状氧化硅5之间、球状氧化硅5之间分别交联在一起。分子内具有环氧基的硅烷衍生物化合物根据情况使基材1与长条状氧化硅2之间、或者基材1与球状氧化硅5之间分别交联在一起。当水蒸气与图2中所示的防雾涂膜6接触时，因为在防雾涂膜6中存在基团3，所述基团3源自分子内具有作为亲水基的聚乙二醇链的硅烷衍生物化合物，所以立即在防雾涂膜6上形成水膜。另一方面，因为源自分子内具有环氧基的硅烷衍生物化合物的基团4使长条状氧化硅2之间、长条状氧化硅2与球状氧化硅5之间、球状氧化硅5之间、基材1与长条状氧化硅2之间、或者基材1与球状氧化硅5之间分别交联在一起，所以形成有高级结构的防雾涂膜6牢固地密接在基材1上。此外，实施方式的防雾涂膜中，长条状氧化硅可包含酸性长条状氧化硅及碱性长条状氧化硅，球状氧化硅可为碱性球状氧化硅。在该实施方式中，酸性长条状氧化硅是指分散于水中时表现酸性的长条状氧化硅。另外，碱性长条状氧化硅是指分散于水中时表现碱性的长条状氧化硅。进而，碱性球状氧化硅是指分散于水中时表现碱性的球状氧化硅。  \n\n[0048] 可将实施方式的防雾涂料组合物应用于基材来形成防雾涂膜。并且，可获得基材具有防雾涂膜的实施方式的防雾物品。作为实施方式的防雾物品，例如可列举：照明装置、前照灯、窗、透镜、透镜盖、监视器、监视器盖等。实施方式的防雾物品具有优异的防雾性能，且即使在防雾物品被暴露在意料之外的高温条件下时，也不会引起流水痕的形成等外观变化。实施方式的防雾涂膜牢固地接着于塑料等基材，密接性较高，因此能够提供一种在高温下的耐久性较高，且长期发挥防雾效果的防雾物品。  \n\n[0049] [实施例]  \n\n[0050] (1)防雾涂料组合物的制作(长条状胶体氧化硅及硅烷衍生物化合物混合物)  \n\n[0051] 将酸性长条状胶体氧化硅(ST‑OUP[固体成分 $15\\%$ ，水分散液]，日产化学工业(股))、碱性长条状胶体氧化硅(ST‑UP[固体成分 $20\\%$ ，水分散液]，日产化学工业(股))、分子内具有聚乙二醇链的硅烷衍生物化合物(Dynasylan  4148[固体成分 $100\\%]$ ，EvonikJapan(股))、分子内具有环氧基的硅烷衍生物化合物(KBM403[固体成分 $100\\%]$ ，信越化学工业(股))、表面活性剂(Neocol‑YSK[固体成分 $70\\%$ ，丙二醇‑水混合分散液]，第一工业制药(股))、表面活性剂(KF640，信越化学工业(股))、以及有机溶剂(丙二醇单甲醚(日本乳化剂(股))、二丙酮醇(东京化成工业(股))加以混合而制作防雾涂料组合物。将各防雾涂料组合物的成分构成示于表1及表2。另外，准备不属于分子内具有聚乙二醇链的硅烷衍生物化合物、分子内具有环氧基的硅烷衍生物化合物中任一者的硅烷衍生物化合物即X‑12‑1098([固体成分 $30\\%$ ，水分散液]，信越化学工业(股))作为硅烷衍生物化合物的一种，用作比较例的防雾涂料组合物。  \n\n[0052] [表1]  \n\n[0053] [表1]防雾涂料组合物的组成及防雾涂膜的评价(实施例)  \n\n[0054]  \n\n<html><body><table><tr><td rowspan=\"2\" colspan=\"3\" rowspan=\"2\">长条状胶体氧化硅</td><td colspan=\"3\">实施例</td></tr><tr><td>1</td><td>2</td></tr><tr><td colspan=\"3\" rowspan=\"2\">防雾涂料 组合物</td><td>ST-OUP</td><td>63.13</td><td>61.71</td></tr><tr><td>ST-UP</td><td>15.78</td><td>15.43</td></tr><tr><td colspan=\"3\" rowspan=\"2\">(重量份) 硅烷衍生物化合物</td><td>Dynasylan4148</td><td>0.33</td><td>0.32</td></tr><tr><td>KBM403</td><td>0.47</td><td>0.46</td></tr><tr><td colspan=\"2\" rowspan=\"2\">表面活性剂</td><td>X-12-1098</td><td></td><td></td><td></td></tr><tr><td>NC-YSK</td><td></td><td>0.28</td><td>0.27</td></tr><tr><td colspan=\"2\" rowspan=\"2\"></td><td>KF640</td><td>0.14</td><td></td><td>0.13</td></tr><tr><td>PGM</td><td></td><td>17.28</td><td>17.35</td></tr><tr><td rowspan=\"2\" colspan=\"2\">溶剂</td><td>DAA</td><td>2.59</td><td></td><td>4.33</td></tr><tr><td>合计</td><td>100</td><td></td><td>100</td></tr><tr><td rowspan=\"7\">评价</td><td rowspan=\"3\">初始涂膜</td><td colspan=\"2\">涂布性</td><td></td><td></td><td></td></tr><tr><td colspan=\"2\"></td><td></td><td>良好 无雾</td><td>良好</td></tr><tr><td colspan=\"2\">密接性</td><td>防雾性</td><td>良好</td><td>无雾</td></tr><tr><td rowspan=\"2\">耐湿热试验后 涂膜</td><td colspan=\"2\">防雾性</td><td>无雾</td><td></td><td>良好 无雾</td></tr><tr><td colspan=\"2\">密接性</td><td>良好</td><td></td><td></td></tr><tr><td rowspan=\"2\">耐热试验后涂 膜</td><td colspan=\"2\">防雾性</td><td>无雾</td><td></td><td>良好 无雾</td></tr><tr><td colspan=\"2\">密接性</td><td>良好</td><td></td><td>良好</td></tr></table></body></html>  \n\n[0055] [表2][0056] [表2]防雾涂料组合物的组成及防雾涂膜的评价(比较例)  \n\n[0057]  \n\n<html><body><table><tr><td rowspan=\"2\" colspan=\"3\" rowspan=\"2\"></td><td rowspan=\"2\"></td><td colspan=\"4\">比较例</td></tr><tr><td>1 2</td><td>3</td><td>4</td><td>5</td></tr><tr><td rowspan=\"8\">防雾 涂料 组合 物 (重量 份)</td><td colspan=\"2\" rowspan=\"2\">长条状胶体氧化 硅</td><td>ST-OUP</td><td>63.13</td><td>62.61</td><td>65.25</td><td>64.55</td><td>58.12</td></tr><tr><td>ST-UP</td><td>15.78</td><td>15.65</td><td>16.31</td><td>16.14</td><td>14.53</td></tr><tr><td colspan=\"2\" rowspan=\"2\">硅烷衍生物化合 物</td><td>Dynasylan 4148</td><td>0.33</td><td>0.33</td><td>0.34</td><td>0.34</td><td>0.31</td></tr><tr><td>KBM403</td><td></td><td></td><td>0.48</td><td>0.48</td><td>0.43</td></tr><tr><td rowspan=\"2\" colspan=\"2\">表面活性剂</td><td>X-12-1098</td><td></td><td>1.10</td><td></td><td></td><td></td></tr><tr><td>NC-YSK</td><td>0.28</td><td>0.27</td><td>0.29</td><td>0.28</td><td>0.25</td></tr><tr><td rowspan=\"2\" colspan=\"2\">溶剂</td><td>KF640</td><td>0.14</td><td>0.14</td><td>0.14</td><td>0.14</td><td>0.13</td></tr><tr><td>PGM DAA</td><td>17.75</td><td>17.31</td><td>17.19</td><td>17.21</td><td>17.48</td></tr><tr><td colspan=\"3\"></td><td>2.59 100</td><td>2.59</td><td></td><td>0.86</td><td>8.75</td></tr><tr><td rowspan=\"6\">评价</td><td rowspan=\"3\">初始涂膜</td><td>合计</td><td></td><td></td><td>100</td><td>100</td><td>100</td><td>100</td></tr><tr><td>涂布性</td><td></td><td>良好</td><td>良好</td><td>良好</td><td>良好</td><td>不良</td></tr><tr><td colspan=\"2\">防雾性</td><td>无雾 良好</td><td>无雾 良好</td><td>无雾 良好</td><td>无雾</td><td>无雾</td></tr><tr><td rowspan=\"2\">耐湿热试 验后涂膜</td><td>密接性</td><td></td><td></td><td>有雾</td><td>无雾</td><td>良好 无雾</td><td>良好 无雾</td></tr><tr><td colspan=\"2\">防雾性</td><td>无雾 不良</td><td>不良</td><td>不良</td><td>不良</td><td>良好</td></tr><tr><td rowspan=\"2\">耐热试验 后涂膜</td><td colspan=\"2\">密接性</td><td>无雾</td><td>有雾</td><td>无雾</td><td>无雾</td><td>无雾</td></tr><tr><td colspan=\"2\">防雾性 密接性</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td></tr></table></body></html>  \n\n[0058] 此外，表1及表2中的缩写的含义如下所述：  \n\n[0059] ST‑OUP：日产化学工业(股)商品名，酸性长条状胶体氧化硅  \n[0060] ST‑UP：日产化学工业(股)商品名，碱性长条状胶体氧化硅  \n[0061] NC‑YSK：Neocol‑YSK，第一工业制药(股)商品名，阴离子系表面活性剂  \n[0062] KF640：信越化学工业(股)商品名，非离子系表面活性剂  \n[0063] PGM：丙二醇单甲醚  \n[0064] DAA：二丙酮醇  \n[0065] Dynasylan  4148：Evonik  Japan(股)商品名，分子内具有聚乙二醇链的以下式所  \n表示的硅烷衍生物化合物：  \n\n[0066] [化5]  \n\n[0067]  \n\n![](images/8ad7670090271af7a728d136975c68e4f1100a43d1c1701c28db969c1d9ba3fc.jpg)  \n\n[0068] (式中，q是相当于所述式1‑1的n的数，r是相当于所述式1‑1的m的数)  \n\n[0069] KBM403：信越化学工业(股)商品名，3‑缩水甘油氧基丙基三甲氧基硅烷，分子内具有环氧基的以下式所表示的硅烷衍生物化合物：  \n\n[0070] [化6]  \n\n[0071]  \n\n![](images/5dbb34e5ec02a9d58b29b941d503f9fd574ead1dbb96995d269f5a1d6f857b75.jpg)  \n\n[0072] X‑12‑1098：信越化学工业(股)商品名，不属于分子内具有聚乙二醇链的硅烷衍生物化合物、分子内具有环氧基的硅烷衍生物化合物中任一者的以下式所表示的硅烷衍生物化合物：  \n\n[0073]  \n\n![](images/cab18b16e4e64ea3a5d9ef3c59f4bb83840d6b137e4f9e13c7257b2f0ec3c0e2.jpg)  \n\n[0075] (2)防雾涂料组合物的制作(长条状胶体氧化硅、球状胶体氧化硅、以及硅烷衍生物化合物混合物)  \n\n[0076] 将酸性长条状胶体氧化硅(ST‑OUP[固体成分 $15\\%$ ，水分散液]，日产化学工业(股))、碱性长条状胶体氧化硅(ST‑UP[固体成分 $20\\%$ ，水分散液]，日产化学工业(股))、碱性球状胶体氧化硅(ST‑N[固体成分 $20\\%$ ，水分散液]，日产化学工业(股))、碱性球状胶体氧化硅(ST‑NXS[固体成分 $15\\%$ ，水分散液]，日产化学工业(股))、分子内具有聚乙二醇链的硅烷衍生物化合物(Dynasylan  4148[固体成分 $100\\%]$ ，Evonik  Japan(股))、分子内具有聚乙二醇链及酰基的硅烷衍生物化合物(2‑[乙酰氧基(聚亚乙氧基)丙基]三乙氧基硅烷，[固体成分 $100\\%]$ ，Gelest  Inc.)、分子内具有聚乙二醇链及氨基甲酸酯基的硅烷衍生物化合物(通过以下所述的方法来合成，氨基甲酸酯硅烷A、氨基甲酸酯硅烷B及氨基甲酸酯硅烷C、氨基甲酸酯硅烷D)、分子内具有环氧基的硅烷衍生物化合物(KBM403[固体成分 $100\\%]$ ，信越化学工业(股))、表面活性剂(Neocol‑YSK，[固体成分 $70\\%$ 、丙二醇‑水混合分散液]，第一工业制药(股))、表面活性剂(KF640，信越化学工业(股))、以及作为有机溶剂的异丙醇(关东化学(股))、丙二醇单甲醚(日本乳化剂(股))及二丙酮醇(东京化成工业(股))加以混合而制作防雾涂料组合物。将各防雾涂料组合物的成分构成示于表3。另外，准备不属于分子内具有聚乙二醇链的硅烷衍生物化合物、分子内具有环氧基的硅烷衍生物化合物中任一者的硅烷衍生物化合物即X‑12‑1098([固体成分 $30\\%$ ，水分散液]，信越化学工业(股))作为硅烷衍生物化合物的一种，用作比较例的防雾涂料组合物(表4)。  \n\n[0077] 此外，实施例中所使用的分子内具有聚乙二醇链及氨基甲酸酯基的硅烷衍生物化合物(氨基甲酸酯硅烷A、氨基甲酸酯硅烷B、氨基甲酸酯硅烷C及氨基甲酸酯硅烷D)是通过以下方式合成的：  \n\n[0078] (2‑1)氨基甲酸酯硅烷A的合成  \n\n[0079] 向 $50\\mathrm{mL}$ 的茄型烧瓶中加入3‑异氰酸基丙基三甲氧基硅烷(东京化成工业(股)[固体成分 $100\\%]$ )6 .6重量份、Uniox $\\mathtt{M}-400$ (甲基封端型聚乙二醇，日油(股)[固体成分$100\\%]$ )16.3重量份，在 $75\\mathrm{{^\\circC}}$ 下搅拌10小时。通过 $^1\\mathrm{H}$ ‑NMR确认到源自异氰酸基的峰消失了，获得以下式所表示的氨基甲酸酯硅烷A：  \n\n[0080] [化8]  \n\n![](images/36ba2c571d8b8b1f7528262a9befbaf47f50002b9d3b1d64f7aceead846d2d8b.jpg)  \n\n[0082] (2‑2)氨基甲酸酯硅烷B的合成  \n\n[0083] 向 $50\\mathrm{mL}$ 的茄型烧瓶中加入KBE‑9007N(3‑异氰酸基丙基三乙氧基硅烷，信越硅胶(股)[固体成分 $100\\%]$ )10 .0重量份、聚乙二醇400(富士胶片和光纯药(股)[固体成分$100\\%]$ )16.2重量份，在 $75\\mathrm{{^\\circC}}$ 下搅拌10小时。通过 $^1\\mathrm{H}$ ‑NMR确认到源自异氰酸基的峰消失了，获得以下式所表示的氨基甲酸酯硅烷B：  \n\n[0084] [化9]  \n\n[0085]  \n\n![](images/577aebd11def9aa4cc77edd3ac24728e43a9d85a99b3d171276541d52e066a2d.jpg)  \n\n[0086] (2‑3)氨基甲酸酯硅烷C的合成  \n\n[0087] 向 $50\\mathrm{mL}$ 的茄型烧瓶中加入KBE‑9007N(3‑异氰酸基丙基三乙氧基硅烷，信越硅胶(股)[固体成分 $100\\%]$ )10.0重量份、及聚乙二醇200(富士胶片和光纯药(股)，[固体成分$100\\%]$ )8.1重量份，在 $75\\mathrm{{^\\circC}}$ 下搅拌10小时。通过 $^1\\mathrm{H}$ ‑NMR确认到源自异氰酸基的峰消失了，获得以下式所表示的氨基甲酸酯硅烷C：  \n\n[0088] [化10]  \n\n![](images/5ce4bea51deb52a46e609eba73c8a527820075a8e3e66d5449219b88b5bcad00.jpg)  \n\n[0090] (2‑4)氨基甲酸酯硅烷D的合成  \n\n[0091] 向 $50\\mathrm{mL}$ 的茄型烧瓶中加入KBE‑9007N(3‑异氰酸基丙基三乙氧基硅烷，信越硅胶(股)[固体成分 $100\\%]$ )10 .0重量份、及聚乙二醇600(富士胶片和光纯药(股)[固体成分$100\\%]$ )24.3重量份，在 $75\\mathrm{{^\\circC}}$ 下搅拌10小时。通过 $^1\\mathrm{H}$ ‑NMR确认到源自异氰酸基的峰消失了，获得以下式所表示的氨基甲酸酯硅烷D：  \n\n[0092] [化11]  \n\n![](images/4d1a1f50c2f76d1d8c3dad390ed4b6bad7ea9a26cb2d31e2a361d658d00f4bdd.jpg)  \n\n[0094] [表3][0095] [表3]防雾涂料组合物的组成及防雾涂膜的评价(实施例)  \n\n[0096] [0099]  \n\n<html><body><table><tr><td rowspan=\"2\" colspan=\"3\"></td><td colspan=\"6\">实施例</td></tr><tr><td>3</td><td>4</td><td>5</td><td>6</td><td>7</td><td>8</td></tr><tr><td rowspan=\"8\">防雾 涂料 组合 物 (重 量 份)</td><td rowspan=\"2\">长条状胶体氧 化硅</td><td>ST-OUP</td><td>25.62 6.40</td><td>25.62 6.40</td><td>25.62 6.40</td><td>25.62 6.40</td><td>25.20 6.40</td><td>25.62</td></tr><tr><td>ST-UP</td><td></td><td></td><td></td><td></td><td></td><td>6.40</td></tr><tr><td rowspan=\"2\">球状胶体氧化 硅 硅烷衍生物化</td><td>ST-N</td><td>5.49 7.32</td><td>5.49 7.32</td><td>5.49 7.32</td><td>5.49 7.32</td><td>5.49 7.32</td><td>5.49 7.32</td></tr><tr><td>ST-NXS Dynasylan</td><td>0.19</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td colspan=\"2\">合物 4148 KBM403</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td colspan=\"2\">乙酰基硅烷</td><td>0.27</td><td>0.27 0.19</td><td>0.27</td><td>0.27</td><td>0.27</td><td>0.27</td></tr><tr><td colspan=\"2\">氨基甲酸酯 硅烷A</td><td></td><td></td><td>0.21</td><td></td><td></td><td></td></tr><tr><td colspan=\"2\">氨基甲酸酯</td><td></td><td></td><td></td><td>0.23</td><td></td><td></td></tr><tr><td colspan=\"2\">硅烷B 氨基甲酸酯</td><td></td><td></td><td></td><td></td><td>0.16</td><td></td></tr><tr><td colspan=\"2\">硅烷C 氨基甲酸酯</td><td></td><td></td><td></td><td></td><td></td><td>0.29</td></tr><tr><td colspan=\"2\"></td><td>硅烷D X-12-1098</td><td></td><td></td><td>1.28</td><td></td><td></td></tr><tr><td colspan=\"2\">表面活性剂 NC-YSK</td><td>0.16</td><td>0.16</td><td>0.16</td><td>0.16</td><td>0.16</td><td>0.16</td></tr><tr><td colspan=\"2\"></td><td>KF640 0.08</td><td>0.08</td><td>0.08</td><td>0.08</td><td>0.08</td><td></td></tr><tr><td colspan=\"2\">溶剂</td><td></td><td></td><td></td><td></td><td></td><td>0.08</td></tr><tr><td colspan=\"2\"></td><td>34.49</td><td>34.49</td><td>34.47</td><td>34.45</td><td>34.52</td><td>34.39</td></tr><tr><td colspan=\"2\">PGM DAA</td><td>18.16 1.82</td><td>18.16 1.82</td><td>18.16 1.82</td><td>18.16</td><td>18.16</td><td>18.16</td></tr><tr><td colspan=\"2\">合计 初始涂膜</td><td>100</td><td>100</td><td>100</td><td>1.82 100</td><td>1.82 100</td><td>1.82 100</td></tr><tr><td rowspan=\"3\">评价</td><td>涂布性</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td></tr><tr><td>防雾性</td><td>无雾</td><td>无雾</td><td>无雾</td><td>无雾</td><td>无雾</td><td>无雾</td></tr><tr><td>密接性</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td></tr><tr><td rowspan=\"3\">耐水试验 后涂膜 耐热试验</td><td>防雾性</td><td>无雾</td><td>无雾</td><td>无雾</td><td>无雾</td><td>无雾</td><td>无雾</td></tr><tr><td>密接性</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td></tr><tr><td>防雾性</td><td>无雾</td><td>无雾</td><td>无雾</td><td>无雾</td><td>无雾</td><td>无雾</td></tr><tr><td rowspan=\"2\">后涂膜</td><td>密接性</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>良好</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td></tr></table></body></html>\n\n[0097] [表4][0098] [表4]防雾涂料组合物的组成及防雾涂膜的评价(比较例)  \n\n<html><body><table><tr><td colspan=\"4\" rowspan=\"2\">防雾</td><td colspan=\"5\">比较例</td></tr><tr><td>6</td><td>7</td><td>8</td><td>9</td><td>10</td></tr><tr><td rowspan=\"9\">涂料 组合 物 (重 量 份)</td><td rowspan=\"2\">长条状胶体 氧化硅</td><td>ST-OUP</td><td>25.62</td><td>25.62</td><td>25.62</td><td>25.20</td><td>25.62</td></tr><tr><td>ST-UP</td><td>6.40</td><td>6.40</td><td>6.40</td><td>6.30</td><td>6.40</td></tr><tr><td rowspan=\"2\">球状胶体氧 化硅</td><td>ST-N</td><td>5.49</td><td>5.49</td><td>5.49</td><td>5.40</td><td>5.49</td></tr><tr><td>ST-NXS</td><td>7.32</td><td>7.32</td><td>7.32</td><td>7.20</td><td>7.32</td></tr><tr><td rowspan=\"9\">硅烷衍生物 化合物</td><td>Dynasylan4148</td><td>0.38</td><td></td><td></td><td>0.40</td><td>0.19</td></tr><tr><td>KBM403</td><td></td><td>0.54</td><td></td><td>0.56</td><td>0.27</td></tr><tr><td>乙酰基硅烷</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>氨基甲酸酯硅烷A</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>氨基甲酸酯硅烷B</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>氨基甲酸酯硅烷C</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>氨基甲酸酯硅烷D</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>X-12-1098</td><td></td><td></td><td>1.28</td><td></td><td></td></tr><tr><td>表面活性剂 NC-YSK</td><td>0.16</td><td>0.16</td><td>0.16</td><td>0.16</td><td>0.16</td></tr><tr><td rowspan=\"4\">溶剂</td><td>KF640</td><td>0.08</td><td>0.08</td><td>0.08</td><td>0.08</td><td>0.08</td></tr><tr><td>IPA</td><td>34.57</td><td>34.41</td><td>33.67</td><td>34.72</td><td>36.31</td></tr><tr><td>PGM</td><td>18.16</td><td>18.16</td><td>18.16</td><td>18.16</td><td>18.16</td></tr><tr><td>DAA</td><td>1.82</td><td>1.82</td><td>1.82</td><td>1.82</td><td></td></tr><tr><td rowspan=\"6\">评价</td><td rowspan=\"3\">初始涂膜</td><td>合计</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td></tr><tr><td>涂布性</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td></tr><tr><td>防雾性</td><td>无雾</td><td>无雾</td><td>无雾</td><td>无雾</td><td>无雾</td></tr><tr><td rowspan=\"2\">耐水试验</td><td>密接性</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td></tr><tr><td>防雾性</td><td>无雾</td><td>有雾</td><td>有雾</td><td>有雾</td><td>无雾</td></tr><tr><td rowspan=\"2\">后涂膜 耐热试验</td><td>密接性</td><td>不良</td><td>良好</td><td>不良</td><td>良好</td><td>不良</td></tr><tr><td>防雾性</td><td>无雾</td><td>有雾</td><td>有雾</td><td>有雾</td><td>无雾</td></tr><tr><td>后涂膜</td><td>密接性</td><td></td><td>良好</td><td>良好</td><td>良好</td><td>良好</td><td>良好</td></tr></table></body></html>  \n\n[0100] 此外，表3、表4中的缩写的含义如下所述：  \n\n[0101] ST‑OUP：日产化学工业(股)商品名，酸性长条状胶体氧化硅  \n[0102] ST‑UP：日产化学工业(股)商品名，碱性长条状胶体氧化硅  \n[0103] ST‑N：日产化学工业(股)商品名，粒径 $12\\mathrm{nm}$ 的碱性球状胶体氧化硅  \n[0104] ST‑NXS：日产化学工业(股)商品名，粒径5nm的碱性球状胶体氧化硅  \n[0105] NC‑YSK：Neocol‑YSK，第一工业制药(股)商品名，阴离子系表面活性剂  \n[0106] KF640：信越化学工业(股)商品名，非离子系表面活性剂  \n[0107] IPA：异丙醇  \n[0108] PGM：丙二醇单甲醚  \n[0109] DAA：二丙酮醇  \n[0110] Dynasylan  4148：Evonik  Japan(股)商品名，分子内具有聚乙二醇链的以  \n\n表示的硅烷衍生物化合物：  \n\n[0111] [化12]  \n\n[0112]  \n\n![](images/91a9f1187750e8bdfe19bd30ddcbd92b66f432f4aac758ba1c039661ce431e12.jpg)  \n\n[0113] (式中,q是相当于所述式1‑1的n的数，r是相当于所述式1‑1的m的数)  \n\n[0114] KBM403：信越化学工业(股)商品名，3‑缩水甘油氧基丙基三甲氧基硅烷，分子内具有环氧基的以下式所表示的硅烷衍生物化合物：  \n\n[0115] [化13]  \n\n[0116]  \n\n![](images/7a41f1690a2f759ee59efd10fef6deb9d2715ad9736445fd35d1a518997381a9.jpg)  \n\n[0117] 乙酰基硅烷：Gelest  Inc.，2‑[乙酰氧基(聚亚乙氧基)丙基]三乙氧基硅烷，分子内具有聚乙二醇链及酰基的以下式所表示的硅烷衍生物化合物：  \n\n[0118] [化14]  \n\n[0119]  \n\n![](images/1e164d9ad4b9d1acb32a062afdc5aebb2ead84406198e5d1bf2ea95ef2afb4e4.jpg)  \n\n[0120] 氨基甲酸酯硅烷A、氨基甲酸酯硅烷B、氨基甲酸酯硅烷C、氨基甲酸酯硅烷D：如上所述的合成品  \n\n[0121] X‑12‑1098：信越化学工业(股)商品名，不属于分子内具有聚乙二醇链的硅烷衍生物化合物、分子内具有环氧基的硅烷衍生物化合物中任一者的以下式所表示的硅烷衍生物化合物：  \n\n[0122] [化15][0124] (3)防雾涂膜的制作  \n\n![](images/328383f91d6a8d9d666836201fe57dd8508402bb15e7a9cfbf9a80fe4b0aa901.jpg)  \n\n[0125] 在聚碳酸酯树脂板基材上涂布各防雾涂料组合物。涂布是通过空气喷涂法进行的。以由防雾涂料组合物所形成后的防雾涂膜的厚度成为1μm的方式进行调整。将涂布有防雾涂料组合物的基材放入至 $110^{\\circ}\\mathrm{C}$ 的烘箱内，加热15分钟使水及有机溶剂蒸发而形成防雾涂膜。由此获得各防雾涂膜试验片。  \n\n[0126] (4)防雾涂膜的涂布性评价  \n[0127] 通过目视来观察防雾涂膜试验片的表面。当可获得均质防雾涂膜时记为“良好”，当在防雾涂膜的表面发现破裂或收缩等时记为“不良”。  \n\n[0128] (5)防雾涂膜的防雾性评价  \n\n[0129] 在比 $60^{\\circ}\\mathrm{C}$ 热水浴的水面高1cm的位置处，将防雾涂膜试验片以涂膜朝下的方式进行配置，使涂膜面向来自热水浴的蒸气。经过1分钟后，通过目视来观察涂膜上是否形成有雾。当涂膜表面未产生雾时记为“无雾”，当涂膜表面产生雾时记为“有雾”。  \n\n[0130] (6)防雾涂膜的密接性评价[0131] 通过依据JIS  K  5600‑5‑6(涂料一般试验方法，与涂膜的机械性质相关的试验法，附着性[交叉切割法])的方法，以目视观察各防雾涂膜试验片的防雾涂膜是否剥离。当未确认到涂膜剥离时记为“良好”，当确认到涂膜剥离时记为“不良”。  \n\n[0132] (7)防雾涂膜的耐湿热性试验  \n\n[0133] 将各防雾涂膜试验片放置在温度 $50^{\\circ}\\mathrm{C}$ 、湿度 $95\\%$ 的环境下，静置24小时。将防雾涂膜试验片从该环境中取出，在室温下静置12小时。  \n\n[0134] (8)耐湿热性试验后的防雾涂膜的防雾性评价[0135] 所述耐湿热性试验后，在比 $40^{\\circ}\\mathrm{C}$ 热水浴的水面高1cm的位置处，将防雾涂膜试验片以涂膜朝下的方式进行配置，使涂膜面向来自热水浴的蒸气。经过10秒钟后，通过目视来观察涂膜上是否形成有雾。当涂膜表面未产生雾时记为“无雾”，当涂膜表面产生雾时记为“有雾”。  \n\n[0136] (9)耐湿热性试验后的防雾涂膜的密接性评价[0137] 所述耐湿热性试验后，通过依据JIS  K  5600‑5‑6(涂料一般试验方法，与涂膜的机械性质相关的试验法，附着性[交叉切割法])的方法，以目视观察各防雾涂膜试验片的防雾涂膜是否剥离。当未确认到涂膜剥离(也包括试验中所使用的透明感压胶带的粘附成分残留在防雾涂膜试验片上的情况)时记为“良好”，当确认到涂膜剥离时记为“不良”。  \n\n[0138] (10)防雾涂膜的耐热性试验  \n\n[0139] 将各防雾涂膜试验片放入至已干燥的 $130^{\\circ}\\mathrm{C}$ 烘箱内，静置72小时，然后再在室温下静置12小时。  \n\n[0140] (11)耐热性试验后的防雾涂膜的防雾性评价[0141] 所述耐热性试验后，在比 $40^{\\circ}\\mathrm{C}$ 热水浴的水面高1cm的位置处，将防雾涂膜试验片以涂膜朝下的方式进行配置，使涂膜面向来自热水浴的蒸气。经过10秒钟后，通过目视来观察涂膜上是否形成有雾。当涂膜表面未产生雾时记为“无雾”，当涂膜表面产生雾时记为“有雾”。  \n\n[0142] (12)耐热性试验后的防雾涂膜的密接性评价[0143] 所述耐热性试验后，通过依据JIS  K  5600‑5‑6(涂料一般试验方法，与涂膜的机械性质相关的试验法，附着性[交叉切割法])的方法，以目视观察各防雾涂膜试验片的防雾涂膜是否剥离。当未确认到涂膜剥离(也包括试验中所使用的透明感压胶带的粘附成分残留在防雾涂膜试验片上的情况)时记为“良好”，当确认到涂膜剥离时记为“不良”。  \n\n[0144] (13)防雾涂膜的耐水性试验  \n\n[0145] 使各防雾涂膜试验片浸渍在 $60^{\\circ}\\mathrm{C}$ 的水中，放置240小时。将防雾涂膜试验片从水中取出，在室温下静置12小时。  \n\n[0146] (14)耐水性试验后的防雾涂膜的防雾性评价[0147] 所述耐水性试验后，在比 $40^{\\circ}\\mathrm{C}$ 热水浴的水面高1cm的位置处，将防雾涂膜试验片以涂膜朝下的方式进行配置，使涂膜面向来自热水浴的蒸气。经过10秒钟后，通过目视来观察涂膜上是否形成有雾。当涂膜表面未产生雾时记为“无雾”，当涂膜表面产生雾时记为“有雾”。  \n\n[0148] (15)耐水性试验后的防雾涂膜的密接性评价[0149] 所述耐水性试验后，通过依据JIS  K  5600‑5‑6(涂料一般试验方法，与涂膜的机械性质相关的试验法，附着性[交叉切割法])的方法，以目视观察各防雾涂膜试验片的防雾涂膜是否剥离。当未确认到涂膜剥离(也包括试验中所使用的透明感压胶带的粘附成分残留在防雾涂膜试验片上的情况)时记为“良好”，当确认到涂膜剥离时记为“不良”。  \n\n[0150] [实施例 $1{\\sim}2$ 及比较例 $1{\\sim}2]$  \n\n[0151] 实施例 $1{\\sim}2$ 、及比较例 $1{\\sim}2$ 是变更了硅烷衍生物化合物的种类及调配量的实验例。将分子内具有聚乙二醇链的硅烷衍生物化合物、与分子内具有环氧基的硅烷衍生物化合物加以并用的实施例 $1{\\sim}2$ 的防雾涂膜在涂布性、防雾性、密接性所有方面都表现出良好的结果，在耐湿热性试验以及耐热性试验后，也在防雾性、密接性方面表现出良好的结果。比较例1未调配分子内具有环氧基的硅烷衍生物化合物。比较例1的防雾涂膜在耐湿热性试验后，表现出密接性降低。比较例2调配了不属于分子内具有聚乙二醇链的硅烷衍生物化合物、分子内具有环氧基的硅烷衍生物化合物中任一者的硅烷衍生物化合物。比较例2的防雾涂膜在耐湿热性试验后，发现密接性及防雾性降低，在耐热性试验后，发现防雾性降低。  \n\n[0152] [实施例 $1{\\sim}2$ 及比较例 $3\\sim5]$  \n\n[0153] 实施例 $1{\\sim}2$ 、及比较例 $3{\\sim}5$ 是变更了作为有机溶剂的二丙酮醇的量的实验例。关于由未调配二丙酮醇的比较例3的防雾涂料组合物所形成的防雾涂膜，发现耐湿热性试验后的密接性降低。关于在防雾涂料组合物中调配0.86重量 $\\%$ 二丙酮醇的比较例4的防雾涂膜，发现耐湿热性试验后的密接性降低，关于在防雾涂料组合物中调配8.75重量 $\\%$ 二丙酮醇的比较例5的防雾涂膜，涂布性欠佳。  \n\n[0154] [实施例 $3{\\sim}8\\bar{.}$ ]  \n\n[0155] 实施例 $3{\\sim}8$ 是变更了硅烷衍生物化合物的种类及调配量的实验例。实施例 $3{\\sim}8$ 都并用了分子内具有聚乙二醇链的硅烷衍生物化合物、及分子内具有环氧基的硅烷衍生物化合物。实施例 $3{\\sim}8$ 的防雾涂膜在涂布性、防雾性、密接性所有方面都表现出良好的结果，耐水性试验后的防雾性、密接性也表现出良好的结果，且耐热性试验后的防雾性、密接性也表现出良好的结果。即便使用分子内具有聚乙二醇链及酰基的硅烷衍生物化合物(乙酰基硅烷)作为分子内具有聚乙二醇链的硅烷衍生物化合物(实施例4)，使用分子内具有聚乙二醇链及氨基甲酸酯基的硅烷衍生物化合物(氨基甲酸酯硅烷 $\\begin{array}{r}{\\mathrm{A}\\sim\\mathrm{D},}\\end{array}$ )作为分子内具有聚乙二醇链的硅烷衍生物化合物(实施例 $5{\\sim}8)$ )，防雾涂膜的涂布性、防雾性、密接性都良好，耐水性试验后的防雾性、密接性也未降低。基于实施例4及6的结果可知，不论分子内具有聚乙二醇链的硅烷衍生物化合物的末端是酯键(实施例4)，还是羟基(实施例6)，都不会对防雾涂膜的性能产生较大影响。另外，基于实施例 $6{\\sim}8$ 的结果可知，如果分子内具有聚乙二醇链的硅烷衍生物化合物中所存在的聚乙二醇链的重复单元的长度 $\\left(\\mathrm{m}\\mathbf{\\Omega},\\mathrm{m}_{1}\\mathbf{\\Omega},\\mathrm{m}_{2}\\right.$ 的数)至少处于 $4\\mathord{\\sim}15$ 的范围内，那么就不会对防雾涂膜的性能产生不良影响。  \n\n[0156] [实施例3及比较例 $6{\\sim}8]$  \n\n[0157] 实施例3、及比较例 $6{\\sim}8$ 是变更了硅烷衍生物化合物的种类及调配量的实验例。将分子内具有聚乙二醇链的硅烷衍生物化合物、及分子内具有环氧基的硅烷衍生物化合物加以并用的实施例3的防雾涂膜在涂布性、防雾性、密接性所有方面都表现出良好的结果，耐水性试验后的防雾性、密接性也表现出良好的结果，且耐热性试验后的防雾性、密接性也表现出良好的结果。比较例6仅调配有分子内具有聚乙二醇链的硅烷衍生物化合物。关于比较例6的防雾涂膜，在耐水性试验后发现密接性降低。比较例7仅调配有分子内具有环氧基的硅烷衍生物化合物。关于比较例7的防雾涂膜，在耐水性试验、耐热性试验后发现防雾性降低。比较例8调配有不属于分子内具有聚乙二醇链的硅烷衍生物化合物、分子内具有环氧基的硅烷衍生物化合物中任一者的硅烷衍生物化合物。比较例8的防雾涂膜在耐水性试验后的防雾性及密接性、以及耐热性试验后的防雾性方面发现降低。  \n\n[0158] [实施例3及比较例 $\\mathsf{\\Pi}^{\\mathsf{-}}\\mathsf{10}_{\\mathsf{-}}^{\\mathsf{-}}$ ]  \n[0159] 比较例9是调配有与实施例3相同的成分，但增大了硅烷衍生物化合物的调配量的实验例。比较例9的防雾涂膜在耐水性试验及耐热性试验后的防雾性方面发现降低。比较例10是除了未调配二丙酮醇以外都与实施例3相同的实验例。比较例10的防雾涂膜在耐水性试验后的密接性方面发现降低。[0160] [符号说明]  \n[0161] 1  基材  \n[0162] 2  长条状氧化硅  \n[0163] 3  源自分子内具有聚乙二醇链的硅烷衍生物化合物的基团[0164] 4  源自分子内具有环氧基的硅烷衍生物化合物的基团[0165] 5  球状氧化硅  \n[0166] 6  防雾涂膜。  \n\n![](images/8e84cbad36ffa99a4408869d5372c2205059535bf0cb6861a0084242a6409760.jpg)  \n图1  \n\n![](images/fda716c46e9ec398c2f3c08d59812ae579050e62460b7fc250cc94c6c776aa51.jpg)  \n图2",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,22 @@
+[
+    {
+        "id": 1,
+        "chunk": "# [12]发明专利申请公开说明书  \n\n[21]申请号 97126279.9  \n\n[51]Int.C]6 C08G 59/40 C09D163/00  \n\n[43]公开日 1999年7月7日  \n\n[11]公开号CN1221759A  \n\n<html><body><table><tr><td>[22]申请日97.12.30[21]申请号97126279.9 [71]申请人陶氏化学公司 地址美国密执根 [72]发明人』·甘G·巴迪尼 K·E·霍夫曼</td><td></td><td>[74]专利代理机构中国国际贸易促进委员会专利商标事 务所 代理人黄泽雄</td></tr><tr><td colspan=\"2\"></td></tr></table></body></html>",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# [54]发明名称用于固化环氧树脂的改进的固化催化剂[57]摘要  \n\n一种含有以下组分的配方：(1)咪唑与一种不饱和化合物的亲核加成加合物，该加合物中每分子含有1个以上咪唑片断;(2)一种环氧树脂，该配方的特征在于，该加合物中有少于 $50\\%$ (当量)咪唑片断被酸中和。该加合物在高温固化或低温固化中用作固化催化剂。配方以粉末涂料形式被制备和涂覆，用作涂层或作为层压制品的基质树脂。它可用于溶剂体系或液体体系。  \n\n专利文献出版社出版  \n\n1.一种用以下步骤制备可固化配方的方法：  \n\n(1)使咪唑与含有至少一个活化的双键的不饱和化合物反应，生成每一分子含有一个以上咪唑片断的亲核加成加合物;以及(2)制备含有该亲核的加成加合物和一种环氧树脂的配方，该方法的特征在于，在亲核的加成加合物中，少于 $50\\%$ （当量)的咪唑片断在步骤(2)以前被酸中和。  \n\n2.根据权利要求1的方法，其中加合物中不大于 $25\\%$ 咪唑片断被酸中和。  \n\n3.根据权利要求2的方法，其中加合物中不大于 $10\\%$ 咪唑片断被酸中和。  \n\n4.根据权利要求3的方法，其中加合物中不大于 $5\\%$ 咪唑片断被酸中和。  \n\n5.根据权利要求4的方法，其中咪唑选自未取代咪唑、2一甲基咪唑、2－乙基-4－甲基咪唑、2－苯基咪唑或N-(3-氨基丙基)咪唑中的任一种。  \n\n6.一种可固化的配方，它含有：  \n\n(1)咪唑与不饱和化合物生成的亲核加成加合物，该加合物中每一分子含有一个以上咪唑片断；以及  \n\n(2)一种环氧树脂，  \n\n两者的比例为每当量环氧树脂用0.05－10当量亲核的加成加合物，其特征在于，在加合物中，有少于 $50\\%$ (当量)的咪唑被酸中和。  \n\n7.一种固化权利要求2所述配方的方法，它通过将配方加热到其固化温度使之固化，其特征在于，固化温度小于 $130\\mathrm{^{\\circ}C}$ C  \n\n8.根据权利要求7的方法，其中可固化的配方为粉末涂料配方。  \n\n9.一种可固化的配方，它含有：  \n\n(a)一种环氧树脂;  \n\n(b)该环氧树脂的一种固化剂，其当量比为每当量环氧树脂用0.05  \n\n－10当量固化剂；以及  \n\n(c)催化数量的、用于环氧树脂与固化剂反应的催化剂，该方法的特征在于，催化剂为咪唑与一种不饱和化合物的亲核加成加合物，在该加合物中，有少于 $50\\%$ (当量)的咪唑片断被酸中和。  \n\n10.根据权利要求9的可固化配方，其中加合物的浓度为5-200毫克当量/当量环氧树脂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 3,
+        "chunk": "# 说明书",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# 用于固化环氧树脂的改进的固化催化剂  \n\n本发明涉及用于固化环氧树脂的催化剂技术，特别是涉及用于粉末配方的催化剂技术。  \n\n用含有环氧树脂、固化催化剂和任选的固化剂的粉末涂覆到基材上的方法来涂布制品是大家熟悉的。通常，可将基材加热，然后将粉末涂覆到仍然热的基材上;或者将粉末涂覆到冷的基材上，然后将基材加热。在这两种情况下，加热使粉末熔融和流动，以便涂布到基材上，然后再固化。适合的方法的例子在U.S.4,358，571(1982年11月9日,Kaufman)第 5列第 5－49 行;Lee & Neville,环氧树脂手册，第 20－15至 20－20 页（McGraw－Hill BookCo.1967）以及Tess,“环氧树脂涂料”，环氧树脂（第2版），772－778页（MarcelDekkerInc.1988)中描述。例如，用静电喷涂或流化床法将涂料涂覆到通常被加热到 $140-240^{\\circ}\\mathrm{C}$ 的金属基材上。  \n\n对于环氧树脂粉末涂料或溶剂基涂料体系的固化来说，许多固化催化剂是已知的。适合的催化剂的例子包括叔胺类和季铵类，以及叔麟类和季麟类。已知的潜在催化剂含有这样一种盐，它含有铵或片断以及弱亲核酸 $\\frac{1}{x^{n}}$ 硼酸或氟硼酸的共轭碱。适合的催化剂和潜在催化剂的例子包括 $\\mathrm{C}_{1}-\\mathrm{C}_{6}$ 低碳烷基三苯基卤化以及以下专利公开的催化剂:US5,202,407(1992年1月24日，Pham等);US4,725,652(1987年3月4日，Bertram等);EPO专利公开0328020A3(1989年8月16日,Bertram等);US5,140,079(1992年8月18日，Muskopf 等）;US5,308,895（1994年 5月3日，Gan等);和US5,169,473(1992年11月8日,Bertram 等)。US4,358,571(1982 年11月9日,Kaufman等)公开通过咪唑或取代咪唑与丙烯酸酯、环氧树脂或异氰酸酯反应，然后用脂肪酸或二元羧酸中和咪唑来制备加合物。这些加合物在 $132\\%(270^{\\circ}\\mathrm{F})$ 下用作环氧树脂的固化剂。  \n\nUS5,175,219(1992年12月29日，Burba 等)公开了：（1)咪唑基化合物与环氧树脂反应生成一种加合物;(2)该加合物与丙烯酸或其衍生物反应,以使加合物中胺的氢原子质子化。生成的加合物在约 $120\\mathrm{^qC}$ 下与环氧树脂反应,使之固化。  \n\n近年来，希望将粉末涂料涂覆到不能经受高温的新基材如木材或塑料上。普通的固化剂和催化剂不适用于这一用途，因为它们在太高的温度下才能固化。需要有各种可固化的环氧化物配方，它们在常温下基本上不与环氧树脂固化，而在不损坏对温度敏感的基材的温度下，它熔融、流动、压固并与环氧树脂形成良好固化的热固性塑料。  \n\n此外，希望在低于普通的固化温度下固化溶剂基环氧化物配方，以便保护基材和节省将配方加热到很高温度所需的时间和费用。需要这样的固化催化剂和可固化的环氧化物配方，它们在常温下是稳定的，而在低于普通的环氧树脂固化温度下可迅速固化，形成良好固化的热固性树脂。  \n\n本发明的一个目的是一种用以下步骤制备可固化配方的方法：(1)咪唑与含有至少一个活化双键的不饱和化合物反应，制成亲核的加成加合物；以及(2)制成含亲核的加成加合物和环氧树脂的配方；该法的特征在于，在步骤(2)以前，在亲核的加成加合物中有小于 $50\\%$ (当量)的咪唑片断用酸中和。  \n\n本发明的第二个目的是提供一种含有以下成分的可固化配方：(1)咪唑与含有至少一个活化双键的不饱和化合物的亲核加成加合物，该加合物的每一分子含有一个以上的咪唑片断；以及(2)环氧树脂，其比例为每当量环氧树脂有0.02－10当量亲核的加成加合物，该配方的特征在于，在加合物中有小于 $50\\%$ (当量)的咪唑片断被酸中和。  \n\n本发明的第三个目的是，如前所述，提供一种通过将配方加热到配方固化的温度来使配方固化的方法，该方法的特征在于，固化温度低于 $130\\mathrm{^{\\circ}C}$ 。本发明的第四个目的是提供这样一种可固化的配方，它含有：  \n\n(1)咪唑和不饱和化合物的亲核加成加合物；以及(2)环氧树脂，  \n该配方的特征在于：  \n(a)含有催化数量的亲核加成加合物，以及  \n(b)该配方还含有用于环氧树脂的固化剂。  \n\n本发明的另一些方面包括亲核的加成加合物作为催化剂的应用，可固化组合物在制备涂料中的应用，层压制品或其他复合制品或模塑制品，以及如此制得的制品。  \n\n该加合物催化环氧基一环氧基固化反应和支化反应。本发明的配方可在约 $130\\mathrm{^q}$ 或更高的温度下固化，制得比使用普通固化催化剂得到的类似涂层有更少膜泡的固化涂层。此外，如用本发明第二个目的所述的配方制成在低于 $130^{\\circ}\\mathrm{C}$ 的温度下固化的稳定的粉末涂料配方，制得用于对温度敏感的应用场合的低温粉末涂料。  \n\n本发明使用一种亲核的加成加合物，它通过咪唑与含有至少一个通过相邻电子抽出基团活化的双健的不饱和化合物反应来制备。对这一应用来说，“亲核加成”按」.March，高等有机化学，第四版，第741－743页(1992)中所述的含义使用。  \n\n不饱和化合物的每一分子含有一个或多个活化的双键片断(Q)。活化的双键片断(Q)优选键联到共同的中心片断(A)。不饱和化合物优选用式I表示：  \n\nA (Q)n  \n\n式中，(A)为如下所述的中心片断，每一 $\\alpha$ 为一活化的双键片断;n为键联到中 $\\therefore S$ 片断的不饱和片断的数目。活化的双键片断(Q)含有一个与活化电子－抽出基团相邻的脂族碳碳双键。适合的电子抽出基团的例子包括醛、酮、酯、酰胺、腈、硝酸盐和碘酸盐片断。优选的活化的双键片断 $(\\mathsf{Q})$ 的例子示于式II：  \n\n$$\n\\begin{array}{c}{0}\\\\ {\\Big\\Vert}\\\\ {-\\mathsf{O}-\\mathsf{C}-\\mathsf{C}\\mathsf{R}^{1}=\\mathsf{C}\\mathsf{R}^{1}{}_{2}}\\end{array}\n$$  \n\n$$\n\\begin{array}{c}{{\\displaystyle\\begin{array}{c}{{0}}\\\\ {{\\left\\|}}\\\\ {{-\\aleph{\\mathbb{R}}-{\\mathbb{C}}-{\\mathbb{C}}{\\mathbb{R}}^{1}={\\mathbb{C}}{\\mathbb{R}}^{1}{}_{2}}}\\end{array}\\right.}}\\end{array}\n$$  \n\n$$\n\\stackrel{\\circ}{\\big\\|}_{-\\mathbf{\\tilde{C}}-\\mathbf{\\tilde{C}}\\mathbf{R}^{1}=\\mathbf{C}\\mathbf{\\tilde{R}}^{1}2}\n$$  \n\n式中，每一 $\\mathbf{R}^{1}$ 独立优选为氢、脂族片断、芳族片断或使活化双键片断连接到相邻单体的键。每一 ${\\bf R}^{1}$ 更优选为氢或烷基，最优选为氢或甲基。这样来选择 ${\\bf R}^{1}$ ，以致使空间阻碍不防碍亲核加成反应。每一 $\\mathbf{R}^{1}$ 优选含有不大于12个碳原子、更优选不大于6个碳原子、最优选不大于4个碳原子。  \n\n每一活化的双键片断(Q)优选含有一个酯基片断，如式II(a)中所示。更优选丙烯酸酯或甲基丙烯酸酯片断。  \n\n中心片断(A)可为单一的单元或为含有多个重复单元的低聚物或聚合物。中心片断如何选择并不重要，只要它不干扰加合物的合成或使用就行。例如，中心片断优选含有以下任何一个或多个片断：烷基片断、芳基环、醚链、酯链、脂族或酚类羟基、缩水甘油醚和/或酯片断、酸片断或卤素原子。优选不含与环氧树脂固化或催化剂环氧树脂固化的片断，如胺片断、羧酸、酰卤或酸酐、硫醇基或羟基。这样来选择中心片断的数均分子重量，以致得到的加合物有所需要的软化温度。例如，数均分子重量优选不大于约5000、更优选不大于约3000。但优选至少约200。  \n\n不饱和化合物每一分子优选平均含有至少约0.5个活化的双键片断、更优选至少约100个活化双键片断、最优选至少约1.5个活化双键片断。每一分子的活化双键片断的最大数目并不重要，但在大多数情况下，优选不大于约10、更优选不大于约6、最优选不大于约  \n\n4。优选的不饱和化合物的例子包括聚丙烯酸酯和聚甲基丙烯酸酯、不饱和聚酯和乙烯基酯树脂。其他例子包括丙烯酸的烷基酯、芳基酯和烷芳基脂。  \n\n不饱和化合物优选为乙烯基酯树脂。乙烯基酯树脂优选为深度的或非深度的的环氧树脂与不饱和酸的反应产物。环氧树脂优选为聚(缩水甘油醚)更优选为深度的或非深度的的双酚的二缩水甘油醚。不饱和酸优选为丙烯酸或甲基丙烯酸。反应优选在催化剂如2,4,6－三(二甲基氨基乙基)酚存在下进行。适合的树脂的例子以及制备方法在U.S4,407,991(1983年10月4日，Messick)和EPO出版0436921A1(1991年7月17日，Wykowski)中公开。乙烯基酯树脂可任选含有未反应的环氧基片断。乙烯基酯片断与环氧基片断的当量比优选大于1:1、更优选至少3:1、更优选至少10:1、最优选至少 $20{:}1$ 0  \n\n不饱和化合物与咪唑反应生成亲核的加成加合物。咪唑如何选择并不重要，只要：  \n\n(1)所选的咪唑可与不饱和化合物通过亲核加成反应生成加合物；以及  \n\n(2)该加合物可通过环氧基－环氧基固化或通过与固化剂反应来催化环氧树脂的固化反应。咪唑优选用式III表示：  \n\n![](images/78c38812180a137d050cbe20a669206c56ff6bfedcede5d8aea1ac3579571302.jpg)  \n\n式中，每一 $\\scriptstyle\\mathrm{R}^{2}$ 独立为氢原子、脂族片断或芳族片断,每一 $\\mathrm{R}^{3}$ 为氢或脂族胺基如3－氨基丙基。每一 $\\scriptstyle\\mathbf{R}^{2}$ 优选为氢或烷基。每一 $\\scriptstyle\\mathbf{R}^{2}$ 和 $\\scriptstyle\\mathrm{\\mathrm{~R}}^{3}$ 优选含有不大于约12个碳原子、更优选不大于约6个碳原子、最优选不大于约4个碳原子。在相邻碳原子上的两个 $\\scriptstyle\\mathbf{R}^{2}$ 片断可任选键联形成环状结构。每一 ${\\mathbb R}^{3}$ 最优选为氢。适合的咪唑的例子包括咪唑、2－甲基咪唑、2-苯基咪唑、2－乙基－4－甲基咪唑和 $\\mathsf{N}-(3-$ 氨基丙基)咪唑。  \n\n优选这样来选择咪唑与不饱和化合物的比例，以使加合物中未反应的游离咪唑浓度最 $11.$ 。反应混合物可含有化学计量过量的咪唑，但优选每当量活化的双键含有不大于约1摩尔咪唑化合物、最优选不大于约0.95摩尔。在反应混合物中咪唑的最小浓度受实际考虑因素的影响，如在最终的加合物中所需的咪唑浓度。反应混合物每当量活化双键片断优选含有至少约0.5摩尔咪唑化合物、更优选至少约0.75摩尔。  \n\n反应温度优选至少约 $50\\mathrm{^qC}$ 、更优选至少约 $100\\mathrm{^{\\circ}C}$ 、最优选至少约 $120^{\\circ}\\mathrm{C}$ 。但优选不大于约 $160^{\\circ}\\mathrm{C}$ 、更优选不大于约 $150^{\\circ}\\mathrm{C}$ 0  \n\n反应优选在聚合抑制剂如氢或氢单甲基醚存在下进行，以便防止通过胶凝生成不饱和树脂，即使如此，某些溶液对形成凝胶仍是特别敏感的，以致必需特别小心。有空间位阻的咪唑如2一乙基－4－甲基咪唑可能反应缓慢，因此需要外加稳定剂如氢，以便为反应提供足够的时间。  \n\n生成的加合物含有 $\\beta-$ 咪唑片断，它优选用式 $\\mathrm{IV}(\\mathsf{a})$ 表示、更优选用式 $\\mathrm{IV(b)}$ 表示：  \n\n![](images/1fd02d54be1a51af400fb2bdfc0f9e3330967ca8a152715c69a53c54bcb69c64.jpg)  \n\n式中，每一乙为 $\\bigstar\\bigcirc$ 上规定的电子抽出基，每一 $\\mathbf{R}^{1}$ 和 ${\\mathrm{R}}^{2}$ 有前面给出的定义和优选实施方案，每一咪唑如上所述优选键联到中心片断上。在加合物中 $\\upbeta^{-}$ 咪唑片断的优选数目取决于加合物打算的用途，并如上所述类似于不饱和酯化合物中活化的双键片断的优选数目。  \n\n加合物优选用式［表示，其中至少一些 $\\mathbf{Q}$ 为 $\\beta-$ 咪唑片断，其余的 $\\mathbf{Q}$ 为活化的双键片断。 $\\beta-$ 咪唑片断与活化的双键片断的当量比优选至少 $1{:}1$ 、更优选至少2：1、最优选至少 $3{:}1$ 。所有的活化的双键片断可转变成 $\\beta^{-}$ 咪唑片断，但是，为了使加合物中的游离咪唑最少，当量比不超过 $20{:}1$ 通常是更实际的。加合物可任选还含有咪唑与环氧基片断或不饱和化合物中的其他反应性基团的反应产物。  \n\n加合物的软化点优选高到足以使它在普通的贮存温度下是固 体、但又低到足以使它在所需的反应温度下软化与粉末环氧树脂压 固的程度。如在实施例中所述的试验测量的加合物的Mettler软化 点优选至少约 $50\\mathrm{^c}$ 、更优选至少约 $60\\mathrm{^c}$ 、最优选至少约 $80\\mathrm{^c}$ 。但优 选小于 $130\\mathrm{^qC}$ 、更优选小于 $100\\mathrm{^{\\circ}C}$ 0  \n\n加合物的数均分子量优选至少约400、更优选到少500。但优选 不大于约1500、更优选不大于约1100。加合物的重均分子量优选至 少约400、更优选至少约500。但优选不大于约2500、更优选不大于 约1200。  \n\n加合物的熔体粘度（在 $150\\mathrm{\\textperthousand}$ 下用有C型锥的ICI锥板式粘度 计测量的)优选至少约90毫帕·秒、更优选至少约140毫帕·秒。但 优选不大于约200毫帕·秒、更优选不大于约1500毫帕·秒。  \n\n加合物最好基本上不含( $0\\%$ (重量))未与不饱和化合物反应的未键联的咪唑，但是其结果常常实际上达不到。优选不大于约 $50\\%$ (重量)咪唑是未键联的咪唑、更优选不大于约 $30\\%$ （重量）最优选不大于约 $20\\%$ （重量)。未键联的咪唑的最小百分数受到实际考虑因素的限制， $\\frac{1}{x^{n}}$ 空间位阻的限制，它通常至少为 $1\\%$ （重量）。  \n\n在先有技术中，咪唑片断在成为环氧化物配方一部分以前通常先用有机酸中和。在本发明中，至少大部分咪唑片断未被质子化（中和)。优选的是，至少约 $50\\%$ (摩尔)咪唑片断未质子化、更优选至少约 $75\\%$ (摩尔)未质子化、更优选至少约 $90\\%$ (摩尔)未质子化、最优选至少约 $95\\%$ (摩尔)未质子化。可能多达 $100\\%$ 未质子化。未质子化的咪唑片断优选以其游离碱的状态存在。  \n\n本发明的配方还含有环氧树脂。环氧树脂优选为缩水甘油醚或酯化合物、更优选缩水甘油醚化合物、最优选深度的或非深度的双酚如双酚A或双酚F的二缩水甘油醚。环氧树脂可为深度的或非深度的，但优选为深度的，更优选在约 $25\\%$ 下为固体。  \n\n其环氧当量(EEW)优选至少约100、更优选至少约200、最优选 至少约500。但其最大EEW并不重要，但优选不大于约2500、更优 选不大于约2000、最优选不大于约1500。其Mettler软化点优选至 少约 $50\\mathrm{^c}$ 、更优选至少约 $60\\mathrm{\\PhiC}$ 、最优选至少约 $65\\mathrm{{C}}$ 。但其 Mettler 软化点优选小于 $130\\mathrm{{\\Phi}}$ 、更优选小于约 $100\\mathrm{^{\\circ}C}$ 0  \n\n适合的环氧树脂的例子包括环氧基粉末涂料树脂、环氧/可溶酚醛树脂、高分子量和中分子量溶液环氧树脂、MDI改性的环氧树脂、(甲基)丙烯酸缩水甘油酯聚合物或共聚物和液体环氧树脂及其共混物。适用于本发明的环氧树脂的具体例子包括双酚A、双酚F和四溴双酚A。各种适合的环氧树脂都可商购。制备方法是本专业的技术人员熟悉的，并在许多常规文献中描述，如Lee&Neville,环氧树脂手册，第2－1至3－24 页（McGraw－Hill BookCo.1967）。环氧树脂也可是US5,112,932公开的液体环氧树脂和四溴双酚A或含环氧官能的唑烷酮共聚物的深度产物。  \n\n加合物与环氧树脂的最佳比例通常取决于配方的物料和用途。  \n\n当加合物在没有单独的固化剂或交联剂的条件下催化固化时，其当量比优选为每当量环氧树脂用至少约0.02当量加合物、更优选至少约0.05当量、最优选至少约0.2当量加合物。最大浓度并不重要，但优选每当量环氧树脂不大于约10当量加合物、更优选不大于约5当量、更优选不大于约2当量、最优选不大于约1当量加合物。环氧树脂与加合物的重量比优选为至少1:10、更优选至少1:1、最优选至少2：1。但环氧树脂与加合物的重量比优选不大于 $10:1$ 、更优选不大于 $5{:}1$ 、最优选不大于 $3{:}1$ Q  \n\n当配方含有固化剂并在升温下固化时，那么数量少得多的加合物是优选的。当量比为每当量环氧树脂优选用至少约5毫克当量(meq)加合物、更优选至少约30毫克当量、最优选至少约80毫克当量加合物。最大浓度并不重要，但每当量环氧树脂优选不大于约200毫克当量加合物、更优选不大于约150毫克当量、更优选不大于约100毫克当量、最优选不大于约50毫克当量加合物。环氧树脂与加合物重量比优选为至少约1份/100份树脂(phr）、更优选至少约3phr、最优选至少约5phr。但环氧树脂与加合物的重量比优选不大于约15phr、更优选不大于约10phr、最优选不大于约5phr。  \n\n适合用于这样配方的固化剂随配方的用途变化，它是本专业的技术人员熟悉的。几种适合的固化剂在Lee&Neville的上述文章第 20－11页以及Tess的上述文章第776－778页中描述。适合的固化剂的例子包括二氰胺和其他胺和酰胺、多元酚以及聚酐， $\\frac{1}{x^{0}}$ 苯乙烯顺酐共聚物。固化剂与环氧树脂的最佳比随所选的固化剂和树脂的用途变化。通常，固化剂与环氧树脂的当量比优选为0.1：1至10:1、更优选0.2:1至 $2{:}1$ o  \n\n含有足以催化环氧树脂固化的加合物的配方还含有一种固化 剂。加合物与固化剂的当量比优选至少 $25:75$ 更优选至少 $50:50.$ 更优选至少 $75:25$ 最优选至少 $90:10.$ 0  \n\n配方可任选含有溶剂，但优选它不含有溶剂，更优选它为粉末涂料配方。溶剂若有的话，优选为有机溶剂。适合的有机溶剂是大家熟悉的，并可商购。选择什么并不重要。适合的溶剂的例子包括：二甲苯、乙二醇醚、酮、甲苯、醇和二甲基甲酰胺。在溶剂中固体的浓度并不重要，但它受实际的考虑因素的影响,如粘度、价格以及是否需要从流出物中回收溶剂等。在大多数情况下，固化浓度优选为20至$80\\%$ (重量)更优选 $40-60\\%$ （重量）。  \n\n配方可任选含有其他适用于它的用途的添加剂。例 $\\frac{1}{x^{n}}$ ，涂料配方可任选含有稳定剂、表面活性剂、流动改进剂、填充剂、颜料和消光剂。制备层压制品和复合材料的配方可任选含有稳定剂、填充剂、流动改进剂和碎纤维。除颜料、填充剂和碎纤维外，添加剂在配方中的浓度优选不大于约 $5\\%$ (重量)更优选不大于约 $3\\%$ (重量)。碎纤维、填充剂和颜料的浓度优选不大于约 $80\\%$ （重量）更优选不大于约 $50\\%$ (重量)。任一种或所有添加剂的浓度都可为 $0\\%$ （重量）。  \n\n通过环氧基一环氧基均聚进行固化的配方优选在至少约 $80\\mathrm{^c}$ 下固化、更优选至少约 $90\\mathrm{{C}}$ 、最优选至少约 $100\\mathrm{\\textperthousand}$ 下固化。但优选在 小于 $130\\mathrm{^q}$ 下固化、更优选小于 $120\\mathrm{\\Phi}$ 、最优选不大于约 $110^{\\circ}\\mathrm{C}$ 下固 化。但是也可在 $200^{\\circ}\\mathrm{C}$ 或最高温度下固化。  \n\n含有较少量加合物和单独固化剂的配方优选在至少约 $120^{\\circ}\\mathrm{C}$ 下 固化、更优选至少约 $130^{\\circ}\\mathrm{C}$ 、最优选至少约 $150\\mathrm{^qC}$ 下固化。最高的固 化温度随用途变化;但在大多数情况下，它不大于约 $250\\mathrm{\\textperthousand}$ 、更优选 不大于约 $220\\mathrm{^qC}$ 0  \n\n本发明的配方可用于普通的环氧树脂用途， $\\frac{1}{x^{0}}$ 涂料、层压和模型应用。例如：  \n\n(a)溶液涂料配方可用以下步骤涂覆：  \n\n(1)用已知的方法涂覆到基材上，如喷涂、刷涂、辊涂、浸涂或静电沉积；以及  \n\n(2)通过加热到适合的固化温度进行固化。  \n\n(b)粉末涂料配方可用以下步骤涂覆：  \n\n(1)将基材加热到适合配方的固化温度；以及  \n\n(2)用已知的方法，如静电喷涂或流化床法将配方涂覆在基材上。  \n\n它们也可用以下步骤涂覆：  \n\n(1)将粉末涂覆到冷基材上，如用静电涂覆方法;以及(2)将粉末和基材加热到粉末流动和固化的温度。  \n\n(c)层压制品可用以下步骤制作：  \n\n(1)将配方浸渍在纤维基材上并加热制成预浸料坯；以及  \n\n(2)在适合于使配方固化的温度下将两层或两层以上的预浸料坏压制在一起。  \n\n(d)模制制品用以下步骤制备：  \n\n(1)将配方注入模子，配方任选含有纤维基材；以及(2)将配方加热使它固化。  \n\n汽车另件的组件如片簧优选用本发明的配方来制作。  \n\n本发明的催化剂也可通过如US5，112，932中公开的粉末涂料或溶剂体系用于电器层压板应用。  \n\n本发明通过以下的操作实施例作进一步地说明。  \n\n操作实施例  \n\n以下实施例只用于说明目的，而不打算作为对说明书或权利要求书的限制。  \n\n加合物的制备。制备本发明加合物的具体试剂以及加合物的性质列入下表I。加合物用以下一般的步骤来制备：  \n\n(1)优选的是，制备深度的环氧树脂。将D.E.R\\*330(Dow化学公司的商标)液体环氧树脂样在铸改性催化剂存在下、在约 $140\\%$ 下、在氮气气氛中与双酚A反应。每种试剂的数量以及生成的深度的树脂的EEW列入表I。（整个表中，各试剂的数量按份量(pbw)表示，除非另加说明。)  \n\n(2)制备乙烯基酯树脂。将由步骤(1)得到的深度的树脂或D.E.R, $^{\\star}330$ 液体环氧树脂的样品加热到 $80-100\\mathrm{^c}$ ，并使恒定的空气流通过树脂鼓泡。大约 $500\\mathrm{{ppm}}$ 氢作为抑制剂加入，并加入丙烯酸或甲基丙烯酸。加入750ppmANCAMINEK54 催化剂，并将温度升至约 $120\\mathrm{^{\\circ}C}$ 。当残留的环氧树脂浓度为约 $7-8\\%$ 时，加入第二片断 750ppmANCAMINE K54 催化剂。当残留环氧树脂的浓度达到表I所示的浓度时，中止反应并降低温度。减少空气流，并用氮气扫吹乙烯基酯树脂。各种试剂和乙烯基酯树脂的残留环氧树脂含量列入表 ${\\mathrm{~I}}_{\\circ}$  \n\n(2)制备乙烯基酯树脂的咪唑加合物。将列入表I的咪唑按几份在约15分钟内加入，以缓和产生的放热。此后，将温度在15分钟内缓慢升至 $140^{\\circ}\\mathrm{C}$ ，并使混合物在 $140^{\\circ}\\mathrm{C}$ 下反应60分钟。回收产物，并冷却。用HPLC测量加合物中残留的咪唑。  \n\n(4)用以下的方法测量Mettler软化点，该法作为Dow化学公司的 RPM－108C法已经公开，它是ASTMD3104法的变通方法。RPM一108C法中的软化点定义为这样一种温度，在该温度下，吊挂在底部有6.35毫米孔的圆柱形杯中的环氧树脂当在空气中以线性速率加热时，它向下流动19毫米距离。  \n\n将样品研磨到粒度小于5毫米。将底部有6.35毫米孔的样品杯放在 $150\\mathrm{^c}$ (对于低分子量样品)或 $200\\%$ (对于高分子量样品)加热板上的铝箔上。将颗粒样加到杯中，一直到它为完全熔融无泡的树脂。从板上取下杯和铝箔，并冷却;然后撕去铝箔，并除去杯外过量的树脂。  \n\n将杯放中Mettler仪器公司的FP5/53型软化点仪中。该仪器有一加热炉和当样品流出杯子时会被遮断的光束。炉温设定到比预计的样品熔点低 $20\\mathrm{{C}}$ ，并让样品在至少30秒达到平衡。然后以$2^{\\circ}\\mathrm{C},$ /分的速率升温，一直到在孔下形成的液滴遮断光束。  \n\n(5)用有C型锥的ICI锥板式粘度计在 $150\\mathrm{^c}$ 下测量熔体粘度。用气相色谱法测定平均分子量。各种试剂和加合物的性质全部列入表 ${\\tt I}_{\\tt o}$  \n\n对于表I来说，“Im”表示咪唑，“2-MI\"表示2－甲基咪唑， $^{*}2-$ PhI\"表示2－苯基咪唑和“2E4MI\"表示2－乙基－4－甲基咪唑。  \n\n<html><body><table><tr><td colspan=\"8\">表I</td></tr><tr><td></td><td>加合物</td><td>1</td><td>2</td><td>3 4</td><td></td><td>5</td><td>6</td></tr><tr><td>液体环氧树脂（pbw）</td><td></td><td>559</td><td>539</td><td>48.94</td><td>55.10</td><td>46.5</td><td>48.46</td></tr><tr><td>双酚A（pbw）</td><td></td><td>57.8</td><td></td><td>-</td><td>1</td><td>-</td><td>5.2</td></tr><tr><td>环氧当量重量</td><td></td><td>180</td><td>240</td><td>180</td><td>180</td><td>180</td><td>240</td></tr><tr><td>甲基丙烯酸（pbw）</td><td></td><td></td><td>209.7</td><td>22.82</td><td>21.17</td><td></td><td></td></tr><tr><td>丙烯酸（pbw）</td><td>210</td><td></td><td></td><td>一</td><td></td><td>18.27</td><td>15.78</td></tr><tr><td>残留环氧基（%）</td><td>0.6</td><td>1.0</td><td></td><td>1.0</td><td>3.6</td><td><1</td><td>1.5</td></tr><tr><td>咪唑选择</td><td>2-MI</td><td>2-MI</td><td>2E4MI</td><td>2-MI</td><td></td><td>2-PhI</td><td>2-PhI</td></tr><tr><td>咪唑量（pbw）</td><td>231</td><td>193.4</td><td>28.23</td><td></td><td>23.73</td><td>35.27</td><td>30.56</td></tr><tr><td>残留咪唑（%）</td><td>1.2</td><td>5.7</td><td>16.3</td><td>5.9</td><td>6.1</td><td></td><td>6.2</td></tr><tr><td>软化温度（℃）</td><td>78</td><td>71.9</td><td>65.8</td><td>76.9</td><td></td><td>82.1</td><td>89.4</td></tr><tr><td>熔体粘度（毫帕秒，150℃）</td><td>370</td><td>190</td><td>110</td><td>360</td><td>270</td><td></td><td>600</td></tr><tr><td>Mn</td><td></td><td>726</td><td>704</td><td>658</td><td></td><td>612</td><td>516</td></tr><tr><td>Mw</td><td></td><td>908</td><td>777</td><td>742</td><td></td><td>878</td><td>1070</td></tr><tr><td>Mz</td><td></td><td>1177</td><td>878</td><td></td><td>846</td><td>1101</td><td>1857</td></tr><tr><td>多分散性</td><td>1</td><td>1.25</td><td>1.10</td><td></td><td>1.13</td><td>1.43</td><td>2.07</td></tr></table></body></html>  \n\n（）  \n  \n\n\n<html><body><table><tr><td>加合物</td><td>7</td><td>8</td><td>9</td><td>10</td><td>11</td><td>12</td></tr><tr><td></td><td>54.97</td><td>52.77</td><td>55.21</td><td>55.00</td><td>56.89</td><td>539.1</td></tr><tr><td>液体环氧树脂（pbw） 双酚A（pbw）</td><td></td><td></td><td>11.25</td><td></td><td>11.59</td><td></td></tr><tr><td>环氧当量重量</td><td>180</td><td>180</td><td>320</td><td>180</td><td>320</td><td>180</td></tr><tr><td>甲基丙烯酸（pbw）</td><td>25.63</td><td>24.61</td><td>17.59</td><td>一</td><td></td><td>235.8</td></tr><tr><td>丙烯酸（pbw）</td><td>－</td><td>-</td><td></td><td>21.57</td><td>15.10</td><td>-</td></tr><tr><td>残留环氧基（%）</td><td>1.0</td><td>1.0</td><td>1.17</td><td>0.95</td><td>0.85</td><td>1.46</td></tr><tr><td>咪唑选择</td><td>Im</td><td>2-MI</td><td>2-MI</td><td>2-MI</td><td>2-MI</td><td>2-MI</td></tr><tr><td>咪唑量（pbw）</td><td>19.4</td><td>22.62</td><td>15.95</td><td>23.43</td><td>16.42</td><td>225.1</td></tr><tr><td>残留咪唑（%）</td><td>4.6</td><td>4.7</td><td>6.1</td><td>1.2</td><td>0.6</td><td>4.1</td></tr><tr><td>软化温度（℃）</td><td>62.8</td><td>69.3</td><td>84.2</td><td>77.9</td><td>92.6</td><td>72</td></tr><tr><td>熔体粘度（毫帕秒， 150 ℃ )</td><td>160</td><td>140</td><td>680</td><td>370</td><td>1520</td><td>1400*</td></tr><tr><td>Mn</td><td>576</td><td>529</td><td>1060</td><td>790</td><td>1139</td><td>1</td></tr><tr><td>Mw</td><td>639</td><td>579</td><td>1716</td><td>972</td><td>1920</td><td></td></tr><tr><td>Mz</td><td>699</td><td>625</td><td>2675</td><td>1284</td><td>3088</td><td></td></tr><tr><td>多分散性</td><td>1.11</td><td>1.09</td><td>1.62</td><td>1.23</td><td>1.69</td><td></td></tr></table></body></html>  \n\n实施例1－－层压  \n\n将加合物12溶于甲乙酮中，得到 $55\\%$ 固含量的溶液。将10克加合物溶液和125克 $\\mathrm{D}.\\mathrm{E}.\\mathrm{R}^{\\star}691\\ \\mathrm{A}80$ 环氧树脂溶液的混合物浸渍在15厘米 $\\times15$ 厘米正方形纺织E玻璃型7628(纺织E玻璃型7628由Inter玻璃公司商购)片上。将经浸渍的片在热空气循环炉中，在$80\\mathrm{^{\\circ}C}$ 下加热4分钟，使溶剂蒸发。制得的预浸料坏含有 $60-65\\%$ 树脂。  \n\n将5片预浸料坏放在两片铜箔之间，并在 $110\\mathrm{{C}}\\cdot0.2$ 巴（24兆帕)下压制20分钟。生成的层压制品的玻璃化转变温度为 $69\\mathrm{{C}}$ 0  \n\n用12克加合物溶液重复实验。生成的层压制品的玻璃化转变温度为 $99\\mathrm{{C}}$ 0  \n\n两层压制品都有良好的外观。  \n\n实施例2－16—粉末涂料  \n\n用以下步骤制备环氧树脂A：首先将6830克 $\\mathrm{D}.\\mathrm{E}.\\mathrm{R}^{\\star}330$ 液体环氧树脂和3170ER级双酚A与500ppm改性催化剂在 $100\\mathrm{^{\\circ}C}$ 、氮气下搅拌；随后将混合物加热到 $140^{\\circ}\\mathrm{C}$ ；随后在 $140^{\\circ}\\mathrm{C}$ 下反应约2小时，一直到树脂在 $120^{\\circ}\\mathrm{C}$ 下的粘度为约5000毫帕·秒；通过加入对甲苯磺酸甲酯使催化剂失活;搅拌30分钟，然后冷却和固化。树脂的目标EEW为约1000。  \n\n用相同的步骤制备环氧树脂B，不同的是在对甲苯磺酸甲酯后立即将 $6.6\\%$ （重量）D.E.N.\\*438(Dow化学公司的商标)环氧/可溶酚醛树脂加到反应混合物中。  \n\n将两个70克D.E.H.\\*85(Dow化学公司的商标)酚醛树脂硬化剂样在 $140^{\\circ}\\mathrm{C}$ 、氮气下熔融。将30克加合物1混入第一样品（硬化剂A)中和30克加合物2混入第二样品(硬化剂B)中。将混合物搅拌15分钟，然后冷却到常温。  \n\n将表II所列的环氧树脂、硬化剂和添加剂按表II所列的比例在实验室混合器中，在420转/分下混合2分钟。将混合物在 $65\\mathrm{^\\circC}$ 和300转/分下在双螺杆挤塑机中熔体挤塑。将挤出物冷却、切碎、研磨和过筛，得到粉末。用静电喷涂将粉末涂覆到钢板上，并将钢板在炉中，在 $110\\mathbb{C}\\setminus120\\mathbb{C}$ 和 $130\\mathrm{^q}$ 下固化20分钟。测试涂层：  \n\n流动－－用肉眼观测，并与高温粉末涂布的样品比较。作为结果，0$\\mathbf{\\Sigma}=\\mathbf{\\Sigma}$ 差， $4=$ 极好。  \n\n柔软性－－间 Erichsen压痕试验。  \n\n抗冲击性－－用ASTMD2794－84试验法，用4磅(1.8公斤)重物施加在直径1/2英寸(1.25厘米)横切面。试验测量施加力而又不破坏的英寸一磅(牛一米)力的数字。  \n\n在20度反射角下的光泽－－用DIN55990试验。  \n\n用在 $35\\mathrm{{C}}$ 下老化6天的粉末重复所有的试验。所有的结果都列入表II。  \n\n<html><body><table><tr><td>实施例</td><td>2</td><td>3</td><td>4</td><td>5</td><td>6</td><td>7</td><td>8</td><td>9</td><td>10</td></tr><tr><td>环氧树脂A（pbw）</td><td>532.8</td><td>532.8</td><td>532.8</td><td>532.8</td><td>532.8</td><td>532.8</td><td>1</td><td></td><td>1</td></tr><tr><td>环氧树脂B（pbw）</td><td>一</td><td>一</td><td>一</td><td></td><td>一</td><td></td><td>461.3</td><td>461.3</td><td>461.3</td></tr><tr><td>硬化剂A（pbw）</td><td>59.2</td><td>59.2</td><td>59.2</td><td>59.2</td><td>59.2</td><td>59.2</td><td></td><td>一</td><td>一</td></tr><tr><td>硬化剂B（pbw）</td><td>一</td><td>一</td><td>一</td><td>一</td><td></td><td>一</td><td>80</td><td>80</td><td>80</td></tr><tr><td>MODAFLOW MFIII (pbw)</td><td>8.0</td><td>8.0</td><td>8.0</td><td>8.0</td><td>8.0</td><td>8.0</td><td>8.1</td><td>8.1</td><td>8.1</td></tr><tr><td>二氧化钛（pbw）</td><td>400</td><td>400</td><td>400</td><td>400</td><td>400</td><td>400</td><td>405.4</td><td>405.4</td><td>405.4</td></tr><tr><td>老化（天）</td><td>0</td><td>0</td><td>0</td><td>6</td><td>6</td><td>6</td><td>0</td><td>0</td><td>0</td></tr><tr><td>涂覆温度（℃）</td><td>110</td><td>120</td><td>130</td><td>110</td><td>120</td><td>130</td><td>110</td><td>120</td><td>130</td></tr><tr><td>流动</td><td>2</td><td>2.5</td><td>3</td><td>1.5</td><td>2.5</td><td>3</td><td>3</td><td>3.5</td><td>4</td></tr><tr><td>Erichsen压痕（毫米）</td><td>一</td><td>8.3</td><td>8.9</td><td>一</td><td>8.0</td><td>8.3</td><td>一</td><td>8</td><td>7</td></tr><tr><td>抗冲击性时－磅（牛顿－米）</td><td></td><td>160 (18.1)</td><td>160 (18.1)</td><td></td><td>160 (18.1)</td><td>160 (18.1)</td><td>一</td><td>140 (15.8)</td><td>160 (18.1)</td></tr><tr><td>光泽{%)</td><td></td><td>101</td><td>100</td><td></td><td>96</td><td>98</td><td></td><td>92</td><td>93</td></tr></table></body></html>\n\nⅡ表  \n\n（）  \n\n\n<html><body><table><tr><td>6 1</td><td>一</td><td>ε t9 6 4</td><td>1</td><td>0 8</td><td></td><td>1 ： 8</td><td>40</td><td>4 1</td><td>0 3 1</td><td></td><td>3</td><td>4 7</td><td>61 1(</td><td>3 9</td></tr><tr><td>5 1</td><td></td><td>m'tS 6 4</td><td></td><td>0 8</td><td></td><td>1 8</td><td>4</td><td>4 １</td><td>0 2 1</td><td>2</td><td>3 6</td><td></td><td>08 6 1 1(</td><td>30 9</td></tr><tr><td></td><td>_</td><td>'19 6 4</td><td></td><td>0 8</td><td></td><td>1 8</td><td>4</td><td>4 1</td><td>0 1 1</td><td></td><td>１</td><td>/</td><td></td><td>1</td></tr><tr><td>1 3</td><td></td><td>6 4</td><td></td><td></td><td>8</td><td>1 8</td><td>5 0 4</td><td>7</td><td>0 3 1</td><td></td><td>3-</td><td></td><td></td><td>3 9</td></tr><tr><td>2 1</td><td></td><td>m19 6 4</td><td></td><td></td><td>0 8</td><td>1 8</td><td>0</td><td>7</td><td>0 2</td><td></td><td>3</td><td></td><td>1</td><td>2 9</td></tr><tr><td>1</td><td>1</td><td>' T9 9</td><td></td><td></td><td>0 8</td><td>1 8</td><td></td><td>7</td><td>1 0 1 1</td><td></td><td>2</td><td>1</td><td></td><td>一</td></tr><tr><td>1</td><td></td><td></td><td></td><td></td><td></td><td>(mqd)</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>） 米</td></tr></table></body></html>  \n\n实施例17  \n\n用以下步骤制备二乙醇胺改性的酚醛树脂硬化剂：(1)将32.8份重(pbw)液体环氧树脂和62.7pbw双酚A在 $100\\mathrm{^{\\circ}C}$ 、氮气下混合；(2)将在 $50\\mathrm{{C}}$ 下熔融的4.5pbw二乙醇胺加入;(3)放热达到 $180\\mathrm{^c}$ 后，冷却到 $150\\mathrm{^c}$ 并保持30分钟。  \n\n将90pbw实施例1的加合物在 $140\\mathrm{^q}$ 、氮气下与10pbw羟基当量重为约104的可溶酚醛树脂混合15分钟。生成的硬化剂组合物的Mettler软化点为约 $83\\mathrm{\\textperthousand}$ ，在 $120^{\\circ}\\mathrm{C}$ 下的熔体粘度为3840毫帕·秒。  \n\n按权利要求2－16的步骤制备粉末涂料配方。该配方含有10，9pbw二醇胺改性的酚类硬化剂、3.5pbw含有加合物的硬化剂组合物、24.9pbwD.E.R.\\*672U环氧树脂、30.7pbwD.E.R.\\*642U环氧树脂、5pbw二氧化钛、22pbw $\\mathrm{BaSO_{4}}$ 、2pbw云母和1 pbwMODAFLOWMFIII流动改进剂。用静电喷涂器将配方涂覆到已预热到 $245\\mathrm{^\\circC}$ 的6毫米钢板上。将涂层在 $245\\mathrm{^qC}$ 下固化2.5分钟。也将粉末手工涂覆到已预热到 $235\\mathrm{{c}}$ 的玻璃板上，并固化约2分钟。用显微镜观测板子，基本上未看到膜泡。  \n\n实施例18  \n\n用实施例17的步骤，将加合物8在 $140^{\\circ}\\mathrm{C}$ 下与羟基当量重为约104的酚醛可溶可熔树脂熔体共混30分钟。加合物与可溶可熔酚醛树脂的重量比为 $90:10\\$ 。共混完全后，共混物的软化点为 $86.7\\mathrm{^{\\circ}C}$ 1在 $150\\mathrm{^{\\circ}C}$ 下熔体粘度为440毫帕·秒，在 $120\\mathrm{^{\\circ}C}$ 下熔体粘度为3360毫帕·秒。  \n\n粉末配方含有636.8重份（pbw）D.E.R.\\*661E环氧树脂、55.2重份共混物、300重份KRONOS2310(由Kronos公司商购)二氧化钛和8.0重份MODAFLOWMFIII（由Monsanto公司商购)流动改进剂，它用实施例2－16的步骤来制备。  \n\n象实施例2－16中公开的那样，将配方涂覆到钢板上，并在$120\\mathrm{^{\\circ}C}$ 和 $110\\mathrm{^{\\circ}C}$ 下固化20分钟。也涂覆并在 $100^{\\circ}\\mathrm{C}$ 下固化30、45、60和75分钟。象实施例2－16那样测试涂覆。结果列入表III。所有的板都进行200次丙酮揉搓，而未观测到破坏。  \n\n表Ⅲ  \n\n\n<html><body><table><tr><td>时间（分）</td><td>温度（℃）</td><td>厚度（微米）</td><td>2</td><td></td><td>Eriese</td><td></td></tr><tr><td>20</td><td>110</td><td>566</td><td>100</td><td>103</td><td>3.8</td><td>110 (11)</td></tr><tr><td>20</td><td>120</td><td>56</td><td>99</td><td>103</td><td>4.6</td><td>90 (10)</td></tr><tr><td>30</td><td>100</td><td>59</td><td>97</td><td>102</td><td>5.6</td><td>30 (3)</td></tr><tr><td>45</td><td>100</td><td>53</td><td>100</td><td>101</td><td>4.6</td><td>50 (6)</td></tr><tr><td>60</td><td>100</td><td>59</td><td>99</td><td>101</td><td>6.0</td><td>50 (6)</td></tr><tr><td>75</td><td>100</td><td>67</td><td>99</td><td>101</td><td>4.1</td><td>40 (5)</td></tr></table></body></html>",
+        "category": " Introduction"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# ChemDFM: A Large Language Foundation Model for Chemistry  \n\nZihan Zhao1 ∗ Da ${{\\bf{M}}{\\bf{a}}^{1}}^{*}$ Lu Chen1,2 † Liangtai Sun1 Zihao Li3 Yi Xia2 Bo Chen2 Hongshen ${\\bf X}{\\bf u}^{1}$ Zichen Zhu1 Su Zhu4 Shuai Fan4 Guodong Shen2 Kai $\\mathbf{Y}\\mathbf{u}^{1,2\\dag}$ Xin Chen2 †  \n\n$^1{\\cal X}$ -LANCE Lab, Department of Computer Science and Engineering MoE Key Lab of Artificial Intelligence, SJTU AI Institute Shanghai Jiao Tong University, Shanghai, China 2Suzhou Laboratory, Suzhou, China   \n3Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs School of Chemistry and Chemical Engineering Shanghai Jiao Tong University, Shanghai, China 4AI Speech Co, .Ltd., Suzhou, China {zhao_mengxin, chenlusz, kai.yu}@sjtu.edu.cn",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# Abstract  \n\nArtificial intelligence (AI) has played an increasingly important role in chemical research. However, most models currently used in chemistry are specialist models that require training and tuning for specific tasks. A more generic and efficient solution would be an AI model that could address many tasks and support free-form dialogue in the broad field of chemistry. In its utmost form, such a generalist AI chemist could be referred to as Chemical General Intelligence. Large language models (LLMs) have recently logged tremendous success in the general domain of natural language processing, showing emerging task generalization and freeform dialogue capabilities. However, domain knowledge of chemistry is largely missing when training general-domain LLMs. The lack of such knowledge greatly hinders the performance of generalist LLMs in the field of chemistry. To this end, we develop ChemDFM, a pioneering LLM for chemistry trained on 34B tokens from chemical literature and textbooks, and fine-tuned using 2.7M instructions. As a result, it can understand and reason with chemical knowledge in free-form dialogue. Quantitative evaluations show that ChemDFM significantly surpasses most representative open-source LLMs. It outperforms GPT-4 on a great portion of chemical tasks, despite the substantial size difference. We have open-sourced the inference codes, evaluation datasets, and model weights of ChemDFM on Huggingface3.",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# 1 Introduction  \n\nWith the rapid development of artificial intelligence (AI), utilizing AI to assist chemical research has garnered increasing attention [Wang et al., 2023b, Back et al., 2024]. Various AI models have been developed for tasks such as property prediction [Zhou et al., 2022, Wu et al., 2023b, Chen et al., 2023], molecular captioning and generation [Xu et al., 2021, Edwards et al., 2022, Perron et al., 2022,  \n\nDu et al., 2024, Lu et al., 2024], and reaction predictions [Schwaller et al., 2020, Wang et al., 2021, Han et al., 2024]. Since BERT [Devlin et al., 2019] and GPT [Radford et al.], efforts have been made to fine-tune pre-trained models for specific chemical tasks [Zhou et al., 2022, Edwards et al., 2022, Liu et al., 2023, Luo et al., 2023, Zhang et al., 2024]. However, these models are typically trained on a meticulously curated dataset to solve a designated task in a particular scenario, leading to a one-to-one relationship between models and tasks. Once out of that specific scenario, they are often not useful, even for highly related tasks. A more attractive and practical AI system should be capable of handling a wide range of chemical tasks under real-world scenarios and conducting free-form human-AI collaborations. Such an AI system necessitates a comprehensive array of chemical competencies, coupled with the ability to comprehend and reason in both chemical and natural languages. This would enable it to work as a research assistant or even collaborator alongside human researchers. This could be an essential step towards eventually achieving Chemical Artificial General Intelligence.  \n\nIn pursuit of a highly integrated AI system for a broad range of chemical challenges, recent advancements in large language models (LLMs) [Du et al., 2022, Touvron et al., 2023a, Xu et al., 2023] brought great new hopes. Numerous studies have demonstrated the remarkable competencies of LLMs in natural language understanding and task generalization [Wei et al., 2021, Xu et al., 2023], deductive reasoning [Wei et al., 2022, Kojima et al., 2022], and tool utilization [Schick et al., 2023, Qin et al., 2024]. These made LLMs shine in traditional natural language processing tasks and accomplish problems that were previously unimaginable and unsolvable, such as handling tasks in unknown scenarios or conducting free-form dialogues with humans. These inherent strengths underscore the viability of employing LLMs as AI-driven research collaborators in the field of chemistry.  \n\nDifferent from general domains, tasks in chemical domains necessitate models to possess additional chemical comprehension capabilities for understanding and reasoning over chemical-specialized language and knowledge. This hinders general domain LLMs from excelling in chemical tasks as they often lack in-depth chemical knowledge [Kristiadi et al., 2024]. For example, molecules are a vital component of the chemical world. Although molecules can be conveyed through naturallanguage-like notations such as SMILES (Simplified Molecular Input Line Entry System), IUPAC names, and molecular formulas, their meanings and intrinsic structures are entirely different from those in natural language. CO represents carbon monoxide in chemistry, not Colorado, while Co represents Cobalt, not a company, and (CO) as part of a SMILES typically represents the carbonyl group. The lack of understanding of these molecular notations severely limits the applicability and performance of general domain LLMs in solving chemistry problems. Therefore, we believe that equipping general-domain LLMs with rich chemical knowledge of task-specific chemical models, as illustrated in Figure 1, is vital for developing LLMs useful in the field of chemistry.  \n\nIn this work, we propose ChemDFM, a Dialogue Foundation Model for Chemistry. ChemDFM takes advantage of the pre-trained LLaMa-13B model [Touvron et al., 2023a], an open-source general-domain LLM, and is further specialized in chemistry through two phases: 1) Domain Pre-training, where the model harvests the chemical knowledge from research articles and textbooks, and 2) Instruction Tuning, where the model familiarizes itself with chemical language and patterns, especially molecule notations. Each phase uses an extensive and diverse collection of chemical data: 1) nearly 34B tokens from over 3.8M chemical pa  \n\n![](images/e597be304841969d07748eab5d2d77d7a4af53c53b6cd55446c415ac69270f28.jpg)  \nFigure 1: Scheme to obtain an LLM for chemistry, through using chemical domain knowledge to train a general-domain LLM.  \n\npers and 1.4K textbooks in chemistry used in Phase I, and 2) over 2.7M instructions crafted from various chemical databases in Phase II. Apart from chemical data, we also incorporated a substantial amount of general-domain data in both phases to make sure that ChemDFM maintains comprehension and reasoning capabilities of natural language while acquiring new chemical knowledge. As a result, ChemDFM can simultaneously handle a wide range of chemical tasks and convey free-form dialogues using the language of chemists, enabling human-AI collaboration in chemical research.  \n\nA series of experiments have been conducted to evaluate the prowess of ChemDFM, including molecule recognition, molecule design, molecular property prediction, and reaction analysis. The results show that ChemDFM achieves advanced performances, surpassing typical open-source LLMs.  \n\n![](images/43ac0a392eaec7b515bfa72edd952364bea2b6d9fd781002d21027e1db76982a.jpg)  \nFigure 2: a) Two-step training procedure to obtain ChemDFM. The icons are generated by the SDXL model provided by Stability $\\bar{\\mathrm{AI}^{5}}$ . b) Various types of tasks ChemDFM is capable of.  \n\nIt even outperforms GPT-4 on most tasks, despite the notable difference in model size. We further compared the performance between ChemDFM and the baseline LLMs in free-form unseen scenarios analogues to real-world scenarios. The test examples were constructed based on the latest chemical papers to avoid possible data leakage. The results show that ChemDFM can generate answers that are more accurate and relevant to the specific questions. These findings suggest that ChemDFM, capable of handling a broad range of chemical tasks and reasoning in both chemical and natural languages, can indeed serve as an AI assistant in chemical research.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2 ChemDFM  \n\nAs outlined in Figure 2, ChemDFM is trained based on LLaMa, a general domain LLM. Domain knowledge of chemistry is instilled in ChemDFM in two steps: Domain Pre-training and Instruction Tuning. Through this two-stage specialization process, ChemDFM “learned” chemistry and gained abilities such as molecule recognition and reaction prediction. The training process is presented below and evaluations of ChemDFM’s capability are elaborated in the next section.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2.1 Domain Pre-training  \n\nData used to train general-domain LLMs must contain knowledge covering a wide range of topics. Such broadness is often accompanied by sacrifices of deepness in each field. While models trained on such data have successfully gained strong natural language understanding and reasoning capabilities, they often fall short when it comes to in-depth specialized knowledge. The lack of domain knowledge is partially responsible for the well-known “hallucination” problem [Huang et al., 2023]. To alleviate this problem, we collected a corpus of data rich in chemical knowledge for domain pre-training, primarily from the two most authoritative sources for chemical knowledge: textbooks and published papers. Textbooks represent the widely accepted knowledge and basic principles of chemistry while published papers offer more details and more up-to-date chemical knowledge, some of which have not been incorporated into textbooks. Specifically, we selected 1.4K chemistry books from LibreTexts6 and Gold Books7 and collected 3.9M open-access papers in chemistry-related topics before January 2022. After further pre-processing and deduplication, we obtained 49M tokens from the textbooks and 34B tokens from the published research articles. To maintain the LLM’s general-domain knowledge and capabilities, we also included highly selective data in the general field, including Wikipedia, Arxiv, Books, StackExchange, GitHub code, WuDao Corpora [Yuan et al., 2021], etc. More details of domain pre-training are available in Appendix Section A.1.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.2 Instruction Tuning  \n\nThe data for the chemical instruction tuning dataset comprises two main categories: chemical knowledge presented in natural language and specialized molecular notations. A dataset containing over 1M question-answering pairs specialized in chemistry was constructed for instruction turning to enhance the model’s capability to process chemistry-related natural language. These data were generated from two sources. The first one is established question-answering datasets, including ARC [Clark et al., 2018], PIQA [Bisk et al., 2020], SciQ [Welbl et al., 2017], and HendrycksTest [Hendrycks et al., 2021]. The other source of questions is middle school exams. We collected open-source exam questions from the Internet and constructed question-answer pairs (with key points or problem-solving strategies when available) for the instruction tuning of ChemDFM.  \n\nWhile natural languages such as English or German are generally descriptive and highly versatile, they are often not the best media to convey chemical knowledge. For example, it is often much easier and more comprehensible to draw the molecular structure of a complicated organic molecule than to describe it using natural language. Generations of chemists have developed many specialized notations, such as molecular formulas and Simplified Molecular Input Line Entry System (SMILES) [Weininger, 1988] notation. This represents a key challenge for LLMs to understand chemistry. A key goal of the instruction tuning stage was to tackle this challenge by familiarizing ChemDFM with the specialized notations. In training ChemDFM, we chose SMILES, one of the most popular notations of molecules, as the main representation for molecules. It uses a sequence of letters to present a molecule, retaining rich structural information such as molecular configuration and chirality in most cases. In addition, its text-like data structure makes it highly compatible with LLMs.  \n\nTo help the model comprehend SMILES, three kinds of molecular data were used: 1. Molecule description (MD) and text-based molecule design (TBMD). Our dataset includes all the SMILES-description pairs from PubChem8, a web-scale chemical database that contains more than 100M compounds. The model was instructed to generate descriptions of given molecules or reversely, generate molecule(s) that match a description. We duplicated samples with descriptions longer than two sentences to further enhance the data quality. 2. Molecular property prediction (MPP). The model was instructed to predict the properties of a given molecule. This data was constructed based on the widely used molecular property prediction benchmark, MoleculeNet [Wu et al., 2018]. 3. Reaction completion (RC). The model was also instructed to complete chemical reactions in which one or more reactants/products were masked randomly. The reactions were sampled from USPTO [Lowe, 2012], the largest open-source chemical reaction database.  \n\nTable 1: Itemized list of our instruction tuning dataset. MD: Molecule Description, TBMD: Text-Based Molecule Design, MPP: Molecular Property Prediction, RC: Reaction Completion, MNA: Molecular Notation Alignment.   \n\n\n<html><body><table><tr><td>Data Type</td><td># samples</td><td>Data Source</td></tr><tr><td>QAs from Datasets</td><td>131K</td><td>ARC, PIQA, SciQ HendrycksTest</td></tr><tr><td>QAs from Exam</td><td>915K</td><td>Internet</td></tr><tr><td>MD</td><td>576K</td><td>PubChem</td></tr><tr><td>TBMD</td><td>576K</td><td>PubChem</td></tr><tr><td>MPP</td><td>102K</td><td>MoleculeNet</td></tr><tr><td>RC</td><td>300K</td><td>USPTO</td></tr><tr><td>MNA</td><td>120K</td><td>PubChem</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# [Round 0]  \n\nHuman:  Chemical reaction equations are typically presented as follows: \"reactant1.reactant2.reactant3...>reagent1.reagent2.reagent3...>product1.product2.product3...\". Each substance, be it a reactant, reagent, or product, is represented using the SMILES notation. You will be given an incomplete chemical reaction equation with missing parts showcased as _\". These voids may stand for one or several substances. Based on the available information in the equation, please predict what the missing substances could be. In your response, list only the missing elements without introducing any additional information.  \n\n![](images/14041f91fd2d33f9b69c098b9d5c8e7dc5f699e97dabaef9af9dc0402c52a9ce.jpg)  \n\n![](images/62d846bcfb24b22410c626e5e3ca70042519043b2e845ecbd1947d0b31e399fe.jpg)  \nFigure 3: Representative question used in instruction tuning.  \n\nIn addition to SMILES, we indirectly include two other widely used notations of molecules, IUPAC names and molecular formulas. We instructed the model to translate between the three notations, e.g. predicting SMILES of a molecule given its IUPAC name and vice versa, allowing it to understand these alternatives. This kind of data is called Molecular Notation Alignment (MNA) in this work.  \n\nTable 1 lists the itemized entries of our instruction tuning dataset. All the data samples take the form of (prompt, returns) tuples, where the prompt is composed of the dialogue format, instructions, and example inputs, and the returns are the expected outputs. Such an example is presented in Figure 3. To diversify the natural language instructions, we used GPT-4 to rephrase instructions for all tasks. The number of different instructions for each task ranges from 20 to 200.  \n\nTo maintain the advanced natural language comprehension abilities, we also included a substantial amount of general domain data for the instruction-tuning of ChemDFM. The ratio of data from the chemical domain to the general domain is roughly 1:2. The instruction tuning of ChemDFM is a full-parameter tuning process with more details in Appendix Section A.2.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 3 Evaluations  \n\nTo assess ChemDFM’s capability in chemistry, we compared its performance against several generalist LLM models: GPT-4 [OpenAI, 2023], LLaMa-2 [Touvron et al., 2023b] and Galactica [Taylor et al., 2022], as they represent very large generalist LLMs, medium-sized generalist LLMs and LLMs tuned for science, respectively. We used ChemLLMBench [Guo et al., 2023] for quantitative evaluation of ChemDFM’s ability in chemistry and then carried out qualitative analyses of ChemDFM’s free-form collaboration capacity, focusing on its superior chemistry-related conversation processing power.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 3.1 Quantitative Evaluation  \n\nChemLLMBench is made of a series of chemical tasks covering a wide range of chemistry-related topics. The standard form of evaluation was conducted on 100 instances randomly sampled from the respective test sets of the tasks. To ensure a fair comparison, we used the same 100 samples when comparing different LLMs, unless otherwise specified. Some non-LLM task-specific models were used for comparisons when available. Detailed explanations of the tasks and the prompt format for ChemDFM can be found in Appendix Section B. Specifically, the quantitative evaluation tasks can be categorized into the following four groups.  \n\n1) Molecule recognition. There are two series of tasks in ChemLLMBench that directly assess the capability to recognize molecules: name prediction and molecule captioning. In the name prediction tasks, a model is asked to translate between different notations for molecules, including SMILES, IUPAC name, and molecular formula. Specifically, it consists of four tasks: SMILES to IUPAC name translation (S2I), IUPAC name to SMILES translation (I2S), SMILES to Molecular Formula translation (S2MF), and IUPAC name to Molecular Formula transla  \n\nTable 2: Accuracy scores in name prediction tasks. Baseline results are from Guo et al. [2023]. S2I: SMILES to IUPAC names translation, I2S: IUPAC names to SMILES translation, S2MF: SMILES to molecule formulas translation, I2MF: IUPAC names to molecule formulas translation.   \n\n\n<html><body><table><tr><td>Model S2I↑</td><td>I2S↑ S2MF↑</td><td>I2MF↑</td></tr><tr><td colspan=\"3\">Task-specific specialist models</td></tr><tr><td>STOUT 55.0</td><td>70.0</td><td></td></tr><tr><td>LLM-based generalist models</td><td></td><td></td></tr><tr><td colspan=\"3\"></td></tr><tr><td>GPT-4 0 LLaMa2-13B-chat 0</td><td>1.2 8.6</td><td>8.4</td></tr><tr><td>Galactica-30B 0</td><td>0 1.0</td><td>0</td></tr><tr><td></td><td>0 0</td><td>0</td></tr><tr><td>ChemDFM-13B 4.0</td><td>11.0 73.0</td><td>51.0</td></tr></table></body></html>  \n\ntion (I2MF). For IUPAC names and SMILES, we normalized the predictions before calculating the accuracy scores, while for molecular formulas, only exact matches are considered correct answers. The molecule captioning tasks further require LLMs to not only recognize the molecule present by a given SMILES notation but also generate a brief description of it using natural language. In these tasks, traditional captioning metrics like BLUE, ROUGE, and METEOR are used to assess the model’s performance on a test set of ChEBI-20 [Edwards et al., 2021].  \n\nBenchmark performance of different models on these two molecule recognition tasks is reported in Table 2 and Table 3, respectively. Table 2 shows that most LLMs, including GPT-4, can hardly complete name prediction tasks, indicating a limited understanding of molecules and ChemDFM outperforms open-source LLMs by a significant margin across all these tasks. This outstanding performance of ChemDFM proves its robust molecule recognition capabilities and validates the effectiveness of our specialization process.  \n\nTable 3: Benchmark results of different models in molecule captioning tasks. †: results from Guo et al. [2023]. \\*: reproduced results.   \n\n\n<html><body><table><tr><td>Model</td><td>BLEU-2个</td><td>BLEU-4↑</td><td>ROUGE-1↑</td><td>ROUGE-2↑</td><td>ROUGE-L↑</td><td>METEOR↑</td></tr><tr><td colspan=\"7\">Task-specific specialistmodels</td></tr><tr><td>Text+Chem T5 [Christofidellis et al., 2023]</td><td>0.625</td><td>0.542</td><td>0.682</td><td>0.543</td><td>0.622</td><td>0.648</td></tr><tr><td>MolXPT [Liu et al., 2023]</td><td>0.594</td><td>0.505</td><td>0.660</td><td>0.511</td><td>0.597</td><td>0.626</td></tr><tr><td>InstructMol [Cao et al., 2023a]</td><td>0.475</td><td>0.371</td><td>0.566</td><td>0.394</td><td>0.502</td><td>0.509</td></tr><tr><td>Mol-Instruction [Fang et al., 2023]</td><td>0.249</td><td>0.171</td><td>0.331</td><td>0.203</td><td>0.289</td><td>0.271</td></tr><tr><td colspan=\"7\">LLM-based generalist models</td></tr><tr><td>GPT-4 (10-shot)</td><td>0.464</td><td>0.365</td><td>0.545</td><td>0.362</td><td>0.459</td><td>0.519</td></tr><tr><td>GPT-4 (0-shot)</td><td>0.062</td><td>0.013</td><td>0.192</td><td>0.040</td><td>0.125</td><td>0.209</td></tr><tr><td>LLaMa-2-13B-chat (10-shot)</td><td>0.197</td><td>0.140</td><td>0.331</td><td>0.193</td><td>0.265</td><td>0.372</td></tr><tr><td>Galactica-30B (10-shot)*</td><td>0.114</td><td>0.055</td><td>0.334</td><td>0.189</td><td>0.330</td><td>0.187</td></tr><tr><td>Galactica-30B (0-shot)</td><td>0.008</td><td>0.002</td><td>0.019</td><td>0.004</td><td>0.015</td><td>0.043</td></tr><tr><td>ChemDFM-13B (0-shot)</td><td>0.321</td><td>0.265</td><td>0.490</td><td>0.374</td><td>0.483</td><td>0.402</td></tr></table></body></html>  \n\nTable 4: Benchmark results of different models in text-based molecule design tasks. †: results from Guo et al. [2023]. \\*: 10-shot results   \n\n\n<html><body><table><tr><td>Model</td><td>Exact↑</td><td>BLEU↑</td><td>Dis↓</td><td>Validity↑</td><td>MACCS↑</td><td>RDK↑</td><td>Morgan↑</td></tr><tr><td colspan=\"8\">Task-specifc specialist models</td></tr><tr><td>MolXPT [Liu et al., 2023]</td><td>21.5</td><td>-</td><td></td><td>98.3</td><td>0.859</td><td>0.757</td><td>0.667</td></tr><tr><td>Text+Chem T5 [Christofidellis et al.,2023]</td><td>32.2</td><td>0.853</td><td>16.87</td><td>94.3</td><td>0.901</td><td>0.816</td><td>0.757</td></tr><tr><td>Mol-Instruction [Fang et al., 2023]</td><td>0.2</td><td>0.345</td><td>41.4</td><td>100</td><td>0.412</td><td>0.231</td><td>0.147</td></tr><tr><td colspan=\"8\">LLM-based generalist models</td></tr><tr><td>GPT-4**</td><td>17.4</td><td>0.816</td><td>21.2</td><td>88.8</td><td>0.867</td><td>0.738</td><td>0.672</td></tr><tr><td>LLaMa-2-13B-chat**</td><td>2.0</td><td>0.626</td><td>34.0</td><td>78.2</td><td>0.679</td><td>0.568</td><td>0.454</td></tr><tr><td>Galactica-30B</td><td>0.0</td><td>0.004</td><td>2738</td><td>95.6</td><td>0.233</td><td>0.109</td><td>0.053</td></tr><tr><td>ChemDFM-13B</td><td>45.0</td><td>0.874</td><td>9.9</td><td>98.0</td><td>0.922</td><td>0.871</td><td>0.798</td></tr></table></body></html>  \n\nIn molecule captioning tasks (as shown in Table 3), ChemDFM also performs far superior to open-source LLMs. The results denote that ChemDFM not only recognizes molecules but also infers their underlying chemical essence and nature. It is worth noting the drastic drop in GPT4’s performance from the ten-shot setting to the zero-shot setting, which indicates that GPT-4 thrives mostly on its extraordinary natural language capabilities to learn from given exemplars while its inherent molecule recognition capability is relatively fragile. Comparatively, ChemDFM achieves comparable performance without the help of exemplars, demonstrating its intrinsic molecule recognition capability.  \n\n2) Text-based molecule design. To evaluate LLM’s efficiency in making qualified molecule designs, ChemLLMBench reverses the molecule captioning tasks and asks the models to generate molecules based on their descriptions. Specifically, in the text-based molecule design task, models are asked to predict the SMILES of the molecule that fits the given description. Two sets of metrics are utilized to measure the performance of these tasks. The first set measures the text-based similarity of the predicted SMILES compared to the golden SMILES, which includes exact match, BLUE, and Levenshtein distance. The second set of metrics measures the chemical similarity of the predicted molecules to the golden molecules, including the validity of the predicted SMILES and the FTS (fingerprint Tanimoto Similarity) [Tanimoto, 1958] in terms of MACCS [und David Metzener, 1988], $\\mathrm{R}\\mathrm{\\bar{D}K}^{\\mathrm{\\bar{g}}}$ , Morgan [Morgan, 1965].  \n\nAs shown in Table 4, ChemDFM outperforms not only the generalist LLMs but also the traditional task-specific specialist models across almost all metrics, which is both surprising and promising. Considering that task-specific specialist models were evaluated on the entire test set, whereas the performance of ChemDFM was initially assessed on only 100 samples, we further evaluated ChemDFM on the complete test set to align with the task-specific models for a fair comparison. The results, shown in Table 7 of the Appendix, further validate the advantage of ChemDFM. The results from Table 4 and 7 unveil two key superiorities of ChemDFM over other models. On the one hand, ChemDFM has effectively established a relationship between SMILES notations and the chemical nature of compounds in our model, which other LLMs lack. On the other hand, ChemDFM benefits from the solid natural language comprehension capabilities inherited from LLaMa, which taskspecific specialist models lack. Altogether, ChemDFM constructs a more comprehensive knowledge system in chemistry, which helps it surpass both generalist and task-specific specialist models.  \n\nTable 5: AUC-ROC scores [Bradley, 1997] of different models in molecular property prediction tasks. Avg: average. †: reproduced results (The results of GPT-4 were obtained in January 2024).   \n\n\n<html><body><table><tr><td>Model</td><td>BACE↑</td><td>BBBP↑</td><td>ClinTox↑</td><td>HIV↑</td><td>Tox21↑</td><td>Avg↑</td></tr><tr><td colspan=\"7\">Task-specific specialist models</td></tr><tr><td>Uni-Mol [Zhou et al., 2022]</td><td>85.7</td><td>72.9</td><td>91.9</td><td>80.8</td><td>79.6</td><td>82.2</td></tr><tr><td>MolXPT [Liu et al., 2023]</td><td>88.4</td><td>80.0</td><td>95.3</td><td>78.1</td><td>77.1</td><td>83.8</td></tr><tr><td>InstructMol [Cao et al., 2023a]</td><td>85.9</td><td>64.0</td><td></td><td>74.0</td><td></td><td></td></tr><tr><td colspan=\"7\">LLM-based generalist models</td></tr><tr><td>GPT-4</td><td>62.5</td><td>61.5</td><td>51.6</td><td>65.9</td><td>55.2</td><td>59.3</td></tr><tr><td>LLaMa-2-13B-chat</td><td>26.0</td><td>60.3</td><td>45.7</td><td>29.0</td><td>51.7</td><td>42.5</td></tr><tr><td>Galactica-30B [Taylor et al., 2022]</td><td>72.7</td><td>59.6</td><td>82.2</td><td>75.9</td><td>68.5</td><td>71.8</td></tr><tr><td>ChemDFM-13B</td><td>78.4</td><td>66.7</td><td>89.9</td><td>73.6</td><td>79.8</td><td>77.7</td></tr></table></body></html>  \n\nTable 6: Accuracy scores of different models in reaction prediction and retrosynthesis tasks. B-H: Buchwald-Hartwig dataset [Ahneman et al., 2018]. Suzuki: Suzuki-Miyaura dataset [Reizman et al., 2016]. YP: Yield Prediction, RP: Reactant Prediction, RS: Reagent Selection, Retro: Retrosynthesis. †: results from Guo et al. [2023]. Please refer to Table $9{\\sim}12$ in the Appendix for complete results.   \n\n\n<html><body><table><tr><td>Model</td><td>YP↑ RP↑</td><td>Retro↑</td><td>RS↑</td></tr><tr><td colspan=\"4\">task-specific specialist models</td></tr><tr><td>UAGNN [Kwon et al., 2022] Chemformer [Irwin et al., 2022]</td><td>96.1</td><td>53.6</td><td>一</td></tr><tr><td colspan=\"4\">93.8 LLM-based generalist models</td></tr><tr><td>GPT-4</td><td>78.2 23.0</td><td>11.4</td><td>45.3</td></tr><tr><td>LLaMa-2-13B-chat</td><td>0.7 3.2</td><td>0.0</td><td>16.0</td></tr><tr><td>Galactica (30B)</td><td>0.4</td><td>1.6</td><td>8.0</td></tr><tr><td>ChemDFM-13B</td><td>81.0</td><td>49.0 12.0</td><td>23.7</td></tr></table></body></html>  \n\n3) Molecular property prediction. The molecular property prediction tasks in ChemLLMBench consist of five tasks from the MoleculeNet [Wu et al., 2018], including BACE, BBBP, HIV, ClinTox, and Tox21. Among them, BACE and BBBP each contain a single balanced binary classification task. HIV contains a single unbalanced binary classification task. ClinTox and Tox21 comprise two and twenty-one unbalanced binary classification tasks, respectively. To address the severe label imbalance in these tasks, the Area Under the Curve of the Receiver Operating Characteristic (AUCROC) metric [Bradley, 1997] was introduced. To better assess the molecular property prediction, we adopted a scaffold-vertical manner for data splitting. Specifically, the molecules from the DeepChem library [Ramsundar et al., 2019] were first grouped based on their Bemis-Murcko scaffold [Bemis and Murcko, 1996] representations. The datasets were then split into training and test sets according to these groups. This method ensures that no molecule sharing the same scaffold would appear in both the training set and the test set. While avoiding information leaking due to mere similarity of molecules, this method also significantly increases the difficulty of the tasks, making the assessment more challenging and meaningful. The results listed in Table 5 show that ChemDFM consistently outperforms other LLMs in all but one molecular property prediction task.  \n\n4) Reaction prediction and retrosynthesis. ChemLLMBench includes four types of tasks targeted at evaluating models’ capability of reaction understanding: Yield Prediction (YP), Reaction Prediction (RP), Reagent Selection (RS), and Retrosynthesis (Retro). The yield prediction tasks ask models to predict whether the given reaction is a high-yield reaction and are constructed based on two High-Throughput experimentation (HTE) datasets: the Buchwald-Hartwig dataset [Ahneman et al., 2018] and the Suzuki-Miyaura dataset [Reizman et al., 2016]. The reaction prediction tasks ask models to predict the product of the given reaction. The USPTO-MIT dataset [Jin et al., 2017] was used to construct these tasks. The retrosynthesis tasks focus on predicting the reactants of the given reactions and are constructed based on the USPTO-50K dataset [Schneider et al., 2016]. The reagent selection tasks focus on selecting the appropriate reactants, solvents, or ligands that lead to a higher yield of the reaction from a list of candidates based on the dataset proposed by Perera et al. [2018]. Accuracy is utilized to measure the performance.  \n\n![](images/4e9036adc0f62b95a01ca275bf678fc24c7ecebf53daac6436545b5bceaba0bd.jpg)  \nFigure 4: Examples of paper reading. Answers from ChemDFM are compared with GPT and the base model LLaMa. Correct and relevant information in the replies is marked in green, correct but irrelevant information in yellow, and wrong information in red. Key points of the answer are marked in bold. Full details and more examples are elaborated in Appendix Section C.1.  \n\nAs depicted in Table 6, ChemDFM’s performance significantly exceeds open-source LLMs in all the reaction-related tasks. When compared to GPT-4, ChemDFM achieved superior performances on 3 out of 4 tasks, but lagged behind on reagent selection tasks. A closer inspection reveals that these reagent selection tasks are multiple-choice questions where models are asked to directly copy the correct SMILES from the candidates listed in the questions. Compared with generative questions such as reaction prediction and retrosynthesis, multiple-choice questions alleviate the models’ burden of generating molecules from scratch. It seems that GPT-4 can indeed better follow the instructions and directly copy corresponding SMILES, while ChemDFM often tries to generate new answers.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3.2 LLM-Based Research Assistant  \n\nTo function as a competent AI assistant researcher, an LLM needs not only strong chemistry skills, but also language skills to comprehend, reason, and communicate with human researchers, primarily in natural language. In the following, we test ChemDFM in two typical scenarios faced by chemistry researchers: reading papers and designing experiments, both of which demand expertise in chemical and natural language skills.  \n\nReading literature and other technical papers is an indispensable part of a researcher’s daily routine. Oftentimes, researchers come across new concepts or expressions that can hinder their understanding of the material. An  \n\n![](images/1bf70d2587f420b24870361d209b6bd07353f7b8e42616fb7c45af2636596f85.jpg)  \nFigure 5: Example showing ChemDFM as an assistant researcher in the design of experiment through free-form dialogue. Key points of the answer are marked in bold. More examples can be found in Appendix Section C.2.  \n\nLLM-based reading partner or assistant can provide instant explanations and answers to such questions. In Figure 4, we compare the answers generated by ChemDFM with those from other LLMs. We have provided three example questions, with more examples in Appendix Section C.1, which are generally consistent with the analysis below. To prevent information leakage, the questions were constructed from chemistry papers published in 2023 only. Since ChemDFM only learned from papers published before 2022, this approach ensures ChemDFM has not learned the answers during training and simulates ChemDFM’s performance as a reading partner or tutor when reading new papers. Q1 represents a question of widely known domain knowledge. All LLMs including ChemDFM provide good answers. However, when questions involve new molecules and reactions (Q2 [Yin et al., 2023] & Q3 [Dargo et al., 2023]), the performances differ. Specifically, LLaMa-2 and Galactica primarily rely on retrieving knowledge from memory, which can result in numerous knowledge points that are correct but irrelevant or even misleading in the context of the questions. GPT-4 shows a primary level of ability to answer questions based on the provided molecules and/or reactions. It effectively answers Q2 but struggles with more complex questions involving complicated molecules such as Q3. In Q3, GPT-4 fails to fully recognize the underlying chemical aspects of the question and proposes methods that could violate the molecule’s catalytic activity. It is also worth noticing that as GPT-4 is a closed-source LLM, it is uncertain whether the literature used to construct the questions is included in GPT-4’s training corpus. Therefore, these \"new papers\" may not be new to GPT-4. In contrast to other LLMs, ChemDFM shows the ability to integrate memory-based knowledge while considering the situation described in the questions, providing key points that are highly relevant to the question. In terms of accuracy, relevance, and overall quality of the answers, ChemDFM largely outperforms other LLMs including GPT-4, demonstrating a better understanding of molecules and reactions, especially in the example of Q3. Apart from presenting key points, ChemDFM also endeavors to expand on its explanation and elaborate on the mechanism of the queried reactions or the proposed solutions, although this occasionally leads to inaccurate answers, as seen in the cases of Q1 and Q2. Please refer to Appendix Section C.1 for a more detailed analysis.  \n\nA knowledgeable discussion partner who is always available and patient would be invaluable for researchers, particularly in the stage of hypothesis generation and design of experiment (DOE). Figure 5 illustrates a scenario inspired by Yin et al. [2023] that showcases ChemDFM’s potential to assist researchers in free-form dialogues as an AI research partner. In this example, a human researcher aimed to selectively oxidize one of the two carbonyl groups of a molecule. The initial solution given by ChemDFM would lead to the oxidation of both carbonyl groups. However, after being alerted and challenged by the human researcher, ChemDFM acknowledged the mistake and proposed two possible strategies: using a weaker oxidation agent/condition or introducing a protecting group. Upon the researcher’s decision to use a protecting group, ChemDFM provided detailed recommendations, including a feasible agent and reaction condition. Throughout the dialogue, ChemDFM exhibited promising capabilities in comprehension (Round 1), error correction (Round 2), and detailing (Round 3), showcasing its efficacy in mastering both chemical and natural language. More examples can be found in Appendix Section C.2.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 4 Related Work  \n\nThere have been several pioneering studies focusing on leveraging LLMs to solve chemical problems. These works typically adopt one of two general strategies. The first one treats LLMs as powerful base models for multi-task training, neglecting their greatest strength in natural language understanding and reasoning [Christofidellis et al., 2023, Fang et al., 2023, Cao et al., 2023a, Zheng et al., 2023, Kim et al., 2024, Yu et al., 2024]. Consequently, the models devised under this framework are confined to solving the specific tasks on which they were trained, losing the ability to tackle unseen tasks or conduct free-form human-AI collaborations. The other strategy exploits LLMs’ strong natural language understanding and reasoning abilities, using them directly to handle complex chemical tasks described in natural language [Hatakeyama-Sato et al., 2023, Cao et al., 2023b, Boiko et al., 2023, Yoshikawa et al., 2023, M. Bran et al., 2024, Ruan et al., 2024]. However, most of them suffer from the fact that generalist LLMs lack an inherent understanding of chemical language and knowledge [Kristiadi et al., 2024]. We argue that an LLM useful in chemistry must learn and reason with both general-domain knowledge and chemical knowledge. In this work, we tried to achieve this by equipping general-domain LLMs with rich chemical knowledge of task-specific chemical models and obtained promising results.  \n\nNotably, this strategy has been successfully applied to develop specialist LLMs for several other scientific domains. For example, Med-PaLM [Singhal et al., 2023] and PMC-LLaMa [Wu et al., 2023a] are specialized LLMs for biology and medicine. Similarly, ChatDoctor [Li et al., 2023] and DrugChat [Liang et al., 2023] also offer LLMs specifically for the medicine field but focus on medical inquiries and drug discoveries. Other domain-specific LLMs have endeavored include education [Dan et al., 2023], materials science [Xie et al., 2023], and geography [Deng et al., 2023]. It is worth noting that most of these works only focus on natural language. Domain-specific languages, which differ significantly from natural languages, such as SMILES in chemistry, are often overlooked.",
+        "category": " Introduction"
+    },
+    {
+        "id": 12,
+        "chunk": "# 5 Conclusion  \n\nIn summary, this paper introduces ChemDFM, a specialist LLM that evolves from a generalist LLM through pre-training and instruction tuning using domain knowledge in chemistry. Quantitative evaluations show ChemDFM’s strong comprehension of molecular notations and reasoning capabilities for chemical knowledge, resulting in excellent performance in a wide range of chemical tasks such as molecular design and reaction analysis. In scenarios such as paper reading and experimental design, ChemDFM shows great potential in wielding chemical and natural languages to assist researchers through dialogue-based, free-form human-AI collaborations.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 13,
+        "chunk": "# Acknowledgments and Disclosure of Funding  \n\nThis work was supported by the National Science and Technology Major Project 2023ZD0120703, the China NSFC Projects (U23B2057, 62106142 and 62120106006), and the Shanghai Municipal Science and Technology Major Project (2021SHZDZX0102).",
+        "category": " References"
+    },
+    {
+        "id": 14,
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+        "category": " References"
+    },
+    {
+        "id": 15,
+        "chunk": "# A Experimental Setups",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 16,
+        "chunk": "# A.1 Domain Pre-training  \n\nChemDFM is pre-trained using the popular framework Megatron-DeepSpeed10 with Zero-2 [Rajbhandari et al., 2020] optimization technique based on LLaMa-13B [Touvron et al., 2023a]. We train ChemDFM using AdamW [Loshchilov and Hutter, 2019] with $(\\beta_{1},\\beta_{2})=(0.9,0.95)$ . During training, our model deals with 4M tokens per batch with a maximum sequence length of 6K. The maximum learning rate is 5e-5 under the cosine learning rate scheduler.  \n\n[Round 0]  \n\n![](images/c700e6755bb9fdc455f61ae5b9aa86769df120f0d6c5cb8d43ddeb0abff1cdc4.jpg)  \nFigure 6: Prompt format of the name prediction tasks",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 17,
+        "chunk": "# A.2 Instruction Tuning  \n\nTo fully exploit the capabilities of the pre-trained model, we employed full-parameter tuning during the instruction tuning stage. The popular framework Deepspeed-Chat [Yao et al., 2023] is leveraged with the Zero-3 optimization technique. We set the learning rate to 1e-5 with a global batch size of 256. To encourage the model to focus more on responding to the requirements rather than memorizing the patterns in prompts, we performed gradient back-propagation only on the tokens of the returns. Specifically, the loss function of our instruction tuning is  \n\n$$\n\\mathcal{L}=-\\frac{1}{|\\mathcal{D}|}\\sum_{i=1}^{|\\mathcal{D}|}\\sum_{j=1}^{n_{i}}l o g\\mathrm{P}(r_{j}|\\mathrm{prompt}_{i},r_{1},r_{2},...,r_{j-1}),\n$$  \n\nwhere $|\\mathcal D|$ is the size of the instruction tuning dataset and $\\mathtt{r e t u n r s}_{i}=(r_{1},r_{2},...,r_{n_{i}})$ . We train ChemDFM using AdamW with $(\\beta_{1},\\beta_{2})=(0.9,0.95)$ and a cosine learning rate scheduler.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# B More Details about ChemLLMBench Evaluations",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# B.1 Molecule Recognition",
+        "category": " Introduction"
+    },
+    {
+        "id": 20,
+        "chunk": "# B.1.1 Task Introduction  \n\nThe name prediction tasks take advantage of the different notations of molecules, including SMILES, IUPAC name, and molecular formula, and ask the models to translate between them. Specifically, it consists of four tasks: SMILES to IUPAC name translation (S2I), IUPAC name to SMILES translation (I2S), SMILES to Molecular Formula translation (S2MF), and IUPAC name to Molecular Formula translation (I2MF). For IUPAC names and SMILES, we normalized the predictions before calculating the accuracy scores, while for molecular formulas, only exact matches are considered correct answers.  \n\nThe molecule captioning tasks further require the LLMs to not only recognize what the molecule given by SMILES is but also understand the basic chemical nature of the molecule so as to generate a brief description of it. Specifically, ChemLLMBench leverages the test set of ChEBI-20 [Edwards et al., 2021] for this task. To measure the performance of this task, ChemLLMBench utilizes a series of traditional captioning metrics, including BLUE, ROUGE, and METEOR.",
+        "category": " Introduction"
+    },
+    {
+        "id": 21,
+        "chunk": "# B.1.2 Prompt Format  \n\nFor the name prediction tasks, we use a simpler prompt compared with that introduced in Guo et al. [2023]. An example is shown in Figure 6  \n\nFor the molecule captioning task, we use the same prompt introduced in Guo et al. [2023].  \n\nTable 7: Benchmark full test-set evaluation results of different models in text-based molecule design tasks. The best results among specialist and generalist models are highlighted in bold, respectively. $^\\dagger$ : reproducing results.   \n\n\n<html><body><table><tr><td>Model</td><td>Exact↑</td><td>BLUE↑</td><td>Dis↓</td><td>Validity↑</td><td>MACCS↑</td><td>RDK↑</td><td>Morgan↑</td></tr><tr><td colspan=\"8\">task-specific specialist models</td></tr><tr><td>MolXPT [Liu et al., 2023]</td><td>21.5</td><td></td><td>-</td><td>98.3</td><td>0.859</td><td>0.757</td><td>0.667</td></tr><tr><td>Text+Chem T5 [Christofidellis et al., 2023]</td><td>32.2</td><td>0.853</td><td>16.87</td><td>94.3</td><td>0.901</td><td>0.816</td><td>0.757</td></tr><tr><td>Mol-Instruction [Fang et al., 2023]</td><td>0.2</td><td>0.345</td><td>41.4</td><td>100</td><td>0.412</td><td>0.231</td><td>0.147</td></tr><tr><td colspan=\"8\">LLM-based generalist models</td></tr><tr><td>Galactica-30B (10-shot)</td><td>0.3</td><td>0.295</td><td>64.3</td><td>82.2</td><td>0.356</td><td>0.239</td><td>0.186</td></tr><tr><td>ChemDFM-13B</td><td>43.2</td><td>0.839</td><td>16.9</td><td>97.6</td><td>0.901</td><td>0.829</td><td>0.759</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# B.2 Text-Based Molecule Design",
+        "category": " Introduction"
+    },
+    {
+        "id": 23,
+        "chunk": "# B.2.1 Task Introduction  \n\nThe test set of ChEBI-20 is also exploited for this task in ChemLLMBench. Models are asked to predict the SMILES of the molecule that fits the given description. Two kinds of metrics are utilized to measure the performance of this task. The first set of metrics measures the text-based similarity of the predicted SMILES compared to the golden SMILES, which includes exact match, BLUE, and Levenshtein distance. The second set of metrics measures the chemical similarity of the predicted molecules compared to the golden molecules. That is mainly composed of the validity of the predicted SMILES and the FTS (fingerprint Tanimoto Similarity) [Tanimoto, 1958] in terms of MACCS [und David Metzener, 1988], RDK11, Morgan [Morgan, 1965].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# B.2.2 Prompt Format  \n\nWe use the same prompt introduced in Guo et al. [2023].",
+        "category": " References"
+    },
+    {
+        "id": 25,
+        "chunk": "# B.2.3 Additional Results  \n\nTo achieve a fair comparison with task-specific specialist models, we evaluate the performance of ChemDFM on the full test set of ChEBI-20 on this task. The results are illustrated in Table 7. ChemDFM surpasses the performance of the advanced specialist models on the major metrics while achieving comparable performance on others. Specifically, ChemDFM outperforms the specialist models on exact match scores and all three FTS-based similarity scores, which indicates that ChemDFM can make more reliable predictions based on the descriptions compared with specialist models.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 26,
+        "chunk": "# B.3 Molecular Property Prediction",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 27,
+        "chunk": "# B.3.1 Task Introduction  \n\nThe molecular property prediction tasks in ChemLLMBench consist of five tasks from MoleculeNet benchmark [Wu et al., 2018], including BACE, BBBP, HIV, ClinTox, and Tox21. Among them, BACE and BBBP are each a balanced binary classification task. HIV is an unbalanced binary classification task. ClinTox and Tox21 comprise two and twenty-one unbalanced binary classification tasks, respectively.",
+        "category": " Introduction"
+    },
+    {
+        "id": 28,
+        "chunk": "# B.3.2 Prompt Format  \n\nWe use the same prompts introduced in Guo et al. [2023].",
+        "category": " References"
+    },
+    {
+        "id": 29,
+        "chunk": "# B.3.3 Additional Results  \n\nDuring evaluations, we leverage a popular and more challenging dataset split provided by DeepChem library [Ramsundar et al., 2019]. We reproduce the results of the baseline models, including GPT-4, LLaMa-2-13B-chat, and Galactica (30B). Apart from the results in the Quantitative Evaluation  \n\nTable 8: AUC-ROC scores [Bradley, 1997] of different models under different settings in molecular property prediction tasks. †reproducing results (The results of GPT-4 were obtained in January 2024).   \n\n\n<html><body><table><tr><td>Model</td><td>BACE↑</td><td>BBBP↑</td><td>ClinTox↑</td><td>HIV↑</td><td>Tox21个</td></tr><tr><td colspan=\"6\">LLM-based generalist models</td></tr><tr><td>GPT-4 (0-shot)</td><td>62.5</td><td>61.5</td><td>51.6</td><td>65.9</td><td>55.2</td></tr><tr><td>GPT-4 (8-shot)</td><td>45.9</td><td>61.8</td><td>59.3</td><td>50.8</td><td>60.6</td></tr><tr><td>LLaMa-2-13B-chat (O-shot)</td><td>26.0</td><td>60.3</td><td>45.7</td><td>29.0</td><td>51.7</td></tr><tr><td>LLaMa-2-13B-chat (8-shot)</td><td>72.9</td><td>52.3</td><td>42.1</td><td>70.8</td><td>45.9</td></tr><tr><td>Galactica-30B [Taylor et al., 2022]</td><td>72.7</td><td>59.6</td><td>82.2</td><td>75.9</td><td>68.5</td></tr><tr><td>ChemDFM-13B (0-shot)</td><td>78.4</td><td>66.7</td><td>89.9</td><td>73.6</td><td>79.8</td></tr><tr><td>ChemDFM-13B (8-shot)</td><td>81.7</td><td>67.9</td><td>85.3</td><td>73.3</td><td>76.7</td></tr></table></body></html>  \n\n[Round 0]  \n\n![](images/ec8badf8bd1d6c94ed620987af271b1f52c9830ceaf535f73e6cc7a0861dd81e.jpg)  \nFigure 7: Prompt format of the reaction prediction and retrosynthesis tasks  \n\nSection of the main text, we also conduct few-shot experiments. The results are shown in Table 8. It is worth noticing that the performances under the few-shot setting are not always better than those under the zero-shot setting. That may be a result of the scaffold-vertical dataset split we use in our experiments. Because under the scaffold-vertical setting, the exemplars provided by the training split may be less helpful for the test samples.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 30,
+        "chunk": "# B.4 Reaction Prediction and Retrosynthesis",
+        "category": " Introduction"
+    },
+    {
+        "id": 31,
+        "chunk": "# B.4.1 Task Introduction  \n\nIn ChemLLMBench, there are four types of tasks targeted at evaluating models’ capabilities of reaction understanding. The yield prediction tasks ask models to predict whether the given reaction is a high-yield reaction and are constructed based on two High-Throughput experimentation (HTE) datasets: the Buchwald-Hartwig dataset [Ahneman et al., 2018] and the Suzuki-Miyaura dataset [Reizman et al., 2016]. The reaction prediction task asks the model to predict the product of the given reaction. ChemLLMBench utilizes the USPTO-MIT dataset [Jin et al., 2017] for this task. The reagent selection tasks focus on selecting the reagent that can maximize the yield of the reaction from a list of candidates. ChemLLMBench constructs three reagent selection tasks based on the dataset proposed by Perera et al. [2018]. The retrosynthesis task focuses on predicting the reactants of the given reactions and is constructed based on the USPTO-50K dataset [Schneider et al., 2016]. Accuracy is utilized to measure the performances except for the ligand selection task which uses top $50\\%$ accuracy.  \n\nTable 9: Accuracy scores of different models in yield prediction tasks. B-H and Suzuki stand for the Buchwald-Hartwig dataset and the Suzuki-Miyaura dataset, respectively. $\\dagger$ : results from Guo et al. [2023]. \\*: 8-shot results   \n\n\n<html><body><table><tr><td>Model</td><td>B-H Suzuki</td></tr><tr><td>task-specific specialist models</td><td></td></tr><tr><td>UAGNN [Kwon et al., 2022] 96.5</td><td>95.7</td></tr><tr><td>LLM-based generalist models</td><td></td></tr><tr><td>80.0 GPT-4+*</td><td>76.4</td></tr><tr><td>LLaMa-2-13B-chat 0.8</td><td>0.6</td></tr><tr><td>Galactica-30B 0.0</td><td>0.8</td></tr><tr><td>ChemDFM-13B 82.7</td><td>79.3</td></tr></table></body></html>  \n\nTable 10: Benchmark results of different models in reaction prediction tasks. †: results from Guo et al. [2023].   \n\n\n<html><body><table><tr><td>Model</td><td>Accuracy</td><td>Validity</td></tr><tr><td>task-specific specialist models Chemformer [Irwin et al., 2022]</td><td>93.8</td><td>100</td></tr><tr><td>Mol-Instruction [Fang et al., 2023] InstructMol [Cao et al., 2023a]</td><td>4.5 53.6</td><td>100 100</td></tr><tr><td>LLM-based generalist models</td><td></td><td></td></tr><tr><td>GPT-4 (20-shot)</td><td>23.0</td><td>93.0</td></tr><tr><td>LLaMa-2-13B-chat (20-shot)</td><td>3.2</td><td>72.2</td></tr><tr><td>Galactica-30B (5-shot)</td><td>3.6</td><td>94.8</td></tr><tr><td>ChemDFM-13B (0-shot)</td><td>49.0</td><td>98.0</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 32,
+        "chunk": "# B.4.2 Prompt Format  \n\nWe reformat the prompt provided by Guo et al. [2023] using the SMILES notations for reactions.   \nSpecifically, the examples of our prompts are illustrated in Figure 7.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 33,
+        "chunk": "# B.4.3 Additional Results  \n\nThe complete results for the yield prediction tasks, the reaction prediction task, the reagent selection tasks, and the retrosynthesis tasks are shown in Table 9, Table 10, Table 12, and Table 11, respectively.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 34,
+        "chunk": "# C More Qualitative Analysis",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 35,
+        "chunk": "# C.1 Paper Reading  \n\nWe first test the models with questions that only involve known knowledge (Figure 8).  \n\nQ-S1 (Q1) is an example of knowledge-intense questions. Models only need to memorize the details and mechanisms of Catellani-type reactions [Catellani et al., 1997] to answer the question correctly. The key point of the answer to this question is “regioselectivity”. While Galactica can hardly answer the question and LLaMa-2 misses the key point of the answer, ChemDFM accurately captures the key point to answer the question and provides a comprehensive answer. GPT-4 gives the best reply as it not only points out “regioselectivity” but also gives the result of the regioselectivity of norbornene. ChemDFM is the only model that tries to provide a detailed description of the mechanism behind the reaction. However, it makes minor mistakes when doing so.  \n\nQ-S2 asks for the regioselectivity of the Diels-Alder reaction [Kloetzel, 1948]. Only ChemDFM successfully answers the key points to this question, which is the result of the regioselectivity. GPT-4 provides a detailed introduction to the Diels-Alder reaction and regioselectivity but fails to answer the specific regioselectivity of the Diels-Alder reaction, while LLaMa-2 only gives the factors that could influence the regioselectivity. They do not answer the question.  \n\n![](images/59a44d9af45e1385b57e8284808895042aac6b9e1e2ae743f533a571806916d9.jpg)  \nFigure 8: Examples of paper reading where only widely known domain knowledge is involved. correct and relevant information in the replies is marked in green, correct but irrelevant information in yellow, and wrong information in red. Key points of the answer are marked in bold.  \n\n![](images/cd4a3f98bfc6ebb0c769837c4e394bdd81592a986d1b491cee8ebf5bf105e20c.jpg)  \nFigure 9: Examples of paper reading where new molecules and reactions are involved. correct and relevant information in the replies is marked in green, correct but irrelevant information in yellow, and wrong information in red. Key points of the answer are marked in bold.  \n\nTable 11: Benchmark results of different models in retrosynthesis tasks. $\\dagger$ : results from Guo et al. [2023].   \n\n\n<html><body><table><tr><td>Model</td><td>Accuracy</td><td>Validity</td></tr><tr><td>task-specific specialist models</td><td></td><td></td></tr><tr><td>Chemformer [Irwin et al., 2022]</td><td>53.6</td><td>100</td></tr><tr><td>LLM-based generalist models</td><td></td><td></td></tr><tr><td>GPT-4 (5-shot)</td><td>11.4</td><td>89.0</td></tr><tr><td>LLaMa-2-13B-chat (20-shot)</td><td>0.0</td><td>72.8</td></tr><tr><td>Galactica-30B (5-shot)</td><td>1.6</td><td>94.8</td></tr><tr><td>ChemDFM-13B (0-shot)</td><td>12.0</td><td>91.0</td></tr></table></body></html>  \n\nTable 12: Benchmark results of different models in reagent selection tasks. We report the result in accuracy scores except for Ligand Selection where we report the top $50\\%$ accuracy score. $\\dagger$ : results from Guo et al. [2023].   \n\n\n<html><body><table><tr><td>Model</td><td>Reactant</td><td>Solvent</td><td>Ligand</td></tr><tr><td colspan=\"4\">LLM-based generalist models</td></tr><tr><td>GPT-4</td><td>29.9</td><td>52.6</td><td>53.4</td></tr><tr><td>LLaMa-2-13B-chat+</td><td>14.5</td><td>5.0</td><td>28.4</td></tr><tr><td>Galactica-30B</td><td>10.7</td><td>10.4</td><td>3.0</td></tr><tr><td>ChemDFM-13B</td><td>24.0</td><td>12.0</td><td>35.0</td></tr></table></body></html>  \n\nAs for Q-S3, ChemDFM, Galactica, and GPT-4, all capture the key point to the answer (“the oxidation of alcohols to aldehydes and ketones”), while ChemDFM and GPT-4 further answer more properties of the Dess-Martin periodinane [Dess and Martin, 1983]. LLaMa-2, on the other hand, gives numerous wrong arguments and misses the key points.  \n\nThen, we ask the models about new molecules and new reactions which are published after January 2022. In this way, we can ensure minimal risk of data leakage and evaluate the models’ capability to handle unforeseen situations. The results are shown in Figure 9 and Figure 10.  \n\nQ-S4 (Q2) is constructed based on Yin et al. [2023]. Because the reaction mentioned in the question is a novel instance, models need to correctly identify the reaction and discover the mechanisms of it before answering the question. In practice, Galactica successfully identifies the key point of the answer, “deprotonate”, but fails to provide other useful information. LLaMa-2, in its reply, fails to identify the reaction mentioned in the question. Most of the information about NaH in its reply is correct but irrelevant to the reaction. GPT-4 identifies the key point of the answer but only gives a rough description of the mechanism of how it works. ChemDFM not only correctly identifies the key point of the answer but also provides an almost correct description of the mechanism.  \n\nQ-S5 is also constructed based on Yin et al. [2023]. All the models can recognize the DIBAL-H as a reducing agent, which is existing knowledge. However, only ChemDFM successfully identifies the reaction site of the new molecule, indicating its strong capabilities to handle unforeseen situations where new molecules and reactions are involved. The main mistake that ChemDFM makes is providing the wrong IUPAC name, which is a challenging task for LLMs even as a separate task (see Table 2 in the main text).  \n\nQ-S6 is constructed based on Wang et al. [2023a] and asks directly for the mechanism of the given reaction. Among the answers, the answer of ChemDFM is the most precise. Galactica and LLaMa-2 give nearly no correct information. Although GPT-4’s answer contains the correct reaction process, it also contains auxiliary processes that do not happen during the reaction, which masks the whole mechanism predicted by GPT-4 wrong. ChemDFM answers the correct reaction process with no excess. The only mistakes ChemDFM makes are again providing the wrong IUPAC names, which is a challenging task for LLMs even as a separate task (see Table 2 in the main text).  \n\nWe also ask several questions focusing more on molecules and less on reactions.  \n\n![](images/0ba025f64fdbbed6fecb072ff5358201f2d3ea5573aa840fb503956782eade8b.jpg)  \nFigure 10: Examples of paper reading where new molecules and reactions are involved. correct and relevant information in the replies is marked in green, correct but irrelevant information in yellow, and wrong information in red. Key points of the answer are marked in bold.  \n\nQ-S7 (Q3), constructed based on Dargo et al. [2023], focus on the modification of catalyst molecules. The molecule mentioned in the question is a novel instance and models need to infer the chemical properties of that molecule to answer the question. The key point of the answer is “introducing electron-withdrawing groups on the aromatic rings” as this method has the potential to increase the acidity while keeping the catalytic ability of the molecule. Among the LLMs, only ChemDFM successfully answers the key point, while others either fail to provide any specific solutions or give wrong solutions which will damage the catalytic ability of the molecule.  \n\nQ-S8, constructed based on Hao et al. [2023], focus on the modification of chiral environment. In the given molecule, there are two chiral centers. GPT-4 identifies the point chiral center and provides candidate methods that are not all correct. The other three models identify the axial chirality which is challenging to identify with only the SMILES notation. Among the three models, Galactica gives almost no detailed method to change the chiral environment, LLaMa-2 gives one correct method with more wrong ones, and ChemDFM provides two correct methods one of which is targeting specifically the axial chirality.  \n\nQ-S9 is constructed on Wang et al. [2023a]. It asks for the coordinate sites between the given molecule and palladium. There are a total of three coordinate sites. GPT-4 and ChemDFM each identify one of them, while Galactica and LLaMa-2 fail to identify any.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 36,
+        "chunk": "# C.2 Dialogue-Based Human-AI Collaboration  \n\nWe demonstrate two more examples of dialogue-based human-AI collaboration based on ChemDFM here. The dialogues are also inspired by the recently published papers to minimize the risk of data leakage and evaluate ChemDFM’s capability to handle unforeseen situations during human-AI collaboration.  \n\nThe dialogue shown in Figure 11 is inspired by Yin et al. [2023]. During the dialogue, the human researcher first asks for the role of LiCl in the given reaction. ChemDFM successfully identifies",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 37,
+        "chunk": "# Round 1",
+        "category": " Introduction"
+    },
+    {
+        "id": 38,
+        "chunk": "# What is the role of LiCl in the process of generating O=C1C=C2C3(CCC2)CC4(C)CCC(C)(C)C4C31C from O=C1C(C(OC)=O)=C2C3(CCC2)CC4(C)CCC(C)(C)C4C31C?  \n\nThe role of LiCl in this process is to act as a catalyst for the reaction. LiCl is added to a solution of the reactants in dry acetone, and it helps to facilitate the Diels-Alder reaction between the diene and dienophile moieties of the two starting materials. In this reaction LiCl serves as a Lewis acid, coordinating with the carbonyl oxygen of one of the starting materials and increasing the electrophilicity of the dienophile. This makes it more reactive towards the diene, which is then able to add to the dienophile to form the final product  \n\n![](images/39abf54487cadbc2d05716ff1c394138499d66535e6b47461839ea997bde1978.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 39,
+        "chunk": "# Round 2  \n\nBut it is not Diels-Alder reaction. The ester group on reactant leaves to form product.  \n\nYou are correct, I apologize for the mistake in my previous response. The process you described is not a Diels-Alder reaction, but rather a decarbonylation reaction. In this reaction, the LiCl catalyst helps to facilitate the loss of the carbonyl group from one of the starting materials, allowing the decarbonylated product to be formed. The exact mechanism by which LiCl promotes this reaction is not entirely clear, but it is believed to involve the formation of a carbanion intermediate that can undergo betaelimination to remove the carbonyl group.  \n\n![](images/32f40bc26c5ec5652af712cf8897f26927d5bbfbc0308c27e93448dd42590257.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 40,
+        "chunk": "# Round 3  \n\nAfter using LiCl, a lithium salt intermediate product was obtained. What should be added next to obtain the final product?  \n\nAfter using LiCl to promote the decarbonylation reaction, the resulting intermediate product will contain a lithium salt. To obtain the final product, the lithium salt can be hydrolyzed by adding water to the reaction mixture. This will cause the lithium salt to precipitate out as a solid, and the resulting supernatant can be isolated and purified to obtain the final product. Alternatively, the lithium salt can be converted back into one of the starting materials by treating it with a proton source, such as acid.  \n\n![](images/e8e5c0a6d163c034951a307ad053d818b863b6dcf81376db155e2685ca380ea3.jpg)  \n\nFigure 11: Example showing ChemDFM as an assistant researcher in the design of experiment through free-form dialogue. Key points of the answer are marked in bold and wrong information in red. The dialogue is inspired by Yin et al. [2023].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 41,
+        "chunk": "# Round 1  \n\nWhat intramolecular reactions will occur when AIBN and Bu3SnH is added to CC(C)(C)[Si](C)(C)OC1(c2cc3c(cc2Br)OCO3)C(=O)N2CCCC23C=C(OC(=O)c2ccccc2)C(=O)C13?  \n\nWhen AIBN and Bu3SnH is added to CC(C)(C)[Si](C)(C)OC1(c2cc3c(cc2Br)OCO3)C $\\scriptstyle(=0)$ )N2CCCC23C $\\scriptstyle:=($ C(OC(=O)c2ccccc2)C(=O)C13, an intramolecular reaction will occur to form a new ring. The reaction involves the formation of a new C-C bond between the carbon adjacent to the carbonyl group and the carbon adjacent to the silicon group in the starting material. This reaction is called the \"ene\" reaction.  \n\n![](images/313f2a6444bce2ddc08b38f2ee1bd54f6ce22569cc4d39053beb9c3391a293ba.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 42,
+        "chunk": "# Round 2  \n\nBut this is a radical debromination reaction.  \n\nYou are correct, I apologize for the error in my previous response. The reaction between AIBN and Bu3SnH in the presence of CC(C)(C)[Si](C)(C)OC1(c2cc3c(cc2Br)OCO3)C(=O)N2CCCC23C=C(OC(=O)c2ccccc2)C(=O)C13 will result in a debromination reaction, not an ene reaction. The debromination reaction will occur at the beta-position of the enone moiety resulting in the formation of a new C-C bond and the release of bromine.  \n\n![](images/5ff1af1dc2427389ca3e13ccb45d531c24b5a82e11b1abb2d5c507c79d884aaa.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 43,
+        "chunk": "# Round 3  \n\nSubsequently, TBAF is added, and what is its purpose?  \n\nTBAF (tetrabutylammonium fluoride) is a source of fluoride ion and will be added to the reaction mixture after the debromination reaction. The purpose of adding TBAF is to hydrolyze the silicon-containing group in the product, thereby removing the protecting group and revealing the alcohol functional group. This step is necessary to allow for further functionalization of the molecule.  \n\n![](images/a99599a94a5e451c8b0ab884fa7e24754e8aa65b4f99c40538afcc5095056686.jpg)  \n\nFigure 12: Example showing ChemDFM as an assistant researcher in the design of experiment through free-form dialogue. Key points of the answer are marked in bold and wrong information in red. The dialogue is inspired by Zhuang et al. [2023].  \n\nthe LiCl as a catalyst while misjudging the type of the reaction. To correct the answer, the human researcher points out the key error in the answer with some important details of the reaction (which can be easily discovered by comparing the product with the reactant). ChemDFM then corrects its mistake with even more details about the reaction process. To further validate whether ChemDFM fully understands the unforeseen reaction, we continue to ask about the post-processing procedure which is necessary to get the final product. ChemDFM successfully captures the key point to the question and gives the correct answer.  \n\nThe dialogue shown in Figure 12 is inspired by Zhuang et al. [2023]. ChemDFM first gives a partially correct answer to the question from the human researcher where it misjudges the position of the newly formed C-C bond and the type of the reaction. With the help of human correction, ChemDFM then realizes the mistakes and corrects them. Then the human researcher further asks about the next reaction that is conducted in Zhuang et al. [2023] without clarifying the current molecule composition of the system or restating the previous reaction. ChemDFM can infer this information from the dialogue history and correctly answer the question.  \n\nIn these dialogues, ChemDFM shows promising capabilities in handling unforeseen situations, error correction, and inferring information from dialogue history. These capabilities can be attributed to the fact that ChemDFM comprehends both natural language and chemical language. This allows a universal language protocol established between ChemDFM and human researchers, enabling meaningful human-AI collaborations.",
+        "category": " Results and discussion"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/Corkuna Introduction.json b/task2/task2-chunks/Corkuna Introduction.json
new file mode 100644
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+++ b/task2/task2-chunks/Corkuna Introduction.json	
@@ -0,0 +1,217 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Corkuna Introduction",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Agenda  \n\n![](images/18b28290de6552cb59fd57629df0d0f648a77d5af23e6c813a840a491df257b4.jpg)  \n\nCompany Introduction  \n\nNano coating technology roadmap and application  \n\nProduct Introduction (BEK/VCN)",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# Corkuna Facility",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# Background  \n\n![](images/f16846697637bc1701fa1a0053852d2259010f82adb33f4dcbc0c6418b1d319b.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# Waterproof is a solid need for the electronics  \n\n![](images/02dcf14199f032ad563da913fbc273aeb9f668ea9cf7b0c3cb02b6ce0b980346.jpg)  \nCell Phone  \n\n![](images/675d47b0551cf496c735251848f39f8178c59314040f40b9d2a470b0b79e4efd.jpg)  \nWearable  \n\n![](images/fa28e8da60a543b03396988de60df633fffc9a87e73d3921a03d506d19f21d60.jpg)  \nEarphone  \n\n![](images/a268745eceaed0449324b3b3a0fcc7f3f014286e135a345862d23c4749a76e54.jpg)  \nUnmanned aerial vehicle  \n\n![](images/1cc3eb0726fee7ab0fd49227ca23b33f792165a7945c900c6e24430873381f20.jpg)  \nAutomotive",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# Background|Waterproof market analysis  \n\nAT-RISK SYSTEMS MARKET   \nTOTAL: 1,150Bn  \n\n![](images/017b3311c62a5c3886287271134086319e6c230ca38ddc62088ed0b1ef9f4f3b.jpg)  \nTOTAL: \\$950Bn  \n\n<html><body><table><tr><td>System</td><td>CAAGR 2017-2022</td></tr><tr><td>Personal Computing</td><td>-1.1%</td></tr><tr><td>Other Computing/Infra.</td><td>8.4%</td></tr><tr><td>MobilePhones</td><td>2.5%</td></tr><tr><td>Communications Infra.</td><td>7.4%</td></tr><tr><td>Consumer</td><td>7.6%</td></tr><tr><td>Automotive</td><td>6.3%</td></tr><tr><td>Industrial</td><td>5.7%</td></tr><tr><td>Medical</td><td>3.7%</td></tr><tr><td>Military/Aerospace</td><td>5.2%</td></tr><tr><td>Total</td><td>3.9%</td></tr></table></body></html>\n\nN318.17 5jd-rugg ed",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# Our Timeline  \n\n![](images/898155ecaf04be755cdfb8c3311f3621ca3948bafef229498921f4a33ea9cf40.jpg)  \n\ngeneration coating product with 2 components and more features planned.  \n\nBEK series launched.",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# Company Introduction  \n\nCorkuna HQ (SH)  \n\nR&D/Production Center  \n\nSales Office  \n\nVietnam Office (CQ1 2020)  \n\nOversea office-CUPT (on going)  \n\n![](images/041317d8b75b77d9fd6ecdc04c182e30ea8a2faa78ffe33263fd6b1418176c38.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# Company Introduction| Core Technical Team  \n\n![](images/9d38a83517d19965f2e0eda99eecb4ad7510dad42399273d256ec04fb55e4c88.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# Technical Roadmap  \n\n![](images/8d54850a200316846ff091b03188b452a5383af401e4931b3cff7b10a38f6299.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 11,
+        "chunk": "# Core Technology  \n\n![](images/fd1b46b9865dec17ce7b3f9ab3227de704d152f04064d17a17189f480e017827.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 12,
+        "chunk": "# Molecular Design & synthesis  \n\nCoating chemicals molecular Coating structure Molecular self assembly  \n\n![](images/e8c21ea1084c1c281c9405176036d3d2d36a7a2be8bb30e0ed175d5ce6e9bbef.jpg)  \n\nCoating Chemicals Lean Production  \n\nManufacture under inert protection Package under inert protection  \n\n![](images/923ab14f0f3b6adc9e159fb2c93c44ba085cd00efcc72d0aa1db6a00ed72dd63.jpg)  \n\nRecipe Design & Formulation  \n\n$\\spadesuit.$ Synergistic technology $\\spadesuit$ Chemical interface modification  \n\n![](images/944fae7f7cccff081b982754d0f8a2fa86eb8623351eb1ec912b131735f66a3e.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# Coating Process Design  \n\n$\\spadesuit$ Surface treatment $\\spadesuit$ Spray/Dispensing $\\spadesuit$ Automation",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 14,
+        "chunk": "# Application background| Development and Trend",
+        "category": " Introduction"
+    },
+    {
+        "id": 15,
+        "chunk": "# Electronics W/P market Share trend in 2022  \n\n![](images/19bc603f51c243d2d42a5b58dbe08ed081a01b5e3d2f328514c37bdef09aa446.jpg)  \nElectronics W/P market Share in 2017",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# W/P Application Category  \n\n![](images/6093306cdda74a021f3b409729eac548dec2763c90bb68a958d7bcf1e194b5d0.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# Mechanical protection  \n\n• Semipermeable vents, cover, foam tape, rubber sealing, etc. • Easy to design and easy to use  \n\n![](images/8d2583733b8f5e738cf1e6be79a2e0f7ad089ffca96e2acce8b41eaaa93ebbbf.jpg)  \n\nBarrier for smaller and more delicate structural design. Not fully waterproof.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# Potting  \n\n• Direct filling on interior PCB boards, etc. • Complete sealing and protection.  \n\n![](images/bd53da1d4adba64ad5eb556cc219b7ff6ebac84b86729c9702bf496cb520f147.jpg)  \n\nHard for repairing.   \nHeat spreading problems.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# PCB board surface conformal coating  \n\n• Direct coating on PCB board.   \nComplete coverage.   \nSaves space for structural design.   \nGood for heat spreading.  \n\n![](images/39d93fabafbf9bc22bab2d4aaf8621b320b34dbb16583e43d8e5f1ff79cb76dc.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# Conformal Coating Category  \n\n![](images/392b71bf07cff1c5555b9b4a84ca158e8a10221680c2379328036b023473b4e5.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 21,
+        "chunk": "# Waterproof paint layer  \n\nSpecial paint with waterproof feature Easy to apply. Lower in cost.  \n\n![](images/3cea4e167606daf2f84ac40e94259bd784de06847656f7da01043272479a1df2.jpg)  \n\nOnly provides a covering layer with basic $w/p$ function. Not complete W/P Rubber-based. Not solvent free",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# Nano Coating Layer  \n\nVery thin layer of specially designed molecules coated on PCB   \nApplied with glue dispenser/PVD/CVD, etc.   \nVery good water and grease proof feature with functional molecule designing.   \nEnvironmental-friendly.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 23,
+        "chunk": "# Application |PCB Nano Coating  \n\n![](images/3630d2c6b353d3596e4e0a26a903be499294141f8cee68f1bea236ed65964e8d.jpg)  \n\nWater/salt/dust/grease proof.  \n\nHard surface substrate for protection.  \n\nFill the gaps and fissures.  \n\n![](images/e9123bec2a84eab58181b6d9d9d08d3be42a8481f4104d9abd27d9e8e52eeeaf.jpg)  \n\n\\*Notice: if on FPC board coating may be required to withstand some shape changing $\\mid\\rightarrow$ flexibility features also recommended.  \n\n![](images/336515a0f4fb7c4812cda12531b2154858d348f5f5e795a1b90ce55bda87bc4a.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# Application| PCB Nano Coating Methods  \n\n![](images/1b22f80991fd26b2763384e2b0fcacafad1ba417a407205e9c23ad6716298f8c.jpg)  \n\n![](images/caa49d304f98dbf814b619397e6af0602311db8a4b5968d553a18dca55163e85.jpg)  \n\n![](images/135dbe7f8403ea38da6be469da4dc5947e9bdb254f5e2b3fc9dda287d9cf9a72.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 25,
+        "chunk": "# PVD  \n\nPhysical vapor deposition. Gasified coating material deposits on the surface forming a very thin protection layer. Higher cost. Longer time. Flexibility cannot be convinced.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 26,
+        "chunk": "# CVD  \n\nChemical vapor deposition. Coating layer is formed through deposition (similar to PVD) and chemical reaction on surface. Higher cost. Longer time. Flexibility cannot be convinced.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 27,
+        "chunk": "# Soaking  \n\nSoak the PCB board directly in the solution of coating material.   \nWith time a protection film will cover the surface.   \nEasy, less time but lower coverage   \nespecially in small gaps.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 28,
+        "chunk": "# Application| PCB Nano Coating Methods",
+        "category": " Introduction"
+    },
+    {
+        "id": 29,
+        "chunk": "# Spraying through dispenser  \n\n![](images/6046dad85d354ae8cfe494b01121c5f4cc3d382dd50748e8f3950dea2a93483b.jpg)  \n\nEasier and convenient to control the coating evenness, thickness and qty of coating material   \nHigh coverage even in gaps and fissures with different spraying angles and spraying pressure adjustment   \nShorter time and less cost compared with PVD/CVD.  \n\n![](images/640c97efbfc78fd362c978f9ce75ee72e5e7db7e9a66d3e1fb9e7981a7700fda.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 30,
+        "chunk": "# Application| PCB Nano Coating Methods  \n\n![](images/9e42c0e59159de2ad392ebe1199b47c361f4024ac78a6985164e854f996ef866.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 31,
+        "chunk": "# Product Introduction | BEK Series  \n\n![](images/4a5923452acaac2ee8caf33f3d428d0508111556ced810f1de4f17a971f721a6.jpg)  \n\nGood adhesion to PCBs, glass, metal, modified plastic, resin and ceramic.  \n\nOne step to use with glue dispenser.  \n\nFor general PCB/FPC and module coating.  \n\n![](images/f9b73be042458fdc397a7a0b71e48bdff58865b71b66e1cf9eeeceb08728482b.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 32,
+        "chunk": "# Product Introduction | BEK Series TDS  \n\n![](images/73c87094103870cbcb36e9419b04e1aa53d16a750b6bfb44a716322813497ef8.jpg)  \n\n<html><body><table><tr><td colspan=\"2\">Properties of Post Treatment Coating</td></tr><tr><td>Coating thickness</td><td>300nm-15um (in accordance with customer needs)</td></tr><tr><td>Glossiness</td><td>High</td></tr><tr><td>Adhesion Cross-Cut Test</td><td>5B</td></tr><tr><td>Abrasion Test</td><td>5000t - 10oo0t (Depend with the usage and substrates)</td></tr><tr><td>Anti-corrosion in salt solution</td><td>Excellent</td></tr><tr><td>Water Contact Angle (Coated on Glass)</td><td>110° (Depend with the usage and substrates)</td></tr><tr><td>Transmittance % (Coated on Glass)</td><td>93% (Glass=91~92%)</td></tr><tr><td>Fluorescent inspection</td><td>Yes</td></tr><tr><td>Working in water</td><td>Electronic Product, No Shell, Over 60min by coating 5-10g/m² (the lifetime for coated electronics working in Water is depended with the usage. )</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 33,
+        "chunk": "# Product Introduction | VCN L1-B and L2 Combo  \n\n![](images/f519cdb9e05f679ac4e570061fd1dbf8df79ab34f5bf00d500a47536414e5884.jpg)  \n\nVCN L1-B: better inner structural filling and better flexibility  \n\nVCN L2: Repels water and oil on the surface. Also providing hard surface texture  \n\nSpecial reaction between groups of L1-B and L2 molecules $\\rightarrow$ strong linking and adhesion.  \n\nTwo steps to apply VCN L1-B and L2 on the surface.",
+        "category": " Introduction"
+    },
+    {
+        "id": 34,
+        "chunk": "# Product Introduction | VCN L1-B and L2 Combo",
+        "category": " Introduction"
+    },
+    {
+        "id": 35,
+        "chunk": "# SEM pictures of VCN L1-B AND l2 layer  \n\n![](images/c93d8951e08c9f5188a0b2a76ac292c55fb179a97e098d70c93f86d8f9315413.jpg)  \n\n![](images/f5c2a0c109253556940482cf5763fa0614b2b2822ba0f1c721f2fe730968d464.jpg)  \n\n![](images/2eea3c4958f1cdc7c5caf65e981a431e42804e0bb56e3de5ff58c4af0effb18e.jpg)  \n\nThe FESEM picture of VCN L1-B displayed a Hilly-like and porous structures that own the high specific surface area can bond with VCN L2.  \n\nThe FESEM picture of VCN L2 displayed a high densely and homogenously structures.  \n\nThe FESEM picture of coated VCN L1-B and L2 that displayed the multilayer and high densely structure.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 36,
+        "chunk": "# Product Introduction | VCN L1-B and L2 Combo  \n\n![](images/9c5ab5ea16a974b74b914ff8d582a1fa5328a7fa48df5fabdaab614d8e7f5fd1.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 37,
+        "chunk": "# Product Introduction | VCN L1-B and L2 Combo TDS  \n\n![](images/8ea6ede93981f64d9f4a41dcb559fedc1b0434e25a167036f9d6d774a0f6582c.jpg)  \n\n<html><body><table><tr><td colspan=\"4\">Properties of Post Treatment Coating</td></tr><tr><td rowspan=\"2\">Dielectric Constant</td><td>2.96(@1MHZ)</td><td>1.669(@1MHZ)</td><td></td></tr><tr><td colspan=\"2\">2.97@10kHZ, 2.75@100kHZ, 2.58@1MHZ (Combined)</td><td></td></tr><tr><td>Dielectric Strength (Fully curing)</td><td colspan=\"3\">> 200V/um (Combined)</td></tr><tr><td>Hardness</td><td colspan=\"3\">2-3H (Coated on Glass substrate)</td></tr><tr><td>Surface Resistance (@24 °C Humidity 50%) Water Contact Angle (Coated on Glass)</td><td colspan=\"2\">6.5x1011 @500V (Combined) 106° - 110° (Depend with the usage and substrates)</td><td></td></tr><tr><td>Transmittance % (Coated on Glass)</td><td>86 % (Glass=91%)</td><td>92 % (Glass=91%)</td><td></td></tr><tr><td>Volume Resistivity Ohms, 24 C, 50% RH</td><td></td><td>8.45x1013@500V (Combined)</td><td></td></tr><tr><td>Dissipation Factor</td><td colspan=\"3\">0.01-0.02@10kHZ, 0.016-0.017@100kHZ, 0.017-0.018@1MHZ (Combined)</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 38,
+        "chunk": "# Product Introduction | Salt Mist Comparison  \n\n<html><body><table><tr><td colspan=\"5\">Salt mist comparison test result</td></tr><tr><td>Category</td><td>NO coating</td><td>Competitor A</td><td>Competitor B</td><td>VCN coating</td></tr><tr><td>Post 24hrs</td><td></td><td></td><td></td><td></td></tr><tr><td> Post 48hrs</td><td></td><td></td><td></td><td></td></tr><tr><td>Post 72hrs</td><td></td><td></td><td></td><td></td></tr><tr><td>Post 96hrs</td><td></td><td></td><td></td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 39,
+        "chunk": "# Product Introduction | Application Method  \n\n![](images/0fc1f11c83bcef7b8a3cb313eb9f2473336d42e3efc286124598ce4b934fd4f0.jpg)  \n\nPCB or FPC fixed in clips then put in the convey belt.  \n\nPlasma surface cleaning and pretreatment  \n\nCoating  \n\nCuring in tunnel oven under certain condition  \n\nFinished product. Can be checked under UV light.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 40,
+        "chunk": "# Corkuna Facility|Production facility  \n\n1. VCN L2 production line   \n2. VCN L1-B production line   \n3. BEK-04 production line   \n4. Auto packing line  \n\n![](images/e8a0bd1999dcf3d565f2d8509c6a82f775a4787ee9a455b7d0b52f2069b628c1.jpg)  \n\n![](images/dcc878c0503a6ba1feeae5ad6a5735941083e6d5c162e67b61525e0445ba2144.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 41,
+        "chunk": "# Corkuna Facility|Production facility  \n\nFlow velocity adjusting during production.  \n\n![](images/0bd1c143747905e7ac73eb7c850fdc511987aecf2e24508d0ba6ebe97a7446a5.jpg)  \n\nCross control material input  \n\nSample collection for quality check.  \n\nFinished product packing.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 42,
+        "chunk": "# Corkuna Facility | Testing Equipment  \n\n![](images/8a4a5478ff3cd64e44272c6234b7da5efffc533b8a4bbe128d0d63a7c4ca9213.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 43,
+        "chunk": "# Corkuna Facility | Application Equipment  \n\n![](images/e4bef8956b81493f1470c25f9907527f0db3fd8fe235e6afec80974768ba6d0d.jpg)  \nHeating chamber  \n\nGlue dispenser  \n\nLaser Demask",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,52 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利申请  \n\n(21)申请号 201880025639.1  \n(22)申请日 2018.05 .14  \n(30)优先权数据2017-123300 2017 .06.23 JP  \n\n(85)PCT国际申请进入国家阶段日2019.10 .17  \n\n(86)PCT国际申请的申请数据PCT/JP2018/018592 2018.05 .14(87)PCT国际申请的公布数据WO2018/235456 JA 2018.12.27(71)申请人 东洋高分子股份有限公司地址 日本大阪  \n\n(72)发明人 筱崎友宽 吉田俊  \n\n(74)专利代理机构 北京康信知识产权代理有限责任公司 11240代理人 纪秀凤  \n(51)Int.Cl .C09D 4/02(2006.01)B32B 27/30(2006.01)B32B 27/36(2006.01)C09D 7/63(2006.01)C09D 7/65(2006.01)",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称  \n\n防雾涂料组合物及使用其涂料组合物的防雾性透明片材",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# (57)摘要  \n\n提供防雾涂料组合物含有：(A)亲水性双酚A型(甲基)丙烯酸酯、(B)反应性非离子表面活性剂、(C)反应性离子液体和(D)聚合性引发剂。防雾涂料组合物优选进一步包含(E)季戊四醇(甲基)丙烯酸酯和(F)尿烷(甲基)丙烯酸酯类树脂。防雾性透明片材具备透明的基材和配置于该基材表面的由上述防雾涂料组合物构成的防雾被膜。  \n\n1.一种防雾涂料组合物，其特征在于，含有：  \n\n(A)亲水性双酚A型(甲基)丙烯酸酯；(B)反应性非离子表面活性剂；(C)反应性离子液体；以及(D)聚合性引发剂。2.根据权利要求1所述的防雾涂料组合物，其特征在于，所述(C)反应性离子液体是由磺酸铵盐构成的液体。3.根据权利要求1或2所述的防雾涂料组合物，其特征在于，进一步包含(E)季戊四醇(甲基)丙烯酸酯。4.根据权利要求1至3中任一项所述的防雾涂料组合物，其特征在于，进一步包含(F)尿  \n烷(甲基)丙烯酸酯类树脂。5.根据权利要求1至4中任一项所述的防雾涂料组合物，其特征在于，相对于100质量份  \n所述(A)成分，所述(B)成分的含量为超过2质量份且20质量份以下。6.根据权利要求1至5中任一项所述的防雾涂料组合物，其特征在于，相对于100质量份  \n所述(A)成分，所述(C)成分的含量为1质量份以上5质量份以下。7.根据权利要求1至6中任一项所述的防雾涂料组合物，其特征在于，所述(B)成分相对  \n于所述(C)成分的含有质量比的(B)/(C)为1以上10以下。8.根据权利要求1至7中任一项所述的防雾涂料组合物，其特征在于，进一步包含均化剂。9.根据权利要求1至8中任一项所述的防雾涂料组合物，其特征在于，所述聚合性引发  \n剂为光聚合引发剂。10.一种防雾性透明片材，其特征在于，具备：透明的基材；和配置于所述基材的表面的、由权利要求1至9中任一项所述的防雾涂料组合物构成的防  \n雾被膜。11.根据权利要求10所述的防雾性透明片材，其特征在于，所述基材是聚对苯二甲酸乙二酯制的基材。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# 防雾涂料组合物及使用其涂料组合物的防雾性透明片材",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001] 本发明涉及防雾涂料组合物及使用其的防雾性透明片材。本申请基于并要求于2017年6月23日提交的日本专利申请第2017-123300号的优先权的权益，该日本申请中记载的全部内容结合于此作为参照。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002] 当基材的表面温度低于周围空气的露点时，在基材的表面会附着水滴产生模糊。在透镜、玻璃窗、透明膜等透明基材以及镜子等反射材料中，表面产生模糊导致损害透射图像或反射图像的可见性。为此，提出了在基材的表面形成赋予防雾效果的涂层来防雾的方法。例如，已经公开有如下方法：通过在透明基材的表面上形成防雾被膜，提高基材表面的亲水性或减小透镜与水的接触角来防止在基材表面上形成水滴，从而防止基材的模糊(例如专利文献1、专利文献2等)。  \n\n[0003] 现有技术文献  \n[0004] 专利文献  \n[0005] 专利文献1：日本专利申请公开第2004-83846号公报[0006] 专利文献2：日本专利申请公开第2007-137937号公报。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0007] 发明要解决的课题  \n[0008] 在各种各样的场合都寻求防雾性。尤其是在伴随着温度急速变化的环境下，也寻求发挥防雾性。进而，寻求一种防雾被膜，不仅防雾被膜刚刚形成后的初始防雾性优异，而且防雾效果可长时间持续的防雾持续性也优异。例如，寻求即使在暴露于水、温水的环境下，防雾性依然持续的防雾被膜及具备了这样的防雾被膜的防雾性透明片材。  \n[0009] 因此，本发明的目的之一是提供能够形成不仅初始防雾性优异、防雾效果可长时间持续的防雾持续性也优异的防雾被膜的防雾涂料组合物以及使用其的防雾性透明片材。[0010] 用于解决课题的手段  \n[0011] 本发明的第一方式涉及的防雾涂料组合物含有：(A)亲水性双酚A型(甲基)丙烯酸酯、(B)反应性非离子表面活性剂、(C)反应性离子液体和(D)聚合性引发剂。  \n[0012] 此外，本申请发明的第二方式涉及的防雾性透明片材具备：透明的基材和配置于该基材表面的由上述防雾涂料组合物构成的防雾被膜。  \n[0013] 发明效果  \n[0014] 根据本申请发明，可提供能够形成不仅初始防雾性优异、防雾效果可长时间持续的防雾持续性也优异的防雾被膜的防雾涂料组合物以及防雾特性优异的防雾性透明片材。",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 具体实施方式  \n\n[0015] [本申请发明的实施方式的说明]  \n\n[0016] 首先列出并说明本申请发明的实施方式。本申请发明涉及的防雾涂料组合物含有：(A)亲水性双酚A型(甲基)丙烯酸酯、(B)反应性非离子表面活性剂、(C)反应性离子液体和(D)聚合性引发剂。  \n\n[0017] 含有(A)亲水性双酚A型(甲基)丙烯酸酯、(B)反应性非离子表面活性剂和(C)反应性离子液体的上述防雾涂料组合物刚刚形成防雾被膜后的初始防雾性优异。其中，具有尤其是在低温环境下发挥防雾性(低温防雾性)的效果。此外，这样的防雾涂料组合物具有使形成了防雾被膜后的基材表面的亲水性持续的效果。通过对基材赋予这样的持续性的亲水性(亲水持续性)，能够形成防雾持续性优异的防雾被膜。  \n\n[0018] 此外，(B)反应性非离子表面活性剂和(C)反应性离子液体还具有使基材表面的接触角减小的效果。通过减小基材表面的接触角，进一步提高防雾效果。进而，通过含有(D)聚合性引发剂，能够提供分子量大，基材表面的保持性优异的防雾被膜。结果，能够形成防雾效果可长时间持续的防雾持续性优异的防雾被膜。  \n\n[0019] 通过像这样含有上述(A)成分至(D)成分，可提供能够形成初始防雾性优异、且防雾效果可长时间持续的防雾持续性也优异的防雾被膜的防雾涂料组合物。  \n\n[0020] 在上述防雾涂料组合物中，(C)反应性离子液体可以是由磺酸铵盐构成的液体。通过含有这样的反应性离子液体，能够更加确实地获得不仅初始防雾性优异，而且防雾效果可长时间持续的防雾持续性也优异的防雾被膜。  \n\n[0021] 上述防雾涂料组合物还可以包含(E)季戊四醇(甲基)丙烯酸酯。通过含有(E)成分，可使后述的防雾被膜的耐水洗性提高，并且赋予防雾被膜柔软度。  \n\n[0022] 上述防雾涂料组合物还可以包含(F)尿烷(甲基)丙烯酸酯类树脂。通过含有(F)成分，可使后述的防雾被膜的耐水洗性提高，并且赋予防雾被膜柔软度。  \n\n[0023] 在上述防雾涂料组合物中，相对于100质量份(A)成分，(B)成分的含量可以是超过2质量份且20质量份以下。通过使(B)成分的含量相对于100质量份(A)成分为超过2质量份，可获得能够更稳定地形成被膜透明度高的防雾被膜的防雾涂料组合物。此外，即使(B)成分的含量相对于100质量份(A)成分为超过20质量份，由于效果饱和，透明性、防雾特性也不会再提高，反而成本会增加。因此，相对于100质量份(A)成分，(B)成分的含量优选为20质量份以下。  \n\n[0024] 在上述防雾涂料组合物中，相对于100质量份(A)成分，(C)成分的含量可以是1质量份以上5质量份以下。只要(C)成分的含量在1质量份以上，就能够更明确地发挥(C)成分带来的防雾特性的提高效果。此外，即使(C)成分的含量相对于100质量份(A)成分超过5质量份，由于效果饱和，透明性、防雾特性也不会再提高，反而成本会增加。因此，相对于(A)成分100质量份，(C)成分的含量优选为5质量份以下。  \n\n[0025] (B)成分相对于(C)成分的含量比(B)/(C)可以是1以上10以下。通过使比(B)/(C)为1以上，能够提供防雾特性更加优异的防雾被膜。此外，即使上述比超过10，由于效果饱和，透明性、防雾特性也不会再发生变化，因此上限优选为10。  \n\n[0026] 上述防雾涂料组合物还可以含有均化剂。通过含有均化剂，可提高防雾涂料组合物的涂布性。进而能够使基材和水的接触角减小，从而不易产生水滴。因此有助于提高防雾效果。  \n\n[0027] 在上述防雾涂料组合物中，聚合性引发剂可以是光聚合引发剂。通过使聚合性引发剂为光聚合引发剂，能够相对容易地进行涂布了防雾涂料组合物后的固化。  \n\n[0028] 本申请发明涉及的防雾性透明片材具备：透明的基材和配置于基材表面的由上述防雾涂料组合物构成的防雾被膜。具备由上述防雾涂料组合物构成的防雾被膜的防雾性透明片材具有优异的透明性和防雾特性。  \n\n[0029] 基材可以是聚对苯二甲酸乙二酯制的基材。由于聚对苯二甲酸乙二酯的透明性优异，因此能够获得片材整体的透明度高的防雾性透明片材。此外，由于聚对苯二甲酸乙二酯的加工性优异，因此能够获得可应用在多种用途的防雾性透明片材。  \n\n[0030] [本申请发明的实施方式的详细说明][0031] 接着，对本申请发明的防雾涂料组合物的一个实施方式进行说明。本实施方式涉及的防雾涂料组合物含有：(A)亲水性双酚A型(甲基)丙烯酸酯(在本申请说明书及权利要求书中也称为“(A)成分”)、(B)反应性非离子表面活性剂(在本申请说明书及权利要求书中也称为“(B)成分”)、(C)反应性离子液体(在本申请说明书及权利要求书中也称为“(C)成分”)和(D)聚合性引发剂(在本申请说明书及权利要求书中也称为“(D)成分”)。在本说明书中，“(甲基)丙烯酸酯”意味着丙烯酸酯及甲基丙烯酸酯中的任一方或两方。  \n\n[0032] [(A)亲水性双酚A型(甲基)丙烯酸酯][0033] 本申请发明的防雾涂料组合物含有亲水性双酚A型(甲基)丙烯酸酯作为(A)成分。亲水性双酚A型(甲基)丙烯酸酯是防雾涂料组合物的主要成分，对涂布了防雾涂料组合物的基材赋予亲水性，有助于提高防雾效果。此外，通过防雾涂料组合物含有亲水性双酚A型(甲基)丙烯酸酯，含有由防雾涂料组合物形成的防雾被膜的离子液体的上述防雾涂料组合物刚刚形成防雾被膜后的尤其是低温防雾性和亲水持续性良好。“亲水性”意味着加入到水中时不发生相分离，可在水中分散或溶于水的树脂。  \n\n[0034] 上述亲水性双酚A型(甲基)丙烯酸酯具有双酚A的两个羟基被具有(甲基)丙烯酸酯基的反应性基团取代的结构。作为亲水性双酚A型(甲基)丙烯酸酯，例如可列举具有由下述通式(1)表示的结构的化合物。  \n\n[0035] [化1]  \n\n![](images/245ca2ac0d2929260a5a7b931c7da74b51fc7027f95126c51153a1707f2647e0.jpg)  \n\n[0037] (式中， $\\mathbb{R}^{1}$ 及R2分别独立地表示氢原子或甲基，m及n分别独立地表示0以上的整数。m$+\\mathrm{n}$ 的值为0以上，优选为4以上，更优选为10以上。)  \n\n[0038] 如上述式(1)所示，在本申请说明书中，亲水性双酚A型(甲基)丙烯酸酯优选含有环氧烷烃改性的双酚A型(甲基)丙烯酸酯。作为环氧烷烃改性的双酚A型(甲基)丙烯酸酯，例如包括环氧乙烷改性的双酚A型(甲基)丙烯酸酯、环氧丙烷改性的双酚A型(甲基)丙烯酸酯等。式(1)中， $\\mathtt{m}+\\mathtt{n}$ 的值越大，亲水性双酚A型(甲基)丙烯酸酯的亲水性越高。如上所述， $\\mathtt{m}+\\mathtt{n}$ 的值优选为4以上、更优选为10以上。作为这样的化合物的优选例子，例如可列举由下述式(2)表示的化合物。  \n\n[0039] [化2]  \n\n![](images/819d20ddf80577a7527069d4852d0c978abe067a1a35c2d9a05510cdbd2b3614.jpg)  \n\n[0041] (式中，m及n分别独立地表示0以上的整数，例如 $\\scriptstyle|{\\mathrm{m+n}}=20,$ )  \n\n[0042] 作为亲水性双酚A型(甲基)丙烯酸酯的市售品的例子，可以列举由第一工业制药株式会社发售的New  Frontier(R)BPE-4(在式(1)中 ， $\\mathsf{R}^{1}$ 及 $\\mathrm{R}^{2}$ 是氢原子， ${\\mathfrak{m}}+{\\mathfrak{n}}=4.$ ) 、NewFrontier(R)BPE-10(在式(1)中， $\\mathbb{R}^{1}$ 及 $\\mathrm{R}^{2}$ 是氢原子， $\\mathrm{m+n}{=}10,$ )、New  Frontier(R)BPE-20(在式(1)中， $\\mathbb{R}^{1}$ 及 $\\mathrm{R}^{2}$ 是氢原子， $\\mathfrak{m}+\\mathfrak{n}=20\\AA,$ )、New  Frontier(R)BPEM-4(在式(1)中， $\\mathrm{R}^{1}$ 及 $\\mathrm{R}^{2}$ 是甲基， $\\mathtt{m}+\\mathtt{n}$ $=4)$ 、New  Frontier(R)BPEM-10(在式(1)中， $\\boldsymbol{\\mathrm{R}}^{1}$ 及 $\\mathrm{R}^{2}$ 是甲基， $\\mathrm{m+n}{=}10,$ )等New  Frontier(R)系列。  \n\n[0043] 亲水性双酚A型(甲基)丙烯酸酯相对于100质量 $\\%$ 防雾涂料组合物的总固体成分的比例以固体成分换算优选为50质量 $\\%$ 以上，更优选为60质量 $\\%$ 以上。通过含有以固体成分换算计为50质量 $\\%$ 以上的亲水性双酚A型(甲基)丙烯酸酯，能够获得可形成防雾特性，尤其是低温防雾性及亲水持续性优异的防雾被膜的防雾涂料组合物。上述比例的上限没有特别限定，但上限例如以固体成分换算计为90质量 $\\%$ 。  \n\n[0044] [(B)反应性非离子表面活性剂]  \n\n[0045] 本申请发明的防雾涂料组合物含有反应性非离子表面活性剂作为(B)成分。反应性非离子表面活性剂主要有助于提高防雾被膜的低温防雾性、提高亲水持续性以及减小接触角。  \n\n[0046] 非离子表面活性剂(非离子性表面活性剂)是具有在溶解于水的状态下不进行离子化的亲水基团的表面活性剂。其中，“反应性非离子表面活性剂”是在分子内具有反应性官能团的非离子表面活性剂。作为上述反应性官能团，例如可列举乙烯基、(甲基)丙烯酰基等含有不饱和键的基团，尤其是含有乙烯性不饱和键的基团。  \n\n[0047] 作为本申请的防雾涂料组合物含有的反应性非离子表面活性剂的例子，可列举由下述式(3)表示的结构的化合物。  \n\n[0048] [化3]  \n\n[0049]  \n\n![](images/341bf1429e3d923b564ce8073333d219eae543cd5ea278f9eb6e862605211c57.jpg)  \n\n[0050] (式中， $\\mathrm{R}^{3}$ 表示碳原子数8至36，且具有3个以上甲基的一价的支链脂肪族烃基或支链的脂肪族酰基，AO表示碳原子数2至4的氧化亚烷基，L表示由下述式(4)表示的基团，z表示1至10的数，X表示氢原子或下述的阴离子性亲水基团或阳离子性亲水基团(优选为氢原子)，m表示0至1000的数，n表示0至1000的数。)  \n\n[0051] [化4]  \n\n[0052]  \n\n[0053] (式中， $\\mathrm{R^{4}}$ 及 $\\mathrm{R}^{5}$ 表示氢原子或甲基，x表示0至12的数，y表示0或1的数。)  \n\n[0054] 阴离子性亲水基团： $\\mathrm{-SO_{3}M_{\\mathrm{\\ell}}-R^{6}-S O_{3}M_{\\mathrm{\\ell}}-R^{7}-C O O M_{\\mathrm{\\ell}}-P O_{3}M_{\\mathrm{\\ell}}-P O_{3}M H}$ 或 $-\\mathrm{C0-R^{8}-C00M}$ (式中，M表示氢原子、碱金属原子、碱土类金属原子或铵(其中，碱土类金属原子为1/2)， $\\mathrm{R}^{6}$ 及R7表示亚烷基， $\\mathrm{R}^{8}$ 表示从二元酸或其酸酐去除羧基后的残基。)  \n\n[0055] 阳离子性亲水基团： $-\\mathrm{R^{9}-N R^{10}R^{11}R^{12}\\bullet\\mathrm{~Y~}}$ 或 $_{\\mathrm{\\ell-Z-NR^{10}R^{11}R^{12}\\bullet\\mathrm{\\Upsilon}}}$ (式中， $\\mathrm{R}^{9}$ 表示亚烷基， $\\mathrm{R}^{10}$ 至 $\\mathrm{R}^{12}$ 表示碳原子数1至4的烷基、碳原子数2至4的链烷醇基或苄基，Y表示卤原子或甲基硫酸基团，Z表示由-CH2CH(OH)CH2-或-CH(CH2OH)CH2-表示的基团。)  \n\n[0056] 上述L优选为具有由下述式(5)表示的结构的基团。  \n\n[0057] [化5] [0058] $-C\\mathrm{{H_{2}-C H=C H_{2}}}$  \n\n[0059] 作为具有由上述式(3)表示的结构的化合物的具体例子，可列举具有由下述式(6)表示的结构的化合物。  \n\n[0060] [化6]  \n\n[0061]  \n\n$$\n\\begin{array}{r}{\\mathsf{C H}_{2}\\mathsf{O C H}_{2}\\mathsf{C H}=\\mathsf{C H}_{2}}\\\\ {\\mathsf{C}_{13}\\mathsf{H}_{27}\\mathsf{O}-\\mathsf{C H}_{2}\\mathsf{C H}-\\mathsf{O}-(\\mathsf{E O})_{\\mathrm{m}}-\\mathsf{H}}\\end{array}\n$$  \n\n(式中，EO是环氧乙烷，m是0至1000的数。)  \n\n[0063] 典型而言，上述式(6)的m为5以上50以下的整数，例如 $\\mathfrak{n}{=}10,20,30$ 或40。  \n\n[0064] 在作为具有由上述式(3)表示的结构的化合物的非离子表面活性剂中，作为市售品的例子，可列举Adekarea  Soap  ER-10、Adekarea  Soap  ER-20、Adekarea  Soap  ER-30、Adekarea  Soap  ER-40、Adekarea  Soap  SR系列以及Adekarea  Soap  SE系列(均为株式会社ADEKA制造)等。  \n\n[0065] 相对于100质量份(A)成分，(B)成分的含量优选为超过2质量份且20质量份以下。通过相对于100质量份(A)成分含有超过2质量份的(B)成分，能够更稳定地形成被膜透明度高的防雾被膜。此外，即使相对于100质量份(A)成分，(B)成分的含量超过20质量份，由于效果饱和，透明性、防雾特性也不会再提高，反而成本会增加。因此，相对于100质量份(A)成分，(B)成分的含量优选为20质量份以下。相对于100质量份的(A)成分，(B)成分的含量的上限更优选为18质量份。  \n\n[0066] [(C)反应性离子液体]  \n\n[0067] 本申请发明的防雾涂料组合物含有反应性离子液体作为(C)成分。离子液体是由阳离子和阴离子构成的离子以液体存在的物质。离子液体是盐，并且是熔点低、在室温附近下为液体的状态的物质。此外，“反应性离子液体”是包含具有反应性官能团的阳离子的物质。作为上述反应性官能团，例如可列举乙烯基、(甲基)丙烯酰基等含有不饱和键的基团，尤其是含有乙烯性不饱和键的基团。  \n\n[0068] 作为上述(C)成分的反应性离子液体的例子，可列举包含具有由下述化学式(7)或下述化学式(8)表示的反应性基团的离子结合性盐的反应性离子液体。[0069] [化7]  \n\n[0070]  \n\n[0071] [化8]  \n\n[0072]  \n\n[0073] (式中， $\\mathrm{R}^{13}$ 及 $\\mathrm{R}^{14}$ 分别独立地表示取代或无取代的碳原子数1至30的直链状、支链状或环状的烷基；取代或无取代的碳原子数6至30的芳基；被取代的或非取代的碳原子数7至31的芳烷基， $\\mathsf{A}^{1}$ 及 $\\mathrm{A}^{2}$ 是碳原子数2至4的直链状或支链状的亚烷基，n是0至50的整数， ${\\boldsymbol{\\mathrm{Q1}}}^{+}$ 及Q2分别独立地表示选自于由具有乙烯性不饱和键的铵离子、具有乙烯性不饱和键的咪唑鎓离子、具有乙烯性不饱和键的吡啶鎓离子、具有乙烯性不饱和键的吡咯烷鎓离子、具有乙烯性不饱和键的吡咯啉离子、具有乙烯性不饱和键的哌啶鎓离子、具有乙烯性不饱和键的吡嗪鎓离子、具有乙烯性不饱和键的嘧啶鎓离子、具有乙烯性不饱和键的三唑鎓离子、具有乙烯性不饱和键的三嗪鎓离子、具有乙烯性不饱和键的喹啉鎓离子、具有乙烯性不饱和键的异喹啉鎓离子、具有乙烯性不饱和键的吲哚鎓离子、具有乙烯性不饱和键的喹喔啉鎓离子、具有乙烯性不饱和键的哌嗪鎓离子、具有乙烯性不饱和键的噁唑啉鎓离子、具有乙烯性不饱和键的噻唑啉鎓离子以及具有乙烯性不饱和键的吗啉鎓离子组成的组中的至少一种。)  \n\n[0074] 相对于100质量份(A)成分，(C)成分的含量优选为1质量份以上5质量份以下。通过相对于100质量份(A)成分，含有1质量份以上的(C)成分，所获得的防雾被膜的防雾特性及亲水持续性成为充分的级别。此外，即使相对于100质量份(A)成分，(C)成分的含量超过5质量份，由于效果饱和，透明性、防雾特性也不会再提高，反而成本会增加。因此，相对于100质量份(A)成分，(C)成分的含量优选为5质量份以下。相对于100质量份(A)成为，(C)成分的含量的下限更优选为1.5质量份。上限更优选为3质量份。  \n\n[0075] (B)成分相对于(C)成分的含量比(B)/(C)优选是1以上10以下。通过使(B)成分的含量相对于上述(C)成分的含量以质量比计为1以上，能够更确实地获得可形成防雾特性，尤其是低温防雾性及亲水持续性优异的防雾被膜的防雾涂料组合物。此外，即使含有质量比(B)/(C)超过10，由于效果饱和，透明性、防雾特性也不会再发生变化，因此优选上限为10。  \n\n[0076] [(D)聚合引发剂]  \n\n[0077] 本实施方式涉及的防雾涂料组合物含有聚合引发剂作为(D)成分。作为聚合引发剂，可列举热聚合引发剂、光聚合引发剂等。其中由于可容易地进行涂布了防雾涂料组合物后的固化这一点，优选光聚合引发剂。进而，光聚合引发剂中优选由紫外线固化的光聚合引发剂。聚合引发剂既可以单独使用一种，也可以组合使用两种以上。  \n\n[0078] 聚合引发剂的量可根据需要适当设定。例如，优选适当地设定，以使相对于100质量份(A)成分的亲水性双酚A型(甲基)丙烯酸酯，(D)成分的聚合引发剂的量为1质量份以上50质量份以下，优选为5质量份以上30质量份以下的范围内。  \n\n[0079] [(E)季戊四醇(甲基)丙烯酸酯]  \n\n[0080] 除上述(A)至(D)成分以外，防雾涂料组合物还可以含有(E)季戊四醇(甲基)丙烯酸酯。  \n\n[0081] (E)成分的季戊四醇(甲基)丙烯酸酯有助于减小防雾被膜表面的接触角。通过上 述(B)成分及(C)成分的相乘效果，能够提高用热水清洗防雾被膜表面后，用布擦拭时的擦 拭掉水后的防雾性。进而，(E)成分有助于提高固化反应性及表面硬度。  \n\n[0082] 作为(E)成分的季戊四醇(甲基)丙烯酸酯的例子，可列举季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、己二醇(甲基)丙烯酸酯等。此外，由于能够赋予亲水性这一点，作为(E)成分的季戊四醇(甲基)丙烯酸酯，优选为环氧烷烃改性的季戊四醇(甲基)丙烯酸酯。  \n\n[0083] 作为市售的(E)季戊四醇(甲基)丙烯酸酯，可列举KAYARAD  DPHA(二季戊四醇五丙烯酸酯和二季戊四醇六丙烯酸酯的混合物)、KAYARAD  DPEA12(环氧乙烯改性二季戊四醇六丙烯酸酯)、KAYARAD  D-330(二季戊四醇三丙烯酸酯)、KAYARAD  D-320(二季戊四醇四丙烯酸酯)以及KAYARAD  D-310(二季戊四醇五丙烯酸酯)(均为日本化药株式会社制)等。其中优选环氧烷烃改性的KAYARAD  DPEA12(环氧乙烷改性的二季戊四醇六丙烯酸酯)。  \n\n[0084] 相对于100质量份(A)成分的亲水性双酚A型(甲基)丙烯酸酯，(E)成分的含量优选为5质量份以上，更优选为10质量份以上。通过相对于100质量份(A)成分的亲水性双酚A型(甲基)丙烯酸酯，含有5质量份以上的(E)成分，能够更加有助于减小接触角、提高擦拭掉水后的防雾性以及赋予防雾被膜柔软度。上限没有特别限制，例如为30质量份。  \n\n[0085] [(F)尿烷丙烯酸酯类树脂]  \n\n[0086] 防雾涂料组合物还可以含有(F)成分的尿烷(甲基)丙烯酸酯类树脂。尿烷丙烯酸酯类树脂可提高防雾涂料组合物的固化反应性。  \n\n[0087] 作为尿烷(甲基)丙烯酸酯类树脂，可列举多元醇化合物和有机聚异氰酸酯的反应产物。  \n\n[0088] 作为上述多元醇化合物，例如可列举乙二醇、丙二醇、新戊二醇、1,6-己二醇、3-甲基 $^{-1,5-},$ 戊二醇、1,9-壬二醇、2-乙基 $^{-2-}$ 丁基-1,3-丙二醇、三羟甲基丙烷、二乙二醇、二丙二醇、聚丙二醇、1 ,4-二羟甲基环己烷、双酚A聚乙氧基二醇、聚四亚甲基二醇等多元醇类；作为上述多元醇类与琥珀酸、马来酸、衣康酸、己二酸、氢化二元酸、邻苯二甲酸、间邻苯二甲酸、对苯二甲酸等多元酸或它们的酸酐类的反应产物的聚酯多元醇类；作为上述多元醇类与ε-己内酯的反应产物的聚己内酯多元醇类；上述多元醇类和上述多元酸或它们的酸酐类的 $\\mathrm{{\\mathfrak{E}}^{-}}$ 己内酯的反应产物；聚碳酸酯多元醇；聚合物多元醇等。  \n\n[0089] 作为上述有机聚异氰酸酯，例如可列举甲苯二异氰酸酯、异佛尔酮二异氰酸酯、苯二亚甲基二异氰酸酯、二苯甲烷-4,4’-二异氰酸酯、二环戊基二异氰酸酯、六亚甲基二异氰酸酯、2,4,4’-三甲基六亚甲基二异氰酸酯、2,2’-4-三甲基六亚甲基二异氰酸酯等。  \n\n[0090] 尿烷(甲基)丙烯酸酯类树脂优选含有尿烷(甲基)丙烯酸酯低聚物。尿烷(甲基)丙烯酸酯低聚物的重均分子量优选为300以上5000以下，更优选为300以上3000以下。  \n\n[0091] 作为市售的上述(F) 成分的尿烷(甲基) 丙烯酸酯类树脂，可列举艺术树脂(Artresin)系列(根上工业株式会社制)。  \n\n[0092] 相对于100质量份(A)成分的亲水性双酚A型(甲基)丙烯酸酯，(F)成分的含量优选为2质量份以上，更优选为3质量份以上。通过相对于100质量份(A)成分的亲水性双酚A型(甲基)丙烯酸酯，含有2质量份以上的(F)成分，可大大有助于赋予防雾被膜耐擦性(硬涂性)，或提高防雾涂料组合物的反应性。上限没有特别限制，例如为10质量份。此外，(F)成分更优选与上述的(E)成分合用。  \n\n[0093] [均化剂]  \n\n[0094] 本实施方式涉及的防雾涂料组合物还可以在不损害发明的效果的范围内含有其它添加成分。例如，本实施方式涉及的防雾涂料组合物还可以含有均化剂。通过含有均化剂，可提高防雾涂料组合物的涂布性。进而能够使防雾被膜和水的接触角减小，不易产生水滴。因此有助于提高防雾效果。  \n\n[0095] 作为上述均化剂，可列举硅类均化剂、氟类均化剂、丙烯酸类均化剂、乙烯类均化剂以及氟类和丙烯酸类复合化的均化剂等。均化剂既可以单独使用一种，或也可以组合使用两种以上。  \n\n[0096] 均化剂的量可根据需要适当设定。例如，适当地设定，以使相对于100质量份(A)成分的亲水性双酚A型(甲基)丙烯酸酯，均化剂的量为1质量份以上50质量份以下，优选为5质量份以上30质量份以下的范围内。  \n\n[0097] [相容剂]  \n\n[0098] 根据需要，防雾涂料组合物可以含有相容剂。上述相容剂可根据上述各成分的相容性适当选择。作为相容剂，例如可列举脂肪族(甲基)丙烯酸酯、脂环式(甲基)丙烯酸酯、芳香族(甲基)丙烯酸酯等。上述脂肪族(甲基)丙烯酸酯、脂环式(甲基)丙烯酸酯、芳香族(甲基)丙烯酸酯可包含羟基、氨基、缩水甘油基、羧酸基(羧基)、磷酸酯基等官能团或聚乙二醇链等改性基团。作为市售的相容剂，可列举Light-Ester系列、Light-Acrylate系列(均为共荣社化学株式会社制)等。相容剂的量可考虑各成分的溶解性适当调节。  \n\n[0099] [溶剂]  \n\n[0100] 根据需要，本实施方式涉及的防雾涂料组合物可以含有溶剂。作为溶剂，可列举甲基乙基酮、丙酮等酮类溶剂；酯类溶剂；PGM(丙二醇单甲醚)等二醇醚类溶剂；醇类溶剂等有机溶剂或水等。这些溶剂可考虑所添加的成分的溶解性适当选择。  \n\n[0101] 此外，考虑各成分的溶解性、组合物涂布性等设定防雾涂料组合物的溶剂的比例。其中，当溶剂的量过多时，涂膜的固化有容易变得不充分的倾向。此外，当溶剂的量过少时，防雾被膜的透明性有容易下降的倾向。防雾涂料组合物中的溶剂的比例没有特别限定，典型而言为防雾涂料组合物的总量的50质量 $\\%$ 以上80质量 $\\%$ 以下，优选为50质量 $\\%$ 以上70质量 $\\%$ 以下，更优选为55质量 $\\%$ 以上65质量 $\\%$ 以下。  \n\n[0102] [其它添加成分]  \n\n[0103] 进而，根据希望的特性，本实施方式涉及的防雾涂料组合物还可以含有除上述成分以外的造膜助剂、抑泡剂、稳定剂、填充剂、粘合促进剂、固化剂、固化促进剂、增塑剂、触变剂、颜料、抗氧化剂等公知的添加剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# [0104] [防雾涂料组合物]  \n\n[0105] 本实施方式涉及的防雾涂料组合物可通过如下方法制备：在甲基乙基酮(MEK)等溶剂中添加(A)亲水性双酚A型(甲基)丙烯酸酯、(B)反应性非离子表面活性剂、(C)反应性离子液体、(D)聚合引发剂、根据需要的(E)环氧乙烷改性二季戊四醇六丙烯酸酯、(F)尿烷(甲基)丙烯酸酯类树脂、均化剂以及其它需要的成分，并投入到搅拌机内搅拌。各成分的投入顺序没有特别限定，本领域技术人员可依照技术常识任意地调节。  \n\n[0106] 在本实施方式中，优选的防雾涂料组合物为相对于100质量份(A)亲水性双酚A型(甲基)丙烯酸酯，含有：1质量份以上20质量份以下、优选为1.5质量份以上18质量份以下的(B)反应性非离子表面活性剂；1质量份以上5质量份以下、优选为1.5质量份以上3质量份以下的(C)反应性离子液体；以及1质量份以上50质量份以下、优选为5质量份以上30质量份以下的(D)聚合性引发剂。(B)成分相对于(C)成分的含量比(B)/(C)更优选为1以上10以下。  \n\n[0107] 在本实施方式中，其它的优选的防雾涂料组合物为相对于100质量份(A)亲水性双酚A型(甲基)丙烯酸酯，含有：1质量份以上、优选为1.5质量份以上18质量份以下的(B)反应性非离子表面活性剂；1质量份以上5质量份以下、优选为1.5质量份以上3质量份以下的(C)反应性离子液体；1质量份以上50质量份以下、优选为5质量份以上30质量份以下的(D)聚合性引发剂；5质量份以上、更优选为10质量份以上且30质量份以下的(E)环氧乙烯改性二季戊四醇六丙烯酸酯；以及2质量份以上、更优选为3质量份以上且10质量份以下的(F)尿烷(甲基)丙烯酸酯类树脂。(B)成分相对于(C)成分的含量比(B)/(C)更优选为1以上10以下。  \n\n[0108] [防雾性透明片材]  \n\n[0109] 接着，对本实施方式涉及的防雾性透明片材进行说明。本实施方式的防雾性透明片材具备：透明的基材和配置于该基材表面的由上述防雾涂料组合物构成的防雾被膜。  \n\n[0110] 防雾性透明的防雾被膜可通过在基材上涂布上述涂料组合物，干燥涂膜而形成。此外，当防雾涂料组合物含有光聚合引发剂时，在涂布后，可通过照射紫外线等光来促进各成分的固化并形成防雾被膜。  \n\n[0111] 作为上述基材，优选玻璃、树脂制(塑料制)的片材或膜等透明的基材。作为上述透明的基材，例如可列举选自于聚对苯二甲酸乙二酯(PET)、聚碳酸酯、聚(甲基)丙烯酸酯等透明树脂的树脂制透明片材或透明膜。  \n\n[0112] 进而，上述防雾被膜具有优异的高温防雾性及低温防雾性。因此，可在较大范围温度环境下发挥防雾效果。此外，由于被膜透明性也优异，因此可用作不损害基材的外观、透过基材的外景图像的可见性的被膜。  \n\n[0113] [用途]  \n\n[0114] 本实施方式涉及的防雾涂敷剂可在较大范围温度环境下发挥防雾效果，并且防雾效果的持续性及被膜透明性优异。因此，可形成相对于塑料成形品、塑料膜、尤其是PET制的素材具有高紧贴性的防雾被膜。  \n\n[0115] 进而，具备由上述防雾涂敷剂构成的防雾被膜的防雾性透明片材还可以用作具备下面的基材的防雾性材料，所述基材是无机玻璃透镜、建筑物的窗户、浴室的窗户、镜子、汽车或火车、飞机、轮船等交通工具的窗户、用于滑雪、游泳等的护目镜、用于面罩、摩托车头盔等的防护罩等。  \n\n[0116] 实施例  \n\n[0117] 以下，参照实施例更具体地说明本发明。本发明的范围不限于这些实施例的记载。  \n\n[0118] 以下的实施例、比较例中配合的成分如下所示。  \n[0119] (A)亲水性双酚A型(甲基)丙烯酸酯(商品名New  Frontier  BPE20G，第一工业制药株式会社制)  \n[0120] (B)反应性非离子表面活性剂(商品名Adekarea  Soap  ER10，株式会社ADEKA制)[0121] (C)反应性离子液体(商品名JI62C01，日本乳化剂株式会社制)  \n[0122] (D)聚合引发剂(商品名DAROCUR(R)4265(50质量 $\\%2,4,6-$ 三甲基苯甲酰基二苯基氧化膦和50质量 $\\%2-$ 羟基 $-2-$ 甲基 $^{-1-}$ 苯基 $\\cdot^{-1-}$ 丙酮的混合物)，BASF  JAPAN株式会社制)[0123] (E)季戊四醇(甲基)丙烯酸酯  \n[0124] 环氧乙烯(EO)改性二季戊四醇六丙烯酸酯(KAYARAD  DPEA12，日本化药株式会社制)。  \n[0125] (F)尿烷(甲基)丙烯酸类树脂  \n[0126] 尿烷丙烯酸酯低聚物、反应性尿烷聚合物混合物(商品名Artresin  H135，根上工业株式会社制)  \n[0127] -相容剂  \n[0128] 2-羟乙基甲基丙烯酸酯(商品名Light-Ester  HO250N，共荣社化学株式会社制)[0129] -溶剂  \n[0130] MEK(甲基乙基酮)  \n[0131] -均化剂A  \n[0132] BYK3560(聚醚大分子单体(macromer)改性丙烯酸酯，BYK  Chemie  JAPAN株式会社制)  \n[0133] -均化剂B  \n[0134] DOW  CORNING(R)67  ADDITIVE(3-(聚氧乙烯)丙基七甲基三硅氧烷，固体成分浓度70质量 $\\%$ 至80质量 $\\%$ ，东丽道康宁株式会社制)  \n[0135] [防雾涂料组合物的制备及防雾被膜的形成]  \n[0136] 根据表1至表2所示的配合将规定量的上述各种成分投入到混炼机中，通过混炼获得防雾涂料组合物。将所获得的防雾涂料组合物涂布在作为基材的聚对苯二甲酸乙二酯(PET)的透明片材上，以使干燥后的膜厚成为大致 $10\\upmu\\mathrm{m}$ ，在 $80^{\\circ}\\mathrm{C}$ 下进行10分钟加热干燥，形成涂膜。通过使用输出密度120W/cm的高压汞灯，对在光源下 $12\\mathrm{{cm}}$ 的位置形成的涂膜以累积光量 $1000\\mathrm{mJ/cm^{2}}$ 照射紫外线使涂膜固化，形成防雾被膜。表2所示的配合与表1所示的配合相比，在进一步含有(E)季戊四醇(甲基)丙烯酸酯、(F)尿烷(甲基)丙烯酸酯类树脂这一点不同。  \n[0137] [防雾被膜的评价]  \n[0138] 接下来根据以下的评价项目对形成了防雾被膜的片材进行评价。评价项目及其评价顺序如下所示。  \n[0139] (1)被膜透明度  \n[0140] 对形成了防雾被膜的片材以目测观察评价被膜的透明度。在评价时，用目测观察透明性、有无雾度。在表1及表2中，对被膜透明的标识为 $^{66}+\\prime^{3}$ ”，对可在被膜上发现模糊、浑浊的标识为“-”。  \n[0141] (2)防雾性的评价  \n\n[0142] (2-1)通常条件下的防雾性的评价  \n\n[0143] 准备上面敞开的容器，注入 $50^{\\circ}\\mathrm{C}$ 至 $60^{\\circ}\\mathrm{C}$ 的温水。准备评价对象的复合片材，用该复合片材覆盖容器的敞开的面，防雾被膜一侧朝下。此时，防雾被膜的表面和温水表面的距离为 $100\\mathrm{mm}\\pm5\\mathrm{mm}$ 。保持静置，目测观察2分钟后的膜表面变化。在表1及表2中，对通过目测观察的结果为复合片材整体透明，并且透过片材可见片材相反一侧的外景的标识为 $^{66}+^{39}$ ”；对片材模糊，并且透过片材不可见片材相反一侧的外景的标识为“-”。  \n\n[0144] (2-2)低温防雾性的评价  \n\n[0145] 将评价对象的复合片材在 $.-15^{\\circ}\\mathrm{C}$ 的环境下放置10分钟，然后取出到室温 $20^{\\circ}\\mathrm{C}\\pm5$ 的环境。观察从室温环境取出后经过60秒后的防雾被膜的表面的模糊情况。在表1及表2中，对通过目测观察的结果为复合片材整体透明，并且透过片材可见片材相反一侧的外景的标识为 $^{66}+\\prime^{3}$ ”；对片材模糊，并且透过片材不可见片材相反一侧的外景的标识为“-”。  \n\n[0146] (2-3)高温防雾性的评价[0147] (i)标准  \n\n[0148] 准备上面敞开的容器，注入 $80^{\\circ}\\mathrm{C}\\pm5$ 的温水。准备评价对象的复合片材，用该复合片材覆盖容器的敞开的面，防雾被膜一侧朝下。此时，防雾被膜的表面和温水表面的距离为$100\\mathrm{mm}\\pm5\\mathrm{mm}$ 。保持静置，观察2分钟后的膜表面变化。在表1及表2中，对通过目测观察的结果为复合片材整体透明，并且透过片材可见片材相反一侧的外景的标识为“ $^{\\boldsymbol{\\mathfrak{\\omega}}}+^{\\mathfrak{p}}$ ”，对片材模糊，并且透过片材不可见片材相反一侧的外景的标识为“-”(下述(ii)、(iii)也同样)。  \n\n[0149] (ii)耐水试验1的高温防雾性的评价[0150] 将评价对象的复合片材浸渍在 $20^{\\circ}\\mathrm{C}$ 至 $30^{\\circ}\\mathrm{C}$ 的室温水中，静置2小时。从常温水中取出片材，使其干燥。干燥后，按照上述“(i)标准”所示的顺序评价片材的高温防雾性。  \n\n[0151] (iii)耐水试验2的高温防雾性的评价[0152] 将评价对象的复合片材浸渍在 $75\\mathrm{{^\\circC}}$ 至 $85^{\\circ}\\mathrm{C}$ 的温水中，静置2小时。从温水中取出片材，使其干燥。干燥后，按照上述“(i)标准”所示的顺序评价片材的高温防雾性。  \n\n[0153] 将比较例1、2及实施例1至14的配合以及被膜透明度和防雾性的评价结果示于表1及表2。在配合的栏中记载的数字表示质量份。  \n\n[0154] 表1  \n\n[0155]  \n\n<html><body><table><tr><td rowspan=\"2\"></td><td colspan=\"2\">比较例</td><td colspan=\"7\">实施例</td></tr><tr><td>1</td><td>2</td><td>1</td><td>2</td><td>3</td><td>4</td><td>5</td><td>6</td><td>7</td></tr><tr><td>(A)</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td></tr><tr><td>(B)</td><td></td><td></td><td>2</td><td>4</td><td>6</td><td>8</td><td>10</td><td>12</td><td>14</td></tr><tr><td>(C)</td><td></td><td>2</td><td>2</td><td>2</td><td>2</td><td>2</td><td>2</td><td>2</td><td>2</td></tr><tr><td>(D)</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td></tr><tr><td>相容剂</td><td></td><td>4</td><td>4</td><td>4</td><td>4</td><td>4</td><td>4</td><td>4</td><td>4</td></tr><tr><td>均化剂A</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td></tr><tr><td>均化剂B</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>MEK</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td></tr><tr><td>合计</td><td>216</td><td>222</td><td>224</td><td>226</td><td>228</td><td>230</td><td>232</td><td>234</td><td>236</td></tr><tr><td><被膜透明度></td><td>+</td><td></td><td>+*1)</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td></tr><tr><td colspan=\"10\"><防雾性></td></tr><tr><td>通常条件</td><td></td><td></td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td></tr><tr><td>低温防雾性</td><td></td><td></td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td></tr><tr><td colspan=\"10\">（高温防雾性）</td></tr><tr><td>标准</td><td></td><td></td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td></tr><tr><td>耐水试验1</td><td></td><td></td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td></tr><tr><td>耐水试验2</td><td></td><td></td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td></tr></table></body></html>  \n\n[0156] $\\star1)$ 虽然是允许范围，但多少有点模糊[0157] 表2  \n\n[0158]  \n\n<html><body><table><tr><td rowspan=\"2\"></td><td colspan=\"7\">实施例</td></tr><tr><td>8</td><td>9</td><td>10</td><td>11</td><td>12</td><td>13</td><td>14</td></tr><tr><td>(A)</td><td>80</td><td>80</td><td>80</td><td>80</td><td>80</td><td>80</td><td>80</td></tr><tr><td>(B)</td><td>2</td><td>4</td><td>6</td><td>8</td><td>10</td><td>12</td><td>14</td></tr><tr><td>(C)</td><td>2</td><td>2</td><td>2</td><td>2</td><td>2</td><td>2</td><td>2</td></tr><tr><td>(D)</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td></tr><tr><td>(E)</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td></tr><tr><td>(F)</td><td>4</td><td>4</td><td>4</td><td>4</td><td>4</td><td>4</td><td>4</td></tr><tr><td>相容剂</td><td>6</td><td>6</td><td>6</td><td>6</td><td>6</td><td>6</td><td>6</td></tr><tr><td>均化剂A</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td></tr><tr><td>均化剂B</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>MEK</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td></tr><tr><td>合计</td><td>220</td><td>222</td><td>224</td><td>226</td><td>228</td><td>230</td><td>232</td></tr><tr><td><被膜透明度></td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td></tr><tr><td colspan=\"8\"><防雾性></td></tr><tr><td>通常条件</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td></tr><tr><td>低温防雾性</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td></tr><tr><td colspan=\"8\">（高温防雾性）</td></tr><tr><td>标准</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td></tr><tr><td>耐水试验1</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td></tr><tr><td>耐水试验2</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td><td>+</td></tr></table></body></html>  \n\n[0159] 如表1的评价结果所示，在(B)反应性非离子表面活性剂和(C)反应性离子液体的任一方均不含有的比较例1中，被膜透明度的评价为透明，但如对防雾性的评价结果所示，几乎未看到防雾效果。  \n\n[0160] 此外，在相对于比较例1的配合，进一步含有(C)反应性离子液体和促进各成分的相容的相容剂的比较例2中，也几乎未看到防雾效果。  \n\n[0161] 相对于此，在含有(B)反应性非离子表面活性剂和(C)反应性离子液体两者的实施例1至14中，对于各防雾性的评价，均发挥了良好的防雾性。  \n\n[0162] 实施例1至14中，在实施例1(相对于100质量份(A)亲水性双酚A型(甲基)丙烯酸酯，(B)反应性非离子表面活性剂的量为2质量份的例子)中，在被膜透明度的评价中多少能够观察到被膜产生模糊。在除此以外的实施例(实施例2至14)中，全部的被膜为透明。当像这样(B)反应性非离子表面活性剂的量为2质量份时，有时能获得被膜透明度不足的防雾被膜。由该结果可知，为了发挥高防雾性，同时更稳定地形成被膜透明度高的防雾被膜，优选相对于100质量份(A)亲水性双酚A型(甲基)丙烯酸酯，(B)反应性非离子表面活性剂的量为超过2质量份，更优选为4质量份以上。  \n\n[0163] 如此，可知由本申请发明的防雾涂料组合物获得的防雾被膜及具备该防雾被膜的防雾性透明片材具有优异的防雾性(常温、低温、高温的全部的防雾性)。进而，通过使(B)反应性非离子表面活性剂的量超过2质量份，可更稳定地形成被膜透明度高的防雾被膜。  \n\n[0164] (3)耐水洗性的评价  \n\n[0165] 准备评价对象的复合片材，在 $30^{\\circ}\\mathrm{C}$ 至 $40^{\\circ}\\mathrm{C}$ 的温水中用手对防雾被膜的表面边揉搓边清洗10次，然后用布擦拭掉水分，使片材干燥。接着，准备上面敞开的容器，注入 $50^{\\circ}\\mathrm{C}$ 至60$\\mathrm{{^\\circC}}$ 的温水。准备干燥后的片材，用该复合片材覆盖容器的敞开的面，防雾被膜一侧朝下。此时，防雾被膜的表面和温水表面的距离为 $100\\mathrm{mm}\\pm5\\mathrm{mm}$ 。保持静置，目测观察2分钟后的膜表面变化。按照模糊少的顺序以4阶段(级别 $\\scriptstyle\\mathrm{A\\longrightarrowB\\longrightarrowC\\longrightarrowD})$ )评价防雾性。级别A至C是允许水平。级别D是由于模糊而片材不透明，是不能够经受实用的水平。将评价结果示于表3及表4。表3所示的配合与表1相同。此外，表4所示的配合与表2相同。  \n\n[0166] 表3  \n\n<html><body><table><tr><td rowspan=\"2\"></td><td colspan=\"2\">比较例</td><td colspan=\"7\">实施例</td></tr><tr><td>1</td><td>2</td><td>1</td><td>2</td><td>3</td><td>4</td><td>5</td><td>6</td><td>7</td></tr><tr><td>(A)</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td></tr><tr><td>(B)</td><td></td><td></td><td>2</td><td>4</td><td>6</td><td>8</td><td>10</td><td>12</td><td>14</td></tr><tr><td>(C)</td><td></td><td>2</td><td>2</td><td>2</td><td>2</td><td>2</td><td>2</td><td>2</td><td>2</td></tr><tr><td>(D)</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td></tr><tr><td>相容剂</td><td></td><td>4</td><td>4</td><td>4</td><td>4</td><td>4</td><td>4</td><td>4</td><td>4</td></tr><tr><td>均化剂A</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td></tr><tr><td>均化剂B</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>MEK</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td></tr><tr><td>合计</td><td>216</td><td>222</td><td>224</td><td>226</td><td>228</td><td>230</td><td>232</td><td>234</td><td>236</td></tr><tr><td>耐水洗性</td><td>D</td><td>D</td><td>C</td><td>C</td><td>C</td><td>C</td><td>B</td><td>B</td><td>B</td></tr></table></body></html>  \n\n[0167]  \n\n[0168] 表4  \n\n<html><body><table><tr><td rowspan=\"2\"></td><td colspan=\"7\">实施例</td></tr><tr><td>8</td><td>9</td><td>10</td><td>11</td><td>12</td><td>13</td><td>14</td></tr><tr><td>(A)</td><td>80</td><td>80</td><td>80</td><td>80</td><td>80</td><td>80</td><td>80</td></tr><tr><td>(B)</td><td>2</td><td>4</td><td>6</td><td>8</td><td>10</td><td>12</td><td>14</td></tr><tr><td>(C)</td><td>2</td><td>2</td><td>2</td><td>2</td><td>2</td><td>2</td><td>2</td></tr><tr><td>(D)</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td></tr><tr><td>(E)</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td></tr><tr><td>(F)</td><td>4</td><td>4</td><td>4</td><td>4</td><td>4</td><td>4</td><td>4</td></tr><tr><td>相容剂</td><td>6</td><td>6</td><td>6</td><td>6</td><td>6</td><td>6</td><td>6</td></tr><tr><td>均化剂A</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td></tr><tr><td>均化剂B</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>MEK</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td></tr><tr><td>合计</td><td>220</td><td>222</td><td>224</td><td>226</td><td>228</td><td>230</td><td>232</td></tr><tr><td>耐水洗性</td><td>C</td><td>B</td><td>A</td><td>A</td><td>A</td><td>B</td><td>B</td></tr></table></body></html>  \n\n[0169]  \n\n[0170] 如表3的评价结果所示，在(B)反应性非离子表面活性剂和(C)反应性离子液体均不含有的比较例1或不含有(B)反应性非离子表面活性剂的比较例2中，耐水洗性为D级别，不充分。相对于此，在含有(B)反应性非离子表面活性剂和(C)反应性离子液体两者的实施例1至7中，耐水洗性提高到C至B级别。  \n\n[0171] 此外，如表4所示的结果，通过进一步包含(E)季戊四醇(甲基)丙烯酸酯、(F)尿烷(甲基)丙烯酸酯类树脂，耐水洗性提高。尤其是在相对于100质量份(A)亲水性双酚A型(甲基)丙烯酸酯，包含：6质量份以上10质量份以下的(B)反应性非离子表面活性剂、2质量份(C)反应性离子液体、8质量份(D)聚合性引发剂、10质量份(E)季戊四醇(甲基)丙烯酸酯和4质量份(F)尿烷(甲基)丙烯酸酯类树脂时(实施例10至12)，示出A级别的优异的耐水洗性。即，明确了由于提高耐水洗性这一点，优选除了上述(A)至(D)成分，进一步包含上述(E)成分及(F)成分。  \n\n[0172] (4)防雾被膜的硬度  \n\n[0173] 对于包含上述(E)成分及(F)成分的实施例8至14的防雾涂料组合物，评价进一步由该防雾涂料组合物形成的防雾被膜的表面硬度。为了评价，测量防雾被膜表面的铅笔硬度。将结果示于表5中。  \n\n[0174] 表5  \n\n[0175]  \n\n<html><body><table><tr><td rowspan=\"2\"></td><td colspan=\"7\">实施例</td></tr><tr><td>8</td><td>9</td><td>10</td><td>11</td><td>12</td><td>13</td><td>14</td></tr><tr><td>(A)</td><td>80</td><td>80</td><td>80</td><td>80</td><td>80</td><td>80</td><td>80</td></tr><tr><td>(B)</td><td>2</td><td>4</td><td>6</td><td>8</td><td>10</td><td>12</td><td>14</td></tr><tr><td>(C)</td><td>2</td><td>2</td><td>2</td><td>2</td><td>2</td><td>2</td><td>2</td></tr><tr><td>(D)</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td><td>8</td></tr><tr><td>(E)</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td></tr><tr><td>(F)</td><td>4</td><td>4</td><td>4</td><td>4</td><td>4</td><td>4</td><td>4</td></tr><tr><td>相容剂</td><td>6</td><td>6</td><td>6</td><td>6</td><td>6</td><td>6</td><td>6</td></tr><tr><td>均化剂A</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td></tr><tr><td>均化剂B</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>MEK</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td></tr><tr><td>合计</td><td>220</td><td>222</td><td>224</td><td>226</td><td>228</td><td>230</td><td>232</td></tr><tr><td>铅笔硬度</td><td>H</td><td>2B</td><td>2B</td><td>2B</td><td>4B</td><td>4B</td><td>4B</td></tr></table></body></html>  \n\n[0176] 如表5所示，当在包含(E)成分及(F)成分的状态下，增加(B)反应性非离子表面活性剂的量时，防雾被膜表面渐渐变得柔软。从防雾被膜的表面硬度的观点出发，尤其优选相对于100质量份(A)亲水性双酚A型(甲基)丙烯酸酯，包含4质量份以上8质量份以下的(B)反应性非离子表面活性剂、2质量份(C)反应性离子液体、8质量份(D)聚合性引发剂、10质量份(E)季戊四醇(甲基)丙烯酸酯和4质量份(F)尿烷(甲基)丙烯酸酯类树脂(实施例9至11)。[0177] (总结)  \n[0178] 由以上的结果可知，通过本申请发明涉及的具有特定组成的防雾涂料组合物，能够形成不仅防雾被膜刚刚形成后的初始防雾性(例如高温防雾性、低温防雾性)优异，防雾效果可长时间持续的防雾持续性也优异的防雾被膜。此外，通过除上述(A)至(D)成分之外，含有(E)成分及(F)成分，能够获得耐水洗性优异，赋予了柔软度的防雾被膜。  \n[0179] 本申请公开的实施方式及实施例全部为示例，应理解不从任何方面限定发明的范围。本发明的范围不只限于所述意思，也包含了权利要求书表示的、和权利要求书等同的意思以及范围内全部的变化。  \n[0180] 工业可利用性  \n[0181] 本申请的防雾涂料组合物及防雾性透明片材在寻求可长时间持续防雾效果的各种领域尤其能够有利地应用。",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,187 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (12) United States Patent Harkal et al.",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (54) WATERDISPERSIBLEEPOXY URETHANE COMPOUNDSANDCOATING COMPOSITIONS  \n\n(75) Inventors: Umesh D. Harkal, Fargo, ND (US); Andrew J.Muehlberg, Fargo, ND (US); Peter A.Edwards, Cokato, MN (US); Dean C. Webster, Fargo, ND (US)  \n\n(73)Assignee: NDSU RESEARCH FOUNDATION, Fargo, ND (US)  \n\n(\\*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 309 days.  \n\n(21) Appl. No.: 12/840,019 (22) Filed: Jul. 20,2010",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# Prior Publication Data  \n\nUS 2011/0263753A1 Oct.27,2011",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# Related U.S. Application Data  \n\n(63） Continuation-in-part of application No. 11/882,754, filed on Aug.3, 2007, now Pat.No.7,776,956, and a (Continued)  \n\n(51) Int. Cl. C09D 175/00 (2006.01) C08G 18/28 (2006.01) (Continued)  \n\n(52) U.S. Cl. CPC ..... C08G 18/2845 (2013.01); C08G 18/2805 (2013.01); C08G 18/706 (2013.01); (Continued)  \n\n(58) Field of Classification Search CPC C09D 175/08; C09D 163/06; C08G 18/2805; C08G 18/2845 (Continued)  \n\n(10) Patent No.: (45) Date of Patent:",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# References Cited",
+        "category": " References"
+    },
+    {
+        "id": 6,
+        "chunk": "# U.S. PATENT DOCUMENTS  \n\n3,484,413 A \\* 12/1969 Kaufman 528/49 3,894.922A\\* 7/1975 Bosso et al. 204/499 (Continued)",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# FOREIGNPATENTDOCUMENTS  \n\nWO 99/03905 A1 1/1999 WO WO 02/31021 A1 4/2002 (Continued)  \n\nOTHERPUBLICATIONS  \n\nBayhydur XP 7l65: Water Dispersible Polyisocyanate, Product Information. Sep. 2002.  \n\n(Continued)  \n\nPrimary Examiner—Michael L Leonard (74) Attorney, Agent, or Firm — J.A. Lindeman & Co., PLLC",
+        "category": " References"
+    },
+    {
+        "id": 8,
+        "chunk": "# ABSTRACT  \n\n环氧氨基甲酸酯 氨基甲酸缩水甘油 The invention relates to novel aqueous coating compositions containing epoxy urethane (glycidyl carbamate) functional resin. An aqueous coating composition comprises a polyfunctional oligomer having at least two epoxy urethane functional groups and a polyalkylene oxide chain, an optional surfactant, and water. The aqueous coating compositions of the invention can be dispersed in water with or without added surfactants to form a dispersion containing no volatile organic solvent. The invention provides a method for making aqueous coating compositions containing epoxy urethane functional resin as well. Water-dispersible epoxy urethane compounds of the aqueous coating compositions are also provided.",
+        "category": " Abstract"
+    },
+    {
+        "id": 9,
+        "chunk": "# 19 Claims, 7 Drawing Sheets  \n\n![](images/b8df5d6ada3de48e5e309c69f482ca45a6c2beaa49fdab875746b7f9db696f78.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# Related U.S. Application Data  \n\ncontinuation-in-part of application No. 12/680,401, filed as application No. PCT/US2008/078112 on Sep. 29,2008.  \n\n(60） Provisional application No. 60/835,433, filed on Aug. 4,2006, provisional application No.61/321,713,filed on Apr. 7, 2010, provisional application No. 60/976,072, filed on Sep.28, 2007.  \n\n(51) Int. Cl. C09D 163/06 (2006.01) C09D 175/08 (2006.01) C08G 18/70 (2006.01) C08G 59/50 (2006.01) C09D 163/00 (2006.01)  \n\n(52) U.S. CI. CPC C08G 59/5026 (2013.01); C09D 163/00 (2013.01); C09D 163/06 (2013.01); C09D 175/08 (2013.01)  \n\n(58) Field of Classification Search USPC 524/591,839,840 See application file for complete search history.",
+        "category": " References"
+    },
+    {
+        "id": 11,
+        "chunk": "# References Cited",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# U.S. PATENT DOCUMENTS  \n\n4,397,993A 8/1983 Tefertiller et al. 4,950,722 A 8/1990 Parker 5,043,381 A 8/1991 Coogan et al. 5,481,027 A \\* 1/1996 Kirchner C07C 275/62 252/8.61 5,717,054 A \\* 2/1998 Schultz C07D 303/22 257/E21.505 6,100,326 A 8/2000 Richter et al. 6,172,159 B1 1/2001 Gaal, Jr. et al. 6,849,337 B2 \\* 2/2005 Ohrbom C08G 18/2845 106/287.22   \n2002/0103319 A1\\* 8/2002 Ohrbom et al. 526/312   \n2010/0285311 A1\\* 11/2010 Steidl et al. 428/339   \n2010/0319580 A1\\* 12/2010 Webster et al. 106/287.2",
+        "category": " References"
+    },
+    {
+        "id": 13,
+        "chunk": "# FOREIGN PATENT DOCUMENTS  \n\nWO 03/060026 A1 7/2003   \nWO 2009/042999 A1 4/2009",
+        "category": " References"
+    },
+    {
+        "id": 14,
+        "chunk": "# OTHERPUBLICATIONS  \n\nHsia Hung-Chung et al., “Glycidyl-Terminated Polyurethane Modified Epoxy Resins: Mechanical Properties, adhesion Properties and Morphology,\" Journal of. Applied.Polymer. Science., 52:1137-1151 (1994).   \nPeter A Edwards et al., “Novel Polyurethane Coating Technology Through Glycidyl Carbamate Chemistry,” JCT Research, 2(7): 517-527 (2005).   \nPeter A. Edwards et al., “Synthesis and Self-Crosslinking of Glycidyl Carbamate Functional Oligomers,” Polymer Preprints., 44(1):54 (2003).   \nDieter Dieterich,“Die Angewandte Makromolekulare Chemie,\" pp. 133-165 (1981).   \nByung Kyu Kim et al., “Waterborne Polyurethanes and Their Properties,\" Journal of Polymer Science: Part A: Polymer Chemistry, 34:1095-1104 (1996). Michael Dvorchak et al.,“A New Water Reducible Blocked Polyisocyanate (NWRBP) for One Component (IK） Polyurethane Coatings,” Proceedings of the International Waterborne，HighSolids, and Powder Coatings Symposium, pp. 405-419 (2000). John A. Escarsega et al., “Water-Reducible PUR Coatings for Military Applications,” Modem Paint and Coatings, pp. 21-30 (1997).   \nMelissa A. Grunlan et al., “Waterborne Coatings with an Emphasis on Synthetic Aspects; An Overview,\" American Chemical Society Symposium Series, pp. 1-26 (1997).   \nRoy E.Hartz,“Reaction During Cure of a Blocked IsocyanateEpoxy Resin Adhesive,\" Journal of Applied Polymer Science, 19:735-746 (1975).   \nAnthony Page et al., “Polyester Resins in Water-Based Urethanes,\" Paint & Ink International, 9(2):37-40 (1996).   \nMichael J. Dvorchak et al., “Water-Reducible Unsaturated Polyester Polymers as Binder for UV-Curable Furniture Coatings,\" Proceedings of the Waterborne, High-Solids, and Powder Coatings Symposium, pp. 253-267 (1989).   \nZhiming W Ang et al.,\"Synthesis and Characterization of UVCurable Waterborne Polyurethane-Acrylate Ionomers for Coatings,\"Journal of Applied Polymer Science, 73:2869-2876 (1999). Jjan-wen Yang et al., “Chain-extended UV-Curable Waterborne Polyurethane-Acrylate,” Gaofenzi Cailiao Kexue Yu Gongcheng, 19(2):199-202 (2003) (with English Abstract).   \nJong Yoon Jang et al.,“Effect of Process Variables on Molecular Weight and mechanical Properties of War-Based Polyurethane Dispersion,\" Colloids and Surfaces, A: Physicochemical and Engineering Aspects, 196:135-143 (2002).   \nG. Guenduez et al.,“Structure-Property Study of Waterborne Polyurethane Coatings with Different Hydrophilic Contents and Polyols,\"Journal ofDispersion Scienceand Technology,25(2):- 228 (2004).   \nQu Jinqing et al.,“Synthesis of High Solid Content Waterborne Polyurethane Dispersion,\"Huagong Xuebao, 54(6):868-871 (2003) (with English Abstract).   \nXiao-hui Song et al, “Effect of PEG Molecular Weight in Hydrophilic Segment on the Crystallization of Cast Film of Waterborne Polyurethane,” Xiamen Daxue Xuebao, Ziran Kexueban, 41(4):463-467 (2002).   \nD.D.Web,“Urethane Systems Reactivity Measurement,\" Journal of Cellular Plastics, pp. 208-212 (1985).   \nH.-W. Ilger et al., “Reaction Kinetics Study of High Resilient Polyurethane Foams,\" Polyurethanes World Congress. pp.305-310 (1987).   \nChen et al., “Preparation and Characterization of Cryogenic Adhesives. I. Glycidyl-Terminated Polyurethane Resins,” J. Applied Polymer Science 51:1199-1206 (1994).   \nFarissey et al.,“The Rearrangement of Glycidyl N-Phenylcarbamate,”Journal of Heterocyclic Chemistry 7:331-333 (1970).   \nEdwards, et al., “Synthesis and Characterization of Glycidyl Carbamate Functional Oligomers,\" Polymer Preprints 44 (1):144- 145 (2003).   \nEdwards, et al.,“Kinetics and Cure of Glycidyl Carbamate Functional Oligomers,\" Polymeric Materials: Science and Engineering 90:455-456 (2004).   \nEdwards, et al.,“Cure Properties of Glycidyl Carbamate Functional Oligomers Reacted with Amines,\"Polymer Preprints 45(1):935-936 (2004).   \nEdwards, et al.,“Synthesis, characterization and self-crosslinking of glycidyl carbamate functional resins,\" Prog. Org. Coat. 57:128-139 (2006).   \nInternational Search Report for PCT/US2008/078112 dated Dec. 24,2008.   \nInternational Preliminary Report on Patentability of PCT/US2008/ 078112 dated Mar. 30, 2010.  \n\n\\* cited by examiner  \n\n![](images/d5fc1860c12118328ea2a2e2fa4d603e614a2105a975d960d8a1e0beb27d497e.jpg)  \nFIG. 1  \n\n![](images/5cf04648a96af4c457eba0c2df8b388f4b8b1c4ca958cb37c647b13893aac17d.jpg)  \n\nFIG.2 SCHEMATIC REPRESENTATION OF THE SYNTHESIS OF WATER DISPERSIBLE GLYCIDYL CARBAMATE RESINS  \n\n![](images/a7a77a8f3af607afe869c98b18b2544d2a691b6f6b3c58d6da813d1e33f47911.jpg)  \nFigure 3: $i j_{\\zeta}$ NMR spectrum of resin R1.  \n\n![](images/923c9a791233945fb3fbaacc8e9226f79a1c395d781e62c1b4fccb75fa4b081d.jpg)  \nFIG.4  \n\n![](images/1586a814fd9d50f49da00203205527c67e2043915c681b5973858460fffd9b10.jpg)  \n\nFIG.5 SCHEMATICREPRESENTATIONOFTHEDISPERSEDPARTICLEOF GLYCIDYLCARBAMATERESIN INWATER.  \n\n![](images/6e7da1790e52c17c5f1a1d43a450b9781a94c9fb250334277b976df15d5874d5.jpg)  \n\n![](images/d385338d7f7f0f805e091aecc7cb9020e869ca4f03efff45f55dd78bc2bbb7dd.jpg)  \nFigure 7: Water contact angle of the glycidyl carbamate coatings.",
+        "category": " References"
+    },
+    {
+        "id": 15,
+        "chunk": "# 2",
+        "category": " Introduction"
+    },
+    {
+        "id": 16,
+        "chunk": "# 1 WATERDISPERSIBLEEPOXYURETHANE COMPOUNDS AND COATING COMPOSITIONS  \n\nCROSS REFERENCE TO RELATED APPLICATIONS  \n\nThis application is a continuation-in-part of U.S. Nonprovisional application Ser. No. 11/882,754, filed 3 Aug. 2007,now U.S.Pat.No.7,776,956, issued 17 Aug.2010, which claims the benefit of U.S. Provisional Application Ser. No. 60/835,433, filed 4 Aug. 2006, both of which are incorporated herein by reference. This application also claims the benefit of U.S. Provisional Application Ser. No. 61/321,713, filed 7 Apr. 2010, which is incorporated herein by reference. This application is also a continuation-in-part of U.S. Nonprovisional application Ser. No. 12/680,401, filed 8 Sep. 2010, which is a National Stage application of International PCT application PCT/US2008/078112, filed 29 Sep. 20o8, which claims the benefit of U.S. Provisional Application Ser.No. 60/976,072, filed 28 Sep.2007, all of which are incorporated herein by reference.",
+        "category": " References"
+    },
+    {
+        "id": 17,
+        "chunk": "# GOVERNMENTRIGHTS  \n\nThis invention was funded at least in part by funds from the U.S. Government (Grant Nos. NVY-1S-2025/617 NDSU, NVY-1S-2026/620 NDSU， FA9550-09-C-0150 (prime), and 861-NVY-2S/NDSU Prime:N00024-05-C4139). The U.S. Government may, therefore, have certain rights in this invention.",
+        "category": " References"
+    },
+    {
+        "id": 18,
+        "chunk": "# FIELDOFTHEINVENTION  \n\nThe invention relates to novel aqueous coating compositions comprising a polyfunctional oligomer having at least two epoxy urethane functional groups and a hydroxylated polyalkylene oxide chain, an optional surfactant, and water. These compositions can be dispersed in water with or without added surfactants to form a dispersion containing no volatile organic solvents. The dispersed polymer can selfcrosslink and can also crosslink with multifunctional amine compounds into a hard, glossy, solvent resistant coating.",
+        "category": " Introduction"
+    },
+    {
+        "id": 19,
+        "chunk": "# BACKGROUND OF THE INVENTION  \n\nThermosetting polymers systems are widely used in many applications including protective coatings, composite materials, and adhesives. Many of these systems involve the reaction of polymers or oligomers with other materials containing mutual reactive groups. For example, hydroxyl functional polymers are crosslinked with functional oligomers,or epoxy resins are crosslinked with polyfunctional amines.  \n\nThe final properties of thermoset coatings are determined by the composition of the reactants used. Epoxy coatings generally exhibit good corrosion performance while polyurethane systems result in coatings having good toughness, abrasion resistance, and durability. Epoxy urethane (glycidyl carbamate) chemistry has the potential of combining epoxy and polyurethane technology into a single system and has been shown to improve toughness in epoxy-amine systems (Hsia H. C. et al., “Glycidyl-Terminated Polyurethane Modified Epoxy Resins: Mechanical Properties, adhesion Properties and Morphology\", J. Appl. Polym. Sci.,52,1134 (1994) and Edwards, P. A. et al., “Novel Polyurethane coating Technology Through Glycidyl Carbamate Chemistry\", JCT Research, 2, 517, (2005)).  \n\nEpoxy urethane (glycidyl carbamate) group is readily synthesized from the reaction of an isocyanate with glycidol:  \n\n![](images/1d846ffcc628e152b0e0ed0a5f71eff32362b5b4f1deb14ddb45cb61cefd5b0f.jpg)  \n\n15 (Tefertiller, N. B.et al., U.S. Pat. No. 4,397,993; Edwards, P. E. et al., Synthesis and Self-Crosslinking of Glycidyl Carbamate Functional Oligomers, Polymer Preprints 2003, 44(1), 54.)  \n\nEpoxy urethane (glycidyl carbamate) functional polymers   \n20 offer some unique opportunities in the formation of thermosetting polymers because the reactivity of an epoxy resin is combined with the physical properties obtained with polyurethanes. Epoxy urethane (glycidyl carbamate) functional oligomers can thermally self-crosslink and also crosslink   \n25 with multifunctional amines. Kinetic experiments have shown that the glycidyl carbamate epoxy is more reactive than conventional glycidyl ether epoxides. Physical properties of the coatings are also excellent and have an excellent combination of both hardness and flexibility.   \n30 There is an increased interest in developing water-dispersible coating compositions to meet the environmental standards. The preparation of conventional polyurethane dispersions is well known in the art (Dietrich, D., Die Ang. Makromol.Chem.,1981,98,133-165; Kim., B.K.et al., J.   \n35Polym.Sci.Polym.Chem.Ed.,1996, Vol.34,1095-1104; Coogan, R. G. et al., U.S. Pat.No. 5,043,381). Waterborne polyurethane dispersions (PUD) require many process steps but yield good properties and are one of popular methods in reducing volatile organic compounds (VOCs). There are   \n40 many resins used in water dispersion chemistry. For example, there are alkyd polyurethane dispersions (Dou, Z., et al., “Low VOC Polyol Alkyd Dispersion and Polyurethane Dispersions,” PCT Int. Appl. WO/2002/031021), hydroxyl functional latexes (Dvorchak, M., et al.,“A new   \n45 water reducible blocked polyisocyanate (NWRBP) for one component (1K) polyurethane coatings,\"Proceedings of the International Waterborne, High-Solids, and Powder Coatings Symposium (2000), $27^{t h}$ 405-419; Escarsega, J. A., et al., “Water reducible PUR coatings for military applica  \n50 tions,\"Modern Paint and Coatings (1997), 87(7), 21, 24-26; Grunlan, M.A., et al. “Waterborne coatings with an emphasis on synthetic aspects; an overview.” ACS Symposium Series (1997), 663 (Technology for Waterborne Coatings), 1-26; Hartz, R. E., “Reaction during cure of a blocked   \n55 isocyanate-epoxy resin adhesive,\" Journal of Applied Polymer Science (1975), 19(3), 735, water reducible polyesters (7 Gaal, R. J., et al., “Water-reducible polyester resins and urethane coatings produced therefrom, \" U.S. (2001); Page, A., et al.,“Polyester resins in water-based urethanes,\" Paint   \n60 Ink International (1996), 9(2), 37,40; Dvorchak, M.J., et al. “Water-reducible unsaturated polyester polymers as binder for UV-curable furniture coatings,\" Proceedings of the Waterborne, High-Solids, and Powder Coatings Symposium (1991), $18^{t h}25\\bar{3}–67$ , and water reducible acrylics (Venditti   \n65 Wang, et al.“Synthesis and characterization of UV-Curable waterborne polyurethane-acrylate ionomers for coatings,' Journal of Applied Polymer Science (1999), 73 (844), 2869-",
+        "category": " Introduction"
+    },
+    {
+        "id": 20,
+        "chunk": "# 3  \n\n2876); and Yang, Jian-wen et al., “Chain-extended UVcurable waterborne polyurethane-acrylate,\" Gaofenzi Cailiao Kexue Yu Gongcheng (2003),19(2), 199-202.  \n\nOne of the major problems with isocyanates when mixing in polyol is that most hydroxyl functional crosslinkers are 5 hydrophobic. In some formulations, this has been overcome by mixing resin particles (Jang, Jong Yoon et al., “Effect of process variables on molecular weight and mechanical properties of water-based polyurethane dispersion,\" Colloids and Surfaces, A: Physicochemical and Engineering 10 Aspects (2002),196(2-3),135-143; Guenduez, G.et al., \"Structure-Property Study of Waterborne Polyurethane Coatings with Different Hydrophilic Contents and Polyols,\" Journal of Dispersion Science and Technology (2004),15 25(2), 217-228) to protect the reaction from hydrolysis (Qu, Jinqing et al., “Syntheses of high solid content waterborne polyurethane dispersion,\" Huagong Xucbao (2003), 54(6), 868-871) or by isocyanate monomer selection (Song, Xiaohui et al., “Effect of PEG molecular weight in hydrophilic 20 segment on the crystallization of cast film of waterborne polyurethane,” Xiamen Daxue Xuebao, Ziran Kexueban (2002), 41(4), 463-467). Two component systems are usually formulated with the isocyanate in excess to alcohol, by using a ratio of isocyanates to alcohol of 2:1 (over-index- 25 ing). These systems require more isocyanate to be used due to competing reactions with water. One way to lessen isocyanate reactivity with water is to increase molecular weight by building the prepolymer (Jang, Jong Yoon et al., “Effect of process variables on molecular weight and 30 mechanical properties of water-based polyurethane dispersion,\" Colloids and Surfaces, A: Physicochemical and Engineering Aspects,”(2002),196(2-3),135-143; Webb,D.D. “Urethane systems reactivity measurement,\" Journal of Cellular Plastics (1985), 21(3), 208-12). The dominant isocya- 35 nate reaction is with an alcohol group (Illger, H. W., et al. “Reaction kinetics study of high resilient polyurethane foams,\" Polyurethanes World Congr. Proc.FSK/SPI (1987), 305-10. Publisher: Technomic, Lancaster, Pa.).  \n\nThere is currently a great need for low or near zero VOC 40 (volatile organic content) systems in developing waterborne resin technology. Therefore, it is advantageous to provide waterborne polyurethane dispersions that provide the performance currently required by the industries with excellent combination of higher reactivity and physical properties of 45 epoxy and polyurethane technology. It would be also desirable that the coating compositions can be dispersed in water with or without added surfactants to form a dispersion containing no volatile organic solvent.",
+        "category": " Introduction"
+    },
+    {
+        "id": 21,
+        "chunk": "# SUMMARYOFTHEINVENTION  \n\nThe invention relates to aqueous coating compositions comprising a polyfunctional oligomer having at least two epoxy urethane functional groups and a polyalkylene oxide 55 chain, an optional surfactant, and water. The invention also provides methods for making an aqueous coating composition comprising a polyfunctional oligomer having at least two epoxy urethane functional groups and a polyalkylene oxide chain, an optional surfactant, and water. The aqueous 60 coating compositions of the invention are completely solvent-free, i.e., do not utilize any co-solvents, such that the content of VOCs is zero while maintaining the dispersibility of the copolymer in water without any co-solvents.  \n\nA water-dispersible epoxy urethane resin of the Formula 65 (I) or Formula (Il) of the aqueous coating composition represents another embodiment of the invention.  \n\n![](images/01cc22f788cc313fe98f43327d15f083feb9d6bbd9af6ebe8d14cb4f268cdc0b.jpg)  \n\nwherein $\\mathrm{R}_{2}$ is independently an optionally substituted, divalent $\\mathrm{C_{1}}\\mathrm{-}\\mathrm{C_{15}}$ alkyl, optionally substituted divalent $\\mathrm{C}_{3}{\\mathrm{-C}}_{15}$ cycloalkyl, or a group selected from  \n\n![](images/d1be859b3d75ba113ab0f0ee922a4e5b9267e7be3646caacb7eae2cd819f597a.jpg)  \n\nand ${\\mathrm{R}}_{3}$ is independently an optionally substituted $\\mathrm{C_{1}}\\mathrm{-}\\mathrm{C_{1}}_{5}$ alkyl or an optionally substituted divalent $\\mathrm{C}_{3}–\\mathrm{C}_{10}$ cycloalkyl.",
+        "category": " Introduction"
+    },
+    {
+        "id": 22,
+        "chunk": "# BRIEFDESCRIPTIONOFTHEFIGURES  \n\nFIG.1 depicts salt spray test panels formulated using an aqueous coating composition of the invention containing  \n\nand epoxy urethane resin at ambient conditions and D.E.R.   \n332 reacted with PACM at $80^{\\circ}\\mathrm{C}$ . for one hour as a control.  \n\nFIG.2 is a schematic representation of the reaction for the synthesis of methoxy poly(ethylene glycol) (mPEG) modified glycidyl carbamate resins.  \n\nFIG. 3 depicts a $^{13}\\mathrm{C}$ NMR spectrum of resin R1.  \n\nFIG. 4 depicts the composition of mPEG modified glycidyl carbamate resins (a) Hydrophilic glycidyl carbamate molecule and (b) Hydrophobic glycidyl carbamate molecule.  \n\nFIG. 5 is a schematic representation of the dispersed particle of glycidyl carbamate resin in water.  \n\nFIG. 6 is a schematic representation of making a waterborne glycidyl carbamate coating formulation.  \n\nFIG. 7 shows a graph of the water contact angle of the glycidyl carbamate coatings.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# DETAILED DESCRIPTION OF THE INVENTION  \n\nThe invention is directed to novel aqueous coating compositions comprising a polyfunctional oligomer having at least two epoxy urethane functional groups and a polyalkylene oxide chain, an optional surfactant, and water.  \n\nThe polyfunctional oligomer is prepared from the reaction of hydrophilic modified polyfunctional isocyanates resin with glycidol. The polyfunctional resin is derived from controlled polymerization or oligomerization of difunctional isocyanates.Free isocyanate is reacted with glycidol to form an epoxy urethane functional resin. The polyfunctional resin also includes a polyfunctional biuret or isocyanurate.  \n\nAny suitable organic polyisocyanate, such as an aliphatic, cycloaliphatic, araliphatic or aromatic polyisocyanate, may be used either singly or in mixtures of two or more. The 3 aliphatic isocyanates provide generally better light stability than the aromatic compounds.Aromatic polyisocyanates, on the other hand, are generally more economical and reactive toward polyols and other poly(active hydrogen) compounds $40$ than aliphatic polyisocyanates. Suitable aromatic polyisocyanates include but are not limited to those selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, a dimer of toluene diisocyanate (available under the Desmodur $\\textsuperscript{\\textregistered}$ trademark from Bayer Materials 4: Science, Leverkusen, Germany), diphenylmethane $^{4,4^{\\prime}}$ -diisocyanate (MDI), 1,5-diisocyanato-naphthalene, 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate, fluorinated and/or silicone containing derivatives of the aforementioned, and mixtures thereof. Examples of useful cycloali- 5( phatic polyisocyanates include but are not limited to those selected from the group consisting of dicyclohexylmethane diisocyanate( $\\mathrm{\\Delta}\\mathrm{H}_{12}$ ， MDI, commercially available under the Desmodur $\\textsuperscript{\\textregistered}$ trademark from Bayer Materials Science, 5: Leverkusen, Germany), isophorone diisocyanate (IPDI), 1,4-cyclohexane diisocyanate (CHDI), 1,4-cyclohexanebis (methylene isocyanate) (BDI), 1,3-bis(isocyanatomethyl) cyclohexane（ $\\mathrm{\\mathrm{~H}}_{6}$ XDI), and mixtures thereof. Examples of useful aliphatic polyisocyanates include but are not limited 60 to those selected from the group consisting of hexamethylene 1,6-diisocyanate (HDI), 1,12-dodecane diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate (TMDI), 2,4,4- trimethyl-hexamethylene diisocyanate (TMDI), 2-methyl-1， 6: 5-pentamethylene diisocyanate, dimer diisocyanate, the urea of hexamethyl diisocyanate, and mixtures thereof. Examples  \n\nof useful araliphatic polyisocyanates include but are not limited to those selected from the group consisting of m-tetramethyl xylylene diisocyanate (m-TMXDI), p-tetramethyl xylylene diisocyanate ( $\\mathrm{{\\widetilde{p}}}$ -TMXDI), 1,4-xylylene diisocyanate (XDI), 1,3-xylylene diisocyanate, or mixtures thereof.  \n\nPreferably, a polyfunctional resin is derived from the diisocyanates to yield resins having more than two isocyanate groups per molecule. This is commonly accomplished by making the isocyanurate or biuret adducts of the diisocyanates.  \n\nPreferably, the polyfunctional resin derived from isocya15 nurate or biuret is selected from the group consisting of TDI (toluene diisocyanate)isocyanurate, TDI biuret, MDI (diphenylmethane diisocyanate)isocyanurate, MDI biuret, HDI (hexamethylene diisocyanate)isocyanurate, HDI biuret, NDI (naphthalene diisocyanate)isocyanurate, NDI biuret, HMDI 20 (hydrogenated MDI)isocyanurate, HMDI biuret, and IPDI (isophorone diisocyanate)isocyanurate and IPDI biuret. More preferably, a polyfunctional resin derived from isocyanurate or biuret consists of HDI (hexamethylene diiso25 cyanate)isocyanurate or HDI biuret.  \n\nThe polyfunctional oligomer of the invention is hydrophilic. Applicable hydrophilic functionality with suitable functional groups can readily be provided with the skilled   \n50 person. Preferably, the polyfunctional oligomer has a polyalkylene oxide chain with 1 to 5O alkylene oxide units, preferably 2 to 20 alkylene oxide units. More preferably, the polyalkylene oxide chain may be an ethylene oxide chain, a   \ni5 propylene oxide chain, or an ethylene propylene oxide chain.  \n\nA hydrophilic polyfunctional isocyanate resin based on hexamethylene diisocyanate and having ethylene oxide units is commercially available and sold under the Bayhydur? XP 7165 tradename by Bayer Materials Science, Leverkusen Germany. Hydrophilic isocyanates may also be synthesized by reacting a polyfunctional isocyanate resin, such as Desmodur $\\textsuperscript{\\textregistered}$ $\\textsf{N}3600$ (Bayer Materials Science, Leverkusen, 45 Germany), with a hydroxyl terminated polyether such as mPEG.  \n\nThe invention also provides a water-dispersible epoxy urethane resin of the Formula (I) or Formula (I) of the aqueous coating composition:  \n\n![](images/4527f15a3bd716581911cda19a278ed56ce76646fb927bec1c730f7368335b28.jpg)  \n\n![](images/14ed75f0f6ddb57163dc5c392da660926acf0d3bda1ea126b4b9c47788d93c20.jpg)  \n\nwherein   \nn ranges from 1 to 50   \n$\\mathrm{R}_{2}$ is independently an optionally substituted, divalent $\\mathrm{C_{1}}\\mathrm{-}\\mathrm{C_{1}}_{5}$ alkyl, optionally substituted divalent $\\mathrm{C}_{3}–\\mathrm{C}_{15}$ cycloalkyl, or a group selected from  \n\n![](images/c32439683581344d30521fb88d216423691043cb6751507f0747916483ac473a.jpg)  \n\nand ${\\mathrm{R}}_{3}$ is independently an optionally substituted $\\mathrm{C_{1}}\\mathrm{-}\\mathrm{C_{15}}$ alkyl or an optionally substituted divalent $\\mathrm{C}_{3}{\\mathrm{-}}\\mathrm{C}_{10}$ cycloalkyl. Preferably, $\\mathrm{R}_{2}$ is $\\begin{array}{r}{-(\\mathrm{CH}^{2})_{6}-,}\\end{array}$ and ${\\mathrm{R}}_{3}$ is a $\\mathrm{C_{1}{-}C_{10}}$ alkyl.  \n\nThe term “alkyl\"” includes straight and branched alkyl groups. The term “cycloalkyl', as used herein, refers to groups having three to ten, preferably three to seven carbon atoms. Suitable cycloalkyls include, but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like. As indicated above, $\\mathrm{R}_{2}$ and ${\\mathrm{R}}_{3}$ may be substituted with any number of substituents or functional moieties. Examples of substituents include, but are not limited to, halo substituents, e.g. F; Cl; Br; or I; a hydroxyl group; a $\\mathrm{C_{1}}\\mathrm{-}\\mathrm{C_{6}}$ alkoxy group, e.g.,— $\\mathrm{OCH}_{3}$ ， ${\\mathrm{-OCH}}_{2}{\\mathrm{CH}}_{3}$ or- $\\mathrm{-OCH}(\\mathrm{CH}_{3})_{2}$ ;a $\\mathrm{C_{1}}\\mathrm{-}\\mathrm{C_{6}}$ haloalkyl group, e.g., ${\\mathrm{-CF}}_{3}$ ${\\mathrm{CH}}_{2}{\\mathrm{CF}}_{3}$ ; or— $\\mathrm{CHCl}_{2}$ $\\mathrm{C_{1}}\\mathrm{-}\\mathrm{C_{6}}$ alkylthio; amino; mono and dialkyl amino groups; — $\\mathrm{\\cdotNO}_{2}$ ；—CN; a sulfate group, and the like.  \n\nSurfactants are commonly used in coating formulations to improve wetting of the substrate by the coating, and wetting",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 24,
+        "chunk": "# 8  \n\nof the pigment by the resin. They can also improve formulating latitude by preventing shocking of the coating composition as various components are added and can increase the service life of the coating by increasing shelf stability.   \n5 Typically, low levels of surfactants are used to accomplish these goals and mixtures of surfactants may be employed to impart one or more of the properties listed above. Surfactants are not generally volatile materials under ambient conditions and remain in the coating during the drying   \n10 process. However, at the low concentrations typically used, little effect on polymer hardness or coating performance is observed. If too much surfactant is used in the aqueous coating composition, the wet coating could exhibit excessive foaming and poor thickening eficiency with thickeners   \n15 while the cured coating could have problems with water sensitivity, poor exterior durability and poor block, stain and print resistance. Thus, surfactants are typically used in the lowest amounts necessary to achieve their beneficial properties while avoiding any detrimental effects.   \n20 Any anionic or nonionic surfactant, as well as mixtures, may be used in a water-based polymer coating composition of the invention. The optional surfactant is present in an amount effective to stabilize a coating formed from the composition. In some formulations, a surfactant is not   \n25 needed in order to obtain a stabile dispersion. Preferably the nonionic surfactant is a polyether nonionic surfactant, more preferably, an alkyl polyglycol ether, an alkyl phenol polyglycol ether, or a mixture thereof. Preferred alkyl phenol polyglycol ethers include ethoxylation products of octylphe  \n30 nol, nonylphenol, diisopropyl phenol, triisopropyl phenol, or mixtures thereof. Preferred alkyl polyglycol ethers include ethoxylation products of lauryl alcohol, oleyl alcohol, stearyl alcohol, or mixtures thereof. Preferred anionic surfactants include alkali metal or ammonium salts of alkyl,   \n35 aryl or alkylaryl sulfonates, sulfates, phosphates. More preferably, the anionic surfactant is selected from sodium lauryl sulfate, sodium octylphenol glycolether sulfate, sodium dodecylbenzene sulfonate, sodium lauryldiglycol sulfate, ammonium tritertiarybutyl phenol and penta- and octa  \n40 glycol sulfonates, sulfosuccinate salts such as disodium ethoxylated nonylphenol half ester of sulfosuccinic acid, disodium n-octyldecyl sulfosuccinate, sodium dioctyl sulfosuccinate, and mixtures thereof. AEROSOL 18 surfactant, a $35\\%$ solution of disodium N-octyldecyl sulfosuccinimate   \n45 in water and AEROSOL OT-75 surfactant, a $75\\%$ solution of sodium dioctyl sulfosuccinate in water, both available from Cytec Industries, Inc. are preferred anionic surfactants. Triton GR-7M is also preferred sulfosuccinate surfactant. In one embodiment, the aqueous coating composition of   \n50 the invention is formulated using 1O to 90 parts, preferably 50 to 70 parts, of a polyfunctional oligomer; 90 to 10 parts, preferably 30 to 50 parts, water; and 0.1 to 10 parts, preferably O.1 to 5 parts, of an optional surfactant, without addition of co-solvent. After mixing the polyfunctional   \n55 oligomer and water, the surfactant may be added for dispersion and, if desired a diluted drop of defoamer, such as BYK 028 by BYK Chemie USA, may be used as a flow aid. The formulation may be mixed at room temperature. A coating formed from an aqueous coating composition of   \n60 the invention may be self-cured by heating to temperatures at or above $120^{\\circ}\\mathrm{~C~}$ . In a preferred embodiment, an aqueous coating composition of the invention contains a curing agent. As is known in the art, curing agents are sold separately from the coating composition. Accordingly, a   \n65 curing agent may be added to an aqueous coating composition of the invention prior to coating. The amount of curing agent used is determined by the stoichiometric ratio of  \n\nepoxy groups of the epoxy urethane (glycidyl carbamate) resin to active amine hydrogens on the amine curing agent. Stoichiometric ratios in the range of 0.5 to 2.0 can be used.  \n\nThe curing agent serves to crosslink the resultant epoxy urethane coating formed using an aqueous coating composition of the invention. The curing agent may be any curing agent known in the art to cure (or crosslink) epoxy resins. The curing agent may be used in the manner and amount known in the art. The curing agents are generally water compatible (i.e., soluble, dilutable and/or dispersible). Suitable curing agents for use with the dispersions include those typically employed with epoxy resins, such as aliphatic, araliphatic and aromatic amines, polyamides, amidoamines and epoxy-amine adducts. The coating may be cured at ambient or elevated (e.g. about $80^{\\circ}\\mathrm{C}.$ ) temperatures.Amine curing agents typically allow the coating to cure at ambient temperatures.  \n\nSuitable amine curing agents are those which are soluble or at least dispersible in an aqueous coating composition of the invention.Amine curing agents known in the art include, for example, diethylenetriamine, triethylenetetramine, tetraethylene-pentamine, etc. as well as 2,2,4- and/or 2,4,4- trimethylhexamethylenediamine; 1,2- and 1,3-diaminopropane; 2,2-dimethylpropylenediamine; 1,4-diaminobutane; 1,6-hexanediamine; 1,7-diaminoheptane; 1,8-diaminooctane; 1,9-diaminononane; 1,12-diaminododecane; 4-azaheptamethylenediamine; N,N\"-bis(3-aminopropyl)butane-1,4- diamine; 1-ethyl-1,3-propanediamine; 2,2(4),4-trimethyl-1, 6-hexanediamin; bis(3-aminopropyl)piperazine; N-aminoethylpiperazine; N,N-bis(3-aminopropyl)ethylenediamine; 2,4(6)-toluenediamine; dicyandiamine; melamine formaldehyde; tetraethylenepentamine; 3-diethylaminopropylamine; ${}_{3,3\"}$ -iminobispropylamine; tetraethylenepentamine; 3-diethylaminopropylamine; and 2,2,4- and 2,4,4-trimethylhexamethylenediamine.Exemplarycycloaliphatic amine curing agents include, but are not limited to, 1,2- and 1,3-diaminocyclohexane; 1,4-diamino-2,5-diethylcyclohexane; 1,4-diamino-3,6-diethylcyclohexane; 1,2-diamino4-ethylcyclohexane; 1,4-diamino-2,5-diethylcyclohexane; 1,2-diamino-4-cyclohexylcyclohexane; isophorone-diamine; norbornanediamine; 4,4'-diaminodicyclohexylmethane; 4,4'-diaminodicyclohexylethane; $^{4,4^{\\prime}}$ -diaminodicyclohexylpropane; 2,2-bis(4-aminocyclohexyl)propane; 3,3'- dimethyl- $^{4,4^{\\prime}}$ -diaminodicyclohexylmethane; 3-amino-1-(4- aminocyclohexyl)propane; 1,3- and 1,4-bis(aminomethyl) cyclohexane; and 1-cyclohexyl-3,4-dimino-cyclohexane.As exemplary araliphatic amines, in particular those amines are employed in which the amino groups are present on the aliphatic radical for example m- and $\\mathfrak{p}$ -xylylenediamine or their hydrogenation products as well as diamide diphenylmethane; diamide diphenylsulfonic acid (amine adduct); $4{,}4\"$ -methylenedianiline;“2,4-bis(p-aminobenzyl)aniline; diethyltoluenediamine; and m-phenylene diamine. The amine curing agents may be used alone or as mixtures.  \n\nSuitable amine-epoxide adducts are, for example, reaction products of diamines such as, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, m-xylylenediamine and/or bis(aminomethyl)cyclohexane with terminal epoxides such as, for example, polyglycidyl ethers of polyhydric phenols listed above.  \n\nPreferably, amine curing agents used with the aqueous coating compositions of the invention are PACM (bis(paraaminocyclohexyl)methane)， Anquamine 419, Anquamine 731, diethylene triamine (DETA), and $^{4,4^{\\prime}}$ -methylene dianiline (MDA). Stoichiometry ratios of amine to oxirane of the aqueous coating compositions may be based on amine hydrogen equivalent weight (AHEW） and on weight per epoxide (WPE). A formulation of 1:1 was based on one epoxide reacted with one amine active hydrogen.  \n\nThe invention also provides a method for making an aqueous coating composition comprising the steps of mixing a polyfunctional oligomer having at least two epoxy urethane functional groups and a hydroxylated polyalkylene oxide chain, an optional surfactant, and water. The method for making an aqueous coating composition may further comprise the step of adding a curing agent to the mixture of ） the polyfunctional oligomer, the surfactant, and water after the dispersion.  \n\nThe aqueous coating compositions of the invention have an excellent combination of physical properties due to the carbamate and epoxide functionality. The coating composi  \n15 tion has excellent cure and high pendulum hardness values as well as good solvent resistance. The aqueous coating composition with epoxy urethane functional resin of the invention shows the improvement in one or more of the following performance parameters, i.e., $\\%$ nonvolatile sol  \n20 ids, flexibility, scratch and mar resistance, and/or chip resistance, in a wide variety of coating compositions and applications, such as primers, basecoats, clearcoats, twocomponent systems, anti-chip coating compositions,water borne coatings, solvent borne coatings, coatings for flexible   \n25 substrates, and the like. Furthermore,water-based coating composition with epoxy urethane functional resin of the invention provide etch resistant coating compositions which have an increased $\\%$ NV (nonvolatile) or decreased VOC (volatile organic content) at a sprayable viscosity.   \n30 An aqueous coating composition of the invention would be applicable for use in a wide variety of coating compositions and applications, such as primers, basecoats, clearcoats, two-component systems, anti-chip coating compositions, water borne coatings, solvent borne coatings,   \n35 coatings for flexible substrates, powder coatings, solventless powder-slurry coatings, solventless liquid coatings, and the like. Furthermore, the aqueous coating composition of the invention may be applied to any substrates, e.g., metal, wood, glass, stone, ceramic materials, concrete, rigid and   \n40 flexible synthetic resins, textiles, leather, and paper. These substrates may first be treated with conventional primers before they are coated.  \n\nAny additional agent used in aqueous coatings, for example, fillers, stabilizers, wetting agents, dispersing agents, adhesion promoters, UV absorbers, HALS, etc.may be incorporated into the coating composition of the invention.While the agents are well-known in the prior art and may be used in the same manner, the amount used should avoid adversely affecting the aqueous coating composition or the resultant coating.  \n\nUpon formulation, an aqueous coating composition of the invention may then be applied to a variety of surfaces, substrates, or articles, e.g., paper, plastic, steel, aluminum, wood, gypsum board, or galvanized sheeting (either primed   \n55 or unprimed). The aqueous coating composition may be applied to a substrate, article, or surface by any of a number of techniques well-known in the art. These include, for example, spray coating, dip coating, roll coating, curtain coating, and the like. For automotive body panels, spray   \n50 coating is preferred. As discussed above, an aqueous coating employing a polymer of the invention may be thermally or ambiently cured. As a further aspect, the present invention relates to a shaped or formed article which has been coated with an aqueous coating composition of the invention.  \n\nA coating composition according to the invention may comprise a pigment (organic or inorganic) and/or other additives and fillers known in the art. Such additives or",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 25,
+        "chunk": "# 11",
+        "category": " Introduction"
+    },
+    {
+        "id": 26,
+        "chunk": "# 12  \n\nfillers include, but are not limited to, leveling, rheology, and flow control agents such as silicones, fluorocarbons, urethanes, or cellulosics; extenders; reactive coalescing aids such as those described in U.S. Pat. No. 5,349,026; flatting agents; pigment wetting and dispersing agents and surfactants; ultraviolet (UV) absorbers; UV light stabilizers; tinting pigments; extenders; defoaming and antifoaming agents; anti-settling, anti-sag and bodying agents; anti-skinning agents; anti-flooding and anti-floating agents; fungicides and mildewcides; corrosion inhibitors; thickening agents; plasticizers; reactive plasticizers; curing agents; or coalescing agents. Specific examples of such additives can be found in Raw Materials Index, published by the National Paint & Coatings Association, 15oo Rhode Island Avenue, NW, Washington, D.C. 20005.",
+        "category": " Introduction"
+    },
+    {
+        "id": 27,
+        "chunk": "# EXAMPLES  \n\nThe following abbreviations and terms are used in the Examples below:  \n\nHDI: hexamethylene diisocyanate PACM: para amino-cyclohexyl methane Anquamine 419: curing agent MEK: methyl ethyl ketone mPEG: methoxy poly(ethylene glycol) ASTM: American Society for Testing and Materials Materials Used in Surfactant-Based Coatings Glycidol was supplied by Dixie Chemical and stored refrigerated to minimize formation of impurities.An isocyanurate trimer of HDI (hexamethylene diisocyanate) with polyethylene oxide (Bayhydur XP 7165) was used as the polyfunctional isocyanate resin with an isocyanate equivalent weight of 230. K-KAT $\\textsuperscript{\\textregistered}$ XC-6212 was supplied by King Industries. TritonTM GR-7M anionic surfactant was provided by Union Carbide and BYK O28 defoamer was provided by BYK Chemie USA. Amines used as hardeners were purchased from Aldrich and provided by Air Products. These include; bis(para-aminocyclohexyl)methane (PACM) and Anquamine 419, respectively. D.E.R. $\\textsuperscript{\\textregistered}$ 332 (DGEBA) was supplied by The Dow Chemical Company.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 28,
+        "chunk": "# Example 1: Synthesis of the Epoxy Urethane Resin  \n\nA $1000\\mathrm{ml}$ four neck round bottom flask with condenser, nitrogen inlet and Model 21O J-KEM temperature controller, 45 mechanical stirrer, with heating mantle were used for synthesis. The reaction vessel was charged with 225.21 grams glycidol and 700 grams of Bayhydur XP 7165 polyfunctional isocyanate resin and 0.112 grams K-KAT $\\textsuperscript{\\textregistered}$ XC-6212 (0.0025 weight percent). The temperature was held at $60^{\\circ}\\mathrm{C}$ .5( and the reaction was monitored and controlled within $+/.$ -two degrees Celsius. Infrared analysis was performed to determine reaction completion by monitoring the disappearance of the isocyanate peak at $2270\\mathrm{cm}^{-1}$ . Epoxy equivalent weights were determined by titration with HBr (ASTM 55 D1652). The theoretical epoxide equivalent weight of the product was 304, which compares with 303 grams/equivalent determined by titration.  \n\nInfrared (FTIR) measurements were performed using a Nicolet Magna-85O FTIR spectrometer. Sample aliquots were taken and coated directly on a potassium bromide salt plate. Omnic FTIR software for Nicolet was used to perform transmission with a final format of absorbance. Spectra acquisitions were based on 64 scans, resolution 4, and a data spacing of $1.98\\mathrm{cm}^{-1}$ . The main compartment was used and set for auto gain to monitor a spectral range of $4000\\mathrm{cm}^{-1}$ to $400~\\mathrm{{cm}^{-1}}$ . Different intervals of the reaction were sampled to monitor disappearance of the isocyanate peak. GRAMS $32~\\mathrm{v}5$ FTIR software was employed for spectral calculations.  \n\nExample 2: Aqueous Coating Compositions of the Invention  \n\nAqueous coating compositions of the invention were formulated using the epoxy urethane resin of Example 1, an   \n10 amine curing agent and water without addition of organic co-solvent. Coatings were formulated using $70\\%$ epoxy urethane resin and $30\\%$ water without addition of cosolvent. After mixing the resin and water, 1-drop Triton GR-7M surfactant was added for dispersion and diluting $1/6$   \n15 of a drop of BYK 028 was used as a flow aid. Formulations were mixed with a glass stir rod, by hand, at room temperature. After the resin was dispersed in water, the amine curing agent, PACM or Anquamine 419，was added. Table 1 illustrates the formulation with actual amounts used. Coat  \n20 ings of from the aqueous coating compositions of the invention were prepared and tested as described below.  \n\nTABLE1   \n\n\n<html><body><table><tr><td>25</td><td colspan=\"6\">Aqueous Coating Composition Formulation</td></tr><tr><td></td><td>Formulation</td><td>Water (g)</td><td>Resin (g)</td><td>PACM (g)</td><td>Anquamine 419 (g)</td><td>Solids (%)</td></tr><tr><td></td><td>1</td><td>3.752</td><td>8.474</td><td>1.450</td><td></td><td>69.3</td></tr><tr><td>30</td><td>2</td><td>4.50</td><td>3.752</td><td>一</td><td>9.710</td><td>69.7</td></tr></table></body></html>  \n\nFilm Preparation:  \n\nThe aqueous coating formulations were applied onto iron phosphated 22 gauge steel test panels purchased from i5 Q-panel. Coating application was made using a drawdown bar for a final dry film thickness of approximately 64 microns for the PACM addition and approximately 71 microns for the Anquamine 419 addition. The coated panels were then air cured or placed in an oven at $80^{\\circ}\\mathrm{~C~}$ .for 60 t0 minutes for crosslinking.  \n\nHardness Measurements:  \n\nHardness of films was evaluated 24 hours after the films cured in an $80^{\\circ}$ C.oven for 60 minutes and also for the air cured coatings. The films were tested for Konig pendulum hardness (ASTM D4366, with the values reported in seconds (sec)).  \n\nReverse Impact Testing:  \n\nASTM D2794 was used as a standard test method for the resistance of organic coatings to the effects of rapid deformation via reverse impact. Coatings were tested one week after cure using a Gardener impact tester (ASTM D 2794). The maximum drop height was 43 inches with a drop weight of 4 pounds. All measurements were performed in triplicate. Crazing or loss of adhesion was noted and inch pounds were determined at film finish failure. Samples that did not fail were noted ${>}172$ in-lbs.  \n\nMEK Double Rubs:  \n\nMethyl ethyl ketone (MEK) double rubs were used to assess the development of cure. The coating was applied to the steel test panel using a casting bar. For the ambient cure system, coated panels were placed in a dust free chamber to cure at room temperature. Panels were removed to determine cure by solvent resistance at the end of 2, 3, and 3.45 hours when PACM was used as the hardener. For the coating formulations Anquamine 419 was less reactive than PACM, measured by solvent resistance were place in the dust free chamber for 24 hours then analyzed for solvent resistance.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 29,
+        "chunk": "# 13  \n\nA 26-ounce hammer with 5-layers of cheesecloth wrapped around the hammerhead was soaked in MEK. After 100 double rubs the hammer was rewet with MEK. The number of double rubs to reach the substrate of the coating was reported. A fully cured coating was based on 40o double rubs without penetrating the coating to the substrate. The number of double rubs to reach the substrate coating was reported.  \n\nGloss Measurements:  \n\nA Gardco $\\textsuperscript{\\textregistered}$ NovoGlossTM GL-NG1001S statistical gloss meter was used to determine gloss. Gloss measurements were performed using three different geometries $20^{\\circ}$ D $60^{\\circ}$ and $85^{\\circ}$ . Geometry was optimized for a specific gloss range. In order to control the performance and linearity of the gloss meter a checking standard was used. The standard tile is a traceable institute standard. In order to obtain gloss differences three measurement geometries were taken.  \n\nProperties of epoxy urethane resin:PACM: Coatings:  \n\nTable 2 shows the physical property results for the resins crosslinked using the two different amines at $80^{\\circ}\\mathrm{~C~}$ .for 1 hour. The coatings had excellent cure and high pendulum hardness values. PACM yields slightly lower impact resistance and is a generally harder coating.A key difference is the equivalent weight and structure of the amine used.  \n\nTABLE2   \n\n\n<html><body><table><tr><td colspan=\"5\">Cure development of oven cured coatings, 80° C. for 1-hour.</td></tr><tr><td>Epoxy urethane resin:</td><td>Dry film thickness (microns)</td><td>Konig Pendulum Hardness (Seconds)</td><td>Impact (Inch- pounds)</td><td>MEKDouble Rubs (Substrate)</td></tr><tr><td>1</td><td>64</td><td>147</td><td>168</td><td>>1000</td></tr><tr><td>PACM 2 Anquamine 419</td><td>71</td><td>94</td><td>>172</td><td>>1000</td></tr></table></body></html>  \n\nGloss readings of the $80^{\\circ}\\mathrm{C}$ .1 hour oven cured coatings are shown in Table 3. The different gloss readings of these two samples are more clearly shown in the $20^{\\circ}$ readings, followed by the $60^{\\circ}$ readings. Gloss readings were higher for the epoxy urethane resin:PACM than for the epoxy urethane resin: Anquamine 419 for all three geometries used.  \n\nTABLE3   \nExample 3: Cure Development Under Ambient Conditions   \n\n\n<html><body><table><tr><td colspan=\"3\">Gloss of oven cured coatings, 80° C. for 1-hour.</td></tr><tr><td>Gloss (degrees)</td><td>2 Anquamine 419</td><td>1 PACM</td></tr><tr><td>20</td><td>22.14</td><td>45.60</td></tr><tr><td>60</td><td>63.03</td><td>69.71</td></tr><tr><td>85</td><td>80.49</td><td>81.05</td></tr></table></body></html>  \n\n14 TABLE 4   \n\n\n<html><body><table><tr><td colspan=\"7\">Cure development of Aqueous Coating Composition 1: PACM Air-cured Coating.</td></tr><tr><td>Epoxy urethane resin</td><td>Dry film thickness (microns)</td><td>Hours to Cure before Testing</td><td>MEK Double Rubs (substrate)</td><td>Konig Pendulum Hardness (seconds)</td><td>Impact (Inch- pounds)</td></tr><tr><td>1</td><td>68</td><td>２</td><td>一</td><td>159</td><td></td></tr><tr><td>PACM</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>二</td><td>二</td><td>3.45</td><td>>143</td><td>143</td><td>164</td></tr></table></body></html>  \n\nCoatings were formulated as in Example 2, and cure development under ambient conditions was evaluated and the results are listed in Tables 4 and 5. Cure develops very rapidly, especially for the PACM-cured coating where full cure is achieved in less than four hours. Both coatings also had good hardness and flexibility after reaching complete cure.  \n\nTABLE5   \n\n\n<html><body><table><tr><td colspan=\"6\">Cure Development of Aqueous Coating Composition 1: Anquamine 419 Air-cured Coating.</td></tr><tr><td>， Epoxy urethane resin</td><td>Dry film thickness (microns)</td><td>Hours to Cure before Testing</td><td>MEK Double Rubs (substrate)</td><td>Konig Pendulum Hardness (seconds)</td><td>Impact (Inch- pounds)</td></tr><tr><td>2. Anquamine</td><td>68</td><td>２</td><td>111</td><td></td><td></td></tr><tr><td></td><td></td><td>3</td><td>113</td><td></td><td></td></tr><tr><td></td><td></td><td>24</td><td>>1000</td><td>106</td><td>>172</td></tr></table></body></html>  \n\nThe epoxy urethane resin:PACM had a slightly lower impact resistance than the epoxy urethane resin:Anquamine   \n30 419 and was generally a harder coating, possibly due to the equivalent weight and structure (cycloaliphatic amine) of the amine used. For ambient curing, the epoxy urethane resin: PACM fully cured within 3.5 hours and the epoxy urethane resin:Anquamine 419 cured over night.Both systems fully   \n35 cured at $80^{\\circ}~\\mathrm{~C~}$ . after a 1-hour cure. The epoxy urethane resin:PACM demonstrated a higher gloss than the epoxy urethane resin: Anquamine 419 for $20^{\\circ}$ D $60^{\\circ}$ ,and $85^{\\circ}$ geometries.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 30,
+        "chunk": "# Example 4: Salt Spray (ASTM B117) Testing of the Epoxy Urethane Resin with Compared to D.E.R.332  \n\nFor salt spray testing, an aqueous coating composition   \n45 was prepared as in Example 2 and a control coating was prepared using D.E.R.332 cured with PACM.Formulations were prepared using stoichiometric amounts of resin and hardener. Coatings were drawn down with a casting bar for a dry film thickness of approximately 75 microns. Coatings   \n50 were cured at $80^{\\circ}\\mathrm{~C~}$ . for one hour. Once cured the panels were scribed to obtain a cross cut. Corrosion performance was performed according to ASTM B117. This is a continuous salt fog at $35^{\\circ}\\mathrm{C}$ . The electrolyte solution is 49.97 grams sodium chloride per 1 liter de-ionized water. The results are   \n55 shown in FIG. 1. Corrosion of the test panels can be observed after being subjected to 450 hours in the salt spray chamber. The D.E.R. 332:PACM test panel had the most corrosion at the scribe (C) and the epoxy urethane resin: PACM began to delaminate (D). The control coating (D.E.R.   \n60 332:PACM) outperformed the epoxy urethane resin:PACM. Materials Used in Surfactant-Free Waterborne Glycidyl Carbamate Coatings  \n\nGlycidol was supplied by Dixie Chemical and stored refrigerated to minimize formation of impurities. The two polyisocyanates used were hexamethylene diisocyanate isocyanurate (Desmodur? N 3600) and hydrophilic isocyanate (Bayhydur $\\textsuperscript{\\textregistered}$ XP 7165) provided by Bayer MaterialScience;  \n\nthese have NCO equivalent weights $\\mathrm{(g/eq)}$ of 180 and 230, respectively. Methoxy poly(ethylene glycol) (mPEG） of number average molecular weights 350, 550, and 750 were obtained from Aldrich. K-KAT $\\textsuperscript{\\textregistered}$ XC-6212, a zirconium chelate complex, was supplied by King Industries and used to catalyze the isocyanate and hydroxyl reactions to form the glycidyl carbamate (GC) resins. All of these reagents were used as received without any further purification. Amine crosslinker, Anquamine? 731 provided by Air products, has a hydrogen equivalent weight $\\mathrm{(gm/H)}$ of 200.The Anquamine $\\textsuperscript{\\textregistered}$ 731 is a water-based curing agent reportedly designed to emulsify and crosslink epoxy resin without the use of any surfactants. Surfactant, Triton $\\textsuperscript{\\textregistered}$ GR-7M (anionic surfactant based on dioctyl sulfosuccinates) obtained from Dow chemical, was used in selected coating formulations.  \n\nExample 5: Synthesis of Surfactant-Free, mPEG-Modified Glycidyl Carbamate Resins  \n\nA $500\\ \\mathrm{ml}$ four neck reaction vessel with condenser, nitrogen inlet and Model 210 J-KEM temperature controller, mechanical stirrer, and water bath used for heating and cooling the flask were used for synthesis. The synthesis was done in two steps.  \n\nIn the first step, the hydroxyl group of mPEG was reacted with a portion of isocyanate groups of the HDI polyisocyanate. The molecular weight and mole $\\%$ of mPEG reacted with isocyanate groups varied from 350, 550, and 750 and $5\\%$ D $10\\%$ ，and $15\\%$ ，respectively.FIG. 2 is a schematic representation of the reaction for the synthesis of mPEG modified GC resins.  \n\nIn the second step, the hydroxyl group of glycidol was reacted with the remaining isocyanate groups of the HDI isocyanate. Table 6 shows the GC resins synthesized.  \n\nA control GC resin was synthesized by reacting glycidol with commercial hydrophilic isocyanate (Bayhydun $\\textsuperscript{\\textregistered}$ XP 7165） containing a polyether chain (the exact molecular weight and $1\\mathrm{mol}\\mathrm{\\%}$ of polyether chain are a trade secret of Bayer MaterialScience).  \n\nTABLE 6   \n\n\n<html><body><table><tr><td colspan=\"4\">GC resins synthesized</td></tr><tr><td>Resin</td><td>mPEG Molecular weight (Mn)</td><td>Mol %ofmPEG</td><td>EEW (gm/eq)</td></tr><tr><td>R1</td><td>350</td><td>5%</td><td>416</td></tr><tr><td>R2</td><td>550</td><td>5%</td><td>369</td></tr><tr><td>R3</td><td>750</td><td>5%</td><td>391</td></tr><tr><td>R4</td><td>350</td><td>10%</td><td>324</td></tr><tr><td>R5</td><td>550</td><td>10%</td><td>373</td></tr><tr><td>R6</td><td>750</td><td>10%</td><td>304</td></tr><tr><td>R7</td><td>350</td><td>15%</td><td>485</td></tr><tr><td>R8</td><td>550</td><td>15%</td><td>417</td></tr><tr><td>R9</td><td>750</td><td>15%</td><td>500</td></tr><tr><td>R10 (Control)</td><td>Made from commercial hydrophilic isocyanate (Bayhydur ? XP 7165)</td><td></td><td>358</td></tr></table></body></html>\n\nEEW $\\mathbf{\\sigma}=\\mathbf{\\sigma}$ epoxy equivalent weight $\\mathrm{(gm/eq)}$  \n\nThe overall stoichiometric equivalent amount of isocyanate,mPEG,and glycidol based on —NCO and —OH groups used for the synthesis of GC resins was maintained at 1:1. The catalyst $\\mathrm{K\\mathrm{-}K A T(\\overline{{{\\mathbb{R}}}})}$ XC-6212, in the form of solution in tertiary butyl acetate ( $1-2\\%$ by wt.), was used for the reaction of isocyanates and hydroxyl groups.  \n\nDuring the synthesis of the modified GC resins, the reaction vessel was charged with Desmodur? $\\textnormal{N}3600$ followed by addition of the required amount of mPEG. The reaction mixture was stirred at $50{-}60^{\\circ}$ C.for about 45-60  \n\nmin. to ensure a homogeneous mixture. The catalyst (K-KAT $\\textsuperscript{\\textregistered}$ XC-6212) amount added after the mixing time was $0.03\\%$ by wt. (of the total reaction mass). The reaction was continued for 4-5 hrs at about $60{-}70^{\\circ}\\mathrm{~C~}$ . before the   \n5 addition of glycidol. Proper temperature control was required for the exothermic reaction of glycidol with isocyanate functional compounds to avoid gelling of the resin during the synthesis. The amount of glycidol added was divided over 3-4 increments added over 4-5 hrs. Glycidol   \n0 addition in the first increment was done at $45^{\\circ}\\mathrm{~C~}$ The subsequent addition of glycidol was done at the temperature about $55{-}60^{\\circ}\\mathrm{~C~}$ . and this temperature was maintained until the isocyanate peak (at $2271~\\mathrm{\\bar{cm}^{-1}}$ )was gone in FTIR.  \n\nA GC resin was also synthesized by reacting Bayhydur $\\textsuperscript{\\textregistered}$ 15 XP 7165 with glycidol. The reaction of Bayhydur $\\textsuperscript{\\textregistered}$ XP7165 with glycidol was done using K-KAT $\\textsuperscript{\\textregistered}$ XC-6212 as a catalyst.  \n\nAn unmodified GC resin was synthesized by reacting Desmodur $\\textsuperscript{\\textregistered}$ N 3600 with glycidol using catalyst K-KAT $\\textsuperscript{\\textregistered}$ XC-6212.  \n\nFTIR measurements were performed using a Nicolet Magna-850 FTIR spectrometer. Sample aliquots were taken and coated directly on a potassium bromide salt plate. Spectra acquisitions were based on 64 scans and a data spacing of $\\bar{1}.98\\mathrm{cm}^{-1}$ . The main compartment was used and set for auto gain to monitor a spectral range of $4000\\mathrm{cm}^{-1}$ to $500~\\mathrm{{cm}^{-1}}$ . The change in band absorption of isocyanate $(2272~\\mathrm{cm^{-1}}).$ ，—OH and—NH( $3750{\\cdot}3000~\\mathrm{cm}^{-1}$ )，amide $(1244~\\mathrm{{cm}^{-1})}$ ， and epoxide $(910~\\mathrm{{cm}^{-1}})_{\\cdot}$ ） bands were used to follow the reaction progress.  \n\nCharacterization of the structures of the synthesized GC resins was done using $^{13}\\mathrm{C}$ NMR. $^{13}\\mathrm{C}$ NMR was carried out using a JEOL-ECA ( ${\\bf\\Psi}_{400}\\bf{M H z}$ ）NMR spectrometer coupled with an auto-sampler accessory. The spectra were run at $24^{\\circ}$   \n35 C.with 1oo0 scans. All the spectra were collected by dissolving 50 to $70~\\mathrm{mg}$ samples in $0.7\\mathrm{\\ml}$ $\\mathrm{CDCl}_{3}$ .The spectra were analyzed using Delta NMR processing and control software (Version 4.3.5).FIG. 3 shows the NMR spectrum of resin R1. The peaks at 45 and 50 ppm for epoxy   \nt0 group and at 59,70, and 72 ppm for mPEG molecule indicated that the epoxy group and mPEG chain were incorporated in the structure of the GC resins.  \n\nEpoxy equivalent weight of the resins was determined by titration with hydrogen bromide (HBr) according to ASTM 45 D1652. A required amount of resin $(0.8\\mathrm{-}1.0~\\mathrm{gm})$ was dissolved in $5{\\mathrm{-}}10~\\mathrm{ml}$ of chloroform and was titrated against a standardized HBr solution prepared in glacial acetic acid. The indicator used was a solution of crystal violet in glacial acetic acid. End point of the titration was the appearance of 50 permanent yellow-green color.  \n\nThe composition of mPEG modified GC resins is illustrated in FIG. 4. Since only a fraction of the initial isocyanate groups are reacted with mPEG, the synthesized resins consist of a mixture of hydrophilic molecules containing 5 mPEG (FIG. 4a) and hydrophobic molecules containing no mPEG (FIG. 4b). While the polyisocyanurate is illustrated as being a trifunctional molecule, the commercial material contains a substantial amount of higher molecular weight adducts.  \n\nDispersion Stability:  \n\nHigh speed dispersion (HSD) was used to prepare resin dispersions in water ( $30\\%$ wt. solids) using a homogenizer C $^{10,000\\mathrm{rpm}}$ for $10\\mathrm{min.}$ ). The required amount of resin and water were mixed in a plastic cup by hand before using the homogenizer. No surfactants/additives were used to prepare the dispersions. The dispersions were kept at ambient conditions and their dispersion stability was evaluated after one, six, and fourteen days. Dispersions of relatively low hydrophilic resins showed phase separation (settlement) while dispersions of highly hydrophilic resins were stable and showed no phase separation.  \n\nDispersion stability was determined by visual examina- n tion to determine if phase separation (settlement) occurred in the test samples. Particle size analysis was performed on the dispersions that did not show any phase separation. The results of dispersion stability study are shown in Table 7. Dispersion stability was found to be strongly dependent 10 upon mPEG chain length and its mol $\\%$ in the GC resins. Resin R1, being the most hydrophobic resin as it contains the smallest mPEG chain length $(\\mathbf{M}_{n}$ of 350) in the smallest $1\\mathrm{mol}\\%$ C $5\\mathrm{mol}\\%$ )could not be dispersed in water using HSD $_{15}$ and remained phase separated all the time. Control GC resin, R10, showed similar behavior to that of R1. Resin R10 did not go in water by HSD and remained phase separated. Resin R2 containing mPEG of molecular weight of 550 at 5 mol $\\%$ showed better dispersibility compared to that of R1. 20 Dispersion made with R2 showed formation of agglomerates at the bottom of container. However, the agglomerates could be redispersed with hand mixing resulting in a good dispersion. Resin R4 showed some phase separation after six days but formed a good dispersion following hand mixing. On the 25 fourteenth day, R4 had resulted in a viscous non-flowable dispersion that upon further dilution with water a flowable dispersion was obtained containing no agglomerates. Resin R7 dispersion was similar to that of R4 dispersion, except R7 formed large agglomerates after diluting with water. 30 Dispersion of resin R5 did not phase separate on the sixth day. The dispersion of resin R5 was found to be slightly phase separated on the fourteenth day but was redispersed well by hand mixing. Dispersions of the resins R3, R6, R8, and R9 showed no phase separation after fourteen days. 35 Particle size analysis of these dispersions did not indicate the formation of large agglomerates over fourteen days. Resins R3, R6, and R9 contained mPEG of 750 molecular weight in 5,10, and $15\\mathrm{\\mol\\\\%}$ .Resin R8 contained mPEG of molecular weight 550 in $15\\mathrm{\\mol\\\\%}$ . Thus, chain length as 40 well as mol $\\%$ modification influenced the dispersion stability.  \n\nTABLE 7   \n\n\n<html><body><table><tr><td colspan=\"8\">Dispersion stability of GC resins after high speed dispersion</td></tr><tr><td></td><td colspan=\"2\">One day</td><td colspan=\"2\">Six davs</td><td colspan=\"2\">Fourteendays</td><td></td></tr><tr><td>Resin</td><td>Dispersion stability</td><td>Particle size (nm)</td><td>Dispersion stability</td><td>Particle size (nm)</td><td>Dispersion stability</td><td>Particle size (nm)</td><td></td></tr><tr><td>R1</td><td>C</td><td></td><td>C</td><td></td><td>C</td><td></td><td></td></tr><tr><td>R2</td><td>B</td><td></td><td>B</td><td></td><td></td><td></td><td></td></tr><tr><td>R3</td><td>A</td><td>25</td><td>A</td><td>11</td><td></td><td>B A</td><td>23</td></tr><tr><td>R4</td><td>B</td><td></td><td>B</td><td>一</td><td></td><td>D</td><td></td></tr><tr><td>R5</td><td>A</td><td>24</td><td>A</td><td>31</td><td></td><td></td><td></td></tr><tr><td>R6</td><td>A</td><td>15</td><td>A</td><td>11</td><td>B A</td><td></td><td>4</td></tr><tr><td>R7</td><td>B</td><td>一</td><td>B</td><td>一</td><td>E</td><td>一</td><td></td></tr><tr><td>R8</td><td>A</td><td>15</td><td>A</td><td>9</td><td>A</td><td>13 3</td><td></td></tr><tr><td>R9</td><td>A</td><td>4</td><td>A</td><td>9</td><td>A</td><td></td><td></td></tr><tr><td>R10</td><td>C</td><td></td><td>C</td><td></td><td>C</td><td></td><td></td></tr></table></body></html>\n\n$\\mathbf{A}=$ no phase separation, $\\mathrm{B}=$ partial phase separation redispersable by hand, $\\mathsf{C}=$ did not disperse in water by HSD and remained phase separated, $\\mathrm{D}=$ non-flowable viscous dispersion became flowable after addition of water and hand mixing, no agglomeration, $\\mathbf{E}=\\mathbf{\\partial}$ non-flowable viscous dispersion, showed large agglomerates after addition of water and hand mixing, —= particle size experiments not performed because dispersions showed phase separation.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 31,
+        "chunk": "# 18  \n\nFIG. 5 is a schematic representation of the dispersed particle of GC resin in water. FIG. 5 shows that the particle consists of hydrophobic GC molecules (containing no mPEG) at the core surrounded by hydrophilic GC molecules with mPEG chains extending out in aqueous medium. It was determined that for any amount or chain length of the mPEG used for modifying the GC resin, less than about $33\\mathrm{\\mol\\\\%}$ of the GC resin molecules contain an mPEG group. The remaining GC resin molecules do not contain an mPEG group. FIG. 5 illustrates this. GC resins contain strong hydrogen bonding groups such as urethane (—NHCO—) and carbonyl $(\\mathrm{-}\\mathrm{CO})$ responsible for their high viscosity. The high viscosity resulting from hydrogen bonding indicates the strong interaction among GC molecules which make them less favorable to interact with water molecules. Modification of GC resin by non-ionic hydrophilic mPEG chain might have disrupted the hydrogen bonding interaction among GC molecules and made them hydrophilic.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 32,
+        "chunk": "# Example 6: Waterborne Glycidyl Carbamate Coating Formulations of the Invention  \n\nWaterborne coating formulations of GC resins were made by mixing the components in water by hand. Specifically, the required amount of resin was dispersed in water (deionized water) in plastic cups using a tongue depressor. To the dispersed GC resins in water, the required amount of amine crosslinker was added by hand. FIG. 6 is a schematic representation of the process employed in making the waterborne GC coating formulations. The resulting formulations were kept at ambient for about $5\\ \\mathrm{min}$ .to stabilize the formulations. After the stabilization time, the coating formulations containing crosslinker were mixed by hand using a tongue depressor for about $5\\mathrm{min}$ . and kept at ambient for about 10-20 min. (induction time) before taking drawdowns. The films were drawndown at 8 mils wet thickness on steel panels (smooth finished Q panels, type QD36, $0.5{\\times}76{\\times}152$ mm) cleaned with $\\mathfrak{p}$ -xylene. The coatings were cured at ambient conditions for about two weeks before determining their water resistance, solvent resistance, and other coating properties. Dry film thickness of the coatings was between $65.70~\\upmu\\mathrm{m}$ ，  \n\nTable 8 shows the coating formulations of the GC resins. GC resins (except R1 and R1O) were dispersed in water without using any surfactant. Surfactant was used to disperse resins Rl and R10, because these resins could not be dispersed in water by hand.  \n\nTABLE8   \n\n\n<html><body><table><tr><td colspan=\"7\">Coating formulations of the GC resins</td></tr><tr><td>55 tions</td><td>Formula-</td><td>Resins</td><td>Resin (wt.%)</td><td>Water (wt.%)</td><td>Surfactant (wt.%)</td><td>Cross- linker (E:A)</td></tr><tr><td></td><td>F1</td><td>R1</td><td>62</td><td>37.3</td><td>0.7</td><td>1:1</td></tr><tr><td></td><td>F2</td><td>R2</td><td>66</td><td>34</td><td>0</td><td>1:1</td></tr><tr><td></td><td>F3</td><td>R3</td><td>63</td><td>37</td><td>0</td><td>1:1</td></tr><tr><td>50</td><td>F4</td><td>R4</td><td>66</td><td>34</td><td>0</td><td>1:1</td></tr><tr><td></td><td>F5</td><td>R5</td><td>67</td><td>33</td><td>0</td><td>1:1</td></tr><tr><td></td><td>F6</td><td>R6</td><td>67</td><td>33</td><td>0</td><td>1:1</td></tr><tr><td>F7</td><td></td><td>R7</td><td>67</td><td>33</td><td>0</td><td>1:1</td></tr><tr><td>F8</td><td></td><td>R8</td><td>66</td><td>34</td><td>0</td><td>1:1</td></tr><tr><td>F9</td><td></td><td>R9</td><td>66</td><td>34</td><td>0</td><td>1:1</td></tr><tr><td>65</td><td>F10 (Control)</td><td>R10 (Control)</td><td>63</td><td>36.3</td><td>0.7</td><td>1:1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 33,
+        "chunk": "# 19",
+        "category": " Introduction"
+    },
+    {
+        "id": 34,
+        "chunk": "# 20  \n\nCoating Performance Water and Solvent Resistance:  \n\nWater resistance of the waterborne GC coatings was determined by water drop test and water double rubs measurement. The water drop test was carried out by placing a drop of water (approximate weight ${\\sim}0.05\\mathrm{gm}\\$ ) on the coating surface. The water drop was covered with a glass slide (of size $2\\ \\mathrm{cm}{\\times}2\\ \\mathrm{cm}$ ）to avoid evaporation of water. The glass slide was removed from the coating surface after 1 hr. The surface of the coating was examined for defects, bubble formation, film delamination, and any permanent marks. Six replicates of each coating formulation were tested. The number of coatings that did not show any surface defects, bubble formation, delamination, and permanent marks was reported. Thus, a water resistance test result reported as “6\" indicates that all six replicates passed the test (i.e., no surface defects, bubble formation, delamination, or permanent marks) and the water resistance was the best.  \n\nMethyl ethyl ketone (MEK) double rubs test was used according to ASTM D 5402 to assess the solvent resistance and development of cure.A 26-ounce hammer with three layers of cheesecloth wrapped around the hammerhead was soaked in MEK. The hammer head was rewet with MEK after 30-50 double rubs. Once the metal panel surface was visible due to removal coating layer during the test, the number of double rubs was noted. The water double rub test was carried out in similar way as that of MEK double rub test by replacing MEK with deionized water.For the water double rub test, the number of double rubs was noted once the bubble formation, film delamination, permanent mark, or appearance of metal surface due to removal of coating was observed.  \n\nWater resistance of GC coatings was found to depend on the molecular weight and mol $\\%$ of mPEG used in the resin synthesis. Table 9 shows the water and solvent resistance of the coatings. Coatings made from the formulations F1, F2, and F4 exhibited excellent water resistance. The formulations F1, F2, and F4 were made from the resins R1, R2, and R4, respectively. Resins R1 and R2 contained 5 mol mPEG having molecular weight of 350 and 550, respectively.Resin R4 contained $10\\mathrm{mol}\\%$ mPEG having molecular weight of 350. Water resistance of the coatings made from control GC resin, R1O (formulation F1O) was inferior to that of the coatings made from the resins R1, R2, and R4 (formulations F1, F2 and F4). Addition of a small amount of surfactant （ $0.7\\%$ by wt.) in coating formulation F1 to disperse GC resin R1, made with low extent of hydrophilic portion (mPEG molecular weight of 350 at $5\\mathrm{mol}\\%$ ), did not appear to affect the water resistance of its coating.  \n\nTABLE9   \n\n\n<html><body><table><tr><td colspan=\"4\">Water and solvent resistance of the coatings.</td></tr><tr><td>Formula- tions</td><td>Water drop test (6=Best)</td><td>Water double rubs</td><td>MEKdouble rubs</td></tr><tr><td>F1</td><td>6</td><td>>400</td><td>>400</td></tr><tr><td>F2</td><td>6</td><td>>400</td><td>>400</td></tr><tr><td>F3</td><td>3</td><td>>400</td><td>>400</td></tr><tr><td>F4</td><td>5</td><td>>400</td><td>>400</td></tr><tr><td>F5</td><td>2</td><td>>400</td><td>>400</td></tr><tr><td>F6</td><td>0</td><td>>400</td><td>>400</td></tr><tr><td>F7</td><td>2</td><td>>400</td><td>>400</td></tr><tr><td>F8</td><td>0</td><td>325</td><td>>400</td></tr><tr><td>F9</td><td>0</td><td>245</td><td>>400</td></tr><tr><td>F10 (Control)</td><td>4</td><td>>400</td><td>>400</td></tr></table></body></html>  \n\nCoatings became more hydrophilic with an increase in mPEG molecular weight and mol $\\%$ which resulted in decrease of their water resistance. Coatings made from the formulations F8 and F9 showed poor water resistance compared to that of the other coatings. The formulations F8 and F9 were made from the resins R8 and R9 and contained the large extent of hydrophilic part, $15\\mathrm{\\mol\\\\%}$ mPEG having molecular weight of 550 and 750, respectively.  \n\nSolvent resistance of the coatings evaluated through MEK double rubs is widely accepted as an indication of development of cure or crosslinking in coatings. A high number of MEK double rubs is considered as an indication of high crosslink density. The extent of crosslinking plays an important role in determining the physical and chemical properties of coatings. See, e.g., Harkal, U D, Muehlberg, A J, Li, J,   \n5 Garrett, J T, Webster, D C, J. Coat. Tech. Res., Manuscript submitted (2009).All of the GC coatings made exhibited excellent solvent resistance through MEK double rubs values reaching above 40o and indicated a development of high crosslink density. The extent of modification of GC resins by   \n） mPEG did not affect the solvent resistance of GC coatings. The results of the water resistance tests suggested that the incorporation of mPEG molecular weight of 350 or 550 with $5\\mathrm{mol}\\%$ or incorporation of mPEG molecular weight of 350 with $10\\mathrm{\\mol\\\\%}$ in GC resins could produce coatings with   \n:5 good water resistance. Another interesting finding was that the addition of a small amount of surfactant to disperse relatively lower hydrophilic GC resin (R1） during coating formulation did not affect water resistance of GC coatings. Excellent solvent resistance of the coatings indicated that the   \n$30$ crosslinking density was developed sufficiently to resist the penetration of solvent (MEK) molecules though the coatings. Thus, tailoring the extent of non-ionic hydrophilic groups in GC resins produced coatings with a good combination of water and solvent resistance.  \n\nWater Contact Angle Testing:  \n\n35 To determine relative hydrophilicity/hydrophobicity of the coating surface, water contact angle was measured using a First Ten Angstrom FTA 100 series instrument. Results of the contact angle measurements correlated well the results of water resistance of the coatings. FIG.7 shows the effect of   \n40 chain length and mol $\\%$ of mPEG on water contact angle value of the GC coating. Increase in molecular weight and mol $\\%$ of mPEG in GC resins decreased the water contact angle indicating the increase in hydrophilicity of the coatings. Water resistance   \n45 of the coatings shown in Table 9 followed a similar trend. Increase in hydrophilicity of the coatings resulted in decrease of water resistance of the coatings. Water resistance evaluated through water drop test and water double rubs of the coatings made from resins R8 and R9 (formulations F8   \n50 and F9, respectively) was lower compared with that of the other coatings. Coatings made from resins R8 and R9 showed relatively lower water contact angle ( $18^{\\circ}$ and $17^{\\circ}$ D respectively) compared with that of the coatings made from the other resins. Resins R8 and R9 contained a large amount   \n55 of the hydrophilic portion, 550 and 750 molecular weight mPEG at $15\\mathrm{\\mol\\\\%}$ .  \n\nThe results of water resistance and contact angle experiments suggested that chain length as well as mol $\\%$ of mPEG in GC resins influenced the relative hydrophilicity of the coatings.  \n\nAppearance:  \n\nWaterborne GC coatings according to the invention were transparent, had high gloss, and did not show any signs of phase separation or haziness. The transparent coating film 65 with no phase separation indicated good coalescence and reaction among dispersed GC resin particles and amine crosslinker.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 35,
+        "chunk": "# 21  \n\nHardness, Reverse Impact Testing, Flexibility, and Cross Hatch Adhesion:  \n\nKonig pendulum hardness of the coatings was measured following ASTM D 4366. The hardness test results are reported in seconds (sec).  \n\nReverse impact strength of the coatings was determined following ASTM D 2794 using a Gardener impact tester. The maximum drop height was 43 inches and the drop weight was 4 pounds. Crazing or loss of adhesion was noted and inch-pounds (in-lbs) were reported at film finish failure. Samples that did not fail were noted as having an impact strength of ${>}172$ in-lbs.  \n\nThe conical mandrel test was also used according to ASTM D 522 for the determination of flexibility of the coatings. The results of the flexibility test were reported as the length of a crack (cm) formed on the coating during the test.  \n\nCross hatch adhesion of the coatings was evaluated using a Gardco cross hatch adhesion instrument following ASTM D 3359.  \n\nWaterborne GC coatings according to the invention showed excellent flexibility, good adhesion, and hardness. Table 10 shows the performance of the GC coatings. All of the GC coatings showed no cracks in conical mandrel bend test indicating excellent flexibility. Reverse impact test showed excellent resistance of the coatings to rapid deformation. The impact resistance value of most of the coatings reached the maximum (172 in-lbs) of the instrument.  \n\nwherein the polyfunctional oligomer comprises a polyfunctional resin derived from an isocyanurate or a biuret compound.  \n\nTABLE10   \n\n\n<html><body><table><tr><td colspan=\"5\">Performance of waterborne GC coatings</td></tr><tr><td>Formula- tions</td><td>Conical Mandrel (0 cm=Best)</td><td>Reverse Impact (in-lbs)</td><td>Konig pendulum hardness (sec)</td><td>Cross-hatch adhesion (5B=Best)</td></tr><tr><td>F1</td><td>0</td><td>>172</td><td>44</td><td>5B</td></tr><tr><td>F2</td><td>0</td><td>128</td><td>97</td><td>4B</td></tr><tr><td>F3</td><td>0</td><td>112</td><td>90</td><td>0B</td></tr><tr><td>F4</td><td>0</td><td>>172</td><td>60</td><td>1B</td></tr><tr><td>F5</td><td>0</td><td>>172</td><td>59</td><td>1B</td></tr><tr><td>F6</td><td>0</td><td>>172</td><td>30</td><td>4B</td></tr><tr><td>F7</td><td>0</td><td>>172</td><td>23</td><td>5B</td></tr><tr><td>F8</td><td>0</td><td>>172</td><td>19</td><td>5B</td></tr><tr><td>F9</td><td>0</td><td>>172</td><td>24</td><td>5B</td></tr><tr><td>F10 (Control)</td><td>0</td><td>>172</td><td>39</td><td>5B</td></tr></table></body></html>  \n\nThe claimed invention is:  \n\n1. An aqueous coating composition comprising a dispersion of:  \n\n3. An aqueous coating composition of claim 1 or claim 2,   \n5 further comprising a curing agent. 4. An aqueous coating composition of claim 3, wherein the polyfunctional resin is selected from the group consisting of toluene diisocyanate isocyanurate, toluene diisocyanate biuret, diphenylmethane diisocyanate isocyanurate,   \n10 diphenylmethane disocyanate biuret, hexamethylene diisocyanate isocyanurate, hexamethylene diisocyanate biuret, naphthalene diisocyanate isocyanurate, naphthalene diisocyanate biuret, hydrogenated diphenylmethane diisocyanate isocyanurate, hydrogenated diphenylmethane diisocyanate   \n15 biuret, isophorone diisocyanate isocyanurate and isophorone diisocyanate biuret; and the $\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{15}$ alkyl terminated polyalkylene oxide is a $\\mathrm{C_{1}{-}C_{10}}$ alkyl terminated polyalkylene oxide and the polyalkylene oxide chain is selected from the group   \n20 consisting of an ethylene oxide chain, a propylene oxide chain, and an ethylene propylene oxide chain. 5. An aqueous coating composition of claim 3, wherein the polyfunctional resin is hexamethylene disocyanate isocyanurate or hexamethylene diisocyanate biuret.   \n25 6. An aqueous coating composition of claim 3, wherein the curing agent is an amine curing agent. 7. An aqueous coating composition of claim 6, wherein the amine curing agent is selected from the group consisting of bis(para-aminocyclohexyl)methane, diethylene triamine,   \n30 and $^{4,4^{\\prime}}$ -methylene dianiline. 8.A method for making a polyfunctional oligomer having at least two epoxy urethane functional groups and a $\\mathrm{C_{1}}\\mathrm{-}\\mathrm{C_{1}}\\varsigma$ alkyl terminated polyalkylene oxide chain comprising the steps of reacting   \n35 (a) methoxy poly(ethylene glycol) with a polyfunctional isocyanate resin derived from an isocyanurate or a biuret compound; and (b) glycidol with said polyfunctional isocyanate resin. 9. A method for making an aqueous coating composition   \n40 comprising the step of mixing a polyfunctional oligomer having at least two epoxy urethane functional groups and a $\\mathrm{C_{1}}\\mathrm{-}\\mathrm{C_{15}}$ alkyl terminated polyalkylene oxide chain and water to form a dispersion, wherein a surfactant is not added to said aqueous coating   \n45 composition wherein the polyfunctional oligomer comprises a polyfunctional resin derived from an isocyanurate or a biuret compound. 10.A method for making an aqueous coating composition of claim 9 comprising the step of mixing   \n50 (a) 10 to 90 parts of a polyfunctional oligomer having at least two epoxy urethane functional groups and a $\\mathrm{C_{1}}\\mathrm{-}\\mathrm{C_{15}}$ alkyl terminated polyalkylene oxide chain; and (b) 90 to 10 parts water. 11.A method for making an aqueous coating composition   \n55 of claim 9 or 10, further comprising the step of adding a curing agent to the mixture of the polyfunctional oligomer and water after the dispersion. 12.A method for making an aqueous coating composition of claim 9 or 10,further comprising, before the mixing step,   \n60 the step of: reacting a $\\mathrm{C_{1}}\\mathrm{-}\\mathrm{C_{15}}$ alkyl terminated polyalkylene oxide modified polyfunctional resin having at least two isocyanates with glycidol to prepare the polyfunctional oligomer.   \n65 13.A method for making an aqueous coating composition of claim 9, wherein the polyfunctional resin is selected from the group consisting of toluene diisocyanate isocyanurate,  \n\n(a) a polyfunctional oligomer having at least two epoxy urethane functional groups and a $\\mathrm{C_{1}}\\mathrm{-}\\mathrm{C_{15}}$ alkyl terminated polyalkylene oxide chain; and (b) water; wherein said aqueous coating composition does not con- 5 tain a surfactant, wherein the polyfunctional oligomer comprises a polyfunctional resin derived from an isocyanurate or a biuret compound. 2. An aqueous coating composition comprising a disper- 6 sion of: (a) 10 to 90 parts of a polyfunctional oligomer having at least two epoxy urethane functional groups and a $\\mathrm{C_{1}}\\mathrm{-}\\mathrm{C_{15}}$ alkyl terminated polyalkylene oxide chain; and (b) 90 to 10 parts water; wherein said aqueous coating composition does not contain a surfactant,",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 36,
+        "chunk": "# 23",
+        "category": " Introduction"
+    },
+    {
+        "id": 37,
+        "chunk": "# 24  \n\ntoluene diisocyanate biuret, diphenylmethane diisocyanate isocyanurate, diphenylmethane diisocyanate biuret, hexamethylene diisocyanate isocyanurate, hexamethylene diisocyanate biuret, naphthalene diisocyanate isocyanurate, naphthalene diisocyanate biuret, hydrogenated diphenylmethane diisocyanate isocyanurate, hydrogenated diphenylmethane diisocyanate biuret, isophorone diisocyanate isocyanurate and isophorone diisocyanate biuret; and  \n\nthe $\\mathrm{C_{1}}\\mathrm{-}\\mathrm{C_{1}}_{5}$ alkyl terminated polyalkylene oxide is a $\\mathrm{C_{1}{-}C_{10}}$ alkyl terminated polyalkylene oxide and the polyalkylene oxide chain is selected from the group consisting of an ethylene oxide chain, a propylene oxide chain, and an ethylene propylene oxide chain.  \n\n14. The method for making an aqueous coating composition of claim 13, wherein the polyfunctional resin is hexamethylene diisocyanate isocyanurate or hexamethylene diisocyanate biuret.  \n\n15. The method for making an aqueous coating composition of claim 11, wherein the curing agent is amine curing agent. 16. The method for making an aqueous coating compo  \n5 sition of claim 15, wherein the amine curing agent is selected from the group consisting of bis(para-aminocyclohexyl)methane, diethylene triamine, and $^{4,4^{\\prime}}$ -methylene dianiline. 17.A substrate, article, or surface coated with an aqueous   \n10 coating composition of claim 1. 18.An aqueous coating composition of claim 4, wherein the $\\mathrm{C_{1}{-}C_{10}}$ alkyl terminated polyalkylene oxide is methoxy polyalkylene oxide. 19.A method for making an aqueous coating composition   \n15 of claim 13, wherein the $\\mathrm{C_{1}{-}C_{10}}$ alkyl terminated polyalkylene oxide is methoxy polyalkylene oxide.",
+        "category": " Materials and methods"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# HTA - An open-source software for assigning heads and tails to SMILES in polymerization reactions  \n\nBrenda de Souza Ferrari,∗ Ronaldo Giro,† Mathias Steiner ‡  \n\nJanuary 15, 2025",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# Abstract  \n\nArtificial Intelligence (AI) techniques are transforming the computational discovery and design of polymers. The key enablers for polymer informatics are machine-readable molecular string representations of the building blocks of a polymer, i.e., the monomers. In monomer strings, such as SMILES, symbols at the head and tail atoms indicate the locations of bond formation during polymerization. Since the linking of monomers determines a polymer’s properties, the performance of AI prediction models will, ultimately, be limited by the accuracy of the head and tail assignments in the monomer SMILES. Considering the large number of polymer precursors available in chemical data bases, reliable methods for the automated assignment of head and tail atoms are needed. Here, we report a method for assigning head and tail atoms in monomer SMILES by analyzing the reactivity of their functional groups. In a reference data set containing 206 polymer precursors, the HeadTailAssign (HTA) algorithm has correctly predicted the polymer class of 204 monomer SMILES, representing an accuracy of $99\\%$ . The head and tail atoms were correctly assigned to 187 monomer SMILES, representing an accuracy of $91\\%$ . The HTA code is available for validation and reuse at https://github.com/IBM/HeadTailAssign.  \n\nKeywords: Polymers, Cheminformatics, Quantum Chemistry, Materials Science, Materials Discovery  \n\n![](images/7a24989afe25ae09249bb56d2202a268b7de60ee95a669bef3e3a64da9372509.jpg)",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# INTRODUCTION  \n\nPolymers are versatile materials with a wide range of applications $^{1-9}$ . Their properties are mainly determined by the way in which the repeat units, or monomers, are connected within the polymer structure. Typically, there are two preferential binding sites per repeat unit, and the respective atomic positions in the structure are labeled “head” and“tail”10. During polymerization, repeat units might connect head-to-tail, head-to-head, or tail-totail11. Depending on how the repeating units are connected, intermolecular interactions between the polymer chains in the material can significantly alter the physical and chemical properties of the polymer12,13.  \n\nIn polymer informatics $^{14}$ , machine learning (ML) techniques are based on machinereadable representations of a polymer’s repeat units, e.g., the Simplified Molecular-Input Line-Entry System (SMILES)15,16. Polymer-SMILES (p-SMILES) is an extension of SMILES in which symbols such as “\\*” indicate the polymerization points of the repeat units. Alternative representations include the “Hierarchical Editing Language for Macromolecules” (HELM)17, the “INternational CHemical Identifier” (InChI)18, and CurlySMILES19. In general, string representations are limited to homopolymers and are not suitable for capturing the stochastic nature of polymers, such as encoding randomly branched polymers, as is the case for CurlySMILES. More recently, BigSMILES $^{\\mathrm{20}}$ has been applied to represent polymers in string format. In BigSMILES, special characters such as “ $\\$7$ and brackets $^{66}\\langle^{93},^{66}\\rangle^{3}$ indicate the position of head and tail bonds between repeat units. As an advancement, BigSMILES can encode copolymers and enables topological representations of polymeric chains in complex polymers. However, BigSMILES strings provide only a qualitative description of a molecular ensemble $^{21}$ . To fully characterize a polymer, a probability and weight must be assigned to each polymer constituent. By providing a standard format for digitalizing data, PolyDAT $^{21}$ serves as a quantitative extension of BigSMILES.  \n\nAlthough string-format representations of polymers require the tagging of head and tail atoms within the repeat units, computational tools that automatically identify these positions do not yet exist. The Open Parser for Systematic IUPAC Nomenclature (OPSIN)22 interprets organochemical nomenclature efficiently by returning as output the SMILES in string format. If an IUPAC polymer name is given as input, OPSIN returns the modified SMILES with head and tail atoms tagged. However, this method is limited to polymers whose nomenclature is already established. The Monomers-to-Polymers tool (M2P) uses known chemical reactions to build polymer chains from monomers23. This approach is limited to cases where a comparison of polymer chains and repeat units reveals the positions of heads and tails.  \n\nIn this work, we report a method for assigning head and tail atoms in monomer SMILES with the objective to obtain polymer repeat units with bond locations. Our HeadTailAssign (HTA) algorithm quantifies the reactivity of the functional groups of the monomer structure and assigns special characters to those positions in the output SMILES (see Fig.1). In the following, we will outline the computational workflow.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# METHODS",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# Algorithm  \n\nThe HTA algorithm identifies the head and tail positions of the repeat units of a polymer by analyzing the nucleophilicity of its functional groups, see the flow chart in figure 2. In short, the algorithm identifies functional groups within the monomer SMILES and rank-orders their reactivity based on quantum chemical calculations. On the basis of this information, the algorithm then assigns the most likely polymerization mechanism, as well as the positions of head and tail atoms.  \n\nThe input, which is provided as a csv file, contains the polymer name and either a reaction SMILES or a monomer SMILES. If a reaction SMILES is provided, HTA identifies the monomer by evaluating the Chemical Similarity between reactants and products. In short, all molecular entities are separated and their fingerprints are calculated using RDKFingerprint within RDKit $^{24}$ . The fingerprints are then compared with Tanimoto Similarity24,25. Finally, HTA selects the reactant SMILES with the highest similarity score as monomer SMILES.  \n\nIn HTA, data processing is performed by three modules: Assigner, Gamess, and Extractor, see Figure 2. The Assigner performs classification tasks and tags head and tail atoms.  \n\nGamess performs the quantum chemical calculations. The Extractor retrieves information from the output files of the quantum chemical simulations.  \n\nThe Assigner itself performs three operations: Get Class, Get Mechanism, and Get Head Tail. The operations define the polymer class, the polymerization mechanism, and head and tail positions. For identifying the polymer class, the monomer SMILES is compared with the SMARTS $^{26}$ of the most common functional groups that define a polymer class. For example, polyamide contains two functional groups: amide and carboxilic acid. If one of the groups is detected as a nucleophilic site, the molecule is classified as a polyamide.  \n\nIn the current version (2.0.0) of HTA, Get Class is able to classify five polymerization groups: polyvinyl, polyamide, polyester, polyether, and polyurethane. The functional groups representative of each class are shown in figure 3. The most common functional group that promotes polymerization of polyvinyl is alkene. However, in some instances, the alkyne group is also involved.  \n\nFor polyamide, a copolymer or a cyclic monomer is required for polymerization. We account for this by means of a primary amine and a carboxylic acid, as well as primary amine and acyl halide. In the case of a cyclic monomer, we have chosen a secondary amide and a heterocycle monomer to broaden the classification of the polyamide class.  \n\nFor polyester formation, either a copolymer or a cyclic monomer is required. In the first case, monomers are represented by an aliphatic alcohol group and a carboxylic acid group, respectively. In the second case, they are represented by a heterocycle group and a carboxylic acid group, respectively.  \n\nPolyether polymerization requires an opening of a ring in the presence of an ether group. Therefore, the two groups were implemented in HTA to represent the polyether class. Finally, for polyurethane formation, the presence of two monomers is necessary, one with an alcohol group, and the other with a cyanate group.  \n\nIf a monomer contains functional groups compatible with multiple class definitions, it is categorized as such. The quantum-chemical calculations then identify the functional group with the highest reactivity, i.e. the most likely polymerization site.  \n\nTo quantify the reactivity of functional groups within the monomers, we have applied the concept of the nucleophilicity index, which is based on natural orbitals for atomic populations. The atomic index of nucleophilicity involving the highest occupied molecular orbital (HOMO) is defined as27:  \n\n$$\nR_{X}={\\frac{\\sum_{\\alpha}^{X}|C_{\\alpha,n}|^{2}}{(1-\\epsilon_{n,n})}}={\\frac{\\sum_{\\alpha}^{X}|C_{\\alpha}|^{2}}{(1-\\epsilon^{\\star})}}\n$$  \n\nwhere $R_{X}$ is the nucleophilicity index of atom $X$ , $C_{\\alpha,n}$ is the Molecular Orbital (MO) expansion coefficient of the $\\alpha$ th atomic orbital on the $n$ th MO, $\\epsilon_{n,n}$ and $\\boldsymbol{\\epsilon}^{\\star}$ are the HOMO energies, $X$ is the atom index, $\\alpha$ is the index of the atomic orbital, and $n$ is the index of the MO.  \n\nWe have calculated the nucleophilicity index $R_{X}$ with the STO-3G basis set by applying Mulliken’s population analysis method $^{28-30}$ . All quantum states functions were calculated at the SCF / RHF theory level using the standard ab initio quantum-chemistry package GAMESS US $^{31}$ , version 2021 R2.  \n\nWe have generated the GAMESS input file with the Gamess module. In short, the module converts the SMILES string into a 3D coordinate file using the Python library Pybel $^{32}$ , a Python wrapper for the OpenBabel $^{33}$ toolkit. The 3D coordinate file is generated by OpenBabel with geometry optimization using the classical Universal Force Field $^{34}$ with 5000 maximum optimization steps. The 3D coordinate file specifies the coordinates and chemical identity of each atom within the monomer. Finally, the Gamess module constructs the GAMESS input file by merging the keywords with the 3D coordinates in xyz format.  \n\nAll information related to Mulliken‘s population of the HOMO is extracted from the GAMESS output file using the Extractor. The module calculates $R_{X}$ for each of the $X$ atoms of the monomer unit and ranks $R_{X}$ in descending order. In a next step, monomers containing two or more functional groups compatible with existing polymer definitions are classified as follows: the functional group with the highest $R_{X}$ is identified as the monomer’s polymerization site and the monomer is assigned to the respective polymer class.  \n\nThe polymerization mechanism is then obtained by using the Get Class routine. The Get Mechanism routine recognizes the class name and assigns a pre-defined mechanism. For instance, if the polymer class is identified as ”polyamide”, the routine assigns the ”polycondensation” mechanism to the polymer. This process is straightforward for all classes, except for the vinyl mechanism, in which subcategories exist. For example, a pro-vinyl monomer can polymerize through radical polymerization, cationic polymerization, or anionic polymerization35. The likelihood depends on polymerization initiator, solvent, and  \n\npolymerization stereochemistry.  \n\nAn option for identifying the most likely mechanism subcategory is to find the polymerization initiator. If the input provided is related to reaction SMILES, the algorithm can detect the presence of an initiator in the reaction path by means of Chemical Similarity.  \n\nAfter classes and mechanisms are assigned, the HTA algorithm identifies the positions of the head and tail atoms in the monomer SMILES, which are labeled with the symbols $^{66*}$ :1” for head and “\\*:2” for tail, respectively. For each polymer class, the algorithm contains information about the organic function in which the most nucleophilic atom is located. For example, in case of vinyl polymers, polymerization should occur at the double bonds and, in some cases, at the triple bond. Using the atom mappings, the nucleophilic atom is selected as head by convention. In the case where the electrophilic atom occurs in the same organic function, which is the case in vinyl polymerization, the tail is selected from the same organic function. In polyamides, the tail atom is located within a different organic function. In that case, HTA selects the organic functions with the electrophilic atom and, by using atom mappings, assigns the tail atom accordingly. For some classes, such as polyethers and polyamides, the monomers may be structured as a cycle or a macrocycle. In those cases, the cycle is opened by SMILES manipulation, and structural errors are checked with a dedicated sanitization process. SMILES sanitization ensures that a valid molecular structure can be generated from a SMILES string36. In this work, we use the term “sanitization” in the context of manipulating SMILES strings using Regex patterning37.  \n\nThe SMILES representation is treated as a sequence of letters without considering the connections between the atoms. For molecules with aliphatic structures, such as vinyl precursors, this simplification leads to acceptable results. However, for complex molecules, such as cyclic precursors, the connections between atoms should be accounted for.  \n\nFinally, the HTA results are compiled in csv format. They include polymer name, reaction with and without atom mappings, assignment results for monomer, polymer class, polymerization mechanism, as well as head and tail atoms.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# Data  \n\nThe validation data set contains 206 data entries in total, with 149 polymers in the vinyl class, 17 in the polyamide class, 25 in the polyester class, 12 in the polyether class, and 3 in the polyurethane class.  \n\n57 polymer names with polymer SMILES that belong to the polyamide, polyester, polyether, polyurethane class, respectively, were found at Polymerdatabase.com $^{38,3}$ 9. 149 polymer names and (some of the) polymer SMILES that belong to the vinyl class were taken from reference40. To complete the data entries, we have created the missing polymer SMILES either from scratch or, alternatively, by conferring OPSIN $^{41}$ . For validation of the HTA algorithm, we have modified the data set by transforming polymer products into precursors, or monomers, on a case-by-case basis. The algorithm could then be tested for detecting the reaction centers of polymerization.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# Validation  \n\nFor HTA validation, we have tested monomers belonging to the following classes: polyamide, polyester, polyether, and polyurethane. In addition, we have considered monomers that undergo vinyl polymerization, which could be radical, cationic, or anionic.  \n\nSpecifically, we have compared the true head and tail positions of SMILES with the positions predicted by HTA. The head and tail positions were considered as unique tokens and the difference between heads and tails was not taken into account.  \n\nTo compare the results for homopolymers, both the ground-truth and the predicted data set are sorted by polymer name, and monomers with heads and tails assigned (mon-HTA). The canonicalization of the SMILES is performed using RDKit, assuring that the labeling is unambiguous. The comparison of the SMILES strings reveals if each mon-HTA entry has the same canonical SMILES in the ground-truth and the predicted data set. Since the number of entries in the validation data set is small, we have visually compared each individual molecular structure. The results are compiled as a Boolean series in the HTA output file, while the ground-truth and predicted structures are visualized as a png image file.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# RESULTS AND DISCUSSION  \n\nWe have validated the performance of the HTA algorithm; see Fig.2, with a data set containing 206 polymer precursors. The validation data set is described in the Methods section, and the link to the data repository is provided in the Data Availability section.  \n\nWe first evaluate the computational efficiency of the HTA algorithm. Performing the HTA assessment of the full data set required a compute time of roughly 40 minutes on a personal computer (11th Gen Intel Core I5-1135G7, Intel Iris Xe Graphics, 16Gb memory DDR4). This correspond to about 10 seconds per monomer SMILES, including the quantumchemical simulations, which indicates that the HTA algorithm could be used for processing larger data sets.  \n\nIn Fig.4, we present four polymer classification examples representing Polyamide, Polyvinyl, Polyether, and Polyurethane. With a reaction SMILES as input, the algorithm performs an initial assessment of Chemical Similarity. Because the validation data set does not contain any polymerization reactions, the algorithm continues with the polymer classification task.  \n\nIn the example shown in Fig.4a, the monomer polymerizes to Nylon 10 by means of a polycondensation process. The algorithm’s Assigner routine identifies two functional groups in the monomer: an amino group and a carboxylic acid group. By accessing the dictionary that maps the functional groups to polymer classes, the algorithm verifies that both groups indicate the polyamide class and the polycondensation mechanism. The head assignment is performed by finding the atom mapping for the nitrogen of the amino group and the tail assignment is performed by finding the atom mapping for the carbon of the carboxylic acid group.  \n\nIn the second example shown in Fig.4b, the HTA algorithm detects a vinyl group and an amide group. On the basis of the functional group selections that define each class, the HTA algorithm cannot match the monomer with a single polymer class. Therefore, the algorithm has to prioritize the functional groups for polymer class assignment. In this case, the vinyl group is selected. The first reason is that the vinyl group has a higher nucleophilicity index. The second reason is that the amide group is not mapped to any polymer class implemented in HTA. Finally, the head and tail positions are assigned to the carbon atoms forming the double bond in the vinyl group, and the structure is sanitized accordingly.  \n\nIn the third example, which is presented in Fig.4c, the monomer is an epoxy heterocycle. For assignment of head and tail, the monomer has to undergo a ring-opening process. Because there is only one functional group in the SMILES string, the assignments of both polymer class and mechanism are straightforward. The head and tail atoms are then assigned as in the previous example.  \n\nIn the fourth example, shown in Fig.4d, a copolymer is represented with polyurethane precursors. In this case, the algorithm identifies the relevant functional groups of each monomer, i.e. the isocyanate groups and hydroxyl groups, and groups them together for assigning the polymer class. The algorithm can now identify that those monomers belong to the polyurethane class and polymerize through polycondensation. The heads and tails are then assigned to each monomer as two separate entities.  \n\nWe have performed the validation of the HTA results by comparing them with the ground truth and the results are shown in Fig.5. Of the 206 polymer precursors in the data set, HTA has correctly predicted the polymer class for 204 of them, which represents and accuracy of $99.0\\%$ , as shown in Fig.5a).  \n\nThe two monomers of the polyester class that were misclassified, poly(caprolactone) and poly(4-hydroxybutyrate), are displayed in the inset of Fig.5a. Both precursors are heterocycles; however, the algorithm has identified them as cyclic monomers and assigned them to the polyether class. Consequently, the head and tail positions were incorrectly assigned as well. To improve prediction accuracy, a future version of the HTA algorithm should include a definition that cyclic precursors can generate polyester oligomers.  \n\nThe validation of the head and tail assignment, see Fig.5b, reveals that the algorithm has correctly assigned the positions in 187 cases, representing an accuracy of 90.8%. Within the polyurethane class all monomers were correctly assigned.  \n\nWithin the polyvinyl class, incorrect head and tail assignments occurred in two of 149 monomers. A possible explanation is the presence of large groups connected by one of the double bonds in their structures. Polymerization of vinyl monomers follows the polyaddition mechanism in which the reactive site, i.e. the double bond, is attacked by an initiator. The initiator breaks the double bond by forming a single bond with one of the carbon atoms.  \n\nThe second carbon atom remains available to grow the polymer chain42. The attack of the double bond follows chemical rules, and there are situations in which the most nucleophilic atom is not available as a reactive site. As shown in Fig.6a, the structures of Poly(2-tbutyl-1,4-butadiene) and Poly(2-bromo-1,4-butadiene) contain t-butyl and bromine groups, respectively. These groups act as electron donors, increasing the electron population of the vicinal carbon atoms. However, because of their voluminous nature, they might also increase the steric hindrance in the region. The current version of the HTA algorithm does not incorporate specific rules for predicting steric hindrance. As a result, the head and tail positions were simply assigned to the region with the highest nucleophilicity.  \n\nIn some cases, we have observed that the head-and-tail assignment is correct but the sanitization of the SMILES structure is incorrect, in particular if a ring-opening process is involved. We show the example of poly(3-hydroxybutyrate) polymer with its heterocycle precursor in Fig.6b). The head and tail positions were correctly assigned to the oxygen atom of the oxetane ring and to the carbon atom of the carbonyl group. However, the ring-opening process performed by the HTA algorithm generated an incorrect SMILES that cannot be visualized.  \n\nIn another example shown in Fig.6b, the polylactic acid polymer was correctly classified as polyester. However, the polymer head was incorrectly assigned to the carbon atom next to the hydroxyl group. Although the carbonyl and hydroxyl groups were correctly identified as the most nucleophilic regions, the sanitization process removed the hydroxyl group from the tail position but left the hydroxyl group in the structure, leading to incorrect head assignment.  \n\nSuch sanitization issues occurred mainly in the polyether class, in which all precursors, except polyacetal, are cyclic structures. As shown in 5b, over 90% of the structures were incorrectly assigned due to issues associated with the ring-opening process. In case of the poly(hexamethylene oxide) polymer, see Fig.6c), the sanitization process did not produce a SMILES structure for visual evaluation. We have observed improper SMILES sequences in 2 cases and improper ring-opening process in 8 cases. In the case of poly(propylene glycol), the sanitization step has generated a proper SMILES structure; however, the ring-opening process was performed in a manner that has led to an incorrect assignment of the tail position.  \n\nThe same issue was observed in the sole instance in which an incorrect assignment was made within the polyamide class. In the example shown in Fig.6d), the ring in the precursor of Nylon 3 was incorrectly sanitized and generated a false structure with the amide bond intact. In general, the opening of the heterocyclic ring is the most significant challenge of the validation process. Future extensions of the HTA algorithm will require a robust sanitization process for complex monomers, such as cyclic precursors. A potential pathway could be the representation of precursor molecules as graphs during the sanitization phase, with atoms designated as nodes and bonds as edges. The graph representation would allow for the assignment of the bond to be broken, indicated by the edges to be deleted. In addition, atoms or groups of atoms could be deleted or added by indicating the respective nodes. For enhancing the accuracy of the head and tail assignment, we suggest considering the HOMO and LUMO orbitals as the nucleophilic and electrophilic sites, respectively. In addition, considering the comprehensive chemical information provided by the frontier orbitals may be beneficial.  \n\nDespite the methodological limitations discussed above, the lack of polymer data outside the polyvynil class has posed a severe limitation for test and validation of the HTA algorithm. We hope that by making the initial data set publicly available, the computational chemistry community can contribute more data to each polymer class. In addition, improving the existing chemical rules and adding new polymerization classes should enhance the usefulness of the HTA algorithm.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# SUMMARY & CONCLUSIONS  \n\nWe have reported HTA, an algorithm for assigning head and tail atoms in monomer SMILES based on the reactivity of their functional groups. In a reference data set of monomer SMILES, the HTA algorithm has correctly predicted the polymer class with an accuracy of 99%. The head and tail atoms were correctly assigned with an accuracy of $91\\%$ .  \n\nFuture extensions of the HTA algorithm will require a robust SMILES sanitization process for complex monomers. For enhancing the accuracy of the head-and-tail assignments, we suggest including an analysis of LUMO and frontier orbitals in the quantum chemical simulation process. A refinement of the implemented chemical rules and the addition of new polymerization classes should lead to further HTA performance enhancements. To overcome the data bottleneck, we encourage researchers to contribute more data to each polymer class of the initial data set.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 10,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nWe thank Matteo Manica and Teodoro Laino (both IBM Research) for their support in the application of HTA.",
+        "category": " References"
+    },
+    {
+        "id": 11,
+        "chunk": "# DATA AVAILABILITY  \n\nThe data set ”input.csv” for validating the HTA algorithm is available under the doi: 10.24435/materialscloud:tx-b9 at:  \n\nhttps://archive.materialscloud.org/record/2025.6  \n\nThe HTA output file ”output hta.csv” is available under the doi: 10.24435/materialscloud:txb9 at:  \n\nhttps://archive.materialscloud.org/record/2025.6",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# CODE AVAILABILITY  \n\nThe HTA source code is available at https://github.com/IBM/HeadTailAssign.",
+        "category": " References"
+    },
+    {
+        "id": 13,
+        "chunk": "# References  \n\n1. M. Y. Yuhazri, A. J. Zulfikar and A. Ginting, IOP Conference Series: Materials Science and Engineering, 2020, 1003, 012135.   \n2. C.-T. Chen and K. S. Suslick, Coordination Chemistry Reviews, 1993, 128, 293–322.   \n3. Y. K. Sung and S. W. Kim, Biomaterials Research, 2020, 24,.   \n4. F. Sabbagh and B. S. Kim, Journal of Controlled Release, 2022, 341, 132–146.   \n5. C. Chen, H. Ou, R. Liu and D. Ding, Advanced Materials, 2019, 32, 1806331.   \n6. Q. Zheng, Z. Duan, Y. Zhang, X. Huang, X. Xiong, A. Zhang, K. Chang and Q. Li, Molecules, 2023, 28, 5091.   \n7. S. Behera and P. A. Mahanwar, Polymer-Plastics Technology and Materials, 2019, 59,   \n341–356.   \n8. K. Sampathkumar, K. X. Tan and S. C. J. Loo, iScience, 2020, 23, 101055.   \n9. J. Chen, Y. Zhu, J. Huang, J. Zhang, D. Pan, J. Zhou, J. E. Ryu, A. Umar and Z. Guo, Polymer Reviews, 2020, 61, 157–193.   \n10. R. W. Lenz, Organic chemistry of synthetic high polymers, Intercience Publishers, New York, 1967.   \n11. A. A. Askadskii, Computational materials science of polymers, Cambridge Int Science Publishing, 2003.   \n12. Q. Wang, R. Takita, Y. Kikuzaki and F. Ozawa, Journal of the American Chemical Society, 2010, 132, 11420–11421.   \n13. N. Sazali, H. Ibrahim, A. S. Jamaludin, M. A. Mohamed, W. N. W. Salleh and M. N. Z. Abidin, IOP Conference Series: Materials Science and Engineering, 2020, 788, 012047.   \n14. L. Chen, G. Pilania, R. Batra, T. D. Huan, C. Kim, C. Kuenneth and R. Ramprasad, Materials Science and Engineering: R: Reports, 2021, 144, 100595.   \n15. D. Weininger, Journal of Chemical Information and Computer Sciences, 1988, 28, 31–36.   \n16. D. Weininger, A. Weininger and J. L. Weininger, Journal of Chemical Information and Computer Sciences, 1989, 29, 97–101.   \n17. T. Zhang, H. Li, H. Xi, R. V. Stanton and S. H. Rotstein, Journal of Chemical Information and Modeling, 2012, 52, 2796–2806.   \n18. S. R. Heller, A. McNaught, I. Pletnev, S. Stein and D. Tchekhovskoi, Journal of Cheminformatics, 2015, 7,.   \n19. A. Drefahl, Journal of Cheminformatics, 2011, 3,.   \n20. T.-S. Lin, C. W. Coley, H. Mochigase, H. K. Beech, W. Wang, Z. Wang, E. Woods, S. L. Craig, J. A. Johnson, J. A. Kalow, K. F. Jensen and B. D. Olsen, ACS Central Science, 2019, 5, 1523–1531.   \n21. T.-S. Lin, N. J. Rebello, H. K. Beech, Z. Wang, B. El-Zaatari, D. J. Lundberg, J. A. Johnson, J. A. Kalow, S. L. Craig and B. D. Olsen, Journal of Chemical Information and Modeling, 2021, 61, 1150–1163.   \n22. D. M. Lowe, P. T. Corbett, P. Murray-Rust and R. C. Glen, Journal of Chemical Information and Modeling, 2011, 51, 739–753.   \n23. N. Wilson, P. St. John and M. Crowley, m2p (Monomers to Polymers), 2020, https: //www.osti.gov/doecode/biblio/44795.   \n24. RDKit: Open-source cheminformatics, https://www.rdkit.org, DOI: 10.5281/zenodo.591637.   \n25. T. T. Tanimoto, Elementary mathematical theory of classification and prediction, International Business Machines Corp., 1958.   \n26. D. C. I. System, Daylight Theory Manual, Daylight Chemical Information System, 2011.   \n27. D. W. Szczepanik and J. Mrozek, Journal of Chemistry, 2013, 2013,.   \n28. R. S. Mulliken, The Journal of Chemical Physics, 1955, 23, 1833–1840.   \n29. R. S. Mulliken, The Journal of Chemical Physics, 1955, 23, 1841–1846.   \n30. R. S. Mulliken, The Journal of Chemical Physics, 1955, 23, 2343–2346.   \n31. G. M. J. Barca, C. Bertoni, L. Carrington, D. Datta, N. De Silva, J. E. Deustua, D. G. Fedorov, J. R. Gour, A. O. Gunina, E. Guidez, T. Harville, S. Irle, J. Ivanic, K. Kowalski, S. S. Leang, H. Li, W. Li, J. J. Lutz, I. Magoulas, J. Mato, V. Mironov, H. Nakata, B. Q. Pham, P. Piecuch, D. Poole, S. R. Pruitt, A. P. Rendell, L. B. Roskop, K. Ruedenberg, T. Sattasathuchana, M. W. Schmidt, J. Shen, L. Slipchenko, M. Sosonkina, V. Sundriyal, A. Tiwari, J. L. Galvez Vallejo, B. Westheimer, M. Wloch, P. Xu, F. Zahariev and M. S. Gordon, The Journal of Chemical Physics, 2020, 152, 154102.   \n32. N. M. O'Boyle, C. Morley and G. R. Hutchison, Chemistry Central Journal, 2008, 2,.   \n33. N. M. O'Boyle, M. Banck, C. A. James, C. Morley, T. Vandermeersch and G. R. Hutchison, J Cheminform, 2011, 3,.   \n34. A. K. Rappe, C. J. Casewit, K. S. Colwell, W. A. Goddard and W. M. Skiff, Journal of the American Chemical Society, 1992, 114, 10024–10035.   \n35. P. Bruice, Organic Chemistry, Pearson/Prentice Hall, 2004.   \n36. The RDKit Book - Molecular Sanitization, https://www.rdkit.org/docs/RDKit_ Book.html#molecular-sanitization, Accessed: 2025-01-08.   \n37. G. Van Rossum and F. L. Drake, Python 3 Reference Manual, CreateSpace, Scotts Valley, CA, 2009.   \n38. Polymerdatabase.com, https://www.polymerdatabase.com/main.html, Accessed: 2023-05-09.   \n39. Wayback Machine of Polymerdatabase.com, https://web.archive.org/web/ 20230324233129/http://polymerdatabase.com/polymer%20index/home.html, Accessed: 2023-05-09.   \n40. J. Bicerano, Prediction of polymer properties, CRC Press, 2002.   \n41. D. M. Lowe, P. T. Corbett, P. Murray-Rust and R. C. Glen, Chemical name to structure: OPSIN, an open source solution, 2011.   \n42. T. A. Saleh and V. K. Gupta, in Synthesis of Nanomaterial–Polymer Membranes by Polymerization Methods, Elsevier, 2016, p. 135–160.   \n43. Quantum chemistry with Python, https://pyscf.org/.   \n44. Q. Sun, X. Zhang, S. Banerjee, P. Bao, M. Barbry, N. S. Blunt, N. A. Bogdanov, G. H. Booth, J. Chen, Z.-H. Cui, J. J. Eriksen, Y. Gao, S. Guo, J. Hermann, M. R. Hermes, K. Koh, P. Koval, S. Lehtola, Z. Li, J. Liu, N. Mardirossian, J. D. McClain, M. Motta, B. Mussard, H. Q. Pham, A. Pulkin, W. Purwanto, P. J. Robinson, E. Ronca, E. R. Sayfutyarova, M. Scheurer, H. F. Schurkus, J. E. T. Smith, C. Sun, S.-N. Sun, S. Upadhyay, L. K. Wagner, X. Wang, A. White, J. D. Whitfield, M. J. Williamson, S. Wouters, J. Yang, J. M. Yu, T. Zhu, T. C. Berkelbach, S. Sharma, A. Y. Sokolov and G. K.-L. Chan, The Journal of Chemical Physics, 2020, 153, 024109.   \n45. Q. Sun, T. C. Berkelbach, N. S. Blunt, G. H. Booth, S. Guo, Z. Li, J. Liu, J. D. McClain, E. R. Sayfutyarova, S. Sharma, S. Wouters and G. K. Chan, WIREs Computational Molecular Science, 2017, 8, e1340.  \n\n46. Q. Sun, Journal of Computational Chemistry, 2015, 36, 1664–1671.  \n\nFigure 1: Visual representation of the HeadTailAssign (HTA) method with Poly(isobutyl acrylate) as an example. Isobutyl acrylate is shown on the left and Poly(isobutyl acrylate) on the right. Based on quantum chemical predictions of nucleophilicity, the HTA method identifies the atomic locations at which polymerization reactions occur and assigns head and tail positions. The 3D molecular structure visualization was generated by using RDKit $^{24}$ . Starting from a SMILES string Hydrogen atoms were added and conformers were created with a distance-geometry-based conformation generator. Finally, the structure was optimized using the UFF force field and the canonical molecular orbital HOMO was calculated using PySCF $^{43-46}$ , using the STO-3G basis set at SCF / RHF theory level.  \n\nFigure 3: Functional groups for the automated polymer class assignment with the HTA algorithm. Functional groups mapped to (a) Polyvinils, (b) Polyamides, (c) Polyesters, (d) Polyethers, and (e) Polyurethanes.  \n\nFigure 4: Representative examples of automated polymer classification and head/tail assignments with the HTA algorithm. (a) Nylon10 - Poly(decano-10-lactam), (b) Polyacrylamide, (c) Poly(ethylene glycol), and (d) Poly[(diethylene glycol)-alt-(1,6-hexamethylene disocyanate)]. The symbol “\\*:1” indicates a head atom, the symbol “\\*:2” indicate a the tail atom. Different colors indicate different functional groups: orange - amino, blue - carboxilic acid, red - vinyl, brown - amide, pink - ether heterocycle, yellow - isocyanate, green - hydroxyl.  \n\nFigure 5: Comparison between HTA predictions and ground truth data. (a) Predicted polymer classes (orange) and ground-truth data (green). An example of an incorrect HTA prediction (miss-classification) is shown with the respective canonical SMILES representation. (b) HTA-based head and tail assignments (red) and ground-truth data (blue). The symbol “\\*:1” indicates a head atom, the symbol $^{66*}$ :2” indicate a the tail atom.  \n\nFigure 6: Representative examples of incorrect head/tail assignments by the HTA algorithm in the class of (a) Polyvinyl, (b) Polyester, (c) Polyether, and (d) Polyamide. The symbol ”\\*” in the canonical SMILES representations indicate incorrect structure sanitization. The symbol $^{66*}$ :1” indicates a head atom, the symbol “ $^{:*}$ :2” indicate a the tail atom. N/A indicates not applicable, since no valid molecular structure was generated.  \n\n![](images/5b342b9a36c6f1caa4bfae51d138dc9185b5904b1c82662be0841bfbbb442112.jpg)  \nFigure 1  \n\n![](images/83f3e3e3fe7024d9eb4d8d92c29c11323e41dd6c687f73e165e2f5cd20acf11f.jpg)  \nFigure 2  \n\n![](images/a70ce56e58f6558e267ee492c8bbd060128c7fb914001d318c689457a60d7981.jpg)  \nFigure 3  \n\n![](images/9bbab022167cda4aa9e2d8dcba7aa73dd0e4df1fa9dbc552b8ff54afe75c1732.jpg)  \nFigure 4  \n\n![](images/979b9b7e625dd6419aa5380b36ba75404cf73369d74ebeb00844d5a65c3a968e.jpg)  \nFigure 5  \n\n![](images/8f1c1fdd4c3479a0a1af09cf7074bb17851f5b9e0bc1d94d9fbd96506b54b9f7.jpg)  \nFigure 6",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# United States Patent [19] Mallya et al.  \n\n[54] HIGH PERFORMANCE PRESSURE-SENSITIVE ADHESIVE POLYMERS  \n\n[75]  Inventors: Prakash Mallya, Pasadena; Colin Smith, Glendale; Sebastian S. Plamthottam, Pasadena, all of Calif.  \n\n[73] Assignee: Avery International Corporation, Pasadena, Calif.  \n\n[21]  Appl. No.: 138,722  \n\n[22] Filed: Dec. 23, 1987  \n\nInt. Cl.4 C08F 26/08   \nU.S. Cl. 526/264; 526/273   \nField of Search 526/264,273  \n\n[56]",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# References Cited",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# U.S. PATENT DOCUMENTS  \n\n3,787,380 1/1974 Stamberger 526/264   \n4,510,197 4/1985 Shah 526/264  \n\nPrimary Examiner---Paul R. Michi Assistant Examiner--Alex H. Walker Attorney, Agent, or Firm—Christie, Parker & Hale  \n\n[57]",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# ABSTRACT  \n\nPressure-sensitive copolymers based on acrylic monomers are provided with high adhesive performance characteristics by the inclusion of a synergistic amount of an N-vinyl lactam monomer and a glycidyl monomer with the bulk of the monomers being an alkyl acrylate and/or methacryiate esters.  \n\n19 Claims, 1 Drawing Sheet  \n\n![](images/9a7518a69c09c2537a7ab2b78414040575afbf5508a02dac87e0b48a7608f166.jpg)  \n\n![](images/9380002e063b154f7a9c11836d7786035e35c81a85431ce50690adfb8acb9816.jpg)",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# HIGH PERFORMANCE PRESSURE-SENSITIVE ADHESIVE POLYMERS",
+        "category": " Title/Abstract"
+    },
+    {
+        "id": 6,
+        "chunk": "# BACKGROUND OF THE INVENTION  \n\nThe present invention is directed to pressure-sensitive adhesive compositions that exhibit high adhesion to high energy surfaces such as aluminum and possess high tack and outstanding holding power at elevated temperatures. Two key monomers are used in combination in the pressure-sensitive adhesives of this invention to impart unique properties to the resulting polymers. The monomers are at least one glycidyl monomer in combination with at least one N-vinyl lactam.  \n\nThe use of giycidyl monomers in pressure-sensitive adhesive has been disclosed in the art.  \n\nU.S. Pat. No. 3,284,423 discloses creep-resistant pressure-sensitive adhesive compositions comprising $35-75\\%$ by weight alkyl acrylate esters containing 6-15 carbon atoms, 10-60% lower alkyl acrylate, 0.1-10% by weight of an ethylenically unsaturated carboxylic acid and $0.1\\mathrm{-}10\\%$ by weight glycidyl ester.  \n\nU.S. Pat. No. 3,893,982 discloses an interpolymer comprising $0.1\\mathrm{-}15\\%$ parts of an ethylenically unsaturated carboxylic acid, 0.1-2% parts of a glycidyl monomer, 35-84.9% parts of an alkyl acrylate or methacrylate and optionally a monomer selected from the group consisting of alpha-olefins containing 2-10 carbon atoms, vinyl esters of alkanoic acids containing $3-10\\mathbf{\\Omega}_{30}$ carbon atoms, ethyl and methyl esters of acrylic and methacrylic acids, acrylonitrile, methacrylonitrile, styrene and vinyl chloride where the polymer has a weight average.. molecular weight in the  range of 10,000-500,000 and between 0.01 and 1 parts by weight per 100 parts of the copolymer of 1,3-bis(dimethyiamino)-2-hydroxypropane to cause the cure of the epoxy group.  \n\nThe art has also taught the use of N-vinyl iactams in polymers.  \n\nU.S. Pat. No. 3,728,148 discloses a pressure-sensitive adhesive for electrical insulating applications comprising of a copolymer of 65-90% by weight of an alkyl acrylate ester, 10--30 by weight of a N-vinyl lactam and 0-20% by weight of a modifying monomer which is copolymerizable with the above. Acidic monomers and amides are excluded as they are claimed to cause undesirable corrosion.  \n\nU.S. Pat. No. 4,181,752 discloses an interpolymer containing 87% by weight isooctyl acrylate, 8% by weight vinyl pyrrolidone, $3\\%$ by weight acrylic acid and $2\\%$ by weight acrylamide.  \n\nU.S. Pat. No. 4,364,972 discloses a pressure-sensitive adhesive tape made by copolymerizing an alkyl acrylate ester with 15 to 50 parts by weight of vinyl pyrrolidone and having a $\\pmb{\\mathrm{\\delta}}\\mathbf{\\kappa}$ -value greater than 100 and when crosslinked has a gel-swell in ethyl acetate in excess of 600%. Advantages claimed are good adhesion to automotive paints, rubber and plastic foam layers.  \n\nU.S. Pat. No. 4,310,509 discloses a 90/10 2-ethyl hexyl acrylate/vinyl pyrrolidone copolymer for making a pressure sensitive adherent for complexing with iodine for anti-microbial activity.  \n\nEuropean Patent Application No. 130080 discloses an emulsion polymerized pressure-sensitive adhesive comprising 2-20% by weight N-vinyl lactam and an alkyl acrylate ester. The claimed use is good adhesion to skin under hot and humid conditions.  \n\nU.S. Pat. No. 4,370,380 is directed to a blend of two polymers. One is a copolymer of $88-99\\%$ by weight of an alkyl acrylate ester with 1-12% by weight of a carboxylic acid with a glass transition temperature $(\\mathtt{T g})$ of less than 0° C. The second polymer is either a homo or a copolymer of N-vinyl lactam with a $\\pmb{\\mathrm{T}}\\pmb{\\mathrm{g}}$ of $20^{\\circ}-150^{\\circ}\\subset$ The blend ratio is 70-99% by weight of the first polymer with 1-30% by weight of the second polymer. The resultant pressure-sensitive adhesive is disclosed to have moisture permeability.  \n\nU.S. Pat. No. 4,150,197 discloses a water vapor permeable pressure-sensitive adhesive comprising a copolymer of. $79-89\\%$ of butyl acrylate, $10-20\\%$ by weight of $\\mathbf{N}.$ -vinyl lactam and $1-5\\%$ by weight of an acidic comonomer.  \n\nNone of the patents or applications discloses a copolymer containing both a giycidyl monomer and Nvinyl iactam monomer.",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# SUMMARY OF THE INVENTION  \n\nIt has now been found that, as part of an acrylic and/or methacrylic ester based polymer system, a glycidyl monomer and a N-vinyl lactam monomer synergistically act to provide unusually high adhesion to high energy surfaces such as aluminum and stainless steel. The pressure-sensitive adhesives of the invention are formed of copolymers containing essentially no crosslinking when polymerized and which contain on a copolymerized basis from about 0.1 to about $2\\%$ by weight of glycidyl monomer, about $1\\%$ to about $20\\%$ by weight, preferably from about 1 to about $10\\%$ by weight of an $\\mathbf{N}.$ vinyl lactam monomer, from O to about 15% by weight of an ethylenically unsaturated carbox：ylic acid, from about 55 to about $85\\%$ by weight an alkyl acrylate or methacrylate ester containing from 4 to about 12 carbon atoms in the alkyl group, from 0 to $35\\%$ by weight of an alkyl acrylate or methacrylate ester containing less than 4 carbon atoms in the alkyl I group, and optionally, one or more other monomers employed to tailor polymer properties, such as glass transition temperature, to end use applications.  \n\nSuch monomers include polystyryl ethyl methacrylate, acetoacetoxy ethyl methacrylate, styrene, alpha olefins, and vinyl esters of alkanoic acids containing greater than 3 carbon atoms and mixtures thereof. Modifying monomer content can range from O to about $35\\%$ by weight of the total monomers.  \n\nThe ratio of monomers is selected to provide a copolymer with glass transition temperature of less than about $-15^{\\circ}\\mathbf{C}.$ and a weight average molecular weight of at least about 200,000, preferably from about 200,000 to about 500,oo0 as determined by size exclusion chromatography using polystyrene for calibration. Polymers of the instant invention may be synthesized by solution, emulsion and bulk polymerization. It is presently preferred that they be formed by solution polymerization. Polymers are cross-linked to the desired extent, prior to use, using heat, ionic additives, actinic or electron beam radiation and the like.  \n\nThe novel polymers on cross-linking exhibit excellent adhesion to high energy surfaces such as aluminum as evidenced by increased peel adhesion with dwell and superior rivet performance as evidenced by reduced tenting as described herein.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# THE DRAWINGS:  \n\nFIG. 1 graphically compares 180: peel adhesion on alodine aluminum panels of two adhesives, one which contains both a glycidyl monomer and a lactam monomer to one containing only a glycidyl monomer.  \n\nFIG. 2 compares $180^{\\circ}$ peel on stainless steel as a function of dwell at two temperature conditions, room temperature and $120^{\\circ}$ C. for compositions of the invention to controls.  \n\nThe room temperature dwell was for 20 minutes and 120° C. dwell was for 30 minutes. After dwelling for 30 minutes at 120° C., the adhesive on the substrate was allowed to equilibrate to room temperature and $180^{\\circ}$ peel determined.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# DETAILED DESCRIPTION  \n\nPressure-sensitive adhesive polymers of the instant invention are prepared by copolymerizing a mixture of 15 monomers comprising from about 55 to about 85% by weight of an alkyl acrylate and/or methacrylate ester containing 4 to about 12 carbon atoms in the alkyl group; from about 0.01 to about $2\\%$ by weight of a glycidyl monomer; from about 1 to about $20\\%$ by 20 weight, preferably from 1 to about $10\\%$ by weight of an N-vinyl lactam monomer; from 0 to 15% by weight, preferably from about 5 to about $13\\%$ by weight of an unsaturated carboxylic acid; from O to about 35% by weight of an alkyl acrylate and/or methacrylate ester 25 containing less than 4 carbon atoms in the alkyl group and optionally from about 0 to 33% by weight of one or more other comonomers to provide a balance of desirable poiymer properties such as glass transition temperature. The precise ratio of the monomers is selected to 30 give a polymer whose glass transition temperature is lower than about -15° C. The polymers of the instant invention have a weight average molecular weight of at least about 200,000, preferably from about 200,000 to about 500,oo0 as determined by size exclusion chroma- 35 tography using polystyrene as the calibrator.  \n\nThe alkyl acrylate and methacrylate esters containing 4 to about 12 carbon atoms in the alkyl group useful in forming the polymers of the instant invention include without limitation 2-ethyl hexyl acrylate, isooctyl acry- - late, butyl acrylate, sec-butyl acrylate, methyl butyl acrylate, 4-methyl-2-pentyl acrylate, isodecyl methacrylate and the like and mixtures thereof. Isooctyl acrylate and 2-ethyl hexyl acrylate are presently preferred.  \n\nThe glycidyl monomers are glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether and mixtures thereof. The presently preferred gylcidyl monomer is glycidyl methacrylate.  \n\nThe N-vinyl lactams monomers which may be used include N-vinyl pyrrolidone, N-vinyl caprolactam, 1- vinyl-2-piperidone, 1-vinyl-5-methyl-2-pyrrolidone, and the like, N-vinyl pyrrolidone is presently preferred.  \n\nEthylenically unsaturated carboxylic acids include acrylic acid, methacrylic acid, fumaric acid, and the like.  \n\nAlkyl acrylate and methacrylate esters containing less than 4 carbon atoms in the alkyi group include methyl acrylate, ethyl acrylate, methyl methacrylate and the like. Methyl acrylate is presently preferred.  \n\nOther monomers which can be included are polystyryl ethyl methacrylate, acetoacetoxy ethyl methacrylate, alpha olefins such as ethylene and propylene and vinyl esters of alkanoic acids containing more than three carbon atoms as well as mixtures thereof. Such monomer concentrations are in the range from 0 to about 35 percent by weight of the total monomers.  \n\nThe copolymers may be synthesized using solution emulsion, and batch polymerization techniques. It is",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 7  \n\npresently preferred to prepare the copolymers in solution using a mixture of solvents. The present preferred solution polymerization involves the use of blends of ethyl acetate and hexane or ethyl acetate and acetone. 5 The ratio of solvents are adjusted to provide a reflux temperature of from about 68° C. to about 78° C. Solids content during polymerization may typicaily range from about 40% to about 60% in order to achieve the desired weight average molecular weight, and yet l0 achieve viscosities that are manageable in the reactor. Reaction occurs in the presence of free-radical initiators, preferably of the azo type, for example, $^{2,2^{\\prime}}$ -azobis (isobutyronitrile). The polymers formed are solvent soluble polymers with essentially no crosslinking. To .5 this end, the glycidyl monomer is preferably limited to 2% by weight of the total monomers to avoid the possibility of cross-linking, by opening of the oxirane group, during polymerization or during aging. Polymers can, as desired, be post-polymerization cross-linked using :0 heat, actinic or electron beam radiation and the like.  \n\nThe unique characteristics of the cross-linked pressure-sensitive adhesive copolymers of the instant invention is a dramatic adhesion to high energy surfaces, such to aluminum and stainless steel, as seen by increased peel adhesion values with dwell times and superior rivet performance, as reflected by reduced tenting. Superior performance requires the presence of both glycidyl and lactam monomers. In the absence of one, poor adhesion to aluminum has been observed, as manifested by poor tenting performance (see Table I). These results are unexpected as a primary purpose in incorporating the N-vinyl lactam is to increase adhesion to vinyl films and painted surfaces. The purpose of the glycidyl group is normally to introduce a latent functional group which could undergo cross-linking at elevated temperatures under use conditions. This was realized by the dramatic improvement in elevated temperature performance even as high as 20o° C. and high levels of shear adhesion failure temperature (SAFT) of polymers containing glycidyl methacrylate as established by Table II. Improved peel adhesion was totally unexpected. While not bound by theory, it is presently believed that chemical reaction occurs between the epoxy groups and functional groups such as hydroxyl groups on the substrate or a complexation reaction occurs between the epoxy groups and the nitrogen of the lactam, with ionic groups such as Al+++ on the substrate leading to increased bond strength.  \n\nAn application of the adhesives of the instant inven0 tion is the marking of truck panels and the like with an adhesive coated vinyl film. The film is applied over a panel which may be a painted or unpainted aluminum panel fixed with aluminum rivets. The ability of the adhesive to conform to the contour of the rivet and not 5 lift appreciably after application is highly desirable. A tendency to lift away is known as “tenting\" and the greater the separation from the rivet the more unsatisfactory is the adhesive.  \n\nThe SAFT test is a test where the adhesive is applied to 0.5\"×1\" overlap on stainless steel to which a 4.5 lb. roll force applied. After dwell of 24 hours, this is placed in an oven and a kilogram load is applied under shear conditions and temperature raised from 40° C. to 200° C. at the rate of 1° C. per minute. The failure temperature is recorded as the shear adhesion failure temperature. This is a measure of the cohesive strength of the adhesive or the ability of the adhesive to maintain a bond at elevated temperatures.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 5  \n\nWhile not limiting, the following illustrate the invention.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# EXAMPLE1  \n\nA monomer mixture was made up by mixing $\\mathfrak{4}23\\ \\mathfrak{g}$ .of 5 2-ethyl hexyl acrylate, 145 g of methyl acrylate, 3.15 g. of glycidyl methacrylate, 12.6 g of N-vinyl pyrrolidone and $\\mathbf{44.1\\g}$ of acrylic acid. $157\\ \\mathsf{g}.$ . of this mixture was introduced to a 2 liter reactor equipped with a pitched. turbine agitator, a reflux condensor and a thermistor. 10 Also added were $\\begin{array}{r}{73.5\\ \\mathbf{g}.}\\end{array}$ of ethyl acetate and ${78.76\\ \\mathsf{g}}$ of hexane. The contents of the reactor were heated to reflux and $0.238{\\bf g}$ of Vazo 64, manufactured and sold by duPont in ${\\mathfrak{s}}.0{\\ \\mathfrak{g}}$ of ethyl acetate was added. Vigorous reflux started in a short time and the contents of the 15 reactor were held for 23 minutes. At this time, the remaining monomers were mixed with ${\\mathfrak{s}}37.2~\\mathbf{g}.$ .of ethy1 acetate, $\\Im5.2\\ \\mathbf{g}$ . of hexane and $\\mathbf{0.707\\g.}$ of Vazo 64 and added as a single feed mixture over 3.5 hrs. All through the feed, temperature was maintained to keep reactor 20 contents under reflux. One hour after end of feed, 0.17 g. Vazo 64 was added in ${\\pmb5}\\{{\\pmb g}.$ ethyl acetate and held for an additional hour. The percentage of solids content at the end of reaction was $46.4\\%$ and the viscosity was 23 Pa.s using $\\#4@12$ on a Brookfield viscometer. 25",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# EXAMPLE 2  \n\nA monomer mixture was made up by mixing 453.6 g. of Isooctyl acrylate, 100.8 g of methyl acrylate, 6.3 g. of glycidyl methacrylate, ${\\tt25.2~g}$ of N-vinyl caprolactam, $\\pm4.1\\ \\mathsf{g}$ of acrylic acid and $\\mathbf{0.945\\:g}$ of Vazo 64. $\\mathbf{157.5\\:g}$ of this mixture was introduced to the reactor with 78.76 g of hexane, 78.76 g of ethyl acetate and heated to reflex. Once vigorous reflux initiated, the contents were held for about 12 minutes and the remaining monomers added along with 537.24 g of ethyl acetate and 75.24 g of hexane as a single feed over 3 hours. Two hours after the end of feed, the contents were cooled.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 14,
+        "chunk": "# EXAMPLE 3",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# Tenting Test  \n\nThere was formed as control 1 a polymer containing 65.7% by weight 2-ethyl hexyl acrylate, 27.3% by weight methyl acrylate and 7% by weight acrylic acid. As Control 2, there was formed a polymer containing 67% by weight 2-ethyl hexyl acrylate, 24% by weight methyl acrylate, 7% acrylic acid, and 2% by weight N-vinyl pyrrolidone. As Control 3, there was formed a polymer containing $65.7\\%$ by weight 2-ethyl hexyl acrylate, $27.2\\%$ by weight methyl acrylate, $7\\%$ by weight acrylic acid and 0.1% by weight glycidyl methacrylate. As Control 4, there was used a polymer containing 65% by weight 2-ethyl hexyl acrylate, 27% by weight methyl acrylate, 7% by weight acrylic acid and 1% by weight glycidyl methacrylate. These were compared for tenting in a rivet test to the polymers of Examples 1 and 2. As a cross-linker in each instance, there was added 0.2 parts by weight of the polymer of aluminum acetyl acetonate. For the rivet tenting test adhesive was transfer coated from a release liner to a cast vinyl facestock, at a coat weight of $30~\\mathbf{g}/\\mathbf{m}^{2}$ The results are given in Table 1, wherein the lower the value reported, the less tenting, i.e., lifting away from the rivet, occurred.  \n\nTable 2 compares the polymer of Example 1 electronbeam (EB) cured at a dosage of 30 kiloGray (kGy) and the polymer of Example 2 also EB cured at a dosage of  \n\n$30\\ensuremath{\\mathrm{\\kGy}}$ . Exampies 1 and 2 exhibited the best combinations of shear and tack.   \n\n\n<html><body><table><tr><td></td><td>Control/ Example*</td><td>Tenting in Rivet Test, mm</td></tr><tr><td>，</td><td>Control 1</td><td>1.42</td></tr><tr><td></td><td>Control 2</td><td>1.32</td></tr><tr><td></td><td>Control 3</td><td>1.37</td></tr><tr><td></td><td>Control 4</td><td>1.25</td></tr><tr><td></td><td>Example I</td><td>0.58</td></tr><tr><td></td><td>Example 2</td><td>1.1</td></tr></table></body></html>\n\n\\*All the polymers were cross-linked with 0.2 parts per hundred parts of the polymer of Aluminum acetyl acetonate.  \n\nTABLE1   \nTABLE 2   \n\n\n<html><body><table><tr><td>180° Peel, NM Stainiess Steei, 20' Dwell 0 Hard PVC. Static Shear, min. 20° C./1 kg 150° C./1 kg 200° C./1 kg Loop Tack, N/M 5 SAFT, °C.</td></tr></table></body></html>\n\nRT Shear, 0.5 × 0.5 inch overlap, Al Facestock SAFT and ET Shear. 0.5 X 1.0 inch overlap, Al Facestock For SAFT, 24 hr. dwell, rate of heating 1° C./minute",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 16,
+        "chunk": "# CONTROL 5 to 8 and EXAMPLES 4 and 5  \n\nThere was compared to the product of Example 2 a copolymer containing 67 parts by weight isooctyl acrylate, 25 parts by weight methyl acrylate, 1 part by weight glycidyl methacrylate, and 7 parts by weight   \n35 acrylic acid (Control 5). Control 5 and Example 2 copolymers were coated to a level of $50~\\mathrm{g}/\\mathrm{m}^{2}$ onto mylar and cured at an electron beam level of $30\\ensuremath{\\mathrm{\\kGy}}$ . A comparison of $180^{\\circ}$ peel on alodine aluminum substrate in Newtons/meter (N/M) as a function of dwell time is   \nI0 shown in FIG. 1 and establishes that the combination of glycidyl methacrylate and vinyl caprolactam produce unusually high $180^{\\circ}$ peels, especially after extended dwell times. FIG. 2 compares 180° peel on stainless steel substrate   \n45 as a function of dweil at room temperature for $20{\\mathrm{~min}}.$ ， utes and dwell at 120° C. for 30 minutes followed by peel testing at room temperature. All polymers employed contained 2-ethyl hexyl acrylate, methyl acrylate and acrylic acid. Control 6 contained no glycidyl   \n50 methacrylate or N-vinyl lactam. Control 7 contained 0.1 part glycidyl methacryiate but no $\\mathbf{N}.$ -vinyl lactam. Control 8 contained 1 part by weight glycidyl methacrylate but no N-vinyl lactam. Example 4 contained 0.1 part by weight glycidyl methacrylate and 2 parts by   \n55 weight N-vinyl pyrrolidone. Example 5 contained 0.1 part by weight glycidyl methacrylate and 4 parts by weight N-vinyl caprolactam per hundred parts total monomer. In each instance, the polymers were EB cured at'a dosage of 30 kGy. The glycidyl methacrylate   \n50 in combination and N-vinyl lactam gives better performance in terms of adhesion to high energy surfaces than the individual constituents of the combination.  \n\nWhat is claimed is:  \n\n1. A pressure-sensitive adhesive comprising a copoly65 mer comprising on a copolymerized basis from about 55 to about $85\\%$ by weight of a monomer selected from the group consisting of alkyl acrylate esters and alkyl methacrylate esters containing from 4 to about 12 carbon atoms in the alkyl group and mixtures thereof, from O to about $35\\%$ by weight of an alkyl acrylate or methacryiate ester containing less than 4 carbon atoms in the alkyl group, from 0.01 to about $2\\%$ by weight of a glycidyl monomer, from about 1 to about $10\\%$ by weight of an N-vinyl lactam, and from O to about $15\\%$ by weight of an unsaturated carboxylic acid, said copolymer having a weight average molecular weight of at least about 2oo,oo0 and a glass transition temperature less than about $-15^{\\circ}\\mathbf{C}$  \n\n2. A pressure-sensitive adhesive as claimed in claim 1 which contains, based on the total weight of monomers, up to about $35\\%$ by weight, of a monomer selected from the group consisting of polystyryl ethyl methacrylate, aceto-acetoxy ethyl methacrylate, styrene, alpha olefins, vinyl esters of alkanoic acids containing more than about three carbon atoms and mixtures thereof.  \n\n3. A pressure-sensitive adhesive as claimed in claim 1 in which the alkyl acrylate is 2-ethyl hexyl acryiate or isooctyl acrylate.  \n\n4. A pressure-sensitive adhesive as claimed in claim 2 in which the alkyl acrylate is 2-ethyl hexyl acrylate or isooctyl acrylate.  \n\n5. A pressure-sensitive adhesive as claimed in claim 1 in which the glycidyl monomer is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether and mixtures thereof.  \n\n6. A pressure-sensitive adhesive as claimed in claim 2 : in which the glycidyl monomer is selected from the group consisting of glycidyl acrylate, glycidyl methacryiate, allyl glycidyl ether and mixtures thereof.  \n\n7. A pressure-sensitive adhesive as claimed in claim 3 in which the glycidyl monomer is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether and mixtures thereof.  \n\n8. A pressure-sensitive adhesive as claimed in claim 4 in which the glycidyl monomer is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether and mixtures thereof.  \n\n9. A pressure-sensitive adhesive as claimed in claim 1 in which the N-vinyl lactam is selected from the group consisting of N-vinyl pyrrolidone, N-vinyl caprolactam and mixtures thereof.  \n\n10. A pressure-sensitive adhesive as claimed in claim   \n2 in which the N-vinyi lactam is selected from the group  \n\nconsisting of N-vinyl pyrrolidone, N-vinyl caprolactam and mixtures thereof.  \n\n11. A pressure-sensitive adhesive as claimed in ciaim 3 in which the N-vinyl lactam is selected from the group consisting of N-vinyl pyrrolidone, N-vinyl caprolactam and mixtures thereof.  \n\n12. A pressure-sensitive adhesive as claimed in claim 4 in which the N-vinyl lactam is selected from the group consisting of N-vinyl pyrrolidone, N-vinyl caprolactam and mixtures thereof.  \n\n13. A pressure-sensitive adhesive as claimed in claim 5 in which the N-vinyl lactam is selected from the group consisting of N-vinyl pyrrolidone, N-vinyl caprolactam and mixtures thereof.  \n\n14. A pressure-sensitive adhesive as claimed in claim 6 in which the N-vinyl lactam is selected from the group consisting of N-vinyl pyrrolidone, N-vinyl caprolactam and mixtures thereof.  \n\n15. A pressure-sensitive adhesive as claimed in claim . 7 in which the N-vinyl lactam is selected from the group consisting of N-vinyl pyrrolidone, N-vinyl caprolactam and mixtures thereof.  \n\n16. A pressure-sensitive adhesive as claimed in claim 8 in which the N-vinyl lactam is selected from the group consisting of N-vinyi pyrrolidone, N-vinyl caprolactam and mixtures thereof.  \n\n17. A pressure-sensitive adhesive as claimed in ciaim 1 in which the formed copolymer is cross-linked by exposure to heat, ionic additive, actinic radiation or electron beam radiation.  \n\n18. A pressure-sensitive adhesive comprising a copolymer comprising frm about 55 to about $85\\%$ of an alkyl acrylate ester selected from the group consisting of isooctyl acrylate and 2-ethyl hexyl acrylate, from 5 about 0.01 to about 2% by weight glycidyl methacrylate, from about 1 to about 10% of a N-vinyl lactam selected from the group consisting of N-vinyl pyrrolidone and N-vinyl caprolactam, from about 5 to 13% by weight unsaturated carboxylic acid, and up to about 0 $35\\%$ by weight methyl acrylate, said polymer having weight average molecular weight from about 200,000 to about 50o,ooo and a glass transition temperature less than about $-15^{\\circ}\\mathbf{C}$  \n\n19. A pressure-sensitive adhesive as claimed in claim 18 in which the formed copolymer is cross-linked by exposure to heat, ionic additive, actinic radiation or electron beam radiation.  \n\n60  \n\n65",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION  \n\nPATENTN0. : 4,812,541   \nDATED : March 14, 1989   \nINVENTOR(S): P. Mallya; C. Smith; S. S. Plamthottam  \n\nIt is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below:",
+        "category": " References"
+    },
+    {
+        "id": 18,
+        "chunk": "# In the Specification:  \n\nColumn 4, line 24, change \"to\" to -- as Column 4, line.6l, after \"force\" insert -- is --  \n\nColumn 5, line 29, change \"Isooctyl\" to -- isooctyl Column 5, line 33, change \"reflex\" to -- reflux  \n\nColumn 6, line 30, change \"coNTROL\" to 1 CONTROLS  \n\nIn the Claims  \n\nColumn 8, line 32, change \"frm\" to -- from",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 19,
+        "chunk": "# Signed and Sealed this Twenty-fourth Day of April, 1990  \n\nAttest:  \n\nHARRY F. MANBECK,JR.  \n\nAttesting Officer  \n\nCommissioner of Patents and Trademarks",
+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,87 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Highly transparent superhydrophilic graphene oxide coating for antifogging  \n\nXuebing Hu a,b,n, Yun Yu b,nn, Yong Wang b, Yongqing Wang a, Jianer Zhou a, Lixin Song b  \n\na Key Laboratory of Inorganic Membrane, Jingdezhen Ceramic Institute, Jingdezhen 333001, China b Key Laboratory of Inorganic Coating Materials, Shanghai Institute of Ceramics, Chinese Academy of Science, Shanghai 201800, China",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# a r t i c l e i n f o",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# a b s t r a c t  \n\nArticle history:   \nReceived 29 March 2016   \nReceived in revised form   \n28 June 2016   \nAccepted 29 June 2016   \nAvailable online 30 June 2016   \nKeywords:   \nGraphene oxide   \nFunctional   \nSuperhydrophilic   \nTransparent   \nAntifogging   \nSurfaces  \n\nThe superhydrophilic property of the surface allows water to spread completely across the surface rather than remain as droplets, thus making the surface antifogging. In this work, graphene oxide was prepared by the modified Hummers method, and the superhydrophilic and highly transparent functional graphene oxide coating had been fabricated on the glass substrate through a spin coating process. The as-prepared coated glass had a static water contact angle of $3.7^{\\circ}$ and a relatively high transmittance reaching about $76\\%$ throughout the visible region. For comparison, we studied the antifogging properties of the graphene oxide coated glass and the bare glass surfaces. The result shows these glass exhibits absolutely different fogging characteristics, and the graphene oxide coated glass has the superior antifogging property.  \n\n$\\circledcirc$ 2016 Elsevier B.V. All rights reserved.",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1. Introduction  \n\nThe wettability of solid surface is an attractive topic due to its importance in fundamental research and practical applications [1]. Water vapor can condense on solid surface at a certain temperature or humidity, and water will form little droplets on a solid surface if the surface is poor hydrophilic or hydrophobic. Therefore the light would be refracted and scattered by water droplets so that the transparent materials turn hazy, which causes fogging problem [2]. Endowing the solid surface with excellent wetting characteristic such as superhydrophilicity is a very efficient way to solve the above-mentioned problem [3]. Nowadays, superhydrophilic surface, a special wettability with a water contact angle of less than $5^{\\circ}$ , has received great attention as antifogging coating [4]. Numerous materials, for example, metal oxide $\\mathrm{TiO}_{2}$ , $z_{\\mathrm{{nO}}}$ , $\\mathsf{S n O}_{2}$ and ${\\mathsf{W O}}_{3}$ ) and graphene had been developed for preparing superhydrophilic surface [5–9].  \n\nFollowing the studies on graphene, graphene oxide (GO) has been widely investigated in recent decade, since its many unique and interesting properties such as large external surface area, excellent corrosion-resistant, good antibacterial property, and high mechanical strength, with the advantage of having a simple and inexpensive synthesis process [10,11]. Nowadays, GO based coating can be used for a wide range of applications such as corrosion protection, bacterial growth inhibition, water treatment and so on [12–14]. In particular, due to the presence of various oxygen containing functional groups such as epoxy, hydroxyl and carbonyl groups on its basal planes and edges, GO exhibits hydrophilic property and its wetting ability can be adjusted by the synthesis process [15–17]. However, it is difficult for common graphene oxide coating to be used as superhydrophilic surface material, since the microstructure and functional groups composition of GO coating can not be tailored easily. The previous preparation methods of superhydrophilic GO coating mostly included the complex step of reduction and bridization [18–20]. Therefore, a fast and facile approach for the high optical transmittance and superhydrophilic GO coating fabrication needs to be explored. Especially, due to the above-mentioned intriguing properties of GO, GO based coating has become a very competitive and promising candidate for anti-fogging application.  \n\nIn the current work, we present a simple and low-cost method for preparing high performance GO coating on the glass substrate. The coating exhibits superhydrophilicity, superior antifogging property and high optical transmittance throughout the visible region. Our work would greatly simplify the fabrication procedure of high performance GO coating and accelerate its promising applications in industry and daily life, such as mirrors, window glasses, windshields of automobiles, and so on.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2. Experimental procedure",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.1. Materials  \n\nMicrocrystalline graphite powders $99.9\\%$ purity) were purchased from Qingdao Sanyuan Graphite Co., Ltd. Potassium permanganate (AR), sodium nitrate (AR), concentrated sulfuric acid (AR, $98\\%$ ), hydrogen peroxide (AR, $30\\mathrm{wt\\%}$ aqueous solution), and quantitative filter paper were purchased from Sinopharm Chemical Reagent Co., Ltd.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.2. Synthesis of GO  \n\nGO was prepared using the modified Hummers method [15]. To remove the onus of oxidant and other inorganic impurity, the GO slurry was washed with the deionized water by repeated vacuum filtration through a $100\\mathrm{nm}$ cellulose acetate membrane. Then the suspension was centrifuged (13,000 rpm for $80\\mathrm{min}_{,}$ ), the supernatant was kept. Finally, the supernatant was diluted with deionized water to a total volume of $200\\mathrm{ml}$ in a $500\\mathrm{ml}$ flask to make a homogeneous GO suspension $(0.2\\mathrm{mg}1^{-1})_{\\cdot}$ ) for storing.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.3. Preparation of GO coating  \n\nGO coating was deposited on the glass substrate by a spin coating process. Initially, the substrate was ultrasonically cleaned in ethanol and deionized water. After cleaning, the substrate was dried at $60^{\\circ}\\mathsf C$ for $^{1\\mathrm{h}}$ . Then, the above-mentioned GO suspension was dropped on the glass substrate and spun at $500\\mathrm{rpm}$ for $10s$ and dried at $60^{\\circ}C$ for $^{3\\mathrm{~h~}}$ to enhance the mechanical property of the coating. The other side of glass substrate was operated by the same procedure. Finally, the both sides of glass substrate were covered with GO coating.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.4. Characterization and measurement methods  \n\nX-ray diffraction (XRD, D8 ADVANCE, Germany) was recorded on a D/max $2550\\mathrm{V}$ diffractometer with Cu Ka radiation $\\scriptstyle\\lambda=0.1542\\mathrm{nm}$ ). X-ray photoelectron spectroscopy (XPS, MICROLAB 310F, Thermo Scientific, UK) spectra were measured using Mg Ka as the exciting resource. The microstructure of the sample was investigated by Transmission electron microscopy (TEM, JEM200CX, Japan). The morphology of as-prepared GO coating was obtained by field emission scanning electron microscopy (FE-SEM, Hitachi SU8220, Japan). The root mean square (RMS) surface roughness of the GO coating was examined with an atomic force microscope (AFM, Bruker, Germany) operating in the tapping mode. The superhydrophilicity of the sample was evaluated with the water contact angle instrument (SL200B, China) by measuring the static contact angle of the deionized water droplet. The transmittance of the samples was carried out by UV–visible spectrophotometer (UV2310, China) at normal incidence in the wavelength between 300 and ${900}\\mathrm{nm}$ . For examination of antifogging property, a GO coated glass and a bare glass were cooled at ca. $-15^{\\circ}C$ for $^{3\\mathrm{h}}$ in a refrigerator, and then exposed to humid laboratory air (room temperature: $20{-}30^{\\circ}\\mathsf C$ , relative humidity: 20– $40\\%$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3. Results and discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3.1. XRD patter, XPS spectrum and microstructure of GO  \n\nThe XRD pattern of GO is shown in Fig. 1a. GO has a low intensity peak at $11.8^{\\circ}$ , which attributes to the (001) reflection of GO. The C 1s XPS spectrum of GO is presented in Fig. 1b. The spectrum is decomposed into three fitted peaks using a Gaussian function. A binding energy of $284.9\\mathrm{eV}$ indicates the existence of C–C sp2 bonds in GO, while $287.1\\ \\mathrm{eV}$ results from C–O bonds (epoxy and hydroxyl groups), and $288.5\\mathrm{eV}$ shows ${\\mathsf{C}}{=}0$ bonds (carbonyl) are formed during the oxidation process [21].  \n\nThe sp2 carbon (C–C) fraction can characterize the oxidation degree in GO, which can be estimated by dividing the area by C 1s peak area [17]. From Fig. 1b, the C–C fraction of GO is about $46.4\\%$ . The result shows there are fewer C–C groups in GO and also reflects GO has more oxygen-containing functional groups. With the increase of these groups, the hydrophilic property of GO will be enhanced [22].  \n\nThe microstructure of GO is inspected by TEM. From Fig. 1c, the average size of GO nanosheets is about $150\\mathrm{nm}$ and GO has excellent dispersibility.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3.2. The surface morphology and wettability of GO coating  \n\nThe surface morphology of the GO coating was characterized by FE-SEM and the tapping mode AFM. As shown in Fig. 2a, it indicates some aggregations have been formed due to the larger amount of GO loading, so that the coating surface is not smooth. The cross-section image of GO coating is shown in Fig. 2b, which indicates the thickness of GO coating is about $100\\mathrm{nm}$ As displayed in Fig. 2c, it is also observed the surface of the coating presents some roughness that possibly arises from the random overlap and aggregation of individual GO sheets. The RMS roughness ups to $9.32\\mathrm{nm}$ .  \n\nFrom Fig. 2d, the static water contact angle (WCA) of $\\sim3.7^{\\circ}$ is observed for GO coating. The small water contact angle suggests the coating represents the superhydrophilic property. From Fig. 2c, we can know the coating surface has a higher surface roughness. According to Wenzel equation [23]:  \n\n![](images/49c8500cafe5a50b4422ae51061ad3ddfbe9db0af3489162532361b0f4995eea.jpg)  \nFig. 1. (a) XRD pattern, (b) XPS spectrum and (c) TEM image of GO.  \n\n![](images/fb03128470b94a57f992d17952ace1a51900f7c0dba6f0e476286025523f3e1d.jpg)  \nFig. 2. FE-SEM images in (a) top view and (b) cross-sectional view of a GO coating, (c) three-dimensional AFM image, (d) water contact angle of GO coating on the glass substrate.  \n\n$$\n\\mathrm{cos\\theta_{w}}=\\gamma\\mathrm{cos\\theta_{e}}\n$$  \n\nwhere $\\uptheta_{\\mathrm{w}}$ is the apparent WCA in Wenzel state, $\\boldsymbol{\\upgamma}$ is the surface roughness factor and $\\uptheta_{\\mathrm{e}}$ is the equilibrium WCA on the horizontal and smooth surface. In the case of a principally hydrophilic surface, a decrease of WCA is predicted following an increase of $\\boldsymbol{\\upgamma}$ .  \n\nAs shown in Fig. 2c, it is clear that there are some corrugations on the coating surface and the RMS surface roughness is $9.32\\mathrm{nm}$ . The results indicate the coating has a higher surface roughness so that the value of $\\boldsymbol{\\upgamma}$ increases, which is beneficial to magnify the intrinsic wetting characteristic of the surface. It has also been further confirmed by Fig. 2d.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3.3. The transmittance of GO coating  \n\nTo evaluate the optical transmission, a comparative test about the transmittance of the bare and GO coated glasses was carried out by UV–visible measurement.  \n\nAccording to the UV–visible spectra in Fig. 3, the GO coated glass shows a high transmittance reaching about $76\\%$ , while the transmittance of the bare glass is about $90\\%$ throughout the visible region. It is observed there was a decrease in transmittance with the GO coated, which can be ascribed to the light reflecting and scattering resulting from the surface roughness and the air-coating and the coating-substrate interfaces [24].  \n\nGenerally, the high roughness and high transmittance is a pair of competitive properties due to extensive light scattering [25]. Interestingly, it can be revealed from the above results of experiment that the GO coated glass has a good transmittance with the  \n\n![](images/ec5071836aee722bf0997f578b0b059235083143aeebbe6cd4b04b7cdbaa8db0.jpg)  \nFig. 3. UV–Vis transmission spectra of GO coated glass and bare glass.  \n\nRMS surface roughness ups to $9.32\\:\\mathrm{nm}$ .",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.4. The antifogging of GO coating  \n\nWe investigated the antifogging properties of the GO coated glass and the bare glass, as shown in Fig. 4. Both glass samples were cooled at ca. $-15^{\\circ}C$ for $^{3\\mathrm{h}}$ in a refrigerator, and then simultaneously exposed to humid laboratory air.  \n\nAs shown in Fig. 4, the bare glass (left) fogged immediately and presented a large amount of tiny condensed droplets causing a significant reduction of the optical transmittance. As a comparison, the GO coated glass (right) remained clear and excellent transparency during the whole antifogging test. Thus, the GO coating should play an active role in antifogging property of glass. This special antifogging ability should be attributed to that the nearly instantaneous spreading of water droplets on the superhydrophilic surface. Thus, water could evaporate soon and the GO coated glass surface was kept clear at all times.  \n\n![](images/8aa7a980079defb554bfe672b93e14f8a2a478dd33ff8b61941ff1d9f69077ef.jpg)  \nFig. 4. Images of the fogging comparison experiment between GO coated glass and bare glass after cooling.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 4. Conclusion  \n\nWe presented a facile route to fabricate highly transparent superhydrophilic GO coating on glass substrate. The resultant superhydrophilic surface shows a static water contact angle of $3.7^{\\circ}$ and a transmittance reaching about $76\\%$ throughout the visible region. We also discussed the antifogging characteristic of GO coated glass and bare glass, the result demonstrates the GO coated glass has a superior antifogging property.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 16,
+        "chunk": "# Acknowledgements  \n\nThe authors gratefully acknowledge the support of this research by the National Natural Science Foundation of China (Grant No. 51262012) and the Foundation of Jiangxi Science and Technology Committee (Grant Nos. 20133ACB20007 and 20161ACB21008). The project also was funded by the Key Laboratory of Inorganic Coating Materials, Chinese Academy of Sciences (Grant No. KLICM-2014-07).",
+        "category": " References"
+    },
+    {
+        "id": 17,
+        "chunk": "# References  \n\n[1] Z. Pan, J.A. Weibel, S.V. Garimella, Influence of surface wettability on transport mechanisms governing water droplet evaporation, Langmuir 30 (2014)  \n\n9726–9730. [2] Y. Yuan, R. Liu, C. Wang, J. Luo, X. Liu, Synthesis of UV-curable acrylate polymer containing sulfonic groups for anti-fog coatings, Prog. Org. Coat. 77 (2014) 785–789. [3] X. Li, B. Shi, M. Li, L. Mao, Synthesis of highly ordered alkyl-functionalized mesoporous silica by co-condensation method and applications in surface coating with superhydrophilic/antifogging properties, J. Porous Mater. 22 (2015) 201–210. [4] P. Chen, Y. Hu, C. Wei, Preparation of superhydrophilic mesoporous $\\mathrm{SiO}_{2}$ thin films, Appl. Surf. Sci. 258 (2012) 4334–4338. [5] R. Dong, S. Jiang, Z. Li, Z. Chen, H. Zhang, C. Jin, Superhydrophilic $\\mathrm{TiO}_{2}$ nanorod films with variable morphology grown on different substrates, Mater. Lett. 152 (2015) 151–154. [6] J. Li, L. Yan, W. Li, J. Li, F. Zha, Z. Lei, Superhydrophilic-underwater superoleophobic ZnO-based coated mesh for highly efficient oil and water separation, Mater. Lett. 153 (2015) 62–65. [7] K. Yadav, B.R. Mehta, K.V. Lakshmi, S. Bhattacharya, J.P. Singh, Tuning the wettability of indium oxide nanowires from superhydrophobic to nearly superhydrophilic: effect of oxygen-related defects, J. Phys. Chem. C 119 (2015) 16026–16032. [8] A. Srinivasan, M. Miyauchi, Chemically stable ${\\sf W O}_{3}$ based thin-film for visiblelight induced oxidation and superhydrophilicity, J. Phys. Chem. C 116 (2012) 15421–15426. [9] J. Rafiee, M.A. Rafiee, Z.Z. Yu, N. Koratkar, Superhydrophobic to superhydrophilic wetting control in graphene films, Adv. Mater. 22 (2010) 2151–2154.   \n[10] Y. Gao, C. Qin, Z. Qiao, B. Wang, W. Li, G. Zhang, R. Chen, L. Xiao, S. Jia, Imaging and spectrum of monolayer graphene oxide in external electric field, Carbon 93 (2015) 843–850.   \n[11] D.R. Dreyer, A.D. Todd, C.W. Bielawski, Harnessing the chemistry of graphene oxide, Chem. Soc. Rev. 43 (2014) 5288–5301.   \n[12] R.K. Upadhyay, N. Soin, G. Bhattacharya, S. Saha, A. Barman, S.S. Roy, Grape extract assisted green synthesis of reduced graphene oxide for water treatment application, Mater. Lett. 160 (2015) 355–358.   \n[13] K. Krishnamoorthy, A. Ramadoss, S.J. Kim, Graphene oxide nanosheets for corrosion-inhibiting coating, Sci. Adv. Mater. 5 (2013) 406–410.   \n[14] J.H. Park, J.M. Park, Electrophoretic deposition of graphene oxide on mild carbon steel for anti-corrosion application, Surf. Coat. Technol. 254 (2014) 167–174.   \n[15] X.B. Hu, Y. Yu, W.M. Hou, J.E. Zhou, L. Song, Effects of particle size and pH value on the hydrophilicity of graphene oxide, Appl. Surf. Sci. 273 (2013) 118–121.   \n[16] R. Rasuli, Z. Mokarian, R. Karimi, H. Shabanzadeh, Y. Abedini, Wettability modification of graphene oxide by removal of carboxyl functional groups using non-thermal effects of microwave, Thin Solid Films 589 (2015) 364–368.   \n[17] X.B. Hu, Y. Yu, J.E. Zhou, L. Song, Effect of graphite precursor on oxidation degree, hydrophilicity and microstructure of graphene oxide, Nano 9 (2014) 1450037.   \n[18] H. Zanin, E. Saito, H.J. Ceragioli, V. Baranauskas, E.J. Corat, Reduced graphene oxide and vertically aligned carbon nanotubes superhydrophilic films for supercapacitors devices, Mater. Res. Bull. 49 (2014) 487–493.   \n[19] L. Kou, C. Gao, Making silica nanoparticle-covered graphene oxide nanohybrids as general building blocks for large-area superhydrophilic coatings, Nanoscale 3 (2011) 519–528.   \n[20] H. Zanin, E. Saito, F.R. Marciano, H.J. Ceragioli, A.E.C. Granato, M. Porcionatto, Fast preparation of nano-hydroxyapatite/superhydrophilic reduced graphene oxide composites for bioactive applications, J. Mater. Chem. B 1 (2013) 4947–4955.   \n[21] T. Kuila, S. Bose, P. Khanra, A.K. Mishra, N.H. Kim, J.H. Lee, A green approach for the reduction of graphene oxide by wild carrot root, Carbon 50 (2012) 914–921.   \n[22] J. Chen, B. Yao, C. Li, G. Shi, An improved Hummers method for eco-friendly synthesis of graphene oxide, Carbon 64 (2013) 225–229.   \n[23] V. Tamilselvan, D. Yuvaraj, R.R. Kumar, K.N. Rao, Growth of rutile $\\mathrm{TiO}_{2}$ nanorods on $\\mathrm{TiO}_{2}$ seed layer deposited by electron beam evaporation, Appl. Surf. Sci. 258 (2012) 4283–4287.   \n[24] J. Bravo, L. Zhai, Z. Wu, R.E. Cohen, M.F. Rubner, Transparent Superhydrophobic films based on silica nanoparticles, Langmuir 23 (2007) 7293–7298.   \n[25] Y.H. Lin, K.L. Su, P.S. Tsai, F.L. Chuang, Y.M. Yang, Fabrication and characterization of transparent superhydrophilic/superhydrophobic silica nanoparticulate thin films, Thin Solid Films 519 (2011) 5450–5455.",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Hydrophilic and superhydrophilic surfaces and materials  \n\nJaroslaw Drelich,\\*a Emil Chibowski,c Dennis Desheng $\\mathbf{Meng}^{b}$ and Konrad Terpilowskic  \n\nReceived 8th May 2011, Accepted 22nd June 2011 DOI: 10.1039/c1sm05849e  \n\nThe term superhydrophilicity is only 11–12 years old and was introduced just after the explosion of research on superhydrophobic surfaces, in response to the demand for surfaces and coatings with exceptionally strong affinity to water. The definition of superhydrophilic substrates has not been clarified yet, and unrestricted use of this term to hydrophilic surfaces has stirred controversy in the last few years in the surface chemistry community. In this review, we take a close look into major definitions of hydrophilic surfaces used in the past, before we review the physics behind the superhydrophilic phenomenon and make recommendation on defining superhydrophilic surfaces and coatings. We also review chemical and physical methods used in the fabrication of substrates on surfaces of which water spreads completely. Several applications of superhydrophilic surfaces, including examples from the authors’ own research, conclude this review.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1. Introduction  \n\nThe interest in manipulating hydrophilicity and hydrophobicity of solid surfaces and producing coatings with either strong or aDepartment of Materials Science and Engineering, Michigan Technological University, Houghton, MI, 49931, USA. E-mail: jwdrelic@mtu.edu bDepartment of Mechanical Engineering—Engineering Mechanics, Michigan Technological University, Houghton, MI, 49931, USA cDepartment of Physical Chemistry-Interfacial Phenomena, Faculty of Chemistry, Maria Curie-Sklodowska University, 20-031 Lublin, Poland poor affinity to water exploded in the last twenty years, especially after a wide acceptance that liquid spreading control can simply be accomplished through changes in surface roughness and topography. Superhydrophobicity, superhydrophilicity, and superwetting are now the most popular topics in wetting studies with many research groups attempting to understand and reveal the physics behind liquid penetrating (or suspending on) the surfaces of complex geometries and structures, often controlled at the sub-microscopic level. The fundamentals of superhydrophobicity, fabrication of water-repelling surfaces and  \n\n![](images/99e6fb7a7aeadbe8e85dee2eb13c56b925576d5e41dcd827ef48db261b837860.jpg)  \nJaroslaw Drelich  \n\nJaroslaw W. Drelich joined Michigan Technological University in 1997 and currently holds the position of Associate Professor of Materials Science and Engineering. His research activities concentrate on surface chemistry and interfacial engineering applied to extractive metallurgy and separation, recycling and surface modification of materials. Dr Drelich has published over 130 technical papers, holds 8 patents and has more than 50 conference presentations to his credit. He  \n\nserves on the External Advisory Board for the Journal of Adhesion Science and Technology and edited several special issues of this journal containing papers on wetting phenomena, atomic force microscopy, and adhesion force measurements.  \n\nEmil Chibowski  \n\n![](images/cf33828a76522c22df4e3da970061f8e324de378d200d220167709c112615a57.jpg)  \n\nEmil Julian Chibowski: born in 1943 in Poland. 1962–1967 studied chemistry at Maria Curie-Sklodowska University, Lublin, Poland where obtained MSc. Since 1967 employed at the Department of Physical Chemistry, at the same University, where in 1973 obtained PhD, in 1981 DSc, and in 1989 the title of Professor of Chemistry. Since 1993 head of the Department of Physical Chemistry. 1988–1989 post doc at Baylor University, Waco, TX; 1991–1992 sabbatical at Gran  \n\nada University; 2000–2001 visiting professor at Jaen University, both in Spain. Fields of interest: interfacial phenomena, wetting, surface free energy, electrokinetic phenomena, effect of magnetic field on the dispersed systems. Published over 200 papers. Cited $>I600$ times, H-index $=I7$ .  \n\n![](images/310b6333b6b761be8227c4634fb58a726314bfb6918f2cfeb8de093fbeb5705a.jpg)  \nFig. 1 Effect of UV radiation on hydrophilicity and transparency of a glass slide coated with a $\\mathrm{TiO}_{2}$ thin film. Water remains in the shape of lenses with a contact angle of $70{-}80^{\\circ}$ on the $\\mathrm{TiO}_{2}$ -coated glass when stored in dark (a and c), but spreads completely when exposed to UV radiation (b and d) (reprinted from ref. 18 with permission).  \n\ncoatings and their applications were reviewed by several authors on a number of occasions since 2005.1–15 However, there has been no extensive review of research on superhydrophilic surfaces, and this paper intends to fill this gap.  \n\nThe terms ‘‘hydrophilic surface’’ and ‘‘hydrophobic surface’’ have been used in the literature for many decades and they are commonly used to describe incongruous behavior of water on a solid surface. A hydrophilic surface has a strong affinity to water whereas a hydrophobic surface repels water. This simple definition, however, is too general for the classification of a variety of different solids having different wetting characteristics, typically studied in three-phase systems with water and air or water and oil as fluids. Surprisingly, a variety of different definitions of hydrophilic and hydrophobic surfaces are used by the diverse scientific community. We found it important to briefly review the most common definitions in this paper.  \n\n![](images/dd6e2ee4c6cbad1008b2acdb359564afdb04bbaaab0c98d2763c8695fbe7ad5b.jpg)  \nFig. 2 Number of papers published in each year between 2000 and 2010 in which terms superhydrophilicity and/or superhydrophilic were used, according to the ISI Web of Knowledge scientific base search.  \n\nThe roots of the term superhydrophilicity date back to 1996, when Onda et al.16,17 published two highly cited papers on the wettability of fractal (rough) surfaces in which the terms superhydrophobic and superwetting surfaces were proposed. Then in 1997 Fujishima et al.18 demonstrated a superhydrophilic effect on a glass slide coated with a thin $\\mathrm{TiO}_{2}$ polycrystalline film (Fig. 1). Although the spreading of water was the result of both hydrophilic properties of anatase exposed to UV radiation and submicroscopic roughness of the coating, the effect of water spreading was entirely attributed to the photoinduced selfcleaning capability of $\\mathrm{TiO}_{2}$ at that time and the term superhydrophilicity was not used. The term appeared for the first time in the technical literature in 2000, in four papers published by three different research groups from Japan.19–22  \n\nDennis Desheng Meng is currently an Assistant Professor at the Department of Mechanical Engineering—Engineering Mechanics of Michigan Tech. Dr Meng obtained his PhD degree in Mechanical Engineering from the University of California at Los Angeles (UCLA) in 2005 along with the Outstanding PhD Award. After he joined Michigan Tech in August 2007, Dr Meng started the Multi-Scale Energy Systems Laboratory (MuSES Lab) to work on micro- and nanotech  \n\n![](images/c769ce25b6712c099868d8ee29f9c6fc1bd1d09b7d109c24963e19b032905eaa.jpg)  \nDennis Desheng Meng  \n\nnology for energy and sustainability. The ongoing research projects in MuSES Lab include electrophoretic deposition of nanomaterials, biomedical application of superhydrophilic surfaces, micropower sources, self-adaptive thermal management, production of metal nanoparticles by short-distance sputtering, and microfluidic fabrication of self-healing materials.  \n\n![](images/288a49cccc8f9dbb8f4772a61c7b140fd2d4fc3c50802aac5f87f12cd20a7beb.jpg)  \nKonrad Terpilowski  \n\nKonrad Terpiłowski was born in Poland in 1979. He studied chemistry at Maria Curie-Sklodowska University in Lublin, Poland, and graduated in 2003 (MSc), then with a PhD in 2010. At present he is an assistant at the Department of Physical Chemistry–Interfacial Phenomena, UMCS, Lublin, Poland. His research work is mainly involved with the surface free energy of solids and stability of dispersed systems.  \n\nSince 2000, the number of papers published on the preparation of superhydrophilic surfaces and coatings persistently increases every year. Fig. 2 shows the number of papers published between 2000 and 2010, in which either ‘‘superhydrophilic’’ or ‘‘superhydrophilicity’’ was used, according to ISI Web of Knowledge.  \n\nThis paper reviews the last-decade of the research in this new field, and goes beyond it. It is organized as follows: first we review the definitions of hydrophilic solids and surfaces, including the most common misconceptions used, to show that there is a necessity for better quantification of this term. In the first section, we also provide examples of naturally occurring hydrophilic solids, which in recent years, are sometimes incorrectly called superhydrophilic. Then, we analyze the issue of complete water spreading on hydrophilic surfaces. High quality superhydrophilic surfaces cannot be fabricated without control over the hydrophilicity of materials used. For this reason we provide a brief overview of the methods commonly used for enhancing hydrophilicity of surfaces. Since all surfaces, particularly hydrophilic ones, are prone to contamination, this topic is also briefly reviewed.  \n\nIn the second half of the paper, we define superhydrophilic surfaces and briefly discuss the means of enhancing spreading of a liquid over non-smooth surfaces. Because roughness and topography of the surface are critically important to the design of smart superhydrophilic surfaces and coatings, we critically review basic models that describe the behavior of liquid on rough surfaces. For all of the current advancements over the last few years, superhydrophilic coatings are still in their infancy but are just now moving toward several possible applications and commercialization. To appreciate this progress, in the last segment of this paper we review the research on superhydrophilic surfaces and coatings, as applied to different possible products and devices.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2. Defining hydrophilic surfaces and examples of hydrophilic materials",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2.1. Solubility criterion  \n\nHistorically substances, including molecules and ions, have been called hydrophilic if they are readily soluble in water, in contrast to hydrophobic substances that are poorly soluble in aqueous environments.23 Hydrophilic solids are often hygroscopic and pick up water from the air.24 Taking simple examples from the kitchen, both salt (sodium chloride; electrolyte) and sugar (sucrose; nonelectrolyte) easily dissolve in water, in large quantities, and both of these substances are therefore classified as hydrophilic, as per this general definition. Since surfaces of salt and sugar crystals are chemically identical to the bulk composition of their crystals, they must be hydrophilic as well. In fact, the mining and mineral processing community has recognized the hydrophilicity of natural salts such as halite (NaCl) and potash (KCl) for a long time. These minerals are not naturally floatable and air bubbles will not stick to their surfaces in water.25 Their hydrophilicity has also been more quantitatively shown in new studies in which finite contact angles for saturated salt solutions were observed for some of the soluble salt crystals such as KI, KCl and ${\\mathrm{NaHCO}}_{3}$ .26,27 Other natural inorganic salts, the majority of organic pharmaceutics, and various artificial and natural organics including many polymers are known to dissolve enthusiastically in water as well. This means that we have already identified a large group of materials that are hydrophilic and have hydrophilic surfaces through simple solubility tests.  \n\nA dissolution test could be misleading however in identification of many solids having hydrophilic surfaces. The solubility process is governed by the balance of intermolecular forces between molecules of liquid and solid, together with an entropy change that accompanies the dissolution and solvation.24 For example, detergents, although soluble in water, are classified under the group of amphipathic substances with dissolution in the aqueous phase controlled by their hydrophilic–lipophilic balance, the presence of type and the amount of polar functional groups.28 Complete spreading of water drops placed on compressed discs of the detergents is prevented by a hydrophobic portion of the surfactant molecules.29 In fact, alignment of surfactant molecules can produce either hydrophilic or hydrophobic moieties and crystallized surfactants form anisotropic crystals with planes of different wetting characteristics.28 Arrangement and directionality of surface atoms and functional groups have, therefore, serious consequences in wettability of surfaces exposed to the wetting liquid. Further, strong covalent and ionic bonding in ceramics or metallic bonding in metals and alloys or large conformational entropy of long polymeric molecules prevents these solids from dissolving in water, though their surfaces usually have a higher affinity for water over air.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2.2. Polar spreads on polar  \n\n‘‘Like dissolves like’’ is a widespread useful rule of thumb for predicting solubility of solids in water. This simplistic approach predicts that any solid with a similar chemical structure to water will dissolve in it; in other words, in water polar solids will dissolve. A similar concept has been adopted for surfaces so hydrophilic surfaces are those having polarity, wherein surface molecules or their chemical groups have an electric dipole or multipole moment. This leads us to the simple but still qualitative definition of hydrophilic surfaces: ‘‘like spreads on like’’ or ‘‘polar spreads on polar.’’ What appears to be a rule of thumb cannot however predict hydrophilicity of metal surfaces. Metal surfaces, if not covered with an oxide layer, have nothing in common with the structure or polarity of water and yet water is known to spread out completely or nearly completely on noble metals such as gold, silver, copper and others (see the next section). In these systems, dispersion forces alone are adequate to induce water spreading on clean surfaces of noble metals.30",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.3. Fine particle partition  \n\nFinely divided solids with hydrophilic surfaces on which water spreads completely tend to sink in water when placed on its surface. Most often fine particles however are not so well wetted by water and they float on the water surface. The relative hydrophilicity/hydrophobicity of such fine particles can also be determined qualitatively by analyzing formation of Pickering emulsions,31 in which powder particles tend to collect at the water/oil interface and act as stabilizers of an emulsion consisting of similar volumes of oil and water.32 The interface becomes concave with respect to the liquid which better wets the particles;  \n\ni.e., an oil-in-water emulsion is formed with hydrophilic $(90^{\\circ}>\\theta$ $>0^{\\circ}$ ) particles and water-in-oil emulsion forms when particles are oleophilic (hydrophobic; $\\theta>90^{\\circ}$ ).33",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.4. Contact angle value criterion  \n\nContact with water or other polar liquid is preferred by hydrophilic surfaces over a nonpolar phase such as air or oil. It is therefore no surprise that a contact angle of $90^{\\circ}$ in a solid–water– air system has become the traditionally popular cut-off for designation of hydrophilic and hydrophobic surfaces. The distinction being that the surface is hydrophobic when the contact angle is larger than $90^{\\circ}$ and hydrophilic when the contact angle (q) is ${<}90^{\\circ}$ .9 An exception to this ninety-degrees cut-off is seen in the mining and mineral processing community. Instead, naturally hydrophobic minerals, also called naturally floatable minerals, are those to which air bubbles attach in water, $\\theta>0^{\\circ}$ .25,34  \n\nA serious practical problem can emerge however when using the contact angle value in defining hydrophilic surfaces. It is related to the means with which the contact angle is measured. For example, solid state can dictate the measuring technique and measurements of contact angles on powder differ from that of the bulk specimen with a flat surface.35 Further, the measured contact angle can be a different value depending on whether it is measured for water that advances (or recently advanced) over a dry surface of the solid or recedes (or recently retreated) from the wet solid surface.36 The difference between advancing contact angle and receding contact angle, known as contact angle hysteresis,37 is common to heterogeneous and rough surfaces,38 and often depends on the volume of liquid used in measurements.39 The contact angle hysteresis value also depends on whether the measurements are done under static or dynamic conditions and the rate of liquid movement.40 Discussion of all the measuring techniques and obstacles with the measurements is beyond this review. Any discussion in this paper refers to static contact angles, including advancing and receding contact angles, measured on flat specimens rather than powder.  \n\nIt is not always recognized that smooth and homogeneous surfaces can demonstrate the contact angle hysteresis.41,42 Formation of stable thin water films of different thicknesses on hydrophilic surfaces is the reason behind this phenomenon. This was explained using the concept of disjoining pressure† introduced by Derjaguin in 1936,43 which operates in a thin layer near the three-phase contact line. It was reported that on surfaces of quartz, glass, and metals,43 two different water films, $a$ -(adsorption) film and ${\\mathfrak{\\beta}}$ -(wetting) film (both of different thickness), can coexist in equilibrium with the bulk water sitting on the solid surface.41 $\\boldsymbol{\\mathfrak{a}}$ -Films are stable films and can be obtained in the course of the adsorption process, during, for example, contact angle measurements in air saturated with water vapors. ${\\mathfrak{\\beta}}$ -Films, on the other hand, are metastable films and can only be obtained by decreasing the thickness of thicker films. As a consequence, the contact angle measuring technique and the methodology of deposition of liquid on a solid surface can influence the type of film that is formed on the hydrophilic surface and the surrounding vicinity of the liquid meniscus and, therefore, affect the measured contact angles.44 We will ignore these problems in this sub-section and eventually return to some of them later.  \n\nAs per our own practical experience, and many others, sessiledrop and captive-bubble techniques are often the methods of choice in static contact angle measurements for bulk materials with smooth surfaces. Contact angles are more reproducible if measured for the water drops/air bubbles having a base diameter of a few millimetres,39 whose size is enlarged/reduced over the ‘‘dry’’ solid area before advancing contact angle measurements or reduced/enlarged over the ‘‘wet’’ solid area before receding contact angle measurements. In both cases, the shape of the water drop/air bubble must be stabilized, typically several seconds before contact angle reading.44 The sessile-drop technique is most commonly used, outside mining and mineral processing laboratories, due to its simplicity. In the captive-bubble method, the required attachment of the gas bubble to the sample immersed in water or other liquid is not always possible if a thick water film remains stable on a solid surface. However, a benefit of the captive-bubble method is that both solid and gas phases are already saturated with water or water vapor and measurements of contact angle are carried out under more stable and reproducible conditions. Additionally, this technique more closely reflects flotation conditions of solid particles in processing of materials.34  \n\nContact angles measured with either the sessile-drop or captivebubble technique although often well reproducible should be repeated several times and statistically valid average values, together with a standard deviation, should be reported. Representative contact angle values can be used for not only identification but also for a classification of hydrophilic and hydrophobic surfaces. In fact, most of the contact angle values (advancing contact angles) published in the past were measured with these techniques, and the values are equal or close to what could be measured using the above-mentioned experimental protocol. $\\ddagger$  \n\nNow returning to our latest definition of the hydrophilic surface, defined by the water (advancing) contact angle less than $90^{\\circ}$ , it can be easily found that most natural and man-made materials could be grouped under this category, including biological membranes, the majority of inorganic minerals such as silicates, hydroxylated oxides, ionic crystals, metallic surfaces, and even the majority of polymers. In fact, it is easier to identify all hydrophobic materials and surfaces since hydrophilic ones are more abundant in nature. Only saturated hydrocarbon-based products such as wax, polyethylene, polypropylene, self-assembled monolayers with hydrocarbon functional groups as well as fluorine-based polymers, hydrocarbons, and monolayers are hydrophobic. Any inclusion of heteroatoms other than fluorine (particularly oxygen) into the structure of hydrocarbons, or even the presence of double or triple bonding, adds a polarity to the polymer or molecule reducing its hydrophobicity and introducing or enhancing hydrophilicity of the surface. There are a number of minerals that are called naturally hydrophobic minerals including graphite, coal, sulfur, molybdenite, stibnite, pyrophyllites, and talc. However, the water contact angles on these minerals were reported to vary from 20 to $88^{\\circ},^{45}$ and therefore their surfaces do not fall under the above definition of hydrophobic. Further, there is not a known ceramic having a hydrophobic surface. Also water contact angles on metals and alloys are less than $90^{\\circ}$ . Metals (other than noble metals) and alloys, however, as a result of oxidation, are typically covered with a thin film of an oxide layer, often hydroxylated, and the contact angles measured on these materials represent wetting properties of this layer and not bare metal/alloy.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.5. Recent definitions  \n\nvan Oss recently proposed to use the free energy of hydration $(\\Delta G_{\\mathrm{sl}})$ as the absolute measure of hydrophilicity and hydrophobicity of both molecules and condensed phases.46 Based on the analysis of the free energy of hydration for a number of different compounds, he found that hydrophobic compounds attract each other in water when $\\Delta G_{\\mathrm{sl}}>-113\\mathrm{\\mJ\\}\\mathrm{m}^{-2}$ , whereas they repel each other when $\\Delta G_{\\mathrm{sl}}<-113\\mathrm{mJ}\\mathrm{m}^{-2}$ .46 He then used this (approximate) value as a cut-off between hydrophilic and hydrophobic materials.  \n\nVogler47 on the other hand proposed a cut-off between hydrophilic and hydrophobic surfaces based on the appearance of long-range attractive hydrophobic forces. Using experimentally measured hydrophobic forces, together with reported wetting characteristics of substrates used in force measurements, he concluded that hydrophilic surfaces are those with a water contact angle of $\\theta<65^{\\circ}$ and a water adhesion tension of $\\tau>30$ $\\mathrm{mN}\\mathrm{m}^{-1}$ .47 We will return to the models proposed by van Oss and Vogler in the next section.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.6. Summary  \n\nTable 1 summarizes all definitions of hydrophilic surfaces discussed in this section, and lists major problems with these definitions. Since almost all of the solids, with the exception of several saturated and fluorinated hydrocarbons, have affinity to water beyond (always existing) London dispersion interactions, a large spectrum of hydrophilic surfaces surrounds our daily activities. Hydrophilic surfaces are not the same, however, and differences in wetting characteristics among them are expected. It would be important, therefore, to classify hydrophilic surfaces into sub-groups based on contact angle values, degree of hydrophilicity, strength of interactions with water, etc.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3. Measure of hydrophilicity and hydrophobicity  \n\nAs for hydrophilic surface it is a surface that ‘‘attracts water’’ and the water contact angle should be less than $90^{\\circ}$ .48 In many papers, as discussed earlier, a zero contact angle is expected for water on a hydrophilic surface. For example in the recent paper Sendner et al.49 wrote: ‘‘one experimentally easily accessible parameter characterizing the surface hydrophobicity is the contact angle which ranges from $I80^{\\circ}$ (for a hypothetical substrate with the same water affinity as vapor) down to $\\theta^{\\circ}$ for a hydrophilic surface’’.  \n\nA true zero contact angle (in algebraic sense) has very serious implications for the energy balance expressed by Young’s equation:49,50  \n\n$$\n\\gamma_{\\mathrm{s}}-\\gamma_{\\mathrm{sl}}=\\gamma_{\\mathrm{l}}\\cos\\theta\n$$  \n\nwhere $\\gamma_{\\mathrm{s}}$ is the solid surface free energy, $\\gamma_{1}$ is the liquid surface free energy (the liquid surface tension), $\\gamma_{\\mathrm{sl}}$ is the solid/liquid interfacial free energy, and $\\theta$ is the equilibrium contact angle.  \n\nNow, if the contact angle is equal to zero indeed, $\\theta=0$ , then cos $\\theta=1$ and eqn (1) reduces to:  \n\n$$\n\\gamma_{\\mathrm{s}}-\\gamma_{\\mathrm{sl}}=\\gamma_{\\mathrm{l}}\n$$  \n\nThis case occurs rarely, if ever, in practical systems and we will discuss this issue more extensively in the next section. The zero contact angle is the limit of applicability of Young’s equation. Visually observed ‘‘zero contact angle’’ does not mean that eqn (2) applies to this situation. Such systems are better characterized by the work of liquid spreading $W_{\\mathrm{s}}$ (also known as the spreading coefficient) which is defined as the work performed to spread a liquid over a unit surface area of a clean and non-reactive solid (or another liquid) at constant temperature and pressure and in equilibrium with liquid vapor:  \n\n$$\nW_{\\mathrm{s}}=\\gamma_{\\mathrm{s}}-\\left(\\gamma_{\\mathrm{l}}+\\gamma_{\\mathrm{sl}}\\right)\n$$  \n\nIn the case of two liquids, all components of eqn (3) are either liquid surface tension or liquid–liquid interfacial tension and are, therefore, measurable. In the case of solids, neither solid surface free energy nor solid–liquid interfacial free energy is easily measurable. However, if the liquid does not spread completely but forms a definite contact angle, then applying Young’s equation allows the work of spreading to be easily calculated from measured contact angles and surface tension of liquid as long as $\\theta>0$ :  \n\n$$\nW_{\\mathrm{s}}=\\gamma_{1}(\\cos\\theta-1)\n$$  \n\nIt is difficult however to determine $W_{\\mathrm{s}}$ for surfaces on which water spreads completely. Zero contact angle would imply zero work of spreading as well. However, $W_{\\mathrm{s}}>0$ (no measurable contact angle) for a complete spreading and $W_{\\mathrm{s}}<0$ for liquids that retreat to lenses with finite contact angle. Therefore the work of spreading could be used as a measure of a solid surface hydrophilicity. The concept is not entirely new as a similar approach was proposed by van Oss.46  \n\nvan Oss proposed to use the free energy of hydration $(\\Delta G_{\\mathrm{sl}})$ as the absolute measure of hydrophilicity and hydrophobicity of both molecules and condensed phases.46 The free energy of hydration (solvation) can be defined by means of the Dupre equation:  \n\n$$\n\\Delta G_{\\mathrm{sl}}=\\gamma_{\\mathrm{sl}}-\\gamma_{\\mathrm{s}}-\\gamma_{\\mathrm{l}}=-W_{\\mathrm{a}}\n$$  \n\nThe absolute value of the free energy of hydration is equal to the work of adhesion $(W_{\\mathrm{a}})$ . Instead of coping with immeasurable solid surface free energy and solid–liquid interfacial free energy, van Oss et al.51–53 proposed to split the surface free energy into components representing Lifshitz–van der Waals and acid–base interactions. Components of the solid surface free energy or liquid surface tension are determined from contact angle measurements using at least three different probing liquids of varying surface tension and polarity. This model however is beyond the scope of this review and will not be discussed here.  \n\nTable 1 Definitions of hydrophilic surfaces, along with their major problems, reviewed in this paper   \n\n\n<html><body><table><tr><td>No.</td><td>Definition of hydrophilic surface</td><td>Problem</td></tr><tr><td>1.</td><td>Readily soluble in water</td><td>Metal oxides, ceramics and amphipathic substances do not dissolve in water, although</td></tr><tr><td></td><td>Like spreads on like (polar spreads on polar)</td><td>some of them are hydrophilic Metals do not fit into this category</td></tr><tr><td>２3</td><td>Partition of particles between the oil and aqueous phase and formation of either water-in-oil or oil- in-water emulsions</td><td>Most of the particles sit at the water-oil interface and quantification of their hydrophilicity is not possible</td></tr><tr><td>4.</td><td>Contact angle less than 90°</td><td>Vast majority of solids, although their bare surface characteristics are very different</td></tr><tr><td>5.</td><td>Thick water film remains stable: no gas bubble attachment (\"zero” receding contact angle)</td><td>Often caused by βfilm (metastability). What is the advancing contact angle?</td></tr><tr><td>6.</td><td>Free energy of hydration less than -113 mJ m-²</td><td>Scale built based on research with compounds instead of solids and more research is needed to determine the value for solids. Solids are often anisotropic—orientation and packing of molecules and atoms will contribute to hydration</td></tr><tr><td>7.</td><td>No long-range hydrophobic forces</td><td>energy Hydrophobic forces between surfaces still stir controversy regarding their origins, range of operation, and wetting characteristic of surfaces between which they operate</td></tr></table></body></html>  \n\nvan Oss also analyzed the free energy of hydration for a number of different molecules and found that hydrophobic molecules which attract each other in water have $\\Delta G_{\\mathrm{sl}}>-113\\:\\mathrm{mJ}$ $\\mathrm{m}^{-2}$ , whereas for hydrophilic molecules $\\Delta G_{\\mathrm{sl}}<-113\\mathrm{\\mJ\\m}^{-2}$ .46 He then used this (approximate) value as the inversion point between hydrophilic and hydrophobic materials.  \n\nEqn (5) can be further modified by substituting Young’s equation:  \n\n$$\n\\Delta G_{\\mathrm{sl}}=-\\gamma_{1}(\\cos\\theta+1)\n$$  \n\nConsidering the crossover value between hydrophilic and hydrophobic surfaces proposed by van Oss, we can calculate the value of the equilibrium contact angle from eqn (6) which describes the transition between hydrophilic and hydrophobic surfaces. The value is $\\theta\\approx56^{\\circ}$ for $\\Delta G_{\\mathrm{sl}}=-113\\mathrm{mJ}\\mathrm{m}^{-2}$ , and as the result indicates a zero water contact angle is not needed for the solid surface to be called hydrophilic. Additionally, this value suggests that hydrophobic surfaces are already those with $56^{\\circ}<\\theta$ $\\mathit{\\Theta}<90^{\\circ}$ . It is interesting to note that a similar cut-off between hydrophilic and hydrophobic surfaces was suggested by Vogler in 1998.47 Based on the analysis of experimental long-range attractive (hydrophobic) forces he came to the conclusion that hydrophilic surfaces are those with a water contact angle of $\\theta<$ $65^{\\circ}$ and a water adhesion tension of $\\tau>30\\mathrm{mN}\\mathrm{m}^{-1}$ . The adhesion tension is defined as:  \n\n$$\n\\tau=\\gamma_{1}\\cos\\theta\n$$  \n\nTaking into account previous recommendations, we propose the classification of hydrophilic and hydrophobic surfaces based on the contact angle, work of spreading, free energy of hydration and water adhesion tension as shown in Table 2. Hydrophilic surfaces are those on which water spreads completely, visually ‘‘zero contact angle.’’ The vast majority of materials, called here weakly hydrophilic and weakly hydrophobic, are those on which water films are unstable and water beads (lenses form) with a contact angle less than $90^{\\circ}$ . Hydrophobic surfaces are those commonly recognized with water contact angles at least $90^{\\circ}$ . We also include superhydrophilic and superhydrophobic surfaces in Table 2 but they will be discussed later.  \n\nTable 2 Proposed measures of hydrophilicity and hydrophobicity of solid surfaces   \n\n\n<html><body><table><tr><td></td><td colspan=\"4\">Measure of hydrophilicity/hydrophobicity (20 °C)</td></tr><tr><td>Type of surfaces</td><td>Contact angle/°</td><td>Water adhesion tension/mJ m-²</td><td>Work of spreading/mJ m-2</td><td>Energy of hydration/mJ m-²</td></tr><tr><td>Superhydrophilic (rough with r > 1)</td><td>~0a</td><td>≥73b</td><td>≥0b</td><td>≤-146b</td></tr><tr><td>Hydrophilic</td><td>~0</td><td>≥73</td><td>≥0</td><td>≤-146</td></tr><tr><td>Weakly hydrophilic</td><td>(56-65°)>θ>0</td><td>73 >  > (30-40)</td><td>0 > Ws > -(32-42)</td><td>-113 > △Gs > -146</td></tr><tr><td>Weakly hydrophobic</td><td>90°>θ> (56-65°)</td><td>(30-40)>>0</td><td>-(32-42)>Ws>-73</td><td>-73 > △Gs > -113</td></tr><tr><td>Hydrophobic</td><td>120°>θ≥90°</td><td>0≥t>-36</td><td>-73> Ws>-109</td><td>-36 > △G>-73</td></tr><tr><td>Superhydrophobic (rough with r > 1)</td><td>θ>150°a</td><td>≤-63b</td><td>Ws ≤-136b</td><td>△Gs1 ≥-10b</td></tr></table></body></html>\n\na Apparent contact angle. b Estimated based on apparent contact angles and using eqn (4), (6), and (7).  \n\nTable 3 Solids on which complete water spreading was observed. References are provided in the text   \n\n\n<html><body><table><tr><td>Type of solids</td><td>Examples of solids on which water spreads</td></tr><tr><td>Minerals</td><td>Cleaved mica, native gold and silver,</td></tr><tr><td>Metals</td><td>quartz, trona, halite Gold, copper, silver, chromium</td></tr><tr><td>Ceramics</td><td>Silica, TiO and other oxides</td></tr><tr><td>Salts</td><td>with dense population of OH groups, glass NaCl, NaF, NaCO</td></tr><tr><td>Biological specimens</td><td>Biological membranes and lipid layers</td></tr><tr><td>cleaned.</td><td>Only if these solids are freshly prepared andlor their surfaces are carefully</td></tr></table></body></html>  \n\nNow the question which we address in the next section is: can water spread completely on flat hydrophilic materials?",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 4. The case of complete spreading on a flat surface  \n\nAs per discussion in the previous section, the first group of hydrophilic solids that we identified is the group of soluble salts. Are these solids perfectly wetted by water? This question has only partially been answered in the technical literature. Past research clearly showed that air bubbles do not attach to either soluble or semi-soluble minerals in water (saturated with these solids).25 This suggests that water films remain stable on surfaces of these minerals. Whether water will spread out on dried surfaces of these minerals is not so obvious, however. For water-soluble solids such as salt or sugar, the measurements of advancing contact angles are either impossible or experimentally difficult and have results which are challenging to interpret. The advancing water contact angle for such ‘‘reactive solids’’54,55 cannot be determined and the angles measured represent values for water with dissolved solid, measured for either partial saturation (under non-equilibrium conditions) or saturated aqueous solutions with surface tensions that differ from the surface tension of pure water.26,27 The substance dissolution also changes the surface topography of the solid, adding a roughness component to the complexity of the three phase system examined. However, infinite advancing water contact angle values have been measured. For example, Miller et al.26,27 determined contact angles on a number of soluble salt crystals. Saturated solutions spread completely on NaCl, NaF, and ${\\bf N a}_{2}{\\bf C O}_{3}$ whereas contact angles as high as 8, 20 and $25^{\\circ}$ were reported for KCl, ${\\mathrm{NaHCO}}_{3}$ , and KI, respectively.  \n\nFurther, commonly used pharmaceutical products are made of a hydrophilic drug powder coated with a protective layer to reduce the kinetics of drug dissolution. Although the drug without protective coating dissolves in water, drops placed on compressed discs (or on single crystals if available) of these anisotropic organic solids will typically not spread out completely. Water contact angles on insulin and lactose as high as $36{-}42^{\\circ}$ and $22\\mathrm{-}28^{\\circ}$ , respectively (E. Chibowski and J. Drelich, unpublished), were estimated in our research using a thin layer wicking technique;56,57 these angles are probably far from equilibrium since neither powder nor water could be equilibrated in such tests.  \n\nIt was reported in the literature that water can spread out completely or nearly completely on just a few nonporous and smooth materials (Table 3). These include glass,1 gold,58 copper,59 silver,59 chromium,24 selected oxides (having OH groups on the surface)60,61 including quartz62 and amorphous silica surface,63 biological specimens (such as biological membranes and lipid layers),46 and cleaved mica.64 However, this was only observed if these materials were freshly prepared and/or their surfaces were carefully cleaned.1,65,66 The surfaces of these solids have strong affinity towards water molecules and have been commonly recognized as hydrophilic, sometimes called solids with strongly hydrophilic surfaces to differentiate them from other hydrophilic surfaces on which the water contact angle is larger than $5\\mathrm{-}10^{\\circ}$ (but less than $90^{\\circ}$ ).{  \n\nAt first glance, zero contact angles should be fairly common. According to Young’s equation, when $\\theta=0$ : $\\gamma_{\\mathrm{s}}\\geq\\gamma_{1}+\\gamma_{\\mathrm{s}1}.\\Vert$ If the water–solid interfacial free energy approaches a near zero value, which probably is the case for solids capable of interacting with water molecules through hydrogen bonding such as oxides with hydroxyl groups on the surface, then all solids with $\\gamma_{\\mathrm{s}}\\ge72.8\\ \\mathrm{mJ}$ $\\mathrm{m}^{-2}$ at ${\\sim}22\\ ^{\\circ}\\mathrm{C}$ could satisfy the conditions of perfect water spreading on them. In fact, metals, alloys, ceramics, and ionic salts67 all have surface free energy higher than $72.8\\mathrm{\\mJ\\m^{-2}}$ and the only known materials with surface free energies less than that of water are organic polymers.68  \n\nThis raises the question if such a wide variety of high-surface energy materials are available to us, why is water spreading and development of thick films not commonly observed on them? Why don’t these materials retain an adsorbed water film at all times? The formation of water films on many inorganic materials, including natural minerals, could probably be observed if oxygen and volatile organics are eliminated from the material’s environment. The high energy of material surfaces is a shortlived state because constituents of surrounding phases either chemically react with the material or adsorb on its surface or both in an attempt to reduce the tensions on the surface and produce a more stable system. An example is an oxide layer, which covers the majority of metals as well as many other singleelemental materials and ceramics. It is the result of chemical reaction of surface elements with oxygen from air or aqueous phases during either material production or service. Mercaptans and many other organic compounds that humans, and other living species, breathe out, diffuse and adsorb, often through strong chemical bonding, on solid surfaces. Any changes to a material’s surface reduce its surface tension, changing also the surface affinity towards water. We will return to the issue of surface contamination in a separate section, whereas corrosion of materials is ignored in this paper and we only discuss the surfaces that remain stable during the time of examination of wetting properties resulting solely from physical interactions.  \n\nIs this possible however to attain zero value for the apparent (water) contact angles\\*\\* on smooth, homogeneous and inert surfaces of the above hydrophilic materials? The question is not easy to answer as determination of the contact angles less than $5-$ $10^{\\circ}$ with commercial contact angle measuring instruments, which typically rely on an image analysis of the shape of either liquid drop or meniscus, is rather difficult.  \n\nSince most scientific research requires that measurements of contact angles are conducted on clean surfaces, we concentrate our attention on such systems. But even if the surface of hydrophilic minerals, metals, or ceramics is well prepared, measurement of a macroscopic water contact angle of zero value is rare, if measured accurately at all, as discussed earlier. It is usually the contact angle that is near zero value. Why a zero water contact angle is difficult to observe on smooth surfaces of hydrophilic materials has been partially answered by Russian scientists through the concept of disjoining pressure and formation of stable thin water films, in fact with microscopic contact angle†† that differs from macroscopic contact angle.69–73 Autophobic properties of a thin film often prevent formation of thick water films. Qualitatively, this can be explained by changes in the surface free energy of a solid surface modified by a water film and properties of the water film that differ from the bulk water. Strong hydrophilic surfaces affect diffusion, rotation, and orientation of water molecules located near the hydrophilic solid surface. As a result, the interfacial water molecules, usually from one to three layers of molecules, are more organized than in the bulk.69–73 Also an interface, and therefore tension, is expected between the ordered thin film of water and the amorphous water bulk.74 The tension at the surface of an organized water layer, if this could be measured, should be less than the surface tension of water.75 Indeed, several measurements showed finite contact angles for water placed on ice, ice representing the frozen structure of water.75–77 For example, Knight reported a (receding) contact angle of $12^{\\circ}$ for water on a somewhat rough surface of ice at a temperature below $0~^{\\circ}\\mathrm{C}$ .76 At a similar temperature, Ketcham and Hobbs found a water contact angle of about $20^{\\circ}$ .77 More recently, the surface free energy of ice was estimated through contact angle measurements with different liquids by van Oss et al.75 and found to be $69.2\\mathrm{~mJ~m}^{-2}$ as compared to $75.8\\mathrm{mJ}\\mathrm{m}^{-2}$ for water at $0{}^{\\circ}\\mathbf{C}$ . This low value of the surface free energy of ice explains the relatively large water contact angles measured experimentally.  \n\nThe presence of molecular or nanometre-sized thin water films on hydrophilic materials is probably more widespread than commonly recognized. Although the measurements of disjoining pressure of water films are still not popular, stable thin water films, including adsorption $\\mathfrak{a}$ -films and wetting $\\upbeta$ -films, were recorded on a few hydrophilic surfaces of materials such as quartz, glass, and metals.43 $\\alpha\\cdot$ -Films are stable films and can be obtained in the course of the adsorption process, during, for example, contact angle measurements in air saturated with water vapor. ${\\mathfrak{\\beta}}$ -Films, on the other hand, are metastable films and can only be obtained by decreasing the thickness of thicker films. It cannot result from water spreading.  \n\nIn summary, the existence of true zero contact angles is still a question worth further study. In practice many researchers use 5 or $10^{\\circ}$ as an arbitrary cut-off for complete spreading of water on hydrophilic surfaces, as well as superhydrophilic surfaces discussed later.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 5. Common methods to produce hydrophilic surfaces  \n\nThe enhancement of hydrophilicity of surfaces can be approached through either deposition of a molecular or microscopic film of a new material, more hydrophilic than the substrate, or by modification of the chemistry of the substrate surface. Molecular modification or deposition of coatings is more common for inorganic substrates whereas modification of surface chemistry is broadly used in the case of polymeric materials. In this section, the most commonly used methods for making surfaces hydrophilic are briefly reviewed. Examples of applications for fabrication of superhydrophilic coatings will be discussed later.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 5.1. Deposited molecular structures  \n\nA number of organic molecules adsorb from either solution or a vapor phase on selected solids, spontaneously organizing into self-assembled monolayers, changing wetting characteristics of the substrate.78 The most commonly studied densely packed molecular structures include alkanethiols on gold,79,80 silver,81–83 copper,81–83 platinum,84,85 and palladium,86 chlorosilanes on silicon oxide,87–90 aluminium,91,92 titanium93 and other oxides,93 phosphonic acids on titanium,94,95 aluminium,96,97 and other oxides.95 Both mono- and multi-layers can be deposited mechanically through a Langmuir–Blodgett film technique, although physically deposited multilayers suffer from poor stability when contacted by liquids.78 Deposited organic layers make the surface hydrophilic if the end group is polar, and not a saturated hydrocarbon-based group or fluorinated group. The groups with the highest hydrophilicity are probably those capable of interacting with water molecules through hydrogen bonding such as –OH, –COOH and POOH.79,80,98 On none of these layers, however, has a zero water contact angle ever been recorded.  \n\nBeside arranging self-assembled monolayers of chemically bonded short functional molecules on inorganic surfaces, a great deal of research has focused on coating of materials with macromolecules and biomacromolecules, which is especially popular in modification of polymers contacting biofluids, including blood.99 Albumin100–102 and heparin103–105 have been widely used as biomacromolecules. Among synthetic polymers, poly(ethylene glycol)99,106,107 and phospholipid-like107–111 macromolecules have been studied extensively. In the typical bioengineering applications of such coatings, however, the hydrophilicity of grafted or physically adsorbed dense structures of biomacromolecules or synthetic macromolecules is usually of secondary importance and both biocompatibility and fouling resistance are more important. These protective coatings are intended to prevent protein adsorption when materials come into contact with biological fluids.112",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 5.2. Modification of surface chemistry  \n\nOver the last few decades, many advances have been made in developing surface treatments by plasma, corona, flame, photons, electrons, ions, X-rays, $\\upgamma$ -rays, and ozone to alter the chemistry of polymer surfaces without affecting their bulk properties.113,114 Plasma treatment, in air or oxygen environment,115,116 corona117,118 and flame117,119 treatments are the most distinguished techniques in oxidation of polymer surfaces.120 In both plasma and corona treatments, the accelerated electrons bombard the polymer with energies 2–3 times that necessary to break the molecular bonds, producing free radicals which generate cross-linking and react with surrounding oxygen to produce oxygen-based functionalities.115 Polar groups being typically created on the surface are hydroxyl, peroxy, carbonyl, carbonate, ether, ester, and carboxylic acid groups.118 In flame treatment, surface combustion of the polymer takes place with formation of hydroperoxide and hydroxyl radicals.119,121 Oxidation depth through flame treatment is around $5\\mathrm{-}10~\\mathrm{{nm}}$ , and over $10\\ \\mathrm{nm}$ for air plasma treatment.122 Plasma, corona and flame treatments end in extensive surface oxidation and result in highly wettable surfaces. Polar groups produced during surface oxidation have a tendency to be buried away in the bulk when in contact with air for extended period of time, but they remain on the surface when in contact with water or any other polar environment.123  \n\nPolymers also oxidize and degrade under a UV (ultraviolet) light, and, for example, polymeric outdoor consumer products need addition of UV absorbers when exposed to the sunlight to inhibit discoloration, cracking, and fading.124,125 UV light has a wavelength in the range $10\\mathrm{nm}$ to $400\\mathrm{nm}$ (energy of $3\\mathrm{eV}$ to $124\\mathrm{eV}$ ), the incident photons of which have enough energy for breaking intermolecular bonds of most of the polymers, promoting structural and chemical changes of the macromolecules.126 The exposure of the polymer to UV radiation causes chain scission, crosslinking, and increases the density of oxygen-based polar groups at the substrate surface, making the surface more hydrophilic.127–130 Recently, UV light has been used to control polymerization reaction and pattern microstructures of different wettability for a variety of applications of microfluidic devices.131  \n\nAlkali treatment of polymers, especially at elevated temperature, can also enhance surface hydrophilicity of polymers.132–134 Hydroxyl and carboxyl groups are among the hydrophilic groups formed on the surface of polymers such as polyolefins and polyethylene terephthalate during their etching with concentrated bases.135,136  \n\nFinally, anodic potential was used to electrochemically treat a conductive oxide surface and control its wetting characteristics.137,138",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 6. Contamination of hydrophilic surfaces and their cleaning  \n\nThe hydrophilic surface must be kept free of contaminants such as airborne organics, moisture and dust particles to preserve its wetting characteristics. A freshly prepared hydrophilic surface when exposed to the laboratory environment tends to achieve its lowest energy (most stable state) by instantaneous changes at the surface, e.g., adsorption of water molecules or organic contaminants. In this way, contamination of hydrophilic surface and consequently a reduction of surface energy occur naturally for many materials.  \n\nThe problem of contamination of high-energy surfaces with organics is not always well recognized in many laboratories. For example, there had been a long standing controversy in both the mining and mineral processing and surface chemistry communities about the hydrophobicity of metals such as native gold and silver.139,140 Water contact angles as high as $55\\ –85^{\\circ}$ were reported in the literature for gold surfaces.140,141 After the work of Bewig and Zisman142 and then of Schrader,59,143 as well as others,58,140 it became clear that pure water can spread out completely over the surface of a freshly prepared clean metal such as gold,58,140,142,143 platinum,142 copper,59 and silver.59 Physical interactions at the metal–water interface are strong and consist solely of dispersion forces.30 The Hamaker constant for metals is an order of magnitude higher than the Hamaker constant for water.24 Unfortunately, reports on stability of hydrophilic surfaces in the laboratory environment as well as typical organics attracted by hydrophilic surfaces and kinetics of their adsorption are rare. Among those, Bewig and Zisman144 showed that even nonpolar vapors of hexane and benzene adsorb on clean surfaces of metals and the temperature of a contaminated metal must be raised by at least $100^{\\circ}$ to remove the last monolayer of these hydrocarbons.  \n\nOne of the first systematic studies reported on the phenomenon of contaminant adsorption at high-energy surfaces was presented by Bartell and Bristol in 1940,145 although the protocols and precautions to prevent contamination of specimens in contact angle measurements were not recognized until decades earlier (see, for example, a brief review in the book by Sutherland and ${\\mathrm{Wark}}^{34},$ ). Bartell and Bristol showed that the wetting characteristics of quartz and glass depend not only on the state of the solid surface but also on the particular day of contact angle measurements. They also found that the measured water contact angles were closely related to the degree of humidity in the atmosphere. White146 reported the kinetics of contact angle change for water drops placed at the surfaces of mica and oxidized surfaces of nickel, aluminium, and nichrome when these materials were exposed to laboratory air. He observed a fast increase in contact angle values in the first 10–20 hours and only a few degrees after that in the next two days. The water contact angle increased from nearly zero value to $15{-}20^{\\circ}$ for mica and nickel and to $32{-}37^{\\circ}$ for aluminium and nichrome.  \n\nWhite146 also showed that the vapor of mineral oil adsorbs less on glass and mica than aluminium and magnesium with transition metals showing the most. Similar observations were made earlier for the adsorption of fatty acids from solutions and vapor phase which showed that there is less adsorption on mica, gold, platinum and chromium than on nickel, iron and copper.147 Both studies revealed that surfaces become contaminated at different rates and to different levels, as a result of adsorption driven by molecule–surface interactions. White also proposed that organics can be gathered from the air by adsorption onto oxidized metal surfaces and therefore used as filling media in storage compartments to maintain surface cleanness of lower energy specimens such as glass or mica.  \n\nEven small quantities of organic contaminants make a large difference in wettability of hydrophilic surfaces.34,58,140 A typical experiment relies on storage of a sample in laboratory air and monitoring periodically the changes in contact angles. Since air quality in each lab is ill-defined and composition can vary substantially from lab to lab,148 the results can be poorly reproducible. They are however very useful in revealing the problem of airborne contamination that researchers can deal with in regular laboratory activities.  \n\nRecent studies suggest that a change of tens of degrees in water contact angles can be observed on glasses and metal oxides as a result of surface contamination with airborne hydrocarbons.65,66,149 When cleaned, metal oxides65,149 and commercial glasses66 demonstrate a water contact angle at a level of a few degrees. Strong hydrophilicity of these materials was reported to degrade, however, during storage in laboratory air under ambient conditions. In 3 to 4 days of storage, the water contact angle increased to $50{-}60^{\\circ}$ for aluminium oxide149 and tin oxide,65 $35{-}38^{\\circ}$ for silica, $80{-}90^{\\circ}$ for titanium oxide and chromium oxide, and to above $100^{\\circ}$ for zirconium oxide.65 The water contact angle increases from 20 to over $50^{\\circ}$ for glasses exposed to ambient air for the same time.66 Interestingly, in the case of both glasses and metal oxides, Takeda et al.65,66 found that the surface OH groups attract organic contaminants and OH group density correlates with the adsorption of organics from the atmosphere.  \n\nHydrophilic surfaces adsorb water from the laboratory environment and the amount of water sitting on the hydrophilic surface depends on the relative humidity. Although the phenomenon of formation and stability of water films at hydrophilic surfaces is important in many areas of science and technology, such as mineral processing, the electronic industry, microtechnology, and many others, not enough research has been done to study the properties of adsorbed water films, including monolayers. It is generally accepted that under ordinary atmospheric conditions, hydrophilic surfaces adsorb at least a monolayer of water. For example, a clean glass surface is covered with a monolayer of adsorbed water at relative humidities of around $30\\text{\\textperthousand}$ at $20{}^{\\circ}\\mathrm{C}$ .150 Formation of a water film composed of as many as twenty molecular layers, or more, may occur at the clean surface of high-energy solids, especially at high relative humidities, ${>}90{\\mathrm{-}}95\\%$ .151 For example, Rhykerd et al.152 measured ellipsometrically the thickness of the adsorbed water film on a fused silica surface and found it ranging from 2.4 to $9.0\\ \\mathrm{nm}$ , depending on the water vapor pressure. Staszczuk153 used gas chromatography to determine the water adsorption isotherm on quartz at $20~^{\\circ}\\mathrm{C}$ and found that about 16 statistical water layers adsorbed from a gas phase saturated with water vapor. Also, similar experiments using the chromatographic technique showed that about 15 statistical water layers may adsorb onto a marble surface.154 Water films with thicknesses from 1.0 to $8.0\\ \\mathrm{nm}$ were also reported for muscovite mica.155  \n\nWater if already present on the hydrophilic surface can probably prevent or at least slow down the adsorption of organic contaminants. Unfortunately the water surface also attracts organics, surface-active contaminants, when open to the laboratory air. Volatile organics are in exhaled breath156 and, therefore, always contaminate laboratory air. After adsorption on a layer of water at sufficient quantities, it is possible that they destabilize the water film, exposing the solid surface to them; something that was probably never studied in detail. Good practice in many surface chemistry labs is, therefore, to keep clean hydrophilic samples immersed in water before using them for experimentation and testing. Such storage is obviously acceptable if the sample’s integrity and surface chemistry remain intact in water.  \n\nMany experimental contact angles are unreliable because of the failure to work with clean solid surfaces. There should be no justification for work with surfaces that have not been prevented from systematic and accidental contamination, and properly tested for contamination. All instrumentation used in preparation of specimens (cutting, polishing, sputtering) should be freed from grease and any other organics, e.g. by washing it with appropriate (nonionic) detergent solutions, organic solvents (benzene, ethanol, chloroform), and/or acids (sulfuric acid– dichromate mixture). Annealing of samples at high temperatures, ${>}500~^{\\circ}\\mathrm{C},$ ,146 oxidizes organics to carbon dioxide and water, this approach can significantly alter the chemistry of the surface and, therefore, is only acceptable to certain inorganic materials. Surfaces of oxides such as quartz, for example, undergo dehydration at such high temperatures which results in the increase of a nearly zero water contact angle to $30{\\-}40^{\\circ}$ .62,157 Thus, the oxide surfaces are not necessarily well wettable by water when clean, and the water contact angle is closely related to the density of OH groups on the oxide surfaces.62,157 Oxide surfaces can be cleaned by degreasing and boiling in $30\\%$ hydrogen peroxide.146 Specimens should be always handled with latex gloves and never kept close to the mouth as breath contains tens, if not hundreds, of volatile organics.156  \n\nThe majority of surface treatments that are commonly used for modification of surface chemistry of polymers such as plasma, corona, flame, photons, electrons, ions, $\\mathbf{X}$ -rays, $\\upgamma$ -rays, and ozone treatments, briefly reviewed in the previous section are also effectively used in cleaning substrates. The use of a particular technique is rather dictated by its availability and applicability to a particular type of solid.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 7. Defining superhydrophilic (superwetting) surfaces  \n\nIn our previous paper,158 we proposed a definition for superhydrophilic (superwetting) surfaces. We also briefly discussed meanings to facilitate superhydrophilicity. Here we repeat our definition and then discuss issues related to manipulation of such surfaces through the control of surface roughness. Before doing that however, we start with a definition of the superhydrophobic surface since the term ‘‘superhydrophobic surface’’ appeared in the literature prior to the term ‘‘superhydrophilic surface’’. Both terms are opposite to each other with respect to solid surface wetting properties. In the last few years, superhydrophobic materials and coatings have attracted attention from a large number of research laboratories, all over the world, as evidenced by the explosion of published papers (see several reviews1–15 on this topic and references therein). The term superhydrophobicity was introduced in 1996 by Onda et al.16,17 to describe unusually high water contact angles, not observed on flat and smooth hydrophobic materials. The commonly accepted meaning of superhydrophobic surface is a surface on which the water (advancing) contact angle is at least $150^{\\circ}$ , and the contact angle hysteresis as well as the sliding (or rolling off) angle‡‡ do not exceed $5\\mathrm{-}10^{\\circ}$ . Superhydrophobic surfaces were inspired by biological specimens,159–178 and their artificial substitutes were manufactured by chemical, physical and/or mechanical modifications of both organic and inorganic materials.1–15 A common feature (not always necessary) of superhydrophobic surfaces is their proper two-level topography, with micro- and nano-sized asperities/posts, similar to what was first observed on lotus leaves and 200 other water-repellent plant species.159–177 Because the scope of this article is focused on superhydrophilic (superwetting) surfaces, the superhydrophobic ones will not be described in detail.  \n\nSince surface roughness is a necessary feature of superhydrophobicity and superhydrophilicity, it can be said that the principle of these phenomena was actually found several decades ago by Wenzel179 and Cassie and Baxter180 who described contact angles and different mechanisms of wetting on rough surfaces. The validity of their equations in description of liquid wetting at superhydrophobic or superhydrophilic surfaces will be discussed later.  \n\nAs mentioned above, the opposite to superhydrophobic is superhydrophilic surface. This type of surface is also of a great interest now,138,181–207 although a strict definition of superhydrophilicity remains to be seen.13 The superhydrophilic surfaces may have many practical applications like antifogging, antifouling or self-cleaning, and others.138,208–215 Superwetting is also important in biological systems, like cell activity, proliferation, signaling activity, etc.216 It is generally accepted that the first prerequisite for a surface to be superhydrophilic (superwetting) is that the water (liquid) apparent contact angle is less than $5^{\\circ}$ . In our previously published note158 we suggested to refer to surfaces as being superhydrophilic (or superwetting) surface only for a textured and/or structured surface (rough and/or porous) possessing roughness factor $r=$ ratio of real surface area to projected surface area) defined by Wenzel equation $\\mathbf{179}$ larger than $r>1$ , on which water (liquid) spreads completely. In the light of the above, clean glass or freshly cleaved mica surfaces (as well as other examples of hydrophilic surfaces discussed earlier) are not superhydrophilic ones, although water can spread over them completely. Such surfaces are simply naturally hydrophilic. In other words, superhydrophilic (superwetting) surfaces cannot be achieved without manipulation of the roughness of hydrophilic materials.  \n\nIn terms of a wicking parameter, $W_{\\mathrm{s}}$ :  \n\n$$\nW_{\\mathrm{s}}=\\gamma_{\\mathrm{sv}}-\\gamma_{\\mathrm{sl}}=\\gamma_{\\mathrm{l}}\\cos\\theta>0\n$$  \n\nA minimum roughness of the surface necessary to initiate liquid wicking that results in zero apparent contact angle is commonly predictable through the Wenzel equation (discussed in the next section):  \n\n$$\nr\\geq\\frac{1}{\\cos\\theta}\n$$  \n\nFig. 3 shows the correlation between the contact angle on a smooth surface of the material (Young’s contact angle; $\\theta$ ) and the minimum value of the roughness factor $(r)$ that is necessary for the rough surface of this material to promote complete spreading of the liquid. It shows that with a moderate roughening of the substrate surface, $r=1.2–2$ , superhydrophilicity or in general, superwetting, should be possible on any material having an intrinsic contact angle less than $60^{\\circ}$ . For materials with $\\theta>65{-}70^{\\circ}$ , the roughening might not be a practical approach due to the extremely high values needed for $r$ , although theoretically liquid on any rough material should spread to zero (or nearly zero) apparent contact angle. In practice however, it is also observed that liquid penetration into the rough structure of the substrate might be difficult. For example, the results presented by Onda et al.16,17 revealed the limitation of liquids to spread completely on extremely rough substrates.  \n\nLiquid drops can remain suspended on many rough and textured surfaces even if the condition given by eqn (9) is fulfilled. It relates to the three-phase system trapped in a meta-stable state,217 and such surfaces should be treated more like porous or solid–air composite materials.218,219 The invasion of the liquid can be inhibited on materials of particular design, geometry, size and contour of surface features and protrusions, and an energetic barrier associated with unfavorable geometry of the substrate for liquid wicking must be overcome.9,220–224 This energetic barrier if larger than the available thermal energy7 needs to be overcome by mechanical means such as vibrations,225,226 impact,227,228 or load imposed on the drop.224,229 By manipulating liquid reentrant profiles on rough features, opposite effects are often desired in which the lack of liquid penetration into protrusions of the rough and textured surface, with liquid drops remaining suspended, is beneficial for the design of superhydrophobic and superoleophilic surfaces. ${\\bf230},{\\bf2}{\\bf31}_{\\mathrm{In}}$ fact special designs are not necessary and using structures of nanotubes232 and nanofibers8,233 as a coating can often provide similar results.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 8. Surface topography effects on wetting: common models and their limitations (Wenzel and Cassie– Baxter models)  \n\nIt is now well accepted that surface topography plays a crucial role in liquid spreading on a solid surface. The surface topography may either enhance or reduce wetting, depending on the contours and size of the protrusions. There are two possible cases of solid surface wetting that may occur, which were outlined a long time ago by Wenzel179 and Cassie–Baxter.180 If the liquid fills in the ‘valleys’ of the rough surface then the apparent (observed) contact angle $\\theta_{\\mathrm{rough}}$ is described by Wenzel’s equation:  \n\n![](images/62ac90cc86a4ce7d90c7fd93f338cc8f629d7d6916f432c8c09ada5ac992069a.jpg)  \nFig. 3 Minimum values of roughness factor necessary to promote complete spreading of liquid on a surface with varying Young’s (intrinsic) contact angle.  \n\nwhere $r$ is the roughness parameter, which expresses the ratio of the true solid surface area to its horizontal projection, and is larger than 1, and $\\theta$ is the equilibrium contact angle that would be measured on a flat surface of the same solid. It can be said that ‘chemistry’ of the surface is reflected in $\\theta$ while the effect of the roughness involves the $r$ parameter.234 McHale et al.234 stated that Wenzel’s equation also predicts changes in the apparent contact angle $\\theta_{\\mathrm{rough}}$ caused by changes in the equilibrium contact angle $\\Delta\\theta$ induced by surface chemistry, which is given as follows:  \n\n$$\n\\Delta\\theta_{\\mathrm{rough}}=r\\left[\\frac{\\sin\\theta}{\\sin\\theta_{\\mathrm{rough}}}\\right]\\Delta\\theta\n$$  \n\nThey concluded that the change in surface chemistry ‘‘is amplified by the rough surface into a large change in the observed contact angle’’. According to eqn (11) for $\\theta=90^{\\circ}$ the amplification factor is equal exactly to the roughness factor $r$ in eqn (10) and approximately for the angles around 90\u0002.234  \n\nWenzel’s equation (eqn (10)) indicates that for suitably large roughness the apparent contact angle drops to zero degrees, $\\theta_{\\mathrm{rough}}=0$ , or increases up to $180^{\\circ}$ , $\\theta=180^{\\circ}$ (‘‘roll-up of the liquid’’). The boundary between these two cases is determined by cos $\\theta=\\pm1/r$ ,234 see eqn (9).  \n\nIn the case of narrow valleys between surface protrusions it may happen that liquid penetration is inhibited with the liquid remaining on top of the protrusions. As a result, the air is trapped beneath the liquid and the liquid then sits on what is commonly referred to as a composite surface; i.e., on asperities of the solid separated by air gaps. In such a case the liquid contact with the solid surface is greatly reduced and the system is described by the Cassie–Baxter equation:180  \n\n$$\n\\cos\\theta_{\\mathrm{C-B}}=\\varphi_{\\mathrm{s}}\\cos\\theta-(1-\\varphi_{\\mathrm{s}})\n$$  \n\nwhere $\\varphi_{\\mathrm{s}}$ is the fraction of the liquid base in contact with the solid surface, $\\varphi_{\\mathrm{s}}<1$ , and $(1-\\varphi_{\\mathrm{s}})$ is the fraction of the liquid base in contact with air pockets. Air is not wetted by water and therefore the water/air contact angle equals to $180^{\\circ}$ . Hence this cosine term leads to the minus sign in the second term of eqn (12). A complete roll-up of a droplet cannot take place on a flat solid surface since there is no natural or man-made hydrophobic material with a water contact angle larger than $118–120^{\\circ}$ (only fluorinated materials/surfaces such as PTFE can exhibit such hydrophobicity). Nevertheless, the Cassie–Baxter equation (eqn (12)) predicts that an enhancement of the contact angle up to its superhydrophobic value $(>150^{\\circ})$ can be obtained by roughening of the solid surface and by manipulating its topography.  \n\nBoth the Wenzel and Cassie–Baxter equations suggest that increasing the surface roughness (or texturing) leads to superhydrophobic states, and by changing the surface chemistry and making the solid more hydrophobic we can observe a transition from the Wenzel to the Cassie–Baxter state.234 Metastability of the liquid configuration is the common problem for liquid in contact with rough and/or textured surfaces, promoting the Cassie– Baxter state. Extra mechanical energy through, for example, vibration or pressure loads on the liquid is sometimes necessary to reinforce a change from a metastable to a stable state. The Cassie– Baxter state is usually easy to recognize as liquid droplet will rolloff the rough surface at a low tilting angle. In the case of the Wenzel state, the droplet sticks to the surface and a large tilting angle is required for roll. It should be noted that a low tilting angle corresponds to a low contact angle hysteresis, i.e. the difference between advancing and receding contact angles.  \n\nHowever, Gao and McCarthy235 in 2007 published a paper ‘‘How Wenzel and Cassie were wrong’’, questioning the validity of both the Wenzel and Cassie–Baxter approaches. They argued that the contact line, and not the contact area, is important in interpretation of the advancing, receding and the contact angle hysteresis. The contact angles are governed by an activation energy, which must be overcome to move the three-phase contact line from one metastable (or stable) state to another. The significance of analyzing the three-phase contact line region in which surface forces operate instead of total surface area under the liquid was well recognized in the past.236–238  \n\nAccording to Gao and McCarthy,235 the contact area is valid as reflected by ‘‘ground-state energy of contact line and the transition states between’’ the subsequent contact lines. A similar conclusion was drawn earlier by Extrand239 for chemically heterogeneous surfaces. Also work by Drelich237 on chemically heterogeneous surfaces and by Moulinet et al.238 on rough surfaces pointed to the same need of analyzing the shape and contortion of the three-phase contact line.  \n\nThe statement of Gao and McCarthy was based on experimental results obtained from three differently prepared two-component (hydrophilic–hydrophobic) surfaces. It was a stimulus to a hot discussion that rolled over Langmuir journal putting forward pro and con arguments.240–244 Nosonovsky240 derived generalized forms of Wenzel and Cassie–Baxter equations concluding that Wenzel’s equation is valid if for a rough surface $r=$ const. However, for a randomly rough surface, a generalized Wenzel equation should be applied, where $r$ is a function of $_{x,y}$ coordinates:  \n\n$$\n\\cos\\theta_{\\mathrm{rough}}=r(x,y)\\cos\\theta\n$$  \n\n$$\n{\\mathrm{where:~}}r(x,y)={\\sqrt{\\left(1+\\left({\\frac{\\mathrm{d}z}{\\mathrm{d}x}}\\right)^{2}+\\left({\\frac{\\mathrm{d}z}{\\mathrm{d}y}}\\right)^{2}\\right)}}\n$$  \n\nThe generalized Cassie–Baxter equation for a composite surface can be expressed in a similar way:  \n\n$$\n\\cos\\theta_{\\mathrm{C-B}}=f_{1}(x,y)\\cos\\theta_{1}+f_{2}(x,y)\\cos\\theta_{2}\n$$  \n\nHere $f_{1}+f_{2}=1$ and $\\theta_{1}$ and $\\theta_{2}$ are contact angles corresponding to the two components, i.e. air and solid. According to Nosonovsky the generalized forms of Wenzel and Cassie–Baxter equations apply to the surfaces whose protrusions and/or heterogeneities are small in comparison to the size of the liquid/vapor interface. Because most superhydrophobic or superhydrophilic surfaces possess multiscale protrusions and valleys, the use of the classical Wenzel or Cassie–Baxter equations is not straightforward as the solid area wetted by liquid is difficult to determine. If the surface roughness is present under the droplet but is absent in the triple contact line, like probably happened in the work of Gao and McCarthy,235 then Young’s equation applies instead of classical Wenzel or Cassie–Baxter, as stated by Nosonovsky.240  \n\nThen Panchagnula and Vedantam241 concluded that the Cassie– Baxter equation is correct if the appropriate surface area fraction is taken into account, i.e., the fraction value of surface areas seen by the contact line during its advancement. Gao and McCarthy242 replied that the Wenzel and Cassie equations ‘‘should be used with knowledge of their faults’’ and that they had considered the contact line instead of the area fractions in earlier published papers, which promoted an understanding of the contact angle hysteresis, the lotus effect, and hydrophobic surfaces.243,244  \n\nMcHale245 put forward the question: ‘‘Cassie and Wenzel: were they really wrong?’’ and gave the answer that these equations can be used if the surface fraction and the roughness parameter appearing therein are taken as global parameters of the surface and not as those defined for the contact area of the droplet. According to him the local form of these equations ‘‘allows patterning of the surface free energy’’. In the case of a superhydrophobic surface the apparent contact angle results from minimization of the surface free energy by small displacements of the contact line. If the droplet penetrates the valleys then the Wenzel wetting mechanism occurs.245 Later Whyman et al.246 published ‘‘rigorous derivation of Young, Cassie–Baxter and Wenzel equations’’. They presume free displacement of the triple contact line and related the potential energy barrier to advancing and receding contact angles. This energy barrier is defined by the liquid adhesion and the solid roughness. Hence, a larger energy barrier causes larger contact angle hysteresis. Moreover, the derivation predicts low contact angle hysteresis for low contact angle values. However, in a broad range of the contact angles $(50-140^{\\circ})$ the contact angle hysteresis does not depend on the equilibrium contact angle, which is not the case for superhydrophobic surfaces. Also, except for very small droplets, the droplet volume does not determine the contact angle hysteresis. However, a larger contact angle hysteresis can be expected for a liquid whose surface tension is lower.246  \n\nFurther, Marmur and Bittoun247 demonstrated theoretically that both the Wenzel and Cassie equations are good approximations of contact angles on imperfect surfaces but it should be recognized that they are valid when the size ratio of the liquid drop to the wavelength of roughness or chemical heterogeneity is sufficiently large. They also showed that local considerations of the shape and length of the contact line and global considerations involving the interfacial area within the contact line do not contradict but complement each other.247  \n\nRecently, also Erbil and Cansoy248 tested the validity of Cassie– Baxter and Wenzel equations to evaluate contact angles on 166 samples having patterned superhydrophobic surfaces (square and cylindrical pillars). They have used literature data recently published in eight papers. It was possible to calculate the roughness parameter from Wenzel’s equation and the fraction of the water/solid contact surface under the droplet to the total projection of the droplet base. Then they compared the calculated values with the experimental ones obtainedfrom the contact angles measuredon flat andrough surfaces, respectively. They found that the Wenzel equation was wrong for most of the tested samples, i.e. $74\\%$ for cylindrical and $58\\%$ for square pillars. Moreover, for the rest of the samples significant deviation from the prediction of the Wenzel equation was also high $(68\\%)$ and it was not thought to be caused by contact angle measurement errors. In the case of the Cassie–Baxter equation the authors have found disagreement in $65\\%$ of samples with cylindrical-pillar patterned surfaces and  \n\n$44\\%$ of samples with square-pillar patterned surfaces. Also deviations from theoretical Cassie–Baxter contact angles were large for most of the samples. These results show that both Wenzel and Cassie–Baxter equations give a more qualitative than quantitative evaluation of the relationship between the contact angles on rough and flat surfaces and still the exact mechanism of rough surface wetting is open for further studies. Also molecular dynamics simulation results obtained by Leroy and Muller-Plathe249 for a nanometre-scale rough graphite showed that Wenzel’s theory fails ‘‘to predict even qualitatively the variation of the solid–liquid surface free energy with respect to the roughness pattern.’’ However, for the Cassie wetting state the solid– liquid surface free energy could be well predicted from the Cassie– Baxter equation. Similar testing on real randomly coarse surfaces has not been carried out yet and results could shed more light on the applicability of the Wenzel and Cassie–Baxter models to many surfaces of practical significance.  \n\nInterpretation of the experimental contact angles on rough substrates is always difficult because of the apparent pinning of the contact line on defects such as edges of asperities, causing departure from the Wenzel assumptions whether in terms of surface area or contact line length.250,251 Both shape and sharpness of roughness features and their edges affect pinning of the contact line as is concluded from a diligent experiment with posts of different shapes performed by Oner and McCarthy.252  \n\nLately Chibowski253 suggested to use water (and other probe liquids as well) contact angle hysteresis for characterization of solid surface wetting properties via calculation of its apparent surface free energy, $\\S\\S\\ \\gamma_{\\mathrm{s}}^{\\mathrm{tot}}$ .50,254–256 The energy can be calculated from the advancing $\\theta_{\\mathrm{adv}}$ and receding $\\theta_{\\mathrm{rec}}$ contact angles of one liquid only whose surface tension is $\\gamma_{1}$ . The equation reads:  \n\n$$\n\\gamma_{\\mathrm{S}}^{\\mathrm{tot}}=\\frac{\\gamma_{1}\\big(1+\\cos\\theta_{\\mathrm{adv}}\\big)^{2}}{\\big(2+\\cos\\theta_{\\mathrm{rec}}+\\cos\\theta_{\\mathrm{adv}}\\big)}\n$$  \n\nThe general feature of the apparent surface free energy as a function of the contact angle hysteresis (CAH) relationship is the decrease in energy with increasing hysteresis. The relative decrease of the apparent surface free energy is strongly sensitive to the advancing contact angle value. With increasing its value the apparent surface free energy drastically decreases even if the contact angle hysteresis is the same. For example, for $\\theta_{\\mathrm{adv}}=120^{\\circ}$ and $\\mathrm{CAH}=10^{\\circ}$ the decrease in the apparent surface free energy amounts to $13.6\\%$ in comparison to its value at zero hysteresis. However, if $\\theta_{\\mathrm{adv}}$ amounts to $170^{\\circ}$ , with the same hysteresis, the energy decreases as much as nearly $60\\%$ Of course, the absolute value of the apparent surface free energy decrease is large in the former case, i.e., from 18.2 to $15.7\\mathrm{mJ}\\mathrm{m}^{-2}$ , in comparison to the decrease in the latter case, i.e., from 0.55 to $0.22\\mathrm{mJ}\\mathrm{m}^{-2}$ .253 These results also show differences between the two mechanisms of the wetting process, i.e., suspended or collapsed drops, for hydrophobic and superhydrophobic surfaces.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# 9. Methods of preparation of superhydrophilic and superwetting surfaces  \n\nMost solids are naturally rough; however, their roughness is usually insufficient to reinforce a superhydrophilic state of the $\\S\\S$ Apparent surface free energy is an imaginary energy calculated based on apparent contact angles.  \n\nmaterial surface. Although, in theory, any natural or synthetic material could be converted to one with superhydrophilic surface by chemical treatment and mechanical roughening or converted to sub-microscopic particles and then deposited to form a superhydrophilic coating, only a few materials have been explored for this approach. Among inorganic materials, titanium oxide $\\mathbf{(\\mathrm{TiO}_{2})^{187-190,192,193,199}}$ and zinc oxide $(Z\\mathrm{nO})^{191,193,257,258}$ are frequently studied because of their photoinduced self-cleaning capability. Also, silica $(\\mathrm{SiO}_{2})^{188,259-265}$ is well studied due to its hydrophilicity and availability at a low price. Films of nanoparticles are often deposited on substrates from solutions/ suspension,188 ink-jet printing,199,200 by a sol–gel technique,187,190 spin coating189,190 or through sputtering.257 Sub-microscopic structures grown from solutions,258,266 through lithographic195 and electrochemical198 techniques, are also used.  \n\nPolymers are also attractive materials for superhydrophilic coatings but their surfaces typically require oxidation. Improvement in hydrophilicity of polymer surfaces, as discussed earlier, can be obtained with many techniques that change surface chemistry such as the surface irradiation using g-rays113 or ion irradiation,186 electron beam,113 plasma267 and corona treatment.116,268,269 In order to make the polymer superhydrophilic the treatment must also have an effect on surface roughness or the chemical treatment must be performed in conjunction with surface roughening.  \n\nIn recent years, coatings with switchable wetting properties have attracted interest from many research groups.270 Several coatings showing a transition from superhydrophobic to superhydrophilic states were demonstrated.184,191,202,205,271 This has been accomplished for films obtained by the sol–gel process, for example upon heating,187,271 as well as by an electrochemical method (aluminium oxidation)198 or coatings.185,189,190,192,194,197,199,204,272 For example, transformation or even reversible transformation, depending on the treatment, of carbon nanotubes or buckypaper from superhydrophilic to superhydrophobic can be achieved by heating in vacuum, UV radiation or ozone treatment.205 Zhang et al.206 obtained micro– nanostructured nylon 6,6 whose as-formed surface was superwetting but after treatment with formic acid and ethanol and then dipping in paraffin wax solution in ethyl ether and drying, reversed to superhydrophobic. A reversible superhydrophilic to superhydrophobic ${\\bf W O}_{3}$ nanostructured film on alumina or tungsten substrates was produced by Gu et al.202 The superhydrophobic film was obtained by covering the surface with $n$ -dodecanethiol from its solution in ethanol, while the superhydrophilic surface was obtained by etching it with sodium dodecylbenzene sulfonate in concentrated ${\\mathrm{HNO}}_{3}$ solution.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 10. Applications of superhydrophilic and superwetting surfaces",
+        "category": " Introduction"
+    },
+    {
+        "id": 20,
+        "chunk": "# 10.1. Anti-fogging surfaces  \n\nThe need for anti-fogging surfaces arises in response to the challenge of visualization under high humidity. Swimming goggles offer an obvious example for such a scenario. Since the relative humidity is a strong function of temperature, the vapor can easily reach its saturation limit due to the temperature fluctuation or at a relatively cold solid surface, such as a lens or transparent wall to see through. As a result, significant condensation in the form of tiny droplets can be induced. The originally transparent solid surfaces will then fog and lose their optical clarity. In recent years, the necessity of anti-fogging surfaces has been highlighted by micro- and nanofluidic applications such as visualization of two phase flow in the cathode microchannels of proton electrolyte membrane fuel cells.273 Similar challenges will also be encountered when stagnant multiphase environments in microreactors (e.g., for cell cultivation274) need to be visualized. Anti-fogging surfaces can also find applications in our daily life. When a food item is packaged and displayed in a refrigerated cabinet, the relative humidity inside the package increases due to the decrease of temperature. Consequently, water tends to condense on the inner surface of packages, which, if treated to be anti-fogging, can enhance the visual displacement of the packaged items.  \n\nA superhydrophilic surface can prevent fog because water spreads on the rough hydrophilic surface to form a thin film instead of droplets. Such an effect can be easily illustrated by placing a piece of superhydrophilic polyester film on top of a cup filled with hot water.275 As Fig. 4 shows, the plasma-treated superhydrophilic polyester film (right side) remained clear due to the formation of a continuous water film. As a comparison, the untreated polyester film (left side) was covered by water droplets and fogged after several minutes. Recent results276 also revealed that similar plasma treatment can also generate superhydrophilic ‘‘nanoturf’’ surface with anti-reflection properties. It is reported that optical transmittance of a nanoturf surface is enhanced up to $92.5\\%$ as compared to a flat PUA surface $(89.5\\%)$ .276  \n\nIt is noted that the superhydrophilic treatment is different from traditional anti-fogging coatings widely used for swimming goggles and eyeglasses. The latter usually employs various surface coatings to make the surface hydrophobic, which tends to have low adhesion with the tiny water droplet formed on it. Such hydrophobic anti-fog surfaces are usually more durable than the superhydrophilic surfaces that can be obtained by existing technology. However, a coating approach might be undesirable in many conditions, such as inside a microchannel. The safety of those chemical agents for biomedical samples and food is questionable especially when the surface is subjected to environments of high temperature and high humidity (e.g., pasteurization process). Other concerns of hydrophobic anti-fog coatings are their efficacy when a polymer film is extruded (process temperature: $200{-}300~^{\\circ}\\mathrm{C})$ , the cost of the chemicals and the relatively small area it can be uniformly applied on.  \n\n![](images/ad6d5c7df695e354fabb580054f4eea4ef2b43ab3249d3bd0c840c0c2f8fa550.jpg)  \nFig. 4 Condensation and optical clarity of polyester films under high relative humidity. Left side: untreated polyester film is fogged. Right side: plasma-treated superhydrophilic polyester film retains optical clarity (reprinted from ref. 275 with permission).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# 10.2. Bio-fouling and its prevention/release  \n\nThe continuous thin water film formed on a hydrophilic or superhydrophilic surface has a profound impact on the surface’s interaction with molecules and microorganisms, including biofouling and biocompatibility (detailed in Section 10.3).  \n\nIn marine engineering, fouling has mainly been used to describe the growth of microorganisms, algae, plant, etc. on a surface (e.g., of a ship) immersed in seawater. Biomedical devices can also be subject to fouling via a deposit of cells and biomolecules (e.g., proteins and DNAs). Fouling usually changes the original property of the surface negatively and significantly impacts the performance of the device or equipment. It is preferable to avoid (or at least slow down) or reverse biofouling, with strategies known as anti-fouling and fouling-release, respectively.277 Biocides, such as a tributyltin moiety (TBT), have been widely used in the anti-fouling coating of marine vessels.278 The concerns on environmental impact, as well as the need for biomedical applications, are driving the development of non-toxic, anti-fouling and fouling-release methods, such as microtopography to mimic the surfaces of shells and scales of marine life.279–281  \n\nSurface chemistry has also been known as a strong factor to affect fouling and its prevention/release. Extensive work by Baier and co-workers since the 1960s has led to the establishment of a predictive curve, as Fig. 5 shows, to show the relationships between the critical surface tension of a solid surface and the degree of biological fouling retention.282 It is understood that fouling is such a complex issue that it cannot be sufficiently explained solely by surface energy or contact angle. However, the Bier curve has been proven to be an effective means to indicate the relative tendency of fouling in many cases, including blood fouling of biomedical devices or implants and bio-fouling of marine vessels.282 Of particular interest has been a region with a relatively low surface energy of $22{-}24\\mathrm{mN}\\mathrm{m}^{-1}$ , known as theta surfaces, which require minimal energy to detach biofilms. As theta surfaces are fouling-release instead of anti-fouling surfaces, external forces (e.g., flow) and intervention are required to periodically remove the already fouled surfaces. It is interesting to look at the end with very high surface energy, or the hydrophilic part of the curve. A trend is clearly seen that for highsurface-energy materials, the degree of fouling actually decreases with surface energy. This can be explained by the strong affinity between the surface and water molecules, which establishes a barrier to prevent interaction between the fouling agent and the surface and thus delays the fouling. Indeed, recent work by Meng’s group has shown significant reduction of fouling by fluorescein and fluorescent proteins after the surfaces are treated to be superhydrophilic.283 It should be noted that such results have been obtained in a relatively short period ( $30~\\mathrm{min}$ incubation time) with static liquid. They are thus mainly intended for applications such as micro total analysis systems $(\\upmu\\mathrm{TAS})$ and not necessarily for long-term prevention and release of biofouling.283 The difference in short-term and long-term284 fouling behaviors of superhydrophilic and hydrophilic surfaces can be attributed to the quick degradation of hydrophilicity.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# 10.3. Other applications in the biomedical field  \n\nHydrophilic coatings have been used in the medical field for the last few decades, for example in catheters, guide wires, and other vascular access devices for fertility, contraception, endoscopy, and respiratory care. Polyvinylpyrrolidone, polyurethanes, polyacrylic acid, polyethylene oxide, and polysaccharides were the main polymeric components in hydrophilic coatings. Reduction in friction was the main goal in the design of hydrophilic coatings. Recently, these coatings are also moving toward antifouling, antimicrobial and/or biologically active surfaces that perform tasks other than imparting lubricity. Also superhydrophilic coatings attracted interest among biomedical engineering research teams. Unfortunately, many claims of superhydrophilic surfaces or coatings do not comply with our definition presented earlier in this paper, as well as in our previous note.158 For this reason, we remind our readers that flat surfaces with strong affinity to water should be simply called hydrophilic. We follow this definition in reviewing recent research activities in improving biocompatibility and affinity to water of implant materials.  \n\n![](images/46ae4923012794ee76e794e4256951f330aad5a72d27cf0c8cc0ad31a0df3fbe.jpg)  \nFig. 5 Baier curve shows a descriptive correlation between the critical surface tension of the surface with the degree of bio-fouling retention (redrawn based on the figure in ref. 282).  \n\nImproving hydrophilicity of polymeric bio-implants. Biomedical applications of polymers include vascular grafts, heart valves, artificial hearts, catheters, breast implants, contact lenses, intraocular lenses, components of extracorporeal oxygenators, dialyzers and plasmapheresis units, coatings for pharmaceutical tablets and capsules, sutures, adhesives, and blood substitutes.285 Stents, lenses, catheters, and implants require biologically nonfouling surfaces to which proteins, lipids and cells do not adhere. Both catheters and lenses are made hydrophilic, although for different purposes. Catheters and guidewires require low friction (coefficient of friction of 0.3 or less) so they are easily maneuvered within the patient’s vasculature.286,287 Hydrophilic coatings were found to provide better lubricity compared to hydrophobic coatings.287,288 Lenses must be wetted by tear fluid to move relatively freely on the eye, providing wearer comfort.289,290 The applied research on surface modification of contact lenses is substantial288,291–295 and mostly deals with making the surface of polymer hydrophilic.  \n\nContact lenses were introduced into the field of vision correction after discovery of highly oxygen permeable silicone hydrogels that satisfy the metabolic needs of the cornea, maintain its physiological health, and can be worn continuously for several days.296,297 However, due to the hydrophobicity of silicone hydrogels they require hydrophilic coatings for improved wettability with tear fluid, wearing comfort and biocompatibility. Contact lenses, when inserted into the eye, accumulate proteins and other tear film components to which bacteria can adhere threatening adverse clinical events.298 Advanced contact lens coatings are not only hydrophilic but also have low biofouling characteristics. Chemical modifications that create low-fouling surfaces have been the area of intensive research not only in the field of vision correction but also in biomedical applications in general. Surface coatings included neutral hydrophilic polymers such as polyacrylamide and poly(ethylene oxide) (PEO),299 phospholipids,300 dextran,301 pullulan,302 and others.303,304 PEO has been the most popular polymer.304,305 Recently, Shimizu et al.306 synthesized hydrophilic silicone hydrogels from 2-methacryloyloxyethyl phosphorylcholine (MPC) and bis(trimethylsilyloxy)-methylsilylpropyl glycerol methacrylate (SiMA) by controlling the surface enrichment of MPC units. New silicone-based hydrogel maintains high oxygen permeability and the MPC units at the surface are responsible for low protein adsorption.  \n\nTitanium-based biomaterials. Due to their high biocompatibility, elastic modulus that closely matches human bone, good ductility, fatigue and tensile strength, titanium (Ti) and Ti-based alloys are very popular for orthopedic implants.307,308 The high biocompatibility of Ti-based biomaterials is attributed to a surface oxide layer. In fact, almost all Ti-based implants undergo some sort of anodization, electropolishing, passivation and/or other treatment, used to control the type of oxide layer, its thickness and surface topography.309 It is only in the last couple of years that photoinduced hydrophilic and photocatalytic cleaning properties of titanium oxides18 have been explored for applications in the area of biomaterial implants. There is sufficient evidence to support the removal of organic contaminants310 and bacteria311 adsorbed on a $\\mathrm{TiO}_{2}$ surface by the photooxidization process. Such self-cleaning is believed to occur particularly in the case of $\\mathrm{TiO}_{2}$ films that exhibit hydrophilicity.310 Self-sterilization capability of $\\mathrm{TiO}_{2}$ surfaces, ignored in the past, will likely be explored by the biomedical industry sector in the near future.  \n\nChanges in the bioactivity of titanium and chromium–cobalt alloy surfaces during their aging and exposure to the ultraviolet (UV) light treatment were recently studied.312,313 The study conducted uncovered a time dependent biological degradation of biomaterials, which was restored by UV phototreatment. The restoration was more closely linked to hydrocarbon contaminant removal than the hydrophilicity induced during UV treatment. These two effects are inter-related because the surface of implant materials has enhanced affinity to water when free of organic contaminants. However, surface OH groups are needed to make the interaction strong through hydrogen bonding.309  \n\nMore recently, Ogawa et al.314,315 demonstrated that UV light treatment of $\\mathrm{TiO}_{2}$ is effective in converting implant material surfaces to hydrophilic ones, and this conversion enhanced osteogenic environment. They found that the number of rat bone marrow-derived osteoblasts cultured and attached to hydrophilic surfaces was substantially greater than on untreated $\\mathrm{TiO}_{2}$ surfaces. Adhesion of a single osteoblast was also enhanced on UV-treated $\\mathrm{TiO}_{2}$ with virtually no surface roughness or topographical features. Osteoblasts on UV-treated $\\mathrm{TiO}_{2}$ surfaces were larger and with increased levels of vinculin expression and focal contact formation, although the density of vinculin or focal contact was not influenced by hydrophilicity.  \n\nThe same research group also found that $\\mathrm{TiO}_{2}$ with restored hydrophilicity has higher albumin and fibronectin protein adsorption, human osteoblast migration, attachment, differentiation, and mineralization than untreated $\\mathrm{TiO}_{2}$ surfaces even if untreated surfaces are freshly prepared.316 Time-related degradation of $\\mathrm{TiO}_{2}$ bioactivity was found to be significant in regular storage conditions, which affected recruitment and function of human osteoblasts. However, UV treatment restored and often enhanced $\\mathrm{TiO}_{2}$ surface bioactivity.  \n\nOgawa et al.314–316 also demonstrated that photofunctionalization of materials can be accomplished through a coating process. Non-Ti biomaterials can be coated with $\\mathrm{TiO}_{2}$ particles which are effective in developing functional biomaterials and improving their bioactivity.  \n\nSuperhydrophilicity for growing bone-like structures. The new generation of orthopedic implants and tissue engineering scaffolds is explored through accurately designed 3D structures of materials.317 Efforts which are underway concentrate on improving the bioactivity and biocompatibility of the core materials used in orthopedic applications such as Ti-based alloys318–321 and polymers.319,321–323 Surface treatments include coating with biomimetic calcium phosphate $(\\mathbf{CaP})$ bioactive layers or chemical modifications to enhance hydroxyapatite formation on the biomaterial surface when in contact with the living bone. Fig. 6 shows examples of porous, superhydrophilic and biocompatible coatings of calcium phosphate produced at Michigan Tech.  \n\nBiological properties of the coated implants and scaffolds depend not only on the chemical composition of the coating but also on its structure. The ideal coating should resemble the structure of natural bone, which is favorable for cell anchoring and cell culture, and should be a run-through 3D structure. Hydroxyapatite and tricalcium phosphate coatings accelerate osteoblast cell attachment and proliferation, reducing the inhalation process and enhancing hard tissue integration.318–321 Hydrophilicity was found to favor deposition of Ca-based bioactive coatings on biomaterials. Recently, Lai et al.317 used hydrophilic–hydrophobic patterned templates to fabricate structured octacalcium phosphate films on bioactive $\\mathrm{TiO}_{2}$ nanotube surfaces. By controlling wettability patterns, desired hierarchically structured OCP films were manufactured.  \n\nWu et al.324 produced a 3D complex-shaped microporous titanium-based scaffold with superhydrophilic surface characteristics via a facile low-temperature alkaline-based hydrothermal process. They achieved a hierarchical structure on the nano- and micro-scale that closely resembles the structural organization of a human bone, and these submicroscopic structures are primarily responsible for the superhydrophilicity of the scaffold. Due to good wettability of material surfaces by alkaline solutions used in the hydrothermal process, it can penetrate the entire exposed scaffold surface despite the complex topographies of the 3D porous scaffold.  \n\n![](images/05e54191fbf28cdf000c540577ad244316f27bd5183a79e178b541cf2b74caa6.jpg)  \nFig. 6 Examples of calcium phosphate biocompatible (superhydrophilic) structures produced on a $\\mathrm{Ti}_{6}\\mathrm{Al}_{4}\\mathrm{V}$ substrate (left),318 a monolayer of thiol of mixed OH and $\\mathrm{CH}_{3}$ end functionality (middle) and a monolayer of thiol with COOH end functionality (right).350  \n\nBiomimetically grown structures favor the formation of a smooth junction between the bone tissue and scaffold and benefit the long-term fixation of the scaffold. The enhancement in hydrophilicity of $\\mathrm{TiO}_{2}$ is closely related to the formation of highly crystallized anatase $\\mathrm{TiO}_{2}$ ,311,325 which can be promoted by increasing the conversion voltage during anodic oxidation or subsequent annealing.325 Although rutile is a more stable titanium oxide, anatase is considered to be more advantageous for medical applications. Anatase adheres more strongly to Ti metal and absorbs more $\\mathrm{PO}_{4}{}^{3-}$ and $\\mathrm{OH^{-}}$ ions in the body fluid, ions which favor formation of a bone-like apatite structure.326,327  \n\nBioactive and superhydrophilic $\\mathrm{TiO}_{2}$ coatings were prepared on PET film substrates using dip coating methods and subsequent glow discharge plasma treatment by Pandiyaraj et al.328 The chemical and morphological characteristics of the cleaned and rough $\\mathrm{TiO}_{2}$ coatings induced the growth of bone like apatite layers from simulated body fluid solution.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# 10.4. Enhanced boiling heat transfer  \n\nKnown as a most efficient cooling approach, boiling has been employed in a broad range of power generation and thermal management devices, such as nuclear power plants,329 refrigeration,330 cooling of electronics331 and chemical reactors.332 Boiling heat transfer can also be significantly affected by surface wettability. Fig. 7 shows a boiling curve which correlates the heat flux with wall superheat. Nucleate boiling starts from point A, with vapor bubbles forming on the overheated surface. The nucleate boiling continues to fully develop from B to C. At point C, the heat flux eventually reaches its maximum value, known as critical heat flux (CHF). Beyond CHF, a continuous vapor film is formed as an effective thermal insulation layer between the coolant and the device surface. Further heating beyond CHF will lead to a dramatic increase of wall temperature and thus device failure. Therefore, CHF marks the maximum heat flux that can be provided by a boiling-based cooler.  \n\nIt is intuitive that the continuous water film formed on a hydrophilic or superhydrophilic surface can delay the formation of a vapor film in boiling and thus improve CHF. Experimentally, vertically aligned nanoforests of hydrophilic/ superhydrophilic nanorods,333 nanowires334,335 and $\\mathrm{CNTs^{336}}$ have shown the potential to significantly improve boiling heat transfer. For example, both CHF and heat transfer coefficient (HTC) have been improved by more than $100\\%$ by this method.334 Such improvements have been attributed to the dramatically increased density of nucleation sites, high surface tension forces of superhydrophilic nanostructures for pumping in fresh liquid and the cavity stability provided by the nanopores.333,334 It has also been shown that a surface with mixed hydrophilic and hydrophobic micropatterns can enhance pool boiling to almost the same degree. For example, $65\\%$ and $100\\%$ improvements on CHF and HTC respectively337 have been achieved with a hydrophilic network decorated by hydrophobic islands of ${\\sim}100~\\upmu\\mathrm{m}$ . In spite of the relatively simple configuration of the surface, the results have been convincingly explained by the fact that the hydrophilic network can prevent formation of the vapor film by attracting liquid while the hydrophobic region can promote nucleation and help to remove gas bubbles efficiently.337",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# 10.5. Other applications  \n\nMany other applications of hydrophilic and superhydrophilic surfaces are not included in the above discussions. For example, hydrophilic modification has been long known as an effective way to improve adhesion.338,339 It has also been explored recently to decrease the impedance of neural microelectrode arrays.340 Switchable wettability may find applications in reconfigurable microfluidic devices, such as droplet-based lab-on-a-chip by electrowetting-based actuation,341,342 liquid microlenses343 and arrayed optics.344 The wettability switching mechanism has been comprehensively reviewed recently.345 More examples as well as their preparation methods can be found in Section 9 of this paper. Surfaces may exhibit tunable wettability from superhydrophilic to superhydrophobic, especially those coated with conductive polymers346 or nanomaterials, such as $z_{\\mathrm{nO}}$ nanorods,347 carbon nanotubes348 and graphene.349 The research on extreme wettability is a highly dynamic field. It can be expected that more applications of the superhydrophilic surface will be developed in the foreseeable future.  \n\n![](images/b4a9e8e345b633772468a399e38dbf4b945494f12c9a23ef53ac720e62b0b23d.jpg)  \nFig. 7 A boiling curve illustrating the formation of nucleation and the correlations between wall superheat and heat flux (prepared based on ref. 351).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 25,
+        "chunk": "# 11. Conclusion and outlook  \n\nWe define superhydrophilic surfaces, and coatings, as rough (and sometimes porous) surfaces (coatings) of materials having affinity to water greater than to nonpolar air. Water spreads completely on these rough surfaces. Flat and smooth surfaces of hydrophilic materials, on which water spreads completely (even if hydrophilicity results from photoinduced or other cleaning), do not belong to this category. The vast majority of materials could be considered hydrophilic due to a polar-type contribution to the solid–water interactions and therefore there is a need to group them under different categories, with different degrees of hydrophilicity. The literature lacks such a classification, posing challenges for researchers to fill this gap of science. In this review paper, using the values of (advancing) water contact angles $(\\theta)$ we have proposed to classify smooth solid surfaces as hydrophilic $(\\theta\\cong0^{\\circ})$ ), weakly hydrophilic $(0<\\theta<(56{-}65^{\\circ}))$ , weakly hydrophobic $((56-65^{\\circ})<\\theta<90^{\\circ})$ and hydrophobic $(90^{\\circ}\\leq\\theta<120^{\\circ})$ . The exact cut-off in the contact angle value separating weakly hydrophilic from weakly hydrophobic materials needs to be determined in future research. Another challenge ahead relates to the meaning and interpretation of water contact angle with zero value, if such a contact angle can be measured experimentally.  \n\nThe research on superhydrophilicity has emerged in the last few years, with a noticeable increase in the number of publications since 2000, and will certainly attract the attention of many research groups in the years to come. In spite of the young age of superhydrophilicity research, many research activities from the past could be considered as a solid foundation for this new subdiscipline. For example, surfaces of hydrophilic materials were roughened in the past to improve adhesion in composites, biocompatibility in implant devices, or simply to enhance spreading of liquids, even so these activities were not linked yet to superhydrophilicity.  \n\nThe progress on fabrication and characterization of superhydrophilic surfaces and coatings, along with understanding of liquid spreading on such materials, is driven by a broad application of superhydrophilic surfaces in products with anti-fogging screens, windows and lenses, anti-fouling coatings, microfluidic devices, biocompatible implant devices, coatings for enhanced boiling heat transfer, foils for food packaging, and many others. There is already a wide spectrum of products available on the market whose design was inspired by the superhydrophilic phenomenon. These products include anti-fogging mirrors for bathrooms and cars, shields of helmets for motorcycles, swimming goggles, lenses of eyeglasses, and safety eyeglasses and shields. Because the research on superhydrophilicity is a highly dynamic field, more interesting products with superhydrophilic surfaces will be developed in the near future.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 26,
+        "chunk": "# Acknowledgements  \n\nThe authors would like to express appreciation to Ryan Lemmens for reading the manuscript and making many valuable suggestions.",
+        "category": " References"
+    },
+    {
+        "id": 27,
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Tukker, Electrowetting-based variable-focus lens for miniature systems, Opt. Rev., 2005, 12(3), 255–259.   \n344 J. Heikenfeld, N. Smith, M. Dhindsa, K. Zhou, M. Kilaru, L. Hou, J. Zhang, E. Kreit and B. Raj, Recent progress in arrayed electrowetting optics, Opt. Photonics News, 2009, 20(1),   \n20–26.   \n345 B. Xin and J. Hao, Reversibly switchable wettability, Chem. Soc. Rev., 2010, 39(2), 769–782.   \n346 L. Xu, W. Chen, A. Mulchandani and Y. Yan, Reversible conversion of conducting polymer films from superhydrophobic to superhydrophilic, Angew. Chem., 2005, 117(37), 6163–   \n6166.   \n347 X. Feng, L. Feng, M. Jin, J. Zhai, L. Jiang and D. Zhu, Reversible super-hydrophobicity to super-hydrophilicity transition of aligned ZnO nanorod films, J. Am. Chem. Soc., 2003, 126(1), 62–63.   \n348 J. Yang, Z. Zhang, X. Men, X. Xu and X. Zhu, Reversible superhydrophobicity to superhydrophilicity switching of a carbon nanotube film via alternation of UV irradiation and dark storage, Langmuir, 2010, 26(12), 10198–10202.   \n349 J. Rafiee, M. A. Rafiee, Z.-Z. Yu and N. Koratkar, Superhydrophobic to superhydrophilic wetting control in graphene films, Adv. Mater., 2010, 22(19), 2151–2154.   \n350 K. C. Baker, Biomimetic Deposition of Porous Calcium-Phosphate Films on Organic Surfaces, Michigan Technological University, Houghton, MI, 2005, p. 101.   \n351 V. P. Carey, Liquid–Vapor Phase-Change Phenomena, Hemisphere, Washington, DC, 1992.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "![](images/22192c46bd4cdf0cf3c40e24285e9999f53c8a643c2433593143d6200dd3c4fb.jpg)",
+        "category": "e to analyze the text segment as it appears to reference an image link, which I cannot access or interpret. If you can provide the text segment directly, I'd be happy to help classify it based on the categories provided."
+    },
+    {
+        "id": 2,
+        "chunk": "# Dr.R.Lomolder Mr.F.Plogmann Mr.P.Speier  \n\n摘要：在一项针对异佛尔酮二异氰酸酯(IPDI)于氨基甲酸酯反应中的选择性之模型研究中,提示了催化剂类型和温度的影响。同时通过选择伯丁醇和仲丁醇作为反应对象,介绍了羟基类型的影响。  \n\n需特别指出的是，催化剂的选择对最终产品的组成有着极重大的影响。模型研究的最重要结论在NCO预聚物的合成中得到了肯定。",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# The influence of temperature,catalyst and coreagent on reactivity of two isocyanate group in isophorone diisocyanate  \n\nAbstract:In a model study for the reactivity of two isocyanate groups of isophorone disocyanate,it reveals the influence of temperature and catalyst in urethane reaction.Using primary and secondary butanol as coreagent the article decribes the influence on type of hydroxy group.It is emphasized that the selection of catalyst has great influence on the composition of final product.In NCO prepolymer synthesis the most important conclusion of this model study is confirmed.",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1概论  \n\n异佛尔酮二异氰酸酯(IPDI)(图1)是在世界范围内制备光稳定性氨基甲酸酯改性涂料用树脂的首选脂环族二异氰酸酯。所能制备的树脂包括PU分散体、氨酯改性醇酸、辐射固化氨基甲酸酯丙烯酸酯和潮气固化异氰酸酯预聚物。除其与众多的共反应物和溶剂有着极广泛的相容性外，本品用途之所以日益得到扩展的主要原因之一是，一个在脂肪族伯位上与一个在脂环族仲位上的IP-DI的两个异氰酸酯基团反应活性不相等。这种不相等所造成的结果是：最终产品粘度低；分子量分布窄；游离的二异氰酸酯单体含量小。过去，IPDI在反应活性上的这种差别曾是探讨的课题。根据对差别成因所作出的许多假设，根据化学计算，反应对象以及根据所采取的试验方法和对试验的解释，人们得到了这样的结果：真有不同反应活性的NCO基团的活性差在0.2:1-12:1的范围内。  \n\n本项研究中的内容包括：在氨基甲酸酯反应中各种催化剂、温度（在所有以前的研究中温度被设定为常数)、位阻和/或醇类的反应活性对模型反应的选择性影响以及其对工业中可予实践体系的适用性。  \n\n与取代基在环己烷上可能的定向相呼应，IPDI分化为顺式(Z)和反式(E)异构体。工业级的IPDI是异构体的混合物，异构体的比例大致为75:25,以顺式(Z)为主。 (图2)  \n\n![](images/b8e626a5bc2570fadaef2cfb0cebc2fd040510d6293ea9ea1afa6276bb1267a1.jpg)  \n图1异佛尔酮二异氰酸酯  \n\n![](images/83931f3e904b64623f2debde0fdf1588a43a6ca37a45898f12a365ef567ecb8b.jpg)  \n图2顺式/反式IPDI异构体  \n\nIPDI与醇类的反应可以以四个速率常数(K1-K4)予以完全的表达。这个常数是与IPDI异构体中每一个异构体上的两个不相等的NCO基(伯/仲)相呼应的。合计起来，要加以考虑的有八个速率常数和八个产物（图3)。对这个非常复杂的体系可以按照其反应速率给予某种清楚明显的简化来加以处理。  \n\n![](images/2f9e3db63d09d80d60e8b6d8cbeae47c5ddc6edcbc3fe31ac6467ca02d54f4c1.jpg)  \n图3IPDI与醇类反应的速率常数  \n\n假设：（a）单氨基甲酸酯单异氰酸酯的氨基甲酸酯官能团对残余异氰酸酯基的反应活性既无催化剂性质、也无阻遇性质的影响；（b）顺式和反式IPDI具有可比的反应活性。  \n\n根据以上假设，图3已被简化成为两个速率常数和四个产物的体系(图4)。  \n\n万万数据  \n\n![](images/fe9ba817407baa6d4dba18fb705ef371d0e3ccf7018242c54906ba3fa8a10131.jpg)  \n图4IPDI的氨基甲酸酯反应的简化动力学模型[K(顺) ${\\bf\\Pi}={\\bf K}$ （反）]  \n\n在一个异氰酸酯处于过量状态，异氰酸酯转化率为已知的体系中，按照Peebles的说法，速率常数的比例可以通过最终产出混合物的游离单体含量来加以确定。按一个非对称的例子所进行的计算，一个计算量为2：1的 $\\boldsymbol{\\mathrm{NCO}}/\\mathrm{~OH~}$ 反应其二异氰酸酯转化率与K1和K2的商I之间产生了一定的相关性。",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2试验部分  \n\n模型反应不用溶剂，是在一个有搅拌的反应器中，在氮气保护下恒温进行。将赫斯公司（Huels AG）的VESTANATIPDI和催化剂加人反应器中，将醇在5h内滴加完。化学计算量为 $\\mathbf{NCO}{:}0\\mathbf{H}=2{:}1_{\\circ}$ 反应持续进行到转化完全为止。以十四碳烷为标准进行凝胶色谱分析以测定其单体含量。在反应中使用1-丁醇，使我们有可能解析IPDI四个单氨基甲酸酯和1－丁醇。所用的1－丁醇和2-丁醇都含有 $<0.2\\%$ 的水，多元醇 $<0.5\\%$ 。水含量是按Karl-Fischer法测定的。叔胺类催化剂是由Aldrich提供；DBTL（二月桂酸二丁基锡)由Elf-Atochem提供;辛酸锌溶解在石油溶剂中，石油溶剂中脂肪族对芳香族的比例为80：20，锌含量为 $8\\%$ ，由Borchers 公司提供。乙酰乙酸铁（FeAcAc）由赫斯公司提供；催化剂Coscat83( $16\\%$ 秘）由Caschem公司提供。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 3结果和讨论",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 3.1应用各种氨基甲酸酯催化剂时的.IPDI",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 选择性  \n\n金属类催化剂（路易氏酸）以及叔胺类催化剂（路易氏碱）在氨基甲酸酯化学中是人所熟知的。表1所示为IPDI/1－丁醇反应的结果，这个反应是在 $\\tt N C O/O H$ 化学计算量2:1的条件下和 $20\\%$ 的温度下进行的。反应使用了 $\\smash{\\mathsf{S n}_{\\searrow}Z_{\\mathbf{n}_{2}}}$ Fe和Bi催化剂，用量按恒定的金属原子／离子浓度确定。实验还使用了四种叔胺催化剂，二氮杂双环[2.2.2]辛烷(DABCO)1,8二氮杂双环－[5.4.0]－十-—烯－7(DBU)，N，N－二甲基环己基胺(DMCA)和1,5-二氮杂一环[2.3.0]壬烯－5(DBN)，四者均按IPDI体系的典型浓度$0.4\\%$ (DBU为 $0.2\\%$ )的量使用。未催化体系亦列出以供参考(表1)。  \n\n表1催化剂对IPDI与1-丁醇的氨基甲酸酯反应的影响  \n\n\n<html><body><table><tr><td>催化剂</td><td>T= k1/k2 完全转化时间</td></tr><tr><td>无</td><td>5.5 8d</td></tr><tr><td>DBTL(0.075%)</td><td>11.5 6h</td></tr><tr><td>辛酸锌(0.42%)</td><td>7 IdX.</td></tr><tr><td>Bi催化剂(0.135%)</td><td>2.5 6h</td></tr><tr><td>FelILAcAc(0.042% )</td><td>5.5 6h</td></tr><tr><td>DABCO(0.4%)</td><td>0.18 1dX.</td></tr><tr><td>DBU(0.2%)</td><td>5.5 同上</td></tr><tr><td>DMCA(0.4%)</td><td>4.4 同上</td></tr><tr><td>DBN(0.4% )</td><td>6.2 3d</td></tr></table></body></html>\n\n$\\mathrm{X}_{\\mathsf{I}}:>6\\mathrm{h},<24\\mathrm{h}$ 条件： $\\mathbf{\\widetilde{NCO}:O H}=2:1,20\\mathbf{\\widetilde{C}}$  \n\n催化的效果是明显的，这是共性。除此之外，催化剂的有效性也存在着差别。除Zn催化体系外，所有的金属催化均比叔胺催化更为有效。令人惊异的是所使用的催化剂类型的选择性。DBTL是本项研究中最具选择性的催化剂。未催化体系的I值为5.5，而对DBTL来说却达到了11.5。就叔胺类而言，DABCO造成了选择性的逆转，而所有其它叔胺类，则未显示出明显的影响。  \n\nDBTL催化剂使选择性显著增加的情形  \n\nHatada和Pappas也曾提及。他们用氢’和碳技术进行核磁共振测定证实，当以DBTL催化时，脂环族仲NCO基无疑更为活泼。很明显，伯NCO基被 $\\beta$ 基取代物、环己烷和与之相邻的甲基有效的遮蔽起来了。  \n\n金属催化之所以使选择性增加的原因可以通过考察这些催化剂的机制找到；金属以路易氏酸的形式发挥作用并通过对羧基的配置而使异氰酸酯基得到活化。活化转变状态对额外空间的需求是导致已经很活泼并且位阻也较小的NCO基优先得到催化的原因。  \n\n叔胺类催化氨基甲酸酯反应主要是通过活化醇的羟基之途径而实现的，但其对NCO基团的活化问题也有人进行过讨论。通过OH基的活化，活化转变状态所要求的空间比使用金属催化剂时的要求要小些。这应该是胺类催化剂没有额外选择性的原因。除DABCO外，叔胺类对IPDI的选择性没有明显的影响。很有意思的是，DABCO所造成的选择性逆转使伯NCO基变得更为活泼。一个可能的解释是，DABCO－1-丁醇络合物的残余游离叔胺官能被更为活泼的仲NCO基所预配位化。通过重组为分子内的大环，活化OH基可以指向伯NCO基。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 3.2温度对IPDI选择性的影响  \n\n已发表对IPDI选择性问题的研究报告均以温度作为一个常数。为了显示温度的影响，作为一个例子，对未催化的体系和使用具有非同寻常催化效果的DBTL的体系进行了研究目的是在 $20-100\\mathrm{\\PhiC}$ 范围内确定温度对选择性的影响。产物的粘度被作为体系更深入的参数。  \n\n对于一个未催化而在 $20-100\\mathrm{\\textperthousand}$ 进行的IPDI/正丁醇（NCO： $\\mathbf{OH}=2\\colon1\\rangle$ 之氨基甲酸酯反应 ${\\boldsymbol\\Gamma}$ 进程和产物粘度来说，如所预期的，随着温度的增加，选择性从 ${\\pmb5.5}(20{\\pmb\\mathrm{\\qquade}})$ ）向反方向变化为 $3.9(100^{\\circ}\\mathrm{C})$ 。较低的选择性导致了二氨基甲酸酯比例增加和粘度的相应增长。在进行未催化树脂合成时，从对粘度和经济性因素( $100\\%$ 的转化在 $20\\%$ 需要8d，而在 $80\\%$ 仅需 $\\boldsymbol{6\\mathrm{h}}$ ）的考虑出发， $60-80\\mathcal{\\mathbf{C}}$ 的温度范围似乎是最佳的。  \n\n![](images/70cef3e05e93bc5f83ddebc3123a2f6d04368c0a0f60550d7ecb503f49ac6b56.jpg)  \n图5IPDI与1-丁醇在氨基甲酸酯反应中使用DBTL催化剂 $0.075\\%$ ） $(\\mathbf{NCO}:\\mathbf{OH}=\\mathbf{2}:\\mathbf{1}_{i}^{\\cdot}$ .IPDI的选择性和最终产物粘度  \n\n图5清楚地显示，DBTL具有更高的选择性，对温度的依赖比未催化体系也更强。然而，在 $100\\%$ 的选择性高于未催化反应在$20\\%$ 时的选择性。有趣的是，产出混合物的粘度在直到 $80\\%$ 温度下几乎保持恒定。对于未催化体系来说，其粘度会随着二氨基甲酸酯浓度提高而有所增加，这是可以预期的。很明显，在产物组成的系列中，包括有单体、单氨基甲酸酯和二氨基甲酸酯。因二氨基甲酸酯含量提高而带来的粘度提高效应会被较高的单体浓度所带来的粘度降低效应所抵销。让人奇怪的是在 $80-100\\mathrm{^c}$ 之间观察到粘度有急剧提高的现象。SFC法确认了在$100\\%$ 的反应混合物中存在有 $2\\%$ 的高分子量组成，这或者是从二氨基甲酸酯得来的脲基甲酸酯或者是IPDI的单异氰酸酯。  \n\n基于在 $40-60\\%$ 范围内的副产物以及万方数据  \n\nDBTL催化后明显的选择性，可得出的结论是，工业性IPDI氨基甲酸酯反应以在此温度范围内实施为宜，且应选择催化体系。  \n\n以凝胶色谱技术对四个单氨基甲酸酯进行分离，就可以以IPDI与1-丁醇的DBTL催化反应温度为函数来显示出顺式和反式IPDI的选择性。关于仲对伯单氨基甲酸酯的比例显示了顺式和反式IPDI的选择性问题，如所预期的，两种异构体都随着温度的提高而表现出选择性下降的情性。反式异构体的选择性明显较高（在 $40-100\\mathrm{\\textperthousand}$ 温度下系数约为2),额外的位阻为2-丁醇。  \n\n为弹性体市场生产的异氰酸酯预聚物通常是以仲OH基占优势的聚丙二醇为基础。因此，把对选择性的研究进一步扩展到位阻更大、而反应性较弱的2-丁醇，则是引起人们兴趣的事。在图6中，就IPDI与1-丁醇和2－丁醇在DBTL催化下的反应对温度的依赖关系作了比较。  \n\n据推测，因2－丁醇的使用致使出现对额外空间的需求，使IPDI的选择性有了进一步的增加。在 $20\\%$ 下的速率常数之比为17,作为比较的数据是使用1－丁醇时的11.5(DBTL)和5.5(未催化)。使用2-丁醇时，在$80\\mathbf{\\%}$ 的转化比使用1－丁醇在 $20\\mathbf{\\%}$ 的转化更具选择性，两条曲线均为平行走向，这意味着选择性对温度的依赖就两者而言是类似的。  \n\n在此项研究中所选用的气相色谱不能把反式IPDI的单异氰酸酯和2-丁醇分离出来。在与2-丁醇的反应中，顺式异构体的选择性增加到了反式异构体与1-丁醇反应时的水平（ $20\\%$ 仲单异氰酸酯／伯单异氰酸酯$\\begin{array}{r l r}{\\mathrm{~}}&{{}}&{=30.1/1\\dot{\\mathrm{~,~}}}\\end{array}$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3.3 回到实践中：NCO预聚物  \n\n用于潮气固化涂料的IPDI预聚物一般是由分子量分布在500－3000之间、含2－3羟基官能团的聚合物所制备，按化学计算量，NCO: $\\mathbf{OH}=1.8\\colon1$ 到2：1。为了说明使用1-丁醇和2-丁醇模型体系结果的适用性，IPDI是与四种不同的多元醇按2：1化学计算量反应的。所使用的多元醇有线型NPG(新戊二醇)，己二酸酯，分子量差不多的聚（四次甲基二醇）醚和聚（丙二醇）醚以及一种分子量为540的三官能聚己酸内酯，后者是以 $75\\%1-$ 甲氧丙基-2-醋酸酯(MOP醋酸酯)溶液的形式使用的(表2)。  \n\n表2基于各种多元醇的IPDI预聚物  \n\n\n<html><body><table><tr><td></td><td></td><td>预聚物</td><td></td></tr><tr><td></td><td>A B</td><td>C</td><td>D</td></tr><tr><td>基础</td><td>聚酯 P - THF</td><td>PPG</td><td>聚己内酯</td></tr><tr><td>多元醇分子量</td><td>1000 1000</td><td>1000</td><td>540</td></tr><tr><td>官能度</td><td>2 2</td><td>2</td><td>3</td></tr><tr><td>固体含量(%)</td><td>100 100</td><td>100</td><td>(MOP醋酸酯）</td></tr></table></body></html>  \n\n表3不同温度下合成预聚物的结果$\\mathbf{\\left\\langleNCO:OH=2:1,DBTL\\right.}-$ 催化剂 $\\mathbf{-0.075\\%}$   \n\n\n<html><body><table><tr><td>A</td><td>B C</td><td>D</td></tr><tr><td>T(℃) 23℃ IPDI 23°℃ Pa·s % Pa·s</td><td>粘度 单体 粘度 单体 粘度 单体 粘度 单体 IPDI 23℃ IPDI % Pa·s % Pa·s</td><td>23℃ IPDI % 4.8 5.0</td></tr><tr><td>20 206 40 216 60 219</td><td>3.9 16.7 4.3 12.2 3.2 4.0 18.7 4.4 12.5 3.3 4.1 19.1 4.4 13.0 3.6</td><td>3.4 4.2 4.2 5.2</td></tr><tr><td>100 264</td><td>4.3 22.8 4.5 16.0 3.7</td><td>4.3 6.5</td></tr><tr><td>80,无 284 催化剂</td><td>6.3 27.2 6.0 15.0 5.7</td><td>5.6 8.8</td></tr></table></body></html>  \n\n按照Wendish等人的说法，脂环族基团更倾向于一个对等的位置。按照这个说法，反式异构体的NCO基正好处于轴线的对等位置上，比顺式异构体的侧位会有更有效的位阻屏蔽效应。(见图6)  \n\n异佛尔酮衍生物的反式异构体伯基团屏蔽性更强，反应性更低的另一效应最近围绕环氧体系而有所报道；在双组分环氧配方中，更多的反式IPDA(异佛尔酮二胺)能使其使用寿命有所延长。  \n\n![](images/d444dc45ef7167cb554bee1b1355e3b7363edbb25201164aee754dc5891a15e7.jpg)  \n图6IPDI与1-丁醇、2-丁醇在氨基甲酸酯反应中的选择性 $\\mathbf{(NCO:OH=2:1}$ ，DBTL－催化剂 $\\mathbf{\\sigma}=\\mathbf{\\sigma}$ $\\mathbf{0.075\\%}$ ）  \n\n表3综合了预聚物合成的结果，包括在各个温度下的催化制备和在 ${\\bf809}\\mathrm{\\overline{{C}}}$ 未经催化制备的结果。这个结果与模型研究的结果非常接近；使用DBTL者，随温度的增加（20-${\\bf60^{\\circ}C}$ ）粘度和单体含量有微小增加；在 $80\\mathbf{\\hat{C}}$ 时反应的未催化体系粘度和单体含量最高。NPG体系在80时所造成的无催化剂反应产物粘度较低 $(15\\mathrm{Pa}.\\mathbf{s})$ ，这似乎令人惊讶，但却与多元醇相对较弱的骨干链热降解可能有关。在 $100\\%$ 催化反应的产物粘度比在${\\bf60^{*}C}$ 反应者显著高出较多，但仍然与模型研究的结果相平行，这与脲基甲酸酯的形成有关。  \n\n在 $100\\%$ 的催化反应与模型研究有显著的偏离。与 ${\\bf60^{\\circ}C}$ 的反应相比，单体含量只有微小的增加(预聚物A-C)。这个结果通过模型与预聚物体系的 ${\\bf\\delta T}$ 对照列于表4中。它表明，IPDI在预聚物合成中更具选择性。由于预聚物与模型体系相比，有着更高的粘度，IPDI单体的扩散更将受到阻碍。这意味着，相当程度的脉基甲酸酯形成作为一个竞争性的反应存在应当予以考虑。这个事实导致最终产物较低的单体含量。这可能被误解为较高的选择性。这种解释因低粘度的 $75\\%$ 预聚物溶液(D体系)而得到了确认。在这个溶液中，在 $100\\%$ 时的单体含量有一个飞跃。  \n\n(下转第49页)  \n\n剪切速率粘度。有时候转换供应商也可解决问题。调配基料制造商亦正发展较能与缔合型增稠剂相容的产品。  \n\n流变助剂的副作用跟配方有关，不可能尽列。可以这样说，由于不同系统有不同作用，实验是不可避免的，但通过仔细筛选及咨询供应商，试验工作量可减至最低。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3总结  \n\n选择流变助剂可以分成几个有系统的步骤，把选择范围缩至几个产品，根据这些步骤可以剔除不适合的产品，避免浪费试验时间。  \n\n最重要的也许是确定需要哪一种流动形态，配方设计者必须为最终产品鉴定清晰一 Titiitiitiiti-iit-ititiiiiii-ii（上接第14页）  \n\n表4合成预聚物(A一D)与模型反应物(1-丁醇,2-丁醇)的速率常数比  \n\n\n<html><body><table><tr><td colspan=\"2\">r</td></tr><tr><td>T(℃)</td><td>1-丁醇 A B D 2-丁醇</td></tr><tr><td>20,DBTL</td><td>11.5 11.5 10.2 14.5 17.0</td></tr><tr><td>40,DBTL 10.5</td><td>16.5 10.9 9.5 12.9 15.0 15.7</td></tr><tr><td>60,DBTL 9.0</td><td>10.5 9.5 12.0 12.2 12.6</td></tr><tr><td>100,DBTL 6.5</td><td>9.3 9.3 7.2 10.1 12.0</td></tr><tr><td>80,无催化剂 4.1 3.6</td><td>4.3 3.2 3.3 4.3</td></tr></table></body></html>  \n\n对预聚物合成和模型反应的I所进行的比较(表4)，本质上已能表现出很好的相关性，不仅是伯羟基／IPDI反应（1-丁醇和A、B、D体系）和仲羟基/IPDI反应（2-丁醇和C体系）的『绝对值如此，而直至 ${\\pmb60}{\\pmb\\Upsilon}$ 时对温度的依赖性以及DBTL催化剂对粘度和单体含量的影响也均如此。  \n\n一般来说，本项研究从粘度、单体含量和经济性角度方面确认了在 $40-60^{\\circ}C$ 温度下使用DBTL催化剂进行IPDI预聚物合成的可行性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 4综述  \n\n异佛尔酮二异氰酸酯(IPDI)在氨基甲酸万方数据  \n\n目标，亦需要明白不同类别助剂的一般特性。供应商提供的产品说明书及数据表上的资料都有帮助，有某些的确是推广的术语，但其中的理论通常都有道理的。配方设计者应花时间阅读，并与供应商讨论具体问题，几分钟的电话时间可以节省几小时的试验工夫。  \n\n三个要点分别是：需要的流动形态、用哪种助溶剂及工厂条件的限制，对有经验的配方设计者这些步骤是显而易见；其他的步骤是微调，只是从几个类似产品中选择一个，在这阶段实验工作是不可避免的。  \n\n显然今天碰到的问题仍需要很多时间解决，但希望循着以上步骤，选择流变助剂在实验室里不再是最花时间的一项。  \n\n酯反应中显示出对温度、催化剂类型和不同反应对象有强烈的依赖性。  \n\n对IPDI的选择性进行的模型研究是以伯和仲丁醇作为反应对象而进行的。这一系列的金属催化剂（Sn、Zn、Bi和 $\\mathbf{Fe}$ )和叔胺类催化剂的影响进行了研究。与未经催化的体系相比较，所有的催化剂均能加速氨基甲酸酯反应。原则上说，金属催化剂可改善IPDI的选择性，而DBTL是最具选择性的催化剂。在一系列的叔胺催化剂中，只有DABCO使选择性逆转。其它叔胺类无显著影响。  \n\n随温度的增加而出现的选择性下降现象一般来说得到了确认。使人惊异的是，DBTL对IPDI的催化却促成了比不用催化剂且在低温下所得到的还要高的选择性，温度提高时尤其如此。  \n\n对影响选择性的另两个因素有所判断。仲丁醇能比伯丁醇产生更高的选择性，这说明了反应对象不同的影响。此外，反式IPDI比IPDI更富选择性。观察到，预聚物合成与模型反应之间存在着很好的相关性。对IPDI预聚物合成的最佳条件可推荐如下：40-60C的温度，使用DBTL催化剂。",
+        "category": " Results and discussion"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,92 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Review",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Research progress of UV-curable polyurethane acrylate-based hardening coatings  \n\nJunchao $\\mathtt{F u}^{\\mathrm{a}}$ , Li Wanga,⁎, Haojie $\\mathrm{Yu^{a,*}}$ , Muhammad Haroona, Fazal Haqa, Wenlei $s\\mathrm{{hi}^{\\mathrm{{b}}}}$ , Bin Wub, Libo Wangc  \n\na State Key Laboratory of Chemical Engineering, College of Chemical and Biochemical Engineering, Zhejiang University, Hangzhou 310027, China b Suzhou Taihu Electric Advanced Material Ltd., Fenhu New & Hi-Tech Industrial Development Zone, Wujiang 215200, China c Ningbo Haoxin YURON New Material Co., Ltd., NO. 7, Dajiang North Road, Jiangkou Sub District, Fenghua 315514, China",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# A R T I C L E I N F O",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# A B S T R A C T  \n\nKeywords:   \nUV-curable   \nPolyurethane acrylate Hardening coatings  \n\nWith the development of society, plastics play a significant role in daily supplies owing to their advantages. Whereas, insufficient scratch resistance and vulnerable plastic surfaces result in the constraint of their range of application fields, for instance, electronic products. Hence, it is a highly desirable objective of researchers to investigate hardening coatings for protecting plastic surfaces, by selecting polyurethane acrylate (PUA) as filmforming materials attributing to their adjustable features. This article reveals components of PUA and principles for its hardening modification, and summaries various methods of hardening modification of PUA-based coatings, such as improving the crosslinking density, strengthening hydrogen bonding, incorporating rigid groups into molecular structure, introducing inorganic nanoparticles into resin matrix and transferring linear PUA into hyperbranched analogs. Moreover, optimal strategies for the preparation of PUA-based hardening films from above five tactics are discussed.",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# 1. Introduction  \n\nPlastic is an indispensable material in the industry to produce daily supplies and high-tech products for specific applications owing to its lightweight, easy process and low cost, such as optical glasses, electronic product shells or protective films of precision instruments and so on. However, as optical resins and instrument housings, the insufficient mechanical strength of plastic results in the constraint of their range of application fields, because poor scratch resistance causes soft plastic surfaces which can be easily damaged [1–3].  \n\nUp to now, there exist many methods to improve the hardness of plastic which can be divided into three groups. One is an additive modification, in which hardening additives are added to plastics. The commonly used hardening additives are rigid inorganic fillers (kaolin or silica hydrated etc.) and fibers. However, these additives have significantly increased the surface roughness of plastic products, which brings bad influence to plastic. Second is blocking or grafting at the molecular level, which can be operated by incorporating polar groups or rigid groups into molecular chains of plastic to increase the crystallinity or rigidity of plastic, respectively. The hardness of plastic can be enhanced, possibly while the other mechanical properties will be affected, such as the considerable decrease in toughness. Third is hardening modification of plastic surface, which means that only the hardness of surface is promoted, and the internal hardness of products does not change. The examples are coating, plating and surface treatment. The coating has lower cost, easier process and slighter influences on the other performances of plastic than the above hardening modifications. So, it is an urgent need to extend the application domain of hardening coatings with high mechanical properties in plastic products.  \n\nCurrently, considerable efforts have been made to investigate highperformance UV-curable coatings through changing materials or operational parameters [4–6]. Compared with thermal curing, UV-curing technology is noted as 5E, which stands for Efficiency, Energy saving, Enabling, Economical, and Environmental friendly [7–12]. Generally, UV-curing systems mainly consist of three basic components: a monoor multifunctional acrylate monomer, an acrylate prepolymer, and a photo-initiator. Until now, diverse sorts of additives are constantly employed in such systems [13,14].  \n\nAs the one of most popular resin, PUA has attracted much attention in UV-curable coatings attributing to its excellent flexibility, prominent adhesion on substrates and a variety of adjustable features. [15] Significant results can be acquired when it is applied in coatings for metals, mobile phones, and other electronic products. However, the density and content of photosensitive groups of the existing photo-curable resins are not abundant, and have influence on the film performance. For example, the hardness of coating films is poor and UV-curing speed is slow which limits its practical applications in some fields [16,17]. Therefore, improving these performances of PUA is priority.  \n\nIn this review paper, the components of PUA and principles for hardening modification of PUA-based coatings is revealed in the first part. Afterward, the second part will be devoted to review diverse methods of its hardening modification. Eventually, a discussion about the optimal approaches for the preparation of PUA hardening coatings will be drawn.",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2. Compositions of PUA and principles for hardening modification of PUA-based coatings  \n\nPUA is an important category of photo-curable crosslinking resins, and is also widely employed in protective coatings. It is based on polyurethane, and then the double bond of acrylates is introduced into the molecular chain terminal of polyurethane, eventually, oligomers are used to initiate double-crosslinking reaction under the action of photoinitiators [18].",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.1. Compositions of PUA  \n\nPUA comprises a significant category of polymeric materials whose properties can be tailored by regulating its compositions, the ratio of polyurethane/polyacrylate or -NCO/−OH, and the structure of raw materials [19–22]. The molecular structure of PUA mainly consists of urethane segments, the main chain of polyols or polyamines, and acrylate hydroxyalkyl ester segments (Fig. 1). The curing characteristics are determined by the acrylates located in the segments, and the structure and composition of the resin backbone mostly affect the properties of products.  \n\nGenerally, researchers frequently employ diisocyanates containing toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI) as the urethane segments, including ethylene diamine (EDA) or ethane glycol (EG) etc. as chain extenders (Table 1) [18]. Attributing to the fact that diisocyanates possess different molecular structures, bringing diverse features for segments, we can acquire the properties of coatings what we want through varying the category or content of diisocyanates. For example, selecting HMDI and MDI for improving mechanical properties of resins owing to the cyclic structure or benzene rings they have, or choosing HDI to receive flexible coatings because of the exiting long-chain alkane, or using IPDI to control the reaction process which can design the chemical structure of compounds ascribing it to the different reactivity of two isocyanate groups of IPDI at low temperature. For the parts of main chain of polyols or polyamines, investigators usually employ polyethylene glycols (PEG), polytetrahydrofuran (PTMEG), poly (caprolactone glycol) (PCL), or polycarbonate diols (PCDL) etc. as flexible chain extenders whose terminals contain many hydroxyl or amino groups (Table 1) which can react with diissocynates by semi-adduct reaction. For the acrylate segments, we constantly choose hydroxyethyl acrylate (HEA) as end-capper to obtain unsaturated bonds. Nevertheless, in order to get compounds containing high functionality, raise the hardness or mechanical properties of coatings after curing, sometimes, we are more willing to introduce trimethylolpropane diallyl ether(TMPDE) or pentaerythritol triacrylate (PETA) containing lots of unsaturated bonds into system which are used as end-capping reagent (Table 1).  \n\nWhereas, in order to follow new policies of sustainable chemistry development, academic and industrial researchers have to seek for some greener resources or processes to replace hazardous chemicals and rigorous reaction conditions [23]. The greener raw materials can be divided into two groups. One is the preparation of non-isocyanate polyurethane (NIPU) by transurethanization polycondensation (Fig. 2), such as the reaction between cyclic carbonate and diamine, representing one of the most promising surrogates to the traditional route for synthesizing polyurethanes [24–28]. Another is discovery of renewable resources, for instance, vegetable oils, which are the most promising sustainable building blocks that can efficiently substitute for fossil-feedstock-derived polyester and polyether polyols [29]. Vegetable oils are triglycerides mainly consisting of saturated and unsaturated fatty acids, such as soybean oil [30], castor oil [31] or jatropha oil [32] and so on. The relationships between structure-property and resulting polyurethanes dramatically depend on the kind of triglyceride used [33], the category of diisocyanates and the degree of cross-linking28].  \n\nIn another aspect, some researchers add several reactive diluents into UV-curing systems (Table 1), such as tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA) or pentaerythritol tetraacrylate (PETTA), not only to decrease the viscosity of curing system, but also to increase the crosslinking density of coating films after cured owning to its plentiful double carbon bonds. For the reason that PUA occupies so many adjustable characteristics which combines the advantages of both acrylic and polyurethane resins, it has high reactivity, excellent flexibility, adhesion, low temperature resistance, abrasion resistance, chemical resistance and elasticity.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.2. Principles for hardening modification  \n\nFor the past few years, a large number of researchers have made much effort to modify the hardness of PUA coatings, some of which show excellent results. [11,12] We can receive the conclusion, whether from strategies they have used or the PUA molecular structure (Fig. 1), existing four techniques to elaborate hardening modification.  \n\nFrom Fig. 1, we can see that PUA can be divided into three sections, section a contains double bond functional groups, which are mainly used for photo-curing crosslinking, section b includes urethane bonds, which forms the hard segments, and section c comprises with weak or no other intermolecular forces, forming the soft segments. Sequentially, some tactics will be utilized. We can select section a to improve the hardness of PUA, promoting its functionality (unsaturated bonds), thereby increasing the crosslinking density to achieve more compact network structures [34], or incorporating some chain extenders that can form more hydrogen bonds into section b or section c reinforcing hydrogen bonding, accordingly strengthening the micro-phase separation or producing mixed phases between hard and soft segments, respectively, and then increasing the hardness [35], or introducing rigid groups (containing cyclic groups) for section c which can promote the hardness of soft segment owing to its rigidity [36]. Certainly, adding some inorganic fillers into the resin, such as nano- $s\\mathrm{iO}_{2}$ or $z_{\\mathrm{{nO}}}$ and so on, can also endow the considerable result of hardness for composite films. [10] The inorganic nanoparticles have capabilities to remarkably improve physical properties of polymers due to the strong interaction between particles and polymer interface caused by nanometer effect and its high specific area. The above strategies can not only be employed alone but also be united, to achieve the best outcomes.  \n\n![](images/fde373c0c2e43d1d2215f732ad74ba994287e5fbc5ffaafb8a14c107031fdea3.jpg)  \nFig. 1. General chemical structure of PUA.  \n\n![](images/69bc1fcc67aee22316961b19f266dbdeeb050647c625e68d78bfeae95e7c121c.jpg)  \nFig. 2. Overview of synthetic routes to polyurethanes. [23] Copyright 2015. Reproduced with permission from American Chemical Society [23]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 3. Strategies of hardening modification of PUA  \n\nFrom the mechanisms of hardened modification for PUA, we can get that there are five methods to enhance the hardness of coating films, which include improving the crosslinking density, strengthening the effect of hydrogen bonding, introducing rigid groups or adding inorganic nanoparticles into matrix to augment the rigidity of films and transferring linear PUA into hyperbranched PUA.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3.1. Improving the crosslinking density  \n\nTheoretically speaking, there are two ways to reinforce the crosslinking density. One is forming multi-functional groups (carbon double bonds) and another is the introduction of silicone coupling agent. Silanol groups produced by the silicone coupling agent will react with each other to form siloxane bonds (Si-O-Si), consequently forming stable Si-O-Si siloxane networks [37]. The crosslinking result of silane coupling agents enhances the hardness and abrasion resistance of coatings.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3.1.1. Polyfunctionality modification  \n\nAs a rule, the modification of double bonds content exists two strategies. One is adding reactive diluents [38] and another is promoting functionality of oligomers [39].  \n\nFor the reactive diluent, Xia et al. [40] synthesized a cluster of UVcurable polyurethane mixed components including (Nethylperfluorooctylsulfonamido) methyl acrylate (EFCSA) and pentaerythritol tetra (3-mercaptopropionate) (PETMP, a reactive oligomer). Subsequently, EFCSA and PETMP reacted with (2-hydroxyethyl acrylate)-terminated polyurethane resin to fabricate coatings (Fig. 3a). With increasing contents of PETMP, the pencil hardness was raised from 2B to HB due to the promotional crosslinking density of coatings caused by the increasing of thiol groups. Meanwhile, one point should be emphasized that this study introduced thiol-ene click reactions into crosslinking system to form polyurethane coatings, offering some benefits like high curing rate, low energy consumption [41] and enhanced mechanical properties due to its high reactivity for emerging highly dense networks. Li et al. [42] used PETA as end-capper and PETTA as reactive diluents to form PETA/PETTA composite system, including many unsaturated double bonds, subsequently enhancing the crosslinking density of films (Fig. 3c). The results revealed that dense network structures were formed by introducing PETTA with higher reactivity into the polyurethane molecule after cured and pencil hardness was improved from 2H to 3H. And the best consequence of mechanical properties was acquired when nearly $35\\mathrm{wt.\\%}$ PETTA was added (Fig. 4d). It was found that if the weight ratio of PETTA was tremendous, it might bring something worse effects to films owing to its high reactivity, which can take the shape of compact networks sharply, and then restrict the diffusion and motion of PETTA or radicals out of networks. In consequence, it brought a reduction of the crosslinking density because of premature termination of polymerization that was caused by partially unreacted double bonds trapped in the polymeric networks [15]. On the same method, Xu et al. [43] introduced tripropylene glycol diacrylate (TPGDA) as a multifunctional acrylate molecule reactive diluents into resins (Fig. 3b) that can form the preferable crosslinking structure, and then raise the coating hardness due to two unsaturated double bond $\\mathbf{\\tilde{\\Sigma}}.\\mathbf{C}=\\mathbf{CH}_{2})$ ) and shorter soft chains of TPGDA. As a whole, we can conclude that reactive diluents play an important role in the film hardness attributing to their high functionality.  \n\n![](images/b4f305dd9a76f73621e253bdd0dc16cd6cbbccedbdd4edebb16b37e03a8e3a56.jpg)  \nFig. 3. a) Preparation process of HFTPU. [40] b) Reaction mechanism of UV-WPUA based on PETA/PETTA [42]. c) The formation of UV-WPUA coating film [43].Copyright 2013. Copyright 2014. Reproduced with permission from John Wiley and Sons [42]. Reproduced with permission from John Wiley and Sons [43].  \n\n![](images/99d4c5deca0cf58a83f8e79afbe2ede692ad07edc47acb7cc962610373d3d1c8.jpg)  \nFig. 4. a) Synthesis process of UV-WPUA emulsion and b) Tensile properties of UV-WPUA. [45] c) Synthesis of fluorinated/methacrylated soybean oil [48]. d) Tensile properties of UV-WPUA [42]. Copyright 2014. Reproduced with permission from Elsevier [45]. Copyright 2009. Reproduced with permission from Elsevier [48]. Copyright 2014. Reproduced with permission from John Wiley and Sons [42].  \n\nFor the functionality of oligomers, Yuan et al. [44] developed a series of PUA oligomers terminated with multiple unsaturated bonds by using PETA as an end-capping reagent. Poly (propylene oxide) and PETA have significant effects to furnish more double bonds, which can increase the content of multi-functional groups. The results demonstrated that the functionality and content of oligomers (PETA content) of PU prepolymer have a huge impact on the film hardness, raising from 4H to 6H when PETA was added. Li et al. [45] introduced both castor oil (CO) and end-capper of PETA into waterborne polyurethane (WPU) molecules to obtain UV-WPUA oligomers containing multiple unsaturated double bonds and polar groups attributing to the high functionality and existing ester groups of CO (Fig. 4a), and the excellent mechanical properties was obtained. Simultaneously, researchers found that when the additive amount of CO was more than $6.86\\%$ , tensile strength received a sharp reduction (Fig. 4b). The excessive crosslinking results in some negative effects in the molecular level, such as molecular chains hardly moved freely and the mechanical strength decreased. Nevertheless, owing to its good advantages, castor oil and its derivatives have been considerably employed in polyurethane coatings field. [39,46,47] In another article, Kahraman et al. [48] used epoxidized soybean oil and methacrylic acid to synthesize methacrylated soybean oil terminated with multiple double bond, and then introduced it into PUA resins to get the harden coating (Fig. 4c). The result exhibited that the modification of film hardness was great, which can be supposed to the modified soybean oil acting as a cross-linking agent, because its polyfunctionality will raise the crosslinking behavior, afterward developing a tight network structure. Coincidentally, Li et al. [30] disclosed the similar consequence that acrylated epoxidized soybean oil (AESO) can increase the crosslinking density and form network structures during the curing process. The reason can be attributed to the fact that AESO contains two types of functional groups: one is hydroxyl groups which can covalently bond by reacting with other reactive groups or form hydrogen bonds to strengthen the effect of intermolecular chains, and the another is double carbon bonds that can be UV-cured.  \n\nObviously, the increment of double bonds content of curing systems or oligomers can make the chemical crosslinking density raise as well, so that the crosslinking network structures of components are more compact, reducing the free space for chain motion. Subsequently, the overall hardness and abrasion resistance of film is enhanced. With aggrandizing functionalities of compounds, however, the viscosity of system remarkably ascend which is not conducive to the leveling of coatings, resulting in insignificant increase in hardness. As a result, the lower viscosity of the system could promote a full crossing-linking reaction to form a denser crossing-linking structure by its leveling of films and motion of free chains [44].  \n\n![](images/b6ceeea9a83e74413a1237f639e8fafbcd6b42f8bfdf96e4c3bc595f21042385.jpg)  \nFig. 5. Schematic diagram of PDMS-based polyurethane acrylate oligomers. [52] Copyright 2011. Reproduced with permission from Elsevier [52]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3.1.2. Siloxanes and silane coupling agents modification  \n\nNumerous researchers have certified that preparing harder films only with siloxanes and silane coupling agents through sol-gel technique can be done successfully [49], which can even raise the pencil hardness of coatings from 2B to 5H [50]. It can be attributed to the formation of stable Si-O-Si siloxane networks [51]. The most studied and applied silicon-containing acrylate monomers are silane coupling agents containing only one silicon atom, such as $\\upgamma$ -methacryloxypropyltrimethoxysilane (MPTMS), trimethylsilyl methacrylate (TMSM) and so on. $\\upgamma$ -Methacryloxypropyltris (trimethylsiloxy) silane containing several silicon atoms is also a commonly used monomer.  \n\nFor the modification of PUA coatings, hydroxy-terminated polydimethylsiloxane (PDMS) was introduced into the soft segments of PUA dispersions by Hwang et al. to reinforce the thermal and surface property (Fig. 5) [52]. From the results, they revealed that the curing rate and conversion of unsaturated bonds were diverse when end-cappers containing different functionality were added. For the conversion of unsaturated bonds, PDMS with mono-functional methacrylate obtained a little increment, but PDMS with high functionality reduced slightly. The reason could be supposed to that the former can be attributed to chain flexibility of PDMS, and the latter may be influenced more by the steric hindrance caused by PDMS. Furthermore, coatings with PDMS, especially including tri-acrylate end-capping, showed high initial modulus and excellent tensile strength and got a sharp reduction of elongation at break due to the polyfunctionality of tri-acrylate endcapping. Park et al. [37] investigated the effect of silane coupling agents in coatings, and introduced acrylic monomer and vinyltrimethoxysilane (VTMS) to acquire the UV-curable polyurethane acrylates (Fig. 6a). The consequences exhibited that as the amount of VTMS augmented, the storage modulus/hardness of the UV-cured coating enhanced significantly and the tensile strength/glass transition temperature raised slightly (Fig. 6b and c), whereas, the elongation at break decreased sharply owing to the occurrence of rigidity by the stable and dense Si-O-Si network structures. Wang et al. [36] adopted  \n\nMPTMS (KH-570) as the silane coupling agent and then found that the introduction of KH-570 can form a more compact spatial structure by increasing crosslinking density, afterwards improving the tensile strength of the latex films properly while keeping other performances well.  \n\nFor silane coupling agents, they can condense by themselves to form the structure of polyhedral oligomeric silsesquioxane (POSS), which can obtain the nanometer effect and excellent mechanical properties. Octavinyl-POSS was incorporated into UV-curing PUA matrixes by Kim et al. [53] to prepare hybrid nanocomposite films with distinctive thermal and mechanical properties. The PUA was consisted of poly (tetramethylene glycol), IPDI and HEA. Researchers found that the Shore A hardness (Hardness value measured by Shore hardness tester) of coating raised from 70 to 85 by adding and increasing POSS content in hybrid coatings. Addition of silicones to the matrix made films harder which can be ascribed to the increment of the cross-linking density as well as the reinforcing effect produced by the multi-functionality and rigidity of octavinyl-POSS. In another research, the silane coupling agent was utilized for the modification of interfacial compatibility. Kim et al. [54] gained the UV-curable PUA based hybrid materials, and MPTMS as a silane coupling agent was incorporated into the matrix to promote interfacial attraction between main organic part and inorganic silicate in the curing system, to receive a high degree of cross-linking and compact organic-inorganic network structure. By adjusting the adding quantity of MPTMS, morphological variation was obtained in Fig. 7. From the figure, we can see that with increasing the additive amount of the silane coupling agent MPTMS, the dispersion of silica particles was remarkably improved, eventually the stable and homogeneous morphology can be observed. Furthermore, this phenomenon delivered a significant information that raising interaction between organic and inorganic phases can substantially suppress the tendency of agglomeration among nano-inorganic particles and bring the silane coupling agent into full play.  \n\nFrom the above discussions, some conclusions can be made that the addition of siloxanes and silane coupling agents reinforce the crosslinking density of the system to form a dense network structure owning to its compact and stable siloxane networks generated from silanol groups, to acquire the effect of improving coatings hardness. Whereas, siloxanes are easily crosslinked together and then make clusters, which brings inferior effects to coatings, such as the low increase in hardness and high reduction of elongation at break after cured [55]. So, in order to receive excellent results of modification, we should control the number of siloxanes in a moderated range.  \n\n![](images/646cd109986830ce5c5445e4efd164e07fa4cfdd4fe5739c16471413a45acb4d.jpg)  \nFig. 6. a) Synthetic route of UV-curable PUAs. b) The storage modulus and c) Stress-strain curves of UV-cured coatings (FPUA $6/0$ , FPUA $_{6/3}$ , FPUA $6/6$ and FPUA 6/ 9). [37] Copyright 2015. Reproduced with permission from Springer Nature [37].  \n\n![](images/66aee6f7485de02b919463fd0b94329d16cdf435304977a48af2e686880a94e3.jpg)  \nFig. 7. SEM images of acrylate $\\mathrm{\\Delta}^{\\prime}\\mathrm{SiO}_{2}$ hybrids without MPTMS, a) $\\mathrm{TEOS}=0.01\\mathrm{mol}$ , b) $0.03\\mathrm{mol}$ , and hybrids with addition of MPTMS, c) $\\mathrm{TEOS}=0.01\\mathrm{mol}$ , d) $0.03\\mathrm{mol}$ . [54] Copyright 2010. Reproduced with permission from Springer Nature [54].  \n\n![](images/cea78c79ee44d5e6902d995339e84f8b797920de3a239572485add264c8a9b2f.jpg)  \nFig. 8. a) Preparation of soybean-oil-based WPU dispersions. b) The relation between glass-transition temperature $(T_{g})$ of the SPU coatings and the hydroxyl number of the MSOL. c) Stress-strain curves for MSOLs-based SPU films with different hydroxyl numbers. [29] Copyright 2008. Reproduced with permission from American Chemical Society [29].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3.2. Strengthening hydrogen bonding  \n\nPUA contains thermodynamically incompatible hard segment and soft segment units. The hydrogen bonding generated between hard segments form physical crosslinking among polymer molecular chains which have a significant effect on physical properties of polymers, and are easy to produce mixed phases, giving the material excellent overall performance [29,56].  \n\nLu et al. [29] incorporated a derivative of soybean oil (MSLO) into prepolymers to prepare a cluster of vegetable-oil-based WPU dispersions, among them, hydroxyl groups of MSLO ranged from $2.4\\mathrm{up}$ to 4.0 (Fig. 8a). Certainly, MSLO can play the role of UV-cured functional groups owing to its unsaturated double bonds as well. In addition, the experimental results disclosed that hydroxyl functionalities of the MSOLs had significant effects in controlling mechanical properties of coatings. With increasing the $-\\mathrm{OH}$ number in MSOL, the $T_{g}$ value and mechanical properties were strengthened due to the higher physical cross-linking in the soft segment provided by hydrogen bonding (Fig. 8b and c). Jofre-Reche et al. [57] modified the abrasion resistance and hardness of PU with polycarbonate diol (PCD) and polytetramethylene glycol diol (PTMEG). The results revealed that PUPTMEG possessed poor abrasion resistance, while the hardness and wear resistance of PU-PCD and PU- $50\\%$ $\\mathrm{PCD}+50\\%$ PTMEG were significantly improved, almost up to 60 Shore A hardness, which attributed to stronger interactions of the carbonate groups in soft segments that were able to create hydrogen bonds with urethane groups of hard segments, producing a higher miscibility of the hard and soft domains and then reinforcing mechanical properties. Definitely, we should note that the role played by hydrogen bonds is mainly augmenting the abrasion resistance of coatings, which makes resins tough owing to its role of buffers, conversely, restricting the improvement of the hardness of films.  \n\nAnother approach is not the modification of oligomers but blending. Zhang et al. [35] successfully acquired a new type of waterborne PUPA ester emulsion through a physical blend between polyurethane emulsion (PU) and polyacrylic ester emulsion (PA). The film properties of  \n\n![](images/500a8f3ab9e167f8ae48d9f86505a1d28bbd23bb578fb1d1b41c3cfa652ba660.jpg)  \nFig. 9. a) Formation of the PUPA polymer particles. [35] b) The different patterns of $\\scriptstyle{\\mathsf{C}}=0$ in polyurethane: (a) free carbonyls, (b) disordered H-bonded carbonyls, (c) ordered H-bonded carbonyls. c) XRD graphs of the WPU and WFPU coatings [59]. Copyright 2013. Reproduced with permission from Springer Nature [35]. Copyright 2017. Reproduced with permission from Elsevier [59].  \n\nPUPA coating was characterized and exhibited reasonable hardness, improving the stability of the PUPA coating by the hydrogen bonding between $\\boldsymbol{\\mathrm{N-H}}$ of PU and $\\scriptstyle0=\\mathbf{C}$ of PA [58]. The forming mechanism of hydrogen bonding between PU and PA was represented and shown in Fig. 9a. From the above researches, it is worth noting that the introduction of more hydrogen bonds into soft segments can increase the interaction between hard and soft segments to enhance mixed phases, and then endow coatings with favorable properties. The method strengthens hydrogen bonding between hard and hard segments to raise micro-phase separation, whereas, also can work pretty well to increase the hardness of films. As an instance, Yang et al. [59] developed a series of novel waterborne fluorinated polyurethane and acquired the conclusion that the increment of H-bonded carbonyl groups in hard domains has a significant effect on crystallization, bringing the increase of crystalline in hard domains (Fig. 9b), which was contributed to raising the hardness of films. All samples showed a strong peak at $2\\Theta=19^{\\circ}$ (Fig. 9c), demonstrating that micro-phase separation between the soft and hard segment was generated to endow coatings with excellent properties because of the crystallinity in the hard domains. This enhancement can be related to the restricted movement of polymer chains caused by the larger degree of hydrogen bonding between the hard and hard segments [29,60]. However, the large degree of micro-phases separation will lead to uneven film surface because of its crystallization on the surface.  \n\nAlthough the hydrogen bonding improves the mechanical properties of materials, its enhancement in hardness is limited, because it mainly improves the abrasion resistance of coatings. The reason can be attributed to taking the shape of buffers by hydrogen bonding, which will absorb impact energy when subjected to force. At the same time, the hydrogen bonds in coatings break at relatively high temperatures, whose thermal stability is relatively poor.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.3. Incorporation of rigid groups  \n\nResearches have shown that rigid groups give the PUA a very high hardness improvement, for example, bisphenol A epoxy resin itself contains benzene rings, whose hardness after curing is very considerable [36]. In contrast, it was demonstrated that the addition of compounds containing tough chains into epoxy resins or PUA coatings will decrease coating hardness and increase damping properties [61]. Rigid groups that can be introduced into PUA include benzene rings or sixmembered heterocyclic rings, especially six-membered heterocyclic rings that can form large $\\uppi$ bonds, such as triazine groups, which not only provide considerable rigidity, but also endow coatings with antiyellowing.  \n\nShi et al. [62] introduced melamine into PUA matrix to get phasechange heat-storage UV-PUA coatings by microencapsulated technology, where melamine-formaldehyde shell and paraffin core were synthesized to form phase change materials. Certainly, the melamine possesses triazine group that can take the shape of large $\\uppi$ bonds. Attributing to dense crosslinking density and rigidity of melamine-formaldehyde, the mechanical properties of films were enhanced [63]. Besides, Pathak et al. [64] selected hexamethoxymethylmelamine (HMMM) as a crosslinking agent, which was incorporated into resin system to prepare films, getting the conclusion that triazine groups of HMMM play a significant role in strengthening mechanical properties of coatings owing to its rigidity. In another study, Mishra et al. [65] synthesized a new intermediate through the reaction between epoxy resin and dimer fatty acid, which called dimer acid modified epoxy (DME) polyol containing both hydroxyl and epoxy groups (Fig. 10a), and then prepared UV-curable polyurethane by adding trimethylolpropane tris(3-mercaptopropionate) as a cross-linking agent. Evaluation of cured samples showed that with incresing the amount of thiol ratio, the significant improvement in storage modulus (Fig. 10b) and hardness can be observed. Furthermore, the high hardness value of coatings can be attributed to the rigidity of DME, which contains rigid phenyl groups.  \n\n![](images/4a73499aced67259f34b0b643e47f9808912903c97eeef98673f9a0d9cd64c90.jpg)  \nFig. 10. a) Synthetic route of DME. b) Storage modulus of cured films. [65] c) Chemical structures of hard/soft monomers containing acrylic groups [66]. Copyright 2017. Reproduced with permission from Springer Nature [65]. Copyright 2017. Reproduced with permission from Elsevier [66].  \n\nIn addition, Yong et al. [66] selected different ratios of hard/soft monomers containing acrylic groups as an adjusting mean to prepare a series of WPUA hybrid emulsions (Fig. 10c). The research disclosed the relationship between mechanical properties and amounts of acrylic monomers. Comparing to the WPU film, the hardness of WPUA coatings increased remarkably owing to the introduction of acrylic monomers, which is due to the reason that the increment of the weight ratio of hard monomers can endow films with rigidity and excellent mechanical properties by considerable phenyl skeleton structures of acrylic monomers. Certainly, they also discovered that each film possessed two $T_{g}$ values, indicating that the phase separation phenomenon existed due to the appearance of hydrogen bonding between hard and hard segments. Hence, they can form buffers by breaking hydrogen bonds when subjected to force, giving coatings toughness. Moreover, Beniah et al. [56] used 1,4-diaminobutane, isophorone diamine, methylene bis(cyclohexyl amine), and bis(aminomethyl) norbornane as chain extenders to investigate the influence between polyhydroxyurethane (PHU) structure and properties of PHUs (Fig. 11a), eventually demonstrating that structure and content of chain extenders played an important role in the properties of PHUs (Fig. 11b and c). The most remarkable improvement in mechanical properties of the resulting PHUs can be obtained when the norbornane-based chain extender was applied owing to the norbornane ring acting as an effective physical cross-linking point since no crystalline structure or hydrogen bonding was observed in their elastomers. This inference was the same as what Jiao et al. [67] got, who synthesized UV-curable PUA oligomers modified with cycloaliphatic epoxide resin.  \n\nOne conclusion we should note is that it is a capital idea to introduce rigid groups into PUA which will significantly improve the hardness of coatings. Whereas, the introduction of benzene rings may result in yellowing of coatings, as benzene ring can be easily oxidized into quinones. In consequence, we should avoid employing materials contained benzene rings to synthesize PUA resins when the appearance of films is a priority.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3.4. Introduction of inorganic nanoparticles  \n\nInorganic nanoparticles can provide excellent mechanical properties for organic/inorganic composites because nano-inorganic fillers are not only small in size but also large in specific surface area. As a result, there exists a strong interaction between particles and polymer interface, which significantly improves physical properties of polymers [68,69].  \n\nGenerally, nano-inorganic fillers that can be introduced into the PUA matrix include silica [70], carbon nitride [17], calcium carbonate [71], alumina [72] and zinc oxide [73] and so on. Lv et al. [16] acquired some waterborne UV-curable $\\mathrm{PUA}/\\mathrm{SiO}_{2}$ nanocomposites via traditional sol-gel method, in which KH-570 was used as the coupling agent of inorganic phases and organic phases, making sure $\\mathrm{{siO}}_{2}$ had good dispersion in the PUA matrix and then incorporated modified- $s\\mathrm{i}0_{2}$ into the ends of the PUA main chains by radical polymerization. Comparing to the physical blending method, from results, it was easier to obtain a uniform emulsion by the sol-gel technique owning to $\\mathrm{{siO}}_{2}$ nanoparticles showing a tendency to aggregate together without any KH-570 added (Fig. 12), which can bring some good effects in practical production applications. At that, comparing with neat PUA, the pencil hardness of $\\mathrm{{PUA}}/{\\mathrm{{SiO}}_{2}}$ coatings enhanced from the HB up to 4H when 6 wt. $\\%$ of silica was added. Certainly, Kim et al. [73] and Xu et al. [74] both also obtained similar consequences by introducing ZnO (Fig. 13a and b) and $\\mathsf{C a C O}_{3}$ (Fig. 13c) into PUA matrix, respectively, in which KH-570 was used as the coupling agent to modify inorganic fillers. Afterward, Liu et al. [75] revealed the relationship between pencil hardness and modified inorganic fillers. As expected, increasing modified fillers loading resulted in apparent improvement of pencil hardness, raising from HB to 2H with $2\\mathrm{wt.\\%}$ filler content. Nevertheless, the pencil hardness occurred a reduction from 2H to H when high filler content was added, which may be caused by the occurrence of inorganic particles aggregation (Fig. 14). As a result, appropriate dispersion of the modified fillers is crucial to take advantage of nanoscale reinforcement and to acquire desired physical and mechanical properties of composites films.  \n\nIn another research, Liao et al. [17] prepared a suite of UV-curable waterborne Wsi-PUA- $\\mathrm{.C_{3}N_{4}}$ composites including vinyl hydroxyl silicone oil and different contents of $\\mathrm{C}_{3}\\mathrm{N}_{4}$ without any couple agents. The results showed that the dispersion of $\\mathrm{C}_{3}\\mathrm{N}_{4}$ particles in composite films were homogeneous when the additive contents of $\\mathrm{C}_{3}\\mathrm{N}_{4}$ were low, endowing composite films with the excellent mechanical property. Nevertheless, agglomerates could be found at higher $\\mathrm{C}_{3}\\mathrm{N}_{4}$ content, which can be supposed to the fact that the high concentration induced phase separation (Fig. 15). Certainly, the pencil hardness of films could increase from 2H to 4H when the content of $\\mathrm{C}_{3}\\mathrm{N}_{4}$ was low. Nam et al. [71] investigated the effect of inorganic nanoparticles $\\mathsf{C a C O}_{3}$ in the UVcurable PUA coating and revealed that the performance of organic/ inorganic nanocomposite film was intensively linked with organicallymodified colloidal $\\mathsf{C a C O}_{3}$ nanoparticles. This was because the weak interfacial interaction between organic phases and inorganic interfaces could be disconnected when the amount of additive $\\mathsf{C a C O}_{3}$ was high, resulting in discontinuity of bond matrix, which gave rise to the disastrous fault of the nanocomposite films. Hence, in order to get highperformance UV-curable PUA nanocomposites coatings, inorganic nanoparticles homogeneously dispersed in organic matrix is crucial.  \n\n![](images/2bc4facc701bc220b8107d411dc5859b0a3a7242226b8aa633b4ea7250b0b555.jpg)  \nFig. 11. a) Synthetic route of PHUs. b) Stress-strain curves of PHUs chain extended with $50\\mathrm{wt.\\%}$ hard-segment content and c) Norbornane diamine at several har segment contents. [56] Copyright 2017. Reproduced with permission from John Wiley and Sons [56].  \n\nAbove of all, something we can discover is that, although PUAs modified with inorganic fillers can raise the hardness of coatings significantly, inorganic nanoparticles may be poorly dispersed due to miserable dispersibility of the high inorganic fillers content in the organic phase, resulting in unfortunate performance enhancement [76]. Therefore, in order to avoid this negative effect, the amount of inorganic filler should be controlled in the appropriate range, because the appropriate dispersion of the nanofillers is crucial to take advantage of nanoscale reinforcement and to obtain desired physical and mechanical properties of nanocomposites [75]. Of course, it must be mentioned that introducing inorganic fillers into the resin matrix will roughen the surface of coatings.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 3.5. Hyperbranched modification  \n\nHyperbranched polymers have advantages of high solubility and reactivity, low solution viscosity and melt viscosity, which are widely used in coatings [77–79]. Modifying PUA with hyperbranched structure not only improve the functionality but also can reduce the viscosity of system, contributing to the dispersion of materials within matrix [80–83]. Some researchers have demonstrated that introducing dendritic hyperbranched PUA into curing system will augment the crosslinking density [84,85] and will form the highly compact structure of films owing to its high functionality.  \n\nJana et al. [86] acquired the hyperbranched core (Fig. 16a) through esterification of pentaerythritol (PE), 2, 2-bis (methylol) propionic acid (DMPA) and trimethylolpropane (TMP), whose branching can be controlled with a varying amount of DMPA as chain extender, and then can form the alkyd polyurethane resin by employing phthalic anhydride and benzoic acid as end-cappers, both containing phenyl groups. The research revealed that with increasing the branching in the hyperbranched core, the pendulum hardness of coatings was reinforced by the introduction of rigid groups of end-cappers. However, the increment of the extent of branching in polyurethane structure lost the orientation or structural regularity of alkyd polyurethane chain, resulting in decreasing the glass transition temperature. In another research, a cluster of hyperbranched polyurethane acrylate (F-HBPUA) with diverse hydroxyl numbers and flexible chains was successfully developed by Xiang et al. [87] (Fig. 16b), and then the effect of generation number and flexible chain on the performances of resin and film was investigated. The results indicated that with increasing generation numbers and chain lengths, the increment of the viscosity was occurred, whereas hardness decreases from F to HB owing to its flexibility which increases with longer soft chains. Certainly, the number of polar groups (nitrogen and oxygen) was raised with the increment of the degree of branching and soft chain length, which strengthened the intermolecular interaction and then endowed good mechanical properties to films. [88,89] Apart from that, Jeong et al. [90] also investigated the effect of degree of HBPUA’s branching on performance, obtaining the result that with increasing the branching from 8 to 16, the hardness of HBPUA coatings enhanced slightly, exhibiting that the effect was not significant. The reason for this phenomenon will be discussed below. Absolutely, one thing for synthesizing oligomers we should be aware is that HBPUA can provoke rapid gelation of the mixed solution in a brief period during preparation owing to its high reactivity. In order to prevent this issue from occurring, sometimes, the reaction was carried out with excess polymerization inhibitors or solvent [31].  \n\n![](images/caa9fd18331bc8a935915710d583716f886ed2ebe8e13cca61a24bd4f5670c9e.jpg)  \nFig. 12. TEM micrographs of PUA and PUA $\\mathrm{\\SiO}_{2}$ hybrid particles: (a) pure PUA, (b) PUA with $4\\mathrm{wt.\\%}$ unmodified $\\mathrm{{SiO}}_{2},$ (c) PUA with $4\\mathrm{wt.\\%}$ modified $\\mathrm{SiO}_{2}$ and (d) PUA with $6\\mathrm{wt.\\%}$ modified $\\mathrm{{SiO}}_{2}$ [16]. Copyright 2015. Reproduced with permission from Royal Society of Chemistry [16].  \n\n![](images/e4288ff7a01ae4da684f8873ef046bd3f1667ea280232bede47f3918bff4fd29.jpg)  \nFig. 13. a) Reaction mechanism of KH-570 with $z_{\\mathrm{{nO}}}$ surface hydroxyl groups. b) The relationship between hardness and modulus values of PUA/ZnO nanocomposite films and ZnO content. [73] c) Brief mechanism of hydrolysis of KH-570 and surface modification of inorganic carbonate [74]. Copyright 2012. Reproduced with permission from Elsevier [73]. Copyright 2018. Reproduced with permission from Springer Nature [74].  \n\n![](images/1ba46e6d4c180fe3a05b5a2841af8a8d1df3a6154f5d8c2d1dfdebf2efc3db04.jpg)  \nFig. 14. SEM micrographs of cross-section of the UV-curable nanocomposite coatings (coated PC) containing a, b $2\\mathrm{wt.\\%}$ and d, e 5 wt. $\\%$ $\\mathrm{TiO}_{2}$ $\\scriptstyle\\phantom{+}_{2}-S\\mathrm{iO}_{2}/\\mathbf{P}$ (MMA-coPMPM), and surface of the UV-curable nanocomposite coatings (coated PC) c 2 wt.% and f 5 wt. $\\%$ $\\mathrm{TiO}_{2}$ - $\\mathrm{SiO}_{2}$ /P(MMA-co-PMPM). [75] Copyright 2018. Reproduced with permission from Springer Nature [75].  \n\nFrom the above research, what we can conclude is that hyperbranched modification both improves functionality and reduces system viscosity, resulting to coatings leveling [91–93]. Nevertheless, singlecomponent hyperbranched polymers have low crosslink density and acquire miserable results after curing. The reason is that although functionalities of polymers are considerable, each of functional groups can be cross-linked together after curing is impossible due to the spherical shape of polymers, which results in a low crosslink density [94–97]. Whereas, if researchers employ it as an additive, especially as an additive of low-functionality PUA, its advantages can be fully exerted, and properties of PUA can be improved well [98].  \n\nZhang et al. [99] chose toluene diisocyanate (TDI) as the main part of PUA matrix. Bifunctional PUA was first prepared by the reaction between polyethylene glycol, hydroxyethyl acrylate and TDI. Subsequently, hyperbranched HBPUA was synthesized via trimethylolpropane as the core of the dendritic polymer, which was used as additives and then introduced into PUA matrix to acquire coatings (Fig. 17a). The results showed that with an increase in HBPUA content, the hardness of coatings improved from 6H to 9H, simultaneously the abrasion resistance and storage modulus also raised markedly (Fig. 17c). Definitely, the cured film with about $10\\mathrm{wt.}\\%$ HBPUA displayed strongly raised tensile strength while the elongation at break received a little reduction. However, the elongation at break was reduced by about $30\\%$ when $20\\mathrm{wt.}\\%$ HBPUA was added, indicating a significant decline in toughness (Fig. 17b). Some researches also disclosed the similar issue that although the rigidity of coatings was reinforced with the increase of crosslink density, the remarkable decrease in elongation at break values resulted in the restrained toughness [31]. And so, it’s a crucial issue that how to keep the toughness constant or decrease slightly while increase the hardness of coatings. One is selecting chain extenders or long soft segments that can generate more hydrogen bonds to promote micro-phases separation or mixed phases [100], which can play a role of the buffer when coatings subjected to force, obtaining the effect of toughness [101]. But for the former, it will lead to uneven coating surface owning to its crystallinity, which is bad for films as the smooth appearance of them is a priority. Another is increasing the content of flexible chain extenders in soft segments, so that PUA chains can easily move, and thus improve the toughness of films. But beyond that, Xiang et al. [87] also certified that as the soft chains increased, the dendritic arms became more flexible, the cured films were more flexible, accordingly. Although the toughening effect can be acquired, the film hardness descended [102]. So, we can receive that only moderate addition of soft chains can keep hardness and toughness both well.  \n\n![](images/b359c529ab1effc66a59036c860f480aab00c5e60d4874bc4f18aeb1b19f6e00.jpg)  \nFig. 15. TEM micrographs of ultra-thin sections taken from the coating samples filled with: a) $0.25\\mathrm{wt.\\%}$ , b) $0.5\\mathrm{wt.}\\%,$ , c) 1.0 wt. $\\%$ and d) $2.0\\mathrm{wt.\\%}$ $\\mathsf{g}\\mathrm{-}\\mathsf{C}_{3}\\mathsf{N}_{4}$ particle [17] Copyright 2015. Reproduced with permission from Elsevier [17].  \n\nGiving a similar example, Zou et al. [103] designed hyperbranched polyurethane (HBPU) by reacting IPDI and poly (tetrahydrofuran), which brought flexible segments for HBPU resin, sequentially generating more hydrogen bonds among molecular chains. HBPU and the linear analog polyurethane (LPU) were used as tougheners in the diglycidyl ether of bisphenol A (DGEBA)/amine system, respectively. This research revealed that the average crosslinking density, comparing with DGEBA/LPU films, DGEBA/HBPU samples were higher attributing to high functionality of HBPU. Furthermore, though adding HBPU raised the crosslink density, the HBPU introduced into matrix enhanced the flexibility of the network structure as well (Fig. 18). It should be noted that the enhancement in toughness is associated with micro-phase separation structures which prevent the crack to freely develop and absorb the impact energy. Apart from that, the stronger interface interaction in the DGEBA/HBPU films promotes the stress transfer when films subjected to force, which is caused by the generation of hydrogen bonding that formed the buffer upon loading.  \n\n![](images/eb8e19a04b94a1fe50d2fc5c2b167d3d5065d1b06e0cb0a9616338ac15c265a6.jpg)  \nFig. 16. a) Scheme of the synthesis of the hyperbranched core. [86] b) Schematic representation for the preparation of F-HBPUA [87]. Copyright 2017. Reproduced with permission from John Wiley and Sons [86]. Copyright 2017. Reproduced with permission from Elsevier [87].  \n\n![](images/79fc80b8b7dfd8b3256ee7493e343c1385d2fc7d40d0466b21bba88e1ceaf933.jpg)  \nFig. 17. a) Synthetic process of PUA/HBPUA UV-curable coatings. b) Stress-strain curves of the cured films. c) Storage modulus (E′) graphs of UV-curable coatings as a function of temperature. [99] Copyright 2016. Reproduced with permission from Royal Society of Chemistry [99].  \n\n![](images/27900aa5eb45069edb84782a067391aeaaf8912ca7992517092ffad1c2f52c05.jpg)  \nFig. 18. The influence of modifier content on the a) impact strength and b) flexural strength. c) Schematic illustration of separate particles in the DGEBA/HBPU films. [103] Copyright 2016. Reproduced with permission from Royal Society of Chemistry [103].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 4. Conclusion  \n\nIn summary, five types of strategies are used for hardening modification of PUA, such as the improvement of the crosslinking density of system, the enhancement in the effect of hydrogen bonding, the incorporation of rigid groups at molecular level, the introduction of inorganic fillers and hyperbranched modification, which have their own advantages and disadvantages. Of these, hyperbranched polyurethane acrylate is optimal because it not only provides polyfunctionality (increasing the cross-linking density), but also reduces system viscosity and contributes to the dispersion of compositions. Although the effect of single hyperbranched polymer on film formation is not very good, its advantages can be maximized when it employs as an additive to coatings. Next one is followed by the introduction of rigid groups owning to their pronounced effect on the hardness of coatings. The material containing rigid groups should be a benzene-free substance which can prevent coatings from yellowing. Furthermore, in order to maximize the increment of hardness, this material will be introduced into the hyperbranched polymer by the formation of hyperbranched nuclei. For the polyfunctional modification, it is a distinct method that using vegetable oils as hyperbranched polyols which can increase the functionality of PUA by epoxidation and ring-opening reaction. In addition, it can be a sustainable route to solve the problem of environment and depletion of the world crude oil stock due to their green and abundant resources, such as palm oil [104] and olive oil [105]. Certainly, siloxanes and silane coupling agents, or inorganic fillers can be introduced into PUA coatings to enhance the hardness of films significantly when the contents of those materials are moderate, which is economical for industrial manufacture. In another expect, we can endow hardening coatings with excellent toughness by the introduction of flexible aliphatic chain or others that can form remarkable hydrogen bonds, accordingly generating physical cross-linking buffers, eventually absorbing impact energy or strengthening stress transfer in the intermolecular chains.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 18,
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Liu, Preparation, characterization and application of UV-curable flexible hyperbranched polyurethane acrylate, Polymers 9 (2017) 552. [99] Q. Zhang, C. Huang, H. Wang, M. Hu, H. Li, X. Liu, UV-curable coating crosslinked by a novel hyperbranched polyurethane acrylate with excellent mechanical properties and hardness, RSC Adv. 6 (2016) 107942–107950.   \n[100] J. Wang, H. Zhang, Y. Miao, L. Qiao, X. Wang, F. Wang, Microphase separation idea to toughen $\\mathrm{CO}_{2}$ -based waterborne polyurethane, Polymer 138 (2018) 211–217.   \n[101] Z. Jiao, Q. Yang, X. Wang, C. Wang, UV-curable hyperbranched urethane acrylate oligomers modified with different fatty acids, Polym. Bull. 74 (2017) 5049–5063.   \n[102] Y. Zhang, A. Asif, W. Shi, Highly branched polyurethane acrylates and their waterborne UV curing coating, Prog. Org. Coat. 71 (2011) 295–301.   \n[103] Z. Zou, X. Liu, Y. Wu, B. Tang, M. Chen, X. Zhao, Hyperbranched polyurethane as a highly efficient toughener in epoxy thermosets with reaction-induced microphase separation, RSC Adv. 6 (2016) 18060–18070.   \n[104] P.K.S. Pillai, M.C. Floros, S.S. Narine, Elastomers from renewable metathesized palm oil polyols, ACS Sustain. Chem. Eng. 5 (2017) 5793–5799.   \n[105] C. Zhang, S.A. Madbouly, M.R. Kessler, Biobased polyurethanes prepared from different vegetable oils, ACS Appl. Mater. Interfaces 7 (2015) 1226–1233.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# (19) United States (12) Patent Application Publication (10) Pub. No.: US 2006/0292209 A Lewandowski et al.",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (54) REACTIVE HYDROPHILIC OLIGOMERS",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# Related U.S. Application Data  \n\n(75） Inventors: Kevin M. Lewandowski, Inver Grove Heights, MN (US); Duane D. Fansler, Dresser, WI (US); Michael S. Wendland, North St. Paul, MN (US); Steven M. Heilmann, Afton, MN (US); Babu N. Gaddam, Woodbury, MN (US)  \n\nCorrespondence Address:   \n3M INNOVATIVE PROPERTIES COMPANY   \nPO BOX 33427   \nST. PAUL, MN 55133-3427 (US)  \n\n(73) Assignee: 3M Innovative Properties Company (21) Appl. No.: 11/463,103 (22) Filed: Aug. 8, 2006  \n\n(63) Continuation-in-part of application No. 10/672,580, filed on Sep.26, 2003.",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# Publication Classification  \n\n(51) Int. Cl. A61L 15/00 (2006.01) (52) U.S. Cl. 424/445; 525/107",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# ABSTRACT  \n\nHydrophilic compositions are described, which are prepared from a first oligomer containing pendent polymerizable groups and pendent hydrophilic groups, crosslinked with a co-reactive second component oligomer possessing photoinitiator groups. The compositions may be used as in preparation of hydrophilic gel coatings or layers for medical devices.",
+        "category": " Abstract"
+    },
+    {
+        "id": 6,
+        "chunk": "# REACTIVEHYDROPHILIC OLIGOMERS  \n\nCROSS REFERENCE TO RELATED APPLICATIONS  \n\n[0001] This application is a continuation in part of U.S. application Ser.No. 10/672,580, filed Sep.26, 2003,the disclosure of which is herein incorporated by reference.",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# TECHNICALFIELDOFTHEINVENTION  \n\n[0002] This  invention  relates to  novel hydrophilic, crosslinkable oligomer compositions and articles prepared therefrom. The compositions can be useful in preparing gel materials and medical articles incorporating such materials, particularly medical articles useful as wound dressings.",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# BACKGROUNDOFTHEINVENTION  \n\n[0003] Historically, exudate from a wound has been treated by absorbing it using a dressing containing an absorbent material. Such dressings have contained a padded absorbent material attached to an adhesive tape backing. The padded absorbent material is applied to the wound to absorb the wound exudate. A difficulty with this type of dressing is that the scab typically forms in and as part of the pad as the wound heals. Thus, when the dressing is removed, the scab is removed. This problem has been addressed by providing a porous film between the absorbent material and the wound to reduce the likelihood that a scab formed will become attached to the absorbent material.  \n\n[0004] More recently the use of so-called “occlusive” dressings for pressure sores and ulcers has gained acceptance. Most of these products are formed from several layers, including at least an inner skin-contacting layer and an outer backing layer. The dressing is applied as a cover for the sore or ulcer in a size providing a margin around the wound area that adhesively seals to the skin.An inner layer contains water-absorptive materials, so that fluid from the wound is absorbed into the layer, making it possible to keep the dressing in place for at least several days. Such occlusive dressings tend to promote healing by maintaining the wound under moist conditions without forming a crust, and serving as a barrier against bacterial infection. Such dressings for \"moist wound healing\" are particularly useful for dermal burns, traumatic skin deficiencies, incised wounds, and the like.  \n\n[0005] A wound care product in current use utilizes a hydrocolloid absorbent. Such a material typically has poor transparency so the treatment state cannot be observed from the outside. Also, such a material can partially lose its integrity after absorbing wound fluid. Flexibility of hydrocolloid dressings can be poor, which makes it difficult to apply the dressing to a bend portion of a body, such as a joint, etc. The portion of the absorbent in contact with the wound is converted to a gel-like material, and, when the dressing is removed, a portion of this absorbent material can be left in the wound, and must be removed to permit examination and/or before applying another dressing.",
+        "category": " Background of the invention"
+    },
+    {
+        "id": 9,
+        "chunk": "# SUMMARYOFTHEINVENTION  \n\n[0006] Though there are known hydrophilic gel materials useful in medical applications such as wound dressings, many do not have the appropriate balance of absorption and cohesive strength. Thus, additional such materials are needed.Further, it can be desirable to provide an occlusive material that is also transparent and/or flexible for use in a medical article such as a wound dressing or wound packing material. Yet further, it can be desirable to provide compositions that are melt-processible.  \n\n[0007] The current invention describes reactive, meltprocessible materials that may be cast on a web and cured by a chain-growth mechanism to yield uniform coatings, particularly gel coatings. The component oligomers and extent of reaction, or crosslink density, can be varied in order to provide specific properties for a range of applications. The molecular weight of these materials is such that they can easily be processed, giving economic and/or environmental advantages. The materials can be subsequently cured through application of actinic energy, such as UV radiation, to yield improved final mechanical properties. Thus, these materials represent a significant advance of the current art.  \n\n[0008]  Briefly, the present invention provides novel hydrophilic, oligomeric compositions prepared from a first oligomer containing pendent hydrophilic groups and pendent polymerizable functional groups, and a co-reactive second component oligomer having pendent photoinitiator groups. The second component oligomer may further comprise polymerizable monomer units having pendent hydrophilic groups. The compositions can be melt-processible.  \n\n[0009]   In one aspect this invention provides a hydrophilic, crosslinkable, oligomeric composition comprising:  \n\n[0010] (a) a first component oligomer comprising a plurality of polymerized monomer units having pendent, free-radically polymerizable functional groups, and pendent, hydrophilic poly(alkylene oxide) groups; [0011] (b) a second component oligomer comprising a plurality of polymerized monomer units having pendent, photoinitiator groups.  \n\n[0012] This invention can have one or more of several advantages. The invention provides a UV crosslinkable composition that produces no or minimal by-products, and that achieves its crosslink density by chain-growth addition. The composition is low in viscosity, readily melt processible and coatable, and has minimal residuals content such as solvents, monomers, plasticizers, by-products of condensation reactions or displacement reactions and/or viscosity modifiers. The compositions can rapidly and reliably prepared without requiring specialized equipment and without generating concerns about potentially toxic or irritating unreacted low molecular weight monomeric species.  \n\n[0013]   In another aspect this invention provides a process for making a substrate bearing a coating of a crosslinked composition (such as a hydrophilic gel） on at least one surface thereof, comprising the steps of:  \n\n[0014] (a） coating the crosslinkable, oligomeric composition of the invention, containing an initiator onto a substrate, and   \n[0015] (b) subjecting the coated crosslinkable composition to sufficient actinic energy to crosslink said composition.  \n\n[0016] For performance, environmental, and economic considerations, photoinitiated polymerization is a particularly desirable method for preparing a coating, such as a gel layer directly on the substrate. With this polymerization technique, it is advantageous to create a composition having coatable viscosity of 10,oo0 centipoise or less (when measured at or below $100^{\\circ}$ C.),coat the composition on the substrate, then crosslink the components to build strength.  \n\n[0017] As used herein, the term “melt processible” or simply “processible” is used to refer to polymer compositions that possess or achieve a suitable low viscosity for coating or extrusion at temperatures less than the decomposition temperature(s) of the oligomers and less than the temperature at which premature gelation occurs, using conventional extrusion equipment without the need for addition of solvents, monomers, plasticizers and/or viscosity modifiers and without the need for extraordinary pressures. Preferably the composition is melt processible at temperatures less than or equal to $100^{\\circ}\\mathrm{~C~}$ ，  \n\n[0018] In one embodiment, this invention provides absorbent medical articles and hydrophilic, polymeric gel materials for use therein, which are preferably transparent. By “gel” (or “polymer gel” or“polymeric gel material” or \"hydrophilic gel\") it is meant a gel material capable of swelling on contact with (or water-based fluids such as body fluids including blood, plasma, and intracellular fluid or fluids similar to body fluids such as physiological saline), but does not dissolve in water. The gels are substantially continuous, i.e., lacking a cellular or void structure (although minor defects such as entrapped air bubbles or fractures may be present) and thus generally in a solid or semi-solid form. The term “gel” is used regardless of the state of hydration. Preferably, the gel does not include water until it comes in contact with a surface from which it absorbs water (e.g., a wound). Significantly, even without water (or other plasticizing agents) preferred embodiments of the gel material of the present invention are flexible.  \n\n[0019] By “absorbent” it is meant that the material is capable of absorbing fluids, particularly body fluids and preferably moderate to heavy amounts of body fluids, while retaining its structural integrity (i.e., remaining sufficiently intact such that it can perform the function of acting as a wound dressing, for example).  \n\n[0020]  Preferably the gel material is transparent and retains its transparency after absorption of fluids. By “transparent” it is meant that when the preferred material is applied to a patient (e.g., at a wound site), the area underlying the dressing can be visualized sufficiently to permit observation of the wound by a health care worker.  \n\n[0021] The term hydrophilic is used herein to describe oligomer compositions, which are capable of absorbing water exposed thereto in significant quantity, typically more than about $50\\%$ by weight, preferably $100\\%$ by weight, more preferably more than $200\\%$ by weight.  \n\n[0022] The application of hydrophilic polymer gels to medical practice is, for example, found in wound dressings, wound packings, adhesives (particularly pressure sensitive adhesives), contact lenses, intraocular lenses, adhesives for biological tissues, adhesion preventing materials, adsorbents for blood purification, base materials for releasing pharmacologic agents, and the like.Materials for dental moldings or impressions are another potential medical article use. Thus, as used herein, “medical” applications encompass dental applications, including dental adhesives, restoratives, coatings, composites, sealants, etc. Because water swelling polymer gels have compositions and mechanical properties similar to those of biological tissues, such gels may be applied in a wide variety of fields in the future.  \n\n[0023]  The ability to vary the crosslink density permits the modification of properties suitable for the various applications described previously. The novel compositions of the present invention cure to form crosslinked compositions possessing tailorable properties such as shear, peel, release, strength, hardness, elasticity, absorbancy and toughness, for example, through selection of the particular constituents, and by control of the crosslink density. While the requirements for medical gels and flexible coatings, for example, are very different, the structure of the material and density of linkages can be altered while still maintaining the same method of forming crosslinked compositions. The maximum crosslink density is predetermined by the percentage of polymerizable functional groups of the first component oligomer and the percentage of photoinitiator groups of the second component oligomer incorporated into the crosslinkable composition. It may also be desirable to partially convert or cure a system for improved processing, while using a subsequent curing stage to obtain final properties.  \n\n[0024] As used herein, the term “crosslinking\" means the formation of a polymeric network of infinite molecular weight and occurs in polymerizations with oligomeric reactants having functionalities greater than two. Additional information may be found in G. Odian, Principles of Polymerization，3rd edition,1991，John Wiley & Sons: New York, p. 1o8. A crosslink is formed between the pendent polymerizable functional groups by a chain growth process.  \n\n[0025] Advantageously, the present invention provides crosslinkable compositions that are readily processed without appreciable residual content such as solvents, monomers,plasticizers and/or viscosity modifiers, and which do not contain byproducts from condensation or displacement reactions. Curable systems containing residual content can give rise to a significant increase in density when transformed from the uncured to the cured state causing a net shrinkage in volume. As is well known, shrinkage can cause a general loss of adhesion in many instances as well as significant movement and unpredictable registration. Shrinkage can also create residual stress in coatings, which can subsequently lead to mechanical failure.  \n\n[0026] The composition of the present invention minimizes shrinkage due to solvent evaporation and/or monomer polymerization. The low shrinkage compositions of this invention are particularly useful in dental, molding applications or in any applications where accurate molding and/or registration are required. The present invention provides a new class of reactive oligomers that may be formulated as $100\\%$ solids, melt processed, cured by actinic radiation means and that exhibit properties that meet or exceed those of solvent-borne or syrup polymers. The present invention provides compositions that exhibit less than $2\\%$ shrinkage, and preferably less than $1\\%$  \n\n[0027] Further, the purity of the materials and clean environment for processing are also important to produce high performance materials. Polymers used for coatings and gels are often desirably delivered without significant amounts of volatile materials (such as monomeric species) to eliminate any contamination. However, the problems of residual volatile materials constitute a much more formidable challenge especially when acceptable limits of migratable, volatile impurities are on the order of a few parts per million. Industries such as medical and food packaging require materials of high purity and lower cost. The composition of the present invention avoids problems due to residuals contamination, having a residuals content of less than 2 weight percent, preferably less than 1 weight percent.",
+        "category": " Abstract"
+    },
+    {
+        "id": 10,
+        "chunk": "# DETAILED DESCRIPTION OF THE INVENTION  \n\n[0028] The present invention provides crosslinkable compositions useful in the preparation of hydrophilic gels. The compositions are prepared from oligomers having pendent polymerizable functional groups and are formed from ethylenically unsaturated monomers. The composition comprises:  \n\n[0029] (a) a first component oligomer comprising a plurality of polymerized monomer units having pendent, free-radically polymerizable functional groups, and a plurality of polymerized monomer units having pendent, hydrophilic poly(alkylene oxide) groups; [0030]  (b) a second component oligomer comprising a plurality of polymerized monomer units having pendent, photoinitiator groups and a plurality of polymerized monomer units having pendent, hydrophilic poly(alkylene oxide) groups.  \n\n[0031] The composition comprises, per 10O parts by weight of a first component, a sufficient amount of said second component to provide greater than two crosslinks per first component oligomer chain when cured or crosslinked. The relative amounts of said first and second component oligomers may vary widely; i.e. from 0.1 to 99.9 parts by weight of the first component oligomer and from 0.1 to 99.9 parts by weight of the second component oligomer. However, the relative amounts are chosen so that the crosslinked composition is hydrophilic, i.e. absorbs at least 50 wt. $\\%$ water.  \n\n[0032]  In one embodiment the first oligomer component (a) comprises:  \n\n[0033] (a) from 20 to 99 parts by weight of polymerized monomer units derived from of an ethylenically-unsaturated monomer having a poly(alkylene oxide) group;   \n[0034] (b) from 0.1 to 35 parts by weight of polymerized monomer units derived from of an ethylenicallyunsaturated monomer having a pendent polymerizable group;   \n[0035](c) from O to 50 parts by weight of polymerized monomer units derived from polar monomer;   \n[0036] (d) from O to 20 parts by weight of polymerized monomer units derived from hydrophobic monomers;   \n[0037]  (e) from O to 10 parts by weight of at least one other monomer.  \n\n[0038] In one embodiment, the second component oligomer comprises:  \n\n[0039] (a) from 0.01 to 99.99 parts by weight of polymerized units of free radically polymerizable; and  \n\n[0040](b) from 99.99 to 0.01 parts by weight of polymerized monomer units derived from an ethylenicallyunsaturated monomer having a pendent photoinitiator group.  \n\n[0041]  Preferably the free radically polymerizable monomers of the second component oligomer are (meth)acryloyl monomers. It will be understood with respect to the above formula, that the oligomeric photoinitiator may have a photoinitiator group on essentially each repeat unit of the oligomer (i.e. ${>}90\\%$ of the repeat units).  \n\n[0042]  In a preferred embodiment the second oligomer component comprises:  \n\n[0043](a) from 20 to 99 parts by weight, preferably 50 to 99 parts by weight, of polymerized monomer units having pendent, hydrophilic poly(alkylene oxide) groups, and   \n[0044] (b) from 0.1 to 25 parts by weight, preferably 0.1 to 10 parts by weight, of polymerized monomer units derived from of an ethylenically-unsaturated monomer having a pendent photoinitiator group;   \n[0045](c) from O to 25 parts by weight, preferably 0.1 to 10 parts by weight, of polymerized monomer units derived from of an ethylenically-unsaturated monomer having a pendent polymerizable group; and   \n[0046] (d) from O to 20 parts by weight, preferably less than 10 parts by weight, of hydrophobic monomers, such as polymerized monomer units derived from (meth)acrylic acid esters, preferably of non-tertiary alkyl alcohols containing 1-14 carbon atoms;   \n[0047] (e) from O to 50 parts by weight of polymerized monomer units derived from a polar monomer; and   \n[0048](f) from O to 40 parts by weight, preferably less than 25 parts by weight, of at least one other monomer (described below).  \n\n[0049] The first and second component oligomers comprise polymerized monomer units derived from of an ethylenically-unsaturated monomer having pendent poly(alkylene oxide) group of the formula:  \n\n$$\n\\mathrm{\\DeltaZ\\mathrm{-}Q\\mathrm{-}(C H(R^{1})\\mathrm{-}C H_{2}\\mathrm{-}Q)_{m}\\mathrm{-}R^{2},}\n$$  \n\nwherein Z is a polymerizable ethylenically usaturated moiety, $\\mathbb{R}^{1}$ is a $\\mathrm{H}$ or a $\\mathrm{C_{1}}$ to $\\mathrm{C}_{4}$ alkyl group, $\\dot{\\mathrm{R}}^{2}$ is a $\\mathrm{H}$ a $\\mathrm{C}_{1}$ to $\\mathrm{C}_{4}$ alkyl group, aryl group, or combinations thereof and m is from 2 to 100, preferably 5 to 20, and Q is a divalent linking group selected from —O—， $\\mathrm{-NR^{1}-}$ ，一 $\\mathrm{CO}_{2}$ —and $\\bar{\\mathrm{-}\\mathrm{CONR^{1}}}$ . In one embodiment, the poly(alkylene oxide) group is a poly(ethylene oxide) (co)polymer. In another embodiment, the pendent poly(alkylene oxide) group is a poly(ethylene oxide-co-propylene oxide) copolymer. Such copolymers may be block copolymers, random copolymers, or gradient copolymers.  \n\n[0050]  Useful ethylenically unsaturated moiety, Z, of the monomer may include:  \n\n![](images/2ac9c6e803b2fd22ec6ad51084ffd67cb4ac5c983e57fd720fb38f23129d7239.jpg)  \n\nwherein $\\mathrm{R}^{3}$ is $\\mathrm{~H~}$ or Me and $\\mathrm{r}{=}1{-}10$ [0051]  The monomer having a poly(alkylene oxide) group can be prepared, for example, by reacting mono- or difunctional alkylene oxide (co)polymers (which are typically commercially available) with reactive ethylenically unsaturated compounds (e.g., acrylates). The functional groups terminating the poly(alkylene oxide) may include hydroxy groups, amine groups and carboxy groups. A variety of reactive ethylenically unsaturated compounds such as acrylate derivatives can be used including, but not limited to, (meth)acrylic acid, (meth)acryloyl chloride, (meth)acrylic anhydride, and 2-isocyanatoethyl (meth)acrylate. Preferably, the monomer is prepared by reacting the mono- or di-functional alkylene oxide (co)polymer with (meth)acrylic anhydride. Typically, if a stoichiometric amount of the ethylenically unsaturated reactant is combined with the monofunctional alkylene oxide (co)polymer (such as a monohydroxy terminated alkylene oxide (co)polymer), $100\\%$ conversion to the monosubstituted product is obtained.  \n\n[0052]  Examples of suitable monofunctional poly(alkylene oxide) monomers include poly(ethylene oxide) (meth)acrylate, poly(propylene oxide) (meth)acrylate, poly(ethylene oxide-propyleneoxide)(meth)acrylate， and combinations thereof. Such monomers preferably include one nonreactive end group such as $\\mathrm{(C_{1}-C_{4})}$ alkoxy, aryloxy (e.g., phenoxy), and $\\mathrm{(C_{1}-C_{4})}$ alkaryloxy. These groups can be linear or branched. These monomers can be of a wide range of molecular weights and are commercially available from sources such as Sartomer Company, Exton, Pa.; Shinnakamura Chemical Co., Ltd., Tokyo, Japan; Aldrich, Milwaukee, Wis.; and Osaka Organic Chemical Ind., Ltd., Osaka, Japan.  \n\n[0053] The first and optionally the second component oligomers of the composition comprise one or more pendent groups that include free-radically polymerizable unsaturation, including (meth)acryloyl, (meth)acryloxy, propargyl, vinyl, allyl, acetylenyl and (meth)acrylamido. Such pendent groups can be incorporated into the oligomer in at least two ways. The most direct method is, for example, to include among the monomer units monomers having two or more free radically polymerizable groups, preferably of differing reactivity.  \n\n[0054] Using the “direct method” of incorporating the pendent, free-radically polymerizable functional group, useful functional monomers include those unsaturated aliphatic, cycloaliphatic, and aromatic compounds having up to about 36 carbon atoms that include a functional group capable of free radical addition such as those groups containing a carbon-carbon double bond including vinyl, vinyloxy, (meth)acrylic, (meth)acrylamido, and acetylenic functional groups.  \n\n[0055] Examples of polyethylenically unsaturated monomers that can be used include, but are not limited to, polyacrylic-functional monomers such as ethylene glycol diacrylate, propylene glycol dimethacrylate, bisphenol-A di(meth)acrylate, trimethylolpropane triacrylate, 1,6-hexanedioldiacrylate, pentaerythritol di-, tri-, and tetraacrylate, and 1,12-dodecanedioldiacrylate; olefinic-acrylic-functional monomers such as allyl methacrylate, 2-allyloxycarbonylamidoethyl methacrylate, and 2-allylaminoethyl acrylate; allyl 2-acrylamido-2,2-dimethylacetate; divinylbenzene; vinyloxy group-substituted functional monomers such as 2-(ethenyloxy)ethyl (meth)acrylate, 3-(ethynyloxy)-1-propene, 4-(ethynyloxy)-1-butene, and 4-(ethenyloxy)butyl-2- acrylamido-2,2-dimethylacetate, and the like. Useful polyunsaturated monomers, and useful reactive/co-reactive compounds that may be used to prepare a polymer having pendent unsaturation are described in greater detail in U.S. Pat. No. 5,741,543 (Winslow et al.), incorporated in its entirety herein by reference.  \n\n[0056] Preferred polyunsaturated monomers are those where the unsaturated groups are of unequal reactivity. Those skilled in the art recognize that the particular moieties attached to the unsaturated groups affect the relative reactivities of those unsaturated groups. For example, where a polyunsaturated monomer having unsaturated groups of equal reactivity (e.g., HDDA) is used, premature gelation of the composition must be guarded against by, for example, the presence of oxygen, which acts as a radical scavenger. Conversely, where a polyunsaturated monomer having unsaturated groups of differing reactivities is used, the more reactive group (such as (meth)acrylate as (meth)acrylamido) preferentially is incorporated into the oligomer backbone before the less reactive unsaturated group (such as vinyl, allyl, vinyloxy, or acetylenic) reacts to crosslink the composition. The direct method is generally not preferred due to difficulty in control of branching and premature gellation.  \n\n[0057] An indirect, but preferred, method of incorporating pendent groups that comprise polymerizable unsaturation into the first and second oligomers is to include among the monomer units of the oligomer some that comprise a reactive functional group. Useful reactive functional groups include, but are not limited to, hydroxyl, amino, oxazolonyl, oxazolinyl, acetoacetyl, azlactonyl, carboxyl, isocyanato, epoxy, aziridinyl, acyl halide, and cyclic anhydride groups. Preferred among these are carboxyl, hydroxyl, amino, azlactonyl and aziridinyl groups. These pendent reactive functional groups are reacted with unsaturated compounds that comprise functional groups that are co-reactive with the reactive pendent functional group. When the two functional groups react, an oligomer with pendent unsaturation results. In some applications, it may be desirable to use less than a stoichiometric equivalent of unsaturated compounds that comprise co-reactive functional groups, so that some of the pendent functional group remain unreacted.  \n\n[0058] Using the “indirect method\" of incorporating the pendent, free-radically polymerizable functional groups, useful reactive functional groups include hydroxyl, secondary amino,oxazolinyl, oxazolonyl， acetyl, acetonyl，carboxyl, isocyanato, epoxy, aziridinyl, acyl halide, vinyloxy, and cyclic anhydride groups. Where the pendent reactive functional group is an isocyanato functional group, the co-reactive functional group preferably comprises a secondary amino or hydroxyl group. Where the pendent reactive functional group comprises a hydroxyl group, the co-reactive functional group preferably comprises a carboxyl, ester, acyl halide, isocyanato, epoxy, anhydride, azlactonyl or oxazolinyl group. Where the pendent reactive functional group comprises a carboxyl group, the co-reactive functional group preferably comprises a hydroxyl, amino, epoxy, isocyanate, or oxazolinyl group. Most generally, the reaction is between a nucleophile and electrophic functional groups.  \n\n[0059] Representative examples of useful monomers having reactive functional groups include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and 2-(2-hydroxyethoxy)ethyl (meth)acrylate; aminoalkyl (meth)acrylates such as 3-aminopropyl (meth)acrylate and 4-aminostyrene; oxazolinyl compounds such as 2-ethenyl-1,3-oxazolin5-one, 2-vinyl-4,4-dimethyl-1,3-oxazolin-5-one, 2-isopropenyl-4,4-dimethyl-1,3-oxazolin-5-one and 2-propenyl-4,4-dimethyl-1,3-oxazolin-5-one; carboxy-substituted compounds such as (meth)acrylic acid and 4-carboxybenzyl (meth)acrylate; isocyanato-substituted compounds such as isocyanatoethyl (meth)acrylate and 4-isocyanatocyclohexyl (meth)acrylate; epoxy-substituted compounds such as glycidyl (meth)acrylate; aziridinyl-substituted compounds such as N-acryloylaziridine and 1-(2-propenyl)- aziridine; and acryloyl halides such as (meth)acryloyl chloride.  \n\n[0060] Preferred functional monomers have the general formula:  \n\npbw, of the crosslinkable composition. Preferred photoinitiator monomers include free-radically polymerizable, ethylenically unsaturated compounds having the functionality represented by the structure:  \n\n![](images/560e916c15f74a9784b23a0a3e63c47b1bebf3c9e32e164eab66d00d66ddd66c.jpg)  \n\nwherein $\\mathrm{R^{\\prime}}$ is $\\mathrm{~H~}$ or a $\\textrm{C1}$ to C4 alkyl group, $\\mathbb{R}^{7},\\mathbb{R}^{8}$ and $\\mathbb{R}^{9}$ are independently a hydroxyl group, a phenyl group, a $\\textrm{C1}$ to C6 alkyl group, or a C1 to C6 alkoxy group.  \n\n[0062]   The photoinitiator monomers may be prepared by the reaction between a polymerizable monomer having a reactive functional group with a photoinitiator compounds having a co-reactive functional group. Representative examples of useful polymerizable monomers having a reactive functional group include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-(2-hydroxyethoxy)ethyl (meth)acrylate; aminoalkyl (meth)acrylates such as 3-aminopropyl (meth)acrylate and 4-aminostyrene; oxazolinyl compounds such as 2-ethenyl-1,3-oxazolin-5- one and 2-propenyl-4,4-dimethyl-1,3-oxazolin-5-one; carboxy-substituted compounds such as (meth)acrylic acid and 4-carboxybenzyl (meth)acrylate;isocyanato-substituted compounds such as isocyanatoethyl (meth)acrylate and 4-isocyanatocyclohexyl (meth)acrylate; epoxy-substituted compounds such as glycidyl (meth)acrylate; aziridinyl-substituted compounds such as N-acryloylaziridine and 1-(2- propenyl)-aziridine; and acryloyl halides such as (meth)acryloyl chloride.  \n\nwherein $\\boldsymbol{\\mathrm{R}}^{5}$ is hydrogen, a $\\mathrm{C}_{1}$ to $\\mathrm{C}_{4}$ alkyl group, or a phenyl group, preferably hydrogen or a methyl group; $\\mathrm{i}^{\\cdot}\\mathrm{k}^{4}$ is a single bond or a divalent linking group that joins an ethylenically unsaturated group to a reactive functional group “A” and preferably contains up to 34, preferably up to 18, more preferably up to 10, carbon and, optionally, oxygen and nitrogen atoms and, when $\\mathrm{R}^{4}$ is not a single bond, is preferably selected from  \n\nin which $\\mathrm{R}^{6}$ is an alkylene group having 1 to 6 carbon atoms, a $5-$ or 6-membered cycloalkylene group having 5 to 10 carbon atoms, or an alkylene-oxyalkylene in which each alkylene includes 1 to 6 carbon atoms or is a divalent aromatic group having 6 to 16 carbon atoms; and A is a functional group, capable of reacting with a co-reactive functional group for the incorporation of a free-radically polymerizable functional group.  \n\n[0063]  Representative examples of photoinitiator compounds having a co-reactive functional group include compounds such as 1-(4-hydroxyphenyl)-2,2-dimethoxyethanone, 1-[4-(2-hydroxyethyl)phenyl]-2,2- dimethoxyethanone, (4-isocyanatophenyl)-2,2-dimethoxy2-phenylethanone, 1-{4-[2-(2,3-epoxypropoxy)phenyl]}-2, 2-dimethyl-2-hydroxyethanone, 1-[4-(2- aminoethoxy)phenyl]-2,2-dimethoxyethanone,and“1-[4- (carbomethoxy)phenyl]-2,2-dimethoxyethanone. Such photoinitiator monomers (and polymeric photoinitiators derived therefrom) are described, for example, in U.S.Pat. No. 5,902,836 (Babu et al.) and U.S. Pat.No. 5,506,279 (Babu et al.), the disclosures of which are herein incorporated by reference.  \n\n[0061]  Ethylenically unsaturated monomers that comprise a radiation-sensitive group, preferably an $\\mathbf{\\alpha}_{\\mathbf{{d}}}$ -cleavage-type photoinitiator group and that are copolymerizable with the described free radically-polymerizable ethylenically unsaturated monomers (hereinafter “photoinitiator monomers\") constitute from 0.01 to about 5 pbw, preferably 0.01 to 3 [0064] Preferred photoinitiators are photoactive compounds that undergo a Norrish I cleavage to generate free radicals that can initiate by addition to the acrylic double bonds. Norrish type 1 photocrosslinkers, especially $\\mathbf{\\alpha}_{\\mathbf{{d}}}$ -cleavage type photoinitiators, are preferred.  \n\n[0065] The first component oligomer, and optionally the second component oligomer may comprise one or more polar monomers. As used herein “polar monomers” are those polymerizable monomers having a water miscibility (water in monomer) of at least 1 wt. $\\%$ ，preferably at least 5 weight $\\%$ without reaching a cloud point and are exclusive of the poly(alkylene oxide) monomer. The first and second component oligomers optionally comprise from O to 50 parts by weight of such polar monomers.  \n\n[0066] Polar monomers can be used to increase the absorbency and/or improve the mechanical properties (e.g. the tensile strength) of the crosslinked polymer used in forming the gel material. Preferred polar monomers can also provide compliance to the resultant polymer. Examples of suitable polar monomers include 2-hydroxyethyl(meth)acrylate (HEMA), 2-hydroxypropyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 4-hydroxybutyl(meth)acrylate, N-vinyl caprolactam, N-vinyl acetamide, N-vinyl pyrrolidone, acrylonitrile, tetrahydrofurfuryl acrylate, acrylamide, mono- or di-N-alkyl substituted acrylamide, (meth)acrylic acid, itaconic acid, beta-carboxyethyl acrylate, glycerol methacrylate, [2-(meth)(acryloyloxy)ethyl]trimethylammonium chloride, [2-(meth)(acryloyloxy)ethylltrimethylammonium methyl sulfate, and combinations thereof. Preferred polar monomers include 2-hydroxyethyl(meth)acrylate (HEMA) N-vinyl pyrrolidone, N-vinyl acetamide, and mixtures thereof, and the like.  \n\n[0067] The first and second oligomers may further comprise hydrophobic monomers.Hydrophobic monomers can be used to reduce (and thereby better control) the absorbency of the polymer used in forming the gel material, and preferably improve the strength of the polymer.  \n\n[0068] Useful classes of hydrophobic monomers include alkyl acrylate esters and amides, exemplified by straightchain, cyclic, and branched-chain isomers of alkyl esters containing $\\mathrm{C}_{1}{\\cdot}\\mathrm{C}_{30}$ alkyl groups and mono- or dialkyl acrylamides containing $\\mathrm{C}_{5}–\\mathrm{C}_{30}$ alkyl groups. Due to $\\mathrm{{T_{g}}}$ and sidechain crystallinity considerations, preferred are those having from $\\mathrm{C}_{5}–\\mathrm{C}_{12}$ alkyl groups, although use of $\\mathrm{C_{1}{-}C_{4}}$ and $\\mathrm{C}_{13}\\mathrm{-C}_{14}$ alkyl groups are also useful if the combinations provide a molecule averaged number of carbon atoms between ${\\mathrm C}_{5}$ and $\\mathrm{C}_{12}$ . However, for many applications, $\\mathrm{C}_{_{12}}$ ， $\\mathrm{C}_{30}$ alkyl groups may be preferred. Useful specific examples of alkyl acrylate esters include: methyl acrylate, ethyl acrylate, n-propyl acrylate, 2-butyl acrylate, iso-amyl acrylate, n-hexyl acrylate, n-heptyl acrylate, isobornyl acrylate, n-octyl acrylate, iso-octyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, lauryl acrylate, tridecyl acrylate, and tetradecyl acrylate. Useful specific examples of alkyl acryamides include mono- and diacryamides having pentyl, hexyl, heptyl, isobornyl, octyl, 2-ethylhexyl, iso-nonyl, decyl, undecyl, dodecyl, tridecyl, and tetradecyl groups may be used.  \n\n[0069]  The first and second component oligomers may further comprise other monomers. The selection of the “other monomers\" useful in preparing the functional oligomer(s) (of the first and second components) is such that the ultimate crosslinked material has properties suitable for its application. For example, “other monomers\" may be used to increase the tensile strength or other mechanical properties, or to control the $\\mathrm{T_{g}}$ of the polymer.  \n\n[0070] Representative examples of “other monomers” include free-radically polymerizable polar monomers having at least one ethylenically unsaturated polymerizable group that are copolymerizable with the aforementioned monomers, and include vinyl monomers such as vinyl acetate, styrenes, allyl ethers, maleic anhydride, and alkyl vinyl ethers.  \n\n[0071] Preferred first and second component oligomers used in forming the gel materials of the present invention include 20 to 99 parts by weight of the monomer units having a poly(alkylene oxide) group. More preferably, the first component oligomer comprises 50 to 99 parts by weight and most preferably 60 to 99 parts by weight of the monomer units having a poly(alkylene oxide) group.  \n\n[0072] Preferred first and optionally second component oligomers of the present invention include 0.1 to 35 parts by weight of the monomer units having a pendent polymerizable functional group. More preferably, the first component oligomers comprise 0.5 to 35 parts by weight, and most preferably 0.5 to 5 parts by weight of the monomer units having a pendent polymerizable functional group.  \n\n[0073]   Preferred first and second component oligomers of the present invention may comprise O to 50 parts by weight of a polar monomer. More preferably, the polar monomer is used in an amount of no greater than about 35 parts by weight, based on the total weight of the oligomer. Most preferably, the polar monomer is used in an amount of no greater than about 30 parts by weight. Preferably, the polar monomer is used in an amount of at least about 5 parts by weight. More preferably, the polar monomer is used in an amount of at least about 10 parts by weight.  \n\n[0074]  Preferred first and second component oligomers of the present invention include no greater than about 20 parts by weight of a hydrophobic monomer. Even more preferably, the hydrophobic monomer is used in an amount of no greater than about 1O parts by weight. Most preferably, the hydrophobic monomer is used in an amount of no greater than about 5 parts by weight of a hydrophobic monomer.  \n\n[0075]  Preferred first and second component oligomers of the present invention include no greater than about 10 parts by weight of “other monomers\", based on the total weight of the oligomer. More preferably, the hydrophobic monomer is used in an amount of less than 5 parts by weight, based on the total weight of the oligomer.  \n\n[0076]  It will be understood in the context of the above description of the first and second oligomers, that the amount of monomer units having pendent poly(alkylene oxide) groups in the first and second component oligomers, and the relative amounts of the first and second component oligomers is such that the cured composition is hydrophilic, as previously defined.  \n\n[0077]   It will be understood in the context of the above description of the first and second oligomers, that the ethylenically-unsaturated monomer possessing a free-radically polymerizable group is chosen such that it is freeradically polymerizable with itself (i.e. with another ethylenically-unsaturated functional group on the first, or optionally the second, component oligomer) and with the pendent photoinitiator group of the second component oligomer. The reactions between pendent, unsaturated functional groups provide a crosslink by forming a covalent bond by free radical addition reactions of ethylenically-unsaturated groups between oligomeric compounds. The pendent functional groups react by a reaction in which no by-product molecules are created (unlike condensation and displacement reactions), and the exemplified reaction partners react by this preferred mode.  \n\n[0078] Where the crosslinkable composition is to be processed using high temperatures and the direct method of including pendent unsaturation has been used, care must be taken not to activate those pendent unsaturated groups and cause premature gelation. For example, hot-melt processing temperatures can be kept relatively low and polymerization inhibitors can be added to the mixture. Accordingly, where heat is to be used to process the composition, the abovedescribed indirect method is the preferred way of incorporating the pendent unsaturated groups.  \n\n[0079] Oligomers of the first and second components have relatively low molecular weight, then build molecular weight (and strength) by a chain-growth process of the oligomers, through the pendent polymerizable functional groups. As result of the relatively low molecular weight, the oligomers are easily processible in operations such as coating, spraying, extrusion and molding, because of the low melt viscosity prior to crosslinking, and without the need for residuals, such as solvents, plasticizers or viscosity modifiers. With the present oligomers, the slope of the log-log plot of viscosity vs. molecular weight $(\\mathbf{M}_{\\mathrm{n}})$ is about 1,whereas for higher molecular weight polymers the slope is 3.4. The oligomers of the present invention provide processibility, and then crosslinking of the oligomers provides the needed physical properties such as toughness, hardness, tensile strength and others that are manifested in the cured state. Unless otherwise indicated molecular weight will refer to number average molecular weight.  \n\n[0080] A composition comprising oligomers of the first and second components have an average degree of polymerization (DP) generally less than about 300. The greater than expected viscosity (for polymers having a degree of polymerization greater than 30o), is attributed to entanglements of polymer chains. It has been shown empirically that polymers or oligomers with less than 300 repeat units are not entangled. Prior to the present invention, unentangled polymers have been shown to be processible but they have low strength. Preferably, both the first and second component oligomers have a degree of polymerization less than about 300.  \n\n[0081]  If desired, higher molecular weight polymers may be blended with lower molecular weight oligomers so that the mixture has a viscosity of 500 to $10{,}000\\mathrm{cPs}$ at temperatures less than $100^{\\circ}\\mathrm{~C~}$ .  \n\n[0082]Molecular weight may be controlled through the use of chain transfer agents and chain retarding agents, including mercaptans, disulfides, triethyl silane, carbon tetrabromide, carbon tetrachloride, alpha-methyl styrene and others such as are known in the art. Useful chain transfer agents also include cobalt chelates, as described in U.S.Pat. Nos. 4,680,352 and 4,694,054, and oligomeric chain transfer agents as exemplified by  \n\n![](images/f83d006fcd00c0f23a982e78d724ac1d83637f65a88fb634fe552e786fcc3818.jpg)  \n\nwherein each R is a lower alkyl group or a functional group (as previously described) and n is a number typically less than 10, as described in U.S. Pat. Nos. 5,362,826 and 5,773,534.  \n\n[0083] As previously described, the composition of the present invention comprises a first oligomer component with a plurality of pendent polymerizable functional groups and pendent hydrophilic groups, a second component with a plurality of pendent co-photoinitiator groups. The physical form of the composition may be a viscous liquid, a low melting solid or a powder, which is related to the glass transition temperature and the molecular weight. The amount of each monomer component and the relative amounts of the first and second component oligomers may be adjusted to obtain compositions having desired hydrophilicity, melt-processibility and mechanical properties.  \n\n[0084]  The oligomers used in forming the gel material of the present invention can be produced by polymerizing the above-described monomers by conventional polymerization methods. Typical polymerization methods that can be used include thermal and/or photochemical as well as bulk and solution polymerization.  \n\n[0085] In a typical solution polymerization method, a monomer mixture is heated with stirring in the presence of a solvent and a polymerization initiator. Examples of the solvent are methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, toluene, xylene, and an ethylene glycol alkyl ether. Those solvents can be used alone or as mixtures thereof. Examples of the polymerization initiator are benzoyl peroxide, cumene hydrop eroxide, diisopropyl peroxydicarbonate, and 2,2'-azobisisobutyronitrile. Those polymerization initiators can be used alone or as mixtures thereof.  \n\n[0086]   In a typical photopolymerization method, a monomer mixture is irradiated with ultraviolet (UV) rays in the presence of a photopolymerization initiator (i.e., photoinitiators). Preferred photoinitiators are those available under the trade designations IRGACURE and DAROCUR from Ciba Speciality Chemical Corp., Tarrytown, N.Y. and include 1-hydroxy cyclohexyl phenyl ketone (IRGACURE 184), 2,2-dimethoxy-1,2-diphenylethan-1-one (IRGACURE 651)，bis(2,4,6-trimethylbenzoyl)phenylphosphineoxide (IRGACURE 819), 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one (IRGACURE2959), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone (IRGACURE 369), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (IRGACURE 907), and 2-hydroxy-2-methyl-1-phenyl propan-l-one (DAROCUR 1173). Particularly preferred photoinitiators are IRGACURE 819,184 and 2959.  \n\n[0087]  These photo-  and  thermal  initiators can be employed in concentrations ranging from about 0.o001 to about 3.0 pbw, preferably from about O.oo1 to about 1.0 pbw, and more preferably from-about 0.0o5 to about 0.5 pbw, per 10o pbw of the monomer composition.  \n\n[0088]  Liquid oligomers may be obtained if the glass transition temperature of the oligomer component is below ambient temperature and the molecular weight of the oligomer component is below entanglement molecular weight (i.e. a degree of polymerization of less than about 30o). Low melting solids may be obtained when the $\\mathrm{{T_{g}}}$ is at or below ambient temperature. Powders may be obtained when the $\\mathrm{{T_{g}}}$ is above ambient temperature. Due to the amount of poly(alkylene oxide) in the oligomers the oligomers are generally low melting solids or liquids.  \n\n[0089] The first oligomer may be prepared (e.g., by solution polymerization followed by isolation) and then combined with a separately prepared second component oligomer. Any residual monomer and/or solvents used in the preparation are generally removed by conventional techniques such as distillation, vacuum evaporation, etc., to reduce the residual content to less than 2 wt. $\\%$ ，prior to crosslinking. Depending on the type of coating process to be used, the relative amounts of the oligomer(s) can vary greatly. The polymerizations may be conducted in the presence of suitable solvents such as ethyl acetate, toluene and tetrahydrofuran that are unreactive with the functional groups of the components of the first and second components.  \n\n[0090] The second component oligomer may be prepared in situ provided that, prior to crosslinking, the residual content is less than 2 wt. $\\%$ ，or the second component oligomer may be separately prepared and added to the oligomer mixture. The crosslinked composition of the invention results from a chain-growth process by reaction of the pendent unsaturated polymerizable groups and the pendent photoinitiator groups. Each of the first and second component oligomers may comprise a mixture of oligomers falling within their respective descriptions.  \n\n[0091] Polymerization to prepare the crosslinked oligomeric composition can be accomplished by exposing the component oligomer mixture to actinic energy in the presence of the photoinitiator group of the second component oligomer. The amount of the first and second component oligomer may be chosen so that the concentration of photoinitiator groups is from about O.ooo1 to about 3.0 pbw, preferably from about 0.0o1 to about 1.0 pbw, and more preferably from-about 0.005 to about 0.5 pbw, per 100 pbw of the composition.  \n\n[0092]   A coatable oligomer composition may be prepared by combining the first and second oligomer component oligomers. Partial conversion of the two components may be necessary to achieve a thickened solution exhibiting a coatable viscosity of from about $500{-}10{,}000\\ {\\mathrm{cPs}}$ at $22^{\\circ}\\mathrm{C}.$ ,more preferably from about 750 to $7500~\\mathrm{cPs}$ ·  \n\n[0093] Once configured into the desired construction, the composition including the first and second oligomer components may be irradiated with activating UV radiation to crosslink the composition. UV light sources can be of two types: 1) relatively low light intensity sources such as blacklights which provide generally $10\\mathrm{\\mW/cm}^{2}$ or less (as measured in accordance with procedures approved by the United States National Institute of Standards and Technology as, for example,with a UVIMAPTM UM 365 L-S radiometer manufactured by Electronic Instrumentation & Technology, Inc., in Sterling, Va.) over a wavelength range of 280 to 400 nanometers and 2) relatively high light intensity sources such as medium pressure mercury lamps which provide intensities generally greater  than 10 $\\mathrm{mW}/\\mathrm{cm}^{\\frac{\\dag}{2}}$ ， preferably between 15 and $\\mathsf{\\bar{450m W}}/\\mathsf{c m}^{2}$ . Where actinic radiation is used to fully or partially crosslink the polymer composition, high intensities and short exposure times are preferred. For example, an intensity of 600 $\\mathrm{\\mW/cm}^{2}$ and an exposure time of about 1 second may be used successfully. Intensities can range from about 0.1 to about $150\\mathrm{mW}/\\mathrm{cm}^{2}$ ， preferably from about 0.5 to about 100 $\\mathrm{mW}/\\mathrm{cm}^{2}$ , and more preferably from about 0.5 to about 50 $\\mathrm{mW}/\\mathrm{cm}^{2}$ ，  \n\n[0094]Accordingly, relatively thick coatings (e.g., at least about $0.025\\mathrm{~mm})$ can be achieved when the extinction coeficient of the photoinitiator is low. Coatings from of 0.5 or more mm thick are possible and are within the scope of the present invention.  \n\n[0095]  Additional advantages of the photopolymerization method are that 1) heating the composition is unnecessary and 2) photoinitiation is stopped completely when the activating light source is turned off.  \n\n[0096]  If so desired, measuring the refractive index of the composition material especially in bulk can be used to monitor the extent of polymerization. The refractive index changes linearly with respect to conversion. This monitoring method is commonly applied in polymerization kinetics work. See discussions about the method in, for example, G. P. Gladyshev and K.M. Gibov, Polymerization at Advanced Degrees of Conversion, Keter Press, Jerusalem (1970).  \n\n[0097] When preparing a crosslinked composition of the invention, it may be expedient for the initiated polymerization reactions to proceed to virtual completion, i.e., depletion of the pendent polymerizable functional groups, at temperatures less than about $70^{\\circ}\\mathrm{C}$ (preferably at $50^{\\circ}\\mathrm{C}$ .or less)with reaction times less than 24 hours, preferably less than 12 hours, and more preferably less than 6 hours. These temperature ranges and reaction rates obviate the need for free radical polymerization inhibitors, which are often added to acrylic systems to stabilize against undesired, premature polymerization and gelation. Furthermore, the addition of inhibitors adds residuals that will remain with the system and inhibit the desired polymerization of the polymer and formation of the crosslinked compositions of the invention. Free radical polymerization inhibitors are often required at processing temperatures of $70^{\\circ}\\mathrm{~C~}$ . and higher for reaction periods of more than about 6 hours.  \n\n[0098] The crosslinked composition can be characterized as a polymer having a first oligomer chain having at least one pendent hydrophilic moiety and the residue of at least one pendent, ethylenically unsaturated moiety chemically bonded to the residue of a second, pendant ethylenically unsaturated moiety of a second oligomer chain. As a polymeric photoinitiator is used, the polymer may be further characterized as having the residue of at least one pendent, ethylenically unsaturated moiety chemically bonded to the residue of a photoinitiator moiety. Preferably each polymer chain comprises a (meth)acrylate polymer chain. Thus, during exposure to UV energy, the free radical resulting from the photoinitiator (of the seond component oligomer) adds to the pendent ethylenically unsaturated moiety to form a crosslink between the oligomer chains upon coupling or propagation with another polymerizable group on another oligomer chain. In general, the present crosslinked composition has effective molecular weight between crosslinks, $(\\mathbf{M}_{\\mathrm{c}})$ , of greater than or equal to 1,o00 and preferably greater than 3,ooo. Effective molecular weight between crosslinks (Mc), may be measured by dynamic mechanical analysis.  \n\n[0099] The degree of crosslinking may be easily controlled by the number and concentration of pendent unsaturated groups and by the number and concentration of photoinitiator groups that are pendent on the oligomer(s). The ratio of photoinitiator groups to pendent, free-radically polymerizable, unsaturated groups can vary from about 1:10,000 to 1:1, depending on the degree of crosslinking desired. Generally the smaller the $\\mathbf{M}_{\\mathrm{c}}$ ，the lower the elasticity and hence harder the crosslinked composition.  \n\n[0100]  When the composition of the invention is used to prepare hydrophilic gel materials for medical applications, the gel can include one or more active agents, such as pharmacologically active agents.Examples include, but are not limited to, growth factors (e.g., TGF, FGF, PDGF, EGF, etc.), antibacterial agents (e.g., penicillins, neomycin sulfate, sulphonamides, sulfadiazine, silver sulfadiazine, trimethoprim, and other antibiotics, as well as povidone iodine, iodine, silver, silver chloride, and chlorhexidine), antifungal agents (e.g.,griseofulvin, chlormidazole hydrochloride, clotrimazole, ketoconazole, miconazole, miconazole nitrate, nistatin, and tolnaftate), disinfectants and antiseptics (e.g., benzalkonium chloride, cetalkonium chloride, chlorhexidine gluconate, ethanol, iodine, methylbenzethonium, povidone iodine, isopropanol, silver, silver oxide, silver salts such as silver lactate and silver chloride, triclosan), local anaesthetics (e.g.,tetracaine, benzocaine, prilocalne, procaine), debriding agents, anti-inflammatory agents (e.g., indomethacin, ketoprofen, dichlofenac, ibuprofen, etc.), astringents, enzymes, nutrients (e.g., vitamins, minerals, oxygen, etc.), drugs for cataplasms (e.g., menthol, camphor, peppermint, capsicum extract, capsaicin, etc.), and odor absorbing agents (e.g.,zeolites, silicates, chitosans, cyclodextrins, etc.). Preferred active agents are antibacterial agents such as povidone iodine, iodine, silver, silver chloride, and chlorhexidine.Active agents can be used alone or as mixtures thereof. They can be added before or after the reaction product of this invention is cured as long as they do not interfere with polymerization of the polymer. Preferably, they are added in an amount or manner that does not interfere with the function or clarity of the finished gel material.  \n\n[0101]Optionally, the gel material of the present invention can include hydrocolloids, typically in the form of particles, although they are not necessarily preferred since they can diminish the transparency of the gel material. Examples of hydrocolloids include, but are not limited to, natural gums, such as plant exudates (gum arabic, ghatti, karaya, and tragacanth); plant seed gums (guar, locust bean and acacia), seaweed extracts (agar, algin, alginate salts and carrageenin), cereal gums (starches and modified starches), fermentation or microbial gums (dextran and xanthan gum), modified celluloses (hydroxymethylcellulose, microcrystalline cellulose and carboxymethylcellulose) pectin, gelatin, casein and synthetic gums (polyvinylpyrrolidone, low methoxyl pectin, propyleneglycol alginates, carboxymethyl locust bean gum and carboxymethyl guar gum) and like water-swellable or hydratable hydrocolloids. The term hydrocolloid is used regardless of the state of hydration. The gel material of the present invention preferably includes an amount of the hydrocolloid such that the material is transparent (preferably, the total light transmittance is greater than $84\\%$ per ASTM D1003-00). Typically, the amount of hydrocolloid, if used, is less than about 5 wt- $\\%$ ,based on the total weight of the gel material.  \n\n[0102] Other additives that can be incorporated into the gel material of the present invention include: viscosity modifiers (e.g., polymeric thickeners such as that commercially available under the trade designation GANTREZ resin from International Specialty Products, Wayne, N.J.); chain transfer or retarding agents (e.g., such as alkyl mercaptans such as dodecyl mercaptan, isooctyl thioglycolate, and alpha-methylstyrene, the latter of which can also be a hydrophobic monomer as discussed above); colorants; indicators; tackifiers; plasticizers (e.g., water, glycerin, polyethylene oxide, polypropylene oxide, and mixtures thereof such as those commercially available under the trade designation PLURONICS from BASF Co., as well as various low molecular compounds capable of plasticizing the polymer); antioxidants; etc. Such additives can be added either before or after the polymerization using techniques known to one of skill in the art. Preferably, if used, they can be added in an amount and manner that does not interfere with the function or clarity of the gel material.  \n\n[0103]  Preferably, the gel material of the present invention is substantially free of residuals, including water. This is advantageous at least because special packaging is not required. Furthermore, residuals can migrate to other parts of a dressing, for example, which can be detrimental to the integrity of the dressing, or into the body of the patient on which the dressing is disposed.  \n\n[0104] Optionally, the gel material may have a patterned surface on at least one major surface thereof. The patterned surface allows greater surface area for absorption of wound exudate when oriented toward the wound surface, while reducing the absorbent surface area in direct or indirect contact with the wound. More significantly, the patterned surface reduces the propensity of the absorbent layer to swell and push against the wound, avoids mushrooming (i.e. expansion of the gel layer through a porous film) and further avoids premature separation of an adhesive layer from the skin.  \n\n[0105]  The optional pattern imparted to the surface of a layer of the gel material may be any suitable preselected three-dimensional pattern. Preferably, the pattern is one that increases the surface area available for absorption and reduces swelling into the wound, retards mushrooming, and/or enhances integrity of the material upon hydration. The pattern can include an array of pattern elements that include, but are not limited to, ridges, channels, mounds, peaks, hemispheres, pyramids, cylinders, cones, blocks, and truncated variations and combinations thereof. The pattern may further include apertures having a predetermined shape and size extending through the thickness of the absorbent layer.  \n\n[0106] The specific pattern element is advantageously chosen to present minimal surface area in contact with a wound or the facing film if present. The minimal surface area further retards the tendency of the gel material to swell into the wound,mushroom, or adhere to the wound site.  \n\nEspecially useful elements include pyramids, cones and truncated versions thereof, and ridges that are triangular in cross section. The elements may be random or non-random in the x direction, the y direction, or both. For ease of manufacture, it is preferable that the pattern comprises a non-random array of elements disposed on the surface of the gel.  \n\n[0107]  If desired, a pattern may also be imparted to the outer face of the gel layer (i.e., the major surface of the gel layer that faces away from the wound surface). Imparting such a pattern increases the surface area of the gel layer and may promote greater evaporation of the fluid from the gel material. The pattern may be the same or different than the pattern on the facing surface of the gel material, as can the size of the pattern elements. Further, the individual elements on either surface of the gel material may be protuberances extending form the surface, or may be depressions in the surface.  \n\n[0108]  An optional patterned surface may be imparted to the gel material by conventional molding techniques. Alternatively, a desired pattern may be imparted using an embossing technique. Examples of such techniques are described in International Publication No. WO 01/60296 A1.  \n\n[0109]   If desired, the gel material may be in direct contact with the wound and/or skin surface. However, direct contact may be provided by other suitable hydrocolloid and hydrogel absorbent materials as well.  \n\n[0110]  In a preferred medical article, the gel material forms a layer that is generally about 25O micrometers (i.e., microns) to about 5ooo micrometers in total thickness.  \n\n[0111]   Optionally, a wound dressing of the invention may include at least two absorbent layers: a first absorbent layer and a second absorbent layer. The first absorbent layer is typically more absorbent than the second absorbent layer, and can retain a greater volume of body fluids than the second absorbent layer. The second absorbent layer is positioned such that it is located between the first absorbent layer and the wound. This second absorbent layer provides integrity to the wound dressing and avoids transfer of the first absorbent layer into the wound.  \n\n[0112] The first absorbent layer typically contains the polymer described above prepared from the oligomeric composition. The second absorbent layer is typically positioned in contact with the first absorbent layer and is typically less absorbent of body fluids than the first absorbent layer. The second absorbent layer can contain the reaction product of an acrylic acid ester of a non-tertiary alcohol having from 4 to 14 carbon atoms; a hydrophilic, ethylenically unsaturated monomer; and a polar, ethylenically unsaturated monomer, although other compositions can be used in the second absorbent layer.  \n\n[0113]  Generally, the second absorbent layer functions as a “barrier” between the first absorbent layer (which may partially “disintegrate” when exudate is unevenly, rapidly absorbed or when it absorbs more than about $500\\%$ )andthe wound.Preferably the second absorbent layer has adhesive properties (or is a pressure sensitive adhesive) and functions to enhance the overall integrity of the wound dressing. In this regard, the second absorbent layer ties the first absorbent layer to a wound-facing layer (or to the wound itself). By having adhesive properties, this second absorbent layer not only aids in controlling the absorption of exudate, but also physically joins other components of the dressing.  \n\n[0114]  As stated above, the first absorbent layer is typically significantly more absorbent than the second absorbent layer, and preferably has an absorbency at least 100 percent greater than the absorbency of the second absorbent layer. The first absorbent layer preferably absorbs at least 200 percent of its weight after immersion in an isotonic saline solution after 24 hours at room temperature.  \n\n[0115]A typical wound dressing of the present invention preferably includes a porous or non-porous facing layer to provide a fluid permeable barrier between the wound site and the gel layer. The facing layer allows transport of moisture (i.e. fluid and vapor) from the wound to the gel layer and may isolate the wound from other components of the dressing. The facing layer is preferably soft, flexible, conformable, non-irritating and non-sensitizing. Any of a variety of polymers may be used including polyurethane, polyethylene, polypropylene, polyamide or polyester materials. Further, the facing layer may be in the form of moisture vapor permeable films, perforated films, woven-, non-woven or knit webs or scrims. A preferred facing layer comprises a polyurethane film.  \n\n[0116] In one useful embodiment, the facing layer is conformable to animal (including human) anatomical surfaces, has a moisture vapor transmission rate (MVTR) of at least 300 grams per square meter per 24 hours at $80\\%$ relative humidity differential at $40^{\\circ}\\mathrm{C}$ (per method of Chen, U.S.Pat. No. 5,733,570), is impermeable to liquid water throughout substantially its entire imperforate area and contains perforations means for passing wound exudate through the facing layer. This means that the facing layer does not pass liquid water under normal wound treatment conditions except at the places in the facing layer that are positively perforated to allow the exudate to pass into the reservoir.  \n\n[0117]   The preferred moisture vapor transmission rate of the facing layer is at least 600 grams per square meter per 24 hours at an $80\\%$ relative humidity differential at $40^{\\circ}\\mathrm{C}$ .The facing layer may further comprise a pressure sensitive adhesive layer. The adhesive coated facing layer preferably has the aforesaid MVTR. Therefore, if the facing layer is impermeable to liquid water except for the perforation means, the adhesive can be permeable to liquid water and vice versa. Porous or non-porous facing layers such as perforated polyamide, polyester, polypropylene, polyethylene, polyether-amide, polyurethanes, chlorinated polyethylene, styrene/butadiene block copolymers (KRATON brand thermoplastic rubber, Shell Chemical Company, Houston, Tex.) and poly(vinyl chloride) and those described in U.S. Pat. No. 3,121,021 (Copeland) that are covered with a pressure sensitive adhesive that is not permeable to liquid water can be used for the facing layer. Optionally these films can be perforated. Additional porous materials include woven and non-woven substrates.  \n\n[0118]   It is preferred that the facing layer have the above mentioned moisture vapor or liquid permeability (1) so that maceration of the skin under the wound dressing does not occur, (2) so that moisture build-up under the facing layer does not cause the facing layer and, therefore, wound dressing to be lifted off the skin, and (3) to enhance proximation of the wound edges. Preferred facing layers are thin polymeric films optionally coated with pressure sensitive adhesive which, in combination, have the above characteristics.  \n\n[0119]   The perforation means in the facing layer are holes or slits or other perforations that conduct the passage of liquid water or wound exudate from the wound into the absorbent layer of the wound dressing. The perforations may additionally extend through an adhesive layer, if the front surface of the facing film (that surface facing toward the wound) is coated with a pressure sensitive adhesive layer.  \n\n[0120]  A backing layer may be present in all of the embodiments of the present invention. Preferably the backing layer is conformable to animal anatomical surfaces, impermeable to liquid water and has a moisture vapor transmission rate of at least 600 grams per square meter per 24 hours at an $80\\%$ relative humidity differential at $40^{\\circ}\\mathrm{~C~}$ \\* The backing layer, in combination with a facing layer, may be constructed to form a reservoir (e.g., a pouch or envelope) that surrounds the gel layer, into which the exudate from the wound passes. This reservoir does not permit liquid water or exudate to pass out of it. Instead, the gel layer absorbs the exudate, and moisture in the exudate passes through the backing layer in a vapor form into the atmosphere. The reservoir dressing permits wound exudate to be rapidly removed from the wound site and prevents liquids or bacteria from outside the dressing to contaminate the wound site.  \n\n[0121] In order to remove moisture vapor, the moisture vapor transmission rate of the backing layer is at least as above noted, and preferably at least 1200 grams per square meter per 24 hours at an $80\\%$ relative humidity differential at $40^{\\circ}\\mathrm{~C~}$  \n\n[0122] The preferred embodiments for the facing and backing layers are thin conformable polymeric films. Generally the films are about 12 microns to about 50 microns in thickness, preferably about 12 microns to about 25 microns. Conformability is somewhat dependent on thickness, thus the thinner the film the more conformable the film. Reference has been made herein to the films utilized in the medical article (e.g., wound dressing) of the present invention being conformable to animal anatomical surfaces. This means that when the films of the present invention are applied to an animal anatomical surface, they conform to the surface even when the surface is moved. The preferred films are conformable to animal anatomical joints. When the joint is flexed and then returned to its unflexed position, the film stretches to accommodate the flexation of the joint but is resilient enough to continue to conform to the joint when the joint is returned to its unflexed condition.  \n\n[0123]   Examples of films which are useful in applicant's invention as facing or backing layers include polyurethanes such as those available under the trade designation ESTANE from B.F. Goodrich, Cleveland, Ohio, elastomeric polyester such as those available under the trade designation HYTREL from E.I. duPont deNemours & Co., Wilmington, Del., blends of polyurethanes and polyesters, polyvinyl chlorides, and polyether-amide block copolymers such as those available under the trade designation PEBAX available from Elf-Atochem. Particularly preferred films for use in the present invention are polyurethane and elastomeric polyester films. The polyurethane and elastomeric polyester films exhibit a resilient property that allows the films to have good conformability.  \n\n[0124] Particularly useful films include “spyrosorbent” films having a differential moisture vapor transmission rate (MVTR). Dressings incorporating spyrosorbent films not only manage wound exudate by absorption, but have the ability to adjust the moisture vapor transmission properties in response to the amount of exudate. Such spyrosorbent films are hydrophilic, moisture vapor permeable and have a relatively high MVTR (wet), and have a differential MVTR ratio (wet to dry) that is greater than 1, and preferably greater than 3:1. The dry MVTR is greater than about $2600\\mathrm{\\dot{g}/m}^{2}/24$ hrs, preferably about 3000 to $4000\\ \\mathrm{g/m}^{2}/24$ hrs.A particularly preferred spyrosorbent film, useful as a backing layer, is a segmented polyurethane such as a segmented polyether polyurethane urea based on polytetramethylene glycol and polyethylene glycol polyols. Such a spyrosorbent films are described in U.S.Pat.Nos. 5,653,699 and 4,849,458 (Reed et al.).  \n\n[0125] Another suitable backing layer is a fluid control film having at least one microstructures-bearing surface with channels that permit directional control of a liquid. This film can be used to transport a fluid to a remote site and thereby facilitate wicking away of a fluid (e.g.,wound exudate). Such a film is disclosed in International Publication No. WO 00/42958.  \n\n[0126]  Many different constructions of a wound dressing are possible with the facing layer, the gel layer, and the backing layer. In one embodiment, the areas of the facing layer and the backing layer are greater than that of the gel layer and the facing layer is bonded to the backing layer, thereby forming a pouch, with the gel disposed between the two. In another embodiment, one of the facing or backing layers may be substantially the same area as the gel layer, and the other of greater area. The greater area of the facing or backing layer forms a periphery to which an adhesive layer and a release liner may be attached. It will further be understood that the facing and/or backing layer may be attached or bonded to the adjacent surface of the gel layer to form a contiguous layer construction, in which the backing and facing layers may be the same or of greater area than the gel layer.Alternatively, the backing and facing layers may be bonded to each other, and may or may not be bonded to the gel layer. In these last constructions, the gel layer is constrained within a pouch created by the attachment of the facing and backing layers to each other. The layers may be bonded to each other by any conventional means such as adhesives, heat-sealing, or other bonding means.  \n\n[0127]   It is preferred that the facing and backing layers of the medical articles of the present invention be at least translucent and more preferably sufficiently transparent so that the wound site to which they are applied can be viewed through the medical article. It is advantageous to view and evaluate the wound and healing thereof without removal of the wound dressing to avoid unnecessary handling of the wound site and exposure of the wound to the environment, which reduces the likelihood of contamination, and avoids the need to cleanse the wound as would be the case were the dressing to be removed. It is preferred that the dressing be both transparent and colorless so that the color of the wound, exudate, and periwound skin may also be evaluated. Preferred transparent films for use as facing and backing layers that allow visual inspection of the wound site include polyurethane films such as those available under the trade designation ESTANE from B.F. Goodrich, Cleveland, Ohio;  \n\nelastomeric polyesters such as those available under the trade designation HYTREL from E.I. duPont deNemours & Co., Wilmington, Del.; and, polyether block amides such as those available under the trade designation PEBAX from Elf Altochem North America, Philadelphia, Pa. Other useful films are those describes in U.S. Pat.No. 4,499,896 (Heinecke); U.S. Pat. No. 4,598,004 (Heinecke); and U.S. Pat. No. 5,849,325 (Heinecke et al).  \n\n[0128] While the facing layer can be attached to the wound by means other than a pressure sensitive adhesive on its surface, it is preferred to use such an adhesive. The presence of the adhesive of the facing layer normally reduces the moisture vapor permeability of the facing layer. Therefore it is preferred that the facing layer is adhesive coated prior to adding a plurality of perforations to the layer. The wound exudate therefore can readily pass through a perforated adhesive coated facing layer. Preferably, both the facing and backing layers are precoated with an adhesive layer to both facilitate bonding of the backing layer to the facing layer (forming a pouch), and bonding of the facing film to the wound site.  \n\n[0129] The facing layer is normally attached to the wound site by means of adhesive that can be continuous or patern coated. The preferred adhesive which can be used with the wound dressings of present invention are the normal adhesives which are applied to the skin such as those described in U.S. Pat. No. Re. 24,906 (Ulrich), particularly a copolymer of $96\\%$ iso-octyl acrylate units and $4\\%$ acrylamide units and a copolymer of $94\\%$ iso-octyl acrylate units and $6\\%$ acrylic acid units. Other useful adhesives are those described in U.S. Pat. No. 3,389,827 that comprise block copolymers having three or more polymer block structures having a general configuration —A—B—A— wherein each A is a thermoplastic polymer block with a glass transition temperature above room temperature (i.e., above about $20^{\\circ}\\mathrm{C}.$ ) having an average molecular weight between about 5000 and 125,oo0 and B is a polymer block of a conjugated diene having an average molecular weight between about 15,000 and 250,oo0. Additional examples of useful adhesives are acrylic adhesives such as iso-octyl acrylate/N-vinyl pyrrolidone copolymer adhesives and crosslinked acrylate adhesives such as for example those described in U.S. Pat. No. 4,112,213 (Waldman). Inclusion in the adhesive of medicaments is useful for enhancing wound healing and the inclusion of antimicrobial agents such as iodine is useful for preventing infection.  \n\n[0130]   The adhesive may optionally be a microsphere adhesive with low trauma properties as described in U.S. Pat. No. 5,614,310 (Delgado et al.); a fibrous adhesive with low trauma properties as described in U.S. Pat. No. 6,171, 985 B1 (Joseph et al.); or have especially good adhesion to wet skin, such as the adhesives described in U.S. Pat. No. 6,198,016 B1 (Lucast et al.), and International Publication Nos.WO 99/13866 and WO 99/13865; multilayered adhesives as disclosed in U.S.Pat.Publication No.2001/0051178 A1 (Blatchford et al.). A particularly preferred adhesive includes $15\\mathrm{\\wt-\\%}$ acrylic acid, $15\\mathrm{\\wt-\\%}$ methoxypolyethylene oxide 400 acrylate, 70 wt- $\\%$ isooctyl acrylate, prepared according to Example 1 of U.S. Pat. No. 5,849,325 (Heinecke et al.).  \n\n[0131] The adhesive may be chosen to be permeable to water or wound exudate, or the adhesive may be pattern coated on the front surface of the wound dressing (i.e. the surface in contact with the wound site, whether it is the front surface of the facing or backing layers) so as to not impede the flow of exudate to the gel layer, i.e. the adhesive may be coated at the periphery of the wound dressing.Alternatively the adhesive layer may be perforated as described for the facing film to provide a fluid path for the exudate.  \n\n[0132]A release liner may be attached to the adhesive layer for ease of handling. Examples of release liners are liners made of or coated with polyethylene, polypropylene and fluorocarbons and silicone coated release papers or polyester films. Examples of the silicone coated release papers are POLYSLIK S-8004, 83 pound $(135.4~\\mathrm{\\g/m}^{2})$ bleached silicone release paper supplied by H.P. Smith Co.. Chicago, Ill., and 80 pound $(130.5\\mathrm{g}/\\mathrm{m}^{2})$ bleached two-sided silicone coated paper (2-80-BKG-157) supplied by Daubert Chemical Co., Dixon, Ill.  \n\n[0133]  A wound dressing of the present invention may also include a frame that allows the dressing to be more easily applied to the wound. The frames are made of a relatively rigid material that maintains the shape of the dressing during handling and application to the wound site. The frame is generally releasably adhered to the back surface of the backing film and is removed after application of the wound dressing. Suitable frames are described in U.S. Pat. No. 5,531,855 (Heinecke et al.) and U.S. Pat. No. 5,738,642 (Heinecke et al.).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# EXAMPLES  \n\n[0134] Unless otherwise noted, all reagents and solvents were or can be obtained from Aldrich Chemical Co., Milwaukee, Wis.  \n\n[0135]  As used herein,   \n[0136] “BHT” refers to butylated hydroxy toluene, also know as 2,6-di-tert-butyl-4-methyl phenol;   \n[0137] “HEMA” refers to 2-hydroxyethyl methacrylate, available from Mitsubishi Rayon Co., Ltd., Tokyo, Japan; [0138] “MPEG” refers to polyethylene glycol methyl ether methacrylate, $\\mathrm{Mw}{=}454~\\mathrm{g/mol}$ ，available from Osaka Organic Chemical Industry, Ltd., Osaka, Japan;   \n[0139]“VDM” refers to vinyl dimethyl azlactone, available from Groupe SNPE, Paris, France;   \n[0140] “DMACM\" refers to N,N'-dimethyl acrylamide; [0141] “NVA” refers to N-vinyl acetamide;   \n[0142] “MPEG-100o” refers to polyethylene glycol methyl ether methacrylate, $\\scriptstyle\\mathrm{Mw=1}100\\ \\mathrm{g/mol}$ .，   \n[0143]“DBU” refers to 1,8-diazabicyclo[5.4.0]undec-7- ene;   \n[0144] “IEM\" refers to 2-isocyanatoethyl methacrylate; [0145] “AIBN\" refers to 2,2'-azobis(isobutyronitrile); [0146] DAROCUR ZLI-3331 refers to 2-propenoic acid, 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl ester, and was obtained from Ciba-Geigy, Hawthorne, N.Y.; [0147] VAZO 52 refers to 2,2-azobis(2,4-dimethylpentanenitrile), available from E.I. du Pont de Nemours and Co., Wilmington, Del.;  \n\n[0148] IRGACURE 184 (IG184) refers to 1-hydroxycylcohexyl phenyl ketone, available from Ciba Specialty Chemical Corp, Tarrytown, N.Y.  \n\nMethods  \n\n[0149] The number average molecular weight $(\\mathbf{M}_{\\mathrm{n}})$ of each composition was determined using gel permeation chromatography (GPC).  \n\n[0150] The absorbency of each exemplary composition was determined by immersing a weighed 3 cm diameter disk of the composition, each having a thickness of approximately $1.1\\ \\mathrm{mm}$ ，in approximately $200~\\mathrm{mL}$ of 0.9 weight percent aqueous $\\mathsf{N a C l}$ . The weight of each sample disk was",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# Preparatory Example 3-7  \n\n[0153]  A series of hydrophilic copolymers were synthesized by charging 5 amber glass bottles with different weight proportions of hydrophilic monomers and $\\mathbf{\\alpha}_{\\mathrm{~\\tiny~d~}}$ -methyl styrene as shown in Table 1. Sufficient ethyl acetate was added to each bottle so that the total monomer concentration was 50 weight percent.VAZO 52 $(0.4\\ \\mathrm{g})$ was added to each bottle. The contents of each bottle was purged with nitrogen gas for 20 minutes and the bottle was capped, using poly(tetrafluoroethylene) thread tape. Each bottle was placed in a Model LLF LAUNDER-O-METER, with the water bath temperature set at $60^{\\circ}\\mathrm{C}.$ ,for 16 hours. Compositions and $\\mathbf{M}_{\\mathrm{n}}$ values for Preparatory Examples 3-7 are shown in Table 1.  \n\nTABLE1   \n\n\n<html><body><table><tr><td colspan=\"8\">Preparatory Examples 3-7</td></tr><tr><td>Preparatory Example</td><td>MPEG(g)</td><td>HEMA(g)</td><td>DMACM(g)</td><td></td><td>NVA(g) MPEG-1000(g)</td><td>Alpha- methylstyrene(g)</td><td>Mn</td></tr><tr><td>3</td><td>93.7</td><td>4.9</td><td rowspan=\"5\"></td><td rowspan=\"5\"></td><td rowspan=\"5\"></td><td>1.0</td><td>43.000</td></tr><tr><td>4</td><td>98.5</td><td>1.0</td><td>0.1</td><td>34.900</td></tr><tr><td>5</td><td>64.1</td><td>4.9</td><td></td><td></td></tr><tr><td>6</td><td></td><td></td><td></td><td>37,100 23,800</td></tr><tr><td>7</td><td></td><td></td><td>98.5</td><td>1.0 0.1</td></tr></table></body></html>  \n\nrecorded as “dry weight.\"After 24 hours, each sample disk was removed from the solution and the excess liquid was allowed to drip off of the disk for 1 minute. The sample disk was again weighed and this weight was recorded as “wet weight.\" The absorbency of each sample disk was calculated as the increase in sample weight, expressed as a percentage of the dry weight, according to the formula  \n\n$100^{*}$ (wet weight-dry weight)/dry weight",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# Preparatory Example 1  \n\n[0151]   A hydrophilic copolymer with photoinitiator pendant groups was synthesized by charging an amber glass bottle with $99.0\\ \\mathrm{g}$ of MPEG, $1.0\\mathrm{g}$ of DAROCUR ZLI-3331, $0.1\\ \\mathrm{g}$ of $\\mathbf{\\alpha}_{\\mathbf{{d}}}$ -methyl styrene, $0.4~\\mathrm{g}$ of VAZO 52 and $100~\\mathrm{g}$ of ethyl acetate. The contents of the bottle were purged with $\\Nu_{2}$ for 20 minutes and the bottle was capped, using poly(tetrafluoroethylene) thread tape (available from 3M Co., St. Paul, Minn.) between the cap and the threads of the bottle. The bottle was placed in a Model LLF LAUNDER-OMETER (available from Atlas Electric Devices Co., Chicago, Ill.), with the water bath temperature set at $60^{\\circ}\\mathrm{C}.$ ,for 16 hours. The resulting polymer had a $\\mathbf{M}_{\\mathrm{n}}$ of 36,900 as determined by GPC.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 14,
+        "chunk": "# Preparatory Example 2  \n\n[0152]  A hydrophilic copolymer with photoinitiator pendant groups was synthesized by charging an amber glass bottle with $65.0~\\mathrm{\\g}$ of MPEG, $35.0\\mathrm{~g~}$ of HEMA, $\\boldsymbol{1.0\\ \\mathrm{g}}$ of DAROCURE ZLI-3331, $4.0\\ \\mathrm{g}$ of $\\mathbf{\\alpha}_{\\mathrm{~d~}}$ -methylstyrene, $0.4\\ \\mathrm{g}$ of AIBN and $90\\ \\mathrm{g}$ of ethyl acetate. The contents of the bottle were purged with nitrogen gas for 20 minutes and the bottle was capped, using poly(tetrafluoroethylene) thread tape. The bottle was placed in a water bath shaker at $65^{\\circ}\\mathrm{~C~}$ .for 24 hours. The resulting polymer had a $\\mathbf{M}_{\\mathrm{n}}$ of 15,700 as determined by GPC.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# Preparatory Examples 8-12  \n\n[0154]  Each solution of the products of Preparatory Examples 3-7 was combined with VDM and a catalytic amount of DBU in an amber bottle. The bottle was agitated in a heated shaker water bath at $60^{\\circ}\\mathrm{C}$ .for 16 hours. The data are given in Table 2.  \n\nTABLE 2   \n\n\n<html><body><table><tr><td></td><td colspan=\"3\">Preparatory Examples 8-12</td></tr><tr><td>Preparatory Example</td><td>Product from Preparatory Example (Component A)</td><td>Wt. Component A (g)</td><td>Wt.VDM (g)</td></tr><tr><td>8</td><td>3</td><td>40.00</td><td>1.07</td></tr><tr><td>9</td><td>4</td><td>40.00</td><td>0.21</td></tr><tr><td>10</td><td>5</td><td>40.00</td><td>1.07</td></tr><tr><td>11</td><td>6</td><td>40.00</td><td>1.07</td></tr><tr><td>12</td><td>7</td><td>6.00</td><td>0.03</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 16,
+        "chunk": "# Preparatory Examples 13-15  \n\n[0155]  Each solution of the products of Preparatory Examples 3-5 was combined with IEM and a catalytic amount of dibutyltin dilaurate in an amber bottle. The bottle was agitated in a heated shaker water bath at $60^{\\circ}\\mathrm{~C~}$ .for16 hours. The data are given in Table 3.  \n\nTABLE3   \n\n\n<html><body><table><tr><td></td><td colspan=\"3\">Preparatory Examples 13-15</td></tr><tr><td>Preparatory Example</td><td>Product from Preparatory Example (Component A)</td><td>Wt. Component A (g)</td><td>Wt.IEM (g)</td></tr><tr><td>13</td><td>3</td><td>40.00</td><td>1.19</td></tr><tr><td>14</td><td>4</td><td>40.00</td><td>0.21</td></tr><tr><td>15</td><td>5</td><td>40.00</td><td>1.19</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 17,
+        "chunk": "# Preparatory Example 16-19  \n\n[0156]  A series of hydrophilic copolymers were synthesized by charging 4 amber glass bottles with different weight proportions of hydrophilic monomers and $\\mathbf{\\alpha}_{\\mathbf{d}}$ -methyl styrene, and VAZO 52 $(0.4\\ \\mathrm{g})$ . Sufficient ethyl acetate was added to each bottle so that the total monomer concentration was 50 weight percent. The contents of each bottle was purged with nitrogen gas for 20 minutes and the bottle was capped, using poly(tetrafluoroethylene) thread tape. Each bottle was placed in a Model LLF LAUNDER-O-METER,with the water bath temperature set at $60^{\\circ}\\mathrm{C}.$ ,for 16 hours. Compositions and $\\mathbf{M}_{\\mathrm{n}}$ values for Examples 16-19 are shown in Table 4.  \n\nIEM in these copolymers, expressed as the weight percentage of IEM in the product, are given in Table 6. This step was performed by agitating the mixture at room temperature for 48 hours.  \n\nTABLE 6   \n\n\n<html><body><table><tr><td colspan=\"2\">Preparatory Examples 24-29</td></tr><tr><td>Preparatory Example</td><td>% by Weight IEM</td></tr><tr><td>24</td><td>0.5</td></tr><tr><td>25</td><td>1.0</td></tr><tr><td>26</td><td>2.0</td></tr></table></body></html>  \n\nTABLE 4   \n\n\n<html><body><table><tr><td colspan=\"7\">Preparatory Examples 16-19</td></tr><tr><td>Preparatory Example</td><td>MPEG(g)</td><td>VDM(g)</td><td>DMACM(g)</td><td>MPEG-1000(g)</td><td>Alpha- methylstyrene(g)</td><td>Mn</td></tr><tr><td>16</td><td>93.7</td><td>4.9</td><td rowspan=\"4\"></td><td rowspan=\"4\"></td><td>1.0</td><td>42,400</td></tr><tr><td>17</td><td>98.5</td><td>1.0</td><td>0.1 1.0</td><td>38,500</td></tr><tr><td>18</td><td>64.1</td><td>4.9</td><td></td><td>45,300</td></tr><tr><td>19</td><td></td><td>29.6</td><td></td><td>13,700</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# Preparatory Examples 20-23  \n\n[0157]   Each solution of the products of Preparatory Examples 16-19 was combined with different proportions of HEMA,BHT ( $(100\\mathrm{ppm})$ , and a catalytic amount of DBU in an amber bottle. The bottle was agitated in a heated shaker water bath at $60^{\\circ}\\mathrm{C}$ . for 16 hours. The data are given in Table 5.  \n\nTABLE5   \n\n\n<html><body><table><tr><td></td><td colspan=\"3\">Preparatory Examples 20-23</td></tr><tr><td>Preparatory Example</td><td>Product from Preparatory Example (Component A)</td><td>Wt. Component A (g)</td><td>Wt.HEMA (g)</td></tr><tr><td>20</td><td>16</td><td>40.00</td><td>0.94</td></tr><tr><td>21</td><td>17</td><td>40.00</td><td>0.19</td></tr><tr><td>22</td><td>18</td><td>40.00</td><td>0.94</td></tr><tr><td>23</td><td>19</td><td>10.00</td><td>0.05</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 19,
+        "chunk": "# Preparatory Example 24-29  \n\n[0158]  A hydrophilic copolymer  was  synthesized  by charging an amber glass bottle with $65.1\\ \\mathrm{g}$ of MPEG, 35.0 $\\mathbf{g}$ of HEMA, $4.0\\ \\mathrm{g}$ of $\\mathbf{a}$ -methyl styrene, $0.4~\\mathrm{g}$ of AIBN and $90\\ \\mathrm{g}$ of ethyl acetate. The contents of the bottle were purged with nitrogen gas for 20 minutes and the bottle was capped, using poly(tetrafluoroethylene) thread tape. The polymerization bottle was placed in a water bath shaker at $65^{\\circ}\\mathrm{C}$ .for 24 hours. The resultant polymer had a $\\mathbf{M}_{\\mathrm{n}}$ of 12,200 as determined by GPC.  \n\n[0159] A series of copolymers with pendent ethylenic unsaturation were prepared by reacting portions of this copolymer with different weight proportions of IEM and a catalytic amount of dibutyltin dilaurate. The proportion of [0160]  A series of films were prepared by mixing either IG184 or different proportions of the solution of the product of Preparatory Example 1 (referred to as Component A in Table 7) with different proportions of each solution of the product of Preparatory Examples 8-15 (referred to as Component B in Table 7). The mixed solutions were separately coated onto a sheet of poly(ethylene terephthalate) (PET) release liner, such as those available under the trade designation “CLEARSIL\", available from CPFilms, Martinsville, Va., and the solvent was evaporated by heating the coatings in an oven at $50^{\\circ}$ for 4 hours. Another layer of PET release liner was then placed on top of the film, providing a coated film between two sections of PET release liner. This was irradiated for 30 minutes using a Sylvania $\\mathrm{F}40/350$ BL lamp (available from OSRAM SYLVANIA, Danvers, Mass.) with the sample approximately $2.5~\\mathrm{cm}$ from the lamp. The composition and absorbency of the films are given in Table 7. For Table 7, when absorbency could not be obtained because the sample lacked suficient strength to be transferred from the solution, the absorbency is given as “N/A.\"  \n\nTABLE 6-continued   \nExample 30-61   \n\n\n<html><body><table><tr><td colspan=\"2\">Preparatory Examples 24-29</td></tr><tr><td>Preparatory Example</td><td>% by Weight IEM</td></tr><tr><td>27</td><td>3.7</td></tr><tr><td>28</td><td>9.0</td></tr><tr><td>29</td><td>17.3</td></tr></table></body></html>  \n\n<html><body><table><tr><td></td><td>Examples 3061</td><td>Component B Preparatory Example</td><td></td></tr><tr><td></td><td>Component A Preparatory Example Example Number (wt %)</td><td>Number (wt %)</td><td>Absor- bency</td></tr><tr><td>30</td><td>1 (50)</td><td>8 (50)</td><td>N/A</td></tr><tr><td>31</td><td>1 (30)</td><td>8 (70)</td><td>119</td></tr><tr><td>32</td><td>1 (70)</td><td>8 (30)</td><td>N/A</td></tr><tr><td>33</td><td>Comparative Example (IG184, 0.2)</td><td>8 (99.8)</td><td>N/A</td></tr><tr><td>34</td><td>1 (50)</td><td>9 (50)</td><td>479</td></tr><tr><td>35</td><td>1 (30)</td><td>9 (70)</td><td>396</td></tr><tr><td>36</td><td>1 (70)</td><td>9 (30)</td><td>516</td></tr><tr><td>37</td><td>Comparative Example (IG184, 0.2)</td><td>9 (99.8)</td><td>620</td></tr><tr><td>38</td><td>1 (50)</td><td>10 (50)</td><td>410</td></tr><tr><td>39</td><td>1 (30)</td><td>10 (70)</td><td>N/A</td></tr><tr><td>40</td><td>1 (70)</td><td>10 (30)</td><td>536</td></tr><tr><td>41</td><td>Comparative Example (IG184, 0.2) 10 (99.8)</td><td></td><td>N/A</td></tr><tr><td>42</td><td>1 (50)</td><td>11 (50)</td><td>N/A</td></tr><tr><td>43</td><td>1 (30)</td><td>11 (70)</td><td>N/A</td></tr><tr><td>44</td><td>1 (70)</td><td>11 (30)</td><td>453</td></tr><tr><td>45</td><td>Comparative Example (IG184, 0.2) 11 (99.8)</td><td></td><td>N/A</td></tr><tr><td>46</td><td>1 (50)</td><td>12 (50)</td><td>781</td></tr><tr><td>47</td><td>1 (30)</td><td>12 (70)</td><td>530</td></tr><tr><td>48</td><td>1 (70)</td><td>12 (30)</td><td>528</td></tr><tr><td>49</td><td>Comparative Example (IG184, 0.2) 12 (99.8)</td><td></td><td>490</td></tr><tr><td>50</td><td>1 (50)</td><td>13 (50)</td><td>349</td></tr><tr><td>51</td><td>1 (30)</td><td>13 (70)</td><td>183</td></tr><tr><td>52</td><td>1 (70)</td><td>13 (30)</td><td>365</td></tr><tr><td>53</td><td>Comparative Example (IG184, 0.2) 13 (99.8)</td><td></td><td>186</td></tr><tr><td>54</td><td>1 (50)</td><td>14 (50)</td><td>355</td></tr><tr><td>55</td><td>1 (30)</td><td>14 (70)</td><td>286</td></tr><tr><td>56</td><td>1 (70)</td><td>14 (30)</td><td>507</td></tr><tr><td>57</td><td>Comparative Example (IG184, 0.2) 14 (99.8)</td><td></td><td>229</td></tr><tr><td>58</td><td>1 (50)</td><td>15 (50)</td><td>358</td></tr><tr><td>59</td><td>1 (30)</td><td>15 (70)</td><td>273</td></tr><tr><td>60</td><td>1 (70)</td><td>15 (30)</td><td>519</td></tr><tr><td>61</td><td>Comparative Example (IG184,0.2) 15 (99.8)</td><td></td><td>245</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 20,
+        "chunk": "# Examples 62-77  \n\n[0161]  A series of films were prepared by mixing either IG184 or different proportions of the solution of the product of Preparative Example 1 (referred to as Component C in Table 8) with different proportions of each solution of the product of Preparative Examples 20-23 (referred to as Component D in Table 8). The mixed solutions were separately coated onto poly(ethylene terephthalate) (PET) release liner, such as those available under the trade designation “CLEARSIL”, available from CPFilms, Martinsville, Va., and the solvent was evaporated by heating the coatings in an oven at $50^{\\circ}$ C. for 4 hours. Another layer of PET release liner was then placed on top of the film, providing a coated film between two sections of PET release liner. This was irradiated as described in Examples 3O-61. For Table 8, when absorbency could not be obtained because the sample lacked sufficient strength to be transferred from the solution, the absorbency is given as “N/A.”  \n\n<html><body><table><tr><td>Example</td><td>Component C Preparatory Example Number (wt %)</td><td>Component D Preparatory Example Number (wt %)</td><td>Absor- bency</td></tr><tr><td>62</td><td>1 (50)</td><td>20 (50)</td><td>N/A</td></tr><tr><td>63</td><td>1 (30)</td><td>20 (70)</td><td>N/A</td></tr><tr><td>64</td><td>1 (70)</td><td>20 (30)</td><td>297</td></tr><tr><td>65</td><td>Comparative Example (IG184, 0.2） 20 (99.8)</td><td></td><td>105</td></tr><tr><td>66</td><td>1 (50)</td><td>21 (50)</td><td>540</td></tr><tr><td>67</td><td>1 (30)</td><td>21 (70)</td><td>574</td></tr><tr><td>68</td><td>1 (70)</td><td>21 (30)</td><td>655</td></tr><tr><td>69</td><td>Comparative Example (IG184, 0.2) 21 (99.8)</td><td></td><td>720</td></tr><tr><td>70</td><td>1 (50)</td><td>22 (50)</td><td>452</td></tr><tr><td>71</td><td>1 (30)</td><td>22 (70)</td><td>182</td></tr><tr><td>72</td><td>1 (70)</td><td>22 (30)</td><td>379</td></tr><tr><td>73</td><td>Comparative Example (IG184, 0.2) 22 (99.8)</td><td></td><td>119</td></tr><tr><td>74</td><td>1 (50)</td><td>23 (50)</td><td>399</td></tr><tr><td>75</td><td>1 (30)</td><td>23 (70)</td><td>325</td></tr><tr><td>76</td><td>1 (70)</td><td>23 (30)</td><td>555</td></tr><tr><td>77</td><td>Comparative Example (IG184, 0.2) 23 (99.8)</td><td></td><td>391</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 21,
+        "chunk": "# Examples 78-83  \n\n[0162]  A series of films were made by mixing equal weights of a solution of each of the products from Preparative Example 24-29 (identified as Component E in Table 9) with a solution of the product of Preparative Example 2. The resultant solutions were separately coated onto poly(ethylene terephthalate) (PET) release liner, such as those available under the trade designation “CLEARSIL\"，available from CPFilms, Martinsville, Va., and the solvent was evaporated by heating the coatings in an oven at $50^{\\circ}\\mathrm{C}$ for 4 hours. Another layer of PET release liner was then placed on top of the film, providing a coated film between two sections of PET release liner. This was irradiated as described in Examples 30-61. The data are given in Table 9.  \n\nTABLE 9   \n\n\n<html><body><table><tr><td></td><td colspan=\"2\">Examples 78-83</td></tr><tr><td>Example</td><td>Component E (Preparatory Example Number)</td><td>Absorbency</td></tr><tr><td>78</td><td>24</td><td>327</td></tr><tr><td>79</td><td>25</td><td>310</td></tr><tr><td>80</td><td>26</td><td>239</td></tr><tr><td>81</td><td>27</td><td>212</td></tr><tr><td>82</td><td>28</td><td>118</td></tr><tr><td>83</td><td>29</td><td>75</td></tr></table></body></html>  \n\n1. A hydrophilic, crosslinkable oligomer composition comprising  \n\n(a) a first component oligomer comprising a plurality of polymerized monomer units having pendent, free-radically polymerizable functional groups, and a plurality of polymerized monomer units having pendent, hydrophilic poly(alkylene oxide) groups; and (b) a second component oligomer comprising a plurality of polymerized monomer units having pendent, photoinitiator groups.  \n\n2. The oligomer composition of claim 1 wherein the composition is melt-processible at temperatures of $100^{\\circ}\\mathrm{~C~}$ or less. 3. The composition of claim 1 wherein said composition has a residual content of less than 2 weight $\\%$ \\* 4. The composition of claim 1, wherein said oligomers a) and bj nave an average aegree ol porymerizauon ol iess tnan 300. 5. The composition of claim 1 wherein each of said oligomers a) and b) have a degree of polymerization of less than 300. 6. The composition of claim 1, wherein said pendent polyalkylene oxide groups of said first component oligomer is of the formula:  \n\n$\\mathrm{(CH(R^{1}){\\mathrm{-}}C H}_{2}{\\mathrm{-}}\\mathrm{O})_{\\mathrm{m}}{\\mathrm{-}}\\mathrm{R}^{2}$ wherein $\\mathbb{R}^{1}$ is a H or a $\\mathrm{C}_{1}$ to $\\mathrm{C_{4}a l k y l}$ group, $\\mathrm{\\bar{R}}^{2}$ .5 $\\mathrm{H}$ ,a $\\mathrm{C}_{1}$ to $\\mathrm{C}_{4}$ alkyl group, aryl, or combinations thereof, and m is from 2 to 100. 7. The composition of claim 1, wherein said pendent   \npoly(alkylene oxide) group is a poly(ethylene oxide)   \n(co)polymer. 8. The composition of claim 1, wherein said pendent   \npoly(alkylene oxide) group is a poly(ethylene oxide-co  \npropylene oxide) copolymer. 9. The composition of claim 1, wherein said second   \ncomponent oligomer further comprises a plurality of poly  \nmerized monomer units having pendent, hydrophilic poly  \n(alkylene oxide) groups. 10. The composition of claim 1 wherein said first oligo  \nmer having pendent unsaturated polymerizable groups is   \nprepared by the reaction of an oligomer having a plurality of   \npendent reactive functional groups with an unsaturated   \ncompounds having co-reactive functional groups. 11. The composition of claim 1O wherein said pendent   \nreactive functional groups are selected from hydroxyl,   \namino, oxazolinyl, oxazolonyl, acetyl acetonyl, carboxyl,   \nisocyanato, epoxy, aziridinyl, acyloyl halide, and cyclic   \nanhydride groups. 12. The composition of claim 1 wherein the second   \ncomponent oligomer is prepared by the reaction of an   \noligomer having a plurality of pendent reactive functional   \ngroups with co-reactive compounds having a photoinitator   \ngroup. 13. The composition of claim 1 which comprises an   \namount of said second component sufficient to provide more   \nthan two crosslinks per first component oligomer chain. 14. The composition of claim 1 which comprises: (a) from 0.01 to 99.9 parts by weight of said first component oligomer, and (b) from 99.9 to 0.1 parts by weight of said second component oligomer, wherein the composition, when crosslinked, can absorb at least 50 wt. $\\%$ water. 15. The composition of claim 1 wherein said first com  \nponent oligomer comprises (a) from 20 to 99 parts by weight of polymerized monomer units derived from an ethylenically-unsaturated monomer having a pendent poly(alkylene oxide) group; (b) from 0.1 to 35 parts by weight of polymerized monomer units derived from of an ethylenically-unsaturated monomer having a pendent polymerizable functional group;  \n\n(c) from 0 to 50 parts by weight of polymerized monomer units derived from a polar monomer; (d) from O to 20 parts by weight of polymerized monomer units derived from a hydrophobic monomer; (e) from O to 10 parts by weight of at least one other monomer.  \n\n16.The oligomer composition of claim 15 wherein said polar monomer c), when present, is selected from the group consisting of substituted (meth)acrylamides, N-vinyl pyrrolidone, N-vinyl caprolactam, acrylonitrile, N-vinyl acetamide, tetrahydrofurfuryl acrylate, acrylamides, and mixtures thereof.  \n\n17. The composition of claim 1 wherein the second oligomer component comprises: (a) from 20 to 99 parts by weight of polymerized monomer units having pendent, hydrophilic poly(alkylene oxide) groups, (b) from 0.1 to 25 parts by weight of polymerized monomer units derived from of an ethylenically-unsaturated monomer having a pendent photoinitiator group; (c) from 0 to 25 parts by weight of polymerized monomer units derived from of an ethylenically-unsaturated monomer having a pendent polymerizable group; (d) from O to 20 parts by weight of hydrophobic monomers; (e) from 0 to 50 parts by weight of polymerized monomer units derived from a polar monomer; and (f) from O to 40 parts by weight, preferably less than 25 parts by weight, of at least one other monomer. 18. A crosslinked composition comprising the composition of claim 1, having an average molecular weight between crosslinks of $\\geq1000$ \\* 19.A process for making a substrate bearing a coating of a crosslinked polymer composition on at least one surface thereof, comprising the steps of: (a) coating onto said substrate the oligomer composition of claim 1; and (b） photochemically crosslinking said first component oligomer and second component oligomer, in the presence of a photoinitiator, by forming covalent bonds between said pendent, free-radically polymerizable functional groups of said first component oligomer said second component oligomer. 20. The process of claim 19 wherein said oligomer composition has been partially converted to a coatable viscosity of from 750 to $7{,}500\\mathrm{cPs}$ at $22^{\\circ}\\mathrm{C}$ prior to step a. 21. The process of claim 19 wherein said oligomer composition comprises (a) per 10O parts by weight of said first component, an amount of said second component sufficient to provide more than two crosslinks per first component oligomer chain; (b) less than 2 parts by weight residuals content. 22. The process of claim 19 wherein the molecular weight $(\\mathbf{M}_{\\mathrm{n}})$ of said first oligomer is less than the entanglement molecular weight.  \n\n23.The process of claim 19 wherein the average degree of polymerization of the first and second component oligomers is $\\leq300$ .   \n24. An absorbent dressing comprising a crosslinked hydrophilic gel absorbent layer of claim 1.   \n25. The absorbent dressing of claim 24 comprising: a permeable facing layer, a backing layer bonded to said facing layer at the periphery, and a hydrophilic gel absorbent layer disposed between the backing and facing layer.  \n\n26. The absorbent dressing of claim 25 having a layer of pressure sensitive adhesive on at least a portion of the front surface of the facing layer. 27. The absorbent dressing of claim 25 wherein the gel layer further comprises a pharmacologically active agent. 28. The absorbent dressing of claim 25 wherein the gel layer further comprises a hydrocolloid. 29.The absorbent dressing of claim 25 wherein the gel layer further comprises a patterned surface.",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Preparation of Water-Resistant Antifog Hard Coatings on Plastic Substrate  \n\nChao-Ching Chang,†,‡ Feng-Hsi Huang,† Hsu-Hsien Chang,† Trong-Ming Don,†,‡ Ching-Chung Chen,‡ and Liao-Ping Cheng\\*,†,‡  \n\n†Department of Chemical and Materials Engineering, and ‡Energy and Opto-Electronic Materials Research Center, Tamkang University, New Taipei City, Taiwan, 25137  \n\n\\*S Supporting Information  \n\nABSTRACT: A novel water resistant antifog (AF) coating for plastic substrates was developed, which has a special hydrophilic/hydrophobic bilayer structure. The bottom layer, acting both as a mechanical support and a hydrophobic barrier against water penetration, is an organic−inorganic composite comprising colloidal silica embedded in a cross-linked network of dipentaethritol hexaacrylate (DPHA). Atop this layer, an AF coating is applied, which incorporates a superhydrophilic species synthesized from Tween-20 (surfactant), isophorone diisocyanate (coupling agent), and 2-hydroxyethyl methacrylate (monomer). Various methods, e.g., FTIR, SEM, AFM,  \n\n![](images/399065e8dca87b266881bcc15e69aed846ac63a559f6f1eb1e5d0b3a04a76b6e.jpg)  \n\ncontact angle, and steam test, were employed to characterize the prepared AF coatings. The results indicated that the size and the continuity of the hydrophilic domains on the top surface increased with increasing added amount of T20, however, at the expense of hardness, adhesiveness, and water resistivity. The optimal T20 content was found to be 10 wt $\\%$ , at which capacity the resultant AF coating was transparent and wearable (5H, hardness) and could be soaked in water for 7 days at $25~^{\\circ}\\mathrm{C}$ without downgrading of its AF capability.",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# INTRODUCTION  \n\nFog forms when saturated water vapor condenses in the form of small droplets capable of scattering visible light on a surface with a temperature lower than the dew point of the vapor. This undesirable phenomenon occurs frequently on bathroom mirrors, eyeglasses, swimming goggles, windshields, camera lens, etc., items which are closely related to our everyday life. Surface fog can reduce the precision of optical and analytical instruments, such as infrared microscopes or bronchoscopes.1,2 In applications where high solar energy input is demanded, such as solar cells, fogging could reduce the light transmittance and bring down the efficiency of energy usage.3  \n\nThe basic concept of antifog is to create a hydrophilic surface such that arriving water droplets would spread and naturally form a continuous or nearly continuous water film on the surface, so that light can transmit directly free of interfering scattering from water microdroplets.4,5  \n\nPreparation of a hydrophilic surface generally falls into three categories: I. Hydrophilic agents are physically introduced into the polymer matrix without chemical bond formation. Usually, a simple process such as solution or melt blending is good enough to yield an effective AF surface. However, the hydrophilic agents may come off the coating surface during cleaning, and thus, stable long-term wettibility cannot be assured. As a result, this approach is only suited to products of short life cycles, such as food packaging.6 II. Chemical modification was performed directly on the surface of interest.7−10 For example, Howarter et al. grafted hydrophilic species, poly(ethylene glycol) (PEG), onto a glass surface through the use of a silane-type coupling agent that bridged PEG and glass. Both good adhesion and hydrophilicity were attained via this method. However, the treated surface became very soft due to the presence of the hydrophilic agent. Even small mechanical impacts can give rise to visible scratching marks. Furthermore, because complex chemical processes were involved, it is impractical to apply this method to substrates of large surface area,8,9 such as building windows. III. Hydrophilic components are incorporated into the coating formula, which is then photo or thermal-cured to form an AF layer on the surface. Unlike method I, the hydrophilic species are chemically cross-linked to the matrix in this case. Although method III is applicable to virtually any kind of substrate materials (plastics are of particular interest), the interface between coating layer and substrate is susceptible to water invasion due to absorption by hydrophilic groups. The AF layer may swell and detach from the substrate in very humid environments.11 Alternatively, on glass substrates, an AF layer may be formed consisting of inorganic oxides such as $\\mathrm{TiO}_{2},\\mathrm{Cd}_{2}\\mathrm{O}_{3},\\mathrm{ZnO},$ or $\\mathrm{ZrO}_{2}$ . Although it has the benefits of good adhesion and surface hardness, the high temperature process associated with oxide formation  \n\nScheme 1. Preparation of (a) Silica Sol and (b) $\\mathbf{MSiO}_{2}$ Sol and Polyacrylate-Silica Thin Film (Bottom Layer)  \n\n![](images/406951866384a8afaea3af1d2af7637a4a532fb71aaaae6f409def656dbabcfd.jpg)  \n\nprecludes it from being applied on plastic materials.12−18 A comprehensive review of the articles for preparation and design of such hydrophilic coatings has been carried out by Feng et al.19 In recent years, biomimetic, raspberry-like, or nanoporous antireflective/antifogging films composed by silica $\\left(\\mathrm{SiO}_{2}\\right)$ and titania (TiO2) nanospheres have been demonstrated.20−28 However, to improve the mechanical durability, robustness, and adhesion of the films, the resultant films have to be calcinated at $500~^{\\circ}\\mathrm{C}$ .  \n\nAs a matter of fact, there are several hurdles to overcome in order to prepare a robust, long-life, antifog coating on plastic substrates. First, if direct surface modification is to be implemented, one should consider the fact that plastics are sensitive to both temperature and solvent damaging. Second, the coating layer should adhere strongly to the substrate and should not deform or peel off when used in highly humid environments or when cleaning is required. Third, hardness of the coating should comply with the application criterion. In the current research, a new approach is adopted in light of the above concerns. The prepared antifog coating has a special bilayer configuration, for which the bottom layer (primer) is a cross-linked network of poly(acrylate) embedded with nanosized silica that provides mechanical strength and adhesiveness. On top of the primer is lain the AF layer, in which surface active agent, Tween 20, is modified and covalently incorporated into the polymer host. Because the top and bottom layers are interlinked by UV-cured poly(acrylate), these two layers are mechanically inseparable and appear transparent as if they were a uniform layer. Furthermore, the coating can be rinsed in water and remain integrality after drying. Thanks to the hydrophobic feature of the primer, water molecules cannot penetrate through the coating and detach it from the substrate. The detailed synthesis and characterization of the developed antifog coating is demonstrated in the following sections.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# EXPERIMENTAL SECTION  \n\nChemicals. 3-(Trimethoxysilyl) propyl methacrylate (MSMA, Degussa), tetraethoxysilane (TEOS, Fluka), sorbitan monolaurate (Tween 20, $M_{\\mathrm{w}}=1227.5,$ Aldrich), isophorone diisocyanate (IPDI, Aldrich), 2-hydroxyethyl methacrylate (2- HEMA, Aldrich), dipentaethritol hexaacrylate (DPHA, Aldrich), Darocure 1173 (Ciba-Geigy), methyl ethyl ketone (MEK, Fluka), 2-propanol (IPA, Aldrich) were at regent grade or higher, and used as received.  \n\nSynthesis of Surface-Modified Silica. The silica sol for the bottom layer was synthesized by a modified sol−gel method, cf. Scheme 1.29−32 An appropriate amount of TEOS was mixed with 2-propanol to form a homogeneous solution. To this solution, the catalyst HCl (aq) $\\left(\\mathsf{p H1.2}\\right)$ was added to induce hydrolysis−condensation of TEOS. The molar ratio of $\\mathrm{{H}}_{2}\\mathrm{{O}/T E{O S}}$ was set to be equal to four. The mixture was stirred for $3\\mathrm{h}$ at room temperature to yield a silica sol, and then additional HCl (aq) $\\left(\\mathsf{p H1.2}\\right)$ and coupling agent, MSMA, with a molar ratio of $\\mathrm{{H}}_{2}\\mathrm{{O}}/\\mathrm{{MSMA}}=3\\$ and $\\mathrm{TEOS/MSMA}=4.5,$ were slowly dropped into the silica sol, cf. Scheme 1b. After reaction for another $^{3\\mathrm{~h~},}$ the surface-modified silica (termed $\\mathrm{MSiO}_{2},$ containing $\\scriptstyle{\\mathrm{C}}={\\mathrm{C}}$ on their surface) was obtained.  \n\nPreparation of the Antifog Coating. Photocurable coating sol was prepared by adding $_{10\\mathrm{~g~}}$ of the multifunctional cross-linking agent (DPHA), $_{0.59\\mathrm{~g~}}$ of the photoinitiator (Darocure 1173), and $17.68\\ \\mathrm{g}$ of 2-propanol into $20\\mathrm{g}$ of the assynthesized $\\mathrm{MSiO}_{2}$ sol with a total solid content (theoretical) adjusted to $30\\mathrm{\\mt\\\\%}$ . The sol was spin-coated on a poly(methyl methacrylate) (PMMA) substrate, and then prebaked at $80~^{\\circ}\\mathrm{C}$ for $40~\\mathsf{s},$ , followed by UV-irradiation (broadband, $250~\\mathrm{mJ/cm}^{2},$ to obtain a cured film. The thickness of the film was measured to be ${\\sim}1.2\\ \\mu\\mathrm{m}$ by interferometry. The radiation power was carefully chosen such that DPHA was only partly cross-linked, allowing for subsequent reaction with the top AF layer during UV-curing of the latter.  \n\n![](images/1265f7594615817bc912d3fb9d5d6658a242c226c0cc135a0e4dc976dfe5ffd5.jpg)  \nScheme 2. (a) Reaction of IPDI and 2-HEMA to Form the Intermediate Molecule 2-HEMA/IPDI and (b) Proposed Reaction Mechanism for the Synthesis of UV Curable Hydrophilic Agent T20  \n\nTo prepare the coating sol for the AF layer, hydrophilic agents were modified first, cf. Scheme 2. Equal number of moles of 2-HEMA and IPDI were stirred in a glass reactor under temperature control. When the temperature reached 50 ${}^{\\circ}\\mathrm{C},$ dibutyltin dilaurate ( $0.1\\%$ of the total weight of 2-HEMA and IPDI) acting as the catalyst was added, and the reaction was allowed to proceed for $^{2\\mathrm{~h~}}$ at $50~^{\\circ}\\mathrm{C}$ . Subsequently, hydrophilic agent (Tween 20) was added and reacted for another $^{2\\mathrm{~h~}}$ . The molar ratio of IPDI/Tween20 was set to 1. The modified Tween 20 was called T20, hereinafter. The AF coating sols for the top layer were prepared by mixing $\\mathrm{T}20$ with the coating sol for the bottom layer, however, with some adjustment of the DPHA content to give 30 wt $\\%$ silica in the coating, cf. Table 1. The formed sol was spin-coated on the partly cured bottom layer, followed by predrying $(80^{\\circ}\\mathrm{C},40\\mathrm{s})$ and UV-curing $(500~\\mathrm{mJ/cm}^{2})$ to obtain an AF layer of ${\\sim}1\\ \\mu\\mathrm{m}$ thick.  \n\nTable 1. Chemical Species for Preparing the Top AF Layer of the Coating   \n\n\n<html><body><table><tr><td>sample name</td><td>MSi02 sol (g)</td><td>T20 (g)</td><td>IPA (g)</td><td>DPHA (g)</td><td>1173 (g)</td></tr><tr><td>AF2</td><td>20</td><td>0.3</td><td>17.68</td><td>9.7</td><td>0.59</td></tr><tr><td>AF4</td><td>20</td><td>0.6</td><td>17.68</td><td>9.4</td><td>0.59</td></tr><tr><td>AF6</td><td>20</td><td>0.9</td><td>17.68</td><td>9.1</td><td>0.59</td></tr><tr><td>AF8</td><td>20</td><td>1.2</td><td>17.68</td><td>8.8</td><td>0.59</td></tr><tr><td>AF10</td><td>20</td><td>1.5</td><td>17.68</td><td>8.5</td><td>0.59</td></tr><tr><td>AF12</td><td>20</td><td>1.8</td><td>17.68</td><td>8.2</td><td>0.59</td></tr><tr><td>AF15</td><td>20</td><td>2.25</td><td>17.68</td><td>7.75</td><td>0.59</td></tr><tr><td>AF96</td><td>2</td><td>24</td><td>1.77</td><td>0.5</td><td>0.59</td></tr></table></body></html>  \n\nFTIR Spectra. Fourier transform infrared (FTIR) absorption spectra of the formed $\\mathrm{{MSiO}}_{2}$ sol and the cured coatings were obtained using a Nicolet 550 spectrometer. Cured thin films were ground with KBr (1:50) and pressed to form a disc for FTIR scanning. Liquid samples were prepared by dropping appropriate amount of the sol onto a KBr disc, and then the solvent was evaporated at $40~^{\\circ}\\mathrm{C}$ for $10~\\mathrm{{min}}$ in a vacuum oven.  \n\nParticle Size Determination. The size and size distribution of particles in the sols were determined by the dynamic light scattering (DLS) analysis using a Zetasizer (Malvern, DTS 1060) at $25~^{\\circ}\\mathrm{C}$ . The instrument was equipped with a monochromatic coherent helium neon laser $\\left(633~\\mathrm{nm}\\right)$ as the light source. A $4\\mathrm{\\mL}$ sample was injected into the quartz cuvette secured on the holder, and then the scattered light was recorded at an angle of $173^{\\circ}$ with respect to the incident beam.  \n\nFilm Surface Observation. The nanoscale morphology of the cured film was observed using a Leo 1530 field emission scanning electron microscope (FE-SEM). The samples were vacuum-dried and then coated with a thin layer (ca. $1.0\\ \\mathrm{nm}\\cdot$ ) of a $\\mathrm{Pt-Pd}$ alloy with a sputter coater equipped with a quartz crystal microbalance thickness controller. The samples were imaged at high magnifications (e.g., $\\mathbf{\\times}100\\mathbf{k})$ under the acceleration voltage of $15\\ \\mathrm{kV}$ via an in-lens detector. Atomic force microscopic (AFM) imaging of the bottom and the AF layers were performed with a Nano Scope scanning probe microscope (CP-II, Veeco). Tapping mode was used to track the surface of the sample via a single crystal silicon probe (Olympus tapping mode etched silicon probe). The spring constant and resonance frequency of the probe were $42{-}80\\mathrm{N}/$ m and ${50{\\mathrm{-}}100\\ \\mathrm{kHz,}}$ respectively. The scanning frequency was $1\\ \\mathrm{Hz}$ . Both topographic diagram and phase contrast diagram were constructed. The former diagram provides information of surface roughness and domain size, whereas the later voltage distribution on the surface.  \n\nContact Angle, Adhesion, and Hardness Measurements. The contact angle between water and AF surface was measured by a FTA 125 contact angle/surface tension analyzer at room temperature. A $6\\mu\\mathrm{L}$ drop of water was placed onto the surface of the coating. The image was taken and the contact angle was measured from shape analysis of the sessile drop. Tape test (CNS 11684), also known as peel test, was carried out to evaluate the adhesion of the coatings on the substrate. The degree of adhesion was defined as the percentage of film residing on the plate after the peel test. The hardness of the cured films was examined by the industrial pencil hardness test (JIS K5400) with pencils of different hardness at a load of 765 g.  \n\nSteam Tests. Steam tests of various coatings were carried out to see their AF performance. Boiling water was added into a beaker to about half full. Then, the sample was placed on the beaker with the coated surface facing down. Vapor condensed on the coating surface was observed and photographed.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# RESULTS AND DISCUSSION  \n\nPreparation and Characterization of the Primer. The primer is an organic−inorganic hybrid material composed of nanosized silica dispersed uniformly in the polymer host.31 The sol−gel process for the synthesis of surface-modified silica, $\\mathrm{MSiO}_{2},$ involves hydrolysis and condensation of TEOS and MSMA. The detailed chemical analyses (FTIR and $^{29}\\mathrm{Si}$ NMR) of this reaction have been documented.23 Particle size of the modified silica was measured to be $\\mathrm{\\sim}7~\\mathrm{nm}$ , consistent with those reported in the literature.29  \n\nThe formed $\\mathrm{{MSiO}}_{2}$ sol was mixed with DPHA, photoinitiator, and 2-propanol and then UV-cured to yield an organic−inorganic hybrid hard coating on PMMA plate.28 Figure 1 shows the effect of UV power on the curing efficiency of a typical sample. A monotonous decrease of the $\\scriptstyle{\\mathrm{C}}={\\mathrm{C}}$ peak signal at $1634~\\mathrm{{\\bar{cm}}^{-1}}$ is indicated with increasing UV irradiation intensity. When the power was set to $500~\\mathrm{mJ/cm}^{2}.$ , the peak was very small, implying that most of the vinyl groups were converted to $\\scriptstyle{\\mathrm{C-C}}$ bonds during the UV-induced cross-linking reaction. In case that only half of the power $250\\ \\mathrm{mJ/cm}^{2}$ was employed, there was still ${\\sim}40\\%$ vinyl groups left unreacted (based on the peak area analysis). The free vinyl groups near the surface region would react with the curing agent, DPHA, in the top AF layer during the second stage curing process. The cured primer exhibited a hardness of 4H according to the pencil test, and it attached firmly to the PMMA substrate with a peeltest adhesion of $100\\%$ . FE-SEM imaging of the primer indicated a uniform surface morphology (Figure S1, Supporting Information), free of organic/inorganic phase domains at the resolution scale of $10\\ \\mathrm{~nm}$ , agreeing with the fact that the coating was a highly transparent thin film. The 3-D topographic AFM diagram of the primer’s surface was extremely smooth with a measured average roughness as small as $1.4\\ \\mathrm{nm}$ (Figure S2, Supporting Information). Curing with a power lower than $250\\mathrm{\\mJ}/\\mathrm{cm}^{2}$ has been tested to give higher residual $\\scriptstyle{\\mathrm{C}}={\\mathrm{C}}$ concentration, however, at the sacrifice of the mechanical strength. In summary, $250~\\mathrm{mJ}/\\mathrm{cm}^{2}$ is appropriate for preparing a smooth coating surface possessing sufficient amount of vinyl groups for making bonds with the multifunctional monomer, DPHA, in the top AF layer during the second stage curing process.  \n\n![](images/32dbbc68f7e65446f6d38ee55bb18ffc1422bd88acd329077f8eee6295f89f20.jpg)  \nFigure 1. FTIR spectra of the UV-cured coatings for the bottom layer, showing the effect of irradiation power.  \n\nPreparation of the AF Layer. The surfactant, Tween-20, was modified to acquire UV photosensitivity by linking to 2- HEMA via the spacer IPDI. The synthetic process involved two steps, as shown in Scheme 2. First, the −OH group of 2-HEMA and $-\\mathrm{\\mathbf{N}}\\mathrm{\\mathbf{C}}\\mathrm{\\mathbf{O}}$ group of IPDI were reacted to form the urethane bond in the molecule, 2-HEMA/IPDI.33 During the course of this reaction, the $-\\mathrm{NH}$ peak in the FTIR spectra (Figure S3, Supporting Information) stemming from the urethane linkage is found at $1529~\\mathrm{{cm}^{-1}}$ whose intensity increases gradually up to $^{\\mathrm{~1~h,~}}$ and afterward it levels-off. Because 2-HEMA and IPDI were initially charged at equal molar amount, the reaction was considered to approach completeness in ca. $^\\textrm{\\scriptsize1h}$ . In the second step, the as-prepared molecule 2-HEMA/IPDI was reacted with Tween-20 to give a dual-functional molecule (T20), bearing both UV-curability and high hydrophilicity. The −NH peak of urethane at $1529~\\mathrm{{cm}^{-1}}$ , signifying the presence of T20, rises progressively over the period of $^\\textrm{\\scriptsize2h}$ . In contrast, the -NCO signal at $22\\dot{6}0~\\mathrm{cm}^{-1}$ declines with time and it vanishes virtually after reaction for $^{2\\mathrm{h},}$ confirming that the second half of -NCO groups in IPDI has all been converted to urethane at the end of reaction (Figure S4, Supporting Information). It should be noted that the $\\scriptstyle{\\mathrm{C}}={\\mathrm{C}}$ groups remain intact throughout the reaction. These groups can be used to cross-link with DPHA during UV curing of the top layer.  \n\nFigure 2 shows the FTIR spectra of a typical bilayer coating, AF10. The $_{\\mathrm{Si-O-Si}}$ band at $\\mathsf{\\bar{1529}~c m^{-1}}$ indicates the presence of $\\mathrm{MSiO}_{2}$ whereas $\\scriptstyle{\\mathrm{C}}={\\mathrm{O}}$ at $1727~\\mathrm{{cm}^{-1}}$ is contributed by 2- HEMA, Tween-20, and DPHA moieties. The small $\\scriptstyle{\\mathrm{C}}={\\mathrm{C}}$ signal suggests that an effective UV-curing has been performed; thereby, a rather hard AF layer (4H) was created (details shown later). The amount of $\\scriptstyle{\\mathrm{C}}={\\mathrm{C}}$ bond can further be reduced by postbaking of the sample at $100^{\\circ}\\mathrm{C}$ . Apparently, baking for $^{\\textrm{1h}}$ . is sufficient to consume most of the residual $\\mathrm{C=C_{\\mathrm{\\lambda}}}$ ; prolonged baking is futile probably due to steric hindrance. The other effect of postbaking is for the compaction of silica particles. As is evident from the spectra, new $_{\\mathrm{Si-O-Si}}$ bonds are formed by alcohol condensation of $_{\\mathrm{Si-O-C}}$ and/or water-condensation of $S_{\\mathrm{i-OH}}$ groups. The bottom layer and bilayer coatings were highly transparent in the visible region. For example, the transmittance of the bilayer coating AF10 is $95{-}98\\%$ in the visible region (Figure S5).  \n\n![](images/5a0ad710e9de3780cc9cde42eabfc7ba8306dd10924415407b962bf9d993432e.jpg)  \nFigure 2. FTIR spectra of the bilayer AF coating AF10.  \n\nAFM was employed to disclose the surface morphology as well as the distribution of T20 within the surface region of various prepared coatings. Figure 3 shows the topographic and voltage contrast diagrams of the surfaces of the primer and sample AF96. The former consists of DPHA and $\\mathrm{MSiO}_{2},$ whereas the latter contains mostly T20 $(96\\%)$ . The topographic diagrams (right part) for these two samples are similar; both surfaces are extremely smooth with measured average roughness of ${\\sim}1\\ \\mathrm{nm}$ . However, their voltage contrast diagrams (left part) are distinctively different. For the primer’s surface, the scanning voltage is above $_{7\\mathrm{V}}$ over the entire surface, except for some sporadic spots. In contrast, for the sample AF96, a small scanning voltage, 1.41 V, covers $\\sim90\\%$ (based on image analysis) of the scanning area. Generally, the voltage value depends both on the roughness and the rigidity of the surface. For a very smooth surface having roughness $<10~\\mathrm{nm}$ , the voltage value is useful for estimating the distribution of hard/ soft domains on the surface.34,35 For example, the primer is a very hard material composed of highly cross-linked DPHA and $\\mathrm{{MSiO}}_{2},$ and thus high scanning voltage is imposed. On the other hand, a relatively low voltage is delivered to the surface of AF96 due to the presence of the soft hydrophilic agent, T20. In this context, by analyzing the voltage contrast diagram, one can differentiate the hydrophilic (soft) from the hydrophobic (hard) zones on a flat AF coating surface. Three typical cases are demonstrated in Figure 4 for comparison. The T20 contents for these coatings are 4, 12, and 15 wt $\\%$ , respectively. From the topographic diagrams (right part), the measured average surface roughness is found to increase just slightly from 1.0 to $3.6~\\mathrm{nm}$ with a large increase of T20 dosage from 4 to 15 wt $\\%$ . On the other hand, the voltage contrast diagrams (left part) use gray scale to manifest areas of different voltages; the light-gray depicts high voltage (hard) regions, whereas the darkgray, low voltage (soft) ones. As is expected, the dark area increases as the T20 content is raised. To estimate the distribution of soft/hard domains on the AF surface, the voltage contrast diagrams are further processed to give black and white bicolor patterns, as shown in Figure 5, with $_{5\\mathrm{~V~}}$ being taken as the border value. This voltage is selected based on two facts: (i) it is close to the arithmetic mean of the highest voltage of the primer’s surface and the lowest voltage of AF96 (Figure 4); (ii) as the lowest voltage of the primer’s surface is $6\\mathrm{V},$ below $_{5\\mathrm{~V~}}$ contribution from the soft segments (T20) is expected to outweigh that from the hard segments (cured DPHA and $\\mathrm{MSiO}_{2}\\mathrm{\\backslash}$ . In fact, bicolor patterns with various cutting-edge voltages over the range $4.5\\substack{-5.5\\mathrm{~V~}}$ have been created, and from them a similar conclusion can be inferred, considering the effect of soft/hard pattern on the AF performance discussed below.  \n\nFrom Figure 5, variation of soft/hard domains with respect to T20 content is clearly illustrated. For the sample AF4, only small separate black dots of ca. $10{-}35~\\mathrm{nm}$ are present, and for the sample AF10, the amount of black dots increases and some of them start to connect with each other. When the T20 content reaches 15 wt $\\%$ , AF15, the black dots interconnect extensively into many continuous regions, which constitute ca. $25\\%$ of the total area. The bicolor diagrams, even with its approximate nature, are useful for understanding the antifog mechanism underlying the prepared AF coatings. Surface fog is generated when impinging water droplets develop to the size that scatters visible light, typical ${>}100\\ \\mathrm{nm},$ , and in case that the growing water droplets contact a hydrophilic area, they will spread to reduce their surface tension. Therefore, AF effect can be achieved as long as the hydrophilic area on the coating surface can form a pattern that prohibits the growth of water droplets beyond ${\\sim}100~\\mathrm{nm}$ , which is manifested in Figure 5. For the sample AF4, water droplets of size as large as ${\\sim}160~\\mathrm{nm}$ (cf. the white area) may rest independently on the coating surface; hence, fog is expected to form on this surface. In contrast, for both AF10 and AF15, the sizes of the hydrophobic domains are all less than $100\\ \\mathrm{nm}$ (average $63\\ \\mathrm{nm}$ for AF10). As arriving water droplets tend to spread into a continuous film, scattering does not occur, and these two coatings will exhibit AF characteristic.  \n\n![](images/7585e7b4cc2b2bb4bfc8684978d2d5e28ceb5abcd76ab4cd2ea202b0066fff34.jpg)  \nFigure 3. AFM voltage (left part) and topographic (right part) diagrams of the coating. (a) Primer and (b) AF96.  \n\n![](images/5a7ed6ed28ef248807e6671f8d34030607e85e6eb8d48a3f24bad3e84a1e67f6.jpg)  \nFigure 4. AFM voltage (left part) and topographic (right part) diagrams of the AF coatings with different T20 contents. (a) AF4, (b) AF10, and (c) AF15.  \n\nAntifog and Hardness Tests. Hardness, contact angle, adhesion, and AF tests of various prepared coatings were performed and the results are summarized in Table 2. The plastic substrate PMMA is relatively soft with a pencil hardness ${<}\\mathrm{{1H}}$ After coated with the primer, its hardness rises to 4H (8H, if fully cured), high enough for general purpose. This surface is, however, relatively hydrophobic with a high water contact angle of $70^{\\circ}$ , and the AF test indicates a misty appearance, cf. Figure 6a. After applying an AF layer on top of the primer, the water contact angle drops dramatically. For example, the contact angle lowers down to $30^{\\circ}$ upon incorporation of $4\\%$ T20 (AF4), and a $10\\%$ T20 dosage (AF10) renders the coating surface extremely hydrophilic such that the deposited droplet spreads automatically with immeasurably small water contact angle. Superb AF performance of this coating is in evidence by the steam test; as shown in Figure 6b, the English letters underneath the beaker are clearly seen for the area sheltered by the AF coating. In general, the hydrophilicity of a coating increases with its T20 content, however, at the expense of the mechanical strength. For example, as shown in Table 2, the hardness of the coatings plunges quickly from 6H to ${<}\\mathrm{{1H}}$ when the T20 content is raised from $4\\%$ to $15\\%$ . The samples AF4 and AF8 are hard enough to serve as a hard-coating surface, yet their poor vapor spreading capability disqualify them to be AF coatings.  \n\n![](images/c9a64501740cbd72b69d1415e4a59ada50b9532138e85f39866c9bbe42b154d7.jpg)  \nFigure 5. AFM voltage (left part) and topographic (right part) diagrams of the AF coatings of different T20 contents. (a) AF4, (b) AF10, and (c) AF15.  \n\nIn real practice, the service life of an AF coating, which relies on its capability to endure water damaging, is of major concern, in addition to the water wettibility and mechanical strength; in particular, when the coating is to be used in highly humid environments. In this regard, various prepared AF coatings were soaked in water for an extended period of time to see their durability against water invasion. The results are summarized in Table 3. Apparently, coatings with T20 content higher than $10\\%$ cannot withstand long-term soaking; for example, the AF layer of the sample AF15 detaches from the primer after immersed in water for 1 day at $25~^{\\circ}\\mathrm{C}.$ In contrast, AF10 retains its outstanding AF performance even after immersion in water at $60~^{\\circ}\\mathrm{C}$ for 1 day. More interestingly, as manifested by the steam test in Figure 6, this coating still performs well even after one year in service at the ambient condition, ${\\sim}25^{\\circ}\\mathrm{C}$ and $\\sim70\\%$ relative humidity.  \n\nTable 2. Contact Angle, Hardness, Adhesiveness, and AF Performance of Coatings   \n\n\n<html><body><table><tr><td>sample name</td><td>hardness</td><td>contact angle (degree)</td><td>adhesion (%)</td><td>AF performance</td></tr><tr><td>PMMA</td><td><1H</td><td>75</td><td></td><td>misty</td></tr><tr><td>BM</td><td>8H</td><td>70</td><td>100%</td><td>misty</td></tr><tr><td>AF4</td><td>6H</td><td>30</td><td>100%</td><td>misty</td></tr><tr><td>AF8</td><td>5H</td><td>17</td><td>100%</td><td>droplet</td></tr><tr><td>AF10</td><td>5H</td><td>~0</td><td>100%</td><td>transparent</td></tr><tr><td>AF12</td><td>2H</td><td>~0</td><td>35%~65%</td><td>transparent</td></tr><tr><td>AF15</td><td><1H</td><td>~0</td><td><35%</td><td>transparent</td></tr></table></body></html>  \n\n![](images/8b305c38b4700cfbb7ec7239e198e51673a53b1ea1ed3db77b7b78c711745c77.jpg)  \nFigure 6. Steam antifog tests of coatings: (a) AF4 and (b) AF10 after 1 year in service.  \n\nTable 3. Contact Angle (Degree) of the AF Coatings after Water Soaking   \n\n\n<html><body><table><tr><td>sample name</td><td>1 day at 25 °C</td><td>7 days at 25 °C</td><td>1 day at 60 °C</td></tr><tr><td>AF8</td><td>18</td><td>18</td><td>20</td></tr><tr><td>AF10</td><td>~0</td><td>~0</td><td>~0</td></tr><tr><td>AF12</td><td>~0</td><td>detach partly</td><td>detach</td></tr><tr><td>AF15</td><td>detach</td><td>detach</td><td>detach</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# CONCLUSION  \n\nA novel photosensitive surfactant composed of Tween20, IPDI, and 2-HEMA was successfully synthesized. This surfactant could undergo copolymerization with the multifunctional crosslinking agent (DPHA) during UV-curing of the coating sol. By means of a hydrophilic/hydrophobic bilayer design, the prepared hard coating not only demonstrated superb antifog performance but also resisted water penetration effectively. Specifically, the coating containing $10\\%$ modified surfactant is transparent, with a high hardness of 5H on PMMA, and can be soaked in water for 7 days at $25~^{\\circ}\\mathrm{C}$ without losing its AF capability.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 6,
+        "chunk": "# ASSOCIATED CONTENT",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# $\\otimes$ Supporting Information  \n\nSEM and 3-D AFM images of the surface of the bottom layer, FTIR spectrum during reactions of IPDI with 2-HEMA and Tween-20 with 2-HEMA/IPDI, and transmission spectra of the single layer and double layer in the visible region. This material is available free of charge via the Internet at http://pubs.acs.org.",
+        "category": " References"
+    },
+    {
+        "id": 8,
+        "chunk": "# AUTHOR INFORMATION",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# Corresponding Author  \n\n$^{*}\\mathrm{E}$ -mail: lpcheng@mail.tku.edu.tw. Phone: +886-2-26215656 ext. 2725 or 2614. Fax: +886-2-26209887.",
+        "category": " References"
+    },
+    {
+        "id": 10,
+        "chunk": "# Notes  \n\nThe authors declare no competing financial interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 11,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nThe authors thank the National Science Council of Taiwan for the financial support (NSC 96-2628-E-032-001-MY3).",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# REFERENCES  \n\n(1) Oguri, K.; Iwataka, N.; Tonegawa, A.; Hirose, Y.; Takayama, K.; Nishi, Y. Misting-free diamond surface created by sheet electron beam irradiation. J. Mater. Res. 2001, 16, 553−557.   \n(2) Leonard, R. L.; Terekhov, A. Y.; Thompson, C.; Erck, R. A.; Johnson, J. A. Antifog coating for bronchoscope lens. Surf. Eng. 2012, 28 (6), 468−472.   \n(3) Briscof, B. J.; Galvin, K. P. The effect of surface fog on the transmittance of light. Sol. Energy 1991, 46, 191−197.   \n(4) Zhao, H.; Beysens, D. From droplet growth to film growth on a heterogeneous surface - condensation associated with a wettability gradient. Langmuir 1995, 11, 627−634.   \n(5) Gao, X. F.; Yan, X.; Yao, X.; Xu, L.; Zhang, K.; Zhang, J. H.; Yang, B.; Jiang, L. The dry-style antifogging properties of mosquito compound eyes and artificial analogues prepared by soft lithography. Adv. Mater. 2007, 19, 2213−2217.   \n(6) Plasman, V.; Caulier, T.; Boulos, N. Polyglycerol esters demonstrate superior antifogging properties for films. Plast. Addit. Compd. 2005, 7, 30−33.   \n(7) Cebeci, F. C.; Wu, Z. Z.; Zhai, L.; Cohen, R. E.; Rubner, M. F. Nanoporosity-driven superhydrophilicity: A means to create multifunctional antifogging coatings. Langmuir 2006, 22, 2856−2862. (8) Howarter, J. A.; Youngblood, J. P. Self-cleaning and anti-fog surfaces via stimuli-responsive polymer brushes. Adv. Mater. 2007, 19, 3838−3843.   \n(9) Howarter, J. A.; Youngblood, J. P. Self-cleaning and next generation anti-fog surfaces and coatings. Macromol. Rapid Commun. 2008, 29, 455−466.   \n(10) Nuraje, N.; Asmatulu, R.; Cohen, R. E.; Rubner, M. F. Durable antifog films from layer-by-layer molecularly blended hydrophilic polysaccharides. Langmuir 2011, 27, 782−791.   \n(11) Machida, M.; Norimoto, K.; Watanabe, T.; Hashimoto, K.; Fujishima, A. The effect of $\\mathrm{SiO}_{2}$ addition in super-hydrophilic property of $\\mathrm{TiO}_{2}$ photocatalyst. J. Mater. Sci. 1999, 34, 2569−2574.   \n(12) Hattori, A.; Kawahara, T.; Uemoto, T.; Suzuki, F.; Tada, H.; Ito, S. Ultrathin $\\mathrm{SiO_{x}}$ film coating effect on the wettability change of $\\mathrm{TiO}_{2}$ surfaces in the presence and absence of UV light illumination. J. Colloid Interface Sci. 2000, 232, 410−413.   \n(13) Fujishima, A.; Rao, T. N.; Tryk, D. A. $\\mathrm{TiO}_{2}$ photocatalysts and diamond electrodes. Electrochim. Acta 2000, 45, 4683−4690.   \n(14) Tadanaga, K.; Morinaga, J.; Minami, T. Formation of superhydrophobic-superhydrophilic pattern on flowerlike alumina thin film by the sol-gel method. J. Sol-Gel Sci. Technol. 2000, 19, 211−214.   \n(15) Sun, R. D.; Nakajima, A.; Fujishima, A.; Watanabe, T.; Hashimoto, K. Photoinduced surface wettability conversion of $\\mathrm{znO}$ and $\\mathrm{TiO}_{2}$ thin films. J. Phys. Chem. B 2001, 105, 1984−1990.   \n(16) Gao, Y. F.; Masuda, Y.; Koumoto, K. Light-excited superhydrophilicity of amorphous $\\mathrm{TiO}_{2}$ thin films deposited in an aqueous peroxotitanate solution. Langmuir 2004, 20, 3188−3194.   \n(17) Lee, B. I.; Lee, E. S.; Byeon, S. H. Assembly of layered rare-earth hydroxide nanosheets and $\\mathrm{SiO}_{2}$ nanoparticles to fabricate multifunctional transparent films capable of combinatorial color generation. Adv. Funct. Mater. 2012, 22, 3562−3569.   \n(18) Tricoli, A.; Righettoni, M.; Pratsinis, S. E. Anti-fogging nanofibrous $\\mathrm{SiO}_{2}$ and nanostructured $\\mathrm{SiO}_{2}–\\mathrm{TiO}_{2}$ films made by rapid flame deposition and in situ annealing. Langmuir 2009, 25, 12578−12584.   \n(19) Feng, X. J.; Jiang, L. Design and creation of superwetting/ antiwetting surfaces. Adv. Mater. 2006, 18, 3063−3078.   \n(20) Gan, W. Y.; Lam, S. W.; Chiang, K.; Amal, R.; Zhao, H. J.; Brungs, M. P. Novel $\\mathrm{TiO}_{2}$ thin film with non-UV activated superwetting and antifogging behaviours. J. Mater. Chem. 2007, 17, 952−954.   \n(21) Liu, X. M.; He, J. H. Hierarchically structured superhydrophilic coatings fabricated by self-assembling raspberry-like silica nanospheres. J. Colloid Interface Sci. 2007, 314, 341−345.   \n(22) Zhang, L. B.; Li, Y.; Sun, J. $\\mathrm{Q.;}$ Shen, J. C. Mechanically stable antireflection and antifogging coatings fabricated by the layer-by-layer deposition process and postcalcination. Langmuir 2008, 24, 10851− 10857.   \n(23) Faustini, M.; Nicole, L.; Boissiere, C.; Innocenzi, P.; Sanchez, C.; Grosso, D. hydrophobic, antireflective, self-cleaning, and antifogging sol-gel coatings: an example of multifunctional nanostructured materials for photovoltaic cells. Chem. Mater. 2010, 22, 4406−4413.   \n(24) Zhang, L.; Qiao, Z. A.; Zheng, M. A.; Huo, Q. S.; Sun, J. Q. Rapid and substrate-independent layer-by-layer fabrication of antireflection- and antifogging-integrated coatings. J. Mater. Chem. 2010, 20, 6125−6130.   \n(25) Han, J. B.; Dou, Y. B.; Wei, M.; Evans, D. G.; Duan, X. Antireflection/antifogging coatings based on nanoporous films derived from layered double hydroxide. Chem. Eng. J. 2011, 169, 371−378.  \n\n(26) Lu, X. Y.; Wang, Z.; Yang, X. L.; Xu, X.; Zhang, L.; Zhao, N.; Xu, J. Antifogging and antireflective silica film and its application on solar modules. Surf. Coat. Technol. 2011, 206, 1490−1494. (27) Lai, Y. K.; Tang, Y. X.; Gong, J. J.; Gong, D. G.; Chi, L. F.; Lin, C. J.; Chen, Z. Transparent superhydrophobic/superhydrophilic $\\mathrm{TiO}_{2}$ - based coatings for self-cleaning and anti-fogging. J. Mater. Chem. 2012, 22, 7420−7426. (28) Zhang, L.; Lu, C. L.; Li, Y. F.; Lin, Z.; Wang, Z. H.; Dong, H. P.; Wang, T. $\\mathrm{Q.;}$ Zhang, X. M.; Li, X.; Zhang, J. H.; Yang, B. Fabrication of biomimetic high performance antireflective and antifogging film by spin-coating. J. Colloid Interface Sci. 2012, 374, 89−95. (29) Huang, F. H.; Chang, C. C.; Oyang, T. Y.; Chen, C. C.; Cheng, L. P. Preparation of almost dispersant-free colloidal silica with superb dispersiblility in organic solvents and monomers. J. Nanopart. Res. 2011, 13, 3885−3897. (30) Lee, C. K.; Don, T. M.; Lai, W. C.; Chen, C. C.; Lin, D. J.; Cheng, L. P. Preparation and properties of nano-silica modified negative acrylate photoresist. Thin Solid Films 2008, 516, 8399−8407. (31) Chen, C. C.; Lin, D. J.; Don, T. M.; Huang, F. H.; Cheng, L. P. Preparation of organic-inorganic nano-composites for antireflection coatings. J. Non-Cryst. Solids 2008, 354, 3828−3835. (32) Chang, C. C.; Oyang, T. Y.; Hwang, F. H.; Chen, C. C.; Cheng, L. P. Preparation of polymer/silica hybrid hard coatings with enhanced hydrophobicity on plastic substrates. J. Non-Cryst. Solids 2012, 358, 72−76. (33) Jun, J. B.; Park, J. G.; Kim, D. H.; Suh, K. D. Blends of polybutyleneterephthalate with ethylene-propylene elastomer containing isocyanate functional group. Eur. Polym. J. 2001, 37, 597−602. (34) Gao, R. L.; Zhang, M. $\\mathrm{Q.;}$ Dixit, N.; Moore, R. B.; Long, T. E. Influence of ionic charge placement on performance of poly(ethylene glycol)-based sulfonated polyurethanes. Polymer 2012, 53, 1203−1211. (35) Hsu, S. H.; Tang, C. M.; Tseng, H. J. Gold nanoparticles induce surface morphological transformation in polyurethane and affect the cellular response. Biomacromol 2008, 9, 241−248.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# RSC Advances  \n\n![](images/5e530ca58501f385d66ed974cb9f1fc411e94544c35b6eba76ac67fb5b844d56.jpg)  \n\nThis is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication.  \n\nAccepted Manuscripts are published online shortly after acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. This Accepted Manuscript will be replaced by the edited, formatted and paginated article as soon as this is available.  \n\nYou can find more information about Accepted Manuscripts in the Information for Authors.  \n\nPlease note that technical editing may introduce minor changes to the text and/or graphics, which may alter content. The journal’s standard Terms & Conditions and the Ethical guidelines still apply. In no event shall the Royal Society of Chemistry be held responsible for any errors or omissions in this Accepted Manuscript or any consequences arising from the use of any information it contains.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# RSC Advances",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# Synthesis and characterization of UV-curable acrylate film modified by functional methacrylate terminated polysiloxane hybrid oligomer  \n\nHongleiWanga,b,c, WeiquLiua,b\\*, ZhenlongYana,b,c, JianquanTana,b,c and Guolun Xia-Houa,b,c  \n\na Guangzhou Institute of Chemistry, Chinese Academy of Sciences, Guangzhou 510650, China  \n\nb Key Laboratory of Cellulose and Lignocellulosics Chemistry, Chinese Academy of Sciences, Guangzhou 510650, China  \n\nc University of Chinese Academy of Sciences, Beijing 100049, China  \n\n\\* Corresponding author: Email: liuwq@gic.ac.cn  \n\nPostal address: Prof. Weiqu Liu, Guangzhou Institute of Chemistry, Chinese Academy of Sciences, Guangzhou 510650, China Tel: +86-20-85231660 Fax: +86-20-85231660",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# Abstract  \n\nA series of novel methacrylate terminated polysiloxane hybrid oligomer and functional acrylate oligomer were synthesized and characterized by GPC, FT-IR and NMR. Functional polysiloxane oligomer was introduced into acrylate UV-curing system to improve its surface and thermal properties. With increasing the content of organosiloxane segments, contact angle data of the UV-cured films increased, suggesting the organosiloxane segments migrated to the top surface. The SEM and EDS results demonstrated the migrating of organosiloxane segments. The refraction indexes results showed that the optical performance didn’t reduce after organosiloxane segments being incorporated. According the TGA curves, the decomposition temperatures of the polysiloxane/acrylate composite UV-cured films were higher than that of pure acrylate UV-cured film, which demonstrated organosiloxane groups enhanced the thermal properties of acrylate film due to the high energy of the Si-C bond. The observation of the fractured-surface morphology showed that the organosiloxane segments floated onto the surface of the UV-cured films.  \n\nKeyword: Methacrylate terminated siloxane; Functional acrylate oligomer; UV-cured film; Hydrophobic surface",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# RSC Advances",
+        "category": " References"
+    },
+    {
+        "id": 6,
+        "chunk": "# 1． Introduction  \n\nUV-curing polymerization is widely used because of its beneficial properties [1-4], such as rapid curing speed, free-VOC, clean and efficient energy and moderate curing condition [5-8]. (Meth)acrylate groups have been employed widely for photopolymerization because of their strong reactivity, their characteristics of optical clarity, mechanical properties, adhesion and chemical stability, showing rapid, near-complete conversions (i.e., on residual unreacted monomers) with low heat generation [9]. Through the proper selection of acrylic/methacrylic monomers and curing agents, the cured polymers can be tailored to specific performance characteristics. Acrylic/methacrylic polymers form materials which are well known for their uses and applications in many important fields especially in the formulation of paints and surface coatings [10, 11]. However, in these applications materials with poor hydrophobicity are not useful unless they are modified. The acrylic/methacrylic polymers are inferior to some silicon-containing materials in terms of elasticity, flexibility, hydrophobicity and the heat resistance ability [12, 13]. In order to meet the need of high-performance coatings in high-technology areas, the UV-curable acrylic/methacrylic coating formulations must be continuously improved.  \n\nPolysiloxanes are the most important class of polymers with a non-carbon backbone, exhibiting a large degree of main-chain flexibility and high thermal stability due to Si-O groups [14-18]. Therefore, polysiloxanes have attracted much",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# RSC Advances  \n\ninterest and are widely used in modifying polyacrylate coatings. Nevertheless, there is a problem that polysiloxane isn’t compatible well with polyacrylate due to their difference of solubility parameters. To solve this problem, many efforts have been made for the purpose of combining these two materials through chemical methods. Bourgeat-Lami, Bai and Zhao et al. researched on synthesis of polysiloxane and polyacrylate through emulsion polymerization [19-21]. Yu et al. synthesized and evaluated two series of polyacrylate-polydimethylsiloxane (PDMS) block and graft copolymers used in anti-icing coatings [22]. Mostly, research focused on incorporating polysiloxane into the main chain of a polymer, most frequently by emulsion polymerization methods, in order to improve the compatibility. However, emulsion polymerization products showed poor hydrophobicity. Thus, there is an ever increasing demand for polysiloxane modified polyacrylate with better defined, improved and novel physical, chemical and mechanical properties. In this research, we prepared polysiloxane oligomers and then introduced acrylic double bonds by the hydrolysis reaction with methacryloxy propyl trimethoxylsilane at a certain stage. Methacrylate terminated polysiloxane (MATSi) was thus obtained. Owing to the partly similar structure of methacryloxy propyl trimethoxylsilane and polyacrylate, the compatibility between functioned polysiloxane and polyacrylate could be improved.  \n\nThe polyacrylate in this work was synthesized as a novel UV-curable polyacrylate (PA). 6-methylheptyl methacrylate was used as the major monomer since it could",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# RSC Advances  \n\nprovide good plasticity and was economic at the same time. Minor amount of hydroxyethylmethacrylate were added to promote adherence property. Glycidyl methacrylate was used to introduce epoxy groups to react with methacrylate (MA) in the following reaction step. Furthermore, a series of organosiloxane modified polyacrylate (OSPAs) at different organosilicone concentration ratios were respectively prepared by mixing PA with MATSi. In the presence of photoinitiator, OSPAs were crosslinked by the radical polymerization of the carbon-carbon double bonds in UV irradiation, and then the OSPA cured composite coatings were fast prepared. In this way, various properties and enhanced performance could be obtained in the form of OSPA cross-linked structure. The obtained polymers were characterized by gel permeation chromatography (GPC), fourier transform infrared (FT-IR) spectroscopy and nuclear magnetic resonance (NMR). Furthermore, the surface hydrophobic, optical, and thermal property of the cross-linked coatings made from obtained polymers was investigated by gel content test, flexibility test, pencil hardness test, contact angle (CA) analysis, refraction index test, scanning electron microscope, energy dispersive spectrometer, differential scanning calorimetry thermograms and thermogravimetric analyzer.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2. Experimental",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.1 Materials  \n\nOctaphenylpolyoxyethylene (OPE) was obtained from Quzhoumingfeng chemical company. Irgacure 1173 was obtained from Ciba Specialty Chemicals.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# RSC Advances  \n\nDodecylbenzene sulfonic acid (DBSA), glycidyl methacrylate (GMA), hydroxyethylmethacrylate (HEMA), 6-methylheptyl methacrylate (MHMA), methacrylic acid (MA) and methacryloxy propyl trimethoxylsilane (KH570) were purchased from Aladding Industrial Corporation. Octamethylcyclotetrasiloxane $\\mathrm{(D_{4})}$ was provided by Guangzhou Jiahua chemical company. Distilled water, methanol, triethanolamine and azobisisobutyronitrile (AIBN) were purchased from Jingke Chemical Glass Instrument Co., Ltd. Butanone, tetrabutyl ammonium bromide (TBAB) and ethylalcohol were purchased from Sinopharm Chemical Reagent Co., Ltd. All the above materials were used as received without further purification.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# 2.2 Synthesis of polyacrylate  \n\nThe polyacrylate was prepared by using 1:1:8 weight ratio of GMA, HEMA and MHMA in the presence of $4\\mathrm{wt\\%}$ AIBN as initiator and butanone as solvent at a temperature of $80^{\\circ}\\mathrm{C}$ . The reaction was carried out in a four-neck reaction kettle equipped with mechanical stirring, nitrogen inlet, water condenser and thermometer. The reaction was carried out for $8\\mathrm{{h}}$ to obtain desired product. Subsequently, butanone was removed by reduced pressure distillation. The retained desired product was labeled as GHM and was transported into another four-neck kettle. Afterwards, a certain amount of MA was added into the kettle in the presence of $0.8\\mathrm{wt\\%}$ TBAB. The reaction was carried out at $102^{\\circ}\\mathrm{C}$ to reach $99.5\\%$ of the conversion determined by standard acid value. After remaining butanone and unreacted MA were discarded by reduced pressure distillation, the product was obtained and labeled as PA. The general  \n\nprocedure was shown in Scheme 1.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# Scheme 1.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 2.3 Synthesis of MATSi  \n\nMATSi was synthesized by emulsion polymerization. The distilled water, surfactants (DBSA and OPE) and monomers $\\mathrm{(D_{4})}$ were added into a four-necked flask equipped with a thermometer, a reflux condenser, a mechanical stirrer and a nitrogen inlet. DBSA acted as acid catalyst as well. Nitrogen was added into the flask to remove oxygen at first. The reaction was carried out for $8\\mathrm{~h~}$ at $80^{\\circ}\\mathrm{C}$ with stirring at about 500rpm. After being neutralized with NaOH solution to stop the reaction, the final latex of PDMS was obtained. Then a certain quality of KH570 was added into PDMS latex. The condensation reaction of PDMS and KH570 was performed at $80^{\\circ}\\mathrm{C}$ for $^{3\\mathrm{~h~}}$ . The copolymers were precipitated in ethanol and dried in vacuum drying oven. The product was purified in ethanol and hexane several times to remove the unreacted monomers and surfactants. Through this procedure, the product was obtained and designated as MATSi. The reaction scheme is shown in Scheme 2.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# Scheme 2.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 2.4 Preparation of OSPA UV curable films  \n\nPA and MATSi where used in relative mass ratios in the range of 100:0 to 90:10 as reported in Table 1. An amount of $5\\mathrm{wt\\%}$ photoinitiator (Irgacure 1173/triethanolamine $\\begin{array}{r l}{=}&{{}2{:}3}\\end{array}$ w/w) was added into each formulation while stirring for 10 min. Triethanolamine was used to avoid the oxygen inhibition during the UV-curing process. Then films were cast onto a glass plate using $5\\%$ w/v solutions of the",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 17,
+        "chunk": "# RSC Advances  \n\ncopolymers in methanol by means of a wire-wound applicator. The coated films were laid in room temperature for at least 5 minutes until the solvent was evaporated. Then the films were irradiated by a high-pressure mercury lamp (500W) for 30s with a distance of $20\\ \\mathrm{cm}$ from lamp to the surface of samples in air atmosphere. The thickness of the final coating was about $100\\upmu\\mathrm{m}$ .  \n\nTable 1.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# 2.5 Characterization  \n\nThe molecular weight and distributions of PA and MATSi oligomer samples were measured at $25^{\\circ}\\mathrm{C}$ by gel permeation chromatography (GPC) on Waters 2410 instrument with THF as the solvent $\\mathrm{(1.0~ml/min)}$ and polystyrene as the calibration standards.  \n\nThe FT-IR spectra were recorded with TENSOR27, Bruker, Germany spectrometer over the range $400{\\cdot}4000{\\mathrm{cm}}^{-1}$ . 1HNMR and $^{29}\\mathrm{Si}$ NMR were recorded with a 400MHz Bruker NMR spectrometer using $\\mathrm{CDCl}_{3}$ as solvent and tetramethylsilane as the internal reference.  \n\nThe gel content method was performed on the cured films by measuring the weight loss after a 48-h extraction at $80^{\\circ}\\mathrm{C}$ , according to the standard test method ASTM D2665-84[23]. Gel content was calculated as:  \n\n$$\n{\\mathrm{Gel~content}}={\\frac{W t}{W o}}\\times100\\%\n$$  \n\nwhere $W_{0}$ is the initial weight of the film, and $W t$ is the final weight after extraction.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 19,
+        "chunk": "# RSC Advances  \n\nFlexibility of the UV-cured films was measured according to standard test method (ASTM D522) for elongation of attached coatings with conical mandrel apparatus (QTY-32, Shanghai Junda Co., China). Pencil hardness test was conducted on UV-cured films according to the Stander test method ASTM D2263.  \n\nThe contact angle measurements were done by an optical contact angle meter (Shanghai Zhongchen, China) at room temperature $(25^{\\circ}\\mathrm{C})$ using water and ethylene glycol as pendant drops. Each sample was tested more than 5 times at different locations and averaged readings were recorded to obtain a reliable value. The surface free energy was calculated by means of geometric–mean equation which was described by Owens and Wendt [24]. According to Owens and Wendt, the surface energy of a given solid can be determined using an equation applied to two liquids [24, 25].  \n\n$$\n(1+\\mathrm{cos}\\Theta)\\gamma_{1}{=}2(\\gamma_{\\mathrm{s}}^{\\mathrm{\\scriptsize~d}}\\gamma_{1}^{\\mathrm{\\scriptsize~d}})^{1/2}+2(\\gamma_{\\mathrm{s}}^{\\mathrm{\\scriptsize~nd}}\\gamma_{1}^{\\mathrm{\\scriptsize~nd}})^{1/2}\n$$  \n\nwhere $\\upgamma_{\\mathrm{s}}$ and $\\upgamma_{\\mathrm{l}}$ are the surface free energies of the solid and pure liquid, respectively. The superscripts $\\cdot_{\\mathrm{d}},$ and ‘nd’ represent the dispersive and non-dispersive contributions to the total surface energy, respectively. Water $\\mathrm{(\\gamma_{l}=}72.8\\mathrm{mJ/m}^{2}$ , $\\gamma_{\\mathrm{l}}^{\\mathrm{d}}{=}21.8$ $\\mathrm{mJ}/\\mathrm{m}^{2}$ , $\\gamma_{\\mathrm{l}}^{\\mathrm{nd}}{=}51\\ \\mathrm{mJ/m}^{2}$ ), ethylene glycol $\\scriptstyle(\\gamma_{1}=48\\mathrm{mJ}/\\mathrm{m}^{2}$ , $\\gamma_{\\mathrm{l}}^{\\mathrm{d}}{=}29\\mathrm{mJ}/\\mathrm{m}^{2}$ , $\\gamma_{\\mathrm{l}}^{\\mathrm{nd}}{=}19\\mathrm{mJ}/\\mathrm{m}^{2})$ . According to Pinnau and Freeman[26], the contact angle, θ, in Eq. (2) was obtained from the following equation:  \n\n$$\n\\scriptstyle\\Theta=\\cos^{-1}(\\frac{c o s\\bar{\\Theta}_{a}+c o s\\bar{\\Theta}_{r}}{2})\n$$  \n\nwhere $\\theta_{\\mathrm{a}}$ and $\\uptheta_{\\mathrm{r}}$ are the advancing and receding contact angles, respectively.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 20,
+        "chunk": "# RSC Advances  \n\nThe refraction index of the coatings was determined by an Abbe refractometer (WAY-2W, Shanghai Electronics Physical Optics Instrument Co., Ltd) at $20^{\\circ}\\mathrm{C}$ .  \n\nScanning electron microscopy (SEM) and Energy dispersive spectrometer (EDS) were performed. Cross-section morphologies and elementary distribution of the fracture cured coating films were studied by environmental scanning electron microscopy (Hitachi S-4800 FESEM) with an energy dispersive spectrometer. For SEM inspection, samples were fixed to aluminum stubs with conductive tape prior to coating with ${\\sim}20~\\mathrm{nm}$ of gold in an Ernest Fullam sputter coater.  \n\nThe thermal stability of cured polymeric materials was determined using a thermogravimetric analyzer (TGA, TG209F3, NETZSCH, Germany). The thermogravimetric analysis of selected coatings were carried out at heating rate of $20^{\\mathrm{{o}}}\\mathrm{C/min}$ under nitrogen atmosphere (flow rate is $30\\mathrm{ml/min}$ ) in the temperature range of $40–600^{\\mathrm{{o}}}\\mathrm{{C}}$ . The differential scanning calorimetry (DSC) thermograms of UV-cured coating samples were performed using the DSC204 (NETZSCH, Germany) over the range from $-60$ to $120^{\\circ}\\mathrm{C}$ at heating rate of $10^{\\mathrm{{o}}}\\mathrm{{C}/\\mathrm{{min}}}$ and held at $120^{\\circ}\\mathrm{C}$ for 5 min to remove the thermal history under $\\Nu_{2}$ atmosphere.  \n\n3. Results and discussion  \n\n3.1 Synthesis and characterization of OSPA  \n\nFive UV-curable organosiloxane modified polyacrylates, OSPA1, OSPA2, OSPA3, OSPA4, OSPA5 were first prepared in this work in order to study the effects of silicon on the properties of UV-curable composite coatings. The general synthetic scheme for",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 21,
+        "chunk": "# RSC Advances  \n\nthe preparation of the copolymers used in the coating formulations is shown in Scheme 1 for PA and in Scheme 2 for MATSi. GPC, FT-IR, 1HNMR and 29SiNMR spectra were performed to measure the structures of the products. The molecular weights and polydispersity index of the oligomers were characterized by GPC. The typical molecular weight distributions for PA and MATSi were shown in Fig. 1. As shown in Table 2, the number-average molecular weight of PA and MATSi are 2740 and $1295\\mathrm{\\g/mol}$ , respectively. The two mono-modal GPC curves suggested the formation of the two oligomers.  \n\nTable 2.  \n\nThe recorded FT-IR spectra of GHM and PA were reported in Fig 2. Compared with the two traces of GHM and PA in Fig. 2, the disappearance of the characteristic absorption peaks of epoxide group at $910~\\mathrm{cm}^{-1}$ indicates the completion of the reaction. The peaks at $1640~\\mathrm{{cm}^{-1}}$ (methacrylate double bond) and $700~\\mathrm{{cm}^{-1}}$ (C-O-H bending) indicate that the epoxy groups have reacted by addition of MA by a ring-opening addition reaction producing one equivalent of hydroxyl groups. Simultaneously, $\\scriptstyle{\\mathrm{C=C}}$ group was introduced into GHM. Absorbance at frequencies characteristic for acrylates (carbonyl $\\scriptstyle{\\mathrm{C=O}}$ stretch at $1720\\mathrm{{cm}^{-1}}$ , C-O stretch four bands $1140\\mathrm{{cm}^{-1}}$ to $1180~\\mathrm{{cm}^{-1}}$ , $1180~\\mathrm{{cm}^{-1}}$ to $1280~\\mathrm{{cm}^{-1}}$ ,etc) are shown [27]. And meanwhile,",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 22,
+        "chunk": "# RSC Advances  \n\nthe characteristic absorption peaks at 1000 and $900~\\mathrm{{cm}^{-1}}$ for C-O is present in the spectra. Skeleton vibration of $\\mathrm{C=C}$ group was also present at $483~\\mathrm{{cm}^{-1}}$ .  \n\nFig. 3 shows the $^{1}\\mathrm{HNMR}$ spectra of PA in $\\mathrm{CDCl}_{3}$ , peaks in the chemical shift range of 0.7-1.2 ppm and 1.3-1.7 ppm are assigned as $\\mathrm{\\-CH}_{3}$ (a, h, l, u, t) and $\\begin{array}{r}{-\\mathrm{CH}_{2}\\left(\\mathsf{b},\\mathsf{i},\\mathsf{m},\\right.}\\end{array}$ ， o, p, q, r), respectively. The protons resonance signals of –CH (s) and $\\mathrm{\\-CH}_{3}$ (g) appear in the region of 1.5-1.6 ppm and $1.7–2.0\\ \\mathrm{ppm}$ , respectively. The chemical shift of 3.6-3.7 ppm is attributed to protons of $\\mathrm{HO-CH}_{2}(\\mathrm{k})$ and the chemical shift signals at 3.8-3.9 ppm are attributed to proton of HO-CH (d). The peaks at the chemical range of 4.0-4.2 ppm are corresponding to O- $\\mathrm{CH}_{2}$ (c, j, e, n). Peaks at 5.64-5.68 ppm and 6.11-6.18 ppm are assigned as the protons of $\\scriptstyle\\mathrm{C=CH}_{2}$ double bonds (f), indicating that epoxide groups reacted with methacrylic acid thus $C{=}C$ photosensitive groups were introduced.  \n\nThe $^{29}\\mathrm{Si}$ NMR signals of mono $\\left(\\mathrm{T}^{1}\\right)$ )-bi $(\\mathrm{T}^{2})$ -and $\\operatorname{tri}(\\mathbf{T}^{3})$ -fold Si-O-linked silicons can be typically observed in -45,…, -50 ppm, -55,…, -60 ppm and -65,…, -70 ppm region, respectively [28]. In Fig.4, the $^{29}\\mathrm{Si}$ NMR spectra of MATSi are shown. The signal at -68.8 ppm is usually assigned to ${\\boldsymbol{\\mathrm{T}}}^{3}$ which represents KH570 after condensation",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# RSC Advances  \n\npolymerization. The signal of ${\\mathrm{D}}^{2}$ appears in the region of -21.8 ppm. It indicates the ring-opening and condensation polymerization reactions of Octamethylcyclotetrasiloxane. Poly(dimethylsiloxane) with hydroxyl group on the end is the product of the reactions. The peak at chemical shift of -19 ppm belongs to $\\mathbf{D}^{1}$ signal of Si-O group in MATSi structure. There are no signals in the region of -45,..., -50 ppm and -55,…, -60 ppm, which indicates there are no T1and T2 Si-O-linked silicons in the MATSi structure. It also manifests completely hydrolysis and condensation reactions of KH570. These results confirm that the MATSi is successfully prepared.  \n\nThe FT-IR method was also used to confirm the reaction between ring-opened $\\mathrm{D}_{4}$ (PDMS) and KH570. From the IR spectra in Fig.5 it can clearly be observed that PDMS having characteristic peaks at $1018~\\mathrm{{cm}^{-1}}$ and $1089~\\mathrm{{cm}^{-1}}$ which are the characteristic absorption peaks of Si-O-Si. Si- $\\mathrm{CH}_{3}$ stretching vibration peak at 797 $\\mathrm{cm}^{-1}$ was also observed. The peaks of Si-OH at $3699~\\mathrm{{cm}^{-1}}$ indicate that the ring in $\\mathrm{D}_{4}$ was opened and formed polysiloxane. The production MATSi was gained after PDMS reacting with KH570. The spectra of MATSi shows additional absorption peaks at $1722\\ \\mathrm{cm}^{-1}(\\mathrm{C}{=}\\mathrm{O})$ and $1639\\ \\mathrm{cm^{-1}(C{=}C)}$ which represents the reaction between PDMS and KH570.  \n\nThe five UV-cured formulations of PA and MATSi are similar to each other and OSPA3 was shown in Fig. 6. After irradiation, the characteristic $C{=}C$ vibrations at $1640\\mathrm{cm}^{-1}$ decreased apparently.  \n\nThe characteristic peaks discussed above demonstrated the UV-curable hybrid oligomers based on acrylate containing organosilicone groups were successfully synthesized.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# 3.2 Degree of conversion in UV curing  \n\nFT-IR spectroscopy was used to determine the degree of conversion during the UV crosslinking reaction. The absorption band at $1640~\\mathrm{{cm}^{-1}}$ due to $\\scriptstyle{\\mathrm{C=C}}$ vibration was monitored using FT-IR to determine the degree of conversion. The degree of conversion was determined using Eq. (4) [29, 30] $\\mathrm{{Degree~of~conversion}}=(1{-}{\\frac{\\mathit{a t}}{\\mathit{a o}}})\\times100\\$ (4) where $A_{o}$ is the absorption before UV exposure and $A_{t}$ is the absorption after UV exposure. The coating formulation was coated on a KBr window and then exposed to UV radiation for 30 s. As shown in Fig. 7, the decrease in peak area of the $C{=}C$ peak at $1640~\\mathrm{{cm}^{-1}}$ was monitored. Table 3 shows the degree of conversion in coatings after 30s of exposure to UV radiation. All of the OSPA formulations reached high conversion.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 25,
+        "chunk": "# RSC Advances  \n\nTable 3  \n\n3.3 Gel content, flexibility and hardness characterization of the UV-cured coatings For the purpose of assessing the amount of insoluble part in cured films and the mechanical properties of the cured coatings, gel content measurements were conducted. In Table 4, the measured values are summarized. The gel content values of all the films are high enough to indicate the nearly complete cross-linked network of the pure PA and the composite OSPAs. In terms of flexibility, all of the composite OSPA samples passed the test of $8\\mathrm{mm}$ and 6mm diameter, and most of them passed the test of $5\\mathrm{mm}$ diameter, while the pure PA sample failed all the test of $8\\mathrm{mm}$ , 6mm and $5\\mathrm{mm}$ diameter. The hardness value of the samples rises from 3H to 6H with the increasing addition of MATSi. The flexibility and hardness test suggests that introduction of flexible silicon-oxygen segments enhanced mechanical properties of the UV-cured coatings.  \n\nTable 4.  \n\n3.4 Surface and optics characterization of the cured coatings In order to determine the effect of organosilicone on surface and optical properties",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 26,
+        "chunk": "# RSC Advances  \n\nof the UV-cured hybrid oligomers films, contact angle and refraction index were tested respectively. Table 5 presents the contact angle of the five samples. It can be seen that contact angle values of both water and ethylene glycol for pure PA film are much lower than any OSPA cured film. With the increasing of MATSi content, the contact angle values on OSPA cured film surfaces showed a gradually increasing change. It was found that based on the increase of organosilicone concentration, OSPA tended to be more hydrophobic compared with the virgin PA. Since organosilicone possesses low surface energy, they can easily move towards the air-polymer interface causing their enrichment on coating surface to some extent [31, 32]. Thereby, the presence of MATSi could lead to a great decrease in the surface free energy, and among these composite films, OSPA5 presented a very low surface free energy value down to $8.89~\\mathrm{mN/m}$ . Surfaces from mixtures of PA/ MATSi with a ratio of 1:0.02 still show hydrophobicity although the organosilicone content is low. The results shown in Table 5 indicate that organosilicone contribute to the surface hydrophobicity.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 27,
+        "chunk": "# Table 5.  \n\nThe refraction index of the coatings was measured by an Abbe refractometer at $20^{\\circ}\\mathrm{C}$ . The obtained refraction indexes for samples OSPA1, OSPA2, OSPA3, OSPA4, and OSPA5 were listed in Fig. 8. As expected the refraction indexes ranged between 1.5612 and 1.5571 and are consistent with expected values for slight amount of",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 28,
+        "chunk": "# RSC Advances  \n\norganosilicone content in the films. The refraction index of the samples gained a very small change with the increase of the organosilicone content which would not affect the optical properties of the composited material.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 29,
+        "chunk": "# Fig. 8  \n\n3.5 Thermal properties of the cured coatings  \n\nOverall weight loss was observed in composite films with different organosilicone content. The TGA traces of all cured coatings are included in Fig.9, and plots of mass loss versus temperature are shown. To gain better understanding of the degradation behavior of the cured composite coatings, virgin PA film was compared with these composites at three specific degradation temperatures: (a) the temperature of the initial $5\\%$ mass loss $(\\mathrm{T}_{5\\%})$ ; (b) the temperature of the $50\\%$ mass loss $(\\mathrm{T}_{50\\%})$ and (c) residual weight percent at $600^{\\mathrm{{o}}}\\mathrm{{C}}$ . Three specific degradation data are summarized in Table 6. It shows that the typical onset temperature of the degradation is higher for the composites than the virgin PA. The thermal stability of the OSPA composites is enhanced relative to that of virgin PA. All the OSPA samples exhibit an apparent higher temperature at $50\\%$ weight loss during decomposition compared with pure PA. The different thermal properties between virgin PA and OSPA may be attributed to some interaction between organosilicone and PA that serves to stabilize the composite. The thermal stability of the composites systematically increases with increasing organosiloxane. The results demonstrate that the incorporated organosiloxane play an",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 30,
+        "chunk": "# RSC Advances  \n\nimportant role during decomposition. The residual silicon-contained compound act as an insulator and mass transport barrier to the volatile products generated during decomposition. Meanwhile, compared with virgin PA, the more complex OSPA network reduced the overall rate of volatiles evolution.  \n\nGlass transition temperature $(T_{\\mathrm{g}})$ of the UV-cured films were investigated by differential scanning calorimetry (DSC). Fig. 10 shows the DSC thermograms of PA and OSPAs. The $T_{\\mathrm{g}}$ value of all the samples are summarized in Table 6. There was an increasing trend of $T_{\\mathrm{g}}$ value as the amount of MATSi in pure PA increasing.  \n\nTable 6. .  \n\nFig. 9.  \n\n3.6 Micro-morphology of the cured coatings  \n\nFig.11 shows the fractured-surface microstructure of the cured films cast onto glass slides from a PA/ MATSi ratio of 98:2, 96:4, 94:6, 92:8 and 90:10. Sample (a) exhibits a uniform distribution for the network of virgin PA. However, the fracture surface of OSPAs showed rougher features than that of virgin PA. These observations also indicate that the distribution of organosilicone copolymer in virgin PA is not homogeneous. In addition, it can be clearly observed that a certain extent of sphere",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 31,
+        "chunk": "# RSC Advances  \n\nwere enriched closed to the air side surface and there were also spheres in the matrix. This observation evidenced that the silicon-contained groups moved towards the air side surface of the cured films. These results can be explained as follows: During the solvent evaporation, silicon-contained groups move towards the top side surface of the UV-cured formulations owing to the poor compatibility with PA. These observations are in good agreement with the results obtained by contact angle value. When the content of MATSi increases, the phase separation appeared and became more obviously at the interphase [33-35]. It can be inferred that the hydrophobic surface may resulted from the silicon-contained segments in MATSi groups. The EDS results in Fig.12 showed energy-spectrum scanning from bottom to top of the film. It also indicated that the silicon-contained groups assembled on the surface of the films which agrees well with SEM and contact angle data. Furthermore, the silicon spheres are always at the end of the crack, which means they could efficiently absorb the energy generated in the fracture process and prevent aggravated fracture.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 32,
+        "chunk": "# 4. Conclusion  \n\nA novel methacrylate terminated polysiloxane was synthesized by hydrolysis reaction using octamethylcyclotetrasiloxane and methacryloxy propyl",
+        "category": " Conclusions"
+    },
+    {
+        "id": 33,
+        "chunk": "# RSC Advances  \n\ntrimethoxylsilane. Methacrylate groups were incorporated into functional polysiloxane oligomer to enhance the compatibility between organosiloxane segments and acrylate film. With the incorporation of organosiloxane OSPA gained increased thermal and mechanical properties compared to the virgin PA. Besides that, it was determined that owing to the hydrophobicity of organosilicone segments, the cured coating films containing PDMS had low surface free energy, and higher thermal degradation temperature. SEM and EDS studies of the coatings depicted that silicon-contained groups gathered on the air-side surface of the cured films. The low cost hydrophobic UV-curable OSPA coatings have a promising combination of physical and mechanical properties which will lead to potential application in industrial coatings fields such as printing inks, paints, adhesives and packaging overcoat film.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 34,
+        "chunk": "# 5. Acknowledgements  \n\nThis study was financially supported by the Program “Tianhe District science and technology plan”.",
+        "category": " References"
+    },
+    {
+        "id": 35,
+        "chunk": "# References  \n\n[1] C. Chen, M. L. Li, Y. J. Gao, J. Nie and F. Sun, RSC Adv., 2015, 5, 33729.   \n[2] D. Knittel and E. Schollmeyer, Polym. Int., 1998, 45 (1): 110-117.   \n[3] K. J. van den Berg, L.G. J. van der Ven and H. J. W. van den Haak, Prog. Org. Coat., 2008, 61: 110-118.",
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+        "chunk": "# RSC Advances  \n\n[17] S. W. Zhang, Z. D. Chen, M. Guo, J. Zhao and X. Y. Liu, RSC Adv., 2014, 4, 30938.   \n[18] M. Alexandre and P. Dubois, Mater. Sci. Eng: R: Reports., 2000, 28(1): 1-63.   \n[19] M. Lin, F. Chu, A. Guyot, J. L. Putaux and E. Bourgeat-Lami, Polymer., 2005, 46: 1331-1337.   \n[20] H. Li, S. Liu, J. Zhao, D. Li and Y. Yuan, Thermochim. Acta., 2013, 573: 32-38.   \n[21] R. Bai, T. Qiu, F. Han, L. He and X. Li, Appl. Surf. Sci., 2012, 258: 7683-7688.   \n[22] ASTM D2665-84, Standard Specification for Poly(Vinyl Chloride) (PVC) Plastic Drain, Waste, and Vent Pipe and Fittings, reapproved 2009.   \n[23] D. Yu, Y. Zhao, H. Li, H. Qi, B. Li and X. Yuan, Prog. Org. Coat., 2013, 76: 1435-1444.   \n[24] D. K. Owens and R. C. Wendt, J. Appl. Polym. Sci., 1969, 12: 1741-1747.   \n[25] T. Ç. Çanak and Đ. E. Serhatlı, Prog. Org. Coat., 2013, 76: 388-399.   \n[26] Formation and modification of polymeric membranes: overview, in: I. Pinnau,B.D. Freeman (Eds.), 214th National Meeting of the American-Chemical-Society, Las Vegas, NE, 1997, pp. 1– 22.   \n[27] V. V. Krongauz, Thermochim. Acta., 2010, 503-504: 70-84.   \n[28] K. Albert, E. Bayer and B. Pfleiderer, J. Chrom., 1990, 506: 343.   \n[29] W. Xiao and W. Tu, J. Chem. Eng. Chin. Univ., 2009, 2: 13.   \n[30] I. Rehman, E. H. Andrews and R. Smith, J. Mater. Sci: Mater. Med., 1996, 7(1): 17-20.   \n[31] H. Tavana, F. Simon, K. Grundke, D. Y. Kwok, M. L Hair and A. W. Neumann,",
+        "category": " References"
+    },
+    {
+        "id": 38,
+        "chunk": "# RSC Advances  \n\nJ. Colloid. Interf. Sci., 2005, 291(2): 497-506.  \n\n[32] Y. S. Kim, J. S. Lee, Q. Ji and J. E. McGrath, Polymer., 2000, 43(25): 7161-7170.   \n[33] Z. Yan, W. Liu, N. Gao, H. Wang and K. Su, Appl. Surf. Sci., 2013, 284: 683-691.   \n[34] M. Sangermano, W. Carbonaro, R. Bongiovanni, R. R. Thomas and C. M. Kausch, Macromol. Mater. Eng., 2010, 295(5): 469-475.   \n[35] W. Liu, S. Ma, Z. Wang, C. Hu and C. Tang, Macromol. Res., 2010, 18(9): 853-861.  \n\nFigure captions:  \n\nScheme 1. Synthesis route of UV-cured PA  \n\nScheme 2. Synthesis route of MATSi  \n\nFigure 1. GPC traces of PA (a) and MATSi (b)  \n\nFigure 2. FT-IR spectra of GHM and PA  \n\nFigure 3. $\\mathrm{^1H}$ NMR spectra of PA  \n\nFigure 4. $^{29}\\mathrm{Si}$ NMR spectra of the synthesis of MATSi  \n\nFigure 5 FT-IR spectra of the synthesis of MATSi  \n\nFigure 6. FT-IR spectra of the synthesis of OSPA  \n\nFigure 7. FT-IR spectra of the UV-curable film formulations of PA and OSPAs. a)  \n\nBefore irradiation; b) After UV-curing  \n\nFigure 8. Refraction Indexes of the UV-cured coatings  \n\nFigure 9. TGA curves of the UV-cured coatings.  \n\nFigure 10. DSC thermograms of the UV-cured PA and OSPA coatings  \n\nFigure 11. SEM images of fractured-surface morphologies of the UV-cured coatings:  \n\n(a)PA; (b)OSPA1; (c)OSPA2; (d)OSPA3; (e)OSPA4; (f)OSPA5.  \n\nFigure 12. EDS images of fractured surface of the UV-cured coatings",
+        "category": " References"
+    },
+    {
+        "id": 39,
+        "chunk": "# RSC Advances  \n\n![](images/44e5fc93a42287494586facecd0d8f89820b94015455baeb9984e9af101c69fd.jpg)  \n\n![](images/948b2014fa182b52204acce90a766d525a7faa8e5600bd4f4c648237aabae0f1.jpg)  \nScheme 1. Synthesis route of UV-cured PA $70{\\times}173{\\ m m}$ $600\\times600$ DPI)  \n\n![](images/6fa80ac3e1eec1ca554dbf580f61cd33af9afe083b40cb2cc97f788a9e9becd0.jpg)  \nScheme 2. Synthesis route of MATSi $21\\times30\\mathsf{m m}$ $600\\times600$ DPI)  \n\n![](images/0f90e4a97015595a317bc21fe68c8b3f117b7c164f922cf33a5068a44942ef7f.jpg)  \nFig.1. GPC traces of PA (a) and MATSi (b) $70\\times49\\mathsf{m m}$ ( $300\\times300$ DPI)  \n\n![](images/a0083c3ee6fd06b29f80d3ecd3aac8c227e5519551719d59c28017297d789d3c.jpg)  \nFig.2. FT-IR spectra of GHM and PA 201x141mm ( $300\\times300$ DPI)  \n\n![](images/70dc5ae7aea8d51b8d7782e0b06d06750d96e2ff74e42fcc9d5219846c52f3a6.jpg)  \nFig.3. $<1>H$ NMR spectra of PA 201x140mm ( $300\\times300$ DPI)  \n\n![](images/4f1c3ef0c6984a3bb163f43d2fc68fc5dd479212bd1706e69c83128d8b2184ba.jpg)  \nFig.4. ${<}29{>}\\mathsf{S i}$ NMR spectra of the synthesis of MATSi $70\\times49\\mathsf{m m}$ $300\\times300$ DPI)  \n\n![](images/bfeda737eb8642494b1e9cd9fd8e3f3006e4df1a2ee2bc394cb24ba7a6bc9e55.jpg)  \nFig.5. FT-IR spectra of the synthesis of MATSi $210{\\times}148\\mathsf{m m}$ ( $300\\times300$ DPI)  \n\n![](images/c61acef0ebd1eacdbbbfe4145beabb8deb2dcef918bfa8fe4b3185c4900e4981.jpg)  \nFig.6. FT-IR spectra of the synthesis of OSPA 201x141mm ( $300\\times300$ DPI)  \n\n![](images/7f1bf37f5e9add8a3caf1c524abb72c5d11e03219c6523668a1fe36f7f9421ba.jpg)  \nFig.7. FT-IR spectra of the UV-curable film formulations of PA and OSPAs. a) Before irradiation; b) After UVcuring. 201x140mm (300 x 300 DPI)  \n\n![](images/d84d689271fb6343e8de700d9bfd15c4f38ea92b88e24b03e9dc3ba49823a024.jpg)  \nFig.8. Refraction Indexes of the UV-cured coatings $70\\times49\\mathsf{m m}$ ( $300\\times300$ DPI)  \n\n![](images/6642d30f10d629705abdb77ec7a986e09043f3253ed7495ca726a442ff941004.jpg)  \nFig.9. TGA curves of the UV-cured coatings $70\\times49\\mathsf{m m}$ $300\\times300$ DPI)  \n\n![](images/a30765e1d7dd9b30750b7bc29f22094bf331cc9a64109e5161ad6c56926af553.jpg)  \nFig.10. DSC thermograms of the UV-cured PA and OSPA coatings $70\\times49\\mathsf{m m}$ $300\\times300$ DPI)  \n\n![](images/37259f855c579e8f8a47a3737f59456601e481584c7b83dd4aac351c1302bef2.jpg)  \nFig.11. SEM images of fractured-surface morphologies of the UV-cured coatings: (a)PA; (b)OSPA1; (c)OSPA2; (d)OSPA3; (e)OSPA4; (f)OSPA5 49x23mm ( $300\\times300$ DPI)  \n\n![](images/45d1d525f6f421fbc6268f69af2bf3838a7db69441a5d0ec7deac070637d2742.jpg)  \n\nFig.12. EDS images of fractured surface of the UV-cured coatings $90\\times90\\mathrm{mm}$ $300\\times300$ DPI)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 40,
+        "chunk": "# RSC Advances  \n\nTable 1. Mass ratio of PA and MATSi.   \n\n\n<html><body><table><tr><td>Samples</td><td>PA (%)</td><td>MATSi (%)</td></tr><tr><td>Pure PA</td><td>100</td><td>0</td></tr><tr><td>OSPA1</td><td>98</td><td>2</td></tr><tr><td>OSPA2</td><td>96</td><td>4</td></tr><tr><td>OSPA3</td><td>94</td><td>6</td></tr><tr><td>OSPA4</td><td>92</td><td>８</td></tr><tr><td>OSPA5</td><td>90</td><td>10</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 41,
+        "chunk": "# RSC Advances  \n\nTable 2. Molecular weights of PA and MATSi oligomers   \n\n\n<html><body><table><tr><td>Samples</td><td> Mna</td><td>PDIb</td></tr><tr><td>PA</td><td>2740</td><td>2.18</td></tr><tr><td>MATSi</td><td>1295</td><td>2.09</td></tr></table></body></html>\n\n$^{\\mathrm{a}}\\mathrm{Mn}$ : the number-average molecular weight, determined by GPC. bPDI:the polydispersity index, determined by GPC.  \n\nTable 3. Degree of conversion of double bonds in the UV cured coatings   \n\n\n<html><body><table><tr><td>Coating</td><td>Conversion (%)</td></tr><tr><td>PA</td><td>95</td></tr><tr><td>OSPA1</td><td>96</td></tr><tr><td>OSPA2</td><td>97</td></tr><tr><td>OSPA3</td><td>99</td></tr><tr><td>OSPA4</td><td>97</td></tr><tr><td>OSPA5</td><td>98</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 42,
+        "chunk": "# RSC Advances  \n\nTable 4.Gel content, flexibility and hardness characterization of the UV-cured coatings.   \n\n\n<html><body><table><tr><td rowspan=\"2\">Samples</td><td rowspan=\"2\">Gel content (%)</td><td colspan=\"3\">Flexibility</td><td rowspan=\"2\">Pencil hardness</td></tr><tr><td>8mm</td><td>6mm</td><td>5mm</td></tr><tr><td>Pure PA</td><td>97</td><td>Fail</td><td>Fail</td><td>Fail</td><td>3H</td></tr><tr><td>OSPA1</td><td>98</td><td>Pass</td><td>Pass</td><td>Fail</td><td>5H</td></tr><tr><td>OSPA2</td><td>97</td><td>Pass</td><td>Pass</td><td>Pass</td><td>6H</td></tr><tr><td>OSPA3</td><td>98</td><td>Pass</td><td>Pass</td><td>Pass</td><td>6H</td></tr><tr><td>OSPA4</td><td>98</td><td>Pass</td><td>Pass</td><td>Pass</td><td>6H</td></tr><tr><td>OSPA5</td><td>98</td><td>Pass</td><td>Pass</td><td>Pass</td><td>6H</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 43,
+        "chunk": "# RSC Advances  \n\nTable 5. Contact angle of the UV-cured coatings.   \n\n\n<html><body><table><tr><td colspan=\"2\">Surface free energy(mN/m)</td><td colspan=\"2\">Contact angle (0)with</td></tr><tr><td></td><td>Ys</td><td>Deionized water</td><td>Ethylene glycol</td></tr><tr><td>PA</td><td>44.28</td><td>94</td><td>55.75</td></tr><tr><td>OSPA1</td><td>11.70</td><td>102.5</td><td>91</td></tr><tr><td>OSPA2</td><td>12.73</td><td>108.5</td><td>91</td></tr><tr><td>OSPA3</td><td>10.36</td><td>108.5</td><td>94.5</td></tr><tr><td>OSPA4</td><td>13.27</td><td>109.5</td><td>91</td></tr><tr><td>OSPA5</td><td>8.89</td><td>114</td><td>99.5</td></tr></table></body></html>\n\n$\\upgamma_{\\mathrm{s}}$ surface free energy of solid.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 44,
+        "chunk": "# RSC Advances  \n\nTable 6. Thermal properties of the UV-cured coatings.   \n\n\n<html><body><table><tr><td>Sample</td><td>T5%</td><td>T50%</td><td>wt% at 600℃</td><td>Tg</td></tr><tr><td>PA</td><td>187.8</td><td>304.1</td><td>0</td><td>15.67</td></tr><tr><td>OSPA1</td><td>220.6</td><td>339.7</td><td>0.3</td><td>22.05</td></tr><tr><td>OSPA2</td><td>211.5</td><td>338.2</td><td>0.9</td><td>24.01</td></tr><tr><td>OSPA3</td><td>190.8</td><td>335.9</td><td>1.2</td><td>27.92</td></tr><tr><td>OSPA4</td><td>183.9</td><td>343.5</td><td>2.7</td><td>27.99</td></tr><tr><td>OSPA5</td><td>224.1</td><td>345.1</td><td>8.2</td><td>27.05</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,202 @@
+[
+    {
+        "id": 1,
+        "chunk": "Stuart G. Croll  \n\nNorth Dakota State University Coatings and Polymeric Materials  \n\nDiagrams by Dr. Olena Shavranska  \n\nCopyright S. G. Croll, NDSU  \n\nSummary  \n\n• Background and Definitions   \nPaint Properties   \n• Viscometers   \n• Solution rheology   \n• Suspension rheology  \n\nRheology  \n\n• Rheology $\\mathbf{\\tau}=$ science of flow and deformation ( materials characteristics)  \n\n• Fluid Mechanics $\\mathbf{\\tau}=$ science of where fluids flow to in given processes.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Importance of Rheology  \n\n• Most convenient state to apply coatings is as a liquid (can also be done as a powder or gas)  \n\n– Brush – Roll – Spray, etc  \n\n• Therefore paint must be made into a liquid form  \n\n– Solution properties – Suspension properties – Mixing – Drying and Curing  \n\nCopyright S. G. Croll, NDSU  \n\nPaint, Inks, Sealants, Caulks, Cosmetics, and Packaged Foods etc.  \n\n• Consist of:  \n\n– Solutions: binder polymers, dispersants, thickeners, cross-linkers  \n\n– Suspensions: latex, pigments, extenders, non-aqueous dispersions, emulsions, defoamers, surfactant micelles  \n\nHow do we define flow properties?  \n\n• Materials flow when pushed (forced) – Stress is important  \n\n• How much they flow is important (changes of shape)  \n\n– Simple liquids require no force to retain their shape  \n\n– How fast they are strained is the important factor that determines how much force is needed",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# Viscosity Definition  \n\n• Liquids’ flow is usually determined by the shear stress imposed, or the change of flow rate through the liquid, Newton’s law:  \n\n$$\n{\\boldsymbol{\\tau}}=\\eta{\\dot{\\boldsymbol{\\gamma}}}\n$$  \n\nWhere  \n\nThis is Newtonian behavior $\\mathbf{\\tau}=\\mathbf{\\tau}$ linear, no time dependence   \nShear rate is the time differential of the shear strain and is given, in shear, by the velocity, $\\nu$ , gradient across the flow:  \n\n$$\n\\dot{\\gamma}=\\frac{\\delta\\nu}{\\delta y}\n$$  \n\nCopyright S. G. Croll, NDSU",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# Viscosity  \n\nViscosity $\\mathbf{\\tau}=\\mathbf{\\tau}$ resistance to flow  \n\n$\\mathbf{\\Sigma}=$ resistance to movement of molecules; solvent, solute and suspended matter through space.   \n\\~ inverse of diffusion coefficient of molecules or particles through the medium  \n\nNewtonian flow is for liquids what Hooke’s law is for solids (elastic solids)  \n\nHowever, since liquids flow to accommodate stress, the complementary variables are stress and strain-rate (in shear usually).",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# Shear Deformation  \n\n• Shear Deformation can be visualized like a pack of cards   \n• A force $F$ is applied to the uppermost volume element (thickness $d y)$ , the material will deform by the displacement $d x$ of adjacent elements.  \n\n• Shear rate $\\mathbf{\\tau}=\\mathbf{\\tau}$ rate of change of the shear strain $\\mathbf{\\Sigma}=$ change in the velocity across the thickness direction (y here) of the element $\\mathbf{\\Sigma}=\\mathbf{\\Sigma}$ [distance/time $\\div$ distance $\\mathbf{\\tau}=\\mathbf{\\tau}/\\mathrm{tim}\\mathbf{e}]=\\mathbf{s}^{-1}$  \n\n• Shear Stress $\\mathbf{\\tau}=\\mathbf{\\tau}$ Shear force, $\\mathrm{~F~}\\div$ Area, A  \n\n![](images/b8bd3f6c1ba4e80a6797182e0188f68d3f21e30b65376001ec67ff19adfdc9e8.jpg)  \nShear Deformation  \n\n<html><body><table><tr><td>Shear Strain</td></tr><tr><td>In shear, strain is not a relative increase in length, area or volume, but a change in shape (angle) given by: 4x</td></tr><tr><td>4y And in the infinitesmal limit by: dx 2</td></tr></table></body></html>  \n\n<html><body><table><tr><td>Units and Conversions</td></tr></table></body></html>  \n\nCopyright S. G. Croll, NDSU   \n\n\n<html><body><table><tr><td></td><td>CGS</td><td>MKS</td><td>SI</td></tr><tr><td>Strain</td><td>dimensionless</td><td>dimensionless</td><td>dimensionless</td></tr><tr><td>Strain rate</td><td>s-1</td><td>s-1</td><td>s-1</td></tr><tr><td>Stress</td><td>dyne/cm²</td><td>Newton/m²</td><td>Pascal (Pa) (=1 Newton/m2)</td></tr><tr><td>Viscosity (liquids)</td><td>Poise (P) (=1 dyne-s/cm²) centipoise (cP) (=0.01 P = 1 m Pa-s)</td><td>Newton-s/m²</td><td>Pa-s (=10 P) mPa-s (= 10-3 Pa-s = 1 cP)</td></tr><tr><td>Modulus (solids)</td><td>dyne/cm²</td><td>Newton/m2</td><td>Pa</td></tr></table></body></html>  \n\n<html><body><table><tr><td>Note: Kinematic Viscosity</td></tr><tr><td>Occasionally used = viscosity/density</td></tr><tr><td>Units: “Stokes\" in c.g.s. m²/s in S.I. or M.K.S.</td></tr><tr><td>Copyright S.G.Croll,NDSU 13</td></tr></table></body></html>  \n\nExamples: orders of magnitude",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# Viscosity Application Shear Rates  \n\nAir,  a Gas $10^{-5}$ Pa.s Water 10-3 Glycerine 1 Syrup $10^{2}$ Glass, a solid $10^{21}$  \n\nBrushing 4000-10000 s-1 Brush Pick-up $5{\\mathrm{~}}{\\mathrm{{s}}}^{-1}$ Spraying $10^{3}-10^{6}$ Settling $\\sim10^{-3}$ Sagging $10^{-2}\\ –\\ 10^{-1}$ Leveling $10^{-1}$ Coil Coating $10^{4}$ Hand Rolling $\\mathord{\\sim}500$  \n\nCopyright S. G. Croll, NDSU",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# Example: Balance of Properties in HousePaint  \n\nDifferent applications have different requirements on viscosity:  \n\nSagging needs high viscosity to counter it   \nLeveling needs low viscosity so brushmarks etc. disappear (note the problem vs. sag)   \nApplication by brush and roll needs a low viscosity so that it is easy (but the coating must level and not sag)   \nIf the brushing or rolling is done at too low a viscosity – the coating is too thin and may bead up   \nThe viscosity has to be high enough that the brush picks up enough paint.   \nSpraying viscosity must be low (for pumping and atomization)  \n\nThe time-dependence and non-linear behavior of typical paint gives us ways to achieve all these properties.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# Leveling Geometry  \n\n![](images/806a020b288aaf3b2fc02e7a33db675ff0f01beefe374faf122af51d65d2620a.jpg)  \n\n<html><body><table><tr><td>Example: Leveling in Newtonian Paint</td></tr><tr><td>Leveling expresses how fast the brushmarks or roller spatter disappear. To a first approximation they disappear exponentially in time: Amplitude(t)= Ampt=o.exp(-t/t.)</td></tr><tr><td>3L'n (2π)4oh3 Where the time constant, t is given by: t, = -</td></tr><tr><td>L = wavelength of the brushmark, longer goes away more slowly, o= surface tension of the fluid, high values help leveling</td></tr><tr><td>speed. h = thickness, so leveling is very sensitive to thickness, thicker coatings level quicker</td></tr></table></body></html>  \n\nExample: Sagging in Newtonian Paint  \n\nThere is a balance of forces between the viscous drag within a paint film and the force of gravity making the paint run down the wall.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# Coating  \n\n$$\n\\scriptstyle{\\dot{\\gamma}}\\left(x\\right)={\\frac{\\rho g\\left(h-x\\right)}{\\eta}}\n$$  \n\n$g=$ acceleration due to gravity $\\rho=$ density of the paint $h=$ thickness of the paint At $x=0$ (outer surface of paint), sag movement is greatest At wall, $x=h$ , there is no movement  \n\n![](images/53bf1fb5bf2d0475a9cdc7ac72d919701332a079e2ba5cde7ba17212be42a1f0.jpg)  \n\nHigh viscosity helps stop movement",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# Real Materials (inc. paints) are NonNewtonian  \n\n• Newtonian liquids are “ideal” – Liquid does not change under flow so viscosity does not change Real Liquids are not ideal – They change so their properties depend on the previous motion They have memory, i.e. $\\mathbf{\\Sigma}=\\mathbf{\\Sigma}$ time dependent – Molecular and particle interactions depend on rate of deformation They are non-linear – They may also be reacting and drying as well",
+        "category": " Introduction"
+    },
+    {
+        "id": 11,
+        "chunk": "# High vs. Low shear rate  \n\n• High Shear rates  \n\n– All specific interactions are overcome by high energy of flow   \n– Viscosity depends mainly on viscosity of solvent and the volume concentration of dissolved or dispersed phases  \n\n• Low Shear rates  \n\nSpecific interactions  remain between components Viscosity is often orders of magnitude higher than at high shear rates because of these interactions  \n\n<html><body><table><tr><td>Time Dependent Behavior = Solid-like behavior (in liquids)</td></tr><tr><td>If liquids have memory, then they have some elements of solid-like behavior and we can use solid-like concepts to describe these attributes:</td></tr><tr><td>Elasticity</td></tr><tr><td>Yield Stress Normal Forces</td></tr><tr><td>Extensional Viscosity The overall combination of viscous and elastic behavior is</td></tr><tr><td>termed “viscoelastic\",as in solids Time-dependent solids, e.g. solid polymers, are also called</td></tr><tr><td>viscoelastic</td></tr><tr><td>PAINTSARE VISCOELASTIC Copyright S.G.Croll,NDSU 21</td></tr></table></body></html>  \n\n<html><body><table><tr><td>Elasticity - a form of time-dependence in liquids</td></tr><tr><td>Liquids may recoil when shearing stops, i.e. solid-like - hence“elasticity” The response to a changing stress or shear rate may not be completely in phase with it - i.e. time-dependent properties (relaxation) - for liquids, the in-phase part of the response is the viscosity and the out-of-phase component is the shear modulus (solid-like part of the response)</td></tr></table></body></html>  \n\n![](images/5e3d8b92d4583f0ff48a87eb35911365f5b4efd891819fcfb994dee32abe6ff9.jpg)  \nCopyright S. G. Croll, NDSU  \n\nWhat if the material does not respond proportionally?  \n\n• Non-linear fluids exhibit a great variety of behaviors.  \n\n– Usually paints, solutions and dispersions are “shear-thinning”   \n– They may exhibit a “yield stress” (plastic behavior)   \n– Sometimes they “shear-thicken”   \n– Occasionally they conform to other jargon  \n\n“Newtonian” liquids are linear and are not timedependent.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# Shear-Thinning Fluids  \n\nViscosity decreases with increasing shear-rate or increasing shear stress,  another term for this is “pseudoplastic” The term does not  imply time-dependence necessarily (but most paints are as well)  \n\nDispersions and solutions are usually shear-thinning above a dilute concentration.  \n\nThe two main reasons for shear-thinning in suspensions:  \n\nBreakdown of flocculation, i.e. releasing more liquid from within the flocc. to lubricate the particles and decrease the effective volume solids.   \nIn non-flocculated systems, often there are inter-particle correlating forces or arrangements that are overcome at higher shear stresses when the system becomes randomized or the particles may order themselves along the direction of flow.  \n\nSolutions shear-thin for similar reasons; entanglements breakdown and molecules elongate along the flow direction",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# As particles align along the flow , the viscosity diminishes.  \n\nLining-up occurs more at both higher deformation rates and longer times. Produces non-linear and time-dependent elements of the viscosity response  \n\n![](images/f0f8612f32859bef43442f2ed26a9abbc74628743f12c0a50f8d3a6a142fa25a.jpg)  \n\nLining-up occurs in spatially confined flows – most coatings applications, and in shear-thinning fluids – most of coatings, see: S. V. Loon, J. Fransaer, C. Clasen, J. Vermant, “String Formation in sheared suspensions in rheologically complex media: The essential role of shear thinning,” J. Rheol., 58(1), 237 – 254, 2014  \n\n![](images/8b47d2b526efb261b48bb52ff6f65873a11a7aa0700f50bd7a506c6537998849.jpg)  \n\n![](images/b5424a79ec76ab1ef961948c8e50e8552b15e3307e459e196e99fbd1eafacf37.jpg)  \nPaints are Shear-Thinning and Time-Dependent, example:  \n\n![](images/a06ff19bbbbeca68082caf08fdd8cb0e043a8b5c37d9497f7ce884b206b12cf1.jpg)  \nCopyright S. G. Croll, NDSU  \n\n![](images/9c45802bcca86e50b95fc161471e43835ee1c50e1c1be9771cc8b702135edcb9.jpg)  \nCopyright S. G. Croll, NDSU",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# “Yield Stress”  \n\n• Some fluids seem not to flow at very low stresses, but only flow above a certain critical stress referred to as the “yield” stress. – This is called “plastic” behavior by analogy to solids.   \n• Below this yield, there is no flow so the viscosity is infinite(?)   \nThere are those who believe that yield cannot really exist (we just need more sensitive rheometers) – but it can be a useful description of fluid behavior.  \n\n![](images/00bc2289b4e20787279dc778feccbef1d7cfc7cd31d18c06e9b2d7ec6ae52e82.jpg)  \n\n![](images/555f3c6e323bfd3b18d81f4503ff8ad44a3d331c5f51c8fc0925d0b02a4cd5a6.jpg)  \nCopyright S. G. Croll, NDSU  \n\n33",
+        "category": " Introduction"
+    },
+    {
+        "id": 15,
+        "chunk": "# Shear-Thickening  \n\nUsually happens at high shear-rates and in systems that are more concentrated. May happen because particles get jammed together and do not have enough room to move around each other quickly enough Disperse phase effectively increases in concentration $\\mathbf{\\sigma}=\\mathbf{\\sigma}$ “dilatant” behavior May also happen because strings of particles tumble at high flow rates. Flocculation can be induced at the high collision rates imposed by high shearrates.  \n\nSee also: E. Brown, H. M Jaeger, “Shear thickening in concentrated suspensions: phenomenology, mechanisms and relations to jamming,” Rep. Prog. Phys. 77 (2014) 046602 (23pp)  \n\n![](images/abc5c8ec24d01496ef791f8214214d491c7f1ecf6ae9b01b1f2c792d5e91a315.jpg)  \nN. J. Wagner, J. F. Brady, \"Shear Thickening in colloidal dispersions, Physics Today, 62(10), 27 - 32 (2009)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# More about Time-Dependence  \n\n“Thixotropic” behavior $\\mathbf{\\tau}=\\mathbf{\\tau}$ viscosity diminishes with time under shear – Very typical behavior in paints, food etc. – Intermolecular or inter-particle interactions breakdown with time under stress • Flocculation, hydrophobic association or polar interactions – Detected in “hysteresis” loop experiments  \n\n• “Rheopexy” is the opposite behavior and unusual  \n\n<html><body><table><tr><td colspan=\"4\">Thixotropic Behavior, some examples (time-dependent) >  between j, and 0</td></tr><tr><td colspan=\"4\">=0 >0</td></tr></table></body></html>  \n\n![](images/86a9c84faf6d4a74ac3a7645dee3bed389e207d14386c527e01b4f65c411ee4c.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# Normal Forces  \n\n• In Newtonian liquids, the shear in one direction does not change the interaction or shape of molecules or particles, so everything remains balanced.  \n\nIn a real liquid, shear changes interactions (depends on their closeness) or causes anisotropy, e.g. orientation of molecules, etc.  \n\n– System is no longer in the initial random configuration   \n– So the stresses in the three cartesian directions (normal directions) may no longer be the same $\\tau_{11}\\neq$ $\\tau_{22}\\neq\\tau_{33}$   \nWe measure “normal forces” as $\\Nu_{1}=\\tau_{11}-\\tau_{22}$ , really the first normal stress difference • $\\mathrm{{N}}_{1}$ usually exerts an outward (positive) force as measured in cone and plate rheometer Can make a difference to brush drag and other properties.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# Extensional viscosity  \n\n• Unusually high extensional viscosity shows up in systems that contain high molecular weight, flexible polymers in solution.  \n\n– causes roller spatter and poor atomization – Stabilizes thick and long strings of paint behind roller, therefore big spatter drops  \n\n• This is an extension property - not a shear property Elongational viscosity $\\mathbf{\\Psi}=\\mathbf{\\Psi}$ stress difference / elongation rate  \n\n• Even Newtonian materials have viscosity in extensional flows $\\mathbf{\\tau}=3\\mathbf{x}$ shear viscosity  \n\nCopyright S. G. Croll, NDSU",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# Dr. Glass’ work (Union Carbide and NDSU)  \n\n![](images/ba29c30b0ce1a935bfdca0905bc1a0c2cf8993a8f1e843c98fa9e79456cc694f.jpg)  \nFigure3.17.Fiber development inrollcoating a high extensional viscosity paint.(From Ref.[29], withpermission.)  \n\nHigh extensional viscosity means that the fibers become large before they break into large spatter droplets, and leave greater roller stipple on the painted surface.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# Rheometers $\\mathbf{\\tau}=\\mathbf{\\tau}$ Viscometers",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 21,
+        "chunk": "# Brookfield: rotating disk or spindle  \n\nimposes a shear-rate field (rate varies across the disk)   \nmeasures the resistance, gives shear stress   \nCalibrated to give viscosity – Needs periodic calibration – Fluid container must be bigger than disk or spindle and provide good clearance underneath   \nQuite useful and accurate but cannot impose much shear stress or rate - limited in application  \n\n![](images/1dc69267f7439c0135823a2a2ac2130ff11251b35dc62dbf8cad2b53a618865b.jpg)  \nCopyright S. G. Croll, NDSU",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 22,
+        "chunk": "# Stormer Viscometer  \n\n![](images/18c0df542e60e170f32c6e25a2cfa03faf72a18b0f916747e0b39b980d10ee1b.jpg)  \n\nImposes a shear stress (very approximately)   \nusing vanes that move through the fluid at   \n200 r.p.m.   \nRotation rate usually monitored by stroboscope   \nMeasure the weight that maintains this rotation rate   \nResult is given in Krebs units (KU)ASTM   \nD562 - difficult to relate to any other,   \nscientific unit for viscosity   \nOriginally intended to emulate stirring   \nOften 90-100 KU is held to provide good brush pick-up performance and is used as a target for the lower shear-rate performance of an architectural paint  \n\nCopyright S. G. Croll, NDSU  \n\n![](images/ea3be5f8f8322de1ca0534caf72dd522af53ef92796ecf600660411d795b9d1c.jpg)  \nCopyright S. G. Croll, NDSU",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 23,
+        "chunk": "# Efflux Cups  \n\n• Measure the time taken for a standard quantity of fluid to pour out of the bottom. • Result is usually given in seconds • Used in Quality Control more than anything else, for low viscosity, sprayed paints! – Common type is the Ford No. 4 cup.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 24,
+        "chunk": "# Schematic of Ford Cup, number 4  \n\n![](images/89f2e620c254fddc64be9d7caf6415d9419ae4ca39ccd3fcdb820d54a33714f6.jpg)  \nCopyright S. G. Croll, NDSU",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 25,
+        "chunk": "# Scientific Viscometers  \n\nThese impose rigorous shear stresses or shear-rates, usually in a rotation sense.  Possibilities:  \n\n$\\succ$ Steady ramps   \n$\\blacktriangleright$ Constant levels   \n$\\succ$ Sinusoidal stresses or shear-rates   \n$\\succ$ Or combinations  \n\nUsually, a wide range of stress or shear-rate is available with very sensitive transducers for measuring the response.  \n\nTwo geometries are common (I) cone and plate (best defined strain-rate and stress) (II) parallel plate (can achieve higher shear-rates)  \n\nTwo types are used:  \n\n(I) controlled stress is the input, resultant shear-rate is measured - most common   \n(II) controlled shear-rate is the input, stress is measured. - requires bigger motors, more expensive",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 26,
+        "chunk": "# Cone and Plate Geometry  \n\n![](images/799c394dbafb8dd0d1125e5c9eca7703821912868d911eb50288b53cb346d509.jpg)  \nCopyright S. G. Croll, NDSU",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 27,
+        "chunk": "# Cone and Plate Geometry  \n\n• Shear Stress is given by:  \n\n$$\n\\tau=\\frac{3T}{2\\pi r^{3}}\n$$  \n\n$\\mathrm{{T}=}$ torque $r=$ radius of cone  \n\nShear-rate is given by: γ = $\\dot{\\gamma}=\\frac{\\omega}{a}$  \n\nWell defined while the angle is less $\\sim4^{\\circ}$ $\\boldsymbol{\\upomega}\\ =$ rotational speed, radians/second ${\\mathfrak{a}}=$ cone angle, radians (see previous slide)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 28,
+        "chunk": "# “I.C.I” Viscometers  \n\nDeveloped by I.C.I Ltd (Imperial Chemical Industries, UK) (paints division now part of AkzoNobel and PPG).  \n\n![](images/8c8e26c29fefa9363ee2e345f07de8e245d004f9fef8cd4f739982f5311fc75b.jpg)  \n\n• Cone and plate viscometers with single or defined range of shear rates  \n\n• Most common form is the model that operates at a shear rate of $10,000\\ \\mathbf{s}^{-1}$ Gauges performance in application process, e.g. brushing etc.  \n\nSupplied by instrument makers.  \n\nhttp://www.researchequipment.com/researchequipment.html",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 29,
+        "chunk": "# Bubble Viscometers  \n\nBubble rises at a speed that can be   \nused to calculate a viscosity Usually determined by comparison to a standard  \n\n![](images/6b5690d6d3c73ec3d72bc6e56f63f822660e3c6311ccbd728cf1fb22b828a019.jpg)  \nCole-Parmer  \n\nQuick and simple but useful only for clear solutions, resins, varnishes  \n\n• Usually reported by the letter grade of the standard closest in bubble speed, A5 through Z10, (0.005 to 1,000 Stokes) ASTM D1131, D1545, D1725 Tubes do have marks, so a timing can be done and a result calculated in standard viscosity units Sets of sealed standards are available, open tubes for your sample, and a holder so that sample tubes are inverted at same time as the standard Accurate provided that temperature does not vary too much and the bubble shape remains stable.  \n\nCopyright S. G. Croll, NDSU",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 30,
+        "chunk": "# Solution Viscosity  \n\n• Overall, solution viscosity depends on:  \n\n– Temperature   \n– Molecular weight   \n– Molecular weight distribution   \n– Solvent viscosity   \n– Polymer-solvent interactions   \n– Concentration",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 31,
+        "chunk": "# Resin Solutions  \n\nHigher molecular weight resins within about $100^{\\circ}\\mathrm{C}$ of their $T_{g}$ seem to follow a WLF (Williams-Landel-Ferry) type of dependence, as do lower molecular weight resins at all temperatures:  \n\n$$\nl n\\ \\eta=\\eta_{r}-{\\frac{c_{I}\\left(T-T_{r}\\right)}{c_{2}+{\\left(T-T_{r}\\right)}}}=27.6-{\\frac{A{\\left(T-T_{g}\\right)}}{B+{\\left(T-T_{g}\\right)}}}\n$$  \n\n• Subscript $^{\\ast}\\mathrm{r}^{\\ast}$ means some curve-fitted reference value. There are “universal” values if one uses the $T_{g}$ of the polymer as the reference. $\\mathrm{A}{\\sim}17.44$ and $\\mathrm{B}{\\sim}51.6$ Important variable is the difference between the actual temperature and $\\mathrm{T_{g}}$ .",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 32,
+        "chunk": "# Resin Solutions  \n\n• Lower $\\mathrm{T_{g}}$ leads to lower viscosity – Polymer is more flexible and thus poses less resistance to flow.  \n\n• At even higher temperatures and molecular weights the temperature dependence is closer to Arrhenuis:  \n\n$$\nl n\\eta{=}l n A^{\\prime}+\\frac{E_{\\nu}}{R T}\n$$  \n\n![](images/82a4e067b65a7d26a940d151ecf3009cb1797453ff51d929467344edd1a35268.jpg)  \nFigure 3.12. Viscosity dependence of standard liquid BPA epoxy resin on temperature. (From Ref.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 33,
+        "chunk": "# Dilute Solutions  \n\n• If a solution is dilute, i.e. the polymer molecules act independently, the solution viscosity can be expressed as:  \n\n$$\nl n~\\eta_{\\boldsymbol{r}}=\\left[\\pmb{\\eta}\\right]c+\\left[\\pmb{\\eta}\\right]^{2}c^{2}\n$$  \n\n$\\eta_{r}$ is the solution viscosity/solvent viscosity $\\mathbf{\\Sigma}=$ relative viscosity  \n\nThe intrinsic viscosity [] depends on the temperature (naturally) and the hydrodynamic volume swept out by the polymer molecule - which in turn depends on the molecular weight:  \n\nMark-Houwink-Skarada equation. $a$ goes from 0.3 to ${\\sim}0.8$  \n\n$$\n\\scriptstyle{[\\pmb{\\eta}]=\\pmb{K}\\pmb{M}^{a}}\n$$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 34,
+        "chunk": "# Characterizing Polymers in Dilute Solutions  \n\n• The Intrinsic Viscosity [] is defined by:  \n\n$$\n\\eta_{r e l}=\\frac{\\eta}{\\eta_{s}}=1+\\big[\\eta\\big]c+k c^{2}+\\dots\n$$  \n\nan alternative to equation on previous slide.  \n\n• It is measured by viscosity measurements taken on a succession of dilute concentration solutions in capillary viscometers (very accurate) – usually in a tightly controlled temperature bath.  \n\nCopyright S. G. Croll, NDSU  \n\n![](images/b581cfa24460d2d599a90972b7680feaa1c73298da262e86c165e5c411924c48.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 35,
+        "chunk": "# Concentrated Solutions  \n\n• There is not so much simplicity on the dependence of the viscosity on concentration:  \n\n$$\nl n\\eta_{r}=\\frac{w_{r}}{k_{I}-k_{2}w_{r}+k_{3}w_{r}^{2}}\n$$  \n\n• This equation works fairly well, $w_{r}=$ weight fraction of the polymer; sometimes simpler equations are fine.   \n• Polymer molecules extend in good solvents and thereby increase viscosity - choice of solvent is crucial. Poor solvents cause polymer molecules to coil upon themselves, and if the solvent is poor enough - the polymer comes out of solution.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 36,
+        "chunk": "# Dispersion Viscosity  \n\nDilute suspensions adhere well to Einstein’s equation: $\\eta_{r}=1+2.5\\phi$ Where $\\phi=$ volume fraction of the suspended particles $\\mathrm{\\sim}<0.1$ The factor of 2.5 assumes that the particles are spheres.  \n\nFor more concentrated suspensions other equations have been proposed. The most common are, (i) the Mooney equation:  \n\n$$\n\\eta_{\\mathrm{~r~}}=e x p\\left[\\frac{2.5\\phi}{I\\mathrm{~-~}\\displaystyle\\frac{\\phi}{\\phi_{\\mathrm{~m~}}}}\\right]\n$$  \n\nAnd, the most successful is (ii) the Krieger-Dougherty equation, but see next slide:  \n\n$$\n\\eta_{r}=\\left(I-\\frac{\\phi}{\\phi_{m}}\\right)^{-2.5\\varphi_{m}}\n$$  \n\nCopyright S. G. Croll, NDSU  \n\n![](images/27a62319727b0e8f91ec5067173c3131e5fa3c453bf9f023fbac351922e417ea.jpg)  \nCopyright S. G. Croll, NDSU",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 37,
+        "chunk": "# How the behavior of a suspension will change with concentration  \n\n![](images/dd2c8c2718e78fae55dfa2b1fdd3e9ba75686eb2ee54eab1d23f3825927faeff.jpg)  \nJ. M. Brader, “Nonlinear rheology of colloidal dispersions,” J. Phys.: Condens. Matter 22 (2010) 363101   \nFigure 3. A schematic illustration of the phase diagram of hard-spheres as a function of volume fraction. Monodisperse systems undergo a freezing transition to an FCC crystal with coexisting densities $\\phi=0.494$ and 0.545. Polydispersity suppresses the freezing transition resulting in a glass transition at $\\phi\\sim0.58$ ,which lies below the random-close-packing value of $\\phi\\sim0.64$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 38,
+        "chunk": "# Dispersion Viscosity  \n\n• Both the Mooney equation and the Krieger-Dougherty equations exhibit infinite viscosity at the maximum packing fraction, $\\Phi_{\\mathrm{m}}$ . The maximum packing fraction is a geometric constraint on the number of particles that can be accommodated in a given arrangement.   \n0.63 – dense random packing of spheres (good 1st.  choice for rheology)   \n0.59 – loose random packing of spheres (good second choice)   \n0.52 – simple cubic packing of spheres   \n0.74 – hexagonal close packing of spheres   \nFlakes, discs and rods may tumble and get in each others way so $\\Phi_{\\mathrm{m}}$ can be as low as 0.1.  \n\nFlocculation usually incorporates solvent into the aggregates and so effectively increases the volume fraction of the solids and so the viscosity becomes much higher.  \n\nCopyright S. G. Croll, NDSU",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 39,
+        "chunk": "# Possible Advance in Rheology of Dispersions (and Granular Matter)  \n\n• F. Boyer, E. Guazzelli, O. Pouliquen, “Unifying Suspension and Granular Rheology,” PRL 107, 188301 (2011) Different, but successful form of the equations for the relative viscosity of dispersions. Draws common ground between suspension and granular flow with viscous and collision contributions.  \n\n![](images/41d72ad8bd4ed88029373717031143642f31700a3b40ca093d4d03023fac6170.jpg)  \n$\\eta_{n}$ correlations of Eilers (red dashed line) and Krieger-Dougherty $\\eta_{s}$ $\\eta_{\\ast}$",
+        "category": " References"
+    },
+    {
+        "id": 40,
+        "chunk": "# Analytical Use of Rheology  \n\n• QC and Control – is it the same as the control material? – Best done at low shear rates (see below)  \n\n• High Shear Rate viscosity – Will it flow/atomize well in the equipment and with the power available?  \n\n• Low Shear Rate viscosity  \n\n– Low shear rates do not break down flocculation or other interactions, so it is good at detecting when materials or their behavior are different   \n– Very sensitive to material differences but only diagnostic by comparison with known control materials  \n\nCopyright S. G. Croll, NDSU",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/SDC-FSI CN109070134B.json b/task2/task2-chunks/SDC-FSI CN109070134B.json
new file mode 100644
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+++ b/task2/task2-chunks/SDC-FSI CN109070134B.json	
@@ -0,0 +1,52 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n(21)申请号 201780019726.1  \n(22)申请日 2017 .02.03  \n(65)同一申请的已公布的文献号申请公布号 CN 109070134 A  \n(43)申请公布日 2018.12.21  \n(30)优先权数据62/291 ,882 2016.02.05 US  \n\n(85)PCT国际申请进入国家阶段日2018.09.25  \n\n(86)PCT国际申请的申请数据PCT/US2017/016405 2017 .02.03(87)PCT国际申请的公布数据WO2017/136658 EN 2017 .08.10(73)专利权人 SDC 科技有限公司地址 美国加利福尼亚州",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# 防雾涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# (57)摘要  \n\n(72)发明人 K.德什潘德　D.黑斯　E.策廷P.蒙尼希  \n\n(74)专利代理机构 中国专利代理(香港)有限公司 72001代理人 麦振声 周李军  \n\n(51)Int.Cl. B05D 3/02(2006.01) C03C 17/32(2006.01) C08G 18/48(2006.01)  \n\n(56)对比文件JP H11140109 A,1999.05.25EP 0399441 A2,1990.11 .28  \n\n审查员 彭晓冬  \n\n权利要求书4页 说明书26页 附图1页  \n\n涂料组合物可以包括在亲水区域中具有反应性基团的一种或多种可辐射固化树脂，包含反应性部分的反应性表面活性剂；和光引发剂，其中，在光引发剂暴露到光能后，一种或多种可辐射固化的树脂被固化以形成亲水网络，其中所述反应性表面活性剂通过将表面活性剂的反应性部分结合到一种或多种可辐射固化的树脂的反应性基团结合到网络。固化涂料提供持久、可洗涤、防雾性质。  \n\n![](images/e9c71478eb9e52dffe46d77986e1fd5b380c889b8e517112e67f509b023e7814.jpg)  \n\n1.一种涂料组合物，当施加到基材并固化时，所述涂料组合物提供透明的可洗涤的防雾涂层，所述涂料组合物包含：  \n\n一种或多种可辐射固化的丙烯酸酯，其具有包含一个或多个亲水烷氧基化物基团的亲水区域，所述一个或多个亲水烷氧基化物基团具有式‑ $\\mathrm{\\Omega(CH_{2})\\Omega_{n}(0-)\\Sigma_{m}^{-}}$ ，其中n等于或大于1且等于或小于3 $;(1\\leqslant\\textrm{n}\\leqslant\\textrm{3})$ 且m等于或大于1且等于或小于10 $(1\\leqslant~\\mathsf{m}\\leqslant~10)$ ；  \n\n基于涂料组合物的重量为0 .5重量 $\\%-4.3$ 重量 $\\%$ 的包含反应性部分的反应性表面活性剂；和  \n\n光引发剂，  \n\n其中，在所述光引发剂暴露到光能后，所述一种或多种可辐射固化的丙烯酸酯被固化以形成亲水网络，其中通过将表面活性剂的反应性部分结合到在一种或多种可辐射固化的丙烯酸酯的亲水区域中的一个或多个丙烯酸酯基团，而将所述反应性表面活性剂结合到网络，和  \n\n其中，将所述可洗涤的防雾涂层在室温水中浸泡1小时，然后在 $25^{\\circ}\\mathrm{C}$ 且 $50\\%$ 相对湿度下干燥12小时后，暴露于来自加热至 $50^{\\circ}\\mathrm{C}$ 的烧杯中的水的水蒸气中1分钟时，所述可洗涤的防雾涂层不起雾。  \n\n2.权利要求1的涂料组合物，还包含分散在整个网络中的金属氧化物纳米颗粒以向涂层提供耐磨性质。  \n\n3.权利要求1或2的涂料组合物，其中所述一种或多种可辐射固化的丙烯酸酯包含乙氧基化丙烯酸酯。  \n\n4.权利要求3的涂料组合物，其中所述乙氧基化丙烯酸酯的浓度为涂料组合物的7重量 $\\cdot\\%-55$ 重量%。  \n\n5.权利要求1‑2或4中任一项的涂料组合物，其中所述亲水网络包含乙氧基化二丙烯酸酯和乙氧基化三丙烯酸酯。  \n\n6.权利要求1的涂料组合物，其中所述一种或多种可辐射固化的丙烯酸酯包括多官能乙氧基化丙烯酸酯单体。  \n\n7.权利要求1‑2、4或6中任一项的涂料组合物，其中所述反应性表面活性剂包括具有一个或多个选自烯基、丙烯酸酯基团和硫醇基的反应性基团的一种或多种反应性表面活性剂。  \n\n8.权利要求1‑2、4或6中任一项的涂料组合物，其中所述反应性表面活性剂包括具有烯基反应性基团的一种或多种反应性表面活性剂，所述一种或多种反应性表面活性剂具有下式： $\\mathrm{(CH_{2}\\ =\\ C H)\\cdot R}$ ，其中R选自醚磺酸酯、磷酸酯、聚醚及其共聚物、烷基醚、和烯基醚。  \n\n9.权利要求1‑2、4或6中任一项的涂料组合物，其中所述反应性表面活性剂包括具有丙烯酸酯反应性基团的一种或多种反应性表面活性剂，所述一种或多种反应性表面活性剂具有下式： $\\mathrm{(CH_{2}=\\ C H C O O)\\cdot R}$ ，其中R选自醚磺酸酯、磷酸酯和聚醚及其共聚物。  \n\n10.权利要求1‑2、4或6中任一项的涂料组合物，其中所述反应性表面活性剂包含具有硫醇反应性基团的一种或多种反应性表面活性剂，所述一种或多种反应性表面活性剂具有下式：(SH)‑R，其中R选自醚磺酸酯、磷酸酯和聚醚及其共聚物。  \n\n11.权利要求1‑2、4、或6中任一项的涂料组合物，还包含非反应性表面活性剂。  \n\n12.权利要求1‑2、4、或6中任一项的涂料组合物，该涂料组合物包含基于涂料组合物的重量为0.5重量 $\\cdot\\%-2$ 重量%的反应性表面活性剂。  \n\n13.一种紫外(UV)可固化涂料组合物，其包含：  \n\n一种或多种可辐射固化的多官能丙烯酸酯，其具有包含一个或多个亲水烷氧基化物基团的亲水区域，所述一个或多个亲水烷氧基化物基团具有式‑ $\\mathrm{\\Omega(CH_{2})\\Omega_{n}(0-)\\Omega_{m}-}$ ，其中n等于或大于1且等于或小于3 $(1\\leqslant\\mathsf{n}\\leqslant3)$ ，且m等于或大于1且等于或小于1 $0\\left(1\\leqslant\\mathrm{m}\\leqslant10\\right)$ )；  \n\n基于涂料组合物的重量为0.5重量 $\\%-4.3$ 重量 $\\%$ 的一种或多种反应性表面活性剂，其中所述反应性表面活性剂具有包含烯基、丙烯酸酯基团、硫醇基或其组合的一个或多个反应性基团；和  \n\n光引发剂，  \n\n其中，在所述光引发剂暴露到UV光能后，所述一种或多种可辐射固化的丙烯酸酯被固化以形成亲水网络，其中通过将一种或多种反应性表面活性剂的一个或多个反应性基团结合到在一种或多种可辐射固化的丙烯酸酯的亲水区域中的一个或多个丙烯酸酯基团，而将所述一种或多种反应性表面活性剂结合到网络，且  \n\n其中当施加到基材并固化时，所述涂料组合物提供透明的可洗涤的防雾涂层，和  \n\n将所述可洗涤的防雾涂层在室温水中浸泡1小时，然后在 $25\\mathrm{{^\\circC}}$ 且 $50\\%$ 相对湿度下干燥12小时后，暴露于来自加热至 $50^{\\circ}\\mathrm{C}$ 的烧杯中的水的水蒸气中1分钟时，所述可洗涤的防雾涂层不起雾。  \n\n14.权利要求13的涂料组合物，还包含分散在整个网络中的金属氧化物纳米颗粒以向涂层提供耐磨性质。  \n\n15.权利要求13‑14中任一项的涂料组合物，其中所述一种或多种可辐射固化的多官能丙烯酸酯包含乙氧基化丙烯酸酯。  \n\n16.权利要求15的涂料组合物，其中所述乙氧基化丙烯酸酯的浓度为涂料组合物的7重量 $\\cdot\\%-55$ 重量%。  \n\n17.权利要求13‑14或16中任一项的涂料组合物，其中所述一种或多种可辐射固化的多官能丙烯酸酯包含多官能乙氧基化丙烯酸酯单体。  \n\n18.权利要求13的涂料组合物，其中所述亲水网络包括乙氧基化二丙烯酸酯和乙氧基化三丙烯酸酯。  \n\n19.权利要求13‑14、16或18中任一项的涂料组合物，其中所述反应性表面活性剂包括具有烯基反应性基团的一种或多种反应性表面活性剂，所述一种或多种反应性表面活性剂具有下式： $\\mathrm{(CH_{2}\\ =\\ C H)\\cdot R}$ ，其中R选自醚磺酸酯、磷酸酯、聚醚及其共聚物、烷基醚、和烯基醚。  \n\n20.权利要求13‑14、16或18中任一项的涂料组合物，其中所述反应性表面活性剂包括具有丙烯酸酯反应性基团的一种或多种反应性表面活性剂，所述一种或多种反应性表面活性剂具有下式： $\\mathrm{(CH_{2}\\ =\\ C H C O0)\\cdot R}$ ，其中R选自醚磺酸酯、磷酸酯和聚醚及其共聚物。  \n\n21.权利要求13‑14、16或18中任一项的涂料组合物，其中所述反应性表面活性剂包含具有硫醇反应性基团的一种或多种反应性表面活性剂，所述一种或多种反应性表面活性剂具有下式：(SH)‑R，其中R选自醚磺酸酯、磷酸酯和聚醚及其共聚物。  \n\n22.权利要求13‑14、16或18中任一项的涂料组合物，还包含非反应性表面活性剂。  \n\n23.权利要求13‑14、16或18中任一项的涂料组合物，该涂料组合物包含基于涂料组合物的重量为0.5重量 $\\%-2$ 重量 $\\%$ 的一种或多种反应性表面活性剂。  \n\n24.  一种由涂料组合物形成的固化涂层，包括：  \n\n亲水网络，其包含一种或多种可辐射固化的丙烯酸酯，所述丙烯酸酯具有包含一个或多个亲水烷氧基化物基团的亲水区域，所述一个或多个亲水烷氧基化物基团具有式‑$\\big(\\mathrm{(CH_{2})\\Sigma_{n}0^{-}}\\big)_{\\mathrm{~m~}^{-}}$ ，其中n等于或大于1且等于或小于 $\\u_{3}(1\\leqslant\\mathrm{~n~}\\leqslant\\ 3)$ 且m等于或大于1且等于或小于10 $(1\\leqslant~\\mathsf{m}\\leqslant~10)$ ；和  \n\n基于涂料组合物的重量为0 .5重量 $\\%-4.3$ 重量 $\\%$ 的包含反应性部分的反应性表面活性剂，其中通过将反应性表面活性剂的反应性部分结合到在一种或多种可辐射固化的丙烯酸酯的亲水区域中的一个或多个丙烯酸酯基团，而将所述反应性表面活性剂结合到亲水网络，  \n\n其中，当施加到基材时，将所述固化涂层在室温水中浸泡1小时，然后在 $25\\mathrm{{^\\circC}}$ 且 $50\\%$ 相对湿度下干燥12小时后，暴露于来自加热至 $50^{\\circ}\\mathrm{C}$ 的烧杯中的水的水蒸气中1分钟时，所述固化涂层不起雾。  \n\n25.权利要求24的涂层，还包括分散在整个网络中的金属氧化物纳米颗粒。  \n\n26.权利要求24的涂层，其中当施加到基材时，所述涂层是透明、耐磨、可洗涤的防雾涂层。  \n\n27.权利要求24‑26中任一项的涂层，其中所述一种或多种可辐射固化的丙烯酸酯包括乙氧基化丙烯酸酯。  \n\n28.权利要求24‑26中任一项的涂层，其中所述亲水网络包含乙氧基化二丙烯酸酯和乙氧基化三丙烯酸酯。  \n\n29.权利要求24的涂层，其中所述一种或多种可辐射固化的丙烯酸酯包括多官能乙氧基化丙烯酸酯单体。  \n\n30.权利要求24‑26或29中任一项的涂层，其中所述反应性表面活性剂包括具有一个或多个选自烯基、丙烯酸酯基团和硫醇基的反应性基团的一种或多种反应性表面活性剂。  \n\n31.权利要求24‑26或29中任一项的涂料组合物，其中所述反应性表面活性剂包含具有烯基反应性基团的一种或多种反应性表面活性剂，所述一种或多种反应性表面活性剂具有下式： $\\mathrm{(CH_{2}\\ =\\ C H)\\cdot R}$ ，其中R选自醚磺酸酯、磷酸酯、聚醚及其共聚物、烷基醚、和烯基醚。  \n\n32.权利要求24‑26或29中任一项的涂料组合物，其中所述反应性表面活性剂包含具有丙烯酸酯反应性基团的一种或多种反应性表面活性剂，所述一种或多种反应性表面活性剂具有下式： $\\mathrm{(CH_{2}\\ =\\ C H C O0)\\cdot R}$ ，其中R选自醚磺酸酯、磷酸酯和聚醚及其共聚物。  \n\n33.权利要求24‑26或29中任一项的涂料组合物，其中所述反应性表面活性剂包含具有硫醇反应性基团的一种或多种反应性表面活性剂，所述一种或多种反应性表面活性剂具有下式：(SH)‑R，其中R选自醚磺酸酯、磷酸酯和聚醚及其共聚物。  \n\n34.权利要求24‑26或29中任一项的涂层，其中所述涂层由涂料组合物形成，所述涂料组合物包含基于涂料组合物的重量为0.5重量 $\\cdot\\%-2$ 重量%的反应性表面活性剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 35.一种制品，包括：  \n\n基材和施加到所述基材的透明、可洗涤的防雾涂层，其中由涂料组合物形成的所述涂层包含：  \n\n亲水网络，其包含一种或多种可辐射固化的丙烯酸酯，所述丙烯酸酯具有包含一个或  \n\n多个亲水烷氧基化物基团的亲水区域，所述一个或多个亲水烷氧基化物基团具有式‑$\\big(\\mathrm{(CH_{2})^{}_{n}0-}\\big)_{\\mathrm{~m~}^{-}}$ ，其中n等于或大于1且等于或小于 $3\\left(1\\leqslant\\mathrm{~n~}\\leqslant\\mathrm{~3\\right)~}$ 且m等于或大于1且等于或小于10 $(1\\leqslant\\mathrm{~m\\leqslant~10})$ ；和  \n\n基于涂料组合物的重量为0 .5重量 $\\%-4.3$ 重量 $\\%$ 的包含反应性部分的反应性表面活性剂，其中通过将表面活性剂的反应性部分结合到在一种或多种可辐射固化的丙烯酸酯的亲水区域中的一个或多个丙烯酸酯基团，而将所述反应性表面活性剂结合到亲水网络，  \n\n其中，将所述涂层在室温水中浸泡1小时，然后在 $25\\mathrm{{^\\circC}}$ 且 $50\\%$ 相对湿度下干燥12小时后，暴露于来自加热至 $50^{\\circ}\\mathrm{C}$ 的烧杯中的水的水蒸气中1分钟时，所述涂层不起雾。  \n\n36.权利要求35的制品，其中所述涂层还包含分散在整个网络中的金属氧化物纳米颗粒。  \n\n37.权利要求35或36的制品，其中所述涂层由涂料组合物形成，所述涂料组合物包含基于涂料组合物的重量为0.5重量 $\\cdot\\%-2$ 重量 $\\cdot\\%$ 的反应性表面活性剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 防雾涂料  \n\n[0001] 相关申请  \n\n[0002] 本申请要求2016年2月5日提交的美国临时申请序列号62/291 ,882和2017年2月3日提交的美国实用新型专利申请号15/423,764的权益和优先权，其全部内容通过引用并入本文。  \n\n[0003] 领域  \n\n[0004] 本公开涉及具有可洗涤、防雾性质和任选的耐磨性质的涂料。本公开还涉及用于制备这种涂料的方法，用这种涂料涂覆基材的方法，和涂覆有这种涂料的制品。  \n\n[0005] 背景  \n\n[0006] 在几种应用中需要永久防雾性质，例如眼科和太阳镜片；安全、军事和运动眼镜及配件；用于汽车、运输、建筑和构建、温室的玻璃制品；工业、销售点和电子显示器；商用冰箱和冷冻器门；镜子；太阳能面板等。  \n\n[0007] 当来自周围空气的水蒸气冷凝在形成小水滴的制品上时发生雾化。当制品的温度低于环境温度时，就会发生这种情况。目前的防雾涂料通常形成亲水特性的光滑表面。表面活性剂用于涂料制剂中以增加固化涂料的表面能，使得液滴能够在基材上成片而不形成球形液滴。产生的水成片效应使光的散射最小化，从而改善可视性。  \n\n[0008] 为了具有持久或永久的防雾性能，防雾涂料通常配制有大量表面活性剂，这可显著降低涂料的硬度。然而，通常，防雾涂料相当快地失去防雾功能，且需要用额外的表面活性剂复原。此外，目前市场上可获得的持久防雾涂料主要是热固化的，且因此在升高温度下需要长的固化时间，这会影响防雾制品制造商的制造成本和产量。另外，许多这些涂料不具有耐磨性质。因此，需要新的快速固化防雾涂料，其具有持久的防雾性质，而不需要复原，以及任选的、更好的耐磨性质。  \n\n[0009] 概述  \n\n[0010] 本公开提供具有持久防雾性质和任选的耐磨性质的快速固化涂料制剂。  \n\n[0011] 在一些方面，提供涂料组合物，所述组合物包含一种或多种可辐射固化的丙烯酸酯，其具有包含一个或多个亲水烷氧基化物基团的亲水区域，所述一个或多个亲水烷氧基化物基团具有式–( $\\left(\\mathrm{CH2}\\right)\\mathrm{n0-}\\right)\\mathrm{m^{-}}$ ，其中n可以等于或大于1且等于或小于3 $(1\\leqslant\\textrm{n}\\leqslant\\ 3)$ )，且m可以等于或大于1且等于或小于 $10\\left(1\\leqslant\\ \\mathrm{m}\\leqslant\\ 10\\right)$ ；包含反应性部分的反应性表面活性剂；和光引发剂，其中，在光引发剂暴露到光能后，所述一种或多种可辐射固化的丙烯酸酯被固化以形成亲水网络，其中通过将表面活性剂的反应性部分结合到在一种或多种可辐射固化的丙烯酸酯的亲水区域中的一个或多个丙烯酸酯基团将所述反应性表面活性剂结合到网络。[0012] 在一些方面，提供紫外(UV)可固化涂料组合物，所述组合物包含：可辐射固化的多官能丙烯酸酯，其具有包含一个或多个亲水烷氧基化物基团的亲水区域，所述一个或多个亲水烷氧基化物基团具有式‑ $\\mathrm{^{\\prime}(C H2)n0\\mathrm{-})m\\mathrm{-}}$ ，其中n可以等于或大于1且等于或小于3 $(1\\leqslant\\mathrm{~n~}$ $\\leqslant3)$ 且m可以等于或大于1且等于或小于 $10\\left(1\\leqslant\\ \\mathrm{m}\\leqslant\\ 10\\right)$ ；一种或多种反应性表面活性剂，其中所述反应性表面活性剂具有包含烯基、丙烯酸酯基团、硫醇基或其组合的一个或多个反应性基团；和光引发剂，其中，在光引发剂暴露到UV光能后，一种或多种可辐射固化的丙烯酸酯被固化以形成亲水网络，其中通过将表面活性剂的反应性部分结合到在一种或多种可辐射固化的丙烯酸酯的亲水区域中的一个或多个丙烯酸酯基团将所述反应性表面活性剂结合到网络。在一些实施方案中，丙烯酸酯是单官能、二官能、三官能或四官能或其组合。[0013] 在一些方面，本公开的涂料组合物在施加到基材并固化时提供透明的可洗涤的防雾涂层。在一些实施方案中，本公开的涂料组合物还包含分散在整个网络中的金属氧化物纳米颗粒以向涂料提供耐磨性质。在一些实施方案中，本公开的涂料组合物还包含非反应性表面活性剂。  \n\n[0014] 在一些方面，本公开提供一种包含亲水网络的固化涂料，所述亲水网络包含具有包含一个或多个亲水烷氧基化物基团的亲水区域的一种或多种丙烯酸酯，所述一个或多个亲水烷氧基化物基团具有式‑( $\\mathrm{(CH2)n0^{-})m^{-}}$ ，其中n可以等于或大于1且等于或小于3 $(1\\leqslant\\mathrm{~n~}$ $\\leqslant3)$ 且m可以等于或大于1且等于或小于1 $0\\left(1\\leqslant\\mathrm{~m\\leqslant~10}\\right)$ ；和包含反应性部分的反应性表面活性剂，其中通过将表面活性剂的反应性部分结合到在一种或多种可辐射固化的丙烯酸酯的亲水区域中的一个或多个丙烯酸酯基团将所述反应性表面活性剂结合到网络。这种涂料可以进一步包括分散在整个网络中的金属氧化物纳米颗粒，且当施加到基材时可以是光学透明的，耐磨的，具有可洗涤的防雾性质。  \n\n[0015] 在一些方面，本公开提供一种包括基材和施加到基材上的透明的可水洗涤的防雾涂料制品，其中所述涂料包含：包含具有包含一个或多个亲水烷氧基化物基团的亲水区域的一种或多种丙烯酸酯的亲水网络，所述一个或多个亲水烷氧基化物基团具有式‑((CH2)$\\mathrm{n0-})\\mathrm{m}^{-}$ ，其中n可以等于或大于1且等于或小于3 $(1\\leqslant\\textrm{n}\\leqslant\\textrm{3})$ 且m可以等于或大于1且等于或小于10( $(1\\leqslant~\\mathsf{m}\\leqslant~10)$ ；和包含反应性部分的反应性表面活性剂，其中通过将表面活性剂的反应性部分结合到在一种或多种可辐射固化的丙烯酸酯的亲水区域中的一个或多个丙烯酸酯基团将所述反应性表面活性剂结合到网络。涂料还可以包含分散在整个网络中的金属氧化物纳米颗粒。  \n\n[0016] 附图简述  \n\n[0017] 通过示例性实施方案的非限制性实例的方式参考所提到的多个附图，在下面的详述中进一步描述本公开，其中在附图的若干视图中，相同的附图标记表示类似的部分，且其中：  \n\n[0018] 图1提供适用于本公开的一些实施方案的可固化树脂和反应性表面活性剂的非限制性实例。  \n\n[0019] 虽然上述附图阐述了目前公开的实施方案，但如在讨论中所指出的，也可以预期其他实施方案。本公开通过表示而非限制的方式呈现说明性实施方案。可以通过本领域技术人员设计出许多其他修改和实施方案，这些修改和实施方案落入本公开的实施方案的原理的范围和精神内。  \n\n[0020] 详述  \n\n[0021] 以下描述仅提供示例性实施方案，且不旨在限制本公开的范围、适用性或配置。相反，示例性实施方案的以下描述将为本领域技术人员提供用于实现一个或多个示例性实施方案的使能描述。应当理解，在不脱离所附权利要求中阐述的本公开的精神和范围的情况下，可以对元件的功能和配置进行各种改变。  \n\n[0022] 在一些实施方案中，本公开提供涂料组合物，其包含(a)具有亲水区和在亲水区中的反应性基团的可辐射固化树脂，和(b)包含可与在聚合物的亲水区中的反应性基团反应的一个或多个反应性基团的反应性表面活性剂。在一些实施方案中，组合物是液体且在暴露到辐射后固化。在固化后，由于树脂的反应性基团和反应性表面活性剂之间的结合形成亲水网络，其中所述反应性表面活性剂结合到网络。在一些实施方案中，当施加到基材并固化时，这种涂料组合物提供光学透明的可洗涤的防雾涂层。在一些实施方案中，涂料可以用水、皂、商业清洁剂和类似的流体洗涤，且仍然保持其防雾性质。在一些实施方案中，组合物可进一步包括金属氧化物纳米颗粒，其在固化后可赋予涂料耐磨性，同时仍保持光学透明性和/或防雾性质。在一些实施方案中，当将本发明的涂料施加到光学透明基材(例如，Gentex  PC镜片)时，本发明的涂料不会增加镜片的雾度。例如，在一些实施方案中， $\\Delta$ 雾度，使用ASTM  D1003标准测量的在涂覆和未涂覆的光学透明基材之间的雾度差为 ${\\sim}0.01\\%$ ，因此表明涂料对雾度没有影响。  \n\n[0023] 在一些实施方案中，本公开的可辐射固化涂料组合物可以包含亲水烷氧基化丙烯酸酯作为可固化或可交联树脂，其在固化后形成亲水网络，反应性表面活性剂的反应性部分可与其结合。在一些实施方案中，树脂在暴露到UV光后可固化以减少组合物的固化时间。反应性表面活性剂与丙烯酸酯网络的结合可向本发明的组合物提供持久的防雾性质。通过使用最小载量的表面活性剂也可以实现持久的、可洗涤的防雾性质。在一些实施方案中，根据下文所述的各种洗涤和擦拭测试，本发明的组合物产生可洗涤的防雾涂层，即，在经受多次洗涤(例如，至少20次洗涤)后保持其防雾性质的涂层。本公开还提供用于制备涂料组合物的方法和这些组合物的使用方法。  \n\n[0024] 例如，本公开的一些方面还提供涂覆有涂料组合物的制品或由这种组合物得到的固化涂层，以及用防雾涂料组合物涂覆基材的方法。在一些实施方案中，由于成分的选择，本发明的涂料是光学透明的，且施加在光学透明基材上，例如用于眼镜的镜片。在一些实施方案中，本发明的涂料可用于制造待施加到冷冻器或冰箱的表面的防雾冷冻膜，或可直接涂覆在冷冻器或冰箱的表面上。  \n\n[0025] 可固化树脂  \n\n[0026] 在一些实施方案中，本公开的可固化树脂包括各种亲水丙烯酸酯，例如烷氧基化丙烯酸酯、丙烯酸缩水甘油酯等。在一些实施方案中，由于存在下式‑((CH2) ${\\mathrm{n0^{-}}}.$ )m的一个或多个基团，这种丙烯酸酯具有一个或多个亲水区域或亲水区。在一些实施方案中， $\\mathfrak{n}$ 可以等于或大于1且等于或小于3 $(1\\leqslant\\textrm{n}\\leqslant\\textrm{3})$ )，m可以等于或大于1且等于或小于10 $(1\\leqslant\\ \\mathrm{m}\\leqslant$ 10)，或二者。在一些实施方案中， $\\mathfrak{n}$ 可以等于2。在一些实施方案中，m可以等于5。以这种方式，可以提供防雾性质所需的合适的亲水环境。  \n\n[0027] 适用于本发明的组合物的丙烯酸酯还包括可与如下所述的反应性表面活性剂的反应性基团反应的反应性基团。例如，这种反应性基团可以包含丙烯酸酯基团。在一些实施方案中，反应性基团可以位于丙烯酸酯的亲水区域和在丙烯酸酯固化后形成的网络中。例如，图1呈现合适的丙烯酸酯10、20的非限制性实例，其具有亲水区域12、22(由于存在烷氧基化物基团)和在亲水区域12、22中的反应性基团14、24。丙烯酸酯10、20可以与亲水区域形成网络，且由于反应性基团34与丙烯酸酯10、20的反应性基团14、24的结合，反应性表面活性剂30可以在网络的亲水区域中结合到或变成被束缚到网络。表面活性剂30还可以具有亲水区域32以使反应性表面活性剂能够存在于亲水网络区中，使得反应性表面活性剂的未束缚侧可以自由地移动到网络表面以产生防雾活性。  \n\n[0028] 在一些实施方案中，可以采用一种或多种乙氧基化丙烯酸酯来形成网络。在一些实施方案中，丙烯酸酯可以包括具有单、二、三或四官能基团的一种或多种丙烯酸酯。在一些实施方案中，丙烯酸酯可以包括多于一种类型的丙烯酸酯单体。在一些实施方案中，可以通过使用多官能乙氧基化丙烯酸酯单体产生网络。在一些实施方案中，乙氧基化二丙烯酸酯和乙氧基化三丙烯酸酯可用于形成网络。  \n\n[0029] 合适的亲水二丙烯酸酯单体的实例包括但不限于乙二醇二丙烯酸酯；乙二醇二甲 基丙烯酸酯；二甘醇二丙烯酸酯；三甘醇二丙烯酸酯；三甘醇二甲基丙烯酸酯；四甘醇二丙 烯酸酯；四甘醇二甲基丙烯酸酯；聚乙二醇二丙烯酸酯；三丙甘醇二丙烯酸酯；三异丙甘醇 二丙烯酸酯；聚丙二醇二甲基丙烯酸酯；衍生自PluronicTM或PolaxamerTM的聚醚二丙烯酸 酯，和衍生自反向PluroincTM的聚醚二丙烯酸酯。  \n\n[0030] 合适的亲水三丙烯酸酯单体的实例包括但不限于乙氧基化三羟甲基丙烷三丙烯酸酯、丙氧基化甘油基三丙烯酸酯、丙氧基化三羟甲基丙烷三丙烯酸酯和三(2‑羟基乙基)异氰脲酸酯三丙烯酸酯。  \n\n[0031] 合适的亲水四丙烯酸酯单体的实例包括但不限于乙氧基化季戊四醇四丙烯酸酯。[0032] 反应性表面活性剂  \n\n[0033] 如上所述，本发明的组合物的反应性表面活性剂可以包含亲水区域，且还可以包括能够与可交联树脂的反应性基团反应的反应性部分或基团。这种反应性部分可以包括但不限于烯基、丙烯酸酯基团、硫醇基或其组合中的一种或多种。应当注意，在将反应产物加入到丙烯酸酯混合物之前，可以使表面活性剂与一种或多种反应性部分反应，或可以同时将表面活性剂和反应性部分加入到丙烯酸酯混合物中。在一些实施方案中，反应性部分可位于反应性表面活性剂的亲水区域或亲水区中。  \n\n[0034] 具有烯基反应性基团的代表性反应性表面活性剂可具有化学通式： $\\left(\\mathrm{CH}_{2}\\ =\\ \\mathrm{CH}\\right)$ ‑R，其中R可选自醚磺酸酯、磷酸酯、聚醚及其共聚物、非离子聚醚、烷基醚、烯基醚和烯属醚，如表1所示。具有带反应性双键的亲水链段的反应性表面活性剂的说明性实例包括但不限于Reasoap  SR10、Reasoap  SR20、Reasoap  ER10、Reasoap  PP70、Emulsogen  APS100。具有烯基反应性基团的反应性表面活性剂的其他非限制性实例示于下表1中。  \n\n[0035] 表1  \n\n<html><body><table><tr><td>化合物</td><td>描述</td></tr><tr><td></td><td>醚磺酸酯 （R可以是烷基、芳基或其他） n=10,11，... M=金属或铵反荷离子</td></tr><tr><td>OP(OOH)</td><td>磷酸酯 n=10,11，..</td></tr><tr><td></td><td>非离子聚醚表面活性剂 （R可以是烷基、芳基或其他） n=10,11，...</td></tr><tr><td></td><td>聚醚硫酸酯 n=4,5.... m=10,11,. M=金属或铵反荷离子</td></tr><tr><td></td><td>聚醚共聚物 1=1,2.. n=1,2... m=1,2.... p=1,2..</td></tr></table></body></html>  \n\n[0036]  \n\n[0037] 具有丙烯酸酯反应性基团的代表性反应性表面活性剂可具有化学通式： $\\left(\\mathrm{CH}_{2}\\right.\\ =$ CHCOO)‑R，其中R可选自醚磺酸酯、磷酸酯、聚醚及其共聚物，如表2所示。具有带反应性丙烯酸酯部分的亲水链段的表面活性剂的说明性实例包括但不限于磺基丙基丙烯酸的金属盐和烷基丙烯酰氧基乙基三烷基铵盐。具有丙烯酸酯反应性基团的反应性表面活性剂的其他非限制性实例示于下表2中。  \n\n[0038] 表2  \n\n<html><body><table><tr><td>化合物</td><td>描述</td></tr><tr><td></td><td>醚磺酸酯 n=10,11. M=金属或铵反荷离子</td></tr><tr><td>OP(OOH)</td><td>磷酸酯 n=1,2</td></tr><tr><td>N(CHSOCH</td><td>聚醚 n=10,11，..</td></tr><tr><td></td><td>非离子聚醚共聚物 n=1,2.. m=1,2...</td></tr></table></body></html>  \n\n[0040] 具有硫醇反应性基团的代表性反应性表面活性剂可具有化学通式：(SH)‑R，其中R可选自醚磺酸酯、磷酸酯、聚醚及其共聚物，如表3所示。在一些实施方案中，具有带反应性硫醇部分的亲水链段的表面活性剂可通过三羟甲基丙烷三(3‑巯基丙酸酯)(TMPTMP)与Reasoap  SR10经由硫醇‑烯反应(参见预混物3)反应获得。在一些实施方案中，具有带反应性硫醇部分的亲水链段的表面活性剂可通过季戊四醇四(3‑巯基丙酸酯)与Reasoap  SR10经由硫醇‑烯反应来反应而获得。具有硫醇反应性的反应性表面活性剂的其他非限制性实例示于下表3中。  \n\n[0041] 表3  \n\n[0042]  \n\n<html><body><table><tr><td>化合物</td><td>描述</td></tr><tr><td></td><td>醚磺酸酯 （R'可以是烷基、芳基或其他） n=10,11,... M=金属或铵反荷离子</td></tr><tr><td></td><td>磷酸酯 n=1,2...</td></tr><tr><td></td><td>非离子聚醚共聚物 n=1，2，. m=1，2,...</td></tr></table></body></html>  \n\n[0043] 在一些实施方案中，反应性表面活性剂的反应性链段在固化过程期间与丙烯酸酯的亲水区反应。以这种方式，在固化后，反应性表面活性剂可以能够与固化的丙烯酸酯网络结合并因此保持在原位(未洗掉或以其他方式除去)，以提供具有持久的防雾性质的涂层。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# [0044] 金属氧化物颗粒  \n\n[0045] 在一些实施方案中，本发明的组合物可以包括分散在整个亲水可交联树脂例如丙烯酸酯的网络中的金属氧化物颗粒。金属颗粒可以向涂料提供硬度和耐磨性。金属氧化物纳米颗粒的合适实例包括但不限于二氧化硅颗粒、氧化钛、氧化铝、氧化锌、氧化锑、氧化锡、锆氧化物及其组合。在一些实施方案中，可以选择金属纳米颗粒的尺寸和浓度，使得所得涂料是光学透明的，同时仍保持其防雾性质和耐磨性质。在一些实施方案中，金属氧化物颗粒是尺寸范围为约5至约50nm的纳米颗粒。在一些实施方案中，金属氧化物颗粒是尺寸范围为约10至约20nm的纳米颗粒。纳米颗粒可以以0至80重量%的浓度存在。  \n\n[0046] 非反应性表面活性剂  \n\n[0047] 在一些实施方案中，可以将非反应性表面活性剂加入到涂料组合物中以进一步增强防雾性质。合适的非反应性表面活性剂包括但不限于磺酸盐、铵盐、磷酸盐、聚乙二醇醚低聚物、亲水聚丙烯酸酯、辛苯氧基聚乙氧基乙醇和非离子聚醚嵌段共聚物。在一些实施方案中，组合物中的非反应性表面活性剂的浓度可以为0至10重量%。在一些实施方案中，组合物中的非反应性表面活性剂的浓度可以为液体的0.5至 $2\\%$ 重量。  \n\n[0048] 光引发剂  \n\n[0049] 在一些实施方案中，组合物可以包含一种或多种光引发剂以在暴露到辐射或光后引发组合物的固化。涂料组合物中存在的一种或多种光引发剂引发并促进可固化树脂的交联，即当涂料组合物暴露到辐射时固化涂料组合物。在一些实施方案中，可选择光引发剂以在暴露到UV光或可见光时发生反应。在一些实施方案中，光引发剂是蓝光光引发剂。在一些实施方案中，为了固化组合物，当H灯泡用于暴露灯泡一分钟时，累积的UV‑A暴露可以在1.0和 $2.5\\mathrm{J}/\\mathrm{cm}^{2}$ 之间。  \n\n[0050] 用于本文公开的涂料组合物的合适的UV辐射敏化光引发剂或引发剂的共混物的实例包括但不限于苯偶姻；被取代的苯偶姻，如苯偶姻醚的丁基异构体；二苯甲酮；被取代的二苯甲酮，如羟基二苯甲酮；2‑羟乙基‑N‑马来酰亚胺；2‑[2‑羟乙基(甲基)氨基]乙醇蒽醌；噻吨酮；α,α‑二乙氧基苯乙酮；2,2‑二甲氧基‑1,2‑二苯基乙‑1‑酮；2‑羟基‑2‑甲基‑1‑苯基‑丙‑1‑酮；二苯基(2,4,6‑三甲基苯甲酰基)氧化膦，苯基乙醛酸甲酯；1‑羟基环己基苯基酮；2‑苄基‑2‑二甲基氨基‑1‑(4‑吗啉代苯基)‑丁酮‑1；2‑二甲基氨基‑2‑(4‑甲基‑苄基)‑1‑(4‑吗啉基‑4‑基‑苯基)‑丁‑1‑酮；2‑甲基‑1‑[4‑(甲硫基)苯基]‑2‑吗啉基丙‑1‑酮；和1‑[4‑(2‑羟基乙氧基)‑苯基]‑2‑羟基‑2‑甲基‑1‑丙烷‑1‑酮。阳离子光酸产生剂可以包括但不限于二苯基[3‑(苯基硫烷基)苯基]锍六氟磷酸盐；二苯基[2‑苯基硫烷基]苯基]锍六氟锑酸盐；三芳基锍与六氟磷酸盐的六氟锑酸盐在碳酸亚丙酯中的混合物；和二芳基碘鎓盐与五氟硼酸盐、六氟锑酸盐或六氟磷酸盐。  \n\n[0051] 任选地，光引发剂增效剂与酰基酮光引发剂例如二苯甲酮一起用作共引发剂。合适的光引发剂增效剂包括例如N‑甲基‑二乙醇胺、三乙醇胺2‑(丁氧基)乙基‑4‑二甲基氨基苯甲酸酯和可以从UCB  Radcure  Chemicals  Corporation ,  Smyrna ,  Ga .作为EBECRYLP104、EBECRYL  P105和EBECRYL  7100市售可得的反应性胺丙烯酸酯，或可以从SartomerCompany ,  Inc .,  Exton ,  Pa市售可得的CN  371、CN  373、CN  384或CN  386。Sartomer将CN373描述为反应性胺丙烯酸酯共引发剂，其可与夺氢光引发剂，例如二苯甲酮或异丙基噻吨酮(TTX)组合使用，以促进自由基聚合。CN  373加速表面固化速度且有助于克服可UV固化涂料和油墨中的氧气抑制。Sartomer将CN  371、CN  384、CN  386、CN  550和CN551描述为二官能和三官能胺丙烯酸酯共引发剂，当其与光敏剂如二苯甲酮一起使用时，促进在UV光下的快速固化。  \n\n[0052] 在一些实施方案中，组合物可以包括可见光光引发剂以在暴露到蓝光(400‑$500\\mathrm{nm})$ 后引发组合物的固化。这些光引发剂可以包括但不限于樟脑醌，苯丙二酮(PPD)，二丙烯酰基氧化膦(Ir819)，包括2,4,6‑三甲基苯甲酰基二苯基氧化膦(TPO)，2,4,6‑三甲基苯甲酰基乙氧基‑苯基氧化膦(TPO‑L)和双(2,4,6‑三甲基苯甲酰基)苯基氧化膦(BAPO)。  \n\n[0053] 在一些实施方案中，光引发剂可选自α羟基酮光引发剂的种类。在一些实施方案中，光引发剂包含Irgacure  500( $50\\%$ 二苯甲酮 $^+$ $50\\%$ 1‑羟基‑环己基‑苯基酮)和Darocure1173(2‑羟基‑2‑甲基‑苯丙酮)中的一种或多种。  \n\n[0054] 可替代地，可在最少使用或不使用光引发剂的情况下使用电子束(EB)辐射固化涂料制剂。  \n\n[0055] 流动改性剂/流平剂  \n\n[0056] 在一些实施方案中，本文公开的涂料组合物可以包括流平剂。流平剂(也可以称为流动控制剂)可以掺入本文所述的涂料组合物中以使组合物更均匀地铺展或在基材表面上流平，并提供与基材的基本上均匀的接触。流平剂的量可以广泛变化，但优选以涂料组合物的固体重量的约 $0.001\\%$ 至约 $10\\%$ 流平剂的量使用。采用任何常规的市售可得的流平剂，其与涂料组合物和基材相容，能够使涂料组合物在基材上流平，且增强涂料组合物和基材之间的润湿性。这种流平剂的非限制性实例包括聚醚，聚硅酮，含氟表面活性剂，聚丙烯酸酯，聚硅酮聚丙烯酸酯如聚硅酮六丙烯酸酯和氟改性的聚丙烯酸酯。实例包括来自Rohm  andHaas的TRITON  X‑100，X‑405和N‑57，聚硅酮例如来自Dow  Corning的Paint  Additive  3，Paint  Additive  29和Paint  Additive  57，来自Momentive(Columbus，OH)的SILWET  L‑77和SILWET  L‑7600，和含氟表面活性剂例如来自3M  Corporation(St .  Paul，MN)的FLUORADFC‑4430。  \n\n[0057] 其他添加剂  \n\n[0058] 其他成分如抗氧化剂、抗静电剂、耐候剂、着色添加剂、UV稳定剂、分散剂、消泡剂、热稳定剂也可以加入到涂料制剂中。抗氧化剂的实例包括十八烷基‑3‑(3,5‑二叔丁基‑4‑羟基苯基)丙酸酯和季戊四醇四[3‑(3,5‑二叔丁基‑4‑羟基苯基)丙酸酯]。  \n\n[0059] 热稳定剂的实例包括亚磷酸三苯酯、三(2,6‑二甲基苯基)亚磷酸酯、三‑(2,4‑二叔丁基‑苯基)亚磷酸酯、三‑(混合的单‑和二‑壬基苯基)亚磷酸酯、二甲基苯膦酸酯和磷酸三甲酯。抗静电剂的实例包括甘油单硬脂酸酯、硬脂酰磺酸钠和十二烷基苯磺酸钠。  \n\n[0060] 已知聚碳酸酯(PC)在紫外(UV)光的暴露下会降解。这个过程被称为自然老化。耐候性材料可在UV暴露下长时间保持其物理性质。为了改善UV暴露下的使用寿命，可以在聚碳酸酯和类似芳族塑料基材的涂料中使用UV吸收剂。UV吸收剂包括但不限于三组化学品：  \n\n1)  2‑羟基‑二苯甲酮(BP)衍生物，商业实例包括但不限于Chimassorb $\\circledast$ 81和Chimassorb$\\circledast$ 90(均来自BASF ,  Germany)；2)  2‑(2‑羟基苯基)‑苯并三唑(HPBT)衍生物，商业实例包括但不限于Tinuvin $\\circledast$ 1130，Tinuvin $\\circledast$ 384‑2，Tinuvin $\\circledast$ 928和Tinuvin $\\circledast$ 900(均来自BASF ,  Germany)；3)  2‑羟基苯基‑均三嗪(HPT)衍生物，商业实例包括但不限于Tinuvin $\\circledast$ 400，Tinuvin $\\circledast$ 405(均来自BASF ,  Germany)。  \n\n[0061] 受阻胺光稳定剂(HALS)也用于有效稳定以抵抗光和自然老化的有害影响。最广泛使用的受阻胺光稳定剂(HALS)主要是2,2,6,6‑四甲基哌啶的衍生物。商业实例包括但不限于Tinuvin $\\circledast$ 152，Tinuvin $\\circledast$ 292(均来自BASF，Germany)。  \n\n[0062] 示例性组合物  \n\n[0063] 本发明的组合物中的丙烯酸酯的浓度可以为约 $4\\%$ 至 $95\\%$ 重量。在一些实施方案中，本发明的组合物中的丙烯酸酯的浓度可以为液体涂料的 $7\\%$ 至 $55\\%$ 重量。在一些实施方案中，反应性表面活性剂的浓度可以为液体涂料的 $0.5\\%$ 至 $30\\%$ 重量。在一些实施方案中，丙烯酸酯和反应性表面活性剂之间的重量比可以在3:1和95:1之间。在一些实施方案中，组合物中的非反应性表面活性剂的浓度可以为液体重量的0.5至 $2\\%$ 。在一些实施方案中，组合物可以包括二氧化硅颗粒。  \n\n[0064] 在一些实施方案中，丙烯酸酯包含一种或多种乙氧基化二丙烯酸酯和一种或多种乙氧基化三丙烯酸酯的混合物。在一些实施方案中，二丙烯酸酯可以包含三甘醇二丙烯酸酯。在一些实施方案中，三丙烯酸酯可以包含乙氧基化三羟甲基丙烷三酰化物。在一些实施方案中，二丙烯酸酯和三丙烯酸酯之间的比率可以在1:3至1:7的范围内。在一些实施方案中，为了增强网络的亲水质，网络可以基本上或完全不含非亲水丙烯酸酯。在一些实施方案中，网络可能缺少非亲水丙烯酸酯或具有疏水区域的丙烯酸酯。在一些实施方案中，组合物可以进一步包括具有烯基反应性基团的反应性表面活性剂，但是可以使用具有丙烯酸酯基团、硫醇基团或这3种基团的组合的表面活性剂。在一些实施方案中，反应性表面活性剂是阴离子表面活性剂。本发明的组合物可进一步包括金属氧化物颗粒，例如二氧化硅，以赋予本发明的涂料的硬度和耐磨性。此外，本发明的组合物可以包括以下中的一种或多种：非反应性表面活性剂，溶剂，光引发剂和流动改性剂。  \n\n[0065] 作为非限制性实例，本公开提供具有以下比率(以干重计)的二氧化硅、二丙烯酸酯和三丙烯酸酯中的一种或多种的组合物。  \n\n[0066] 在一些实施方案中，组合物可以包含约15至约 $50\\%$ 重量的二丙烯酸酯，和任选地约5至约 $60\\%$ 重量的二丙烯酸酯，和约50至约 $85\\%$ 重量的三丙烯酸酯，和任选地约40至约 $100\\%$ 重量的三丙烯酸酯。  \n\n[0067] 在一些实施方案中，组合物可以包含约 $50\\%$ 至约 $70\\%$ 的金属氧化物颗粒，和任选地约 $15\\%$ 至约 $80\\%$ 重量的金属氧化物颗粒，和约 $30\\%$ 至约 $50\\%$ 重量的三丙烯酸酯，和任选地，约20至约 $85\\%$ 重量的三丙烯酸酯。  \n\n[0068] 在一些实施方案中，组合物可以包含约50至约 $71\\%$ 重量的金属氧化物颗粒，和任选地约30至约 $80\\%$ 重量的金属氧化物颗粒；约4至约 $25\\%$ 重量的二丙烯酸酯，和任选地约4至约$30\\%$ 重量的二丙烯酸酯，和约20至约 $50\\%$ 重量的三丙烯酸酯，和任选地约16至约 $70\\%$ 重量的三丙烯酸酯。  \n\n[0069] 作为非限制性实例，本公开提供以下组合物：  \n\n[0070] 在一些实施方案中，组合物可以包含在总涂料中约4至约 $35\\%$ 重量的二丙烯酸酯，且在一些实施方案中，任选地包含约2至约 $45\\%$ 重量的二丙烯酸酯；在总涂料中约15至约 $60\\%$ 重量的三丙烯酸酯，和任选地约10至约 $75\\%$ 重量的三丙烯酸酯；和约0.5至约 $2\\%$ 重量的反应性表面活性剂，和任选地约0.5至约 $30\\%$ 重量的反应性表面活性剂。在一些实施方案中，组合物还可以包含以下中的一种或多种：约0.5至约 $2\\%$ 重量的非反应性表面活性剂，和任选地约0 .5至约 $10\\%$ 重量的非反应性表面活性剂；约40至约 $65\\%$ 重量的溶剂，和任选地约40至约 $70\\%$ 重量的溶剂；和约1至约 $4\\%$ 重量的光引发剂和流动改性剂，和任选地0.5至约 $5\\%$ 重量的光引发剂和流动改性剂。  \n\n[0071] 在一些实施方案中，组合物可以包含在总涂料中约15至约 $50\\%$ 重量的金属氧化物颗粒，和任选地约5至约 $60\\%$ 重量的金属氧化物颗粒；在总涂料中约9至约 $35\\%$ 重量的三丙烯酸酯，且任选地约5至约 $60\\%$ 重量的三丙烯酸酯；和约0.5至约 $2\\%$ 重量的反应性表面活性剂，和任选地约0.5至约 $30\\%$ 重量的反应性表面活性剂。在一些实施方案中，组合物还可以包含以下中的一种或多种：约0.5至约 $2\\%$ 重量的非反应性表面活性剂，且在一些实施方案中，任选地约0.5至约 $10\\%$ 重量的非反应性表面活性剂；约40至约 $65\\%$ 重量的溶剂，且在一些实施方案中，任选地约30至约 $70\\%$ 重量的溶剂；和约1至约 $4\\%$ 重量的光引发剂和流动改性剂，且在一些实施方案中，任选地1至约 $5\\%$ 重量的光引发剂和流动改性剂。  \n\n[0072] 在一些实施方案中，组合物可以包含在总涂料中约15至约 $50\\%$ 重量的金属氧化物颗粒，和任选地约5至约 $70\\%$ 重量的金属氧化物颗粒；在总涂料中约1至约 $20\\%$ 重量的二丙烯酸酯，和任选地约1至约 $30\\%$ 重量的二丙烯酸酯；在总涂料中约6至约 $35\\%$ 重量的三丙烯酸酯，和任选地约4至约 $50\\%$ 重量的三丙烯酸酯；和约0.5至约 $2\\%$ 重量的反应性表面活性剂，和任选地约0.5至约 $30\\%$ 重量的反应性表面活性剂。在一些实施方案中，组合物还可以包含以下中的一种或多种：约40至约 $65\\%$ 重量的溶剂，且在一些实施方案中，任选地约10至约 $70\\%$ 重量的溶剂；和约1至约 $4\\%$ 重量的光引发剂和流动改性剂，且在一些实施方案中，任选地1至约 $5\\%$ 重量的光引发剂和流动改性剂。  \n\n[0073] 在一些实施方案中，组合物可以包含在总涂料中约15至约 $50\\%$ 重量的金属氧化物颗粒，且在一些实施方案中，任选地约5至约 $70\\%$ 重量的金属氧化物颗粒；在总涂料中约1至约 $20\\%$ 重量的二丙烯酸酯，且在一些实施方案中，任选地约1至约 $30\\%$ 重量的二丙烯酸酯；在总涂料中约6至约 $35\\%$ 重量的三丙烯酸酯，且在一些实施方案中，任选地约4至约 $50\\%$ 重量的三丙烯酸酯；约0.5至约 $2\\%$ 重量的反应性表面活性剂，且在一些实施方案中，任选地约0.5至约 $30\\%$ 重量的反应性表面活性剂。在一些实施方案中，组合物还可以包含以下中的一种或多种：约0.5至约 $2\\%$ 重量的非反应性表面活性剂，且在一些实施方案中，任选地约0.5至约 $10\\%$ 重量的非反应性表面活性剂；约40至约 $65\\%$ 重量的溶剂，且在一些实施方案中，任选地约10至约 $70\\%$ 重量的溶剂；约1至约 $4\\%$ 重量的光引发剂和流动改性剂，且在一些实施方案中，任选地1至约 $5\\%$ 重量的光引发剂和流动改性剂。  \n\n[0074] 基材/制品  \n\n[0075] 本文公开的涂料组合物可以作为涂料施加到刚性或柔性基材。合适的基材材料包括但不限于透明塑料，例如聚碳酸酯(PC)，极化聚碳酸酯，聚酰胺，聚丙烯酸类，聚甲基丙烯酸甲酯(PMMA)，聚氯乙烯，聚双烯丙基碳酸酯，烯丙基二甘醇碳酸酯(ADC)聚合物，聚对苯二甲酸乙二醇酯(PET)，聚环烷酸乙二醇酯，三乙酸纤维素(CTA)聚合物，乙酸丁酸纤维素(CAB)聚合物，聚氨酯，聚环硫醚和聚硫氨酯。如果需要，可以在适当预处理的情况下使用其他基材，包括各种聚烯烃，氟化聚合物，金属和玻璃，例如钠钙玻璃，硼硅酸盐玻璃，丙烯酸类玻璃及其他类型的玻璃。可以用本公开的涂料涂覆的制品的实例包括但不限于安全眼镜、光学镜片、护目镜、面罩、用于头盔的面板、用作建筑中的窗户的玻璃制品，以及用作汽车、公共汽车、火车、飞机和其他运输车辆的挡风玻璃或窗户的玻璃制品、多功能LED、LCD显示器、浴室镜、淋浴镜和固定装置。涂料也可以施用于商业冷冻器门、冰淇淋冷冻器门和熟食柜。在一些实施方案中，为了增加本发明的组合物对基材的粘合性，可以对基材进行表面处理和/或用底漆涂覆。在一些实施方案中，可以使用基于丙烯酸酯的底漆，特别是对于PMMA基材。  \n\n[0076] 另外，通过将所公开的组合物涂覆在薄的柔性基材如PC或PET膜制备的涂覆制品可以进一步安装/应用于需要防雾功能的制品，例如安全眼镜、光学镜片、护目镜、面罩、用于头盔的面板、用作建筑中的窗户的玻璃制品，以及用作汽车、公共汽车、火车、飞机和其他运输车辆中的挡风玻璃或窗户的玻璃制品、多功能LED、LCD显示器、浴室和淋浴镜。防雾柔性膜还可以经由可重新定位的光学透明粘合剂(例如压敏粘合剂)施加到商业冷冻器门、冰淇淋冷冻器门和显示器、熟食柜，以防止结霜和雾化。  \n\n[0077] 本文所述的涂料组合物可以任何合适的方式施加到基材。例如，本公开的组合物可以通过常规方法例如流涂、喷涂、幕涂、浸涂、旋涂、缝模涂覆、辊涂等施加到固体基材以形成基材上的连续表面膜。然后涂料组合物通过将涂覆的基材暴露到由UV灯提供的UV辐射、由可见光灯提供的可见光辐射，或在一些实施方案中，由EB促进剂提供的EB辐射，或这些的组合来固化，本领域技术人员已知所有这些技术。另外，通过在薄的柔性基材如PC或  \n\nPET膜上涂覆所公开的组合物制备的涂覆制品可以经由在刚性基材上的干法或湿法层压来安装或改装。  \n\n[0078] 在一些实施方案中，提供具有可洗涤防雾性质的制品的方法包括处理制品的表面并将本公开的可洗涤防雾涂料施加到表面，其中所述涂料可进一步是光学透明的，耐磨的，或二者。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 实施例  \n\n[0079] 以下实施例仅是代表性的不应当用于限制本公开的范围。对于实施例中公开的方法和组合物存在多种备选设计。因此，所选实施例主要用于说明本文公开的设备和方法的原理。  \n\n[0080] 测试描述：  \n\n[0081] 膜厚度：基于光谱反射率方法，用Filmetrics  F20‑CP分光光度计在632 .8nm的波长下测量固化涂料的膜厚度。  \n\n[0082] 雾度：通过根据ASTM  D1003标准用Haze‑gard  Plus雾度计(BYK‑Gardner，Columbia，Md.)测量雾度来评价固化涂料的透光性和光散射性质。  \n\n[0083] 黄色指数：黄色指数根据ASTM  E‑313在Shimadzu  UV‑1601  UV‑Vis分光光度计(Shimadzu  Scientific  Instruments  of  Kyoto，Japan)上测量。  \n\n[0084] 粘合性：粘合性是涂料粘合到基材的能力。使用一卷压敏胶带3M  Brand  SCOTCHTM600胶带测试初始粘合性。测试如下进行：1)在固化涂料中用可伸缩的剃刀刀片造成5  X  5网格的交叉线(约2mm间隔)；2)在交叉线区域上牢固地按下胶带(使用压舌器)；3)在 $90\\pm$ 30s后，以 ${180}^{\\circ}$ °的角度或尽可能靠近基材拉出胶带；4)通过使用适当的视觉控制检查涂覆的基材来检查涂料的除去；5)还在显微镜下检查对象区域；6)未受影响的区域的实际计数报告为粘合百分比(当粘合仅沿线受到影响时，估计值转换为百分比)。  \n\n[0085] 沸水粘合性：在将涂覆的样本在沸水中浸泡1小时后，对于某些样品也以与上述相同的方式测试粘合性。  \n\n[0086] 钢丝绒磨损：通过YT‑520钢丝绒测试仪测量的钢丝绒磨损给出在用标准等级的钢丝绒摩擦后的涂覆材料的耐磨性/耐刮擦性的定性测定。日本钢丝绒级0000(特细)用于测试。通过机器在约2”  x  2”区域中摩擦涂覆的表面进行10次冲击。测试以 $50\\mathrm{g}$ 的重量开始。如果涂料没有产生刮擦，则重量增加到 $100\\mathrm{g}$ 。因此，重量逐渐增加直到在涂料上观察到刮擦。例如，钢丝绒耐力等级为 $200\\mathrm{g}$ 的固化涂料在 $200\\mathrm{g}$ 的最小载荷下显示刮擦。  \n\n[0087] Bayer磨损测试：Bayer磨损测试是涂覆样本的耐磨性相对于未涂覆的CR39标准的耐磨性的定量测量。该测试在Colts  Laboratory  BTE磨损测试仪中使用 $500\\mathrm{g}$ Norton  ZF＃12  Alundum磨损介质进行。未涂覆的Silor  Optical  CR‑39  Plano镜片用作标准。在600次冲击后，注意到涂覆样本和CR39标准的雾度变化。Bayer比率报告为未涂覆的CR39标准的雾度百分比差除以涂覆样本的雾度百分比差。  \n\n[0088] Ta ber测试 ：Ta ber磨损测试 用具有 $500\\mathrm{g}$ 辅助负载重量和CS‑10F轮 (Ta berIndustries，North  Tonawanda，N .Y .)的Teledyne  Model  5155  Taber  Abrader(TaberIndustries ，North  Tonawanda ，N .Y .) 进行。在测量之前 ，用ST‑11光面石 (TaberIndustries，North  Tonawanda，N .Y .)使轮光面化。通过在光面石上25转CS‑10F轮来进行光面化。用配备有Taber磨损固定器(BYK‑Gardner，Columbia，Md .)的Haze‑gard  Plus(BYK‑Gardner，Columbia，Md .)记录样品的初始雾度4次。在样品上进行100次CS‑10F轮循环后，用配备有Taber磨损固定器(BYK‑Gardner，Columbia，Md .)的Haze‑gard  Plus(BYK‑Gardner，Columbia，Md .)再记录雾度4次。然后针对初始雾度读数和使用CS‑10F轮100次循环后的雾度读数确定平均雾度。然后报告100个循环的平均雾度读数和初始雾度读数之间的差。  \n\n[0089] 防雾性质  \n\n[0090] 呼气测试：通过将涂覆的基材保持在距测试仪约2.5至7.5cm进行呼气测试。测试仪吹在样品上以故意产生雾。如果在测试期间在涂覆的基材上没有出现雾，则涂料组合物通过呼吸测试。如果在表面上出现雾，则涂料组合物未通过该测试。  \n\n[0091] 初始防雾测试：通过将涂覆的基材放置在含有 $60^{\\circ}\\mathrm{C}$ 水源的烧杯上方的标准高度$(1^{\\mathfrak{v}})$ 下进行初始防雾测试。将涂覆的基材暴露到来自 $60^{\\circ}\\mathrm{C}$ 水的水蒸气1分钟。如果在该测试期间在涂覆的基材上出现雾，则记录出现雾花费的时间。如果在暴露1分钟期间没有出现雾，则认为涂料“通过”初始防雾测试。  \n\n[0092] 水浸泡防雾测试：将涂覆的基材在室温下浸泡在水中1小时。然后将涂覆的样本从水中取出，悬浮在 $25^{\\circ}\\mathrm{C},50\\%\\mathrm{RF}$ H的架子上12小时，并通过将涂覆的基材放置在含有 $50^{\\circ}\\mathrm{C}$ 的水的烧杯上1分钟来测试防雾性质。如果在该测试期间在涂覆的基材上出现雾，则记录出现雾所花费的时间。如果在暴露1分钟期间没有出现雾，则认为涂料“通过”1h水浸泡防雾测试。  \n\n[0093] 此外，根据EN166/EN168方案，使用YT‑810防雾化测试仪(由Yin‑Tsung  Co .，Ltd制造)测试12h调整的水浸的涂覆样本的防雾性质。测试包括将涂覆的基材放置在测试仪上。当测试开始时，将涂覆的基材暴露到 $50^{\\circ}\\mathrm{C}$ 蒸汽，并使激光通过镜片。通过在8秒(s)的暴露中减少激光的透射来确定雾化量。如果在8s期间激光透射率低于初始读数的 $80\\%$ ，则涂料未通过雾测试，否则，它被评定为通过。  \n\n[0094] 擦拭测试后的防雾  \n\n[0095] 干布擦拭测试‑用干燥的微纤维布擦拭涂覆的基材20次。在20次擦拭之后，通过呼气测试和 $60^{\\circ}\\mathrm{C}$ 烧杯测试评估防雾性质一分钟。如果两个测试都通过，则认为涂覆的基材通过干布擦拭防雾测试。  \n\n[0096] IPA擦拭测试‑将微纤维布用异丙醇浸泡，且然后擦过涂覆表面一次。在擦拭后，通过呼气测试和 $60^{\\circ}\\mathrm{C}$ 烧杯测试评价防雾性质。这构成一个IPA擦拭循环。如果涂覆的基材通过两个测试，则使其干燥30分钟并重新测试。报告在没有雾化的情况下完成的循环次数。  \n\n[0097] 湿布擦拭测试‑将微纤维布浸泡在水中。用湿布擦拭涂覆的基材十次。在擦拭10次后，使涂覆的样本干燥1分钟，并通过呼气测试和 $60^{\\circ}\\mathrm{C}$ 烧杯测试测试防雾性质。这构成一个湿布擦拭循环。如果涂覆的基材通过两个测试，则在 $25\\mathrm{{^\\circC}}$ 和 $50\\%\\mathrm{RH}$ 下调节24h并重新测试。报告在没有雾化的情况下完成的循环次数。  \n\n[0098] 洗涤测试后的防雾  \n\n[0099] 自来水洗涤测试‑将涂覆的基材放置在流动的自来水下，并用湿微纤维布擦拭表面20次。在20次擦拭后，使涂覆的部分在环境条件下干燥30分钟。然后通过呼气测试和 $60^{\\circ}\\mathrm{C}$ 烧杯测试进行测试。这构成一个水洗涤循环。如果涂覆的基材通过两个测试，则将其在25$\\mathrm{{^\\circC}}$ ， $50\\%$ RH下平衡24h并重新测试。报告在没有雾化的情况下完成的循环次数。  \n\n[0100] 皂和自来水洗涤测试‑将涂覆的部分用1wt%的“Simple  Green”清洁剂在水中的溶液擦拭一次，然后放置在流动的自来水下并用湿微纤维布擦拭二十次。在20次擦拭后，使涂覆的样品在环境条件下干燥1小时。然后通过呼气测试和 $60^{\\circ}\\mathrm{C}$ 烧杯测试测试样品的防雾性质。这构成一个皂水洗涤循环。如果涂覆的基材通过两个测试，则在 $25\\mathrm{{^\\circC}}$ ， $50\\%\\mathrm{RH}$ 下调节 $24\\mathrm{h}$ ，且然后重新测试。报告在没有雾化的情况下完成的循环次数。  \n\n[0101] 擦拭和洗涤循环在下表4中总结。 [0102] 表4  \n\n<html><body><table><tr><td rowspan=\"2\"></td><td rowspan=\"2\">测试名称</td><td colspan=\"2\">初始测试</td><td rowspan=\"2\">循环之间的持续 时间</td></tr><tr><td>方法</td><td>防雾测试之 前的时间</td></tr><tr><td rowspan=\"3\">擦拭测试</td><td>干布擦拭测试</td><td>用干布擦拭10次</td><td>立即</td><td></td></tr><tr><td>IPA擦拭测试</td><td>用IPA浸泡布擦拭1次</td><td>立即</td><td>30分钟</td></tr><tr><td>湿布擦拭测试</td><td>用水浸泡布擦拭10次</td><td>1分钟</td><td>24小时</td></tr><tr><td rowspan=\"2\">洗涤测试</td><td>自来水测试</td><td>在自来水下用布擦拭20次</td><td>30分钟</td><td>24小时</td></tr><tr><td>皂/自来水测试</td><td>用皂布擦拭1次，接着在 自来水下擦拭20次</td><td>1小时</td><td>24小时</td></tr></table></body></html>  \n\n[0104] 洗涤和擦拭测试(机器) ：可洗涤性测试仪(AB5005自动可洗涤性测试， $\\mathrm{TQC}$ Thermimport质量控制，Capelle  aan  den  Ussel，荷兰)，由机械装置组成，海绵在其上安装在固定臂上，施加重量，等于施加到测试材料的 $300\\mathrm{g}$ 力。经测试的材料为涂覆的涂底漆的PET膜。在测试期间，在所公开的测试1000和5000次循环中，将海绵在测试材料的表面上重复移动指定的循环次数。当海绵移动过表面时，液体以 $0.3\\mathrm{{m}1/\\mathrm{{min}}}$ 的速率施加到表面。测试的液体包括去离子水、无氨Windex和配方409清洁剂。在完成指定的循环后，通过用纸巾擦拭使测试材料干燥，且然后测试防雾性能。如果材料在洗涤后通过防雾测试，则确定涂料在指定数目的擦拭后保持防雾性能。如果立即防雾测试失败，则记录防雾恢复所需的时间。如果防雾性能没有恢复，涂料将被确定为永久性防雾失败。  \n\n[0105] 冷冻器测试：仅测试涂覆在 $125\\upmu\\mathrm{m}$ 厚的聚碳酸酯膜上的样品。用双面胶带将涂覆膜固定到玻璃绝缘被动冷冻器门。将冷冻器设定到指定温度，且使系统平衡至少1小时。门打开至少 ${\\cdot60}^{\\circ}$ °。如果涂料保持无雾至少6秒，则涂料通过测试。记录外部环境温度和相对湿度。  \n\n[0106] 在设定为 $\\mathrm{^-12.2^{\\circ}C}$ 的被动冷冻器上进行“平均冷冻器使用”模拟。门每隔10分钟打开，持续6秒的持续时间，直到1小时。测量雾清除的时间长度并测量各个涂覆制品的雾百分比 $(\\%)$ 。环境温度为 $20.9^{\\circ}\\mathrm{C}$ ，相对湿度为 $53.4\\%$ 。  \n\n[0107] 以下是本申请中提及的化学品和其他材料的缩写的描述：MEK‑AC‑2140Z：甲基乙基酮中的胶体二氧化硅分散体(Nissan  Chemical  America  Corporation)；PGM‑AC‑2140Y：在1‑甲氧基‑2‑丙醇中的胶体二氧化硅分散体(Nissan  Chemical  America  Corporation)；TMPTMP：三羟甲基丙烷三(3‑巯基丙酸酯)(Aldrich)；SR272：三甘醇二丙烯酸酯(SartomerAmericas)；SR454：乙氧基化(3)三羟甲基丙烷三丙烯酸酯(Sartomer  Americas)；SR499：乙氧基化(6)三羟甲基丙烷三丙烯酸酯(Sartomer  Americas)；SR9035：乙氧基化(15)三羟甲基丙烷三酰化物(Sartomer  Americas) ；SR415：乙氧基化(20)三羟甲基丙烷三丙烯酸酯(Sartomer  Americas)；3‑EGA：三甘醇二丙烯酸酯(Kyoeisha)；REASOAP  SR‑10：反应性阴离子醚硫酸盐表面活性剂(Adeka) ；REASOAP  SR‑20：反应性阴离子醚硫酸盐表面活性剂(Adeka)；REASOAP  ER‑10：反应性非离子醚表面活性剂(Adeka)；Emulsogen  APS‑100：烯丙基聚亚烷基二醇醚硫酸盐的非离子无APEO铵盐(Clariant)；Igepal  CA‑720：聚氧乙烯(12)异辛基苯基醚(Sigma  Aldrich)；Brij  30：聚氧乙烯(4) 月桂基醚(ACROS  Organics)；Brij58：聚氧乙烯二醇十六烷基醚(ACROS  Organics)；OT‑75：二辛基磺基琥珀酸钠( $75\\%$ 在水和醇中)，(Cytec  Industries，Inc .)；Schercoquat  IAS‑PG：异硬脂酰氨基丙基乙基二铵乙基硫酸盐和丙二醇(Lubrizol)；PM：1‑甲氧基‑2‑丙醇；TMPTA：三羟甲基丙烷三丙烯酸酯；NPC‑ST‑30：Organo  SiO2(Nissan  Chemical  America  Corporation)；Pelex  OT‑P：双(2‑乙基己基)磺基琥珀酸多库酸钠(Kao  Corp.)；Witcobond  240：水性聚氨酯分散体(Chemtura)；FZ‑2105：Dow  Corning  Toray；Paraloid  A‑11：热塑性丙烯酸树脂(Dow)；Dymax  XR‑9416：水可稀释的氨基甲酸酯丙烯酸酯(Dymax) ；BYK‑333：聚醚改性的聚二甲基硅氧烷(Byk) ；Coatosil  7602：具有环氧乙烷侧链的聚硅酮共聚物(Momentive)；和NeoRez  R9679：脂族水性氨基甲酸酯(DSM  Coating  Resins，LLC)。  \n\n[0108] 以下是本申请中提到的基材的描述：PC镜片：聚碳酸酯眼科镜片；CR‑39：CR‑39TM聚双烯丙基碳酸酯眼科镜片；MR‑7：MR‑7TM聚硫氨酯眼科镜片；Trivex：TrivexTM氨基甲酸酯眼科镜片；PET膜：双轴取向聚对苯二甲酸乙二醇酯膜；PC板：Bayer  MakrolonTM聚碳酸酯片；PC膜：125um厚的PC基材；涂底漆的PET膜：双轴取向聚对苯二甲酸乙二醇酯膜的专有处理；和PMMA：聚(甲基丙烯酸甲酯)。  \n\n[0109] 预混物：  \n\n[0110] 以下预混物用于实施例。预混物1：将135.01克SR9035加入到含有24.65g配备有磁力搅拌棒的3‑EGA的圆底烧瓶。将内容物在室温下连续搅拌30分钟。在搅拌30分钟后，在室温下在不断搅拌下缓慢加入850 .65克MEK‑AC‑2140Z，且将混合物搅拌过夜。然后使用Buschi  Rotovap在 $40^{\\circ}\\mathrm{C}$ 和730  mTorr下真空蒸馏混合物。然后将浓缩的树脂用192g的PM二醇醚稀释。然后将混合物转移到适合于包装可UV固化涂料的加盖棕色容器中并使其冷却至室温。预混物2：将70克OT75( $75\\%$ 固体的水溶液)加入到含有30克Schercoquat  IAS‑PG的容器中，并使用磁力搅拌棒连续搅拌4小时。预混物3：将75克REASOAP  SR10加入到含有25克TMPTMP的圆底烧瓶中，并使用机械混合器在 $70\\mathrm{{^\\circC}}$ 下搅拌8小时。然后将混合物转移到适合于包装可UV固化涂料的加盖棕色容器中并冷却至室温。预混物4：使用磁力搅拌棒将15克Witcobond  240与85克PM在容器中混合30分钟。预混物5：在 $250\\mathrm{mL}$ 容器中，将 $35.8\\mathrm{g}$ Eastek1400加入到128.5g去离子水并用磁性搅拌棒搅拌10分钟。将 $35.9\\mathrm{g}$ PM加入到混合物并使用磁力搅拌棒搅拌30分钟。预混物6：将70克PM乙酸酯和30克Paraloid  A‑11在 $60^{\\circ}\\mathrm{C}$ 下混合3小时。预混物7：将90克PM与10克BYK‑333在环境条件下混合30分钟。  \n\n[0111] 实施例1：  \n\n[0112] 将94 .7克预混物1、1 .47克预混物2、1 .50克预混物3和2.29克Darocur  1173加入到容器，并使用磁力搅拌棒在室温下搅拌30分钟。然后使涂料混合物静置1小时。[0113] 根据施加方式，通过用PM稀释进一步调节固体的涂料混合物。经由浸涂、刮涂棒、流涂和旋涂以各种方式施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。固化的样品通过水浸泡防雾测试，粘合性测试，并具有至多200克的钢丝绒耐磨性。当施加到PC镜片时，该制剂具有2.79的Bayer耐磨性。当流涂到Bayer  Makrolon聚碳酸酯片上时，该样品通过水浸泡防雾测试，并具有 $250\\mathrm{g}$ 的钢丝绒耐磨性。如前所述测试涂覆镜片的擦拭测试。这些涂料通过IPA测试至多10个循环，湿擦拭测试至多14个循环，且自来水洗涤测试至多21个循环。  \n\n[0114] 在底漆层即预混物4上，已将实施例1施用于CR‑39、MR‑7、Trivex和PC镜片。当施加到底漆层时，固化涂料通过水浸泡防雾测试，和沸水粘合性测试。  \n\n[0115] 下表5显示在Bayer  Makrolon聚碳酸酯片上流涂，接着在 $2.0\\mathrm{J/cm}^{2}$ 下固化后，实施例1的固化涂料的性质。  \n\n[0116] 表5 [0117]  \n\n<html><body><table><tr><td>性质</td><td>实施例1</td></tr><tr><td>厚度 (um)</td><td>4-6</td></tr><tr><td>雾度(%)</td><td>0.26</td></tr><tr><td>初始防雾测试</td><td>通过</td></tr><tr><td>水浸泡防雾测试</td><td>通过</td></tr><tr><td>粘合性</td><td>通过</td></tr><tr><td>钢丝绒 (g)</td><td>250g</td></tr><tr><td>Taber (100 rev)</td><td>5.71</td></tr></table></body></html>  \n\n[0118] 下表6显示实施例1的固化涂料的擦拭和洗涤测试后的防雾性质。  \n\n[0119] 表6  \n\n[0120]  \n\n<html><body><table><tr><td></td><td>测试名称</td><td>#测试的循 环</td><td>#通过的循 环</td></tr><tr><td rowspan=\"3\">擦拭测试</td><td>干布擦拭测试</td><td>1</td><td>1</td></tr><tr><td>IPA擦拭测试</td><td>10</td><td>10</td></tr><tr><td>湿布擦拭测试</td><td>直到失效</td><td>14</td></tr><tr><td rowspan=\"2\">洗涤测试</td><td>自来水测试</td><td>直到失效</td><td>21</td></tr><tr><td>皂/自来水测试</td><td>直到失效</td><td>21</td></tr></table></body></html>  \n\n[0121] 下表7显示涂覆在不同眼科镜片基材上的实施例1的固化涂料的性质(旋涂，在$2.0\\mathrm{J/cm}^{2}$ 下固化)。研究中使用的所有基材均通过表面处理设备进行表面处理，并在涂覆之前通过常规抛光方法抛光；将表面处理镜片基材用预混物4旋涂在经表面处理的那侧上，空气干燥90min，且然后用实施例1的涂料旋涂。  \n\n[0122] 表7  \n\n[0123]  \n\n<html><body><table><tr><td rowspan=\"2\">性质</td><td colspan=\"4\">基材</td></tr><tr><td>CR-39</td><td>MR-7</td><td>Trivex</td><td>PC镜片</td></tr><tr><td>厚度（um）</td><td>4.9</td><td>4.8</td><td>4.7</td><td>5.2</td></tr><tr><td>雾度（%)</td><td>0.21</td><td>0.30</td><td>0.26</td><td>0.53</td></tr><tr><td>初始防雾测试</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾测试</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>粘合性</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>沸水粘合性</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr></table></body></html>  \n\n[0124] 下表8显示实施例1的固化涂料在 $100\\upmu\\mathrm{m}$ 厚的预处理PET膜上的性质。经由流涂技术施加涂料并在 $2.0\\mathrm{J/cm}^{2}$ 下固化。  \n\n[0125] 表8  \n\n[0126]  \n\n<html><body><table><tr><td rowspan=\"2\">性质</td><td colspan=\"2\">PET膜预处理</td></tr><tr><td>电晕（30s）</td><td>用预混物5预涂 覆*</td></tr><tr><td>厚度（um）</td><td>3.9-5.0</td><td>6.0-8.0</td></tr><tr><td>雾度（%）</td><td>1.5-2.0</td><td>1.46</td></tr><tr><td>初始防雾</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾机器测试</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾测试</td><td>通过</td><td>通过</td></tr><tr><td>粘合性</td><td>通过</td><td>通过</td></tr></table></body></html>  \n\n[0127] \\*PET膜通过用预混物5流涂进行预处理，并在环境条件下干燥30min。  \n\n[0128] 实施例2：  \n\n[0129] 使用磁力搅拌棒在室温下将69 .88克预混物1、1 .09克预混物2、1 .11克REASOAPSR‑10、1 .69克Darocure  1173、0 .37克Tergitol $15\\mathrm{-}\\mathrm{s}-7$ 和25.86克PM混合30分钟。在混合后，在施加到基材之前使制剂静置1小时。经由浸涂和旋涂以各种方式施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。固化后的样品通过水浸泡防雾测试、粘合性测试，并具有至多150克的钢丝绒耐磨性。当施加到PC镜片时，该制剂具有2.82的Bayer耐磨性。  \n\n[0130] 实施例3：  \n\n[0131] 使用磁力搅拌棒在室温下混合69 .88克预混物1、1 .09克预混物2、0 .83克REASOAPSR‑10、0 .28克TMPTMP、1 .69克Darocure  1173、0 .37克Tergitol  15‑s‑7和25 .86克PM  30分钟。在混合后，使制剂静置1小时。经由浸涂和旋涂以各种方式施加涂料。涂覆的部分在  \n\nFusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。固化的样品通过水浸泡防雾测试、粘合性测试，并具有至多150克的钢丝绒耐磨性。当施加到PC镜片时，该制剂具有3.30的Bayer耐磨性。  \n\n[0132] 下表9显示固化涂料实施例1‑3的性质。经由浸涂在成品平聚碳酸酯镜片上涂覆涂料并在 $2.0\\mathrm{J/cm}^{2}$ 下固化。  \n\n[0133] 表9  \n\n<html><body><table><tr><td>性质</td><td>实施例1</td><td>实施例2</td><td>实施例3</td></tr><tr><td>厚度（um）</td><td>6.5</td><td>6.5</td><td>6.5</td></tr><tr><td>雾度（%）</td><td>0.28</td><td>0.30</td><td>0.35</td></tr><tr><td>初始防雾测试</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾机 器测试</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾测 试</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>粘合性</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>钢丝绒（g）</td><td>200</td><td>150</td><td>200</td></tr></table></body></html>  \n\n[0134]  \n\n[0135] 实施例4：  \n\n[0136] 使用磁力搅拌棒在室温下将41 .26克SR9035、7 .64克3‑EGA、1 .09克预混物2、1 .11克预混物3、1.69克Darocur  1173和46.84克PM混合30分钟。通过旋涂施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。固化的样品通过水浸泡防雾测试、粘合性测试，并具有至多<50克的钢丝绒耐磨性。当施加到PC镜片时，该制剂具有0.40的Bayer耐磨性。  \n\n[0137] 实施例5：  \n\n[0138] 使用磁力搅拌棒在室温下将69 .88克预混物1、4 .44克REASOAP  SR‑10、1 .69克Darocure  1173、0 .37克Tergitol $15\\mathrm{-}\\mathrm{s}^{\\ensuremath{-}7}$ 和25.86克PM混合30分钟。在混合后，在施加到基材之前使混合物静置1小时。经由浸涂和旋涂以各种方式施加涂料。涂覆的部分在FusionUV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。固化的样品通过水浸泡防雾测试、粘合性测试，并具有至多100克的钢丝绒耐磨性。当施加到PC镜片时，该制剂具有2.40的Bayer耐磨性。  \n\n[0139] 下表10显示实施例1‑6的固化涂料的性质。所有涂料经由旋涂在成品平聚碳酸酯镜片上施加。涂覆的镜片在 $2.0\\mathrm{J/cm}^{2}$ 下固化。  \n\n[0140] 表10[0142] 实施例6：  \n\n<html><body><table><tr><td rowspan=\"5\"></td><td>性质</td><td></td><td>实施例1实施例2实施例3</td><td></td><td></td><td>实施例4实施例5</td></tr><tr><td>厚度（um）</td><td>4.1</td><td>4.0</td><td>4.4</td><td>4.0</td><td>4.5</td></tr><tr><td>雾度(%)</td><td>0.25</td><td>0.31</td><td>0.29</td><td>0.30</td><td>0.22</td></tr><tr><td>初始防雾 测试</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防 雾机器测 试</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td></td><td>水浸泡防 雾测试</td><td>通过 通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>粘合性</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>钢丝绒（g）</td><td>200</td><td>150</td><td>150</td><td><50</td><td>100</td></tr><tr><td>Bayer</td><td>2.79</td><td>2.82</td><td>3.3</td><td>0.4</td><td>2.4</td></tr></table></body></html>  \n\n[0143] 使用磁力搅拌棒在室温下将69 .88克预混物1、1 .09克预混物2、1 .11克REASOAPSR‑10、1 .69克Darocur  1173、0 .37克Tergitol  15‑s‑7和65克PM混合30分钟。在混合后，使制剂静置1小时。在San  Diego ,  CA的SolarGard涂覆并固化PET膜。这些样品通过水浸泡防雾测试，且表现出至多400克的钢丝绒耐磨性。  \n\n[0144] 在另一组实验中，实施例6也经由刮涂棒施加到PC膜上。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。这些样品通过水浸泡防雾、初始粘合性，并表现出至多200克的钢丝绒耐磨性。  \n\n[0145] 下表11显示施加到涂底漆的PET和PC膜的实施例6的固化样品的性质。通过刮涂棒施加涂料并使用UV固化。  \n\n[0146] 表11  \n\n[0147]  \n\n<html><body><table><tr><td>性质</td><td>涂底漆的PET膜*</td><td>PC膜</td></tr><tr><td>厚度 (um)</td><td>4.5</td><td>3.0-8.0</td></tr><tr><td>雾度(%)</td><td>0.20-0.40</td><td>0.20-0.35</td></tr><tr><td>初始防雾测试</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾测试</td><td>通过</td><td>通过</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 说　明　书  \n\n<html><body><table><tr><td>钢丝绒</td><td>400g</td><td>200 g</td></tr><tr><td>粘合性</td><td>100%</td><td>100%</td></tr><tr><td>YI</td><td>1.58</td><td>1.19-1.30</td></tr></table></body></html>\n\n[0148] \\*在Solar  Gard ,  San  Diego ,  CA涂覆和固化  \n\n[0149] 下表12说明在 $125\\upmu\\mathrm{m}$ 厚的聚碳酸酯膜上涂覆至4微米厚的实施例6。在被动冷冻器门上进行涂覆样品的冷冻器测试。  \n\n[0150] 表12  \n\n[0151]  \n\n<html><body><table><tr><td colspan=\"4\"></td><td>把手</td><td>折页</td><td>LTF300</td></tr><tr><td>温度 (F）</td><td>温度 (C）</td><td>室温（C）</td><td>室内相对湿度 (%)</td><td>6秒测试</td><td>6秒测试</td><td>6秒测试</td></tr><tr><td>10</td><td>-12.2</td><td>22.7</td><td>47.8</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>5</td><td>-15</td><td>21.7</td><td>52.4</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>0</td><td>-17.8</td><td>20.5</td><td>60.7</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>-5</td><td>-20.6</td><td>20.9</td><td>60.5</td><td>通过</td><td>通过</td><td>通过</td></tr></table></body></html>  \n\n[0152] 下表13说明在 $125\\upmu\\mathrm{m}$ 厚的聚碳酸酯膜上涂覆至4微米厚的实施例6。在设定为‑12.2$\\mathrm{{^\\circC}}$ 的被动冷冻器上进行涂覆样品的冷冻器测试。门每10分钟打开，持续6秒的持续时间，直至1小时。测量雾清除的时间长度，且测量单个涂覆制品的雾百分比 $\\left(\\%\\right)$ 。环境室温为20 .9$\\mathrm{{^\\circC}}$ ，相对湿度为 $53.4\\%$ 。  \n\n[0153] 表13  \n\n[0154]  \n\n<html><body><table><tr><td>时间(min)</td><td>清除时间 (Sec)</td><td>平均雾化(%)</td></tr><tr><td>Ｏ</td><td>Ｏ</td><td></td></tr><tr><td>10</td><td>Ｏ</td><td></td></tr><tr><td>20</td><td></td><td>Ｏ</td></tr><tr><td>30</td><td></td><td></td></tr><tr><td>40</td><td>0</td><td>Ｏ</td></tr><tr><td>50</td><td></td><td>Ｏ</td></tr><tr><td>60</td><td>Ｏ</td><td>Ｏ</td></tr></table></body></html>  \n\n[0155] 下表14显示在1000和5000次循环的机器洗涤测试后涂覆的PET膜的防雾性质。[0156] 表14  \n\n[0157]  \n\n<html><body><table><tr><td>清洁液体</td><td>循环数目</td><td>测试方法</td><td>防雾测试之前的调整 时间</td><td>实施例6</td></tr><tr><td rowspan=\"2\">Windex（无氨）</td><td>1000</td><td rowspan=\"6\">防雾 (60℃，烧 杯，1min）</td><td>0min</td><td>通过</td></tr><tr><td>5000</td><td>0min</td><td>通过</td></tr><tr><td rowspan=\"2\">Formula409清洁 剂</td><td>1000</td><td>0min</td><td>通过</td></tr><tr><td>5000</td><td>0min</td><td>通过</td></tr><tr><td rowspan=\"7\">去离子水</td><td rowspan=\"2\">1000</td><td rowspan=\"2\">0min 15min</td><td></td><td>未通过</td></tr><tr><td></td><td>未通过</td></tr><tr><td rowspan=\"6\">5000</td><td rowspan=\"3\"></td><td>30min</td><td>通过</td></tr><tr><td>0min</td><td>未通过</td></tr><tr><td>15min</td><td>未通过</td></tr><tr><td>30min 1小时</td><td></td><td>未通过 未通过</td></tr><tr><td rowspan=\"2\"></td><td></td><td>未通过</td></tr><tr><td>2小时 18小时</td><td>通过</td></tr></table></body></html>  \n\n[0158] 实施例7：  \n\n[0159] 使用磁力搅拌棒在室温下将69 .04克预混物1、1 .06克预混物2、1 .08克REASOAPSR‑10、1 .69克Darocur  1173、1 .57克Capstone  FS‑35和25 .56克PM混合30分钟。在混合后，使制剂静置1小时。经由旋涂在PC、CR‑39、MR‑7和Trivex镜片上施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。这些样品通过水浸泡防雾和初始粘合性。用于涂覆的PC样品的Bayer为2.68，且钢丝绒耐磨性为200克。当施加到包括CR‑39、MR‑7和Trivex的其他基材时，这些样品保持防雾性质、粘合性，表现出200克的钢丝绒耐磨性，和2.5的Bayer磨损。  \n\n[0160] 实施例7也施用于背面常规表面处理的PC、CR‑39、MR‑7、MR‑8、MR‑10和Trivex镜片。首先将预混物4施加到选定的基材，然后是实施例7。使用来自LTI  Coa tingTechnologies，LLC的CrystalSpin  SV旋涂和固化装置施加和固化所有涂料。所有涂覆的基材都通过水浸泡防雾测试、粘合性，并表现出200克的钢丝绒抗性。这些涂料还通过15分钟的沸水粘合性测试。  \n\n[0161] 下表15显示涂覆在不同眼科镜片基材上的实施例7的固化涂料的性质(旋涂，使用Fusion  UV单元在 $2.0\\mathrm{J/cm}^{2}$ 下固化)。研究中使用的所有基材均通过表面处理设备进行表面处理，并在涂覆之前通过常规抛光方法抛光。将表面处理的镜片基材用预混物4旋涂在经表面处理的那侧并在旋转的同时干燥45秒，且然后用实施例7的涂料旋涂。  \n\n[0162] 表15  \n\n<html><body><table><tr><td rowspan=\"7\"></td><td>涂料</td><td>实施例7</td><td>实施例7</td><td>实施例7</td><td>实施例7</td><td>实施例7</td></tr><tr><td>底漆</td><td>预混物4</td><td>预混物4</td><td>没有</td><td>预混物4</td><td>预混物4</td></tr><tr><td>基材</td><td>CR39</td><td>聚碳酸酯</td><td>聚碳酸酯</td><td>MR7</td><td>Trivex</td></tr><tr><td>外观</td><td></td><td></td><td></td><td></td><td>平滑/优异平滑/优异平滑/优异平滑/优异平滑/优异</td></tr><tr><td>厚度 (mm)</td><td>4.8</td><td>4.9</td><td>4.4</td><td>4.9</td><td>4.4</td></tr><tr><td>雾度（%）</td><td>0.35</td><td>0.26</td><td>0.22</td><td>0.30</td><td>0.19</td></tr><tr><td>初始防雾测试</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾机器测试</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>粘合性</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>沸水粘合性100C，1h</td><td>通过</td><td>通过</td><td>未通过</td><td>通过</td><td>通过</td></tr><tr><td>钢丝绒（g）</td><td>200</td><td>200</td><td>200</td><td>200</td><td>200</td></tr><tr><td>Bayer比率</td><td>2.5</td><td>2.5</td><td>2.68</td><td>2.5</td><td>2.5</td></tr></table></body></html>  \n\n[0164] 下表16显示涂覆在不同眼科镜片基材上的实施例7的固化涂料的性质(旋涂，使用Crystal  Spin  SV单元在 $2.0\\mathrm{J/cm}^{2}$ 下固化)。研究中使用的所有基材均通过表面处理设备进行表面处理，并在涂覆之前通过常规抛光方法抛光。将表面处理的镜片基材在CrystalSpinSV单元内用预混物4旋涂在经表面处理的那侧，并在旋转的同时干燥45秒，且然后用实施例7的涂料旋涂。  \n\n[0165] 表16 [0167] 实施例7a：  \n\n<html><body><table><tr><td rowspan=\"7\">66]</td><td></td><td>基材厚度（mm）雾度（%）</td><td></td><td>YI</td><td>钢丝绒 (g）</td><td>粘合性</td><td></td><td>初始防雾测试水浸泡防雾测试</td></tr><tr><td>Poly</td><td>5.8</td><td>0.22</td><td>0.98</td><td>200</td><td>100%</td><td>通过</td><td>通过</td></tr><tr><td>MR-7</td><td>5.7</td><td>0.21</td><td>1.88</td><td>200</td><td>100%</td><td>通过</td><td>通过</td></tr><tr><td>MR-8</td><td>5.8</td><td>0.25</td><td>1.92</td><td>200</td><td>100%</td><td>通过</td><td>通过</td></tr><tr><td>MR-10</td><td>5.8</td><td>0.22</td><td>1.69</td><td>200</td><td>100%</td><td>通过</td><td>通过</td></tr><tr><td>CR-39</td><td>5.1</td><td>0.21</td><td>0.90</td><td>200</td><td>100%</td><td>通过</td><td>通过</td></tr><tr><td>TrivexTM</td><td>5.1</td><td>0.19</td><td>0.96</td><td>200</td><td>98%</td><td>通过</td><td>通过</td></tr></table></body></html>  \n\n[0168] 使用磁力搅拌棒在室温下将69 .04克预混物1、1 .06克预混物2、1 .69克Darocur1173、1 .57克Capstone  FS‑35和25 .56克PM混合30分钟。在混合后，使制剂静置1小时。经由旋涂在PC镜片上施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。这些样品未通过水浸泡防雾并通过初始粘合性。  \n\n[0169] 实施例7b：  \n\n[0170] 使用磁力搅拌棒在室温下将69 .04克预混物1、1 .06克OT‑75、1 .69克Darocur1173、1 .57克Capstone  FS‑35和25 .56克PM混合30分钟。在混合后，使制剂静置1小时。经由旋涂在PC镜片上施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。这些样品未通过水浸泡防雾并通过初始粘合性。  \n\n[0171] 下表17显示与样品9相比不含反应性表面活性剂组合的固化样品的性质。将涂料旋涂在PC镜片上，并使用Fusion  UV固化单元在 $2.0\\mathrm{J/cm}^{2}$ 下固化。  \n\n[0172] 表17  \n\n[0173]  \n\n<html><body><table><tr><td>性质</td><td>实施例7</td><td>实施例7a</td><td>实施例7b</td></tr><tr><td>厚度 (um)</td><td>4.2</td><td>4.0</td><td>4.0</td></tr><tr><td>雾度 (%)</td><td>0.22</td><td>0.19</td><td>0.11</td></tr><tr><td>初始防雾测试</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾测试</td><td>通过</td><td>未通过</td><td>未通过</td></tr><tr><td>粘合性</td><td>通过</td><td>通过</td><td>通过</td></tr></table></body></html>  \n\n[0174] 实施例8：  \n\n[0175] 使用磁力搅拌棒在室温下将69 .04克预混物1、1 .06克预混物2、1 .08克EmulsogenAPS‑100、1 .69克Darocur  1173、1 .57克Capstone  FS‑35和25 .56克PM混合30分钟。在混合后，使制剂静置1小时。经由旋涂在PC镜片上施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。固化的样品通过水浸泡防雾，未通过初始粘合性，并表现出200克的钢丝绒耐磨性。  \n\n[0176] 实施例9：  \n\n[0177] 使用磁力搅拌棒在室温下将69 .04克预混物1、1 .06克预混物2、1 .08克REASOAPSR‑20、1 .69克Darocur  1173、1 .57克Capstone  FS‑35和25 .56克PM混合30分钟。在混合后，使制剂静置1小时。经由旋涂在PC镜片上施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。固化的样品通过水浸泡防雾，未通过初始粘合性，并表现出150克的钢丝绒耐磨性。  \n\n[0178] 下表18显示不同反应性表面活性剂组合的固化样品的性质。将涂料旋涂在GentexPC镜片上，并使用Fusion  UV固化单元在 $2.0\\mathrm{J/cm}^{2}$ 下固化。  \n\n[0179] 表18  \n\n[0180]  \n\n<html><body><table><tr><td>性质</td><td>实施例7</td><td>实施例8</td><td>实施例9</td></tr><tr><td>厚度 (um)</td><td>4.2</td><td>4.0</td><td>4.1</td></tr><tr><td>雾度(%)</td><td>0.22</td><td>0.27</td><td>0.27</td></tr><tr><td>初始防雾测试</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾测试</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>粘合性</td><td>通过</td><td>未通过</td><td>未通过</td></tr></table></body></html>  \n\n[0181] 实施例10：  \n\n[0182] 使用磁力搅拌棒在室温下将69.04克预混物1、1 .06克Igepal  CA‑720、1 .08克预混物3、1 .69克Darocur  1173、1 .57克Capstone  FS‑35和25 .56克PM混合30分钟。在混合后，使制剂静置1小时。经由旋涂在PC镜片上施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。这些样品通过水浸泡防雾和初始粘合。  \n\n[0183] 实施例11：  \n\n[0184] 使用磁力搅拌棒在室温下将69 .04克预混物1、1 .06克Igepal  CA‑720、1 .08克REASOAP  SR‑10、1 .69克Darocur  1173、1 .57克Capstone  FS‑35和25 .56克PM混合30分钟。在混合后，使制剂静置1小时。经由旋涂在PC镜片上施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。这些样品通过水浸泡防雾和初始粘合。  \n\n[0185] 实施例12：  \n\n[0186] 使用磁力搅拌棒在室温下将69 .04克预混物1、1 .06克Igepal  CA‑720、1 .08克REASOAP  ER‑10、1 .69克Darocur  1173、1 .57克Capstone  FS‑35和25 .56克PM混合30分钟。在混合后，使制剂静置1小时。经由旋涂在PC镜片上施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。这些样品通过水浸泡防雾和初始粘合。  \n\n[0187] 下表19显示使用Igepal的不同非反应性表面活性剂的固化样品的性质。将涂料旋涂在Gentex  PC镜片上，并使用Fusion  UV固化单元在2.0J/cm 下固化。  \n\n[0188] 表19  \n\n[0189]  \n\n<html><body><table><tr><td>性质</td><td>实施例10</td><td>实施例11</td><td>实施例12</td></tr><tr><td>厚度 (um)</td><td>4.4</td><td>4.0</td><td>4.3</td></tr><tr><td>雾度(%)</td><td>0.23</td><td>0.21</td><td>0.28</td></tr></table></body></html>  \n\n<html><body><table><tr><td>初始防雾测试</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾测试</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>粘合性</td><td>通过</td><td>通过</td><td>通过</td></tr></table></body></html>  \n\n[0190] 实施例13：  \n\n[0191] 使用磁力搅拌棒在室温下将69 .04克预混物1、1 .06克预混物2、1 .08克REASOAPSR‑10、1 .00克Irgacure  500、1 .57克Capstone  FS‑35和25 .56克PM混合30分钟。在混合后，使制剂静置1小时。经由旋涂在PC上施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。这些样品未通过水浸泡防雾并通过初始粘合性。该涂料表现出1 .72的Bayer磨损。  \n\n[0192] 下表20显示使用不同光引发剂的性质比较。将涂料旋涂在背面PC上，并使用Fusion  UV固化单元在 $2.0\\mathrm{J/cm}^{2}$ 下固化。  \n\n[0193] 表20  \n\n[0194]  \n\n<html><body><table><tr><td>性质</td><td>实施例7</td><td>实施例13</td></tr><tr><td>厚度 (um)</td><td>4.2</td><td>4.1</td></tr><tr><td>雾度(%)</td><td>0.25</td><td>0.24</td></tr><tr><td>初始防雾测试</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾测试</td><td>通过</td><td>未通过</td></tr><tr><td>粘合性</td><td>通过</td><td>通过</td></tr><tr><td>Bayer</td><td>2.68</td><td>1.72</td></tr><tr><td>YI</td><td>1.31</td><td>1.16</td></tr></table></body></html>  \n\n[0195] 实施例14：  \n\n[0196] 将6.75克预混物6与93.15克PM和0.1克预混物7混合1小时。使液体静置，且然后流涂在PMMA板上并在环境条件下干燥30分钟。然后使用磁力搅拌棒在室温下将69.04克预混物1、1 .06克预混物2、1 .08克预混物3、1 .69克Darocur  1173、1 .57克Capstone  FS‑35和25.56克PM混合30分钟。在混合后，使制剂静置1小时。然后经由刮涂棒将该液体施加到涂覆有底漆的PMMA。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。该涂料通过初始粘合和水浸泡防雾。  \n\n[0197] 下表21显示施加到具有底漆的PMMA板的实施例14的性质。  \n\n[0198] 表21  \n\n[0199]  \n\n<html><body><table><tr><td>底漆</td><td>涂料厚度 (um)</td><td>雾度(%)</td><td>粘合性</td><td>初始防雾测试</td><td>水浸泡防雾测试</td><td>钢丝绒磨损(g)</td></tr><tr><td>实施例14</td><td>10.9</td><td>0.48</td><td>通过</td><td>通过</td><td>通过</td><td>200</td></tr></table></body></html>  \n\n[0200] 实施例15：  \n\n[0201] 使用磁力搅拌棒在室温下将332克PGM‑AC‑2140Y、9 .9克SR‑272、52 .9克SR‑9035、4 .44克REASOAP  SR‑10、4 .5克预混物2、6 .8克Darocur  1173、1 .5克Tergitol $15\\mathrm{-}\\mathrm{s}^{\\phantom{-}}7$ 和168克PM混合30分钟。在混合后，使制剂静置1小时。经由刮涂棒将涂料施加到涂底漆的PET基材。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。这种涂料未通过初始粘合性，并通过水浸泡防雾。  \n\n[0202] 下表22显示实施例6和实施例15的固化样品的性质，其经由刮涂棒施加到 $50\\mathrm{{um}}$ 厚的涂底漆的PET膜，并使用Fusion  UV固化单元在2.0J/cm 下固化。  \n\n[0203] 表22  \n\n[0204]  \n\n<html><body><table><tr><td>性质</td><td>实施例6</td><td>实施例15</td></tr><tr><td>厚度 (um)</td><td>4.5</td><td>4.0-6.9</td></tr><tr><td>雾度 (%)</td><td>0.20-0.40</td><td>0.34</td></tr><tr><td>粘合性 (%)</td><td>通过</td><td>未通过</td></tr><tr><td>初始防雾</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾测试</td><td>通过</td><td>通过</td></tr></table></body></html>  \n\n[0205] 实施例16：  \n\n[0206] 根据US  6 ,946 ,498  B2的教导，将 $3.38\\mathrm{g}$ 去离子水加入到 $73.88\\mathrm{g}$ NPC‑ST‑30中并在室温下搅拌。将5 .16g  A‑174缓慢滴入到搅拌的混合物中并混合2小时。然后将 $11.12\\mathrm{g}$ TMPTA加入到搅拌的混合物，接着加入 $3.28\\mathrm{g}0\\mathrm{T}-75$ 并使其混合12小时。然后将 $\\mathrm{1.59g}$ Darocur  1173加入到混合物中并在室温下再混合30分钟。通过刮涂棒将涂料施加到PET膜或PC板。涂覆的部分在Fusion  UV固化装置中用H灯泡在 $1.0\\mathrm{J/cm}^{2}$ 下固化。样品不通过水浸泡防雾测试。  \n\n[0207] 下表23显示经由刮涂棒施加的实施例16的固化涂料的性质，并在 $1.0\\mathrm{J/cm}^{2}$ 下固化。  \n\n[0208] 表23  \n\n<html><body><table><tr><td rowspan=\"11\">[0209]</td><td>性质</td><td>实施例16</td><td>实施例16</td></tr><tr><td>基材</td><td>PET</td><td>PC板</td></tr><tr><td>厚度（um）</td><td>3.5</td><td>3.5</td></tr><tr><td>雾度（%）</td><td>1.1</td><td>0.39</td></tr><tr><td>初始防雾测试</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾机器测试</td><td>未通过</td><td>未通过</td></tr><tr><td>水浸泡防雾测试</td><td>未通过</td><td>未通过</td></tr><tr><td>粘合性</td><td>未通过</td><td>未通过</td></tr><tr><td>钢丝绒（g）</td><td>500</td><td>500</td></tr></table></body></html>  \n\n[0210] 本文引用的所有专利、专利申请和公开的参考文献均通过引用整体并入本文。应当强调，本公开的上述实施方案仅仅是设施方式的可能实施例，仅仅是为了清楚地理解本公开的原理而提出。在不偏离本发明的精神和原理的情况下，可以对上述一个或多个实施方案进行许多变化和修改。可以了解，上文公开的和其他特点和功能中的一些或其替代方案可以理想地组合到许多其他不同的系统或应用。所有这些修改和变化在此旨在包括在本公开的范围内，落入所附权利要求的范围内。  \n\n![](images/2c9df8a72656fe5b98776b9b4f50e2cac49c80806014c3ad5a98434a53de0218.jpg)  \n\n![](images/8cb481f25b9a3aed6119139060fcb7012a369e551fe3d981f3fb613bd4dda5da.jpg)  \n图 1",
+        "category": " Results and discussion"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,52 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19)中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (12)发明专利  \n\n(21)申请号 201780019726.1  \n(22)申请日 2017 .02.03  \n(65)同一申请的已公布的文献号申请公布号 CN 109070134 A  \n(43)申请公布日 2018.12.21  \n(30)优先权数据62/291 ,882 2016.02.05 US  \n\n(85)PCT国际申请进入国家阶段日2018.09.25  \n\n(86)PCT国际申请的申请数据PCT/US2017/016405 2017 .02.03(87)PCT国际申请的公布数据WO2017/136658 EN 2017 .08.10(73)专利权人 SDC 科技有限公司地址 美国加利福尼亚州",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (54)发明名称",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# 防雾涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# (57)摘要  \n\n(72)发明人 K.德什潘德　D.黑斯　E.策廷P.蒙尼希  \n\n(74)专利代理机构 中国专利代理(香港)有限公司 72001代理人 麦振声 周李军  \n\n(51)Int.Cl. B05D 3/02(2006.01) C03C 17/32(2006.01) C08G 18/48(2006.01)  \n\n(56)对比文件JP H11140109 A,1999.05.25EP 0399441 A2,1990.11 .28  \n\n审查员 彭晓冬  \n\n权利要求书4页 说明书26页 附图1页  \n\n涂料组合物可以包括在亲水区域中具有反应性基团的一种或多种可辐射固化树脂，包含反应性部分的反应性表面活性剂；和光引发剂，其中，在光引发剂暴露到光能后，一种或多种可辐射固化的树脂被固化以形成亲水网络，其中所述反应性表面活性剂通过将表面活性剂的反应性部分结合到一种或多种可辐射固化的树脂的反应性基团结合到网络。固化涂料提供持久、可洗涤、防雾性质。  \n\n![](images/e9c71478eb9e52dffe46d77986e1fd5b380c889b8e517112e67f509b023e7814.jpg)  \n\n1.一种涂料组合物，当施加到基材并固化时，所述涂料组合物提供透明的可洗涤的防雾涂层，所述涂料组合物包含：  \n\n一种或多种可辐射固化的丙烯酸酯，其具有包含一个或多个亲水烷氧基化物基团的亲水区域，所述一个或多个亲水烷氧基化物基团具有式‑ $\\mathrm{\\Omega(CH_{2})\\Omega_{n}(0-)\\Sigma_{m}^{-}}$ ，其中n等于或大于1且等于或小于3 $;(1\\leqslant\\textrm{n}\\leqslant\\textrm{3})$ 且m等于或大于1且等于或小于10 $(1\\leqslant~\\mathsf{m}\\leqslant~10)$ ；  \n\n基于涂料组合物的重量为0 .5重量 $\\%-4.3$ 重量 $\\%$ 的包含反应性部分的反应性表面活性剂；和  \n\n光引发剂，  \n\n其中，在所述光引发剂暴露到光能后，所述一种或多种可辐射固化的丙烯酸酯被固化以形成亲水网络，其中通过将表面活性剂的反应性部分结合到在一种或多种可辐射固化的丙烯酸酯的亲水区域中的一个或多个丙烯酸酯基团，而将所述反应性表面活性剂结合到网络，和  \n\n其中，将所述可洗涤的防雾涂层在室温水中浸泡1小时，然后在 $25^{\\circ}\\mathrm{C}$ 且 $50\\%$ 相对湿度下干燥12小时后，暴露于来自加热至 $50^{\\circ}\\mathrm{C}$ 的烧杯中的水的水蒸气中1分钟时，所述可洗涤的防雾涂层不起雾。  \n\n2.权利要求1的涂料组合物，还包含分散在整个网络中的金属氧化物纳米颗粒以向涂层提供耐磨性质。  \n\n3.权利要求1或2的涂料组合物，其中所述一种或多种可辐射固化的丙烯酸酯包含乙氧基化丙烯酸酯。  \n\n4.权利要求3的涂料组合物，其中所述乙氧基化丙烯酸酯的浓度为涂料组合物的7重量 $\\cdot\\%-55$ 重量%。  \n\n5.权利要求1‑2或4中任一项的涂料组合物，其中所述亲水网络包含乙氧基化二丙烯酸酯和乙氧基化三丙烯酸酯。  \n\n6.权利要求1的涂料组合物，其中所述一种或多种可辐射固化的丙烯酸酯包括多官能乙氧基化丙烯酸酯单体。  \n\n7.权利要求1‑2、4或6中任一项的涂料组合物，其中所述反应性表面活性剂包括具有一个或多个选自烯基、丙烯酸酯基团和硫醇基的反应性基团的一种或多种反应性表面活性剂。  \n\n8.权利要求1‑2、4或6中任一项的涂料组合物，其中所述反应性表面活性剂包括具有烯基反应性基团的一种或多种反应性表面活性剂，所述一种或多种反应性表面活性剂具有下式： $\\mathrm{(CH_{2}\\ =\\ C H)\\cdot R}$ ，其中R选自醚磺酸酯、磷酸酯、聚醚及其共聚物、烷基醚、和烯基醚。  \n\n9.权利要求1‑2、4或6中任一项的涂料组合物，其中所述反应性表面活性剂包括具有丙烯酸酯反应性基团的一种或多种反应性表面活性剂，所述一种或多种反应性表面活性剂具有下式： $\\mathrm{(CH_{2}=\\ C H C O O)\\cdot R}$ ，其中R选自醚磺酸酯、磷酸酯和聚醚及其共聚物。  \n\n10.权利要求1‑2、4或6中任一项的涂料组合物，其中所述反应性表面活性剂包含具有硫醇反应性基团的一种或多种反应性表面活性剂，所述一种或多种反应性表面活性剂具有下式：(SH)‑R，其中R选自醚磺酸酯、磷酸酯和聚醚及其共聚物。  \n\n11.权利要求1‑2、4、或6中任一项的涂料组合物，还包含非反应性表面活性剂。  \n\n12.权利要求1‑2、4、或6中任一项的涂料组合物，该涂料组合物包含基于涂料组合物的重量为0.5重量 $\\cdot\\%-2$ 重量%的反应性表面活性剂。  \n\n13.一种紫外(UV)可固化涂料组合物，其包含：  \n\n一种或多种可辐射固化的多官能丙烯酸酯，其具有包含一个或多个亲水烷氧基化物基团的亲水区域，所述一个或多个亲水烷氧基化物基团具有式‑ $\\mathrm{\\Omega(CH_{2})\\Omega_{n}(0-)\\Omega_{m}-}$ ，其中n等于或大于1且等于或小于3 $(1\\leqslant\\mathsf{n}\\leqslant3)$ ，且m等于或大于1且等于或小于1 $0\\left(1\\leqslant\\mathrm{m}\\leqslant10\\right)$ )；  \n\n基于涂料组合物的重量为0.5重量 $\\%-4.3$ 重量 $\\%$ 的一种或多种反应性表面活性剂，其中所述反应性表面活性剂具有包含烯基、丙烯酸酯基团、硫醇基或其组合的一个或多个反应性基团；和  \n\n光引发剂，  \n\n其中，在所述光引发剂暴露到UV光能后，所述一种或多种可辐射固化的丙烯酸酯被固化以形成亲水网络，其中通过将一种或多种反应性表面活性剂的一个或多个反应性基团结合到在一种或多种可辐射固化的丙烯酸酯的亲水区域中的一个或多个丙烯酸酯基团，而将所述一种或多种反应性表面活性剂结合到网络，且  \n\n其中当施加到基材并固化时，所述涂料组合物提供透明的可洗涤的防雾涂层，和  \n\n将所述可洗涤的防雾涂层在室温水中浸泡1小时，然后在 $25\\mathrm{{^\\circC}}$ 且 $50\\%$ 相对湿度下干燥12小时后，暴露于来自加热至 $50^{\\circ}\\mathrm{C}$ 的烧杯中的水的水蒸气中1分钟时，所述可洗涤的防雾涂层不起雾。  \n\n14.权利要求13的涂料组合物，还包含分散在整个网络中的金属氧化物纳米颗粒以向涂层提供耐磨性质。  \n\n15.权利要求13‑14中任一项的涂料组合物，其中所述一种或多种可辐射固化的多官能丙烯酸酯包含乙氧基化丙烯酸酯。  \n\n16.权利要求15的涂料组合物，其中所述乙氧基化丙烯酸酯的浓度为涂料组合物的7重量 $\\cdot\\%-55$ 重量%。  \n\n17.权利要求13‑14或16中任一项的涂料组合物，其中所述一种或多种可辐射固化的多官能丙烯酸酯包含多官能乙氧基化丙烯酸酯单体。  \n\n18.权利要求13的涂料组合物，其中所述亲水网络包括乙氧基化二丙烯酸酯和乙氧基化三丙烯酸酯。  \n\n19.权利要求13‑14、16或18中任一项的涂料组合物，其中所述反应性表面活性剂包括具有烯基反应性基团的一种或多种反应性表面活性剂，所述一种或多种反应性表面活性剂具有下式： $\\mathrm{(CH_{2}\\ =\\ C H)\\cdot R}$ ，其中R选自醚磺酸酯、磷酸酯、聚醚及其共聚物、烷基醚、和烯基醚。  \n\n20.权利要求13‑14、16或18中任一项的涂料组合物，其中所述反应性表面活性剂包括具有丙烯酸酯反应性基团的一种或多种反应性表面活性剂，所述一种或多种反应性表面活性剂具有下式： $\\mathrm{(CH_{2}\\ =\\ C H C O0)\\cdot R}$ ，其中R选自醚磺酸酯、磷酸酯和聚醚及其共聚物。  \n\n21.权利要求13‑14、16或18中任一项的涂料组合物，其中所述反应性表面活性剂包含具有硫醇反应性基团的一种或多种反应性表面活性剂，所述一种或多种反应性表面活性剂具有下式：(SH)‑R，其中R选自醚磺酸酯、磷酸酯和聚醚及其共聚物。  \n\n22.权利要求13‑14、16或18中任一项的涂料组合物，还包含非反应性表面活性剂。  \n\n23.权利要求13‑14、16或18中任一项的涂料组合物，该涂料组合物包含基于涂料组合物的重量为0.5重量 $\\%-2$ 重量 $\\%$ 的一种或多种反应性表面活性剂。  \n\n24.  一种由涂料组合物形成的固化涂层，包括：  \n\n亲水网络，其包含一种或多种可辐射固化的丙烯酸酯，所述丙烯酸酯具有包含一个或多个亲水烷氧基化物基团的亲水区域，所述一个或多个亲水烷氧基化物基团具有式‑$\\big(\\mathrm{(CH_{2})\\Sigma_{n}0^{-}}\\big)_{\\mathrm{~m~}^{-}}$ ，其中n等于或大于1且等于或小于 $\\u_{3}(1\\leqslant\\mathrm{~n~}\\leqslant\\ 3)$ 且m等于或大于1且等于或小于10 $(1\\leqslant~\\mathsf{m}\\leqslant~10)$ ；和  \n\n基于涂料组合物的重量为0 .5重量 $\\%-4.3$ 重量 $\\%$ 的包含反应性部分的反应性表面活性剂，其中通过将反应性表面活性剂的反应性部分结合到在一种或多种可辐射固化的丙烯酸酯的亲水区域中的一个或多个丙烯酸酯基团，而将所述反应性表面活性剂结合到亲水网络，  \n\n其中，当施加到基材时，将所述固化涂层在室温水中浸泡1小时，然后在 $25\\mathrm{{^\\circC}}$ 且 $50\\%$ 相对湿度下干燥12小时后，暴露于来自加热至 $50^{\\circ}\\mathrm{C}$ 的烧杯中的水的水蒸气中1分钟时，所述固化涂层不起雾。  \n\n25.权利要求24的涂层，还包括分散在整个网络中的金属氧化物纳米颗粒。  \n\n26.权利要求24的涂层，其中当施加到基材时，所述涂层是透明、耐磨、可洗涤的防雾涂层。  \n\n27.权利要求24‑26中任一项的涂层，其中所述一种或多种可辐射固化的丙烯酸酯包括乙氧基化丙烯酸酯。  \n\n28.权利要求24‑26中任一项的涂层，其中所述亲水网络包含乙氧基化二丙烯酸酯和乙氧基化三丙烯酸酯。  \n\n29.权利要求24的涂层，其中所述一种或多种可辐射固化的丙烯酸酯包括多官能乙氧基化丙烯酸酯单体。  \n\n30.权利要求24‑26或29中任一项的涂层，其中所述反应性表面活性剂包括具有一个或多个选自烯基、丙烯酸酯基团和硫醇基的反应性基团的一种或多种反应性表面活性剂。  \n\n31.权利要求24‑26或29中任一项的涂料组合物，其中所述反应性表面活性剂包含具有烯基反应性基团的一种或多种反应性表面活性剂，所述一种或多种反应性表面活性剂具有下式： $\\mathrm{(CH_{2}\\ =\\ C H)\\cdot R}$ ，其中R选自醚磺酸酯、磷酸酯、聚醚及其共聚物、烷基醚、和烯基醚。  \n\n32.权利要求24‑26或29中任一项的涂料组合物，其中所述反应性表面活性剂包含具有丙烯酸酯反应性基团的一种或多种反应性表面活性剂，所述一种或多种反应性表面活性剂具有下式： $\\mathrm{(CH_{2}\\ =\\ C H C O0)\\cdot R}$ ，其中R选自醚磺酸酯、磷酸酯和聚醚及其共聚物。  \n\n33.权利要求24‑26或29中任一项的涂料组合物，其中所述反应性表面活性剂包含具有硫醇反应性基团的一种或多种反应性表面活性剂，所述一种或多种反应性表面活性剂具有下式：(SH)‑R，其中R选自醚磺酸酯、磷酸酯和聚醚及其共聚物。  \n\n34.权利要求24‑26或29中任一项的涂层，其中所述涂层由涂料组合物形成，所述涂料组合物包含基于涂料组合物的重量为0.5重量 $\\cdot\\%-2$ 重量%的反应性表面活性剂。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 35.一种制品，包括：  \n\n基材和施加到所述基材的透明、可洗涤的防雾涂层，其中由涂料组合物形成的所述涂层包含：  \n\n亲水网络，其包含一种或多种可辐射固化的丙烯酸酯，所述丙烯酸酯具有包含一个或  \n\n多个亲水烷氧基化物基团的亲水区域，所述一个或多个亲水烷氧基化物基团具有式‑$\\big(\\mathrm{(CH_{2})^{}_{n}0-}\\big)_{\\mathrm{~m~}^{-}}$ ，其中n等于或大于1且等于或小于 $3\\left(1\\leqslant\\mathrm{~n~}\\leqslant\\mathrm{~3\\right)~}$ 且m等于或大于1且等于或小于10 $(1\\leqslant\\mathrm{~m\\leqslant~10})$ ；和  \n\n基于涂料组合物的重量为0 .5重量 $\\%-4.3$ 重量 $\\%$ 的包含反应性部分的反应性表面活性剂，其中通过将表面活性剂的反应性部分结合到在一种或多种可辐射固化的丙烯酸酯的亲水区域中的一个或多个丙烯酸酯基团，而将所述反应性表面活性剂结合到亲水网络，  \n\n其中，将所述涂层在室温水中浸泡1小时，然后在 $25\\mathrm{{^\\circC}}$ 且 $50\\%$ 相对湿度下干燥12小时后，暴露于来自加热至 $50^{\\circ}\\mathrm{C}$ 的烧杯中的水的水蒸气中1分钟时，所述涂层不起雾。  \n\n36.权利要求35的制品，其中所述涂层还包含分散在整个网络中的金属氧化物纳米颗粒。  \n\n37.权利要求35或36的制品，其中所述涂层由涂料组合物形成，所述涂料组合物包含基于涂料组合物的重量为0.5重量 $\\cdot\\%-2$ 重量 $\\cdot\\%$ 的反应性表面活性剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 防雾涂料  \n\n[0001] 相关申请  \n\n[0002] 本申请要求2016年2月5日提交的美国临时申请序列号62/291 ,882和2017年2月3日提交的美国实用新型专利申请号15/423,764的权益和优先权，其全部内容通过引用并入本文。  \n\n[0003] 领域  \n\n[0004] 本公开涉及具有可洗涤、防雾性质和任选的耐磨性质的涂料。本公开还涉及用于制备这种涂料的方法，用这种涂料涂覆基材的方法，和涂覆有这种涂料的制品。  \n\n[0005] 背景  \n\n[0006] 在几种应用中需要永久防雾性质，例如眼科和太阳镜片；安全、军事和运动眼镜及配件；用于汽车、运输、建筑和构建、温室的玻璃制品；工业、销售点和电子显示器；商用冰箱和冷冻器门；镜子；太阳能面板等。  \n\n[0007] 当来自周围空气的水蒸气冷凝在形成小水滴的制品上时发生雾化。当制品的温度低于环境温度时，就会发生这种情况。目前的防雾涂料通常形成亲水特性的光滑表面。表面活性剂用于涂料制剂中以增加固化涂料的表面能，使得液滴能够在基材上成片而不形成球形液滴。产生的水成片效应使光的散射最小化，从而改善可视性。  \n\n[0008] 为了具有持久或永久的防雾性能，防雾涂料通常配制有大量表面活性剂，这可显著降低涂料的硬度。然而，通常，防雾涂料相当快地失去防雾功能，且需要用额外的表面活性剂复原。此外，目前市场上可获得的持久防雾涂料主要是热固化的，且因此在升高温度下需要长的固化时间，这会影响防雾制品制造商的制造成本和产量。另外，许多这些涂料不具有耐磨性质。因此，需要新的快速固化防雾涂料，其具有持久的防雾性质，而不需要复原，以及任选的、更好的耐磨性质。  \n\n[0009] 概述  \n\n[0010] 本公开提供具有持久防雾性质和任选的耐磨性质的快速固化涂料制剂。  \n\n[0011] 在一些方面，提供涂料组合物，所述组合物包含一种或多种可辐射固化的丙烯酸酯，其具有包含一个或多个亲水烷氧基化物基团的亲水区域，所述一个或多个亲水烷氧基化物基团具有式–( $\\left(\\mathrm{CH2}\\right)\\mathrm{n0-}\\right)\\mathrm{m^{-}}$ ，其中n可以等于或大于1且等于或小于3 $(1\\leqslant\\textrm{n}\\leqslant\\ 3)$ )，且m可以等于或大于1且等于或小于 $10\\left(1\\leqslant\\ \\mathrm{m}\\leqslant\\ 10\\right)$ ；包含反应性部分的反应性表面活性剂；和光引发剂，其中，在光引发剂暴露到光能后，所述一种或多种可辐射固化的丙烯酸酯被固化以形成亲水网络，其中通过将表面活性剂的反应性部分结合到在一种或多种可辐射固化的丙烯酸酯的亲水区域中的一个或多个丙烯酸酯基团将所述反应性表面活性剂结合到网络。[0012] 在一些方面，提供紫外(UV)可固化涂料组合物，所述组合物包含：可辐射固化的多官能丙烯酸酯，其具有包含一个或多个亲水烷氧基化物基团的亲水区域，所述一个或多个亲水烷氧基化物基团具有式‑ $\\mathrm{^{\\prime}(C H2)n0\\mathrm{-})m\\mathrm{-}}$ ，其中n可以等于或大于1且等于或小于3 $(1\\leqslant\\mathrm{~n~}$ $\\leqslant3)$ 且m可以等于或大于1且等于或小于 $10\\left(1\\leqslant\\ \\mathrm{m}\\leqslant\\ 10\\right)$ ；一种或多种反应性表面活性剂，其中所述反应性表面活性剂具有包含烯基、丙烯酸酯基团、硫醇基或其组合的一个或多个反应性基团；和光引发剂，其中，在光引发剂暴露到UV光能后，一种或多种可辐射固化的丙烯酸酯被固化以形成亲水网络，其中通过将表面活性剂的反应性部分结合到在一种或多种可辐射固化的丙烯酸酯的亲水区域中的一个或多个丙烯酸酯基团将所述反应性表面活性剂结合到网络。在一些实施方案中，丙烯酸酯是单官能、二官能、三官能或四官能或其组合。[0013] 在一些方面，本公开的涂料组合物在施加到基材并固化时提供透明的可洗涤的防雾涂层。在一些实施方案中，本公开的涂料组合物还包含分散在整个网络中的金属氧化物纳米颗粒以向涂料提供耐磨性质。在一些实施方案中，本公开的涂料组合物还包含非反应性表面活性剂。  \n\n[0014] 在一些方面，本公开提供一种包含亲水网络的固化涂料，所述亲水网络包含具有包含一个或多个亲水烷氧基化物基团的亲水区域的一种或多种丙烯酸酯，所述一个或多个亲水烷氧基化物基团具有式‑( $\\mathrm{(CH2)n0^{-})m^{-}}$ ，其中n可以等于或大于1且等于或小于3 $(1\\leqslant\\mathrm{~n~}$ $\\leqslant3)$ 且m可以等于或大于1且等于或小于1 $0\\left(1\\leqslant\\mathrm{~m\\leqslant~10}\\right)$ ；和包含反应性部分的反应性表面活性剂，其中通过将表面活性剂的反应性部分结合到在一种或多种可辐射固化的丙烯酸酯的亲水区域中的一个或多个丙烯酸酯基团将所述反应性表面活性剂结合到网络。这种涂料可以进一步包括分散在整个网络中的金属氧化物纳米颗粒，且当施加到基材时可以是光学透明的，耐磨的，具有可洗涤的防雾性质。  \n\n[0015] 在一些方面，本公开提供一种包括基材和施加到基材上的透明的可水洗涤的防雾涂料制品，其中所述涂料包含：包含具有包含一个或多个亲水烷氧基化物基团的亲水区域的一种或多种丙烯酸酯的亲水网络，所述一个或多个亲水烷氧基化物基团具有式‑((CH2)$\\mathrm{n0-})\\mathrm{m}^{-}$ ，其中n可以等于或大于1且等于或小于3 $(1\\leqslant\\textrm{n}\\leqslant\\textrm{3})$ 且m可以等于或大于1且等于或小于10( $(1\\leqslant~\\mathsf{m}\\leqslant~10)$ ；和包含反应性部分的反应性表面活性剂，其中通过将表面活性剂的反应性部分结合到在一种或多种可辐射固化的丙烯酸酯的亲水区域中的一个或多个丙烯酸酯基团将所述反应性表面活性剂结合到网络。涂料还可以包含分散在整个网络中的金属氧化物纳米颗粒。  \n\n[0016] 附图简述  \n\n[0017] 通过示例性实施方案的非限制性实例的方式参考所提到的多个附图，在下面的详述中进一步描述本公开，其中在附图的若干视图中，相同的附图标记表示类似的部分，且其中：  \n\n[0018] 图1提供适用于本公开的一些实施方案的可固化树脂和反应性表面活性剂的非限制性实例。  \n\n[0019] 虽然上述附图阐述了目前公开的实施方案，但如在讨论中所指出的，也可以预期其他实施方案。本公开通过表示而非限制的方式呈现说明性实施方案。可以通过本领域技术人员设计出许多其他修改和实施方案，这些修改和实施方案落入本公开的实施方案的原理的范围和精神内。  \n\n[0020] 详述  \n\n[0021] 以下描述仅提供示例性实施方案，且不旨在限制本公开的范围、适用性或配置。相反，示例性实施方案的以下描述将为本领域技术人员提供用于实现一个或多个示例性实施方案的使能描述。应当理解，在不脱离所附权利要求中阐述的本公开的精神和范围的情况下，可以对元件的功能和配置进行各种改变。  \n\n[0022] 在一些实施方案中，本公开提供涂料组合物，其包含(a)具有亲水区和在亲水区中的反应性基团的可辐射固化树脂，和(b)包含可与在聚合物的亲水区中的反应性基团反应的一个或多个反应性基团的反应性表面活性剂。在一些实施方案中，组合物是液体且在暴露到辐射后固化。在固化后，由于树脂的反应性基团和反应性表面活性剂之间的结合形成亲水网络，其中所述反应性表面活性剂结合到网络。在一些实施方案中，当施加到基材并固化时，这种涂料组合物提供光学透明的可洗涤的防雾涂层。在一些实施方案中，涂料可以用水、皂、商业清洁剂和类似的流体洗涤，且仍然保持其防雾性质。在一些实施方案中，组合物可进一步包括金属氧化物纳米颗粒，其在固化后可赋予涂料耐磨性，同时仍保持光学透明性和/或防雾性质。在一些实施方案中，当将本发明的涂料施加到光学透明基材(例如，Gentex  PC镜片)时，本发明的涂料不会增加镜片的雾度。例如，在一些实施方案中， $\\Delta$ 雾度，使用ASTM  D1003标准测量的在涂覆和未涂覆的光学透明基材之间的雾度差为 ${\\sim}0.01\\%$ ，因此表明涂料对雾度没有影响。  \n\n[0023] 在一些实施方案中，本公开的可辐射固化涂料组合物可以包含亲水烷氧基化丙烯酸酯作为可固化或可交联树脂，其在固化后形成亲水网络，反应性表面活性剂的反应性部分可与其结合。在一些实施方案中，树脂在暴露到UV光后可固化以减少组合物的固化时间。反应性表面活性剂与丙烯酸酯网络的结合可向本发明的组合物提供持久的防雾性质。通过使用最小载量的表面活性剂也可以实现持久的、可洗涤的防雾性质。在一些实施方案中，根据下文所述的各种洗涤和擦拭测试，本发明的组合物产生可洗涤的防雾涂层，即，在经受多次洗涤(例如，至少20次洗涤)后保持其防雾性质的涂层。本公开还提供用于制备涂料组合物的方法和这些组合物的使用方法。  \n\n[0024] 例如，本公开的一些方面还提供涂覆有涂料组合物的制品或由这种组合物得到的固化涂层，以及用防雾涂料组合物涂覆基材的方法。在一些实施方案中，由于成分的选择，本发明的涂料是光学透明的，且施加在光学透明基材上，例如用于眼镜的镜片。在一些实施方案中，本发明的涂料可用于制造待施加到冷冻器或冰箱的表面的防雾冷冻膜，或可直接涂覆在冷冻器或冰箱的表面上。  \n\n[0025] 可固化树脂  \n\n[0026] 在一些实施方案中，本公开的可固化树脂包括各种亲水丙烯酸酯，例如烷氧基化丙烯酸酯、丙烯酸缩水甘油酯等。在一些实施方案中，由于存在下式‑((CH2) ${\\mathrm{n0^{-}}}.$ )m的一个或多个基团，这种丙烯酸酯具有一个或多个亲水区域或亲水区。在一些实施方案中， $\\mathfrak{n}$ 可以等于或大于1且等于或小于3 $(1\\leqslant\\textrm{n}\\leqslant\\textrm{3})$ )，m可以等于或大于1且等于或小于10 $(1\\leqslant\\ \\mathrm{m}\\leqslant$ 10)，或二者。在一些实施方案中， $\\mathfrak{n}$ 可以等于2。在一些实施方案中，m可以等于5。以这种方式，可以提供防雾性质所需的合适的亲水环境。  \n\n[0027] 适用于本发明的组合物的丙烯酸酯还包括可与如下所述的反应性表面活性剂的反应性基团反应的反应性基团。例如，这种反应性基团可以包含丙烯酸酯基团。在一些实施方案中，反应性基团可以位于丙烯酸酯的亲水区域和在丙烯酸酯固化后形成的网络中。例如，图1呈现合适的丙烯酸酯10、20的非限制性实例，其具有亲水区域12、22(由于存在烷氧基化物基团)和在亲水区域12、22中的反应性基团14、24。丙烯酸酯10、20可以与亲水区域形成网络，且由于反应性基团34与丙烯酸酯10、20的反应性基团14、24的结合，反应性表面活性剂30可以在网络的亲水区域中结合到或变成被束缚到网络。表面活性剂30还可以具有亲水区域32以使反应性表面活性剂能够存在于亲水网络区中，使得反应性表面活性剂的未束缚侧可以自由地移动到网络表面以产生防雾活性。  \n\n[0028] 在一些实施方案中，可以采用一种或多种乙氧基化丙烯酸酯来形成网络。在一些实施方案中，丙烯酸酯可以包括具有单、二、三或四官能基团的一种或多种丙烯酸酯。在一些实施方案中，丙烯酸酯可以包括多于一种类型的丙烯酸酯单体。在一些实施方案中，可以通过使用多官能乙氧基化丙烯酸酯单体产生网络。在一些实施方案中，乙氧基化二丙烯酸酯和乙氧基化三丙烯酸酯可用于形成网络。  \n\n[0029] 合适的亲水二丙烯酸酯单体的实例包括但不限于乙二醇二丙烯酸酯；乙二醇二甲 基丙烯酸酯；二甘醇二丙烯酸酯；三甘醇二丙烯酸酯；三甘醇二甲基丙烯酸酯；四甘醇二丙 烯酸酯；四甘醇二甲基丙烯酸酯；聚乙二醇二丙烯酸酯；三丙甘醇二丙烯酸酯；三异丙甘醇 二丙烯酸酯；聚丙二醇二甲基丙烯酸酯；衍生自PluronicTM或PolaxamerTM的聚醚二丙烯酸 酯，和衍生自反向PluroincTM的聚醚二丙烯酸酯。  \n\n[0030] 合适的亲水三丙烯酸酯单体的实例包括但不限于乙氧基化三羟甲基丙烷三丙烯酸酯、丙氧基化甘油基三丙烯酸酯、丙氧基化三羟甲基丙烷三丙烯酸酯和三(2‑羟基乙基)异氰脲酸酯三丙烯酸酯。  \n\n[0031] 合适的亲水四丙烯酸酯单体的实例包括但不限于乙氧基化季戊四醇四丙烯酸酯。[0032] 反应性表面活性剂  \n\n[0033] 如上所述，本发明的组合物的反应性表面活性剂可以包含亲水区域，且还可以包括能够与可交联树脂的反应性基团反应的反应性部分或基团。这种反应性部分可以包括但不限于烯基、丙烯酸酯基团、硫醇基或其组合中的一种或多种。应当注意，在将反应产物加入到丙烯酸酯混合物之前，可以使表面活性剂与一种或多种反应性部分反应，或可以同时将表面活性剂和反应性部分加入到丙烯酸酯混合物中。在一些实施方案中，反应性部分可位于反应性表面活性剂的亲水区域或亲水区中。  \n\n[0034] 具有烯基反应性基团的代表性反应性表面活性剂可具有化学通式： $\\left(\\mathrm{CH}_{2}\\ =\\ \\mathrm{CH}\\right)$ ‑R，其中R可选自醚磺酸酯、磷酸酯、聚醚及其共聚物、非离子聚醚、烷基醚、烯基醚和烯属醚，如表1所示。具有带反应性双键的亲水链段的反应性表面活性剂的说明性实例包括但不限于Reasoap  SR10、Reasoap  SR20、Reasoap  ER10、Reasoap  PP70、Emulsogen  APS100。具有烯基反应性基团的反应性表面活性剂的其他非限制性实例示于下表1中。  \n\n[0035] 表1  \n\n<html><body><table><tr><td>化合物</td><td>描述</td></tr><tr><td></td><td>醚磺酸酯 （R可以是烷基、芳基或其他） n=10,11，... M=金属或铵反荷离子</td></tr><tr><td>OP(OOH)</td><td>磷酸酯 n=10,11，..</td></tr><tr><td></td><td>非离子聚醚表面活性剂 （R可以是烷基、芳基或其他） n=10,11，...</td></tr><tr><td></td><td>聚醚硫酸酯 n=4,5.... m=10,11,. M=金属或铵反荷离子</td></tr><tr><td></td><td>聚醚共聚物 1=1,2.. n=1,2... m=1,2.... p=1,2..</td></tr></table></body></html>  \n\n[0036]  \n\n[0037] 具有丙烯酸酯反应性基团的代表性反应性表面活性剂可具有化学通式： $\\left(\\mathrm{CH}_{2}\\right.\\ =$ CHCOO)‑R，其中R可选自醚磺酸酯、磷酸酯、聚醚及其共聚物，如表2所示。具有带反应性丙烯酸酯部分的亲水链段的表面活性剂的说明性实例包括但不限于磺基丙基丙烯酸的金属盐和烷基丙烯酰氧基乙基三烷基铵盐。具有丙烯酸酯反应性基团的反应性表面活性剂的其他非限制性实例示于下表2中。  \n\n[0038] 表2  \n\n<html><body><table><tr><td>化合物</td><td>描述</td></tr><tr><td></td><td>醚磺酸酯 n=10,11. M=金属或铵反荷离子</td></tr><tr><td>OP(OOH)</td><td>磷酸酯 n=1,2</td></tr><tr><td>N(CHSOCH</td><td>聚醚 n=10,11，..</td></tr><tr><td></td><td>非离子聚醚共聚物 n=1,2.. m=1,2...</td></tr></table></body></html>  \n\n[0040] 具有硫醇反应性基团的代表性反应性表面活性剂可具有化学通式：(SH)‑R，其中R可选自醚磺酸酯、磷酸酯、聚醚及其共聚物，如表3所示。在一些实施方案中，具有带反应性硫醇部分的亲水链段的表面活性剂可通过三羟甲基丙烷三(3‑巯基丙酸酯)(TMPTMP)与Reasoap  SR10经由硫醇‑烯反应(参见预混物3)反应获得。在一些实施方案中，具有带反应性硫醇部分的亲水链段的表面活性剂可通过季戊四醇四(3‑巯基丙酸酯)与Reasoap  SR10经由硫醇‑烯反应来反应而获得。具有硫醇反应性的反应性表面活性剂的其他非限制性实例示于下表3中。  \n\n[0041] 表3  \n\n[0042]  \n\n<html><body><table><tr><td>化合物</td><td>描述</td></tr><tr><td></td><td>醚磺酸酯 （R'可以是烷基、芳基或其他） n=10,11,... M=金属或铵反荷离子</td></tr><tr><td></td><td>磷酸酯 n=1,2...</td></tr><tr><td></td><td>非离子聚醚共聚物 n=1，2，. m=1，2,...</td></tr></table></body></html>  \n\n[0043] 在一些实施方案中，反应性表面活性剂的反应性链段在固化过程期间与丙烯酸酯的亲水区反应。以这种方式，在固化后，反应性表面活性剂可以能够与固化的丙烯酸酯网络结合并因此保持在原位(未洗掉或以其他方式除去)，以提供具有持久的防雾性质的涂层。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# [0044] 金属氧化物颗粒  \n\n[0045] 在一些实施方案中，本发明的组合物可以包括分散在整个亲水可交联树脂例如丙烯酸酯的网络中的金属氧化物颗粒。金属颗粒可以向涂料提供硬度和耐磨性。金属氧化物纳米颗粒的合适实例包括但不限于二氧化硅颗粒、氧化钛、氧化铝、氧化锌、氧化锑、氧化锡、锆氧化物及其组合。在一些实施方案中，可以选择金属纳米颗粒的尺寸和浓度，使得所得涂料是光学透明的，同时仍保持其防雾性质和耐磨性质。在一些实施方案中，金属氧化物颗粒是尺寸范围为约5至约50nm的纳米颗粒。在一些实施方案中，金属氧化物颗粒是尺寸范围为约10至约20nm的纳米颗粒。纳米颗粒可以以0至80重量%的浓度存在。  \n\n[0046] 非反应性表面活性剂  \n\n[0047] 在一些实施方案中，可以将非反应性表面活性剂加入到涂料组合物中以进一步增强防雾性质。合适的非反应性表面活性剂包括但不限于磺酸盐、铵盐、磷酸盐、聚乙二醇醚低聚物、亲水聚丙烯酸酯、辛苯氧基聚乙氧基乙醇和非离子聚醚嵌段共聚物。在一些实施方案中，组合物中的非反应性表面活性剂的浓度可以为0至10重量%。在一些实施方案中，组合物中的非反应性表面活性剂的浓度可以为液体的0.5至 $2\\%$ 重量。  \n\n[0048] 光引发剂  \n\n[0049] 在一些实施方案中，组合物可以包含一种或多种光引发剂以在暴露到辐射或光后引发组合物的固化。涂料组合物中存在的一种或多种光引发剂引发并促进可固化树脂的交联，即当涂料组合物暴露到辐射时固化涂料组合物。在一些实施方案中，可选择光引发剂以在暴露到UV光或可见光时发生反应。在一些实施方案中，光引发剂是蓝光光引发剂。在一些实施方案中，为了固化组合物，当H灯泡用于暴露灯泡一分钟时，累积的UV‑A暴露可以在1.0和 $2.5\\mathrm{J}/\\mathrm{cm}^{2}$ 之间。  \n\n[0050] 用于本文公开的涂料组合物的合适的UV辐射敏化光引发剂或引发剂的共混物的实例包括但不限于苯偶姻；被取代的苯偶姻，如苯偶姻醚的丁基异构体；二苯甲酮；被取代的二苯甲酮，如羟基二苯甲酮；2‑羟乙基‑N‑马来酰亚胺；2‑[2‑羟乙基(甲基)氨基]乙醇蒽醌；噻吨酮；α,α‑二乙氧基苯乙酮；2,2‑二甲氧基‑1,2‑二苯基乙‑1‑酮；2‑羟基‑2‑甲基‑1‑苯基‑丙‑1‑酮；二苯基(2,4,6‑三甲基苯甲酰基)氧化膦，苯基乙醛酸甲酯；1‑羟基环己基苯基酮；2‑苄基‑2‑二甲基氨基‑1‑(4‑吗啉代苯基)‑丁酮‑1；2‑二甲基氨基‑2‑(4‑甲基‑苄基)‑1‑(4‑吗啉基‑4‑基‑苯基)‑丁‑1‑酮；2‑甲基‑1‑[4‑(甲硫基)苯基]‑2‑吗啉基丙‑1‑酮；和1‑[4‑(2‑羟基乙氧基)‑苯基]‑2‑羟基‑2‑甲基‑1‑丙烷‑1‑酮。阳离子光酸产生剂可以包括但不限于二苯基[3‑(苯基硫烷基)苯基]锍六氟磷酸盐；二苯基[2‑苯基硫烷基]苯基]锍六氟锑酸盐；三芳基锍与六氟磷酸盐的六氟锑酸盐在碳酸亚丙酯中的混合物；和二芳基碘鎓盐与五氟硼酸盐、六氟锑酸盐或六氟磷酸盐。  \n\n[0051] 任选地，光引发剂增效剂与酰基酮光引发剂例如二苯甲酮一起用作共引发剂。合适的光引发剂增效剂包括例如N‑甲基‑二乙醇胺、三乙醇胺2‑(丁氧基)乙基‑4‑二甲基氨基苯甲酸酯和可以从UCB  Radcure  Chemicals  Corporation ,  Smyrna ,  Ga .作为EBECRYLP104、EBECRYL  P105和EBECRYL  7100市售可得的反应性胺丙烯酸酯，或可以从SartomerCompany ,  Inc .,  Exton ,  Pa市售可得的CN  371、CN  373、CN  384或CN  386。Sartomer将CN373描述为反应性胺丙烯酸酯共引发剂，其可与夺氢光引发剂，例如二苯甲酮或异丙基噻吨酮(TTX)组合使用，以促进自由基聚合。CN  373加速表面固化速度且有助于克服可UV固化涂料和油墨中的氧气抑制。Sartomer将CN  371、CN  384、CN  386、CN  550和CN551描述为二官能和三官能胺丙烯酸酯共引发剂，当其与光敏剂如二苯甲酮一起使用时，促进在UV光下的快速固化。  \n\n[0052] 在一些实施方案中，组合物可以包括可见光光引发剂以在暴露到蓝光(400‑$500\\mathrm{nm})$ 后引发组合物的固化。这些光引发剂可以包括但不限于樟脑醌，苯丙二酮(PPD)，二丙烯酰基氧化膦(Ir819)，包括2,4,6‑三甲基苯甲酰基二苯基氧化膦(TPO)，2,4,6‑三甲基苯甲酰基乙氧基‑苯基氧化膦(TPO‑L)和双(2,4,6‑三甲基苯甲酰基)苯基氧化膦(BAPO)。  \n\n[0053] 在一些实施方案中，光引发剂可选自α羟基酮光引发剂的种类。在一些实施方案中，光引发剂包含Irgacure  500( $50\\%$ 二苯甲酮 $^+$ $50\\%$ 1‑羟基‑环己基‑苯基酮)和Darocure1173(2‑羟基‑2‑甲基‑苯丙酮)中的一种或多种。  \n\n[0054] 可替代地，可在最少使用或不使用光引发剂的情况下使用电子束(EB)辐射固化涂料制剂。  \n\n[0055] 流动改性剂/流平剂  \n\n[0056] 在一些实施方案中，本文公开的涂料组合物可以包括流平剂。流平剂(也可以称为流动控制剂)可以掺入本文所述的涂料组合物中以使组合物更均匀地铺展或在基材表面上流平，并提供与基材的基本上均匀的接触。流平剂的量可以广泛变化，但优选以涂料组合物的固体重量的约 $0.001\\%$ 至约 $10\\%$ 流平剂的量使用。采用任何常规的市售可得的流平剂，其与涂料组合物和基材相容，能够使涂料组合物在基材上流平，且增强涂料组合物和基材之间的润湿性。这种流平剂的非限制性实例包括聚醚，聚硅酮，含氟表面活性剂，聚丙烯酸酯，聚硅酮聚丙烯酸酯如聚硅酮六丙烯酸酯和氟改性的聚丙烯酸酯。实例包括来自Rohm  andHaas的TRITON  X‑100，X‑405和N‑57，聚硅酮例如来自Dow  Corning的Paint  Additive  3，Paint  Additive  29和Paint  Additive  57，来自Momentive(Columbus，OH)的SILWET  L‑77和SILWET  L‑7600，和含氟表面活性剂例如来自3M  Corporation(St .  Paul，MN)的FLUORADFC‑4430。  \n\n[0057] 其他添加剂  \n\n[0058] 其他成分如抗氧化剂、抗静电剂、耐候剂、着色添加剂、UV稳定剂、分散剂、消泡剂、热稳定剂也可以加入到涂料制剂中。抗氧化剂的实例包括十八烷基‑3‑(3,5‑二叔丁基‑4‑羟基苯基)丙酸酯和季戊四醇四[3‑(3,5‑二叔丁基‑4‑羟基苯基)丙酸酯]。  \n\n[0059] 热稳定剂的实例包括亚磷酸三苯酯、三(2,6‑二甲基苯基)亚磷酸酯、三‑(2,4‑二叔丁基‑苯基)亚磷酸酯、三‑(混合的单‑和二‑壬基苯基)亚磷酸酯、二甲基苯膦酸酯和磷酸三甲酯。抗静电剂的实例包括甘油单硬脂酸酯、硬脂酰磺酸钠和十二烷基苯磺酸钠。  \n\n[0060] 已知聚碳酸酯(PC)在紫外(UV)光的暴露下会降解。这个过程被称为自然老化。耐候性材料可在UV暴露下长时间保持其物理性质。为了改善UV暴露下的使用寿命，可以在聚碳酸酯和类似芳族塑料基材的涂料中使用UV吸收剂。UV吸收剂包括但不限于三组化学品：  \n\n1)  2‑羟基‑二苯甲酮(BP)衍生物，商业实例包括但不限于Chimassorb $\\circledast$ 81和Chimassorb$\\circledast$ 90(均来自BASF ,  Germany)；2)  2‑(2‑羟基苯基)‑苯并三唑(HPBT)衍生物，商业实例包括但不限于Tinuvin $\\circledast$ 1130，Tinuvin $\\circledast$ 384‑2，Tinuvin $\\circledast$ 928和Tinuvin $\\circledast$ 900(均来自BASF ,  Germany)；3)  2‑羟基苯基‑均三嗪(HPT)衍生物，商业实例包括但不限于Tinuvin $\\circledast$ 400，Tinuvin $\\circledast$ 405(均来自BASF ,  Germany)。  \n\n[0061] 受阻胺光稳定剂(HALS)也用于有效稳定以抵抗光和自然老化的有害影响。最广泛使用的受阻胺光稳定剂(HALS)主要是2,2,6,6‑四甲基哌啶的衍生物。商业实例包括但不限于Tinuvin $\\circledast$ 152，Tinuvin $\\circledast$ 292(均来自BASF，Germany)。  \n\n[0062] 示例性组合物  \n\n[0063] 本发明的组合物中的丙烯酸酯的浓度可以为约 $4\\%$ 至 $95\\%$ 重量。在一些实施方案中，本发明的组合物中的丙烯酸酯的浓度可以为液体涂料的 $7\\%$ 至 $55\\%$ 重量。在一些实施方案中，反应性表面活性剂的浓度可以为液体涂料的 $0.5\\%$ 至 $30\\%$ 重量。在一些实施方案中，丙烯酸酯和反应性表面活性剂之间的重量比可以在3:1和95:1之间。在一些实施方案中，组合物中的非反应性表面活性剂的浓度可以为液体重量的0.5至 $2\\%$ 。在一些实施方案中，组合物可以包括二氧化硅颗粒。  \n\n[0064] 在一些实施方案中，丙烯酸酯包含一种或多种乙氧基化二丙烯酸酯和一种或多种乙氧基化三丙烯酸酯的混合物。在一些实施方案中，二丙烯酸酯可以包含三甘醇二丙烯酸酯。在一些实施方案中，三丙烯酸酯可以包含乙氧基化三羟甲基丙烷三酰化物。在一些实施方案中，二丙烯酸酯和三丙烯酸酯之间的比率可以在1:3至1:7的范围内。在一些实施方案中，为了增强网络的亲水质，网络可以基本上或完全不含非亲水丙烯酸酯。在一些实施方案中，网络可能缺少非亲水丙烯酸酯或具有疏水区域的丙烯酸酯。在一些实施方案中，组合物可以进一步包括具有烯基反应性基团的反应性表面活性剂，但是可以使用具有丙烯酸酯基团、硫醇基团或这3种基团的组合的表面活性剂。在一些实施方案中，反应性表面活性剂是阴离子表面活性剂。本发明的组合物可进一步包括金属氧化物颗粒，例如二氧化硅，以赋予本发明的涂料的硬度和耐磨性。此外，本发明的组合物可以包括以下中的一种或多种：非反应性表面活性剂，溶剂，光引发剂和流动改性剂。  \n\n[0065] 作为非限制性实例，本公开提供具有以下比率(以干重计)的二氧化硅、二丙烯酸酯和三丙烯酸酯中的一种或多种的组合物。  \n\n[0066] 在一些实施方案中，组合物可以包含约15至约 $50\\%$ 重量的二丙烯酸酯，和任选地约5至约 $60\\%$ 重量的二丙烯酸酯，和约50至约 $85\\%$ 重量的三丙烯酸酯，和任选地约40至约 $100\\%$ 重量的三丙烯酸酯。  \n\n[0067] 在一些实施方案中，组合物可以包含约 $50\\%$ 至约 $70\\%$ 的金属氧化物颗粒，和任选地约 $15\\%$ 至约 $80\\%$ 重量的金属氧化物颗粒，和约 $30\\%$ 至约 $50\\%$ 重量的三丙烯酸酯，和任选地，约20至约 $85\\%$ 重量的三丙烯酸酯。  \n\n[0068] 在一些实施方案中，组合物可以包含约50至约 $71\\%$ 重量的金属氧化物颗粒，和任选地约30至约 $80\\%$ 重量的金属氧化物颗粒；约4至约 $25\\%$ 重量的二丙烯酸酯，和任选地约4至约$30\\%$ 重量的二丙烯酸酯，和约20至约 $50\\%$ 重量的三丙烯酸酯，和任选地约16至约 $70\\%$ 重量的三丙烯酸酯。  \n\n[0069] 作为非限制性实例，本公开提供以下组合物：  \n\n[0070] 在一些实施方案中，组合物可以包含在总涂料中约4至约 $35\\%$ 重量的二丙烯酸酯，且在一些实施方案中，任选地包含约2至约 $45\\%$ 重量的二丙烯酸酯；在总涂料中约15至约 $60\\%$ 重量的三丙烯酸酯，和任选地约10至约 $75\\%$ 重量的三丙烯酸酯；和约0.5至约 $2\\%$ 重量的反应性表面活性剂，和任选地约0.5至约 $30\\%$ 重量的反应性表面活性剂。在一些实施方案中，组合物还可以包含以下中的一种或多种：约0.5至约 $2\\%$ 重量的非反应性表面活性剂，和任选地约0 .5至约 $10\\%$ 重量的非反应性表面活性剂；约40至约 $65\\%$ 重量的溶剂，和任选地约40至约 $70\\%$ 重量的溶剂；和约1至约 $4\\%$ 重量的光引发剂和流动改性剂，和任选地0.5至约 $5\\%$ 重量的光引发剂和流动改性剂。  \n\n[0071] 在一些实施方案中，组合物可以包含在总涂料中约15至约 $50\\%$ 重量的金属氧化物颗粒，和任选地约5至约 $60\\%$ 重量的金属氧化物颗粒；在总涂料中约9至约 $35\\%$ 重量的三丙烯酸酯，且任选地约5至约 $60\\%$ 重量的三丙烯酸酯；和约0.5至约 $2\\%$ 重量的反应性表面活性剂，和任选地约0.5至约 $30\\%$ 重量的反应性表面活性剂。在一些实施方案中，组合物还可以包含以下中的一种或多种：约0.5至约 $2\\%$ 重量的非反应性表面活性剂，且在一些实施方案中，任选地约0.5至约 $10\\%$ 重量的非反应性表面活性剂；约40至约 $65\\%$ 重量的溶剂，且在一些实施方案中，任选地约30至约 $70\\%$ 重量的溶剂；和约1至约 $4\\%$ 重量的光引发剂和流动改性剂，且在一些实施方案中，任选地1至约 $5\\%$ 重量的光引发剂和流动改性剂。  \n\n[0072] 在一些实施方案中，组合物可以包含在总涂料中约15至约 $50\\%$ 重量的金属氧化物颗粒，和任选地约5至约 $70\\%$ 重量的金属氧化物颗粒；在总涂料中约1至约 $20\\%$ 重量的二丙烯酸酯，和任选地约1至约 $30\\%$ 重量的二丙烯酸酯；在总涂料中约6至约 $35\\%$ 重量的三丙烯酸酯，和任选地约4至约 $50\\%$ 重量的三丙烯酸酯；和约0.5至约 $2\\%$ 重量的反应性表面活性剂，和任选地约0.5至约 $30\\%$ 重量的反应性表面活性剂。在一些实施方案中，组合物还可以包含以下中的一种或多种：约40至约 $65\\%$ 重量的溶剂，且在一些实施方案中，任选地约10至约 $70\\%$ 重量的溶剂；和约1至约 $4\\%$ 重量的光引发剂和流动改性剂，且在一些实施方案中，任选地1至约 $5\\%$ 重量的光引发剂和流动改性剂。  \n\n[0073] 在一些实施方案中，组合物可以包含在总涂料中约15至约 $50\\%$ 重量的金属氧化物颗粒，且在一些实施方案中，任选地约5至约 $70\\%$ 重量的金属氧化物颗粒；在总涂料中约1至约 $20\\%$ 重量的二丙烯酸酯，且在一些实施方案中，任选地约1至约 $30\\%$ 重量的二丙烯酸酯；在总涂料中约6至约 $35\\%$ 重量的三丙烯酸酯，且在一些实施方案中，任选地约4至约 $50\\%$ 重量的三丙烯酸酯；约0.5至约 $2\\%$ 重量的反应性表面活性剂，且在一些实施方案中，任选地约0.5至约 $30\\%$ 重量的反应性表面活性剂。在一些实施方案中，组合物还可以包含以下中的一种或多种：约0.5至约 $2\\%$ 重量的非反应性表面活性剂，且在一些实施方案中，任选地约0.5至约 $10\\%$ 重量的非反应性表面活性剂；约40至约 $65\\%$ 重量的溶剂，且在一些实施方案中，任选地约10至约 $70\\%$ 重量的溶剂；约1至约 $4\\%$ 重量的光引发剂和流动改性剂，且在一些实施方案中，任选地1至约 $5\\%$ 重量的光引发剂和流动改性剂。  \n\n[0074] 基材/制品  \n\n[0075] 本文公开的涂料组合物可以作为涂料施加到刚性或柔性基材。合适的基材材料包括但不限于透明塑料，例如聚碳酸酯(PC)，极化聚碳酸酯，聚酰胺，聚丙烯酸类，聚甲基丙烯酸甲酯(PMMA)，聚氯乙烯，聚双烯丙基碳酸酯，烯丙基二甘醇碳酸酯(ADC)聚合物，聚对苯二甲酸乙二醇酯(PET)，聚环烷酸乙二醇酯，三乙酸纤维素(CTA)聚合物，乙酸丁酸纤维素(CAB)聚合物，聚氨酯，聚环硫醚和聚硫氨酯。如果需要，可以在适当预处理的情况下使用其他基材，包括各种聚烯烃，氟化聚合物，金属和玻璃，例如钠钙玻璃，硼硅酸盐玻璃，丙烯酸类玻璃及其他类型的玻璃。可以用本公开的涂料涂覆的制品的实例包括但不限于安全眼镜、光学镜片、护目镜、面罩、用于头盔的面板、用作建筑中的窗户的玻璃制品，以及用作汽车、公共汽车、火车、飞机和其他运输车辆的挡风玻璃或窗户的玻璃制品、多功能LED、LCD显示器、浴室镜、淋浴镜和固定装置。涂料也可以施用于商业冷冻器门、冰淇淋冷冻器门和熟食柜。在一些实施方案中，为了增加本发明的组合物对基材的粘合性，可以对基材进行表面处理和/或用底漆涂覆。在一些实施方案中，可以使用基于丙烯酸酯的底漆，特别是对于PMMA基材。  \n\n[0076] 另外，通过将所公开的组合物涂覆在薄的柔性基材如PC或PET膜制备的涂覆制品可以进一步安装/应用于需要防雾功能的制品，例如安全眼镜、光学镜片、护目镜、面罩、用于头盔的面板、用作建筑中的窗户的玻璃制品，以及用作汽车、公共汽车、火车、飞机和其他运输车辆中的挡风玻璃或窗户的玻璃制品、多功能LED、LCD显示器、浴室和淋浴镜。防雾柔性膜还可以经由可重新定位的光学透明粘合剂(例如压敏粘合剂)施加到商业冷冻器门、冰淇淋冷冻器门和显示器、熟食柜，以防止结霜和雾化。  \n\n[0077] 本文所述的涂料组合物可以任何合适的方式施加到基材。例如，本公开的组合物可以通过常规方法例如流涂、喷涂、幕涂、浸涂、旋涂、缝模涂覆、辊涂等施加到固体基材以形成基材上的连续表面膜。然后涂料组合物通过将涂覆的基材暴露到由UV灯提供的UV辐射、由可见光灯提供的可见光辐射，或在一些实施方案中，由EB促进剂提供的EB辐射，或这些的组合来固化，本领域技术人员已知所有这些技术。另外，通过在薄的柔性基材如PC或  \n\nPET膜上涂覆所公开的组合物制备的涂覆制品可以经由在刚性基材上的干法或湿法层压来安装或改装。  \n\n[0078] 在一些实施方案中，提供具有可洗涤防雾性质的制品的方法包括处理制品的表面并将本公开的可洗涤防雾涂料施加到表面，其中所述涂料可进一步是光学透明的，耐磨的，或二者。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 实施例  \n\n[0079] 以下实施例仅是代表性的不应当用于限制本公开的范围。对于实施例中公开的方法和组合物存在多种备选设计。因此，所选实施例主要用于说明本文公开的设备和方法的原理。  \n\n[0080] 测试描述：  \n\n[0081] 膜厚度：基于光谱反射率方法，用Filmetrics  F20‑CP分光光度计在632 .8nm的波长下测量固化涂料的膜厚度。  \n\n[0082] 雾度：通过根据ASTM  D1003标准用Haze‑gard  Plus雾度计(BYK‑Gardner，Columbia，Md.)测量雾度来评价固化涂料的透光性和光散射性质。  \n\n[0083] 黄色指数：黄色指数根据ASTM  E‑313在Shimadzu  UV‑1601  UV‑Vis分光光度计(Shimadzu  Scientific  Instruments  of  Kyoto，Japan)上测量。  \n\n[0084] 粘合性：粘合性是涂料粘合到基材的能力。使用一卷压敏胶带3M  Brand  SCOTCHTM600胶带测试初始粘合性。测试如下进行：1)在固化涂料中用可伸缩的剃刀刀片造成5  X  5网格的交叉线(约2mm间隔)；2)在交叉线区域上牢固地按下胶带(使用压舌器)；3)在 $90\\pm$ 30s后，以 ${180}^{\\circ}$ °的角度或尽可能靠近基材拉出胶带；4)通过使用适当的视觉控制检查涂覆的基材来检查涂料的除去；5)还在显微镜下检查对象区域；6)未受影响的区域的实际计数报告为粘合百分比(当粘合仅沿线受到影响时，估计值转换为百分比)。  \n\n[0085] 沸水粘合性：在将涂覆的样本在沸水中浸泡1小时后，对于某些样品也以与上述相同的方式测试粘合性。  \n\n[0086] 钢丝绒磨损：通过YT‑520钢丝绒测试仪测量的钢丝绒磨损给出在用标准等级的钢丝绒摩擦后的涂覆材料的耐磨性/耐刮擦性的定性测定。日本钢丝绒级0000(特细)用于测试。通过机器在约2”  x  2”区域中摩擦涂覆的表面进行10次冲击。测试以 $50\\mathrm{g}$ 的重量开始。如果涂料没有产生刮擦，则重量增加到 $100\\mathrm{g}$ 。因此，重量逐渐增加直到在涂料上观察到刮擦。例如，钢丝绒耐力等级为 $200\\mathrm{g}$ 的固化涂料在 $200\\mathrm{g}$ 的最小载荷下显示刮擦。  \n\n[0087] Bayer磨损测试：Bayer磨损测试是涂覆样本的耐磨性相对于未涂覆的CR39标准的耐磨性的定量测量。该测试在Colts  Laboratory  BTE磨损测试仪中使用 $500\\mathrm{g}$ Norton  ZF＃12  Alundum磨损介质进行。未涂覆的Silor  Optical  CR‑39  Plano镜片用作标准。在600次冲击后，注意到涂覆样本和CR39标准的雾度变化。Bayer比率报告为未涂覆的CR39标准的雾度百分比差除以涂覆样本的雾度百分比差。  \n\n[0088] Ta ber测试 ：Ta ber磨损测试 用具有 $500\\mathrm{g}$ 辅助负载重量和CS‑10F轮 (Ta berIndustries，North  Tonawanda，N .Y .)的Teledyne  Model  5155  Taber  Abrader(TaberIndustries ，North  Tonawanda ，N .Y .) 进行。在测量之前 ，用ST‑11光面石 (TaberIndustries，North  Tonawanda，N .Y .)使轮光面化。通过在光面石上25转CS‑10F轮来进行光面化。用配备有Taber磨损固定器(BYK‑Gardner，Columbia，Md .)的Haze‑gard  Plus(BYK‑Gardner，Columbia，Md .)记录样品的初始雾度4次。在样品上进行100次CS‑10F轮循环后，用配备有Taber磨损固定器(BYK‑Gardner，Columbia，Md .)的Haze‑gard  Plus(BYK‑Gardner，Columbia，Md .)再记录雾度4次。然后针对初始雾度读数和使用CS‑10F轮100次循环后的雾度读数确定平均雾度。然后报告100个循环的平均雾度读数和初始雾度读数之间的差。  \n\n[0089] 防雾性质  \n\n[0090] 呼气测试：通过将涂覆的基材保持在距测试仪约2.5至7.5cm进行呼气测试。测试仪吹在样品上以故意产生雾。如果在测试期间在涂覆的基材上没有出现雾，则涂料组合物通过呼吸测试。如果在表面上出现雾，则涂料组合物未通过该测试。  \n\n[0091] 初始防雾测试：通过将涂覆的基材放置在含有 $60^{\\circ}\\mathrm{C}$ 水源的烧杯上方的标准高度$(1^{\\mathfrak{v}})$ 下进行初始防雾测试。将涂覆的基材暴露到来自 $60^{\\circ}\\mathrm{C}$ 水的水蒸气1分钟。如果在该测试期间在涂覆的基材上出现雾，则记录出现雾花费的时间。如果在暴露1分钟期间没有出现雾，则认为涂料“通过”初始防雾测试。  \n\n[0092] 水浸泡防雾测试：将涂覆的基材在室温下浸泡在水中1小时。然后将涂覆的样本从水中取出，悬浮在 $25^{\\circ}\\mathrm{C},50\\%\\mathrm{RF}$ H的架子上12小时，并通过将涂覆的基材放置在含有 $50^{\\circ}\\mathrm{C}$ 的水的烧杯上1分钟来测试防雾性质。如果在该测试期间在涂覆的基材上出现雾，则记录出现雾所花费的时间。如果在暴露1分钟期间没有出现雾，则认为涂料“通过”1h水浸泡防雾测试。  \n\n[0093] 此外，根据EN166/EN168方案，使用YT‑810防雾化测试仪(由Yin‑Tsung  Co .，Ltd制造)测试12h调整的水浸的涂覆样本的防雾性质。测试包括将涂覆的基材放置在测试仪上。当测试开始时，将涂覆的基材暴露到 $50^{\\circ}\\mathrm{C}$ 蒸汽，并使激光通过镜片。通过在8秒(s)的暴露中减少激光的透射来确定雾化量。如果在8s期间激光透射率低于初始读数的 $80\\%$ ，则涂料未通过雾测试，否则，它被评定为通过。  \n\n[0094] 擦拭测试后的防雾  \n\n[0095] 干布擦拭测试‑用干燥的微纤维布擦拭涂覆的基材20次。在20次擦拭之后，通过呼气测试和 $60^{\\circ}\\mathrm{C}$ 烧杯测试评估防雾性质一分钟。如果两个测试都通过，则认为涂覆的基材通过干布擦拭防雾测试。  \n\n[0096] IPA擦拭测试‑将微纤维布用异丙醇浸泡，且然后擦过涂覆表面一次。在擦拭后，通过呼气测试和 $60^{\\circ}\\mathrm{C}$ 烧杯测试评价防雾性质。这构成一个IPA擦拭循环。如果涂覆的基材通过两个测试，则使其干燥30分钟并重新测试。报告在没有雾化的情况下完成的循环次数。  \n\n[0097] 湿布擦拭测试‑将微纤维布浸泡在水中。用湿布擦拭涂覆的基材十次。在擦拭10次后，使涂覆的样本干燥1分钟，并通过呼气测试和 $60^{\\circ}\\mathrm{C}$ 烧杯测试测试防雾性质。这构成一个湿布擦拭循环。如果涂覆的基材通过两个测试，则在 $25\\mathrm{{^\\circC}}$ 和 $50\\%\\mathrm{RH}$ 下调节24h并重新测试。报告在没有雾化的情况下完成的循环次数。  \n\n[0098] 洗涤测试后的防雾  \n\n[0099] 自来水洗涤测试‑将涂覆的基材放置在流动的自来水下，并用湿微纤维布擦拭表面20次。在20次擦拭后，使涂覆的部分在环境条件下干燥30分钟。然后通过呼气测试和 $60^{\\circ}\\mathrm{C}$ 烧杯测试进行测试。这构成一个水洗涤循环。如果涂覆的基材通过两个测试，则将其在25$\\mathrm{{^\\circC}}$ ， $50\\%$ RH下平衡24h并重新测试。报告在没有雾化的情况下完成的循环次数。  \n\n[0100] 皂和自来水洗涤测试‑将涂覆的部分用1wt%的“Simple  Green”清洁剂在水中的溶液擦拭一次，然后放置在流动的自来水下并用湿微纤维布擦拭二十次。在20次擦拭后，使涂覆的样品在环境条件下干燥1小时。然后通过呼气测试和 $60^{\\circ}\\mathrm{C}$ 烧杯测试测试样品的防雾性质。这构成一个皂水洗涤循环。如果涂覆的基材通过两个测试，则在 $25\\mathrm{{^\\circC}}$ ， $50\\%\\mathrm{RH}$ 下调节 $24\\mathrm{h}$ ，且然后重新测试。报告在没有雾化的情况下完成的循环次数。  \n\n[0101] 擦拭和洗涤循环在下表4中总结。 [0102] 表4  \n\n<html><body><table><tr><td rowspan=\"2\"></td><td rowspan=\"2\">测试名称</td><td colspan=\"2\">初始测试</td><td rowspan=\"2\">循环之间的持续 时间</td></tr><tr><td>方法</td><td>防雾测试之 前的时间</td></tr><tr><td rowspan=\"3\">擦拭测试</td><td>干布擦拭测试</td><td>用干布擦拭10次</td><td>立即</td><td></td></tr><tr><td>IPA擦拭测试</td><td>用IPA浸泡布擦拭1次</td><td>立即</td><td>30分钟</td></tr><tr><td>湿布擦拭测试</td><td>用水浸泡布擦拭10次</td><td>1分钟</td><td>24小时</td></tr><tr><td rowspan=\"2\">洗涤测试</td><td>自来水测试</td><td>在自来水下用布擦拭20次</td><td>30分钟</td><td>24小时</td></tr><tr><td>皂/自来水测试</td><td>用皂布擦拭1次，接着在 自来水下擦拭20次</td><td>1小时</td><td>24小时</td></tr></table></body></html>  \n\n[0104] 洗涤和擦拭测试(机器) ：可洗涤性测试仪(AB5005自动可洗涤性测试， $\\mathrm{TQC}$ Thermimport质量控制，Capelle  aan  den  Ussel，荷兰)，由机械装置组成，海绵在其上安装在固定臂上，施加重量，等于施加到测试材料的 $300\\mathrm{g}$ 力。经测试的材料为涂覆的涂底漆的PET膜。在测试期间，在所公开的测试1000和5000次循环中，将海绵在测试材料的表面上重复移动指定的循环次数。当海绵移动过表面时，液体以 $0.3\\mathrm{{m}1/\\mathrm{{min}}}$ 的速率施加到表面。测试的液体包括去离子水、无氨Windex和配方409清洁剂。在完成指定的循环后，通过用纸巾擦拭使测试材料干燥，且然后测试防雾性能。如果材料在洗涤后通过防雾测试，则确定涂料在指定数目的擦拭后保持防雾性能。如果立即防雾测试失败，则记录防雾恢复所需的时间。如果防雾性能没有恢复，涂料将被确定为永久性防雾失败。  \n\n[0105] 冷冻器测试：仅测试涂覆在 $125\\upmu\\mathrm{m}$ 厚的聚碳酸酯膜上的样品。用双面胶带将涂覆膜固定到玻璃绝缘被动冷冻器门。将冷冻器设定到指定温度，且使系统平衡至少1小时。门打开至少 ${\\cdot60}^{\\circ}$ °。如果涂料保持无雾至少6秒，则涂料通过测试。记录外部环境温度和相对湿度。  \n\n[0106] 在设定为 $\\mathrm{^-12.2^{\\circ}C}$ 的被动冷冻器上进行“平均冷冻器使用”模拟。门每隔10分钟打开，持续6秒的持续时间，直到1小时。测量雾清除的时间长度并测量各个涂覆制品的雾百分比 $(\\%)$ 。环境温度为 $20.9^{\\circ}\\mathrm{C}$ ，相对湿度为 $53.4\\%$ 。  \n\n[0107] 以下是本申请中提及的化学品和其他材料的缩写的描述：MEK‑AC‑2140Z：甲基乙基酮中的胶体二氧化硅分散体(Nissan  Chemical  America  Corporation)；PGM‑AC‑2140Y：在1‑甲氧基‑2‑丙醇中的胶体二氧化硅分散体(Nissan  Chemical  America  Corporation)；TMPTMP：三羟甲基丙烷三(3‑巯基丙酸酯)(Aldrich)；SR272：三甘醇二丙烯酸酯(SartomerAmericas)；SR454：乙氧基化(3)三羟甲基丙烷三丙烯酸酯(Sartomer  Americas)；SR499：乙氧基化(6)三羟甲基丙烷三丙烯酸酯(Sartomer  Americas)；SR9035：乙氧基化(15)三羟甲基丙烷三酰化物(Sartomer  Americas) ；SR415：乙氧基化(20)三羟甲基丙烷三丙烯酸酯(Sartomer  Americas)；3‑EGA：三甘醇二丙烯酸酯(Kyoeisha)；REASOAP  SR‑10：反应性阴离子醚硫酸盐表面活性剂(Adeka) ；REASOAP  SR‑20：反应性阴离子醚硫酸盐表面活性剂(Adeka)；REASOAP  ER‑10：反应性非离子醚表面活性剂(Adeka)；Emulsogen  APS‑100：烯丙基聚亚烷基二醇醚硫酸盐的非离子无APEO铵盐(Clariant)；Igepal  CA‑720：聚氧乙烯(12)异辛基苯基醚(Sigma  Aldrich)；Brij  30：聚氧乙烯(4) 月桂基醚(ACROS  Organics)；Brij58：聚氧乙烯二醇十六烷基醚(ACROS  Organics)；OT‑75：二辛基磺基琥珀酸钠( $75\\%$ 在水和醇中)，(Cytec  Industries，Inc .)；Schercoquat  IAS‑PG：异硬脂酰氨基丙基乙基二铵乙基硫酸盐和丙二醇(Lubrizol)；PM：1‑甲氧基‑2‑丙醇；TMPTA：三羟甲基丙烷三丙烯酸酯；NPC‑ST‑30：Organo  SiO2(Nissan  Chemical  America  Corporation)；Pelex  OT‑P：双(2‑乙基己基)磺基琥珀酸多库酸钠(Kao  Corp.)；Witcobond  240：水性聚氨酯分散体(Chemtura)；FZ‑2105：Dow  Corning  Toray；Paraloid  A‑11：热塑性丙烯酸树脂(Dow)；Dymax  XR‑9416：水可稀释的氨基甲酸酯丙烯酸酯(Dymax) ；BYK‑333：聚醚改性的聚二甲基硅氧烷(Byk) ；Coatosil  7602：具有环氧乙烷侧链的聚硅酮共聚物(Momentive)；和NeoRez  R9679：脂族水性氨基甲酸酯(DSM  Coating  Resins，LLC)。  \n\n[0108] 以下是本申请中提到的基材的描述：PC镜片：聚碳酸酯眼科镜片；CR‑39：CR‑39TM聚双烯丙基碳酸酯眼科镜片；MR‑7：MR‑7TM聚硫氨酯眼科镜片；Trivex：TrivexTM氨基甲酸酯眼科镜片；PET膜：双轴取向聚对苯二甲酸乙二醇酯膜；PC板：Bayer  MakrolonTM聚碳酸酯片；PC膜：125um厚的PC基材；涂底漆的PET膜：双轴取向聚对苯二甲酸乙二醇酯膜的专有处理；和PMMA：聚(甲基丙烯酸甲酯)。  \n\n[0109] 预混物：  \n\n[0110] 以下预混物用于实施例。预混物1：将135.01克SR9035加入到含有24.65g配备有磁力搅拌棒的3‑EGA的圆底烧瓶。将内容物在室温下连续搅拌30分钟。在搅拌30分钟后，在室温下在不断搅拌下缓慢加入850 .65克MEK‑AC‑2140Z，且将混合物搅拌过夜。然后使用Buschi  Rotovap在 $40^{\\circ}\\mathrm{C}$ 和730  mTorr下真空蒸馏混合物。然后将浓缩的树脂用192g的PM二醇醚稀释。然后将混合物转移到适合于包装可UV固化涂料的加盖棕色容器中并使其冷却至室温。预混物2：将70克OT75( $75\\%$ 固体的水溶液)加入到含有30克Schercoquat  IAS‑PG的容器中，并使用磁力搅拌棒连续搅拌4小时。预混物3：将75克REASOAP  SR10加入到含有25克TMPTMP的圆底烧瓶中，并使用机械混合器在 $70\\mathrm{{^\\circC}}$ 下搅拌8小时。然后将混合物转移到适合于包装可UV固化涂料的加盖棕色容器中并冷却至室温。预混物4：使用磁力搅拌棒将15克Witcobond  240与85克PM在容器中混合30分钟。预混物5：在 $250\\mathrm{mL}$ 容器中，将 $35.8\\mathrm{g}$ Eastek1400加入到128.5g去离子水并用磁性搅拌棒搅拌10分钟。将 $35.9\\mathrm{g}$ PM加入到混合物并使用磁力搅拌棒搅拌30分钟。预混物6：将70克PM乙酸酯和30克Paraloid  A‑11在 $60^{\\circ}\\mathrm{C}$ 下混合3小时。预混物7：将90克PM与10克BYK‑333在环境条件下混合30分钟。  \n\n[0111] 实施例1：  \n\n[0112] 将94 .7克预混物1、1 .47克预混物2、1 .50克预混物3和2.29克Darocur  1173加入到容器，并使用磁力搅拌棒在室温下搅拌30分钟。然后使涂料混合物静置1小时。[0113] 根据施加方式，通过用PM稀释进一步调节固体的涂料混合物。经由浸涂、刮涂棒、流涂和旋涂以各种方式施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。固化的样品通过水浸泡防雾测试，粘合性测试，并具有至多200克的钢丝绒耐磨性。当施加到PC镜片时，该制剂具有2.79的Bayer耐磨性。当流涂到Bayer  Makrolon聚碳酸酯片上时，该样品通过水浸泡防雾测试，并具有 $250\\mathrm{g}$ 的钢丝绒耐磨性。如前所述测试涂覆镜片的擦拭测试。这些涂料通过IPA测试至多10个循环，湿擦拭测试至多14个循环，且自来水洗涤测试至多21个循环。  \n\n[0114] 在底漆层即预混物4上，已将实施例1施用于CR‑39、MR‑7、Trivex和PC镜片。当施加到底漆层时，固化涂料通过水浸泡防雾测试，和沸水粘合性测试。  \n\n[0115] 下表5显示在Bayer  Makrolon聚碳酸酯片上流涂，接着在 $2.0\\mathrm{J/cm}^{2}$ 下固化后，实施例1的固化涂料的性质。  \n\n[0116] 表5 [0117]  \n\n<html><body><table><tr><td>性质</td><td>实施例1</td></tr><tr><td>厚度 (um)</td><td>4-6</td></tr><tr><td>雾度(%)</td><td>0.26</td></tr><tr><td>初始防雾测试</td><td>通过</td></tr><tr><td>水浸泡防雾测试</td><td>通过</td></tr><tr><td>粘合性</td><td>通过</td></tr><tr><td>钢丝绒 (g)</td><td>250g</td></tr><tr><td>Taber (100 rev)</td><td>5.71</td></tr></table></body></html>  \n\n[0118] 下表6显示实施例1的固化涂料的擦拭和洗涤测试后的防雾性质。  \n\n[0119] 表6  \n\n[0120]  \n\n<html><body><table><tr><td></td><td>测试名称</td><td>#测试的循 环</td><td>#通过的循 环</td></tr><tr><td rowspan=\"3\">擦拭测试</td><td>干布擦拭测试</td><td>1</td><td>1</td></tr><tr><td>IPA擦拭测试</td><td>10</td><td>10</td></tr><tr><td>湿布擦拭测试</td><td>直到失效</td><td>14</td></tr><tr><td rowspan=\"2\">洗涤测试</td><td>自来水测试</td><td>直到失效</td><td>21</td></tr><tr><td>皂/自来水测试</td><td>直到失效</td><td>21</td></tr></table></body></html>  \n\n[0121] 下表7显示涂覆在不同眼科镜片基材上的实施例1的固化涂料的性质(旋涂，在$2.0\\mathrm{J/cm}^{2}$ 下固化)。研究中使用的所有基材均通过表面处理设备进行表面处理，并在涂覆之前通过常规抛光方法抛光；将表面处理镜片基材用预混物4旋涂在经表面处理的那侧上，空气干燥90min，且然后用实施例1的涂料旋涂。  \n\n[0122] 表7  \n\n[0123]  \n\n<html><body><table><tr><td rowspan=\"2\">性质</td><td colspan=\"4\">基材</td></tr><tr><td>CR-39</td><td>MR-7</td><td>Trivex</td><td>PC镜片</td></tr><tr><td>厚度（um）</td><td>4.9</td><td>4.8</td><td>4.7</td><td>5.2</td></tr><tr><td>雾度（%)</td><td>0.21</td><td>0.30</td><td>0.26</td><td>0.53</td></tr><tr><td>初始防雾测试</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾测试</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>粘合性</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>沸水粘合性</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr></table></body></html>  \n\n[0124] 下表8显示实施例1的固化涂料在 $100\\upmu\\mathrm{m}$ 厚的预处理PET膜上的性质。经由流涂技术施加涂料并在 $2.0\\mathrm{J/cm}^{2}$ 下固化。  \n\n[0125] 表8  \n\n[0126]  \n\n<html><body><table><tr><td rowspan=\"2\">性质</td><td colspan=\"2\">PET膜预处理</td></tr><tr><td>电晕（30s）</td><td>用预混物5预涂 覆*</td></tr><tr><td>厚度（um）</td><td>3.9-5.0</td><td>6.0-8.0</td></tr><tr><td>雾度（%）</td><td>1.5-2.0</td><td>1.46</td></tr><tr><td>初始防雾</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾机器测试</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾测试</td><td>通过</td><td>通过</td></tr><tr><td>粘合性</td><td>通过</td><td>通过</td></tr></table></body></html>  \n\n[0127] \\*PET膜通过用预混物5流涂进行预处理，并在环境条件下干燥30min。  \n\n[0128] 实施例2：  \n\n[0129] 使用磁力搅拌棒在室温下将69 .88克预混物1、1 .09克预混物2、1 .11克REASOAPSR‑10、1 .69克Darocure  1173、0 .37克Tergitol $15\\mathrm{-}\\mathrm{s}-7$ 和25.86克PM混合30分钟。在混合后，在施加到基材之前使制剂静置1小时。经由浸涂和旋涂以各种方式施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。固化后的样品通过水浸泡防雾测试、粘合性测试，并具有至多150克的钢丝绒耐磨性。当施加到PC镜片时，该制剂具有2.82的Bayer耐磨性。  \n\n[0130] 实施例3：  \n\n[0131] 使用磁力搅拌棒在室温下混合69 .88克预混物1、1 .09克预混物2、0 .83克REASOAPSR‑10、0 .28克TMPTMP、1 .69克Darocure  1173、0 .37克Tergitol  15‑s‑7和25 .86克PM  30分钟。在混合后，使制剂静置1小时。经由浸涂和旋涂以各种方式施加涂料。涂覆的部分在  \n\nFusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。固化的样品通过水浸泡防雾测试、粘合性测试，并具有至多150克的钢丝绒耐磨性。当施加到PC镜片时，该制剂具有3.30的Bayer耐磨性。  \n\n[0132] 下表9显示固化涂料实施例1‑3的性质。经由浸涂在成品平聚碳酸酯镜片上涂覆涂料并在 $2.0\\mathrm{J/cm}^{2}$ 下固化。  \n\n[0133] 表9  \n\n<html><body><table><tr><td>性质</td><td>实施例1</td><td>实施例2</td><td>实施例3</td></tr><tr><td>厚度（um）</td><td>6.5</td><td>6.5</td><td>6.5</td></tr><tr><td>雾度（%）</td><td>0.28</td><td>0.30</td><td>0.35</td></tr><tr><td>初始防雾测试</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾机 器测试</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾测 试</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>粘合性</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>钢丝绒（g）</td><td>200</td><td>150</td><td>200</td></tr></table></body></html>  \n\n[0134]  \n\n[0135] 实施例4：  \n\n[0136] 使用磁力搅拌棒在室温下将41 .26克SR9035、7 .64克3‑EGA、1 .09克预混物2、1 .11克预混物3、1.69克Darocur  1173和46.84克PM混合30分钟。通过旋涂施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。固化的样品通过水浸泡防雾测试、粘合性测试，并具有至多<50克的钢丝绒耐磨性。当施加到PC镜片时，该制剂具有0.40的Bayer耐磨性。  \n\n[0137] 实施例5：  \n\n[0138] 使用磁力搅拌棒在室温下将69 .88克预混物1、4 .44克REASOAP  SR‑10、1 .69克Darocure  1173、0 .37克Tergitol $15\\mathrm{-}\\mathrm{s}^{\\ensuremath{-}7}$ 和25.86克PM混合30分钟。在混合后，在施加到基材之前使混合物静置1小时。经由浸涂和旋涂以各种方式施加涂料。涂覆的部分在FusionUV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。固化的样品通过水浸泡防雾测试、粘合性测试，并具有至多100克的钢丝绒耐磨性。当施加到PC镜片时，该制剂具有2.40的Bayer耐磨性。  \n\n[0139] 下表10显示实施例1‑6的固化涂料的性质。所有涂料经由旋涂在成品平聚碳酸酯镜片上施加。涂覆的镜片在 $2.0\\mathrm{J/cm}^{2}$ 下固化。  \n\n[0140] 表10[0142] 实施例6：  \n\n<html><body><table><tr><td rowspan=\"5\"></td><td>性质</td><td></td><td>实施例1实施例2实施例3</td><td></td><td></td><td>实施例4实施例5</td></tr><tr><td>厚度（um）</td><td>4.1</td><td>4.0</td><td>4.4</td><td>4.0</td><td>4.5</td></tr><tr><td>雾度(%)</td><td>0.25</td><td>0.31</td><td>0.29</td><td>0.30</td><td>0.22</td></tr><tr><td>初始防雾 测试</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防 雾机器测 试</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td></td><td>水浸泡防 雾测试</td><td>通过 通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>粘合性</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>钢丝绒（g）</td><td>200</td><td>150</td><td>150</td><td><50</td><td>100</td></tr><tr><td>Bayer</td><td>2.79</td><td>2.82</td><td>3.3</td><td>0.4</td><td>2.4</td></tr></table></body></html>  \n\n[0143] 使用磁力搅拌棒在室温下将69 .88克预混物1、1 .09克预混物2、1 .11克REASOAPSR‑10、1 .69克Darocur  1173、0 .37克Tergitol  15‑s‑7和65克PM混合30分钟。在混合后，使制剂静置1小时。在San  Diego ,  CA的SolarGard涂覆并固化PET膜。这些样品通过水浸泡防雾测试，且表现出至多400克的钢丝绒耐磨性。  \n\n[0144] 在另一组实验中，实施例6也经由刮涂棒施加到PC膜上。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。这些样品通过水浸泡防雾、初始粘合性，并表现出至多200克的钢丝绒耐磨性。  \n\n[0145] 下表11显示施加到涂底漆的PET和PC膜的实施例6的固化样品的性质。通过刮涂棒施加涂料并使用UV固化。  \n\n[0146] 表11  \n\n[0147]  \n\n<html><body><table><tr><td>性质</td><td>涂底漆的PET膜*</td><td>PC膜</td></tr><tr><td>厚度 (um)</td><td>4.5</td><td>3.0-8.0</td></tr><tr><td>雾度(%)</td><td>0.20-0.40</td><td>0.20-0.35</td></tr><tr><td>初始防雾测试</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾测试</td><td>通过</td><td>通过</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 说　明　书  \n\n<html><body><table><tr><td>钢丝绒</td><td>400g</td><td>200 g</td></tr><tr><td>粘合性</td><td>100%</td><td>100%</td></tr><tr><td>YI</td><td>1.58</td><td>1.19-1.30</td></tr></table></body></html>\n\n[0148] \\*在Solar  Gard ,  San  Diego ,  CA涂覆和固化  \n\n[0149] 下表12说明在 $125\\upmu\\mathrm{m}$ 厚的聚碳酸酯膜上涂覆至4微米厚的实施例6。在被动冷冻器门上进行涂覆样品的冷冻器测试。  \n\n[0150] 表12  \n\n[0151]  \n\n<html><body><table><tr><td colspan=\"4\"></td><td>把手</td><td>折页</td><td>LTF300</td></tr><tr><td>温度 (F）</td><td>温度 (C）</td><td>室温（C）</td><td>室内相对湿度 (%)</td><td>6秒测试</td><td>6秒测试</td><td>6秒测试</td></tr><tr><td>10</td><td>-12.2</td><td>22.7</td><td>47.8</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>5</td><td>-15</td><td>21.7</td><td>52.4</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>0</td><td>-17.8</td><td>20.5</td><td>60.7</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>-5</td><td>-20.6</td><td>20.9</td><td>60.5</td><td>通过</td><td>通过</td><td>通过</td></tr></table></body></html>  \n\n[0152] 下表13说明在 $125\\upmu\\mathrm{m}$ 厚的聚碳酸酯膜上涂覆至4微米厚的实施例6。在设定为‑12.2$\\mathrm{{^\\circC}}$ 的被动冷冻器上进行涂覆样品的冷冻器测试。门每10分钟打开，持续6秒的持续时间，直至1小时。测量雾清除的时间长度，且测量单个涂覆制品的雾百分比 $\\left(\\%\\right)$ 。环境室温为20 .9$\\mathrm{{^\\circC}}$ ，相对湿度为 $53.4\\%$ 。  \n\n[0153] 表13  \n\n[0154]  \n\n<html><body><table><tr><td>时间(min)</td><td>清除时间 (Sec)</td><td>平均雾化(%)</td></tr><tr><td>Ｏ</td><td>Ｏ</td><td></td></tr><tr><td>10</td><td>Ｏ</td><td></td></tr><tr><td>20</td><td></td><td>Ｏ</td></tr><tr><td>30</td><td></td><td></td></tr><tr><td>40</td><td>0</td><td>Ｏ</td></tr><tr><td>50</td><td></td><td>Ｏ</td></tr><tr><td>60</td><td>Ｏ</td><td>Ｏ</td></tr></table></body></html>  \n\n[0155] 下表14显示在1000和5000次循环的机器洗涤测试后涂覆的PET膜的防雾性质。[0156] 表14  \n\n[0157]  \n\n<html><body><table><tr><td>清洁液体</td><td>循环数目</td><td>测试方法</td><td>防雾测试之前的调整 时间</td><td>实施例6</td></tr><tr><td rowspan=\"2\">Windex（无氨）</td><td>1000</td><td rowspan=\"6\">防雾 (60℃，烧 杯，1min）</td><td>0min</td><td>通过</td></tr><tr><td>5000</td><td>0min</td><td>通过</td></tr><tr><td rowspan=\"2\">Formula409清洁 剂</td><td>1000</td><td>0min</td><td>通过</td></tr><tr><td>5000</td><td>0min</td><td>通过</td></tr><tr><td rowspan=\"7\">去离子水</td><td rowspan=\"2\">1000</td><td rowspan=\"2\">0min 15min</td><td></td><td>未通过</td></tr><tr><td></td><td>未通过</td></tr><tr><td rowspan=\"6\">5000</td><td rowspan=\"3\"></td><td>30min</td><td>通过</td></tr><tr><td>0min</td><td>未通过</td></tr><tr><td>15min</td><td>未通过</td></tr><tr><td>30min 1小时</td><td></td><td>未通过 未通过</td></tr><tr><td rowspan=\"2\"></td><td></td><td>未通过</td></tr><tr><td>2小时 18小时</td><td>通过</td></tr></table></body></html>  \n\n[0158] 实施例7：  \n\n[0159] 使用磁力搅拌棒在室温下将69 .04克预混物1、1 .06克预混物2、1 .08克REASOAPSR‑10、1 .69克Darocur  1173、1 .57克Capstone  FS‑35和25 .56克PM混合30分钟。在混合后，使制剂静置1小时。经由旋涂在PC、CR‑39、MR‑7和Trivex镜片上施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。这些样品通过水浸泡防雾和初始粘合性。用于涂覆的PC样品的Bayer为2.68，且钢丝绒耐磨性为200克。当施加到包括CR‑39、MR‑7和Trivex的其他基材时，这些样品保持防雾性质、粘合性，表现出200克的钢丝绒耐磨性，和2.5的Bayer磨损。  \n\n[0160] 实施例7也施用于背面常规表面处理的PC、CR‑39、MR‑7、MR‑8、MR‑10和Trivex镜片。首先将预混物4施加到选定的基材，然后是实施例7。使用来自LTI  Coa tingTechnologies，LLC的CrystalSpin  SV旋涂和固化装置施加和固化所有涂料。所有涂覆的基材都通过水浸泡防雾测试、粘合性，并表现出200克的钢丝绒抗性。这些涂料还通过15分钟的沸水粘合性测试。  \n\n[0161] 下表15显示涂覆在不同眼科镜片基材上的实施例7的固化涂料的性质(旋涂，使用Fusion  UV单元在 $2.0\\mathrm{J/cm}^{2}$ 下固化)。研究中使用的所有基材均通过表面处理设备进行表面处理，并在涂覆之前通过常规抛光方法抛光。将表面处理的镜片基材用预混物4旋涂在经表面处理的那侧并在旋转的同时干燥45秒，且然后用实施例7的涂料旋涂。  \n\n[0162] 表15  \n\n<html><body><table><tr><td rowspan=\"7\"></td><td>涂料</td><td>实施例7</td><td>实施例7</td><td>实施例7</td><td>实施例7</td><td>实施例7</td></tr><tr><td>底漆</td><td>预混物4</td><td>预混物4</td><td>没有</td><td>预混物4</td><td>预混物4</td></tr><tr><td>基材</td><td>CR39</td><td>聚碳酸酯</td><td>聚碳酸酯</td><td>MR7</td><td>Trivex</td></tr><tr><td>外观</td><td></td><td></td><td></td><td></td><td>平滑/优异平滑/优异平滑/优异平滑/优异平滑/优异</td></tr><tr><td>厚度 (mm)</td><td>4.8</td><td>4.9</td><td>4.4</td><td>4.9</td><td>4.4</td></tr><tr><td>雾度（%）</td><td>0.35</td><td>0.26</td><td>0.22</td><td>0.30</td><td>0.19</td></tr><tr><td>初始防雾测试</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾机器测试</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>粘合性</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>沸水粘合性100C，1h</td><td>通过</td><td>通过</td><td>未通过</td><td>通过</td><td>通过</td></tr><tr><td>钢丝绒（g）</td><td>200</td><td>200</td><td>200</td><td>200</td><td>200</td></tr><tr><td>Bayer比率</td><td>2.5</td><td>2.5</td><td>2.68</td><td>2.5</td><td>2.5</td></tr></table></body></html>  \n\n[0164] 下表16显示涂覆在不同眼科镜片基材上的实施例7的固化涂料的性质(旋涂，使用Crystal  Spin  SV单元在 $2.0\\mathrm{J/cm}^{2}$ 下固化)。研究中使用的所有基材均通过表面处理设备进行表面处理，并在涂覆之前通过常规抛光方法抛光。将表面处理的镜片基材在CrystalSpinSV单元内用预混物4旋涂在经表面处理的那侧，并在旋转的同时干燥45秒，且然后用实施例7的涂料旋涂。  \n\n[0165] 表16 [0167] 实施例7a：  \n\n<html><body><table><tr><td rowspan=\"7\">66]</td><td></td><td>基材厚度（mm）雾度（%）</td><td></td><td>YI</td><td>钢丝绒 (g）</td><td>粘合性</td><td></td><td>初始防雾测试水浸泡防雾测试</td></tr><tr><td>Poly</td><td>5.8</td><td>0.22</td><td>0.98</td><td>200</td><td>100%</td><td>通过</td><td>通过</td></tr><tr><td>MR-7</td><td>5.7</td><td>0.21</td><td>1.88</td><td>200</td><td>100%</td><td>通过</td><td>通过</td></tr><tr><td>MR-8</td><td>5.8</td><td>0.25</td><td>1.92</td><td>200</td><td>100%</td><td>通过</td><td>通过</td></tr><tr><td>MR-10</td><td>5.8</td><td>0.22</td><td>1.69</td><td>200</td><td>100%</td><td>通过</td><td>通过</td></tr><tr><td>CR-39</td><td>5.1</td><td>0.21</td><td>0.90</td><td>200</td><td>100%</td><td>通过</td><td>通过</td></tr><tr><td>TrivexTM</td><td>5.1</td><td>0.19</td><td>0.96</td><td>200</td><td>98%</td><td>通过</td><td>通过</td></tr></table></body></html>  \n\n[0168] 使用磁力搅拌棒在室温下将69 .04克预混物1、1 .06克预混物2、1 .69克Darocur1173、1 .57克Capstone  FS‑35和25 .56克PM混合30分钟。在混合后，使制剂静置1小时。经由旋涂在PC镜片上施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。这些样品未通过水浸泡防雾并通过初始粘合性。  \n\n[0169] 实施例7b：  \n\n[0170] 使用磁力搅拌棒在室温下将69 .04克预混物1、1 .06克OT‑75、1 .69克Darocur1173、1 .57克Capstone  FS‑35和25 .56克PM混合30分钟。在混合后，使制剂静置1小时。经由旋涂在PC镜片上施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。这些样品未通过水浸泡防雾并通过初始粘合性。  \n\n[0171] 下表17显示与样品9相比不含反应性表面活性剂组合的固化样品的性质。将涂料旋涂在PC镜片上，并使用Fusion  UV固化单元在 $2.0\\mathrm{J/cm}^{2}$ 下固化。  \n\n[0172] 表17  \n\n[0173]  \n\n<html><body><table><tr><td>性质</td><td>实施例7</td><td>实施例7a</td><td>实施例7b</td></tr><tr><td>厚度 (um)</td><td>4.2</td><td>4.0</td><td>4.0</td></tr><tr><td>雾度 (%)</td><td>0.22</td><td>0.19</td><td>0.11</td></tr><tr><td>初始防雾测试</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾测试</td><td>通过</td><td>未通过</td><td>未通过</td></tr><tr><td>粘合性</td><td>通过</td><td>通过</td><td>通过</td></tr></table></body></html>  \n\n[0174] 实施例8：  \n\n[0175] 使用磁力搅拌棒在室温下将69 .04克预混物1、1 .06克预混物2、1 .08克EmulsogenAPS‑100、1 .69克Darocur  1173、1 .57克Capstone  FS‑35和25 .56克PM混合30分钟。在混合后，使制剂静置1小时。经由旋涂在PC镜片上施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。固化的样品通过水浸泡防雾，未通过初始粘合性，并表现出200克的钢丝绒耐磨性。  \n\n[0176] 实施例9：  \n\n[0177] 使用磁力搅拌棒在室温下将69 .04克预混物1、1 .06克预混物2、1 .08克REASOAPSR‑20、1 .69克Darocur  1173、1 .57克Capstone  FS‑35和25 .56克PM混合30分钟。在混合后，使制剂静置1小时。经由旋涂在PC镜片上施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。固化的样品通过水浸泡防雾，未通过初始粘合性，并表现出150克的钢丝绒耐磨性。  \n\n[0178] 下表18显示不同反应性表面活性剂组合的固化样品的性质。将涂料旋涂在GentexPC镜片上，并使用Fusion  UV固化单元在 $2.0\\mathrm{J/cm}^{2}$ 下固化。  \n\n[0179] 表18  \n\n[0180]  \n\n<html><body><table><tr><td>性质</td><td>实施例7</td><td>实施例8</td><td>实施例9</td></tr><tr><td>厚度 (um)</td><td>4.2</td><td>4.0</td><td>4.1</td></tr><tr><td>雾度(%)</td><td>0.22</td><td>0.27</td><td>0.27</td></tr><tr><td>初始防雾测试</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾测试</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>粘合性</td><td>通过</td><td>未通过</td><td>未通过</td></tr></table></body></html>  \n\n[0181] 实施例10：  \n\n[0182] 使用磁力搅拌棒在室温下将69.04克预混物1、1 .06克Igepal  CA‑720、1 .08克预混物3、1 .69克Darocur  1173、1 .57克Capstone  FS‑35和25 .56克PM混合30分钟。在混合后，使制剂静置1小时。经由旋涂在PC镜片上施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。这些样品通过水浸泡防雾和初始粘合。  \n\n[0183] 实施例11：  \n\n[0184] 使用磁力搅拌棒在室温下将69 .04克预混物1、1 .06克Igepal  CA‑720、1 .08克REASOAP  SR‑10、1 .69克Darocur  1173、1 .57克Capstone  FS‑35和25 .56克PM混合30分钟。在混合后，使制剂静置1小时。经由旋涂在PC镜片上施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。这些样品通过水浸泡防雾和初始粘合。  \n\n[0185] 实施例12：  \n\n[0186] 使用磁力搅拌棒在室温下将69 .04克预混物1、1 .06克Igepal  CA‑720、1 .08克REASOAP  ER‑10、1 .69克Darocur  1173、1 .57克Capstone  FS‑35和25 .56克PM混合30分钟。在混合后，使制剂静置1小时。经由旋涂在PC镜片上施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。这些样品通过水浸泡防雾和初始粘合。  \n\n[0187] 下表19显示使用Igepal的不同非反应性表面活性剂的固化样品的性质。将涂料旋涂在Gentex  PC镜片上，并使用Fusion  UV固化单元在2.0J/cm 下固化。  \n\n[0188] 表19  \n\n[0189]  \n\n<html><body><table><tr><td>性质</td><td>实施例10</td><td>实施例11</td><td>实施例12</td></tr><tr><td>厚度 (um)</td><td>4.4</td><td>4.0</td><td>4.3</td></tr><tr><td>雾度(%)</td><td>0.23</td><td>0.21</td><td>0.28</td></tr></table></body></html>  \n\n<html><body><table><tr><td>初始防雾测试</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾测试</td><td>通过</td><td>通过</td><td>通过</td></tr><tr><td>粘合性</td><td>通过</td><td>通过</td><td>通过</td></tr></table></body></html>  \n\n[0190] 实施例13：  \n\n[0191] 使用磁力搅拌棒在室温下将69 .04克预混物1、1 .06克预混物2、1 .08克REASOAPSR‑10、1 .00克Irgacure  500、1 .57克Capstone  FS‑35和25 .56克PM混合30分钟。在混合后，使制剂静置1小时。经由旋涂在PC上施加涂料。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。这些样品未通过水浸泡防雾并通过初始粘合性。该涂料表现出1 .72的Bayer磨损。  \n\n[0192] 下表20显示使用不同光引发剂的性质比较。将涂料旋涂在背面PC上，并使用Fusion  UV固化单元在 $2.0\\mathrm{J/cm}^{2}$ 下固化。  \n\n[0193] 表20  \n\n[0194]  \n\n<html><body><table><tr><td>性质</td><td>实施例7</td><td>实施例13</td></tr><tr><td>厚度 (um)</td><td>4.2</td><td>4.1</td></tr><tr><td>雾度(%)</td><td>0.25</td><td>0.24</td></tr><tr><td>初始防雾测试</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾测试</td><td>通过</td><td>未通过</td></tr><tr><td>粘合性</td><td>通过</td><td>通过</td></tr><tr><td>Bayer</td><td>2.68</td><td>1.72</td></tr><tr><td>YI</td><td>1.31</td><td>1.16</td></tr></table></body></html>  \n\n[0195] 实施例14：  \n\n[0196] 将6.75克预混物6与93.15克PM和0.1克预混物7混合1小时。使液体静置，且然后流涂在PMMA板上并在环境条件下干燥30分钟。然后使用磁力搅拌棒在室温下将69.04克预混物1、1 .06克预混物2、1 .08克预混物3、1 .69克Darocur  1173、1 .57克Capstone  FS‑35和25.56克PM混合30分钟。在混合后，使制剂静置1小时。然后经由刮涂棒将该液体施加到涂覆有底漆的PMMA。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。该涂料通过初始粘合和水浸泡防雾。  \n\n[0197] 下表21显示施加到具有底漆的PMMA板的实施例14的性质。  \n\n[0198] 表21  \n\n[0199]  \n\n<html><body><table><tr><td>底漆</td><td>涂料厚度 (um)</td><td>雾度(%)</td><td>粘合性</td><td>初始防雾测试</td><td>水浸泡防雾测试</td><td>钢丝绒磨损(g)</td></tr><tr><td>实施例14</td><td>10.9</td><td>0.48</td><td>通过</td><td>通过</td><td>通过</td><td>200</td></tr></table></body></html>  \n\n[0200] 实施例15：  \n\n[0201] 使用磁力搅拌棒在室温下将332克PGM‑AC‑2140Y、9 .9克SR‑272、52 .9克SR‑9035、4 .44克REASOAP  SR‑10、4 .5克预混物2、6 .8克Darocur  1173、1 .5克Tergitol $15\\mathrm{-}\\mathrm{s}^{\\phantom{-}}7$ 和168克PM混合30分钟。在混合后，使制剂静置1小时。经由刮涂棒将涂料施加到涂底漆的PET基材。涂覆的部分在Fusion  UV固化单元中用H灯泡在 $2.0\\mathrm{J/cm}^{2}$ 下固化。这种涂料未通过初始粘合性，并通过水浸泡防雾。  \n\n[0202] 下表22显示实施例6和实施例15的固化样品的性质，其经由刮涂棒施加到 $50\\mathrm{{um}}$ 厚的涂底漆的PET膜，并使用Fusion  UV固化单元在2.0J/cm 下固化。  \n\n[0203] 表22  \n\n[0204]  \n\n<html><body><table><tr><td>性质</td><td>实施例6</td><td>实施例15</td></tr><tr><td>厚度 (um)</td><td>4.5</td><td>4.0-6.9</td></tr><tr><td>雾度 (%)</td><td>0.20-0.40</td><td>0.34</td></tr><tr><td>粘合性 (%)</td><td>通过</td><td>未通过</td></tr><tr><td>初始防雾</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾测试</td><td>通过</td><td>通过</td></tr></table></body></html>  \n\n[0205] 实施例16：  \n\n[0206] 根据US  6 ,946 ,498  B2的教导，将 $3.38\\mathrm{g}$ 去离子水加入到 $73.88\\mathrm{g}$ NPC‑ST‑30中并在室温下搅拌。将5 .16g  A‑174缓慢滴入到搅拌的混合物中并混合2小时。然后将 $11.12\\mathrm{g}$ TMPTA加入到搅拌的混合物，接着加入 $3.28\\mathrm{g}0\\mathrm{T}-75$ 并使其混合12小时。然后将 $\\mathrm{1.59g}$ Darocur  1173加入到混合物中并在室温下再混合30分钟。通过刮涂棒将涂料施加到PET膜或PC板。涂覆的部分在Fusion  UV固化装置中用H灯泡在 $1.0\\mathrm{J/cm}^{2}$ 下固化。样品不通过水浸泡防雾测试。  \n\n[0207] 下表23显示经由刮涂棒施加的实施例16的固化涂料的性质，并在 $1.0\\mathrm{J/cm}^{2}$ 下固化。  \n\n[0208] 表23  \n\n<html><body><table><tr><td rowspan=\"11\">[0209]</td><td>性质</td><td>实施例16</td><td>实施例16</td></tr><tr><td>基材</td><td>PET</td><td>PC板</td></tr><tr><td>厚度（um）</td><td>3.5</td><td>3.5</td></tr><tr><td>雾度（%）</td><td>1.1</td><td>0.39</td></tr><tr><td>初始防雾测试</td><td>通过</td><td>通过</td></tr><tr><td>水浸泡防雾机器测试</td><td>未通过</td><td>未通过</td></tr><tr><td>水浸泡防雾测试</td><td>未通过</td><td>未通过</td></tr><tr><td>粘合性</td><td>未通过</td><td>未通过</td></tr><tr><td>钢丝绒（g）</td><td>500</td><td>500</td></tr></table></body></html>  \n\n[0210] 本文引用的所有专利、专利申请和公开的参考文献均通过引用整体并入本文。应当强调，本公开的上述实施方案仅仅是设施方式的可能实施例，仅仅是为了清楚地理解本公开的原理而提出。在不偏离本发明的精神和原理的情况下，可以对上述一个或多个实施方案进行许多变化和修改。可以了解，上文公开的和其他特点和功能中的一些或其替代方案可以理想地组合到许多其他不同的系统或应用。所有这些修改和变化在此旨在包括在本公开的范围内，落入所附权利要求的范围内。  \n\n![](images/2c9df8a72656fe5b98776b9b4f50e2cac49c80806014c3ad5a98434a53de0218.jpg)  \n\n![](images/8cb481f25b9a3aed6119139060fcb7012a369e551fe3d981f3fb613bd4dda5da.jpg)  \n图 1",
+        "category": " Results and discussion"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/SMiPoly┐╔║╧│╔╛█║╧╬я╨щ─т┐т╡─╔·│╔╩╣╙├╗∙╙┌╣ц╘Є╡─╛█║╧╖┤╙ж.json b/task2/task2-chunks/SMiPoly┐╔║╧│╔╛█║╧╬я╨щ─т┐т╡─╔·│╔╩╣╙├╗∙╙┌╣ц╘Є╡─╛█║╧╖┤╙ж.json
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+++ b/task2/task2-chunks/SMiPoly┐╔║╧│╔╛█║╧╬я╨щ─т┐т╡─╔·│╔╩╣╙├╗∙╙┌╣ц╘Є╡─╛█║╧╖┤╙ж.json
@@ -0,0 +1,72 @@
+[
+    {
+        "id": 1,
+        "chunk": "# SMiPoly: Generation of a Synthesizable Polymer Virtual Library Using Rule-Based Polymerization Reactions  \n\nMitsuru Ohno,\\* Yoshihiro Hayashi, Qi Zhang, Yu Kaneko, and Ryo Yoshida\\*  \n\nCite This: J. Chem. Inf. Model. 2023, 63, 5539−5548",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# ACCESS  \n\nMetrics & More  \n\nArticle Recommendations  \n\nSupporting Information  \n\nABSTRACT: Recent advances in machine learning have led to the rapid adoption of various computational methods for de novo molecular design in polymer research, including high-throughput virtual screening and inverse molecular design. In such workflows, molecular generators play an essential role in creation or sequential modification of candidate polymer structures. Machine learningassisted molecular design has made great technical progress over the past few years. However, the difficulty of identifying synthetic routes to such designed polymers remains unresolved. To address this technical limitation, we present Small Molecules into Polymers (SMiPoly), a Python library for virtual polymer generation that implements 22 chemical rules for commonly applied polymerization reactions. For given small organic molecules to form a candidate monomer set, the SMiPoly generator conducts possible polymerization reactions to generate an exhaustive list of potentially synthesizable polymers. In this study, using 1083 readily available monomers, we generated 169,347 unique polymers forming seven different molecular types: polyolefin, polyester, polyether, polyamide, polyimide, polyurethane, and polyoxazolidone. By comparing the distribution of the virtually created polymers with approximately 16,000 real polymers synthesized so far, it was found that the coverage and novelty of the SMiPoly-generated polymers can reach 48 and $53\\%$ , respectively. Incorporating the SMiPoly library into a molecular design workflow will accelerate the process of de novo polymer synthesis by shortening the step to select synthesizable candidate polymers.  \n\n![](images/c6bb04d570f5ef74cd3ac4b847c054e12983cf4fffb330e5e854a9a0bb03b4d2.jpg)",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# INTRODUCTION  \n\nIn recent years, data-driven and computer-aided molecular design technologies have spread rapidly1,2 across various areas of materials research, such as drug discovery,3,4 catalyst design,5−8 and polymer design.9−12 The task of molecular design boils down to the forward and backward predictions.13 The objective of the forward prediction is to obtain a forward mapping from any given chemical structure to its properties. In a conventional scenario, supervised learning is performed to learn the structure−property relationships. In the backward prediction, the inverse mapping of the forward model is obtained to identify promising chemical structures that exhibit desired properties. The most traditional approach to solving the inverse problem is to perform high-throughput virtual screening; millions or billions of candidate molecules are computationally created, and the forward model is used to determine whether their properties fall into the target region or not.14−16 Alternatively, adaptive heuristic search algorithms, such as evolutionary computatio n,17−19 Bayesian optimization,20 particle swarm optimization,21 and Monte Carlo computation11,13,22 have also been used to iteratively modify the candidate molecules to achieve the desired properties.  \n\nHere, the performance of molecular generators plays a key role in determining the success or failure of molecular design.  \n\nTraditionally, virtual libraries have been constructed by probabilistically recombining chemical fragments from which substituent groups or ring structures of existing molecules are pre-extracted.17,23 Recently, molecular generators using statistically trained generative models have also become widely used.24 For example, a probabilistic language model is trained to generate simplified molecular input line entry system (SMILES)25 strings by converting existing molecules into the training string set.11,13,15,22 Alternatively, deep generative models based on the graph representation of molecules have been studied extensivel y.26−28 While the traditional methods limit the searchable space to a combination of predefined fragment sets, generative machine-learning models can create novel molecules from a wider chemical space. However, it is not guaranteed that such computationally designed virtual molecules are feasible to synthesize.29 One way to overcome this drawback is to use synthetic reaction models.30,31 From a large set of synthetic reactions of organic compounds in a public database, a deep neural network is trained to predict the synthetic products of a given set of reactants.32 In addition to such generative machine-learning models, rule-based models compiling prior knowledge of chemical reactions,14 hybrid models of machine learning and rule-based methods,16,24,33 and retrosynthetic analysis34,35 have been proposed. By feeding commercially available reactants to such a prediction model, a virtual library can be constructed in which synthesizability and synthetic routes are taken into account.  \n\nThe aforementioned methodologies have been developed primarily for designing small molecules. However, the development of general-purpose polymer generators has lagged far behind that of small molecule generators. Thus far, polymer repeating units with their chemical structures have been generated by statistical generative models trained from existing polymers in the same manner as the generation of small molecules. Wu et al.11 designed and synthesized three amorphous polymers with high thermal conductivity by solving an inverse problem using a probabilistic language model trained on synthetic polymers recorded in the polymer properties database PoLyInfo.36 In addition, several applications of polymer generative models have been reported for inverse design for the dielectric constant and solubility of polymers.16,37,38 Ma and Luo15 constructed a virtual library of more than one million polymers using a deep language generative model trained on the synthetic polymers in PoLyInfo as well. Methodological and practical research on the computational design of polymeric materials is less advanced than for small molecules.39,40 The lack of data resources for polymeric materials is a significant bottleneck. Furthermore, the synthesis of computationally generated polymers presents a greater technical hurdle than for small materials; in order to estimate the synthesizability of the generated polymers, it is necessary to break a designed polymer down into starting monomers and investigate their availability. Computational methodologies for this have not been well studied.  \n\nRecently, Kim et al.16 provided a generative model of synthetically accessible polymer repeating units with a rulebased polymerization reaction algorithm. Using this system, they constructed a database called the Open Macromolecular Genome (OMG) that contains highly synthesizable virtual polymers. The OMG will be an important database for datadriven polymer research, but there is room for improvement in the definition of rule sets. From the viewpoint of synthetic organic chemistry, the reactivity of a substrate is influenced by the steric and electrical effects of the substituents in the reaction center. Furthermore, as pointed out in that paper, the selectivity of the reaction is influenced by coexisting functional groups in the reactant molecule. Therefore, it is necessary to provide reaction rules that take these factors into account.  \n\nIn this study, we built a virtual library generator for polymers that implements a comprehensive rule set for practically applied polymerization reactions with a Python open-source library, Small Molecules into Polymers (SMiPoly). The generators implement 22 reaction rules that consist of six chain polymerization reactions and 16 step-growth polymerization reactions. The types of polymerization reactions used in actual polymer synthesis are quite limited compared to the overall organic synthetic reactions. Our rule set covers a significant portion of common polymerization reactions considered in previous studies.41−44  \n\nUsing 1083 input monomers carefully selected based on availability, cost, safety, and legal compliance, seven classes of polymers, i.e., polyolefins, polyesters, polyethers, polyamides, polyimides, polyurethanes, and polyoxazolidones, were polymerized in silico. The generated virtual polymers have significantly promising synthesizability with the navigation of polymerization routes. The distribution of the 169,347 generated polymers and nearly 16,000 synthesized polymers forming the 21 polymer classes in PoLyInfo were compared to systematically and quantitatively evaluate the coverage and novelty of the virtual library with respect to the existing polymers. Our library generator covered approximately $50\\%$ of the chemical space of the polymers synthesized to date, and approximately $50\\%$ of the polymers produced were outside the distribution of the existing polymers.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# METHODS  \n\nThe SMiPoly library implements a rule set of 22 polymerization reactions, which consists of two submodules, “monc.py” and “polg.py” (Figure 1). The submodule “monc.py” extracts monomers from the given set of starting molecules and classifies them into 19 different monomer classes by checking whether or not to include polymerizable functional groups of the 22 polymerization reactions. The submodule “polg.py” applies the functional group transformations programmed into an applicable polymerization reaction to generate the chemical structure of a polymer repeating unit from the given one or two starting monomers. The current implementation is capable of generating seven classes of polymers. In the following, each step is described in detail.  \n\n![](images/43a5dcb639b689f55ac275d7f0612a1a9baae28837132154768f292478ac639a.jpg)  \nFigure 1. Workflow of the monomer classification and the polymer generation with SMiPoly.  \n\nPolymerization Reactions. The 22 polymerization reactions are classified in accordance with domain knowledge as summarized in Figure 2.41,42,44 The definition of the terms follows the chemical terminology of the International Union of Pure and Applied Chemistry (IUPAC)43,45 except for “stepgrowth polymerization” and “addition-condensation” as described below.  \n\nAt first, we classified common polymerization reactions into two types: chain polymerization and step-growth polymerization. These two types are classified according to the reaction mechanism of the polymer chain growth. The polymerization reactions in which the growth of a polymer chain proceeds exclusively by a chain reaction are categorized as chain polymerization, and others are defined as step-growth polymerization. The step-growth polymerization here indicates a polymerization reaction in which the growth of polymer chains proceeds by reactions between molecules of all degrees of polymerization. The chain polymerization can be further classified into addition chain polymerization and ring-opening chain polymerization on the basis of the type of chemical reactions involved in the growth step. The step-growth polymerization can be classified into three types: polycondensation, polyaddition, and addition-condensation. The additioncondensation here means a polymerization reaction in which addition and condensation reactions are repeated alternately.  \n\n![](images/7c99c5520db5b138060cd7c4435b4fd39702489c8ed349cc6382832ac4386640.jpg)  \nFigure 2. Classification of polymerization reactions implemented in the SMiPoly library. The definition of the terms is in accordance with the chemical terminology of the International Union of Pure and Applied Chemistry (IUPAC)43,45 except for “step-growth polymerization” and “additioncondensation”.  \n\nEach reaction class consists of several polymerization reactions defined by specific functional group transformations. A polymerization reaction is expressed as a set of the starting monomer(s) and the functional group transformation represented by reaction SMiles ARbitrary Target Specification (SMARTS).46 The 22 polymerization reactions currently implemented and their functional group transformations represented by reaction SMARTS are summarized in Table 1, and illustrative examples of the rule-specific functional group transformations are shown in Table ??. The current rule set can generate the seven polymer classes: polyolefin, polyester, polyether, polyamide, polyimide, polyurethane, and polyoxazolidone.  \n\nChain polymerization is applied to a single starting monomer having at least one polymerizable functional group. Step-growth polymerization reactions are applied to two starting monomers with at least two polymerizable functional groups within each molecular entity or a single monomer with two different functional groups for the same polymerization reaction.  \n\nSelection and Mapping Monomers to Polymerization Reactions. First, from the given set of starting molecules, we select those that can form monomers in the polymerization reaction rule set according to the presence or absence of the class-specific functional groups. The monomer or monomer pair is then mapped to an applicable polymerization reaction depending on the presence or absence of polymerizable functional groups in the reaction rule. The polymerizable functional groups in the rule set include vicinal and/or geminal functional groups as summarized in Table 1. Here, starting molecules containing incompatible functional groups are automatically excluded from the calculation.  \n\nIn this study, 1083 starting molecules were manually extracted from the literature and lists of commercially available compounds. Their chemical structures were expressed in SMILES strings.25 SMiPoly’s submodule “monc.py” classified the 1083 compounds into 19 monomer classes according to the presence or absence of the class-specific functional groups. In the step-growth polymerization, the upper and lower limits for the occurrence number of a polymerizable functional group in a given monomer were limited to the default values of 2 and 4, respectively. The classification result is summarized in Tables 2 and 3, respectively.  \n\nLibrary Generation. To generate a virtual polymer library, an applicable set of polymerization reactions is performed according to the classification of a given monomer set. Polymerizable functional groups identified by “polg.py” are denoted by asterisks. If necessary, an option can be specified to limit the class of polymers generated. The generator lists all applicable monomer combinations for a given polymerization reaction according to the pre-computed monomer class and converts one or two starting monomers to products. The polymerization of polyolefins by addition chain polymerization and polyesters and polyamides composed of monomers with two different functional groups for the same polymerization reaction within the same molecular entity produces bipolymers as well as homopolymers. Polymers with regioisomeric structures were treated as different compounds. The relation between monomer classes, polymerization reactions, and polymer classes is illustrated in Figure S1.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# RESULTS AND DISCUSSION  \n\nAs summarized in Table 2, the 1083 starting molecules were classified into one or more of the 19 different monomer classes according to the presence or absence of the class-specific reaction sites. From these monomers, a total of 574,837 virtual polymers were generated by applying the 22 reaction rules. Here, polymers with the same repeating units but different starting monomers were distinguished. These virtual polymers constituted the seven polymer classes (polyolefin, polyester, polyether, polyamide, polyimide, polyurethane, and polyoxazolidone) as summarized in Table 3. Each of these polymers is defined by a single repeating unit because the current virtual library consists of either homopolymers or alternation copolymers. The class of polyolefins is given by homopolymers and binary alternating copolymers that are generated from all combinations of the olefin and/or cyclic olefin monomers. The  \n\nTable 1. 22 Polymerization Reactions with Monomer Classes To Be Applied, and Their Functional Group Transformations   \n\n\n<html><body><table><tr><td colspan=\"6\">ReactionSMARTS</td></tr><tr><td colspan=\"6\">polymer class monomer class 1</td></tr><tr><td rowspan=\"2\">1</td><td colspan=\"2\"> polymerization reaction</td><td></td><td rowspan=\"2\"> reaction type</td><td rowspan=\"2\"> addition chain polymerization</td></tr><tr><td colspan=\"3\">polyolefin vinyl</td></tr><tr><td colspan=\"5\"></td></tr><tr><td rowspan=\"2\">2</td><td>[CX3;H2,H1,H0:1]=[C;H2,H1,H0:2] >*-[C:1][C:2]-* polyolefin</td><td>cyclic olefin</td><td></td><td rowspan=\"2\">addition chain polymerization</td></tr><tr><td rowspan=\"2\"></td><td colspan=\"3\">[CX3;R:1]=[CX3;R:2]>*-[CX4;R:1][CX4;R:2]-*</td></tr><tr><td colspan=\"5\">polyolefin</td></tr><tr><td rowspan=\"3\">3b</td><td>vinyl</td><td>vinyl [ CX3;H2,H1,H0;!R:1]=[CX3;H2,H1,H0;!R:2].[CX3;H2,H1,H0;!R:3]=[CX3;H2,H1,H0;!R:4]></td><td> addition chain polymerization</td><td rowspan=\"3\"></td></tr><tr><td>*-[CX4:1][CX4:2][CX4:3][CX4:4]-*</td><td></td><td></td></tr><tr><td colspan=\"3\">polyolefin vinyl</td></tr><tr><td rowspan=\"3\">4b</td><td></td><td>cyclic olefin [CX3;H2,H1,H0;!R:1]=[CX3;H2,H1,HO;!R:2].[CX3;H1,H0;R:3]=[CX3;H1,H0;R:4]></td><td></td><td rowspan=\"3\"> addition chain polymerization</td></tr><tr><td>*-[CX4:1][CX4:2][CX4:3][CX4:4]-*</td><td></td><td></td></tr><tr><td colspan=\"3\">polyolefin cyclic olefin</td></tr><tr><td rowspan=\"2\">sb 6</td><td></td><td>[CX3;H1,H0;R:1]=[CX3;H1,H0;R:2].[CX3;H1,H0;R:3]=[CX3;R:4]>*-[CX4:1][CX4:2][CX4:3][CX4:4]-*</td><td>cyclic olefin</td><td rowspan=\"2\"> addition chain polymerization</td></tr><tr><td rowspan=\"2\"> polyester</td><td colspan=\"3\">lactone ring-opening chain polymerization</td></tr><tr><td rowspan=\"2\">7</td><td>[CX3;R:1](=[OX1])[OX2;R:2]>(*-[CX3:1](=[OX1]).[OX2:2]-*)</td><td></td><td rowspan=\"2\"> polycondensation</td></tr><tr><td rowspan=\"2\"></td><td colspan=\"3\">polyester hydroxy carboxylic acidc</td></tr><tr><td rowspan=\"2\">8b</td><td>polyester hydroxy carboxylic acid</td><td>([OX2H1;$(OC=*):1].[CX3:2](=[O])[OX2H1])>(*-[OX2:1].[CX3:2](=[O])-*）</td><td> polycondensation</td></tr><tr><td colspan=\"3\">hydroxy carboxylic acidc ([OX2H1;!$(OC=*):1].[CX3:2](=[O])[OX2H1]}).([OX2H1;!$(OC=*):3].[CX3:4](=[O])[OX2H1])></td></tr><tr><td rowspan=\"3\">9</td><td>(*-[OX2:1].[CX3:2](=[O])[OX2:3].[CX3:4](=[O])-*)</td><td></td><td></td></tr><tr><td></td><td>di/polycarboxylic acid di/polyol</td><td rowspan=\"2\">polycondensation</td></tr><tr><td colspan=\"3\">polyester</td></tr><tr><td rowspan=\"2\"></td><td></td><td></td><td>([CX3:1](=[O])[XH1,CBr][CX3:2](=[O])[OXH1CBr]).([O,S;X;H1;$([OS]C=*):3].[O,S;X;H1;$([O,S]C=*):4])></td><td rowspan=\"2\"></td></tr><tr><td colspan=\"3\">(*-[CX3:1](=[O]).[CX3:2](=[O])-[O,S;X2;!$([O,S]C=*):3].[O,S;X2;!$([O,S]C=*):4]-*)</td></tr><tr><td rowspan=\"3\">10</td><td>polyesterd ([O,S;X2;H1;!$([O,S]C=*):1].[O,S;X2;H1;!$([O,S]C=*):2]).[C-]#[O+]></td><td>di/polyol carbon monoxidee</td><td rowspan=\"2\"> polycondensationf</td></tr><tr><td>(*-[O,S;X2;!$([O,S]C=*):1].[O,S;X2;!$([O,S]C=*):2][CX3](=[O])-*)</td><td></td></tr><tr><td>polyester cyclic anhydride</td><td>epoxide</td><td> ring-opening chain polymerization</td></tr><tr><td rowspan=\"2\">11</td><td></td><td>[C,c;R:1][CX3,c;R](=[OX1])[OX2,o;R][CX3,c;R](=[OX1])[C,c;R:2].[CX4;R:3]1[OX2;R:4][CX4;R:5]1></td><td rowspan=\"2\"></td></tr><tr><td colspan=\"3\">([C,c:1][CX3](=[OX1])(-*).[C,c:2][CX3](=[OX1])[OX2][CX4:3][CX4:5][OX2:4]-*)</td></tr><tr><td>12</td><td>polyether epoxide</td><td></td><td> ring-opening chain polymerization</td></tr><tr><td colspan=\"2\"></td><td>[CX4;H2,H1,H0;R:1]1[O;R][C;R:2]1>*-[CX4:1][CX4:2][O]-*</td><td></td></tr><tr><td colspan=\"2\">13</td><td>hindered phenol</td><td> polycondensationg</td></tr><tr><td colspan=\"2\"></td><td>[c]1([OH1:1])[c:2][c:3][c;H1:4][c:5][c:6]1>[c]1([OX2:1]-[*])[c:2][c:3][c:4](-*)[c:5][c:6]1</td><td> polycondensation</td></tr><tr><td colspan=\"2\">14 polyetherh</td><td>bis(p-halogenated aryl)sulfone di/polyol (without thiol)</td><td></td></tr><tr><td colspan=\"2\"></td><td>[c:1]1[c:2]p[c:3]([F,CLBr,1]})[c:4][c:][c:6]1[SX4](=[OX1])(=[OX1])[c:7]2[c:8][c:9][c:10]([F,CLBr,1])[c:11][c:12]2. ([OX2;H1;!$([O,S]C=*):13].[OX2;H1;$([O,S]C=*):14])></td><td></td></tr><tr><td colspan=\"2\"></td><td>[c:1]1[c:2][c:3](-[*])[c:4][c:5][c:6]1[SX4](=[OX1])(=[OX1])[c:7]2[c:8][c:9][c:10]([OX2;1$([O,s]C=*):13].</td><td></td></tr><tr><td colspan=\"2\">15 polyetheri</td><td>[OX2;!$([O,S]C=*):14]-[*])[c:11][c:12]2</td><td> polycondensation</td></tr><tr><td colspan=\"2\"></td><td>bis(p-fluoroaryl)ketone di/polyol (without thiol)</td><td>[c:1]1[c:2][c:3]([F])[c:4][c:5][c:6]1[CX3](=[OX1])[c:7]2[c:8][c:9][c:10]([F])[c:11][c:12]2.([OX2;H1;!$([O,S]C=*):13].</td></tr><tr><td colspan=\"2\">[OX2;H1;!$([O,s]C=*):14])></td><td></td><td></td></tr><tr><td colspan=\"2\">[OX2;!$([O,S]C=*):14]-[*])[c:11][c:12]2</td><td>[c:1]1[c:2][c:3](-[*])[c:4][c:5][c:6]1[CX3](=[OX1])[c:7]2[c:8][c:9][c:10]([OX2;!$([O,S]C=*):13].</td><td></td></tr><tr><td colspan=\"2\">16 polyamide</td><td>lactam</td><td> ring-opening chain polymerization</td></tr><tr><td colspan=\"2\"></td><td>[CX3;R:1](=[OX1])[NX3;R:2]>(*-[CX3:1](=[OX1])[NX3:2]-*)</td><td> polycondensation</td></tr><tr><td colspan=\"2\">17</td><td>polyamide amino acidc ([NX3;H2,H1;!$(OC=*):1].[CX3:2](=[O])[OX2H1])>(*-[NX3:1].[CX3:2](=[O])-*)</td><td></td></tr><tr><td colspan=\"2\">18b</td><td>amino acidc amino acidc</td><td> polycondensation</td></tr><tr><td colspan=\"2\"> polyamide</td><td>([N&X3;H2,H1;!$(NC=*):1].[CX3:2](=[O])[OX2H1]).([N&X3;H2,H1;!$(NC=*):3].[CX3:4](=[O])[OX2H1])></td><td></td></tr><tr><td colspan=\"2\"></td><td></td><td></td></tr><tr><td colspan=\"2\"> polyamide</td><td>(*-[NX3;!$(NC=*):1].[CX3:2](=[O])[NX3;!$(NC=*):3][CX3:4](=[O])-*)</td><td></td></tr><tr><td colspan=\"2\">19</td><td>di/polycarboxylic acid di/polyamine</td><td> polycondensation</td></tr><tr><td colspan=\"2\"></td><td>([CX3:1](=[O])[OXH1,CBr][CX3:2](=[O])[OX2H1,CI,Br]).([N&X3;H2,H1;$(NC=*):3].[N&X3;H2,H1;!$(NC=*):4])></td><td></td></tr><tr><td colspan=\"2\"></td><td>(*-[CX3:1](=[O]).[CX3:2](=[O])-[NX3;!$(NC=*):3].[NX3;!$(NC=*):4]-*)</td><td></td></tr><tr><td colspan=\"2\">20</td><td>di/polycyclic anhydride primary di/polyamine</td><td> polycondensation</td></tr><tr><td colspan=\"2\">polyimide</td><td>([CX3,c;R:1](=[OX1])[OX2,o;R][CX3,c;R:2](=[OX1]).[CX3,c;R:3](=[OX1])[OX2,0;R][CX3,c;R:4](=[OX1])).</td><td></td></tr><tr><td colspan=\"2\"></td><td></td><td></td></tr><tr><td colspan=\"2\"></td><td>([C,c:5][NX3;H2;!$(N[C,S]=*)].[C,c:6][NX3;H2;!$(N[C,S]=*)])></td><td></td></tr><tr><td colspan=\"2\"></td><td></td><td></td></tr><tr><td colspan=\"2\">polyurethane</td><td>([CX3,c;R:1](=[OX1])[NX3;R]([C,c:5][C,c:6]-*)[CX3,c;R:2](=[OX1]),[CX3,c;R:3](=[OX1])[NX3;R](-*)[CX3;R:4](=[OX1]))</td><td></td></tr><tr><td colspan=\"2\">21 （[NX2:1]=[CX2]=[OX1,SX1:2].[NX2:3]=[CX2:4]=[OX1,SX1:5]).</td><td>di/polyisocyanate di/polyol</td><td> polyaddition</td></tr></table></body></html>  \n\nTable 1. continued   \n\n\n<html><body><table><tr><td></td><td>polymer class polymerization reaction</td><td> monomer class 1</td><td>monomer class 2</td><td>reaction type</td></tr><tr><td colspan=\"5\">22</td></tr><tr><td rowspan=\"4\"></td><td colspan=\"3\">([OX2,SX2;H1;!$([O,S]C=*):6].[OX2,SX2;H1;!$([O,S]C=*):7])> (*-[CX3](=[OX1,X1:2])[NX3:1][X3:3][CX3:4](=[OX1,SX1:5])[OX2,SX2;$([O,S]C=*):6][X2,SX2;!$([O,S]C=*):]-*)</td></tr><tr><td colspan=\"3\">polyoxazolidone di/polyepoxide di/polyisocyanate polyaddition</td></tr><tr><td colspan=\"3\">([CX4;H2,H1,H0;R:1]1[OX2;R:2][CX4;H1,H0;R:3]1.[CX4;H2,H1,H0;R:4]2[OX2;R:5][CX4;H1,H0;R:6]2). ([OX1,SX1:7]=[CX2:8]=[NX2:9].[OX1,SX1:10]=[CX2:11]=[NX2:12])></td></tr><tr><td colspan=\"3\">(*-[OX2:2][CX4:3]([CX4:1]-*).[CX4;R:6]1[OX2;R:5][CX2;R:8](=[OX1,SX1:7])[NX3;R:9][CX4;R:4]1.</td></tr></table></body></html>  \n\naThe 7 different polymer classes can be generated by the 22 polymerization rules. bBipolymer. $^c\\mathrm{A}$ monomer with two different functional groups for the same polymerization reaction within the same molecular entity. dPolycarbonate. eSynthetic equivalent of phosgene. fOxidative carbonylation in the case of CO. gUsually oxidative polymerization was applied. hPolyethersulfone (PES) was generated. iPolyetherketone (PEK) or polyetheretherketone was generated.  \n\nTable 2. Result of Monomer Classification   \n\n\n<html><body><table><tr><td>monomer class</td><td>no. of compounds</td></tr><tr><td>vinyl</td><td>462</td></tr><tr><td>cyclic olefin</td><td>52</td></tr><tr><td>epoxid</td><td>71</td></tr><tr><td>lactone</td><td>13</td></tr><tr><td>lactam</td><td>1</td></tr><tr><td>hydroxy carboxylic acid</td><td>7</td></tr><tr><td>amino acid</td><td>1</td></tr><tr><td>hindered phenol</td><td>8</td></tr><tr><td>bis(p-halogenated aryl) sulfone</td><td>4</td></tr><tr><td>bis(p-fluoroaryl)ketone</td><td>1</td></tr><tr><td>di/poly epoxide</td><td>14</td></tr><tr><td>di/polycarboxylic acid</td><td>85</td></tr><tr><td>di/polyol (include thiol)</td><td>162</td></tr><tr><td>di/polyol (without thiol)</td><td>132</td></tr><tr><td>di/polyamine</td><td>149</td></tr><tr><td>primary di/polyamine</td><td>143</td></tr><tr><td>di/polyisocyanate</td><td>19</td></tr><tr><td>cyclic carboxylic acid ahnydride</td><td>33</td></tr><tr><td>di/polycyclic catboxylic acid anhydride</td><td>28</td></tr></table></body></html>  \n\nTable 3. Number of SMiPoly-Generated Polymers Classified into Seven Polymer Classes   \n\n\n<html><body><table><tr><td> polymer class</td><td> no. of generated polymers</td></tr><tr><td>polyolefin</td><td>523,080</td></tr><tr><td>polyester</td><td>25,204</td></tr><tr><td>polyether</td><td>868</td></tr><tr><td>polyamide</td><td>15,554</td></tr><tr><td>polyimide</td><td>5,445</td></tr><tr><td>polyurethane</td><td>4,200</td></tr><tr><td>polyoxazolidone</td><td>486</td></tr><tr><td>total</td><td>574,837</td></tr></table></body></html>  \n\nclasses of polyesters and polyamides consist of homopolymers and binary alternating copolymers generated from the combinations of hydroxy or amino carboxylic acid. The other polymer classes are all composed of homopolymers. Figure 3 depicts several examples of generated polymers for each polymer class along with their polymerization reactions. The Supporting Information provides more randomly selected examples that belong to the seven different polymer classes (Figure S2).  \n\nWe investigated the degree of overlap or coverage and novelty between the distributions of polymers synthesized to date and the virtually created polymers. As the set of existing polymers, 16,223 polymers were extracted from PoLyInfo, the world’s largest database of synthetic polymers. The uniform manifold approximation and projection (UMAP)47 of all polymers with their chemical structures in PoLyInfo and the SMiPoly virtual library is displayed in Figure 4, which shows that SMiPoly is generally able to cover the distribution of existing polymers. A more detailed, quantitative evaluation was performed for each of the seven polymer classes as described below.  \n\nPoLyInfo defines 21 different polymer classes based on its own classification criteria. The polymer classes are identified by the first three letters of the polymer ID (referred to as PID in PoLyInfo), such as P01, P02, P03, etc. Here, the definitions of polymer classes in SMiPoly and PoLyInfo do not exactly match. To eliminate ambiguity in the classification criteria, the polymers generated by SMiPoly and those recorded in PoLyInfo were reclassified to 21 classes using the classifier function (poly.polyinfo_classifier) in the Python library RadonPy,48 which mimics the classification criterion of PoLyInfo’s 21 classes. The six classes of RadonPy that were consistent with SMiPoly and PoLyInfo were used for comparison. The correspondence of the six classes with the RadonPy’s 21 classes, SMiPoly’s seven classes, and PoLyInfo’s 21 classes is summarized in Table 4. In addition, only polymers with two asterisks in the SMILES string of the repeating unit, i.e., linear homopolymers and alternating copolymers, were considered for comparison because it is difficult to represent the branching and cross-linking polymers with SMILES. Further elimination of structural redundancy reduced the number of polymers produced by SMiPoly to 169,347 using the “poly.full_match_smiles_listself” function of RadonPy.48  \n\nHere, we denote the sets of actually synthesized and virtual polymers belonging to a certain polymer class by $S_{\\mathrm{{R}}}$ and $s_{\\mathrm{v}},$ respectively. We assessed the coverage and novelty of $S_{\\mathrm{v}}$ with respect to $S_{\\mathrm{{R}}}$ as follows:  \n\n(1) Evaluate the pairwise similarity between all polymers in $S_{\\mathrm{{R}}}$ and $S_{\\mathrm{v}}$ . As the similarity measure, we employed the Tanimoto coefficient, in which the chemical structure of each polymer was transformed into a 2048-bit vector with an extended connectivity fingerprint with a radius of three atoms (ECFP6).49 To consider the repeating structure of polymers, the ECFP6 descriptor was constructed after generating the macrocyclic oligomer with 10-mer of the repeating unit using RadonPy.4   \n(2) Set the threshold values of the Tanimoto coefficient as $\\gamma\\in$ $\\{0,0.1,...,0.9,1\\}$ .   \n(3) Coverage: calculate the percentage of polymers in $S_{\\mathrm{{R}}}$ with a similarity greater than γ to those in $S_{\\mathrm{v}}$ .   \n(4) Novelty: calculate the percentage of polymers in $S_{\\mathrm{v}}$ with a similarity less than $\\gamma$ to those in $S_{\\mathrm{{R}}}$ .   \n(5) Vary the threshold $\\gamma$ from 0 to 1, and draw a curve representing the balance between (1-coverage) and novelty (coverage−novelty (CN) curve) as shown in Figures 5 and 6.  \n\n![](images/2dfe89588a7a23d3b6229ae69c38de9784bd49b84badc1993196f9e7289de4a4.jpg)  \n\n![](images/06d24df4e9d7284ec0a412af653583244aefc2f4864ba3ba145c051b6202a148.jpg)  \ndifferent polymer classes and their polymerization reactions: (a) polyolefin, (b) polyester, (c) polyether, (d) polyamide, (e) polyimide, (f) polyurethane, and $\\mathbf{\\eta}(\\mathbf{g})$ polyoxazolidone.  \n\nThe CN curve shows an upward or downward convex pattern depending on the inclusive relationship of the distributions of $S_{\\mathrm{{R}}}$ and $\\dot{S}_{\\mathrm{v}}$ . If the two distributions are nearly coincident, the CN curve is drawn on the $45^{\\circ}$ line. If the distribution of $S_{\\mathrm{v}}$ encompasses $s_{\\mathrm{{R}}},$ the CN curve deviates slightly from the $45^{\\circ}$ line and shows an upward convex pattern. This is the most desirable virtual library, given that it contains reasonably novel and diverse polymers while maintaining a high coverage of existing ones. Conversely, if the virtual library set fails to reproduce a part of the synthetic polymers, the CN curve shows downward convexity. This is visually illustrated in Figure S3.  \n\nFigure 5 summarizes the CN curves for each of the six polymer classes and the distributions of $S_{\\mathrm{R}}$ and $S_{\\mathrm{v}}$ visualized on a two-dimensional plane by performing UMAP.47 The virtual libraries for polyamide, polyimide, and polyurethane, which exhibited moderately upward convex CN curves, achieved wellbalanced coverage and novelty. When the threshold of Tanimoto similarity was set to $\\gamma\\geq0.5.$ , the coverage and novelty were approximately 67 and $45\\%$ for polyamide, 70 and $59\\%$ for polyimide, and 70 and $52\\%$ for polyurethane, respectively. The CN curves for polyether showed a slightly downward convex pattern. The coverage and novelty were 51 and $38\\%$ when the threshold was set to $\\gamma\\geq0.5$ .  \n\nWe also investigated the coverage with respect to all 16,223 polymers in PoLyInfo (Figure 6). The coverage and novelty of the 169,347 virtual polymers for all these polymers were 48 and $53\\%$ under $\\gamma\\geq0.5.$ , respectively.  \n\nThe performance of the rule-based virtual polymer generator depends on the diversity of the starting monomer set and the comprehensiveness of polymerization reaction rules. As shown by the UMAP projection in Figure 6, the current SMIPoly virtual library clearly failed to cover some regions of the existing polymer distribution in PoLyInfo, which are denoted by regions A−C (see example polymers belonging to each region in Figure S4 in the Supporting Information). The presence of region A was due to the fact that the current SMiPoly does not implement the condensation reaction of hydroxycarboxylic acids and amino acids even though both types of monomers were included when the library was created. Region B arose because the starting monomer set did not include the relevant molecules; as shown in Table 2, the starting monomer set contains very few amino acid molecules. The polymers belonging to region C were mainly polyarylenes. The current SMiPoly could not cover this area because polymerization reactions with aryl coupling reactions and their monomers were undefined. This is the main reason for the low coverage and novelty in the generation of the class of polyethers. The class of polyethers defined by PoLyInfo (P07 and P37) includes polyoxides with chain structures as well as polymers with cyclic structures including $\\scriptstyle{\\mathrm{C-O-C}}$ bonds and acetal structures in the main chain, but the current SMiPoly does not support these polymerization reactions or monomers.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# CONCLUSIONS  \n\nTo generate synthesizable virtual polymer candidates, we have developed the Python library SMiPoly that implements 22 chemical rules for polymerization reactions. For any given set of starting molecules, the generator creates synthetic products by conducting automatically selected polymerization reactions applicable to the input monomers. All polymers produced are potentially synthesizable.  \n\nIn this study, using 1083 available monomers, we generated 169,347 unique linear polymers forming seven different types of polymers, such as polyolefin, polyester, polyether, polyamide, polyimide, polyurethane, and polyoxazolidone. The reaction space that can be represented by the current release of SMiPoly covers approximately $50\\%$ $(\\gamma\\ge0.5)$ of the entire chemical space of polymers synthesized to date. When focusing on nitrogen containing polymers defined by SMIPoly, it covered $70\\%$ of the corresponding chemical space with around $50\\%$ novelty $(\\gamma\\geq$ 0.5). The coverage can be monotonically increased by further expanding the list of raw monomers and the set of polymerization reactions.  \n\n![](images/fe46c2736fc416b4402a52d5d858dd34d27026369707a6c716070e50a26bd7d3.jpg)  \n· Polyolefins (hydrocarbons) Polystyrenes Polyvinyls · Polyacrylics · Polyhalo-olefins · Polydienes Polyethers Polysulfides Polyesters Polyamides ? Polyurethanes Polyureas Polyimides Polyanhydrides Polycarbonates Polyimines Polysilanes Polyphosphazenes Polyketones Polysulfones · Polyphenylenes   \nFigure 4. UMAP projection of all polymers with their chemical structures in (a) PoLyInfo (16,223 polymers) and (b) SMiPoly virtual library (169,347 polymers). ECFP6 descriptor, which was constructed after generating the macrocyclic oligomer with 10-mer of the repeating unit, was used as input of the UMAP. The 21 classes of the polymer backbones are color-coded according to the classification of RadonPy.  \n\nTable 4. Correspondence of Polymer Classes between Existing Polymers in PoLyInfo, 21 Classes of RadonPy, and Seven Classes of SMiPoly-Generated Polymers   \n\n\n<html><body><table><tr><td> polymer class</td><td> RadonPy</td><td>PoLyInfo PIDa</td><td> SMiPoly</td><td>no. of polymers in PoLyInfo</td><td> no. of polymers in SMiPoly</td></tr><tr><td>polyolefin</td><td>hydrocarbon of polyolefin</td><td>P01, P31</td><td>polyolefin</td><td>3,139</td><td>139,990</td></tr><tr><td rowspan=\"6\"></td><td>polystyrene</td><td>P02, P32</td><td></td><td></td><td></td></tr><tr><td> polyvinyl</td><td>P03, P33</td><td></td><td></td><td></td></tr><tr><td> polyacrylate</td><td>P04,P34</td><td></td><td></td><td></td></tr><tr><td> halogenated polyolefin</td><td>P05, P35</td><td></td><td></td><td></td></tr><tr><td>polydiene</td><td>P06,P36</td><td></td><td></td><td></td></tr><tr><td> polyester</td><td>P09, P39</td><td>polyester</td><td>2,775</td><td>9,903</td></tr><tr><td>polyester polyether</td><td>polyether</td><td>P07, P37</td><td> polyether</td><td>4,692</td><td>5,547</td></tr><tr><td> polyamide</td><td> polyamide</td><td>P10, P40</td><td> polyamide</td><td>5,059</td><td>14,402</td></tr><tr><td> polyimide</td><td>polyimide</td><td>P13, P43</td><td>polyimide</td><td>2,755</td><td>6,553</td></tr><tr><td> polyurethane</td><td> polyurethane</td><td>P11, P41</td><td>polyurethane polyoxazolidone</td><td>695</td><td>2,772</td></tr><tr><td colspan=\"4\"> no. of unique polymers</td><td>16,223</td><td>169,347</td></tr></table></body></html>  \n\nHere, we remark on a comparison with the OMG virtual polymer database, which was created using a rule-based polymerization algorithm similar to SMiPoly; OMG contains approximately 12 million virtual polymers generated from 17 different polymerization reaction rules using approximately 80,000 small molecules as starting materials. Table S2 in the Supporting Information summarizes whether each of the 21 polymer classes of PoLyInfo can be generated by SMiPoly and OMG. Currently, SMiPoly implements $59\\%$ (10/17) of the reaction rules defined in the OMG, and the OMG implements $36\\%$ (8/22) of the reaction rules defined in SMiPoly.  \n\nFinally, the limitations of the current version of SMiPoly are summarized. For example, it is necessary to extend the rule set of polymerization reactions, such as ring-opening metathesis polymerization (ROMP), addition-condensation polymerization to generate phenol and/or melamine resin, and main-chain growth with aryl coupling reaction. The difficulty in defining these polymerization reactions arises from the complexity of defining the monomer structures to be reacted. In addition, in order to improve the accuracy of monomer selection and polymerization reaction prediction, olefin monomers need to be further classified in detail. More importantly, although branched polymers play an important role in the development of thermosetting polymers, the generation of branched polymers cannot be handled by the current version of SMiPoly. Since this limitation is due to SMILES-based modeling, it is necessary to introduce a structural representation that can handle stochastic polymer structures such as BigSMILES.50  \n\n![](images/4317311d37f81eba74120272d6bb153a1bd82e63095033aabb1809ccc418fd0f.jpg)  \nFigure 5. For each class of polymers, the coverage and novelty of the virtual library relative to existing polymers are evaluated based on CN curves and visual inspection of UMAP projections of the two sets of chemical structures: (a) polyolefin, (b) polyester, (c) polyether, (d) polyamide, (e) polyimide, and (f) polyurethane.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 7,
+        "chunk": "# ASSOCIATED CONTENT",
+        "category": " References"
+    },
+    {
+        "id": 8,
+        "chunk": "# Data Availability Statement  \n\nThe source code of SMiPoly is available from the GitHub website(https://github.com/PEJpOhno/SMiPoly). A sample script to generate the polymer library is in the directory named “sample_script”. The list of starting molecules is stored in the directory “sample_data”. The list of the selected monomers and generated polymers is also available.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# $\\bullet$ Supporting Information  \n\nThe Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jcim.3c00329.  \n\nAdditional experimental details, materials, and methods, including (1) functional group transformations in the polymerization reaction rules (Table S1), (2) monomer class, polymerization reaction, and polymer class (Figure S1), (3) generated polymers belonging to seven different polymer classes and their polymerization reactions (Figure S2), (4) drawing CN curve (Figure S3), (5) examples of polymers belonging to Regions $_{\\mathrm{A-C}}$ in Figure 6 (Figure S4), and (6) comparison of polymerization reaction rule sets between SMiPoly and OMG (Table S2) (PDF)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# AUTHOR INFORMATION  \n\nCorresponding Authors Mitsuru Ohno − Daicel Corporation, 530-0011 Osaka, Japan; $\\circledcirc$ orcid.org/0000-0002-4588-1927; Email: mt_ohno@ jp.daicel.com Ryo Yoshida − The Institute of Statistical Mathematics, Research Organization of Information and Systems, Tachikawa, Tokyo 190-8562, Japan; The Graduate University for Advanced Studies, SOKENDAI, Tachikawa, Tokyo 190-8562, Japan; National Institute for Materials Science, 305-0047 Ibaraki, Japan; orcid.org/0000-0001- 8092-0162; Email: yoshidar@ism.ac.jp   \nAuthors Yoshihiro Hayashi − The Institute of Statistical Mathematics, Research Organization of Information and Systems, Tachikawa, Tokyo 190-8562, Japan; The Graduate University for Advanced Studies, SOKENDAI, Tachikawa, Tokyo 190-8562, Japan; $\\circledcirc$ orcid.org/0000-0002-7650- 4083 Qi Zhang − The Institute of Statistical Mathematics, Research Organization of Information and Systems, Tachikawa, Tokyo 190-8562, Japan Yu Kaneko − Daicel Corporation, 530-0011 Osaka, Japan; orcid.org/0000-0001-8617-0876  \n\nComplete contact information is available at: https://pubs.acs.org/10.1021/acs.jcim.3c00329",
+        "category": " Abstract"
+    },
+    {
+        "id": 11,
+        "chunk": "# Author Contributions  \n\nM.O. and R.Y. designed and conceived the project, and wrote a preliminary draft of the paper. M.O. designed and developed the SMiPoly library, and performed the experiments with assistance from Y.H., ${\\bf{\\cal Z}}.{\\bf{\\cal Q}}.,$ and Y.K. M.O., Y.H., and R.Y. wrote and revised the manuscript. All authors discussed the result and commented on the manuscript.",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# Notes  \n\nThe authors declare no competing financial interest.  \n\n![](images/aff97ee7e75321f40a66f30f25b4e17fb536b1fd678223ee70d40ac333132876.jpg)  \nFigure 6. Coverage and novelty of virtual libraries with respect to existing polymers are evaluated based on the CN curve and visual inspections of th distribution of polymers’ chemical structures constituting the two sets by UMAP projections.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nThis work was supported in part by MEXT under “Program for Promoting Researches on the Supercomputer Fugaku” (Project ID: hp210264 to R.Y.), JST CREST Grant Number JPMJCR19I3, and the Grant-in-Aid for Scientific Research (A) 19H01132 from the Japan Society for the Promotion of Science (JSPS).",
+        "category": " Acknowledgments"
+    },
+    {
+        "id": 14,
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PMID: 32975943   \n(31) Zhang, $\\mathrm{Q.;}$ Liu, C.; Wu, S.; Yoshida, R. Bayesian Sequential Stacking Algorithm for Concurrently Designing Molecules and Synthetic Reaction Networks. arXiv preprint arXiv:2204.01847 2022, (32) Mikulak-Klucznik, B.; et al. Computational planning of the synthesis of complex natural products. Nature 2020, 588, 83−88. (33) Badowski, T.; Gajewska, E. P.; Molga, K.; Grzybowski, B. A. Synergy Between Expert and Machine-Learning Approaches Allows for Improved Retrosynthetic Planning. Angew. Chem., Int. Ed. 2020, 59, 725−730.   \n(34) Chen, L.; Kern, J.; Lightstone, J. P.; Ramprasad, R. Data-assisted polymer retrosynthesis planning. Appl. Phys. Rev. 2021, 8, No. 031405. (35) Taniwaki, H.; Kaneko, H. Molecular design of monomers by considering the dielectric constant and stability of the polymer. Polym. Eng. Sci. 2022, 62, 2750.   \n(36) Otsuka, S.; Kuwajima, I.; Hosoya, J.; Xu, Y.; Yamazaki, M. PoLyInfo: Polymer Database for Polymeric Materials Design. 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B.; Merna, J.; Moad, G.; Russell, G. T.; Théato, P.; Topham, P. D.; Sosa Vargas, L. Reconsidering terms for mechanisms of polymer growth: the “step-growth” and “chain-growth” dilemma. Polym. Chem. 2022, 13, 2262−2270.   \n(42) Odian, G. Principles of polymerization; John Wiley & Sons, 2004. (43) Jenkins, A. D.; Kratochvíl, P.; Stepto, R. F. T.; Suter, U. W. Glossary of basic terms in polymer science (IUPAC Recommendations 1996). Pure Appl. Chem. 1996, 68, 2287−2311.   \n(44) Kagiya, T. A Classification of Polymerization Reaction. Kobunshi 1964, 13, 855−858. 854,   \n(45) Compendium of Chemical Terminology [Internet]. https:// goldbook.iupac.org, cited: 2023-04-08.   \n(46) Daylight. SMARTS: a language for describing molecular patterns [Internet]. https://www.daylight.com/dayhtml/doc/theory/theory. smarts.html, cited: 2022-10-14.   \n(47) McInnes, L.; Healy, J.; Melville, J. Umap: Uniform manifold approximation and projection for dimension reduction. arXiv preprint arXiv:1802.03426 2018,   \n(48) Hayashi, Y.; Shiomi, J.; Morikawa, J.; Yoshida, R. RadonPy: automated physical property calculation using all-atom classical molecular dynamics simulations for polymer informatics. npj Comput. Mater. 2022, 8, 222.   \n(49) Rogers, D.; Hahn, M. Extended-Connectivity Fingerprints. J. Chem. Inf. Model. 2010, 50, 742−754. PMID: 20426451.   \n(50) Lin, T.-S.; Coley, C. W.; Mochigase, H.; Beech, H. K.; Wang, W.; Wang, Z.; Woods, E.; Craig, S. L.; Johnson, J. A.; Kalow, J. A.; Jensen, K. F.; Olsen, B. D. BigSMILES: A Structurally-Based Line Notation for Describing Macromolecules. ACS Cent. Sci. 2019, 5, 1523−1531. PMID: 31572779.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "North Dakota State University Coatings and Polymeric Materials  \n\n<html><body><table><tr><td>Paint Ingredients (reminder)</td></tr><tr><td>Most paints have four broad types of ingredients: Binder Pigment Additives</td></tr><tr><td>Solvent - controls viscosity, wetting (thus adhesion) and carries everything in the application stages.</td></tr><tr><td>Notable Exceptions (dealt with elsewhere in course):</td></tr><tr><td>1. 100% solids UV curable (the monomer is the medium) 2. Powder coatings (air is the delivery medium)</td></tr></table></body></html>  \n\nBackground. How much solvent is used in paints? 2005 data U.S. Census Bureau statistics - 2005 Manufacturing Profiles (Paint Varnish and Lacquer): Architectural coatings Exterior solvent type 80,161,000 gallons Interior solvent type 58,827, 000 gallons Architectural Lacquers  6,936,000 gallons Product Finishes for original equipment manufactures, excluding marine coatings 398,673,000 gallons containing solvent Special - purpose coatings 155,629,000 gallons - mainly solvent borne   \nTotal $\\sim$ 700,000,000 gallons of paint $\\textcircled{6}$ 3 lb/gal solvent $\\mathbf{\\sigma}=\\mathbf{\\sigma}$ 210,000,000 lb solvent or \\~ 20,000,000 gallons of solvent   \nIn addition, even waterborne coatings (no totals given here) contain cosolvents and plasticisers that contribute significantly to solvent emissions.  \n\n<html><body><table><tr><td>Choice of Solvent 1. greatly determined by the choice of the other ingredients</td></tr><tr><td>“Binders\" - Hold everything together and provide adhesion to the substrate · Binders are usually organic polymers ：Very convenient and versatile technology ： End use requires high molecular weight or X-linking</td></tr></table></body></html>  \n\nChoice of solvents  \n\n2. other issues. • Compatibility with dissolved ingredients (from previous) - Maintaining high solids content • Toxicity and other environmental issues Viscosity • Evaporation Rate • Surface Tension • Others, e.g. resistivity (for electrostatic application) • Cost",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Roles for Solvents/Summary of Module  \n\n• Reaction medium  \n\nKinetics, Concentration, Reactant, e.g. reactive diluent, or end group   \n– See polymer synthesis modules  \n\n• Carrier – this module – Viscosity – Necessary for wetting a surface – compatibility with polymers is very important may need to replace a hazardous solvent with less hazardous substitute.  \n\n• Leave when required to do so – this module - Evaporation behavior is very important",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# Viscosity of Polymer Solutions  \n\n• Viscosity  \n\nresistance to flow,   \n– friction between molecules   \n– Larger molecules produce more friction   \n– Depending on the concentration, larger molecules get entangled » Viscosity increases greatly   \n– The larger molecules within a distribution determine the viscosity   \n– The greater the compatibility between polymer and solvent the more the polymer coil expands  \n\n» And so the viscosity increases  \n\nWe need to provide a usefully high molecular weight at a practical viscosity - one of the reasons for latex polymers – low viscosity means good leveling, flow out and gloss  \n\nViscosity increases greatly with concentration in polymer solutions.  \n\n![](images/732e67d1840df0dc915147218c87794e68daaebb436fe759197d235303ef5df2.jpg)  \n\nNote logarithmic axes.  \n\nThe exact nature of the curve varies with chemical structure, but depends hugely on molecular weight (see next)  \n\nThe requirement for high solids means that there is a restriction on the molecular weight that can be used.  \n\nStuart Croll  \n\nViscosity increases greatly with molecular size (weight)  \n\nEntanglement depends on concentration, molecular size and compatibility with the solvent (how much the molecule spreads out).  \n\n![](images/76dc2a49e0a1152f0c2d82549b52c186692313f2cc2b7c5173634dd20bcda5d8.jpg)  \n\n![](images/7f00482ca0505ad6827b043432ddd10c2dfe09082e73e45d571a95265819f98f.jpg)  \n\nLog. (Molecular Weight)  \n\nStuart Croll",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# Wetting  \n\n• Processes that depend on wetting – Spreading – Adhesion  \n\n• Necessary for optimizing contact between  \n\n– Soluble coating ingredients $\\&$ particulate materials   \n– Coating &  substrate » (Usually amounts to displacing air)   \n– Wetting is important  \n\nYoung’s Equation for surface wetting Cos $\\breve{\\theta}=(\\gamma_{s\\nu}-\\gamma_{s\\mathcal{V}})/\\gamma_{l\\nu}$ $\\theta=$ contact angle $\\gamma_{l\\nu}=$ liquid-vapor surface tension, (the only one easily controlled)  \n\nFor wetting, $\\theta$ should be small , i.e. the drop spreads, which means that $\\gamma_{l\\nu}$ should be low.  \n\n![](images/554d4adb2ed294e8eace56bdde5ee76bb6708b34384a8f13b9fce638edc647fb.jpg)  \n\nGood wetting $\\mathbf{\\tau}=\\mathbf{\\tau}$ even spreading; penetration of rough surface areas; $\\mathbf{\\Sigma}=\\mathbf{\\Sigma}$ intimate contact between coating and substrate $\\mathbf{\\Sigma}=$ adhesion; film properties; good corrosion resistance  \n\nStuart Croll  \n\n<html><body><table><tr><td>Surface Tension of Liquids - some examples</td></tr><tr><td>Water 72 mN/m [=dyn/cm] Acetone 23.5 1-propanol 23.3 Ethyl acetate 23.4 1-Butanol 25 MEK 24</td></tr></table></body></html>  \n\n![](images/eb585dac14c702707fd2432be01b80878b5d1e43d9c08cf6144d43a3004aee63.jpg)  \n\n![](images/6e435b180fe04c90d9dce73c958b1a6e8e60a8d07b18e54a98bc7fcb37a1cc9e.jpg)  \n\n![](images/6beb658ee2511409ebcfea0ac9b41b59fbc7f2cd5fdfc234b4d93a575e38edaf.jpg)  \n\nIn practice, dissolving a polymer is a slow process (thus many are created in solution)  \n\nStep 1: solvent diffuses into a polymer body and produces a swollen gel  \n\nStep 2: if the polymer-polymer   \nforces can be overcome by the   \npolymer-solvent interactions   \npolymer is released from the gel –rate limiting step –polymer chains are released into the bulk solution where they may be separate or entangled.  \n\nStuart Croll",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# Solubility Parameters: Based on Thermodynamics  \n\nWhat we are aiming for is:  \n\na useful scheme so that we can find out which solvents will dissolve a given polymer, or - How we can substitute one solvent for another  \n\nFirst two laws of thermodynamics are equivalent to considering Gibbs Free Energy, $G,$ if temperature and pressure are constant.  \n\nCriterion for dissolution is that upon mixing, G should  be reduced.  \n\n- thus solution must have a lower Gibbs Free Energy than the separate components.  \n\n$$\n\\varDelta G_{m i x i n g}=\\varDelta H_{m i x i n g}-T.\\ A S_{m i x i n g}\n$$  \n\n$\\varDelta H=$ change in enthalpy, $\\varDelta S=$ change in entropy $\\begin{array}{r l}{T}&{{}=}\\end{array}$ temperature, K  \n\nStuart Croll  \n\n<html><body><table><tr><td>I. Entropy of mixing</td></tr><tr><td>In a regular solution △S =-RN[ flog f,+flog f]</td></tr><tr><td>Where: f= molar fraction (i.e.<1) so log(f) is negative Change of entropy is positive, i.e. increasing entropy N = number of molecules</td></tr><tr><td>R = Gas Constant Entropy increase always helps mixing since it reduces</td></tr><tr><td>- Increasing temperature helps miscibility (see equation on previous slide) AGmixing</td></tr><tr><td>This theory ignores the entropy change since it always helps dissolution rather than controlling it</td></tr><tr><td></td></tr><tr><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>I. Enthalpy of mixing (Hildebrand and Scott - Regular Solutions)</td></tr><tr><td>Enthalpy = interaction (or cohesive) energy density, Cii Interactions between like molecules within materials 1-1 & 2-2 must become mixed interactions,i.e. 1-2,in the solution.</td></tr><tr><td>Enthalpy changes = C11 + C22 - 2C21 (both type 1 and type 2 change)</td></tr><tr><td>Bertelot's approximation: C21 = (C11.C22)1/2</td></tr><tr><td>How do we measure these interactions, i.e. energy holding the molecules together? identify as cohesive energy/volume</td></tr><tr><td>How do we measure cohesive energy/volume (Cii)?</td></tr><tr><td>= heat of vaporization Stuart Croll 18</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# Enthalpy of Mixing - consequences  \n\n<html><body><table><tr><td colspan=\"2\"></td></tr><tr><td colspan=\"2\">after some algebra: AHmixing = Vm1N.[C11/2 - C221/2]2</td></tr><tr><td colspan=\"2\">Vm= molar volume averaged over mixture Φ= volume fraction of each Φ+ Φ= 1,</td></tr><tr><td colspan=\"2\">AHmixing is usualy a positive quantity, so we need to minimize it to get 4G to be negative (given help from entropy changes).</td></tr><tr><td>1. is easier,</td><td> Solvents with small molar volumes, Vm, reduce AHmixing so dissolving</td></tr><tr><td>2.</td><td>e.g. acetone is a small molecule and a very useful solvent The product ΦΦ is smaller when one of the concentrations is small</td></tr><tr><td></td><td>i.e. dissolving a small amount of solute is always easier than trying to dissolve a lot</td></tr><tr><td>3.</td><td>If we can make C1 = C22, then the enthalpy change is minimized, i.e. zero i.e. the two materials are identical</td></tr></table></body></html>  \n\n<html><body><table><tr><td>Solubility Parameter</td></tr><tr><td>Hildebrand identified a solubility parameter for a given material as:</td></tr><tr><td>8 = C1/2 etc.= (cohesive energy density)1/2 = (AEevap/ Vsolwent)1/2</td></tr><tr><td>See equation on previous slide. Thus materials should stand a better chance of mixing when their solubility parameters more closely match, i.e. difference in Ci is</td></tr><tr><td>minimized. What do we have?</td></tr><tr><td>A mixing parameter that uses enthalpy (only), i.e. depends on energy, i.e. chemistry, i.e. like dissolves like!</td></tr><tr><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# Having a single value for the solubility parameter has proved to be too simple.  \n\nSolubility parameter, $\\delta,$ must include all the contributions from how materials interact in solution  \n\n– dispersion,   \n– polar and   \n– hydrogen bonding interactions  \n\nEach type of interaction is represented by a component of  – represented in a three dimensional cartesian space  \n\n» dispersion » polar » hydrogen  \n\n $\\mathbf{\\Sigma}=\\mathbf{\\Sigma}$ distance to the origin $=(\\delta_{\\mathrm{d}}^{~2}+\\delta_{\\mathrm{p}}^{~2}+\\delta_{\\mathrm{h}}^{~2})^{1/2}$ $\\mathbf{\\Sigma}=$ Hansen scheme (dominates these days)  \n\n![](images/afa908d4b6caf33c962f25853677e6f263b8a84f74942182d352c822fca219a5.jpg)  \n\nCrowley, Teague, and Lowe (Eastman Chemical, 1966) published [Journal of Paint Technology Vol $39\\#504$ , Jan 1967] a representation with the Hildebrand parameter, a hydrogen bonding number, and the dipole moment (lumps the dispersion into the overall value).  \n\nStuart Croll",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# Interactions $\\mathbf{\\tau}=\\mathbf{\\tau}$ reasons how materials can differ  \n\n• “London” Dispersion forces  \n\n– Van der Waals forces   \n– Interactions between instantaneous dipoles induced by a neighboring dipole.   \n– Occurs in all materials to roughly same extent   \n– Weak ${\\sim}1/\\mathrm{r}^{6}$  \n\nPolar interactions  \n\n– from dipoles due to asymmetric charge (electrons) distribution on a molecule – Polar molecules have higher dielectric constant  \n\n» Alkanes and polyethylene dielectric constant ${\\sim}2$ » Ethanol \\~ 24 and water ${\\sim}79$  \n\n• Hydrogen Bonding Short range interaction mediated between the hydrogen bonds (tends to be used as a catch-all for other interactions as well)",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# Quantitative Compatibility?  \n\nFor high miscibility or ease of replacement  the solubility parameters must be very close.  \n\nIn a three-dimensional solubility parameter co-ordinate system the square of the distance between points representing two materials is given by (like any 3-D cartesian space):  \n\n$$\n(\\Delta\\delta)^{2}=(\\delta_{\\mathrm{d1}}\\textrm{-}\\delta_{\\mathrm{d2}})^{2}+(\\delta_{\\mathrm{p1}}\\textrm{-}\\delta_{\\mathrm{p2}})^{2}+(\\delta_{\\mathrm{h1}}\\textrm{-}\\delta_{\\mathrm{h2}})^{2}\n$$  \n\nIn the original Hansen scheme this distance, $\\Delta\\delta$ , should be less than 1 for good solubility or miscibility.  \n\nExperiment seems to indicate that a more useful expression would be  \n\n$$\n1\\geq4(\\delta_{\\mathrm{d1}}-\\delta_{\\mathrm{d2}})^{2}+(\\delta_{\\mathrm{p1}}-\\delta_{\\mathrm{p2}})^{2}+(\\delta_{\\mathrm{h1}}-\\delta_{\\mathrm{h2}})^{2}\n$$  \n\nAiming for a target in solubility parameter space.  \n\nIn principle the possible   \nsolvents for the solute lie   \nwithin the sphere.   \nAnything further away from   \nthe target than $\\Delta\\delta$ is not likely to be a solvent (or replacement solvent)   \nhttp://pirika.com/NewHP/PirikaE /polymer-solvent.html   \nHas applets  \n\n![](images/e639a5d6d1b79f6d21404848d7544a327e56052e1af35745ff739e4182653c6e.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# Practical application of Solubility Parameter  \n\n• (separation) radius $\\mathbf{\\Psi}=\\mathbf{\\Psi}_{1}$ does not work  \n\n$$\nR^{2}=(\\delta-\\delta_{d})^{2}+(\\delta-\\delta_{p})^{2}+(\\delta-\\delta_{h})^{2}\n$$  \n\nSphere: center $\\delta_{d},$ $\\delta_{p}$ , $\\delta_{h},$ radius $R$  \n\n• Solubility is seldom a sphere in solubility parameter space  \n\n• A better way to approach to matching materials is to plot the solubility space for each material and see how much they overlap  \n\n– More overlap the better   \n– But this requires a great deal more information   \n– Less popular",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# Determining Solubility Parameters  \n\n• Try many known solvents and see what works best for your unknown and deduce the values of the three components of the solubility parameter.  \n\n• Or, measure viscosity of polymer solution as a function of solubility parameter of the solvent  \n\n– Solubility parameter is given by solvent giving highest value of viscosity  \n\n» The most compatible solvent swells a polymer the most and increases viscosity the most.  \n\nCalculate values: quantum chemistry",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# Other considerations on choosing a perfect solvent.  \n\n• Remember – you may not want a perfect solvent – The solution viscosity may be too high if the polymer extends its conformation too far  \n\n• Not all of the reactive groups may react if the polymer, or oligomer is too tightly coiled in solution – Crosslinking density may be less than you thought it should be  \n\n• The compatibility of the ingredients may change as they react or evaporate – Phase separation leads to imperfections in the quality of the final film  \n\n<html><body><table><tr><td colspan=\"6\"></td></tr><tr><td>Quinoline</td><td>Solvent</td><td>Dispersion</td><td>Polar</td><td>Hydrogen Bonding</td><td>Molar Volume</td></tr><tr><td></td><td></td><td>19.4</td><td>7.0</td><td>7.6</td><td>118.0</td></tr><tr><td>Stearicacid</td><td></td><td>16.3</td><td>3.3</td><td>5.5</td><td>326.0</td></tr><tr><td>Styrene Succinic anhydride</td><td></td><td>18.6</td><td>1.0</td><td>4.1</td><td>115.6</td></tr><tr><td></td><td></td><td>18.6</td><td>19.2</td><td>16.6</td><td>66.8</td></tr><tr><td></td><td>1.1.2.2-Tetrabromoethane</td><td>22.6</td><td>5.1</td><td>8.2</td><td>116.8</td></tr><tr><td></td><td>1.1.2.2-Tetrachloroethane</td><td>18.8</td><td>5.1</td><td>9.4</td><td>105.2</td></tr><tr><td>Tetrachloroethylene</td><td></td><td>19.0</td><td>6.5</td><td>2.9</td><td>101.1</td></tr><tr><td>Tetraethylorthosilicate</td><td></td><td>13.9</td><td>0.4</td><td>0.6</td><td>224.0</td></tr><tr><td>*Tetrahydrofuran</td><td></td><td>16.8</td><td>5.7</td><td>8.0</td><td>81.7</td></tr><tr><td>Tetrahydronaphthalene</td><td></td><td>19.6</td><td>2.0</td><td>2.9</td><td>136.0</td></tr><tr><td>Tetramethylurea *Toluene</td><td></td><td>16.7</td><td>8.2</td><td>11.0</td><td>120.4</td></tr><tr><td></td><td></td><td>18.0</td><td>1.4</td><td>2.0</td><td>106.8</td></tr><tr><td></td><td>Tributyl phosphate</td><td>16.3</td><td>6.3</td><td>4.3</td><td>345.0</td></tr><tr><td></td><td>Trichlorobiphenyl</td><td>19.2</td><td>5.3</td><td>4.1</td><td>187.0</td></tr><tr><td>*Trichloroethylene</td><td>1.1.1-Trichloroethane</td><td>16.8</td><td>4.3</td><td>2.0</td><td>99.3</td></tr><tr><td>Trichlorofluoromethane</td><td></td><td>18.0</td><td>3.1</td><td>5.3</td><td>90.2</td></tr><tr><td></td><td></td><td>15.3</td><td>2.0</td><td>0.0</td><td>92.8</td></tr><tr><td>Tricresylphosphate</td><td>1.1.2-Trichlorotrifluoroethane</td><td>14.7</td><td>1.6</td><td>0.0</td><td>119.2</td></tr><tr><td>Tridecylalcohol</td><td></td><td>19.0</td><td>12.3</td><td>4.5</td><td>316.0</td></tr><tr><td>Triethanolamine</td><td></td><td>14.3</td><td>3.1</td><td>9.0</td><td>242.0</td></tr><tr><td>Triethylamine</td><td></td><td>17.3</td><td>22.4</td><td>23.3</td><td>133.2</td></tr><tr><td>Triethyleneglycol</td><td></td><td>17.8</td><td>0.4</td><td>1.0</td><td>138.6</td></tr><tr><td></td><td></td><td>16.0</td><td>12.5</td><td>18.6</td><td>114.0</td></tr><tr><td></td><td>Triethylene glycol monooleyl ether</td><td>13.3</td><td>3.1</td><td>8.4</td><td>418.5</td></tr><tr><td></td><td>Triethylphosphate</td><td>16.7</td><td>11.4</td><td>9.2</td><td>171.0</td></tr><tr><td></td><td>Trifluoroaceticacid</td><td>15.6</td><td>9.9</td><td>11.6</td><td>74.2</td></tr><tr><td>Water is</td><td>Trimethylbenzene</td><td>17.8</td><td>0.4</td><td>1.0</td><td>133.6</td></tr><tr><td></td><td>2.2.2.4-Trimethylpentane</td><td>14.1</td><td>0.0</td><td>0.0</td><td>166.1</td></tr><tr><td>different</td><td>2.2.4-Trimethyl-1.3-pentanediol M.I.butyral</td><td>15.1</td><td>6.1</td><td>9.8</td><td>227.4</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>→</td><td>Trimethylphosphate</td><td>16.7</td><td>15.0</td><td>42.2</td><td>115.8</td></tr><tr><td></td><td></td><td></td><td>1.0</td><td>3.1</td><td></td></tr><tr><td>Xylene</td><td>o-xylene</td><td>17.6 17.8</td><td>1.0</td><td>3.1</td><td>123.3 121.2</td></tr></table></body></html>\n\n\\*Indicates use in author's standard set of test solvents  \n\n<html><body><table><tr><td>Solubility Parameters for Mixtures</td></tr><tr><td></td></tr><tr><td>Blending Solvents, e.g. to dissolve a particular polymer or replace another solvent:</td></tr><tr><td>Combine linearly using volume fractions, e.g.</td></tr><tr><td>8dispersion(blend) = Φ1d1+Φ2d2+Φ3d3+ ..Φndn Spolar(blend) = Φ1 p1 + Φ p2 +Φ3 p3 +..中p Odn</td></tr><tr><td>Shydrogen bnding(blend) = Φ1 Sh1 + Φ2 Sh2 + Φ3 Sh3 + ... Φn Shn</td></tr><tr><td></td></tr><tr><td></td></tr><tr><td></td></tr></table></body></html>  \n\nExample Will toluene dissolve PMMA? $(\\delta_{\\mathrm{d1}}-\\delta_{\\mathrm{d2}})^{2}+(\\delta_{\\mathrm{p1}}-\\delta_{\\mathrm{p2}})^{2}+(\\delta_{\\mathrm{h1}}-\\delta_{\\mathrm{h2}})^{2}$ $(18.2\\textrm{-}18.0)^{2}+(10.3\\textrm{-}1.4)^{2}+(7.7\\textrm{-}2.0)^{2}=(10.6)^{2}>1$ Actually, a  solution is possible, depending on the molecular weight. $R$ must be larger than 1 for (probably) both materials (see elsewhere), and/or neither solubility behavior is a sphere Solubility Parameters are only a guide!",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# Example  \n\n• If we could mix $70\\%$ vol. Ethanol with $30\\%$ MEK, what would be the solubility parameters of the resultant (assuming miscibility)?  \n\ndispersion(blend) $=\\ 0.7\\mathrm{x}15.8\\ +\\ 0.3\\mathrm{~x}16=15.86$ polar(blend) = $0.7\\mathrm{~x~}8.8+0.3\\mathrm{~x~}9.0=8.86$ hydrogen bnding(blend) = $0.7\\textbf{x}19.4+0.3\\textbf{x}5.0=15.08$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# Solubility Parameter Data for Examples  \n\n<html><body><table><tr><td>Material</td><td>8d,Dispersion</td><td>8p,Polar</td><td>Sh,Hydrogen Bonding</td><td>Radius</td></tr><tr><td>PMMA</td><td>18.2</td><td>10.3</td><td>7.7</td><td>8.6</td></tr><tr><td>Epoxy</td><td>20.4</td><td>12.0</td><td>11.5</td><td>12.7</td></tr><tr><td>Polystyrene</td><td>20.8</td><td>5.6</td><td>4.2</td><td>12.7</td></tr><tr><td>Toluene</td><td>18.0</td><td>1.4</td><td>2.0</td><td></td></tr><tr><td>MEK</td><td>16</td><td>9</td><td>5</td><td></td></tr><tr><td>Ethanol</td><td>15.8</td><td>8.8</td><td>19.4</td><td></td></tr><tr><td>Dodecane</td><td>16.0</td><td>0</td><td>0</td><td></td></tr><tr><td>Acetone</td><td>15.5</td><td>10.4</td><td>7.0</td><td></td></tr><tr><td>Texanol</td><td>15.2</td><td>6.2</td><td>9.8</td><td></td></tr></table></body></html>  \n\nUnfortunately, exact numbers depend on measurement method and the molecular weight, and details of polymer structure.  \n\nWhat works for polymers?  \n\n• Single polymers in solvents – using solubility parameters often works – Entropy changes associated with polymer solutions tend to be small – Monomers already tied up in polymer Cannot mix freely to make a big difference in entropy  \n\n• Entropy is very  important when mixing two polymers imagine difficulty of mixing two large, complicated molecules  \n\n• Compatibility between polymers or issues of molecular weight or concentration – Go to Flory - Huggins Theory  \n\nStuart Croll",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# Limitations Of Solubility Parameters  \n\n• Do not predict solubility of all polymers in all solvents – All models are simplifications and don’t work exactly   \n• Miscibility is governed by changes in enthalpy and does not account for entropic changes.   \n• Oversimplification of hydrogen-bonding effects   \nMolecular weight effect not included - see Flory-Huggins theory  \n\nPractical solution is to remember that it is only an approximation",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# Flory-Huggins Theory  \n\nFlory-Huggins theory calculates a compatibility parameter $\\boldsymbol{\\chi}$ . For miscibility $\\chi$ must be less than $\\chi_{c}$ Materials that are more similar have lower values of $\\boldsymbol{\\chi}$  \n\n$$\n\\chi_{c}=\\frac{1}{2}\\Biggl(\\frac{1}{x_{a}^{1/2}}+\\frac{1}{x_{b}^{1/2}}\\Biggr)^{2}\n$$  \n\n$x=$ degree of polymerization, $\\mathbf{\\Psi}=1$ for a solvent and large for a polymer, so $\\chi_{\\mathrm{c}}$ is ${\\sim}0.5$ $\\mathbf{\\Sigma}=$ large for both polymers in a mixture , so $\\chi_{\\mathrm{c}}$ is very small for mixing of two polymers, i.e. it is difficult for polymers to mix  \n\nFlory-Huggins is not usually invoked until we have mixtures of polymers.",
+        "category": " Introduction"
+    },
+    {
+        "id": 17,
+        "chunk": "# Latest Theory on how polymers solvate  \n\n• J. Dudowicz, K. F. Freed, J. F. Douglas, “Solvation of polymers as mutual association. I. General theory,” J. Chem.  Phys.,138, 164901 (2013)  \n\n• J. Dudowicz, K. F. Freed, J. F. Douglas, “Solvation of polymers as mutual association. II. Basic thermodynamic properties,” J. Chem.  Phys.,138, 164902 (2013)",
+        "category": " References"
+    },
+    {
+        "id": 18,
+        "chunk": "# Evaporation Rates  \n\n• Evaporation rate is characteristic of a solvent  \n\n$\\mathbf{\\Sigma}=\\mathbf{\\Sigma}$ Weight loss/area/time   \n– Sensitive to temperature, partial vapor pressure of itself in the atmosphere, surface area vs. volume   \n– Evaporation of some solvents is sensitive to humidity (water is a solvent too) So it is usually defined relative to the rate of evaporation rate of n-butyl acetate  \n\n• Many solvents do not completely evaporate from a coating  \n\n– Enough affinity between polymer and solvent – Crosslinking traps the molecules",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# Evaporation?  \n\n• Molecules escape the surface of a liquid all the time (even well below their boiling point)  \n\n– Depending on how fast the molecules are moving » Depends on temperature   \n– Produces the vapor pressure   \nLiquid boils when its vapour pressure $\\mathbf{\\tau}=\\mathbf{\\tau}$ atmospheric pressure   \n• Boiling point value is a useful parameter to express the overall volatility   \n• The degree to which molecules escape depends on their attraction for each other and how much energy is needed for a molecule to get enough energy",
+        "category": " Introduction"
+    },
+    {
+        "id": 20,
+        "chunk": "# The Need for Evaporation Rate Control  \n\nMany application properties are controlled by how fast solvents leave:  \n\n• Wet edge (can you paint around a window frame fast enough for the paint to blend in where you started?)   \n• Levelling depends on viscosity and surface tension   \n• Sagging depends on viscosity   \n• How wet the atomized spray is when it arrives   \n• Orange Peel effects - surface tension driven convection cells set up as solvent evaporates   \n• Will the reactants diffuse together and react well?   \n• Will the coating go hard quickly enough?   \n• Will all the solvent escape and not form a skin and blister?  \n\nStuart Croll",
+        "category": " Introduction"
+    },
+    {
+        "id": 21,
+        "chunk": "# Evaporation Rate  \n\n• Relative evaporation rate $\\underline{{\\mathbf{\\omega}}}=\\underline{{\\mathrm{Time}}}_{90}.$ (N-butyl acetate) $\\mathrm{Time}_{90}$ (solvent under test)  \n\n• Measured by weighing – usually to $90\\%$ weight loss – Soaked filter paper (surface area remains constant) » Solvent and filter paper may interact – Shell “evapometer” ASTM D3539.76 (automatic weighing device)  \n\n• Can be calculated from Raoult’s Law if you know the activity coefficients of the mixture ingredients – Activity coefficients can be calculated – UNIFAC group contribution theory or computational chemistry  \n\n![](images/81990084984fcf7f9db6d56f7085acf3b12879824f5dfd404f3f6f4ed0d235e9.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 22,
+        "chunk": "# Evaporation from Coatings  \n\n• Initial period is like the solvent (mixture) alone – Controlled by the vapor pressure of the solvent above the coating  \n\nRate slows down  \n\n– Controlled by diffusion through coating as film forms – Rate also diminishes as solvent reservoir runs out  \n\nEnergy required in baking is the heat required to raise the temperature (specific heat) of the coating to some temperature (near Boiling Point) that permits the solvent to escape suitably plus the heat of vaporization  \n\n<html><body><table><tr><td colspan=\"4\">Evaporation Rate: Examples [CRC Handbook of Chemistry and Physics; A. L. Rocklin, JCT, Vol. 48, No. 622, pp. 45 - 57 (1976)]</td></tr><tr><td colspan=\"4\">Solvent Boiling Point Specific Heat Heat of Vaporization</td></tr><tr><td>rate</td><td>℃ J/g/K</td><td>J/g (at B.P.)</td><td></td></tr><tr><td>Acetone</td><td>56 2.17</td><td>502</td><td>9.3</td></tr><tr><td>Cyclohexane</td><td>81</td><td>1.84 356</td><td>6</td></tr><tr><td>Ethanol</td><td>78</td><td>2.44 838</td><td>2.3</td></tr><tr><td>Ethyl Acetate</td><td>77</td><td>1.94 363</td><td>6</td></tr><tr><td>MEK</td><td>80</td><td>2.2 435</td><td>5.1</td></tr><tr><td>MIBK</td><td>116</td><td>2.13 345</td><td>3.3</td></tr><tr><td>Methanol</td><td>65</td><td>2.53 1100</td><td>3.2</td></tr><tr><td>N-butylacetate</td><td>126</td><td>1.96 363</td><td>1</td></tr><tr><td>Toluene</td><td>111</td><td>1.71 361</td><td>2.1</td></tr><tr><td>Water</td><td>100</td><td>4.2 2258</td><td>0.64</td></tr><tr><td colspan=\"4\">· Polar materials need more heat to raise temperature and separate molecules,particularly water. Specific heat - internal modes of vibration · Vaporization － separating molecules</td></tr></table></body></html>  \n\n<html><body><table><tr><td>Background Information: VOC Calculations</td></tr><tr><td>VOC Determination, see ASTM D 3960 In general: VOC = Total Weight of Volatiles - Total Weight of Exempt Solvent - Weight of Water</td></tr><tr><td>Total Volume of Paint - Volume of Exempt Solvent - Volume of Water</td></tr><tr><td>Solvent Systems: VOC = (1O0 - NVW) [Wt./gal.] /100</td></tr><tr><td>Conversion: VOC [gram/Liter] = 119.84 x VOC [lbs./gal.]</td></tr><tr><td>Stuart Croll 44</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# Organic Solvents in Coatings  \n\n• VOC solvents are easy to use – Range available to dissolve many polymers » Many polymer chemistry options available – Range of evaporation rates available – Low surface tension – Many choices of solvent – Film formation usually done from polymer solution » But other options are possible  \n\nProblems with organic solvents.  \n\n• Flammable, and therefore dangerous   \n• Fumes or liquid may be toxic or otherwise harmful   \n• Many engage in atmospheric photochemistry and the byproducts affect greenhouse effect etc. and in combination with $\\mathsf{N O}_{\\mathrm{x}}$ produce ozone at low altitudes.  \n\nThus we limit the solvent content of paints and coatings etc.  \n\nA reason for water-borne coatings",
+        "category": " Introduction"
+    },
+    {
+        "id": 24,
+        "chunk": "# Water as Solvent, 1  \n\n• The solvent determines what we can get into solution – Water does not give us many options for water soluble polymers » Use latex or other emulsions, acid/base functionality, cosolvents  \n\n• Stabilization mechanism depends on dielectric properties of medium  \n\n– Water has high dielectric constant (very polar)   \n– Charge stabilization works $\\mathbf{\\Sigma}=\\mathbf{\\Sigma}$ useful (& cheap), but prone to abuse » Repulsive potential is higher in media of high dielectric constant - see DLVO theory » Don’t have to rely on steric stabilization only",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 25,
+        "chunk": "# Water as Solvent, 2  \n\nWater as a solvent has some disadvantages:  \n\n– High surface tension » Use surfactants   \n– Slow evaporating compared to common solvents » Evaporation greatly affected by ambient humidity   \n– High heat capacity and latent heat of evaporation   \n– Permits metallic corrosion  \n\n• Advantages  \n\n– Benign material – Plentiful, cheap supply (so far)  \n\nSummary – how to choose solvents • Viscosity – depends on compatibility • Wetting of pigments and substrates – Depends on surface tension  \n\n• Dissolution of binders etc. – Depends on compatibility • Leaving when job is done – Depends on evaporation rate",
+        "category": " Introduction"
+    },
+    {
+        "id": 26,
+        "chunk": "# Background: Laws of Thermodynamics (Not for a test)  \n\n1.  The amount of work needed to change the state of a system depends only on the change effected and not the means or the intermediate stages in the process. $\\mathbf{\\sigma}=\\mathbf{\\sigma}$ You cannot win  \n\n2.  No process is possible whose sole result is the complete conversion of heat into work $\\mathbf{\\sigma}=\\mathbf{\\sigma}$ You cannot break even  \n\n3.  In a system that is in internal thermodynamic equilibrium, the entropy tends to zero as the temperature tends to zero. $\\mathbf{\\sigma}=\\mathbf{\\sigma}$ You cannot get out of the game  \n\nKieffer’s Reduction: Prof. William F. Kieffer.",
+        "category": " Introduction"
+    },
+    {
+        "id": 27,
+        "chunk": "# Background: Definitions  \n\nRaoult’s Law:  \n\nVapor Pressure due to  a solution ingredient $\\mathbf{\\tau}=\\mathbf{\\tau}$ vapor pressure of pure ingredient  x its molar fraction » i.e. linear combination that works in “ideal” gases  \n\nAzeotrope is a mixed solution that boils at a constant temperature.  The vapor has same composition as the mixture.  B.P. may be higher or lower than either component by itself.  Therefore a mixture distills over, or is left.  E.g. alcohols and water.  \n\n– Non-ideal gases may provoke azeotropy if the resultant pressure is larger than the sum of the pure vapor pressures the component(s) \"don't like\" to be in the liquid phase. » this corresponds to smaller attractions between molecules in the mixture than in the pure components  \n\n– In other cases, azeotropy occurs because attractions between unlike molecules in mixtures are greater than those in the pure components.  \n\nStuart Croll  \n\n<html><body><table><tr><td>om J. H. Hildebrand and R. L. Scott, “Regular Solutions\", Prentice Englewood Cliffs,N. J. 1962</td><td></td></tr><tr><td></td><td> Scatchard-Hildebrand Equation</td></tr><tr><td></td><td>Cohesive Energy of a mole of liquid mixture ²x²++2²²</td></tr><tr><td></td><td>Mixture xv+xV -E</td></tr><tr><td></td><td>v= molar volume; x= molar fraction For pure components -E=cU etc. and if we assume that for</td></tr><tr><td></td><td>liquids at normal temperatures the vapour is ideal, we can identify -E with the heat of vapourisation</td></tr><tr><td></td><td>If we transform to volume fractions, Φ and Φ, then -EMixre =(c²+2c+C22²)(x+xV)</td></tr><tr><td></td><td>Energy of mixing:</td></tr><tr><td></td><td>△E=EMixre-Ex-Ex =(xv+x)(c-2c+C)</td></tr><tr><td></td><td>=(x+x)(c1²-c2）²</td></tr><tr><td></td><td>If c12=(C1C22)1/2 etc.</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 28,
+        "chunk": "# From same source  \n\nEntropy of mixing,  \n\n• If we have $N_{\\imath}$ and $N_{2}$ molecules of each of two sorts on a lattice, the entropy of mixing is given by:  \n\n$$\n{\\frac{\\Delta S_{M i x i n g}}{k}}=N_{1}\\ln\\left({\\frac{N_{1}+N_{2}}{N_{1}}}\\right)+N_{2}\\ln\\left({\\frac{N_{1}+N_{2}}{N_{2}}}\\right)\n$$  \n\n• Or, in entropy/mole of mixture  \n\n$$\n\\frac{\\Delta s_{M i x i n g}}{R}=-\\big(x_{1}\\ln x_{1}+x_{2}\\ln x_{2}\\big)\n$$",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/Synthesis and characterization of UV curable urethane acrylate oligomers containing ammonium salts for anti-fog coatings.json b/task2/task2-chunks/Synthesis and characterization of UV curable urethane acrylate oligomers containing ammonium salts for anti-fog coatings.json
new file mode 100644
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+++ b/task2/task2-chunks/Synthesis and characterization of UV curable urethane acrylate oligomers containing ammonium salts for anti-fog coatings.json	
@@ -0,0 +1,87 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Synthesis and characterization of UV curable urethane acrylate oligomers containing ammonium salts for anti-fog coatings  \n\nJ.W. Hong a, H.K. Cheon a, S.H. Kim a, K.H. Hwang a,  H.K. Kim b,∗  \n\na Department of Biochemical and Polymer Engineering, Chosun University, Gwangju 501-759, South Korea b Institute of Photonics &Surface Treatment, Q-Sys Co.Ltd., Gwangju, 61007, South Korea",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# a r t i c l e i n f o",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# a b s t r a c t  \n\nArticle history:   \nReceived 12 August 2016   \nReceived in revised form 2 March 2017   \nAccepted 6 March 2017   \nAvailable online 15 May 2017  \n\nKeywords:   \nUV-curing   \nAnti-fog   \nPhoto-DSC   \nSalts   \nCoating properties  \n\nUV-curable urethane acrylate oligomer (UV-UAO) containing ammonium salts,  suitable for  anti-fog (AF) coatings was synthesized. The expected UV-UAO structure was confirmed by FT-IR and $^1\\mathrm{H}$ NMR. This UVUAO was then formulated with reactive monomers and photoinitiator to form coating formulas. In order to compare the UV-curing behavior of  UV-UAO  with  conventional oligomers, the photopolymerization of UV-UAO and  SK  cytech EBECRYL-series urethane acrylates (EB  8210  and  EB  9260)  was  investigated by photo-differential scanning calorimetry (Photo-DSC). The  anti-fog properties of UV-cured AF coating were investigated by  contact  angle  test  and  anti-fog test.  Coating properties such as  pencil  hardness, pendulum hardness, gloss,  and  adhesion  of the UV-cured films  containing UV-UAO were investigated. The results showed that  the concentration of UV-UAO in  the  coating  formulation had  a great influence on the anti-fog properties of  UV-cured AF  coating. Especia  lly,  UV-cured AF  coating  containing UV-UAO 65 wt.%  showed excellent anti-fog properties without  sacrificing other  desirable properties such as  pencil hardness and  adhesion.  \n\n$\\mathfrak{C}$ 2017  Elsevier B.V.  All  rights reserved.",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1. Introduction  \n\nIn the past several years, there has been increasing interest in anti-fog coatings. In general, fog occurs when the difference between air temperature and dew point is generally less than $2.5^{\\circ}\\mathsf{C}.$ This fog begins to form when water vapor condenses onto a surface to form discrete and dispersed light–diffusing water droplets, thereby restricting light transmission and optical efficiency [1]. This undesirable fogging phenomenon occurs frequently on optical materials that are in use in everyday life such as bathroom mirrors, eyeglasses, safety glasses, swimming goggles, windshields, camera lenses, and skis as well as on analytical and medical instruments. In order to overcome this predicament, a method of applying an anti-fog treatment on the surface has been suggested.  \n\nThe basic concept of anti-fog is to create a hydrophilic surface that prevents the condensation of water in the form of small droplets so that light can transmit directly free of interference from scattering by the water droplets. In the early stages of anti-fog coating development, non-reactive anti-fog agents were conventionally introduced into a polymer matrix without chemical bonding. However, they do not produce stable long-term anti-fog properties because the anti-fog agents can be easily wiped off or partially lost during cleaning.  \n\nAccordingly, various materials and processes have been suggested for durable anti-fog coatings. For example, Maechler et al. have reported on a multilayer transparent anti-fog coating on a polycarbonate (PC) [2]. Nuraje at al. have reported on mechanically durable, long-lasting antifog coatings based on polysaccharides [3]. Cebeci et al. prepared stable superhydrophilic nanoporous thin films fabricated from layer-by-layer assembled silica nanoparticles and a polycation [4]. Chang et al. have developed a special hydrophilic/hydrophobic bilayer structure [5]. Yuan et al. have reported on UV curable hydrophilic acrylate polymers containing a sulfonic acid group for anti-fog coatings [6]. However, many of these fabrication processes involve complicated multi-steps and are often time consuming, which poses a hindrance for practical application. Accordingly, our research interest is to develop UV curable anti-fog coatings that can be obtained without the need for cumbersome and complicated synthesis and fabrication processes. This UV curable coating also offers other advantages such as higher productivity, energy savings, and lower capital investment for curing facilities.  \n\nIn this study, UV curable urethane acrylate oligomer containing ammonium salts for anti-fog coating was developed, and its antifog effectiveness and the surface properties of the coating network were investigated.  \n\n![](images/bc340d1c610cb8ebdd2b6663b2294eefa82257af5a993522eb0145dcd8ebf7b6.jpg)  \nScheme 1. Preparation of Ammonium Salt Monomer.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2. Experimental",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.1. Materials  \n\nThe monomers, including ethanolamine, and 2-butanone were purchased from Aldrich Chemicals and purified by vacuum distillation. SY-40M (glycidyl ether of C12 and C14 alcohol) was purchased from Sakamoto Yakuhin Kogyo Co., Ltd. (Japan), and was used without purification. Dimethyl sulfate was purchased from Aldrich Chemicals and purified by vacuum distillation prior to use. Isophorone diisocyanate (IPDI) was purchased from Evonik. Dibutyltin dilaurate (DBTDL) was purchased from Air Products. TLC Silica gel $60\\mathsf{F}_{254}$ (Merck) was used for TLC analysis. Pentaerythritol triacrylate (PETA) and dipentaerythritol hexaacrylate (DPHA) were all supplied by Miwon Specialty Chemical Co., Ltd. (Korea).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.2. Synthesis of ammonium salt (AS) monomer  \n\nEthanolamine $\\cdot10.16\\mathrm{g},0.166\\mathrm{mol}$ ) was added to a $250\\mathrm{mL}$ threeneck flask equipped with water bath, thermometer, refluxing condenser, dropping funnel, and magnetic stirring bar, and heated to $60^{\\circ}C$ with stirring. $86.55{\\mathrm{g}}$ of alkyl glycidyl ether (Sy 40M) was slowly added and the mixture was maintained for $^{2\\mathrm{h}}$ at $70^{\\circ}\\mathsf C$ . Dimethyl sulfate $\\cdot20.99,0.166\\mathrm{mol}$ ) and methyl ethyl ketone (MEK, $29.8{\\mathrm{g}}{\\mathrm{,}}$ were added dropwise to the stirred mixture over $3\\ensuremath{\\mathrm{h}}$ , while maintaining the temperature at $60^{\\circ}\\mathsf C.$ The salt group of the final product was identified by the titration of the remaining amine group with $0.1\\mathsf{N}$ HCl solution. $80\\%$ of the total amine group was converted into quaternary ammonium group. The reaction product was identified with $^1\\mathrm{H}$ NMR $(\\mathsf{C D C l}_{3}$ , ${300}\\mathrm{MHz}\\mathrm{\\cdot}$ ): 4.17 ppm $(\\mathrm{N^{+}{-}C H_{2}C\\underline{{{H}}}(-0H){-}C H_{2}})$ , $4.01\\mathrm{ppm}$ $(\\mathsf{N}^{+}{-}\\mathsf{C H}_{2}\\mathsf{C}\\underline{{H}}20\\mathsf{H})$ , 3.52 ppm $(\\mathrm{CH}_{2}\\mathrm{CH}(-0\\mathrm{H}){-}\\mathrm{C}\\underline{{{H2}}}{-}0),$ 3.43 ppm $(\\mathsf{N}{+}{-}\\mathsf{C}\\underline{{H}}_{2}\\mathsf{C}\\mathsf{H}_{2}{0}\\mathsf{H})$ , 3.39 ppm $\\left(\\mathsf{N}^{+}{-}\\mathsf{C}\\underline{{H}}_{2}\\mathsf{C}\\mathsf{H}(\\mathsf{O}\\mathsf{H})\\mathsf{C}\\mathsf{H}_{2}\\right)$ , 3.29 ppm ( $\\left(\\mathsf{N}^{+}{-}\\mathsf{C}\\underline{{{H_{3}}}}^{\\cdot}$ ), 1.22 ppm ${\\mathrm{O}}({\\mathrm{CH}}_{2}){\\mathrm{C}}\\underline{{{H}}}_{3};$ (Scheme 1).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.3. UV-curable urethane acrylate oligomer (UV-UAO) with ammonium salt  \n\nTo a solution of IPDI $\\left(34.5\\mathrm{g},0.16\\mathrm{mol}\\right)$ ), and PETA $(100\\mathrm{g})$ in MEK $\\mathrm{\\cdot100mL)}$ , DBTDL $(0.25{\\mathrm{g}})$ was added dropwise at $10^{\\circ}\\mathsf C$ with stirring. After complete addition, the mixture was stirred at $10^{\\circ}\\mathsf C$ for $\\boldsymbol{4\\mathrm{h}}$ . The reaction progress was analyzed by TLC using ethyl acetate: hexane $=1{:}2$ $(\\nu/\\nu)$ . And then, the AS monomer $(96.2{\\mathrm{g}})$ in MEK $(20\\mathrm{mL})$ was added to the above reaction product over 4 h, while maintaining the temperature at $20^{\\circ}\\mathsf C$ The reaction product was identified with $^1\\mathrm{H}$ NMR ( $\\mathrm{\\CDCl}_{3}$ , ${300}\\mathrm{MHz}^{\\cdot}$ and FT-IR: $^1\\mathrm{H}$ NMR $(\\mathsf{C D C l}_{3})$ ): 7.9 ppm $(-\\mathsf{N}H-)$ , $6.35{-}6.25\\mathrm{ppm}$ $\\scriptstyle(-{\\mathsf{C H}}={\\mathsf{C}}{\\underline{{H_{2}}}}$ ), $5.81{-}5.72\\mathrm{ppm}$ $\\scriptstyle(-{\\mathsf{C H}}={\\mathsf{C}}{\\underline{{{H_{2}}}}}$ ), $6.03\\substack{-5.92\\mathrm{ppm}}$ $(\\mathrm{-}\\mathsf{C}\\underline{{H}}\\mathrm{=}\\mathsf{C}\\mathsf{H}_{2}$ ); FT-IR spectrum: $-\\mathsf{N H}$ stretching $3300\\mathsf{c m}^{-1}$ ), ${\\mathsf{C}}{\\mathrm{-}}{\\mathsf{H}}$ deformation mode of the acryl groups $(811\\mathrm{cm}^{-1}$ ) (Scheme 2).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.4. Coating formulation and curing procedure  \n\nUV curable anti-fog (AF) compositions were prepared by mixing homogenously UV-UAO with reactive diluents (PETA:DPHA $_{.=8.5:1.5}$ by weight) and the photoinitiator (1- Hydrophenyl ketone, Irgacure 184 from Ciba Specialty Chemicals, maximum peak of absorption: $245{-}330\\mathrm{nm}$ ). Different amounts of UV-UAO $(55-70\\mathrm{wt}.\\%)$ were added into the above composition and the photoinitiator concentration was kept constant at $5\\mathrm{wt.\\%}$ all on the basis of final formulation. A $20\\mathrm{-}\\upmu\\mathrm{m}$ thick coating of the resin composition was applied on the polycarbonate (PC) using bar applicator and then cured with $80\\mathsf{W/c m}$ light a medium pressure mercury lamp of conventional UV equipment.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.5. Water contact angle and anti-fog tests  \n\nThe water contact angle of the UV-cured AF coating surface was determined by an SEO 300A from Surface & Electro-Optics Co., Ltd. This system is based on the sessile drop method. Temperature and relative humidity in the laboratory were within the range of  \n\n![](images/2545c52988ce1fea59b12cbf432ba0421c5eb983ffa72ddb047e3d3d8b7099f6.jpg)  \nScheme 2. Preparation of UV-UAO.  \n\n$21^{\\circ}\\mathsf{C}_{-}25^{\\circ}\\mathsf{C}$ and $30\\%$ , respectively. DI water was used as probing liquids.  \n\nAnti-fog properties were evaluated through two separate testing methods: First, a steam anti-fog test is done as follows. Hot water $(80^{\\circ}\\mathsf{C})$ was added into a cup to about half full. Then, the sample was placed on the cup with the coated surface facing down. Vapor condensed on the coating surface was observed and photographed [5]. Second, a cold anti-fog test is done as follows. The sample was put into a $-20^{\\circ}C$ refrigerator for 1 h and taken out in a $50\\%$ humidity environment.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 2.6. Curing monitoring and coating properties  \n\nThe different photo calorimetry (Photo-DSC) experiments were conducted using a differential scanning calorimeter equipped with a photocalorimetric accessory (TA 5000/DSC 2920). The initiation light source was a 200 W high-pressure mercury lamp: the UV light intensity at the sample was $35\\mathrm{mW}/\\mathrm{cm}^{2}$ over a wavelength range of $200{-}440\\mathrm{nm}$ . The sample was placed in uncovered aluminum pans. TA Instruments software was employed to obtain the results from the photo-DSC experiments.  \n\nmeasured on Leneta test papers using a gloss meter from Sheen Co. (ASTM D 523). The recorded values were an average of five measurements. The adhesion of the coating was measured by using the cross-cut kit by Precision Gage & Tool Co. as described in ASTM D3359. A crosshatch pattern is made through the film to the substrate. Pressure-sensitive tape is applied over the crosshatch cut. Tape is removed by pulling it off rapidly back over itself at close to an angle of $180^{\\circ}$ . Adhesion is assessed on a 0–5 scale. Then the adhesion test was examined before the anti-fogging tests at $25^{\\circ}\\mathsf{C}$ and under relative humidity $30\\%$ .  \n\nThe surface hardness of the cured film was measured by using graphite pencils of increasing hardness as described in ASTM D 3363-74. Pendulum hardness (ASTM D4366-84) was measured as the time taken for the oscillations of a pendulum to reduce from $6^{\\circ}$ to $3^{\\circ}$ (König ref. 707KP from Sheen). The gloss of the coating was",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3. Results and discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3.1. Curing behavior of UV-UAO  \n\nThe UV-curing behavior of the synthesized UV-UAO was compared with that of SK cytech EBECRYL-series urethane acrylate oligomers commonly used in UV-curable systems by Photo-DSC. The photo-DSC exotherms for the photopolymerization of EB 8210, EB 9260, and UA-UAO are illustrated in Fig. 1. The filled circles, open circles, and filled downward triangles are the measured heat flow of EB 8210, EB 9260, and UV-UAO, respectively. From the peak symmetry, induction time, and the time to peak maximum, one can obtain information such as the optimum ratio of monomer to oligomer, the photoinitiator efficiency, and the curing rate [7]. The amounts of heat released, induction time, peak to maximum, and the ultimate percentage conversions derived from Fig. 1 are collected in Table 1.  \n\n![](images/d1ec799a76c657b6871af27519ff3326f717f5c830819b179655c226e759a51b.jpg)  \nFig. 1. Photo-DSC exothermic curves for the photopolymerization of EB 8210, EB 9260, and UV-UAO.  \n\nTable 1 Data from photo-DSC studies on EB 8210, EB 9260, and UV-UAO (IT, induction time; PM, time to peak maximum).   \n\n\n<html><body><table><tr><td>Sample</td><td>Functionality</td><td>Mw (g/mol)</td><td>△H (J/g)</td><td>IT (s)</td><td>PM (s)</td><td>Conversion (%)</td></tr><tr><td>EB8210</td><td>4</td><td>600</td><td>310</td><td>1.00</td><td>1.98</td><td>83</td></tr><tr><td>EB 9260</td><td>3</td><td>1500</td><td>163</td><td>1.08</td><td>1.98</td><td>58</td></tr><tr><td>AF-UAO</td><td>3</td><td>830</td><td>154</td><td>1.10</td><td>2.58</td><td>53</td></tr></table></body></html>  \n\nTable 2 Curing Parameters of UV-cured AF coatings.   \n\n\n<html><body><table><tr><td>Sample</td><td>AF1</td><td>AF2</td><td>AF3</td><td>AF4</td></tr><tr><td>UV-UAO content (%)</td><td>55</td><td>60</td><td>65</td><td>70</td></tr><tr><td> H(J/g)</td><td>302</td><td>298</td><td>287</td><td>208</td></tr><tr><td>Induction Time (sec)</td><td>1.12</td><td>1.00</td><td>0.96</td><td>1.02</td></tr><tr><td>Time to Peak Maximum (sec)</td><td>2.76</td><td>1.98</td><td>1.92</td><td>2.34</td></tr><tr><td>Conversion (%)</td><td>75</td><td>74</td><td>70</td><td>59</td></tr></table></body></html>  \n\nAs expected, the results show (Table 1) that tetra functional EB 8210 with low molecular weight has the shortest induction time and the shortest time to peak maximum as well as the highest value of $\\Delta{\\sf H}$ , indicating the fastest reaction system. Meanwhile, the synthesized UV-UAO and EB 9260 have a similar value for induction time, and UV-UAO has the longest time to peak maximum. In addition, the conversion of the UV-UAO is lower than that of EB 8210 and EB 9260, as shown by the lower value of $\\Delta{\\sf H}$ . This may be a result of the steric effect of quaternary ammonium salts. As shown, although the photopolymerization efficiency of the UV-UAO is lower than that of the commercially available EB 8210, it is similar to that of EB 9260 under the same experimental conditions. Therefore, it is obvious that the synthesized UV-UAO is suitable for practical use in UV coating formulations as the oligomer.  \n\nAt this point, it is necessary to investigate the effects of UV-UAO concentration on the curing behavior of the UV-curable coating formulations. The photo-DSC exotherms for photopolymerization containing variable concentrations of UV-UAO in the coating formulations are shown in Fig. 2; while the amount of the measured heat flow, the induction time, the time to peak maximum, and the ultimate percentage conversion are collected in Table 2.  \n\nHeat flow and percentage conversion decrease as the concentration of UV-UAO increases (Fig. 2 and Table 2); however, the AF3 containing $65\\%$ of UV-UAO has the shortest induction time and the shortest peak maximum, indicating that the initial curing rate is faster than that of the other AF samples. Although the mechanism for this improved initial curing rate is not clear yet, it can be tentatively explained as follows: The addition of UV-UAO into the UV coating formulation increases slightly the viscosity of the AF coating formulation. In general, it is known that increasing the viscosity of the coating decreases the oxygen diffusion into the coating and improves the surface cure [8]. Therefore, it could be expected that the improved curing rate may be attributed to oxygen inhibition. In addition, there is a sudden drop in curing properties as the UV-UAO concentration is increased above $65\\%$ . It is supposed that there are potential incompatibility problems with other components present in the coating formulation.  \n\n![](images/9c3134755512c2be3edb084d439f92c77bc957cf2c1ca3c23cb1e3b050db086e.jpg)  \nFig. 2. Photo-DSC exotherms for the photopolymerization of formulations AF1-AF4.  \n\n![](images/813f540bccb34bdfe088db7cfb97264baa1b04d3e3831248c30300b6d0cc96ce.jpg)  \nFig. 3. Steam anti-fog test of uncoated PC (left) and formula AF 3 coated PC (right).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.2. Antifogging properties  \n\nIn order to investigate the anti-fog properties of the prepared UV-cured anti-fog (AF) coatings containing variable concentrations of UV-UAO in the coating formulations, the water contact angle and AF tests of UV-cured AF coatings were examined under a variety of different fogging conditions and the results are summarized in Table 3. The neat PC surface is relatively hydrophobic with a high water contact angle of $74^{\\circ}$ , and the AF test shows a fog appearance (Figs. 3 and 4). After applying a UV-cured AF coating on PC, the water contact angle drops markedly from $58^{\\circ}$ to $5^{\\circ}$ as the content of UV-UAO in the formulation increases from $55\\%$ to $70\\%$ (Table 3). Especially, the AF 3 and AF4 with $65\\%$ and $70\\%$ of UV-UAO in the formulation exhibited lower static water contact angle values $\\mathrm{\\cdot}\\mathrm{AF}3=6^{\\circ}$ , ${\\mathsf{A F}}4=5^{\\circ}$ ) than the AF 1 and AF 2, suggesting that the addition of the UV-UAO into the coating formulation was effective for increasing the surface hydrophilicity of the hydrophobic PC substrate. The hydrophilic OH group and quaternary ammonium salts of UV-UAO were expected to provide excellent anti-fog capability to the coating film because both groups are able to imbibe water on the surface layer, and this hydrophilic surface decreases the water droplet contact angle and provides the anti-fog performance.  \n\nTable 3 Anti-fog test and coating properties of UV-cured AF coatings.   \n\n\n<html><body><table><tr><td colspan=\"2\">Sample</td><td>AF1</td><td>AF2</td><td>AF3</td><td>AF4</td></tr><tr><td rowspan=\"2\">Contact Angle（°）</td><td>Initial</td><td>58</td><td>50</td><td>6</td><td>5</td></tr><tr><td>After water soaking</td><td>56</td><td>49</td><td>5</td><td>Partly detached</td></tr><tr><td rowspan=\"2\">Antifog performance</td><td>Cold-fog test</td><td>fogging</td><td>Some -fogging</td><td>Anti-fog</td><td>Anti-fog</td></tr><tr><td>Steam-fog test</td><td>fogging</td><td>Some -fogging</td><td>Anti-fog</td><td>Anti-fog</td></tr><tr><td colspan=\"2\">Pendulum Hardness</td><td>208</td><td>213</td><td>228</td><td>203</td></tr><tr><td colspan=\"2\">Pencil Hardness</td><td>1H</td><td>1H </td><td>2H</td><td>1H</td></tr><tr><td colspan=\"2\">Gloss</td><td>133.5</td><td>134.8</td><td>135.2</td><td>135.5</td></tr><tr><td colspan=\"2\">Adhesion/cross-cuta</td><td>0</td><td>0</td><td>0</td><td>3</td></tr></table></body></html>\n\na 0: The edges of the cuts are completely smooth; none of the squats of the lattice are detached, 3: A cross-cut area significantly greater than $15\\%$ , but not significantly greater than $35\\%$ , is affected.  \n\n![](images/b981701bb4122e807df61732a8dc7d18140a22a5008c3d2669530d056cce0f37.jpg)  \nFig. 4. Cold anti-fog test of uncoated PC (left) and AF 3 coated PC (right) after removal from $-20^{\\circ}C$ freezer to humid environment.  \n\nIn practice, the durability of AF coatings is of major concern, in addition to the initial water wettability, particularly when the coating is to be used in high humidity conditions. In this regard, in order to test anti-fog durability, various AF coatings were soaked in water for an extended period of time. It was found that AF 4 with $70\\%$ UV-UAO content cannot withstand long-term water soaking with the AF layer of the AF 4 detaching partly from the PC substrate after being immersed in water for 1 day at $25^{\\circ}\\mathsf C$ whereas AF 3 with good water wettability and anti-fog performance retains its outstanding anti-fog durability (Table 3).  \n\nThe anti-fog performance of the AF 3 coatings is shown by the steam-fog test and the cold-fog test, and AF 1 and AF 2 do not exhibit acceptable anti-fog performance (Table 3). In the case of AF 4, excellent anti-fog ability was observed in the initial stages; however, it did not provide anti-fog durability. In contrast, AF 3 provided excellent antifogging capability under a variety of different fogging environments. In the steam fog test, the formula AF 3 coated PC (right part) was seen clearly and retained good transparency; however, the uncoated PC (left part) fogged immediately (Fig. 3). A more aggressive cold-fog test was performed by placing the AF 3 coated PC and the uncoated PC in a freezer at $-20^{\\circ}C$ for 1 h. Both samples were then removed into a humid environment. The uncoated PC (left part) was wholly fogged; however, the AF 3 coated PC (right part) remained fog free (Fig. 4).  \n\n![](images/869f57aed041489dcf3c3f49ec977b7acfeb234f9b9d92348909551387f1f40f.jpg)  \nFig. 5. FTIR-ATR spectra of UV-cured AF films at the film-air interfaces: (a) AF 1 (UV-UAO 55 wt.%); (b) AF 2 (UV-UAO 60 wt.%); (c) AF 3 (UV-UAO 65 wt.%).  \n\nHenceforth we will not discuss AF 4 because its anti-fog properties and conversion from Photo-DSC are outside the specification required in this paper.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3.3. Coating properties and degree of surface curing  \n\nSince pencil hardness and pendulum hardness are determined primarily by structural parameters such as cross-link density, it is appropriate to consider the cross-link density of the samples [9,10]. It is known that PC is relatively soft and tough with a pencil hardness $<2\\tt B$ . After being coated with AF coating formulation containing UV-UAO, its hardness was raised to 2H (AF 3 coating), which is sufficiently high for general purposes. Among the UV-cured AF coatings, AF 3 exhibited the highest pendulum and pencil hardness compared with the other AF coatings (Table 3), suggesting that the cross-link density of the AF 3 is higher than that of the other AF coatings.  \n\nIn order to confirm the above results, the unreacted acrylic double bonds at the film-air interface of the UV-cured AF coating films were measured by FTIR-ATR, and the results showed clearly (Fig. 5)  \n\nthat the intensity at $811\\mathrm{cm}^{-1}$ decreases with increasing amounts of UV-UAO. Since the infrared band at $811\\mathrm{cm}^{-1}$ is attributable to the $C{\\mathrm{-}}\\mathrm{H}$ deformation mode of the acryl groups, it can be concluded that the addition of UV-UAO into the formulation increases the degree of surface curing. These FTIR-ATR results are in very good agreement with the results of the pencil and pendulum hardness tests.  \n\nIn light of these results, it is evident that adding UV-UAO at $65\\%$ results in a cured film that achieves a good balance between anti-fog properties and hardness, two characteristics that are often difficult to achieve at the same time.  \n\nWe then turned to other coating properties such as gloss and adhesion. All of the UV-cured AF films containing UV-UAO (except that with $70\\mathrm{wt\\%}$ of UV-UAO) exhibited excellent adhesive properties for PC (Table 3). Since adhesion was related to the ion content, the higher ion content in the UV-cured AF films may increase the ion strength, which may improve the adhesion between the film and the PC substrate. In addition, increasing the UV-UAO concentration from 55 wt. $\\%$ to 70 wt. $\\%$ produced no detectable difference in gloss (Table 3).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 4. Conclusions  \n\nThis work demonstrates that UV-UAO is a useful oligomer that can provide excellent anti-fog properties for a UV-cured coating under a variety of environmental conditions. Surfaces coated with a coating formulation containing UV-UAO are capable of spreading and absorbing water, thereby preventing fog formation on the optical substrate. Specially, AF 3 containing UV-UAO 65 wt. $\\%$ in a coating formulation achieves a good balance between anti-fog properties and surface hardness. This UV curable anti-fog coating with UV-UAO also offers desirable product features such as simple wet chemical application methods and a fast curing process for maximum process yields.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 17,
+        "chunk": "# References  \n\n[1] J.A. Howarter, J.P. Youngblood, Macromol. Rapid Commun. 29 (2008) 455–466.   \n[2] L. Maechler, C. Sarra-Bournet, P. Chevallier, N. Gherardi, G. Laroche, Plasma Chem. Plasma Process. 31 (2011) 175–187.   \n[3] N. Nuraje, R. Asmatulu, R.E. Cohen, M.F. Rubner, Langmuir 27 (2011) 782–791.   \n[4] F.C. Cebeci, Z. Wu, L. Zhai, R.E. Cohen, M.F. Rubner, Langmuir 22 (2006) 2856–2862.   \n[5] C.C. Chang, F.H. Huang, H.H. Chang, T.M. Don, C.C. Chen, L.P. Cheng, Langmuir 28 (2012) 17193–17201.   \n[6] Y. Yuan, R. Liu, C. Wang, J. Luo, X. Liu, Prog. Org. Coat. (2014) 785–789.   \n[7] J.W. Hong, H.W. Lee, J. Korean Ind. Eng. Chem. 5 (1994) 860.   \n[8] R. Schwalm, UV Coating: Basics, Recent Development and New Applications, 2007, pp. 179–184.   \n[9] H.K. Kim, Y.B. Kim, J.D. Cho, J.W. Hong, Prog. Org. Coat. 48 (2003) 34–42.   \n[10] H.K. Kim, H.T. Ju, J.W. Hong, Eur. Polym. J. 39 (2003) 2235–2241.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,92 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Synthesis of UV-curable acrylate polymer containing sulfonic groups for anti-fog coatings  \n\nYan Yuan, Ren Liu, Chunlin Wang, Jing Luo, Xiaoya Liu ∗  \n\nThe Key Laboratory of Food Colloids and Biotechnology, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, China",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 2,
+        "chunk": "# a r t i c l e i n f o  \n\nArticle history:   \nReceived 5 November 2013   \nReceived in revised form   \n10 December 2013   \nAccepted 1 January 2014   \nAvailable online 23 January 2014   \nKeywords:   \nUV-curable   \nSulfonic group   \nAcrylate   \nAnti-fog",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# a b s t r a c t  \n\nA series of UV curable hydrophilic acrylate polymers containing sulfonic acid group was prepared via free radical copolymerization using  2-acrylamido-2-methyl propane sulfonic acid  (AMPS)  as  hydrophilic monomer, which were  used  as  prepolymers for  anti-fog coatings. The  expected structures were  confirmed by FT-IR, $^1\\mathrm{H}$ NMR  and  gel permeation chromatography (GPC).  These UV-curable acrylate polymers were then mixed  with reactive diluents and  photoinitiator to  form  coating formulas. Various  substrates were coated with  these  formulas and  cured  under  UV  exposure to  obtain  transparent coatings with  good adhesion and hardness. The anti-fog properties of  UV-cured coating were measured by  contact angle test and anti-fog test. The results showed that  the AMPS content in  prepolymer had a  great  influence on  the anti-fog properties of  UV-cured coating. The formula  was  optimized and the  corresponding UV-curing anti-fog coating was  manufactured. The  test results indicated that  the  coatings showed  good  mechanical properties, great  optical transparency and  excellent anti-fog performance.  \n\n$\\mathfrak{C}$ 2014 Elsevier B.V. All rights reserved.",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1. Introduction  \n\nWater vapor can condense on solid surface at a certain temperature or humidity, and water on surface forms little droplets if the solid surface has a very high surface energy. Therefore the light is refracted and scattered by water droplets and the transparent materials turn hazy, which causes fogging problems. Many optical devices are suffering from fogging problems, such as eyeglasses, mirrors, windshields and many other devices in special fields [1–4]. There are two efficient ways to solve the problem. One is to heat the device to make water vapor non-condensing, and the other is to provide the solid surface with wetting characteristics such as hydrophilicity [5] or even super hydrophilicity [6]. Although the former method is efficient, the cost of energy limits its wide application.  \n\nHydrophilic surfaces that have contact angles with water of less than $40^{\\circ}$ are often explored as anti-fog coatings. The main reason is that condensing water droplets on this type of surface can rapidly spread into a uniform and non-light-scattering water film [7,8]. In this case, although condensation still occurs, the surface remains optically clear. The key to this approach is the use of materials which can strongly interact with water molecules and/or have a high capacity to absorb water. Hydrophilic polymeric systems containing hydroxyl groups $(\\mathrm{-OH})$ , amino group $\\left(\\mathrm{-NH}_{2}\\right).$ , carboxyl group ( COOH) or sulfonic group $(-S0_{3}\\mathrm{H})$ are often utilized in antifog formulas [9,10]. However, the preparation of optical quality thin-film coatings with these hydrophilic functionalities exhibiting both good coating characteristics and mechanical durability is still a great challenge.  \n\nHerein, a new coating system with good anti-fog properties and mechanical properties was presented. This new coating system was based on a UV-curable hydrophilic polymer which was prepared via free radical copolymerization with 2-acrylamido-2- methyl propane sulfonic acid (AMPS) as hydrophilic monomer. After UV-curing, the resultant coating exhibited good anti-fog properties as well as good mechanical properties.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2. Experimental",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.1. Materials  \n\nMethyl methacrylate (MMA), 2-ethylhexyl acrylate (EHA), 2-hydroxyethyl methacrylate (HEMA), 2-acrylamido-2-methyl propane sulfonic acid (AMPS), isophorone diisocyanate (IPDI), $^{2,2^{\\prime}}$ - azobisisobutyronitrile (AIBN), potassium hydroxide (KOH), methyl alcohol (MeOH), dibutyltin dilaurate (DBTDL), 4-methoxyphenol (MEHQ), acetic ether (EAc), N,N-dimethylformamide (DMF) were all purchased from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China).  \n\n![](images/c7a4642c1b3d33715de204fc6f4e7f129deb1cea9c57d6fc5fad11cd3bfc037a.jpg)  \nScheme 1. The synthetic route of IU-PHEMA.  \n\n1-Hydroxycyclohexyl phenyl ketone (HCPK), 1,6-hexanediol diacrylate (HDDA), ethoxylated trimethylolpropane triacrylate (EOTMPTA), trifunctional acid ester (CD9051), phosphate (w190) were all supplied by Jiangsu Kuangxin Photosensitivity Newmaterial Stock Co., Ltd. (Wuxi, China).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.2. Synthesis of prepolymer  \n\nAn isocyanate-containing unsaturated monomer named as HIp was prepared via nucleophilic addition of IPDI and HEMA. The molar ratio of two reactants was 1:1 and the temperature was maintained at $40^{\\circ}\\mathsf C$ .  \n\nA series of sulfo-group-containing acrylate copolymers (PHEMA) were synthesized via free radical copolymerization of AMPS, HEMA, EHA and MMA. AIBN-initiated bulk copolymerizations of monomers were carried out at $90^{\\circ}\\mathsf C.$ . The concentration of AIBN was fixed equal to $2\\times10^{-3}$ mol per mol of all monomers. The prepared PHEMA then reacted with Hip to introduce urethane groups and cross-linkable double bonds into the side chain of polymer, which led to a UV-curable copolymer named as U-PHEMA. Finally, the IU-PHEMA, a prepolymer for antifog coating, was obtained by ionization of U-PHEMA with KOH–methanol solution. The whole synthetic route is shown in Scheme 1.  \n\nIn the experiment, a series of IU-PHEMA prepolymers were prepared to investigate the influence of AMPS content on anti-fog properties. Table 1 shows the amount of each component used in the reaction.  \n\nTable 1 Composition of IU-PHEMA in copolymerization.   \n\n\n<html><body><table><tr><td>No.</td><td>HEMA</td><td>EHA</td><td>MMA</td><td>AMPS</td><td>IPDI</td><td>HEMA</td><td>AMPS%</td></tr><tr><td>IU-PHEMA01</td><td>21.95</td><td>24.72</td><td>11.24</td><td>1.00</td><td>25.00</td><td>16.01</td><td>1%</td></tr><tr><td>IU-PHEMA03</td><td>21.95</td><td>22.72</td><td>11.24</td><td>3.00</td><td>25.00</td><td>16.01</td><td>3%</td></tr><tr><td>IU-PHEMA05</td><td>21.95</td><td>20.72</td><td>11.24</td><td>5.00</td><td>25.00</td><td>16.01</td><td>5%</td></tr><tr><td>IU-PHEMA07</td><td>21.95</td><td>18.72</td><td>11.24</td><td>7.00</td><td>25.00</td><td>16.01</td><td>7%</td></tr><tr><td>IU-PHEMA08</td><td>21.95</td><td>17.72</td><td>11.24</td><td>8.00</td><td>25.00</td><td>16.01</td><td>8%</td></tr><tr><td>IU-PHEMA10</td><td>21.95</td><td>15.72</td><td>11.24</td><td>10.00</td><td>25.00</td><td>16.01</td><td>10%</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.3. Preparation of anti-fog coating  \n\nThe IU-PHEMA was mixed with photoinitiator and reactive diluents to obtain formulas. HDDA and EOTMPTA were chosen as the reactive diluents to increase the double bond content, and CD9051 and w190 were used to improve the adhesion of formula on glass. Then the formula was coated on clean substrates to obtain a transparent film. The compositions of all formulas were shown in Table 2.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.4. Measurements  \n\nThe number-average molecular weight $(M_{\\mathfrak{n}})$ and molecular weight distribution or polydispersity index PDI $(M_{\\mathrm{W}}/M_{\\mathrm{n}})$ of the polymers were determined at $25^{\\circ}\\mathsf{C}$ with WATERS GPC-1515(GPC), using DMF as eluent at a flow rate of $1.0\\mathrm{mL}\\mathrm{min}^{-1}$ . The molecular weight and polydispersity index data were compared against broad standards of PEG. FT-IR spectra were recorded with a Bomem FTLA 2000-104 using the potassium bromide (KBr) disk sampling technique. $^1\\mathrm{H}$ NMR spectrum for IU-PHEMA was obtained by an AVANCE III ${400}\\mathrm{MHz}$ Digital NMR spectrometer at $25^{\\circ}\\mathsf C$ , using DMSO-d6 as solvent.  \n\nTable 2 Composition of UV-curable anti-fog coatings.   \n\n\n<html><body><table><tr><td>Formula</td><td>Resin</td><td>Resin content</td><td>HDDA</td><td>EOTMPTA</td><td>CD9051</td><td>Phosphate</td><td>HCPK</td></tr><tr><td>FA1</td><td>IU-PHEMA01</td><td>70</td><td>10</td><td>10</td><td>5</td><td>2</td><td>3</td></tr><tr><td>FA2</td><td>IU-PHEMA03</td><td>70</td><td>10</td><td>10</td><td>5</td><td>2</td><td>3</td></tr><tr><td>FA3</td><td>IU-PHEMA05</td><td>70</td><td>10</td><td>10</td><td>5</td><td>2</td><td>3</td></tr><tr><td>FA4</td><td></td><td>70</td><td>10</td><td>10</td><td>5</td><td>2</td><td>3</td></tr><tr><td>FA5</td><td></td><td>50</td><td>20</td><td>20</td><td>5</td><td>2</td><td>3</td></tr><tr><td>FA6</td><td>IU-PHEMA07</td><td>40</td><td>25</td><td>25</td><td>5</td><td>2</td><td>3</td></tr><tr><td>FA7</td><td></td><td>30</td><td>30</td><td>30</td><td>5</td><td>2</td><td>3</td></tr><tr><td>FA8</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>IU-PHEMA08</td><td>5040</td><td>2025</td><td>2025</td><td>５５</td><td>２2</td><td>33</td></tr><tr><td>FA10</td><td></td><td>50</td><td>20</td><td>20</td><td>5</td><td>2</td><td>3</td></tr><tr><td>FA11</td><td>IU-PHEMA10</td><td>40</td><td>25</td><td>25</td><td>5</td><td>2</td><td>3</td></tr></table></body></html>  \n\nContact angles were measured using a DATA physics OCA40 contact angle goniometer equipped with an environmental chamber. Three drops of water were used for each measurement, and the average contact angle values were reported. Samples for testing were cured on a slide.  \n\nThe coatings are prepared on one side of clean substrates and cured under UV lamp. One part of each substrate is coated and the other part is uncoated. Then samples are held above hot water $(80^{\\circ}\\mathsf{C})$ for 15 s, which is called the anti warm fog test.  \n\nAs comparison, an anti cold fog test is done as follows. The coatings are prepared on both sides of clean substrates and cured under UV lamp. One part of each substrate side is coated and the other part is uncoated. Then the samples are put into a $-15^{\\circ}\\mathsf C$ refrigerator for $10\\mathrm{min}$ and taken out in a $50\\%$ humidity environment.  \n\nTo evaluate the oil resistance of samples, coated panels were immersed in oleic acid at room temperature. To examine the chemical resistance, samples were immersed in $0.5\\mathrm{mol}\\mathrm{L}^{-1}\\mathrm{H}_{2}\\mathrm{S}0_{4}$ , $\\boldsymbol{1}\\mathrm{mol}\\mathrm{L}^{-1}$ NaOH and $50\\%$ ethanol, respectively.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3. Results and discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3.1. Characterizations of U-PHEMA  \n\nThe FT-IR spectra of PHEMA, HIp and U-PHEMA are shown in Fig. 1. From Fig. 1(a), the absorption peaks of $\\mathsf{C}{=}\\mathsf{C}$ at $1640\\mathsf{c m}^{-1}$ and $\\scriptstyle{\\mathrm{H-C=}}$ at $810\\mathrm{cm}^{-1}$ disappear, which is an evidence that all the monomers have reacted during the copolymerization. Besides, the peak of $s{=}0$ at about $1400\\mathrm{cm}^{-1}$ is observed, indicating the introduction of sulfonic group in the polymer. From Fig. 1(b), the appearance of the characteristic peaks of $\\mathsf{C}{=}\\mathsf{C}$ at $1640\\mathsf{c m}^{-1}$ and $810\\mathrm{cm}^{-1}$ indicates HEMA has successfully reacted with IPDI. As shown in Fig. 1(c), the disappearance of peak at $2236\\mathrm{cm}^{-1}$ indicates the successful reaction between $-\\mathsf{N C O}$ in HIp and $-\\mathsf{O H}$ in PHEMA. What is more, the presence of $\\mathsf{C}{=}{\\mathsf{C}}$ at $1640\\mathrm{cm}^{-1}$ and $\\scriptstyle{\\mathrm{H-C=}}$ at $810\\mathrm{cm}^{-1}$ indicates that photo-crosslinkable double bond has been successfully introduced into the polymer. Fig. 2 shows the $^1\\mathrm{H}$ NMR spectrum of U-PHEMA. The peak a at $7.9\\mathrm{ppm}$ is related to group of $-N\\mathsf{H}-$ , peaks b at 6.1 ppm and $5.8\\mathsf{p p m}$ are assigned to the ${\\mathrm{HC}}{=}{\\mathrm{CH}}$ , and peak c, d and e belong to $\\scriptstyle0=\\mathsf{C}-\\mathsf{C}-\\mathsf{H}$ in the structure of polymer. Based on the above results, it can be concluded that U-PHEMA has been successfully synthesized.  \n\n![](images/0f7504affbe80e35e0190893d64f50252ca356da972ba091d60879e6f9f1ad83.jpg)  \nFig. 1. FT-IR spectra of PHEMA (a), HIp (b), and U-PHEMA (c).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3.2. Glass transition temperature of IU-PHEMA  \n\nFig. 3 shows the DSC curves of IU-PHEMA with different AMPS content. It can be observed that AMPS content does not have any effects on the glass transition temperature of IU-PHEMA. It can be explained by that the amount of AMPS is not enough to influence the glass transition temperature.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3.3. Anti-fog test of IU-PHEMA  \n\nTable 3 shows the anti-fog test of UV-cured anti-fog coatings. An overview of Tables 2 and 3 shows that the anti-fog ability of coatings is affected by two major factors. One is the amount of AMPS in IU-PHEMA prepolymers, and the other one is the content of IU-PHEMA in formulas. When the amount of AMPS in IU-PHEMA is above $7\\%$ and the amount of IU-PHEMA in formulas is above $50\\%$ , the coatings exhibit the anti-fog performance. During the UV-curing process, it is likely that the sulfonic groups are trapped in the polymer network, which makes the surface of the film less hydrophilic. Therefore the content of AMPS in prepolymer and the content of prepolymer in formulas have to reach a certain value to ensure sufficient sulfo-group on the surface. Fig. 4 shows the anti-fog tests of formula FA8 on PC plate. It shows that the part with anti-fog coating left keeps good transparency both in anti warm and cold fog tests, which demonstrates the coating prepared by formula FA8 provides the anti-fog performance.  \n\n![](images/f1e31c2ccd858a31063ea6228dfa20ec46a88f063508716eb91c06c2de9db6e7.jpg)  \nFig. 2. $^1\\mathrm{H}$ NMR spectrum of U-PHEMA.  \n\nTable 3 The anti-fog test of UV-cured anti-fog coatings.   \n\n\n<html><body><table><tr><td>Formula</td><td>FA1</td><td>FA2</td><td>FA3</td><td>FA4</td><td>FA5</td><td>FA6</td><td>FA7</td><td>FA8</td><td>FA9</td><td>FA10</td><td>FA11</td></tr><tr><td>Water contact angle</td><td>75</td><td>72</td><td>66</td><td>9.4</td><td>12.4</td><td>54</td><td>59</td><td>11.2</td><td>57</td><td>10.6</td><td>63</td></tr><tr><td>Anti-fog test</td><td>Fogging</td><td>Fogging</td><td>Fogging</td><td>Anti-fog</td><td>Anti-fog</td><td>Fogging</td><td>Fogging</td><td>Anti-fog</td><td>Fogging</td><td>Anti-fog</td><td>Fogging</td></tr></table></body></html>  \n\n![](images/cd93318cc55108f2d60973d609909ec78ee15a0084a5f00e4c10fe8ebe0c54be.jpg)  \nFig. 3. DSC curves of IU-PHEMA with different AMPS content.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.4. Mechanical properties of UV-cured anti-fog coatings  \n\nTable 4 gives the film properties of UV-cured anti-fog coatings. Three different transparent substrates (PMMA, PC and glass) were used in the test. It can be seen that the UV-cured coatings exhibit great adhesion and good resistance on various substrates except glass. Although the hydroxyl groups in the IU-PHEMA prepolymer make formulas interact with substrates surface more easily, the surface of glass is so smooth that few resins show a good adhesion on it. The hardness of the coating is an important factor affecting the abrasion and scratch resistance. Hard coatings give better scratch resistance, and abrasion resistance is also affected by surface friction. From Table 4, it is shown that the pencil and pendulum hardness increased with the increasing amount of reactive diluents. The enhancement in hardness can be attributed from the enhanced crosslinking density of the film, which results in higher reactive diluents content in the UV-curing formula. The above results demonstrate that the UV-curing coating with proper formula provides great coating characteristics.  \n\n![](images/a042b10da482d170dbaac83b1dc5879d674599a12bb30b255fb5899882f11600.jpg)  \nFig. 5. UV–vis spectra of three different plates with and without UV-cured coatings.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3.5. Transparency of UV-cured anti-fog coatings  \n\nTransparency is a key indication for films of anti-fog coatings. Bad transparency limits the film application in optical instruments fields [8]. To evaluate the optical transmission, the UV-cured coatings on various substrates were investigated in the wavelength range of $300{-}800\\mathrm{nm}$ . Fig. 5 shows UV–vis spectra of three different plates with and without UV-cured coatings. For all three substrates, a slight decrease in transmittance with UV-cured coating indicated good transparency of the UV-cured coatings. Besides, the images of the UV-cured coatings on various substrates were also shown in Fig. 6. A clear observation showed that all the prepared UV-cured coatings are totally transparent. Both of the results demonstrate that UV-cured anti-fog coatings with IU-PHEMA have good optical transparency and they can be potential used in transparent optical instruments fields.  \n\n![](images/e0bfa665bba88165b9e718a1ebd93312305b54c8877610d8a6567d45dba4e39b.jpg)  \nFig. 4. Anti-fog tests of formulation FA8 on PC plate. (a) Anti warm fog test and (b) anti cold fog test. The left part of the plate is coated with the anti-fog coating and the right one is without.  \n\nTable 4 The film properties of UV-curing formula of IU-PHEMA.   \n\n\n<html><body><table><tr><td>Formula</td><td>Substrate</td><td>Adhesion/cross-cut</td><td>Pencil hardness</td><td>Pendulum hardness (s)</td><td>Acid resistance</td><td>Alkali resistance</td><td>Ethanol resistance</td><td>Oleic acid resistance</td></tr><tr><td>FA7</td><td>Glass</td><td>２２</td><td>3H</td><td>96</td><td><3 days</td><td><3 days</td><td><3 days</td><td><3 days</td></tr><tr><td>FA6</td><td>Glass</td><td></td><td>3H</td><td>79</td><td><3 days</td><td><3 days</td><td><3 days</td><td><3 days</td></tr><tr><td>FA5</td><td>Glass</td><td>2</td><td>2H</td><td>69</td><td><3 days</td><td><3 days</td><td><3 days</td><td><3 days</td></tr><tr><td></td><td>Glass</td><td>2</td><td>2H</td><td>44</td><td><3 days</td><td><3 days</td><td><3 days</td><td><3 days</td></tr><tr><td>FA4</td><td>PC-plate</td><td>0</td><td>2H</td><td>43</td><td>>10 days</td><td>>10 days</td><td>>10 days</td><td>>10 days</td></tr><tr><td></td><td>PMMA-plate</td><td>0</td><td>2H</td><td>49</td><td>>10 days</td><td>>10 days</td><td>>10 days</td><td>>10 days</td></tr><tr><td>FA8</td><td>PC-plate</td><td>0</td><td>2H</td><td>72</td><td>>10 days</td><td>>10 days</td><td>>10 days</td><td>>10 days</td></tr><tr><td>FA9</td><td>PC-plate</td><td>0</td><td>2H</td><td>83</td><td>>10 days</td><td>>10 days</td><td>>10 days</td><td>>10 days</td></tr><tr><td>FA10</td><td>PC-plate</td><td>0</td><td>2H</td><td>66</td><td>>10 days</td><td>>10 days</td><td>>10 days</td><td>>10 days</td></tr><tr><td>FA11</td><td>PC-plate</td><td>0</td><td>3H</td><td>85</td><td>>10 days</td><td>>10 days</td><td>>10 days</td><td>>10 days</td></tr></table></body></html>  \n\n![](images/9d3b7410a2cc628037807563303a191e3fbde2695b8f8cac7032b047e3c92eea.jpg)  \nFig. 6. The images of three different plates with and without UV-cured coatings. The upper are substrates with UV-cured coating and the lower are clean substrates: (a) glass, (b) PC plate, and (c) PMMA plate.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 4. Conclusion  \n\nIn this article, a new series of UV-curable hydrophilic polyacrylate containing sulfonic groups were synthesized. When the content of AMPS in the prepolymer was over $7\\%$ and the content of prepolymer in the formula was at least $50\\%$ , the UV-cured coatings could achieve anti-fog properties. Also, the formula coated on PC, PMMA and glass plates showed great mechanical properties and good transparency except for bad adhesion on glass plate.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 17,
+        "chunk": "# Acknowledgements  \n\nThis work was supported by the National Nature Science Foundation of Jiangsu Province (No. BK20130153) and the Fundamental Research Funds for the Central Universities (No. JUSRP1021).",
+        "category": " References"
+    },
+    {
+        "id": 18,
+        "chunk": "# References  \n\n[1] L. Maechler, C. Sarra-Bournet, P. Chevallier, N. Gherardi, G. Laroche, Plasma Chem. Plasma Process. 31 (2011) 175–187.   \n[2] H.D. Hwang, C.H. Park, J.I. Moon, H.J. Kim, T. Masubuchi, Prog. Org. Coat. 72 (2011) 663–675.   \n[3] S.J. Dain, A.K. Hoskin, C. Winder, D.P. DingsdagdOphthal, Physiol. Opt. 19 (1999) 357–361.   \n[4] P. Chevallier, S. Turgeon, C. Sarra-Bournet, R. Turcotte, G. Laroche, Appl. Mater. Int. 3 (2011) 750–758.   \n[5] N. Nuraje, R. Asmatulu, R.E. Cohen, M.F. Rubner, Langmuir 27 (2011) 782–791.   \n[6] R. Wang, K. Hashimoto, A. Fujishima, M. Chikuni, E. Kojima, A. Kitamura, M. Shimohigoshi, T. Watanabe, Nature 338 (1997) 431–432.   \n[7] F.C. Cebeci, Z. Wu, L. Zhai, R.E. Cohen, M.F. Rubner, Langmuir 22 (2006) 2856–2862.   \n[8] J.A. Howarter, J.P. Youngblood, Macromol. Rapid Commun. 29 (2008) 455–466.   \n[9] D. Radloff, C. Boeffel, H.W. Spiess, Macromolecules 29 (1996) 1528–1534.   \n[10] Y.K. Lai, Y.X. Tang, J.J. Gong, D.G. Gong, L.F. Chi, C.J. Lin, Z. Chen, J. Mater. Chem. 22 (2012) 7420–7426.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,102 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (12) United States Patent Karunakaran et al.",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (54) ANTIFOG COATING COMPOSITION AND METHODOFMAKINGTHEREOF  \n\n(71）Applicants:Raghuraman Govindan Karunakaran, Bangalore (IN); Indumathi Ramakrishnan, Bangalore (IN); Andreas Haeuseler, Nordhein-Westfalen (DE); Keith J. Weller, Rensselaer, NY (US)  \n\n(72) Inventors: Raghuraman Govindan Karunakaran, Bangalore (IN); Indumathi Ramakrishnan, Bangalore (IN); Andreas Haeuseler, Nordhein-Westfalen (DE); Keith J. Weller, Rensselaer, NY (US)  \n\n(73） Assignee: MOMENTIVE PERFORMANCEMATERIALS INC., Waterford, NY(US)  \n\n(\\*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 609 days.  \n\n(21)Appl.No.: 14/995,417 (22) Filed: Jan. 14, 2016",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# Prior Publication Data  \n\nUS 2017/0204313A1 Jul.20,2017  \n\n(51) Int. Cl. C08K 3/18 (2006.01) C09D 133/12 (2006.01) C09K 3/18 (2006.01) C09D 4/06 (2006.01)   \n(52) U.S. Cl. CPC C09K 3/18 (2013.01); C09D 4/06 (2013.01); C09D 133/12 (2013.01)  \n\n(10) Patent No.: US 10,377,933 B2   \n(45) Date of Patent: Aug.13, 2019  \n\n(58) Field of Classification Search CPC C09K 3/18; C09D 133/12 USPC 524/284 See application file for complete search history.",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# References Cited",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# U.S. PATENT DOCUMENTS  \n\n5,180,760 A 1/1993 Oshibe 5,244,935A 9/1993 Oshibe 8,106,124 B2 1/2012 Ougitani 2003/0203991 A1\\* 10/2003 Schottman C08K3/22 523/334 2005/0074557 A1\\* 4/2005 Patchen C09K3/18 427/421.1 2010/0304150 A1\\* 12/2010 Zheng C09D 183/06 428/414 2013/0308189 A1 11/2013 Gloege",
+        "category": " References"
+    },
+    {
+        "id": 6,
+        "chunk": "# FOREIGNPATENTDOCUMENTS  \n\nEP 1845141 10/2007   \nJP 2004-182914 7/2004",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# OTHERPUBLICATIONS  \n\nInternational Searching Authority European Patent Office, International Search Report and Writte Opinion for International Application No. PCT/US2016/067113, dated Jul. 17,2017.  \n\n\\* cited by examiner   \nPrimary Examiner—Deve E Valdez   \n(74)Attorney, Agent, or Firm—McDonald Hopkins   \nLLC; James Abruzzo",
+        "category": " References"
+    },
+    {
+        "id": 8,
+        "chunk": "# ABSTRACT  \n\nThe present technology relates to an antifog coating composition comprising a matrix, a hydrophilic compound, and a surfactant. The antifog coating composition may further comprise a thermal or a photo-initiator. The antifog coating composition may be applied to a polycarbonate substrate.  \n\n19 Claims, No Drawings",
+        "category": " Abstract"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# 1 ANTIFOGCOATINGCOMPOSITIONAND METHODOFMAKINGTHEREOF  \n\ning from 1 to 3 carbon atoms; a methacrylate, and an acrylate group; wherein a is an integer from O to 1;  \n\n$\\mathrm{R}_{2}$ is independently chosen from $\\mathrm{H}$ or $\\mathrm{CH}_{3}$ ▪  \n\nFIELD  \n\nThe present technology relates to an antifog coating composition, methods of making an antifog coating composition, and articles comprising antifog coatings formed from such compositions. In particular, the present technology relates to an antifog coating composition comprising a matrix, a hydrophilic component, and a surfactant. The antifog coating composition may further comprise a thermal or a photo-initiator. The antifog coating compositions may be applied to a substrate, such as a plastic substrate, to coat the substrate.The coatings exhibit good adhesion and excellent antifog properties.  \n\nFogging occurs when the surface temperature of a material is lower than the dew point of water vapor, resulting in condensation of the water vapor on the material. Fogging of automobile headlights, windshields, mirrors, eyeglasses, swimming goggles, camera lens, etc., can be problematic.  \n\nCurrent antifog coatings are normally prepared by physically introducing hydrophilic moieties into a polymer matrix without any chemical bond formation. A simple process such as melt blending produces antifog surfaces, however, the hydrophilic moieties may wear off during cleaning of the coating and stable long-term application cannot be assured. Thus, there remains a need for robust, long-life, antifog coatings.  \n\nThe present technology provides, in one aspect, an antifog coating composition comprising at least one thermoplastic matrix or polymer matrix, at least one hydrophilic component, and at least one surfactant. The antifog coating composition can be applied to a substrate to prevent fogging. In an embodiment, the antifog coating composition further comprises a thermal initiator or a photo-initiator.  \n\n${\\mathrm{R}}_{3}$ is independently selected from the group consisting of 5 H, an alkyl group having from 1 to 6 carbon atoms, a hydroxy group, an alkoxy group having from 1 to 3 carbon atoms, a methacrylate, and an acrylate group;",
+        "category": " Introduction"
+    },
+    {
+        "id": 11,
+        "chunk": "# SUMMARY  \n\nA is independently selected from the group consisting of O, a substituted or unsubstituted linear alkyl group having   \n10 from 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted divalent aromatic group having from 6 to 20 carbon atoms, an alkylene oxide, and a   \n158 substituted or unsubstituted divalent heterocyclic group having from 5 to 20 carbon atoms;  \n\nIn one embodiment, the matrix is an acrylate matrix. In one embodiment, the thermoplastic matrix comprises poly (methylmethacrylate) (PMMA） or polycarbonate (PC), polyether ether ketone (PEEK), polyimide (PI) or a combination thereof.  \n\n$\\mathbf{A^{\\prime}}$ is independently selected from H, a substituted or unsubstituted linear alkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group hav:o ing from 1 to 20 carbon atoms, a substituted or unsubstituted divalent aromatic group having from 6 to 20 carbon atoms, a substituted or unsubstituted divalent heterocyclic group having from 5 to 20 carbon atoms, a methacrylate, and an acrylate group;  \n\n:5B is independently selected from O, a substituted or unsubstituted linear alkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted divalent aromatic group having from 6 to 20 carbon atoms, 0 a substituted or unsubstituted divalent heterocyclic group having from 5 to 20 carbon atoms, and a bisphenol A unit; wherein e is an integer from 0 to 1;",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# BACKGROUND  \n\nwherein n is an integer from 1 to 5 and m is an integer from 0 to 5.  \n\nIn one embodiment, the hydrophilic mono- or multifunctional acrylate is selected from a poly(ethyleneoxy)methacrylate, a poly(ethyleneoxy)acrylate, a poly(ethyleneoxy) monomethylether acrylate,apoly(ethyleneoxy) monomethylether methacrylate, a pentaerythritol triacrylate, a glycerol dimethacrylate, a glycerol diacrylate, a bisphenolA-glycerol tetraacrylate, a bisphenol-A-glycerol diacrylate, a bisphenol-A-ethyleneoxy diacrylate, or a combination of two or more thereof.  \n\nIn one embodiment, the hydrophilic compound is a hydro philic epoxy compound comprising the formula (II):  \n\nIn one embodiment, the hydrophilic compound is a hydro- 50 philic mono- or multifunctional acrylate comprises the formula (I):  \n\n55  \n\n![](images/bfebaec6aac200b41582674b8620014f15f47f9976cf225f8d625be0e93f674a.jpg)  \n\n![](images/dc28c8fc246133b2edc90f7d68ff330bf5c7745f9ece8b68d1fe5e7f67e1b2e4.jpg)  \n\nwherein:  \n\n$\\mathrm{R}_{1}$ is independently selected from the group consisting of O; H; a linear alkyl group containing from 1 to 5 carbon atoms; a linear alkyl group containing from 1 to 5 carbon atoms substituted with a hydroxy or an alkoxy group; an aromatic group; a hydroxy group; an alkoxy group contain  \n\nwherein:  \n\n$\\mathrm{R}_{4;\\l}$ $\\mathrm{R}_{5}$ ，and ${\\mathrm{R}}_{6}$ are independently chosen from H, a linear alkyl group having from 1 to 5 carbon atoms, an aromatic   \n60 group, a hydroxy group, or an alkoxy group having from 1 to 3 carbon atoms; Q is independently chosen from a linear alkylene group having from 1 to 6 carbon atoms, a cycloalkylene group having from 6 to 10 carbon atoms, a divalent aromatic group   \n65 having 6 to 20 carbon atoms, or a divalent heterocyclic group having from 5 to 20 carbon atoms; and wherein $\\mathfrak{p}$ is an integer from O to 5.  \n\nIn one embodiment, the hydrophilic epoxy compound is a bisphenol-A substituted epoxy group.  \n\nIn one embodiment, the thermoplastic matrix is an acrylate matrix.  \n\nIn one embodiment, the thermoplastic matrix may be chosen from polyether esters, polyester esters, thermoplastic polyurethanes (TPU), styrene ethylene butadiene styrene (SEBS), acrylonitrile butadiene styrene (ABS), styrene acrylonitrile (SAN), polyamide (PA), acrylate styrene acrylate block copolymer (ASA), polybutylene terephthalate (PBT), polycarbonate (PC), polyether block amide (PEBA), polyalkyl methacrylates and acrylates, including polymethyl methacrylate (PMMA), polyoxymethylene (POM), polyvinylchloride (PVC), polyether ether ketone (PEEK), polyimide (PI), or a combination of two or more thereof.  \n\nIn one embodiment, the surfactant is a non-ionic surfactant. In one embodiment, the non-ionic surfactant is selected from a fatty alcohol, cetyl alcohol, stearyl alcohol, cetostearyl alcohol, oleyl alcohol, or a combination of two or more thereof.  \n\nIn one embodiment, the surfactant is selected from sorbitan esters; polyethoxylated sorbitan esters; oleochemical derivative (e.g, Finafog PET (tradename), from Fine Organics); PEG monolaurate; polyethylene glycol octadecyl ether (e.g.,BRIJ $\\textsuperscript{\\textregistered}$ O20, from Sigma Aldrich); polyoxyethylene stearyl ether; polyoxyethylene nonylphenyl ether, branched (e.g, Igepal $\\textsuperscript{\\textregistered}$ CO 720, from Sigma Aldrich); poly(oxyethylene) tridecyl ether; PEG-20 sorbitan monolaurate (e.g, Tween? 20, from Sigma Aldrich); PEG-20 sorbitan monolearate (e.g， Tween $\\textsuperscript{\\textregistered}$ 80, from Sigma Aldrich); sorbitan monostearate (e.g., Span $\\textsuperscript{\\textregistered}$ 60, from Sigma Aldrich), methacrylate Tween? 20 (from Sigma Aldrich), $\\mathrm{SiO}_{2}$ -Tween $\\textsuperscript{\\textregistered}$ 20 (from Sigma Aldrich), Grand 6047 (from Momentive), Ecosure EH-9 (from Dow Chemicals),Mecostat $\\textsuperscript{\\textregistered}$ 3/752 (from Mecastat), Mecostat $^\\mathrm{\\textregistered}$ 3/749 (from Mecostat) or a combination of two or more thereof. In one embodiment, the surfactant is a suitable sorbitan ester. Suitable sorbitan esters include, but are not limited to Tweens (e.g., Tween $\\textsuperscript{\\textregistered}$ 20, Tween $\\textsuperscript{\\textregistered}$ 80, methacrylate Tween $\\textsuperscript{\\textregistered}$ 20, and $\\mathrm{SiO}_{2}$ -Tween $\\textsuperscript{\\textregistered}$ 20 all are from Sigma Aldrich) and Spans (e.g., Span $\\textsuperscript{\\textregistered}$ 60).  \n\nIn one embodiment, the surfactant is selected from a sorbitan ester, a polyethoxylated sorbitan ester, a polyoxyethylene glycol alkyl ether; a polyoxypropylene glycol alkyl ether; a glucoside alkyl ether; a polyoxyethylene glycol octylphenol ether; a polyoxyethylene glycol alkylphenol ether; a polyoxyethylene glycol sorbitan alkyl ester; a sorbitan alkyl ester; or a combination of two or more thereof.  \n\nIn one embodiment, the surfactant is selected from an oleochemical derivative (e.g.， Finafog PET), PEG monooleate, PEG monolaurate, polyethylene glycol octadecyl ether (e.g., BRIJ $\\textsuperscript{\\textregistered}$ 020),polyoxyethylene nonylphenyl ether, branched (e.g., Ipegal $\\textsuperscript{\\textregistered}$ CO 720, poly(oxyethylene) tridecyl ether; PEG-20 sorbitan monolaurate (e.g., Tween $\\textsuperscript{\\textregistered}$ 20); PEG-20 sorbitan monolearate (e.g., Tween $\\textsuperscript{\\textregistered}$ 80); sorbitan monostearate (e.g., Span $\\textsuperscript{\\textregistered}$ 60), Methacrylate Tween $\\textsuperscript{\\textregistered}$ 20, $\\mathrm{SiO}_{2}$ -Tween? 20, or a combination of two or more thereof.  \n\nIn one aspect of the invention, the antifog coating composition comprises a polymer matrix,a hydrophilic compound, a surfactant, and a photo-initiator or a thermal initiator. In one embodiment, the thermal initiator comprises benzoyl peroxide or $^{4,4^{\\prime}}$ -azobisisobutyronitrile (AIBN). In another embodiment, the photo-initiator comprises bis(2,4, 6-trimethylbenzoyl)-phenylphosphineoxide (Irgacure $\\textsuperscript{\\textregistered}$ 819, from BASF); 1-Hydroxycyclohexyl phenyl ketone (Irgacure $\\textsuperscript{\\textregistered}$ 184, from BASF); or a combination of two or more thereof.  \n\nIn one aspect of the invention, the antifog coating composition comprises about 10-70 wt $\\%$ PMMA, about 10-40 wt $\\%$ glycerol dimethacrylate, about 10-40 wt $\\%$ of a surfactant, and about 2-5 wt $\\%$ 1-Hydroxycyclohexyl phenyl ketone (Irgacure $\\textsuperscript{\\textregistered}$ 184, from BASF).  \n\nIn another aspect of the invention, the antifog composition comprises a coating formulation comprising about 40-65 wt $\\%$ PMMA, about 15-20 wt $\\%$ glycerol dimethacrylate, about 15-20 wt $\\%$ of a surfactant, and about 2-5 wt 1-Hydroxycyclohexyl phenyl ketone (Irgacure $\\textsuperscript{\\textregistered}$ 184, from BASF).  \n\nIn one embodiment of the invention, the matrix includes poly(methylmethacrylate)(PMMA); the hydrophilic monoor multifunctional component is selected from poly(ethyl  \n15 eneoxy)methacrylate, poly(ethyleneoxy)-acrylate, poly(ethyleneoxy)monomethylether acrylate, poly(ethyleneoxy)- monomethylether methacrylate, pentaerythritol triacrylate, glycerol dimethacrylate, glycerol diacrylate, bisphenol-Aglycerol tetraacrylate, bisphenol-A-glycerol diacrylate, bis  \n20 phenol-A-ethyleneoxy diacrylate, or combination of two or more thereof; and a surfactant chosen from an oleochemical derivative (e.g., Finafog PET), poly(ethyleneglycol) monolaurate, poly(ethyleneglycol) monooleate, poly(ethyleneglycol) sorbitan monolaurate (e.g., Tween 20), poly(oxyethyl  \n25 ene) (10) tridecyl ether, polyethylene glycol octadecyl ether (e.g.， BRIJ $\\textsuperscript{\\textregistered}$ 20, polyoxyethylene nonylphenyl ether, branched (e.g., Igepal $\\textsuperscript{\\textregistered}$ 720, sorbitan monostearate (Span $\\textsuperscript{\\textregistered}$ 60)，Grand 6047， Ecosure EH-9， Mecostat? 3/752, Mecostat? 3/749 or a combination of two or more thereof.   \n30 In one aspect of the invention, the antifog compositions comprises a hydrophilic mono- or multifunctional acrylate such as poly(ethyleneoxy)methacrylate, poly(ethyleneoxy) acrylate, poly(ethyleneoxy)-monomethylether acrylate, poly (ethyleneoxy)monomethylether methacrylate, pentaerythri  \n35 tol triacrylate, glycerol dimethacrylate, glycerol diacrylate, bisphenol-A-glycerol tetraacrylate, bisphenol-A-glycerol diacrylate, bisphenol-A-ethyleneoxy diacrylate, or a combination of two or more thereof added onto the matrix comprising a thermoplastic (e.g., PMMA) and at least one   \n40 surfactant selected from, an oleochemical derivative (e.g., Finafog PET), poly(ethyleneglycol) monolaurate, poly(ethyleneglycol) monooleate, poly(ethyleneglycol) sorbitan monolaurate (e.g., Tween $\\textsuperscript{\\textregistered}$ 20), poly(oxyethylene) (10) tridecyl ether, polyethylene glycol octadecyl ether (e.g.,   \n45 BRIJ $\\textsuperscript{\\textregistered}$ 20), polyoxyethylene nonylphenyl ether, branched (e.g., Igepal $\\textsuperscript{\\textregistered}$ 720), Grand 6047, Ecosure EH-9, Mecostat $\\textsuperscript{\\textregistered}$ 3/752, Mecostat? 3/749, sorbitan stearate (e.g., Span? 60), or a combination of two or more thereof. In one aspect, the present technology provides a substrate   \n50 where at least a portion of a surface thereof is coated with an antifog composition in accordance with any of the foregoing aspects or embodiments. In embodiments, the substrate is chosen from an acrylic polymer, a polyamide, a polyimide, an acrylonitrile-styrene copolymer, a styrene  \n55 acrylonitrile-butadiene terpolymer, a polyvinyl chloride, a polyethylene, a polycarbonate, a copolycarbonate, a highheat polycarbonate, or a combination of two or more thereof.  \n\nThese and other aspects and embodiments are further understood with reference to the following detailed descrip tion.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# DETAILEDDESCRIPTION  \n\nThe present invention provides an antifog coating composition. In one aspect of the invention, the antifog composition comprises at least one polymer matrix, at least one hydrophilic component, and at least one surfactant. In one embodiment, the present invention further includes a thermal or a photo-initiator. In accordance with the present technology, the hydrophilic component is cross-linked into the polymer matrix upon curing the matrix. The coating provides good adhesion to a substrate along with excellent antifog properties. In particular, it has been found that incorporating a hydrophilic acrylate into the composition and polymer matrix provides a composition and coating exhibiting excellent antifog properties as well as other desired coating properties.  \n\nThe polymer matrix may be chosen from suitable polymer materials including, but not limited to, thermoplastic elastomers, such as for example polyether esters, polyester esters, thermoplastic polyurethanes (TPU), styrene ethylene butadiene styrene (SEBS), acrylonitrile butadiene styrene (ABS), styrene acrylonitrile (SAN), polyamide (PA), acrylate styrene acrylate block copolymer (ASA), polybutylene terephthalate (PBT), polycarbonate (PC), polyether block amide (PEBA), polyalkyl methacrylates and acrylates, polyoxymethylene (POM), polyvinylchloride (PVC), polyether ether ketone (PEEK), polyimide (PI) or a combination of two or more thereof. Particularly suitable matrices include PMMA or PC.  \n\nIn one embodiment, the matrix comprises at least about 45 wt $\\%$ , in another embodiment at least about $50\\mathrm{wt\\%}$ , in yet another embodiment at least about 55 wt $\\%$ ，in still yet another embodiment about at least about $60\\mathrm{\\textrm{wt}\\%}$ ，in a further embodiment at least about 65 wt $\\%$ ，or in another further embodiment at least about 70 wt $\\%$ of the total weight of the antifog composition.  \n\nIn one embodiment, the matrix comprises from about 45 wt $\\%$ to about $70\\mathrm{wt}\\%$ ，from about $45\\mathrm{wt\\%}$ to about 65 wt $\\%$ ,from about 45 wt $\\%$ to about $60\\mathrm{wt\\%}$ ，or from about 45 wt $\\%$ to about 55 wt $\\%$ of the composition. In another embodiment the matrix comprises from about $50\\mathrm{\\mt\\\\%}$ to about $70\\mathrm{wt\\%}$ ,or in yet another embodiment from about 50 wt $\\%$ to about 65 wt $\\%$ of the composition.  \n\nIn one embodiment, the matrix comprises less than about $70\\mathrm{wt}\\%$ of the antifog composition, in another embodiment less than about $65\\mathrm{wt\\%}$ and in yet another embodiment less than about $60\\mathrm{wt\\%}$ of the antifog composition. In particular, it has been found that the adhesion to a substrate is improved when the polymer matrix material is at least about $50\\mathrm{wt\\%}$ Here as elsewhere in the specification and claims, numerical values can be combined to form new and non-disclosed ranges.  \n\nIn one aspect, the hydrophilic component of the antifog composition includes at least one hydrophilic acrylate. In one embodiment, the hydrophilic acrylate may be chosen from a compound of the formula (I):  \n\n![](images/dd6c70c922b7a248a99c384bf929e23ed0ce7878dde2343f69e1048442913c94.jpg)  \n\nwherein:  \n\n$\\mathrm{R}_{1}$ is independently selected from the group consisting of O; H; a linear alkyl group containing from 1 to 5 carbon atoms; a linear alkyl group containing from 1 to 5 carbon atoms substituted with a hydroxy or an alkoxy group; an aromatic group; a hydroxy group; an alkoxy group containing from 1 to 3 carbon atoms; a methacrylate, and an acrylate group; wherein a is an integer from O to 1;  \n\n$\\mathrm{R}_{2}$ is independently chosen from H or $\\mathrm{CH}_{3}$ ▪  \n\n${\\mathrm{R}}_{3}$ is independently selected from the group consisting of 5 H, an alkyl group having from 1 to 6 carbon atoms, a hydroxy group, an alkoxy group having from 1 to 3 carbon atoms, a methacrylate, and an acrylate group;  \n\nA is independently selected from the group consisting of O, a substituted or unsubstituted linear alkyl group having 10 from 1 to 2O carbon atoms, a substituted or unsubstituted cycloalkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted divalent aromatic group having from 6 to 20 carbon atoms, an alkylene oxide, and a substituted or unsubstituted divalent heterocyclic group hav15 ing from 5 to 20 carbon atoms;  \n\nA' is independently selected from H, a substituted or unsubstituted linear alkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted 0 divalent aromatic group having from 6 to 20 carbon atoms, a substituted or unsubstituted divalent heterocyclic group having from 5 to 20 carbon atoms, a methacrylate, and an acrylate group;  \n\nB is independently selected from O, a substituted or   \n25 unsubstituted linear alkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted divalent aromatic group having from 6 to 20 carbon atoms, a substituted or unsubstituted divalent heterocyclic group   \n30 having from 5 to 20 carbon atoms, and a bisphenol A unit; wherein e is an integer from O to 1;  \n\nwherein n is an integer from 1 to 5 and m is an integer from 0 to 5.  \n\nIn one embodiment, A may be a divalent hydrocarbon 35 radical or may be an oxygen atom. The divalent hydrocarbon radical may be a substituted or unsubstituted aliphatic, cyclic, or aromatic containing radical. The divalent hydrocarbon radical may be an alkylene, cycloalkylene, alkenylene, or an arylene.  \n\n40 As used herein, the terms “alkylene\",“cycloalkylene\", \"alkylene\",“alkenylene\", and “arylene” alone or as part of another substituent refers to a divalent radical derived from an alkyl, cycloalkyl, heteroalkyl, alkynyl, alkenyl, or aryl group, respectively. The respective radicals can be substi  \n45 tuted or unsubstituted, linear or branched.  \n\nIn embodiments, A is chosen from an oxygen atom, an alkylene (a divalent radical) group having 1 to 10 carbon atoms; an alkylene group having 2 to 8 carbon atoms; or an alkylene group having 4 to 6 carbon atoms. In embodiments, :0 A is an alkylene group having 1 to 4 carbon atoms. In embodiments, A is methylene. In one embodiment, A is a divalent aryl radical having 6 to 30 carbon atoms. In embodiments, A is a phenyl radical, a tolyl radical, a xylyl radical, etc.  \n\n55 In one embodiment, A is a divalent heterocyclic group (having 5 to 20 carbon atoms). As used herein, the term \"heterocyclic\" refers to a cyclic compound that has atoms of at least two different elements as members of its ring(s) (e.g.. carbon and oxygen). In one embodiment, the compound   \n60 includes carbon and at least one heteroatom selected from nitrogen, oxygen, sulfur, phosphorus, or a combination of two or more thereof.  \n\nIn one embodiment, the hydrophilic mono- or multifunctional acrylate is selected from a poly(ethyleneoxy)methacrylate, a poly(ethyleneoxy)acrylate, a poly(ethyleneoxy) monomethylether acrylate, a poly(ethyleneoxy) monomethylether methacrylate, a pentaerythritol triacrylate,",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 14,
+        "chunk": "# 7  \n\na glycerol dimethacrylate, a glycerol diacrylate, a bisphenolA-glycerol tetraacrylate, a bisphenol-A-glycerol diacrylate, a bisphenol-A-ethyleneoxy diacrylate, or a combination of two or more thereof.  \n\nExemplary hydrophilic acrylates are shown below in for- 5 mulae (I)(a)-I(j).  \n\n![](images/fd6110e6ef17fa59ee245dbad307ebe853da338ec20ad4ac5654c92f35d3d7fe.jpg)  \n\n![](images/6cabc6bb5f7b8637aea096dd2a66edd2407d51f716309be6a1b7423648b6103b.jpg)  \n\nIn one aspect, the hydrophilic component of the antifog composition includes at least one hydrophilic epoxy com- 65 pound. In one embodiment, the hydrophilic epoxy compound may be chosen from a compound of the formula (II):",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# 10  \n\n![](images/4806e2f817e0c4d3a04709e825ae065c74aa414598a201458b76305424f2b9ce.jpg)  \n\nwherein:  \n\n$\\mathrm{R}_{4}$ ， ${\\mathrm{R}}_{5}$ ，and $\\mathrm{R}_{6}$ are independently chosen from H, a linear alkyl group having from 1 to 5 carbon atoms, an aromatic group, a hydroxy group, or an alkoxy group having from 1 to 3 carbon atoms;  \n\nQ is independently chosen from a linear alkylene group having from 1 to 6 carbon atoms, a cycloalkylene group having from 6 to 10 carbon atoms, a divalent aromatic group having 6 to 20 carbon atoms, or a divalent heterocyclic group having from 5 to 20 carbon atoms; and wherein $\\mathfrak{p}$ is an integer from 0 to 5.  \n\nIn one embodiment, the hydrophilic epoxy compound is a bisphenol-A substituted epoxy groups of following formula (II)(a):  \n\nlearate (e.g, Tween? 80, from Sigma Aldrich); sorbitan monostearate (e.g., Span? 60, from Sigma Aldrich), methacrylate Tween $\\textsuperscript{\\textregistered}$ 20 (from Sigma Aldrich), $\\mathrm{SiO}_{2}$ -Tween $\\textsuperscript{\\textregistered}$ 20 (from Sigma Aldrich), Grand 6047 (from Momentive),   \n5 Ecosure EH-9 (from Dow Chemicals),Mecostat? 3/752 (from Mecastat), Mecostat? 3/749 (from Mecostat) or a combination of two or more thereof. In one embodiment, the surfactant is a suitable sorbitan ester. Suitable sorbitan esters include, but are not limited to Tweens (e.g., Tween? 20.   \n10 Tween $\\mathbb{R}$ 80, methacrylate Tween $\\textsuperscript{\\textregistered}$ 20, and $\\mathrm{SiO}_{2}$ -Tween?20 all are from Sigma Aldrich) and Spans (e.g., Span $\\textsuperscript{\\textregistered}$ 60). In one embodiment, the surfactant is chosen from an oleochemicalderivative(e.g， Finafog PET)， PEG   \n15 monooleate, PEG monolaurate, polyethylene glycol octadecyl ether (e.g., BRIJ? 020), polyoxyethylene nonylphenyl ether, branched (e.g, Ipegal $\\textsuperscript{\\textregistered}$ CO 720, poly(oxyethylene) tridecyl ether; PEG-20 sorbitan monolaurate (e.g, Tween $\\textsuperscript{\\textregistered}$ 20); PEG-20 sorbitan monolearate (e.g,Tween $\\textsuperscript{\\textregistered}$ 80; sorbi  \n20 tan monostearate (e.g., Span $\\textsuperscript{\\textregistered}$ 60), Methacrylate Tween $\\textsuperscript{\\textregistered}$ 20, $\\mathrm{SiO}_{2}$ -Tween $\\textsuperscript{\\textregistered}$ 20, or a combination of two or more thereof.  \n\nIn one embodiment the surfactant is chosen from:  \n\n![](images/e7e09ce11af929111374a90ce4f2251a7f445dcc7b0db4d6b2809a1470a6ca75.jpg)  \n35  \n\nwherein $\\scriptstyle\\mathrm{n=0}$ to3  \n\nIn one embodiment, the hydrophilic component is present in an amount of from about $15\\mathrm{~wt~\\%~}$ to about $30\\mathrm{\\wt\\\\%}$ ,in another embodiment from about $20\\mathrm{wt\\%}$ to about 30 wt $\\%$ ， in yet another embodiment from about 25 wt $\\%$ to about 30 wt $\\%$ ; in still yet another embodiment from about $15\\mathrm{\\wt\\\\%}$ to about $25\\mathrm{wt}\\%$ ，or in a further embodiment from about 20 wt $\\%$ to about 25 wt $\\%$ based on the total weight of the antifog composition.  \n\nIn one aspect of the invention, the antifog composition includes a surfactant. Suitable surfactants include, but are not limited to, non-ionic surfactants. Examples of suitable non-ionic surfactants include sorbitan esters, polyethoxylated sorbitan esters, polyoxyethylene glycol alkyl ethers; 50 polyoxypropylene glycol alkyl ethers; glucoside alkyl ethers; polyoxyethylene glycol octylphenol ethers; polyoxyethylene glycol alkylphenol ethers; polyoxyethylene glycol sorbitan alkyl esters; sorbitan alkyl esters; or a combination of two or more thereof. 55  \n\nIn one embodiment, the surfactant is chosen from a fatty alcohol, cetyl alcohol, stearyl alcohol, cetostearyl alcohol, oleyl alcohol or a combination of two or more thereof.  \n\nIn one embodiment, the surfactant is selected from sorbitan esters; polyethoxylated sorbitan esters; oleochemical 60 derivative (e.g, Finafog PET (tradename), from Fine Organics); PEG monolaurate; polyethylene glycol octadecyl ether (e.g.,BRIJ $\\textsuperscript{\\textregistered}$ O20, from Sigma Aldrich); polyoxyethylene stearyl ether; polyoxyethylene nonylphenyl ether, branched (e.g, Igepal $\\textsuperscript{\\textregistered}$ CO 720, from Sigma Aldrich); poly(oxyeth- 65 ylene) tridecyl ether; PEG-20 sorbitan monolaurate (e.g, Tween $\\textsuperscript{\\textregistered}$ 20, from Sigma Aldrich); PEG-20 sorbitan mono  \n\n![](images/e2d4919fbd9ae67155b3bec2f3f1352841b8f58893f10d1a80e22247cae9dccb.jpg)  \n\n![](images/6abde19fc1a1ee1c94da7d39c5f6b098807ea480b975307e3f132ffbd74df660.jpg)  \n\nor a combination of two or more thereof.  \n\nIn one embodiment, the surfactant is present in an amount of from about $10\\ \\mathrm{\\mt}\\ \\%$ to about 40 wt $\\%$ ，in another embodiment from about 15 wt $\\%$ to about 30 wt $\\%$ , in yet another embodiment from about $20\\mathrm{wt\\%}$ to about $30\\mathrm{\\wt\\\\%}$ D and in still yet another embodiment from about $25\\mathrm{\\wt\\\\%}$ to about 30 wt $\\%$ ; and in a further embodiment from about 15 wt $\\%$ to about $25\\mathrm{\\wt\\\\%}$ ，or in another further embodiment from about $20\\mathrm{wt\\%}$ to about $25\\mathrm{\\wt\\\\%}$ based on total weight of the antifog composition.  \n\nIn one aspect of the invention, the antifog composition may include a photo-initiator. A photo-initiator can initiate free radical polymerization and/or cross-linking by the use of light. Suitable photo-initiators include, but are not limited 3. to, benzoin methyl ether, diethoxyacetophenone, benzoylphosphine oxide, 2-hydroxy-2-methyl propiophenone (HMPP), 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy2-methyl-1-phenyl-propan-l-one (trade name: darocur 1173, from BASF), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hy- 4 droxy-2-methyl-1-propane-l-one (trade name: Darocur 2959 from BASF) and 1-Hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184 from BASF). Examples of benzoylphosphine initiators include 2,4,6-trimethylbenzoyldiphenylophosphine oxide; bis-(2,6-dichlorobenzoyl)-4-N- 4. propylphenylphosphine oxide; and bis-(2,6- dichlorobenzoyl)-4-N-butylphenylphosphine oxide. Reactive photo-initiators that can be incorporated, for example, into a macromer or can be used as a special monomer are also suitable. Examples of reactive photo- 5 initiators include those disclosed in EP 632329,which is herein incorporated by reference in its entirety. The polymerization can then be triggered off by actinic radiation, for example light, in particular UV light of a suitable wavelength. The spectral requirements can be controlled accord- 5 ingly, if appropriate, by addition of suitable photosensitizers.  \n\nIn one embodiment, the photo-initiator is 1-hydroxycyclohexyl phenyl ketone (Irgacure $\\textsuperscript{\\textregistered}$ 184, from BASF), bis (2,4,6-trimethylbenzoyl)-phenylphosphineoxide (Irgacure $\\textsuperscript{\\textregistered}$ 819, from BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1- one (Darocur $\\textsuperscript{\\textregistered}$ 1173, from BASF),2,2-dimethoxy-1,2-diphenylethan-l-one (Irgacure $\\textsuperscript{\\textregistered}$ 651,from BASF),2,4, 6-trimethylbenzoylphenyl phosphinate (Lucirin $\\mathbb{R}$ TPO-L, from BASF), (Lucirin $\\textsuperscript{\\textregistered}$ TPO-S from BASF), combination of two. In one embodiment, the thermal intiator is benzoyl peroxide (BPO）or $^{4,4^{\\prime}}$ -azobisisobutyronitrile （AIBN）or combination of these two.  \n\nIn one aspect of the invention, the antifog composition may include a thermal initiator. A thermal initiator can initiate free radical polymerization and/or cross-linking by the use of heat. Suitable thermal initiators include, but are   \n5 not limited to tert-amyl peroxybenzoate; 4,4-azobis(4-cyanovaleric acid); 1,l'-azobis(cyclohexanecarbonitrile); 2,2'- azobisisobutyronitrile (AIBN); benzoyl peroxide (BPO);   \n2,2-bis(tert-butylperoxy)butane;1,1-bis(tert-butylperoxy) cyclohexane; 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane;   \n10 2,5-bis(tert-Butylperoxy)-2,5-dimethyl-3-hexyne; bis(1- (tert-butylperoxy)-1-methylethyl)benzene; 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane; tert-butyl hydroperoxide; tert-butyl peracetate; tert-butyl peroxide; tert-butyl peroxybenzoate; tert-butylperoxy isopropyl carbonate;   \n15 cumene hydroperoxide; cyclohexanone peroxide; dicumyl peroxide; lauroyl peroxide; 2,4-pentanedione peroxide; peracetic acid; potassium persulfate.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 16,
+        "chunk": "# 12  \n\nIn one embodiment, the thermal initiator is benzoyl peroxide (BPO) or $^{4,4^{\\prime}}$ -azobisisobutyronitrile (AIBN） or combination of these two.  \n\nIn one embodiment, the photo-initiator is present in an amount of from about $1\\mathrm{\\mt\\%}$ to about 6 wt $\\%$ or in another embodiment from about 2 wt $\\%$ to about 4 wt $\\%$ ，basedon total weight of the antifog composition.  \n\nIn one embodiment, the antifog composition comprises a coating formulation comprising from about $10\\mathrm{wt}\\%$ to about 70 wt $\\%$ thermoplastic matrix; from about $10\\mathrm{wt}\\%$ to about $40\\mathrm{wt}\\%$ hydrophilic mono or multifunctional acrylates; and from about $10\\mathrm{wt}\\%$ to about $40\\upnu\\upnu\\%$ surfactant, based on total weight of the antifog composition. In one embodiment, the coating formation further includes about $1\\mathrm{\\mt\\%}$ to about $5\\mathrm{\\wt\\\\%}$ of a thermal or a photo-initiator.  \n\nIn one embodiment of the invention, the matrix includes poly(methylmethacrylate)(PMMA); the hydrophilic component is chosen from glycerol dimethacrylate, bisphenol A glycerolate diacrylate, bisphenol A ethoxylate diacrylate, or a combination of two or more thereof; and a surfactant chosen from an oleochemical derivative (e.g, Finafog PET), poly(ethyleneglycol)monolaurate, poly(ethyleneglycol) monooleate, poly(ethyleneglycol) sorbitan monolaurate (e.g., Tween 20), poly(oxyethylene) (10) tridecyl ether, polyethylene glycol octadecyl ether (e.g., BRIJ? 20), polyoxyethylene nonylphenyl ether, branched (e.g, Igepal $\\textsuperscript{\\textregistered}$ 720), Sorbitan stearate (e.g., Span $\\textsuperscript{\\textregistered}$ 60), or a combination of two or more thereof.  \n\nIn one aspect of the invention, the antifog compositions comprises a hydrophilic acrylate such as poly(ethyleneoxy) methacrylate, poly(ethyleneoxy)acrylate, poly(ethyleneoxy) monomethylether acrylate, poly(ethyleneoxy)monomethy  \n50 lether methacrylate, pentaerythritol triacrylate, glycerol dimethacrylate, glycerol diacrylate, bisphenol-A-glycerol tetraacrylate, bisphenol-A-glycerol diacrylate, bisphenol-Aethyleneoxy diacrylate, or a combination of two or more thereof added onto the matrix comprising a thermoplastic   \n55(e.g., PMMA) and at least one surfactant selected from, an oleochemical derivative (e.g, Finafog PET), poly(ethyleneglycol) monolaurate, poly(ethyleneglycol) monooleate, poly(ethyleneglycol) sorbitan monolaurate (e.g., Tween? 20), poly(oxyethylene) (10) tridecyl ether, polyethylene gly  \n60 col octadecyl ether (e.g., BRIJ $\\textsuperscript{\\textregistered}$ 20), polyoxyethylene nonylphenyl ether, branched (e.g, Igepa) $|\\textcircled{8}$ 720), sorbitan stearate (e.g.， Span $\\textsuperscript{\\textregistered}$ 60),or a combination of two or more thereof.  \n\nThe antifog composition may be applied to suitable polymeric substrates that may include, but are not limited to, organic polymeric materials such as acrylic polymers, e.g., poly(methylmethacrylate), polyamides, polyimides, acrylo",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 17,
+        "chunk": "# 13  \n\nnitrile-styrene copolymer, styrene-acrylonitrile-butadiene terpolymers, polyvinyl chloride, polyethylene, polycarbonates, copolycarbonates, high-heat polycarbonates, and any other suitable material.  \n\nThe antifog composition may be applied to the substrate  5 as a film or coating that has a thickness (e.g., dry film thickness) in a range of about $0.5~{\\upmu\\mathrm{m}}$ to about $25~{\\upmu\\mathrm{m}}$ ；in another embodiment from about $1\\upmu\\mathrm{m}$ to about $20\\upmu\\mathrm{m}$ ； in yet another embodiment from about $1\\upmu\\mathrm{m}$ to about $25\\upmu\\mathrm{m}$ ； in still yet another embodiment from about $0.5\\upmu\\mathrm{m}$ to about $20\\upmu\\mathrm{m}$ ；1( in a further embodiment from about $1\\ \\upmu\\mathrm{m}$ to about $15\\ \\upmu\\mathrm{m}$ · in an even further embodiment from about $1\\upmu\\mathrm{m}$ to about 10 $\\upmu\\mathrm{m}$ ； or in still an even further embodiment from about $1\\upmu\\mathrm{m}$ to about $5\\upmu\\mathrm{m}$ . In one embodiment, the film or coating has a thickness in a range of about $4~{\\upmu\\mathrm{m}}$ to about $20~{\\upmu\\mathrm{m}}$ ；in 1: another embodiment from about ${5\\upmu\\mathrm{m}}$ to about $25\\upmu\\mathrm{m}$ ； in yet another embodiment from about ${5\\upmu\\mathrm{m}}$ to about $25\\upmu\\mathrm{m}$ ； in still yet another embodiment from about $5\\upmu\\mathrm{m}$ to about $20~{\\upmu\\mathrm{m}}$ .D in a further embodiment from about $5\\upmu\\mathrm{m}$ to about $15\\ \\upmu\\mathrm{m}$ · or in yet another further embodiment from about $5~{\\upmu\\mathrm{m}}$ to2( about $10~{\\upmu\\mathrm{m}}$ . In an embodiment, the film or coating has a thickness of less than about $50~{\\upmu\\mathrm{m}}$ ； and in another embodiment less than about $30~{\\upmu\\mathrm{m}}$  \n\nThe antifog composition may be thermal or UV cured after applying the formulation onto a suitable polymeric substrate (e.g., polycarbonate substrates) thereby covalently cross-linking the hydrophilic diacrylates into the polymer matrix. The polymer matrix (primer matrix) provides excellent adhesion to a substrate (e.g., polycarbonate), mechanical durability, and very good optical clarity. The hydrophilic component and the photo-initiator undergo covalent crosslinking and are then incorporated into the thermoplastic matrix (e.g., PMMA).  \n\nAs previously described, the present antifog compositions can be used to coat a variety of substrates. The compositions : are particularly suitable to provide a coating to prevent or substantially limit fogging of such substrates. As such, substrates coated with the present antifog coating compositions may be used in a variety of applications including, but not limited to, automobile headlights, windshields, eyeglasses, goggles, mirrors, storage containers, windows, camera lens, etc.  \n\nThe following examples are illustrative and not to be construed as limiting of the technology as disclosed and claimed herein.  \n\nwater immersion was done by immersing the coated panels in $65^{\\circ}\\mathrm{C}$ hot water followed by cross hatch adhesion test at different time intervals.  \n\nHumidity Test: Initial optical properties as well as anti-fog property was measured as mentioned above. Then the coated substrates were placed in a Humidity chamber with relative humidity (R.H.) $60\\%$ and $85\\%$ at room temperature as well as at $85^{\\circ}\\mathrm{~C~}$ .After the treatment, the substrates were subjected to optical property measurement as well as the anti-fog property.  \n\nContact Angle Measurements: The water contact angle values were measured by placing ${5\\upmu\\mathrm{l}}$ water droplets onto the coated substrate using a Goniometer. Three measurements were made and the average value was recorded.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# Preparation of Anti-Fogging Coating Resin  \n\nCoating of Antifog Resin onto PC Substrate—Flow Coating Method  \n\nThe PC substrates were cleaned with isopropanol and dried at room temperature (RT) for $20\\ \\mathrm{min}$ .The filtered solutions of above antifog resin formulation were flow coated onto the PC substrate, by applying the coating solution using a squeeze bottle. The coated substrates were air-dried at room temperature for 5 min and subsequently at $75^{\\circ}\\mathrm{~C~}$ .for 5 min in an air-oven. The substrates were then cured in the UV curing machine with UVA intensity of $30{-}150\\mathrm{mW}/\\mathrm{cm}^{2}$ . The antifog film coated PC substrates were subjected to fog testing and optical measurements.  \n\nComposition with PMMA, Hydrophilic Mono- (or) Multifunctional (Meth) Acrylates and Different Surfactants  \n\nThe formulations were made with PMMA (45-55 wt $\\%$ ， glycerol dimethacrylate $(20-25\\mathrm{wt}\\%$ )and surfactants (20-25 wt $\\%$ ）(PEG monolaurate,BRIJ $\\textsuperscript{\\textregistered}$ O20, P2393 and Igepal $\\textsuperscript{\\textregistered}$ CO720,Tween $\\textsuperscript{\\textregistered}$ 20,Methacrylate Tween? 20, Tween $\\textsuperscript{\\textregistered}$ 20 functionalized Silica NPs, Grand 6047, Ecosure EH-9, Mecostat? 3/752, Mecostat? $3/749$ ). Each formulation was coated on a PC substrate and then the optical properties were measured and subjected to fog test at $60^{\\circ}\\mathrm{C}$ . In formulations lacking a surfactant, the PC substrate fogged immediately. When the coating formulation included a surfactant, the PC substrate showed anti-fogging behavior as shown below in Table 1. The presence of surfactant plays a key role in obtaining the antifog behavior.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 19,
+        "chunk": "# Examples  \n\nVarious coating formulations with different ratios of PMMA, hydrophilic mono- or multifunctional (meth) acry- 5C late and surfactants were prepared and tested to evaluate various properties such as adhesion, fogging, humidity, contact angle, and others. Testing was conducted using the following tests:  \n\nOptical Measurements: The $\\%$ Transmittance and Haze 55 were measured using BYK Haze GardTM Instrument ASTM D1003 (BYK instruments).  \n\nFilm metrics: The thicknesses of the coated films were measured using filmmetrics using the refractive index of the coated materials.  \n\nFog Test Studies: Tests were performed according to the ASTM test standards D1735-14. The coated panels were subjected to Fog Test Studies at $60^{\\circ}\\mathrm{~C~}$  \n\nWater Soak Adhesion Test: The initial adhesion was measured using a cross hatch adhesion test according to ASTM D3002/D3359. The adhesion is rated in a scale of 5 B-O B, TB indicative of highest adhesion. Adhesion after  \n\nTABLE 1   \n\n\n<html><body><table><tr><td>Properties of Antifog coatings with different surfactants Here the composition is PMMA 45-55%; Bisphenol-A-ethoxylate diacrylate 20-25%; Irgacure 184 - (2-6) %; Surfactant listed</td></tr><tr><td>below (20-25%)in Table 1 for Examples 1-13. Comparative Example 1 (no surfactant), it is PMMA - 65-75%; Bisphenol-A- ethoxylate diacrylate-18-23%; Irgacure ? 184 (1-5%).</td></tr></table></body></html>  \n\n<html><body><table><tr><td>5 Example</td><td>Additive/Surfactant</td><td>%T</td><td>Haze</td><td>Fogging Time (Sec)</td></tr><tr><td>Comparative</td><td>No Surfactant</td><td>89.0</td><td>0.65</td><td>2-5 Sec.</td></tr><tr><td>Example 1 Example 2</td><td>Finafog PET</td><td></td><td>0.89</td><td>>45 Sec.</td></tr><tr><td>Example 3</td><td>Igepal? 720</td><td>89.3 89</td><td>0.24</td><td>>45 Sec.</td></tr><tr><td>0 Example 4</td><td>PEG monolaurate</td><td>89</td><td>0.32</td><td>>45 Sec.</td></tr><tr><td>Example 5</td><td>BRIJ?020</td><td>89</td><td>0.73</td><td>>45 Sec.</td></tr><tr><td>Example 6</td><td>P2393</td><td>88.9</td><td>0.36</td><td>>45 Sec.</td></tr><tr><td>Example 7</td><td>Tween ? 20</td><td>89.0</td><td>0.2</td><td>>45 Sec</td></tr><tr><td>Example 8</td><td>SiO-Tween?20</td><td>89.2</td><td>0.73</td><td>>45 Sec</td></tr><tr><td>Example 9</td><td>Methacrylate Tween ? 20</td><td>88.4</td><td>0.33</td><td>>45 Sec</td></tr><tr><td>5 Example 10</td><td>Grand 6047</td><td>88.6</td><td>0.43</td><td>>45 Sec.</td></tr><tr><td>Example 11</td><td>Ecosure EH-9</td><td>88.5</td><td>0.39</td><td>>45 Sec.</td></tr></table></body></html>  \n\nTABLE 1-continued   \n\n\n<html><body><table><tr><td>Properties of Antifog coatings with different surfactants Here the composition is PMMA 45-55%; Bisphenol-A-ethoxylate diacrylate 20-25%; Irgacure 184 - (2-6) %; Surfactant listed below (20-25%) in Table 1 for Examples 1-13.Comparative Example 1 (no surfactant), it is PMMA - 65-75%; Bisphenol-A-</td></tr></table></body></html>  \n\n<html><body><table><tr><td>Example Additive/Surfactant</td><td></td><td>%T</td><td>Haze</td><td>Fogging Time (Sec)</td></tr><tr><td>Example 12</td><td>Mecostat ? 7/352</td><td>88.5</td><td>0.36</td><td>>45 Sec.</td></tr><tr><td>Example 13</td><td>Mecostat ? 7/349</td><td>88.8</td><td>0.33</td><td>>45 Sec.</td></tr></table></body></html>  \n\nExample 1 contained the following formulation: PMMA 15 (72 wt $\\%$ )，Bisphenol-A-ethoxylate diacrylate $(22\\mathrm{\\wt\\\\%})$ _， Surfactant (O wt $\\%$ ),Irgacure $\\textsuperscript{\\textregistered}$ 184 (4 wt $\\%$ ，  \n\n16 TABLE 2-continued   \n\n\n<html><body><table><tr><td colspan=\"4\">Properties of Antifog coatings with different hydrophilic acrylates Here the composition is PMMA 52%; Finafog PET 22%; Irgacure ? 184 - 4%; Hydrophilic multi-functional (meth) acrylates (22%) as shown in Table 2.</td></tr><tr><td>Example (meth)acrylates</td><td>Hydrophilic Multifunctional</td><td>%T</td><td>Haze</td><td>Fogging Time (Sec)</td></tr><tr><td>Example 15</td><td>Bisphenol-A-Glycerolate</td><td>89.0</td><td>0.46</td><td>>45 Sec.</td></tr><tr><td>Example 16</td><td>diacrylate Bisphenol-A-Ethoxylate diacrylate</td><td>91.2</td><td>0.43</td><td>>45 Sec.</td></tr></table></body></html>  \n\nExample 2-13 contained the following formulation: PMMA (52 wt $\\%$ )，Bisphenol-A-ethoxylate diacrylate( $(22_{\\mathrm{~\\20~}}$ wt $\\%$ ), Surfactant (22 wt $\\%$ )，Irgacure $\\textsuperscript{\\textregistered}$ 184 (4 wt $\\%$ ， Composition with PMMA, Finafog PET and Different Hydrophilic Multifunctional (Meth)Acrylates  \n\nFormulation were made with PMMA $52\\mathrm{wt}\\%$ ),Finafog PET $22\\mathrm{\\wt\\\\%}$ ） and one of the three hydrophilic acrylates namely, Glycerol dimthacrylate (or) Bisphenol-A-ethoxylate diacrylate (or) Bisphenol-A-glycerolate diacrylate (22 wt $\\%$ )and $4\\mathrm{wt\\%}$ photoinitiator. PC Substrates were cleaned with deionized water and isopropanol and dried at room temperature for $20\\mathrm{min}$ . prior to coating. These formulations  \n\nExample 17 contained the following formulation: PMMA $(52\\%)$ , Hydrophilic mono- (or) multi-functional (meth)acrylate $(22\\%)$ ， Surfactant (Finafog PET) $(22\\%)$ and photoinitiator (Irgacure $\\textsuperscript{\\textregistered}$ 184) $(4\\%)$ .  \n\nExample 18 contained the following formulation: PMMA $(60\\%)$ , Hydrophilic mono- (or) multi-functional (meth)acrylate $(18\\%)$ ， Surfactant (Finafog PET） $(18\\%)$ and photoinitiator (Irgacure $\\textsuperscript{\\textregistered}$ 184) $(4\\%)$ ：  \n\nPolycarbonate substrates (PC substrates) were coated separately with either the coating of Example 17 or Example 18. Various properties of the coating were evaluated. The results of the various testing methods are summarized below in Table 3.  \n\nTABLE3   \n\n\n<html><body><table><tr><td colspan=\"5\">Summary of various testing methods of Examples 17 and 18.</td></tr><tr><td>Test Studies Properties</td><td></td><td>Comparative Example PC Substrate - No Coating</td><td>Coating Example 17</td><td>PC -Antifog PC - Antifog Coating Example 18</td></tr><tr><td>Water soak Adhesion Test @65°C.for 10days</td><td>Adhesion</td><td>N/A</td><td>5B</td><td>5B</td></tr><tr><td>Humidity Chamber @</td><td>Antifog (Before)</td><td>1-2 Sec.</td><td>>30 Sec</td><td>>30 Sec</td></tr><tr><td>85°C.&R.H.85%</td><td>After treatment</td><td>1-2 Sec.</td><td>>30 Sec</td><td>>30 Sec</td></tr><tr><td>BoilingWater Soak Test</td><td>Antifog (Before)</td><td>1-2 Sec.</td><td>>30 Sec</td><td>>30 Sec</td></tr><tr><td>@100°C. for 1 h</td><td>After treatment</td><td>1-2 Sec.</td><td>3-8 Sec.</td><td>4-8 Sec.</td></tr><tr><td>Repeated Fog Cycles</td><td>Antifog</td><td>1-2 Sec.</td><td>>30 Sec</td><td>>30 Sec</td></tr><tr><td>(up to 15 cycles) Heat Treatment @130°</td><td>Antifog (Before)</td><td>1-2 Sec.</td><td>>30 Sec</td><td>>30 Sec</td></tr><tr><td>C.for 1 h</td><td>After treatment</td><td>1-2 Sec.</td><td>>30 Sec</td><td>>30 Sec</td></tr></table></body></html>  \n\nwere each flow coated on a PC substrate and then the optical properties were measured. Each PC substrate was subjected 5( to fog test at $60^{\\circ}\\mathrm{C}$ PC substrates coated with a formulation containing these hydrophilic acrylates showed antifog properties as shown below in Table 2. It appears that covalently cross-linking hydrophilic monomers along with the surfactants to the polymeric system (e.g., PMMA), it is possible to 5: fabricate antifog coating.  \n\nTABLE 2   \n\n\n<html><body><table><tr><td colspan=\"3\">Properties of Antifog coatings with different hydrophilic acrylates Here the composition is PMMA 52%; Finafog PET 22%; Irgacure ? 184 - 4%; Hydrophilic multi-functional (meth)acrylates (22%)as shown in Table2.</td></tr><tr><td>Example</td><td>Hydrophilic Multifunctional (meth)acrylates %T</td><td>Fogging Time (Sec)</td></tr></table></body></html>\n\nExample 14 Glycerol Dimethacrylate 89.3 0.89 >45 Sec.  \n\nFormulations were also tested to determine ideal ranges for reagents including amounts for thermoplastic matrices, hydrophilic acrylates, and surfactants. Table 4 below describes Formulations 1-5,which were assessed for suitable antifog properties and suitable adhesion to substrate.  \n\nTABLE4   \n\n\n<html><body><table><tr><td colspan=\"6\">Assessment of Various Amounts of Reagents</td></tr><tr><td>Composition</td><td>PMMA</td><td>Hydrophilic Monomers</td><td>Surfac- tants</td><td>Antifog Property</td><td>Adhesion to Substrate</td></tr><tr><td>A</td><td>40%</td><td>30%</td><td>30%</td><td>Yes</td><td>No</td></tr><tr><td>B</td><td>70%</td><td>15%</td><td>15%</td><td>Yes</td><td>Yes</td></tr><tr><td>C</td><td>80%</td><td>10%</td><td>10%</td><td>No</td><td>Yes</td></tr><tr><td>D</td><td>50%</td><td>20%</td><td>30%</td><td>Yes</td><td>Yes</td></tr><tr><td>E</td><td>52%</td><td>22%</td><td>22%</td><td>Yes</td><td>Yes</td></tr></table></body></html>  \n\nVarious coating formulations with different ratios of thermoplastic matrix, glycerol dimethacrylate, and Finafog PET were prepared and tested to evaluate anti-fogging properties and adhesion to substrate (Table 4). Embodiments of the invention showed no fogging, good adhesion to the substrate, and good optical clarity.  \n\nWhile the invention has been described with reference to various exemplary embodiments, it will be appreciated that modifications may occur to those skilled in the art, and the present application is intended to cover such modifications and inventions as fall within the spirit of the invention.  \n\nWhat is claimed is:  \n\n1.An antifog coating composition comprising at least one thermoplastic matrix, at least one hydrophilic compound, and at least one surfactant, wherein the at least one hydrophilic compound is a hydrophilic acrylate having formula (I):  \n\n![](images/5b7f5895f225920d29880769de4e8529d2883caafea8a6ab16d15e1b40aaed85.jpg)  \n\nwherein:  \n\n$\\mathrm{R}_{1}$ is independently selected from the group consisting of O; H; a linear alkyl group containing from 1 to 5 carbon atoms; a linear alkyl group containing from 1 to 5 carbon atoms substituted with a hydroxy or an alkoxy group; an aromatic group; a hydroxy group; an alkoxy group containing from 1 to 3 carbon atoms; a methacrylate, and an acrylate group; wherein a is an integer from 0 to 1;  \n\n$\\mathrm{R}^{2}$ is independently chosen from $\\mathrm{~H~}$ or $\\mathrm{CH}_{3}$ · $\\mathrm{R}^{3}$ is independently selected from the group consisting of H, an alkyl group having from 1 to 6 carbon atoms, a hydroxy group, an alkoxy group having from 1 to 3 carbon atoms, a methacrylate and an acrylate group;  \n\nA is independently selected from the group consisting of 4( O, a substituted or unsubstituted linear alkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted divalent aromatic group having from 6 to 20 carbon atoms, an 4: alkylene oxide, and a substituted or unsubstituted divalent heterocyclic group having from 5 to 20 carbon atoms;  \n\n$\\mathbf{A^{\\prime}}$ is independently selected from H,a substituted or unsubstituted linear alkyl group having from 1 to 20 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted divalent aromatic group having from 6 to 20 carbon atoms, a substituted or unsubstituted divalent heterocyclic group having from 5 to 20 carbon 55 atoms, a methacrylate and an acrylate group;  \n\nB is independently selected from O, a substituted or unsubstituted linear alkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted divalent aromatic group having from 6 to 20 carbon atoms,a substituted or unsubstituted divalent heterocyclic group having from 5 to 20 carbon atoms, and a bisphenol A unit e is an integer from O to 1;  \n\nwherein n is an integer from 1 to 5 and m is an integer from O to 5.  \n\n2. The antifog coating composition of claim 1, further comprising at least one photo-initiator or at least one thermal initiator.  \n\n3. The antifog coating composition of claim 1, wherein the at least one hydrophilic acrylate is selected from the group consisting of a poly(ethyleneoxy)methacrylate, a poly (ethyleneoxy)acrylate, a poly(ethyleneoxy)monomethylether acrylate, a poly(ethyleneoxy)monomethylether methacrylate, apentaerythritol triacrylate, a glycerol dimethacrylate, a glycerol diacrylate, a bisphenol-A-glycerol tetraacrylate, a bisphenol-A-glycerol diacrylate, a bisphenol-A-ethyleneoxy diacrylate, and a combination thereof.  \n\n4. The antifog coating composition of claim 1, wherein   \nL5 the at least one thermoplastic matrix is selected from the group consisting of a polyether ester, a polyester ester, a thermoplastic polyurethane, a styrene ethylene butadiene styrene, an acrylonitrile butadiene styrene, a styrene acrylonitrile, polyamide, an acrylate styrene acrylate block copo  \n20 lymer, polybutylene terephthalate, a polycarbonate, a polyether block amide, a polymethyl methacrylate, a polyoxymethylene, a polyvinylchloride, and a combination thereof.  \n\n25 5. The antifog coating composition of claim 1, wherein the at least one thermoplastic matrix is chosen from polycarbonate, polymethyl methacrylate, or a combination thereof.  \n\n6. The antifog composition of claim 1, wherein the at least one surfactant is selected from the group consisting of a sorbitan ester, a polyethoxylated sorbitan ester, a polyoxyethylene glycol alkyl ether, a polyoxypropylene glycol alkyl ether, a glucoside alkyl ether, a polyoxyethylene glycol octylphenol ether, a polyoxyethylene glycol alkylphenol ether, a polyoxyethylene glycol sorbitan alkyl ester, a sorbitan alkyl ester, and a combination thereof.  \n\n7. The antifog coating composition of claim 1, wherein the at least one thermoplastic matrix is present in an amount of about 10 wt $\\%$ to about 70 wt $\\%$ ，the at least one hydrophilic acrylate is present in an amount of about $10~\\mathrm{wt}$ $\\%$ to about $40\\mathrm{wt\\%}$ ， and the at least one surfactant is present in an amount of about 10 wt $\\%$ to about $40\\mathrm{\\wt\\\\%}$ ，each weight percent based on the total weight of the composition.  \n\n8. The antifog composition of claim 7, further comprising at least one photo-initiator present in an amount of about 1 wt $\\%$ to about $5\\mathrm{wt\\%}$ .  \n\n9. An antifog coating composition comprising:   \n(a) at least one acrylate matrix;   \n(b) at least one hydrophilic acrylate having the formula (I) or formula (II):  \n\n![](images/cf583ac0bd53a637cd631cbdf4b3b67ad6281849b3954bc3e1637270f3c26300.jpg)  \n\nwherein:  \n\n$\\mathrm{R}_{1}$ is independently selected from the group consisting of 0; H; a linear alkyl group having from 1 to 5 carbon atoms optionally substituted by a hydroxy or an alkoxy group; an aromatic group; a hydroxy group; an alkoxy group having from 1 to 5 carbon atoms; a methacrylate; and an acrylate group; wherein a is an integer from 0 to 1;",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 20,
+        "chunk": "# 19  \n\n$\\mathrm{R}^{2}$ is independently chosen from H or $\\mathrm{CH}_{3}$ $\\mathrm{R}^{3}$ is independently selected from the group consisting of H, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, an alkoxy group having from 1 to 3 carbon atoms, a methacrylate and an acrylate group;  \n\nA is independently selected from the group consisting of O, a substituted or unsubstituted linear alkyl group having from 1 to 2O carbon atoms, a substituted or unsubstituted cycloalkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted divalent aromatic group having from 6 to 20 carbon atoms, an alkylene oxide, and a substituted or unsubstituted divalent heterocyclic group having from 5 to 20 carbon atoms;  \n\nA' is independently selected from the group consisting of 1: H, a substituted or unsubstituted linear alkyl group having from 1 to 2O carbon atoms, a substituted or unsubstituted cycloalkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted divalent aromatic group having from 6 to 20 carbon atoms, a 2( substituted or unsubstituted divalent heterocyclic group having from 5 to 20 carbon atoms, a methacrylate, and an acrylate group;  \n\nB is independently selected from O, a substituted or unsubstituted linear alkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted divalent aromatic group having from 6 to 20 carbon atoms, a substituted or unsubstituted divalent heterocyclic group having from 5 to 20 carbon atoms and a bisphenol A unit; wherein e is an integer from 0 to 1;  \n\nwherein n is an integer from 1 to 5 and m is an integer from 0 to 5; or  \n\n35  \n\n![](images/e17465877563501673e531ba229c4657b7225f65e9ce953ed344dd44259fd0cf.jpg)  \n\nwherein $\\mathrm{R}_{4},\\mathrm{R}_{5}$ ，and $\\mathrm{R}_{6}$ are independently selected from the group consisting of H, a linear alkyl group having from 1 to 5 carbon atoms, an aromatic group, a hydroxy group, and an alkoxy group having from 1 to 3 carbon atoms;  \n\nQis independently selected from the group consisting of a linear alkylene group having from 1 to 6 carbon atoms, a cycloalkylene group having from 1 to 10 carbon atoms, a divalent aromatic group having from 6 to 20 carbon atoms, and a divalent heterocyclic group having from 5 to 20 carbon atoms;  \n\nwherein $\\mathfrak{p}$ is an integer from O to 5; and (c) at least one non-ionic surfactant.  \n\n10. The antifog coating composition of claim 9, wherein the at least one hydrophilic acrylate is selected from the group consisting of a poly(ethyleneoxy)methacrylate, a poly (ethyleneoxy)acrylate, a poly(ethyleneoxy)monomethylether acrylate, a poly(ethyleneoxy)monomethylether methacrylate, apentaerythritol triacrylate,aglycerol dimethacrylate, a glycerol diacrylate, a bisphenol-A-glycerol tetraacrylate, a bisphenol-A-glycerol diacrylate, a bisphenol-A-ethyleneoxy diacrylate, and a combination thereof.  \n\n11. The antifog coating composition of claim 9, wherein the at least one non-ionic surfactant is selected from the group consisting of a sorbitan ester, a polyethoxylated sorbitan ester, a polyoxyethylene glycol alkyl ether, a polyoxypropylene glycol alkyl ether, a glucoside alkyl ether, a polyoxyethylene glycol octylphenol ether, a polyoxyethylene glycol alkylphenol ether, a polyoxyethylene glycol sorbitan alkyl ester, a sorbitan alkyl ester and a combination thereof.  \n\n12.The antifog coating composition of claim 9, wherein the at least one acrylate matrix is present in an amount of about $10\\mathrm{wt}\\%$ to about $70\\mathrm{wt}\\%$ the at least one hydrophilic acrylate is present in an amount of about 10 wt $\\%$ to about $40\\mathrm{wt\\%}$ , and the non-ionic surfactant is present in an amount of about $10\\mathrm{\\mt\\\\%}$ to about $40\\mathrm{\\wt\\\\%}$ ，each weight percent based on total weight of the composition.  \n\n13.The antifog composition of claim 12, further comprising a photo-initiator present in an amount of about 1 wt $\\%$ to about $5\\mathrm{wt\\\\%}$ \\*  \n\n14. An article comprising a substrate and the antifog coating composition of claim 1 disposed on at least a portion of a surface thereof.  \n\n15. The article of claim 14, wherein:  \n\na) the thermoplastic matrix is polymethyl methacrylate and is present from about 10 wt $\\%$ to about $70\\mathrm{wt}\\%$ D b) the hydrophilic compound is hydrophilic acrylate and is present from about $10\\mathrm{\\wt\\\\%}$ to about $40\\mathrm{wt\\\\%}$ . c) the surfactant is a non-ionic surfactant and is present from about 10 wt $\\%$ to about 40 wt $\\%$ ； and d) the antifog coating composition further comprising (1) about 1 wt $\\%$ to about 5 wt $\\%$ photo-initiator or (2）1 wt $\\%$ to about 5 wt $\\%$ thermal initiator, wherein each wt $\\%$ is based on the total weight of the composition.  \n\n16. The article of claim 14, wherein the substrate is selected from the group consisting of an acrylic polymer, a polyamide, a polyimide, an acrylonitrile-styrene copolymer, a styrene-acrylonitrile-butadiene terpolymer, a polyvinyl chloride, a polyethylene, a polycarbonate, a copolycarbonate and a combination thereof.  \n\n17. The article of claim 14, wherein the substrate is polycarbonate.  \n\n18. The article of claim 14,wherein the article is an automobile headlight, a windshield, eyeglasses, goggles, a mirror, a storage container, a window or a camera lens.  \n\n19. The article of claim 14 wherein the article has a fogging time, as measured in accordance with the Fog Test Studies, of greater than 45 seconds.",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,42 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19) United States (12) Patent Application Publication (1o) Pub. No.: US 2003/0148113 A1 Chen (43) Pub. Date: Aug. 7, 2003",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (54) ANTI-FOG COATING COMPOSITION, PROCESS, AND ARTICLE  \n\n(52) U.S. Cl. 428/428; 428/429 (75) Inventor: Mao Chen, Evansville, IN (US) Correspondence Address: Hanh T. Pham GE Plastics One Plastics Avenue Pittsfield, MA 01201 (US)  \n\n(73） Assignee: General Electric Company (21) Appl. No.: 10/062,646 (22) Filed: Jan.31, 2002",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# Publication Classification  \n\n(51） Int. Cl.7 B32B 17/00",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# ABSTRACT  \n\nAn anti-fog coating composition comprises a silicone polymer or oligomer, a water dispersible polyurethane polymer or oligomer, and water. A process for forming an anti-fog film comprises applying the anti-fog coating composition to a substrate and coalescing the silicone and polyurethane compounds to form the film. In another embodiment, the process for forming the anti-fog film comprises applying the components of the anti-fog coating composition to a substrate and crosslinking the components to form the anti-fog film. The components generally include a polyol, an isocyanate, a catalyst, and a silicone polymer or oligomer.",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# ANTI-FOG COATING COMPOSITION, PROCESS, AND ARTICLE  \n\nBACKGROUND OF THEINVENTION [0001] The present disclosure relates to coating compositions, and more particularly, to coating compositions that form films exhibiting anti-fog and/or anti-condensation properties.  \n\n[0002]  There are numerous instances in which optically clear articles would be enhanced if they were resistant to the formation of a fog on a surface of the article, for example, in window applications such as for greenhouses.  \n\n[0003]  In general, fog and condensation formation occur under conditions of high humidity and high temperature or at interfacial boundaries where there is a large temperature and humidity difference. Coatings that reduce the tendency for surfaces to “fog up\" have been reported. These so-called anti-fog coatings improve the wettability of a surface by allowing a thin layer of water film to form on the surface instead of discrete droplets. Known anti-fog coatings include, for example, coatings using ammonium soap, such as mixtures of an alkyl ammonium carboxylates with a surface active agent, for example, a sulfated or sulfonated fatty material; salts of sulfated alkyl aryloxypolyalkoxy alcohol; or alkylbenzene sulfonates. Other common anti-fog coating compositions use colloidal silica to provide water resistance. However, colloidal silica coating compositions generally have a high solvent content and are generally less effective for controlling condensation. Other common antifog compositions require chemical crosslinking to form a cohesive film. Although less solvent is used, the chemical crosslinking can significantly affect film properties.A highly crosslinked coating can cause the coated film to be brittle whereas low crosslinking can result in chalking, i.e., a powdery film that degrades or disperses upon contact with an aqueous solution.  \n\n[0004] Although the above noted coating formulations have addressed some of the problems in the field,none provides a total solution. Most of the formulations have low moisture absorptivity, long moisture release time, and/or poor water and solvent resistance. For example, watersoluble silicone resins synthesized from hydrophilic functional group-bearing silane compounds generally have poor water resistance, inadequate film hardness and poor weathering resistance. Some of these formulations also have inefficient fabrication processes, e.g. a long coat curing tim. To be useful in most commercial applications, the anti-fog coating should possess high clarity, possess a long shelf life prior to coating, exhibit impact resistance properties suitable for the intended application,be able to absorb and release moisture simultaneously, and be able to resist water and conventional organic solvents, such as alcohols, alkylbenzenes (e.g., toluene), glycol ethers (e.g., propylene glycol monomethyl ether), and alkyl ketones (e.g., methyl ethyl ketone).",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# SUMMARYOFTHEINVENTION  \n\n[0005]  Disclosed herein is an anti-fog coating composition comprising a silicone compound, a water dispersible polyurethane compound, and water.  \n\n[0006] A process for forming an anti-fog film on a substrate comprises applying an aqueous coating composition to the substrate, wherein the aqueous coating composition comprises a silicone compound, a water dispersible poly urethane compound, and water; and coalescing the silicone compound and polyurethane compound to form a film.  \n\n[0007] In another embodiment, a process for forming an anti-fog film comprises applying a coating composition to a substrate,wherein the coating composition comprises a silicone compound, an isocyanate, a polyol and a catalyst; and crosslinking the coating composition to form a film, wherein crosslinking comprises heating the substrate to a temperature and for a time effective to form the film.  \n\n[0008]  A glass or plastic article having an anti-fogging surface comprises a glass or plastic substrate and an anti-fog coating disposed on at least one surface of the substrate, the anti-fog coating comprising a silicone compound, a water dispersible polyurethane compound, and water.  \n\n[0009] In another embodiment, glass or plastic article having an anti-fogging surface comprises a glass or plastic substrate; and an anti-fog coating disposed on at least one surface of the substrate, the anti-fog coating comprising a crosslinked film formed from a silicone, an isocyanate, a polyol and a catalyst.  \n\n[0010]  These and other features will be apparent from the following detailed description.",
+        "category": " Abstract"
+    },
+    {
+        "id": 7,
+        "chunk": "# DETAILED DESCRIPTION OF THE INVENTION  \n\n[0011] An anti-fog,water based coating composition is obtained by combining a silicone compound having a hydrophilic functional group with a water dispersible polyurethane compound.A film formed from the anti-fog coating composition is primarily formed by coalescence, a process that causes the silicone and polyurethane compounds to flow into each other and form a continuous film.Advantageously, the resulting films exhibit, among others, low solvent retention, durability, and flexibility.  \n\n[0012] In general, a formulation of the coating composition comprises a silicone polymer or oligomer, a water dispersible polyurethane polymer or oligomer, and water. The silicone polymer or oligomer is about O.1 to about 20 parts by weight of the formulation, with about 1 to about I O parts by weight more preferred, and with about 1 to about 5 parts by weight even more preferred. The water dispersible polyurethane polymer or oligomer is about 5 to about 50 parts by weight of the formulation,with about 10 to about 40 parts by weight more preferred, and with about 20 to about 30 parts even more preferred. The remainder of the formulation comprises an aqueous solvent, i.e., water and an optional co-solvent miscible with water. Any co-solvent included in the formulation is preferably about 1 to about 10 parts per weight and more preferably, about 5 to 10 parts by weight of the formulation. The sum of the weights of the compounds preferably totals 100 parts by weight. Of course, other compounds (such as a UV absorbers, tight stabilizers, pigments, dyes, etc.) may be added to or omitted from a formulation, in which case the relative amounts of each of the compounds would be adjusted accordingly to total 100 parts by weight, as would be apparent to one skilled in the art in view of this disclosure.  \n\n[0013] The term silicone as used herein includes polymers or oligomers of organosiloxanes (and moieties derived therefrom) wherein each organo group is independently selected from the group consisting( of alkyl groups such as $\\mathbf{C}_{1}$ to $\\mathbf{C}_{12}$ alkyl groups, for example.At least one or more of the organo groups contain one or more hydrophilic functional groups. Any hydrophilic functional group may be used. Examples of suitable hydrophilic functional groups include— $\\mathbf{\\bar{\\Omega}}_{C\\mathbf{O}_{2}\\mathrm{H}}$ ；—OH; —NH; oxyethylene segments, other nitrogen containing organic functional groups,—SH; ester, urethane, and isocyanate groups. In a preferred embodiment, functional group is a weak acid group. It is preferred that the silicone polymer or oligomer does not include strong acids such as sulfonic acid functional groups. The presence of strong acids such as the sulfonic acid groups in the silicone polymer or oligomer (and the amines that are commonly used to neutralize the acid) can degrade the polymer film formed from the coating composition, cause discoloration result in poor weathering performance, or result in a film exhibiting high water sensitivity. The preferred functional groups provide room temperature curing sites for film coalescence, act as dispersing aids by lowering the surface energy of the aqueous dispersion, and/or lower the minimum film forming temperature.  \n\n[0014] Preferred silicone resins are organosiloxanes, free from sulfonic acid functional groups, having the general formula:  \n\n$$\n\\mathbf{M_{a}M_{b}^{\\prime}D_{c}D_{d}^{\\prime}T_{e}}\\mathbf{T_{f}}\\mathbf{Q_{g}},\n$$  \n\n[0015] wherein the subscripts a, c, d, e, f, and $\\mathbf{g}$ are zero or a positive integer, subject to the limitation that the sum of the subscripts b, $\\mathrm{~d~}$ ,and f is one or greater: $\\mathbf{M}$ has the formula: $\\mathrm{R}_{3}^{1}\\ \\mathrm{SiO}_{1/2}$ ，where each ${\\bf R}^{1}$ is independently a monovalent hydrocarbon radical having from one to forty carbon atoms; $\\mathbf{M}^{\\prime}$ has the formula: $\\mathrm{R}_{3-\\mathrm{h}}^{2}\\mathrm{R}_{\\mathrm{~h}}^{\\mathrm{~\\bar{3}~}}\\mathrm{SiO}_{1/2}$ , wherein each ${\\bf R}^{2}$ and $\\mathbb{R}^{3}$ are independently monovalent hydrocarbon radicals having from one to forty carbon atoms, and the subscript h is 1, 2, or 3; D has the formula: $\\mathrm{R}_{\\ 2}^{4}\\ \\mathrm{SiO}_{2/2}$ ，wherein each R4 is independently a monovalent hydrocarbon radical having from one to forty carbon atoms; $\\mathbf{D^{\\prime}}$ has the formula: $\\mathbb{R}_{~2.}^{5}$ $\\mathbf{\\Omega}_{1}\\mathbf{R}^{6}{}_{1}\\mathbf{,SiO}_{2/2}$ ，wherein each of $\\mathbf{R}^{5}$ and R6 is independently a monovalent hydrocarbon radical having from one to forty carbon atoms, and the subscript i is 1 or 2; Thas the formula: $\\mathrm{R}^{7}\\mathrm{SiO}_{3/2}$ ，wherein each ${\\bf R}^{7}$ is a monovalent hydrocarbon radical having from one to forty carbon atoms; $\\mathrm{T}^{\\dag}$ has the formula: $\\mathrm{R}^{\\mathrm{8}}\\mathrm{SiO}_{3/2}$ ,wherein $\\mathbb{R}^{\\mathrm{s}}$ is a monovalent hydrocarbon radical having from one to forty carbon atoms; and Q has the formula: SiO4/2\\*  \n\n[0016]  More preferably, the silicone is an ionic or nonionic siloxane alkoylate having the general formula:  \n\n![](images/a45b23d0423b491e7deec71d162040d83192cc8ecdf810f1ff215651e05a9c50.jpg)  \n\n[0017]  wherein each of $\\mathbb{R}^{9-17}$ are independently a monovalent hydrocarbonyl radical, $\\mathrm{R}^{18}$ is of the general formula: $\\mathrm{R^{19}-\\dot{Z}-(C_{m}H_{(2m-1)}R^{20}O)_{j}(C_{n}H_{2n}O)_{k}R^{21}}$ , m and n are integers greater than or equal to $\\mathbf{0;j}$ and $\\mathbf{k}$ are integers treater than or equal to O. subject to the proviso that the sum of $\\mathbf{j}{+}\\mathbf{k}$ is greater than or equal to 1; Z is $\\mathrm{H}$ ,—O—.—S—,—SHCO—,—NH—,or $\\mathrm{-NH}_{2}\\mathrm{-};\\mathrm{R}^{19}$ is a divalent hydrocarbylene radical, $\\scriptstyle\\mathbf{R}^{20}$ and $\\scriptstyle\\mathbf{R}^{21}$ are independently hydrogen, alkyl, hydroxyalkyl, amino, amido, amineoxide, cyano, isocyano, aryl, arylene,carboxy, alkoxy, halogen,haloalkyl, haloalkyoxy, sulfo, sulfamo, phophono, salts thereof, combinations comprising at least one of the foregoing, and the like; and wherein $\\mathbf{x}$ and y are integers greater than or equal to 0, subject to the proviso that $\\mathbf{x}{+}\\mathbf{y}$ is greater than or equal to 1.  \n\n[0018] Preferred silicone resins are polydimethylsiloxanes.Exemplary polydimethylsiloxanes include, but are not limited to, poly[dimethylsiloxane-co-methyl(3-hydroxypropyl)siloxane]-graft-poly(ethylene glycol) methyl ether, poly [dimethylsiloxane-co-[3-[2-(2-hydroxyethoxy)ethoxy]propyl]methylsiloxane, poly[dimethylsiloxane-co-(3- aminopropyl)methtylsiloxane], poly[dimethylsiloxane-comethyl(3-hydroxypropyl)siloxane]-graft poly(ethylene/ propylene glycol) methyl ether, poly[dimethylsiloxane-comethyl(3-hydroxypropyl)siloxane]-graft-tetrakis(1,2- butylene glycol), poly(dimethylsiloxane-co-alkyl methylsiloxane), poly[dimethylsiloxane-co-methyl(stearoyloxyalkyl)siloxane], poly[dimethylsiloxane-co-methyl(3- hydroxypropyl)siloxane]-graft-poly(ethylene/propylene glycol), poly[dimethylsiloxane-co-methyl(3-hydroxypropyl)siloxane]-graft-poly(ethylene glycol) [3-(trimethylammonio)propyl chloride, poly[dimethylsiloxane-co-methyl(3- hydroxypropyl)siloxane]-graft-poly(ethylene glycol) 3-aminopropyl ether, poly[dimethylsiloxane-co-methyl(3,3, 3-trifluoropropyl)siloxane], poly(dimethylsiloxane bis[[3- [(2-aminoethyl)amino]propyl]dimethoxysilyl]ether, and poly(dimethylsiloxane) ethoxylate/propoxylated.  \n\n[0019] The term water dispersible polyurethane, generally refers to a polymeric or oligomeric material, the backbone of which comprises a multiplicity of urethane linkages, —O—CO-NH—, and may also contain one or more urea linkages:—NH—CO—NH—, and may also contain one or more thiocarbamate linkages: —S—CO—NH—and combinations thereof.  \n\n[0020] The water dispersible polyurethanes are preferably formed from compositions comprising an organic isocyanate component reactive with an active hydrogen-containing component(s), and a catalyst.  \n\n[0021] The organic isocyanate components used in the preparation of the water dispersible polyurethane preferably are those having the general formula:  \n\n$$\n\\mathbf{Q(NCO)_{i}}\n$$  \n\n[0022]  wherein i is an integer of two or more and Q is an organic radical having a valence of i, wherein i is greater than 2. Q can be a substituted or unsubstituted hydrocarbon group (i.e., an alkylene or an arylene group). Q can be a group having the formula $\\mathrm{Q^{1}{-}\\dot{Z}{-}\\mathrm{Q^{1}}}$ wherein $\\mathbf{Q}^{1}$ is an alkylene or arylene group and $z$ is $\\mathrm{-0\\mathrm{-},\\mathrm{-}0\\mathrm{-}Q^{1}\\ S.}$ $-\\mathrm{C}(\\mathrm{O})-$ 。 $-\\bar{\\bf S}-$ ， $-\\mathrm{{\\bfS}}{-\\mathrm{{\\bf{Q}}}^{1}}.$ S—，—sO— or $-\\mathrm{sO}_{2}-$ Examples of such compounds include hexamethylene diisocyanate, 1,8-diisocyanato-p-methane, xylyl diisocyanate. diisocyanatocyclohexane, phenylene diisocyanates, tolylene diisocyanates, including 2,4-tolylene diisocyanate, 2,6- tolylene diisocyanate, and crude tolylene diisocyanate, bis(4-isocyanatophenyl)methane, chlorophenylene diisocyanates, diphenylmethane $^{.4,4^{\\prime}}$ -diisocyanate (also known as 4,4'-diphenyl methane diisocyanate, or MDI) and adducts thereof,naphthalene-1,5-diisocyanate.triphenylmethane-4,  \n\n4',4\"-triioscyanate, isopropylbenzene-alpha-4-diisocyanate, and polymeric isocyanates such as polymethylene polyphe nylisocyanate.  \n\n[0023]  The active  hydrogen-containing component includes polyhydroxyl-containing compounds, such as hydroxyl-terminated polyhydrocarbons (U.S. Pat. No. 2,877,212); hydroxyl-terminated polyformals (U.S. Pat. No. 2,870,097); fatty acid triglycerides (U.S. Pat. Nos.2,833,730 and 2,878,601); hydroxyl-terminated polyesters (U.S. Pat. Nos. 2,698,838, 2,921,915,2,591,884, 2,866,762, 2,850, 476,2,602,783,2,729,618,2,779,689, 2,811,493, and 2,621, 166); hydroxymethyl-terminated perfluoromethylenes (U.S. Pat. Nos. 2,911,390 and 2,902,473); polyalkylene ether glycols (U.S. Pat. No.2,808,391 British Pat. No. 733,624); polyalkylene ether glycols (U.S. Pat.No.2,808,391; British Pat. No. 733,624); polyalkylenearylene ether lycols (U.S. Pat. No. 2,808,391); polycarbonate polyol (U.S. Pat. Nos. 6,087,051 and 6,057,034) and polyalkylene ether triols (U.S. Pat. No. 2,866,774).  \n\n[0024] Preferred polyhydroxyl-containinig materials are the polycaronate polyols and polyether polyols. The polycarbonate polyols may be, for example, polycarbonatediols which are obtainable by a reaction of a short chain dialkylcarbonate and a component selected from aforementioned polyether polyols, polyesterpolyols, and diol components such as 2-methylpropanediol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-],5-pentanediol, neopentyl glycol, 1,5-octanediol, 1,4-bis-(hydroxymethyl)cyclohexane, and the like. The short chain dialkylcarbonate may be $\\mathbf{C}_{1-4}$ alkylcarbonates such as, for example, dimethylcarbonate and diethylecarbonate. Examples of commercially available polycarbonate diol may be DESMOPHENE 2020E (manufactured by Sumitomo Bayer Co., Ltd.), DN-980, DN-982 and DN-983 (manufactured by Japan Polyurethane Industry Co., LTD).  \n\n[0025]   Polyether polyols may be obtained by the chemical addition of alkylene oxides, such as ethylene oxide, propylene oxide and mixtures thereof to water or polyhydric organic compounds, such as ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butanediol,1,4-butanediol, 1,5-pentanediol,1,2-hexylene glycol 1,10-decanediol, 1,2-cyclohexanediol, 2-butene-1,4-diol, 3-cyclohexene-1,1-dimethanol, 4-methyl-3-cyclolhexene-1, 1-dimethanol, 3-methylene-1,5-pentanediol, diethylene glycol, (2-hydroxyethoxy)-1-propanol, 4-(2-hydroxyethoxy)-1- butanol, 5-(2-hydroxypropoxy)-1-pentanol,1-(2- hydroxymethoxy)-2-hexanol, 1-(2-hydroxypropoxy)-2- octanol, 3-allyloxy-1.5-pentanediol, 2-allyloxymethyl-2- methyl-1,3-propanediol, [4,4-pentyloxy)-methyl]-1,3- propanediol, 3-(o-propenylphenoxy)-1,2-propanediol, 2,2'- diisopropylidenebis(p-phenyleneoxy)diethanol, glycerol, 1,2,6-hexanetriol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, 3-(2-hydroxyethoxy)-1,2- propanediol, 3-(2-hydroxypropoxy)-1,2-propanediol, 2,4-dimethyl-2-(2-hydroxyethoxy)-methylpentanediol-1,5; 1,1,1-tris[2- hydroxyethoxy) methyl]-ethane, 1,1,1-tris[2- hydroxypropoxy)-methyl] propane, diethylene glycol, dipropylene glycol, pentaerythritol, sorbitol, sucrose, lactose, alpha-methylglucoside, alpha-hydroxyalkylglucoside, novolac resins,phosphoric acid,benzenephosphoric acid, polyphosphoric acids such as tripolyphosplhoric acid and tetrapolyphosphoric acid, ternary condensation products, and the like. The alkylene oxides employed in producing polyoxyalkylene polyols normally have from 2 to 4 carbon atoms. Propylene oxide and mixtures or propylene oxide with ethylene oxide are preferred. The polyols listed above can be used per se as the active hydrogen compound.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# [0026]   A preferred class of polyether polyols is generally represented by the following formula:  \n\n$$\n\\mathrm{R}[\\mathrm{(OCH_{n}H_{2n})_{z}O H}]_{\\mathrm{a}}\n$$  \n\n[0027] wherein $\\mathbf{R}$ is hydrogen or a polyvalent hydrocarbon radical, a is an integer (i.e., 1 or 2 to 6 to 8) equal to the valence of R, n in each occurrence is an integer from 2 to 4 inclusive (preferably 3) and $\\textbf{z}$ in each occurrence is an integer having, a value of from 2 to about 200, preferably from 15 to about 100.  \n\n[0028]  Additional active hydrogen-containing compounds are the polymers of cyclic esters. The preparation of cyclic ester polymers from at least one cyclic ester monomer is well documented in the patent literature as exemplified by U.S. Pat.Nos.3,021,309 through 3,021,317,3,169,945, and 2,962,524. Suitable cyclic ester monomers include, but are not limited to, delta-valerolactone; epsilon-caprolactone; zeta-enantholactone; the monoalkyl-valerolactones, e.g. the monomethyl-,monoethyl-, and monohexyl-valerolactones.  \n\n[0029] Cyclic ester/alkylene oxide copolymers can also be prepared by reacting a mixture comprising cyclic ester and alkylene oxide monomers, an interfacial agent such as a solid, relatively high molecular weight poly(vinylstearate) or lauryl methacrylate/vinyl chloride copolymer (reduced viscosity in cyclohexanone at $30^{\\circ}\\mathrm{C}$ from about 0.3 to about 1.0),in the presence of an inert normally-liquid saturated aliphatic hydrocarbon vehicle such as heptane and phosphorus pentafluoride as the catalyst therefore, at an elevated temperature, e.g.,about $80^{\\circ}~\\mathrm{C}$ ，  \n\n[0030]   Another type of active hydrogen-containing materials are the polymer polyol compositions obtained by polymerizing ethylenically unsaturated monomers in a polyol as described in U.S. Pat No. 3,383,351. Suitable monomers for producing such compositions include acrylonitrile, vinyl chloride, styrene, butadiene, vinylidene chloride and other ethylenically unsaturated monomers as identified and described in the above-mentioned U.S. patent. The polymer polyol compositions can contain from 1 to about 70 weight percent $(\\mathrm{wt}\\%)$ ,preferably about 5 to about $50\\mathrm{wt}\\%$ and most preferably about 10 to about 40 wt $\\%$ monomer polymerized in the polyol. Such compositions are conveniently prepared by polymerizing the monomers in the selected polyol at a temperature of about $40^{\\circ}\\mathrm{~C~}$ .to about $150^{\\circ}\\mathrm{~C~}$ . in the presence of a free radical polymerization catalyst such as peroxides, persulfates, percarbonate, perborates and azo compounds.  \n\n[0031] The exact polyol or polyols employed depends upon the desired characteristics of the polyurethane. In particular, variation in the polyol component and the structure of the amine in the chain extension process for forming the polyurethane can yield a wide range of moduli and toughness.  \n\n[0032] Catalysts include various inorganic metal compounds and metal compounds that include certain organic groups. Metal acetyl acetonates are preferred, based on metals such as aluminum, barium, cadmium, calcium, cerium (III), chromium (III), cobalt (II), cobalt (II), copper (II). indium, iron (Il), lanthanium, lead (II), manganese (II), manganese (II), neodymium, nickel (Il), palladium (II), potassium, samarium, sodium, terbium, titanium, vanadium, yttrium, zinc and zirconium. A common catalyst is bis(2,4- pentanedionate） nickel (I) (also known as nickel acetylacetonate or diacetylacetonate nickel) and derivatives thereof such as diacetonitrilediacetylacetonato nickel, diphenylnitirilediacetylacetonato nickel, bis(triphenylphosphine)diacetyl acetylacetonato nickel, and the like.  \n\n[0033]  Optionally, the water dispersible polyurethane may contain additional water dispersible components such as an acrylate, polyester or the like. Alternatively, these moieties may be chemically attached to the polyurethane to prevent phase separation or other film coating defect.  \n\n[0034] Suitable commercially available water dispersible polyurethanes include BAYHYDROL 121 available from Baser Corporation, WITCOBOND available from Witco Corporation, Q-THANE available from K J Quinn. Inc., K-FLEX available from King Industries, and FLEXANE available from the Air Products and Chemicals, Inc.  \n\n[0035] Depending on the particular silicone polymer or oligomer, the use of the co-solvent may be employed. Suitable co-solvents include N-methyl pyrrolidone,glycol ethers, isopropanol and combinations comprising, at least one of the foregoing co-solvents. In a preferred embodiment, the co-solvent is N-methyl pyrrolidone.  \n\n[0036] The coating compositions can additionally contain other additives and adjuvants, such as adherence modulators (linear silicone polymers or resins bearing vinyl, epoxy, vinyl ether, alcohol and the like functional groups), pigments (for example titanium dioxide and iron oxide), photosensitizing agents, fillers (alumina trihydrate, silica, talc, calcium carbonate, clay, and the like), dyes fungicidal, bactericidal and anti-microbial agents, antistatic agents, particulates which control the friction or surface contact areas, defoamers,buffers to control ply of the coating compositions, corrosion inhibitors and the like. Use of UV absorbers or light stabilizers, such as hindered amine light stabilizers, can be used to further impart UV resistance. Other additives may also be used, if desired.  \n\n[0037] The formulations are prepared by admixing the components together. Preferably, the formulations are prepared by adding a dilute silicone polymer or oligomer solution or dispersion to the water dispersible polyurethane dispersion.  \n\n[0038] Water and/or additional co-solvent is then added to achieve the desired solids content and viscosity. The additives and adjuvants, if present, may be added at any stage of the mixing process.  \n\n[0039] In another embodiment, the anti-tog coating composition is prepared by admixing the silicone polymer or oligomer with the components that form the water dispersible polyurethane, i.e., polyol, isocyanate and catalyst in a suitable solvent, coating a solution of the admixture, and curing the coated formulation to form a crosslinked film.  \n\n[0040] In another embodiment, the anti-fog coating formulation is prepared by admixing the silicone polymer or oligomer with the components that form the water dispersible polyurethane, i.e., polyol, isocyanate and catalyst, coating a substrate with the dispersion, and curing the coated formulation to form a coalesced film. In this embodiment, the silicone polymer or oligomer preferably comprises a functional group that is preferably a weak acid, e.g.,a carboxylic acid moiety. In this manner, the silicone component is chemically attached to the polyurethane and the resulting film is formed by coalescence. Advantageously, physical loss due of the silicone compound due to evaporation or the like is prevented.  \n\n[0041]  Any number of coating methods may be employed to coat the anti-fog coating composition onto a surface of a desired substrate, for example, roller coating,wire-bar coating,dip coating,extrusion coating, air knife coating, curtain coating, slide coating,blade coating, doctor coating,or gravure coating.  \n\n[0042] Preferably, the coated film is heat treated to form the coalesced or crosslinked polymeric network. Suitable temperatures for forming the coalesced or crosslinked polymeric network in the coating composition are preferably at about room temperature to about $150^{\\circ}\\mathrm{~C~}$ ，with $50^{\\circ}\\mathrm{~C~}$ .to $130^{\\circ}\\mathrm{~C~}$ . more preferred and with $100^{\\circ}\\mathrm{~C~}$ .to about $120^{\\circ}\\mathrm{~C~}$ even more preferred. The duration of heating should be effective to form the film and is preferably about 2 to about 60 minutes. These temperatures and times are not intended to be limiting, however, since those of ordinary skill in the art will recognize that the temperatures and times utilized will vary according to the actual physical characteristics of the formed coating (e.g., coating layer thickness, additives, ratios of components,etc.). Even so, as a general rule, the higher the treating temperature utilized, the more quickly the coalesced polymeric network forms in the coating composition.  \n\n[0043] The coat weight of the anti-fog coating is not particularly restricted, but ,should generally be in the range from about $0.5\\:\\mathrm{g}/\\mathrm{m}^{2}$ to about $15\\:\\mathrm{g}/\\bar{\\mathrm{m}}^{2}$ depending on the film thickness. For most applications, the thickness of the coating is preferably at about 0.5 to about 15 micrometers.  \n\n[0044]   The coatings are typically used to provide anti-fog properties to a surface of a substrate, wherein the substrate comprises a plastic or glass material. Suitable plastic materials include polyester, cellulose esters polycarbonate, polystyrene, poly(vinyl acetate), polyolefins, and the like. The substrate thickness is not particularly restricted, and usually depends entirely upon the application. Typical thicknesses are about O.oo5 inches to about 0.5 inches or monolithic structures, and about 4 millimeter to about 16 millimeters for structured substrates. The substrate may be pretreated to enhance adhesion of the anti-fog coating.  \n\n[0045] The following examples illustrate the disclosure without limitation. All parts are given by weight unless otherwise indicated.  \n\nEXAMPLE 1 [0046]  An anti-fog coating formulation is as follows.   \n\n\n<html><body><table><tr><td>Component</td><td>Amount (grams)</td></tr><tr><td>Polyol (RUCOFLEX S-1028)</td><td>20.0</td></tr><tr><td>Polyisocyanate (DESMODUR N-75)</td><td>10.0</td></tr><tr><td>Silicone</td><td>4.0</td></tr><tr><td>(poly[dimethylsiloxane-co-</td><td></td></tr></table></body></html>  \n\n-continued   \n\n\n<html><body><table><tr><td>Component</td><td>Amount (grams)</td></tr><tr><td>[3-[2-(hydroxyethoxy)ethoxy]</td><td></td></tr><tr><td>propyl]methyl-siloxane)</td><td></td></tr><tr><td>Catalyst (dibutylin dilaurate)</td><td>0.05</td></tr><tr><td>Diacetone alcohol</td><td>6.0</td></tr><tr><td>t-Butanol</td><td>60.0</td></tr></table></body></html>  \n\n[0047]  The formulation was applied to a polycarbonate substrate and dried in an oven at an elevated temperature forming a crosslinked film. The anti-fog film formed on the polycarbonate substrate exhibited improved flexibility e.g., elongation was greater than $50\\%$  \n\nEXAMPLE 2 [0048]  An anti-fog coating formulation is as follows.   \n\n\n<html><body><table><tr><td>Component</td><td>Amount (grams)</td></tr><tr><td>Polypropylene glycol diol (Mol. Wt.~1000, ARCO)</td><td>22.5 g</td></tr><tr><td>Hydrogenated diphenyl methane diisocyanate</td><td>9.8 g</td></tr><tr><td>Dimethylol propionic acid</td><td>1.25 g</td></tr><tr><td>Diethylene triamine</td><td>0.63g</td></tr><tr><td>Triethylamine</td><td>0.92 g</td></tr><tr><td>N-methyl-pyrrolidinone</td><td>16.5 g</td></tr><tr><td>Poly[dimethylsiloxane-co-methyl(3-</td><td>4.0g</td></tr><tr><td>hydroxypropyl)siloxane-graft- [poly(ethylene glycol) methyl ether]-</td><td></td></tr><tr><td>[poly(ethylene glycol)</td><td></td></tr><tr><td>Dibutyltin dilaurate</td><td>0.05 g</td></tr><tr><td>Water</td><td>44.4g</td></tr></table></body></html>  \n\n[0049] In this example, the silicone compound is chemically attached to the polyurethane during formation of an aqueous dispersion. Polypropylene glycol diol, dimethylol propionic acid (dissolved in $\\%$ of the N-methyl-pyrrolidinone), and dibutyltin dilaurate are charged into a reactor with temperature control under a nitrogen environment at a temperature about $80^{\\circ}\\mathrm{~C~}$ . Hydrogenated diphenyl methane diisocyanate is added slowly to the reactor and the reaction is continued for 3 hours until the theoretical $N C O\\ \\%$ is reached. The reaction mixture is then cooled to $60^{\\circ}\\mathrm{~C~}$ Triethylamine is then added to neutralize the acid functionalities. Water is then added with vigorous agitation to form the dispersion. To this a diethylene triamine/N-methylpyrrolidinone/water solution is added to complete chain extension and the reaction is kept for 2 hours. The resulting polyurethane dispersion had a solids content of about 35 to about 40-weight $\\%$  \n\n[0050] The dispersion is then applied to a substrate and dried at an elevated temperature in an oven. The resulting film is formed by coalescence and exhibited anti-fog properties.  \n\n[0051] An anti-fog coating formulation is as follows.   \n\n\n<html><body><table><tr><td>Component</td><td>Amount (grams)</td></tr><tr><td>Silicone compound (poly[dimethylsiloxane-co-</td><td>2</td></tr><tr><td>[3-[2-(hydroxyethoxy)ethoxy] propyl]methyl-siloxane)</td><td></td></tr><tr><td>Polyurethane Aqueous Dispersion (BAYHYDROL 121)</td><td>58</td></tr><tr><td>UV Absorber (TINUVIN 400, Ciba Specialty Chemicals)</td><td>1.5</td></tr><tr><td>UV Light Stabilizer (UVENUL 3058, BASE Corp.)</td><td>0.05</td></tr><tr><td>Water</td><td>38.45</td></tr></table></body></html>  \n\n[0052]The coating composition of Example 2 was applied at a thickness of about 8 micrometers to a polycarbonate film and dried at $130^{\\circ}\\mathrm{~C~}$ .for 30 minutes. The properties of the coated substrate were evaluated and are summarized in Table 1.  \n\nTABLE1   \n\n\n<html><body><table><tr><td>TEST</td><td>RESULTS</td></tr><tr><td>Fogging Time</td><td>Greater than 60 seconds</td></tr><tr><td>Sheeting Performance</td><td>No bead or droplet formation</td></tr><tr><td>Xenon Arc accelerated</td><td>YI ≤ about 2, no delamination after</td></tr><tr><td>weathering</td><td>3000 hours</td></tr><tr><td>QUVB (FS-40) accelerated</td><td>YI ≤ about 6, no delamination after</td></tr><tr><td>weathering</td><td>3000 hours</td></tr><tr><td>Impact Resistaiice</td><td>≥ about 160 to about 200 pounds</td></tr></table></body></html>  \n\n[0053]  Fogging time is expressed as the time it takes to visually form a fog on a surface of the coating by placing the coating T inch above a vessel of water (coating surface facing the water). The water was heated to a temperature of $55^{\\circ}$ C. No fogging was observed after 60 seconds of exposure.  \n\n[0054]  Sheeting performance is a qualitative measure of the anti-condensation properties commonly used for measuring the applicability of the product for greenhouse window applications.A stream of water is applied to the coated surface at a $45^{\\circ}$ angle and its flow pattern is observed. If the water flow forms a continuous path, the performance is considered acceptable. In contrast, if the water forms a bead or droplets upon the surface, the performance is considered unacceptable. Acceptable sheeting performance was observed for the coated substrate.  \n\n[0055] The weatherability testing,included exposing the coated surface of the substrate to a xenon arc light source or a QUVB light source. An Atlas Ci35 Xenon Arc weatherometer was employed for exposing the coating to the xenon light source and included a borosilicate glass filter element for filtering wavelengths less than about 290 nanometers. The weathering cycle included a 16O-minute exposure at $70^{\\circ}$ C.and $50\\%$ relative humidity followed by a 5 minute cool down in the dark and a 15-minute water spray. The average irradiance was 0.77-watts/square meter at 340 nanometers. The weathering cycle was continuously repeated for a period of 3000 hours. Under these conditions, the yellowing index (YI) indicated that yellowing was minimal. Moreover, the coated samples did not show any visible signs of delamination.  \n\n[0056] The QUVB weathering device was outfitted with an FS40 lamp. Samples were disposed in the chamber of the device. The weathering cycle included exposure to the FS40 lamp for a period of 8 hours at $70^{\\circ}\\mathrm{~C~}$ followed by 4 hours of dark time at $50^{\\circ}\\mathrm{~C~}$ . The weathering cycle was continuously repeated for a total time period of 3ooo hours. No delamination was observed after exposure and yellowing was minimal.  \n\n[0057] The impact resistance was measured in accordance with ASTM D2794. The test was conducted on a $10\\ \\mathrm{mil}$ double wall polycarbonate sheet with a coating thickness of 8 microns. The results clearly show that the use of polyurethane in the coating composition maintains the impact resistance of the coated sample. Impact resistance was greater than 160-200 pounds.  \n\n[0058] Advantageously, the coating compositions can be used to form films exhibiting excellent anti-fog and anticondensation properties. Moreover, the coating compositions show fast drying behavior resulting in improved productivity cycles, use less solvent usage than prior art compositions, show less degradation during extrusion, and maintain sufficient impact strength for use in numerous applications.  \n\n[0059] While the invention has been described with reference to an exemplary embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition,many modifications may be made to adapt a particular situation or material to the teaching s of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.  \n\nWhat is claimed is:  \n\n1. An anti-fog coating composition comprising a silicone compound free from a sulfonic acid functional group, a water dispersible polyurethane compound, and water.  \n\n2. The anti-fog coating composition according to claim 1. wherein the silicone compound is present in the coating composition at about 0.1 to about 20 weight percent, and wherein the polyurethane compound polymer present in the coating composition is about 5 to about 5O weight percent, based on the total weight of the coating composition.  \n\n3. The aqueous coating composition according to claim 1, wherein the silicone compound is of the formula:  \n\n$$\n\\mathrm{{\\bfM_{a}M_{b}D_{c}D_{d}^{\\prime}T_{e}T_{f}Q_{g}}},\n$$  \n\nwherein the subscripts a, c, d, e, f, and $\\mathbf{g}$ are zero or a positive integer, subject to the limitation that the sum of the subscripts b, d, and $\\mathrm{\\Phi_{f}}$ is one or greater; M has the formula: $\\mathrm{R}_{3}^{\\mathrm{~\\bar{1}~}}\\mathrm{SiO}_{1/2}$ ，wherein each $\\bar{\\mathbf{R}^{1}}$ is independently a monovalent hydrocarbon radical having from one to forty carbon atoms; $\\mathbf{M}^{\\prime}$ has the formula: $\\breve{\\mathrm{R}}{}^{2}{}_{3-\\mathrm{h}}\\mathrm{R}{}^{3}{}_{\\mathrm{h}}\\mathrm{SiO}_{1/}$ $_2$ ，wherein each ${\\mathrm{R}}^{2}$ and ${\\mathrm{R}}^{3}$ are independently monovalent hydrocarbon radicals having from one to forty carbon atoms, and the subscript h is 1, 2, or 3; D has the formula: $\\mathbf{R}_{\\:2}^{4}\\mathbf{SiO}_{2/2}$ ，wherein each ${\\bf R}^{4}$ is independently a monovalent hydrocarbon radical having from one to forty carbon atoms; $\\mathbf{D^{\\prime}}$ has the formula: $\\mathbf{R}_{2-1}^{\\lessgtr}\\mathbf{R}_{1}^{6}\\mathbf{SiO}_{2/2}$ wherein each of $\\mathbf{R}^{5}$ and $\\mathbb{R}^{6}$ is independently a monovalent hydrocarbon radical having from one to forty carbon atoms, and the subscript i is_1 or 2; T has the formula: $\\mathbf{R}^{7}\\mathbf{SiO}_{3/2}$ ，wherein each ${\\bf R}^{7}$ is a monovalent hydrocarbon radical having from one to forty carbon atoms; $\\mathrm{T}^{\\prime}$ has the formula: $\\mathrm{R}^{8}\\mathrm{SiO}_{3/2}$ ，wherein $\\mathbb{R}^{\\mathrm{s}}$ is a monovalent hydrocarbon radical having from one to forty carbon atoms: and Q has the formula: $\\mathrm{SiO}_{4/2}$ ·  \n\n4. The aqueous coating composition according to claim 1, wherein the silicone compound is an ionic or nonionic siloxane alkoylate of the formula:  \n\n![](images/7f28592851417bcfa74be79004cf34abf6ac641a1de3d86bf9dace81f61d9cdc.jpg)  \n\nwherein each of $\\mathbf{R}^{9}$ through $\\mathbf{R}^{17}$ are independently a monovalent hydrocarbonylradical,and $\\mathbb{R}^{18}$ is $\\mathrm{R}^{19}{-}\\dot{\\mathrm{Z}}{-}(\\mathrm{C}_{\\mathrm{m}}\\mathrm{H}_{(2\\mathrm{m}-}$ $\\mathrm{1)R^{20}\\mathrm{\\dot{O})_{j}(C_{n}H_{2n}O)_{k}}{R^{21}}}$ , wherein in and n are integers greater than or equal to O; j and $\\mathbf{k}$ are integers greater than or equal to O, subject to the proviso that the sum of $\\mathbf{j}{+}\\mathbf{k}$ is greater than or equal to $\\scriptstyle1;Z$ is $\\mathrm{~H~}$ ，—0—， $\\bf-s-$ $\\mathrm{-}\\mathrm{\\mathbf{S}H-}$ ，—CO—， ${\\mathrm{-NH-}}$ ，or $-\\mathrm{NH}_{\\gamma}{\\mathrm{-}};\\mathrm{~}\\mathrm{R}^{19}$ is a divalent hyrdocarbylene radical, $\\operatorname{R}^{20}$ and $\\mathbb{R}^{\\Bar{2}1}$ are independently hydrogen, alkyl, hydroxyalkyl, amino, amido, amineoxide, cyano, isocyano, aryl, arylene, carboxy, alkoxy, halogen, haloalkyl, haloalkyoxy,sulfo, sulfamo, phophono, salts thereof, combinations comprising at least one of the foregoing moieties, and wherein $\\mathbf{x}$ and $\\mathbf{v}$ are integers greater than or equal to 0, subject to the proviso that $\\mathbf{x}{+}\\mathbf{y}$ is greater than or equal to 1. 5. The coating composition according to claim 1, further comprising an additive selected from the group comprising a UV absorber, an antistatic agent, pigments, photosensitizing agents, fillers, dyes, fungicidal, bactericidal and antimicrobial agents, antistatic agents, particulates which control the friction or surface contact areas, defoamers, buffers to control $\\mathrm{pH}$ of the coating compositions,corrosion inhibitors, combinations comprising at least one of the foregoing, and the like.  \n\n6. The coating composition according to claim 1,further comprising a co-solvent selected from the group consisting of N-methyl pyrrollidone, glycol ether, isopropanol, and combinations comprising at least one of the foregoing co-solvents.  \n\n7. The coating composition according to claim 1,wherein the silicone compound is chemically bound to the polyurethane compound.  \n\n8.The coating composition according to claim 6, wherein the co-solvent present in the coating composition is about 5 to about 1O weight percent, based on the total weight of the coating composition.  \n\n9. A process for forming an anti-fog film on a substrate comprising  \n\napplying an aqueous coating composition to the substrate, wherein the aqueous coating composition comprises a silicone compound free from a sulfonic acid group, a water dispersible polyurethane compound, and water; and  \n\ncoalescing the silicone compound and polyurethane compound to form a film on the substrate.  \n\n10. The process according to claim 9, wherein the silicone compound comprises the formula:  \n\n$$\n\\mathbf{M_{a}M_{b}^{\\prime}D_{c}D_{d}^{\\prime}T_{e}}\\mathbf{T_{f}}\\mathbf{Q_{g}},\n$$  \n\nwherein the subscripts a,c, d, e,f, and $\\mathbf{g}$ are zero or a positive integer, subject to the limitation that the sum of the subscripts b, d, and $\\mathrm{\\Phi_{f}}$ is one or greater; M has the formula: $\\mathrm{R}^{\\bar{1}}{}_{3}\\mathrm{SiO}_{1/2}$ ,wherein each ${\\bf R}^{1}$ is independently a monovalent hydrocarbon radical having from one to forty carbon atoms; M' has the formula: $\\mathrm{R}_{3-\\mathrm{h}}^{\\bar{2}},\\mathrm{R}_{\\mathrm{~h}}^{3}\\mathrm{SiO}_{1/}$ 2,wherein each $\\mathbf{R}^{2}$ and $\\mathbb{R}^{3}$ are independently monovalent hydrocarbon radicals having from one to forty carbon atoms, and the subscript h is 1, 2, or 3; D has the formula: $\\mathrm{R}_{\\ 2}^{4}\\mathrm{SiO}_{2/2}$ ，wherein each $\\mathrm{R}^{4}$ is independently a monovalent hydrocarbon radical having from one to forty carbon atoms: D' has the formula: $\\bar{\\mathbf{R}^{5}}_{2-1},\\mathbf{R}^{6}_{1}\\mathbf{SiO}_{2/}$ 2,wherein each of $\\mathbf{R}^{5}$ and $\\mathbb{R}^{6}$ is independently a monovalent hydrocarbon radical having from one to forty carbon atoms, and the subscript i is 1 or 2; T has the formula: $\\mathbf{R}^{7}\\mathbf{SiO}_{3/2}$ ，wherein each ${\\bf R}^{7}$ is a monovalent hydrocarbon radical having from one to forty carbon atoms; T' has the formula: $\\mathrm{\\bar{R}}^{\\mathrm{s}}\\mathrm{SiO}_{3/2}$ ,wherein $\\bar{\\mathbf{R}^{\\mathrm{s}}}$ is a monovalent hydrocarbon radical having from one to forty carbon atoms: and Q has the formula: $\\mathrm{SiO}_{4/2}$  \n\n11.The process according to claim 9, wherein the silicone compound is an ionic or nonionic siloxane alkoylate of the formula:  \n\n![](images/0df25caf7625c7b60a0ad2317d908118a377b0ac5cca5f046cc7fbae488e967d.jpg)  \n\nwherein each of $\\mathbf{R}^{9-17}$ are independently a monovalent hydrocarbonyl radical, $\\mathbb{R}^{18}$ is of the general formula: $\\mathbf{R}^{19}$ $\\bar{\\mathrm{Z}}\\mathrm{-}(\\mathrm{C_{m}H_{\\mathrm{(2m-1)}}R^{20}O)_{j}(\\mathrm{C_{n}H_{2n}O)_{k}R^{21}}}$ , m and n are integers greater than or equal to $\\mathbf{0;j}$ and k are integers greater than or equal to O subject to the proviso that the sum of j $\\mathrm{i+k}$ is greater than or equal to 1; Z is $\\mathrm{~H~}$ P $\\mathrm{-O-}$ ,—S- -SH—,—CO—， ${\\mathrm{-NH}{\\mathrm{-}}},$ or $\\mathrm{-NH_{2}\\mathrm{-;\\thinspaceR^{19}}}$ is a divalent hydrocarbylene radical, $\\mathbf{R}^{20}$ and $\\mathbf{R}^{\\bar{2}1}$ are independently hydrogen, alkyl, hydroxyalkyl, amino, amido, amineoxide, cyano, isocyano, aryl, arylene, carboxy, alkoxy, halogen, haloalkyl, haloalkyoxy, sulfo, sulfamo, phophono, salts thereof, combinations comprising at least one of the foregoing, and the like; and wherein $\\mathbf{x}$ and $\\mathbf{y}$ are integers greater than or equal to 0, subject to the proviso that $\\mathbf{x}+\\mathbf{y}$ is greater than or equal to 1.  \n\n12. The process according to claim 9, further comprising heating the substrate to a temperature of about $20^{\\circ}\\mathrm{~C~}$ .to about $150^{\\circ}\\mathrm{~C~}$ ，  \n\n13.The process according to claim 9, wherein the substrate comprises a polyester, a cellulose ester, a polycarbonate,a polystyrene, a polyvinyl acetate,a polyolefin, and combinations comprising at least one of the foregoing.  \n\n14.The process according to claim 9, wherein the aqueous coating composition further comprises a co-solvent selected from the group consisting of N-methyl pyrrolidone, glycol ether, isopropanol, and combinations comprising at least one of the foregoing co-solvents.  \n\n15.The process according to claim 9, wherein the silicone compound is chemically bound to the polyurethane com pound.  \n\n16. The process according to claim 14, wherein the co-solvent is about 5 to about 10 weight percent of the coating composition.  \n\n17. A glass or plastic article having an anti-fogging surface comprising:  \n\na glass or plastic substrate, and an anti-fog coating disposed on at least one surface of the substrate, the anti-fog coating comprising a silicone compound free of a sulfonic acid function group, a water dispersible polyurethane compound, and water.  \n\n18.The glass or plastic article of claim 17, wherein the silicone compound is of the formula:  \n\n$$\n\\mathbf{M_{a}M_{b}D_{c}D_{d}^{\\prime}T_{e}T_{f}Q_{g}},\n$$  \n\nvherein the subscripts a, c, d, e, f, and $\\mathbf{g}$ are zero or a positive integer, subject to the limitation that the sum of the subscripts b, d, and f is one or greater; M has the formula: $\\mathrm{R}^{\\bar{1}}{}_{3}\\mathrm{SiO}_{1/2}$ ,wherein each R is independently a monovalent hydrocarbon radical having from one to forty carbon atoms. $\\mathbf{M^{\\prime}}$ has the formula: $\\mathrm{{\\bf{R}}}^{2}{}_{3-\\mathrm{{h}}}\\mathrm{{R}}^{3}{}_{\\mathrm{h}}\\mathrm{{SiO}}_{1/}$ 2, wherein each ${\\tt R}^{2}$ and ${\\mathbb{R}}^{3}$ are independently monovalent hydrocarbon radicals having from one to forty carbon atoms, and the subscript hi is 1, 2, or 3; D has the formula: $\\mathrm{R}^{4}{}_{2}\\mathrm{SiO}_{2/2}$ ，wherein each $\\mathrm{R}^{4}$ is independently a monovalent hydrocarbon radical having from one tofortycarbon atoms; ${\\bf D}^{\\prime}$ has the formula: $\\begin{array}{r}{\\mathbf{R}_{\\:2}^{5}.}\\end{array}$ $\\mathrm{iR}^{6}{}_{\\mathrm{i}}\\mathrm{SiO}_{2/2}$ , wherein each of $\\mathbf{R}^{5}$ and $\\mathrm{~\\bf~R~}^{6}$ is independently a monovalent hydrocarbon radical having from one to forty carbon atoms, and the subscript i is 1 or 2; T has the formula: $\\mathrm{R}^{7}\\mathrm{SiO}_{3/2}$ ，wherein each ${\\bf R}^{7}$ is a monovalent hydrocarbon radical having from one to forty carbon atoms; T' has the formula: $\\mathrm{\\bar{R}}^{\\mathrm{s}}\\mathrm{SiO}_{3/2}$ ,wherein $\\mathrm{R}^{\\mathrm{\\bar{s}}}$ is a monovalent hydrocarbon radical having from one to forty carbon atoms; and Q has the formula: $\\mathrm{SiO}_{4/2}$ ；  \n\n19.The glass or plastic article of claim 17, wherein the silicone compound is an ionic or nonionic siloxane alkoylate of the formula:  \n\n![](images/4957f15157ddb57604d2886b706f86491dc32e320155654160658951256f62e5.jpg)  \n\nwherein each of $\\mathbf{R}^{9-17}$ are independently a monovalent hydrocarbonyl radical, $\\mathbb{R}^{18}$ is of the general formula: $\\mathbf{R}^{19}$ $\\dot{\\mathrm{Z}}\\mathrm{-}(\\mathrm{C_{m}H_{(2m-1)}R^{20}O)_{j}(\\mathrm{C_{n}H_{2n}O)_{k}R^{21}}}$ ， $\\mathbf{m}$ and n are integers greater than or equal to 0; $\\mathrm{j}$ and k are integers greater than or equal to O, subject to the proviso that the sum of $\\mathrm{j+k}$ is greater than or equal to 1:Z is $\\mathrm{~H~}$ 。 $^{-0-}$ ，—S—， $-\\mathrm{SH}-$ CO—，—NH—,or $\\mathrm{-NH}_{2}\\mathrm{-};\\mathrm{R}^{19}$ is a divalent hyrdocarbylene radical. $\\mathbb{R}^{20}$ and $\\mathbb{R}^{2\\Bar{1}}$ are independently hydrogen, alkyl, hydroxyalkyl, amino, amido,amineoxide, cyano, isocyano, aryl, arylene,carboxy, alkoxy, halogen, haloalkyl, haloalkyoxy, sulfo, sulfamo, phophono, salts thereof, combinations comprising at least one of the foregoing, and the like; and wherein $\\mathbf{x}$ and $\\mathbf{y}$ are integers greater than or equal to O, subject to the proviso that $\\mathbf{x}{+}\\mathbf{y}$ is greater than or equal to 1.  \n\n20. The glass or plastic article of claim 17, wherein the plastic substrate comprises a material selected from the group of polycarbonate, cellulose esters, polystyrene, polyvinyl acetate, polyolefins, polyester, and the like.  \n\n21. A process for forming an anti-fog film, the process comprising:  \n\napplying a coating composition to a substrate, wherein the coating composition comprises a silicone compound free from a sulfonic acid functional group, an isocyanate, a polyol and a catalyst; and  \n\ncrosslinking the coating composition to form the anti-fog film,wherein the crosslinking comprises heating the substrate to a temperature and for a time effective to form the film.  \n\n22. The process according to claim 21,wherein the silicone compound comprises the formula:  \n\n$$\n\\mathrm{{\\bfM_{a}M_{b}D_{c}D_{d}^{\\prime}T_{e}T_{f}Q_{g}}},\n$$  \n\nwherein the subscripts a, c, d, e, f, and $\\mathbf{g}$ are zero or a positive integer, subject to the limitation that the sum of the subscripts b, d, and f is one or greater; M has the formula: $\\mathrm{R}_{3}^{1}\\mathrm{SiO}_{1/2}$ ，wherein each ${\\bf R}^{1}$ is independently a monovalent hydrocarbon radical having from one to forty carbon atoms; $\\mathbf{M}^{\\prime}$ has tie formula: $\\mathrm{R}^{\\bar{2}}{}_{3\\mathrm{-h}}\\mathrm{R}^{3}{}_{\\mathrm{h}}\\mathrm{SiO}_{1/2}$ wherein each ${\\mathrm{R}}^{2}$ and $\\mathbb{R}^{3}$ are independently monovalent hydrocarbon radicals having from one to forty carbon atoms, and the subscript h is 1,2, or 3; D has the formula: $\\mathrm{R}_{~2}^{4}\\mathrm{SiO}_{2/2}$ ,wherein each $\\mathrm{R}^{4}$ is independently a monovalent hydrocarbon radical having from one to forty carbon atoms; ${\\bf D}^{\\prime}$ has the formula: $\\mathbf{R}^{5}{}_{2-1}\\mathbf{R}^{6}{}_{1}\\mathbf{SiO}_{2/2}$ ， wherein each of $\\mathbf{R}^{5}$ and $\\mathbb{R}^{6}$ is independently a monovalent hydrocarbon radical having from one to forty carbon atoms, and the subscript i is 1 or 2; T has the formula: $\\mathbf{R}^{7}\\mathbf{SiO}_{3/2}$ ，wherein each ${\\bf R}^{7}$ is a monovalent hydrocarbon radical having from one to forty carbon atoms; $\\mathrm{\\DeltaT^{\\prime}}$ has the formula: $\\mathrm{R}^{\\mathrm{8}}\\mathrm{SiO}_{3/2}$ ，wherein $\\mathbb{R}^{\\mathrm{s}}$ is a monovalent hydrocarbon radical having from one to forty carbon atoms; and Q has the formula: $\\mathrm{SiO}_{4/2}$ ·  \n\n23. The process according to claim 2, wherein the silicone compound is an ionic or nonionic siloxane alkoylate of the formula:  \n\n![](images/47827cf4ff7bafc2d60eef243b674811628e2d008dfd5df25a6a8cecbeed3888.jpg)  \n\nwherein each of $\\mathbf{R}^{9-17}$ are independently a monovalent hydrocarbonyl radical, $\\mathbf{R}^{18}$ is of the general formula: $\\mathrm{R}^{19}-$ $\\dot{\\mathrm{Z}}\\mathrm{-}(\\mathrm{C_{m}H_{(2m-1)}R^{20}O)_{j}(\\mathrm{C_{n}H_{2n}O)_{k}R^{21}}}$ ,m and n are integers greater than or equal to O; j and k are integers greater than or equal to 0, subject to the proviso that the sum of $\\mathbf{j}{+}\\mathbf{k}$ is greater than or equal to 1; $Z$ is $\\mathrm{H,-O-,-s-,-sH-,}$ -CO—， ${\\mathrm{-NH-}}$ or $-\\mathrm{NH}_{2}{\\mathrm{-}};\\mathrm{R}^{9}$ is a divalent hyrdocarbylene radical, $\\scriptstyle\\mathbf{R}^{20}$ and $\\mathbf{R}^{21}$ are independently hydrogen, alkyl, hydroxyalkyl, amino, amido, amineoxide, cyano, isocyano, aryl, arylene,carboxy, alkoxy, halogen, haloalkyl, haloalkyoxy, sulfo, sulfamo, phophono, salts thereof, combinations comprising at least one of the foregoing, and the like; and wherein $\\mathbf{x}$ and $\\mathbf{y}$ are integers greater than or equal to O, subject to the proviso that $\\mathbf{x}+\\mathbf{y}$ is greater than or equal to 1.  \n\n24.The process according to claim 21, wherein crosslinking the coating composition to form the anti-fog film comprises heating the substrate to a temperature of about $20^{\\circ}\\mathrm{C}$ to about $150^{\\circ}$ C.  \n\n25. The process according to claim 21,wherein the substrate comprises a polyester, a cellulose ester, a polycarbonate, a polystyrene, a polyvinyl acetate, a polyolefin, and combinations comprising at least one of the foregoing.  \n\n26.The process according to claim 21, wherein the polyol comprises a polycarbonate polyol.  \n\n27. A glass or plastic article having an anti-fogging surface comprising:  \n\na glass or plastic substrate; and an anti-fog coating disposed on at least one surface of the substrate, the anti-fog coating comprising a crosslinked film formed from a silicone, an isocyanate, a polyol and a catalyst.  \n\n28. The glass or plastic article of claim 27, wherein the silicone compound comprises the formula:  \n\n$$\n\\mathbf{M_{a}M_{b}^{\\prime}D_{c}D_{d}^{\\prime}T_{e}T_{f}Q_{g}},\n$$  \n\nwherein the subscripts a, c, d, e, f, and $\\mathbf{g}$ are zero or a positive integer, subject to the limitation that the sum of the subscripts b, d, and I is one or (greater: M has the formula: $\\mathrm{R}_{3}^{1}\\mathrm{SiO}_{1/2}$ ，wherein each ${\\bf R}^{1}$ is independently a monovalent hydrocarbon radical having from one to forty carbon atoms; $\\mathbf{M}^{\\prime}$ has the formula: $\\mathrm{R}_{3-\\mathrm{h}}^{2}\\mathrm{R}_{\\mathrm{~h}}^{3}\\mathrm{SiO}_{1/}$ $\\scriptstyle2,$ wherein each ${\\mathrm{R}}^{2}$ and ${\\bf R}^{3}$ are independently monovalent hydrocarbon radicals having from one to forty carbon atoms, and the subscript h is 1, 2, or 3; D has the formula: $\\mathrm{R}_{~2}^{4}\\mathrm{SiO}_{2/2}$ ，wherein each $\\mathrm{R}^{4}$ is independently a monovalent hydrocarbon radical having from one to forty carbon atoms; ${\\bf D}^{\\prime}$ has the formula: $\\mathbf{R}_{2-1}^{5}\\mathbf{R}_{1}^{6}\\mathbf{SiO}_{2/2}$ wherein each of $\\mathbf{R}^{5}$ and $\\mathbf{R}^{6}$ is independently a monovalent hydrocarbon radical having from one to forty carbon atoms, and the subscript i is 1 or 2; T has the formula: ${\\bf R}^{7}{\\bf S}\\mathrm{i}\\mathrm{O}_{3/2}$ ，wherein each ${\\bf R}^{7}$ is a monovalent hydrocarbon radical having from one to forty carbon atoms; T' has the formula: $\\mathrm{R}^{8}\\mathrm{SiO}_{3/2}$ ，wherein $\\textstyle\\mathrm{R}^{8}$ is a monovalent hydrocarbon radical having from one to forty carbon atoms; and Q has the formula: $\\mathrm{SiO}_{4/2}$  \n\n29.The glass or plastic article of claim 27, wherein the silicone compound is an ionic or nonionic siloxane alkoylate of the formula:  \n\n![](images/c10048675bd0f3b63bf49adbd9d47ec51efb418f7bde2d954b48d733fa9470c6.jpg)  \n\nwherein each of $\\mathbf{R}^{9-17}$ are independently a monovalent hydrocarbonyl radical, $\\mathbb{R}^{18}$ is of the general formula: $\\mathrm{R}^{19}-$ $\\dot{\\mathrm{Z}}\\mathrm{-}(\\mathrm{C_{m}H_{(2m-1)}R^{20}O)_{j}(\\mathrm{C_{n}H_{2n}O)_{k}R^{21}}}$ ,m and n are integers greater than or equal to O; j and k are integers greater than or equal to O, subject to the proviso that the sum of $\\mathbf{j}{+}\\mathbf{k}$ is greater than or equal to 1; $z$ is $\\mathrm{~H~}$ ，—O—，—S—，—SH—  \n\nCO—.—NH—,or $-\\mathrm{NH}_{2}{\\mathrm{-}};\\mathrm{R}^{19}$ is a divalent hyrdocarbylene radical, $\\mathbb{R}^{20}$ and $\\mathbb{R}^{21}$ are independently hydrogen, alkyl, hydroxyalkyl, amino, amido, amineoxide, cyano, isocyano, aryl, arylene,carboxy, alkoxy, halogen, haloalkyl, haloalkyoxy, sulfo sulfamo, phophono, salts thereof, combinations comprising at least one of the foregoing, and the like; and wherein $\\mathbf{x}$ and $\\mathbf{y}$ are integers greater than or equal to 0. subject to the proviso that $\\mathbf{x}+\\mathbf{y}$ is greater than or equal to 1.  \n\n30. The glass or plastic article of claim 27, wherein the polyol comprises a polycarbonate polyol.",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,57 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19) United States (12) Patent Application Publication (10) Pub. No.: US 2008/0076851 A1 Goldberg et al. (43) Pub. Date: Mar. 27, 2008",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (54) HYDROPHILIC SURFACE MODIFICATION OF CONTACTLENSES",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# Publication Classification  \n\n(76） Inventors: Eugene P. Goldberg, Mt. Dora, FL (US); Khalid Mentak, San Ramon, CA (US); Daniel Urbaniak, Aliso Viejo, CA (US); Amin Elachchabi, Hamden, CT (US)  \n\nCorrespondence Address: MILES & STOCKBRIDGE PC 1751PINNACLEDRIVE SUITE 500 MCLEAN, VA 22102-3833 (US)  \n\n(21) Appl. No.: 11/892,965   \n(22) Filed: Aug. 28, 2007",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# Related U.S. Application Data  \n\n(60）Provisional application No. 60/840,469, filed on Aug. 28,2006.  \n\n(51) Int. Cl. C08J 3/28 (2006.01) G02B1/04 (2006.01)   \n(52) U.S. Cl. 523/106",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# ABSTRACT  \n\nAn improved method for modifying the surface of an article, the surface adapted for contact with living tissue of a human or non-human animal, by the gamma- or electron beamirradiation induced polymerized, chemically grafted coating thereon of a hydrophilic monomer to form a hydrophilic graft polymer coating of the polymerized monomer or mixture of monomers, the improvement comprising conducting the gamma- or electron beam-irradiation induced graft polymerization in an aqueous solution containing a hydrophilic polymer under conditions whereby the hydrophilic polymer is at least partially entrapped in the graft polymerized coating.",
+        "category": " Abstract"
+    },
+    {
+        "id": 6,
+        "chunk": "# HYDROPHILIC SURFACE MODIFICATION OF CONTACTLENSES  \n\nFIELDOFTHEINVENTION  \n\n[0001]   The present invention relates to contact lenses and the like and methods for improving the surfaces thereof.",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# BACKGROUND OF THE INVENTION  \n\n[0002] At the present time, contact lenses (CL) and the like which are intended for contact with sensitive tissue surfaces are constructed of materials having the necessary physical properties to enable their use for the intended application such as extended wear CLs; however, they suffer from the disadvantage that due to the generally hydrophobic nature of tissue contacting surfaces thereof, they exhibit undesired properties and significant damage may occur to fragile or sensitive tissues by adhesion and manipulation or movement on contact with the CLs.  \n\n[0003]A variety of different types of processes for preparing hydrophilic polymeric coatings on an“inert” hydrophobic substrate have been disclosed in the prior art. For example, surface treatments with various oxidizing agents and primers prior to applying a hydrophilic coating have been described in the literature.  \n\ntreating contact lenses to enhance the lubricity of the surfaces thereof and improve the overall biocompatibility thereof.  \n\n[0004]In contact lens (CL) manufacture, plasma treatment has been used to render the surface wettable, more lubricious, and the lens more comfortable to wear. However, a plasma treatment as part of high volume production requires a considerable investment in equipment and is difficult to integrate into automated production processes. For example, a batch process plasma treatment requires high vacuum conditions and the CL must be dried before exposure to the plasma. Thus, polymeric article such as a CL that is wet from prior hydration or purification by solvent extraction must be dried\\~thereby adding time and equipment expense in the overall lens production process. In addition, drying a hydrogel type contact lenses often affects the shape and optical quality in an irreversible manner and may create superficial cracks. Therefore, it would be highly desirable to covalently bind of a stable hydrophilic layer to an“inert\" surface by a process that avoids plasma treatment.  \n\n[0005] In U.S.Pats.Nos. 4,806,382; 4,961,954; 5,094, 876; 5,100,689; 5,108,776; 4,876; 5,290,548; 5,376,400; 5,885,566; 6,387,379; 5,804,263 and 5,698,192, there are described improved methods for producing hydrophilic, gamma- or electron beam-irradiation induced polymerized and chemically grafted coatings on instruments, devices such as contact lenses and the like so constructed of a variety of polymeric materials.  \n\n[0006] The invention described in the above-noted patents is predicated on the discovery of certain process conditions and parameters that produce thin, hydrophilic, gammairradiation polymerized and chemically grafted coatings of N-vinylpyrrolidone (NVP), copolymerized NVP and 2-hydroxyethyl-methacrylate(HEMA)，(NVP-HEMA）or HEMA-PHEMA) on the surfaces of articles adapted for contact with living tissue of a human or non-human animal, e.g.， surgical instruments, medical devices, prosthetic implants, contact lenses and the like constructed of a wide variety of plastic materials.  \n\n[0007]  It is an object of the present invention to provide improved contact lenses as well as improved methods for",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# SUMMARYOFTHEINVENTION  \n\n[0008] One embodiment of the invention relates to an improved method for modifying a plastic surface of an article, the surface adapted for contact with living tissue of a human or non-human animal, by the gamma- or electron beam-irradiation induced polymerized, chemically grafted coating thereon of a hydrophilic monomer such as N-vinylpyrrolidone(NVP)，2-hydroxyethylmethacrylate (HEMA), dimethylacrylamide (DMA) and the like as well as mixtures thereof with each other or with up to about 50 wt. $\\%$ ，based on the total monomer weight, of an ionic monomer, salt of an ionic monomer or mixture thereof, so as to form a hydrophilic graft polymer coating of the polymerized monomer or mixture of monomers, the improvement comprising conducting the gamma-irradiation induced graft polymerization in an aqueous solution also containing a hydrophilic polymer.  \n\n[0009] Another embodiment of the invention relates to articles of manufacture prepared according to the abovedescribed method.",
+        "category": " Abstract"
+    },
+    {
+        "id": 9,
+        "chunk": "# DETAILED DESCRIPTION OF THE INVENTION  \n\n[0010]  The present invention is predicated on the discovery that the inclusion of pre-polymerized hydrophilic polymers in the monomer or monomer/mixture subjected to high energy radiation induced graft polymerization on surfaces of articles designed for contact with tissue such as contact lenses, for example, results in the production of surfaces wherein the pre-polymerized polymer is entrapped or enmeshed in the graft coating as it forms, resulting in surfaces with enhanced lubricity and improved biocompatibility than similar methods carried out on the absence of such polymers. The invention described here for CL surface treatment is therefore a technique which is easy to perform with standard equipment under ambient conditions, and which is thus more feasible for an automated production process.  \n\n[0011] As noted above, hydrophilic surface modification using high-energy radiation has been described in the prior art. The object of this invention is to provide an improved process for hydrophilic surface modification using high energy radiation suitable for contact lens modification that may be easily integrated into high speed automated CL manufacturing. Additionally, the high-energy irradiation step could allow simultaneous surface grafting and sterilization.  \n\n[0012]   Contact lenses of any type may be surface modified according to the method of the invention, including silicone copolymers, hydrogels and RGPs; both Disposable Hydrogel CLs and Extended Wear CLs. Various hydrophilic polymers and monomers may be used in the method of the invention.For example, PVP (Plasdone K-90, C30, C15, and C 10), Gamma polymerized PVP, PHEMA, etc. Monomers employable in the practice of the invention include NVP, HEMA dimethylacrylamide CDMA), and the like. It is a critical feature of the invention that mixtures of monomers and polymers are used.  \n\n[0013]The term “hydrophilic polymer” as used herein refers to a synthetic polymer composed of molecular segments that render the polymer as a whole “hydrophilic” or naturally occurring polymeric materials that are hydrophilic. As utilized herein, the term “biocompatible polymer\" is used to refer to any polymer that is susceptible to implantation in a host (e.g., human host) and does not elicit any adverse reactions.  \n\n[0014] Preferred synthetic polymers are highly pure or are purified to a highly pure state such that the polymer is biocompatible. Hydrophilic polymers useful herein include, but are not limited to homo-, co-, terpolymers or polymers comprising a polymer backbone that comprises polar heteroatoms (i.e., wherein the polar heteroatoms present within the polymer backbone of the hydrophilic polymers include, but are not limited to, oxygen, nitrogen, sulfur, or phosphorous), such as: polyalkylene oxides, particularly polyethylene glycol, polyethylene oxide, and poly(ethylene oxide)- poly(propylene oxide) copolymers, including block and random copolymers; polyols such as glycerol, polyglycerol (particularly highly branched polyglycerol), propylene glycol and trimethylene glycol substituted with one or more polyalkylene oxides, e.g., mono-, di- and tri-polyoxyethylated glycerol, mono- and di-polyoxyethylated propylene glycol, and mono- and di-polyoxyethylated trimethylene glycol; polyoxyethylated sorbitol, polyoxyethylated glucose; acrylic acid polymers and analogs and copolymers thereof, such as polyacrylic acid per se, polymethacrylic acid, poly(hydroxyethylmethacrylate), poly(hydroxyethylacrylate), poly(methylalkylsulfoxide methacrylate), poly(methylalkylsulfoxide acrylate) and copolymers of any of the foregoing with additional acrylate species such as aminoethyl acrylate and mono-2-(acryloxy)-ethyl succinate; polymaleic acid; poly(acrylamides) such as polyacrylamide per se, poly(methacrylamide), poly(dimethylacrylamide), polydimethylaminoethyl methacrylate, polydimethylaminopropyl methacrylamide, poly(acrylamide/dimethylaminoethyl methacrylate), poly(methacrylic acid/dimethylaminoethyl methacrylate), poly(acrylamide/dimethylaminopropyl methacrylamide), poly(2-acrylamido-2-methyl propane sulfonic acid/dimethylaminoethylmethacrylate),poly(acylic acid/dimethylaminopropylmethacrylamide),  poly(methacrylic acid/dimethylaminopropyl methacrylamide); poly(N-isopropyl-acrylamide); poly(olefinic alcohol)s such as poly(vinyl alcohol); poly(N-vinyl lactams) such as poly(vinyl pyrrolidone), poly(N-vinyl caprolactam), and copolymers thereof; polyoxazolines, including poly(methyloxazoline)andpoly(ethyloxazoline);polyvinylamines; polyethylene glycol, polypropylene glycol, branched polyethylene imine, polyvinyl pyrrolidone, polylactide, poly(lactide-co-glycolide), polysorbate, polyethylene oxide, poly(ethylene oxide-co-propylene oxide), poly(oxyethylated) glycerol, poly(oxyethylated) sorbitol, poly(oxyethylated glucose), polymethyloxazoline, polyethyloxazoline, polyhydroxyethyloxazoline, polyhydroxypropyloxazoline, polyvinyl alcohol, poly(hydroxyalkylcarboxylic acid), polyhydroxyethyl acrylic acid, polyhydroxypropyl methacrylic acid, polyhydroxyvalerate, polyhydroxybutyrate, polyoxazolidine, polyaspartamide, polysialic acid, polyalkylene oxide, polyalkyleneimine, polyalkylene amine, polyalkene sulfide, polyalkylene sulfonate, polyalkylene sulfone, poly(alkylenesulfonylalkyleneimine); celluloses; polyamides; polyetheramines; polyethyleneimines; polyhydroxyetheramines; polylysines; polysulfones; gums; starches; cationic starches (formed by reacting a starch, such as corn, maize, waxy maize, potato, tapioca, and the like, with the reaction product of epichlorohydrin and trialkylamine) and derivatives, mixtures and copolymers thereof.  \n\n[0015] Suitable biocompatible hydrophilic monomers for use in the practice of the invention include ethylenically unsaturated $\\mathrm{C}_{3}–\\mathrm{C}_{6}$ carboxylic acids, such as acrylic acid, alkyl acrylic acids (particularly methacrylic acid), itaconic acid, maleic acid, fumaric acid, acrylamidomethyl-propanesulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, vinyllactic acid, and styrene sulfonic acid; allylamine and allylamine salts formed with an inorganic acid, e.g., hydrochloric acid; d $\\mathrm{i-C_{1}-C}_{3}$ -alkylamino- $\\mathrm{.C}_{2}\\mathrm{.C}_{6}$ -alkyl acrylates and methacrylates such dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethylmethacrylate, dimethylaminopropyl acrylate, dimethylaminobutyl acrylate, dimethylaminoneopentyl acrylate and dimethylaminoneopentyl methacrylate; olefinically unsaturated nitriles, such as acrylonitrile; diolefinically unsaturated monomers, particularly diallylammonium compounds such as dimethyldiallylammonium chloride, dimethyldiallylammonium bromide, diethyldiallylammonium chloride,methyl-t-butyldiallylammonium methosulfate, methyl-n-propyldiallylammonium chloride, dimethyldiallylammonium hydrogensulfate, dimethyldiallylammonium dihydrogenphosphate, di-n-butyldiallylammonium bromide, diallylpiperidinium bromide, diallylpyrrolidinium chloride  and  diallylmorpholinium  bromide; N-vinylpyrrolidone; N-vinylformamide; acrylamide and substituted acrylamides, such as N-methylolacrylamide and $\\mathrm{C}_{1}–\\mathrm{C}_{3}$ alkyl acrylamides, particularly methacrylamide; N-vinylimidazole and N-vinylimidazoline; and other monomers, typically ethylenically unsaturated monomers, preferably vinyl monomers, substituted with at least one hydrophilic functionality such as a carboxylate, a thiocarboxylate, an amide, an imide, a hydrazine, a sulfonate, a sulfoxide, a sulfone, a sulfite, a phosphate, a phosphonate, a phosphonium, an alcohol, a thiol, a nitrate, an amine, an ammonium, or an alkyl ammonium group - $[\\mathrm{NHR}^{\\mathrm{1}}\\mathrm{R}^{\\mathrm{2}}]^{+}$ ,wherein $\\mathbb{R}^{1}$ and $\\mathrm{R}^{2}$ are alkyl substituents and the group is associated with a negatively charged anion, e.g., a halogen ion, nitrate, etc; carboxymethyl cellulose (CMC), hyaluronic Acid (HA) and mixtures thereof.  \n\n[0016]  It will be understood by those skilled in the art that any of the high energy graft polymerization methods described in the patents listed above may be utilized in the practice of the invention. The grafting procedure may include methods in which the grafting solution has an osmolarity similar to that of normal saline, i.e. iso-osmolar, to allow the contact lenses to remain in the grafting solution after irradiation prior to use. The following are typical descriptions of procedures for representative embodiments of this invention:",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# EXAMPLE1  \n\n[0017] Silicone copolymer contact lenses were placed in tubes containing $10\\mathrm{ml}$ of a deionized water (DI) solution of polyvinylpyrrolidone (PVP/K-90） and N-vinylpyrrolidone (NVP) in a w/w ratio of 4:1 and a total concentration of 10 wt $\\%$ . Tubes were placed in a carousel holder that rotated around a gamma source at a distance of ${\\sim}4\"$ and samples were irradiated to a total dose of O.1 Mrad at a dose rate of \\~480 rads/min. The CLs were washed in DI water. They were highly hydrophilic (contact angle ${\\sim}20^{\\circ}$ )，more lubricious to the touch and the hydrophilic gamma graft coating was stable to repeated dry-wet cycling.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# EXAMPLE2  \n\n[0018]  The process of Example 1 was carried out under:  \n\n1] Conditions in which the aqueous solution was $2\\%$ KOH or NaOH and therefore at a high pH;  \n\n2] Conditions in which the polymer-monomer mix ratio is varied from 1:4 to ${>}4{:}1$ and the total solution concentration is varied from $1\\%$ to $25\\%$ ·  \n\n[0019]  3] Conditions in which the polymer in the polymermonomer mix is carboxymethyl cellulose (CMC), hyaluronic Acid (HA), PDMA, polymethacrylic acid (PMAA), PEG, and other hydrophilic, bioacceptable water soluble natural or synthetic polymers;  \n\n4] Conditions in which other hydrophilic or hydrophobic CL materials are substrates;  \n\n5] Conditions under which a beneficial ophthalmic drug is incorporated into the graft coating, either during the graft process or after, to afford bioactivity, e.g., an antibiotic, antiinflammatory, and antiglaucoma agents;  \n\n6] Conditions under which grafting is achieved simultaneously with radiation sterilization at total dosed up to 5Mrad, all with results similar to those produced in Example 1.  \n\n[0020]The contact lenses and other optical devices which may be modified according to the method of the invention may be constructed according to any conventional method such as, e.g., the methods described in U.S. Pat. Nos. 5,290,892; 5,693,095; and 5,331,073.  \n\n[0021]  The entire contents and disclosures of each of the above-noted U.S. patents and references are incorporated herein by reference. Unless otherwise stated, all percentages expressed herein are by weight.  \n\n1. In a method for modifying the surface of an article, said surface adapted for contact with living tissue of a human or non-human animal, by the gamma- or electron beam-irradiation induced polymerized, chemically grafted coating thereon of a hydrophilic monomer to form a hydrophilic graft polymer coating of the polymerized monomer or mixture of monomers, the improvement comprising conducting the gamma- or electron beam-irradiation induced graft polymerization in an aqueous solution containing a hydrophilic polymer under conditions whereby said hydrophilic polymer is at least partially entrapped in the graft polymerized coating.  \n\n2. The method of claim 1 wherein said hydrophilic polymer is a homo-, co-, terpolymer or polymer comprising a polymer backbone that comprises polar heteroatoms (i.e., wherein the polar heteroatoms present within the polymer backbone of the hydrophilic polymers include, but are not limited to, oxygen, nitrogen, sulfur, or phosphorous), selected from the group consisting of polyalkylene oxides, particularly polyethylene glycol, polyethylene oxide, and poly(ethylene oxide)-poly(propylene oxide) copolymers, including block and random copolymers; polyols such as glycerol, polyglycerol (particularly highly branched polyglycerol), propylene glycol and trimethylene glycol substituted with one or more polyalkylene oxides,e.g., mono-, diand tri-polyoxyethylated glycerol, mono- and di-polyoxyethylated propylene glycol, and mono- and di-polyoxyethylated trimethylene glycol; polyoxyethylated sorbitol, poly oxyethylated glucose; acrylic acid polymers and analogs and copolymers thereof, such as polyacrylic acid per se, polymethacrylic acid, poly(hydroxyethylmethacrylate), poly(hydroxyethylacrylate), poly(methylalkylsulfoxide methacrylate), poly(methylalkylsulfoxide acrylate) and copolymers of any of the foregoing with additional acrylate species such as aminoethyl acrylate and mono-2-(acryloxy)-ethyl succinate; polymaleic acid; poly(acrylamides) such as polyacrylamide per se, poly(methacrylamide), poly(dimethylacrylamide), polydimethylaminoethyl methacrylate, polydimethylaminopropyl methacrylamide, poly(acrylamide/dimethylaminoethyl methacrylate), poly(methacrylic acid/dimethylaminoethyl methacrylate), poly(acrylamide/ dimethylaminopropyl methacrylamide), poly(2-acrylamido2-methyl propane sulfonic acid/dimethylaminoethyl methacrylate),poly (acrylic acid/dimethylaminopropyl methacrylamide), poly(methacrylic acid/dimethylaminopropyl methacrylamide); poly(N-isopropyl-acrylamide); poly(olefinic alcohol)s such as poly(vinyl alcohol); poly(N-vinyl lactams) such as poly(vinyl pyrrolidone), poly(N-vinyl caprolactam), and copolymers thereof; polyoxazolines, including poly(methyloxazoline) and poly(ethyloxazoline); polyvinylamines; polyethylene glycol, polypropylene glycol, branched polyethylene imine, polyvinyl pyrrolidone, polylactide, poly(lactide-co-glycolide), polysorbate, polyethylene oxide, poly(ethylene oxide-co-propylene oxide), poly(oxyethylated) glycerol, poly(oxyethylated) sorbitol, poly(oxyethylated glucose), polymethyloxazoline, polyethyloxazoline, polyhydroxyethyloxazoline,polyhydroxypropyloxazoline, polyvinyl alcohol, poly(hydroxyalkylcarboxylic acid),polyhydroxyethyl acrylic acid, polyhydroxypropyl methacrylic acid, polyhydroxyvalerate, polyhydroxybutyrate, polyoxazolidine, polyaspartamide, polysialic acid, polyalkylene oxide, polyalkyleneimine, polyalkylene amine, polyalkene sulfide, polyalkylene sulfonate, polyalkylene sulfone, poly(alkylenesulfonylalkyleneimine); celluloses; polyamides; polyetheramines; polyethyleneimines；polyhydroxyetheramines; polylysines; polysulfones; gums; starches; cationic starches (formed by reacting a starch, such as corn, maize, waxy maize, potato, tapioca, and the like, with the reaction product of epichlorohydrin and trialkylamine) and derivatives, mixtures and copolymers thereof.  \n\n3. The method of claim 1 wherein said hydrophilic monomer is selected from the group consisting of ethylenically unsaturated $\\mathrm{C}_{3}–\\mathrm{C}_{6}$ carboxylic acids, such as acrylic acid, alkyl acrylic acids (particularly methacrylic acid), itaconic acid, maleic acid, fumaric acid, acrylamidomethylpropanesulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, vinyllactic acid, and styrene sulfonic acid; allylamine and allylamine salts formed with an inorganic acid, e.g., hydrochloric acid; di- $\\mathrm{.C_{1}.C_{3}}$ -alkylamino ${\\bf\\cdot C}_{2}{\\bf-C}_{6}$ -alkyl acrylates and methacrylates such dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminobutyl acrylate, dimethylaminoneopentyl acrylate and dimethylaminoneopentyl methacrylate; olefinically unsaturated nitriles, such as acrylonitrile; diolefinically unsaturated monomers, particularly diallylammonium compounds such as dimethyldiallylammonium chloride, dimethyldiallylammonium bromide, diethyldiallylammonium chloride,methyl-t-butyldiallylammonium methosulfate, methyl-n-propyldiallylammonium chloride, dimethyldiallylammonium hydrogensulfate, dimethyldiallylammonium dihydrogenphosphate, di-n-butyldiallylammonium bromide, diallylpiperidinium bromide, diallylpyrrolidinium chloride and diallylmorpholinium bromide; N-vinylpyrrolidone; N-vinylformamide; acrylamide and substituted acrylamides, such as N-methylolacrylamide and $\\mathrm{C}_{1}{\\cdot}\\mathrm{C}_{3}$ alkyl acrylamides, particularly methacrylamide; N-vinylimidazole and N-vinylimidazoline; and other monomers, typically ethylenically unsaturated monomers, preferably vinyl monomers, substituted with at least one hydrophilic functionality such as a carboxylate, a thiocarboxylate, an amide, an imide, a hydrazine, a sulfonate, a sulfoxide, a sulfone, a sulfite, a phosphate, a phosphonate, a phosphonium, an alcohol, a thiol, a nitrate, an amine, an ammonium, or an alkyl ammonium group - $[\\mathrm{NHR}^{1}\\mathrm{R}^{2}]^{+}$ ,wherein $\\mathbb{R}^{1}$ and $\\mathrm{R}^{2}$ are alkyl substituents and the group is associated with a negatively charged anion, e.g., a halogen ion, nitrate, etc; carboxymethyl cellulose (CMC), hyaluronic Acid (HA) and mixtures thereof.  \n\n4. The method of claim 1 wherein said hydrophilic monomer is part of a mixture thereof with up to about 50 wt. $\\%$ , based on the total monomer weight, of an ionic monomer, salt of an ionic monomer or a mixture thereof.  \n\n5. The article produced by the method of claim 1. 6. The article of claim 4 comprising a contact lens. 7. The contact lens of claim 5 comprising a silicone copolymers, a hydrogel, a RGP, a Disposable Hydrogel Contact Lens or an Extended Wear Contact Lens.  \n\n8.An article of manufacture comprising packaging material and an article having a surface adapted for contact with living tissue of a human or non-human animal contained within said packaging material, wherein said surface of said article has been modified to enhance contact with said living tissue, and wherein said packaging material comprises a label which indicates that said article is especially adapted for said contact.  \n\n9. The article of manufacture of claim 8 wherein said article having a surface adapted for contact with living tissue of a human or non-human animal is a contact lens.",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,187 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19) United States (12) Patent Application Publication Hess et al.",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (54) RADICAL CURABLE ANTI-FOG COATINGS  \n\n(71） Applicant: SDC Technologies, Inc., Irvine, CA(US)  \n\n(72） Inventors: David Hess, Mission Viejo, CA (US); Kiranmayi Deshpande, Irvine, CA (US); Andreas Schneider, Fullerton, CA (US); Ren-Zhi Jin, Irvine, CA (US)  \n\n(21)Appl.No.: 17/492,755 (22) Filed: Oct.4,2021  \n\n(10) Pub. No.: US 2022/0106497 A1   \n(43) Pub. Date: Apr.7, 2022  \n\nC08J 7/046 (2006.01) C09D 5/00 (2006.01)  \n\n(52) U.S. Cl. CPC C09D 175/08 (2013.01); C08J 2469/00 (2013.01); C08G 18/4841 (2013.01); C08G 18/0852 (2013.01); C08G 18/44 (2013.01); C08G 18/4825 (2013.01); C08G 18/3206 (2013.01); C08G 18/6517 (2013.01); C08G 18/4018 (2013.01); C08G 18/4808 (2013.01); C08J 7/046 (2020.01); C09D 5/00 (2013.01); C08G 2290/00 (2013.01); C08J 2375/08 (2013.01); C08G 18/755 (2013.01)  \n\nRelated U.S. Application Data (60） Provisional application No. 63/087,724, filed on Oct. 5,2020.",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# Publication Classification  \n\n(51) Int. Cl. C09D 175/08 (2006.01) C08G 18/75 (2006.01) C08G 18/48 (2006.01) C08G 18/08 (2006.01) C08G 18/44 (2006.01) C08G 18/32 (2006.01) C08G 18/65 (2006.01) C08G 18/40 (2006.01)",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# ABSTRACT  \n\nThe present disclosure provides a coating composition comprising an initiator, a radical curable polyurethane having ethylenically unsaturated functional groups, and a liquid phase, wherein the radical curable polyurethane having ethylenically unsaturated functional groups comprises the reaction products of A) a polyol component; B) a polyisocyanate component; C) an isocyanate-reactive surfactant; and D) isocyanate-reactive component having ethylenically unsaturated functional groups. The resulting cured polyurethane coating resists surface damage by fine particles and has at least washable anti-fog properties, if not permanent anti-fog properties. Articles prepared with a coating according to this invention are also disclosed.",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# RADICAL CURABLE ANTI-FOG COATINGS  \n\nRELATEDAPPLICATIONS  \n\n[0001] This application claims priority to U.S. Provisional Application No.63/087,724, filed on Oct.5, 2020, the entire disclosure of which is incorporated herein by reference.  \n\n“K-mark\") are included in EN 168.Thus, the eye wear with cured coatings that offer resistance to fog and pass tests specified in EN 168 are considered to have EN 166 N-mark. Similarly, the eye wear with cured coatings which pass EN 168 tests for resistance to surface damage by fine particles are considered to have EN 166 K-mark.",
+        "category": " References"
+    },
+    {
+        "id": 6,
+        "chunk": "# FIELD  \n\n[0002] The present disclosure relates to coating compositions that form coatings that offer resistance to fog as well as resistance to surface damage or wear by fine particle abrasion. The present disclosure also relates to processes for making the anti-fog coating compositions, processes for coating substrates with the anti-fog coating compositions, and articles coated with such anti-fog coating compositions.",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# BACKGROUND  \n\n[0003]  Permanent anti-fog properties are desired in several applications such as ophthalmic and sun lenses; safety, military and sports eyewear and accessories; glazing for automotive, transportation, building and construction, greenhouses; industrial, point-of-sale and electronics displays; commercial refrigerators and freezer doors; mirrors; solar panels, and others.  \n\n[0004]  Fogging occurs when the water vapor from surrounding air condenses on an article forming small water droplets. This happens when the article is at a lower temperature than that of the environment. Current anti-fog coatings usually form smooth surfaces that are hydrophilic in nature. Surfactants are used in the coating formulation to increase the surface energy of the cured coatings enabling the droplet to sheet instead of forming spherical droplets on the substrate. The resulting water sheeting effect minimizes the scattering of light thereby improving visibility.  \n\n[0005] In order to have long-lasting, or permanent, antifog performance, anti-fog coatings are typically formulated with large amounts of surfactants that can considerably lower the hardness of the coatings.However, oftentimes, the anti-fog coatings lose the anti-fog functionalities rather quickly and need to be rejuvenated with additional surfactants. Moreover, the long-lasting anti-fog coatings available on the market today are principally thermally cured and thus require long cure times at elevated temperatures that can impact manufacturing cost and productivity of anti-fog article manufacturers. Additionally, many of these coatings do not have abrasion resistant properties. Accordingly, there is a need for new fast-curing anti-fog coatings with longlasting anti-fog properties without the need for rejuvenation, and better abrasion resistant properties.  \n\n[0006] Resistance to fogging and resistance to surface damage by fine particles are essential criteria for eye wear to be considered as personal protection equipment. Furthermore, personal protective eyewear is ideally required to pass European Standard EN 166 (e.g.,EN 166, rev. 2001）to obtain certification. EN 166 includes several tests for different safety requirements namely, stability to elevated temperatures, resistance to ultraviolet radiation, corrosion, ignition, fogging, surface damage by large particles/fine particles etc. Test methods included in EN 166 certification are EN 167, which includes optical test methods and EN 168, which includes non-optical test methods. Resistance to fogging of the oculars (referred to as “N-mark\") and resistance to surface damage by fine particles (referred to as",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# SUMMARY  \n\n[0007] Free radical polymerization is commonly used for rapid polymerization and curing of coatings. Both thermal and radiation-induced free radical polymerization are prevalent methods. The present anti-fog and wear resistant coating compositions of the present disclosure may be produced using either thermal or/and radiation-induced radical polymerization. In particular, aspects of the present disclosure provide fast-curing coating composition formulations with permanent and/or water-washable anti-fog properties and resistance to surface damage by fine particles.  \n\n[0008]   The coating composition comprises a mixture comprising an initiator, a radical curable polyurethane having ethylenically unsaturated functional groups, and a liquid phase. The polyurethane having ethylenically unsaturated functional groups comprises the reaction products of A) a polyol component; B) a polyisocyanate component; C） an isocyanate-reactive surfactant; and D) isocyanate-reactive component having ethylenically unsaturated functional groups.  \n\n[0009] In aspects of the present disclosure, the compositions cure upon exposure to UV (Ultra Violet) radiation to provide a substrate, such as eyewear, with wear resistance properties and water-washable and/or permanent anti-fog properties. In aspects of the present disclosure, the compositions can cure upon exposure to thermal radiation, to provide a substrate, such as eyewear, with water-washable and/or permanent anti-fog properties. In aspects of the present disclosure, the compositions can cure upon exposure to UV and thermal radiation to provide a substrate, such as eyewear, with wear resistance properties and water-washable and/or permanent anti-fog properties. Water-washable and/or permanent anti-fog properties are obtained through chemical bonding of the reactive surfactant within the polymeric network of cured polyurethane. Water-washable and/or permanent anti-fog properties are also achieved by using minimal loading of the surfactant.  \n\n[0010] In aspects of the present disclosure, the compositions include a photoinitiator to initiate the radical cure of the composition. In aspects of the present disclosure, the compositions include a thermal radical initiator to initiate the thermal radical cure of the composition. In aspects of the present disclosure, the compositions include a photoinitiator and a thermal radical initiator to initiate the radical cure of the composition. In aspects of the present disclosure, the compositions do not include an initiator and use electron beam radiation to initiate the radical cure of the composition.",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# DETAILEDDESCRIPTION  \n\n[0011] Unless otherwise indicated herein, the phrase“permanent anti-fog properties” refer to anti-fog properties that do not dissipate or leach away over time.  \n\n[0012] Unless otherwise indicated herein, the phrase \"water-washable anti-fog properties\" refer to anti-fog properties that pass the N-mark test described herein.  \n\n[0013] Unless otherwise indicated herein, the phrase “wear-resistant\" or“wear-resistance” refers to coatings that are resistant to surface damage by fine particles and pass the \"K-mark” test.  \n\n[0014]   The present disclosure provides an anti-fog coating composition with permanent and/or water-washable anti-fog properties and wear-resistance to surface damage by fine particles. The coating composition comprises a mixture comprising an initiator, a radical curable polyurethane having ethylenically unsaturated functional groups, and a liquid phase. The polyurethane having ethylenically unsaturated functional groups comprises the reaction products of A） a polyol component; B) a polyisocyanate component; C） an isocyanate-reactive surfactant; and D) an isocyanate-reactive component having ethylenically unsaturated functional groups. Aspects of the present disclosure yield anti-fog coatings with at least EN-166 N mark (anti-fog) and K mark (wear resistance) performance.  \n\n[0015] The present disclosure further provides processes for making the coating compositions and methods of use of such compositions. Free radical polymerization is commonly used for rapid polymerization and curing of coatings. Both thermal and radiation-induced free radical polymerization are prevalent methods. The present anti-fog and wear resistant coating compositions of the present disclosure may be produced using either thermal or/and radiation-induced radical polymerization. Upon cure, a hydrophilic polymeric polyurethane network is formed from the coating compositions with the reactive surfactant bound to the network due to the binding between the reactive groups of the polymer resins (e.g., polyol, polyisocyanate, and isocyanate-reactive component having ethylenically unsaturated functional groups) and reactive surfactants. The bonding of the reactive surfactant to the polyurethane polymer network provide long lasting anti-fog properties to the present coating composition when applied to a substrate and cured. The coating compositions of the present disclosure yield anti-fog coatings with both EN-166 N and K mark performance, if not anti-fog and/or wear resistance performance superior to N-mark and/or K-mark. In accordance with some aspects of the present disclosure, the coating compositions result in coatings with permanent anti-fog properties and/or water-washable anti-fog properties. In further aspects, coating compositions retain their anti-fog properties after being subjected to multiple washes, for example, at least 20 washes, according to various wash anti-fog tests described below.  \n\n[0016]  In accordance with aspects of the present disclosure, the coating compositions include a hydrophilic alkoxylated acrylate as all or part of the isocyanate-reactive component having ethylenically unsaturated functional groups. This acrylate, upon cure, further contributes to the hydrophilicity, and thus the permanent anti-fog properties of the polyurethane polymeric network forming the coating,while providing the crosslinkable acrylate functionality (i.e., ethylenically unsaturated functional group) reaction sites.  \n\n[0017] Optionally, the coating compositions of the present disclosure may further include metal oxide nanoparticles that can impart further abrasion-resistant properties to the coating, upon cure, while still retaining optical transparency and/or fog resistant properties.  \n\n[0018] The present disclosure also provides articles coated with a coating formed from the coating compositions of the present disclosure. The coatings are optically transparent and are applied on optically transparent substrates, such as lenses for eyeglasses. In accordance with aspects of the present disclosure, the instant coatings may be used in cold applications, such as in ski goggles or an anti-fog freezer film or coating on transparent surfaces of a freezer or refrigerator.",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# Liquid Phase  \n\n[0019] As discussed above, the coating compositions of the present disclosure comprises an initiator, a radical curable polyurethane having ethylenically unsaturated functional groups, and a liquid phase. Suitable liquid phases include water, organic solvents, and combinations thereof. [0020] The selection of suitable organic solvents used as the liquid phase of the coating compositions described herein is dependent upon the selection of constituent components reacted to form the polyurethane, including those solvents able to dissolve the selected polyols and solvents that do not readily react with the polyisocyanates. Examples of suitable organic solvents useful for such reactions include ketones such as methylethylketone, methylisobutyl ketone, diacetone alcohol, 3,3-dimethyl-2-butanone, and pentanedione; N-methyl pyrrolidone; acetonitrile; esters; glycol esters; and tertiary alcohols such as tertiary-butyl alcohol and tertiary-amyl alcohol.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# Initiator  \n\n[0021]  As discussed above, in some aspects, the coating compositions of the present disclosure comprise an initiator. Suitable initiators for use with the compositions of the present disclosure include, but are not limited to, any suitable thermal radical initiator and/or photoinitiator that initiate radiation curing of the polyurethane acrylate of the coating composition. In other words, the initiator initiates and advances the crosslinking of the curable resins, i.e., curing of the coating composition when the coating composition is exposed to radiation. Thus, in accordance with the present disclosure, the coating compositions comprise a thermal radical initiator, a photoinitiator, or a combination of a thermal radical initiator and a photoinitiator.  \n\n[0022] The thermal radical initiator initiates curing when exposed to thermal radiation, including but not limited to heat. The thermal initiator is not particularly limited, and includes an azo initiator, a peroxide initiator, a persulfate initiator, a redox initiator, and combinations thereof.  \n\n[0023] Examples of suitable azo initiators include, but are not limited to, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33),2,2'-azobis(2-amidinopropane) dihydrochloride (VAZO 50), 2,2'-azobis(2,4-dimethylvaleronitrile) (VAZO 52), 2,2'-azobis(isobutyronitrile) (VAZO 64), 2,2'- azobis-2-methylbutyronitrile (VAZO 67), 1,l-azobis(l-cyclohexanecarbonitrile)(VAZO 88）(all available from DuPont Chemical), 2,2'-azobis(2-cyclopropylpropionitrile), and 2,2'-azobis(methylisobutyrate) (V-601) (available from Wako Pure Chemical Industries, Ltd), and the like.  \n\n[0024] Examples of suitable peroxide initiators include, but are not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di(4-t-butylcyclohexyl) peroxydicarbonate (Perkadox 16S) (available from Akzo Nobel), di(2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11) (available from Elf Atochem), t-butyl peroxy-2-ethyl hexanoate (Trigonox 21-C50) (available from Akzo Nobel), dicumyl peroxide, and the like.  \n\n[0025] Examples of suitable persulfate initiators include, but are not limited to, potassium persulfate, sodium persulfate, and ammonium persulfate.  \n\n[0026] Examples of suitable redox (oxidation and reduction) initiators include, but are not limited to, a combination of the persulfate initiator and a reducing agent such as sodium metabisulfite and sodium bisulfite; a combination of an organic peroxide and a tertiary amine-based system, such as a system based on benzoyl peroxide and dimethylaniline; and a system based on an organic hydroperoxide and a transition metal, such as a system based on cumene hydroperoxide and cobalt naphthate.  \n\n[0027]  Examples  of  other  thermal  radical  initiators include, but are not limited to, pinacols such as tetraphenyl 1,1,2,2-ethanediol, and the like.  \n\n[0028] The thermal radical initiator preferably comprises an azo initiator or a peroxide initiator. Further preferred are 2,2'-azobis(methylisobutyrate), benzoyl peroxide, dicumyl peroxide, t-butyl peroxypivalate and di(4-t-butylcyclohexyl) peroxydicarbonate, and a mixture of these.  \n\n[0029] The photoinitiator initiates curing of the compositions upon exposure to radiation or light. Suitable photoinitiators may be selected to react when exposed to UV light or visible light such as blue light photoinitiators.  \n\n[0030] Examples of suitable UV radiation sensitive photoinitiators or blends of initiators used in coating compositions disclosed herein include, but are not limited to, benzoin; substituted benzoins such as butyl isomers of benzoin ethers; benzophenone; substituted benzophenones such as hydroxy benzophenone; 2-hydroxyethyl-N-maleimide; 2-[2-hydroxyethyl(methyl)amino]ethanolanthraquinone; thioxanthone; $^{\\mathbf{{\\alpha}}_{\\mathbf{{\\alpha}}}\\mathbf{{\\alpha}}}\\mathbf{{\\alpha}}_{\\mathbf{{\\alpha}}}\\mathbf{{\\alpha}}_{\\mathbf{{\\alpha}}}\\mathbf{{\\alpha}}_{\\mathbf{{\\alpha}}}\\mathbf{{\\alpha}}_{\\mathbf{{\\alpha}}}\\mathbf{{\\alpha}}_{\\mathbf{{\\alpha}}}\\mathbf{{\\alpha}}_{\\mathbf{{\\alpha}}}\\mathbf{{\\alpha}}_{\\mathbf{{\\alpha}}}\\mathbf{{\\alpha}}_{\\mathbf{{\\alpha}}}\\mathbf{{\\alpha}}_{\\mathbf{{\\alpha}}}\\mathbf{{\\alpha}}_{\\mathbf{{\\alpha}}}\\mathbf{{\\alpha}}_{\\mathbf{{\\alpha}}}\\mathbf{{\\alpha}}_{\\mathbf{{\\alpha}}}\\mathbf{{\\alpha}}_{\\mathbf{{\\alpha}}}\\mathbf{{\\alpha}}_{\\mathbf{{\\alpha}}}\\mathbf{{\\alpha}}_{\\mathbf{{\\alpha}}}\\mathbf{{\\alpha}}_{\\mathbf{{\\alpha\\alpha}}}\\mathbf{{\\alpha}}_{\\mathbf{{\\alpha\\alpha}}}_\\mathbf{{\\alpha}}_{\\mathbf{\\alpha}}\\mathbf{{\\alpha}}_\\mathbf{\\alpha}_{\\mathbf{\\alpha}}_{\\mathbf{\\alpha}}_\\mathbf{\\alpha}_{\\alpha}\\mathbf{\\alpha}_{\\alpha}_\\mathbf{\\alpha}\\mathbf{}\\mathbf{\\alpha}_{\\alpha}\\mathbf{\\alpha}_\\mathbf{\\alpha}\\mathbf{\\alpha}}_\\mathbf{\\alpha}_{\\alpha\\mathbf\\alpha}{\\alpha}_\\mathbf{\\alpha\\alpha}\\mathbf{\\alpha}\\mathbf\\mathbf{\\alpha}\\mathbf{\\alpha\\alpha}\\mathbf\\mathbf{\\alpha}\\mathbf\\mathbf{\\alpha}\\mathbf\\alpha\\mathbf{\\alpha}\\mathbf\\mathbf{\\alpha\\alpha}\\mathbf\\mathbf{\\alpha\\alpha}\\mathbf\\mathbf\\mathbf{\\alpha\\alpha\\alpha}\\mathbf\\mathbf\\mathbf{\\alpha\\alpha\\alpha}\\mathbf\\mathbf\\mathbf{\\alpha\\alpha\\alpha\\alpha\\alpha\\alpha\\alpha\\mathbf\\alpha}\\mathbf\\mathbf\\mathbf\\mathbf{\\alpha\\alpha\\alpha\\alpha\\alpha\\alpha\\alpha\\mathbf\\alpha\\mathbf\\alpha\\mathbf\\alpha\\alpha\\alpha\\mathbf\\alpha\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta\\delta$ -diethoxyacetophenone; 2,2-dimethoxy-1, 2-diphenylethan-1-one; 2-hydroxy-2-methyl-1-phenyl-propan-1-one; diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenyl glyoxylic acid methyl ester; 1-hydroxylcyclohexyl phenyl ketone; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one;  \n\n2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1- one; and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2- methyl-l-propane-l-one. Cationic photoacid generators may include but are not limited to diphenyl[3-(phenylsulfanyl)phenyllsulfonium hexafluorophosphate; diphenyl[2- phenylsulfanyl)phenyllsulfonium hexafluoroantimonate; mixtures of triarylsulfonium with hexafluoroantimonate of hexafluorophosphate salts in propylene carbonate; and diaryl iodonium salts with pentafluoroborate, hexafluoroantimonate or hexafluorophosphate.  \n\n[0031] Optionally, photoinitiator synergists are employed as coinitiators in conjunction with acyl ketone photoinitiators such as for example benzophenone. Suitable photoinitiator synergists include, for example, N-methyl-diethanol amine, triethanolamine 2-(butoxy)ethyl-4-dimethylaminobenzoate and reactive amine acrylates commercially available as EBECRYL P104,EBECRYL P105, and EBECRYL 7100 from UCB Radcure Chemicals Corporation, Smyrna, Ga. or CN 371,CN 373,CN 384,or CN 386 available commercially from Sartomer Company, Inc., Exton, Pa. Sartomer describes $\\mathrm{CN}\\ 373$ as a reactive amine acrylate coinitiator that can be used in combination with a hydrogen abstracting photoinitiator, such as benzophenone or isopropyl thioxanthone (ITX), to promote free radical polymerization. CN 373 accelerates surface cure speed and helps overcome oxygen inhibition in UV curable coatings and inks. Sartomer describes CN 371, CN 384, CN 386, CN 550, and CN551 as di- and tri-functional amine acrylate coinitiators which, when used in conjunction with a photosensitizer, such as benzophenone, promote rapid curing under UV light.  \n\n[0032] As discussed above, suitable photoinitiators include a visible light photoinitiator to initiate curing of the composition upon exposure to blue light $400{-}500\\ \\mathrm{nm})$ _ Such photoinitiators may include, but are not limited to, camphorquinone, phenylpropanedione (PPD), bisacrylphosphine oxide (IRGACURE 819), include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), 2,4,6-trimethylbenzoylethoxy-phenylphosphine oxide (TPO-L), and bis(2,4,6- trimethylbenzoyl)phenylphosphine oxide (BAPO).  \n\n[0033] In some embodiments, the photoinitiator is selected from a family of alpha hydroxyl ketone photoinitiators. In some embodiments, the photoinitiators comprises one or more of IRGACURE 500 ( $50\\%$ Benzophenone $+50\\%$ 1-hydroxy-cyclohexyl-phenyl ketone) and Darocure 1173 (2-hydroxy-2-methyl-propiophenone).  \n\n[0034] The coating compositions may be alternatively cured using electron beam (EB) radiation with minimal to no use of initiators. Accordingly, in some aspects of the present disclosure the coating compositions do not include an initiator.  \n\n[0035] The coating compositions of the present disclosure comprise one or more initiator in amounts ranging from $0.3{-}6~\\mathrm{wt}~\\%$ ，based on the total weight solids of the coating composition, including 0.4-5.9 wt $\\%$ n $0.8{-}5.8~\\mathrm{wt}~\\%$ 09.-5.7 wt $\\%$ 。 $1{-}5.5\\ \\mathrm{wt}\\ \\%$ ，1.5-5wt $\\%$ 2-4.75wt $\\%$ ，and 2.5-4.5 wt $\\%$ ， based on the total weight solids of the coating composition.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# Radical Curable Polyurethane  \n\n[0036] As discussed above, the coating compositions of the present disclosure comprises a radical curable polyurethane. This polyurethane is radically curable because it has ethylenically unsaturated functional groups. Unless otherwise indicated herein, ethylenically unsaturated functional groups may refer to a functional group formed from a compound that can be represented by the following formula where R1, R2, R3, and R4 are independently selected from H, hydrocarbyl, or substituted hydrocarbyl groups.  \n\n![](images/5eaab95f87d08242a67ce84bfdaec04e2ed3a569f50ac836b75c3d78e474c81c.jpg)  \n\n[0037] The radical curable polyurethane having ethylenically unsaturated functional groups of the present disclosure is the reaction product of (A) a polyol, (B) a polyisocyanate, (C) an isocyanate-reactive surfactant, and (D) an isocyanatereactive component having ethylenically unsaturated functional groups.  \n\n[0038]   In accordance with the coating compositions of the present disclosure, any isocyanate-reactive compound having unsaturated reactive functionality can be substituted for component (D), the isocyanate-reactive component having ethylenically unsaturated functional groups.Suitable isocyanate-reactive compounds having unsaturated reactive functionality include isocyanate reactive alkenyl compounds, such as isocyanate-reactive compounds having an ethylenically unsaturated reactive group, including but not limited to reactive vinyl groups, reactive acrylate groups, reactive methacrylate groups, reactive allyl groups, and the like.  \n\n[0039]  The coating compositions of the present disclosure comprise at least one radical curable polyurethane having ethylenically unsaturated functional groups in amounts ranging from $85{-}97.5\\mathrm{wt\\%}$ , based on the total weight solids of the coating composition, including 87-96 wt $\\%$ ，88-95.5 wt $\\%$ ，and $87{\\cdot}95\\mathrm{\\wt\\}\\%$ ，based on the total weight solids of the coating composition.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# [0040](A) Polyols  \n\n[0041] Polyols used in accordance with coating compositions of the present disclosure include at least one polyol comprising (a) a diol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof, and/or (b） a triol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof.Examples of such polyols suitable for use to form the radical curable polyurethane include a diol having polyethylene oxide side chain segments; an alkyl diol; an alkyl triol, a polycarbonate diol; a polycarbonate triol; or combinations thereof. Suitable diols having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof used in accordance with the coating compositions disclosed herein include those described in U.S. Pat. No. 8,642,180 (the entire contents of which are incorporated by reference herein), preferably a polypropylene oxide and polyethylene oxide block copolymer diol comprising polyethylene oxide in the main chain in an amount ranging from about $10\\%$ to about $25\\%$ by weight of the polyol, including $10\\%$ to $25\\%$ D $14\\%$ to $22\\%$ ,and $17\\%$ to $19\\%$ by weight of the polyol. Suitable triols having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof used in accordance with the coating compositions disclosed herein include those described in U.S. Pat. No.8,642,180, preferably a polypropylene oxide and polyethylene oxide copolymer triol comprising from about $60\\%$ to about $95\\%$ polyethylene oxide by weight of the polyol, including $60\\%$ to $95\\%$ 。 $65\\%$ to $90\\%$ D $70\\%$ to $85\\%$ , and $75\\%$ to $80\\%$ polyethylene oxide by weight of the polyol.  \n\n[0042] In accordance with aspects of the present disclosure, such polyols have one or more hydrophilic regions or domains due to the presence of one or more groups of the following formula:— $((\\mathrm{CH}_{2})_{n}\\mathrm{O-})_{m}$ . In some embodiments, n can be equal or greater than 1 and equal or less than 3 $(1\\leq n\\leq3)$ , m can be equal or greater than 1 and equal or less than10 $(1\\mathrm{{sm}\\leq10})$ ,or both. In some embodiment, n may be equal to 2. Suitable polyols include polyethylene oxide, ethylene glycol, propylene glycol, polypropylene oxide and mixtures thereof. Specific examples of commercially available suitable polyols include, but are not limited to POLY-G 83-34, PLURONICS, and POLAXIMERS. The polyols may additionally further comprise other polyols in addition to polyols (a) and/or (b) described above. Examples of such optional additional polyols include, but are not limited to polycarbonate polyols, polyether polyols, and polyester polyols, including polycarbonate diols or triols, polyether diols or triols, and polyester diols or triols.  \n\n[0043] The coating compositions of the present disclosure comprise one or more polyol in amounts ranging from 10-60 wt $\\%$ , based on the total weight solids of the radical curable polyurethane, including 10.5-59 wt $\\%$ ，11-58.5 wt $\\%$ ，12-58 wt $\\%$ $15{-}55\\mathrm{wt\\%}$ D $10{-}20\\mathrm{wt}\\%$ n $20–50\\mathrm{wt}\\%$ ，25-48wt $\\%$ and 35-45 wt $\\%$ based on the total weight solids of the radical curable polyurethane.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 14,
+        "chunk": "# [0044](B) Polyisocyanates  \n\n[0045] Polyisocyanates used in accordance with coating compositions of the present disclosure include compounds having more than one isocyanate functionality (i.e., multifunctional isocyanates). Examples of such compounds include, but are not limited to, diisocyanates, trisocyanates, derivatives of diisocyanates and triisocyanates capable of forming polyurethane linkages, and combinations thereof. Diisocyanates are isocyanates with an isocyanate functionality of two. Examples of diisocyanates include isophorone diisocyanate hexamethylene diisocyanate (HDI), xylene diisocyanate (XDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate any diisocyanates derived from the foregoing， and combinations thereof. Triisocyanates are isocyanates with an isocyanate functionality of three. Triisocyanates include derivatives of diisocyanates, such as an HDI biuret. Because of their better light stability than the aromatic poly isocyanates, aliphatic polyisocyanates, including but not limited to aliphatic diisocyanates or aliphatic triisocyanates, are preferred for the polyurethane coating compositions described herein. IPDI-type and HDItype diisocyanates are aliphatic isocyanates. Specific examples of commercially avail able polyisocyanates include Desmophen I, Desmophen N75, and Desmophen W.  \n\n[0046]  The coating compositions of the present disclosure comprise one or more polyisocyanates in amounts ranging from $5.60\\ \\mathrm{wt}\\ \\%$ ，based on the total weight solids of the radical curable polyurethane, including 8-58 wt $\\%$ ，15-55wt $0\\%$ ，5-20wt $\\%$ ，20-50wt $\\%$ ，25-45wt $\\%$ and 35-40 wt $\\%$ based on the total weight solids of the radical curable polyurethane.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# [0047] (C) Isocyanate-Reactive Surfactant  \n\n[0048]The reactive surfactants used in accordance with the present disclosure comprise hydrophilic regions and reactive functionality (moieties) or groups capable of reacting with the reactive groups of the resins that react to form the radical curable polyurethane of the present disclosure. Such reactive moieties include, but are not limited to, one or more of a hydroxyl group, a thiol group, an amine group, or combination thereof. Other representative reactive surfactants with an isocyanate reactive group include compounds having a general chemical formula of: B-R, where B represents a hydroxyl, a thiol, an amine, or combination thereof and where R can be selected from quaternary ammonias, ether sulfonates, phosphoric acid esters, polyethers and copolymers thereof, nonionic polyethers, alkyl ethers, alkenyl ethers, and olefinic ethers. Specific examples of commercially available isocyanate-reactive surfactants include, but are not limited to IGEPAL CO-720, CIRRASOL G-265, TERGITOL15-S-7, TEGOMER D-3403.  \n\n[0049]  The coating compositions of the present disclosurecomprise one or more isocyanate-reactive surfactant inamounts ranging from 1-50 wt $\\%$ , based on the total weightsolids of the radical curable polyurethane, including 1.5-48wt $\\%$ ，1.75-45wt $\\%$ ，1.5-20wt $\\%$ ，1.5-10wt $\\%$ ，1.75-10wt$\\%$ ，1.5-5wt $\\%$ ，1.75-5wt $\\%$ ，1.5-4.5wt $\\%$ ，1.75-4.5wt $\\%$ 1.5-3.5 wt $\\%$ ，1.75-3.5 wt $\\%$ 1.5-3.0 wt $\\%$ ，1.75-3.0 wt $\\%$ D  \n\n8-45wt $\\%$ ,10-40 wt $\\%$ ,12-45 wt $\\%$ $15\\small{-}35\\ \\mathrm{wt}\\ \\%$ and 11-16 wt $\\%$ based on the total weight solids of the radical curable polyurethane.  \n\n[0050](D) Isocyanate-Reactive Component having Reactive Ethylenically Unsaturated Functionality  \n\n[0051]  Suitable isocyanate-reactive component having ethylenically unsaturated functional groups can be represented by the following formula, Y—R—X, where $\\mathrm{Y}$ is the ethylenically unsaturated functional groups, where R may be selected from polyethers, polyalkanes, polyalkenes, polyesters, or other chain extending group, and X may be selected from hydroxyl, amine, thiols,or other isocyanate reactive group. Nonlimiting examples of suitable isocyanate-reactive surfactants having ethylenically unsaturated functional groups include, but are not limited to, acrylates, preferably hydrophilic acrylates such as alkoxylated acrylates, glycidyl acrylates and the like.  \n\n[0052]  Such hydrophilic acrylates have one or more hydrophilic regions or domains due to the presence of one or more groups of the following formula: — $((\\mathrm{CH}_{2})_{n}\\mathrm{O-})_{m},$ where, n can be equal or greater than 1 and equal or less than 10( $\\mathrm{{1\\leqn\\leq10}}$ ), m can be equal or greater than 1 and equal or less than 10( $\\scriptstyle1\\leq m\\leq10 $ , or both. In aspects of the present disclosure, n may be equal to 2. In aspects of the present disclosure, m may be equal to 5. In aspects of the present disclosure, one or more alkoxylated acrylates may be employed to form the network. Specific examples of such alkoxylated acrylates include 4-hydroxybutyl acrylate, hydroxy ethyl methacrylate, hydroxy ethyl methacrylate, 2-hydroxy propyl acrylate, hydroxypropyl methacrylate, and glycerol monomethacrylate.  \n\n[0053]The ethylenically unsaturated functional groups of the isocyanate-reactive compounds having ethylenically unsaturated functional groups suitable for use with the instant compositions may be a reactive group that can react with a reactive group of the additional reactive surfactant, described below. For example, such reactive group can comprise the acrylate group.  \n\n[0054]  The coating compositions of the present disclosure comprise one or more isocyanate-reactive compounds having ethylenically unsaturated functional groups in amounts ranging from 1-25 wt $\\%$ , based on the total weight solids of the radical curable polyurethane, including 1.5-20 wt $\\%$ 1.5-10 wt $\\%$ ,1.75-10 wt $\\%$ ，1.5-5wt $\\%$ ,1.75-5wt $\\%$ ,1.5-3 wt $\\%$ ，1.75-3wt $\\%$ ,3-20wt $\\%$ ,6-18 wt $\\%$ $6.5{-}15\\mathrm{wt\\%}$ ，and 7-12.5 wt $\\%$ based on the total weight solids of the radical curable polyurethane.  \n\n[0055] (E) Optional Radical Reactive Surfactants [0056]  As described above, the reactive surfactants of the present compositions comprise hydrophilic regions and also include reactive functional groups capable of reacting with the reactive groups of the resins (e.g., isocyanates) that react to form the radical curable polyurethane of the present disclosure. Optionally, the coating compositions of the present disclosure may contain radical reactive surfactants having reactive functional groups including, but are not limited to, one or more of an alkenyl group, an acrylate group, a thiol group, or combination thereof. Accordingly, the radical reactive surfactant as disclosed herein comprise hydrophilic regions and also include reactive functionality (moieties) or groups capable of reacting one or more of an alkenyl group, an acrylate group, a thiol group or combination thereof. It should be noted that the radical reactive surfactant may be allowed to react with one or more reactive moieties either prior to adding the product of the reaction to the acrylate mix, or the radical reactive surfactant and the reactive moiety can be added to the acrylate mix at the same time. [0057]  A representative radical reactive surfactant having an alkenyl reactive group may have a general chemical formula of: ( $\\mathrm{\\CH}_{2}{=}\\mathrm{CH}$ )—R, where R can be selected from ether sulfonates, phosphoric acid esters, polyethers and copolymers thereof, nonionic polyethers, alkyl ethers, alkenyl ethers, and olefinic ethers, as shown in Table 1. Specific examples of commercially available radical reactive surfactants having hydrophilic segments with reactive double bond include, but are not limited to, REASOAP SR10, REASOAP SR20,REASOAPER10,REASOAPPP70,EMULSOGEN APS100. Additional non-limiting examples of reactive surfactant with an alkenyl reactive group are presented in Table 1 below.  \n\n![](images/65638a00a380675fb8e9569ade32fb7985f9d3fc975662536b7f488510433a01.jpg)  \n\nTABLE 1-continued   \n\n\n<html><body><table><tr><td>Compound</td><td>Description</td></tr><tr><td>Nonionic polyether surfactant (R' can be alkyl, aryl or other) n = 10, 11, . OR OH H</td></tr><tr><td>Polyether sulfates n = 4,5, DSO3M+ m = 10, 11, </td></tr><tr><td>n=1,2, m=1,2,.</td></tr><tr><td>M+ = metal or ammonium HC</td></tr><tr><td>counterion Polyether copolymer</td></tr><tr><td>1 =1,2, </td></tr></table></body></html>  \n\n[0058] A representative radical reactive surfactant with an acrylate reactive group may have a general chemical formula of: $(\\mathrm{CH}_{2}{\\mathrm{=}}\\mathrm{CHCOO}){\\mathrm{-}}\\mathrm{R}$ ，where R can be selected from ether sulfonates, phosphoric acid esters, polyethers and copolymers thereof, as shown in Table 2. Ilustrative examples of surfactants having hydrophilic segments with reactive acrylate moiety include, but are not limited to, metal salts of sulfopropylacrylic acid, and alkylacryloxyethyl trialkylammonium salts. Additional non-limiting examples of radical reactive surfactant with an acrylate reactive group are presented in Table 2 below.  \n\nTABLE 2-continued   \n\n\n<html><body><table><tr><td>Compound</td><td>Description</td></tr><tr><td>OH Im 0</td><td>Non-ionic Polyether Copolymers n=1,2,. m = 1,2, ...</td></tr></table></body></html>  \n\nTABLE2   \n\n\n<html><body><table><tr><td>Compound</td><td>Description</td></tr><tr><td>O</td><td>Ether Sulfonate n = 10,11,.. M+ = metal or</td></tr><tr><td>SO3M+</td><td>ammonium counterion</td></tr><tr><td>OP(O)(OH)2</td><td>Phosphoric acid ester n = 1,2, ...</td></tr><tr><td></td><td></td></tr><tr><td>N(CH3)3SOCH3</td><td>Polyethers n = 10,11, .</td></tr></table></body></html>  \n\n[0059] In some embodiments, the reactive segments of the radical reactive surfactant react with hydrophilic domains of the acrylates during the curing process. In this manner, upon curing, the radical reactive surfactant may be able to bind to the cured acrylate network and thus remain in place (not washed off or otherwise removed) to provide the coating with long-lasting anti-fog properties.  \n\n[0060]  A representative radical reactive surfactant with a thiol reactive group may have a chemical formula of: (SH)—R, where R can be selected from ether sulfonates, phosphoric acid esters, polyethers and copolymers thereof, as shown in Table 3. In some embodiments, a surfactant having hydrophilic segments with reactive thiol moiety can be obtained by reacting trimethylolpropane tris (3-mercaptoproprionate) (TMPTMP)with REASOAP SR10 via thiolene reaction. In some embodiments, a surfactant having hydrophilic segments with reactive thiol moiety can be obtained by reacting pentaerythritol tetrakis(3-mercaptoproprionate) with REASOAP SR10 via thiol-ene reaction.  \n\nAdditional non-limiting examples of radical reactive surfactant with a thiol reactive are presented in Table 3 below.  \n\nglycidyl acrylates, alkoxylated vinyls, and the like. Such acrylates have one or more hydrophilic regions or domains [0061] The coating compositions of the present disclosure comprise one or more radical reactive surfactants in amounts ranging from 0-20 wt $\\%$ based on the total weight solids of the radical curable polyurethane, including $2{\\cdot}18\\ \\mathrm{wt}\\ \\%$ ,5-15 wt $\\%$ $8–12\\mathrm{\\wt\\\\%}$ ,9-11 wt $\\%$ ,3-4 wt $\\%$ $7.8\\mathrm{wt}\\%$ ,and 16-18 wt $\\%$ based on the total weight solids of the radical curable polyurethane.  \n\n![](images/fc600f807b6c0d46346e9a276e36775215bf560456bf9c6300f6797ce6963fe8.jpg)  \n\n[0062] (F） Optional Radical Reactive Ethylenically Unsaturated Resins  \n\n[0063] As discussed above, the coating compositions of the present disclosure comprises a radical curable polyurethane that is the reaction product of (A） a polyol, (B） a polyisocyanate, (C) an isocyanate-reactive surfactant, and (D) an isocyanate-reactive component having ethylenically unsaturated functional groups. Optionally, the coating compositions of the present disclosure may further comprise radical reactive ethylenically unsaturated resins, i.e., an ethylenically reactive compound that is not reactive with isocyanate functionality.  \n\n[0064] Preferred ethylenically unsaturated resins include those with hydrophilic properties, such as hydrophilic acrylates including but not limited to alkoxylated acrylates, due to the presence of one or more groups of the following formula:— $((\\mathrm{CH}_{2})_{n}\\mathrm{O-})_{m}$ ，where, n can be equal or greater than 1 and equal or less than 10( $(1\\mathsf{s n s}10)$ ,m can be equal or greater than 1 and equal or less than 10( $(1\\mathsf{{s m}{\\le}10})$ ，or both. In aspects of the present disclosure, n may be equal to 2. In aspects of the present disclosure, m may be equal to 5. In aspects of the present disclosure, one or more ethoxylated acrylates may be employed to form the network. In aspects, the acrylates include one or more acrylates with mono, di, tri, or tetrafunctional groups. In aspects, the acrylates include more than one type of acrylate monomer. In aspects, the network can be generated by use of multifunctional ethoxylated acrylate monomers. In aspects, ethoxylated diacrylates and ethoxylated triacrylates are employed to form the network.  \n\n[0065]  Examples of suitable hydrophilic diacrylate monomers include, but are not limited to, ethylene glycol diacrylate; ethylene glycol dimethacrylate; diethylene glycol diacrylate; triethylene glycol diacrylate; triethylene glycol dimethacrylate; tetraethylene glycol diacrylate; tetraethylene glycol dimethacrylate; polyethylene glycol diacrylate; tripropylene glycol diacrylate; triisopropylene glycol diacrylate; polypropylene glycol dimethacrylate; polyether diacrylates derived from PLURONIC or POLAXAMER, and polyether diacrylates derived from reverse PLURONIC.  \n\n[0066] Examples of suitable hydrophilic triacrylate monomers include, but are not limited to, ethoxylated trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, propoxylated trimethylolpropane triacrylate, and tris(2-hydroxyethyl) isocyanurate triacrylate.  \n\n[0067]  Examples of  suitable hydrophilic  tetraacrylate monomers include, but are not limited to, ethoxylated pentaerythritol tetraacrylate.  \n\n[0068]  The ethylenically unsaturated resins suitable for use with the instant compositions also include a reactive group that can react with a reactive group of the radical reactive surfactant, described above. For example, such reactive group can comprise the acrylate group. In some embodiments, the reactive group may be located in the hydrophilic region of the acrylates and/or in the hydrophilic region network formed upon cure of the acrylates.  \n\n[0069] (G) Optional Metal Oxide Particles [0070] In accordance with some aspects of the present disclosure, the coating compositions may optionally further include metal oxide particles dispersed throughout the network of the radical curable polyurethane and the resins used to form the polyurethanes. The metal particles may provide hardness and abrasion resistant properties to the coatings formed from the coating compositions. Suitable examples of metal oxide nanoparticle include, but are not limited to, silica particles, titania, alumina, zinc oxides, antimony oxide, tin oxide, zirconium oxides, and combinations thereof. The size and concentration of the metal nanoparticles can be selected such that the resulting coatings are optically transparent, while still retaining their fog resistant properties and wear resistant properties. In some aspects, the metal oxide particles are nanoparticles with sizes ranging from about 5 to about $50\\mathrm{nm}$ ，including 5 to $50\\mathrm{nm}$ ,10to 45 nm,15 to $40\\ \\mathrm{nm}$ ，20to $35~\\mathrm{{nm}}$ ，and 25 to $30\\ \\mathrm{nm}$ In some aspects, the metal oxide particles are nanoparticles with sizes ranging from about 10 to about $20~\\mathrm{nm}$ . The nanoparticles may be present in an amount ranging from O and 70 wt $\\%$ by weight based on the total weight solids of the radical curable polyurethane, including 5 to $60\\mathrm{wt\\%}$ ，10to $50\\mathrm{wt\\%}$ D 15 to 40 wt $\\%$ ，and 20 to 30 wt $\\%$ by weight based on the total weight solids of the radical curable polyurethane.  \n\n[0071] $\\mathrm{(H)}$ Optional Non-Reactive Surfactants [0072] In accordance with some aspects of the present disclosure, the coating compositions may optionally further comprise non-reactive surfactants. The non-reactive surfactants may be added to the coating composition to further enhance anti-fog property. These non-reactive surfactants can be added at any point to the coating compositions, including during and after for reaction that forms the radical curable polyurethane acrylate. Suitable non-reactive surfactants include, but are not limited to, sulfonic acid salts, ammonium salts, phosphate salts, polyethylene glycol ether oligomers, hydrophilic polyacrylates, octophenoxypolyethoxyethanols, and nonionic polyether block copolymers. In some aspects, the non-reactive surfactant may be present in an amount ranging between O and $15\\mathrm{\\textrm{wt}\\%}$ by weight based on the total weight solids of the radical curable polyurethane, including 3-12 wt $\\%$ $5.10\\ \\mathrm{wt}\\ \\%$ ，and 6-9 wt $\\%$ by weight based on the total weight solids of the radical curable polyurethane. In some aspects, the concentration of non-reactive surfactant in the composition may range between 0.5 and $6\\mathrm{wt}\\%$ based on the total weight solids of the radical curable polyurethane, including $0.5\\mathrm{-}5\\mathrm{wt}\\%$ 0.5-4 wt $\\%$ D $1{-}3\\ \\mathrm{wt}\\ \\%$ , and 1.5-2.5 wt $\\%$ based on the total weight solids of the radical curable polyurethane.  \n\n[0073] (I) Optional Flow Modifiers/Leveling Agents [0074] In accordance with some aspects of the present disclosure, the coating compositions disclosed herein may optionally further include a leveling agent. The leveling agent, which may also be known as a flow-control agent, may be incorporated into the coating compositions described herein to spread the composition more evenly or level on the surface of the substrate and to provide substantially uniform contact with the substrate. The amount of the leveling agent can vary widely but preferably is used in an amount ranging from about O to about $10\\mathrm{wt}\\%$ based on weight solids of the coating composition, including O-10 wt $\\%$ ，2-8wt $\\%$ ，and 4-6 wt $\\%$ based on weight solids of the coating composition. Any conventional, commercially available leveling agent which is compatible with the coating composition and the substrate, which is capable of leveling the coating composition on a substrate, and which enhances wetting between the coating composition and the substrate may be employed. Non-limiting examples of such leveling agents include polyethers, silicones, fluorosurfactants, polyacrylates, silicone polyacrylates such as silicone hexaacrylate, and fluoromodified polyacrylates.Examples include BYK 350, BYK 354,BYK 356, CAPSTONE FS-35,CAPSTONE FS-31, CAPSTONE FS-61, TRITON X-100, X-405, and N-57 from Rohm and Haas, silicones such as Paint Additive 3, Paint Additive 29, and Paint Additive 57 from Dow Corning, SILWET L-77 and SILWET L-7600 from Momentive (Columbus, Ohio), and fluorosurfactants such as FLUORAD FC-4430 from 3M Corporation (St. Paul, Minn.).  \n\n[0075](J) Other Optional Additives [0076] Other additives such as an antioxidant, antistatic agent, polymeric additive (e.g. polyvinylpyrrolidone), weather resistive agent, tint additive, UV stabilizer, dispersing agent, defoamer, heat stabilizer, may also be added to the coating formulation. Examples of antioxidants include octadecyl-3-(3,5-di-tertbutyl-4-hydroxyphenyl) propionate, and pentaerythrityltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].  \n\n[0077] Examples of heat stabilizers include triphenyl phosphite, tris-(2,6dimethylphenyl)phosphite, tris-(2,4-di-tbutyl-phenyl)phosphite, tris-(mixed mono-and di-nonylphenyl)phosphite, dimethylbenzene phosphonate and trimethyl phosphate. Examples of the antistatic agent include glycerolmonostearate, sodium stearyl sulfonate, and sodium dodecylbenzenesulfonate.  \n\n[0078] Polycarbonates (PC) are known to degrade under the exposure of ultraviolet (UV) light. This process is known as weathering. A weatherable material can maintain its physical properties for a prolonged time under the UV exposure. In order to improve service life under UV exposure,a UV absorber may be needed in the coating for polycarbonate and similar aromatic plastic substrates. UV absorbers include, but are not limited to, three groups of chemicals: 1） 2-hydroxy-benzophenones (BP） derivatives, commercial examples include, but are not limited to, CHIMASSORB 81 and CHIMASSORB 9O (both from BASF, Germany); 2) 2-(2-hydroxyphenyl)-benzotriazole (HPBT) derivatives, commercial examples include, but are not limited to,TINUVIN 1130, TINUVIN 384-2,TINUVIN 928 and TINUVIN 900 (all from BASF, Germany); 3） 2-hydroxyphenyl-s-triazines (HPT） derivatives, commercial examples include, but are not limited to, TINUVIN 400, TINUVIN 405 (both from BASF, Germany).  \n\n[0079] Hindered amine light stabilizers (HALS） are also used for effective stabilization against the detrimental effects of light and weathering. The most widely used hindered amine light stabilizers (HALS) are mainly derivatives of 2,2,6,6-tetramethyl piperidine. Commercial examples include, but are not limited to, TINUVIN 152,TINUVIN 292 (both from BASF, Germany).  \n\n[0080] Those of ordinary skill in this field would know how much or how to determine how much of the various additives is necessary to achieve the desired result in the coating composition or the coating formed from the coating composition. Generally, no more than about $10\\mathrm{wt}\\%$ based on the total weight solids of the coating composition, of total additives are added to the coating compositions of the present disclosure, including no more than $10\\mathrm{wt}\\%$ ,no more than 7 wt $\\%$ , no more than 4 wt $\\%$ ，no more than 1 wt $\\%$ D and 0 wt $\\%$ based on the total weight solids of the coating composition.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 16,
+        "chunk": "# Substrates/Articles  \n\n[0081] The coating compositions disclosed herein can be applied as a coating to rigid or flexible substrates. Suitable substrate materials include, but are not limited to, transparent plastics such as polycarbonate (PC), polarized polycarbonate, polyamide, polyacrylic, polymethylmethacrylate (PMMA), polyvinylchloride, polybisallyl carbonate, allyl diglycol carbonate (ADC) polymer, polyethylene terephthalate (PET)， polyethylene naphthenate, cellulose triacetate (CTA) polymer, cellulose acetate butyrate (CAB) polymer, polyurethane, polyepisulfide, and polythiourethane. Other substrates including various polyolefins, fluorinated polymers, metals and glass, such as soda-lime glass, borosilicate glass, acrylic glass among other types of glass, can be used with appropriate pretreatments, if necessary. Examples of articles that may be coated with coatings of the present disclosure include, but are not limited to, safety eyewear, optical lenses, goggles, face shields, face plates for helmets, glazing used as windows in buildings, and glazing used as windshields or windows in automobiles, buses, trains, airplanes, and other transportation vehicles, multifunctional LED, LCD displays, bathroom mirrors, shower mirrors and fixtures. Coating may also be applied to commercial freezer doors, ice cream freezer doors and deli cases. In some embodiments, to increase adhesion of the present composition to the substrates, the substrates may be subjected to surface treatments and/or coated with primers. In some embodiments, acrylate-based primers may be used, particularly with PMMA substrates.  \n\n[0082]  Additionally, the coated articles prepared by coating the disclosed compositions on thin flexible substrates like PC or PET film can further be mounted/applied to the articles that require anti-fog functionality for example safety eyewear, optical lenses, goggles, face shields, face plates for helmets, glazing used as windows in buildings, and glazing used as windshields or windows in automotives, buses, trains, airplanes, and other transportation vehicles, multifunctional LED, LCD displays, bathroom and shower mirrors. The coatings of the present disclosure can be cast as films, which can also be applied via a repositionable optically transparent adhesive, such as a pressure sensitive adhesive, to commercial freezer doors, ice cream freezer doors and displays, deli cases to prevent frost formation and fogging.  \n\n[0083] The coating compositions described herein can be applied in any suitable manner to a substrate. For example, the compositions of the present disclosure can be applied to solid substrates by conventional methods, such as flow coating， spray coating, curtain coating, dip coating， spin coating, slot-die coating, roll coating, and the like to form a continuous surface film on the substrate. The coating compositions are then cured by exposing the coated substrate to UV radiation provided by UV lamps, visible light radiation provided by visible light lamps or, in some embodiments, EB radiation provided by EB accelerators, or a combination of these, all of these techniques being known to those skilled in the art. Additionally, the coated articles prepared by coating the disclosed compositions on thin flexible substrates like PC or PET film can be installed or retrofitted via dry or wet lamination on rigid substrates.  \n\n[0084] In accordance with the present disclosure, a method of providing an article with anti-fog properties comprises applying to the surface the coating compositions of the present disclosure and curing the coating composition on the surface. The curing includes exposing the coating composition applied to the substrate to heat or thermal radiation, light radiation, and/or electron beam radiation. The heat or thermal radiation to the applied coating is 50 to $150^{\\circ}\\mathrm{C}$ . for 1 minute to 4 hours, preferably from 100 to $125^{\\mathrm{{o}}}$ C.for 2 minutes to 1 hour. If the heat or thermal cure is used in combination with another radical cure mechanism such as the UV cure, the heat or thermal radiation to the applied coating is 50 to $150^{\\circ}\\mathrm{~C~}$ . for 1 minute to 60 minutes. [0085] UV Cure Units that can be used for UV exposure include a Fusion Conveyor Unit or a Vela 3D UV Cure Unit. A Fusion Conveyor Units are available from Heraeus Noblelight America, Gaithersburg, Md. A Vela 3D UV Cure Unit is available from Vela Technologies, Inc. San Diego, Calif. [0086]   The cumulative UV radiation exposure needed for curing is between 1.5 to $3.0\\ \\mathrm{J/cm}^{2}$ when using a Fusion H bulb for an exposure bulb for one minute. Using visible light generated by an LED light source of XY UV-2 UV-LED curing system available from Shenzhen Height-LED Optoelectronics Technology Co.,Ltd, Shenzhen, China, with peak emission wavelength of $460{\\pm}20~\\mathrm{nm}$ and intensity of from 200 to $300\\mathrm{\\mW/cm}^{2}$ at a distance of 1 to $20\\ \\mathrm{cm}$ from the LED light source, the coating compositions of the present disclosure can be cured in 1 to $30\\mathrm{min}$ In accordance with aspects of the present disclosure, the coating compositions form coatings having permanent anti-fog properties. In accordance with aspects of the present disclosure, the coating compositions form coatings water-washable anti-fog properties. In accordance with aspects of the present disclosure, the coating compositions form wear-resistant coatings, or in other words, coatings that are resistant to surface damage by fine particles. In accordance with aspects of the present disclosure, the coating compositions form coatings having permanent anti-fog, water-washable anti-fog, and wear resistant properties.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 17,
+        "chunk": "# EXAMPLES  \n\n[0087]  The following examples are merely representative and should not be used to limit the scope of the present disclosure.A large variety of alternative designs exists for the methods and compositions disclosed in the examples.  \n\nThe selected examples are therefore used mostly to demonstrate the principles of the devices and methods disclosed herein.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# Description of Tests:  \n\n[0088] Film Thickness: Film thickness of cured coating was measured with a Filmetrics F20-CP Spectrophotometer at wavelength of 632.8 nanometers (nm) based on spectral reflectance methodology.  \n\n[0089]  Haze: Light transmission and light-scattering properties of the cured coating was evaluated by measuring haze according to ASTM D 1003 standard with a Haze-gard Plus (BYK-Gardner, Columbia, Md.) hazemeter.  \n\n[0090] Adhesion: Adhesion is the ability of a coating to adhere to a substrate. The initial adhesion was tested using a roll of pressure sensitive tape 3M Brand SCOTCH 600 tape, Adhesion is also tested with Nichiban $\\#405$ tape.The test was carried out as follows: 1) a cross-hatch of a $5{\\times}5$ grid, approximately $2\\mathrm{mm}$ apart was made with a retractable razor blade into the cured coating; 2) the tape was pressed down firmly (using a tongue depressor) over the crosshatched area; 3) after $90{\\pm}30\\ \\mathfrak{s}$ , tape was pulled at an angle of $180^{\\circ}$ or as close to substrate as possible; 4) a check for the removal of the coating was made by examination of the coated substrate using appropriate visual control; 5) the subject area was also inspected under a microscope; 6) the actual count of unaffected areas was reported as percent adhesion (when adhesion was affected along a line only, the estimate is converted into percentages).  \n\n[0091] K-mark (Abrasion Resistance to Fine Particles): The abrasion resistance to fine particles was tested according to the EN166/EN168 protocol. An anti-fog article is loaded on a rotating holder in a Cadex Falling Sand tester. $3\\mathrm{kg}$ of sand is loaded into a funnel that is 6 feet above the surface of the rotating article. After the full $3~\\mathrm{kg}$ of sand impinges the rotating articles surface, the article is removed and washed with soap and water. After washing, the article is blown dry with filtered compressed air. The sample is then loaded into a Cadex Light Diffusion measurement device. The light diffusion must be less than $5\\operatorname{cd}/\\operatorname{m}^{2*}\\mathrm{lx}$ to pass this test.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 19,
+        "chunk": "# Anti-Fog Properties  \n\n[0092] Initial Anti-fog Test: Initial anti-fog test was carried out by positioning a coated substrate at a standard height (1\") above a beaker containing a source of $60^{\\circ}\\mathrm{C}$ water.The coated substrate was exposed to water vapor from the $60^{\\circ}\\mathrm{C}$ water for 1 minute. If fog appeared on the coated substrate during this test, the time taken for the appearance of the fog was recorded. If no fog appeared during 1 minute of exposure, then the coating was considered to “pass” the initial anti-fog test.  \n\n[0093] Water Soak Anti-fog Test: A coated substrate was soaked in water at room temperature for 1 hour. The coated specimen was then removed from the water, suspended on a rack at $25^{\\circ}\\mathrm{C}.$ ? $50\\%$ RH for 12 hours and tested for anti-fog property by placing the coated substrate above beaker containing water at $50^{\\circ}\\mathrm{C}$ . for 3 minutes. If fog appeared on the coated substrate during this test, the time taken for the appearance of the fog was recorded. If no fog appeared during 1 minute of exposure, then the coating was considered to “pass” the 1 h water soak anti-fog test.  \n\n[0094] N-mark: In addition the anti-fog property of $12\\mathrm{~h~}$ conditioned water-soaked coated specimens was tested using a YT-810 Resistance to Fogging Tester (manufactured by Yin-Tsung Co.,Ltd) according to the EN166/EN168 protocol. This procedure constitutes the N-mark test. The test involves placing the coated substrate onto the tester. When the test is started, the coated substrate is exposed to $50^{\\circ}$ C. steam, and a laser is passed through the lens. The amount of fogging was determined by reduction in the transmission of the laser light over 8 seconds (s) of exposure. The coating fails the fog test if the laser transmission falls below $80\\%$ of the initial reading during the 8 s period, if not, it is rated as a pass.  \n\n[0095] The following is a description of the substrates referred to in the application: PC Lens: Polycarbonate Ophthalmic Lens; CR-39: CR-39 Polybisallyl Carbonate Ophthalmic Lens; MR-7: MR-7 Polythiourethane Ophthalmic Lens; PC Plaque: Bayer MAKROLON Polycarbonate Sheet.  \n\n[0096] The current invention consists of the synthetic product of isocyanate-reactive surfactants, hydrophilic polyols and isophorone diisocyanate. Specifically, the following examples illustrate practical formulations of the invention. The following table includes descriptions of the chemicals referred to in the examples:  \n\n<html><body><table><tr><td>Common Name</td><td>Chemical</td><td>Manufacturer</td><td>Product Purpose</td></tr><tr><td>TRIMET</td><td>trimethylol ethane</td><td>Geo Specialty Chemicals, Inc</td><td>Polyol</td></tr><tr><td>Ethylene glycol</td><td>Ethylene glycol</td><td>Allentown, PA Sigma-Aldrich St. Louis, MO</td><td>Polyol</td></tr><tr><td>POLY-G 83-34</td><td>Trifunctional Polyethylene oxide-co-polypropylene oxide</td><td>Monument Chemical Indianapolis, IN</td><td>Polyol</td></tr><tr><td>ETERNACOLL UH200</td><td>Polycarbonate diol</td><td>UBE America, Inc New York, NY</td><td>Polyol</td></tr><tr><td>TEGOMER D3403</td><td>Ethoxylated polyether</td><td>Evonik Corporation Hopewell, VA</td><td>Polyol</td></tr><tr><td>PEG Mw300</td><td>Polyethylene glycol</td><td>Sigma-Aldrich St. Louis, MO</td><td>Polyol</td></tr><tr><td>DAA</td><td>polymer Diacetone alcohol</td><td>Univar Downers Grove, IL</td><td>Solvent</td></tr><tr><td>PM Glycol Ether</td><td>2-methoxy propanol</td><td>Univar Downers Grove, IL</td><td>Solvent</td></tr></table></body></html>  \n\n-continued   \nExample 1   \n\n\n<html><body><table><tr><td>Common Name</td><td>Chemical</td><td>Manufacturer</td><td>Product Purpose</td></tr><tr><td>FOMREZ UL-22</td><td>Dimethyltin mercaptide</td><td>Galata Chemicals Southbury, CT</td><td>Catalyst</td></tr><tr><td>Aerosol OT-75</td><td>Sulfosuccinate surfactant</td><td>Cytec Industries, Inc Woodland Park, NJ</td><td>Surfactant</td></tr><tr><td>SCHERCOQUAT</td><td>Quaternary Amine</td><td>Lubrizol</td><td>Surfactant</td></tr><tr><td>IAS-PG CIRRASOL G-265</td><td>Surfactant</td><td>Brecksville,OH Croda Coatings and</td><td></td></tr><tr><td></td><td>Fatty amine quaternary ammonium salt</td><td>Polymers Edison, NJ</td><td>Reactive Surfactant</td></tr><tr><td>TERGITOL 15-s-7</td><td>Secondary alcohol ethoxylate</td><td>Sigma-Aldrich St. Louis, MO</td><td>Reactive Surfactant</td></tr><tr><td>SURFCON 94</td><td>Proprietary Surfactant Mix</td><td>FSI Coatings Technology Irvine, CA</td><td>Reactive Surfactant mix</td></tr><tr><td>CAPSTONE FS-35</td><td>Nonionic fluorosurfactant</td><td>Chemours Newark,DE</td><td>Surfactant</td></tr><tr><td>BYK 356</td><td>Polyacrylate-based surfactant additive</td><td>BYK USA, Inc Wallingford,CT</td><td>Surfactant</td></tr><tr><td>K60</td><td>Polyvinylpyrrolidone polymer</td><td>Ashland Columbus, OH</td><td>Additive</td></tr><tr><td>SOKALAN K-17</td><td>Polyvinylpyrrolidone polymer Acrylate-functionalized</td><td>BASF Florham Park, NJ Nissan Chemical America</td><td>Additive</td></tr><tr><td>PGM-AC-2140Y</td><td>Organosilicate sol</td><td>Corporations Houston,TX</td><td>Additive</td></tr><tr><td>IPDI</td><td>Isophorone diisocyanate</td><td>Covestro LLC Pittsburgh, PA</td><td>Polyisocyanate</td></tr><tr><td>IRGACURE 1173</td><td>2-hydroxy-2-methyl-propiophenone</td><td>BASF Florham Park, NJ</td><td>Photoinitiator</td></tr><tr><td>IRGACURE 184</td><td>Hydroxyketone</td><td>BASF Florham Park, NJ</td><td>Photoinitiator</td></tr><tr><td>AIBN</td><td>Azobisisobutyronitrile</td><td>Sigma-Aldrich Oakville,ON</td><td>Thermal radical initiator</td></tr><tr><td>VAM-110</td><td>Oil-soluble azo polymerization initiator</td><td>Wako Chemicals USA Inc Richmond, VA</td><td>Thermal radical initiator</td></tr><tr><td>VA-086</td><td>Water-soluble azo itiator</td><td>Wako Chemicals USA Inc Richmond, VA</td><td>Thermal radical initiator</td></tr><tr><td>3-EGA</td><td>3-ethylene glycol diacrylate</td><td>Arkema King of Prussia, PA</td><td>Ethylenically unsaturated</td></tr><tr><td>4-HBA</td><td>4-hydroxybutylacrylate</td><td>San Estes Corporation New York, NY</td><td>crosslinker Isocyanate-reactive ethylenically</td></tr></table></body></html>  \n\n[0097] $_{19.74\\mathrm{~g~}}$ of trimethylolethane, $9.87~\\mathrm{\\ttg}$ of ethylene glycol, $78.97\\ \\mathrm{g}$ of POLY-G 83-34, and $276.41\\textrm{g}$ of DAA were loaded into a round-bottom flask and mixed at $50^{\\circ}\\mathrm{C}$ until dissolved. $195.85\\ \\mathrm{g}$ isophorone diisocyanate, $9.87\\ \\mathrm{{g}}$ of ETERNACOLL UH200, and $63.18\\mathrm{g}$ of TEGOMER D3403 were added to the flask. $0.18\\mathrm{\\g}$ ofFOMREZ UL-22 was then added to the flask and mixed at $70^{\\circ}\\mathrm{C}$ .for 30 minutes.188.35 $\\mathbf{g}$ DAA, $\\mathrm{15.07~g}$ Aerosol OT-75, $6.46\\ \\mathrm{g}$ SCHERCOQUAT IAS-PG, $59.23\\ \\mathrm{g}$ CIRRASOL G-265, $1.97\\mathrm{g}$ TERGITOL15- $\\mathbf{s}{-}7$ ，and $0.18\\ \\mathrm{g}$ FOMREZ UL-22 were added to the round bottom flask and allowed to mix at $70^{\\circ}\\mathrm{~C~}$ .for 1 hour.After mixing, $63.18\\mathrm{~g~}$ 4-hydroxybutyl acrylate and $0.18\\mathrm{~g~}$ FOMREZ UL-22 were added to the mixture and allowed to mix for 30 minutes at $70^{\\circ}\\mathrm{~C~}$ ·  \n\n[0098] $11.85\\mathrm{~g~}$ trimethylolethane and $0.18\\mathrm{~g~}$ UL-22 were added to the round bottom flask and mixed for 2 hours at $70^{\\circ}$ C. After mixing the flask was cooled to room temperature.  \n\n[0099] After the mixture is cooled, $726\\mathrm{~g~}1$ -methoxy propanol and $18.73\\ \\mathrm{g}$ of IRGACURE 1173 were added and mixed at room temperature for 1 hour. The sample was dipcoated onto a polycarbonate lens and cured using a Vela 3D (UV) cure unit at $\\scriptstyle2.0\\mathrm{J}/\\mathrm{cm}^{2}$ . Cured coating properties are shown in Table 4.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 20,
+        "chunk": "# Example 2  \n\n[0100] $25.00~\\mathrm{g}$ of trimethylolethane, $10.00\\ \\mathrm{g}$ of ethylene glycol, $100.00\\ \\mathrm{g}$ of POLY-G 83-34, and $276.41\\ \\mathrm{g}$ of DAA were loaded into a round-bottom flask and mixed at $50^{\\circ}\\mathrm{C}$ · until dissolved. $215.00\\mathrm{g}$ isophorone diisocyanate, $10.00{\\mathrm{g}}$ of ETERNACOLL UH200, and $60.00{\\mathrm{g}}$ of TEGOMERD3403 were added to the flask. $0.18\\mathrm{\\g}$ ofFOMREZUL-22 was then added to the flask and mixed at $70^{\\circ}\\mathrm{~C~}$ .for 30 minutes. [0101] $_{125.00\\mathrm{~g~}}$ SURFCON 94 and $0.18\\mathrm{~g~}$ FOMREZ UL-22 were added to the round bottom flask and allowed to mix at $70^{\\circ}\\mathrm{~C~}$ . for 1 hour. After mixing, $75.00\\mathrm{\\g}$ 4-hydroxybutyl acrylate and $0.18\\mathrm{g}$ FOMREZ UL-22 were added to the mixture and allowed to mix for 30 minutes at $70^{\\circ}\\mathrm{~C~}$ [0102] $15.00\\ \\mathrm{g}$ trimethylolethane and $0.18\\mathrm{~g~}$ UL-22 were added to the round bottom flask and mixed for 2 hours at $70^{\\circ}$ C. After mixing the flask was cooled to room temperature. [0103]  After the mixture is cooled, $725\\ \\mathrm{~g~}1$ -methoxy propanol and $20.22\\ \\mathrm{g}$ of IRGACURE 1173 were added and mixed at room temperature for 1 hour. The sample was dipcoated onto a polycarbonate lens and cured using a Vela 3D (UV) cure unit at $2.0\\mathrm{J}/\\mathrm{cm}^{2}$ . Cured coating properties are shown in Table 4.  \n\ndipcoated onto a polycarbonate lens and cured using a Vela 3D (UV) cure unit at $2.0\\mathrm{J}/\\mathrm{cm}^{2}$ . Cured coating properties are shown in Table 4.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 21,
+        "chunk": "# Example 3  \n\n[0104] $7.79\\ \\mathrm{\\g}$ of trimethylolethane, $4.54\\mathrm{~g~}$ of ethylene glycol, $37.63\\mathrm{~g~}$ of POLY-G 83-34, and $181.68\\mathrm{~g~}$ of DAA were loaded into a round-bottom flask and mixed at $50^{\\circ}\\mathrm{C}$ until dissolved. $77.86\\ \\mathrm{g}$ isophorone diisocyanate, $6.49\\ \\mathrm{g}$ of ETERNACOLL UH200, and $31.14\\ \\mathrm{g}$ of TEGOMER D3403 were added to the flask. $0.08\\ \\mathrm{g}$ ofFOMREZ UL-22 was then added to the flask and mixed at $70^{\\circ}\\mathrm{~C~}$ .for 30 minutes. [0105] $90.84\\ \\mathrm{~g~}$ DAA, $7.26\\ \\mathrm{\\g}$ Aerosol OT-75, $3.11\\ \\mathrm{\\g}$ SCHERCOQUATIAS-PG,28.55 CIRRASOL G-265,1.04 g TERGITOL15-s-7, and $0.18\\mathrm{~g~}$ FOMREZ UL-22 were added to the round bottom flask and allowed to mix at $70^{\\circ}$ C.for 1 hour. After mixing, $16.87\\ \\mathrm{g}4$ -hydroxybutyl acrylate and $0.08\\mathrm{\\g}$ FOMREZ UL-22 were added to the mixture and allowed to mix for 30 minutes at $70^{\\circ}\\mathrm{~C~}$ [0106] $5.19\\ \\mathrm{g}$ trimethylolethane and $0.08{\\mathrm{~g~}}$ UL-22 were added to the round bottom flask and mixed for 2 hours at $70^{\\circ}$ C. After mixing the flask was cooled to room temperature. [0107]  After the mixture is cooled, $363\\mathrm{~g~}1$ -methoxy propanol and $9.37~\\mathrm{g}$ of IRGACURE 1173 were added and mixed at room temperature for 1 hour. The sample was dipcoated onto a polycarbonate lens and cured using a Vela 3D (UV) cure unit at $2.0\\mathrm{J}/\\mathrm{cm}^{2}$ . Cured coating properties are shown in Table 4.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 22,
+        "chunk": "# Example 4 (Comparative)  \n\n[0108] $1.78\\mathrm{~g~}$ of trimethylolethane, $1.75\\mathrm{~g~}$ of ethylene glycol, $41.26\\ \\mathrm{g}$ of POLY-G 83-34, and $79.10\\mathrm{g}$ of DAA were",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 23,
+        "chunk": "# Example 5  \n\n[0111] $100\\mathrm{g}$ of Example 1 was mixed with $0.4\\ \\mathrm{g}$ of3-EGA for 1 hour at room temperature conditions. The sample was dipcoated onto a polycarbonate lens and cured using a Vela 3D (UV) cure unit at $\\mathsf{2.0~J}/\\mathrm{cm}^{2}$ . Cured coating properties are shown in Table 4.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 24,
+        "chunk": "# Example 6  \n\n[0112] $100\\mathrm{g}$ of Example 3 was mixed with $0.4\\ \\mathrm{g}$ of3-EGA for 1 hour at room temperature conditions. The sample was dipcoated onto a polycarbonate lens and cured using a Vela 3D (UV) cure unit at $2.0\\mathrm{J}/\\mathrm{cm}^{2}$ . Cured coating properties are shown in Table 4.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 25,
+        "chunk": "# Example 7  \n\n[0113] $100\\ \\mathrm{g}$ of Example 1 was mixed with $0.2\\ \\mathrm{g}$ of3-EGA for 1 hour at room temperature conditions. The sample was dipcoated onto a polycarbonate lens and cured using a Vela 3D (UV) cure unit at $2.0\\mathrm{J}/\\mathrm{cm}^{2}$ . Cured coating properties are shown in Table 4.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 26,
+        "chunk": "# Example 8  \n\n[0114] $100\\mathrm{g}$ of Example 3 was mixed with $0.2\\ \\mathrm{g}$ of3-EGA for 1 hour at room temperature conditions. The sample was dipcoated onto a polycarbonate lens and cured using a Vela 3D (UV) cure unit at $2.0\\mathrm{J}/\\mathrm{cm}^{2}$ . Cured coating properties are shown in Table 4.  \n\nTABLE 4   \nExample 9   \n\n\n<html><body><table><tr><td colspan=\"8\">Cured coating properties of Examples 1-8.</td></tr><tr><td></td><td>Thickness (um)</td><td>Haze (%)</td><td>Adhesion (%)(Scotch Anti-fog 3M600, 3 pulls)</td><td>Initial (60°C., 3 min)</td><td>Water Soak Anti-fog Test (50°C., 3 min)</td><td>N-Mark (anti-fog)</td><td>to Damage by fine particles, En166)</td></tr><tr><td>Example 1</td><td>8.0</td><td>0.15</td><td>100%</td><td>Pass</td><td>Pass</td><td>Pass</td><td>Pass</td></tr><tr><td>Example 2</td><td>8.7</td><td>0.17</td><td>100%</td><td>Pass</td><td>Pass</td><td>Pass</td><td>Pass</td></tr><tr><td>Example 3</td><td>7.5</td><td>0.35</td><td>100%</td><td>Pass</td><td>Pass</td><td>Pass</td><td>Fail</td></tr><tr><td>Example 4</td><td>8.0</td><td>0.20</td><td>100%</td><td>Pass</td><td>Fail</td><td>Fail</td><td>Fail</td></tr><tr><td>Example 5</td><td>8.8</td><td>0.16</td><td>100%</td><td>Pass</td><td>Pass</td><td>Pass</td><td>Pass</td></tr><tr><td>Example 6</td><td>8.7</td><td>0.14</td><td>100%</td><td>Pass</td><td>Pass</td><td>Pass</td><td>Pass</td></tr><tr><td>Example 7</td><td>8.1</td><td>0.18</td><td>100%</td><td>Pass</td><td>Pass</td><td>Pass</td><td>Pass</td></tr><tr><td>Example 8</td><td>8.8</td><td>0.17</td><td>100%</td><td>Pass</td><td>Pass</td><td>Pass</td><td>Pass</td></tr></table></body></html>  \n\nloaded into a round-bottom flask and mixed at $50^{\\circ}\\mathrm{C}$ .until dissolved. $19.70\\mathrm{~g~}$ of isophorone diisocyanate, $6.22\\ {\\tt g}$ of ETERNACOLL UH200, $16.44\\mathrm{g}$ of CIRRASOL G-265, and $10.38\\ \\mathrm{g}$ of PEG Mw30o were added to the flask. $0.08~\\mathrm{g}$ of FOMREZ UL-22 was then added to the flask and mixed at $70^{\\circ}\\mathrm{~C~}$ .for 30 minutes.  \n\n[0109] $16.50\\mathrm{g}$ IPDI, $15.20\\ \\mathrm{g}\\ \\cdot$ 4-hydroxybutylacrylate, and $0.08\\mathrm{~g~}$ FOMREZ UL-22 were added to the round bottom flask and allowed to mix at $70^{\\circ}\\mathrm{~C~}$ . for 1 hour.  \n\n[0110]  After the mixture is cooled, $114.40\\ \\mathrm{g}$ of 1-methoxy propanol and $3.87~\\mathrm{g}$ of IRGACURE 1173 were added and mixed at room temperature for 1 hour. The sample was [0115] $\\ensuremath{19.74\\mathrm{\\g}}$ of trimethylolethane, $9.87~\\mathrm{\\ttg}$ of ethylene glycol, $78.97\\ \\mathrm{g}$ of POLY-G 83-34, and $276.41\\textrm{g}$ of DAA were loaded into a round-bottom flask and mixed at $50^{\\circ}\\mathrm{C}$ until dissolved. $195.85\\ \\mathrm{g}$ of isophorone disocyanate, $9.87\\ \\mathrm{g}$ of ETERNACOLL UH200, and $63.18\\mathrm{~g~}$ of TEGOMER D3403 were added to the flask. $0.18\\mathrm{~g~}$ of FOMREZ UL-22 was then added to the flask and mixed at $70^{\\circ}$ C.for 30 minutes.  \n\n[0116]152.0 SURFCON 94 and $0.18\\mathrm{~g~}$ FOMREZ UL-22 were added to the round bottom flask and allowed to mix at $70^{\\circ}~\\mathrm{C}$ . for 1 hour. After mixing, $63.18\\mathrm{~g~}$ 4-hydroxybutyl acrylate and $0.18\\mathrm{~g~}$ FOMREZ UL-22 were added to the mixture and allowed to mix for 30 minutes at $70^{\\circ}\\mathrm{~C~}$ [0117] $\\ensuremath{11.85\\mathrm{~g~}}$ trimethylolethane and $0.18\\mathrm{~g~}$ UL-22 were added to the round bottom flask and mixed for 2 hours at $70^{\\circ}$ C.After mixing the flask was cooled to room temperature.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 27,
+        "chunk": "# Example 10  \n\n[0118]  To $7.00~\\mathrm{g}$ of the Example 9, $\\ensuremath{1.75\\mathrm{~g~}}$ of PGM-AC2140Y was added while stirring. After mixing for $15~\\mathrm{min}$ 1 utes, $3.00~\\mathrm{g}$ of PM glycol ether was added while stirring. This was followed by addition of $0.05\\mathrm{~g~}$ thermal radical initiator (AIBN). $0.10~\\mathrm{g}$ of $10\\%$ BYK 356 in PM, and 0.04 g of mixture of CAPSTONE FS35 and SCHERCOQUAT IAS-PG in the ratio 1:25, were added. The coating solution was mixed for $30~\\mathrm{min}$  \n\n[0119] Coated parts were prepared by flow coating the liquid formulations on polycarbonate substrate. All the parts were air dried for 1 min. Thermal curing was then initiated at $90^{\\circ}\\mathrm{C}$ . for 3 min and completed at $90^{\\circ}\\mathrm{C}$ for 4 hrs. Coated properties are listed in Table 5.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 28,
+        "chunk": "# Example 11  \n\n[0120] To $7.00~\\mathrm{g}$ of the Example 9, $\\ensuremath{1.75\\mathrm{~g~}}$ of PGM-AC2140Y was added while stirring. After mixing for 15 minutes, $3.00~\\mathrm{g}$ of PM glycol ether was added while stirring. This was followed by addition of $0.05\\mathrm{~g~}$ thermal radical initiator (VAM-110). $0.10\\mathrm{~g~}$ of $10\\%$ BYK 356 in PM, and $\\mathbf{0.04\\g}$ of mixture of CAPSTONE FS35 and SCHERCOQUAT IAS-PG in the ratio 1:25, were added. The coating solution was mixed for $30~\\mathrm{min}$ ·  \n\n[0121] Coated parts were prepared by flow coating the liquid formulations on polycarbonate substrate. All the parts were air dried for 1 min. Thermal curing was then initiated at $90^{\\circ}\\mathrm{C}$ for 3 min and completed at $115^{\\circ}\\mathrm{C}$ .for $^{2\\mathrm{h}}$ Coated properties are listed in Table 5.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 29,
+        "chunk": "# Example 11A  \n\n[0122] Another set of coated parts using the same liquid formulation of Example 11 were prepared by flow coating on polycarbonate substrates. Parts were air dried for $1~\\mathrm{min}$  \n\nThermal curing was then initiated at $90^{\\circ}\\mathrm{~C~}$ . for 3 min and completed at $110^{\\circ}\\mathrm{C}$ .for $45\\mathrm{{min}}$ Coated properties are listed in Table 5.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 30,
+        "chunk": "# Example 12  \n\n[0123] To $7.00~\\mathrm{g}$ of the Example 9, $\\ensuremath{1.75~\\mathrm{g}}$ of PGM-AC2140Y was added while stirring. After mixing for $15~\\mathrm{min}$ utes, $3.00~\\mathrm{g}$ of PM glycol ether was added while stirring. This was followed by addition of $0.05\\mathrm{~g~}$ thermal radical initiator (VA-086). $0.10\\mathrm{{g}}$ of $10\\%$ BYK 356 in PM, and 0.04 g of mixture of CAPSTONE FS35 and SCHERCOQUAT IAS-PG in the ratio 1:25, were added. The coating solution was mixed for $30~\\mathrm{min}$  \n\n[0124] Coated parts were prepared by flow coating the liquid formulations on polycarbonate substrate. All the parts were air dried for 1 min. Thermal curing was then initiated at $90^{\\circ}\\mathrm{C}$ for 3 min and completed at $100^{\\circ}\\mathrm{C}$ .for $^{4\\mathrm{h}}$ .Coated properties are listed in Table 5.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 31,
+        "chunk": "# Example 13  \n\n[0125]To $50.00\\ \\mathrm{g}$ of Example 9, $0.74\\ \\mathrm{g}$ of IRGACURE 184 and $30.00\\ \\mathrm{g}$ of a $10\\%$ mix of SOKALAN K17 in PM were added. The mixture was agitated for at least 20 minutes prior to coating.  \n\n[0126] Coated parts were prepared by flow coating the liquid formulations on polycarbonate substrate. All the parts were air dried for 1 min. and initially thermally cured at $90^{\\circ}$ C.for $3\\mathrm{min}$ . The cure was completed using a Vela 3D (UV) Cure Unit at $2.0\\mathrm{\\J}/\\mathrm{cm}^{2}$ . Coated properties are listed in Table 6.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 32,
+        "chunk": "# Example 14  \n\n[0127] To $50.00\\ \\mathrm{g}$ of Example 9, $0.74\\ \\mathrm{g}$ of IRGACURE 184 and $10.00\\ \\mathrm{g}$ of a $30\\%$ K60 in water were added. After mixing for 2 minutes, $20.00\\textrm{g}$ of PM was added to the beaker. The mixture was agitated for at least 2O minutes prior to coating.  \n\n[0128] Coated parts were prepared by flow coating the liquid formulations on polycarbonate substrate. All the parts were air dried for 1 min, and initially thermally cured at $90^{\\circ}$ C.for $3\\mathrm{min}$ . The cure was completed using a Vela 3D (UV) cure unit at $2.0\\ \\mathrm{J}/\\mathrm{cm}^{2}$ Coated properties are listed in Table 6.  \n\nTABLE5   \n\n\n<html><body><table><tr><td colspan=\"6\">Comparison of Coating Performance of Thermal Cure Samples of Examples 10-12</td></tr><tr><td>(%)</td><td>Thickness (um)</td><td>Haze 3M 600,</td><td>Adhesion (Scotch 3 pulls)</td><td>Initial Anti-fog (60°C., 3 min)</td><td>Water Soak Anti-fog Test (50°C.， 3 min)</td><td>N-Mark (anti-fog)</td></tr><tr><td>Example 10</td><td>7.3</td><td>0.40</td><td>Pass</td><td>Pass</td><td>Pass</td><td>Pass</td></tr><tr><td>Example 11</td><td>8.8</td><td>0.35</td><td>Pass</td><td>Pass</td><td>Pass</td><td>Pass</td></tr><tr><td>Example 11A</td><td>8.6</td><td>0.4</td><td>Pass</td><td>Pass</td><td>Pass</td><td>Pass</td></tr><tr><td>Example 12</td><td>9.5</td><td>0.30</td><td>Pass</td><td>Pass</td><td>Pass</td><td>Pass</td></tr></table></body></html>  \n\nTABLE6   \n\n\n<html><body><table><tr><td colspan=\"7\">Comparison of Coating Performance of Examples 13 and 14</td></tr><tr><td>Thickness</td><td>(um)</td><td>Haze (%)</td><td>Adhesion (Scotch 3M 600, 3 pulls)</td><td>Initial Anti-fog (60°C., 3 min)</td><td>Water Soak Anti-fog Test (50°C.，N-Mark 3 min)</td><td>(anti-fog)</td></tr><tr><td>Example 13</td><td>6.0-8.0</td><td>0.44</td><td>Pass</td><td>Pass</td><td>Pass</td><td>Pass</td></tr><tr><td>Example 14</td><td>2.0-4.0</td><td>>1.0</td><td>Pass</td><td>Pass</td><td>Pass</td><td>Pass</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 33,
+        "chunk": "# Example 15 (Comparative)  \n\n[0129]  In accordance with JP H11-140109, a prepolymer was synthesized in the laboratory (Synthesis II, Table 9). The formulations were mixed overnight (15a, 15b, 15c, Table 1O). These formulations were then applied to a polycarbonate substrate and cured with a Fusion Conveyor (UV) cure unit. The coatings did not pass K-mark or N-mark. Table 11 shows the comparative example performance summary for these coating formulations.  \n\nTABLE 9   \n\n\n<html><body><table><tr><td colspan=\"4\">Synthesis II products</td></tr><tr><td>1</td><td>Anhydrous Citric acid</td><td>34.6</td><td>g Mix at</td></tr><tr><td>2</td><td>Polyethyleneglycol diglycidyl ether (200)</td><td>207.6</td><td>g 90°C.</td></tr><tr><td>3</td><td>Dimethylamine Hydrochloride</td><td>3</td><td>g for 3 h</td></tr><tr><td>4</td><td>Acrylic acid</td><td>57.9</td><td>g</td></tr><tr><td>5</td><td>Hydroquinone</td><td>0.3</td><td></td></tr></table></body></html>  \n\nTABLE10   \n\n\n<html><body><table><tr><td colspan=\"4\">Comparative Example Formulations</td></tr><tr><td></td><td>Example 15a</td><td>Example 15b</td><td>Example 15c</td></tr><tr><td>Synthesis II</td><td>60 g</td><td>45g</td><td>40g</td></tr><tr><td>M-220 Tri Propylene glycol diacrylate</td><td>30g</td><td>0g</td><td>0g</td></tr><tr><td>M-240 Tetraethylene glycol diacrylate</td><td>0g</td><td>45g</td><td>40g</td></tr><tr><td>Adeka ER-10</td><td>10 g</td><td>10g</td><td>20g</td></tr><tr><td>IRGACURE 184</td><td>3g</td><td>3g</td><td>3g</td></tr></table></body></html>  \n\nTABLE11   \n\n\n<html><body><table><tr><td colspan=\"4\">Comparative Example Performance Summary</td></tr><tr><td></td><td>Example 15a</td><td>Example 15b</td><td>Example 15c</td></tr><tr><td>Thickness (um)</td><td>Cannot Measure</td><td>8.0-15.0</td><td>8.0-15.0</td></tr><tr><td>Haze (%)</td><td>16.0</td><td>0.84</td><td>1.26</td></tr><tr><td>Initial AF</td><td>Fog free for</td><td>Fog free for</td><td>Fog free for</td></tr><tr><td>(60°C., 3 min)</td><td>less than 30 s</td><td>less than 30 s</td><td>less than 30 s</td></tr><tr><td>Water-Soak</td><td>Fail</td><td>Fail</td><td>Fail</td></tr><tr><td>Anti-Fog Test</td><td>Fail</td><td>Fail</td><td>Fail</td></tr><tr><td>K-mark</td><td>Fail</td><td>Fail</td><td>Fail</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 34,
+        "chunk": "# Example 16 (Comparative)  \n\n[0130] Following U.S. Pat.No.8,642,180, Example 5 was synthesized in the lab as a comparative example. The coating liquid was applied to polycarbonate substrates via dipcoating and exposed to UV radiation in a Vela 3D cure unit at $2.0\\ \\mathrm{J/cm}^{2}$ . The coating liquid remained tacky to the touch and did not cure under UV radiation.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 35,
+        "chunk": "# Example 17 (Comparative)  \n\n[0131] U.S. Pat. No. 10,221,331 outlines a UV curable formulation that offers washable anti-fog with high steel wool abrasion resistance but not resistance to surface damage by fine particles (EN166 K Mark). The coating compositions of the present disclosure are directed to specially engineered urethane acrylate, which is thermally curable and/or UV curable, with exceptional anti-fog property passing $\\mathrm{EN}166\\mathrm{N}$ mark and resistance to surface damage by fine particles passing EN166 K Mark.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 36,
+        "chunk": "# Example 18  \n\n[0132] $\\boldsymbol{100}\\ \\mathrm{g}$ of Example 2 was mixed with $0.25\\mathrm{~g~}$ of azobisisobutyronitrile (AIBN) overnight at room temperature conditions. The sample was dipcoated onto a polycarbonate lens. Samples were initially cured at $90^{\\circ}\\mathrm{~C~}$ .for at least 5 minutes and cure was completed using a Vela 3D (UV) cure unit at $2.0\\ \\mathrm{J/cm}^{2}$ . Cured coating properties are shown in Table 7.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 37,
+        "chunk": "# Example 19  \n\n[0133] $\\boldsymbol{100}\\mathrm{~g~}$ of Example 2 was mixed with $0.38\\mathrm{~g~}$ of AIBN overnight at room temperature conditions. The sample was dipcoated onto a polycarbonate lens. Samples were initially cured at $90^{\\circ}\\mathrm{C}$ . for at least 5 minutes and cure was completed using a Vela 3D (UV) cure unit at $2.0\\mathrm{\\J}/\\mathrm{cm}^{2}$ · Cured coating properties are shown in Table 7.  \n\nTABLE7   \nExample 20   \n\n\n<html><body><table><tr><td colspan=\"8\">Dual Radical Cure Coating Properties</td></tr><tr><td>Sample</td><td>Thickness (um)</td><td>Haze (%)</td><td>Initial Adhesion (%)</td><td>Initial AF</td><td>N-mark</td><td>K-mark</td></tr><tr><td>Example18</td><td>9.3</td><td>0.47</td><td>100%</td><td>Pass</td><td>Pass</td><td>Pass</td></tr><tr><td>Example 19</td><td>9.6</td><td>0.39</td><td>100%</td><td>Pass</td><td>Pass</td><td>Pass</td></tr></table></body></html>  \n\n[0134] Example 2 was dipcoated onto a polycarbonate lens and cured using a Fusion Conveyor UV cure unit at 2.0 $\\mathrm{J}/\\mathrm{cm}^{2}$ . Cured coating properties are shown in Table 8.  \n\nTABLE8   \n\n\n<html><body><table><tr><td colspan=\"7\">Fusion Conveyor Cure Unit Performance</td></tr><tr><td>Sample</td><td>Thickness (mm)</td><td>Haze (%)</td><td>Adhesion Initial (%)</td><td>AF</td><td>N-Mark</td><td>K-mark</td></tr><tr><td>Example 20</td><td>9.2</td><td>0.35</td><td>100%</td><td>Pass</td><td>Pass</td><td>Pass</td></tr></table></body></html>  \n\n[0135] While the present disclosure describes exemplary aspects of coating compositions, articles, and methods in detail, the present disclosure is not intended to be limited to the disclosed aspects. Also, certain elements of exemplary aspects disclosed herein are not limited to any exemplary aspects, but instead apply to all aspects of the present disclosure.  \n\n[0136] The terminology as set forth herein is for description of the aspects of this disclosures only and should not be construed as limiting the disclosure as a whole. All references to singular characteristics or limitations of the present disclosure shall include the corresponding plural characteristic or limitation, and vice versa, unless otherwise specified or clearly implied to the contrary by the context in which the reference is made. Unless otherwise specified, “a,”“an,\" “the,\" and “at least one\" are used interchangeably. Furthermore, as used in the description and the appended claims, the singular forms “a,”“an,” and “the” are inclusive of their plural forms, unless the context clearly indicates otherwise. [0137]To the extent that the term “includes” or “including” is used in the description or the claims, it is intended to be inclusive in a manner similar to the term “comprising\" as that term is interpreted when employed as a transitional word in a claim. Furthermore, to the extent that the term “or” is employed (e.g., A or B) it is intended to mean “A or B or both.\" When the applicants intend to indicate“only A or B but not both”then the term “only A or B but not both”will be employed. Thus, use of the term “or” herein is the inclusive, and not the exclusive use.Furthermore, the phrase \"at least one of A, B, and C” should be interpreted as “only A or only B or only C or any combinations thereof.\"  \n\n[0138] The coating compositions, articles, and associate methods of making the coating composition or the article of the present disclosure can comprise, consist of, or consist essentially of the essential elements of the disclosure as described herein, as well as any additional or optional element described herein or which is otherwise useful in coating applications.  \n\n[0139]  All percentages, parts, and ratios as used herein are by weight of the total composition, unless otherwise specified. All ranges and parameters, including but not limited to percentages, parts, and ratios, disclosed herein are understood to encompass any and all sub-ranges assumed and subsumed therein, and every number between the endpoints. For example, a stated range of $^{\\ast}1$ to $10^{\\circ}$ should be considered to include any and all sub-ranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less (e.g., 1 to 6.1, or 2.3 to 9.4), and to each integer (1, 2, 3, 4, 5, 6, 7, 8, 9, and 10) contained within the range.  \n\n[0140] Any combination of method or process steps as used herein may be performed in any order, unless otherwise specified or clearly implied to the contrary by the context in which the referenced combination is made.  \n\n1. A coating composition comprising a mixture of an initiator, a radical curable polyurethane having ethylenically unsaturated functional groups, and a liquid phase, wherein the radical curable polyurethane having ethylenically unsaturated functional groups comprises the reaction products of:  \n\nA. a polyol component;   \nB. a polyisocyanate component;   \nC. an isocyanate-reactive surfactant; and   \nD. isocyanate-reactive component having ethylenically unsaturated functional groups.  \n\n2.The coating composition of claim 1 wherein the isocyanate-reactive component having ethylenically unsaturated functional groups is present in an amount ranging from 1 wt $\\%$ and $25\\mathrm{\\wt\\\\%}$ based on the total weight solids of the radical curable polyurethane.  \n\n3. The coating composition of claim 1, wherein the isocyanate-reactive component having an ethylenically unsaturated functional groups comprises an isocyanate-reactive alkoxylated acrylate.  \n\n4. The coating composition of claim 1, wherein an isocyanate-reactive surfactant is selected from quaternary ammonias, ether sulfonates, phosphoric acid esters, polyethers, polyether copolymers, alkyl ethers, alkenyl ethers, olefinic ethers, and combinations thereof.  \n\n5. The coating composition of claim 1, wherein the isocyanate-reactive surfactant is present in amounts ranging from 1-50 wt $\\%$ based on the total weight solids of the radical curable polyurethane.  \n\n6. The coating composition of claim 1, wherein the polyol comprises a diol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof, and/or (b) a triol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof.  \n\n7. The coating composition of claim 1, wherein the liquid   \nphase comprises water, an organic solvent, or a combination   \nthereof. 8. The coating composition of claim 3, wherein the   \nalkoxylated acrylate comprises a hydroxyl group. 9. The composition of claim 1, further comprising a   \nnon-reactive surfactant. 10. The coating composition of claim 1, further compris  \ning metal oxide nanoparticles. 11. The coating composition of claim 1, further compris  \ning multifunctional alkoxylated acrylate monomers. 12. The coating composition of claim 1, further compris  \ning a radical reactive surfactant having reactive functional   \ngroups comprising one or more of an alkenyl group, an   \nacrylate group, a thiol group, or combination thereof. 13. An article comprising: a substrate and a transparent   \nanti-fog coating applied onto the substrate, wherein the   \ncoating is formed from the coating composition of claim 1. 14. The coating composition of claim 1, wherein, when   \ncured on a substrate, the coating has water-washable anti-fog   \nproperties. 15. The coating composition of claim 1,wherein, when   \ncured on a substrate, the coating has wear-resistant proper  \nties. 16.The coating composition of claim 1,wherein, when   \ncured on a substrate, the coating has water-washable anti-fog   \nproperties and wear-resistant properties. 17.A coating composition comprising a mixture of an   \nelectron-beam curable polyurethane having ethylenically   \nunsaturated functional groups and a liquid phase, wherein  \n\nthe radical curable polyurethane having ethylenically unsaturated functional groups comprises the reaction products of:  \n\nA. a polyol component;   \nB. a polyisocyanate component;   \nC. an isocyanate-reactive surfactant; and   \nD. isocyanate-reactive component having ethylenically unsaturated functional groups.  \n\n18. An article comprising a substrate and the coating composition of claim 17 cured thereon.  \n\n19. The coating composition of claim 1, wherein, when cured, the coating formed from the coating composition has at least one of the EN166 K-mark, EN166 N-mark, or both the EN166 K-mark and EN166 N-mark.  \n\n20.The coating composition of claim 17, wherein, when cured, the coating formed from the coating composition has at least one of the EN166 K-mark, EN166 N-mark, or both the EN166 K-mark and EN166 N-mark.",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# (12) United States Patent Iwazumi et al.",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (54) ANTI-FOG POLYURETHANE COATING COMPOSITIONS  \n\n(75） Inventors: Masanori Iwazumi, Irvine, CA (US); Walter S. Creasy, Bridgewater, NJ (US); Robert G. LaCasse, Flemington, NJ (US)  \n\n(73） Assignee: SDC Technologies, Inc., Irvine, CA(US)  \n\n(\\*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 104 days.  \n\n(21)Appl.No.: 13/445,971 (22) Filed: Apr.13,2012 (65) Prior Publication Data  \n\nUS 2012/0308828 A1 Dec.6,2012",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# Related U.S. Application Data  \n\n(60）Provisional application No. 61/491,597, filed on May 31,2011.  \n\n(51) Int. Cl. B32B27/40 (2006.01) B32B27/32 (2006.01) B32B27/36 (2006.01) C08K5/5465 (2006.01) B05D 3/00 (2006.01)  \n\n5,316,791 A 5/1994 Farber et al. 5,798,409 A 8/1998 Ho 5,877,254 A 3/1999 La Casse et al. 6,569,533 B1 5/2003 Uchida et al. 6,780,516 B2 8/2004 Chen 6,897,281 B2 5/2005 Lubnin et al. 7,097,704 B1 8/2006 Pae 2005/0182154 A1\\* 8/2005 Berge et al. 523/160 2006/0014099 A1 1/2006 Faler et al. 2009/0081292 A1 3/2009 Otomo et al. 2010/0130701 A1 5/2010 Lahdensuo 2010/0256283 A1 10/2010 Kagata et al.  \n\n(10) Patent No.: (45) Date of Patent:",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# OTHERPUBLICATIONS  \n\nSurfactants Types and Uses, Laboratory of Formulation, Interfaces Rheology and Processes, FIRP Booklet #E300-A, Universidad de Los Andes, Merida-Venezuela, Version $\\#2$ ，2002.   \nFormulating Polyurethane Dispersions, Werner J.Blank, King Industries Inc., Norwalk, CT, accessed via the internet at wernerblank.com on Apr.9,2010.   \nUrethane-Acrylic Hybrid Polymers: Performance as 1K Coatings, Ernest C. Galgoci et al., Air Products and Chemicals, Inc., presented at The Society of the Plastics Industry/Epoxy Resin Formulators Division Spring Conference in Toronto, Canada, Apr. l-3,2001. International Search Report for International Application No. PCT/ US2012/033414, dated Jul.9, 2012.   \nWritten Opinion for International Application No. PCT/US2012/ 033414, dated Jul.9,2012.  \n\n\\* cited by examiner  \n\n(52) U.S. Cl. USPC 428/423.1; 428/423.3; 428/423.7; 428/424.6; 428/424.8; 428/425.6; 427/385.5; 524/501; 524/105",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# ABSTRACT  \n\n58) Field of Classification Search USPC 428/423.3, 423.7,424.6, 424.8, 425.6, 428/423.1; 427/385.5; 524/104, 501 See application file for complete search history.  \n\nPrimary Examiner— Thao T.Tran   \n(74)Attorney, Agent,or Firm—Calfee, Halter & Griswold   \nLLP  \n\nPolyurethane coating compositions that provide transparent, abrasion-resistant, and water-washable anti-fog coatings when applied to a substrate and cured are described herein. These polyurethane coating compositions have surfactants that are chemically associated with the polyurethane so as to not leach out or wash away when the coating surface is soaked or washed with water. The polyurethane coating compositions comprise isocyanate-reactive surfactants, isocyanatereactive salts of surfactants, carboxylic-reactive surfactants, or combinations thereof that are chemically bonded to the polyurethane.Articles coated with such polyurethane coating compositions, and processes for applying the coating compositions to a substrate, are also provided herein.",
+        "category": " Abstract"
+    },
+    {
+        "id": 6,
+        "chunk": "# References Cited",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# U.S.PATENTDOCUMENTS  \n\n3,935,146A 1/1976 Noll et al.   \n4,143,181 A 3/1979 Cahn et al.   \n5,262,475A 11/1993 Creasy",
+        "category": " References"
+    },
+    {
+        "id": 8,
+        "chunk": "# 25 Claims, No Drawings",
+        "category": " Abstract"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# 1 ANTI-FOGPOLYURETHANECOATING COMPOSITIONS  \n\nCROSS-REFERENCE TORELATED APPLICATION  \n\nThis application claims priority to and any other benefit of U.S. Provisional Patent Application Ser. No. 61/491,597, filed on May 31, 2011, and entitled“ANTI-FOG POLYURETHANE COATING COMPOSITIONS,” the entire disclo- 1( sure of which is incorporated by reference herein.",
+        "category": " Introduction"
+    },
+    {
+        "id": 11,
+        "chunk": "# FIELDOFTHEINVENTION  \n\nThe present invention relates to anti-fog coating composi- 15 tions.More particularly, the present invention relates to polyurethane coating compositions that provide transparent, abrasion-resistant, and water-washable anti-fog coatings when applied to a substrate and cured. The present invention also relates to articles coated with such polyurethane coating com- 20 positions and processes for applying the coating compositions to a substrate. The anti-fog polyurethane coating compositions are applied directly to the substrate or directly to a primer-coated substrate and cured, or the coating compositions are cast into unsupported films for later attachment to 25 the substrate.",
+        "category": " Introduction"
+    },
+    {
+        "id": 12,
+        "chunk": "# BACKGROUND  \n\nTransparent films are being increasingly used as coatings 3 for various glass and plastic articles, such as glass or plastic optical lenses; goggles; face shields; face plates for helmets; automobile windshields; substrates used between temperature differentials, i.e., frozen food display doors; and the like. Organic polymer coatings, such as polyurethanes, are par- 3 ticularly useful in providing self-supporting surfaces or coatings for such applications, in that these transparent materials can provide high strength and improved abrasion resistance to the surface. However, such polyurethane coatings have a high susceptibility to fogging (also referred to as frosting under 4 certain conditions) on their surfaces, which wiping of the surface cannot always adequately remedy.  \n\nFog appears when moisture condenses on a hydrophobic surface and is drawn into tiny droplets that scatter light. The scattering of the light gives the surface the appearance of a fog. Hydrophilic surfaces, on the other hand, will absorb the condensed moisture into the surface preventing the tiny light scattering droplets from forming.However, at some point the hydrophilic surface may reach saturation of the moisture, thus resulting in the formation of light scattering water droplets on the surface and resulting in poor anti-fog coatings. Hydrophilic surfaces which absorb the condensed moisture may also swell in an undesirable manner. Hydrophilic and hydrophobic surfaces can be modified by surface active agents, which are also known as surfactants, to spread or sheet the water across the surface. Surfactants containing both hydrophilic and hydrophobic segments act to minimize surface tension of the water with respect to the surface in an effect called “wetting.\" The“wetting” of the surface spreads or sheets the water out across the surface, thus minimizing the light scattering effect of the water droplets.  \n\nSurfactants are used to provide anti-fog properties to both hydrophilic and hydrophobic surfaces, including polyurethane polymer surfaces formed from polyurethane coatings. These surfactants can be physically associated with the polyurethane surface, such as being applied externally as a temporary film by wiping or spraying the surface.Alternatively, the surfactants can be mixed in with the polyurethane coating composition before it is applied to a substrate, so that the surfactant becomes physically trapped within the polyurethane polymer structure as the polyurethane cures. Such surfactants that are only physically associated with the polyurethane coating are easily washed off or leached away, thereby resulting in temporary anti-fog properties for the polyurethane surface.",
+        "category": " Introduction"
+    },
+    {
+        "id": 13,
+        "chunk": "# SUMMARY  \n\nThe polyurethane coating compositions described herein, when applied to a substrate and cured, provide transparent, abrasion-resistant, and water-washable anti-fog coatings. These polyurethane coating compositions have surfactants that are chemically associated with the polyurethane so as to minimize leaching out or washing away when the surface of a coating formed from the coating compositions is soaked or washed with water.  \n\nIn accordance with the embodiments of this invention, the coating compositions comprise isocyanate-reactive surfactants, isocyanate-reactive salts of surfactants, carboxylic-reactive surfactants, or combinations thereof that are chemically bonded to the polyurethane. In addition, the polyurethane comprises hydrophilic main chain segments, hydrophilic side chain segments, or combinations thereof in an amount ranging from about $0.01\\%$ to about $40\\%$ by weight of the solids of the polyurethane.  \n\nThe polyurethane coating compositions comprise （A）a first mixture comprising a first polyurethane and a first liquid phase selected from the group consisting of water, an organic solvent, and combinations thereof; or (B) a second mixture comprising a second polyurethane and a second liquid phase selected from the group consisting of water, an organic solvent, and combinations thereof; or (C) a third mixture comprising a third polyurethane and a third liquid phase selected from the group consisting of water, an organic solvent, and combinations thereof.  \n\nThe first polyurethane comprises the reaction products of a   \n40 first polyol component comprising a diol having polyethylene oxide side chain segments and at least one additional polyol component different than the first polyol component, a first polyisocyanate component, and a dihydroxy-carboxylic acid neutralized by a carboxylic-reactive amphoteric surfactant to   \n45 form a salt of the amphoteric surfactant. The first polyisocyanate component comprises at least one polyisocyanate selected from the group consisting of diisocyanates, triisocyanates, derivatives of diisocyanates and triisocyanates capable of forming polyurethane linkages, and combinations   \n50 thereof. The first polyurethane includes hydrophilic side chain segments in an amount ranging from about $0.01\\%$ to about $20\\%$ by weight of the solids of the first polyurethane.  \n\nThe second polyurethane comprises the reaction products of a second polyol component and at least one additional polyol component different than the second polyol component, a second polyisocyanate component comprising at least one partially blocked tri-functional polyisocyanate, an isocyanate-reactive salt of a surfactant, and an isocyanate-reactive cationic surfactant. The second polyol component comprises at least one of (a) a diol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof, or (b) a triol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof. The second polyurethane includes hydrophilic main chain segments in an amount ranging from about $0.01\\%$ to about $20\\%$ by weight of the solids ofthe second polyurethane.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3  \n\nThe third polyurethane comprises the reaction products of a third polyol component and at least one additional polyol component different than the third polyol component, a third polyisocyanate component, an isocyanate-reactive salt of a surfactant, and an isocyanate-reactive cationic surfactant. The third polyol component comprises a diol having polyethylene oxide side chain segments and at least one of (a) a diol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof, or (b) a triol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof. The third polyisocyanate component comprises (i) at least one polyisocyanate selected from the group consisting of diisocyanates, triisocyanates, derivatives of diisocyanates and triisocyanates capable of forming polyurethane linkages, and combinations thereof, and (ii) at least one partially blocked tri-functional polyisocyanate. The third polyurethane includes hydrophilic main chain segments, hydrophilic side chain segments, or combinations thereof in an amount ranging from about $0.01\\%$ to about $40\\%$ by weight of the solids of the third polyurethane.  \n\nThe coating compositions in accordance with the embodiments of this invention comprise aqueous polyurethane dispersions, organic solvent polyurethane solutions, or mixtures of an aqueous polyurethane dispersion and an organic solvent polyurethane solution.  \n\nIn accordance with other embodiments, articles coated with the anti-fog polyurethane coating compositions and processes for applying the coating compositions to a substrate are provided.  \n\nThe anti-fog polyurethane coating compositions described herein are directly applied to substrates or primer-coated substrates, and then cured, or they are cast as a free-form or self-supporting films that are applied to a substrate after having already cured. The free-form films optionally include an adhesive backing on one or both sides for application to one surface of a substrate or application in-between substrates.  \n\nThe present compositions are applied as coatings to a substrate surface and are sufficiently flexible to withstand further processing of the substrate, such as molding or shaping, without loss of its properties. A variety of substrates can be employed. Among the preferred substrate materials include transparent plastics such as polycarbonate, acrylic, polyvinylchloride, polybisallyl carbonate, polyethylene terephthalate, polyethylene naphthenate, polyurethane, and polythiourethane. Other substrates include various polyolefins, fluorinated polymers, metals and glass, such as soda-lime glass, borosilicate glass, and acrylic glass among other types of glass, are also used, and if necessary, are used with appropriate pretreatments.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# DETAILEDDESCRIPTION",
+        "category": " Introduction"
+    },
+    {
+        "id": 16,
+        "chunk": "# In General  \n\nUnless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description ofthe invention herein is for describing particular embodiments only and is not intended to be limiting of the invention. The present invention may be embodied in different forms, and the reference to the specific embodiments of this application should not be construed to limit the invention to the embodiments described herein. Rather, these embodiments are provided for thoroughness and completeness of this disclosure.  \n\nAs used in the description of the invention and the appended claims, the singular forms “a,\"“an,” and “the\" are intended to include the plural forms as well, unless the context clearly indicates otherwise.  \n\n5 Unless otherwise indicated (e.g., by use of the term “precisely\"), all numbers expressing quantities, properties such as molecular weight, reaction conditions, and so forth as used in the specification and claims are to be understood as being modified in all instances by the term “about.\" Accordingly, l0 unless otherwise indicated, the numerical properties set forth in the following specification and claims are approximations that may vary depending on the desired properties sought to be obtained in embodiments of the present invention.  \n\nDescribed herein are polyurethane coating compositions   \n15 that provide transparent, abrasion-resistant, and water-washable anti-fog coatings when applied to a substrate. Embodiments of these coating compositions include aqueous polyurethane dispersions, organic solvent polyurethane solutions, or mixtures of an aqueous polyurethane dispersion and an   \n20 organic solvent polyurethane solution. The polyurethane coating compositions comprise isocyanate-reactive surfactants, isocyanate-reactive salts of surfactants, carboxylic-reactive surfactants， or combinations thereof chemically bonded to the polyurethane structure. These chemically   \n25 bonded surfactants provide resistance to fogging by modifying the hydrophilicity or hydrophobicity of the surface of the polyurethane coating applied to the substrate. The surfactants decrease the surface tension of water as it condenses on the surface of the coating. By decreasing the surface tension of   \n30 the water, the surfactants cause the water to sheet out across the surface, rather than form the tiny droplets that cause light to scatter and give the appearance of fog on the surface of the coating. These surfactants also are useful in dispersing the polyurethane into water to form the aqueous dispersion   \n35 embodiments of the coating compositions in accordance with this invention.  \n\nFurthermore, the polyurethane coating compositions described herein comprise hydrophilic polyurethane polymers or prepolymers that provide anti-fogging properties and also contribute to the dispersibility of the polyurethane in a liquid phase. The polyurethane polymeric particles are made hydrophilic by adding hydrophilic segments to the polyurethane structure, either in the main chain, i.e., backbone, of the polyurethane, or as side chains, i.e., pendant segments. The hydrophilic segments include hydrophilic main chains, hydrophilic side chains, and combinations thereof, and comprise from about $0.01\\%$ to about $40\\%$ by weight of solids of the polyurethane.  \n\nIn general, a polyurethane is a polymer characterized by   \n50 the occurrence of urethane groups $[-\\mathrm{NH\\mathrm{~\\_~C=}O\\mathrm{-}O\\mathrm{-}}]$ and urea groups $[-\\mathrm{N-H-(C=O)}]\\mathrm{-NH-}]$ in a macromolecular chain. The urethane groups are formed by polyaddition reactions of polyisocyanates with polyols in the presence of a catalyst and other additives or additional reactants. The   \n55 urea groups are formed by polyaddition reactions of polyisocyanates and polyamines. Polyisocyanates are polymer molecules with two or more isocyanate functional groups, i.e., $\\scriptstyle\\mathrm{R}^{1}-(\\mathrm{N=C=O})_{n\\geq2}$ , and polyols are polymer molecules with two or more hydroxyl functional groups, i.e., $\\mathrm{R}^{2}-(\\mathrm{OH})_{n\\geq2}$   \n60 Polyamines are polymer molecules containing two or more amino functional groups, i.e., $\\mathrm{R}^{3}{\\mathrm{-}}(\\mathrm{NH}_{2})_{n\\geq2}$ . The polyurethane forming reactions take place in suitable organic solvents.  \n\nThe coating compositions described herein comprise a 55 mixture of at least one polyurethane and a liquid phase. Suitable liquid phases include water, organic solvents, and mixtures of water and organic solvents. Examples of suitable organic solvents include ketones such as methylethylketone, methylisobutyl ketone, diacetone alcohol, 3,3-dimethyl-2- butanone, and pentanedione; N-methyl pyrrolidone; acetonitrile; esters; glycol esters; glycol ethers such as propylene glycol monomethyl ether (PGME)， dipropylene glycol methyl ether, ethylene glycol n-butyl ether, diethylene glycol n-butyl ether, and diethylene glycol methyl ether; alcohols such as methanol, ethanol, n-butanol, isobutanol, and isopropanol; and tertiary alcohols such as tertiary-butyl alcohol, and tertiary-amyl alcohol.Different liquid phases can be selected based on the suitability to the intended application of the coating composition.For example, using organic solvents as all or part of the liquid phase improves wetting on hydrophobic substrates or substrates that do not readily accept aqueous-based compositions, such as dirty or silane treated glass, polycarbonate plastics with a waxy mold release, or plastics like polyethylene terephthalate, polypropylene, and polymethylpentene. Substituting water for all or part of the organic solvents in the liquid phase can reduce the amount of VOC's (volatile organic components) in the coating composition, and if prepared in the form of an aqueous dispersion, can result in a longer shelf life than other certain organic solvent based polyurethane coating compositions, e.g., two-component solvent-based polyurethane systems.  \n\nTherefore, in accordance with one embodiment, the coat- 2 ing compositions described herein comprise a polyurethane solution. In this embodiment, the coating composition is a mixture of at least one polyurethane and a liquid phase comprising an organic solvent.  \n\nIn accordance with another embodiment, polyurethane 3( coating compositions described herein comprise an aqueous polyurethane dispersion. In this embodiment, the coating composition is a mixture of at least one polyurethane and a liquid phase comprising water. The polyurethane is dispersed as polyurethane particles in the water to form the aqueous 35 dispersion.  \n\nIn accordance with another embodiment, the coating compositions described herein comprise a mixture of an aqueous polyurethane dispersion and an organic solvent polyurethane solution. In this embodiment, the coating composition is a mixture of at least one polyurethane and a liquid phase comprising water and an organic solvent. At least a portion of the polyurethane present in the mixture is dispersed as polyurethane particles in the water to form the aqueous dispersion part of the mixture. The residual non-dispersed polyurethane present in the mixture, which is miscible with the organic solvent, dissolves to form the solution part of the mixture.  \n\nIsocyanates readily react with any molecule or compound having an active hydrogen. Therefore, as used herein, the term “isocyanate-reactive” refers to any molecule or compound having an active hydrogen that readily reacts with isocyanate groups. Examples of such active hydrogen compounds  include compounds or molecules containing hydroxyl or amine functional groups. Similarly, the term “active hydrogen\" compound refers to any molecule or compound having a source of active hydrogen capable of reaction with other molecules or compounds, including being capable of reacting with isocyanate groups. The term “carboxylicreactive” refers to any base that reacts with a carboxylic acid functional group in a neutralization reaction to form a salt.  \n\nThe polyurethane coating compositions described herein include isocyanate-reactive cationic surfactants, isocyanatereactive salts of surfactants, carboxylic-reactive surfactants, or combinations thereof that are chemically bonded to the polyurethane.As used herein, an isocyanate-reactive salt of a surfactant refers to a salt of a surfactant that is isocyanatereactive or refers to constituent components of a salt that,  \n\nthrough an intermediate reaction, forms a salt of a surfactant. Accordingly, isocyanate-reactive salts of surfactants comprise salts having active hydrogen molecules or comprise each of the acids or bases used to form the salt. The chemical bond of these surfactants or salts of the surfactants to the polyurethane polymer structure minimizes leaching or erosion of the surfactant, thereby retaining anti-fogging characteristics of the coating applied to the substrate (i.e., in the faun of a coating composition directly applied to the substrate or 0 primer-coated substrate and subsequently cured, or in the form of a self-supporting film applied to the substrate), even after repeated washing or soaking of the coating.  \n\nThe coating compositions described herein have extremely long-lasting anti-fog characteristics relative to non-chemically bonded surfactants or surfactants that are only physically associated with the polyurethane polymer present in other polyurethane coatings. In addition to adding long-lasting anti-fog characteristics, the isocyanate-reactive surfactants, the isocyanate-reactive salts of surfactants, or the carboxylic-reactive surfactants at least partially or wholly act as a dispersing agent for aqueous polyurethane dispersion embodiments of the coating compositions described herein. Polyols  \n\nThe polyurethane coating compositions described herein comprise a polyurethane having hydrophilic polymer segments in the main polyurethane chain or hydrophilic polymer segments in pendant or side chains of the polyurethane polymer.  \n\nThe composition of the polyurethane determines the properties of the cured polyurethane coating. More specifically, the polyols that react with the isocyanates to form the polyurethane determine the properties of the polyurethane coating when cured. The polyols generally are active hydrogen mol  \n35 ecules, which make them isocyanate-reactive. Suitable polyols used herein include polycarbonate polyols, polyether polyols, and polyester polyols, preferably low molecular weight polyols, including low molecular weight polycarbonate diols or triols, polyether diols or triols, and polyester diols   \n40 or triols. Other suitable polyols include polyhydric alcohols and alkoxylated polyols; amide-containing polyols; polyacrylic polyols; epoxy polyols; polyhydric polyvinyl alcohols; or mixtures of any of the aforementioned polyols. The reaction of the polyols and isocyanates to form the polyure  \n45 thane takes place in an organic solvent at high temperatures. The composition of the polyol determines the solubility of the polyol in the organic solvent. High molecular weight polyols, especially those containing primarily urethane linkages, are generally not compatible with organic solvents, and therefore   \n50 are not preferred as a component for creating the polyurethane coating compositions described herein. Preferred polyols used herein include diols and triols, including but not limited to low molecular weight polycarbonate diols or triols, polyether diols or triols, or polyester   \n55 diols or triols. Suitable low molecular weight diols or triols include polyols having a molecular weight $(\\mathbf{M}_{\\scriptscriptstyle W})$ or average molecular weight distribution $(\\mathbf{M}_{n})$ range from about 500 to about 60o0, preferably from about 10o0 to about 5000. Examples of polyols include polyethylene glycol; trimethylol   \n60 propane monoethoxylate methyl ether; polyhexamethylene carbonate diol; or poly(1,4-butanediol). Additionally, nonpolymeric (i.e., monomeric) triols, such as trimethylolethane or trimethylolpropane, are used to form embodiments of the polyurethanes described herein. The rigidity and abrasion   \n65 resistance of the cured polyurethane coating improves with the use of triols, as the third functional hydroxyl group of the triol promotes and enhances crosslinking in the cured coating.  \n\nThe selection of the polyol modifies the hydrophilicity of the polyurethane, which affects the fog resistance of the cured polyurethane coating as well as dispersibility of the polyurethane in the liquid phase of a dispersion.Hydrophilic polyols, or polyols containing hydrophilic segments, add to the hydrophilic character of the polyurethane.Examples of hydrophilic polyols include alkoxylated polyether polyols, such as polyols containing polyethylene oxide (e.g., polyethylene glycol in low molecular weight compounds or polyoxyethylene) or polypropylene oxide (polyoxypropylene) segments. These segments comprise the main polymer chain (i.e., polymer backbone) of the polyol, or side chains (i.e., pendant chains) of the polyol, or segments of both the main and side chains of the polyol. Preferred for the polyurethane coating compositions described herein are hydrophilic polyether polyols containing polyethylene oxide main or side chain segments, polypropylene oxide main or side chain segments, or combinations thereof. Examples of suitable hydrophilic polyols include polyethylene glycol; trimethylol propane monoethoxylate methyl ether; diols having polyethylene oxide segments in the main chain, the side chain, or both the main chain and side chain; diols having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof; and triols having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof.  \n\nExamples of specific suitable hydrophilic polyols include a diol having polyethylene oxide side chains comprising from about $72\\%$ to about $90\\%$ polyethylene oxide by weight of the polyol, preferably about $75\\%$ to about $90\\%$ polyethylene oxide by weight of the polyol. This hydrophilic diol having polyethylene oxide side chains is the product of a two step reaction. The first reaction is between a hexamethylene diisocyanate and a mono-methoxy-polyethylene glycol having an average $\\mathbf{M}_{n}$ of about 1ooo.The product of the first reaction is then reacted with diethanolamine to form the hydrophilic diol having polyethylene oxide side chains comprising from about $72\\%$ to about $90\\%$ polyethylene oxide by weight of the polyol.  \n\nAn example of a specific suitable diol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof includes a polypropylene oxide and polyethylene oxide block copolymer diol comprising polyethylene oxide in the main chain in an amount ranging from about $10\\%$ to about $25\\%$ by weight of the polyol, preferably polyethylene oxide in the main chain ranging from about $15\\%$ to about $20\\%$ by weight of the polyol. An example of such a block copolymer diol is Pluronic L-62 (commercially available from BASF Corp of Germany).  \n\nAn example of a specific suitable triol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide， and combinations thereof includes a polypropylene oxide and polyethylene oxide copolymer triol comprising from about $60\\%$ to about $95\\%$ polyethylene oxide by weight of the polyol, preferably from about $75\\%$ to about $90\\%$ polyethylene oxide by weight of the polyol.An example of such a copolymer triol is Poly G 83-34 (commercially available from Arch Chemicals, Inc. of Norwalk, Conn.).  \n\nThe hydrophilic segments in the main or side chains in the polyol can lead to corresponding hydrophilic main or side chains segments in the polyurethane. The polyurethane coating compositions comprise hydrophilic polyurethane main chain segments, hydrophilic polyurethane side chain segments, or combinations thereof in an amount ranging from  \n\nabout $0.01\\%$ to about $40\\%$ by weight of the solids of the polyurethane, preferably from about $7\\%$ to about $25\\%$ by weight of the solids, more preferably from about $10\\%$ to about $20\\%$ by weight of the solids. Hydrophilic main chain segments comprise from O to about $20\\%$ by weight of solids of the polyurethane, preferably from O to about $15\\%$ by weight of the solids. Hydrophilic side chain segments comprise from about $0.01\\%$ to about $20\\%$ by weight of the solids of the polyurethane, preferably from about $3\\%$ to about $17\\%$ . by weight of the solids.  \n\nPreferred hydrophilic polyurethane polymer main chain segments include polyethylene oxide, polypropylene oxide, or combinations thereof. Accordingly, preferred hydrophilic main chain segments comprise polyethylene oxide, polypro  \n5 pylene oxide, or combinations thereof in an amount ranging from 0 to about $20\\%$ by weight of the solids of the polyurethane, more preferably from O to about $15\\%$ by weight of the solids. The preferred hydrophilic side chain segments comprise polyethylene oxide in an amount ranging from about   \n:0 $0.01\\%$ to about $20\\%$ by weight of the solids of the polyurethane, more preferably from about $3\\%$ to about $17\\%$ by weight of the solids.  \n\nPolyisocyanates  \n\nPolyols react with polyisocyanates to form a polyurethane.   \n25 As used herein, polyisocyanates are multi-functional isocyanates that have isocyanate functionality of greater than or equal to two. Reacting an excess of polyisocyanates with the polyols forms a polyurethane prepolymer, which is a polyurethane polymer with isocyanate-terminated end groups   \n30 capable of chain extending to a higher molecular weight polyurethane. The polyurethane prepolymer forms as long as the ratio of the isocyanate functional groups of the polyisocyanate to the hydroxyl functional groups of the polyols is greater than or equal to about 1.1:1, i.e., the ratio of the   \n35 isocyanate moiety to hydroxyl moiety present during the reaction is greater than or equal to about 1.1:1.  \n\nAt the broadest level, polyisocyanates can be classified as either aliphatic or aromatic polyisocyanates. Aliphatic polyisocyanates generally have better light stability than aromatic polyisocyanates.  \n\nSuitable polyisocyanates used in the polyurethane coating compositions described herein include multi-functional isocyanates such as diisocyanates, triisocyanates, derivatives of diisocyanates and triisocyanates capable of forming polyure  \n45 thane linkages, and combinations thereof. Diisocyanates are isocyanates with an isocyanate functionality of two. Examples of diisocyanates include isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), xylene diisocyanate (XDI), toluene diisocyanate (TDI), diphenylmethane   \n50 diisocyanate any diisocyanates derived from the foregoing, and combinations thereof. Triisocyanates are isocyanates with an isocyanate functionality of three. Triisocyanates include derivatives of diisocyanates, such as an HDI biuret. Because of their better light stability than the aromatic poly  \n55 isocyanates, aliphatic polyisocyanates, including but not limited to aliphatic diisocyanates or aliphatic triisocyanates, are preferred for the polyurethane coating compositions described herein. IPDI-type and HDI-type diisocyanates are aliphatic isocyanates.  \n\nCertain embodiments of the polyurethane coating compositions described herein include partially blocked or wholly blocked polyisocyanates. Suitable blocking agents used to block the polyisocyanates include active-methyl-type, lactam-type, alcohol-type, oxime-type, and phenolic-type blocking agents. Non-limiting examples of blocking agents include dimethylpyrazole (DMP), i.e., 3,5-dimethylpyrazole; methylethylcetoxime (MEKO); diethyl malonate (DEM);  \n\nand the like. Preferred are the DMP-type blocking agent because unblocking occurs at temperatures lower than about $120^{\\circ}\\mathrm{~C~}.$ ,which is better suited for applications that are sensitive to high temperatures, such as curing a coating on a polycarbonate lens or sheet. Blocking agents that are activated at higher temperatures, such as the previously mentioned oxime-, lactam-, alcohol-, and phenolic-type blocking agents, are better suited for applications where temperature is not an issue, such as curing coatings on metal or glass substrates.  \n\nSuitable partially blocked polyisocyanates include partially blocked tri-functional polyisocyanates, such as partially blocked triisocyanates or partially blocked biurets of certain diisocyanates, such as partially blocked HDI biurets. In the partially blocked tri-functional polyisocyanate, of the three isocyanate functional groups, two isocyanate functional groups are blocked with a blocking agent, e.g., DMP, and the third isocyanate functional group is unblocked. The partially blocked polyisocyanate is prepared by reacting two moles of blocking agent for every one mole of tri-functional isocyanate, i.e., two moles of blocking agent for every three moles of isocyanate functional groups. Suitable partially blocked triisocyanates are commercially available, such as the commercially available partially blocked triisocyante Trixene DP9C/ 012 from Baxenden Chemicals Ltd. of the United Kingdom. An example of a commercially available wholly blocked polyisocyanate is Trixene BI 7961 of Baxenden Chemicals Ltd, which is a wholly blocked HDI biuret.  \n\nPolyurethane Formation with Surfactants  \n\nThe use of a hydrophilic polyol to create a hydrophilic 3 polyurethane, i.e., a polyurethane with hydrophilic main or side chain segments, does not alone provide water-washable anti-fog properties in the cured polyurethane coating (see for example Comparative Examples 1-3,which illustrate that hydrophilic polyurethanes alone do not exhibit anti-fog prop- 3 erties in the cured polyurethane coating). Similarly, in some embodiments, the use of a hydrophilic polyol to create a hydrophilic polyurethane does not alone support the dispersibility of the polyurethane in the liquid phase. The addition of a surfactant chemically bonded to the hydrophilic polyure- 4 thane polymer structure, in accordance with the polyurethane coating compositions described herein, results in waterwashable anti-fog properties in the cured polyurethane and also supports the dispersion of the polyurethane in a water or combination water and organic solvent liquid phase.  \n\nThe reaction of the polyols, including at least one hydrophilic polyol, and polyisocyanates takes place in the presence of isocyanate-reactive cationic surfactants, isocyanate-reactive salts of surfactants, isocyanate-reactive carboxylic acids, or combinations thereof which allow these isocyanate-reactive compounds to chemically bond to the main chain or backbone of the polyurethane structure. The isocyanate-reactive cationic surfactant and the isocyanate-reactive salt of a surfactant each directly form a covalent bond attachment to the resulting polyurethane, either as part of the main chain or a side chain. The isocyanate-reactive carboxylic acid directly forms a covalent bond to the resulting polyurethane and provides a reaction site for a carboxylic-reactive amphoteric surfactant, i.e., the carboxylic acid functional group covalently bonded to the polyurethane reacts with an amphoteric surfactant in a neutralization reaction to form a salt of an amphoteric surfactant chemically bonded to the polyurethane.  \n\nFirst Mixture  \n\nIn accordance with one embodiment, the coating compo- 6: sitions comprise a mixture of a polyurethane and a liquid phase selected from the group consisting of water, an organic  \n\nsolvent, and combinations thereof. The polyurethane comprises the reaction products of polyols, including a diol having polyethylene oxide side chain segments and at least one other polyol different than the diol having polyethylene oxide side chain segments, at least one polyisocyanate, and a dihydroxy-carboxylic acid. In accordance with this embodiment, the polyurethane comprises from about $0.01\\%$ to about $20\\%$ hydrophilic side chain segments by weight of the solids of the polyurethane. The hydrophilic side chain segments include ） those described herein, preferably polyethylene oxide.  \n\nSuitable polyisocyanates used in accordance with the coating composition of this embodiment include multi-functional isocyanates such as diisocyanates, triisocyanates, derivatives of diisocyanates and triisocyanates capable of forming polyurethane linkages, and combinations thereof.An example of a specific preferred polyisocyanate includes IPDI.  \n\nAs described above, polyols used in accordance with this embodiment include a diol having polyethylene oxide side chain segments and at least one other polyol different than the   \n20 diol having polyethylene oxide side chain segments.An example of a suitable diol having polyethylene oxide side chains includes those described herein, preferably a diol having polyethylene oxide side chains comprising polyethylene oxide in an amount ranging from about $72\\%$ to about $90\\%$ by   \n25 weight of the polyol. Other suitable polyols include the polyols described herein, such as a diol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof; a triol having main chain segments selected from the group consist  \n30 ing of polyethylene oxide, polypropylene oxide, and combinations thereof; an alkyl diol; an alkyl triol; a polycarbonate diol; a polycarbonate triol; or combinations thereof.  \n\nThe polyurethane resulting from this reaction amongst the polyols, polyisocyanates, and dihydroxy-carboxylic acid has carboxylic acid functional groups incorporated by covalent bonds to the main chain of the polyurethane structure. In accordance with this embodiment, a carboxylic-reactive amphoteric surfactant is introduced and reacts with this polyurethane. The amphoteric surfactant acts as a base and reacts with the carboxylic acid functional group in a neutralization reaction to ionically bond the amphoteric surfactant to the carboxylic acid functional group present in the polyurethane structure.  \n\nAs a result of this neutralization reaction, the polyurethane   \n45 has a side chain, i.e., pendant, salt ofan amphoteric surfactant chemically bonded to the main chain of the polyurethane polymer structure. This chemically bonded side chain amphoteric surfactant salt of the polyurethane affects the anti-fog properties of the cured polyurethane coating. In the   \n50 dispersion embodiments of this coating composition, this surfactant salt also supports the dispersibility of the polyurethane in the liquid phase. Without intending to be limited by any theories, the inventors believe that the ionic character of the salt of the amphoteric surfactant allows the surfactant to   \n55 orient with respect to the surface of cured polyurethane coating or to orient within the dispersed polyurethane particles to enhance the anti-fog and disperability properties associated with the polyurethane. The chemical bonding of the carboxylic-reactive amphoteric surfactant to the backbone of the   \n60 polyurethane polymer results in a long-lasting anti-fog coating that remains after repeated washing of the surface of the polyurethane coating, after soaking the coating in water, or after both repeated washing and soaking.  \n\nThe dihydroxy-carboxylic acids used in accordance with the present embodiment are isocyanate-reactive. The dihydroxy-carboxylic acid covalently bonds to the polyurethane polymer structure specifically through a condensation reaction of each of the two isocyanate-reactive hydroxyl functional groups of the dihydroxy-carboxylic acid to an isocyanate functional group of a polyisocyanate, such as a diisocyanate, to covalently bond the carboxylic functional group as a segment in the main chain of the polyurethane. This ensures that the ionic bond formed during the neutralization reaction between the amphoteric surfactant and the carboxylic acid functional group is covalently anchored within the main chain of the polyurethane.  \n\nSuitable dihydroxy-carboxylic acids include any carboxylic acid having at least two hydroxyl functional groups. Dihydroxy-carboxylic acids are represented by the general form of $(\\mathrm{OH})_{2}\\mathrm{R}^{4}(\\mathrm{COOH}).$ wherein $\\bar{\\mathsf{R}^{4}}$ is an unbranched or branched alkyl group having from about one to about 12 carbon atoms. Examples of dihydroxy-carboxylic acids include, without limitation, dimethylolpropionic acid (DMPA), dimethylolbutanoic acid (DMBA), and other dihydroxy-derivatives of ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic, decanoic acid, dodecanoic acid, and the like.A preferred dihydroxy-carboxylic acid used in the polyurethane coating compositions includes DMPA. As described above, such carboxylic acid functional groups covalently incorporated into the main chain of the polyurethane polymer are neutralized by the amphoteric surfactant to form a salt of the amphoteric surfactant.  \n\nAmphoteric surfactants,which may also sometimes be referred to as zwitterionic surfactants, are carboxylic-reactive surfactants that generally carry an overall formal net charge of zero, and therefore carry a net neutral charge. However, these surfactants carry different formal charges on different atoms within the compound.Having different formal charges within the surfactant compound gives the amphoteric surfactant the flexibility to act as a cationic surfactant, an anionic surfactant, or a non-ionic surfactant depending on the pH of the solution or the environment surrounding the amphoteric surfactant. Amphoteric surfactants are generally derived from cationic compounds, such as quaternary ammonium, phosphonium, and sulfonium compounds, and include an anionic substituent group such as a carboxylate, sulfonate, sulfate, phosphate, phosphonate, and the like.  \n\nExamples of preferred amphoteric surfactants include amine oxides and alkyl betaines.Amine oxides are oxides of tertiary amines and are represented by the general form of $\\mathrm{R}_{3}^{5}\\dot{-}\\dot{\\mathrm{N}}^{+}\\dot{-}\\mathrm{O}^{-}$ ，wherein $\\mathrm{R}^{\\bar{5}}$ is selected from the group consisting of a hydrogen, an unbranched alkyl group having from about 8 to about 18 carbon atoms, and combinations thereof, and wherein at least one $\\mathrm{R}^{5}$ is an unbranched alkyl group having from about 8 to about 18 carbon atoms.Alkyl betaines, another type of suitable amphoteric surfactant, may be represented by the general form $\\mathrm{R}^{6}-\\mathrm{N}^{+}-(\\mathrm{CH}_{3})_{2}-\\mathrm{CH}_{2}-$ $\\scriptstyle(\\mathrm{C=O})\\ \\mathrm{-}\\mathrm{O}^{-}$ ，wherein $\\mathrm{R}^{6}$ preferably is an unbranched alkyl group having from about 8 to about 18 carbon atoms. $\\dot{\\mathrm{R}}^{6}$ further includes an unbranched alkyl group having from about 8 to about 18 carbon atoms with amido functionality. An example of an alkyl betaine with amido functionality is lauramidopropyl betaine. Those of ordinary skill in the art understand that amine oxides or alkyl betaines are added in an amount sufficient to neutralize the carboxylic acid functional groups on the polyurethane. The neutralized amines from the surfactant salts of amphoteric surfactants and carboxylic acid functional groups comprise from about $2\\%$ to about $15\\%$ by weight of the solids of the polyurethane, preferably from about $5\\%$ to about $12\\%$ by weight of the solids.  \n\nIn accordance with this embodiment of the coating compositions described herein, the polyisocyanates optionally further comprise blocked polyisocyanates. A non-limiting example of a blocked polyisocyanate used is a DMP blocked  \n\nHDI biuret. In addition to the curative properties of blocked polyisocyanates, the introduction of blocked polyisocyanates enhances the abrasion resistance of the cured coatings. This is shown in Examples 3 and 4 below. The only difference ；between the coating compositions of Examples 3 and 4 is that a DMP blocked HDI biuret is added to the polyurethane prepolymer mixture of Example 4 as an additive after the prepolymer reaction and after the prepolymer has cooled. In such compositions incorporating the blocked polyisocyanate, 0 the blocked polyisocyanates comprise from O to about $10\\%$ by weight of the solids of the polyurethane, preferably from about O to about $5\\%$ by weight ofthe solids. The cured coating of Example 4 exhibits better abrasion resistance formed with the blocked polyisocyanate than the comparable cured coat5 ing of Example 3 formed without the blocked polyisocyanate. The cured coating of Example 4 exhibits an increase in haze of about $10.7\\%$ after the falling sand abrasion test, which is less than the about $16.3\\%$ increase in haze for this same test of the cured coating of Example 3. The smaller increase in haze 0 after the falling sand abrasion test shows that the coating of Example 4 exhibits a greater resistance to abrasion than the coating of Example 3. Therefore, the addition of the blocked polyisocyanate to Example 4, in what would otherwise be an identical coating composition to Example 3, enhances the 5 abrasion resistance of the cured coating.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 17,
+        "chunk": "# Second Mixture  \n\nIn accordance with another embodiment, the coating compositions comprise a mixture of a polyurethane and a liquid phase selected from the group consisting of water, an organic   \n30 solvent, and combinations thereof. The polyurethane comprises the reaction products of polyols, at least one partially blocked tri-functional polyisocyanate, an isocyanate-reactive salt of surfactant, and an isocyanate-reactive cationic surfactant. The polyols used in accordance with this embodiment   \n35 include at least one of (a) a diol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof, or (b) a triol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combi  \n40 nations thereof. The polyols also include at least one other polyol different than (a) and (b). Because the salt of a surfactant and the cationic surfactant are each isocyanate-reactive, the salt of a surfactant and cationic surfactant react with free isocyanate functional groups when reacted in the presence of   \n45 the polyols and polyisocyanates during the reaction forming the polyurethane. In accordance with this embodiment, the polyurethane comprises from about $0.01\\%$ to about $20\\%$ hydrophilic main chain segments by weight of the solids of the polyurethane. The hydrophilic main chain segments   \n50 include those described herein, preferably polyethylene oxide, polypropylene oxide, or combinations thereof. As described above, polyols used in accordance with this embodiment include at at least one other polyol different than (a) a diol having main chain segments selected from the group   \n55 consisting of polyethylene oxide, polypropylene oxide, and combinations thereof, and (b) a triol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof. Examples of such polyols suitable for this embodiment   \n60 include the polyols described herein, such as a diol having polyethylene oxide side chain segments; an alkyl diol; an alkyl triol; a polycarbonate diol; a polycarbonate triol; or combinations thereof.  \n\nSuitable diols having main chain segments selected from i5 the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof used in accordance with this embodiment include those described herein, preferably a polypropylene oxide and polyethylene oxide block copolymer diol comprising polyethylene oxide in the main chain in an amount ranging from about $10\\%$ to about $25\\%$ by weight of the polyol.  \n\nSuitable triols having main chain segments selected from 5 the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof used in accordance with this embodiment include those described herein, preferably a polypropylene oxide and polyethylene oxide copolymer triol comprising from about $60\\%$ to about $95\\%$ polyethylene oxide  1( by weight of the polyol.  \n\nIn accordance with this embodiment, the polyisocyanates comprise partially blocked tri-functional polyisocyanates, such as partially blocked triisocyanates or partially blocked biurets of diisocyanates, e.g., a partially blocked HDI biuret. As described above, of the three isocyanate functional groups in the partially blocked tri-functional isocyanate, two isocyanate functional groups are blocked with a blocking agent, e.g., DMP, and the third isocyanate functional group is unblocked. Moreover, in accordance with this embodiment, blocked polyisocyanates comprise from about $5\\%$ to about $60\\%$ by weight of the solids of the polyurethane.  \n\nThe use of partially blocked polyisocyanates described in the foregoing also advantageously enhances resistance to chemicals in the cured coating. Besides being fog resistant after repeated washing and soaking with water and besides exhibiting abrasion resistance (see Example 8), it has been unexpectedly discovered that cured coatings prepared with partially blocked polyisocyanates in accordance with this embodiment withstand washing with chemicals, such as washing the cured coating with toluene or methylethylketone. Accordingly, the resulting cured coatings of this embodiment provides long-lasting anti-fog, abrasion-resistant, and chemical-resistant properties.  \n\nIn accordance with the present embodiment, the polyiso- 35 cyanates optionally further comprise a polyisocyanate such as diisocyanates, triisocyanates, derivatives of diisocyanates and triisocyanates capable of forming polyurethane linkages, and combinations thereof as described herein. The isocyanate-reactive salt of a surfactant, the isocyanate-reactive cat- 4( ionic surfactant, and the polyols react in the presence of (a) at least one polyisocyanate, i.e., diisocyanates, triisocyanates, derivatives of diisocyanates and triisocyanates capable of forming polyurethane linkages, and combinations thereof, and (b) at least one partially blocked tri-functional polyiso- 45 cyanate. An example of a preferred polyisocyanate used in this embodiment includes IPDI. Moreover, the polyisocyantes used in accordance with this embodiment comprise from about $0\\%$ to about $30\\%$ by weight of the solids of the polyurethane, preferably from about $0\\%$ to about $21\\%$ by 5( weight of the solids.  \n\nAlso in accordance with this embodiment, the isocyanatereactive salt of a surfactant contemplated herein is the product of a neutralization reaction between an acid of an anionic surfactant and a base containing at least one isocyanate-reactive functional group, such as a hydroxyl functional group, so as to incorporate the isocyanate-reactive functionality into the salt. Suitable isocyanate-reactive anionic salts of surfactants include active hydrogen amine salts of alkyl sulfonic acids, active hydrogen amine salts of alkybenzene sulfonic acids, amino-alcohol sulfonates, particularly sulfonates having an alkyl chain with at least about 16 carbon atoms in the chain. Preferably, the isocyanate-reactive salt of a surfactant is mono-functional, i.e., the isocyanate-reactive salt of a surfactant preferably has a single isocyanate-reactive functional group. The mono-functional salt of a surfactant forms side chains covalently bonded to the polyurethane main chain with the surfactant salt's single isocyanate-reactive functional group. One example of such mono-functional preferred salt includes a salt of dimethylaminomethylpropanol and dodecylbenzene sulfonic acid. The isocyanate-reactive salt of a surfactant comprises from about $0.1\\%$ to about $7\\%$ by weight ofthe solids of the polyurethane, preferably from about $2\\%$ to about $5\\%$ by weight of the solids.  \n\nWithout intending to be limited by any theories, the inventors believe that the ionic bond forming the salt portion of the isocyanate-reactive salt of a surfactant compound allows the hydrophilic and hydrophobic segments of the surfactant to orient to the surface of the polyurethane in the cured coating to provide anti-fog effects for the cured coating and to orient relative to the polyurethane within the coating composition to aid in the dispersibility of the polyurethane in the liquid phase of the dispersion embodiments of this coating composition.  \n\nIn accordance with this embodiment, the isocyanate-reactive cationic surfactant comprises a quaternary ammonium, phosphonium, or sulfonium surfactant having at least one   \n20 isocyanate-reactive functional group and a long hydrocarbon chain hydrophobic tail. The long chain hydrophobic hydrocarbon tail of the isocyanate-reactive cationic surfactant generally has at least about 16 carbon atoms and includes amido functional groups, preferably the long chain hydrophobic tail   \n25 has at least about 18 carbon atoms. Also, the isocyanatereactive cationic surfactant preferably has two hydrophilic isocyanate-reactive functional groups, i.e., the isocyanatereactive cationic surfactant is di-functional. The two hydrophilic isocyanate-reactive functional groups include an   \n30 alkoxylated chain terminated with a hydroxyl functional group. These two hydrophilic groups react with free isocyanate functional groups present in the reaction mixture to covalently bond the di-functional isocyanate-reactive cationic surfactant as part of the main chain of the polyurethane.   \n35 The alkoxylated segments on the two chains include, but are not limited to, hydroxyethyl functional groups, which further adds to the hydrophilic character of the overall polyurethane polymer structure.Examples of suitable di-functional isocyanate cationic surfactants include bis(polyhydroxyethyl) qua  \n40 ternary ammonium surfactants having stearamide or stearamidopropyl functional groups or N,N-bis(2-hydroxyethyl)- n-(3-dodecyloxy-2-hydroxypropyl) methylammonium sulfate. The isocyanate-reactive cationic surfactant comprises from about $0.1\\%$ to about $20\\%$ by weight of the solids   \n45 of the polyurethane, preferably from about $4\\%$ to about $10\\%$ by weight of the solids. The combination of the isocyanate-reactive cationic surfactant with the isocyanate-reactive salt of a surfactant enhances the anti-fog properties of the cured polyurethane   \ni0 coating and also enhances the dispersibility of the polyurethane in the dispersion embodiment of this coating composition. In addition, this combination of the isocyanate-reactive cationic surfactant with the isocyanate-reactive salt of a surfactant in the coating composition further improves the anti  \ni5 fog properties of the resulting coating over a respective coating from a composition having only the isocyanate-reactive salt of a surfactant (i.e., compare Example 5 below with Example 8).  \n\nIn accordance with the present embodiment, optional, non reactive surfactants can be mixed in to the polyurethane coating composition during or after the reactions forming the polyurethane to enhance or supplement the anti-fog properties of the resulting cured coating.For example, in the context of preparing a dispersion in accordance with this embodiment (as discussed below), the non-reactive surfactant can be mixed with the coating composition during any of the polyurethane prepolymer, dispersion, and final polymerization steps. Examples of suitable types of non-reactive surfactants include anionic surfactants, cationic surfactants, and non ionic surfactants. The preferred type of non-reactive surfactants are anionic surfactants.  \n\nIn certain embodiments, without intending to be limited by any theories, the inventors believe that the addition of a nonreactive anionic surfactant to the polyurethane comprising the isocyanate-reactive salt of a surfactant and the isocyanatereactive cationic surfactant develops an ionic relationship with the cationic surfactant incorporated into the main chain of the polyurethane polymer, which reduces the leaching or erosion of the non-reactive anionic surfactant from the polyurethane coating. A non-limiting specific example of a nonreactive anionic surfactant is sodium dioctylsulfosuccinate. Third Mixture  \n\nIn accordance with another embodiment, the coating compositions comprise a mixture of a polyurethane and a liquid phase selected from the group consisting of water, an organic solvent, and combinations thereof. The polyurethane comprises the reaction products of polyols; polyisocyanates, including at least one polyisocyanate and at least one partially blocked tri-functional polyisocyanate; an isocyanate-reactive salt of surfactant; and an isocyanate-reactive cationic surfactant. The polyols used in accordance with this embodiment include at least one of (a) a diol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof, or (b) a triol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof. The polyols also include (c) a diol having polyethylene oxide side chain segments and (d) at least one otherpolyol different than (a), (b), and (c). In accordance with this embodiment, the polyurethane comprises hydrophilic main chain segments, hydrophilic side chain segments, or combinations thereof in an amount ranging from about $0.01\\%$ to about $40\\%$ by weight of the solids of the polyurethane. The hydrophilic side chain segments include those described herein, preferably polyethylene oxide. The hydrophilic main chain segments include those described herein, preferably polyethylene oxide, polypropylene oxide, or combinations thereof.  \n\nAs described above, polyols used in accordance with this embodiment include (d) at at least one other polyol different than (a) a diol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof, (b) a triol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof, and (c) a diol having polyethylene oxide side chain segments. Examples of such polyols include the polyols described herein, such as an alkyl diol, an alkyl triol, a polycarbonate diol, a polycarbonate triol, or combinations thereof.  \n\nAn example of a suitable diol having polyethylene oxide side chains includes those described herein, preferably a diol having polyethylene oxide side chains comprising polyethylene oxide in an amount ranging from about $72\\%$ to about $90\\%$ by weight of the polyol.  \n\nSuitable diols having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof include those described herein, preferably a polypropylene oxide and polyethylene oxide block copolymer diol comprising polyethylene oxide in the main chain in an amount ranging from about $10\\%$ to about $25\\%$ by weight of the polyol.  \n\nSuitable triols having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof used in accordance with this embodiment include those described herein, preferably a polypropylene oxide and polyethylene oxide copolymer triol comprising from about $60\\%$ to about $95\\%$ polyethylene oxide by weight of the polyol.  \n\n5 The polyisocyanates used in accordance with this embodiment include (i) at least one polyisocyanate as described herein, i.e., diisocyanates, triisocyanates, derivatives of diisocyanates and triisocyanates capable of forming polyurethane linkages, and combinations thereof, and (ii) at least one par0 tially blocked tri-functional polyisocyanate. The partially blocked tri-functional polyisocyanates include those described herein, preferably a partially blocked triisocyanate or a partially blocked biuret of a diisocyanate. In accordance with this embodiment, the blocked polyisocyanates comprise 5 from about $5\\%$ to about $60\\%$ by weight of the solids of the polyurethane.  \n\nSuitable isocyanate-reactive salts of a surfactant used in accordance with this embodiment include those described herein, preferably the mono-functional isocyanate-reactive 20 salts of a surfactant described above.The isocyanate-reactive salt ofa surfactant comprises from about $0.1\\%$ to about $7\\%$ by weight of the solids of the polyurethane, preferably from about $0.1\\%$ to about $5\\%$ by weight of the solids. Suitable isocyanate-reactive cationic surfactants used in accordance 25 with this embodiment include those described herein, preferably the di-functional isocyanate reactive cationic surfactants described above. The isocyanate-reactive cationic surfactant comprises from about $0.1\\%$ to about $20\\%$ by weight of the solids of the polyurethane, preferably from about $0.1\\%$ to 30 about $10\\%$ by weight of the solids.  \n\nIn accordance with the present embodiment, optional, nonreactive surfactants as described herein, preferably non-reactive anionic surfactants, can be mixed in to the polyurethane coating composition during or after the reactions forming the polyurethane.  \n\nFourth Mixture  \n\nIn accordance with another embodiment, the polyurethane coating compositions result from a combination of the first mixture described herein and the second mixture described 40 herein.As discussed in greater detail above, the first mixture comprises a liquid phase and a polyurethane. The polyurethane of the first mixture comprises the reaction products of polyols, including a diol having polyethylene oxide side chain segments and atleast one other polyol different than the 45 diol having polyethylene oxide side chain segments, at least one polyisocyanate, and a dihydroxy-carboxylic acid neutralized by a carboxylic-reactive amphoteric surfactant to form a salt of the amphoteric surfactant. The second mixture, as discussed in greater detail above, comprises a liquid phase 50 and a polyurethane. The polyurethane of the second mixture comprises the reaction products of polyols, at least one partially blocked tri-functional polyisocyanate, an isocyanatereactive salt of surfactant, and an isocyanate-reactive cationic surfactant. The polyols used in the second mixture include at 55 least one of (a) a diol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof, or (b) a triol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations 60 thereof. The polyols used in the second mixture also include at least one other polyol different than (a) and (b). The liquid phase for the first mixture, the second mixture, or both the first mixture and the second mixture is selected from the group consisting of water, an organic solvent, and combinations 65 thereof.  \n\nFurtherin accordance with the coating compositions of this embodiment, additional liquid selected from the group consisting of water, an organic solvent, and combinations thereof is added in suitable amounts to the combination of the first mixture and second mixture to obtain the desired viscosity suitable for the intended application.  \n\nOrganic Solvents Used in Polyurethane Formation  \n\nThe selection of suitable organic solvents used in the polyurethane formation reactions for the coating compositions described herein is dependent upon the selection of constituent components reacted to form the polyurethane, including those solvents able to dissolve the selected polyols and solvents that do not readily react with the polyisocyanates. Examples of suitable organic solvents useful for such reactions include ketones such as methylethylketone, methylisobutylketone, diacetone alcohol, 3,3-dimethyl-2-butanone, and pentanedione; N-methyl pyrrolidone; acetonitrile; esters; glycol esters; and tertiary alcohols such as tertiary-butyl alcohol and tertiary-amyl alcohol.  \n\nCatalysts  \n\nIn addition, catalysts are added along with the reactants used to prepare the polyurethane. Suitable catalysts useful for the preparation ofthe polyurethane prepolymer include metal carboxylates (i.e., metal salts of carboxylic acids), such a tin(I) ethylhexanoate, dibutyltindilaurate, and dibutylin bis (octylmaleate).  \n\nAqueous Dispersions  \n\nWith respect to the aqueous dispersion embodiment of the coating compositions described herein, the preparation of the aqueous polyurethane dispersion can generally be classified as taking place within three steps, although one of ordinary skill in the art would understand that these three steps are not mutually exclusive from each other. Moreover, this specification describes the present embodiment in the context of these steps for clarity, and the embodiments or features of the present invention should not be construed as being limited to these steps or dispersions in general.Furthermore, these three steps should not be construed as being limited to this order, but rather these steps can take place in a different orders, or can take place concurrently, or in combinations thereof.  \n\nIn general, the three steps include 1) a polyurethane prepolymer formation step, 2) a dispersion step, and 3) a final 4( polymerization step. The first step generally relates to the creation of a polyurethane prepolymer through reactions between the polyisocyanates and polyols in an organic solvent at high temperatures. The prepolymer is a polyurethane molecule having isocyanate-terminated functional groups. 4: The prepolymer is formed when the poloyls react with a surplus of the polyisocyanates, preferably when the stoichiometric ratio of isocyanate functional groups of the polyisocyanates to the hydroxyl functional groups of the polyols is greater than or equal to about 1.1:1.Any suitable polyols and 5( polyisocyanates, as described herein, can be used to form the prepolymers in accordance with the embodiments of the coating compositions of the present invention. Additional components used to form the polyurethanes as described herein are also present in the reactions forming the polyurethane 5: prepolymer. For example, a dihydroxy-carboxylic acid, an isocyanate-reactive salt of a surfactant, and an isocyanatereactive cationic surfactant are present for certain embodiments during the reactions forming the polyurethane prepolymer.  \n\nThe second step generally includes the dispersion of the prepolymer into the liquid phase, i.e., water or water in combination with an organic solvent, to form a stable colloidal dispersion. Polyurethane prepolymers are generally dispersed into the liquid phase with the aid of a dispersing agent, which can be anionic, cationic, or non-ionic dispersing agents. An example of an anionic dispersing agent is an  \n\nanionic surfactant, such as the tertiary amine triethanolamine. Examples of cationic dispersing agents include quaternary ammonium surfactants. Non-ionic dispersing agents can include non-ionic surfactants, i.e., hydrophilic segments in 5 the polyurethane polymer structure such as polyethylene oxide segments in the main chain or side chains. By reacting the dispersing agent with the polyurethane prepolymer, the prepolymer gains water miscible or solvable groups that aid in dispersing the prepolymer particle in the liquid phase. The carboxylic-reactive amphoteric surfactant used in accordance with embodiments of the coating compositions described herein are added prior to or during the dispersion step.  \n\nIn this second basic step of preparing polyurethane disper  \n15 sion, the polyurethane prepolymer can be dispersed in the presence of water or another liquid medium with the aid of agitation such as mechanical stress or mechanical mixing to form the dispersed phase of the aqueous dispersion. The mechanical stress includes high shear mechanical stress or   \n20 mixing caused with the aid of a device such as a high shear disperser, a homogenizer, or other device capable of dispersing polyurethane particles. The dispersion takes place during or after the addition of the carboxylic-reactive amphoteric surfactant in certain embodiments, which neutralizes car  \n25 boxylic acid functional groups present on the polyurethane prepolymer to form a salt of the amphoteric surfactant chemically bonded to the prepolymer and which assists in the dispersibility of the polyurethane. The dispersion step also preferably occurs after the isocyanate-reactive salt of a surfactant   \n30 and isocyanate-reactive cationic surfactant are added to embodiments of the coating compositions described herein. These surfactants also assist in the dispersibility of the polyurethane.  \n\nThe third step in preparing an aqueous polyurethane dispersion is the final polymerization step. The final polymerization step is the extension of the polyurethane polymer chains to a higher molecular weight polyurethane polymer. The isocyanate-terminated end groups in the prepolymer react in the presence of the chain extenders, such as multifunctional amines, multi-functional polyols, urea, or combinations thereof, to extend the polyurethane prepolymers to the higher molecular weight dispersed polyurethane polymer particles. Specific examples of suitable chain extenders useful in accordance with the coating compositions described herein include hydrazine monohydrate, aqueous hydrazine $(30\\%)$ ， 1,6-hexanediamine, 2-(2-aminoethyl)aminoethanol, or combinations thereof. The three steps used to describe this process of preparing dispersions are not mutually exclusive of each other, the final polymerization step can take place before, during, or after the dispersion step.  \n\nDescriptions of the final polymerization is not intended to belimiting. Often it is desirable to produce compositions with lower molecular weights by reducing the amount of chain 55 extension agent or omitting the chain extension agent altogether. Therefore, in some embodiments, the polyurethane prepolymer, a lower molecular weight polyurethane produced with a reduced amount of chain extenders, or both the prepolymer and the lower molecular weight polyurethane are 50 the polyurethanes in the final coating composition.  \n\nSimilarly, the descriptions provided herein with respect to the dispersion steps are not intended to be limited to only water-based dispersions. As discussed above, in some embodiments, the non-aqueous liquids, such as organic solvents, are substituted for water to disperse or dissolve the described polyurethane compositions to promote suitability for specific applications.  \n\nApplication  \n\nUpon obtaining the final coating composition, the aqueous polyurethane dispersion, the organic solvent polyurethane solution, or the mixture of an aqueous polyurethane dispersion and an organic solvent polyurethane solution are cooled to a storage stable temperature, such as ambient temperature. The coating composition is ready to be applied as coating to a substrate, which upon curing,forms a transparent, abrasionresistant, and water-washable anti-fog coating. The coating is applied directly to the substrate or is cast as a free-form film that is later applied to the substrate.  \n\nAn effective amount of a leveling or flow-control agent optionally is incorporated into the coating composition described herein to spread more evenly or level the composition on the surface of the substrate and to provide substantially uniform contact with the substrate. The amount of the leveling or flow control agent can vary widely but is used in an amount sufficient to provide the coating composition with from about 10 to about ${5,000\\ \\mathrm{ppm}}$ of the leveling or flow control agent.Any conventional, commercially available leveling or flow control agent which is compatible with the coating composition and the substrate, which is capable of leveling the coating composition on a substrate, and which enhances wetting between the coating composition and the substrate is employed. Non-limiting examples of such flowcontrol agents include polyethers, silicones, fluorosurfactants, polyacrylates, or fluoro-modified polyacrylates.  \n\nThe polyurethane coating compositions described herein are applied in any suitable manner to a substrate.For example, the compositions of the invention are applied to solid substrates by conventional methods, such as flow coating, spray coating, curtain coating, dip coating, spin coating, roll coating, and the like to form a continuous surface film on the substrate.  \n\nThe polyurethane coating compositions are also prepared as free-form or unsupported films that are applied to the substrate as the film after curing. The free-form film is prepared in any suitable manner known to those skilled in the art, such as a preparing a free film through casting, spraying, molding, injection, frothing or similar techniques. The freeform film optionally has an adhesive or tack bonded to at least one surface of the film so as to allow the free-form film to bond to the substrate through the adhesive.  \n\nThe polyurethane coating compositions described herein are applied as a coating to rigid substrate surfaces or substrate 4: surfaces that are sufficiently flexible to withstand further processing of the substrate, such as molding or shaping, without loss of its properties.A variety of substrates are employed. Among the preferred substrate materials include transparent plastics such as polycarbonate, acrylic, polyvinylchloride, 5( polybisallyl carbonate, polyethylene terephthalate, polyethylene naphthenate, polyurethane, and polythiourethane. Other substrates include various polyolefins, fluorinated polymers, metals and glass, such as soda-lime glass, borosilicate glass, acrylic glass among other types of glass, are used 5: with appropriate pretreatments, if necessary. In some embodiments, hydrophobic substrates or substrates which do not readily accept aqueous-based coating compositions are used. Non-limiting examples of such substrate materials include dirty or silane treated glass, polycarbonate plastics 6( with a waxy mold release, or plastics like polypropylene and polymethylpentene. The substrate optionally has an adhesive or tack bonded to any uncoated surface.  \n\nA feature of some embodiments of the polyurethane coating compositions described herein is the ability to dry to an essentially tack-free state at temperatures below $100^{\\circ}~\\mathrm{{C}}$ \\* when applied as a coating to an article. Clean-room conditions are not always practical in the higher temperature commercial ovens used for final curing. Coatings which do not dry tack-free can pick up dust or other airborne debris present in these non-clean-room higher temperature curing ovens, thereby reducing the quality and cosmetic appearance of such coatings. Therefore, drying the coatings to a tack-free condition in clean-room ovens at lower temperatures, e.g., temperatures below $100^{\\circ}~{\\mathrm{C}}.$ , before moving the articles to the higher temperature non-clean room ovens provides advantages over coating compositions which do not dry tack-free.A higher molecular weight of the polyurethane polymer structure improves the ability of the polyurethane coatings to dry tack-free. In accordance with embodiments of the polyurethane coating compositions disclosed herein, reacting unblocked multi-functional isocyanates with polyols provides a higher molecular weight polyurethane polymer structure as compared to reacting wholly or partially blocked multi-functional isocyanates with such polyols. Specific embodiments of the coating compositions described herein which dry tack-free include Examples 1-4, 9, and 10-12.  \n\nThe present anti-fog coating compositions, when applied directly or as free-form films to substrates, are used in a wide variety of applications. For example, the anti-fog coatings can   \n25 be applied on ophthamalic substrates, such as optical lenses for use in eyeglasses or sunglasses, lenses used in protective eyewear, and the like. The anti-fog coatings are applied in automotive applications (including automobiles, commercial vehicles, and motorcycles), such as on windshields, windows,   \n30 instrument gauge coverings, interior surfaces of headlamps, interior surfaces of dome lights, and the like. The coatings are applied in applications that often are subjected to or are constantly subjected to humidity or temperature conditions that would tend to cause fogging.Non-limiting examples of appli  \n35 cations having such conditions are washroom mirrors, storefront windows, and refrigeration units, such as clear refrig erator or freezer doors used in grocery stores or supermarkets. Other Embodiments In accordance with further embodiments of the present   \n40 invention, articles are provided. The articles comprise a substrate and a coating formed on at least one surface of the substrate. The coating is formed by curing a coating composition in accordance with the polyurethane coating compositions described herein directly on the substrate or a primer  \n45 coated substrate or by applying a free-form film prepared from the polyurethane coating compositions described herein.  \n\nIn accordance with further embodiments of the present invention, processes are provided. In one embodiment, the process comprises applying the polyurethane coating compositions described herein to at least one surface of a substrate. The coating compositions are applied directly to the substrate or a primer-coated substrate by flow coating, spray coating, curtain coating, dip coating, spin coating, roll coating,or other suitable technique to create a continuous film on the at least one surface of the substrate. The coating composition applied to the at least one surface of the substrate is cured to form a transparent, abrasion-resistant, water-washable anti-fog coating.  \n\n0 In another embodiment, the process comprises applying a free-form film prepared from the coating compositions described herein to at least one surface of a substrate to form a transparent, abrasion-resistant, water-washable anti-fog coating. The free-form film cures prior to applying to the at   \ni5 least one surface of the substrate. The process further comprises adhering the free-form film to the substrate by an adhesive bonded to at least one surface of the film.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# 21  \n\nThe following analytical test methods and examples are for purposes of illustration only and are not intended to limit the scope of the invention as defined in the claims which are appended hereto.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 19,
+        "chunk": "# ANALYTICAL TEST METHODS  \n\nParameters and values used to quantify certain elements of the present invention, including but not limited to, the examples presented herein are described in detail as follows:  \n\nSubstrate used: Unless otherwise indicated in the Examples below, polycarbonate substrates, including polycarbonate lenses or polycarbonate sheets, are used.  \n\nApplication of the aqueous polyurethane dispersion to a lens: Five or six polycarbonate lenses are dip-coated in the aqueous polyurethane dispersion coating composition having a 12 inch/min draw speed for each Example described herein. Several of the dip-coated lenses described in the Examples are allowed to dry or are subject to other pre-curing conditions for a period oftime prior to curing. The coated lenses are then treated with heat at a specific temperature for a specified amount of time to cure the coating applied to the lens. Different polyurethane coated lenses are used for the different types of tests within each Example, i.e., one coated lens is used for the adhesion test and another coated lens is used for the anti-fogging tests.  \n\nCoating thickness measurement: The measurement of the coating thickness of the polyurethane coated polycarbonate lens is made using an F-20 Film Measurement Unit with a contact stage, available from Filmetrics, Inc. of San Diego, Calif. The coating thickness reported in the Examples is an average value of the coating thickness for the 5 or 6 lenses per Example.  \n\nAdhesion test: The polyurethane coated polycarbonate lens is soaked in boiling water for 1 hour. After cooling and drying, a cross-hatched pattern is made on the coating of the lens with a razor blade. Tape is then applied to the crosshatched section of the coated lens.After the tape is applied, the tape is removed from the coating. The application and removal of the tape is repeated three times. If any of the coating is removed from the lens due to the repeated application and removal of the tape, then the coating composition fails the test. If none of the coating is removed from the lens during the repeated application and removal of the tape, then them coating composition passes the test. The tape used in accordance with the adhesion test is Scotch $\\textsuperscript{\\textregistered}$ brand tape, Scotch 600 from 3M Company of St. Paul, Minn.  \n\nInitial anti-fogging test: Without the polyurethane coated lens being treated or modified in any other manner, i.e., before soaking the coated polycarbonate lens in water, the coated lens is placed at a standard height above a source of $50^{\\circ}\\mathrm{C}$ water in a manner to expose the lens to water vapor from the water source for 3 minutes. If no fog appears on the polyurethane coated lens in this period of time, the coating composition passes the initial anti-fogging test. Otherwise, if fog appears on the coated lens, then the coating composition fails the initial anti-fogging test.  \n\nAnti-fogging after soaking for 1 hour test: A coated polyurethane lens is soaked in water at room temperature for 1 hour.After allowing the coated lens to recover for 12 hours from the soaking, this coated lens is placed at the standard height above a source of $50^{\\circ}\\mathrm{C}$ .water in a manner to expose the lens to water vapor from the water source for at least 8 seconds in accordance with EN166/EN168 anti-fog performance specifications. If no fog appears on the polyurethane coated lens in this period of time, the coating composition passes this anti-fogging test. Otherwise, if fog appears on the coated lens, then the coating composition fails this anti-fogging test.  \n\nInitial haze test: The percent haze of the coated polycar 5 bonate lens is measured using a Haze-Gard Plus available from BYK Gardner USA of Columbia, Md. The measurement of the haze using the Haze-Gard Plus is a quantification of the amount of light scattered as a result of the transmission of the light through the coated polycarbonate lens. The initial 10 haze percent is measured shortly after curing the polyurethane coating on the substrate lens and before any other coated lens is modified or treated in any other way, i.e., before soaking the coated polycarbonate lens in water or before 1 subjecting the lens to falling sand.  \n\nHaze after soaking for 1 hour test: The percent haze of the coated lens is measured with the Haze-Gard Plus immediately after soaking the coated lens in room temperature water for 1 hour. Haze greater than or equal to about $1\\%$ is visible on 0 the surface of the coated lens substrate. Conversely, haze less than or equal to about $1\\%$ is not visible on the coated lens. The haze test after soaking passes if thelens is clear andhaze is not visible on the coated lens.  \n\nFalling sand abrasion test: A coated polycarbonate lens is   \n25 set on an HP-1160 Gardner Falling Sand Apparatus, available from Paul N. Gardner Company of Pompano Beach, Fla. Three (3) kilograms of ASTM 20-30 sand falls through the HP-1160 Apparatus onto the coated polycarbonate lens in accordance with EN166/168 specification.After washing the   \n30 coated polycarbonate lens with soap and water to remove residual sand from the coated lens, the percent haze of this coated lens is measured with the Haze-Gard Plus.Examples described herein refer to an “increase in haze\"after the falling sand abrasion test. This “increase in haze” is the arithmetic   \n35 difference between the percent haze measurement taken after the falling sand test and the initial haze percent measurement, i.e., increase in haze=[(percent haze after falling sand test)- (initial percent haze)].  \n\nList of Materials and/or Abbreviations Used in the Following Examples:  \n\n2-dimethylamine-2-methylpropan-l-ol: An amine salt having an isocyanate reactive hydroxyl group.  \n\nAqueous amine oxide surfactant solution: A N,N-Dimethyldodecylamine N-oxide solution (about $30\\%$ or greater solution of active amine oxide in water), commercially available from Sigma-Aldrich Corp. of St. Louis, Mo.  \n\nAqueous betaine surfactant solution: A N,N-Dimethyl-Ndodecylglycine betaine surfactant solution (about $35\\%$ active alkyl betaine in water), commercially available as EMPIGEN $\\textsuperscript{\\textregistered}$ BB detergent from Sigma-Aldrich Corp. of St. Louis, Mo.  \n\nCirrasol G-265: A quaternary ammonium surfactant having two polyethylene oxide side chains and the hydrophobic chain containing stearamide functionality commercially available from Uniquema Co. of Chicago, Ill.  \n\nSodium dioctylsulfosuccinate: A non-reactive anionic surfactant salt, commercially available for example from Cytec Industries, Inc. of Woodland Park, N.J.  \n\nDMAMP DBS solution: A 2-dimethylamine-2-methylpropan-l-ol salt of dodecylbenzene sulfonic acid solution ( $86\\%$ in xylene).  \n\nIPDI: An isophorone diisocyanate, commercially available as VESTANAT $\\textsuperscript{\\textregistered}$ IPDI from Evonik Degussa Gmbh. of Germany.  \n\nPC 2000: A polyhexamethylene carbonate diol with a $\\mathbf{M}_{\\scriptscriptstyle W}$ of about 20oo, commercially available from Sigma-Aldrich Corp. of St. Louis, Mo.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 20,
+        "chunk": "# 23  \n\nPEG 1000: A polyethylene glycol with an average $\\mathbf{M}_{n}$ ,of about 1,ooo, commercially available from Sigma-Aldrich Corp. of St. Louis, Mo.  \n\nPEO side-chained diol: A diol with an average $\\mathbf{M}_{n}$ of about 1275 having polyethylene oxide side chains. The polyethylene oxide comprises about $78\\%$ by weight of this diol. This polyol is a reaction product of a two step reaction in which a hexamethylene diioscyanate is reacted with a mono-methyoxy-polyethylene glycol ofhaving an $\\mathbf{M}_{n}$ ,ofabout 1,000. The mono-functional mono-methyoxy-polyethylene-glycol reacts with one isocyanate functional group of the diisocyanate, and the residual isocyanate functional group is reacted with a diethanolamine to result in this diol compound having polyethylene oxide side chains.  \n\nPluronic L-62: A polyethylene oxide and polypropylene 1: oxide block copolymer diol with a $\\mathbf{M}_{\\boldsymbol{w}}$ of about 2100.The block copolymer comprises polyethylene oxide segments only in the main chain or backbone of the block copolymer diol. The polyethylene oxide segments comprise about $17\\%$ (wt) of the block copolymer diol. Pluronic L-62 is commer- 2( cially available from BASF Corp of Germany.  \n\nPoly G 83-34: A polyethylene oxide and polypropylene oxide copolymer triol with a $\\mathbf{M}_{\\boldsymbol{w}}$ of about 5000. The copolymer triol comprises $80\\%$ (wt) polyethylene oxide and $20\\%$ (wt) polypropylene oxide. The Poly G 83-34 is commercially available from Arch Chemicals, Inc. of Norwalk, Conn.  \n\nPTF 10o0: A poly(1,4-butanediol), i.e., a poly(tetrahydrofuran） with an average $\\mathbf{M}_{n}$ ，of about 1,ooo, commercially available from Sigma-Aldrich Corp. of St. Louis, Mo.  \n\nQuaternary amine surfactant solution: A hexadecyltrim- 3C ethylammonium hydroxide solution ( $10\\%$ active amine surfactant in water), commercially available from Tokyo Chemical Industry $\\mathrm{Co}$ , Ltd. of Japan.  \n\nTegomer D3403: A trimethylol propane monoethoxylate methyl ether with an average $\\mathbf{M}_{n}$ ，of about 1,220, commer- 3: cially available from Evonik Degussa Gmbh. of Germany.  \n\nTin catalyst: A tin(II)-ethylhexanoate catalyst, commercially available from Sigma-Aldrich Corp. of St. Louis, Mo.  \n\nTriton X-165: An aqueous non-ionic polyethylene glycol ether surfactant solution $(70\\%)$ , commercially available from Sigma-Aldrich Corp. of St. Louis, Mo.  \n\nTrixene DP9C/O12: A triisocyanate partially blocked with a 3,5-dimethylpyrazole blocking agent. Trixene DP9C/012 is commercially available in a propylene glycol monomethyl ether acetate (PM acetate) solution comprising $70\\%$ solids content from Baxenden Chemicals Ltd. of the United Kingdom.  \n\nTrixene BI 7961: An HDI biuret blocked with a 3,5-dimethylpyrazole blocking agent. Trixene BI 7961 is commercially available in a light aromatic hydrocarbon solvent (naptha solvent) comprising about from $68\\%$ to about $72\\%$ solids content from Baxenden Chemicals Ltd. of the United Kingdom.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 21,
+        "chunk": "# EXAMPLES  \n\n55",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# Example 1",
+        "category": " Introduction"
+    },
+    {
+        "id": 23,
+        "chunk": "# Preparation of an Aqueous Polyurethane Dispersion with an Amphoteric Surfactant  \n\n21.1 grams (g) of IPDI, $28.2\\ \\mathrm{g}$ of PC 2000, $2.1\\mathrm{\\g}$ of trimethylolpropane, $3.2~\\mathrm{g}$ of dimethylolpropionic acid, $\\mathrm{8.1~g}$ of Tegomer D3403， and $35\\mathrm{~g~}$ of methylethylketone are mixed together. The mixture is heated to $70^{\\circ}\\mathrm{C}.$ ，and $_{0.01\\mathrm{~g~}}$ of tin 6: catalyst is added. The mixture is then reacted for 3 hours in a nitrogen environment. After the reaction finishes, the result  \n\ning polyurethane prepolymer mixture is cooled to $40^{\\circ}\\mathrm{C}$ 40.3 $\\mathbf{g}$ polyurethane prepolymer mixture is then dispersed into $51.2\\mathrm{g}$ of water and $7.0\\ \\mathrm{g}$ of aqueous betaine surfactant solution with a high shear disperser. $0.25\\mathrm{~g~}$ of hydrazine-monohydrate and $0.58\\mathrm{g}$ of 1,6-hexanediamine are also added during dispersion with the high shear disperser, resulting in an aqueous polyurethane dispersion having about $27\\%$ solids by weight of the dispersion. The resulting polyurethane comprises about $10\\%$ polyethylene oxide side chains by weight of the solids of the polyurethane and about $10\\%$ neutralized amines by weight of the solids of the polyurethane.  \n\nThe measured viscosity of the aqueous polyurethane dispersion is 34 centiPoise (cps) at $25^{\\circ}\\mathrm{C}$ A polycarbonate lens is dip-coated in the aqueous polyurethane dispersion at a 12 inch/min draw speed. The dip-coated lens is dried for $30\\mathrm{min}$ at room temperature. This drying results in the coating being tack-free. The coated lens then is cured at $90^{\\circ}\\mathrm{C}$ . for 2 hours. The resulting coated lens has a coating thickness of about 14.2 micrometers $(\\upmu\\mathrm{m})$ . Haze is about $0.30\\%$ for the initial haze test and about $0.21\\%$ after soaking in water for 1 hour. The increase in haze after the falling sand abrasion test is about $12.8\\%$ . The coated lens also passes each of the adhesion test, the initial anti-fogging test, and the anti-fogging after soaking for 1 hour test, i.e., the coated lens remains fog-free for at least 8 seconds after having soaked the coated lens in water for 1 hour (in accordance with EN166/EN168 specifications).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 24,
+        "chunk": "# Example 2",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 25,
+        "chunk": "# Preparation of an Aqueous Polyurethane Dispersion with an Amphoteric Surfactant  \n\n$24.7\\mathrm{g}$ of IPDI, $14.7\\mathrm{g}$ of PC 2000, $3.2\\ \\mathrm{g}$ of trimethylolpropane, $3.0\\mathrm{g}$ of dimethylolpropionic acid, $\\mathbf{15.3\\:g}$ of PEO-side chained diol, $1.9\\ \\mathrm{g}$ of PTF 1000, and $35\\mathrm{\\g}$ of acetonitrile are mixed together. The mixture is heated to $70^{\\circ}\\mathrm{C}$ ,and $0.01\\mathrm{g}$ of tin catalyst is added. The mixture is then reacted for 3 hours in a nitrogen environment. After the reaction finishes, the resulting polyurethane prepolymer mixture is cooled to $40^{\\circ}\\mathrm{C}$ .40.9 g of polyurethane prepolymer mixture is then dispersed into $\\bar{5}1.2\\mathrm{~\\bar{g}~}$ of water and $\\bar{7.4}\\dot{\\mathrm{g}}$ of aqueous amine oxide surfactant solution with a high shear disperser. $0.55\\mathrm{~g~}$ of hydrazinemonohydrate is also added during dispersion with the high shear disperser, resulting in an aqueous polyurethane dispersion having about $28\\%$ solids by weight of the dispersion. The resulting polyurethane comprises about $17\\%$ polyethylene oxide side chains by weight of the solids of the polyurethane and about $8\\%$ neutralized amines by weight of the solids of the polyurethane.  \n\nThe measured viscosity of the aqueous polyurethane dispersion is 39 cps at $25^{\\circ}\\mathrm{C}$ A polycarbonate lens is dip-coated in the aqueous polyurethane dispersion at a 12 inch/min draw speed. The dip-coated lens is dried for $30\\mathrm{min}$ at room temperature. This drying results in the coating being tack-free. The coated lens then is cured at $90^{\\circ}\\mathrm{~C~}$ .for 2 hours.The resulting coatedlens has a coating thickness of about $11.5\\upmu\\mathrm{m}$ Haze is about $0.24\\%$ for the initial haze test and about $0.60\\%$ after soaking in water for 1 hour. The increase in haze after the falling sand abrasion test is about $15.2\\%$ . The coated lens also passes each of the adhesion test, the initial anti-fogging test, and the anti-fogging after soaking for 1 hourtest, i.e., fog-free for at least 8 seconds (EN166/EN168).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 26,
+        "chunk": "# Example 3",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 27,
+        "chunk": "# Preparation of an Aqueous Polyurethane Dispersion with an Amphoteric Surfactant  \n\n$22.0\\mathrm{g}$ of IPDI, $20.2\\mathrm{g}$ of PC 2000, 2.1 g of trimethylolpropane, $3.2~\\mathrm{g}$ of dimethylolpropionic acid, $9.1\\ \\mathrm{g}$ of PEO-side",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 28,
+        "chunk": "# 25  \n\nchained diol, $5.9\\ \\mathrm{g}$ of PEG 1000, and $35\\mathrm{g}$ of methylethylketone are mixed together. The mixture is heated to $70^{\\circ}\\mathrm{C}.$ ,and $0.01\\ \\mathrm{g}$ of tin catalyst is added. The mixture is then reacted for 3 hours in a nitrogen environment.After the reaction finishes, the resulting polyurethane prepolymer mixture is cooled to $40^{\\circ}$ C. $37.2\\ {\\mathrm{g}}$ of polyurethane prepolymer mixture is then dispersed into $53.3\\ \\mathrm{g}$ of water and $\\boldsymbol{7.3\\ \\mathrm{g}}$ of aqueous amine oxide surfactant solution with a high shear disperser. $0.25\\mathrm{g}$ of hydrazine-monohydrate and $0.59\\mathrm{g}$ of 1,6-hexanediamine are also added during dispersion with the high shear disperser, 1 resulting in an aqueous polyurethane dispersion having about $27\\%$ solids by weight of the dispersion. The resulting polyurethane comprises about $10\\%$ polyethylene oxide side chains by weight of the solids of the polyurethane, about $10\\%$ polyethylene oxide main chains by weight of the solids of the 1 polyurethane, and about $8\\%$ neutralized amines by weight of the solids of the polyurethane.  \n\nThe measured viscosity of the aqueous polyurethane dispersion is 63 cps at $25^{\\circ}\\mathrm{C}.\\mathrm{A}$ polycarbonate lens is dip-coated in the aqueous polyurethane dispersion at a 12 inch/min draw speed. The dip-coated lens is dried for $30\\mathrm{min}$ at room temperature. This drying results in the coating being tack-free. The coated lens then is cured at $90^{\\circ}\\mathrm{~C~}$ .for 2 hours. The resulting coatedlens has a coating thickness of about $11.0\\upmu\\mathrm{m}$ Haze is about $0.30\\%$ for the initial haze test and about $0.42\\%$ after soaking in water for 1 hour. The increase in haze after the falling sand abrasion test is about $16.3\\%$ . The coated lens also passes each of the adhesion test, the initial anti-fogging test, and the anti-fogging after soaking for 1 hour test, i.e., fog-free for at least 8 seconds (EN166/EN168).  \n\n30",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 29,
+        "chunk": "# Example 4",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 30,
+        "chunk": "# Preparation of an Aqueous Polyurethane Dispersion with an Amphoteric Surfactant and Blocked Polyisocyanates  \n\n$21.8\\mathrm{g}$ of IPDI, $19.0\\mathrm{g}$ of PC 2000, 2.1 g of trimethylolpropane, $3.2~\\mathrm{g}$ of dimethylolpropionic acid, $9.1\\ \\mathrm{g}$ of PEO-side chained diol, $5.9\\ \\mathrm{g}$ of PEG 1000, and $35\\mathrm{g}$ of methylethylketone are mixed together. The mixture is heated to $70^{\\circ}\\mathrm{C}.$ ,and $0.01\\ \\mathrm{g}$ of tin catalyst is added. The mixture is then reacted for 3 hours in a nitrogen environment. The resulting polyurethane prepolymer mixture is cooled to $40^{\\circ}\\mathrm{C}.$ ,and $1.4\\ \\mathrm{g}$ of Trixene BI 7961 is added to the mixture. $_{37.1\\mathrm{~g~}}$ of the resulting polyurethane prepolymer mixture is then dispersed into 53.4 $\\mathbf{g}$ of water and $7.3\\mathrm{g}$ of aqueous amine oxide surfactant solution with a high shear disperser. $0.25\\mathrm{~g~}$ of hydrazine-monohydrate and $0.59\\mathrm{g}$ of 1,6-hexanediamine are also added during dispersion with the high shear disperser, resulting in an aqueous polyurethane dispersion having about $25\\%$ solids by weight of the dispersion. The resulting polyurethane comprises about $10\\%$ polyethylene oxide side chains by weight of the solids of the polyurethane, about $10\\%$ polyethylene oxide main chains by weight of the solids of the polyurethane, about $1.7\\%$ blocked isocyanates by weight of the solids of the polyurethane, and about $8\\%$ neutralized amines by weight of the solids of the polyurethane.  \n\nThe measured viscosity of the aqueous polyurethane dispersion is 47 cps at $25^{\\circ}\\mathrm{C}.\\mathrm{A}$ polycarbonate lens is dip-coated in the aqueous polyurethane dispersion at a 12 inch/min draw speed. The dip-coated lens is dried for $30\\mathrm{min}$ at room temperature. This drying results in the coating being tack-free. The coated lens then is cured at $90^{\\circ}\\mathrm{~C~}$ .for 2 hours. The resulting coated lens has a coating thickness of about $8.5\\upmu\\mathrm{m}$ Haze is about $0.14\\%$ for the initial haze test and about $0.30\\%$ after soaking in water for 1 hour. The increase in haze after the falling sand abrasion test is about $10.7\\%$ .The coated lens also passes each of the adhesion test, the initial anti-fogging test, and the anti-fogging after soaking for 1 hour test, i.e., fog-free for at least 8 seconds (EN166/EN168).  \n\nExample 5  \n\nPreparation of a Polyurethane Mixture with an Isocyanate-Reactive Salt of a Surfactant and Partially Blocked Polyisocyanates  \n\n$24.7\\ \\mathrm{g}$ Trixene DP9C/012, $4.2\\ \\mathrm{g}$ Poly G 83-34, $\\boldsymbol{1.1\\mathrm{\\g}}$ Pluronic L-62, $0.5\\mathrm{~g~}$ trimethylolethane, $0.6\\ \\mathrm{g}$ triethanolamine, and $5.0\\mathrm{g}$ DMAMP DBS solution ( $86\\%$ in xylene) are added to $4.1\\mathrm{gN}$ -methyl pyrrolidone, $4.5\\mathrm{g}$ tertiary amyl alcohol, 7.9 g methylethylketone, and $\\mathbf{0.9}\\mathbf{g}2{\\mathcal{A}}$ -pentanedione and mixed together. The mixture is heated to $60^{\\circ}\\mathrm{C}$ and then reacted for 8 hours in a nitrogen environment.Following the reaction, the resulting polyurethane prepolymer mixture is cooled to $30^{\\circ}$ C. The cooled polyurethane prepolymer mixture fails to disperse in water. The resulting polyurethane comprises about $3\\%$ polyethylene oxide side chains by weight of the solids of the polyurethane, about $10\\%$ polyethylene oxide main chains by weight of the solids of the polyurethane, and about $44\\%$ blocked polyisocyanates by weight of the solids of the polyurethane.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 31,
+        "chunk": "# Example 6  \n\nPreparation of an Aqueous Polyurethane Dispersion with a Isocyanate-Reactive Cationic Surfactant and Partially Blocked Polyisocyanates  \n\n35 $19.5\\mathrm{g}$ Trixene DP9C/012, $1.2{\\mathrm{g}}$ PEG 1000, $4.6\\:\\mathrm{gPC}$ 2000, $0.6\\ \\mathrm{g}$ trimethylolpropane, $3.8\\:\\mathrm{g}$ Tegomer D3403, $1.2\\mathrm{g}$ Cirrasol G-265, and $0.002{\\mathrm{~g~}}$ tin catalyst are added to $4.0\\ \\mathrm{g}$ methylethylketone and $2.8\\mathrm{~g~}$ diacetone alcohol and are mixed together. The mixture is heated to $60^{\\circ}\\mathrm{C}.$ and then reacted for   \n40 6 hours in a nitrogen environment.Following the reaction, the resulting polyurethane prepolymer mixture is cooled to $30^{\\circ}$ C. The polyurethane prepolymer mixture is then dispersed in $63.0\\ \\mathrm{g}$ of distilled water, $0.34\\mathrm{g}1,6$ -hexanediamine, and 0.15 $\\ g30\\%$ aqueous hydrazine with a high shear disperser, result  \n45 ing in a stable aqueous polyurethane dispersion having about $24\\%$ solids by weight of the dispersion. The resulting polyurethane comprises about $6\\%$ polyethylene oxide side chains by weight of the solids of the polyurethane, about $14.6\\%$ polyethylene oxide main chains by weight of the solids of the   \n50 polyurethane, and about $36.2\\%$ blocked polyisocyanates by weight of the solids of the polyurethane. The measured viscosity of the aqueous polyurethane dispersion is 37 cps at $25^{\\circ}\\mathrm{C}$ A polycarbonate lens is dip-coated in the aqueous polyurethane dispersion at a 12 inch/min draw   \n55 speed. The dip-coated lens is cured at $120^{\\circ}\\mathrm{~C~}$ . for 1 hour resulting in a coating with a thickness of about $7.9\\upmu\\mathrm{m}$ .Haze is about $0.8\\%$ for the initial haze test. The haze is about $1.1\\%$ after soaking in water for 1 hour and remains clear at this $1.1\\%$ haze. The increase in haze after the faling sand abrasion   \n50 test is about $5.5\\%$ . The polyurethane coated lens dip-coated with the aqueous polyurethane dispersion also passes each of the adhesion test and the initial anti-fogging test. However, the coated lens fails the anti-fogging after soaking for 1 hour test, i.e., not fog-free for at least 8 seconds. This polyurethane   \n55 coating exhibits resistance to washing by chemicals such as separate washing by each of isopropyl alcohol, tolulene, and methylethylketone.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 32,
+        "chunk": "# 27 Example 7",
+        "category": " References"
+    },
+    {
+        "id": 33,
+        "chunk": "# 28",
+        "category": " Introduction"
+    },
+    {
+        "id": 34,
+        "chunk": "# Preparation of an Aqueous Polyurethane Dispersion with a Isocyanate-Reactive Cationic Surfactant and Partially Blocked Polyisocyanates  \n\n$\\ensuremath{4.6\\mathrm{~g~}}$ IPDI, $5.5\\ \\mathrm{g}$ DP9C/012, $7.8\\ \\mathrm{g}$ PC 2000, $0.7\\ \\mathrm{g}$ trimethylolpropane, $3.2\\ \\mathrm{g}$ PEO-side chained diol, $2.1\\ \\mathrm{g}$ Cirrasol G-265, and $0.011\\ \\mathrm{g}$ tin catalyst are added to $10.3\\ \\mathrm{g}\\mathrm{N}$ -methyl pyrrolidone and $2.2\\mathrm{~g~}$ diacetone alcohol and are mixed together. The mixture is heated to $65^{\\circ}\\mathrm{C}$ . and then reacted for 3 hours in an inert atmosphere. Following the reaction, the resulting polyurethane prepolymer mixture is cooled to $40^{\\circ}$ C. The cooled polyurethane prepolymer mixture is then dispersed in $66.6\\mathrm{g}$ of distilled water and $0.65{\\mathrm{g}}2$ (2-aminoethyl) aminoethanol with a high shear disperser, resulting in a stable aqueous polyurethane dispersion having about $24\\%$ solids by weight of the dispersion. The resulting polyurethane comprises about $11\\%$ polyethylene oxide side chains by weight of the solids of the polyurethane, about $2\\%$ polyethylene oxide main chains by weight of the solids of the polyurethane, and about $11.7\\%$ blocked polyisocyanates by weight of the solids of the polyurethane.  \n\nThe measured viscosity of the aqueous polyurethane dispersion is 54 cps at $25^{\\circ}\\mathrm{C}.\\mathrm{A}$ polycarbonate lens is dip-coated in the aqueous polyurethane dispersion at a 12 inch/min draw speed. The dip-coated lens is cured at $120^{\\circ}~\\mathrm{C}$ .for 1 hour resulting in a coating with a thickness of about $8.1\\upmu\\mathrm{m}$ .Haze is about $0.18\\%$ for the initial haze test and about $0.25\\%$ after soaking in water for 1 hour. The increase in haze after the falling sand abrasion test is about $1.0\\%$ . The polyurethane coated lens dip-coated with the aqueous polyurethane dispersion also passes the adhesion test. However, the coated lens fails the initial anti-fogging test and the anti-fogging after soaking for 1 hour test, i.e., not fog-free for at least 8 seconds. This polyurethane coating exhibits resistance to washing by chemicals such as isopropyl alcohol but does not show resistance to separate washing by each of tolulene or methylethylketone.  \n\nPreparation of an Aqueous Polyurethane Dispersion   \nwith an Isocyanate-Reactive Salt of a Surfactant, an Isocyanate-Reactive Cationic Surfactant, and Partially Blocked Polyisocyanates  \n\n22.4 gDP9C/012, $3.9\\mathrm{g}$ Poly G 83-34, $1.0\\mathrm{g}$ Pluronic L-62, $0.4\\ \\mathrm{g}$ trimethylolethane, $2.0\\mathrm{g}$ Cirrasol G-265, $1.0\\mathrm{g}\\mathrm{DMAMP}$ DBS, and $0.11\\ \\mathrm{\\ttg}$ tin catalyst are added to $2.6\\mathrm{~g~N~}$ -methyl pyrrolidone plus $4.7\\:\\mathrm{g}$ methylethylketone, $2.8\\:\\mathrm{g}$ tertiary amyl alcohol, $\\mathbf{0.6\\g\\2}\\mathcal{A}$ -pentanedione and $4.0\\ \\mathrm{g}$ diacetone alcohol and are mixed together. The mixture is heated to $60^{\\circ}\\mathrm{C}$ .and then reacted for 6 hours in a nitrogen atmosphere. Following the reaction, the resulting polyurethane prepolymer mixture is cooled and then dispersed in $59.0\\mathrm{g}$ of distilled water, $0.1\\ \\mathrm{g}$ trimethylolethane, and $\\boldsymbol{0.2\\mathrm{~g~}}$ triethanolamine with a high shear disperser, resulting in a stable aqueous polyurethane dispersion having about $24\\%$ solids by weight of the dispersion. The resulting polyurethane comprises about $3\\%$ polyethylene oxide side chains by weight of the solids of the polyurethane, about $12\\%$ polyethylene oxide main chains by weight of the solids of the polyurethane, and about $48\\%$ blocked polyisocyanates by weight of the solids of the polyurethane.  \n\nin the aqueous polyurethane dispersion at a 12 inch/min draw speed. The dip-coated lens is cured at $120^{\\circ}~\\mathrm{C}$ .for 1 hour resulting in a coating with a thickness of about $12.1\\upmu\\mathrm{m}$ .Haze is about $0.17\\%$ for the initial haze test and about $0.58\\%$ after soaking in water for 1 hour. The increase in haze after the falling sand abrasion test is about $1.7\\%$ . The coated lens also passes each of the adhesion test, the initial anti-fogging test, and the anti-fogging after soaking for 1 hour test, i.e., fog-free for at least 8 seconds (EN166/EN168). This polyurethane coated lens also does not fog when exposed to the water vapor in excess of 30 seconds (ASTM F659), in excess of 60 seconds, or in excess of 900 seconds. This polyurethane coating exhibits resistance to washing by chemicals such as separate washing by each of isopropyl alcohol, tolulene, and methylethylketone.  \n\nThe measured viscosity of the aqueous polyurethane dispersion is 32 cps at $25^{\\circ}\\mathrm{C}.\\mathrm{A}$ polycarbonate lens is dip-coated",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 35,
+        "chunk": "# Example 9  \n\nPreparation of an Aqueous Polyurethane Dispersion with an Isocyanate-Reactive Salt of Surfactant, a Isocyanate-Reactive Cationic Surfactant, a Non-Reactive Anionic Surfactant, and Partially Blocked Polyisocyanates  \n\n$3.1\\ \\mathrm{g}$ IPDI, $3.6\\ \\mathrm{g}$ DP9C/012, $3.0~\\mathrm{g}$ PC 2000, $0.3\\mathrm{~g~}$ trimethylolpropane, $2.3\\ \\mathrm{g}$ PEO side-chained diol, $1.0\\ \\mathrm{g}$ Poly G 83-34, $\\boldsymbol{1.3\\ \\mathrm{g}}$ Cirrasol G-265, $0.7\\ \\mathrm{g}$ DMAMP DBS solution, $0.9\\ \\mathrm{g}$ sodium dioctylsulfosuccinate, and $_{0.011\\mathrm{~g~}}$ tin catalyst are added to $5.1\\mathrm{\\g}$ N-methyl pyrrolidone and $2.2\\ \\mathrm{g}$ diacetone alcohol and are mixed together. The mixture is heated to $65^{\\circ}$ C. and then reacted for 3 hours in an inert atmosphere. Following the reaction, the resulting polyurethane prepolymer mixture is cooled to $40^{\\circ}\\mathrm{C}$ The cooled polyurethane prepolymer mixture is then dispersed in $75.7\\mathrm{\\bar{g}}$ of distilled water and $0.4\\mathrm{~g~}2$ -(2-aminoethyl)aminoethanol with a high shear disperser, resulting in a stable aqueous polyurethane dispersion having about $16\\%$ solids by weight of the dispersion. The resulting polyurethane comprises about $12\\%$ polyethylene oxide side chains by weight of the solids of the polyurethane, about $6\\%$ polyethylene oxide main chains by weight of the solids of the polyurethane, and about $11\\%$ blocked polyisoI cyanates by weight of the solids of the polyurethane.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 36,
+        "chunk": "# Example 8  \n\nThe measured viscosity of the aqueous polyurethane dispersion is 29 cps at $25^{\\circ}\\mathrm{C}$ A polycarbonate lens is dip-coated in the aqueous polyurethane dispersion at a 12 inch/min draw speed. The dip-coated lens is cured at $120^{\\circ}\\mathrm{~C~}$ .for 1 hour   \n45 resulting in a coating with a thickness of about $8.3\\upmu\\mathrm{m}$ .Haze is about $0.25\\%$ for the initial haze test and about $0.23\\%$ after soaking in water for 1 hour. The increase in haze after the falling sand abrasion test is about $1.2\\%$ . The coated lens passes each of the adhesion test, the initial anti-fogging test,   \n50 and the anti-fogging after soaking for 1 hour test, i.e., fog free for at least 8 seconds (EN166/EN168). This polyurethane coated lens does not fog when exposed to the water vapor in excess of 30 seconds (ASTM F659), in excess of 60 seconds, or in excess of 900 seconds. This polyurethane coating exhib  \n55 its resistance to washing by chemicals such as separate washing by each of isopropyl alcohol, tolulene, and methylethylketone.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 37,
+        "chunk": "# Example 10  \n\nPreparation of an Aqueous Polyurethane Dispersion   \nfrom the Combination of the Aqueous Polyurethane Dispersion of Example 3 and the Aqueous Polyurethane Dispersion of Example 8  \n\n$_{\\textrm{100~g}}$ of the aqueous polyurethane dispersion from Example 8 is mixed with $100\\ \\mathrm{g}$ of the aqueous polyurethane",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 38,
+        "chunk": "# 30  \n\ndispersion from Example 3, producing an aqueous polyurethane dispersion containing $25\\%$ solids by weight of the dispersion. To reduce viscosity, an additional $100\\ \\mathrm{g}$ water is added with agitation, resulting in a stable, hazy aqueous polyurethane dispersion having about $17\\%$ solids by weight of the dispersion. The resulting polyurethane comprises about $6.7\\%$ polyethylene oxide side chains by weight of the solids of the polyurethane, about $10.9\\%$ polyethylene oxide main chains by weight of the solids of the polyurethane, about $4.2\\%$ neutralized amines by weight of the solids of the polyurethane, and about $22.6\\%$ blocked polyisocyanates by weight of the solids of the polyurethane.  \n\nA polycarbonate lens is dip-coated in the aqueous polyurethane dispersion at a 12 inch/min draw speed. The dip-coated lens is dried at room temperature for 5 minutes and then is dried at $85^{\\circ}\\mathrm{C}$ .for an additional 10 minutes. The coating on the lens is tack-free following the drying at $85^{\\circ}\\mathrm{C}$ .The tackfree coated lens is cured at $120^{\\circ}\\mathrm{~C~}$ for 1 hour resulting in a coating with a thickness of about $8.1\\upmu\\mathrm{m}$ \\*  \n\nThe increase in haze after the falling sand abrasion test is about $3.2\\%$ . In a separate test, the coated lens also exhibits little increase in haze when exposed to boiling water for two hours. The coated lens also passes each of the adhesion test, the initial anti-fogging test, and the anti-fogging after soaking for 1 hour test, i.e., fog free for at least 8 seconds (EN166/ EN168). This polyurethane coated lens also does not fog when exposed to the water vapor in excess of 30 seconds (ASTM F659), in excess of 60 seconds, or in excess of 7200 seconds (2 hours), both before and after soaking in water for 1 hour. Additionally, the coated lens does not fog when exposed to the water vapor in excess of 30 seconds, in excess of 60 seconds, or in excess of 7200 seconds after soaking in water for 24 hours (followed by a 12 hour recovery period). This polyurethane coating exhibits resistance to washing by chemicals such as separate washing by each of isopropyl alcohol, diacetone alcohol, and methylethylketone.  \n\ncoating thickness of about $6.9\\upmu\\mathrm{m}$ . This coated lens performs the same as the coated lens described in Example 10 with respect to haze, fogging, abrasion, adhesion, and resistance to chemicals.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 39,
+        "chunk": "# Example 12  \n\nPreparation of an Organic Solvent Polyurethane Solution from the Combination of the Prepolymer of Example 3 and the Prepolymer of Example 8  \n\n$50\\ \\mathrm{g}$ of the prepolymer of Example 3 and $50\\textrm{g}$ of the prepolymer of Example 8 are mixed together and are added to $185.5\\mathrm{~g~}$ 1-methoxy-2-propanol with agitation, resulting in a homogenous, clear polyurethane solution. The resulting polyurethane solution comprises essentially all non-aqueous solvents, i.e., the solution is essentially free of water. The polyurethane solution has about $20\\%$ solids by weight of the solution. The resulting polyurethane comprises about $9.0\\%$ polyethylene oxide side chains by weight of the solids of the polyurethane, about $11.5\\%$ polyethylene oxide main chains by weight of the solids of the polyurethane, and about $22.6\\%$ blocked polyisocyanates by weight of the solids of the polyurethane.  \n\n25 The measured viscosity of the organic solvent polyurethane solution is about 25 cps at $25^{\\circ}\\mathrm{C}.$ After vigorous shaking of the a sample of this solution, no foaming is observed in the sample. A polycarbonate lens is dip-coated in the polyurethane solution at a 12 inch/min draw speed. The dip-coated   \n30 lens is dried at room temperature for 5 minutes and then is dried at $85^{\\circ}\\mathrm{C}$ . for an additional 1O minutes. The coating on the lens is tack-free following the drying at $85^{\\circ}\\mathrm{C}$ The tackfree coated lens is cured at $120^{\\circ}\\mathrm{C}$ . for 1 hour resulting in a coating with a thickness of about $5.8~{\\upmu\\mathrm{m}}$ . This coated lens   \n35 performs substantially the same as the coated lens described in Example 10 with respect to haze, fogging, abrasion, adhesion, and resistance to chemicals.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 40,
+        "chunk": "# Example 11  \n\nPreparation of a Mixture of an Aqueous Polyurethane Dispersion and an Organic Solvent Polyurethane Solution from the Combination of the Prepolymer of Example 3 and the Prepolymer of  \n\nExample 8 with an Amphoteric Surfactant  \n\n$50\\ \\mathrm{g}$ of the prepolymer of Example 3 and $50\\ \\mathrm{g}$ of the prepolymer ofExample 8 are mixed together and are added to a mixture of $93\\ \\mathrm{g}\\ 1$ -methoxy-2-propanol and $93\\ \\mathrm{g}$ water. 5.8 g aqueous amine oxide surfactant solution, $0.20\\mathrm{g}$ hydrazine monohydrate, and $0.47\\mathrm{g}$ hexanediamine chain extenders are added to the prepolymer mixture with agitation resulting in a hazy aqueous polyurethane dispersion and an organic solvent polyurethane solution mixture. The resulting polyurethane mixture has a solid content of about $20\\%$ by weight of the polyurethane mixture. The resulting polyurethane comprises about $8.2\\%$ polyethylene oxide side chains by weight of the solids of the polyurethane, about $10.3\\%$ polyethylene oxide main chains by weight of the solids of the polyurethane, about $2.9\\%$ neutralized amines by weight of the solids of the polyurethane, and about $20.4\\%$ blocked polyisocyanates by weight of the solids of the polyurethane.  \n\nA polycarbonate lens is dip-coated in the aqueous polyurethane dispersion at a 12 inch/min draw speed. The dip-coated lens is dried at room temperature for 5 minutes and then is dried at $85^{\\circ}\\mathrm{C}$ .for an additional 1O minutes. The coating on the lens is tack-free following the drying at $85^{\\circ}\\mathrm{C}$ .The tackfree coated lens is cured at $120^{\\circ}\\mathrm{~C~}$ .for 1 hour resulting in a",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 41,
+        "chunk": "# Comparative Example 1  \n\n40",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 42,
+        "chunk": "# Preparation of an Aqueous Polyurethane Dispersion  \n\n$23.3\\ \\mathrm{g}$ of IPDI, $\\boldsymbol{7.1\\ \\mathrm{g}}$ of PC 2000, $2.1\\ \\mathrm{g}$ of trimethylolpropane, $29.6\\mathrm{g}$ of Tegomer D3403, $2.8\\:\\mathrm{g}$ of 1,6-hexanediol, and   \n45 $35\\mathrm{g}$ of acetonitrile are mixed together. The mixture is heated to $70^{\\circ}\\mathrm{C}.$ ,and $_{0.01\\mathrm{~g~}}$ of tin catalyst is added. The mixture is then reacted for 3 hours in a nitrogen environment. After the reaction finishes, the resulting polyurethane prepolymer mixture is cooled to $40^{\\circ}\\mathrm{~C~}$ $45.2~\\mathrm{g}$ of the cooled polyurethane   \n50 prepolymer mixture is dispersed in $51.7\\mathrm{g}$ of water with a high shear disperser. $\\mathbf{0.62\\g}$ of hydrazine-monohydrate is also added during dispersion with the high shear disperser, resulting in an aqueous polyurethane dispersion having about $30\\%$ solids by weight of the dispersion. The resulting polyurethane   \n55 comprises about $40\\%$ polyethylene oxide side chains by weight of the solids of the polyurethane.  \n\nThe measured viscosity of the aqueous polyurethane dispersion is 70 cps at $25^{\\circ}\\mathrm{C}$ A polycarbonate lens is dip-coated in the aqueous polyurethane dispersion at a 12 inch/min draw speed. The dip-coated lens is dried for $30\\mathrm{min}$ at room temperature and then is cured at $90^{\\circ}\\mathrm{C}$ for 2 hours. The resulting coatedlens has a coating thickness of about $18.0\\upmu\\mathrm{m}$ .Haze is about $0.80\\%$ for the initial haze test. The coated lens cannot be seen through after soaking in water for 1 hour and has a haze of about $75.0\\%$ .The haze is not measured after the falling sand abrasion test because all of the sand could not be washed off the coated lens. This polyurethane coated lens",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 43,
+        "chunk": "#",
+        "category": "ovide the text segment you would like me to analyze."
+    },
+    {
+        "id": 44,
+        "chunk": "# 32  \n\nfails both the initial anti-fogging test and the anti-fogging test after soaking in water for 1 hour because fog is observed on this polyurethane coated lens during each test. This coated lens passes the adhesion test.  \n\ntest and the anti-fogging after soaking for 1 hour test, i.e., fog-free for at least 8 seconds (EN166/EN168). However, this coated lens fails the initial anti-fogging test with visible fog on the lens appearing during the 3 minutes of the test.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 45,
+        "chunk": "# Comparative Example 2  \n\nComparative Example 4",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 46,
+        "chunk": "# Preparation of an Aqueous Polyurethane Dispersion  \n\n$22.9\\mathrm{g}$ of IPDI, $14.5\\mathrm{g}$ of PC 2000, $2.2\\mathrm{g}$ of trimethylolpropane, $22.6\\mathrm{g}$ of Tegomer D3403, $2.9\\:\\mathrm{g}$ of 1,6-hexanediol, and $35\\mathrm{g}$ of acetonitrile are mixed together. The mixture is heated to $70^{\\circ}\\mathrm{C}.$ ，and $_{0.01\\mathrm{~g~}}$ of tin catalyst is added. The mixture is then reacted for 3 hours in a nitrogen environment. After the reaction finishes, the resulting polyurethane prepolymer mixture is cooled to $40^{\\circ}$ C. $_{45.2\\mathrm{~g~}}$ of the cooled polyurethane prepolymer mixture is dispersedin $51.7\\mathrm{g}$ of water with a high shear disperser. $\\mathbf{0.62\\g}$ of hydrazine-monohydrate is also added during dispersion with the high shear disperser, resulting in an aqueous polyurethane dispersion having about $30\\%$ solids by weight of the dispersion. The resulting polyurethane comprises about $31\\%$ polyethylene oxide side chains by weight of the solids of the polyurethane.  \n\nThe measured viscosity of the aqueous polyurethane dispersion is 72 cps at $25^{\\circ}\\mathrm{C}.\\mathrm{A}$ polycarbonate lens is dip-coated in the aqueous polyurethane dispersion at a 12 inch/min draw speed. The dip-coated lens is dried for 30 min at room temperature and then is cured at $90^{\\circ}\\mathrm{C}$ for 2 hours. The resulting coated lens has a coating thickness of about $19.0\\upmu\\mathrm{m}$ .Haze is about $0.66\\%$ for the initial haze test. The coated lens cannot be seen through after soaking in water for 1 hour and has a haze of about $37.0\\%$ .The haze is not measured after the falling sand abrasion test because all of the sand could not be washed off the coated lens. This polyurethane coated lens fails both the initial anti-fogging test and the anti-fogging after soaking for 1 hour test because fog is observed on this polyurethane coated lens during each test. This coated lens passes the adhesion test.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 47,
+        "chunk": "# Preparation of a Polyurethane Mixture  \n\n$21.6\\ \\mathrm{g}$ of IPDI, $31.0\\mathrm{g}$ of PC 2000, $2.1\\ \\mathrm{g}$ of trimethylolpropane, $7.4\\ \\mathrm{g}$ of Tegomer D3403, $2.8\\ \\mathrm{g}$ of 1,6-hexanediol, and $35\\mathrm{g}$ of acetonitrile are mixed together. The mixture is heated to $70^{\\circ}\\mathrm{C}.$ ,and $0.01\\ \\mathrm{g}$ of tin catalyst is added. The mixture is then reacted for 3 hours in a nitrogen environment.After the reaction finishes, the resulting polyurethane mixture is cooled to $40^{\\circ}\\mathrm{C}$ $_{45.2\\mathrm{~g~}}$ of the cooled polyurethane mixture fails to disperse in $51.8\\ \\mathrm{g}$ of water with a high shear disperser. The resulting polyurethane comprises about $10\\%$ polyethylene oxide side chains by weight of the solids of the polyurethane.  \n\nComparative Example 5",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 48,
+        "chunk": "# Preparation of a Polyurethane Mixture with Cationic Surfactant  \n\n$25.4\\mathrm{g}$ of IPDI, $24.8\\mathrm{g}$ of PC 2000, $0.5\\mathrm{g}$ of trimethylolpropane, $4.0\\ \\mathrm{g}$ of dimethylolpropionic acid, $9.9\\ \\mathrm{g}$ of Tegomer D3403, $2.5\\mathrm{\\g}$ of 1,6-hexanediol, and $30\\ \\mathrm{g}$ of acetonitrile are mixed together. The mixture is heated to $70^{\\circ}\\mathrm{C}$ ,and $0.01\\mathrm{g}$ of tin catalyst is added.The mixture is then reacted for 3 hours in a nitrogen environment.After the reaction finishes, the resulting polyurethane mixture is cooled to $40^{\\circ}$ C. $27.9\\ \\mathrm{g}$ of the cooled polyurethane mixture fails to disperse into a mixture of $47.4\\ \\mathrm{g}$ of water and $24.8\\ \\mathrm{g}$ of quaternary amine surfactant solution with high shear disperser. The resulting polyurethane comprises about $12\\%$ polyethylene oxide side chains by weight of the solids of the polyurethane and about $10\\%$ neutralized amine by weight of the solids of the polyurethane.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 49,
+        "chunk": "# Comparative Example 3  \n\n40  \n\nComparative Example 6",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 50,
+        "chunk": "# Preparation of an Aqueous Polyurethane Dispersion Preparation of an Aqueous Polyurethane Dispersion  \n\n$22.2\\ \\mathrm{g}$ of IPDI, $22.8\\mathrm{g}$ of PC 2000, $2.1\\ \\mathrm{g}$ of trimethylolpropane, $15.0\\mathrm{g}$ of Tegomer D3403, $2.8\\:\\mathrm{g}$ of 1,6-hexanediol, and $35\\mathrm{g}$ of acetonitrile are mixed together. The mixture is heated to $70^{\\circ}\\mathrm{C}.$ ，and $0.01\\mathrm{\\g}$ of tin catalyst is added. The mixture is then reacted for 3 hours in a nitrogen environment. After the reaction finishes, the resulting polyurethane prepolymer mixture is cooled to $40^{\\circ}\\mathrm{~C~}$ $45.2~\\mathrm{g}$ of the cooled polyurethane prepolymer mixture is dispersed in $51.8\\mathrm{g}$ of water with a high shear disperser. $\\mathbf{0.60\\g}$ of hydrazine-monohydrate is also added during dispersion with the high shear disperser, resulting in an aqueous polyurethane dispersion having about $30\\%$ solids by weight of the dispersion. The resulting polyurethane comprises about $20\\%$ polyethylene oxide side chains by weight of the solids of the polyurethane.  \n\nThe measured viscosity of the aqueous polyurethane dispersion is 60 cps at $25^{\\circ}\\mathrm{C}.\\mathrm{A}$ polycarbonate lens is dip-coated in the aqueous polyurethane dispersion at a 12 inch/min draw speed. The dip-coated lens is dried for 30 min at room temperature and then is cured at $90^{\\circ}\\mathrm{C}$ for 2 hours. The resulting coated lens has a coating thickness of about $10.6\\upmu\\mathrm{m}$ .Haze is about $0.22\\%$ for the initial haze test. The haze is about $1.3\\%$ after soaking in water for 1 hour and is visible on the coated lens. The increase in haze after the falling sand abrasion test is about $32.8\\%$ . The coated lens passes each of the adhesion  \n\n$21.8\\mathrm{g}$ of IPDI, $27.2\\mathrm{g}$ of PC 2000, $2.1\\ \\mathrm{g}$ of trimethylolpro  \n45 pane, $11.1\\ \\mathrm{g}$ of Tegomer D3403, $2.8\\:\\mathrm{g}$ of 1,6-hexanediol, and $35\\mathrm{g}$ of acetonitrile are mixed together. The mixture is heated to $70^{\\circ}\\mathrm{C}.$ ,and $_{0.01\\mathrm{~g~}}$ of tin catalyst is added. The mixture is then reacted for 3 hours in a nitrogen environment. After the reaction finishes, the resulting polyurethane prepolymer mix  \n50 ture is cooled to $40^{\\circ}\\mathrm{~C~}$ $45.2~\\mathrm{g}$ of the cooled polyurethane prepolymer mixture is dispersed in $51.8\\mathrm{g}$ of water with a high shear disperser. $\\mathbf{0.60\\g}$ of hydrazine-monohydrate is also added during dispersion with the high shear disperser, resulting in an aqueous polyurethane dispersion having about $30\\%$   \n55 solids by weight of the dispersion.The resulting polyurethane comprises about $15\\%$ polyethylene oxide side chains by weight of the solids of the polyurethane.  \n\nThe measured viscosity of the aqueous polyurethane dispersion is 50 cps at $25^{\\circ}\\mathrm{C}$ A polycarbonate lens is dip-coated in the aqueous polyurethane dispersion at a 12 inch/min draw speed. The dip-coated lens is dried for $30\\mathrm{min}$ at room temperature and then is cured at $90^{\\circ}\\mathrm{C}$ for 2 hours. The resulting coated lens has a coating thickness of about $8.6\\upmu\\mathrm{m}$ .Haze is about $0.30\\%$ for the initial haze test and $0.52\\%$ after soaking in water for 1 hour. The increase in haze after the falling sand abrasion test is about $19.8\\%$ . This polyurethane coated lens fails both the initial anti-fogging test and the anti-fogging",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 51,
+        "chunk": "# 33",
+        "category": " Introduction"
+    },
+    {
+        "id": 52,
+        "chunk": "# 34  \n\nafter soaking for 1 hour test because fog is observed on this polyurethane coated lens during each test. This coated lens passes the adhesion test.  \n\nComparative Example 7  \n\nPreparation of an Aqueous Polyurethane Dispersion with a Non-Reactive Surfactant  \n\n$103\\mathrm{g}$ of the aqueous polyurethane dispersion of Compara- 10 tive Example 6 is mixed with ${4\\mathrm{g}}$ of Triton X-165.A polycarbonate lens is dip-coated in the aqueous polyurethane dispersion at a 12 inch/min draw speed. The dip-coated lens dries for $30\\mathrm{min}$ at room temperature and then is cured at $90^{\\circ}\\mathrm{C}$ .for 2 hours. The resulting coated lens has a coating thickness of 15 about $8.6\\upmu\\mathrm{m}$ . The coated lens passes the adhesion test and the initial anti-fogging test. This polyurethane coated lens however fails the anti-fogging after soaking for 1 hour test because this coated lens fogs within the 8 seconds of exposing it to the $50^{\\circ}\\mathrm{C}$ water vapors. 20  \n\nIt will be understood that various changes may be made without departing from the scope of the invention, which is not to be considered limited to what is described in the description.  \n\nWhat is claimed is:  \n\n1.A coating composition that provides a transparent, abra  \nsion-resistant, water-washable anti-fog coating when applied   \nto a substrate and cured, comprising: (A) a first mixture comprising a first polyurethane and a first liquid phase selected from the group consisting of 30 water, an organic solvent, and combinations thereof, wherein the first polyurethane comprises the reaction products of: (i) a first polyol component and at least one additional polyol component different than the first polyol com- 35 ponent, wherein the first polyol component comprises a diol having polyethylene oxide side chain segments, (ii) a first polyisocyanate component comprising at least one polyisocyanate selected from the group consisting of diisocyanates, triisocyanates, derivatives of 40 diisocyanates and triisocyanates capable of forming polyurethane linkages, and combinations thereof, and (iii) a dihydroxy-carboxylic acid neutralized by a carboxylic-reactive amphoteric surfactant to form a salt of the amphoteric surfactant, wherein the first polyurethane includes hydrophilic side chain segments in an amount ranging from about $0.01\\%$ to about $20\\%$ by weight of the solids of the first polyurethane; or (B) a second mixture comprising a second polyurethane 50 and a second liquid phase selected from the group consisting of water, an organic solvent, and combinations thereof, wherein the second polyurethane comprises the reaction products of: (i) a second polyol component and atleast one additional 55 polyol component different than the second polyol component, wherein the second polyol component comprises at least one of: (a) a diol having main chain segments selected from the group consisting of polyethylene oxide, 60 polypropylene oxide, and combinations thereof, or (b) a triol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof, (ii) a second polyisocyanate component comprising at 65 least one partially blocked tri-functional polyisocyanate,  \n\n(iii) an isocyanate-reactive salt of a surfactant, and  \n\n(iv) an isocyanate-reactive cationic surfactant, wherein the second polyurethane includes hydrophilic main chain segments in an amount ranging from about $0.01\\%$ to about $20\\%$ by weight of the solids of the second polyurethane; or (C) a third mixture comprising a third polyurethane and a third liquid phase selected from the group consisting of water, an organic solvent, and combinations thereof, wherein the third polyurethane comprises the reaction products of: (i) a third polyol component and at least one additional polyol component different than the third polyol component, wherein the third polyol component comprises a diol having polyethylene oxide side chain segments and at least one of: (a) a diol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof, or (b) a triol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof, (ii) a third polyisocyanate component comprising:   \n25 (a) at least one polyisocyanate selected from the group consisting of diisocyanates, triisocyanates, derivatives of diisocyanates and triisocyanates capable of forming polyurethane linkages, and combinations thereof, and (b) at least one partially blocked tri-functional polyisocyanate, (iii) an isocyanate-reactive salt of a surfactant, and (iv) an isocyanate-reactive cationic surfactant, wherein the third polyurethane includes hydrophilic main chain segments, hydrophilic side chain segments,or combinations thereof in an amount ranging from about $0.01\\%$ to about $40\\%$ by weight of the solids of the third polyurethane. 2. The composition of claim 1, wherein the hydrophilic   \n40 side chain segments comprise polyethylene oxide. 3. The composition of claim 1, wherein the hydrophilic main chain segments are selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof.   \n45 4. The composition of claim 1, wherein the at least one additional polyol component comprises a diol having polyethylene oxide side chain segments; a diol having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof; a triol   \n50 having main chain segments selected from the group consisting of polyethylene oxide, polypropylene oxide, and combinations thereof; an alkyl diol; an alkyl triol; a polycarbonate diol; a polycarbonate triol; or combinations thereof. 5. The composition of claim 1, wherein the dihydroxy  \n55 carboxylic acid is selected from the group of compounds having the formula $\\mathrm{(OH)}_{2}\\mathrm{R}^{4}\\mathrm{(COOH)}$ ，wherein $\\mathrm{R}^{\\dot{4}}$ is an unbranched or branched alkyl group having from about 1 to about 12 carbon atoms. 6. The composition of claim 1, wherein the carboxylic  \n60 reactive amphoteric surfactant is selected from the group consisting of: (a) an amine_ oxide having the formula $\\mathrm{R}_{3}^{~5}\\mathrm{-}\\mathrm{N}^{+}\\mathrm{-}\\mathrm{O}^{-}$ wherein $\\mathrm{R}^{5}$ is selected from the group consisting of a hydrogen, an unbranched alkyl group having from about 8 to about 18 carbon atoms, and combinations thereof, and wherein at least one $\\mathrm{R}^{5}$ is an unbranched alkyl group having from about 8 to about 18 carbon atoms; and",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 53,
+        "chunk": "#  \n\n35 (b)an alkyl betaine having the formula $\\mathrm{R}^{6}{\\longrightarrow}\\mathrm{N}^{+}{\\longrightarrow}(\\mathrm{CH}_{3})_{2}$ $\\mathrm{-CH}_{2}\\mathrm{-}(\\mathrm{C=O})\\mathrm{-}\\mathrm{O^{-}}$ ，wherein $\\mathrm{R}^{6}$ is an unbranched alkyl group having from about 8 to about 18 carbon atoms. 7. The composition of claim 1, wherein the first polyiso- 5   \ncyanate component further comprises a blocked polyisocy  \nanate. 8. The composition of claim 1, wherein the second poly  \nisocyanate component further comprises a polyisocyanate   \nselected from the group consisting of diisocyanates, triisocy- 1(   \nanates, derivatives of diisocyanates and triisocyanates   \ncapable of forming polyurethane linkages, and combinations   \nthereof. 9. The composition of claim 1, wherein the at least one   \npartially blocked tri-functional polyisocyanate has 1 free iso- 1:   \ncyanate functional group and 2 blocked isocyanate functional   \ngroups. 10. The composition of claim 1, wherein the isocyanate  \nreactive salt of a surfactant comprises the reaction products of   \na neutralization reaction between an acid of an anionic sur- 2(   \nfactant and a base having an isocyanate-reactive functional   \ngroup. 11. The composition of claim 10, wherein the isocyanate  \nreactive salt of a surfactant comprises a salt of dimethylami  \nnomethylpropanol and dodecylbenzene sulfonic acid. 2 12. The composition of claim 1, wherein the isocyanate  \nreactive cationic surfactant comprises a quaternary ammo  \nnium surfactant having 2 hydrophilic isocyanate-reactive   \nfunctional groups and a hydrophobic hydrocarbon chain hav  \ning at least about 18 carbon atoms. 3 13. The composition of claim 12, wherein the 2 hydrophilic   \nisocyanate-reactive functional groups comprise hydroxy  \nethyl functional groups and the hydrophobic hydrocarbon   \nchain comprises stearamide or stearamidopropyl functional   \ngroups. 3 14. The composition of claim 12, wherein the isocyanate  \nreactive cationic surfactant comprises bis(hydroxyethyl) qua  \nternary ammonium surfactants having stearamide or steara  \nmidopropyl functional groups. 15. The composition of claim 1, wherein the organic sol- 4(   \nvent comprises a ketone, N-methyl pyrrolidone, acetonitrile,   \ndiacetone alcohol, an ester, a glycol ester, a glycol ether, a   \ntertiary alcohol, or combinations thereof. 16. The composition of claim 1, wherein the composition   \ncomprises an aqueous polyurethane dispersion, an organic 4:   \nsolvent polyurethane solution, or a mixture of an aqueous   \npolyurethane dispersion and an organic solvent polyurethane   \nsolution. 17. The composition of claim 1, wherein the first polyure  \nthane, the second polyurethane, or the third polyurethane 5(   \nfurther comprises the reaction products of a chain extender   \nselected from the group consisting of multi-functional   \namines, multi-functional polyols, urea, and combinations   \nthereof. 18. The composition of claim 1, wherein the first polyure- 5:  \n\nthane, the second polyurethane, or the third polyurethane comprises a prepolymer.  \n\n19. The composition of claim 1 comprising the first mixture, wherein the dihydroxy-carboxylic acid is selected from the group of compounds having the formula $\\mathrm{(OH)}_{2}\\mathrm{R}^{4}$ (COOH), wherein $\\mathrm{R}^{4}$ is an unbranched or branched alkyl group having from about 1 to about 12 carbon atoms; and wherein the carboxylic-reactive amphoteric surfactant is selected from the group consisting of an amine oxide and an alkyl betaine. 20.The composition of claim 1 comprising the second mixture, wherein the at least one partially blocked tri-functional polyisocyanate has 1 free isocyanate functional group and 2 blocked isocyanate functional groups; wherein the isocyanate-reactive salt of a surfactant comprises the reaction products of a neutralization reaction between an acid of an anionic surfactant and a base having an isocyanate-reactive functional group; and wherein the isocyanate-reactive cationic surfactant comprises a quaternary ammonium surfactant having 2 hydrophilic isocyanate-reactive functional groups and a hydrophobic hydrocarbon chain having at least about 18 carbon atoms. 21. The composition of claim 1 comprising the third mixture, wherein the at least one partially blocked tri-functional polyisocyanate has 1 free isocyanate functional group and 2 blocked isocyanate functional groups; wherein the isocyanate-reactive salt of a surfactant comprises the reaction products of a neutralization reaction between an acid of an anionic surfactant and a base having an isocyanate-reactive functional group; and wherein the isocyanate-reactive cationic surfactant comprises a quaternary ammonium surfactant having 2 hydrophilic isocyanate-reactive functional groups and a hydrophobic hydrocarbon chain having at least about 18 carbon atoms. 22. The composition of claim 1 further comprising a combination of the first mixture and the second mixture. 23.An article, comprising a substrate and a coating formed on at least one surface of the substrate by curing a coating composition prepared from the coating composition of claim 16. 24.The article ofclaim 23, wherein the substrate comprises a polycarbonate material, an acrylic material, a polyvinylchloride material, a polybisallyl carbonate material, a polyethylene terephthalate material, a polyethylene naphthenate material, a polyolefin material, a polyurethane material, a polythiourethane material, a fluorinated polymer material, metal, acrylic glass, or glass. 25.A process, comprising applying the coating composition ofclaim 1 to at least one surface of a substrate and curing the coating composition applied to the at least one surface of the substrate to form a transparent, abrasion-resistant, waterwashable anti-fog coating.",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/UV-curable anti-fog coatings.json b/task2/task2-chunks/UV-curable anti-fog coatings.json
new file mode 100644
index 0000000..53318ee
--- /dev/null
+++ b/task2/task2-chunks/UV-curable anti-fog coatings.json	
@@ -0,0 +1,47 @@
+[
+    {
+        "id": 1,
+        "chunk": "# UV-Curable Anti-Fog 医 Coatings  \n\nA t c ertain t emperature aand h um d ty, water vap or i n a ir c ondenses on s olid surfaces. Because water has much higher surface energy t han most solid surfaces, the c ondensed w ater u sually t akes t he form of s mall d roplets, which scatter light and cause haziness. Fogging is a severe problem for a lot of optical devices, such as lenses, m irrors, w indshields and visors et al. Basically, there are two ways to avoid hazy water condensation. One i s t o c ontrol t he t emperature a nd h umidity s o t hat water c ondensation c an n ot hap pen. F or exa mple, s ome devices use heating elements to keep the temperature high enough th at w ater c annot c ondense; s ome d evices a re purged by inert gases or dry air to remove moisture. These approaches are very effective, but consume energy and they are ex pensive. The ot her approach i s t o u se a nti-fog c oatings on t he optical devices. A nti-fog c oatings c an p revent hazy water condensation and maintain the optical clarity. Obviously, this is a better approach, because anti-fog coatings are cheaper and consume no energy to operate. Considering the anti-fog mechanism, it is possible to categorize anti-fog coatings into three types.  \n\nType I:  The coatings remove water condensation by absorbing liquid water into the coating. Type I c oatings can b e s aturated whe n moi sture lev el i s t oo h igh, a nd do not respond to water condensation quickly; therefore they are not very effective.  \n\nType I I: The c oatings lo wer t he s urface e nergy of water, a nd the condensed water evenly wets the surface. Usually, Type II anti-fog coatings carry extractable surfactants.1 W hen wa ter co ndenses o n t he coa ting surface, t he s urfactants di ssolve in to t he li quid w ater and br ing down its surface energy so that water w ill wet the s urface ev enly. T ype I I c oatings w ork e ffectively a s long a s e nough s urfactants c an b e ex tracted i nto w ater; however, surfactants can be washed away by water, and Type II anti-fog coatings will lose their anti-fog property gradually. I n ad dition, b ecause it t akes t ime fo r w ater t o dissolve surfactants, Type II coatings will not respond to water condensation very quickly. When suddenly exposed to high humidity, some Type II coatings can immediately get fogged and it will take some time for them to turn clear.  \n\nType I II: The se c oatings ha ve a s uper-hydrophilic surface. Water has a very low contact angle, less than $5^{\\circ}$ , on s uperhydrophilic s urfaces, a nd w ater c ondensed on a s uper-hydrophilic s urface w ill ev enly s pread ou t v ery quickly. No s urfactants ne ed t o b e ex tracted f rom t he super-hydro hilic coatings; t ey work instantly with little d lay ttime. Sup er-hydrophilic c oatings2 p erform b  tter than the other two types of anti-fog coatings.  \n\nIn this paper, we discuss UV-curable super-hydrophilic anti-fog c oatings. UV -curable an ti-fog c oatings3 c an b e cured i nstantaneously. They c onsume le ss e nergy t o produce and, more importantly, they can be produced in a roll-to-roll process at high speed.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Experimental  \n\nSilica na noparticles, a s a 1 $\\ensuremath{\\mathrm{0-15}}\\ensuremath{\\mathrm{n~m~p~}}$ article s ize, $3\\:0\\%$ dispersion in m ethanol, w ere u sed e ither dir ectly wi thout modification o r w ere m odified b y p olyethylene g lycolmodified silane and acrylate/methacrylate-modified silanes.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 3,
+        "chunk": "# Synthesis of Polyethylene Glycol-Modified Silane  \n\nMonomethyl ether polyethylene glycol (mPEG) $(\\mathrm{Mw}=1100)$ ) was dissolved in toluene and the mixture was dried. At room temperature a nd u nder n itrogen, a mola r e quivalent (with respect to the mPEG) of 3-isocyantopropyl trimethoxysilane was added drop wise to the reaction mixture. A few d rops of dibutyl tin dilaurate were added as a c atalyst. The r eaction mixture w as t hen s tirred c ontinuously fo r $24\\mathrm{h}$ at $5\\ 0^{\\mathrm{{o}}}\\mathrm{{C}}$ . The r eaction w as mon itored by i nfrared s pectroscopy; the is ocyanate s ignal is  a $\\mathrm{t}2271\\mathrm{cm}^{-1}$ . U pon c ompletion, approximately t wo t hirds of t he t oluene w as r emoved by rotary evap oration a nd t he m PEG t rimethoxysilane w as precipitated into hexane and washed several times. The resulting s olid w as d ried a nd cha racterized by 1 H N MR. Reaction yields of $>90\\%$ were obtained.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# Silica Nanoparticle Surface Modification  \n\nThe s urface of s ilica na noparticles w as f unctionalized with mPEG triethoxysilane and 3-(trimethoxysilyl)propyl  \n\n![](images/a75f137016b80648862c96978f55d98032c6486c422030e1048fe86982d85b5d.jpg)  \nFIGURE 1 | Polycarbonate sheet (left) and PET sheet (right) coated by a roll-to-roll process.  \n\nTABLE 1 | Modification of silica nanoparticles.   \n\n\n<html><body><table><tr><td rowspan=\"3\">Material</td><td colspan=\"2\">Modified Silicon Oxide Particle</td></tr><tr><td></td><td></td></tr><tr><td>A</td><td>B</td></tr><tr><td>Silicon oxide nanoparticles, 30% solid in methanol</td><td>29.0</td><td>28.8</td></tr><tr><td>3-(trimethoxysilyl)propyl acrylate</td><td>1.1</td><td></td></tr><tr><td>3-(trimethoxysilyl)propyl methacrylate</td><td></td><td>1.1</td></tr><tr><td>mPEG trimethoxysilane</td><td>2.1</td><td>3.0</td></tr><tr><td>Hydroquinone monoethyl ether</td><td>0.02</td><td>0.02</td></tr><tr><td>Methanol (solvent)</td><td>67.7</td><td>67.1</td></tr><tr><td>Total</td><td>100</td><td>100</td></tr></table></body></html>  \n\nTABLE 2 | Anti-fog coating formulation.   \n\n\n<html><body><table><tr><td rowspan=\"2\">Material</td><td colspan=\"4\">Formulation</td></tr><tr><td>C (%)</td><td>D (%)</td><td>E (%)</td><td>F (%)</td></tr><tr><td>Silicon oxide nanoparticle</td><td></td><td>20.4</td><td>-</td><td></td></tr><tr><td>Modified silicon oxide particle A</td><td>28.9</td><td>-</td><td>-</td><td>28.9</td></tr><tr><td>Modified silicon oxide particle B</td><td></td><td>-</td><td>29.7</td><td></td></tr><tr><td>PEG diacrylate</td><td>6.8</td><td>5.1</td><td></td><td>6.8</td></tr><tr><td>PEG dimethacrylate</td><td>-</td><td>-</td><td>7.0</td><td></td></tr><tr><td>Sulfo propyl acrylate potassium salt</td><td>0.3</td><td>0.2</td><td>-</td><td></td></tr><tr><td>Sulfo propyl methyacrylate potassium salt</td><td></td><td></td><td>0.3</td><td>-</td></tr><tr><td>Water</td><td>2.4</td><td>1.8</td><td>2.5</td><td>2.4</td></tr><tr><td>Irgacure184</td><td>0.4</td><td>0.3</td><td>0.3</td><td>0.4</td></tr><tr><td>Methanol (solvent)</td><td>61.3</td><td>72.2</td><td>60.4</td><td>61.6</td></tr><tr><td>Total</td><td>100</td><td>100</td><td>100</td><td>100</td></tr></table></body></html>  \n\nTABLE 3 | Rating of anti-fogging performance.   \n\n\n<html><body><table><tr><td>Antifogging Performance</td><td>Rating</td><td>Annotations</td></tr><tr><td>No</td><td>1</td><td>Zero visible, poor light transmission</td></tr><tr><td>No</td><td>2</td><td>Zero visible, poor light transmission</td></tr><tr><td>Poor</td><td>4</td><td>Poorvisible</td></tr><tr><td>Fair</td><td>6</td><td>Discontinuous film of water</td></tr><tr><td>Good</td><td>8</td><td>Discontinuous film of water, mostly transparent</td></tr><tr><td>Excellent</td><td>10</td><td>Completely transparent</td></tr></table></body></html>  \n\nTABLE 4 | Performance of the anti-fog coatings.   \n\n\n<html><body><table><tr><td rowspan=\"2\"></td><td colspan=\"2\">Anti-Fogging Rating</td></tr><tr><td>Before Water Wash</td><td>After Water Wash*</td></tr><tr><td>Formulation C</td><td>10</td><td>10</td></tr><tr><td>Formulation D</td><td>10</td><td>10</td></tr><tr><td>Formulation E</td><td>10</td><td>10</td></tr><tr><td>Formulation F</td><td>2</td><td>2</td></tr></table></body></html>\n\n\\* The coated samples were washed with water for 10 seconds.  \n\nTABLE 5 | Properties of anti-fog coatings produced by roll-to-roll process.  \n\n<html><body><table><tr><td>Properties</td><td>Value</td></tr><tr><td>Pencil hardness</td><td>H on PET, 2B on polycarbonate</td></tr><tr><td>Refractive index</td><td>1.48</td></tr><tr><td>Thickness</td><td>6 μm</td></tr><tr><td>Transmittance (%)</td><td>93.4</td></tr><tr><td>Clarity</td><td>99.8</td></tr><tr><td>Yellownessindex</td><td>No change from the uncoated substrate</td></tr><tr><td>Haze</td><td>0.27</td></tr><tr><td>Steelwoolabrasion*△Haze</td><td>1.87</td></tr></table></body></html>\n\n$\\ast_{250~9}$ load, #0000 steel wool, 10 double rub, and then measure haze value  \n\nacrylate or 3- (trimethoxysilyl)propyl methacrylate. Table 1 sho ws t he a mount of e ach c omponent u sed i n t he reaction. The m ixtures were stirred at r oom temperature overnight to finish the reaction.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# Coating Formulation  \n\nFormulations were prepared by mixing modified or unmodified s ilicon o xide na noparticles w ith r eactive diluents, polyethylene glycol diacrylate $\\mathrm{(Mw=575~g~moF^{1}}$ ), sulfopropyl ac rylate p otassium salt, a nd a phot oinitiator, 1-hydroxycyclohexyl b enzophenone. The s ulfopropyl acrylate potassium salt was added as a s olution in water. The exact weights used for coatings are shown in Table 2. All the liquid coatings have a solid content of about $12\\%$ .  \n\nCoatings were applied on PE T or p olycarbonate she ets using # 16 w ire w ound r od. The c oatings w ere d ried for ha lf a m inute, a nd t hen c ured u nder a $3\\ \\mathrm{~00~W~p~}$ er inch me rcury vap or la mp at a do se of 1 J/ $\\mathrm{cm}^{2}$ in  a nitrogen at mosphere. The t hicknesses of t he c ured coatings were ab out $5\\mathrm{m}$ icrometers. The c oated s amples were cha racterized by c ross-hatch ad hesion t est, p encil hardness, optical properties and steel wool scratch test.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# Results and Discussion  \n\nAll c ured c oatings ha ve $100\\%$ ad hesion on t reated PE T and polycarbonate substrate, $99\\%$ optical clarity and over $90\\%$ transmittance. The anti-fog properties of the coatings were t ested by hold ing a c oated substrate for 15 seconds above warm water at $50^{\\circ}\\mathrm{C}$ . The c oating p erformance i s rated to the degree of fogging/transparency. If the coating fogs c ompletely, ha ving n o t ransparency, it i s rat ed a s 1. I f t he c oating do es n ot fog at a ll, s taying c ompletely transparent, it is rated as 10. A complete description of the rating and degree of fogging is given in Table 3.  \n\nAnti-fog p erformance o f c oatings i s li sted in  T able 4. A ll t he c oatings w ith t he s ulfonate s alt ha ve p erfect anti-fog p roperties; t he c oating w ithout s ulfonate s alt has p oor an ti-fog p roperties. Typ ically, i onic gr oups are mo re h ydrophilic t han e thylene g lycol g roups, a nd that is  p robably th e r eason th at c oatings c ontaining sulfonate s alt h ave b etter p erformance in  t he f ogging test. B ecause a ll t he c omponents a re c rosslinked i nto a p olymer ne twork, a fter t he c oatings w ere w ashed by water t heir a nti-fog p erformance d id n ot cha nge. It a lso has n o e ffect on a nti-fog p erformance whe ther ac rylates or met hacrylates w ere u sed. H owever, met hyacrylates polymerize much slower than acrylates. When coating E i s cured i n a ir, t he c oating i s very t acky b ecause of t he oxygen inhibition. There is no obvious difference between coating C and coating E, when they are cured in nitrogen.  \n\nThe mo dification of s ilica na noparticles ha s n o e ffect on a nti-fog p erformance of t he c oatings. B ecause t he modified s ilica n anoparticles ar e c ovalently link ed in to the p olymer ne twork, t he mo dified s ilica na noparticles should g ive t he c oating b etter s cratch r esistance. Si nce silica nanoparticles without modification can already give good mechanical properties, surface modification of silica nanoparticles is not always necessary.  \n\nThe c oating w ith n on-modified s ilica p articles w as applied by a roller coater on flexible PET and polycarbonate sheet. The c oating w as ap plied a nd c ured c ontinuously at $5\\mathrm{m}$ /min i n a r oll-to-roll p rocess. A s sho wn i n T able 5 a nd Figure 1 , t he c oated t ransparent she ets ha ve g ood op tical a nd mechanical properties and uniform thickness.  \n\n![](images/8fac616f9d7f6703a016901fe3f26b668e353f1e4df67c862aedab6e9e6a73f5.jpg)  \n\nAnti-fog coatings were also tested at both high and low temperatures, a nd t hey w orked v ery w ell b etween - $20~^{\\mathrm{o}}\\mathrm{C}$ and $90^{\\mathrm{{o}}}\\mathrm{{c}}$ . A s sho wn i n F igure 2 , a p iece of $\\mathrm{\\Deltap}$ artially c oated polycarbonate plat e w as plac ed on a c up of $90^{\\mathrm{{o}}}\\mathrm{{C}}$ c offee. The plate w as i nitially at r oom t emperature. Whe n it w as ex posed to the moisture from $90~^{\\mathrm{~o~c~}}$ coffee, the uncoated area was immediately fogged, while the coated area always stayed clear. In t he lo w-temperature t est, t he c oated s amples w ere c ooled down t o - $20^{\\mathrm{o}}\\mathrm{C}$ , a nd t hen w ere ex posed t o $60\\%$ h umidity room temperature air. The coated area stayed clear, while the uncoated area was quickly fogged.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# Conclusion  \n\nUV-curable anti-fog coatings were developed. The coatings comprise i norganic na noparticles a nd U V-curable h ydrophilic materials. The c oatings c an p revent fogg ing at t emperatures between $-20{}^{\\mathrm{o}}\\mathrm{C}$ a nd $90^{\\mathrm{{o}}}\\mathrm{{c}}$ . The c oatings sho w exc ellent op tical clarity, good hardness and scratch resistance. \u0002",
+        "category": " Conclusions"
+    },
+    {
+        "id": 8,
+        "chunk": "# References  \n\n1 Radisch, Helmer; Scholz, Werner. US Patent, 4,609,688. 2 Cebeci, F .Ç.; W u, Z .; Z hai, L .; C ohen, R .E.; R ubner, M .F. Langmuir 2006, 22, 2856-2862. 3 Meijers, Guido, Thies, Jens Christoph; Nijenhuis, Atze Jan. International Patent Application, 2009, WO 2009/118415.  \n\nThis p aper w as p resented a t t he R adTech 20 10 T echnology E xpo a nd Co nference, Baltimore, MD, www.radtech.org.  \n\n![](images/6b857a994871e1bcc4cddea15f68fc370e20ab7cba0307c59ff5a0a557940261.jpg)",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# Elcometer 456 Coating Thickness Gauge. One gauge–A world full of applications.  \n\nThe key to the superiority of the 456 is its measurement system featuring a range of interchangeable probes  \n\nAll Ferrous models will accept ANY Ferrous 456 probe   \nAll Non-Ferrous models will accept ANY Non-Ferrous 456 probe   \nAll Dual FNF models will accept ANY 456 probe High speed accurate readings Three memory options–Basic, Standard,Top Easy to use menu driven display-available in 22 languages Standard and pre-defined calibration options   \nIntegral and separate probe options  \n\nUS & Canada 800.521.0635 $\\cdot$ www.elcometer.com  \n\nCopyright of Paint & Coatings Industry is the property of BNP Media and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use.",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# A review on protective polymeric coatings for marine applications  \n\nShatakshi Verma $\\textcircled{1}$ , Smita Mohanty, S. K. Nayak $\\circleddash$ American Coatings Association 2019  \n\nAbstract The main objective of this review is to discuss the recent research on polymer-based surface coatings contributing to the protection against marine biofouling based on the knowledge available in literature, supplemented by means of figures, mechanism illustrations, mathematical models, and equations. A need for studies on the mathematical behavior of such coatings is emphasized, composed of quantitative evaluation of foul-release performance of coatings using mathematical equations of the concerned parameters. Apart from the synthesis of protective polymeric coatings, understanding the relationship between characteristics of coating materials and accompanying foulrelease and antifouling mechanism is important. In this regard, efforts have been made to equally evaluate, simulate, and measure the appropriate performance of the coatings. By examining the physicochemical and mechanical properties of the polymers, adhesion behavior has been found to be one of the prerequisites for the success of polymeric coatings for marine applications. The potential development of a broad spectrum of methods used to evaluate the foul-release performance of polymeric coatings depending on adhesion behavior of fouling organisms with the coatings has been discussed. From the analysis of the factors affecting degradation of coatings, environmental interference is declared a key factor for complete degradation of polymeric coatings. This review opens up new research directions to improve the adhesion performance of polymeric coatings for ship hulls designed with tunable viscoelasticity by the incorporation of elastomeric polymers (like polydimethylsiloxane) into stiff polymers (like epoxy resins) with and without the utilization of additives, modifiers, and nano-fillers. In addition, it provides methods to improve the foul-release performance of such coatings that work on adhesion behavior of biofouling species attached to the coating surface.",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# Graphical abstract  \n\n![](images/7494b8dd659e0c7c8fff507d02cb4278732ec2691f79b76121fe834f13ba325a.jpg)  \n\nKeywords Polymeric coatings, Foul-release, Adhesion strength, Epoxy–PDMS (polydimethylsiloxane) hybrids",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# Introduction  \n\nMarine biofouling is the undesirable adhesion and settlement of various marine species (flora and fauna) classified in two broad categories: microorganisms (bacteria, algae, diatoms, sponges) and macroorganisms (mussels, balanus, barnacles, hydroids, etc.).1–3 The adverse effects of marine biofouling on the performance of marine vessels include deterioration of the vessel’s surface, increase in weight of the vessel, reduction in speed, increased fuel consumption, increase in the emission of $\\mathrm{SO}_{x}$ , $\\mathrm{NO}_{x}$ , $\\mathrm{CO}_{2}$ ), causing a threat to the marine environment, leading to the worldwide problem related to loss of billions of dollars per year on fuel and maintenance.2,4 Polymeric materials play a vital role in manufacturing of surface coatings, which endeavor to protect and preserve various substrates from corrosion, wear, or any sort of chemical and biological invasion.5  \n\nPolymers entered the field of advanced application, during the last 15 years, noticing an abrupt increase in their demand in the field of research and development contributing in several ways to the betterment of mankind. The results of a survey on scientific production from the years 2000 to 2016 revealed that half of the global scientific production deals with polymers and polymer modifications.6 Most of the protective coatings contain several types of long-chain polymers. Altering the nature of polymers, under the influence of inorganic and/or organic precursors, they are often processed from multicomponent solutions, in which macromolecular and solvent species interact in complicated ways to influence material structures and functions to bring about new technologies for the coating industry.7,8 Surface coating is a simple and efficient method for the protection of metals by outsourcing polymeric materials, normally to serve the following purpose—to protect the surface, or to control friction and wear, or to alter physical properties, by modifying the reactivity of polymers by adding one or more functionalities to them.9 Coatings are indispensable to the industrial sector of every nation’s economy. The amelioration in numerous advanced coating technologies can be done by the combination of advantageous bulk properties of polymeric materials with surface-selective chemical conversions or surface modifications.5  \n\nThe prerequisite for designing multifunctional polymeric coatings is to manufacture a material with conflicting properties like flexibility, hardness, ease of handling, thermal stability, low surface energy, corrosion, abrasion, chemical, and foul resistance along with good adhesion to the substrate.10 The primary concern for the success of polymeric coatings is its appropriate and sufficient curing behavior resulting in threedimensional crosslinked networks. In this regard, Pathania et al.11 studied the polymer coatings with respect to their crosslinking phenomenon, along with the various parameters that control crosslinking in polymeric coatings, like diffusion studies. Polymer coatings can be synthesized by various methods and the solvent plays a crucial role, due to the presence of variety of polymers available to mankind from rubbery to glassy polymers.11  \n\nThe synergistic effect of polymeric coatings opens a new arena of research in various directions, likewise, the combination of superhydrophobic and biomimetic polymeric materials results in a large number of potential applications. Polymer coatings incorporated with foreign materials like superhydrophobic particles or nanofillers serve as a boon for the coating industry.1 Guangzhao et al.13 studied the self-renewing ability of certain polymeric resins like rosin, acrylic resin, and chlorinated rubber, giving rise to the selfsmoothening surface of the protective coating. The polymer coatings developed were able to form a selfpolishing surface, possessing antifouling capability in both static as well as dynamic conditions.13 Wooley et al.14 studied another excellent class of polymers for the formulation of robust, sustainable polymer coatings with long-term retention in properties. To enhance the general coating properties like flexibility, hardness, and adhesion, liquid crystalline polymers were employed for their excellent environmental, chemical, and weather resistance, wide thermal stability range, and fracture toughness. Block copolymers have attracted many researchers since the development of the first living polymer which was synthesized 50 years ago.14 The surface tension properties of polymer surfaces were greatly exploited for the design of hydrophobic segments by the past researchers as stated by Wynne et al.15 The increasing capability of polymers is being continuously tailored to fulfill the specific needs of the society, by chemically modifying their surfaces and/or bulk properties via wet chemistry or by following the route of physical or biological modifications as described in the literature.6 In a similar context, Wei Huang et al.16 described a means of modifying solid polymers at their surface for partial fulfillment of potential applications that was proposed in their work, which intends to incorporate a few surface-active additives at the time of polymer fabrication.16 A variety of polymers like surface-active, zwitterionic, polysaccharides, and hydrophilic polymers (such as polyethylene glycol), have been used to synthesize functional polymer coatings and brushes, polycationic, and fouling-release coatings for marine applications.1 Garcia et al.18 extensively reviewed research contributing to the utilization of polysiloxanes, acrylic and methacrylic polymers, hyperbranched and dendritic polymers, as potential and safe precursors for the synthesis of environmentally benign marine coatings. Du et al.19 in their study on extensively used polymeric materials to design and formulate antifouling surfaces and coatings against protein and bacterial adsorption reported about hydrophilic, hydrophobic, zwitterionic, polysaccharides and other potential polymers with respective mechanism of antifouling action. 19–21 The synergistic effect of amphiphilic polymer coatings employing liquid crystalline polymers gives rise to superior coating technologies, stable in environmentally challenging conditions, resulting in dynamic and robust crosslinked polymer coatings.22 Ferrari and Benedetti23 thoroughly studied the role of self-healing polymers for the development of surface-finishing superhydrophobic surfaces. Thus, polymeric coatings serve as a type of green technology and thereby find potential applications in the fields of fouling and corrosion prevention.23  \n\nAccording to the American Coatings Association (ACA), out of several coatings (Fig. 1),24 marine coatings have been explored extensively as highperformance coatings, employing state-of-the-art technologies. These coatings have been based on advanced polymer technologies, manufacturing effective products brought to the market on a regular basis by leading coating industries.25 The major class of foulingrelease coatings is a group of synthetic polymers generally called low surface energy polymers (like siloxane and fluoropolymers).26 Several excellent reviews $^{1-4,27-33}$ have covered existing trends on marine protective coatings based on polymeric materials being the potential monomers of coatings either employed in a matrix or reinforcement form. In both forms, polymers fill the implementation gap of the conventional TBT or metal-based coatings, thereby being nonhazardous for marine environments.  \n\nMost studies dealing with the development of antifouling and foul-release coatings lack studies on innovation in performance evaluation of such systems through the development of self-sufficient laboratory setups to measure the antifouling and foul-release performance of the formulated paints in terms of toxicity levels, adhesion strength, drag-reduction efficiency, bacterial adhesion, etc. Therefore, in this regard to bridge the gap between the prevailing systems and the future developments in the field of marine coatings, this review lays emphasis on the performance evaluation of such coatings. More emphasis on the determination of variables like attachment strength, rate of adhesion, hydrolytic degradation of polymer, velocity gradient determination, antidrag performance, growth of algal bloom, removal force, and swelling ratio has been given. The methodology for evaluation of mechanical strength using shear lag model, measurement of vertical force from the buoyancy force, dispersion studies, and encapsulation time of fillers using Taylor’s model in the case of filled polymer systems, role of binders and antioxidants in the design of antifouling and foul-release polymeric coatings have been discussed. This article reviews the recent progress on protective coatings for marine applications and suggests the quantitative approach to judge the antifouling as well as foul-release efficacy of the designed surface coatings.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# Polymeric coatings for marine applications  \n\nPolymeric surface coatings can bestow a wide range of functionalities, and depending upon the functionality, they also make a way for suitable applications. Suitable here denotes the ability of the polymeric coatings to tune them according to the desired profile of application. Apart from this, the coating must fulfill several requirements like adhesion to the substrate, desired mechanical and functional properties, viz. scratch/wear resistance, hydrophobicity/hydrophilicity, antibacterial, antifouling, antistatic, chemical resistance, etc.6 Another important condition for suitability is temperature of coating application, without damaging the substrate onto which coating is applied. Pertaining to their extended usages and increased applications in marine paint industry, these have been grouped into three broad categories: superhydrophobic, antifouling, and foul-release coatings, which have been used for centuries and engineered recently for specialized protective applications.34  \n\n![](images/641ffcc2bb279dffbd33b3506b74ee335ba10857ea04f15990077fbc56167cb2.jpg)  \nFig. 1: The types of coatings as per ACA and US Census Bureau Current Industrial Report MA 325F",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# Superhydrophobic coatings  \n\nA drop of water placed on a surface of the polymer is good enough to determine wettability of the surface and can be distinguished as hydrophilic on spreading, whereas hydrophobic on beading or rolling off (Fig. 2). Moreover, the receding or advancing contact angle values can be obtained by simply tilting the polymer surface on which the drop rests, not more than 10\u0003.15,35 Superhydrophobicity in nature defined in the terms of Fihri et al.36 is a physicochemical phenomenon inherited by low surface energy, rendering the surface extremely difficult to wet. The theory of superhydrophobicity is well expressed in terms of the most traditional and essential equation in the science of wetting. The Young’s equation (1) explains the inverse of water repellency, i.e., wettability in terms of contact angle (h)36,37  \n\n$$\n\\cos\\theta=\\frac{\\gamma_{\\mathrm{sv}}-\\gamma_{\\mathrm{sl}}}{\\gamma_{\\mathrm{lv}}}\n$$  \n\nwhere $\\gamma_{\\mathrm{sv}},~\\gamma_{\\mathrm{sl}}$ , and $\\gamma_{\\mathrm{lv}}$ refer to the interfacial surface tension values of solid, liquid and gas, respectively. The Young’s equation is suitable for predicting the contact angle values of flat, perfectly smooth surfaces with the homogeneous interface, defined by three-phase contact line at water, air, and polymer surface,15,36,37 whereas for the wetting of heterogeneous interface, more complicated route needs to be followed as developed by Wenzel and Cassie–Baxter.36 For rough and chemically heterogeneous surface36 the contact angle can be determined by the Wenzel model which assumed that the water droplets penetrate inside the roughness troughs and tend to completely wet the surface35 with negligible effect of gravity. The contact angle is given by the Wenzel’s equation37  \n\n$$\n\\cos\\theta=R_{\\mathrm{f}}\\cos\\theta_{\\mathrm{L}}\n$$  \n\nwhere $R_{\\mathrm{f}}$ denotes the ratio of the actual surface area to its flat projected area, and $\\theta_{\\mathrm{{L}}}$ denotes the contact angle of the liquid on the surface.  \n\nFor rough and heterogeneous surfaces composed of two fractions or more, the value of contact angle is given by the Cassie–Baxter model35 assuming the droplet sitting on top of asperities creating air pockets trapped among themselves generating a composite solid–air–liquid interface as depicted in Fig. 3. The wetting behavior of this regime is well suited for liquidrepellent surfaces, and the value of contact angle is determined by the following equation37  \n\n$$\n\\mathbf{cos}\\theta=f_{1}\\cos\\theta_{1}+f_{2}\\cos\\theta_{2}\n$$  \n\nwhere $f_{1}$ and $f_{2}$ are the fractional area with respective contact angle $\\theta_{1}$ and $\\theta_{2}$ . Similarly, for composite interface the contact angle can be calculated using Cassie–Baxter equation comprised of solid–liquid fraction and liquid–air fraction where $f_{1}$ is replaced by $f_{\\mathrm{SL}}$ and $\\theta$ by $\\theta_{\\mathrm{{L}}}$ for solid–liquid fraction and $f_{2}$ by ${f_{\\mathrm{LA}}}^{37}$  \n\n![](images/ff66910c0787dad24943ca1360964fbe0ec480abe546016437543f7882b3d3b5.jpg)  \nFig. 2: Schematic representation of the various types of wetting regimes between substrate and water droplet  \n\n![](images/c90ebfe48d06389edd4851c327615bc4cd8763b5901c28b183e685d4e7148f23.jpg)  \nFig. 3: Progress of wetting behavior for different wetting regimes of a droplet on a flat surface (a) Young’s model, (b) Wenzel model, (c) Cassie–Baxter model with different surface roughness.36 Copyright 2017, reproduced with kind permission from Elsevier  \n\n$$\n\\cos\\theta=R_{\\mathrm{f}}\\cos\\theta_{\\mathrm{L}}-f_{\\mathrm{LA}}(R_{\\mathrm{f}}\\cos\\theta_{\\mathrm{L}}+1).\n$$  \n\nStatic contact angle measurement is not sufficient for the determination of unexpected wetting behavior of the polymeric coatings. In this regard, Wynne et al.15 came forward with an approach on Wilhelmy balance method for dynamic contact angle (DCA) evaluation, which helps to eliminate the ‘‘contamination gap’’ for marine waters by examining the ‘‘leaching’’ of contaminants in water. The leachates tend to alter the contact angle values by reducing the surface tension of water. This method reports the change in the values of contact angle according to the depth and zones of immersion and emersion of hydrophobic (Fig. 4a) and hydrophilic coatings (Fig. 4b).15  \n\n![](images/347763b64914e08caa90eee331b2beafd12dd22fdcfa7c8df38e6375f26e43f8.jpg)  \nFig. 4: Pictorial representation of sequence of immersion and emersion phenomenon observed in (a) hydrophobic and (b) hydrophilic coatings. Where $I_{1},I_{2},I_{3}$ denote the progressive stages of immersion in water contact and $\\pmb{\\cal E}$ denotes the emersion. $)_{A1},\\theta_{A2},\\theta_{A3}$ denotes the advancing contact angles at different stages of immersion, whereas $\\theta_{\\mathsf{R}}$ denotes the receding contact angle  \n\nFurther, for recording the dynamics of contact angle measurement, efforts were made by Nair et al.15 to calculate the dynamic contact angle $\\mathbf{\\dot{\\rho}}(\\theta)$ , employing an experimental setup with a glass surface coverslip coated with the polymeric coating; hung from a sensitive electrobalance with vertical force, $F_{\\ast}$ given by the following equation  \n\n$$\nF=P\\gamma L\\cos{\\theta}-F_{\\mathrm{b}}\n$$  \n\nwhere $P$ denotes the perimeter of coated slides and $F_{\\mathrm{b}}$ denotes the buoyancy force proportional to the depth of immersion.15  \n\nIn context of fabrication of superhydrophobic coatings, a tremendous increase in superhydrophobicity was achieved in a study by Huang et al.,38 reporting WCA greater than $170^{\\circ}$ by dip coating nano- $\\mathrm{TiO}_{2}$ (P25) on hastealloy substrate, the process shown in (Fig. 5). Mostly, the film was suitable for marine applications since it showed superhydrophobicity even after being corroded with strong acids.38  \n\nMartin and Bhushan35 described a means of modifying the surface of polydimethylsiloxane from hydrophobic to superhydrophobic by coating it with $\\mathrm{SiO}_{2}$ nanoparticles incorporated in methylphenyl silicone resin binder. The results found that the novel formulation possesses self-cleaning, antifouling, lowdrag, and antismudge properties apart from superhydrophobicity.35 The induction of superhydrophobicity in any polymeric surface coating is followed by added advantages of anticorrosiveness, abrasion resistance, cohesion strength, and many more. In this regard, improvement of other coating properties brought at the advent of superhydrophobicity has been discussed in the findings of Fihri et al.36 on polymer-based superhydrophobic coatings on steel substrates, listed in Table 1.  \n\n![](images/a3e59a9df5752fe32676854dbfd57055969291d60cf65c5befe4d57acdbdd808.jpg)  \nFig. 5: $\\pmb{\\Tilde{\\Pi}}\\pmb{0_{2}}$ suspension containing $\\pmb{\\Tilde{\\mathbf{liO}}_{2}}$ nanoparticles as precursor, leading to a hierarchical structure with high water contact angle of $173.7^{\\circ}$ .38 Copyright 2012, reproduced with kind permission from Elsevier  \n\nTable 1: Improvement in the hydrophobicity of polymer coatings on value addition of nanoparticles36   \n\n\n<html><body><table><tr><td rowspan=\"2\">S. no.</td><td rowspan=\"2\"> Polymer matrix</td><td rowspan=\"2\"> Nanoparticles embedded</td><td rowspan=\"2\">%Wt loading/ratio</td><td colspan=\"2\">Contact angle (°)</td><td rowspan=\"2\"> Properties improved</td><td rowspan=\"2\">Referen nos.</td></tr><tr><td>Pristine</td><td>Blend</td></tr><tr><td>1.</td><td>Polyurethane</td><td>Molybdenum disulfide</td><td>20-55.6</td><td>87</td><td>157</td><td>Surface roughness, abrasion resistance, superhydrophobicity</td><td>39</td></tr><tr><td>2.</td><td>Fluorinated polysiloxane</td><td>Steric acid-modified ZnO</td><td>13:7</td><td>一</td><td>166</td><td>Excellent durability, corrosion resistance</td><td>40</td></tr><tr><td>3.</td><td>Teflon tailings</td><td>Tetrafluoroethylene and hexafluoropropylene</td><td></td><td>一</td><td>> 165</td><td>Uniformity,superhydrophobicity</td><td>41</td></tr><tr><td>4.</td><td>Fluoride latex</td><td>Phosphating material</td><td></td><td>155</td><td>168</td><td>Corrosion resistance, good stability in salt spray environment</td><td>42</td></tr><tr><td>5.</td><td>PTFE</td><td>Polyphenylene sulfide</td><td>40 vol%</td><td>一</td><td>165</td><td>Good cohesion strength, high and low temp. resistance</td><td>43</td></tr><tr><td>6.</td><td>Epoxy resin</td><td>Fatty acids and epoxidized oleic acid</td><td>5</td><td></td><td>160.5</td><td>Corrosion barrier properties</td><td>44</td></tr></table></body></html>  \n\nWang et al.45 asserted an enormous increase in superhydrophobicity of the coatings by employing very rarely used nanofiller, electrochemically exfoliated graphite (EEG) incorporated into polydimethylsiloxane matrix. The prepared surfaces obeyed the Cassie– Baxter model with WCA value of $160^{\\circ}$ indicating water droplets in a suspended state instead of penetrating the surface and exhibited excellent self-cleaning properties, able to withstand water and sand-impact tests. The contact angle measurements captured spherical droplets, whereas the SEM images revealed a nanoflower structure on the surface of Al alloy and steel substrates, as demonstrated in Fig. 6.45  \n\nWang et al.46 discussed the synthesis of PDMS–ZnO nanocomposite coating having surface microstructures able to restore themselves on account of strong mechanical stability along with robust abrasion resistance toward any surface degradation. The coating qualified as a potential candidate to be used in protective applications such as anti-icing, superhydrophobic, as well as nonfouling (Fig. 7).46  \n\nIn continuing theme of polymeric superhydrophobic marine coating research, Mo et al.47 reported a facile approach for fabricating protective coating from methylhydrosilicone oil and stearic acid-modified $\\mathrm{TiO}_{2}$ nanoparticles with the highest water contact value of $1\\dot{5}1.5^{\\circ}$ .47 Cong et al.48 formulated PDMSbased superhydrophobic coatings and successfully compared the effect of concentration of $\\mathrm{TiO}_{2}$ and $\\mathrm{SiO}_{2}^{-}$ nanoparticle incorporated into PDMS matrix on the repellent properties. The contact angle values were reported as follows—(a) $\\mathrm{PDMS}/\\mathrm{TiO}_{2}$ -NPs (30 $w t\\%$ )— $154.69^{\\circ}$ (b) $\\mathrm{PDMS}/\\mathrm{SiO}_{2^{-}}$ NPs (40 $\\mathrm{wt\\%}$ )— $152.46^{\\circ}$ . The TEM results supported the microroughness of fractured surfaces revealing that the $\\mathrm{TiO}_{2}$ nanoparticles showed more dispersion. Moreover, superhydrophobic property was imparted to the coatings by low surface energy of PDMS moieties and microscale roughness of $\\mathrm{TiO}_{2}$ nanoparticle clusters along with the photocatalytic property stable up to 6 months.48 Similar findings were reported by Bokobza and Diop49 by generating titania nanoparticles synthetically in post-crosslinked networks by using a novel protocol. The TEM images revealed two-phase structure, and the fillers were dispersed homogeneously in the PDMS matrix. There exists a strong interface between the polymer and the filler leading to excellent mechanical properties.49  \n\nSurface tension plays a crucial role, in altering the hydrophobic nature of the surface coatings when any liquid phase comes in contact with the solid-coated substrate. In this regard, the Owens–Wendt–Kaeble approach was employed by Martinelli et al.50 for surface tension calculation of the coatings, with the help of predetermined contact angle (h) values. The geometric mean of the interfacial surface tension c) is given by the following equations50  \n\n![](images/1f6642da97bc95dc469b02c4534c5286830b5126f670b3a1a0eaf10e54f68125.jpg)  \nFig. 6: (a) Appearance of water droplets on superhydrophobic surface (b) contact angle measurement reporting $160^{\\circ}$ (c) Contact angle measurement at tilt angle of ${\\mathfrak{s o}}$ (d), (e) SEM images of superhydrophobic composite coating representing nanoflower structures (f) Colorful magnification.45 Copyright 2016, reproduced with kind permission from Elsevier  \n\n![](images/9db5dcd9d2f3bc1d554b4ffa0aadacb2af50ac8c510323e4b447c4f521c08077.jpg)  \nFig. 7: The water contact angle values recorded for (a) uncoated substrate (b) coated substrate (left) and the surface regeneration mechanism of PDMS-ZnO superhydrophobic coating (right).46 Copyright 2015, reproduced with kind permission from Springer  \n\n$$\n\\begin{array}{l}{\\gamma=\\gamma^{\\mathrm{d}}+\\gamma^{\\mathrm{p}}}\\\\ {\\gamma_{12}=\\gamma_{1}+\\gamma_{2}-2\\big(\\gamma_{1}^{\\mathrm{d}}\\gamma_{2}^{\\mathrm{d}}\\big)^{0.5}}\\end{array}\n$$  \n\nCombining equation (7) with Young’s equation (1), equation (7) can be rewritten as follows:  \n\n$$\n\\gamma_{\\mathrm{L}}(1+\\cos\\theta)=2\\Big[\\big(\\gamma_{\\mathrm{S}}^{\\mathrm{d}}\\gamma_{\\mathrm{L}}^{\\mathrm{d}}\\big)^{0.5}+\\big(\\gamma_{\\mathrm{S}}^{\\mathrm{p}}\\gamma_{\\mathrm{L}}^{\\mathrm{p}}\\big)^{0.5}\\Big]\n$$  \n\nwhere $\\gamma^{\\mathrm{d}}$ denotes the nonpolar component of interfacial surface tension, i.e., dispersive and hydrogen bonding component, and $\\gamma^{\\mathrm{p}}$ denotes the polar component representing dipole–dipole interactions. Equation (8) consists of two unknowns, to be solved via simultaneous equations, provided that the value of contact angle (h) has been determined by sessile drop technique.50–52  \n\n![](images/703c5790dd49223166bb185e06c548d63c720b9429f78dd26609f103ed77796f.jpg)  \nFig. 8: Schematic illustration of Marine biofouling—its reasons and consequences. (a) Image of deteriorated coating system (b) Coating delamination because of Biocorrosion-Exposure to atmosphere (c) Deposited hard fouling over ship hull-Exposure to seawater  \n\nThe roll-off angle is defined as the tilting angle at which the droplet of any solvent (water, methylene iodide, etc.) used in sessile drop technique begins to roll-off on a surface. The expression for determining the roll-off or sliding angle was given by Brockway et al.53 as follows:  \n\n$$\nF_{\\mathrm{ad}}=2R\\gamma(1+\\cos\\theta)\\sqrt{\\varnothing_{\\mathrm{T}}}=\\rho V g\\sin\\alpha\n$$  \n\nwhere $F_{\\mathrm{ad}}$ is the lateral adhesive force between the droplet and the solid surface, $R$ is the mean radius of the contact line, $\\gamma$ is the surface tension of water, $\\sqrt{\\varnothing_{\\mathrm{T}}}$ is the wetting solid fraction, $\\rho$ is the density of water, $V$ is the volume of the droplet, $g$ is the acceleration due to gravity, and a is the roll-off angle.53,54  \n\nA simpler approach for the measurement of surface energy was reported by Zhou et al.55 by utilizing the equation of state method, as follows55  \n\n$$\n\\sigma_{\\mathrm{s}}=\\gamma_{\\mathrm{sl}}-\\sigma_{\\mathrm{l}}\\cdot\\cos\\theta\n$$  \n\n$$\n\\gamma_{\\mathrm{sl}}=\\sigma_{\\mathrm{l}}+\\sigma_{\\mathrm{s}}-2\\sqrt{\\sigma_{\\mathrm{l}}\\cdot\\sigma_{\\mathrm{s}}}\\cdot\\mathrm{e}^{-\\beta\\left(\\sigma_{\\mathrm{l}}-\\sigma_{\\mathrm{s}}\\right)^{2}}\n$$  \n\n$$\n\\cos\\theta=-1+2\\sqrt{\\frac{\\sigma_{\\mathrm{s}}}{\\sigma_{\\mathrm{l}}}}\\cdot\\mathrm{e}^{-\\beta(\\sigma_{\\mathrm{l}}-\\sigma_{\\mathrm{s}})^{2}}\n$$  \n\nwhere $\\sigma_{\\mathrm{{s}}}$ denotes the surface energy of the solid, $\\sigma_{\\mathrm{l}}$ denotes the surface energy of the liquid, $\\gamma_{\\mathrm{sl}}$ gives the interfacial tension of the solid/liquid phase and $\\theta$ is the contact angle.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# Antifouling coatings  \n\nThe process of bacterial colonization is an irreversible adhesion consisting of many stages of recruitment of microorganisms on the surface of marine structures, whether protected or unprotected, making it impossible to reduce biofouling once it has been formed over the solid surface (Fig. 8). Antifouling (AF) coatings are essential for preventing the growth of fouling on immersed structures due to the environmental and economical benefits. Thus, there is an urgent need of the hour to develop effective coatings to protect the surface of underwater objects from adhesion of various microorganisms.19,56 As per the norms imposed by IMO, new antifouling systems qualifying the implementation gap for AF polymer coating have been designed as viable alternatives to banned TBT paints and other tin-free biocide-based replacements. The green strategies for AF coatings were discussed as a part of two approaches (1) detachment of biofoulants and (2) preventing biofoulants attachment in an extensive review using triangular approach on amphiphilicity, superhydrophobicity and topographic nature of marine coatings by Ayda et al.33  \n\n![](images/92471e3ffaa3530fe1fb3efe344a7f073ff0a3c13cd4444e3e12ad0543d37700.jpg)  \nFig. 9: Various approaches to design antifouling surfaces.30 Reproduced with kind permission from JOHN WILEY AND SONS LICENSE, 2010  \n\nThe various approaches used to classify antifouling coatings are represented in Fig. 9. These approaches are based on the type of biofouling species attached and the concurrent type of polymer employed for the synthesis of such coatings to impart resistance against the attachment of a particular biofoulant.30  \n\nAF coatings are the paints applied on the solid hull surface to prevent it from unwanted attachment of microorganism through biocide release either from porous films or from ablative paints that continuously ablate biocides in water with time by dissolving themselves into marine water.1 According to Bressy et al.,4 AF coatings can be categorized into two types: chemically active coatings (generally toxic) and nontoxic coatings. The chemically active coatings are further divided into biocide-based and enzyme-based coatings, both functioning on dissolution mechanism. This explains the intensive search for new effective biocide-based polymer composites that can be as effective as those containing tin and copper.4 A concise review on the fundamental structure–property relationship and mechanism of antifouling polymers with their capability of being a fascinating class is presented with a particular focus on recent developments by Zhang and Chiao.31",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# Progress in antifouling technology  \n\nThe progress made in the interdisciplinary study on fabrication of robust AF surfaces may bring new ideas to the current research on multidefense AF coatings for marine applications. The AF performance of the fabricated coating surfaces depends upon the following three factors33  \n\n1. The length scale of coating roughness, ascribed to the topography,   \n2. The percentage of air incursions entrapped at the interface as per the Cassie–Baxter model,   \n3. The capability of the coating to hold and to stick to the interface.  \n\nHydrophilic polymers like glycocalyx-mimetic peptoids have been used as efficient antifouling materials due to the formation of a strong hydration layer at polymer–water interface providing higher interfacial strength. Subsequently, this prevents bacterial adhesion, recruitment, and colonization along with protein adsorption by inhibiting the exchange of enzymes and lipids among the microorganisms.19,21 A layer of hydration develops due to the formation of hydrogen bonds between the hydrophilic polymers and water interface, whereas ionic solvation takes place for zwitterionic polymers.19,20,56 T he hydrophobic polymers exhibit different mechanisms for fouling prevention, similar to that of lotus-leaf with microfibrils on its surface representing hierarchical nanostructures preventing the coated surface from fouling.19,57 Du et al.19 described a valuable means of synthesizing antifouling paints by grafting silicificated polyaniline nanofiber arrays (SPNAs) over the solid base of HPAPD film. The resultant formulation showed excellent adhesion to steel substrate, corrosion resistance to ASW (artificial seawater) and possessed remarkable antifouling properties, repelling marine bacteria like E. coli, and deterring the adhesion of proteins.19  \n\n![](images/cc2c81f0c07102091193c66f15dca276a525dee5fc921b938f19ec28f089f6f1.jpg)  \nFig. 10: General framework for the characterization of antifouling performance of the copolymers. Reprinted with permission from reference (58). Copyright 2017, American Chemical Society  \n\nThe pioneers well-known for the development of antifouling coating technologies, Duong et al.58 reported a generalized framework for the synthesis and characterization of polysiloxane-based copolymers using RAFT agents59 emphasizing that the antifouling performance of the diblock copolymers were better than that of the triblock copolymers, (Fig. 10).58  \n\nThe predetermined time-based study to carry out the hydrolytic degradation test of polymer films was conducted by incubating the samples in ASW. The mass loss (in $\\mathrm{wt\\%}$ ) was determined using the following equation  \n\n$$\n\\mathrm{loss}(\\%)=\\frac{w_{o}-w_{t}}{w_{o}-w_{\\mathrm{pvc}}}\\times100\\\n$$  \n\nwhere $w_{o}$ and $w_{t}$ are the initial and final (at time $=t$ ) weights of the PVC substrate coated with synthesized copolymer compositions and $w_{\\mathrm{pvc}}$ represents the weight of the substrate foil. After the bacterial attachment studies were conducted, the crystal violet (CV) solution was extracted from the inoculated wells and the relative rate of adhesion was measured by the following equation58  \n\n$$\n\\mathrm{\\adhesion=\\frac{\\left(OD_{with\\bacteria}-O D_{b l a n k}\\right)_{c o a t i n g}}{\\left(O D_{w i t h\\ b a c t e r i a}-O D_{b l a n k}\\right)_{P S c o n t r o l}}\\times100}\n$$  \n\nwhere ODwith bacteria and $\\mathrm{\\Gamma_{OD_{blank}}}$ represent the optical density of the CV solution with bacteria and without bacteria.58 Antifouling field studies as per French standard (NF T 34-552) led to the determination of an efficacy parameter $N$ , evaluated from a distance of $1\\mathrm{cm}$ from the edges of the panel. The parameter, $N$ , was defined by the following equation  \n\n![](images/db1be9c040c66d7c6ba30b9ee26ca3ae69021d2c5abe23982a28a7e0e181c72f.jpg)  \nFig. 11: Antifouling field studies performed at Toulon Bay, France. D and T stand for diblock and triblock, $5k$ and $10k$ represents the molecular weight of PDMS. Ref. stands for the reference standard. Reprinted with permission from reference (58). Copyright 2017, American Chemical Society  \n\n$$\n{\\cal N}=\\Sigma(\\mathrm{IF}\\times\\mathrm{SF})\n$$  \n\nwhere SF is defined as the severity parameter, responsible for the frictional drag penalty of ship hulls generated on account of increased surface roughness due to foulers, whereas IF is the intensity factor which gives an estimated percentage of the surface covered by variety of macrofoulers, directly proportional to the molecular weight of the polymer employed for coating fabrication as shown in Fig. 11.  \n\nIn the succeeding work, they reported about the thermal characteristics of such well-defined diblock copolymers60 in which the thermal behavior and stability of PDMS-based diblock copolymers was extensively studied. After obtaining the DSC thermograms, it was found that these diblock copolymers have two distinct $T_{g}$ values. Therefore, the value of $T_{\\mathrm{g}2}$ (second Tg) was obtained from Fox–Flory equation61,62 given as follows:  \n\n$$\nT_{g}=T_{g\\infty}-{\\frac{K}{M_{n}}}\n$$  \n\n$$\n\\frac{1}{T_{g}}=\\frac{W_{1}}{T_{g1}}+\\frac{W_{2}}{T_{g2}}\n$$  \n\nwhere $W_{1}$ and $W_{2}$ are the weight fractions of each component.  \n\nAnother work by Bressy and team63 was comprised of the synthesis of environmentally benign hybrid antifouling coatings known as FRC/SPC antifouling coatings. The field studies conducted post-synthesis showed excellent antifouling properties after 7 months of immersion and, also good foul-release properties were obtained.63  \n\nPretti et al.64 studied the effect of bismuth catalyzed coatings on leaching rates and AF performance of marine coatings under toxicity analysis and its effect on microorganisms was studied subjected to ecotoxicological assessment. The blended three layer AF coatings revealed lipophobic character, attributed to the low surface energy of fluorinated polymers. It was concluded from the toxicity assessment that the tin-based ions exhibit acute toxicity of lower degree to different species of marine lives, fisheries, invertebrates, and juvenile, to name a few.64–67 When compared to Cubased leachates/catalyst, bismuth is found to be an ecosustainable alternative to the traditionally used catalysts for the preparation of surface-active polymeric coatings.64 Song et al.68 reported a case study on marine pollution caused by leachates at South Yellow Sea of China. They fabricated an antifouling coating by incorporating a mixture of sodium benzoate (NaB) and sodium pyrithione (NaPt) as potential biocides into commercial silicone matrix (Sylgard 184). The nylon and bamboo coated substrates were prevented against macroalgae ( $U.$ Prolifera), by inhibiting the entire growth of the propagules. The rate of adhesion $(r)$ was calculated from the density of settlement of microorganisms using the following equation68  \n\n$$\nr={\\frac{\\left(C_{\\mathrm{b}}-C_{i}\\right)}{C_{\\mathrm{b}}}}\n$$  \n\nwhere $C_{\\boldsymbol{\\mathrm{b}}}$ and $C_{\\mathrm{i}}$ denote the density of micro-propagules in blank and experimental containers. The plotted results obtained from the Tukey test suggested that NaB formulated soluble matrix antifouling paint was optimized for $1\\ \\mathrm{wt\\%}$ of NaB incorporation as durable antifouling paint without rapid leaching of its constituents into the marine environment.68  \n\nThe coating science on microtopography and nanotopography surface design goes with the evolution of coatings on biomimetic structures inspired from sharks, whales, shells, oysters, etc. by the incorporation of natural products, to yield long-lasting antifouling systems. In this regard, Chambers et al.69 introduced a new methodology to incorporate natural products into the coating system and later analyze their performance layerwise. The present approach comprised an antifouling additive, a crude Chondruscrispus extract incorporated into the resin system as a booster biocide. The results of the rigorous field immersion test carried out for 42 and 105 days of immersion were reported in Fig. 12.69  \n\nA similar research was carried out by Svenson and team70 by exploiting the antibacterial property of polygodial (drimane sesquiterpene) as the natural product transformed into alkenes which undergo epoxidation to provide a series of 11 drimane compounds. The macrofouling activity of the 11 synthesized materials was inspected under the influence of 12 different types of biological species. The successful biofouling inhibition was witnessed in artificial and in natural seawater environments inhibiting the growth of micro- and macrofoulers at the surface.70 Another recent work on incorporating natural products for antifouling coating fabrication was reported by Ding et al.71 using nonleaking capsaicin (active component of chili peppers) as the natural product blended with PDMS-block copolymer. The capsaicin particles were bonded chemically with $\\mathrm{CoFe}_{2}\\mathrm{O}_{4}^{-}/$ gelatin nanospheres, on account of which the synthesized coatings possessed nonleaking environment-friendly AF approach. The optical study showed the lowest cell settlement for Navicula subminuscula due to an active layer of capsaicin inhibiting the settlement of microorganism without leaching out of the coating surface.71  \n\nChitosan-based nanocomposite antifouling coatings were recently fabricated by blending chitosan nanoleaves with biocides (basically, transition metal/metal oxide nanoparticles) like zinc oxide72 and copper oxide.73 Abiraman and team73 synthesized chitosan coatings by incorporating copper oxide into chitosan matrix under different reaction conditions and their feasibility with various parameters as a function of antifouling performance was studied deeply. The synthesized nanoleaves were blended into the polymers with accurate mechanical properties (like polyurethane) to enhance the durability of the system, coated on three different substrates: wood, mild steel and cement. The SEM results revealed the formation of micro-size domains of copper oxide nanoparticles. The HRTEM results revealed that the copper oxide embedded chitosan nanoleaves were $14~\\mathrm{nm}$ wide and $98~\\mathrm{nm}$ to $171\\ \\mathrm{nm}$ long. Outstanding biofouling efficiency was witnessed against a set of three algae, namely Arthrospira, Chlorella, and Amphora. The growth of algal bloom was determined by quantifying the amount of chlorophyll derived from a scratched portion of algae from the fouled coating surface, utilizing a method reported by Lichtenthaler.74 The algae cell count can be measured using Neubauer hemocytometer. The pigment concentration was calculated from the following equation, assuming that the factors responsible for algal growth temperature, pressure and surface roughness remains unperturbed:  \n\n$$\n\\mathrm{Chl}-a\\Big(\\frac{\\mathrm{mg}}{\\mathrm{L}}\\Big)=11.24\\times A_{661.6}-2.404\\times A_{644.8}\n$$  \n\nwhere the pigment concentrations were obtained by inserting the measured absorbance values denoted by $\\cdot_{a}\\cdot{}$ in micrograms per milliliter of plant extract solution. The above equation is based on the redetermined specific absorption coefficients, denoted by $\\boldsymbol{A}_{661.6}$ and $A_{644.8}$ , listed in reference (74). The results proved the efficiency of chitosan nanoleaves coating as environmentally benign coatings by prohibiting leaching out into the marine atmosphere.73 Similar findings were reported by Al-Naamani et al.,72 when they studied the incorporation of zinc oxide $(Z\\mathrm{nO})$ biocide into chitosan polymer matrix for the optimization of antifouling efficiency of the fabricated coatings. The swelling and solubility studies reported a steep fall in the swelling ratio attributed to more compact, tightly bound and fully crosslinked three-dimensional structures formed due to nano- $.Z_{\\mathrm{{nO}}}$ particles. A controlled release of biocidal $\\mathrm{znO}$ nanoparticles was ensured by ICP analysis, rendering it safe to blend with chitosan polymer. The immediate effect of photocatalysis under the influence of white light for contact killing of microorganisms lasted for a shorter span, thus proving it to be less harmful to the marine environment.72  \n\n![](images/e5d9c34487ec0dd4d66183c51e28f3f9a9c5d8b4bc255c30a4d34da5059fd7d4.jpg)  \nFig. 12: Field-immersion test images of the coated specimens.69 Copyright 2014, reproduced with kind permission from Elsevier  \n\nBinders are known to be the film-forming component of paints, mostly referred to as resins, which combine with solvents to deliver a successful paint technology with desired dry film thickness (DFT). This result-oriented approach of the binders serves as a boon for the coating industry, especially for antifouling paints. Generally, these resins are polymeric compounds divided into two categories—convertible and nonconvertible, which undergo polymerization reaction after being applied onto the substrate, whereas the latter already exists in polymerized form, and only needs to be coated after blending with the solvent.75 The role of binders in successful functioning of AF paints was discussed in a patent by Proudlock and Dennington76 who claimed to possess an invention on synthesis of a binder system with optimum rate of hydrolysis to produce two methacrylate polymers with pigment volume concentration (PVC) between 30 and $50~\\mathrm{wt\\%}$ , using zinc oxide pigment to make the system antifouling active.76  \n\n![](images/6ead712561204bbe0b6dda5ee086a9dd7b1474dc0e7a4e3ef11fdc1d5199c2bb.jpg)  \nFig. 13: Laboratory setup to promote the growth of mussels, plaque, and shellfish in a $\\sim12,000\\mathrm{-}\\mathsf{L}$ aquarium, where siphon was used to produce surge and other parts to produce adhesion. Reprinted with permission from reference (77). Copyright 2016, American Chemical Society  \n\nThe role of antioxidants to deter marine biofouling was studied by Wilker et al.77 by taking a step toward environmental sustainability. The health hazards imposed by AF coatings can be assessed by a novel technique, reported as follows—a total of ten marine biofouling species were maintained in an aquarium setup (Fig. 13), exposed to the immediate vicinity of the coated specimen observing their survival for 3 days. After undergoing a rigorous procedure, the weight of the extracted samples of species was rounded up to three decimal place and the condition index $(C I)$ was calculated using the following equation77,78  \n\n$$\n\\mathrm{CI}={\\frac{\\mathrm{dry}\\ m e a t\\ w e i g h t}{\\mathrm{dry}\\ \\mathrm{shell}\\ w e i g h t}}\\times100\n$$  \n\nUnder the category of filler-based antifouling coatings, the following research contributions are noteworthy. The fabrication of PDMS–FTDS (perfluorodecyltrichlorosilane) antifouling coatings was carried out by Li et al.79 in one-step procedure by incorporating zinc oxide as nanofiller for imparting antifouling efficacy to the nanocomposite coatings coated onto steel (Q-235) substrates. The SEM analysis confirmed the presence of FTDS on the surface of the coating specimen by forming a layer over the protrusions caused by $\\dot{Z}\\mathrm{nO}$ nanoparticles, filling the air pockets. The wettability measurements revealed that the critical surface tension values obtained from Zismann plot were very low on the order of $19\\mathrm{\\mN/\\Omega}$ m and in case of complete wetting also, the coatings were able to resist fouling.79 Oldani et al.80 reported a facile route for impregnating the perfluoropolyether (PFE) film with ceramic oxides, where $\\mathrm{TiO}_{2}$ and $\\mathrm{ZrO}_{2}$ particles were used to formulate multilayer AF coating. The particulate fouling test was conducted to evaluate the resistance of coatings toward $\\mathrm{CaSO_{4}}$ particles, where the solution was heated in a tank and pumped through a tube sample, internally lined by sample coatings (Fig. 14). The foulants deposited were quantified by the weight differences and then normalized in function in terms of surface area and time of exposure. After $^{72\\mathrm{~h~}}$ , a fouling of only $2\\%$ was observed on $\\mathbf{Z}\\mathbf{r}\\mathbf{O}_{2}$ -based coating, whereas it was $10\\%$ for $\\mathrm{TiO}_{2}$ -based multilayer coating.80  \n\n![](images/1cc97c1966651164d2fb5a4c3efee77995503ada7920dc912c461a97c32d90b0.jpg)  \nFig. 14: Schematic of the test rig used for fouling mitigation assessment. R-heating element, TCthermocouple, $\\pmb{P}$ -pump, FM-float flowmeter.80 Copyright 2015, reproduced with kind permission from Elsevier  \n\n![](images/4fcd3e0658df131e73d2e2b6f720031ce47cc582cc31faff39c9926ee1a89c62.jpg)  \nFig. 15: The structure of novel hybrid biocide-incorporated PDMS coating-preparation and characterization.81 Copyright 2017, reproduced with kind permission from Springer  \n\nThe novel dual-nature multifunctional antifouling coatings based on biocide incorporation using allyltrimethoxysilane as precursor of the reaction, coated onto mild steel (S-36) substrates were synthesized by Suleiman et al.81 (Fig. 15). The five different types of biocides namely Irgarol, 1,1-dimethylbiguanide hydrochloride, silver nanoparticle dispersion, titanium nanosize powder, 1-hydroxycyclohexyl phenyl ketone, followed by MOLY-white 101 used as the corrosion inhibitor, were incorporated into the PDMS polymer matrix. The SEM analysis revealed dense, homogeneous and microcrack-free surface. The biocide-embedded PDMS hybrid coatings were declared antifouling and anticorrosion driven; they were ideal and suitable for the overall protection of marine structures.81",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# Foul-release coatings  \n\nMany foul-release (FR) systems are available commercially; the development of an efficient product entirely based on the FR properties is still a far cry. A rational study needs to be done to completely understand the actual polymeric materials, post-determining from a massive screening of available polymers to locate the materials having actual role in releasing the growth of various microorganisms. Still, the broadspectrum activity of foul-release polymers is questioned by the huge diversity of polymers; their structure–property relationship and attachment mechanisms has not been found. Therefore, in this regard, literature revealed that no systems would ever prevent fouling of a surface totally; yet potential attempts can be made to reduce it to a large extent. The hurdles in the path of development of foul-release coatings can be slower testing time, cost of fabrication, time-consuming environmental assessments, government regulations and the dependency of market on antifouling coating technology. On the other hand, polysiloxane-based FR coatings already yield good results on fast-moving vehicles. Further studies on the influence of mechanical and surface properties on adhesion phenomenon will orientate the research on polysiloxane-based foul-release coatings for navigation of vessels at a minimum or slower speed. The most significant advances in the field of foul-release coatings have been recently collected in an excellent review by Selim et al.3  \n\nThe usage of foul-release coatings prevents the accumulation of heavy metals like Cu, Zn, and their oxide nanoparticles from settling into the deep-sea beds in the form of sediments, different from antifouling systems. Mikael et al.82 consolidated the valuable feedback on the ban of copper-based biocide leachate coatings through a survey targeting a particular questionnaire answered by a team of experts comprising of academician, researcher, marine legislation, marine product specialist and shipping industry management. All favorable responses from different professional roles were collected upon cost analysis and efficiency revealing the future prospects of nonstick coatings. This comprehensive information provides a valuable insight into a fruitful research on foul-release coatings and suggests the development of upcoming marine antibiofouling green technologies.82 The understanding of the mechanism of foul-release coatings is essential for the development of such systems and to differentiate them from the biocide-based antifouling coating systems, as depicted symbolically in Fig. 16.",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# Silicone elastomer-based foul-release polymer coatings  \n\nSilicone-based elastomers possess the properties required for good fouling release, like low surface energy on the order of less than $22~\\mathrm{mN/m}$ and low modulus within a range of $1.4{-}3\\ \\mathrm{MPa}$ .50 The foulants adhere weakly to the surface of these elastomers, facilitating easy release of marine fouling with the aid of hydrodynamic shear of moving water. In the past decades, multifarious properties of specialty polymers like siloxane and fluoropolymers have been exploited to develop marine foul-release coatings (Fig. 17)3,14,83,84 leading to the formation of not only block but also linear, graft and hyperbranched structures.85 Fluoropolymers are the second most widely used polymers after siloxane class moieties for foul-release applications due to their high electronegativity and low polarizability, which in turn leads to weak London dispersion forces, cohesive and adhesive forces, which contribute to low surface energy and higher water contact angle values.35  \n\n![](images/13296ee077f6491e3fa64c19f306f4146284b7dcc369f253463d14c834140084.jpg)  \nFig. 16: Schematic illustration of mechanism of (a) foul-release and (b) antifouling coating systems  \n\nPolydimethylsiloxane along with its different functionalities has been widely used nowadays as the basis of commercially available ‘‘foul-release coatings,’’ enabling the researchers to develop more out of it and implement such systems by extending their usage for industrial coating applications. The release rate efficiency of functionalized and nonfunctionalized PDMS-based coatings (blends, composites, block copolymers) was estimated to be five times higher than that of other hydrophilic surfaces, establishing low interactions with proteins and other enzymes.83,86 In the context of proving polydimethylsiloxane as the potential candidate for foul-release marine coating application, Stevens and team87 took efforts to prove PDMS as harmless for the marine environment. Although PDMS fluids ultimately sink as sediments in deep-sea beds, there were no adverse effects found on a wide range of marine species. After an in-depth study of the sediments generated by the sludge disposal from various sources, it was found that the dry weight concentration of PDMS was between 0.03 and $2.3~\\mathrm{{mg/}}$ kg only, details of the findings are mentioned in Table 2.87  \n\n![](images/41a05d1bbd8ddf3f5e2dede146b57c8e9b1976717e9b56f8317a6f350779bc77.jpg)  \nFig. 17: The schematic representation of multitudinous properties of foul-release polymers  \n\nAll the data cited above, obtained from the analysis, reveal that PDMS is the optimum and the safest polymer to be employed for environment-friendly marine coating research. Since PDMS with high sheer and physical size of the molecule is used for the synthesis of marine polymeric coatings, it restricts its absorption into other organisms.  \n\nThe hydrophobic nature of PDMS, depicted in Fig. 18 is attributed to the presence of methyl groups at the surface. When PDMS comes in contact with three-phase contact line of water, a partial/incomplete wetting is observed on hydrophobic PDMS surface. The low surface energy of PDMS and the low surface tension, on the order of less than $19\\ \\mathrm{mN/m}$ , makes it viable for foul-release applications by reducing the interaction between marine organisms and the coating surface. The microorganisms that are weakly adhered onto the coatings surface via van der Waals forces are easy to release, since they are loosely bound to the coating surface.  \n\n![](images/e1eca6f7828e3ca683efc87b1e98f40f29e09c39c32034ac8ce811fe971d2d0c.jpg)  \nFig. 18: Water-repellent nature of PDMS due to the presence of hydrophobic $(-C H_{3})$ segments which leads to phase separation between the two distinct phases  \n\nTable 2: Concentration of PDMS in marine surface sediments from areas used for disposal of sewage sludge87 Copyright 2001, reproduced with kind permission from Elsevier   \n\n\n<html><body><table><tr><td>S. no.</td><td>Sample location</td><td colspan=\"2\">Concentration (mg/kg dry wt)</td><td>References</td></tr><tr><td></td><td></td><td>Mean</td><td>Max.value</td><td></td></tr><tr><td>1.</td><td>Uncontaminated area</td><td>< 0.03</td><td>0.04</td><td>CEFAS88</td></tr><tr><td>2.</td><td>Liverpool Bay</td><td>0.33</td><td>2.3</td><td>CEFAS88</td></tr><tr><td>3.</td><td>Boston Harbour, USA</td><td>16.6</td><td>34.2</td><td>Powell et al.89</td></tr></table></body></html>  \n\nCallow et al.90 described a means of depositing nanocomposite siloxane films using PACVD (plasmaassisted CVD) technique over glass slide to determine the biofouling resistance potential of foul-release coatings. The XPS analysis revealed that upon immersion, the carbon content kept on decreasing layer by layer from the coating surface. Adhesion strength was measured with the help of biological assays, growth of sporelings of macroalgae (Ulva linza) and marine bacteria (Pseudomonas fluorescens) was counterchecked by measuring the wall shear stress of the coatings, when subjected to water jet. Focusing on the deposition parameters, authors suggested that extended cleaning time and temperature of deposition affected the degree of crosslinking of the polymer film resulting in production of more robust polymeric coatings suitable for foul-release applications.90 Navabpour et al.91 emphasized the mechanical properties of the siloxane-based marine coatings deposited on glass and steel substrates by using a hybrid of PACVD–PVD deposition techniques. The results from scratch test indicate a high level of mechanical robustness by resisting scratch tracks up to $35\\mathrm{~N~}$ , except for coating (B) which started to wear beyond the load of $35\\mathrm{~N~}$ under higher rates of shearing (Fig. 19).91  \n\nAntioxidants stop the formation of glue by terminating the crosslinking reactions at the coating–water interface which hinders formation of linking pathways between the extracellular polymeric substance (EPS) secreted by microorganisms and the coating surface.77,92 A potential attempt was made by Wilker and team77 to curb marine pollution by reinventing the surface chemistry through surface modification by replacing harmful biocides with harmless antioxidants, equally potential antifoulants as biocides. In the present work, three different types of antioxidants (1) anisole, (2) 2, 6-di-tert-butyl-4-methylphenol (BHT), and (3) 2, 6-di-tert-butylphenol (DTBP) were blended with a solvent and coated on aluminum panels with the help of epoxy primer. The foul-release performance of the designed coatings was accessed by making a comparison between the reference control compound, 3, 5-di-tert-butyltoluene (DBT), and the novel designed system. The results revealed that such a system was based on the notion that a variation in the wt% loading of the antioxidant will alter foul-release performance of the system.77  \n\n![](images/d0c56ef9a6a2f2837939ec35809b9f50e53bf1df1d12c58ad73f47c5693b1e22.jpg)  \nFig. 19: Scratch tracks for various coatings deposited on M42 steel, obtained using a $200\\mathrm{-}\\upmu\\mathrm{m}$ -diameter diamond tip.91 Copyright 2010, reproduced with kind permission from Elsevier",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# Amphiphilic block copolymer-based foul-release coatings  \n\nThe limitations of foul-release coatings being not suitable for stagnant environment and eventually failing at sailing speeds below 20–25 knots for most vessels. This fact makes way for the instigation of amphiphilic coatings as the prospective research in foul-release coating field having the properties of both hydrophobic as well as hydrophilic surfaces. These coatings provide a topological and chemically compositional platform and complex surface to the fouling organisms (like larvae), reducing their adhesion by obstructing both hydrophilic as well as hydrophobic interactions between the organism’s secretions and the coating surface.50 An extensive review by Yilgor93 emphasized the silicone containing diblock and triblock copolymers synthesized using the following polymerization techniques: (1) anionic polymerization, (2) ring-opening polymerization, (3) atom-transfer radical polymerization, (4) step-growth polymerization and (5) chemical combination of preformed blocks, focusing on the functionality and the reactivity of the silicone polymers.93  \n\nBlock copolymerizaton is a breakthrough technology used to develop desired properties with fusion of siloxane or/and fluorinated polymers, well-known to possess the following characteristics: low elastic modulus, low surface energy,94 higher surface enrichment and microphase separation, high purity,95 and chemical and weather resistance. It is a controlled polymerization technique,96 with benefits of complete consistent wetting, thermotropic mesophase formation, wellordered liquid crystalline surface domains, oleophobicity, thermodynamic and surface stability.97 Nevertheless, the surface chemistry of the twin polymers remains misapprehended, and as a result, it is unable to reach the desired level of effective surface control.98 Therefore, in order to understand the surface chemistry depicting in detail the surface aggregation, accumulation and segregation of two or more polymer matrices, the recent developments by various researchers are amalgamated and reported as follows.  \n\nDiblock copolymers of PDMS and poly(perfluorooctylethyl acrylate) were synthesized by Martinelli et al.85 leading to the formation of smectic structures. A probe length of $4\\mathrm{nm}$ of GISAXS equipment confirmed the presence of fluoroalkyl helices as the main constituent at the surface, and at the same time the presence of PDMS below $4\\mathrm{nm}$ level can be speculated. DCA value of $110^{\\circ}$ was reported owing to the hydrophobic nature of PDMS. The obtained coatings were highly oriented with approx. $1\\mathrm{nm}$ thickness of fluoropolymer aggregation on the surface, giving excellent release properties suitable for marine coating application.85 Albert et al.99 in a conference proceeding reported the significance of amphiphilic block copolymers that are well-known to impart hydrophilicity by altering the surface properties of PDMS prepolymer by the embodiment of zwitterionic polymers for enhancement in foul-release performance of the coatings.99,100 Similar findings on amphiphilic networks were reported by DeSimone et al.101 They synthesized copolymer networks from polyethylene glycol (PEG) and perfluoropolyether (PPFE) and monitored the effect of humidity on curing behavior resulting in different surface properties. The highest dynamic contact angle value reported was $110.8^{\\circ}$ for high humid condition cured coatings. Such coatings cured under ambient humid ( $24\\%$ -low and $57\\%$ -high) conditions were reported as unique foul-release coatings since the fouling generated can be removed easily from the coating substrate by the application of water jet.101 Bodkhe and team102 reported the fabrication of amphiphilic PDMS-polyurethane coatings capable of fighting the microorganisms (N. incerta, ${\\bar{H}}.$ pacifica, C. lytica) and the macroorganisms (adult barnacles and macroalga) when exposed to artificial seawater (ASW) environment. The surface stratification and surface reconstruction properties led to the generation of more hydrophilic structures successful in deterring a wide variety of marine fouling organisms delivering a smooth foul-release performance.102  \n\nEkin and Webster103 synthesized triblock copolymers of PDMS and polycaprolactone crosslinked with polyurethane revealing good underwater performance with low surface energy and desired toughness.103 Tingfa et al.104 intermixed polyurethane and acrylic latex to yield poly(siloxane-ether-urethane)-acrylic hybrids. The hybrid coatings consisted of properties of waterborne emulsions as well as adhesives. The surface hydrophobicity was reported to increase from $72.5^{\\circ}$ to $101^{\\circ}$ , attributed to phase separation, which gives rise to self-stratification and enhances foulrelease properties. Because of excellent elongation, the water resistance and surface roughness properties also improved.104  \n\nThe problem of surface accumulation of polymers over one another was common and has been explored by many researchers in the past. To overcome the prevailing issue Liu et al.13 formulated PDMS and polyurea copolymeric coatings with good mechanical properties. The images of the coated panels, after immersion at South China Sea for a duration of 60 days, are represented in Fig. 20. The results are valid up to a speed of 18 knots for $200\\mathrm{~h~}$ under navigation and also in suspended conditions since the coatings adhered strictly onto the substrate.13  \n\nSimilar findings on siloxane-polyurethane amphiphilic block polymer coatings were reported by Sommer et al.105 using ground titanium dioxide as the potential pigment copolymerized along with the monomers. The results of pseudobarnacle adhesion and leachate toxicity analysis revealed that the percentage removal of marine bacteria remained unchanged but the gloss performance increased dramatically.105 In continuing theme of titanium dioxide embodiment into polymeric materials, a study on the effect of photocatalysis on curing characteristics of the synthesized copolymeric coatings was reported by Safty et al.106 (Fig. 21). The polarized light microscopy results revealed surface homogeneity since the bactericidal titanium dioxide nanoparticles were dispersed homogeneously inside the polymer matrix. The laboratory biological assays and field immersion tests demonstrated that the results were on par with the desired foul-release performance of the commercial coatings.106,107  \n\n![](images/aeb1d66f648d4f92cd7dd8eecea4fe9f1763ffd1eec62d9a4d0e7c7faadb405a.jpg)  \nFig. 20: Photographs of coated panels after static immersion in South China Sea for 60 days. Reprinted with permission from.13 Copyright 2016, American Chemical Society  \n\n![](images/f86082f637a4f3f953c04f5276acba5acd59fef410708e7bed739ccb404403c0.jpg)  \nFig. 21: Photocatalysis of PDMS/TiO2 nanocomposite coating under the influence of UV light.106 Copyright 2016, reproduced with kind permission from Elsevier  \n\nIn extensive research based on high-throughput (HT) combinatorial approach,108 a total of 75 FR coatings were synthesized by Majumdar et al.109 by incorporating quaternary ammonium salts (QAS) into siloxane matrix reporting a tremendous improvement in hydrophobicity and foul-release performance against marine bacteria, C. lytica. Minimum leachate toxicity was reported for 69 coatings out of the 72 investigated coatings. In addition, the combinatorial approach was successful in determining the optimum and broad-spectrum antimicrobial activity of trimethoxysilane functional QAS (QAS-TMS) incorporated PDMS coatings out of 60 unique coating compositions. The strong antimicrobial performance exhibited by synthesized coatings was attributed to the segregation of QAS rich domains over the coating–air interface.110 In the continuing theme, an advanced combinatorial high-throughput (C/HT) FR laboratory assay was utilized in consecutive work by Majumdar et al.111 to synthesize QAS-functional alkoxysilane incorporated PDMS AF/FR hybrid coatings, cured using methyltriacetoxysilane. A total of 24 different formulations were exposed to high-throughput bacterial and diatom assays reporting strong antimicrobial performance manifested by ethoxy silane groups of QAS molecules.111 In another work, copolymer of methylhydrosiloxane–dimethylsiloxane (PMHS– PDMS) was amalgamated with tethered QAS, later moisture cured and cast over bare and primed aluminum disks for the evaluation of AF performance against ASW bioassays. The effect of hydride equivalent weight of copolymer on AF/FR hybrid performance of moisture-cured coatings was evaluated and $29\\ \\mathrm{wt\\%}$ QAS concentration was reported as optimized composition with maximum biocidal activity.112 The combination of different biocides can bring about a significant amelioration in protein adhesion and biofilm retraction performance of the siloxane tethered AF coatings. These findings were corroborated in consecutive research by Ye et al.113 through the incorporation of triclosan and $\\mathbf{C{-}14\\mathrm{~OAS}}$ into PDMS matrix tested against fibrinogen as model globular protein. The research outcome confirmed restructured surfaces by biocide incorporation into PDMS matrix which resulted in biocidal retraction, increased AF performance and reduced biofouling growth.113 In addition, the sum frequency generation (SFG) spectroscopy was utilized to study polymer-structured surfaces of silanol-terminated PDMS-QAS tethered hybrid coatings. Also, a track of coating surface interaction with air, water, solvent, and nutrient– growth medium (NGM) interface was maintained using SFG. The antimicrobial performance of the biocide-tethered coating toward E. coli, S. aureus, and C. albicans immersion assays was found to be dependent on alkyl chain length of the QAS molecule.114 The previously discussed research contributions serve as a breakthrough in siloxane-urethane coating chemistry for protecting marine structures from biofouling.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# Nonfouling technology based on (epoxy resins-PDMS) hybrids  \n\nEpoxy resins have been used in coating industries since inception, for protecting vessels with highquality paint technology applied onto ship hulls as well as deck and superstructures subjected to salt spray, weather conditions, and cargo spillage. Although the painted deck surface is continuously abraded by foot traffic and cargoes, it is able to withstand hard wear and repeated cleaning.115,116 In the past era, before the discovery of purely foulrelease polymer (PDMS) for potential foul-release applications, epoxy coatings were recoated by chlorinated rubber forming an impervious coat to water for preventing fouling.116 The unique properties like thermal stability, multiphased chemistry, biocompatibility, environment friendliness, and low toxicity, enables PDMS to be utilized as an effective material to be blended with epoxy resins.117 PDMS has been used as the potential precursor for the synthesis of protective polymer coatings because of reduction in its frictional drag resistance, elevation in corrosion and marine biofouling resistance and hydrophobicity of the designed system. The downside of polysiloxane-based coatings has been accompanied by poor adhesion and mechanical properties resulting in easy damage during navigation, ultimately reducing the performance and lifetime of the coatings. In this regard, one of the effective synthesis pathway to improve the mechanical properties of the protective coatings is either the introduction of epoxy resin segments and/or the incorporation of additional fillers and modifiers into the base polymer matrix.33 The possibility of combining the advantages of polysiloxane and epoxy resins has attracted extensive attention of many researchers in the past decade. This combination would endow fabricated polymeric coatings better thermal, oxidative stability, and lower temperature flexibility than neat epoxy resin and better mechanical and abrasion properties than neat polydimethylsiloxane.  \n\n![](images/195008768068683349a21a853d0ef836b56dab8fd0f46c16102debeb8202ee61.jpg)  \nFig. 22: Combined catalogue of the properties of epoxy– PDMS-filled and unfilled systems",
+        "category": " Introduction"
+    },
+    {
+        "id": 12,
+        "chunk": "# Nonfouling (epoxy resin-PDMS)-unfilled coating systems  \n\nThe blending avenue of epoxy resins with siloxane polymers opened multidirectional research areas for many researchers in the past decade reporting numerous reasons for blending the two polymers. A possibility to combine the advantages of both the polymers would bestow enhancement in the following properties as represented in Fig. 22.16,55,118–122 A paradigm shift in the attractive silicone polymer chemistry was studied by Yilgor et al.93 revealing numerous advantages of silicone polymers, entitling them to be blended with thermoset polymers like epoxy resins to foster unique copolymers suitable for eclectic applications.93  \n\nIn the nineteenth century Riffle et al.123 gave noteworthy contributions in the field of fabricating elastomeric epoxy networks by utilizing polysiloxane modifiers via equilibrium polymerization technique. The types of siloxane modifiers depending on the endterminated functionality were discussed along with an in-depth reaction kinetics of the two polymers. The results from conversion vs time plots showed that the siloxane polymers had higher reactivity when compared to amines, used as curing agents. The resultant films were turbid, tough and durable, suitable for hardcore applications for safeguarding marine structures.123  \n\nCopolymers of epoxy resins and polydimethylsiloxane with different functionalities like hydroxyl, aminopropyl were synthesized, deploying an assorted range of PDMS with molecular weights (between 650 and  \n\n![](images/e40cc5b004ddc98496930870b75145663acf981c6da2fdcc79e85323808a1e46.jpg)  \nFig. 23: The synthesis route of epoxy–PDMS core–shell microspheres.124 Copyright 2014, reproduced with kind permission from Springer  \n\n$24{,}000\\ \\mathrm{g/mol})$ . The intercrosslinking network (ICN) mechanism was employed for the formulation of foulresistant coatings using epoxy resins and silicone phosphorous polymers, by Kumar et al.118 The immunity against fouling was accessed by determining the growth size (in mm) of the barnacle species (Balanus variegatus) and the volume $\\%$ of growth on the mild steel coated substrates recorded against time frame of 30–200 days. It was reported that the minimum and maximum size of the barnacles grown over the substrate surface was $4~\\mathrm{mm}$ and $8~\\mathrm{mm}$ , with $10\\%$ of barnacles found dead. The use of different curing agents for epoxy resins and the incorporation of silicone in epoxy resin matrix led to an improvement in the antifouling performance of the coatings.118  \n\nThe reactive compatibility of the epoxy–PDMS system for various applications was investigated by Baselga et al.120 to develop a tougher thermoset material system exhibiting gradient structure initially phase separated, later diminished on the phase boundaries along with the curing profile. As evident from SEM and $\\mathbf{X}$ -ray microanalysis results, the microhardness and the domain size of gradient were homogenized over the course of time portraying miscible and fully compatible microstructures.120 The dispersion of polysiloxanes into epoxy resin matrix was improved in a research study by Rajagopal et al.124 by employing core–shell microsphere analogy using suspension polymerization technique (Fig. 23). The siloxane core and epoxy shell led to the formation of elastomeric microspheres.124  \n\nThe presence of spherical cavities was confirmed by studying the fractured surfaces obtained from mechanical tests. The SEM images along with the elemental composition of a single microsphere revealed that the maximum amount of silicon was present in the core as compared with the composition of shell (Fig. 24).  \n\nThe Halpin–Tsai model124,125 and the Lewis–Neilson model124,126 were used for prediction of modulus of epoxy–composites under the influence of adhesion between the polymer (epoxy resin) and the modifier/toughening agent (PDMS). The results of the study were in close agreement with rubber cavitation mechanism resulting in development of toughened epoxy systems attributed to incorporation of siloxane class.124 Similar findings on IPN coating networks of epoxy and siloxane were reported by Jia et al.127 revealing no clear interface between the two phases ranging in nanoscale, marking the successful polymerization of IPNs suitable for marine coating applications.  \n\nThe surface modification of such epoxy–PDMS blends was carried out by Jannesari et al.121 where they transformed the partial compatibilization of epoxy–PDMS blends to full compatibilization by segregating the dual PDMS-rich and epoxy-rich phases into an individual phase. Later, the irregular dispersion in the blended specimen was cleared after overcoming the following factors responsible for immiscibility of the blends as reported by ${\\mathrm{W}}{\\mathrm{u}}^{128}$ difference in (1) matrix viscosity, (2) mixing shear stress, (3) interfacial tension of two polymers, and (4) viscosity ratio of dispersed phase to continuous phase. The Taylor’s dispersion model was employed for dispersion studies, to find a relation between dispersed phase particle size and the viscosity ratio given by the following equation  \n\n$$\nr={\\left({2\\Gamma p^{\\mp0.84}}\\right)}/{\\eta_{m}\\gamma}\n$$  \n\n![](images/3935eb142beee20b490682fd9e3a5cbe2a17e49836923a0c204092e750fec903.jpg)  \nFig. 24: (a) Cross-sectional SEM image of a PDMS-epoxy core–shell elastomeric microsphere, (b) EDX analysis of the shell, (c) EDX analysis of the core.124 Copyright 2017, reproduced with kind permission from Springer  \n\nwhere $r$ is the number-average particle size, $\\gamma$ is the shear rate, $\\Gamma$ is the interfacial tension between the two components resulting in dispersion, $p$ is the viscosity ratio of the dispersed and matrix phase viscosities. The case study depending upon the value of $p$ was discussed as follows128  \n\nCase-I: For all $p>1$ ; the exponent is positive. Case-II: For all $p<1$ ; the exponent is negative. Case-III: For $p=1$ ; blend of equiviscous components, acquires the finest morphology.  \n\nFurthermore, surface studies revealed that the hydrophilic surface of the neat epoxy coating specimen transforms to a hydrophobic surface upon the incorporation of hydroxy-terminated PDMS fulfilling a prerequisite of foul-release coatings which can be attributed to the water-repellent nature of PDMS.121 Similar findings were reported by Romo-Uribe et al.129 describing the dispersion of PDMS as rubber phase in droplet form, dispersed into epoxy-rich matrix. The droplet’s size summed up from histograms of droplet diameters fostered from AFM micrographs lies between 0.6 and $0.8~{\\upmu\\mathrm{m}}$ , initially phase separated leading to the interpenetration of siloxane moieties into epoxy phase. The increase in toughness was attributed to the energy absorption capacity of functional rubber-rich phase, imparting the blend’s desirable mechanical and thermal stability, making it suitable for structural coating applications.129  \n\nThe advantages of modification of epoxy resins with PDMS of amine functionality have been reported by Huang et al.16 leading to oleophobic upgradation of the surfaces.16,130 The present approach provided a way to synthesize triblock copolymers of polyether and PDMS by modifying epoxy resins. The ESCA investigation estimated the degree of PDMS accumulation over the substrate trio (PTFE, steel and silicone rubber). The results revealed that the formulated blends cast over stainless steel possess stick-flip phenomena along with increased hydrophobicity and lower value of coefficient of static friction $(\\mu_{\\mathrm{s}})$ .16 Zhou et al.55 synthesized epoxy–siloxane hybrid coating systems via silicone intermediate synthesis with appropriate methoxy content and without the incorporation of any internal reinforcement. It possessed strength equivalent to that of the filled systems coated on aluminum substrates. The epoxy–siloxane-grafted polymer coatings were synthesized with better mechanical properties, heat resistance and amphipathic nature contributing toward foul-release applications.55  \n\nApart from superior mechanical properties, adhesion to the substrate is one of the prerequisites for maintaining the stability and lifespan of protective coatings, independent of the substrate surface and its make. The poor adhesion of coating to the hull substrate leads to coating delamination, which gives rise to several prospects of ship hull coating disintegration. The most likely phenomenon to take place is corrosion, under the influence of highly humid atmospheric conditions with high moisture content in and around the sea. This is depicted in Fig. 25, which shows ship hull degradation in possible ways, subjected to static and dynamic exposure of consecutive cycles of high and low tides conditions prevailing for prolonged periods, captured under the influence of Bay of Bengal, India.  \n\nThe adhesion strength is mostly dependent on the physical and chemical interactions between the substrate and the polymeric coating. The adhesion strength and pull of behavior of the epoxy–silicone dual-layered antifouling coatings were discussed by  \n\n![](images/3fb093830b7ac5adf32d049d58605d1d883495b80afa774dffec5006923f4fdd.jpg)  \nFig. 25: (a) Degradation of ship hull due to the breakdown of protective coating layer leading to biocorrosion, (b) the visible underwater growth suspended onto the ship hull surface, (c) growth of freshwater algae and seaweeds attached to the hull, (d) the on-shore growth of adult barnacles and mussels adhered strongly to the concrete surface, (e) the continuous and steady recruitment of biofouling progressively led to the permanent settlement of macroorganisms  \n\nKohl et al.131 to emphasize thickness of coating which is directly proportional to the coating toughness, attributable to the generation of more stiffer bonds between the copolymers. The structure of the duplex coating is illustrated in Fig. 26.131  \n\nThe extension of the Kendall model (1971)132 was carried out to determine pull-off force of a metal cylinder attached to the dual-layered epoxy–PDMS antifouling coating. The adhesion strength of elastomers depends upon the elastic properties, surface energy, bulk modulus, and contact radius. The following equation was developed by Kendall to quantify the critical pull-off force $(\\bar{P}_{\\mathrm{c}})$ required to detach a rigid cylinder attached to thin elastomeric glue film on a metal substrate:  \n\n$$\nP_{\\mathrm{c}}=\\pi a^{2}\\bigg(\\frac{2w_{\\mathrm{a}}K}{t}\\bigg)^{1/2}\n$$  \n\nwhere $t$ denotes the thickness of the coating, $w_{\\mathbf{a}}$ denotes the Dupre’s work of adhesion between the cylinder and the elastomer, $K$ denotes the bulk modulus, and a is the contact radius.132",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# Nonfouling (epoxy resin–PDMS)-filled coating systems  \n\nTo impart additional benefits of improved hydrophobicity, foul-resistance and durability to the existing epoxy–PDMS coating system, it needs to be blended with various additives. These additives can be added in different concentrations in terms of $w t\\%$ or $1\\%$ playing the role of either a potential filler or a modifier focusing to instigate the desired property into the polymer coating system. The most frequently used inorganic fillers to modify the properties of prevailing coating systems are fumed silica, calcium carbonate, titanium dioxide, iron oxide, carbon black, natural sepiolite, MWCNT, graphene and fluorographene.133,134 In the past few studies, these fillers were used to improve the tensile modulus and hydrophobicity of the surface coatings.93,121,135 Beyond mutual copolymerization, the basic polymers (epoxy resin and PDMS) were also blended with engineering plastics like polyamide-6 to impart permanent surface modification to existing polymeric structures, attributed to the bond chemistry and the linkages among them.93,136 The reported methods in literature extend significantly to the available toolbox used for the incorporation of additives (both polymer and metal) into the epoxy–PDMS coating system.  \n\n![](images/9ceb3b88d8bba2cbe8293661315bb2c10ab1a4812690f7297b5503568563c621.jpg)  \nFig. 26: Epoxy–silicone (PDMS elastomer) duplex coating on steel substrate.131 Copyright 1999, reproduced with kind permission from Springer  \n\n![](images/8f5e83fbdbd787d56fdd44e6818a0949d4ef17ddfb06db1f6ceef3f53ab89b3b.jpg)  \nFig. 27: Dispersion of silica nanoparticles in PDMS-Epoxy nanocomposite coatings.138 Copyright 2017, reproduced with kind permission from Elsevier  \n\nSaravanan et al.137 synthesized epoxy–PDMS-filled nanohybrid systems using titanium dioxide as the nanofiller coated on mild steel substrates. The morphological studies revealed the uniform distribution of $\\mathrm{TiO}_{2}$ nanoparticles, and the salt spray test confirmed the fruitful addition of $\\mathrm{TiO}_{2}$ by inhibiting corrosion. High crosslinking density and consequent hydrophobicity of the coatings repelled and resisted fouling products. The disinfectant property of titanium dioxide nanoparticles adds up to the antibacterial performance of coatings entitling them for effective nonfouling applications.137 Ammar et al.138 fabricated epoxy– PDMS hybrid coatings and utilized finely powdered silicon dioxide as a nanofiller, incorporated via solution intercalation method in different weight ratios. As evident from SEM micrographs (Fig. 27), uniform dispersion of silica nanoparticles throughout the host polymeric matrix with rough surface was obtained. The contact angle results revealed remarkable enhancement in hydrophobicity of the filled hybrid coatings with a contact angle value of $132^{\\circ}$ and superior electrochemical properties leading to better anticorrosive performance.138  \n\nXu et al.139 formulated epoxy–PDMS-filled systems consisting of silicon dioxide as potential filler along with the aid of two compatibilizers (GPTMS and ATS) added in predetermined proportions. The research emphasized microcrack prevention by modulating the sequence of addition of monomers and coupling agents, and later transparent (gel-like) cured hybrid systems were obtained. The increased hydrophobic character of the formulations was attributed to methyl groups, which penetrated well into the epoxy–filler matrix. The solvent-free $\\mathrm{SiO}_{2}$ -modified epoxy–siloxane hybrids led to the development of nonporous hydrophobic segments suitable for marine structural protective applications.139  \n\nDuraibabu et al.140 synthesized tetrafunctional epoxy resin, later copolymerized with synthesized nano-zinc oxide ( $1\\ \\mathrm{nm}$ to $50\\ \\mathrm{nm}$ ) coated on mild steel substrates. The TEM results revealed spherical morphology and monodispersity of the zinc oxide nanoparticles. Antimicrobial tests were conducted employing the bacterial culture (E. coli) (code-ATCC 8739), utilizing inhibition zone method. The antibacterial performance was ascribed to the rough surface texture and the electrostatic interaction of $\\scriptstyle z_{\\mathrm{nO}}$ nanoparticles with the cell surfaces of microorganisms. Similar findings were reported by Ramesh et al.141 on the synthesis of epoxy–PDMS blend coatings along with the incorporation of zinc oxide nanoparticles in varied proportions via solution intercalation method to yield nanocomposite coatings with improved hydrophobicity (max. CA value $=128^{\\circ}$ ) and anticorrosive performance.141  \n\nThe adhesion strength of the epoxy–PDMS-filled systems was evaluated by Esfandeh et al.142 by studying the different ways to coat aluminum substrates by using top coat and tie coat layers, under the influence of various adhesion promoters. The SEM image revealed good compatibility and adhesion between the two polymers, as depicted in Fig. 28. From the field immersion studies conducted for a duration of 7 months and at a depth of $11\\mathrm{~m~}$ beneath the sea, it was found that the intermediate tie coat of silicone– epoxy with $1\\ \\mathrm{wt\\%}$ silane top coat showed no delamination and maintained better fouling resistance.142  \n\n![](images/6d219aa37a8634cb174a18ecba633024a1aedb6f824393a77e2ee42b03f50b91.jpg)  \nFig. 28: SEM image at the interface of epoxy base coat and intermediate layer (silicone/epoxy, 1 $w t\\%$ silane).142 Copyright 2010, reproduced with kind permission from Elsevier",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# Role of fillers and additives in PDMS-based coatings  \n\nThe role of fillers and additives added in the form of nanoparticles to alter wettability of the base matrix yield either self-cleaning or superhydrophobic surfaces as is well discussed in the literature. The consequence of addition of fillers and additives on the properties of the polymer coating system is discussed as follows.  \n\nFor PDMS polymer the swelling ratio analysis was done by Bokobza and Diop49 reporting swelling ratio inversely proportional to the degree of interaction between the rubber and the filler. Swelling is undesirable and swelling ratio gives the measure of resistance offered by vulcanizates to swell within the solvents. Theory of swelling is generally applied to evaluate the total network chain density, which is given by the following equation49  \n\n$$\n\\nu=\\nu_{\\mathrm{r}}+\\nu_{\\mathrm{f}}\n$$  \n\nwhere $\\nu_{\\mathrm{r}}$ represents the number of effective network chains in the unfilled rubber and $\\nu_{\\mathrm{f}}$ represents the number of additional chains produced by bonding to the filler. The significance of swelling measurement over stress–strain measurements is that the amount of additional crosslinking can also be determined, affected by the presence of filler which is free from hydrodynamic reinforcement.49 In order to calculate the equilibrium swelling ratio $(Q_{\\mathrm{r}})$ of the rubber phase, it is assumed that the filler particles do not swell in the solvent phase, given by the following equation  \n\n$$\nQ_{\\mathrm{r}}={\\frac{Q-\\phi}{1-\\phi}}\n$$  \n\nwhere $\\phi$ is the volume fraction of the filler and $\\boldsymbol{Q}$ is the equilibrium ratio of the composite, expressed as follows:  \n\n$$\nQ={\\frac{V}{V_{\\mathrm{d}}}}\n$$  \n\nwhere $V$ denotes the volume of the sample and the solvent, and $V_{\\mathrm{d}}$ denotes the volume of the dry sample. It was observed that the increase in the filler content resulted in consequent decrease in the swelling ratio on account of restricted alignments due to the incorporation of filler at higher loadings.49  \n\nThe mechanical strength of PDMS was increased by incorporation of ‘‘closite $20\\mathrm{A}^{,,}$ nanoclay into HTPDMS (hydroxy-terminated polydimethylsiloxane), the analysis was done via shear lag model of indentation and FEA (finite element analysis). The objective was to derive the interfacial shear stress function of composite films and to measure the shear strength of nanocomposites reinforced by organically modified nanoclay platelets. As the indenter tip penetrates the elastic surface of the film, it deforms at the interface, and the interfacial shear stress can be quantified by the following equation  \n\n$$\n\\tau=\\tau_{\\mathrm{{max}}}\\sin\\left(\\frac{\\pi r}{\\frac{\\lambda_{o}}{2}}\\right),\\quad0\\leq r\\leq\\frac{\\lambda_{o}}{2}\n$$  \n\nwhere $\\tau_{\\mathrm{max}}$ denotes the maximum stress at the interface before yield. It was found that the interfacial shear strength is inversely proportional to the percentage weight of the nanoclay content, related to the shear thinning behavior of nanoclay particles. Moreover, the authors also reported optimum filler loading percentage as $5\\ \\mathrm{wt\\%}$ of nanoclay, since the maximum elastic modulus value was obtained for the same.143  \n\nWouters et al.144 fabricated a nanocomposite coating by incorporating inorganic, anisotropic, functionalized nanoparticles into the PDMS matrix. Two pathways for functionalizing sepiolite nanoparticles were used, namely ion-exchange and covalent functionalization. The coatings were subjected to biofilm formation, and later the obtained biofilms were exposed to the shear forces under turbulent flow and the quantification was done using the following equation144  \n\nThe surface topology results were in accordance with the Cassie–Baxter model, stating that interfacial tension played a significant role in altering the surface chemistry of the coatings. The interaction between two particles and between particle and coating determines the morphology and topology to account for aggregation, agglomeration and uniform dispersion of the nanoparticles throughout the polymer matrix.144 Zhang and team145 reported a mathematical approach for the determination of time of interaction of hydrophilic silica microparticles with an oligomer. The filler particles were rapidly encapsulated in PDMS matrix under the effect of capillary drag along with the gradient of surface energy as the driving force, $\\Delta\\gamma$ . By dimensional analysis, the time needed for encapsulation is represented by the following equation  \n\n$$\n\\tau\\sim\\frac{\\eta L}{\\Delta\\gamma}\n$$  \n\nwhere $\\eta$ represents the viscosity of the elastomer (PDMS) which retards the encapsulation process, and $\\mathrm{~L~}$ denotes the diameter of silica microparticle.145",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# Mathematical evaluation of foul-release performance  \n\nThe macrofoulers such as invertebrates, adult barnacles and their spores tend to adhere to certain selective surfaces according to the topography suitable to furnish sufficient adhesion with the coating surface. The interfacial properties responsible for the initial settlement of marine fouling and its subsequent growth are topography, wettability, and chemical heterogeneity; also considered as factors determining the foul-release performance.50 The joint-use of short-time rotary experiments, polymer reaction engineering and kinetic data studies can be brought together to provide empirical inputs for the development of mathematical models. They can be utilized to simulate the lifetime performance of the synthesized coatings in a study of just a couple of minutes.2 The flexible development of mathematical equations employed for the evaluation of foul-release performance of the coatings is a need of the hour.  \n\nJiang et al.83 referred the coating–water interface as a synthetic surface where foul-release activity takes place and described its durability mechanism with respect to modes of adhesion failure. The release ability of foulants is said to be directly proportional to the surface free energy of the substrate and to the modulus (gE)1/2,83,146 whereas in terms of fracture mechanics, the stress required to separate a foulant from the surface of the coating is given by the following equation  \n\n$$\n\\mathrm{Stress}={W E_{\\mathrm{c}}}{}_{/}^{1/2}\n$$  \n\nwhere $W$ is the work of adhesion, $E_{\\mathrm{c}}$ is the composite modulus of the adhesive matrix and the coating, and $a$ is the radius of contact.50 The minuscule contact angle of water droplets serves as a sharp knife, which scrapes off fouling from the substrate surface, releasing the microorganisms that were stabilized via electrostatic and weak van der Waals forces, resulting in the simple removal of micro- and macrofoulers.37 It is worthwhile to notice that degree of fouling assessment is dependent on the following parameters and can be determined by using any one of the ways37,147  \n\n1. Determination of critical velocity.   \n2. Measurement of adhesion strength.   \n3. Modeling the flow induced forces.   \n4. Measurement of wear resistance of surface.   \n5. Measurement of elastic stress.  \n\nLarsson et al.147 described a means of evaluating the mechanical adhesion strength of barnacle species (Balanus improvisus) by developing a hydrodynamic model based on assessment of local flow velocities close to the vessel’s hull, confirmed by the foulingrelease measurements for three different levels of barnacles. High-velocity sweeps were preferred over mean velocities for the organism detachment prediction, which were later expressed in terms of the boundary layer and fracture properties.147 The velocity gradient is described in the model of hydrodynamic forces acting on settled barnacles over a relatively smooth surface and is given by the following equation  \n\n$$\nu(z)=\\frac{u_{*}}{K}\\textcircled{1}\\frac{z}{z_{o}}\n$$  \n\nwhere $u(z)$ is the mean velocity parallel to the substrate at a distance $z$ above the surface, $u_{*}$ represents the friction velocity, K is von Karman’s constant and $z_{o}$ denotes the roughness parameter.147 Wouters et al.144 provided a simple tool for fouling-release performance evaluation of the benchmark coatings on the basis of percentage of biofilm formation; stating that the biofilm formation does not solely depend on surface wettability, as parameters like swelling characteristics need to be determined as well. The bar graph represents the performance of various formulated coatings in comparison to the reference siloxane coatings and the epoxy standard, which showed $100\\%$ performance from biofilm formation (Fig. 29).144  \n\n![](images/dbb03f4f6e490316238f56f00fad003a06dd991b85c536d5692a2002c4ed2ac9.jpg)  \nFig. 29: Performance of the coatings in relation to the respective benchmark coatings. Patterned bar $\\mathbf{\\sigma}=\\mathbf{\\sigma}$ formation of biofilm; unpatterned bar $\\mathbf{\\sigma}=\\mathbf{\\sigma}$ biofilm release.144 Copyright 2010, reproduced with kind permission from Elsevier  \n\n![](images/e97615161c29b5c08f65385f6fc6a139b79fe32c71181eeecf575f516ea32118.jpg)  \nFig. 30: A schematic of the rheometer apparatus.148 Copyright 2016, reproduced with kind permission from Elsevier  \n\nFeng Zhou et al.148 proposed an excellent way of evaluating the foul-release characteristics of the designed coatings by using rheometer apparatus (Fig. 30). This work supplies valuable evidence for the evaluation of drag-reduction efficiency for several potential applications such as foul-release, antifouling, superhydrophobicity and antidrag characteristics.148  \n\nThe antidrag performance on account of apparent boundary slippage can be evaluated by detecting a lower shear stress value, exerted over the bottom surface of the coating recorded by a process controller or an installed computer. Therefore, the drag-reduction efficiency can be estimated by the following equation  \n\n![](images/dde18c9badcaee39ab99224ac47fca548200abc8c147c82cf64e9644c8ac4d25.jpg)  \nFig. 31: Representation of the adhesion test carried out by clamping thread of the plaque, pulled apart from the substrate surface. Reprinted with kind permission from reference (77). Copyright 2016, American Chemical Society  \n\n$$\nD_{\\mathrm{E}}=\\frac{\\tau_{\\mathrm{non-slip}}-\\tau_{\\mathrm{slip}}}{\\tau_{\\mathrm{non-slip}}}\\times100\n$$  \n\nwhere $\\tau_{\\mathrm{non-slip}}$ and $\\tau_{\\mathrm{slip}}$ denote the shear stress exerted at the coating wall at no-slip and slip boundary conditions, respectively.149–152  \n\nWilker et al.77 reported a method for adhesion study which significantly extends the available toolbox used for foul-release assessments. The test was carried out to check the pull-off adhesion force of the mussels adhered to the surface of the coated panels, by clamping the threads uniformly in between the platens of the Instron 5544 materials testing machine, as depicted in Fig. 31.  \n\nThe maximum stress value obtained at the pulling rate of $10\\ \\mathrm{mm/min}$ was considered as the magnitude of removal force. Next, the adhesion of individual plaques was calculated by dividing the removal force by the area occupied by the plaque, mathematically expressed as follows:  \n\nZhang et al.94 performed an in-depth comparative analysis of five different types of commercial foulrelease coatings for their performance evaluation against two microrganisms, namely diatom and Ulva spore. Spearman’s rank correlation test was used to establish correlation and consistency between laboratory and field immersion tests. Evaluation of static and dynamic foul-release performances was done as per ASTM D 3623 and ASTM D 4939, respectively. The results of the study revealed that the value of Spearman’s coefficient $(r_{\\mathrm{{s}}})$ was between 0.975 and 0.949 for both (diatom and Ulva spore) which did not show much difference in the values, hence proving the validity of correlation.94 Kohl et al.131 enlisted the mechanical factors contributing toward the release behavior of the epoxy–silicone antifouling coatings where the release behavior of the microorganisms over the coating surface was accessed using a standard pulloff test. The significance of such tests lies in the determination of mechanical factors (like fracture energy) and thickness of the coating layer establishing an efficient mode of release of marine biofouling.122  \n\n![](images/6b33c8652d490ec41896da5b117d376113bbd2b918025d32649fb81117a10c43.jpg)  \nFig. 32: Antifouling micromixer surfaces thwarting biofouling  \n\nIn a recent research by Balazs et al.153 the surface topography of the coating when maintained like sawtooth structure, can be a breakthrough in inhibiting marine fouling without harming the environment. They assumed the coating surface as sawtooth structure and the microorganisms adhering to the surface as mobile microcapsules (Fig. 32). A constant shear force (replicated as the hydrodynamic drag of water) was applied to rupture bonds between two microcapsules, and this force also transported the separated capsules away from the water layer. This computation modeling was based on ‘‘herringbone chaotic mixers’’ to optimize the micromixer coating surfaces, utilizing the two models: the lattice Boltzmann method (LBM) for fluid dynamics and the lattice spring method (LSM) for the micromechanics of capsules. The calculated force acting between the inter-capsule bonds was termed as the Hookean spring force, and the formation or rupture of bonds was modeled through ‘‘Bell model.’’153",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# Conclusions  \n\nScience has given the world an increasingly diverse range of polymeric coatings that improve the performance and durability of metals and other industrial building materials. With an increased focus on sustainability, there has been a growing demand for highquality industrial coatings that can be applied to prefabricated and custom-built structures. The technology of long-chain molecular coatings has improved drastically since the 1960s. In the current era, marine industries use a variety of surface coatings to shield the interior and exterior of important structures. Polymeric coatings protect the treated substrate from weather, UV rays, corrosion and most importantly from marine biofouling.34 Polymeric materials play a vital role in the fabrication of protective coatings for various applications. In the field of marine application, the major contribution is made by the siloxane and fluoropolymers directing the research in safeguarding marine structures to the core. The diversified types of metals mainly aluminum, mild steel and their alloys are protected against the threats of corrosion and fouling by the implementation of surface coatings. Although much has been accomplished, urgent demands and great challenges remain to create more robust antifouling/foul-release coatings for shielding marine vessels from the adverse effects of biofouling.  \n\nPolydimethylsiloxane (PDMS)-based coatings are used to protect the base of ship hull against marine biofouling exposed for long time. The elastomeric potential application of pristine PDMS polymer is limited by the risk of adhesion failure due to its low surface energy and extremely low chemical reactivity. Thereby, with the objective of imparting desired mechanical stability by increasing the mechanical strength of PDMS, it is blended with polymers like epoxy resins. It prevents the blend coating from microcracking and establishes cohesion at the coating–metal interface. The converse of blending PDMS with epoxy resins also holds true, since the brittle character of epoxy thermosets needs to be overcome by imparting toughness through the embodiment of elastic siloxane backbone.  \n\nAmphiphilic polymers are very promising as current generation antifouling materials due to their outstanding dual-nature properties. The metallic inorganic nanoparticles and their oxides have been incorporated into the blend of polymeric systems on account of interactive filler/polymer interface. By imparting functionalization to the pristine polymers, it leads to the successful fabrication of cost-effective and reliable nonstick marine nanocomposite coatings for ship hulls.  \n\nThe role of such potential fillers has been discussed and quantified using mathematical and analytical tools. Such models help in determining the controlled biocide release mechanisms and their quantification, which are later distinguished as toxic and nontoxic systems. Also, their development would help to cut down long time duration taken by traditional empirical methods to formulate new foul-release systems. Thereby, the mathematical studies dealing with the influence of surface properties and process parameters on adhesion phenomena, responsible for easy release of fouling organisms are oriented and discussed in the last section of the review. To avoid the serious problem of ice formation on ship hulls, systems such as temperature independent foul-release coatings should be designed to remain stable and functional under deep-sea freezing temperatures. Another desirable system would include the combination of oil fouling and biofouling resistant coatings since at the stage of oil fouling, the polymeric coating properties like superhydrophobicity, mechanical stability, and others degrade and eventually fail.46 Therefore, the underlying principle of foulrelease performance evaluation, adhesion, and mechanical strength measurement under complex marine conditions should be further studied to sustain the development of robust nonfouling polymeric surface coatings for protecting marine structures.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 17,
+        "chunk": "# References  \n\n1. Telegdi, J, Trif, L, Romnszki, S, ‘‘Smart Anti-biofouling Composite Coatings for Naval Applications.’’ In: Montemor, MF (ed.) Smart Composite Coatings and Membranes, pp. 123–155. Woodhead Publishing, Sawston (2015)   \n2. Yebra, DM, Kiil, S, Dam-Johansen, K, ‘‘Antifouling Technology: Past, Present and Future Steps Towards Efficient and Environmentally Friendly Antifouling Coatings.’’ Prog. Org. Coat., 50 (2) 75–104 (2004)   \n3. Selim, MS, Shenashen, MA, El-Safty, SA, Higazy, SA, Isago, H, Elmarakbi, A, ‘‘Recent Progress in Marine FoulRelease Polymeric Nanocomposite Coatings.’’ Prog. Mater. Sci., 87 1–32 (2017)   \n4. Lejars, M, Margallian, A, Bressy, C, ‘‘Fouling Release Coatings: A Nontoxic Alternative to Biocidal Antifouling Coatings.’’ Chem. Rev., 112 (8) 4347–4390 (2011)   \n5. 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+    {
+        "id": 1,
+        "chunk": "# Acrylic coatings with surprising antifogging and frost-resisting properties†  \n\nCite this: Chem. Commun., 2013, 49, 11764  \n\nJie Zhao,a Anthony Meyer,a Li $\\mathsf{M a}^{\\mathrm{b}}$ and Weihua Ming\\*a  \n\nReceived 28th August 2013, Accepted 24th October 2013  \n\nDOI: 10.1039/c3cc46561f www.rsc.org/chemcomm  \n\nWe report an unusually effective antifogging/frost-resisting coating based on conventional acrylic polymers. The intriguing antifogging property originated from the delicate balance between the hydrophilicity and hydrophobicity of the acrylic copolymers of 2-(dimethylamino)- ethyl methacrylate and methyl methacrylate, as well as between the water-swellability of the copolymer and the cross-linked network due to ethylene glycol dimethacrylate.  \n\nMany antifogging coatings have recently been developed to mitigate fogging problems following changes in environmental conditions for a variety of applications such as eyeglasses, goggles, lenses, mirrors, and display devices in analytical and medical instruments.1–11 Most of the antifogging coatings are hydrophilic or superhydrophilic coatings, primarily due to their ability to significantly reduce light scattering by only allowing water to condensate in a thin-film-like form. Superhydrophilic coatings with water contact angles smaller than $5^{\\circ}$ demonstrate a good antifogging property, but generally require complicated procedures to fabricate surface texture,7,12–15 which is the prerequisite to obtain superhydrophilicity (except superhydrophilic $\\mathrm{TiO}_{2}$ coatings,5,6 which however require UV illumination). In addition, many coatings of this type may not resist frost formation. A superhydrophobic surface with special mosquito-eyelike topography was hypothesized to be antifogging,16 but its fabrication remains a technical challenge.  \n\nRecently, it has been demonstrated that antifogging behavior can be obtained by cleverly combining hydrophilic and hydrophobic segments in a coating, such as coatings with both perfluoroalkyl groups and poly(ethylene glycol) (PEG) segments,17 and coatings with zwitter-wettability via layer-by-layer assembly involving PEG segments.18  \n\nWhen a subject surface is in contact with moist air under different conditions (e.g., higher or lower temperature), micrometerscale water (fogging) or ice droplets (frost) may form during the first few seconds of contact. Antifogging behavior at this initial stage is extremely important, since subsequent fogging or frosting may be much less severe or even diminish since the subject has ‘‘adapted’’ to the environmental temperature and humidity after a while. With this understanding, we designed and prepared antifogging acrylic coatings, on the basis of the delicate hydrophilic–hydrophobic balance of the acrylic copolymers of methyl methacrylate (MMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA), poly(MMA-coDMAEMA), as well as the balance between the water-swellability of the copolymer and the cross-linked network due to ethylene glycol dimethacrylate (EGDMA).  \n\nIn our coatings, linear poly(MMA-co-DMAEMA) and cross-linked PEGDMA formed a semi-interpenetrated polymer network (SIPN).19 The molar ratio between the MMA and DMAEMA units was varied to tailor the hydrophilic–hydrophobic balance of the copolymer, which would enable water to diffuse through the coating, yet the polymer did not dissolve in water. In the meantime, the presence of the PEGDMA network would prevent the copolymer from being overswollen by water, thus ensuring coating stability.  \n\nWe first synthesized poly(MMA-co-DMAEMA)s by free radical polymerization (details in $\\mathrm{ESI\\dagger}$ ) with the following MMA/DMAEMA molar ratios: $50/50,40/60,30/70$ , and $20/80$ The random copolymer (as indicated by a single $T_{\\mathrm{g}},\\mathrm{ESI}\\dag$ ) was then dissolved in toluene $(10~\\mathrm{wt\\%})$ together with different amounts of EGDMA $(0.1\\mathrm{-}2\\mathrm{wt\\%}$ relative to the copolymer), spin-coated on glass slides, and finally cured by UV $(\\mathrm{ESI\\dag})$ . The final smooth coatings ( $\\sim450\\ \\mathrm{nm}$ in thickness), containing $0.5\\mathrm{wt\\%}$ polymerized EGDMA unless otherwise stated, were labeled according to the DMAEMA content; for instance, Copolymer-70 indicates that the DMAEMA molar content was $70\\%$ in the copolymer.  \n\nVarious samples were first stored in a freezer at $-20~^{\\circ}\\mathbf{C}$ for $30~\\mathrm{min}$ , and photographs were taken after the sample was exposed to ambient conditions for 5 s. The control, a hydrophilic glass, fogged severely (Fig. 1a), so did a hydrophobically (perfluoroalkyl, Rf)-modified glass (Fig. 1b). Apparently, typical hydrophobic coatings are not suitable for antifogging applications.18 The observed fog was initially frost, which turned into fog as the sample temperature increased. In sharp contrast, there was neither frost nor fog formation at all (Fig. 1c) for Copolymer-70; excellent clarity was obviously maintained. The sample Copolymer-60 showed some improvement but the antifogging performance was not as good as Copolymer-70. These results clearly suggested that the hydrophilic DMAEMA units played a crucial role in antifogging performance.  \n\n![](images/c801f18751130423e37190a11c9b83c863a2cbcb2e2c1a4e5e93ab5ef991fe6f.jpg)  \nFig. 1 Photos of different glass slides: (a) control glass, (b) Rf-modified glass, (c) Copolymer-70, and (d) Copolymer-60, first stored at $-20^{\\circ}\\mathsf C$ for $30~\\mathrm{{min}}$ and then exposed to ambient lab conditions for 5 s.  \n\nTo evaluate the antifogging performance more quantitatively, light transmission over the $400{\\mathrm{-}}700\\ \\mathrm{nm}$ range was collected on an Agilent 8453 UV-vis spectrophotometer. Prior to fogging tests, Copolymer-70 and Copolymer-60 coatings on glass exhibited light transmission as high as the control glass $(\\sim92\\%$ , Fig. 2a) over the wavelength range of $400{\\mathrm{-}}700\\ \\mathrm{nm}$ , indicating that the random copolymer layer had a negligible effect on glass transmittance. However, the transmission on the Rf-modified sample was significantly lower $(\\sim77\\%)$ .  \n\nAfter being subjected to the same frosting/fogging test as above, the light transmission was again monitored. In the case of the control glass and Rf-modified glass, the light transmission decreased to below $20\\%$ (Fig. 2b), obviously due to severe fogging/frosting. On the copolymer coating surface, there appeared to be a strong dependence of transmission on the DMAEMA content (Fig. 2b). Both Copolymer70 and Copolymer-80 maintained high transmission $(>90\\%).$ on par with the values before the fogging test, which again confirmed that fog/frost formation on these surfaces was completely suppressed. In contrast, a significant decrease in transmission was observed on Copolymer-60 and Copolymer-50, obviously due to the lower DMAEMA content in these coatings. In the copolymer coatings, the DMAEMA content should be high enough to attract water molecules to diffuse into the polymer layer; however, excessive DMAEMA units (in the case of Copolymer-80) would lead to over-swelling of the polymer by water (despite the PEGDMA network), thus reducing the stability of the coating upon contact with water. Therefore, there is a critical balance between water-swellability and coating stability, and Copolymer-70 with $70\\%$ DMAEMA in the copolymer $(T_{\\mathrm{{g}}}{:40}\\ ^{\\circ}{\\bf{C}};{\\bf{E S I}}{\\dag})$ , which was coupled with $0.5~\\mathrm{\\wt\\%}$ cross-linked PEGDMA (shown below), was the optimal coating with excellent antifogging/frostresisting performance without compromising coating stability.  \n\nTo optimize light transmission and coating stability, we varied the EGDMA content $(0.1{-}2~\\mathrm{wt\\%}$ against the copolymer content) in Copolymer-70 and subjected the samples to a similar fogging test. The light transmission of the samples with high EGDMA contents (1 and $2\\ \\mathrm{wt\\%}$ ) was significantly lower than their counterparts with lower EGDMA contents (Fig. 3). Higher EGDMA contents, after polymerization, led to a dense cross-linked network that would likely restrict the copolymer chain mobility when water molecules diffused into and swelled the copolymer, resulting in lower antifogging capability. With the lower contents of EGDMA (0.1 and $0.5\\mathrm{wt\\%}$ , the cross-link network would be more diluted (compared to the samples with higher EGDMA contents), allowing the copolymer to swell to a greater extent by water and leading to better antifogging performance. However, when the EGDMA content was too low $\\left(0.1\\mathrm{wt\\%}\\right)$ , the coating appeared to be less stable, as indicated by blushing when the coating was submerged in water for $24\\mathrm{~h~}$ . Therefore, there is also an intricate interplay between coating swellability, cross-link network, and coating stability to achieve the best possible antifogging performance for the copolymer-based coatings. Copolymer-70 with $0.5~\\mathrm{wt\\%}$ of EGDMA appeared to be the optimum combination.  \n\nTo reveal the origin of the antifogging/frost-resisting properties of the copolymer coatings, we monitored the water contact angle (CA)  \n\n![](images/e17bb970664c14c495c08c226f5392837d1d33b86263be528f324d85da2c48f6.jpg)  \nFig. 2 Light transmission at the normal incident angle for various samples: (a) as-prepared samples and (b) 5 s under ambient conditions after being stored at $-20^{\\circ}C$ for $30~\\mathrm{min}$ . The spikes in the spectra were due to the light bulb.  \n\n![](images/bf286e92af429a4776d1b561d7960988ea99f66277579d82b19035bd0511cc14.jpg)  \nFig. 3 Light transmission at the normal incident angle for Copolymer-70 with different amounts of EGDMA, 5 s under ambient conditions after being stored at $-20^{\\circ}\\mathsf C$ for $30~\\mathrm{min}$ .  \n\n![](images/beffbdbbd0a5accfdbeb60f9075b3013a1b57705f09e0f22fc3ff2f0f1603c22.jpg)  \nFig. 4 (a) Water contact angle evolution on various samples as a function of time. (b) Diameter change of the water droplet on various samples over the $600\\varsigma$ period, expressed as $\\Delta D/D_{0},$ where $\\Delta D=D-D_{0},$ and $D_{0}$ and $D$ are the initial diameter (time zero) and the diameter at different times, respectively, of the wetted area by the water droplet.  \n\nchange on these surfaces under ambient conditions. During the $600\\mathrm{~s~}$ period, all the water CAs decreased (Fig. 4a), in part due to water evaporation; for instance, CA decreased by $10^{\\circ}$ on the control glass and Rf-Si-modified glass, about $13^{\\circ}$ for Copolymer-50 and Copolymer-60. On the other hand, more than $20^{\\circ}$ of CA decrease was observed on both Copolymer-70 and -80 surfaces, clearly suggesting that some water had gone somewhere else other than getting evaporated. The initial CAs for the copolymers were $60–70^{\\circ}$ , demonstrating that a coating does not have to be superhydrophilic to be effectively antifogging (similar to recent findings by Rubner and Cohen et al.18). We also simultaneously monitored the change in the diameter of the water contact area on the surface (Fig. 4b). No change in the diameter was observed for Rf-Si-modified glass, and there was even slight decrease for the control glass. In contrast, the diameter increased on all four copolymer-based surfaces: ${\\sim}12\\%$ for Copolymer-70 and $18\\%$ for Copolymer-80, respectively, and smaller increase for other two coatings with lower DMAEMA contents over the 600 s period. This observation definitely suggests that water had diffused into the copolymer coating, causing the expansion of the droplet contact area with the polymer surface, and the more DMAEMA segments in the coating, the more significant the water diffusion became. This remarkable water-absorbing capability, coupled with the coating stability due to the cross-linked PEGDMA network, contributed to the excellent antifogging/ frost-resisting properties of Copolymer-70.  \n\nThe Copolymer-70 coating was also exposed to boiling water steam; when the time of exposure was less than 5 s, no fogging occurred, but the surface did fog after longer periods of exposure. A possible cause for the poor antifogging behavior at high temperatures is the low critical solution temperature (LCST) of DMAEMA-based polymers. Pure PDMAEMA has a LCST of 38 to $40^{\\circ}\\mathrm{C}$ in water,20 so the copolymer with $70\\%$ DMAEMA was expected to have a slightly higher LCST. When the copolymer was exposed to boiling water steam, the temperature of the copolymer would increase to be above its LCST, making the copolymer no longer hydrophilic. As a consequence, water molecules could not diffuse into the polymer layer, leading to poor antifogging performance. Work is underway to employ polymer systems without this LCST issue, to obtain antifogging coatings at high temperatures.  \n\nA possible antifogging mechanism for this new type of antifogging coatings is as follows. When molecular water in moist air from either a warmer or colder environment starts to condensate on the antifogging surface, the water molecules are immediately and rapidly absorbed into the hydrophilic segments of the copolymer (Fig. 5), not allowing (micro)droplets to form on the coating surface (fogging or frosting). Once inside the copolymer coating, water molecules may exist in the nonfreezing state,18 due to the strong polymer–water hydrogen-bonding,21,22 avoiding formation of a large light-scattering water domain.  \n\n![](images/c79ea8956be286af0af7b671ea0d9dbcc14c9daa89d2c6ed26c9a6e09f40ee42.jpg)  \nFig. 5 Schematic illustration of the antifogging mechanism in the copolymer coating.  \n\nIn conclusion, we have prepared very effective antifogging/frostresisting coatings based on simple acrylic copolymers. The experimental procedure was simple and straightforward. The antifogging/ frost-resisting properties originated from the delicate balance between the hydrophilicity and hydrophobicity of the acrylic copolymer, as well as between the water-swellability of the copolymer and the cross-linked network. Due to its simplicity, this type of coating may be widely applicable in display devices, optical lenses, eyeglasses, mirrors, and other areas.  \n\nFinancial support from USDA/NIFA is gratefully acknowledged.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 2,
+        "chunk": "# Notes and references  \n\n1 L. Zhang, Y. Li, J. Sun and J. Shen, Langmuir, 2008, 24, 10851.   \n2 L. Zhang, Z. Qiao, M. Zheng, Q. Huo and J. Sun, J. Mater. Chem., 2010, 20, 6125.   \n3 J. R. Premkumara and S. B. Khoo, Chem. Commun., 2005, 640.   \n4 N. Nuraje, R. Asmatulu, R. E. Cohen and M. F. Rubner, Langmuir, 2011, 27, 782. 5 R. Wang, K. Hashimoto, A. Fujishima, M. Chikuni, E. Kojima and A. Kitamura, Nature, 1997, 388, 431.   \n6 R. Wang, K. Hashimoto, A. Fujishima, M. Chikuni, E. Kojima, A. Kitamura, M. Shimohigoshi and T. Watanabe, Adv. Mater., 1998, 10, 135.   \n7 (a) F. C. Cebeci, Z. Z. Wu, L. Zhai, R. E. Cohen and M. F. Rubner, Langmuir, 2006, 22, 2856; (b) N. Nuraje, R. A. Asmatulu, R. E. Cohen and M. F. Rubner, Langmuir, 2011, 27, 782.   \n8 P. Chevallier, S. Turgeon, C. Sarra-Bournet, R. Turcotte and G. Laroche, ACS Appl. Mater. Interfaces, 2011, 3, 750.   \n9 X. Liu, X. Du and J. He, ChemPhysChem, 2008, 9, 305.   \n10 J. A. Howarter, K. L. Genson and J. P. Youngblood, ACS Appl. Mater. Interfaces, 2011, 3, 2022.   \n11 L. Xu and J. He, ACS Appl. Mater. Interfaces, 2012, 4, 3293.   \n12 J. Xiong, S. N. Das, J. P. Kar, J.-H. Choi and J.-M. Myoung, J. Mater. Chem., 2010, 20, 10246.   \n13 N. J. Shirtcliffe, G. McHale, M. I. Newton, C. C. Perry and P. Roach, Chem. Commun., 2005, 3135.   \n14 D. Tahk, T. Kim, H. Yoon, M. Choi, K. Shin and K. Y. Suh, Langmuir, 2010, 26, 2240.   \n15 X. Li and J. He, ACS Appl. Mater. Interfaces, 2012, 4, 2204.   \n16 X. F Gao, X. Yan, X. Yao, L. Xu, K. Zhang, J. Zhang, B. Yang and L. Jiang, Adv. Mater., 2007, 19, 2213.   \n17 J. A. Howarter and J. P. Youngblood, Macromol. Rapid Commun., 2008, 29, 455.   \n18 H. Lee, M. L. Alcaraz, M. F. Rubner and R. E. Cohen, ACS Nano, 2013, 7, 2172.   \n19 A. Aleman, et al., Pure Appl. Chem., 2007, 79, 1801.   \n20 G. Burillo, E. Bucio, E. Arenas and G. P. Lopez, Macromol. Mater. Eng., 2007, 292, 214.   \n21 H. Ohno, M. Shibayama and E. Tsuchida, Makromol. Chem., 1983, 184, 1017.   \n22 M. S. Sanchez, G. G. Ferrer, M. M. Pradas and J. L. G. Ribelles, Macromolecules, 2003, 36, 860.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# A facile approach to UV-curable super-hydrophilic polyacrylate coating film grafted on glass substrate  \n\nTao Liang, Hongqiang Li, Xuejun Lai, Xiaojing Su, Lin Zhang, Xingrong Zeng  \n\n$\\circleddash$ American Coatings Association 2016  \n\nAbstract The super-hydrophilic polymer coating film can easily be be peeled off from a substrate with the existence of water, which is a fatal drawback in practical applications. Herein, a facile approach is proposed to prepare UV-curable super-hydrophilic polyacrylate coating film that is chemically grafted on the surface of $\\gamma$ -methacryloxypropyltrimethoxysilanemodified glass substrate. Fourier transform infrared spectroscopy and scanning electron microscopy confirmed that the polyacrylate coating films were successfully grafted onto the glass substrate and exhibited rough micro-groove structure. The obtained polyacrylate coating film possessed super-hydrophilicity with the water contact angle close to nearly zero as well as good transmittance and antifogging property.  \n\nKeywords UV-curable, Polyacrylate, Glass substrate, Super-hydrophilicity, Antifogging",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# Introduction  \n\nIn recent years, super-hydrophilic materials have been paid more and more attention, due to their potential applications in biological medicine,1 water harvesting,2 self-cleaning,3 antifogging,4 electroactive material,5 and microfluidic devices.6 When a water droplet falls onto textured and/or structured materials (rough and/ or porous), it will spread completely and quickly to form a thin liquid film, and the contact angle is nearly zero, and these materials can be thought to be superhydrophilic.7  \n\nCurrently, there are three important strategies to prepare super-hydrophilic coating films. The first one, including chemical vapor deposition8 and sol–gel method,9,10 is to use the photo-chemically active materials such as $\\mathrm{TiO}_{2}$ and $\\mathrm{znO}$ that can become super-hydrophilic under ultraviolet (UV) light exposure.11–13 However, when the film is placed in a dark environment, it will lose the super-hydrophilicity within a few hours. The second one, including layerby-layer assembly14 and electrostatic spinning,15 is to fabricate or modify the surface chemical and geometric microstructure into a texture surface or porous films, which can absorb the water on solid surface and promote the residual water droplet to spread out on the interface of solid and water. Unfortunately, the above two methods require harsh reagents16 and multistep processes,17 and are hard for end-use. The third one is to directly prepare super-hydrophilic polymer coating films using hydrophilic monomers such as acrylic acid,18 poly(ethylene glycol) monomethacrylate,19 and 2-(methacryloyloxy) ethyl phosphorycholine20 by UV-initiated polymerization. Due to the low cost,21 simple process,22 high efficiency, and lack of pollution,23 this method is considered as a very promising one to prepare the super-hydrophilic coating films. However, it is difficult to obtain superhydrophilicity only with the hydrophilic monomers. Furthermore, the obtained super-hydrophilic coating films are easy to be peeled off from the substrate with the existence of water, which is a fatal drawback in practical application.  \n\nIn this article, we first used a piranha solution to treat glass substrate so as to increase the number of hydroxyl groups, and then the substrate was further modified by $\\gamma$ -methacryloxypropyltrimethoxysilane (MPS) to introduce $C{=}\\dot{C}$ double bond. The superhydrophilic polyacrylate coating films chemically grafted onto glass substrate was prepared with 2- methacrylatoethyl trimethyl ammonium chloride (DMC) and trimethylolpropane triacrylate (TMPTA) as hydrophilic monomer and crosslinker, respectively, by UV-initiated polymerization. The chemical structure and micromorphology of the film were characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM); the effect of the contact time and monomer ratio on the contact angle were studied; the transmittance and antifouling property were also investigated.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# Experimental",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# Materials  \n\n2-Methacrylatoethyl trimethyl ammonium chloride (DMC, $72\\mathrm{\\mt{\\%}}$ in water solution) was purchased from General Electric Co., Ltd (USA). TMPTA, MPS, and 2-hydroxy-2-methylpropiophenone (Darocur 1173) were provided by Aladdin Reagent Co., Ltd (China). Sulfuric acid $\\mathrm{(H}_{2}\\mathrm{SO}_{4}$ , $98\\%$ ) and ethanol were purchased from Guangzhou Chemical Reagent Factory (China). Hydrogen peroxide $\\left(\\mathrm{H}_{2}\\mathrm{O}_{2}\\right)$ , $30\\%$ ) was supplied by Chinasu Specialty Products $\\mathbf{\\boldsymbol{C}}\\mathbf{\\boldsymbol{o}}$ , Ltd (China). Glass slide was purchased from Chinasu Sail Brand Products $\\mathrm{Co}$ ., Ltd (China); the length, width, and thickness were 76.2, $25.4~\\mathrm{mm}$ , and $1{-}1.2~\\mathrm{mm}$ , respectively. All materials were used as received without further purification.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# Modification of glass substrate  \n\nGlass slides were first treated by submerging in a freshly prepared piranha solution containing $70\\%$ $\\mathrm{H}_{2}\\mathrm{SO}_{4}$ and $\\hat{30\\%}$ $\\bar{\\mathbf{H}_{2}\\mathbf{O}_{2}}$ at $90^{\\circ}\\mathrm{C}$ for $^{\\textrm{1h}}$ , and then rinsed with copious amounts of deionized water, and the hydroxylated glass substrates were obtained.24 Then, $\\boldsymbol{10}\\ \\mathrm{g}$ MPS was added into $190~\\mathrm{g}$ ethanol solution $(V_{\\mathrm{ethanol}}/V_{\\mathrm{water}}=2)$ in a $500~\\mathrm{mL}$ beaker and stirred for $^{1\\mathrm{~h~}}$ at room temperature. Subsequently, the solution was heated to $70^{\\circ}\\mathrm{C}$ , the hydroxylated glass substrates were put into and kept for $45~\\mathrm{{min}}$ , then taken out and placed in a vacuum oven at $110^{\\circ}\\mathrm{C}$ for $^\\textrm{\\scriptsize1h}$ for further reaction. At last, the glass substrates were thoroughly rinsed with ethanol by ultrasonic for three times at room temperature, then dried in vacuum oven at $40^{\\circ}\\mathrm{C}$ for $24\\mathrm{~h~}$ , and the MPS-modified glass substrates were prepared.25",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# Preparation of super-hydrophilic polyacrylate coating films chemically grafted on glass substrate  \n\nAppropriate amount of DMC solution, TMPTA, Darocur 1173, and ethanol were uniformly mixed, and the obtained solution was dripped and scraped onto the MPS-modified glass substrate by flat-plate knife coater, and then exposed at UV light (INTELLIRAY 400, Uvitron International, Inc., USA) for $400\\ \\mathrm{s}$ ； the distance between the samples and the center of the UV light lamp was $15\\ \\mathrm{cm}$ . With ethanol evaporating and the occurrence of UV-curing reaction, the films with the average thickness at $13\\pm1~{\\upmu\\mathrm{m}}$ were obtained. The formulations for UV-curable super-hydrophilic polyacrylate coating films are listed in Table 1, and the preparation process for the superhydrophilic coating films chemically grafted on glass substrate is shown in Fig. 1.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# Characterization  \n\nTo confirm the chemical structure of the modified glass and the glass with super-hydrophilic polyacrylate coating film, FTIR was carried on a Tensor 27 (Bruker, Germany) spectrometer. The spectra were acquired over the range $4000{\\mathrm{-}}600~{\\mathrm{cm}}^{-1}$ , the scanning was performed with a resolution of $4~\\mathrm{cm}^{-1}$ , and all the spectra were collected 48 times to ensure accuracy.  \n\nAccording to reference 26, sessile drop contact angle measurement was performed with deionized water using DSA100 contact angle analyzer (KRUSS, Germany) equipped with a video capture. A total of $1~\\upmu\\mathrm{L}$ of deionized water was dropped onto a dry coating film with a micro-syringe at room temperature. The obtained water contact angles were the mean values measured from five different places on the surface. All water contact angle measurements were performed in room temperature with the humidity of $20{-}40\\%$ .  \n\nThe morphology of the coating film was observed with Phenom TM scanning electron microscope (FEI, Holland) at an accelerated voltage of $5\\mathrm{kV}$ . The chemical composition of the prepared coating films was measured by energy dispersive $\\mathbf{X}$ -ray spectroscopy (EDS) performed in SEM. All the samples were sputtering coated with Au prior to observation.  \n\nTable 1: Formulations for UV-curable super-hydrophilic polyacrylate coating films   \n\n\n<html><body><table><tr><td>Samples</td><td>Mass (DMC)/Mass (TMPTA)</td><td>DMC solution (g)</td><td>TMPTA (g)</td><td>Darocur 1173 (g)</td><td>Ethanol (g)</td></tr><tr><td>S1</td><td>9/1</td><td>4.0</td><td>0.32</td><td>0.16</td><td>20.0</td></tr><tr><td>S2</td><td>8/2</td><td>4.0</td><td>0.72</td><td>0.16</td><td>20.0</td></tr><tr><td>S3</td><td>7/3</td><td>4.0</td><td>1.23</td><td>0.16</td><td>20.0</td></tr><tr><td>S4</td><td>6/4</td><td>4.0</td><td>1.92</td><td>0.16</td><td>20.0</td></tr><tr><td>S5</td><td>5/5</td><td>4.0</td><td>2.88</td><td>0.16</td><td>20.0</td></tr></table></body></html>  \n\n![](images/11b0beb6d565b9035e540bfd9d361ceeefd8e110ffa3007ef9f70f766bdbda9e.jpg)  \nFig. 1: Schematic for UV-curable super-hydrophilic polyacrylate coating film chemically grafted on glass substrate  \n\n![](images/39d202665c472648ff2c62e9b8b651359c4310fb11b863992f0721608dca8e8d.jpg)  \nFig. 2: FTIR spectra of (a) pure glass, (b) MPS-modified glass, and (c) UV-curable polyacrylate coating film (S2) chemically grafted on glass substrate  \n\nUV-Vis spectra were recorded using Lambda 950 UV-Vis–NIR spectrometer (PE, America), with air as reference. The transmission of wavelength ranged from 300 to $800\\ \\mathrm{nm}$ , which was taken to evaluate the film transparency.  \n\nIn order to measure the antifogging property, the pure glass and the glass grafted with super-hydrophilic coating film were cooled at $-18^{\\circ}\\mathrm{C}$ in a refrigerator for  \n\n$30~\\mathrm{{min}}$ and then moved to atmospheric environment with the humidity of $20{-}40\\%$ . After $90~\\mathrm{s}$ the images were taken using Nex-5T camera (Sony, Japan).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# Results and discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# FTIR analysis  \n\nFTIR spectra of pure glass, MPS-modified glass, and UV-curable polyacrylate coating film (S2) chemically grafted on glass substrate are shown in Fig. 2. Compared to the spectrum of pure glass, two new absorption peaks at 1727 and $164\\dot{0}~\\mathrm{cm}^{-1}$ were observed in the spectrum of MPS-modified glass, which were attributed to the carboxyl group and $\\scriptstyle\\mathbf{C}=\\mathbf{C}$ bonds, respectively. The peaks at 938 and $1481~\\mathrm{cm}^{-1}$ were ascribed to the stretching vibration of $\\mathrm{\\mathbf{Si}\\mathrm{-}\\mathbf{OH}}$ and deformation vibration of $\\mathrm{CH}_{2}$ , and the peak at $1155~\\mathrm{cm}^{-1}$ was probably assigned to the asymmetric stretching vibration of $\\mathrm{Si-}$ $\\mathrm{\\Gamma}_{\\mathrm{{O-}\\bar{\\mathrm{{Si}}}}}$ from the reaction of functional groups between MPS and hydroxylated glass.26 In the spectrum of S2, the absorption peak at $1092~\\mathrm{cm}^{-1}$ was assigned to quaternary ammonium in DMC, and the characteristic peaks between 2850 and $2925~\\mathrm{{cm}^{-1}}$ were ascribed to $\\mathrm{\\bar{C}\\mathrm{-}H}$ stretching vibration from $\\mathrm{CH}_{3}$ and $\\mathrm{CH}_{2}$ in DMC and TMPTA. Furthermore, the strong absorption peaks at 1725 and $1300~\\mathrm{cm}^{-1}$ , which were attributed to the stretching vibration of $\\scriptstyle\\mathbf{C=O}$ and $\\scriptstyle{\\mathrm{C-O}}$ in DMC and TMPTA, were also observed, indicating that DMC and TMPTA had been successfully grafted onto the modified glass.  \n\n![](images/709b07fa9f48300c987b521845d4da9601ed37a4d898b09fe63608aa06060d0e.jpg)  \nFig. 3: SEM images of super-hydrophilic polyacrylate coating film (S2) acquired at (a) ${\\pmb5000}\\times$ magnification, EDS analyses of the film on the electron image with mapping of (b) carbon, (c) oxygen, and (d) chloride elements  \n\n![](images/73b9b21e6e7541f63e636a3e6a755e241c4cfd6f2362240080c3078176a20ecc.jpg)  \nFig. 4: Images for water contact angle of (a) pure glass and (b) MPS-modified glass; Images for water contact angle of the glass coated with S2 at (c) 0 s and (d) 2.5 s",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# Surface morphology  \n\nFigure 3 shows SEM images of super-hydrophilic polyacrylate coating film (S2), and EDS analyses of the film on the electron image with mapping of (b) carbon, (c) oxygen, and (d) chloride elements. As seen in Fig. 3a, the super-hydrophilic polyacrylate coating film exhibited obvious rough micro-groove structure. It might be related to the volatilization of ethanol and the formation of the crosslinking structure during the UVcuring process. It is known that increasing roughness is beneficial for the improvement of the hydrophilicity of hydrophilic solid surface.27 For example, in order to improve hydrophilicity, Dong et al. incorporated silica nanoparticles into the polymer coating film to increase roughness.28 Undoubtedly, to fabricate roughness is one of the most robust and efficient methods to improve the hydrophilicity of the coating films. From EDS mapping images shown in Figs. 3b–d, it demonstrate that $67.10~\\mathrm{wt\\%}$ of carbon, $21.25~\\mathrm{wt\\%}$ of oxygen, and $11.65~\\mathrm{wt\\%}$ of chloride elements are uniformly distributed on the surface of coating film. Furthermore, Si element is not detected, indicating that the modified glass substrate is covered completely by the coating film.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# Super-hydrophilicity  \n\nThe super-hydrophilicity of pure glass, MPS-modified glass, and the UV-curable super-hydrophilic polyacrylate coating film was investigated by a contact angle analyzer. The images for water contact angle of pure glass and MPS-modified glass are presented in Figs. 4a and b. The water contact angle of the pure glass and MPS-modified glass are at almost $3\\bar{1}^{\\circ}$ and $74.5^{\\circ}$ , respectively. Obviously, the MPS-modified glass is more hydrophobic than pure glass, which is due to the hydrophobic MPS. This result also indicates that  \n\nMPS was successfully grafted onto the glass surface. Figures $_{4\\mathrm{c}}$ and d show the images for water contact angle of the glass coated with S2 at 0 and $2.5\\mathrm{~s~}$ . When the contact time increased from 0 to $2.5\\mathrm{~s~}$ , the water contact angle rapidly decreased from almost $180^{\\circ}$ to less than $10^{\\circ}$ , which verified the super-hydrophilicity of the film S2. It may be due to the following reasons: the first one was the roughness of the coating film (see Fig. 3), which plays an important role for superhydrophilicity.29,30 The second one was the crosslinking network structure formed during the UV-curing process. In addition, the existence of the hydrophilic groups, such as cationic monomer DMC and trimethyl ammonium ions, also plays a role for the superhydrophilicity of the coating film.  \n\nIn order to further investigate the super-hydrophilicity of the UV-curable polyacrylate coating film, the evolution of contact angle and base diameter of water drops with contact time on the coating film were investigated, as shown in Fig. 5. It is easy to observe the occurrence of water contact angle hysteresis caused by capillary phenomena.31 Before $\\mathrm{10~\\dot{s}}{}_{\\mathrm{;}}$ , with contact time increasing, the water contact angle decreased considerably to nearly zero and the base diameter of the water droplet increased rapidly. With contact time further increasing, the water contact angle was almost unchangeable, while the base diameter still kept an increasing tendency, though the increasing rate had a little decrease. This phenomenon can be explained as follows: when water droplet contacted the film, the hydrophilic groups introduced by DMC quickly adsorbed the water, and then transferred water to its surrounding, which led to the rapid decrease of the water contact angle and the increase of the base diameter of the water droplet. With contact time increasing, the water would flow into and fill the near micro-grooves and crosslinking network,32 and then the rest of the water would further spread to the larger area. At this stage, the water contact angle was almost unchanged, while the base diameter of the water droplet still increased.  \n\n![](images/629a61d7c3ab782878bfd4458dc4fe93d861f500f0d0961090eb23fc61ebe2d7.jpg)  \nFig. 5: Evolution of contact angle and base diameter of water drops with contact time on UV-curable polyacrylate coating film (S2)  \n\nFigure 6 shows the effect of mass(DMC)/- mass(TMPTA) on water contact angle of the UVcurable polyacrylate coating films. With mass(DMC)/- mass(TMPTA) decreasing from $9/1$ to 5/5, the water contact angle decreased first and increased later. When the mass ratio was at $8/2$ , the water contact angle reached the lowest value of near zero. Under the irradiation of UV light and the initiation role of Darocur 1173, DMC not only reacts with TMPTA and MPS grafted on glass substrate, but also reacts with itself, which will have a large effect on the formation of the micro-groove structure and the crosslinking degree of the coating film. In particular, low crosslinking degree is beneficial for the water penetrating into the crosslinking structure of the film, while high crosslinking degree restrains the water into the crosslinking structure. Therefore, with mass(DMC)/mass(TMPTA) increasing from $9/1$ to 8/2, the crosslinking degree increased and the dense network was formed, which resulted in the decrease of the contact angle.33 However, with the further increase of mass(DMC)/- mass(TMPTA), the contact angle increased instead.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# Transmittance  \n\nTransmittance is one of the important factors for the practical applications of the super-hydrophilic coating films, especially in the fields with high requirements on safety and appearance, such as auto windshields and glass curtain wall. Figure 7 shows UV-Vis spectra and optical photographs of pure glass and the glass grafted with super-hydrophilic polyacrylate coating films. From UV-Vis spectra shown in Fig. 7, the transmittance of the glass grafted with super-hydrophilic polyacrylate coating films were a little lower than that of pure glass between 300 and $400~\\mathrm{nm}$ . However, when the wavelength was above $400~\\mathrm{nm}$ , the transmittance was almost same. The slightly low transmittance of super-hydrophilic coating films between 300 and $400~\\mathrm{nm}$ should be due to the roughness of the film, which resulted in the higher light scattering. However, the refractive index of the polymer was lower than that of pure glass, which was beneficial for the improvement of the transmittance. In addition, from the inserted optical photographs, it can be seen that there was no difference between the two photographs, and the glass grafted with the super-hydrophilic polyacrylate coating films exhibited the same good transmittance as pure glass.  \n\n![](images/a1af2e66b8626621174d6402be39c19fa5294e7d65768aa24faa65940100c651.jpg)  \nFig. 6: Effect of mass(DMC)/mass(TMPTA) on water contact angle of UV-curable polyacrylate coating films  \n\n![](images/d97f87b0ff7c84e20fc049283840d5e38914690fe6805da8a5592062f7adc1cc.jpg)  \nFig. 7: UV-Vis spectra of pure glass, glass grafted with S1, S2, and S3, and the insert shows an optical photographs of pure glass (left) and the glass grafted with S2 (right)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# Antifogging property  \n\nAntifogging property is important for the surfaces that need to be free of fog to reduce safety hazards. Figure 8 shows antifogging images for pure glass and the glass chemically grafted with UV-curable superhydrophilic polyacrylate coating film. It is obvious that pure glass was easy to be fogged and became illegible, whereas the glass grafted with UV-curable superhydrophilic polyacrylate coating film still remained clear and exhibited excellent antifogging property, which was because the condensed water droplets could rapidly spread out on the super-hydrophilic coating film and the probable light scatting phenomenon was eliminated. More importantly, the films are chemically grafted onto the surface of glass substrate, so it is durable in practical applications, even if being used at humid environment or with the existence of water.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# Conclusion  \n\nA UV-curable super-hydrophilic polyacrylate coating film chemically grafted onto the MPS-modified glass substrate was successfully prepared using DMC and TMPTA as hydrophilic monomer and crosslinker, respectively. The UV-curable super-hydrophilic polyacrylate coating film appeared as a rough micro-groove structure and possessed super-hydrophilicity. With mass(DMC)/mass(TMPTA) decreasing, the water contact angle of the coating films decreased first and increased latterly. When the mass ratio was $8/2$ , the water contact angle reached the lowest value at nearly zero. The UV-curable super-hydrophilic polyacrylate coating film also exhibited excellent transmittance and antifogging property. This approach to prepare the UV-curable super-hydrophilic polymer coating film has the characteristic of high efficiency and simplicity, which are needed in practical applications. Besides glass, the UV-curable polymer coating film can also be chemically grafted onto other inorganic or metal substrates modified by silane coupling agent.  \n\n![](images/628175e4f29b290c079a06bbdf7fff25a736d47421cb828d84b051e4b00e50d6.jpg)  \nFig. 8: Antifogging images of (a) pure glass and (b) glass grafted with S2",
+        "category": " Conclusions"
+    },
+    {
+        "id": 15,
+        "chunk": "# References  \n\n1. Manabe, K, Nishizawa, S, Kyung, KH, Shiratori, S, ‘‘Optical Phenomena and Antifrosting Property on Biomimetics Slippery Fluid-Infused Antireflective Films Via Layer-by-Layer Comparison with Superhydrophobic and Antireflective Films.’’ ACS Appl. Mater. Interfaces, 6 (16) 13985–13993 (2014)   \n2. Liu, G, Cai, M, Wang, X, Zhou, F, Liu, W, ‘‘Core-ShellCorona-Structured Polyelectrolyte Brushes-Grafting Magnetic Nanoparticles for Water Harvesting.’’ ACS Appl. Mater. Interfaces, 6 (14) 11625–11632 (2014)   \n3. Huang, JJ, Lee ‘‘Self-Cleaning and Antireflection Properties of Titanium Oxide Film by Liquid Phase Deposition.’’ Surf. Coat. Technol., 231 (25) 257–260 (2013)   \n4. Zhou, G, He, J, Xu, L ‘Antifogging Antireflective Coatings on Fresnel Lenses by Integrating Solid and Mesoporous Silica Nanoparticles.’’ Micropor. Mesopor. Mat., 176 41–47 (2013)   \n5. Shankar, R, Ghosh, TK, Spontak, RJ, ‘‘Electromechanical Response of Nanostructured Polymer Systems with No Mechanical Pre-Strain.’’ Macromol. Rapid. Comm., 28 (10) 1142–1147 (2007)   \n6. Goel, P, Kumar, S, Sarkar, J, Singh, JP, ‘‘Mechanical Strain Induced Tunable Anisotropic Wetting on Buckled PDMS Silvernanorods Arrays.’’ ACS Appl. Mater. Interfaces, 7 (16) 8419–8426 (2015)   \n7. Drelich, J, Chibowski, E, ‘‘Superhydrophilic and Superwetting Surfaces: Definition and Mechanisms of Control.’’ Langmuir, 26 (24) 18621–18623 (2010)   \n8. Sobczyk-Guzenda, A, Szymanowski, H, Jakubowski, W, Błasin´ ska, A, Kowalski, J, Gazicki-Lipman, M, ‘‘Morphology, Photocleaning and Water Wetting Properties of Cotton Fabrics, Modified with Titanium Dioxide Coatings Synthesized with Plasma Enhanced Chemical Vapor Deposition Technique.’’ Surf. Coat. Technol., 217 51–57 (2013)   \n9. Chen, Y, Zhang, C, Huang, W, Yang, C, Huang, T, Situ, Y, Huang, H, ‘‘Synthesis of Porous $\\mathrm{ZnO/TiO}_{2}$ Thin Films with Superhydrophilicity and Photocatalytic Activity Via a Template-Free Sol–Gel Method.’’ Surf. Coat. Technol., 258 531– 538 (2014)   \n10. Lim, HS, Kwak, D, Lee, DY, Lee, SG, Cho, K, ‘‘UV-Driven Reversible Switching of a Roselike Vanadium Oxide Film Between Superhydrophobicity and Superhydrophilicity.’’ $J.$ . Am. Chem. Soc., 129 (14) 4128–4129 (2007)   \n11. Wang, R, Hashimoto, K, Fujishima, A, Chikuni, M, Kojima, E, Kitamura, A, Shimohigoshi, M, Watanabe, T, ‘‘LightInduced Amphiphilic Surfaces.’’ Nature, 388 431–432 (1997)   \n12. Fujishima, A, Zhang, X, Tryk, DA, ‘ $\\mathrm{TiO}_{2}$ Photocatalysis and Related Surface Phenomena.’’ Surf. Sci. Rep., 63 (12) 515– 582 (2008)   \n13. Lai, Y, Tang, Y, Gong, J, Gong, D, Chi, L, Lin, C, Chen, Z, ‘‘Transparent Superhydrophobic/Superhydrophilic $\\mathrm{TiO}_{2}$ - Based Coatings for Self-Cleaning and Anti-fogging.’’ $J.$ Mater. Chem., 22 7420–7428 (2012)   \n14. de Leon, A, Advincula, RC, ‘‘Reversible Superhydrophilicity and Superhydrophobicity on a Lotus-Leaf Pattern.’’ ACS Appl. Mater. Interfaces, 6 (24) 22666–22672 (2014)   \n15. Raza, A, Ding, B, Zainab, G, El-Newehy, M, Al-Deyab, SS, Yu, J, ‘‘In situ crosslinked Superwetting Nanofibrous MemA, 2 10137–10145 (2014)   \n16. Yang, J, Yin, L, Tang, H, Song, H, Gao, X, Liang, K, Li, C, ‘‘Polyelectrolyte-Fluorosurfactant Complex-Based Meshes with Superhydrophilicity and Superoleophobicity for Oil/ Water Separation.’’ Chem. Eng. J., 268 245–250 (2015)   \n17. Cebeci, FC¸ , Wu, Z, Zhai, L, Cohen, RE, Rubner, MF, ‘‘Nanoporosity-Driven Superhydrophilicity: A Means to Create Multifunctional Antifogging Coatings.’’ Langmuir, 22 (6) 2856–2862 (2006)   \n18. Kessler, F, Kuhn, S, Radtke, C, Weibel, DE, ‘‘Controlling the Surface Wettability of Poly(sulfone) Films by UVAssisted Treatment: Benefits in Relation to Plasma Treatment.’’ Polym. Int., 62 (2) 310–318 (2013)   \n19. Homayoonfal, M, Akbari, A, Mehrnia, MR, ‘‘Preparation of Polysulfone Nanofiltration Membranes by UV-Assisted Grafting Polymerization for Water Softening.’’ Desalination, 263 (1–3) 217–225 (2010)   \n20. Yang, B, Duan, X, Huang, J, ‘‘Ultrathin, Biomimetic, Superhydrophilic Layers of Crosslinked Poly(phosphobetaine) on Polyethylene by Photografting.’’ Langmuir, 31 (3) 1120–1126 (2015)   \n21. Abuhabib, AA, Mohammad, AW, Hilal, N, Rahman, RA, Shafie, AH, ‘‘Nanofiltration Membrane Modification by UV Grafting for Salt Rejection and Fouling Resistance Improvement for Brackish Water Desalination.’’ Desalination, 295 16–25 (2012)   \n22. Ge, J, Lee, H, He, L, Kim, J, Lu, Z, Kim, H, Goebl, J, Kwon, S, Yin, Y, ‘‘Magnetochromatic Microspheres: Rotating Photonic Crystals.’’ J. Am. Chem. Soc., 131 (43) 15687– 15694 (2009)   \n23. Wolpers, A, Vana, P, ‘‘UV Light as External Switch and Boost of Molar-Mass Control in Iodine-Mediated Polymerization.’’ Macromolecules, 47 (3) 954–963 (2014)   \n24. Guo, W, Ruckenstein, E, ‘‘Modified Glass Fiber Membrane and its Application to Membrane Affinity Chromatography.’’ J. Membr. Sci., 215 (1–2) 141–155 (2003)   \n25. Chen, Z, Chen, F, Zeng, F, Li, J, ‘‘Preparation and Characterization of the Charged $\\mathrm{PDMC}/\\mathrm{Al}_{2}\\mathrm{O}_{3}$ Composite Nanofiltration Membrane.’’ Desalination, 349 106–114 (2014)   \n26. Ghicov, A, Schmuki, P, ‘‘Self-Ordering Electrochemistry: A Review on Growth and Functionality of $\\mathrm{TiO}_{2}$ Nanotubes and Other Self-Aligned $\\mathbf{MO}_{x}$ Structures.’’ Chem. Commun., 20 2791–2808 (2009)   \n27. Wenzel, RN, ‘‘Resistance of Solid Surfaces to Wetting by Water.’’ Ind. Eng. Chem., 28 (8) 988–994 (1936)   \n28. Dong, H, Ye, P, Zhong, M, Pietrasik, J, Drumright, R, Matyjaszewski, K, ‘‘Superhydrophilic Surfaces Via Polymer$\\mathrm{SiO}_{2}$ Nanocomposites.’’ Langmuir, 26 (19) 15567–15573 (2010)   \n29. Wu, Z, Lee, D, Rubner, MF, Cohen, RE, ‘‘Structural Color in Porous, Superhydrophilic, and Self-Cleaning $\\mathrm{SiO}_{2}/\\mathrm{TiO}_{2}$ Bragg Stacks.’’ Small, 3 (8) 1445–1451 (2007)   \n30. Liu, X, Du, X, He, J, ‘‘Hierarchically Structured Porous Films of Silica Hollow Spheres Via Layer-By-Layer Assembly and their Superhydrophilic and Antifogging Properties.’’ Chemphyschem, 9 (2) 305–309 (2008)   \n31. Volpe, CD, Siboni, S, ‘‘A ‘Conveyor Belt’ Model for the Dynamic Contact Angle.’’ Eur. J. Phys., 32 (4) 1019–1032 (2011)   \n32. Shimizu, T, Goda, T, Minoura, N, Takai, M, Ishihara, K, ‘‘Super-Hydrophilic Silicone Hydrogels with Interpenetrating Poly(2-Methacryloyloxyethyl Phosphorylcholine) Networks.’’ Biomaterials, 31 (12) 3274–3280 (2010)   \n33. Cai, M, Zhang, J, Chen, Y, Cao, J, Leng, M, Hu, S, Luo, X, ‘‘Preparation and Characterization of Chitosan Composite Membranes Crosslinked by Carboxyl-Capped Poly(Ethylene Glycol).’’ Chin. J. Polym. Sci., 32 (2) 236–244 (2014)",
+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,32 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Multifunctional “Hydrogel Skins” on Diverse Polymers with Arbitrary Shapes  \n\nYan Yu, Hyunwoo Yuk, German A. Parada, You Wu, Xinyue Liu, Christoph S. Nabzdyk, Kamal Youcef-Toumi, Jianfeng Zang, and Xuanhe Zhao\\*  \n\nSlippery and hydrophilic surfaces find critical applications in areas as diverse as biomedical devices, microfluidics, antifouling, and underwater robots. Existing methods to achieve such surfaces rely mostly on grafting hydrophilic polymer brushes or coating hydrogel layers, but these methods suffer from several limitations. Grafted polymer brushes are prone to damage and do not provide sufficient mechanical compliance due to their nanometer-scale thickness. Hydrogel coatings are applicable only for relatively simple geometries, precluding their use for the surfaces with complex geometries and features. Here, a new method is proposed to interpenetrate hydrophilic polymers into the surface of diverse polymers with arbitrary shapes to form naturally integrated “hydrogel skins.” The hydrogel skins exhibit tissue-like softness (Young’s modulus $\\approx30\\left\\lvert\\mathsf{k P a}\\right\\rvert$ ), have uniform and tunable thickness in the range of $5-25\\upmu\\mathrm{m}$ , and can withstand prolonged shearing forces with no measurable damage. The hydrogel skins also provide superior low-friction, antifouling, and ionically conductive surfaces to the polymer substrates without compromising their original mechanical properties and geometry. Applications of the hydrogel skins on inner and outer surfaces of various practical polymer devices including medical tubing, Foley catheters, cardiac pacemaker leads, and soft robots on massive scales are further demonstrated.  \n\nPolymer-based devices with complex geometry are ubiquitous in a wide range of areas including bioengineering,[1] medical and clinical devices,[2,3] microfluidics,[4] and soft robotics.[5,6] In many applications, these polymer devices are used in close contact with human body. For instance, the intravenous delivery of therapeutic fluids, a routine procedure for hospitalized patients, is accomplished by using different types of vascular catheters.[7] Moreover, soft robotic devices such as heart sleeves[8] and drug delivery reservoirs[9] have been recently proposed as surgically implantable devices. However, the majority of polymers used in these devices (e.g., polypropylene, polyethylene, poly(vinyl chloride) (PVC), polyurethane (PU), silicone rubbers, and natural rubbers) have much higher elastic moduli (e.g., Young’s modulus of $1\\ \\mathrm{MPa}$ to 1  GPa) than that of soft tissues in human body (e.g., Young’s modulus of 1 to $100~\\mathrm{kPa})$ .[10,11] This stark mismatch in mechanical properties, coupled with the lack of biofunctionality, gives rise to numerous issues and complications during their clinical use such as tissue trauma, biofouling, thrombosis, and foreign-body reaction.[1,2,12–17] To address these shortcomings, it is necessary to modify the device surfaces to better match the properties of biological tissues.[2,13,18]  \n\nThe most common strategy for surface modification involves grafting hydrophilic polymer chains (such as poly(N-vinylpyrolidone) or poly (ethylene oxide)/poly(ethylene glycol)) to the polymeric surfaces.[17,19–21] The resulting surfaces are hydrophilic and lubricious due to the water absorption of the grafted polymers, and show improved antifouling properties as compared to uncoated surfaces.[17,21] These coatings, however, are only a few nanometers thick and do not decrease the hardness of the underlying polymeric surface (Figure S1, Supporting Information). Moreover, the grafted polymers are prone to damage when subjected to abrasion, shearing or other mechanical loading. More recently, omniphobic surface coatings based on liquid-filled microstructures have been adopted for various materials and devices to provide nonstick, slippery, and antifouling properties.[22–24] While these liquid-infused coatings exhibit better mechanical robustness than the grafted polymers, they fail to provide tissue-matching properties such as mechanical compliances or high water contents.[22]  \n\nAnother common strategy involves coating hydrogel layers on the surfaces of devices,[8,25–27] owing to hydrogels’ favorable similarities with biological tissues in mechanical and chemical properties.[18,28–30] Given its straightforward but effective nature, interfacial bonding between the hydrogels and the polymer substrates has been one of the most widely utilized strategies to introduce soft hydrogel coatings on diverse polymer devices.[25,26,31–33] In this approach, hydrogel coatings are typically introduced to the polymer devices either in form of solid preformed crosslinked networks[25,27,32,33] or liquid pregel solutions that are then cured on the surface.[26,31] Recent advances in robust interfacial bonding between tough hydrogels and diverse polymers have enabled hydrogel coatings with improved mechanical robustness,[25,26,31] solving previously existing issues of poor hydrogel–substrate adhesion and poor mechanical properties of common hydrogels. However, there are still unresolved challenges. Hydrogel coatings fabricated by molding or dip-coating typically result in relatively thick hydrogel layers (over $50~{\\upmu\\mathrm{m}}$ ), with shapes determined by the shape of the mold or dip-coated surface used. These challenges greatly hinder the ability to conformally adapt to devices with complex surface geometries and fine features (Figure S1, Supporting Information).  \n\nHere, we report a simple yet effective strategy to interpenetrate crosslinked hydrophilic polymers (namely “hydrogel skins”) into the surfaces of diverse polymers including silicone rubbers, polyurethane, PVC, nitrile rubber, and natural rubber with arbitrary shapes. Owing to the unique combination of hydrophobic (i.e., water insoluble) initiators absorbed to the polymer surfaces and hydrophilic (i.e., water soluble) initiators dissolved in the hydrogel pregel solution, the hydrogel skins can be formed in situ on the surfaces, conformally adapting to complex and fine geometries of the polymer substrates. The resultant hydrogel skins exhibit micrometer-scale tunable thickness ranging from 5 to $25~{\\upmu\\mathrm{m}}$ with tissue-like softness (Young’s modulus $\\approx~30~\\mathrm{\\kPa}_{\\mathrm{\\ell}}$ ) and mechanical robustness. The proposed method can impart superior low-friction, antifouling, and ionically conductive surfaces to polymer devices without altering their original bulk mechanical properties or geometries. We further demonstrate applications of the hydrogel skins on various practical polymer devices with complex geometries including medical tubing, Foley catheters, cardiac pacemaker leads, and soft robots.  \n\nThe essential idea and procedures for coating the hydrogels skins are illustrated in Figure 1. Unlike the existing methods of grafting polymer brushes or bonding separate hydrogel layers, we introduce a thin and uniform hydrogel-polymer interpenetrated layer on the outermost surface of polymer substrates. In order to achieve successful formation of the hydrogel skins, we adopt an interfacial interpenetration strategy based on a combination of surface-absorbed hydrophobic (i.e., water insoluble) initiators for the polymer substrates and hydrophilic (i.e., water soluble) initiators for the hydrogel pregel solutions. We first introduce a surface-bound diffusion layer of hydrophobic initiators on the pristine polymer substrates by treating their surfaces with $10\\ \\mathrm{wt\\%}$ hydrophobic photo- or thermoinitiators (e.g., benzophenone, 4-methyl benzophenone, benzoyl peroxide, azobisisobutyronitrile) in organic solution (e.g., ethanol, isopropanol, acetone) via swelling-driven surface absorption.[25,34] Then, the treated polymer substrates are fully immersed into a hydrogel pregel solution bath composed of hydrophilic photo- or thermoinitiators (e.g., Irgacure-2959, $\\alpha$ -ketoglutaric acid, ammonium persulfate, potassium persulfate) and hydrogel monomers (e.g., acrylamide (AAm), acrylic acid (AA), N,N-dimethylacrylamide (DMAA), N-vinylpyrrolidone (VP), and hydroxyethyl methacrylate (HEMA)) in aqueous solution. During the subsequent polymerization of the hydrogel pregel solution by UV (for photoinitiators) or heat (for thermosinitiators), the hydrophobic initiators (absorbed on the polymer substrate) serve as grafting agents for the hydrogel polymers to crosslink with the substrate polymer chains as well as oxygen scavengers to alleviate the oxygen inhibition effect.[25,35,36] Meanwhile, the hydrophilic initiators provide polymerization of hydrogel monomers into hydrogel polymers within and above the surface-bound diffusion layer of the polymer substrates. Notably, most polymer substrates are hydrophobic and swell only in organic solvents (e.g., ethanol, acetone) but not in water, allowing the surface-absorption of hydrophobic initiators dissolved in organic solvents by diffusion.[25,34] Furthermore, the insolubility of hydrophobic initiators in water prevents the diffusion of surface-absorbed hydrophobic initiators toward the aqueous hydrogel pregel solution, effectively limiting the reactions (i.e., polymerization, interpenetration, and grafting) within the surface-bound diffusion layer. This unique combination of selective and bounded diffusion of hydrophobic initiators enables the formation of hydrogel skins via an interfacial interpenetration process. Thereafter, the uncrosslinked hydrogel polymer solution is removed by washing with water to obtain the polymer substrates with hydrogel skins. We find that the unreacted hydrogel monomers and ungrafted polymers are mostly removed within the washing step (1 h with agitation). When the washed sample is immersed in water for the next 5 days, only negligible monomers or polymers leach out the hydrogel skin (Figure S2, Supporting Information).  \n\n![](images/cfa38fa1c4997fe695ea3ec5aeaf97a7a5207569b27070698091bd4258c38b7f.jpg)  \nFigure 1.  Schematic illustration of hydrogel skin preparation procedures. First, polymer substrates are treated with a hydrophobic initiator organic solution. Then, the treated polymer substrates are immersed into a hydrogel monomer aqueous solution containing hydrophilic initiators. After curing and washing the hydrogel monomer solution, uniform, and thin hydrogel skins are formed on the polymer surface by the surface-bound formation of hydrogel-polymer interpenetrating networks.  \n\nThe unique surface-bound formation of these hydrogel skins provides highly conformal hydrogel coatings on arbitraryshaped polymer substrates in a wide range of length scales without compromising their original geometries (Figure 2). At large scales, uniform hydrogel skins can be formed on the entire surface of the complex octet-truss-shaped structure made from a silicone rubber (Ecoflex 30, Smooth-On) (Figure 2a). At small scales, uniform hydrogel coatings can be formed on polymer devices like a poly(dimethylsiloxane) (PDMS; Sylgard 184, Dow Corning) microfluidic chip (minimum feature size of $20~\\upmu\\mathrm{m})$ without affecting the original fine features (Figure  2b). Moreover, the thickness of the hydrogel skins can be easily tuned, ranging from thin coatings $(\\approx10~\\upmu\\mathrm{m}$ as shown in Figure  2c; Figure S3b, Supporting Information) to thick coatings $(\\approx25~\\upmu\\mathrm{m}$ as shown in Figure 2d; Figure S3c, Supporting Information) by adjusting the monomer concentration and the polymerization conditions (see the Experimental Section). The hydrogel skins are also relatively smooth and uniform, although the thick ones may exhibit roughness due to their swelling and the subsequent appearance of surface instabilities.[37,38] The hydrogel skins also exhibit long-term stability in aqueous environment with negligible thickness changes during 7 days of soaking in water (Figure S4, Supporting Information).  \n\nSince the proposed method does not rely on specific characteristics of the polymer substrate, it can be applied on a wide range of common polymers with various geometries and applications (Table S1, Supporting Information). In this work, we show that hydrogel skins can be introduced to silicone rubbers (e.g., PDMS and Ecoflex), PU, PVC, nitrile rubber, and natural rubber (Figures S5 and S6, Supporting Information).  \n\nFurthermore, hydrogel skins can be based on a broad range of commonly used hydrogel monomers such as AA, AAm, DMAA, VP, and HEMA (Figures S5 and S7, Supporting Information). The reaction conditions for diverse combinations of polymer substrates and hydrogels are summarized in Table S2 of the Supporting Information, and the confocal microscope images of the hydrogel skins from several representative combinations are shown in Figures S6 and S7 of the Supporting Information.  \n\nWe conduct a set of experiments to quantify the mechanical properties of the hydrogel skins (Figure  3). We first investigate the mechanical properties of the hydrogel skins in order to assess their ability to introduce soft tissue-like surfaces on the polymer substrates. Surface elastic modulus measurements by AFM nanoindentation of the pristine PDMS and the PDMS with AAm-based hydrogel skin ( $25~{\\upmu\\mathrm{m}}$ thick) show that the presence of the hydrogel skins provide low Young’s modulus $\\mathrm{'}E=27.4\\pm7.44~\\mathrm{kPa}$ ), which is comparable to soft tissues in human body $(E=1{-}100\\ \\mathrm{kPa})^{[10,15]}$ and two orders of magnitudes lower than the pristine PDMS $(E=2.01\\pm0.128\\mathrm{{\\MPa}}$ ) (Figure  3a,b). Considering that the hydrogel skin is present only on the outermost $25~{\\upmu\\mathrm{m}}$ of the polymer substrate, the introduction of the hydrogel skin does not alter the bulk elastic modulus of the substrate (PDMS, 1  mm thick) (Figure  3c). Note that PDMS substrates are used for the measurements instead of Ecoflex substrates due to Ecoflex’s Young’s moduli $'E=\\approx30\\ \\mathrm{kPa})$ comparable to that of the hydrogel skins.  \n\nFurthermore, the hydrogel skin can offer a highly lubricious surface on the polymer substrate. We measure the friction coefficients of pristine Ecoflex, Ecoflex with grafted PAAm brushes $(\\approx100\\ \\mathrm{nm}$ thick),[39] and Ecoflex with an AAm-based hydrogel skins ( $25~{\\upmu\\mathrm{m}}$ thick) under varying pressures $(3{-}160~\\mathrm{~kPa})$ (Figure 3d). The presence of the hydrogel skin provides significantly lower friction coefficients than both pristine and PAAm brushes-grafted substrates under all tested pressures. Notably, the hydrogel skin exhibits negligible increase in friction coefficient under increasing pressures while the PAAm brush grafted and the pristine Ecoflex substrates show substantial increase in their friction coefficients with the applied pressure (Figure 3d).  \n\nIn order to investigate the mechanical robustness of the hydrogel skins, we evaluate mechanical damage of the hydrogel skins against short-term and long-term mechanical loadings. We find that the hydrogel skins show no visible damages after repeated scratching with a blunt steel needle, demonstrating adequate scratch and puncture resistance (Figure S8 and Video S1, Supporting Information). Moreover, high stretchability of the hydrogel skins allows recovery from highly deformed state without damage such as crack or delamination (Figure S9, Supporting Information). We also evaluate long-term mechanical robustness by monitoring the change in the coefficient of friction during prolonged shearing under pressure against a steel plate (for 0–3600 s at $3\\ \\mathrm{kPa}$ pressure) (Figure  3e). The hydrogel skin exhibits extraordinary robustness against long-term wear, showing negligible increase in friction coefficient over time and no visible damage even after $10\\mathrm{{h}}$ of continuous shearing (Figure 3f; Figure S10, Supporting Information). By contrast, the PAAm brush grafted and pristine Ecoflex substrates suffer from the gradual elevation in friction coefficient over time, largely due to wear-induced increase in surface roughness.[40] Interestingly, the friction coefficient difference between the PAAm brush-grafted and pristine Ecoflex substrates nearly disappears after 1200 s of shearing, indicating the degradation of the grafted PAAm brushes by mechanical wear (Figure  3f). The superior mechanical robustness of the hydrogel skins can be attributed to the unique hydrogel-polymer interpenetrating network structure. Unlike weak and brittle grafted polymer brushes and conventional hydrogel coatings, the interpenetration of the substrate and hydrogel chains yields a significant increase in mechanical robustness, analogous to double-network tough hydrogels.[41,42]  \n\n![](images/89004b8ee5c2fc78ba1cb0202616fefbede1e0fcc0592ab5447241cd3bec0817.jpg)  \nFigure 2.  Hydrogel skins on diverse arbitrary shaped polymers. a) Octet truss structures made of Ecoflex with and without hydrogel skins. Hydrogel skins are colorized by green food dye. b) Confocal microsco y images of PDMS microfluidic chips with and without hydrogel skins. PDMS and hydrogel skins are colorized by Nile red and fluorescein, respectively. c,d) Confocal microscope images of thin (c) and thick (d) hydrogel skins on the PDMS substrates to illustrate the uniformity and tunable thickness of hydrogel skins. PDMS and hydrogel skins are colorized by Nile red and fluorescein, respectively.  \n\n![](images/28a8f0fd9cc194feb1b163dcb94d12d04c1acec0098cb8f0e1591f43899af6fc.jpg)  \nFigure 3.  Mechanical properties of hydrogel skins. a,b) Nanoindentation curves for PDMS substrates without (a) and with (b) hydrogel skins. Values for Young’s modulus indicate the average and the standard deviation $[n=20$ repeats). c) Nominal stress v sus stretch curves for PDMS substrates with and without hydrogel skins. d) Friction coefficients of pristine Ecoflex, Ecoflex grafted with PAAm brush, and Ecoflex with hydrogel skins under different normal pressures ( $n=3$ repeats). e) Friction coefficients of pristine Ecoflex, Ecoflex grafted with PAAm brush, and Ecoflex 30 with hydrogel skins at $3\\mathsf{k P a}$ normal pressure after the extended periods of friction testing ( $[n=3$ repeats). f) Confocal microscopy images of hydrogel skins before and after $\\rceil0\\mathrm{~h~}$ friction testing. Ecoflex and hydrogel skins are colorized by Nile red and fluorescein, respectively.  \n\nIn addition to the mechanical softness and low-friction characteristics, the hydrogel skins can provide superior antifouling property to the polymer devices. To evaluate the antifouling performance of the hydrogel skins, we quantitatively compare the density of bacteria (Escherichia coli (E. coli)) adhered to the thin and thick hydrogel skins (10  and $25~{\\upmu\\mathrm{m}}$ based on AAm and PDMS substrates, respectively) as well as the PAAm brush grafted and the pristine PDMS substrates (Figure  4a). Both thin and thick hydrogel skins exhibit much lower level of E. coli adhesion $(\\approx80$ and ${\\approx}5$ counts per $\\mathrm{mm}^{2}$ for thin and thick skins, respectively) than the pristine PDMS $_{|\\approx1300}$ counts per $\\mathrm{mm}^{2}$ ) and the PAAm brush grafted PDMS $(\\approx180$ counts per $\\mathrm{mm}^{2}$ ) substrates (Figure 4b). The hydrogel skin’s resistance to bacterial adhesion may delay the subsequent formation of biofilms and can be desirable for biomedical device coatings.[22–24]  \n\nOwing to the hydrogel skins’ high water contents that can dissolve ionic species, the hydrogel skins can endow ionic conductivity to the polymer devices as well. The resultant ionically conductive hydrogel skins (or ionic skins) can serve as a thin, conformal, and transparent ionic conductor with high ionic conductivity ( $1\\mathrm{S}\\mathrm{m}^{-1}$ with $3\\mathrm{~M~}$ LiCl) and high stretchability (over six times of the original length) for various electrically insulating polymer devices with complex shapes. Notably, the ionic skins exhibit the relation between electrical resistance and stretch as $R/R_{0}=\\lambda^{2}$ , where $R_{0}$ is the resistance before deformation and $R$ is the resistance after stretch of $\\lambda$ times from the original length, similar to the ionically conductive bulk hydrogels (Figure  4c).[43–46] To demonstrate the ionic skins on polymer devices with complex geometry, we introduce uniform DMAAbased hydrogel skins with dissolved LiCl salt (3 m concentration) on the outer surface of an Ecoflex tube with diameter of $3\\mathrm{cm}$ . The ionic skins provide ionic conductivity on the electrically insulating Ecoflex tube which can light up an LED with an AC power source connected to the ionic skins (Figure 4d). Note that various types of salts can be used for the preparation of ionic skins such as NaCl to replace LiCl for better biocompatibility.  \n\nThe broad applicability of the proposed hydrogel skins to a wide range of polymer devices enables us to explore various applications otherwise unachievable with conventional hydrogel coatings (Table S1, Supporting Information). We first demonstrate applications of the hydrogel skins on various commonly used biomedical devices such as cardiac pacemaker leads, medical tubing, and Foley catheters (Figure  5). Unlike other hydrogel coating approaches, the hydrogel skins are formed on all submerged polymer surfaces regardless of size or orientation, but not on nonpolymeric materials (i.e., metals or ceramics) (Figure 1). For example, we show that thin and uniform AAm-based hydrogel skins ( $25~{\\upmu\\mathrm{m}}$ thick) can be successfully formed on the PU surface of long and highly flexible cardiac pacemaker leads without affecting the metallic electrodes at the end of the pacing leads (Figure 5a).  \n\nWhile tubes are one of the most frequently used geometries in polymer devices in biomedical and clinical applications (Table S1, Supporting Information), previous approaches have failed to selectively coat inner and/or outer surfaces of tube devices. By contrast, the versatility of the proposed method enables uniform hydrogel coating of both inner and outer surfaces of polymer tubes or only one of them. For example, DMAA-based hydrogel skins $25~{\\upmu\\mathrm{m}}$ thickness) can be formed on both inner and outer surfaces of a PVC tubing (Figure 5b) and a silicon Foley catheter (Figure 5c) as well as on inner surface alone for a PVC tubing (Figure S11, Supporting Information). Notably, hydrogel skins can also be coated on the Foley catheter balloon and remain on the device upon inflation of the balloon, demonstrating the versatility of the proposed method (Figure  5c). High scalability of the fabrication process further allows the formation of hydrogel skins on long tube devices such as $1.5\\mathrm{~m~}$ long segment of PVC tubing in a single preparation (Figure S11, Supporting Information).  \n\n![](images/9163a38ab790c80d6866444522b3128e89f0790ba091d69e84d571a770a57270.jpg)  \nFigure 4.  Antifouling and ionically conductive properties of hydrogel skins. a) Fluorescence microscopy images of E. coli adhered to pristine PDMS, PDMS grafted with PAAm brush, and PDMS with hydrogel skins after $24\\ h$ incubation. b) The number of adhered E. coli per unit area $(\\mathsf{m}\\mathsf{m}^{2})$ for each substrate $\\overset{\\cdot}{n}=3$ repeats). c) Normalized electrical resistance versus stretch for Ecoflex sheet with ionic skins. Hydrogel skins are colorized by blue food dye. d) The ionic skins on an Ecoflex tube connected with an AC power source can light up an LED.  \n\nAs another example, existing soft robots are typically made of elastomers such as PDMS and Ecoflex in complex shapes depending on their functions and applications.[6] While hydrogel coatings can be beneficial for several soft robotic applications including medical soft robots (to decrease tissue trauma due to material rigidity and high friction)[8] and pipe leak detection soft drones (to decrease friction between robots and pipes),[47] it has been challenging to introduce hydrogel coatings on soft robots due to the complex geometries of soft robots. The advantages of the proposed hydrogel skins can open new opportunities to incorporate hydrogel coatings for these previously inaccessible soft robotic applications. As an example, we introduce a uniform AAm-based hydrogel skin to a soft drone (Ecoflex as body material) for leak detection in pipes (Figure  6a). We find that hydrogel skins on the soft drones can provide highly lubricious interfaces substantially reducing fluctuations in travel speed within the pipe smaller than the drones ( $51~\\mathrm{mm}$ diameter drone in $49.25~\\mathrm{\\mm}$ diameter pipe) (Figure  6b; Video S2, Supporting Information).  \n\nAs one of the most promising routes to seamlessly integrate hydrogels’ unique benefits into existing devices, hydrogel coatings on polymer devices possess a great potential in a wide range of applications. In this study, we develop a simple yet effective method to introduce thin and uniform hydrogel skins readily applicable for diverse combinations of polymers and hydrogels. We demonstrate the ability to form micrometer-scale thin uniform hydrogel layer on highly complex geometries without compromising fine features in the polymer substrate as small as $20~{\\upmu\\mathrm{m}}$ . Hydrogel skins boast tissue-like softness together with superior mechanical robustness, low-friction, antifouling performance, and ionic conductivity. We further show representative applications of the hydrogel skins for various polymer devices including cardiac pacemaker leads, medical tubing, Foley catheters, and pipe leak detecting soft drones, all of which are previously unachievable with conventional hydrogel coating methods. With this unprecedented capability, this work has the potential to open new avenues toward untapped opportunities for integrative hydrogel technologies and their important applications, including biomedical and clinical devices, wearable devices, and soft robotics.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Experimental Section  \n\nMaterials: All chemicals were obtained from Sigma-Aldrich and used as received, unless otherwise noted. Silicone substrates were prepared by casting commercially available silicone resins into acrylic molds. PDMS substrates were casted by using Sylgard 184 (Dow Corning) mixture (base resin and catalyst in 10:1 weight ratio). Ecoflex 30 substrates were casted by using Ecoflex 30 (Smooth-On) mixture (Part A and Part B in 1:1 weight ratio). PU, PVC, nitrile rubber, and natural rubber substrates were obtained from McMaster-Carr and cleaned with isopropanol and deionized water before use. Octet truss structures were prepared by casting Ecoflex 30 mixture into a 3D printed mold. Microfluidic chips were prepared by casting Sylgard 184 mixture on a soft lithography mold (designed by collaborators in the Kamm group, MIT MechE). Cardiac pacemaker leads (PACEL Bipolar Pacing Catheter, St. Jude Medical) and Foley catheter (Bardia Foley Catheter 20Fr, C. R. Bard) were obtained from 4MD Medical Solutions. PVC tubes and balls (stainless steel, glass, polypropylene, and neoprene rubber) were obtained from McMaster– Carr and cleaned with isopropanol and deionized water before use.  \n\n![](images/a319ccf7ba53c72076ac9a0adc5773e73f8d64be4a4804496ac812258d3af5f5.jpg)  \nFigure 5.  Applications of hydrogel skins on medical devices. a) Polyurethane (PU) pacemaker leads with and without hydrogel skins on outer surface. Hydrogel skins are colorized by blue food dye. b) PVC tubing with and without hydrogel skins on both inner and outer surfaces. Hydrogel skins are colorized by green food dye. c) Silicone Foley catheters with and without hydrogel skins on both inner and outer surfaces. Hydrogel skins are intact even after inflation of balloon. Hydrogel skins are colorized by green food dye.  \n\nPreparation of Hydrogel Skins on Diverse Polymers: The polymer substrates were first cleaned with isopropanol and deionized water followed by drying under nitrogen flow. To enhance wettability of the polymer substrates, the substrates were treated by atmospheric plasma by a plasma cleaner (PDC-001, Harrick Plasma) for 3  min. The plasma treated polymer substrates were then immersed into a hydrophobic initiator (benzophenone, 4-methylbenzophenone, benzoyl peroxide, azobisisobutyronitrile) organic solution (ethanol, isopropanol, acetone) for $3{-}5\\mathsf{\\ m i n}$ . After gently rinsing with isopropanol followed by drying under nitrogen flow, the substrates were immersed into a hydrogel monomer (acrylic acid, acrylamide, N,N-dimethylacrylamide, N-vinylpyrrolidone, hydroxyethyl methacrylate) aqueous solution containing hydrophilic initiator (Irgacure-2959, $\\alpha$ -ketoglutaric acid, ammonium persulfate, potassium persulfate). To form hydrogel skins, the monomer solution bath was subjected to either UV irradiation (CL-1000, UVP) for photoinitiators or $80~^{\\circ}\\mathsf{C}$ oven for 30–90  min. After formation of hydrogel skins, unreacted regents were thoroughly rinsed with a large amount of deionized water for $24\\mathrm{~h~}$ . Typical protocols for various combinations of polymers and hydrogels is summarized in Table S2 of the Supporting Information.  \n\n![](images/e3c7039e51e5244f00009a1ea0424d379613220c7cd74fb961c0315153d596cc.jpg)  \nFigure 6.  Applications of hydrogel skins on soft robots. a) Pipe leak detection soft drones and their travel through PVC pipes with and without hydroge skins. Hydrogel skins are colorized by green food dye. b) The travel speed of the soft drones inside the PVC pipes with and without hydrogel skins. Th drone with hydrogel skins show much smoother travel than the pristine drone.  \n\nImaging of Hydrogel Skins: Due to optical transparency of hydrogel skins, different dyes were utilized to facilitate imaging and characterization of hydrogel skins. For macroscale photographs, samples were immersed in $2\\%$ aqueous green or blue food dye (McCormick) solution for 1  min to colorize hydrogel skins. The colorized samples were lightly rinsed with flowing water to remove excess dye solution from the surface before imaging by a digital camera (D7000, Nikon). For confocal microscope images, a hydrophobic Nile red dye $\\lambda_{\\mathtt{e m i s s i o n}}\\approx600\\ \\mathsf{n m}_{\\beta}$ ) was added to Sylgard 184 mixture prior to casting PDMS substrate to allow visualization of the polymer substrate while hydrogel skins were immersed in an aqueous fluorescein solution $(\\lambda_{\\mathrm{emission}}\\approx570\\ \\mathrm{nm})$ to visualization of hydrogel skins. All confocal microscope images were obtained by an upright confocal microscope (SP8, Leica) using the $z$ -stack acquisition program (slice thickness $\\approx~1~\\upmu\\mathrm{m})$ . For cross-section imaging, samples were immersed in $2\\%$ aqueous blue food dye (McCormick) solution for 1 min to provide better contract to hydrogel skins. The colorized samples were lightly rinsed with flowing water to remove excess dye solution from the surface before imaging by a compound microscope (Eclipse LV100ND, Nikon). For high-resolution surface imaging, samples were sputtered with gold and imaged by a scanning electron microscope (6010LA, JEOL).  \n\nLeaching Tests: Hydrogel skins based on acrylic acid were formed on PDMS substrates and cut into square samples $(4~c m\\times4~c m$ ) before leaching tests. Each square sample was placed in $700~\\mathsf{m L}$ deionized water in separate containers. PDMS substrates without hydrogel skin were also placed in deionized water as control. The amount of acrylic acid monomer and polymer leached into the solution was monitored based on absorbance at $285~\\mathsf{n m}$ (reference wavelength $350~\\mathsf{n m})$ ) at various time points by a UV–vis spectrophotometer (BioMate 3S, Thermo Scientific).  \n\nMechanical Characterizations: Young’s moduli of samples were obtained by fitting force versus indentation depth curve with a JKR model.[48] Nanoindentation tests were performed by an atomic force microscope (MFP-3D, Asylum Research) with $50~\\mathsf{n m}$ indentation depth. To avoid drying of hydrogel skins, nanoindentation tests were done within water bath equipped in the atomic force microscope. Uniaxial tensile tests were performed by a mechanical tester (Z2.5, Zwick/ Roell) at strain rate of $0.1\\ s^{-1}$ . Scratching tests of hydrogel skins were performed by using a blunt-tip 26-gauge stainless steel needle (Nordson EFD) under the compound microscope.  \n\nFriction Coefficient Measurements: Friction coefficients of samples were measured by a rotational rheometer (AR-G2, TA Instruments) in normal force control mode with $20~{\\mathsf{m m}}$ steel parallel plate fixtures. The friction coefficients were obtained by following the previously reported protocol.[26] Briefly, pristine Ecoflex 30, Ecoflex 30 grafted with PAAm brush,[19] and Ecoflex 30 with thick hydrogel skins ( $25~{\\upmu\\mathrm{m}}$ based on AAm) were prepared and cut into square samples $(4~{\\mathsf{c m}}\\times4~{\\mathsf{c m}})$ . Then, each sample was loaded into the rheometer and a set of normal pressures $(3-160\\mathsf{k P a})$ was applied to the sample immersed in deionized water bath at steady-state shear rate of $0.5\\ {\\mathsf{s}}^{-1}$ .  \n\nAntifouling Tests: An engineered E. coli strain that constitutively expresses green fluorescent protein was prepared by following the previously reported protocol,[32,49] and cultured in Luria-Bertani broth (LB broth) overnight at $37^{\\circ}\\mathsf C$ . ${\\mathrm{~\\mathbb~{~l~}~}}\\upmu\\up L$ of bacteria culture diluted in $7m L$ of fresh LB broth was placed on samples $[1c m\\times1c m)$ and incubated for $24\\mathrm{~h~}$ at $37^{\\circ}\\mathsf C$ After the incubation, the samples were taken out and rinsed with phosphate buffered saline to remove the free-floating bacteria, and imaged with a fluorescence microscope (Eclipse LV100ND, Nikon). The number of adhered E. coli on the samples per unit area $(\\mathsf{m}\\mathsf{m}^{2})$ was counted by ImageJ.  \n\nPreparation and Characterizations of Ionic Skins: To introduce ionic conductivity to the hydrogel skins, Ecoflex 30 sheets or tubes were introduced with hydrogel skins $25\\ \\upmu\\mathsf{m}$ based on DMAA), and then immersed in the $3\\mathrm{~M~}$ LiCl solution for $\\textsf{l h}$ . To introduce a pristine Ecoflex area between two ionic skins, a Kapton tape was applied on the Ecoflex tube during the hydrogel skin formation. To light up an LED on the ionic skins, each side of the ionic skins were connected to an AC power source (5 V peak-to-peak voltage at $1\\ \\mathsf{k H z}$ sine input). The electrical properties of the ionic skins were measured using the four-point method following the previously reported protocols.[25,50]  \n\nPipe Soft Drone Tests: Pipe leak detecting soft drones were prepared by following the previously reported protocol[47] and introduced with hydrogel skins ( $25\\ \\upmu\\mathrm{m}$ based on AAm). The soft drones travel tests were performed by using a clear PVC pipe ( $49.25~\\mathsf{m m}$ diameter) with $20\\mathsf{k P a}$ applied water pressure. The speed of drone travel inside the pipe was obtained by analyzing the recorded footage of tests (Video S2, Supporting Information).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 3,
+        "chunk": "# Supporting Information  \n\nSupporting Information is available from the Wiley Online Library or from the author.",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# Acknowledgements  \n\nY.Y., H.Y., and G.A.P. contributed equally to this work. H.Y., Y.Y., G.A.P., and X.Z. conceived the idea and designed the study. Y.Y., H.Y., and G.A.P. prepared samples and conducted the experiments. Y.W. and K.Y.-T. performed and analyzed the pipe soft robot experiments. Y.Y. and X.L. performed the antifouling experiments. H.Y., G.A.P., Y.Y., and X.Z. analyzed and interpreted the result, and wrote the manuscript. The authors thank to Dr. Alan F. Schwartzman in MIT DMSE NanoMechanical Technology Laboratory for his help with AFM nanoindentation experiments. This work is supported by National Science Foundation (CMMI-1661627). H.Y. acknowledges the financial support from Samsung Scholarship.",
+        "category": " Acknowledgements"
+    },
+    {
+        "id": 5,
+        "chunk": "# Conflict of Interest  \n\nThe authors declare no conflict of interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 6,
+        "chunk": "# Keywords  \n\nantifouling, biomedical devices, coatings, hydrogels, low friction, polymer devices  \n\nReceived: November 2, 2018 Revised: November 26, 2018 Published online:  \n\n[1]\t A. J. T.  Teo, A.  Mishra, I.  Park, Y.-J.  Kim, W.-T.  Park, Y.-J.  Yoon, ACS Biomater. Sci. Eng. 2016, 2, 454.   \n[2]\t Y.  Onuki, U.  Bhardwaj, F.  Papadimitrakopoulos, D. J.  Burgess, J. Diabetes Sci. Technol. 2008, 2, 1003.   \n[3]\t Ž.  Marjanovic´-Balaban, D.  Jelic´, Polymeric Biomaterials in Clinical Practice, Springer, Berlin, Germany 2018, pp. 101–117.   \n[4]\t S. Haeberle, R. Zengerle, Lab Chip 2007, 7, 1094.   \n[5]\t F. Ilievski, A. D. Mazzeo, R. F. Shepherd, X. Chen, G. M. Whitesides, Angew. Chem. 2011, 123, 1930.   \n[6]\t D. Rus, M. T. Tolley, Nature 2015, 521, 467.   \n[7]\t E.  Bouza, M.  Guembe, P.  Munoz, Int. J. Antimicrob. Agents 2010, 36, S22.   \n[8]\t E. T.  Roche, M. A.  Horvath, I.  Wamala, A.  Alazmani, S.-E.  Song, W.  Whyte, Z.  Machaidze, C. 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P. Johnson, T. L. Vu, D. E. Bolgen, S. Rifai, A. R.  hansen, M.  Aizenberg, M.  Super, J.  Aizenberg, D. E.  Ingber, Nat. Biotechnol. 2014, 32, 1134.   \n[25]\t H.  Yuk, T.  Zhang, G. A.  Parada, X.  Liu, X.  Zhao, Nat. Commun. 2016, 7, 12028.   \n[26]\t G. A.  Parada, H.  Yuk, X.  Liu, A. J.  Hsieh, X.  Zhao, Adv. Healthcare Mater. 2017, 6, 1700520.   \n[27]\t D. Wirthl, R. Pichler, M. Drack, G. Kettlguber, R. Moser, R. Gerstmayr, F.  hartmann, E.  Bradt, R.  Kaltseis, C. M.  Siket, S. E.  Schausberger, S. Hild, S. Bauer, M. Kaltenbrunner, Sci. Adv. 2017, 3, e1700053.   \n[28]\t N. A. Peppas, J. Z. Hilt, A. Khademhosseini, R. Langer, Adv. Mater. 2006, 18, 1345.   \n[29]\t A. S. Hoffman, Adv. Drug Delivery Rev. 2012, 64, 18.   \n[30]\t E. Caló, V. V. Khutoryanskiy, Eur. Polym. J. 2015, 65, 252.   \n[31]\t H.  Yuk, T.  Zhang, S.  Lin, G. A.  Parada, X.  Zhao, Nat. Mater. 2016, 15, 190.   \n[32]\t X.  Liu, T.-C.  Tang, E.  Tham, H.  Yuk, S.  Lin, T. K.  Lu, X.  Zhao, Proc. Natl. Acad. Sci. USA 2017, 114, 2200.   \n[33]\t Q. Liu, G. Nian, C. Yang, S. Qu, Z. Suo, Nat. Commun. 2018, 9, 846.   \n[34]\t M. H. Schneider, Y. Tran, P. Tabeling, Langmuir 2011, 27, 1232.   \n[35]\t G. Dorman, G. D. Prestwich, Biochemistry 1994, 33, 5661.   \n[36]\t W. Yang, B. Rånby, Macromolecules 1996, 29, 3308.   \n[37]\t K. Saha, J. Kim, E. Irwin, J. Yoon, F. Momin, V. Trujillo, D. V. Schaffer, K. E. Healy, R. C. Hayward, Biophys. J. 2010, 99, L94.   \n[38]\t M. K. Kang, R. Huang, J. Mech. Phys. Solids 2010, 58, 1582.   \n[39]\t Y.  Wang, H.-H.  Lai, M.  Bachman, C. E.  Sims, G. P.  Li, N. L. Allbritton, Anal. Chem. 2005, 77, 7539.   \n[40]\t M. Barquins, Wear 1992, 158, 87.   \n[41]\t J.-Y.  Sun, X.  Zhao, W. R. K.  Illeperuma, O.  Chaudhuri, K. H.  Oh, D. J. Mooney, J. J. Vlassak, Z. Suo, Nature 2012, 489, 133.   \n[42]\t X. Zhao, Soft Matter 2014, 10, 672.   \n[43]\t C. Keplinger, J.-Y. Sun, C. C. Foo, P. Rothemund, G. M. Whitesides, Z. Suo, Science 2013, 341, 984.   \n[44]\t J.-Y. Sun, C. Keplinger, G. M. Whitesides, Z. Suo, Adv. Mater. 2014, 26, 7608.   \n[45]\t C.-C. Kim, H.-H. Lee, K. H. Oh, K. H. J.-Y. Sun, Science 2016, 353, 682.   \n[46]\t M. S.  Sarwar, Y.  Dobashi, C.  Preston, J. K. M.  Wyss, S.  Mirabbasi, J. D. Wyndham, Sci. Adv. 2017, 3, e1602200.   \n[47]\t Y. Wu, K. Kim, M. F. Henry, K. Youcef-Toumi, IEEE/RSJ Int. Conf. on Intelligent Robots and Systems (IROS), IEEE, Piscataway, NJ, USA 2017, pp. 6075–6082.   \n[48]\t K. L. Johnson, K. Kendall, A. Roberts, Proc. R. Soc. A 1971, 324, 301.   \n[49]\t X.  Liu, H.  Yuk, S.  Lin, G. A.  Parada, T.-C.  Tang, E.  Tham, C.  de  la Fuente-Nunez, T. K. Lu, X. Zhao, Adv. Mater. 2018, 30, 1704821.   \n[50]\t C. H. Yang, B. Chen, J. J. Lu, J. H. Yang, J. Zhou, Y. M. Chen, Z. Suo, Extreme Mech. Lett. 2015, 3, 59.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# ADVANCED MATERIALS  \n\nSupporting Information  \n\nfor Adv. Mater., DOI: 10.1002/adma.202002710  \n\nWet-Style Superhydrophobic Antifogging Coatings for Optical Sensors  \n\nJongsun Yoon, Min Ryu, Hyeongjeong Kim, Gwang-Noh Ahn, Se-Jun Yim, Dong-Pyo Kim,\\* and Hyomin Lee\\*  \n\nCopyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2020.",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# Supporting Information",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# Wet-Style Superhydrophobic Antifogging Coatings for Optical Sensors  \n\nJongsun Yoon, Min Ryu, Hyeongjeong Kim, Gwang-Noh Ahn, Se-Jun Yim, Dong-Pyo Kim\\*, and Hyomin Lee\\*",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# WILEY-VCH",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# Experimental Section",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# Materials  \n\nChitosan (CHI, low molecular weight), Carboxymethyl cellulose (CMC, $\\mathrm{Mw}=250{,}000\\ \\mathrm{g}$ $\\mathrm{mol^{-1}}.$ ), Cationic silica nanoparticles LUDOX® CL ( $30\\mathrm{wt}\\%$ $\\mathrm{SiO}_{2}$ suspension in water, average particle size of $12\\ \\mathrm{nm}$ , and specific surface area of $220{\\mathrm{~m}}^{2}{\\mathrm{~g}}^{-1}.$ ), Anionic silica nanoparticles LUDOX® HS-40 ( $40\\ \\mathrm{wt}\\%$ $\\mathrm{SiO}_{2}$ suspension in water, average particle size of $12\\ \\mathrm{nm}$ , and specific surface area of $220{\\mathrm{~m}}^{2}{\\mathrm{~g}}^{-1}.$ ), Silicone oil (viscosity $10~\\mathrm{cSt}$ at $25~^{\\circ}\\mathrm{C}$ ), Acetic acid, and 2-Hydroxy-2-methylpropiophenone (Darocur 1173) were purchased from Sigma-Aldrich (Korea). Negative photoresist (SU-8 50, Microchem), Perfluoropolyether (PFPE)-urethane methacrylate (Fluorolink® MD700, Solvay), and Polydimethylsiloxane (PDMS, Sylgard® 184, Dow Corning) were used for lithography. Sand (40-100 mesh) was purchased from Acros Organics. Glass slides $76\\times26\\times1~\\mathrm{mm}$ ) were purchased from Marienfeld.  \n\nPolymer-Silica Nanocomposite Fabrication via Layer-by-Layer Assembly: Sequential stacking of polymer and nanoparticle layers were performed using a StratoSequence 8 spin dipper (nanoStrata Inc.), controlled by StratoSmart operating software. The concentrations of CHI, CMC, positive charged $\\mathrm{SiO}_{2}$ , and negative charged $\\mathrm{SiO}_{2}$ in the dipping solutions were 1 $\\mathrm{mg\\ml^{-1}}$ , $1~\\mathrm{mg~ml^{-1}}$ , $0.03\\%$ (w/w), and $0.03\\%$ (w/w), respectively. For CHI, $0.3\\%$ (v/v) acetic acid (Sigma-Aldrich) was added prior to dissolving the polymer and was filtered with $5~{\\upmu\\mathrm{m}}$ pore filter (Millex®) after stirring overnight. Deionized water ( $18.2~\\mathrm{M}\\Omega\\cdot\\mathrm{cm}$ at $25~^{\\circ}\\mathrm{C}$ ) was used for all aqueous solutions. The dipping time in each solutions was $10~\\mathrm{min}$ followed by three rinsing steps (2, 1, and $1\\mathrm{min}^{\\cdot}$ ) in deionized water. The polymeric reservoir, (CHI/CMC)n ( $\\mathrm{\\dot{n}=}$ number of bilayers) was produced by alternately dipping in CHI and CMC solutions with rinsing steps in between. The polymer-silica nanocomposite was prepared by additionally depositing two complementary interacting nanoparticles on the polymeric reservoir.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# WILEY-VCH  \n\nCold-Fog Transition Test: The cold-fog transition test described in Figure 1e and Figure 1f was performed by incubating glasses coated with various types of films in a $-15^{\\circ}\\mathrm{C}$ freezer for 12 hours and subsequent transfer to ambient lab conditions ( $21~^{\\circ}\\mathrm{C}$ , $35\\%$ RH). The cold-fog transition test described in Figure 3b and Figure 3e was conducted by contacting the coated glasses with a Peltier plate $\\left(-20^{\\circ}\\mathrm{C}\\right)$ for 1 minute and exposure to an ambient condition $(25^{\\circ}\\mathrm{C}$ , $22\\%$ RH) for 10 seconds. The optical photographs were obtained by a digital microscope (AM4113, Dino-Lite). For the observation of surface-induced fog, an inverted microscope (Eclipse Ti2, Nikon) was used. The cold-fog transition test described in Figure S5 was performed by incubating micro-pillar assembled polymer-silica nanocomposite in a $4~^{\\circ}\\mathrm{C}$ freezer for 1 hour and subsequent transfer to a temperature and humidity condition of $50~^{\\circ}\\mathrm{C}$ , $55\\%$ RH.  \n\nLow Surface Energy Micro-Pillar Array Transfer on the Polymer-Silica Nanocomposite via Two-Step Lithography: To transfer the micro-pillar array, SU-8 pillar array was fabricated using typical lithography with a negative photoresist (SU-8 50). PDMS was poured onto the master and cured in an oven set at $70~^{\\circ}\\mathrm{C}$ for 3 hours. Then, photocurable PFPE polymer precursor containing $4\\%$ (w/w) Darocur 1173 was poured into the PDMS microwell and the excess was removed using a razorblade. Prior to attachment and curing, the polymer-silica nanocomposite was infused with a silicone oil to avoid PFPE film formation on the polymersilica nanocomposite. UV with an intensity of $20\\mathrm{mW}\\mathrm{cm}^{-2}$ was irradiated for 5 min to induce photocuring of the independent PFPE pillars. The residue was washed off with acetone.  \n\nOther Measurements: The thickness of the films were characterized using profilometry (Dektak XT, Bruker). The Fourier transform infrared (FT-IR) spectra were collected using FT-IR spectroscopy (PerkinElmer) in transmittance mode. The X-ray photoelectron spectroscopy (XPS) spectra were obtained at the 4D beamline in the Pohang Accelerator",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# WILEY-VCH  \n\nLaboratory (PAL). The refractive index of the polymer and the silica layer was measured using spectroscopic ellipsometry (M-2000, J.A. Woollam). The water contact angles were measured using goniometry (SmartDrop, FemtoBiomed Inc.). The transmission spectra of the substrates were measured by spectrophotometer (UV-1800, Shimadzu) with a scanning rate of $50\\mathrm{nm\\sec^{-1}}$ . To demonstrate the utility of the wet-style superhydrophobic antifogging coating, an image sensor (Pixy2) was used to identify the specific colors in various simulated conditions.  \n\n![](images/f0bbcdb774ad87d3f5b6ad0ddd0052fc2563f2de9dc8421db5e4b36d32bc7e57.jpg)  \nFigure S1. (a) The thickness of the polymeric reservoir with respect to the number of bilayers (n) of (CHI/CMC). (b) Transmission spectra of the polymeric reservoir, $(\\mathrm{CHI/CMC)_{n}}$ .  \n\n![](images/22e5099fdd4a40e4ef5ba334544127873aedfa5dd9a3e5c6fcdb1e309e0e1813.jpg)  \nFigure S2. XPS spectra of the polymer-silica nanocomposite (blue line) and polymeric reservoir (green line) (a) O 1s spectra, (b) Si 2p spectra.  \n\n![](images/03f412d4f5145d728b4ee93f7ddd6dcb07ee51ec49d535c3ae12c449834d3f2c.jpg)  \nFigure S3. (a) The thickness of the polymer-silica nanocomposites with respect to the number of bilayers (n) of $\\mathrm{(SiO_{2}/S i O_{2}}$ ). (b) Transmission spectra of the polymer-silica nanocomposites, $\\mathrm{(CHI/CMC)_{30}(S i O_{2}/S i O_{2})_{n}}$ .  \n\n![](images/bdb7317c6108b493c24e95ceea72fa850795b76575bb4e61b7088a7b87de628c.jpg)  \nFigure S4. FT-IR spectra of the (a) individual materials used in the wet-style superhydrophobic antifogging coating and (b) the coating in each step during the assembly.  \n\n![](images/9fe424ea88d0358ed1f3c7d52f292833e6982ea21b2be3d55c83dfdaac5b9607.jpg)  \nFigure S5. (a) A plot showing the water advancing (black bar), and receding (red bar) contact angles of the wet-style superhydrophobic antifogging coatings after exposure to various solvents for 1 hour (micro-pillar interval/diameter value of 4.0). (b) Optical photographs taken after transfer to an environmental chamber equilibrated at $50~^{\\circ}\\mathrm{C}$ , $55\\%$ RH from a $4^{\\circ}\\mathrm{C}$ refrigerator for the wet-style superhydrophobic antifogging coatings treated with various solvents. The scale bar is $1\\mathrm{cm}$ .  \n\n![](images/596ec72813e8a38ba027cab08fc9bf65cfec1b2878c95fc93248bab072c0e5d5.jpg)  \nFigure S6. Scanning electron microscopy (SEM) images of the substrates after two-step lithography. (a) Bare glass. (b) Polymeric reservoir. (c) Silica nanoporous film. (d) Polymersilica nanocomposite coated glass. The scale bar is $100\\upmu\\mathrm{m}$ .  \n\n![](images/0d7905174b0704ba30b3e8a9c76a3db10c9cd7fbe63ac8a5fb066f3d0cbb457b.jpg)  \nFigure S7. Transmission spectra of the wet-style superhydrophobic antifogging coatings with respect to the micro-pillar interval to diameter ratio $(I/D)$ with a fixed micro-pillar diameter of $25\\upmu\\mathrm{m}$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# WILEY-VCH  \n\n![](images/4019c428711fb45426f817c3b71bba5a4e6424a91b108ee26fb223fe5237cbd0.jpg)  \nFigure S8. Optical micrograph of the wet-style superhydrophobic antifogging coating before and after removal of the contaminant (sand, 40-100 mesh) via self-cleaning. The scale bar is $100\\upmu\\mathrm{m}$ .  \n\n![](images/17cc6e35cc6e3a542475f0f6ae020b6babd01ee95f7d93f81f9a10823ecd9ab5.jpg)  \nFigure S9. Transmission spectra of the various films under ambient condition (before) and in a fogging condition (after).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# Supporting Movies  \n\nMovie S1. The application of the wet-style superhydrophobic antifogging coating on a curved surface.  \n\nMovie S2. Mechanical durability test of the wet-style superhydrophobic antifogging coating.  \n\nMovie S3. Water droplet repellency of the wet-style superhydrophobic antifogging coating under the fogging condition.",
+        "category": " Results and discussion"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/admi.201801018.json b/task2/task2-chunks/admi.201801018.json
new file mode 100644
index 0000000..24e8ee6
--- /dev/null
+++ b/task2/task2-chunks/admi.201801018.json
@@ -0,0 +1,67 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Tough Particle-Based Double Network Hydrogels for Functional Solid Surface Coatings  \n\nRiku Takahashi, Kouichi Shimano, Haruka Okazaki, Takayuki Kurokawa, Tasuku Nakajima, Takayuki Nonoyama, Daniel R. King, and Jian Ping Gong\\*  \n\nCoating solid surfaces with tough hydrogels is necessary for the practical application of hydrogels in various fields. Here a simple yet versatile method for coating tough double network (DN) hydrogels onto a wide range of solid surfaces, including various materials and geometries is reported. Particlebased double network (P-DN) gels that combine ease-of-use and significantly strong mechanical properties are utilized. The P-DN gel coating process involves two steps. First, the solid surface (plastic, rubber, ceramic, and/ or metal) is treated to form a thin, physically bound primer layer containing radical initiators. The pre-gel solution is then applied to the treated surface, followed by photo-induced polymerization. The P-DN gel coatings show high toughness, with one notable formulation reaching over $\\mathsf{1000}\\mathsf{I m}^{-2}$ in a $90^{\\circ}$ peeling test. The coatings also show high stability against long-term water-storage, elevated temperatures, and solvent exposure. Moreover, it is demonstrated that the P-DN gel-coated surfaces exhibit low friction properties with high wear resistance, by pin-on-flat tests. The simple coating process can be used even on surfaces with complex geometries, including 3D shapes. This work will enable the use of DN gels in applications such as biocompatible lubricants, scratch resistance coatings, and anti-fouling paints.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1. Introduction  \n\nHydrogels consist mostly of water, supported by a 3D crosslinked polymer network. They exhibit many unique properties such as low friction,[1–3] biocompatibility,[4–6] permeability,[7,8] antifouling,[9–11] optical clarity,[12] and so on. However, despite these impressive attributes, synthetically derived hydrogels tend to be very fragile, limiting their applicability.  \n\nOver the last 15 years, many strong and/or tough hydrogels have been developed with a variety of chemical structures, including slide-ring gels,[13] nanocomposite gels,[14] double network (DN) gels,[15,16] and hybrid gels.[17–19] These studies have demonstrated that, in general, incorporating energy dissipation mechanisms into crosslinked hydrophilic polymer networks can result in tough hydrogels. For example, chemically cross-linked DN gels are a unique form of interpenetrating network gel with highly contrasting network structures. The first network is rigid and brittle, acting as a sacrificial network, while the second network is soft and stretchable. During deformation, the covalent bonds of the first network rupture extensively dissipate energy, prior to global fracture. In the case of hybrid gels that also consist of two interpenetrating networks, such as alginate-polyacrylamide (PAAm) gels, energy dissipation occurs due to the dissociation of physical bonds of the alginate network.[18] Chemical DN gels are elastic, while hybrid gels based on physical sacrificial bonds are viscoelastic, which results in their mechanical properties having strong temperature and deformation rate dependence. The development of extraordinarily strong and tough hydrogels enables us to explore various practical applications of hydrogels. To achieve these goals, hydrogels must be capable of robustly bonding to a wide variety of solid surfaces, including various materials and complicated shapes. It is necessary to utilize a proper coating method depending on the type of hydrogel.  \n\nSeveral attempts have been made to form robust bonds between tough hydrogels and other surfaces. For example, our group has developed a method to robustly bond tough bulk DN hydrogels to porous solids by connecting the bulk surface DN hydrogel to the double networks formed in the solid pores with a soft and stretchable second network that has long chains. High bonding strength ${\\approx}1000\\ \\mathrm{~J~}\\ \\mathrm{m}^{-2}$ , comparable to the fracture strength of bulk DN gels, has been reached.[20] Later, Zhao’s group succeeded in strongly bond PAAm hybrid hydrogels to diverse, nonporous solid surfaces by chemically anchoring the long-chain PAAm network to the surface via silanation.[21] Strong interfacial toughness values of over $1000\\ \\mathrm{J\\m^{-2}}$ , approaching the toughness of the gel itself, have been reached.[18] In addition to this, they successfully achieved elastomer/hydrogel hybrids with strong interfacial toughness (over $1000\\mathrm{~J~m}^{-2})$ ), using elastomer surface modification with benzophenone to activate elastomer surfaces for hydrogel grafting.[22] More recently, Mooney’s group achieved bonding of PAAm-alginate hydrogels to wet biological tissues.[23] In this case, they used a bridging polymer that can bond to the tissues through electrostatic interactions, covalent bonds, and physical interpenetration, which also leads to strong interfacial toughness of over $1000\\mathrm{~J~m}^{-2}$ . These studies have clearly shown that the strength of a bonded gel is not only related to the chemical/physical anchorage at the interface, but also strongly related to the properties of the bulk hydrogels. To create a robust coating, both a strong interface and tough hydrogels are required; the strong interface enables energy transfer from the surface to the bulk hydrogel, which resists detachment through internal energy dissipation mechanisms.[20–24]  \n\nThe aim of this study is to establish a simple method to coat DN gels onto diverse nonporous solid surfaces. Previous studies on bulk DN gels have shown that these materials have low surface sliding friction,[2] low wearing,[6] and excellent antifouling to barnacles.[10] The excellent surface properties of DN gels make them functional coating materials for antifouling paints, low friction medical devices, wearing-resistance surface layers, and so on. However, classic DN gels are not easily applicable as a coating material, because their unique structure/properties and two-step network synthesis method results in the following issues: (1) the swollen first network gel is extremely brittle, and thus difficult to handle as a coating, (2) the substantial swelling of the first network after polymerization induces large swelling mismatch at the interface, leading to delamination of the coating, and (3) the multistep solidification fabrication process makes them difficult to coat on surfaces with complicated geometry.  \n\nOur strategy to overcome these difficulties is to utilize a particle gel-based double network (P-DN) hydrogel technique.[25,26] This technique relies on the first brittle network hydrogel being dispersed as microparticles in the second monomer solution which is subsequently polymerized. After the polymerization of the second network, a composite structure is formed, where the bulk second network interpenetrates with the first network particles, resulting in covalently trapped double network particles inside a stretchable matrix. The obtained P-DN gels, also called a microgel-reinforced hydrogel, show comparable toughness with normal DN gels that have a bicontinuous DN structure.[26] Since the solidification of P-DN gels is through a one-step polymerization of the second network, the fabrication process of P-DN gels is suitable for large areas and arbitrary shape coatings, in which the swollen first network particle “paste” can be applied freely prior to polymerization of the second network, minimizing swelling mismatch.[27] The “paste” precursor of the P-DN gel enables us to easily obtain tough, free-formable, and large-area hydrogel coatings.  \n\nTo achieve bonding, interfacial bridging between the second network of the P-DN hydrogel and the solid surface is required. Our strategy to form the interface bridging is inducing, on the solid surface, a primer layer containing radical initiators by pretreating the surface with a solution containing poly(vinyl acetate) (PVAc) and initiator (Figure 1a).[28] Upon drying, PVAc forms a strong physical coating layer on diverse surfaces (plastic, rubber, ceramic, and metal), with embedded initiator. A similar approach was utilized for coating hydrogels to elastomer surfaces by Zhao and co-workers.[22] This primer method has been shown to be a reliable method to form strong interfaces. We then apply the pre-gel solution that contains the brittle first network gel particles and second network monomer to the surface. To prevent drying and to control the coating thickness, a glass plate with spacer covers the surface of pre-gel solution (Figure 1b). Polymerization of the second monomer takes place from the initiator embedded in the primer layer to form the second network that is strongly bonded to the surface via covalent bonding to the primer layer (Figure 1c and Figure  S1, Supporting Information). By using this approach, we can easily obtain robust hydrogel coatings that exhibit functional properties such as high wettability, low friction, and wear resistance (Figure 1d). The approach is further applied to coating diverse materials (plastics, rubbers, ceramics, and metals) as well as surfaces with complex 3D shapes.  \n\n![](images/601dbb6a71f4dcea17dd2fdbc7f7283759091eb08bf07183747dfd2e2b6bd68f.jpg)  \nFigure 1.  Schematic illustration of the coating process of particle-based double network hydrogels (P-DN gels) onto a solid surface. a) An acetone solution containing benzophenone initiator and poly(vinyl acetate) (PVAc) was coated on the solid substrate. After evaporation of the acetone solvent, a PVAc primer layer containing initiat the ubstrate. b) The sor solution of P-DN gel, containing monomer of second network, acrylamide (AAm), and particle gels of the firs rk, poly(2-a mide-2-methylpropane sulfonic acid sodium salt) (PNaAMPS), was applied to the solid substrate covered with the th n to maintain a flat surface and prevent drying of the solution during polymerization. Durin etwork was polymerized from the initiator in the primer layer. This network penetrates the first network of the gel par h ydr yer strongly bound to the substrate. d) The fabricated tough hydrogel coating exhibits improved surface propertie l w friction, high wettability, and wear resistance.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2. Result and Discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2.1. Mechanical Properties of the P-DN Gel  \n\nThe mechanical strength of the P-DN gels was strongly related to the crosslinking concentration of the first network particles for a fixed particle concentration, as presented by the stress– strain curves in Figure 2b. We found that the modulus and fracture stress increased, while the extensibility remained almost constant with increasing first network cross-linker concentration until $4\\mathrm{mol}\\%$ , where the fracture stress of the P-DN gel reached a maximum value, $2.4~\\mathrm{MPa}$ . This result indicates that the P-DN gels exhibited the characteristic double network effect when the cross-linker concentration of the first network was below $4\\mathrm{mol\\%}$ .[15,16] In this region, we envision that the second network gel transfers sufficient load to the first network particles to cause rupture of the first network, which dissipates significant amount of energy.[15,16,25,26,29] Once these particles have been fractured, the second network will continue to stretch until failure, resulting in global fracture of the sample. When the crosslinking concentration in the first network particles was larger than $4\\mathrm{mol}\\%$ , the modulus, fracture stress, and fracture strain all decreased with increasing cross-linker concentration. In this region, we conjecture that the strength of the first network particles became too high, and the second network is not able to transfer enough force to cause fracture of the first network particles prior to second network fracture. This causes catastrophic fracture to occur entirely in the second network, resulting in decreased work of extension. In this case, the first network particle gels do not serve as sacrificial bonds, and the resulting mechanical response no longer exhibits a double network effect.  \n\n![](images/9d45343924cc0776d58982e088697e482e4c2ce88077b2c17714e896e6dad125.jpg)  \nFigure 2.  Tough P-DN hydrogel films prepared based on the double network concept. a) Photographs of the fabrication process of particle-based double network gels (P-DN gel). (i) PNaAMPS gel microparticles in the dried powder state; (ii) PNaAMPS particles swollen in AAm aqueous solution to form a “paste”; (iii) Tough P-DN gel film. PNaAMPS particles and PAAm network act as a rigid/brittle first network and soft/ductile second network, respectively. b) Tensile stress–strain curves of P-DN gels with varying first network crosslinking concentration (testing velocity of $\\mathsf{l o o}\\mathsf{m m}\\mathsf{m i n}^{-1}$ ). The particle concentration in the P-DN gel is fixed as $0.075\\mathrm{~g~}\\mathsf{m}\\bar{\\mathsf{L}}^{-1}$ . c) Work of extension of the P-DN gels with varying first network crosslinking concentration. The dark blue, light blue, and gray lines represent different particle concentrations in the P-DN gel. The error bars are standard deviation from the results of 3–5 samples, and were smaller than the symbol unless otherwise present.  \n\nSubsequently, we studied the effect of particle concentration in P-DN gels. As shown in Figure 2c, and in agreement with the preceding paragraph, the work of extension reached a maximum around $4\\mathrm{\\mol}\\%$ cross-linker for the different particle concentrations. For the fixed cross-linking density $(4\\mathrm{mol}\\%)$ , the highest work of extension was achieved when the particle concentration was $0.015\\ \\mathrm{g\\mL^{-1}}$ (see Figure S2, Supporting Information). This result indicates that there is an optimum particle concentration in the P-DN gels to effectively exhibit high strength and toughness. This agrees with the result of the conventional double network, which states that the ratio of the first to the second network should be a moderate value to maximize toughness.[30,31] For the rest of the experiments, $4\\mathrm{mol}\\%$ and $0.015\\ \\mathrm{g\\mL^{-1}}$ were chosen for the cross-linker concentration of the particle gels and the particle concentration for the P-DN gels, respectively.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2.2. Robust Coating of P-DN Gels  \n\nHomogenous coating layers were formed on the solid substrate. Figure 3a shows typical photos of a polyethylene (PE) substrate before (Figure 3a-i) and after (Figure 3a-ii) coating of the P-DN gel. The coating strength of the tough P-DN gels was investigated by using a $90^{\\circ}$ peeling test, as shown in Figure 3a-iii. Typical force–displacement curves of the peeling test for samples with varied initiator concentration in the primer layer are shown in Figure 3b. The peeling behaviors can be classified into three cases, depending on the benzophenone concentration in solution for the primer layer formation: (1) completely peeled off without gel fracture, (2) peeled off with gel fracture, and (3) gel fractures without peeling. This result indicates that the initiator concentration in the primer layer not only changes the intrinsic bridging strength at the interface, but also changes the properties of the bulk hydrogel. That is, the failure mode changes are governed by the competition between the stress to fracture the gel $(\\sigma_{\\mathrm{c,gel}})$ and the stress to peel off the interface $(\\upsigma_{\\mathrm{interface}})$ . When the initiator concentration is low $(0.3\\mathrm{-}0.6\\mathrm{\\quad}\\mathrm{wt}\\%)$ , interfacial rupture (case (1)) occurs due to a low density of bridging polymers at the interface $(\\sigma_{\\mathrm{c,gel}}\\gg\\sigma_{\\mathrm{interface}})$ . On the other hand, when the initiator concentration is intermediate $(0.6{-}2.0\\ \\mathrm{wt}\\%)$ , we observed a thin residual hydrogel layer on substrate for all gel samples after the peeling tests, indicating case (2) failure. This result indicates that after the occurrence of a few debonding events at the interface, the interfacial crack shifts into the P-DN gel, causing fracture of the bulk P-DN gel $(\\sigma_{\\mathrm{c,gel}}\\sim\\sigma_{\\mathrm{interface}})$ . In this case, the peeling strength is determined by the tearing energy of the P-DN gel, which is confirmed by comparison with the reported tearing energy of the bulk P-DN gels.[25] Furthermore, we investigated the influence of the coating thickness $(0.5{-}2.0\\ \\mathrm{mm})$ ) on peeling strength for intermediate initiator concentration $(0.6~\\mathrm{wt\\%})$ (see Figure S3, Supporting Information). From this test, we can see a trend of increasing peeling strength with increasing coating thickness in the observed thickness range. It is considered that a thicker coating avoids stress concentrations at the interface, resulting in high adhesion energy. When the initiator concentration is higher $(>3.0\\ \\mathrm{wt}\\%)$ , the density of bridging polymers is significantly high, resulting in case (3) failure, which is the rupture of gel without any interfacial debonding $(\\sigma_{\\mathrm{c,gel}}\\ll\\sigma_{\\mathrm{interface}})$ . In this case, the mechanical properties of the gel coating should decrease due to the high concentration of initiator that leads to the formation of relatively short polymer chains. To maximize the toughness of the coating, we need sufficiently high interfacial strength, and also tough gels which can dissipate bulk energy. This result indicates that if we can increase $\\sigma_{\\mathrm{interface}}$ without decreasing $\\sigma_{\\mathrm{c,gel}}$ , we can further enhance the robust hydrogel coating.  \n\n![](images/b9e54b6e16905cef25f026cb70b41d62ae18cfb112df0cab747c48339085bab4.jpg)  \nFigure 3.  Robustness of the P-DN gel coatings on solid surfaces. a) Photographs of an uncoated (i) and P-DN gel coated (ii) polyethylene substrate. To easily visualize the hydrogel coating, the P-DN gel was swollen in water containing a dye, Alcian blue $(0.05~\\mathrm{wt\\%})$ . (iii) A photograph of the $90^{\\circ}$ peeling test of the P-DN coated substrate. Silicone rubber was introduced to prevent elongation of the hydrogel along the peeling direction. Before the peeling test, the P-DN coated samples were immersed in pure water to reach the equilibrium state. b) Normalized force–displacement curves of the peeling tests of P-DN gel films with varying initiator concentration in the primer layer (testing velocity of $30\\mathsf{m m}\\mathsf{m i n}^{-1}.$ ). The values shown in the legend of the plot are the concentrations of benzophenone in the pretreatment solution. The cross-linker concentration of the particles and particle concentration in the P-DN gel were fixed as $4m o l\\%$ and $0.075\\ \\mathrm{g\\mL^{-1}}$ , respectively. Measured force was normalized by the width of the samples. The peeling behaviors can be divided into three cases: (1) completely peeled off without gel fracture, (2) peeled off with gel fracture, and (3) gel fractures without peeling. These cases are governed by the competition between the strength to fracture the gel $(\\sigma_{\\tt c,g e l})$ and the strength to peel off the interface $(\\sigma_{\\mathrm{interface}})$ .  \n\nTo verify this assumption, we attempted to increase the $\\sigma_{\\mathrm{interface}}$ by increasing the surface roughness of the substrate, which increases the effective surface area. A hot press method was utilized to obtain the PE substrates with increased surface roughness (Figure 4a). Three types (#30, #150, #220) of commercially available patterned glass substrates (ISHIMOTO. Co., Ltd.) were heated to $100~^{\\circ}\\mathrm{C}$ and the PE substrates were pressed onto the glass substrate with $800\\mathrm{\\Pa}$ of pressure (Figure 4a-i). After cooling the sample to $25~^{\\circ}\\mathrm{C}$ , we obtained substrates that have various roughness, characterized by the area ratio, $S_{\\mathrm{a}}$ , the ratio between the surface area measured by a 3D-laser scanning microscope (KEYENCE) and the pristine (flat) surface area (Figure 4b). Then, the P-DN gel was coated on the rough PE substrates as shown in Figure 4a-iii. Typical force–displacement curves of the peeling test for samples with 0.3 and $0.6~\\mathrm{wt\\%}$ benzophenone initiator concentration in the primer layer are shown in Figure 4c,d, respectively. When the initiator concentration is $0.3\\mathrm{wt}\\%$ , the peeling behavior changes from case (1) to case (2) with increasing surface area of the substrate. Furthermore, in the case of the $0.6~\\mathrm{wt\\%}$ initiator, increasing the surface area changed the peeling behavior from case (2) to case (3), showing high peeling strength of over $1000\\ \\mathrm{J\\m^{-2}}$ . This result indicates that the increase in surface area from the rough surfaces provided high interfacial bonding strength, resulting in robust coatings when combined with the high toughness of the P-DN gel. We note that the bonding strength at the interface between the substrate and the primer layer (PVAc) is stronger than that between the primer layer and the gel or the strength of the bulk P-DN gel. Because the presence of benzophenone in the primer layer, which can cause branching via transfer reaction in polymeric system, may result in some covalent bonding between the primer layer and PE substrates.[32]  \n\n![](images/ab9713d831b69df71cbf2279a58430c19bf6bb2ebc7ad16050d707b647f4abad.jpg)  \nFigure 4.  Surface roughness effect on the peeling strength. a) Schematic illustration for preparation of hydrogel coatings on rough polyethylene (PE) surface. The rough PE substrates were fabricated by a hot press method. b) Surface morphology of the rough PE substrates. Four different roughness values, $S_{a},$ which was determined by measured surface area divided by initial (flat) surface area, were prepared. c,d) Normalized force–displacement curves of the peeling tests of P-DN gel film with 0.3 and $0.6~\\mathrm{wt\\%}$ benzophenone initiator concentrations in the primer layer (testing velocity of $30\\mathsf{m m}\\mathsf{m i n}^{-1}$ ). The cross-linker concentration of particles and particle concentration in the P-DN gel were fixed as $4m o l\\%$ and $0.0\\dot{7}5\\ \\mathrm{g}\\ \\dot{\\mathsf{m L}^{-1}}$ , respectively. Measured force was normalized by the width of the samples. Silicone rubber was used to prevent elongation of the hydrogel along the peeling direction. Before the peeling test, the P-DN coated samples were immersed in pure water to reach the equilibrium state.  \n\nBy utilizing the sample prepared with $0.3\\mathrm{wt}\\%$ benzophenone in the primer layer and an optimized pre-gel solution (4 m AAm, $0.01\\mathrm{mol}\\%$ $\\boldsymbol{N,N^{\\prime}}$ -methylenebis(acrylamide) (MBAA), $0.015~\\mathrm{\\mg~\\mL^{-1}}$ dry PNaAMPS gel particles synthesized at $4\\mathrm{mol\\%}$ MBAA), we further investigated the stability of the coatings by exposing the coated samples in various conditions (see Figure S4, Supporting Information). The sample did not show any apparent change even after storage in pure water $(25~^{\\circ}\\mathrm{C})$ for $282\\mathrm{~d~}$ , indicating long-term stability (Figure S4a, Supporting Information). After being immersed in hot water $(80~^{\\circ}\\mathrm{C})$ for $24\\mathrm{h}$ , the P-DN gel coatings still exhibit strong bonding, indicating excellent thermostability (Figure S4b, Supporting Information). The sample immersed in acetone, a poor solvent, for 4 days did not show delamination, indicating good resistance to swelling/ deswelling induced interfacial mismatching (Figure S4c, Supporting Information).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.3. Functional Properties of P-DN Gel Coatings  \n\nThe most practical use of tough hydrogel coatings is for modifying the surface properties of solid substrates. By using the coating method introduced here, we can modify solid surfaces to have valuable functions based on hydrogel properties such as high wettability, antifouling, low friction, small molecule retention capacity, and high biocompatibility.[1–12,33,34] Moreover, taking advantages of the high toughness of P-DN gels, we can increase the wear resistance to solid substrates. Herein, to demonstrate the functional properties of P-DN gel coatings such as high wettability, low friction, and wear resistance, we prepared PE substrates coated with tough P-DN gels at the optimized coating condition $(0.3~\\mathrm{wt\\%}$ benzophenone in the primer layer, pre-gel solution of $4\\mathrm{~M~}$ AAm, $0.01\\mathrm{mol}\\%$ MBAA, $0.015~\\mathrm{mg~mL^{-1}}$ dry PNaAMPS gel particles synthesized at $4\\mathrm{mol}\\%$ MBA A). The gel-coated samples were immersed in water for one week after synthesis to reach the equilibrium state (thickness: $300\\upmu\\mathrm{m}$ in the swollen state).  \n\nFirst, we measured the contact angles of water on the P-DN gel coated PE, PAAm (traditional single network hydrogel) coated PE, and pristine PE substrate, respectively (Figure 5a). We confirmed that the hydrogel-coated substrates exhibit high wettability due to the hydrophilic surface properties of hydrogels. Second, to evaluate the sliding friction of the samples, we performed a reciprocating pin-on-flat test as shown in Figure 5b.[35] The tests were conducted in pure water $(25~^{\\circ}\\mathrm{C})$ using an instrument with a motor-driven stage that oscillates a flat specimen beneath a fixed alumina ball (diameter: $10~\\mathrm{mm}$ ). The hydrogel-coated samples (substrate size: length $\\times$ width $\\times$ thickness $\\mathbf{\\tau}=100\\ \\mathrm{mm}\\times50\\ \\mathrm{mm}\\times2\\ \\mathrm{mm})$ were fabricated using the method as mentioned above and the bottom surface of the samples were fixed onto the testing area with double-sided tape. The vertical load, average sliding speed, reciprocating cycles, and sliding distance were 1 N, $500\\ \\mathrm{mm\\min^{-1}}$ , 300 cycles, and $35~\\mathrm{mm}$ , respectively. From the measured friction force $(F)$ (see Figure S5, Supporting Information) and vertical load $(\\mathbb{W})$ , we estimated the coefficient of friction $(\\mu)$ from $\\mu=\\operatorname{F}/\\operatorname{W}.$ The static friction, $\\mu_{0}$ , and dynamic friction, $\\mu_{\\mathrm{d}},$ were estimated from $F_{0}$ (max force) and $F_{\\mathrm{d}}$ (average force), respectively, in the time profiles of the friction during sliding. At the initial state, we found that the hydrogel-coated samples showed lower friction than the bare PE substrate, especially the dynamic friction, as shown in Figure 5c-i. This result indicates that utilizing hydrogel coatings was an effective approach to reduce friction under water. Additionally, after 300 cycles of the sliding test, the coefficient of static friction of the bare PE substrate dramatically increased due to surface wearing. However, the hydrogel-coated samples maintained low friction. Indeed, the P-DN gel coating did not show any wear tracks, indicating strong wear resistance compared to the single network PAAm hydrogel (Figure 5c-ii, iii). These results enable us to explore various practical applications of tough hydrogel coatings.  \n\n![](images/4f0f97a0f66add2d8d6e5be523256c8e69bc3a0dd6e94402f7dd51996f01a8df.jpg)  \nFigure 5.  Surface properties of the hydrogel coating. a) Contact angles of water on a polyethylene substrate (i), pure PAAm coated (ii), and P-DN gel coated polyethylene substrate (iii). Hydrogel coatings (thickness: $300\\ \\upmu\\mathrm{m};$ exhibit high wettability. b) Schematic illustration of the setup for a friction measurement (pin-on-flat test). c) Coefficient of static and dynamic friction on the PE substrate or hydrogel coated surfaces. (i) After 300 cycles of friction testing, hydrogel coatings maintained low friction, similar to the initial state. (ii) Photographs of the coating surface of PAAm and (iii) P-DN gel after 300 cycles of friction testing. Due to the high toughness of the P-DN gel, the gel coating shows little wear damage. The friction load, velocity, and track length are 1 N, $500\\ m\\ m\\mathrm{~min^{-1}}$ , and $35~\\mathsf{m m}$ , respectively. The inset scale represents $500\\upmu\\mathrm{m}$ . Experimental details are shown in the Supporting Information.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.4. Versatility of P-DN Hydrogel Coatings  \n\nThe above result suggests that by using a thin primer layer, the P-DN hydrogel coating method can be applied to diverse solid surfaces. Furthermore, taking advantage of the one-step fabrication of P-DN gels, this method has the potential to coat surfaces with complicated 3D shapes. First, we coated various flat substrates by using the method mentioned in Figure 1. We used zirconium oxide, copper, and polybutadiene as representative ceramic, metal, and rubber specimens, respectively. The optimized coating condition $(0.3\\ \\mathrm{wt\\%}\\$ benzophenone in the primer layer, pre-gel solution of $4\\mathrm{~M~}$ AAm, $0.01\\mathrm{mol}\\%$ MBAA, $0.015\\mathrm{mg}\\mathrm{mL}^{-1}$ dry PNaAMPS gel particles synthesized at $4\\mathrm{mol}\\%$ MBA A) was used for the coating. From the $90^{\\circ}$ peeling test, adhesion strength of P-DN gel coating on polybutadiene rubber showed similar peeling strength to the PE substrate (see Figure S6, Supporting Information). Although the primer layer does not possess chemical bonds with the inorganic surface, it is able to adhere strongly due to physical bonds such as Van der Waals forces. The coatings exhibited excellent adhesiveness even after swelling the hydrogels, as shown in Figure 6a. Therefore, using a thin primer layer by simple solution casting provides a general method to pretreat the coating surfaces where chemical treatments may not be possible. These results demonstrate that by coating tough hydrogels onto solid substrates, we can easily obtain functional surfaces which exhibit low friction and high wear resistance.  \n\nWe next attempted to coat P-DN gels on surfaces with complicated 3D structures (Figure 6b-i, ii). We used a PE model frog for this experiment. By using a brush (or spray-gun), the primer layer precursor solution $(0.3\\ \\mathrm{wt\\%}$ initiator and $1\\mathrm{\\mt{\\%}}$ PVAc in acetone), and then the pre-gel solution ( $\\mathrm{~4~}\\mathrm{~M~}$ AAm, $0.01\\mathrm{\\mol}\\%$ MBAA, $0.015\\mathrm{\\mg\\mL^{-1}}$ dry PNaAMPS gel particles synthesized at $4\\mathrm{mol}\\%$ MBA A) were applied to the model. After that, UV radical polymerization was carried out under an argon atmosphere with a UV lamp for $^{8\\mathrm{~h~}}$ to form the P-DN hydrogel coating layer. To visualize the coating layer easily, the hydrogel-coated model was dyed with Alcian blue $(0.05\\ \\mathrm{wt\\%})$ . As shown in Figure 6b-iii, we successfully obtained tough P-DN gel coatings on complex solid surfaces with robust adhesion. Because of the nonuniformity of the thickness of the coating and large distribution of particle size of gel (from 10 to $200\\upmu\\mathrm{m}$ ), surface roughness is induced after immersing the painted model in water due to inhomogeneous swelling of the gel. To minimize the swelling inhomogeneity, we can use smaller or homogenously sized particles that can be obtained by sieving or through other means. However, even if the coated surface has some inherent roughness, hydrogel coatings on complicated 3D shapes have great potential for practical use, such as coating the exterior surfaces of ships for antifouling and coating medical equipment for minimally invasive procedures.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 3. Conclusions  \n\nIn summary, tough P-DN hydrogel coatings for various solid substrates have been successfully developed. We systematically investigated the mechanical properties of P-DN gels and found the suitable conditions for making tough P-DN gels. By coating the substrates (plastic, ceramic, metal, and rubber) with a primer layer containing proper concentrations of initiator, we can synthesize tough P-DN gels on surfaces with robust bonding. The peeling strength of the hydrogel coating is strongly related to the competition between the strength to break the gel and the strength to peel at the interface. In the toughest peeling case, little debonding occurred at the interface, and the interfacial crack moved into the bulk of the P-DN gel, causing fracture of the bulk P-DN gel. Therefore, using tough P-DN gels as a coating is a novel method to fabricate robust hydrogel coatings. Another useful aspect of using tough hydrogels is that the coatings are sufficiently robust to exhibit wear resistance with low friction. Moreover, taking advantage of the free-formability of P-DN gels, we successfully attained tough P-DN gel coatings on complicated 3D shapes. These demonstrations suggest that hydrogels can be used for a variety of real-world applications where tough coatings are required.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 9,
+        "chunk": "# 4. Experimental Section  \n\nMaterials: 2-Acrylamide-2-methylpropane sulfonic acid sodium salt (NaAMPS) was purchased from Toagosei Co., Ltd. and used as received for the rigid/brittle first network. Acrylamide (AAm) (Jundei Chemical Co., Ltd.) was recrystallized from chloroform and used for the soft/ductile second network. MBAA (Tokyo Kasei Co., Ltd.), as a cross-linker for both NaAMPS and AAm gels, was recrystallized from ethanol. 2-Oxoglutaric acid (α-keto) (Wako Pure Chemical Industries, Ltd.), as an UV initiator for the gelation reaction, was used as received. Benzophenone (Wako Pure Chemical Industries, Ltd.), as an UV initiator for coating of gels on substrates, was used as received. PVAc (Wako Pure Chemical Industries, Ltd.), as an initiator support layer, was used as received.  \n\n![](images/87efe36eda138bca05d884e13780525d53e6b58e0f6e70c5dca62b1f819db151.jpg)  \nFigure 6.  Universality of the hydrogel coating on various solid surfaces. a) Tough P-DN gel coating on (i) ceramic $(Z\\r\\Gamma O_{2})$ , (ii) metal (copper), and (iii) rubber (polybutadiene). The coatings $0.3\\mathrm{\\wt\\%}$ benzophenone in the primer layer, pre-gel solution of 4 m AAm, $0.01\\mathrm{\\mol\\%}$ MBAA, $0.075~\\mathrm{mg~mL^{-1}}$ dry PNaAMPS gel particles synthesized at $4m o l\\%$ MBAA) exhibited excellent adhesiveness, and resist peeling due to friction and bending. b) Freeform P-DN coating on a complicated 3D shape. (i) Schematic illustration of the coating method. The photographs represent (ii) uncoated and (iii) coated samples, respectively. Due to the nonuniformity of the thickness of the coatings, surface roughness was induced by the swelling of the P-DN gel. To easily visualize the hydrogel coating, the P-DN gel was swollen in water containing a dye $(0.05\\mathrm{~wt\\%~}$ Alcian blue).  \n\nPreparation of Particle-Based DN Gels: The P-DN gel films were synthesized using a method similar to the one previously described in the literature.[25] PNaAMPS particles and a PAAm network were used as the rigid/brittle first network and the soft/stretchable second network, respectively. To determine the optimal conditions for making strong and tough P-DN gels, P-DN gel films were systematically synthesized by varying the first network crosslinking concentration and particle concentration. Sheet-like P-DN gels were synthesized through a twostep sequential free-radical polymerization.[25] In the first step of the first network particle preparation, MBAA $(0.5{-}6~\\mathsf{m o l}\\%)$ and $\\alpha$ -keto $(0.1\\ m\\circ1\\%)$ were added to 1 m NaAMPS solution (the molar percentages of MBAA and $\\alpha$ -keto were in relative to the NaAMPS monomer). The solution was poured into reaction cells consisting of a pair of glass plates with a $\\textsf{l m m}$ silicone spacer. Photoinduced free radical polymerization was carried out under argon atmosphere with a UV lamp for $\\mathsf{10~h}$ (UV light intensity was $3.9\\ m\\backslash\\forall c m^{-2}$ ). After that, the as-prepared PNaAMPS gels were roughly ground with a spoon into particles and dried using a vacuum oven for $24\\mathrm{~h~}$ . Subsequently, the dried particles were finely ground with a multibead shocker (Yasui Kikai Co., Ltd.), resulting in particles ranging in size from 10 to $200~{\\upmu\\mathrm{m}}$ (Figure 2a-i). Then, the first network particles were added into the AAm aqueous solution $(4~\\mathsf{M})$ containing MBAA $(0.01\\ m\\circ|\\%)$ and $\\alpha$ -keto $(0.01\\ m\\circ|\\%)$ , where the concentration of PNaAMPS dried particles to AAm solution was varied in the range of $0.005{-}0.030\\ m g\\ m L^{-1}$ , to obtain paste-like precursors of the P-DN gels (Figure 2a-ii). After that, the particle gel solution was poured into the reaction cell consisting of a pair of glass plates with a $\\textsf{l m m}$ silicone spacer. The AAm monomers were photopolymerized with the UV lamp for $8\\ h$ to obtain the P-DN gel sheets (Figure 2a-iii). The P-DN gels in pure water exhibit isotropic swelling, showing an equilibrium thickness of $1.5~\\mathsf{m m}$ .  \n\nCoating P-DN Hydrogels on Solid Substrates: A $2\\mathsf{m m}$ thick PE plate was immersed in the pretreatment solution $(0.7-6~\\mathrm{wt\\%}$ benzophenone, $1\\mathrm{wt\\%}$ PVAc in acetone) for 5 min, then dried in a vacuum oven under reduced pressure for 5 min to form the primer layer. This cycle was repeated twice and performed in a vial shielded from light at room temperature. Then, the pre-gel solution containing $4\\mathrm{~M~}$ AAm, $0.01\\ m\\mathrm{o}1\\%$ MBAA (in relative to AAm), $0.075\\mathrm{\\mg\\mL^{-1}}$ PNaAMPS gel particles synthesized at $4m o l\\%$  \n\nMBA A, was poured onto the pretreated substrates. After that, a flat glass plate was placed on the pre-gel solution with a $0.5\\ \\mathsf{m m}$ thick spacer to prevent evaporation of the solution and control the coating thickness. UV radical polymerization was carried out under an argon atmosphere with a UV lamp for $\\mathsf{10~h}$ , during which the PAAm network was formed and the P-DN gel was bonded onto the solid surface via the primer layer. It should be noted that the pre-gel solution did not contain any radical initiator, and the polymerization of the PAAm network was initiated by the benzophenone in the primer layer. Due to the restriction in the lateral direction, the coated P-DN gel swelled only in the thickness direction in pure water, resulting in a thickness of $1.0\\mathsf{m m}$ .  \n\nVarious types of solid surface substrates, such as ceramic (zirconium oxide, $Z r O_{2}\\mathrm{,}$ ), metal (copper, $\\mathsf{C u}$ ), and rubber (polybutadiene), were also coated with P-DN gels using a $0.3\\mathrm{wt\\%}$ benzophenone concentration. Other conditions were the same as that for the PE coating. Before use, all substrates were washed with pure water.  \n\nTensile Experiments: To characterize the mechanical properties of the P-DN gels, uniaxial tensile tests were performed at equilibrium water swelling conditions using a tensile-compressive tester (Tensilon RTC1310A, Orientec Co.). The P-DN gel sheet, with a thickness of $1.5\\ \\mathsf{m m}$ , was cut into dog bone shape (gauge length: $12\\mathsf{m m}$ , width: $2~\\mathsf{m m}$ ) and the sample was stretched along the length direction at an extension velocity of $\\mathsf{l o}0\\mathsf{m m}\\mathsf{m i n}^{-1}$ . The tensile stress was defined as the ratio between the force generated during the elongation and the initial crosssectional area. Tensile strain was defined as the ratio between the length change during elongation and the initial length of the sample. The work of extension was calculated from the area below the stress–strain curve.  \n\n$90^{\\circ}$ Peeling Tests: The peeling strength between the P-DN gel and PE substrate was measured using a standard $90^{\\circ}$ peeling test (ISO 8510–1) with a mechanical testing machine (Tensilon RTC-1310A, Orientec Co.). As part of the sample preparation process, half of the PE substrate was masked with adhesive tape to prevent chemical bonding to the substrate, which creates the arm for the peeling test. Then, the P-DN gels were coated onto the substrate, forming chemical bonds with the unmasked region of the substrate. A sample with a gel layer coating thickness of $\\mathsf{1.0~m m}$ was cut to specific dimensions (length: $\\mathsf{100~m m}$ , width: $5~\\mathsf{m m}$ ) by using a cutting machine (Dumb Bell Co., Ltd.). To prevent stretching of the P-DN gel, a relatively stiff silicone rubber sheet was bonded onto the back surface of the hydrogel by the same method as the coating process for P-DN gels onto the solid substrates. The PE substrate was fixed to the jig of the tester using an instant glue (Toagosei Co., Ltd.). The samples were tested according to a standard $90^{\\circ}$ peeling test with a constant peeling velocity of $30\\ m m\\ m i n^{-1}$ . When the measured force reached a plateau, the value was treated as the peeling force. The peeling strength was determined by dividing the peeling force with the width of the sample.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# Supporting Information  \n\nSupporting Information is available from the Wiley Online Library or from the author.",
+        "category": " References"
+    },
+    {
+        "id": 11,
+        "chunk": "# Acknowledgements  \n\nR.T. and K.S. contributed equally to this work. This research was financially supported by a Grant-in-Aid for Scientific Research (S) (No. 17H06144) and Grant-in-Aid for JSPS Fellows (No. 15J01078) from Japan Society for the Promotion of Science (JSPS). R.T. was supported by MEXT through Program for Leading Graduate Schools (Hokkaido University “Ambitious Leader’s Program”).",
+        "category": " Acknowledgements"
+    },
+    {
+        "id": 12,
+        "chunk": "# Conflict of Interest  \n\nThe authors declare no conflict of interest.",
+        "category": " References"
+    },
+    {
+        "id": 13,
+        "chunk": "# Keywords  \n\ncoating, double network gels, low friction, tough hydrogel, wear resistance  \n\nReceived: July 6, 2018 Revised: August 16, 2018 Published online:  \n\n[1]\t J. P.  Gong, T.  Kurokawa, T.  Narita, G.  Kagata, Y.  Osada, G. Nishimura, M. Kinjo, J. Am. Chem. Soc. 2001, 123, 5582.   \n[2]\t D. Kaneko, T. Tada, T. Kurokawa, J. P. Gong, Y. Osada, Adv. Mater. 2005, 17, 535.   \n[3]\t S. Ma, B. Yu, X. Pei, F. Zhou, Polymer 2016, 98, 516. [4]\t K. J. Lee, S. I. Yun, Polymer 2018, 139, 86.   \n[5]\t P.  Li, Y.  F.  Poon, W.  Li, H.  Y.  Zhu, S.  H.  Yeap, Y.  Cao, X.  Qi, C. Zhou, M. Lamrani, R. W. Beuerman, E. T. Kang, Y. Mu, C. M. Li, M. W. Chang, S. S. J. Leong, M. B. Chan-Park, Nat. Mater. 2011, 10, 149.   \n[6]\t K.  Yasuda, N.  Kitamura, J.  P.  Gong, K.  Araki, H.  J.  Kwon, S.  Onodera, Y.  M.  Chen, T.  Kurokawa, G.  Kanaya, Y.  Ohmiya, Y. Osada, Macromol. Biosci. 2009, 9, 307.   \n[7]\t N.  Hirota, Y.  Kumaki, T.  Narita, J.  P.  Gong, Y.  Osada, J.  Phys. Chem. B 2000, 104, 9898.   \n[8]\t M. C. Branco, D. J. Pochan, N. J. Wagner, J. P. Schneider, Biomaterials 2010, 31, 9527.   \n[9]\t X.  Cao, M.  E.  Pettit, S.  L.  Conlan, W.  Wagner, A.  D.  Ho, A.  S.  Clare, J. A. Callow, M. E. Callow, M. Grunze, A. Rosenhahn, Biomacromolecules 2009, 10, 907.   \n[10]\t T.  Murosaki, T.  Noguchi, K.  Hashimoto, A.  Kakugo, T.  Kurokawa, J.  Saito, Y.  M.  Chen, H.  Furukawa, J.  P.  Gong, Biofouling 2009, 25, 657.   \n[11]\t L.  Xie, F.  Hong, C.  He, C.  Ma, J.  Liu, G.  Zhang, C.  Wu, Polymer 2011, 52, 3738.   \n[12]\t J. Franklin, Z. Y. Wang, Chem. Mater. 2002, 14, 4487.   \n[13]\t Y. Okumura, K. Ito, Adv. Mater. 2001, 13, 485.   \n[14]\t K. Haraguchi, T. Takehisa, Adv. Mater. 2002, 14, 1121.   \n[15]\t J. P. Gong, Y. Katsuyama, T. Kurokawa, Y. Osada, Adv. Mater. 2003, 15, 1155.   \n[16]\t J. P. Gong, Soft Matter 2010, 6, 2583.   \n[17]\t T.  L.  Sun, T.  Kurokawa, S.  Kuroda, A.  B.  Ihsan, T.  Akasaki, K. Sato, M. A. Haque, T. Nakajima, J. P. Gong, Nat. Mater. 2013, 12, 932.   \n[18]\t J.  Y.  Sun, X.  Zhao, W.  R.  K.  Illeperuma, O.  Chaudhuri, K.  H.  Oh, D. J. Mooney, J. J. Vlassak, Z. Suo, Nature 2012, 489, 133.   \n[19]\t H. Guo, N. Sanson, D. Hourdet, A. Marcellan, Adv. Mater. 2016, 28, 5857.   \n[20]\t T. Kurokawa, H. Furukawa, W. Wang, Y. Tanaka, J. P. Gong, Acta Biomater. 2010, 6, 1353.   \n[21]\t H.  Yuk, T.  Zhang, S.  Lin, G.  A.  Parada, X.  Zhao, Nat.  Mater. 2016, 15, 190.   \n[22]\t H.  Yuk, T.  Zhang, G.  A.  Parada, X.  Liu, X.  Zhao, Nat.  Commun. 2016, 7, 12028.   \n[23]\t J.  Li, A.  D.  Celiz, J.  Yang, Q.  Yang, I.  Wamala, W.  Whyte, B.  R.  Seo, N. V. Vasilyev, J. J. Vlassak, Z. Suo, D. J. Mooney, Science 2017, 357, 378.   \n[24]\t J. Yang, R. Bai, Z. Suo, Adv. Mater. 2018, 30, 1800671.   \n[25]\t J. Saito, H. Furukawa, T. Kurokawa, R. Kuwabara, S. Kuroda, J. Hu, Y. Tanaka, J. P. Gong, N. Kitamura, K. Yasuda, Polym. Chem. 2011, 2, 575.   \n[26]\t J. Hu, K. Hiwatashi, T. Kurokawa, S. M. Liang, Z. L. Wu, J. P. Gong, Macromolecules 2011, 44, 7775.   \n[27]\t H.  Muroi, R.  Hidema, J.  Gong, H.  Furukawa, J.  Solid Mech. Mater. Eng. 2013, 7, 163.   \n[28]\t Y.  M.  Chen, Y.  Katsuyama, J.  P.  Gong, Y.  Osada, J.  Phys.  Chem.  B 2003, 107, 13601.   \n[29]\t X. Zhao, Soft Matter 2014, 10, 672.   \n[30]\t Y. Tanaka, R. Kuwabara, Y. H. Na, T. Kurokawa, J. P. Gong, Y. Osada, J. Phys. Chem. B 2005, 109, 11559.   \n[31]\t Y.  H.  Na, Y.  Katsuyama, R.  Kuwabara, T.  Kurokawa, Y.  Osada, M. Shibayama, J. P. Gong, e-J. Surf. Sci. Nanotechnol. 2005, 3, 8.   \n[32]\t J. Deng, L. Wang, L. Liu, W. Yang, Prog. Polym. Sci. 2009, 34, 156.   \n[33]\t T.-Y.  Liu, S.-Y.  Chen, Y.-L.  Lin, D.-M.  Liu, Langmuir 2006, 22, 9740.   \n[34]\t Y. Qiu, K. Park, Adv. Drug Delivery Rev. 2001, 53, 321.   \n[35]\t V. Saikko, Wear 1993, 166, 169.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Supporting Information  \n\nfor Adv. Sci., DOI 10.1002/advs.202200072  \n\nEffective Antifogging Coating from Hydrophilic/Hydrophobic Polymer Heteronetwork  \n\nJunhe Shi, Liju Xu and Dong Qiu\\*",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# Supporting Information",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# Effective Anti-fogging Coating from Hydrophilic/Hydrophobic Polymer Hetero-Network  \n\nJunhe $S h i^{a,b}$ , Liju $X u^{a,*}$ , and Dong Qiua,b,\\* a Beijing National Laboratory for Molecular Sciences, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China b University of Chinese Academy of Sciences, Beijing 100049, China E-mail: xuliju@iccas.ac.cn; dqiu@iccas.ac.cn",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# Materials and methods  \n\nMaterials. Polyvinyl alcohol 1799 (PVA-1799, $98-99\\%$ hydrolyzed, Aladdin), dimethyl sulfoxide (DMSO, Aladdin), 3-(Trimethoxysilyl) propyl methacrylate (TPM, Alfa), 2,2-bimethoxy-2-phenylacetophenone (DMPA, $98\\%$ , Alfa) and other chemicals (Sinopharm Chemical Reagent Co. Ltd.) were used without further purification. Pure water $\\cdot18.2\\:\\mathrm{M}\\Omega^{.}\\mathrm{cm})$ was generated by an ELGA Purelab system. Preparation of PVA-WI coating. PVA with the mass of $3.6~\\mathrm{g}$ was dissolved in $15~\\mathrm{ml}$ water and stirred for $2\\mathrm{h}$ at $95^{\\circ}\\mathrm{C}.$ After defoaming, the resultant solution was spread on the glass slides to produce a uniform liquid layer with different thickness (25, 100, $200~{\\upmu\\mathrm{m}})$ using a wet film coater. To obtained dry PVA-WI coated substrates, the samples were dried at $25^{\\circ}\\mathrm{C}$ for $24\\mathrm{h}$ .  \n\nPreparation of PVA-SI coating. The oxygen plasma-treated glass slides were first immersed in a mixture solution with $90~\\mathrm{\\ml}$ ethanol, $10~\\mathrm{\\ml}$ water, 5 ml 3-glycidoxypropyltrimethoxysilane and $100\\upmu\\mathrm{l}$ acetic acid at room temperature for 12 h. After thorough cleaning, the epoxy-functionalized glass slides were prepared. PVA with the mass of $3.6\\ \\mathrm{g}$ was dissolved in $15~\\mathrm{ml}$ water ( $\\mathrm{\\boldmath~\\pH}=2\\$ ) and stirred for $2\\mathrm{~h~}$ at $95^{\\circ}\\mathrm{C}$ [1,2] After defoaming, the resultant solution was spread on the epoxy-functionalized glass slides to produce a uniform liquid layer with different thickness (25, 100, $200~{\\upmu\\mathrm{m}}$ ) using a wet film coater. The samples were placed in $60^{\\circ}\\mathrm{C}$ oven for 12 hours to complete chemical grafting of PVA. To obtained dry PVA-SI coated substrates, the samples were dried at $25^{\\circ}\\mathrm{C}$ for $24\\mathrm{h}$ .  \n\nMeasurement of anti-fogging performance. The anti-fogging performance was characterized by a hot-vapor testing. Concretely, the samples were held above a water bath containing water with constant temperature, and the distance between the samples and the surface of the water was $5\\ \\mathrm{cm}$ . To investigate the anti-fogging properties of the samples, the light transmission over the 300-800 nm wavelength range was collected using a UV-Vis spectrophotometer during fogging tests. For comprehensive evaluation and direct comparison, the average transmission over the 400-800 nm wavelength was defined and obtained from the following equation:  \n\n$$\nT\\%={\\frac{\\int_{400}^{800}{x d x}}{800-400}}\n$$  \n\nThe repeated anti-fogging tests were carried on a $60^{\\circ}\\mathrm{C}$ water bath. The sample was first exposed to hot water vapor $(60^{\\circ}\\mathsf{C})$ for $10~\\mathrm{{min}}$ (denoted as the wet-state). After a drying process at $25^{\\circ}\\mathrm{C}$ for $12\\mathrm{~h~}$ (denoted as the dry-state), the second anti-fogging test  \n\nwas carried, etc.  \n\nMeasurement of volume and mass swelling ratio. The diameter, height and mass of the dry PVA/PTPM film was firstly measured as $\\mathrm{d}_{0},\\mathrm{h}_{0}$ and $\\mathbf{m}_{0}$ , and then immersed into water at $20^{\\circ}\\mathrm{C}$ After reaching equilibrium swelling, the swollen PVA/PTPM film was taken out, and the diameter and height were measured again as $\\mathbf{d}_{\\mathrm{w}},\\mathrm{h}_{\\mathrm{w}}$ and $\\mathrm{m}_{\\mathrm{w}}$ . The volume and mass swelling ratio denoted as $\\mathrm{Q}_{\\mathrm{V}}$ and $Q_{\\mathrm{M}}$ was obtained from the following equations:   \n$\\begin{array}{r l}&{\\mathrm{Q}_{\\mathrm{V}}=(\\mathrm{d}_{\\mathrm{W}}{}^{\\ast}\\mathrm{h}_{\\mathrm{t}}-\\mathrm{d}_{0}{}^{\\ast}\\mathrm{h}_{0})/\\mathrm{d}_{0}{}^{\\ast}\\mathrm{h}_{0}\\times100\\%}\\\\ &{}\\\\ &{\\mathrm{Q}_{\\mathrm{M}}=\\left(\\mathrm{m}_{\\mathrm{w}}-\\mathrm{m}_{0}\\right)/\\mathrm{m}_{0}\\times100\\%}\\end{array}$   \nMeasurement of water contact angles. The water contact angles were measured using a contact angle meter (OCA25, Germany).   \nAttenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). ATR-FTIR spectra were collected in wavenumber range of $4000{\\cdot}400~\\mathrm{cm}^{-1}$ on a Bruker Einox 55 instrument assisted by ATR attachments.   \nLap shear adhesion test. The adhesive strengths of the PVA/PTPM and PVA network were investigated by shear-lap tests with two substrates of four materials (i.e., glass, PMMA, aluminum and steel). For adhesion tests, the adhesives (PVA/PTPM HN) were applied to one end of the adherend. This end was then covered by another adherend end with an overlap area of $25~\\mathrm{mm}\\times25~\\mathrm{mm}$ in a lap shear configuration. The adherends were pressed together and allowed to keep in water for 5 days at room temperature before testing. Lap shear adhesion tests were performed on an Instron 3365 testing machine with a $5~\\mathrm{kN}$ load cell. The adherends were pulled apart at a  \n\nspeed of $5\\ \\mathrm{mm/min}$ until failure occurred. The adhesion strength was calculated by dividing the force at failure with the overlap area.  \n\n90-dgree peeling test. The 90-dgree peeling test was performed with a universal tensile mechanical (Instron 5567) through pulling the gel sheet with a stiff backing from the substrate (i.e., glass). The peeling fixture maintained the peeling angle to be 90 degrees during the test via a pulley connected to the crosshead of the machine (test standard: ASTM D 2861). The rectangular hydrogels $\\mathrm{80~mm}\\times20\\mathrm{\\mm}\\times2\\mathrm{\\mm}$ ) were used for the 90-dgree peeling test at a speed of $5\\ \\mathrm{mm/min}$ . The interfacial toughness was calculated by dividing the steady-state (or plateau) peeling force with the sample width.  \n\nRheological measurements. The rheology experiment of the PVA-TPM and PVA/PTPM solutions (before and after UV irradiation) were measured at $25^{\\circ}\\mathrm{C}$ using an TA Company's strain control rheometer ARES-G2. According to the concentration of solutions, the cone with the diameter of $25~\\mathrm{mm}$ and the cone angle of $1.024^{\\circ}$ was selected to test the rheological properties. The oscillation frequency sweep range was 0.1-100 Hz. Strain sweep was performed at a fixed frequency of $1\\:\\mathrm{Hz}$ for each sample, and the strain sweep range was $0.1\\sim20\\%$ to determine the linear region. Finally, the strain of $5\\%$ was selected, which kept samples in the linear viscoelastic region. Cryogenic scanning electron microscopy (Cryo-SEM) experiments. The specimens were transferred into a Cryo-preparation chamber (LEICA EM ACE600) under vacuum and sublimed by cooling to $-100^{\\circ}\\mathsf{C}$ for about $20~\\mathrm{min}$ . The frozen surface of the specimens was coated with $\\mathrm{\\sfPt}$ in order to make it conductive in an argon environment ( $15~\\mathrm{mA}$ for 200 s). Then the specimens were transferred to the cryostage of $-137^{\\circ}\\mathrm{C}$ in the microscope (S-4300, HITACHI, Ltd, Japan). Finally, images were recorded using a $3\\mathrm{kV}$ landing energy and $10\\upmu\\mathrm{A}$ current.  \n\nShore hardness test. The shore durometer was placed on the sample and tested by pressing.  \n\nScratching test. The PVA/PTPM HN coatings at dry and wet states were repeatedly scratched using a piece of $500\\textrm{g}$ weight wrapped with a spectacle cloth. The transmittance of PVA/PTPM HN coatings was measured after 50 cycles of dynamic scratching.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# Supplemental Movie  \n\nThe movie showed the superb anti-fogging performance of the PVA/PTPM HN coated glass slide compared with the pristine one. When exposed to hot water vapor $(60^{\\circ}\\mathrm{C})$ , the glass with PVA/PTPM HN coating maintained clear visions after $300~\\mathrm{s}.$ while the pristine glass slide showed blurred visions at $10~\\mathrm{s}$ .",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# Supplemental Figures  \n\n![](images/3d29223dced74d44a5ae9a1d9b842d1bf3089be34c57405811c5b950bd8ed7c2.jpg)  \n\n![](images/3ae7748795c65cada62b79e11ddff09c84bf853a7fc0b2dda1f9c2e3664a441a.jpg)  \nFigure S1. The water contact angle of the PVA/PTPM HN coating and bare glass over time.  \n\nabsorption peak representing $\\scriptstyle\\mathbf{C}=\\mathbf{C}$ double bond $(1635~\\mathrm{~cm}^{-1})$ disappeared after photoinitiated polymerization. And the wavenumber of $C{=}0{-}0$ ester group (1710 $\\mathrm{cm}^{-1}$ ) had a blue-shift to $1730\\mathrm{cm}^{-1}$ , owing to the destroy of conjugated structure.  \n\n![](images/baa8a2f8a19f3f475eb3b4ab4d810f9aad091a1f760823d1b52d67993c88b4e1.jpg)  \nFigure S2. FT-IR spectra of the PVA/PTPM, PVA/TPM and pure PVA solutions. The   \nFigure S3 Rheological characterization of PVA/PTPM and PVA/TPM solutions. The  \n\nviscosity of the PVA/PTPM solution increased compared with the PVA/TPM solution, indicating the formation of PTPM network.  \n\n![](images/ee045754d259bd6d38a477e262bd860f8117f56c01a1a19b80d2309429569214.jpg)  \nFigure S4. (a) The average transmittance of PVA/PTPM HN coatings with different  \n\nmass ratio of PVA/PTPM and various thickness on glass slides. (b) Wet-contact adhesion strength of PVA/PTPM HN with different mass ratio of PVA/PTPM on glass. (c) The average transmittance of PVA/PTPM HN coatings with the PVA/PTPM mass ratio of 17/1 on glass with varying thickness over time when exposed to hot water vapor $(60^{\\circ}\\mathrm{C})$ . (d) Anti-fogging duration of PVA/PTPM HN coatings with the PVA/PTPM mass ratio of 17/1 on glass with varying thickness.  \n\n![](images/3a8fc85c4d1d7a934c6e7f5351dc0b36e52bbe1379b633facec0cd1a7db41570.jpg)  \nFigure S5. Contact angle measurements of the PVA-SI coating during the different preparation stage.  \n\n![](images/a05e29512d89a97b6010ca4c1d8370e2c438a25217bc1b1e9e0725ef13e5cb66.jpg)  \nFigure S6. Transmission spectra of the (a-c) PVA/PTPM HN, (d-f) PVA-WI and (g-i)  \n\nPVA-SI coatings on glass slides with the thickness of (a, d, g) $25~{\\upmu\\mathrm{m}}$ , (b, e, h) $100\\upmu\\mathrm{m}$  \n\nand (c, f, i) $200\\upmu\\mathrm{m}$ .  \n\n![](images/d6c68bd116d0025162bb1c395f32d2549ffc0b90e6e300f63f133dc25058eee5.jpg)  \nFigure S7. Surface morphology of (a-c) PVA/PTPM HN, (d-f) PVA-WI and (h-i)  \n\nPVA-SI coatings on glass slides with the thickness of (a, d, g) $25\\upmu\\mathrm{m}$ , (b, e, h) $100\\upmu\\mathrm{m}$ , (c, f, i) $200~{\\upmu\\mathrm{m}}$ . The thickened fragile PVA-WI coating was prone to generate wrinkles caused by the unstable adhesion and the PVA-SI tended to form image distortion as heterogeneous swelling behavior of PVA network, while the PVA/PTPM HN coating maintained smooth and transparency when simultaneously increasing the thickness and test time of anti-fogging, indicating the stable interfacial adhesion and uniform network structure.  \n\n![](images/daf6e54866557534f74d83fdb0b2a31b419086333900a0ccd5bfa610f5ca32fc.jpg)  \nFigure S8. Water absorption of PVA/PTPM HN coatings with different thickness.  \n\n![](images/c03957e911e4bfa203d67e9a356c3b6c33a8ef4496c11d551fe2b717c1350282.jpg)  \nFigure S9. Cryo-SEM images of the (a) PVA/PTPM HN coating (DMSO route)  \n\nprepared by solvent displacement from DMSO to water and (b) PVA/PTPM HN coating (water route) fabricated directly in water.  \n\n![](images/6bcf5040a675999ab53126ccce52f51638d44500394d9c1345ff0b713d776761.jpg)  \nFigure S10. Optical photos of the PVA/PTPM gels prepared through DMSO route  \n\n(left) and water route (right).  \n\n![](images/1d359f066eca65bad3e9debaa3d11c47152f755af923d6b741e2e33607e52561.jpg)  \nFigure S11. (a) The average transmittance of PVA/PTPM HN (Water route) and  \n\nPVA/PTPM HN (DMSO route) coatings with various thickness on glass slides. (b) Optical images of PVA/PTPM HN (Water route) and PVA/PTPM HN (DMSO route) coatings with the same thickness of $100~{\\upmu\\mathrm{m}}$ on glass slides. Serious blur of image was observed on glass slide with PVA/PTPM HN (water route) coating caused by phase separation of TPM in water.  \n\n![](images/fd6be720552cf9a1368b8276fb648818337a35620f6bcaa072544bde28efab17.jpg)  \nFigure S12. Adhesion strength of PVA/PTPM HN on glass and PMMA substrates at dry state.  \n\n![](images/deacd14bdbd79b0bffe9264148d64cdbf59ff81ff422dbb991c1128bb46ca538.jpg)  \nFigure S13. Optical images showing the bonded glass plates by PVA/PTPM HN can  \n\nlift a hydrothermal reactor with a weight of $5\\mathrm{kg}$ in air (left) and water (right).  \n\n![](images/050cd590f3843a8aeb2bc72eee54c4d17aab36a8e6288149489df8f80abedf65.jpg)  \n\nFigure S14. Optical images of mixed adhesive failure for two glass plates glued by the adhesive wet PVA/PTPM HN after a lap shear test.  \n\n![](images/653f6bf3dc9696eea7690d7e321d8b927e7dcf2fa57b9569075926b7ebe6d3eb.jpg)  \nFigure S15. The 90-dgree peeling test of PVA/PTPM HN coating. (a) Photograph of  \n\nPVA/PTPM HN coating during peeling test. (b) Interfacial toughness-displacement curves of PVA/PTPM HN coating.  \n\n![](images/01e0ae71993e2950c491c6982b7fb4bd336a8cfb9a771dc20c900a6b9c7ef684.jpg)  \nFigure S16. Mechanism for the strong adhesion of the wet PVA/PTPM HN on  \n\nPMMA. The PMMA substrate can be swollen by DMSO and the TPM monomers can penetrate into the PMMA surface to form topological entanglements between PTPM and PMMA after polymerization, which contributed to the superb adhesion of the wet PVA/PTPM HN on PMMA.  \n\n![](images/ce564235bf443420861e06b83904e06c146e77210626ff48b4b2e2a71e54ee78.jpg)  \nFigure S17. Wet-contact adhesion strength of the PVA network on glass and PMMA substrates.  \n\n![](images/4aef016e391ffb1e91b0bfa5a51f8f45a6efa793bbcbba4517742f71e7c8acf3.jpg)  \nFigure S18. Wet-contact adhesion strength of PVA/PTPM HN gluing two dissimilar  \n\nsubstrates with distinct properties.  \n\n![](images/71e06473ef8b8f30a5122d4174101ce981b7d604fb5a7c0c56ddd50f6fa33c7e.jpg)  \nFigure S19. (a) The average transmittance of PVA-WI and PVA/PTPM HN coatings on PMMA with varying thickness over time when exposed to hot water vapor $(60^{\\circ}\\mathsf{C})$ .  \n\n(b) Surface morphology of PVA/WI (bottom) and PVA/PTPM HN (top) coatings on PMMA with the thickness of $25~{\\upmu\\mathrm{m}}$ , $100\\upmu\\mathrm{m}$ , $200\\upmu\\mathrm{m}$ after exposed to hot vapor $(60^{\\circ}\\mathsf{C})$ for 5 min (left), 10 min (middle) and $20\\ \\mathrm{min}$ (right), respectively. The thickened fragile PVA-WI coating was prone to generate wrinkles caused by the unstable adhesion, while the PVA/PTPM HN coating maintained smooth and transparency when simultaneously increasing the thickness and test time of anti-fogging, attributed to the stable interfacial adhesion and uniform network structure. (c) Anti-fogging duration of PVA-SI and PVA/PTPM HN coatings on glass slides with varying thickness.  \n\n![](images/5a204120e02e4dd07c254a79d3d53066b9f665a09776d0ed8f8f3559d870becd.jpg)  \nFigure S20. Shore hardness test of PVA/PTPM HN coating at dry and wet states.  \n\n![](images/e83f61be26c856672c5bc93aa33b898d02660aac20ae5dc1c4747335a31e8195.jpg)  \nFigure S21. Measured transmittance of the PVA/PTPM HN coatings at dry and wet  \n\nstates after a $5\\mathrm{N}$ load of dynamic scratching.  \n\n![](images/fef582d723af63975c69e2697acfffeb37b51c017598a705ea13aecd091d5dbd.jpg)  \nFigure S22. Transmission spectra of the PVA/PTPM HN coating on glass slides with  \n\nthe same thickness of $100~{\\upmu\\mathrm{m}}$ over time under (a) $20^{\\circ}\\mathrm{C},$ (b) $40^{\\circ}\\mathrm{C},$ (c) $60^{\\circ}\\mathsf{C}$ (d) $80^{\\circ}\\mathrm{C}$ and  \n\n(e) $100^{\\circ}\\mathsf{C}$  \n\n![](images/6e452b74e9bc3fe7812abcca231dbf36da78a51e066306272a4b26ae50ec1f73.jpg)  \nFigure S23. Mass (a) and volume (b) swelling ratio of PVA (DMSO route) and  \n\nPVA/PTPM HN (DMSO route) in water over time. (c) Optical images of PVA/PTPM HN (DMSO route) before (top) and after (bottom) swelling in water.  \n\n![](images/80a2c73f1b09fac515c285b86d5fbe479d69bdddba7025bae86a6d0c8d81d581.jpg)  \nFigure S24. Optical images of PVA/PTPM HN (top) and PVA-WI (bottom) coatings  \n\nafter soaking in $20^{\\circ}\\mathrm{C}$ water for 1 day and 3 days.  \n\n![](images/3d00090d6fc2c004b96a6811498a9c6d175919d448567b4ebfe0ab5e97196aab.jpg)  \nFigure S25. Fingerprints on PVA/PTPM HN coated (left) and uncoated (right) glass slides after rinsing with water.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# References  \n\n[1] W. Zhang, X. Zou, F. Wei, H. Wang, G. Zhang, Y. Huang, Y. Zhang, Compos. Pt. B-Eng. 2019, 162, 500.   \n[2] X. Yu, J. Zhao, C. Wu, B. Li, C. Sun, S. Huang, X. Tian, Mater. Des. 2020, 194, 108956.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Supporting Information for  \n\nDesign of Abrasion Resistant, Long-lasting Anti-Fog Coatings  \n\nBrian Macdonald1, Fan-Wei Wang2, Brian Tobelmann1, Jing Wang3, Jason Landini1, Nipuli   \nGunaratne2, Joseph Kovac4, Todd Miller5, Ravi Mosurkal5, Anish Tuteja1,2,6,7,\\*   \n1 Department of Materials Science and Engineering, University of Michigan, Ann Arbor, MI   \n48109, USA   \n2 Department of Chemical Engineering, University of Michigan, Ann Arbor 48109, MI, USA   \n3 Department of Mechanical Engineering University of Michigan, Ann Arbor, MI 48109, USA   \n4 Department of Aerospace Engineering, University of Michigan, Ann   \nArbor 48109, MI, USA   \n5Protection Materials Division, Soldier Protection Directorate, US Army DEVCOM Soldier   \nCenter, 15 General Greene Avenue, Natick, MA 01760   \n6 Department of Macromolecular Science and Engineering, University of Michigan, Ann   \nArbor, MI 48109, USA   \n7 Biointerfaces Institute, University of Michigan, Ann Arbor, MI 48109, USA   \n\\*Corresponding author. Email: atuteja $@$ umich.edu  \n\nFourier Transform Infrared Spectroscopy (FTIR)  \n\nInfrared spectrum measurement was conducted by a Nicolet 6700 FTIR spectrometer (Thermo Scientific) with an ATR (diamond crystal) and a frequency range of $400{-}4{,}000\\ \\mathrm{cm^{-1}}$ . Antifog samples were coated on polycarbonate and analyzed as a function of UV time. To confirm the crosslinking of adjacent pyrrolidone groups within PVP and within the presence of $\\mathrm{H}_{2}\\mathrm{O}_{2}$ , the $\\scriptstyle{\\mathrm{C=O}}$ group was tracked for samples with varying UV time. Figure 1A demonstrates that a 10-minute UV time – the UV time utilized for our experiments – was sufficient to produce crosslinking of adjacent PVP. To investigate the self-reacting nature of the toughening agent, PETRA solutions were made to analyze the curing properties with a concentration of $0.090\\mathrm{g/ml}$ in a 0.091:0.900 mixture of $30\\%$ hydrogen peroxide and 1-Propanol. The PETRA solution was sprayed onto small polycarbonate strips ( $1/2\\mathrm{~x~}1$ inch) and cured under UV at varying times. Figure S1B displays a segment of an FTIR spectrum for pure PETRA on polycarbonate. The peak at $820\\mathrm{cm}^{-1}$ pertaining to acrylate functional groups shows a decrease with increasing UV time 1. This indicates that PETRA oligomers self-crosslink in the presence of hydrogen peroxide and UV irradiation. After 10 minutes, there is a notable decrease in the acrylate peak which indicates crosslinking, and the formation of a partial S-IPN.  \n\n![](images/77968d1458d4135fdc4ad8813e763c3be7bd120a20f9a5466c764a373fad9b13.jpg)  \nFigure S1. A) Change in $\\scriptstyle{\\mathrm{C=O}}$ bond for a PVP antifog coated polycarbonate as a function of UVC exposure time. B) Change in acrylate peak of pure PETRA coated polycarbonate with increasing UVC exposure  \n\nThe thin polymer strips were fabricated by developing a $0.053\\mathrm{g/ml}$ solution of PVP in 1-propanol, water, and $30\\%$ $\\mathrm{H}_{2}\\mathrm{O}_{2}$ with volume ratios of 0.931:0.029:0.040 respectively. PETRA/1-Propanol solutions were also developed and added to the PVP solution with a volume of 2ml. The PETRA/1- Propanol solutions varied depending on the desired mass ratio of PETRA/PVP. 5mL of the final PVP-based solutions was dispensed into a silicone mold with dimensions of $76.2\\mathrm{x}50.8\\mathrm{x}1.2\\mathrm{mm}$ and allowed to dry for 2 days. The dried film and mold were then placed under UVC for 30 minutes (to ensure that the strip was cured sufficiently). Once cured, the polymer sheet was cut to ${\\sim}7.5-$ 8mm widths and lengths of $\\sim76\\mathrm{mm}$ . The cut samples were immediately sandwiched between two glass plates and allowed to uniformly dry completely for ${>}10$ hours in relative humidity $<20\\%$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 2,
+        "chunk": "# Dynamic Mechanical Analysis (DMA)  \n\nAn RSA-G2 DMA (TA Instruments) was utilized to conduct tensile tests on PVP and PVP/PETRA thin strips. Each sample was secured with untextured flat grips, with a spacing of $35\\mathrm{mm}$ . A strain rate of $0.035\\upmu\\mathrm{m}/\\mathrm{s}$ was used for each sample. The relative humidity of the testing room was maintained at $20\\text{\\textperthousand}$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 3,
+        "chunk": "# Hansen Solubility Parameters:  \n\nHansen solubility parameters were measured by dissolving a small amount (3-5 drops) of surfactant into $10\\mathrm{ml}$ of solvent. The solvents consisted of DI water, Methanol (Fisher Scientific), Ethanol (Fisher Scientific), 1-Propanol (Fisher Scientific), 2-Propanol (Fisher Scientific), Dimethyl Formamide (Fisher Scientific), 1-Hexanol (Sigma-Aldrich), Dimethyl Sulfoxide (Fisher Scientific), Ethyl Acetate (Sigma-Aldrich), Toluene (Fisher Scientific), Benzene (Fisher Scientific), Cyclohexane (Acros Organics), Decane (Sigma-Aldrich), Pentane (Fisher Scientific), n-Heptane (Acros Organics), O-Xylene (Acros Organics), Perfluorohexane (Alfa Aesar), Formamide (Sigma-Aldrich), Acetonitrile (Fisher Scientific), Acetic Acid, (Fisher Scientific) Propylene Carbonate (Alfa Aesar), Methyl Acetate (Acros Organics), Chloroform (Fisher Scientific), and $30\\%$ Hydrogen Peroxide (Fisher Scientific). Once added to the solvent, the solutions were mixed briefly in a vortexer (Vortex-Genie 2 - Scientific Industries, Inc). The solutions were visually inspected to determine their solubility within each solvent and noted. The data (either miscible or immiscible) was plugged into the HSPiP version 5.3.09 and Hansen solubility parameters and sphere radii were generated. The results are listed in Table S1.  \n\nTable S1. Hansen solubility parameters calculated by HSPiP software. \\*PVP parameters were taken from the HSPiP database.   \n\n\n<html><body><table><tr><td></td><td>8D</td><td>8P</td><td>8H</td><td>R</td></tr><tr><td>PS20</td><td>17.06 ±1.4</td><td>7.93 ±1.2</td><td>19.3 ±0.7</td><td>18.9</td></tr><tr><td>PS80</td><td>16.76 ±0.65</td><td>7.81 ±1.25</td><td>19.22 ±0.65</td><td>18.9</td></tr><tr><td>PS85</td><td>13.57 ±0.65</td><td>3.64 ±1.25</td><td>14.17 ±0.95</td><td>15.7</td></tr><tr><td>SPAN20</td><td>13.15 ±2.6</td><td>0.10 ±1.35</td><td>12.6 ±1.35</td><td>14.6</td></tr><tr><td>SPAN80</td><td>13.67 ±1.8</td><td>0.09 ±2.35</td><td>9.64 ±1.2</td><td>11.7</td></tr><tr><td>PVP*</td><td>18.1</td><td>10</td><td>18</td><td>8</td></tr></table></body></html>  \n\nTable S2. Select Surfactants and corresponding HLB values and $\\mathbf{S}^{*}$ values.   \n\n\n<html><body><table><tr><td>Slip Additive</td><td>Hydrophilic- Lipophilic Balance (HLB)</td><td>Miscibility Parameter (S*)</td></tr><tr><td>PS20</td><td>16.7</td><td>-0.515</td></tr><tr><td>PS80</td><td>15.0</td><td>-0.504</td></tr><tr><td>PS85</td><td>11.0</td><td>0.062</td></tr><tr><td>SPAN20</td><td>8.6</td><td>0.357</td></tr><tr><td>SPAN80</td><td>4.3</td><td>0.506</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# Friction Coefficient  \n\nThe steady-state dynamic friction coefficient was measured with a Shimpo model FG-7005 force gauge. The force gauge was attached horizontally to a motorized stage which traveled at a controlled velocity of $74~{\\upmu\\mathrm{m/s}}$ . An aluminum block with dimensions of $44\\mathrm{x}50\\mathrm{x}24\\mathrm{mm}$ and with a standard nonwoven cleanroom wipe (Texwipe TX606) adhered to the $44\\mathrm{x}24\\mathrm{mm}$ face was pushed across each surface with the force gauge. The substrates were secured onto a level adjacent stage statically with double-sided tape. Force data was taken every 0.2 seconds and was pushed for 60 seconds. Table S3 displays the average dynamic friction coefficients for the plateaued regions.  \n\nTable S3. Average steady-state friction coefficients of polycarbonate and antifog coated polycarbonate.   \n\n\n<html><body><table><tr><td>Surface</td><td>Average Coefficient</td><td>Friction</td></tr><tr><td>Polycarbonate</td><td>0.522</td><td></td></tr><tr><td>PVP</td><td>0.598</td><td></td></tr><tr><td>PVP/20%PETRA</td><td>0.599</td><td></td></tr><tr><td>15% SPAN80</td><td>0.139</td><td></td></tr><tr><td>15% SPAN20</td><td>0.152</td><td></td></tr><tr><td>15% PS85</td><td>0.171</td><td></td></tr><tr><td>15% PS80</td><td>0.196</td><td></td></tr><tr><td>15% PS20</td><td>0.167</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# Abrasion Testing  \n\nWe utilized the Taber abrader to conduct the ASTM D4060 tests which evaluates the durability and wear resistance of organic coatings. This test has been shown to correlate very well with the long-term durability of organic coatings and paints, and has been widely utilized to be able to predict the long-term performance of different organic coatings since the 1930s. Additionally, the wearing action of the abrader typically pulls the coating away from the surface during the abrasion cycles. Thus, the adhesion to the substrate can be a significant contributor (and therefore an indirect measure) to the overall wear resistance of a given coating. All substrates were abrasion tested with a Taber Linear abrader Model 5750 with a stroke length of 1 inch and frequency of 60 cycles/minute. $32\\mathrm{x}32\\ \\mathrm{mm}$ samples were abraded with a stroke length of 0.5 inches. A CS-5 abrasion tip was used for each test and was purchased from the Taber manufacturer. Between each test, the CS-5 was washed with IPA to remove potential debris or surfactant. The number of cycles varied between ${\\sim}10$ and 8000 depending on the tests. The weight varied between $300\\mathrm{g}$ and $1050\\mathrm{g}$ .  \n\n![](images/aa569f36877a849aef522f81c2b069dcd4c2b4535440324828149a5f562f1053.jpg)  \nFigure S2. Linear Tabor abrasion setup for antifog coated polycarbonate and the SEM image of the microstructure of the CS-5 felt tip abrasion tip.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# Controlled Wiping Simulation  \n\nTo be able to uniformly abrade a large sample surface, and thereby evaluate the impact of normal, everyday wiping on the developed coatings antifog performance, we modified the Taber abrader to include a common microfiber lens wipe which was attached to a 1” x 1” block of soft foam and mounted to the raster arm of the abrader. The samples were mounted to the apparatus in the same fashion as prior and wiped with the custom lens wipe fixture with a stroke length of 1 inch and frequency of 60 cycles/min. For 32x32 mm samples, 1-inch polycarbonate spacers were placed on either side of the sample to allow full range of motion of the raster arm.  \n\nTable S4. List of experiments demonstrating material and additive effects on sequential abrasion resistance to CS-5 Tabor Abrasion under increasing mass. A $\\checkmark$ indicates the absence of visible abrasion after abrasion cycles and $\\cdot$ indicates the presence of obvious abrasion. Each cycle was done in succession per sample.   \n\n\n<html><body><table><tr><td>PVP</td><td>Composition Coating</td><td colspan=\"7\">Abrasion Cycle and Qualitative Result</td></tr><tr><td>%PETRA</td><td>Slip Additive</td><td>5000 (300g)</td><td>Cycles</td><td>1000 (550g)</td><td>Cycles</td><td>1000 (800g)</td><td>Cycles</td><td>1000 (1050g)</td><td>Cycles</td></tr><tr><td></td><td>10% PS80</td><td>×</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>0%</td><td>15% PS80</td><td>√</td><td></td><td></td><td></td><td>X</td><td></td><td>×</td><td></td></tr><tr><td></td><td>20% PS80</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td>×</td><td></td></tr><tr><td></td><td>10% PS80</td><td>×</td><td></td><td></td><td></td><td>X</td><td></td><td></td><td></td></tr><tr><td>10%</td><td>15% PS80</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>20% PS80</td><td>?</td><td></td><td>√</td><td></td><td></td><td></td><td>√</td><td></td></tr><tr><td></td><td>10% PS80</td><td></td><td></td><td></td><td></td><td>X</td><td></td><td></td><td></td></tr><tr><td>15%</td><td>15% PS80</td><td></td><td></td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td></tr><tr><td></td><td>20% PS80</td><td></td><td></td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td></tr><tr><td></td><td>10% PS80</td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td></tr><tr><td>20%</td><td>15% PS80</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>20% PS80</td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td></tr><tr><td></td><td>10% PS20</td><td>?</td><td></td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td></tr><tr><td>20%</td><td>15% PS20</td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td></td><td>20% PS20</td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td></tr><tr><td></td><td>10% SPAN80</td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td></tr><tr><td>20%</td><td>15% SPAN80</td><td></td><td></td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td></tr><tr><td></td><td>20% SPAN80</td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td></tr><tr><td>20%</td><td>15% SPAN20</td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td></tr><tr><td>20%</td><td>15% PS85</td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td><td></td><td></td></tr></table></body></html>  \n\n![](images/c3a0874f2083309e18e8a04aadf5f8ed3a0af86f89a6b75da7d27093413908c4.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# Scanning Electron Microscopy  \n\nScanning electron micrographs were obtained with a Tescan MIRA3 FEGSEM. A beam intensity of 7, an accelerating voltage of $7\\mathrm{kV}$ , and a working distance between 9-11mm were used for each micrograph.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# Linear Stylus Profilometry  \n\nSurface roughness was measured via a Dektak 6M stylus profilometer. A 5mg stylus force, a segment length of $2000\\upmu\\mathrm{m}$ , and a raster time of 120 seconds were used for each measurement. At least 4 spatially separated segments were measured for each sample (abraded and unabraded).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# Homemade Fog Tester  \n\nExperimental structure for fogging tests  \n\nExperiments were conducted in a stainless-steel chamber (Figure S3A) with an observation window (the outer diameter of 6 inches and the inner diameter of 4 inches) (Figure S3B). The coated polycarbonate plates $35\\mathrm{mm}\\times35\\mathrm{mm}\\times1\\mathrm{mm}$ ) (Figure S3C) were held with a cylindrical glass (a diameter of 1.5 inches and a height of 0.5 inches) (Figure S3D) and an aluminum plate $(32\\mathrm{mm}\\mathrm{x}32\\mathrm{mm}$ , with text design) (Figure S3E) by a holder (Figure S3F) with a square Teflon window (the inner dimension of $25~\\mathrm{mm}$ and outer dimension of $47~\\mathrm{mm}$ ) fixed on the cooling platform with screws. The aluminum plates were mounted onto a copper pillar $20\\mathrm{mm}\\times20\\mathrm{mm}$ ) (Figure S3G) using fast-drying silver paint (Ted Pella, Inc., USA). Liquid cooling channels (Figure S3H) were built into the opposite end of the copper pillar with ethylene glycol (Arcos Organics, USA) pumped through by an MS immersion thermostat (Lauda, Germany) and cooled by $1/2\\mathrm{HP}$ glycol chiller (Penguin Chillers, USA). The temperature is controlled by the circulator in a precision of $\\pm0.1^{\\circ}\\mathrm{C}$ . The entire portion of copper was insulated from the environment with a Teflon enclosure (a diameter of $11.5~\\mathrm{cm}$ ) (Figure S3I) and was mounted to the test chamber. A type-T thermocouple (OMEGATM, USA) was used to measure the temperature of the sample surface. A temperature/humidity gauge iTHX-W3-2 (OMEGATM, USA) (Figure S3J) was mounted on the top of the chamber to obtain the humidity/temperature readings. A self-made humidity-controlled box (Figure S3K) was linked to the top of the chamber to blow humid air into the chamber. The other side of the box was connected to an air supply with an adjustable valve. The dry air from the air supply was blown to the box which stores water to gain humidity and then to the chamber to control the humidity. The air went out of the chamber through the air outlet (Figure S3L) at the bottom of the chamber.  \n\n![](images/11d93e9ac33e71a93c555fe246ef6e7fb38c7add1f0146dd2f4b40711288aa09.jpg)  \nFigure S3. A schematic diagram of the test chamber.  \n\nExperimental setup for fogging test  \n\nThe circulator was first held at the temperature of $40.0{\\pm}0.1\\ ^{\\circ}\\mathrm{C}$ to control the surface temperature of the sample at $28{\\pm}1~^{\\circ}\\mathrm{C}$ to prevent any fogging before the test. After the humidity was controlled at $65\\pm1\\ \\%$ relative humidity and the temperature was $22{\\pm}2\\ ^{\\circ}\\mathrm{C}$ , the target value of the circulator was changed to $5.0{\\pm}0.1~^{\\circ}\\mathrm{C}$ (surface temperature of the sample would be $14{\\pm}0.5\\ ^{\\circ}\\mathrm{C}$ ) and the experiment started. The fogging evolution on the sample was captured by a single-lens camera D3200 (Nikon, Japan) with a $150\\ \\mathrm{mm}\\ \\mathrm{f}/2.8$ Macro 1:1 lens (Irix, Switzerland) and a $28~\\mathrm{mm}$ long spacer (Photo Plus, USA) at the rate of 1 frame per minute controlled by RC-N2II ShutterBoss II timer remote switch (Vello, USA) with a light source VM-160 LED macro ring light (Bolt, USA). The experiment duration was 45 min for normal fogging tests and 20 min for the cyclic fogging test (15 cycles in total).  The detailed humidity and temperature changes during the experiment are listed in the supplemental materials. A reference image was placed behind the substrate, and between them, a 1-inch glass spacer to enhance the effect of image distortion from a fog. Images were captured every minute, for 40 minutes. The reference image provides the ability to visually display fogging properties over time and is used to measure image distortion caused by fogging. Image distortion was analyzed with an open-source ImageJ plugin utilized and developed by Lee et al 2.  \n\nHumidity and temperature change during the experiments  \n\nThe humidity and temperature change are shown in Figure S4. The humidity changed from $65{\\pm}1$ $\\%$ to $54\\pm1\\%$ and stayed stable from about 10 minutes after the experiments began. The sampleto-sample variation of different test samples and different coatings is within $1\\%$ , showing the consistency of the experimental manipulation. On the other hand, the temperature changed from  \n\n$29^{\\circ}\\mathrm{C}$ to $14~^{\\circ}\\mathrm{C}$ and maintained stable from about 10 minutes, which is similar to the trend of the humidity. Near 10 minutes, the temperature became lower than $15^{\\circ}\\mathrm{C}$ which is estimated to be near the dew point of the system (estimated under the condition of $65\\%$ relative humidity and $22^{\\circ}\\mathrm{C}$ temperature), leading to the beginning of the fogging which can be observed from the experiments.  \n\n![](images/19f63477a5e98f0ae2000f63c71b1e0ac8a51e7b9a8daf3236058ffc23daddc2.jpg)  \nFigure S4.  The humidity and temperature evolution during the experiments. The red cross denotes the temperature corresponding to the secondary y-axis. The hollow orange triangle, the hollow grey diamond, and the hollow yellow circle respectively denote the humidity records during the fogging tests of PS 85 coating, SPAN 20 coating, and PVP coating. All the error bars are obtained from the standard deviations from triplet trials.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# Fog Tester developed at the US Army Soldier Center, Natick, MA  \n\nThe fog tester consisted of an environmentally controlled chamber, a head form and a radiator disposed within the chamber.  The radiator was connected to a liquid cooling system.  A humidifier device was configured to deliver a flow of warm moist air towards the frontal portion of the head form, and the surface of the eyewear. A camera within the head form aligned with an eye position opening was configured to detect a target image within the chamber while the flow of warm moist air is delivered. A processor was configured to calculate a contrast difference between the background of the target image detected by the camera and the resolution bars of the target image detected by the camera. The final pass/fail criteria for anti-fog substrates or eyewear were determined based on the contrast ratio data equal to less than $7\\%$ Haze.  \n\nIn a typical fog testing experiment, the sample glass plate or eyewear was inserted into the enclosure via iris ports or open top of the environmental chamber as required. The humidifier system was turned on for 15 minutes or until the eyewear equilibrated to the humid conditions. The sample plate was placed in front of the eye of the head form with a clamp and the angle. The tilt angle was adjusted until the full field view of the camera image readout was obtained. The test time was fixed to 60 seconds (at 2 frames per second record rate) and the data was collected.  The measurement was repeated two more times, waiting for 5 minutes in between the tests.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# UV-Vis Optical Properties  \n\nTransmittance and transmission haze were measured with a Shimadzu UV-2600. Transmittance haze is the fraction of light scattered when the incident light passes through a transparent material and describes the optical clarity of a material 3. Experimentally, haze was measured by the total transmittance of the sample $\\mathrm{(T_{s})}$ and the diffusion rate of both the sample $\\mathrm{(DT_{s})}$ ) as well as the instrument $(\\mathrm{DT_{ins}})$ ) using a UV-vis spectrophotometer equipped with an integrating sphere. The haze percentage was calculated by the following equation:  \n\n$$\n\\%\\mathrm{{Haze}=(}D T_{\\mathrm{{s}}}-D T_{\\mathrm{{ins}}})/T_{\\mathrm{{s}}}\\times100\\%\n$$  \n\nComparison to Commercial Antifog Solutions Optix 55 (Purchased from Amazon), Revision Military Anti-Fog Cloth (Purchased from Amazon), and Gear Aid McNett Tactical OP Drops (Purchased from Amazon) temporary antifog solutions were all applied to the substrates using the directions indicated by the manufacturers. The Exxene HCF-100 Anti-Fog Coating formulation (Donated by Exxene Corporation) was applied to the substrates via flow coating method and cured on a $110^{\\circ}\\mathrm{C}$ hotplate for 1 hour.  \n\n![](images/2b38d29a19bb2c91ec86a6ce31828c2ec147b2e23c12b275f53e58bdc6683258.jpg)  \nFigure S5. Static water contact angles for different commercial antifog coatings, as well as the optimal PS20 coating developed in our work.  \n\nFigure S5 shows the static water contact angle for the different commercial coatings and treatments tested in our work, as well as the optimal PS 20 coating. The temporary antifog solutions (Optix and Ops Drops) yielded low contact angles due to their hydrophilic properties and high degrees of freedom when compared to crosslinked coatings. Exxene yielded relatively high contact angles but offered time-dependent absorbing capabilities over the course of 5 minutes. Unlike  \n\nExxeene, the contact angle of our PS20 durable antifog coating yielded comparatively low contact angle values.  \n\n![](images/c9acf01f6f5934a2a1a2d50bf9d528757ebcfad20a0fd9422261fbe50684ea50.jpg)  \nFigure S6. Change in roughness of commercial antifog formulations and, polycarbonate (PC), and the PS20 antifog coating after 8000 CS-5 abrasion cycles.  \n\nFigure S6 demonstrates that the temporary coatings did not yield significant wear resistance, but did perform better than bare polycarbonate. This finding agrees well with the durability data of surfactant additive antifog coatings. Since the temporary agents exist as free antifogging macromolecules on the surface, they impart a lubricating or slip effect and therefore a degree of wear resistance. However, unlike our coating which contains embedded surfactant within the film network, these ephemeral antifog solutions can only offer wear resistance for a short duration and can be easily removed mechanically. Exxene does not contain any additive, but is characteristically durable as polyurethane and therefore proved to be highly wear-resistant. However, the wear resistance inherently compromised the performance of antifogging.  \n\nA.  \n\n![](images/64d6de6de3f497ea784408c1c49e44136bcdab2f0a68210b0855aa404f510902.jpg)  \n\nC.  \n\n![](images/0b0b305e1eea8215590d59397c0c749bdcd35035a4ed6e06854ab3871c6683c4.jpg)  \nFigure S7. Longevity of static water contact angle performance with extended exposure time to normal environmental conditions. Contact angle at A) time $=0$ min, B) time $=1~\\mathrm{min}$ , and C) time $=5\\mathrm{min}$ .  \n\nThe comparative performance longevity of each antifog formulation was assessed by monitoring the contact angle of each week. The samples were kept in open-air normal laboratory conditions between sampling and like previous contact angle measurements, time-series contact angle data were taken to observe the absorbency of the coatings. As shown in Figures 5 and 7, the contact angle for the crosslinked polymer coatings (PVP, PS20, Exxene) decreases notably with time, indicating the absorption of water. Plasma-treated polycarbonate and Optix do not show considerable contact angle change over the course of 5 minutes (contact angle change here is due to evaporation and pinning of the contact line). Over the course of 5 weeks, increases in contact angles due to ambient air contamination increase the contact angle for all coating except the PS20 durable antifog coating. This is particularly true for the Optix antifog coating being that it exists as a thin layer of hydrophilic molecules. The crosslinked PVP and Exxene coatings also yield increases in contact angle, owing to contamination. The PS20 coating being both crosslinked and imbibed with hydrophilic slip additive allows for significant enhancements in hydrophilic longevity.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# References  \n\n(1) Kunwong, D.; Sumanochitraporn, N.; Kaewpirom, S. Curing Behavior of a UV-curable Coating Based on Urethane Acrylate Oligomer: the Influence of Reactive Monomers. Sonklanakarin Journal of Science and Technology 2011, 33 (2), 201.   \n(2) Lee, H.; Alcaraz, M. L.; Rubner, M. F.; Cohen, R. E. Zwitter-wettability and Antifogging Coatings with Frost-resisting Capabilities. ACS Nano 2013, 7 (3), 2172-2185. DOI:   \n10.1021/nn3057966.   \n(3) Yang, D. K.; Chien, L. C.; Doane, J. Cholesteric Liquid Crystal/polymer Dispersion for Haze‐free Light Shutters. Appl. Phys. Lett. 1992, 60 (25), 3102-3104. DOI: 10.1063/1.106765.",
+        "category": " References"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/am7b05286_si_001.json b/task2/task2-chunks/am7b05286_si_001.json
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+++ b/task2/task2-chunks/am7b05286_si_001.json
@@ -0,0 +1,17 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Supporting Information",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# Amphiphilic Antifogging/Anti-icing Coatings Containing POSS-PDMAEMA- $b$ -PSBMA  \n\nChuan Li, Xiaohui Li, Chao Tao, Lixia Ren, Yunhui Zhao, Shan Bai, and Xiaoyan Yuan\\*  \n\nSchool of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300072, China  \n\nE-mail: yuanxy $@$ tju.edu.cn; xyuan28 $@$ yahoo.com  \n\nMaterials. Aminopropyllsobutyl POSS (apPOSS) was purchased from Hybrid Plastics, USA, and used as received. 2-(Dimethylamino) ethyl methacrylate (DMAEMA, $598.5\\%$ ), 2-bromoisobutyryl bromide (BIBB, $599\\%$ ) and ethyl-2-bromoisobutanoate (EBIB, $599\\%$ ) were supplied by Beijing Bailingwei Technology Co. Ltd., China. [2-(Methacryloyloxy) ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA, AR), 1,1,4,7,10,10-hexamethyl-triethylenetetramin (HMTETA, $597\\%$ ) , Igracure 2959 (AR), triethylamine (TEA, $599\\%$ ), 2,2,2-trifluoroethanol (AR) and ethyleneglycol dimethacrylate (EGDMA, $59\\%$ ) were obtained from Tianjin Xi'ensi Aupu Technology Co. Ltd., China. DMAEMA and EGDMA were passed through an alumina column to remove inhibitor. BIBB, EBIB, SBMA, HMTETA, TEA and Igracure 2959 were used without further purification. CuBr (AR) was bought from Tianjin Kermel Chemical Reagent Co. Ltd., China, and was dissolved in glacial acetic acid for $24\\mathrm{~h~}$ to remove $\\mathrm{CuBr}_{2}$ , and washed with methanol and glacial acetic acid for three times, and then dried under vacuum. All other reagents were supplied by Tianjin Yuanli Chemical Co. Ltd., China, and used as received without further purification.  \n\nSynthesis of POSS-Br Initiator. POSS-Br as atom transfer radical polymerization (ATRP) initiator was prepared according to the reference.1 ApPOSS $(0.8745~\\mathrm{g},\\ 1\\ \\mathrm{mmol})$ and TEA 1 $\\mathrm{0.1518~g,}1.5\\mathrm{\\mmol}\\mathrm{}\\mathrm{},$ and THF $(20~\\mathrm{mL})$ ) were charged into a three-necked flask and degassed for at least three times. Degassed BiBB $\\mathrm{(0.2759~g,1.2~mmol}$ , dissolved in $10~\\mathrm{ml}$ THF) solution was slowly added into the flask at $0{}^{\\circ}\\mathrm{C}$ . The solution was magnetically stirred for $^{\\textrm{1h}}$ in an ice/water bath and then maintained at room temperature to react for another $12\\mathrm{~h~}$ . The precipitate was removed by filtration, and the filtrate was washed with a saturated aqueous solution of sodium bicarbonate and NaCl. Anhydrous sodium sulfate was added into the organic layer to eliminate residual moisture. Then, macroinitiator POSS-Br was obtained by removing solvent by a rotary evaporator and followed by vacuum drying (yield $75\\%$ ).  \n\nSynthesis of POSS-PDMAEMA. POSS-PDMAEMA was synthesized by using POSS-Br as an ATRP macroinitiator. The mixture of POSS-Br $(0.1024\\ \\mathrm{g},0.1\\ \\mathrm{mmol})$ , DMAEMA $(1.8865\\ {\\mathrm{g}},$ 12 mmol), HMTETA $(0.0277~\\mathrm{g},\\ 0.12~\\mathrm{mmol})$ and THF $(2\\mathrm{~ml})$ ) was injected into the $10\\mathrm{mL}$ standard Schlenk flask. Highly pure nitrogen was filled the flask and then oxygen was removed by three freeze-pump-thaw cycles. Subsequently, CuBr $0.0144\\ \\mathrm{g},0.1\\ \\mathrm{mmol}$ ) was added quickly to the flask. Three freeze-pump-thaw cycles were carried out again to remove residual oxygen. The mixture was reacted at $50^{\\circ}\\mathrm{C}$ for 1.5, 2 and $2.5\\mathrm{h}$ , respectively, and terminated by dropping a few THF droplets into the flask. The solution was passed through a neutral alumina column to intercept ${\\mathrm{Cu}}^{2+}$ and concentrated in a rotary evaporator. Finally, POSS-PDMAEMA polymers with three different polymerization degrees, i.e., POSS-PDMAEMA $50$ , POSS-PDMAEMA70, and POSS-PDMAEMA90, were obtained by precipitating into cold $n$ -hexane and followed by drying in a vacuum oven for $24\\mathrm{h}$ .  \n\nSynthesis of POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\mathbf{b}$ -PSBMA. In order to obtain block copolymer POSS-PDMAEMA- $b$ -PSBMA, ATRP initiator POSS-Br was first synthesized, and followed by POSS-PDMAEMA-Br preparation from ATRP of DMAEMA. Using POSS-PDMAEMA-Br as the macroinitiator, three POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA block copolymers with different polymerization degrees were synthesized via subsequent ATRP of SBMA. Typically, POSS-PDMAEMA-Br (0.01 mmol), SBMA (1 mmol) and HMTETA $(0.2\\mathrm{mmol})$ ) were dissolved in $6~\\mathrm{mL}$ mixed solvent of methanol-water $(1/1,\\mathbf{v}/\\mathbf{v})$ and were injected into the $25~\\mathrm{mL}$ standard Schlenk flask. The solution was degassed by three freeze-pump-thaw cycles under nitrogen atmosphere and then CuBr (0.1 mmol) was added quickly to the flask. Three freeze-pump-thaw cycles subsequently were carried out again to exclude remaining oxygen. The reaction mixture was stirred at $25~^{\\circ}\\mathrm{C}$ for $40\\mathrm{{h}}$ . POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA block copolymers were obtained by dialysis against deionized water for 3 days (MWCO 2000) and recovered by lyophilization. The POSS-PDMAEMA- $b$ -PSBMA block copolymers with different polymerization degrees and similar DMAEMA to PSBMA ratios, POSS- $\\mathrm{\\cdotD}_{50}–b–\\mathrm{S}_{7}$ , POSS- $\\cdot\\mathrm{D}_{70}{-}b{-}\\mathrm{S}_{10}$ , and POSS- $\\mathrm{\\cdotD}_{90}–b–\\ensuremath{\\mathrm{S}}_{13}$ were prepared.  \n\nSynthesis of PDMAEMA- $\\mathbf{\\delta}_{\\mathbf{b}}$ -PSBMA. Similar to the synthesis of POSS-PDMAEMA- $\\cdot b$ - PSBMA, block copolymer PDMAEMA ${.50}$ - $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA7 without POSS was synthesized by using ethyl-2-bromoisobutanoate as the initiator and followed by using PDMAEMA50-Br as the macroinitiator. PDMAE $\\mathrm{MA}_{50}$ -Br (0.01 mmol), SBMA (1 mmol) and HMTETA $(0.2\\mathrm{mmol})$ ) were dissolved in $6~\\mathrm{mL}$ mixed solvent of methanol-water $(1/1,\\mathbf{v}/\\mathbf{v})$ and were injected into the $25~\\mathrm{mL}$ standard Schlenk flask. The solution was degassed by three freeze-pump-thaw cycles under nitrogen atmosphere and then CuBr (0.1 mmol) was added quickly to the flask. Three freeze-pump-thaw cycles subsequently were carried out again to exclude remaining oxygen. The reaction mixture was stirred at $25~^{\\circ}\\mathrm{C}$ for $40\\mathrm{~h~}$ . The PDMAEMA $_{50}$ - $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA7 block copolymer i.e., $\\mathrm{D}_{50}–b–\\mathrm{S}_{7}$ , was obtained by dialysis against deionized water for 3 days (MWCO 2000) and recovered by lyophilization.  \n\nCharacterizations of POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\pmb{b}$ -PSBMA. $\\mathrm{^{1}H\\ N M R}$ spectra were recorded on an INOVA ${500}~\\mathrm{MHz}$ spectrometer (USA) using $\\mathrm{CDCl}_{3}$ and $\\mathrm{D}_{2}\\mathrm{O}$ as solvents. $\\mathrm{^{1}H\\ N M R}$ spectra of apPOSS, POSS-Br, POSS-PDMAE $\\mathrm{\\uA_{70}}$ , POSS-PDMAEMA $70$ - $\\cdot b$ -PSBMA10 are shown in Figure S1. In comparison with the $\\mathrm{^1H}$ NMR spectrum of POSS- $\\cdot\\mathrm{NH}_{2}$ shown in Figure S1(a), there are representative δH (ppm) at 3.26 (f), 1.96 (h), 6.75 (g) in Figure S1(b), verifying that the initiator POSS-Br was successfully synthesized.2 For POSS-PDMAEMA70 (Figure S1(c)), the appearance of signals of DMAEMA δH (ppm) at 0.89-1.05 (a), 1.82-1.96 (b), 2.32 (d), 2.61 (e), 4.07 (f) and typical δH (ppm) at 0.60 (c) of POSS- $\\mathrm{\\cdotNH}_{2}$ could prove the structure of POSS-PDMAEMA70. Compared with POSS-PDMAEMA $70$ (Figure S1(c)), the chemical structure of POSS-PDMAEMA $70$ - $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA10 (Figure S1(d)) could be confirmed by the evident δH (ppm) at S-3  \n\n4.00 (a), 2.61 (b), 2.19 (c, j), 1.70-1.83 (d, l), 0.77-1.00 (e, p), 3.09 (f), 3.50 (g), 4.35 (h), 2.83 (i),   \n3.66 (k).3  \n\n![](images/271dcad5f089ed3b6a8f6fb249884d5745774bf4f12554588de715b7fc2d2bfe.jpg)  \nFigure S1. $\\mathrm{^{1}H\\ N M R}$ spectra of apPOSS (a), POSS-Br (b), POSS-PDMAEMA $^{70}$ in $\\mathrm{CDCl}_{3}$ (c), and POSS- $\\cdot\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ in ${\\bf D}_{2}\\mathrm{O}$ (d).  \n\nFourier-transform infrared (FTIR) spectra of POSS-Br, POSS-PDMAEMA70, $\\mathrm{POSS-D}_{70^{-}}b.$ S10 were obtained on a Perkin-Elmer Spectrum 100 spectrometer (USA) using KBr pellet technique. As shown in Figure S2, the stretching vibration characteristic peak of Si-O-Si at $1112~\\mathrm{{cm}^{-1}}$ is apparent. The peak at $2954~\\mathrm{{cm}^{-1}}$ and $1323~\\mathrm{{cm}^{-1}}$ are attributed to the C-H stretching vibration and the C-H bending vibration, respectively. The signal at $695~\\mathrm{{cm}^{-1}}$ belongs to the C-Br stretching vibration.4,5 The data mentioned above further verify that POSS-Br was synthesized. In the FTIR spectra of POSS-PDMAEMA70, it is easily to find three C-H characteristic peaks at $2950~\\mathrm{cm}^{-1}$ , $2822~\\mathrm{{cm}^{-1}}$ and $2776~\\mathrm{{cm}^{-1}}$ . Meanwhile, the signals at $1723~\\mathrm{{cm}^{-1}}$ , $1457~\\mathrm{{cm}^{-1}}$ , $1270~\\mathrm{{cm}^{-1}}$ and 1112 $\\mathrm{cm}^{-1}$ belong to characteristic absorption bands of $\\scriptstyle\\mathbf{C=O}$ , C-N, $\\mathrm{CH}_{2}$ , and Si-O-Si respectively. All the date above mentioned demonstrates that POSS-PDMAEMA70 was prepared by ATRP. After copolymering with SBMA, we could find there was a new characteristic peak at $1039~\\mathrm{{cm}^{-1}}$ associated to the stretching vibration peak of $\\scriptstyle{\\mathsf{S}}=0$ , indicating the successful introduction of SBMA blocks. The peak appearance of C-O at $1149~\\mathrm{{cm}^{-1}}$ and the weaken strength of peak 1270 $\\mathrm{cm}^{-1}$ also proved the structure of POSS- $\\cdot\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ .6,7  \n\n![](images/a1874b6d00029e3d31c9b72a7f8e1b3e9bb22530edda1cd6b29962d729f7d9a1.jpg)  \nFigure S2. FTIR of POSS-Br, POSS-PDMAEMA70 and POSS- $\\cdot\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ .  \n\nThe molecular weight and polydispersity of the prepared copolymers PDMAEMA50, POSS-PDMAEMA with different polymerization degrees and $\\mathrm{D}_{50}–b–\\mathrm{S}_{7}$ were determined on a Waters 1515-2414 gel permeation chromatography (GPC, USA) with THF as the eluent and polystyrene as calibration. The polydispersity of the prepared polymers POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA were measured using a Viscotek’s GPC system with sodium acetate buffer $(0.5~\\mathrm{M}$ of NaAc and $0.5{\\mathrm{~M~}}$ of HAc, $\\mathrm{pH}=\\sim4.5)\\$ as the eluent at $30~^{\\circ}\\mathrm{C}$ at a flow rate of $1.0~\\mathrm{{mL}\\mathrm{{min}^{-1}}}$ . As shown in Figure S3, the unimodal GPC traces of POSS-PDMAEMA50, POSS-PDMAE $\\mathrm{\\uA_{70}}$ , POSS-PDMAEMA90, $\\mathrm{DMAEMA}_{50}$ , $\\mathrm{POSS-D}_{50^{-}}b{\\cdot}\\mathrm{S}_{7}$ , $\\mathrm{POSS-D}_{70}–b–\\mathrm{S}_{10}.$ , POSS- $\\mathrm{\\bfD}_{90}–b–\\mathrm{\\bfS}_{13}$ and $\\mathrm{D}_{50^{-}}b{-}S_{7}$ represented narrow polydispersity with PDI values of 1.27, 1.26, 1.22, 1.08, 1.07, 1.08, 1.11, and 1.19, respectively, indicating that the controlled polymerization was achieved. Because the molecular weight of zwitterionic polymers was difficult to measure by GPC, so we employed $\\mathrm{^{1}H}$ NMR and GPC to determine the molecular weight of the copolymers in this work. The molecular weight of POSS-PDMAEMA and POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA copolymers were calculated through the $\\mathrm{^{1}H N M R}$ method, but the molecular weight of $\\mathbf{PDMAEMA}_{50}$ and $\\mathrm{D}_{50^{-}}b{-}S_{7}$ were acquired by GPC due to its difficulty to adopt the $\\mathrm{^{1}H N M R}$ spectra by the integration of proton $\\mathrm{^{1}H N M R}$ feature signals.  \n\n![](images/4b53682a5979749255c0f4ae692d113fde9b0cf5bb5a547c7f5054a11ef1bdc3.jpg)  \nFigure S3. GPC curves of POSS-PDMAE $\\mathbf{MA}_{50}$ (a), POSS-PDMAE $\\mathbf{MA}_{70}$ (b), POSSPDMAEMA90 (c), $\\mathrm{DMAEMA_{50}}$ (d) and $\\mathrm{D}_{50^{-}}b{-}S_{7}$ (e) by using THF as the eluent, (A), and POSS- $\\mathbf{\\cdotD_{50}}–b\\mathbf{-S_{7}}$ (f), POSS- $\\cdot\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ (g) and POSS- $\\mathrm{\\cdotD}_{90^{-}}b{-}\\mathrm{S}_{13}$ (h) by using a sodium acetate buffer as the eluent (B).  \n\nThermal gravimetric analysis (TGA) was implemented on a TA Q50 instrument (USA) under nitrogen atmosphere at a heating rate of $10~\\mathrm{{^{\\circ}C/m i n}}$ from 20 to $800~^{\\circ}\\mathrm{C}$ . The TGA tests of POSS-Br, POSS-PDMAEMA70, POSS-PDMAEMA $70$ - $b$ -PSBMA10 were carried out. As shown in Figures S4, the TGA curve of POSS-Br reveals that $T_{\\mathrm{d}}$ at $5\\%$ mass loss is about $223.9\\ ^{\\circ}\\mathrm{C}$ due to its excellent thermodynamic stability, probably resulting from the existence of Si-O-Si bonds. Pure PDMAEMA showed total decomposition at about $500~^{\\circ}\\mathrm{C}$ in the reference.8 In this work, the mass of $\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ decreased to about zero at the end of measurement. For POSS-PDMAE $\\mathbf{MA}_{70}$ and $\\mathrm{POSS-D}_{70}–b–\\ensuremath{\\mathrm{S}}_{10}$ , the mass loss reaches $95.2\\%$ at $500~^{\\circ}\\mathrm{C}$ , and whereafter the mass of polymers remains unchanged, demonstrating the existence of the POSS component in the copolymers.  \n\n![](images/b377cbd859d4b90691c74b825ea562d11bb4c532d029b8ebf1153331e0ad3666.jpg)  \nFigure S4. TGA curves of POSS-Br (a), POSS-PDMAEMA70 (b), POSS- $\\mathrm{\\cdotD}_{70^{-}}b{-}\\mathrm{S}_{10}$ (c), and $\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ (d).  \n\nThermal remediation behavior and stability of the SIPN coatings. The sample C-POSS- $\\cdot\\mathrm{D}_{90}–b–\\mathrm{S}_{13}$ showed self-healing by vapor after scratched by a clean blade. The score disappeared completely after about 3 min as shown in Figure S5.  \n\n![](images/b315366679a4c375e671b421eae27aee3c4853139419911e4a0568690fe226f5.jpg)  \nFigure S5. Photographs of the C-POSS- $\\mathrm{.D}_{90}$ -b-S13 coating with a scratch (a), and the healable coating by vapor (b).  \n\nFigure S6(a) shows the condition of the $\\mathrm{POSS-D}_{70^{-}}b{\\mathrm{-}}\\mathrm{S}_{10}$ coating before immersed in deionized water, suggesting that the coating was as transparent as bare glass. Figure S6(b) shows the condition of the POSS- $\\cdot\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ coating during immersion in deionized water. An enough amount of deionized water was filled in the beaker, in which the coating sample was immersed. Figure S6(c) shows the condition of the $\\mathrm{POSS-D}_{70^{-}}b{\\mathrm{-}}\\mathrm{S}_{10}$ coating after immersion in deionized water for about $30~\\mathrm{min}$ . It can be seen that bare glass was obscure by water droplets, while the coating still kept its good transmittance. Thus, the coatings contain POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA show great stability for long-lasting utilities.  \n\n![](images/3073a8caf340ec30304ff5c23781ec638bcc9382422be089f4fbbadb1aeb41d1.jpg)  \nFigure S6. Photographs of the C-POSS- $\\cdot\\mathrm{D}_{70}{-}b{-}\\mathrm{S}_{10}$ coating before (a), during (b) and after immersed in deionized water (c).  \n\nATR-FTIR analysis of the SIPN coatings. Chemical surface characterization of the prepared SIPN coatings was analyzed by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR, Perkin-Elmer Spectrum100, USA). Figure S7 shows ATR-FTIR spectra of the prepared coatings. The characteristic absorption peaks at $2822~\\mathrm{{cm}^{-1}}$ and $2776\\mathrm{cm}^{-1}$ are attributed to C-H vibration of the $\\J\\mathrm{-N}(\\mathrm{CH}_{3})_{2}$ group from PDMAEMA, while the peak at 2950 $\\mathrm{cm}^{-1}$ belongs to C-H stretching vibration from other groups. Meanwhile, the signals at $1723\\mathrm{cm}^{-1}$ , $1270~\\mathrm{{cm}^{-1}}$ and $1457~\\mathrm{{cm}^{-1}}$ belong to characteristic absorption bands of $\\scriptstyle\\mathbf{C=O}$ , C-N and $\\mathrm{CH}_{2}$ , respectively. Furthermore, the characteristic absorption peak at $1039~\\mathrm{{cm}^{-1}}$ is related to stretching vibration peak of $\\scriptstyle{\\mathsf{S}}=0$ in PSBMA. In addition, the absorbance of the O-H stretching bands of hydrogen bonding was detected at $3414~\\mathrm{{cm}^{-1}}$ . The wavenumber range $1204{\\cdot}1085\\ \\mathrm{cm}^{-1}$ in the curves of Figure S7(a,b,c) include the peaks of $\\mathbf{C}\\mathbf{-}\\mathbf{O}$ at $1149\\mathrm{cm}^{-1}$ and Si-O-Si at $1112\\mathrm{cm}^{-1}$ .4 And, curve Figure S7(d) shows the peak at $1149~\\mathrm{{cm}^{-1}}$ , which is attributed to characteristic absorption band of C-O.4  \n\n![](images/02718d47f0d96d4eb97733a7995e2f9c272373d48b063d20501c2bcd959a381e.jpg)  \nFigure S7. ATR-FTIR spectra of the SIPN coatings of C-POSS- $\\cdot\\mathrm{D}_{50^{-}}b{-}S_{7}$ (a), C-POSS-D70-b-S10 (b), C-POSS- $\\mathrm{\\bfD}_{90^{-}}b.\\mathrm{\\bfS}_{13}$ (c), and $\\mathrm{C}{\\cdot}\\mathrm{D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ (d).  \n\nTEM analysis of the SIPN Coatings. The SIPN coating morphologies were observed under a JEOL JEM100CXII transmission electron microscope (TEM, Japan) at $100\\mathrm{kV}$ . TEM samples were prepared by dropping a droplet of the dilute copolymer solutions ( $1\\mathrm{\\mt{\\%}}$ in trifluoroethanol) on a thin carbon-coated copper grid, and then UV-curing in a XL-1000 ultraviolet cross-linker apparatus (USA) for 30min. As seen from these images (Figure S8), the aggregated POSS clusters are in the size range of $10{\\sim}80~\\mathrm{nm}$ , and well dispersed.  \n\n![](images/22105b4b182b3f7f6933f24c2261d05a5a7bf65488e9d1dbc57e477ae1e711b9.jpg)  \nFigure S8. TEM images of the SIPN coatings of C-POSS-D $50$ -b-S7 (a), C-POSS-D $^{70}$ -b-S10 (b), C-POSS- $\\cdot\\mathrm{D}_{90}–b–\\mathrm{S}_{13}$ (c), and $\\mathrm{C}{\\cdot}\\mathrm{D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ (d).  \n\nDSC analysis of the SIPN Coatings. The SIPN coatings were analyzed by a TA Q2000 differential scanning calorimetry machine (DSC, USA). The samples containing a certain amount of deionized water were prepared by adding water into the SIPN coatings (about $4{\\sim}5~\\mathrm{mg}$ ) scraped from the glass slide, and keeping them in the aluminium pans for 10 days at room temperature. The heating rate had a negligible effect on the content of non-freezable bond water and bond water as shown in Table S1.  \n\nTable S1. Water contents in different states in the samples analyzed by DSC at different heating rates   \n\n\n<html><body><table><tr><td rowspan=\"2\">Sample</td><td rowspan=\"2\">Heating rate</td><td rowspan=\"2\">Wc (mg/mg)</td><td colspan=\"6\">Freezable water Wf (mg/mg)</td><td rowspan=\"2\">Non-freezable Bond bond water water Wb</td></tr><tr><td>Wf</td><td colspan=\"2\">Freezable bond water</td><td colspan=\"2\">Freezable free water</td></tr><tr><td></td><td>(C/min)</td><td></td><td>(mg/mg)</td><td>Wfb (mg/mg)</td><td>Tfbm (℃)</td><td>Wff (mg/mg)</td><td>Tffm (℃)</td><td>Wnfb (mg/mg)</td><td>(mg/mg)</td></tr><tr><td>C-POSS-D50-b-S7</td><td>5</td><td>1.21</td><td>0.76</td><td>0.13</td><td>-14.88</td><td>0.63</td><td>-1.56</td><td>0.45</td><td>0.58</td></tr><tr><td rowspan=\"4\">C-POSS-D7o-b-S10</td><td>10</td><td></td><td>0.76</td><td>0.14</td><td>-14.01</td><td>0.62</td><td>-1.30</td><td>0.45</td><td>0.59</td></tr><tr><td>15</td><td></td><td>0.76</td><td>0.14</td><td>-13.10</td><td>0.62</td><td>-1.07</td><td>0.45</td><td>0.59</td></tr><tr><td>5</td><td>1.20</td><td>0.77</td><td>0.11</td><td>-17.54</td><td>0.66</td><td>-2.06</td><td>0.43</td><td>0.54</td></tr><tr><td>10</td><td></td><td>0.77</td><td>0.16</td><td>-17.42</td><td>0.61</td><td>-1.91</td><td>0.43</td><td>0.59</td></tr><tr><td>C-POSS-D90-b-S13</td><td>15</td><td></td><td>0.77</td><td>0.15</td><td>-14.61</td><td>0.62</td><td>-1.73</td><td>0.43</td><td>0.58</td></tr><tr><td rowspan=\"4\"></td><td>5</td><td>1.22</td><td>0.77</td><td>0.14</td><td>-15.34</td><td>0.63</td><td>-1.96</td><td>0.45</td><td>0.59</td></tr><tr><td>10</td><td></td><td>0.77</td><td>0.14</td><td>-15.01</td><td>0.63</td><td>-1.50</td><td>0.45</td><td>0.59</td></tr><tr><td>15</td><td></td><td>0.77</td><td>0.15</td><td>-14.50</td><td>0.62</td><td>-1.11</td><td>0.45</td><td>0.60</td></tr><tr><td>5</td><td>1.24</td><td>0.72</td><td>0.11</td><td>-16.55</td><td>0.61</td><td>-2.41</td><td>0.52</td><td>0.63</td></tr><tr><td>C-D50-b-S7</td><td>10</td><td></td><td>0.72</td><td>0.09</td><td>-16.34</td><td>0.63</td><td>-2.13</td><td>0.52</td><td>0.61</td></tr><tr><td></td><td>15</td><td></td><td>0.72</td><td>0.12</td><td>-15.13</td><td>0.60</td><td>-1.87</td><td>0.52</td><td>0.64</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 3,
+        "chunk": "# References  \n\n(1) Ma, L.; Geng, H. P.; Song, J. X.; Li, J. Z.; Chen, G. X.; Li, Q. F. Hierarchical Self-Assembly of Polyhedral Oligomeric Silsesquioxane End-Capped Stimuli-Responsive Polymer: From Single Micelle to Complex Micelle. J. Phys. Chem. B 2011, 115, 10586-10591. (2) Shao, Y.; Aizhao, P.; Ling, H. POSS End-Capped Diblock Copolymers: Synthesis, Micelle Self-Assembly and Properties. J. Colloid Interface Sci. 2014, 425, 5-11. (3) Zhang, M. M.; Shen, W.; Xiong, Q. Q.; Wang, H. W.; Zhou, Z. M.; Chen, W. J.; Zhang, Q. Q. Thermo-Responsiveness and Biocompatibility of Star-Shaped Poly[2-(dimethylamino) ethyl methacrylate]- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -Poly(sulfobetaine methacrylate) Grafted on $\\upbeta$ -Cyclodextrin Core. Rsc Adv. 2015, 5, 28133-28140. (4) Li, Y. M.; Xu, B.; Bai, T.; Liu, W. G. Co-Delivery of Doxorubicin and Tumor-Suppressing p53 Gene Using a POSS-Based Star-Shaped Polymer for Cancer Therapy. Biomaterials 2015, 55, 12-23. (5) Liu, Y. H.; Yang, X. T.; Zhang, W. A.; Zheng, S. X. Star-Shaped Poly(ε-caprolactone) with Polyhedral Oligomeric Silsesquioxane Core. Polymer 2006,47, 6814-6825. (6) Chou, Y. N.; Chang, Y.; Wen, T. C. Applying Thermosettable Zwitterionic Copolymers as General Fouling-Resistant and Thermal-Tolerant Biomaterial Interfaces. ACS Appl. Mater. Interfaces 2015, 7, 10096-10107. (7) Dong, Z.; X, Mao, J.; Wang, D. P.; Yang M. Q.; Wang W. C.; Bo S. Q.; Ji X. L. Tunable Dual-Thermoresponsive Phase Behavior of Zwitterionic Polysulfobetaine Copolymers Containing Poly(N,N-dimethylaminoethylmethacrylate)-Grafted Silica Nanoparticles in Aqueous Solution. Macromol. Chem. Phys. 2014, 215, 111-120. (8) Zhang, P.; Yang, J. H.; Li, W. C.; Wang, W.; Liu, C. J.; Griffith, M.; Liu, W. G. Cationic Polymer Brush Grafted-Nanodiamond via Atom Transfer Radical Polymerization for Enhanced Gene Delivery and Bioimaging. J. Mater. Chem. 2011, 21, 7755-7764.",
+        "category": " References"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/am9b09610_si_001.json b/task2/task2-chunks/am9b09610_si_001.json
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+++ b/task2/task2-chunks/am9b09610_si_001.json
@@ -0,0 +1,17 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Supporting Information",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# Transparent and Scratch-Resistant Antifogging Coatings with Rapid Self-Healing Capability  \n\nBang Liang†‡, Zhenxing Zhong†‡, Erna Jia†‡, Guangyu Zhang\\*†, Zhaohui Su\\*†‡ †State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, P. R. China  \n\n‡University of Science and Technology of China, Hefei, 230026, P. R. China \\*Correspondence should be addressed to Z.S. (zhsu@ciac.ac.cn) or G.Z. (zhanggy608@ciac.ac.cn)  \n\n![](images/1978e0636fcc17c702b7ca60de3a41785580f6337d10fb09e43bab4f4d6e6254.jpg)  \nFigure S1. (a) Synthesis of SBS, and (b) $^{1}\\mathrm{H-NMR}$ spectrum of SBS in DMSO-d6. (c) Modification of the silica nanoparticles with SBS to introduce sulfobetaine groups to the surfaces of the nanoparticles. (d) FTIR spectra of plain and modified silica nanoparticles. The presence of the Si-O-C bending peak at $\\sim1510\\ \\mathrm{cm^{-1}}$ as well as the $\\mathrm{CH}_{2}$ stretching and scissoring peaks at $\\sim2950$ and ${\\sim}1480~\\mathrm{cm^{-1}}$ respectively confirms the grafting of the organic species to the silica surface.  \n\n![](images/e3de168182a0e5b5ea6b03e7e14ee65cde2b4dc566e3b229cae192c94c926fb2.jpg)  \nFigure S2. ThPea atmehtiercskne1ss Uonitf p(SBMA7-co-HEMA3) composite coating analyzed with step profiler.  \n\n![](images/7399aad7b95d66c2e4bc78ccc0386ce6dd6a0a09860111ccd9797915ef23f353.jpg)  \nFigure S3. TEM images of p(SBMA7-co-HEMA3) filled with (a) $2.5\\mathrm{wt\\%}$ plain and (b) $2.5\\mathrm{wt\\%}$ and (c) $7.5~\\mathrm{wt\\%}$ modified silica nanoparticles, respectively, and (d) UV-vis spectra of these three coatings. These data show that silica nanoparticles aggregate in the coating at a content higher than $5\\mathrm{wt\\%}$ , resulting in decreased transparency.  \n\n![](images/62db90176e14b5dbd20ab040d6d524447fbe35a61c807deccda6c81307aa114d.jpg)  \nFigure S4. (a) X-ray photoelectron spectrum (XPS) of the p(SBMA7-co-HEMA3) composite coating. (b) Optical micrograph of the composite coating after a cross-tape test, showing no detachment of the coating or debris. (c) Thickness of the composite coating as a function of immersion time in deionized water, showing stability of the coating in aqueous environment.  \n\nXPS measurements were performed on a Thermo-Electron ESCALAB250 spectrometer equipped with a monochromatic Al X-ray source $(1486.6~\\mathrm{eV})$ at a $90^{\\circ}$ takeoff angle with $20~\\mathrm{eV}$ pass energy. The S2p, N1s, Si2s and Si2p peaks observed for coated glass are consistent with the presence of the coating on the substrate.  \n\n![](images/5043ff2d9d47a7f5be7176dc09367b2af6230613bfd74b2eec6f1fa1cfebf785.jpg)  \n\nFigure S5. (a) Optical images of the composite coating upon exposure to spray produced by a humidifier (left) for 1, 5 and $10\\mathrm{~h~}$ , respectively (right), and (b) corresponding UV-vis spectra. Both results show that the coating remains clear.  \n\n![](images/fb8ad73717ef604c67af4aa472cb32bb7743908c5afabcc5503508862e8323aa.jpg)  \nFigure S6. Time profiles (three independent tests) of ice adhesion strength on the surface of bare glass.  \n\n![](images/95ac50a660c5cfd3c708fbb4f339f6fa7fb6496db1ad1ac6362b091cf79e977b.jpg)  \nFigure S7. Photograph of a pencil hardness tester.  \n\n![](images/0b3d6873ddfcf74a98119b52d6955794c1d4d6fb2f6bdb062dd3ea48164e3abd.jpg)  \nFigure S8. (a) Optical images of the $1^{\\mathrm{st}}$ and the $20^{\\mathrm{th}}$ cycles of the coating cut and healed at the same region. (b) Raman spectra of the coating as-prepared and after 20 cut-and-heal cycles at the same region.  \n\n![](images/dd4cf9030fa57fed64b44e2c4ef49d7c10b5cba8f7741384d42e0c4ade290820.jpg)  \nFigure S9. Healing time as a function of thickness of the p(SBMA7-co-HEMA3) composite coating (for repairing a cut of $250~{\\upmu\\mathrm{m}}$ width through the coating thickness exposing the substrate).  \n\n![](images/18a5e9eba0fcb784a8c3496eddb89fe643e9c54a917e1fb5b0370af47b971062.jpg)  \nFigure S10. (a) Antifogging performance and (b) UV-vis spectra of the composite coating with different HEMA contents in the copolymer.  \n\n![](images/e5a2d0f8b2b5c6059d70d08ae91eed2071b2844e3cd6e5c397aad5a7c3fb7446.jpg)  \nFigure S11. QCM-D frequency shift of (a) bare electrode and (b) electrode coated with the composite coating in contact with a BSA solution in PBS $\\mathrm{~(~1~~mg/mL)~}$ . The experimental procedure is described in the literature.1  \n\n![](images/492c78c41959c56f777411abcac9b617e92e5a92fc68977200326c6419767749.jpg)  \nFigure S12. (a) Snapshots showing a soybean oil droplet sticks on scratched coating (top), but is lifted on the coating that has healed the scratches (bottom) after immersion in water. (b) Mass of BSA adsorbed on a scratched coating vs. that on a healed one.  \n\nTable S1. Pencil Hardness for Coatings of Different HEMA Contents in the Copolymer   \n\n\n<html><body><table><tr><td>HEMA content</td><td>0 mol%</td><td>15 mol%</td><td>30 mol%</td></tr><tr><td>pencil hardness</td><td>4H</td><td>4H</td><td>4H</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 3,
+        "chunk": "# Reference  \n\n1. Liang, B.; Zhang, G.; Zhong, Z.; Sato, T.; Hozumi, A.; Su, Z. Substrate-independent polyzwitterionic coating for oil/water separation membranes. Chem. Eng. J. 2019, 362, 126-135.",
+        "category": " References"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/am9b21871_si_001.json b/task2/task2-chunks/am9b21871_si_001.json
new file mode 100644
index 0000000..0a8ef1d
--- /dev/null
+++ b/task2/task2-chunks/am9b21871_si_001.json
@@ -0,0 +1,22 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Supporting Information  \n\nAntifogging/Antibacterial Coatings Constructed by",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 2,
+        "chunk": "# N-Hydroxyethylacrylamide and Quaternary",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# Ammonium-Containing Copolymers  \n\nShan Bai, Xiaohui Li\\*, Yunhui Zhao, Lixia Ren, Xiaoyan Yuan\\*  \n\nSchool of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300350, China  \n\n\\* E-mail: lixiaohui@tju.edu.cn; yuanxy $@$ tju.edu.cn  \n\nMaterials. Aminopropylisobutyl polyhedral oligomeric silsesquioxane (POSS- $\\mathrm{\\cdotNH}_{2}$ , $98\\%$ ) was purchased from Hybrid Plastics, USA and used without further purification. 2-(Dimethylamino)ethyl methacrylate (DMAEMA, $98.5\\%$ ) from J&K Scientific, China, N-(2-hydroxyethyl) acrylamide (HEAA, $98\\%$ ) from Energy Chemical and glycidyl methacrylate (GMA, $595\\%$ ) from TCI Chemical Industrial Development, China were filtered through an neutral alumina column before use. 2-Aminoethyl methacrylate hydrochloride (AEMA, $90\\%$ ) from Jiuding Chemical Technology, China, 1,3,5-triformylbenzene (TFB, $99\\%$ ) from Bide Pharmatech, China were used as received. (3-Aminopropyl)trimethoxysilane (APTES, $90\\%$ ), $^{2,2^{\\circ}}$ -azobisisobutyrobutyl acrylate (AIBN), 1-bromobutane $(>99\\%)$ , 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC, $98\\%$ ) and 4-dimethylaminopyridine (DMAP, $99\\%$ ) were purchased from Tianjin Heowns Biochemical Technology Co. Ltd., China. Triethylamine (TEA, ${\\tt>}99\\%$ ) and $^{4,4^{\\prime}}$ -azobis(4-cyanvaleric acid) (ACVA) were purchased from Tianjin Kemiou Chemical Reagent Co. Ltd., China, and ACVA was used after recrystallization in ethanol. 4-Cyanopentanoic acid dithiobenzoate (CPADB) was synthesized according to previous report.1 Mueller-Hinton broth (MHB) and nutrient agar were supplied by Beijing Aoboxing Biological Technology, China. Gram-positive bacteria Staphylococcus aureus (S. aureus, ATCC 6538) and gram-negative bacteria Escherichia coli (E. coli, ATCC 8739) were incubated in MHB at $37^{\\circ}\\mathrm{C}$ for $24\\mathrm{~h~}$ . LIVE/DEAD® BacLightTM bacterial viability kit (L13152) were purchased from ThermoFisher Scientific, USA.  \n\nSynthesis of POSS-CPADB. CPADB ( $\\left(0.56\\mathrm{~g},2.0\\mathrm{~mmol}\\right)$ , EDC $(1.15\\mathrm{~g},\\:6.0\\mathrm{~mmol})$ and DMAP $(0.15\\mathrm{~g},\\ 1.2\\mathrm{~mmol})$ were dissolved in $20~\\mathrm{mL}$ DCM. After stirring and degassing with nitrogen for $30\\mathrm{min}$ , a solution of POSS- $\\mathrm{\\cdotNH}_{2}$ $(2.10\\ \\mathrm{g},2.4\\ \\mathrm{mmol})$ in 2 mL DCM was added to the mixture and continued to stir at room temperature under nitrogen atmosphere for $12\\mathrm{~h~}$ . Then, the mixture was concentrated and purified by column chromatography using petroleum ether/ethyl acetate $(4/1,\\nu/\\nu)$ as eluent to obtain POSS-CPADB. $^{1}\\mathrm{H}$ NMR spectrum ( $\\mathrm{CDCl}_{3}$ , δ ppm): $\\delta=4.43$ (6), $\\updelta=3.98$ (3), $\\delta=3.74$ (7), $\\delta=3.40$ (9), $\\delta=3.15$ (4, 8), $\\updelta=2.13\\ –1.90$ (2), $\\delta=1.77$ (11), $\\delta=$ 1.37 (10, 14), $\\delta=1.14–1.02$ (1), $\\updelta=0.99–0.83$ (12, 13, 15).  \n\nSynthesis of Quaternary Ammonium Compounds. Quaternary ammonium compounds (QAC) was synthesized referring to literature procedure.2 DMAEMA $\\left(9.33\\mathrm{~g},0.06\\mathrm{~mol}\\right)$ and 1-bromobutane $(8.95\\mathrm{~g},0.065\\mathrm{~mol})$ ) were charged into a $100~\\mathrm{{mL}}$ volume flask. Then, $30~\\mathrm{mL}$ acetonitrile was added as solvent and the mixture was stirred at $50^{\\circ}\\mathrm{C}$ for $52\\mathrm{~h~}$ . The obtained monomer was purified by washing with diethyl ether five times and dried under vacuum at room temperature to afford a white power. $^{1}\\mathrm{H}$ NMR of QAC (CDCl3, δ ppm): $\\delta=6.15$ , 5.68 (1, 1’), 4.66 (3), 4.17 (4), 3.66(6), 3.53 (5), 1.94 (2), 1,76 (8), 1.42 (7), 0.99 (9).  \n\nSynthesis of POSS-P(QAC-co-AEMA). POSS-P(QAC-co-AEMA) copolymer was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Typically, QAC ( $588.0~\\mathrm{mg}$ , 2 mmol), AEMA $\\cdot82.8~\\mathrm{mg},0.5~\\mathrm{mmol})$ , POSS-CPADB ( $11.4~\\mathrm{mg},$ , $0.01\\ \\mathrm{mmol}\\$ ) and AIBN $(0.4~\\mathrm{mg},0.0025~\\mathrm{mmol})$ dissolved in EtOH ( $\\mathrm{1~mL}$ ) were added into a 10 mL Schlenk flask. The flask was deoxygenated by three consecutive freeze-pump-thaw cycles before the polymerization was conducted at $70^{\\circ}\\mathrm{C}$ for $10\\mathrm{~h~}$ , and then quenched by rapid cooling immersion of the flask into iced water. The synthesized copolymer of POSS-P(QAC-co-AEMA) was precipitated into $n$ -hexane for five times and subsequently dialyzed for 3 days to lyophilize.  \n\nSynthesis of P(HEAA-co-GMA). The copolymer of P(HEAA- $\\scriptstyle\\cdot c o$ -GMA) was synthesized by traditional free radical polymerization. Briefly, HEAA ( $516.0~\\mathrm{mg}$ , mmol) and GMA $(49.0~\\mathrm{mg},$ , mmol) were dissolved in mixed solvent of $\\mathrm{EtOH}/\\mathrm{H}_{2}\\mathrm{O}\\left(1/1,\\nu/\\nu\\right)$ , then $2.8~\\mathrm{mg}$ ACVA was added as the thermal initiator. After degassing by nitrogen for $30\\ \\mathrm{\\min}$ , the polymerization was performed at $65^{\\circ}\\mathrm{C}$ for $10\\mathrm{{h}}$ , and then the reaction mixture was precipitated in acetone. A certain volume of deionized water was added to the copolymer immediately after drying under vacuum at room temperature for storage of P(HEAA-co-GMA).  \n\nCharacterizations of POSS-P(QAC-co-AEMA) and P(HEAA-co-GMA) Copolymers. Proton nuclear magnetic resonance ( $\\mathrm{^{1}H}$ NMR) spectroscopy (Bruker $400~\\mathrm{{MHz}}$ , Germany) was used to confirm the chemical structure of the prepared copolymers. Aqueous gel permeation chromatography (GPC) was conducted to measure the number-average molecular weight $(\\overline{{M}}_{n})$ of the synthesized copolymers, which was performed on a Viscotek’s GPC system using poly(ethylene glycol) as standards for calibration. The eluent was $0.5\\mathrm{~M~}$ acetic acid/0.5 M sodium acetate buffer solution $\\mathrm{(pH}\\ \\approx4.5\\$ with a flow rate of 1 mL/min. For synthesis POSS-P(QAC-co-AEMA), quaternary ammonium compound (QAC) was first prepared by quaternization of DMAEMA with 1-bromobutane to obtain $N.$ -(2-(methacryloyloxy)ethyl)- $.N,$ , $N.$ -dimethylbutan aminium bromide. Hydrophobic POSS was introduced owing to its enhanced stability and mechanical properties by taking POSS-CPADB as a RAFT agent for copolymerization of QAC and AEMA. As shown in Figure S1(a), the chemical shifts of double bond protons at 6.2-5.5 ppm disappeared and a broad peak of 2.13-1.86 ppm derived from methylene in the backbone chain could be observed, suggesting the copolymerization has been performed. All other chemical shifts were shown in the spectrum. It could be calculated from $^{1}\\mathrm{H}$ NMR spectrum that actual ratio of QAC and AEMA is 3:1 and the number-average molecular weight $(\\overline{{M}}_{n})$ of POSS-P(QAC-co-AEMA) copolymer obtained from GPC is $12.0\\times10^{4}$ . $\\mathrm{^{1}H}$ NMR and GPC results of P(HEAA- $.c o$ -GMA) copolymer were given in Figure S1(b). Compared with the spectra of HEAA and GMA, it could be seen from copolymer spectrum that each peak has corresponding proton attribution and the actual ratio of the two monomers is 15:1, which was consistent with the feeding ratio, indicating HEAA and GMA have similar competition rate in the process of copolymerization.3 The molecular weight of P(HEAA- $c o$ -GMA) is $9.94\\times10^{4}$ .  \n\n![](images/809faa535ef989f56632e284282b321c92cee3a03d6cea0565b5a8be74de0083.jpg)  \nFigure S1. (A) $^{1}\\mathrm{H}$ NMR spectra of POSS-CPADB, QAC, AEMA and copolymer POSS-P(QAC-co-AEMA), (B) $^{1}\\mathrm{H}$ NMR spectra of GMA, HEAA and copolymer P(HEAA-co-GMA), (C) GPC retention curves of the two synthesized copolymers.  \n\nThickness of the Coatings. Scanning electron microscopy (Hitachi SU1510, Japan) was used to measure the thickness of the prepared coatings by observing the cross-sections after liquid nitrogen quenching. It was obtained from the SEM images showed in Figure S2 that the thickness of neat PPQA coating was $9.14{\\pm}0.39~\\upmu\\mathrm{m}$ , which was larger than that of neat PHG coating $(6.74{\\pm}0.17~\\upmu\\mathrm{m})$ . However, the three blending coatings, $\\mathrm{PPQA}_{2}/\\mathrm{PHG}_{1}$ , $\\mathrm{PPQA_{1}/P H G_{1}}$ , and $\\mathrm{PPQA_{1}/P H G_{2}}$ had similar thickness of $7.34{\\pm}0.36\\$ , $7.57{\\pm}0.59\\$ and $7.13{\\pm}0.22\\ \\upmu\\mathrm{m}$ , respectively.  \n\n![](images/05934013601eb88ef1152c40922991c77bbb758053389d56840c87b23a9d966a.jpg)  \nFigure S2. SEM images of the cross-sections for different coatings.  \n\nAntifogging Properties of $\\mathbf{PQA_{1}}/\\mathbf{PHG_{1}}$ Coating. To investigate the effect of POSS on coating properties, the copolymer of P(QAC-co-AEMA) was also synthesized via RAFT polymerization. GPC result $(8.50\\times10^{4}$ ) indicated that it had similar molecular weight to POSS-P(QAC-co-AEMA). $\\mathrm{PQA_{1}/P H G_{1}}$ coating was also prepared by blending P(QAC-co-AEMA) with P(HEAA-co-GMA) at a ratio of $1/1$ . The antifogging performance of $\\mathrm{PPQA_{1}/P H G_{1}}$ and $\\mathrm{PQA_{1}/P H G_{1}}$ blending coatings were evaluated and compared to explain the effect of POSS on antifogging performance. As shown in Figure S3(a), $\\mathrm{PPQA_{1}/P H G_{1}}$ and $\\mathrm{PQA_{1}/P H G_{1}}$ coatings exhibited indistinguishable antifogging performance under both hot-vapor and cold-warm conditions. Furthermore, visible light transmittance of the two blending coatings was recorded immediately after removing them from $\\mathopen{}\\mathclose\\bgroup\\left.-20^{\\circ}\\mathrm{C}\\aftergroup\\egroup\\right.$ condition (Figure S3(b)). Compared with POSS-containing blending coating, $\\mathrm{PQA_{1}/P H G_{1}}$ coating showed a slightly increased transmittance only in lower wavelength range, probably ascribed to the absence of hydrophobic POSS. Therefore, it could be concluded that POSS had little effect on antifogging performances in the whole range of visible light wavelength.  \n\n![](images/5762215a760f2e523286b12c626aed9c66dba33d8b80f4adffbcf539c561e95a.jpg)  \nFigure S3. (a) Antifogging performance of $\\mathrm{PPQA_{1}/P H G_{1}}$ and $\\mathrm{PQA_{1}/P H G_{1}}$ coatings. (B Transmittance of $\\mathrm{PPQA_{1}/P H G_{1}}$ and $\\mathrm{PQA_{1}/P H G_{1}}$ coatings during cold-warm antifogging test.  \n\nStability of the Coatings. The stability of the blending coatings was evaluated by firstly immersing the coatings into PBS buffer $\\mathrm{(pH~7.4)}$ at $37^{\\circ}\\mathrm{C}$ for $30~\\mathrm{min}$ , followed by testing their antifogging performance with hot-vapor method. As shown in Figure S4, though decreased transparency was observed for PPQA and PHG coating due to their original inferior antifogging ability, the three blending coatings of $\\mathrm{PPQA_{2}/P H G_{1}}$ , PPQA1/PHG1and $\\mathrm{PPQA_{1}/P H G_{2}}$ were still effective in preventing fog formation after immersion, suggesting their stability and long-last utilities to some extent. To investigate the effect of POSS on coating stability, $\\mathrm{PQA_{1}/P H G_{1}}$ coating were also treated with the same way. It could be seen that after $30~\\mathrm{min}$ of immersion, $\\mathrm{PQA_{1}/P H G_{1}}$ coating showed some dissolution on the edges, in contrast, all the prepared POSS-contained coatings kept the intact morphology, which demonstrated that the introduced POSS was favor of enhancement of coating stability.  \n\n![](images/aa2254dd8318c323dda580f596acad9996f3fc1ed5c3379c1000be64ab678a71.jpg)  \nFigure S4. Hot-vapor antifogging performance of the prepared coatings after immersing them into PBS buffer for $30\\mathrm{min}$ .  \n\nAntibacterial Properties of $\\mathbf{PQA_{1}}/\\mathbf{PHG_{1}}$ Coating. The minimal inhibitory concentrations (MIC) of P(QAC-co-AEMA) copolymer against $S.$ . aureus and $E$ . coli were tested and the compared results with that of POSS-P(QAC- $c o$ -AEMA) were shown in Figure S5(a). It could be seen that the MIC values of P(QAC-co-AEMA) were 128 and $256~\\upmu\\mathrm{g/mL}$ towards S. aureus and E. coli, respectively, being the same as that of POSS-P(QAC-co-AEMA) copolymer. Furthermore, the antibacterial properties of $\\mathrm{PQA_{1}/P H G_{1}}$ coating were also investigated via standard plate count method. As shown in Figure S5(b), the two coatings also exhibited comparable antibacterial activity against both bacteria strains. It was concluded that POSS had little effect on antibacterial property in this work.  \n\n![](images/f1723af2f0e478cdfd2e28cdc58f2d7d7c1144ffc9fc32cb4db09d001d603512.jpg)  \nFigure S5. (a) Growth inhibition rates of POSS-P(QAC-co-AEMA) and P(QAC-co-AEMA) copolymers aqueous solution with a series of concentrations against S. aureus and $E$ . coli. (b) Growth inhibition rates of the $\\mathrm{PPQA_{1}/P H G_{1}}$ and $\\mathrm{PQA_{1}/P H G_{1}}$ blending coatings calculated by standard plate count methods. All data were obtained from at least three samples.  \n\nRecycling Antibacterial Properties of the Coatings. In this work, the long-term and recycling antibacterial property of the blending coatings was investigated by first placing coating samples above the boiling water $90\\%$ RH, $70{\\sim}80^{\\circ}\\mathrm{C}\\$ for $30~\\mathrm{min}$ , followed by evaluating their antibacterial activity again via standard plate count method. As shown in Figure S6, all the prepared coatings maintained almost the same bacterial growth inhibition rates as before, which could indicate the long-term and recycling antibacterial property to some extent.  \n\n![](images/d539e31c8774b7cdbd4a6e55cc5b6b10e126b709f0ac6dcb85359cb11ed1b48c.jpg)  \nFigure S6. Bacterial growth inhibition rates of the prepared coatings after exposing foggy condition $\\sim90\\%$ RH, $70{\\sim}80^{\\circ}\\mathrm{C}\\$ for $30\\mathrm{min}$ .  \n\nCytotoxicity of the Coatings. The cytotoxicity of the coating against L929 has been detected by CCK-8 assay. As shown in Figure S7, the relative cell viabilities for all the prepared coatings were less than $60\\%$ . It was probably due to the quaternary ammonium compounds and the cell adhesion on the coating surfaces. In addition, 1,3,5-triformylbenzene, as an aldehyde compound, may also had effect on cytotoxicity.  \n\nRelative cell viability $(\\%)=(O D_{\\mathrm{coating}}/O D_{\\mathrm{positive~control}}){\\times}100$  \n\n![](images/0c49aa38c2a4373dd99376afc4e278aa683ed7682062acbca246b41d913d83da.jpg)  \nFigure S7. Relative cell viability against L929 on different coatings after $24\\mathrm{h}$ at $37^{\\circ}\\mathrm{C}$ .  \n\nVideo S1. The video of the antifogging performance in vivo of bare glass.  \n\nVideo S2. The video of the antifogging performance in vivo of $\\mathrm{PPQA_{1}/P H G_{2}}$ coating.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# REFERENCES  \n\n(1) Li, X. H.; Zhang, K. Q.; Zhao, Y. H.; Zhu, K. Y.; Yuan, X. Y. Formation of Icephobic Film from POSS-Containing Fluorosilicone Multi-Block Methacrylate Copolymers. Prog. Org. Coat. 2015, 89,150-159. (2) Wan, X.; Zhang, Y.; Deng, Y.; Zhang, Q.; Li, J.; Wang, K.; Li, J.; Tan, H.; Fu, Q. Effects of Interaction between a Polycation and a Nonionic Polymer on Their Cross-Assembly into Mixed Micelles. Soft Matter 2015, 11, 4197-4207. (3) Zhao, C.; Zheng, J. Synthesis and Characterization of Poly(N-hydroxyethylacrylamide) for Long-Term Antifouling Ability. Biomacromolecules 2011, 12, 4071-4079.",
+        "category": " References"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/ao4c03563_si_001.json b/task2/task2-chunks/ao4c03563_si_001.json
new file mode 100644
index 0000000..8b0d5fd
--- /dev/null
+++ b/task2/task2-chunks/ao4c03563_si_001.json
@@ -0,0 +1,12 @@
+[
+    {
+        "id": 1,
+        "chunk": "Supporting Information",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# Preparation of Antifog Hard Coatings Based on CarboxyFunctionalized Polyhedral Oligomeric Silsesquioxane Crosslinked with Oligo(ethylene glycol)s  \n\nJun Nakagawa, Seiya Morinaga, and Yoshiro Kaneko\\*  \n\nGraduate School of Science and Engineering, Kagoshima University, Kagoshima 890-0065, Japan  \n\n\\*Corresponding author, E-mail: ykaneko@eng.kagoshima-u.ac.jp (Y. Kaneko)  \n\n![](images/a623f7e192f5ea2d04ade73675ae826b2d6e3b8eadd9c1d43e6c90742ad3b7a7.jpg)  \nFigure S1. $\\mathrm{^{1}H}$ NMR spectrum of POSS-C in DMSO- $\\cdot d_{6}$ . The chemical shifts were referenced to DMSO (δ 2.5).  \n\n![](images/8d9edb5995a44e3fee95231d763fc832fcd565d23869530e2c2341440722211f.jpg)  \nFigure S2. $^{29}\\mathrm{Si}$ NMR spectrum of POSS-C in DMSO- $.d_{6}$ at $40^{\\circ}\\mathrm{C}$ . A small amount Cr(acac)3 was added as a relaxation agent. The chemical shifts were referenced to TMS (δ 0.0).  \n\n<html><body><table><tr><td>HO H n</td><td>n=1</td><td>n=2</td><td>n=3</td><td>n=4</td><td>n=5</td><td>n=6</td></tr><tr><td>COOH OH (POSS-C) (OEG) 5 ： 1</td><td>goshima University goshima University goshima University</td><td>goshima University goshima Universil goshima University</td><td>ima University ima University</td><td>shima University shima University shima University</td><td>shima University shima University shima University</td><td>oshima University oshima University oshima University</td></tr><tr><td>COOH OH (POSS-C) (OEG) 2 1</td><td>Kagoshima Univer Kagoshima Univ agoshima Unive</td><td>Kagoshima Univ Kagoshima Uni</td><td>Universi</td><td>oshima shima University shima Univers</td><td>goshima Universit goshin goshimaUniver</td><td>agoshima Univers agoshima Univers agoshima Univers</td></tr><tr><td>COOH OH (POSS-C) (OEG) 1 1</td><td>Kagoshima Unive agoshima Univer Kagoshima Unive</td><td>agoshima Univ agoshima Uni agoshima Unive</td><td>agoshima Univer agoskima Univers</td><td>goshima Unive 0</td><td>hima Univ</td><td>Kagoshima Univ Kagoshima Univ</td></tr></table></body></html>  \n\n![](images/e90f5889a03a5d963ac9bf14212c7b24110fdf938bf479c953e898e488da9e8c.jpg)  \nFigure S3. Appearance of POSS-C/OEG coatings.   \nFigure S4. UV-Vis spectra of a glass substrate and POSS-C/OEG coating $(n=4$ , $\\mathrm{COOH}{\\mathrm{:OH}}=2{:}1\\$ ).  \n\n![](images/574f1c663d94875dab0e942126a18b17caacb78034479429c9b40c1a74d05638.jpg)  \nFigure S5. (a) SEM image and (b) EDX pattern of POSS-C/OEG coating $(n=4$ , $\\mathrm{COOH}{\\mathrm{:OH}}=2{:}1$ ).  \n\n![](images/eee1544f23012fb89597507b45a36d666a6c61af011a8877c1c50e54c07ddab4.jpg)  \nFigure S6. Photo of the equipment used for antifogging evaluation.",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/ap4c00912_si_001.json b/task2/task2-chunks/ap4c00912_si_001.json
new file mode 100644
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--- /dev/null
+++ b/task2/task2-chunks/ap4c00912_si_001.json
@@ -0,0 +1,7 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Supporting Information  \n\nRobust UV-Curable Dual-Cross-Linked Coating with Increased Transparency, Long-Term Antifogging, and Efficient Antibacterial Performances  \n\nLina Zhang [1,3], Kai Feng\\*[1], Yizhe Liu [1,2], Fangrong Wu [1], Yubo Liu [1,2], Bo $\\mathrm{Yu}^{[2]}$ Xiaowei Pei [1,2], Lijia Liu[3], Chunhong Zhang[3] Yang $\\mathrm{Wu}^{*[1,2,4]}$ , Feng Zhou [2] [1] Yantai Zhongke Research Institute of Advanced Materials and Green Chemical Engineering, Shandong Laboratory of Advanced Materials and Green Manufacturing at Yantai, Yantai, Shandong 264006, PR China.   \n[2] State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Science, Lanzhou, Gansu 730000, PR China.   \n[3] Yantai Research Institute of Harbin Engineering University, Yantai, Shandong 264006, PR. China.   \n[4] Qingdao Centre of Resource Chemistry and New Materials, Qingdao, Shandong  \n\n266100, PR China.  \n\nCorresponding Authors: Yang Wu, Email: yangwu@licp.cas.cn Kai Feng, Email: kaifeng@amgm.ac.cn  \n\n![](images/c0bb05813c4c70d223893d4450fe6b3cf7a13ce055854e16cf46e32754aeac2b.jpg)  \nFigure S1. The fine spectrum of nitrogen and bromine of PET and pMDHAB−AA  \n\ncopolymer.  \n\n![](images/6dd7859da4fc5185f3d4b6b0275eef3cf9e979faf7e9dd2a802cb8169edd261d.jpg)  \nFigure S2. DTG curves of pDMAEMA−AA copolymer and pMDHAB−AA copolymer.  \n\n![](images/4e5bafefeab4403bd3b0e62e444eb29b8bab302cc8ed88d1f45fff154f45dd8a.jpg)  \nFigure S3. The cross-sectional SEM images of pMDHAB−AA coating.  \n\n![](images/7ff62d8f92bad4e7722e61ef3c70d951d37d80de6c20b50901b1b35827083808.jpg)  \nFigure S4. AFM images of PET surface.  \n\n![](images/2106dad24ce41871e7ef0da5ebc090491fbb677593aef69698cbc52c7ee2ef73.jpg)  \n\nFigure S5. (a) The thermal weight loss of different crosslinked coatings. (b) DTG curves of different crosslinked coatings.  \n\n![](images/0cd6cb5169f054400ccd62dfc1054cac93b56559069a8b888a5148fe13e233de.jpg)  \nFigure S6. Transmittance of pMDHAB−AA coatings after different dry-wet alternate  \n\nanti-fog test cycles with hot-vapor method.  \n\n![](images/24601ec255621f38bdf46b0546bf4a07fb04e13a7ef3e7b33eb799aef683d3de.jpg)  \nFigure S7. (a) Bending tests of a pMDHAB-AA coating. (b) The transmittance of the  \n\ncoating after bent 100 times. (c) Optical microscope image before coating bending. (d) Optical microscope image after coating bending.",
+        "category": " Results and discussion"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/bai-et-al-2020-antifogging-antibacterial-coatings-constructed-by-n-hydroxyethylacrylamide-and-quaternary-ammonium.json b/task2/task2-chunks/bai-et-al-2020-antifogging-antibacterial-coatings-constructed-by-n-hydroxyethylacrylamide-and-quaternary-ammonium.json
new file mode 100644
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@@ -0,0 +1,72 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Antifogging/Antibacterial Coatings Constructed by N‑Hydroxyethylacrylamide and Quaternary Ammonium-Containing Copolymers  \n\nShan Bai, Xiaohui Li,\\* Yunhui Zhao, Lixia Ren, and Xiaoyan Yuan\\*  \n\nCite This: ACS Appl. Mater. Interfaces 2020, 12, 12305−12316",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# ACCESS  \n\nE Metrics & More  \n\nSupporting Information  \n\n![](images/ba55c7b861b6b000bdb486f6f78e545cfa1f23b9cd4f78965429d8af6233d48d.jpg)  \n园 Article Recommendations  \n\nABSTRACT: Endoscopic surgery has gained widespread applications in various clinical departments, and endoscope surfaces with antifogging and antibacterial properties are essential for elaborate procedures. In this work, novel antifogging/antibacterial coatings were developed from a cationic copolymer and a hydrophilic copolymer, polyhedral oligomeric silsesquioxane-poly(quaternary ammonium compound-co-2-aminoethyl methacrylate hydrochloride) [POSS-P(QAC-co-AEMA)] and poly( $\\mathrm{\\Delta}N$ -hydroxyethylacrylamide-co-glycidyl methacrylate) [P(HEAA-co-GMA)] via a facile and green blending method. Such transparent coatings showed excellent antifogging performance under both in vitro and in vivo fogging conditions, mainly attributed to the high water-absorbing capability of HEAA and QAC. Antibacterial assays proved that the blending coatings had a superior antibacterial property, which could be improved with the proportion of POSS-P(QAC-co-AEMA) because of the bactericidal efficiency of cationic QAC. Meanwhile, owing to the high hydratability of HEAA, the blending coatings exhibited a bacteria-repelling property. By simply tuning the blending ratio of POSS-P(QAC-co-AEMA) and P(HEAA-co-GMA), the comprehensive bacteria-killing and bacteria-repelling properties of the coatings were achieved. Moreover, after incubating with red blood cells, the prepared blending coatings presented a lower hemolytic rate of less than $5\\%$ . The findings provided a potential means for addressing the challenge of fogging and bacterial contamination occurring in endoscopic lenses and other medical devices.  \n\nKEYWORDS: antifogging coatings, antibacterial properties, quaternary ammonium compounds, N-hydroxyethylacrylamide, enhanced hydration",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# INTRODUCTION  \n\nOver the past decade, endoscopic surgery has been widely accepted as a minimally invasive approach and applied in various clinical departments because it has a precise small-cut and rapid recovery characteristics as compared with open surgery.1 During a safe and successful endoscopic procedure such as laparoscopy and colonoscopy, maintaining a clear vision is paramount, which can improve precision, reduce operative time, and even prevent inadvertent injury. Meanwhile, microbial colonization and biofilm formation on the surfaces of endoscopes is another impediment for a safe surgery.3−5  \n\nThe main reason of optical loss is endoscopic lens fogging, which is caused by the discrepancies in temperature and humidity between ambient conditions and in vivo.2 Most antifogging approaches for medical devices are based on traditional methods, for instance, spraying antifogging reagents or employing heating apparatus, but they show disadvantages of short residual action, cumbersome procedure, high medical expenses, and so on.6,7 Currently, developing coating surfaces with enhanced antifogging performance has been gaining much attention to solve the atomization problem.8−19 In addition to superhydrophilic and superhydrophobic strategies, applying a water-absorbing coating with amphiphilicity to a surface is an effective antifogging approach, where the condensed water molecules or the moist vapor can be rapidly imbibed into the bulk of the coating, followed by uniform diffusion of the absorbed water molecules to prevent the formation of a large and light-scattering water domain.8−14,20−23  \n\n![](images/411e11998af045cf8c9e04cabff9ffc93914638a33c5db847e428a5e42d48883.jpg)  \nFigure 1. (A) Synthesis of POSS-P(QAC-co-AEMA) and P(HEAA-co-GMA) copolymers. (B) Schematic preparation of the blending coatings.  \n\nAs invasive medical devices, endoscopes are prone to be heavily contaminated and associated with the healthcareassociated infections. On one hand, it is inevitable for endoscopes to be contaminated by environmental bacteria during storage, and the endoscopic environments provide favorable conditions for bacterial proliferation and subsequent biofilm formation.24,25 In addition, clinically used endoscopes comprise a high bioburden of microbes that originate from patients, and it is difficult to clean and disinfect the used devices due to their complex and delicate structure.26 Therefore, a dual-functional antifogging/antibacterial surface is in high demand in the field of endoscopy to prevent fogging and bacterial contamination.  \n\nIn recent years, comprehensive antibacterial coatings have been broadly developed to solve the problems of microbial infections in medical device surfaces.27−33 Nevertheless, only a few studies have focused on the development of antifogging and antibacterial surfaces so far.16,34−37 For instance, robust poly(vinyl alcohol)/poly(acrylic acid)/silver composite films with antifogging and antibacterial properties were prepared, where the abundant hydroxyl groups in the polymers could prevent fog formation and distributed silver nanoparticles endowed the composite films with bactericidal activity.34 Zhang et al. fabricated a multifunctional coating for antifogging, self-cleaning, and antimicrobial properties on the basis of zwitterionic peptides. The superhydrophilicity of zwitterionic material could strongly bind to water molecules and thus impart the coating with excellent antifogging performance and resistance to bacterial adhesion.16 However, the antibacterial properties of these prepared antifogging/ antibacterial surfaces were achieved by either an active-attack bacteria-killing or a passive-defense bacteria-repelling mechanism. Despite their general effectiveness, both the surfaces have inherent limitations for practical applications. Bacteria would grow rapidly and form a stubborn biofilm once attached onto the passive-defense surfaces, whereas for the active-attack bacteria-killing surfaces, continuous contamination of dead bacteria and debris is the fatal weakness, which causes the bactericidal groups to be shielded and thus greatly reduces the killing efficiency.38,39  \n\nQuaternary ammonium compounds (QACs) display broadspectrum bactericidal activity by destructive interaction with the cell membrane and subsequent enzyme inactivation, and fhoaovde ibnedeunstarpyp, iwedasitnewmataenrytreladtsmseunct,hansdbisomoend.i4c0a−l43maAtemrioanlsg, them, (meth)acrylic derivatives-related QACs are generally employed as antibacterial materials. A series of alkyl bromides with different alkyl chain lengths were used to quaternize poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA), and the results suggested that PDMAEMA quaternized with 1-bromobutane (PDMAEMA-C4) exhibited balanced membrane-disrupting activity and biocompatibility.44,45 Owing to two hydrogen-bond donors of amide groups and hydroxyl groups in $N.$ -(2-hydroxyethyl)acrylamide (HEAA), (polyHEAA)-based materials exhibit strong resistance to bacterial attachment, protein nonspecific adsorption, and cell adhesion.46−49 The hydration ability of a copolymer can be enhanced by incorporation of HEAA. Additionally, it was reported that hydroxyl groups are instrumental in improving the hemocompatibility of cationic polymers.50  \n\nIn this study, the dual-functional antifogging/antibacterial coatings that combine bacteria-killing and bacteria-repelling abilities were developed by blending polyhedral oligomeric silsesquioxane-poly(N-(2-(methacryloyloxy)ethyl)-N,N-dimethylbutan ammonium bromide-co-2-aminoethyl methacrylate hydrochloride) [POSS-P(QAC-co-AEMA)] and poly(N-hydroxyethyl acrylamide-co-glycidyl methacrylate) [P(HEAA-coGMA)]. Incorporation of AEMA and GMA was performed to crosslink the two random copolymers, and a small quantity of 1,3,5-triformylbenzene (TFB) was added as a co-crosslinker to further react with the amino and hydroxyl groups in the copolymers as well as amino-modified glass substrates, forming a chemically crosslinked stable system. Hydrophobic POSS was introduced to facilitate coating stability and mechanical properties.11,51,52 The antifogging and antibacterial properties of the blending coatings with different blending ratios were evaluated by hot-vapor and cold-warm antifogging tests, standard plate count method, bacterial antiadhesive assays, and growth inhibition to acquire the optimized blending ratios.  \n\nTable 1. Compositions and Number-Average Molecular Weights of the Synthesized Copolymers   \n\n\n<html><body><table><tr><td rowspan=\"2\"></td><td colspan=\"2\">feeding ratio (mol/mol)</td><td colspan=\"2\">actual ratioa (mol/mol)</td><td colspan=\"2\">molar compositionb (mol/mol)</td><td rowspan=\"2\">Mnc (x104)</td><td rowspan=\"2\">Dc</td></tr><tr><td>copolymer QAC/AEMA</td><td>HEAA/GMA</td><td>QAC/AEMA</td><td>HEAA/GMA</td><td>QAC/AEMA</td><td>HEAA/GMA</td></tr><tr><td>POSS-P(QAC-co-AEMA)</td><td>200:50</td><td></td><td>3.03:1</td><td></td><td>342:113</td><td></td><td>12.0</td><td>1.32</td></tr><tr><td>P(HEAA-co-GMA)</td><td></td><td>300:20</td><td></td><td>14.28:1</td><td></td><td>795:55.7</td><td>9.94</td><td>1.24</td></tr></table></body></html>\n\naDetermined by $^1\\mathrm{H}$ NMR spectra. bCalculated by the GPC results and actual molar ratios. cObtained from GPC using poly(ethylene glycol) as the standard.  \n\nTable 2. Compositions for Preparation of the Antifogging/Antibacterial Coatings   \n\n\n<html><body><table><tr><td>coating</td><td>POSS-P(QAC-co-AEMA) (mg)</td><td>P(HEAA-co-GMA) (mg)</td><td> TFB (mg)</td><td> POSS-P(QAC-co-AEMA)/P(HEAA-co-GMA) mass ratio (mg/mg)</td></tr><tr><td>PPQAa</td><td>18</td><td>0</td><td>0.54</td><td>1:0</td></tr><tr><td>PPQA/PHGb</td><td>12</td><td>6</td><td>0.54</td><td>1:0.5</td></tr><tr><td>PPQA/PHGb</td><td>9</td><td>9</td><td>0.54</td><td>1:1</td></tr><tr><td>PPQA/PHGb</td><td>6</td><td>12</td><td>0.54</td><td>1:2</td></tr><tr><td>PHGa</td><td>0</td><td>18</td><td>0.54</td><td>0:1</td></tr></table></body></html>\n\naOne-component coatings were prepared from POSS-P(QAC-co-AEMA) or P(HEAA-co-GMA) only. bBlending coatings were prepared from POSS-P(QAC-co-AEMA) and P(HEAA-co-GMA) with different mass ratios.  \n\nAdditionally, antifogging is considered as the principal intention in vivo.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# EXPERIMENTAL SECTION  \n\nSynthesis of POSS-P(QAC-co-AEMA) and P(HEAA-co-GMA) Copolymers. As shown in Figure 1A, the QAC and $N_{\\sun}$ - hydroxyethylacrylamide (HEAA)-containing copolymers, that is, POSS-P(QAC- $c o$ -AEMA) and P(HEAA- $_{c o}$ -GMA), for the blending coating preparation were synthesized via reversible addition− fragmentation chain transfer (RAFT) polymerization and free radical polymerization, respectively. QAC was prepared by quaternization of 2-(dimethylamino)ethyl methacrylate (DMAEMA) with 1-bromobutane. The hydrophobic component was incorporated by modifying the RAFT agent of CPADB with aminopropylisobutyl polyhedral oligomeric silsesquioxane $\\left(\\mathrm{POSS-NH}_{2}\\right)$ ) to obtain POSS-CPADB.53 Compositions and molecular weights of POSS-P(QAC-co-AEMA) and P(HEAA-co-GMA) copolymers are given in Table 1. It is worth mentioning that the copolymer compositions obtained by combining gel permeation chromatography (GPC) results with actual molar ratios were higher than their feeding, probably due to the copolymer aggregating in the eluent when determining molecular weight by GPC. Detailed synthesis procedures and the characterizations of their chemical structure by proton nuclear magnetic resonance $\\mathrm{\\Omega^{\\prime1}H\\ N M R})$ spectroscopy and GPC are described in the Supporting Information and Figure S1.  \n\nPreparation of the Blending Coatings. The preparation process of the blending coatings is schematically illustrated in Figure 1B. Bare glass was first treated with oxygen plasma (18 W, $^{60\\mathrm{~s},}$ Harrick Plasma PDC-32G-2, USA) to produce abundant hydroxyl groups, followed by immersing into (3-aminopropyl)- trimethoxysilane/methanol solution $(5\\%,{\\bf v}/{\\bf v})$ for $^{4\\mathrm{~h~}}$ and sonicating with methanol and ethanol in sequence to provide amino-functionalized surfaces. The successful surface modifications were demonstrated by the change of the water contact angle (WCA) for each surface as also presented in Figure 1B. Then, copolymers with various POSS-P(QAC-co-AEMA)/P(HEAA-co-GMA) blending mass ratios and a certain amount of TFB (Table 2) were dissolved in $200~\\mu\\mathrm{L}$ of ethanol (P(HEAA-co-GMA) stored in aqueous solution with a concentration of $60~\\mathrm{mg/mL}$ ). A determined volume of the mixture was drop-coated onto the modified glass slides to allow the crosslinking of POSS-P(QAC-co-AEMA), P(HEAA-co-GMA), and TFB for antifogging tests. It was also cast onto a cropped square glass in $1\\times1~\\mathrm{cm}^{2}$ for antibacterial and hemolytic analysis. All coated samples were dried at room temperature and subsequently thermalcured at $40~^{\\circ}\\mathrm{C}$ overnight. The resultant coatings with different blending ratios were denoted as PPQA, $\\mathrm{PPQA_{2}/P H G_{1}},$ $\\mathrm{PPQA_{1}/}$ $\\mathrm{PHG}_{\\mathrm{1}},$ $\\mathrm{\\bar{PPQA}_{1}/P H G}_{2},$ and PHG, which showed the thicknesses of  \n\n$9.14\\pm0.39\\$ , $7.34\\pm0.36,$ $7.57\\pm0.59.$ , $7.13\\pm0.22,$ and $6.74\\pm0.17$ $\\mu\\mathrm{m},$ respectively (Figure S2). Overall, a green blending strategy, where water and ethanol were employed as solvents, was developed to prepare the dual-functional coatings with desired antifogging and antibacterial properties.54  \n\nCharacterizations of the Blending Coatings. The mean WCA, droplet diameter $(D)_{\\cdot}$ , and their evolution within $400\\mathrm{~s~}$ were recorded on a contact angle meter (Shanghai Zhongchen Instrument JC2000D, China) at room temperature. Each coating was analyzed at least three times. Variation of the wetted surface area (S) for various coatings was further calculated by the following equation  \n\n$$\n\\Delta S/S_{0}=\\frac{S_{(t)}-S_{0}}{S_{0}}=\\frac{\\pi{D_{(t)}}^{2}/4-S_{0}}{S_{0}}\n$$  \n\nwhere $D_{(t)}$ and $S_{(t)}$ are defined as the droplet diameter and wetted surface area at a given time, respectively. $S_{0}$ is the original wetted surface area. Attenuated total reflectance−Fourier transform infrared spectroscopy (ATR−FTIR) (TENSO 27 spectrometer, Germany) was employed to confirm the chemical structure of the blending coatings. To test transparency and quantitively determine the antifogging properties of the coatings, visible light transmittance values of the double-coated surfaces were collected on a $722\\ s$ visible spectrophotometer (Shanghai Jinghua Technology Instruments, China) in the wavelength range of $400{-}800\\ \\mathrm{nm}$ before and after the samples were placed at $-20\\ ^{\\circ}\\mathrm{C}$ for $30~\\mathrm{\\min}$ . The surface morphology and root-mean-square roughness $(R_{\\mathrm{q}})$ values of the prepared coatings were observed by atomic force microscopy (AFM) (Benyuan Nano-Instruments CSPM5500A, China).  \n\nAntifogging Tests. Glass substrates were coated with a copolymer coating on both sides. To perform the antifogging tests in vitro, the samples were held ${\\mathfrak{s}}\\mathrm{cm}$ above hot water $(80~^{\\circ}\\dot{\\mathrm{C}})$ for $10~\\mathsf{s}$ and in a refrigerator $(-20\\ ^{\\circ}\\mathrm{C})$ for $30~\\mathrm{min}$ with the purpose of hotvapor and cold-warm antifogging tests, respectively, followed by moving the samples to ambient conditions and taking photographs immediately.  \n\nTo further assess the antifogging performance in vivo, a rabbit oral cavity with a digital endoscope (Hangzhou Jingjiying Hardware Store, China) was used as the animal model. All procedures involving animals comply with the Tianjin Experimental Animal Management Ordinance, China. The circular coating sample with a diameter of 4.9 mm was first prepared and fixed between the endoscope lens and its protective sleeve. Then, the structural component of the digital endoscope was placed into the rabbit’s oral cavity and maintained for a certain time. The process was recorded from endoscope insertion onward.  \n\nAntibacterial Tests. Minimum inhibitory concentrations (MIC) of the synthesized copolymers were first determined. Typically, 4096 $\\mu\\mathrm{g}$ of the copolymer was first dissolved in $2~\\mathrm{mL}$ of sterile phosphate buffered saline (PBS) and then diluted with the serial two-fold method to obtain a series of copolymer solutions with varying concentrations. The copolymer solution $(100~\\mu\\mathrm{L})$ with a certain concentration and $100\\mu\\mathrm{L}$ of bacterial suspension $(3\\times10^{5}\\mathrm{CFU/mL})$ ) were added into each well. The bacterial suspension with equal volume of sterile PBS was set as the positive control and $100~\\mu\\mathrm{L}$ of pure Mueller−Hinton broth (MHB) diluted with $100~\\mu\\mathrm{L}$ of sterile PBS buffer was used as the negative control. After incubating the plate at $37^{\\circ}\\mathrm{C}$ at the speed of $80\\ \\mathrm{rpm}$ for $^{24\\mathrm{h},}$ the optical density (OD) at $600\\mathrm{nm}$ of the microorganism solutions was recorded. The MIC value was defined as the lowest concentration of copolymer, where no visual growth of bacteria was found. The bacterial growth inhibition rate was determined according to eq 2  \n\n![](images/e6fa0cc81b80f468dbd3c41d00ee54d7e600daa4b9363a031eb4108fa9ca0524.jpg)  \nFigure 2. (A) ATR−FTIR spectra of the prepared copolymer coatings. (B) Transmittance curves of the double-coated samples and bare glass in the wavelength range of $400{-}800~\\mathrm{nm}$ . (C) AFM topographic images and root-mean-square $(R_{\\mathrm{q}})$ roughness of the coatings over a scope of $4\\times4$ $\\mu\\mathrm{m}^{2}$ with the tapping mode.  \n\n$$\n=\\frac{O D_{\\mathrm{positive\\control}}-O D_{\\mathrm{sample}}}{O D_{\\mathrm{positive\\control}}-O D_{\\mathrm{negative\\control}}}\\times100\n$$  \n\nFor the coating samples, the antibacterial activities were estimated by the standard plate count method. The test coatings sterilized in ultraviolet before the test were placed into a 24-well plate, followed by adding the bacterial suspension $(200~\\mu\\mathrm{L},~3~\\times~10^{\\bar{4}}~\\mathrm{CFU/mL})$ and MHB $(600\\mu\\mathrm{L})$ . After culturing for $^{24\\mathrm{h},}$ , the bacterial suspension was diluted with an appropriate factor and $10\\mu\\mathrm{L}$ of the diluted suspension was spread on nutrient agar. A sample of bare glass was the positive control. The bacterial colonies were photographed, and the colony numbers $(N)$ were counted after overnight incubation. The bacterial growth inhibition rate was calculated from eq 3  \n\n$$\n(\\%)=\\frac{N_{\\mathrm{positive\\control}}-N_{\\mathrm{sample}}}{N_{\\mathrm{positive\\control}}}\\times100\n$$  \n\nScanning electron microscopy (SEM, Hitachi SU1510, Japan) was employed to evaluate the bacterial morphology and adhesion. Typically, $500~\\mu\\mathrm{L}$ of bacterial suspension $\\left({3\\times10^{5}\\mathrm{CFU/mL}}\\right)$ was dropped on each sterile coating in a 24-well plate, separately. After culturing for $^{4\\mathrm{h}}$ at $37^{\\circ}\\mathrm{C},$ the coatings were gently rinsed with sterile PBS thrice to take out the loosely attached bacteria. Then, the bacteria that attached on coating surfaces were fixed with $2.5\\%$ glutaraldehyde solution at $4^{\\circ}\\mathrm{C}$ for $^{2\\mathrm{h},}$ followed by rinsing with sterile PBS buffer. Dehydration was performed with a series of ethanol aqueous solutions (25, 50, 75, 95, and $100\\%$ ).  \n\nThe live/dead assay was performed to reveal the bacterial viability and population after contacting with the copolymer coatings. Oneside coated samples in $1\\times1~\\mathrm{cm}^{2}$ area were first individually put into a 24-well plate, then $500\\mu\\mathrm{L}$ of bacterial suspension $\\left(3\\times10^{6}\\mathrm{CFU/mL}\\right)$ and $500\\mu\\mathrm{L}$ of MHB were added into each well. After culturing for $6\\mathrm{{h}}$ at $37\\ ^{\\circ}\\mathrm{C},$ the coatings were rinsed thrice with sterile pure water and stained with $200\\mu\\mathrm{L}$ of propidium iodide (PI)/SYTO 9 mixture for 15 min in the dark. Subsequently, the samples were washed with sterile water again for discarding the residual dye solution, and the stained samples were mounted between a slide and a coverslip and observed under a fluorescence microscope (Nikon Eclipse Ti-S, Japan).  \n\nHemolytic Test. The hemolytic assay was performed as described in refs 16 and 55. In brief, fresh sheep blood was diluted with PBS buffer $\\mathrm{(pH~7.4)}$ and then centrifuged at $2000~\\mathrm{rpm}$ for $10\\ \\mathrm{\\min},$ followed by discarding the supernatants and repeating the above step twice. The washed red blood cell (RBCs) was diluted with PBS in a ratio of 1:9. Then, $500~\\mu\\mathrm{L}$ of $10\\%$ RBC suspension was placed on each prepared $1\\times1~\\mathrm{cm}^{2}$ coating in a 24-well plate, and subsequently $500~\\mu\\mathrm{L}$ of PBS buffer was also added into each well. After incubating at $37^{\\circ}\\mathrm{C}$ for $^{2\\mathrm{h},}$ the whole blood solutions were centrifuged at 2000 rpm for $10\\ \\mathrm{min}$ . Then, aliquots $\\left(100~\\mu\\mathrm{L}\\right)$ of the supernatants were transferred into a 96-well plate, and the OD values at $541~\\mathrm{nm}$ were measured. The untreated blood suspension and blood diluted with water were used as the negative and positive controls, respectively. The hemolysis was calculated by the following eq 4  \n\n$$\n\\mathrm{Hemolysis\\:(\\%)}=\\frac{O D_{\\mathrm{sample}}-O D_{\\mathrm{negative\\:control}}}{O D_{\\mathrm{positive\\:control}}-O D_{\\mathrm{negative\\:control}}}\\times100\\\n$$  \n\n![](images/d98850fab3abe99e8b3bd6b7c05186fa014616328965e0321ad83e30f7846c97.jpg)  \nFigure 3. In vitro antifogging study. (A) Antifogging performances of the prepared coatings with both hot-vapor and cold-warm method. (B) Transmittance of the coatings and bare glass during the cold-warm antifogging test. (C) Evolution of WCA and wetted surface area (S) of the coating samples within $400\\mathrm{~s~}$ . Wetted surface area variation is expressed as $\\Delta S/S_{0},$ where $\\Delta S=S_{(t)}-S_{0},S_{(t)}$ and $S_{0}$ are the wetted surface areas at a given time and initial moment, respectively.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# RESULTS AND DISCUSSION  \n\nThe dual-functional antifogging/antibacterial coatings with various POSS-P(QAC-co-AEMA)/P(HEAA- $_c o$ -GMA) ratios were successfully prepared. According to the blending ratios, the resultant coatings were denoted as $\\mathrm{PPQA}_{2}/\\mathrm{PHG}_{1},$ $\\mathrm{PPQA_{1}/}$ $\\mathrm{PHG}_{1},$ and $\\mathrm{PPQA_{1}/P H G_{2}},$ respectively. As control, two onecomponent coatings were also prepared from POSS-P(QACco-AEMA) and P(HEAA-co-GMA), which were expressed as PPQA and PHG, respectively. Antifogging, bacteria-killing, and bacteria-repelling properties of the blending coatings were systematically evaluated to investigate the relationships between polymer compositions and the coatings’ performance.  \n\nCharacterizations of the Antifogging/Antibacterial Coatings. The structure of the prepared blending coatings was confirmed by ATR−FTIR spectra as shown in Figure 2A. The characteristic peak at $1723~\\mathrm{{\\bar{c}m}^{-1}}$ was attributed to $\\scriptstyle{\\mathrm{C}}={\\mathrm{O}}$ stretching vibration of the ester group, and the absorption peak at $1552~\\mathrm{{cm}^{-1}}$ was corresponding to $\\mathrm{\\DeltaN-H}$ bending vibration of the amide group in HEAA.56 With the adding of P(HEAA-coGMA), the intensity of the peak at $1552~\\mathrm{{cm}^{-1}}$ strengthens gradually, whereas the peak of $1723~\\mathrm{{cm}^{-1}}$ becomes weaker. Moreover, the absorption peak at $3270~\\mathrm{{cm}^{-1}}$ belonged to the $\\mathrm{\\DeltaN-H}$ and $_\\mathrm{O-H}$ stretching vibrations, that were present in all prepared coatings except for the POSS-P(QAC-co-AEMA) coated surface.57 All of the above results indicate that the PPQA/PHG blending coatings have been successfully prepared. One of the basic requirements for antifogging coating is the transparency of the coating itself. Visible light transmittance of the blending coatings as well as bare glass were collected (Figure 2B). The prepared PPQA/PHG blending coatings exhibited highly visible light transmittance of $85.0\\mathrm{-}90.0\\%$ approximately, comparable to that of bare glass $\\left(86.8-91.2\\%\\right)$ , indicating good compatibility of POSS-P(QAC-co-AEMA) and P(HEAA-co-GMA). Whereas for the PPQA and PHG coatings, the visible light transmittance values in the wavelength range of $400{-}800~\\mathrm{nm}$ were $79.6\\mathrm{-}84.6$ and $76.9\\mathrm{-}80.8\\%$ , respectively, which are lower than those of bare glass and the prepared PPQA/PHG blending coatings, this was probably due to the higher crosslinking density present in onecomponent PPQA and PHG coatings, decreasing the smoothness of the coating surfaces.  \n\nThe surface morphology of the copolymer coatings was further explored by AFM. It could be obtained from Figure 2C that the root-mean-square roughness $R_{\\mathrm{q}}$ values of PPQA, $\\mathrm{PPQA}_{2}/\\mathrm{PHG}_{1},$ $\\mathrm{PPQA_{1}/P H G_{1}},$ $\\mathrm{PPQA_{1}/P H G_{2}}$ and PHG coatings were 13.9, 0.7, 0.9, 0.8, and $22.3\\ \\mathrm{nm},$ respectively. The nanoscaled roughness indicated that smooth surfaces were formed, which can facilitate optical transparency.21 Meanwhile, the decreased $R_{\\mathrm{q}}$ values of the PPQA/PHG blending coatings indicate smoother surface topography, suggesting that the two copolymers exhibited good compatibility and no phase separation appeared during the blending process. The higher roughness of the PPQA and PHG coating surfaces could be attributed to strong interactions between the copolymer itself.  \n\nAntifogging Performance. Antifogging performance of the blending coatings was evaluated by both qualitative and quantitative measurements.8−11,16−18 First, optical images were photographed during both hot-vapor and cold-warm antifogging tests as showed in Figure 3A. The bare glass fogged up immediately either placing them over boiling water or after storing in a refrigerator for $30\\mathrm{min}$ , whereas the coated surfaces maintained visible clearness under hot-vapor antifogging measurement, demonstrating a remarkable antifogging behavior. It could be seen that all coatings kept free of fog and the green plants can be seen obviously after storing at $-20\\ ^{\\circ}\\mathrm{C},$ except for the PPQA and PHG coatings, indicating that the foggy environments were harsher with cold-warm method compared with hot-vapor method. The three blending coatings, $\\mathrm{PPQA}_{2}/\\mathrm{PHG}_{1},$ $\\mathrm{PPQA_{1}/P H G_{1}},$ and $\\mathrm{PPQA_{1}/P H G_{2}},$ qualitatively showed raised transmittance in comparison with the bare glass substrate when exposed to foggy conditions, indicating their excellent antifogging performance. It was mainly attributed to quaternary ammonium, hydroxyl, and amide groups in POSS-P(QAC-co-AEMA) and P(HEAA-coGMA), which can absorb water molecules from the environment and diffuse to prevent a large water domain formation, thus avoiding or reducing light scattering and refraction.  \n\n![](images/a6560ba0c8080bc31038a4af62b62361964d71f3cd1b0780073c17dadd78c1f7.jpg)  \nFigure 4. In vivo antifogging study. (A) Schematic illustration of the in vivo antifogging test using a rabbit oral cavity model, showing photographs of the real digital endoscope and the preparation of the test sample. The circular coating samples ( $\\dot{d}=4.9\\ \\mathrm{mm}$ ) were fitted between the lens and an elastic protective sleeve. (B) Digital photographs of the rabbit’s maxilla taken from the video at different time points.  \n\nSecond, the antifogging properties of the blending coatings were further quantitatively characterized on a visible spectrophotometer, where visible light transmittances of each double-coated surface were collected when exposed to ambient conditions after keeping at $-20~^{\\circ}\\mathrm{C}$ for $30~\\mathrm{min}$ . As shown in Figure 3B, the visible light transmittance of $\\mathrm{PPQA}_{2}/\\mathrm{PHG}_{1},$ $\\mathrm{PPQA_{1}/P H G_{1}},$ and $\\mathrm{PPQA_{1}/P H G_{2}}$ coatings maintained at $84-$ $90\\%$ and almost the same as those of the coated surfaces before freezing. These results indicated that antifogging properties of the prepared PPQA/PHG blending coatings were almost unaffected by the blending ratios. In contrast, bare glass only has a light transmittance of $28-36\\%$ because of strong light scattering phenomenon. During the cold-warm antifogging test, it could be seen that the light transmittance of PPQA and PHG coatings were $^{67-78}$ and $52\\mathrm{-}67\\%$ , respectively, which was consistent with the above results of optical images. The discounted antifogging behavior was probably due to their higher crosslinking density in comparison with the other three coatings that blended POSS-P(QAC-co-AEMA) with P(HEAA-co-GMA). Furthermore, the antifogging performance of $\\mathrm{PPQA_{1}/P H G_{1}}$ and POSS-free $\\mathrm{PQA_{1}/P H G_{1}}$ coatings was compared, and the result suggested that POSS had little effect on antifogging ability of the blending coatings prepared in this work (Figure S3), but it was demonstrated that the introduction of POSS was beneficial to the coating stability (Figure S4).  \n\nIt is widely accepted that surface wettability plays a significant role in antifogging performance. To investigate the origin and difference in antifogging capability of the prepared copolymer coatings, time-dependent WCA measurements over a 400 s period were performed and the results are shown in Figure 3C. Evidently, all coating surfaces had an initial WCA value about $110^{\\circ}$ and then gradually dropped until stable, which was in contrast to that of bare glass (tiny change with time due to water evaporation). It was considered that the prepared coatings belonged to the typical water-absorbed coatings that show the WCA in the range of 40−110°.14 Reasonably, the antifogging properties of the prepared coatings were attributed to the strong water absorption capability, and subsequently spread it into a hydrated film via hydrogen bonds. Compared with the one-component coatings of PPQA and PHG, the blending $\\mathrm{PPQA}_{2}/\\mathrm{PHG}_{1},$ $\\mathrm{PPQA_{1}/P H G_{1}},$ and $\\mathrm{PPQA_{1}/P H G_{2}}$ coatings displayed a relative rapid decrease of WCA to $57.7\\pm0.9$ , $53.8\\pm0.4_{;}$ , and $63.6\\pm1.4^{\\circ}$ within $400\\ \\mathrm{s},$ respectively, more quickly than both PPQA and PHG coatings (stable WCA values were $82.2~\\pm~3.1$ and $74.5~\\pm~4.0^{\\mathrm{\\bar{o}}}.$ , respectively), resulting in an enhancement of the antifogging performance. It was assumed that the rapid decrease of WCA was probably due to the formation of moderate crosslinking density in the PPQA/PHG blending coatings, which was more conducive to the water absorption process. Further comparison of the wettability of the PPQA/PHG coating exhibited that the $\\mathrm{PPQA_{1}/P H G_{1}}$ coating surface was the most hydrophilic. As mentioned above, PHG coating was highly crosslinked owing to many more crosslinking sites of hydroxyl groups, thus its water-absorbing capability was restricted to some extent, resulting in unsatisfactory antifogging performance. On the other hand, the coating would become more hydrophobic with increased content of POSS-containing copolymer POSSP(QAC-co-AEMA). In consequence, no matter whose content is higher, it is not helpful to absorb water molecules for coated surfaces. In order to study the wetting properties more indepth, Figure 3C showed the wetted surface area evolution $(\\bar{\\Delta S}/S_{0})$ over $400\\mathrm{~s~}$ time interval for the coated samples as well as bare glass. The wetted surface area of bare glass remained nearly unvaried with time, whereas all coated surfaces had an increased trend in wetted surface area, indicating that the water droplets had spread. For PPQA/PHG blending coatings, the values of $\\Delta S/S_{0}$ kept going up to nearly $100\\%$ within $400\\ \\mathrm{s}.$ . However, after an increase of $50\\%$ over the first $^{60\\mathrm{~s,~}}$ the wetted surface areas of PPQA and PHG coatings remained unchanged. These results also demonstrated that the blending coatings had stronger water-absorbing capability than that of one-component coatings.  \n\n![](images/c42f9166e9ad83b38c463218247b6025ee0df8c822076ecf7d213538e5d1a0c4.jpg)  \nFigure 5. Antibacterial properties. (A) Growth inhibition rates of POSS-P(QAC-co-AEMA) copolymers in aqueous solutions with a sequence of concentrations against S. aureus and $E$ . coli. (B) Photographs of bacterial colonies of S. aureus and $E_{\\sun}$ coli after incubation with various coatings and bare glass at $37~^{\\circ}\\mathrm{C}$ for $24\\mathrm{~h~}$ . (C) Growth inhibition rates of the prepared coatings calculated by standard plate count methods. All data were obtained from at least three samples.  \n\nAntifogging is considered as the principal intention when emphasized for use in vivo. Therefore, the superior in vivo antifogging effects of the blending coatings were further demonstrated by using a rabbit oral cavity model as shown in Figure 4A. The endoscope images of the whole operating process were recorded. For each, the digital photographs at predetermined moments $(\\sim2,\\sim30,$ and ${\\sim}60~\\mathrm{s}$ ) were captured from the corresponding video and are presented in Figure 4B. Fog formed immediately on the bare glass surface after it was put into the humid oral environment, and visible optical loss occurred after insertion for about $30\\mathrm{~s~}$ due to strong light scattering (Figure 4B and Video S1). It is noteworthy that some visual acuity still remained at $^{2\\ s,}$ indicating that the blurry vision was caused by the endoscope lens fogging, rather than being out of focus. Fortunately, all coated samples remained optically clear and the rabbit’s maxillae were highly visible at $^{30\\mathrm{~s,~}}$ demonstrating the antifogging performance. Furthermore, it could be seen that after $^{60}\\ s,$ the onecomponent coatings, especially for PHG coating, had a compromised antifogging property in comparison with the other three PPQA/PHG coatings. It was consistent with the results of the antifogging tests in vitro, but the blending coatings such as $\\mathrm{PPQA_{1}/P H G_{2}}$ still kept visually clear even under strong fogging conditions for $120\\ s$ (Video S2), showing high efficiency in preventing fog formation.  \n\nAntibacterial Properties. The antibacterial activity was first evaluated by testing MIC of copolymers against both Gram-positive bacteria, Staphylococcus aureus and Gramnegative bacteria, Escherichia coli. As shown in Figure 5A, the cationic copolymer of POSS-P(QAC-co-AEMA) had MIC values of 128 and $256~\\mu\\mathrm{g/mL}$ toward S. aureus and E. coli, respectively, which displayed reasonable antibacterial activity in comparison with antimicrobial polypeptides, antibiotic, or sliver-based antibacterial systems that exhibited MIC lower than $100~\\mu\\mathrm{g/mL}$ or even less than $10~\\mu\\mathrm{g/mL}.^{58-61}$ On the other hand, P(HEAA-co-GMA) has no antibacterial activity due to the lack of antimicrobial groups.  \n\nThe antibacterial properties of the copolymer coatings were investigated via the standard plate count method. As illustrated in Figure 5B, there were lots of bacteria colonies covered on a plate of the control sample. In sharp contrast, almost no colonies could be observed on cationic PPQA coating plates, both toward S. aureus and E. coli, suggesting that cationic QAC has excellent bactericidal activity. The blending coatings with different PPQA/PHG ratios of $2/1,1/1$ , and $1/2$ were also detected in this measurement. It could be seen from Figure 5B that there were also no bacteria colonies on the $\\mathrm{PPQA_{2}/P H G_{1}}$ plate and with the increased ratio of POSS-P(QAC-co-AEMA), the number of bacterial colonies declined, whereas PHG coating exhibited a similar result as that of bare glass. It could be concluded from the above results that hydroxyl-containing copolymer P(HEAA-co-GMA) had almost no contribution to bactericidal performance, but appropriate incorporation into coatings could still maintain the antibacterial performance compared with the PPQA sample.  \n\nThe antibacterial activities of the prepared coatings were further quantitatively investigated to obtain the growth inhibition rates by counting the number of bacteria colonies as shown in Figure 5B. It can be seen in Figure 5C that the growth inhibition rates of PPQA and $\\mathrm{PPQA}_{2}/\\mathrm{PHG}_{1}$ coatings nearly hit $99.9\\%$ against S. aureus and E. coli. With the increase of P(HEAA-co-GMA) content, $\\mathrm{PPQA_{1}/P H G_{1}},$ $\\mathrm{PPQA_{1}/P H G}_{2},$ and PHG coatings showed reduced bacterial growth inhibition rates at $67.2\\pm{\\:3.9}_{}$ , $47.7\\pm9.2\\$ , and $1.7\\pm5.3\\%$ , respectively, against E. coli. It could be assumed that the PPQA/PHG ratio had a significant effect on the antibacterial properties of the blending coatings. Meanwhile, it could be observed that the growth inhibition rate of $\\mathrm{PPQA_{1}/P H G_{1}}$ also reached $99.9\\%$ against S. aureus, indicating that the antibacterial activity of the prepared blending coatings against S. aureus was stronger than that of $E_{\\rightleftarrows}$ . coli, which was in accordance with the MIC results. This could be possibly related to the bacterial cell structure.62,63 Compared with Gram-positive S. aureus, an additional lipopolysaccharide-containing membrane was present in the structure of the Gram-negative $E$ . coli, thus making membrane destruction more difficult. Moreover, the antibacterial activities of POSS-free copolymer of P(QAC-coAEMA) and $\\mathrm{PQA_{1}/P H G_{1}}$ blending coating were also tested (Figure S5). The results indicated that POSS had little effect on antibacterial properties in this study. In addition, as suggested for potential applications for endoscopes, the blending coatings were also demonstrated to have long-term and recycling antibacterial property (Figure S6).  \n\nThe bacteria-associated infection begins with the adhesion of bacteria to the device surfaces. Therefore, endowing surfaces with bacteria-repellency is critical for biomaterial applications. Both S. aureus and E. coli were used to assess bacterial attachment on the coating surfaces. The bacterial attachment on the coating and bare glass, as well as bacterial morphology after incubation with the prepared coatings for $6\\mathrm{~h~}$ were observed by SEM (Figure 6). It could be seen that a large number of bacteria adhered on the PPQA coating and bare glass surface. Bacterial attachment on the blending coating surfaces decreased gradually with the increased amount of P(HEAA-co-GMA). Few bacteria were observed on the PHG coating surface, suggesting superior bacteria-repellent ability. Hydrogen-bonding interactions with hydroxyl and amide groups make the PHG coating surface form a hydrated layer to resist bacterial adhesion. On the other hand, drastic morphologic evolvements were witnessed either in S. aureus or E. coli, in which the bacteria membranes became wrinkled after incubation with PPQA coating, whereas the control of both S. aureus and E. coli on bare glass displayed a structurally intact cell wall. This could be attributed to the strong antibacterial activity of cationic QAC groups which could disrupt the membrane of bacteria by initial contact through an electrostatic effect and passive diffusion of the polymer chains (the alkyl chains) through the cell wall.  \n\nFurthermore, bacterial viability was detected on a fluorescence microscope after staining. Green fluorescent dye (STYO 9) generally labels all bacteria, whereas red fluorescent dye (PI) penetrates only bacteria with damaged membranes. As shown in Figure 7, numerous dead cells were seen both on the PPQA and $\\mathrm{PPQA}_{2}/\\mathrm{PHG}_{1}$ surfaces after incubation for $6\\mathrm{{h}}$ This phenomenon confirms again that the cationic POSSP(QAC-co-AEMA) copolymer plays a vital role for antibacterial activities. Because of the hydrophilicity of P(HEAA$c o$ -GMA), the amount of bacteria attached on $\\mathrm{PPQA_{1}/P H G_{2}}$ and PHG surfaces significantly decreased, demonstrating their excellent bacteria-repellent property. The tendency agreed well with that observed in SEM images. $\\mathrm{PPQA_{1}/P H G_{1}}$ coating showed an effective bacteria-repelling performance, and maintained bacterial growth inhibition rates of 99.9 and $67.2\\%$ against S. aureus and E. coli, respectively, being considered as the optimum in this work. It could be concluded from the above antibacterial and bacterial adhesion results that it was meaningful to balance the ratio of bactericidal POSSP(QAC-co-AEMA) and anti-adhesive P(HEAA-co-GMA) for achieving the best comprehensive antibacterial performance.  \n\n![](images/ef3d257d13c511d0c32a4076d19a6559efd56986aa2f3fb6b19507c4fefe5cec.jpg)  \nFigure 6. SEM images of S. aureus (A) and E. coli (B) adhering to the prepared coatings after incubation for $^{6\\mathrm{~h~}}$ .  \n\n![](images/efd9a639ce8194823cb4811563f109fc028e46d5bafb612c305f1c5688f69c1e.jpg)  \nFigure 7. Fluorescent images of S. aureus (A) and $E$ . coli (B) on the prepared coating surfaces after incubation for $\\epsilon\\mathrm{h}$ . Red indicates dead bacteria, and green refers to live bacteria.  \n\nHemolytic Analysis. One of the challenges of cationic antibacterial materials is hemolytic activity. In this work, hemolytic rates of the resultant coatings were measured, and the results are shown in Figure 8. Pure water and PBS buffer were chosen as the positive and negative controls, respectively. After incubating with RBCs for $^{2\\mathrm{h}}$ , cationic PPQA coating had a hemolytic rate of $13.25\\pm0.40\\%$ , whereas for PHG coating, almost no hemolysis was observed $\\left(-0.06~\\pm~0.50\\%\\right)$ , suggesting compatibility with RBCs. It could be seen that the hemolysis rates of $\\mathrm{PPQA_{2}/P H G_{1}},$ $\\mathrm{PPQA_{1}/P H G_{1}},$ and $\\mathrm{PPQA_{1}/P H G_{2}}$ were $0.33\\pm\\:0.28$ , $0.86\\pm\\:0.03$ , and $3.89\\pm$ $0.01\\%$ , respectively, and all of them were less than $5\\%$ , meeting the clinical application requirement.64 After blending with P(HEAA-co-GMA), the hemolysis of the coatings reduced obviously as compared with that in the PPQA coating, which was because hydroxyl groups could interact with RBC surfaces by weak hydrogen-bonding, and thus protect RBCs from being destroyed,65 which was consistent with the previous work.66,67 The cytotoxicity of the coatings was also tested (Figure S7), though the cytotoxicity was not low.  \n\n![](images/2c8f292bd213b48d5cc3f9412250adb38d7d82d541d1f262a654154976cc8dcc.jpg)  \nFigure 8. Hemolysis of the prepared blending coatings showing low values in comparison to the homopolymer PPQA coatings. All data were obtained from at least three samples and shown as the mean $\\pm$ standard deviation.  \n\nThe prepared PPQA/PHG blending coatings had antifogging and antibacterial properties simultaneously. As illustrated in Figure 9, both the cationic polyelectrolyte of QAC and two hydrogen-bond donor-containing HEAA in copolymers are responsible for rapidly absorbing water molecules from the environment and diffusing them into the bulk of the coatings via hydrogen-bonding interactions, that can greatly reduce light reflection or refraction and endow the surfaces with antifogging performance. The antibacterial properties of the blending coatings are triggered by the bacteria-killing and bacteriarepelling balance that was provided by positively charged POSS-P(QAC-co-AEMA) and hydrophilic P(HEAA-co-GMA), respectively. The coexistence of hydroxyl and amide groups rendered HEAA as a strong hydratable, which prevented the initial attachment of bacteria onto the device surfaces. Meanwhile, QAC was employed to kill the residual adhered bacteria through immobilizing the negative bacterial cell envelopes via electrostatic interaction and disrupting the membrane structure by alkyl chains. The dual functionality of the blending coatings suggests the excellent potential of this type of functionalization for medical devices.  \n\n![](images/8f72cf162eba325932e4f0d511ca6f032e0cda9f1c7dd28003a76cb362d317b7.jpg)  \nFigure 9. Illustration of antifogging and antibacterial performances of the PPQA/PHG blending coatings. Both cationic and hydroxylcontaining copolymers are responsible for the antifogging performance due to water absorption and diffusion, and they also provide bacteria-killing and bacteria-repelling properties.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# CONCLUSIONS  \n\nIn this work, transparent, antifogging and antibacterial blending coatings were successfully prepared by casting the mixed copolymer solution of POSS-P(QAC-co-AEMA) and P(HEAA-co-GMA) in a simple and green approach. The two random copolymers are compatible as demonstrated by high transparency comparable to that of bare glass and nanoscaled roughness of the coating surfaces. Based on the hydrophilic HEAA and QAC, the resultant coatings with various blending ratios could effectively prevent fog formation under hot-vapor and cold-warm conditions. Meanwhile, in vivo antifogging study suggested that the PPQA/PHG blending coatings can remain optically clear under humid oral environments. Furthermore, it was found that the PPQA coating showed remarkable antibacterial property and the increased ratio of POSS-P(QAC-co-AEMA) in blending coatings could improve the bactericidal effect. On the other hand, neat PHG coating showed strong resistance to bacterial attachment. By tuning the bacteria-killing and bacteria-releasing properties among the copolymers of POSS-P(QAC-co-AEMA) and P(HEAA-coGMA), the blending coating with $1/1$ mass ratio simultaneously showed effective bacteria-repelling performance and maintained bacterial growth inhibition rates of 99.9 and $67.2\\%$ against S. aureus and E. coli, respectively, as well as the low hemolytic rate of $0.86\\pm0.03\\%$ . This work provides a facile approach to develop an antifogging/antibacterial polymeric coating, which could be potentially applied in medical devices of endoscopy or other related fields such as food preservation.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 7,
+        "chunk": "# ASSOCIATED CONTENT",
+        "category": " References"
+    },
+    {
+        "id": 8,
+        "chunk": "# $\\bullet$ Supporting Information  \n\nThe Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.9b21871.  \n\nMaterials, synthesis procedures of QAC, POSS-CPADB, POSS-P(QAC-co-AEMA), and P(HEAA-co-GMA), as well as their characterizations by $^{1}\\mathrm{H}$ NMR and GPC; thickness, stability, recycling antibacterial properties, and cytotoxicity of the coatings, and antifogging and antibacterial properties of $\\mathrm{PQA_{1}/P H G_{1}}$ coating (PDF)  \n\nIn vivo antifogging performance of bare glass (AVI) In vivo antifogging performance of the $\\mathrm{PPQA_{1}/P H G_{2}}$ coating (AVI)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# AUTHOR INFORMATION",
+        "category": " References"
+    },
+    {
+        "id": 10,
+        "chunk": "# Corresponding Authors  \n\nXiaohui Li − School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300350, China; $\\circledcirc$ orcid.org/ 0000-0003-3179-6585; Email: lixiaohui@tju.edu.cn Xiaoyan Yuan − School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300350, China; orcid.org/0000-0002-2895-3730; Email: yuanxy@ tju.edu.cn",
+        "category": " Abstract"
+    },
+    {
+        "id": 11,
+        "chunk": "# Authors  \n\nShan Bai − School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300350, China Yunhui Zhao − School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300350, China Lixia Ren − School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300350, China; orcid.org/0000-0001-7659-0025  \n\nComplete contact information is available at: https://pubs.acs.org/10.1021/acsami.9b21871",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# Notes  \n\nThe authors declare no competing financial interest.",
+        "category": " References"
+    },
+    {
+        "id": 13,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nThis work is financially supported by the National Natural Science Foundation of China under grant 51603143 (X.L.) and the Natural Science Foundation of Tianjin, China via grant 18JCQNJC03800 (X.L.) and 17JCZDJC37500 (X.Y.). Prof. Junmei Zhu at Tianjin Institute of Medical and Pharmaceutical Science, China, is appreciated for providing support of the in vivo antifogging test.",
+        "category": " References"
+    },
+    {
+        "id": 14,
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Commun. 2019, 10, 4792.   \n(59) Zhang, Y.; He, X.; Ding, M.; He, W.; Li, J.; Li, J.; Tan, H. Antibacterial and Biocompatible Cross-Linked Waterborne Polyurethanes Containing Gemini Quaternary Ammonium Salts. Biomacromolecules 2018, 19, 279−287.   \n(60) Lin, J.; Chen, X.; Chen, C.; Hu, J.; Zhou, C.; Cai, X.; Wang, W.; Zheng, C.; Zhang, P.; Cheng, J.; Guo, Z.; Liu, H. Durably Antibacterial and Bacterially Antiadhesive Cotton Fabrics Coated by Cationic Fluorinated Polymers. ACS Appl. Mater. Interfaces 2018, 10, 6124−6136.   \n(61) Oliver, S.; Wagh, H.; Liang, Y.; Yang, S.; Boyer, C. Enhancing the Antimicrobial and Antibiofilm Effectiveness of Silver Nanoparticles Prepared by Green Synthesis. J. Mater. Chem. B 2018, 6, 4124−4138. (62) Li, Z.; Zhou, P.; Zhou, F.; Zhao, Y.; Ren, L.; Yuan, X. Antimicrobial Eugenol-Loaded Electrospun Membranes of Poly(epsilon-caprolactone)/Gelatin Incorporated with REDV for Vascular Graft Applications. Colloids Surf., B 2018, 162, 335−344.   \n(63) Voo, Z. X.; Khan, M.; Narayanan, K.; Seah, D.; Hedrick, J. L.; Yang, Y. Y. Antimicrobial/Antifouling Polycarbonate Coatings: Role of Block Copolymer Architecture. Macromolecules 2015, 48, 1055− 1064.   \n(64) Zhang, J.; Zhu, Y.; Song, J.; Yang, J.; Pan, C.; Xu, T.; Zhang, L. Novel Balanced Charged Alginate/PEI Polyelectrolyte Hydrogel that Resists Foreign-Body Reaction. ACS Appl. Mater. Interfaces 2018, 10, 6879−6886.   \n(65) Allison, B. C.; Applegate, B. M.; Youngblood, J. P. Hemocompatibility of Hydrophilic Antimicrobial Copolymers of Alkylated 4-Vinylpyridine. Biomacromolecules 2007, 8, 2995−2999. (66) Yuan, H.; Yu, B.; Fan, L.-H.; Wang, M.; Zhu, Y.; Ding, X.; Xu, F.-J. Multiple Types of Hydroxyl-Rich Cationic Derivatives of PGMA for Broad-Spectrum Antibacterial and Antifouling Coatings. Polym. Chem. 2016, 7, 5709−5718.   \n(67) Huang, Y.; Ding, X.; Qi, Y.; Yu, B.; Xu, F.-J. ReductionResponsive Multifunctional Hyperbranched Polyaminoglycosides with Excellent Antibacterial Activity, Biocompatibility and Gene Transfection Capability. Biomaterials 2016, 106, 134−143.",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Antifogging/Antibacterial Coatings Constructed by N‑Hydroxyethylacrylamide and Quaternary Ammonium-Containing Copolymers  \n\nShan Bai, Xiaohui Li,\\* Yunhui Zhao, Lixia Ren, and Xiaoyan Yuan\\*  \n\nCite This: ACS Appl. Mater. Interfaces 2020, 12, 12305−12316",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# ACCESS  \n\nE Metrics & More  \n\nSupporting Information  \n\n![](images/0493553c694a908e068ee41356a36feb3de88f93a282713a97ecac8e03ae3f32.jpg)  \n园 Article Recommendations  \n\nABSTRACT: Endoscopic surgery has gained widespread applications in various clinical departments, and endoscope surfaces with antifogging and antibacterial properties are essential for elaborate procedures. In this work, novel antifogging/antibacterial coatings were developed from a cationic copolymer and a hydrophilic copolymer, polyhedral oligomeric silsesquioxane-poly(quaternary ammonium compound-co-2-aminoethyl methacrylate hydrochloride) [POSS-P(QAC-co-AEMA)] and poly( $\\dot{N}$ -hydroxyethylacrylamide-co-glycidyl methacrylate) [P(HEAA-co-GMA)] via a facile and green blending method. Such transparent coatings showed excellent antifogging performance under both in vitro and in vivo fogging conditions, mainly attributed to the high water-absorbing capability of HEAA and QAC. Antibacterial assays proved that the blending coatings had a superior antibacterial property, which could be improved with the proportion of POSS-P(QAC-co-AEMA) because of the bactericidal efficiency of cationic QAC. Meanwhile, owing to the high hydratability of HEAA, the blending coatings exhibited a bacteria-repelling property. By simply tuning the blending ratio of POSS-P(QAC-co-AEMA) and P(HEAA-co-GMA), the comprehensive bacteria-killing and bacteria-repelling properties of the coatings were achieved. Moreover, after incubating with red blood cells, the prepared blending coatings presented a lower hemolytic rate of less than $5\\%$ . The findings provided a potential means for addressing the challenge of fogging and bacterial contamination occurring in endoscopic lenses and other medical devices.  \n\nKEYWORDS: antifogging coatings, antibacterial properties, quaternary ammonium compounds, N-hydroxyethylacrylamide, enhanced hydration",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# INTRODUCTION  \n\nOver the past decade, endoscopic surgery has been widely accepted as a minimally invasive approach and applied in various clinical departments because it has a precise small-cut and rapid recovery characteristics as compared with open surgery.1 During a safe and successful endoscopic procedure such as laparoscopy and colonoscopy, maintaining a clear vision is paramount, which can improve precision, reduce operative time, and even prevent inadvertent injury. Meanwhile, microbial colonization and biofilm formation on the surfaces of endoscopes is another impediment for a safe surgery.3−5  \n\nThe main reason of optical loss is endoscopic lens fogging, which is caused by the discrepancies in temperature and humidity between ambient conditions and in vivo.2 Most antifogging approaches for medical devices are based on traditional methods, for instance, spraying antifogging reagents or employing heating apparatus, but they show disadvantages of short residual action, cumbersome procedure, high medical expenses, and so on.6,7 Currently, developing coating surfaces with enhanced antifogging performance has been gaining much attention to solve the atomization problem.8−19 In addition to superhydrophilic and superhydrophobic strategies, applying a water-absorbing coating with amphiphilicity to a surface is an effective antifogging approach, where the condensed water molecules or the moist vapor can be rapidly imbibed into the bulk of the coating, followed by uniform diffusion of the absorbed water molecules to prevent the formation of a large and light-scattering water domain.8−14,20−23  \n\n![](images/2a589968b9c8b9df439b1cc8f24b8174302535415c5057a86729ebb84f7dbf98.jpg)  \nFigure 1. (A) Synthesis of POSS-P(QAC-co-AEMA) and P(HEAA-co-GMA) copolymers. (B) Schematic preparation of the blending coatings.  \n\nAs invasive medical devices, endoscopes are prone to be heavily contaminated and associated with the healthcareassociated infections. On one hand, it is inevitable for endoscopes to be contaminated by environmental bacteria during storage, and the endoscopic environments provide favorable conditions for bacterial proliferation and subsequent biofilm formation.24,25 In addition, clinically used endoscopes comprise a high bioburden of microbes that originate from patients, and it is difficult to clean and disinfect the used devices due to their complex and delicate structure.26 Therefore, a dual-functional antifogging/antibacterial surface is in high demand in the field of endoscopy to prevent fogging and bacterial contamination.  \n\nIn recent years, comprehensive antibacterial coatings have been broadly developed to solve the problems of microbial infections in medical device surfaces.27−33 Nevertheless, only a few studies have focused on the development of antifogging and antibacterial surfaces so far.16,34−37 For instance, robust poly(vinyl alcohol)/poly(acrylic acid)/silver composite films with antifogging and antibacterial properties were prepared, where the abundant hydroxyl groups in the polymers could prevent fog formation and distributed silver nanoparticles endowed the composite films with bactericidal activity.34 Zhang et al. fabricated a multifunctional coating for antifogging, self-cleaning, and antimicrobial properties on the basis of zwitterionic peptides. The superhydrophilicity of zwitterionic material could strongly bind to water molecules and thus impart the coating with excellent antifogging performance and resistance to bacterial adhesion.16 However, the antibacterial properties of these prepared antifogging/ antibacterial surfaces were achieved by either an active-attack bacteria-killing or a passive-defense bacteria-repelling mechanism. Despite their general effectiveness, both the surfaces have inherent limitations for practical applications. Bacteria would grow rapidly and form a stubborn biofilm once attached onto the passive-defense surfaces, whereas for the active-attack bacteria-killing surfaces, continuous contamination of dead bacteria and debris is the fatal weakness, which causes the bactericidal groups to be shielded and thus greatly reduces the killing efficiency.38,39  \n\nQuaternary ammonium compounds (QACs) display broadspectrum bactericidal activity by destructive interaction with the cell membrane and subsequent enzyme inactivation, and fhoaovde ibnedeunstarpyp, iwedasitnewmataenrytreladtsmseunct,hansdbisomoend.i4c0a−l43maAtemrioanlsg, them, (meth)acrylic derivatives-related QACs are generally employed as antibacterial materials. A series of alkyl bromides with different alkyl chain lengths were used to quaternize poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA), and the results suggested that PDMAEMA quaternized with 1-bromobutane (PDMAEMA-C4) exhibited balanced membrane-disrupting activity and biocompatibility.44,45 Owing to two hydrogen-bond donors of amide groups and hydroxyl groups in $N.$ -(2-hydroxyethyl)acrylamide (HEAA), (polyHEAA)-based materials exhibit strong resistance to bacterial attachment, protein nonspecific adsorption, and cell adhesion.46−49 The hydration ability of a copolymer can be enhanced by incorporation of HEAA. Additionally, it was reported that hydroxyl groups are instrumental in improving the hemocompatibility of cationic polymers.50  \n\nIn this study, the dual-functional antifogging/antibacterial coatings that combine bacteria-killing and bacteria-repelling abilities were developed by blending polyhedral oligomeric silsesquioxane-poly(N-(2-(methacryloyloxy)ethyl)-N,N-dimethylbutan ammonium bromide-co-2-aminoethyl methacrylate hydrochloride) [POSS-P(QAC-co-AEMA)] and poly(N-hydroxyethyl acrylamide-co-glycidyl methacrylate) [P(HEAA-coGMA)]. Incorporation of AEMA and GMA was performed to crosslink the two random copolymers, and a small quantity of 1,3,5-triformylbenzene (TFB) was added as a co-crosslinker to further react with the amino and hydroxyl groups in the copolymers as well as amino-modified glass substrates, forming a chemically crosslinked stable system. Hydrophobic POSS was introduced to facilitate coating stability and mechanical properties.11,51,52 The antifogging and antibacterial properties of the blending coatings with different blending ratios were evaluated by hot-vapor and cold-warm antifogging tests, standard plate count method, bacterial antiadhesive assays, and growth inhibition to acquire the optimized blending ratios.  \n\nTable 1. Compositions and Number-Average Molecular Weights of the Synthesized Copolymers   \n\n\n<html><body><table><tr><td rowspan=\"2\"></td><td colspan=\"2\">feeding ratio (mol/mol)</td><td colspan=\"2\">actual ratioa (mol/mol)</td><td colspan=\"2\">molar compositionb (mol/mol)</td><td rowspan=\"2\">Mnc (x104)</td><td rowspan=\"2\">Dc</td></tr><tr><td>copolymer QAC/AEMA</td><td>HEAA/GMA</td><td>QAC/AEMA</td><td>HEAA/GMA</td><td>QAC/AEMA</td><td>HEAA/GMA</td></tr><tr><td>POSS-P(QAC-co-AEMA)</td><td>200:50</td><td></td><td>3.03:1</td><td></td><td>342:113</td><td></td><td>12.0</td><td>1.32</td></tr><tr><td>P(HEAA-co-GMA)</td><td></td><td>300:20</td><td></td><td>14.28:1</td><td></td><td>795:55.7</td><td>9.94</td><td>1.24</td></tr></table></body></html>\n\naDetermined by $^1\\mathrm{H}$ NMR spectra. bCalculated by the GPC results and actual molar ratios. cObtained from GPC using poly(ethylene glycol) as the standard.  \n\nTable 2. Compositions for Preparation of the Antifogging/Antibacterial Coatings   \n\n\n<html><body><table><tr><td>coating</td><td>POSS-P(QAC-co-AEMA) (mg)</td><td>P(HEAA-co-GMA) (mg)</td><td> TFB (mg)</td><td> POSS-P(QAC-co-AEMA)/P(HEAA-co-GMA) mass ratio (mg/mg)</td></tr><tr><td>PPQAa</td><td>18</td><td>0</td><td>0.54</td><td>1:0</td></tr><tr><td>PPQA/PHGb</td><td>12</td><td>6</td><td>0.54</td><td>1:0.5</td></tr><tr><td>PPQA/PHGb</td><td>9</td><td>9</td><td>0.54</td><td>1:1</td></tr><tr><td>PPQA/PHGb</td><td>6</td><td>12</td><td>0.54</td><td>1:2</td></tr><tr><td>PHGa</td><td>0</td><td>18</td><td>0.54</td><td>0:1</td></tr></table></body></html>\n\naOne-component coatings were prepared from POSS-P(QAC-co-AEMA) or P(HEAA-co-GMA) only. bBlending coatings were prepared from POSS-P(QAC-co-AEMA) and P(HEAA-co-GMA) with different mass ratios.  \n\nAdditionally, antifogging is considered as the principal intention in vivo.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# EXPERIMENTAL SECTION  \n\nSynthesis of POSS-P(QAC-co-AEMA) and P(HEAA-co-GMA) Copolymers. As shown in Figure 1A, the QAC and $N_{\\sun}$ - hydroxyethylacrylamide (HEAA)-containing copolymers, that is, POSS-P(QAC- $c o$ -AEMA) and P(HEAA- $_{c o}$ -GMA), for the blending coating preparation were synthesized via reversible addition− fragmentation chain transfer (RAFT) polymerization and free radical polymerization, respectively. QAC was prepared by quaternization of 2-(dimethylamino)ethyl methacrylate (DMAEMA) with 1-bromobutane. The hydrophobic component was incorporated by modifying the RAFT agent of CPADB with aminopropylisobutyl polyhedral oligomeric silsesquioxane $\\left(\\mathrm{POSS-NH}_{2}\\right)$ ) to obtain POSS-CPADB.53 Compositions and molecular weights of POSS-P(QAC-co-AEMA) and P(HEAA-co-GMA) copolymers are given in Table 1. It is worth mentioning that the copolymer compositions obtained by combining gel permeation chromatography (GPC) results with actual molar ratios were higher than their feeding, probably due to the copolymer aggregating in the eluent when determining molecular weight by GPC. Detailed synthesis procedures and the characterizations of their chemical structure by proton nuclear magnetic resonance $\\mathrm{\\Omega^{\\prime1}H\\ N M R})$ spectroscopy and GPC are described in the Supporting Information and Figure S1.  \n\nPreparation of the Blending Coatings. The preparation process of the blending coatings is schematically illustrated in Figure 1B. Bare glass was first treated with oxygen plasma (18 W, $^{60\\mathrm{~s},}$ Harrick Plasma PDC-32G-2, USA) to produce abundant hydroxyl groups, followed by immersing into (3-aminopropyl)- trimethoxysilane/methanol solution $(5\\%,{\\bf v}/{\\bf v})$ for $^{4\\mathrm{~h~}}$ and sonicating with methanol and ethanol in sequence to provide amino-functionalized surfaces. The successful surface modifications were demonstrated by the change of the water contact angle (WCA) for each surface as also presented in Figure 1B. Then, copolymers with various POSS-P(QAC-co-AEMA)/P(HEAA-co-GMA) blending mass ratios and a certain amount of TFB (Table 2) were dissolved in $200~\\mu\\mathrm{L}$ of ethanol (P(HEAA-co-GMA) stored in aqueous solution with a concentration of $60~\\mathrm{mg/mL}$ ). A determined volume of the mixture was drop-coated onto the modified glass slides to allow the crosslinking of POSS-P(QAC-co-AEMA), P(HEAA-co-GMA), and TFB for antifogging tests. It was also cast onto a cropped square glass in $1\\times1~\\mathrm{cm}^{2}$ for antibacterial and hemolytic analysis. All coated samples were dried at room temperature and subsequently thermalcured at $40~^{\\circ}\\mathrm{C}$ overnight. The resultant coatings with different blending ratios were denoted as PPQA, $\\mathrm{PPQA_{2}/P H G_{1}},$ $\\mathrm{PPQA_{1}/}$ $\\mathrm{PHG}_{\\mathrm{1}},$ $\\mathrm{\\bar{PPQA}_{1}/P H G}_{2},$ and PHG, which showed the thicknesses of  \n\n$9.14\\pm0.39\\$ , $7.34\\pm0.36,$ $7.57\\pm0.59.$ , $7.13\\pm0.22,$ and $6.74\\pm0.17$ $\\mu\\mathrm{m},$ respectively (Figure S2). Overall, a green blending strategy, where water and ethanol were employed as solvents, was developed to prepare the dual-functional coatings with desired antifogging and antibacterial properties.54  \n\nCharacterizations of the Blending Coatings. The mean WCA, droplet diameter $(D)_{\\cdot}$ , and their evolution within $400\\mathrm{~s~}$ were recorded on a contact angle meter (Shanghai Zhongchen Instrument JC2000D, China) at room temperature. Each coating was analyzed at least three times. Variation of the wetted surface area (S) for various coatings was further calculated by the following equation  \n\n$$\n\\Delta S/S_{0}=\\frac{S_{(t)}-S_{0}}{S_{0}}=\\frac{\\pi{D_{(t)}}^{2}/4-S_{0}}{S_{0}}\n$$  \n\nwhere $D_{(t)}$ and $S_{(t)}$ are defined as the droplet diameter and wetted surface area at a given time, respectively. $S_{0}$ is the original wetted surface area. Attenuated total reflectance−Fourier transform infrared spectroscopy (ATR−FTIR) (TENSO 27 spectrometer, Germany) was employed to confirm the chemical structure of the blending coatings. To test transparency and quantitively determine the antifogging properties of the coatings, visible light transmittance values of the double-coated surfaces were collected on a $722\\ s$ visible spectrophotometer (Shanghai Jinghua Technology Instruments, China) in the wavelength range of $400{-}800\\ \\mathrm{nm}$ before and after the samples were placed at $-20\\ ^{\\circ}\\mathrm{C}$ for $30~\\mathrm{\\min}$ . The surface morphology and root-mean-square roughness $(R_{\\mathrm{q}})$ values of the prepared coatings were observed by atomic force microscopy (AFM) (Benyuan Nano-Instruments CSPM5500A, China).  \n\nAntifogging Tests. Glass substrates were coated with a copolymer coating on both sides. To perform the antifogging tests in vitro, the samples were held ${\\mathfrak{s}}\\mathrm{cm}$ above hot water $(80~^{\\circ}\\dot{\\mathrm{C}})$ for $10~\\mathsf{s}$ and in a refrigerator $(-20\\ ^{\\circ}\\mathrm{C})$ for $30~\\mathrm{min}$ with the purpose of hotvapor and cold-warm antifogging tests, respectively, followed by moving the samples to ambient conditions and taking photographs immediately.  \n\nTo further assess the antifogging performance in vivo, a rabbit oral cavity with a digital endoscope (Hangzhou Jingjiying Hardware Store, China) was used as the animal model. All procedures involving animals comply with the Tianjin Experimental Animal Management Ordinance, China. The circular coating sample with a diameter of 4.9 mm was first prepared and fixed between the endoscope lens and its protective sleeve. Then, the structural component of the digital endoscope was placed into the rabbit’s oral cavity and maintained for a certain time. The process was recorded from endoscope insertion onward.  \n\nAntibacterial Tests. Minimum inhibitory concentrations (MIC) of the synthesized copolymers were first determined. Typically, 4096 $\\mu\\mathrm{g}$ of the copolymer was first dissolved in $2~\\mathrm{mL}$ of sterile phosphate buffered saline (PBS) and then diluted with the serial two-fold method to obtain a series of copolymer solutions with varying concentrations. The copolymer solution $(100~\\mu\\mathrm{L})$ with a certain concentration and $100\\mu\\mathrm{L}$ of bacterial suspension $(3\\times10^{5}\\mathrm{CFU/mL})$ ) were added into each well. The bacterial suspension with equal volume of sterile PBS was set as the positive control and $100~\\mu\\mathrm{L}$ of pure Mueller−Hinton broth (MHB) diluted with $100~\\mu\\mathrm{L}$ of sterile PBS buffer was used as the negative control. After incubating the plate at $37^{\\circ}\\mathrm{C}$ at the speed of $80\\ \\mathrm{rpm}$ for $^{24\\mathrm{h},}$ the optical density (OD) at $600\\mathrm{nm}$ of the microorganism solutions was recorded. The MIC value was defined as the lowest concentration of copolymer, where no visual growth of bacteria was found. The bacterial growth inhibition rate was determined according to eq 2  \n\n![](images/f43b3616543656bbae3d014b22d4e77ff762ad396d10c1399d25f95aad694aaa.jpg)  \nFigure 2. (A) ATR−FTIR spectra of the prepared copolymer coatings. (B) Transmittance curves of the double-coated samples and bare glass in the wavelength range of $400{-}800~\\mathrm{nm}$ . (C) AFM topographic images and root-mean-square $(R_{\\mathrm{q}})$ roughness of the coatings over a scope of $4\\times4$ $\\mu\\mathrm{m}^{2}$ with the tapping mode.  \n\n$$\n=\\frac{O D_{\\mathrm{positive\\control}}-O D_{\\mathrm{sample}}}{O D_{\\mathrm{positive\\control}}-O D_{\\mathrm{negative\\control}}}\\times100\n$$  \n\nFor the coating samples, the antibacterial activities were estimated by the standard plate count method. The test coatings sterilized in ultraviolet before the test were placed into a 24-well plate, followed by adding the bacterial suspension $(200~\\mu\\mathrm{L},~3~\\times~10^{\\bar{4}}~\\mathrm{CFU/mL})$ and MHB $(600\\mu\\mathrm{L})$ . After culturing for $^{24\\mathrm{h},}$ , the bacterial suspension was diluted with an appropriate factor and $10\\mu\\mathrm{L}$ of the diluted suspension was spread on nutrient agar. A sample of bare glass was the positive control. The bacterial colonies were photographed, and the colony numbers $(N)$ were counted after overnight incubation. The bacterial growth inhibition rate was calculated from eq 3  \n\n$$\n(\\%)=\\frac{N_{\\mathrm{positive\\control}}-N_{\\mathrm{sample}}}{N_{\\mathrm{positive\\control}}}\\times100\n$$  \n\nScanning electron microscopy (SEM, Hitachi SU1510, Japan) was employed to evaluate the bacterial morphology and adhesion. Typically, $500~\\mu\\mathrm{L}$ of bacterial suspension $\\left({3\\times10^{5}\\mathrm{CFU/mL}}\\right)$ was dropped on each sterile coating in a 24-well plate, separately. After culturing for $^{4\\mathrm{h}}$ at $37^{\\circ}\\mathrm{C},$ the coatings were gently rinsed with sterile PBS thrice to take out the loosely attached bacteria. Then, the bacteria that attached on coating surfaces were fixed with $2.5\\%$ glutaraldehyde solution at $4^{\\circ}\\mathrm{C}$ for $^{2\\mathrm{h},}$ followed by rinsing with sterile PBS buffer. Dehydration was performed with a series of ethanol aqueous solutions (25, 50, 75, 95, and $100\\%$ ).  \n\nThe live/dead assay was performed to reveal the bacterial viability and population after contacting with the copolymer coatings. Oneside coated samples in $1\\times1~\\mathrm{cm}^{2}$ area were first individually put into a 24-well plate, then $500\\mu\\mathrm{L}$ of bacterial suspension $\\left(3\\times10^{6}\\mathrm{CFU/mL}\\right)$ and $500\\mu\\mathrm{L}$ of MHB were added into each well. After culturing for $6\\mathrm{{h}}$ at $37\\ ^{\\circ}\\mathrm{C},$ the coatings were rinsed thrice with sterile pure water and stained with $200\\mu\\mathrm{L}$ of propidium iodide (PI)/SYTO 9 mixture for 15 min in the dark. Subsequently, the samples were washed with sterile water again for discarding the residual dye solution, and the stained samples were mounted between a slide and a coverslip and observed under a fluorescence microscope (Nikon Eclipse Ti-S, Japan).  \n\nHemolytic Test. The hemolytic assay was performed as described in refs 16 and 55. In brief, fresh sheep blood was diluted with PBS buffer $\\mathrm{(pH~7.4)}$ and then centrifuged at $2000~\\mathrm{rpm}$ for $10\\ \\mathrm{\\min},$ followed by discarding the supernatants and repeating the above step twice. The washed red blood cell (RBCs) was diluted with PBS in a ratio of 1:9. Then, $500~\\mu\\mathrm{L}$ of $10\\%$ RBC suspension was placed on each prepared $1\\times1~\\mathrm{cm}^{2}$ coating in a 24-well plate, and subsequently $500~\\mu\\mathrm{L}$ of PBS buffer was also added into each well. After incubating at $37^{\\circ}\\mathrm{C}$ for $^{2\\mathrm{h},}$ the whole blood solutions were centrifuged at 2000 rpm for $10\\ \\mathrm{min}$ . Then, aliquots $\\left(100~\\mu\\mathrm{L}\\right)$ of the supernatants were transferred into a 96-well plate, and the OD values at $541~\\mathrm{nm}$ were measured. The untreated blood suspension and blood diluted with water were used as the negative and positive controls, respectively. The hemolysis was calculated by the following eq 4  \n\n$$\n\\mathrm{Hemolysis\\:(\\%)}=\\frac{O D_{\\mathrm{sample}}-O D_{\\mathrm{negative\\:control}}}{O D_{\\mathrm{positive\\:control}}-O D_{\\mathrm{negative\\:control}}}\\times100\\\n$$  \n\n![](images/c00c0ed36b95673bb20d2a92260ab94fa9b8216a8ab08d24a4b02cc834d2be8b.jpg)  \nFigure 3. In vitro antifogging study. (A) Antifogging performances of the prepared coatings with both hot-vapor and cold-warm method. (B) Transmittance of the coatings and bare glass during the cold-warm antifogging test. (C) Evolution of WCA and wetted surface area (S) of the coating samples within $400\\mathrm{~s~}$ . Wetted surface area variation is expressed as $\\Delta S/S_{0},$ where $\\Delta S=S_{(t)}-S_{0},S_{(t)}$ and $S_{0}$ are the wetted surface areas at a given time and initial moment, respectively.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# RESULTS AND DISCUSSION  \n\nThe dual-functional antifogging/antibacterial coatings with various POSS-P(QAC-co-AEMA)/P(HEAA- $_c o$ -GMA) ratios were successfully prepared. According to the blending ratios, the resultant coatings were denoted as $\\mathrm{PPQA}_{2}/\\mathrm{PHG}_{1},$ $\\mathrm{PPQA_{1}/}$ $\\mathrm{PHG}_{1},$ and $\\mathrm{PPQA_{1}/P H G_{2}},$ respectively. As control, two onecomponent coatings were also prepared from POSS-P(QACco-AEMA) and P(HEAA-co-GMA), which were expressed as PPQA and PHG, respectively. Antifogging, bacteria-killing, and bacteria-repelling properties of the blending coatings were systematically evaluated to investigate the relationships between polymer compositions and the coatings’ performance.  \n\nCharacterizations of the Antifogging/Antibacterial Coatings. The structure of the prepared blending coatings was confirmed by ATR−FTIR spectra as shown in Figure 2A. The characteristic peak at $1723~\\mathrm{{\\bar{c}m}^{-1}}$ was attributed to $\\scriptstyle{\\mathrm{C}}={\\mathrm{O}}$ stretching vibration of the ester group, and the absorption peak at $1552~\\mathrm{{cm}^{-1}}$ was corresponding to $\\mathrm{\\DeltaN-H}$ bending vibration of the amide group in HEAA.56 With the adding of P(HEAA-coGMA), the intensity of the peak at $1552~\\mathrm{{cm}^{-1}}$ strengthens gradually, whereas the peak of $1723~\\mathrm{{cm}^{-1}}$ becomes weaker. Moreover, the absorption peak at $3270~\\mathrm{{cm}^{-1}}$ belonged to the $\\mathrm{\\DeltaN-H}$ and $_\\mathrm{O-H}$ stretching vibrations, that were present in all prepared coatings except for the POSS-P(QAC-co-AEMA) coated surface.57 All of the above results indicate that the PPQA/PHG blending coatings have been successfully prepared. One of the basic requirements for antifogging coating is the transparency of the coating itself. Visible light transmittance of the blending coatings as well as bare glass were collected (Figure 2B). The prepared PPQA/PHG blending coatings exhibited highly visible light transmittance of $85.0\\mathrm{-}90.0\\%$ approximately, comparable to that of bare glass $\\left(86.8-91.2\\%\\right)$ , indicating good compatibility of POSS-P(QAC-co-AEMA) and P(HEAA-co-GMA). Whereas for the PPQA and PHG coatings, the visible light transmittance values in the wavelength range of $400{-}800~\\mathrm{nm}$ were $79.6\\mathrm{-}84.6$ and $76.9\\mathrm{-}80.8\\%$ , respectively, which are lower than those of bare glass and the prepared PPQA/PHG blending coatings, this was probably due to the higher crosslinking density present in onecomponent PPQA and PHG coatings, decreasing the smoothness of the coating surfaces.  \n\nThe surface morphology of the copolymer coatings was further explored by AFM. It could be obtained from Figure 2C that the root-mean-square roughness $R_{\\mathrm{q}}$ values of PPQA, $\\mathrm{PPQA}_{2}/\\mathrm{PHG}_{1},$ $\\mathrm{PPQA_{1}/P H G_{1}},$ $\\mathrm{PPQA_{1}/P H G_{2}}$ and PHG coatings were 13.9, 0.7, 0.9, 0.8, and $22.3\\ \\mathrm{nm},$ respectively. The nanoscaled roughness indicated that smooth surfaces were formed, which can facilitate optical transparency.21 Meanwhile, the decreased $R_{\\mathrm{q}}$ values of the PPQA/PHG blending coatings indicate smoother surface topography, suggesting that the two copolymers exhibited good compatibility and no phase separation appeared during the blending process. The higher roughness of the PPQA and PHG coating surfaces could be attributed to strong interactions between the copolymer itself.  \n\nAntifogging Performance. Antifogging performance of the blending coatings was evaluated by both qualitative and quantitative measurements.8−11,16−18 First, optical images were photographed during both hot-vapor and cold-warm antifogging tests as showed in Figure 3A. The bare glass fogged up immediately either placing them over boiling water or after storing in a refrigerator for $30\\mathrm{min}$ , whereas the coated surfaces maintained visible clearness under hot-vapor antifogging measurement, demonstrating a remarkable antifogging behavior. It could be seen that all coatings kept free of fog and the green plants can be seen obviously after storing at $-20\\ ^{\\circ}\\mathrm{C},$ except for the PPQA and PHG coatings, indicating that the foggy environments were harsher with cold-warm method compared with hot-vapor method. The three blending coatings, $\\mathrm{PPQA}_{2}/\\mathrm{PHG}_{1},$ $\\mathrm{PPQA_{1}/P H G_{1}},$ and $\\mathrm{PPQA_{1}/P H G_{2}},$ qualitatively showed raised transmittance in comparison with the bare glass substrate when exposed to foggy conditions, indicating their excellent antifogging performance. It was mainly attributed to quaternary ammonium, hydroxyl, and amide groups in POSS-P(QAC-co-AEMA) and P(HEAA-coGMA), which can absorb water molecules from the environment and diffuse to prevent a large water domain formation, thus avoiding or reducing light scattering and refraction.  \n\n![](images/b6cc9fe089f4484e8fc635225a8b5b7b12293456882402af7c320e712b9ac385.jpg)  \nFigure 4. In vivo antifogging study. (A) Schematic illustration of the in vivo antifogging test using a rabbit oral cavity model, showing photographs of the real digital endoscope and the preparation of the test sample. The circular coating samples ( $\\dot{d}=4.9\\ \\mathrm{mm}$ ) were fitted between the lens and an elastic protective sleeve. (B) Digital photographs of the rabbit’s maxilla taken from the video at different time points.  \n\nSecond, the antifogging properties of the blending coatings were further quantitatively characterized on a visible spectrophotometer, where visible light transmittances of each double-coated surface were collected when exposed to ambient conditions after keeping at $-20~^{\\circ}\\mathrm{C}$ for $30~\\mathrm{min}$ . As shown in Figure 3B, the visible light transmittance of $\\mathrm{PPQA}_{2}/\\mathrm{PHG}_{1},$ $\\mathrm{PPQA_{1}/P H G_{1}},$ and $\\mathrm{PPQA_{1}/P H G_{2}}$ coatings maintained at $84-$ $90\\%$ and almost the same as those of the coated surfaces before freezing. These results indicated that antifogging properties of the prepared PPQA/PHG blending coatings were almost unaffected by the blending ratios. In contrast, bare glass only has a light transmittance of $28-36\\%$ because of strong light scattering phenomenon. During the cold-warm antifogging test, it could be seen that the light transmittance of PPQA and PHG coatings were $^{67-78}$ and $52\\mathrm{-}67\\%$ , respectively, which was consistent with the above results of optical images. The discounted antifogging behavior was probably due to their higher crosslinking density in comparison with the other three coatings that blended POSS-P(QAC-co-AEMA) with P(HEAA-co-GMA). Furthermore, the antifogging performance of $\\mathrm{PPQA_{1}/P H G_{1}}$ and POSS-free $\\mathrm{PQA_{1}/P H G_{1}}$ coatings was compared, and the result suggested that POSS had little effect on antifogging ability of the blending coatings prepared in this work (Figure S3), but it was demonstrated that the introduction of POSS was beneficial to the coating stability (Figure S4).  \n\nIt is widely accepted that surface wettability plays a significant role in antifogging performance. To investigate the origin and difference in antifogging capability of the prepared copolymer coatings, time-dependent WCA measurements over a 400 s period were performed and the results are shown in Figure 3C. Evidently, all coating surfaces had an initial WCA value about $110^{\\circ}$ and then gradually dropped until stable, which was in contrast to that of bare glass (tiny change with time due to water evaporation). It was considered that the prepared coatings belonged to the typical water-absorbed coatings that show the WCA in the range of 40−110°.14 Reasonably, the antifogging properties of the prepared coatings were attributed to the strong water absorption capability, and subsequently spread it into a hydrated film via hydrogen bonds. Compared with the one-component coatings of PPQA and PHG, the blending $\\mathrm{PPQA}_{2}/\\mathrm{PHG}_{1},$ $\\mathrm{PPQA_{1}/P H G_{1}},$ and $\\mathrm{PPQA_{1}/P H G_{2}}$ coatings displayed a relative rapid decrease of WCA to $57.7\\pm0.9$ , $53.8\\pm0.4_{;}$ , and $63.6\\pm1.4^{\\circ}$ within $400\\ \\mathrm{s},$ respectively, more quickly than both PPQA and PHG coatings (stable WCA values were $82.2~\\pm~3.1$ and $74.5~\\pm~4.0^{\\mathrm{\\bar{o}}}.$ , respectively), resulting in an enhancement of the antifogging performance. It was assumed that the rapid decrease of WCA was probably due to the formation of moderate crosslinking density in the PPQA/PHG blending coatings, which was more conducive to the water absorption process. Further comparison of the wettability of the PPQA/PHG coating exhibited that the $\\mathrm{PPQA_{1}/P H G_{1}}$ coating surface was the most hydrophilic. As mentioned above, PHG coating was highly crosslinked owing to many more crosslinking sites of hydroxyl groups, thus its water-absorbing capability was restricted to some extent, resulting in unsatisfactory antifogging performance. On the other hand, the coating would become more hydrophobic with increased content of POSS-containing copolymer POSSP(QAC-co-AEMA). In consequence, no matter whose content is higher, it is not helpful to absorb water molecules for coated surfaces. In order to study the wetting properties more indepth, Figure 3C showed the wetted surface area evolution $(\\bar{\\Delta S}/S_{0})$ over $400\\mathrm{~s~}$ time interval for the coated samples as well as bare glass. The wetted surface area of bare glass remained nearly unvaried with time, whereas all coated surfaces had an increased trend in wetted surface area, indicating that the water droplets had spread. For PPQA/PHG blending coatings, the values of $\\Delta S/S_{0}$ kept going up to nearly $100\\%$ within $400\\ \\mathrm{s}.$ . However, after an increase of $50\\%$ over the first $^{60\\mathrm{~s,~}}$ the wetted surface areas of PPQA and PHG coatings remained unchanged. These results also demonstrated that the blending coatings had stronger water-absorbing capability than that of one-component coatings.  \n\n![](images/d997da2700c52159add4edc2ac9a95c5ca4d94f915a59c584008fe5e12827d4f.jpg)  \nFigure 5. Antibacterial properties. (A) Growth inhibition rates of POSS-P(QAC-co-AEMA) copolymers in aqueous solutions with a sequence of concentrations against S. aureus and $E$ . coli. (B) Photographs of bacterial colonies of S. aureus and $E_{\\sun}$ coli after incubation with various coatings and bare glass at $37~^{\\circ}\\mathrm{C}$ for $24\\mathrm{~h~}$ . (C) Growth inhibition rates of the prepared coatings calculated by standard plate count methods. All data were obtained from at least three samples.  \n\nAntifogging is considered as the principal intention when emphasized for use in vivo. Therefore, the superior in vivo antifogging effects of the blending coatings were further demonstrated by using a rabbit oral cavity model as shown in Figure 4A. The endoscope images of the whole operating process were recorded. For each, the digital photographs at predetermined moments $(\\sim2,\\sim30,$ and ${\\sim}60~\\mathrm{s}$ ) were captured from the corresponding video and are presented in Figure 4B. Fog formed immediately on the bare glass surface after it was put into the humid oral environment, and visible optical loss occurred after insertion for about $30\\mathrm{~s~}$ due to strong light scattering (Figure 4B and Video S1). It is noteworthy that some visual acuity still remained at $^{2\\ s,}$ indicating that the blurry vision was caused by the endoscope lens fogging, rather than being out of focus. Fortunately, all coated samples remained optically clear and the rabbit’s maxillae were highly visible at $^{30\\mathrm{~s,~}}$ demonstrating the antifogging performance. Furthermore, it could be seen that after $^{60}\\ s,$ the onecomponent coatings, especially for PHG coating, had a compromised antifogging property in comparison with the other three PPQA/PHG coatings. It was consistent with the results of the antifogging tests in vitro, but the blending coatings such as $\\mathrm{PPQA_{1}/P H G_{2}}$ still kept visually clear even under strong fogging conditions for $120\\ s$ (Video S2), showing high efficiency in preventing fog formation.  \n\nAntibacterial Properties. The antibacterial activity was first evaluated by testing MIC of copolymers against both Gram-positive bacteria, Staphylococcus aureus and Gramnegative bacteria, Escherichia coli. As shown in Figure 5A, the cationic copolymer of POSS-P(QAC-co-AEMA) had MIC values of 128 and $256~\\mu\\mathrm{g/mL}$ toward S. aureus and E. coli, respectively, which displayed reasonable antibacterial activity in comparison with antimicrobial polypeptides, antibiotic, or sliver-based antibacterial systems that exhibited MIC lower than $100~\\mu\\mathrm{g/mL}$ or even less than $10~\\mu\\mathrm{g/mL}.^{58-61}$ On the other hand, P(HEAA-co-GMA) has no antibacterial activity due to the lack of antimicrobial groups.  \n\nThe antibacterial properties of the copolymer coatings were investigated via the standard plate count method. As illustrated in Figure 5B, there were lots of bacteria colonies covered on a plate of the control sample. In sharp contrast, almost no colonies could be observed on cationic PPQA coating plates, both toward S. aureus and E. coli, suggesting that cationic QAC has excellent bactericidal activity. The blending coatings with different PPQA/PHG ratios of $2/1,1/1$ , and $1/2$ were also detected in this measurement. It could be seen from Figure 5B that there were also no bacteria colonies on the $\\mathrm{PPQA_{2}/P H G_{1}}$ plate and with the increased ratio of POSS-P(QAC-co-AEMA), the number of bacterial colonies declined, whereas PHG coating exhibited a similar result as that of bare glass. It could be concluded from the above results that hydroxyl-containing copolymer P(HEAA-co-GMA) had almost no contribution to bactericidal performance, but appropriate incorporation into coatings could still maintain the antibacterial performance compared with the PPQA sample.  \n\nThe antibacterial activities of the prepared coatings were further quantitatively investigated to obtain the growth inhibition rates by counting the number of bacteria colonies as shown in Figure 5B. It can be seen in Figure 5C that the growth inhibition rates of PPQA and $\\mathrm{PPQA}_{2}/\\mathrm{PHG}_{1}$ coatings nearly hit $99.9\\%$ against S. aureus and E. coli. With the increase of P(HEAA-co-GMA) content, $\\mathrm{PPQA_{1}/P H G_{1}},$ $\\mathrm{PPQA_{1}/P H G}_{2},$ and PHG coatings showed reduced bacterial growth inhibition rates at $67.2\\pm{\\:3.9}_{}$ , $47.7\\pm9.2\\$ , and $1.7\\pm5.3\\%$ , respectively, against E. coli. It could be assumed that the PPQA/PHG ratio had a significant effect on the antibacterial properties of the blending coatings. Meanwhile, it could be observed that the growth inhibition rate of $\\mathrm{PPQA_{1}/P H G_{1}}$ also reached $99.9\\%$ against S. aureus, indicating that the antibacterial activity of the prepared blending coatings against S. aureus was stronger than that of $E_{\\rightleftarrows}$ . coli, which was in accordance with the MIC results. This could be possibly related to the bacterial cell structure.62,63 Compared with Gram-positive S. aureus, an additional lipopolysaccharide-containing membrane was present in the structure of the Gram-negative $E$ . coli, thus making membrane destruction more difficult. Moreover, the antibacterial activities of POSS-free copolymer of P(QAC-coAEMA) and $\\mathrm{PQA_{1}/P H G_{1}}$ blending coating were also tested (Figure S5). The results indicated that POSS had little effect on antibacterial properties in this study. In addition, as suggested for potential applications for endoscopes, the blending coatings were also demonstrated to have long-term and recycling antibacterial property (Figure S6).  \n\nThe bacteria-associated infection begins with the adhesion of bacteria to the device surfaces. Therefore, endowing surfaces with bacteria-repellency is critical for biomaterial applications. Both S. aureus and E. coli were used to assess bacterial attachment on the coating surfaces. The bacterial attachment on the coating and bare glass, as well as bacterial morphology after incubation with the prepared coatings for $6\\mathrm{~h~}$ were observed by SEM (Figure 6). It could be seen that a large number of bacteria adhered on the PPQA coating and bare glass surface. Bacterial attachment on the blending coating surfaces decreased gradually with the increased amount of P(HEAA-co-GMA). Few bacteria were observed on the PHG coating surface, suggesting superior bacteria-repellent ability. Hydrogen-bonding interactions with hydroxyl and amide groups make the PHG coating surface form a hydrated layer to resist bacterial adhesion. On the other hand, drastic morphologic evolvements were witnessed either in S. aureus or E. coli, in which the bacteria membranes became wrinkled after incubation with PPQA coating, whereas the control of both S. aureus and E. coli on bare glass displayed a structurally intact cell wall. This could be attributed to the strong antibacterial activity of cationic QAC groups which could disrupt the membrane of bacteria by initial contact through an electrostatic effect and passive diffusion of the polymer chains (the alkyl chains) through the cell wall.  \n\nFurthermore, bacterial viability was detected on a fluorescence microscope after staining. Green fluorescent dye (STYO 9) generally labels all bacteria, whereas red fluorescent dye (PI) penetrates only bacteria with damaged membranes. As shown in Figure 7, numerous dead cells were seen both on the PPQA and $\\mathrm{PPQA}_{2}/\\mathrm{PHG}_{1}$ surfaces after incubation for $6\\mathrm{{h}}$ This phenomenon confirms again that the cationic POSSP(QAC-co-AEMA) copolymer plays a vital role for antibacterial activities. Because of the hydrophilicity of P(HEAA$c o$ -GMA), the amount of bacteria attached on $\\mathrm{PPQA_{1}/P H G_{2}}$ and PHG surfaces significantly decreased, demonstrating their excellent bacteria-repellent property. The tendency agreed well with that observed in SEM images. $\\mathrm{PPQA_{1}/P H G_{1}}$ coating showed an effective bacteria-repelling performance, and maintained bacterial growth inhibition rates of 99.9 and $67.2\\%$ against S. aureus and E. coli, respectively, being considered as the optimum in this work. It could be concluded from the above antibacterial and bacterial adhesion results that it was meaningful to balance the ratio of bactericidal POSSP(QAC-co-AEMA) and anti-adhesive P(HEAA-co-GMA) for achieving the best comprehensive antibacterial performance.  \n\n![](images/429b3b5276d210511c97edbc5da2fd8117509a831b23ae8336253f18b1f74d67.jpg)  \nFigure 6. SEM images of S. aureus (A) and E. coli (B) adhering to the prepared coatings after incubation for $^{6\\mathrm{~h~}}$ .  \n\n![](images/400d704dd8db621cad70108265259056cee5130f3155b67bd0308c20ba9e1812.jpg)  \nFigure 7. Fluorescent images of S. aureus (A) and $E$ . coli (B) on the prepared coating surfaces after incubation for $\\epsilon\\mathrm{h}$ . Red indicates dead bacteria, and green refers to live bacteria.  \n\nHemolytic Analysis. One of the challenges of cationic antibacterial materials is hemolytic activity. In this work, hemolytic rates of the resultant coatings were measured, and the results are shown in Figure 8. Pure water and PBS buffer were chosen as the positive and negative controls, respectively. After incubating with RBCs for $^{2\\mathrm{h}}$ , cationic PPQA coating had a hemolytic rate of $13.25\\pm0.40\\%$ , whereas for PHG coating, almost no hemolysis was observed $\\left(-0.06~\\pm~0.50\\%\\right)$ , suggesting compatibility with RBCs. It could be seen that the hemolysis rates of $\\mathrm{PPQA_{2}/P H G_{1}},$ $\\mathrm{PPQA_{1}/P H G_{1}},$ and $\\mathrm{PPQA_{1}/P H G_{2}}$ were $0.33\\pm\\:0.28$ , $0.86\\pm\\:0.03$ , and $3.89\\pm$ $0.01\\%$ , respectively, and all of them were less than $5\\%$ , meeting the clinical application requirement.64 After blending with P(HEAA-co-GMA), the hemolysis of the coatings reduced obviously as compared with that in the PPQA coating, which was because hydroxyl groups could interact with RBC surfaces by weak hydrogen-bonding, and thus protect RBCs from being destroyed,65 which was consistent with the previous work.66,67 The cytotoxicity of the coatings was also tested (Figure S7), though the cytotoxicity was not low.  \n\n![](images/cd703b064509b4f7402132549bf67e6b35e00b29ccc18efc80f4890dc961d5d1.jpg)  \nFigure 8. Hemolysis of the prepared blending coatings showing low values in comparison to the homopolymer PPQA coatings. All data were obtained from at least three samples and shown as the mean $\\pm$ standard deviation.  \n\nThe prepared PPQA/PHG blending coatings had antifogging and antibacterial properties simultaneously. As illustrated in Figure 9, both the cationic polyelectrolyte of QAC and two hydrogen-bond donor-containing HEAA in copolymers are responsible for rapidly absorbing water molecules from the environment and diffusing them into the bulk of the coatings via hydrogen-bonding interactions, that can greatly reduce light reflection or refraction and endow the surfaces with antifogging performance. The antibacterial properties of the blending coatings are triggered by the bacteria-killing and bacteriarepelling balance that was provided by positively charged POSS-P(QAC-co-AEMA) and hydrophilic P(HEAA-co-GMA), respectively. The coexistence of hydroxyl and amide groups rendered HEAA as a strong hydratable, which prevented the initial attachment of bacteria onto the device surfaces. Meanwhile, QAC was employed to kill the residual adhered bacteria through immobilizing the negative bacterial cell envelopes via electrostatic interaction and disrupting the membrane structure by alkyl chains. The dual functionality of the blending coatings suggests the excellent potential of this type of functionalization for medical devices.  \n\n![](images/cb2da9d85d03aa4639f69c4b1e81f2e90aeba158ed20a67b11ac0cd6dbac07d7.jpg)  \nFigure 9. Illustration of antifogging and antibacterial performances of the PPQA/PHG blending coatings. Both cationic and hydroxylcontaining copolymers are responsible for the antifogging performance due to water absorption and diffusion, and they also provide bacteria-killing and bacteria-repelling properties.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# CONCLUSIONS  \n\nIn this work, transparent, antifogging and antibacterial blending coatings were successfully prepared by casting the mixed copolymer solution of POSS-P(QAC-co-AEMA) and P(HEAA-co-GMA) in a simple and green approach. The two random copolymers are compatible as demonstrated by high transparency comparable to that of bare glass and nanoscaled roughness of the coating surfaces. Based on the hydrophilic HEAA and QAC, the resultant coatings with various blending ratios could effectively prevent fog formation under hot-vapor and cold-warm conditions. Meanwhile, in vivo antifogging study suggested that the PPQA/PHG blending coatings can remain optically clear under humid oral environments. Furthermore, it was found that the PPQA coating showed remarkable antibacterial property and the increased ratio of POSS-P(QAC-co-AEMA) in blending coatings could improve the bactericidal effect. On the other hand, neat PHG coating showed strong resistance to bacterial attachment. By tuning the bacteria-killing and bacteria-releasing properties among the copolymers of POSS-P(QAC-co-AEMA) and P(HEAA-coGMA), the blending coating with $1/1$ mass ratio simultaneously showed effective bacteria-repelling performance and maintained bacterial growth inhibition rates of 99.9 and $67.2\\%$ against S. aureus and E. coli, respectively, as well as the low hemolytic rate of $0.86\\pm0.03\\%$ . This work provides a facile approach to develop an antifogging/antibacterial polymeric coating, which could be potentially applied in medical devices of endoscopy or other related fields such as food preservation.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 7,
+        "chunk": "# ASSOCIATED CONTENT",
+        "category": " References"
+    },
+    {
+        "id": 8,
+        "chunk": "# $\\bullet$ Supporting Information  \n\nThe Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.9b21871.  \n\nMaterials, synthesis procedures of QAC, POSS-CPADB, POSS-P(QAC-co-AEMA), and P(HEAA-co-GMA), as well as their characterizations by $^{1}\\mathrm{H}$ NMR and GPC; thickness, stability, recycling antibacterial properties, and cytotoxicity of the coatings, and antifogging and antibacterial properties of $\\mathrm{PQA_{1}/P H G_{1}}$ coating (PDF)  \n\nIn vivo antifogging performance of bare glass (AVI) In vivo antifogging performance of the $\\mathrm{PPQA_{1}/P H G_{2}}$ coating (AVI)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# AUTHOR INFORMATION",
+        "category": " References"
+    },
+    {
+        "id": 10,
+        "chunk": "# Corresponding Authors  \n\nXiaohui Li − School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300350, China; $\\circledcirc$ orcid.org/ 0000-0003-3179-6585; Email: lixiaohui@tju.edu.cn Xiaoyan Yuan − School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300350, China; orcid.org/0000-0002-2895-3730; Email: yuanxy@ tju.edu.cn",
+        "category": " References"
+    },
+    {
+        "id": 11,
+        "chunk": "# Authors  \n\nShan Bai − School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300350, China Yunhui Zhao − School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300350, China Lixia Ren − School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300350, China; orcid.org/0000-0001-7659-0025  \n\nComplete contact information is available at: https://pubs.acs.org/10.1021/acsami.9b21871",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# Notes  \n\nThe authors declare no competing financial interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 13,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nThis work is financially supported by the National Natural Science Foundation of China under grant 51603143 (X.L.) and the Natural Science Foundation of Tianjin, China via grant 18JCQNJC03800 (X.L.) and 17JCZDJC37500 (X.Y.). Prof. Junmei Zhu at Tianjin Institute of Medical and Pharmaceutical Science, China, is appreciated for providing support of the in vivo antifogging test.",
+        "category": " References"
+    },
+    {
+        "id": 14,
+        "chunk": "# REFERENCES  \n\n(1) Peters, B. S.; Armijo, P.; Krause, C.; Choudhury, S.; Oleynikov, D. Review of Emerging Surgical Robotic Technology. Surg. Endosc. 2018, 32, 1636−1655.   \n(2) Manning, T. G.; Perera, M.; Christidis, D.; Kinnear, N.; McGrath, S.; O’Beirne, R.; Zotov, P.; Bolton, D.; Lawrentschuk, N. Visual Occlusion During Minimally Invasive Surgery: A Contemporary Review of Methods to Reduce Laparoscopic and Robotic Lens Fogging and Other Sources of Optical Loss. J. Endourol. 2017, 31, 327−333.   \n(3) Hervé, R.; Keevil, C. Persistent Residual Contamination in Endoscope Channels; A Fluorescence Epimicroscopy Study. Endoscopy 2016, 48, 609−616.   \n(4) Balan, G. G.; Sfarti, C. V.; Chiriac, S. A.; Stanciu, C.; Trifan, A. Duodenoscope-Associated Infections: A Review. Eur. J. Clin. Microbiol. Infect. Dis. 2019, 38, 2205−2213.   \n(5) Ciccozzi, M.; Cella, E.; Lai, A.; Florio, L. D.; Antonelli, F.; Fogolari, M.; Di Matteo, F. 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Enhancing Antifogging/Frost-Resisting Performances of Amphiphilic Coatings via Cationic, Zwitterionic or Anionic Polyelectrolytes. Chem. Eng. J. 2019, 357, 667−677.   \n(10) Wang, W.; Lu, P. P.; Fan, Y.; Tian, L. M.; Niu, S. C.; Zhao, J.; Ren, L. $\\scriptstyle\\mathrm{Q}\\$ A Facile Antifogging/Frost-Resistant Coating with SelfHealing Ability. Chem. Eng. J. 2019, 378, 122173.   \n(11) Li, C.; Li, X.; Tao, C.; Ren, L.; Zhao, Y.; Bai, S.; Yuan, X. Amphiphilic Antifogging/Anti-icing Coatings Containing POSSPDMAEMA- $\\cdot b$ -PSBMA. ACS Appl. Mater. Interfaces 2017, 9, 22959−22969.   \n(12) Lee, H.; Alcaraz, M. L.; Rubner, M. F.; Cohen, R. E. ZwitterWettability and Antifogging Coatings with Frost-Resisting Capabilities. ACS Nano 2013, 7, 2172−2185.   \n(13) Lee, H.; Gilbert, J. B.; Angilè, F. E.; Yang, R.; Lee, D.; Rubner, M. F.; Cohen, R. E. Design and Fabrication of Zwitter-Wettable Nanostructured Films. ACS Appl. Mater. 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Interfaces 2017, 9, 37511−37523. (39) Li, X.; Wu, B.; Chen, H.; Nan, K.; Jin, Y.; Sun, L.; Wang, B. Recent Developments in Smart Antibacterial Surfaces to Inhibit Biofilm Formation and Bacterial Infections. J. Mater. Chem. B 2018, 6, 4274−4292.   \n(40) Ganewatta, M. S.; Miller, K. P.; Singleton, S. P.; MehrpouyaBahrami, P.; Chen, Y. P.; Yan, Y.; Nagarkatti, M.; Nagarkatti, P.; Decho, A. W.; Tang, C. Antibacterial and Biofilm-Disrupting Coatings from Resin Acid-Derived Materials. Biomacromolecules 2015, 16, 3336−3344.   \n(41) Galié, S.; Garcia-Gutierrez, C.; Miguelez, E. M.; Villar, C. J.; Lombo, F. Biofilms in the Food Industry: Health Aspects and Control Methods. Front. Microbiol. 2018, 9, 898.   \n(42) Zhang, C.; Cui, F.; Zeng, G.-m.; Jiang, M.; Yang, Z.-z.; Yu, Z.- g.; Zhu, M.-y.; Shen, L.-q. Quaternary Ammonium Compounds (QACs): A Review on Occurrence, Fate and Toxicity in the Environment. Sci. 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Colloid Interface Sci. Commun. 2018, 23, 21−28.   \n(48) Zhang, Y.; Zhang, S.; Wu, S. Room-Temperature Fabrication of $\\mathrm{TiO}_{2}$ -PHEA Nanocomposite Coating with High Transmittance and Durable Superhydrophilicity. Chem. Eng. J. 2019, 371, 609−617. (49) Zhao, C.; Zheng, J. Synthesis and Characterization of Poly(Nhydroxyethylacrylamide) for Long-Term Antifouling Ability. Biomacromolecules 2011, 12, 4071−4079.   \n(50) Xu, F.-J. Versatile Types of Hydroxyl-Rich Polycationic Systems via O-Heterocyclic Ring-Opening Reactions: From Strategic Design to Nucleic Acid Delivery Applications. Prog. Polym. Sci. 2018, 78, 56− 91.   \n(51) Peng, J.; Liu, B.; Gao, S.; Zhu, K.; Zhao, Y.; Li, X.; Yuan, X. Enhanced Anti-Icing Properties of Branched PDMS Coatings with Self-Regulated Surface Patterns. Sci. China: Technol. Sci. 2020, 63, doi: DOI: 10.1007/s11431-019-1482-x.   \n(52) Gao, S.; Liu, B.; Peng, J.; Zhu, K.; Zhao, Y.; Li, X.; Yuan, X. Icephobic Durability of Branched PDMS Slippage Coatings CoCrossLinked by Functionalized POSS. ACS Appl. Mater. Interfaces 2019, 11, 4654−4666.   \n(53) Zhang, W.; Fang, B.; Walther, A.; Müller, A. H. E. Synthesis via RAFT Polymerization of Tadpole-Shaped Organic/Inorganic Hybrid Poly(acrylic acid) Containing Polyhedral Oligomeric Silsesquioxane (POSS) and Their Self-Assembly in Water. Macromolecules 2009, 42, 2563−2569.   \n(54) Chen, J.; Wei, D.; Gong, W.; Zheng, A.; Guan, Y. HydrogenBond Assembly of Poly(vinyl alcohol) and Polyhexamethylene Guanidine for Nonleaching and Transparent Antimicrobial Films. ACS Appl. Mater. Interfaces 2018, 10, 37535−37543.   \n(55) Fan, X.-l.; Hu, M.; Qin, Z.-h.; Wang, J.; Chen, X.-c.; Lei, W.-x.; Ye, W.-y.; Jin, $\\mathrm{Q.;}$ Ren, K.-f.; Ji, J. Bactericidal and Hemocompatible Coating via the Mixed-Charged Copolymer. ACS Appl. Mater. Interfaces 2018, 10, 10428−10436.   \n(56) Xiao, M.; González, E.; Monterroza, A. M.; Frey, M. Fabrication of Thermo-Responsive Cotton Fabrics Using Poly(vinyl caprolactam-co-hydroxyethyl acrylamide) Copolymer. Carbohydr. Polym. 2017, 174, 626−632.   \n(57) Zhao, C.; Chen, $\\mathrm{Q.;}$ Patel, K.; Li, L.; Li, X.; Wang, $\\mathrm{Q.;}$ Zhang, G.; Zheng, J. Synthesis and Characterization of pH-Sensitive Poly(N2-hydroxyethyl acrylamide)-Acrylic acid (poly(HEAA/AA)) Nanogels with Antifouling Protection for Controlled Release. Soft Matter 2012, 8, 7848−7857.   \n(58) Zhang, K.; Du, Y.; Si, Z. Y.; Liu, Y.; Turvey, M. E.; Raju, C.; Keogh, D.; Ruan, L.; Jothy, S. L.; Reghu, S.; Marimuthu, K.; De, P. P.; Ng, O. T.; Mediavilla, J. R.; Kreiswirth, B. N.; Chi, Y. R.; Ren, J. H.; Tam, K. C.; Liu, X.-W.; Duan, H.; Zhu, Y.; Mu, Y.; Hammond, P. T.; Bazan, G. C.; Pethe, K.; Chan-Park, M. B. Enantiomeric Glycosylated Cationic Block co-beta-Peptides Eradicate Staphylococcus aureus Biofilms and Antibiotic-Tolerant Persisters. Nat. 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X.; Khan, M.; Narayanan, K.; Seah, D.; Hedrick, J. L.; Yang, Y. Y. Antimicrobial/Antifouling Polycarbonate Coatings: Role of Block Copolymer Architecture. Macromolecules 2015, 48, 1055− 1064.   \n(64) Zhang, J.; Zhu, Y.; Song, J.; Yang, J.; Pan, C.; Xu, T.; Zhang, L. Novel Balanced Charged Alginate/PEI Polyelectrolyte Hydrogel that Resists Foreign-Body Reaction. ACS Appl. Mater. Interfaces 2018, 10, 6879−6886.   \n(65) Allison, B. C.; Applegate, B. M.; Youngblood, J. P. Hemocompatibility of Hydrophilic Antimicrobial Copolymers of Alkylated 4-Vinylpyridine. Biomacromolecules 2007, 8, 2995−2999. (66) Yuan, H.; Yu, B.; Fan, L.-H.; Wang, M.; Zhu, Y.; Ding, X.; Xu, F.-J. Multiple Types of Hydroxyl-Rich Cationic Derivatives of PGMA for Broad-Spectrum Antibacterial and Antifouling Coatings. Polym. Chem. 2016, 7, 5709−5718.   \n(67) Huang, Y.; Ding, X.; Qi, Y.; Yu, B.; Xu, F.-J. 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+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# (12) United States Patent Laas et al.",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (54) MODIFIED POLYISOCYANATES  \n\n(75） Inventors: Hans-Josef Laas, Bergisch Gladbach (DE); Reinhard Halpaap, Odenthal (DE)  \n\n(73）Assignee: Bayer Aktiengesellschaft, Leverkusen (DE)  \n\n（\\*） Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 69 days.  \n\n(21) Appl. No.: 10/276,344   \n(22) PCT Filed: May 7, 2001   \n(86) PCT No.: PCT/EP01/05143 $\\S371$ (c)(1), (2), (4) Date: Nov. 14, 2002   \n(87) PCT Pub. No.: WO01/88006 PCT Pub.Date: Nov. 22, 2001   \n(65) Prior Publication Data US 2004/0034162 A1 Feb. 19, 2004",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# (30) Foreign Application Priority Data  \n\nMay 18, 2000 (DE) 100 24624  \n\n(51) Int. CI.7 C08G 18/30 (52) U.S. Cl. 524/840; 528/71; 560/25; 252/182.22; 428/423.1  \n\n(58)Field of Search 252/182.22; 560/25; 528/71; 524/840; 428/423.1  \n\n(10) Patent No.: US 6,767,958 B2   \n(45) Date of Patent: Jul. 27, 2004",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# References Cited",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# U.S.PATENTDOCUMENTS  \n\n2,660,574A \\*11/1953 Wilford et al. 528/371   \n4,056,564A 11/1977 Wolf et al. 260/512C   \n4,433,095A 2/1984 Hombach et al. 524/563   \n4,663,377A 5/1987 Hombach et al. 524/196   \n5,098,983A 3/1992 Mosbach et al. 528/59   \n5,194,487 A 3/1993 Jacobs 524/591   \n5,334,637 A 8/1994 Zwiener et al. 524/539   \n5,389,718 A 2/1995 Potter et al. 524/591   \n5,473,011 A 12/1995 Laas et al. 524/840   \n5,594,148 A 1/1997 Wroblowsky et al. ... 548/263.6   \n6,426,414 B1 7/2002 Laas et al. 544/222",
+        "category": " References"
+    },
+    {
+        "id": 6,
+        "chunk": "# FOREIGNPATENTDOCUMENTS  \n\n<html><body><table><tr><td>CA</td><td>1 061 043</td></tr><tr><td>DE</td><td>8/1979 1495 745 6/1969</td></tr><tr><td>EP</td><td>0 324370 7/1989</td></tr><tr><td>EP</td><td>0 703255 3/1996</td></tr><tr><td>GB</td><td>1 447 612 8/1976</td></tr></table></body></html>  \n\n\\* cited by examiner  \n\nPrimary Examiner—Rachel Gorr   \n(74)Attorney, Agent, or Firm—Joseph C. Gil; Thomas W. Roy",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# ABSTRACT  \n\nThe present invention relates to a modified polyisocyanate which is the reaction product of a polyisocyanate with 2-(cyclohexylamino)-ethanesulfonic acid and/or 3-(cyclohexylamino)-propanesulfonic acid, to a process for preparing these modified polyisocyanates, to coating compositions containing these modified polyisocyanates and to coated substrates prepared from these coating compositions.",
+        "category": " Abstract"
+    },
+    {
+        "id": 8,
+        "chunk": "# 15 Claims, No Drawings",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# 1 MODIFIED POLYISOCYANATES",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# BACKGROUNDOFTHEINVENTION  \n\nThe invention relates to modified polyisocyanates and polyisocyanate mixtures, a process for their preparation and their use as starting components in the preparation of polyurethane plastics, in particular as crosslinking agents for water-soluble or —dispersible paint binders or binder components with groups which are reactive towards isocyanate groups.  \n\nAgainst the background of increasingly stricter environmental legislation, water-dispersible polyisocyanates have gained importance for various fields of use in recent years. They are currently used in particular as crosslinking components for high-quality water-dilutable two-component polyurethane paints (2C PU paints) or as an additive for aqueous dispersion adhesives, are used for crosslinking aqueous dispersion in textile finishing or formaldehyde-free textile printing inks and moreover are also suitable, for example, as auxiliary substances for wet-strength finishing of paper (cf.e.g.EP-A0 959 087 and literature cited herein).  \n\nIn practice, practically exclusively nonionic polyisocyanates modified hydrophilically with the aid of polyethers are currently employed for all these fields of use. The preparation of such water-dispersible polyisocyanates is discussed in detail,for example,in EP-A 0 959 087, page 2,lines 25-46.  \n\nIn spite of their wide market acceptance for the most diverse uses, however, polyether-modified polyisocyanates have a number of main disadvantages. Because of a very high viscosity maximum which is to be overcome during dispersing, for example, they can often be incorporated homogeneously into aqueous media only by applying considerable shear forces (e.g. high-speed stirrers). The high polyether content required for adequate dispersibility,in particular for use as crosslinking agents in aqueous 2C PU paints, furthermore imparts a permanent hydrophilicity to the coatings obtained.  \n\nTo bypass these disadvantages, attempts have also already been made to prepare self-dispersible polyisocyanates modified hydrophilically by incorporation of ionic groups.  \n\nEP-A0 443 138,EP-A0 510 438 and EP-A0 548 669 describe, for example, polyisocyanate mixtures which con- 4: tain chemically bonded carboxyl groups. Such polyisocyanates can indeed be stirred into aqueous systems in very fine division after neutralization of the carboxyl groups without high shear forces being necessary, but they have a completely inadequate storage stability, especially in the 5( neutralized form. Because of the known catalytic activity of the carboxylate group, a polymerization of the isocyanate groups already starts at room temperature, for example with trimerization to polyisocyanurates or formation of $\\mathbf{a}$ -nylon structures, which as a rule leads to gelling of the product 5: after a few days.  \n\nEP-A0 703 255 describes ionically hydrophilized wateremulsifiable polyisocyanates which comprise, as emulsifiers, reaction products of polyisocyanate and any desired hydroxy-, mercapto- or amino-functional compounds with at least one sulfuric acid group or anion thereof. Sulfuric acid builder components which are mentioned here as preferred for the preparation of the emulsifiers are hydroxysulfonic acids with aliphatically bonded OH groups or salts of such hydroxy-sulfonic acids, for example specific polyether-sulfonates, such as are marketed e.g. under the name Tegomer $\\mathbf{\\cdot}(\\mathbf{\\widehat{B}})$ (Th. Goldschmidt A G, Essen, D E), bisulfite adducts on unsaturated alcohols, such as are obtainable e.g. in accordance with the doctrine of DE-A2 417 664, DE-A 2 437 218 or DE-A 2 446 440, hydroxyethane- and hydroxypropanesulfonic acid and aminosulfobetaines, which can be prepared by quaternization of tertiary amino alcohols with 1,3-propanesultone. However, these hydrophilizing agents also have a number of disadvantages.  \n\nThus, for example, hydroxypropanesulfonic acid is in equilibrium with its anhydride, 1,3-propanesultone,which is classified as carcinogenic. It can therefore be handled on an industrial scale, in particular, exclusively in the form of aqueous solutions and is consequently unsuitable in principle as a builder component for the preparation of modified polyisocyanates.  \n\n5 On the other hand, hydroxyethanesulfonic acid, polyether-sulfonates of the Tegomer $\\textsuperscript{\\textregistered}$ type and the bisulfite adducts on unsaturated alcohols mentioned are also available as anhydrous products in the form of their sodium salts on a large industrial scale. The use of these sodium salts 0 indeed in principle allows the preparation of wateremulsifiable polyisocyanates, but these have only a very limited suitability for use as crosslinking components in aqueous paint systems. Because of the only low compatibility of alkali-neutralized sulfonate groups with conventional 5 paint binders, their use in aqueous 2C PU paints in general leads to cloudy, in some cases inhomogeneous coatings. In contrast to the volatile neutralization amines conventionally employed in dispersions, the sodium ion remains in the paint film even after curing and imparts a permanent hydrophi0licity to this.  \n\nAll the hydroxysulfonic acids proposed as hydrophilic components in EP-A 0 703 255 moreover lead, as the concrete embodiment examples of this publication demonstrate, as a rule to significantly yellow-coloured polyisocyanates, which also obstructs a use of these products as crosslinking components in high-quality paint systems. For the reasons mentioned, polyisocyanates modified with sulfonate groups have not yet been able to establish themselves on the market.  \n\nThe object of the present invention was therefore to provide new water-dispersible polyisocyanates which are suitable for all the fields of use of water-dispersible polyisocyanates and do not have the disadvantages of the prior art. These new polyisocyanates should be based on readily accessible,toxicologically acceptable builder components which allow a free choice of the neutralizing agent, and in particular should be readily compatible with conventional paint binders.  \n\nIt has been possible to achieve this object by providing the water-dispersible polyisocyanates or polyisocyanate mixtures according to the invention which are described below in more detail. To simplify the description of the present invention, in the following the term“polyisocyanates\" synonymously also means mixtures of various polyisocyanates.",
+        "category": " Introduction"
+    },
+    {
+        "id": 11,
+        "chunk": "# SUMMARY OF THE INVENTION  \n\nThe present invention is based on the surprising observation that, in spite of their melting points of above ${\\bar{3}}00^{\\circ}\\mathrm{C}.$ 2-(cyclohexylamino)-ethanesulfonic acid and 3-(cyclohexylamino)-propanesulfonic acid, which in general are used as zwitter-ionic biological buffer substances, can already be reacted with polyisocyanates under very mild reaction conditions in the presence of a suitable neutralization amine, storage-stable, light-coloured products which can be emulsified in water in finely divided form being obtained. This was surprising, since a number of other",
+        "category": " Introduction"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 4  \n\naminosulfonic acids which are very similar in structure cannot be reacted with polyisocyanates even under considerably more drastic conditions.  \n\nAlthough the use of compounds containing sulfonate groups for the preparation of hydrophilic polyisocyanates is co-mentioned globally in some publications, for example EP-A0 061 628 and EP-A0 206 059, the subject matter of which is polyether-modified polyisocyanates, and hydroxysulfonic acids and aminosulfonic acids are also mentioned as suitable builder components for water-dispersible crosslinking agents in EP-A 0 469 389, it has not been possible for the expert to obtain any indication from these publications, as in the same way from the doctrine of EP-A $\\bar{0}703255$ , of the particular suitability of 2-(cyclohexylamino)-ethanesulfonic acid and 3-(cyclohexylamino)-propanesulfonic acid for the preparation of water-dispersible polyisocyanates.  \n\nThe present invention therefore provides modified polyisocyanates which are obtainable by reaction of polyisocyanates with 2-(cyclohexylamino)-ethanesulfonic acid and/or 3-(cyclohexylamino)-propanesulfonic acid. These are dispersible in water after neutralization of at least a proportion of the sulfonic acid groups. The invention also provides the use of these sulfonic acids for the preparation of waterdispersible polyisocyanates.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# DETAILED DESCRIPTION OF THE INVENTION  \n\nThe dispersibility of polyisocyanates already modified with, for example, ethylene oxide polyether units is considerably improved by the modification according to the invention with 2-(cyclohexylamino)-ethanesulfonic acid and/or 3-(cyclohexylamino)-propanesulfonic acid, so that the use of external emulsifiers or the use of high shear forces can be dispensed with, which considerably simplifies the preparation of the ready-to-use formulations. This is a further aspect of the present invention.  \n\nIn particular, polyisocyanates with a) an average isocyanate functionality of at least 1.8, b) a content of isocyanate groups (calculated as NCO; molecular weight $\\scriptstyle\\mathtt{\\tilde{=}}42$ ) of 4.0 to 26.0 wt. $\\%$ ， c) a content of sulfonate groups (calculated as ${\\mathrm{SO}}_{3}{}^{-}$ · molecular weight $\\scriptstyle\\cdot=80$ ) of 0.1 to 7.7 wt. $\\%$ and optionally d) a content of ethylene oxide units bonded within polyether chains (calculated as $\\mathrm{C}_{2}\\mathrm{H}_{2}\\mathrm{O}$ molecularweight $_{=44}$ )of 0 to 19.5 wt. $\\%$ ，wherein the polyether chains contain a statistical average of 5 to 55 ethylene oxide units,  \n\nwhich are obtainable by reaction of aliphatic, cycloaliphatic, araliphatic and/or aromatic polyisocyanates with 2-(cyclohexylamino)-ethanesulfonic acid and/or 3-(cyclohexylamino)-propanesulfonic acid are provided according to the invention.  \n\nThe invention also provides a process for the preparation of these modified polyisocyanates.For this, a polyisocyanate is reacted with 2-(cyclohexylamino)-ethanesulfonic acid and/or 3-(cyclohexylamino)-propanesulfonic acid, it being possible for this reaction to be carried out in the presence of polyalkylene oxide polyether alcohols containing ethylene oxide units and/or the polyisocyanates employed optionally already containing such units. For neutralization of sulfonic acid groups, the reaction is carried out in the presence of tertiary amines.  \n\nIn particular, the reaction is carried out by a procedure in which  \n\nA)a polyisocyanate component with an average function  \n5 ality of 2.O to 5.O and a content of aliphatically, cycloaliphatically, araliphatically and/or aromatically bonded isocyanate groups (calculated as NCO; molecular weighi $\\scriptstyle\\mathbf{\\bar{\\alpha}}=42$ )of 8.0 to 27.0 wt. $\\%$ B) 0.3 to 25.0 wt. $\\%$ , based on the total weight of compo  \n10 nents A) and B), of 2-(cyclohexylamino)-ethanesulfonic acid and/or 3-(cyclohexylamino)-propanesulfonic acid and optionally C) up to 25 wt. $\\%$ , based on the total weight of components A),B) and C),of a monohydric polyalkylene oxide   \n15 polyether alcohol containing a statistical average of 5 to 35 ethylene oxide units, in the presence of D) 0.2 to 2.0 equivalents, based on the sulfonic acid groups of component B), of a tertiary amine   \n20 are reacted with one another observing an equivalent ratio of NCO groups to groups which are reactive towards NCO groups of 2:1 to 400:1. The nature and ratio of amounts of the starting compounds mentioned are otherwise chosen here such that the resulting reaction products meet the   \n25 conditions mentioned above under a) to d).  \n\nThe invention also provides the use of these polyisocyanates as starting components in the preparation of polyurethane plastics, in particular as crosslinking agents for watersoluble or -dispersible paint binders or paint binder components in the production of coverings using aqueous coating compositions based on such binders or binder components.  \n\nFinally, the invention also provides the use of these polyisocyanates as starting components in the preparation of blocked polyisocyanates which are water-dispersible or present as a dispersion in water.  \n\nComponent A) to be employed in the process according to the invention as a rule has an average NCO functionality of 2.0 to 5.0, preferably 2.3 to 4.5, a content of isocyanate ）groups of 8.0 to 27.0 wt. $\\%$ ， preferably 14.0 to 24.0 wt. $\\%$ and a content of monomeric diisocyanates of less than 1 wt. $\\%$ ，preferably less than O.5 wt. $\\%$ . It comprises at least one organic polyisocyanate with aliphatically, cycloaliphatically, araliphatically and/or aromatically bonded isocyanate 5 groups.  \n\nThe polyisocyanates of component A) are any desired polyisocyanates which are built up from at least two diisocyanates and are prepared by modification of simple aliphatic, cycloaliphatic, araliphatic and/or aromatic diiso  \n50 cyanates and have a uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure,such as are described by way of example,for example,in J.Prakt.Chem.336 (1994) 185-200, in DE-A 1 670 666,DE-A1 954 093,DE-A2 414 413,DE-A2 452   \n55532,DE-A2 641380,DE-A3700209,DE-A3900 053 and DE-A3 928 503 or inEP-A0 336 205,EP-A0 339 396 and EP-A0 798299. Suitable diisocyanates for the preparation of such poly isocyanates are any desired diisocyanates which are acces  \n50 sible by phosgenation or by phosgene-free processes, for example by thermal urethane cleavage. Preferred isocyanates are those of the molecular weight range of 140 to 400 with aliphatically, cycloaliphatically, araliphatically and/or aromatically bonded isocyanate groups, such as e.g. 1,4-   \n55 diisocyanatobutane, 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2- dimethylpentane, 2,2,4- and 2,4,4-trimethyl-1,6-",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# 6  \n\ndiisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4- diisocyanatocyclohexane, 1,3- and 1,4-bis(isocyanatomethyl)-cyclohexane, 1-isocyanato-3,3,5- trimethyl-5-isocyanatomethylcyclohexane (isophoronediisocyanate, IPDI), $^{4,4^{\\prime}}$ -diisocyanatodicyclohexylmethane, 1-isocyanato-1-methyl-4(3)isocyanato-methylcyclohexane, bis-(isocyanatomethyl)-norbornane, 1,3- and 1,4-bis-(2- isocyanato-prop-2-yl)-benzene (TMXDI), 2,4- and 2,6- diisocyanatotoluene (TDI)， 2,4'- and $4,4^{\\prime}-$ diisocyanatodiphenylmethane (MDI), 1,5- diisocyanatonaphthalene or any desired mixtures of such diisocyanates.  \n\nThe starting components A) are preferably polyisocyanates of the type mentioned with exclusively aliphatically and/or cycloaliphatically bonded isocyanate groups.  \n\nVery particularly preferred starting components A) are polyisocyanates with an isocyanurate structure which are based on HDI, IPDI and/or $^{4,4^{\\prime}.}$ diisocyanatodicyclohexylmethane.  \n\nIn addition to these hydrophobic polyisocyanates, however, polyisocyanates which are modified hydrophilically with the aid of ethylene oxide polyethers and such as are obtainable, for example, by the processes described in EP-A 0 959 087, page 2, lines 25-46 are also suitable as starting compounds A).  \n\nComponent B) is 2-(cyclohexylamino)-ethanesulfonic acid (CHES), 3-(cyclohexylamino)-propanesulfonic acid (CAPS) or any desired mixtures of these two aminosulfonic acids. These compounds are known, they are in crystalline form as zwitter-ionic substances, and have melting points above $300^{\\circ}$ C. The preparation of CHES and CAPS is described, for example, in Bull. Soc.Chim.France 1985, 463 and in Z. Chem. 7, 151 (1967).  \n\nThese aminosulfonic acids B) are employed in the process according to the invention in amounts of 0.3 to 25 wt. $\\%$ D preferably 0.5 to 25 wt. $\\%$ ，based on the total weight of components A) and B).  \n\nComponents C) which are optionally co-used are monohydric polyalkylene oxide polyether alcohols which contain a statistical average of 5 to 35, preferably 7 to 30 ethylene oxide units per molecule, such as are accessible in a manner known per se by alkoxylation of suitable starter molecules (see e.g. Ullmanns Encyclopadie der technischen Chemie, 4th edition, volume 19, Verlag Chemie, Weinheim p. 31-38).  \n\nAs suitable starter molecules for the preparation of the 45 polyether alcohols C) employed in the process according to the invention there may be mentioned here by way of example: saturated monoalcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secbutanol, the isomeric pentanols, hexanols, octanols and 5C nonanols, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexane, 3-ethyl-3-hydroxymethyloxetane, or tetrahydrofurfuryl alcohol; unsaturated alcohols, such as allyl alcohol, 1,1- 55 dimethyl-allyl alcohol or oleyl alcohol, aromatic alcohols such as phenol, the isomeric cresols or methoxyphenols, araliphatic alcohols, such as benzyl alcohol, anisyl alcohol or cinnamyl alcohol; secondary monoamines, such as dimethylamine， diethylamine, dipropylamine，6C diisopropylamine, di-n-butylamine, diisobutylamine, bis-(2- ethylhexyl)-amine, N-methyl- and N-ethylcyclohexylamine or dicyclohexylamine, and heterocyclic secondary amines, such as morpholine, pyrrolidine, piperidine or 1H-pyrazole.  \n\nPreferred starter molecules are saturated monoalcohols having up to 4 carbon atoms. Methanol is particularly preferably used as the starter molecule.  \n\nAlkylene oxides which are suitable for the alkoxylation reaction are,in particular, ethylene oxide and propylene oxide,which can be employed in the alkoxylation reaction in any desired sequence or also as a mixture.  \n\nThe polyalkylene oxide polyether alcohols C) are either pure polyethylene oxide polyethers or mixed polyalkylene oxide polyethers, the alkylene oxide units of which comprise ethylene oxide units to the extent of at least $30\\mathrm{\\mol}\\mathrm{\\}\\%$ preferably to the extent of at least $40\\mathrm{mol}\\%$ ·  \n\n10 Preferred starting components C) for the process according to the invention are pure polyethylene glycol monomethyl ether alcohols which contain a statistical average of 7 to 30, very particularly preferably 7 to 25 ethylene oxide units.  \n\n15 The polyether alcohols C) are employed in the process according to the invention, if at all, in amounts of up to 25 wt. $\\%$ , preferably up to 20 wt. $\\%$ ,based on the total weight of components A), B) and C).  \n\nTertiary amines D) are employed in the process according   \n20 to the invention for neutralization of the sulfonic acid groups of starting components B). These are, for example, tertiary monoamines, such as e.g. trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine,   \n25 N-methylpiperidine or $\\mathbf{N}$ -ethylpiperidine, or tertiary diamines, such as e.g. 1,3-bis-(dimethylamino)-propane, 1,4-bis-(dimethylamino)-butane or $\\mathbf{N},\\mathbf{N}^{\\prime}$ ， dimethylpiperazine.However, tertiary amines which carry groups which are reactive towards isocyanates are also   \n30 suitable, but less preferred, neutralization amines, for example alkanolamines, such as e.g. dimethylethanolamine, methyldiethanolamine or triethanolamine.  \n\nThese neutralization amines D) are employed in the process according to the invention in those amounts which correspond to an equivalent ratio of tertiary amino groups to sulfonic acid groups of component B) of 0.2 to 2.0, preferably 0.5 to 1.5.  \n\nTo carry out the process according to the invention, the starting components A), B) and optionally C) are reacted with one another in the presence of a tertiary amine D) at temperatures of 40 to $150^{\\circ}\\mathrm{~C~}$ ，preferably 50 to $\\mathrm{1~30^{\\circ}~C.}$ ， observing an equivalent ratio of NCO groups to groups which are reactive towards NCO groups of 2:1 to 400:1, preferably 4:1 to 250:1, preferably until the theoretically calculated NCO content is reached.  \n\nThe presence of the tertiary amine D) as a rule catalyses the reaction of components A), B) and optionally C) sufficiently, but further conventional catalysts known from polyurethane chemistry can optionally be employed to 50 accelerate the reaction in the process according to the invention, for example further tert. amines, such as triethylamine, pyridine, methylpyridine, benzyldimethylamine, N,N-endoethylenepiperazine, N-methylpiperidine, pentamethyldiethylenetriamine, N,N55 dimethyl-aminocyclohexane or N,N'-dimethylpiperazine, or metal salts, such as iron(Il) chloride, aluminium tri(ethylacetoacetate), zinc chloride, zinc(II) n-octanoate, zinc(II) 2-ethyl-1-hexanoate, zinc(II) 2-ethylcaproate, zinc(II) stearate,zinc(II) naphthenate,zinc(II) acetylacetonate, tin 50 (Il) n-octanoate, tin(Il) 2-ethyl-1-hexanoate, tin(II) ethylcaproate, tin(II) laurate, tin(II) palmitate, dibutyltin(IV) oxide, dibutyltin(IV) dichloride, dibutyltin(IV) diacetate, dibutyltin(IV) dimaleate, dibutyltin(IV) dilaurate, dioctyltin (IV) diacetate or molybdenum glycollate, or any desired 55 mixtures of such catalysts.  \n\nThese catalysts are employed in the process according to the invention, if at all, in an amount of O.0o1 to 2 wt. $\\%$ D",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 16,
+        "chunk": "#",
+        "category": "ovide the text segment you would like me to analyze."
+    },
+    {
+        "id": 17,
+        "chunk": "# 8  \n\npreferably 0.005 to 0.5 wt. $\\%$ ,based on the total weight of the reaction partners.  \n\nThe process according to the invention can optionally be carried out in a suitable solvent which is inert towards isocyanate groups.Suitable solvents are, for example, the conventional paint solvents which are known per se, such as e.g.ethyl acetate, butyl acetate, ethylene glycol monomethyl or -ethyl ether-acetate, 1-methoxyprop-2-yl acetate, 3-methoxy-n-butyl acetate, acetone,2-butanone, 4-methyl2-pentanone, cyclohexanone, toluene, xylene, chlorobenzene, white spirit, more highly substituted aromatics such as are commercially available, for example,under the names Solvent Naphtha, Solvesso $\\textsuperscript{\\textregistered}$ ,Isopar $\\textsuperscript{\\textregistered}$ ,Nappar $\\textsuperscript{\\textregistered}$ (Deutsche EXXON CHEMICAL GmbH, Cologne, DE) and Shellsol $\\textsuperscript{\\textregistered}$ (Deutsche Shell Chemie GmbH, Eschbom, DE), carbonic acid esters, such as dimethyl carbonate,diethyl carbonate, 1,2-ethylene carbonate and 1,2-propylene carbonate, lactones, such as $\\upbeta$ -propiolactone, $\\upgamma$ -butyrolactone, e-caprolactone and $\\epsilon$ -methylcaprolactone, and also solvents such as propylene glycol diacetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl and butyl ether-acetate, N-methylpyrrolidone and $\\mathbf{N}$ -methylcaprolactam, or any desired mixtures of such solvents.  \n\nIn the process according to the invention, the nature and ratios of amounts of the starting components are otherwise chosen, in the context of the statements made, such that the resulting polyisocyanates correspond to the statements made above under a) to d), wherein a) the average NCO functionality is preferably 2.0 to 4.8, particularly preferably 2.4 to 3.8, b) the NCO content is preferably 7.0 to 23.0 wt. $\\%$ particularly preferably 10.0 to 22.0 wt. $\\%$ ，c) the content of sulfonate groups (calculated as ${\\mathrm{SO}_{3}}^{-}$ ； molecularweight $\\scriptstyle\\mathtt{\\bar{\\alpha}}=80$ is preferably 0.2 to 6.3 wt. $\\%$ ， particularly preferably 0.6 to 4.8 wt. $\\%$ ,and d) the content of ethylene oxide units bonded within polyether chains is preferably up to 17 wt. $\\%$ particularly preferably up to 15 wt. $\\%$ ，  \n\nThe process products according to the invention are clear, practically colourless polyisocyanates of the composition already mentioned above which can easily be converted into sedimentation-stable dispersions by merely stirring into water, without using high shear forces.  \n\nThe outstanding dispersibility already at low sulfonate group contents in compounds with high NCO contents and comparatively high functionalities is an advantage in particular for the use of the polyisocyanates according to the invention in aqueous 2C PU paints, since highly crosslinked coatings which have in particular, in addition to a very good resistance to solvents and chemicals, an excellent resistance to water because of the low content of hydrophilic groups can be obtained in this manner.  \n\nFurther non-hydrophilized polyisocyanates, in particular paint polyisocyanates of the abovementioned type, can optionally also be added to the polyisocyanates prepared by the process according to the invention before the emulsification, the ratios of amounts preferably being chosen such that the resulting polyisocyanate mixtures meet the conditions mentioned above under a) to d), and are consequently also polyisocyanates according to the invention, since these in general comprise mixtures of  \n\n(i) polyisocyanates modified hydrophilically according to the invention and   \n(ii) non-modified polyisocyanates of the type mentioned by way of example.  \n\nIn such mixtures the process products according to the invention take over the function of an emulsifier for the subsequently admixed content of non-hydrophilic polyisocyanates.  \n\nThe polyisocyanates according to the invention are valuable starting materials for the preparation of polyisocyanate plastics by the isocyanate polyaddition process.  \n\nFor this, the polyisocyanates are preferably employed in the form of aqueous emulsions, which can be reacted in combination with polyhydroxy compounds dispersed in water in the sense of aqueous two-component systems.  \n\nThe polyisocyanates according to the invention are particularly preferably used as crosslinking agents for paint 10 binders or paint binder components which are dissolved or dispersed in water and have groups which are reactive towards isocyanate groups, in particular alcoholic hydroxyl groups, in the production of coatings using aqueous coating compositions based on such binders or binder components. 15 The combining of the crosslinking agent, optionally in emulsified form, with the binders or binder components can be carried out here by simple stirring before processing of the coating compositions by any desired methods, using mechanical aids known to the expert or also using two20 component spray guns.  \n\nIn this connection, paint binders or paint binder components which may be mentioned by way of example are: polyacrylates which are dissolved or dispersed in water and contain hydroxyl groups, in particular those of the molecular   \n25 weight range of 1,000 to 10,000, which, with organic polyisocyanates as crosslinking agents, are valuable twocomponent binders, or optionally urethane-modified polyester resins containing hydroxyl groups, of the type known from polyester and alkyd resin chemistry, which are dis  \n30 persed in water. All binders which are dissolved or dispersed in water and contain groups which are reactive towards isocyanates are in principle suitable as reaction partners for the polyisocyanate mixtures according to the invention. These also include, for example, polyurethanes or polyureas   \n35 which are dispersed in water and can be crosslinked with polyisocyanates on the basis of the active hydrogen atoms present in the urethane or urea groups.  \n\nThe polyisocyanate mixtures according to the invention are in general employed in the use according to the invention 40 as crosslinking components for aqueous paint binders in those amounts which correspond to an equivalent ratio of NCO groups to groups which are reactive towards NCO groups, in particular alcoholic hydroxyl groups, of 0.5:1 to 2:1.  \n\nThe polyisocyanate mixtures according to the invention can also optionally be admixed in minor amounts to nonfunctional aqueous paint binders to achieve quite specific properties, for example as an additive to improve adhesion.  \n\nThe polyisocyanates according to the invention can of   \n50 course also be employed in a form blocked with blocking agents known per se from polyurethane chemistry, in combination with the abovementioned aqueous paint binders or paint binder components in the sense of aqueous onecomponent PU stoving systems. Suitable blocking agents   \n55 are, for example,malonic acid diethyl ester, acetoacetic ester, acetone oxime, butanone oxime,ε-caprolactam, 3,5- dimethylpyrazole, 1,2,4-triazole, dimethyl-1,2,4-triazole, imidazole or any desired mixtures of these blocking agents.  \n\nPossible substrates for the aqueous coatings formulated 60 with the aid of the polyisocyanates according to the invention are any desired substrates, such as e.g. metal, wood, glass, stone, ceramic materials, concrete, rigid and flexible plastics, textiles, leather and paper, which can optionally also be provided with conventional primers before the 65 coating.  \n\nThe aqueous coating compositions which are formulated with the polyisocyanates according to the invention and to",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# 9  \n\nwhich the conventional auxiliary substances and additives in the paint sector, such as e.g. flow auxiliaries, coloured pigments, fillers, matting agents or emulsifiers, can optionally be added in general already have good paint properties on drying at room temperature.  \n\nHowever, they can of course also be dried under forced conditions at elevated temperature or by stoving at temperatures up to $260^{\\circ}\\mathrm{~C~}$ \\*  \n\nBecause of their outstanding emulsifiability in water, 10 which allows a homogenous, particularly finely divided distribution in aqueous paint binders, the use of the polyisocyanates according to the invention as crosslinking components for aqueous polyurethane paints leads to coatings with outstanding optical properties, in particular high sur- 15 face gloss, flow and high transparency.  \n\nIn addition to the preferred use as crosslinking components for aqueous 2C PU paints, the polyisocyanates according to the invention are outstandingly suitable as crosslinking agents for aqueous dispersion adhesives, leather and textile coatings or textile printing pastes, as AOX-free papermaking auxiliaries or also as additives for mineral building materials, for example concrete or mortar compositions.  \n\nThe following examples serve to further illustrate the invention. Unless noted otherwise, all the percentage data relate to the weight.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# EXAMPLES  \n\nExample 3   \n\n\n<html><body><table><tr><td>Solids content:</td><td>80%</td></tr><tr><td>NCO content:</td><td>16.1%</td></tr><tr><td>NCO functionality:</td><td>3.4</td></tr><tr><td>Viscosity (23° C.):</td><td>660 mPas</td></tr><tr><td>Colour number:</td><td>10 APHA</td></tr><tr><td>Sulfonate group content:</td><td>0.9%</td></tr><tr><td>Ethylene oxide content:</td><td>0.0%</td></tr></table></body></html>  \n\n$900\\textrm{g}$ (4.97 eq) of a polyisocyanate which contains isocyanurate groups and is based on HDI, with an NCO   \n15 content of $23.2\\%$ ，an average NCO functionality of 3.2 (according to GPC), a content of monomeric HDI of $0.1\\%$ and a viscosity of $1{,}200~\\mathrm{{mPas}}$ $(23^{\\circ}\\mathrm{~C~})$ are stirred together with $\\mathrm{100~g}$ (0.45 eq) CAPS and 57 g $\\left(0.45~\\mathrm{mol}\\right)$ dimethylcyclohexylamine under dry nitrogen for 1O hours at $80^{\\circ}\\mathrm{~C~}$   \n20 After cooling to room temperature, a practically colourless clear polyisocyanate mixture according to the invention with the following characteristic data is present:",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 20,
+        "chunk": "# Example 1  \n\nExample 4   \n\n\n<html><body><table><tr><td>25</td><td>Solids content:</td><td>100%</td></tr><tr><td></td><td>NCO content:</td><td>18.0%</td></tr><tr><td></td><td>NCO functionality:</td><td>2.9</td></tr><tr><td></td><td>Viscosity (23° C.):</td><td>9,200 mPas</td></tr><tr><td></td><td>Colour number:</td><td>25 APHA</td></tr><tr><td>30</td><td>Sulfonate group content:</td><td>3.4%</td></tr><tr><td></td><td>Ethylene oxide content:</td><td>0.0%</td></tr></table></body></html>  \n\n$950\\mathrm{~g~}$ (4.90 eq) of a polyisocyanate which contains isocyanurate groups and is based on 1,6-diisocyanatohexane (HDI), with an NCO content of $21.7\\%$ ，an average NCO functionality of 3.5 (according to GPC), a content of monomeric HDI of $0.1\\%$ and a viscosity of $3,000\\mathrm{mPas}$ $(23^{\\circ}\\mathrm{C})$ ， are stirred together with $50\\mathrm{g}(0.23\\mathrm{eq})$ 3-(cyclohexylamino)- propanesulfonic acid (CAPS), $29\\mathrm{g}\\left(0.23\\mathrm{mol}\\right)$ dimethylcyclohexylamine and $257\\mathrm{g}1$ -methoxyprop-2-yl acetate under dry nitrogen for 5 hours at $80^{\\circ}\\mathrm{~C~}$ After cooling to room temperature, a practically colourless clear solution of a polyisocyanate mixture according to the invention with the following characteristic data is present:  \n\n$900\\textrm{g}$ (4.65 eq) of the polyisocyanate described in example 1 which contains isocyanurate groups and is based on HDI are stirred together with $50\\ \\mathrm{g}$ (0.23 eq) CAPS, $29\\mathrm{g}$ $\\mathrm{0.23~mol})$ dimethylcyclohexylamine, $50\\ \\mathrm{g}$ (0.10 eq) of a monofunctional polyethylene oxide polyether started on ’ methanol and having an average molecular weight of 500 and $257\\mathrm{g}$ dipropylene glycol dimethyl ether as the solvent under dry nitrogen for 6 hours at $80^{\\circ}\\mathrm{~C~}$ After cooling to room temperature,a practically colourless clear solution of a polyisocyanate mixture according to the invention with the following characteristic data is present:  \n\nExample 2   \n\n\n<html><body><table><tr><td>Solids content:</td><td>80%</td></tr><tr><td>NCO content:</td><td>15.7%</td></tr><tr><td>NCO functionality:</td><td>3.3</td></tr><tr><td>Viscosity (23° C.):</td><td>590 mPas</td></tr><tr><td>Colour number:</td><td>15 APHA</td></tr><tr><td>Sulfonate group content:</td><td>1.4%</td></tr><tr><td>Ethylene oxide content:</td><td>0.0%</td></tr></table></body></html>\n\n55  \n\nExample 5   \n\n\n<html><body><table><tr><td>Solids content:</td><td>80%</td></tr><tr><td>NCO content:</td><td>14.1%</td></tr><tr><td>NCO functionality:</td><td>3.3</td></tr><tr><td>Viscosity (23° C.):</td><td>630 mPas</td></tr><tr><td>Colour number:</td><td>10 APHA</td></tr><tr><td>Sulfonate group content:</td><td>1.4%</td></tr><tr><td>Ethylene oxide content:</td><td>3.6%</td></tr></table></body></html>  \n\n$970\\mathrm{g}\\left(5.0\\mathrm{eq}\\right)$ of the polyisocyanate described in example 1 which contains isocyanurate groups and is based on HDI are stirred together with $30\\mathrm{g}(0.14\\mathrm{eq})$ 2-(cyclohexylamino)- ethanesulfonic acid (CHES), $18\\mathrm{~g~}(0.14\\mathrm{~mol})$ dimethylcyclohexylamine and $255\\mathrm{g}$ dipropylene glycol dimethyl ether under dry nitrogen for 4 hours at $80^{\\circ}~\\mathrm{C},$ After cooling to room temperature, a practically colourless clear solution of a polyisocyanate mixture according to the invention with the following characteristic data is present:  \n\n$1.357\\mathrm{g}\\left(3.84\\mathrm{eq}\\right)$ of a polyisocyanate which is in the form of a $70\\%$ solution in butyl acetate, contains isocyanurate groups and is based on 1-isocyanato-3,3,5-trimethyl-5- isocyanatomethylcyclohexane (IPDl), with an NCO content of $11.9\\%$ ， an average NCO functionality of 3.3 according to GPC), a content of monomeric IPDI of $0.2\\%$ and a viscosity of $650\\mathrm{mPas}$ $(23^{\\circ}\\mathrm{C})$ are stirred together with $50\\mathrm{g}(0.23\\mathrm{eq})$ CAPS, $29\\mathrm{~g~}$ C $\\mathrm{0.23mol},$ ）dimethylcyclohexylamine and a further $34\\mathrm{g}$ butyl acetate under dry nitrogen for 12 hours at $80^{\\circ}$ C. After cooling to room temperature, a practically colourless clear solution of a polyisocyanate mixture according to the invention with the following characteristic data is present:  \n\n<html><body><table><tr><td>Solids content:</td><td>70%</td></tr><tr><td>NCO content:</td><td>10.3%</td></tr><tr><td>NCO functionality:</td><td>3.1</td></tr><tr><td>Viscosity (23° C.):</td><td>810 mPas</td></tr><tr><td>Colour number:</td><td>10-15 APHA</td></tr><tr><td>Sulfonate group content:</td><td>1.2%</td></tr><tr><td>Ethylene oxide content:</td><td>0.0%</td></tr></table></body></html>  \n\n<html><body><table><tr><td colspan=\"2\">-continued</td></tr><tr><td>NCO functionality:</td><td>3.7</td></tr><tr><td>Viscosity (23° C.):</td><td>1,800 mPas</td></tr><tr><td>Colour number:</td><td>150 APHA</td></tr><tr><td>Sulfonate group content:</td><td>1.0%</td></tr><tr><td>Ethylene oxide content:</td><td>13.2%</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 21,
+        "chunk": "# Example 9  \n\n$950\\ \\mathrm{~g~}$ (4.90 eq) of the polyisocyanate described in example 1 which contains isocyanurate groups and is based on HDI are stirred together with $50\\ \\mathrm{~g~}$ (0.36 eq) 2-methylaminoethanesulfonic acid (methyltaurine), $\\boldsymbol{46}_{\\mathrm{~\\scriptsize~g~}}$ $\\left(0.36~\\mathrm{~mol}\\right)$ dimethylcyclohexylamine and $262\\ \\mathrm{~g~}$ 1-methoxyprop-2-yl acetate under dry nitrogen at $80^{\\circ}\\mathrm{~C~}$ \\* After 8 hours the reaction mixture is still cloudy and inhomogeneous. Even after increasing the temperature to $120^{\\circ}\\mathrm{~C~}$ and a further 4 hours the starting components have not reacted with one another. Methyltaurine settles in crystalline form as a sediment in the dark yellow-coloured reaction mixture.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 22,
+        "chunk": "# Comparison",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# Example 6",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 24,
+        "chunk": "# Preparation of Emulsions  \n\n$\\mathrm{100~g}$ deionized water were added to in each case $35\\mathrm{g}$ of the polyisocyanate mixtures according to the invention,   \n15 dissolved to $80\\%$ ,from example $1,2$ and 4, $40\\ \\mathrm{g}$ of the $70\\%$ solution from example 5 and $25\\mathrm{~g~}$ of the polyisocyanate mixture according to the invention from example 3 in each case in a conical flask, corresponding to a solids content of in each case approx. 20 wt. $\\%$ ,and the mixtures were then   \n20 in each case stirred for $1~\\mathrm{min}$ with the aid of a magnetic stirrer at $900\\mathrm{rpm}$ . The emulsions obtained by this procedure were still completely stable even after a standing time of 5 h. They showed neither visible evolution of $\\mathrm{CO}_{2}$ nor precipitates or sediment. The average particle sizes were deter  \n25 mined with the aid of a Zetasizer apparatus (Malvern Instruments GmbH, Herrenberg, DE) as a measure of the dispersibility of the various polyisocyanate mixtures. The following table shows the values found.  \n\n30",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 25,
+        "chunk": "# Example 7",
+        "category": " Introduction"
+    },
+    {
+        "id": 26,
+        "chunk": "# Comparison  \n\n$950\\ \\mathrm{\\g}$ (4.90 eq) of the polyisocyanate described in 35 example 1 which contains isocyanurate groups and is based on HDI are stirred together with $50\\ \\mathrm{~g~}$ (0.40 eq) 2-aminoethanesulfonic acid (taurine), $51\\mathrm{g}\\left(0.40\\mathrm{mol}\\right)$ dimethylcyclohexylamine and $263\\textrm{g}1$ -methoxyprop-2-yl acetate under dry nitrogen at $80^{\\circ}\\mathrm{~C~}$ .After 8 hours the 40 reaction mixture is still cloudy. Even after increasing the temperature to $120^{\\circ}~\\mathrm{C}$ . and a further 6 hours the starting components have not reacted with one another. Methyltaurine settles as a crystalline sediment in the yellow-coloured reaction mixture.  \n\n<html><body><table><tr><td>Polyisocyanate mixture from</td><td>Average particle size [nm]</td></tr><tr><td>Example 1</td><td>116</td></tr><tr><td>Example 2</td><td>412</td></tr><tr><td>Example 3</td><td>83</td></tr><tr><td>Example 4</td><td>93</td></tr><tr><td>Example 5</td><td>242</td></tr></table></body></html>  \n\nExample 10",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 27,
+        "chunk": "# Use as Crosslinking Agents for Aqueous 2C PU Paints",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 28,
+        "chunk": "# Example 8",
+        "category": " Introduction"
+    },
+    {
+        "id": 29,
+        "chunk": "# Comparison Analogously to EP-B 0 703 255, Example 5  \n\n$800\\ \\mathrm{~g~}$ (4.13 eq) of the polyisocyanate described in example 1 which contains isocyanurate groups and is based on HDI are stirred together with $200\\mathrm{g}\\left(0.30\\mathrm{eq}\\right)$ of a sodium polyethylene oxide polyether diol-sulfonate (Tegome) $r_{\\bigstar}$ DS-3404,Th.Goldschmidt AG,Essen, DE; OH number: 84, sulfonate group content: approx. $6.0\\%$ ,ethylene oxide content: approx. $82.2\\%$ and $250\\mathrm{g}$ 1-methoxyprop-2-yl acetate as the solvent under dry nitrogen for 5 hours at $80^{\\circ}\\mathrm{C}$ After cooling to room temperature, a yellowish clear solution of a water-dispersible polyisocyanate mixture with the following characteristic data is present:  \n\n100 parts by wt. of an aqueous, hydroxy-functional poly  \n45 acrylate dispersion which is free from co-solvent and has a solids content of $45\\%$ and an OH content of $2.5\\%$ ,based on the solid resin, substantially comprising $48.0\\%$ methyl methacrylate, $27.4\\%$ n-butyl acrylate, $21.6\\%$ hydroxy- ${\\bf\\cdot C}_{3}$ alkyl methacrylate (addition product of propylene oxide on   \n50 methacrylic acid) and $3.0\\%$ acrylic acid, were mixed with 0.5 parts by wt. of a commercially available defoamer (Foamaster $\\textsuperscript{\\textregistered}$ TCX, Henkel KGA, DE). 39.5 parts by wt. of the polyisocyanate mixture according to the invention from example 1 (corresponding to an equivalent ratio of isocy  \n55 anate groups to alcoholic hydroxyl groups of 1:1) were added to this mixture and the mixture was homogenized by intensive stirring $(2{,}000~\\mathrm{rpm})$ .The solids content was then adjusted to $40\\%$ by addition of water.  \n\nFor comparison, a paint was prepared from 100 parts by $^{60}$ wt. of the hydroxy-functional polyacrylate dispersion described above and 48.0 parts by wt.of the polyisocyanate according to EP-B $0\\ 703\\ 255$ from example 8 (corresponding to an equivalent ratio of isocyanate groups to alcoholic hydroxyl groups of 1:1) by the process described 65 above.  \n\nThe processing time of the paints ready for application was about 3 hours. The paints were applied to glass plates in a wet film layer thickness of $150\\mu\\mathrm{m}$ (approx. $60\\ \\mu\\mathrm{m}$ dry) and, after evaporation in air for 20 minutes, were dried under forced conditions（ $(30\\mathrm{\\min}/60^{\\circ}\\mathrm{\\C}.\\$ .Paint films with the following properties were obtained:  \n\n<html><body><table><tr><td>Polyisocyanate from</td><td>Example 1</td><td>Example 8 (comparison)</td></tr><tr><td>Film optical properties</td><td>clear</td><td>cloudy</td></tr><tr><td>Gloss, visuallya)</td><td>0</td><td>5</td></tr><tr><td>Pendulum hardness [s] after 1 d/7 db)</td><td>125/143</td><td>79/105</td></tr><tr><td>Resistance to solventsc) water (30 min)</td><td>0</td><td>5</td></tr><tr><td>isopropanol/water 1:1 (1 min)</td><td>0</td><td>3</td></tr><tr><td>MPA/xylene 1:1 (1 min)</td><td>0</td><td>1</td></tr><tr><td>butyl glycol (1 min)</td><td>0</td><td>2</td></tr><tr><td>acetone (1 min)</td><td>1</td><td>4</td></tr></table></body></html>\n\na)Evaluation: 0 (very good)-5 (poor) bKonig pendulumhardness (DIN53157) Evaluation: 0-5( $0=$ paint film unchanged; $5=$ completely dissolved)  \n\nThe comparison shows that the use of the polyisocyanates according to the invention from example 1 leads to a clear, high-gloss, hard and solvent-resistant paint film, while using the polyisocyanate containing sodium sulfonate groups from example 8 a cloudy and considerably softer coating is obtained,which moreover is not water-resistant and not sufficiently solvent-resistant.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 30,
+        "chunk": "# Example 11",
+        "category": " Introduction"
+    },
+    {
+        "id": 31,
+        "chunk": "# Preparation of a Blocked Polyisocyanate  \n\n$350~\\mathrm{g}$ (1.31 eq)of the polyisocyanate mixture according $35$ to the invention from example 1 are initially introduced into the reaction vessel at $70^{\\circ}\\mathrm{~C~}$ . and $\\ensuremath{126\\mathrm{~g~}}$ (1.31 eq) 3,5- dimethylpyrazole are added in portions in the course of 30 min such that the temperature of the reaction mixture does not exceed $80^{\\circ}\\mathrm{C}$ When the addition has ended, the mixture 40 is subsequently stirred for approx.2 hours at $70^{\\circ}\\mathrm{C}.$ until free isocyanate groups are no longer detectable by IR spectroscopy. After cooling to $40^{\\circ}$ C., $539\\mathrm{~g~}$ deionized water are allowed to run in, with vigorous stirring, in the course of 30 min. A finely divided bluish-tinged dispersion of a blocked 45 polyisocyanate with the following characteristic data is obtained:  \n\n<html><body><table><tr><td>Solids content:</td><td>40%</td></tr><tr><td>Content of blocked NCO groups:</td><td>5.4%</td></tr><tr><td>NCO functionality:</td><td>3.7</td></tr><tr><td>Viscosity (23° C.):</td><td>160 mPas</td></tr><tr><td>Co-solvent content:</td><td>6.9%</td></tr></table></body></html>  \n\nWhat is claimed is:  \n\n1.A modified polyisocyanate which comprises the reaction product of a polyisocyanate with 2-(cyclohexylamino)- ethanesulfonic acid and/or 3-(cyclohexylamino)- 6 propanesulfonic acid.  \n\n2. The modified polyisocyanate of claim 1 wherein the modified polyisocyanate has  \n\na) an average isocyanate functionality of at least 1.8, b) a content of isocyanate groups (calculated as NCO; MW 42) of 4.0 to 26.0 wt. $\\%$ ·  \n\n14 c) a content of sulfonate groups (calculated as $\\mathrm{SO}_{3}.$ 一; MW 80) of 0.1 to 7.7 wt. $\\%$ and d) a content of ethylene oxide units (calculated as $\\mathrm{C}_{2}\\mathrm{H}_{2}\\mathrm{O}$ .。 MW 44) bound within polyether chains of O to 19.5 wt. $\\%$ , wherein the polyether chains contain an average of 5 to 55 ethylene oxide units. 3. The modified polyisocyanate of claim 1 wherein the   \nmodified polyisocyanate has a) an average isocyanate functionality of 2.0 to 4.8, b) a content of isocyanate groups (calculated as NCO; MW 42) of 7,0 to 23.0 wt. $\\%$ ， c) a content of sulfonate groups (calculated as $\\mathrm{SO}_{3}.$ ; MW 80) of 0.2 to 6.3 wt. $\\%$ and d) a content of ethylene oxide units (calculated as $\\mathrm{C}_{2}\\mathrm{H}_{2}\\mathrm{O}$ .。 MW 44) bound within polyether chains of O to 17.0 wt. $\\%$ ，wherein the polyether chains contain an average of 7 to 30 ethylene oxide units. 4. The modified polyisocyanate of claim 1 wherein said   \npolyisocyanate is an aliphatic, cycloaliphatic, araliphatic   \nand/or aromatic polyisocyanate. 5. The modified polyisocyanate of claim 1 wherein said   \npolyisocyanate is an aliphatic and/or cycloaliphatic polyiso  \ncyanate. 6.A process for the preparation of a modified polyisocy  \nanate which comprises reacting a polyisocyanate with   \n2-(cyclohexylamino)-ethanesulfonic acid and/or   \n3-(cyclohexylamino)-propanesulfonic acid in the presence   \nof a tertiary amine. 7. The process of claim 6 which comprises carrying out   \nthe reaction in the presence of a polyalkylene oxide poly  \nether alcohol containing ethylene oxide units and/or wherein   \nsaid polyisocyanate contains chemically incorporated eth  \nylene oxide polyether units. 8. The process of claim 6 which comprises reacting at an   \nequivalent ratio of NCO groups to isocyanate-reactive   \ngroups of 2:1 to 400:1 A) a polyisocyanate component having an average functionalityof2.0to 5.0 and acontent of aliphatically, cycloaliphatically, araliphatically and/or aromatically bound isocyanate groups (calculated as NCO; MW 42) of 8.0 to 27.0 wt. $\\%$ with B) 0.3 to 25.0 wt. $\\%$ ， based on the total weight of components A) and B), of 2-(cyclohexylamino)- ethanesulfonic acid and/or 3-(cyclohexylamino)- propanesulfonic acid and C) up to 25 wt. $\\%$ , based on the total weight of components A), B) and C), of a monohydric polyalkylene oxide polyether alcohol containing an average of 5 to 35 ethylene oxide units, in the presence of D) 0.2 to 2.O equivalents, based on the sulfonic acid groups of component B), of a tertiary amine. 9.The processof claim 6 which comprises reacting at an   \nequivalent ratio of NCO groups to isocyanate-reactive   \ngroups of 4:1 to 250:1 A) a polyisocyanate component having an average functionality of 2.3 to 4.5 and a content of aliphatically and/or cycloaliphatically bound isocyanate groups (calculated as NCO; MW 42) of 14.0 to 24.0 wt. $\\%$ with B)0.5 to 25.0 wt. $\\%$ ， based on the total weight of components A) and B), of 2-(cyclohexylamino)- ethanesulfonic acid and/or 3-(cyclohexylamino)- propanesulfonic acid and",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 32,
+        "chunk": "# 15",
+        "category": " Introduction"
+    },
+    {
+        "id": 33,
+        "chunk": "# 16  \n\nC) up to 20 wt. $\\%$ ,based on the total weight of components A),B) and C), of a monohydric polyalkylene oxide polyether alcohol containing an average of 5 to 35 ethylene oxide units, in the presence of D)0.5 to 1.5 equivalents, based on the sulfonic acid 5 groups of component B), of a tertiary amine. 10. The process of claim 6 wherein said polyisocyanate is prepared from at least two molecules of 1,6- diisocyanatohexane, 1-isocyanato-3,3,5-trimethyl-5- isocyanatomethylcyclohexane and/or 4,4'- 1( diisocyanatodicyclohexylmethane. 11. The process of claim 6 wherein said tertiary amine comprises an aliphatically and/or cycloaliphatically substituted tertiary amine.  \n\n12. The process of claim 6 wherein said tertiary amine comprises triethylamine, dimethylcyclohexylamine and/or N-methylmorpholine. 13.An aqueous coating composition containing a watersoluble or water-dispersible binder and the modified polyisocyanate of claim 1 as the crosslinking agent. 14. The aqueous coating composition of claim 13 wherein the modified polyisocyanate is blocked with a blocking agent for isocyanate groups. 15.A substrate coated with coating composition of claim 13.",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,27 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Thiol-Epoxy Polymerization via an AB Monomer: Synthetic Access to High Molecular Weight Poly( $\\beta$ -hydroxythio-ether)s  \n\nSelmar Binder, Ikhlas Gadwal, Andreas Bielmann, Anzar Khan  \n\nDepartment of Materials, ETH-Z€urich, 8093 Z€urich, Switzerland Correspondence to: A. Khan (E-mail: anzar.khan $@$ mat.ethz.ch)  \n\nReceived 11 March 2014; accepted 8 April 2014; published online 00 Month 2014   \nDOI: 10.1002/pola.27212  \n\nABSTRACT: A synthetic route is developed for the preparation of an AB-type of monomer carrying an epoxy and a thiol group. Base-catalyzed thiol-epoxy polymerization of this monomer gave rise to poly $\\beta$ -hydroxythio-ether)s. A systematic variation in the reaction conditions suggested that tetrabutyl ammonium fluoride, lithium hydroxide, and 1,8-diazabicycloundecene (DBU) were good polymerization catalysts. Triethylamine, in contrast, required higher temperatures and excess amounts to yield polymers. THF and water could be used as polymerization mediums. However, the best results were obtained in bulk conditions. This required the use of a mechanical stirrer due to the high viscosity of the polymerization mixture. The polymers obtained from the AB monomer route exhibited significantly higher molecular weights $(M_{\\mathrm{w}}=47,700,$ $M_{\\mathrm{n}}=23,200~\\mathrm{g/mol})$ than the materials prepared from an AA/BB type of the monomer system $(M_{\\mathrm{w}}=10,000$ , $M_{\\mathrm{n}}{=}5400~\\mathrm{g/mol)}$ . The prepared reactive polymers could be transformed into a fluorescent or a cationic structure through postpolymerization modification of the reactive hydroxyl sites present along the polymer backbone. $\\circledcirc$ 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 00, 000–000  \n\nKEYWORDS: addition polymerization; functionalization of polymers; thiol-epoxy reaction; polyelectrolytes; click polymerization  \n\nINTRODUCTION Robust, efficient, and orthogonal (REO) approaches to macromolecular synthesis have revolutionized the manner in which functional soft materials are being prepared.1–11 Inspired by this philosophy, recently, efficient, and robust coupling reaction between a thiol and an epoxy unit11–14 was demonstrated to give access to a new family of reactive polymers referred to as poly( $\\displaystyle{\\beta}$ -hydroxythioether)s.11(c) The polymerization process is shown to occur in the presence of moisture and air from commercially available and inexpensive monomers and the resulting polymers could be converted into functionalized structures in a single postpolymerization step. The synthetic ease, commercial availability of the building blocks, modular nature of the process, and avenue for functionalization suggested that this new family of polymers could find wide ranging applications.  \n\nIn the previous design,11(c) however, synthesis of poly( $\\mathrm{\\Delta}\\cdot\\mathrm{\\Delta}\\beta$ - hydroxythio-ether)s was accomplished through a polyaddition reaction between AA and BB types of monomers. The advantage associated with this approach lies in the commercial availability of a variety of di-thiol and di-epoxide molecules. The disadvantage, however, is that the attainable degree of polymerization in an AA/BB system is highly sensitive to the functional group stoichiometry.15 A failure to meet the 1:1 functional group balance prevents the formation of high molecular weight polymers as the excess functionality can act as a chain terminator. To satisfy the stringent requirement of stoichiometric balance, the monomers utilized should be of very high purity and should be weighed, measured, and transferred into the reaction vessel with utmost precision. In contrast, utilization of an AB system for the polymerization reaction alleviates these issues due to an inherent balance of the two reactive groups in a single molecule. Placing two mutually reactive functionalities on the same molecule, however, may not be a straightforward affair. This requires careful development of a synthetic strategy that involves orthogonal organic transformations of the functional groups. Nonetheless, this task is worth undertaking as, in principal, high degrees of polymerization could be achieved using an AB monomer system. Therefore, in this work, we discuss the synthesis of an AB type of monomer for the synthesis of relatively high molecular weight poly( $\\beta$ -hydroxythio-ether)s through the thiolepoxy polyaddition reaction (Scheme 1). Furthermore, we demonstrate that these polymers represent a general reactive scaffold that can be transformed into a desired functionalized structure.  \n\n![](images/41b75aca32aaa3916fa7cf163b0ca34fda3c7eaba9a8560f2cc3787c7f58afbf.jpg)  \nSCHEME 1 Synthesis and functionalization of poly $\\boldsymbol{{\\mathrm{\\cdot}}}\\beta$ -hydroxythio-ether)s through an AB monomer.  \n\n![](images/bb84fb7fc2f8a7367ce2d8185506d578aa3d158ff7802024263ba661b8288ebe.jpg)  \nFIGURE 1 ${}^{1}\\mathsf{H N M R}$ of compounds 1 (bottom), 2 (middle), and AB monomer 3 (top) in $\\mathsf{C D C l}_{3}$ . Tetramethylsilane (TMS) was used as an internal standard.  \n\n![](images/383a932e301ec9d7b681b678af79e9c11f118132955ea6cf4dbe619e52eeadc3.jpg)  \nFIGURE 2 Crude GPC traces showing evolution of molecular weight in the thiol-epoxy polyaddition reaction as a function of polymerization time.",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# RESULTS AND DISCUSSION  \n\nIn the present context, an AB monomer is comprised of a molecule carrying a free thiol and an epoxide unit (Scheme 1). Thiols are excellent nucleophiles under basic conditions and epoxides are sensitive to an acidic environment. Therefore, synthesis of an AB monomer suitable for the thiol-epoxy polymerization may be problematic to prepare under acidic or basic conditions. Hence, we referred to free radical chemistry (chemically neutral conditions) for the synthesis of such a bifunctional monomer. For this, a thiol group of bis-mercaptoethyl ether, 1, was allowed to react with an alkene functionality of allyl glycidyl ether, 2, under ambient light and aerobic conditions at room temperature (Scheme 1). It is known that exposure of alkenes to air results in the formation of peroxides that can catalyze the addition of thiols to the alkene functionality.16 This process is self-catalytic in nature, and known to be accelerated by light. This furnished the AB monomer 3 carrying the necessary thiol and epoxide functionalities. To confirm the free radical nature of the coupling reaction between precursors 1 and 2, a free radical inhibitor, 2,6-ditert-butyl-4-methylphenol (BHT) was added to the reaction mixture. In this case, no coupling product was observed even after 2 days of reaction time. This suggested that the coupling reaction in between molecules 1 and 2 was free radical in nature. Monomer 3 was purified through a flash column chromatography technique as some degradation of the monomer, presumably due to sensitivity of the epoxide unit, was observed upon its prolonged stay on the silica gel column. Once purified, the monomer could be stored for a few weeks under inert conditions and at low temperatures. The reaction between molecules 1 and 2 to generate monomer 3 could be followed with the help of $^1\\mathrm{H}$ NMR spectroscopy, as olefin resonances at 4.1, 5.2, and 5.9 ppm could no longer be observed upon free radical coupling reaction. Moreover, a new signal could be observed at $1.8~\\mathrm{ppm}$ due to the newly formed methylene group in 3 (designated with $\\mathbf{\\dot{e}}^{\\prime}$ in Fig. 1). The purity of monomer 3 could be verified with the help of elemental analysis, which showed that the theoretical ratio of elements (C, H, O, and S) were in excellent agreement to the experimentally determined values (Supporting Information Fig. S1).  \n\nTo establish optimum polymerization conditions, a series of test reactions using freshly prepared monomer was carried out in tetrahydrofuran (THF) (Fig. 2) and the resulting polymerization mixture was precipitated into either diethyl ether or an ethyl acetate/hexane (1:3) mixture (Table 1). It was observed that the polymerization yield was low in diethyl ether and high in ethyl acetate/hexane mixture. The low polymerization yield and relatively high molecular weights observed upon precipitation into diethyl ether indicate polymer fractionation. Therefore, only the results obtained through precipitation into ethyl acetate/hexane mixture are compared.  \n\nTABLE 1 Thiol-Epoxy Polymerization of Monomer 3   \n\n\n<html><body><table><tr><td>Entry</td><td>Catalyst</td><td>T (C)</td><td>Time (h)</td><td>Solvent</td><td>Conc. (mM)</td><td>Mn (g/mol)</td><td>Mw (g/mol)</td><td>PDI (Mw/Mn)</td><td>Precip.</td><td>Yield (%)</td></tr><tr><td>1</td><td>TEA</td><td>25</td><td>24</td><td>THF</td><td>398</td><td></td><td></td><td>_</td><td>_</td><td>-</td></tr><tr><td>２</td><td>TEA</td><td>50</td><td>22</td><td>THF</td><td>398</td><td>10,800</td><td>18,000</td><td>1.66</td><td>EA/Hex</td><td>84</td></tr><tr><td>3</td><td>TBAF</td><td>25</td><td>24</td><td>THF</td><td>398</td><td>10,600</td><td>23,600</td><td>2.22</td><td>Ether</td><td>48</td></tr><tr><td>4</td><td>TBAF</td><td>50</td><td>22</td><td>THF</td><td>398</td><td>7,500</td><td>11,700</td><td>1.55</td><td>Ether</td><td>48</td></tr><tr><td>５</td><td> DBU</td><td>25</td><td>22</td><td>THF</td><td>398</td><td>6,200</td><td>10,800</td><td>1.74</td><td>EA/Hex</td><td>78</td></tr><tr><td>6</td><td>LiOH</td><td>25</td><td>24</td><td>THF/H2O</td><td>398</td><td>41,100</td><td>75,900</td><td>1.84</td><td>Ether</td><td>52</td></tr><tr><td>7</td><td>LiOH </td><td>25</td><td>3</td><td>H2O</td><td>398</td><td>13,200</td><td>26,800</td><td>2.03</td><td>Ether</td><td>20</td></tr><tr><td>8</td><td>LiOH</td><td>50</td><td>22</td><td>THF/H2O</td><td>398</td><td>15,900</td><td>28,500</td><td>1.79</td><td>EA/Hex</td><td>60</td></tr><tr><td>９</td><td>TEA</td><td>25</td><td>20</td><td>THF</td><td>792</td><td>一</td><td>一</td><td></td><td></td><td></td></tr><tr><td>10</td><td>TEA</td><td>50</td><td>20</td><td>THF</td><td>792</td><td>9,400</td><td>16,600</td><td>1.76</td><td>EA/Hex</td><td>83</td></tr><tr><td>11</td><td> TBAF</td><td>25</td><td>20</td><td>THF</td><td>792</td><td>9,300</td><td>16,800</td><td>1.80</td><td>EA/Hex</td><td>68</td></tr><tr><td>12</td><td>LiOH</td><td>25</td><td>20</td><td>THF/H2O</td><td>792</td><td>23,100</td><td>46,800</td><td>2.02</td><td>Ether</td><td>72</td></tr><tr><td>13</td><td>LiOH</td><td>25</td><td>3</td><td>H2O</td><td>792</td><td>20,700</td><td>39,500</td><td>1.90</td><td>EA/Hex</td><td>38</td></tr><tr><td>14</td><td>LiOH</td><td>25</td><td>14</td><td>Bulk</td><td>-</td><td>23,200</td><td>47,700</td><td>2.02</td><td>EA/Hex</td><td>99</td></tr><tr><td>15</td><td>LiOH </td><td>25</td><td>24</td><td>Bulk</td><td>-</td><td>24,600</td><td>51,300</td><td>2.08</td><td>EA/Hex</td><td>93</td></tr></table></body></html>\n\n$7\\:\\mathrm{mol\\%}$ of the catalyst was used except in entries 2, 9, and 10 in which the catalyst was used as a co-solvent (1:1 vol/vol); molecular weight determination was done through gel permeation chromatography (GPC) using polystyrene standards; precipitation was carried out either in diethyl ether or a $25\\%$ ethyl acetate (EA) in hexane (Hex) solvent mixture.  \n\n![](images/5323594e6af34d896c6452944c8b588fc2c14689dcdd9b72b5e74c787999de92.jpg)  \nFIGURE 3 GPC traces of purified polymer 4 (solid line $\\c=$ entry 15, dash line $\\O=$ entry 14, dash dot line $\\O=$ entry 10, and small dash line $\\O=$ entry 11 in Table 1).  \n\nInitially, triethylamine (TEA) was used as a catalyst due to its mild nature. However, no polymer formation was observed in this reaction at room temperature. Therefore, the reaction temperature was increased to $50~^{\\circ}\\mathrm{C}$ and TEA was used as a co-solvent. These changes resulted in the formation of polymer 4. However, the molecular weight of the generated polymer remained low $(M_{\\mathrm{w}}=18,000$ , $M_{\\mathrm{n}}=10{,}800$ $\\mathrm{g/mol}\\mathrm{\\Delta}$ . The polymerization catalyst was then changed to tetrabutylammonium fluoride (TBAF). TBAF is soluble in a variety of organic solvents as well as water, and known to be a good catalyst for the thiol-epoxy reaction.11(e),17 In the presence of TBAF, polymer formation could be observed at room temperature. The molecular weight of the polymer, however, still remained low $(M_{\\mathrm{w}}=16,800$ , $M_{\\mathrm{n}}{=}9300~\\mathrm{g/mol})$ . Increasing the reaction temperature did not alter the outcome of the polymerization reaction. Therefore, lithium hydroxide was used as the polymerization catalyst. This catalyst has been used with significant success for the thiol-epoxy coupling reaction in small molecular18 as well as polymeric11(a– c) systems. This reaction produced a relatively higher molecular weight polymer $(M_{\\mathrm{w}}=28,500$ , $M_{\\mathrm{n}}{=}15{,}900\\mathrm{g/mol})$ . Encouraged by these results, bulk polymerizations were carried out using LiOH as the polymerization catalyst. This, however, required the use of a mechanical stirrer due to the high viscosity of the polymerization mixture. These polymerizations produced high molecular weight polymers $(M_{\\mathrm{w}}=47,700$ , $M_{\\mathrm{n}}{}=23,200~\\mathrm{g/mol})$ with quantitative polymerization yields in a highly reproducible fashion. In general, the molecular weights produced via polymerization of an AB monomer (Fig. 3) were found to be significantly higher (Table 1) than the molar mass of the polymers obtained through an AA/BB route.11(c)  \n\nIn $^1\\mathrm{H}$ NMR spectroscopy, upon polymerization, the epoxide proton resonance (designated $\\mathrm{^{\\prime}g^{\\prime}}$ in Fig. 1) at $3.2~\\mathrm{ppm}$ shifted to about 3.9 ppm (designated ‘e’ in Fig. 4) due to the opening of the epoxide ring and subsequent formation of the hydroxyl group. The hydroxyl group formation was also evident through IR spectroscopy in which a broad band could be observed at $3450~\\mathrm{cm}^{-1}$ (Fig. 5). MALDI-TOF mass spectrometry measurements showed an expected peak interval of 252 Da corresponding to the molecular weight of the repeat unit in polymer 4 (Fig. 6).  \n\n![](images/84177cd6a65416191c81da22e7950e4627e3734c5ab8de0212db0444ebeb5665.jpg)  \nFIGURE 4 $^1\\mathsf{H}$ NMR of polymers 4 (bottom) and 5 (top) in $\\mathsf{C D C l}_{3}$ . TMS was used as an internal standard.  \n\n![](images/ee71f9a89f0ad3f959f9ec0ba5617dfa997108ac134c761e9260dcd4ef05517c.jpg)  \nFIGURE 5 IR spectra of polymers 4 (top) and 5 (bottom).  \n\nThe hydroxyl groups of polymer 4 (Entry 6, Table 1) could be used as an anchor point to install functional groups to the polymer backbone. To demonstrate this, a fluorescent moiety, pyrene, could be attached to the polymer chain through an esterification reaction. The postfunctionalization conversion of the hydroxyl to ester group was determined to be $85\\mathrm{-}90\\%$ by comparing the area integration of signals located at 3.9 (precursor polymer 4) and $5.1\\ \\mathrm{ppm}$ (functionalized structure 5) (Fig. 4). In the IR spectra, a decrease in the intensity of the broad hydroxyl band at $3450~\\mathrm{cm}^{-1}$ and the appearance of an ester-carbonyl signal at $1710~\\mathrm{{cm}}^{-1}$ (Fig. 5) were observed after the functionalization reaction. These data supported the structure determined by the $^1\\mathrm{H}$ NMR spectroscopy. UV–vis spectroscopy further established the presence of pyrene units in polymer 5 as this polymer exhibited absorption bands in the range of $225\\substack{-375}\\ \\mathrm{nm}$ (Fig. 7). Due to functionalization with a pyrene chromophore, polymer 5 exhibited fluorescence emission properties upon excitation at $347\\ \\mathrm{nm}$ (Fig. 8). The fluorescence emission spectrum of polymer 5 was comprised well-defined bands at 376, 397, and $424\\ \\mathrm{nm}$ belonging to the pyrene monomer, and a broad and structure-less band centered at $483\\ \\mathrm{nm}$ belonging to the pyrene excimer. Thermal analysis indicated that the polymers were stable up to $290{-}295^{\\circ}\\mathrm{C}$ . A significant difference was observed in the glass transition property of the polymers. Polymer 4 exhibited a $T_{\\mathrm{g}}$ of $-51~^{\\circ}\\mathrm{C}$ (Supporting Information Fig. S2). As expected, substitution with the pyrene group increased the $T_{\\mathrm{g}}$ in polymer 5 to $-33\\ ^{\\circ}\\mathsf{C}$ . MALDI-TOF mass analysis further confirmed the molecular structure of the repeat unit in polymer 5 (Supporting Information Fig. S3).  \n\n![](images/91565d3073df1f28e27648f6c3d0c8df024314e648cb119eb51862056f73d99f.jpg)  \nFIGURE 6 MALDI-TOF mass spectra of polymer 4 (entry 15 in Table 1).  \n\n![](images/6db5ee729e54095a040c3bf5ee1f21364c969f159a5d1e8db7587d9c19c6f6ed.jpg)  \nFIGURE 7 UV–vis spectra of pyrene-functionalized polymer 5 in chloroform.  \n\n![](images/06b82edca1ab1759e36c1443fa1e300c1be5b868e553c46807df1a0a3a17581f.jpg)  \nFIGURE 8 Fluorescence emission spectrum of polymer 5 upon excitation at $347~\\mathsf{n m}$ .  \n\n![](images/8579520c33adedc3e9011071453f18593d45ca3aaca2ba0d02181d8e0d3d5afe.jpg)  \nFIGURE 9 $^1\\mathsf{H}$ NMR of polymers 6 in DMSO- $\\cdot{\\mathsf{d}}_{6}$ (bottom) and ${\\mathsf{D}}_{2}{\\mathsf{O}}$ (top).  \n\nTo demonstrate the generality of the reactive scaffold, the secondary hydroxyl groups of polymer 4 (Entry 15, Table 1) were functionalized with the $t$ -butoxycarbonyl (Boc)-protected glycine molecule. A successful functionalization was evident by the appearance of a signal at $5.1\\ \\mathrm{ppm}$ from the proton located adjacent to the newly formed ester group and the proton resonance signal of the Boc unit at $1.4~\\mathrm{ppm}$ (Supporting Information Fig. S4). Finally, the Boc groups could be removed under acidic conditions. This gave rise to a polymer carrying a primary ammonium site alongside the polymer backbone. In deuterated dimethylsulfoxide $\\left(\\mathrm{DMSO-}d_{6}\\right)$ ), the ammonium signal could be observed at 8.4 ppm. This functionalized cationic polymer (6) was completely soluble in water (Fig. 9). Therefore, $^1\\mathrm{H}$ NMR study could also be carried out in deuterated water $\\left(\\mathsf{D}_{2}0\\right)$ , which confirmed that the signal at $8.4~\\mathrm{ppm}$ in DMSO- $\\cdot d_{6}$ belonged to the ammonium group as it could no longer be observed in $\\mathtt{D}_{2}0$ due to a fast exchange with deuterium.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 3,
+        "chunk": "# CONCLUSIONS  \n\nIn conclusion, a synthetic route is developed for the preparation of an AB type of monomer suitable for thiol-epoxy polymerization. For this, a thiol unit of bis-mercaptoethyl ether was coupled to the alkene functionality of allyl glycidyl ether in a free radical fashion. This afforded the desired monomer carrying the two reactive groups—a thiol and an epoxide— necessary for the thiol-epoxy polymerization reaction. A systematic variation in the reaction conditions suggested that TBAF, LiOH, and DBU were good polymerization catalysts. TEA, on the other hand, required higher temperatures and an excess amount to produce polymers. THF and water could be used as polymerization mediums. The best results, however, were obtained in bulk conditions. This, however, necessitated the use of a mechanical stirrer due to the high viscosity of the polymerization mixture. The synthesized polymers could be converted into a fluorescent or a cationic structure through postpolymerization modification reaction of the hydroxyl units. The functionalized polymers exhibited substituent dependent properties. Most importantly, the molecular weight of the polymers resulting from the present AB monomer route was found to be significantly higher than the molecular weight of the polymers prepared through a previously reported AA/BB approach.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 4,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nFinancial support from SNSF is acknowledged. AK thanks A. D.   \nSchl€uter for support.",
+        "category": " References"
+    },
+    {
+        "id": 5,
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Binauld, M. Ibert, P. Fuertes, J.-P. Pascault, E. Fleury, J. Bernard, E. Drockenmuller, Macromolecules 2010, 43, 17–19; (g) A. Qin, J. W. Y. Lam, B. Z. Tang, Macromolecules 2010, 43, 8693–8702; (h) A. Qin, J. W. Y. Lam, B. Z. Tang, Chem. Soc. Rev. 2010, 39, 2522–2544; (i) H. Li, J. Wang, J. Z. Sun, R. Hu, A. Qin, B. Z. Tang, Polym. Chem. 2012, 3, 1075–1083; (j) J. Wang, J. Mei, R. Hu, J. Z. Sun, A. Qin, B. Z. Tang, J. Am. Chem. Soc. 2012, 134, 9956–9966; (k) J. Han, D. Zhu, C. Gao, Polym. Chem. 2013, 4, 542–549.   \n10 For linear polymer synthesis through thiol-ene reaction, please see; (a) H. Mutlu, A. N. Parvulescu, P. C. A. Bruijnincx, B. M. Weckhuysen, M. A. R. Meijer, Macromolecules 2012, 45, 1866–1878; (b) C. Lluch, J. C. Ronda, M. Gali\u0002a, G. Lligadas, V. C\u0003adiz, Biomacromolecules 2010, 11, 1646–1653; (c) O. Tu€r€unc¸, L. M. Espinosa, M. A. R. Meier, Macromol. Rapid Commun. 2011, 32, 1357–1361; (d) J. W. Robinson, H. Schlaad, Chem. Commun. 2012, 48, 7835–7837; (e) J. Vandenbergh, K. Ranieri, T. Junkers, Macromol. Chem. Phys. 2012, 213, 2611–2617; (f) F. Deubel, V. Bretzler, R. Holzner, T. Helbich, O. Nuyken, B. Rieger, R. Jordan, Macromol. Rapid Commun. 2013, 34, 1020– 1025; (g) O. Berg, T. Dispinar, B. Hommez, F. E. D. Prez, Eur. Polym. J. 2013, 49, 804–812; (h) K. Dan, S. Ghosh, Polym. Chem. 2014. doi:10.1039/C4PY00078A.   \n11 (a) S. De, A. Khan, Chem. Commun. 2012, 48, 3130–3132; (b) S. De, C. Stelzer, A. Khan, Polym. Chem. 2012, 3, 2342–2345; (c) A. Bra€ndle, A. Khan, Polym. Chem. 2012, 3, 3224–3227; (d) I. Gadwal, A. Khan, Polym Chem. 2013, 4, 2440–2444; (e) N. Cengiz, J. Rao, A. Sanyal, A. Khan, Chem. Commun. 2013, 49, 11191–11193; (f) I. Gadwal, J. Rao, J. Baettig, A. Khan, Macromolecules 2014, 47, 35–40; (g) S. P. Li, J. Han, C. Gao, Polym. Chem. 2013, 4, 1774–1787; (h) S. Li, C. Gao, Polym. Chem. 2013, 16, 4450–4460; (i) J. S. Basuki, L. Esser, H. T. T. Duong, Q. Zhang, P. Wilson, M. R. Whittaker, D. M. Haddleton, C. Boyer, T. P. Davis, Chem. Sci. 2014, 5, 715–726.   \n12 For application of thiol/epoxy chemistry on surfaces, see: (a) R. Iwata, R. Satoh, Y. Iwasaki, K. Akiyoshi, Colloid and Surface B: Biointerfaces 2008, 62, 288–298; (b) S. B. Rahane, R. M. Hensarling, B. J. Sparks, C. M. Stafford, D. L. Patton, J. Mater. Chem. 2012, 22, 932–943.   \n13 For application of thiol/epoxy chemistry for nanoparticle functionalization, see: X. J. Song, J. Hu, C. C. Wang, Colloid Surf. A: Physicochem. Eng. Aspects 2011, 380, 250–256.   \n14 For application of thiol/epoxy chemistry for network synthesis, see reference 11e and; (a) J. A. Carioscia, J. W. Stansbury, C. N. Bowman, Polymer 2007, 48, 1526–1532; (b) Y. Jian, Y. He, Y. Sun, H. Yang, W. Yang, J. Nie, J. Mater. Chem. 2013, 1, 4481–4489; (c) M. Pepels, I. Filot, B. Kluperman, H. Goossens, Polym. Chem. 2013, 4, 4955–4965.   \n15 (a) W. H. Carothers, Chem. Rev. 1931, 8, 353–426; (b) G. Odian, Principles of Polymerization, Wiley: New York, 1991. 16 Please see page 388 of the following review article for more details: F. R. Mayo, C. Walling, Chem. Rev. 1940, 27, 351–412. 17 D. Albanese, D. Landini, M. Penso, Synthesis-Stuttgart 1994, 34–36.   \n18 N. Azizi, A. Khajeh-Amiri, H. Ghafuri, M. Bolourtchian, Phosphorous Sulfur Silicon 2010, 185, 1550–1557.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "Article",
+        "category": "the provided text segment \"Article,\" it is not possible to determine the specific content or context of the segment, as \"Article\" does not provide any information about hydrophilic polymers or their context within a paper. If you have a specific segment that contains more detailed information related to hydrophilic polymers, please provide that text for a more accurate classification. \n\nFor the text segment provided, here is the classification:\n\nCategory: References"
+    },
+    {
+        "id": 2,
+        "chunk": "# Fast UV-Curable Zwitter-Wettable Coatings with Reliable Antifogging/Frost-Resisting Performances  \n\nHao Zhong 1,2, Xiaoxiao Liu 2, Boxin Yu $3\\textcircled{\\mathbb{P}}$ and Shengzhu Zhou 4,\\*  \n\nCitation: Zhong, H.; Liu, X.; Yu, B.; Zhou, S. Fast UV-Curable Zwitter-Wettable Coatings with Reliable Antifogging/Frost-Resisting Performances. Biomimetics 2022, 7, 162. https://doi.org/10.3390/ biomimetics7040162  \n\nAcademic Editors: Zhengzhi Mu and Wenxin Cao  \n\nReceived: 2 September 2022   \nAccepted: 10 October 2022   \nPublished: 13 October 2022  \n\nPublisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.  \n\nCopyright: $\\circledcirc$ 2022 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/).  \n\n1 Agriculture College, Yanbian University, Yanbian 133002, China   \n2 Institute of Animal Husbandry and Veterinary Medicine, Jilin Academy of Agricultural Sciences, Changchun 130119, China   \n3 Department of General Practice, The First Hospital of Jilin University, Changchun 130021, China   \n4 Department of Anesthesiology, The Second Hospital of Jilin University, Changchun 130061, China Correspondence: zhoushengzhu@jlu.edu.cn  \n\nAbstract: Antifogging surfaces with unique properties to migrate severe fog formation have gained extensive interest, which is of particular interest for transparent substrates to obtain high visibility and transparency. To date, a large number of strategies including superhydrophilic or superhydrophobic surfaces and titanium dioxide $\\mathrm{(TiO}_{2}\\mathrm{)}$ )-based composite coatings have been developed based on different mechanisms. Although these surfaces exhibit effective antifogging properties, the rigid nanostructures, cumbersome preparation, and the need for UV light excitation largely limit their widespread applications. Herein, we report a zwitter-wettable antifogging and frost-resisting coating through a fast UV-curable cross-linking of copolymer with benzophenone groups. A series of random copolymers consisting of hydrophilic hydroxyethyl methacrylate (HEA), hydrophobic methyl methacrylate (MMA), and benzophenone-based acrylate units are developed by thermally triggered free-radical polymerization. Upon UV light irradiation, a highly efficient antifogging/frost-resisting coating is covalently bonded on a polycarbonate plate surface, maintaining a light transmission higher than $85\\%$ , which was confirmed in both high and low temperature anti-fog tests. Moreover, the wetting behaviors reveal that the antifogging performance exhibited by the zwitter-wettable surface mainly relies on its surface water-adsorbing capability to imbibe condensed water vapor on the surface outmost layer. Notably, the antifogging/frost-resisting behaviors can be well regulated by adjusting the hydrophilic/hydrophobic units, due to the proper balance between the wateradsorption and coating stability. Owing to its simplicity, low-cost preparation and high efficiency, this UV-curable acrylate antifogging coating may find a wide range of applications in various display devices in analytical and detection instruments.  \n\nKeywords: antifogging; frost-resisting; zwitter-wettable; UV illumination; acrylate coating",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# 1. Introduction  \n\nFogging and frosting are prevalent in nature and cause a lot of inconvenience to humans daily [1–10]. Owing to the rapid changes in temperature and humidity, saturated water vapor in the air condenses and forms fog droplets on the solid substrates [11]. The formation of fog droplets will not only cause surface wetting, but also has a great impact on the light transmission of the transparent materials, resulting in a significant reduction in their view clarity [12,13]. For example, the presence of a fog layer can largely reduce the solar energy conversion rate of solar panels [14–16]. Severe fog formation can blur the vision of vehicle drivers, which can easily cause traffic accidents [17]. In addition, in the field of medical testing, fogging of the testing lens during surgery can even cause catastrophic medical accidents [9,18]. So far, a large number of antifogging strategies have been designed and prepared to mitigate severe fogging and frosting. Among those, superhydrophilic surfaces that can get extremely low water contact angles within 0.5 s or less, have the ability to significantly reduce light scattering by allowing water to spread into a thin film [19,20]. For conventional superhydrophilic surfaces, both high surface energy and suitable roughness scales are extremely necessary to enhance the surface super-wetting behaviors [21]. Till now, various techniques such as plasma etching [22], layer-by-Layer (LbL) [23], templating method [24] have been adopted to develop the superhydrophilic antifogging surfaces. However, those techniques generally require either complicated procedures or special instruments to get the appropriate surface roughness. Additionally, the superhydrophilic surfaces can also be prepared by introducing the photochemically active materials (e.g., $\\mathrm{TiO}_{2}$ ) into its coating [25,26]. However, most of those coatings must be exposed under UV illumination to obtain the superhydrophilic anti-fogging properties. On the other hand, some superhydrophobic surfaces also displayed antifogging behaviors due to its super-repellency against water droplets [27–29]. Considering the micro-scale fog droplets formed on the surface, only some special superhydrophobic surfaces with precisely controlled roughness and topography can exhibit the qualified antifogging ability. Typical superhydrophobic surfaces are opaque and have very low light transmission, not to mention that the micro and nano structures are easily damaged and not easy to handle, all of which lead to difficulties in the application of the anti-fogging properties of superhydrophobic surfaces.  \n\nRecently, some coatings with zwitter-wettability have been reported to have good anti-fogging behavior [30–35]. Unlike the previously reported superhydrophilic or superhydrophobic surfaces, these zwitter-wettable coatings have moderate water absorption capacity. The anti-fogging mechanism of the coatings is believed to be that their coatings can strongly adsorb water vapor to their bulk materials rather than forming condensed water droplets on the surfaces, finally resulting in a totally clear coating surface. Some zwitterionic wettable coatings were prepared by grafting with oligomers consisting of perfluoroalkyl and polyethylene glycol (PEG) segments [36] or by a layer-by-layer (LbL) assembly method based on chitosan/Nafion systems [37]. More recently, some polymeric coatings with a semi-interpenetrating polymer network (SIPN) have been developed, through a binary or terpolymer acrylic polymers. Moreover, some zwitter-wettable coatings with both antifogging/antibacterial performances can also be developed by the combination of a cationic copolymer and a hydrophilic copolymer [38,39]. Although good anti-fog properties have been obtained for these coatings, there is still a strong demand for preparing these wettable coatings by a more rapid and convenient method.  \n\nAlthough the coatings exhibit effective antifogging performances because of the wateradsorbing behaviors, the inhaled water may turn into ice crystal under an extremely cold condition below the water freezing point, which inevitably decrease the light transmission. Nature always offers immense inspirations for creating functional material and surfaces. The roots of some overwintering plants, with high water content, can tolerate extremely cold temperatures. The key to this property is that the water present in the roots is in a nonfreezing or intermediate water states, thus avoiding the formation of ice crystal as well as the damage of plant cells [40–42].  \n\nInspired by this concept, we herein develop a zwitter-wettable acrylate coating with antifogging and frost-resisting performances through a facile UV-curable cross-linking of copolymer with benzophenone groups. Initially, a series of copolymers consisting of hydrophilic hydroxyethyl methacrylate (HEA), hydrophobic methyl methacrylate (MMA), and benzophenone-based acrylate (BP-Acrylate) units were synthesized by thermally triggered radical polymerization. The hydrophilic-hydrophobic balance of the copolymers can be well adjusted by adjusting the molar ratio of HEA/MMA. The structure and molecular weight of the prepared copolymers were investigated by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). Subsequently, the copolymers were coated on the surface of PC plates to obtain covalently bonded anti-fogging coatings under UV light. The anti-fog and anti-frost properties were investigated, and the antifogging mechanism was studied by surface wetting behavior.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2. Materials and Methods",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2.1. Materials  \n\nHydroxyethyl methacrylate (HEA, $98\\%$ ) and hydrophobic methyl methacrylate $(99\\%)$ were obtained from Aladdin (Shanghai, China). Control PC plates (BN-HFR, $2\\mathrm{mm}$ in thickness) were provided by Bornsun (Shenzhen Bornsun Industrial Co, Shenzhen, China). 4-Benzoylphenyl acrylate (4-BP acrylate, $98\\%$ ) was bought from Anhui Yousheng Biotechnology Company. $^{2,2^{\\prime}}$ -azobis(2-methylpropionitrile) (AIBN, $98\\%$ ) were purchased from Sigma-Aldrich (Shanghai, China). All solvents including N,N-dimethylformamide (DMF, $98\\%$ ), acetone $(99\\%)$ Tetrahydrofuran (THF, $98\\%$ ) were purchased from Aladdin (Shanghai, China). All other chemicals were analytical grade reagents and used without any further purification. Deionized water $(18.25\\mathrm{M}\\Omega\\mathrm{cm})$ ) was made in the laboratory.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.2. Synthesis of BP-Acrylate-Based Copolymers  \n\nA series of acrylate copolymers were synthesized via free radical copolymerization containing HEA, MMA, and 4-BP acrylate monomers, with AIBN as the thermal initiator. Three acrylate monomers of HEA $(3.0\\mathrm{g})$ , MMA $(7.0\\mathrm{g})$ and 4-BP acrylate $(0.5\\:\\mathrm{g})$ and AIBN (0.21g, ${\\sim}2\\%$ of total mass weight of monomers) were dissolved in $10~\\mathrm{mL}$ DMF to get a homogeneous solution. The mixture was maintained at $60^{\\circ}C$ for $^{12\\mathrm{h},}$ and then dialyzed against distilled water using 5 kDa MWCO dialysis tubing with a regenerated cellulose membrane for $24\\mathrm{h}$ with 3 water changes to remove the organic solvent and unreacted monomer. The sample was labeled as $\\mathrm{P}{-}30\\%$ according to the mass percentage of HEA $(30~\\mathrm{wt.\\%})$ to the total mass weight of HEA and MMA. Similarly, other products with different mass percentage of HEA (50, 70, and $90\\mathrm{wt.\\%}$ ) to the total mass weight of HEA and MMA were also prepared and labeled as $\\mathrm{P}{-}50\\%$ , $\\mathrm{P-}70\\%$ $\\mathrm{P-}90\\%$ , accordingly. All the purified copolymers $(\\mathrm{P}{-}30\\%$ , $\\mathrm{P}{-}50\\%$ , $\\mathrm{P-}70\\%$ $\\mathrm{P-}90\\%$ ) were dissolved in D6-DMSO to get a uniform solution, respectively. $^1\\mathrm{H-NMR}$ measurements were carried out on $400\\mathrm{MHzNMR}$ spectrometer from Bruker Biospin. About $100~\\mathrm{{mg}}$ of polymer was dissolved in $1\\mathrm{mL}$ in d6-DMSO solvent. The related chemical structures were characterized by the $^1\\mathrm{H}$ NMR spectra and the monomer unit ratios of the copolymer were also calculated by the peak integration values of the spectra.  \n\nAdditionally, number-average molecular weights (Mn) and molecular weight distributions (polydispersity index, $\\mathrm{PDI}=\\mathrm{Mw/Mn})$ of copolymers were determined by gel permeation chromatography (GPC) using a series of linear Tskgel Super columns (AW3000 and AW5000), with OPTILAB DSP Interferometric Refractometer (Wyatt Technology) as the detector. The eluent was DMF at a flow rate of $1.0\\mathrm{mL}\\mathrm{min}^{-1}$ . Monodispersed polystyrene standards were used to generate the calibration curve. The Mn of the copolymers was in the scope ranging from 63.4 to $79.1\\mathrm{kDa}$ , with the PDI in the range of 1.3 to 1.6.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.3. Preparation of Zwitter-Wettable Polymeric Coatings  \n\nThe PC plates were cut into rectangular pieces $(2.5\\times7.5\\mathrm{cm})$ , and then sonicated in ethanol and water and completely dried in a vacuum oven. The resultant copolymers were dissolved in acetone to get $10\\mathrm{\\:wt.\\%}$ solutions. After being immersed into the copolymer solution for $60{\\mathrm{~s}},$ , and suspended in the air for $20\\mathrm{s}.$ , the copolymer coated PC plates were illuminated by UV lamp for 3 min (300 W, $360\\mathrm{nm}$ , High-pressure mercury lamp, Kangxiao Photoelectric Technology) to get the UV curable coatings. The prepared coatings were washed by acetone, and dried in a vacuum oven at $80\\ ^{\\circ}C,$ which was nominated as $C{-}30\\%$ , $C{-}50\\%$ , $C{-}70\\%$ $C{-}90\\%$ , respectively.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.4. Antifogging and Frost-Resisting Evaluations  \n\nThe general anti-fogging properties were first tested by a warm breath. The following antifogging test in a high temperature was carried out as follows: A $250~\\mathrm{mL}$ beaker with $100~\\mathrm{{mL}}$ DI water was placed on a hot plate and the water was adjusted at $80~^{\\circ}C$ with thermocouple. When the water temperature is stable, the samples were placed the water vapor with the coated surface facing down. Moreover, the frost-resisting test was executed by storing the samples in a freezer at $-20{}^{\\circ}\\mathrm{C}$ for $^{2}\\mathrm{h},$ and then the samples were exposed to ambient conditions ( ${\\sim}20^{\\circ}\\mathrm{C},$ $30{-}40\\%$ relative humidity) to observe the frost formation. The surface fogging and frosting behaviors were evaluated by UV-Vis Spectrophotometer (Agilent Cary 60) with a light transmittance in the range of $400{-}700\\mathrm{nm}$ and the antifogging and frost-resisting phenomenon were recorded by digital camera. To maintain the consistency of experimental conditions, the exposure time was measured within 3 s after the sample was placed between the camera and the test images.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.5. Time-Dependent Surface Wetting Behavior  \n\nAccording to previously reported method [31], contact angle measurements over time were performed for the samples of $C{-}30\\%$ , $C{-}50\\%$ , $C{-}70\\%$ , and $C{-}90\\%$ , with a control PC plate a reference. About $10~\\upmu\\mathrm{L}$ water droplets were added to the sample surfaces, and then the changes of water contact angles as well as the wetting diameters over time were recorded every $4\\:s$ during the $80~\\mathrm{s}$ incubation period. By analyzing the changes of the contact angle values and the wetting diameters with time, the mechanism of the antifogging behavior for the zwitter-wettable surface can be explained.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.6. Coating Stability  \n\nThe resultant samples were subjected to three types of tests to evaluate their antifogging stability in different aggressive environments, including UV irradiation, water immersion, and thermal aging treatment. The optimal samples of $C{-}70\\%$ were chosen as the representative examples, the changes of the surface antifogging performances after the treatments were evaluated. UV irradiation test was conducted by exposing the coating to a UV lamp with a radiation intensity of $0.8\\mathrm{m}\\mathrm{W}\\mathrm{cm}^{-2}$ at $\\lambda=-360\\mathrm{nm}$ for $24\\mathrm{h}$ . For the water immersion test, the samples were socked in DI water $(45^{\\circ}\\mathrm{C})$ for $24\\mathrm{h}$ . Moreover, the coatings were placed in an oven at $100^{\\circ}\\mathrm{C}$ for $24\\mathrm{h}$ to conduct the thermal aging test.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3. Results and Discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3.1. Preparation and Properties of the Zwitter-Wettable Coatings  \n\nThe zwitter-wettable coating was successfully prepared according to the following procedure. First, the copolymers were synthesized by a thermally triggered free-radical polymerization reaction with the hydrophilic HEA, hydrophobic MMA and 4-BP-acrylate units. Herein, the 4-BP-acrylate groups were served as UV photo-initiator to immobilize the copolymer on the PC substrate surface. The mechanism of the UV triggered surface grafting is that the BP-based groups were excited under UV irradiation to a singlet state and jump to a triplet state which then underwent hydrogen-abstracting reaction from substrates while the resulting BP radicals tended to participate in coupling reaction to covalently bond the copolymers to the substrate surface [43]. By adjusting the mass percentages of the HEA/MMA, the surface zwitter-wettable behaviors can be well controlled. A great number of hydrophilic HEA units in the copolymer backbone could enhance its water adsorption capability, hence improving its antifogging performance. The Mn of the copolymers for $\\mathrm{P}{-}30\\%$ , $\\mathrm{P}{-}50\\%$ , $\\mathrm{P-}70\\%$ , $\\mathrm{P-}90\\%$ were 79.1 KDa, $71.3\\mathrm{KDa}$ , 69.2 KDa, and $63.4\\mathrm{KDa}$ , respectively, as determined form the GPC test.  \n\nThe chemical structures of the copolymer were investigated by H-NMR analysis (Figure 1a). The methylene $\\scriptstyle(\\mathrm{CO-CH}_{2}-\\mathrm{CH}_{2})$ resonance from polyHEA segment appears at $3.9\\mathrm{ppm}$ . The other methylene $(\\mathrm{-CH}_{2}\\mathrm{-CH}_{2}\\mathrm{-OF}$ H) and the methyl protons from poly(MMA) appeared at around $3.6\\mathrm{ppm}$ . Moreover, multiple proton peaks at around 6.8, 7.6, 7.8 ppm were attributed to the benzophenone groups. Taken together, those 1H NMR results confirmed the successful preparation of the copolymers. Additionally, the molar ratios of HEA/MMA/4-BP acrylate in copolymers were also roughly estimated by the peak intergration of the $^1\\mathrm{H}$ NMR spectra which were consistent with the initial feed ratio by conversion to mass fractions as mentioned before. After being treated under UV light irradiation and sufficient cleaning to eliminate the unbonded copolymers, the resulting coatings $(C{-}30\\%$ , $C{-}50\\%$ , $C{-}70\\%,$ and $C{-}90\\%$ ) were evaluated by ATR-FTIR spectroscopy to hcehemcikc atlhecochmepmoisciatliocnomofptohsietisounrfoafctehse(sFuirgfuacres1(bF)i.gTurhe1br).oaTdhebbarnodadatb3a5n4d0act $3540\\mathrm{cm}^{-1}$ rsotem thmein−gOfrHo smtrtehtec $-\\mathrm{OH}$ shtorewtcehdinogbsvhiouwseednohbavnioceusmenhtadnucemtoe int cdrueea steodinHcrEeaAs ecdonHteEnAt hceonctoepnotlsyinmtehrse cTohpeolCym=eOrs.stTrehtec $C=\\mathrm{O}$ satnredtscihninHg EbaAn,dMs iMnAH,EaAn,dM4-MBPA acnrydla4-teBPwaecrrey-a lbastervwedreatls\\~o17o3b0scermv−e1,diant ${\\sim}1730\\mathrm{cm}^{-1}$ , ipnrdeisceanticnegotfhethperecsoepncoleyomf tehrse conptohlyemseurbssotrnatehes ascuebs.strate surfaces.  \n\n![](images/1db9e77cb9559c779343de14d3db01d0dc10906ddcb32227a6fe2000934bbfed.jpg)  \niFgiugruere1.1. $^1\\mathrm{H}$ NMR sspecttra (a) and FT-IR specctrtraa( b( )b)ofofP(PH(HE EMA-Aco--coM-MAM)Aco)pcolpyomlyerms.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# .32..2.Antnitfiofogggiing Perfformances  \n\nBefeoforreeanttiiffogging test, the liighttttrranssmisisisoionnvavlauleuseosfotfhtehceocatoiantgisn $(C-30\\%$ ,0 $C{-}50\\%$ , $C{-}70\\%,$ and $C{-}90\\%$ ) were evaluated with the control PC plate as the reference, as displayed in Figure 2a. All the coatings demonstrated high light transmission values (more than $91\\%$ ), which were comparable to that of the bare PC plate $({\\sim}92\\%)$ . The results demonstrated that the introduced coatings on the surface possessed good light transparency, the coating trmattedritahlaitstehlfe idnotersondoutcceaducsoeatinygsigonitfihceanstulrifgahcteapbossosrepstsieodn gHoodwleivgehrt, tjruastnsthpraoruegnchya, osiatminplge bmreattehrifaolgigtisneglfexdpoersimneontt,caculseearadnifyfesriegnncieficnatnhte laingtihftogagbisnogrpteirofonr.mHaoncweeovfetrh,ej hsraomupglhe sausrifamcep lceanbrbeaftohufnodg.gCinogmepxarpedritomtehnet ,balucrlreadrpdiicftfuereonbcse irnvetdhebyatnhtiefcoogngtirnolglepnesr,f mtahnecseuroffatcehsetsraeamtepdlebsyuarnftaicfoegcgaingbceofaotiungds.foCrobmotphartheedgtogtghlesbalunrdregldaspsiecstusrheo wobesdecrlveeard hveiecwosntbreohlinledntsh,etlheen s(uFrifgaucres2tbr)e.  \n\nsAshoonewoefdthcleamrosvti eprwesvablehnitnda tuhreal epnhsen(Foimgeunrae 2fob)g.droplets can form on a variety of surfaces under the right conditions, which can trigger severe light reflection and refraction and reduce the light transmission of transparent substrates. Antifogging surfaces are often considered to be one of the most promising strategies for mitigating fog formation, but their performances can be significantly affected by different fogging environments. In this section, antifogging tests in either hot $(80^{\\circ}\\mathrm{C})$ fog conditions were first conducted, and the related antifogging performances were qualitatively and quantitatively recorded. As for the antifogging test, all the coated PC films were placed above $5\\mathrm{cm}$ over the hot water $(80^{\\circ}\\mathrm{C})$ for $60\\mathrm{{s}}$ with the coated side face down, the fogging images were recorded with a digital camera and the light transmission were examined by UV-vis spectrophotometer immediately (Figure 3a,b). For the control PC plates, a heavy fog layer rapidly appeared on the downside surface upon exposure to water vapor. Prolonging the exposure time to $60~\\mathrm{s}$ made these situation even worse, larger fog droplets stemming from the vapor condensation gradually appeared on the film surface, finally leading to a completely nontransparent film. The fog layer formed caused the background image blurred. When the exposure time was extended to $60\\ \\mathsf{s},$ dense droplets of fog gradually appeared on the film surface, finally resulting in a completely opaque film. For comparison, the coated samples exhibited quite different antifogging behaviors. The $C{-}30\\%$ and $C\\mathrm{-}50\\%$ samples showed good anti-fogging performance in the initial period of $_{5-6s}$ . As the incubation time was prolonged, a tendency of fog droplet formation and becoming larger began to appear on the surface. When prolonging the incubation time to $60~\\mathsf{s},$ , non-continuous hydration layers were formed on both two $C{-}30\\%$ and $C\\mathrm{-}50\\%$ surfaces. In contrast, both the $C{-}70\\%$ and $C{-}90\\%$ displayed remarkably enhanced antifogging performances in hot and humid environments.  \n\n![](images/c6e9105481438d2dac63e457f65b24bd7fa2fad3afd51fc66f8fa61649062382.jpg)  \nrEFeiWg2u.r(ea2) L(ai)gLhitgthrtatnrasnmsimsisisoion att the norrmalailnicnidciednteanntgalenfgolre vfaoriovuasrsiaomusplsesa umnpdlersaumnbdi7enrotf ictoiondnist.ioAnsn.tiAfnotgifgoignginpgeprefrofrormaance  of treatteeddlelnesnsursfuarcfeascaeftserafatesirmaplsei bmrpelatehbfroegagtihngftoegstgion tbhotehPthCe-bPaCs-ebadsegdogogleglse(s $\\scriptstyle(\\mathbf{b},\\mathbf{c})$ eyegllaassesseswiwthitohneolneenslecnoastecdoatnedthaenodthtehreuontchoearteud.n  \n\n![](images/cce4f0cf4945aaeb8d8c8f35e7502078b494a696f07d2d9b065cd6ff10e0a4c6.jpg)  \nFsiugrureet3i.m(ae) Pwhaotsoeixmtaegnesdoefdthteosa6m0psl,esd $C{-}30\\%$ , $C{-}50\\%$ , $C{-}70\\%$ , $C{-}90\\%$ ,dwuitahltlhyeacopnptreoalrPeCdploante acsea, rfeifneraelnlcye,raefsteurltbiening ienxpaocseodmtoplmeotiestlywaotperavqaupeorffilorm6.0Fso( $5\\mathrm{cm}$ ambopvaeriasn $80~^{\\circ}C$ ewactoeratbeatdh)s. (bi)teTdheqreuliateddligffhetrtreantsmainstsifoongogvierntghebreahnageviof $400{-}800~\\mathrm{{nm}}$ 3at0t%heanordmaCl-i5n0ci%denstaamngplleefsor resultant coatings with the control PC plate as reference.  \n\nThe antifogging properties of the sample surfaces were also evaluated quantitatively, by immediately collecting the light transmission over the range of $400{\\mathrm{-}}700\\ \\mathrm{nm}$ . The overall transmittance results are generally consistent with the anti-fog images, with all samples exhibiting very different light transmissions. Among these, the control PC plates exhibited relatively low transmittance values $({\\sim}34\\%)$ in the 400–800 range, compared to an initial value of ${\\sim}92\\%$ prior to the fogging test. For the coated samples, the antifogging performances of the samples were closely related to the contents of hydrophilic monomers in the copolymers, with a progressive increase in light transmission from $52\\%$ to $61\\%$ for $C{-}30\\%$ and $C\\mathrm{-}50\\%$ accompanied by an increase in HEA content. Previous reports have confirmed that the presence of hydrophilic components in the coating can effectively absorb the fog droplets formed on the surface [32]. More hydrophilic components in the coating will result in a stronger water absorption capability, which also enhances the surface antifogging performance. When the HEA mass percentage was increased to $70\\%$ , the $C{-}70\\%$ coating achieved ${\\sim}90\\%$ light transmission even after fogging test. However, by continually increasing the HEA mass content to $90\\%$ , the light transmission of the $C{-}90\\%$ showed a slight decrease in light transmission. This phenomenon may be due to the excessive content of hydrophilic component in the coating, which absorbs excessive water vapor and causes excessive swelling of the coating, finally resulting in a reduction of its surface light transmission. Therefore, $C{-}70\\%$ proved to be the optimal sample to get the superior antifogging effect against hot moist air.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.3. Frost-Resisting Performances  \n\nBesides the hot temperature antifogging performance, the frost-resisting property is also critical for a functional surface to get more broad antifogging applications. When water vapor in a humid environment comes into contact with a cold surface, the water vapor at the low temperature material interface becomes supersaturated and quickly condenses on the surface to form fog droplets first and subsequently turns into a frost layer due to the extremely low surface temperature. Since this type of frost layer is formed directly from condensed water droplets on the surface, it has a severe reflective and interfering behavior toward light, which greatly reduces the transmittance of visible light. To challenge a harsh fogging situation, the samples were stored in a refrigerator at $-20^{\\circ}C$ for $^{2\\mathrm{h}}$ and then exposed to the ambient condition $\\cdot{\\sim}20^{\\circ}\\mathrm{C},$ $35\\mathrm{-}40\\%$ relative humidity) (Figure 4a,b). When the control PC plates were transferred from an extremely cold environment to an ambient environment, a fog layer was formed on the surface immediately, which was then converted into a frost layer due to the cold temperature of the substrate. Both the fog and frost layers formed on the surface have serious impacts on the light transmission of the sample, and only a very blurred image can be observed through the control PC plate. In comparison, the coated samples showed varied surface frost-resisting performances. The $C{-}30\\%$ did not display substantial frost-resisting performance and the background image was very unclear. In contrast, the $C\\mathrm{-}50\\%$ showed an obviously enhanced frost-resisting behavior, while the $C{-}70\\%$ and $C{-}90\\%$ samples both displayed significantly enhanced frost-resisting performances, with no fog or frost layer present on the surface during the whole frosting test, although the $C{-}70\\%$ sample showed even superior clarity than that of the $C{-}90\\%$ . The light transmission confirmed that the frost-resisting performances of the samples were closely related to the hydrophilic HEA contents, both the $C{-}70\\%$ and $C{-}90\\%$ showed higher light transmissions than $88\\%$ . Similar to the antifogging results mentioned above, the coatings with excessive HEA will weaken the frost resistance. Previous studies have confirmed that excessive hydrophilic content in copolymer can lead to excessive water uptake by the coatings, which can produce inhomogeneous water domains during the frost formation at low temperatures, thus remarkably reducing the light transmission to certain extent [30].  \n\n![](images/daac1b468f56f3bba4761e14c473554b953043330ed8418261c9a0dacd7da3be.jpg)  \nFgiugruere4 .4(.a()a)PPhhoottooiimages of  the samples $C{-}30\\%$ , $C{-}50\\%$ ,% $C{-}70\\%$ ,% $C{-}90\\%$ ,%w, itwhithethceonctoronltrPoCl  PplCatpe as a reference, the samples were first stored in a refrigerator $(-20^{\\circ}\\mathrm{C})$ for $2\\mathrm{h},$ and the photo images were collected after being exposed to ambient conditions $(20^{\\circ}\\mathrm{C},30{-}35\\%$ relative humidity). (b) The related light transmission over the range of $400{-}800\\mathrm{nm}$ at the normal incident angle for resultant coatings with the control PC plate as reference.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 43.4S. uSrufrafcaeceWetetiting Behaviors  \n\nhTehewetetitninggprroperttiies of the sample surffacess haavveeaasisginginfiicfiacnatnetffefcftecotnotnhetihreairntai-n ofgogignigngpeprefrofrormaancnecse.s.AAmonogngthtehem,mt,htehesuspueprehrhyyddrorophiliiliccssurrfface  issussed  to acchiieve t ntthi-efaongtgi-ifnog gpienrgfopremrfaonrcmeabnycef obrymfionrgmiansgmaosomthooatnhdanudn iufonrifmorhmyhdryadtriaotniotnhitnhilnalyaeyrebrybyr rlaypsipdlryeasdpirneagdfiong dforgopdlreotsploetnstohnetshuerfsaucrfe,acwe,hiwlehitlheethseuspueprehryhdyrdorpohpohboibcicssuurfrafacceessrrepell the micro-sized fog droplets from the surface by using the unique super-repellence of the surface. To investigate the anti-fogging performance of the amphiphilic hydrophilic surface, the wettability of the sample surface with time was also investigated. To understand the anti-fogging mechanism of the zwitter-wettable coating surface, the time depended water CA values was monitored, and the changes of the CA values as well as the diameter cAhavnagleusesofwastermdornoitpolertedo,n athnedctohateincghasunrgfeasceofwetrhereCcAordveadluienseacsh $4\\:s$ linatsertvhael wditahmine $80\\mathrm{{s}}$ ienscoufbawtiaotnerpedriopdl(eFtiognurteh5e).c  \n\ncAusbsahtioown pienriFoigdu(rFei5gau,rtehe5)c.ontrol PC plate showed relatively high CA values ${\\sim}88^{\\circ}$ , and the CA values only showed a slight decrease during the incubation time of $80\\mathrm{{s}}$ . The result confirmed that the saturated water vapor tends to generate tiny droplets on the hydrophobic surface when it encounters a temperature change. The coated surface also exhibited relatively high initial contact angles, with CA values of ${\\sim}70^{\\circ}$ , $65^{\\circ}$ , $53^{\\circ}$ , and $49^{\\circ}$ for $C{-}30\\%$ , $C{-}50\\%$ , $C{-}70\\%$ , and $C{-}90\\%$ , respectively, which is quite different from typical superhydrophilic antifogging surfaces with very low water CA $(\\leq5^{\\circ})$ . These results confirm that an antifogging surface does not need to be superhydrophilic to diffuse condensed droplets into a thin water layer. It was noteworthy that the water CA value of the coated surface varied with time and decreases significantly during the incubation time. The CA of the water droplets on the bare PC plates surface decreased by only $3^{\\circ}$ during the 80 s incubation time of the water droplet on the surface. In contrast, the CA of the $C{-}30\\%$ dropped significantly, from an initial $65^{\\circ}$ to $50^{\\circ}$ , with a CA decrease of ${\\sim}15^{\\circ}$ . The continuous increase in the content of hydrophilic HEA units resulted in more pronounced decreases in CA values. More significant decreases in CA values, ${\\sim}20^{\\circ}$ , $29^{\\circ}$ , and $30^{\\circ}$ were observed on the $C{-}50\\%$ , $C{-}70\\%$ and $C{-}90\\%$ surfaces, respectively. These results indicated that the higher content of HEA units in the copolymer could result in a stronger water absorption capacity, which was closely related to the antifogging properties of the surface.  \n\n![](images/2aebe946d6b78081a0a63b55aadf9b83fcb178cc32f2799e86a7fccae5feae3d.jpg)  \niFgiugruere5 5(. )(aC) hCahnagnegsesofofwawtaetrercocnotnatcatctanagnlgeleoonnththeecocoataitninggssurfrfaacce witithiin $80~\\mathrm{s}$ incubatiion time. (b) Diameter changes of water droplet on coating surface within $80\\ \\mathrm{s},$ which was expressed as $\\Delta\\mathrm{D}/\\mathrm{Do},$ where $\\Delta\\mathrm{D}=\\mathrm{D}$ - Do and Do is the initial wetted diameter of the water droplet (time $=0$ s) and $\\mathrm{~D~}$ is the wetted diameter of the water droplet at certain time. All the data were the average of three times recorded in 4 s interval.  \n\nIsnsahdodwitinoin, tFhieguvraeri5atai,otnhoefcwonatrero ldProCplpeltatdeiasmheotwereodvrerltaitimveloynhtihgehcoCatAedvaslurefsac\\~e nwdatshaelsCoAe valaluateesdo(nFliygusrheo5wbe).dTahselicgohatedescruerfasce sduwritnhgmthoreeinHcEuAbactoiontnetnitmeexhoifbi8t0eds.aT esmuolrtecpornofniromunecdedthiantcrtehaesesiantuwreatteidngwdaiatemretvearpcormtpeanrdesdto tghenbearraetePtCinsyurfdarcoep. lAetms ong ythderom,pthoe $C{-}30\\%$ facned $C{-}50\\%$ istaemnpcloeusnstheorsweadt ${\\sim}22\\%$ rantdu $24\\%$ iancrgea.sTehine cwoetatiendg  sduiarfmaecte ra. xFhuirbtihterdirneclraetaisveliyn hHigEhAicnoitnitaelnctolendtatcot ancgolnetsi,nuwoituhs iCncArevasleuienswofet\\~ti7n0g° d6i5a°m, e5t3e°r, awnitdh ${\\sim}37\\%$ 0a%n ,d ${\\sim}43\\%$ ,inCc-r7e0as%e faonudndC-o9n0t%h,er $C{-}70\\%$ avneldy $C{-}90\\%$ hsiusrfqaucietse. dTifhfiesrepnhtefnromentyopni ufpuretrheyrdcronpfihrimliecdatnhteiffoagctgitnhagtstuhrefhacyedsrowpihtihlicveHrEyAlosewgwmeatnetrinCtAhe(c≤o5°a)t.inTghfeasceilirteasteusltshec adsorption of water, which leads to an expansion of the water wetting area. Together with the anti-fogging results, we can get the conclusion that this zwitterionic wettable coatings with a suitable hydrophilic-hydrophobic balance possess a suitable hydrophilichydrophobic balance and thus have excellent antifogging properties.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# h3e.58.0SsurifnaceuSbtatbiiolinty  \n\nrTohpepseudrfsaicgenipfriocapnertltiye,sfrof tmheancoiantiitinagl  6m5a°ytobe50af°f,ecwtietdh awhCeAn dexecproesaesdetofs\\~o1m5°e. hTahreshc nenuvoiursoninmcernetas(e .ign. tUheVcirornatdeinatiofn,hwyadtreorpihmilmicerHsiEonA, huenaitstrreeastumlteendt),inwhmicohreinptruornocuanc elecaredatsoesa iwneCakAenvianlgueosr.evMeonrleosisgonfifsiucrafnatc edaenctriefaosgegsining fCuAnctviaolnuseas,n\\~d2s0e°r,io2u9°s,lyaanfdfe3ct0°thwe blisfertivmeed ofnththeefuCn-c5t0io%n,alCs-7u0rf%acae.nTdoCv-e9r0if%y swuhreftahcers,trhesrpeescutlitvinelgys.aTmhpelsesrweseureltsafifnecdtiecda hbayt the ahibgohvertrceoanttmenetntosf, tHheE $C{-}70\\%$ ssianmtphle scowpeorleysmuebrjec toeudldtoreUsuVl irirnadaiastiron,gewratwera bismormpetrisoionnc,apnadcihteya,twtrheiacthmewnat,s rcelsopsecltyivrelya,taenddtothtehier saunrtfifaoceggaintigfopgrgoipnegrptireospoefr tihese  swuerfea quaIntitadtidvietliyons,tutdhie dv,aaricactoirodninogftowtahterabdorovep-lemtedntiiaomnetdearnotivfeorggtinmgeteosnt (tFhiegucroeat6e).dAsfuterrf $24\\mathrm{h}$ UV irradiation $(0.8\\mathrm{mW}\\mathrm{cm}^{-2}$ , $360\\mathrm{nm},$ , the $C{-}70\\%$ maintained more than $90\\%$ light transmission. The following fogging test confirmed that the antifogging performance of the UV-irradiated samples was slightly reduced compared to its initial antifogging behavior $({\\sim}90\\%)$ of the samples without UV irradiation, but still maintained a high light transmission rate of more than $87\\%$ . For those samples immersed in water bath for $24\\mathrm{h},$ and the surface 3s7til%l amnaidnt\\~a4i3ne%dirneclrateiavselyfohuignhdliognht threanCs-m70itt%anacned $(\\sim89\\%)$ , asnudrfalcseos.poTshsies spehdewniothmehingohnlyf hefrficioenftiarnmtiefdogtghiengfapcetrftohramt atnhcee.hyMdoroeopvheilri,cthHeEsaAmspelegsmaelsnot eixnhtibhietecdoeaxticnelglefnatctilhietratmeaslt dstsaobriplitiyoanftoefrwbeaitnegr,hweahtiecdhilneand sotvoenanat $100^{\\circ}\\mathrm{C}$ ifonr $24\\mathrm{h},$ ewiwtha ${\\sim}88\\%$ ltitginhtgtraarensa.mTisosgioetnhaefrterw hfeogagnitin-gfotgesgti.nTgorgestuhletrs, twhe acabnovgetretshuel tcsodneclmuosinostnrtahteadt thiastzthweittperreipoanriecdwseatmtapblles choavtei weitxhceallesnuti tcaobalteinhgysdtarobiplihtiyliac-nhdycdarnopmhaionbtiacinbsailganicfiecapnotsasenstisfoagsgiunitgapblreo pheyrtdireospehvielinca-fhtyerd hboeibnigc tbraelatendcebaynUdVthirursadhiatvieo ne,xcwealtlernitmanmteifrosigogni,nagndprhoepaetirntigetsr.eatment.  \n\n![](images/4be6adc5bd1d2ac431aef01e4dbc6a2a93712f4a7322c380da0a26bb712bec83.jpg)  \nFigure 6. Norrmalilized lgighthtrtarnasnsmimsisisoinonofotfhtehCe- $C{-}70\\%$ udnerdedriffdeirffeenrtetnrteattremaetnmtsenatnsdaintsdaintst faongtigfionggpienrfgorpemrafonrcems,anbcyese,xbpyoseixnpgotshiengsatmheplseasmtop lemsotisotmwoaitsetrwvatpeorrvfaorp o6r0fsor( $60\\mathrm{~s~}$ ( $5\\mathrm{cm}$ atbhoev8e0t°hCe $80~^{\\circ}C$ bwathe)r. bath).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 4. Conclusions  \n\nWe have successfully developed a zwitter-wettable antifogging and frost-resisting coatings, through a UV-curable copolymer consisting of HEA, MMA, and 4-BP acrylate. Owing to the introduced BP groups in the copolymer chains, the copolymers can be easily bonded on the PC substrate surface upon a convenient UV light irradiation. Because of the suitable hydrophilic-hydrophobic balance, the $C{-}70\\%$ was considered as the optimized sample, exhibiting both remarkably high antifogging and frost-resisting performances, with more than $85\\%$ light transmission. The antifogging mechanism beneath the coating as revealed by its time-dependent wetting behavior mainly relied on its surface wateradsorbing capability to imbibe condensed water vapor on the surface outmost layer, hence avoiding the surface fog formation. In addition, the stability of the coating was studied by exposing the coating to UV radiation, water immersion and heat treatment, and the results showed that the treated coatings still maintained good antifogging properties. Benefiting from the merits of simplicity, low-cost preparation, and high efficiency of the coating preparation, we believe that this UV-curable acrylate antifogging coating may find a wide range of applications in various display devices, ranging from goggles to medical detection devices.  \n\nAuthor Contributions: Formal analysis, methodology, original draft writing, H.Z.; conceptualization, investigation, X.L.; manuscript review, B.Y.; project administration, S.Z. All authors have read and agreed to the published version of the manuscript.  \n\nFunding: This research was funded by Science and Technology Development Plan Project of Jilin Province [No. YDZJ202201ZYTS123].  \n\nData Availability Statement: The data presented in this study are available upon request from the corresponding author.  \n\nConflicts of Interest: The authors declare no conflict of interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 18,
+        "chunk": "# References  \n\n1. Liu, X.; He, J. Progress in Antifogging Technology-from Surface Engineering to Functional Surfaces. Prog. Chem. 2010, 22, 270–276.   \n2. Feng, C.; Zhang, Z.; Li, J.; Qu, Y.; Xing, D.; Gao, X.; Zhang, Z.; Wen, Y.; Ma, Y.; Ye, J. A Bioinspired, Highly Transparent Surface with Dry-Style Antifogging, Antifrosting, Antifouling, and Moisture Self-Cleaning Properties. Macromol. Rapid Commun. 2019, 40, 1800708. [CrossRef] [PubMed]   \n3. Fu, D.; Chu, Z.; Fan, X.; Jia, Z.; Teng, M. Study on Surface Wetting Property Regulation of Greenhouse Film and its Antifogging Performance. J. Coat. Technol. Res. 2022, 19, 1199–1209. [CrossRef]   \n4. Liu, S.; Han, Y.; Qie, J.; Chen, S.; Liu, D.; Duo, L.; Chen, H.; Lin, Q. Environment Friendly Superhydrophobic and Transparent Surface Coating via Layer-by-layer Self-assembly for Antifogging of Optical Lenses. J. Biomater. Sci. Polym. Ed. 2022, 33, 847–857. [CrossRef]   \n5. Patel, P.; Choi, C.K.; Meng, D.D. 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Yang, L.; Huo, R.; Zhang, B. Dual Functional Coatings with Antifogging and Antimicrobial Performances for Endoscope Lens, via Facile Adsorption-cross-linking Strategy. Colloids Surf. B Biointerfaces 2021, 206, 111933. [CrossRef]   \n19. England, M.W.; Urata, C.; Dunderdale, G.J.; Hozumi, A. Anti-Fogging/Self-Healing Properties of Clay-Containing Transparent Nanocomposite Thin Films. ACS Appl. Mater. Interfaces 2016, 8, 4318–4322. [CrossRef]   \n20. Fromel, M.; Sweeder, D.M.; Jang, S.; Williams, T.A.; Kim, S.H.; Pester, C.W. Superhydrophilic Polymer Brushes with High Durability and Anti-fogging Activity. ACS Appl. Polym. Mater. 2021, 3, 5291–5301. [CrossRef]   \n21. Choi, M.; Xiangde, L.; Park, J.; Choi, D.; Heo, J.; Chang, M.; Lee, C.; Hong, J. Superhydrophilic Coatings with Intricate Nanostructure Based on Biotic Materials for Antifogging and Antibiofouling Applications. Chem. Eng. J. 2017, 309, 463–470. [CrossRef]   \n22. Mundo, R.D.; d’Agostino, R.; Palumbo, F. Long-Lasting Antifog Plasma Modification of Transparent Plastics. ACS Appl. Mater. Interfaces 2014, 6, 17059–17066. [CrossRef] [PubMed]   \n23. Zhang, L.; Li, Y.; Sun, J.; Shen, J. Mechanically Stable Antireflection and Antifogging Coatings Fabricated by the Layer-by-Layer Deposition Process and Postcalcination. Langmuir 2008, 24, 10851–10857. [CrossRef] [PubMed]   \n24. Liu, X.; Du, X.; He, J. Hierarchically Structured Porous Films of Silica Hollow Spheres via Layer-by-Layer Assembly and Their Superhydrophilic and Antifogging Properties. Chemphyschem 2008, 9, 305–309. [CrossRef]   \n25. Park, S.; Moon, H. Antifogging, Antireflective, and Highly Transparent Coatings Fabricated with SiO2 and TiO2 Nanoparticles. Sci. Adv. Mater. 2017, 9, 1560–1565. [CrossRef]   \n26. Zeman, P.; Takabayashi, S. Self-cleaning and Antifogging Effects of TiO2 Films Prepared by Radio Frequency Magnetron Sputtering. J. Vac. Sci. Technol. A Vac. Surf. Film. 2002, 20, 388–393. [CrossRef]   \n27. Gao, X.; Yan, X.; Yao, X.; Xu, L.; Zhang, K.; Zhang, J.; Yang, B.; Jiang, L. The Dry-Style Antifogging Properties of Mosquito Compound Eyes and Artificial Analogues Prepared by Soft Lithography. Adv. Mater. 2007, 19, 2213–2217. [CrossRef]   \n28. Yoon, J.; Ryu, M.; Kim, H.; Ahn, G.N.; Yim, S.J.; Kim, D.P.; Lee, H. Wet-Style Superhydrophobic Antifogging Coatings for Optical Sensors. Adv. Mater. 2020, 32, 2002710. [CrossRef]   \n29. Wang, N.; Wang, Q.; Xu, S. A Review on Applications of Superhydrophobic Materials in Civil Engineering. Adv. Eng. Mater. 2022, 24, 2101238. [CrossRef]   \n30. Zhao, J.; Meyer, A.; Ma, L.; Wang, X.; Ming, W. Terpolymer-based SIPN Coating with Excellent Antifogging and Frost-resisting Properties. RSC Adv. 2015, 5, 102560–102566. [CrossRef]   \n31. Zhao, J.; Meyer, A.; Ma, L.; Ming, W. Acrylic Coatings with Surprising Antifogging and Frost-Resisting Properties. Chem. Commun. 2013, 49, 11764–11766. [CrossRef] [PubMed]   \n32. Lee, H.; Alcaraz, M.L.; Rubner, M.F.; Cohen, R.E. Zwitter-Wettability and Antifogging Coatings with Frost-Resisting Capabilities. ACS Nano 2013, 7, 2172–2185. [CrossRef] [PubMed]   \n33. Bai, S.; Li, X.; Zhang, R.; Li, C.; Zhu, K.; Sun, P.; Zhao, Y.; Ren, L.; Yuan, X. Enhancing Antifogging/Frost-resisting Performances of Amphiphilic Coatings via Cationic, Zwitterionic or Anionic Polyelectrolytes. Chem. Eng. J. 2019, 357, 667–677. [CrossRef]   \n34. Tao, C.; Bai, S.; Li, X.; Li, C.; Ren, L.; Zhao, Y.; Yuan, X. Formation of Zwitterionic Coatings with an Aqueous Lubricating Layer for Antifogging/Anti-icing Applications. Prog. Org. Coat. 2018, 115, 56–64. [CrossRef]   \n35. Wang, W.; Lu, P.; Fan, Y.; Tian, L.; Niu, S.; Zhao, J.; Ren, L. A Facile Antifogging/frost-resistant Coating with Self-healing Ability. Chem. Eng. J. 2019, 378, 122173. [CrossRef]   \n36. Howarter, J.A.; Youngblood, J.P. Self-Cleaning and Next Generation Anti-Fog Surfaces and Coatings. Macromol. Rapid Commun. 2008, 29, 455–466. [CrossRef]   \n37. Lee, H.; Gilbert, J.B.; Angilè, F.E.; Yang, R.; Lee, D.; Rubner, M.F.; Cohen, R.E. Design and Fabrication of Zwitter-Wettable Nanostructured Films. ACS Appl. Mater. Interfaces 2015, 7, 1004–1011. [CrossRef]   \n38. Tang, R.; Muhammad, A.; Yang, J.; Nie, J. Preparation of Antifog and Antibacterial Coatings by Photopolymerization. Polym. Adv. Technol. 2014, 25, 651–656. [CrossRef]   \n39. Park, C.; Kim, T.; Kim, Y.-I.; Lee, M.W.; An, S.; Yoon, S.S. Supersonically Sprayed Transparent Flexible Multifunctional Composites for Self-cleaning, Anti-icing, Anti-fogging, and Anti-bacterial Applications. Compos. Part B: Eng. 2021, 222, 109070. [CrossRef]   \n40. Hatakeyama, T.; Naoi, S.; Iijima, M.; Hatakeyama, H. Locust bean gum hydrogels formed by freezing and thawing. Macromol. Symp. 2005, 224, 253–262. [CrossRef]   \n41. Hsiao, T.C. Plant Responses to Water Stress. Annu. Rev. Plant Physiol. 1973, 24, 519–570. [CrossRef]   \n42. Benlloch, M.; Arboleda, F.; Barranco, D.; Fernández-Escobar, R. Response of Young Olive Trees to Sodium and Boron Excess in Irrigation Water. HortScience 1991, 26, 867–870. [CrossRef]   \n43. Deng, J.; Wang, L.; Liu, L.; Yang, W. Developments and New Applications of UV-induced Surface Graft Polymerizations. Prog. Polym. Sci. 2009, 34, 156–193. [CrossRef]",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Terpolymer-based SIPN coating with excellent antifogging and frost-resisting properties†  \n\nJie Zhao,a Anthony Meyer,a Li Ma,b Xiaojun Wangb and Weihua Ming\\*a  \n\nDOI: 10.1039/c5ra21399a  \n\nwww.rsc.org/advances",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# Introduction  \n\nFogging and/or frosting can severely reduce visibility and transparency of a substrate because of the prism effect of small water droplets. Many coatings have recently been developed1–20 to mitigate fogging problems for various applications such as eyeglasses, cameras, mirrors, goggles, and display devices in analytical instrument. An extensively used strategy has been to apply a superhydrophilic coating, primarily due to its ability to signicantly reduce light scattering by only allowing water to condensate like a thin lm.8–19 However, it generally requires complicated procedures to fabricate textured surfaces8–16 or UV illumination17–19 for $\\mathrm{TiO}_{2}$ based coatings to obtain superhydrophilicity. Moreover, these superhydrophilic surfaces may fail to resist frost formation since ice would still form from the thin water layer when conditions are right.  \n\nIt has been recently demonstrated that antifogging behavior does not have to reply on superhydrophilicity and can be obtained by cleverly combining hydrophilic and hydrophobic segments in a coating.1,21–24 For instance, Youngblood et al. developed self-cleaning and antifogging coatings by  \n\nWe prepared an effective antifogging/frost-resisting coating by forming a semi-interpenetrating polymer network (SIPN) on the basis of a linear, random terpolymer poly(2-(dimethylamino)ethyl methacrylateco-N-vinylpyrrolidone-co-methyl methacrylate), poly(DMAEMA-co-NVP-co-MMA), and a network of poly(ethylene glycol dimethacrylate). The excellent antifogging/frost-resisting property was mainly attributed to a balanced hydrophilicity/hydrophobicity of the terpolymer with the optimal DMAEMA/NVP/ MMA molar ratio at 40/30/30. Compared to our previous work using poly(DMAEMA-co-MMA), the terpolymer-based coating demonstrated excellent antifogging property against both low- and hightemperature moist air, by eliminating the lower critical solution temperature related to the DMAEMA segments in the binary copolymer. By monitoring the coating thickness change during the fogging/ frosting test, it appeared that water molecules could rapidly be absorbed into and desorbed from the terpolymer-based coating, implying long-term effectiveness of the antifogging/frost-resisting coating.  \n\ncombining both peruoroalkyl groups and poly(ethylene glycol) (PEG) segments.21 Cohen and Rubner et al. designed and prepared zwitter-wettable coatings showing excellent antifogging/frost-resisting properties via layer-by-layer assembly involving PEG segments22 or a chitosan/cellulose complex.23 Compared to a superhydrophilic antifogging surface, the coatings with balanced hydrophilicity/ hydrophobicity can imbibe rapidly water molecules from the surrounding vapor, thus preventing the formation of water droplets on the coating surface.  \n\nRecently, we developed an effective antifogging/frostresisting coating on the basis of a semi-interpenetrating polymer network (SIPN) comprising a linear, binary acrylic copolymer poly(2-(dimethylamino)ethyl methacrylate-co-methyl methacrylate), poly(DMAEMA-co-MMA), and a cross-linked network due to ethylene glycol dimethacrylate (EGDMA).1 The SIPN coating showed excellent antifogging/frost-resisting properties against cold moist air; however, its antifogging performance became poor when exposed to hot moist air due to the lower critical solution temperature (LCST) associated with the DMAEMA segments.1 We envisage that partial replacement of the DMAEMA segments by another hydrophilic monomer may help eliminate the LCST effect in the binary copolymer poly(DMAEMA-co-MMA). Here we report the design and synthesis of a series of terpolymers, poly(2-(dimethylamino) ethyl methacrylate-co-N-vinylpyrrolidone-co-methyl methacrylate), poly(DMAEMA-co-NVP-co-MMA), and the subsequent preparation of antifogging/frost-resisting coatings on the basis of a SIPN from poly(DMAEMA-co-NVP-co-MMA) and PEGDMA against both cold and hot moist air.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# Experimental section",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# Materials  \n\nMonomers including DMAEMA $(98\\%)$ , $N$ -vinylpyrrolidone (NVP, $99\\%$ ), and EGDMA $(99\\%)$ were purchased from Aldrich, and MMA $(99\\%)$ was obtained from Alfa Aesar. Free radical initiators, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone (HHMP, $98\\%$ ) and azobisisobutyronitrile (AIBN, $99\\%$ ), were obtained from Aldrich. Solvents such as dimethylformamide (DMF), toluene, and chloroform were purchased from Fisher. All chemicals were used as received.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# Synthesis of poly(DMAEMA-co-NVP-co-MMA) terpolymer  \n\nAll terpolymers were synthesized by free radical polymerization. A typical procedure is described as follows. Three monomers, DMAEMA (4.8 g), NVP (4.5 g) and MMA $\\left(3.0{\\ g}\\right)$ (molar percentage: $30\\%$ DMAEMA, $40\\%$ NVP, and $30\\%$ MMA) were added into DMF in a $100~\\mathrm{{mL}}$ ask to obtain $10~\\mathrm{wt\\%}$ solution; then, the thermal initiator AIBN $[0.5\\mathrm{wt\\%}$ with respect to the total monomer mass) was added. Aer being purged by argon for $20\\ \\mathrm{min}$ , the polymerization was carried out at $70~^{\\circ}\\mathbf{C}$ for $^{24\\mathrm{~h~}}$ under magnetic stirring $\\left(200\\mathrm{\\rpm}\\right)$ . The nal terpolymer, designated as $\\mathrm{T}{-}30$ according to the DMAEMA molar percentage, was puried by dissolution in chloroform and precipitation in cyclohexane (twice), and dried in a vacuum oven. Similarly, other terpolymers were synthesized with the MMA amount xed at $30~\\mathrm{mol\\%}$ : T-40, $40\\%$ DMAEMA and $30\\%$ NVP; T-50: $50\\%$ DMAEMA and $20\\%$ NVP.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# Preparation of SIPN coatings  \n\nGlass slides $(1.5\\ \\times\\ 1.5\\ \\mathrm{cm}^{2})$ ) were sonicated consecutively in acetone and ethanol for $30\\mathrm{min}$ , followed by blow-drying with air. A terpolymer $(2.0\\mathrm{~g})$ , EGDMA $(0.5~\\mathrm{\\wt\\%}$ with respect to the terpolymer), and HHMP $2.0~\\mathrm{wt\\%}$ relative to EGDMA) were dissolved in toluene $\\mathrm{(20.0~mL)}$ to obtain a homogeneous solution. The mixture was then spun-coated on clean glass slides at various rates (400, 800, 1500 and $3000\\mathrm{rpm}$ ) for $15{\\mathrm{~s}}.$ The spun-coated lm was then cured under UV irradiation in a UVP CL-1000 ultraviolet cross-linker apparatus ( $365~\\mathrm{nm}$ , 15 W) for $45~\\mathrm{min}$ , and dried in a vacuum oven at $70~^{\\circ}\\mathrm{C}$ for $24\\mathrm{~h~}$ . The smooth SIPN coatings (on glass) based on terpolymers T-30, T-40, and $\\mathrm{T}{\\cdot}50$ were labelled as SIPN-T-30, SIPN-T-40, and SIPN-T-50, respectively. The root-meansquare (RMS) surface roughness of SIPN coatings was typically 2–3 nm over an area of $2\\times2~\\upmu\\mathrm{m}^{2}$ , as determined by atom force microscopy (AFM) on an NT-MDT NTEGRA Prima instrument in the semi-contact mode with a gold-coated cantilever NSG 10.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# Fogging/frosting test  \n\nAntifogging tests against hot moist air were conducted by holding the samples $5\\ \\mathrm{cm}$ above a hot water bath $(80~^{\\circ}\\mathbf{C})$ for different periods of time (15, 30, 45 and 60 s) with a glass as the control. A more aggressive fogging/frosting test was performed by placing these samples in a freezer at $-20{}^{\\circ}\\mathbf{C}$ for $30\\mathrm{min}$ and photographs were taken aer the samples were exposed to ambient conditions $({\\sim}20\\ ^{\\circ}{\\bf C}$ , $50\\%$ relative humidity) for 5 s. To evaluate the antifogging/frost-resisting performance more quantitatively, light transmission over the $400{\\mathrm{-}}700\\ \\mathrm{nm}$ range was collected on an Agilent 8453 UV-Vis spectrophotometer during fogging/frosting tests. To examine antifogging mechanism, time-dependent water contact angles on all SIPN coatings were collected on a Ram´e-Hart 290 instrument (every 10 s over 600 s period).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# Monitoring lm thickness change during fogging/frosting tests  \n\nLight transmission data collected from UV-Vis measurements were also used to monitor the coating thickness change for the coatings that remained to be transparent during fogging/ frosting tests. Refraction index and coating thickness were simultaneously determined by tting the interference fringes in the transmission prole, $T(\\lambda)$ , as a function of wavelength, $\\lambda,^{25}$  \n\n$$\nT(\\lambda)=\\frac{T_{\\mathrm{sa}}(\\lambda)T_{\\mathrm{afs}}(\\lambda)}{1-R_{\\mathrm{sfa}}(\\lambda)R_{\\mathrm{sa}}(\\lambda)},\n$$  \n\nwhere $T_{\\mathrm{sa}}(\\lambda)$ and $T_{\\mathrm{afs}}(\\lambda)$ are the interference upon transmissions through the substrate-air and air-lm-substrate systems, respectively, and $R_{\\mathrm{sfa}}(\\lambda)$ and $R_{\\mathrm{sa}}(\\lambda)$ are the interference upon reections from the substrate-lm-air and substrate-air systems, respectively. Both $T_{\\mathrm{afs}}$ and $R_{\\mathrm{sfa}}$ are dependent on the refractive index and thickness of the test lm.25 Transmission spectrum of the glass slide was also needed and measured before lm coating, which was tted to a two-coefficient Cauchy equation.26 Normal incidence on the test lm was adopted for measurement conguration. By curve tting the raw data, the coating thickness was determined according to eqn (1). This method provides a noninvasive and instantaneous measurement of thickness and refractive index of a transparent lm. The coating thickness was veried by AFM on an NT-MDT NTEGRA Prima instrument in the semi-contact mode.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# Other measurements  \n\nGlass transition temperature $\\left(T_{\\mathrm{g}}\\right)$ was measured on a TA Instruments DSC Q100 instrument, over the range of $-50$ to 120 ${}^{\\circ}\\mathbf{C}$ at a heating rate of $10^{\\circ}{\\bf C}\\operatorname*{min}^{-1}$ . NMR spectra were collected on an Agilent $400~\\mathrm{{MHz}}$ instrument with $\\mathbf{CDCl}_{3}$ as the solvent. Number-average molecular weight $\\left(M_{\\mathrm{n}}\\right)$ and polydispersity index, PDI $\\left(M_{\\mathrm{w}}/M_{\\mathrm{n}}\\right)$ of the terpolymers were determined by gel permeation chromatography (GPC) equipped with a Waters 515 HPLC pump and Water Styragel HT3/HT4 columns, using DAWN EOS 18-Angle Laser Light Scattering Instrument (Wyatt Technology) and OPTILAB DSP Interferometric Refractometer (Wyatt Technology) as detectors, with DMF as the elute (ow rate: $1\\mathrm{mL}\\mathrm{min}^{-1}$ , at room temperature); the molecular weights were calibrated with polystyrene standards.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# Results and discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# Preparation and properties of terpolymer poly(DMAEMA-coNVP-co-MMA)  \n\nAs mentioned earlier, we already developed SIPN coatings on the basis of a binary copolymer, poly(DMAEMA-co-MMA) with the optimal DMAEMA/MMA molar ratio at 70/30 and PEGDMA (0.5 $\\mathrm{wt\\%}$ relative to the copolymer), which demonstrated excellent antifogging/frost-resisting properties against cold moist air.1 However, due to the LCST associated with the DMAEMA segments, the antifogging performance became poor when the coating was exposed to hot moist air (the temperature of the water bath was 80 ${}^{\\circ}\\mathbf{C}]$ . A logical solution to this issue appeared to be to replace some of the DMAEMA segments with another hydrophilic monomer that, when polymerized, would not lead to a LCST while maintaining the desired hydrophilic/hydrophobic balance in a new terpolymer.  \n\nWe decided to incorporate a third, hydrophilic monomer, NVP, to partially replace DMAEMA to obtain the terpolymer (poly(DMAEMA-co-NVP-co-MMA), Scheme 1) and, subsequently, to form a SIPN coating comprising the terpolymer and a network of polymerized EGDMA $(0.5~\\mathrm{wt\\%}$ relative to the copolymer1). We rst synthesized terpolymers with balanced hydrophobicity and hydrophilicity from three monomers, DMAEMA, NVP, and MMA, by conventional free radical polymerization. The $M_{\\mathrm{n}}$ of the terpolymers, measured from GPC, was about 30 000 (Table 1). The molar ratio of the three monomeric units in the nal terpolymers, as determined via $\\mathbf{\\Omega}^{1}\\mathbf{H}\\mathbf{-}\\mathbf{NMR}$ , was in good agreement with the feed ratio (Table 1). It should be noted that a single glass transition temperature $\\left(T_{\\mathrm{g}}\\right)$ was observed for each of three terpolymers (Table 1), clearly pointing to the random distribution of the three monomeric units in the nal terpolymers. This is crucial for the terpolymers to be used in antifogging/frostresisting coatings, since a random copolymer would not lead to (micro)phase separation in the coating, thus ensuring optical clarity of the coating. In addition, the $T_{\\mathrm{g}}$ of the terpolymer could be easily tuned by varying its composition (Table 1): a higher NVP content, with the MMA content being xed at about $30\\mathrm{mol\\%}$ , led to a higher $T_{\\mathrm{g}}$ for the terpolymer.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# Antifogging performance against hot moist air  \n\nWe rst examined the antifogging performance of terpolymerbased coatings against hot moist air. Compared to the completely fogged control glass, different antifogging performances were observed on the SIPN-T coating surfaces. Aer 15 s exposure to the hot water vapor, no fogging was observed for both SIPN-T-30 and SIPN-T-40 (Fig. 1a). However, some fogging was observed for SIPN-T-50 (photo not shown). Exposure to hot moist air for longer periods of time further revealed difference between SIPN-T-30 and SIPN-T-40 (Fig. $1\\mathrm{c}\\ \\&\\ \\mathrm{d}$ , and video clip in $\\mathrm{ESI\\dagger}_{\\mathrm{\\Phi}}$ ): while SIPN-T40 clearly maintained high transparency, SIPN-T-30 did show some compromise in optical clarity (the le part of the sample, in particular) despite that its surface remained to be free of fog. The observed slight whitening for SIPN-T-30 resembles the water-blushing effect of a water-borne polymer coating,27,28 which is due to water sorption into the coating and subsequent formation of water domain. Therefore, the slightly reduced transparency of SIPN-T-30 (more below) aer exposure to hot moist air for more than 30 s may be attributed to the excessive water-absorbing capacity due to the larger amount of very hydrophilic NVP segments, which in turn might have led to the formation of free water domains in the coating.  \n\nTable 1 Properties of terpolymers synthesized by free radical polymerization   \n\n\n<html><body><table><tr><td></td><td colspan=\"2\">DMAEMA:NVP:MMA</td><td colspan=\"3\"></td></tr><tr><td>Terpolymer</td><td>Feed molar ratio</td><td>Final molar ratio</td><td>Mn</td><td>PDI</td><td>Tg (C)</td></tr><tr><td>T-30</td><td>30:40:30</td><td>27:39:34</td><td>33000</td><td>2.5</td><td>72</td></tr><tr><td>T-40</td><td>40:30:30</td><td>40:30:30</td><td>30000</td><td>2.3</td><td>61</td></tr><tr><td>T-50</td><td>50:20:30</td><td>48:20:32</td><td>31000</td><td>2.4</td><td>43</td></tr></table></body></html>  \n\nTo evaluate the antifogging performance more quantitatively, light transmission over the $400{\\mathrm{-}}700\\ \\mathrm{\\nm}$ range was collected before and aer all samples were exposed to hot moist air for $60~\\mathrm{s}.$ . Prior to the fogging test, SIPN-T-40 and SIPN-T-50 showed comparable light transmission, about $92\\%$ , to the control glass, indicating that the SIPN coating based on the random terpolymer had a negligible effect on the glass transmission (Fig. 2a), while for SIPN-T-30, the coating with the highest NVP content, there appeared to be slight reduction in light transmission, especially in the short wavelength range. Upon exposure to hot moist air for $60~\\mathrm{s}$ , the light transmission decreased to below $40\\%$ for the control glass (Fig. 2b), obviously due to severe fogging. For the three SIPN coatings, the light transmission appeared to strongly depend on the NVP content in the terpolymer (Fig. 2b): the largest reduction in light transmission was observed for SIPN-T-50 (from $92\\%$ to ${\\sim}60\\%$ ) and there was about $10\\%$ decrease for SIPN-T-30; in contrast, SIPN-T-40 maintained high light transmission $(\\sim90\\%)$ .  \n\n![](images/4ca24a1e1dc84b5df3f2ece01a4318a87911bbffc121ded6a054734c7436d000.jpg)  \nScheme 1 Chemical structure of a random terpolymer poly(DMAEMA-co-NVP-co-MMA), and the subsequent preparation of a SIPN coating on the basis of the terpolymer.  \n\n![](images/a67e73cc27727d737bb79cb982d2a9dca7b3b71ba1e59f8ef0e587a66cd93e8b.jpg)  \nFig. 1 Photos of different samples: (left) control glass, (middle) SIPNT-40, and (right) SIPN-T-30: (a) $15\\mathsf{s,}$ (b) $30\\mathsf{s},$ (c) 45 s and (d) 60 s after exposure to hot moist air (5 cm above a $80~^{\\circ}\\mathsf{C}$ water bath) under ambient lab conditions $(\\sim20^{\\circ}\\mathsf C,$ $50\\%$ relative humidity).  \n\nThe poor antifogging performance for SIPN-T-50 was likely due to the relatively high DMAEMA content $(\\sim50\\mathrm{\\mol\\%})$ in the terpolymer $\\mathrm{T}{\\cdot}50$ , which might have failed in overcoming the LCST effect in the binary copolymer poly(DMAEMA-co-MMA). Therefore, it appeared to be critical to reduce the total DMAEMA content in the terpolymer below a threshold to eliminate LCST. On the other hand, if there was too much NVP segments in the terpolymer (T-30), the SIPN coating may become too hydrophilic, potentially allowing free water domain to form which would in turn lead to light scattering and reduced light transmission27,28 (water blushing, as discussed above). Therefore, the DMAEMA/NVP molar ratio (with the MMA amount being xed) in the terpolymer played a vital role in designing effective antifogging coating, and the DMAEMA/NVP/MMA molar ratio of 40/30/30 has proven to the optimal ratio for excellent antifogging effect against hot moist air.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# Frost-resisting performance  \n\nThe frost-resisting performance was evaluated by visually examining the sample appearance 5 s aer it was taken out of a freezer at $-20{}^{\\circ}\\mathbf{C}$ for $30~\\mathrm{min}$ . The control glass lost its transparency completely (Fig. 3a), due to severe frosting that later turned into fog under ambient condition. For SIPN-T-30, some haziness was clearly seen (Fig. 3b), likely due to the presence of the free water domain (which might crystallize into ice initially), as discussed above. In sharp contrast, neither frost nor fog formation was observed on SIPN-T-40 that retained high transparency throughout the test (Fig. 3c and video clip in $\\mathrm{ESI\\dagger}$ .  \n\nLight transmission data were also collected for the samples undergoing the frost test. Not surprisingly, the control glass suffered the biggest drop in light transmission due to frosting (Fig. 4), followed by SIPN-T-30 for which only $70\\%$ transmission remained aer 5 s under ambient conditions. High transmission $(\\sim90\\%)$ was observed for SIPN-T-40, indicating that frost formation was completely suppressed. SIPN-T-50 also demonstrated acceptable frost-resisting performance with the transmission value at ${\\sim}88\\%$ (the LCST effect due to the DMAEMA segments was not a factor for frost-resisting property). Once again, the DMAEMA/NVP molar ratio in the terpolymer (with the MMA content being xed) had signicant impact on the frost-resisting performance of the coatings. The sample SIPN-T-40 appeared to have the optimal hydrophilic/ hydrophobic balance, allowing it to excel in both antifogging and frost-resisting performance.  \n\nSince the antifogging/frost-resisting property of our SIPN coating is directly related to its water-absorbing capability, we examined the inuence of coating thickness on the antifogging performance. A thicker coating, presumably with higher waterabsorbing capacity, would likely lead to better antifogging behavior. By adjusting the spin-coating rate, we were able to tune the thickness of SIPN-T-40 from $390\\pm30\\mathrm{nm}$ $3000~\\mathrm{rpm})$ , to $490\\pm20\\mathrm{nm}$ $(1500~\\mathrm{rpm})$ , $780\\pm50\\mathrm{nm}$ $\\left({800}~\\mathrm{rpm}\\right)$ , and $920\\pm$ 60 $\\left(400\\mathrm{rpm}\\right)$ , as determined by AFM. It turned out that only the thinnest coating of $390\\mathrm{nm}$ developed some haziness during the frosting test and the rest all demonstrated excellent antifogging/frost-resisting behavior. To guarantee good antifogging/frost-resisting performance for our SIPN coatings, the coating has to be sufficiently thick to be capable of absorbing, rapidly and fully, water molecules from the surrounding into the coating.  \n\n![](images/d7229ae832d8fc3a49ce48b1a0bac3d8ae6ae5a22f7d5d18d660d28a0b9c97d7.jpg)  \nFig. 2 Light transmission at the normal incident angle for various samples (a) before and (b) after 60 s exposure to hot moist air (5 cm above a 80 $^{\\circ}{\\mathsf C}$ water bath) under ambient lab conditions $(\\sim20^{\\circ}C,$ $50\\%$ relative humidity).  \n\n![](images/8fe456de5b0b59c7c64227aa2eef3487ab0dd2747bfb2020e4b279acb40be1b8.jpg)  \nFig. 3 Photos of different samples: (a) control glass, (b) SIPN-T-30, and (c) SIPN-T-40, which were first stored at $-20^{\\circ}\\mathsf C$ for $30\\mathrm{\\min}$ and then exposed for 5 s to ambient lab conditions ${\\mathrm{\\sim}}20^{\\circ}\\mathsf{C}.$ , $50\\%$ relative humidity).  \n\n![](images/f93d805aced3b6fca98d805fda3fc67a9dd9d7f87d8f416fca43258736a302fb.jpg)  \nFig. 4 Light transmission at the normal incident angle for various samples, exposed for $5s$ to ambient conditions ${\\mathrm{.}}{\\sim}20^{\\circ}\\mathsf{C}.$ , $50\\%$ relative humidity) after being stored at $-20^{\\circ}C$ for $30\\mathrm{\\min}$ .  \n\nIt should be noted that we also prepared SIPN coatings on the basis of a binary random copolymer poly(NVP-co-MMA) with varying NVP/MMA molar ratios. However, these coatings did not show antifogging/frost-resisting performance as good as SIPNT-40, probably due to the strong water-absorbing NVP segments in the copolymer that might have easily led to the formation of discrete free water domain, thus reducing light transmission.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# Surface wettability of SIPN coating  \n\nTo investigate the origin of the antifogging/frost-resisting property of the SIPN coatings, we collected time-dependent water contact angles (CA) on these samples under ambient conditions. The initial water CA on all SIPN coatings was greater than $60^{\\circ}$ , which signicantly differs with the CA (approaching $0^{\\circ^{\\circ}}$ ) on a superhydrophilic antifogging coating and reinforces the recent ndings from us1 and others21–24 that a coating does not have to be superhydrophilic to be effectively antifogging. During the 600 s time interval, the water CAs on all SIPN coatings showed a substantial decrease (Fig. 5a), much more than the decrease due to water evaporation (e.g., on the control glass). This clearly indicated that some water had been imbibed into the coating layer. The higher the NVP content in the terpolymer, the more signicant the CA decrease was observed $\\left(\\mathrm{SIPN–T–30}>\\mathrm{SIPN–T–40}>\\mathrm{SIPN–T–50}\\right)$ , which is consistent with the high water-absorbing capability of the hydrophilic NVP segments.  \n\nThe changes in the diameter of the water contact area on the sample surface were also simultaneously monitored (Fig. 5b). No change (even slight decrease) in the diameter was observed on the control glass, while the water contact diameter increased by about $9\\%$ for SIPN-T-50 over the 600 s period, similar to the increase we observed previously for the antifogging coating1 based on the binary copolymer poly(DMAEMA- $_{\\cdot c o}$ -MMA) (DMAEMA/MMA molar ratio: 70/30). On the other hand, the water contact diameter dramatically increased by ${\\sim}40\\%$ and $53\\%$ (Fig. 5b) for SIPN-T-40 and SIPN-T-30, respectively. Obviously, water molecules had diffused into these terpolymerbased SIPN coatings and led to signicant expansion of the droplet contact area with the coating surface. The much greater increase of the water contact diameter in these two coatings further indicated that the NVP segments in the terpolymer were indeed more “water-loving” than the DMAEMA segments. However, too many NVP units in the terpolymer would lead to too much water being imbibed into the coating and the formation of discrete free domain, thus compromising its antifogging performance (as in the case of SIPN-T-30). Therefore, the ability we render to a coating to allow rapid diffusion of water molecules into the coating, while not forming discrete water domain in the coating, appears to be the key in obtaining highly effective antifogging/frost-resisting coating, such as SIPN-T-40.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# Long-term effectiveness of SIPN coating  \n\nTo evaluate long-term effectiveness of our SIPN coatings, SIPNT-40 was subject to multiple cycles of fogging/frosting tests and a more practical, bathroom test. The optical transparency of the SIPN-T-40 coating maintained throughout the fogging/frosting test allowed us to monitor the variation of the coating thickness, as derived from the light transmission data.25 Aer the 920 nm thick SIPN-T-40 was stored at $-20\\ ^{\\circ}\\mathbf{C}$ for $30\\ \\mathrm{min}$ , it was exposed to ambient conditions ( ${\\bf\\sim}20^{\\circ}{\\bf C}$ , $50\\%$ relative humidity).  \n\n![](images/202b104f26c72ce0826637df086e9f9d53040957569709ecc73deccf84a4e36f.jpg)  \nFig. 5 (a) Water contact angle evolution on various samples as a function of time. (b) Diameter change of the water droplet on various samples over the $600\\ s$ period as expressed as $\\Delta D/D_{0}$ , where $\\Delta D=D-D_{0}$ , and $D_{0}$ and $D$ (shown in the inset) are the initial diameter (time zero) and the diameter at different times, respectively, of the wetted area by the water droplet.  \n\nThe coating thickness increased by $36\\%$ aer 30 s (Fig. 6a) relative to the initial thickness, suggesting the coating had taken up a substantial amount of water. Water molecules should exist as bound water (non-freezing water) to the hydrophilic segments of the terpolymer.1,22 In addition, since SIPN-T40 remained completely transparent over the test period, there should be no discrete free water domain in the coating; otherwise, reduced light transmission would have been observed.27,28 Aer $60~\\mathrm{s}$ , the coating thickness decreased signicantly (Fig. 6a) to about $17\\%$ above its initial thickness, revealing that some water molecules had somehow “le” the coating. It was interesting to notice that, aer about $150~\\mathrm{s}$ , the coating had almost recovered to its original thickness; in other words, most of the absorbed water had been released from the coating, despite that the exact mechanism of water departure remained unclear.  \n\nThe rapid recovery of the thickness for the antifogging/frostresisting coating is an obvious advantage: the coating is ready for the next antifogging action. SIPN-T-40 was subject to four more frosting tests and, indeed, during each test the variation of the coating thickness followed the similar trend to Fig. 6a. The original coating thickness was restored in a short period of time $\\left(2.5\\mathrm{-}3\\mathrm{min}\\right)$ ) under ambient conditions. The variation in the coating thickness at room temperature was also directly reected in the transmission prole (Fig. 6b). The coating aer 30 s at room temperature following the rst freezing ( $30\\mathrm{min}$ at $-20$ ${}^{\\circ}\\mathbf{C}]$ , Fig. 6b-ii, appeared to have very similar transmission spectrum with the same coating aer $30~\\mathrm{s}$ at room temperature following the h freezing (Fig. 6b-iii), indicating there was a similar amount of bound water in the coating during the rst and h frosting test. Furthermore, the transmission spectrum (Fig. 6b-iv) for the coating aer $200\\mathrm{~s~}$ at room temperature following the h freezing resembled closely to the original coating (Fig. 6b-i), revealing that the coating thickness had restored to its original thickness. The reversible change of the coating thickness implied that the antifogging property of our coating would be long-term effective.  \n\nSIPN-T-40, together with a control glass, was mounted on a bathroom mirror and visually examined for possible fogging immediately aer a shower for 6 months (with typically one shower a day being taken). As clearly shown in Fig. 7, SIPN-T-40 remained to be perfectly antifogging aer about 180 showers, while the control glass as well as the mirror completely fogged up. Indeed, the terpolymer-based SIPN coating has remained antifogging aer at least 6 months.  \n\n![](images/35876b34445745c8da28c5636cfe300e507f0af4baaa1abce9eb175852e8369a.jpg)  \nFig. 6 (a) Thickness change for SIPN-T-40, relative to the original coating thickness, following a frosting test: 30–150 s at room temperature after the coating was stored at $-20^{\\circ}\\mathsf C$ for $30\\mathrm{min}$ . (b) Zoomed-in transmission raw data (in dots) and fitting solid lines by eqn (1) for SIPN-T-40: (i) the original coating; (ii) 30 s at room temperature after first freezing (stored at $-20^{\\circ}C$ for $30\\mathrm{min})$ ); (iii) 30 s at room temperature after 5th freezing; and (iv) 200 s at room temperature after 5th freezing.  \n\n![](images/4a028d6a576b7098ccc33190a488d8934e3a8cb0340ff3629204acc85bda2d78.jpg)  \nFig. 7 Photo of two samples (a) SIPN-T-40 and (b) control glass on a bathroom mirror, immediately after a shower on day 181.  \n\nIn summary, we prepared antifogging/frost-resisting coatings on the basis of a SIPN comprising random, linear terpolymer poly(DMAEMA-co-NVP-co-MMA) and cross-linked PEGDMA. By carefully balancing the hydrophilic DMAEMA and NVP segments and hydrophobic MMA segments in the terpolymer, the LCST effect in a binary poly(DMAEMA-co-MMA)-based coating was completely eliminated, leading to excellent antifogging/frost-resisting properties against both hot and cold moist air for a terpolymer coating (SIPN-T-40) with the optimal DMAEMA/NVP/MMA molar ratio of 40/30/30. The antifogging/ frost-resisting property of the SIPN-based coating can be attributed to its capability of absorbing rapidly water vapour from the surrounding, yet not allowing the formation of discrete water domain in the coating, thus ensuring optical transparency for the coating during fogging/frosting tests. The fact that water molecules can quickly depart from the coating renders this type of antifogging/frost-resisting coating longterm effective.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# Acknowledgements  \n\nFinancial support of this research from USDA/NIFA (Award No.   \n2011-67022-30229) is gratefully acknowledged.",
+        "category": " References"
+    },
+    {
+        "id": 17,
+        "chunk": "# Notes and references  \n\n1 J. Zhao, A. Meyer, L. Ma and W. Ming, Chem. Commun., 2013, 49, 11764.   \n2 A. Tricoli, M. Righettoni and S. Pratsinis, Langmuir, 2009, 25, 12578.   \n3 P. Chevallier, S. Turgeon, C. Sarra-Bournet, R. Turcotte and G. Laroche, ACS Appl. Mater. Interfaces, 2011, 3, 750.   \n4 L. Introzzi, J. M. Fuentes-Alventosa, C. A. Cozzolino, S. Trabattoni, S. Tavazzi, C. L. Bianchi, A. Schiraldi, L. Piergiovanni and S. Farris, ACS Appl. Mater. Interfaces, 2012, 4, 3692.   \n5 L. Zhang, Z. Qiao, M. Zheng, Q. Huo and J. Sun, J. Mater. Chem., 2010, 20, 6125.   \n6 J. A. Howarter and J. P. Youngblood, Adv. Mater., 2007, 19, 3838.   \n7 X. Zhang and J. He, Chem. Commun., 2015, 51, 12661.   \n8 J. Xiong, S. N. Das, J. P. Kar, J. H. Choi and J. M. Myoung, J. Mater. Chem., 2010, 20, 10246.   \n9 H. Dong, P. Ye, M. Zhong, J. Pietrasik, R. Drumright and K. Matyjaszewski, Langmuir, 2010, 26, 15567.   \n10 D. Lee, M. F. Rubner and R. E. Cohen, Nano Lett., 2006, 6, 2305.   \n11 F. C. Cebeci, Z. Wu, L. Zhai, R. E. Cohen and M. F. Rubner, Langmuir, 2006, 22, 2856.   \n12 N. Nuraje, R. Asmatulu, R. E. Cohen and M. F. Rubner, Langmuir, 2010, 27, 782.   \n13 Y. Li, J. Zhang, S. Zhu, H. Dong, F. Jia, Z. Wang, Z. Sun, L. Zhang, Y. Li, H. Li, W. Xu and B. Yang, Adv. Mater., 2009, 21, 4731.   \n14 X. Liu, X. Du and J. He, ChemPhysChem, 2008, 9, 305.   \n15 L. Xu and J. He, ACS Appl. Mater. Interfaces, 2012, 4, 3293.   \n16 L. Zhang, Y. Li, J. Sun and J. Shen, Langmuir, 2008, 24, 10851.   \n17 R. Wang, K. Hashimoto, A. Fujishima, M. Chikuni, E. Kojima, A. Kitamura, M. Shimohigoshi and T. Watanabe, Nature, 1997, 388, 431.   \n18 M. Miyauchi, A. Nakajima, K. Hashimoto and T. Watanable, Adv. Mater., 2000, 12, 1923.   \n19 Y. Lai, Y. Tang, J. Gong, D. Gong, L. Chi, C. Lin and Z. Chen, J. Mater. Chem., 2012, 22, 7420.   \n20 X. F. Gao, X. Yan, X. Yao, L. Xu, K. Zhang, J. Zhang, B. Yang and L. Jiang, Adv. Mater., 2007, 19, 2213.   \n21 J. A. Howarter and J. P. Youngblood, Macromol. Rapid Commun., 2008, 29, 455.   \n22 H. Lee, M. L. Alcaraz, M. F. Rubner and R. E. Cohen, ACS Nano, 2013, 7, 2172.   \n23 H. Lee, J. B. Gilbert, F. E. Angile, R. Yang, D. Lee, M. F. Rubner and R. E. Cohen, ACS Appl. Mater. Interfaces, 2015, 7, 1004.   \n24 X. Zhang and J. He, Sci. Rep., 2015, 5, 9227.   \n25 K. C. Jena and D. K. Horea, Am. J. Phys., 2011, 79, 256.   \n26 D. J. Griffiths, Introduction to Electrodynamics, Prentice-Hall, Upper Saddle River, NJ 07458, 1999, p. 404.   \n27 N. Starostin, S. Harvey and G. Carlson, Scanning, 2008, 30, 78.   \n28 Z. Aguirreurreta, J. Dimmer, I. Willerich, J. de la Cal and J. R. Leiza, Macromol. Mater. Eng., 2015, 9, 925.",
+        "category": " References"
+    },
+    {
+        "id": 18,
+        "chunk": "# Conclusions",
+        "category": " Conclusions"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,62 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Preparation of Water-Resistant Antifog Hard Coatings on Plastic Substrate  \n\nChao-Ching Chang,†,‡ Feng-Hsi Huang,† Hsu-Hsien Chang,† Trong-Ming Don,†,‡ Ching-Chung Chen,‡ and Liao-Ping Cheng\\*,†,‡  \n\n†Department of Chemical and Materials Engineering, and ‡Energy and Opto-Electronic Materials Research Center, Tamkang University, New Taipei City, Taiwan, 25137  \n\n\\*S Supporting Information  \n\nABSTRACT: A novel water resistant antifog (AF) coating for plastic substrates was developed, which has a special hydrophilic/hydrophobic bilayer structure. The bottom layer, acting both as a mechanical support and a hydrophobic barrier against water penetration, is an organic−inorganic composite comprising colloidal silica embedded in a cross-linked network of dipentaethritol hexaacrylate (DPHA). Atop this layer, an AF coating is applied, which incorporates a superhydrophilic species synthesized from Tween-20 (surfactant), isophorone diisocyanate (coupling agent), and 2-hydroxyethyl methacrylate (monomer). Various methods, e.g., FTIR, SEM, AFM,  \n\n![](images/399065e8dca87b266881bcc15e69aed846ac63a559f6f1eb1e5d0b3a04a76b6e.jpg)  \n\ncontact angle, and steam test, were employed to characterize the prepared AF coatings. The results indicated that the size and the continuity of the hydrophilic domains on the top surface increased with increasing added amount of T20, however, at the expense of hardness, adhesiveness, and water resistivity. The optimal T20 content was found to be 10 wt $\\%$ , at which capacity the resultant AF coating was transparent and wearable (5H, hardness) and could be soaked in water for 7 days at $25~^{\\circ}\\mathrm{C}$ without downgrading of its AF capability.",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# INTRODUCTION  \n\nFog forms when saturated water vapor condenses in the form of small droplets capable of scattering visible light on a surface with a temperature lower than the dew point of the vapor. This undesirable phenomenon occurs frequently on bathroom mirrors, eyeglasses, swimming goggles, windshields, camera lens, etc., items which are closely related to our everyday life. Surface fog can reduce the precision of optical and analytical instruments, such as infrared microscopes or bronchoscopes.1,2 In applications where high solar energy input is demanded, such as solar cells, fogging could reduce the light transmittance and bring down the efficiency of energy usage.3  \n\nThe basic concept of antifog is to create a hydrophilic surface such that arriving water droplets would spread and naturally form a continuous or nearly continuous water film on the surface, so that light can transmit directly free of interfering scattering from water microdroplets.4,5  \n\nPreparation of a hydrophilic surface generally falls into three categories: I. Hydrophilic agents are physically introduced into the polymer matrix without chemical bond formation. Usually, a simple process such as solution or melt blending is good enough to yield an effective AF surface. However, the hydrophilic agents may come off the coating surface during cleaning, and thus, stable long-term wettibility cannot be assured. As a result, this approach is only suited to products of short life cycles, such as food packaging.6 II. Chemical modification was performed directly on the surface of interest.7−10 For example, Howarter et al. grafted hydrophilic species, poly(ethylene glycol) (PEG), onto a glass surface through the use of a silane-type coupling agent that bridged PEG and glass. Both good adhesion and hydrophilicity were attained via this method. However, the treated surface became very soft due to the presence of the hydrophilic agent. Even small mechanical impacts can give rise to visible scratching marks. Furthermore, because complex chemical processes were involved, it is impractical to apply this method to substrates of large surface area,8,9 such as building windows. III. Hydrophilic components are incorporated into the coating formula, which is then photo or thermal-cured to form an AF layer on the surface. Unlike method I, the hydrophilic species are chemically cross-linked to the matrix in this case. Although method III is applicable to virtually any kind of substrate materials (plastics are of particular interest), the interface between coating layer and substrate is susceptible to water invasion due to absorption by hydrophilic groups. The AF layer may swell and detach from the substrate in very humid environments.11 Alternatively, on glass substrates, an AF layer may be formed consisting of inorganic oxides such as $\\mathrm{TiO}_{2},\\mathrm{Cd}_{2}\\mathrm{O}_{3},\\mathrm{ZnO},$ or $\\mathrm{ZrO}_{2}$ . Although it has the benefits of good adhesion and surface hardness, the high temperature process associated with oxide formation  \n\nScheme 1. Preparation of (a) Silica Sol and (b) $\\mathbf{MSiO}_{2}$ Sol and Polyacrylate-Silica Thin Film (Bottom Layer)  \n\n![](images/406951866384a8afaea3af1d2af7637a4a532fb71aaaae6f409def656dbabcfd.jpg)  \n\nprecludes it from being applied on plastic materials.12−18 A comprehensive review of the articles for preparation and design of such hydrophilic coatings has been carried out by Feng et al.19 In recent years, biomimetic, raspberry-like, or nanoporous antireflective/antifogging films composed by silica $\\left(\\mathrm{SiO}_{2}\\right)$ and titania (TiO2) nanospheres have been demonstrated.20−28 However, to improve the mechanical durability, robustness, and adhesion of the films, the resultant films have to be calcinated at $500~^{\\circ}\\mathrm{C}$ .  \n\nAs a matter of fact, there are several hurdles to overcome in order to prepare a robust, long-life, antifog coating on plastic substrates. First, if direct surface modification is to be implemented, one should consider the fact that plastics are sensitive to both temperature and solvent damaging. Second, the coating layer should adhere strongly to the substrate and should not deform or peel off when used in highly humid environments or when cleaning is required. Third, hardness of the coating should comply with the application criterion. In the current research, a new approach is adopted in light of the above concerns. The prepared antifog coating has a special bilayer configuration, for which the bottom layer (primer) is a cross-linked network of poly(acrylate) embedded with nanosized silica that provides mechanical strength and adhesiveness. On top of the primer is lain the AF layer, in which surface active agent, Tween 20, is modified and covalently incorporated into the polymer host. Because the top and bottom layers are interlinked by UV-cured poly(acrylate), these two layers are mechanically inseparable and appear transparent as if they were a uniform layer. Furthermore, the coating can be rinsed in water and remain integrality after drying. Thanks to the hydrophobic feature of the primer, water molecules cannot penetrate through the coating and detach it from the substrate. The detailed synthesis and characterization of the developed antifog coating is demonstrated in the following sections.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# EXPERIMENTAL SECTION  \n\nChemicals. 3-(Trimethoxysilyl) propyl methacrylate (MSMA, Degussa), tetraethoxysilane (TEOS, Fluka), sorbitan monolaurate (Tween 20, $M_{\\mathrm{w}}=1227.5,$ Aldrich), isophorone diisocyanate (IPDI, Aldrich), 2-hydroxyethyl methacrylate (2- HEMA, Aldrich), dipentaethritol hexaacrylate (DPHA, Aldrich), Darocure 1173 (Ciba-Geigy), methyl ethyl ketone (MEK, Fluka), 2-propanol (IPA, Aldrich) were at regent grade or higher, and used as received.  \n\nSynthesis of Surface-Modified Silica. The silica sol for the bottom layer was synthesized by a modified sol−gel method, cf. Scheme 1.29−32 An appropriate amount of TEOS was mixed with 2-propanol to form a homogeneous solution. To this solution, the catalyst HCl (aq) $\\left(\\mathsf{p H1.2}\\right)$ was added to induce hydrolysis−condensation of TEOS. The molar ratio of $\\mathrm{{H}}_{2}\\mathrm{{O}/T E{O S}}$ was set to be equal to four. The mixture was stirred for $3\\mathrm{h}$ at room temperature to yield a silica sol, and then additional HCl (aq) $\\left(\\mathsf{p H1.2}\\right)$ and coupling agent, MSMA, with a molar ratio of $\\mathrm{{H}}_{2}\\mathrm{{O}}/\\mathrm{{MSMA}}=3\\$ and $\\mathrm{TEOS/MSMA}=4.5,$ were slowly dropped into the silica sol, cf. Scheme 1b. After reaction for another $^{3\\mathrm{~h~},}$ the surface-modified silica (termed $\\mathrm{MSiO}_{2},$ containing $\\scriptstyle{\\mathrm{C}}={\\mathrm{C}}$ on their surface) was obtained.  \n\nPreparation of the Antifog Coating. Photocurable coating sol was prepared by adding $_{10\\mathrm{~g~}}$ of the multifunctional cross-linking agent (DPHA), $_{0.59\\mathrm{~g~}}$ of the photoinitiator (Darocure 1173), and $17.68\\ \\mathrm{g}$ of 2-propanol into $20\\mathrm{g}$ of the assynthesized $\\mathrm{MSiO}_{2}$ sol with a total solid content (theoretical) adjusted to $30\\mathrm{\\mt\\\\%}$ . The sol was spin-coated on a poly(methyl methacrylate) (PMMA) substrate, and then prebaked at $80~^{\\circ}\\mathrm{C}$ for $40~\\mathsf{s},$ , followed by UV-irradiation (broadband, $250~\\mathrm{mJ/cm}^{2},$ to obtain a cured film. The thickness of the film was measured to be ${\\sim}1.2\\ \\mu\\mathrm{m}$ by interferometry. The radiation power was carefully chosen such that DPHA was only partly cross-linked, allowing for subsequent reaction with the top AF layer during UV-curing of the latter.  \n\n![](images/1265f7594615817bc912d3fb9d5d6658a242c226c0cc135a0e4dc976dfe5ffd5.jpg)  \nScheme 2. (a) Reaction of IPDI and 2-HEMA to Form the Intermediate Molecule 2-HEMA/IPDI and (b) Proposed Reaction Mechanism for the Synthesis of UV Curable Hydrophilic Agent T20  \n\nTo prepare the coating sol for the AF layer, hydrophilic agents were modified first, cf. Scheme 2. Equal number of moles of 2-HEMA and IPDI were stirred in a glass reactor under temperature control. When the temperature reached 50 ${}^{\\circ}\\mathrm{C},$ dibutyltin dilaurate ( $0.1\\%$ of the total weight of 2-HEMA and IPDI) acting as the catalyst was added, and the reaction was allowed to proceed for $^{2\\mathrm{~h~}}$ at $50~^{\\circ}\\mathrm{C}$ . Subsequently, hydrophilic agent (Tween 20) was added and reacted for another $^{2\\mathrm{~h~}}$ . The molar ratio of IPDI/Tween20 was set to 1. The modified Tween 20 was called T20, hereinafter. The AF coating sols for the top layer were prepared by mixing $\\mathrm{T}20$ with the coating sol for the bottom layer, however, with some adjustment of the DPHA content to give 30 wt $\\%$ silica in the coating, cf. Table 1. The formed sol was spin-coated on the partly cured bottom layer, followed by predrying $(80^{\\circ}\\mathrm{C},40\\mathrm{s})$ and UV-curing $(500~\\mathrm{mJ/cm}^{2})$ to obtain an AF layer of ${\\sim}1\\ \\mu\\mathrm{m}$ thick.  \n\nTable 1. Chemical Species for Preparing the Top AF Layer of the Coating   \n\n\n<html><body><table><tr><td>sample name</td><td>MSi02 sol (g)</td><td>T20 (g)</td><td>IPA (g)</td><td>DPHA (g)</td><td>1173 (g)</td></tr><tr><td>AF2</td><td>20</td><td>0.3</td><td>17.68</td><td>9.7</td><td>0.59</td></tr><tr><td>AF4</td><td>20</td><td>0.6</td><td>17.68</td><td>9.4</td><td>0.59</td></tr><tr><td>AF6</td><td>20</td><td>0.9</td><td>17.68</td><td>9.1</td><td>0.59</td></tr><tr><td>AF8</td><td>20</td><td>1.2</td><td>17.68</td><td>8.8</td><td>0.59</td></tr><tr><td>AF10</td><td>20</td><td>1.5</td><td>17.68</td><td>8.5</td><td>0.59</td></tr><tr><td>AF12</td><td>20</td><td>1.8</td><td>17.68</td><td>8.2</td><td>0.59</td></tr><tr><td>AF15</td><td>20</td><td>2.25</td><td>17.68</td><td>7.75</td><td>0.59</td></tr><tr><td>AF96</td><td>2</td><td>24</td><td>1.77</td><td>0.5</td><td>0.59</td></tr></table></body></html>  \n\nFTIR Spectra. Fourier transform infrared (FTIR) absorption spectra of the formed $\\mathrm{{MSiO}}_{2}$ sol and the cured coatings were obtained using a Nicolet 550 spectrometer. Cured thin films were ground with KBr (1:50) and pressed to form a disc for FTIR scanning. Liquid samples were prepared by dropping appropriate amount of the sol onto a KBr disc, and then the solvent was evaporated at $40~^{\\circ}\\mathrm{C}$ for $10~\\mathrm{{min}}$ in a vacuum oven.  \n\nParticle Size Determination. The size and size distribution of particles in the sols were determined by the dynamic light scattering (DLS) analysis using a Zetasizer (Malvern, DTS 1060) at $25~^{\\circ}\\mathrm{C}$ . The instrument was equipped with a monochromatic coherent helium neon laser $\\left(633~\\mathrm{nm}\\right)$ as the light source. A $4\\mathrm{\\mL}$ sample was injected into the quartz cuvette secured on the holder, and then the scattered light was recorded at an angle of $173^{\\circ}$ with respect to the incident beam.  \n\nFilm Surface Observation. The nanoscale morphology of the cured film was observed using a Leo 1530 field emission scanning electron microscope (FE-SEM). The samples were vacuum-dried and then coated with a thin layer (ca. $1.0\\ \\mathrm{nm}\\cdot$ ) of a $\\mathrm{Pt-Pd}$ alloy with a sputter coater equipped with a quartz crystal microbalance thickness controller. The samples were imaged at high magnifications (e.g., $\\mathbf{\\times}100\\mathbf{k})$ under the acceleration voltage of $15\\ \\mathrm{kV}$ via an in-lens detector. Atomic force microscopic (AFM) imaging of the bottom and the AF layers were performed with a Nano Scope scanning probe microscope (CP-II, Veeco). Tapping mode was used to track the surface of the sample via a single crystal silicon probe (Olympus tapping mode etched silicon probe). The spring constant and resonance frequency of the probe were $42{-}80\\mathrm{N}/$ m and ${50{\\mathrm{-}}100\\ \\mathrm{kHz,}}$ respectively. The scanning frequency was $1\\ \\mathrm{Hz}$ . Both topographic diagram and phase contrast diagram were constructed. The former diagram provides information of surface roughness and domain size, whereas the later voltage distribution on the surface.  \n\nContact Angle, Adhesion, and Hardness Measurements. The contact angle between water and AF surface was measured by a FTA 125 contact angle/surface tension analyzer at room temperature. A $6\\mu\\mathrm{L}$ drop of water was placed onto the surface of the coating. The image was taken and the contact angle was measured from shape analysis of the sessile drop. Tape test (CNS 11684), also known as peel test, was carried out to evaluate the adhesion of the coatings on the substrate. The degree of adhesion was defined as the percentage of film residing on the plate after the peel test. The hardness of the cured films was examined by the industrial pencil hardness test (JIS K5400) with pencils of different hardness at a load of 765 g.  \n\nSteam Tests. Steam tests of various coatings were carried out to see their AF performance. Boiling water was added into a beaker to about half full. Then, the sample was placed on the beaker with the coated surface facing down. Vapor condensed on the coating surface was observed and photographed.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# RESULTS AND DISCUSSION  \n\nPreparation and Characterization of the Primer. The primer is an organic−inorganic hybrid material composed of nanosized silica dispersed uniformly in the polymer host.31 The sol−gel process for the synthesis of surface-modified silica, $\\mathrm{MSiO}_{2},$ involves hydrolysis and condensation of TEOS and MSMA. The detailed chemical analyses (FTIR and $^{29}\\mathrm{Si}$ NMR) of this reaction have been documented.23 Particle size of the modified silica was measured to be $\\mathrm{\\sim}7~\\mathrm{nm}$ , consistent with those reported in the literature.29  \n\nThe formed $\\mathrm{{MSiO}}_{2}$ sol was mixed with DPHA, photoinitiator, and 2-propanol and then UV-cured to yield an organic−inorganic hybrid hard coating on PMMA plate.28 Figure 1 shows the effect of UV power on the curing efficiency of a typical sample. A monotonous decrease of the $\\scriptstyle{\\mathrm{C}}={\\mathrm{C}}$ peak signal at $1634~\\mathrm{{\\bar{cm}}^{-1}}$ is indicated with increasing UV irradiation intensity. When the power was set to $500~\\mathrm{mJ/cm}^{2}.$ , the peak was very small, implying that most of the vinyl groups were converted to $\\scriptstyle{\\mathrm{C-C}}$ bonds during the UV-induced cross-linking reaction. In case that only half of the power $250\\ \\mathrm{mJ/cm}^{2}$ was employed, there was still ${\\sim}40\\%$ vinyl groups left unreacted (based on the peak area analysis). The free vinyl groups near the surface region would react with the curing agent, DPHA, in the top AF layer during the second stage curing process. The cured primer exhibited a hardness of 4H according to the pencil test, and it attached firmly to the PMMA substrate with a peeltest adhesion of $100\\%$ . FE-SEM imaging of the primer indicated a uniform surface morphology (Figure S1, Supporting Information), free of organic/inorganic phase domains at the resolution scale of $10\\ \\mathrm{~nm}$ , agreeing with the fact that the coating was a highly transparent thin film. The 3-D topographic AFM diagram of the primer’s surface was extremely smooth with a measured average roughness as small as $1.4\\ \\mathrm{nm}$ (Figure S2, Supporting Information). Curing with a power lower than $250\\mathrm{\\mJ}/\\mathrm{cm}^{2}$ has been tested to give higher residual $\\scriptstyle{\\mathrm{C}}={\\mathrm{C}}$ concentration, however, at the sacrifice of the mechanical strength. In summary, $250~\\mathrm{mJ}/\\mathrm{cm}^{2}$ is appropriate for preparing a smooth coating surface possessing sufficient amount of vinyl groups for making bonds with the multifunctional monomer, DPHA, in the top AF layer during the second stage curing process.  \n\n![](images/32dbbc68f7e65446f6d38ee55bb18ffc1422bd88acd329077f8eee6295f89f20.jpg)  \nFigure 1. FTIR spectra of the UV-cured coatings for the bottom layer, showing the effect of irradiation power.  \n\nPreparation of the AF Layer. The surfactant, Tween-20, was modified to acquire UV photosensitivity by linking to 2- HEMA via the spacer IPDI. The synthetic process involved two steps, as shown in Scheme 2. First, the −OH group of 2-HEMA and $-\\mathrm{\\mathbf{N}}\\mathrm{\\mathbf{C}}\\mathrm{\\mathbf{O}}$ group of IPDI were reacted to form the urethane bond in the molecule, 2-HEMA/IPDI.33 During the course of this reaction, the $-\\mathrm{NH}$ peak in the FTIR spectra (Figure S3, Supporting Information) stemming from the urethane linkage is found at $1529~\\mathrm{{cm}^{-1}}$ whose intensity increases gradually up to $^{\\mathrm{~1~h,~}}$ and afterward it levels-off. Because 2-HEMA and IPDI were initially charged at equal molar amount, the reaction was considered to approach completeness in ca. $^\\textrm{\\scriptsize1h}$ . In the second step, the as-prepared molecule 2-HEMA/IPDI was reacted with Tween-20 to give a dual-functional molecule (T20), bearing both UV-curability and high hydrophilicity. The −NH peak of urethane at $1529~\\mathrm{{cm}^{-1}}$ , signifying the presence of T20, rises progressively over the period of $^\\textrm{\\scriptsize2h}$ . In contrast, the -NCO signal at $22\\dot{6}0~\\mathrm{cm}^{-1}$ declines with time and it vanishes virtually after reaction for $^{2\\mathrm{h},}$ confirming that the second half of -NCO groups in IPDI has all been converted to urethane at the end of reaction (Figure S4, Supporting Information). It should be noted that the $\\scriptstyle{\\mathrm{C}}={\\mathrm{C}}$ groups remain intact throughout the reaction. These groups can be used to cross-link with DPHA during UV curing of the top layer.  \n\nFigure 2 shows the FTIR spectra of a typical bilayer coating, AF10. The $_{\\mathrm{Si-O-Si}}$ band at $\\mathsf{\\bar{1529}~c m^{-1}}$ indicates the presence of $\\mathrm{MSiO}_{2}$ whereas $\\scriptstyle{\\mathrm{C}}={\\mathrm{O}}$ at $1727~\\mathrm{{cm}^{-1}}$ is contributed by 2- HEMA, Tween-20, and DPHA moieties. The small $\\scriptstyle{\\mathrm{C}}={\\mathrm{C}}$ signal suggests that an effective UV-curing has been performed; thereby, a rather hard AF layer (4H) was created (details shown later). The amount of $\\scriptstyle{\\mathrm{C}}={\\mathrm{C}}$ bond can further be reduced by postbaking of the sample at $100^{\\circ}\\mathrm{C}$ . Apparently, baking for $^{\\textrm{1h}}$ . is sufficient to consume most of the residual $\\mathrm{C=C_{\\mathrm{\\lambda}}}$ ; prolonged baking is futile probably due to steric hindrance. The other effect of postbaking is for the compaction of silica particles. As is evident from the spectra, new $_{\\mathrm{Si-O-Si}}$ bonds are formed by alcohol condensation of $_{\\mathrm{Si-O-C}}$ and/or water-condensation of $S_{\\mathrm{i-OH}}$ groups. The bottom layer and bilayer coatings were highly transparent in the visible region. For example, the transmittance of the bilayer coating AF10 is $95{-}98\\%$ in the visible region (Figure S5).  \n\n![](images/5a0ad710e9de3780cc9cde42eabfc7ba8306dd10924415407b962bf9d993432e.jpg)  \nFigure 2. FTIR spectra of the bilayer AF coating AF10.  \n\nAFM was employed to disclose the surface morphology as well as the distribution of T20 within the surface region of various prepared coatings. Figure 3 shows the topographic and voltage contrast diagrams of the surfaces of the primer and sample AF96. The former consists of DPHA and $\\mathrm{MSiO}_{2},$ whereas the latter contains mostly T20 $(96\\%)$ . The topographic diagrams (right part) for these two samples are similar; both surfaces are extremely smooth with measured average roughness of ${\\sim}1\\ \\mathrm{nm}$ . However, their voltage contrast diagrams (left part) are distinctively different. For the primer’s surface, the scanning voltage is above $_{7\\mathrm{V}}$ over the entire surface, except for some sporadic spots. In contrast, for the sample AF96, a small scanning voltage, 1.41 V, covers $\\sim90\\%$ (based on image analysis) of the scanning area. Generally, the voltage value depends both on the roughness and the rigidity of the surface. For a very smooth surface having roughness $<10~\\mathrm{nm}$ , the voltage value is useful for estimating the distribution of hard/ soft domains on the surface.34,35 For example, the primer is a very hard material composed of highly cross-linked DPHA and $\\mathrm{{MSiO}}_{2},$ and thus high scanning voltage is imposed. On the other hand, a relatively low voltage is delivered to the surface of AF96 due to the presence of the soft hydrophilic agent, T20. In this context, by analyzing the voltage contrast diagram, one can differentiate the hydrophilic (soft) from the hydrophobic (hard) zones on a flat AF coating surface. Three typical cases are demonstrated in Figure 4 for comparison. The T20 contents for these coatings are 4, 12, and 15 wt $\\%$ , respectively. From the topographic diagrams (right part), the measured average surface roughness is found to increase just slightly from 1.0 to $3.6~\\mathrm{nm}$ with a large increase of T20 dosage from 4 to 15 wt $\\%$ . On the other hand, the voltage contrast diagrams (left part) use gray scale to manifest areas of different voltages; the light-gray depicts high voltage (hard) regions, whereas the darkgray, low voltage (soft) ones. As is expected, the dark area increases as the T20 content is raised. To estimate the distribution of soft/hard domains on the AF surface, the voltage contrast diagrams are further processed to give black and white bicolor patterns, as shown in Figure 5, with $_{5\\mathrm{~V~}}$ being taken as the border value. This voltage is selected based on two facts: (i) it is close to the arithmetic mean of the highest voltage of the primer’s surface and the lowest voltage of AF96 (Figure 4); (ii) as the lowest voltage of the primer’s surface is $6\\mathrm{V},$ below $_{5\\mathrm{~V~}}$ contribution from the soft segments (T20) is expected to outweigh that from the hard segments (cured DPHA and $\\mathrm{MSiO}_{2}\\mathrm{\\backslash}$ . In fact, bicolor patterns with various cutting-edge voltages over the range $4.5\\substack{-5.5\\mathrm{~V~}}$ have been created, and from them a similar conclusion can be inferred, considering the effect of soft/hard pattern on the AF performance discussed below.  \n\nFrom Figure 5, variation of soft/hard domains with respect to T20 content is clearly illustrated. For the sample AF4, only small separate black dots of ca. $10{-}35~\\mathrm{nm}$ are present, and for the sample AF10, the amount of black dots increases and some of them start to connect with each other. When the T20 content reaches 15 wt $\\%$ , AF15, the black dots interconnect extensively into many continuous regions, which constitute ca. $25\\%$ of the total area. The bicolor diagrams, even with its approximate nature, are useful for understanding the antifog mechanism underlying the prepared AF coatings. Surface fog is generated when impinging water droplets develop to the size that scatters visible light, typical ${>}100\\ \\mathrm{nm},$ , and in case that the growing water droplets contact a hydrophilic area, they will spread to reduce their surface tension. Therefore, AF effect can be achieved as long as the hydrophilic area on the coating surface can form a pattern that prohibits the growth of water droplets beyond ${\\sim}100~\\mathrm{nm}$ , which is manifested in Figure 5. For the sample AF4, water droplets of size as large as ${\\sim}160~\\mathrm{nm}$ (cf. the white area) may rest independently on the coating surface; hence, fog is expected to form on this surface. In contrast, for both AF10 and AF15, the sizes of the hydrophobic domains are all less than $100\\ \\mathrm{nm}$ (average $63\\ \\mathrm{nm}$ for AF10). As arriving water droplets tend to spread into a continuous film, scattering does not occur, and these two coatings will exhibit AF characteristic.  \n\n![](images/7585e7b4cc2b2bb4bfc8684978d2d5e28ceb5abcd76ab4cd2ea202b0066fff34.jpg)  \nFigure 3. AFM voltage (left part) and topographic (right part) diagrams of the coating. (a) Primer and (b) AF96.  \n\n![](images/5a7ed6ed28ef248807e6671f8d34030607e85e6eb8d48a3f24bad3e84a1e67f6.jpg)  \nFigure 4. AFM voltage (left part) and topographic (right part) diagrams of the AF coatings with different T20 contents. (a) AF4, (b) AF10, and (c) AF15.  \n\nAntifog and Hardness Tests. Hardness, contact angle, adhesion, and AF tests of various prepared coatings were performed and the results are summarized in Table 2. The plastic substrate PMMA is relatively soft with a pencil hardness ${<}\\mathrm{{1H}}$ After coated with the primer, its hardness rises to 4H (8H, if fully cured), high enough for general purpose. This surface is, however, relatively hydrophobic with a high water contact angle of $70^{\\circ}$ , and the AF test indicates a misty appearance, cf. Figure 6a. After applying an AF layer on top of the primer, the water contact angle drops dramatically. For example, the contact angle lowers down to $30^{\\circ}$ upon incorporation of $4\\%$ T20 (AF4), and a $10\\%$ T20 dosage (AF10) renders the coating surface extremely hydrophilic such that the deposited droplet spreads automatically with immeasurably small water contact angle. Superb AF performance of this coating is in evidence by the steam test; as shown in Figure 6b, the English letters underneath the beaker are clearly seen for the area sheltered by the AF coating. In general, the hydrophilicity of a coating increases with its T20 content, however, at the expense of the mechanical strength. For example, as shown in Table 2, the hardness of the coatings plunges quickly from 6H to ${<}\\mathrm{{1H}}$ when the T20 content is raised from $4\\%$ to $15\\%$ . The samples AF4 and AF8 are hard enough to serve as a hard-coating surface, yet their poor vapor spreading capability disqualify them to be AF coatings.  \n\n![](images/c9a64501740cbd72b69d1415e4a59ada50b9532138e85f39866c9bbe42b154d7.jpg)  \nFigure 5. AFM voltage (left part) and topographic (right part) diagrams of the AF coatings of different T20 contents. (a) AF4, (b) AF10, and (c) AF15.  \n\nIn real practice, the service life of an AF coating, which relies on its capability to endure water damaging, is of major concern, in addition to the water wettibility and mechanical strength; in particular, when the coating is to be used in highly humid environments. In this regard, various prepared AF coatings were soaked in water for an extended period of time to see their durability against water invasion. The results are summarized in Table 3. Apparently, coatings with T20 content higher than $10\\%$ cannot withstand long-term soaking; for example, the AF layer of the sample AF15 detaches from the primer after immersed in water for 1 day at $25~^{\\circ}\\mathrm{C}.$ In contrast, AF10 retains its outstanding AF performance even after immersion in water at $60~^{\\circ}\\mathrm{C}$ for 1 day. More interestingly, as manifested by the steam test in Figure 6, this coating still performs well even after one year in service at the ambient condition, ${\\sim}25^{\\circ}\\mathrm{C}$ and $\\sim70\\%$ relative humidity.  \n\nTable 2. Contact Angle, Hardness, Adhesiveness, and AF Performance of Coatings   \n\n\n<html><body><table><tr><td>sample name</td><td>hardness</td><td>contact angle (degree)</td><td>adhesion (%)</td><td>AF performance</td></tr><tr><td>PMMA</td><td><1H</td><td>75</td><td></td><td>misty</td></tr><tr><td>BM</td><td>8H</td><td>70</td><td>100%</td><td>misty</td></tr><tr><td>AF4</td><td>6H</td><td>30</td><td>100%</td><td>misty</td></tr><tr><td>AF8</td><td>5H</td><td>17</td><td>100%</td><td>droplet</td></tr><tr><td>AF10</td><td>5H</td><td>~0</td><td>100%</td><td>transparent</td></tr><tr><td>AF12</td><td>2H</td><td>~0</td><td>35%~65%</td><td>transparent</td></tr><tr><td>AF15</td><td><1H</td><td>~0</td><td><35%</td><td>transparent</td></tr></table></body></html>  \n\n![](images/8b305c38b4700cfbb7ec7239e198e51673a53b1ea1ed3db77b7b78c711745c77.jpg)  \nFigure 6. Steam antifog tests of coatings: (a) AF4 and (b) AF10 after 1 year in service.  \n\nTable 3. Contact Angle (Degree) of the AF Coatings after Water Soaking   \n\n\n<html><body><table><tr><td>sample name</td><td>1 day at 25 °C</td><td>7 days at 25 °C</td><td>1 day at 60 °C</td></tr><tr><td>AF8</td><td>18</td><td>18</td><td>20</td></tr><tr><td>AF10</td><td>~0</td><td>~0</td><td>~0</td></tr><tr><td>AF12</td><td>~0</td><td>detach partly</td><td>detach</td></tr><tr><td>AF15</td><td>detach</td><td>detach</td><td>detach</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# CONCLUSION  \n\nA novel photosensitive surfactant composed of Tween20, IPDI, and 2-HEMA was successfully synthesized. This surfactant could undergo copolymerization with the multifunctional crosslinking agent (DPHA) during UV-curing of the coating sol. By means of a hydrophilic/hydrophobic bilayer design, the prepared hard coating not only demonstrated superb antifog performance but also resisted water penetration effectively. Specifically, the coating containing $10\\%$ modified surfactant is transparent, with a high hardness of 5H on PMMA, and can be soaked in water for 7 days at $25~^{\\circ}\\mathrm{C}$ without losing its AF capability.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 6,
+        "chunk": "# ASSOCIATED CONTENT",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# $\\otimes$ Supporting Information  \n\nSEM and 3-D AFM images of the surface of the bottom layer, FTIR spectrum during reactions of IPDI with 2-HEMA and Tween-20 with 2-HEMA/IPDI, and transmission spectra of the single layer and double layer in the visible region. This material is available free of charge via the Internet at http://pubs.acs.org.",
+        "category": " References"
+    },
+    {
+        "id": 8,
+        "chunk": "# AUTHOR INFORMATION",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# Corresponding Author  \n\n$^{*}\\mathrm{E}$ -mail: lpcheng@mail.tku.edu.tw. Phone: +886-2-26215656 ext. 2725 or 2614. Fax: +886-2-26209887.",
+        "category": " References"
+    },
+    {
+        "id": 10,
+        "chunk": "# Notes  \n\nThe authors declare no competing financial interest.",
+        "category": " References"
+    },
+    {
+        "id": 11,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nThe authors thank the National Science Council of Taiwan for the financial support (NSC 96-2628-E-032-001-MY3).",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# REFERENCES  \n\n(1) Oguri, K.; Iwataka, N.; Tonegawa, A.; Hirose, Y.; Takayama, K.; Nishi, Y. Misting-free diamond surface created by sheet electron beam irradiation. J. Mater. Res. 2001, 16, 553−557.   \n(2) Leonard, R. L.; Terekhov, A. Y.; Thompson, C.; Erck, R. A.; Johnson, J. A. Antifog coating for bronchoscope lens. Surf. Eng. 2012, 28 (6), 468−472.   \n(3) Briscof, B. J.; Galvin, K. P. The effect of surface fog on the transmittance of light. Sol. Energy 1991, 46, 191−197.   \n(4) Zhao, H.; Beysens, D. From droplet growth to film growth on a heterogeneous surface - condensation associated with a wettability gradient. Langmuir 1995, 11, 627−634.   \n(5) Gao, X. F.; Yan, X.; Yao, X.; Xu, L.; Zhang, K.; Zhang, J. H.; Yang, B.; Jiang, L. The dry-style antifogging properties of mosquito compound eyes and artificial analogues prepared by soft lithography. Adv. Mater. 2007, 19, 2213−2217.   \n(6) Plasman, V.; Caulier, T.; Boulos, N. Polyglycerol esters demonstrate superior antifogging properties for films. Plast. Addit. Compd. 2005, 7, 30−33.   \n(7) Cebeci, F. C.; Wu, Z. Z.; Zhai, L.; Cohen, R. E.; Rubner, M. F. Nanoporosity-driven superhydrophilicity: A means to create multifunctional antifogging coatings. Langmuir 2006, 22, 2856−2862. (8) Howarter, J. A.; Youngblood, J. P. Self-cleaning and anti-fog surfaces via stimuli-responsive polymer brushes. Adv. Mater. 2007, 19, 3838−3843.   \n(9) Howarter, J. A.; Youngblood, J. P. Self-cleaning and next generation anti-fog surfaces and coatings. Macromol. Rapid Commun. 2008, 29, 455−466.   \n(10) Nuraje, N.; Asmatulu, R.; Cohen, R. E.; Rubner, M. F. Durable antifog films from layer-by-layer molecularly blended hydrophilic polysaccharides. Langmuir 2011, 27, 782−791.   \n(11) Machida, M.; Norimoto, K.; Watanabe, T.; Hashimoto, K.; Fujishima, A. The effect of $\\mathrm{SiO}_{2}$ addition in super-hydrophilic property of $\\mathrm{TiO}_{2}$ photocatalyst. J. Mater. Sci. 1999, 34, 2569−2574.   \n(12) Hattori, A.; Kawahara, T.; Uemoto, T.; Suzuki, F.; Tada, H.; Ito, S. Ultrathin $\\mathrm{SiO_{x}}$ film coating effect on the wettability change of $\\mathrm{TiO}_{2}$ surfaces in the presence and absence of UV light illumination. J. Colloid Interface Sci. 2000, 232, 410−413.   \n(13) Fujishima, A.; Rao, T. N.; Tryk, D. A. $\\mathrm{TiO}_{2}$ photocatalysts and diamond electrodes. Electrochim. Acta 2000, 45, 4683−4690.   \n(14) Tadanaga, K.; Morinaga, J.; Minami, T. Formation of superhydrophobic-superhydrophilic pattern on flowerlike alumina thin film by the sol-gel method. J. Sol-Gel Sci. Technol. 2000, 19, 211−214.   \n(15) Sun, R. D.; Nakajima, A.; Fujishima, A.; Watanabe, T.; Hashimoto, K. Photoinduced surface wettability conversion of $\\mathrm{znO}$ and $\\mathrm{TiO}_{2}$ thin films. J. Phys. Chem. B 2001, 105, 1984−1990.   \n(16) Gao, Y. F.; Masuda, Y.; Koumoto, K. Light-excited superhydrophilicity of amorphous $\\mathrm{TiO}_{2}$ thin films deposited in an aqueous peroxotitanate solution. Langmuir 2004, 20, 3188−3194.   \n(17) Lee, B. I.; Lee, E. S.; Byeon, S. H. Assembly of layered rare-earth hydroxide nanosheets and $\\mathrm{SiO}_{2}$ nanoparticles to fabricate multifunctional transparent films capable of combinatorial color generation. Adv. Funct. Mater. 2012, 22, 3562−3569.   \n(18) Tricoli, A.; Righettoni, M.; Pratsinis, S. E. Anti-fogging nanofibrous $\\mathrm{SiO}_{2}$ and nanostructured $\\mathrm{SiO}_{2}–\\mathrm{TiO}_{2}$ films made by rapid flame deposition and in situ annealing. Langmuir 2009, 25, 12578−12584.   \n(19) Feng, X. J.; Jiang, L. Design and creation of superwetting/ antiwetting surfaces. Adv. Mater. 2006, 18, 3063−3078.   \n(20) Gan, W. Y.; Lam, S. W.; Chiang, K.; Amal, R.; Zhao, H. J.; Brungs, M. P. Novel $\\mathrm{TiO}_{2}$ thin film with non-UV activated superwetting and antifogging behaviours. J. Mater. Chem. 2007, 17, 952−954.   \n(21) Liu, X. M.; He, J. H. Hierarchically structured superhydrophilic coatings fabricated by self-assembling raspberry-like silica nanospheres. J. Colloid Interface Sci. 2007, 314, 341−345.   \n(22) Zhang, L. B.; Li, Y.; Sun, J. $\\mathrm{Q.;}$ Shen, J. C. Mechanically stable antireflection and antifogging coatings fabricated by the layer-by-layer deposition process and postcalcination. Langmuir 2008, 24, 10851− 10857.   \n(23) Faustini, M.; Nicole, L.; Boissiere, C.; Innocenzi, P.; Sanchez, C.; Grosso, D. hydrophobic, antireflective, self-cleaning, and antifogging sol-gel coatings: an example of multifunctional nanostructured materials for photovoltaic cells. Chem. Mater. 2010, 22, 4406−4413.   \n(24) Zhang, L.; Qiao, Z. A.; Zheng, M. A.; Huo, Q. S.; Sun, J. Q. Rapid and substrate-independent layer-by-layer fabrication of antireflection- and antifogging-integrated coatings. J. Mater. Chem. 2010, 20, 6125−6130.   \n(25) Han, J. B.; Dou, Y. B.; Wei, M.; Evans, D. G.; Duan, X. Antireflection/antifogging coatings based on nanoporous films derived from layered double hydroxide. Chem. Eng. J. 2011, 169, 371−378.  \n\n(26) Lu, X. Y.; Wang, Z.; Yang, X. L.; Xu, X.; Zhang, L.; Zhao, N.; Xu, J. Antifogging and antireflective silica film and its application on solar modules. Surf. Coat. Technol. 2011, 206, 1490−1494. (27) Lai, Y. K.; Tang, Y. X.; Gong, J. J.; Gong, D. G.; Chi, L. F.; Lin, C. J.; Chen, Z. Transparent superhydrophobic/superhydrophilic $\\mathrm{TiO}_{2}$ - based coatings for self-cleaning and anti-fogging. J. Mater. Chem. 2012, 22, 7420−7426. (28) Zhang, L.; Lu, C. L.; Li, Y. F.; Lin, Z.; Wang, Z. H.; Dong, H. P.; Wang, T. $\\mathrm{Q.;}$ Zhang, X. M.; Li, X.; Zhang, J. H.; Yang, B. Fabrication of biomimetic high performance antireflective and antifogging film by spin-coating. J. Colloid Interface Sci. 2012, 374, 89−95. (29) Huang, F. H.; Chang, C. C.; Oyang, T. Y.; Chen, C. C.; Cheng, L. P. Preparation of almost dispersant-free colloidal silica with superb dispersiblility in organic solvents and monomers. J. Nanopart. Res. 2011, 13, 3885−3897. (30) Lee, C. K.; Don, T. M.; Lai, W. C.; Chen, C. C.; Lin, D. J.; Cheng, L. P. Preparation and properties of nano-silica modified negative acrylate photoresist. Thin Solid Films 2008, 516, 8399−8407. (31) Chen, C. C.; Lin, D. J.; Don, T. M.; Huang, F. H.; Cheng, L. P. Preparation of organic-inorganic nano-composites for antireflection coatings. J. Non-Cryst. Solids 2008, 354, 3828−3835. (32) Chang, C. C.; Oyang, T. Y.; Hwang, F. H.; Chen, C. C.; Cheng, L. P. Preparation of polymer/silica hybrid hard coatings with enhanced hydrophobicity on plastic substrates. J. Non-Cryst. Solids 2012, 358, 72−76. (33) Jun, J. B.; Park, J. G.; Kim, D. H.; Suh, K. D. Blends of polybutyleneterephthalate with ethylene-propylene elastomer containing isocyanate functional group. Eur. Polym. J. 2001, 37, 597−602. (34) Gao, R. L.; Zhang, M. $\\mathrm{Q.;}$ Dixit, N.; Moore, R. B.; Long, T. E. Influence of ionic charge placement on performance of poly(ethylene glycol)-based sulfonated polyurethanes. Polymer 2012, 53, 1203−1211. (35) Hsu, S. H.; Tang, C. M.; Tseng, H. J. Gold nanoparticles induce surface morphological transformation in polyurethane and affect the cellular response. Biomacromol 2008, 9, 241−248.",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Synthesis of acrylate-based UV/thermal dual-cure coatings for antifogging  \n\nBolong Yao, Haiping Zhao, Likui Wang, Yun Liu, Chunsen Zheng, Hongping Li, Changqing Sun  \n\n$\\circleddash$ American Coatings Association 2017  \n\nAbstract A dual-cure hydrophilic acrylate polymer was synthesized via radical polymerization with acrylic acid (AA), isophorone diisocyanate (IPDI), 2-acrylamide-2-methylpropane sulfonic acid (AMPS), hydroxyethyl acrylate (HEA), and 3-(trimethoxysilyl)propyl-2-methyl-2-methacrylate (MPS) as monomers, then used as prepolymer for antifog coating with tetraethylorthosilicate (TEOS) as a novel crosslinker. The prepolymer was mixed with crosslinking agent and photoinitiator to form coating formulas. The coating was characterized by nuclear magnetic resonance (NMR), Fourier-transform infrared (FTIR) spectroscopy, and contact angle measurements. The results indicated that the dosage of AMPS and TEOS had great influence on the antifog performance. With an increasing TEOS amount, the hardness, adhesion, water resistance, impact resistance, and thermal stability of the films were improved, at the expense of transparency; with increasing dosage of AMPS, the hydrophilicity of the film increased at the expense of water resistance. Optimum coating properties could be obtained when the amount of AMPS was $7\\%$ and that of TEOS was $5.5\\%$ . Scanning electron microscopy (SEM) and atomic force microscopy (AFM) results showed that some $\\mathrm{SiO}_{2}$ microspheres were formed and microphase separation occurred between the macromolecular segments, yielding the excellent coating properties.  \n\nKeywords TEOS, Antifogging, Dual cure, Acrylate",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# Introduction  \n\nTransparent substrates (such as glass) play an important role in daily life.1–4 Due to the high surface energy, condensation of droplets occurs when the temperature of the substrate surface is below the ambient water vapor dew point. These droplets lead to light refraction and scattering, causing transparent materials to become hazy, resulting in many problems and even causing serious harm.5 At present, there are two main methods to solve this problem: electric heating and antifog coating.6 Although the former method is effective, inconvenience and energy consumption limit its wide application. According to antifogging theory, two types of coatings have been researched: superhydrophobic and superhydrophilic.6 Superhydrophobic coatings mainly utilize the gravity of droplets to allow dew condensation to tumble down to achieve the antifogging effect.7–11 However, efficiency remains a major problem, and poor adhesion and mechanical properties such as hardness and scratch resistance also limit wide application of this method. These disadvantages can be overcome more easily when using superhydrophilic coatings, where water droplets on the surface of such coatings rapidly spread into a water film that does not scatter light.12–15 In this case, if dew condensation occurs, the surface can still remain optically clear. Rubner’s group16 adopted a layered self-assembly method to deposit $\\mathrm{SiO}_{2}^{-}$ nanoparticles and polyelectrolyte alternately to form a superhydrophilic porous film. The contact angle was less than $5^{\\circ}$ , with excellent antifogging performance. Also, Zoromba et al.17 developed an ultraviolet (UV)-curable urethane acrylate antifog coating. However, the majority of inorganic nanoparticles require complex preparation processes and they are difficult to coat, usually requiring sintering,18 while it is difficult to obtain a balance between hydrophilicity and water resistance when using organic polymers. The hydrophilicity of a surface mainly relies on various strongly hydrophilic groups, such as hydroxyl, carboxyl, and sulfonic acid.19 On such surfaces, water can penetrate and swell the film.  \n\nIn this work, acrylic ester was used as the main chain because of its good transparency. Hydrophilic monomer 2-acrylamide-2-methylpropane sulfonic acid (AMPS) was introduced to enhance the hydrophilicity of the film. The main chain of acrylic resin was modified with 3-(trimethoxysilyl)propyl-2-methyl-2- methacrylate (MPS), and tetraethylorthosilicate (TEOS) was used as a novel curing agent. The hydroxyl groups from MPS and TEOS, respectively, undergo a dehydration condensation reaction to generate a large number of Si–O–Si bonds20,21 under alkaline conditions. Because Si–O–Si bonds easily migrate to the coating surface during curing, a dense Si–O–Si network structure can form on the surface, giving the film excellent water resistance and mechanical properties. The film is ultimately cured by adding a photoinitiator and reactive diluents through the double bonds introduced into the main chain from halfblocked polyurethane. The other advantage of this approach is that use of tetraethylorthosilicate (TEOS) introduces a large number of hydroxyl groups. The formed $_{\\mathrm{Si-O-Si}}$ bonds with low surface tension bring the hydroxyl groups to the coating surface. This design ensures hydrophilicity and also imparts the coating with excellent mechanical properties and water resistance. Contact angle measurements, atomic force microscopy (AFM), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM) were applied to study the properties of films with different TEOS contents.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# Experimental",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# Materials  \n\nIsophorone diisocyanate (IPDI) was supplied by Bayer Co. Ltd. (Germany). 2-Acrylamido-2-methylpropane sulfonic acid (AMPS) was purchased from SongChuan Industrial Additives Co. Ltd. (ShanDong, China). Hydroxyethyl acrylate (HEA) and 3-(trimethoxysilyl)propyl-2-methyl-2-methacrylate (MPS) were supplied by Sigma-Aldrich Co. Ltd. (Shanghai, China). Trimethylol propane triacrylate (15EO-TMPTA), azobisisobutyronitrile (AIBN), acrylic acid (AA), leveling agent (3288), and tetraethylorthosilicate (TEOS) were purchased from Aladdin Reagent Co. Ltd. (Shanghai, China). Dibutyltin dilaurate (DBTDL), 4-methoxyphenol (MEHQ), $N\\mathrm{,}N$ -dimethylformamide (DMF), photoinitiator (1173), ammonia, acetone (ACE), deuterated dimethyl sulfoxide (DMSO), ethanol, anhydrous methanol, and isopropanol were all supplied by Sinopharm Chemical Reagent Co. Ltd. (Shanghai, China).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# Synthesis of prepolymer  \n\nAA and HEA had been pretreated to remove polymerization inhibitor. A series of acrylate copolymers (PAAMH) were synthesized via free-radical copolymerization. A mixture of AA, AMPS, HEA, MPS, and DMF was added into a dried $250\\mathrm{-mL}$ four-necked flask equipped with mechanical stirrer, condenser, ${\\bf N}_{2}$ catheters, and pressure-equalizing dropping funnel. The mixture was stirred at room temperature under ${\\bf N}_{2}$ protection and gradually heated to $80^{\\circ}\\mathrm{C}$ . AIBN $3\\%$ of total monomer weight) was dissolved in a small amount of DMF, half of which was then added into the flask dropwise via the constant-pressure dropping funnel for $^{1\\mathrm{~h~}}$ at $80^{\\circ}\\mathrm{C}$ , and reacted for another $\\Bar{3}\\Bar{\\mathbf{h}}$ at $80^{\\circ}\\mathrm{C}$ . The remaining initiator was then added to the flask at the same dripping speed, and reacted for another $^{3\\mathrm{~h~}}$ .  \n\nNucleophilic addition of IPDI and HEA was employed to prepare an isocyanate-containing unsaturated monomer, IPHE. A mixture of IPDI, HEA, MEHQ, ACE, and DBTDL was added into a dried $250\\mathrm{-mL}$ four-necked flask equipped with mechanical stirrer, condenser, ${\\bf N}_{2}$ catheters, and pressure-equalizing dropping funnel, then gradually heated to $55^{\\circ}\\mathrm{C}$ and allowed to react for $2\\mathrm{~h~}$ . The isocyanate (NCO) content was monitored during the reaction using the standard dibutylamine backtitration method. Upon reaching the theoretical NCO value, the product was cooled to room temperature, transferred to another pressureequalizing dropping funnel, then added dropwise to the PAAMH. At the same time, additional catalyst DBTDL was added and reacted at $80^{\\circ}\\mathrm{C}$ for about $^{3\\mathrm{~h~}}$ until the NCO content reached another theoretical value. Reaction completion was confirmed by disappearance of the FTIR absorption peak at $22\\dot{7}0~\\mathrm{cm}^{-1}$ corresponding to stretching vibration of NCO group. During the above process, acetone was added to adjust the viscosity of the IPHE prepolymer. Finally, the acetone was removed to afford PAAMH-IH with $30~\\mathrm{wt\\%}$ solid content. The whole synthetic route is shown in Fig. 1. The compositions of all formulas used are presented in Table 1.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# Preparation of antifog coatings  \n\nPAAMH-IH was mixed with $3{\\mathrm{-}}4\\ \\mathrm{wt}\\%$ photoinitiator (Irgacure 1173), $0.3\\ \\mathrm{wt\\%}$ leveling agent 3288, and $25\\ \\mathrm{wt\\%}$ reactive diluents 15EO-TMPTA, and a certain amount of TEOS was introduced, as presented in Table 2. We chose 15EO-TMPTA as the reactive diluents to increase the double-bond content. The $\\mathrm{pH}$ value was adjusted to ${\\sim}13$ using aqueous ammonia (concentration ${\\sim}25\\%$ ), followed by quick stirring at room temperature. The solution was then coated on clean glass slides by dipping, and was then slowly dried at $50^{\\circ}\\mathrm{C}$ for $5\\mathrm{~h~}$ . The resulting films were heated in an oven at $70^{\\circ}\\mathrm{C}$ for another $2\\dot{\\mathrm{~h~}}$ . Finally, the films were irradiated using a 1200-W UV $(200-400~\\mathrm{nm})$ ) lamp for 30 s at room temperature.  \n\n![](images/c181a78292328702bcef4c58ce30dd5d7229f555f168b8c5da2c4a5fa0bc9bf7.jpg)  \nFig. 1: Synthesis and curing process of PAAMH-IH  \n\nTable 1: Components of PAAMH resin   \n\n\n<html><body><table><tr><td rowspan=\"2\">Sample</td><td colspan=\"6\">Content (g)</td><td rowspan=\"2\">W(AMPS) (%)℃</td></tr><tr><td>AA</td><td>HEAa</td><td>AMPS</td><td>MPS</td><td>HEAb</td><td>IPDI</td></tr><tr><td>PAAMH-IH-2%</td><td>10.00</td><td>6.00</td><td>0.72</td><td>2.00</td><td>6.00</td><td>11.50</td><td>2%</td></tr><tr><td>PAAMH-IH-4%</td><td>10.00</td><td>6.00</td><td>1.48</td><td>2.00</td><td>6.00</td><td>11.50</td><td>4%</td></tr><tr><td>PAAMH-IH-6%</td><td>10.00</td><td>6.00</td><td>2.26</td><td>2.00</td><td>6.00</td><td>11.50</td><td>6%</td></tr><tr><td>PAAMH-IH-8%</td><td>10.00</td><td>6.00</td><td>3.09</td><td>2.00</td><td>6.00</td><td>11.50</td><td>8%</td></tr><tr><td>PAAMH-IH-10%</td><td>10.00</td><td>6.00</td><td>3.94</td><td>2.00</td><td>6.00</td><td>11.50</td><td>10%</td></tr></table></body></html>\n\na Content of HEA on main chains; b Content of HEA on side chains; c Percentage of AMPS in total monomers  \n\nTable 2: Components of PAAMH-IH resin   \n\n\n<html><body><table><tr><td rowspan=\"2\">Sample</td><td colspan=\"5\">Content (g)</td><td rowspan=\"2\">W(TEOS) (%)</td></tr><tr><td>PAAMH-IH</td><td>TEOS</td><td>Ammonia</td><td>15EO-TMPTA</td><td>1173</td></tr><tr><td>PAAMH-IH-a</td><td>1.00</td><td>0.02</td><td>0.04</td><td>0.02</td><td>0.03</td><td>1.83%</td></tr><tr><td>PAAMH-IH-b</td><td>1.00</td><td>0.04</td><td>0.04</td><td>0.02</td><td>0.03</td><td>3.67%</td></tr><tr><td>PAAMH-IH-c</td><td>1.00</td><td>0.06</td><td>0.04</td><td>0.02</td><td>0.03</td><td>5.50%</td></tr><tr><td>PAAMH-IH-d</td><td>1.00</td><td>0.08</td><td>0.04</td><td>0.02</td><td>0.03</td><td>7.34%</td></tr><tr><td>PAAMH-IH-e</td><td>1.00</td><td>0.10</td><td>0.04</td><td>0.02</td><td>0.03</td><td>9.17%</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# Characterization  \n\nA Fourier-transform infrared spectrophotometer (FTLA2000-104, ABB Bomem of Canada) was used to confirm the chemical structure of IPHE, PAAMH, and PAAMH-IH. Purified product was dissolved in deuterated DMSO with tetramethylsilane (TMS) as internal standard. Then, $^1\\mathrm{H}$ and $^{13}\\mathrm{C}$ NMR spectra were recorded using a Bruker $500~\\mathrm{MHz}$ NMR (Avance III) to confirm the structure of PAAMH. Scanning electron microscopy (SEM, S4800, Hitachi) and atomic force microscopy (AFM, MultiMode 8, Bruker) were used to investigate the coating morphology. Samples were diluted to $15\\ \\mathrm{wt\\%}$ solid content with DMF, dripped onto a silicon wafer, and cured. The water resistance of the film was measured with reference to GB/T 1733- 1993 ‘‘determination of resistance to water of films.’’ Film hardness was measured with reference to GB/T 6739-2006 ‘‘paint and varnish pencil method to determine the hardness.’’ Adhesion was tested with reference to GB/T 9286-1998 ‘‘paint and varnish film crossgrid test.’’ Dried film (approximately $10\\ \\mathrm{cm}\\times5\\ \\mathrm{cm}$ ) was fixed on millimeter grid paper (grid: $1\\ \\mathrm{mm}\\ \\times\\ 1$ mm), and Scotch tape (3M, width $1.5\\ \\mathrm{cm}$ ) was pasted tightly onto the glass substrate. The number of grids covered by tape was recorded as $A_{0}$ . The tape was then pulled off quickly at angle of $180^{\\circ}$ , and the number of grids covered by the remaining film was recorded as $A$ . The adhesion22 of the film was then calculated as  \n\n$$\n{\\mathrm{Adhesion~}}(\\%)={\\frac{\\mathrm{A}}{\\mathrm{A}_{0}}}\\times100\n$$  \n\nThe test results were categorized into six grades, from 0 as the best to 6 as the worst. Impact strength was tested with reference to GB/T 1732-1993 ‘‘film impact resistance test.’’ Water absorption was investigated by immersing dried resin film (approximately $\\mathrm{{\\bar{1}}c m}\\times\\mathrm{{\\bar{1}}c m}$ , weight $M_{0.}$ ) into water for $\\bar{24}\\mathrm{{h}}$ . The film was then taken out of the water, and after the water on the surface had been removed using filter papers, the film was weighed immediately $(M_{1})$ . The water absorption22 of the film was then calculated as  \n\n![](images/f22bed839062018aa98bbd0b9af7c67e135d6fb64accd8bd6f6e32c505b7c402.jpg)  \nFig. 2: FTIR spectra of (a) PAAMH-IH, (b) PAAMH, and (c) IPHE  \n\nWater absorption $(\\%)=\\frac{M_{\\mathrm{1}}-M_{\\mathrm{0}}}{M_{\\mathrm{0}}}\\times100.$  \n\nContact angles were tested using a DataPhysics OCA40 equipped with environmental chamber. Three drops of water were used for each measurement, and average contact angle values were recorded. Samples were prepared on transparent glass, with another, analogous glass used as background, and a doublebeam UV–Vis spectrophotometer (Beijing, TU-1901) was used to measure the transparency of the coating. Differential scanning calorimetry (DSC, Netzsch 204F1, Germany) measurements were carried out in the temperature range from $-20$ to $150^{\\circ}\\mathrm{C}$ under ${\\bf N}_{2}$ atmosphere at heating rate of $30^{\\circ}\\mathrm{C/min}$ . To test their antifog properties, different samples were held above hot water $({\\bar{8}}0^{\\circ}\\mathrm{C})$ for $15\\mathrm{~s~}$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# Results and discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# FTIR spectroscopy  \n\nThe FTIR spectra of IPHE, PAAMH, and PAAMHIH are shown in Fig. 2. Comparing spectra (a) and (c), the peaks at 1527 and $3360~\\mathrm{cm}^{-1}$ correspond to $-\\mathrm{\\mathbf{N}\\mathrm{\\mathbf{H}}}$ bending vibration and stretching vibration. The peak at $3300~\\mathrm{cm}^{-1}$ in spectrum (b) corresponds to hydroxyl absorption. As shown in Fig. 2, the absorption peak of $\\scriptstyle{\\mathrm{C=C}}$ stretching vibration at about $1640^{\\cdot}\\mathrm{cm}^{-1^{\\cdot}}$ disappeared from curve (b), indicating completion of the free-radical polymerization process. The reappearance of the $C{=}C$ absorption peak in curve (a) indicates successful introduction of IPHE. Comparing curves (c) and (a), the absorption peak of –NCO for IPHE at $2270~\\mathrm{{cm}^{-1}}$ disappeared from curve (a), indicating successful reaction of IPHE with PAAMH. Additionally, a strong absorption peak due to a sulfonic group was observed at about $11\\dot{7}0~\\mathrm{cm}^{-1}$ , suggesting successful introduction of AMPS. A weak absorption peak at $1020~\\mathrm{cm}^{-1}$ is attributed to $_{\\mathrm{Si-O-Si}}$ stretching, indicating successful introduction of MPS.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# $\\mathbf{\\nabla}^{I}H$ and $^{I3}C$ NMR analysis  \n\n$^1\\mathrm{H}$ and $^{13}\\mathrm{C}$ NMR techniques were employed to further confirm the structure of the prepolymer. The spectra for PAAMH are shown in Fig. 3, showing peaks for two methylene protons from the main chain $\\left(\\mathrm{-CH}_{2}\\mathrm{-}\\right)$ at $1.20~\\mathrm{ppm}$ and from two methyl protons $\\left(\\mathrm{CH}_{3^{-}}\\right)$ linking with acrylamide at 1.31 ppm. The signal for methylene $(-\\mathrm{CH}_{2}\\mathrm{-}\\mathrm{SO}_{3}\\mathrm{H})$ protons directly attached to sulfonic acid group appeared at $3.45~\\mathrm{ppm}$ . In combination with the FTIR spectra, the $^1\\mathrm{H}$ NMR spectrum further indicates introduction of AMPS. The signals at 4.08 and $1.44~\\mathrm{ppm}$ are due to two methylene protons directly connected with ester bond from both MPS and HEA. The signal for a methylene group (OH– $\\mathrm{CH}_{2^{-}}\\mathrm{\\rangle}$ ) proton directly connected to hydroxyl groups appears at $2.23~\\mathrm{ppm}$ , proving successful introduction of MPS and HEA.  \n\nThe $^{13}\\mathrm{C}$ NMR spectrum showed no peaks at $\\delta$ of $100{-}165~\\mathrm{ppm}$ , indicating no olefin. The saturated carbon $\\left(-\\mathrm{CH}_{2}\\mathrm{-CH}_{2}-\\right)$ absorption peak at $-2.1$ to $43\\ \\mathrm{ppm}$ further demonstrates that the AA, AMPS, MPS, and HEA double bonds were fully open. Both the $^1\\mathrm{H}$ and $^{13}\\mathrm{C}$ NMR spectra confirm synthesis of PAAMH.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# Water contact angle and water absorption of antifog coatings  \n\nFigure 4 shows the water contact angle (CA) and water absorption of the different PAAMH-IH prepolymers. Note that the CA decreased while the water absorption rose with increasing AMPS content. For AMPS content of $10\\%$ , the water absorption by the film reached $18.2\\%$ and the surface was swelled and tacky, thus being unusable. This result can mainly be attributed to the increasing sulfonic acid group content.19 Considering the balance between CA and water resistance, the optimum content of AMPS in the prepolymer was $^{6-}$ $8\\%$ . Regarding the dosage of curing agent (TEOS), all used prepolymer PAAMH-IH- $6\\%$ .",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# Transparency of antifog coatings  \n\nThe transparency of antifog coatings is crucial for their applications, as poor transparency limits their application in optical instruments.23 Figure 5 shows UV–Vis spectra of cured films with different TEOS contents (Table 2). With increasing TEOS content, the light transmission (at $700~\\mathrm{nm},$ ) reduced from above 95 to $85\\%$ , and the transparency was greatly affected. This is probably because, although most silanol (Si–OH) in the main chain reacted with MPS to form $_{\\mathrm{Si-O-Si}}$ bonds, a small amount of TEOS remained, forming $\\mathrm{SiO}_{2}$ nanoparticles, as shown in Figs. 6a–6c; all images show $\\mathrm{SiO}_{2}$ microspheres unevenly distributed on the coating surface, which reduced the transparency.  \n\n![](images/69e814c08962eb4f4a6d56fb3b5e25b7453f5886c89d0967e809f7b99874ae84.jpg)  \nFig. 3: (a) $\\mathsf{\\Omega}^{1}\\mathsf{H}$ and (b) $\\boldsymbol{^{13}0}$ NMR spectra of PAAMH",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# Spreading time and contact angle  \n\nThe spreading time and CA of the PAAMH-IH films with different TEOS contents are shown in Fig. 7. As the TEOS content was increased from 1.83 to $9.17\\%$ , the CA decreased from $25.7^{\\circ}$ to $9.8^{\\circ}$ . This is mainly because TEOS formed hydroxyl groups on the coating surface, enhancing its hydrophilicity. During the crosslinking process, although some of the hydroxyl groups dehydrated and formed Si–O–Si bonds, there were still a large number of hydroxyl groups that failed to form $_{\\mathrm{Si-O-Si}}$ bonds. The formed Si–O–Si with low surface energy and poor compatibility easily migrates to the film surface during the curing process, taking hydroxyl groups to the film surface for microphase separation. According to curve (e) in Fig. 7, the TEOS content was higher than the other four groups, but the CA still showed an upward trend instead. Maybe more TEOS formed $\\mathrm{SiO}_{2}$ nanoparticles that were embedded into the film during curing, and the amount of hydroxyl groups that migrated to the surface decreased. Figure 7 shows that the spreading times on the coating (droplet volume $2~\\upmu\\mathrm{L}$ ) were very short, all being below $1500~\\mathrm{{\\bar{ms}}}$ .  \n\n![](images/4bda75366c2c5e577d5c3d63da7de62a98e094db1e78c655a3d8851c25f36fd3.jpg)  \nFig. 4: Water contact angle and water absorption of PAAMH-IH  \n\n![](images/0040058bf32ea49f1c07d306916827e2fdd35a987ad9f97e29c40b9287a5bc58.jpg)  \nFig. 5: Transparency of antifog coatings",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# AFM analysis of antifog coatings  \n\nFigure 8 shows AFM two-dimensional (2D) height maps and phase patterns for the PAAMH-IH films. The 2D height maps show that all the surfaces were smooth within a small range, all having average roughness $\\left(R_{\\mathrm{a}}\\right)$ close to 1.025. The coating flatness in regions without microspheres was still good. In general, lighter areas of AFM phase images correspond to hard segments while darker areas correspond to soft segments. The phase maps of the surfaces of the coatings in Fig. 8 show significant differences between light and dark, indicating distinct microphase separation. The gradual expansion of discontinuous dark areas from PAAMH-IH-a to PAAMH-IH-e indicates more obvious microphase separation with increasing TEOS dosage.  \n\n![](images/50b925d98477075b3aedd070750254c72dd46e1e98cbfd0d388e14580fec92cc.jpg)  \nFig. 7: Water contact angle and spreading time for (a) PAAMH-IH-a, (b) PAAMH-IH-b, (c) PAAMH-IH-c, (d) PAAMHIH-d, and (e) PAAMH-IH-e  \n\n![](images/dcf7cc6f9c1a6c43183d2932a493afb858d19e1f0cd79021360f424a970f3e5c.jpg)  \nFig. 6: SEM images of PAAMH-IH coatings: (a) PAAMH-IH-a, (b) PAAMH-IH-c, and (c) PAAMH-IH-e  \n\n![](images/1e5b93369d56111158ea014bd2fd9f74d05f5e3c75c3f6b75f027342e0815126.jpg)  \nFig. 8: AFM images of PAAMH-IH, (a) PAAMH-IH-a, (b) PAAMH-IH-c, and (c) PAAMH-IH-e  \n\n![](images/b1db7b2158e64fa661f006b4dc1202768b6ce20ca6979379b2020dd4a32f8d4b.jpg)  \nFig. 9: DSC curves of PAAMH-IH: (a) uncured, (b) thermally cured with TEOS, (c) UV cured, and (d) dual cured",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# DSC analysis  \n\nFigure 9 shows the DSC curves for PAAMH-IH. The curve for pure resin without curing is (a). Curve (b) is for the crosslinked film with just thermal curing with TEOS. Curve (c) is for the crosslinked film with just UV curing. Curve (d) is for the film with dual curing. Comparing (a) and (b), one finds that the glass transition temperature $(T_{\\mathrm{g}})$ of the film increased from 0.45 to $20.12^{\\circ}\\mathrm{C}$ , indicating the occurrence of the crosslinking reaction during film curing with formation of a crosslinked network structure. Comparing (a) and (c), the $T_{\\mathrm{g}}$ of the film rose from 0.45 to $73.62^{\\circ}\\mathrm{C}$ ， indicating that UV curing also occurred. Comparing (a), (b), (c), and (d), the gradually increasing $T_{\\mathrm{g}}$ confirms that a dual-curing reaction occurred.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# Mechanical performance and water resistance of coatings  \n\nTable 3 presents the film properties of the coatings with different TEOS content. The results in Table 3 show that all samples exhibited high pencil hardness, with the highest reaching 3H. This can be attributed to high crosslink density of the polymer and large cohesive energy of crosslinked molecules. According to the impact resistance results, with increasing TEOS content, the impact strength also increased. No cracking or peeling phenomena were observed on the surfaces after impact. The maximum impact strength reached $70\\ \\mathrm{cm}$ . The maximum adhesion grade of the film reached 0. This is because the silane coupling agent (MPS) in the main chain of PAAMH-IH reacted with hydroxyl groups on the glass substrate surface to form $\\dot{\\mathrm{Si-O-}}\\dot{\\mathrm{Si}}$ bonds. After soaking for $24\\mathrm{~h~}$ , none of the coatings showed whitening phenomenon, indicating excellent water resistance. These results demon  \n\nTable 3: Effects of amount of TEOS on film properties   \n\n\n<html><body><table><tr><td>Test item</td><td colspan=\"5\">TEOS (wt%)</td></tr><tr><td></td><td>PAAMH-IH-a</td><td>PAAMH-IH-b</td><td>PAAMH-IH-C</td><td>PAAMH-IH-d</td><td>PAAMH-IH-e</td></tr><tr><td>Pencil hardness</td><td>2H</td><td>3H</td><td>3H</td><td>3H</td><td>3H</td></tr><tr><td>Adhesion grade</td><td>1</td><td>1</td><td>0</td><td>0</td><td>0</td></tr><tr><td>Water resistance</td><td>No whitening</td><td>No whitening</td><td>No whitening</td><td>No whitening</td><td>No whitening</td></tr><tr><td>Impact resistance (mm)</td><td>60</td><td>65</td><td>70</td><td>70</td><td>70</td></tr></table></body></html>  \n\n![](images/6afd7bba107891a2b0c037016dfbd06db9482f7098de0375229b910bc7a91595.jpg)  \n\n![](images/41fbf23d640d8f8dbddc7682983db39fbe0ee780dd54b1532aa16c752b124170.jpg)  \nFig. 10: 1 Antifog property of coatings: (a) PAAMH-IH-a, (b) PAAMH-IH-b, (c) PAAMH-IH-c, (d) PAAMH-IH-d, (e) PAAMH-IH-e. 2 Comparison of transparency of films  \n\nstrate that the UV-cured coating with proper formula exhibited excellent coating performance.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# Antifog property of coatings  \n\nThe antifog property of the coatings was tested, and the results are shown in Fig. 10-1. The transparency of the films is compared in Fig. 10-2. In each graph, the glass on the right is coated with PAAMH-IH antifog coating while the left side is left uncoated for reference. As shown by these pictures, the glass with antifog coating remained transparent while the uncoated glass became hazy due to water condensation. With increasing TEOS content, the transparency decreased, as shown in Fig. 10-2.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# Conclusions  \n\nA functional resin was successfully synthesized using IPDI, AMPS, HEA, MPS, and AA as raw materials. Mixing with TEOS as novel crosslinking agent enabled preparation of antifog coatings. DSC curves confirmed the crosslinking reaction between MPS and TEOS during film formation, resulting in a crosslinked network structure. AFM images revealed microphase separation on the coating surface with migration of Si– O–Si bonds to the surface of the coating, leading to good adhesion, hardness, and water resistance, compared with traditional antifog coatings.  \n\nVarious characterization techniques were applied to determine the optimum amounts of AMPS and TEOS. When the amount of AMPS was increased from 2 to $10\\%$ , the hydrophilicity of the coating increased, but the water absorption also increased, reaching a value of $18.2\\%$ , indicating poor water resistance. When the amount of TEOS was increased from 1.83 to $9.17\\%$ , the hardness, hydrophilicity, and water resistance increased, but the transparency decreased. Overall, the coating produced using $6{-}8\\%$ AMPS and $5.5\\%$ TEOS showed excellent antifog performance and mechanical properties.  \n\nAcknowledgments This work was financially supported by the Natural Science Foundation of China (No. 51302109) and Natural Science Foundation of Jiangsu Province (BK20130144).",
+        "category": " Conclusions"
+    },
+    {
+        "id": 19,
+        "chunk": "# References  \n\n1. Nuraje, N, Asmatulu, R, Cohen, RE, Rubner, MF, ‘‘Durable Antifog Films From Layer-by-Layer Molecularly Blended Hydrophilic Polysaccharides.’’ Langmuir, 27 (2) 782–791 (2011) 2. Thompson, CS, Fleming, RA, Zou, M, ‘‘Transparent Selfcleaning and Antifogging Silica Nanoparticle Films.’’ J. Sol. Energy Mater. Sol. Cells, 115 (10) 108–113 (2013)  \n\n3. Zhang, L, Qiao, ZA, Huo, Q, Sun, J, ‘‘Rapid and SubstrateIndependent Layer-by-Layer Fabrication of Antireflectionand Antifogging-Integrated Coatings.’’ J. Mater. Chem., 20 (29) 6125–6130 (2010)   \n4. Chevallier, P, Turgeon, S, Sarra-Bournet, C, Turcotte, R, Laroche, G, ‘‘Characterization of Multilayer Anti-fog Coatings.’’ J. Appl. Mater. Interfaces, 3 (3) 750–758 (2011)   \n5. Zhao, J, Ma, L, Millians, W, Wu, T, Ming, W, ‘‘DualFunctional Antifogging/Antimicrobial Polymer Coating.’’ J. Appl. Mater. Interfaces, 8 (13) 8737–8742 (2016)   \n6. Lee, DI, Son, BG, Bae IJ, ‘‘Anti-fog Heat Generating Glass System and Method For Controlling The Same.’’ US patent 8,870,394, 2014   \n7. Gao, XF, Yan, X, Yao, X, Liang, X, Kai, Z, Zhang, JH, Bai, Y, Lei, J, ‘‘The Dry-Style Antifogging Properties of Mosquito Compound Eyes and Artificial Analogues Prepared by Soft Lithography.’’ J. Adv. Mater., 19 (17) 2213– 2217 (2007)   \n8. Lee, H, Alcaraz, ML, Rubner, MF, Cohen, RE, ‘‘ZwitterWettability and Antifogging Coatings with Frost-resisting Capabilities.’’ ACS Nano, 7 (3) 2172–2185 (2013)   \n9. Wang, JJ, Wang, DS, Wang, J, Zhao, WL, Wang, CW, ‘‘High Transmittance and Superhydrophilicity of Porous $\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ Bi-layer Films without UV Irradiation.’’ J. Surf. Coat. Tech., 205 (12) 3596–3599 (2011)   \n10. Lai, YK, Tang, YX, Gong, JJ, Gong, DG, Chi, LF, Lin, CJ, ‘‘Transparent Superhydrophobic/Superhydrophilic $\\mathrm{TiO}_{2}$ - based Coatings for Self-cleaning and Anti-fogging.’’ J. Mater. Chem., 22 (15) 7420–7426 (2012)   \n11. Chen, Y, Zhang, YB, Shi, L, Jing, L, Xin, Y, Yang, TT, ‘‘Transparent Superhydrophobic/Superhydrophilic Coatings for Self-cleaning and Anti-fogging.’’ Appl. Phys. Lett., 101 (3) 033701-1–033701-4 (2012)   \n12. Han, J, Dou, Y, Wei, M, Evans, DG, Duan, X, ‘‘Antireflection/Antifogging Coatings Based on Nanoporous Films Derived from Layered Double Hydroxide.’’ Chem. Eng. J., 169 (1–3) 371–378 (2011)   \n13. Liu, XM, Xin, D, He, J, ‘‘Hierarchically Structured Porous Films of Silica Hollow Spheres via Layer-by-Layer Assembly and Their Superhydrophilic and Antifogging Properties.’’ ChemPhysChem, 9 (2) 305–309 (2008)   \n14. Zhang, L, Li, Y, Sun, J, Shen, J, ‘‘Mechanically Stable Antireflection and Antifogging Coatings Fabricated by the Layer-by-Layer Deposition Process and Postcalcination.’’ Langmuir, 24 (19) 10851–10857 (2006)   \n15. Miyauchi, M, Nakajima, A, Hashimoto, K, Watanabe, T, ‘‘A Highly Hydrophilic Thin Film Under $1\\ \\upmu\\mathrm{W}/\\mathrm{cm}^{2}$ UV Illumination.’’ J. Adv. Mater., 12 (24) 1923–1927 (2000)   \n16. Cebeci, FC, Wu, Z, Zhai, L, Cohen, RE, Rubner, MF, ‘‘Nanoporosity-driven Superhydrophilicity A Means to Create Multifunctional Antifogging Coatings.’’ Langmuir, 22 (6) 2856–2862 (2006)   \n17. Zoromba, MST, Preparation and Characterization of New Nanostructured Organic/Inorganic Composite Coatings for Anti-fog Applications. Clausthal University of Technology, D. Faculty of Natural and Material Sciences, ClausthalZellerfeld (2009)   \n18. Liu, XM, He, J, ‘‘Hierarchically Structured Superhydrophilic Coatings Fabricated by Self-assembling Raspberry-Like Silica Nanospheres.’’ J. Colloid Interface Sci., 314 (1) 341– 345 (2007)   \n19. Yuan, Y, Liu, R, Wang, C, Luo, J, Liu, X, ‘‘Synthesis of UVcurable Acrylate Polymer Containing Sulfonic Groups for Anti-fog Coatings.’’ J. Prog. Org. Coat., 77 (4) 785–789 (2014)   \n20. Wong, YJ, Zhu, L, Teo, WS, Tan, YW, Yang, Y, Wang, C, Chen, H, ‘‘Revisiting the Stober Method Inhomogeneity in Silica Shells.’’ J. Am. Chem. Soc., 133 (30) 11422–11425 (2011)   \n21. Liu, H, Li, HL, Ding, ZL, Fu, AP, Wang, HY, Guo, PZ, Yu, JQ, Wang, CG, Zhao, XS, ‘‘Preparation of Porous Hollow $\\mathrm{SiO}_{2}$ Spheres by A Modified Stober Process Using MF Microspheres as Templates.’’ J. Clust. Sci., 23 (2) 273–285 (2012)   \n22. Pi, P, Chen, X, Wen, X, Xu, S, Cheng, J, ‘‘Preparation and Characterization of Ambient-Temperature Self-crosslinkable Water-Soluble Acrylic Resin for PE Film Ink.’’ J. Coat. Technol. Res., 13 (1) 73–80 (2016)   \n23. Howarter, JA, Youngblood, JP, ‘‘Self-Cleaning and Next Generation Anti-Fog Surfaces and Coatings.’’ Macromol. Rapid Commun., 29 (6) 455–466 (2008)",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# (12) United States Patent Barr et al.",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (54) FUNCTIONAL POLYMER  \n\n(75） Inventors: Robert K. Barr, Shrewsbury, MA (US); Edgardo Anzures, Westborough, MA (US); Daniel E. Lundy, Winchendon, MA (US)  \n\n(73） Assignee: Rohm and Haas Electronic Materials LLC, Marlborough, MA (US)  \n\n(\\*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 263 days.  \n\n(21） Appl.No.: 10/391,154 (22) Filed: Mar. 18, 2003 (65) Prior Publication Data  \n\nUS 2004/0063027 A1 Apr.1,2004",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# Related U.S. Application Data  \n\n(60） Provisional application No. 60/432,875, filed on Dec. 12, 2002, provisional application No. 60/414,759, filed on Sep. 30, 2002, provisional application No. 60/414,758, filed on Sep.30, 2002.  \n\n(51) Int. Cl. C08F 2/46 (2006.01) C08G 73/06 (2006.01) G03C 1/73 (2006.01)   \n(52) U.S. Cl. 522/34; 522/34; 522/35; 522/48; 522/50; 528/423; 430/286.1   \n(58) Field of Classification Search 430/270.1; 526/319 See application file for complete search history.",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# References Cited",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# U.S. PATENT DOCUMENTS  \n\n3,719,638 A 3/1973 Huemmer et al.   \n3,928,299 A 12/1975 Rosenkranz et al.   \n4,040,925 A 8/1977 McGinniss   \n4,186,069 A 1/1980 Muzyczko et al.   \n4,224,398 A 9/1980 Muzyczko et al.   \n4,273,851 A 6/1981 Muzyczko et al.   \n4,308,394A 零 12/1981 Shuster et al. 560/51   \n4,537,855 A 8/1985 Ide   \n(10) Patent No.: US 7,148,265 B2   \n(45) Date of Patent: Dec.12, 2006  \n\n4,795,787A 1/1989 Walz 4,910,119 A 3/1990 Schneller et al. 4,912,018 A 3/1990 Osuch et al. 4,992,354A 2/1991 Axon et al. 5,037,913 A 8/1991 Leussler et al. 5,068,262 A 11/1991 Noguchi 5,108,870 A 4/1992 Shalom 5,153,323 A 10/1992 Rossman et al. 5,415,972 A 5/1995 Mayes 5,492,790 A 2/1996 Hishiro 5,583,163A 12/1996 Muller 5,683,856 A 11/1997 Aoai et al. 5,712,078 A 1/1998 Huang et al. 5,719,008 A 2/1998 Hozumi et al. 5,733,714 A 3/1998 McCulloch et al. 5,807,927 A 9/1998 Stockinger et al. 5,869,220 A 2/1999 Hallock et al. 5,910,395 A 6/1999 Li et al. 5,919,599 A \\* 7/1999 Meador et al. 430/271.1 5,945,489 A 8/1999 Moy et al. 6,007,833A 12/1999 Chudzik et al. 6,025,410 A 2/2000 Moy et al. 6,153,349 A 11/2000 Ichikawa et al. 6,156,345 A 12/2000 Chudzik et al. 6,165,677 A 12/2000 Yako 6,207,356 B1 3/2001 Banba et al. 6,242,597 B1 6/2001 Gupta et al. 6,251,569 B1 6/2001 Angelopoulos et al. 6,297,328 B1 10/2001 Collins et al. 6,406,828 B1 6/2002 Szmanda et al. 6,455,479 B1 9/2002 Sahbari 6,458,517 B1 10/2002 Nohara et al.   \n04/0063026 A1\\* 4/2004 Barr et al. 430/270.1   \n04/0063030 A1 4/2004 Barr et al.   \n04/0224259 A1\\* 11/2004 Anzures et al. 430/281.1",
+        "category": " References"
+    },
+    {
+        "id": 6,
+        "chunk": "# FOREIGN PATENT DOCUMENTS  \n\nEP 0 469584B1 3/1997  \n\n\\* cited by examiner  \n\nPrimary Examiner—Rosemary Ashton (74)Attorney, Agent, or Firm—John J. Piskorski",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# ABSTRACT  \n\nA polymer having $\\mathbf{\\alpha}_{\\alpha,\\beta}$ unsaturated groups and a group that generates a free radical when exposed to actinic radiation. The polymer may be self-cross-linking.  \n\n7 Claims, No Drawings",
+        "category": " Abstract"
+    },
+    {
+        "id": 8,
+        "chunk": "# 1 FUNCTIONALPOLYMER  \n\nThis application claims the benefit of U.S. Provisional Application(s) No(s).: 60/414,759,filed Sep. 30, 2002, 60/414,758, filed Sep.30, 2002, 60/432,875, filed Dec.12, 2002.",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# BACKGROUND OF THE INVENTION  \n\nThe present invention is directed to a functional polymer. 1 More specifically, the present invention is directed to a functional polymer having unsaturated groups and produces a free radical upon exposure to actinic radiation.  \n\nPolymers are employed for numerous purposes in a wide variety of industries. Functional polymers that readily form films on a surface are highly desirable for use in the fields of lithography, optical data storage, decorative pigments, adhesives, cosmetics, paints, shellack, security applications or active and passive optical elements such as polarizers, optical retarders or color filters, electrophotographic imaging members, and the like.  \n\nIn addition to polymers, acrylates, methacrylates and other unsaturated monomers are employed in coatings, adhesives, sealants, and elastomers, and may be cross-linked by ultraviolet light (UV) radiation or peroxide initiated free radical cure. Such monomers are typically low molecular weight compounds that may be volatile or readily absorbed through skin and may cause adverse health effects. Additionally, many such unsaturated monomers are unstable in compositions, thus they precipitate out of solution during storage reducing the shelf life of the composition. Further, many unsaturated monomers precipitate out of processing solution leaving an undesirable scum or residue, which may contaminate articles or manufacturing apparatus. Reducing the monomer content of compositions may overcome some of the foregoing problems, however, unsaturated monomers are often needed to provide the cross-linking component in a composition.  \n\nIn addition to unsaturated monomers, photoinitiators employed in compositions sensitive to actinic radiation also create unwanted problems. Many photoinitiators are insoluble in aqueous or polar diluents because of their aromatic structures. As a result such photoinitiators precipitate out of solution to contribute to the undesirable scum and residue caused by unsaturated monomers. Such a problem is especially found in a number of photoresists. Also, such photoinitiators may be absorbed through the skin creating a hazard to workers.  \n\nPhotoresists include at least a resin binder, a cross-linking monomer or oligomer and a photoinitiator. A wide variety of polymeric binders may be used in photoresists. Such polymeric binders may include, as polymerized components, one or more acid functional monomers such as acrylic acid or methacrylic acid. Photoresists may be employed in a number of industries. Such industries include, but are not limited to, the electronics industry such as the manufacture of printed wiring boards, photomasks, planographic printing plates and semiconductors, color filters for use in color liquid crystal display devices, and color image pick-up elements.  \n\nA photoresist may be either positive-acting or negative- 6( acting. For negative-acting photoresists, coating layer portions that are exposed to activating radiation polymerize or cross-link in a reaction between a photoactive compound and polymerizable agents of the photoresist composition. Consequently, the exposed coating portions are rendered 6: less soluble in a developer solution than unexposed portions. For positive-acting photoresists, exposed portions are ren  \n\ndered more soluble in a developer solution while areas not exposed remain comparatively less developer soluble.  \n\nPhotoresists also may be either liquid or dry film. Liquid photoresists are disposed, coated, or applied on a substrate and then cured.Dry film photoresists may be laminated to a substrate. One problem with many photoresists is that they are difficult to strip from electrolytically plated circuit boards using conventional alkaline aqueous stripping solutions, e.g. $3\\%$ sodium hydroxide solutions. If the photoresist is not completely stripped and removed, ragged metal circuit lines may result after etching and may cause short-circuiting of the board.  \n\nOrganic-based (amine- or organic solvent-containing) alkaline stripping solutions may be used which produce smaller stripped particles to facilitate stripping. While such organic-based strippers remove photoresist better than inorganic-based strippers, they are expensive relative to inorganic-based strippers (e.g. sodium or potassium hydroxide) and have more waste treatment and environmental concerns associated with them. Solvent-strippable photoresists are much less desirable due to workplace regulations limiting or reducing solvent emissions.  \n\nAnother problem associated with many photoresists is the build-up of organic scum and residue from uncured photo  \n25 resist, as briefly mentioned above. Such organic scum and residue may deposit on various articles and apparatus during the manufacture of products made using photoresists such as printed wiring boards, developer solutions and developer apparatus. Much of the organic scum and residue is caused   \n30 by unsaturated monomers and oligomers such as (meth) acrylate-based compounds and photoactive agents having numerous aromatic groups. Examples of such photoactive agents that may form part of the scum and residue include, but are not limited to, imidazole dimers, benzophenones,   \n35 acetophenones, anthraquinones, naphthaquinones, and triazine-based compounds. Such contaminants are not readily water-soluble or water-dispersible after they form residues in solution or deposit on an article or apparatus.As dissolved photoresists build up in solution (developer loading)   \n40 insoluble organic materials begin to form in the developing tank eventually forming scum or residue. Presence of antifoam additives (added to developer solutions to minimize foaming) increases the tendency for residue and scum to form. As the level of scum builds chances increase for a   \n45 redeposit of the scum and residue onto the developed circuit board. Such redeposited residues cause a retardation of etching solution (etching chemistries have difficulty penetrating organic residues) and cause plating inhibition. Where etch is retarded, circuit shorts form causing a defec  \n50 tive circuit board. In addition to increasing potential for defective circuit boards, the residue and scum also make cleaning equipment difficult, thus increasing maintenance time and cost in circuit board manufacturing. U.S.Pat.No.5,945,489 andU.S.Pat.No. 6.025,410 both   \n55 to Moy et al. (also see “Novel Resins That Cure Without Added Photoinitiator\" by Sheridan et al. Chemistry II-New Chemistry, RadTech 2002, pages 462-474 (Technical Conference Proceedings)) disclose photosensitive oligomers that may be cross-linked without an added photoinitiator. The   \n60 patents disclose that a Michael addition of acetoacetate donors to multifunctional acrylate receptor compounds yields polyesters with reactive pendent acrylate groups, which may be cross-linked in a subsequent curing reaction. The patents state that pendent methyl ketone substituents   \n65 serve as an internal photoinitiator. Upon exposure to UV radiation, an acyl radical with the methyl substituent is believed to be formed which acts as a photoinitiator, thus  \n\nphotoinitiators are not added to compositions containing the oligomers. Such oligomers are liquid oligomers, which may be employed as decorative coatings on wood and metal substrates. Odor generated from unreacted photoinitiators and skin absorption of unreacted photoinitiators is avoided, thus compositions containing such oligomers may be employed in materials that include medical and food contact applications.However, such oligomers are not believed to be suitable for use in photoresists because they are not alkali developable, and are not photosensitive at wavelengths greater than $320~\\mathrm{{nm}}$ . Accordingly, the oligomers of Moy et al. are limited in their applications.  \n\nAccordingly, in view of the foregoing problems there is a need for photosensitive compositions having components that are more water-soluble or water-dispersible and eliminate or reduce contamination of articles.",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# SUMMARYOFTHEINVENTION  \n\nThe present invention is directed to a polymer having $\\mathbf{\\alpha}_{\\mathbf{{\\alpha}}_{\\mathbf{{\\beta}}}}$ -unsaturation and a group that generates a free radical upon exposure of the compound to actinic radiation, the polymer has an average molecular weight of at least 1000 daltons.  \n\nThe polymers may be employed in various photosensitive compositions, such as coatings, adhesives, decorative pigments, and compositions employed in lithography, optical data storage, active and passive optical elements such as polarizers, optical retarders or color filters, and electrophotographic imaging members. The polymers also are suitable for use in photoresists.  \n\nThe $\\mathbf{\\alpha}_{\\mathbf{{\\alpha}}}\\mathbf{{\\alpha}}_{\\mathbf{{\\alpha}}}\\mathbf{{\\beta}}_{\\mathbf{{\\alpha}}}$ -unsaturated functional groups of the polymers of the present invention enable the polymers to self-cross-link, thus compositions containing the polymers have no additional unsaturated monomers or have reduced amounts of unsaturated monomers in contrast to many conventional photosensitive compositions. The free radicals generated by the polymers may act as a photoinitiator, thus compositions containing polymers of the present invention also eliminate or reduce the amounts of added photoinitiator to the compositions. Accordingly, compositions containing polymers of the present invention eliminate or at least reduce scum and residue formation caused by unsaturated monomers and many photoinitiators found in conventional photosensitive compositions.  \n\nAdditionally, the polymers of the present invention may have hydrophilic components such that the polymers are water-soluble or water-dispersable. When polymers of the present invention are employed in photoresists, such watersolubility or water-dispersability helps eliminate or reduces scum and residue formation caused by uncured photoresists. Further, the hydrophilicity of the polymers of the present invention also improves developability and strippability of photoresists containing the polymers.  \n\nElimination or reduction of unsaturated monomers and photoinitiators reduces the solids content of the photoresist, thus enabling an increase of the diluent or liquid portion of the photoresist. Accordingly, the present invention also is directed to a liquid photoresist. Additionally, reduction of the chemical components of the photoresist reduces the cost in manufacturing of the photoresist.  \n\nIn addition to $\\mathbf{\\alpha}_{\\mathbf{{\\alpha}}_{\\mathbf{{\\beta}}}}$ -unsaturation and having an integral photoinitiator, polymers of the present invention also may have dyes, stripping agents, plasticizers, surfactants and other components used in photosensitive compositions joined to them. Thus, polymers of the present invention may compose the entire solids fraction of a photosensitive composition.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# DETAILED DESCRIPTION OF THE INVENTION  \n\nA “moiety” within the scope of the present invention means a distinct structural component of the functional   \n10 polymer and is synonymous with the term“group\". The term \"polymer\" means both polymer and copolymer. A“capping group” is a group that is at a terminus of a polymer's backbone. “Pendent\" means a structural component of the functional polymer that is joined to or suspended from the   \n15 main chain or backbone of the functional polymer by a chemical bond. “(Meth)acrylate\" means both acrylate and methacrylate and (meth)acrylic means both acrylic and methacrylic.“Monomer” or “oligomer” means any ethylenically or acetylenically unsaturated compound that may be   \n20 polymerized.“Functional group” means a component of a functional polymer that adds serviceability or processability to the polymer or permits the polymer to have a function in a composition other than just as a binder component. “Hydrophilic” within the scope of the present invention   \n25 means water-soluble or water-dispersable.“Water-soluble” within the scope of the present invention means that a compound or polymer swells or dissolves in water at normal temperatures (from above $0^{\\circ}$ C.to $100^{\\circ}\\mathrm{~C~}$ .at 1 atmosphere pressure). “Water-dispersable” within the scope of the   \n30 present invention means that a compound or polymer forms an emulsion, micro-emulsion or suspension in water at normal temperatures.All numerical ranges are inclusive and combinable in any order, except where it is logical that such numerical ranges are constrained to add up to $100\\%$   \n35 Polymers of the present invention have $\\upalpha,\\upbeta$ -unsaturation and a group that generates a free radical upon exposure of the polymers to actinic radiation, the polymers have an average molecular weight of at least 10oo daltons. Polymers having the $\\mathbf{\\alpha}_{\\alpha,\\upbeta}$ -unsaturation and the group that generates a   \n40 free radical are film forming functional polymers. The film forming functional polymers have a main chain or backbone that is derived from $\\mathbf{\\alpha}_{\\alpha,\\beta}$ -ethylenically or acetylenically unsaturated polymerizable monomers or oligomers or combinations thereof and terminate with at least one free unsat  \n45 urated group at either end of the polymer. In addition to the at least one free unsaturated group at either end of the polymer, at least one monomer or oligomer employed to make the polymer backbone may have one or more groups that are free to react with another compound to   \n50 join that other compound to the polymer to form a pendent functional group. Pendent functional groups may terminate in one or more $\\mathbf{\\alpha}_{\\alpha,\\upbeta}$ -ethylenically or acetylenically unsaturated functional group or another type of functional group. Functional groups enable the polymer to self-cross-link,   \n55 generate a free radical, make the polymer hydrophilic or add additional functional components to the polymer.Functional groups make the polymer and compositions in which the polymer is used serviceable or processable. Serviceable, for example, means that the polymer and compositions in which   \n60 the polymer is used may be coated on a substrate, durable against solutions such as plating solutions, has less postexposure back cross-linking， or is sensitive to light at wavelengths of at least $300\\mathrm{nm}$ . Processability, for example, means that the polymer and compositions in which the   \n65 polymer is used may be developed, stripped, or have an affinity for adhesion to metals. Compounds that may be joined to the polymer to form functional groups or moieties",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# 6  \n\non the polymer include, but are not limited to, photoinitiators, plasticizers, surfactants, dyes, stripping agents or combinations thereof. Any compound or component that may be joined to a polymer to improve the serviceability or processability of the polymer or a composition in which the polymer is used may be employed to practice the present invention. Specific examples of such compounds are disclosed below.  \n\nFunctional polymers may be prepared by any suitable method known in the art. One method of preparing func- 10 tional polymers is to first functionalize one or more monomers or oligomers that are employed to compose the polymer backbone followed by free radical polymerization of the monomers or oligomers or combinations thereof, thus forming a polymer with pendent functional groups. For example, 15 monomers or oligomers having free hydroxyl (-OH), carboxyl $(\\mathrm{-\\mathrm{\\COOH})}$ ，or ester （—COO—R,where R is an organic moiety) groups may react with compounds having free hydroxyl groups, carboxyl groups, ester groups, aminyl $(\\mathrm{-NH}_{2}$ or —NHR), or isocyanate (—NCO) groups to form 20 pendent groups. Examples of such reactions include addition reactions or condensation reactions. Examples of such addition reactions include nucleophilic, electrophilic and free radical addition reactions. Other examples of reactions include, but are not limited to, ether formation, transesteri- 25 fication, anhydride formation, amide formation or, urea formation. Such reaction methods and conditions to carry out the reactions are well known in the art. See Morrison and Boyd, “Organic Chemistry\", $3^{r d}$ edition, New York University, 1973, and March,“Advanced Organic Chemistry, Reac- 30 tions, Mechanisms, and Structures” ${\\bar{2}}^{n d}$ edition, McGrawHill Book Company, 1977. Free radical polymerization of the monomers or oligomers or combinations thereof follow to form a functional polymer. Conditions for free radical polymerization of monomers and oligomers are well known 35 in the art. Free radical polymerization of functionalized monomers or oligomers may be performed in suspension solution (from $60^{\\circ}\\mathrm{C}$ .to $80^{\\circ}\\mathrm{C}.$ )or emulsion (from $-20^{\\circ}\\mathrm{~C~}$ to $60^{\\circ}\\mathrm{~C~}.$ ) form. Pressures employed are near or at 1 atmosphere. Peroxide initiators may be employed in the 40 polymerization process such as dibenzoyl peroxide. Azo initiators also may be employed such as 2,2'-azobis(2 methylpropane nitrile) or 2,2'-azobis(2-methylbutane-nitrile).  \n\nAlternative processes for preparing a functional polymer are anionic polymerization, condensation polymerization or 4: by post polymerization functionalization. In post polymerization functionalization, the main chain or polymer backbone and the functional pendent components are prepared separately. Monomers or oligomers or combinations thereof, which compose the backbone, may be joined by free radical 5( polymerization. Compounds that compose the functional pendent groups may be prepared by any suitable method known in the art. Such compounds need only have one free reactive group as described above to bond with a free reactive group on the polymer backbone.After the synthesis 5: of the separate components that make up the polymer, they are then joined together in a separate reaction process to form the final functional polymer. Examples of chemical bonds formed between a polymer backbone and a pendent functional group are an ether bond R—O—P, where R is as  6( defined above and $\\mathrm{\\DeltaP}$ is a polymer backbone, an ester bond P—COO—R, or RCOO—P.  \n\nAnother example of such a reaction is between an isocyanate compound and a reactive group from a polymer backbone. After the polymer backbone is prepared, the polymer backbone is mixed with an isocyanate compound at reaction temperatures below $80^{\\circ}\\mathrm{C}$ . Mixing and heating are continued until the reaction is complete. Typically, the reaction continues for 1 hour to 8 hours. Reactions that take place occur between a free isocyanate group on the isocyanate compound and a hydroxyl group, carboxyl group,or primary or secondary aminyl functional group attached to the polymer backbone. One mole of free isocyanate reacts with one mole of a hydroxyl, carboxyl, or primary or secondary aminyl on the polymer main chain. The reaction may be self quenching.Water, alcohol, or other chemical species with labile hydrogen, and a suitable catalyst, such as triethylamine, may be added at the end of the reaction to quench any free isocyanate.Also, a suitable polymerization inhibitor may optionally be added to prevent premature cross-linking of terminal ethylenically or acetylenically unsaturated moieties such as a (meth)acrylate moiety. Reaction completion may be determined by using standard analytical instruments well known in the art.  \n\nThe synthesis may be carried out in the presence of an inert dry solvent (inert to reaction conditions), for example, an ether, an ester, ketones, nitriles, sulfones or phosphoric acid esters. To accelerate the reactions, any suitable catalyst employed in polymerization reactions may be used. Tin containing catalysts are an example. Stabilizers or polymerization inhibitors may optionally be added to the reaction steps to stabilize free-radical polymerization.  \n\nFree isocyanate, i.e. $-\\mathrm{N}{=}\\mathrm{C}{=}\\mathrm{O}$ , reacts with a hydroxyl group from the polymer backbone, or a hydroxyl group from a carboxyl group from the polymer backbone to form a R—NH—C(O)—P linkage where $\\mathrm{~\\bf~P~}$ is the polymer backbone, and R is an organic moiety. Examples of R include, but are not limited to substituted and unsubstituted alkyl, aryl, alkylaryl, or cycloaliphatic. Specific examples include a urethane group containing compound such as a biuret group.   \n5 A free isocyanate that reacts with a primary or secondary amine moiety joined to the polymer backbone forms a R—NH—C(O)—NR'-G-P urea (carbamide) linkage where $\\mathbb{R}^{1}$ includes, but is not limited to, hydrogen, a linear, branched or unsubstituted or substituted alkyl, or an unsubstituted or substituted aryl. Substituent groups include, but are not limited to, halogen, such as fluorine, bromine, chloride or iodine, hydroxyl, carboxyl, or primary or secondary amine.A substituent group replaces a hydrogen on a carbon atom. G is an organic moiety that joins the nitrogen   \n5 to the polymer chain. G includes, but is not limited to, an alkyl, or a substituted aryl where the nitrogen is joined to the aryl by an alkyl chain. The alkyl of G may be linear or branched $\\displaystyle(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{24})$ alkyl. A free isocyanate that reacts with a polyalkoxylated moiety from the polymer backbone forms $\\mathrm{a}\\mathrm{R{\\longrightarrow}N H{\\longrightarrow}C(O){\\longrightarrow}O(A O)_{x}{\\longrightarrow}C(O){\\longrightarrow}P}$ linkage where A is a linear or branched $(\\mathbf{C_{1}}\\mathrm{-C_{24})a l k y l}$ and $\\mathbf{x}$ is an integer from 0 to 1,000, preferably from 1 to 200. R, as defined above, may terminate in one or more functional groups such as ethylenically or acetylenically unsaturated moieties that permit functionalized polymers of the present invention to self cross-link as in photoresist compositions described below.  \n\nThe main chain or backbone of functional polymers of the present invention may be derived from monomers or oligomers which include, but are not limited to, acid functional monomers, base functional monomers,water-soluble functional monomers, urethane oligomers or mixtures thereof.  \n\nExamples of suitable ethylenically or acetylenically unsaturated monomers include, but are not limited to: (meth) acrylic acid, (meth)acrylamides, alkyl (meth)acrylates, alkenyl (meth)acrylates, aromatic (meth)acrylates, vinyl aromatic monomers, nitrogen-containing compounds and their thio-analogs, substituted ethylene monomers, cyclic olefins, ubstituted cyclic olefins, and the like. Preferred monomer nclude (meth)acrylic acid, alkyl (meth)acrylates and viny iromatic monomers.  \n\nTypically, the alkyl (meth)acrylates useful in the present invention are $\\mathrm{(C_{1}-C_{24})}$ Dalkyl (meth)acrylates. Suitable alkyl (meth)acrylates include, but are not limited to, “low cut\" alkyl (meth)acrylates, “mid cut\" alkyl (meth)acrylates and \"high cut\" alkyl (meth)acrylates.  \n\n“Low cut\" alkyl (meth)acrylates are typically those where the alkyl group contains from 1 to 6 carbon atoms. Suitable low cut alkyl (meth)acrylates include, but are not limited to: methyl methacrylate, methyl acrylate, ethyl acrylate, propyl methacrylate, butyl methacrylate, butyl acrylate, isobutyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, cyclohexyl acrylate and mixtures thereof.  \n\n\"Mid cut\" alkyl (meth)acrylates are typically those where the alkyl group contains from 7 to 15 carbon atoms. Suitable mid cut alkyl (meth)acrylates include, but are not limited to: 2-ethylhexyl acrylate (\"EHA\"), 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, isodecyl methacrylate (based on branched $\\mathrm{(C_{10})a l k y l}$ isomer mixture), undecyl methacrylate, dodecyl methacrylate (also known as lauryl methacrylate), tridecyl methacrylate, tetradecyl methacrylate (also known as myristyl methacrylate), pentadecyl methacrylate and mixtures thereof. Particularly useful mixtures include dodecyl-pentadecyl methacrylate, a mixture of linear and branched isomers of dodecyl, tridecyl, tetradecyl and pentadecyl methacrylates; and lauryl-myristyl methacrylate.  \n\n“High cut\" alkyl (meth)acrylates are typically those where 3 the alkyl group contains from 16 to 24 carbon atoms. Suitable high cut alkyl (meth)acrylates include, but are not limited to: hexadecyl methacrylate, heptadecyl methacrylate, octadecyl methacrylate, nonadecyl methacrylate, cosyl methacrylate, eicosyl methacrylate and mixtures thereof. 3: 35 Particularly useful mixtures of high cut alkyl (meth)acrylates include, but are not limited to: cetyl-eicosyl methacrylate, which is a mixture of hexadecyl, octadecyl, cosyl and eicosyl methacryl ate; and cetyl-stearyl methacrylate, which is a mixture of hexadecyl and octadecyl methacrylate.  \n\nThe mid-cut and high-cut alkyl (meth)acrylate monomers described above are generally prepared by standard esterification procedures using technical grades of long chain aliphatic alcohols, and these commercially available alcohols are mixtures of alcohols of varying chain lengths 4 containing between 10 and 15 or 16 and 20 carbon atoms in the alkyl group.Examples of these alcohols are the various Ziegler catalyzed ALFoL alcohols from Vista Chemical company, i.e.,ALFOL 1618 and ALFOL 1620, Ziegler catalyzed various NEoDoL alcohols from Shell Chemical Company, i.e. 5 NEODoL 25L, and naturally derived alcohols such as Proctor & Gamble's TA-1618 and CO-1270. Consequently, for the purposes of this invention, alkyl (meth)acrylate is intended to include not only the individual alkyl (meth)acrylate product named, but also to include mixtures of the alkyl 5 (meth)acrylates with a predominant amount of the particular alkyl (meth)acrylate named.  \n\nThe alkyl (meth)acrylate monomers useful in the present invention may be a single monomer or a mixture having different numbers of carbon atoms in the alkyl portion. Also, the (meth)acrylamide and alkyl (meth)acrylate monomers useful in the present invention may optionally be substituted. Suitable optionally substituted (meth)acrylamide and alkyl (meth)acrylate monomers include, but are not limited to: hydroxy $(\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{20}){\\mathrm{alkyl}}$ (meth)acrylates, dialkylamino $(\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{20})$ alkyl (meth)arylates, dialkaylamino $\\displaystyle(\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{20,})$ alkyl (meth)acrylamides, preferably, hydroxy( $\\mathrm{\\DeltaC}_{2}\\mathrm{-}C_{6}$ )alkyl (meth)  \n\nacrylates, dialkylamino $(\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{6})$ alky1 (meth)acrylates, dialkylamino $\\displaystyle{(C_{2}-C_{6})}$ alkyl (meth)acrylamides.  \n\nParticularly useful substituted alkyl (meth)acrylate monomers are those with one or more hydroxyl groups in the alkyl radical, especially those where the hydroxyl group is found at the $\\upbeta$ -position (2-position) in the alkyl radical. Hydroxyalkyl (meth)acrylate monomers in which the substituted alkyl group is a $(\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{6})\\mathrm{alkyl}$ ， branched or unbranched, are preferred. Suitable hydroxyalkyl (meth)acrylate monomers ）include, but are not limited to: 2-hydroxyethyl methacrylate (\"HEMA\"), 2-hydroxyethyl acrylate (\"HEA\"), 2-hydroxypropyl methacrylate, 1-methyl-2-hydroxyethyl methacrylate, 2-hydroxy-propyl acrylate, 1-methyl-2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl ） acrylate and mixtures thereof.  \n\nHydroxy poly opened-ring lactone polyalkylene oxide (meth)acrylates as described in U.S. Pat. No. 6,045,973 may be employed. Suitable hydroxy polyalkylene oxide (meth) acrylates prepared from poly(propylene glycol) (meth)acry  \n20 lates, poly(propylene glycol) alkyl ether (meth)acrylates, poly (propylene glycol) phenyl ether (meth)acrylates, poly (propylene glycol) 4-nonylphenol ether (meth)acrylates, poy (ethylene glycol) (meth)acrylates, poly(propylene/ethylene glycol) (meth)acrylates, poly(ethylene glycol)alkyl ether   \n25 (meth)acrylates, poly(ethylene glycol) phenyl ether (meth) acrylates, poly(propylene/ethylene glycol) alkylether (meth) acrylates and mixtures thereof may be employed. The poly (alkylene oxide) may have from 1 to 50 degrees of polymerization. Such compounds may also be joined to the   \n30 polymer backbone as a pendent functional group via an isocyanate group by reacting the hydroxyl of the poly (alkylene oxide) with an isocyanate of a polyisocyanate. A free isocyanate may then be reacted with a reactive group on the polymer backbone to join it to the polymer. Other substituted monomers useful in the present invention are those with a tertiary amino group or alkylamino group. Examples include, but are not limited to: dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, N-methylaminoethyl methacrylamide, N-methyl-aminopro  \n40 pyl methacrylamide, N-methylaminobutyl methacrylamide, N-ethylaminoethyl methacrylamide, N-ethylaminopropyl methacrylamide, N-ethylaminobutyl methacrylamide, N-(1, 1-dimethyl-3-oxobutyl) acrylamide, N-(1,3-diphenyl-1- ethyl-3-oxobutyl) acrylamide, N-(l-methyl-1-phenyl-3-ox  \n45 obutyl) methacrylamide, and 2-hydroxyethyl acrylamide, N-methacrylamide of aminoethyl ethylene urea, N-maleimide of dimethylaminopropylamine and mixtures thereof.  \n\nOther substituted (meth)acrylate monomers useful in the present invention are silicon-containing monomers such as $\\upgamma$ -propyl $\\mathrm{tri}({\\mathrm C}_{1}{-}{\\mathrm C}_{6})$ alkoxysilyl (meth)acrylate, $\\upgamma$ -propyl tri $(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{6}$ Dalkylsilyl (meth)acrylate, -propyl di $\\mathrm{(C_{1}-C_{6}}$ Dalkoxy $(\\mathrm{C_{1}}\\mathrm{-C_{6}}$ Dalkylsilyl (meth)acrylate, $\\upgamma$ -propyl $\\mathrm{{di}(C_{1}-C_{6})a l k y l}$ $\\mathrm{(C_{1}-C_{6,})}$ alkoxysilyl(meth)acrylate,vinyl $\\mathrm{tri}({\\mathrm C}_{1}{-}{\\mathrm C}_{6})$ alkoxysilyl (meth)acrylate, vinyl $\\mathrm{di}(\\mathrm{C_{1}{-}C_{6})a l k o x y(\\mathrm{C_{1}{-}C_{6})}}$ alkylsilyl (meth)acrylate, vinyl $(\\mathrm{C_{1}-C_{6}})\\mathrm{alkoxydi}(\\mathrm{C_{1}-C_{6}})$ alkylsilyl (meth)acrylate, vinyl $\\mathrm{tri}({\\mathrm C}_{1}{-}{\\mathrm C}_{6})$ alkylsilyl (meth) acrylate,2-propylsilsesquioxane (meth)acrylate and mixtures thereof.  \n\nThe vinyl aromatic monomers useful as unsaturated   \n60 monomers in the present invention include, but are not limited to: styrene, hydroxystyrene, $\\mathbf{\\alpha}_{\\mathrm{~d~}}$ -methylstyrene, vinyltoluene, p-methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinylxylenes, and mixtures thereof. The vinylaromatic monomers also include their corresponding substituted   \n65 counterparts, such as halogenated derivatives, i.e., containing one or more halogen groups, such as fluorine, chlorine or bromine; and nitro, cyano, $\\displaystyle{(\\mathrm{C_{1}}\\mathrm{-}\\mathrm{C_{10}})}$ alkoxy, halo $\\mathrm{(C_{1}-C_{10})}$  \n\nalkyl, carb $\\displaystyle{(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{10})}$ alkoxy, carboxy, amino, $\\mathrm{(C_{1}-C_{10})}$ alkylamino derivatives and the like.  \n\nThe nitrogen-containing compounds and their thio-analogs useful as unsaturated monomers in the present invention include, but are not limited to: vinylpyridines such as 2-vinylpyridine or 4-vinylpyridine; $\\mathrm{(C_{1}-C_{8})}$ alkyl substituted N-vinyl pyridines such  as 2-methyl-5-vinyl-pyridine, 2-ethyl-5-vinylpyridine, 3-methyl-5-vinylpyridine, 2,3-dimethyl-5-vinyl-pyridine, and 2-methyl-3-ethyl-5-vinylpyridine; methyl-substituted quinolines and isoquinolines; N-vinylcaprolactam; N-vinylbutyrolactam; N-vinylpyrrolidone; vinyl imidazole; N-vinyl carbazole; N-vinyl-succinimide; (meth)acrylonitrile; o-, m-, or p-aminostyrene; hydroxystylene; maleimide; N-vinyl-oxazolidone; N,N-dimethyl aminoethyl-vinyl-ether; ethyl-2-cyano acrylate; vinyl acetonitrile; N-vinylphthalimide; N-vinyl-pyrrolidones such as N-vinyl-thio-pyrrolidone, 3 methyl-1-vinyl-pyrrolidone, 4-methyl-1-vinyl-pyrrolidone, 5-methyl-1-vinyl-pyrrolidone, 3-ethyl-1-vinyl-pyrrolidone, 3-butyl-1-vinyl-pyrrolidone, 3,3-dimethyl-1-vinyl-pyrrolidone, 4,5-dimethyl-1-vinyl-pyrrolidone, 5,5-dimethyl-1-vinyl-pyrrolidone, 3,3,5- trimethyl-1-vinyl-pyrrolidone, 4-ethyl-1-vinyl-pyrrolidone, 5-methyl-5-ethyl-1-vinyl-pyrrolidone and 3,4,5-trimethyl-1- vinyl-pyrrolidone; vinyl pyrroles; vinyl anilines; and vinyl piperidines.  \n\nThe substituted ethylene monomers useful as unsaturated monomers in the present invention include, but are not limited to: vinyl acetate, vinyl formamide, vinyl chloride, vinyl fluoride, vinyl bromide, vinylidene chloride, vinylidene fluoride, vinylidene bromide, tetrafluoroethylene, trifluoroethylene, trifluoromethyl vinyl acetate, vinyl ethers and itaconic anhydride.  \n\nSuitable cyclic olefin monomers useful in the present invention are $(\\mathrm{C}_{5}\\mathrm{-}\\mathrm{C}_{10})$ cyclic olefins, such as cyclopentene, cyclopentadiene, dicylopentene, cyclohexene, cyclohexadi- 3: ene, cycloheptene, cycloheptadiene, cyclooctene, cyclooctadiene, norbornene, maleic anhydride and the like. Such cyclic olefins also include spirocyclic olefin monomers such as spirocyclic norbornenyl monomers, spirocyclic cyclohexene monomers, spirocyclic cyclopentene monomers and 4( mixtures thereof. Suitable substituted cyclic olefin monomers include, but are not limited to, cyclic olefins having one or more substituent groups selected from hydroxy, aryloxy, halo, $({\\bf C}_{1}{-}{\\bf C}_{12})\\mathrm{alkyl}$ ， $\\displaystyle{(C_{1}-C_{12})}$ haloalkyl, $\\displaystyle{(C_{1}-C_{12})}$ hydroxyalkyl, $\\mathrm{(C_{1}-C_{12})}$ halohydroxyalkyl such as $(\\mathrm{CH}_{2})_{n}\\mathrm{C}(\\mathrm{CF}_{3})_{2}$ 4 OH where $\\mathrm{n}^{\\prime}{=}0$ to 4, $(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{12})$ alkoxy, thio, amino, $\\mathrm{(C_{1}-C_{6})}$ alkylamino, $\\mathrm{(C_{1}-C_{6})}$ dialkylamino, $\\mathrm{(C_{1}-C_{12})}$ alkylthio, carbo $\\mathrm{(C_{1}-C_{20})}$ Dalkoxy，carboo $\\mathrm{(C_{1}-C_{20})}$ haloalkoxy, $(\\mathbf{C}_{1}\\mathbf{-}\\mathbf{C}_{12})\\mathbf{acyl}$ $\\mathrm{(C_{1}-C_{6,}}$ alkylcarbonyl $(\\mathbf{C_{\\mathrm{1}}}\\mathrm{-}\\mathbf{C_{\\mathrm{6}}})\\mathbf{a}\\mathbf{l}\\mathbf{k}\\mathbf{y}\\mathbf{l}$ ，and the like. Particularly suitable substituted cyclic olefins include maleic anhy- 5( dride and cyclic olefins containing one or more of hydroxy, aryloxy, $(\\mathbf{C}_{1}{-}\\mathbf{C}_{12})\\mathrm{alkyl}$ ， $\\displaystyle{(C_{1}-C_{12})}$ haloalkyl， $\\displaystyle{(C_{1}-C_{12})}$ hydroxyalkyl, $\\mathrm{(C_{1}-C_{12})}$ halohydroxyalkyl, carbo $\\left(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{20}\\right)$ alkoxy, and carbo $\\mathrm{(C_{1}-C_{20})}$ haloalkoxy. It will be appreciated by those skilled in the art that the alkyl and alkoxy substitu- 5: ents may be optionally substituted, such as with halogen, hydroxyl, cyano, $\\displaystyle{(C_{1}-C_{6,}^{\\mathrm{~~}}}$ alkoxyl, mercapto, $\\displaystyle{(C_{1}-C_{6,})}$ Dalkylthio, amino, or acid labile leaving group. Suitable carbo $\\displaystyle{\\bigl(}\\mathrm{C}_{1}{-}\\mathrm{C}_{20}{\\bigr)}$ alkoxy substituents include, but are not limited to, those of the formula C(O)O-LG, wherein LG is a leaving 60 group including, but are not limited to, alkyl groups having 4 or more carbon atoms with at least one quaternary carbon atom bonded directly to a carboxylate oxygen such as tert-butyl esters, 2,3-dimethylbutyl esters, 2-methylpentyl esters, 2,3,4-trimethylpentyl esters, alicyclic esters, acetals 6: or ketals from vinyl ethers or enols such as —O— $\\mathrm{(CH(CH}_{3})$ $\\mathrm{OC}_{2}\\mathrm{H}_{5},$ )or—o— $\\mathrm{(CH}_{2}\\mathrm{OC}_{2}\\mathrm{H}_{5}\\mathrm{)}$ , tetrahydropyran. Suitable alicyclic esters as leaving groups include adamantyl, methyladamantyl, ethyladamantyl, methylnorbornyl, ethylnorbornyl, ethyltrimethylnorbornyl, ethyl fenchol and the like.  \n\nAny of a wide variety of difunctional branch-point mono  \n5 mers are suitable for use in preparing the functional polymers of the present invention provided that such branchpoint monomers contain a backbone comprising one or more base cleavable functionalities or moieties, where such functionalities are disposed between the polymerizable groups of   \nl0 the branch-point monomer. By “base cleavable functionality\" is meant any functionality or group that can be cleaved by a base such as hydroxide ion, alkoxide ion, ammonia or amines.  \n\nA wide variety of difunctional branch-point monomers ； containing base cleavable moieties may be used. Such branch-point monomers have the structure",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# A'-Z-B  \n\n20 where $\\mathbf{A^{\\prime}}$ and B each include one or more polymerizable groups, and Z includes one or more base cleavable groups. Suitable polymerizable groups for $\\mathbf{A^{\\prime}}$ and B include, but are not limited to, isocyanate $(^{64}-\\mathrm{{NCO}^{3})}$ ， $\\mathrm{R}_{1}\\mathrm{R}_{2}\\mathrm{C}=\\mathrm{CR}_{3}-$ $\\mathrm{R_{1}{\\mathrm{-}}C{\\mathrm{=}}C{\\mathrm{-}}}$ ， $\\mathrm{R_{1}R_{2}C=C R_{4}C(O)=O}$ 一， $\\mathrm{R}_{1}\\mathrm{R}_{2}\\mathrm{C}{=}\\mathrm{CR}_{4}-$   \n25 O—，and $\\mathrm{\\longrightarrow}\\mathrm{C(O)}\\mathrm{\\longrightarrow}\\mathrm{O}\\mathrm{\\longrightarrow}\\mathrm{R}_{5}$ ；wherein $\\mathrm{R}_{1}$ ， ${\\mathrm{R}_{2}}$ and $\\mathrm{R}_{4}$ are independently selected from H, $\\mathrm{(C_{1}-C_{4})}$ Dalkyl and halo; $\\mathrm{R}_{5}$ is selected from H, $(\\mathrm{C_{1}-C_{4}})\\mathrm{alkyl}$ ， and $\\mathrm{NR}_{6}\\mathrm{R}_{7}$ ； and $\\mathrm{R}_{6}$ and $\\mathrm{R}_{7}$ are independently selected from H and $\\mathrm{(C_{1}-C_{4}}$ Dalkyl.In addition to one or more base cleavable groups, the group Z   \n30 may optionally include one or more spacer groups. Z may suitably have the general formula $\\mathrm{S}_{x4}(\\mathrm{BCG})_{y4}$ whereinS is a spacer group; (BCG) is a base cleavable group; $\\mathbf{\\Deltax}_{4}{=}0{-}20$ and $\\mathrm{y}_{4}{=}1{-}30$ . It is preferred that $y_{4}{=}2–20$ . Suitable spacer groups include, but are not limited to, alkyleneoxy, aryle  \n351 neoxy， $\\displaystyle(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{20})$ alkylene,substituted $(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{20})$ Dalkylene, $\\displaystyle(\\mathrm{C}_{6}{-}\\mathrm{C}_{20})$ aralkylene, substituted $(\\mathrm{C}_{6}{-}\\mathrm{C}_{20})$ aralkylene, and the like. Suitable alkyleneoxy groups have the general formula $(\\mathrm{~\\longrightarrowCHR_{8}\\mathrm{\\longrightarrowCH}_{2}O\\mathrm{\\longrightarrow}})_{n3}$ $(\\mathrm{~\\longrightarrow~}\\mathrm{OCHR}_{8}\\mathrm{\\ensuremath~{\\longrightarrow~}}\\mathrm{CH}_{2}\\mathrm{\\ensuremath~{\\longrightarrow~}})_{m3}$ or $(-\\mathrm{O-}$ $\\mathrm{CH}_{2}{\\longrightarrow}\\mathrm{CH}_{2}{\\longrightarrow}\\mathrm{CH}_{2}{\\longrightarrow})_{p3}$ ,where $\\mathrm{R}_{8}$ .s1 $\\mathrm{H}$ of $\\mathrm{CH}_{3}$ and ${\\bf n}_{3}$ ${\\mathfrak{m}}_{3}$   \n40 and ${\\mathfrak{p}}_{3}$ are each 1-1000. Exemplary alkylenoxy groups include ethyleneoxy, propyleneoxy and ethyleneoxy/propyleneoxy mixtures. Aryleneoxy or arylene ether spacers include phenyleneoxy (phenylene ether) spacers having the general formula $(\\mathrm{~-~}\\mathrm{C}_{6}\\mathrm{H}_{4}\\mathrm{-~}\\mathrm{O}\\mathrm{-})_{z3}$ where $\\mathbf{z}_{3}{=}1{-}1000$ , biphe  \n451 nylene ethers, phenanthryl ethers, naphthyl ethers, and mixtures thereof. When two or more spacer groups are used, they may be the same or different.  \n\nSuch spacer groups may be selected to provide additional properties. For example, alkyleneoxy spacers, such as ethyleneoxy and/or propyleneoxy moieties, may help to emulsify the polymeric binders for use in water borne photoresists. Spacers having extended chain length may also provide improved flexibility and be particularly useful in conformal photoresist formulations. The choice of such spacer groups depend upon the particular use of the polymer and the other components in the formulation, and is within the ability of one skilled in the art.  \n\nAny base cleavable group is suitable for use in Z, but is preferably selected from anhydrides (—C(O)-O—(O)   \n0 $\\mathrm{C-})$ ，esters $(\\longrightarrow\\mathrm{C(O){\\longrightarrow}O\\longrightarrow})$ ，carbonates, sulfonyl esters $(-\\mathrm{SO}_{2}\\mathrm{-}\\mathrm{O}_{-})$ and the like, and more preferably esters. It is more preferred that the difunctional branch-point monomers contain 2 or more base cleavable groups and still more preferably 3 or more base cleavable groups. Particularly   \ni5 suitable difunctional branch-point monomers contain 4 base cleavable groups, and more particularly 4 or more ester linkages. It is further preferred that the difunctional branch",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 14,
+        "chunk": "# 11  \n\npoint monomer contain as polymerizable end groups moieties that also contain one or more base cleavable functionalities, such as (meth)acrylate esters. When the difunctional branch-point monomers contain 2 or more base cleavable groups, such groups may be directly bonded to each other or may be separated by one or more spacer groups. An exemplary structure for such branch-point monomers having multiple base cleavable groups is A' $(\\mathrm{S}1)_{x1}$ (BCG)1- $(\\mathrm{S}2)_{x2}$ 1 $(\\mathrm{BCG})2\\ –(\\mathrm{S}3)_{x3}-$ B,wherein S1, S2 and S3 refer to spacer groups 1-3, respectively, (BCG)1 and (BCG)2 refer to base cleavable groups 1 and 2, respectively, $\\mathbf{x}1+\\mathbf{x}2+\\mathbf{x}3=0-20$ ,and A', B, S, (BCG) and B are as defined above. Other suitable structures having more or fewer spacers and/or base cleavable groups or different configurations of such groups are well within the ability of those skilled in the art.  \n\nSuitable difunctional branch-point monomers useful in preparing the polymers of the present invention include, but are not limited to, acrylic anhydride, methacrylic anhydride, and ester linkage containing monomers having (meth)acrylate end groups. Exemplary difunctional branch-point monomers including one or more urethane linkages and having (meth)acrylate end groups are: pdmbi-pcp0200-pdmbi, pdmbi-pcp0201-pdmbi, pdmbi-pcp0230-pdmbi, eh6cl4-hdippg1000-hdi-eh6cl4, eh6cl4-hdi-pcp0230-hdi-eh6cl4, eh6cl4-hdi-ppg425-hdi-dmpa-hdi-ppg425-hdi-eh6cl4, 2hema-hdi-pcp0230-hdi-ppg425-hdi-pcp0230-hdi-2hema, 2hema-hdi-pcp0230-hdi-peg400-hdi-pcp0230-hdi-2hema, 2hema-hdi-pcp0200-hdi-pcp0230-hdi-pcp0200-hdi-2hema, e6hem-hdi-pcp0200-hdi-pcp0230-hdi-pcp0200-hdi-e6hem, e6hem-hdi-pcp0200-hdi-ppg1000-hdi-pcp0200-hdi-e6hem, e6hem-hdi-ppg425-hdi-pcp0230-hdi-ppg425-hdi-e6hem, e6hem-hdi-ppg1000-hdi-pcp0230-hdi-ppg1000-hdi-e6hem, e6hem-hdi-pcp0230-hdi-ppg425-hdi-pcp0230-hdi-e6hem, ande6hem-hdi-ppg1000-hdi-pcp0201-hdi-ppg1000-hdie6hem. In the above described difunctional branch-point monomers, each “dash\" represents a urethane group (formed when an isocyanate group reacts with a hydroxyl group) between the adjacent moieties. Such urethane linkages are not required in the present branch-point monomers. The abbreviations for the moieties are: hd $_{=1}$ ,6-hexamethylene diisocyanate; $\\mathtt{p c p0200=T o N E^{T M}}$ Polyol 0200 Diol (containing carboxylic ester groups); $\\mathrm{pcp}0201{=}\\mathrm{ToNE}^{\\mathbf{TM}}$ Polyol 0201 Diol (contains carboxylic ester groups); $\\mathtt{p c p0230=T o N E^{T M}}$ Polyol_ O230 Diol (contains carboxylic ester groups); $\\mathsf{p p g425}\\mathrm{=}$ polypropylene glycol having a molecular weight of approximately 425; ppg1000=polypropylene glycol having a molecular weight ofapproximately1000; dmpa=dimethylolpropionic acid; pdmbi $^{=3}$ -isopropenyl-alpha,alpha-dimethylbenzyl isocyanate; 2hema $_{1=2}$ -hydroxyethyl methacrylate (contains ester group and a polymerizable end group)； e6hem=ethoxylated hydroxyethyl methacrylate (contains ester group and a polymerizable end group); and eh6cl4=ethoxylated caprolactone-derived methacrylate (contains ester groups and a polymerizable end group). Such branch-point monomers are generally commercially available or may be readily prepared by known methods. ToNETM is a trademark for polycaprolactone diols, available from the Dow Chemical Company (Midland, Mich.). Other suitable polycaprolactone diols are available from Solvay under the CAPA brand name. Typically, the molecular weight of the branch-point monomers is $\\geq450$ and preferably from 450 to 6000.  \n\nMore than one difunctional branch-point monomer may be used to prepare the functional polymers. Thus, mixtures of difunctional branch-point monomers may advantageously be used in the present invention. The total amount of such difunctional branch-point monomers in the functional polymers may be from 0.1 to 100 wt $\\%$ based upon the total veight of the monomers used to prepare the polymei ypically from 0.1 to $25\\mathrm{\\wt\\\\%}$ ， and more typically from 0. 0 $10\\mathrm{\\mi\\%}$  \n\nPolymers of the present invention contain sufficient acid ； functionality to render the polymers soluble and removable upon development. The term “acid functionality” refers to any functionality capable of forming a salt upon contact with alkaline developer, such as dilute alkaline aqueous sodium or potassium hydroxide, e.g.1 to $3\\mathrm{wt\\%}$ solutions. Suitable acid functionality includes, but is not limited to, carboxylic acids, sulfonic acids, phosphonic acids and phenols. The polymers have an acid number of up to 250, preferably up to 200. Typical ranges of acid numbers are from 15 to 250 and preferably from 50 to 250. Such acid numbers are based on the amount of KOH (potassium hydroxide) in mg to D neutralize $\\mathrm{~1~g~}$ (dry weight) of polymer.  \n\nPreferably, functional polymers of the present invention have multiple ester links in the backbone or in pendent side chains, or in the backbone and in the pendent chains. Such ester links permit quick and clean removal of the functional polymers from a substrate using a stripping agent. Quick and clean removal is highly desirable in a photoresist. Preferably, functional polymers have from 2 or more ester links in the backbone or in the pendent side chains or in both the backbone and chains. Preferably the functional polymers have from 5 or more ester links, more preferably from 10 to 50 ester links, most preferably from 20 to 40 ester links in the backbone and/or pendent side chains. Such polyester links may be derived from the hydroxy poly opened-ring lactone or hydroxy polyalkylene oxide (meth)acrylates described above.  \n\nIn one embodiment of the present invention, isocyanate compounds used to prepare the functional polymers of the present invention include urethane/ethylenically or acetylenically unsaturated isocyanates. Such compounds have a —NHC(O)— moiety, at least one free isocyanate group   \n35 $(-\\mathrm{N}{=}\\mathrm{C}{=}\\mathrm{O})$ , and an ethylenically or acetylenically unsaturated moiety such as a (meth) acrylate that is at a terminus of the isocyanate compound. Biuret ethylenically or acetylenically unsaturated isocyanates have a —NH—C(O)- N—C(O)—NH—moiety, at least one free isocyanate group   \n40andanethylenicallyor acetylenically unsaturated moiety at a terminus of the compound. Examples of such compounds include, but are not limited to, the following general formulas:  \n\nIII; or  \n\nIV  \n\n![](images/48bfd283fb9ec191d40906627a8f6603f65f56bbae34c7b3b3e23100e43227d9.jpg)  \n\nwhere $Z^{\\prime}$ includes, but is not limited to, alkyl, alkylene, cycloalkyl, aryl, heterocyclic alkyl, heteroaryl, a polymer such as a copolymer including a branched polymer or branched copolymer; Y includes, but is not limited to, alky, alkylene, cycloalkyl, aryl, heterocyclic alkyl, heteroaryl, $-(\\mathrm{(CH_{2})_{\\it u}\\mathrm{\\bar{\\longrightarrow}0\\mathrm{-\\bar{\\jmath}_{\\nu}\\mathrm{\\bar{\\longrightarrow}(C H_{2})_{\\it w}\\mathrm{\\bar{\\longrightarrow}\\mathrm{\\Lambda}_{\\mathrm{B}}}}}}}}$ or— $-(\\mathrm{(C\\dot{H}_{2})_{\\boldsymbol{u}}\\mathrm{-\\nablaC(O)\\dot{-}\\quad}}$ $\\mathrm{O-}\\mathrm{)}_{\\nu}\\mathrm{\\longrightarrow(CH}_{2}\\mathrm{)}_{w}\\mathrm{\\longrightarrow}$ where u, and w are integers of from 1 to 10, and $\\mathbf{v}$ is an integer of from O to greater than 1,000, preferably from 1 to 200, most preferably from 5 to $1\\dot{0}.\\mathrm{R}^{\\dot{2}}$ is hydrogen or $\\mathrm{(C_{1}-C_{4})}$ alkyl. Preferably $\\mathrm{R}^{2}$ is hydrogen or methyl. Hetero-atoms include, but are not limited to, oxygen, sulfur, and nitrogen. The alkyl, alkylene, cycloalkyl, aryl,heterocyclic alkyl, heteroaryl and polymers may be unsubstituted or substituted.Examples of suitable substituent groups include, but are not limited to, carboxyl, hydroxyl, $\\mathrm{(C_{1}-C_{4})}$ alkyl), aminyl such as a_ primary or secondary aminyl, or hydroxyaminyl, or —CN.  \n\nExamples of suitable alkyl groups include, but are not limited to, linear or branched $\\mathrm{(C_{1}-C_{20})}$ alkyl. Examples of alkenyl, cycloakyl or aryl groups include, but are not limited to, linear or branched $\\displaystyle(\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{20})$ alkenyl, $\\displaystyle(C_{5}{-}C_{6})$ cycloalky such as an isophorone, and $(\\mathrm{C}_{5}\\mathrm{-}\\mathrm{C}_{6})$ aryl such as phenyl.  \n\nThe isocyanate compounds with at least one free isocyanate group may be prepared by any suitable method known in the art. Monoisocyanates with functional groups such as (meth)acrylate groups, diisocyanates or triisocyanates that may be employed are either known or may be prepared by analogy to known compounds. Examples of suitable diisocyanates and triisocyanates include, but are not limited to, ethylene diisocyanate, propylene diisocyanate, butylene-1, 3-diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, 2,4-dimethyl-6-ethyloctamethylene diisocyanate, cyclohexylene diisocyanate, cyclopentylene diisocyanate, 1,4-diisocyanatomethyl-cyclohexane, 1,3-diisocyanatoethyl-cyclohexane, toluylene diisocyanate, 3,3,5-trimethyl-1-isocyanato-5-isocyanatomethylcyclohexane,2-butene-1,4-diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate biuret, 1,6- hexamethylene diisocyanate trimer, or isophorone diisocyanate trimer. Many of the foregoing listed diisocyantes and triisocyantes as well as the biurets and trimers may be purchased from Lyondell (located at 122 Melanney St., Houston, Tex.) or Bayer (located at 100 Bayer Rd., Pittsburg, Pa. 15025).  \n\nIsocyanates such as the diisocyanates and triisocyanates described above may then be reacted with a suficient amount of one or more hydroxyl containing compounds such that one free isocyanate group is left to react with the polymer backbone prepared as described above. As men- ：4 tioned above, the reaction mole ratio of hydroxyl group to isocyanate group is about 1:1.Any suitable compound with at least one free hydroxyl group to react with an isocyanate group may be employed. An isocyanate compound of the present invention also may be reacted with another isocy- 5 anate compound having at least one free hydroxyl group. Hydroxyalkyl, hydroxyalkenyl, hydroxyaryl compounds and the like are examples of such compounds that may be employed. Hydroxyalkyl (meth)acrylates are one example of \\*suitable compounds. Hydroxyethyl (meth)acrylate or $55$ hydroxypropyl (meth)acrylate (n or iso compounds） are examples of hydroxyl group-containing esters that are suitable. Other suitable hydroxyalkyl (meth)acrylates include, but are not limited to, 2-hydroxy-butyl (meth)acrylate, 4-hydroxy-butyl (meth)acrylate, 2-hydroxy-cyclohexyl (meth) acrylate, 2-hydroxyethylmethacrylate, and the like. Suitable polyethylene glycol mono (meth)acrylates also may be employed such as, but not limited to, diethylene glycol mono (meth)acrylate, triethylene glycol mono (meth)acrylate and the like. Hydroxyalicyclic (meth)acrylates, and hydroxyaromatic (meth)acrylates such as bis phenol A 6 dimethacrylate also may be employed.U.S. Pat.No. 4,019, 972 discloses a method of preparing urethanes.  \n\nFunctional groups that are to be joined to the polymer backbone and have free reactive groups, such as isocyanate groups, may be reacted with compounds having $\\mathbf{\\alpha}_{\\alpha,\\upbeta}$ -ethylenically or acetylenically unsaturated groups to extend the functional pendent groups. Such compounds with unsaturated groups include, but are not limited to, a compound having a formula:  \n\n$$\n\\mathrm{CH}_{2}\\mathrm{=CHR^{3}-C(O)-O-(A_{1})\\mathrm{-(B_{1})-(C_{1})-H}}\n$$  \n\n10 where $\\mathrm{R}^{3}$ is hydrogen or methyl, $(\\mathrm{A}_{1})$ ， $\\left(\\operatorname{B}_{1}\\right)$ and $\\mathrm{(C_{1})}$ are in any order, $(\\mathbf{A}_{1})$ is a chain formed of from 1 to 40 alkoxylate monomers, aromatic-substituted alkoxylate monomers having from 1 to 20 carbon atoms, or mixtures thereof, $\\mathrm{(B_{1})}$ is either absent or is a chain formed of from 1 to 40 alkoxylate   \n15 monomers, or aromatic-substituted alkoxylate monomers having from 1 to 20 carbon atoms, or mixtures thereof, and the monomer composition of $\\left(\\mathrm{B}_{1}\\right)$ being different than the monomer composition of $(\\mathbf{A}_{1})$ ,and $\\mathrm{(C_{1})}$ is a chain formed of from 1 to 40 open-ring lactone monomers having from 2 to   \n20 21 carbon atoms. In addition to unsaturated groups, functional polymers generate a free-radical upon exposure to actinic radiation. Free-radical generating monomers or oligomers may be derived from Michael addition reactions of at least one   \n25 diketone or at least one acetoacetate derivative functional donor compound and at least two multifunctional acrylate receptor compounds. The resulting free-radical generating oligomer may contain both capping and pendent acrylate groups which are capable of cross-linking upon exposure to actinic radiation. Michael addition reactions are catalyzed   \n30 by a strong base such as diazabicyclo-undecene (DBU). Other cyclic amidines, for example diazabicyclo-nonene (DBN) and guanidines, also are suitable for catalyzing Michael addition reactions. U.S.Pat. No. 5,945,489 and U.S.Pat. No. 6,025,410 disclose Michael addition reactions.   \n35Preferablytheoligomerswhichgenerateafredcal absorb light at $300~\\mathrm{nm}$ or greater. Such oligomers may be part of the polymer backbone or joined to a pendent group.  \n\nA hydrophilic compound which generates a free-radical polymerization initiator of the present invention may have a general formula:  \n\n![](images/e9fdf3483f48d9d14e2314ff7e31198e0902fb3b8373549ef9388a616e8d8635.jpg)  \n\nwhere m is an integer of from at least 1, generally from 1 to 100, preferably from 5 to 50, R\" and R\"\" may be the same or different and may be groups that provide the oligomer with water-solubility or water-dispersable, R\" and $\\mathrm{R}^{\\dag\\dag}$ may include, but are not limited to unsubstituted or substituted $(\\mathbf{C_{6}}\\mathbf{-}\\mathbf{C_{14}})\\mathbf{aryl}$ such as unsubstituted or substituted phenyl, unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl,unsubstituted or substituted phenanthryl, linear or branched $(\\mathbf{C_{1}}\\mathbf{-}\\mathbf{C_{15}})\\mathbf{a}1\\mathbf{ky}1$ ， linear or branched   \n50 $(\\dot{C_{2}}\\dot{C_{15}})$ hydroxyalky, substituted or unsubstituted $(\\mathrm{C}_{5}{-}\\mathrm{C}_{14})$ heterocyclic aryl where the heteroatom is S, N, or O, or linear or branched $(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{5})$ aminylalkyl,- $\\mathrm{-NR_{\\mathrm{9}}R_{\\mathrm{10}}}$ where $\\mathrm{R}_{9}$ and $\\mathrm{R}_{10}$ are the same or different and may be hydrogen, $\\displaystyle{(\\mathrm{C}_{1}-\\mathrm{C}_{3})}$ alkyl or $\\mathrm{(C_{1}-C_{4})}$ hydroxyalkyl. Substituents include,   \n55 but are not limited to, $(\\mathbf{C_{1}}\\mathbf{-}\\mathbf{C_{5}})\\mathbf{alkoxy}$ ，hydroxyl, $\\displaystyle(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{5})$ hydroxyalkyl, $(\\mathbf{C}_{1}\\mathbf{-}\\mathbf{C}_{5})\\mathbf{a}\\mathbf{l}\\mathbf{k}\\mathbf{y}1$ $\\displaystyle{(C_{1}-C_{5})}$ carboxyalkyl, $(\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{5})$ ester, $({\\dot{\\mathrm{C}}}_{1}{-}{\\dot{\\mathrm{C}}}_{5})$ aminylalkyl, phenyl, hydroxyphenyl, $\\mathrm{-NO}_{2}$ D  \n\nsulfonate, phosphate, $-\\mathrm{\\mathrm{SH}}$ D $\\displaystyle{(C_{1}-C_{5})}$ thioalkyl, acetyl, benzoyl, aldehyde, $\\displaystyle{(C_{1}-C_{5})}$ ketyl, and the like.Preferably, R\" or $\\mathbb{R}^{\\dag\\dag}$ is unsubstituted or substituted phenyl, unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, $(\\mathbf{C}_{1}\\mathrm{-}\\mathbf{C}_{8})\\mathbf{a}\\mathbf{l}\\mathbf{k}\\mathbf{y}\\mathbf{l}$ ， $(\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{10})$ hydroxyalkyl, unsubstituted or substituted $(\\mathrm{C}_{5}\\mathrm{-}\\mathrm{C}_{10})$ heterocyclic aryl, or $\\displaystyle{(C_{1}-C_{5})}$ aminyla1kyl. $\\mathrm{R}\"$ and $\\mathrm{R}^{\\dag\\dag}$ also may be $\\mathrm{-O-R_{11}}$ ，where $\\mathrm{R}_{11}$ is the same as $\\mathrm{R}\"$ and R\" described above.  \n\nR\", R\" and $\\mathrm{R}_{11}$ groups also may absorb light at $300\\mathrm{nm}$ to $365\\mathrm{nm}$ or greater. The most preferred R\", R\" and $\\mathrm{R}_{11}$ are water-soluble or water-dispersable and absorb light at 300 nm to $365~\\mathrm{nm}$ or greater.  \n\n$\\mathbf{R^{\\prime}}$ also may be a water-soluble or a water-dispersable group. R' may be a group which provides sufficient acid groups such that the polymer may be developed with an aqueous or aqueous base solution. R' may have an acid number of at least 50. Preferably,R' is water-soluble or water-dispersable and absorb light at $300~\\mathrm{{nm}}$ or greater. R' may be derived from acid functional monomers, non-acid functional monomers, alkylene oxides, polyesters, urethanes, or mixtures thereof. Urethanes are compounds that have at least one —CO(NH)— moiety, and biurets are urethanes that have at least one —NH—CONH—CONHmoiety in the structure. Examples of suitable oligomers are disclosed in U.S.Pat.No. 6,045,973, U.S.Pat.No. 6,166, 245,U.S. Pat.No.6,207,347 B1, U.S.Pat. No. 6,268,111 B1,U.S.Pat.No. 6,319,653,U.S.Pat.No. 6,322,951 B1, and U.S. Pat.No. 6.329,123 B1.  \n\nWhile not being bound by theory, it is believed that the pendent ketone substituents, as shown in formula VI, are the source of the free-radical polymerization initiator. Such pendent ketone substituents are integral to the compound and are internal or “built-in\" photoinitiators. Integral means that the ketone substitutent is a basic structural component of the polymer.  \n\nIn another embodiment of the invention a source of the free-radical may be a photoinitiator compound.Examples of such photoinitiators include, but are not limited to, imidazole dimers, benzophenones, thioxanthones, ketals, benzoin ethers, acetophenones, anthraquinones, naphthaquinones, or triazine-based compounds. Imidazole dimers such as heaxaarylbiimidazoles (HABl) are very useful in photosensitive formulations, such as in photoresists.  \n\nA hexaarylbiimidazole with a reactive group which may undergo an addition or condensation reaction with a reactive group of a carrier component as described above has a general formula:  \n\nalkyloxy or alkylthio. At least one of $\\mathrm{R}_{13}$ D $\\mathrm{R}_{14}$ and $\\mathrm{R}_{15}$ is a reactive group which may react with a reactive group of the carrier compound. Such reactive groups may have a labile hydrogen, such as in hydroxyl or aminyl groups. Examples   \n5 of reactive groups include, but are not limited to, $\\mathrm{-N}(\\mathrm{CH}_{2}\\mathrm{-OCH}_{3})_{2}$ ， carboxyl, ester, thio or isocyanate. Examples of spacer groups with reactive groups include, but are not limited to, $(\\mathrm{C}_{1}$ to $\\mathrm{C}_{12}\\mathrm{\\cdot}$ hydroxyalkyl, $(\\mathrm{C}_{1}$ to $\\mathbf{C}_{12}\\mathbf{\\Psi},$ carboxyalkyl, $\\mathrm{\\langleC_{1}}$ to $\\mathrm{C}_{12}$ Daminylalkyl, $\\displaystyle(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{12})$ alkylester, or   \n10 hydroxyalkyloxy such as —(O $\\mathrm{\\longrightarrowCH_{2}\\mathrm{\\longrightarrowCH_{2})O H}}$ ，-(0- $\\mathrm{CH}_{2}{\\mathrm{-}}\\mathrm{CH}_{2}{\\mathrm{-}}\\mathrm{CH}_{2})\\mathrm{OH}$ and— $\\mathrm{(O{\\_}C H_{2}{\\_}C H_{2}{\\_}C H_{2}}$ $\\mathrm{CH}_{2}\\mathrm{OH}$ $\\mathrm{(C_{1}}$ to $\\mathrm{C}_{12}\\mathrm{,}$ aliphaticisocyanate， $(\\mathrm{C}_{5}-\\mathrm{C}_{8})\\mathrm{cy-}$ cloaliphatic isocyanate or ( $\\mathrm{\\Delta}\\mathrm{C}_{5}$ to $\\mathrm{C}_{6}$ Daromatic isocyanate. Any aliphatic, aromatic or cycloaliphatic group with a   \n15 reactive group attached to it may perform as a spacer group. Preferably, the reactive group is joined to the photoinitiator by a spacer group.A spacer is preferred because bonding the photoinitiator to the carrier component is easier and less disruptive of the photoinitiator capability to form a poly  \n20 merization initiator. Preferred reactive groups are $\\mathrm{\\langleC_{1}}$ to $C_{6}$ hydroxy alkyl or $\\mathrm{\\langleC_{1}}$ to $C_{6})$ aminyl alkyl. In addition to $\\mathrm{R}_{15}$ equaling $\\mathrm{R}_{13}$ and $\\mathrm{R}_{14}$ $\\mathrm{R}_{15}$ also may be a halogen group such as chloro, bromo, or fluoro.  \n\nExamples of alkyl groups having 1 to 4 carbon atoms are 25 methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and test-butyl. Examples of suitable aryl groups having from 6 to 10 carbon atoms are phenyl, naphthyl, ortho-tolyl, metatolyl and para-tolyl. Both the alkyl and the aryl groups may be functionalized with a reactive group such as hydroxyl, 30 aminyl or other reactive groups discussed above.  \n\nHydrophobic photoactive compounds may be prepared by any suitable method known in the art. For example, hexaarylbiimidazole compounds may be prepared by oxidative coupling of triphenylimidazoles. Preparation of substituted triphenylimidazoles is described in U.S. Pat. No. 3,748,557,U.S.Pat.No.4,311,783,and U.S.Pat.No. 4,622,286. In some cases, reaction mixtures in which more than one hexaarylbiimidazole is produced can be used without complete separation and purification as described in U.S. Pat.No. 4,622,286.  \n\nAn example of forming substituted triphenylimidazoles used in the oxidation procedures to prepare the hexaarylbiimidazoles can be prepared by refluxing, in glacial acetic acid containing ammonium acetate, benzil with an appro45 priately substituted benzaldehyde or a benzil and benzaldehyde which are both suitably substituted, then drowning the reaction mass in water or in an ammoniun hydroxide solution, filtering and purifying the product by recrystalization; or by refluxing a benzoin and a benzaldehyde in methanol in 50 the presence of copper acetate and ammonia; or by heating a benzil and a benzaldehyde at $180^{\\circ}\\mathrm{~C~}$ .to $190^{\\circ}\\mathrm{~C~}$ in formamide as described in U.S.Pat.No.3,784,557.Benzils and substituted benzils may be prepared by any suitable method in the literature such as by oxidizing corresponding 55 benzoins as disclosed in U.S. Pat. No. 4,144,156.  \n\n![](images/c943a3f0b1ddb71d51505f7b4063a677aafed591ebb8a41a2765c5deb09f896b.jpg)  \n\nAnother method for forming a photoinitiator component with a reactive group is to react the photoinitiator, such as hexarrylbiimidazole, with an alkyl ether or ester in a Friedal Crafts reaction. The ether or ester group on the alkyl chain   \n60 or spacer group attached to the photoinitiator is cleaved to get a hydroxyl group on the spacer group. The photoinitiator may then be reacted with a reactive group on a carrier component by an addition or condensation reaction to form a photoinitiator of the present invention. Such addition and   \n65 condensation reactions, as well as the conditions under which they proceed, are well known in the art. Other photoinitiators such as thioxanthones, ketals, benzoin ethers,  \n\n$\\mathrm{R}_{13}$ ， $\\mathrm{R}_{14}$ and $\\mathrm{R}_{15}$ are the same or different and may be a hydrogen, unsubstituted or substituted alkyl, alkoxy, unsubstituted or substituted aryl, aryloxy, hydroxyl, aminyl, carboxyl, ester, thio, isocyanate,- $\\mathrm{-N}(\\mathrm{CH}_{2}\\mathrm{-OCH}_{3})_{2}$ ,hydroxy",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# 17  \n\nbenzophenones, acetophenones, anthraquinones, napthaquinones and triazine-based compounds may be functionalized with reactive groups by analogy using similar procedures.  \n\nExamples of such addition reactions that may occur 5 include the reaction of a hydroxyl, carboxyl or aminyl reactive group on the photoinitiator or joined to the photoinitiator by a spacer group with an isocyanate pendent group on the carrier component to obtain a urethane (-NHCOO—)，amide（—NHCO—）or urea bond （—NH- 10 CONH—) between the carrier component and the photoinitiator. Alternatively, an isocyanate group attached to the photoinitiator, or an isocyanate group joined to the photoinitiator by a spacer may react with a hydroxyl, carboxyl or aminyl functional group on the carrier component to form 15 the same types of urethane, amide and urea bonds.Examples of suitable isocyanates which may be employed are described above. Ester bonds $({\\mathrm{-}}\\mathrm{COOR})$ also may form to join a photoinitiator to a carrier such as a reaction between an acid group and an alcohol group. R represents an organic 20 moiety described above.  \n\nIn addition to the photoinitiators described above, aromatic chromophores may be employed in the present invention. Aromatic chromophores have groups such as phenyl and naphthyl, which are sensitive to light at wavelengths of : from $320\\ \\mathrm{nm}$ to $450\\ \\mathrm{nm}$ . Typically, such aromatic chromophores are light sensitive from $340~\\mathrm{nm}$ to $400\\mathrm{nm}$ ,more typically from $350\\mathrm{nm}$ to $365\\mathrm{nm}$ . While not being bound by any theory, it is believed that the aromatic groups of the chromophore provide the light sensitivity in the range of 320 nm to $450\\ \\mathrm{nm}$ . Examples of such aromatic chromophores include, but are not limited to, phenylacridine, or substituted phenylacridines. Such aromatic chromophores may be joined to a polymer by the same methods that the photoinitiators described above may be joined to a polymer.  \n\nExamples of other suitable compounds include, but are not limited to, plasticizers, surfactants, and complex surfactants. One example of a suitable plasticizer which may be bonded to a chain or backbone of a functional polymer is a urethane plasticizer having formula VIII.  \n\nVIII  \n\n$Z_{1}$ is the group $\\mathrm{R}_{16}$ is $\\mathrm{R}_{19}$ or $\\mathrm{CONH{\\mathrm{-}}\\mathrm{R}_{19}},$ $\\mathrm{R}_{17}$ and $\\mathrm{R}_{18}$ are hydrogen atoms or methyl groups,  \n\n![](images/b8997a7e146ce6100763b386cc8d7252b2e6bd96a24daf2e76ba8e021ab2dca1.jpg)  \n\n$\\mathrm{R}_{19}$ is a saturated aliphatic group with 1 to 20 carbon atoms,  \n\nn is zero or a whole number from 1 to 15, $\\mathbf{m}^{\\prime}$ is whole number from 2 to 4, $\\boldsymbol{\\mathrm{\\tt~p^{\\prime}~}}$ is zero or a whole number from 1 to 4, $\\mathbf{k}^{\\prime}$ is a whole number from 2 to 12, ${\\bf r}^{\\prime}$ is a whole number from 4 to 12, and $\\boldsymbol{\\mathrm{n^{\\prime}{+}}}\\boldsymbol{\\mathrm{p^{\\prime}}}$ is a whole number from 1 to 10, and wherein _ $\\mathrm{R}_{16}{=}\\mathrm{R}_{19}$ if $\\ensuremath{\\mathbf{p}}^{\\prime}{=}0$ D $\\mathrm{R_{16}{=}C O N H{\\mathrm{{-}}}\\mathrm{R_{10}}}$ if $\\mathrm{\\Delta}\\mathrm{n}{'}{=}0$  \n\nBecause the urethane of formula VIlI terminates in aliphatic or cycloaliphatic groups, a functional group such as a halogen may be added to at least one of the terminal groups in order for the urethane to react with a polymer backbone or pendent group.  \n\nExamples of water-soluble or water-emulsifiable surfactants that may be joined to a polymer include alkoxylated emulsifiers. A suitable alkoxylated emulsifier is one having the general formula:  \n\nwherein 一 $X_{1}$ is one of the following groups:  \n\n$$\n\\mathrm{R}_{20}{\\longrightarrow}\\mathrm{O}{\\cdot}(\\mathrm{A}^{\\prime\\prime}\\mathrm{O})_{n^{\\prime\\prime}}\\mathrm{~-}\\mathrm{H}\n$$  \n\nwhere A\"O are alkylene oxide units selected from ethylene oxide units $\\left(\\mathrm{CH}_{2}{\\longrightarrow}\\mathrm{CH}_{2}{\\longrightarrow}\\mathrm{O}\\right)$ and propylene oxide units $\\mathrm{(CH(CH_{3}){\\_}C H_{2}{\\_}O)}$ or $\\mathrm{(CH_{2}{\\mathrm{-}}C H(C H_{3}){\\mathrm{-}}O)}$ and mixtures of ethylene and propylene oxide units, either in the mixture of molecules, where $\\mathrm{R}_{20}$ is a hydrophobic group, typically a hydrocarbon group, $\\boldsymbol{\\mathrm{n}}\"$ is between 8 and 200, preferably between 15 and 40. Preferably, $\\mathrm{R}_{20}$ is a tristyrylphenol.  \n\nDyes may also be joined to functional compounds of the present invention. Suitable dyes include, but are not limited to, triphenylmethane dyes, azo dyes, polyazo dyes, anthraguinones, eosin, eosinate, thazine, fluorocein, phthalein,   \n45 xanthene, oxazine, aniline based, anionic and cationic dyes. Such dyes may be joined to the functional polymer by any suitable method in the art. Such dyes have one or more free reactive groups such as, for example, sulfinate, amino,or hydroxyl groups that may react with a group on the polymer.   \n50 An exemplary method of joining a dye to a polymer is to place a spacer group on one of the ring structures of the dye molecule employing a Friedal Crafts reaction as described above for the photoinitiators. Once the dye molecule has a spacer group, the reactive group on the spacer is then reacted   \n55 with a reactive group of a functional polymer as described above. The functional polymers have an average molecular weight range of at least 10oo daltons. More typically, the average molecular weight range of the functional polymers   \n50 is from 10,o0o daltons to 500,o0o daltons. Molecular weights may be measured by such methods as GPC (gel permeation chromatography) or SEC (size exclusion chromatography). The functionalized polymers of the present invention may be functionalized with one or more pendent   \n55 functional moieties in ranges of from 1.O to as high as 100 mole percent of reactive sites on the polymer backbone, typically from about 2.0 to about 20 mole percent, more  \n\n$\\mathrm{Y}_{1}$ is a saturated apliphatic or cycloaliphatic group with 2 to 12 carbon atoms,  \n\ntypically from about 5.0 to about 15 mole percent. Complete functionalization of the polymer backbone with pendent groups is not always desirable because such groups as hydroxyl and carboxyl groups on the backbone provide for solubility in alkaline solutions. Such solubility is highly desirable when the functionalized polymer is employed in photoresist. Acid functionality of the main chain may be a carboxylic acid functionality or may include, for example, a sulfonic acid or phosphoric acid functionality.  \n\nThe functionalized polymers of the present invention are film forming polymers that may be employed in any industry where polymer film coatings are desired. Such industries include, but are not limited to lithography, electrophotographic imaging members, optical data storage, decorative pigments, adhesives, cosmetics, security applications or active and passive optical elements such as polarizers, optical retarders or color filters, paints and other surface coating compositions. The functionalized polymers also have good flexibility, and are readily soluble in aqueous alkaline solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, and the like. Because the functionalized polymers have good flexibility and solubility, the functionalized polymers are especially useful in photoresist compositions, particularly in liquid imaging photoresists. The high solubility of the functionalized polymers in aqueous alkaline solutions enables photoresists made with the functionalized polymers to be easily stripped, thus preventing short circuiting on a circuit board. Additionally, undesirable and costly strippers such as organic-based, amine or organic solvent-containing strippers may be avoided. Thus, excessive waste treatment procedures may be eliminated from the printed wiring board procedures as well as environmental and worker safety concerns associated with such organic-based strippers. Good flexibility also provides for a photoresist that is not brittle and does not readily chip. Chipping, due to brittleness, can lead to circuit defects in printed wiring boards.  \n\nThe functionalized polymers also have good adhesion to metal surfaces due to their pendent functional groups. The functionalized polymers are also self cross-linking, thus the functionalized polymers may be employed as the sole crosslinking agent in a photoresist composition. Advantageously, cross-linking monomers or oligomers employed in conventional photoresists may be eliminated. Thus, premature polymeriztion between the various components of a photoresist composition are avoided. Accordingly, both the stability and the shelf life of such photoresists are improved.  \n\nBecause the functional polymers are hydrophilic, they are suitable for use in liquid photoresists, such as waterborne photoresists. Such photoresists may be positive-working or negative-working. Functionalized polymers of the present invention compose from $5\\%$ by weight to $90\\%$ by weight of the photoresist composition. Preferably the functionalized polymers comprise from $25\\%$ by weight to $70\\%$ by weight, most preferably from $30\\%$ by weight to $50\\%$ by weight of the liquid photoresist composition. In addition to a diluent, the balance of the photoresist composition may optionally include additional binder polymers, cross-linking monomers or oligomers, and conventional additives as described below. Diluents employed include water an organic solvent or mixtures thereof. A mono-alcohol or a polyol is a preferred organic diluent. Water is the most preferred diluent.  \n\nOptional cross-linking agents may be employed, but are preferably excluded. Such cross-linking agents include a monomer, or a short chain oligomer having ethylenic unsaturation, particularly, $\\mathbf{\\alpha}_{\\mathrm{{\\alpha}}}\\mathbf{\\mathrm{{\\alpha}}}_{\\mathrm{{\\alpha}}}\\mathbf{\\mathrm{{\\beta}}}$ -ethylenic unsaturation functionality of 2 or greater. A mixture of conventional monofunctional and multi-functional monomers may be used. Such optional cross-linking agents are included in amounts of from $5\\%$ to $15\\%$ by weight of the photoresist.  \n\nOptionally the functionalized polymers of the present 10 invention may contain an additional photoinitiator chemical system. Preferably such photoinitiators are excluded. The photoinitiator chemical system may compose from $0.1\\%$ to $5\\%$ by weight of the photoresist composition. Conventional photoinitiators or photoinitiator systems may be employed.  \n\nPhotoresist compositions of the present invention may also include an optional color former. Color formers are employed in amounts of from $0.1\\%$ to $1.0\\%$ by weight of the composition. Examples of suitable color formers include, but are not limited to, diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl-p-phenylenediamine, p-toluidine, $^{4,4^{\\prime}}$ -biphenyldiamine, o-chloroaniline， leuco crystal violet, leuco malachite green, and the like.  \n\nAdditionally, the photoimageable compositions may contain a wide variety of additional adjuvants including stabilizers, flexibilizing agents, adhesion promoters, plasticizers, fillers or mixtures thereof. Such adjuvants are additives that contribute to the effectiveness of the primary ingredients. Optionally, additional polymeric or resin binders may be added to the liquid photoresists. Such additional polymeric binders may include, as polymerized components, one or more acid functional monomers such as (meth)acrylic acid. For example, U.S. Pat. No. 5,952,153, discloses polymeric binders that have suficient acid functionality to be employed in the photoresists of the present invention. When employed, such polymers may be used in amounts of from $5\\%$ to $20\\%$ by weight of the photoresist composition.  \n\nProcessing of the liquid photoresist compositions is by any suitable means employed in the art. For example,a   \n40 photoimageable composition layer formed from a liquid composition is applied to a substrate, such as a surface, of a metal-clad board. An example of a suitable metal is copper. Any substrate on which a liquid photoresist may be applied may be employed. The liquid photoresist composition may   \n45 be applied to a substrate by any known means, such as spinning, dipping or roller coating. Once applied, most of the diluent is removed and the photoresist is then exposed to actinic radiation through appropriate artwork. Exposure to actinic radiation polymerizes the cross-linking components   \n50 in the light-exposed areas, if the photoresist is negativeworking, resulting in a cross-linked structure that is resistant to developer. Next, the unexposed portion of the photoresist is developed in dilute alkaline aqueous solution, such as a $1\\%$ sodium carbonate solution. The alkali solution causes   \n55 salt formation with carboxylic acid groups of the functionalized polymer rendering the unexposed portions of the photoresist soluble and removable. After development, an etchant may be used to remove metal from areas where the photoresist was removed thereby forming a printed circuit   \n$_{60}$ pattern. The remaining photoresist may be removed using an appropriate stripper, such as $1\\%$ to $3\\%$ sodium or potassium hydroxide aqueous solution.Organic based developers, such as tetraalkylammonium hydroxide based developers, may be used but are less preferred.  \n\n55The following examples are intended to further illustrate the present invention but are not intended to limit the scope of the invention.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 16,
+        "chunk": "# 21 EXAMPLE1  \n\nPolymer of Methacrylic Acid and Methyl Methacrylate functionalized with: 1,6-Hexamethylene Diisocyanate Biuret—Polypropoxylated Hydroxypropylmethacrylate Moieties  \n\nA homogeneous solution containing 62.0 grams of methacrylic acid and 265.0 grams of methyl methacrylate was prepared. $75\\%$ by weight of the homogeneous solution were transferred into a second flask. The homogeneous solution of the first flask was diluted to $26.0\\%$ by weight solids and the homogeneous solution of the second flask was diluted to $86.50\\%$ by weight solids by adding sufficient methyl ethyl ketone.  \n\nThe first flask was mixed and heated to reflux under atmospheric conditions. 2.0 grams of $^{2,2^{\\dag}}$ -azobis (2-methylbutyronitrile) was added to the reaction mixture, mixed and held at reflux for about 3O minutes.  \n\n6.25 grams of 2,2'-azobis (2-methylbutyronitrile) was mixed with 38.0 grams of methyl ethyl ketone and fed into the first flask along with the contents of the second flask over 4 hours while maintaining reflux. An additional amount of 9.0 grams of methyl ethyl ketone was then added to the first flask and the mixture was refluxed for an additional hour.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 17,
+        "chunk": "# 22  \n\nIn a separate clean dry air sparged addition funnel, 193.0 grams of polypropoxylated hydroxypropylmethacrylate (hydroxyl number $^{-158}$ ）was weighed out. The polypropoxylated hydroxypropylmethacrylate was added to the flask   \n5 containing the 1,6-hexamethylene diisocyanate biuret over about 1 hour with mixing and maintaining a temperature of $35^{\\circ}\\mathrm{C}$ The addition funnel was then rinsed with 118.0 grams of methyl ethyl ketone to remove any remaining polypropoxylated hydroxypropylmethacrylate. The rinse was added   \n.0 to the flask containing the biuret with a temperature increased to $60^{\\circ}\\mathrm{C}$ . The reaction was maintained for 3 hours at $60^{\\circ}\\mathrm{C}$ The reaction was monitored to determine completion of the synthesis of a urethane acrylate moiety by known analytical methods in the art.  \n\n5 The functionalized polymer was prepared by weighing out 763.0 grams of the acrylic polymer ( $47\\%$ solids）and 55.0 grams of methyl ethyl ketone to a clean, dry air sparged flask. The combination was mixed and heated to $45^{\\circ}\\mathrm{C}$ .The urethane/acrylate moiety was then added to the acrylic :0 polymer over about 1 hour. 0.50 grams of Irganox $\\textsuperscript{\\textregistered}$ 1076 and 28.0 grams of methyl ethyl ketone was added to the reaction mixture. The reaction contents were held at $45^{\\circ}\\mathrm{C}$ for 3 hours with constant mixing. The polymer main chain was 6 mole percent functionalized with the moiety. P rep!5 resents the polymer backbone with one functional moiety attached.  \n\n![](images/70a69e0dfc8e2448f45d94e6d66a317a4efe8582dbfff142c5b04b13e0015e79.jpg)  \n\n4.55 grams of 2,2'-azobis (2-methylbutyronitrile) were dissolved in 48.0 grams of methyl ethyl ketone and mixed. The mixture was then added to the first flask over a period of 90 minutes while maintaining reflux.  \n\n55  \n\n8.5 grams of 2,2'-azobis (2-methylbutyronitrile) were mixed with 48.0 grams of methyl ethyl ketone and then fed into the reaction mixture over about 150 minutes while maintaining reflux. An additional amount of 23.0 grams of methyl ethyl ketone were added to the reaction mixture. At the end of the reaction, 2,2'-azobis (2-methylbutyronitrile) was thermally killed off to below parts per million concentrations. The acrylic polymer main chain or back bone product was set aside.  \n\n150.0 grams of 1,6-hexamethylene diisocyante biuret $(23.0\\%$ NCO) were added to a clean dry, nitrogen sparged flask. 0.06 grams of dibutylin dilaurate, 0.05 grams of Irganox $\\textsuperscript{\\textregistered}$ 1076 (antioxidant) and 160.0 grams of methyl ethyl ketone were also added to the flask. The flask was sparged with dry air and stoppered. The components were mixed and heated at about $35^{\\circ}\\mathrm{~C~}$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# EXAMPLE2  \n\nPolymer of 2-Hydroxyethyl Methacrylate,   \nMethacrylic Acid and Methyl Methacrylate Functionalized with: Isophorone Diisocyanate—Polypropoxylated Hydroxypropylmethacrylate Moieties  \n\nThe step of preparing the acrylic polymer backbone was the same as in the method described in Example 1 above except that 70.0 grams of 2-hydroxyethyl methacrylate was added to the mixture of methacrylic acid and methyl methacrylate.  \n\nThe reaction conditions for preparing the functionalized pendent groups were the same as described in Example 1 above except that 1 mole of isophorone diisocyanate was reacted with about one mole of hydroxy methacrylate to form a isophorone diisocyante hydroxy methacrylate moiety.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 19,
+        "chunk": "# 23  \n\nThe isocyanate groups of the isophorone diisocyanate hydroxy methacrylate moiety were reacted with the hydroxyl groups of the 2-hydroxyethyl methacrylate moiety under the conditions described in Example 1 to form a functionalized polymer with functionalized pendent groups as shown below. The polymer was 6 mole percent functionalized. P represents the polymer backbone.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 20,
+        "chunk": "# 24 EXAMPLE 3  \n\n![](images/e2ca7f100846617d0686c05e98381ec2a8d1f42abc8512517b6d679c1e0d5db1.jpg)  \n\nSynthesis of 1,6-Hexamethylene Diisocyanate Trimer-Polyalkoxylated Hydroxyalkyl (meth)acrylate, or a 1,6-Hexamethylene   \nDiisocyanate Trimer-Hydroxyalkyl (meth)acrylate   \n(urethane/acrylate with at least one free isocyanate)  \n\n10  \n\nOne mole of 1,6-hexamethylene diisocyanate trimer is added to a clean dry, nitrogen sparged flask. 0.06 grams of dibutylin dilaurate, 0.05 grams of Irganox $\\mathbb{R}$ (antioxidant) 15 and 160.0 grams of methyl ethyl ketone are also added to the flask. The flask is sparged with dry air and stoppered. The components are mixed and heated at $35^{\\circ}\\mathrm{C}$ Two moles of a polyalkoxylated hydroxyalkyl (meth)acrylate, or two moles 20 of hydroxyalkyl (meth)acrylate are added to the flask, mixed with the trimer, and heated at $35^{\\circ}\\mathrm{~C~}$ .for one hour. The reaction temperature is increased to $60^{\\circ}\\mathrm{C}$ and the reaction 25 is maintained for 3 hours. The resulting compound has the following general structure where n is an integer of from 0 to 1000, preferably from 1 to 200, 1 is an integer of from 1 to $10,\\mathrm{~m~}$ is an integer of from 1 to 10 and $\\mathrm{R}^{3}$ is (meth) 30 acrylate.  \n\n![](images/530f5ae9da8db93ad5aacd85c5cec1b8ddf3a77e2631438f82002a67343c6731.jpg)  \n\nThe foregoing urethane/acrylate with one free isocyanate 65 group may be reacted with a polymer main chain containing free carboxyl, hydroxyl, or aminyl groups to form a functionalized polymer of the present invention.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 21,
+        "chunk": "# 25 EXAMPLE 4",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 22,
+        "chunk": "# Synthetic Procedure  \n\n$60\\textrm{g}$ of a diacrylate acceptor compound (formula IX 5 below）and $0.5\\mathrm{~g~}$ of diazabicyclo-undecene (DBU） are weighed into a $500~\\mathrm{ml}~3$ -neck round bottom flask equipped with a mechanical stirrer and addition funnel. $15.0~\\mathrm{g}$ of an acetoacetate derived donor compound (formula X below) is weighed into the addition funnel. The acceptor compound 10 and DBU are mixed for 5 minutes prior to addition of the donor compound. The donor compound is then added dropwise to the stirred acceptor/DBU mixture over a 15 minute period. The solution is warmed to 54 degrees Celsius after addition of the donor compound is complete. After the 1s exotherm subsided in 100 minutes, a viscous yellow liquid is obtained which does not gel upon standing.  \n\n![](images/240c076d4dbee188d7d96dd1aea9abea97d6ce7fe986c7885d583998e75d4983.jpg)  \n\nwhere $\\mathbf{R^{\\prime}}$ is a radical derived from a urethane oligomer having a formula:",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 23,
+        "chunk": "# 26  \n\nparts of cold water whereupon 3.1 parts of reaction product precipitate. The product is isolated by filtration and purified by recrystalling twice from ethanol. The product, a chlorinated hydroxybutyl imidazole, is a white crystalline solid.  \n\nTo 1.1 parts of the above prepared imidazole dissolved in 100 parts of ethanol containing 12 parts of potassium hydroxide is added 450 parts of a $1\\%$ by weight water solution of potassium ferricyanide at a rate of 5 parts per minute for 1.5 hours with continuous stirring. The oxidation reaction product in an amount of 1.0 parts precipitates from the reaction mixture, is isolated by filtration, and is washed with water until free from ferricyanide. The product is dried at $56^{\\circ}\\mathrm{C}$ for eight hours at $0.1~\\mathrm{mm}$ . mercury pressure after predrying overnight in a vacuum oven at $50^{\\circ}\\mathrm{C}$ It is solvated with two moles of enthanol for every three moles of biimidazole. The product is a biimidazole having the general formula shown below.  \n\nA portion of the ethanol-solvated product was dried azeotropically with cyclohexane to produce non-solvated ’ material. Recrystallization from ether also yields the nonsolvated product.  \n\n30  \n\n![](images/fe69bdc7937e07f330da0f6fe4b277cc20c03f74d591fec6e5bb7fd9cdf78ac3.jpg)  \n\nThe oligomer of the above reaction between donor compound XI and acceptor compound $\\mathrm{\\DeltaX}$ has the following general formula:  \n\n![](images/f1d2605019c1baaae0bc871fc580857dc6b9144ac1136c477cb94fed2430e146.jpg)  \nEXAMPLE5  \n\n40 The above photoactive component is then reacted with the pendent carboxyl groups of an oligomer composed of methylmethacrylate and acrylic acid to bind the photoactive component with the oligomer by an ester linkage. The oligomer is prepared by free radical polymerization of the   \n45 methylmethacrylate and acrylic acid monomers. The methylmethacrylate and acrylic acid monomers are obtainable from Rohm and Haas Company. The reaction takes place in an aqueous acidic environment. The reactants are refluxed in the acidic environment from $90^{\\circ}\\mathrm{~C~}$ .to $100^{\\circ}\\mathrm{~C~}$ .to obtain a   \n50 water-soluble photoinitiator yield of from $85\\%$ to $90\\%$ by weight.  \n\n![](images/5027d4d80aeb9f96d44e0d25f0ebf45973d8d1b3c661b8a57f43a8f5c862dc28.jpg)  \nTo 2.1 parts of hydroxybutyl substituted benzil (0.01 mole) dissolved in 50 parts of glacial acetic acid containing 6 parts of ammonium acetate (0.078 mole) is added 1.4 parts of o-chlorobenzaldehyde (O.o1 mole), and the solution is refluxed for 2 hours. The solution is then drowned in 200  \n\nThe hydrophilic photoinitiator containing compound may be employed as a cross-linking agent or further polymerized and employed as a polymer binder in a photoresist formu；lation. Upon exposure to light, a radical from the photoactive component is generated to polymerize the cross-linking agents of the formulation.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 24,
+        "chunk": "# EXAMPLE6",
+        "category": " Introduction"
+    },
+    {
+        "id": 25,
+        "chunk": "# Synthesis of Functionalized Copolymer  \n\nA homogeneous solution containing 197 grams of methacrylic acid, 512 grams of methyl methacrylate and 79 grams of poly(ethoxylated) monomethacrylate was prepared. $75\\%$ by weight of the homogeneous solution were prepared into a second flask. The homogeneous solution of",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 26,
+        "chunk": "# 27  \n\nthe first flask was diluted to $25\\%$ by weight solids and the homogeneous solution of the second flask was diluted to $60\\%$ be weight solids by adding sufficient methyl ethyl ketone.  \n\nThe first flask was mixed and heated to reflux under atmospheric conditions. 2.0 grams of 2,2'-azobis (2-methylbutyronitirle) was added to the reaction mixture, mixed and held at reflux for 30 minutes.  \n\n6.0 grams of 2,2'-azobis (2-methylbutyronitirle) was mixed with about 40 grams of methyl ethyl ketone and fed into the first flask along with the contents of the second flask over 4 hours while maintaining reflux.An additional amount of 9.0 grams of methyl ethyl ketone was then added to the first flask and the mixture was refluxed for an additional hour.  \n\n5.0 grams of 2,2'-azobis (2-methylbutyronitrile) were dissolved in 50.0 grams of methyl ethyl ketone and mixed. The mixture was then added to the first flask over a period of 90 minutes while maintaining reflux.  \n\n9.0 grams of 2,2'-azobis (2-methylbutyronitrile) were mixed with 50.0 grams of methyl ethyl ketone and then fed into the reaction mixture over 150 minutes while maintaining reflux. An additional amount of 25.0 grams of methyl ethyl ketone were added to the reaction mixture. At the end of the reaction, 2,2'-azobis (2-methylbutyronitirle) was thermally killed off to below parts per million concentrations. The acrylic copolymer main chain or backbone was set aside.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 27,
+        "chunk": "# 28 EXAMPLE7  \n\n5.31 grams of 1,6-hexamethylene diisocyanate biuret $(23.\\%$ free-NCO) were added to a clean dry, nitrogen sparged flask. 0.06 grams of dibutylin dilaurate, 0.05 grams of Irganox $\\textsuperscript{\\textregistered}$ 1076 (antioxidant) and 160.0 grams of methyl ethyl ketone were also added to the flask. The flask was sparged with dry air and stoppered. The components were mixed and heated at $35^{\\circ}\\mathrm{~C~}$  \n\nIn a separate clean dry air sparged addition funnel, 15.97 grams of poly(ethoxylate-b-caprolactone) monomethacrylate oligomer was weighed out. The oligomer was added to the flask containing the 1,6-hexamethylene diisocyanate biuret over 1 hour with mixing and maintaining a temperatureof $35^{\\circ}\\mathrm{C}$ The addition funnel was then rinsed with 118.0 grams of methyl ethyl ketone to remove any remaining oligomer. The rinse was added to the flask containing the biuret with a temperature increased to $60^{\\circ}\\mathrm{~C~}$ The reaction was maintained for 3 hours at $60^{\\circ}\\mathrm{~C~}$ . the reaction was monitored to determine completion of the synthesis of a urethane acrylate moiety by high pressure liquid chromatography (HPLC).  \n\nThe functionalized polymer was prepared by weighing out 763.0 grams of the acrylic copolymer ( $47\\%$ solids) and 50.0 grams of methyl ethyl ketone to a clean, dry air sparged flask. The combination was mixed and heated to $45^{\\circ}\\mathrm{C}$ .The urethane/acrylate moiety was then added to the acrylic polymer over 1 hour 0.50 grams of Irganox $\\textsuperscript{\\textregistered}$ 1076 and 30.0 grams of methyl ethyl ketone was added to the reaction mixture. The reaction contents were held at $45^{\\circ}\\mathrm{~C~}$ .for 3 hours with constant mixing. The resulting copolymer was composed of 25 mole $\\%$ of methyacrylic acid, 65 mole $\\%$ of methyl methacrylate and 10 mole $\\%$ of poly(ethoxylated) monomethacrylate residues. The copolymer main chain was 6 mole $\\%$ functionalized with the moiety.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 28,
+        "chunk": "# Synthesis of a Functionalized Copolymer  \n\n5 A homogeneous solution containing 77.5 grams of 2-hydroxyethyl methacrylate, 194 grams of methacrylic acid, and 504 grams of methyl methacrylate was prepared. $75\\%$ by weight of the homogeneous solution was transferred to a second flask. The homogeneous solution of the first flask   \n10 was diluted to $25\\%$ by weight solids and the homogeneous solution of the second flask was diluted to $60\\%$ by weight solids by adding sufficient methyl ethyl ketone.  \n\nThe first flask was mixed and heated to reflux under atmospheric conditions. 2.0 grams of 2,2'-azobis (2-meth5 ylbutyronitirle) was added to the reaction mixture, mixed and held at reflux for 30 minutes.  \n\n6.25 grams of 2,2'-azobis (2-methylbutyronitirle) was mixed with 40.0 grams of methyl ethyl ketone and fed into the first flask along with the contents of the second flask over 4 hours while maintaining reflux. An additional amount of 9.0 grams of methyl ethyl ketone was then added to the first flask and the mixture was refluxed for an additional hour.  \n\n5.0 grams of 2,2'-azobis (2-methylbutyronitrile) were dissolved in 50.0 grams of methyl ethyl ketone and mixed. The mixture was then added to the first flask over a period of 90 minutes while maintaining reflux.  \n\n9.0 grams of 2,2'-azobis (2-methylbutyronitirle) were mixed with 50.0 grams of methyl ethyl ketone and then fed into the reaction mixture over 150 minutes while maintain30 ing reflux. An additional amount of 23.0 grams of methyl ethyl ketone were added to the reaction mixture.At the end of the reaction, $^{2,2^{\\dag}}$ -azobis (2-methylbutyronitirle) was thermally killed off to below parts per million concentrations. The acrylic polymer main chain or backbone product was set 35 aside.  \n\n150.0 grams of 1,6-hexamethylene diisocyanate biuret $23.0\\%$ -NCO) were added to a clean dry, nitrogen sparged flask. 0.06 grams of dibutylin dilaurate, 0.05 grams of Irganox $\\textsuperscript{\\textregistered}$ 1076 (antioxidant) and 160.0 grams of methyl ethyl ketone were also added to the flask. The flask was sparged with dry air and stoppered. The components were mixed and heated at $35^{\\circ}\\mathrm{~C~}$  \n\nIn a separate clean dry air sparged addition funnel, 190.0 grams of poly(ethoxylate- $\\cdot\\mathbf{b}$ -caprolactone)monomethacrylate oligomer was weighed out. The oligomer was added to the flask containing the 1,6-hexamethylene diisocyanate biuret over 1 hour with mixing and maintaining a temperature of $35^{\\circ}\\mathrm{C}$ . The addition funnel was then rinsed with 120.0 grams of methyl ethyl ketone to remove any remaining oligomer The rinse was added to the flask containing the biuret with a temperature increased to $60^{\\circ}\\mathrm{~C~}$ The reaction was maintained for 3 hours at $60^{\\circ}\\mathrm{C}$ . The reaction was monitored to determine completion of the synthesis of the urethane acrylate moiety.  \n\n55 The functionalized polymer was prepared by weighing out 750.0 grams of the acrylic copolymer and 55.0 grams of methyl ethyl ketone to a clean, dry air sparged flask. The combination was mixed and heated to $45^{\\circ}\\mathrm{C}$ The urethane/ arcrylate moiety was then added to the acrylic copolymer   \n60 over 1 hour. 0.50 grams of Irganox $\\textsuperscript{\\textregistered}$ 1076 and 30.0 grams of methyl ethyl ketone was added to the reaction mixture. The reaction contents were held at $45^{\\circ}\\mathrm{C}$ . for 3 hours with constant mixing. The polymer main chain was 6 mole percent functionalized with the moiety.  \n\n55 What is claimed is:  \n\n1. A polymer comprising $\\mathbf{\\alpha}_{\\mathrm{{\\alpha}}}\\mathbf{\\mathrm{{\\alpha}}}_{\\mathrm{{\\alpha}}}\\mathbf{\\mathrm{{\\alpha}}}_{\\mathrm{{\\alpha}}}$ -unsaturation and a photoinitiator joined to the polymer, the photoinitiator generates a",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 29,
+        "chunk": "# 29",
+        "category": " Introduction"
+    },
+    {
+        "id": 30,
+        "chunk": "# 30  \n\nfree radical when exposed to actinic radiation, the photoinitiator is chosen from an imidazole dimer, an anthraquinone, a naphthaquinone, a ketal, a triazine compound, or combinations thereof, the polymer has an average molecular weight of at least 1000 daltons.  \n\n2. The polymer of claim 1, further comprising multiple ester links. 3. The polymer of claim 2, wherein the ester links in the polymer are greater than 2. 4. The polymer of claim 1, wherein the polymer has one 10 or more side chains comprising greater than 2 ester links.  \n\n5. The polymer of claim 1, wherein the imidazole dimer is a hexaarylbiimidazole. 6. The polymer of claim 1, further comprising a stripping agent, a plasticizer, surfactant, aromatic chromophore, dye, or combinations thereof joined to the polymer. 7. The polymer of claim 1, wherein the polymer has an average molecular weight of from 10,00o daltons to 500,000 daltons.",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/functionalized polymer.json b/task2/task2-chunks/functionalized polymer.json
new file mode 100644
index 0000000..176b1b4
--- /dev/null
+++ b/task2/task2-chunks/functionalized polymer.json	
@@ -0,0 +1,127 @@
+[
+    {
+        "id": 1,
+        "chunk": "# (19) United States (12) Patent Application Publication (1o) Pub. No.: US 2004/0224259 A1 Anzures et al. (43) Pub. Date: Nov. 11, 2004",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# (54) FUNCTIONALIZED POLYMER",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# Related U.S. Application Data  \n\n(75） Inventors: Edgardo Anzures, Westborough, MA (US); Robert K. Barr, Shrewsbury, MA (US); Yueping Fu, Shrewsbury, MA (US)  \n\n(60) Provisional application No. 60/432,875, filed on Dec. 12,2002.",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# Publication Classification  \n\nCorrespondence Address: EDWARDS & ANGELL, LLP P.O. Box 9169 Boston, MA 02209 (US)  \n\n(51) Int. CI.7 G03C 1/73   \n(52) U.S. Cl. 430/281.1",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# ABSTRACT  \n\n(73） Assignee: Shipley Company, L.L.C., Marlbor-ough, MA  \n\n(21) Appl. No.: 10/733,611   \n(22) Filed: Dec.11,2003  \n\nA functionalized copolymer containing a main chain derived from polymerizable monomers and pendent functional groups terminated with one or more $\\mathbf{\\alpha}_{\\mathbf{{\\alpha}}}\\mathbf{\\alpha}_{\\mathbf{{\\alpha}}}\\mathbf{\\alpha}_{\\mathbf{{\\alpha}}}$ or $\\upbeta$ ethylenically or acetylenically unsaturated groups. The functionalized copolymers are self cross-linking and are suitable for use as binders.",
+        "category": " Abstract"
+    },
+    {
+        "id": 6,
+        "chunk": "# FUNCTIONALIZED POLYMER",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# BACKGROUND OF THEINVENTION  \n\n[0001] The present invention is directed to a functionalized polymer. More specifically, the present invention is directed to a functionalized polymer that improves the performance of photosensitive compositions.  \n\n[0002] Polymers are employed for numerous purposes in a wide variety of industries. Such industries include lithography, optical data storage, decorative pigments, adhesives, cosmetics, security applications or active and passive optical elements such as polarizers, optical retarders or color filters, and electrophotographic imaging members.  \n\n[0003] In lithography, polymers are employed in photopolymerizable compositions such as photoresists. Polymers may function as a binder for photoresist compositions. Other components of photoresists include cross-linking monomers that cross-link after exposure to actinic radiation, and photoinitiators.Photoinitiators initiate the cross-linking reaction between the cross-linking monomers upon light exposure. Other additives included in photoresists include anti-striation reagents, plasticizers, speed enhancers, fillers, dyes, and the like. Because polymer binders compose a majority of a photoresist, a photoresist derives most of its properties from the polymer binder fraction.  \n\n[0004]  Photoresists may be primary photoimaging resists or secondary photoimaging resists. Primary photoresists are used to form temporary coatings on substrates. Secondary photoresists are hardenable and form permanent layers, e.g., solder masks. Photoresists are used to make printed circuits, printing plates, solder masks and the like. Photoresists have various requisites such as etching resistance, heat resistance, adhesion and developable in developer solutions such as highly alkaline solutions. However, the lithographic industry has found that the synthesis of a polymer that may be employed in a photoresist and that satisfies all of the requisites for a photoresist is difficult. For example, a polymer having a polyacrylate main chain or backbone can be easily synthesized, but such a polymer has poor etching resistance and has difficulties in the developing process. In order to secure etching resistance,workers in the art have considered adding an alicyclic unit to the main chain. However, to form such a copolymer is difficult.  \n\n[0005]As the technology level of printed circuit boards increases towards finer lines/spaces, the demand placed on the photoresist materials used to produce such boards becomes greater. This in turn places a greater burden on the photoresist formulator to accommodate improved performance, without a decrease in production level or an increase in manufacturing cost of the photoresist product. Similar considerations apply for use of photopolymerizable compositions in proofing and flexographic printing.  \n\n[0006] For use in the manufacture of printed circuit boards having fine lines/spaces, it is critical that the photoresist used posses properties such that, upon imaging, the exposed and developed photoresist affords photoresist patterns having good sidewall geometry (i.e., sidewalls are smooth, planar and form an angle of $90^{\\circ}$ with respect to the substrate surface, and are free of imperfections such as mousebites, gouges, foots, etc.). Photoresists that afford good sidewall geometry perform better in printed circuit board manufacture than otherwise comparable photoresists that do not afford good sidewall geometry. Photoresists that do afford good sidewall geometry exhibit higher resolution, are useful in production of finer line/space printed circuit boards, and give fewer defects and higher yields in printed circuit board manufacture.  \n\n[0007] Circuit lines and spaces on circuit boards have continued to shrink as more circuitry needs to be fit onto smaller surfaces. At the same time, metal plating heights have increased above the thickness of the photoresist. This causes the metal to hang over the photoresist resulting in a very narrow space containing the photoresist being encapsulated by metal overplating. The photoresist may then be trapped by the plated overhang and stripping is made difficult. If the photoresist is not stripped clean, ragged metal circuit lines result after etching which are unusable. Such circuit lines can cause short-circuiting on the board.  \n\n[0008] Some manufacturers have tried thicker photoresists to accommodate the increasing plating heights. However, such an approach is more expensive and limits resolution of the circuit lines. Many manufacturers use organic-based (amine- or organic solvent-containing) alkaline stripping solutions that produce a smaller stripped particle to facilitate stripping. While the organic strippers, e.g., solutions containing trimethylamine or tetramethylammonium hydroxide, remove the photoresist, such strippers are expensive relative to alkaline aqueous strippers (sodium hydroxide and potassium hydroxide), and have more waste treatment and environmental concerns associated with them. Further, due to emphasis in the industry on reducing solvent emissions in the workplace, solvent-strippable photoresists are much less desirable than the aqueous-strippable. Accordingly, there is a need for improved primary imaging photoresists.  \n\n[0009]   Secondary imaging photoresists also suffer from a number of problems. To best serve their intended purpose, secondary imaging photoresists such as solder masks desirably exhibit a high degree of chemical resistance to solder and the fluxes used in soldering operations. Solder masks also desirably have a high degree of thermal resistance relative to the elevated temperatures used in soldering operations. Many solder masks produced from photosensitive compositions are deficient in these regards, having tendencies to degrade, blister or separate from circuit boards under conditions of soldering applications. Yet other photosensitive resin compositions produce solder masks that are excessively brittle with increased tendency to chip and flake under conditions encountered in handling and processing of circuit boards on which they are arranged. Attempts at solving such problems often are counter-productive, i.e., generating problems associated with the photosensitive composition itself such as premature curing, instability, short shelf-life and the like.  \n\n[0010]  Instability of a photoresist composition results in a short shelf-life. Instability may result from the cross-linking monomers included in the photoresist composition.Prior to exposure of a photoresist composition to actinic radiation, each monomer is a potential reactant with another monomer. If not properly stored or when the photoresist is prematurely exposed to a radiation source, the monomers may prematurely react, thus spoiling the composition and reducing shelf-life. Also, after exposure of the photoresist composition to actinic radiation, a fair proportion of the cross-linking monomers may not react. The photopolymerization process never reaches $100\\%$ conversion, thus there is always free monomer existing in cured states. Improper curing of the photoresist may occur resulting in brittle or poorly chemically resistant photoresist.  \n\n[0011] Unreacted monomers also may migrate through cover sheets composed of polyethylene to polyethylene/ polyester interface of a dry film roll. Such unreacted monomers may act as a lubricant at the interface and cause slippage and distortion. The monomers may plasticize the photoresist resulting in edge fusion of the dry film rolls. Since the monomer may be on the cover sheet, there is a chance for human contact with such monomers, thus presenting a health hazard to workers handling the dry film. Art work used in the imaging steps also may be contaminated with unreacted monomer which presents another avenue of worker contact with the monomers. Unreacted monomers also may leach into various processing solutions, such as plating solutions, to adversely affect the performance of the solutions. Additionally, monomers may cause scum and residue formation in developer and/or stripper solutions as well as on equipment.  \n\n[0012] Waste treatment of photoresist is another problem. Conventional waste treatment schemes involve a process in which the pH of the waste stream is lowered by the addition of acid. This causes pH-sensitive materials such as the polymer binder of the photoresist to precipitate out of solution for easy disposal. However, monomers are typically not as $\\mathfrak{p H}$ -sensitive as polymers and as a result are more difficult to treat than the polymer binders, thus presenting an environmental hazard.  \n\n[0013]  Formulation of a primary imaging photoresist and a secondary imaging photoresist involves a careful balancing of factors, often seemingly inconsistent, in order to attain desirable properties in the photoresist and to address the numerous foregoing problems. As mentioned above photoresists contain numerous components such as polymer binders, various monomers, photoinitiators, dyes and other additives. Because polymer binders compose a majority of the photoresist, a photoresist derives most of its properties from the polymer binder fraction.  \n\n[0014] U.S.Pat. No. 5,962,190 and U.S. Pat.No. 6,180, 323 both to McKeever disclose a photoresist which allegedly has improved sidewall geometry and broad development latitude due to the polymer binder. However, McKeever does not address such parameters as improved line adhesion with faster stripping ability, or reduced scum and residue formation. Typically, good fine line adhesion is sacrificed for faster stripping. Accordingly, there is a need for a polymer that improves stripping ability of photoimageable compositions with aqueous strippers, provides good adhesion, and provides a stable photoresist composition to improve shelf-life.",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# SUMMARY OF THE INVENTION  \n\n[0015]   A compound which includes a backbone having a formula:  \n\n$$\n(\\mathrm{A)_{u}(B)_{v}(C)_{w}(D)_{x}(E)_{y}(F)_{z}}\n$$  \n\n[0016] where Ais derived from one or more hydroxyalkyl (meth)acrylate, B is derived from one or more hydroxy polyalkyleneoxide (meth)acrylate, $\\mathrm{^c}$ is derived from one or more alkyl(meth)acrylate, D is derived from one or more (meth)acrylic acid, E is derived from one or more vinyl aromatic monomer, nitrogen containing compound or thioanalog of a nitrogen containing compound, silicon containing monomer, substituted ethylene monomer, or cyclic olefin monomer, and F is derived from one or more hydroxy poly opened-ring lactone polyalkylene oxide (meth)acrylate, where u, v,w, x, y and $\\textbf{z}$ are weight percentages of the monomers in the backbone, where u is O to $30\\%$ ,vis O to $30\\%$ ,w is 5 to $70\\%$ , x is 5 to $40\\%$ ,y is O to $20\\%$ and $\\mathbf{z}$ is 0 to $30\\%$ with the proviso that at least one of u, v or $\\mathbf{z}$ is greater than O, and at least one of A, B, C, D, E and F has at least one pendent functional group.  \n\n[0017]  The present invention also is directed to a photopolymerizable composition which includes a polymeric binder having a formula:  \n\n$$\n(\\mathbf{A})_{\\mathrm{u}}(\\mathbf{B})_{\\mathrm{v}}(\\mathbf{C})_{\\mathrm{w}}(\\mathbf{D})_{\\mathrm{x}}(\\mathbf{E})_{\\mathrm{y}}(\\mathbf{F})_{\\mathrm{z}}\n$$  \n\n[0018] where Ais derived from one or more hydroxyalkyl (meth)acrylate, B is derived from one or more hydroxy polyalkyleneoxide (meth)acrylate, C is derived from one or more alkyl(meth)acrylate, D is derived from one or more (meth)acrylic acid,E is derived from one or more vinyl aromatic monomer, nitrogen containing compound or thioanalog of a nitrogen containing compound, silicon containing monomer, substituted ethylene monomer, or cyclic olefin monomer, and F is derived from one or more hydroxy poly opened-ring lactone polyalkylene oxide (meth)acrylate, where u, v, w, x, y and $\\textbf{z}$ are weight percentages of the monomers in the backbone,where $\\mathfrak{u}$ is O to $30\\%$ ,vis O to $30\\%$ ,w is 5 to $70\\%$ ， $\\mathbf{x}$ is 5 to $40\\%$ ,y is O to $20\\%$ and $\\mathbf{z}$ is 0 to $30\\%$ with the proviso that at least one of u,v or $\\textbf{z}$ is greater than O, and at least one of A, B, C, D, E and F has at least one pendent functional group; and a photoinitiator. Optionally, the photopolymerizable composition may include at least one ethylenically unsaturated monomer as a cross-linking agent.  \n\n[0019] In another aspect, the present invention is directed to a method of imaging which includes the steps of (1) providinga photopolymerizable composition which includes a compound having a formula:  \n\n$$\n(\\mathrm{A)_{u}(B)_{v}(C)_{w}(D)_{x}(E)_{y}(F)_{z}}\n$$  \n\n[0020] where Ais derived from one or more hydroxyalkyl (meth)acrylate, $\\mathbf{B}$ is derived from one or more hydroxy polyalkyleneoxide (meth)acrylate, C is derived from one or more alkyl(meth)acrylate, D is derived from one or more (meth)acrylic acid, E is derived from one or more vinyl aromatic monomer, nitrogen containing compound or thioanalog of a nitrogen containing compound, silicon containing monomer, substituted ethylene monomer, or cyclic olefin monomer, and $\\mathrm{~F~}$ is derived from one or more hydroxy poly opened-ring lactone polyalkylene oxide (meth)acrylate, where u, v, w, X, y, and z are weight percentages of the monomers in the backbone,where u is O to $30\\%$ ,vis O to $30\\%$ ,wis 5 to $70\\%$ ， $\\mathbf{x}$ is 5 to $40\\%$ ,y is O to $20\\%$ and $\\mathbf{z}$ is O to $30\\%$ with the proviso that at least one of u, v or $\\mathbf{z}$ is greater than O, and at least one of A, B, C, D, E and F has at least one pendent functional group; optionally, at least one ethylenically unsaturated monomer; and a photoinitiator; (2) applying the photopolymerizable composition to a substrate; (3） imagewise exposing the photopolymerizable composition to actinic radiation to form a polymerized composition;  \n\nand (4) developing the imagewise exposed photopolymerized composition to form an image on the substrate.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# DETAILEDDESCRIPTIONOFTHE INVENTION  \n\n[0021] Surprisingly, the present invention provides for a photopolymerizable composition having improved fine line adhesion with faster stripping, and faster strip time with smaller strip mode. Such improvements do not typically occur together in photopolymerizable compositions.  \n\n[0022] Another advantage of the present invention is the elimination or at least reduction in the amount of ethylenically unsaturated monomers that are used in the photopolymerizable composition as cross-linking agents. Photopolymerization processes do not reach $100\\%$ conversion. Accordingly, there is free monomer in the cured state of the composition. Such monomers may migrate through cover sheets on which a photopolymerizable composition is laminated. The monomer may then act as a lubricant causing roll slippage and distortion in a dry film. Additionally, workers may be exposed to the monomers that have migrated through the cover sheets presenting a toxic hazard. Such migration of monomers may also contaminate artwork employed in lithography. Monomers also may leach into various processing solutions such as developer and stripping solutions during the manufacture of printed wiring boards and adversely affect the performance of the solutions and the quality of the boards. They also may plasticize dry film photopolymerizable compositions resulting in edge fusion in a dry film roll.Accordingly, the present invention eliminates or at least reduces the foregoing problems encountered with monomers.  \n\n[0023] Also, compositions that have reduced monomer content are easier to waste treat. Conventional waste treatment schemes involve a process in which the $\\mathrm{pH}$ of the waste treatment stream is lowered by the addition of acid. This causes pH sensitive materials such as polymer binders to precipitate out of solution.The resultant solution becomes clear and free of waste. Monomers typically are not as $\\mathrm{\\pH}$ sensitive as polymer binders and as a result are more difficult to treat than polymers. Further, elimination or reduction of monomers eliminates or at least reduces scum and residue formation. Accordingly, the present invention provides for a more environmentally friendly composition.  \n\n[0024] A primary objective of the present invention is to provide an improved functionalized polymer.  \n\n[0025] Another objective of the present invention is to provide a functionalized polymer that can act as the sole cross-linking component in a photopolymerizable composition.  \n\n[0026]   An additional objective of the present invention is to provide for a water-soluble or water-emulsifiable binder polymer for photopolymerizable compositions.  \n\n[0027] A further objective of the present invention is to provide for a photoresist composition having improved fine line adhesion with faster stripping, and faster stripping with smaller strip mode.  \n\n[0028] Other objectives and advantages of the invention may be ascertained by a person of skill in the art upon reading the description of the invention and the appended claims.  \n\n[0029] A“moiety\" within the scope of the present invention means a distinct structural component of a functionlized polymer and is synonymous with the term “group\". The term “polymer\" means both polymer and copolymer.“Pendent\" means a structural component of the functionalized polymer that is joined to or suspended from the main chain or backbone of the functionalized polymer by a chemical bond. “(Meth)acrylate” means both acrylate and methacrylate and (meth)acrylic means both acrylic and methacrylic.“Monomer\" means any ethylenically or acetylenically unsaturated compound that may be polymerized.  \n\n[0030] The present invention is directed to a compound having a backbone with pendent functional groups, a photopolymerizable composition including the compound having a backbone and functional pendent groups, and a method of producing an image on a substrate using the photopolymerizable composition. Surprisingly, the photopolymerizable composition has improved resolution with improved fine line adhesion, fine line adhesion with faster stripping and faster stripping with a smaller strip mode. Typically a photopolymerizable composition with good resolution has decreased fine line adhesion,and with good fine line adhesion the rate of stripping is compromised. Also, when stripping is improved the strip mode typically increases. The foregoing problems are addressed by a compound having a formula:  \n\n$$\n(\\mathbf{A})_{\\mathbf{u}}(\\mathbf{B})_{\\mathbf{v}}(\\mathbf{C})_{\\mathbf{w}}(\\mathbf{D})_{\\mathbf{x}}(\\mathbf{E})_{\\mathbf{y}}(\\mathbf{F})_{\\mathbf{z}}\n$$  \n\n[0031]   where Ais derived from one or more hydroxyalkyl (meth)acrylate, B is derived from one or more hydroxy polyalkylene oxide (meth)acrylate, C is derived from one or more alkyl(meth)acrylate, D is derived from one or more (meth)acrylic acid,E is derived from one or more vinyl aromatic monomer, nitrogen containing compounds or thioanalogs of nitrogen containing compounds, silicon containing monomer, substituted ethylene monomer, or cyclic olefin monomer, and F is derived from one or more hydroxy poly opened-ring lactone polyalkylene oxide (meth)acrylate, to compose the backbone of the compound or polymer, where u, v, w, x, y and $\\mathbf{z}$ are weight percentages of monomers in the backbone, u is 0 to $30\\%$ ,vis 0 to $30\\%$ ,wis 5 to $70\\%$ ,xis 5 to $40\\%$ ,y is O to $20\\%$ and $\\mathbf{z}$ is O to $30\\%$ with the proviso that at least one or u, v or $\\textbf{z}$ is greater than O, and at least one of A, B, C, D, E and F has at least one pendent functional group. The sum of u, V, W, x, y and $\\mathbf{z}$ for a given polymer is $100\\%$ by weight.  \n\n[0032] The polymers of the present invention are $15\\%$ to $70\\%$ (mole $\\%$ ）hydroxyl capped.Hydroxyl capped, within the scope of the present invention, refers to the mole percent of free or unreacted hydroxyl groups or moieties on the polymer backbone. Mole percent of a polymer is determined by infrared analysis or determined by the amount of each starting material. Such methods are well known in the art. Hydroxyl capping provides for a polymer that may react with another compound to form a functional polymer as discussed below. Hydroxyl capping also provides for a water-soluble or water-emulsifiable compound.  \n\n[0033] Hydroxyalkyl (meth)acrylate monomers that may be employed to prepare the polymer include, but are not limited to, hydroxyalkyl (meth)acrylates with one or more hydroxyl groups in the alkyl radical, especially those where the hydroxyl group is found at the $\\upbeta$ -position (2-position) in the alkyl radical. Hydroxyalkyl (meth)acrylate monomers in which the substituted alkyl group is a $\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{6}$ alkyl, branched or unbranched, are preferred. Suitable hydroxyalkyl (meth)acrylate monomers include, but are not limited to, 2-hydroxyethyl methacrylate (\"HEMA\"), 2-hydroxyethyl acrylate (\"HEA\"), 2-hydroxypropyl methacrylate, 1-methyl-2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 1-methyl-2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate or mixtures thereof. Preferred hydroxyalkyl (meth)acrylate monomers are HEMA, 1-methyl-2-hydroxyethyl methacrylate,2-hydroxypropyl methacrylate and mixtures thereof.A mixture of the latter two monomers is commonly referred to as “hydroxypropyl methacrylate” or “HPMA\".  \n\n[0034]  Suitable hydroxy polyalkylene oxide (meth)acrylates and hydroxy poly opened-ring lactone polyalkylene oxide (meth)acrylates may be prepared from poly(propylene glycol) (meth)acrylates, poly(propylene glycol) alkyl ether (meth)acrylates, poly (propylene glycol) phenyl ether (meth)acrylates, poly(propylene glycol) 4-nonylphenol ether (meth)acrylates, poy(ethylene glycol) (meth)acrylates, poly(propylene/ethylene glycol) (meth)acrylates, poly(ethylene glycol)alkyl ether (meth)acrylates, poly(ethylene glycol) phenyl ether (meth)acrylates, poly(propylene/ethylene glycol) alkylether (meth)acrylates and mixtures thereof. The poly(alkylene oxide) may have from 1 to 50 degrees of polymerization.Examples of such compounds are disclosed in formula (V) below. Such compounds may also be joined to the polymer backbone as a pendent functional group via an isocyanate group as described below.  \n\n[0035] Alkyl (meth)acrylates useful in the present invention may be a single monomer or a mixture having different numbers of carbon atoms in the alkyl portion. Examples of alkyl (meth)acrylates useful in the present invention are $(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{24})$ Dalkyl (meth)acrylates. Suitable alkyl (meth)acrylates include, but are not limited to, “low cut” alkyl (meth)acrylates,“mid cut\" alkyl (meth)acrylates and “high cut” alkyl (meth)acrylates.  \n\n[0036]“Low cut” alkyl (meth)acrylates are those where the alkyl group contains from 1 to 6 carbon atoms. Suitable low cut alkyl (meth)acrylates include, but are not limited to: methyl methacrylate, methyl acrylate, ethyl acrylate, propyl methacrylate, butyl methacrylate, butyl acrylate, isobutyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, cyclohexyl acrylate and mixtures thereof. Such low cut alkyl (meth)acrylates are preferred, especially those with 3 to 5 carbon atoms in the alkyl group.A most preferred low cut alkyl(meth)acrylate is n-butyl acrylate. Surprisingly, such alkyl (meth)acrylates, provide for a composition that has faster development time without a change in strip time, and helps to reduce scum and residue build-up in developer solutions.  \n\n[0037]“Mid cut\" alkyl (meth)acrylates are those where the alkyl group contains from 7 to 15 carbon atoms. Suitable mid cut alkyl (meth)acrylates include, but are not limited to: 2-ethylhexyl acrylate (\"EHA\"), 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, isodecyl methacrylate (based on branched $\\mathrm{(C_{10})}$ alkyl isomer mixture), undecyl methacrylate, dodecyl methacrylate (also known as lauryl methacrylate), tridecyl methacrylate, tetradecyl methacrylate (also known as myristyl methacrylate), pentadecyl methacrylate and mixtures thereof. Particularly useful mixtures include dodecyl-pentadecyl methacrylate, a mixture of linear and branched isomers of dodecyl, tridecyl, tetradecyl and pentadecyl methacrylates; and lauryl-myristyl methacrylate.  \n\n[0038]“High cut\" alkyl (meth)acrylates are those where the alkyl group contains from 16 to 24 carbon atoms. Suitable high cut alkyl (meth)acrylates include, but are not limited to: hexadecyl methacrylate, heptadecyl methacrylate, octadecyl methacrylate, nonadecyl methacrylate, cosyl methacrylate, eicosyl methacrylate and mixtures thereof. Particularly useful mixtures of high cut alkyl (meth)acrylates include, but are not limited to: cetyl-eicosyl methacrylate,which is a mixture of hexadecyl, octadecyl, cosyl and eicosyl methacryl ate; and cetyl-stearyl methacryl ate, which is a mixture of hexadecyl and octadecyl methacrylate.  \n\n[0039] The mid-cut and high-cut alkyl (meth)acrylate monomers described above may be prepared by standard esterification procedures using technical grades of long chain aliphatic alcohols, and these commercially available alcohols are mixtures of alcohols of varying chain lengths containing between 10 and 15 or 16 and 20 carbon atoms in the alkyl group. Examples of these alcohols are the various Ziegler catalyzed ALFOL alcohols from Vista Chemical company,i.e.,ALFOL 1618 and ALFOL 1620,Ziegler catalyzed various NEODOL alcohols from Shell Chemical Company, i.e.NEODOL 25L, and naturally derived alcohols such as Proctor & Gamble's TA-1618 and CO-1270. Consequently, for the purposes of this invention, alkyl (meth)acrylate is intended to include not only the individual alkyl (meth)acrylate product named, but also to include mixtures of the alkyl (meth)acrylates with a predominant amount of the particular alkyl (meth)acrylate named.  \n\n[0040]  Suitable nitrogen-containing monomers are (meth)acrylamides. (Meth)acrylamides of the present invention may optionally be substituted. Suitable optionally substituted (meth)acrylamide monomers include, but are not limited to, dialkylamino $(\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{20,\\dag})$ )alkyl (meth)arylates, dialkaylamino $(\\mathrm{C}_{2}{\\cdot}\\mathrm{C}_{20})\\mathrm{alkyl}$ (meth)acrylamides, preferably, dialkylamino $\\mathrm{(C}_{2}\\mathrm{-}\\mathrm{C}_{6})$ Dalkyl(meth)acrylates,dialkylamino( $\\mathrm{\\tilde{C}}_{2}–\\mathrm{C}_{6})$ alkyl (meth)acrylamides.  \n\n[0041]  Other suitable nitrogen-containing monomers useful to prepare the polymer are those with an amino group or alkylamino group. Examples include, but are not limited to: methylaminoethyl methacrylate, methylaminoethyl acrylate, N-methylaminoethyl methacrylamide, N-methyl-aminopropyl methacrylamide, N-methylaminobutyl methacrylamide, N-ethylaminoethyl methacrylamide, N-ethylaminopropyl methacrylamide, N-ethylaminobutyl methacrylamide, N-(1, 1-dimethyl-3-oxobutyl) acrylamide, N-(1,3-diphenyl-1- ethyl-3-oxobutyl) acrylamide, N-(1-methyl-1-phenyl-3-oxobutyl) methacrylamide， and 2-hydroxyethyl acrylamide, N-methacrylamide of aminoethyl ethylene urea, N-maleimide of dimethylaminopropylamine and mixtures thereof.  \n\n[0042] Additional nitrogen-containing compounds and their thio-analogs useful as unsaturated monomers to prepare the polymer include, but are not limited to: vinylpyridines such as 2-vinylpyridine_or 4-vinylpyridine; $(\\mathrm{C_{1}}\\overline{{\\cdot}}$ ${\\bf C}_{8,}^{\\mathrm{~\\tiny~{~\\cdot~}~}}$ alkyl substituted N-vinyl pyridines such as 2-methyl-5- vinyl-pyridine， 2-ethyl-5-vinylpyridine，3-methyl-5- vinylpyridine, 2,3-dimethyl-5-vinyl-pyridine, and 2-methyl  \n\n3-ethyl-5-vinylpyridine; methyl-substituted quinolines and isoquinolines; N-vinylcaprolactam; N-vinylbutyrolactam; N-vinylpyrrolidone; vinyl imidazole; N-vinyl carbazole; N-vinyl-succinimide; (meth)acrylonitrile; o-, m-, orp-aminostyrene; hydroxystylene; maleimide; N-vinyl-oxazolidone; N,N-dimethyl aminoethyl-vinyl-ether; ethyl-2-cyano acrylate; vinyl acetonitrile; N-vinylphthalimide; N-vinylpyrrolidones such as N-vinyl-thio-pyrrolidone, 3-methyl-1- vinyl-pyrrolidone, 4-methyl-1-vinyl-pyrrolidone, 5-methyl1-vinyl-pyrrolidone, 3-ethyl-1-vinyl-pyrrolidone, 3-butyl-1- vinyl-pyrrolidone, 3,3-dimethyl-1-vinyl-pyrrolidone, 4,5- dimethyl-1-vinyl-pyrrolidone, 5,5-dimethyl-1-vinylpyrrolidone, 3,3,5-trimethyl-1-vinyl-pyrrolidone, 4-ethyl-1- vinyl-pyrrolidone， 5-methyl-5-ethyl-1-vinyl-pyrrolidone and 3,4,5-trimethyl-1-vinyl-pyrrolidone; vinyl pyrroles; vinyl anilines; and vinyl piperidines.  \n\n[0043]   Other monomers useful in the present invention are silicon-containing monomers such as $\\upgamma$ -propyl $\\mathrm{tri}(\\mathrm{C}_{1}-$ $\\mathrm{C}_{6,}$ Dalkoxysilyl (meth)acrylate, $\\upgamma$ -propyl $\\mathrm{tri}(\\mathrm{C}_{1}{-}\\mathrm{C}_{6})$ alkylsilyl (meth)acrylate, $\\upgamma$ -propyl $\\mathrm{{di}(C_{1}{-}C_{6})a l l k o x y(C_{1}{-}C_{6}){s}}$ lkylsilyl (meth)acrylate, $\\upgamma$ -propyl $\\mathrm{{di}(C_{1}{-}C_{6})a l k y l(C_{1}{-}C_{6})}.$ alkoxysilyl (meth)acrylate, vinyl $\\mathrm{tri}(\\mathrm{C}_{1}{-}\\mathrm{C}_{6})$ alkoxysilyl (meth)acrylate, vinyl $\\mathrm{{di}(C_{1}{-}C_{6})a l l k o x y(C_{1}{-}C_{6}){:}}$ alkylsilyl (meth)acrylate, vinyl $\\displaystyle\\left(\\mathrm{C}_{1}–\\mathrm{C}_{6}\\right)$ alkoxydi $\\mathrm{(C_{1}-C_{6})}$ alkylsilyl(meth)acrylate, vinyl $\\mathrm{tri}(\\mathrm{C}_{1}{-}\\mathrm{C}_{6})$ alkylsilyl (meth)acrylate, 2-propylsilsesquioxane (meth)acrylate and mixtures thereof.  \n\n[0044] The vinyl aromatic monomers useful as unsaturated monomers in the present invention include, but are not limited to: styrene, hydroxystyrene, $\\mathbf{\\alpha}\\propto$ -methylstyrene, vinyltoluene, p-methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinylxylenes, and mixtures thereof. The vinylaromatic monomers also include their corresponding substituted counterparts, such as halogenated derivatives, i.e., containing one or more halogen groups, such as fluorine, chlorine or bromine; and nitro, and cyano.  \n\n[0045] The substituted ethylene monomers useful as unsaturated monomers in the present invention include, but are not limited to: vinyl alcohols, vinyl acetate,vinyl formamide， vinyl chloride, vinyl fluoride, vinyl bromide, vinylidene chloride,vinylidene fluoride，vinylidene bromide,tetrafluoroethylene,trifluoroethylene,trifluoromethyl vinyl acetate, vinyl ethers and itaconic anhydride.  \n\n[0046] Suitable cyclic olefin monomers useful in the present invention are $(\\mathrm{C}_{5}–\\mathrm{C}_{10})$ cyclic olefins, such as cyclopentene, cyclopentadiene, dicylopentene, cyclohexene, cyclohexadiene, cycloheptene, cycloheptadiene, cyclooctene,cyclooctadiene,norbornene,maleic anhydride and the like. Such cyclic olefins also include spirocyclic olefin monomers such as spirocyclic norbornenyl monomers,spirocyclic cyclohexene monomers, spirocyclic cyclopentene monomers and mixtures thereof. Suitable substituted cyclic olefin monomers include, but are not limited to, cyclic olefins having one or more substituent groups selected fromhydroxy, aryloxy,halo, $(\\mathrm{C_{1}-C_{12}})\\mathrm{alkyl}$ ， $(\\mathrm{C}_{1}\\mathrm{-}$ ${\\bf C}_{12})$ haloalkyl, $\\displaystyle{(C_{1}-C_{12})}$ hydroxyalkyl, or 一 $\\mathrm{(C_{1}-}$ $\\mathbf{C}_{12}\\mathbf{\\Psi},$ halohydroxyalkyl. Particularly suitable substituted cyclic olefins include maleic anhydride and cyclic olefins containing one or more of hydroxy, aryloxy, $({\\mathrm{C_{1}}}{\\mathrm{-}}{\\mathrm{C_{12}}}){\\mathrm{alkyl}}$ D $(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{12})$ haloalkyl, $\\displaystyle{(C_{1}-C_{12})}$ hydroxyalkyl, $(\\mathrm{C_{1}}^{-}$ ${\\bf C}_{12}\\rangle$ halohydroxyalkyl, carbo $\\mathrm{C}_{1}–\\mathrm{C}_{20},$ alkoxy, and carbo $\\mathrm{(C_{1}\\mathrm{\\cdot}}$ 1 $\\mathrm{C}_{20,}$ haloalkoxy.  \n\n[0047] The molecular weight of the polymer backbone may range from 1,000 to 30,000 daltons. The polymer backbone may be made by any suitable method in the art such as free-radical polymerization. For example,monomers chosen from the list above are dissolved in an appropriate solvent and heated in a reaction vessel in the presence of a thermal free radical initiator to initiate polymerization. Examples of suitable initiators include, but are not limited to,peroxide compounds, such as dibenzoyl peroxide, and azo compounds, such as 2,2'-azobis(2-methylpropanenitrile)， 2,2'-azobis(2-methylbutanenitrile)， $^{2,2^{\\prime}}$ -azobis(2,4- dimethylethylpentanenitrile), and 1,1'-azobis(cyclohexanecarbonitrile).  \n\n[0048]  Functional polymers  within the  scope of the present invention may be prepared by a post polymerization functionalization process. In post polymerization functionalization, the main chain or backbone and the functional pendent components are prepared separately. After the preparation of each of the separate components that make up the polymer are prepared, they are then joined together in a separate reaction process to form the final functionalized polymer product.  \n\n[0049]  After the polymer is prepared, the free hydroxyl groups or aminyl groups on the polymer are bonded with a compound that has at least one $\\mathbf{\\alpha}_{\\mathrm{{{d},\\beta}}}$ -ethylenically or acetylenically unsaturated group or another reactive group to form a functional group pendent from the polymer backbone. Reactions of the hydroxyl group may involve the breaking of the $\\mathrm{O-}\\mathrm{H}$ bond with removal of hydrogen in which a group replaces the hydrogen. Aminyl groups on the polymer backbone may be joined to compounds with functional groups by known amine reactions such as conversion into amides. Any compound that may react with the hydroxyl or aminyl group of the polymer and has at least one unsaturated group or another reactive group may be employed. The unsaturated group enables the polymer to cross-link with another polymer when exposed to actinic radiation. Additional reactive groups of the pendent functional group which do not react with the hydroxyl or aminyl groups from the polymer backbone may react with other compounds to extend and modify the functional pendent groups. The functional pendent groups permit the reduction or elimination of cross-linking agents in photopolymerizable compositions.  \n\n[0050]   An example of a reactive group that may react with a hydroxyl or aminyl group of the polymer backbone is the isocyanate group (i.e.— $\\scriptstyle\\mathbf{N}=\\mathbf{C}=\\mathbf{O}$ ). The polymer backbone may be mixed with an isocyanate compound at reaction temperatures below $80^{\\circ}\\mathrm{C}$ Preferably, reaction temperatures are run at mild temperatures of from $20^{\\circ}\\mathrm{C}$ . to $60^{\\circ}\\bar{\\mathrm{~C~}}$ Mixing and heating are continued until the reaction is complete. Typically, the reaction continues for 1 hour to less than 8 hours, preferably from 4 to 6 hours. Advantageously, the method of the present invention is performed over short time periods, thus less energy is utilized in preparing the functionalized polymer than conventional methods. Reactions that take place occur between a free isocyanate group on the isocyanate compound and a hydroxyl group, carboxyl group, or primary or secondary aminyl functional group attached to the polymer main chain or backbone.One mole of free isocyanate react with one mole of a hydroxyl, carboxyl, or primary or secondary aminyl on the polymer main chain. The reaction may be self-quenching. There is believed to be no source of free radicals, or a source of cations or anions at the end of the reaction between the isocyanate group(s)  \n\nand hydroxyl, carboxyl, or aminyl group(s) on the polymer backbone. As a precaution water, alcohol, or other chemical species with labile hydrogen, and a suitable catalyst, such as triethylamine,may be added at the end of the reaction to quench any free isocyanate.Also,a suitable polymerization inhibitor may optionally be added to prevent premature cross-linking of terminal ethylenically or acetylenically unsaturated moieties such as a (meth)acrylate moiety.Reaction completion may be determined by using standard analytical instruments well known in the art.  \n\n[0051] The methods according to the present invention may be carried out in the presence of an inert dry solvent, for example, an ether such as diisopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran or 1,2-dimethoxy propane; an ester such as butyrolactone, ethylene glycol carbonate or propylene glycol carbonate; an ether ester such as methoxyethyl acetate, ethoxyethyl acetate, 1-methoxypropyl-2-acetate, 2-methoxypropyl-1-acetate,1-ethoxypropyl-2-acetate or 2-ethoxypropyl-1-acetate; ketones such as acetone or methyethyl ketone; nitriles such as acetonitirle, propionitrile or methoxypropionitrile; sulfones such as sulfolan, dimethylsulfone or diethylsulfone; and phosphoric acid esters such as trimethyl phosphate or triethyl phosphate. The processes may also be carried out without such solvents.  \n\n[0052] To accelerate the reactions of the methods of the present invention, any suitable catalyst employed in polymerization reactions can be used. Tin containing catalysts are preferred, such as dibutylin dilaurate, tin(II) octoate or dibutylin dimethoxide. Such catalysts are employed in an amount of from $0.001\\%$ to $2.5\\%$ by weight, preferably from $0.005\\%$ to $1.5\\%$ by weight based on the amount of reactants.  \n\n[0053]  Stabilizers  or  polymerization  inhibitors may optionally be added to the reaction steps to stabilize freeradical polymerization.Polymerization inhibitors are added to reaction mixtures in amounts of from $0.001\\%$ to $2\\%$ by weight, in particular from $0.005\\%$ to $1.0\\%$ by weight of the reactants.Examples of such inhibitors include, but are not limited to, hydroquinones, or hydroquinone monoalkyl ethers, 2,6-di-tert-butylphenols, such as 2,6-di-tert-butylcresol, nitrosamines, phenothiazines or phosphorous esters.  \n\n[0054]Free isocyanate (i.e.— $\\scriptstyle\\cdot\\Nu=\\Nu=\\O$ ）reacts witha hydroxyl group from the polymer backbone, or a hydroxyl group from a carboxyl group from the polymer backbone to form a R—NH—C(O)—P linkage where $\\mathrm{~\\bf~P~}$ is the polymer backbone, and R is an organic variable pendent group from the isocyanate group. Specific examples include a urethane group containing compound such as a biuret group containing compound.A free isocyanate that reacts with a primary or secondary amine moiety joined to the polymer backbone forms a R—NH—C(O)—NR-G-P urea (carbamide) linkage where ${\\bf R}^{1}$ includes, but is not limited to, hydrogen a linear, branched or unsubstituted or substituted alkyl, or an unsubstituted or substituted aryl. Substituent groups include, but are not limited to, halogen, such as fluorine, bromine, chloride or iodine,hydroxyl,carboxyl, or aminyl. A substituent group replaces a hydrogen on a carbon atom. G is an organic moiety that joins the nitrogen to the polymer chain. G includes, but is not limited to, an alkyl, or a substituted aryl where the nitrogen is joined to the aryl by an alkyl chain. The alkyl of G may be linear or branched $\\mathrm{(C_{1}-C_{24})}$ alkyl. A free isocyanate that reacts with a polyalkoxylated moiety from the polymer backbone forms a R—NH— $\\mathrm{C(O){\\overline{{-}}O(A O)_{m}}{\\overline{{-}}C(O){-}P}}$ linkage where A is a linear or branched $(\\mathrm{C}_{1}\\mathrm{-}\\mathrm{C}_{24})$ alkyl, and m is an integer from O to 1,000, preferably from 1 to 200. R may terminate in one or more functional groups such as ethylenically or acetylenically unsaturated moieties that permit functionalized polymers of the present invention to self cross-link as in photoresist compositions described below.  \n\n[0055] In one embodiment of the present invention, isocyanate compounds used to prepare the functionalized polymers of the present invention include urethane/ethylenically or acetylenically unsaturated isocyanates. Such compounds have a —NHC(O)— moiety, at least one free isocyanate group, and an ethylenically or acetylenically unsaturated moiety such as a (meth) acrylate that is at a terminsus of the isocyanate compound.Biuret ethylenically or acetylenically unsaturated isocyanates have a —NH—C(O)—N—C(O)- NH— moiety, at least one free isocyanate group and an ethylenically or acetylenically unsaturated moiety at a terminus of the compound. Examples of such compounds include, but are not limited to, the following general formulas:  \n\n![](images/01bd5d4ef4b754b9615aa90a3c5800244b09f10738b876a2683f4291ee964cef.jpg)  \n\n[0056] where $z$ includes, but is not limited to, alkyl, alkylene,cycloalkyl, aryl, heterocyclic alkyl, heteroaryl, a polymer such as a copolymer including a branched polymer or branched copolymer; Y includes, but is not limited to, alky, alkylene, cycloalkyl, aryl, heterocyclic alkyl, heteroaryl，- $-(\\mathrm{(CH_{2})_{n}{\\longrightarrow}}\\mathrm{-}\\mathrm{\\O{\\longrightarrow}})_{\\mathrm{o}}{\\longrightarrow}(\\mathrm{CH_{2}})_{\\mathrm{p}}{\\longrightarrow},$ or $\\mathrm{((CH_{2})_{n}-}$ $\\mathrm{C(O){-}O{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}O\\mathrm{-}$ where n,andp are integers of from 1 to 10, and o is an integer of from O to greater than 1,000, preferably from 1 to 200, most preferably from 5 to $10.\\mathrm{R}^{2}$ is hydrogen or or $\\mathrm{(C_{1}\\mathrm{-}C_{4})}$ alkyl. Preferably ${\\mathrm{R}}^{2}$ is hydrogen or methyl. Hetero-atoms include, but are not limited to, oxygen, sulfur, and nitrogen. The alkyl, alkylene, cycloalkyl, aryl, heterocyclic alkyl, heteroaryl and polymers may be unsubstituted or substituted.  \n\n[0057]  Examples of suitable substitutent groups include, but are not limited to, carboxyl, hydroxyl, $\\mathrm{(C_{1}\\mathrm{-}C_{4})}$ alkyl, aminyl such as a primary or secondary aminyl, or hydroxyaminyl, or —CN.  \n\n[0058] Examples of suitable alkyl groups include, but are not limited to, linear or branched $\\left(\\mathrm{C}_{1}–\\mathrm{C}_{20}\\right)$ alkyl. Examples of alkenyl, cycloakyl or aryl groups include, but are not limited to, linear or branched $(\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{20})$ alkenyl, $(\\mathrm{C}_{5}–\\mathrm{C}_{6})$ cycloalky such as an isophorone, and $(C_{5}–C_{6})$ aryl such as phenyl.  \n\n[0059] Functional groups that are to be joined to the polymer backbone and have free reactive groups, such as isocyanate groups, may be reacted with compounds having $\\mathbf{\\alpha}_{\\mathbf{{\\alpha}}_{\\mathbf{{\\beta}}}}$ -ethylenically or acetylenically unsaturated groups to extend the functional pendent groups. Such compounds with unsaturated groups include but are not limited to a compound having a formula:  \n\n$$\n\\mathrm{CH}_{2}\\mathrm{=CHR^{3}-C(O)-O-(A_{1})-(B_{1})-(C_{1})-H}\n$$  \n\n[0060] where ${\\mathbb R}^{3}$ is hydrogen or methyl, $(\\mathbf{A}_{1})$ ， $\\mathrm{(B_{1})}$ and $\\mathrm{(C_{1})}$ are in any order, $(\\mathbf{A}_{1})$ is a chain formed of from 1 to 40 alkoxylate monomers, aromatic-substituted alkoxylate monomers having from 1 to 20 carbon atoms, or mixtures thereof, $\\mathbf{\\left(B_{1}\\right)}$ is either absent or is a chain formed of from 1 to 40 alkoxylate monomers, or aromatic-substituted alkoxylate monomers having from 1 to 20 carbon atoms, or mixtures thereof, and the monomer composition of $\\mathbf{\\left(B_{1}\\right)}$ being different than the monomer composition of $(\\mathbf{A}_{1})$ ，and $\\mathrm{(C_{1})}$ is a chain formed of from 1 to 40 open-ring lactone monomers having from 2 to 21 carbon atoms.  \n\n[0061] Isocyanate compounds with at least one free isocyanate group may be prepared by any suitable method known in the art. Monoisocyanates, diisocyanates, triisocyanates,or polyisocyanates (four or more free isocyanate groups) that may be employed are either known or may be prepared by analogy to known compounds. Examples of suitable diisocyanates and triisocyanates include, but are not limited to,ethylene diisocyanate, propylene diisocyanate, butylene-1,3-diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, 2,4-dimethyl6-ethyloctamethylene diisocyanate,cyclohexylene diisocyanate, cyclopentylene diisocyanate, 1,4-diisocyanatomethyl-cyclohexane, 1,3-diisocyanatoethyl-cyclohexane, toluylene diisocyanate, 3,3,5-trimethyl-1-isocyanato-5-isocyanatomethyl-cyclohexane， 2-butene-1,4-diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate biuret, 1,6-hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, bis phenol A dimethacrylate capped with 2-hydroxethylmethacrylate capped with 1,6-hexamethylene diisocyanate trimer, and the like. Many of the foregoing listed diisocyantes and triisocyantes as well as the biurets and trimers may be purchased from Lyondell (located at 122 Melanney St., Houston, Tex.) or Bayer (located at 100 Bayer Rd., Pittsburg, Pa. 15025).  \n\n[0062] Isocyanates described above may then be reacted with a sufficient amount of one or more hydroxyl containing compounds, such as compounds of formula (V) above, such that one free isocyanate group is left to react with the main chain prepared as described above.As mentioned above, the reaction mole ratio of hydroxyl group to isocyanate group is 1:1.Any suitable compound with at least one free hydroxyl group to react with an isocyanate group may be employed. An isocyanate compound of the present invention also may be reacted with another isocyanate compound having at least one free hydroxyl group. Hydroxyalkyl, hydroxyalkenyl, hydroxyaryl compounds and the like are examples of such compounds that may be employed. Hydroxyalkyl (meth)acrylates are one example of suitable compounds. Hydroxyethyl (meth)acrylate or hydroxypropyl (meth)acrylate (n or iso compounds) are examples of hydroxyl groupcontaining esters that are suitable. Other suitable hydroxyalkyl (meth)acrylates include, but are not limited to, 2-hydroxy-butyl (meth)acrylate, 4-hydroxy-butyl (meth)acrylate, 2-hydroxy-cyclohexyl (meth)acrylate, 2-hydroxyethylmethacrylate, and the like.Suitable polyethylene glycol mono (meth)acrylates also may be employed such as, but not limited to, diethylene glycol mono (meth)acrylate, triethylene glycol mono (meth)acrylate and the like. Hydroxyalicyclic (meth)acrylates, and hydroxyaromatic (meth)acrylates such as bis phenol A dimethacrylate also may be employed. U.S. Pat.No. 4,019,972 discloses a method of preparing urethanes that may be employed to practice the present invention.  \n\n[0063] The functionalized polymers have  an  average molecular weight range of from about 5,ooo daltons to over 50,000 daltons. The functionalized polymers of the present invention may be functionalized with one or more pendent functional moiety in ranges of from 1.O to as high as 100 mole percent of reactive sites on the polymer backbone, preferably from 25 to 65 mole percent, most preferably from 35 to 55 mole percent. Complete functionalization of the polymer backbone is not always desirable because such groups as hydroxyl and carboxyl groups provide for solubility in aqueous alkaline solutions. Such solubility or hydrophilic character is highly desirable when the functionalized polymer is employed in photoresist. Acid values of the functionalized polymers range from at least $25~\\mathrm{mg}$ of potassium hydroxide/gram of polymer, preferably from at least $90\\mathrm{mg}$ , more preferably from at least $120\\mathrm{mg}$ ，and most preferably up to $300~\\mathrm{mg}$ . Typical acid number ranges are from $50~\\mathrm{mg}$ to $250~\\mathrm{mg}$  \n\n[0064] The functionalized polymers of the present invention may be employed in both primary imaging photoresists or in secondary imaging photoresists such as in solder masks. The functionalized polymers may act as both the binder polymer for the photoresist as well as the sole cross-linking agent in the photoresist composition. However, cross-linking monomers or oligomers may optionally be added to the photoresist composition. Functionalized polymers of the present invention compose from $30\\%$ by weight to $95\\%$ by weight of the photoresist composition. Preferably the functionalized polymers comprise from $55\\%$ by weight to $95\\%$ by weight, most preferably from $75\\%$ by weight to $95\\%$ by weight of the photoresist composition. The balance of the photoresist composition may include conventional additives as described below.  \n\n[0065]  Optional  cross-linking  agents  that  may  be employed include a monomer, or a short chain oligomer having ethylenic unsaturation, particularly, $\\mathbf{\\alpha}_{\\mathrm{~\\alpha~}}\\mathbf{\\beta}_{\\mathrm{~\\alpha~}}$ -ethylenic unsaturation functionality of 2 or greater. A mixture of monofunctional and multi-functional monomers may be used. Examples of monomers suitable for photoinitiated polymerizatioin include, but are not limited to, (meth)acrylic acid,maleic acid, fumaric acid, citraconic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-hydroxyethyl acrylol phosphate, 2-hydroxypropyl acrylol phosphate, 2-ethyl hexyl acrylate,n-butyl acrylate,n-hexyl acrylate,methyl (meth)acrylate, hydroxy ethyl acrylate, butyl (meth)acrylate, octyl acrylate, 2-ethoxy ethyl (meth)acrylate, t-butyl acrylate,1,5-pentanediol di(meth)acrylate, N,N-diethylaminoethyl acrylate, ethylene glycol diacrylate, 1,3-propanediol di(meth)acrylate, decamethylene glycol di(meth)acrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylol propane diacrylate, glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, 2,2-di(p-hydroxyphenyl)-propane dimethacrylate, triethylene glycol diacrylate, polyoxyethyl2-2-di(p-hydroxyphenyl)-propane dimethacrylate, triethylene glycol dimethacrylate, polyoxypropyltrimethylol propane triacrylate,ethylene glycol dimethacrylate, butylene glycol dimethacrylate, butylene glycol dimethacryalte, 1,2, 4-butanetriol trimethacrytlate, 2,2,4-triemthyl-1,3-pentanediol dimethacrylate, pentaerythritol trimethacrylate, 1-phenyl ethylene-1,2-dimethacrylate, pentaerythritol tetramethylacrylate, trimethylol propane trimethacrylate, 1,4- benzenediol dimethacryl ate; styrene and alkyl- and aromatic-substituted styrene, such as 2-methyl styrene and vinyl toluene and vinyl esters, such as vinyl (meth)acrylate. Also useful are (meth)acrylate terminated urethane oligomers prepared from hydroxy functional mono(meth)acrylates such as those described in U.S. Pat.No.5,744,282.The optional monomers or oligomers are included in the photoresists of the present invention in reduced amounts from conventional photoresists. Cross-linking monomers may be included in amounts from $5\\%$ to $20\\%$ by weight of the composition.Preferably such monomers are left out of the photopolymerizable compositions.  \n\n[0066]  To initiate cross-linking of the functionalized polymers of the present invention or the optional monomers or oligomers upon exposure to actinic radiation, the photoimageable compositions of the present invention contain a photoinitiator chemical system. The photoinitiator chemical system may contain from between $0.1\\%$ to $15\\%$ by weight of the photoresist composition. Suitable photoinitiators include, but are not limited to 9-phenylacridine, n-phenylglycine， aromaticketones (E.g, benzophenone, N,N\"tetramethyl-4,4'-diaminobenzophenone， N,N'-tetraethyl-4,4'-diaminobenzophenon, 4-methoxy- $\\cdot4^{\\prime}$ dimethylaminobenzophenone, 3,3'-dimethyl-4-methoxybenzophenone， p,p'-bis(dimethylamino) benzophenone, $\\mathsf{p}\\mathsf{,p^{\\prime}}$ ， bis(diethylamino)-benzophenone,anthraquinone, 2-ethylanthraquinone, naphthaquinone, phenanthraquinone, benzoins (e.g., benzoin, benzoinmethylether, benzoinethylether, benzoinisopropylether, benzoin-n-butylether, benzoinphenylether， methylbenzoin, ethylbenzoin， and the like), benzyl derivatives (e.g., dibenzyl, benzyldiphenyldisulfide, benzyldimetehylketal (SIC), and the like), acridine derivatives (9-phenylacridine, 1,7-bis(9-acridinyl)heptane, and the like), thioxanthones (2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthixanthone, 2-isopropylthixanthone, and the like), acetophenones (e.g., 1,1-dichloroacetophenone, p-t-butyldichloroacetophenone, 2,2-diethoxyacetphenone, 2,2-dimethoxy-2- phenylacetophenone, 2,2-dichloro-4-phenoxyacetopehnone, and the like), 2,4,5-triarylimidazole dimers (e.g., 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl imidazole dimer, 2-(0- flurophenyl)-4,5-diphenylimidazole dimer, 2-(0- methoxyphenyl)4,5-diphenylimidazole dimer, 2-(pmethoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(pmethoxyphenyl)-5-phenylimidazole dimer, 2-(2,4- dimethoxyphenyl)-4,5-diphenylimidazole dimer, or 2-(pmethylmercaptophenyl)-4,5-diphenylimidazole dimmer) Though not a free-radical generator, triphenylphosphine may be included in the photoinitiator chemical system as a catalyst.  \n\n[0067] The photopolymerizable compositions may also include one or more plasticizers in amounts of from $0.5\\%$ to  \n\n$10.0\\%$ by weight of the composition.Examples of suitable plasticizers include, but are not limited to, phthalate ester (e.g., dibutylphthalate, diheptylphthalate, dioctylphthalate, and diallylphthalate), glycols (e.g., polyethylene glycol, and polypropylene glycol), glycol esters (e.g., triethylene-glycodiacetate,tetraethylene-glycoldiacetate,dipropylene-glycol-dibenzoate), phosphate esters (tricresylphosphate, triphenylphosphate), amides (p-toluenesulfoneamide, benzensulfoneamide, N-n-butylacetoneamide), aliphatic dibasic acid esters (diisobutyl-adipate, dioctyladipate, dimethylsebacate, dioctylazelate, dibutylmalate, triethylcitrate, tributylcitrate, triethylacetylcitrate, tri-n-propylacetylcitrate, tri-n-butylacetylcitrate, butyl-laurate, dioctyl-4,5-diepoxycyclohexane-1,2-dicarboxylate， glycerinetriacetylesters, dipropyleneglycol dibenzoate, polyethyleneglycol200 dibenzoate, sucrose benzoate, or trioctyl trimellitate.  \n\n[0068] Photopolymerizable compositions of the present invention may also include a color former. Color formers are employed in amounts of from $0.1\\%$ to $1.0\\%$ by weight of the composition.Examples of suitable color formers include, but are not limited to, diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl- $\\mathfrak{p}$ -phenylenediamine, p-toluidine， $^{4,4^{\\prime}}$ -biphenyldiamine， o-chloroaniline， leuco crystal violet, or leuco malachite green.  \n\n[0069] Additionally, the photoimageable compositions may contain a wide variety of additional components as are well known in the art, including additional polymers, such as those that might be used to effect a final hardened cure of a solder mask, dyes, stabilizers, flexibilizing agents, rheology agents, or fillers. A wide variety of additional polymeric or resin binders may be added to the photoresists. Such additional polymeric binders may include, as polymerized components,one or more acid functional monomers such as (meth)acrylic acid. For example, U.S. Pat. No. 5,952,153 discloses polymeric binders that have sufficient acid functionality to be employed in the photoresists of the present invention. When employed, such polymers may be used in amounts of from $5\\%$ to $20\\%$ by weight of the photoresist composition.  \n\n[0070] Processing of the photopolymerizable compositions is by any suitable method employed in the art. For example, a photopolymerizable composition layer, either formed from a liquid composition or transferred as a layer from a dry film, is applied to a substrate, such as a copper surface, of a metal-clad board. Other suitable metals include, but are not limited to, copper alloys, nickel, tin, zinc, gold, silver, platinum, or palladium. When a liquid photoresist composition is used, it may be applied to a substrate by any known means, such as spinning, dipping, roller coating and the like. When a dry film is used, the dry film is composed of a liquid photoimageable composition dried onto a flexible sheet, e.g., polyethylene terephthalate. Optionally, a protective sheet, e.g., polyethylene, is provided on the surface of the dried photoimageable layer opposite the support sheet before the film is rolled into reels. The protective sheet is removed prior to application, e.g., lamination, to the metalclad board. Once applied, the photoimageable composition layer is then exposed to actinic radiation through appropriate artwork. Exposure to actinic radiation polymerizes the cross-linking components in the light-exposed areas resulting in a cross-linked structure that is resistant to developer. Next, the composition is developed in dilute alkaline aqueous solution, such as a $1\\%$ sodium carbonate solution. The alkali solution causes salt formation with carboxylic acid groups of the functionalized polymer rendering the unexposed portions of the photoresist soluble and removable. After development, an etchant may be used to remove metal from areas where the photoresist was removed thereby forming a printed circuit. The remaining photoresist is then removed using an appropriate stripper, such as $1\\%$ to $3\\%$ sodium or potassium hydroxide aqueous solution. Organic based developers, such as tetraalkylammonium hydroxide based developers, may be used but are less preferred for the reasons discussed above.  \n\n[0071] Surprisingly, the present invention provides for a photopolymerizable composition having improved fine line adhesion with faster stripping, and faster strip time with smaller strip mode. Such improvements do not typically occur together in photopolymerizable compositions. Additionally, the particles of photopolymerized material that are stripped are reduced in size in contrast to conventional photopolymerizable material. Particle sizes range from 2 to 30 millimeters. Conventional photoresists have particle sizes from 2 millimeters to large size sheets of meters in size. If strip mode is large, the particles may collect on board manufacturing apparatus wheels and wheel bars contaminating the apparatus. Typically when a photopolymerized material has a fast stripping time the particle size is large. Accordingly, the present invention has unexpected improvements.  \n\n[0072] Another advantage of the present invention is the elimination or at least reduction in the amount of ethylenically unsaturated monomers that are used in the photopolymerizable composition. The functionalized polymer may be the only cross-linking agent in a photopolymerizable composition. Photopolymerizable processes do not reach $100\\%$ conversion. Accordingly, in conventional photoresists free monomer exists in the cured state of the composition. Such monomers may migrate through cover sheets on which a photopolymerizable composition is laminated. The monomers may then act as lubricants causing roll slippage and distortion. Additionally, workers may be exposed to the monomers that have migrated through the cover sheets presenting a toxic hazard. Such migration of monomers may also contaminate artwork employed in lithography. Monomers also may leach into various processing solutions during the manufacture of printed circuit boards and adversely affect the performance of the solutions and the quality of the boards. The monomers may also plasticize dry film photopolymerizable compositions resulting in edge fusion in a dry film roll. The present invention, by reducing or eliminating cross-linking monomers, eliminates or at least reduces the foregoing problems.  \n\n[0073] Also, compositions that have reduced or no monomer content are easier to waste treat. Conventional waste treatment schemes involve a process in which the $\\mathrm{pH}$ of the waste treatment stream is lowered by the addition of acid. This causes pH sensitive materials such as polymer binders to precipitate out of solution.The resultant solution becomes clear and free of waste. Monomers typically are not $\\mathrm{\\pH}$ sensitive and as a result are more difficult to treat than polymers. Thus, the present invention provides for a more environmentally friendly composition and one which is easier to waste treat because the amount of monomers in the composition is either eliminated or at least reduced.  \n\n[0074] The following examples are intended to further illustrate the present invention but are not intended to limit the scope of the invention.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# EXAMPLE1",
+        "category": " Introduction"
+    },
+    {
+        "id": 11,
+        "chunk": "# Copolymer 1 Preparation  \n\n[0075] A homogeneous solution containing 250 grams of methacrylic acid, 100 grams of poly(ethoxylate-b-caprolactone) monomethacrylate with 6 ethoxylations and 650 grams of methyl methacrylate was prepared. $75\\%$ by weight of the homogeneous solution were transferred into a second flask. The homogeneous solution of the first flask was diluted to $26.0\\%$ by weight solids and the homogeneous solution of the second flask was diluted to $60\\%$ by weight solids by adding sufficient methyl ethyl ketone.  \n\n[0076]The first flask was mixed and heated to reflux under atmospheric conditions. 11 grams of 2,2'-azobis (2-methylbutyronitrile) was added to the reaction mixture, mixed and held at reflux for about 30 minutes.  \n\n[0077] 18  grams of $^{2,2^{\\prime}}$ -azobis (2-methylbutyronitrile) was mixed with 38.0 grams of methyl ethyl ketone and fed into the first flask along with the contents of the second flask over 4 hours while maintaining reflux.An additional amount of 9.0 grams of methyl ethyl ketone was then added to the first flask and the mixture was refluxed for an additional hour.  \n\n[0078] 15 grams of 2,2'-azobis (2-methylbutyronitrile) were dissolved in 48.0 grams of methyl ethyl ketone and mixed. The mixture was then added to the first flask over a period of 90 minutes while maintaining reflux.  \n\n[0079] 24 grams of 2,2'-azobis (2-methylbutyronitrile) were mixed with 48.0 grams of methyl ethyl ketone and then fed into the reaction mixture over 15O minutes while maintaining reflux.An additional amount of 23.0 grams of methyl ethyl ketone were added to the reaction mixture. At the end of the reaction, 2,2'-azobis (2-methylbutyronitrile) was thermally killed off to below parts per million concentrations. The copolymer formed contained 68.1 mole $\\%$ of methyl methacrylate, 30.5 mole $\\%$ of methacrylic acid and 1.4 mole $\\%$ of poly(ethoxylate-b-cparolactone) monomethacrylate residues. The copolymer was $95.0\\%$ hydroxyl capped.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# EXAMPLE2",
+        "category": " Introduction"
+    },
+    {
+        "id": 13,
+        "chunk": "# Copolymer 2 Preparation  \n\n[0080] A homogeneous solution containing 250 grams of methacrylic acid, 650 grams of methyl methacrylate and 100 grams of 2-hydroxyethyl methacrylate was prepared. $75\\%$ by weight of the homogeneous solution were transferred into a second flask. The homogeneous solution of the first flask was diluted to $25\\%$ be weight solids and the homogeneous solution of the second flask was diluted to $60\\%$ by weight solids by adding sufficient methyl ethyl ketone.  \n\n[0081]The first flask was mixed and heated to reflux under atmospheric conditions.11 grams of 2,2'-azobis (2-methylbutyronitrile) was added to the reaction mixture, mixed and held at reflux for 30 minutes.  \n\n[0082] 18 grams of 2,2'-azobis (2-methylbutyronitirle) was mixed with 40.0 grams of methyl ethyl ketone and fed into the first flask along with the contents of the second flask over 4 hours while maintaining reflux.An additional amount of 10.0 grams of methyl ethyl ketone was then added to the first flask and the mixture was refluxed for an additional hour.  \n\n[0083] 15 grams of 2,2'-azobis (2-methylbutyronitirle) were dissolved in 50.0 grams of methyl ethyl ketone and mixed.The mixture was then added to the first flask over a period of 90 minutes while maintaining reflux.  \n\n[0084] 24 grams of 2,2'-azobis (2-methylbutyronitrile) were mixed with 50.0 grams of methyl ethyl ketone and then fed into the reaction mixture over 15O minutes while maintaining reflux.An additional amount of 20.0 grams of methyl ethyl ketone were added to the reaction mixture.At the end of the reaction, 2,2'-azobis (2-methylbutyronitirle) was thermally killed off to below parts per million concentration. The copolymer formed contained 63.8 mole $\\%$ of methyl methacrylate, 28.6 mole $\\%$ of methacrylic acid and 7.6 mole $\\%$ or 2-hydroxyethyl methacrylate residues. The copolymer was $17.6\\%$ hydroxyl capped.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 14,
+        "chunk": "# EXAMPLE3",
+        "category": " Introduction"
+    },
+    {
+        "id": 15,
+        "chunk": "# Copolymer 3 Preparation  \n\n[0085] A homogeneous solution containing 250 grams of methacrylic acid, 650 grams of methyl methacrylate, and 100 grams of poly(ethoxylated) monomethacrylate with 6 ethoxylations was prepared. $75\\%$ be weight of the homogeneous solution were transferred into a second flask. The homogeneous solution of the first flask was diluted to $25\\%$ by weight solids and the homogeneous solution of the second flask was diluted to $60\\%$ be weight solids by adding suficient methyl ethyl ketone.  \n\n[0086]The first flask was mixed and heated to reflux under atmospheric conditions. 11 grams of 2,2'-azobis (2-methylbutyronitirle) was added to the reaction mixture, mixed and held at reflux for 30 minutes.  \n\n[0087] 18 grams of 2,2'-azobis (2-methylbutyronitrile) was mixed with 40 grams of methyl ethyl ketone and fed into the first flask along with the contents of the second flask over 4 hours while maintaining reflux.An additional amount of 10.0 grams of methyl ethyl ketone was then added to the first flask and the mixture was refluxed for an additional hour.  \n\n[0088] 15 grams of 2,2'-azobis (2-methylbutyronitirle) were dissolved in 50 grams of methyl ethyl ketone and mixed.The mixture was then added to the first flask over a period of 90 minutes while maintaining reflux.  \n\n[0089] 24 grams of 2,2'-azobis (2-methylbutyronitrile) were mixed with 50.0 grams of methyl ethyl ketone and then fed into the reaction mixture over 150 minutes while maintaining reflux.An additional amount of 25.0 grams of methyl ethyl ketone were added to the reaction mixture. At the end of the reaction, 2,2'-azobis (2-methylbutyronitrile) was thermally killed off to below parts per million concentrations. The copolymer was composed of 67.0 mole $\\%$ of methyl methacrylate, 30.0 mole $\\%$ methacrylic acid and 3.0 mole $\\%$ poly(ethoxylated) monomethacrylate residues. The copolymer was $45.1\\%$ hydroxyl capped.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 16,
+        "chunk": "# EXAMPLE4",
+        "category": "s that the text segment provided is incomplete, as it only includes a placeholder \"# EXAMPLE4\" without any actual content regarding hydrophilic polymers. Therefore, I will need the actual text segment to analyze and classify it appropriately. \n\nPlease provide the full text segment you'd like me to analyze, and I'll be able to determine which part of a paper it belongs to."
+    },
+    {
+        "id": 17,
+        "chunk": "# Copolymer 4 Preparation  \n\n[0090] A homogeneous solution containing 250 grams of methacrylic acid, 650 grams of methyl methacrylate, 100 grams of 2-hydroxyethyl methacrylate, and 2.0 grams of n-butyl acrylate was prepared. $75\\%$ by weight of the homogeneous solution were transferred into a second flask. The homogeneous solution of the first flask was diluted to $26.0\\%$ by weight solids and the homogeneous solution of the second flask was diluted to $60\\%$ by weight solids by adding sufficient methyl ethyl ketone.  \n\n[0091]The first flask was mixed and heated to reflux under atmosphereic conditions. 11 grams of 2,2'-azobis (2-methylbutyronitrile) was added to the reaction mixture,mixed and held at reflux for 30 minutes.  \n\n[0092] 18 grams of 2,2'-azobis (2-methylbutyronitrile) was mixed with 40.0 grams of methyl ethyl ketone and fed into the first flask along with the contents of the second flask over 4 hours while maintaining reflux.An additional amount of 9.0 grams of methyl ethyl ketone was then added to the first flask and the mixture was refluxed for an additional hour.  \n\n[0093] 15 grams of 2,2'-azobis (2-methylbutyronitrile) were dissolved in 50.0 grams of methyl ethyl ketone and mixed. The mixture was then added to the first flask over a period of 90 minutes while maintaining reflux.  \n\n[0094] 24 grams of 2,2'-azobis (2-methylbutyronitrile) were mixed with 50.0 grams of methyl ethyl ketone and then fed into the reaction mixture over 15O minutes while maintaining reflux.An additional amount of 23.0 grams of methyl ethyl ketone were added to the reaction mixture. At the end of the reaction, 2,2'-azobis (2-methylbutyronitrile) was thermally killed off to below parts per million concentrations. The copolymer was composed of 59.6 mole $\\%$ of methyl methacrylate, 28.9 mole $\\%$ of methacrylic acid, 7.6 mole $\\%$ 2-hydroxyethyl methacrylate and 3.9 mole $\\%$ of n-butyl acrylate. The copolymer was $17.4\\%$ hydroxyl capped.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# EXAMPLE5",
+        "category": " Introduction"
+    },
+    {
+        "id": 19,
+        "chunk": "# Functional Testing of Photoresists  \n\n[0095] Two photopolymerizable compositions were prepared using one of copolymers 2 or 4 in each photopolyerizable composition.Each photopolymerizable composition was composed of the components of Table 1.  \n\nTABLE1   \n\n\n<html><body><table><tr><td>Component</td><td>Wt %</td><td>Function</td></tr><tr><td>Copolymer 2 or 4</td><td>66.75</td><td>Polymer Binder</td></tr><tr><td>Bis A ethoxylate dimethacrylate</td><td>13.67</td><td>Photopolymerizable oligomer</td></tr><tr><td>Alkylene oxide, mono methacrylate</td><td>10.80</td><td>Photopolymerizable monomer</td></tr><tr><td>Michler's ethyl ketone</td><td>0.05</td><td>UV absorber</td></tr><tr><td>Lophine dimmer (bis-</td><td>3.50</td><td>Color activator/photoinitiator</td></tr><tr><td>chlorimidazole)</td><td></td><td></td></tr><tr><td>Leuco crystal violet</td><td>0.40</td><td>Color formor</td></tr><tr><td>Malachite green</td><td>0.05</td><td>Dye</td></tr><tr><td>Phthalate</td><td>4.48</td><td>Plasticizer</td></tr><tr><td>Benzophenone</td><td>3.0</td><td>Photoinitiator</td></tr><tr><td>Modaflow ?</td><td>0.10</td><td>Flow control agent</td></tr></table></body></html>  \n\n[0096]  Each composition  was prepared  in  7:1 2-butanone:2-propanol at $50\\%$ solids.Each solution was coated onto separate biaxially orientated 80 gauge polyester films and dried to $1\\%$ or less retained solvent.The coated mixtures were then laminated onto mechanically scrubbed 1 oz/FR  \n\n$4/1$ oz clad copper composite using a hot roll laminator at $110^{\\circ}\\mathrm{~C~}$ .at 2 meters/minute and 3 bar pressure.  \n\n[0097]   Breakpoint in seconds was determined for each of the photopolymerizable compositions. The developer employed was a $1\\%$ by weight sodium carbonate monohydrate aqueous solution. The time measured was the time each coated panel took to reach the $50\\%$ point in the conveyorized spray developer. Results for each copolymer are in Table 2 below.  \n\n[0098]   A second set of laminated materials with each type of copolymer were then imaged on a UV printer through an appropriate phototool with an adjusted exposure to obtain a copper step of 7 as measured with a Stouffer $\\circledast21$ step wedge (exposure unit settings varied as shown in Table 2). The exposed panels were then tested for both fine line adhesion (stress test for adhesion) and cross-hatch adhesion (macroscopic observation of adhesion with a scale of 1-5 with 5 being the best adhesion) of the photopolymerized compositions. The exposed panels were then developed in a $1\\%$ sodium carbonate monohydrate solution at $30^{\\circ}\\mathrm{~C~}$ . using a conveyorized spray developer at 26 psi with residence time adjusted such that the break point occurred at $50\\%$ of the chamber length, followed by several spray rinses using deionized water.  \n\n[0099]  Etching was accomplished using a 2N cupric chloride/hydrochloric acid solution at $45^{\\circ}\\mathrm{~C~}$ 、in a conveyorized etcher equipped with multiple spray nozzles. The etch resolution of each photopolymerized composition was measured using a scanning electron micrograph (SEM). The etched boards were then stripped of the imaged, developed and etched photopolymerized compositions in a $3\\%$ by weight sodium hydroxide solution as $52^{\\circ}\\mathrm{~C~}$ in a conveyorized stripping unit equipped with multiple spray nozzles followed by a spray rinse of deionized water. The stripping time and mode of each photopolymerized composition was recorded as shown in Table 2.  \n\ncompositions of the present invention provide an improved binder material and photoresist.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 20,
+        "chunk": "# EXAMPLE6",
+        "category": " Introduction"
+    },
+    {
+        "id": 21,
+        "chunk": "# Synthesis of Functionalized Copolymer  \n\n[0103] A homogeneous solution containing 197 grams of methacrylic acid, 512 grams of methyl methacrylate and 79 grams of poly(ethoxylated) monomethacrylate was prepared. $75\\%$ by weight of the homogeneous solution were prepared into a second flask. The homogeneous solution of the first flask was diluted to $25\\%$ by weight solids and the homogeneous solution of the second flask was diluted to $60\\%$ be weight solids by adding sufficient methyl ethyl ketone.  \n\n[0104]The first flask was mixed and heated to reflux under atmospheric conditions. 2.0 grams of 2,2'-azobis (2-methylbutyronitirle) was added to the reaction mixture,mixed and held at reflux for 30 minutes.  \n\n[0105] 6.0 grams of 2,2'-azobis (2-methylbutyronitirle) was mixed with about 40 grams of methyl ethyl ketone and fed into the first flask along with the contents of the second flask over 4 hours while maintaining reflux. An additional amount of 9.0 grams of methyl ethyl ketone was then added to the first flask and the mixture was refluxed for an additional hour.  \n\n[0106] 5.0 grams of 2,2'-azobis (2-methylbutyronitrile) were dissolved in 50.0 grams of methyl ethyl ketone and mixed. The mixture was then added to the first flask over a period of 90 minutes while maintaining reflux.  \n\n[0107] 9.0 grams of 2,2'-azobis (2-methylbutyronitrile) were mixed with 50.0 grams of methyl ethyl ketone and then fed into the reaction mixture over 150 minutes while maintaining reflux.An additional amount of 25.0 grams of methyl ethyl ketone were added to the reaction mixture.At the end [0100] The two copolymers of the present invention had good fine line adhesion values, good cross hatch adhesion values, good strip times for removing cured photopolymerized material from the panels and good plating resolution.  \n\nTABLE2   \n\n\n<html><body><table><tr><td>Copolymer In Photoresist</td><td>B.P. (Sec)</td><td>Exposure Unit Setting</td><td>Etch Resolution (microns)</td><td>Plating Resolution (microns)</td><td>Fine Line Adehsion (microns)</td><td>Cross Hatch Adesion (5 = best)</td><td>Developed Sidewall (10 = best)</td><td>Strip Time (sec)</td><td>Strip Mode (mm)</td><td>Residue (mg)</td></tr><tr><td>2</td><td>29</td><td>24</td><td>80</td><td>35</td><td>80</td><td>4</td><td>1</td><td>29</td><td>20-30</td><td>17.4</td></tr><tr><td>4</td><td>19</td><td>14</td><td>60</td><td>30</td><td>60</td><td>5</td><td>4</td><td>30</td><td>5-10</td><td>4.9</td></tr></table></body></html>  \n\n[0101] Copolymer 4 which contained n-butyl acrylate showed side wall improvement over copolymer 2 which contained 2-hydroxyethyl methacrylate as well as reduced residue deposit. Thus, the addition of an n-butyl acrylate monomer to the copolymer binder further improved the properties of the photoresist of the present invention.  \n\n[0102] Unexpectedly, the compositions of the present invention showed good fine line adhesion with good plating resolution, good adhesion with fast stripping, and a fast stripping time with a low strip mode. Accordingly, The of the reaction, 2,2'-azobis (2-methylbutyronitirle) was thermally killed off to below parts per million concentrations. The acrylic copolymer main chain or backbone was set aside.  \n\n[0108]  5.31 grams of 1,6-hexamethylene diisocyanate biuret $(23.\\%$ free-NCO) were added to a clean dry, nitrogen sparged flask. 0.06 grams of dibutylin dilaurate, 0.05 grams of Irganox $\\textsuperscript{\\textregistered}$ 1076 (antioxidant) and 160.0 grams of methyl ethyl ketone were also added to the flask. The flask was sparged with dry air and stoppered. The components were mixed and heated at $35^{\\circ}\\mathrm{~C~}$  \n\n[0109]  In a separate clean dry air sparged addition funnel, 15.97 grams ofpoly(ethoxylate-b-caprolactone) monomethacrylate oligomer was weighed out. The oligomer was added to the flask containing the 1,6-hexamethylene diisocyanate biuret over 1 hour with mixing and maintaining a temperature of $35^{\\circ}\\mathrm{C}$ The addition funnel was then rinsed with 118.0 grams of methyl ethyl ketone to remove any remaining oligomer. The rinse was added to the flask containing the biuret with a temperature increased to $60^{\\circ}\\mathrm{C}$ The reaction was maintained for 3 hours at $60^{\\circ}\\mathrm{~C~}$ the reaction was monitored to determine completion of the synthesis of a urethane acrylate moiety by high pressure liquid chromatography (HPLC).  \n\n[0110] The functionalized polymer was prepared by weighing out 763.0 grams of the acrylic copolymer ( $47\\%$ solids) and 50.0 grams of methyl ethyl ketone to a clean, dry air sparged flask. The combination was mixed and heated to $45^{\\circ}\\mathrm{~C~}$ The urethane/acrylate moiety was then added to the acrylic polymer over 1 hour 0.50 grams of Irganox $\\textsuperscript{\\textregistered}$ 1076 and 30.0 grams of methyl ethyl ketone was added to the reaction mixture. The reaction contents were held at $45^{\\circ}\\mathrm{C}$ . for 3 hours with constant mixing. The resulting copolymer was composed of 25 mole $\\%$ of methyacrylic acid, 65 mole $\\%$ of methyl methacrylate and 10 mole $\\%$ of poly(ethoxylated) monomethacrylate residues. The copolymer main chain was 6 mole $\\%$ functionalized with the moiety.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 22,
+        "chunk": "# EXAMPLE7",
+        "category": " Introduction"
+    },
+    {
+        "id": 23,
+        "chunk": "# Synthesis of a Functionalized Copolymer  \n\n[0111]  A homogeneous solution containing 77.5 grams of 2-hydroxyethyl methacrylate, 194 grams of methacrylic acid, and 504 grams of methyl methacrylate was prepared. $75\\%$ by weight of the homogeneous solution was transferred to a second flask. The homogeneous solution of the first flask was diluted to $25\\%$ by weight solids and the homogeneous solution of the second flask was diluted to $60\\%$ by weight solids by adding sufficient methyl ethyl ketone.  \n\n[0112]The first flask was mixed and heated to reflux under atmospheric conditions. 2.0 grams of $^{2,2^{\\prime}}$ -azobis (2-methylbutyronitirle) was added to the reaction mixture,mixed and held at reflux for 3O minutes.  \n\n[0113] 6.25 grams of 2,2'-azobis (2-methylbutyronitirle) was mixed with 40.0 grams of methyl ethyl ketone and fed into the first flask along with the contents of the second flask over 4 hours while maintaining reflux.An additional amount of 9.0 grams of methyl ethyl ketone was then added to the first flask and the mixture was refluxed for an additional hour.  \n\n[0114] 5.0 grams of 2,2'-azobis (2-methylbutyronitrile) were dissolved in 50.0 grams of methyl ethyl ketone and mixed.The mixture was then added to the first flask over a period of 90 minutes while maintaining reflux.  \n\n[0115] 9.0 grams of 2,2'-azobis (2-methylbutyronitirle) were mixed with 50.0 grams of methyl ethyl ketone and then fed into the reaction mixture over 15O minutes while maintaining reflux.An additional amount of 23.0 grams of methyl ethyl ketone were added to the reaction mixture. At the end of the reaction, 2,2'-azobis (2-methylbutyronitirle) was thermally killed off to below parts per million concentrations. The acrylic polymer main chain or backbone product was set aside.  \n\n[0116] 150.0 grams of 1,6-hexamethylene diisocyanate biuret ( $23.0\\%$ -NCO) were added to a clean dry, nitrogen sparged flask. 0.06 grams of dibutylin dilaurate, 0.05 grams of Irganoxe 1076 (antioxidant) and 160.0 grams of methyl ethyl ketone were also added to the flask. The flask was sparged with dry air and stoppered. The components were mixed and heated at $35^{\\circ}\\mathrm{~C~}$ ·  \n\n[0117]  In a separate clean dry air sparged addition funnel, 190.0\"grams of poly(ethoxylate-b-caprolactone)monomethacrylate oligomer was weighed out. The oligomer was added to the flask containing the 1,6-hexamethylene diisocyanate biuret over 1 hour with mixing and maintaining a temperature of $35^{\\circ}\\mathrm{~C~}$ . The addition funnel was then rinsed with 120.0 grams of methyl ethyl ketone to remove any remaining oligomer. The rinse was added to the flask containing the biuret with a temperature increased to $60^{\\circ}\\mathrm{C}$ .The reaction was maintained for 3 hours at $60^{\\circ}\\mathrm{~C~}$ .The reaction was monitored to determine completion of the synthesis of the urethane acrylate moiety.  \n\n[0118]   The functionalized polymer  was  prepared  by weighing out 750.0 grams of the acrylic copolymer and 55.0 grams of methyl ethyl ketone to a clean, dry air sparged flask. The combination was mixed and heated to $45^{\\circ}\\mathrm{C}$ .The urethane/arcrylate moiety was then added to the acrylic copolymer over 1 hour. 0.50 grams of Irganox $\\textsuperscript{\\textregistered}$ 1076 and 30.0 grams of methyl ethyl ketone was added to the reaction mixture. The reaction contents were held at $45^{\\circ}\\mathrm{~C~}$ .for 3 hours with constant mixing. The polymer main chain was 6 mole percent functionalized with the moiety.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 24,
+        "chunk": "# EXAMPLE8",
+        "category": " Introduction"
+    },
+    {
+        "id": 25,
+        "chunk": "# Preparation of a Printed Circuit Board  \n\n[0119] Functionalized copolymers from Examples 7 and 8 are used to prepare two separate photoimageable compositions disclosed in the table below.  \n\nTABLE3   \n\n\n<html><body><table><tr><td>Component</td><td>Wt %</td><td>Function</td></tr><tr><td>Example 6 or Example 7</td><td>91.22</td><td>Polymer Binder</td></tr><tr><td>Michler's ethyl ketone</td><td>0.05</td><td>UV absorber</td></tr><tr><td>Lophine dimmer (bis-chlorimidazole)</td><td>3.50</td><td>Color activator/</td></tr><tr><td></td><td></td><td>photoinitiator</td></tr><tr><td>Leuco crystal violet Malachite green</td><td>0.40</td><td>Color formor</td></tr><tr><td></td><td>0.05</td><td>Dye</td></tr><tr><td>Phthalate</td><td>4.48</td><td>Plasticizer</td></tr><tr><td>Benzophenone</td><td>3.0</td><td>Photoinitiator</td></tr><tr><td>Modaflow ?</td><td>0.10</td><td>Flow control agent</td></tr></table></body></html>  \n\n[0120]  Each photopolymerizable composition is prepared in a 7:1 2-butanone:2-propanol at $50\\%$ solids. The solutions are coated onto separate biaxially orientated 80 gauge polyester films and dried to $1\\%$ or less retained solvent. The coated mixtures are then laminated onto mechanically scrubbed FR-4 copper clad composites using a hot roll laminator at $110^{\\circ}\\mathrm{~C~}$ . at 2 meters/minute and 3 bar pressure.  \n\n[0121] The laminated material is then imaged on a UV printer through an appropriate phototool. The exposed composites are developed in a $1\\%$ sodium carbonate monohydrate solution at $30^{\\circ}\\mathrm{~C~}$ . using a conveyorized spray developer at 26 psi with residence time adjusted so that the break point occurred at $50\\%$ of the chamber length followed by several spray rinses using tap water and deionized water.  \n\n[0122]   Etching was accomplished using a 2N cupric chloride/hydrochloric acid solution at $50^{\\circ}\\mathrm{~C~}$ in a conveyorized etcher equipped with multiple spray nozzles. The etched board is then stripped of the imaged developed and etched photopolymerized composition in a $3\\%$ sodium hydroxide solution at $55^{\\circ}\\mathrm{C}$ in a conveyorized stripping unit equipped with multiple spray nozzles followed by a spray rinse of tap water. The result is a quality printed circuit boards.  \n\nWhat is claimed is:  \n\n1.A compound comprising a backbone having a formula:  \n\n$$\n(\\mathrm{A)_{u}(B)_{v}(C)_{w}(D)_{x}(E)_{y}(F)_{z}}\n$$  \n\nwhere A is derived from one or more hydroxyl alkyl (meth)acrylate, B is derived from one or more hydroxy polyalkyleneoxide (meth)acrylate, C is derived from one or more alkyl(meth)acrylate, D is derived from one or more (meth)acrylic acid, E is derived from one or more vinyl aromatic monomer, nitrogen containing compound or thio-analog of a nitrogen containing compound, silicon containing monomer, substituted ethylene monomer, or cyclic olefin monomer, and F is derived from one or more hydroxy poly opened-ring lactone polyalkylene oxide (meth)acrylate, where u, v, W, X,y and z are weight percentages of the monomers in the backbone, where u is O to $30\\%$ ,v is O to $30\\%$ ,W is 5 to $70\\%$ $\\mathbf{x}$ is 5 to $40\\%$ ,yis O to $20\\%$ and $\\mathbf{z}$ is O to $30\\%$ with the proviso that at least one or u,V or $\\textbf{z}$ is greater than O, and at least one or A, B, C, D, E and $\\mathrm{~F~}$ has at least one pendent functional group.  \n\n2. The compound of claim 1, wherein the substituted alkyl (meth)acrylatecompriseshydoxyalkyl (meth)acrylate monomers where the substituted alkyl group is a branched or unbranched $(\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{6})\\mathrm{alkyl}$ ▪  \n\n3.The compound to claim 2, wherein the hydroxyalkyl (meth)acrylate monomer is 2-hydroxyalkyl (meth)acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 1-methyl-2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 1-methyl-2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylate, or 2-hydroxybutyl acrylate.  \n\n4. The compound of claim 3, wherein the hydroxyalkyl (meth)acrylates have a degree of polymerization of from 1 to 20.  \n\n5. The compound of claim 1, wherein the alkyl group has from 1 to 24 carbon atoms.  \n\n6.The compound of claim 1,wherein the pendent functional group is derived from a compound that reacts with a hydroxyl group or amine group on the backbone of the copolymer to form a bond, the pendent functional group comprises at least one $\\mathbf{\\alpha}_{\\alpha,\\beta}$ -ethylenically or acetylenically unsaturated moiety.  \n\n7. The compound of claim 6, wherein the pendent functional group is derived from monoisocyanates, diisocyanates, triisocyanates, polyisocyanates, or mixtures thereof.  \n\n8.The compound of claim 7,wherein the diisocyanates, triisocyanates or polyisocyanates are bonded through a free isocyanate group to a free hydroxyl group of a compound having a formula:  \n\n$$\n\\mathrm{CH}_{2}{=}\\mathrm{CHR}^{3}{\\operatorname{\\_}{C(O)}}{\\operatorname{\\_}{=}}0{\\operatorname{\\_}{=}}(\\mathrm{B_{1}}){\\operatorname{-}}(\\mathrm{C_{1}}){\\operatorname{-}}\\mathrm{H}\n$$  \n\nwherein $\\mathbb{R}^{3}$ is hydrogen or methyl, $(\\mathbf{A}_{1})$ ， $\\mathbf{(B_{1})}$ and $\\mathrm{(C_{1})}$ are in any order, $(\\mathbf{A}_{1})$ is a chain formed of from 1 to 40 alkoxylate monomers, aromatic-substituted alkoxylate monomers having from 1 to 20 carbon atoms,or mixtures thereof, $\\mathbf{\\left(B_{1}\\right)}$ is either absent or is a chain formed of from 1 to 40 alkoxylate monomers, or aromatic-substituted alkoxylate monomers having from 1 to 20 carbon atoms, or mixtures thereof, and the monomer composition of $\\mathbf{\\left(B_{1}\\right)}$ being different than the monomer composition of $(\\mathbf{A}_{1})$ ，and $\\left(\\mathrm{C}_{1}\\right)$ is a chain formed of from 1 to 40 open-ring lactone monomers having from 2 to 21 carbon atoms.  \n\n9. A photopolymerizable composition comprising a) a polymeric binder having a formula:  \n\n$$\n(\\mathbf{A})_{\\mathbf{u}}(\\mathbf{B})_{\\mathbf{v}}(\\mathbf{C})_{\\mathbf{w}}(\\mathrm{D}_{\\mathbf{x}}(\\mathbf{E})_{\\mathbf{y}}(\\mathbf{F})_{\\mathbf{z}}\n$$  \n\nwhere A is derived from one or more hydroxyl substituted alkyl (meth)acrylate, B is derived from one or more hydroxy polyalkyleneoxide (meth)acrylate, C is derived from one or more alkyl (meth)acrylate, D is derived from one or more (meth)acrylic acid, E is derived from one or more vinyl aromatic monomer, nitrogen containing compound or thio-analog of a nitrogen containing compound， silicon containing monomer, substituted ethylene monomer, or cyclic olefin monomer, and F is derived from one or more hydroxy poly opened-ring lactone polyalkylene oxide (meth)acrylate where u, v, w, x, y and z are weight percentages of the monomers in the backbone, where u is O to $30\\%$ D $\\mathbf{v}$ is O to $30\\%$ ,wis 5 to $70\\%$ $\\mathbf{x}$ is 5 to $40\\%$ D y is O to $20\\%$ and $\\mathbf{z}$ is 0 to $30\\%$ with the proviso that at least one of u, v or $\\mathbf{z}$ is greater than O, and at least one of A, B, C, D,E and $\\mathrm{~F~}$ has at least one pendent functional group; and  \n\nb) one or more photoinitiators.  \n\n10. The photopolymerizable composition of claim 9, wherein the hydroxyl substituted alkyl (meth)acrylates are branched or unbranched hydroxyq $\\mathrm{\\cdot}\\mathrm{C}_{2}\\mathrm{-}\\mathrm{C}_{6})$ alkyl (meth)acrylates.  \n\n11. The photopolymerizable composition of claim 9, wherein the functional pendent group has one or more $\\mathbf{\\alpha}_{\\alpha,\\beta}$ -ethylenically or acetylenically unsaturated group.  \n\n12. The photopolymerizable composition of claim 11, wherein the functional pendent group having the one or more $\\lvert\\mathbf{\\alpha}\\rvert_{\\mathbf{\\alpha}},\\beta$ -ethylenically or acetylenically unsaturated group is derived from a monoisocyanate, diisocyanate, triisocyanate, or polyisocyante.  \n\n13. The photopolymerization composition of claim 9, further comprising cross-linking agents, plasticizers, fillers, rheology agents, stripping agents, dyes, stabilizers, or mixtures thereof.  \n\n14. A method of imaging comprising:  \n\na) providing a photopolymerizable composition comprising: 1) a compound having a formula: $(\\mathrm{A})_{\\mathrm{u}}(\\mathrm{B})_{\\mathrm{v}}(\\mathrm{C})_{\\mathrm{w}}(\\mathrm{D})_{\\mathrm{x}}(\\mathrm{E})_{\\mathrm{y}}(\\mathrm{F})_{\\mathrm{z}}$  \n\nwhere A is derived from one or more hydroxy substituted alkyl (meth)acrylate, B is derived from one or more hydroxy polyalkylene oxide (meth)acrylate, C is derived from one or more alkyl (meth)acrylate, D is derived from one or more (meth)acrylic acid, E is derived from one or more vinyl aromatic monomer, nitrogen containing compound, silicon containing monomer, substituted ethylene monomer, or cyclic olefin monomer, or thio-anolog of a nitrogen containing compound, and $\\mathrm{~F~}$ is one or more poly opened-ring lactone polyalkylene oxide (meth)acrylate, where u, V, W, X, y and z are weight percentages of the monomers in the backbone,where u is O to  \n\n$30\\%$ , V is O to $30\\%$ ,wis 5 to $70\\%$ $\\mathbf{x}$ is 5 to $40\\%$ , y is 0 to $20\\%$ and $\\mathbf{z}$ is O to $30\\%$ with the proviso that at least one of u, v or $\\mathbf{z}$ is greater than O, and at least one of A,B,C, D, E and $\\mathrm{~F~}$ has at least one pendent functional group, and 2) one or more photoinitiators;   \nb) applying the photopolymerizable compositioin to a substrate;   \nc) imagewise exposing the photopolyrnerizable composition to actinic radiation to form a polymerized composition; and   \nd) developing the imagewise exposed photopolymerized compositon to form an image on the substrate.  \n\n15. The method of claim 14, further comprising a step of etching away metal on the substrate exposed during developing. 16. The method of claim 15, further comprising the step of stripping away the photopolymerized composition from the developed and etched board to form a printed circuit board. 17. The method of claim 16, wherein the metal on the substrate comprises copper, copper alloy, nickel, gold, platinum, silver, tin, zinc, or palladium.",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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+++ b/task2/task2-chunks/gui2020.json
@@ -0,0 +1,62 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Few-Layer Black Phosphorus as an Artificial Substrate for DNA Replication  \n\nJie Gui, Yunfei Bai, Huizhen Li, Jian Peng, Yufan Huang, Liping Sun,\\* and Jian Weng\\*  \n\nCite This: ACS Appl. Nano Mater. 2020, 3, 1775−1782",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# ACCESS I Metrics & More  \n\nArticle Recommendations  \n\nSupporting Information  \n\nABSTRACT: DNA replication is the basis for biological inheritance in nature. The plasma membrane of prokaryotic bacteria might provide a supporting surface for the attachment of either polymerase or DNA during in vivo DNA replication. In order to understand that fixing DNA or polymerase on the membrane is important for highly efficient DNA replication, we develop a system to mimic prokaryotic DNA replication. We introduce a two-dimensional nanomaterial, few-layer black phosphorus (BP), which shares some similar properties with bacteria plasma membrane in dimension, surface group, surface charge, hydrophilicity, and thickness. Either polymerase or DNA primer is immobilized on a BP surface to initiate in vitro DNA replication. The results show that BP could promote DNA replication with high efficiency in both cases. The DNA yield is increased to more than 6 times and nonspecific products are reduced significantly. This discovery might deepen our understanding about the role of immobilization of the replication component on the membrane and application of BP as an artificial substrate for DNA replication. KEYWORDS: 2D nanomaterials, DNA replication, cell membrane, black phosphrous, biomimic  \n\n![](images/86f6c82fb8c7edd234ff9332f246b962f64d3e4a84290a9f073351e1961d95de.jpg)",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# INTRODUCTION  \n\nFew-layer black phosphorus (BP) is a two-dimensional (2D) nanomaterial widely used in the photoelectronic field because of its tunable band gap and anisotropic properties.1 In addition, BP has many biomedical applications, such as cancer imaging, cancer therapy, drug delivery, and various types of biosensing owing to its large surface area and excellent biocompatibility and biodegradability.2−5 The exposed lone pairs at the BP surface make phosphorus very reactive to oxygen, leading to the formation of negatively charged phosphate ions covered on its surface.6,7 Some strategies have been developed to enhance its stability. Xinget al. demonstrated that three-dimensional graphene oxide $(\\mathrm{GO})/$ BP hybrid aerogels exhibit excellent photothermal stability in ambient conditions.8 Yu’s group found that ${\\mathrm{Ag}}^{+}$ can be spontaneously adsorbed on the BP surface via cation $-\\pi$ interactions, rendering BP more stable in air.9 Although BP is unstable in water and air, its degradation products, phosphorus oxides, are nontoxic to the human body.  \n\nDNA replication is one of the most rapid and efficient processes that take place within cells. Genetic information is transferred from parent to progeny organisms by the faithful replication of parental DNA. The ability of cells to maintain a high degree of order depends on the accurate duplication of  \n\nDNA.10,11 Some researchers suggest that a bacteria plasma membrane might provide a supporting surface for DNA replication, and chromosomal DNA might be anchored on the bacterial membrane surface to form a DNA/membrane complex to initiate DNA replication. The origin of replication (oriC) of the Escherichia coli chromosome might bind with high affinity to the cell membrane.12,13 Similarly, the nuclear matrix (or skeleton) in eukaryotic cells could also provide a framework for efficient and precise genome duplication.14 The replication complexes might be attached to the nuclear matrix when DNA is replicated.15 Therefore, a supporting surface, such as plasma membrane or nuclear matrix, may be very important for the in vivo DNA replication process. Anionic phospholipids, such as phosphatidylglycerol and cardiolipin, would play a role in bacteria chromosomal replication by regulating the initiator protein DnaA. The activated initiator protein DnaA at the cell membrane recognizes and binds the oriC site of the bacterial chromosome to initiate DNA  \n\n![](images/868c00371c50f2ad9c7e9f4521a2ab12395f5e2bdb6af70e4408127142f8d1bf.jpg)  \nFigure 1. Comparison of the plasma membrane and BP. (a) The plasma membrane consists of a lipid bilayer. The phospholipid has a polar headgroup and two hydrophobic hydrocarbon tails. X represents a hydrogen or alcohol headgroup attached to the phosphate group of the  \n\nmembrane. (b) BP is composed of several layers of black phosphorene. Its surface is covered by phosphate ions. The yellow area represents the hydrophilic region, while the purple area represents the hydrophobic region. TEM images of the plasma membrane of $E_{\\sun}$ . coli $\\tt D H S\\alpha$ (c) and BP (d). (e) High-resolution P 2p XPS spectrum of BP. (f) $\\zeta$ potentials of the bacteria membrane $\\cdot{-}26.8~\\mathrm{mV})$ and BP $\\left(-30.4~\\mathrm{mV}\\right)$ . The contact angles of the bacteria plasma membrane of E. coli $\\mathtt{D H S}\\alpha$ $(\\mathbf{g})$ and BP (h). AFM curves and height profiles of the bacteria plasma membrane (i) and BP (j).  \n\nFigure 1. continued   \nTable 1. Similarities between the Plasma Membrane and BP   \n\n\n<html><body><table><tr><td></td><td> dimension</td><td> surface group</td><td>surface charge (§ potential), mV</td><td> hydrophilicity (contact angle), deg</td><td>thickness, nm</td></tr><tr><td>plasma membrane</td><td>2D</td><td> phosphate group</td><td>-26.8</td><td>16.1</td><td>4.0</td></tr><tr><td>BP</td><td>2D</td><td> phosphate group</td><td>-30.4</td><td>15.3</td><td>4.6</td></tr></table></body></html>  \n\nreplication.16,17 When anionic phospholipids are depleted, the chromosomal replication of E. coli is inhibited. Although a lot of effort has been expended to investigate the DNA/membrane or polymerase/membrane complex of the bacteria, it is still unclear how the membrane assists in DNA replication.18−22  \n\nCurrently, there are two putative models to explain the DNA replication mechanism: train and factory models. In the train model, the DNA template is fixed and DNA polymerase moves along the DNA template like a train on a track. In the factory model, the DNA polymerase is stationary and DNA is pulled through.23 In both models, the DNA polymerase or DNA might be attached to a fixed site to facilitate DNA replication, which remains elusive to date. In order to understand the role of fixing the polymerase or DNA on plasma membrane for DNA replication, we develop a simple system to mimic the replication site associated with the membrane. We introduce 2D BP as an artificial substrate to promote in vitro DNA replication.  \n\nAlthough the chemical structure and mechanical performance of BP are very different from that of the plasma membrane, BP also shares some similar properties, including (1) 2D planar structure, (2) surface phosphate-containing groups, (3) surface negative charge, (4) hydrophilic surface, and (5) nanoscale thickness (Figure 1). We immobilize either polymerase or DNA on the BP surface (Scheme S1) to replicate DNA. The results show that BP displays excellent capability to improve the efficiency of DNA synthesis by increasing the DNA yield to more than 6 times and reducing the nonspecific products significantly. It could be used as an artificial substrate for DNA replication and an efficient enhancer for in vitro DNA amplification techniques.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# RESULTS AND DISCUSSION  \n\nSimilarities of the Plasma Membrane and BP. The planar phospholipid bilayer of the plasma membrane (Figure 1c) is a natural 2D material. BP also shows a similar 2D structure (Figure 1d,j). The surface of the plasma membrane is covered with phosphate-containing groups. The existence of a $_{\\mathrm{P-O}}$ bond resulting from BP oxidation is confirmed by X-ray photoelectron spectroscopy (XPS) spectrum (Figure 1e). The two strong peaks at 129.7 and $131.6\\ \\mathrm{eV}$ correspond to the $2\\mathrm{p}_{3/2}$ and $2\\mathsf{p}_{1/2}$ orbitals of zerovalent phosphorus, respectively. The weak peak at $133.9\\mathrm{eV}$ is the signal of oxidized phosphorus $\\left(\\mathrm{P-O}\\right)$ .24 The plasma membrane surface carries negative charges ( $-26.8\\mathrm{\\bar{\\mV}}$ because of the negatively charged phosphate group (Figure 1f). Similarly, the BP surface is also negatively charged $\\left(-30.4~\\mathrm{\\mV}\\right)$ , which originated from oxidized phosphorus compounds on its surface. The plasma membrane possesses a hydrophilic surface and a hydrophobic core, which is attributed to the hydrophobic fatty acid tails of the phospholipid buried in the interior and the phosphatecontaining hydrophilic headgroup exposed outside26 (Figure 1a). The contact angle $(\\theta)$ of the bacteria plasma membrane of E. coli is $16.1^{\\circ}$ (Figure ${\\mathrm{lg}}{\\mathrm{,}}$ ), confirming the hydrophilicity of the membrane surface. Likewise, the surface of BP is also hydrophilic $\\mathit{\\theta}=15.3^{\\circ}.$ ; Figure 1h). The thickness of the phospholipid bilayer measured as the phosphorus-to-phosphorus spacing is about $4.0\\ \\mathrm{nm},^{27}$ which is also confirmed by atomic force microscopy (AFM; Figure 1i). The AFM image indicates that the thickness of BP is $4.6\\pm1.2\\ \\mathrm{nm}$ (Figure 1j), which is close to the thickness of the plasma membrane. The above results suggest that BP and the plasma membrane are similar in their 2D structure, thickness, surface phosphate group, negative charge, and hydrophilic surface (Table 1).  \n\nImmobilization of DNA/Polymerase on the BP Surface. In order to investigate the role of fixation for DNA replication, first we immobilized DNA polymerase on the BP surface to initiate in vitro DNA replication in our system. Polymerase chain reaction (PCR) was chosen as a model reaction to evaluate the in vitro DNA amplification efficiency on the surface of BP because of its wide applications in biomedical fields, such as genomic studies, clinical diagnosis, and forensic identification. 28−31 Similar to the factory model, when DNA polymerase is fixed on the BP surface, DNA templates move through the polymerase (Scheme S1a). We immobilized $P f u$ polymerase on the BP surface by either physical adsorption or chemical bonding (Figure 2a,b). 2- Methylimidazole was used to activate the phosphate groups on BP.21 $P f u$ polymerase was conjugated with BP through the reaction between the amino group of polymerase and the phosphate group of BP. Fourier transform infrared spectra (FTIR) and XPS spectra confirmed the conjugation of ${P f u}$ polymerase with BP (Figure S1).  \n\nIn agarose gel electrophoresis, the target band intensity of the amplified products responds to the yield of DNA amplification. The smear or wrong bands located outside the target band position come from nonspecific amplification.22 We found that new DNA strands with a length of 689 bp were successfully synthesized. Both BP and $P f u$ complexes of physical adsorption or chemical bonding could enhance the DNA replication efficiency (Figure 2c). However, because of a sophisticated and time-consuming cross-linking process to obtain chemically bonded $\\mathrm{BP}/P f u$ polymerase, we used physically adsorbed $P f u$ polymerase in subsequent experiments.  \n\nAfter $P f u$ polymerase was physically adsorbed on BP, with increasing BP concentration $(0.02{-}0.32~\\mathrm{\\mg~\\mL^{-1}})$ , the intensity of the target band at 689 bp increased and the smear bands disappeared gradually (Figure 2d). At $0.08~\\mathrm{mg}$ $\\mathrm{mL}^{-1}$ BP, a maximum yield, which was over 6 times that of the control sample without BP (Figure S2), was reached. The yield and specificity of DNA replication increased with the BP concentration, suggesting that BP could promote DNA replication. Then we thoroughly investigated the effect of BP on DNA amplification at different conditions. We found that BP could improve both the specificity and yield of DNA replication in wide ranges of template DNA $(2{-}400~\\mathrm{pg}~\\mu\\mathrm{L}^{-1})$ , primer concentration $\\left(0.4\\mathrm{-}0.08\\mathrm{\\overset{\\sim}{m}M}\\right)$ , and annealing temperature $(25-65~^{\\circ}\\mathrm{C})$ (Figure $S3a,\\mathrm{b,e},$ ). Moreover, it reduced the amplification from 30 to 20 cycles and the extension time from 1 to $0.5\\mathrm{\\min}$ (Figure S3c,d). Thus, BP could significantly shorten the optimization time of in vitro DNA amplification, saving both time and cost. Besides promoting short-fragment amplification, BP can also help the amplification of longer target DNA (3015−5225 bp) and three-round DNA amplification (Figure S4). In addition, we also investigated the effect of BP on DNA amplification using different DNA polymerases. BP could significantly improve the specificity and yield of these polymerases (Figure S5). All of the above results show that BP could promote the DNA replication efficiency in multiple aspects.  \n\n![](images/01479bc715389d57606d1782dec3e030b966054e1809f5676a45020ee1ae0f16.jpg)  \nFigure 2. Fixation of DNA polymerase on BP to promote in vitro DNA amplification. (a) Schematic of $P f u$ polymerase adsorbed on the BP surface. (b) Schematic of $P f u$ polymerase fixed on the BP surface by chemical bonding. (c) DNA amplification using $P f u$ polymerase fixed on BP. (c) Control sample without BP: (1) physically adsorbed $P f u$ polymerase; (2) chemically bonded $P f u$ polymerase. The concentration of BP is $0.08\\mathrm{\\mg\\mL^{-1}}$ . (d) DNA amplification with $P f u$ polymerase adsorbed on BP. BP concentrations increase from 0.02 to $\\mathrm{0.32~mg~mL^{-1}}$ . M: DNA marker. C: control sample without BP. (e) Fluorescent spots of the amplified products in the supernatant and BP precipitation after centrifugation.  \n\nThe polymerase was fixed on the BP surface by electrostatic interaction because the isoelectric point of $P f u$ polymerase is 8.5; therefore, $P f u$ is positively charged in a buffer $\\left(\\mathrm{pH}~7.4\\right)$ and can be adsorbed onto a negatively charged BP surface. The $\\zeta$ potential of BP increased from $-24.9$ to $-9.39\\ \\mathrm{mV}$ after the addition of $P f u$ polymerase (Figure S6). This result shows that there is strong electrostatic interaction between BP and $P f u$ polymerase. The low dissociation constant $\\left(K_{\\mathrm{d}}=1.39\\times10^{-6}\\right.$ M) determined by isothermal titration calorimetry indicates a high affinity of $P f u$ polymerase with BP. The negative Gibbs free energy change $\\mathrm{'}\\Delta G=-32.35\\ \\mathrm{kJ\\moL^{-1}}$ ; Figure S7) also suggests spontaneous binding of Pfu polymerase with BP.32 AFM showed that $P f u$ polymerase molecules were adsorbed onto BP (Figure S8). The height of $\\mathrm{BP}/P f u$ increased from 4.6 nm of BP to $10.5\\ \\mathrm{~nm}$ of $\\mathbb{B P}/P f u$ . Bicinchoninic acid measurement confirmed that $69\\%$ of Pfu polymerase was adsorbed onto the BP surface (Figure S9). A fluorescent spots study was performed to investigate whether DNA replication might occur on the BP surface. We used SYBR green I to dye the amplification product at different replication cycles because the fluorescent dye SYBR green I can enter the minor groove of double-stranded DNA (dsDNA).33 The spots of BP precipitation after centrifugation at 1−15 cycles were much brighter than those of the supernatant without BP, indicating that DNA amplification of the initial 15 cycles would occur on the surface of BP (Figure 2e and Table S6).  \n\nReal-time PCR (RT-PCR) was performed to monitor the amplification of a targeted DNA molecule during the amplification process. The threshold cycle $\\left(C_{\\mathrm{T}}\\right)$ represents the PCR cycle at which the fluorescent signal passes the fixed threshold. At the same initial concentration of template DNA, a smaller $C_{\\mathrm{T}}$ value indicates that the amplified DNA products can reach the threshold more quickly. The $C_{\\mathrm{T}}$ values decreased gradually after the ddition of BP, suggesting that BP would facilitate DNA amplification (Figure S10a). The melting temperature $\\left(T_{\\mathrm{m}}\\right)$ is the temperature at which the dsDNA strand separates. As the BP concentration increases, $T_{\\mathrm{m}}$ decreases from 73.8 to $71.4~^{\\circ}\\mathrm{C},$ indicating that BP might enhance the separation of dsDNA. Melting curve analysis indicated that BP decreased the $T_{\\mathrm{m}}$ value of dsDNA and accelerated the dsDNA denaturation process to obtain more single-stranded DNA (ssDNA; Figure S10b), which would benefit DNA replication on the surface of BP. The oxidized phosphorus compound could bind the $-\\mathrm{NH}$ or $\\scriptstyle{\\mathrm{C}}={\\mathrm{O}}$ groups of the exposed bases of ssDNA by hydrogen bonding between $\\scriptstyle\\mathrm{P=O\\cdotN\\bar{H}}$ or $\\mathrm{P-OH\\cdotO=C}$ , resulting in strong interaction between ssDNA and BP.34  \n\nImmobilization of a DNA Primer on the BP Surface. On the other hand, $\\mathsf{A l}^{3+}$ -modified BP $\\left(\\mathrm{BP-Al}^{3+}\\right)$ was used to fix the ${\\boldsymbol{5}}^{\\prime}$ -thiolated forward primer on the BP surface by $_{\\mathrm{Al}-S}$ bonding. Fluorescent intensity measurements confirmed that the DNA primer was immobilized on the ${\\mathrm{BP}}{\\cdot}{\\mathrm{Al}}^{3+}$ surface (Figure S11). This system could represent the train model because the DNA primer is fixed on the BP surface and the polymerase moves along the DNA template (Figure 3a).  \n\nThe new DNA products were amplified on the BP surface, and the yield increased gradually with increasing concentration of the BP- $\\mathbb{A}^{3+}$ -F1 DNA primer (Figure 3b). The DNA yield with BP was obviously higher than that of the control sample without BP (Figure 3c). A fluorescent spots study of 1−30 cycles showed that the precipitation of BP exhibited much stronger fluorescence than the supernatant, indicating that DNA replication would occur on the BP surface (Figure 3d). These results show that fixation of either the polymerase or the DNA primer could be effective in promoting in vitro DNA replication on the BP surface.  \n\nEffect of the Five Properties of BP on in Vitro DNA Amplification. In order to understand the importance of the five factors of membrane for DNA amplification, we changed the 2D dimension, surface phosphate group, surface charge, hydrophilicity, and thickness of BP, respectively, and compared their effects on in vitro DNA amplification. First, we used $\\mathrm{H}_{2}\\mathrm{O}_{2}$ as the oxidant to destroy the 2D structure of BP.  \n\n![](images/acda4cac22769111d3ee0b2efcea0209fa9131f7f7f5f37d6495a76b72d3e0fb.jpg)  \nFigure 3. BP promotes in vitro DNA amplification by immobilization of the DNA primer on the $\\mathrm{BP\\mathrm{\\cdot}A l^{3+}}$ surface. (a) Schematic of DNA replication on BP with a fixed forward primer. The forward DNA primer (black) is fixed on the BP surface. (b) Effect of the concentration of F1 DNA primer fixed on the BP surface upon DNA amplification. ${\\mathrm{BP}}{\\cdot}{\\mathrm{Al}}^{3+}$ was incubated with thiolated F1 DNA primer and centrifuged to remove unbound primers. The precipitate (BP$\\mathbb{A}^{3+}$ -F1 primer) was collected and redispersed in water. A total of $_{0-5}$ $\\mu\\mathrm{L}$ of BP- $\\mathbf{\\cdotAl}^{3+}$ -F1 primer was added to the amplification system. (c) DNA amplification using DNA fixed on BP. M: DNA marker. C: control sample with BP. The primers were not fixed on BP. 1: F1 DNA primer fixed on BP. (d) DNA amplification occurs on the BP surface supported by a fluorescent spots study. The concentration of BP and ${\\mathrm{B}}{\\bar{\\mathrm{P}}}{\\cdot}{\\mathrm{Al}}^{3+}$ is $\\mathrm{0.08~mg~mL^{-1}}$ .  \n\nTransmission electron microscopy (TEM) images showed that the 2D structure of BP was damaged by $\\mathrm{H}_{2}\\mathrm{O}_{2}$ oxidation (Figure 4a). XPS spectra suggested that the oxidation degree of BP increased with increasing concentration of $\\mathrm{H}_{2}\\mathrm{O}_{2}$ (Figure S12). The DNA replication efficiency decreased with increasing oxidation degree of BP (Figure 4a), confirming the important role of the 2D structure of BP in promoting DNA replication.  \n\nSecond, we used sodium dodecyl sulfate (SDS) with a sulfonic group and poly(acrylic acid) (PAA) with a carboxyl group to modify the surface of BP (Figures 4b and S13). We found that BP with phosphate groups promotes in vitro DNA amplification, while BP/SDS and BP/PAA inhibited DNA replication (Figure 4b). We also modified BP with sodium monododecyl phosphate (SDP) and found that it inhibited DNA replication (Figure S14, band 2), indicating that both the phosphate group and BP sheets play important roles in promoting PCR. Althought SDS and SDP contain phosphate groups, their hydrophobic dodecyl chains can penetrate the hydrophobic protein core, thus disrupting the tertiary and secondary structures of $P f u$ polymerase.35 As a result, DNA replication was inhibited. The exact function of phosphate groups for DNA replication remains unclear. Modifying different nanomaterials with phosphate functional groups might help to explain the mechanism for BP-promoted DNA replication.  \n\nThird, we investigated the effect of charge on DNA amplification, while negative surface charge is another common property of BP and the plasma membrane. We used neutral poly(ethylene glycol) (PEG), positively charged lysine, and chitosan to modify BP. For neutral PEG-modified BP (Figure  \n\n4c, band 2), the DNA replication efficiency decreased compared with that of negatively charged BP (band 1). After lysine and chitosan modification, the $\\zeta$ potentials of modified BP increased from $-30.4~\\mathrm{mV}$ of BP to $-6.9\\ \\mathrm{mV}$ of BP/lysine and $16.8\\ \\mathrm{mV}$ of BP/chitosan, respectively (Figure $\\mathsf{4c})$ , and DNA replication was completely inhibited (Figure 4c, bands 3 and 4). Thus, negative surface charge plays an important role in DNA replication. The effect of negative charge on DNA replication still needs further investigation, such as applying an electric field to control the surface charge of BP.  \n\nTo understand that the hydrophilic surface is also important for DNA amplification, BP was modified with weakly hydrophobic $\\mathrm{\\hat{(}C H_{3}C H_{2})_{2}N C H_{2}-}$ (DEMA) and strongly hydrophobic 2-naphthalenethiol (2-NAT). The contact angles of modified BP increased from $15.3^{\\circ}$ of BP to $50.1^{\\circ}$ of BP/ DEMA and $119.2^{\\circ}$ of BP ${\\bf-A l}^{3+}2\\mathrm{NAT}$ (Figure $\\mathrm{4d}\\`_{,}$ ). The result shows that DNA amplification was also completely inhibited by hydrophobic BP/DEMA and ${\\mathrm{BP}}{\\cdot}{\\mathrm{Al}}^{3+}2{\\mathrm{NAT}}$ (Figure 4d, bands 2 and 3). These results suggest that the hydrophilic BP surface also makes an important contribution to DNA replication.  \n\nFinally, we explored the effect of the BP thickness on DNA replication. We prepared BP with different thicknesses (86.3, 42.4, and $4.8~\\mathrm{nm}$ , respectively; Figures $_{4\\mathrm{e}}$ and S15). BP with a thickness $(4.8~\\mathrm{nm})$ close to that of the plasma membrane (4.0 nm) has the best chance to promote DNA replication (Figure 4e, band 3). The above studies demonstrated that destroying any of the five aspects of BP would reduce the DNA replication efficiency. Therefore, all five properties are important for DNA replication. Despite the similarities of BP with the plasma membrane, the following aspects still need further investigation. The phospholipid membrane is permeable, and therefore part of the DNA polymerase or DNA could insert within the membrane, which is not possible in BP. Second, the phospholipid membrane is soft and has a potential curvature to its interface, while BP is a flat and rigid sheet. Finally, the lipid molecules are mobile and can diffuse in the plasma membrane, therefore changing the properties of the local DNA polymerase when they adsorb to its surface. Further study is required to investigate whether these properties are important in the replication process and how they contribute to the amplification rate.  \n\nHere we also compared BP with several other nanomateri$\\mathrm{als}^{36-38}$ owning part of the five similarities (Figure $S16\\mathrm{a}-\\mathrm{c}$ and Table S7). GO has no surface phosphate group. Few-layer boron nitride (BN) sheets are hydrophobic and possess neither a surface phosphate group nor a negative charge. Gold nanoparticles (GNPs) are zero-dimensional (0D) nanomaterials with no surface phosphate group. At a fixed concentration $(0.08~\\mathrm{mg~mL^{-1}}),$ , BP showed the best performance, followed by GNPs, GO, and BN (Figure S17a). We explored the optimized concentrations of GO, BN, and GNPs for DNA amplification (Figure $\\mathrm{S16d-f)}$ . Although all of them showed enhanced efficiency, BP displayed the strongest amplification without any smears, indicating its superiority over other nanomaterials (Figure S17b). BP had the lowest $C_{\\mathrm{T}}$ values in both fixed and optimal concentrations (Figure S17c,d), which suggests that BP would accelerate DNA amplification. BP is more biocompatible than the other nanomaterials because of its similar structure to the plasma membrane (Figure 1a). Another unique advantage of BP is that it can be degraded into biocompatible phosphorus oxides without any residual. However, GO, BN, and GNPs are all nondegradable materials;  \n\n![](images/cc29f2848ae12571dffefc114e790cdee25f34faa30af61e9b5a17c6c967c607.jpg)  \nFigure 4. Effect of the five properties of BP on in vitro DNA amplification. (a) BP with intact 2D structure promotes DNA amplification. The 2D dimension of BP is damaged by $\\mathrm{H}_{2}\\mathrm{O}_{2}$ . Samples $_{1-7}$ are amplification products with BP oxidized by 0, 0.01, 0.02, 0.04, 0.05, 0.06, and $0.07\\%$ $\\mathrm{H}_{2}\\mathrm{O}_{2},$ respectively. The TEM images show the damaged structure of BP. (b) BP with phosphate groups promotes in vitro DNA amplification: (1) BP $\\mathrm{(P\\bar{O}_{4}{}^{3-})}$ ; (2) BP/SDS $(\\mathrm{SO}_{3}\\mathrm{^{-}})$ ; (3) BP/PAA $(\\mathrm{COO^{-}})$ . (c) Negatively charged BP promotes in vitro DNA amplification: (1) BP $(-)$ ; (2) BP/PEG (neutral); (3) BP/lysine $\\left(+\\right)$ ; (4) BP/chitosan $\\left(+\\right)$ . $\\zeta$ potentials of BP, BP/PEG, BP/lysine, and BP/chitosan are $-30.4_{;}$ $-20.2$ , $-6.9,$ and $16.8~\\mathrm{mV},$ respectively. (d) BP with hydrophilic surface promotes in vitro DNA amplification: (1) BP (hydrophilic); (2) BP/DEMA (weakly hydrophobic); (3) ${\\mathrm{BP}}{\\cdot}{\\mathrm{Al}}^{3+}2{\\mathrm{NAT}}$ (strongly hydrophobic). The contact angles of BP, BP/DEMA, and B ${\\mathrm{.P}}{\\mathrm{-}}{\\mathrm{Al}}^{3+}2{\\mathrm{N}}{\\mathrm{AT}}$ are $15.3^{\\circ}$ , $50.1^{\\circ};$ , and $119.2^{\\circ}.$ respectively. (e) BP with smaller thickness promotes DNA replication. The thicknesses of BP in samples 1−3 are 86.3, 42.4, and $4.8\\ \\mathrm{nm},$ respectively. M: DNA marker. C: control sample without BP. The concentrations of BP and modified BP are both $0.08~\\mathrm{mg~mL^{-1}}$ .  \n\nthus, an additional purification process is required to remove these materials, which could be harmful for subsequent transformation, transcription, or sequencing procedures. Compared with 0D BP quantum dots and soft BP hydrogels composed of agarose and PEGylated BP sheets, which have been used in cancer therapy and imaging,2,39 few-layer BP sheets mimic the 2D plasma membrane and are more suitable as artificial substrates for DNA replication. Although BP has negligible cytotoxicity, its instability has limited its commercialization. Strategies to enhance the ambient stability of BP and prolong its preservation time need to be developed to promote the biomedical applications of BP. For example, Lei et al. offers an efficient approach to preventing BP sheets from oxidation by adatom decoration on BP, which could significantly shift their conduction-band minimum below the $\\mathrm{O}_{2}/\\mathrm{O}_{2}^{-}$ redox potential.40  \n\nThe above results suggest that mimicking all five properties of the plasma membrane might be important to promote in vitro DNA replication. Meanwhile, we also sequenced the amplification products in the absence or presence of BP. The sequence alignment showed no difference. One example of the 4024 bp amplified product sequencing is given in Figure S18. The result indicates that BP could not only improve DNA replication but also maintain the fidelity of $P f u$ polymerase.  \n\nDNA Amplification of Clinical Samples with BP. For sophisticated DNA samples extracted from clinical samples or multiple-round $\\operatorname{PCR},$ nonspecific DNA fragments and low yield remain a problem. We investigated the effect of BP on human mitochondrial DNA amplification. Figure S19 shows that BP improved the efficiency of three-round PCR and could amplify long DNA fragments. These results indicate that BP could also be used to improve the replication efficiency of clinical DNA samples.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# CONCLUSIONS  \n\nOur study demonstrated that BP shares five similar properties with a phospholipid plasma membrane, including its 2D dimension, surface group, surface charge, hydrophilicity, and thickness. Fixing DNA or polymerase on the BP surface could promote DNA replication with high efficiency. This study opened up more opportunities for the application of BP as an artificial substrate for DNA replication and an efficient enhancer for in vitro DNA amplification techniques.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 6,
+        "chunk": "# ASSOCIATED CONTENT",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# $\\bullet$ Supporting Information  \n\nThe Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsanm.9b02456.  \n\nMaterials and methods, schematic view of DNA replication models on the surface of BP, characterization of the $\\ensuremath{\\mathrm{BP}}\\cdot\\ensuremath{\\boldsymbol{P}}\\ensuremath{\\boldsymbol{f u}}$ complex, effect of BP on PCR, measurements of BP and $P f u$ polymerase interaction, calculation of the maximum amount of DNA molecules on BP and the amount of DNA obtained at each PCR cycle, RT-PCR, fluorescent intensity measurement of ssDNA-modified BP, XPS spectra of BP with different oxidation degrees, FTIR spectra of SDS- and PAAmodified BP, effect of SDP-modified BP on $\\mathrm{PCR},$ AFM images of BP with different thicknesses, comparison of the effects of different nanomaterials on $\\mathrm{PCR},$ effect of BP on the fidelity of $P f u$ polymerase, and effect of BP on PCR of DNA isolated from clinical samples (PDF)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# AUTHOR INFORMATION",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# Corresponding Authors  \n\nLiping Sun − Key Laboratory of Biomedical Engineering of Fujian Province, Department of Biomaterials, College of Materials, Xiamen University, Xiamen 361005, P. R. China; $\\circledcirc$ orcid.org/0000-0001-8707-7446; Phone: $+86-592$ - 2183181; Email: sunliping@xmu.edu.cn Jian Weng − Key Laboratory of Biomedical Engineering of Fujian Province, Department of Biomaterials, College of Materials, Xiamen University, Xiamen 361005, P. R. China; $\\circledcirc$ orcid.org/0000-0002-5813-6061; Phone: $+86-592$ - 2183181; Email: jweng@xmu.edu.cn  \n\nAuthors Jie Gui − Key Laboratory of Biomedical Engineering of Fujian Province, Department of Biomaterials, College of Materials, Xiamen University, Xiamen 361005, P. R. China; $\\circledcirc$ orcid.org/ 0000-0001-8562-6990 Yunfei Bai − Key Laboratory of Biomedical Engineering of Fujian Province, Department of Biomaterials, College of Materials, Xiamen University, Xiamen 361005, P. R. China Huizhen Li − Key Laboratory of Biomedical Engineering of Fujian Province, Department of Biomaterials, College of Materials, Xiamen University, Xiamen 361005, P. R. China; $\\circledcirc$ orcid.org/0000-0002-1773-6749 Jian Peng − Key Laboratory of Biomedical Engineering of Fujian Province, Department of Biomaterials, College of Materials, Xiamen University, Xiamen 361005, P. R. China Yufan Huang − Department of Breast Surgery, The First Affiliated Hospital of Xiamen University, Xiamen 361003, P. R. China  \n\nComplete contact information is available at: https://pubs.acs.org/10.1021/acsanm.9b02456",
+        "category": " References"
+    },
+    {
+        "id": 10,
+        "chunk": "# Author Contributions  \n\nL.S. and J.W. designed the experiments, performed data interpretation, and wrote the manuscript. J.G., Y.B., H.L., and J.P. performed the experiments and analyzed the data. Y.H. collected clinical samples.",
+        "category": " References"
+    },
+    {
+        "id": 11,
+        "chunk": "# Funding  \n\nThis work was supported by the National Natural Science Foundation of China (Grants 81872415 and 81571764).",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# Notes  \n\nThe authors declare no competing financial interest.  \n\nREFERENCES   \n(1) Eswaraiah, V.; Zeng, Q.; Long, Y.; Liu, Z. Black phosphorus nanosheets: synthesis, characterization and applications. Small 2016, 12 (26), 3480−3502.   \n(2) Qiu, M.; Wang, D.; Liang, W.; Liu, L.; Zhang, Y.; Chen, X.; Sang, D.; Xing, C.; Li, Z.; Dong, B.; Xing, F.; Fan, D.; Bao, S.; Zhang, H.; Cao, Y. Novel concept of the smart NIR-light-controlled drug release of black phosphorus nanostructure for cancer therapy. Proc. Natl. Acad. Sci. U. S. A. 2018, 115 (3), 501−506.   \n(3) Tao, W.; Kong, N.; Ji, X.; Zhang, Y.; Sharma, A.; Ouyang, J.; Qi, B.; Wang, J.; Xie, N.; Kang, C.; Zhang, H.; Farokhzad, O.; Kim, J. Emerging two-dimensional monoelemental materials (Xenes) for biomedical applications. Chem. Soc. Rev. 2019, 48 (11), 2891−2912. (4) Qiu, M.; Singh, A.; Wang, D.; Qu, J.; Swihart, M.; Zhang, H.; Prasad, P. 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Biotechnol. 2016, 100 (10), 4255−4267.   \n(20) Lemon, K. P.; Grossman, A. D. The extrusion-capture model for chromosome partitioning in bacteria. Genes Dev. 2001, 15 (16), 2031−2041.   \n(21) Cook, P. R. Molecular biology - The organization of replication and transcription. Science 1999, 284 (5421), 1790−1795.   \n(22) Prasad, D.; Muniyappa, K. The anionic phospholipids in the plasma membrane play an important role in regulating the biochemical properties and biological functions of RecA proteins. Biochemistry 2019, 58 (9), 1295−1310.   \n(23) Lemon, K. P.; Grossman, A. D. Localization of bacterial DNA polymerase: evidence for a factory model of replication. Science 1998, 282 (5393), 1516−1519.   \n(24) Tao, W.; Zhu, X.; Yu, X.; Zeng, X.; Xiao, $\\mathrm{Q.;}$ Zhang, X.; Ji, X.; Wang, X.; Shi, J.; Zhang, H.; Mei, L. Black Phosphorus Nanosheets as a Robust Delivery Platform for Cancer Theranostics. Adv. Mater. 2017, 29 (1), 1603276.   \n(25) Brent, J. R.; Ganguli, A. K.; Kumar, V.; Lewis, D. J.; McNaughter, P. D.; O’Brien, P.; Sabherwal, P.; Tedstone, A. A. On the Stability of Surfactant-Stabilised Few-Layer Black Phosphorus in Aqueous Media. RSC Adv. 2016, 6 (90), 86955−86958.   \n(26) Van Meer, G.; Voelker, D. R.; Feigenson, G. W. Membrane lipids: where they are and how they behave. Nat. Rev. Mol. Cell Biol. 2008, 9 (2), 112−124.   \n(27) Garrett, R. H.; Grisham, C. M. Biochemistry; Higher Education Press, 2015.   \n(28) Ottesen, E. A.; Hong, J. W.; Quake, S. R.; Leadbetter, J. R. Microfluidic digital PCR enables multigene analysis of individual environmental bacteria. Science 2006, 314 (5804), 1464−1467. (29) Lynch, C.; Fleming, R. A review of direct polymerase chain reaction of DNA and RNA for forensic purposes. Wiley Interdisciplinary Reviews: Forensic Science 2019, 1, e1335.   \n(30) Lohrmann, R.; Orgel, L. E. Prebiotic activation processes. Nature 1973, 244 (5416), 418−420.   \n(31) Green, M. R.; Sambrook, J. Polymerase Chain Reaction. Molecular Cloning: A Laboratory Manual; Cold Spring Harbor Laboratory Press, 2012; Chapter 7.   \n(32) Janek, T.; Czyżnikowska, Ż.; Łukaszewicz, M.; Gałȩzowska, J. The effect of Pseudomonas fluorescens biosurfactant pseudofactin II on the conformational changes of bovine serum albumin: Pharmaceutical and biomedical applications. J. Mol. Liq. 2019, 288, 111001.   \n(33) Dragan, A. I.; Pavlovic, R.; McGivney, J. B.; Casas-Finet, J. R.; Bishop, E. S.; Strouse, R. J.; Schenerman, M. A.; Geddes, C. D. SYBR Green I: Fluorescence Properties and Interaction with DNA. J. Fluoresc. 2012, 22 (4), 1189−1199.   \n(34) Jeffrey, G. A.; Saenger, W. Hydrogen bonding in biological structures; Springer Science & Business Media, 2012.   \n(35) Poghosyan, A. H.; Schafer, N. P.; Lyngsø, J.; Shahinyan, A. A.; Pedersen, J. S.; Otzen, D. E. Molecular dynamics study of ACBP denaturation in alkyl sulfates demonstrates possible pathways of unfolding through fused surfactant clusters. Protein Eng., Des. Sel. 2019, No. gzz037.   \n(36) Chen, P.; Pan, D.; Fan, C.; Chen, J.; Huang, K.; Wang, D.; Zhang, H.; LI, Y.; Feng, G.; Liang, P.; He, L.; Shi, Y. Gold nanoparticles for high-throughput genotyping of long-range haplotypes. Nat. Nanotechnol. 2011, 6 (10), 639−644.   \n(37) Jia, J.; Sun, L.; Hu, N.; Huang, G.; Weng, J. Graphene enhances the specificity of the polymerase chain reaction. Small 2012, 8 (13), 2011−2015.   \n(38) Li, H.; Huang, J.; Lv, J.; An, H.; Zhang, X.; Zhang, Z.; Fan, C.; Hu, J. Nanoparticle PCR: Nanogold-assisted PCR with enhanced specificity. Angew. Chem., Int. Ed. 2005, 44 (32), 5100−5103.   \n(39) Sun, Z.; Zhao, Y.; Li, Z.; Cui, H.; Zhou, Y.; Li, W.; Tao, W.; Zhang, H.; Wang, H.; Chu, P. K.; Yu, X. F. $\\mathrm{TiL}_{4}$ -coordinated black phosphorus quantum dots as an efficient contrast agent for in vivo photoacoustic imaging of cancer. Small 2017, 13 (11), 1602896.  \n\n(40) Lei, S.; Shen, H.; Sun, Y.; Wan, N.; Yu, H.; Zhang, S. Enhancing the ambient stability of few-layer black phosphorus by surface modification. RSC Adv. 2018, 8 (26), 14676−14683.",
+        "category": " References"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/herkert-et-al-2022-characterization-of-per-and-polyfluorinated-alkyl-substances-present-in-commercial-anti-fog-products.json b/task2/task2-chunks/herkert-et-al-2022-characterization-of-per-and-polyfluorinated-alkyl-substances-present-in-commercial-anti-fog-products.json
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@@ -0,0 +1,92 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Characterization of Per- and Polyfluorinated Alkyl Substances Present in Commercial Anti-fog Products and Their In Vitro Adipogenic Activity  \n\nNicholas J. Herkert, Christopher D. Kassotis, Sharon Zhang, Yuling Han, Vivek Francis Pulikkal, Mei Sun, P. Lee Ferguson, and Heather M. Stapleton\\*",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# Cite This: Environ. Sci. Technol. 2022, 56, 1162−1173",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# ACCESS  \n\nMetrics & More  \n\nArticle Recommendations  \n\nSupporting Information  \n\nABSTRACT: Anti-fog sprays and solutions are used on eyeglasses to minimize the condensation of water vapor, particularly while wearing a mask. Given their water-repellent properties, we sought to characterize per- and polyfluorinated alkyl substance (PFAS) compounds in four anti-fog spray products, five anti-fog cloth products, and two commercial fluorosurfactant formulations suspected to be used in preparing anti-fog products. Fluorotelomer alcohols (FTOHs) and fluorotelomer ethoxylates (FTEOs) were detected in all products and formulations. While 6:2 FTOH and the 6:2 FTEO polymeric series were predominant, one anti-fog cloth and one formulation contained 8:2, 10:2, 12:2, 14:2, and 16:2 FTOH and FTEO polymeric series. PFAS concentrations varied in samples and were detected at levels up to $25,000~\\mu\\mathrm{g/mL}$ in anti-fog sprays and $185,000~\\mu\\mathrm{g}$ $(\\mathrm{g}\\ \\mathrm{cloth})^{-1}$ in anti-fog cloth products. The total organic fluorine (TOF) measurements of anti-fog products ranged from 190 to $20,700~\\mu\\mathrm{g/mL}$ in sprays and 44,200 to $131,500\\mu\\mathrm{g}\\:(\\mathrm{g}\\:\\mathrm{cloth})^{-1}$ in cloths. Quantified FTOHs and FTEOs accounted for $1-99\\%$ of TOF mass. In addition, all four anti-fog sprays and both commercial formulations exhibited significant cytotoxicity and adipogenic activity (either triglyceride accumulation and/or pre-adipocyte proliferation) in murine 3T3-L1 cells. Results suggest that FTEOs are a significant contributor to the adipogenic activity exhibited by the anti-fog sprays. Altogether, these results suggest that FTEOs are present in commercial products at toxicologically relevant levels, and more research is needed to fully understand the health risks from using these PFAS-containing products.  \n\n![](images/819c3201c797574b3b257d4717d3c4284e60a010d1bf7dff1a0f908704ef1526.jpg)  \n\nKEYWORDS: PFAS, fluorotelomer ethoxylate (FTEOs), anti-fog, adipogenic activity, endocrine disruptors, 3T3-L1",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# INTRODUCTION  \n\nDue to the COVID19 pandemic, there has been an increase in the use of protective gear, including masks and face shields, particularly among medical staff and other essential workers. The fogging of eyeglasses while wearing full protective gear can be challenging, and a variety of approaches are used to overcome this problem, including applying dish soap, hand sanitizer, iodophor (iodine complexed with a solubilizing agent), or antifogging agents to the goggles.1 Anti-fog solutions have been one of the solutions recommended by health care professionals to help prevent fogging of glasses while wearing masks.2−4 Many of these products are marketed as “safe” and “non-toxic”; however, the ingredients on these products are not fully disclosed, although the ingredients listed on some products indicate the presence of fluorinated compounds. Given that they provide a water-repellant property, it seemed likely that these products could contain per- and polyfluoroalkyl substances (PFAS).  \n\nPFAS are a large class of chemical compounds that have been used for their stain- and water-repellent properties in commercial products for decades.5−15 Due to the widespread use of PFAS, they have been detected nearly ubiquitously in environmental matrices and human serum. $7,9,\\dot{11},13,14,\\dot{1}6-23$ PFAS have been shown to have a number of toxicological effects in laboratory studies and have been associated with thyroid disorders, immunotoxic effects, and various cancers in epidemiology studies.20,24−28  \n\nMost research to date has focused on perfluoroalkyl acids (PFAAs), such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), which are known to be more toxic than many other studied PFAS. However, there are multiple classes of PFAS. For example, fluorotelomer alcohols (FTOHs) are primarily used in the production of PFAS for commercial applications,6,29−36 a lthough FTOHs are sometimes used directly in fast food packaging and stain- and waterrepellent textiles.31,37−39 Due to these direct and indirect uses (i.e., manufacturing residual) of FTOHs in commercial products, they have been widely detected in environmental samples and human serum. $^{6,30,40^{\\bullet}-42}$ FTOHs are of particular concern in the indoor environment where they are released from commercial products and are frequently a dominant class of PFAS detected in dust and indoor air. $^{17,33,41,43-52}$ Previous studies have shown that FTOHs and other precursor compounds can transform to more toxic and stable ionic PFAAs via aerobic and metabolic pathways.6,9,29,41,43,53−63 This could be particularly important for exposure in the indoor environment as FTOHs measured in indoor air have been found to be significantly correlated with serum PFAAs, suggesting that metabolic transformations are occurring in the body and that exposure to FTOHs may be a source of exposure to the more toxic PFAS in the indoor environment.64,65  \n\n![](images/6339433745782fa3071db0fd04d7c86394a3e8a4ab60211299c4debb3c769c33.jpg)  \nFigure 1. Analytical workflow for sample analysis (left) and chemical structures identified in anti-fog products (right). A represents FTOHs, B represents FTEOs, C represents fluorotelomer ethers, D represents fluorotelomer fumarates, and E represents FTEO ethers. Compounds were identified with $n$ as 6, 8, 10, 12, 14, or 16; $n_{2}$ as 6, 8, or $10;n_{3}$ as $6$ ; and $x$ ranging from 1 to 8 via GC−MS analysis and from 2 to 13 via LC-MS analysis.  \n\nFluorotelomer ethoxylates (FTEOs), in contrast, are a class of fluorinated compounds that have been infrequently studied. Frömel and Knepper (2010) studied the biodegradation of FTEOs from commercial mixtures in a wastewater treatment plant (WWTP),66 but to the best of our knowledge, FTEOs have not yet been identified in any commercial products. Several types of polyethoxylated surfactants, and some PFAS, have been shown to induce adipogenesis in vitro, implicating them as potential endocrine disruptors;67−71 however, no research has determined if fluorinated polyethoxylates could produce similar effects.  \n\nGiven that these anti-fog products claim to prevent condensation of water vapor on eyeglasses, we sought to determine if these products contained a PFAS chemistry. The two main objectives of this study were to (1) identify and characterize PFAS compounds present in commercially available anti-fog sprays and cloth wipes and (2) investigate the adipogenic activity of the anti-fog sprays in a common in vitro pre-adipocyte model. More specifically, 10 non-ionic PFAS were targeted via gas chromatography (GC)−high-resolution mass spectrometry (HRMS) methods and 28 ionic PFAS were targeted via liquid chromatography−mass spectrometry (LC− MS/MS) methods. Additional analyses using high-performance liquid chromatography (HPLC)−HRMS methods were employed to quantify novel analytes (FTEOs) in anti-fog products and two PFAS commercial formulations. HPLC combined with charged aerosol detection (CAD) was employed to determine ethoxymer distribution in commercial mixtures, and an ion chromatography method was used to measure total organic fluorine (TOF) in all anti-fog samples and commercial mixtures. In vitro assays were also used to characterize the adipogenic activity in anti-fog sprays, commercial formulations, and individual analytes of interest. Figure 1 illustrates a simplified version of the sample workflow and analyses used that are presented in full in the Methods and Materials section.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# METHODS AND MATERIALS  \n\nAnti-fog Consumer Products and Commercial Formulations. Four anti-fog sprays and five anti-fog cloths were purchased from Amazon.com. The products were selected based on the highest number of positive reviews at the time of purchase (Table S1). Two commercially relevant non-ionic fluorosurfactant formulations were also analyzed. A 6:2 FTEO mixture (polyethylene oxide and mono(3,3,4,4,5,5,6,6,7,7,8,8,8)-tridecafluorooctyl ether; CAS#: 52440-44-4) was obtained from BOC Sciences, and a legacy sample of Zonyl FSN-100 (E.I. du Pont de Nemours & Company) was received as a gift of Prof. Jennifer Field (Oregon State University).  \n\nAnalytical Methods for GC Analysis PFASs in Anti-fog Products. Anti-fog sprays were diluted in a variety of analytical grade solvents (hexane, ethyl acetate, acetone, and dichloromethane) to determine which solution was optimal for GC−MS analysis. Based on the peak responses on a Q-Exactive GC  \n\nOrbitrap, acetone produced the optimal results. Serial dilutions of anti-fog sprays were created in acetone and spiked with isotopically labeled 2-perfluorohexyl-[1,2-13C2]-ethanol(6:2) and 2-perfluorooctyl-[1,2-13C2]-ethanol(8:2) (Wellington Laboratories, Guelph, Ontario). Anti-fog cloth products were analyzed by cutting and weighing out ${\\sim}0.5\\mathrm{g}$ of sections of cloth and extracting via sonication in $10~\\mathrm{\\mL}$ of 1:1 hexane/ dichloromethane three times. A small aliquot of the combined extract was added to a GC vial, diluted with ethyl acetate to 1 ${\\mathrm{mL}},$ and spiked with 13C 6:2 FTOH and 13C 8:2 FTOH. All samples were analyzed in triplicates.  \n\nThe samples were analyzed based on previously published methods.72 Briefly, FTOHs were analyzed on a Q Exactive GC hybrid quadrupole-Orbitrap GC−MS/MS system (Thermo Scientific) operated in the full-scan positive chemical ionization (PCI) mode. Seven additional PFAS precursor compounds were screened but not found in any samples analyzed (Table S2). The GC was equipped with an Agilent J&W DB-WAX GC capillary column ( $30\\mathrm{m}\\times0.25\\mathrm{mm}\\mathrm{ID}$ and $0.25\\mu\\mathrm{m}$ film thicknesses) with methane as the reagent gas flowing at $1.5~\\mathrm{\\mL/min}$ . The programmable temperature vaporizer inlet was operated in the splitless injection mode with a 1 μL injection. The GC oven temperature program was $50~^{\\circ}\\mathrm{C}$ for $2~\\mathrm{min}$ , $50{-}70~^{\\circ}\\mathrm{C}$ at $3^{\\circ}\\mathrm{C}/$ $\\mathrm{min},70{-}130^{\\circ}\\mathrm{C}$ at $10^{\\circ}\\mathrm{C}/\\mathrm{min},130{-250}$ at $20^{\\circ}\\mathrm{C}/\\mathrm{min},$ and held for $20\\mathrm{min}$ . The ion source was kept at $250^{\\circ}\\mathrm{C}$ . The samples were run with a scan range of $70{-}1050m/z$ and quantified using the TraceFinder software. The analytes were measured with a standard targeted approach that included a five-point calibration curve and included the use of isotopically labeled standards.  \n\nLC−MS/MS Methods for Ionic PFAS Analysis. Ionic PFAS were analyzed by an Agilent 1260 Infinity II LC system coupled to an Agilent 6460A triple quadrupole mass spectrometry $\\left(\\mathrm{LC-MS/MS}\\right)$ . Chromatographic separation was achieved under gradient conditions using a C18 column (Agilent Zorbax Eclipse XDB-C18, $4.6\\times50\\ \\mathrm{mm}$ and $1.8\\ \\mu\\mathrm{m}$ particle size) preceded by a $4.6\\times5~\\mathrm{mm}~\\mathrm{XDB-C18}$ guard column. The mobile phases water (A) and methanol (B) were both modified with $2\\ \\mathrm{mM}$ ammonium acetate. The gradient program is as follows: initial condition $30\\%$ B, held for $1.5\\mathrm{min}$ , increased to $95\\%$ B over $2\\mathrm{min}$ , held for $6\\mathrm{min}$ , increased to $100\\%$ B over $3~\\mathrm{min}$ , returned to the initial condition $30\\%$ B over 0.5 min, and held for $5.5\\ \\mathrm{min}$ . The flow rate was $0.4~\\mathrm{mL/min}$ , the column temperature was $45^{\\circ}\\mathrm{C},$ and the injection volume was 20 $\\mu\\mathrm{L}$ . Quantification was performed using multiple reaction monitoring transitions and run in the electrospray negative mode. Full results for ionic PFAS are presented in Table S3. Analytes were measured with a standard targeted approach that included a five-point calibration curve and included the use of isotopically labeled standards.  \n\nHPLC−CAD Methods for Characterizing Ethoxymer Distribution. FTEOs in the 6:2 FTEO fluorosurfactant formulation were separated and quantified by HPLC with CAD using an Ultimate 3000 HPLC with a Corona CAD RS Ultra detector (Thermo Fisher Scientific). The separation was conducted as described previously for alkylphenol ethoxylate surfactants using a mixed-mode high-performance size exclusion chromatography method.73 The column (Shodex MSPak GF310 4D, $150\\times4.6~\\mathrm{mm}_{;}$ , cross-linked polyvinyl alcohol phase) was held at $60^{\\circ}\\mathrm{C}$ and operated under gradient conditions with a flow rate of $0.2\\mathrm{mL}/\\mathrm{min}$ . The mobile phases were water (A) and methanol (B). From the initial conditions of $50{:}50\\mathrm{A/B}$ , solvent B was increased to $100\\%$ in $22.7\\mathrm{min}$ with a 10 min hold at $100\\%$ B. The column was returned to initial conditions in $\\ensuremath{5}\\ensuremath{\\mathrm{{min}}}$ and held for post-run equilibration for 10 additional minutes. The sample injection volume was ${\\mathfrak{s}}\\mu\\mathrm{L}$ . The charged aerosol detector was operated at a $25~^{\\circ}\\mathrm{C}$ nebulizer temperature and $10\\:\\mathrm{Hz}$ data acquisition with a digital filter setting of 3. The CAD response is proportional to the total mass (quantity) injected for nonvolatile compounds, and this response does not vary appreciably depending on the functional group or chemical structure across a wide range of molecule classes. 6:2 FTEO ethoxymers were identified by the corresponding retention time from analogous HPLC−HRMS analysis (below), and the relative quantity of each individual ethoxymer in the mixture was calculated as the $\\%$ of the total peak area for the full HPLC−CAD chromatogram. Three replicate analyses were conducted. This analysis provided a high-confidence quantification of the 6:2 FTEO ethoxymers present in the 6:2 FTEO fluorosurfactant formulation acquired from BOC Sciences. Due to the complexity of the mixture (extensive co-elution of different FTEO ethoxymers), we were unable to characterize the Zonyl FSN-100 via HPLC−CAD analysis.  \n\nHPLC−HRMS Methods for FTEO Quantification in Commercial Products. 6:2 FTEO ethoxymers were quantified in anti-fog sprays and cloth extracts by HPLC−HRMS. The HPLC separation conditions were exactly as described above (HPLC-CAD methods). Detection was performed using an Orbitrap Fusion Lumos Tribrid high-resolution mass spectrometer (Thermo Fisher Scientific) operated in the positive-ion electrospray mode. The source conditions were electrospray voltage $=3300\\mathrm{~V~}$ , sheath gas and auxiliary $\\mathtt{g a s}=35$ and 7 arbitrary units, respectively, ion transfer tube temperature $=350$ ${}^{\\circ}\\mathrm{C},$ and vaporizer temperature $=275^{\\circ}\\mathrm{C}$ . Spectra were acquired in the Orbitrap analyzer at 240,000 resolution over an $m/z$ range of $300{-}1100$ and an ion funnel RF amplitude of $60\\%$ . Spectral acquisition was internally calibrated using the Easy-IC reagent ion source to achieve mass accuracy typically ${<}1~\\mathrm{ppm}$ (RMS). Quantitation of individual 6:2 FTEO ethoxymers was conducted from accurate mass extracted ion chromatograms $\\left(2\\mathrm{ppm}\\right)$ with external standard quantitation versus a six-point calibration curve prepared from 0.1 to $50~\\mu\\mathrm{g/mL}$ $\\Sigma6{:}2$ FTEO. Anti-fog sprays were diluted 1:1000 or 1:100 in 50:50 methanol/water, and dichloromethane extracts of anti-fog cloths were evaporated to dryness under a gentle nitrogen stream and reconstituted in an equal volume of methanol prior to dilution (1:1000) in 50:50 methanol/water. The injection volumes were $5\\mu\\mathrm{L}$ in all cases. This analysis provided a highconfidence quantification of the 6:2 FTEO ethoxymers present in the anti-fog products with the use of the 6:2 FTEO fluorosurfactant formulation characterized via HPLC−CAD as described above.  \n\nTOF Measurement. All anti-fog products and the 6:2 FTEO commercial formulation were analyzed for TOF using previously published methods.74 TOF in this context refers to organic-bound fluorine or organofluorine. The fluorine contents in the four anti-fog sprays and the 6:2 FTEO formulation were diluted by methanol and water and then analyzed in triplicates by a Mitsubishi AQF-2100H furnace system. The fluorine atoms in all forms were mineralized into fluoride by combustion, which was then absorbed into reagent water. The formed fluoride concentration was quantified by a Dionex ICS-3000 ion chromatography (IC) to back-calculate the total fluorine (TF) concentrations in the samples. The same anti-fog spray samples were also diluted by water and analyzed for their inorganic fluoride (IF) concentrations directly using IC. The TOF was determined as the difference between the TF and IF levels in the same sample.75 In all the tested anti-fog spray samples, the TF levels were dominated by TOF, with IF contributing to $0.07-$ $1.43\\%$ of TF levels.  \n\n![](images/6001d78bcb167acb51b8ee8e1baaa8558df05b0a6e068d3a085e24122517c7ea.jpg)  \nFigure 2. Cytotoxicity and cell health measures for anti-fog sprays and constituent chemicals. 3T3-L1 pre-adipocytes were differentiated while exposed to sprays and constituent chemicals and then assayed for DNA content (cytotoxicity), ATP production (cell viability), and fluorescent microscopy (qualitative visual confirmation). The DNA content reported as increase (pre-adipocyte proliferation) or decrease (cytotoxicity) relative to differentiated solvent control response. ATP production reported as a decrease in ATP produced relative to differentiated solvent control response. Data presented as mean $\\pm\\operatorname{SEM}$ from three independent experiments. Fluorescence microscopy used as a third confirmatory measure of toxicity for anti-fog sprays (green fluorescence measures triglyceride accumulation staining and blue fluorescence represents nuclear staining).  \n\nThe five cloth samples were analyzed in triplicate for extractable organofluorine to represent their TOF levels. Each cloth sample $(0.05\\mathrm{g)}$ was extracted by $1\\mathrm{mL}$ of hexane:dichloromethane $\\left(1{:}1~\\mathbf{v}/\\mathbf{v}\\right)$ mixture under sonication three times. The combined extracts were diluted by methanol, combusted in the Mitsubishi furnace system, and analyzed for fluoride after combustion.  \n\nAdipogenesis Evaluation of Anti-fog Solutions. 3T3- L1 cells (Zenbio cat# SP-L1-F, lot# 3T3062104, passage 8-12;  \n\nTable 1. Concentrations of FTOH and 6:2 FTEOs in Anti-fog Sprays and Clothsa   \n\n\n<html><body><table><tr><td rowspan=\"2\"></td><td colspan=\"4\">Concentration (μg/mL)</td><td colspan=\"5\">Concentration (μg/g)</td></tr><tr><td> Spray A</td><td> Spray B</td><td> Spray C</td><td> Spray D</td><td>Cloth A</td><td>Cloth B</td><td>Cloth C</td><td>Cloth D</td><td>Cloth E</td></tr><tr><td>6:2FTOH</td><td>10,600</td><td>25.8</td><td>3.46</td><td>3.43</td><td>1.29</td><td>3.95</td><td>38.4</td><td>7.94</td><td>9.62</td></tr><tr><td>8:2FTOH</td><td></td><td>-</td><td>-</td><td>-</td><td>127</td><td>-</td><td></td><td></td><td></td></tr><tr><td>10:2FTOH</td><td></td><td></td><td>1</td><td>一</td><td>15.5</td><td>-</td><td></td><td></td><td>-</td></tr><tr><td>6:2FTEO1b</td><td>N.Q.</td><td>N.Q.</td><td>N.Q.</td><td>N.Q.</td><td>N.Q.</td><td>N.Q.</td><td>N.Q.</td><td>N.Q.</td><td>N.Q.</td></tr><tr><td>6:2FTEO2</td><td>35.2</td><td>1.08</td><td>0.193</td><td>0.194</td><td>1.29</td><td>53.3</td><td>126</td><td>208</td><td>244</td></tr><tr><td>6:2FTEO3</td><td>129</td><td>2.55</td><td>0.8</td><td>0.804</td><td>3.64</td><td>260</td><td>566</td><td>746</td><td>726</td></tr><tr><td>6:2FTEO4</td><td>1010</td><td>16.2</td><td>8.84</td><td>8.89</td><td>28.9</td><td>2770</td><td>6140</td><td>7340</td><td>5780</td></tr><tr><td>6:2FTEO5</td><td>2670</td><td>42.8</td><td>33</td><td>32.1</td><td>99</td><td>9420</td><td>22,100</td><td>23,400</td><td>17,200</td></tr><tr><td>6:2FTEO6</td><td>2790</td><td>50.1</td><td>52.9</td><td>51.4</td><td>134</td><td>12,200</td><td>29,200</td><td>33,200</td><td>21,300</td></tr><tr><td>6:2FTEO7</td><td>2200</td><td>46.8</td><td>64.6</td><td>63</td><td>125</td><td>12,200</td><td>29,300</td><td>30,400</td><td>20,800</td></tr><tr><td>6:2FTEO8</td><td>1720</td><td>44.3</td><td>73.4</td><td>75.9</td><td>104</td><td>10,600</td><td>26,300</td><td>28,400</td><td>18,900</td></tr><tr><td>6:2FTEO9</td><td>1280</td><td>35.4</td><td>76</td><td>78.3</td><td>77.9</td><td>7540</td><td>21,900</td><td>21,500</td><td>15,800</td></tr><tr><td>6:2FTEO10</td><td>964</td><td>28</td><td>77.6</td><td>79.7</td><td>57.2</td><td>5380</td><td>16,500</td><td>17,000</td><td>11,800</td></tr><tr><td>6:2FTEO11</td><td>616</td><td>17.2</td><td>67.3</td><td>66</td><td>35.7</td><td>3280</td><td>11,100</td><td>10,900</td><td>7830</td></tr><tr><td>6:2FTEO12</td><td>429</td><td>9.53</td><td>39.8 31.1</td><td>49.2</td><td>25</td><td>1720</td><td>6800</td><td>6230</td><td>4450</td></tr><tr><td>6:2FTEO13</td><td>517</td><td>7.19</td><td></td><td>57.1</td><td>7.34</td><td>1680</td><td>6090</td><td>5930</td><td>3120</td></tr><tr><td>∑ionic PFASc</td><td>1.37</td><td>0.062</td><td>0.019</td><td>0.037</td><td>2.09</td><td>0.156</td><td>1.51</td><td>2.68</td><td>0.825</td></tr><tr><td>∑PFAS TOF measurement</td><td>25,000 20,700</td><td>327</td><td>529</td><td>566</td><td>702</td><td>67,100</td><td>176,000</td><td>185,000</td><td>128,000</td></tr><tr><td>% TOF explained by FTEOs and</td><td>(508)</td><td>221 (3)</td><td>202 (2)</td><td>190 (1)</td><td>46,800 (5200)</td><td>44,200 (2200)</td><td>131,500 (2200)</td><td>92,000 (2700)</td><td>73,900 (2900)</td></tr><tr><td>FTOHs</td><td>60%</td><td>57%</td><td>88%</td><td>99%</td><td>1%</td><td>55%</td><td>48%</td><td>72%</td><td>62%</td></tr></table></body></html>  \n\naTOF measurements are reported as the average of triplicate analysis, with standard deviations in parenthesis. $^{b}6{:}2\\mathrm{FTEO1}$ was unable to be quantified via HPLC−HRMS methods as the other FTEOs were and is denoted as $\\mathrm{N.Q.}$ cSee Table S3 for the list of ionic PFAS quantified.  \n\nResearch Triangle Park, NC) were maintained as described in detail previously68,69,76,77 in pre-adipocyte media (Dulbecco’s modified Eagle’s mediumhigh glucose; DMEM-HG; Gibco cat# 11995, supplemented with $10\\%$ bovine calf serum and $1\\%$ penicillin and streptomycin). The cells were seeded into 96-well tissue culture plates (Greiner cat# 655090), grown to confluency, and allowed $^{48\\mathrm{~h~}}$ to undergo growth arrest and initiate clonal expansion. The medium was then replaced with controls and/or test solution dilutions in differentiation cocktail media (DMEM-HG with $10\\%$ fetal bovine serum, $1\\%$ penicillin/ streptomycin, $1.0\\:\\:\\mu\\mathrm{g/mL}$ human insulin, and $0.5\\ \\mathrm{\\mM}\\ 3\\$ - isobutyl-1-methylxanthine, IBMX). After $^{48\\mathrm{~h~}}$ of induction, the medium was replaced with fresh dilutions of all test chemicals and treatments in adipocyte maintenance media (differentiation media without IBMX), and this was refreshed every 2−3 days until the plates were assayed. 10 days after induction, the plates were assayed for triglyceride accumulation and pre-adipocyte proliferation. The medium was removed from the plates, and the cells were rinsed with Dulbecco’s phosphate-buffered saline (DPBS; Gibco cat # 14040), removed, and replaced with a 200 $\\mu\\mathrm{L}$ dye mixture $[19~\\mathrm{mL}$ of DPBS, 1 drop/ $\\mathrm{\\DeltamL}$ of NucBlue Live ReadyProbes Reagent (Thermo cat #R37605) and $500\\mu\\mathrm{L}$ of 40 $\\mu\\mathrm{g/mL}$ Nile Red (Sigma 72485-100MG)]. The plates were protected from light and incubated at room temperature for approximately $40\\mathrm{min}$ , and then the fluorescence was measured using excitation at $485\\mathrm{nm}$ and emission at ${572}\\mathrm{nm}$ for Nile Red and 360 and $460\\ \\mathrm{nm}$ for NucBlue, respectively.  \n\nFor triglyceride accumulation data, percent activities were calculated relative to the maximal rosiglitazone-induced fold induction over the intra-assay differentiated vehicle control ( $0.1\\%$ dimethyl sulfoxide) responses. The DNA content was calculated as percent change from differentiated vehicle control responses for each chemical at each concentration and was then used to normalize the total triglyceride values to obtain the triglyceride content per unit DNA (a proxy for triglyceride accumulation per cell). DNA content measurements in the adipogenesis assay can denote either pre-adipocyte proliferation (positive responses) and/or cytotoxicity (negative values) across a dose response. However, the DNA content assays can occasionally provide non-specific increases in this system, so two additional cell health measures were included to provide consensus determinations of toxicity. First, visual confirmation (qualitative) was performed using a Zeiss LSM 800 fluorescence confocal imaging system (Figure 2) to assess specific versus nonspecific staining and cell integrity. After fluorescence measurements and microscopy, the CellTiter-Glo 2.0 assay (Promega cat # PRG9242) was utilized to assess the metabolic activity of cells via ATP measurements. Briefly, $100\\mu\\mathrm{L}$ of media was removed from plates and replaced with $100~\\mu\\mathrm{L}$ of the CellTiter-Glo reagent, mixed, incubated for $10~\\mathrm{{min}}$ , and then read on a plate reader for quantification of luminescence. All three cell health determinations were compared to determine the potential cytotoxic responses by our test chemicals. Four technical (replicates within each assay plate) and three biological replicates (separate cell passages/assays) were performed for every tested chemical and concentration for each of these assays. Given the lack of available information on commercial sprays and contaminants present, we tested these at 1:1000 dilutions from the actual product. In contrast, we performed more controlled dose response ranges for individual and defined mixtures, where we had more information available to select realistic toxicological dosing concentrations below presumed toxicity.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# RESULTS AND DISCUSSION  \n\nProduct Characterization. Several different PFAS were detected in all products, and their chemical backbones are summarized in Figure 1. FTOHs and FTEOs were detected in every product. 6:2 FTOH and the 6:2 FTEO series were the predominant PFAS compounds observed and were detected in every product. FTEO ethoxymers were identified via GC− HRMS and HPLC−HRMS/MS by predicting the exact mass for each isomer up to 15 ethoxy units and monitoring for the protonated molecular ion in each sample. Identifications were additionally confirmed with fragments common to 6:2 FTOH and the series (Table S4). Ethoxymers in the 6:2 FTEO polymeric series were detected from 1 to 8 ethoxy units using GC−MS and from 2 to 13 ethoxy units using HPLC−HRMS. While the 6:2 compounds were most widely detected in samples, 8:2, 10:2, 12:2, 14:2, and 16:2 FTOH and FTEO series were detected in anti-fog cloth A. All products contained similar PFAS, some of which are novel and, to our knowledge, have not been reported in the literature. All products, except for anti-fog spray A, had a compound that included two partially fluorinated chains (6:2 fluorination pattern) connected by a single ether bond (Figure 1c). Anti-fog spray A instead was found to contain two partially fluorinated chains (6:2 fluorination pattern) with a fumarate diester bridge. Anti-fog cloth A also had similar compounds (i.e., ester-bonded fluorinated chains) with $6{:}2-$ 8:2, 8:2−8:2, 8:2−10:2, and 10:2−10:2 fluorination patterns (Table S4). In our method, the 8:2−12:2 fluorotelomer ether appeared to coelute with the isomeric 10:2−10:2 fluorotelomer ether (Figure S11). Larger fluorotelomer ethers were likely present but not observed using GC−HRMS due to their high masses. It seems possible that these compounds were not intentionally produced but were instead the result of side dimerization reactions, for example, manufacturing byproducts. One anti-fog spray (A) and two anti-fog cloths (C&D) also contained compounds with two partially fluorinated chains (6:2 fluorination pattern) connected by an ethoxyl chain length ranging from 1 to 8. Chemical identifiers, including CAS number, IUPAC Name, SMILES, and INCHI-Key, for all the identified PFAS compounds are listed in the Supporting Information (Table S5). Seven additional non-ionic PFAS (including 6:2 fluorotelomer acrylate, 6:2 fluorotelomer methacrylate, and 8:2 fluorotelomer acrylate) were targeted for quantification in this study but were not detected in products (Table S2).  \n\nThe concentration of 6:2 FTOH in the anti-fog sprays ranged from 3.43 to $10,600\\:\\mu\\mathrm{g/mL}$ (Table 1). While we did screen for 4:2, 8:2, 10:2, 12:2, 14:2, and 16:2 FTOH in all products, no other FTOHs were detected in any of the anti-fog sprays. In the anti-fog cloths, the levels of 6:2 FTOH ranged from 1.29 to 38.4 $\\mu\\mathrm{g}(\\mathrm{gcloth})^{-1}$ . Both 8:2 FTOH and 10:2 FTOH were detected in cloth A at 127 and $15.5~\\mu\\mathrm{g}$ $(\\mathrm{gcloth})^{-1}$ , respectively. 12:2 FTOH, 14:2 FTOH, and 16:2 FTOH were also detected in cloth A but were not quantified due to the lack of authentic standards. Qualitatively, 12:2 FTOH and 14:2 FTOH were present at levels equal to or greater than 6:2 FTOH in this product based on standard-normalized instrument responses (Table S6). The median FTOH concentrations reported here in these sprays and cloths are similar to what has previously been stone/wood sealants.33,38,39 However, the upper limit detected reported in food contact paper, treated textiles, floor waxes, and in anti-fog products ( $\\mathbf{\\widetilde{\\mu}}_{10,600}\\mu\\mathbf{g}/\\mathbf{m}\\mathbf{L})$ is an order of magnitude higher than previously measured.  \n\nIn general, the FTEOs were present in anti-fog products at levels greater than FTOHs (Tables 1 and S6). The $\\Sigma6{:}2$ $\\mathrm{FTEO}_{2-13}$ was present at levels up to $14{,}400~\\mu\\mathrm{g/mL}$ in sprays and up to $185,000~\\mu\\mathrm{g}$ $\\left(\\mathrm{g}\\ c l\\mathrm{oth}\\right)^{-1}$ in the cloths. In general, the anti-fog cloths had much greater levels of FTEOs relative to FTOHs (Table S6). Intuitively, this may be explained by the fact that the volatile FTOHs are likely not retained well on the cloths for extended periods of time. The 8:2, 10:2, 12:2, 14:2, and 16:2 FTEO series were also identified via GC−HRMS in anti-fog cloth A, all from 1 to 8 ethoxy units, respectively, though not quantified due to the lack of authentic standards.  \n\nAnti-fog products were also analyzed for a suite of 28 ionic PFAS, including PFSAs, PFCAs, FTSAs, FTCAs, diPAPs, GenX, and FOSAA using LC−MS/MS (Table S3). Many ionic PFAS were detected in products at trace levels (Table S3). Σ(ionic PFAS) ranged from 19 to $1370\\mathrm{ng/mL}$ in anti-fog sprays and 156 to $2680~\\mathrm{{\\bar{n}g}~(\\mathrm{g}~\\ c l o t h)^{-1}}$ in anti-fog sprays. Perfluoroalkyl carboxylic acids were the most abundant PFAS with PFBA or PFHxA being most prevalent in anti-fog sprays and PFHpA or PFPeA being most prevalent in anti-fog cloths. While a nonnegligible amount of legacy ionic PFAS was detected in these products, they were present at levels several orders of magnitude lower than FTOHs and FTEOs.  \n\nTOF contents of the anti-fog products were also quantified (Table 1). Of the four anti-fog sprays, spray A had the highest TOF content of $20,700\\:\\mu\\mathrm{g/mL}$ with sprays B, C, and $\\mathrm{~D~}$ at 221, 202, and $190~\\mu\\mathrm{g/mL},$ respectively. For the five anti-fog cloths, the TOF contents ranged from $44,200\\mu\\mathrm{g}(\\mathrm{gcloth})^{-1}$ in cloth B to $131,500~\\mu\\mathrm{g}~(\\mathrm{g}~\\mathrm{cloih})^{-1}$ in cloth C. These TOF values are higher than the extractable organic fluorine concentrations measured in cosmetics (up to $1720\\mu\\mathrm{g}\\mathrm{g}^{-1})^{78}$ and total fluorine (TF) concentrations measured up to $\\mathrm{{\\bar{6}0}~}\\mu\\mathrm{g\\g^{-1}}$ in fast food packaging.10 It makes an intuitive sense that anti-fog products, with the sole purpose of water repellency, would have higher fluorine content than cosmetics or food packaging, where PFASs are an additive.  \n\n6:2 FTOH and $\\Sigma6{:}2$ FTEOs accounted for $57-99\\%$ of TOF levels in anti-fog sprays and for $1-72\\%$ of TOF levels in anti-fog cloths (Table 1). The trace levels of ionic PFAS detected in antifog products only accounted for $0.01{-}0.03\\%$ of TOF in the antifog sprays and an even smaller portion in anti-fog cloths. Presumably, the remaining fluorine mass was associated with the PFAS discussed above. This is especially relevant for anti-fog cloth A, where 8:2, 10:2, 12:2, 14:2, and 16:2 FTEOs were present in the product. In anti-fog cloth A, 8:2 FTEOs and 10:2 FTEOs were present at levels that appear to be over an order of magnitude higher than the 6:2 FTEOs based on instrument normalized responses (Table S6). For the other products, the unquantified PFAS, namely, 6:2 fluorotelomer fumarate, $6{:}2-$ 6:2 fluorotelomer ether, $6{:}2\\mathrm{FTEO}_{1},$ and ethoxymers of a chain length ${>}13$ , likely account for the remaining fluorine mass quantified by the TOF measurements. For example, 6:2 fluorotelomer fumarate was the second most abundant peak (behind 6:2 FTOH) in spray A, which likely explains the lower contribution of TOF explained by our quantitative analysis. Similarly, $6{:}2{-}6{:}2$ fluorotelomer ethers were the second most abundant peak (behind 6:2 FTOH) in spray B, and this spray was the only spray to contain FTEO ethers, which we were unable to quantify (Table S6). This again likely explains the lower contribution of TOF explained by our quantitative analysis. These results suggest that, while there may still be unidentified PFAS in these products, we have identified the most prevalent compounds.  \n\n![](images/45aba5d972c1bd1a604eca21a4e319f4d389a6c1992f2d00f0ff13c0cf0e4a66.jpg)  \nFigure 3. Anti-fog sprays and fluorinated components induce pre-adipocyte differentiation. 3T3-L1 pre-adipocytes were differentiated while exposed to sprays and constituent chemicals and then assayed for triglyceride accumulation (marker of adipocyte differentiation) via Nile red neutral lipid droplet staining. Triglyceride accumulation is depicted for the anti-fog spray commercial products (A) and for the fluorinated component chemicals and commercial mixtures (B). Data presented as percent triglyceride accumulation per cell (normalized to DNA content) relative to the maximal intraassay response for the rosiglitazone positive control. Data presented as mean $\\pm$ SEM from three independent experiments. Data for triglyceride accumulation per cell at doses that were deemed cytotoxic are not shown.  \n\nCharacterization of Non-Ionic Fluorosurfactant Formulations. After identifying the FTEOs in these anti-fog products, we sought to determine the commercial PFAS source of these compounds and provide an estimate of their contribution in the products. We acquired an older Zonyl FSN-100 formulation from Dr. Jennifer Field (Oregon State University) and purchased a new FTEO formulation (hereafter referred to as $^{*}6{:}2$ FTEO formulation”) from BOC Sciences for PFAS characterization. The 6:2 FTEO formulation contained 6:2 FTOH, the 6:2 FTEO series, and 6:2-6:2 fluorotelomer ether (Table S6). 6:2 FTOH was present in the 6:2 FTEO formulation at a concentration of $7310\\pm140\\mu\\mathrm{g/g}$ . The Zonyl FSN-100 formulation, in contrast, contained FTOHs and FTEO series for 6:2, 8:2, 10:2, 12:2, 14:2, and 16:2 fluorination patterns, as well as 6:2−6:2, 6:2−8:2, 8:2−8:2, 8:2−10:2, and 10:2−10:2 fluorotelomer ethers (Table S6). 6:2, 8:2, and 10:2 FTOH were present at $834\\pm120$ , $754\\pm26,$ , and $482\\pm28\\mu\\mathrm{g/g},$ respectively, in the Zonyl FSN-100 formulation. The TOF measured in the 6:2 FTEO formulation was $447.57\\pm11.55\\mathrm{mg}$ $\\mathbf{g}^{-1}$ . Due to the limitations on the available amount, we were unable to conduct TOF analysis on the Zonyl FSN-100 mixture.  \n\nHPLC−CAD was used to quantify the ethoxymer distribution of the 6:2 FTEO formulation. The distribution peaked at six EO, with an asymmetric profile favoring shorter chains (Table S7), consistent with commercial production via ethylene oxide polymerization on an alcohol hydrophobe. Ethoxylate chain lengths from 2 to 13 accounted for $92.74\\%$ of the formulation (Table S7). Presumably, 6:2 FTOH, 6:2 FTEO1, and 6:2−6:2 fluorotelomer ether account for the remaining percentage, though it could not be confirmed via HPLC−CAD analysis. Due to the complexity of the mixture (extensive co-elution of different FTEO ethoxymers), we were unable to quantitatively characterize the Zonyl FSN-100 via HPLC−CAD analysis.  \n\nThe 6:2 FTEO formulation most closely resembled the formulation present in sprays C and D and cloths B and C, while the Zonyl FSN-100 formulation most closely resembled the formulation present in cloth A. Spray B and cloths D and E all appear to be produced from the same chemical formulation, not identified in this study, which includes the 6:2 FTEO ethers. Spray A, while similar to the 6:2 FTEO formulation, included the 6:2 fluorotelomer fumarate in the place of 6:2−6:2 fluorotelomer ether, suggesting that it may stem from a different FTEO commercial mixture that was likely manufactured using a modified procedure.  \n\nAdipogenic Activity of Anti-fog Spray Products. Since prior research observed high adipogenic activity for similar polyethoxylated surfactants,69,71 we sought to determine if these fluorinated ethoxylate products and mixtures would also elicit activity. All the four anti-fog spray solutions, both commercial formulations, and four individual component chemicals present in the sprays (6:2 FTOH, 8:2 FTOH, diethylene glycol butyl ether, and 1-butoxypropanol) were characterized for their potential toxicity using several metrics, including assessments of cytotoxicity (DNA content), cell viability (ATP production), and a qualitative microscopy evaluation. All of these were also assessed for their adipogenic activity (triglyceride accumulation and pre-adipocyte proliferation) in murine 3T3-L1 preadipocytes. Cloths were not tested.  \n\nFigure 2 presents the results from the cell health/cytotoxicity testing. In general, the commercial anti-fog spray products were much more toxic than any of the individual chemicals present in the sprays (e.g., 6:2 FTOH, 8:2 FTOH, diethylene glycol butyl ether, and 1-butoxypropanol) or commercial chemical mixtures tested (i.e., 6:2 FTEO mixture and Zonyl FSN-100). Anti-fog spray A inhibited cell viability at doses of 10,000 and 100,000 $\\mu\\mathrm{g/mL}$ based on cell viability (ATP production) and visual confirmation via microscopy, despite DNA content measurements appearing to increase at $10,000~\\mu\\mathrm{g/mL}$ . Anti-fog B marginally inhibited the cell viability at concentrations of 1000 and $10,000\\mu\\mathrm{g/mL}$ (ATP production), with normal microscopy and positive effects on DNA content at these doses. At 100,000 $\\mu\\mathrm{g/mL},$ all three measures demonstrated consistent toxicity. Anti-fog sprays C and D were most toxic, with cell viability and visual confirmation suggesting cytotoxicity at doses $\\geq1000\\mu\\mathbf{g}/$ $\\mathrm{mL}$ (despite apparent increase in DNA content at $100,000\\mu\\mathrm{g/}$ mL). Of the individual chemicals and commercial mixtures, 8:2 FTOH was cytotoxic at the highest dose ${'}46\\ \\mu\\mathrm{g/mL}$ and 100 $\\mu\\mathbf{M})$ in both DNA and ATP content assays. The Zonyl FSN-100 formulation inhibited cell viability at the highest dose $(50~\\mu\\mathrm{g}/\\$ mL), though there were no apparent effects on DNA content. 6:2 FTOH, the 6:2 FTEO formulation, and both nonfluorinated additives (diethylene glycol butyl ether and 1- butoxypropanol) did not demonstrate cytotoxicity at any doses tested in this study. At concentrations below the cytotoxicity thresholds discussed above, anti-fog sprays exhibited a range of adipogenic activities. Triglyceride accumulation is presented in Figure 3 and is only shown for doses that were not deemed cytotoxic based on the three measures described above. Anti-fog A exhibited the greatest degree of activity, with approximately $145\\%$ triglyceride accumulation induced at $1000\\mu\\mathrm{g/mL},$ relative to the maximal rosiglitazone-induced (positive control) response (set at $100\\%$ ). Anti-fog A also promoted pre-adipocyte proliferation, with $40\\%$ increased DNA content relative to the differentiated vehicle control at $1000~\\mu\\mathrm{g/mL}$ (Figure 2). Antifog B exhibited minor adipogenic activity, with $22\\%$ triglyceride accumulation induced at $10,000~\\mu\\mathrm{g/mL},$ and $32\\%$ increased DNA content at $1000\\mu\\mathrm{g/mL}$ . Anti-fog sprays C and D exhibited 71 and $41\\%$ triglyceride accumulation at $100\\:\\:\\mu\\mathrm{g/mL}$ , respectively, and neither promoted significant cell proliferation (i.e., increased DNA content) at any concentration tested.  \n\nOf the individual chemicals tested, 6:2 FTOH exhibited minor adipogenic activity, with $13\\%$ triglyceride accumulation induced at $36\\mu\\mathrm{g/mL}$ $(100\\mu\\mathrm{M})$ and no effects on pre-adipocyte proliferation. Similarly, 8:2 FTOH exhibited $11\\%$ triglyceride accumulation at $\\sim5\\mu\\mathrm{g/mL}$ $(10\\mu\\mathbf{M})$ . The two non-fluorinated additives were inactive for both triglyceride accumulation and proliferation (Figure S1). In contrast, the commercial mixtures exhibited robust adipogenic activity. The 6:2 FTEO formulation and Zonyl FSN-100 formulation exhibited 109 and $66\\%$ triglyceride accumulation at $50~\\mu\\mathrm{g/mL},$ , respectively. The 6:2 FTEO formulation also promoted $24\\%$ pre-adipocyte proliferation at $10|\\mathrm{\\Omega}\\mu\\mathrm{g/mL},$ though the Zonyl FSN-100 had no proliferative effects.  \n\nWe have previously reported the adipogenic activities of a small number of PFAS, including 6:2 and 8:2 FTOHs, neither of which exhibited significant activity in our assay previously (at lower concentrations than we tested herein).68 However, 8:2 fluorotelomer acrylate $\\left(1H,1H,2H,2H\\right.$ -heptadecafluorodecyl acrylate) exhibited significant effects on triglyceride accumulation in our hands,68 and others have demonstrated adipogenic effects for other PFAS in this model.67 We have also previously reported extremely potent and efficacious triglyceride accumulation and pre-adipocyte proliferation for various alkylphenols and alcohol polyethoxylates.69 It is therefore perhaps unsurprising that the ethoxylated fluorotelomer compounds identified in this study exhibit activity in this assay. We should note that our results provide a note of caution on the interpretation of highthroughput toxicity testing. While some chemicals exhibited an apparent increase in DNA content at high doses (e.g., sprays A, C, and D), fluorescent imaging and cell viability assays confirmed cell death at these concentrations (Figure 2).  \n\nLast, we sought to estimate the potential PFAS exposure by using these sprays as indicated. We measured the density of each defogger spray (Table S8). Based on these densities, and our measurement of PFAS, we estimate that approximately $2.5\\%$ of the mass of spray A is composed of PFAS, whereas in sprays B, C, and D, PFAS ranged from 0.03 to $0.06\\%$ . Therefore, a $1000\\mu\\mathrm{g}/\\$ mL dose of spray A would be $\\sim25\\mu\\mathrm{g/mL}$ total PFAS and would fall between the 5 and $50~\\mu\\mathrm{g/mL}$ dose of the 6:2 FTEO formulation. The $135\\%$ triglyceride accumulation observed at $1000\\mu\\mathrm{g/mL}$ of spray A correlates well with the interpolated 25 $\\mu\\mathrm{g/mL}$ activity ( $\\mathord{\\sim}100\\%$ triglyceride accumulation) observed at for the 6:2 FTEO commercial mixture. Since we were able to completely characterize spray A (the ingredient list was on the product bottle) and we know that the two non-fluorinated additives present in spray A were not active in our assay, we can conclude that the 6:2 FTEOs are a significant driver to the adipogenic activity exhibited by spray A in our model.  \n\nSimilarly, the $10,000\\mu\\mathrm{g/mL}$ dose of spray B would be ${\\sim}3\\mu\\mathrm{g}/$ mL total PFAS (i.e., dose of the 6:2 FTEO formulation). The $20\\%$ triglyceride accumulation observed at $10,000~\\mu\\mathrm{g/mL}$ of spray B correlates well with the $3~\\mu\\mathrm{g/mL}$ activity $(\\sim30\\%$ triglyceride accumulation) observed for the 6:2 FTEO commercial mixture. While we were unable to completely characterize spray B, we can reasonably postulate that the 6:2 FTEOs are a significant driver of the adipogenic activity exhibited by spray B in our model.  \n\nSprays C and D are more difficult to interpret within our assay due to high levels of cytotoxicity. Sprays C and D demonstrate equivalent effects on triglyceride accumulation to A at $10~\\mu\\mathrm{g}/\\$ mL, despite having much lower total PFAS levels in the product. This high degree of cytotoxicity and adipogenic activity cannot be predicted by the known levels of PFAS in these products. Contrary to sprays A and B, sprays C and D had several highly abundant features present in the chromatogram that we were unable to identify. These features were present at levels many orders of magnitude higher than the any fluorinated compound identified in the sprays, contrary to what was observed in sprays A and B. Therefore, contrary to the strong line of evidence we have for 6:2 FTEO driving activity in sprays A and B, we believe that the unidentified additives may be driving the activity for sprays C and D that we see in our model. Though without a true identification, we cannot be certain.  \n\nImplications. While we only measured a small number of anti-fog products, we found that FTOHs and FTEOs were quantitatively important components in all of them. The FTEOs explained a majority of the TOF measured in the samples, demonstrating the importance of the TOF (or similar) approach, as a regular targeted method would have been insufficient to characterize the full PFAS content in these samples. The presence of PFAS compounds in these anti-fog products is unsurprising, though the quantity was unexpected. Using the measured densities of each spray, we estimate that ${\\sim}3.5\\mathrm{\\mg}$ of PFAS is discharged to the target surface and surrounding environment with each pump of spray A. Sprays B, C, and $\\mathrm{~D~}$ all fall below $100\\mu\\mathrm{g}$ of PFAS per use (Table S8). To put this in context, if only $1\\%$ of the total PFAS from each use of the spray enters the body (via inhalation/dermal absorption), the PFAS exposure would equate to $1-35~\\mu\\mathrm{g}$ of PFAS. This amount of PFAS exposure is a $14{-}500\\times$ greater dose than one would receive if consuming $1\\mathrm{L}$ of water at the U.S. EPA health advisory level for PFAS/PFOA of 70 part per trillion $(\\mathrm{ng/L})$ . The application notes for spray A state that one application will be effective for ${\\sim}24\\mathrm{h},$ which indicates that this product has the potential to be a significant daily exposure source. In addition, the instructions on spray A recommended rubbing the product onto the eyeglass surface with your finger. Given the mobility of FTOHs in the indoor environment, these products have the potential to be an important source of PFAS precursors in the indoor environment (namely, air and dust). Previous studies have shown that FTOHs in air are correlated with serum PFAA levels, suggesting that they may be an important precursor class for PFAAs that are more toxic and have longer half-lives in the body.64,79  \n\nSignificant effects on triglyceride accumulation were observed for all four anti-fog sprays and on pre-adipocyte proliferation for two of the four solutions. Even at concentrations as low as 10 $\\mu\\mathrm{g/mL},$ anti-fog spray A exhibited ${\\sim}20\\%$ triglyceride accumulation or equivalent to approximately $\\textit{s}_{\\mathrm{nM}}$ of the positive control, rosiglitazone. Importantly, the biological activity was observed at an in vitro dose that is less than the dose applied to eyeglasses from one pump of the spray based on their densities (the $1000~\\mu\\mathrm{g/mL}$ in vitro dose is equivalent to $\\sim190~\\mu\\mathrm{g}$ of solution, with approximately 1000 times the quantity released in each spray). Sprays C and $\\mathrm{~D~}$ similarly exhibited significant triglyceride accumulation at the $10~\\mu\\mathrm{g/mL}$ dose, though it is unclear how much of this activity is attributable to FTEOs. Regardless of the main driver of adipogenic activity in sprays C and D, it is similarly observed at an in vitro dose that is less than the dose applied to eyeglasses from one pump of the spray, thereby warranting the concern.  \n\nWhile the production and use of anti-fog products is a clear potential exposure source of FTEOs, little is known about their fate in the human body or the environment. Frömel and Knepper (2010) found FTEOs biodegraded in a WWTP under aerobic conditions to FTEO carboxylates (FTEOC), with little evidence of them degrading beyond that.66 However, further research is needed to fully understand the potential pathways for FTEOs to degrade further to FTOHs and subsequently stable ionic PFAA. Given that the aforementioned study only analyzed FTEO biodegradation under a single set of conditions, there is still much unknown about the biodegradation potential of these compounds. Even less is known about the transformation of FTEOs via metabolic processes, as it has not been studied.  \n\nTo the best of our knowledge, no research to date has been conducted to determine how widespread FTEOs are used in consumer products and how much of it is being produced every year. These products were manufactured in several different countries, specifically the United States, China, and Korea (Table S1), and therefore, it seems likely that there is global use of these products. This is especially pertinent given the recent EU ban on long-chain perfluorinated carboxylic acids (C9-14 PFCAs), their salts and precursors that will take effect in February 2023,80 and the progress toward more restrictive regulation in the United States.81 While a majority of the analytes detected in this study were short-chain PFAS (C6), one sample and one commercial mixture contained long-chain PFAS (C10−C16 FTOHs/FTEOs). These analytes could be classified as precursors for long-chain PFCAs and would thus be subject to the new EU regulations. More research is needed to elucidate the uses of these novel compounds in commercial products.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# ASSOCIATED CONTENT",
+        "category": " References"
+    },
+    {
+        "id": 8,
+        "chunk": "# $\\bullet$ Supporting Information  \n\nThe Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.est.1c06990.  \n\nAdditional plots for adipogenesis results, additional information for the anti-fog products, as well as chemical descriptors, structures, mass-to-charge ratios, spectra, and relative response ratios for identified fluorinated compounds; results in full for LC−MS analysis of ionic PFAS and fluorotelomer ethoxymer distribution in commercial FTEO formulation determined by HPLC−CAD analysis; and PCI spectra for all the identified PFAS in this study (PDF)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# AUTHOR INFORMATION  \n\nCorresponding Author Heather M. Stapleton − Nicholas School of the Environment, Duke University, Durham, North Carolina 27708, United States; $\\circledcirc$ orcid.org/0000-0002-9995-6517; Phone: (919) 613-8717; Email: heather.stapleton@duke.edu",
+        "category": " References"
+    },
+    {
+        "id": 10,
+        "chunk": "# Authors  \n\nNicholas J. Herkert − Nicholas School of the Environment, Duke University, Durham, North Carolina 27708, United States; $\\circledcirc$ orcid.org/0000-0002-3286-8934   \nChristopher D. Kassotis − Institute of Environmental Health Sciences and Department of Pharmacology, Wayne State University, Detroit, Michigan 48202, United States   \nSharon Zhang − Nicholas School of the Environment, Duke University, Durham, North Carolina 27708, United States   \nYuling Han − Department of Civil and Environmental Engineering, University of North Carolina at Charlotte, Charlotte, North Carolina 28223, United States   \nVivek Francis Pulikkal − Department of Civil and Environmental Engineering, University of North Carolina at Charlotte, Charlotte, North Carolina 28223, United States   \nMei Sun − Department of Civil and Environmental Engineering, University of North Carolina at Charlotte, Charlotte, North Carolina 28223, United States   \nP. Lee Ferguson − Nicholas School of the Environment and Department of Civil and Environmental Engineering, Duke University, Durham, North Carolina 27708, United States; $\\circledcirc$ orcid.org/0000-0002-8367-7521  \n\nComplete contact information is available at: https://pubs.acs.org/10.1021/acs.est.1c06990  \n\nNotes The authors declare no competing financial interest.",
+        "category": " References"
+    },
+    {
+        "id": 11,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nThis research was supported in part by a grant from the Environment Protection Agency (CR-83948201-0; H.M.S.), a major research instrumentation grant from the National Science Foundation (CBET-1828257; H.M.S.), the National Institute of Environmental Health Sciences (R00 ES030405; C.D.K.), and the North Carolina Policy Collaborative through an appropriation from the North Carolina General Assembly (Y.H., V.F.P., and M.S.). We also wish to thank Michael and Annie Falk for establishing the Falk Exposomics Laboratory (H.M.S. and P.L.F.). Last, we wish to thank Duncan Hay for assistance with laboratory analysis.",
+        "category": " Acknowledgments"
+    },
+    {
+        "id": 12,
+        "chunk": "# REFERENCES  \n\n(1) Hu, Y. Prevention of Fogging of Protective Eyewear for Medical Staff During the COVID-19 Pandemic. J. Emerg. Nurs. 2020, 46, 564− 566.   \n(2) Hazanchuk, V. How to Wear a Face Mask Without Fogging Your Glasses. EyeSmart; The American Academy of Ophthalmic, 2021. (3) How to Keep Your Glasses From Fogging Up While Wearing a Mask. Health Essentials; Cleveland Clinic, 2020.   \n(4) Vence, T. The Best Anti-Fog for Glasses and a Mask. Wirecutter; The New York Times Company, 2021.   \n(5) Barzen-Hanson, K. A.; Roberts, S. C.; Choyke, S.; Oetjen, K.; McAlees, A.; Riddell, N.; McCrindle, R.; Ferguson, P. L.; Higgins, C. P.; Field, J. A. Discovery of 40 Classes of Per- and Polyfluoroalkyl Substances in Historical Aqueous Film-Forming Foams (AFFFs) and AFFF-Impacted Groundwater. Environ. Sci. Technol. 2017, 51, 2047− 2057. (6) Buck, R. C.; Franklin, J.; Berger, U.; Conder, J. M.; Cousins, I. T.; De Voogt, P.; Jensen, A. A.; Kannan, K.; Mabury, S. A.; van Leeuwen, S. P. Perfluoroalkyl and polyfluoroalkyl substances in the environment: terminology, classification, and origins. Integrated Environ. Assess. Manag. 2011, 7, 513−541.   \n(7) Houtz, E. F.; Higgins, C. P.; Field, J. A.; Sedlak, D. L. Persistence of perfluoroalkyl acid precursors in AFFF-impacted groundwater and soil. Environ. Sci. Technol. 2013, 47, 8187−8195.   \n(8) Houtz, E. F.; Sutton, R.; Park, J.-S.; Sedlak, M. Poly-and perfluoroalkyl substances in wastewater: Significance of unknown precursors, manufacturing shifts, and likely AFFF impacts. Water Res. 2016, 95, 142−149.   \n(9) Prevedouros, K.; Cousins, I. T.; Buck, R. C.; Korzeniowski, S. H. Sources, fate and transport of perfluorocarboxylates. Environ. Sci. Technol. 2006, 40, 32−44.   \n(10) Schaider, L. A.; Balan, S. A.; Blum, A.; Andrews, D. $\\mathrm{Q.;}$ Strynar, M. J.; Dickinson, M. E.; Lunderberg, D. M.; Lang, J. R.; Peaslee, G. F. Fluorinated compounds in US fast food packaging. Environ. Sci. Technol. 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Total Environ. 2016, 553, 266−275.   \n(49) Winkens, K.; Giovanoulis, G.; Koponen, J.; Vestergren, R.; Berger, U.; Karvonen, A. M.; Pekkanen, J.; Kiviranta, H.; Cousins, I. T. Perfluoroalkyl acids and their precursors in floor dust of children’s bedrooms−Implications for indoor exposure. Environ. Int. 2018, 119, 493−502.   \n(50) Wu, Y.; Romanak, K.; Bruton, T.; Blum, A.; Venier, M. Per- and polyfluoroalkyl substances in paired dust and carpets from childcare centers. Chemosphere 2020, 251, 126771.   \n(51) Xu, Z.; Fiedler, S.; Pfister, G.; Henkelmann, B.; Mosch, C.; Völkel, W.; Fromme, H.; Schramm, K.-W. Human exposure to fluorotelomer alcohols, perfluorooctane sulfonate and perfluorooctanoate via house dust in Bavaria, Germany. Sci. Total Environ. 2013, 443, 485−490.   \n(52) Zheng, G.; Boor, B. E.; Schreder, E.; Salamova, A. Indoor exposure to per- and polyfluoroalkyl substances (PFAS) in the childcare environment. Environ. Pollut. 2020, 258, 113714.   \n(53) Butt, C. M.; Muir, D. C. G.; Mabury, S. A. Biotransformation pathways of fluorotelomer-based polyfluoroalkyl substances: A review. Environ. Toxicol. Chem. 2014, 33, 243−267.   \n(54) Frömel, T.; Knepper, T. P. Mass spectrometry as an indispensable tool for studies of biodegradation of surfactants. Trac. Trends Anal. Chem. 2008, 27, 1091−1106.   \n(55) Gebbink, W. A.; Berger, U.; Cousins, I. T. Estimating human exposure to PFOS isomers and PFCA homologues: the relative importance of direct and indirect (precursor) exposure. Environ. Int. 2015, 74, 160−169.   \n(56) Liu, J.; Lee, L. S.; Nies, L. F.; Nakatsu, C. H.; Turco, R. F. Biotransformation of 8: 2 fluorotelomer alcohol in soil and by soil bacteria isolates. Environ. Sci. Technol. 2007, 41, 8024−8030.   \n(57) Liu, J.; Wang, N.; Szostek, B.; Buck, R. C.; Panciroli, P. K.; Folsom, P. W.; Sulecki, L. M.; Bellin, C. A. 6-2 Fluorotelomer alcohol aerobic biodegradation in soil and mixed bacterial culture. Chemosphere 2010, 78, 437−444.   \n(58) Martin, J. W.; Mabury, S. A.; O’Brien, P. J. Metabolic products and pathways of fluorotelomer alcohols in isolated rat hepatocytes. Chem.-Biol. Interact. 2005, 155, 165−180.   \n(59) Nilsson, H.; Kärrman, A.; Rotander, A.; van Bavel, B.; Lindström, G.; Westberg, H. Inhalation exposure to fluorotelomer alcohols yield perfluorocarboxylates in human blood? Environ. Sci. Technol. 2010, 44, (60) Rand, A. A.; Mabury, S. A. Is there a human health risk associated with indirect exposure to perfluoroalkyl carboxylates (PFCAs)? Toxicology 2017, 375, 28−36.   \n(61) Wang, N.; Szostek, B.; Buck, R. C.; Folsom, P. W.; Sulecki, L. M.; Gannon, J. T. 8-2 Fluorotelomer alcohol aerobic soil biodegradation: Pathways, metabolites, and metabolite yields. Chemosphere 2009, 75, 1089−1096.   \n(62) Wang, Z.; Cousins, I. T.; Scheringer, M.; Hungerbühler, K. Fluorinated alternatives to long-chain perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkane sulfonic acids (PFSAs) and their potential precursors. Environ. 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The effects of perfluorinated chemicals on adipocyte differentiation in vitro. Mol. Cell. Endocrinol. 2015, 400, 90−101.   \n(68) Kassotis, C. D.; Hoffman, K.; Stapleton, H. M. Characterization of Adipogenic Activity of Semi-volatile Indoor Contaminants and House Dust. Environ. Sci. Technol. 2017, 51, 8735−8745.   \n(69) Kassotis, C. D.; Kollitz, E. M.; Ferguson, P. L.; Stapleton, H. M. Nonionic ethoxylated surfactants induce adipogenesis in 3T3-L1 cells. Toxicol. Sci. 2018, 162, 124−136.   \n(70) Bowers, R. R.; Temkin, A. M.; Guillette, L. J.; Baatz, J. E.; Spyropoulos, D. D. The commonly used nonionic surfactant Span 80 has RXRα transactivation activity, which likely increases the obesogenic potential of oil dispersants and food emulsifiers. Gen. Comp. Endocrinol. 2016, 238, 61−68.   \n(71) Temkin, A. M.; Bowers, R. R.; Magaletta, M. E.; Holshouser, S.; Maggi, A.; Ciana, P.; Guillette, L. J.; Bowden, J. A.; Kucklick, J. R.; Baatz, J. E. Effects of crude oil/dispersant mixture and dispersant components on PPAR γ activity in vitro and in vivo: identification of dioctyl sodium sulfosuccinate (DOSS; CAS# 577-11-7) as a probable obesogen. Environmental health perspectives 2016, 124, 112−119.   \n(72) Shoeib, M.; Harner, T.; Lee, S. C.; Lane, D.; Zhu, J. Sorbentimpregnated polyurethane foam disk for passive air sampling of volatile fluorinated chemicals. Anal. Chem. 2008, 80, 675−682.   \n(73) Ferguson, P. L.; Iden, C. R.; Brownawel, B. J. Analysis of nonylphenol and nonylphenol ethoxylates in environmental samples by mixed-mode high-performance liquid chromatography-electrospray mass spectrometry. J. Chromatogr. A 2001, 938, 79−91.   \n(74) Han, Y.; Pulikkal, V. F.; Sun, M. Comprehensive Validation of the Adsorbable Organic Fluorine Analysis and Performance Comparison of Current Methods for Total Per- and Polyfluoroalkyl Substances in Water Samples. ACS ES&T Water 2021, 1, 1474−1482.   \n(75) Dubocq, F.; Wang, T.; Yeung, L. W. Y.; Sjöberg, V.; Kärrman, A. Characterization of the Chemical Contents of Fluorinated and Fluorine-Free Firefighting Foams Using a Novel Workflow Combining Nontarget Screening and Total Fluorine Analysis. Environ. Sci. Technol. 2019, 54, 245−254.   \n(76) Kassotis, C. D.; Masse, L.; Kim, S.; Schlezinger, J. J.; Webster, T. F.; Stapleton, H. M. Characterization of adipogenic chemicals in three different cell culture systems: implications for reproducibility based on cell source and handling. Sci. Rep. 2017, 7, 42104.   \n(77) Kassotis, C. D.; Hoffman, K.; Phillips, A. L.; Zhang, S.; Cooper, E. M.; Webster, T. F.; Stapleton, H. M. Characterization of adipogenic,   \nPPARgamma, and TRbeta activities in house dust extracts and their   \nassociations with organic contaminants. Sci. Total Environ. 2021, 758,   \n143707. (78) Schultes, L.; Vestergren, R.; Volkova, K.; Westberg, E.; Jacobson,   \nT.; Benskin, J. P. Per- and polyfluoroalkyl substances and fluorine mass   \nbalance in cosmetic products from the Swedish market: implications for   \nenvironmental emissions and human exposure. Environ. Sci.: Processes   \nImpacts 2018, 20, 1680−1690. (79) Fraser, A. J.; Webster, T. F.; Watkins, D. J.; Strynar, M. J.; Kato,   \nK.; Calafat, A. M.; Vieira, V. M.; McClean, M. D. Polyfluorinated   \ncompounds in dust from homes, offices, and vehicles as predictors of   \nconcentrations in office workers’ serum. Environ. Int. 2013, 60, 128−   \n136. (80) Perfluoroalkyl chemicals (PFAS). https://echa.europa.eu/hot  \ntopics/perfluoroalkyl-chemicals-pfas (July 12, 2021). (81) EPA’s Per- and Polyfluoroalkyl Substances (PFAS) Action Plan.   \nReport 823-R-18-004; U.S. Environmental Protection Agency:   \nWashington, DC, 2019.",
+        "category": " References"
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+        "id": 13,
+        "chunk": "# Recommended by ACS",
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+    },
+    {
+        "id": 14,
+        "chunk": "# Molecular Characterization of the Thermal Degradation of Per- and Polyfluoroalkyl Substances in Aqueous FilmForming Foams via Temperature-Programmed Thermal ...  \n\nChristopher P. West, Patrick W. Fedick, et al. MARCH 20, 2023 ENVIRONMENTAL SCIENCE & TECHNOLOGY LETTERS  \n\nREAD",
+        "category": " References"
+    },
+    {
+        "id": 15,
+        "chunk": "# Per- and Polyfluoroalkyl Substances in Toilet Paper and the Impact on Wastewater Systems  \n\nJake T. Thompson, Timothy G. Townsend, et al. MARCH 01, 2023 ENVIRONMENTAL SCIENCE & TECHNOLOGY LETTERS  \n\nREAD",
+        "category": " References"
+    },
+    {
+        "id": 16,
+        "chunk": "# Impacts of Environmental and Engineered Processes on the PFAS Fingerprint of Fluorotelomer-Based AFFF  \n\nSarah Balgooyen and Christina K. Remucal DECEMBER 27, 2022 ENVIRONMENTAL SCIENCE & TECHNOLOGY  \n\nREAD",
+        "category": " References"
+    },
+    {
+        "id": 17,
+        "chunk": "# Per- and Polyfluoroalkyl Substances in Field-Collected Light Non-Aqueous Phase Liquids  \n\nEmerson C. Christie, Jennifer A. Field, et al. FEBRUARY 09, 2023   \nACS ES&T WATER  \n\nREAD",
+        "category": " References"
+    },
+    {
+        "id": 18,
+        "chunk": "# Get More Suggestions >",
+        "category": " Introduction"
+    }
+]
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+    {
+        "id": 1,
+        "chunk": "# 心血管植介入体表面抗凝涂层近十年进展王禹贺，李燕，蒙奎霖，满佳，李永健，陈皓生",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# A Critical Review on Anticoagulant Coatings on Cardiovascular Implants in the Past 10 Years  \n\nWANG Yuhe,  LI Yan,  MENG Kuilin,  MAN Jia,  LI Yongjian,  CHEN Haosheng  \n\n在线阅读 View online: https://doi.org/10.16078/j.tribology.2022016  \n\n您可能感兴趣的其他文章Articles you may be interested in",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# 心血管植介入体表面抗凝涂层近十年进展  \n\n王禹贺1, 李  燕1, 蒙奎霖1, 满  佳2, 李永健1, 陈皓生1\\*(1. 清华大学 摩擦学国家重点实验室, 北京 100084;2. 山东大学 高效洁净机械制造教育部重点实验室, 山东 济南 250061)  \n\n摘   要: 心血管植介入体已被广泛用于治疗各种心血管疾病. 然而，植介入体表面和血液之间的接触会导致血栓，进而显著增加了血栓疾病的发病率和死亡率. 为降低血栓风险，在植介入体表面修饰抗凝涂层是预防血栓的常用方法. 本文中作者综述了近十年中不同心血管植介入体表面的抗凝涂层技术，重点回顾了应用于四种典型的心血管植介入体(包括人工心脏瓣膜、血管支架、心室辅助装置和导管)的抗凝涂层的进展. 最后，总结了每种植介入体表面的理想设计，并展望了心血管植介入体表面抗凝涂层技术的未来，对推进心血管植介入体的设计开发和应用具有重要意义.  \n\n关键词: 抗凝涂层; 心血管植介入体; 人工心脏瓣膜; 血管支架; 心室辅助装置; 导管  \n\n中图分类号: R318.08文献标志码: A  \n\n文章编号: 1004-0595(2023)04–0446–23",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# A Critical Review on Anticoagulant Coatings on Cardiovascular Implants in the Past 10 Years  \n\nWANG Yuhe1, LI Yan1, MENG Kuilin1, MAN Jia2, LI Yongjian1, CHEN Haosheng1  \n\n(1. State Key Laboratory of Tribology, Tsinghua University, Beijing 100084, China 2. Key Laboratory High Efficiency & Clean Mech Manufacture, Shandong University, Shandong Jinan 250061, China) Abstract: Cardiovascular implants have been widely used as a treatment for various cardiovascular diseases. However, the contact between implant surface and blood will cause thrombus that leads to significant morbidity and mortality worldwide. To reduce the risk of thrombus, immobilizing anticoagulant coatings on the implant surface is a common method to realize anticoagulation. In this review, we focus on the anticoagulant coatings on different cardiovascular implants in the past 10 years. We review the advance on the anticoagulant coatings of four typical cardiovascular implants including artificial heart valves, vascular stents, ventricular assist devices, and catheters. In the end, we conclude the ideal design for each implant and look ahead to the future of the cardiovascular anticoagulant coatings. It is of great significance to improve the design and application of cardiovascular implants.  \n\nKey words: anticoagulant coatings; cardiovascular implants; artificial heart valve; vascular stent; ventricular assist devices; catheters  \n\n心血管疾病已成为全世界范围内首要的致死原因. 世界卫生组织的数据显示，每年有1 790万人死于心血管疾病[1]. 为应对心血管疾病及带来的器官和组织病变，心血管植介入体，如人工心脏瓣膜[2]、血管支架[3]、心室辅助装置[4]和导管[5]，已被广泛用作退化器官的替代物. 心血管器械中的摩擦学问题根据摩擦副的不同可分为3类[6]：(1)心血管设备中的运动部件产生的机械磨损和摩擦；(2)血流在各种心血管设备的表面产生的流体摩擦；(3)在植入或原位正常功能过程中，装置与人体软组织之间发生的摩擦. 其中，血流在植介入体表面形成的流体摩擦会触发异常的凝血机制，从而形成血栓，这给心血管植入器械的设计和应用带来巨大的挑战.  \n\n1964年，Davie等[7]和Macfarlane等[8]首次描述了凝血行为，并概述了通过蛋白水解剪切激活的酶原级联的基本原理. 在正常人体内，凝血和纤溶系统之间复杂的相互作用维持着体内止血行为的平衡，然而，心血管植介入体的人工表面会打破这种平衡，并通过凝血机制中的接触激活途径引发血栓[9]. 植介入体的表面由一系列相互关联的过程促进凝血，包括蛋白质吸附、血小板和白细胞黏附、凝血酶生成和补体激活[10].血浆蛋白在植介入体表面的快速吸附是形成血栓的第一步，一般在几分钟内完成；随后，凝血酶在材料表面产生并促进凝血级联反应，如纤维蛋白原转换成纤维蛋白. 随后，血流在植介入体表面产生流体摩擦，表面吸附的纤维蛋白原与血液中的血小板发生黏附，并进一步引起血小板的激活，并为凝血酶的生成创造1个病灶，最终形成血栓. 目前，主要通过口服抗凝药物与对植介入体表面进行抗凝修饰来预防血栓[11].  \n\n根据植介入体表面与血液接触的异常凝血机理，其抗凝路线可分为阻断凝血路径和实现介入器械周围组织正常化两类. 阻断凝血路径主要包括药物涂层和生物惰性涂层，其中药物涂层是将活性抗凝药物固定在植介入体表面上，调节凝血和补体系统，并减少进一步的炎症反应；生物惰性涂层通过减少植介入体表面和血液成分之间的相互作用来抑制血液活化. 而植介入器械周围组织正常化通过模拟天然细胞内皮的表面来实现抗凝.  \n\n抗凝药物涂层主要包括肝素、血栓调节素和水蛭素等. 其中，肝素是目前最重要的抗凝药物之一. 肝素于1963年首次作为涂层被应用于人工心脏瓣膜[12]，现在已广泛应用于商业心血管植介入体. 肝素的五糖序列可以与抗凝血酶结合，从而改变抗凝血酶的构象，并将抗凝血酶介导的各种丝氨酸蛋白酶凝血因子的抑制率提高 $100{\\sim}1~000$ 倍. 在相关文献[13]中可以找到关于医用肝素涂层的详细论述. 血栓调节素(Thrombo-modulin, TM)是一种由内皮细胞(Endothelial cell, EC)表达的跨膜蛋白，于1992年首次应用[14]，其原理是通过凝血酶-血栓调节蛋白复合物激活蛋白C，激活的蛋白C使凝血因子Va和VIIIa失活，从而抑制凝血酶的产生[15]. 生物惰性涂层包括有机惰性涂层和无机惰性涂层，作为血液中最为丰富的蛋白质，白蛋白自1984年以来，已被广泛用于减少纤维蛋白黏附和减少聚乙烯材料上的血小板激活[16]. 另一种有机聚合物，聚乙二醇(Polyethylene glycol, PEG)，于1991年开始应用[17].PEG通过“接枝”的方法共价连接到表面，形成线性聚合物刷，进而排斥蛋白质吸附. 1991年以来，两性离子，如2-甲基丙烯酰氧乙基磷酰胆碱(2-Methacryloylox-yethyl phosphorylcholine, MPC)也被开发出来，其具有减少补体激活和蛋白质黏附效果[18]. 这类涂层最突出的特点是显著减少蛋白质黏附和血小板活化. 此外，尽管聚多巴胺(Polydopamine, PDA)不直接参与抗凝，但其可以自发吸附到不同的表面上，并为涂层材料提供优异的生物相容性[19]. 随后，受猪笼草的启发，Wong等[20]在2011年开发了润滑、注入液体和多孔表面(Slip-pery, liquid-infused, porous surface, SLIPS)的概念. 在针对血液的SLIPS技术中，通过将平滑且无缺陷的液体全氟化碳(Liquid perfluorocarbons, LP)固定在植介入体表面，涂层可以实现排斥血液中的蛋白和血小板[21]的功能，并具有自修复能力. 无机生物惰性涂层的材料主要包括类金刚石(Diamond-like carbon, DLC)[22]、热解炭(Pyrolytic carbon, PyC) 和钛 等. DLC是无定形碳的亚稳态形式[25]，该材料于1953年被研制出来，并在1971年首次被命名为DLC[22]. 由于DLC的疏水性和表面光滑性，已广泛应用于心室辅助装置[26].另一种碳基涂层PyC是一种由碳氢化合物气体热解形成的合成材料，自1969年以来已成为机械心脏瓣膜上最受欢迎的涂层. 这些无机涂层一般具有较好生物相容性和优异的物理性能.  \n\n实现植介入体周围组织正常化一般通过模拟血管壁表层的天然构造或功能以实现优异的血液相容性. 如将EC预先接种在植介入体表面，可以有效降低植介入体血栓形成和新生内膜纤维增生. 这种方法于1978被首次报道[27]. 此外，1997年发现的内皮祖细胞(Endothelial progenitor cell, EPC)，可以快速实现自我内皮化[28]. 然而，直接固定EC十分复杂. 因此，纤连蛋白[29]和胶原蛋白[30]等细胞外基质蛋白以及能够在体内捕获EC的抗体或特异性生长因子，如CD34抗体[31]也得到广泛应用. 此外， $\\mathrm{TiO}_{2}$ 涂层也可以用来诱导(引导)内皮细胞黏附及增殖[32].  \n\n典型抗凝涂层的历史以及四种常见的心血管植介入体如图1所示，相关抗凝涂层的原理列于表1中.在本文中，我们重点介绍了近10年来四种常见心血管植介入体抗凝涂层的研究进展，包括人工心脏瓣膜、血管支架、心室辅助装置和导管. 为了便于读者根据其感兴趣的植介入体查阅信息，本文中按照抗凝涂层技术所应用的植介入体分别进行综述.  \n\n![](images/dfa6a1507d377aa6d6f29eabaf5af219011ecf0c28eb7fd381da13e1106fe37c.jpg)  \nFig. 1    The cardiovascular implants and history of anticoagulant coatings: (a) artificial heart valve; (b) vascular stent; (c) ventricular assist devices; (d) catheters (created with BioRender.com.) 图 1    心血管植介入体和抗凝涂层的历史：(a)人工心脏瓣膜；(b)血管支架；(c)心室辅助装置；(d)导管  \n\n表 1    心血管植介入体上典型抗凝涂层的原理  \nTable 1    Principle of typical anticoagulant coatings on cardiovascular implants   \n\n\n<html><body><table><tr><td>Classification</td><td>Material</td><td>Typical coating</td><td>Characteristics</td><td>Birth</td></tr><tr><td colspan=\"3\">Blocking coagulation pathway</td><td>Bind to antithrombin to prevent the clot</td><td>1963[12]</td></tr><tr><td rowspan=\"7\"></td><td>Polypeptides</td><td>TM</td><td>The thrombin-thrombomodulin complexes activate protein C, which inactivates Va and VIla to suppress the thrombin generation</td><td>1992[14]</td></tr><tr><td></td><td>Albumin</td><td>Reduce fibrin adhesion and platelet activation</td><td>1984[6]</td></tr><tr><td>Organic bioinert</td><td>PEG</td><td>Decrease the adhesion of proteins and cells such as fibrinogen, platelets, and leukocytes</td><td>1991[7]</td></tr><tr><td> polymers</td><td>MPC</td><td>Minimize the adsorption of protein, suppress the platelet activation, and control</td><td>1992[18]</td></tr><tr><td></td><td>PDA</td><td>the coagulation cascade Adsorb to a broad range of biomaterials and provide a good biocompatibility</td><td>2007[19]</td></tr><tr><td></td><td>LP</td><td>Repel protein, cell and blood</td><td>2014[21]</td></tr><tr><td>Inorgaic car on n</td><td>DLC</td><td></td><td>19531221</td></tr><tr><td rowspan=\"5\">Normalizing tissue surrounding implants</td><td></td><td>PyC Ti</td><td></td><td>1969[23] 1986[241</td></tr><tr><td rowspan=\"2\">Cells</td><td>EC</td><td>Direct endothelialization</td><td>1978[27]</td></tr><tr><td>EPC</td><td>Realize self-endothelialization</td><td>1997[28]</td></tr><tr><td>Proteins</td><td>Fibronectin Collagen</td><td>Capture ECs to mimic in-vivo environment</td><td>1985[29] 1985[30]</td></tr><tr><td colspan=\"3\">CD34 antibody</td><td></td></tr></table></body></html>",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# 1    人工心脏瓣膜  \n\n人工心脏瓣膜已被广泛用于替代病理性心脏瓣膜[33]. 自1952年第一个人工心脏瓣膜被植入体内以来[34]，人们已开发出多种人工心脏瓣膜. 如图2所示，根据其材质和制作工艺可以分为机械心脏瓣膜(Mechanicalheart valve, MHV)、生物心脏瓣膜(Bioprosthetic heartvalve, BHV)和组织工程心脏瓣膜(Tissue engineeredheart valve, TEHV)[35]. 但是，人工心脏瓣膜表面与血液的接触很容易引起血栓，并导致瓣叶运动减少、瓣叶接合受损、瓣叶增厚、有效通道面积改变、跨瓣压力梯度增加和经瓣反流等情况[36]. 如果缺乏抗凝手段，患者很容易发生中风[37]. 因此，人工心脏瓣膜置换后需要长期抗凝，目前有很多研究尝试通过抗凝涂层来实现人工心脏瓣膜表面的全面抗凝.  \n\n![](images/fad9ba3a9c84d6f5cbd7262a85c224801dc0d157a62d28c33de48275af6a352a.jpg)  \nFig. 2    Artificial heart valves and their coatings: (a) multi-in-one strategy on the bioprosthetic heart valve realized multi-functional anticoagulation [38]; (b) superhydrophobic coating on the mechanical heart valve to repel platelet and red blood cell [39]; (b1) SEM micrograph of the morphology of the superhydrophobic coating; (b2) SEM micrograph of the thickness of superhydrophobic coating; (b3) surface topography profile of the superhydrophobic coating; (c) ECM coating on the tissue engineered heart valve can capture ECs and induce endothelialization [40]   \n图 2    人工心脏瓣膜和抗凝涂层：(a)生物心脏瓣膜上的多合一策略涂层实现多功能抗凝；(b)机械心脏瓣膜上的超疏水涂层以排斥血小板和红细胞；(b1)表面超疏水涂层形貌的SEM照片；(b2)超疏水涂层厚度的SEM照片;(b3)超疏水涂层的表面高度形貌；(c)组织工程心脏瓣膜上的细胞外基质涂层可以捕获EC并引起内皮化",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 1.1 阻断凝血路径  \n\n肝素是人工心脏瓣膜上使用最重要的抗凝涂层之一[41]. 最近的研究集中在肝素和生物分子联用策略，以实现抗凝血和增强生物相容性. 与肝素联用的碱性成纤维细胞生长因子(Basic fibroblast growth factor,bFGF)通过逐层沉积技术作为多种功能分子被包被在脱细胞的猪主动脉心脏瓣膜瓣叶上[42]. 结合到瓣叶上的肝素和bFGF的量与培养介质中的浓度成比例，在生理条件下，肝素和bFGF从包被的瓣叶中释放可以保持生物活性持续4天以上. 此外，肝素-壳聚糖[43]、肝素-血管内皮生长因子(Vascular endothelial growth factor,VEGF)[44]和肝素-基质细胞衍生因子(SDF-1α)[45]也被用作多重抗凝药物表面. 体内试验结果表明，这类多层膜可以减少血小板的黏附和活化，并被血液中的内皮祖细胞覆盖. 此外，研究发现单独的肝素涂层可以减少生物瓣膜上的组织钙化[41].  \n\n利伐沙班(Rivaroxaban, RIVA)是一种口服Xa因子抑制剂，通过抑制游离Xa因子和凝血酶原酶活性以及凝块结合的Xa因子，可以有效阻断凝血酶生成从而提供持续的抗凝作用. 王云兵等[38]将载有RIVA的纳米凝胶和可分离的PEG修饰在生物瓣膜表面，建立了一种多合一的方法来修饰生物瓣膜，使其具有长期抗血栓形成性能，并能加速由葡萄糖触发的内皮化. 图2(a)所示为该涂层的抗凝原理，葡萄糖氧化酶催化葡萄糖氧化产生 $\\mathrm{H}_{2}\\mathrm{O}_{2}$ 和局部酸性环境，产生的 $\\mathrm{H}_{2}\\mathrm{O}_{2}$ 刺激纳米凝胶释放RIVA以获得持续的抗血栓功能. 结果表明，该表面黏附的血小板很少，证明了RIVA的纳米凝胶涂层具有良好的持续抗凝能力. 此外，Wang等[46]进一步通过RIVA结合抗炎药物涂层在生物瓣膜上实现了材料和组织良好的相容.  \n\n有机和无机生物惰性涂层均已应用于人工心脏瓣膜. 对于有机生物惰性涂层，PEG基的水凝胶被用来防止蛋白质黏附. Grande等[47]首先将表面胺基与NHS-PEG-丙烯酸酯反应，同时让葡萄糖吸收到瓣膜主体中. 之后，将葡萄糖氧化酶、PEG二丙烯酸酯(PEGDA)和铁离子加入到体系中，引发自由基聚合，将PEGDA水凝胶结合到表面的丙烯酸酯位点. 结果显示在瓣膜样品上形成的薄层能够有效避免蛋白质黏附，而不显著影响表面机械性能. 此外，Roseen等[48]还尝试了在表面沉积PEG双丙烯酰胺的水凝胶涂层. 在本研究中，将表面黏附性、机械性能和固定性能方面对涂覆的样品与生理组织和未涂覆的戊二醛固定的组织进行比较. 研究结果显示沉积的涂层在整个瓣膜瓣叶表面是连续的，并且样品显示其在蛋白质黏附和机械硬度方面可恢复至生理水平. 此外，已知稳定交联的纤维蛋白较难形成血栓. 因此，通过孵育 $15~\\mathrm{min}$ 可以将纤维蛋白凝胶涂覆在快速降解的冠形聚醚醚酮增强环上[49]，该方法制备的瓣膜在长期试验中功能良好，移植物的重塑导致瓣膜组织具有较佳的稳定性.  \n\n无机涂层，如PyC[50]、超纳米晶金刚石[51]、石墨烯[52]以及氧化钛和氮化钛[53]已应用于机械瓣膜中. 尽管PyC由于其相对良好的耐磨性、抗疲劳性、血液相容性、化学惰性和无毒而成为机械瓣膜中最受欢迎的涂层，但目前基于PyC的机械瓣膜仍需要配合使用华法林来预防血栓. 另一方面，超疏水涂层在抗凝方面也显示出潜力. Hatoum等[39]在瓣膜表面沉积了商业化的超疏水涂层[Rust-oil never wet clear spray，图2(b)]，该涂层的超疏水效应减少了血凝块的黏附. 但是，由于瓣膜表面承受较高的剪切应力，涂层的血液动力学性能没有得到改善[39,54]，进而影响了瓣膜的性能，超疏水抗凝涂层技术仍需要进一步改进.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 1.2 组织正常化  \n\nEC预接种是一种有效的内皮化方法. 例如，EC和成纤维细胞已经被成功接种到聚氨酯心脏瓣膜支架上[55]. 另外，固定SDF-1α和碱性成纤维细胞生长因子可以改善去细胞异种心脏瓣膜上内皮祖细胞的再细胞化，在搅拌生物反应器中得到了验证，可以促进再细胞化[56]. 然而，目前的预接种方法较为复杂. 是将多种不同的细胞标记物应用于体内吸引EPC或EC. Jordan等[57]在猪肺动脉瓣的基底上涂覆了内皮祖细胞标记物CD133抗体. 在移植到绵羊肺部位置之前，用自体内皮祖细胞重新接种基底或与CD133抗体结合. 结果显示CD133抗体组在植入1个月后在涂层表面结合了EC，而未处理组和细胞接种组结合较少的EC或间质细胞. Schmidt等[58]实现了基于羊水来源祖细胞的心脏瓣膜. 他们在研究中将胎儿人羊膜祖细胞从常规采样的羊水中分离出来，并通过CD133磁珠分选；之后，将CD133衍生的细胞接种到由可快速生物降解的聚合物制成的心脏瓣膜瓣叶支架上. 分化的 $\\mathrm{CD}{133}^{+}$ 细胞通过内皮NO合成酶和TM表现出了EC的功能性特征，结果显示内皮化组织随细胞外基质成分的产生而形成.  \n\n除了抗体，细胞外基质蛋白涂层也可以加速自体体内的内皮化. 图2(c)展示了一种细胞基质涂层的方法，该方法可增强聚苯乙烯-嵌段异丁烯-嵌段苯乙烯(SIBS)的生物相容性[40]. 细胞外基质涂层不仅减少了蛋白质和血小板的吸附，还抑制了免疫反应，并诱导了组织再生. 此外，Lintas等[59]开发了基于细胞外基质的经导管主动脉瓣置换技术，通过绵羊的体外研究和体内急性研究，证明了包被细胞外基质的组织工程心脏瓣膜的可行性. 此外，脱细胞心血管植介入体上的纤连蛋白表面涂层已被证明是可行的，并在体循环中持续至少8周[60]. 血管内皮生长因子已被用作细胞标志物，并与不同的生物相容性材料偶联用于内皮化.通过1，4-丁二醇二缩水甘油醚的交联，可以开发具有血管内皮生长因子-透明质酸水凝胶涂层的杂化心包[61].通过在体大鼠皮下植入模型，研究了人脐静脉EC在心包、血小板黏附和钙化上的黏附和生长潜力，研究结果显示有较少的血小板黏附. 在另一项研究中，内皮生长因子-岩藻依聚糖的聚电解质多层膜被用于开发功能性生物心脏瓣膜[62]，评估聚电解质多层膜涂层瓣膜的血液相容性、EC的黏附和生长潜力，结果展现了抗血栓形成和非钙化特性的能力. 此外，Theodoridis等[63]研究发现，细胞通讯网络因子1 (Cellular commu-nication network factor 1)被用于支持再内皮化. 所有表面均未观察到血栓生成，老年绵羊中瓣膜基质细胞的再增殖显示了基质引导再生的能力，并证实了脱细胞基质对于老年个体心脏瓣膜置换的适用性.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 1.3 挑战与展望  \n\n尽管人工心脏瓣膜已经发展了50多年，但依然需要面对复杂的血流动力学环境[64]. 人工心脏瓣膜上的抗凝涂层面临的主要挑战是长期承受由瓣叶运动和高剪切应力引起的机械磨损、摩擦以及动态流动条件，这将导致抗凝涂层的损失，并增加了抗凝涂层的工艺难度. 药物或内皮化涂层因此很难牢固地修饰在机械瓣膜的表面，大多数机械瓣膜都是通过化学气相沉积法涂覆抗凝效果相对较差的无机涂层，机械瓣膜仍然容易形成血栓，更重要的是，机械瓣膜的设计使得其剪应力 $(150{\\sim}380\\ \\mathrm{Pa})$ 超过了血小板的阈值，导致血小板的异常激活. 因此，植入机械瓣膜后，患者通常需要长期口服抗凝剂和维生素K拮抗剂，如华法林，但这将增加出血风险. 然而，由于使用寿命更长，机械瓣膜依然是大多数年轻患者的首选. 对于生物瓣膜，由于戊二醛在制造过程中被用作基底，因而目前具有更好的生物相容性涂层的生物瓣膜在植入多年后容易钙化，直接影响了瓣膜的寿命. 虽然有研究开发了一些抗钙化的策略，但仍缺乏长期实践检验，因此，生物瓣膜大多被老年病人选用. 近年来，大量研究集中在新兴的组织工程心脏瓣膜的设计，由于其持续时间和抗凝作用的效果更均衡，因此在改善现有的瓣膜使用状况方面非常具有潜力，但是该方面的研究尚不成熟，仍缺乏有力的临床实践数据.  \n\n本节中涉及的抗凝涂层列于表2中. 目前的抗凝涂层尚不能完全满足人工心脏瓣膜的要求，在过去的10年里，复合涂层因其多元的抗凝机理而备受关注，该涂层可以实现前期的阻断凝血途径和后期的组织正常化的有机结合，在抗凝效果和寿命上实现兼顾，尽管缺少有力的临床实践，但仍不失为一种有潜力的彻底解决人工心脏瓣膜凝血问题的理想抗凝涂层.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2    血管支架  \n\n冠状动脉疾病是当前世界上三大致死原因之一[65-66]，其特征为内皮下斑块破裂诱发血栓最终导致动脉狭窄. 心血管支架作为一种支撑血管的植入器械，已经成为患者的“救命神器”，被列为本世纪十大医学突破之一[67]. 在结构上，支架是一种小型、复杂的圆柱形中空结构，其中包括一系列的支柱和连接元件[68-69].植入的支架起到维持体内血管内腔形状的作用[70].  \n\n经过科学家的努力，已经开发了三代支架以减少支架植入手术后的不良反应. 从裸金属支架(Bare-metalstent, BMS)到药物洗脱支架(Drug-eluting stent, DES)，再到最近研发的生物可吸收支架，该领域正在不断发展[71]. 遗憾的是，由于晚期再狭窄、血栓形成等临床并发症，目前的支架在很大程度上仍不能完全满足临床的需求. 目前，在临床上首选的是金属支架，因为其比聚合物支架具有更好的机械性能和射线不透性[72]. 为了解决支架植入后血栓形成的问题，表面涂层技术得到广泛的研究，以提高血管支架的血液相容性，减少病人对全身抗凝的需求. 黄楠等[32,73-76]在通过涂层药物或生物分子对金属支架进行修饰，以增强抗血栓形成、抗再狭窄和/或内皮化方面进行了大量研究，并在临床中得到广泛的应用.",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.1 阻断凝血路径  \n\n目前，血管支架中已经出现了一系列商业化的肝素涂层技术，如CORLINE $\\textsuperscript{\\textregistered}$ Heparin Surface[77]、Hepa-med™涂层[78]以及Carmeda肝素结合[79]等. CORLINE $\\textsuperscript{\\textregistered}$ 肝素表面由未分级肝素大分子复合物组成，其通过交联剂与多胺载体链共价连接[77]. 在Hepamed™涂层的设计中，聚乙烯基硅氧烷首先共价连接到支架表面，然后将表面接枝到聚乙烯基硅氧烷上，然后嫁接聚乙烯亚胺. 最后，肝素与聚乙烯亚胺共价偶联[78]. Carmeda肝素涂层使用肝素分子还原端和材料底物之间的单个共价键进行连接[79]，进而生成稳定的非浸出涂层，厚度为数百纳米.  \n\n除了商业肝素涂层技术外，还有几种新型涂层技术. 如图3(a)所示，使用内皮生理功能中的关键分子：肝素和NO来模拟内皮的涂层，即将肝素和产生NO的化合物硒代胱胺依次结合在含胺膜上[80]. 此外，还可以使用仿生三明治状逐层沉积来模拟EC功能. 在该项研究中，壳聚糖和肝素作为聚电解质，同时使用儿茶素/铜(EGCG/Cu)复合物[81]. 该策略为心血管植入式医疗器械的改造提供了一种便捷、通用的方法. 在另一项研究中，两个血管活性部分：可以生成NO的有机硒(SeCA)以及EPC靶向肽，通过生物正交缀合到支架表面[82]，结果显示可以显著抑制血栓形成和平滑肌细胞(Smooth muscle cells, SMC)迁移，促进EPC募集和增殖，防止支架内再狭窄.  \n\n此外，受植物酚胺化学策略的启发，Qiu等[83]结合了植物多酚、单宁酸(TA)和凝血酶抑制剂比伐卢定(BVLD)的生物学功能，定制了具有多种表面功能的心血管支架. 他们首先在支架表面制备了等离子体聚合烯丙胺的含胺涂层，然后基于酚胺化学(即迈克尔加成反应)在碱性溶液中依次偶联TA和BVLD，以实现TA和BVLD在支架表面的协同改性. 结果表明，TA和BVLD的联合作用促进了支架的快速再内皮化，减少了体内的内膜增生，并减少了与再狭窄和晚期支架血栓形成相关的临床并发症. 此外，结合抗凝和抗炎药物的血管支架涂层技术正在迅速发展. 通过肝素/NONOate纳米颗粒(Hep/NONOates)为支架表面开发双药物缓释涂层以实现原位抗凝和促内皮化[84]，其具有良好的稳定性和抗凝活性，可有效促进内皮化，提高药物洗脱支架的安全性和有效性. 此外，还开发了具有亲水性(肝素)和疏水性(雷帕霉素)药物的介孔二氧化硅涂层，用于快速抗凝和长期抗组织增殖. 结果表明，肝素和雷帕霉素的释放可持续30天以上，表明介孔二氧化硅和疏水性药物涂层具有应用于BMS表面改性的潜力[85].  \n\n表 2    人工心脏瓣膜的抗凝涂层  \nTable 2    Anticoagulant coatings on artificial heart valves   \n\n\n<html><body><table><tr><td>Coating</td><td>Substrate</td><td>Coating method Application</td><td></td><td>Pros</td><td>Cons</td><td>Ref</td></tr><tr><td>Heparin</td><td></td><td>Covalently attachment</td><td>BHV</td><td>Better anticoagulant effect</td><td> Hardly withstand shear force</td><td>2017[41]</td></tr><tr><td>Heparin-bFGF</td><td rowspan=\"6\">Dellellularized porcine</td><td rowspan=\"6\">Intermolecular</td><td>BHV</td><td rowspan=\"5\">Multi-function for inhibiting coagulation cascade and promoting long term effect</td><td rowspan=\"6\">Lack of clinical practice and has the risk of calcification</td><td>2010[42] 2012[43]</td></tr><tr><td>Heparin-chitosan</td><td>BHV</td><td></td></tr><tr><td></td><td>TEHV</td><td>2013[44]</td></tr><tr><td>Heparin-VEGF Heparin-SDF-1α</td><td>TEHV</td><td>2015[45]</td></tr><tr><td>heart ECM</td><td></td><td>2021[38]</td></tr><tr><td>RIVA PEGDA</td><td>interactions</td><td>BHV BHV</td><td> Prevents protein adhesion and</td><td>PEGDA coating is</td><td>2022[46] 2020[47]</td></tr><tr><td>PEGDAA</td><td></td><td></td><td>BHV</td><td>does not significantly affect surface mechanical properties Offers the potential to tightly</td><td>discontinuous and require further optimized to increase the coverage and thickness</td><td>2020[48]</td></tr><tr><td>Fibrin gel</td><td>Polycarbonate/ Polycaprolactone</td><td>Intermolecular interactions</td><td>TEHV</td><td>control the mechanical, degradation, and bioactive properties of grafting</td><td>Longer-term follow-up studies is required</td><td>2017[49]</td></tr><tr><td>Microstructure Ultrananocrystalline</td><td>PyC</td><td>Pulsed laser deposition</td><td>MHV</td><td>Robust and potential to promote endothelialization</td><td>Requires clinical practice</td><td>2018[50]</td></tr><tr><td>diamond Graphene</td><td>PMMA</td><td>Chemical vapor deposition</td><td>MHV BHV</td><td>Robust and relatively good biocompatibility</td><td>Anticoagulant effect is not very good</td><td>2015[51] 2016[52]</td></tr><tr><td>TiO，TiN</td><td>Ti</td><td>Plasma immersion ion implantation</td><td>MHV</td><td>Robust and relatively good biocompatibility</td><td>Improved compatibility</td><td>2006[53]</td></tr><tr><td>Rust-OleumNeverWet</td><td>PyC</td><td>and deposition Ionic bonding</td><td>MHV</td><td>Repel proteins and cells, and minimal impact on valve</td><td>Further research to investigate long-term valve performance</td><td>2020[39]</td></tr><tr><td>Clear Spray ECs and fibroblasts</td><td>PU</td><td></td><td>TEHV</td><td>hemodynamics</td><td></td><td>2017[54] 2012[55]</td></tr><tr><td>ECs</td><td>Dellellularized ovine heart ECM</td><td></td><td>TEHV</td><td colspan=\"3\"></td></tr><tr><td></td><td rowspan=\"4\">Dellellularized porcine</td><td></td><td>TEHV</td><td rowspan=\"5\">Biocompatibility, non- thrombotic, non-teratogenic, long-term durability and growth potential</td><td rowspan=\"6\">1.High shear stress can destroy the coating integrity 2. Require clinical practice</td><td>2018[56]</td></tr><tr><td>CD133 antibody</td><td>Covalent</td><td></td><td>2012[57] 2007[58]</td></tr><tr><td></td><td>attachment</td><td>TEHV</td><td>2020[40]</td></tr><tr><td>ECM</td><td></td><td>TEHV</td><td>2018[59]</td></tr><tr><td>Fibronectin</td><td>Intermolecular</td><td>TEHV BHV</td><td>2013[60] 201961]</td></tr><tr><td>VEGF-hyaluronic acid VEGF-fucoidan</td><td></td><td>interactions</td><td>BHV</td><td></td><td></td><td>2018(62]</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Cellular communication network factor 1</td><td>Dellellularized ovine heart ECM</td><td>Covalent attachment</td><td>BHV</td><td></td><td></td><td>2015[63]</td></tr></table></body></html>  \n\n生物相容性聚多巴胺在血管支架的生物惰性涂层方面得到应用. 最近，在裸金属冠状动脉支架表面涂上1层稳定的聚多巴胺层，然后将2-溴异丁酰溴(BIBB)共价固定在聚多巴胺层表面，以引入聚合反应所需的烷基溴引发基团[86]. 如图3(b)所示，通过表面诱导原子转移自由基聚合(SI-ATRP)进而在裸316L不锈钢(SS)金属支架上构建甲基丙烯酸磺乙酯(SBMA)/甲基丙烯酸缩水甘油酯(GMA)双功能复合涂层. 然后作为NO供体的二亚乙基三胺(NONOate)通过GMA单元的活性环氧基团连接到聚合物刷上以产生NO释放[87-91].改进后的支架表面保持高水平的抗凝活性和NO的持续释放，显著抑制血栓形成，促进EC生长.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 2.2 组织正常化  \n\n内皮不仅可以预防血栓形成，还可以介导SMC的迁移和增殖. 支架上的快速再内皮化为预防支架内再狭窄和晚期支架血栓形成提供了一种可行性方法. 近年来，预接种ECs的方法已经产生了一些有希望的实验室结果. 然而，制备涂层的过程既昂贵又耗时[92-93].此外，ECs的来源、种植后的脱落以及细胞培养过程中的感染仍然是其进一步发展的障碍. 在血管愈合过程中，内皮层的再生可以来自邻近ECs迁移或循环中ECs的募集[94-96]. 自然愈合方法为植入后材料的体内/原位内皮化提供了一种良好的替代策略[95-97]. 制造具有化学和物理性质的材料以诱导相邻ECs迁移或直接从循环中捕获内源性循环ECs的方法对于原位内皮化尤为重要. CD34是一种细胞表面抗原，表达在血管EC[98]、EPCs[99]和造血祖细胞[100]中. 最近，开发了一种EPC捕获支架，其表面涂有CD34抗体以捕获循环EPC，进而实现快速原位内皮化[99,101]. CD34抗体涂层支架已表现出显著减少新内膜形成的效果. 然而，临床试验结果表明，由于循环EPCs的含量极低[99]，使得EPCs的增殖和分化难以准确控制[102]，因此抗再狭窄作用并不如预期的那样显著. 如图3(c)所示，将ECs特异性配体固定到基底上的方法，以刺激EPC和血管ECs的优先黏附和生长，这对于快速原位内皮化至关重要.  \n\nLin等[103]通过将CD34抗体固定在肝素/胶原蛋白多层膜上，制备了涂有EC选择性的涂层. 将CD34抗体固定在细胞相容性和抗凝剂基底上表现出EC选择性并快速实现原位再内皮化. 此外，Sun等[104]采用Ni-Ti合金片模拟支架，他们以聚多巴胺为基础构建了生物因子涂层的镍钛合金片，嫁接肝素并涂附VEGF和CD34抗体. 结果表明，所构建的支架具有良好的生物相容性，能有效促进表面内皮化.  \n\nEPC的特征是表达CD133、CD34和VEGF受体-2(VEGFR2、Flk-1)[105-106]. 根据EPC在支架表面的黏附强度，已开发了明胶、VEGFR2、CD34或CD133抗体等几种底物[107-108]. 结果表明，EPCs在抗CD133涂层支架表面的附着力显著高于抗VEGFR2和抗CD34涂层支架. 此外，剪切应力在一定程度上可以促进EPC增殖和NO分泌. 与其他两种底物相比，EPC在抗CD133抗体的底物上表现出更强的黏附性[109]. 此外，与BMS相比，抗CD133抗体涂层支架(CD133支架)可以通过图 3    血管支架上的三种涂层示意图：(a)肝素化表面的依次固定策略[80]；(b) SS-PSBMA-PGMA-NONOate共聚物刷接枝在316L不锈钢支架上的示意图[86](PSBMA为聚缩水甘油基磺乙基甲基丙烯酸酯；PGMA为聚甲基丙烯酸缩水甘油酯)；(c)带有固定化 EPC、抗CD34或抗CD133抗体的血管支架涂层  \n\n![](images/45b5c866d1d3e1518cf3127411c54922ac7088c2b681788bdaf173afe55cc0fb.jpg)  \nFig. 3    Schematic of three coatings on the vascular stent: (a) a sequential co-immobilization strategy to realize a heparinized surface[80]; (b) the schematic of SS-PSBMA-PGMA-NONOate copolymer brushes grafting on 316L SS stent[86](PSBMA, polyglycidyl sulfoethyl methacrylate; PGMA, polyglycidyl methacrylate); (c) the vascular stent coating with immobilized EPCs, anti-CD344 or anti-CD133 antibodies  \n\n其优异的EPC捕获能力加速再内皮化[110-111]. 最近，已经报道了一种用于生化表面修饰的多步骤策略，合成了一种新的、有效且生物相容性的血管内植介入体，该植介入体涂有固定的抗CD133抗体[112]，能有效捕获EPC并减少SMC增殖.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 2.3 挑战与展望  \n\n理想的支架应具有良好的生物相容性、柔韧性、运输性、较强的径向力和透视下良好的射线不透性.其几乎对血管壁不造成创伤，炎症反应小，促进再内皮化，并最终促进血管愈合和重塑[113-116].  \n\n本节中涉及的用于血管支架上的抗凝涂层列于表3中. BMS上的涂层主要用于控制生物相容性、降解率以及蛋白质吸附，并允许足够的内皮化以确保更好的临床效果以减少再狭窄和血栓形成. 目前该技术的研究重点是面向钛合金、镍钛合金和316L不锈钢进一步增强EC的迁移或附着. 特别是联合使用多种涂层技术，例如在肝素/胶原多层膜上固定抗CD34抗体，可能是有效延缓支架血栓形成的可行手段. 然而，一些临床问题尚未得到解决，如BMS和DES的新生内膜增生、晚期支架血栓形成和炎症反应以及响应性和生物可吸收支架力学性能的不足[117]. 要克服这一不足，需科学家进一步开发支架装置，进而对其长期稳定性和失效机理进行深入分析.  \n\n第二代血管支架——药物洗脱支架具有靶向性好、局部组织中药物浓度高以及副作用小等特点，使得其在冠脉支架市场占据主导地位. 然而，裸金属支架进行表面涂层处理或药物洗脱支架，大多都基于金属作为支架材料，这是因为金属材料具有良好的机械特性，可以在保持装置形状和完整性的同时提供狭窄血管所需的支撑力，但金属材料的不可降解性是一、二代血管支架最大的局限性. 因此，第三代血管支架—聚合物或金属基生物可吸收支架应运而生. 生物可吸收支架即可对狭窄血管提供支撑力，又可在一段时间后进行自降解，并在重塑过程后溶解或吸收，然而，这项技术目前仍处于临床试验阶段[118]. 因此，目前仍然尚未完全解决支架表面血栓形成等问题，还需对支架材料及涂层技术在其力学性能、促内皮化、抑制炎症发生以及抑制内膜增生等方面进行深入研究.  \n\n表 3    血管支架上的抗凝涂层  \nTable 3    Anticoagulant coatings on vascular stents   \n\n\n<html><body><table><tr><td>Coating</td><td>Substrate</td><td>Coating method</td><td>Pros</td><td>Cons</td><td>Ref</td></tr><tr><td>Heparin</td><td>Titanium alloy, Ni-Ti alloy</td><td></td><td>Covalent attachment Prevent platelet activation and Hardly withstand mechanical suppress smooth muscle cell</td><td>damage and may induce</td><td>2008[77] 1998[78] 1983[79]</td></tr><tr><td>Heparin and NO</td><td>316L stainless steel</td><td>Chemical co- immobilization</td><td>migration proliferation The sustained release of</td><td>thrombocytopenia</td><td>2019[80]</td></tr><tr><td>EGCG/Cu complex</td><td>PLLA</td><td>Intermolecular interactions</td><td>heparin and continuous generation of NO at the blood/material interface can</td><td>Cause neointima hyperplasia response and inflammatory</td><td>2020[81]</td></tr><tr><td>NO-generating SeCA and the EPC-targeting peptide</td><td rowspan=\"4\">316L stainless steel</td><td>Bioorthogonal conjugation</td><td>mimic the basic function of ECs and reduce intimal hyperplasia Combat the inflammation,</td><td>response</td><td>2020[82]</td></tr><tr><td>Plant polyphenol, TA, and BVLD</td><td>Phenolic-amine chemistry strategy</td><td>thrombogenicity, promote re- endothelialization and inhibit intimal hyperplasia and stenosis in vivo</td><td>Induce tissue factor and enhance thrombogenicity</td><td>2020[83]</td></tr><tr><td>Hep/NONOates</td><td>Electrostatic interaction Evaporation-induced</td><td>Good stability and</td><td>Heparin can induce thrombocytopenia</td><td>2020[84]</td></tr><tr><td>Mesoporous silica SBMA/ GMA bifunctional</td><td>self-assembly method“ Chemical polymerization</td><td>anticoagulant activity, promote endothelialization, and simple</td><td>The releasing rate of heparin is low</td><td>2019[85] 2020[86]</td></tr><tr><td>composite</td><td rowspan=\"2\">Titanium alloy, Ni-Ti alloy Ni-Ti alloy</td><td rowspan=\"2\">Covalent attachment</td><td rowspan=\"2\">Strong binding force, good biocompatibility, accelerate the re-endothelialization and simultaneously inhibit SMCs expansion</td><td rowspan=\"2\">The process is costly and requires long cell culture periods</td><td>2005[92]</td></tr><tr><td></td><td>2007[93] 2005[99] 2006[101] 2010[103] 2021 [104] 2012[107] 201[108] 2015[109]</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3    心室辅助装置  \n\n由于左心室收缩功能障碍引起心力衰竭的发病率呈现指数增长，已经成为一种全球性的流行病[119].心脏移植供体的供应短缺使得心室辅助装置(VADs)和全人工心脏(TAHs)作为一种替代治疗方法得到快速发展[120].  \n\nVADs可以根据其机械作用方式(即脉动流、连续流)或其工作原理(即轴流泵、离心泵)进行分类[120]. 第一代心脏泵是脉动流泵，如Berlin heart excor, thor-atec TCI pump，Heartmate PVAD以及Heartmate XVE等.第二代心脏泵是连续流泵，例如HeartMate (HM) II和Jarvik $2000^{[121]}$ . 第三代心脏泵是磁悬浮泵，如Heart-ware  HVAD， Berlin  heart  incor  LVAD， DuraHeart，VentrAssist LVAD[119,122-124].  \n\n20世纪30年代，TAH第一次在试验中被植入到动物体内. 然而，由于TAH的几何形状、供电、生理和生物因素等方面的缺陷，目前只有一种TAH被批准用于临床应用[125]. 最近，又出现了多款创新性的TAH模型，包括：CardioWest SynCardia TAH[126]，AbioCor TAH[127]和Carmat TAH[128]. TAHs的材料包括涤纶、硅橡胶、钛、聚乙烯、PyC、ePTFE、AngioFLEX和PU等.  \n\n血栓栓塞、出血和感染是VADs的主要并发症. 血栓的形成涉及到VADs表面与血液接触后引起的凝血酶和血小板的激活，以及高剪切率导致的血小板激活[129]. 以HeartMate II LAVD为例，植入后3个月内血栓发生率高达 $8.4\\%$ . 如果这类血栓患者未进行心脏移植手术或心脏泵置换的话，其死亡率高达 $48\\%^{[130]}$ . 为了避免VADs的相关并发症，研究人员设计了各种抗凝涂层，用于改善VADs的血液相容性.",
+        "category": " Introduction"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.1 阻断凝血路径  \n\nCarmeda生物活性表面已被应用于由Berlin HeartGmbH开发的心脏泵，用以避免血栓在泵内沉积，使心脏泵能够在患者体内长期稳定地运行. Koster等[136]使用Carmeda表面技术在Berlin Heart VAD上制备PU和未分离肝素的涂层. 结果表明，肝素包覆VAD未引起血栓形成反应或免疫反应. 此外，Hetzer等[122]还针对用Carmeda法涂有肝素的Berlin Heart Incor轴流泵进行了研究，没有在冠状动脉中发现任何血栓栓塞事件. 在植入患者体内近1年以后，有活性的肝素涂层仍可以与VADs表面紧密结合[137-138].  \n\n另一种基于生物抗凝剂的涂层是将经过基因工程改造的，能产生NO的SMC种植在LVADs上，可以构建NO释放的涂层[139]. 与EC层相似，经过GTP环水解酶基因转染NO合成酶的SMC通过释放NO可以显著地降低血小板对表面的黏附. 将能产生NO的基因工程SMC植入左室导管后，试验结果表明，在体内和体外流动条件下，SMC能很好地黏附在泵表面[139].  \n\nMPC聚合物已应用于VAD，图4(a1)所示为磷脂在MPC聚合物表面的吸附原理图[132]. Yamazaki等[140]将经MPC涂层改性的EVAHEART离心血泵植入7头小牛体内，对其进行评估，没有发现MPC涂层表面有血栓形成. 从长期来看，EVAHEART心脏泵具有良好的血液相容性. 此外，Kihara等[141]对MPC涂层和DLC涂层的EVAHEART LVADs进行了研究. 在这项研究中，他们将4个MPC涂层的LVAD和8个DLC涂层的LVAD植入小牛体内，结果表明MPC涂层具有较高的生物相容性水平，有利于避免血栓的形成，与DLC涂层类似. 此外，MPC涂层由于其易于应用和可以减少抗凝治疗，显示出更大的潜力，可以有效提高LVADs的抗凝性能. Someya等[142]用MPC涂层对一种名为MedTech Dispo的离心式心脏泵的血液接触表面进行了改良，并将该泵植入了7头左心搭桥的小牛体内. 体内试验结果表明，MPC涂层可以在至少2周内有效防止血栓的形成. 此外，他们还研究了等离子体诱导MPC接枝聚合技术，并将MPC链连接到TiAl6V4钛合金表面[143]. 试验结果表明，相对于对照组，MPC表面血小板的沉积和活化减少. 然而，由于MPC涂层的生物降解性，其寿命有限，这意味着植入一段时间后，患者仍需要接受抗凝治疗. 与TiN和DLC涂层相比，MPC涂层在VADs上的强度和稳定性较差[141]. 因此，MPC涂层应通过中间层和连接剂与VADs表面形成强共价键连接，提高涂层的耐久性和稳定性.  \n\n贻贝可以黏附几乎所有类型的基底，包括钛基底.如图4(a2)所示，树突状聚甘油(MI-dPG)和线性聚甘油(lPG)的仿生贻贝组合涂层具有细胞排斥特性、生物相容性和补体激活功能[133]. Kulka等[133]研究表明，lPG功能化的MI-dPG涂层可以防止细胞黏附，包括人肺泡基底上皮癌细胞和鸡成纤维细胞. 此外，涂层对血小板的黏附和活化有一定的抑制作用. 最后，MI-dPG涂层在Berlin Heart GmbH上具有较好的抑制细胞和血小板黏附的作用.  \n\n![](images/c8f591f3dfbfaac3e867d542e7113dacf1c359b5215b3d68435eedd6315b3b01.jpg)  \nFig. 4    The anticoagulation coatings on VADs: (a) magnetically levitated pumps[131]: (a1) MPC coatings could adsorb phospholipids from the blood, producing a surface with good natural blood compatibility[132]; (a2) mussel-inspired coatings could prevent the primary adhesion of protein and cells from the bloodstream[133]; (b) total artificial heart[125]: (b1) expanded polytetrafluorethylene (ePTFE) [134]; (b2) angioflex (proprietary polyether urethane)[127]; (c) continuous-flow pumps[131]: the feature size of the microstructure (gratings) was designed to maximize cell adhesion and migration[135].   \n图 4    VADs上的抗凝涂层：(a)磁悬浮泵[131]：(a1) MPC涂层可以从血液中吸附磷脂，产生具有良好自然血液相容性的表面[132].(a2)仿生贻贝设计的涂层可以防止血液中蛋白质和细胞的初次黏附[133]；(b)全人工心脏[125]：(b1)膨胀聚四氟乙烯(ePTFE)[134]；(b2) angioflex (一种专用的聚醚聚氨酯)[127]；(c)连续流心脏泵[131]：微结构(光栅)特征尺寸的设计可以最大化EC的黏附和迁移[135]  \n\n膨化聚四氟乙烯(ePTFE)已广泛用于与血液接触的表面，并显示出低凝血性. 因此，应用这种材料研制出了CARMAT TAHs的人工心室的弹性隔膜，其血小板活化和纤维蛋白沉积的水平与肝素包被的医用级聚氯乙烯(PVC)相似[图4(b1)][134]. Angioflex是一种专有的聚醚聚氨酯，也被用于光滑心室和三叶瓣膜的血液接触表面[图4(b2)]所示[127]. AbioCor TAH 通过在体外试验[144]和体内试验[145]的测试证明了这种材料在长期试验中的可行性，未发生血栓形成、栓塞事件或血液损伤的事件.  \n\nDLC是一种亚稳态的无定形碳，包含类金刚石位点和石墨位点的组合，其中一些键由氢终止[25]. 常见的DLC薄膜沉积工艺有脉冲激光沉积、阴极电弧沉积、直接离子束沉积以及等离子体增强化学气相沉积等方法. 由于疏水性和表面光滑性，DLC涂层具有优秀的生物相容性和良好的血液相容性(血小板黏附最小)[26,146-147]. 自1998年以来，DLC涂层已被用于VAD.Yamazaki等[148]将DLC涂层应用于Sun Medical离心泵的血液接触面，以提高该产品的血液相容性. 体内试验表明，这款心脏泵长期血液相容性良好，可无故障连续工作6个月以上. VentrAssist公司生产的可植入旋转血泵，在与血液接触的表面涂有DLC涂层[149]. EVAHE-ART VADs也涂有DLC涂层. 在动物试验中，将EVA-HEART VADs植入20头牛体内，心脏泵的持续工作时间为30\\~196天[150]. 由于VADs的高转速和高剪切速率，DLC涂层技术应用于VADs的主要局限性是存在微裂纹和膜破裂的风险[120]. 一种具有弹性特征的改性DLC涂层有望改善VAD的血液相容性[151].  \n\n钛合金是VAD的主要材料之一. 氧化钛涂层不仅能提高心脏泵的耐磨性，而且具有与抛光钛相似的血液相容性[152]. Klein等[152]测试了等离子体电解氧化(PEO)、抛光钛(Ti Gr 5)和未进行表面处理钛的血液相容性，发现在分析的血液相容性标志物中，材料之间几乎没有显著差异. BioMedFlexreg(BMF)涂层是一种硬碳薄膜涂层，具有高弯曲强度、抗辐射性和耐磨性.Mielke等[153]在VAD轴承表面涂覆了 $2{\\sim}4~\\upmu\\mathrm{m}$ 厚的Bio-  \n\nMedFlexreg涂层，发现BMF涂层表面没有出现涂层失效，而 $57\\%$ 的DLC轴承出现了划痕. 因此，BMF涂层被Cleveland heart pumps应用作为替代的轴颈轴承材料.超晶金刚石(Ultrananocrystalline diamond)是一种极其光滑、低成本、高生物相容性、低磨损、低摩擦以及化学惰性的金刚石涂层，应用于Jarvik 2000心室辅助装置. Jarvik Heart公司的VAD组件经过了机械和模拟血液流体力学测试. 结果表明，超晶金刚石界面具有优秀的耐久性和抗血栓性[154]. Carmat TAHs是将生物与合成物的混合膜纳入TAHs的首次成功尝试. Jansen等[134]用戊二醛处理过的牛心包在Carmat TAHs的人工心室中修饰了膈膜的血接触面. 他们发现血小板活化和在心包组织上的纤维蛋白和血细胞沉积与医用肝素包覆PVC相似.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3.2 组织正常化  \n\n与其他的表面形貌相比，细长的、阵列型的纳米尺度或微米尺度的表面形貌可以增强EC的附着力和功能[131,155]. 在高剪切应力的动态环境下，具有表面织构的接触面可以有效地提高EC附着的稳定性[156]. 此外，具有表面织构的血液接触表面可以提高血液相容性，因为血液成分会保留在表面织构之中，形成1个生物层，避免血栓栓塞事件的发生，降低长期LVADs患者血栓栓塞的风险[157].  \n\n将含有PU和二甲基乙酰胺颗粒的织构表面作为LVAD血接触面的一部分，表面织构会捕获血液成分，形成稳定的新生内膜层[158]. Potthoff等[159]通过选择和优化衬底的纳米几何结构，最大限度地提高ECs的迁移和对于流动诱导剪切力的抵抗效果. 适当的表面微观结构可以提高内皮化在超高壁面剪切应力水平下的稳定性，这种环境恰恰与由心脏泵诱导的高剪切应力流动环境类似[160]. Stefopoulos等[135]设计并验证了一种新的诱导内皮化的策略，将表面织构和种植EC的区域设计相结合[图4(c)]. 与没有表面织构的对照组相比，这种策略只用了一半的时间就达到完全内皮化.利用合理设计的模板可以在 $2~\\mathrm{mm}$ 厚的PDMS上进行最初始的EC种植.  \n\n表面织构技术作为增强内皮化的有效方式，已被应用于商用VAD产品，如HeartMate I LVAD的烧结钛纹理表面和完整的PU线状纹理. 试验证明，HeartMateI LVAD的表面织构能促进EC的稳定黏附，有助于改善血液相容性[161]. 此外，还有一种EC快速播种的技术，将烧结Ti与EC连接起来，通过降低血小板的黏附，最大限度地降低了血栓形成的风险[162].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 3.3 挑战与展望  \n\nVADs涂层仍面临许多挑战，其中两个最主要的挑战分别是由心脏泵产生的高剪切应力所引起的涂层损伤以及涂层的耐久性和长期有效性. 本节中提及的VADs抗凝涂层列于表4中. 虽然抗凝药物涂层比惰性涂层表现出更好的血液相容性，但对于长期或永久植入的VADs而言，TiN涂层和DLC涂层在高流速或剪切应力下更稳定和持久. 表面织构可诱导EC层的形成，实现良好的血液相容性，但表面织构的设计不当会导致严重血栓形成[163]. 诱导EC涂层在体内的功能活性和细胞黏附的可靠性仍然是需要关注的主要问题. 基于现有的涂层技术，DLC涂层是一种相对长期稳定可靠的选择，可以与适当的表面微观结构设计相结合，实现更好的血液相容性. 在未来，有机惰性涂层、梯度和多层聚合物涂层的发展有望加强聚合物涂层与钛基基体之间的界面结合. 对于内皮化涂层，最重要的工作是增强生物材料和EC层的结合，以适应VADs的高壁面剪切应力.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 4    导管  \n\n随着全球人口老龄化和人类医疗水平的提高，对医用导管的需求不断增加. 医用导管主要分为介入导管和非介入导管. 介入导管是可以插入体内的细导管，为药物输送[164]或手术设备植入[165]创造通道，非介入导管是粗导管，主要用于外部血液运输或循环. 当医用导管暴露在血液中时，血浆蛋白和血小板会黏附在导管表面. 之后，凝血因子会在不溶性纤维蛋白网络形成之前被激活，这将导致血栓的形成[166]，血栓并发症，甚至死亡[167]. 在临床治疗中，静脉注射肝素通常用于预防血栓形成和减少凝血相关并发症. 然而，大量使用肝素会诱发出血、超敏反应、血小板增多、呼吸困难和其他不良反应[168]. 因此，已经有许多研究尝试在医用导管的壁面上构建涂层，以实现有效的抗凝，同时减少抗凝药物的使用.",
+        "category": " Introduction"
+    },
+    {
+        "id": 18,
+        "chunk": "# 4.1 阻断凝血路径  \n\n通过在医用导管表面涂覆抗凝药物，可以有效改善导管的生物相容性，减少血栓形成，减轻术后全身炎症反应. 此外，抗凝药物涂层可以避免抗凝药物直接注射到血液中引起的不良后果，如出血、超敏反应、血小板减少和呼吸困难等. 如图5(a1)所示，Gao等[169]通过用海藻酸钠/肝素复合物固定表面来修饰聚氯乙烯导管. 聚氯乙烯导管表面经浓硫酸酸化后，浸入含多氨基的聚乙烯亚胺中，用氨基进行修饰，然后用磷",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 表 4    心室辅助装置上的抗凝涂层  \n\nTable 4    Anticoagulant coatings in VADs   \n\n\n<html><body><table><tr><td></td><td></td><td>rao</td><td>Application</td><td>gS Pros</td><td>Cons</td><td>Ref</td></tr><tr><td>Coating PU and</td><td>Substrate</td><td>Coating method</td><td>EXCOR pumps</td><td></td><td>1. Coating damage caused</td><td>2016[16]</td></tr><tr><td> heparin</td><td></td><td></td><td>Beri Heart Incor axal l eake he homologni eneae by the at </td><td>reactions</td><td>by high shear stress 2. The durability and long-</td><td>2004[122]</td></tr><tr><td>Heparin</td><td>Titanium alloys</td><td></td><td>flow pumps</td><td>2. Reduce thrombin</td><td> term effectiveness of the</td><td></td></tr><tr><td>Genetically engineced</td><td></td><td>Covalently attachment</td><td>HeartMate LVAD</td><td>prouetindin pae</td><td>coating required for supplement</td><td>1998[139]</td></tr><tr><td>MPC</td><td> Pure titanium</td><td></td><td>EVAHEART centrifugal pumps</td><td></td><td></td><td>2002[140] 2003[41]</td></tr><tr><td>MPC</td><td>Acrylic resin and polyetherimide</td><td></td><td>MedTech Dispo VADs' impeller, rotor and</td><td></td><td>1.Limited lifetime because of their biodegradability and</td><td>2009[142]</td></tr><tr><td>MPC</td><td>Titanium alloys</td><td></td><td>housing Rotary blood pump</td><td>1.Excellent blood compatibility in long-term</td><td>easy to dissolve 2. Weak interfacial bonding</td><td>2009[43]</td></tr><tr><td>Polyglycerol</td><td>Titanium alloys</td><td></td><td>Berlin Heart GmbH Artificial ventricles of</td><td>2. Repel cells and platelets efficiently</td><td>between polymeric coatings and titanium-based</td><td>2020[133]</td></tr><tr><td>ePTFE</td><td>ePTFE</td><td>Corona treatment</td><td>CARMAT TAHs Ventricles and trileaflet</td><td></td><td>substrates</td><td>2012[134]</td></tr><tr><td>Polyether urethane</td><td>Angioflex (polyetherure-thane)</td><td>Covalently attachment</td><td>valves of AbioCor TAHs</td><td></td><td></td><td>1993[44]</td></tr><tr><td>Titanium oxidation</td><td></td><td>Plasma electrolytic oxidation</td><td>Passively levitated VADs</td><td>1.More stable and durable in high flow velocity or</td><td></td><td>2020[152]</td></tr><tr><td>DLC</td><td>Titanium alloys</td><td>2-phase ion beam</td><td>Sun Medical centrifugal pump VentrAssist</td><td>shear stress for long-term or 1. Worse hemocompatibility permanent implantation than biological coatings and</td><td></td><td>1998[148]</td></tr><tr><td>DLC</td><td></td><td>deposition</td><td>implantable rotary blood pumps</td><td>VADs</td><td>organic coatings</td><td>2003[149]</td></tr><tr><td>DLC BMF</td><td>VAD journal bearing</td><td></td><td>EVAHEART VADs Cleveland Heart pumps</td><td>2.Excellent biocompa- tibility and excellent</td><td>2.The risk of microcracks and film breakdown because</td><td>2006[150] 2010[153]</td></tr><tr><td>Ultrananocrys talline</td><td>Silicon carbide and Ti</td><td>Chemical vapor</td><td>Jarvik 2000 Heart</td><td>least platelet adherence) 3.Easy to process coating of complex shape</td><td>hemocompa-tibility (theof VADs\"high rotate speed and shear rate</td><td>2016[154]</td></tr><tr><td>diamond Bioprosthetic</td><td>alloy</td><td>deposition Intermolecular</td><td></td><td></td><td></td><td></td></tr><tr><td>pericardial tissue</td><td>Bovine pericardium</td><td>interactions</td><td>CARMAT TAHs</td><td>1. Induce the formation of</td><td>1. Unsuitable textured surfaces can also result in</td><td>2012[134]</td></tr><tr><td>Microtextured surface</td><td>Cyclic olefin copolymer</td><td>Covalently attachment</td><td>LVAD</td><td></td><td></td><td>2014[159] 2014[160]</td></tr><tr><td>Microtextured surface</td><td>Cyclic olefin _copolymer and PDMS</td><td></td><td></td><td>EC layers controllably,</td><td>severe thrombosis 2. Induced ECs coatings'</td><td>2016[135]</td></tr><tr><td>Microtextured surface</td><td>Titanium alloys</td><td> Particle casting</td><td>HeartMate LVAD</td><td>efficiently and quickly 2.Excellent</td><td>functional liveness in vivo and reliability of cell</td><td>2006[158]</td></tr><tr><td></td><td></td><td></td><td></td><td>hemocompatibility 3. Improve the stability of</td><td>attachment under high shear</td><td></td></tr><tr><td>ECs</td><td>Sintered Ti</td><td>Covalently attachment</td><td>VADs</td><td>EC layers</td><td>stress istill a major problem 3.Hard to process, high</td><td>2016[62]</td></tr></table></body></html>  \n\n酸氢二钠将海藻酸钠和肝素直接固定在修饰表面，构建海藻酸钠-肝素复合涂层. 海藻酸盐-肝素复合涂层可以改善聚氯乙烯导管的亲水性，增强生物相容性.涂层还可以减少血小板对表面的黏附和活化，以改善抗血栓形成性能. 与体内的无涂层导管移植物相比，表面涂有肝素的膨体聚四氟乙烯导管的闭塞性血栓明显减少，流通性显著改善. Bae等[171]采用等离子辉光放电法制备肝素固定化聚氨酯导管. 通过将聚氨酯导管接枝羧基，并依次与聚环氧乙烷和肝素反应，得到肝素涂层导管. 因此，肝素涂层导管具有很好的抗凝  \n\n血性和血液相容性.  \n\nYau等[172]研究了玉米胰蛋白酶抑制剂在导管表面构建抗凝血涂层. 玉米胰蛋白酶抑制剂能可逆地与人凝血因子FXIIa的活性位点相互作用，而不抑制其他蛋白酶. 因此，玉米胰蛋白酶抑制剂可以阻断凝血因子XII，以减轻导管在血浆系统中引起的凝血，从而减少血栓形成. 此外，Brisbois等[173]在Elast-eon E2As聚合物中掺入了S-硝酰基-乙酰青霉胺，利用浸涂法制造了可释放NO的导管，这种导管可以在长达20天的时间内稳定释放生理水平的NO. 由于NO具有减少血小板黏附和活化的特性，导管可以实现抗凝. 结果表明，与对照组相比，S-亚硝基-n-乙酰丙胺/E2As导管能显著减少血栓和细菌的黏附.  \n\n生物惰性有机涂层因其良好的血液相容性和抗血栓性而被广泛应用于医用导管的抗凝. 由于化学键的存在，生物可降解聚合物涂层可以稳定地与导管基底结合，因此涂层可以在血液的高压力和高剪切速率下工作. 一些可生物降解的聚合物涂层可以改变导管表面的亲水性和疏水性，以减少血液成分(如纤维蛋白原和血小板)的黏附. 对可生物降解聚合物涂层的研究有很多，在抗血栓和抗菌性能方面显示出巨大的潜力. 如图5(a2)所示，Smith等[170]通过用聚合磺基甜菜碱(polySB)修饰PU导管构建了一种稳定的聚合物涂层，此涂层可以将水分子配位到导管表面. 两性离子聚合物涂层可以减少蛋白质和细胞对导管表面的黏附，因为两性离子基团协调了游离水和结合水. 结果表明，涂层能显著减少血液与导管表面的相互作用，减少血栓形成和炎症. Li等[174]通过将一种键合单体，N-丙烯酰甘氨酰胺(NAGA)或N-丙烯酰亚胺-碳酰二肼(NASC)与一种抗菌单体和甲基丙烯酸锌(ZMA)共聚，构建了一种二元共聚物水凝胶导管. 由于ZMA有很强的亲水性，可以抵抗纤维蛋白和血小板的黏附，因此，导管可以减少血栓的形成.  \n\n磷酰胆碱和季铵通过传统的自由基共聚被用于合成可生物降解的聚合物涂层，并使用简单的浸涂来实现共聚物涂层的长期稳定性[175]. 由于磷酰胆碱的细胞膜仿生基团，磷酰胆碱和含阳离子的共聚物涂层具有很好的抗血栓性. 此外，季铵的阳离子基团也提供了很好的杀菌性能. 在另一项研究中，通过使用丙烯酰胺和丙烯酸构建了一种保形适配的载有抗菌剂的多合一水凝胶涂层[176]. 通过体外血液循环试验证实了水凝胶涂层的抗凝血性能，结果表明，该涂层可以减少血小板的吸附和活化，并且没有溶血的风险. 此外，抗血栓形成的聚-2-甲氧基乙基丙烯酸酯(PMEA)涂层已经应用于心肺机回路. Kariya等[177]评估了用于中心静脉端口导管系统的PEMA涂层的抗血栓形成性.PEMA涂层可以减少积聚，并通过冲洗促进血栓从系统中冲洗出来，以实现抗凝.  \n\n![](images/a0ad797a461343540a6da39ce2bae8c41af1a584cc287d5cada3e7b8a5273673.jpg)  \nFig. 5    The anticoagulation coatings on catheters: (a1) immobilization of composite $\\mathrm{SA/HEP}^{[169]}$ ; (a2) polySB modification of PICC surface[170]; (b) schematic of blood repellency on TLP surfaces[21] 图 5    导管上的抗凝涂层：(a1)复合SA/HEP的固定化[169]；(a2) PICC表面的PolySB修饰[170]；(b) TLP表面排斥血液的示意图[21]  \n\nLi等[178]制备了一种基于高碘酸钠存在条件下PDA纳米粒子和银纳米粒子快速形成和累积的超亲水涂层. 在亲水化学成分和纳米颗粒堆叠表面形貌的协同作用下，该涂层具有超亲水性，通过排斥蛋白质来实现抗凝. 同时，由于银离子的存在，涂层具有抗菌性能. 此外，SLIPS涂层能有效减少血栓的形成. 如图5(b)所示，Leslie等[21]使用改进的SLIPS技术构建了一种应用于医用导管光滑表面的抗凝血涂层. 导管的光滑表面与栓系的全氟化碳共价结合，然后涂上1层可移动的液态全氟萘烷. SLIPS涂层可应用于几乎任何导管材料表面，有效排斥全血，减少血液成分和细菌的黏附，实现体内外抗凝. 在动脉血的高压和高剪切速率下，SLIPS涂层可以保持稳定. Wang等[179]开发了一种基于自适应液体门控膜的导管，该导管可以适应导管尺寸，减少血栓形成并定位释放药物. 采用静电纺丝法构建导管的微孔聚偏氟乙烯基底，提供毛细作用力吸附门控液. 由于基底亲和力强，生物相容性好，液态全氟萘烷、Krytox 100、Krytox 103以及硅油500是常用的门控液. 由于流体的独特能力，SLIPS涂层可以根据压力调整尺寸. 因此，采用SLIPS涂层包覆的导管可以抵抗血液成分的黏附，减少血栓形成，并控制药物在指定位置的释放.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# 4.2 挑战与展望  \n\n医用导管与流动的血液直接接触并长期暴露在血液的剪切作用下. 因此，导管上的抗凝涂层需要在血液剪切下保持稳定，并且不从导管表面脱落. 同时，导管的原材料和涂层均应具有生物相容性，对人体无害，不释放有毒物质. 此外，由于对导管的需求量较大，抗凝导管或涂层的制备工艺应适合大规模生产，并应考虑大量使用过的医用导管的回收情况. 本节中导管上应用的抗凝涂层列于表5中，尽管文献中报道的涂层具有各自良好的效果，但是这些涂层缺点的共性问题是缺乏实践的检验.  \n\n目前，减少导管内血栓形成和实现导管抗凝最广泛使用的方法是通过共价键将肝素固定在导管表面，但仍有一定的局限性. 表面结合的肝素不稳定且容易浸出，由于细长管表面的剪切力，导致抗凝活性逐渐降低. 大多数生物惰性涂层在抗凝效果方面略逊于肝素涂层，但具有更好的抗菌性能. SLIPS策略最有可能实现抗凝作用，且具有自愈功能，但使用寿命仍需要更多实践来加以验证和改善. 通过与抗凝药物的分子间相互作用来改变导管原材料很可能是实现导管高效稳定抗凝的最佳方法.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# 5    展望  \n\n随着心血管植介入器械的不断发展，其表面的抗凝涂层研究引起了广泛关注. 现有研究对植介入体表面的涂层和改性技术进行了许多尝试，然而，涂层或植介入体本身的效果或持续时间仍未能完全令人满意，因此目前临床中大多仍需要配合抗凝药物使用.  \n\n抗凝涂层的选择首先需要考察植介入体本身的应用场景，如人工心脏瓣膜、血管支架以及心室辅助装置需要长期的不断使用，因此其寿命和稳定性十分重要，在设计时需要考虑其血液流场、植介入体基底和涂层坚固程度等影响；而对于短期使用的植介入体，如部分导管，则可以更多考虑其抗凝效果，尽量减少抗凝药物的使用，同时兼顾炎症等其他问题.  \n\n抗凝药物涂层是目前使用最广泛的阻断凝血途径的涂层之一，具有优异的抗凝性能. 肝素作为最成功的涂层之一，已广泛用于商业植介入体，并在血管支架上取得巨大成功. 然而，对于人工心脏瓣膜和心室辅助装置，由于持续的打开、关闭和泵送，表层的肝素链容易在非生理流动和高剪切应力下从载体链上撕下. 目前，新型的肝素涂层多与其他生物分子偶联，实现抗凝过程中前期优秀的抗凝效果以及结合后期的组织正常化，这是多功能和高效抗凝的主要发展思路. 人工机械心脏瓣膜一般选用PyC和DLC等更为耐用的惰性涂层，尽管这些涂层的抗凝效果不够理想，但仍无法被其他抗凝涂层替代. 随着人工合成聚合物的发展，通过设计兼顾多种特性的表面性质，有希望实现抗凝和耐用的平衡. 另一方面，植介入体周围组织恢复正常化的涂层理论上可以承受生理血流并防止多种并发症，包括出血、再狭窄和闭塞的风险，因此得到了极大关注. 在组织工程心脏瓣膜和血管支架上涂覆细胞外基质，以及在机械心脏瓣膜、血管支架和心室辅助装置上制作微结构的无机PyC、DLC是目前正在研究加速内皮化的常用方法. 然而，内皮化的过程较为复杂，目前临床上尚未取得积极的结果.  \n\n目前，抗凝涂层的应用还受到多方面的制约. 首先，涂层在剪切下的剥离以及基底的疲劳是实现长期抗凝面临的主要问题. 涂层和基底之间需要具有强大的附着力，同时基底的材料需要很好的耐用度. 然而，坚固的涂层通常缺乏良好的抗凝效果. 其次，必须了解材料表面形成血栓的明确机制. 尽管血液和植介入体间的相互作用已经研究了一百多年，但是复杂的血液成分，如纤维蛋白原、血小板和红细胞等在其表面",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# 表 5    导管上的抗凝涂层  \n\nTable 5    Anticoagulant coatings on catheters   \n\n\n<html><body><table><tr><td>Coating</td><td>Substrate</td><td>Coating method</td><td>Application</td><td>Pros</td><td>Ref</td></tr><tr><td>Heparin</td><td>PVC</td><td>Covalently attachment</td><td>Non-interventional catheter</td><td>Lower protein adhesion, inhibition of intrinsic coagulation pathways, good density</td><td>2013[69]</td></tr><tr><td>Heparin</td><td>PU</td><td>Ionic bond</td><td>Intravascular catheters</td><td>and stability Inhibits fXIla activity, induces less fXI</td><td>1999[171]</td></tr><tr><td>Corn trypsin inhibitor</td><td>PU</td><td>Covalently attachment</td><td> Intravascular catheters</td><td>activation and prolongs clotting time in human plasma Long-term NO release, enhanced shelf-life</td><td>2012[172]</td></tr><tr><td>S-nitroso-N- acetylpenicillamine</td><td>Elast-eon E2As polymer</td><td>Intermolecular interactions</td><td>Artificial blood vessel</td><td>stability, significantly reduces the number of thrombi and bacterial adhesion Significant reduction in thrombus</td><td>2015[173]</td></tr><tr><td>Poly-Sulfobetaine</td><td>PU N-acryloyl</td><td>Covalently attachment</td><td>Intravascular catheters</td><td>accumulation and reduced microbial adhesion to surfaces, thereby aleviating host inflammation</td><td>2012[170]</td></tr><tr><td>Zinc methacrylate Phosphorylcholine- and</td><td>glycinamide/ N- acryloylsemi-carbazide</td><td>Intermolecular interactions</td><td>Intravascular catheters Non-interventional</td><td>Excellent antibacterial properties, resists</td><td>2021[14]</td></tr><tr><td>Cation-bearing Acrylamide, acrylic acid,</td><td>PLA</td><td>Covalently attachment</td><td>catheter</td><td>fibrinogen and platelet adhesion, improves blood compatibility</td><td>2020[175]</td></tr><tr><td>Benzophenone, AgN03 PMEA</td><td>PVC</td><td>Intermolecular interactions</td><td>Non-interventional catheter</td><td></td><td>2021 [176]</td></tr><tr><td>Polydopamine, silver nanoparticles</td><td>PU PVC</td><td>Covalently attachment</td><td>Intravascular catheters Non-interventional catheter</td><td>Repel proteins adhesion Reduced non-specific adsorption of proteins, significant antibacterial properties</td><td>2020[177]1 2020[178]</td></tr><tr><td>LP LP, Krytox 100,</td><td>polycarbonate, PVC, PET, etc Polyvinylidene fluoride</td><td>Capillary force</td><td>Non-interventional catheter</td><td>Excellent anti-adhesion characteristics</td><td>2014[21] 2020[17]</td></tr></table></body></html>  \n\n形成血栓的机制仍然未被完全揭示. 第三，具有不同机械性能的植介入体的基底，如软导管、刚性血管支架以及弹性支架等，限制了抗凝涂层的通用性. 最后，植介入体上的工况，如静态、旋转和往复等不同运动情况，使涂层处于不同的工作条件. 血液流动和剪切力不仅会导致血栓形成，还会破坏涂层. 以双叶机械瓣膜为例，真实的生理条件是脉动的，但在打开和关闭阶段有时会伴随射流. 更复杂的是，该心脏瓣膜在开启阶段有正向射流，在关闭阶段有外围射流、基准射流和铰链反向射流，这些都导致在设计其表面涂层时需要额外考虑. 从我们的角度来看，植介入体表面的抗凝涂层尚未有通用的策略，植介入体材料和结构设计的协同改进才能实现理想的抗凝涂层.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
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+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Zwitter-Wettability and Antifogging Coatings with Frost-Resisting Capabilities  \n\nHyomin Lee,† Maria L. Alcaraz,† Michael F. Rubner,‡,\\* and Robert E. Cohen†,\\* †Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States and ‡Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States  \n\nABSTRACT Antifogging coatings with hydrophilic or even superhydrophilic wetting behavior have received significant attention due to their ability to reduce light scattering by film-like condensation. However, under aggressive fogging conditions, these surfaces may exhibit frost formation or excess and nonuniform water condensation, which results in poor optical performance of the coating. In this  \n\n![](images/14f058a733ad9ade8d8bd248ba5331a250b3934a78c72bb4cab81a69b94d02bf.jpg)  \n\npaper, we show that a zwitter-wettable surface, a surface that has the ability to rapidly absorb molecular water from the environment while simultaneously appearing hydrophobic when probed with water droplets, can be prepared by using hydrogen-bonding-assisted layer-by-layer (LbL) assembly of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA). An additional step of functionalizing the nano-blended PVA/PAA multilayer with poly(ethylene glycol methyl ether) (PEG) segments produced a significantly enhanced antifog and frost-resistant behavior. The addition of the PEG segments was needed to further increase the nonfreezing water capacity of the multilayer film. The desirable high-optical quality of these thin films arises from the nanoscale control of the macromolecular complexation process that is afforded by the LbL processing scheme. An experimental protocol that not only allows for the exploration of a variety of aggressive antifogging challenges but also enables quantitative analysis of the antifogging performance via real-time monitoring of transmission levels as well as image distortion is also described.",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# KEYWORDS: antifogging $\\cdot$ zwitter-wettability $\\cdot$ antifrost $\\cdot$ layer-by-layer $\\cdot$ wetting  \n\nver the past decade, many research groups1\u000133 have worked to develop stable, effective antifogging (AF) coatings capable of handling a wide range of environmental challenges. Although many of these AF coatings perform satisfactorily in specifically defined antifogging challenges including such tests as the Erlenmeyer steam test and the cold-fog test,1\u000133 there is no single quantitative test that provides all the information needed to assess the full optical performance of the coating. For example, even coatings that maintain high levels of light transmission during an aggressive fogging challenge, under specific conditions may produce significant image distortion due to excess or nonuniform water condensation (Supporting Information Figure S1a). Thus, to truly understand the key parameters necessary for designing widely applicable antifogging coatings, it is essential to evaluate both light transmission and image distortion effects under a wide range of controlled environmental conditions.  \n\nIn this work, we establish an experimental protocol that allows for the exploration of a variety of aggressive antifogging challenges by controlling not only the initial substrate temperature $(T_{\\mathrm{i}})$ but also the environmental conditions in which the AF behavior is recorded, such as temperature $(T_{\\mathsf{f}})$ and relative humidity $(\\%R H_{f})$ . This protocol also enables quantitative analysis of the antifogging performance via real-time monitoring of transmission levels as well as image distortion. Although others22,33 have attempted to quantitatively characterize antifogging performance by measuring time-dependent light transmission or haze values in accordance with ASTM standards, these methodologies may not always reveal the true optical performance of the coating.  \n\nIn the process of using this new protocol to evaluate our antifog coatings, we realized that, under some extreme conditions, many coatings fail to maintain high transmission levels coupled with low image distortion values. As a result, we worked to develop a \\* Address correspondence to rubner@mit.edu (M.F.R), recohen@mit.edu (R.E.C).  \n\nReceived for review October 31, 2012 and accepted January 29, 2013.  \n\nPublished online January 29, 2013   \n10.1021/nn3057966  \n\nsuperior antifog coating that could handle aggressive temperature/humidity conditions including those that would normally produce severe frosting on surfaces. Herein, we describe the development of a new coating system that maintains excellent optical clarity under conditions that would normally produce extreme fogging and/or frosting.  \n\nThis new coating system is based on a layer-by-layer (LbL)-assembled multilayer comprised of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA). Previously, we have shown that hydrogen-bonded multilayer thin films consisting of PVA and PAA can be assembled under acidic conditions $\\left(\\mathsf{p}\\mathsf{H}2.0\\right)$ and further stabilized to withstand higher pH conditions by a thermal crosslinking treatment.34 Although this multilayer coating exhibits good antifog properties, we find that an additional step of adding poly(ethylene glycol methyl ether) (PEG) segments throughout the resultant LbLassembled multilayer film produces significantly enhanced antifog and antifrosting behavior. Antifrosting in this context refers to the ability of a coating to resist frost formation when a sample is held at very low initial substrate temperatures $(T_{\\mathrm{i}},$ where ${{T}_{\\mathrm{i}}}$ is less than the freezing temperature of water) and then exposed to higher temperatures and high humidity.  \n\nIn contrast to many antifogging coatings with hydrophilic1 or even superhydrophilic21,30 wetting behavior, PEG-functionalized PVA/PAA LbL-assembled multilayer films exhibit abnormally high initial water contact angles $(\\sim110^{\\circ})$ ), followed by a transient decay to lower contact angle values over a period of several minutes. These unusually high initial water contact angles are quite remarkable considering that the multilayer coating comprises only very hydrophilic polymers that are water-soluble in non-cross-linked forms and wellknown for their ability to strongly interact with water molecules. Unlike conventional hydrophobic surfaces, these coatings have the distinct capacity to alter reversibly their surface structure in order to minimize their interfacial free energy with a surrounding medium. In addition, this new nanostructured multilayer coating can simultaneously present a very hydrophobic character to water droplets (close to a Teflon-like surface) and exhibit the capacity to absorb a substantial amount of molecularly dispersed, nonfreezing water via hydrogen-bonding interactions.35\u000137 We refer to this unique combination of properties as “zwitterwettability” and note that such behavior requires a specific combination of molecular and structural features that are readily created by controlling the processing parameters and materials used in the layer-by-layer nanoscale assembly process.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 3,
+        "chunk": "# RESULTS  \n\nWe previously reported that multifunctional thin film coatings composed of PVA and PAA could be layer-by-layer assembled under low pH conditions and subsequently stabilized to high pH by either postassembly thermal or chemical treatments.34 We anticipated that the resultant hydrogel-like multilayers would be good candidates for preparing hydrophilictype antifogging coatings with performance similar to coatings based on multilayers assembled from hydrophilic polysaccharides.1 To screen these coatings and compare to other control surfaces, samples were conditioned at $-20^{\\circ}C$ and subsequently exposed to ambient lab conditions $(22\\pm1~^{\\circ}\\mathsf{C},40\\pm10\\%\\mathsf{R H}$ ).  \n\nAs revealed in Figure ${1}\\mathsf{b},$ under these conditions, hydrophilic glass (soda lime glass substrate treated with oxygen plasma using the procedure described previously34) and a 30-bilayer PVA/PAA multilayer film both exhibit initial high levels of frost formation followed by a slow clearing to a more transparent state. In the case of a hydrophobic fluorosilane-treated glass, the frosting persists for at least $30~\\mathsf{s}$ . Thus, under this particular challenge, both hydrophobic and hydrophilic glass as well as glass coated with a PVA/PAA multilayer thin film did not exhibit acceptable antifrost behavior.  \n\nTo enhance the antifrost behavior of the PVA/PAA multilayer film, PEG molecules were reacted into the film as schematically illustrated in Figure 1a. The abundance of free hydroxyl and carboxylic acid groups in the as-assembled film allows for facile thermal and chemical modifications that enhance the stability of the film and provide additional functionality. Asassembled films (30 bilayers, $1610\\pm7$ nm in thickness) were thermally cross-linked at $140^{\\circ}{\\mathsf{C}}$ for 5 min to form ester linkages. Hydroxyl-terminated poly(ethylene glycol methyl ether) $(M_{\\mathrm{w}}=5000\\ \\mathrm{g/mol})$ molecules were then reacted with the pH-stabilized films in phosphate buffer saline (PBS) solutions $\\left(\\mathsf{p H}\\sim7.4\\right)$ ) using glutaraldehyde chemistry. The reaction was performed while the films are in a highly swollen state and after the PEG molecules have been allowed ample time $(20\\mathsf{m i n})$ ) to diffuse throughout the film structure. Thus, the PEG molecules are dispersed throughout the entire film and not simply grafted onto the surface. Successful loading of the covalently attached PEG molecules throughout the multilayer film was confirmed by using a probe molecule as previously described34 (for more details, see Supporting Information (Figure S2)). In addition, no significant change in thickness was observed after the PEG chemistry (thickness after reaction $1600\\pm29\\mathrm{nm},$ , consistent with the conclusion that this reaction is not producing a dense grafted surface layer of PEG molecules. The final PEG-functionalized multilayer exhibited excellent optical quality and was uniform except at the edges of the glass slide, as is sometimes observed when glass slide size samples are coated with multilayers. Figure 1b shows the dramatic enhancement of antifrost behavior that results from this additional PEG chemistry. In contrast to the as-assembled multilayer and the control glass",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# ARTICLE",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# ARTICLE  \n\n![](images/e8267931b850a0c12184b543c534557788c9ef57ca6843771fc1743155697522.jpg)  \nFigure 1. (a) Schematics showing the fabrication of the antifogging coating including reacting a thermally stabilized PVA/ PAA multilayer film with poly(ethylene glycol methyl ether) (PEG) molecules. (b) Photographs taken immediately and $305$ after transfer to ambient lab conditions $(22\\pm1^{\\circ}\\mathsf{C},40\\pm10\\%\\mathsf{R H})$ from a $-20^{\\circ}C$ freezer. Only the PEG-functionalized 30-bilayer PVA/PAA multilayer film resisted frost formation at the early and later stages of exposure. MIT logo in the figure was used with permission of Massachusetts Institute of Technology.  \n\n![](images/f25f96dd70894ea922bb6ecfb7be8e2b630cc314e6474c88141f73dd84ce3cf7.jpg)  \nFigure 2. Experimental apparatus (real-time monitoring of transmission and distortion image analysis) used to quantify antifogging performance.  \n\nsamples, the PEG-functionalized multilayer remains frost-free during the entire experiment.  \n\nTo more completely assess the antifog/antifrost capability of this promising new coating system, realtime monitoring of both light transmission and image distortion was conducted under a variety of temperature/ humidity profiles relevant to common fogging conditions, as shown in Figure 2. In order to provide context, PEG-functionalized multilayers were compared to a number of different control surfaces and coatings. A complete description of the testing apparatus and procedures can be found in the Methods section.  \n\nFigure 3 shows the normalized light transmission versus time of various coatings after exposure to $37^{\\circ}\\mathsf C,$ $80\\%$ RH conditions with variation in $T_{\\mathrm{i}}$ . Light transmission was normalized to the incident light intensity without any sample present. The level of image distortion observed from video images and the corresponding",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# ARTICLE  \n\n![](images/b8c544379438d50d9fb853380af5d964ebc887ee44618666e47acee726495885.jpg)  \nFigure 3. Normalized light transmission versus time of various coatings on glass after exposure to $37^{\\circ}C,$ , $80\\%$ RH conditions (black: $T_{\\mathrm{i}}=22.5{\\ ^{\\circ}C},$ red: $T_{\\mathrm{i}}=-11.2^{\\circ}{\\mathsf C},$ , blue: $T_{\\mathrm{i}}=-19.6^{\\circ}\\mathsf{C})$ . Light transmission was normalized to the incident light intensity averaged over the 421 573 nm range without any sample present. Below are images recorded through the sample at the indicated times and their corresponding $\\mathfrak{a}$ values. (a) Hydrophilic glass. (b) Hydrophobic glass. (c) PVA/PAA multilayer film ( $140^{\\circ}\\mathsf C,$ 5 min). (d) PEG-functionalized PVA/PAA multilayer film.  \n\ncorrelation coefficient values (R) are also shown. The correlation coefficient $(\\upalpha)$ has a scale of 0 to 1, where 1 means no distortion and complete matching of the two images and 0 means no correlation among the images. Values of $\\upalpha$ above 0.95 correspond to essentially distortionfree behavior, while $\\upalpha$ below 0.5 corresponds to unacceptably poor visual clarity. Compared to the results shown in Figure 1b, these experiments were conducted in a more challenging environment for antifogging, i.e., in more humid final conditions $(37^{\\circ}\\mathsf C,80\\%$ RH) compared to ambient lab conditions $(22\\pm1^{\\circ}\\mathsf C,40\\pm10\\%\\mathsf R\\mathsf H)$ .  \n\nIn the case of hydrophilic glass (water advancing contact angle of $8\\pm1^{\\circ}.$ ), high transmission and low image distortion levels are observed under the least challenging fogging conditions $(T_{\\mathrm{i}}=22.5^{\\circ}\\mathsf{C})$ . This behavior is consistent with what has been reported38 for hydrophilic surfaces. In sharp contrast however, under more aggressive fogging conditions, there is an initial sharp drop in transmission levels followed by a recovery to values above $90\\%$ . This early stage drop in transmission is due to frost formation facilitated by a conditioning temperature $(T_{\\mathrm{i}})$ that is below the freezing point of water. Of particular note is the fact that even though high transmission levels are recovered after the frost clears, images viewed through the glass samples are clearly distorted, as revealed by visual observation and by decreasing R values with lower temperature conditioning. Relatively high transmission levels are promoted in part by the presence of a low refractive index layer of water condensed on the surface $(n_{\\mathrm{water}}\\approx1.33)$ compared to that of the glass substrate $(\\boldsymbol{n}_{\\mathfrak{g l a s s}}\\approx1.5)$ . Condensed water layers on both sides of the substrate enhance transmission levels via an antireflection mechanism, even though their presence also produces image distortion that would be undesirable for many optical applications. These very hydrophilic surfaces also become less water wettable with aging under normal laboratory conditions. The net result as shown in the Supporting Information Figure S3a (“bare glass”) is lower transmission levels and corresponding decreasing $\\mathfrak{a}$ values during fog testing. This is a well-known problem that occurs with highly energetic, very hydrophilic surfaces.39  \n\nFigure 3b shows the normalized light transmission and image distortion for the hydrophobic (advancing water contact angle of $112\\pm1^{\\circ},$ fluorosilane-treated glass. Results reveal that not only does this hydrophobic coating exhibit significant distortion due to frosting and fogging but also the transmission values remain very low during the entire testing period. Clearly, typical hydrophobic surfaces are not well suited for handling an aggressive fogging challenge. In the case of a glass slide coated with the polymer poly(methyl methacrylate) (PMMA) (advancing water contact angle of $72\\pm2^{\\circ}.$ ), it was also found that low transmission values and high image distortion occurred during testing (Supporting Information Figure S3b).  \n\nWhen the PVA/PAA multilayer film was subjected to the same testing protocols (Figure 3c), it was found that samples conditioned at room temperature $(T_{\\mathrm{i}}=$ $22.5~^{\\circ}\\mathsf{C})$ maintained high transmission and low image distortion values during the entire testing period. However, decreasing $T_{\\mathrm{i}}$ to $-11.2~^{\\circ}C$ and further to $-19.6~^{\\circ}C$ results in significant frost formation in the initial stages of the experiment and in corresponding reductions in $\\textstyle\\mathbf{\\alpha}\\mathbf{\\alpha},$ to 0.79 and 0.58, respectively. Note also that after 10 s in the latter cases, the transmission levels are high even though the sample promotes significant image distortion. In sharp contrast to all of the samples tested, adding PEG segments to the PVA/PAA multilayer film produced a coating that maintained high normalized transmission levels (above $90\\%$ ) and low image distortion (R values of 0.98) regardless of the initial conditioning temperature (Figure 3d). Thus, even under the most aggressive testing conditions, this coating effectively inhibits both frost formation and fogging.  \n\nOn the basis of the full set of antifogging results for the various surfaces examined in this study, the following conclusions can be made. Hydrophilic glass surfaces can be effective at preventing fogging under mild conditions but are not able to prevent initial stage frost formation when samples are conditioned at temperatures below the freezing point of water. In addition, such surfaces can promote significant image distortion even after clearing of the frost. Commonly prepared hydrophobic surfaces, on the other hand, are unable to prevent fogging or frost formation under the conditions explored in this study. It is generally accepted that good antifog behavior is typically associated with surfaces that exhibit an advancing water droplet contact angle of less than $40^{\\circ}$ .12,38 Hydrophobic surfaces are classically defined as having an initial advancing water droplet contact angle of $90^{\\circ}$ or higher and are generally not considered to be effective at preventing fog or frost formation. As will be discussed shortly, PVA/PAA multilayers, both as-prepared and PEG-functionalized, exhibit hydrophobic character when probed with water droplets (initial advancing contact angle ${\\sim}100^{\\circ}$ or higher). Clearly the excellent antifrost and antifogging capability of the PEGfunctionalized multilayers is not consistent with conventional wisdom and warrants further clarification and understanding.  \n\nWetting Properties of PEG-Functionalized PVA/PAA Multilayer Films. To investigate the origin of the excellent antifrost capabilities of PEG-functionalized PVA/PAA multilayers, time-dependent contact angle measurements were conducted for the three hydrophobic surfaces examined in this study: hydrophobic glass, as-prepared PVA/PAA multilayers, and PEG-functionalized PVA/PAA multilayers. As shown in Figure 4b, the surfaces of all of these coatings exhibited initial advancing water droplet contact angles of greater than $100^{\\circ}$ . In the case of the hydrophobic fluorosilane-treated glass (initial contact angle $112\\pm1^{\\circ})$ , the contact angle remains nearly constant with time. For the PVA/PAA multilayers and PEG-functionalized PVA/PAA multilayers, the initial contact angle $(111\\pm3^{\\circ}$ for PVA/PAA multilayers and $117\\pm12^{\\circ}$ for PEG-functionalized PVA/PAA multilayers) drops slowly to much lower values over the course of the experiment, reaching about $70^{\\circ}$ for the PVA/PAA multilayer and about $50^{\\circ}$ for the PEG-functionalized PVA/PAA multilayer after $600\\ s$ . Not unexpectedly, the multilayer systems exhibit time-dependent behavior that is often attributed to transient surface reconstruction associated with a reorganization of hydrophilic functional groups to the surface in response to the water droplet $^{40-45}$ Also note that the initial water contact angle of the PEG-functionalized PVA/PAA multilayer is essentially the same as that measured for the unmodified multilayer film. The observation of similar contact angles is consistent with the conclusion that a dense top layer of PEO is not grafted onto the surface.  \n\nIn order to investigate this change in water contact angle more in depth, a drop shape analysis method was applied as reported previously.41 Goniometry allows extraction of the droplet height $(h)$ , droplet width $(r_{\\mathrm{b}}),$ , and also its contact angle (θ) versus time as shown in Figure 4a. The spherical cap model was employed to determine the wetted surface area and the droplet volume. The initial droplet volume calculated using this model matched well with the actual water dispensed. The wetted surface area and droplet volume changes with time for the various samples were compared by using the equation given below.  \n\n$$\nS(t)~=~\\pi{r_{\\mathrm{b}}}^{2}(t)\n$$  \n\n$$\nV(t)=\\frac{\\pi{r_{\\mathrm{b}}}^{2}(t)h(t)}{3}\\frac{(2+\\cos\\theta(t))}{(1+\\cos\\theta(t))}\n$$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# ARTICLE",
+        "category": "fy the text segment you provided about hydrophilic polymers accurately, I need to have the content of that segment itself. Please provide the specific text so I can analyze it and determine which part of a paper it corresponds to."
+    },
+    {
+        "id": 8,
+        "chunk": "# ARTICLE  \n\n![](images/048f09cabfcc47009e8de42d630a02683918a85ea6ee1258c597f738f2beb8d5.jpg)  \nFigure 4. (a) Schematic representation of the spherical cap model used for the calculation of wetted surface area and droplet volume. (b) Water contact angle evolution over time (600 s) for three samples exhibiting hydrophobic behavior. (c) Wetted surface area evolution over time (600 s) for the three samples expressed as $\\Delta S/S_{\\circ}$ where $\\Delta S=S-S_{\\circ}$ and $S_{\\circ}$ is the initial wetted surface area at $\\pmb{t}=\\pmb{0}$ . (d) Water droplet volume evolution over time (600 s) for three samples expressed as $\\Delta V/V_{\\circ}$ where $\\Delta{}V=$ $\\pmb{V}-\\pmb{V}_{\\circ}$ and $\\boldsymbol{v_{\\circ}}$ is the initial water droplet volume at $\\scriptstyle t=0$ . Filled symbols denote the average of three or more independent data points every $20~\\mathsf{s}$ .  \n\nwhere $S(t)$ and $V(t)$ define the wetted surface area and volume of the drop as a function of time, respectively. Figure $4c$ shows how the normalized wetted surface area changes with time for these samples. While the surface area for the hydrophobic fluorosilane-treated glass does not change with time, the data for the multilayer samples indicate an increase in the wetted surface area consistent with spreading of the water drops. For the PEG-functionalized PVA/PAA multilayer film, the wetted surface area increased nearly $300\\%$ over the $600s$ time interval. However, from Figure 4d, where the normalized volume change with time is plotted, no significant difference in volume was observed (small, $10{-}20\\%$ decreases in volume can be anticipated due to evaporation of water from the droplets). From the multilayer results, it was concluded that the spreading of the water droplet dominates relative to the absorption of water into the film from the droplet over the 600 s of the experiment. Furthermore, PEG-functionalized PVA/PAA multilayer films exhibit a much faster evolving spreading of a water drop than the PVA/PAA multilayer films, suggesting that the surface reconstructs from a high initial to a lower final water contact angle more quickly for the PEG-functionalized PVA/PAA multilayer film.  \n\nIt was unexpected for the PVA/PAA multilayer film and PEG-functionalized PVA/PAA multilayer film to exhibit such high values of the initial advancing water droplet contact angle $(\\theta_{\\mathrm{w}})$ . Two main factors were considered as possible sources of this unusual behavior: (A) the presence of hydrophobic acetate groups in the partially hydrolyzed PVA polymer and (B) water droplet induced surface deformation at the three-phase contact line due to the intrinsically “soft” nature of the PVA/PAA multilayer film.  \n\nIn the former case, it is to be recognized that the PVA used in the PVA/PAA multilayer films contains $11-16\\%$ acetate-bearing repeat units.34 It is possible that these relatively hydrophobic moieties preferentially orient and become trapped at the film/air interface during the heating process used to thermally cross-link the film $140^{\\circ}{\\mathsf C}$ for 5 min under vacuum). Similar abnormally high water contact angles have been reported before.46\u000149 For example, nanocomposite poly(N-isopropylacrylamide) (PNIPA) films with clay network structures exhibited $\\theta_{\\mathrm{w}}$ values in the range $100-131^{\\circ}$ . The authors attributed this behavior to the alignment of $N$ -isopropyl groups of PNIPA chains at the gel air interface. Consistent with the notion that the acetate groups are sufficiently hydrophobic to influence wettability, measurements of $\\theta_{\\mathrm{w}}$ of poly(vinyl acetate) and partially hydrolyzed PVA with $11-16\\%$ acetate groups (films covalently bonded to a glass substrate and heated at $140^{\\circ}{\\mathsf C}$ for 5 min under vacuum) revealed advancing contact angles of $75\\pm$ $2^{\\circ}$ and $75\\pm5^{\\circ}$ , respectively. In contrast, fully hydrolyzed PVA with $1-3\\%$ acetate groups exhibits a contact angle of $58\\pm1^{\\circ}$ after a similar heat treatment (see Supporting Information (Figure S4)).  \n\nWith regard to the latter possibility, it was reported recently50 that on thin soft substrates Young's law fails when there is substantial deformation near the threephase contact line. Under such circumstances, the macroscopically observed contact angle increases and the substrate is effectively less wettable. As shown in the Supporting Information (Figure S5), PVA/PAA multilayer films that have been thermally cross-linked at $140^{\\circ}{\\mathsf{C}}$ for 5 min show significant substrate deformation at the three-phase contact line after a hemispherical droplet of water is fully evaporated; more heavily cross-linked systems $140^{\\circ}\\mathsf C,$ 10 and $30~\\mathrm{{min}}$ ) do not show this behavior. On the basis of the previous predictions,50 one would expect the contact angle to increase by a maximum of about $10^{\\circ}$ as a result of this effect. The additional enhancement in contact angle may be attributed to the chemical structure/mobility of the polymer matrix. It has been reported that the extent to which a gel surface may become hydrophobic by reorientation and conformational changes depends on the chemical structure of the polymer in the gel matrix and also on the mobility of the individual chain segments.46 The effect of polymer mobility on the hydrophobicity of a hydrogel has been studied previously,49 where a soft mobile gelatin gel with over $95\\%$ water content was found to have water contact angle in the range $90-120^{\\circ}$ .  \n\nIt should be noted that others have suggested51 that a rough surface could also contribute to the observation of very high values of $\\theta_{\\mathrm{w}}.$ . However, as reported previously,34 PVA/PAA multilayer films have $R_{\\tt a}$ roughness values of about $0.6\\mathsf{n m}$ for ${\\sim}1.5\\mu\\mathrm{m}$ thick films, while the roughness of PEG-functionalized PVA/ PAA multilayer films is about $1.8\\mathsf{n m}$ . Thus an enhancement of $\\theta_{\\mathrm{w}}$ due to high surface roughness was assumed to be negligible for both surfaces. We therefore conclude that the abnormally high initial values of $\\theta_{\\mathrm{w}}$ observed on both PVA/PAA multilayer films and PEGfunctionalized PVA/PAA multilayer films derive from the combined effects of the initially surface-enriched hydrophobic acetate moieties, the softness of the multilayer film, and the mobility of chain segments near the surface.  \n\nCondensation Experiments. One might expect that more hydrophobic surfaces inhibit the condensation of water by suppressing nucleation and that this effect might play a role in antifogging behavior.52\u000155 To determine if the various surfaces investigated exhibited differences in water condensation during fogging conditions, the maximum amount of water condensed from moist air and steam was investigated. Various coatings (PVA/PAA multilayer film, PEG-functionalized PVA/PAA multilayer film, hydrophilic glass, and hydrophobic glass) were incubated at $-20^{\\circ}C$ for $1\\mathsf{h}.$ , and the mass change versus time was measured immediately after transfer to ambient lab conditions $(22\\pm1^{\\circ}\\mathsf{C},40\\pm$ $10\\%$ RH). The maximum amount of water condensed was more or less the same $(5-7~\\mathsf{m g})$ for all of the coatings investigated regardless of their wetting properties except for the PVA/PAA multilayer film, which exhibited a larger amount of condensed water $(9\\:\\mathrm{mg})$ during the measured time period. Thus, no correlation between the amount of water condensed and antifrost/antifogging behavior was observed.  \n\nEffect of Elevated Temperature and Relative Humidity on Macroscopic Water Drop Profiles. The transient nature of the contact angle with time for the PVA/PAA-based multilayer coatings (Figure 4b) was previously attributed to surface functional group reorganizations in response to the presence of the probe water droplet. To examine if conditioning (for $1\\ h$ before water droplets added) the coatings in humid environments at higher temperatures would influence this effect, the evolution of macroscopic water drop profiles was examined in controlled environments at elevated temperature and higher humidity $(37\\ ^{\\circ}{\\mathsf C},\\ 80\\%$ RH). Both the PEG-functionalized and as-assembled PVA/ PAA multilayers show faster decreases in contact angles with time and reach lower values of the contact angle when incubated and then probed in a higher humidity, higher temperature environment, as shown in Figure 5a, b, and c. However, even after conditioning in an environment that would be expected to render the coatings more hydrophilic due to reorganization of hydrophilic groups to the surface as reported previously by others,43 the PEG-functionalized multilayer still exhibits an initial water droplet contact angle above $90^{\\circ}$ for the first $25s$ of the experiment. In order to study this behavior in detail, another simple test was performed. A water drop was placed on a PEGfunctionalized PVA/PAA multilayer film after being transferred to ambient lab conditions $(22\\pm1^{\\circ}{\\mathsf C},$ $40\\pm10\\%$ RH) from a $-20~^{\\circ}C$ freezer, as shown in Figure 5d. As revealed in this image, the coated section of the glass remains frost-free, indicating that molecularly condensed water has been effectively absorbed by the film. However, a water drop placed on top of this frost-free coating exhibits a water contact angle above $90^{\\circ}$ . Thus, this unusual surface simultaneously presents a very hydrophobic character, but also has the capacity to absorb a substantial amount of molecularly dispersed water. We refer to this unique combination of properties as “zwitter-wettability”, as shown in Figure 5e.  \n\nEffect of Thermal Cross-Linking on Wetting Behavior. PVA/ PAA multilayer films were thermally treated to varying extents to ascertain how increased cross-linking might influence wetting and antifrost behavior. Previously,",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# ARTICLE",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# ARTICLE  \n\n![](images/5d426658777ea958ebc471b8880ac948f96078f30b614ed4a0bc298668ac15a2.jpg)  \nFigure 5. (a) Photographs of water drop profiles versus time on a PEG-functionalized PVA/PAA multilayer film in $37^{\\circ}C,80\\%$ RH conditions. (b) Water contact angle evolution over time (600 s) for a PVA/PAA multilayer film in ambient conditions and $37^{\\circ}\\mathsf C,$ $80\\%$ RH conditions. (c) Water contact angle evolution over time (600 s) for a PEG-functionalized PVA/PAA multilayer film in ambient lab conditions $(22\\pm1^{\\circ}\\mathsf{C},40\\pm10\\%\\mathsf{R H})$ and $37^{\\circ}\\mathsf{C}$ , $80\\%$ RH conditions. (d) Photograph of a water drop placed on PEGfunctionalized PVA/PAA multilayer film after being transferred to ambient lab conditions $(22\\pm1^{\\circ}\\mathsf C,$ $40\\pm10\\%$ RH) from $-20^{\\circ}C$ . Inset photograph shows the zoomed-in image of the water drop with a contact angle above $90^{\\circ}$ . Only the PEGfunctionalized PVA/PAA multilayer coated part of the glass resist frost formation. (e) Schematic representation of zwitterwettability. MIT logo in the figure was used with permission of Massachusetts Institute of Technology.  \n\nwe have reported34 that increasing the heating extent either by time or temperature alters the cross-link density of the multilayer film. Figure 6b shows how the swelling ratio (defined here as the ratio of the thickness of a film in contact with DI water to that of a dry film) changes with increase in heating time. For the $140^{\\circ}\\mathsf C,$ 5 min treated sample, the swelling ratio was 3.6, and as the heating time increased from 5 to $30\\mathrm{min}$ , a decrease in swelling ratio was observed: the corresponding values of swelling ratio were 2.9 and 2.3, respectively. Decreasing swelling ratios are consistent with an increase in cross-link density (Supporting Information Table S1). Figure 6a shows the transmission versus time plots of PVA/PAA multilayer films after exposure to $37^{\\circ}\\mathsf C$ $80\\%$ RH conditions for samples with the different thermal treatments. It is evident from the transmission experiment as well as the distortion analysis that increasing the cross-linking density is detrimental to the antifogging performance. Furthermore, a comparison of the transient water contact angle profiles of the PVA/PAA multilayer films with increasing cross-linking density (Figure 6c) revealed that the initial water contact angle of a PVA/PAA multilayer film decreases from $111\\pm3^{\\circ}$ to $77\\pm4^{\\circ}$ , and $70\\pm3^{\\circ}$ , with increasing cross-linking times. The abnormally high initial water contact angle $(\\sim110^{\\circ})$ shown for the $140^{\\circ}\\mathsf C,$ 5 min treated PVA/PAA multilayer film is lost for the more heavily cross-linked systems and becomes closer to what was found for a poly(vinyl acetate)-coated glass $(75\\pm1^{\\circ})$ . Thus, a more cross-linked film behaves as a more conventional hydrophilic coating. This result supports the hypothesis that the enhanced contact angle is due to the combined effects of a flexible surface enriched in hydrophobic acetate moieties and the softness of the multilayer film as mentioned earlier.  \n\nEffect of Overall Film Thickness and Type of Polymer Top Layer on Antifog/Antifrosting Behavior. The effects of bilayer number (or overall film thickness) and the type of polymer that was used in the last deposition step of the LbL assembly on antifog/antifrosting capabilities were investigated. The PVA/PAA multilayer films mentioned throughout this article are prepared by thermally cross-linking a 30 bilayer PVA/PAA multilayer film $((\\mathsf{P V A}/\\mathsf{P A A})_{30})$ on a glass substrate for 5 min at $140^{\\circ}\\mathsf{C};$ the 30 bilayer films are typically approximately ${\\sim}1.5\\ \\mu\\mathsf{m}$ in overall film thickness. In order to explore the effect of overall film thickness, a six-bilayer PVA/PAA",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# ARTICLE  \n\n![](images/26de400ecd8efd41dc6c72a53c78c57420d1a2e5d07bcc52e278897acd26ebac.jpg)  \nFigure 6. (a) Normalized transmission versus time after exposure to $37^{\\circ}\\mathsf C,$ $80\\%$ RH conditions of PVA/PAA multilayer films thermally cross-linked with different heating times (5, 10, 30 min). Right photos are images recorded through the samples after $30~\\mathsf{s}$ and their corresponding R values. (b) Swelling ratio of PVA/PAA multilayer films with varying cross-linking treatments. (c) Water contact angle evolution over time (600 s) for PVA/PAA multilayer films in ambient conditions varying cross-linking treatments. Open symbols denote the average of three independent data points every $\\boldsymbol{10\\ s}$ .  \n\nmultilayer film $(\\sim100\\ \\mathsf{n m})$ and its PEG-functionalized counterpart were prepared. Transmission experiments and distortion image analysis on these thinner samples were performed, and the results (Supporting Information, Figure S7) show clearly that the antifog/antifrost performance of the six-bilayer films was inferior to the 30-bilayer films. Similar observations have been reported previously,1 where a minimum critical thickness of the film was necessary to achieve acceptable antifogging performance.  \n\nThe outermost layer effect was also investigated by ending the multilayer assembly with PVA: $(\\mathsf{P V A}/\\mathsf{P A A})_{30.5}$ . The noninteger value of Z indicates that the assembly process ends with the same polymer used to start the process; that is, the film is topped with the hydrogenbonding acceptor PVA. As shown in the Supporting Information (Figure S8), regardless of which layer is on the top, functionalizing the PVA/PAA multilayer film with PEG results in excellent frost-resisting films.  \n\nInhibition of Frost Formation. PVA/PAA multilayer films and PEG-functionalized PVA/PAA multilayer films are essentially soft coatings that have an abundance of hydrophilic functional groups that can absorb a substantial amount of water vapor from moist air. This property makes this system an extremely interesting platform for antifogging applications. However, it still remains a question why PEG-functionalized PVA/PAA multilayer films inhibit frost formation after incubation at very low temperatures and manage condensed water in such a way that minimizes image distortion. It has been reported35,37,56 that water absorbed in certain polymer systems can exist in different states including nonfreezing (molecularly bound) and melting point depressed states. In this case, the water molecules are presumably molecularly dispersed as a result of strong polymer\u0001water hydrogen-bonding interactions and hence are not capable of freezing at the usual temperature. One might expect that if this is the case in the PEG-functionalized PVA/PAA multilayer coatings, excess water on the surface could freeze, but water dispersed throughout the film would experience a depressed freezing point or none at all. In order to explore this hypothesis, samples were pre-exposed to different amounts of water prior to cooling $(-20\\ ^{\\circ}\\mathsf{C})$ and subsequently tested under frost-forming conditions (Figure 7). Pretreatments before incubating in a freezer included (I) drying in ambient conditions, (II) immersion in DI water for 20 seconds followed by an exposure to compressed air just to remove the excess water layer on the top, and (III) immersion in DI water for 20 seconds followed by immediate transfer into the freezer. The observation of interference patterns after the treatment for sample II confirmed that the film absorbed a substantial amount of water prior to incubation in a freezer. As shown in Figure 7b, only sample III exhibited ice formation, with the surface ice eventually sliding across the film top surface. Sample II supports the idea that water existing in the multilayer",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# a",
+        "category": " Introduction"
+    },
+    {
+        "id": 13,
+        "chunk": "# ARTICLE  \n\n![](images/4e8b78b15e2d41ec78f83e86b84ef8fbb1987d1129dbabfc3f2a2b42222f28ee.jpg)  \nFigure 7. Frost formation experiment of PEG-functionalized PVA/PAA multilayer films with different water pretreatments. Samples were subjected to a $-19.6~^{\\circ}C$ freezer for 1 h and exposed to ambient conditions $(22\\pm1^{\\circ}\\mathsf{C},40\\pm10\\%\\mathsf{R H})$ ). (a) Schematic representation of how condensed water is presented after exposure to ambient conditions for differently pretreated PEG-functionalized PVA/PAA multilayer films: (I) Dry PEG-functionalized PVA/PAA multilayer film, (II) wet PEGfunctionalized PVA/PAA multilayer film, (III) water-soaked PEG-functionalized PVA/PAA multilayer film. (b) Corresponding photos taken immediately and 30 and 60 s after exposure to ambient conditions for differently pretreated PEG-functionalized PVA/PAA multilayer films. Arrow indicates the direction of increase in time. MIT logo in the figure was used with permission of Massachusetts Institute of Technology.  \n\nfilm is nonfreezing and therefore imparts a resistance to frost formation even when a film is treated at temperatures below the normal freezing point of water.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# DISCUSSION  \n\nClassically, a hydrophobic surface is defined as a surface that supports a water droplet advancing contact angle of $90^{\\circ}$ or higher. The PVA/PAA multilayer coatings, both as-prepared and PEG-functionalized, satisfy this simple definition. Both multilayer systems also exhibit a zwitter-wettable character, that is, the ability to rapidly absorb molecular water from the environment while simultaneously appearing hydrophobic when probed with water droplets. However, in the case of the PEG-functionalized multilayer, its special chemical and molecular architecture imparts a combination of physical properties that turn out to be uniquely suited for the prevention of frost formation and fogging. This combined zwitter-wettable and frost-resistant character requires a number of key molecular and structural features including (1) a surface enriched in hydrophobic moieties and (2) an abundance of available hydrophilic functional groups within the material that strongly hydrogen bond with water to produce a sufficient amount of nonfreezing water molecules. When these elements are in place, it is possible to create frost-resistant coatings that simultaneously exhibit both hydrophobic and hydrophilic characteristics.  \n\nThe as-prepared PVA/PAA multilayer comes close to achieving all of the required elements, but only after adding PEG molecules does it become fully capable of resisting frost formation. The hydrophilic segments of both $\\mathsf{P E G}^{35}$ and $\\mathsf{P V A}^{56}$ are known to interact strongly with absorbed water molecules via hydrogen-bonding interactions to produce a nonfreezing bound state. Ultimately, however, it is the amount of nonfreezing water the material can accommodate that determines its effectiveness as an antifrost coating. The capacity of a material for absorbing a large amount of nonfreezing water is determined by its cross-link density (both physical and covalent), level of crystallinity, and level of competitive hydrogen bonding of the system.35\u000137,56 In all of these cases, increases of the parameter will decrease the amount of nonfreezing water the system can accommodate. For the as-prepared multilayer, the molecularly blended hydrogen-bonded complex created by the nanoscale layer-by-layer assembly process ensures that crystallization of the PVA molecules will be limited or nonexistent. This same complexation, on the other hand, also reduces the amount of molecular interactions possible with water molecules (competitive hydrogen bonding). Likewise, the low level of covalent cross-linking needed to stabilize the multilayer also decreases the nonfreezing water capacity of the system. Thus, the addition of PEG segments is needed to further increase the nonfreezing water capacity of the multilayer. The nanoscale layer-by-layer process for creating these PEG-containing multilayer films57\u000159 makes it possible to optimize many of the key parameters responsible for the antifrost behavior. We therefore anticipate that further optimization of the structures of the polymers used and the assembly process could result in an as-prepared multilayer that exhibits antifrosting properties comparable to the PEGfunctionalized system. It should also be noted that in the absence of nanoscale LbL assembly, cast films of the same PVA/PAA composition are rough and turbid (clearly not of optical quality), as shown in Figure S6. The enabling role of this nanoscale processing methodology is thus very apparent and critically important to the results presented in this paper.  \n\nThe unusual hydrophobic nature of the multilayer is also a consequence of the structure and surface organization of the molecular complex formed by the layer-by-layer assembly process and subsequent chemical cross-linking. Previous reports of hydrophilic gels with unusually high advancing water droplet contact angles46\u000149 conclude that this attribute is associated with the stable alignment of hydrophobic chain segments at the substrate surface. To achieve this alignment, the level of cross-linking and interchain molecular complexation (for multicomponent polymer systems) must be low enough to allow sufficient molecular mobility for the surface segments to achieve the required stable molecular conformations. As noted in this paper, increasing levels of cross-linking reduce the advancing contact angle to levels expected for a cross-linked homopolymer of partially hydrolyzed PVA (about $75^{\\circ}$ ). Increasing levels of cross-linking and complexation also would be expected to decrease the compliance of the multilayer, thereby reducing the enhancement in contact angle due to the “softness effect” described in the Results section. Thus, to realize hydrophobic behavior that is observed even when a sample is incubated in a high humidity environment and preloaded with nonfreezing water, it is essential that the energetics favor surface alignment of the hydrophobic chain segments even when exposed to gas phase water. This was accomplished in the PVA/ PAA multilayers by utilizing partially hydrolyzed PVA (provides the needed hydrophobic acetate groups), assembling under controlled pH conditions (controls the complexation process), and limiting the level of postassembly cross-linking. It should be noted that the hydrophobic character of this multilayer system may help to overcome a major problem with antifog coatings based on extremely hydrophilic, high surface energy materials, namely, a high susceptibility to fouling by low surface energy contaminates.12,60 Additional work is required to confirm this possibility.  \n\nFinally, we note that the observation of zwitterwettability is possible due to differences in the way water interacts with a surface when it is in a gas phase molecular state versus a droplet state. In the latter case, the liquid surface tension of water $(\\gamma_{\\mathsf{L V}})$ dominates the initial interaction of the drop with the surface due to strong hydrogen bonding of water molecules within the water droplet. In contrast, molecularly dispersed water molecules in the atmosphere can directly diffuse into the multilayer film and interact with the abundant embedded hydrophilic groups. The net result is an ability to present simultaneously both hydrophobic character to water droplets and hydrophilic character to gas phase water molecules. This is possible, even after the thin film has absorbed a significant amount of water, as has been observed in certain polymer hydrogels.46\u000149",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# CONCLUSION  \n\nIn summary, we show that zwitter-wettable surfaces, surfaces that simultaneously present a hydrophobic character and have the capacity to absorb a substantial amount of molecularly dispersed water, can be prepared using hydrogen-bonding-assisted LbL assembly of PVA and PAA. Real-time monitoring of transmission as well as distortion image analysis revealed that when PEG segments were reacted throughout the PVA/PAA multilayer, a coating was produced that maintained high normalized transmission levels and low image distortion regardless of the initial conditioning temperature. The net result was a coating system that effectively inhibited both frost formation and fogging.  \n\nStatic water contact angle and swelling experiments indicated that the abnormally high initial advancing water contact angle of the multilayer platform $(>100^{\\circ})$ was attributed to the presence of surface-enriched hydrophobic acetate groups and the softness of the multilayer film. An abundance of hydrophilic functional groups within the material allows water droplets placed on a surface to spread by surface reconstruction and for molecularly dispersed water molecules to strongly hydrogen bond to produce nonfreezing water molecules. The addition of PEG to the PVA/PAA multilayer film provides an additional capacity to absorb nonfreezing water and an improvement in antifrost behavior.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 16,
+        "chunk": "# ARTICLE",
+        "category": " Introduction"
+    },
+    {
+        "id": 17,
+        "chunk": "# METHODS  \n\nMaterials. Asahiklin (AK225, Asahi Glass Company), poly(vinyl alcohol) $(M_{\\mathrm{w}}=131000\\mathrm{~g/mol}$ , PD $\\mid\\:=\\:1.50.$ , $87-89\\%$  \n\n$99+\\%$ ACS reagent, Sigma-Aldrich), poly(glycidyl methacrylate) $(M_{\\mathrm{w}}=25000\\mathrm{g/mol}$ , $10\\%$ solution in MEK, Polysciences), poly(methyl methacrylate) $(M_{\\mathrm{w}}\\ =\\ 540000\\ \\mathrm{g/mol}\\$ , Scientific Polymer Products), poly(ethylene glycol methyl ether) $(M_{\\mathrm{w}}=$ $5000\\mathrm{{g/mol}}$ , Sigma-Aldrich), and $1H,1H,2H,2H$ -perfluorodecyltrichlorosilane (Sigma-Aldrich) were used as received. Standard soda lime glass microscope slides and phosphate buffer saline were obtained from VWR. Deionized water (DI, $18.2~\\mathsf{M}\\Omega\\cdot\\mathsf{c m},$ , Milli-Q) was used in all aqueous polymer solutions and rinsing procedures.  \n\nGlass Substrate Pretreatment. The glass substrates were first degreased by sonication in a $4\\%$ (v/v) solution of Micro-90 (International Products Co.) for 15 min and subsequently sonicated twice in DI water for 15 min and dried with compressed air. They were then treated with oxygen plasma (PDC-32G, Harrick Scientific Products, Inc.) for 2 min at 150 mTorr. This glass is denoted here as hydrophilic glass and was used as the substrate for all the polymer coatings that were produced by layer-by-layer assembly. However, specifically for the PVA/PAA system, additional poly(glycidyl methacrylate) anchoring chemistry was included in order to covalently bond the first layer of PVA to the substrate, following the protocol described in our previous work.34  \n\nCoating Methodology. LbL assemblies of PVA and PAA were constructed using a Stratosequence VI spin dipper (Nanostrata Inc.) controlled using StratoSmart v6.2 software. LbL assembly employed dipping times of $10\\mathrm{\\min}$ for the polymer solutions, followed by three rinses of 2, 1, and 1 min. The concentration of the polymer solutions was $1\\ \\mathrm{mg/mL},$ and the pH of these solutions and the rinse water was adjusted to $\\mathsf{p H}2.0$ with $0.1~\\mathsf{M}$ HCl or 0.1 M NaOH. The nomenclature for LbL films follows the following conventions: (hydrogen bonding acceptor/donor $)_{Z}$ where Z is the total number of bilayers deposited. The PVA/PAA multilayer film mentioned throughout this article is prepared by thermally cross-linking $(P V A/P A A)_{30}$ on a glass substrate for 5 min at $140^{\\circ}\\mathsf C,$ unless other conditions are specified. The PEGfunctionalized PVA/PAA multilayer film was prepared by immersing a PVA/PAA multilayer film in a $10\\:\\mathrm{mg/mL}$ PEG solution $\\left(\\mathsf{p H}2.0\\right)$ for 20 min. Then the sample was soaked at $30~^{\\circ}\\mathsf{C}$ in $0.13\\%$ (w/w) glutaraldehyde in PBS for 10 min, rinsed with DI water, and dried with compressed air. PMMA-coated glass was prepared by dissolving PMMA in Asahiklin at a concentration of $10~\\mathrm{mg/mL}$ . An approximately $150\\mathsf{n m}$ thick coating was deposited onto a pretreated glass substrate by dip-coating for $1\\ h$ and heating the film for $1\\ h$ at ${\\sim}60^{\\circ}C$ to completely evaporate the solvent. Pretreated glass substrates were treated with $1H,1H,2H,2H$ -perfluorodecyltrichlorosilane by first placing them, along with a few drops of the reactive fluoroalkylsilane liquid, inside a Teflon canister under an inert nitrogen atmosphere and then sealing the canister and heating it overnight at $110^{\\circ}{\\mathsf{C}}$ to result in hydrophobic fluorosilane-treated glass.61  \n\nFilm Characterization. Dry film thicknesses were measured using a Tencor P16 surface profilometer with a $2\\ \\mu\\mathsf{m}$ stylus tip, a $2\\mathsf{m g}$ stylus force, and a scanning rate of $50\\mu\\mathrm{m}/s$ . Water contact angle measurements were performed using a RameHart model 590 goniometer after vertically dispensing droplets of deionized water on various coatings. Water contact angles were measured as deionized water was supplied via a syringe into sessile droplets (drop volume $\\sim10\\mu\\mathrm{L})$ ). Measurements were taken at three different spots on each film, and the reported uncertainties are standard deviations associated with these contact angle values. The evolutions of water drop profiles in a controlled environment $(37^{\\circ}\\mathsf C,80\\%$ RH) were measured by taking movies of the water drop inside the environmental chamber. Then, ImageJ software was used to fit the extracted images with the built-in angle tool. To determine the swelling ratio, a custom-built quartz cell was used in conjunction with a J.A. Woollam XLS-100 spectroscopic ellipsometer as described previously.34 Data were collected between 400 and $1000\\mathsf{n m}$ at a $70^{\\circ}$ incidence angle and analyzed with WVASE32 software. Condensation experiments were performed by preparing the samples on glass substrates of dimension $37.5\\:\\mathrm{mm}\\times25.0\\:\\mathrm{mm}$ , equilibrating in the freezer set at $-20^{\\circ}C$ for $1\\mathfrak{h}$ , and measuring the mass change versus time immediately after transfer to ambient lab conditions using a digital scale balance (model Ag204, Mettler Toledo Instruments).  \n\nAntifogging Characterization. The quantitative antifogging performance on various coatings was evaluated in part by a customized setup in an environmental chamber as shown in Figure 2. Measurements were conducted by performing visible light transmission measurements (light source: tungsten lamp (421 nm $-573\\ \\mathsf{n m}$ ), detector: InstaSpec II, Oriel Instruments, monochromator: $125~\\mathrm{~mm}$ spectrography/monochromator, model 77400, Oriel Instruments) on a sample in a controlledhumidity glovebox (environmental chamber, Electro-Tech Systems, Inc.). Optical fibers were used to measure the normalized transmission values inside the environmental chamber. Before measuring the real-time transmission behavior inside the controlled environment, the samples were first allowed to equilibrate for $1\\mathrm{~h~}$ in a freezer set at a designated temperature $(T_{\\mathrm{i}})$ before being moved to the environmental chamber, which was maintained at $37^{\\circ}C,$ $80\\%$ RH. Samples were transferred using a secondary container, and the exposure time was measured within 3 s after the sample was placed in the environmental chamber.  \n\nFor the image distortion analysis, styrofoam was used as an insulator to inhibit the condensation of water vapor on the inner wall of the environmental chamber. A microscopy test chart was used for the test image. A reference video was taken with no sample between the camera and the test image. Exposure time was measured within 3 s after the sample was placed between the camera and the test image. Photos were extracted from the video at 5 and $30s$ after exposure and referenced as target images. Distortion image analysis62 was conducted by examining pixel intensity array subsets on two corresponding images (reference and target images) and extracting the deformation mapping function that relates the images, allowing a correlation coefficient to be obtained as shown in the Supporting Information (Figure S1b). Also, it should be noted that transmission measurement and image distortion analysis were conducted consecutively on the same sample with drying steps (in ambient conditions) in between.  \n\nConflict of Interest: The authors declare no competing financial interest.  \n\nSupporting Information Available: Distortion image analysis, spectrofluorometry study of PEG-functionalized PVA/PAA multilayer film, real-time monitoring of transmission and its relevant distortion image analysis on bare glass and PMMA-coated glass, water contact angle measurements on various coatings, substrate deformation at the three-phase contact line of PVA/PAA multilayer film, estimation of cross-link density from swelling ratio, photograph of a film prepared from a solution of PVA and PAA, real-time monitoring of transmission and its relevant distortion image analysis of a PVA/PAA multilayer film and PEG-functionalized multilayer with six bilayers, photograph showing the top layer effect on antifog/antifrosting. This material is available free of charge via the Internet at http://pubs. acs.org.  \n\nAcknowledgment. We thank the Center for Materials Science and Engineering (CMSE), the Institute for Soldier Nanotechnologies (ISN), for use of their characterization facilities. We also thank J. Kleingartner for helpful discussions during the preparation of the manuscript and S. Srinivasan and K. Park for assistance with the contact angle measurements in the environmental chamber. This work was partially supported by a Samsung Scholarship and in part by the MRSEC Program of the National Science Foundation under award number DMR 0819762.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# REFERENCES AND NOTES  \n\n1. Nuraje, N.; Asmatulu, R.; Cohen, R. E.; Rubner, M. F. Durable Antifog Films from Layer-by-Layer Molecularly Blended Hydrophilic Polysaccharides. Langmuir 2010, 27, 782–791.   \n2. Howarter, J. A.; Genson, K. L.; Youngblood, J. P. Wetting Behavior of Oleophobic Polymer Coatings Synthesized from Fluorosurfactant-Macromers. ACS Appl. Mater. Interfaces 2011, 3, 2022–2030.",
+        "category": " References"
+    },
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Anti-Fogging Nanofibrous $S_{\\mathrm{i}}{\\mathsf{O}}_{2}$ and Nanostructured $\\mathsf{S i O}_{2}\\mathrm{-}\\mathsf{T i O}_{2}$ Films Made by Rapid Flame Deposition and in Situ Annealing. Langmuir 2009, 25, 12578–12584.   \n8. Shoji, A.; Fukushima, T.; Kumar, D. S.; Kashiwagi, K.; Yoshida, Y. Surface Modification of Plasma Polymerized Silicon Resin Films Produced at Different Gas Atmospheres. J. Photopolym. Sci. Technol. 2006, 19, 241–244.   \n9. Patel, P.; Choi, C. K.; Meng, D. D. Superhydrophilic Surfaces for Antifogging and Antifouling Microfluidic Devices. J. Lab. Autom. 2010, 15, 114–119.   \n10. Matsuda, A.; Matoda, T.; Kogure, T.; Tadanaga, K.; Minami, T.; Tatsumisago, M. Formation and Characterization of Titania Nanosheet-Precipitated Coatings via Sol\u0001Gel Process with Hot Water Treatment under Vibration. Chem. Mater. 2005, 17, 749–757.   \n11. Lu, X.; Wang, Z.; Yang, X.; Xu, X.; Zhang, L.; Zhao, N.; Xu, J. Antifogging and Antireflective Silica film and Its Application on Solar Modules. Surf. Coat. Technol. 2011, 206, 1490–1494.   \n12. Howarter, J. A.; Youngblood, J. P. Self-Cleaning and Next Generation Anti-Fog Surfaces and Coatings. Macromol. Rapid Commun. 2008, 29, 455–466.   \n13. Dong, H.; Ye, P.; Zhong, M.; Pietrasik, J.; Drumright, R.; Matyjaszewski, K. Superhydrophilic Surfaces via Polymer $\\mathsf{S i O}_{2}$ Nanocomposites. Langmuir 2010, 26, 15567–15573.   \n14. Du, X.; Liu, $\\mathsf{x}.,$ Chen, H.; He, J. Facile Fabrication of Raspberry-like Composite Nanoparticles and their Application as Building Blocks for Constructing Superhydrophilic Coatings. J. Phys. Chem. C 2009, 113, 9063–9070.   \n15. Zorba, V.; Chen, X.; Mao, S. S. Superhydrophilic $\\mathsf{T i O}_{2}$ Surface without Photocatalytic Activation. Appl. Phys. Lett. 2010, 96, 093702–093704.   \n16. Zhang, L.; Qiao, Z.-A.; Zheng, M.; Huo, Q.; Sun, J. Rapid and Substrate-Independent Layer-by-Layer Fabrication of Antireflection- and Antifogging-Integrated Coatings. J. Mater. Chem. 2010, 20, 6125–6130.   \n17. Zhang, L.; Li, Y.; Sun, J.; Shen, J. Mechanically Stable Antireflection and Antifogging Coatings Fabricated by the Layer-by-Layer Deposition Process and Postcalcination. Langmuir 2008, 24, 10851–10857.   \n18. You, J.-H.; Lee, B.-I.; Lee, J.; Kim, H.; Byeon, S.-H. Superhydrophilic and Antireflective $\\mathsf{L a}({\\mathsf{O H}})_{3}/\\mathsf{S i O}_{2}$ -Nanorod/ Nanosphere Films. J. Colloid Interface Sci. 2011, 354, 373–379.   \n19. Wang, J.-J.; Wang, D.-S.; Wang, J.; Zhao, W.-L.; Wang, C.-W. High Transmittance and Superhydrophilicity of Porous $\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ Bi-Layer Films without UV Irradiation. Surf. Coat. Technol. 2011, 205, 3596–3599.   \n20. Tahk, $\\mathsf{D}\\mathsf{;}$ Kim, T.-i.; Yoon, H.; Choi, M.; Shin, K.; Suh, K. Y. Fabrication of Antireflection and Antifogging Polymer Sheet by Partial Photopolymerization and Dry Etching. Langmuir 2010, 26, 2240–2243.   \n21. Cebeci, F. C-.; Wu, Z.; Zhai, L.; Cohen, R. E.; Rubner, M. F. Nanoporosity-Driven Superhydrophilicity: A Means to Create Multifunctional Antifogging Coatings. Langmuir 2006, 22, 2856–2862.   \n22. Chevallier, P.; Turgeon, S. P.; Sarra-Bournet, C.; Turcotte, R. L.; Laroche, G. T. Characterization of Multilayer Anti-Fog Coatings. ACS Appl. Mater. Interfaces 2011, 3, 750–758.   \n23. Chien, D. M.; Viet, N. N.; Van, N. T. K.; Phong, N. T. P. Characteristics Modification of $\\mathsf{T i O}_{2}$ Thin Films by Doping with Silica and Alumina for Self-Cleaning Application. J. Exp. Nanosci. 2009, 4, 221–232.   \n24. Du, X.; He, J. Facile Fabrication of Hollow Mesoporous Silica Nanospheres for Superhydrophilic and Visible/Near-IR Antireflection Coatings. Chem.\u0001Eur. J. 2011, 17, 8165– 8174.   \n25. Gan, W. Y.; Lam, S. W.; Chiang, K.; Amal, R.; Zhao, H.; Brungs, M. P. Novel $\\mathsf{T i O}_{2}$ Thin Film with Non-UV Activated Superwetting and Antifogging Behaviours. J. Mater. Chem. 2007, 17, 952–954.   \n26. Han, J.; Dou, Y.; Wei, M.; Evans, D. G.; Duan, X. Antireflection/ Antifogging Coatings Based on Nanoporous Films Derived from Layered Double Hydroxide. Chem. Eng. J. 2011, 169, 371–378.   \n27. Kwak, G.; Jung, S.; Yong, K. Multifunctional Transparent ZnO Nanorod Films. Nanotechnology 2011, 22, 115705.   \n28. Lam, S.; Soetanto, A.; Amal, R. Self-Cleaning Performance of Polycarbonate Surfaces Coated with Titania Nanoparticles. J. Nanopart. Res. 2009, 11, 1971–1979.   \n29. Law, W. S.; Lam, S. W.; Gan, W. Y.; Scott, J.; Amal, R. Effect of Film Thickness and Agglomerate Size on the Superwetting and Fog-Free Characteristics of $\\mathsf{T i O}_{2}$ Films. Thin Solid Films 2009, 517, 5425–5430.   \n30. Lee, D.; Rubner, M. F.; Cohen, R. E. All-Nanoparticle ThinFilm Coatings. Nano Lett. 2006, 6, 2305–2312.   \n31. Li, Y.; Zhang, J.; Zhu, S.; Dong, H.; Jia, F.; Wang, $z_{\\cdot\\mathrm{{\\rangle}}}$ Sun, Z.; Zhang, L.; Li, Y.; Li, H.; et al. Biomimetic Surfaces for HighPerformance Optics. Adv. Mater. 2009, 21, 4731–4734.   \n32. Liu, X.; Du, X.; He, J. Hierarchically Structured Porous Films of Silica Hollow Spheres via Layer-by-Layer Assembly and Their Superhydrophilic and Antifogging Properties. ChemPhysChem 2008, 9, 305–309.   \n33. Introzzi, L.; Fuentes-Alventosa, J. M.; Cozzolino, C. A.; Trabattoni, S.; Tavazzi, S.; Bianchi, C. L.; Schiraldi, A.; Piergiovanni, L.; Farris, S. “Wetting Enhancer” Pullulan Coating for Antifog Packaging Applications. ACS Appl. Mater. Interfaces 2012, 4, 3692–3700.   \n34. Lee, H.; Mensire, R.; Cohen, R. E.; Rubner, M. F. Strategies for Hydrogen Bonding Based Layer-by-Layer Assembly of Poly(vinyl alcohol) with Weak Polyacids. Macromolecules 2012, 45, 347–355.   \n35. Lin, C.; Gitsov, I. Synthesis and Physical Properties of Reactive Amphiphilic Hydrogels Based on Poly(pchloromethylstyrene) and Poly(ethylene glycol): Effects of Composition and Molecular Architecture. Macromolecules 2010, 43, 3256–3267.   \n36. Qu, X.; Wirsén, A.; Albertsson, A. C. Novel pH-Sensitive Chitosan Hydrogels: Swelling Behavior and States of Water. Polymer 2000, 41, 4589–4598.   \n37. Ostrowska-Czubenko, J.; Gierszewska-Druz_yn\u0002ska, M. Effect of Ionic Crosslinking on the Water State in Hydrogel Chitosan Membranes. Carbohydr. Polym. 2009, 77, 590– 598.   \n38. Briscoe, B. J.; Galvin, K. P. The Effect of Surface Fog on the Transmittance of Light. Sol. Energy 1991, 46, 191–197.   \n39. Engländer, T.; Wiegel, D.; Naji, L.; Arnold, K. Dehydration of Glass Surfaces Studied by Contact Angle Measurements. J. Colloid Interface Sci. 1996, 179, 635–636.   \n40. Wang, Y.; Dong, Q.; Wang, Y.; Wang, H.; Li, G.; Bai, R. Investigation on RAFT Polymerization of a Y-Shaped Amphiphilic Fluorinated Monomer and Anti-Fog and OilRepellent Properties of the Polymers. Macromol. Rapid Commun. 2010, 31, 1816–1821.   \n41. Farris, S.; Introzzi, L.; Biagioni, P.; Holz, T.; Schiraldi, A.; Piergiovanni, L. Wetting of Biopolymer Coatings: Contact Angle Kinetics and Image Analysis Investigation. Langmuir 2011, 27, 7563–7574.   \n42. Horinouchi, A.; Atarashi, H.; Fujii, Y.; Tanaka, K. Dynamics of Water-Induced Surface Reorganization in Poly(methyl methacrylate) Films. Macromolecules 2012, 45, 4638–4642.   \n43. Vaidya, A.; Chaudhury, M. K. Synthesis and Surface Properties of Environmentally Responsive Segmented Polyurethanes. J. Colloid Interface Sci. 2002, 249, 235–245.",
+        "category": " References"
+    },
+    {
+        "id": 20,
+        "chunk": "# ARTICLE",
+        "category": " Abstract"
+    },
+    {
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+        "chunk": "# ARTICLE  \n\nRuckenstein, E.; Gourisankar, S. V. Surface Restructuring of Polymeric Solids and Its Effect on the Stability of the Polymer;Water Interface. J. Colloid Interface Sci. 1986, 109, 557–566.   \n45. Crowe-Willoughby, J. A.; Genzer, J. Formation and Properties of Responsive Siloxane-Based Polymeric Surfaces with Tunable Surface Reconstruction Kinetics. Adv. Funct. Mater. 2009, 19, 460–469.   \n46. Holly, F. J.; Refojo, M. F. Wettability of Hydrogels I. Poly(2-hydroxyethyl methacrylate). J. Biomed. Mater. Res. 1975, 9, 315–326.   \n47. Haraguchi, K.; Li, H.-J.; Okumura, N. Hydrogels with Hydrophobic Surfaces: Abnormally High Contact Angles for Water on PNIPA Nanocomposite Hydrogels. Macromolecules 2007, 40, 2299–2302.   \n48. Haraguchi, K.; Li, H.-J.; Song, L. Unusually High Hydrophobicity and Its Changes Observed on the Newly-Created Surfaces of PNIPA/Clay Nanocomposite Hydrogels. J. Colloid Interface Sci. 2008, 326, 41–50.   \n49. Yasuda, H.; Sharma, A. K.; Yasuda, T. Effect of Orientation and Mobility of Polymer Molecules at Surfaces on Contact Angle and Its Hysteresis. J. Polym. Sci., Polym. Phys. Ed. 1981, 19, 1285–1291.   \n50. Style, R. W.; Dufresne, E. R. Static Wetting on Deformable Substrates, from Liquids to Soft Solids. Soft Matter 2012, 8, 3177–3184.   \n51. Cassie, A. B. D.; Baxter, S. Wettability of Porous Surfaces. Trans. Faraday Soc. 1944, 40, 0546–0550.   \n52. Varanasi, K. K.; Hsu, M.; Bhate, N.; Yang, W.; Deng, T. Spatial Control in the Heterogeneous Nucleation of Water. Appl. Phys. Lett. 2009, 95, 094101.   \n53. Beysens, D. The Formation of Dew. Atmos. Res. 1995, 39, 215–237.   \n54. Koutsky, J. A.; Walton, A. G.; Baer, E. Heterogeneous Nucleation of Water Vapor on High and Low Energy Surfaces. Surf. Sci. 1965, 3, 165–174.   \n55. Moazed, K. L.; Hirth, J. P. On the Contact Angle in Heterogeneous Nucleation upon a Substrate. Surf. Sci. 1965, 3, 49–61.   \n56. Cha, W.-I.; Hyon, S.-H.; Ikada, Y. Microstructure of Poly(vinyl alcohol) Hydrogels Investigated with Differential Scanning Calorimetry. Makromol. Chem. 1993, 194, 2433–2441.   \n57. Kim, H.; Doh, J.; Irvine, D. J.; Cohen, R. E.; Hammond, P. T. Large Area Two-Dimensional B Cell Arrays for Sensing and Cell-Sorting Applications. Biomacromolecules 2004, 5, 822–827.   \n58. Salloum, D. S.; Schlenoff, J. B. Protein Adsorption Modalities on Polyelectrolyte Multilayers. Biomacromolecules 2004, 5, 1089–1096.   \n59. Cortez, C.; Quinn, J. F.; Hao, X.; Gudipati, C. S.; Stenzel, M. H.; Davis, T. P.; Caruso, F. Multilayer Buildup and Biofouling Characteristics of PSS-b-PEG Containing Films. Langmuir 2010, 26, 9720–9727.   \n60. Gemici, Z.; Schwachulla, P. I.; Williamson, E. H.; Rubner, M. F.; Cohen, R. E. Targeted Functionalization of Nanoparticle Thin Films via Capillary Condensation. Nano Lett. 2009, 9, 1064–1070.   \n61. Meuler, A. J.; Chhatre, S. S.; Nieves, A. R.; Mabry, J. M.; Cohen, R. E.; McKinley, G. H. Examination of Wettability and Surface Energy in Fluorodecyl POSS/Polymer Blends. Soft Matter 2011, 7, 10122–10134.   \n62. Chinga, G.; Syverud, K. Quantification of Paper Mass Distributions within Local Picking Areas. Nord. Pulp Paper Res. J. 2007, 22, 441–446.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Amphiphilic Antifogging/Anti-Icing Coatings Containing POSSPDMAEMA‑b‑PSBMA  \n\nChuan Li, Xiaohui Li, Chao Tao, Lixia Ren, Yunhui Zhao, Shan Bai, and Xiaoyan Yuan\\*  \n\nSchool of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University Tianjin 300072, China  \n\nSupporting Information  \n\nABSTRACT: Highly transparent antifogging/anti-icing coatings were developed from amphiphilic block copolymers of polyhedral oligomeric silsesquioxane-poly[2-(dimethylamino)- ethyl methacrylate]-block-poly(sulfobetaine methacrylate) (POSS-PDMAEMA-b-PSBMA) with a small amount of ethylene glycol dimethacrylate (EGDMA) via UV-curing. The excellent antifogging properties of the prepared coatings were originated from the hygroscopicity of both PDMAEMA and PSBMA blocks in the semi-interpenetrating polymer network (SIPN) with polymerization of EGDMA and  \n\n![](images/c70b509ae5daf223902423f10b9749fd9c0a97c88c9f668a02c189df753abb13.jpg)  \n\nhydrophobic POSS clusters aggregated on the surface. PDMAEMA with a lower critical solution temperature and PSBMA with an upper critical solution temperature in the block copolymers facilitated dispersion and absorption of water molecules into the SIPN coatings, fulfilling the enhanced antifogging function. Analysis of differential scanning calorimetry further confirmed that there was bond water and nonfreezable bond water in the SIPN coatings. The amphiphilic SIPN coatings exhibited the antiicing ability with a freezing delay time of more than $2~\\mathrm{min}$ at $-15^{\\circ}\\mathrm{C},$ owing to the aggregation of hydrophobic POSS groups and the self-lubricating aqueous layer generated by nonfreezable bond water on the surface. The prepared transparent antifogging/ anti-icing coatings could have novel potential applications in practice.  \n\nKEYWORDS: amphiphilic coating, semi-interpenetrating polymer network, POSS, antifogging, anti-icing",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# INTRODUCTION  \n\nFormation of fog is ascribed to condensed water droplets caused by unexpected changes in temperature and humidity, bringing about optical opacity of transparent surfaces such as windshields, periscopes, and display devices in the analytical instruments.1−3 To alleviate the trouble of fog, superhydrophilic polymer films have been extensively investigated because their surfaces can quickly absorb and spread condensed water droplets, forming a continuous aqueous layer that allows light to pass through without too much scattering.2−5 Superhydrophobic surfaces were also applied to mitigate fogging problems and impart to these surfaces an antifogging performance.6,7 Nevertheless, the preparation of highly transparent antifogging coatings still remained a challenge, especially because of the meticulous preparation process of the superhydrophilic and superhydrophobic surfaces with micro-/ nano-structures, which possibly limited their applications.5−7  \n\nIn the recent years, amphiphilic coatings have been developed to achieve effective antifogging properties via the synergistic strategy of hydrophilic and hydrophobic components.3,8−10 Cohen et al. prepared zwitter-wettable antifogging coatings by layer-by-layer assembly from chitosan and Nafion with a nanoscale-thin hydrophobic capping layer, enabling water vapor to diffuse rapidly into the underlying hydrophilic coatings. Triggered by the hydrophilic/hydrophobic balance, Ming et al. fabricated a semi-interpenetrating polymer network (SIPN) coating from an acrylate copolymer, namely, poly(2- (dimethylamino)-ethyl methacrylate-co-methyl methacrylate), via polymerization of ethylene glycol dimethacrylate (EGDMA) to achieve antifogging.9,10 In contrast to superhydrophilic or superhydrophobic antifogging coatings, amphiphilic coatings displayed high initial water contact angles (CAs), which subsequently decreased to low values within a period of time.8 ,9 Water or vapor molecules could be rapidly absorbed from the surrounding environment and spread in the coatings by a hydrogen-bond interaction in the form of nonfreezable water, rather than condensed as drops of liquid water on the surface. $^{2-4,8-10}$ The hydrophobicity of amphiphilic coatings also facilitated dispersion of water molecules into the coatings.3,8−10  \n\nIn addition to the antifogging capability, the amphiphilic coatings exhibited frost-resistance3,10 or anti-icing properties.11,12 For example, a small amount (1 wt $\\%$ ) of amphiphilic copolymer poly(dimethylsiloxane) (PDMS)-poly(ethylene glycol) (PEG, $25\\%$ ) was introduced in the smooth PDMS coating and then a viscous lubricating liquid-like layer could generate at the coating surface, which exhibited icephobicity with a lower ice adhesion strength.11 Amphiphilic cross-linked hyperbranched fluoropolymers containing water-absorbing PEG chains also demonstrated anti-icing properties for potential engineering applications.12 Alternatively, the surfaces consisting of cross-linked hygroscopic polymers such as poly(acrylic acid) could be infused with water, bringing about a self-lubricating aqueous layer for the anti-icing purpose.13,14 Moreover, slippery liquid infused nanostructured surfaces could exhibit icerepellency behaviors,15,16 a s well as excellent optical transparency.17 The aqueous layer self-lubricating coatings with distinguished antifogging/anti-icing abilities would exhibit a great advantage in the practical applications.11−14  \n\n![](images/1e84236c01662b78ac8b4bfab6f4fd07f91ad714830620a7ce1d0916b27f9500.jpg)  \nScheme 1. Schematic Illustration of the Synthesis of POSS-PDMAEMA-b-PSBMA  \n\nTable 1. Compositions of the Prepared Block Copolymers   \n\n\n<html><body><table><tr><td rowspan=\"2\"> sample</td><td rowspan=\"2\">feeding composition DMAEMA/SBMA (mol/mol)</td><td rowspan=\"2\">molar composition DMAEMA/SBMA in the copolymera (mol/mol)</td><td rowspan=\"2\">Mna (× 104)</td><td rowspan=\"2\">PDI</td></tr><tr><td></td></tr><tr><td>POSS-D50-b-S7</td><td>50:7</td><td>43:7 (6.14:1)</td><td>0.97</td><td>1.07</td></tr><tr><td>POSS-D7o-b-S10</td><td>70:10</td><td>65:11 (5.91:1)</td><td>1.43</td><td>1.08</td></tr><tr><td>POSS-D90-b-S13</td><td>90:13</td><td>95:15 (6.33:1)</td><td>2.02</td><td>1.11</td></tr><tr><td>D5o-b-S7</td><td>50:7</td><td>40:11 (3.64:1)</td><td>0.96</td><td>1.19</td></tr></table></body></html>\n\naThe molar composition and the number-average molecular weight of the POSS-PDMAEMA- $\\mathbf{\\nabla}_{b}$ -PSBMA block copolymers (abbreviated as POSS$\\mathrm{D}_{50^{-}}b{-}S_{7},$ $\\mathrm{POSS-D}_{70^{-}}b{\\cdot}\\mathrm{S}_{10},$ and $\\mathrm{POSS-D}_{90}–b–\\ensuremath{\\mathrm{S}}_{13},$ respectively) were estimated by $\\mathrm{^{1}H}$ NMR spectra, and the result of PDMAEMA- $\\cdot\\boldsymbol{b}$ -PSBMA (abbreviated as $\\mathrm{D}_{50}–b–S_{7},$ ) was determined by GPC.  \n\nAs we know, dual-thermosensitive block copolymers can be prepared from a lower critical solution temperature (LCST) polymer such as poly(N-isopropylacrylamide) and poly(N,Ndimethylaminoethyl methacrylate) (PDMAEMA), and an upper critical solution temperature (UCST) polymer such as zwitterionic poly(sulfobetaine methacrylate) (PSBMA) or a random copolymer of poly(acrylamide-co-acrylonitrile).18−20 The random or block copolymers could display both LCST and UCST characteristics in the aqueous solution ,18−20 even though they were grafted from silica nanoparticles.18 Thus, it can be assumed that antifogging/anti-icing coatings can be developed by combining PDMAEMA with LCST and PSBMA with UCST, which could possibly give rise to a self-lubricating aqueous layer when exposed to water or vapor and synergistically enhance the antifogging and anti-icing performances. Meanwhile, PDMAEMA was chosen as the main part of the amphiphilic polymers because of its good film-forming property on substrates and fine stability. In contrast, due to strongly electrostatic and hydrogen-bond interactions with water, zwitterionic PSBMA could regulate and control the hydrophilicity of polyhedral oligomeric silsesquioxane-poly[2- (dimethylamino)ethyl methacrylate]-block-poly(sulfobetaine methacrylate) (POSS-PDMAEMA- $b$ -PSBMA) and enhance the antifogging/anti-icing performances of the amphiphilic SIPN coatings. In addition, the zwitterionic PSBMA component could possibly reduce the freezing point of water, as stated in refs 21, 22.  \n\nAccording to our previous studies on POSS-containing fluorosilicone block copolymers, POSS groups with a low surface energy could migrate and aggregate on the coating surfaces, endowing them with hydrophobicity for antiicin g.23−26 By integrating POSS with both PDMAEMA and PSBMA via atom transfer radical polymerization (ATRP), in this work, we prepared the amphiphilic SIPN coatings from POSS-PDMAEMA- $b$ -PSBMA block copolymers with a small amount $10\\mathrm{\\wt\\}\\%$ of EGDMA via UV-curing. We supposed that PDMAEMA and PSBMA blocks in the cross-linked PEGDMA network coupled with hydrophobic POSS groups could facilitate absorption of water or vapor molecules into the coatings to enhance the antifogging performance. In addition, the amphiphilic SIPN coating was expected to decrease the water freezing-point by forming a self-lubricating aqueous layer at the surface so as to keep high transmittance under foggy conditions and display the anti-icing properties.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# EXPERIMENTAL SECTION  \n\nSynthesis of POSS-PDMAEMA-b-PSBMA. The POSS-PDMAEMA- $\\cdot b$ -PSBMA block copolymers were synthesized via ATRP of DMAEMA by using POSS-Br as an initiator according to ref 27, followed by ATRP of SBMA by using POSS-PDMAEMA−Br as a macroinitiator (Scheme 1). Three POSS-PDMAEMA- $\\mathbf{\\nabla}_{b}$ -PSBMA block copolymers with different polymerization degrees were prepared, whereas block copolymer PDMAEMA- $\\cdot\\boldsymbol{b}$ -PSBMA without POSS by using ethyl-2-bromoisobutanoate as the initiator was also synthesized as the control. According to the references, stronger hydrogen-bonded water molecules can form on the zwitterionic SBMA surfaces rather than on the surface of PEG,28 and a small amount of SBMA in the PDMAEMA- $\\cdot\\boldsymbol{b}$ -PSBMA block copolymers still exhibited a dualthermoresponsive performance.20 Given that PDMAEMA chains played a key role in antifogging,9,10 we further designed the block copolymers with a higher DMAEMA content. To obtain similar molar ratios of DMAEMA to those of SBMA, three block copolymers, that is, POSS-PDMAEMA50-b-PSBMA7, $\\mathrm{POSS–PDMAEMA_{70}–}k$ - $\\mathrm{\\cdotPSBMA_{10}},$ and $\\mathrm{POSS-PDMAEMA}_{90}–b–\\mathrm{PSBMA}_{13},$ were synthesized. Compositions of the prepared block copolymers, abbreviated as $\\mathrm{POSS-D}_{50}–b–S_{7},$ $\\mathrm{POSS-D}_{70}–b–S_{10},$ $\\mathrm{POSS-D}_{90}–b–S_{13}$ and $\\mathrm{D}_{50}–b–\\mathrm{S}_{7},$ respectively, are shown in Table 1. Detailed synthesis of the block copolymers and their characterizations by $\\mathrm{^{1}H}$ NMR, Fourier transform infrared (FTIR), gel permeation chromatography (GPC), and thermogravimetric analysis (TGA) are given in the Supporting Information (Figures S1−S4).  \n\n![](images/0fc67a97fb2d236c93622604eb2c4998a732305f578a0cc4cdca14db0c6a2a8b.jpg)  \nB: exposed at ambient conditions after stored at -20 °C   \nFigure 1. Photographs of the glass slides partially covered with the SIPN coatings containing $\\mathrm{POSS-D}_{50^{-}}b{\\cdot}S_{7}$ (a), $\\mathrm{POSS-D}_{70}–b–S_{10}$ (b), $\\mathrm{POSS-D}_{90^{-}}b$ - $S_{13}^{\\phantom{-}}$ (c), and $\\mathrm{D}_{50}{-}b{-}S_{7}$ (d), respectively, over boiling water $\\mathrm{\\sim}80^{\\circ}\\mathrm{C},$ $100\\%$ relative humidity) (A), and exposed quickly at ambient conditions ${\\widetilde{\\mathbf{\\Gamma}}}\\sim20$ ${}^{\\circ}\\mathrm{C},$ $55\\%$ relative humidity) right after being stored at $-20~^{\\circ}\\mathrm{C}$ for $45\\ \\mathrm{min}$ (B).  \n\nPreparation of the SIPN Coatings. A given amount of the block copolymer $(\\mathrm{POSS-D}_{50^{-}}b{-}S_{7},$ $\\mathrm{POSS-D}_{70}–b–S_{10},$ $\\mathrm{POSS-D}_{90^{-}}b{\\mathrm{-}}\\mathrm{S}_{13},$ or $\\mathrm{D}_{50^{-}}$ $\\left.b{-}S_{7}\\right)$ ) was dissolved in 2,2,2-trifluoroethanol to prepare a $25~\\mathrm{mg/mL}$ polymer solution. EGDMA (10 wt $\\%$ based on the copolymer) and Igracure 2959 UV photoinitiator (2 wt $\\%$ ) were also added. The polymer coatings were prepared by casting $0.2{\\mathrm{~mL}}$ of the polymer solution onto a half of a clean glass slide (both sides) and then placing them under UV conditions $(\\bar{365}\\ \\mathrm{nm},\\ 15\\ \\mathrm{W},\\ 1800\\ s)$ in an XL-1000 ultraviolet cross-linker apparatus for the polymerization of EGDMA. The transmittance of the SIPN coatings containing the block copolymers, $\\mathrm{POSS-D}_{50^{-}}b{-}S_{7},$ $\\mathrm{POSS-D}_{70^{-}}b{\\cdot}\\mathrm{S}_{10},$ $\\mathrm{POSS-D}_{90}–b–S_{13},$ and $\\mathrm{D}_{50}–b–S_{7},$ denoted as $\\mathrm{C-POSS-D}_{50}–b–S_{7},$ $\\mathrm{C-POSS-D}_{70^{-}}b{\\cdot}\\mathrm{S}_{10},$ C-POSS$\\mathrm{D}_{90}–b–S_{13},$ and $\\mathrm{C-D}_{50}{\\cdot}b{\\cdot}S_{7},$ respectively, were obtained by further airdrying at room temperature. The thickness of the obtained SIPN coatings was about $10\\ \\mu\\mathrm m$ .  \n\nCharacterizations. Atomic force microscope (AFM) images were obtained by a CSPM5500A microscope AFM machine (Benyuan Nano-Instruments, China) equipped with an E-type vertically engaged piezoelectric scanner and operated in a tapping-mode at room temperature. X-ray photoelectron spectroscopy (XPS) measurements were performed on a Perkin-Elmer PHI 5000C ECSA system, utilizing an excitation source of Al $\\mathrm{K}\\alpha$ radiation under a pressure of ${\\sim}6.7\\times$ $10^{-6}$ Pa at $45^{\\circ}$ . Water CAs of the SIPN coatings and their evolution were recorded by a JC2000D CA meter (Shanghai Zhongchen Equipment Co. Ltd., China) to examine the wettability of the samples with deionized water drops $(5\\mu\\mathrm{L})$ .  \n\nAntifogging Tests. The antifogging property was tested with the hot-vapor and cold−warm methods, separately. Generally, the glass slide covered by the SIPN coatings on one half of it was put over hot vapor (above about $5{\\mathrm{~cm~high}}, $ ) by placing it on top of a glass beaker that contained hot water $\\mathrm{\\sim}80\\ ^{\\circ}\\mathrm{C},$ $100\\%$ relative humidity), and the sample transparency was recorded immediately. In addition, the appearance of the samples was recorded quickly when they were exposed to a warm, humid environment $(\\sim20\\ ^{\\circ}\\mathrm{C},$ $55\\%$ relative humidity) right after being stored in a $-20{}^{\\circ}\\mathrm{C}$ freezer for $45\\ \\mathrm{min}$ . The transmittance of the samples was also measured in a 722s visible spectrophotometer (Shanghai Jinghua Technology Instrument Co.  \n\nLtd., China) ranging from 400 to $800~\\mathrm{{\\nm}}$ for the quantitative measurement.  \n\nAnti-Icing Tests. The freezing delay time $(T_{\\mathrm{D}})$ of water droplets on the SIPN coatings was measured to test the anti-icing performance. The specimen was placed on a cold-plate (Tianjin Jing Yi Industry & Trade Co. Ltd., China), which was controlled at $-15~^{\\circ}\\mathrm{C}.$ . Once a deionized water droplet $(5~\\mu\\mathrm{L})$ dropped on the coating surface, its appearance was recorded in every second, and the time when the water droplet became ice completely, that is, when a sharp tip appeared on the droplet top, was regarded as the freezing delay time.  \n\nDifferential Scanning Calorimetry (DSC) Analysis. The bond water amount in the SIPN coatings was analyzed by DSC (TA Q2000). The samples for the DSC measurements containing a certain amount of deionized water were prepared by adding water into the SIPN coatings (about ${4{-}5\\ }\\mathrm{mg},\\nonumber$ , which were scraped from the glass slide. The sample was kept and stabilized in the aluminium pan for 10 days at room temperature. When no mass changes were confirmed during a period of several days, the samples were tested in the following procedure by purging nitrogen gas. The sample was first cooled from 20 to $-70~^{\\circ}\\mathrm{C}$ at a cooling rate of $5~\\mathrm{{^\\circC/min}}$ and maintained for $3\\mathrm{min}$ . Then, it was heated to $20~^{\\circ}\\mathrm{C}$ at a heating rate of $5~{^\\circ}\\mathrm{C}/\\mathrm{min}$ and subsequently held at $20~^{\\circ}\\mathrm{C}$ for around $3\\ \\mathrm{min}$ . The cooling−heating cycle was also conducted in the same manner at heating/cooling rates of 10 and $15~\\mathrm{{^{\\circ}C/m i n}}$ , respectively. The total water content $\\Bar{(}W_{\\mathrm{c}})$ , the freezable water content $(W_{\\mathrm{f}})_{\\cdot}$ , the nonfreezable bond water content $(W_{\\mathrm{nfb}})_{\\cdot}$ , and the bond water content $(W_{\\mathfrak{b}})$ in the samples were calculated according to the following equations.29−33  \n\n$$\nW_{\\mathrm{c}}=m_{\\mathrm{w}}/m_{\\mathrm{c}}\n$$  \n\n$$\nW_{\\mathrm{f}}=A_{\\mathrm{c}}/{\\left(334m_{\\mathrm{c}}\\right)}\n$$  \n\n$$\nW_{\\mathrm{nfb}}=W_{\\mathrm{c}}-W_{\\mathrm{f}}\n$$  \n\n$$\nW_{\\mathrm{b}}=W_{\\mathrm{fb}}+W_{\\mathrm{nfb}}\n$$  \n\nwhere $m_{\\mathrm{w}}$ and $m_{\\mathrm{c}}$ represent the masses of water and the coating, respectively, in the samples, and $A_{\\mathrm{c}}\\left(\\mathrm{J}/\\mathrm{g}\\right)$ refers to the integral melting peak area in the heating curves. Here, we hypothesize that the enthalpies of both free and freezable water are equal to $334\\mathrm{J/g},$ the specific heat of water fusion.29 During the analysis, the freezable bond water content $(W_{\\mathrm{fb}})$ was corresponding to the area of the symmetric peak at around $-15~^{\\circ}\\mathrm{C}$ in the heating curves, and the free water content $(W_{\\mathbb{H}})$ (that is freezable) was the difference between $W_{\\mathrm{f}}$ and $W_{\\mathrm{fb}}$ according to refs 29, 30. Therefore, the bond water content $(W_{\\mathfrak{b}})$ was the sum of $W_{\\mathrm{fb}}$ and $W_{\\mathrm{nfb}}$ . The melting temperatures of the freezable bond water $(T_{\\mathrm{fbm}})$ and the freezable free water $\\left(T_{\\mathrm{ffm}}\\right)$ were designated as the peak temperatures of the fitting symmetric peak and the melting peak, respectively, in the heating curves of the samples.  \n\n![](images/97c7d96a8dc5575eead3271b10f9b941566f0cb623dabe2ace65cbc070c74de8.jpg)  \nFigure 2. Transmittance of the SIPN coatings before (A) and after (B) storing at $-20~^{\\circ}\\mathrm{C}$ for $45\\ \\mathrm{min}$ , and exposed quickly to a warm, humid surrounding ${\\bf\\tilde{\\mu}}_{\\sim20}\\circ_{\\bf C}$ , $55\\%$ relative humidity).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# RESULTS AND DISCUSSION  \n\nAntifogging Properties. The antifogging performance of the SIPN coatings was demonstrated with the hot-vapor and cold−warm methods. For the hot-vapor method, the glass slides with both sides partially coated by the SIPN coatings were placed $5\\ \\mathrm{cm}$ high above boiling water $(\\sim80~^{\\circ}\\mathrm{C},$ $100\\%$ relative humidity). As shown in Figure 1A, it can be seen that the uncoated areas of the bare glass slides were apparently covered by small condensed water droplets of hot vapor, resulting in optical opacity. In contrast, the other halves of the glass slides with the SIPN coatings still remained highly transparent. The excellent antifogging properties of all of the samples could be attributed to the hydrophilic PDMAEMA and PSBMA blocks in the copolymers and the cross-linked PEGDMA network, which allowed water molecules to be rapidly absorbed into the SIPN coating and possibly spread over the coating surface, similar to the situation stated in refs 8, 34. It was supposed that surface hydration of the prepared coatings could occur owing to the hydrogen-bonded interactions of water molecules with PDMAEMA and PSBMA blocks as well as PEGDMA.28 When water molecules entered into the coatings, hydrogen bonds between water and polymer chains could be formed in the SIPN coatings at a molecular level due to the presence of oxygen atoms of ester and ether groups in PDMAEMA, PSBMA, and PEGDMA chains, as well as nitrogen atoms in the structure of PDMAEMA, ensuring the excellent optical transparency. Moreover, because of the electrostatic attraction of zwitterionic groups, the hydrogenbonded interaction between hydrophilic PSBMA and water molecules is stronger than that between water and PDMAEMA or PEGDMA chains in the coatings.28,35  \n\nIn addition, when the temperature exceeded the LCST (about $48\\ ^{\\circ}\\mathrm{C}\\ '$ ) of PDMAEMA,20 the random coil conformation of the PDMAEMA chains tended to collapse due to the break of hydrogen-bonded interactions between the polymer and water molecules, resulting in the gathering tendency of PDMAEMA chains.20 The PDMAEMA chains, however, were restricted by the cross-linked network and could not aggregate to some extent. Therefore, the contractive force caused by gathering of the PDMAEMA chains could give rise to free voids for dispersion of water molecules in the SIPN coatings.  \n\nThe antifogging performance of the SIPN coatings was also evaluated with the cold−warm method. The SIPN coatings were first stored in a $-20~^{\\circ}\\mathrm{C}$ freezer for $45\\mathrm{\\min}$ and then rapidly exposed to a warm, humid environment $\\mathrm{\\Omega}^{\\prime}{\\sim}20\\ ^{\\circ}\\mathrm{C},$ , $55\\%$ relative humidity). As shown in Figure 1B, the uncoated parts of the glass slides were fogged severely and the words and patterns under the container became heavily blurred due to light scattering. In contrast, the coated parts displayed high transparency, indicating the excellent antifogging performance of the SIPN coatings. When water molecules were absorbed in the coatings, hydrogen bonds between water and the polymer molecules were subsequently generated at a molecular level.28 In addition, when the temperature was inferior to the UCST $(\\sim5^{\\circ}\\mathrm{C})$ of PSBMA,20 the random coil of the PSBMA chains tended to collapse due to the strong interchain ionic interactions between the PSBMA chains, resulting in a gathering tendency of PSBMA chains.18−20 Therefore, water molecules were conducive to well dispersion in the SIPN coatings, which was attributed to the contractive force generated by the trend of gathering of PSBMA blocks under the limitation of the cross-linked PEGDMA structure.  \n\nThe antifogging properties were quantitatively characterized by measuring the transmittance of the bare glass and the coated parts of the glass slides in the range of a visible light wavelength from 400 to $800\\ \\mathrm{nm}$ (Figure 2). The optical transmittances of $\\mathrm{C-POSS-D}_{50}–b–S_{7},$ $\\mathrm{C-POSS-D}_{70^{-}}b{\\cdot}\\mathrm{S}_{10},$ $\\mathrm{C-POSS-D}_{90^{-}}b{\\cdot}\\mathrm{S}_{13},$ and $\\mathrm{C-D}_{50}{\\cdot}b{\\cdot}S_{7}$ were 87.2−89.2, 88.0−90.2, 89.0−91.2, and $85.9-\\$ $88.6\\%$ , respectively, which were quite similar to those of the bare glass $\\left(85.1-91.0\\%\\right)$ . The transmittance of the SIPN coatings containing POSS-PDMAEMA- $b$ -PSBMA slightly increased with the rise of the molecular weight of the block copolymers, and all of the SIPN coatings with or without POSS exhibited minor differences in the transmittance (Figure 2A). As shown in Figure 2B, during the cold−warm antifogging test, the transmittance of the bare glass decreased sharply to about $61.5\\substack{-63.2\\%}$ due to the formation of fog on the surface. The transmittance of the SIPN coatings containing $\\mathrm{POSS-D}_{50^{-}}b{-}S_{7},$ $\\mathrm{POSS-D}_{70^{-}}b{\\mathrm{-}}\\mathrm{S}_{10},$ and $\\mathrm{POSS-D}_{90}–b–S_{13}$ still remained 87.1−89.8, $87.1\\mathrm{-}90.0,\\$ and $88.0\\mathrm{-}90.4\\%$ , respectively, with trivial variations compared to the values before tests, showing an excellent antifogging performance. The SIPN coating containing $\\mathrm{D}_{50}–b$ - $S_{7}$ without POSS became $86.4\\substack{-88.7\\%}$ , also exhibiting a good antifogging property but inferior to that of the coatings containing POSS-related copolymers. It was suggested that there was an important effect of hydrophobic POSS groups on the antifogging performance of the SIPN coatings.  \n\n![](images/926451a18518239886bb992a4a4c770bd2db3c9a4eb1c9ae5a7539f0b3b4912f.jpg)  \nFigure 3. AFM images over a scope of $10\\ \\mu\\mathrm{m}\\times10\\ \\mu\\mathrm{m}$ of the SIPN coatings containing $\\mathrm{POSS-D}_{50^{-}}b{\\cdot}S_{7}$ (a), $\\mathrm{POSS-D}_{70}–b–S_{10}$ (b), $\\mathrm{POSS-D}_{90}–b–S_{13}$ (c), and $\\mathrm{D}_{50}–b–S_{7}$ (d).  \n\nTable 2. Surface Elemental Atomic Percentages of the SIPN Coatings Detected by XPS   \n\n\n<html><body><table><tr><td> sample</td><td>C 1s (atom %)</td><td>O ls (atom %)</td><td>N ls (atom %)</td><td>S 2p (atom %)</td><td>Si 2p (atom %)</td><td>bulk Si (atom %)</td></tr><tr><td>C-POSS-D50-b-S,</td><td>72.3</td><td>20.3</td><td>3.7</td><td>0.7</td><td>3.1</td><td>1.21</td></tr><tr><td>C-POSS-D7o-b-S10</td><td>72.9</td><td>19.9</td><td>3.6</td><td>1.2</td><td>2.5</td><td>0.82</td></tr><tr><td>C-POSS-D90-b-S13</td><td>70.2</td><td>21.2</td><td>3.5</td><td>0.9</td><td>4.2</td><td>0.58</td></tr><tr><td>C-D5o-b-S7</td><td>79.1</td><td>17.9</td><td>2.3</td><td>0.5</td><td></td><td></td></tr></table></body></html>  \n\nFor different structures of the polymeric coatings with or without POSS, the $\\mathrm{C-D}_{50}\\mathrm{-}b{\\mathrm{-}}\\mathrm{S}_{7}$ coating exhibited low transmittance before and after fogging in comparison with C-POSS$\\mathrm{D}_{50}–b–\\mathrm{S}_{7},$ indicating that the incorporation of POSS led to an active effect on the transmittance of the coating. It was assumed that the aggregated POSS groups on the SIPN coating surfaces could facilitate water dispersion into the amphiphilic SIPN coatings. However, for the amphiphilic SIPN coatings with similar structures, the transmittance of the coatings slightly increased before and after fogging with the rise of the molecular weight of the POSS-containing block copolymers. It was indicated that the introduction of POSS resulted in a slight negative effect on the transmittance, which did not decrease too much. It was assumed that the POSS-PDMAEMA- $\\cdot b$ -PSBMA copolymers could regulate and control the wettability of the amphiphilic SIPN coatings.  \n\nIn addition, the SIPN coatings may possess the ability of “thermal remediation” because the score scratched by a clean blade could be healed by vapor. The score on the $\\mathrm{C}{\\cdot}\\mathrm{POSS}{\\cdot}\\mathrm{D}_{70^{-}}$ $b{-}S_{10}$ coating disappeared completely when the sample was exposed over the hot vapor for $3~\\mathrm{min}$ , as shown in Figure S5. The phenomenon may be explained by the fact that the molecular chains of collapse could be reorganized under the drive of water vapor due to the partially cross-linked network of the SIPN coating as well as the hydrogen-bond interactions between water and the polymeric molecules.3,36 Moreover, the SIPN coatings demonstrated great stability when immersed in water, suggesting their long-lasting utilities, as shown in Figure S6. With the healable antifogging performance and stability, the SIPN coatings of the POSS-PDMAEMA- $\\cdot b$ -PSBMA block copolymers could have versatile potential applications.  \n\nSurface Characteristics of the SIPN Coatings. AFM was employed to observe the surface morphology of the SIPN coatings. As shown in Figure 3, all $\\mathrm{C-POSS-D}_{50}–b–S_{7},$ C-POSS$\\mathrm{D}_{70}{-}b{-}\\mathrm{S}_{10},$ $\\mathrm{C-POSS-D}_{90}–b–S_{13},$ and $\\mathrm{C-D}_{50}{\\cdot}b{\\cdot}\\ensuremath{\\mathrm{S}}_{7}$ samples exhibited smooth coating surfaces. Their root-mean-square roughness $(R_{\\mathrm{q}})$ values were estimated at ca. 0.6, 0.8, 0.5, and $1.0\\ \\mathrm{nm}$ , respectively. It was proved that an integrated film structure was successfully cross-linked by polymerization of EGDMA, endowing the SIPN coatings with preferable surface morphology.  \n\nSurface compositions of the SIPN coatings were measured by XPS. All of the element percentages on the coating surfaces, that is, C, N, O, S, and Si, are shown in Table 2. The theoretical bulk contents of the Si element, calculated from the molecular weight of the copolymers and the SIPN coating compositions, are also introduced in Table 2. It can be seen that the surface Si amounts of the amphiphilic SIPN coatings containing POSS  \n\n![](images/129652f5c52cc20ffc66b0b14c9c4f743e38d15a03f674c50a3199a58262917a.jpg)  \nFigure 4. Variation of the water CA values on the different SIPN coatings with time in $150\\ s$ (A), and the diameter evolution $\\left(\\Delta D/D_{0}\\right)$ of the droplets on the coating surfaces during the recorded period (B), where $\\Delta D=D-D_{0},D_{0}$ is the original diameter $\\left(t=0~s\\right)$ and $D$ is the diameter of the water droplet on the coating surface at a given time.  \n\n![](images/44fd7115cdc1b556ca72c4584b93bf611c670fbab28b9503fd1614d1822e751b.jpg)  \nFigure 5. Optical images of the water droplets on the bare glass slide and the SIPN coatings containing $\\mathrm{POSS-D}_{50^{-}}b{-}S_{7},$ $\\mathrm{POSS-D}_{70^{-}}b{\\cdot}{\\cal S}_{10},$ $\\mathrm{POSS–D}_{90}$ $b\\mathrm{-}S_{13},$ and $\\mathrm{D}_{50}–b–S_{7}$ during the freezing process. The freezing delay time $(T_{\\mathrm{D}})$ of each sample was observed. The temperature of the cool-plate was controlled at $-15~^{\\circ}\\mathrm{C}$ .  \n\nPDMAEMA- $b$ -PSBMA copolymers detected by XPS were all higher than those of their bulk Si contents, respectively. It was suggested that the POSS groups could possibly aggregate on the coating surfaces due to their low surface energy and endow the SIPN surfaces with the hydrophobic property.24−26 ATR− FTIR spectra were also applied to analyze and confirm the chemical structure of the SIPN coatings containing $\\mathrm{POSS-D}_{50}.$ - ${b/}{}_{{b/}{}}$ $\\mathrm{POSS-D}_{70^{-}}b{\\mathrm{-}}\\mathrm{S}_{10},$ $\\mathrm{POSS-D}_{90}–b–\\ensuremath{\\mathrm{S}}_{13},$ and $\\mathrm{D}_{50}–b–S_{7}$ block copolymers, as shown in Figure S7.  \n\nTo further examine the morphology of the aggregated POSS clusters in the SIPN coatings, the samples prepared by adding a droplet of dilute copolymer solutions (1 wt $\\%$ in trifluoroethanol) on copper grids and UV-curing were observed under a transmission electron microscope (TEM). As shown in Figure S8, it can be found that the aggregated POSS clusters were well dispersed within the polymer matrix with a size of $10{-}80~\\mathrm{nm},$ which coincided with ref 37. The size of the POSS aggregates tended to decrease with the increase of the relative molecular weight of POSS-PDMAEMA- $\\cdot b$ -PSBMA due to the relative reduction of the POSS proportion in the copolymers. In fact, the size (less than $100\\mathrm{nm}\\mathrm{\\Omega}$ ) of the POSS clusters was far smaller than the wavelength of visible light and hence the optical properties exhibited trivial discrepancy between samples with and without POSS. Besides, the discrete POSS clusters on the coating surfaces would not affect the absorption of water molecules into the hygroscopic polymers and play an important role in regulating and controlling the dispersion of water molecules in the coatings. The POSS clusters could be analogous to the outermost layer of hollow silica nanoparticles for antifogging and antireflective thin films, as reported by Zhang.38 Therefore, the surface structure of the $\\mathrm{C-D}_{50}{\\cdot}b{\\cdot}\\ensuremath{\\mathrm{S}}_{7}$ coating lacking the POSS function was different from that of the coatings containing POSS-PDMAEMA- $\\cdot b$ -PSBMA copolymers, exhibiting a slightly lower transmittance (Figure 2B) than the latter.  \n\nWettability of the SIPN Coatings. Changes of the water CA values of the SIPN coatings with time were recorded carefully under ambient conditions for $150\\ s.$ . As shown in Figure 4A, all $\\mathrm{C-POSS-D}_{50}–b–S_{7},$ $\\mathrm{C-POSS-D}_{70}–b–S_{10},$ and C$\\mathrm{POSS-D}_{90}–b–S_{13}$ coatings exhibited high initial CA values of around $105^{\\circ}$ , whereas the initial CA value of the $\\mathrm{C-D}_{50}{\\cdot}b{\\cdot}\\ensuremath{\\mathrm{S}}_{7}$ coating was about $60^{\\circ}$ . The results coincided with the recent findings in the references that an effective antifogging coating could not be superhydrophilic.3,8−10 Particularly, the C-POSS$\\mathrm{D}_{90}–b–S_{13}$ coating had a higher initial CA value $\\left(105.8\\pm0.4^{\\circ}\\right)$ , followed by a rapid decrease to $43.3\\pm1.3^{\\circ}$ in $60~\\mathsf{s}$ and $31.4\\pm$ $0.7^{\\circ}$ in ${150\\mathrm{\\s}},$ which was mainly attributed to the discrete POSS clusters on the coating surface and water-absorbing polymer chains inside. During the measurement, the water CA values on all SIPN surfaces decreased rapidly in $^{30\\mathrm{~s,~}}$ similar to the situation of the coatings containing strongly hydrophilic polymers such as poly(vinyl alcohol)/poly(acrylic acid) and chitosan/carboxymethyl cellulose, as reported by Cohen et al.4,8 The water CA values on all SIPN coatings decreased much more quickly at an early time due to water dispersion than water evaporation. It was suggested that water molecules could diffuse well into the SIPN coatings in a short time, similar to the results in ref 8.  \n\nTo further analyze the wettability of the SIPN coatings, the diameter development of the water droplets on the coating surfaces was also calculated as shown in Figure 4B. It can be seen that the diameter of the droplet on the bare glass was almost constant during the measurement period, whereas the diameter of the water droplet on the $\\mathrm{C-D}_{50}{\\cdot}b{\\cdot}S_{7}$ coating increased by about $35\\%$ . However, the variation of the droplet diameters on the $\\mathrm{C-POSS-D}_{50}–b–S_{7},$ $\\mathrm{C-POSS-D}_{70^{-}}b{\\cdot}\\mathrm{S}_{10},$ and C$\\mathrm{POSS-D}_{90}–b–S_{13}$ coatings increased by 70, 73, and $84\\%$ , respectively, demonstrating that the water droplets spread fast on the coating surfaces containing the POSS-related copolymers and dispersed well into the coatings. Moreover, the higher the polymer molecular weight, the faster the water droplet spread. Among the block copolymers, $\\mathrm{C-POSS-D}_{90}–b–\\ensuremath{\\mathrm{S}}_{13}$ with the highest molecular weight $(2.02\\times10^{4})$ exhibited the fastest water absorption process, whereas the SIPN coatings containing $\\mathrm{POSS-D}_{50^{-}}b{\\cdot}S_{7}$ (with a molecular weight of $0.97\\times$ $10^{4})$ and $\\mathrm{POSS-D}_{70^{-}}b{\\cdot}{\\ensuremath{\\mathrm{S}}}_{10}$ (with a molecular weight of $1.43\\times$ $10^{4^{\\cdot}}$ ) demonstrated similar water-dispersion speeds. Thus, the enhanced antifogging property could be caused by the strong hydrophilic blocks embedded in the cross-linked PEGDMA network and the hydrophobic POSS groups on the coating surfaces.  \n\nAnti-Icing Properties. The freezing delay time of water droplets on the SIPN coatings was recorded at $-15~^{\\circ}\\mathrm{C}$ to evaluate the anti-icing properties. As shown in Figure 5, it can be observed that the SIPN coating containing $\\mathrm{D}_{50}–b–S_{7}$ showed a short freezing delay time of $^{10\\ s,}$ that is, the water droplet became ice as quickly as it did on the bare glass. In contrast, all of the three coatings containing the POSS-PDMAEMA- $b$ - PSBMA block copolymers presented a freezing delay time of more than $^{124\\ s,}$ much longer than that of the $\\mathrm{C-D}_{50}{\\cdot}b{\\cdot}S_{7}$ coating without POSS. Particularly, the C-POSS- $\\mathrm{\\cdotD}_{50}{\\cdot}b{\\cdot}S_{7}$ coating exhibited a longer freezing delay time of 334 s compared with $\\mathrm{C}\\mathrm{-POSS}\\mathrm{-}\\bar{\\mathrm{D}}_{70}\\mathrm{-}b\\mathrm{-}\\mathrm{S}_{10}$ and $\\mathrm{C-POSS-D}_{90}–b–\\ensuremath{\\mathrm{S}}_{13}$ with similar freezing delay times of about $124\\ \\mathbf{s}.$ . This phenomenon could be attributed to the following reasons. First, the POSS groups with a low surface free energy have the ability of improving the surface icephobicity as shown in POSScontaining methacrylate coatings.24,25,39 Second, a certain amount of water molecules could be interacted with the hydrophilic PDMAEMA- $\\cdot b$ -PSBMA copolymers inside the cross-linked coatings as nonfreezable bond water through hydrogen bonds,8−10,28 a nd the freezing point of water could be decreased by the zwitterionic groups of PSBMA in the coatings.21 Finally, the POSS-PDMAEMA-b-PSBMA coating surfaces, which comprised the hydrophobic POSS groups on the coating surfaces and hydrophilic components in the SIPN coatings, could motivate the formation of a self-lubricating aqueous layer11,13,14 and subsequently endow the coatings with the anti-icing properties. In other words, the POSS clusters on the $\\mathrm{C}{\\cdot}\\mathrm{POSS}{\\cdot}\\mathrm{D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ coating surface could give rise to a hydrophobic surface, whereas the hygroscopic PDMAEMA and PSBMA chains were well distributed beneath them. And then, a self-lubricating aqueous layer could form when the coating absorbed water molecules.13,16 The surface structure of the coating is similar to the self-lubricating water layer fabricated by cross-linked hygroscopic polymers inside the micropores of silicon wafer surfaces, as put forward by Chen et al.13 However, the hydrophilic $\\mathrm{C-D}_{50}{\\cdot}b{\\cdot}S_{7}$ coating surface without hydrophobic components could be a reservoir of water molecules rather than a self-lubricating aqueous layer.13,16  \n\nIn fact, there were water molecules in the amphiphilic coating surfaces to maintain the presence of the self-lubricating aqueous layer.11,13 The results of the freezing delay time for each sample exhibited a trend of decrease with the increase of the molecular weight of the copolymers. When the molecular weight of the copolymers was lower than a certain value, the total content of POSS aggregated on the coating surface would be higher, whereas the relative proportion of the hydrophilic components would drop. The freezing process of a water droplet on the bare glass and the hydrophilic $\\mathrm{C-D}_{50}{\\cdot}b{\\cdot}S_{7}$ coating without POSS presented much shorter delay times in about $10\\ s,$ very similar to the case of the general polyacrylate coating.40 With the contribution of POSS, the $\\mathrm{\\bar{C}-P O S S-D_{50}}–b–S_{7},$ $\\bar{\\mathrm{C}}{\\cdot}\\mathrm{POSS}{\\cdot}\\mathrm{D}_{70}{-}b$ - $S_{10},$ and $\\mathrm{C-POSS-D}_{90}–b–\\ensuremath{\\mathrm{S}}_{13}$ coatings exhibited freezing delay times of more than $2~\\mathrm{min}$ . It could be suggested that the POSS groups played an important role in regulating and controlling superior hydrophobic/hydrophilic balance of the coating surface to form a self-lubricating aqueous layer with an antiicing performance. Therefore, $\\mathrm{C}\\mathrm{-}\\mathrm{POSS-}\\mathrm{D}_{50}\\mathrm{-}b\\mathrm{-}\\mathrm{S}_{7}$ coating, which has the lowest content of hydrophilic units, exhibited the longest freezing delay time, whereas $\\mathrm{C-D}_{50}{\\cdot}b{\\cdot}S_{7}$ could only prevent water from freezing in a short time.  \n\nNonfreezable Bond Water Amount in the SIPN Coatings. To further understand the antifogging/anti-icing properties of the SIPN coatings, the amounts of bond water, nonfreezable bond water, and freezable water in the coatings were analyzed by DSC. Figure 6 shows the DSC thermograms of the samples with the similar water content $\\left(W_{\\mathrm{c}}\\approx1.22\\right)$ in the heating process at a rate of $10~{^\\circ}\\mathrm{C}/\\mathrm{min},$ , whereas the results of sample $\\mathrm{\\bar{C}-P O S S-D_{90}}–b–S_{13}$ with different water contents and the pure deionized water were also included. It can be seen that most of the melting peaks in the heating scans of the samples could be fitted into two peaks, a smaller one at around $-20$ to $-17\\ ^{\\circ}\\mathrm{C}$ and a sharp one at $^{-8}$ to $0~^{\\circ}\\mathrm{C}$ close to the melting point of pure deionized water. The smaller and the sharp peaks could correspond to the melting enthalpies of freezable bond water $(W_{\\mathrm{fb}})$ and freezable free water $(W_{\\mathrm{ff}})$ , respectively, depending on the different endothermic states in the melting process.29,30 By quantitatively comparing the water contents in different states, we could verify the existence of the nonfreezable bond water in the SIPN coatings.29−33  \n\nTable 3 summarizes the water contents in different states determined by DSC. In the $\\mathrm{C-POSS-D}_{50}–b–S_{7},$ $\\mathrm{C-POSS-D}_{70}–b.$ $S_{10},$ $\\mathrm{C-POSS-D}_{90^{-}}b{\\cdot}\\mathrm{S}_{13},$ and $\\mathrm{C-D}_{50}{\\cdot}b{\\cdot}S_{7}$ coating/water binary systems, when total water content $W_{\\mathrm{c}}\\approx1.22,$ the measured nonfreezable bond water contents $(W_{\\mathrm{nfb}})$ were 0.45, 0.43, 0.45, and $0.52\\mathrm{\\mg/mg},$ respectively, showing similar nonfreezable bond water contents in all of the SIPN coatings. In addition, the total bond water contents exhibited similar results of about $0.59{-}0.61~\\mathrm{mg/mg},$ indicating that all of the SIPN coatings with or without POSS may have a similar situation of polymer− water interactions at a molecular level via hydrogen bonds.28−33  \n\n![](images/dbb77df5391c9420340e8d55dace8e47fd83176aac0b584ad69baae2a316d183.jpg)  \nFigure 6. DSC heating curves of the SIPN coatings with a total water content $(W_{c})$ of approximately 1.22, and the sample $\\mathrm{C-POSS-D}_{90}–b.$ - $S_{13}$ with different water contents at a heating rate of $10~{^\\circ}\\mathrm{C}/\\operatorname*{min}$ . The DSC heating scan of pure deionized water was also added as a control.  \n\nIn addition, the DSC heating curves of $\\mathrm{C\\mathrm{-}\\bar{P}O S S\\mathrm{-}D_{90}\\mathrm{-}}b\\mathrm{-}\\mathrm{S_{13}}$ with different water contents are specially shown in Figure 6. We selected four $W_{\\mathrm{c}}$ values, 1.22, 0.83, 0.53, and $0.26~\\mathrm{mg/mg},$ for comparison. It can be seen that as the water content decreased, the melting points of the free water as well as all the contents of water in different states tended to reduce (Table 3). It was noticed that when $W_{\\mathrm{c}}=0.26$ , only one melting peak was detectable in the DSC heating curve, and it was difficult to distinguish the different states of water in this case. It was assumed that the smaller amount of water in the sample could possibly appear only in the state of freezable water because the melting peak was close to the melting peak $T_{\\mathrm{ffm}}$ values of $^{-7}$ to $-3~^{\\circ}\\mathrm{C}$ of other samples and higher than the $T_{\\mathrm{fbm}}$ values of about $^{-17}$ to $-14~^{\\circ}\\bar{\\mathrm{C}}$ (Table 3).  \n\nA sufficient amount of the nonfreezable bond water in the SIPN coatings played an important role for the excellent antifogging/anti-icing properties. In fact, the nonfreezable bond water formed by the polymer−water interactions via hydrogen bonds may vary with hydrophilic polar groups and hydrophobic nonpolar groups.41 Therefore, the similar nonfreezable bond water contents in all of the SIPN coatings was dominated by the polymeric structure, especially the hydrophilic components. In fact, the $\\mathrm{C-POSS-D}_{50}–b–S_{7},$ $\\mathrm{C-POSS-D}_{70}–b–S_{10},$ $\\mathrm{C-POSS–D}_{90}\\mathrm{.}$ $b{-}S_{13},$ and $\\mathrm{C-D}_{50}{\\cdot}b{\\cdot}S_{7}$ coatings exhibited quite close nonfreezable bond water contents even when detected at different heating rates of 5, 10, or $15~{^\\circ}\\mathrm{C}/\\mathrm{min},$ as shown in Table S1. The different heating rates exerted no significant influence on the nonfreezable bond water contents, suggesting well absorption of water in all of the SIPN coatings with or without POSS. Containing similar nonfreezable water contents, the SIPN coating with or without POSS demonstrated different antifogging/anti-icing properties, further confirming the important role of POSS on the coating surface.  \n\nThe SIPN coatings, which contained POSS-PDMAEMA-bPSBMA and comprised both low surface energy and hydrophilic blocks, endowed the surfaces with the optimum antifogging/anti-icing performances. As illustrated in Figure 7, hydrophobic POSS clusters that aggregated on the coating surfaces featured the amphiphilic surface of the SIPN coatings containing POSS-PDMAEMA- $b$ -PSBMA block copolymers. The hygroscopic polymeric components of the coatings manipulated water molecules to disperse well into the hydrophilic matrix via hydrogen-bonded interactions. On the basis of the POSS clusters and the self-lubricating aqueous layer formed by the nonfreezable bond water on the surface, the amphiphilic SIPN coating containing POSS-PDMAEMA-bPSBMA block copolymers exhibited excellent antifogging/antiicing performances over the hydrophilic SIPN coating without POSS.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# CONCLUSIONS  \n\nIn this work, we developed an amphiphilic SIPN coating containing block copolymers of POSS-PDMAEMA- $b$ -PSBMA with a cross-linked PEGDMA network. The obtained SIPN coatings that comprised both low surface energy and hydrophilic components endowed the coatings with optimal antifogging/anti-icing performances. The excellent antifogging properties were originated primarily from the hygroscopicity of PDMAEMA and PSBMA blocks embedded in the cross-linked  \n\nTable 3. Different Water Contents in the SIPN Coatings Analyzed by DSC   \n\n\n<html><body><table><tr><td colspan=\"2\"></td><td colspan=\"5\">freezable water</td><td colspan=\"2\"></td></tr><tr><td></td><td>W.</td><td>Wf</td><td colspan=\"2\">freezable bond water</td><td colspan=\"2\">freezable free water</td><td rowspan=\"2\">non-freezable bond water Wnfb</td><td rowspan=\"2\"> bond water Wb</td></tr><tr><td> sample</td><td>(mg/mg)</td><td>(mg/mg)</td><td>Wb (mg/mg)</td><td>Trom (°C)</td><td>Wff (mg/mg)</td><td>Ttfm (°)</td></tr><tr><td>C-POSS-D50-b-S7</td><td>1.21</td><td>0.76</td><td>0.14</td><td>-4.01</td><td>0.62</td><td>-1.30</td><td>(mg/mg) 0.45</td><td>(mg/mg) 0.59</td></tr><tr><td>C-POSS-D7o-b-S10</td><td>1.20</td><td>0.77</td><td>0.16</td><td>-17.42</td><td>0.61</td><td>-1.91</td><td>0.43</td><td>0.59</td></tr><tr><td>C-POSS-D90-b-S13</td><td>1.22</td><td>0.77</td><td>0.14</td><td>-15.01</td><td>0.63</td><td>-1.50</td><td>0.45</td><td>0.59</td></tr><tr><td rowspan=\"4\"></td><td>0.83</td><td>0.61</td><td>0.15</td><td>-16.14</td><td>0.46</td><td>-3.35</td><td>0.22</td><td>0.37</td></tr><tr><td>0.53</td><td>0.39</td><td>0.10</td><td>-16.79</td><td>0.29</td><td>-7.38</td><td>0.14</td><td>0.24</td></tr><tr><td>0.26</td><td>0.26</td><td></td><td></td><td>0.26</td><td>-8.76</td><td></td><td></td></tr><tr><td>1.24</td><td>0.72</td><td>0.09</td><td>-16.34</td><td>0.63</td><td>-2.13</td><td>0.52</td><td>0.61</td></tr></table></body></html>  \n\n![](images/40cfc0aedb00c713a850688445ad9aeb3d0feab02b8d184acece8ae329aa361e.jpg)  \nFigure 7. Illustration of amphiphilic SIPN coatings containing POSS-PDMAEMA- $\\cdot\\boldsymbol{b}$ -PSBMA (A) and PDMAEMA-b-PSBMA (B) with a cross-linked PEGDMA network. Hydrophobic POSS aggregated on the surface and strongly hydrophilic chains distributed beneath them endowed the amphiphilic SIPN coatings with excellent antifogging/anti-icing performances in comparison with the hydrophilic SIPN coating.  \n\nPEGDMA network, as well as the hydrophobic POSS aggregated on the surface. The amphiphilic SIPN coatings with POSS groups had excellent transparency due to rapid water absorption in the coatings. PDMAEMA with LCST and PSBMA with UCST facilitated the dispersion of water molecules to enhance the antifogging behaviors. In addition, a self-lubricating aqueous layer formed by nonfreezable bond water at the surface endowed the amphiphilic SIPN coatings with great anti-icing performance, which had a freezing delay time of more than $2\\ \\mathrm{min}$ . The amphiphilic antifogging/antiicing coatings combining POSS and PDMAEMA- $b$ -PSBMA would contribute to novel potential applications in the future, such as transparent substrates in airplanes and lenses in medical instruments.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 6,
+        "chunk": "# ASSOCIATED CONTENT",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# $\\otimes$ Supporting Information  \n\nThe Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.7b05286.  \n\nCharacterizations of the POSS-PDMAEMA- $b$ -PSBMA block copolymers by $^{1}\\mathrm{H}~\\mathrm{NMR},$ FTIR spectra, GPC, and TGA techniques, and the characterizations of the SIPN  \n\ncoatings by TEM and DSC. The thermal remediation pictures of the SIPN coating by a digital camera were also presented (PDF)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# AUTHOR INFORMATION  \n\nCorresponding Author   \n$^{*}\\mathrm{E}$ -mail: yuanxy@tju.edu.cn, xyuan28@yahoo.com. ORCID   \nXiaoyan Yuan: 0000-0002-2895-3730   \nNotes   \nThe authors declare no competing financial interest.",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nThis work is financially supported by National Natural Science Foundation of China (Nos. 51603143 and 51273146).",
+        "category": " References"
+    },
+    {
+        "id": 10,
+        "chunk": "# REFERENCES  \n\n(1) Di Mundo, R.; D’Agostino, R.; Palumbo, F. Long-Lasting Antifog Plasma Modification of Transparent Plastics. ACS Appl. Mater. Interfaces 2014, 6, 17059−17066.  \n\n(2) Wang, Y.; Li, T. Q.; Li, S. H.; Sun, J. $\\mathsf{Q}.$ Antifogging and FrostResisting Polyelectrolyte Coatings Capable of Healing Scratches and Restoring Transparency. Chem. Mater. 2015, 27, 8058−8065.   \n(3) Li, Y. X.; Fang, X.; Wang, Y.; Ma, B. H.; Sun, J. $\\mathsf{Q}.$ Highly Transparent and Water-Enabled Healable Antifogging and Frostresisting Films Based on Poly(vinyl alcohol)-Nafion Complexes. Chem. Mater. 2016, 28, 6975−6984.   \n(4) Lee, H.; Alcaraz, M. L.; Rubner, M. F.; Cohen, R. E. ZwitterWettability and Antifogging Coatings with Frost-Resisting Capabilities. ACS Nano 2013, 7, 2172−2183.   \n(5) Zhang, J. L.; Severtson, S. J. Fabrication and Use of Artificial Superhydrophilic Surfaces. J. Adhes. Sci. Technol. 2014, 28, 751−768. (6) Lai, Y. K.; Tang, Y. X.; Gong, J. 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J.; Hatton, B. D.; Grinthal, A.; Aizenberg, J. Bioinspired Self-Repairing Slippery Surfaces with Pressure-Stable Omniphobicity. Nature 2011, 477, 443− 447.   \n(16) Ozbay, S.; Yuceel, C.; Erbil, H. Y. Improved Icephobic Properties on Surfaces with a Hydrophilic Lubricating Liquid. ACS Appl. Mater. Interfaces 2015, 7, 22067−22077.   \n(17) Yao, X.; Dunn, S. S.; Kim, P.; Duffy, M.; Alvarenga, J.; Aizenberg, J. Fluorogel Elastomers with Tunable Transparency, Elasticity, Shape-Memory, and Antifouling Properties. Angew. Chem., Int. Ed. 2014, 53, 4418−4422.   \n(18) Dong, Z. X.; Mao, J.; Wang, D. P.; Yang, M. $\\mathrm{Q.;}$ Wang, W. C.; Bo, S. $\\mathrm{Q.;}$ Ji, X. L. Tunable Dual-Thermoresponsive Phase Behavior of Zwitterionic Polysulfobetaine Copolymers Containing Poly(N,Ndimethylaminoethylmethacrylate)-Grafted Silica Nanoparticles in Aqueous Solution. Macromol. Chem. Phys. 2014, 215, 111−120. (19) Zhang, H.; Tong, X.; Zhao, Y. Diverse Thermoresponsive Behaviors of Uncharged UCST Block Copolymer Micelles in Physiological Medium. Langmuir 2014, 30, 11433−11441.   \n(20) Sun, H.; Chen, X. L.; Han, X.; Liu, H. L. Dual Thermoresponsive Aggregation of Schizophrenic PDMAEMA-bPSBMA Copolymer with an Unrepeatable pH Response and a Recycled $\\mathrm{CO}_{2}/\\mathrm{N}_{2}$ Response. Langmuir 2017, 33, 2646−2654. (21) Chernyy, S.; Järn, M.; Shimizu, K.; Swerin, A.; Pedersen, S. U.; Daasbjerg, $\\operatorname{K}.$ ; Makkonen, L.; Claesson, P.; Iruthayaraj, J. Superhydrophilic Polyelectrolyte Brush Layers with Imparted Anti-Icing Properties: Effect of Counter Ions. ACS Appl. Mater. Interfaces 2014, 6, 6487−6496.   \n(22) He, Z.; Xie, W. J.; Liu, Z. $\\mathrm{Q.;}$ Liu, G. M.; Wang, Z. W.; Gao, Y. $\\mathrm{Q.;}$ Wang, J. J. Tuning Ice Nucleation with Counterions on Polyelectrolyte Brush Surfaces. Sci. Adv. 2016, 2, No. e1600345. (23) Liu, B.; Zhang, K. $\\mathrm{Q.;}$ Tao, C.; Zhao, Y. H.; Li, X. H.; Zhu, K. Y.; Yuan, X. Y. Strategies for Anti-Icing: Low Surface Energy or LiquidInfused? RSC Adv. 2016, 6, 70251−70260.   \n(24) Zhang, K. $\\mathrm{Q.;}$ Li, X. H.; Zhao, Y. H.; Zhu, K. Y.; Li, Y. C.; Tao, C.; Yuan, X. Y. UV-Curable POSS-Fluorinated Methacrylate Diblock Copolymers for Icephobic Coatings. Prog. Org. Coat. 2016, 93, 87−96. (25) Li, X. H.; Zhang, K. $\\mathrm{Q.;}$ Zhao, Y. H.; Zhu, K. Y.; Yuan, X. Y. Formation of Icephobic Film from POSS-Containing Fluorosilicone Multi-Block Methacrylate Copolymers. Prog. Org. Coat. 2015, 89, 150−159.   \n(26) Li, B.; Li, X. H.; Zhang, K. $\\mathrm{Q.;}$ Li, H.; Zhao, Y. H.; Ren, L. X.; Yuan, X. Y. Synthesis of POSS-Containing Fluorosilicone Block Copolymers via RAFT Polymerization for Application as Non-Wetting Coating Materials. Prog. Org. Coat. 2015, 78, 188−199.   \n(27) Ma, L.; Geng, H. P.; Song, J. X.; Li, J. Z.; Chen, G. X.; Li, Q. F. Hierarchical Self-Assembly of Polyhedral Oligomeric Silsesquioxane End-Capped Stimuli-Responsive Polymer: From Single Micelle to Complex Micelle. J. Phys. Chem. B 2011, 115, 10586−10591.   \n(28) Leng, C.; Hung, H. C.; Sieggreen, O. A.; Li, Y. T.; Jiang, S. Y.; Chen, Z. Probing the Surface Hydration of Nonfouling Zwitterionic and Poly(ethylene glycol) Materials with Isotopic Dilution Spectroscopy. J. Phys. Chem. C 2015, 119, 8775−8780.   \n(29) Weise, U.; Maloney, T.; Paulapuro, H. Quantification of Water in Different States of Interaction with Wood Pulp Fibres. Cellulose 1996, 3, 189−202.   \n(30) Nwaka, D.; Tahmasebi, A.; Tian, L.; Yu, J. The Effects of Pore Structure on the Behavior of Water in Lignite Coal and Activated Carbon. J. Colloid Interface Sci. 2016, 477, 138−147.   \n(31) Tahmasebi, A.; Yu, J. L.; Su, H. X.; Han, Y. N.; Lucas, J.; Zheng, H. L.; Wall, T. A Differential Scanning Calorimetric (DSC) Study on the Characteristics and Behavior of Water in Low-Rank Coals. Fuel 2014, 135, 243−252.   \n(32) Nakano, T.; Nakaoki, T. Coagulation Size of Freezable Water in Poly(vinyl alcohol) Hydrogels Formed by Different Freeze/Thaw Cycle Periods. Polym. J. 2011, 43, 875−880.   \n(33) Ostrowska-Czubenko, J.; Pieróg, M.; Gierszewska-Drużyńska, M. Water State in Chemically and Physically Crosslinked Chitosan Membranes. J. Appl. Polym. Sci. 2013, 130, 1707−1715.   \n(34) Zhao, J.; Meyer, A.; Ma, L.; Wang, J.; Ming, W. TerpolymerBased SIPN Coating with Excellent Antifogging and Frost-Resisting Properties. RSC. Adv. 2015, 5, 102560−102566.   \n(35) Leng, C.; Hung, H. C.; Sun, S. W.; Wang, D. Y.; Li, Y. T.; Jiang, S. Y.; Chen, Z. Probing the Surface Hydration of Nonfouling Zwitterionic and PEG Materials in Contact with Proteins. ACS Appl. Mater. Interfaces 2015, 7, 16881−16888.   \n(36) Zhang, X.; He, J. H. Hydrogen-Bonding-Supported Self-Healing Antifogging Thin Films. Sci. Rep. 2015, 5, No. 9227.   \n(37) Ullah, A.; Ullah, S.; Khan, G. S.; Shah, G. M.; Hussain, Z.; Muhammad, S.; Siddiq, M.; Hussain, H. Water Soluble Polyhedral Oligomeric Silsesquioxane Based Amphiphilic Hybrid Polymers: Synthesis, Self-Assembly, and Applications. Eur. Polym. J. 2016, 75, 67−92.   \n(38) Zhang, X.; He, J. H. Antifogging Antireflective Thin Films: Does the Antifogging Layer Have to Be the Outmost Layer? Chem. Commun. 2015, 51, 12661−12664.   \n(39) Meuler, A. J.; Smith, J. D.; Varanasi, K. K.; Mabry, J. M.; McKinley, G. H.; Cohen, R. E. Relationships between Water Wettability and Ice Adhesion. ACS Appl. Mater. Interfaces 2010, 2, 3100−3110.  \n\n(40) Li, X. H.; Zhao, Y. H.; Li, H.; Yuan, X. Y. Preparation and Icephobic Properties of Polymethyltrifluoropropylsiloxane-Polyacrylate Block Copolymers. Appl. Surf. Sci. 2014, 316, 222−231. (41) Varma-Nair, M.; Costello, C. A.; Colle, K. S.; King, H. E. Thermal Analysis of Polymer-Water Interactions and Their Relation to Gas Hydrate Inhibition. J. Appl. Polym. Sci. 2007, 103, 2642−2653.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Transparent and Scratch-Resistant Antifogging Coatings with Rapid Self-Healing Capability  \n\nBang Liang,†,‡ Zhenxing Zhong,†,‡ Erna Jia,†,‡ Guangyu Zhang,\\*,† and Zhaohui Su\\*,†,‡  \n\n†State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences,   \nChangchun 130022, P. R. China   \n‡University of Science and Technology of China, Hefei 230026, P. R. China  \n\nSupporting Information  \n\nABSTRACT: Typical antifogging coatings based on hydrophilic polymers are soft and susceptible to mechanical damage. In this paper, an antifogging coating that is both scratch-resistant and self-healing is fabricated by copolymerizing sulfobetaine methacrylate and 2-hydroxyethyl methacrylate in the presence of sulfobetaine-modified silica nanoparticles in one pot. The coating is highly efficient in preventing fog formation at the surface and reducing ice adhesion, and is resistant to fouling by oil and protein, due to the strong hydration ability of the zwitterionic moieties. The composite coating is resistant to scratching and abrasion under normal use conditions to maintain its transparency due to increased hardness by the filled silica nanoparticles and is able to heal completely within several minutes severe scratches and cuts inflicted in harsh conditions, owing to the water-assisted reversibility of the electrostatic and hydrogen-bonding interactions holding together the polymer components and the silica nanoparticles. The multiple desirable properties demonstrated and the simple fabrication process of the coating offers great potential in many practical applications.  \n\n![](images/2a59ca55dbd822574baf7a88aea773d2f4ea44fd0073dade61157a9bcdb52f86.jpg)  \n\nKEYWORDS: antifogging, transparent, scratch-resistant, self-healing, antifouling",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# INTRODUCTION  \n\nFogging on transparent substrates such as automobile windshields, eyeglasses, and medical/analytical instrument lenses results in significant scattering of visible light and thus reduces light transmission through the substrates, which can cause inconvenience and even adverse consequences in practical applications.1−5 Over the past decade, extensive research has been carried out in order to prevent fogging on the substrates. Among the various approaches reported, one effective strategy is constructing a thin hydrophilic polymer coating on the surface of the transparent substrate, for example poly(ethylene glycol) (PEG),3 acrylic polymers,6 and polymeric quaternary ammonium salts,7 which can effectively prevent fog formation by spreading the condensed water droplets into a thin continuous water film. However, these hydrophilic polymer-based antifogging coatings are soft and susceptible to mechanical damage such as scratching and abrasion, leading to deteriorating transparency and antifogging properties.8 In order to solve this problem, research effort has been focused on endowing the polymeric coating with selfrepairing character, so that the coating can recover its transparency and hydrophilicity after being damaged.8−11 Self-healing materials can recover damaged structure and functions autonomously with external stimuli.12,13 While extrinsic self-healing materials require an embedded external healing component for repair, intrinsic self-healing materials interactions14−17 or dynamic covalent bonds,18−21 providing a can repair the damage via inherent reversible noncovalent practical and convenient avenue to construct thin films with self-healing ability. Recently, self-healing polymeric antifogging coatings have been reported by several groups. For instance, Sun et al. demonstrated that antifogging films based on thick polyelectrolyte multilayer (PEM) assembly10,11 and homogeneous hydrophilic polymeric complexes8 can quickly heal cuts and scratches autonomously in the presence of water. Hozumi et al. prepared antifogging coatings from simple mixtures of polyvinylpyrrolidone and aminopropyl-functionalized nanoclay platelets, and showed that they can heal cuts readily by absorbing water from humid air.9 However, these materials usually are composed of soft building blocks held together by relatively weak interactions in order to achieve high mobility to facilitate the healing process, and as a result self-healing coatings tend to be soft and lack mechanical robustness and long-term durability.22,23 It is well known that inorganic nanofillers can effectively enhance the mechanical strength of polymer material, and this idea has been adopted to improve the scratch-resistance of polymer films.24−26 Recently, Sun et al. introduced $\\mathbf{CaCO}_{3}$ nanoparticles into PEM film assembled from poly(acrylic acid) and poly(ethylenimine) and demonstrated that the nanoparticles can render the healable film more robust and scratch-resistant.27 Despite the progress, fabrication of coatings with good scratch-resistant and self-healing properties is still a challenging task because the dynamic healing based on weak interactions is compromised when strong interactions are introduced to enhance the hardness necessary for scratch-resistance,23,28,29 and in particular, development of a robust antifogging coating remains to be explored. In addition, antifogging coatings in general are high in surface energy and therefore are susceptible to contamination and loss of their antifogging property. Consequently, antifouling property must be considered in the design and fabrication of next-generation antifogging coatings.3 .30  \n\n![](images/4945a2d9a30177b8c3db405e59700911acf1ca69052f3d89516a9561410ec8eb.jpg)  \nFigure 1. Schematic illustration of the scratch-resistant and self-healing composite coating.  \n\n![](images/fe4727fe5d77264a473167460cb2ae7f9f6a6857159c3db8bd9f4d15fafafce4.jpg)  \nFigure 2. $(\\mathsf{a},\\mathsf{b})$ TEM images of $\\mathrm{\\p(SBMA_{7}\\mathrm{-co-HEMA_{3}},}$ ) filled with $5.0\\mathrm{wt}\\%$ (a) plain and (b) modified silica nanoparticles, respectively. (c) UV−vis spectra of the $\\mathrm{\\p(SBMA_{7}\\mathrm{-}c o\\mathrm{-}H E M A_{3})}$ ) coatings filled with silica nanoparticles. (d) FTIR spectra of $\\mathsf{p}(\\mathsf{S B M A}_{7}\\mathsf{-c o-H E M A}_{3})$ with and without modified silica nanoparticles in comparison with that of $\\mathrm{{\\ttpSBMA}}.$  \n\n![](images/cb6fff18c6761bafa6240c2cc5ba403e564c5a7fabacdca12bac4f6ed99735e5.jpg)  \nFigure 3. (a) Antifogging performance of a $\\mathsf{p}(\\mathrm{SBMA}_{7^{-}}\\mathrm{co}\\mathrm{-}\\mathrm{HEMA}_{3})$ ) coating filled with $5.0\\mathrm{\\mt\\\\%}$ silica nanoparticles. (b) FTIR spectra of the coating as prepared and after the antifogging test. (c) Time profiles (three independent tests) of ice adhesion strength on a coated glass. (d) Average ice adhesion strength on a coated glass compared with that on a bare glass.  \n\nIn this work, we report a self-healing antifogging coating based on polyzwitterion copolymer reinforced by silica nanoparticles. The composite is easily prepared in one pot, and by varying the co-monomer ratio we can readily tune the interactions among the polymer components and the silica nanoparticles, producing a coating that can both resist typical scratching and abrasion to maintain its transparency, and quickly repair severe damages inflicted in harsh conditions. The transparent coating is highly efficient in preventing fogging and reducing ice adhesion and is resistant to fouling by oil and protein.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# RESULTS AND DISCUSSION  \n\nThe simple coating fabrication process is schematically illustrated in Figure 1. The coating was synthesized by free radical solution polymerization. Silica nanoparticles were added to increase the hardness of the transparent coating. However, when plain silica particles were used directly, the nanoparticles aggregated in the polymer matrix, resulting in significant scattering and reduction of optical transparency (Figure 2c). To improve the dispersion of silica nanoparticles in the aqueous system, their surfaces were first modified with a hydrophilic silane coupling agent carrying a sulfobetaine group (SI, Figure S1).31 The sulfobetaine groups introduced to the surface can increase the hydrophilicity of the nanoparticles and reduce their aggregation via the stable water layer around the surface.31 The modified silica nanoparticles were well dispersed in an aqueous solution of the hydrophilic monomers, sulfobetaine methacrylate (SBMA) and 2-hydroxyethyl methacrylate (HEMA) with a 7:3 mole ratio, and the polymerization was carried out at $25^{\\circ}\\mathrm{C}$ for $20\\mathrm{min}$ to obtain a viscosity suitable for spin-coating, and the mixture was then spin-coated on the substrate and cured by heating at $80~^{\\circ}\\mathrm{C}$ for $^{2\\mathrm{~h~}}$ to complete the polymerization to produce a clear coating (coded $\\mathsf{p}(\\mathsf{S B M A}_{7^{-}}\\mathsf{c o}{\\mathrm{-}}\\mathrm{HEMA}_{3})$ herein). Figure 2b displays transmission electron microscopic (TEM) images of the coating filled with silica nanoparticles (5.0 wt $\\%$ relative to the polymer), which show uniform distribution of the modified nanoparticles in the polymer matrix, in contrast to the severe aggregation observed for the plain silica nanoparticles. Apparently, the sulfobetaine moieties grafted to the silica nanoparticles have significantly improved their compatibility with the matrix via the electrostatic and dipole interactions with the same sulfobetaine groups of the polymer.32,33 As seen in Figure 2c, a glass slide with a $\\mathsf{p}(\\mathrm{SBMA}_{7}\\mathrm{-co-HEMA}_{3})$ composite coating of ${\\sim}3.8\\ \\mu\\mathrm{m}$ thickness (SI, Figure S2) containing 5.0 wt $\\%$ silica nanoparticles exhibits $\\sim90\\%$ transmittance in the entire visible region, almost identical to that of the uncoated one, showing excellent transparency of the coating.  \n\nFigure 2d shows FTIR spectrum of the composite coating, which exhibits absorption peaks at ${\\sim}1710$ and ${\\sim}1480~\\mathrm{cm}^{-1}$ corresponding to the $\\scriptstyle{\\mathrm{C}}={\\mathrm{O}}$ stretching and the $\\mathrm{CH}_{3}$ bending of the SBMA unit, respectively.34 More interestingly, the strong ${S0}_{3}^{-}$ stretching peak, observed at ${\\sim}1034~\\mathrm{cm}^{-1}$ for SBMA homopolymer $(\\mathrm{pSBMA}),^{35}$ is found to shift to a lower frequency of ${\\sim}1028~\\mathrm{cm}^{-1}$ for the copolymer composite. This shift is ascribed to hydrogen-bonding interactions between the sulfonate group in the sulfobetaine unit and the hydroxyl group in the HEMA unit.34 This provides evidence of additional interactions besides the electrostatic and dipole interactions among the polymeric components and the modified silica nanoparticles, as schematically illustrated in Figure 1, which help stabilize the dispersion of the nanoparticles in the system25,27 and facilitate the self-healing of the film, as we will discuss later.  \n\n![](images/df2c341f00e1c56cb10e712f29841e78843c7d76a4169514113d0acbaf930c14.jpg)  \nFigure 4. (a) Photograph of a $\\begin{array}{r l}{\\lefteqn{\\operatorname{p}\\big(\\mathrm{SBMA}_{7^{-}}\\mathrm{co}{\\mathrm{-}}\\mathrm{HEMA}_{3}\\big)}\\quad}&{{}}\\end{array}$ coating filled with 5.0 wt $\\%$ modified silica nanoparticles (right) and an unfilled one (left) after 500 abrasion cycles, and (b) UV−vis spectra of the two coatings before and after the abrasion test.  \n\nTo investigate the adhesion between the coating and the substrate, a cross-tape test was conducted according to the ASTM D3359 standard.36 No detachment of the coating or debris was observed under optical microscope (SI, Figure S4), which indicates a highest level of adhesion (5B) between the coating and the substrate by the ASTM standard, attributed to the stable covalent bonds between the coating and the substrate, as well as good mechanical integrity and strength of the coating due to its strengthened cross-linking network structure. These structural characteristics also endow the superhydrophilic coating with excellent stability and adhesion to the substrate in aqueous environment (SI, Figure S4).  \n\nNext, the antifogging property of the composite coating was examined. Two glass slides, one bare and the other coated, were first stored in a freezer at $-20{}^{\\circ}\\mathrm{C}$ and then exposed to the atmosphere at room temperature. As shown in Figure 3a, the bare glass fogged in a few seconds, and the alphabets behind the glass were blurred due to the scattering of light by the water droplets condensed on the glass, whereas the coated glass remained clear, and the alphabets behind the glass were highly visible, confirming the excellent antifogging property of the coating. Figure 3b compares FTIR spectra of a composite coating recorded before and after the antifogging test, respectively. The broad OH stretching band at ${\\sim}3450~\\mathrm{cm^{-1}}$ increases dramatically, and the OH bending at $\\sim1640~\\mathrm{cm^{-1}}$ also becomes more intense, suggesting the absorption of a large amount of water by the coating. By gravimetric analysis, the mass increase of the coating was found to be ${\\sim}40\\%$ . As a reference, the coating can absorb up to $\\sim160\\%$ water when immersed in water for $^{24\\ \\mathrm{h},}$ showing outstanding hydration ability of the polymer. Obviously, the polyzwitterion-based coating can quickly absorb water molecules from the environment to form a highly hydrated layer at the surface, making it superhydrophilic,37,38 and subsequently condensed water spreads completely on this surface and no droplets are formed. In fact, upon direct exposure to the spray produced by a humidifier for extended periods of time, the coating was found to suppress fog formation and exhibit the same optical transparency (SI, Figure S5). Moreover, water molecules absorbed from the atmosphere by the polyzwitterion-based coating largely exist as bound water, which maintains a liquidlike state even at low temperatures and can act as a selflubricating interfacial layer to reduce ice adhesion.39 Figure 3c presents typical profiles of ice adhesion strength versus time, which shows that the ice adhesion strength increases quickly to a maximum value and then abruptly drops to zero when the ice is detached from the surface. The maximum value of the curve is defined as the ice adhesion strength according to the characteristic of cohesive breakage.39−41 As shown in Figure 3d, the coated glass exhibits a much lower ice adhesion strength of $62~\\mathrm{KPa}$ as compared with that for bare glass (245 KPa) (SI, Figure S6), indicating that the coating is an excellent material for anti-icing application as well.42  \n\nScratch-resistance is an important property for coatings, especially for the ones for optical applications. The hardness of the coatings prepared with various silica nanoparticle contents were assessed by a pencil hardness test on the basis of the ASTM D3363 standard,43 using pencils ranging from 6B (the softest) to 6H (the hardest) (SI, Figure S7). The unfilled $\\mathsf{p}(\\mathsf{S B M A}_{7^{-}}\\mathsf{c o}\\mathrm{-HEMA}_{3})$ coating was rather soft, with a pencil hardness of HB, whereas the ones reinforced with 2.5 and 5.0 wt $\\%$ silica exhibited significantly enhanced hardness of 2H and 4H, respectively. The latter was chosen for a further scratchresistance experiment, where the coatings were subjected to repeated abrasion using a cylindrical metal (with a weight of $_{500\\mathrm{~g)}}$ whose bottom was covered with a piece of ramie cloth,25,27 and the results are presented in Figure 4a. After 500 abrasion cycles, the unfilled $\\mathrm{p}(\\mathrm{SBMA}_{7^{-}}\\mathrm{co}{\\cdot}\\mathrm{HEMA}_{3})$ coating was heavily damaged, with numerous grooves clearly observed at the surface, and the optical transparency of the coating as measured by UV−vis spectroscopy was greatly reduced, with the transmittance at $550~\\mathrm{nm}$ decreasing from ${\\sim}90\\%$ to $60\\%$ . Meanwhile, after the same treatment, no visible scratches were identified on the surface of the coating containing 5.0 wt $\\%$ modified silica nanoparticles, and the transparency remained the same before and after the test, with a transmittance of $\\sim90\\%$ at $550~\\mathrm{nm}$ (Figure 4b). These two experiments clearly demonstrate that the modified silica nanoparticles added to the polyzwitterion coating can significantly enhance its hardness without compromising the optical transparency, and endow the coating with scratch-resistance ability that is adequate for handling mild abrasions in daily application settings.  \n\nNevertheless, the coating in use may accidentally be damaged by some harder objects, and the scratches inflicted would strongly reduce the transparency of the coating. This issue can be resolved if the coating can repair the damages autonomously to recover its original properties. To simulate use under harsh conditions, the $\\mathsf{p}\\big(\\mathrm{SBMA}_{7}\\mathrm{-co-HEMA}_{3}\\big)$ composite coating (with 5.0 wt $\\%$ silica) was rubbed repeatedly with a piece of 2000-grit sandpaper. Numerous shallow grooves appeared on the scratched coating, and the alphabets behind the coated glass became unclear, and the transmittance at $550~\\mathrm{nm}$ decreased from $90\\%$ to $70\\%$ . Then, the coating was dipped into deionized water for mere 2 s and quickly removed.  \n\n![](images/10dbdc023eb10187a0b5c3212d60fee76dcd00c5c58d1a7ac5176d325f1a71e9.jpg)  \nFigure 5. (a) Optical microscopic images (left) and photographs (right) of the $\\begin{array}{r}{\\mathrm{p}(\\mathrm{SBMA}_{7^{-}}\\mathrm{co}{\\mathrm{-}}\\mathrm{HEMA}_{3})}\\end{array}$ ) coating filled with 5.0 wt $\\%$ silica before (top) and after healing (bottom). (b) UV−vis spectra of the composite coating as-prepared, scratched, and healed. (c) Photographs (left) and optical microscopic images (right) of the damaged (top) and healed coating (bottom) (scale bars: $50\\mu\\mathrm{m}\\mathrm{,}$ ). (d) Healing of coatings of copolymers with 0, 15, and 30 mol $\\%$ HEMA, respectively (from left to right; scale bars: $50~\\mu\\mathrm{m}\\mathrm{\\ddot{\\Omega}}$ ).  \n\nWithin $2\\ \\mathrm{min}$ in lab environment at room temperature, the scratches on the coating surface completely disappeared, and the alphabets behind the coated glass became clear again, with the transmittance at $550~\\mathrm{nm}$ recovering to $90\\%$ , showing rapid self-healing ability of the coating assisted by water (Figure 5 a,b).  \n\nOccasionally severe damages can occur, so the healing ability of the coating under such circumstances was also investigated. A cut of ${\\sim}250~\\mu\\mathrm{m}$ width in the coating was made by a blade, exposing the underlying glass substrate. Again, the damaged film was dipped into deionized water for 2 s and then allowed to heal in lab environmentat room temperature, and within 6 min the scar disappeared completely and the transparency was recovered (Figure 5c). The cutting/healing cycle was repeated at the same location for 20 times (when the experiment was terminated), and the coating was found to completely recover its surface appearance, composition, and hardness at the damaged location after healing (SI, Figure S8). Considering that a film so thin $(3.8\\mu\\mathrm{m})$ can heal scars of a width more than 65 times of its thickness so quickly and so many times, its ability to repair large structural damages is truly amazing. In fact, thicker films can self-heal even faster (SI, Figure S9). For example, at $22.5~\\mu\\mathrm{m}$ thickness the coating can repair a cut of the same width within $2.5\\ \\mathrm{min}$ . This is because in thicker films, more polymer segments are available to relocate to the damaged section and to fill the void created by the damage.9,10,44 By the same token, thinner coatings are expected to heal more slowly and may not be able to repair large damages completely when the thickness is further reduced. But their antifogging and scratch-resistance properties should be the same, because the polyzwitterion film remains superhydrophilic at several tens of nanometer thickness,39 and the silica nanoparticles that render the coating scratch-resistant are only $30\\ \\mathrm{nm}$ in diameter.  \n\nIn order to explore the healing mechanism, the polyzwitterion coatings loaded with 5.0 wt $\\%$ silica nanoparticles and of the same thickness $(3.8~\\mu\\mathrm{m})$ but different HEMA contents were prepared, and subjected to the same cut-and-heal test. The cut in the pSBMA coating, which contained no HEMA units, recovered only partially after $^{10\\mathrm{~h~}}$ showing rather weak healability of the homopolymer. Replacing $15\\mathrm{\\mol\\}\\%$ of the SBMA units with HEMA, the $\\mathrm{\\Omega_{3}(S B M A_{8.5}–c o–H E M A_{1.5})}$ coating repaired the scar completely in $30~\\mathrm{\\min}$ . Further increasing the HEMA content to $30\\mathrm{\\mol\\\\%},$ , the $\\mathsf{p}(\\mathsf{S B M A}_{7}{\\mathsf{-c o-}}$ $\\begin{array}{r}{\\mathrm{HEMA}_{3}.}\\end{array}$ ) coating completely healed the damage in $6~\\mathrm{min},$ , as described above. Finally, a $\\mathsf{\\Omega}_{\\mathrm{p}}({\\mathrm{SBMA}}_{\\mathrm{7}}{\\mathrm{-co-HEMA}}_{3})$ coating containing no silica nanoparticles was found to heal its scar even slightly faster, in $\\textsf{S}_{\\operatorname*{min}}$ (Figure 5d). As illustrated in Figure 1, electrostatic interactions and hydrogen-bonding are the major forces holding together the linear polymer chains as well as the sulfobetaine-modified nanoparticles, which exhibit strong reversibility with the assistance of water, endowing the material with water-facilitated healing ability.34,44 Upon exposure to water, the damaged coating can absorb a large quantity of water molecules to weaken the electrostatic and the hydrogen-bonding interactions among its components to increase their mobility. Moreover, hydrogen-bonding interactions among the components are more susceptible to water disruption than electrostatic interactions.45 Therefore, the copolymer with a higher HEMA (the only hydrogen-bond donor in the system) content is weakened to a greater extent by water molecules absorbed, resulting in higher mobility of the components and hence improved healability of the coating. Then, in the healing process, the mobile polymer chains and the nanoparticles in the hydrated coating migrate to the damaged region due to the difference in chemical potential, where the electrostatic and hydrogen-bonding interactions reform, repairing the damages in the coating. Meanwhile, the optical transparency and antifogging performance of the coating was not affected by the copolymer composition (SI, Figure S10), because both SBMA and HEMA polymers are amorphous and hydrophilic. The hardness of the coating was not impacted either by the SBMA/HEMA ratio (SI, Table S1) since it mainly depends on the silica content. It should be pointed out that further increasing the HEMA content, although benefits the healability, can weaken the coating when immersed in water to such extent that the coating may fall apart.  \n\n![](images/2ef7d6cea1d7046a33796fd0d44482d2fd2a72b699ee9d5b6f9eb70f0c7ef6c1.jpg)  \nFigure 6. (a) Snapshots showing a soybean oil droplet sticks on bare glass (top) but is lifted on a glass coated with $\\mathsf{p}(\\mathrm{SBMA}_{7^{-}}\\mathrm{co}{\\mathrm{-}}\\mathrm{HEMA}_{3})$ with 5.0 wt $\\%$ modified silica (bottom) after immersion in water. (b) Mass of bovine serum albumin adsorbed on a bare Au electrode and a coated one.  \n\nFinally, the antifouling property of the coating was evaluated. In general, due to their high surface energy, hydrophilic surfaces are easily stained by the low surface energy contaminants, such as various oils and biological species.30 As seen in Figure 6a, soybean oil easily wet both bare glass slide and the $\\mathrm{p}(\\mathrm{SBMA_{7}{\\mathrm{-}}c o{\\mathrm{-}}H E M A_{3})}$ coating, contaminating the hydrophilic surfaces in a similar way. When the stained surfaces were placed in contact with water, however, the oil staining the $\\mathsf{p}(\\mathsf{S B M A}_{7^{-}}\\mathsf{c o}\\mathrm{-HEMA}_{3})$ coating was quickly lifted and removed completely from the surface, showing excellent antifouling performance by the coating, whereas the one on bare glass remained. This can be attributed to the strong waterbinding ability of the zwitterionic groups.46 In addition, the $\\mathrm{p}(\\mathrm{SBMA}_{7}\\mathrm{-co-HEMA}_{3})$ composite coating is resistant to biofouling. Protein adsorption on a coated substrate was found to be reduced by more than two thirds compared with that on a bare Au electrode (Figure 6b and Figure S11). The favorable protein resistance property of the coating is again due to the strong hydration ability of the zwitterionic groups, which can interact with water molecules and form a dense quasiliquid water layer, efficiently preventing protein adhesion to the surface.47,48 Furthermore, we found that the antifouling ability of the coating is lost when the coating is scratched extensively and can be readily recovered upon healing (SI, Figure S12), again demonstrating excellent healing ability of the coating.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# CONCLUSIONS  \n\nIn summary, we have demonstrated a robust and transparent antifogging coating based on a polyzwitterion copolymer reinforced by silica nanoparticles. The silica nanoparticles were modified with sulfobetaine moieties to not only improve dispersion of the nanoparticles in the hydrophilic polymer matrix, but also make them reversible cross-linking points. By tuning the electrostatic and hydrogen-bonding interactions among the polymer components and the silica nanoparticles, we obtained a coating that is able to resist scratching and abrasion under normal use conditions to maintain its transparency, as well as rapidly repair severe damages inflicted in harsh conditions to restore its functions. The transparent coating is highly efficient in preventing fogging at the surface and reducing ice adhesion, and is resistant to fouling by oil and protein, due to the strong hydration ability of the zwitterionic moieties. The coating material can be easily prepared in one pot and cast on the substrate with good adhesion, showing great potential in commercial application.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 5,
+        "chunk": "# EXPERIMENTAL SECTION  \n\nMaterials. Sulfobetaine methacrylate (SBMA), γ-methacryloxypropyl trimethoxysilane (MPSi), and 1,3-propane sultone were obtained from Energy Chemical Co., Ltd. Silica nanoparticles (average diameter of $30\\ \\mathrm{nm}$ ) were purchased from Xiya Chemical Reagents Company. (N,N-dimethyl-3-aminopropyl)trimethoxysilane (DMASi), ammonium persulfate, and 2-hydroxyethyl methacrylate (HEMA) were purchased from J&K Chemical Co., Ltd. Acetone, sodium phosphate, potassium dihydrogen phosphate, sodium chloride, potassium chloride, toluene, and sodium metasulfite were purchased from Beijing Chemical Reagents Company. Bovine serum albumin (BSA) was purchased from Shanghai Sangon Biotechnology Co., Ltd. Soybean oil was purchased from a local supermarket. Water used in all experiments was produced by a PGeneral GWA-UN4 purification system ( $18.2~\\mathrm{M}\\Omega{\\cdot}\\mathrm{cm}$ resistivity).  \n\nInstruments and Characterization. Film thickness was measured on the KLA-Tencor P-117/P-7 profiler. UV−vis spectra were acquired on a TU1901 spectrometer (Beijing Purkinje General Instrument Co., Ltd). FTIR spectra were recorded on a Nicolet 870 infrared spectrometer equipped with a smart ATR accessory with 256 scans at a resolution of $\\bar{2}\\mathrm{cm}^{-1}$ . Optical micrographs were obtained on a polarized optical microscope (Leica DLMP, GER). Morphology of nanoparticles in the coatings was observed on a TEM (Hitachi model H-900). Protein adsorption was analyzed using a quartz crystal microbalance with dissipation (QCM-D, E1, Q-Sense, Sweden) equipped with an AT-cut quartz crystal resonator.  \n\nSurface Modification of the Silica Nanoparticles. Silica nanoparticles were modified as described in the literature.31 First, 3- [dimethyl(3-(trimethoxysilyl)propyl)ammonio]propane-1-sulfonate (SBS) was synthesized. Briefly, DMASi $\\left(5.0\\ \\mathrm{g},24\\ \\mathrm{mmol}\\right)$ and 1,3- propane sultone $(3.0~\\mathrm{~g},~25~\\mathrm{~mmol})$ were dissolved in $25~\\mathrm{\\mL}$ of anhydrous acetone under nitrogen, and the mixture was stirred for 6 h. The white precipitate was collected and dried at room temperature with a yield of $90.5\\%$ . Silica nanoparticles $\\left(50\\mathrm{mg}\\right)$ were sonicated in 5 $\\mathrm{mL}$ of water for $30\\ \\mathrm{min}$ Then, $9.5~\\mathrm{mg}$ of SBS were added to the mixture, which was stirred constantly for $^{6\\mathrm{~h~}}$ at $80~^{\\circ}\\mathrm{C}.$ . Next, the mixture was centrifuged at ${5000}~\\mathrm{rpm}$ for $30~\\mathrm{min}$ and the centrifugate was collected and washed three times with deionized water to remove the physically adsorbed molecules. The final centrifugate was dried at $80~^{\\circ}\\mathrm{C}$ and stored under vacuum.  \n\nFabrication of the $\\mathsf{P}(\\mathsf{S B M A}_{7}\\mathsf{-c o-H E M A}_{3})$ Coating. The substrates were first cleaned with boiling piranha solution (7:3, $98\\%$ $\\mathrm{H}_{2}S\\mathrm{O}_{4}{:}30\\%\\ \\mathrm{H}_{2}\\mathrm{O}_{2})$ for $^\\mathrm{~1~h~}$ and then rinsed with water and dried under nitrogen. The freshly cleaned substrates were then immersed in an MPSi solution in anhydrous toluene $\\left(1{:}60,{\\bf v/v}\\right)$ at $80~^{\\circ}\\mathrm{C}$ for $^{2\\mathrm{~h,~}}$ rinsed with toluene to remove the physically adsorbed molecules and dried with a stream of nitrogen. Silica nanoparticles (2.5 or 5.0 wt $\\%$ relative to the total mass of SBMA and HEMA) were sonicated in 2.5 mL of water for $20~\\mathrm{min},$ and a mixture of SBMA/HEMA (7/3 mole ratio), ammonium persulfate $(1.0\\mathrm{mol}\\%)$ and sodium metasulfite (0.5 mol $\\%$ ) was added. The solution was stirred at $25~^{\\circ}\\mathrm{C}$ to allow the polymerization to proceed for $20~\\mathrm{min}.$ , and then spin-cast on the pretreated substrate. The coating was heated at $80~^{\\circ}\\mathrm{C}$ for $^{2\\mathrm{h}}$ to complete the polymerization and the bonding between the coating and the MPSi-modified substrate.  \n\nCoating Property Evaluation. The antifogging property was assessed by placing the specimens in a freezer maintained at $-20~^{\\circ}\\mathrm{C}$ for 1 h before exposing them to the atmosphere $\\sim30\\%$ relative humidity) at room temperature. The anti-icing performance was evaluated by the ice adhesion strength measurements as described in the literature.39,50 Hardness was estimated according to ASTM D3363 standard using pencils of a hardness ranging from 6B to 6H. A pencil was selected to mark a line on the specimen. If a scratch was left on the surface by this pencil, it would be replaced with a softer one and the test repeated until no scratch was left on the coating, and the hardness of the last pencil used was considered as the “pencil hardness” of the coating. The scratch-resistance performance of a surface was evaluated by rubbing it repeatedly with a cylindrical metal covered with a piece of ramie cloth at a pressure of $12\\ \\mathrm{KPa}$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# ASSOCIATED CONTENT",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# $\\otimes$ Supporting Information  \n\nThe Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.9b09610.  \n\nNMR spectrum of SBS, FTIR of bare and modified silica, thickness of the coating, TEM images of the coating filled with different silica nanoparticles, XPS of the coating, optical micrograph of the coating after cross-tape test, coating stability in water, antifogging performance at long exposure time, ice adhesion strength of bare glass, photographs of pencil hardness tester, healing of repeated damage at the same region, healing time as a function of coating thickness, antifogging performance of coating with different copolymer composition, and more antifouling data (PDF)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# AUTHOR INFORMATION  \n\nCorresponding Authors $^{*}\\mathrm{E}$ -mail: zhanggy608@ciac.ac.cn (G.Z.). $^*\\mathrm{E}$ -mail: zhsu@ciac.ac.cn (Z.S.).  \n\nORCID  \n\nZhaohui Su: 0000-0002-1530-8142",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# Author Contributions  \n\nAll authors have given approval to the final version of manuscript.",
+        "category": " Abstract/Introduction/Materials and methods/Results and discussion/Conclusions/References"
+    },
+    {
+        "id": 10,
+        "chunk": "# Notes  \n\nThe authors declare no competing financial interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 11,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nThis work was supported by the National Natural Science Foundation of China (21429401).  \n\nREFERENCES   \n(1) Wang, ${\\mathrm{R}}.{\\mathrm{}}{\\mathrm{,}}$ Hashimoto, K.; Fujishima, A.; Chikuni, M.; Kojima, E.; Kitamura, A.; Shimohigoshi, M.; Watanabe, T. Light-Induced Amphiphilic Surfaces. Nature 1997, 388, 431−432.   \n(2) Gao, X.; Yan, X.; Yao, X.; Xu, L.; Zhang, K.; Zhang, J.; Yang, B.; Jiang, L. The Dry-Style Antifogging Properties of Mosquito Compound Eyes and Artificial Analogues Prepared by Soft Lithography. Adv. Mater. 2007, 19, 2213−2217.   \n(3) Howarter, J. A.; Youngblood, J. P. Self-Cleaning and Anti-Fog Surfaces via Stimuli-Responsive Polymer Brushes. Adv. Mater. 2007, 19, 3838−3843.   \n(4) Lee, H.; Alcaraz, M. L.; Rubner, M. F.; Cohen, R. E. ZwitterWettability and Antifogging Coatings with Frost-Resisting Capabilities. ACS Nano 2013, 7, 2172−2185.   \n(5) Han, Z.; Feng, X.; Guo, Z.; Niu, S.; Ren, L. Flourishing Bioinspired Antifogging Materials with Superwettability: Progresses and Challenges. Adv. Mater. 2018, 30, No. e1704652.   \n(6) Zhao, J.; Meyer, A.; Ma, L.; Ming, W. Acrylic coatings with surprising antifogging and frost-resisting properties. Chem. Commun. 2013, 49, 11764−11766.   \n(7) Zhao, J.; Ma, L.; Millians, W.; Wu, T.; Ming, W. Dual-Functional Antifogging/Antimicrobial Polymer Coating. ACS Appl. Mater. Interfaces 2016, 8, 8737−8742.   \n(8) Li, Y.; Fang, X.; Wang, Y.; Ma, B.; Sun, J. Highly Transparent and Water-Enabled Healable Antifogging and Frost-Resisting Films Based on Poly(vinyl alcohol)−Nafion Complexes. Chem. Mater. 2016, 28, 6975−6984.   \n(9) England, M. W.; Urata, C.; Dunderdale, G. J.; Hozumi, A. AntiFogging/Self-Healing Properties of Clay-Containing Transparent Nanocomposite Thin Films. ACS Appl. Mater. Interfaces 2016, 8, 4318−4322.   \n(10) Wang, Y.; Li, T.; Li, S.; Sun, J. Antifogging and Frost-Resisting Polyelectrolyte Coatings Capable of Healing Scratches and Restoring Transparency. Chem. Mater. 2015, 27, 8058−8065.   \n(11) Xu, F.; Li, X.; Li, Y.; Sun, J. Oil-Repellent Antifogging Films with Water-Enabled Functional and Structural Healing Ability. ACS Appl. Mater. Interfaces 2017, 9, 27955−27963.   \n(12) Blaiszik, B. J.; Kramer, S. L. B.; Olugebefola, S. C.; Moore, J. S.; Sottos, N. R.; White, S. R. Self-Healing Polymers and Composites. Annu. Rev. Mater. Res. 2010, 40, 179−211.   \n(13) Wu, D. Y.; Meure, S.; Solomon, D. Self-healing polymeric materials: A review of recent developments. Prog. Polym. Sci. 2008, 33, 479−522.   \n(14) Wang, Z.; van Andel, E.; Pujari, S. P.; Feng, H.; Dijksman, J. A.; Smulders, M. M. J.; Zuilhof, H. Water-repairable zwitterionic polymer coatings for anti-biofouling surfaces. J. Mater. Chem. B 2017, 5, 6728− 6733.   \n(15) Wang, C.; Wu, H.; Chen, Z.; McDowell, M. T.; Cui, Y.; Bao, Z. Self-healing chemistry enables the stable operation of silicon microparticle anodes for high-energy lithium-ion batteries. Nat. Chem. 2013, 5, 1042−1048.   \n(16) Burnworth, M.; Tang, L.; Kumpfer, J. R.; Duncan, A. J.; Beyer, F. L.; Fiore, G. L.; Rowan, S. J.; Weder, C. Optically healable supramolecular polymers. Nature 2011, 472, 334−337.   \n(17) Nakahata, M.; Takashima, Y.; Yamaguchi, H.; Harada, A. Redox-responsive self-healing materials formed from host-guest polymers. Nat. Commun. 2011, 2, 511.   \n(18) Lu, Y. X.; Guan, Z. Olefin Metathesis for Effective Polymer Healing via Dynamic Exchange of Strong Carbon-Carbon Double Bonds. J. Am. Chem. Soc. 2012, 134, 14226−31.   \n(19) Amamoto, Y.; Otsuka, H.; Takahara, A.; Matyjaszewski, K. Selfhealing of Covalently Cross-Linked Polymers by Reshuffling Thiuram Disulfide Moieties in Air under Visible Light. Adv. Mater. 2012, 24, (20) Ji, S.; Cao, W.; Yu, Y.; Xu, H. Visible-Light-Induced SelfHealing Diselenide-Containing Polyurethane Elastomer. Adv. Mater. 2015, 27, 7740−7745.   \n(21) Cash, J. J.; Kubo, T.; Bapat, A. P.; Sumerlin, B. S. RoomTemperature Self-Healing Polymers Based on Dynamic-Covalent Boronic Esters. Macromolecules 2015, 48, 2098−2106.   \n(22) Cordier, P.; Tournilhac, F.; Soulié-Ziakovic, C.; Leibler, L. Selfhealing and thermoreversible rubber from supramolecular assembly. Nature 2008, 451, 977−980.   \n(23) Wang, C.; Liu, N.; Allen, R.; Tok, J. B.-H.; Wu, Y.; Zhang, F.; Chen, Y.; Bao, Z. A Rapid and Efficient Self-Healing ThermoReversible Elastomer Crosslinked with Graphene Oxide. Adv. Mater. 2013, 25, 5785−5790.   \n(24) Sangermano, M.; Messori, M. Scratch Resistance Enhancement of Polymer Coatings. Macromol. Mater. Eng. 2010, 295, 603−612. (25) Liu, X.; Zhou, L.; Liu, F.; Ji, M.; Tang, W.; Pang, M.; Sun, J. Exponential growth of layer-by-layer assembled coatings with welldispersed ultrafine nanofillers: a facile route to scratch-resistant and transparent hybrid coatings. J. Mater. Chem. 2010, 20, 7721.   \n(26) Seo, J. Y.; Han, M. Multi-functional hybrid coatings containing silica nanoparticles and anti-corrosive acrylate monomer for scratch and corrosion resistance. Nanotechnology 2011, 22, No. 025601. (27) Li, Y.; Chen, S.; Li, X.; Wu, M.; Sun, J. Highly Transparent, Nanofiller-Reinforced Scratch-Resistant Polymeric Composite Films Capable of Healing Scratches. ACS Nano 2015, 9, 10055−10065. (28) Luo, F.; Sun, T. L.; Nakajima, T.; Kurokawa, T.; Zhao, Y.; Sato, K.; Ihsan, A. B.; Li, X.; Guo, H.; Gong, J. P. Oppositely Charged Polyelectrolytes Form Tough, Self-Healing, and Rebuildable Hydrogels. Adv. Mater. 2015, 27, 2722−2727.   \n(29) Chen, Y.; Kushner, A. M.; Williams, G. A.; Guan, Z. Multiphase design of autonomic self-healing thermoplastic elastomers. Nat. Chem. 2012, 4, 467−472.   \n(30) Howarter, J. A.; Youngblood, J. P. Self-Cleaning and Next Generation Anti-Fog Surfaces and Coatings. Macromol. Rapid Commun. 2008, 29, 455−466.   \n(31) Estephan, Z. G.; Jaber, J. A.; Schlenoff, J. B. Zwitterionstabilized silica nanoparticles: toward nonstick nano. Langmuir 2010, 26, 16884−9.   \n(32) Bredas, J. L.; Chance, R. R.; Silbey, R. Head-head Interactions in Zwitterionic Associating Polymers. Macromolecules 1988, 21, 1633. (33) Georgiev, G. S.; Kamenska, E. B.; Vassileva, E. D.; Kamenova, I. P.; Georgieva, V. T.; Iliev, S. B.; Ivanov, I. A. Self-Assembly, Antipolyelectrolyte Effect, and Nonbiofouling Properties of Polyzwitterions. Biomacromolecules 2006, 7, 1329−1334.   \n(34) Guo, W.; Li, X.; Xu, F.; Li, Y.; Sun, J. Transparent Polymeric Films Capable of Healing Millimeter-Scale Cuts. ACS Appl. Mater. Interfaces 2018, 10, 13073−13081.   \n(35) Li, G.; Xue, H.; Cheng, G.; Chen, S.; Zhang, F.; Jiang, S. Ultralow Fouling Zwitterionic Polymers Grafted from Surfaces Covered with an Initiator via an Adhesive Mussel Mimetic Linkage. J. Phys. Chem. B 2008, 112, 15269−15274.   \n(36) ASTM D3359. Standard Test Methods for Measuring Adhesion by Tape Test, ASTM International, https://www.astm.org/DATABASE. CART/HISTORICAL/D3359-09.htm.   \n(37) Leng, C.; Hung, H.-C.; Sieggreen, O. A.; Li, Y.; Jiang, S.; Chen, Z. Probing the Surface Hydration of Nonfouling Zwitterionic and Poly(ethylene glycol) Materials with Isotopic Dilution Spectroscopy. J. Phys. Chem. C 2015, 119, 8775−8780.   \n(38) Li, C.; Li, X.; Tao, C.; Ren, L.; Zhao, Y.; Bai, S.; Yuan, X. Amphiphilic Antifogging/Anti-Icing Coatings Containing POSSPDMAEMA-b-PSBMA. ACS Appl. Mater. Interfaces 2017, 9, 22959−22969.   \n(39) Liang, B.; Zhang, G.; Zhong, Z.; Huang, Y.; Su, Z. Superhydrophilic Anti-Icing Coatings Based on Polyzwitterion Brushes. Langmuir 2019, 35, 1294−1301.   \n(40) Kim, P.; Wong, T. S.; Alvarenga, J.; et al. Liquid-Infused Nanostructured Surfaces with Extreme Anti-Ice and Anti-Frost Performance. ACS Nano 2012, 6, 6569−6577.  \n\n(41) Dou, R.; Chen, J.; Zhang, Y.; Wang, X.; Cui, D.; Song, Y.; Jiang, L.; Wang, J. Anti-icing Coating with an Aqueous Lubricating Layer. ACS Appl. Mater. Interfaces 2014, 6, 6998−7003. (42) Lv, J.; Song, Y.; Jiang, L.; Wang, J. Bio-Inspired Strategies for Anti-Icing. ACS Nano 2014, 8, 3152−3169. (43) ASTM D3363. Standard Test Method for Film Hardness by Pencil Test, ASTM International, https://www.astm.org/Standards/ D3363.htm. (44) Wang, X.; Liu, F.; Zheng, X.; Sun, J. Water-enabled self-healing of polyelectrolyte multilayer coatings. Angew. Chem. Int. Ed. 2011, 50, 11378−11381. (45) Glendening, E. D.; Streitwieser, A. Natural energy decomposition analysis: An energy partitioning procedure for molecular interactions with application to weak hydrogen bonding, strong ionic, and moderate donor−acceptor interactions. J. Chem. Phys. 1994, 100, 2900−2909. (46) He, K.; Duan, H.; Chen, G. Y.; Liu, X.; Yang, W.; Wang, D. Cleaning of Oil Fouling with Water Enabled by Zwitterionic Polyelectrolyte Coatings: Overcoming the Imperative Challenge of Oil-Water Separation Membranes. ACS Nano 2015, 9, 9188−9198. (47) Leng, C.; Han, X.; Shao, $\\mathrm{Q.;}$ Zhu, Y.; Li, Y.; Jiang, S.; Chen, Z. In Situ Probing of the Surface Hydration of Zwitterionic Polymer Brushes: Structural and Environmental Effects. J. Phys. Chem. C 2014, 118, 15840−15845. (48) Zhang, Z.; Chao, T.; Chen, S.; Jiang, S. Superlow Fouling Sulfobetaine and Carboxybetaine Polymers on Glass Slides. Langmuir 2006, 22, 10072−10077. (49) Liu, M.; Matsuda, T. Siloxane Zwitterions: Synthesis and Surface Properties of Crosslinked Polymers. J. Appl. Polym. Sci. 1975, 19, 1221−1225. (50) Chen, J.; Luo, Z.; Fan, $\\mathrm{Q.;}$ Lv, J.; Wang, J. Anti-Ice Coating Inspired by Ice Skating. Small 2014, 10, 4693−4699.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Design of Abrasion-Resistant, Long-Lasting Antifog Coatings  \n\nBrian Macdonald, Fan-Wei Wang, Brian Tobelmann, Jing Wang, Jason Landini, Nipuli Gunaratne, Joseph Kovac, Todd Miller, Ravi Mosurkal, and Anish Tuteja\\*  \n\nCite This: ACS Appl. Mater. Interfaces 2024, 16, 13018−13028",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# ACCESS  \n\nMetrics & More  \n\nArticle Recommendations  \n\nSupporting Information  \n\nABSTRACT: Fog formation is a common challenge for numerous applications, such as food packaging, mirrors, building windows, and freezer/refrigerator doors. Most notably, fog forms on the inner surfaces of prescription glasses and safety eyewear (particularly when used with a mask), face shields, and helmet lenses. Fogging is caused by the distortion of light from condensed water droplets present on a surface and can typically be prevented if the surface static water contact angle $\\mathbf{\\eta}(\\theta)$ is less than ${\\sim}40^{\\circ}$ . Such a low contact angle can be readily achieved by either increasing the substrate surface energy or by engineering surface nanotexture. Unfortunately, such nanotexture can be readily damaged with use, while high surface energy substrates get covered with low surface energy foulants over time. Consequently, even with numerous ephemeral antifog coatings, currently there are no commercially available, durable, and permanent antifog coatings. Here we discuss the development of a new class of high-performance antifog coatings that are abrasion-resistant and long-lasting. These polyvinylpyrrolidone-based coatings, designed based on the classical Ratner−Lancaster wear model, dramatically outperform the base polymer, as well as all tested commercially available antifog coatings. Specifically, these coatings exhibit $\\mathrm{\\a>400\\%}$ increase in fogging time compared to base polymer, $\\mathfrak{a}>50,000\\%$ increase in wear resistance, and excellent long-term antifog performance. The developed coatings also significantly outperformed all tested commercially available antifog coatings in terms of their antifog performance, wear resistance, and long-term cyclical performance. Additionally, the key design strategies employed here\u0001 incorporation of toughening agents and hydrophilic slip additives\u0001offer a new approach to developing high-performance, durable antifog coatings based on other well-known antifog polymers.  \n\n![](images/b726223f3c8464c51dbf3ac599e770be77de68dac2bfaf8860a72b3886a115fd.jpg)  \n\nKEYWORDS: surface science, polymers, antifog, tribology, interfacial phenomena",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# 1. INTRODUCTION  \n\nSurface fogging is typically caused by the condensation of water microdroplets on cold surfaces which scatter light, rendering ordinarily transparent surfaces hazy.1 Fogging typically occurs when the static water contact angle on the surface $\\theta~>~40^{\\circ}$ .1 Fogging adversely affects a variety of transparent surfaces such as prescription glasses,2 safety eyewear,3 swimming goggles,4 camera lenses,5 Hazmat face shields,6 and soldier eyewear.7,8 Additional negative impacts of fogging include the reduction of efficient solar energy conversion,9 and the contamination of medical devices.10 To mitigate surface fogging, highly hydrophilic coatings (water contact angle ${<}40^{\\circ}$ ) are preferable, though some studies have demonstrated antifog performance with hydrophilic coatings that possess somewhat higher contact angles.11,12 Such coatings can maintain optical transparency and clarity,13 and can dry faster via convection than hydrophobic surfaces.14  \n\nThe design of hydrophilic antifog coatings typically employs one or both of the following strategies: modifying the surface chemistry or surface texture. A common approach to increase surface wetting is by increasing the coatings surface energy via plasma treatment.15,16 However, plasma-treated materials typically succumb to “hydrophobic recovery,” where the material loses its hydrophilic properties due to the deposition of lower surface energy molecules from the environment (such as different silicones, waxes, and other organic molecules), and/or the diffusion of low energy molecules from within the coating to the air interface.16,17  \n\nMicro- and/or nanotextured surfaces have also been utilized for developing hydrophilic antifog coatings. Such surfaces can significantly reduce the apparent contact angles on the surface as the water droplets fully wet the porous texture and are in the Wenzel state.18 Notable examples of this approach include microfabricated nanocones and nanopillars, which display good antifogging properties.19,20 S uch textured surfaces typically require highly precise and expensive fabrication/ processing conditions, making scalability and cost a significant concern. The durability of the fabricated textures is also an issue, as the precisely produced micro- or nanostructures are highly susceptible to damage and wear during use.  \n\n![](images/41287e19a542adc88e312862c921fa22da4bdb4dc584b87e0660efa921165e60.jpg)  \n\n![](images/5943363775684c557351030d3717bba4bd687fce537bfdf9af2d02b34b2f6d78.jpg)  \nFigure 1. (A) A schematic illustrating the different components and the fabrication methodology to produce a durable, high-performance antifog coating. (B) Optical images highlighting the enhanced antifog performance due to the addition of a hydrophilic slip additive. (C) A schematic and scanning electron microscopy images illustrating the friction and wear reduction induced via the addition of a hydrophilic slip additive.  \n\nCeramic coatings such as titania and zinc oxide have also been investigated for antifog applications. On these coatings, water contact angle can decrease dramatically upon UV exposure.1,21−24 However, despite their performance and inherent durability, ceramic coatings often require high temperature calcination, eliminating the possibility of using plastic substrates such as polycarbonate, commonly utilized for producing safety glasses or goggle lenses. Additionally, such coatings are also vulnerable to the deposition of lower surface energy molecules from the environment (due to their high solid surface energy) and as such cannot provide long-term antifog performance.  \n\nAntifog coatings can additionally be fabricated by utilizing relatively high surface energy polymers such as polyethylene glycol,25 poly(vinyl alcohol),11 polyvinyl acetate,11 polyvinylpyrrolidone,26 as well as the recently developed zwitterionic and amphiphilic polymers.27−29 These hydrophilic polymers have low water contact angles, and most are able to absorb moisture to further reduce the water contact angles over time.26,29 However, such polymeric antifogging coatings can typically be easily damaged via mechanical abrasion and may lose their performance after prolonged exposure to a fogging environment.  \n\nFinally, layer-by-layer self-assembly of cationic and anionic polymers has also been utilized to form highly effective antifog coatings.30−33 This methodology, however, can suffer from the need for extensive surface preparation and long dip- and/or cure-times. Additionally, while many of the developed coatings can display high pencil hardness, most of the coatings can still be readily damaged by mechanical abrasion. Overall, the current strategies for the fabrication of antifog coatings suffer from either poor mechanical durability and/or loss of performance over the long-term due to their inherently high surface energy. Consequently, despite numerous temporary, commercial antifog coatings, there are no high-performance permanent, durable antifog coatings available in the market.  \n\nWith the benefits of easier fabrication, processing, lower weight, feasible application to plastic substrates, and lower cost, polymer coatings are well-suited for the development of durable, long-term, antifog coatings. The mechanical durability of polymeric coatings during abrasion can be described by the Ratner−Lancaster relation as  \n\n$$\nW=C\\mu{\\left({\\frac{1}{H\\varepsilon_{\\mathrm{u}}\\sigma_{\\mathrm{u}}}}\\right)}\n$$  \n\nwhere $W$ is the wear rate (defined as the abraded material volume per unit travel distance of the abraser), $C$ is a constant, $\\mu$ is the friction coefficient, $H$ is the coating hardness, and $\\varepsilon_{\\mathrm{u}}$ and $\\sigma_{\\mathrm{u}}$ are the strain and stress at tensile break, respectively.34,35 This relation illustrates that the polymer wear coefficient is proportional to the interfacial friction coefficient and inversely proportional to the film hardness, and the strain and stress at tensile break.34 Therefore, increasing the coating hardness, tensile stress, and strain at break and reducing the surface frictional coefficient can increase the polymer wear resistance.  \n\nThough eq 1 provides important material design criteria for developing durable polymeric coatings, there are two major challenges specific to the design of hydrophilic antifogging coatings. First, hydrophilic polymers tend to have a narrow range of miscibility, limiting the number of additives that can be used to enhance their hardness and tensile properties. Second, the high surface energy of the hydrophilic antifogging polymeric coatings inherently results in a high work of adhesion, which can lead to a high friction coefficient.36,37 Although several attempts have been made to engineer wearresistant polymeric antifog coatin g,26,38−40 thus far it has not been possible to simultaneously overcome these two material design challenges.  \n\nHerein, we report the systematic design and fabrication of durable polymeric antifogging coatings that simultaneously demonstrate high surface hardness, stress, strain at break, and a low friction coefficient. These coatings are fabricated by utilizing a cross-linked polyvinylpyrrolidone (PVP) matrix, which is modified with two critical additives for the simultaneous enhancement of antifogging performance, as well as mechanical durability. We have also developed a facile two-step spray-coating process to apply these coatings onto a wide variety of plastic surfaces as shown in Figure 1A. This fabrication process can be readily scaled up, and as shown in Figure 1A, the developed coating is highly effective at preventing fogging. As described in detail below, the fabricated coatings are over $400\\%$ more effective at preventing the appearance of fog than unmodified PVP, and readily surpass the long-term performance of different commercially available antifog coatings (Figure 1B). In addition, our antifogging coatings display a higher toughness and a friction coefficient that is $300\\%$ lower than that of PVP alone. Consequently, they can survive more than 500-fold $(50,000\\%$ increase) additional mechanical abrasion cycles before failure when compared with unmodified PVP coatings (Figure 1C). Overall, our work shows that the Ratner−Lancaster relation can be used to systematically design high-performance antifog coatings that are simultaneously abrasion-resistant and long-lasting.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2. MATERIALS AND METHODS  \n\n2.1. Antifog Coating Fabrication. 2.1.1. Solution Parameters. A $0.0265~\\mathrm{g/mL}$ solution of $1300\\mathrm{kDa}$ PVP (Sigma-Aldrich) and 0.001 $\\mathbf{g}/\\mathbf{m}\\mathbf{L}$ benzophenone (Sigma-Aldrich) was made by dissolving the polymer in a solution containing 1-propanol (Fischer Scientific), distilled water, and $15\\%$ Hydrogen peroxide (Fisher Scientific). The volumetric ratio of these three solvents was 0.931:0.029:0.040 respectively. The surfactants and cross-linker were later dissolved in solutions of 1-propanol in order to dilute and add to the PVP solution. Polysorbate 20, polysorbate 80, polysorbate 85, Span 20 or Span 80 (all purchased from Sigma-Aldrich) were dissolved in 1- propanol in varying concentrations. Pentaerythritol tetraacrylate (PETRA) (Sigma-Aldrich) was also dissolved in 1-propanol in varying concentrations. PETRA and surfactant solutions were added to the solvent mixture to achieve a volume ratio of 0.895 1-propanol: 0.027 DI water: 0 $.03915\\%\\mathrm{H}_{2}\\mathrm{O}_{2}$ : 0.019 PETRA/1-propanol solution: 0.019 surfactant/1-propanol solution (PVP now at $0.0254~\\mathrm{mg/mL}$ ). All contents were stirred in a glass septa-jar until fully dissolved $\\cdot{>}2$ h). Concentrations of PETRA or surfactants are with respect to the mass of PVP.  \n\n2.1.2. Coating Fabrication. Impact-resistant polycarbonate strips (purchased from McMaster-Carr) of 1 in. width and $1/16$ in. thickness were cut to 4 in. slides for testing. Polycarbonate strips were first cleaned with isopropyl alcohol and blown dry before exposure to $30~\\mathrm{W}$ oxygen plasma (Harrik Plasma Cleaner PDC-001) for $10~\\mathrm{min}$ . Once treated with plasma, the samples were coated using a homebuilt automated spray coating apparatus. The plasma-treated samples were placed at a distance of $20\\ \\mathrm{cm}$ from the spray gun. The automated spray coater with spray gun (HVLP mini touch up ATD-6903) maintained parameters set to a linear speed of ${\\sim}20\\ \\mathrm{cm/s},$ 2 spray passes, and spray pressure of 20 psi. The solutions were then dispensed into the spray reservoir and sprayed onto the plasmatreated polycarbonate. This allowed for the fabrication of coatings with a consistent thickness and surface texture. Immediately after, the coatings were subjected to UVA (UVP 100 W Longwave Mercury Spot Lamp) and UVC (UVP XX-40S Bench Lamp $2.6\\mathrm{\\mW/cm^{2}}$ ) exposure at a distance of $12\\mathrm{cm}$ from the lamps for a period of $10\\mathrm{min}$ . Commercially available antifog coatings: Optix 55 Anti Fog Treatment for Anti-Reflective Lenses (Optix) (purchased from Optix 55), Op Drops Anti-Fog and Lens Cleaner (Ops Drops) (purchased from Gear Aid), Revision wipes (Revision Military), and  \n\nExxene HCF-100 (Exxene Corporation) were fabricated following the instructions provided on the products.  \n\n2.1.3. Evaluation of Coating Properties and Antifog Performance. Infrared spectrum measurement was conducted by a Nicolet 6700 FTIR spectrometer (Thermo Scientific). The indentation hardness measurement and the tensile tests of PVP and PVP/ PETRA thin strips were conducted by utilizing the Hysitron TI 950 TriboIndenter (Bruker) and an RSA-G2 DMA (TA Instruments), respectively. The detailed sample fabrication for PVP and PVP/ PETRA thin strips and the raw stress−strain data for each coating formulation are provided in the Supporting Information.  \n\nThe Hansen solubility parameters were calculated by using the HSPiP software (version 5.3.09). The friction coefficients were measured with a Shimpo model FG-7005 force gauge. The coating’s mechanical durability was evaluated via both abrasion testing and wiping. The images of samples before and after abrasion were captured by a scanning electron microscope (SEM) Tescan Mira3 FEG SEM (Tescan). The surface roughness was measured by a Dektak 6M stylus profilometer. Fogging tests were conducted in a homemade fog tester, and a fog tester developed at the US Army Soldier Center, Natick, MA. The pass criterion for antifog substrates or eyewear was that the change in the measured contrast ratio before and after fogging be $<7\\%$ . Additional information on the fog tester developed at the US Army Soldier Center, Natick, MA, can be found elsewhere.41 See the Supporting Information for additional details.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 3. RESULTS AND DISCUSSION  \n\n3.1. Optimization of Coating Toughness. PVP can selfcross-link via the condensation of local succinimide groups in the presence of hydrogen peroxide and UVC radiation.26,42 The reaction results in a polymer network that is resistant to dissolution in humid or aqueous environments. Thus, PVP has been widely utilized previously as an antifog coating that can survive several fogging/defogging cycles.42−45 However, this self-cross-linking still leaves the coating vulnerable to adhesive failure from the underlying substrate. The addition of benzophenone can facilitate the strong adhesion of the PVP coating to different underlying polymeric substrates (such as the polycarbonate used here) via covalent bonding after exposure to UVA radiation.26 Unfortunately, this cross-linked PVP can still be brittle and therefore easily fractured. To overcome this limitation, we added a miscible tetrafunctional oligomer pentaerythritol tetraacrylate (PETRA) cross-linker to increase the toughness of PVP. The chemical structure of PETRA is shown in Figure 1A. PETRA can help generate a semi interpenetrating polymer network (S-IPN) through a selfreaction between the acrylate groups. The self-reaction of PETRA was confirmed via FTIR (Figure S1), which demonstrates a significant decrease in the acrylate peak after $10\\ \\mathrm{min}$ of UV exposure. Substrate UV exposure during the process was minimized to avoid degradation of the underlying polycarbonate.46  \n\nFigure 2A shows the hardness values for the different PVP coatings as a function of PETRA weight $\\%$ . The self-crosslinking and the cross-linking with PETRA both increased the coatings hardness by over $100~\\mathrm{{MPa}}$ . This increase in hardness is expected to reduce the coatings wear rate as predicted by eq 1. The hardness of PVP with varying amounts of PETRA was effectively unchanged at weight fractions of up to $40\\%$ . The toughness of the PVP coatings was, however, enhanced significantly via the addition of PETRA. Tensile test data from the cross-linked PVP and PVP−PETRA films (Figure 2B,C) showed that the coating ductility was notably increased with the addition of up to $20\\%$ PETRA. Figure 2B also illustrates an increase in the stress−strain product at the breaking point, from 0.3 to $1.3~\\mathrm{MPa}$ , for the self-cross-linked PVP and cross-linked PVP with $20\\%$ PETRA respectively. As described earlier, the increase in the product of the tensile stress and strain at break correlates inversely with the coating wear rate (eq 1).  \n\n![](images/0a7b752f122748e542099fe2778e5bd84e71fc4c591e81d904011558b92ddfb5.jpg)  \nFigure 2. (A) Indentation hardness values for polycarbonate, PVP, and cross-linked PVP with increasing concentration of PETRA. (B) Stress−strain product at break/tear onset for PVP and cross-linked PVP with increasing concentration of PETRA. (C) Stress vs strain curve for PVP and PVP with $20\\%$ PETRA highlighting the increase in PVP toughness through the addition of PETRA. (D) Optical images showing the brittle failure for PVP and the ductile failure for PVP with $20\\%$ PETRA.  \n\nFrom the data shown in Figure 2C, it can be observed that the self-cross-linked PVP exhibited a brittle failure, while PVP/ $20\\%$ PETRA exhibited a ductile tearing failure. The difference in the films fracture with and without the PETRA additive is also clear from the optical images shown in Figure 2D. Thus, the maximum enhancement of coating toughness was achieved via the addition of 20 wt $\\%$ PETRA, which simultaneously increased the coating hardness, stress−strain product at the breaking point, and thereby likely the overall coating durability, as may be predicted by eq 1.  \n\n3.2. Reducing the Coating’s Friction Coefficient. Based on the Ratner−Lancaster relation, further enhancement of the wear-resistant properties of the coating can be achieved by reducing the coating’s coefficient of friction (COF). To achieve this reduction, we introduced miscible slip additives into the PVP−PETRA network to form a lubricating layer. Slip additives are relatively low molecular weight macromolecules that are blended into a polymer matrix. Owing to the differences in surface energies between the PVP matrix and the free-slip agents, these macromolecules can partially migrate to the air interface via diffusion, forming an interfacial, ultrathin lubricant layer.47 Identifying slip additives that are miscible with PVP and other antifog polymers while maintaining antifogging properties presents a unique challenge. The majority of slip additives, for example, different oils and fatty amides,48 are not miscible with hydrophilic antifog polymers like PVP. We identified and utilized a class of amphiphilic macromolecular surfactants as slip additives for PVP. Specifically, the surfactants identified include sorbitan monooleate (SPAN80), sorbitan monolaurate (SPAN20), polyoxyethylene sorbitan trioleate (PS85), polyoxyethylene sorbitan monooleate (PS80), and polyoxyethylene sorbitan monolaurate (PS20). These amphiphilic macromolecules were selected because of their broad solubility in different polymer matrices, which results from their asymmetric polar molecular structure.  \n\n![](images/970f055e03ee6676b8e5b247d1d2158a28ee98c5f6fa74cbafe2746d30fe242e.jpg)  \nFigure 3. Hansen solubility spheres for PVP, PS20, PS80, and SPAN80, as well as the miscibility factor $(S^{*})$ values for each system.  \n\n![](images/9cccf35a1b6038234f4989d9c9755ff10ee90c29f3a9c3596a43e285827ae4d5.jpg)  \nFigure 4. (A) Miscibility factors and HLB values for the different surfactant additives. SEM micrograph insets demonstrate the surface phase separation of the surfactants from the PVP matrix. (B) Coefficient of friction (COF) values for PVP, PVP with PETRA and PVP with the different surfactant additives. The inset shows the variation of the COF with $S^{*}$ values. (C) The variation of the COF with surfactant HLB values.  \n\nThe surfactants and their miscibility with PVP were analyzed by utilizing Hansen solubility parameters. Hansen solubility parameters are related to the sum of cohesive energy densities, consisting of hydrogen bonding, polar forces, and dispersive forces intrinsically exerted by a given compound.49 By experimentally determining the good and poor solvents for the different slip agents and subsequently utilizing the HSPiP software (see the Materials and Methods section), we estimated their solubility parameters and generated a solubility sphere in Hansen space for each molecule (Table S1).  \n\nThe Hansen solubility spheres for each component enable calculation of the miscibility factor $(S^{*})$ . The miscibility parameter, $S^{*,50}$ can be defined as  \n\n$$\nS^{*}=\\frac{\\Delta R-R_{\\mathrm{{surfactant}}}+R_{\\mathrm{{matrix}}}}{2R_{\\mathrm{{matrix}}}}\n$$  \n\nwhere $\\Delta R$ is the distance in 3D solubility space between the centers of the surfactants and PVP’s solubility spheres, with their radii denoted by $R_{\\mathrm{surfactant}}$ and $R_{\\mathrm{matrix}},$ respectively.  \n\n$S^{*}$ can be conceptualized as the degree of spherical overlap between two Hansen spheres and indicates the level of miscibility between two molecules.50,51 A negative $S^{*}$ value implies that the two molecules are miscible, and the more negative the value for $S^{*}$ , the more miscible the two molecules. Figure 3 displays the Hansen solubility spheres and $S^{*}$ values between the different surfactants and PVP. The data shows that $S^{*}$ values decrease in the order of $\\mathrm{SPAN80}>\\mathrm{SPAN}20>$ $\\mathrm{PS}85>\\mathrm{PS}80>\\mathrm{PS}20.$ . Only PS80-PVP and PS20-PVP systems have negative $S^{*}$ values, indicating that both PS80 and PS20 are highly miscible with PVP (Figure 4A).  \n\nThe surfactant hydrophilic−lipophobic balance value (HLB) is another important dimensionless parameter for evaluating surfactant miscibility within the PVP matrix. HLB values relate to the hydrophilic or hydrophobic nature of a nonionic surfactant.52 In general, molecules with HLB values ${>}10$ are hydrophilic, while those with HLB values $<10$ are hydrophobic. For antifogging applications, hydrophilic chemistry is preferred, and therefore surfactants with higher HLB values should be preferred as slip additives. Based on its higher HLB values, and miscibility within the PVP matrix, we selected PS20 as the optimal slip additive for PVP in order to maximize the antifog performance of the developed coatings. The HLB values and $S^{*}$ values for the different surfactants are provided in Table S2.  \n\nNext, we measured the coefficient of friction (COF) values for PVP, and PVP with different added surfactants. The COF values are shown in Figure 4B, and the values are listed in Table S3. From the data, it is clear that all the surfactants can significantly reduce the friction coefficient for PVP. The red dashed line shows the friction coefficient for uncoated polycarbonate. Both PVP and toughened $\\mathrm{PVP}/20\\%$ PETRA coatings increase the surface friction coefficient relative to uncoated polycarbonate. This is consistent with previous work that shows that increasing the substrate surface energy typically increases the surface friction coefficient.36,37 The addition of $15\\%$ surfactant into the PVP/ $20\\%$ PETRA matrix induces a nearly threefold reduction in COF. Interestingly, the coefficient of friction was found to be independent of both $S^{*}$ (Figure 4B inset) and HLB values for the different surfactants (Figure 4C).  \n\n![](images/ef240c09ee020eea3e9fbdad210eb626f988e86051127cbd09db679fc8e55772.jpg)  \nFigure 5. (A) Optical and SEM images for polycarbonate and different coated polycarbonate substrates after sequential Taber abrasion with a CS-5 abrader. (B) Change in RMS roughness before and after sequential abrasion cycles.  \n\n![](images/f90b56807abc2b8a1f352d9920379e6229e805c3a736799f71343a2595c5fdaf.jpg)  \nFigure 6. (A) Static water contact angles for PC, PVP, and PVP with increasing mass $\\%$ of PETRA. (B) Static water contact angles for $\\mathrm{PVP}/20\\%$ PETRA with $15\\%$ of varying surfactant additives.  \n\n3.3. Abrasive Wear Resistance. The abrasive wear resistance of different antifogging coatings was tested by using a standard linear Taber Abrasion apparatus with a CS-5 abrader (Figure S2). The data in Table S4 shows that polycarbonate, PVP, and PVP−PETRA were easily abraded after a few abrasion cycles $(\\sim10)$ below $300~\\mathrm{g}$ of applied load within the Taber apparatus. In comparison, the cross-linked PVP with $15\\%$ PS80 was able to survive 5000 cycles of abrasion under the same applied load (i.e., $a>500\\times$ increase in wear resistance), and even remained intact after another 1000 cycles of abrasion under a higher $550\\ \\mathrm{g}$ load. Adding the toughening agent PETRA allowed the coatings to survive the same abrasion as PVP−PS80, and an additional two sequences of 1000 abrasion cycles with increasing loads of 800 and 1050 g. In addition, the enhanced wear resistance of PVP with $20\\%$ PETRA and $15\\%$ surfactant slip additive was found to be independent of the choice of slip additive (Figure 5 and Table S4). This observation agrees well with the data reported earlier which shows that the friction coefficient of the PVP coatings was independent of the choice of added surfactant. Figure 5A shows SEM micrographs for polycarbonate and polycarbonate coated with the different PVP films after Taber abrasion. Each film was abraded with the following protocol: 5000 cycles under a $300\\mathrm{g}$ load, 1000 cycles under a $550\\mathrm{g}$ load, 1000 cycles under $\\mathbf{800}~\\mathbf{g}$ load, and 1000 cycles under $\\boldsymbol{1050}\\mathrm{\\g}$ load. The macroscale damage from the abrasion cycles can be readily seen on polycarbonate, polycarbonate coated with PVP and $\\mathrm{PVP}/20\\%$ PETRA. The surface root-mean-square (RMS) roughness before and after abrasion is shown in Figure 5B. Polycarbonate, polycarbonate coated with PVP, and PVP/ PETRA yielded notably higher changes in surface roughness after abrasion, indicating significant abrasive wear during the Taber testing. Meanwhile, substrates coated with PVP− PETRA with $15\\%$ surfactant yielded minimal changes in roughness after all the sequentially harsh abrasion cycles described above.  \n\n3.4. Antifog Performance. Figure 6A displays the static water contact angle of polycarbonate, PVP, and PVP with increasing concentration of PETRA over a period of $5\\ \\mathrm{min}$ after water-surface contact. As expected, hydrophobic polycarbonate showed only minor changes in contact angle over a period of 5 min due to evaporation. PVP-based coatings on the other hand are water-absorbing, causing the contact angle to significantly decrease over time. PVP-coated polycarbonate displays a contact angle below the $40^{\\circ}$ threshold in about a minute, and the addition of up to $20\\%$ PETRA did not notably change the coating’s contact angle despite the cross-linker’s hydrophobic properties. This minimal effect on contact angle is advantageous due to the enhancement of wear resistance provided by PETRA.  \n\nNext, we evaluated the impact of adding different surfactants on the observed antifog properties. As described above, all of the surfactant containing coatings contain PVP, $20\\%$ PETRA, and $15\\%$ of the surfactant. For simplicity, we will denote the different surfactant containing coatings as PS20, PS80, PS85, SPAN20, and SPAN80 based on the surfactant utilized. Figure 6B shows the impact of the HLB values on the measured water contact angles for the different coatings. The addition of SPAN 80 notably increases the contact angle of the antifog coating beyond that of pure PVP. As the HLB values increase up to 16.7 for PS20, the contact angle is reduced to near that of unmodified PVP.  \n\nAntifog testing on the different coatings was conducted in an environmental chamber that enabled precise control of the environmental humidity and substrate temperature (Figures S3 and S4). Briefly, the surface temperature of all samples was reduced to $14\\pm0.5{}^{\\circ}\\mathrm{C}$ (below the dew point) and the relative humidity was maintained to $54~\\pm~1\\%$ . The analysis and quantification of fogging utilized a modification to a previously reported testing methodology developed by Lee et al.29 Our modified testing methodology (see the Materials and Methods section and the Supporting Information) allowed for the direct evaluation of long-term antifogging performance under controlled, sustained humidity, and surface temperature. To the best of our knowledge, such a methodology has not been previously utilized for evaluating the antifog performance of various coatings. Unlike most previously developed antifog testing methodologies, our testing can not only discriminate between antifogging and fogging surfaces but also measure the performance of different antifog coatings over long periods of sustained fogging conditions. This enables quantitative performance comparison between different high-performing antifog coatings based on the change in optical transmissivity over time.  \n\nFigure 7 shows optical images from the different fogging experiments conducted on pure polycarbonate and polycarbonate coated with PVP, PS20, PS80, PS85, SPAN20, and SPAN80 samples. At about the $10\\ \\mathrm{min}$ mark, the substrate reaches the set cooling temperature, and fogging begins on the polycarbonate control surface. Unmodified PVP coatings demonstrated antifogging properties for up to $20\\ \\mathrm{min}$ , while the PVP coatings incorporating the SPAN 20 and SPAN 80 surfactants fogged up almost immediately due to their low HLB values, which resulted high water contact angles. The higher HLB values for the different polysorbate surfactants enabled enhanced antifogging properties. Figure 8A,B show the changes in image correlation factor (ICF) over time for each coating tested within our fogging chamber. The ICF values at any time point during the fogging experiment are calculated by measuring the digital image correlation between two images of the same area before and after fogging. The ICF quantifies visual clarity and scales from 0 to 1, where 1 means no distortion (i.e., the image after fogging perfectly correlates with the image before fogging) and 0 means no correlation among the images. Usually, values of $\\alpha$ above 0.95 indicate no image distortion, while $\\alpha$ values below 0.5 indicate poor visual clarity.29 Figure 8A shows the ICF values for the polycarbonate (PC), PVP, and PS20 samples during the fogging experiment. The PC surface fogs after ${\\sim}10\\ \\mathrm{\\min}$ , and the ICF values decrease continuously for the duration of the experiment. The PVP surface was able to prevent fogging for ${\\sim}15\\ \\mathrm{min}$ $\\mathrm{\\hbar}\\sim5~\\mathrm{min}$ of antifogging as it takes ${\\sim}10~\\mathrm{min}$ for the sample to cool below the dew point) with the ICF dropping to below 0.90 until it fully fogs with an ICF value of ${\\sim}0.50$ . The PS20 coating was able to fully eliminate fogging throughout the duration of the entire experiment and maintained ICF values ${>}0.96$ . This demonstrates a significant enhancement in antifog properties when compared with unmodified PVP. Figure 8B compares the performance of the PS20 coating to that of the more hydrophobic SPAN 80 and SPAN 20 coatings. It can be observed that both SPAN 20 and SPAN 80 coatings are unable to prevent fogging and perform worse than unmodified polycarbonate.  \n\n![](images/df8b4ad74dda8d09b47ede1a7260d7ccc67e95e8f0ae17e71694eaa7e975d085.jpg)  \nFigure 7. Optical images for polycarbonate, and different coated polycarbonate substrates within a controlled environment, fogging chamber (relative humidity $\\mathbf{\\Phi}=\\sim54\\%$ and substrate temperature of ${\\sim}14~^{\\circ}\\mathrm{C}\\ '$ over a period of $40\\ \\mathrm{min}$ .  \n\nAn interesting phenomenon observable from the data shown in Figure 8B is the recovery of the ICF values (transparency) for PVP, and the SPAN coatings after extended fogging times. This somewhat surprising observation can be explained based on the transition from small-scale dropwise condensation to larger scale film-wise condensation on the fogged surfaces. The formation of a continuous water film, as opposed to discrete droplets (which scatter light), increases the transmissivity for these fogged surfaces. Although this recovery is observed, it does not occur rapidly enough to be considered to be sufficiently antifogging.  \n\nAll polysorbate-based coatings demonstrated good antifog performance as shown in Figure 8C. The differences in performance between each polysorbate additive can be related to their HLB values. PS85, having the higher HLB value fogs at around the $10\\ \\mathrm{min}$ mark (ICF values ${\\sim}0.90\\$ ), but recovers almost immediately. This rapid, but quickly dissipating fog can also be seen in optical images (Figure 7). For the higher HLB value PS80 and PS20 coatings, no fogging occurred throughout the duration of the experiment and minor differences in the data shown are likely due to image distortion. PS20 samples had minimal condensation and no fogging and proved to be exceedingly wear-resistant.  \n\n![](images/97e5412c7a5f23edaa98e7e0b6d239c0b13624785bd639187a477968044a40c0.jpg)  \nFigure 8. (A) The ICF values for the optimized PS20 coating compared with PVP and PC over a time period of $40~\\mathrm{min}$ in the fogging chamber. (B) ICF values for the PVP coatings with $20\\%$ PETRA and three different surfactant additives (PS 20, SPAN 20, and SPAN 80). (C) ICF values for PVP coatings with different polysorbate surfactants. (D) ICF values during cyclic fog testing. We report the ICF values after $20~\\mathrm{min}$ for each fogging cycle. PVP and polycarbonate reference lines indicate ICF values for these reference substrates in the first fogging cycle after $20~\\mathrm{min}$ . (E) $\\%$ transmission and (F) $\\%$ haze vs light wavelength for polycarbonate and polycarbonate coated with $\\mathrm{PVP}/20\\%$ PETRA/ $15\\%$ surfactant before fogging.  \n\n![](images/fc239bb06a921e48845bb5d8e2b7cbba1ef3346a558e86473a08185ebe3bbade.jpg)  \nFigure 9. (A) ICF values as a function of time for PC, optimized PS 20 coating, and different commercial coatings\u0001revision wipes, Optix, Exxene, and Ops drops. Optical images for the different samples after $40~\\mathrm{min}$ in the fogging chamber are also shown. (B) Fog testing after wiping each sample 500 times with a microfiber lens wipe. Optix was tested immediately after wiping and one PS20 coating was tested immediately after wiping, while another was tested after $24{\\mathrm{~h}}.$ . Optical images for the different samples after $10\\ \\mathrm{min}$ in the fogging chamber are also shown.  \n\nThe best performing antifog formulation, PS20, was also examined in terms of repeated fog exposure. For this experiment, $20~\\mathrm{min}$ fog cycles were used, and an initial heating step was utilized to ensure similar levels of condensation for each cycle (see the Materials and Methods section and the  \n\nSupporting Information). Figure 8D reports the ICF values for the PS20 coating at the final 20th minute of each cycle. The dashed lines for polycarbonate and PVP indicate the ICF values at fog onset on those samples after about $10~\\mathrm{min}$ in the fogging chamber. The data shows that even after 15 cycles, the highly durable PS20 coating maintains its excellent antifog performance. It is important to note that the fogging procedure employed here is significantly more aggressive than what has been typically utilized in previous work, such as directly breathing on a cold surface. Figure 8E,F demonstrate the optical properties of uncoated PC and different coated substrates. As shown in Figure 8E, no discrimination can be made between the coatings based on UV−vis transmittance data alone since all curves overlap. However, $\\%+\\mathrm{Iaze}$ spectra for each coating in Figure 8F yielded notable differences. The data in Figure 8F show that the haze caused by the PS 20 coating is essentially identical to the uncoated polycarbonate and that the amount of haze caused by the coated surface seemed to correlate with the $S^{*}$ values, with the lowest $S^{*}$ values causing the least amount of haze. This is likely due to the increase in the miscibility between the surfactant and the PVP matrix with decreasing $S^{*}$ values.  \n\n3.5. Comparison to Commercial Antifogging Coatings. To validate the wear and antifog performance of the optimized PS20 antifog coating formulation, it was compared against three commonly sold temporary antifog treatments and one commercial polyurethane-based antifog coating. Figure 9A demonstrates the antifog performance of the PS20 coating against different temporary coatings such as Optix, Ops Drops, Revision wipes, and an Exxene HCF-100 commercial antifog coating. The samples were fog tested in the same manner as previously described. The tests reveal that Optix and the PS20 coating demonstrated excellent, sustained antifogging properties despite Optix being a temporary solution. Ops Drops performed to a lesser degree, while Revision appeared to yield negligible antifogging benefits. Exxene was able to delay fogging for ${\\sim}20~\\mathrm{min}$ but fogged soon after as indicated by a decline in ICF values. Water contact angle measurements and abrasion testing on the different commercial coatings are provided in Figures S5 and S6. Since the temporary antifog agents exist as free macromolecules on the surface, they impart a lubricating effect on the surface and therefore provide a degree of wear resistance. However, unlike our coating which contains embedded slip additive within the film network, these ephemeral antifog solutions can only offer wear resistance for a short duration and can be easily removed mechanically. Exxene does not contain any slip additives but is composed of a durable polyurethane and therefore proved to be highly wear resistant. However, as described earlier, the coating demonstrates relatively poor antifog performance.  \n\nTo confirm that the excellent antifog performance of our coatings is not an artifact of our antifog testing methodology, we also conducted fog testing of the fabricated PS20 coatings and a few commercial coatings (Revision and Ops Drops) in a fog tester developed by the US Army Soldier Center (see the Materials and Methods section). Images from that test are shown in Figure 10. Only the PS 20 coatings passed the US Army antifog test, while the other commercial coatings failed, validating the excellent antifog performance of the PS 20 coating.  \n\nNext, we evaluated the regenerative properties of our optimized PS 20 coating. Figure 9B shows the antifogging performance of the Optix and PS20 coatings after 500 Taber abrasion cycles with a microfiber lens wipe. Fog testing was conducted both immediately after the wiping cycles, and a day later. As can be seen from the data, the antifog properties of PS20 declined slightly after 500 wiping cycles, but eventually improved as the test progressed. When the fogging tests were conducted 1 day after the 500 microfiber wipes, the coating maintained ICF values $>0.9$ throughout the duration of the test. In comparison, the antifog properties of Optix coating are completely depleted after 500 microfiber wipes, and the surfaces displayed immediate, and nonrecoverable fogging.  \n\n![](images/affe69d1487b9ad851fcb8d9c8ab43d1faa3775a2cd5e6f329a989aab0633cdb.jpg)  \nFigure 10. Comparative antifog performance for uncoated polycarbonate, wear-resistant PS20 coating, and two different commercial antifog coatings\u0001revision wipes, Ops drops within a fog tester developed by US Army soldier research center (see the Materials and Methods section). Visual pictures from the fog tester camera show the haze in each sample at intervals of $20~\\mathrm{s}$ .  \n\nAdditionally, we measured the long-term water contact angle values on our coating, as well as plasma-treated polycarbonate, Optix, Exxene, and cross-linked PVP. Over the course of 5 weeks, our coating maintained its low water contact angles while all other formulations experienced a gradual increase (Figure S7) likely due to surface fouling from low surface energy molecules present in the environment. This data highlights how the use of surfactants can overcome one of the major challenges associated with antifog coatings−degradation in performance over the long-term due to fouling from low surface energy molecules.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 4. CONCLUSIONS  \n\nIn this work, we have engineered different abrasion-resistant antifog coatings that can maintain their properties over the long-term. These coatings were developed based on the classic Ratner−Lancaster relation wear model for polymers and utilized the introduction of coating toughening agents and low-friction slip additives within a previously well studied polymer with antifog properties\u0001PVP. The additives identified in this work enhanced the abrasion resistance of the coating by over 500-fold when compared with unmodified PVP. Additionally, HLB values, and a unique miscibility factor that utilizes the Hansen solubility parameters $(S^{*})$ , were investigated as criteria for enhancing antifogging performance and coating durability. We illustrated that friction reduction is independent of additive HLB values and $S^{*}$ , while the optical clarity and the antifog ability can be improved by lower $S^{*}$ and higher HLB values, respectively. Our optimized PVP antifog coating demonstrates continuous antifogging performance and strong wear resistance, and significantly outperformed all tested commercially available antifog coatings in terms of antifog performance, wear resistance, and long-term cyclical performance. Overall, the incorporation of toughening agents and hydrophilic slip additives to existing hydrophilic antifog polymers offers a new strategy for developing high-performance, and durable antifog coatings.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 7,
+        "chunk": "# ASSOCIATED CONTENT",
+        "category": " References"
+    },
+    {
+        "id": 8,
+        "chunk": "# $\\bullet$ Supporting Information  \n\nThe Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.3c17117.  \n\n(A) Change in $\\scriptstyle{\\mathrm{C}}={\\mathrm{O}}$ bond for a PVP antifog coated polycarbonate as a function of UVC exposure time, (B) change in acrylate peak of pure PETRA coated polycarbonate with increasing UVC exposure, Hansen solubility parameters calculated by HSPiP software, select Surfactants and corresponding HLB values and $S^{*}$ values, average steady-state friction coefficients of polycarbonate and antifog coated polycarbonate, linear Tabor abrasion setup for antifog coated polycarbonate and the SEM image of the microstructure of the CS-5 felt tip abrasion tip, list of experiments demonstrating material and additive effects on sequential abrasion resistance to CS-5 Tabor Abrasion under increasing mass, a schematic diagram of the test chamber, the humidity and temperature evolution during the experiments, static water contact angles for different commercial antifog coatings, as well as the optimal PS20 coating developed in our work, change in roughness of commercial antifog formulations and, polycarbonate (PC), and the PS20 antifog coating after 8000 CS-5 abrasion cycles, longevity of static water contact angle performance with extended exposure time to normal environmental conditions (PDF)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# AUTHOR INFORMATION",
+        "category": " References"
+    },
+    {
+        "id": 10,
+        "chunk": "# Corresponding Author  \n\nAnish Tuteja − Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States; Department of Chemical Engineering, Department of Macromolecular Science and Engineering, and Biointerfaces Institute, University of Michigan, Ann Arbor, Michigan 48109, United States; orcid.org/0000-0002- 2383-4572; Email: atuteja@umich.edu",
+        "category": " References"
+    },
+    {
+        "id": 11,
+        "chunk": "# Authors  \n\nBrian Macdonald − Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States   \nFan-Wei Wang − Department of Chemical Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States; $\\circledcirc$ orcid.org/0000-0002-6401-4255   \nBrian Tobelmann − Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States   \nJing Wang − Department of Mechanical Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States; $\\circledcirc$ orcid.org/0000-0002-7757-1261   \nJason Landini − Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States   \nNipuli Gunaratne − Department of Chemical Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States   \nJoseph Kovac − Department of Aerospace Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States  \n\nTodd Miller − Protection Materials Division, Soldier Protection Directorate, US Army DEVCOM Soldier Center, Natick, Massachusetts 01760, United States Ravi Mosurkal − Protection Materials Division, Soldier Protection Directorate, US Army DEVCOM Soldier Center, Natick, Massachusetts 01760, United States; $\\circledcirc$ orcid.org/ 0000-0002-2769-2292  \n\nComplete contact information is available at: https://pubs.acs.org/10.1021/acsami.3c17117",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# Author Contributions  \n\nThe manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.",
+        "category": " References"
+    },
+    {
+        "id": 13,
+        "chunk": "# Funding  \n\nThis work was financially supported by the US Army DEVCOM Soldier Center, Natick, MA, (Contract#: FA9300- 20-F-9801)# which is gratefully acknowledged and approved for Public Release (PAO #PR2023-204).",
+        "category": " References"
+    },
+    {
+        "id": 14,
+        "chunk": "# Notes  \n\nThe authors declare no competing financial interest.",
+        "category": " References"
+    },
+    {
+        "id": 15,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nB.M thanks the National Science Foundation for the NSF GRFP Fellowship in support of this work. We thank Andrea Poli for the instruction and usage of the RSA-G2 DMA. R.M. thanks Joseph Palomba and David Ziegler for the help in the Antifog testing. The authors acknowledge the financial support of the University of Michigan College of Engineering and technical support from the Michigan Center for Materials Characterization.",
+        "category": " References"
+    },
+    {
+        "id": 16,
+        "chunk": "# REFERENCES  \n\n(1) Duran, I. $|\\mathrm{R}.|$ ; Laroche, G. Current trends, Challenges, and Perspectives of Anti-fogging Technology: Surface and Material Design, Fabrication Strategies, and Beyond. Prog. Mater. Sci. 2019, 99, 106−186. (2) Gustave, A. Anti-fogging Eyeglasses. U.S. Patent 3,160,735 A, 1964. (3) Dain, S. J.; Hoskin, A. K.; Winder, C.; Dingsdag, D. P. Assessment of Fogging Resistance of Anti-fog Personal Eye Protection. Ophthalmic. Physiol. Opt. 1999, 19 (4), 357−361. (4) Crebolder, J. M.; Sloan, R. B. Determining the Effects of Eyewear Fogging on Visual Task Performance. Appl. Ergon. 2004, 35 (4), 371−381. (5) Margrain, T. H.; Owen, C. The Misting Characteristics of Spectacle Lenses. Ophthalmic. Physiol. Opt. 1996, 16 (2), 108−114. (6) Practical Considerations for Management of Pediatric Victims during Hazmat Decontamination, 2005. Citeseer. (accessed). (7) Caretti, D. M.; Conye, K. Development of an Objective Method of Respiratory Protective Mask Lens Fogging: Data Acquisition and Image Processing Proof of Concept. Ph.D. Thesis, Oak Ridge Institute for Science and Education, Oak Ridge, TN, ADA 417285, 2003. (8) Luria, S. M.; Neri, D. F.; Kinney, J. S.; Paulson, H. M.; Naval Submarine Medical Research Lab Groton CT. Cold Weather Goggles: Optical Evaluation. I; Naval Submarine Medical Research Laboratory, Naval Medical Research and Development Command, 1982. (9) Lu, X.; Wang, Z.; Yang, X.; Xu, X.; Zhang, L.; Zhao, N.; Xu, J. Antifogging and Antireflective Silica Film and its Application on Solar Modules. Surf. Coat. Technol. 2011, 206 (6), 1490−1494. (10) Lawrentschuk, N.; Fleshner, N. E.; Bolton, D. M. Laparoscopic Lens Fogging: a Review of Etiology and Methods to Maintain a Clear Visual Field. J. Endourol. 2010, 24 (6), 905−913.  \n\n(11) Zhang, X.; He, J. Hydrogen-bonding-supported Self-healing Antifogging Thin Films. Sci. Rep. 2015, 5 (1), 9227.   \n(12) Li, Y.; Fang, X.; Wang, Y.; Ma, B.; Sun, J. Highly Transparent and Water-enabled Healable Antifogging and Frost-resisting Films Based on Poly (Vinyl Alcohol)-Nafion Complexes. Chem. Mater. 2016, 28 (19), 6975−6984.   \n(13) Briscoe, B. J.; Galvin, K. P. The Effect of Surface Fog on the Transmittance of Light. Sol. Energy 1991, 46 (4), 191−197.   \n(14) Bhardwaj, R.; Agrawal, A. Tailoring Surface Wettability to Reduce Chances of Infection of COVID-19 by a Respiratory Droplet and to Improve the Effectiveness of Personal Protection Equipment. Phys. Fluids 2020, 32 (8), 081702.   \n(15) Patel, P.; Choi, C. K.; Meng, D. D. Superhydrophilic Surfaces for Antifoqging and Antifouling Microfluidic Devices. JALA 2010, 15 (2), 114−119.   \n(16) Di Mundo, R.; d’Agostino, R.; Palumbo, F. Long-lasting Antifog Plasma Modification of Transparent Plastics. ACS Appl. Mater. Interfaces 2014, 6 (19), 17059−17066.   \n(17) Chen, F.; Liu, J.; Cui, Y.; Huang, S.; Song, J.; Sun, J.; Xu, W.; Liu, X. Stability of Plasma Treated Superhydrophobic Surfaces under Different Ambient Conditions. J. Colloid Interface Sci. 2016, 470, 221−228.   \n(18) Wenzel, R. N. Resistance of Solid Surfaces to Wetting by Water. Ind. Eng. Chem. Res. 1936, 28 (8), 988−994.   \n(19) Park, K.-C.; Choi, H. J.; Chang, C.-H.; Cohen, R. E.; McKinley, G. H.; Barbastathis, G. Nanotextured Silica Surfaces with Robust Superhydrophobicity and Omnidirectional Broadband Supertransmissivity. ACS Nano 2012, 6 (5), 3789−3799.   \n(20) Xu, H.; Liu, L.; Wu, F.; Xu, D.; Lu, N. Fabrication of Biomimetic Patterns for High Transmission and Antifogging Property. RSC Adv. 2015, 5 (35), 28014−28018.   \n(21) Utech, S.; Bley, K.; Aizenberg, J.; Vogel, N. Tailoring Reentrant Geometry in Inverse Colloidal Monolayers to Control Surface Wettability. J. Mater. Chem. A 2016, 4 (18), 6853−6859.   \n(22) da Silva, M. N.; Santilli, C. V.; Pulcinelli, S. H. Wettability and Photodegradation Activity of Sol-gel Dip-coated Zinc Oxide Films. J. Sol-Gel Sci. Technol. 2012, 63 (2), 230−234.   \n(23) Maino, G.; Meroni, D.; Pifferi, V.; Falciola, L.; Soliveri, G.; Cappelletti, G.; Ardizzone, S. Electrochemically Assisted Deposition of Transparent, Mechanically Robust TiO 2 Films for Advanced Applications. J. Nanopart. Res. 2013, 15 (11), 2087.   \n(24) Wang, R.; Hashimoto, K.; Fujishima, A.; Chikuni, M.; Kojima, E.; Kitamura, A.; Shimohigoshi, M.; Watanabe, T. Light-induced Amphiphilic Surfaces. Nature 1997, 388 (6641), 431−432.   \n(25) Haga, M.; Onisawa, Y.; Shimizu, K. Plastic Lenses and Method of Producing the Same. U.S. Patent 5,985,420 A, 1999.   \n(26) Grube, S.; Siegmann, K.; Hirayama, M. A Moisture-absorbing and Abrasion-resistant Transparent Coating on Polystyrene. J. Coat. Technol. Res. 2015, 12 (4), 669−680.   \n(27) Howarter, J. A.; Youngblood, J. P. Self-Cleaning and Next Generation Anti-Fog Surfaces and Coatings. Macromol. Rapid Commun. 2008, 29 (6), 455−466.   \n(28) Ezzat, M.; Huang, C.-J. Zwitterionic Polymer Brush Coatings with Excellent Anti-fog and Anti-frost Properties. RSC Adv. 2016, 6 (66), 61695−61702.   \n(29) Lee, H.; Alcaraz, M. L.; Rubner, M. F.; Cohen, R. E. Zwitterwettability and Antifogging Coatings with Frost-resisting Capabilities. ACS Nano 2013, 7 (3), 2172−2185.   \n(30) Cebeci, F. C. ̧ ; Wu, Z.; Zhai, L.; Cohen, R. E.; Rubner, M. F. Nanoporosity-driven Superhydrophilicity: a Means to Create Multifunctional Antifogging Coatings. Langmuir 2006, 22 (6), 2856−2862. (31) Chevallier, P.; Turgeon, S.; Sarra-Bournet, C.; Turcotte, R.; Laroche, G. Characterization of Multilayer Anti-fog Coatings. ACS Appl. Mater. Interfaces 2011, 3 (3), 750−758.   \n(32) Florea-Spiroiu, M.; Achimescu, D.; Stanculescu, I.; Purica, M.; Gavrila, R.; Peretz, S. Anti-fog Chitosan/sodium Lauryl Ether Sulfate Films. Polym. Bull. 2013, 70, 3305−3316.  \n\n(33) Nuraje, N.; Asmatulu, R.; Cohen, R. E.; Rubner, M. F. Durable Antifog Films from Layer-by-layer Molecularly Blended Hydrophilic Polysaccharides. Langmuir 2011, 27 (2), 782−791. (34) Lancaster, J. Abrasive Wear of Polymers. Wear 1969, 14 (4), 223−239. (35) Shipway, P.; Ngao, N. Microscale Abrasive Wear of Polymeric Materials. Wear 2003, 255 (1−6), 742−750. (36) Ton-That, C.; Teare, D.; Bradley, R. Friction, Surface Oxidation, and Polar Free Energy for Polymer Surfaces by Chemical Force Microscopy. Chem. Mater. 2000, 12 (8), 2106−2111. (37) Myshkin, N.; Kovalev, A. Adhesion and Surface Forces in Polymer Tribology\u0001A Review. Friction 2018, 6 (2), 143−155. (38) Nocita, D.; Critchlow, G.; Haworth, B.; Forte, G.; Hollingbery, L.; Kay, C. Novel Super-hydrophilic Coatings with Enhanced Adhesion on Polyolefin Substrate Obtained by Gravure Deposition of True Amphiphilic Block Co-polymer Water Dispersions. Int. J. Adhes. Adhes. 2022, 112, 103032. (39) Xiang, J.; Liu, X.; Liu, Y.; Wang, L.; He, Y.; Luo, L.; Yang, G.; Zhang, X.; Huang, C.; Zhang, Y. Synthesis of a Novel Anti-fog and High-transparent Coating with High Wear Resistance Inspired by Dry Rice Fields. Chem. Eng. Sci. 2021, 242, 116749. (40) Yuan, Y.; Liu, R.; Wang, C.; Luo, J.; Liu, X. Synthesis of UVcurable Acrylate Polymer Containing Sulfonic Groups for Anti-fog Coatings. Prog. Org. Coat. 2014, 77 (4), 785−789. (41) Ziegler, D. P., Gary; Giardini, Stephen. Fog Tester; United States, 2021. (42) Zhu, X.; Lu, P.; Chen, W.; Dong, J. Studies of UV Crosslinked Poly (N-vinylpyrrolidone) Hydrogels by FTIR, Raman and Solid-state NMR Spectroscopies. Polymer 2010, 51 (14), 3054−3063. (43) England, M. W.; Urata, C.; Dunderdale, G. J.; Hozumi, A. Antifogging/Self-healing Properties of Clay-containing Transparent Nanocomposite Thin Films. ACS Appl. Mater. Interfaces 2016, 8 (7), 4318−4322. (44) England, M. W.; Sato, T.; Urata, C.; Wang, L.; Hozumi, A. Transparent Gel Composite Films with Multiple Functionalities: Long-lasting Anti-fogging, Underwater Superoleophobicity and Antibacterial Activity. J. Colloid Interface Sci. 2017, 505, 566−576. (45) Sato, T.; Amano, A.; Dunderdale, G. J.; Hozumi, A. Transparent Composite Films Showing Durable Antifogging and Repeatable Self-Healing Properties Based on an Integral Blend Method. Langmuir 2022, 38 (32), 9874−9883. (46) Ramani, R.; Ranganathaiah, C. Degradation of Acrylonitrilebutadiene-styrene and Polycarbonate by UV Irradiation. Polym. Degrad. Stab. 2000, 69 (3), 347−354. (47) Höfer, R. Processing and Performance Additives for Plastics. 2012. (48) Cooper, I.; Tice, P. A. Migration Studies on Fatty Acid Amide Slip Additives from Plastics into Food Simulants. Food Addit. Contam. 1995, 12 (2), 235−244. (49) Hansen, C. M. Hansen Solubility Parameters: A User’s Handbook; CRC Press, 2007. (50) Golovin, K.; Boban, M.; Mabry, J. M.; Tuteja, A. Designing Self-Healing Superhydrophobic Surfaces with Exceptional Mechanical Durability. ACS Appl. Mater. Interfaces 2017, 9 (12), 11212−11223. (51) Boban, M.; Golovin, K.; Tobelmann, B.; Gupte, O.; Mabry, J. M.; Tuteja, A. Smooth, All-Solid, Low-Hysteresis, Omniphobic Surfaces with Enhanced Mechanical Durability. ACS Appl. Mater. Interfaces 2018, 10 (14), 11406−11413. (52) Griffin, W. C. Calculation of HLB values of Non-ionic Surfactants. J. Soc. Cosmet. Chem. 1954, 5, 249−256.",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Emerging Trends in Machine Learning: A Polymer Perspective Tyler B. Martin\\* and Debra J. Audus\\*  \n\n![](images/929c64894068bb7968d30b73839ccca3dda2c2deaa3d3985497ca343dd19b3a9.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Read Online",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# ACCESS  \n\nMetrics & More  \n\nABSTRACT: In the last five years, there has been tremendous growth in machine learning and artificial intelligence as applied to polymer science. Here, we highlight the unique challenges presented by polymers and how the field is addressing them. We focus on emerging trends with an emphasis on topics that have received less attention in the review literature. Finally, we provide an outlook for the field, outline important growth areas in machine learning and artificial intelligence for polymer science and discuss important advances from the greater material science community.  \n\n![](images/379df12f52d820c9b680740ddc3180ba498b5dd53b636272e8b6a0ec65fb7693.jpg)  \nArticle Recommendations  \n\nKEYWORDS: Polymers, Machine Learning, Artificial Intelligence, Autonomous Experimentation, Transfer Learning, Explainability, Optimization, Inverse Design, Deep Learning, Open Science",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# INTRODUCTION  \n\nArtificial intelligence (AI) has already revolutionized our daily lives from self-driving cars to semantic language translation to tailored content feeds and beyond. The latest AI image generation models can transform text strings into images that can be nearly indistinguishable from high-quality human generated art and photography.1 In medicine, machine learning (ML) models are being used to identify carcinogens and diagnose diseases such as Parkinson’s that, previously, could not be identified from biomarkers.2,3 Decades long scientific problems, such as the classic “protein folding” problem, are being tackled by AI that produce results which approach the resolution of our best measurements.4 With each major advance, it is clear that we have yet to realize the full impact of AI and ML.  \n\nEven within the materials science community, the application of ML and AI techniques is becoming routine.5−8 For the purposes of this article, ML is the use of mathematical models to perform well-defined data tasks such as clustering, classification, or regression. AI is a more difficult term to define, but generally refers to the emergent “behaviors” that arise from complex stacks of ML and data models. Given that these terms are often used interchangeably, for simplicity we will refer to ML rather than AI and ML in this article. Over the past five years or so, there has been tremendous progress in the application of these methods to polymer problems as detailed in numerous perspectives and reviews.9−20 Polymers focused researchers are using ML to accelerate the discovery of new materials and new knowledge, as well as working to overcome barriers such as data scarcity. For example, ML has enabled the generation of potential new polymer chemistries,21 new materials for gas separation membranes,22 prediction of properties for sequence defined polymers,23 bioplastic design,24 guidance for improving 3D printing,25 improved contrast agents for magnetic resonance imaging (MRI) measurements,26 and methods for improved predictions of very small data sets.27  \n\nDespite this progress, the field is still plagued by a variety of challenges that arise from both the unique and nonunique problems associated with polymer science. Unlike many kinds of materials, the structure of polymers is inherently stochastic rather than a single structure. This makes the representation of polymers in ML models a challenge. Furthermore, “big data” ML (i.e., data set sizes close to a billion) is currently out of reach for the polymer community as there are no publicly available databases that provide enough well-tagged polymer data to support such an endeavor. Many of the key measurements leveraged in the polymer community rely on instruments made by manufacturers that do not provide open interfaces and data models for their devices, impeding the creation of databases and making the integration of these devices into high-throughput and automation platforms nearly impossible. Table 1 expands upon the current list of challenges facing the polymers community and categorizes them into broad areas.  \n\nIn this paper, we first give an overview in Creating an ML Pipeline and then provide Updates on two of the largest challenges that continue to plague the polymers community: Data and Polymer Representations. Next, we highlight growth areas, many of which have received less focus in recent polymer reviews, in New Progress. Since polymer ML is a rapidly growing field, especially since 2017, we focus on recent studies and limit discussion on topics that are well-covered in recent reviews, such as the application of ML to simulations (see refs 11 and 28) and inverse design (see ref 15). Finally, we conclude with an Outlook section that provides an editorial assessment on several of the areas of new progress and discusses important, but less discussed topics including the role of Open Science and Best Practices and Challenge Problems within the ML space. To further guide the reader, we have provided key connections between the outstanding challenges and how the polymer community is addressing these challenges as categorized by paper subsections in Table 1.  \n\nTable 1. Challenges Facing the Polymer Machine Learning Community   \n\n\n<html><body><table><tr><td>category</td><td> challenge</td><td> paper section</td></tr><tr><td>polymer nature</td><td> polymer structure is stochastic and hierarchical</td><td> Data, Polymer Representations, Deep Learning</td></tr><tr><td> polymer nature</td><td>morphology is process history dependent</td><td>Data, Domain Knowledge, Optimization and Inverse Design</td></tr><tr><td>polymer nature, community</td><td>data is not produced in standardized formats</td><td> Data, Polymer Representations, Unsupervised Analysis</td></tr><tr><td>community</td><td>(meta)data is not complete, accessible, or shared</td><td>Data, Unsupervised Analysis, Open Science</td></tr><tr><td>community</td><td>code is not accessible or open</td><td>Open Science</td></tr><tr><td>community</td><td>available data is small and disperse</td><td>Data, Data Fusion and Transfer Learning, Domain Knowledge, Open Science, Beyond Polymer Autonomous</td></tr><tr><td>community</td><td>analyses are not reproducible</td><td>Open ScienceBest Practices and Challenge Problems</td></tr><tr><td>community</td><td> models do not provide uncertainty quantification</td><td>Data, Autonomous Experimentation, Data Fusion and Transfer Learning, Best Practices and Challenge Problems</td></tr><tr><td>community</td><td>models are not explainable</td><td>Interpretability and Explainability, Domain Knowledge, Unsupervised Analysis</td></tr><tr><td>community</td><td>models do not extrapolate</td><td>Domain Knowledge</td></tr><tr><td>hardware</td><td>custom hardware is hard to use and adapt outside of Autonomous Experimentation initial study</td><td></td></tr><tr><td>hardware</td><td>commercial hardware has poorly documented or closed interfaces</td><td>Beyond Polymer Autonomous</td></tr><tr><td>all </td><td>large combination of skills needed to carry out studies</td><td>Data, Autonomous Experimentation, Beyond Polymer Autonomous </td></tr></table></body></html>  \n\n![](images/fb8ee1244ed31d096fd88e78328e7da3f8219ffd93205ee728997579cecc9ece.jpg)  \nFigure 1. Typical pipeline for polymer ML. We emphasize that due to the rapidly growing field of $\\mathbf{ML}$ , this pipeline does not cover all potential use cases. Acronyms include Gaussian process regression (GPR), neural network (NN), mean squared error (MSE).",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# CREATING AN ML PIPELINE  \n\nHere, we provide a brief overview of the steps from conceptualization to a production ML model as shown in Figure 1. We emphasize that these steps are often a simplification of the complicated pipelines that are currently being constructed and used in production environments and that we only seek to provide a broad overview for the uninitiated reader. We direct the reader to other resources for more complete treatments of ML and model building.29−32  \n\nThe first and most important step in developing a production ML model is problem identification. In polymer science, the there are typically two ultimate goals for ML: materials/process design and knowledge discovery. For materials/process design, example goals could be a new polymer chemistry, a new processing protocol or a new formulation. These challenges often fall under the umbrella of inverse design and normally involve property optimization. For example, selecting the polymer with the highest thermal conductivity33 or balancing multiple objectives.34 For the goal of knowledge discovery, an example could be what processing parameters are essential for a given application. However, a specific ML pipeline might have an intermediate goal such as polymer characterization (including property prediction), generating a fast surrogate model (such as replacing time-consuming experiments or simulations) or generating a database (such as a list of possible polymers or extraction of data from the literature).  \n\nThe second step is data collection, generation, and selection. This could involve running new experiments or simulations, taking data from handbooks (online or otherwise), using other historical data or a combination thereof. Since ML is a datadriven technique, data selection and data quality are particularly important. Missing metadata or improperly collected data can influence models in ways that are difficult to identify and diagnose. For many polymer applications, processing history plays an essential role and this information must be captured in the metadata for ML models to be effective. At this step, if applicable, it is recommended to consider the uncertainty and determine the intrinsic error in the data set as an ML model cannot make predictions at a higher accuracy then the original data set unless additional knowledge is encoded in the model. Next, the data may need to be cleaned. This involves everything from identifying biases in the data set (such as certain values being more likely than others) to finding outliers (which could be either erroneous or interesting data) to normalizing the data.  \n\nThe fourth step is featurization. This includes converting chemistry into machine readable quantities (i.e., features), a process known as fingerprinting. This can be done with handcrafted features or using ML techniques to automatically perform the featurization. Examples of featurization include images being fed into convolutional neural networks (where the convolutional layers automatically featurize the data) or encoding the chemistry and bond connectivity of molecules in graph neural networks. At this stage, it is also advisable to identify correlations between features and determine if fewer features can be used especially if there is data scarcity.  \n\nNext is model selection. There are a variety of ML models crafted for different tasks. For example, in regression, which can be used for property prediction, a continuous output, such as density, is predicted as a function of an input, such as chemistry.  \n\nClassification is similar, but the output is a discrete class such as phase separated versus homogeneous. Both of these tasks are considered supervised since the training data is labeled with an output (e.g., the density value or homogeneous/separated class). Clustering is used to group data together and can be used to identify different phases even if the type of phase is unknown. Dimensionality reduction can be used to generate knowledge by projecting complicated, high dimensional data onto a lower dimensional space that may be easier to interpret. Clustering and dimensionality reduction are considered unsupervised when the data is unlabeled (e.g., the categories in clustering are not known a priori). Generative models are designed to generate new data from existing data, such as new polymer structures from a list of previously synthesized polymers. As is becoming increasingly common, hybrid models are used where multiple ML models are combined. This can be relatively straightforward, such as performing dimensionality reduction on the features prior to another task in order to improve performance. Alternatively, it can be more complicated and integrated with other tasks such as optimization. Independent of the chosen task, key aspects in model choice are simplicity, uncertainty quantification, and performance.  \n\nAfter model selection is model training. This includes separating the training data into batches for separate training, testing, and cross-validation. In also includes optimizing the hyperparameters of the model. This step is particularly important because bad choices of hyperparameters can lead to models with suboptimal predictions and additionally lead to difficulty in the benchmarking step. Success in optimization may depend on the algorithm for optimization, the optimizer parameters and the quantity being optimized (e.g., minimizing mean squared error).  \n\nBenchmarking is particularly important as many aspects of ML (similar to numerics) are still an art form rather than a science. Since model training can be time-consuming, prototyping is highly recommended. It is usually useful to compare more complicated models with simpler models to determine if the additional complexity is helpful or not. Benchmarking could include comparing different model types, different hyperparameters, different data sets, different featurization schemes, etc. Often it is done by comparing error metrics such as mean squared error, $R^{2}$ , or, in the case of classification, $F_{1}$ score. At this stage, visualization of the results is also recommended since few error metrics capture a full picture of the performance. Concerns might include extrapolation or if there are classes that are more accurate than others. For visualization, parity plots can be useful.  \n\nFinally, there is the production model. At this point, the model can be used for its intended purpose (e.g., materials/process design or knowledge discovery). Many model varieties are much faster to execute than they are to train and therefore can be applied repeatedly, or in real time after training. At this point, we highly encourage readers to share their models, benchmarking, generating code and data. As discussed in Open Science, this will ultimately further the two key goals of ML for polymers: acceleration of new materials discovery and new science.  \n\nWhile the above steps describe many ML models in polymer science, ML is a growing field that can defy categorization. Pipelines can become much more complicated by not only combining different ML models as previously discussed, but also by combining data from different sources as discussed in Data Fusion and Transfer Learning and by active learning, a technique where new data is selected iteratively and the ML model is updated. This framework will be discussed in more detail in Autonomous Experimentation.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# UPDATES",
+        "category": " Abstract"
+    },
+    {
+        "id": 7,
+        "chunk": "# Data  \n\nML, by definition, relies on data. As shown in Table 1, ML for polymers has many data challenges. First, there is the issue of not having enough data. Large ML models such as Megatron-Turing Natural Language Generation,35 an advanced language model, and AlphaFold2,4 an accurate predictor of protein structure, rely on enormous data corpora covering billions to hundreds of billions of words or protein sequences.36 Second, there is the issue of not having enough quality data. For example, the glass transition temperature is an important property where there are several data sets, and yet even combining curated data sets can yield large uncertainties. Jha et al. explicitly explored this by combining three curated data sets (two handbooks and one online resource) and found that the intrinsic uncertainty was around $40~\\mathrm{K},^{37}$ which is likely prohibitively large for use in polymer design. They found that using predictions of the median yielded uncertainties roughly similar to the intrinsic or irreducible uncertainty. Thus, the only way to improve the model further is to improve the data. This case study highlights that the issue of data quality is a subtle one and intricately intertwined with the issue of metadata, the contextual information for the data. Polymers are particularly complicated because (1) they are intrinsically stochastic in nature\u0001 composed not of a single molecule type, but an ensemble of different structures, (2) their properties can significantly depend on their processing history, (3) measurements can often depend on instrument settings, and (4) uncertainty quantification in both the data and metadata is often critical. Thus, it is essential to capture and ultimately use both the data and metadata in ML pipelines. Proprietary and nonstandardized data formats further exacerbate these issues. A list of different methods for obtaining data and considerations is shown in Table 2. Note that these considerations are directly related to the aforementioned challenges.  \n\nTo tackle these data and metadata related issues, which are ultimately issues associated with making data Findable, Accessible, Interoperable and Reusable (FAIR),38 there are several options. First, there are painstakingly curated handbooks and online resources, many of which include relevant metadata. However, the data set sizes are fixed and the sources can be varied resulting in heterogeneous data. Refer to Table 1 of refs 12, 13, and 14 for useful lists of such resources.  \n\nTable 2. Methods for Obtaining Data and Corresponding Considerations   \n\n\n<html><body><table><tr><td>method</td><td>considerations</td></tr><tr><td>manual high-throughput experiments</td><td>very limited data set sizes need custom hardware</td></tr><tr><td>high-throughput simulations natural language processing</td><td>need specialized skill set need specialized skill set data can be heterogeneous</td></tr><tr><td>curated databases</td><td>need specialized skill set metadata may not be available uncertainty may not be available</td></tr><tr><td></td><td>limited data set sizes data can be heterogeneous metadata may not be available</td></tr><tr><td>user populated databases</td><td>uncertainty may not be available data collection may be manual (no API) data can be heterogeneous metadata may not be available uncertainty may not be available</td></tr></table></body></html>  \n\nAnother option is high-throughput experiments.39 This idea is not a new one as detailed in a recent comment16 and has the benefit of incorporating the relevant metadata from the start by ensuring that experiments are performed consistently. However, it cannot be broadly applied as some systems and measurements are unsuited for such experiments due to long measurement times or difficult to automate material processing steps. Furthermore, the development of high-throughput platforms can be prohibitively costly in time, money, and resources. Despite this, many researchers have pursued the development of high-throughput techniques and one branch of this field will be discussed in the Autonomous Experimentation section below.  \n\nThere are also high-throughput simulations,40−45 which face the same benefits and challenges as high-throughput experiments with the notable differences that data and metadata from simulations are intrinsically machine readable and that simulations are often not quantitatively predictive of experiments. Thus, for polymer design, simulations are used to identify potential candidates41 or in the case of property predictions, experimental and simulation data must be merged or otherwise used.42,43  \n\nAn orthogonal approach is to use ML itself to find polymer data that is published in the literature, an approach known as natural language processing (NLP). There has been some promising progress in this area notably in identifying polymer names,46 recognizing that the same polymer is referred to by different name s,47 developing pipelines for property extraction,48,49 and generating knowledge via word embeddings, which represent words as vectors.50 However, the issue of deciphering the polymer name and capturing all of the relevant metadata is still not fully solved. Nonetheless, it is a promising area. For example, Lin et al. developed PolyName2Structure, which takes in polymer names (common, source, or structure) and then predicts monomers, predicts reactions, and simulates those reactions in order to yield a polymer structure.51 Progress in the broader materials domain6 shows that NLP may be a promising approach to not only get materials data, but also materials knowledge. However, for the average polymer ML developer, the skill set required to use NLP is likely prohibitive, especially since NLP suffers from many of the same problems as manually curated data sets from a data user perspective.  \n\nFinally, another approach is to provide a resource where individual polymer scientists can deposit their data and metadata through a robust data model. This is the idea behind MaterialsMine,52,53 which focuses on nanocomposite and mechanical metamaterials, and the Community Resource for Innovation in Polymer Technology (CRIPT), which considers all varieties of polymeric materials.54 MaterialsMine currently serves not only as a data resource, but also provides additional features on their platform to process and visualize data. For full details, we refer the reader to their Web site52 and article.53 For CRIPT, a key part of this resource will be making it easier for polymer scientists to do science through advanced search, data visualization and private data sharing prepublication. For more information, see their Web site.54 It builds on ideas that are already being implemented in industry,55 and brings them to the public domain. Furthermore, it enables polymer ML by following FAIR data practices including the use of an API (Application Programming Interface) and a web-based interface for both data deposit and access.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# Polymer Representations  \n\nFor ${\\mathrm{ML}},$ chemical structures must be represented in a machine readable format. Utilizing advances in the representation of small molecules, there are a variety of methods that have been developed to address this problem. As detailed in prior review s,14,15 common options include using group contribution methods, converting line notations to numerical vectors called fingerprints through open software such as RDKit,56 using a graph based representation along with graph convolutional neural networks to represent a 3D molecule in 2D, directly using line notation in text-based ML methods, and developing handcrafted, hierarchical fingerprints to replace or supplement the previously described fingerprints.  \n\nThus, far, most of these methods have focused on homopolymers ignoring the stochastic nature of polymers. A key advance in capturing the stochasticity of polymers is the development of an extension of simplified molecular-input lineentry system (SMILES) to polymers known as BigSMILES, as shown in Figure 2.57 More recently, PolyGrammar was developed to describe polyurethanes using a hypergraph representation.58 However, there is not yet a method to generate fingerprints that encode the stochasticity for all varieties of polymers. The issue of polymer stochasticity is acute for copolymers, polyolefins, and complicated polymer architectures. Kuenneth et al.59 find that for random copolymers, they can simply weight the homopolymer fingerprints by the relative fractions of the two monomers. However, a general solution when there are a large number of different monomers, where the ensemble plays an important role, or the structure of the polymer is nonlinear are not fully solved. One recent effort in this direction using data from simulations found that sequence defined polymers were best represented by a recurrent neural network.60 In a notable work, Patel et al. looked at different ways of encoding sequence and compared their results to nonsequence-specific methods.61 They considered four different data sets, one of which was experimental. Ultimately, they found that the best methods depend on both the property being predicted and the data set. Based on their results, they recommend encoding polymer size, including chemical based information as opposed to one hot encoding when chemistry and extrapolation are important, and making use of the polymer sequence if it is known. Recent work by Aldeghi and Coley worked to address the issue of ensembles of polymers. 62 Specifically, they represented polymers by graphs where atoms were represented by nodes and bonds are represented by edges. Bonds between different monomers were assigned different weights based on their average probability thus allowing one to distinguish a diblock copolymer from a random copolymer. However, this work still needs to be extended to the case of conditional bonding probabilities.  \n\n![](images/501baab43792537b55d9f37f28e0e3029895de89a6873aa62efc6d3cb0555ec4.jpg)  \nFigure 2. Depictions demonstrating how BigSMILES captures different polymer chemistries. Reprinted from ref 57. Copyright 2019 American Chemical Society.  \n\nPerhaps, the largest learning lesson from advances in polymer representation is that the optimal representation is highly likely to depend on the problem at hand (e.g., chemistry, ML model, task), as well as on the amount of data available for training. These interactions will often be nontrivial leading back to a key tenet of ML\u0001that prototyping is essential. Nonetheless, basic guidance such as including metrics that matter (e.g., molecular mass if a property is sensitive to molecular mass) will continue to be important.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# NEW PROGRESS",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# Autonomous Experimentation  \n\nActive learning is an approach in which a ML agent, which generally consists of one or more unsupervised and/or supervised models, is responsible for choosing which data gets added to its training corpus in an iterative fashion.32 This approach is useful when the acquisition of the data is expensive, e.g. when the materials are costly to synthesize or the measurement is slow and tedious. A common class of active learning is Bayesian Optimization (BO) in which the property to be optimized is cast within a Bayesian statistical framework. Of particular importance in these methods is the acquisition function which determines which data point or set of data will be added to the training corpus. Common acquisition functions include pure exploration, pure exploitation, expected improvement, and Thompson sampling.32,64  \n\nWithin the materials community, autonomous experimentation platforms are being developed to perform experiments with little to no intervention from human scientists by leveraging active learning algorithms. These automated and autonomous experiments promise to help scientists discover materials with optimized properties more quickly, map phase spaces more accurately, and use less material in the pursuit of these goals. Automated and high-throughput robotic platforms do not require breaks and can operate with higher precision and repeatability than their human counterparts. Furthermore, automated systems tend to naturally integrate with databases and materials ML platforms as the metadata for each sample is likely already digitized as part of the preparation process. Most importantly though, automated and autonomous experiments free the scientist to spend less time and energy on the tedium of running a particular experiment and more time on interpreting the data and planning the next one.  \n\nWhile there have been several recent studies focusing on developing active learning techniques for polymers using premeasured data sets, theory or simulations,65−70 here we focus on experimentally realized autonomous platforms. These studies either directly or indirectly address key challenges in applying ML to polymers as outlined in Table 1. Building automated platforms requires a confluence of skills (from machining to robotics to software development) that can be difficult to find in a single researcher or polymer research group, so these studies are often collaborative. A reality of polymer materials is they are often used or studied in nonequilibrium or kinetically trapped states and that their properties are processing history dependent. Automated platforms can help mitigate or facilitate the study of process history and nonequilibrium phenomena through their control and repeatability. Furthermore, robotic automation often provides a more direct route to quantifying certain parts of the uncertainty in material synthesis.  \n\n![](images/1a6052809c11cecabafff05a9da62f63921db374cb1f5e4c9b5f0de7d7da4bdd.jpg)  \nFigure 3. Schematics and pictures of two autonomous experimentation platforms. (a) Automated continuous flow reactor for optimizing copolymer synthesis of $^{19}\\mathrm{F}$ MRI agents. Reprinted from ref 26. Copyright 2021 American Chemical Society. (b) Automated mixing and characterization platform for studying surfactant properties and phase behavior. Reprinted with permission under a Creative Commons CC-BY 4.0 License from ref 63. Copyright 2021 CellPress.  \n\nWhile significant work has gone into developing synthesis platforms and methods that mostly focus on small-molecule71−73 and colloida $^{74-77}$ synthesis, comparatively less focus has been given to polymer synthesis.78 In the last several years, several groups have taken advantage of the versatility of reversible addition−fragmentation chain transfer (RAFT) polymerization and constructed automated copolymer synthesis platforms.26,79−83 These studies seek to find the polymer sequence or reaction conditions that achieves an optimal material property such as $^{19}\\mathrm{F}$ magnetic resonance signal (MRI) signal for contrast agents,26 retained enzyme efficiency for protein stabilizers,79 or simply the conversion and dispersity of the synthesis itself.80Figure 3a shows one such autonomous synthesis platform from ref 26.  \n\nBeyond synthesis, there are recent studies that focus on optimizing the design of polymer formulations rather than polymer chemistry. In these works, the goal is to find the component composition or processing conditions that optimizes some material property of interest. These include optimizing the degradation behavior of organic photovoltaic films,84 the gelation time and bacterial activity of living silk hydrogels,85 the melting point and electrical properties of deep eutectic solvents,86 and the physical properties and cost of surfactant solutions.63 The inclusion of cost as an optimization variable is notable in that it ensures that the final results balance performance against the bill of materials needed to make the sample, likely making the results more useful to industrial scientists. The idea of including secondary optimization variables can be extended to experimental nonidealities (e.g., slow motor axes, hysteresis) in order to increase the efficiency of the robotic exploration of a material property space.87Figure 3b shows an autonomous formulation platform from ref 63.  \n\nThese studies present a mix of semiautomated26,63,84 and fully automated79,80 platforms. For semiautomated cases, the authors chose to manually perform key processing, purification, or measurement steps rather than attempting to automate them. While fully automated platforms might allow for higher throughput, the development cost, in both money and time, can often outweigh the benefit when the scientific goals of the study can be achieved with minimized, rather than zero user interaction. Furthermore, active learning researchers from outside of the polymer community point out that “human-inthe-loop” agents or “human-machine teaming” can produce better results by taking advantage of the strengths of both humans and machines.69,88,89  \n\nThese above studies present significant variation in the kind of ML models employed in their autonomous agents. For several of the studies,79,80 BO approaches were used with Gaussian Process (GP) models as surrogate optimization functions. Langner et al. chose to use Bayesian neural networks in order to avoid the very poor performance scaling $(O(N^{3}))$ that GPs exhibit with problem size.84 There are methods to improve the performance of GPs for large problems, but they are not necessarily applicable in all cases.90 Interestingly, Reis et al. avoided BO approaches entirely and instead leveraged an AutoML model which predicted ${}^{\\mathrm{i}9}\\mathrm{F}$ MRI signal strength from monomer composition.26 When using an AutoML framework, rather than choosing a specific ML model (e.g., neural network or random forest model) a variety of models are trained and automatically chosen to maximize performance.91,92 By evaluating this model on a grid of monomer composition, the authors could choose the compositions that the model predicted had the highest performance. While this approach loses some of the flexibility and statistical rigor of the BO approaches, it represents an simple and accessible agent to implement and embraces the prototyping nature of ML.  \n\nThere are also several efforts at user facilities and national laboratories to build shareable, open platforms to enable active learning studies. The Polybot system at Argonne National Laboratory offers several stations (synthesis, characterization, processing) between which samples can be shuttled using an mobile platform with a robot arm.93 The Autonomous Formulation Laboratory (AFL) at the National Institute of Standards and Technology is another automation platform designed for conducting machine guided experiments on liquid formulations on neutron and X-ray scattering beamlines.94 These efforts are in the spirit of Open Science, which will be discussed in more detail in the eponymous section below.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# Interpretability and Explainability  \n\nOften polymer scientists desire not only the answer to a problem, such as which polymer material exhibits optimal properties, but also an understanding of why that material is optimal. In the broader ML field this is known as explainable artificial intelligence, or simply, XAI.95 Most efforts in XAI focus either on glass-box models, which are natively explainable (and possibly interpretable) or posthoc methods, which provide explainability for a black box model such as a neural network. This relates to the ultimate ML goal of knowledge generation.  \n\nGlass-box models, as their name suggests, provide insight into how the ML model makes predictions. This is in comparison to black-box models which only provide the prediction and no insight or explanation. Two common approaches are linear models, where the connection between input and output is straightforward, and symbolic regression, where the goal is to create an analytic function that depends on the features. One method that applies both of these approaches is the least absolute shrinkage and selection operator (LASSO) method.96 The basic concept behind LASSO is to combine linear regression with a regularization term that encourages the learned prefactors to be exactly zero, as opposed to small values as in Kernel Ridge Regression.97 The regularization is controlled through a prefactor with larger values corresponding to fewer nonzero prefactors in the linear regression. Thus, LASSO can be used to create linear models that are intrinsically interpretable. It can also be used for symbolic regression by creating a large number of potential terms by combining features through simple or complicated functions (e.g., $x_{1}x_{3}^{2}$ where $x_{1}$ and $x_{3}$ are features) and then selecting only the most salient terms. Two limitations of LASSO are its inability to handle both very large numbers of potential terms and highly correlated terms. To overcome these challenges the sure independence screening and sparsifying operator (SISSO) method was developed.98 SISSO first creates a very large $(O(10^{10}))$ number of features. Then sure independence screening (SIS) is used to correlate the features with the target output keeping only the highest ranked features. Next, a sparsifying operator (SO) is applied to determine the optimal n-dimensional feature vector. This process continues for successively larger $\\mathfrak{n}$ -dimensions until a target error is achieved. Pilania et al. used SISSO in two different ways.99 In the first case, they approached the problem via interpretability by selecting the single most important feature that is a function of the original selection of features. This resulted in an analytic model for the glass transition temperature of polyhydroxyalkanoate polymers with excellent error. In the second case, they used SISSO to create enhanced features under the assumption that mathematical combinations of features that are better correlated with the target property should improve performance compared to using the original features directly.  \n\nSymbolic regression can also be implemented in other ways. (GPSR)100 a different approach is taken to yield an analytic For example, in genetic programming symbolic regression expression that describes the output as a function of a subset of the features. Here, both a list of features and a list of mathematical operators $(\\mathrm{e.g.,\\}+,\\ -,\\times,\\div)$ are provided. They are then represented as a tree with the features as the leaves and operators as nonterminal nodes as depicted in Figure 4a for the expression for polymer entropy. The optimal tree is then determined using evolutionary algorithms such as a genetic algorithm. The benefit of this method is that the search is potentially performed over a larger space. Although, GPSR has yet to be applied in the polymers domain to our knowledge, it has been used for other materials.101,102  \n\n![](images/d2518153dfd583fb32e0ede322fdfbc18c0190abc24138ac59cb902064920ffa.jpg)  \nFigure 4. (a) Tree representation of the equation for polymer entropy $\\scriptstyle\\left(\\bar{\\phi}/N\\ln\\phi\\right)$ . Features $\\cdot\\phi$ and $N_{\\downarrow}$ depicted in orange) are leaves and operators $(\\mathrm{e.g.},\\mathrm{\\times};$ depicted in blue) are nonterminal nodes. (b) SHAP values for the prediction of the radius of gyration $(R_{\\mathrm{g}})$ of sequence defined copolymers. Features including degree of polymerization, monomer in a good solvent ([W]), monomer in a bad solvent ([R]), monomer in a theta solvent $\\left(\\left[\\mathrm{Tr}\\right]\\right)$ , and relative sequence entropy. The figure shows that the degree of polymerization has the largest effect of the features and that larger degrees of polymerization correspond to larger values of $R_{\\mathrm{g}}$ . Monomers in a good solvent have a similar interpretation. Monomers in bad solvent and theta solvent are anticorrelated and have a significantly smaller effect on $R_{\\mathrm{g}}$ . Reprinted in part with permission under a Creative Commons CC-BY 4.0 License from ref 34. Copyright 2021 The Authors.  \n\n![](images/de882a47f1587d2d75c1f82f518062c1ce43e84a73f149befe21b5b4a2800d84.jpg)  \nFigure 5. (a) Example of multitask learning, where the property of interest is fed in as an additional one hot encoded vector. Properties to predict include the glass transition temperature $(T_{\\mathrm{g}})_{\\mathrm{\\ell}}$ , the melting temperature $\\left(T_{\\mathrm{m}}\\right)$ , and the degradation temperature $\\left(T_{\\mathrm{d}}\\right)$ . Reprinted from ref 27. Copyright 2019 American Chemical Society. (b) Example of reusing nodes from a neural network trained on small-molecule-specific heat capacity at constant volume $(C_{\\nu})$ to predict polymeric-specific heat capacity at constant pressure $(C_{\\mathfrak{p}})$ . Reprinted in part from ref 59. Copyright 2021 American Chemical Society. (c) Example of multifidelity modeling. Reprinted from ref 114. Copyright 2020 American Chemical Society.  \n\nThere are also other techniques such as explainable boosting machines (EBMs).103 EBMs are a form of a generalized additive model where the output is typically a sum of nonlinear and nonsmooth functions of each feature. This means that the relative contribution of each feature on the output is trivial to discern. Although they can be slow to train, evaluation is quick and accuracy can be on par with black-box models. Instead, the main limitation is that the additive model assumption may not be an accurate assumption for every system or problem.  \n\nThere are also a variety of posthoc analysis methods. The most common methods are SHapley Additive exPlanations (SHAP)104 and Local Interpretable Model-Agnostic Explanations (LIME).105 Both of these approaches are model agnostic. SHAP takes a game theoretic approach to determine the impact of all the features on a given output. Specifically, for a single training data point, each feature is assigned a SHAP value where the sum of all of the SHAP values is equal to the difference between the given output and the expected output across all of the training data. These SHAP values can then be computed across the entire training data set to give an overall understanding of how different features affect the predicted results including the magnitude of such predictions. An example of such a plot is shown in Figure 4b. LIME uses a different approach. First, one chooses a particular output that they want to explain. Then the input is perturbed in various ways. Next, a local (often linear) model is trained weighting data points that are closer to the desired state that was queried. The local model can then be used to describe why the original ML model made its predictions for a given instance.  \n\nIn the context of polymers, SHAP has been used to investigate the contributions of various features.34,79,106,107 For example, it has been used to determine which functional groups and polymer properties are most predictive of membrane permeability.106 It has also been used to look at the effect of monomer type and degree of polymerization on protein stability for polymer−protein hybrids. In this example, they also used active learning and probed how the SHAP values changed as a function of the iteration.79 Recently, Amamoto et al. used both SHAP and LIME to understand important regions in 2D wide-angle X-ray diffraction and small-angle X-ray scatting measurements when using convolutional neural networks to predict polymer type and annealing temperature.108 Although more simplistic than both SHAP and LIME, partial dependence plots (PDP), which show the marginal effect of only one or two key features can provide qualitative guidance. For example, Bejagam et al. look at the two most important features and determine its nonlinear effect on the melting temperature.109 Ultimately, they conclude that molecular compactness plays a key role.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# Data Fusion and Transfer Learning  \n\nThe goal of data fusion is to achieve synergy by combining, potentially several, but at least two different data sets. This is analogous to the motivation for multimodal measurements in a non-ML context.110 Data fusion can be accomplished both in the context of supervised and unsupervised learning. However, as detailed in a general review,11 there are still a variety of outstanding issues such as combining different data types and accurately handling uncertainty.  \n\nNonetheless, data fusion has already shown promise in polymer science, specifically in the form of multitask learning where one model is used to predict multiple quantities. Kuenneth et al. have shown that it can be used to simultaneously predict 36 different polymer properties.107 Ultimately, they found that multitask learning where the desired property is encoded via augmenting the feature input with a property selector works better than either having the ML model predict all of the properties as an output, or predicting each property individually. This is directly a consequence of using neural nets as their ML model and, during model training, this mode of operation allows the optimizer to more effectively use sparse data. A graphical depiction of this scheme as applied to random copolymers59 is shown in Figure 5a. Multitask learning has also been used to predict properties from images of nanocomposites using a convolutional neural network112 and to simultaneously denoise and predict sample characteristics from X-ray hyperspectral images using an autoencoder.113  \n\nRelated to data fusion, transfer learning is a ML technique where information is transferred between tasks (e.g., predictions of glass transition temperature or melting temperature), domains (e.g., polymer literature or webpages) or both. Since information is often transferred from a data-rich task or domain, known as the source, to a data-poor task or domain, known as the target, it allows for improved predictions for the target for smaller data set sizes. Challenges with transfer learning include selecting the appropriate source, selecting the optimal ML model and, critically, how the information is transferred. We refer the reader to an excellent general review on the topic.115 Within polymer science, transfer learning is increasingly being used.27,116−120 For example, Li et al. used it to reconstruct microstructures and generate structure−property predictions for nanocomposites. In this particular case, they use a deep convolutional neural net trained on a nonscientific corpus for their source domain.116 Transfer learning has also been used to make property predictions for extremely small data sets by Yamada et al. Their approach involved generating a large number of potential models that predicted other properties. These models varied both in the model itself, as well as the target property. One example using neural networks is shown in Figure 5b. They then tested all of the models and determined which ones performed best. This allowed for accurate predictions with data set sizes of $O(10)$ .27 Most recently, Lu et al. first trained an unsupervised encoder on TEM images. Then they transferred this encoder to perform other tasks such as morphology classification and nanowire segmentation. Ultimately, for morphology classification, they found they needed less than 10 labeled images per class and, if the underlying distribution was known a priori, only a single labeled image per class was necessary.120 These results are particularly exciting, since manual labeling of data is time-consuming and error prone. Another related concept is that of multifidelity models. These models can be thought of as transfer learning where the source task and the target task predict the same quantity, but at two different levels of fidelity, or accuracy. In this case, the source task is the lower fidelity model that is data-rich, while the target task is a higher fidelity model that is data-poor. For this particular case, a common approach is to train the high fidelity model to learn the scaled difference between the data and the low fidelity model.121 As an example, Venkatram et al. used this technique to predict the tendency to crystallize as a function of chemistry with the high fidelity data set composed of experimental results and the low fidelity data set composed of predictions from group contribution methods.114 This scheme is shown in Figure 5c. By making use of the low fidelity information, they were able to reduce their root mean squared error by almost a factor of 2 compared to a model trained on only the high fidelity data. Similarly, this approach has also been used to predict polymer bandgap.122",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# Domain Knowledge  \n\nA promising area that is just starting to gain traction in ML as applied to polymer science is the idea of using domain knowledge\u0001our cumulative knowledge of polymer science to enhance ML models. Although this is not a new idea in ML it is a powerful one, as detailed in two general123,124 and one materials focused125 reviews. It is also related to the concept of inductive bias,126 where models are modified to bias toward certain solutions over others independent of the training data (e.g., enforcing known constraints). Ultimately, incorporation of domain knowledge can potentially improve both interpolation and extrapolation for the small data set sizes that are common in polymer science. Furthermore, in principle, domain knowledge can be leveraged to address process history dependent data.  \n\nIncorporating domain knowledge can range from conceptually simple to complex. Domain knowledge has commonly been used to select the appropriate feature s127 for a ML model or to enforce known constraints118,128 s uch as transitional invariance. In both of these cases, less data is needed for the same accuracy for interpolation and, in many cases, extrapolation as the constraints and feature correllations do not need to be learned.  \n\nAn exciting idea for incorporating domain knowledge is to make use of theory, which has the possibility of not only improving the ML models, but also working toward explainability and interpretability. For example, Menon et al. developed a hierarchical ML approach.129 First, they use simple physical models to predict basic physical properties. Then, they use the physical properties as features for LASSO to predict a complicated target property. The physics are directly included via the simple physical models, and the final expression is explainable due to the use of LASSO as depicted in Figure 6. More recently, Audus et al. explored different methods for incorporating imperfect theory into ML models with the goal of improving interpolation, extrapolation and explainability.130 Using the simple case study of the size of a single chain in different solvent qualities, they found that as one incorporates more knowledge all of the key metrics improved. They also found that, when the numerical values of the theory were encoded, predicting the difference between the theory and the data performed best, but that further improvement could be achieved by using the functional form of the theory. Incorporating the full functional form of the theory had the added benefit of being easy to interpret.",
+        "category": " Introduction"
+    },
+    {
+        "id": 14,
+        "chunk": "# Deep Learning  \n\nAnother trend in ML in polymer science is the use of advanced deep learning techniques. Examples include recurrent neural networks (RNNs), which are designed to handle sequences such as the sequence in a copolymer,21,23,60,61,119 variational autoencoders (VAEs), which are composed of an encoder and a decoder with a smaller latent space in between,113,131 reinforcement learning (RL),33 where an agent takes an action and then receives a reward, generative adversarial networks (GAN),132 composed of a generator and a discriminator, and graph neural networks (GNNs),62 which are designed to handle graph based data such as a polymer structure. An example of RL is shown in Figure 7. For a detailed description of these methods, we refer the reader to recent reviews.7,8,14,15  \n\n![](images/d31865e9a95f9c3734a6095888349200db29be2f07fcc5ac5b9be69a25e52f34.jpg)  \nFigure 6. Example of hierarchical ML as applied to 3D printed biopolymers. The input, including polymer concentration $(C_{\\mathrm{ink}})$ , nozzle speed $\\left(\\nu_{\\mathrm{{T}}}\\right)$ , flow rate $(Q),$ and nozzle diameter $\\left(D_{\\mathrm{nozzle}}\\right)$ , is linked to the middle layers represented by physical quantities such as ink viscosity $\\eta_{\\mathrm{ink}}$ through simple physical models. Statistical inference in the form of LASSO then used to predict the desired quantity of the difference between the expected and the observed dimensions $(\\epsilon)$ . Note that the feature space for LASSO was extended by considering second order terms. Reprinted in part from ref 25. Copyright 2020 American Chemical Society.  \n\n![](images/dc89fe9ec1f86c9ebe84fc017a04e6972f03281d2b7fdc33ceca614a60c2e027.jpg)  \nFigure 7. Reinforcement learning scheme to generate polymers with high thermal conductivity (TC). $\\mathrm{PG}_{\\mathrm{baseline}}$ is a polymer generator trained on the PI1M data set. $\\mathrm{PG}_{\\mathrm{TC}}$ is a polymer generator that is trained to maximize TC. $\\mathrm{PG}_{\\mathrm{TC}}$ is sampled to create the generated polymers (P), which are passed to the regressor to predict TC. The generated polymers and TC are the used to calculate the loss function used in training $\\mathrm{PG}_{\\mathrm{TC}}$ . Reprinted from ref 33. Copyright 2022 American Chemical Society.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# Enhanced Scattering  \n\nIn small-angle X-ray and neutron scattering (SAS) of polymer and soft material systems, the challenge of interpreting data often matches or exceeds the challenge of preparing samples or conducting the experiment itself. This is in part due to the nature of the measurement and in part due to the great variety of microstructures that polymer materials exhibit. In order to interpret SAS data, there exists a library of geometric and phenomenological analytical models that researchers much choose from in order to extract physical meaning from the measurement.134 Due to the “phase problem”,135 there are likely many models that will fit a measured data set (as described by χ2 minimization), even if they are not proper descriptors of the underlying structure. This makes choosing the correct scattering model a difficult but incredibly important task.  \n\nIn light of this, several authors have developed ML models which attempt to guide the users toward the most probable analytical models that describe their data.133,136,137 In all cases, the authors constructed a library of theoretical data and explored a variety of supervised ML algorithms (including AutoML). Figure 8 shows the goodness-of-fit surface calculated using a GP that is interpolating across the parameter space of a complex scattering model. By combining this surrogate model with a kNearest Neighbors classifier, the authors are able to identify the correct scattering model for a given data set with high accuracy.133 They show that using the GP as a surrogate model, rather than using the analytical models directly, considerably increased the number of times that the correct model appeared in the top three predictions of the classifier. While similar to this work, the software package from Politi et al. is also notable in that it includes automated feature engineering in order to increase the classification accuracy of the overall method.137  \n\nIn addition to model-selection schemes, Jayaraman and coworkers have developed the computational reverse-engineering analysis for scattering experiments (CREASE) method which seeks to reconstruct three-dimensional structures of polymer materials from SAS data using genetic optimization.138−140 These authors leverage supervised, surrogate models in lieu of expensive analytical and simulation computations in order greatly reduce the convergence time of their method.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# Unsupervised Analysis  \n\nDimensionality reduction is a class of unsupervised approaches for analyzing unlabeled data. These methods can validate old wisdom and provide new insight into data sets because they rely on fewer assumptions and a priori knowledge (i.e., labels) than many supervised methods. For example, these approaches were recently used to reconstruct the periodic table from just a feature vector composed of simple atomic properties.141 In addition, unsupervised methods provide a path toward leveraging data that is too large, tedious or complex to analyze or label by hand e.g., from high-throughput experiments or large scale simulations. The trade-off for dimensionality reduction methods is that interpreting the meaning of data projected onto an unknown subspace can be challenging. Despite this, recent works have leveraged these methods to positive effect.  \n\nSeveral groups have used unsupervised methods to analyze the local and global 3-D structure of polymer simulations.142−144 Parker et al. surveyed various unsupervised (and supervised) methods for the task of identifying conformational transitions of polymers adsorbed to nanowire s.144 A key finding of this work is that, while all unsupervised methods surveyed were able to distinguish the different conformations of the polymer, most required specific data prepossessing to be effective. Statt et al. used the Uniform Manifold Approximation and Projection (UMAP) method to understand copolymer assembly as a function of monomer sequence.142 UMAP is a nonlinear manifold learning technique that focuses on preserving both the local and global structure of data.145 Using UMAP, the authors were able to not only identify common global structures in their simulations (e.g., strings, membranes, vesicles) but also how much each monomer contributed to a structure. These results were exemplified in 3-D simulation snapshots where the beads were colored by “structure”, a unique and powerful way to analyze heterogeneous simulation structures.  \n\n![](images/397b6fc7513a0860cb8c43ac670662942cb47682ae9b3cdefd085386747ff8e2.jpg)  \nFigure 8. Result of an ML-guided fitting process for small-angle scattering data. The neighborhood of the closest scattering model found is used to generate interpolations to determine whether a better fit to the data can be found. Reprinted with permission from ref 133. Copyright 2020 International Union of Crystallography.  \n\nResearchers have also used UMAP to better understand the chemical origins of optimized materials found via active learning algorithm s.26,34Figure 9 shows a UMAP projection of a copolymer computational space that was explored using an autonomous platform while trying to optimize ${}^{\\mathrm{i9}}\\mathrm{F}$ MRI signal.26 These data show that areas of highest signal fall into chemically similar regions and that two of the six comonomers dominate the high-signal regions. While this observation could likely have been learned by careful analysis of the data itself, the UMAP projection makes the conclusion clear and obvious.  \n\nSomewhat analogously to the above autonomous studies, Rodriguez et al. used Principle Component Analysis (PCA) and T-distributed stochastic neighbor embedding (t-SNE) as visualization and screening tools.86 They leveraged these methods to visualize and aid in the process of down-selecting candidates for high-throughput analysis from a material library that was too large to analyze in full.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# Optimization and Inverse Design  \n\nAs previously stated, one of the ultimate goals of ML for polymers is materials/process design. This often takes the form of optimization, most commonly property optimization .22−24,63,109,117 It is important to note that while most efforts have focused on optimizing the chemistry or formulation, one can also optimize the materials processing steps (e.g., annealing, film casting, mixing conditions). One can also simultaneously optimize multiple quantities.34,63 Materials optimization falls into the category of inverse design where the goal is to find an input (e.g., synthesis or processing parameters) that yields a desired output (e.g., material property). Inverse design can include other components such as generative models and high-throughput screening .33,131 For example, Ma and co-workers use a polymer generator that maximizes the thermal conductivity (see Figure 7).33 For additional details on inverse design, we direct the reader to a recent, comprehensive review by Sattari and co-workers.15",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# OUTLOOK",
+        "category": " Conclusions"
+    },
+    {
+        "id": 19,
+        "chunk": "# Interpretability and Explainability  \n\nAs ML continues to mature for polymer science, we expect to see an increase in the focus on interpretability and explainability. A better understanding of the ML model means that the user will have an improved intuition on when the model may extrapolate accurately or when it might fail which should accelerate the discovery of new knowledge.  \n\nHowever, the appropriate use of improvements in interpretability and explainability will depend on the specific problem and data availability. For example, linear models and their extensions, including generalized additive models or use of basis functions, provide clear connections between inputs and outputs. However, the underlying assumptions of these models may not be valid. For example, EBMs will be unable to correctly capture a complicated nonlinear relationship between two features. Thus, they must be used carefully, recognizing that while the models are explainable, they may not represent the true underlying physics. Symbolic regression will be particularly powerful when applied to problems where an analytic solution exists but is unknown. Since this assumption may not be valid, one potential path forward is to break up the problem into different regimes each with its own analytic solution. Symbolic regression can then be used separately in those different regimes to get different expressions depending on the features. To determine such regimes, one can use unsupervised clustering techniques first. In the future, it will be interesting if symbolic regression can be extended to consider more complicated operators such as integrals and derivatives, which will extend the power of symbolic regression, although at the expense of additional complexity.  \n\n![](images/62b76f970a89038ed39fcab929e4849f04812eef50487eb9a08297ca2e52cbf4.jpg)  \nFigure 9. (a) UMAP projection of a copolymer compositional space with the ML predicted $^{19}\\mathrm{F}$ MRI signal-to-noise color coded. Circled samples represent experimentally validated water-soluble structures. (b) UMAP projection of a copolymer compositional space with the major comonomer component color coded. Circled samples represent experimentally validated water-soluble structures. Reprinted in part from ref 26. Copyright 2021 American Chemical Society.  \n\nSince the aforementioned glass-box models ultimately have their limitations, there will still be a place for complex, black-box ML models such as deep neural networks or graph neural networks. In these cases, we expect to see increased use of posthoc explainability techniques such as SHAP and LIME. Although these techniques focus on local rather than global explainability, they can still provide knowledge in addition to the predictions from the models.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# Data Fusion and Transfer learning  \n\nWhether data fusion is successful or not will ultimately depend on the context. Data fusion will be the most successful when desired quantities are correlated, allowing knowledge of feature representation for one task to be related to feature representation for another task. This can partially be determined in advance by explicitly looking at correlations between desired quantities. Ultimately, methods such as multitask learning may benefit some predictions but not others. Nonetheless, data fusion is potentially a powerful way for imputing unknown values in scarce data sets that are common in polymer physics.  \n\nAs general advances are made in transfer learning, they can often be adapted to the polymers space. In the future, it will be interesting to see what the full toolbox of techniques look like beyond the current commonly used methods such as freezing parts of neural networks, learning the difference between the source and the target, and augmenting the target with the source. Even as the toolbox is built out, the role of prototyping will still likely be important as demonstrated by Yamada et al.27  \n\nAs such advances in transfer learning continue, they are also likely to impact multifidelity models, since a multifidelity model can be thought of as a transfer learning problem where the low fidelity, data rich task serves as the source while the high fidelity, data poor task serves as the target. However, advances in multifidelity are not necessarily limited to transfer learning. Instead the multifidelity nature can be explicitly taken into account by utilizing the relative cost of generating low fidelity data versus high fidelity data, e.g., in the context of active learning.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# Domain Knowledge  \n\nThe decision of when to apply domain knowledge can be thought of by considering first where one is on the spectrum of knowledge and data. At one extreme, we have perfect understanding of a system; in this case, data is not required. At the other extreme, there is data but a complete lack of knowledge. Almost all cases fall in between. As long as polymer science and ML continue to reside in a data poor and domain knowledge rich regime, we expect the use of domain knowledge in ML to grow by leveraging advances in related fields such as transfer learning and explainability. Important considerations when choosing to incorporate domain knowledge include whether soft or hard constraints should be used, how best to capture a polymer scientist’s intuition, how much data is available, if extrapolation is important and, finally, the role of explainability.  \n\nThe choice of the type of constraint can be very important; some problems involve hard constraints such as translational invariance in simulations whereas others such as phase equilibria may seem to have such constraints but in practice do not due to kinetics. In the latter situation, soft constraints nudging the system in the correct direction but allowing violation of the constraint are critical to avoiding overconfidence and negative transfer in a transfer learning context. There is also the issue of how best to incorporate domain knowledge, which is a developing field. This can range from the examples already provided to having polymer scientists create training data for an ML model, for example, by encoding their intuition via providing a probability of a material being of use. This can be further advanced by leveraging ideas such as active learning. The amount of data is also important. In more complex, data rich environments, it may be more fruitful to use ML to learn the best features rather than rely on intuition. For example, Wang et al. showed that, for the task of structure property prediction, using a convolutional neural network works better than the traditional, intuitive two point statistics as input for a neural network.112 There is also the consideration of extrapolation. Using domain knowledge can potentially prevent unphysical extrapolation. Finally, in some cases incorporating domain knowledge can be used for explainability. One interesting approach is to use ML to learn a simplified representation. For example, Cubuk et al. use ML to generate a structural quantity that predicts microscopic rearrangements and show that it correlates strongly to measures of plasticity in glassy systems.146  \n\n![](images/90b62a6fae9bef372dc623402da7d0a9e53d10d8f94c7d28b630bdd7b7eb18ae.jpg)  \nFigure 10. Schematic of the UNESCO defined pillars of open science. Adapted with permission under a Creative Commons CC-BY-SA 3.0 IGO License from UNESCO Recommendation on Open Science; https://unesdoc.unesco.org/ark:/48223/pf0000379949 (accessed 2022-11-26).147 Copyright 2021 UNESCO.  \n\nWhen these considerations are taken into account, incorporating domain knowledge in ML has a exciting future as ML can enhance qualitative data, such as from coarse-grained simulations or theories, and potentially even elevate it to be quantitative. In this context, ideas from multifidelity modeling will also be relevant.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# Open Science  \n\nIncreasingly, there is a community led effort toward adopting the principles of Open Science. While different authors define Open Science differently, a recent comprehensive review defines Open Science as “the transparent and accessible knowledge that is shared and developed through collaborative networks.”148 A United Nations Educational, Scientific, and Culturual Organization (UNESCO) workshop report states that “the core values Open Science stem f rom the rights-based, ethical, epistemological, economic, legal, political, social, multi-stakeholder and technological implications of opening science to society and broadening the principles of openness to the whole cycle of scientif ic research”.147Figure 10 highlights these core values. Working toward these goals can be achieved via open source journals such as ACS Polymers Au, use of preprint servers such as arXiv149 and ChemRxiv,150 sharing of data or the sharing of code. There are also efforts such as the MLExchange that seek to provide an easy interface for users to store, share, and execute their ML models.151 It has previously been found that in general, the benefits to individual researchers for following Open Science principles are numerous including increased citations and funding opportunities.152  \n\nThere are at least four large barriers that often prohibit scientists from broadly sharing data: understanding best practices, knowing where to put the data, knowing how to represent the data, and having the time to clean and, ultimately, share the data. The currently accepted best practice and gold standard is FAIR data. The principles behind FAIR data are explicitly detailed in Box 2 of Wilkinson et al.38 and provide a simple checklist for a researcher to determine if their data is FAIR or not. However, some items in the checklist still need to be addressed by the larger community. For example, “R1.3. (meta)data meet domain-relevant community standards” supposes that a community standard exists. Such topics are currently being addressed by the Materials Research Data Alliance (MaRDA).153 For where to put the data, there are several options available such as the Materials Data Facility,154,155 Zenodo,156 figshare,157 MaterialsMine,53,158−160 a Community Resource for Innovation in Polymer Technology (CRIPT),54 institution-specific resources, etc. To help make data FAIR, Scientif ic Data serves as a peer-reviewed, open-access journal for describing research data sets, which has already been used for polymers (e.g., ref 40). In terms of how to represent the data, this is still an area of active research being addressed by MaRDA,153 MaterialsMine,53,158−160 CRIPT,54,161 and others.162 However, the single largest barrier to FAIR data is the time that is necessary to clean and share the data. Thus, the efforts of MaterialsMine and CRIPT are notable as they provide additional benefits with the goal of making things net easier for polymer scientists to deposit their data. For example, MaterialsMine provides advanced visualization and CRIPT provides advanced search capabilities allowing one to find similar chemistries, polymer architectures and properties, among others.  \n\nCombined with the advances in shared data, it could be argued that the explosion of ML research in materials science was partly catalyzed by the existence of open source ML codebase s.163−168 While this is a code-centric perspective, the ability of a nonexpert to sample various powerful ML algorithms cannot be minimized. A group whose expertise is in polymer synthesis does not need to learn advanced graphics processing unit (GPU) programming to train a convolutional neural net, they simply install Tensorflow or Pytorch and download a network model from Github.164,165 A formulation engineer can leverage Bayesian optimization and GP calculations without a formal background in statistical modeling.166−169  \n\nWhile the importance of open software for materials science is not a new idea,170 the broad application of ML techniques by nonexperts has brought about new challenges. While open packages make it easy for everyone to leverage powerful techniques, they do not always force users to use them correctly. It is important that developers include heavy guardrails, error checking, and documentation in their codebases to ensure that their tools are used correctly. Furthermore, it is imperative that, upon publication of their work, researchers provide their analyses and ML codebases for other groups to use and scrutinize. When code is released, is important that the code is written with good software engineering principles in mind so that it can be easily maintained and used by the community. These principles include concepts like version control, automated unit testing, code style guidelines, user and API documentation and semantic versioning. Organizations like Software Carpentry36,171 seek to increase the code literacy among scientists, but, as of the writing of this article, do not include detailed software engineering principles in their educational materials beyond covering version-control. The importance of code-sharing, software engineering principles, and detailed documentation need to be emphasized in research funding and by publishers and principle investigators.",
+        "category": " Introduction"
+    },
+    {
+        "id": 23,
+        "chunk": "# Best Practices and Challenge Problems  \n\nSimilar to all specializations within polymer science, ML also has its own set of best practices to ensure good science. A recent guide focused on materials in general172 details several of these. This guide breaks best practices into categories such as data, modeling, benchmarking, and reproducibility. For example, data best practices include choosing a data set, data set composition, use of uncertainities and splitting train-validation-test splits, while modeling includes model choice, data scaling, and hyperparameter optimization. Prototyping is particularly important in ML. There are many times, where it is not a priori clear which models or which data manipulation techniques, such as normalization, will work best. Ultimately, the shortest route to production code will be trying different things and finding which works best. In the context of polymer design, a key test of the model is if it can be used in production, which may require the synthesis of new molecules.22,117 While this may be a tedious or costly step, it is important if model is to be truly validated.  \n\nReducing the barrier to experimental validation is part of the motivation for the development of automatic and autonomous experimentation platforms.  \n\nRelated to this, benchmarking is particularly important as benchmarking allows other researchers to understand when various models work better than others and if there are any general conclusions. For example, as detailed in Polymer Representations, benchmarking has clarified that, to date, there is no single best representation that works for all problems.173 Benchmarking is not only limited to feature selection, but also includes model selection and data selection.45,174  \n\nFrom a broader community perspective and related to benchmarking is the idea of grand challenges, such as the critical assessment of protein structure prediction (CASP) competition for protein folding,175 which accelerates progress within subfields on important problems. Specifically, the need for grand challenges has been called out in the Materials Genome Initiative Strategic Plan released in November of 2021.176",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# Beyond Polymer Autonomous  \n\nWhile the polymers community has started to develop and adopt autonomous and high-throughput techniques, the greater (hard) materials and chemistry communities have been rigorously pursuing this field as evidenced by the many recent reviews.71,73−76,89,177,178 While there are some barriers to directly adopting techniques from these fields, there is still much to learn and adapt from them and we will discuss a few key results here.  \n\nThere have been many nonpolymer studies on the topics of autonomous formulation exploration and phase-mapping and many of them make use of theory informed or constrained models, similar to what was discussed in the Domain Knowledge section above. $^{87,179-186}$ In order to increase the accuracy of their phase-identification from X-ray diffraction measurements (XRD), Suram et al. used a customized non-negative matrix factorization (NMF) approach in which they incorporated physical knowledge of solid state phase diagrams such as Gibb’s phase rule and XRD peak-shifting due to alloying.182 ,183 Under similar motivations, Chen et al. used an unsupervised, autoencoder approach in which they construct a latent subspace of meaningful variables and then express constraints with these variables.180 Kusne et al. also leveraged domain knowledge in their agent but, interestingly, also demonstrated that employing multitask learning to combine the task of property optimization with that of identifying phase boundaries is more efficient than performing either task alone.179,185 Finally, McDannald et al. identify the magnetic ordering transition using neutron diffraction by encoding physical details of the measurement (e.g., hysteresis, appropriate parameter distributions) and further by automatically selecting from a set of analytical models for the final analysis.87 Each of these studies presents lessons that should be adaptable to the process of phase mapping of polymer materials. As discussed above, the incorporation of domain knowledge into ML models greatly increases the accuracy of the model and reduces the data needed to achieve that accuracy. The polymers community has a rich array of theories and models that can be used to enhance autonomous agents and phasemapping tasks.  \n\nAs outlined in Table 1, one of the key challenges of applying autonomous techniques is the construction, operation, and maintenance of the robotic platform itself. In addition to domain-specific and ML expertise, building an autonomous platform requires a confluence of skills (machining, fabrication, electronic design, embedded software, robotics) that do not commonly overlap with polymers research groups. In a recent perspective, MacLeod et al. write about the importance and challenges of building flexible, multiuse robotic platforms.187 In a separate work, they also demonstrate how flexible platforms can identify the temperature−conductivity Pareto front in metallic thin films.188  \n\nOutside of autonomous, there are also several ML developments from the greater materials community worth highlighting. Gomes et al. have developed an unsupervised background subtraction methodology based on NMF techniques and have applied it to XRD and Raman spectroscopy data sets of metaloxide samples.189 The fact that this method is unsupervised means it does not require examples of background spectra and can be applied to unlabeled data. Furthermore, while demonstrated on XRD and Raman measurements, the construction of the approach is sufficiently general such that it should be applicable to many other measurements and kinds of materials. In their recent paper, Liang et al. develop a ML algorithm to automatically process images from reflection highenergy electron diffraction measurements of epitaxial thin films of iron oxides.190 The authors combine image segmentation, transfer learning, unsupervised clustering, and traditional mathematical analyses in order to extract diffraction peaks from the images, process them, and cluster them into phases. The work is a nice demonstration of how many individual ML methods can be brought together to automate a tedious analysis that is traditionally done by hand.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 25,
+        "chunk": "# SUMMARY  \n\nThe communities of polymer physics and chemistry are working to realize the promise of machine learning and, along the way, they are discovering and addressing key challenges arising from the unique nature of polymer materials. Researchers are developing methods to represent the statistical nature of polymer structure and encode polymer domain knowledge in machine learning models. Autonomous experimentation techniques, which are far more established in other materials and chemistry fields, are being adopted and extended by polymers researchers to synthesize, characterize, and formulate materials more rapidly, with higher resolution, and at reduced cost. Partly in an effort to tackle problem of having few, small, poorly annotated data sets, efforts to use transfer learning which leverage larger data sets from others fields are starting to bear fruit. Overall, the future of machine learning is bright for polymer materials, but there is still much work to be done.  \n\nIn order to unlock the true potential of machine learning, the polymer community must become more collaborative. Highquality open data, codebases, and benchmarks are essential to continued forward progress. Shared data sets must be provided with robust metadata, in accordance with FAIR data principles. Both analysis and production codes should be written with shareability, maintainability, and reuse in mind. Benchmarks should be created that provide a “ground-truth” that researchers can use to validate their methods and to make claims of improvement against. These practices will aid the adoption and advancement of machine learning within the polymer community, thereby accelerating materials and knowledge discovery in future studies.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 26,
+        "chunk": "# AUTHOR INFORMATION",
+        "category": " References"
+    },
+    {
+        "id": 27,
+        "chunk": "# Corresponding Authors  \n\nTyler B. Martin − National Institute of Standards and Technology, Gaithersburg, Maryland 20899, United States; $\\circledcirc$ orcid.org/0000-0001-7253-6507; Email: tyler.martin $@$ nist.gov   \nDebra J. Audus − National Institute of Standards and Technology, Gaithersburg, Maryland 20899, United States; $\\circledcirc$ orcid.org/0000-0002-5937-7721; Email: debra.audus@ nist.gov  \n\nComplete contact information is available at: https://pubs.acs.org/10.1021/acspolymersau.2c00053",
+        "category": " References"
+    },
+    {
+        "id": 28,
+        "chunk": "# Author Contributions  \n\nCRediT: Tyler B. Martin writing-original draft (equal), writingreview & editing (equal); Debra J. Audus writing-original draft (equal), writing-review & editing (equal).",
+        "category": " References"
+    },
+    {
+        "id": 29,
+        "chunk": "# Notes  \n\nThe authors declare no competing financial interest.",
+        "category": " References"
+    },
+    {
+        "id": 30,
+        "chunk": "# REFERENCES  \n\n(1) Ramesh, A.; Dhariwal, P.; Nichol, A.; Chu, C.; Chen, M.Hierarchical Text-Conditional Image Generation with CLIP Latents. arXiv2022, https://arxiv.org/abs/2204.06125 (submitted 2022-04-13; accessed 2022-12-05).   \n(2) Yang, Y.; Yuan, Y.; Zhang, G.; Wang, H.; Chen, Y.-C.; Liu, Y.; Tarolli, C. G.; Crepeau, D.; Bukartyk, J.; Junna, M. R.; Videnovic, A.; Ellis, T. D.; Lipford, M. C.; Dorsey, R.; Katabi, D. Artificial intelligenceenabled detection and assessment of Parkinson’s disease using nocturnal breathing signals. Nature medicine 2022, 28, 2207−2215. (3) Mittal, A.; et al. Artificial intelligence uncovers carcinogenic human metabolites. Nat. Chem. Biol. 2022, 18, 1204−1213.   \n(4) Jumper, J.; Evans, R.; Pritzel, A.; Green, T.; Figurnov, M.; Ronneberger, O.; Tunyasuvunakool, K.; Bates, R.; Žídek, A.; Potapenko, A.; et al. Highly accurate protein structure prediction with AlphaFold. Nature 2021, 596, 583−589.   \n(5) Morgan, D.; Jacobs, R. 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G.; Bakshy, E.BoTorch: A Framework for Efficient MonteCarlo Bayesian OptimizationAdvances in Neural Information Processing Systems 33. 2020.https://proceedings.neurips.cc/paper/2020   \n(169) Noack, M.; et al.gpCAM2022; https://github.com/lbl-camera/ gpCAM (accessed 2022-11-26).   \n(170) Meredig, B. Five high-impact research areas in machine learning for materials science. Chem. Mater. 2019, 31, 9579−9581.   \n(171) Wilson, G. Carpentry web site. http://software-carpentry.org (accessed 2022-11-26).   \n(172) Wang, A. Y.-T.; Murdock, R. J.; Kauwe, S. K.; Oliynyk, A. O.; Gurlo, A.; Brgoch, J.; Persson, K. A.; Sparks, T. D. Machine learning for materials scientists: An introductory guide toward best practices. Chem. Mater. 2020, 32, 4954−4965.   \n(173) Palizhati, A.; Torrisi, S. B.; Aykol, M.; Suram, S. K.; Hummelshoj, J. S.; Montoya, J. H. Agents for sequential learning using multiple-fidelity data. Sci. Rep. 2022, 12, 13.   \n(174) Liang, Q. H.; Gongora, A. E.; Ren, Z. K.; Tiihonen, A.; Liu, Z.; Sun, S. J.; Deneault, J. R.; Bash, D.; Mekki-Berrada, F.; Khan, S. A.; Hippalgaonkar, K.; Maruyama, B.; Brown, K. A.; Fisher, J.; Buonassisi, T. Benchmarking the performance of Bayesian optimization across multiple experimental materials science domains. Npj Computational Materials 2021, 7, 10.   \n(175) Protein Structure Prediction Center; https://predictioncenter.org (accessed 2022-11-23).   \n(176) Materials Genome Initiative Strategic Plan2021; https://www. mgi.gov/sites/default/files/documents/MGI-2021-Strategic-Plan.pdf (accessed 2022-08-15).   \n(177) Montoya, J. H.; Aykol, M.; Anapolsky, A.; Gopal, C. B.; Herring, P. K.; Hummelshøj, J. S.; Hung, L.; Kwon, H.-K.; Schweigert, D.; Sun, S.; Suram, S. K.; Torrisi, S. B.; Trewartha, A.; Storey, B. D. Toward Applied Physics Reviews 2022, 9, 011405.   \n(178) Rahmanian, F.; Flowers, J.; Guevarra, D.; Richter, M.; Fichtner, M.; Donnely, P.; Gregoire, J. M.; Stein, H. S. Enabling Modular Autonomous Feedback-Loops in Materials Science through Hierarchical Experimental Laboratory Automation and Orchestration. Advanced Materials Interfaces 2022, 9, 2101987.   \n(179) Kusne, A. G.; Yu, H.; Wu, C.; Zhang, H.; Hattrick-Simpers, J.; DeCost, B.; Sarker, S.; Oses, C.; Toher, C.; Curtarolo, S.; et al. On-thefly closed-loop materials discovery via Bayesian active learning. Nat. Commun. 2020, 11, 5966.   \n(180) Chen, D.; Bai, Y. W.; Ament, S.; Zhao, W. T.; Guevarra, D.; Zhou, L.; Selman, B.; van Dover, R. B.; Gregoire, J. M.; Gomes, C. P. Automating crystal-structure phase mapping by combining deep learning with constraint reasoning. Nature Machine Intelligence 2021, 3, 812−822.   \n(181) Gomes, C. P.; Bai, J.; Xue, Y.; Björck, J.; Rappazzo, B.; Ament, S.; Bernstein, R.; Kong, S.; Suram, S. K.; van Dover, R. B.; Gregoire, J. M. CRYSTAL: a multi-agent AI system for automated mapping of materials crystal structures. MRS Commun. 2019, 9, 600−608.   \n(182) Suram, S. K.; Xue, Y.; Bai, J.; Le Bras, R.; Rappazzo, B.; Bernstein, R.; Bjorck, J.; Zhou, L.; van Dover, R. B.; Gomes, C. P.; Gregoire, J. M. Automated Phase Mapping with AgileFD and its Application to Light Absorber Discovery in the V-Mn-Nb Oxide System. ACS Comb. Sci. 2017, 19, 37−46.   \n(183) Xue, Y.; Bai, J.; Le Bras, R.; Rappazzo, B.; Bernstein, R.; Bjorck, J.; Longpre, L.; Suram, S. K.; van Dover, R. B.; Gregoire, J.; Gomes, C. P.Phase-Mapper: An AI Platform to Accelerate High Throughput Materials Discovery. 2016; https://ui.adsabs.harvard.edu/abs/ 2016arXiv161000689X (accessed 2022-11-26).   \n(184) Tian, Y.; Lookman, T.; Xue, D. Z. Efficient sampling for decision making in materials discovery\\*. Chinese Physics B 2021, 30, 050705.   \n(185) Kusne, A. G.; McDannald, A.; DeCost, B.; Oses, C.; Toher, C.; Curtarolo, S.; Mehta, A.; Takeuchi, I. Physics in the Machine: Integrating Physical Knowledge in Autonomous Phase-Mapping. Frontiers in Physics 2022, 10, 6.   \n(186) Ament, S.; Amsler, M.; Sutherland, D. R.; Chang, M. C.; Guevarra, D.; Connolly, A. B.; Gregoire, J. M.; Thompson, M. O.; Gomes, C. P.; van Dover, R. B. Autonomous materials synthesis via hierarchical active learning of nonequilibrium phase diagrams. Science Advances 2021, 7, 12.   \n(187) MacLeod, B. P.; Parlane, F. G. L.; Brown, A. K.; Hein, J. E.; Berlinguette, C. P. Flexible automation accelerates materials discovery. Nat. Mater. 2022, 21, 722−726.   \n(188) MacLeod, B. P.; Parlane, F. G. L.; Rupnow, C. C.; Dettelbach, K. E.; Elliott, M. S.; Morrissey, T. D.; Haley, T. H.; Proskurin, O.; Rooney, M. B.; Taherimakhsousi, N.; et al. A self-driving laboratory advances the Pareto front for material properties. Nat. Commun. 2022, 13, 995. (189) Ament, S. E.; Stein, H. S.; Guevarra, D.; Zhou, L.; Haber, J. A.; Boyd, D. A.; Umehara, M.; Gregoire, J. M.; Gomes, C. P. Multicomponent background learning automates signal detection for spectroscopic data. npj Computational Materials 2019, 5, 77.   \n(190) Liang, H. T.; Stanev, V.; Kusne, A. G.; Tsukahara, Y.; Ito, K.; Takahashi, R.; Lippmaa, M.; Takeuchi, I. Application of machine learning to reflection high-energy electron diffraction images for automated structural phase mapping. Physical Review Materials 2022, 6, 063805.",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Preparation of Antifog Hard Coatings Based on CarboxyFunctionalized Polyhedral Oligomeric Silsesquioxane Cross-Linked with Oligo(ethylene glycol)s  \n\nJun Nakagawa, Seiya Morinaga, and Yoshiro Kaneko\\*  \n\nCite This: ACS Omega 2024, 9, 28895−28902",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 2,
+        "chunk": "# ACCESS  \n\nMetrics & More  \n\nABSTRACT: In this study, we prepared antifog hard coatings by heating a mixture of carboxy-functionalized polyhedral oligomeric silsesquioxane (POSS-C) and oligo(ethylene glycol)s (OEGs, HO( $\\mathrm{\\mathop{CH}}_{2}\\mathrm{CH}_{2}\\mathrm{O})_{n}\\mathrm{H}$ , $\\begin{array}{r l r}{n}&{{}=}&{1-6\\ '}\\end{array}$ in $^{N,N}$ -dimethylformamide, applying the mixture onto a glass substrate, and subsequently removing the solvent via heating. In addition, we evaluated the water resistance, hardness, and antifogging performance of the coatings. In particular, the coating produced at a 2:1 functional group ratio of POSS-C to tetraethylene glycol (OEG, $n=4{\\dot{,}}$ ) coating exhibited high surface hardness (6H), as determined using pencil scratch testing. The coating remained clear after exposure to the vapor of warm water at $40~^{\\circ}\\mathrm{C}$ at a height of $2\\ \\mathrm{cm}$ for $^{10\\ s,}$ demonstrating its antifogging property. Furthermore, no dissolution or cracking was observed when the POSS-C/OEG coating ${\\mathit{\\check{n}}}=4{\\mathit{\\check{\\mathbf{\\Psi}}}} $ , $\\mathrm{COOH/OH}=2{:}1\\rangle$ was immersed in water at room temperature for $^\\textrm{\\scriptsize1h}$ , confirming its water resistance. The Fourier transform infrared/attenuated total reflectance results showed the formation of ester bonds, indicating the construction of a network structure that enhanced the water resistance and hardness of the coating.  \n\n![](images/87c72c8b681830da3d3e610b2c76f5061fc056f15773b5ac8fee867cf1aaddc8.jpg)",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# INTRODUCTION  \n\nFogging occurs when light is diffusely scattered by small water droplets formed via the condensation of water vapor on cool surfaces upon rapid changes in environmental factors, such as temperature, humidity, and air circulation. Antifogging technologies have been widely utilized in automobile windshields, eyeglasses/goggles, bathroom mirrors, solar panels, and analytical/medical devices.  \n\nVarious antifogging materials have been developed based on rendering surface hydrophobicity (water repellency) to minimize water droplet adhesion or inducing hydrophilicity to promote the formation of a thin continuous water layer.1− Coating the substrate surface with hydrophobic materials typically involves lowering the surface free energy using lowenergy materials.4−7 However, the generation of intricate surface morphologies over a wide range is challenging. Moreover, poor adhesion to the substrate and the opacity of the coating further restrict the applicability of such coatings for antifogging purposes.  \n\nTherefore, surface coating using hydrophilic/water-absorbing materials has become the mainstream approach for the preparation of antifogging materials. Hydrophilic/waterabsorbing materials can be classified into two categories: inorganic materials, such as titanium dioxide and silica,8−16 a nd hydrophilic organic polymers. Titanium dioxide exhibits superhydrophilicity upon UV irradiation, making it suitable for antifog coatings. Silica-based coatings prepared under hightemperature conditions provide hydrophilic surfaces, enabling antifogging properties. However, the reliance on UV irradiation and high-temperature treatment limits indoor use and hinders applications on resin substrates. Meanwhile, hydrophilic organic polymer coatings can be utilized as versatile antifog coatings owing to their excellent formability.17−31 They incorporate hydrophilic groups, such as hydroxy, carboxy, ammonium, and sulfo groups. For example, polyacrylate coatings with various hydrophilic groups exhibit antifogging properties.32 Nonetheless, their hardnesses are generally lower than those of inorganic materials. Consequently, the transparency and antifogging properties gradually deteriorate because of scratching and abrasion. Therefore, the development of antifog hard coatings utilizing organic−inorganic hybrid materials is highly desired.33−38 For instance, organic−inorganic hybrid coatings obtained by incorporating 3-trimethoxysilylpropyl methacrylate into silica and subsequently performing the radical polymerization of acrylate monomers have been reported.39  \n\nRecently, antifog hard coatings utilizing silsesquioxane (SQ) have been increasingly employed. Based on the number of organic substituents (R) and oxygen atoms bonded to the silicon atom, siloxanes are classified into M (3 organic substituents and 1 oxygen atom), D (2 organic substituents and 2 oxygen atoms), T (1 organic substituent and 3 oxygen atoms), and $\\mathrm{\\DeltaQ}$ units (only oxygen atoms). SQ comprises only T unit, and its unit composition is denoted as $\\mathrm{RSiO}_{1.5}$ .40 Representative $s\\mathrm{Q}$ structures include a ladder-like structure, fully condensed cage structure, incompletely condensed cage structure, and double-decker structure. Fully condensed cage oligomers are referred to as polyhedral oligomeric SQs (POSSs), which find extensive applications across various fields.41−43 Furthermore, various side chain functional groups exist for SQs. In particular, our research group developed ladder-like polySQs with ammonium,44,45 carboxy,46 sulfo,47 and phosphonic acid48 groups, and POSQs with ammonium,49−55 carboxy,56,57 and imidazolium58−61 groups. In addition to these regularly structured SQs, polySQs that possess hydrophilic functional groups can be used to prepare antifog hard coatings owing to the combination of the rigid framework derived from T structures of siloxane bonds and hydrophilic side chains.  \n\nFor example, coatings based on polySQs obtained via the hydrolytic polycondensation (sol−gel reaction) of silane coupling agents bearing amino or glycidyl groups have been investigated.62−64 In addition, we have developed antifog hard coatings based on polyamides obtained via the polycondensation of POSS possessing amino and carboxy groups on side chains. This preparation involved the use of a condensation agent, 1-(3-(dimethylamino)propyl)-3-ethylcarbodiimide hydrochloride (EDC) and $N$ -hydroxysuccinimide (NHS), and heating at $80~^{\\circ}\\mathrm{C}$ in dehydrated dimethyl sulfoxide (DMSO) for $^{1\\bar{2}\\mathrm{~h~}}$ .65 Although this coating exhibited excellent antifogging properties and hardness, it tends to delaminate upon water immersion. The development of coatings with superior antifogging performance, hardness, and water resistance holds significant potential to realize their practical applications.  \n\nIn this study, we developed water-resistant antifog hard coatings by combining carboxy-functionalized POSS (POSSC) with mechanical robustness and hydrophilicity and oligo(ethylene glycol)s (OEGs) with film-formability, slight flexibility, and hydrophilicity.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# EXPERIMENTAL SECTION  \n\nMaterials. 2-Cyanoethyltriethoxysilane (CETES, $98\\%$ ), ethylene glycol $(99.5\\%)$ , diethylene glycol $(99.5\\%)$ , triethylene glycol $(99\\%)$ , tetraethylene glycol $(95\\%)$ , pentaethylene glycol $(95\\%)$ , and hexaethylene glycol $(98\\%)$ were purchased from Tokyo Chemical Industry Co., Ltd. (Tokyo, Japan). Trifluoromethanesulfonic acid (HOTf, $99\\%$ ) was obtained from Kanto Chemical Co., Inc. (Tokyo, Japan). Sodium hydroxide $\\left({\\mathrm{NaOH}},\\ 97\\%\\right)$ and polyethylene glycol with an average molecular weight of 1000 (PEG1000) were purchased from Nacalai Tesque Inc. (Kyoto, Japan). Ethanol $(99\\%)$ was purchased from Nippon Alcohol Hanbai $\\scriptstyle{\\mathrm{Co}}$ ., Ltd. (Tokyo, Japan). Amylene-stabilized chloroform $(99\\%)$ , $N,N$ -dimethylformamide (DMF, $99.5\\%)$ , acetonitrile $(99.5\\%)$ , acetone $(99\\%)$ , and hydrochloric acid (HCl, $35{-}37\\%)$ were purchased from FUJIFILM Wako Pure Chemical Co., Ltd. (Osaka, Japan). All reagents and solvents were used without further purification.  \n\nPreparation of Carboxy-Functionalized Rod-like PolySQ and POSS-C. Carboxy-functionalized rod-like polySQ was prepared as a precursor for POSS-C as described previously, with minor adjustments.46 After adding a $2.0\\ \\mathrm{mol}$ $\\hat{\\mathrm{~\\bf~L~}}^{-1}$ NaOH aqueous solution $\\left(60\\ \\mathrm{mL},\\ 120\\ \\mathrm{mmol}\\right)$ to CETES $\\left(8.871\\ \\mathrm{g},\\ 40\\ \\mathrm{mmol}\\right)$ while stirring at room temperature, the resulting solution was continuously stirred for $^{15^{\\mathrm{~h~}}}$ . Subsequently, the mixture was heated at ca. $50~^{\\circ}\\mathrm{C}$ in an open system until the solvent completely evaporated. After the crude product was maintained at $100^{\\circ}\\mathrm{C}$ in an oven for $^{2\\mathrm{h}}$ , 1.0 mol $\\bar{\\mathbf{L}^{-1}}$ HCl aqueous solution $\\mathrm{120~mL,}$ $120~\\mathrm{mmol}_{,}$ ) was added at room temperature (ca. $25~^{\\circ}\\mathrm{C}\\ '$ . This solution was further heated at ca. $50~^{\\circ}\\mathrm{C}$ in an open system until the solvent completely evaporated (ca. 6 h). Water $(25~\\mathrm{mL})$ ) was added to the resulting solid product, and the mixture was promptly stirred using a spatula for $1~\\mathrm{min}$ . Immediate suction filtration was performed to eliminate sodium chloride generated from the reaction of ${\\mathrm{\\DeltaNaOH}}$ and HCl. In this operation, it is important to stir and filter quickly as prolonged stirring causes all the products to dissolve in water. This operation was repeated three times. The resulting solid was dried under reduced pressure at room temperature, yielding a white powdered product $\\left(5.304\\ \\mathrm{g},\\right.$ quantitative yield).  \n\nPOSS-C was prepared with slight adjustments to the method reported in the literature.57 First, $0.50\\ \\mathrm{mol}\\ \\mathrm{L}^{-1}$ HOTf aqueous solution ( $\\mathrm{i00mL}$ , $50~\\mathrm{\\mmol}$ ) was added to carboxyfunctionalized rod-like polySQ $\\left(4.171\\ \\mathrm{\\g},\\ 33.33\\ \\mathrm{\\mmol\\uni}\\right)$ it). Subsequently, the solution was heated at ca. $60~^{\\circ}\\mathrm{C}$ for $20~\\mathrm{min}$ , and the resulting solution was stirred at room temperature for $^{2\\mathrm{~h~}}$ . Then, the solution was heated at ca. $50~^{\\circ}\\mathrm{C}$ in an open system until the solvent completely evaporated (ca. $5.5\\mathrm{~h~}_{\\cdot}$ ). At this stage, the solution remained in a liquid state owing to the presence of HOTf. The resulting liquid was subsequently held in an oven at $100~^{\\circ}\\mathrm{C}$ for $^\\mathrm{~2~h~}$ . After cooling to room temperature, acetone $(8.4~\\mathrm{mL})$ ) was added. This solution was poured into a mixed solvent of acetone and chloroform $(1{:}9\\mathrm{v}/\\$ $\\mathbf{v},416~\\mathrm{mL}$ ) and stirred at room temperature for ca. $15\\mathrm{~h~}$ . The insoluble part was separated by filtration and washed with acetonitrile (ca. $25~\\mathrm{mL},$ 5 times). Then, the insoluble part was dissolved in acetone (ca. $25~\\mathrm{mL}$ ), and the acetone-soluble part was separated using filtration. Finally, acetone was evaporated, and the resulting solid product was dried under reduced pressure at room temperature, yielding a white powdered product $(0.707\\ \\mathrm{g},$ yield $17\\%$ ). The structure of POSS-C was confirmed by $^{1}\\mathrm{H}$ and $^{29}\\mathrm{Si}$ NMR spectra (Figures S1 and S2). In this study, a mixture of octamer, decamer, and dodecamer POSS in a molar ratio of 10:75:15 was used for the coating preparation as described below (Scheme 1).  \n\nPreparation of POSS-C/OEG Coatings. The glass substrate $(48~\\mathrm{\\mm}\\ \\times\\ 28~\\mathrm{\\mm}$ , thickness: $1.3~\\mathrm{\\mm}^{\\cdot}$ ) was ultrasonically cleaned in ethanol (ca. 3 min) and hydrophilized using plasma equipment (Plasma Modifier PM100, Yamato Scientific Co., Ltd., Tokyo, Japan). This plasma treatment of the glass substrate was performed by flowing oxygen at a flow rate of $100~\\mathrm{{mL}~\\mathrm{{min}^{-1}}}$ for $30~\\mathsf{s}$ and then irradiating the plasma for $3~\\mathrm{min}$ . To ensure a consistent coating area for the applied solution on the glass substrate, a Teflon seal was affixed to the glass substrate, resulting in an area of $840~\\mathrm{mm}^{2}$ ( $30\\ \\mathrm{mm}\\times28\\$ $\\mathrm{mm}\\mathrm{\\'{\\Omega}}$ ). The weights and molar quantities of POSS-C and OEG in the reaction described below are provided as an example of the reaction involving tetraethylene glycol (OEG, $n=4,$ ). POSS-C $[0.0125\\mathrm{~\\textsubscript~{~g}~}0.1\\$ mmol based on repeating units (carboxy groups)] and tetraethylene glycol $\\left(0.0051\\textrm{g},\\ 0.025\\right.$ mmol, $0.05\\ \\mathrm{mmol}$ based on hydroxy groups) were dissolved in DMF $(0.3~\\mathrm{mL})$ . The mixture was stirred at $80~^{\\circ}\\mathrm{C}$ for $^{\\mathrm{~1~h,~}}$ resulting in a homogeneous solution. This solution was then applied onto the glass substrate $840~\\mathrm{mm}^{2}$ ( $\\left30\\mathrm{\\mm}\\times28\\mathrm{\\mm}\\right.$ ). The coated substrate was heated in an open system on a hot plate (setting temperature: $50~^{\\circ}\\mathrm{C}^{\\cdot}$ ) for $^\\textrm{\\scriptsize1h}$ to remove DMF. Subsequently, the substrate was treated in an oven at $150~^{\\circ}\\mathrm{C}$ for $30~\\mathrm{min}$ to prepare POSS-C/OEG coatings ${\\mathit{n}}=4$ , COOH/ ${\\mathrm{OH}}=2{:}1{\\dot{\\mathrm{}}}$ ). $\\mathrm{COOH/OH}=2{:}1$ means the molar ratio of carboxy groups in POSS-C to hydroxy groups in OEG. Other POSS-C/OEG coatings were also prepared similarly, where $\\\"n\\\"$ represents the degree of polymerization of OEG, and $^{\\mathrm{*}}\\mathrm{COOH/OH^{\\mathrm{*}}}$ indicates the molar ratio of carboxy groups in POSS-C to hydroxy groups in OEG.  \n\n![](images/6e63272ee17fb2389624f4a07ae8cecbb11e9d997257f4dd82d72c4f2fe9c8e6.jpg)  \nScheme 1. Preparation of Antifog Hard Coatings with Water Resistance (POSS-C/OEG $\\displaystyle\\left(n=1-6\\right)$ Coatings)  \n\nMeasurements. The UV−vis spectra were measured using a JASCO V-630 spectrophotometer (JASCO Corporation, Tokyo, Japan). The surface morphology of the coatings was observed via scanning electron microscopy (SEM) using the FEI Quanta 250 instrument (FEI Company Japan Ltd., Tokyo, Japan). The chemical compositions of the coatings were analyzed using energy-dispersive X-ray spectroscopy (EDX) embedded into the FEI Quanta 250 device. The Fourier transform infrared/attenuated total reflectance (FTIR/ATR) spectra were recorded using an IRSprit-T (SHIMADZU CORPORATION, Kyoto, Japan). The pencil hardness was measured using a pencil scratch tester (TP GIKEN Co., Osaka, Japan) at an angle of $45^{\\circ}$ under a loading of $750~\\mathrm{g}$ . The pencil used was made by Mitsubishi Pencil Co., Ltd. (Tokyo, Japan). The lead of the pencils was ground perpendicularly to make an angle of $90^{\\circ}$ before each pencil hardness measurement. The water contact angles of the coatings were evaluated using a water-drop contact-angle meter (SImage Entry 6, Excimer, Inc., Kanagawa, Japan). The amount of water droplet was 3.6 $\\mu\\mathrm{L},$ and the contact angle of the water droplet was measured with a charge-coupled device camera using the half angle method. The antifogging performance of the coatings was evaluated by placing the coating surface facing down at a distance of $2\\mathrm{cm}$ from warm water at $40~^{\\circ}\\mathrm{C}$ and exposing it to water vapor. The water resistance of the coatings was evaluated by immersing them in water at room temperature for $^{\\mathrm{~1~h,~}}$ wiping off water droplets on the surface, and observing the state of the coatings.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# RESULTS AND DISCUSSION  \n\nPreparation of POSS-C/OEG Coatings. The preparation of the water-resistant antifog hard coatings, POSS-C/OEG coatings, was performed as follows. A DMF solution of POSSC and OEG was heated and stirred under a closed system and then applied on glass substrates. Subsequently, the coated substrates were heated for $^\\textrm{\\scriptsize1h}$ in an open system to remove DMF. The coatings were further heated in an oven at $150~^{\\circ}\\mathrm{C}$ for $30~\\mathrm{min}$ to promote esterification (Scheme 1). All coatings prepared in this study were colorless and transparent (Figure S3). As a representative example, UV−vis measurement was performed on the POSS-C/OEG coating ( ${\\mathit{\\check{n}}}=4$ , COOH/OH $=2{:}1\\$ ), which showed over $98\\%$ transmittance in the visible wavelength region (Figure S4). From the SEM image of this coating, a smooth surface at the micrometer scale was observed (Figure S5a), and a peak corresponding to silicon atom was detected in the EDX pattern (Figure S5b), indicating the presence of POSS-C components on the surface.  \n\nWater Resistance of POSS-C/OEG Coatings. To evaluate water resistance, the coated glass substrates were immersed in water at room temperature for $^{\\textrm{1h}}$ and then taken out to observe the appearance of the coatings. POSS-C/OEG coatings ${\\bf\\zeta}_{n}=1$ , COOH/ $\\mathrm{{'OH}}=5{:}1$ , 2:1, and 1:1) and POSSC/OEG coatings ${\\mathit{\\check{n}}}=2,$ $\\mathrm{COOH/OH}=5{:}1$ and 2:1) were dissolved upon immersion in water (runs $_{1-5}$ in Table 1), suggesting the absence of the cross-linked network structure. This was verified by the FTIR/ATR results (Figures 1a,b, $^{2\\mathrm{a},\\mathrm{b}}$ , and 3a), which showed the absence of absorption peaks at ca. $1730~\\mathrm{cm}^{-1}$ attributed to ester bonds. When the coatings were prepared on glass substrates using ethylene glycol and diethylene glycol alone, respectively, and heated in an oven at $150^{\\circ}\\mathrm{C},$ they disappeared in ca. $5{-}10~\\mathrm{min}$ . This implies that ethylene glycol and diethylene glycol evaporated before the formation of ester bonds with POSS-C, resulting in a coating of POSS-C alone that dissolved in water.  \n\nIn the POSS-C/OEG coating ( ${\\mathit{\\check{n}}}=2$ , COOH/ $\\mathrm{{{OH}=1:1}}$ ), POSS-C/OEG coatings ${\\mathit{\\acute{n}}}=3,$ COOH/ $\\mathrm{{OH}}=5{:}1$ , 2:1, and 1:1), and POSS-C/OEG coating ${\\mathit{\\check{n}}}=4{\\mathit{\\check{\\mathbf{\\Psi}}}}$ , $\\mathrm{COOH/OH}=5{:}1\\$ ), numerous fine cracks were observed (runs $_{6-10}$ in Table 1). In the FTIR spectra, although the absorption peaks attributed  \n\nTable 1. Summary of Water Resistance, Surface Hardness, Antifogging Performance, and Water Contact Angle of POSS-C/ OEG Coatings   \n\n\n<html><body><table><tr><td colspan=\"4\">feed molar ratioa</td><td rowspan=\"2\">surface hardnessc</td><td rowspan=\"2\">time to keep antifoggingd (s)</td><td rowspan=\"2\">water contact angle</td></tr><tr><td> run </td><td>coating</td><td>COOH/OH</td><td> water resistanceb</td></tr><tr><td>1</td><td>POSS-C/OEG (n = 1)</td><td>5:1</td><td>dissolved</td><td>4H</td><td>20</td><td>80°</td></tr><tr><td>2</td><td>POSS-C/OEG (n = 1)</td><td>2:1</td><td>dissolved</td><td>4H</td><td>14</td><td>76°</td></tr><tr><td>3</td><td>POSS-C/OEG (n = 1)</td><td>1:1</td><td>dissolved</td><td>5H</td><td>13</td><td>76°</td></tr><tr><td>4</td><td>POSS-C/OEG (n = 2)</td><td>5:1</td><td>dissolved</td><td>5H</td><td>5</td><td>76°</td></tr><tr><td>5</td><td>POSS-C/OEG (n = 2)</td><td>2:1</td><td>dissolved</td><td>4H</td><td>15</td><td>76°</td></tr><tr><td>6</td><td>POSS-C/OEG (n = 2)</td><td>1:1</td><td>cracked</td><td>6H</td><td>8</td><td>93°</td></tr><tr><td>7</td><td>POSS-C/OEG (n = 3)</td><td>5:1</td><td>cracked</td><td>6H</td><td>10</td><td>82°</td></tr><tr><td>8</td><td>POSS-C/OEG (n = 3)</td><td>2:1</td><td>cracked</td><td>6H</td><td>5</td><td>83°</td></tr><tr><td>9</td><td>POSS-C/OEG (n = 3)</td><td>1:1</td><td>cracked</td><td>7H</td><td>5</td><td>83°</td></tr><tr><td>10</td><td>POSS-C/OEG (n = 4)</td><td>5:1</td><td>cracked</td><td>5H</td><td>17</td><td>83°</td></tr><tr><td>11</td><td>POSS-C/OEG (n = 4)</td><td>2:1</td><td> not dissolved not cracked</td><td>6H</td><td>10</td><td>79°</td></tr><tr><td>12</td><td>POSS-C/OEG (n = 4)</td><td>1:1</td><td>not dissolved not cracked</td><td>3H</td><td>9</td><td>67°</td></tr><tr><td>13</td><td>POSS-C/OEG (n = 5)</td><td>5:1</td><td>not dissolved not cracked</td><td>3H</td><td>6</td><td>98°</td></tr><tr><td>14</td><td>POSS-C/OEG (n = 5)</td><td>2:1</td><td>not dissolved not cracked</td><td>HB</td><td>8</td><td>80°</td></tr><tr><td>15</td><td>POSS-C/OEG (n = 5)</td><td>1:1</td><td>not dissolved not cracked</td><td>less than 2B</td><td>12</td><td>78°</td></tr><tr><td>16</td><td>POSS-C/OEG (n = 6)</td><td>5:1</td><td>not dissolved not cracked</td><td>less than 2B</td><td>6</td><td>72°</td></tr><tr><td>17</td><td>POSS-C/OEG (n = 6)</td><td>2:1</td><td>not dissolved not cracked</td><td>less than 2B</td><td>9</td><td>73°</td></tr><tr><td>18</td><td>POSS-C/OEG (n = 6)</td><td>1:1</td><td>not dissolved not cracked</td><td>less than 2B</td><td>40</td><td>40°</td></tr><tr><td>19 POSS-C</td><td></td><td></td><td>dissolved</td><td>5H</td><td>40</td><td>73°</td></tr><tr><td>20 PEG1000</td><td></td><td></td><td>dissolved</td><td>less than 2B</td><td>120</td><td>5°</td></tr></table></body></html>  \n\naFeed molar ratio of the COOH group in POSS-C to the OH group in OEG. bThe coated glass substrate was immersed in water at room temperature for $^\\textrm{\\scriptsize1h}$ and then taken out to observe the appearance of the coating. cThe surface hardness of coatings was evaluated using pencil scratch testing. dThe evaluation of antifogging properties was performed by placing the coated glass substrate with the coated side facing down 2 cm above warm water at $40~^{\\circ}\\mathrm{C}$ to for water vapor exposure and observing the antifogging behavior.  \n\n![](images/fbff527cb60a8d0f9deacdc7cc5f09124f56fd08c41c01e398bacf9c72550dbd.jpg)  \nFigure 1. FTIR/ATR spectra of POSS-C/OEG coatings [(a) $n=1$ , (b) $n=2.$ , (c) $n=3,$ , (d) $n=4,$ , (e) $n=5.$ , and (f) $n=6\\bar{.}$ (the feed molar ratio of the COOH group in POSS-C to the OH group in OEG was 5:1) and $(\\mathbf{g})$ POSS-C coating.  \n\nto the ester bond (ca. $1730~\\mathrm{cm}^{-1}$ ) were not clearly observed (Figures 1c,d, 2c, and $^{3\\mathrm{b,c}},$ ), their partial insolubility led to the expectation of the presence of partial cross-linking between the carboxy groups in POSS-C and the hydroxy groups in OEG. However, some un-cross-linked components dissolved as soluble components, leading to vacant spaces and the emergence of cracks due to contraction during drying. When the coating was prepared via triethylene glycol alone using the same procedure and heated in an oven at $150~^{\\circ}\\bar{\\mathrm{C}},$ , it disappeared in ca. $15\\ \\mathrm{min}_{,}$ , suggesting the partial evaporation of triethylene glycol during the coating preparation process and the subsequent insufficient cross-linking.  \n\n![](images/b94566a0fd86956fd4dc6b7c981e764f2e02e0a0e87e710f526f05c140ec9422.jpg)  \nFigure 2. FTIR/ATR spectra of POSS-C/OEG coatings [(a) $n=1$ , (b) $n=2,$ (c) $n=3.$ , (d) $n=4$ , (e) $n=5,$ and (f) $n=6\\bar{}$ (the feed molar ratio of the COOH group in POSS-C to the OH group in OEG was 2:1).  \n\nMeanwhile, POSS-C/OEG coatings ${\\mathit{\\check{n}}}=4,$ $\\mathrm{COOH/OH=}$ 2:1 and 1:1), POSS-C/OEG coatings ${\\mathit{n}}={\\mathfrak{I}},$ , $\\mathrm{COOH/OH=}$ 5:1, 2:1, and 1:1), and POSS-C/OEG coatings $\\left(n\\ =\\ 6,\\right.$ $\\mathrm{COOH/OH}=5{:}1$ , 2:1, and 1:1) did not dissolve or crack (runs 11−18 in Table 1). Based on the FTIR/ATR results, absorption peaks at ca. $1730~\\mathrm{cm}^{-1}$ attributed to ester bonds were observed in the coatings that did not dissolve or crack, in addition to the absorption peaks at ca. $1700~\\mathrm{{cm}^{-1}}$ due to carboxy groups dimerized through hydrogen bonding (Figures 1e,f, 2d−f, and $3\\mathrm{d-f)}$ . These results suggest the construction of a three-dimensional cross-linked network structure.  \n\n![](images/b10f068146d659bfd32397e0b9509c50b09597fe6ec17c9112c51003412c4d00.jpg)  \nFigure 3. FTIR/ATR spectra of POSS-C/OEG coatings [(a) $n=1$ , (b) $n=2.$ , (c) $n=3.$ , (d) $n=4,$ , (e) $n=5.$ , and (f) $n=6\\dot$ (the feed molar ratio of the COOH group in POSS-C to the OH group in OEG was 1:1).  \n\nHardness of POSS-C/OEG Coatings. The surface hardness of the POSS-C/OEG coatings was evaluated using a pencil scratch testing. The pencil hardness of POSS-C/OEG coatings $\\left(n=1{-}4\\right)$ prepared using OEG with lower molecular weights ranged from 3H to 7H, demonstrating a considerably high surface hardness (runs 1−12 in Table 1). Conversely, the pencil hardness of POSS-C/OEG coatings ( ${\\mathit{n}}={\\mathfrak{s}}$ and 6) was found to be less than 2B to $3\\mathrm{H}$ , revealing a decrease in surface hardness with increasing molecular weight of OEG (runs $14-$ 18 in Table 1). This is due to the higher proportion of organic components within the coating as the molecular weight of OEG increased. Among these coatings, only the POSS-C/ OEG coating ${\\mathit{\\check{n}}}=4,$ , $\\mathrm{COOH/OH}=2{:}1\\$ ) exhibited a lack of dissolution or cracking in the water resistance tests and demonstrated high surface hardness (6H) in the pencil scratch test $\\mathrm{'run~}11$ in Table 1).  \n\nThe POSS-C/OEG coating ${\\bf\\dot{\\rho}}_{n}=4,$ , $\\mathrm{COOH/OH=1:1}\\cdot$ ) and POSS-C/OEG coating $\\mathbf{\\psi}_{n}~=~\\mathfrak{s}_{\\mathrm{:}}$ , $\\mathrm{COOH/OH}~=~5{:}1)$ also showed reasonably good performance in the evaluation of water resistance and surface hardness (runs 12 and 13 in Table 1); however, their surface hardness (3H) was lower than that of the POSS-C/OEG coating ${\\mathit{\\check{n}}}=4{\\mathit{\\check{\\Psi}}}$ , $\\mathrm{COOH}/\\mathrm{OH}\\ =\\ 2{:}1\\right)$ (6H). We assume that the POSS-C/OEG coating $(n~=~4$ , $\\mathrm{COOH/OH}~=~1{:}1\\right)$ has a higher proportion of organic components compared to the POSS-C/OEG coating $(n=4,$ $\\mathrm{CO\\bar{O}H/O H}=2{:}\\mathrm{\\bar{1}}\\rangle$ ) because of the higher molar ratio of OEG, resulting in decreased surface hardness. Meanwhile, for the POSS-C/OEG coating $\\left(n=5,\\mathrm{COOH}/\\mathrm{OH}=5{:}1\\right)$ ), OEG with a higher molecular weight leads to the lower surface hardness as described above.  \n\nAntifogging Property of POSS-C/OEG Coatings. The evaluation of antifogging properties was performed by placing the coated glass substrate with the coated side facing down 2 cm above warm water $(40~^{\\circ}\\mathrm{C})$ for water vapor exposure and observing the antifogging behavior (Figure S6). Figure 4 shows the antifogging behavior of all coatings performed in this study. In particular, the POSS-C/OEG coating ( ${\\mathit{n}}=4,$ $\\mathrm{COOH/OH=}$ 2:1) maintained its antifogging state for $10~\\mathsf{s}$ after exposure to water vapor (Figure 4k and run 11 in Table 1), which, along with excellent water resistance and surface hardness (6H), proved its potential as an antifog hard coating.  \n\n![](images/99e31ca169072afa8f1e5fde4800b20d7f0d8b2c1bbf6352038e7747969a99ae.jpg)  \nFigure 4. Antifogging behavior of POSS-C/OEG coatings ${\\Big[}n=1{\\Big.}$ , $\\mathrm{COOH/OH=\\bar{(a)}}$ 5:1, (b) 2:1, and (c) 1:1], POSS-C/OEG coatings $[n=2,$ $\\mathrm{COOH/OH=\\left(d\\right.}$ ) 5:1, (e) 2:1, and (f) 1:1], POSS-C/OEG coatings $\\left[n=3,\\mathrm{COOH/OH=\\left(g\\right)}\\right.$ 5:1, (h) 2:1, and (i) 1:1], POSSC/OEG coatings ${\\big[}n=4$ , $\\mathrm{COOH/OH=(j)}$ 5:1, (k) 2:1, and (l) 1:1], POSS-C/OEG coatings $\\left[n=5,\\mathrm{COOH/OH}=\\left(\\mathrm{m}\\right)\\right.$ 5:1, (n) 2:1, and (o) 1:1], POSS-C/OEG coatings $\\left[n=6,\\right.$ $\\mathrm{COOH/OH=\\left(p\\right)}$ 5:1, (q) 2:1, and (r) 1:1], (s) POSS-C coating, and (t) PEG1000 coating upon exposure to water vapor.  \n\nWater Contact Angles of POSS-C/OEG Coatings. The water contact angles of the POSS-C/OEG coatings were measured to comprehend their antifogging mechanism (Figure $\\left\\langle{5{\\mathrm{a}}-{\\mathrm{\\mathbf{r}}}}\\right\\rangle$ . For comparison, the coatings of POSS-C and PEG1000 were prepared using the same method (Figure 5s,t). Because the OEGs used as the starting materials were liquid, the coatings could not be produced using them alone. As an alternative, PEG1000 was chosen as a compound containing ether bonds for comparison.  \n\nThe water contact angles of the POSS-C and PEG1000 coatings were 73 and $5^{\\circ}$ , respectively (Figure 5s,t, and runs 19 and 20 in Table 1). In contrast, the POSS-C/OEG coating ( $\\overset{\\cdot}{n}$ $=4$ , $\\mathrm{COOH/OH}=2{:}1$ ) exhibited a water contact angle of $79^{\\circ}$ (Figure $5\\mathrm{k}$ and run 11 in Table 1), surpassing those of the POSS-C and PEG1000 coatings. Presumably, the POSS-C/ OEG coating ${\\mathit{\\check{n}}}=4,$ $\\mathrm{COOH}/\\mathrm{OH}=2{:}1\\$ ) with a network structure formed by ester bonds possesses small pores, resulting in a slight a lotus leaf effect, which leads to a higher water contact angle compared to the coatings of POSS-C or PEG1000 alone. Alternatively, when the POSS-C/OEG coating $(n~=~4$ , $\\mathrm{COOH/OH}~=~2{:}1\\rangle$ with small pores is exposed to water vapor, water molecules enter the pores as vapor. Then, they cool down, and the resulting water fills the pores of the coating uniformly, suppressing light scattering.  \n\n![](images/bee473a557f2f6416dbddb8624b8dbbd260114a24f1c1ac43b6695c244ef3436.jpg)  \nFigure 5. Water contact angles of POSS-C/OEG coatings ${\\Big[}n=1{\\Big.}$ , $\\mathrm{COOH/OH}=\\left(\\begin{array}{l l}{}\\end{array}\\right)$ (a) 5:1, (b) 2:1, and (c) 1:1], POSS-C/OEG coatings $[n=2,$ $\\mathrm{COOH/OH=\\left(d\\right.}$ ) 5:1, (e) 2:1, and (f) 1:1], POSS-C/OEG coatings $[n=3]$ , $\\mathrm{COOH/OH=\\left(g\\right)}$ 5:1, (h) 2:1, and (i) 1:1], POSSC/OEG coatings $\\iota=4,\\mathrm{COOH/OH=\\left(j\\right)}$ 5:1, (k) 2:1, and (l) 1:1], POSS-C/OEG coatings $\\left[n=5,\\mathrm{COOH/OH}=\\left(\\mathrm{m}\\right)\\right.$ 5:1, (n) 2:1, and (o) 1:1], POSS-C/OEG coatings $\\left[n=6,\\mathrm{COOH/OH=\\left(p\\right)}\\right.$ 5:1, (q) 2:1, and (r) 1:1], (s) POSS-C coating, and (t) PEG1000 coating.  \n\nMechanism of Water-Resistant Antifog Hard Coating Formation. First, the antifogging mechanism during water vapor exposure is discussed. It is believed that the carboxy groups in POSS-C and the ether chains in OEG, which are hydrophilic components, contribute to the antifogging properties of the coatings. Furthermore, small pores exist within the POSS-C/OEG coating ${\\mathit{\\check{n}}}=4{\\mathit{\\check{\\Psi}}} $ , $\\mathrm{COOH/OH}=2{:}1\\AA$ ) with a network structure. When exposed to water vapor, water molecules enter these pores, where they cool down, and the resulting water fills the pores of the coating uniformly. This is expected to suppress light scattering, ultimately resulting in the manifestation of antifogging properties.  \n\nNext, we describe the mechanism of the observed hardcoating property through pencil scratch testing. The surface hardness of the coating composed solely of POSS-C was determined to be 5H. Based on this observation, it is considered that the robust hardness $\\mathrm{(6H)}$ of the developed POSS-C/OEG coating $\\left(n=4,\\mathrm{COOH}/\\mathrm{OH}=2{:}1\\right)$ ) stems from the sturdy framework inherent to POSS-C. In addition, the construction of a network structure upon the formation of ester bonds contributes to the enhanced hardness. Moreover, this network structure provides insolubility to the coating; thus, it can be regarded as the mechanism underlying water resistance.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# CONCLUSIONS  \n\nIn this study, a water-resistant antifog hard coating, POSS-C/ OEG coating ${\\mathit{n}}=4{\\mathit{\\Omega}}$ , $\\mathrm{COOH}/\\mathrm{OH}=2{:}1\\rangle$ , was obtained by mixing POSS-C and tetraethylene glycol in a 2:1 feed molar ratio based on their functional groups (COOH and OH groups) and heating the mixture in DMF, followed by its application onto a glass substrate and evaporating the solvent via heating. When the POSS-C/OEG coating ${\\mathit{\\Delta}}_{n}=4{\\mathit{\\Delta}}_{\\mathrm{:}}$ COOH/ $\\mathrm{OH}=2{:}1$ ) was exposed to water vapor at a height of $2\\ \\mathrm{cm}$ above warm water at $40\\ ^{\\circ}\\mathrm{C},$ the coated surface remained clear for ca. $^{10\\mathrm{~s},}$ , and it demonstrated a surface hardness of 6H. Even after immersion in water at room temperature for $^{\\textrm{1h,}}$ the coating did not dissolve or crack, exhibiting excellent water resistance. The antifog hard coatings developed in this study may evolve into applications for antifogging in resin window glass, which is expected in future automobile lightweighting efforts, due to their significantly high surface hardness.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 7,
+        "chunk": "# ASSOCIATED CONTENT",
+        "category": " References"
+    },
+    {
+        "id": 8,
+        "chunk": "# $\\bullet$ Supporting Information  \n\nThe Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.4c03563.  \n\n$\\mathrm{^{1}H}$ and $^{29}\\mathrm{Si}$ NMR spectra of POSS-C, appearance of POSS-C/OEG coatings, UV−vis spectrum and SEM and EDX of the POSS-C/OEG coating ${\\mathit{n}}=4{\\mathit{\\!}}$ , COOH/ $\\mathrm{OH}~=~2{:}1$ ), and photos of the equipment used for antifogging evaluation (PDF)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# AUTHOR INFORMATION  \n\nCorresponding Author Yoshiro Kaneko − Graduate School of Science and Engineering, Kagoshima University, Kagoshima 890-0065, Japan; $\\circledcirc$ orcid.org/0000-0001-6386-9166; Email: ykaneko@eng.kagoshima-u.ac.jp",
+        "category": " References"
+    },
+    {
+        "id": 10,
+        "chunk": "# Authors  \n\nJun Nakagawa − Graduate School of Science and Engineering, Kagoshima University, Kagoshima 890-0065, Japan Seiya Morinaga − Graduate School of Science and Engineering, Kagoshima University, Kagoshima 890-0065, Japan  \n\nComplete contact information is available at: https://pubs.acs.org/10.1021/acsomega.4c03563",
+        "category": " References"
+    },
+    {
+        "id": 11,
+        "chunk": "# Author Contributions  \n\nIndividual author contributions are as follows: J.N. contributed to almost all of the experimental work and wrote the paper. S.M. contributed to UV−vis, SEM, EDX and water contact angle measurements after water vapor exposure. Y.K. designed the research, directed this study, and edited the paper.",
+        "category": " Abstract/Introduction/Materials and methods/Results and discussion/Conclusions/References \n\nThe text segment appears to outline the contributions of individual authors to the research paper, which is typically found in the \"Author Contributions\" section. However, since \"Author Contributions\" is not one of the provided categories, it does not fit uniquely into the given options. If I have to classify it under one of the provided categories, it is closely associated with the \"Results and discussion\" section as it reflects on the contributions towards data collection and analysis, which often happens in the context of those sections. However, it could be argued that it belongs more appropriately under an informative section not listed. \n\nConsequently, the closest classification would be:\n\nCategory: Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# Notes  \n\nThe authors declare no competing financial interest.",
+        "category": " References"
+    },
+    {
+        "id": 13,
+        "chunk": "# ABBREVIATIONS  \n\n$s\\mathrm{Q}_{\\varepsilon}$ silsesquioxane; POSS, polyhedral oligomeric silsesquioxane; POSS-C, carboxy-functionalized polyhedral oligomeric silsesquioxane; OEG, oligo(ethylene glycol); UV−vis, UV− visible; SEM, scanning electron microscopy; EDX, energydispersive X-ray spectroscopy; FTIR/ATR, Fourier-transform infrared spectroscopy/attenuated total reflection; EDC, 1-(3- (dimethylamino)propyl)-3-ethylcarbodiimide hydrochloride; NHS, N-hydroxysuccinimide; DMSO, dimethyl sulfoxide; CETES, 2-cyanoethyltriethoxysilane; HOTf, trifluoromethanesulfonic acid; PEG1000, polyethylene glycol with an average molecular weight of 1000; DMF, N,N-dimethylformamide",
+        "category": " References"
+    },
+    {
+        "id": 14,
+        "chunk": "# REFERENCES  \n\n(1) Chen, Y.; Zhang, Y.; Shi, L.; Li, J.; Xin, Y.; Yang, T.; Guo, Z. Transparent Superhydrophobic/Superhydrophilic Coatings for SelfCleaning and Anti-Fogging. Appl. Phys. Lett. 2012, 101, 033701. (2) Wang, Y.; Gong, X. Special Oleophobic and Hydrophilic Surfaces: Approaches, Mechanisms, and Applications. J. Mater. Chem. A 2017, 5, 3759−3773.   \n(3) Zhao, J.; Song, L.; Ming, W. Antifogging and Frost-Resisting Polymeric Surfaces. Adv. Polym. Sci. 2018, 284, 185−214.   \n(4) Sun, Z.; Liao, T.; Liu, K.; Jiang, L.; Kim, J. H.; Dou, S. X. Fly-Eye Inspired Superhydrophobic Anti-Fogging Inorganic Nanostructures. Small 2014, 10, 3001−3006.   \n(5) Shang, Q.; Zhou, Y. Fabrication of Transparent Superhydrophobic Porous Silica Coating for Self-Cleaning and AntiFogging. Ceram. Int. 2016, 42, 8706−8712.   \n(6) Syafiq, A.; Vengadaesvaran, B.; Ahmed, U.; Rahim, N. A.; Pandey, A. K.; Bushroa, A. R.; Ramesh, K.; Ramesh, S. Facile Synthesize of Transparent Hydrophobic Nano- $\\mathbf{CaCO}_{3}$ Based Coatings for Self-Cleaning and Anti-Fogging. Mater. Chem. Phys. 2020, 239, 121913.   \n(7) Qiu, Z.; Lin, H.; Zeng, L.; Liang, Y.; Zeng, C.; Hong, R. UltraScratch-Resistant, Hydrophobic and Transparent OrganosiliconEpoxy-Resin Coating with a Double Cross-Link Structure. Appl. Sci. 2022, 12, 4854.   \n(8) Watanabe, T.; Nakajima, A.; Wang, R.; Minabe, M.; Koizumi, S.; Fujishima, A.; Hashimoto, K. Photocatalytic Activity and Photoinduced Hydrophilicity of Titanium Dioxide Coated Glass. Thin Solid Films 1999, 351, 260−263.   \n(9) Matsuda, A.; Kogure, T.; Muto, H.; Sakai, M.; Tadanaga, K.; Minami, T.; Tatsumisago, M. Titania Nanocrystals-Dispersed Coatings from $\\mathrm{SiO}_{2}–\\mathrm{TiO}_{2}$ Gel Films through Hydrolysis and Dissolution. Key Eng. Mater. 2006, 317−318, 565−568.   \n(10) Tricoli, A.; Righettoni, M.; Pratsinis, S. E. Anti-Fogging Nanofibrous $\\mathrm{SiO}_{2}$ and Nanostructured $\\mathrm{SiO}_{2}–\\mathrm{TiO}_{2}$ Films Made by Rapid Flame Deposition and In Situ Annealing. Langmuir 2009, 25, 12578−12584.   \n(11) Lai, Y.; Tang, Y.; Gong, J.; Gong, D.; Chi, L.; Lin, C.; Chen, Z. Transparent Superhydrophobic/Superhydrophilic $\\mathrm{TiO}_{2}$ -Based Coatings for Self-Cleaning and Anti-Fogging. J. Mater. Chem. 2012, 22, 7420−7426.   \n(12) Park, J. T.; Kim, J. H.; Lee, D. Excellent Anti-Fogging DyeSensitized Solar Cells Based on Superhydrophilic Nanoparticle Coatings. Nanoscale 2014, 6, 7362−7368.  \n\n(13) Lai, Y.; Huang, J.; Cui, Z.; Ge, M.; Zhang, K. Q.; Chen, Z.; Chi, L. Recent Advances in $\\mathrm{TiO}_{2}$ -Based Nanostructured Surfaces with Controllable Wettability and Adhesion. Small 2016, 12, 2203−2224. (14) Ye, L.; Zhang, Y.; Song, C.; Li, Y.; Jiang, B. A Simple Sol-Gel Method to Prepare Superhydrophilic Silica Coatings. Mater. Lett. 2017, 188, 316−318. (15) Chemin, J. B.; Bulou, S.; Baba, K.; Fontaine, C.; Sindzingre, T.; Boscher, N. D.; Choquet, P. Transparent Anti-Fogging and SelfCleaning $\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ Thin Films on Polymer Substrates Using Atmospheric Plasma. Sci. Rep. 2018, 8, 9603. (16) Xi, R.; Wang, Y.; Wang, X.; Lv, J.; Li, X.; Li, T.; Zhang, X.; Du, X. Ultrafine Nano- $\\mathrm{TiO}_{2}$ Loaded on Dendritic Porous Silica Nanoparticles for Robust Transparent Antifogging Self-Cleaning Nanocoatings. Ceram. Int. 2020, 46, 23651−23661. (17) Howarter, J. A.; Youngblood, J. P. Self-Cleaning and Next Generation Anti-Fog Surfaces and Coatings. Macromol. Rapid Commun. 2008, 29, 455−466. (18) Tahk, D.; Kim, T.; Yoon, H.; Choi, M.; Shin, K.; Suh, K. Y. Fabrication of Antireflection and Antifogging Polymer Sheet by Partial Photopolymerization and Dry Etching. Langmuir 2010, 26, 2240−2243. (19) Chevallier, P.; Turgeon, S.; Sarra-Bournet, C.; Turcotte, R.; Laroche, G. Characterization of Multilayer Anti-Fog Coatings. ACS Appl. 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Zwitterionic Polymer Brush Coatings with Excellent Anti-Fog and Anti-Frost Properties. RSC Adv. 2016, 6, 61695−61702. (26) Hong, J. W.; Cheon, H. K.; Kim, S. H.; Hwang, K. H.; Kim, H. K. Synthesis and Characterization of UV Curable Urethane Acrylate Oligomers Containing Ammonium Salts for Anti-Fog Coatings. Prog. Org. Coat. 2017, 110, 122−127. (27) Yao, B.; Zhao, H.; Wang, L.; Liu, Y.; Zheng, C.; Li, H.; Sun, C. Synthesis of Acrylate-Based UV/Thermal Dual-Cure Coatings for Antifogging. J. Coat. Technol. Res. 2018, 15, 149−158. (28) Bai, S.; Li, X.; Zhang, R.; Li, C.; Zhu, K.; Sun, P.; Zhao, Y.; Ren, L.; Yuan, X. Enhancing Antifogging/Frost-Resisting Performances of Amphiphilic Coatings via Cationic, Zwitterionic or Anionic Polyelectrolytes. Chem. Eng. J. 2019, 357, 667−677. (29) Zhang, T.; Fang, L.; Lin, N.; Wang, J.; Wang, Y.; Wu, T.; Song, P. Highly Transparent, Healable, and Durable Anti-Fogging Coating by Combining Hydrophilic Pectin and Tannic Acid with Poly(ethylene terephthalate). Green Chem. 2019, 21, 5405−5413. (30) Zhao, J.; Lu, P.; Song, L.; Tian, L.; Ming, W.; Ren, L. Highly Efficient Antifogging and Frost-Resisting Acrylic Coatings from OneStep Thermal Curing. Colloids Surf., A 2020, 585, 124160. (31) Zhong, H.; Liu, X.; Yu, B.; Zhou, S. Fast UV-Curable ZwitterWettable Coatings with Reliable Antifogging/Frost-Resisting Performances. Biomimetics 2022, 7, 162. (32) Raula, M.; Kar, S.; Ansari, F.; Das, S.; Ghosh, S. K. ZwitterWettable Acrylic Polymeric Coating on Glasses for Anti-Fog Applications. J. Appl. Polym. Sci. 2020, 137, 49303.  \n\nFogging Behavior of Water-Absorbing Polymer Films Derived from Isosorbide-Based Epoxy Resin. Mater. Lett. 2016, 180, 81−84.   \n(34) England, M. W.; Urata, C.; Dunderdale, G. J.; Hozumi, A. AntiFogging/Self-Healing Properties of Clay-Containing Transparent Nanocomposite Thin Films. ACS Appl. Mater. Interfaces 2016, 8, 4318−4322.   \n(35) Zhang, W.; Zhu, L.; Ye, H.; Liu, H.; Li, W. Modifying a Waterborne Polyacrylate Coating with a Silica Sol for Enhancing AntiFogging Performance. RSC Adv. 2016, 6, 92252−92258.   \n(36) Topçu Kaya, A. S.; Cengiz, U. Fabrication and Application of Superhydrophilic Antifog Surface by Sol-Gel Method. Prog. Org. Coat. 2019, 126, 75−82.   \n(37) Liang, B.; Zhong, Z.; Jia, E.; Zhang, G.; Su, Z. Transparent and Scratch-Resistant Antifogging Coatings with Rapid Self-Healing Capability. ACS Appl. Mater. Interfaces 2019, 11, 30300−30307. (38) Shi, J.; Xu, L.; Qiu, D. Effective Antifogging Coating from Hydrophilic/Hydrophobic Polymer Heteronetwork. Adv. Sci. 2022, 9, No. e2200072.   \n(39) Chang, C. C.; Huang, F. H.; Chang, H. H.; Don, T. M.; Chen, C. C.; Cheng, L. P. Preparation of Water-Resistant Antifog Hard Coatings on Plastic Substrate. Langmuir 2012, 28, 17193−17201. (40) Baney, R. H.; Itoh, M.; Sakakibara, A.; Suzuki, T. Silsesquioxanes. Chem. Rev. 1995, 95, 1409−1430.   \n(41) Chen, S.; Li, X.; Li, Y.; Sun, J. Intumescent Flame-Retardant and Self-Healing Superhydrophobic Coatings on Cotton Fabric. ACS Nano 2015, 9, 4070−4076.   \n(42) Yanagie, M.; Kaneko, Y. Preparation of Irrefrangible Polyacrylamide Hybrid Hydrogels Using Water-Dispersible Cyclotetrasiloxane or Polyhedral Oligomeric Silsesquioxane Containing Polymerizable Groups as Cross-Linkers. Polym. Chem. 2018, 9, 2302− 2312.   \n(43) Kowalczyk, A.; Kowalczyk, K.; Gziut, K. Synthesis of Monoacryloxypropyl-POSS-Based Hybrid Epoxyacrylate Copolymers and Their Application in Thermally Curable Structural Self-Adhesive Tapes. Polymers 2019, 11, 2058.   \n(44) Kaneko, Y.; Iyi, N.; Kurashima, K.; Matsumoto, T.; Fujita, T.; Kitamura, K. Hexagonal-Structured Polysiloxane Material Prepared by Sol-Gel Reaction of Aminoalkyltrialkoxysilane without Using Surfactants. Chem. Mater. 2004, 16, 3417−3423.   \n(45) Kaneko, Y. Ionic Silsesquioxanes: Preparation, Structure Control, Characterization, and Applications. Polymer 2018, 144, 205−224.   \n(46) Toyodome, H.; Kaneko, Y.; Shikinaka, K.; Iyi, N. Preparation of Carboxylate Group-Containing Rod-like Polysilsesquioxane with Hexagonally Stacked Structure by Sol-Gel Reaction of 2-Cyanoethyltriethoxysilane. Polymer 2012, 53, 6021−6026.   \n(47) Kaneko, Y.; Toyodome, H.; Mizumo, T.; Shikinaka, K.; Iyi, N. Preparation of a Sulfo-Group-Containing Rod-Like Polysilsesquioxane with a Hexagonally Stacked Structure and Its Proton Conductivity. Chem.\u0001Eur. J. 2014, 20, 9394−9399.   \n(48) Harada, A.; Shikinaka, K.; Ohshita, J.; Kaneko, Y. Preparation of a One-Dimensional Soluble Polysilsesquioxane Containing Phosphonic Acid Side-Chain Groups and Its Thermal and ProtonConduction Properties. Polymer 2017, 121, 228−233.   \n(49) Kaneko, Y.; Shoiriki, M.; Mizumo, T. Preparation of Cage-Like Octa(3-aminopropyl)silsesquioxane Trifluoromethanesulfonate in Higher Yield with a Shorter Reaction Time. J. Mater. Chem. 2012, 22, 14475−14478.   \n(50) Tokunaga, T.; Shoiriki, M.; Mizumo, T.; Kaneko, Y. Preparation of Low-Crystalline POSS Containing Two Types of Alkylammonium Groups and Its Optically Transparent Film. J. Mater. Chem. C 2014, 2, 2496−2501.   \n(51) Imai, K.; Kaneko, Y. Preparation of Ammonium-Functionalized Polyhedral Oligomeric Silsesquioxanes with High Proportions of Cagelike Decamer and Their Facile Separation. Inorg. Chem. 2017, 56, 4133−4140.   \n(52) Matsumoto, T.; Kaneko, Y. Effect of Reaction Temperature and Time on the Preferential Preparation of Cage Octamer and Decamer 1060−1067.   \n(53) Hasebe, R.; Kaneko, Y. Control of Crystalline-Amorphous Structures of Polyhedral Oligomeric Silsesquioxanes Containing Two Types of Ammonium Side-Chain Groups and Their Properties as Protic Ionic Liquids. Molecules 2019, 24, 4553.   \n(54) Matsumoto, T.; Kaneko, Y. Correlation between Molecular Structures and Reaction Conditions (Temperature-Pressure-Time) in the Preparation of Secondary, Tertiary, and Quaternary AmmoniumFunctionalized Polyhedral Oligomeric Silsesquioxanes. J. Sol-Gel Sci. Technol. 2020, 95, 670−681.   \n(55) Kaneko, Y. Superacid-Catalyzed Preparation of Ionic Polyhedral Oligomeric Silsesquioxanes and Their Properties, Polymerization, and Hybridization. J. Sol-Gel Sci. Technol. 2022, 104, 588− 598.   \n(56) Liu, J.; Kaneko, Y. Preparation of Polyhedral Oligomeric Silsesquioxanes Containing Carboxyl Side-Chain Groups and Isolation of a Cage-Like Octamer Using Clay Mineral. Bull. Chem. Soc. Jpn. 2018, 91, 1120−1127.   \n(57) Kozuma, T.; Kaneko, Y. Preparation of Carboxyl-Functionalized Polyhedral Oligomeric Silsesquioxane by a Structural Transformation Reaction from Soluble Rod-Like Polysilsesquioxane. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2511−2518.   \n(58) Ishii, T.; Enoki, T.; Mizumo, T.; Ohshita, J.; Kaneko, Y. Preparation of Imidazolium-Type Ionic Liquids Containing Silsesquioxane Frameworks and Their Thermal and Ion-Conductive Properties. RSC Adv. 2015, 5, 15226−15232.   \n(59) Harada, A.; Koge, S.; Ohshita, J.; Kaneko, Y. Preparation of a Thermally Stable Room Temperature Ionic Liquid Containing CageLike Oligosilsesquioxane with Two Types of Side-Chain Groups. Bull. Chem. Soc. Jpn. 2016, 89, 1129−1135.   \n(60) Maeda, D.; Ishii, T.; Kaneko, Y. Effect of Lengths of Substituents in Imidazolium Groups on the Preparation of Imidazolium-Salt-Type Ionic Liquids Containing Polyhedral Oligomeric Silsesquioxane Structures. Bull. Chem. Soc. Jpn. 2018, 91, 1112− 1119.   \n(61) Kaneko, Y. Ionic Liquids Containing Silsesquioxane and Cyclic Siloxane Frameworks. Chem. Rec. 2023, 23, No. e202200291.   \n(62) Maeda, T.; Hamada, T.; Tsukada, S.; Katsura, D.; Okada, K.; Ohshita, J. Antifogging Hybrid Materials Based on Amino-Functionalized Polysilsesquioxanes. ACS Appl. Polym. Mater. 2021, 3, 2568− 2575.   \n(63) Hamada, T.; Sugimoto, T.; Maeda, T.; Katsura, D.; Mineoi, S.; Ohshita, J. Robust and Transparent Antifogging Polysilsesquioxane Film Containing a Hydroxy Group. Langmuir 2022, 38, 5829−5837. (64) Hamada, T.; Maeda, T.; Kawashima, K.; Sugimoto, T.; Tanaka, A.; Tanaka, Y.; Katsura, D.; Mineoi, S.; Kaneko, Y.; Ohshita, J. Effect of the Amine Hydrochloride Salt on the Antifogging Properties of Amino-Functionalized Polysilsesquioxane. ACS Appl. Polym. Mater. 2023, 5, 1596−1605.   \n(65) Kozuma, T.; Mihata, A.; Kaneko, Y. Preparation of Soluble POSS-Linking Polyamide and Its Application in Antifogging Films. Materials 2021, 14, 3178.",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Superhydrophilic and Superamphiphilic Coatings  \n\nSandro Olveira, Ana Stojanovic, and Stefan Seeger Department of Chemistry, University of Zurich, Zurich, Switzerland",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# 3.1 INTRODUCTION  \n\nThe concept of superhydrophilicity was introduced following intensive research on superhydrophobic surfaces and in response to a request for coatings and surfaces that display strong affinity to water [1]. When water droplets are in contact with a superhydrophilic surface, they completely spread over the surface. When such a surface additionally enables total spreading of oily droplets (superoleophilic property), it is defined as superamphiphilic. Over the past decade, surfaces exhibiting superhydrophilicity or superamphiphilicity have been the subjects of immense interest because of their potential applications in various fields, including the development of ­microfluidic devices, liquid–liquid separation membranes, antifogging, antireflective, self‐cleaning, and antifouling coatings [2–7].  \n\nIn 2000, the term superhydrophilicity was used for the first time in papers ­published by three different research groups from Japan [1, 8, 9]. Earlier, in 1997, Wang et al. published a seminal paper on a superamphiphilic coating that consisted of a $\\mathrm{TiO}_{2}$ polycrystalline film [10].  \n\nThis chapter reviews the current state of research on superhydrophilic and superamphiphilic coatings, and it is organized as follows: Section 3.2 summarizes important fundamentals and definitions that apply to artificial superhydrophilic and superamphiphilic surfaces. The next section (Section 3.3) presents (i) examples of naturally occurring superhydrophilic and/or superamphiphilic surfaces and (ii) the most prominent examples of artificial superwetting coatings are illustrated in Section 3.4. Since high‐quality coatings exhibiting superhydrophilicity or superamphiphilicity cannot be produced without manipulation and control of surface ­chemistry and surface structure, Section  3.5 contains an overview of the most common techniques used for manufacturing such coatings. Then, the next section (Section 3.6) describes the most explored applications of superhydrophilic and superamphiphilic coatings, which include antifogging films, antireflective ­coatings, enhanced boiling heat transfer, separation membranes, and smart surfaces with reversible switching abilities. Section 3.7 provides an overview of commercially available superhydrophilic and superamphiphilic coatings. In the last Section 3.8 conclusions about the current state of research and commercial applications of these superwetting coatings are drawn.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 3.2 BASIC CONCEPTS OF SUPERHYDROPHILICITY  \n\nSurface wettability is generally characterized by the value of the contact angle. A surface is called superhydrophilic (or alternatively, superwetting) if the apparent contact angle of water on the surface is less than $5^{\\circ}$ . In addition to either superhydrophilicity or superhydrophobicity, a surface can also exhibit either superoleophilicity or superoleophobicity. On a superoleophilic surface, the contact angle of a polar droplet exhibits a value lower than $10^{\\circ}$ . A surface that is both superhydrophilic and superoleophilic is called superamphiphilic.  \n\nThe wettability of a solid surface is controlled by the surface free energy and the geometric structure of the surface. Commonly, the presence of polar groups on the surface decreases the contact angle of liquids. Water can completely spread over a few smooth surfaces, including those of glass [11], quartz [12], amorphous silica [13], gold [14], selected oxides (carrying OH groups on the surface) [15], and selected self‐assembled monolayers with OH‐based functionalities (OH, COOH, POOH). Such strong affinity for water is typically short term, and in the presence of any contamination, the contact angle increases to a few tens of degrees [16, 17]. According to Young’s equation, the contact angle of a liquid drop on a solid surface results from equilibrium between cohesive forces in the liquid and adhesive forces between the solid and the liquid [18]. For a certain liquid, the predominant contribution to the contact angle originates from the interfacial character of the solid material, which is related to its surface structure [19]. Wettability is determined by the surface free energy of a solid surface, which is commonly expressed by Young’s equation,  \n\n$$\n\\mathrm{cos}\\theta={\\frac{\\gamma_{\\mathrm{{sv}}}-\\gamma_{\\mathrm{{sl}}}}{\\gamma_{\\mathrm{{lv}}}}}\n$$  \n\nHere, $\\theta$ is the contact angle in Young’s mode, and $\\gamma_{_\\mathrm{{lv}}},\\gamma_{_\\mathrm{{sv}}},$ and $\\gamma_{_\\mathrm{lv}}$ are the three ­different types of surface tension (liquid/vapor, solid/vapor, and solid/liquid) involved in the system.  \n\nIn recent studies, Drelich et al. suggested that surfaces are truly superhydrophilic only if the surface is textured and/or structured [20, 21]. Rough or porous surfaces ­possess a roughness factor $r$ (where $r$ is the ratio of the real surface area to the projected  \n\nsurface area) that is defined by the Wenzel equation [22]. The Wenzel theory predicts that, for any rough surface, the actual surface area will be greater than the geometric surface area. This surface ratio is called the roughness factor and is defined by  \n\n$$\nr=\\frac{\\mathrm{cos}\\theta}{\\mathrm{cos}\\theta^{*}}\n$$  \n\nwhere $\\theta$ and $\\boldsymbol{\\theta}^{*}$ are the actual and geometric contact angles, respectively. In other words, an increase in the surface area (due to the presence of texture) amplifies the natural hydrophilicity of the material.  \n\nHence, according to the definition by Drelich et al., truly superhydrophilic ­surfaces possess roughness factors greater than one, and water spreads completely over them. Figure  3.1 shows the relationship between the contact angle on a smooth surface (Young’s contact angle, $\\theta$ ) and the minimum value of the roughness factor $(r)$ that is required for the same surface to promote complete spreading of the liquid. The figure shows that with moderate roughening of the surface in which $r$ is between 1.2 and 2, superhydrophilicity should be conceivable on any material having an intrinsic contact angle less than $60^{\\circ}$ . For materials with $\\theta{>}65{-}70^{\\circ}$ , roughening might not be practical, since extremely high values for $r$ are needed. Theoretically, on any rough material, a liquid should spread to zero (or nearly zero) apparent contact angle; however, in practice, liquid penetration into the rough structure of a substrate might be difficult. Such a system is essentially a three‐phase system trapped in a metastable state, and the surface should be treated more like a porous or solid–air composite material [23, 24].  \n\n![](images/58099ab2c5899654780cbdd53546070d6929688f7d4863670ef7bbc2a0bf6de9.jpg)  \nFig. 3.1  Minimum values of roughness factor necessary to promote the complete spreading of liquid on a surface with varying Young’s (intrinsic) contact angle. Used with permission from Ref. 21. $\\mathbb{O}$ Royal Society of Chemistry.  \n\nBesides being rough, porous surfaces also can exhibit superhydrophilic properties via wicking. Wicking or spontaneous imbibition is the suction of a liquid into a porous medium due to negative capillary pressure created at the liquid–air interface [25]. Wetting on a three‐dimensional (3D) porous surface that exhibits a 3D capillary effect was investigated theoretically by Quéré et al. [24, 26, 27] According to the authors, a “hemi‐wicking” behavior is likely on superhydrophilic 3D porous media; this behavior is between droplet spreading and penetration. The critical contact angle, $\\theta_{\\mathrm{c}}$ , below which the penetration of the porous surface by a liquid will take place, is given by  \n\n$$\n\\cos\\theta_{\\mathrm{c}}=\\frac{1-\\varphi_{\\mathrm{s}}}{r-\\varphi_{\\mathrm{s}}}\n$$  \n\nwhere $\\varphi_{s}$ is the solid fraction remaining dry during the wicking process and $r\\left(\\geq1\\right)$ is the surface roughness. For a porous surface, $r$ goes to infinity, and (3.3) predicts that the microstructure will be fully invaded by any liquid having a contact angle (as measured on a flat surface) of less than $90^{\\circ}$ . For rough surfaces ( ${\\bf\\zeta}_{r>1}$ but not infinity), the critical angle can vary between 0 and $90^{\\circ}$ . In the case of 3D porous materials, it is possible to switch from a superhydrophobic to a superhydrophilic state by slight changes in the surface chemistry [28]. This extreme transition in wetting behavior is enabled by the fact that only filled or empty pores are energetically favorable. Thus, compared to roughness‐induced superhydrophilicity, porosity‐induced superhydrophilicity offers some unusual possibilities for designing functional surfaces. In this regard, nanoporous thin films are particularly attractive since, in contrast to ­microporous films, they do not scatter light due to their small pore size [29].  \n\nBesides 3D capillary effects, a surface can be completely wetted by a 2D capillary effect. The 2D capillary effect has been observed on metal oxide semiconductors [30]. In general, ultraviolet (UV) light induces the formation of hydrophilic and oleophilic nanodomains on the surface. These different domains lead to nanostructured and microstructured flow channels for both aqueous and oily liquids. Channels for water flow are formed by oleophilic walls, while those for oily liquids are formed by hydrophilic walls; these structures may exhibit behavior that resembles the 2D capillary effect [31]. The hydrophilic areas are higher in position than oleophilic areas; this increases the formation of flow channels [30]. When a liquid droplet comes in contact with such a surface, it will flow along these nano‐ and microchannels and form a very thin film on the surface. This effect usually leads to superamphiphilicity; it was first observed in $\\mathrm{TiO}_{_2}$ coatings. The existence of surface superamphiphilicity has been explained as follows: after UV illumination, oxygen vacancies are created in the surface, and these vacancies induce the translation of the corresponding $\\mathrm{Ti^{4+}}$ sites to $\\mathrm{Ti}^{3+}$ . The as‐formed $\\mathrm{Ti}^{3+}$ sites are favorable to dissociate water molecules and further monolayers or multilayers of water form by molecular adsorption [32]. This results in the formation of surface hydrophilic domains, while leaving the rest of the surface oleophilic. In many cases, 2D and 3D capillary effects can coexist and work cooperatively on the same surface [30].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# 3.3  NATURALLY OCCURRING SUPERHYDROPHILIC AND SUPERAMPHIPHILIC SURFACES  \n\nDuring evolution, plants and animals developed complex strategies to handle liquids, particularly for water management. With their sophisticated surface structures, living organisms can react to the environmental changes and deal with the extreme living conditions. There is enormous diversity in biological, multifunctional, and protective surfaces formed in different environments [33]. One of the most prominent examples is the surface of the lotus leaf, which exhibits extraordinary purity because of its extreme water‐repellent properties. The reason for this superhydrophobic behavior, discovered by Barthlott in the 1990s, [34] is a surface structure consisting of an epicuticular wax layer and a microscopic papillae structure. The wax causes low surface energy and the papillae, which consist of further branch‐like nanostructures, provide high surface roughness. These two features, the chemical composition and the topographic micro‐ and nanostructure of the surface, are most important for determining the wettability of a surface [35, 36]. In contrast to the lotus leaf, some plants show superhydrophilic properties. If a drop of water comes in contact with the surface of such plants, it will spread within seconds or even milliseconds. With regard to wetting behavior and environmental conditions, superhydrophilic plants can be divided into three groups: those that are permanently wet, those on which water is absorbed at surfaces, and those on which water spreads over surfaces. [37] The leaves of submerged water plants, for example, Anubias barteri, have permanently wet surfaces that consist of smooth cell surfaces without any waxes, papilla, or hairs. Plants that absorb water have porous surfaces or pores or multicellular hairs. For example, Sphagnum mosses consist of pores $10{-}20\\upmu\\mathrm{m}$ in diameter) that form a sponge‐like surface structure; this enables the plant to absorb amount of water that is up to 20 times the weight of the plant itself. This strategy of absorbing water is particularly important as a way for rootless plants to take up nutrients and as a way for plants to retain water in dry areas where dew is almost the only water source [38]. Ruellia devosiana belongs to the group of plants on which water spreads on surfaces. The leaves of this plant contain a complex surface with different cell types, including hair papilla, papilla cells, and glands; such a complex surface can spread a $5\\mathrm{-}\\upmu\\updownarrow$ drop of water within 0.2 s [38]. This is the fastest spreading behavior known for a plant species. Such a superhydrophilic surface is very important for plants in areas having high densities of precipitation, such as rainforests. Fast spreading creates a larger water–air interface, leading to an increase in evaporation, compared to hydrophilic, hydrophobic, or superhydrophobic surfaces. Through fast evaporation, a smooth gas exchange at the surface is ensured, and the growth of microorganisms at the surface is hindered. [37] The leaves of $R$ . devosiana show another interesting property. If a $10\\mathrm{-}\\upmu\\mathrm{l}$ droplet of oil is placed on its leaf, it also spreads to a flat film within 0.6 s. Surprisingly, water on a vertically oriented leaf stripe can move against gravity. Within 31 s, water on a leaf can move a vertical distance of $5\\mathrm{cm}$ . This phenomenon of water transport without any pressure against gravity might be exploited in applications of liquid‐transport devices [39].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# 3.4  ARTIFICIAL SUPERHYDROPHILIC COATINGS",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 3.4.1 $\\bar{\\mathsf{T i O}}_{2}$ Coatings  \n\nThe first superamphiphilic coating that consisted of a thin $\\mathrm{TiO}_{2}$ polycrystalline film from anatase sol on a glass substrate was reported by Wang et al. [10]. When the thin $\\mathrm{TiO}_{_2}$ film is exposed to UV radiation, the surface turns from slightly hydrophilic to superhydrophilic. The film exhibits a water contact angle of $72^{\\circ}\\pm1^{\\circ}$ before UV irradiation (Fig. 3.2a). After irradiation, water droplets spread on the film, resulting in a contact angle of $(0\\pm1)^{\\circ}$ (Fig. 3.2b). This change in wettability is more obvious when a $\\mathrm{TiO}_{2}$ ‐coated glass is exposed to water vapor. Without UV irradiation, the glass fogs (Fig. 3.2c), but upon irradiation, the glass becomes transparent (Fig. 3.2d), displaying an outstanding antifogging effect.  \n\nAll nonpolar liquids (e.g., glycerol trioleate and hexadecane) spread across the surface upon UV irradiation, exhibiting contact angles of $(0\\pm1)$ [10]. The same wettability change is observed on both anatase and rutile $\\mathrm{TiO}_{_2}$ surfaces, independent of their photocatalytic activities. Even after storage in dark conditions for a few days, the high amphiphilicity of the $\\mathrm{TiO}_{2}$ surface was maintained. A longer storage period induced a gradual increase in the water contact angle, revealing the surface wettability trend toward hydrophobicity. However, high amphiphilicity was repeatedly regenerated by  \n\n![](images/ea5a66eb4976e966b520bdcb2c949898a2a227968b494bbf07083a78e5fd13cc.jpg)  \nFig. 3.2  (a) A hydrophobic surface before ultraviolet irradiation. (b) A highly hydrophilic surface after ultraviolet irradiation. (c) Exposure of a hydrophobic $\\mathrm{TiO}_{2}$ ‐coated glass to water vapor. The formation of fog (small water droplets) hinders the view of the text on paper placed behind the glass. (d) Result of ultraviolet irradiation, creating an antifogging surface. The high hydrophilicity prevents the formation of water droplets, making the text clearly visible. Used with permission from Ref. 10. $\\mathbb{O}$ Nature Publishing Group.  \n\n![](images/90f7acfeaf337aea9f2861c4d3ff1baec24459e720913fa07bc025b6502a3826.jpg)  \nFig. 3.3  Mechanism of hydrophilicity on surfaces coated by $\\mathrm{TiO}_{2}$ . Under UV radiation, the valence of $\\mathrm{Ti^{4+}}$ changes to $\\mathrm{Ti}^{3+}$ , accompanied by the release of $\\mathbf{O}_{2}$ . This creates oxygen vacancies on the surface that can be occupied by water; hence, the surface becomes more hydrophilic. Used with permission from Ref. 42. $\\mathbb{O}$ Elsevier.  \n\nUV irradiation. The formation of a microstructured composite between hydrophilic and oleophilic phases, which is a result of the photogenerated $\\mathrm{Ti}^{3+}$ defects at definite sites, is considered to account for this unique behavior [40]. As a consequence, water can spread rapidly on a UV‐illuminated $\\mathrm{TiO}_{2}$ surface, which imparts superhydrophilic properties. ZnO possesses the same photoinduced hydrophilicity mechanism [41]. Increasing the concentration of nano‐ $\\mathrm{\\cdotTiO}_{_2}$ on a surface increases the number of accessible oxygen vacancies, thereby increasing the capacity for water absorption. Figure 3.3 illustrates the hydrophilicity mechanism for a $\\mathrm{TiO}_{2}$ ‐coated surface.  \n\nWhen placed in a dark environment, $\\mathrm{TiO}_{_2}$ ‐based surface coatings typically lose their superhydrophilic properties within minutes to hours; this limits their practical applications. In order to improve that Machida et al. found that by adding $30\\mathrm{mol}\\%$ $\\mathrm{SiO}_{_2}$ to a $\\mathrm{TiO}_{_2}$ coating, the contact angle of water is low immediately after the production, and hydrophilicity is preserved in a dark place [43]. At this point, extensive research has focused on chemical modifications to solid surfaces, such as ion doping, [44] metal deposition, [45] semiconductor coupling, [11, 20, 46], and further ­compositing with $\\mathrm{SiO}_{2}$ . [47] Moreover, superhydrophilicity might also be strengthened by increasing surface acidity or the number of hydroxyl groups at the surface.  \n\nToday, there are numerous studies dealing with superhydrophilic self‐cleaning surfaces containing titanium, but the majority of these publications still use glass as a standard substrate. On the other hand, one of excellent potential target for photoinduced cleaning, UV protection, and antimicrobial effects is the textile industry [48]. Special clothes, especially those that are endangered by staining with heavy ­contaminants such as soot, oils, or lubricants, are good candidates for applying superhydrophilic self‐cleaning surfaces. This is particularly important in the case of textile products that are either utilized outdoors or cannot be washed (because of their size or water sensitivity). Recently, a $\\mathrm{TiO}_{_2}$ coating was reported to be deposited on textile material using radiofrequency plasma‐enhanced chemical vapor deposition (RF PECVD) technique [49]. In this procedure, titanium (IV) chloride was used as the titanium source, oxygen was supplied as $\\mathbf{O}_{2}$ gas, and a cotton fabric served as the substrate. The stability of the coating remains unchanged after washing the fabric in a detergent solution, even after subsequent storage for 18 months. The number of nanoparticles absorbed on surfaces of fabrics and subsequent superhydrophilicity are affected by the efficiency of pretreatments [50]. For instance, studies have been performed on the effectiveness of some pretreatment methods, such as activating textile surfaces using plasma and vacuum UV irradiation [50, 51]. In these methods, fabric surfaces were modified by introducing negatively charged groups, thereby increasing the hydrophilicity of the fabrics. Alternatively, cross‐linking agents can be used to immobilize $\\mathrm{TiO}_{_2}$ nanoparticles on surfaces of the wool [52].  \n\nBesides glass and textile substrates, Ti‐containing mesoporous silica thin films (Ti‐MSTFs) have been prepared on Al and Al–Mg alloy substrates via a sol–gel/ spin‐coating method [53]. This coating method is applicable to various materials that have low thermal resistance. The resulting Al and Al–Mg alloy substrates coated with Ti‐MSTFs had highly hydrophilic properties, even under dark conditions, and showed photo‐induced superhydrophilicity under UV irradiation.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 3.4.2 $\\mathsf{S i O}_{2}$ Coatings  \n\nPrevious examples illustrate that addition of $\\mathrm{SiO}_{2}$ to titanium enhances the ­durability of superhydrophilic coatings. However, very recently, superhydrophilic coatings have been reported to be produced from mesoporous $\\mathrm{SiO}_{_2}$ without the addition of titanium [54]. The early theory established by Quéré et al. suggests that it is possible to enhance the wetting property of a surface by introducing roughness at the right scale [23, 55]. As a result, a mesoporous $\\mathrm{SiO}_{_2}$ superhydrophilic thin film was ­produced by the sol–gel method. When one coating layer of the film was applied, the contact angle for water decreased below $5^{\\circ}$ in $4\\mathrm{s}$ ; on films coated 6–12 times, the contact angle decreased below $5^{\\circ}$ in less than 1 s. Thus, superhydrophilicity increases as the number of coatings increases. The mechanism for such behavior can be understood from the simple relation derived by Wenzel et al. (see Section 3.2).  \n\nIn addition to mesoporous substances, nanostructured materials having structural elements between 1 and $100\\mathrm{nm}$ have the potential to improve surface functionalities of thin films. Materials with well‐ordered pores have been intensely investigated in many fields, including catalytic chemistry, adsorption chemistry, electrochemistry, and materials science. The most important families of silica‐based porous materials are zeolites, which have microporous structures with pore sizes less than $2\\mathrm{nm}$ , and mesoporous silicas, which have mesoporous structures with pore sizes between 2 and $50\\mathrm{nm}$ . Mesoporous structures have been formed via evaporation‐induced self‐assembly methods. The significant hydrophilic behavior can be achieved when transparent mesoporous silica thin films containing single‐site photocatalysts are used. The single‐site photocatalysts include moieties of Ti‐, V‐, Cr‐, Mo‐, and W‐oxide; [56] these photocatalysts show exclusive and remarkable catalytic properties that are not demonstrated by bulk catalysts [57, 58]. Because of electron localization, substitution sites for heteroatoms would attract water molecules; therefore, these materials become hydrophilic. After coating, the materials exhibit significant hydrophilic properties under dark conditions and photoinduced superhydrophilicity under UV irradiation. Among them, the W‐containing mesoporous silica thin film shows the best hydrophilic properties. This coating can be applied to various materials, including Al, Al–Mg alloys, and polycarbonate.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 3.5 METHODS FOR FABRICATING SUPERHYDROPHILIC AND SUPERAMPHIPHILIC SURFACES  \n\nMost solids are naturally rough, but their roughness is usually insufficient to reinforce a superhydrophilic state on a material surface. Inspired by naturally occurring examples of plants with superwetting properties for both water and oily liquids, such as R. devosiana, scientists have started creating artificial surfaces that exhibit similar properties [37]. Within the past decade, many different methods and materials have been implemented for the production of superhydrophilic and superamphiphilic surfaces on various substrates. Here, we review the most common techniques used for producing these coatings.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 3.5.1 Sol–Gel Method  \n\nIn general, the sol–gel method is used to synthesize porous network structures. It is a low‐temperature technique that is simple, affordable, and easy to control. By adjusting the composition of the precursor solution along with the hydrolysis and polycondensation processes, the resulting films can exhibit different morphologies and can contain different chemical components at the surface. The sol–gel method is widely used and is a convenient process for coating surfaces to obtain superhydrophilic and/ or superamphiphilic properties.  \n\n$\\mathrm{TiO}_{2}$ –polydimethylsiloxane $(\\mathrm{TiO}_{2}\\mathrm{-PDMS})$ composite films can be prepared by the sol–gel method from a $\\mathrm{Ti(OBu)_{4}}$ ‐benzoylacetone solution containing PDMS [59]. Contact angles measured for the $\\mathrm{TiO}_{2}{\\mathrm{-PDMS}}$ thin films show a wettability transition from hydrophobic to superhydrophilic states after treatment with oxygen plasma for $\\mathrm{{1s.Ma}}$ et al. [60] used this conventional technique to produce transparent mesoporous silica coatings that showed permanent superamphiphilicity with very fast spreading rates of within a few microseconds. To form the sol, they mixed tetraethyl orthosilicate (TEOS) and a poloxamer (Pluronic F‐127) with nitric acid; the solution was stirred at room temperature for $2\\mathrm{h}$ . Next, glass substrates were spin‐ coated with the sol, and further drying steps were performed. The approach aimed to create a superamphiphilic surface by increasing the roughness of an amphiphilic ­surface. Therefore, they introduced mesopores on the surface and obtained a ­superamphiphilic coating without using UV illumination. The ability of water and oily liquids, such as hexadecane, to spread with a contact angle of $0^{\\circ}$ on this surface is caused by high surface energy and high surface roughness. The high surface energy results from Si–O–Si and Si–OH groups present on the surface. The high capillary pressure inside the mesopores leads to the fast spreading mentioned above. Furthermore, the coating is transparent, because the pore diameter is in the range of $10\\mathrm{nm}$ , and therefore much less than the wavelength of visible light. This is an important feature with regard to possible industrial applications.  \n\nKako and Ye used a similar sol–gel method to produce a complex oxide $\\mathbf{(InNbO_{4})}$ coating with UV‐induced superamphiphilic properties [61]. A powder of $\\mathrm{In}(\\mathrm{NO}_{3})_{3}$ and niobium ethoxide was mixed in ethanol and spin‐coated on a quartz substrate. After 30 s of UV exposure, the contact angle of a water droplet changes from $55^{\\circ}$ to less than $5^{\\circ}$ , indicating superhydrophilicity. Moreover, the contact angles of $\\mathrm{CH}_{2}\\mathrm{I}_{2}$ and dodecane decrease to $15^{\\circ}$ and $0^{\\circ}$ , respectively, on such a surface. $\\mathrm{InNbO}_{4}$ is the first complex oxide to show superamphiphilicity after UV illumination.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3.5.2 Layer‐By‐Layer Assembly  \n\nIn 1966, Iler published a method for creating multilayers of inorganic “colloidal particles” without using any organic molecules; the method is now known as layer‐by‐ layer (LbL) deposition [62]. He reported that multilayers of oppositely charged nanoparticles can be assembled by the sequential adsorption of oppositely charged nanoparticles onto substrates from aqueous suspensions. Although Iler’s work did not attract attention at the time, 25 years later, Decher et al. developed the LbL process to fabricate multilayer thin films from oppositely charged polyelectrolytes. [63] Over the past 15 years, the LbL technique has received enormous attention. To enhance the wettability of the films, micro‐ or nanoparticles are commonly integrated to increase surface roughness. The LbL assembly has the advantage of precisely controlling the film thickness; thus, it is a desirable technique for fabricating ­transparent coatings. Liu and He [64] reported an LbL method for obtaining superhydrophilic coatings, in which raspberry‐like silica nanospheres were prepared by the electrostatic self‐assembly of polyelectrolytes and monodispersed silica nanoparticles of two different sizes.  \n\nAlternatively, the production of superhydrophilic coatings composed completely of nanoparticles has been proposed [65]. In addition, thin films consisting of $\\mathrm{TiO}_{_2}$ and $\\mathrm{SiO}_{2}$ nanoparticles have been prepared via LbL deposition. The presence of nanopores in $\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ nanoparticle coatings leads to useful ­functionalities, including antireflective and antifogging properties. The last step of this method includes calcination at high temperatures. This well‐known calcination process burns out the polymer component of the film and fuses the silica nanoparticles together via the formation of stable siloxane bridges [66]. Unfortunately, the high temperatures employed during this curing process also limit the substrate materials that can be coated; plastics with low melting points are not suitable for this type of coating.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3.5.3 Electrochemical Methods  \n\nElectrochemical methods include electrochemical deposition, anodization, galvanic cell reactions, and electrochemical polymerization. These are facile methods for ­constructing rough surfaces, regardless of the size and shape of the substrate.  \n\nShibuichi et al. have shown that the treatment of the surface of an aluminum plate with anode oxidation leads to superamphiphilic properties [67]. The plate was dipped into an acidic solution, and oxidation was performed at a current density of $10\\mathrm{mA}/\\mathrm{cm}^{2}$ . This method increases surface roughness; in fact, the analysis of the aluminum ­surface showed it to be fractal. Such a rough surface showed superwettable properties for both polar and nonpolar solvents.  \n\nNanostructured conducting polymers generally show superhydrophilic properties. Among these, the surface of polyaniline exhibits amphiphilic behavior. Therefore, Zhang et al. used an electrochemical‐template‐free method for the direct deposition of nanostructured polyaniline (PANI) on a substrate such as stainless steel [68]. This substrate was chosen, because it is widely used in industrial equipment. The PANI nanofibers were prepared using sulfuric acid and aniline at $0.85\\mathrm{V}$ on a stainless steel electrode. The structure and size of the nanofibers can be controlled by polymerization time. A water droplet on this modified PANI surface spreads very fast and reaches a contact angle of $5^{\\circ}$ within a few milliseconds. Droplets of organic solvents, such as acetone and hexane, spread even faster than a water droplet. Such a ­superamphiphilic surface is of high interest from both scientific and industrial ­viewpoints, as PANI shows simple nonredox doping/dedoping chemistry, is environmentally stable, and the superwetting property is permanently stable. This method exemplifies a convenient way for producing polymer‐functionalized surfaces that exhibit superamphiphilic properties.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3.5.4 Electrospinning  \n\nElectrospinning is a technique used to produce fibers with diameters ranging from micrometers to nanometers [69, 70]. In this technique, the sample solution is pumped through a nozzle to which a high electric voltage is applied. Owing to the evaporation of the solvent, the solution jet solidifies and forms fibers that are deposited on a collector. The final morphology strongly depends on the starting solution concentration.  \n\nSuperhydrophilic surfaces can be generated by $\\scriptstyle\\alpha-\\mathrm{Fe}_{2}\\mathrm{O}_{3}$ nanofibers with contact angles of $0^{\\circ}$ for water [71]. The $\\scriptstyle\\mathbf{\\alpha}\\mathbf{-Fe}_{2}\\mathbf{O}_{3}$ nanofibers are produced by electrospun poly(vinyl alcohol)/ferrous acetate composite nanofiber precursors and high‐­temperature calcination in air. The experimental results show that the morphology and crystalline phase of $\\scriptstyle\\alpha-\\mathrm{Fe}_{2}\\mathrm{O}_{3}$ nanofibers are influenced by the content of ferrous acetate in composite nanofibers and the calcination temperature. By controlling the calcination temperature, the magnetic property of $\\scriptstyle\\alpha-\\mathrm{Fe}_{2}\\mathrm{O}_{3}$ nanofibers can be tuned from superparamagnetic to ferromagnetic.  \n\nSuperamphiphilic coating applicable to textiles can be produced by electrospinning. Lim et al. [72] fabricated Janus fabrics with superwetting properties by using polyacrylonitrile (PAN) as the starting material. The method is very useful, because it enables the synthesis of micro‐ and nanofibers with definite diameters that can be coated on different substrates. To produce superamphiphilic Janus fabrics, a polymer solution of PAN, dimethylformamide, and TEOS was electrospun into nanofibers. Next, the fibrous mats were heated at $200^{\\circ}\\mathrm{C}$ , and the polymer solution mentioned earlier was electrospun onto the treated mats. Then, the mats were peeled from the substrate. This simple method provides a new way for producing functionally smart materials, which are of high interest for possible industrial applications.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3.5.5 Etching  \n\nEtching is often used as an additional step in many procedures to improve the roughness of substrates on different scales. For example, Kim et al. demonstrated a facile chemical etching method for fabricating a superamphiphilic surface on a silicon wafer [73]. On a clean silicon wafer, gold nanoclusters were deposited by thermal evaporation and etched in an $\\mathrm{HF/H}_{2}\\mathrm{O}_{2}/\\mathrm{DI}$ water solution. The gold clusters catalyzed the etching process at room temperature; therefore, the wafer was selectively etched. Next, the surface was coated with a self‐assembled monolayer material. The surface of the silicon wafer showed superamphiphilic behavior, upon exposure of a coated wafer to deep UV light $(\\lambda\\sim254\\mathrm{nm})$ .  \n\nA silicon wafer exhibiting superhydrophilicity can be produced by an electroless (EE) silicon etching method [74]. The EE method is a top–down technique that can be used to modify the morphology of the surface with nanoscale structures over a large area at room temperature.  \n\nIn industry, titanium alloys are often coated with commercially pure titanium (Ti) via physical vapor deposition (PVD), especially if they are used in the clinical sector, such as in the hospital. The coated surfaces have high roughness and show superoleophilicity. A droplet of mineral oil spreads with a critical contact angle of about $0^{\\circ}$ , while the contact angle of water droplet was $145^{\\circ}$ , indicating hydrophobicity. Jennissen and Lüers developed a simple chemical treatment to improve the wetting properties of such commercially available Ti‐PVD surfaces to superamphiphilicity [75]. After cleaning, the samples are etched with chromosulfuric acid at $240^{\\circ}\\mathrm{C}$ for $30\\mathrm{min}$ . A water droplet spread on the treated Ti‐PVD surface to a critical contact angle of $0^{\\circ}$ , indicating additional superhydrophilicity.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.5.6  Plasma Treatment  \n\nBecause of its ease in handling and very effective results, plasma treatment is one of the most used techniques for producing superhydrophilic or superamphiphilic ­surfaces. Oxygen plasma treatment modifies the surface properties of polymers, resulting in the hydrophilization of their surfaces [76]. The roughness and ­morphology of a treated polymer surface depend on the time of exposure [77].  \n\nZimmermann et al. used this method to prepare superamphiphilic surfaces based on a silicone nanofilament coating [78]. First, a desired substrate, such as a glass slide, was coated with silicone nanofilaments via a simple CVD coating at room temperature. The resulting surface was completely wetted by a droplet of hexadecane, which indicates superoleophilic and superhydrophobic properties. After exposing the surface to oxygen plasma, droplets of both hexadecane and  water spread completely on the surface, thus showing superamphiphilic properties.  \n\nLiu et al. used a plasma method to introduce superamphiphilic properties to a ­surface consisting of carbon nanotubes (CNT) that were decorated with silver nanoparticles (Ag) [79]. First, a silicon‐wafer substrate was coated with a paste of $\\mathbf{Ag}@\\mathbf{CNT}.$ By treating the modified substrate with Ar plasma, the contact angle of a water droplet decreased from $85^{\\circ}$ to almost $0^{\\circ}$ within $5\\mathrm{{min}}$ . The treated surface also showed superoleophilic properties with contact angles of $0^{\\circ}$ for diiodomethane and ethylene glycol. The plasma treatment increases the number of hydrophilic functional groups, such as hydroxyl and carboxyl groups, on the surface. In addition, proton donor components are increased, which leads to an increase in oleophilicity due to the capillary effect. This approach can be used, for instance, for the production of superamphiphilic Ag‐CNT electrodes.  \n\nPolymeric superamphiphilic surfaces were produced by Ellinas et al. using a plasma etching method [80]. Polystyrene colloid particles were deposited on a poly(methylmethacrylate) (PMMA) surface via spin coating. This colloidal lithography was followed by oxygen plasma etching, leading to a surface with highly ordered arrays of micropillars of PMMA. The height and diameters of the pillars can be adjusted very accurately by controlling the etching time and voltage. This method led to high surface roughness due to the introduced micro/nanoscale topography. The superwetting properties of such a nanotextured surface are stable over a long time.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3.5.7  Hydrothermal Method  \n\nThe hydrothermal method is a wet chemical procedure in which single crystals are synthesized in hot water under high pressure. This method allows precise control over crystal morphology and composition.  \n\nA microwave‐assisted hydrothermal method for the fabrication of superamphiphilic titanate network (STN) films was developed by Li et al. [81]. The SNT films consisted of twisted multiwalled titanate nanotubes grown on a Ti foil. Compared to other hydrothermal methods, this method is rapid $(10\\mathrm{min})$ and simple. Droplets of both polar and nonpolar solvents spread immediately with contact angles below $1^{\\circ}$ . On untreated Ti samples, the contact angles for water and $\\mathrm{CCl}_{4}$ were $73^{\\circ}$ and $15^{\\circ}$ , respectively. This facile production method also allows the integration of other atoms, such as PbS or CdS. This is of high interest for possible indoor applications, because Ti‐containing coatings demand UV light. By modifying the surface with materials sensitive to visible light, such as $\\mathrm{Pb}\\mathrm{S}$ or CdS, the capability for light absorption can be shifted to longer wavelengths. Films of PbS‐STN and CdS‐STN were produced via the same microwave‐assisted hydrothermal method and showed superamphiphilicity similar to the STN films. Compared to $\\mathrm{TiO}_{2}$ surfaces, the superamphiphilicity remained permanently stable, even after 6 months, without the need for light illumination.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 3.5.8 Dip Coating  \n\nDip coating is a very simple and popular method for creating thin films. Uniform films can be applied to flat or cylindrical substrates. A related technique often used in industrial applications is spin coating.  \n\nChen et al. developed a superhydrophilic, superamphiphilic, scratch‐resistant coating via a dip‐coating process [82]. The coating consisted of aggregated zeolite nanoparticles, which resulted in the useful properties mentioned earlier. The ­prepared surfaces had higher roughness and strength compared to amorphous $\\mathrm{SiO}_{2}$ surfaces. In  addition, the coatings showed a high antireflective and superamphiphilic properties that are of high interest in, for instance, the production of solar panels.  \n\nIn addition, surfaces with tunable wettability for guiding water droplets can be produced by dip coating [83]. For example, silicon nanowires can be dip‐coated in dodecyltrichlorosilane to attain a superhydrophobic state, and then the wettability can be converted to hydrophilic via UV‐enhanced photodecomposition.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 3.5.9  Phase Separation  \n\nThe phase‐separation method is commonly used for the fabrication of porous polymer coatings. In this method, the starting material is typically a polymer solution or a polymer blend, and phase separation is induced by changing temperature or pressure or both. For example, porous polymers with switchable wettability can be produced by the condensation of organo‐triethoxysilane in a mixture of an organic solvent and water [28].  \n\nIn another approach, Zhang et al. reported a one‐step production method for a superhydrophilic polymer surface. A nylon 6,6 plate was swelled by formic acid and then immersed in a coagulate bath to induce precipitation. Microparticles with ­nano‐ protrusions were generated and linked together, covering the surface. After drying, the as‐formed surface showed superhydrophilic abilities due to the hydrophilic nature of nylon and the network of micro/nano flower‐like particles [84]. Poly(l‐lactic acid) substrates can be prepared using a phase‐separation‐based method. Using argon‐ plasma posttreatment, the wettability of the surfaces can be controlled in the range from superhydrophobic to superhydrophilic [85].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# 3.5.10  Templating Method  \n\nTemplating is an effective method for constructing surfaces with highly controlled morphology. The inverse of a template can be formed and replicated again for producing positive replicas and offering the possibility to template natural biosurfaces.  \n\nNanoporous anodic aluminum oxide (AAO) has been commonly used for the pressure‐driven imprint process. By choosing AAO replications with different pore diameters and channel lengths, the diameter and height of surface‐projecting ­nanostructures can be controlled [86–88].  \n\nAnother widely used template material is polystyrene. Li et al. used a polystyrene colloidal monolayer as a template to produce a hierarchically ordered $\\mathrm{TiO}_{_2}$ ­hemispherical array with hexagonal not‐close‐packed tops [89]. The obtained coating exhibited excellent superhydrophilicity with a contact angle of $0^{\\circ}$ without UV radiation. A very novel approach for making superhydrophobic/superhydrophilic patterns is based on printing an “ink” (an ethanol solution of a phospholipid) on a porous superhydrophobic surface [90].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 3.6 APPLICATIONS",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# 3.6.1 Self‐Cleaning  \n\nOne of the most attractive applications, which is already being commercialized, is the production of self‐cleaning coatings. Self‐cleaning coatings are broadly classified into two major categories: superhydrophilic (water contact angles close to $0^{\\circ}$ ) and superhydrophobic (water contact angles ${>}150^{\\circ}$ ). Both clean themselves by the action of water. On a superhydrophilic surface, water spreads, and pollutants can be removed by a stream of water [91]. Water spreads because adhesive forces between the liquid and the substrate play a more important role than internal cohesive forces within the liquid [92]. In addition, these strong adhesive forces between water and surface prevent interactions between impurities and the surface, enabling their easy removal [93]. Water penetrates between impurities and the surface so that the impurities can be washed away [37]. On superhydrophilic surfaces, traces of water will evaporate much faster than on superhydrophobic surfaces, thereby contributing to a cleaner surface. On superhydrophilic coatings consisting of $\\mathrm{TiO}_{_2}$ or other semiconductor materials, two self‐cleaning mechanisms can occur [94]. One is the photocatalytic effect that is induced by sunlight to chemically breakdown organic pollutants. This effect is a consequence of its semiconductor nature [95]. Photocatalytic properties of $\\mathrm{TiO}_{_2}$ are beyond the scope of this chapter and can be found elsewhere [96]. The decomposed impurities can be easily washed away by water that immediately spreads to a film on superhydrophilic surfaces [97]. The other self‐cleaning mechanism involved in $\\mathrm{TiO}_{_2}$ coatings is the superoleophilic effect. Superamphiphilic surfaces enhance self‐ cleaning, because oily liquids spread completely, thereby increasing the contact area with the $\\mathrm{TiO}_{_2}$ coating and promoting the faster decomposition of contaminants.  \n\nThe self‐cleaning features of superhydrophilic and/or superamphiphilic surfaces are useful for a broad range of possible applications. For example, a soiled kitchen exhaust fan consisting of plastic cannot be cleaned only with water. However, if the exhaust fan is coated with a superhydrophilic and/or superamphiphilic surface, oily contaminants can easily be removed by a stream of water [97]. Traffic signs soiled by exhaust gases from automobiles could be cleaned in the same way or even by rainfall [94]. Self‐cleaning is of particular interest for building walls and windows where cleaning is very difficult. A building wall (such as in $\\operatorname{Fig}3.4)$ can be cleaned just by rainwater, saving cleaning costs and time [97].  \n\n![](images/738e07800e5961b6c141cc72b9059c992528b5f4ae5aafa29f5d3e77b08e1d00.jpg)  \nFig. 3.4  Comparison of a conventional tent material (left) and a self‐cleaning material coated with $\\mathrm{TiO}_{_2}$ (right). Used with permission from Ref. 98. $\\circleddash$ The Japan Society of Applied Physics.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# 3.6.2  Antifogging and Antireflective Coatings  \n\nAntifogging surfaces are needed to maintain visibility through transparent surfaces in high‐humidity environments. Since relative humidity is a strong function of temperature, a vapor can easily reach its saturation limit in response to changes in ­temperature. In addition, condensation often occurs when a cold surface rapidly comes into contact with warm moist air. The resulting condensation appears as tiny droplets. These droplets randomly scatter light, causing the surfaces to be translucent or foggy. A superhydrophilic coating can prevent fogging, because water spreads on the rough hydrophilic surface to form a thin film instead of droplets. In addition to antifogging, superhydrophilic coatings commonly exhibit antireflective properties.  \n\nGenerally speaking, surface roughness and transparency are competitive ­properties. Hydrophilicity increases as surface roughness increases, while the transparency of rough surfaces often decreases owing to the Mie scattering effect [99]. Antireflective properties reduce glare and maximize the amount of light passing through, an effect that shows promise for improving materials used in greenhouses and solar‐cell panels. As a consequence, it is of great importance to develop a simple method for fabricating transparent and superhydrophilic coatings with specific functional properties. To facilitate commercialization, such coatings also need to be mechanically stable and cost‐effective.  \n\nAntireflective properties are very important for the production of solar modules, because solar conversion efficiency depends on optical transmission [82]. Son et al. showed that the efficiency of solar panels coated with a superhydrophilic surface is reduced by only $1.4\\%$ after 12 weeks in an outdoor environment. In comparison, the efficiency of uncoated solar panels is reduced by $7.8\\%$ [3].  \n\nRubner’s Research Group at the Massachusetts Institute of Technology (MIT) fabricated a superhydrophilic polyelectrolyte multilayer film with exceptional ­antifogging and antireflective properties [29]. This film was created from LbL assembled $\\mathrm{SiO}_{2}$ nanoparticles and a polycation. With suitable control over the processing conditions $\\mathrm{\\Phi_{\\mathrm{pH}}}$ , concentration, etc.) and proper choice of nanoparticle size, ­multifunctional nanoporous thin‐film coatings were created. The resulting film was superhydrophilic, antifogging, and significantly suppressed the reflection of light (antireflective). To improve mechanical durability, the final deposited film was heated to about $500^{\\circ}\\mathrm{C}$ for $^{4\\mathrm{h}}$ . After this process, the resulting thin‐film coating could withstand aggressive rubbing and easily passed a standard scotch‐tape peel test. A simple experiment was carried out to demonstrate the antifogging properties of the obtained superhydrophilic coating. Two glass slides, one coated and the other uncoated, were placed in a refrigerator at $-18^{\\circ}\\mathrm{C}$ for some time. After removal from the refrigerator, the coated slide remained transparent and not fogged, while water condensate readily formed on the uncoated slide. On a coated surface, water remains on a wet surface as a continuous sheet instead of dewetting to form droplets. This property of coated films provides the opportunity for maintaining good visibility even when the nanopores in the film are fully saturated with water. Since these coatings are nanoporous structures composed of $\\mathrm{SiO}_{2}$ and air‐filled pores, their refractive index lies between those of silica $(n\\approx1.45)$ and air $(n=1)$ ); this makes them good candidates for antireflective applications.  \n\nAs one of the first and most prominent superhydrophilic coatings, $\\mathrm{TiO}_{_2}$ (discussed earlier) also possesses impressive antifogging properties. However, the need for UV radiation to produce desirable surface properties remains a major drawback to using this coating material [10]. To eliminate this drawback, porous $\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ (TS) composite thin‐film coatings with superhydrophilic performance have been produced by a sol–gel process under template‐free conditions [47]. When the $\\mathrm{SiO}_{_2}$ content was set to $20\\%$ , the TS composite coatings exhibited a water contact angle of $2.5^{\\circ}$ without UV radiation, and the time needed for a water droplet to completely spread over the surface was less than $1\\mathrm{s}$ . The resulting coatings showed excellent antifogging properties, which are attributed to the instantaneous spreading of droplets absorbed on the coated glass surface to form sheets similar to a water membrane. The water therefore evaporates immediately, providing quicker drying of the surface and keeping it clear for a long time (Fig. 3.5).  \n\nThere are approaches other than $\\mathrm{TiO}_{_2}$ technology for obtaining antifogging and antireflective coatings [100, 101]. You et al. produced a thin‐film coating of $\\mathrm{La(OH)}_{3}$ nanorods on a glass substrate by simple self‐stacking methods [102]. These single layer coatings significantly reduced reflective losses for visible light. To improve the roughness of these coatings, silica nanoparticles were deposited. The resulting $\\mathrm{La(OH)}_{3}/\\mathrm{SiO}_{2}$ film showed nanoporosity‐driven superhydrophilicity and the antifogging property with no significant loss in the antireflective property.  \n\n![](images/7e8aef52f636ab3c39a32114aa4ec0cfc504461e96e4e790e350ce07e50faf72.jpg)  \nFig. 3.5  Comparison of antifogging behavior of a bare glass slide (right) with a slide partially coated (left) with superhydrophilic porous TS film. Used with permission from Ref. 47. $\\mathbb{O}$ Elsevier.  \n\nRecently, a novel antifogging coating has been developed for plastic substrates; the coating consists of a hydrophilic/hydrophobic bilayer structure [103]. The bottom layer is hydrophobic colloidal silica, which acts as a mechanical support and a hydrophobic barrier against water penetration. Atop this layer, an antifogging coating was applied; this top layer incorporates a superhydrophilic species synthesized from Tween‐20 (surfactant), isophorone diisocyanate (coupling agent), and 2‐hydroxyethyl methacrylate (monomer). The resulting coating was transparent, wearable, and could be soaked in water for 7 days at $25^{\\circ}\\mathrm{C}$ without downgrading its antifogging capability.  \n\nBesides superhydrophilic and highly hydrophilic surfaces [104–107], the so‐ called zwitter‐wettable surfaces also exhibit excellent antifogging and antifrost properties [108]. Zwitter‐wettable coatings have the ability to rapidly absorb molecular water from the environment while simultaneously appearing hydrophobic when probed with water droplets (Fig. 3.6). They are prepared by using hydrogen‐bonding assisted LbL assembly of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA). In an additional step, functionalizing the nanoblended PVA/PAA multilayer with poly(ethylene glycol methyl ether) (PEG) segments produced significantly enhanced antifogging and frost‐resistant properties.  \n\nAntifogging coatings undoubtedly impact diverse applications such as sports and sanitary equipment, lenses for optical devices, automobile windshields, windows, eyeglasses, camera lenses, or any other transparent glass or plastic surface. For example, when a food item is packaged and displayed in a refrigerated cabinet, the relative humidity inside the package increases because of the decrease in temperature. Consequently, water tends to condense on the inner surfaces of packages, which, if treated to be antifogging, can enhance the visual display of the packaged items. Commercially available antifogging and antireflective coatings will be discussed in the following sections.  \n\n![](images/5fb70577a11ea5208f36f871501b6bacd16bec26e0b181f085b8064f3371faa9.jpg)  \nFig. 3.6  (a) Temporal evolution of water‐drop profiles on a PEG‐functionalized PVA/PAA multilayer film at $37^{\\circ}\\mathrm{C}$ and $80\\%$ RH. (b) Changes in water contact angle over time for a PVA/PAA multilayer film at $37^{\\circ}\\mathrm{C}$ and $80\\%$ RH. (c) Changes in water contact angle over time for a PEG‐functionalized PVA/PAA multilayer film at $22\\pm1^{\\circ}\\mathrm{C}$ and $40\\pm10\\%$ RH and at $37^{\\circ}\\mathrm{C}$ and $80\\%$ RH. (d) Photograph of a water drop placed on a PEG‐functionalized PVA/ PAA multilayer film after being transferred from $-20^{\\circ}\\mathrm{C}$ to $22\\pm1^{\\circ}\\mathrm{C}$ , $40\\pm10\\%$ RH. Inset photograph shows the magnified image of the water drop with a contact angle above $90^{\\circ}$ . Only the glass coated with PEG‐functionalized PVA/PAA multilayer resists formation of frost. (e) Schematic of zwitter‐wettability. MIT logo in the figure is used with permission from the Massachusetts Institute of Technology. Used with permission from Ref. 108. $\\mathbb{O}$ American Chemical Society.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# 3.6.3  Antifouling Properties  \n\nFouling is the deposition of an unwanted material on solid surfaces to the detriment of function. In marine engineering, fouling refers to the growth of microorganisms, algae, plants, etc., on a surface immersed in seawater.  \n\nIn membrane technologies, fouling is the deposition of retained particles, macromolecules, and salts at the membrane surface or inside the pores. This fouling is caused by interactions between the membrane surface and the foulants in many ­different forms. The foulants not only physically interact with the membrane surface but also chemically degrade the membrane material [109]. It is generally assumed that fouling decreases with an increase in the hydrophilicity of the polymeric material. This assumption seems reasonable, since with an increase in membrane surface hydrophobicity, hydrophobic organic molecules are driven toward the surface, enhancing surface contamination. Water separation membranes should be designed to maximize their surface affinity with water so as to increase their resistance to fouling [110]. Antifouling properties arise because of the strong hydration layer of the hydrophilic surface, which opposes the adsorption of molecules and particles on the membrane surface [111]. Elimelech et al. experimentally confirmed these hypotheses by producing superhydrophilic thin‐film composite membranes on which increased resistance to fouling was observed [112, 113].  \n\nBiomedical devices can be subjected to fouling via the deposition of surplus cells, proteins, and biomolecules. Patel et al. recently examined two types of superhydrophilic surfaces as potential surfaces in microfluidic devices: [6] polyester films treated by oxygen plasma and indium–tin‐oxide‐coated glasses treated by an electrochemical method. Fluorescence microscopy studies confirmed the significantly reduced adhesion of fluorescein and fluorescent proteins after the surfaces were treated to be superhydrophilic, thereby indicating their potential for antifouling applications.  \n\nMany types of hydrophilic polymer surfaces with suitable wettability and antifouling properties, especially bio‐antifouling, have been proposed and prepared by surface‐initiated controlled radical polymerization of vinyl monomers with specially designed hydrophilic functional groups; this process leads to densely grafted polymers on the solid surface, which are the so‐called polymer brushes [114, 115]. Kobayashi et al. investigated the behavior of different polyelectrolyte polymer brushes [116]. They observed that polyelectrolyte brushes repel both air bubbles and hexadecane in water. Even when silicone oil was spread on the polyelectrolyte brush surfaces in air, once they were immersed in water, the oil quickly rolls up and detaches from the brush surface. Figure 3.7 shows the contact angle of silicone oil on the surface of a poly[2-(methacryloyloxy)ethyl phosphorylcholin] (PMCP) brush and on an unmodified silicon wafer in air and in water. The oil detachment observed on the superhydrophilic polyelectrolyte brush in water was caused by low adhesive forces between the brush and the oil; this could contribute to its excellent antifouling and self‐cleaning properties.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# 3.6.4  Enhanced Boiling Heat Transfer  \n\nOver the past 80 years heat transfer under boiling conditions has been investigated by numerous scientists worldwide [117, 118]. One of the most important parameters in the performance of pool boiling is the critical heat flux (CHF). The CHF is the maximum heat flux at which boiling heat transfer sustains its high cooling efficiency. When a surface reaches CHF, it is coated with a vapor film, which then interferes with contact between the surface and the liquid and decreases the heat‐transfer efficiency. Subsequently, the system temperature increases, and if it exceeds the limits of its containment materials, system breakdown occurs. Because of this, every  \n\nThe right figures are schematic images of the oil on brush in the left photographs.  \n\n![](images/e8c93088012c2c75308480157da59d04009220e8d32f247d573032a41554532d.jpg)  \nFig. 3.7  Wettability‐reversion phenomena of a silicone oil droplet $(5.0\\upmu\\mathrm{l}$ , Shin‐Etsu Chemical Co. KF‐96‐100CS) on a PMPC brush (a, b) in air and (c,d) in water. Photograph (c) (side view) displays an oil droplet on a PMPC brush substrate in water, showing superoleophobicity, with a contact angle of $173^{\\circ}$ . Used with permission from Ref. 116. $\\mathbb{O}$ American Chemical Society.  \n\nsystem integrates a safety margin by operating at a heat flux much lower than CHF;   \nof course, this safety measure limits the efficiency of the system.  \n\nIn 1993, Wang and Dhir showed that CHF can be increased by enhancing surface wettability [119]. Since then, a number of studies have reported that surface wettability is an important factor affecting boiling heat transfer [120, 121]. In 1995, Choi introduced the concept of nanofluids [122]. Nanofluids are a new class of nanotechnology‐based heat‐transfer fluids, engineered by dispersing and stably suspending nanoparticles (with dimensions on the order of $1{-}50\\mathrm{nm},$ ) in traditional heat‐transfer fluids. The base fluids include water, ethylene, oil, biofluids, and polymer solutions. Various materials are commonly used as nanoparticles, including chemically stable metals (e.g., copper, gold, silver), metal oxides (e.g., alumina, bismuth oxide, silica, titania, zirconia), ­several allotropes of carbon (e.g., diamond, CNTs, fullerenes), and functionalized nanoparticles [123]. Vertically aligned nanoforests of hydrophilic/ superhydrophilic nanorods [124], nanowires [125], and water‐based alumina nanofluids [126] have shown the potential for considerably improving boiling heat transfer. The increase in CHF is attributed to roughness, high surface‐tension forces of superhydrophilic ­nanostructures for pumping in fresh liquid, and capillary wicking phenomena [127].  \n\nPhan et al. investigated the influence of surface wettability on nucleate boiling heat transfer by varying the water contact angle [120]. It was found that increasing surface wettability increases the vapor‐bubble departure radius and reduces the bubble emission frequency. Hsu et al. coated a plain copper surface with silica nanoparticles and found that the superhydrophilic surface with a contact angle less than $10^{\\circ}$ has a larger CHF than the hydrophilic one with a contact angle of $16^{\\circ}$ [121]. The superhydrophilic surface exhibits an increase in CHF of approximately $100\\%$ compared to a plain copper surface. For superhydrophilic surfaces, small bubbles form on the surface when the wall temperature is $100^{\\circ}\\mathrm{C}$ (illustration in Fig.  3.8). These small growth bubbles move and merge with other bubbles and then depart the surface. However, the size and number of growth bubbles on the heating surface both increase when the surface is more hydrophobic, as shown in Fig. 3.8b and c. Fig. 3.8d shows the effects of growth bubbles during boiling on a superhydrophobic surface; bubbles spread over the surface and coalesce with bubbles formed at other sites, causing a large area of the surface to be covered with a vapor film [13]. This vapor film interferes with contact between the surface and the surrounding liquid and decreases heat‐transfer efficiency.  \n\n![](images/a97b98487fb68e6d375d4359d39d2cbd32bc15639c8d2bba193cdbfe47cc6f73.jpg)  \nFig. 3.8  Effects of surface wettability on the growth of bubbles during boiling on (a) superhydrophilic surface, (b) hydrophilic surface, (c) hydrophobic surface, and (d) superhydrophobic surface. In (d), the bubbles coalesce into a thin film that impedes heat transfer from the surface. Used with permission from Ref. 120. $\\mathbb{C}$ Elsevier.  \n\nSince CHF is the upper limit for nucleate boiling, the enhancement of CHF offers the potential for major improvements in the performance of many practical applications. For example, the use of superhydrophilic coatings with higher CHFs could enable the effective thermal management of even smaller and more powerful electronic devices, improve power‐up rates in commercial nuclear plants, allow the design of more compact heat exchangers for the chemical industry, among others.  \n\n![](images/e692db6669748958a96d7a9ade29a69edaf3dfc237822d31e2beb07714a86132.jpg)  \nFig. 3.9  Energy‐saving system in which exterior surfaces of buildings are covered with a $\\mathrm{TiO}_{2}$ coating. The coating is made superhydrophilic by exposure to UV radiation in sunlight and then by pumping of stored rainwater over those surfaces. Evaporation of water from the surfaces helps cool the building and reduces load on air conditioning equipment. Used with permission from Ref. 98. $\\circledcirc$ The Japan Society of Applied Physics.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# 3.6.5 Efficient Water Evaporation  \n\nA current problem in big cities around the world is the so‐called “heat island phenomenon.” Increasing amounts of exhaust gases from traffic and decreasing areas of lakes and green land significantly increase temperatures in cities. Hashimoto et al. suggested the use of superhydrophilic surfaces to prevent the heat island phenomenon. The facades of a building equipped with a superhydrophilic surface can be completely covered by a thin water film. Through quick and efficient water evaporation, the building can be cooled by the flux in latent heat (Fig. 3.9). Therefore, if small amounts of collected rainwater are continuously sprinkled onto the superhydrophilic surface, the temperature increase in cities could be reduced. Thinner water layers (in the range of $0.1\\mathrm{mm}$ ) improve the efficiency of cooling buildings and the surrounding air. The decrease in temperature brings another positive impact: less air conditioning is needed, leading to a total decrease in energy consumption of more than $10\\%$ .",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 25,
+        "chunk": "# 3.6.6 Switchable and Patterned Wettability Coatings  \n\nCombining the two extremes, superhydrophilicity and superhydrophobicity on the same surface in precise 2D patterns opens the possibilities for exciting new functionalitiesinawidevarietyofapplications.Generally,superhydrophilic–­superhydrophobic patterned surfaces are used to control bioadhesive and nonbioadhesive regions. The “switch” between the two regimes can be triggered by heat, light, or a solvent.  \n\nSwitching between superhydrophobicity and superhydrophilicity in porous materials was predicted theoretically and demonstrated experimentally using a thermally induced change in contact angle [28]. The porous materials used in that study were produced by a phase‐separation method. Reaction occurs through the hydrolysis of the ethoxy groups and the polymerization of the silanol groups thus formed. Polymerization causes a decrease in the dipole moment, leading to hydrophobic phase separation. The dried material had organic groups on its surface, causing the foam to be superhydrophobic, but after thermal treatment to $400^{\\circ}\\mathrm{C}$ , the surface was superhydrophilic. [48] This sudden hydrophilic–hydrophobic transition is due to the cross‐linking of the silica backbone, which causes the redistribution of organic groups from the surface into the bulk of the material. In porous materials, the transition is very sharp, and because the pores can only be empty or filled, partial states are not energetically favored. Beside porous surfaces, rough surfaces also can exhibit wetting transitions [74].  \n\nHan et al. showed that superhydrophilic channels photo‐patterned in a superhydrophobic porous polymer layer can separate peptides of different hydrophobicities and isoelectric points by 2D thin‐layer chromatography [128]. Recently, another facile and versatile method has been presented for creating superhydrophilic patterns in superhydrophobic porous polymer films by UV‐initiated photografting [129]. The extreme difference in wettability between superhydrophilic and superhydrophobic areas permits the use of superhydrophilic patterns as microfluidic channels. The method allows precise control of the size and geometry of photo‐grafted superhydrophilic patterns. For mixed polymer brushes that consist of incompatible hydrophobic and hydrophilic components attached to a substrate, the top morphology and composition of the films can be switched by exposure to different solvents, which in turn results in changes in the surface energy and water contact angle [30, 130, 131].  \n\nThere are many emerging technologies that can benefit from the combination of extreme wettabilities on one substrate. Some of those advantages are patterning of complex geometries with liquids, production of cell microarrays, offset printing, and control of the adhesion of proteins, cells, or bacteria.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 26,
+        "chunk": "# 3.6.7 Other Applications  \n\nBesides the main applications of self‐cleaning and antifogging, superhydrophilic surfaces are also very suitable for filtration processes. For example, Sun et al. found that a superhydrophilic polypropylene filter shows remarkable filtration efficiency and may serve as an ultrafilter. Opposite, uncoated polypropylenes filter presents poor filtration properties because of its hydrophobic properties [132]. The superhydrophilic property of substrates, particularly of metals, can also be used for the attachment of biocoats as BMP‐2. These coatings exhibit bioactive properties in bone and are therefore suited for implants [133].  \n\nThe examples of applications mentioned above illustrate the immense range of potential applications of superhydrophilic surfaces. There is continuing development of novel and improved superhydrophilic surfaces for new applications. However, the remaining question is how many of possible applications are already being implemented in real products. This question is addressed in the following section.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 27,
+        "chunk": "# 3.7 COMMERCIAL COATINGS  \n\nSome of the aforementioned technologies are already commercialized products available in the market. This section gives a sampling of companies that offer superhydrophilic products in different industrial fields. On the one hand, there are finished products for end users, and on the other hand, there are chemical solutions that can be easily sprayed onto a surface to obtain superhydrophilic properties.  \n\nIn particular, coatings containing $\\mathrm{TiO}_{_2}$ nanoparticles are widely offered for different uses. One of the first products in the market with a self‐cleaning property was a glass cover for lights in tunnels [98]. These covers are mainly used in tunnels in Japan; they remain clean due to a photocatalytic process induced by sodium lamps that emit UV light. In contrast, conventional glass covers are covered by exhaust compounds (Fig. 3.10), leading to dark tunnels.  \n\nThe German company “GXC Coatings GmbH” offers a group of GXC NuGlass PK coatings that modify different surface substrates, including glass, polycarbonate, polymethylmethacrylate, and various metals. The coating includes $\\mathrm{TiO}_{_2}$ nanoparticles and exhibits a self‐cleaning effect. It is mainly used in cover panels for exterior lighting systems in the automotive industry, for covers of measuring instruments, and in architectural elements [134].  \n\nSelf‐cleaning windows constitute a major part of the market of superhydrophilic products. The first glass with self‐cleaning properties, “Pilkington Active,” was introduced by the British company Pilkington in 2001 [135]. The technology is based on $\\mathrm{TiO}_{_2}$ particles; the surface exhibits superhydrophilicity and can decompose dirt with the help of sunlight [136, 137]. Pilkington ActiveTM windows are easily cleaned by rain and are therefore used in many public and private buildings, including the Town Hall in France, the Britomart Transport Centre in New Zealand, and the Hilton Hotel in Finland. Besides the construction industry, the technology is also used in the automotive industry for the production of side mirrors for cars [98, 138].  \n\n![](images/1605b7c2f52dae9604eb960a5ec26a136e6e76dc65a1168ee184239df3fc1f9a.jpg)  \nFig. 3.10  Glass covers on lighting fixtures in a highway tunnel. Without a $\\mathrm{TiO}_{_2}$ coating, the covers are darkened by automobile exhaust (left). With a $\\mathrm{TiO}_{_2}$ coating, the covers remain clean (right). Used with permission from Ref. 98. $\\mathbb{O}$ The Japan Society of Applied Physics.  \n\nIn 2001, Saint Gobain, a competitor of Pilkington, presented a product called SGG Aquaclean at the international building exhibition Batimat [139, 140]. In contrast to most other self‐cleaning surfaces, the self‐cleaning effect is based only on the superhydrophilic property of the surface without any catalytic effect; it can be applied to all building elements that are exposed to rain. Only 1 year later, PPG Industries introduced a self‐cleaning glass called Sun Clean [141]. Similar to almost all ­self‐ cleaning windows, the Sun Clean coating is based on $\\mathrm{TiO}_{_2}$ technology and is mainly used in commercial building applications [142]. There are many other competitors in the market offering self‐cleaning windows, including, for example, Neat Glass from Cardinal Glass Industries [143]. This company claims that Neat Glass shows the same self‐cleaning effects as Pilkington Active and Sun Clean, but it also transmits more visible light and reflects less. This coating consists of a mixture of titanium dioxide and silicon dioxide [144].  \n\nBesides self‐cleaning windows, there are other superhydrophilic materials developed for use in the construction industry. In 2002, the Japanese company Toto Ltd. introduced a superhydrophilic and photocatalytic paint for walls called Hydrotect [145, 146]. The system consists of three‐layer painting that can be easily applied on outside walls to produce a self‐cleaning surface. The technology is based on $\\mathrm{TiO}_{_2}$ nanoparticles; besides self‐cleaning, it also leads to surfaces that can purify the atmosphere by a catalytic process. Toto Ltd. claims that up to now, more than 1000 public and private buildings are equipped with the Hydrotect technology. Compared to uncoated buildings, the walls stay much cleaner (see Fig. 3.11). For example, the facade of a Toyota factory in Aichi is coated with Hydrotect to make a contribution toward sustainable production [148]. One of the leading manufacturers of ceramic tiles, Casalgrande Padana, developed, in cooperation with Toto Ltd Bios Self Cleaning Ceramics®, a product line of porcelain tiles with self‐cleaning properties. The products are based on the Hydrotect technology from Toto and can be used in both interior and exterior architectural applications [149]. The tiles also exhibit antibacterial and smell‐reducing properties, making them very suited for indoor applications [150, 151]. Alcoa Architectural Products used the Hydrotect technology to offer a self‐cleaning aluminum panel suited for facades; the product is called Reynobond with EcoClean [152]. The panels also clean the surrounding air by a photocatalytic effect [153].  \n\n![](images/592069fe82d20bd92347cf5da99fc1289b60fe2307eef760fbfa9111f65ecedc.jpg)  \nFig. 3.11  Effects of outdoor weathering (left) on a superhydrophilic building façade and (right) on a façade not treated with a superhydrophilic coating. Used with permission from Ref. 147. $\\mathbb{O}$ Alcoa Inc.  \n\nSelf‐cleaning is not the only important property of superhydrophilic surfaces that has been commercialized. There are already products in the market with antifogging properties. The company Akzente Oberflächen‐ und Vertriebs GmbH in Germany developed an antifogging coating based on plastics [154]. Acryl groups are a main component used during the synthesis of the plastics. The antifogging coating is mainly used in the production of motorcycle helmets and goggles.  \n\nThe products mentioned above are mainly suited for specific applications. In addition, some superhydrophilic products in the market can be used in our daily lives. Superhydrophilic coating solutions that can be easily sprayed on various substrates to get self‐cleaning glasses or antifogging contact lenses are offered by several companies, including Laiyang Zixilai Environmental Protection Technology Co., Ltd. and Tomorrow Nano Science and Technology Co. in China and iCoat Company in America [155–157]. For example, the product IC No‐Fog from iCoat can be applied to various lens materials, both plastic and glass.  \n\nThis selection of superhydrophilic products shows that such novel technologies will improve living standards and make contributions to solve important everyday problems.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 28,
+        "chunk": "# 3.8 CONCLUSIONS AND OUTLOOK  \n\nThe production of superhydrophilic and superamphiphilic coatings is a new and interesting field in research and industry. Since 2000, research on superwetting coatings has expanded, resulting in a significant increase in the number of publications.  \n\nGenerally, artificial superhydrophilicity and/or superamphiphilicity can be achieved by two ways: a texture‐induced method or a photoinduced strategy. Texture‐ induced superhydrophilicity is attained by creating rough surface structures on materials having high surface energies. Alternatively, photoinduced superhydrophilicity using $\\mathrm{TiO}_{_2}$ and $z_{\\mathrm{{nO}}}$ has attracted significant attention as an intriguing phenomenon that can provide antifogging and self‐cleaning properties. Regardless of which mechanism is used, it is clear that the incorporation of superhydrophilicity into commercial products can have significant benefits. Superhydrophilic coatings are already being used to impart features such as self‐cleaning, antifogging, and antireflecting; these coatings can also improve heat transfer from solid surfaces, which enables the fast cooling of surfaces.  \n\nSignificant studies have focused on the production of superhydrophilic surfaces with additional features, including wettability switching, patterning, and gradient wetting. These surfaces are expected to have exciting applications in microfluidics, microarrays, offset printing, etc.  \n\nHowever, there are still many challenges in the production of artificial superhydrophilic coatings. For instance, the production of photoinduced coatings having superhydrophobicity faces serious obstacles in terms of cost and materials.When texture‐induced superhydrophilicity is used as a production method, another challenge is poor mechanical stability, which is currently addressed through self‐­curing and self‐healing mechanisms. The investigation of these mechanisms should provide further future opportunities. In particular, coatings containing $\\mathrm{TiO}_{_2}$ have to be improved, because they are easily wiped off or damaged due to the lack of hardness. Up to now, most photoinduced coatings can only be used for outdoor applications, because superhydrophilicity is induced by UV light. Therefore, there is a need to develop superhydrophilic coatings with high hardness and optical transparency but without any need for external stimuli. Some research groups have already started to develop such coatings, but they are in the minority [158–160]. Although some superhydrophilic coatings are in the market, there is a demand for new technologies that provide superhydrophilic coatings with stable properties and that can be scaled‐up for commercial production.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 29,
+        "chunk": "# References  \n\n1.\t Fujishima, A., Rao, T. N., Tryk, D. A. (2000) $\\mathrm{TiO}_{2}$ photocatalysts and diamond ­electrodes, Electrochimica Acta, 45: 4683–4690.   \n2.\t Tahk, D. et al. (2010) Fabrication of antireflection and antifogging polymer sheet by partial photopolymerization and dry etching, Langmuir, 26: 2240–2243.   \n3.\t Son, J. et al. (2012) A practical superhydrophilic self cleaning and antireflective surface for outdoor photovoltaic applications, Solar Energy Materials and Solar Cells, 98:46–51.   \n4.\t Anandan, S. et al. (2013) Super‐hydrophilic graphene loaded $\\mathrm{TiO}_{2}$ thin‐film for self cleaning applications, ACS Applied Materials & Interfaces, 5: 207–212.   \n5.\t Yang, Y.‐F., Li, Y., Li, Q.‐L., Wan, L.‐S., Xu, Z.‐K. (2010) Surface hydrophilization of microporous polypropylene membrane by grafting zwitterionic polymer for anti‐biofouling, Journal of Membrane Science, 362: 255–264.   \n6.\t Patel, P., Choi, C. K., Meng, D. D. 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Available at http:// tmsearch.uspto.gov/bin/gate.exe?f=searchss&state=4807:rgnnt6.1.1. (accessed February 11, 2015.)   \n141.  PPG Industries. PPG Introduces SUNCLEAN Self‐Cleaning Glass for Commercial Applications. Available at http://www.ppg.com/en/newsroom/news/Pages/20121022B. aspx. (accessed December 6, 2014.)   \n142.  PPG Industries. How It Works: Self‐Cleaning Window Glass Technology. Available at http://www.ppg.com/en/newsroom/news/pages/20121022b.aspx. (accessed February 11, 2015.)   \n143.  Cardinal Glass Industries. Let Nature Service Your Windows. Available at http://www. cardinalcorp.com/products/neat‐glass/. (accessed December 6, 2014.)   \n144.  Cardinal Glass Industries. Architectural Glass Guide. Available at http://www. cardinalcorp.com/wp‐content/uploads/pdf/cardinal‐architectural‐brochure.pdf. (accessed December 6, 2014.)   \n145.  TOTO. HYDROTECT. Available at http://de.toto.com/technologie/technologie‐einzelan sicht/Technology/show/HYDROTECT/. (accessed December 6, 2014.)   \n146.  Japan Echo Inc. Self‐Cleaning Walls and Windows. Available at http://web‐japan.org/ trends/08_sci‐tech/sci090116.html. (accessed December 6, 2014.)   \n147.  Alcoa Architectural Products. The EcoClean The EcoClean™ Self Cleaning Process. Available at http://www.alcoa.com/bcs/aap_eastman/ecoclean/en/pdfs/Web_support_ slides_self_cleaning.pdf. (accessed December 6, 2014.)   \n148.  ARCHmatic. Superhydrophilie verspricht selbst‐ und luftreinigende Fassaden. Available at http://www.baulinks.de/webplugin/2010/1944.php4. (accessed December 6, 2014.)   \n149.  Casalgrande Padana S.p.A. A New Step Forward in the Area of Bioactive Ceramics. Available at http://www.casalgrandepadana.com/index.cfm/1,869,2432,0,html/A‐NEW‐ STEP‐FORWARD‐IN‐THE‐AREA‐OF‐BIOACTIVE‐CERAMICS#.UWGe‐1ccfmg. (accessed December 6, 2014.)   \n150.  TOTO. Casalgrande Padana Launch Bios Self Cleaning Ceramics® with HYDROTECT $\\textsuperscript{\\textregistered}$ . Available at http://gb.toto.com/news/press‐releases/press‐releases/?tx_ttnews[tt_news]=284&c. (accessed February 11, 2015.)   \n151.  Mauro Manfredini. Percorsi in Ceramica. Available at http://www.casalgrandepadana. com/index.cfm/1,869,2432,0,html/A-NEW-STEP-FORWARD-IN-THE-AREA-OFBIOACTIVE-CERAMICS. (accessed February 11, 2015.)   \n152.  Alcoa Architectural Products. Smog‐Eating Buildings? Available at http://www.alcoa. com/aap/north_america/pdf/ecoclean/EcoClean_Newsletter1.pdf. (accessed December 6, 2014.)   \n153.  ARCHmatic. Aluminiumfassaden als Schmutz‐ und Smogvernichter. Available at http:// www.baulinks.de/webplugin/2011/1287.php4. (accessed December 6, 2014.)   \n154.  Akzente Oberflächen‐ und Vertriebs GmbH. Antifog Beschichtung. Available at http:// www.akzente‐hc.de/antifog‐beschichtung.html. (accessed December 6, 2014.)   \n155.  Focus Technology Co. L. Super Hydrophilic Nano Self Cleaning Coating for Car Glass Building Walls. Available at http://www.made‐in‐china.com/showroom/laiyangzixilai/ product‐detailkMSxVTRGHKpN/China‐Super‐Hydrophilic‐Nano‐Self‐Cleaning‐ Coating‐for‐Car‐Glass‐Building‐Walls.html. (accessed December 6, 2014.)   \n156.  weiku. Nano Self‐Cleaning and AntiBacteria Coating. Available at http://en.zixilai.com/ products_list/&pmcId=26.html. (accessed February 11, 2015.)   \n157.  iCoat Company. IC No‐Fog. Available at http://www.icoatcompany.com/ICNoFog.aspx. (accessed December 6, 2014.)   \n158.  Forbes, P. (2008) Self‐cleaning materials: lotus leaf‐inspired nanotechnology, Scientific American Magazine, 8: 1–5.   \n159.  Yamasaki, S. et al. (2010) Development of the organic‐inorganic hybrid super‐­hydrophilic layer, Fuji film Research & Development, 55: 29–33.   \n160.  Zorba, V., Chen, X., Mao, S. S. (2010) Superhydrophilic $\\mathrm{TiO}_{_2}$ surface without ­photocatalytic activation, Applied Physics Letters, 96: 093702–093703.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# PAPER 光学的 Optically transparent super-hydrophobic thin film fabricated by reusable polyurethane-acrylate (PUA) mold  \n\nTo cite this article: J-S Park et al 2018 J. Micromech. Microeng. 28 025004  \n\nView the article online for updates and enhancements.",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# Related content  \n\n- Polyurethane-acrylate-based hydrophobic   \nfilm: Facile fabrication, characterization, and application   \nJongsung Park, Bui Quoc Huy Nguyen, Ji  \nKwan Kim et al. - Hierarchical surfaces for enhanced selfcleaning applications   \nAriadna Fernández, Achille Francone, Lasse H Thamdrup et al. Surface modified nano-patterned SU-8 pillar array optically transparent superhydrophobic thin film   \nYoungsam Yoon, Dong-Weon Lee and Jeong-Bong Lee",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# Recent citations  \n\n- Self-cleaning of glass surface to maximize   \nthe PV cell efficiency   \nAdnan Ayaz et al   \nLarge scale roll-to-roll production of   \npolyurethane-acrylate-based hydrophobic   \nfilm: a next-generation protection layer for   \nsolar devices   \nJongsung Park et al Polyurethane-acrylate-based hydrophobic film: Facile fabrication, characterization, and application   \nJongsung Park et al  \n\n![](images/a34f791530e311910fe7c080b8b2dfa9db85e97e818465884707ffc282b3ab79.jpg)",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# lopebooks  \n\nBringing together innovative digital publishing with leading authors from the global scientific community  \n\nStart exploring the collection-download the first chapter of every titlefor free  \n\nhis content was downloaded from IP address 59.71.241.21 on 25/04/2021 at 07:27",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# 超疏水 Optically transparent super-hydrophobic 制造 thin film fabricated by reusable polyurethane-acrylate (PUA) mold 模型  \n\nJ-S Park1, J-H Park1 and D-W Lee $1,2\\textcircled{\\circ}$  \n\n1  MEMS and Nanotechnology Laboratory, School of Mechanical Engineering, Chonnam National   \nUniversity, Gwangju, Republic of Korea   \n2  Center for Next-generation Sensor Research and Development, Chonnam National University, Gwangju   \n61186, Republic of Korea  \n\nE-mail: mems@jnu.ac.kr (D W Lee)  \n\nReceived 26 September 2017, revised 16 November 2017   \nAccepted for publication 4 December 2017   \nPublished 4 January 2018  \n\n![](images/c71918b3c1b69d347915a318aa74022c2998fb351b84f5a51bff054df20a2c5d.jpg)",
+        "category": " Abstract"
+    },
+    {
+        "id": 6,
+        "chunk": "# Abstract  \n\nIn this paper, we describe a simple manufacturing method for producing an optically transparent super-hydrophobic polymer thin film using a reusable photo-curable polymer mold. Soluble photoresist (PR) molds were prepared with under-exposed and under-baked processes, which created unique hierarchical micro/nano structures. The reverse phase of the PR mold was replicated on the surface of polydimethylsiloxane (PDMS) substrates. The unique patterns on the replicated PDMS molds were successfully transferred back to the UV curable polyurethane-acrylate (PUA) using a laboratory-made UV exposure system. Continuous production of the super-hydrophobic PDMS thin film was demonstrated using the reusable PUA mold. In addition, hydrophobic nano-silica powder was sprayed onto the micro/nano structured PDMS surfaces to further improve hydrophobicity. The fabricated PDMS thin films with hierarchical surface texturing showed a water contact angle $\\geqslant150^{\\circ}$ . Excellent optical transmittance within the range of visible light of wavelengths between $400{-}800\\mathrm{nm}$ was experimentally confirmed using a spectrophotometer. High efficiency of the super-hydrophobic PDMS film in optical transparency was also confirmed using solar panels. The fabricated PUA molds are very suitable for use in roll-to-roll or roll-to-plate systems which allow continuous production of super-hydrophobic thin films with an excellent optical transparency.  \n\nKeywords: super-hydrophobic, polydimethylsiloxane, UV curable PUA, artificial lotus leaf, nano-silica  \n\nSupplementary material for this article is available online (Some figures may appear in colour only in the online journal)",
+        "category": " Abstract"
+    },
+    {
+        "id": 7,
+        "chunk": "# Introduction  \n\nA super-hydrophobic surface has the characteristic of being highly hydrophobic, i.e. very difficult to wet. Generally, the contact angle of water droplets is ${>}150^{\\circ}$ at the hydrophobic surface and the roll-off angle is ${<}10^{\\circ}$ [1]. There is tremendous effort to create artificial super-hydrophobic surfaces with water contact angles $\\geqslant150^{\\circ}$ that provides various advantages such as better drag reduction, self-cleaning, and anti-sticking effects. Most proposals for super-hydrophobic surfaces have been inspired by the natural world. A common feature of many proposals is the utilization of a dual scale (micro and nano) structure, which have proven to be an effective way for creating super-hydrophobic surfaces [2–4]. A variety of materials, such as black silicon, carbon nanotubes, and polymers, has been widely studied to realize the hierarchical micro-/nano-structured surface similar to a lotus leaf [5–7]. However, these proposals are still struggling with technical issues, such as transparency, scalability, manufacturing cost, and flexibility.  \n\nFor optically transparent surfaces, the material of films should be inherently transparent and the surface roughness should be smaller than the wavelength of visible light. Polymers, such as polymethyl methacrylate (PMMA), polystyrene (PS), and polydimethyl-siloxane (PDMS), have been widely studied in fields requiring high optical transparency. In recent years, studies using water-repellent functional groups, such as fluorine-silane on nano-silica particles, and chemical coating methods, such as titanium dioxide $\\left(\\mathrm{TiO}_{2}\\right)$ and silicon dioxide $(\\mathrm{SiO}_{2})$ , have been conducted. Such a chemical coating method can easily improve water repellency and it has an advantage of not being limited by the shape of the object being coated. However, the long-term durability of the superhydrophobicity coating is poor and discoloration of the film due to chemical reactions with the coating material often occurs. One-step fabrication of optically transparent film based on a PDMS material was reported in our previous report [8]. The unique PDMS structure greatly improves hydrophobicity, but it is difficult to reuse because thick photoresists (PR), more than $40\\ \\mu\\mathrm{m}$ , are used as the mold structure. Further, multiple coatings of the PR are desirable to generate better hierarchical micro-/nano-structures with reverse structures. This method is not easy to reproduce in fabricating the PR mold and requires a lot of processing time.  \n\nThe primary goal of this study is to report a new fabrication method for optically transparent super-hydrophobic thin films that overcomes the drawbacks of currently available manufacturing methods. Thick PR molds with reversed hierarchical structures were prepared using a modified photolithography processes. Next, the unique structure of the PR molds is replicated on the PDMS surface, which is similar to the surface of lotus leaves. The structure is then re-replicated to the photocurable polymer layer for the purpose of reusing the mold. The reusability of the photo-curable polymer is well suited for high volume production processes, such as a roll-to-roll or roll-to-plate process. Optically transparent PDMS thin films prepared from reusable molds have significantly improved hydrophobicity compared to general PDMS thin films without surface structures. In addition, the excellent elasticity and adhesion of the PDMS material can be extended to various curved surfaces without using additional adhesives. The new manufacturing process and successful experimental results reveal that the proposed idea has great potential for diverse uses of the super-hydrophobic transparent PDMS thin film.",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# Experimental methods  \n\nFigure 1 shows a photograph and schematic of a real and artificial lotus leaf, respectively. The hierarchical structure of the lotus leaf is made of a characteristic epidermis and covering wax layer. The epidermis of the lotus plant contains papillae that are $10{-}20\\ \\mu\\mathrm{m}$ tall and $10{-}15\\ \\mu\\mathrm{m}$ wide. As shown in figure 1(a), the epidermis surface with microstructures is covered with epicuticular waxes. These superimposed waxes are hydrophobic and form the second layer of the hierarchically double-layered structure. As shown in figure  1(b), the dual structures of the lotus leaf are successfully mimicked using a unique PR mold. In conventional photolithography, a vertical sidewall is strongly desirable during the exposure and development processes. Here, we hypothesize that a combination of soft-baking and UV exposure conditions created unexpected patterns, which is undesirable in conventional photolithography. However, the unique negative patterns of the PR are relatively useful for super-hydrophobic applications once the shapes are transferred to the PDMS. The pure PDMS has a water contact angle between about $90^{\\circ}$ and $100^{\\circ}$ when there are no structures on the surface. This contact angle can be significantly improved by adding surface structures. The super-hydrophobic water-repellent hierarchical structures of the PDMS surface also provide self-cleaning effects, a behavior that is very attractive in engineering applications. However, one of the drawbacks of this method is the utilization of the PR as a mold material. An organic solvent used to separate the super-hydrophobic PDMS film from the PR mold completely dissolves the PR mold and makes it impossible to reuse.  \n\nPDMS is known as optically clear, non-toxic, and nonflammable material. It is also known as dimethicone, which is a type of silicone oil. The water contact angle is close to $100^{\\circ}$ on a flat PDMS surface and can be increased up to $150^{\\circ}$ when additional processes are performed on the flat PDMS. The improved method for fabricating optically transparent surface-textured PDMS thin films is shown in figure 2. The thick AZ4620 PR is multi-coated on a 4 in silicon wafer (figure 2(b)). After coating the first PR, the soft-baking process is performed in a convection oven at $55~^{\\circ}\\mathrm{C}$ for $3\\mathrm{min}$ . The second PR coating is then repeated using the same process condition as for the first layer. After the third PR coating, the multi-layered PR is soft-baked again in a convention oven at $55~^{\\circ}\\mathrm{C}$ for $45\\mathrm{min}$ . A significant under soft-baking process condition allows the thick PR to maintain a certain amount of solvents, which enhances the dissolution rate of the PR. In general, the thick PR layer requires an increased soft-baking time when the convection oven is employed for the baking process. When the PR is cured in ovens, the solvent starts to evaporate from the PR surface. The cured PR surface layer disturbs continuous evaporation of solvent from the PR; the solvents remaining inside the PR are evaporated through the cured PR surface layer. The underexposed and under-baked positive PR technique is optimized to make the desired reverse image of the hierarchical micro/nano structures (figure 2(c)). In this way, it is possible to mimic the surface of Lotus leaf with negative patterns.  \n\nThe PDMS monomer (base) and curing agent are mixed with a known ratio (10:1) and the mixture is placed in a desiccator to de-gas in a vacuum. The degassed PDMS solution is gently poured on the severely under-baked PR mold and then placed in a vacuum oven again. The spin-coated PDMS sample is degassed until trapped bubbles are completely removed from interface between the PDMS and the PR mold (figure 2(d)). The thickness of the cured PDMS layer is about $2\\mathrm{mm}$ , which is controllable using a changing spin speed and number of PDMS coating layers. Next, the PDMS layer is cured at ${>}80^{\\circ}\\mathrm{C}$ for $\\mathtt{4h}$ . Finally, the super-hydrophobic PDMS film is replicated by removing the PR mold with an acetone solution (figure 2(e)). To optimize the photolithography processes, various temperatures and exposure times were tested during the preliminary experiments. When the temperature for soft-bake was increased, the depth of developed area was decreased and the head of pillar structures was increased.  \n\n![](images/c0f16f76700fe3c1d671b7f0e540463473b2dd8e0660e74d3e7670a444f6ddaf.jpg)  \nFigure 1.  Optical image for (a) natural Lotus leaf and (b) process flow for fabrication of artificial lotus leaf based on PDMS.  \n\n![](images/cbf51f397597910b6f2a2959a9cd1ce36439808c39ea14bdfdd68b16ea9bb89e.jpg)  \nFigure 2.  (a)–(i) Schematic of improved fabrication process employing reusable molds, (j) scanning electron microscope images showing the fabricated micro/nano structured PDMS structures before and after nano silica coating and (k) optical image of water droplet on surfacepatterned PDMS film.  \n\nThe maximum temperature for the fabrication of desired mold structures was about $70~^{\\circ}\\mathrm{C}$ . Subsequently, the liquid phase UV-curable PUA is poured on the replicated PDMS film with unique structures on the surface (figure 2(f)). Next, the UV-curable PUA is solidified for 20 s using a laboratorymade UV system (figure $2(\\mathrm{g)}$ ) with an optical power of $5\\mathrm{mW}$ The cured PUA is then separated from the replicated PDMS mold (figure $2(\\mathrm{h})_{,}^{\\cdot}$ ). The UV-curable PUA is prepared using 4-hydroxybutyl acrylate $(85\\%)$ , acrylic acid $(11\\%)$ , ethylene glycol dimethacrylate $(1\\%)$ , and $2^{\\prime}$ -dimethoxy-2- phenylacetone phenone $(3\\%)$ . The fabricated PUA mold is very useful for repeatable production of the super-hydrophobic PDMS thin film. This is very important because reliable and continuous production of PDMS thin films with the surface texturing can be possible by using the same mold. Further, nano-silica is sprayed on the PDMS surface (figure 2(i)) with a certain distance and angle. These nano-materials slightly increase the water contact angle. Figure 2(j) shows SEM images of replicated optically transparent super-hydrophobic PDMS films with and without additional nano-silica coating processes. The measured water contact angle on the thin PDMS film is shown in figure 2(k). Figure 3 shows atomic-force microscopy (AFM) images of a pure PDMS and nano-silica coated PDMS substrates. AFM images indicate that the average roughness (Ra) value increased from $0.529\\mathrm{nm}$ to $44.5\\mathrm{nm}$ after coating the nano-silica on the PDMS surface.  \n\n![](images/a0ae52a10123ceefbc5400a5ed32e776d043346f683c21ac0873f50d3dc33065.jpg)  \nFigure 3.  Atomic force microscope images (a) before and (b) after nano-silica coating on PDMS films with flat surfaces.  \n\n![](images/b9deea1a9d52ddd6e0817ced233f0f4cb087dceaa1e0db46b6129f5b463b99db.jpg)  \nFigure 4.  Optical images of (a) hydrophobic PDMS positive mold (b) replicated UV-curable polymer mold (c) re-replicated super-hydrophobic PDMS film fabricated from the UV-curable polymer mold and (d) repeated fabrication of PDMS thin films with an ultra-hydrophobic surface.  \n\n![](images/08f94e857ff9fa545a9a55df44eaee651393d3ef1f2dfd288e62afaef78f8310.jpg)  \nFigure 5.  (a) and (b) Water contact angle with increasing number of water droplets on super-hydrophobic PDMS films and the pitch distance of the pillar structure. (c) and (d) Dynamic contact angle and sliding angle as a function of volume of water droplets.  \n\nOne of the great advantages of the proposed fabrication method is the use of the reusable and scalable PUA mold. The method does not require additional chemical treatment during the separation of the cured PDMS film from the UV-cured polymer mold with negative structures. The cured PDMS film can be easily and sufficiently detached from the PUA mold even with a small mechanical force. In addition, the hydrophobic characteristics are further improved after employing an additional nanoparticle (e.g. nano-silica) coating on the replicated PDMS thin film. Figure 4(a) show a SEM image of the fabricated PDMS mold with surface textures. The surface textures of the PDMS were successfully replicated to the PUA thin film as shown in figure  4(b). Figure  4(c) show a SEM image of the surface-textured PDMS re-replicated by using the replicated PUA mold. Figure 4(d) show optical images of continuously produced super-hydrophobic PDMS thin films using the reusable PUA mold. The size of the super waterrepellent PDMS film is about $15\\times15\\mathrm{cm}^{2}$ . The water contact angle, light transmittance, and self-cleaning effect were systematically investigated using various techniques.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# Results and discussion  \n\nFigure 5(a) shows the change of water contact angle as a function of pillar height $(30-60~\\mu\\mathrm{m})$ . Although there is a small difference in contact angle depending on the height of the pillar, it is almost negligible within the error ratio. Next, contact angle experiments were performed according to the spacing between pillar structures, as shown in figure  5(b). Experimental results show that the contact angle and transparency have opposite characteristics. When the pillar pitch is between $60~\\mu\\mathrm{m}$ and $100\\ \\mu\\mathrm{{m}}$ , the super-hydrophobicity of the PDMS surface was very good but the optical transparency decreased in comparison with the pure PDMS films. In contrast, the transparency was excellent at a pitch of $120\\ \\mu\\mathrm{m}$ to $190\\ \\mu\\mathrm{{m}}$ , but the super-hydrophobicity drastically decreased. According to the experimental results, a pitch between $100\\mu\\mathrm{{m}}$ and $120\\ \\mu\\mathrm{m}$ was excellent for both transparency and hydrophobicity. Figure  5(c) shows the dynamic test (water contact angel) results for the PDMS film with a height of $30\\mu\\mathrm{m}$ and pitch of $120\\ \\mu\\mathrm{m}$ . The fabricated PDMS thin films with hierarchical surface texturing showed a water contact angle $\\geqslant150^{\\circ}$ at different water volume from 1 to $10\\mathrm{mm}$ in diameter. Experimental results for sliding angle of various water droplets are also shown in figure 5(d). As the volume of water increased, the sliding angle of the water droplet decreased from $14^{\\circ}$ to $6^{\\circ}$ .  \n\n![](images/ae5b1aa9bb6eb814088923d2ca9bf503a4a331b716212a4b25a6dee0ded021c2.jpg)  \nFigure 6.  (a) Optical transmittance as a function of wavelength for two different PDMS films, with and without nano-silica coating, and (b) optical image of super-hydrophobic PDMS film placed on a printed paper.  \n\nIn preliminary studies, the water contact angle value was measured for $5~\\mu1$ of water. However, this is insufficient as a basis for replicating water repellency in the natural world, such as a rain shower with much different water volumes. For this reason, the water contact angle value was measured with continuous increasing water droplet volumes (minimum $1\\mu1$ to maximum $30~\\mu\\mathrm{l}$ ). The replicated super-hydrophobic film maintains a water contact angle of more than $150^{\\circ}$ for all water volumes. This proves that the optically transparent superhydrophobic film has excellent water repellency. Hence, it is expected that water repellency will be maintained even in a real rain shower. To evaluate the transparency of PDMS films fabricated using the reusable photo-curable polymer mold with a pitch distance of $120\\ \\mu\\mathrm{m}$ , the transmittance in the visible region ${(400-800\\mathrm{nm})}$ was measured using a UV–Visible spectrometer. Two different types of PDMS films, with and without nano-silica, were employed for characterization, and the transmittance of the PDMS films were compared, as shown in figure 6(a). The water contact angle increased from about $138^{\\circ}$ to $158^{\\circ}$ after the nanosilica coating (figures S1 and S2 (stacks.iop.org/JMM/28/025004/mmedia)). In the case of PDMS films without nano-silica coating, the average transmittance was close to $98.9\\%$ . The value slightly decreased to $95.7\\%$ when nano-silica was coated on the PDMS films using a spray method. However, both thin films still showed a high light transmittance suitable for practical applications. These results indicate that the hierarchical micro/nano structures formed on the thin PDMS film do not significantly affect the optical transparency of the thin film. Figure 6(b) also shows an optical image of ultra-hydrophobic PDMS film placed on a printed paper. Excellent transparency of the film was confirmed by verifying the visibility of letters printed on the paper in various colors. To confirm the super-hydrophobic behavior of the PDMS thin film, blue dyed water droplets were dropped on the film; the high water contact angle was also confirmed because the water droplet easily slipped.  \n\nPDMS thin films with different pitch distances were fabricated to evaluate the relationship between the pitch distance and the optical transparency. The prepared PDMS films were attached on a black background with white letters printed on it and the optical transparency was evaluated using a microscope. Figure  7(a) shows the optical images of PDMS thin films with different pitch distances from $80~\\mu\\mathrm{m}$ to $190\\ \\mu\\mathrm{{m}}$ . When the distance was more than $140~\\mu\\mathrm{m}$ , the hierarchical micro/nano structures formed on the PDMS film had little effect on the transmittance. Magnified images of pillars from the top and side views are shown in figures 7(b) and (c). As shown in figure  7(c), an array of water-repellent structures with a mushroom shape was exactly duplicated using the reusable PUA mold.  \n\nLotus leaves are always cleaned with only a rain shower, i.e. they exhibit the self-cleaning effect [9, 10]. The duplicated super-hydrophobic PDMS film is also expected to have the self-cleaning behaviors due to their unique surface structures, similar to lotus leaves. A preliminary experiment investigating this issue was conducted. The PDMS thin film was placed on top of a white paper with black letters (figure 8(a)). Next, the PDMS surface was contaminated with gray dust obtained from a vacuum cleaner (figure 8(b)) and water droplets were then continuously applied to the contaminated PDMS surface, as shown in figure 8(c). After a few minutes, the contaminated surface was clearly clean due to the surface’s self-cleaning ability, as shown in figure  8(d). The results were also compared with that from normal PDMS films with a planar surface; water alone did not completely remove the contamination on the flat PDMS surface. An additional cleaning process was required to completely remove the contamination. The basic experimental results indicate that the proposed PDMS thin films with the super-hydrophobicity and self-cleaning ability have great potential for applications in various engineering areas.  \n\n![](images/bd5f45551a57a341bcc33d06ddb39f686c880263b0b9473cc9b24fe5f1032a71.jpg)  \nFigure 7.  (a) Optical images showing the transmittance of the PDMS films when the pitch distance increased from 80 to $190\\mu\\mathrm{m}$ , and SEM images of the fabricated micro/nano structured PDMS, (b) top view and (c) side view of the micro/nano structured PDMS thin film.  \n\n![](images/e70ac88bf85cfd4c14fdb47595b206beca1c1f6a06997958d0cc37447f816daa.jpg)  \nFigure 8.  Optical images showing the self-cleaning ability of the super-hydrophobic PDMS thin film, (a) initial status, (b) contaminated with gray dust, (c) continuous application of water droplets, and (d) surface cleaned with water droplets.  \n\n![](images/c904a32a669b64d780ac64c13c091e01ecf1a6938b9f430c1df598f191f22449.jpg)  \nFigure 9.  Optical images of (a) solar cell without film on the surface and (b) solar cell covered with super-hydrophobic film.  \n\nTable 1.  Experimental results of coated and uncoated solar cells under various light sources.   \n\n\n<html><body><table><tr><td></td><td>A. Solar panel</td><td>B. Solar panel + hydrophobic film</td><td>Efficiency (A/B)× 100%</td></tr><tr><td>Sunlight</td><td>1.52V</td><td>1.52V</td><td>100%</td></tr><tr><td>LED (white)</td><td>0.78V</td><td>0.77V</td><td>98%</td></tr><tr><td>Yellow lamp</td><td>0.71V</td><td>0.71V</td><td>100%</td></tr><tr><td>UV (360nm)</td><td>1.61V</td><td>1.60 V</td><td>99%</td></tr></table></body></html>  \n\nTo verify the further utility of the self-cleaning transparent thin film, the fabricated PDMS thin film was applied as a protection layer to a solar panel, as shown in figures 9(a) and (b). Because solar cells use sunlight as an energy source, they are exposed to the outside environment. Accordingly, solar cell surfaces are often contaminated with environmental dust, resulting in lowered light transmission and photoelectric conversion efficiency. In the solar cell, an antifouling film with high transparency that does not affect energy efficiency and maintains its own cleanliness without special management is required. The $10\\times6\\mathrm{cm}^{2}$ solar panel was fully covered by the fabricated super-hydrophobic PDMS thin film as shown in figure  9(b). No chemical treatment and adhesive layer were required for attachment and even when detaching from the panel. The energy loss was compared with the output voltage before and after PDMS film attachment. Four different light sources, sunlight, LED light (white), yellow light, and UV light $360\\mathrm{nm})$ were employed for characterization. Results indicate that there was $1-2\\%$ voltage loss for the LED and UV light experiments (table 1). Under the sunlight and yellow light condition, the solar cell had the highest output voltage, and voltage loss was almost negligible values.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# Conclusion  \n\nThis paper proposed a new fabrication method for continuous production of optically transparent super-hydrophobic PDMS thin films. A unique surface of the PDMS thin film fabricated by a PR mold was re-replicated to a reusable PUA mold. Employing the photo-curable PUA mold extremely simplified the production process to generate these PDMS thin films with the unique surface. Various PDMS thin films with different pitch distances were fabricated to obtain the optimized conditions for transparency and hydrophobicity. In addition, nano-silica coating was also applied to further improve the hydrophobicity of the PDMS thin film. Excellent self-cleaning ability and optical transparency were exper­ imentally confirmed using a solar panel. The new fabrication process and successful experimental results reveal that the proposed method has significant potential for many engineering applications.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 11,
+        "chunk": "# Acknowledgments  \n\nThis work was supported by Commercialization Promotion Agency for R&D Outcomes (COMPA) funded by the Ministry of Science, ICT and Future Planning (MSIP) (No 2016K000209).",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# ORCID iDs  \n\nD-W Lee $\\circledcirc$ https://orcid.org/0000-0002-0847-4505",
+        "category": " References"
+    },
+    {
+        "id": 13,
+        "chunk": "# References  \n\n[1] Yoon Y, Lee D W and Lee J B 2012 Surface modified nanopatterned SU-8 pillar array optically transparent superhydrophobic thin film J. Micromech. Microeng. 22 035012   \n[2] Feng L, Li S, Li Y, Li H, Zhang L, Zhai J, Song Y, Liu B, Jiang L and Zhu D 2001 Super-hydrophobic surfaces: from natural to artificial Adv. Mater. 14 1857–60   \n[3] Lin T S, Wu C F and Hsieh C T 2006 Enhancement of waterrepellent performance on functional coating by using the Taguchi method Surf. Coat. Technol. 200 5253–8   \n[4] Dai S, Ding W, Wang Y, Zhang D and Du Z 2011 Fabrication of hydrophobic inorganic coatings on natural lotus leaves for nanoimprint stamps Thin Solid Films 519 5523–7   \n[5] Xiu Y, Zhu L, Hess D W and Wong C P 2007 Hierarchical silicon etched structures for controlled hydrophobicity/ superhydrophobicity Nano Lett. 7 3388–93   \n[6] Inoue Y, Yoshimira Y, Ikeda Y and Kohno A 2000 Ultrahydrophobic fluorine polymer by Ar-ion bombardment Colloids Surf. B 19 257–61   \n[7] Li S, Li H, Wang X, Song Y, Liu Y, Jiang L and Zhu D 2002 Super-hydrophobicity of large-area honeycomb-like aligned carbon nanotubes J. Phys. Chem. B 106 9274–6   \n[8] Yoon Y, Lee D W and Lee J B 2013 Fabrication of optically transparent PDMS artificial lotus leaf film using underexposed and underbaked photoresist mold J. Microelectromech. Syst. 22 1073–80   \n[9] Patankar N A 2004 Mimicking the lotus effect: influence of double roughness structures and slender pillars Langmuir 20 8209–13   \n[10] Park J and Lee D 2017 Highly reproducible and scalable transparent PDMS thin film with super-hydrophobic surface Int. National Conf. of IEEE MEMS 2017 (Las Vegas, 22–26 January) pp 679–82",
+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,52 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Polymer-Based Black Phosphorus (bP) Hybrid Materials by in Situ Radical Polymerization: An Effective Tool To Exfoliate bP and Stabilize bP Nanoflakes  \n\nElisa Passaglia,\\*,† Francesca Cicogna,† Federica Costantino,† Serena Coiai,† Stefano Legnaioli,† Giulia Lorenzetti,† Silvia Borsacchi,† Marco Geppi,†,‡ Francesca Telesio,§ Stefan Heun, $\\left\\{\\Phi\\right\\}$ Andrea Ienco,∥ Manuel Serrano-Ruiz, and Maurizio Peruzzini  \n\n†Istituto di Chimica dei Composti Organometallici (CNR-ICCOM), SS Pisa, Via Moruzzi 1, 56124 Pisa, Italy ‡Dipartimento di Chimica e Chimica Industriale (DCCI), Via Moruzzi 13, 56121 Pisa, Italy §NEST, Istituto Nanoscienze-CNR and Scuola Normale Superiore, Piazza San Silvestro 12, 56127 Pisa, Italy ∥Istituto di Chimica dei Composti Organometallici (CNR-ICCOM), Via Madonna del Piano 10, 50019 Sesto Fiorentino, Italy  \n\n\\*S Supporting Information  \n\nABSTRACT: Black phosphorus (bP) has been recently investigated for next generation nanoelectronic multifunctional devices. However, the intrinsic instability of exfoliated bP (the bP nanoflakes) toward both moisture and air has so far overshadowed its practical implementation. In order to contribute to fill this gap, we report here the preparation of new hybrid polymer-based materials where bP nanoflakes $\\left(\\mathrm{bPn}\\right)$ exhibit a significantly improved stability. The new materials have been prepared by different synthetic paths including: (i) the mixing of conventionally liquidphase exfoliated bP (in dimethyl sulfoxide, DMSO) with poly(methyl methacrylate) (PMMA) solution; (ii) the direct exfoliation of bP in a polymeric solution; (iii) the in situ radical polymerization after exfoliating bP in the liquid monomer (methyl methacrylate, MMA). This last methodology concerns the preparation of stable suspensions of bPn−MMA by sonication-assisted liquid-phase exfoliation (LPE) of bP in the presence of MMA followed by radical polymerization. The hybrids characteristics have been compared in order to evaluate the bP dispersion and the effectiveness of the bPn interfacial interactions with polymer chains aimed at their long-term environmental stabilization. The passivation of the bPn is particularly effective when the hybrid material is prepared by in situ polymerization. By using this synthetic methodology, the nanoflakes, even if with a gradient of dispersion (size of aggregates), preserve their chemical structure from oxidation (as proved by both Raman and $\\ensuremath{^31\\mathrm{{p}}}$ -solid state NMR studies) and are particularly stable to air and UV light exposure. The feasibility of this approach, capable of efficiently exfoliating bP while protecting the bPn, has been then verified by using different vinyl monomers (styrene and $N.$ -vinylpyrrolidone), thus obtaining hybrids where the nanoflakes are embedded in polymer matrices with a variety of intriguing thermal, mechanical, and solubility characteristics.  \n\n![](images/ab76effac1f6032a5117aa6df781bed59841f4efc98492a4fcceee6745735848.jpg)",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# INTRODUCTION  \n\nBlack phosphorus (bP) is nowadays one of most studied 2D layered systems.1 With its capability to form 2D structures similar to graphene, but with electronic properties potentially better suited to transistors or solar cells, bP and its exfoliated derivatives, phosphorene (a single layer of bP) or bP nanoflakes $\\left(\\mathsf{b}\\mathsf{P}\\bar{\\mathbf{n}}\\right)$ , have captured the attention of researchers around the world. Condensed matter physicists, chemists, semiconductor device engineers, and material scientists are in-depth studying the possible applications of bP and bPn in different fields.2,3 Similarly to graphite and transition metal dichalcogenides (TMDCs), bP has a layered structure but a unique puckered single-layer geometry responsible for its interesting properties. The bPn have been reported to exhibit a high mobility of 1000 $\\mathrm{cm}^{2}\\:\\mathrm{V}^{-1}\\:s^{-1}$ for a sample of thickness $\\textsf{S n m}$ with high current ON/OFF ratio of $10^{5}$ .4,5 In addition, due to the characteristic P atom arrangement, the carrier mobility is anisotropic in the plane and the direct electronic band gap depends on flake thickness.4−6 In particular, bP is a p-type semiconductor which possesses a direct band gap of $0.3\\ \\mathrm{eV};$ ; more interestingly, the bPn has again a direct band gap which increases up to approximately $2{\\mathrm{~eV}}$ for the monolayer. These features make bP a promising material for novel applications in nanoelectronic and nanophotonic devices which cover the entire range of the visible spectrum.3 For example, exfoliated $\\mathbf{b}\\mathrm{Pn}$ (mechanically or via laser irradiation technique)7,8 has been used in field emitter devices for the development of practical electron sources. Other interesting applications concern the use of exfoliated bP as humidity sensors9,10 with performance depending on the thickness/number of nanosheets and being competitive with TMDCs11,12  \n\nHowever, the literature concerning the bP and bPn properties, their reactivity (including also the possibility of surface functionalization or decoring), and their stability in different environments points out that the combination of air (oxygen), water (humidity), and light (UV radiations) causes the easy degradation of these materials.13−16 It is also reported that the degradation is faster with decreasing layer number and thus flake thickness (on going from bulky bP to single layer $\\mathbf{\\widehat{b}P n}_{\\mathbf{\\widehat{\\mu}}}^{\\dagger}$ ).17 This is for the moment one of the main drawbacks limiting the use of this material. Therefore, exfoliated bP has to be stabilized to prevent degradation. This has been done through suitable coatings such as layered materials (hexagonal boron nitride),18 oxides $\\left(\\mathrm{Al}_{2}\\mathrm{O}_{3}\\right),^{19}$ or polymers. Among these, polymer coating is the easiest, with particular reference to poly(methyl methacrylate) (PMMA), which is known to efficiently preserve mechanically exfoliated bP flakes.7 Besides, mechanical exfoliation of bP is not a scalable technology which limits its use in applications.  \n\nNotably, polymers have been recognized as favorable in breaking down the strong interlayer interactions among nanostructured layered materials20 to design hybrids with performance suitable for optoelectronics or nonlinear optical (NLO) devices, chemiresistors, temperature, and deformation sensors.21 Depending on the possibility of establishing specific interactions, the agglomeration of thin bP layered flakes, once generated by liquid-phase exfoliation (LPE) technology, can be avoided by embedding them with polymer chains, like in the case of polystyrene.22 In addition, the final polymer nanocomposites can preserve the structure and the properties of individual components, realize synergistic effects between different substrates, endow new properties, and develop devices for different applications; PEDOT:PSS, poly-L-lysine, polyaniline, and polycarbonate have been used to design semiconductors, sensing platforms for medical detection, pseudocapacitors, and pulsed fiber lasers23−26 which are generally obtained by covering the bPn surfaces or by mixing their suspension with the polymers.  \n\nBy considering this scenario, the present work proposes, for the first time, a study focused on the preparation of stabilized bPn embedded in polymers through hybrids preparation able to maintain or even to improve the structural properties of bP. In place of the previously reported exfoliation methods that use a mechanical tool (scotch tape) or LPE with nonfriendly solvents, that are difficult to remove from the devices (as for example, dimethyl sulfoxide, DMSO), here, for the first time, bP has been exfoliated in the PMMA matrix by using strategies aimed at improving both the exfoliation level (phosphorene or bPn being the target) and the structural and morphological stability of the exfoliated material. In particular, the bP has been directly exfoliated in the liquid vinyl monomer, the methyl methacrylate (MMA), without solvents, and after the addition of a radical initiator, the hybrid material has been obtained by in situ radical polymerization. For comparison purposes, PMMAbased composites have also been prepared by the direct bP exfoliation in polymer solution or by starting from bPn previously exfoliated by LPE with DMSO and successively dispersed in the PMMA matrix.  \n\nThese new materials have been characterized by combining different techniques: dynamic light scattering (DLS), Fourier transform infrared (FTIR) and Raman spectroscopies, X-ray diffraction (XRD), $\\ensuremath{{}^{31}\\mathrm{P}}$ -solid state NMR (SSNMR), atomic force microscopy (AFM), size exclusion chromatography (SEC), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA) have been used to in-depth examine the structural features, the morphology, and the thermal properties of components as soon as the hybrids have been obtained and also after several months. The collected results gather information about the stability of the chemical structure of bPn in the polymer matrix over time and after UV light irradiation in air. The in situ radical polymerization has been thus used to produce hybrids starting from different vinyl monomers, styrene (Sty), and $N.$ -vinylpyrrolidone (NVP) to prove the feasibility and the significance of the methodology here developed.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# EXPERIMENTAL SECTION  \n\nMaterials. All the materials (polymers and reagents) and the solvents below were used as received without further purification: methyl methacrylate (MMA), $99\\%$ from Sigma-Aldrich, $d=0.963~\\mathrm{mg/}$ mL, MW: $100.12~\\mathrm{g/mol};$ 1-vinyl-2-pyrrolidone (NVP), $299\\%$ from Sigma-Aldrich, $d=1.043~\\mathrm{mg/mL},$ MW: $\\mathrm{111.14~g/mol};$ styrene (Sty), $299\\%$ from Sigma-Aldrich, $\\begin{array}{l l l}{d}&{=}&{0.906~\\mathrm{\\mg/mL;}}\\end{array}$ poly(methyl methacrylate) (PMMA) from Sigma-Aldrich, MW: 120 000 D; polystyrene (PS) from Repsol, MW: 164 500 D; poly(vinylpyrrolidone) (PVP) from Sigma-Aldrich, MW: 29 000 D; $^{2,2^{\\prime}}$ - azobis(2-methylpropionitrile) (AIBN), $98\\%$ from Sigma-Aldrich, MW: $164.21~\\mathrm{g/mol};$ ; dimethyl sulfoxide (DMSO), ACS reagent $299.5\\%$ from Sigma-Aldrich, MW: $78.13~\\mathrm{g/mol};$ chloroform, ACS reagent $\\ge99.8\\%$ from Sigma-Aldrich, MW $119.38~\\mathrm{g/mol}$ ; acetone, ACS reagent $299.5\\%$ from Sigma-Aldrich, MW: $58.08~\\mathrm{g/mol}$ ; methanol, ACS reagent $99.8\\%$ from Sigma-Aldrich, MW: $32.04~\\mathrm{g/mol}.$ ; diethyl ether, ACS reagent $\\ge99.8\\%$ from Carlo Erba (CAS: 60-29-7), MW: $74.12\\mathrm{\\g/mol};$ ; propanol, ACS reagent $\\ge99.5\\%$ from Sigma-Aldrich (CAS: 67-63-0), MW: $60.10~\\mathrm{g/mo\\bar{l}}$ ; $n$ -heptane, ACS reagent $298.5\\%$ from Sigma-Aldrich, MW: $100.2\\mathrm{\\g/mol};$ anisole, $99\\%$ from SigmaAldrich, MW: $108.14~\\mathrm{g/mol}.$  \n\nInstruments and Characterization. The micro-Raman analysis was performed using a Renishaw micro-Raman inVia instrument equipped with a 1800 grooves/ $\\mathrm{{\\dot{m}m}}$ diffraction grating, a CCD detector, and a $50\\times$ magnifying lens. The instrument has a Nd:YAG laser source at $\\lambda=532~\\mathrm{{nm}}$ wavelength. The samples were analyzed as polymer films or powder (bP); the measurements as well as the imaging were obtained on different portions of each specimen, and the power on the samples was about $1.5~\\mathrm{mW}$ .  \n\nX-ray diffraction (XRD) patterns of hybrids and bP were acquired at room temperature with a PANalytical X’PERT PRO diffractometer, employing $\\operatorname{Cu}\\ \\mathrm{K}\\alpha$ radiation $(\\lambda=1.54187\\mathrm{~\\AA~})$ ) and a parabolic MPDmirror for $\\mathtt{C u}$ radiation. The diagrams were acquired in a $2\\theta$ range between $5.0^{\\circ}$ and $80.0^{\\circ}\\ .$ , using a continuous scan mode with an acquisition step size of $0.0263^{\\circ}$ or $0.0131^{\\circ}$ and a counting time of 150 s.  \n\nDynamic light scattering (DLS) analyses were carried out at room temperature by using the Malvern Zetasizer nano instrument (model: ZEN1600) equipped with a HeNe laser $(633\\ \\mathrm{nm},\\ 4\\ \\mathrm{mW})$ and an avalanche photodiode detector with an angle of $173^{\\circ}$ . The DLS data were processed and analyzed with Dispersion Technology Software (Malvern Instruments).  \n\nFourier transform infrared (FTIR) and attenuated total reflectance (ATR-FTIR) spectra were recorded at room temperature with a Perkin-Elmer Two Spectrometer equipped with an ATR accessory with diamond crystal. The spectra were generally acquired between 4000 and $400~\\mathrm{{cm}^{-1}}$ with a resolution of $\\bar{4}~\\mathrm{cm}^{-1}$ using 16 scans.  \n\nNumber-average molecular weight $\\left(\\overline{{M}}_{\\mathrm{n}}\\right)$ and weight-average molecular weight $(\\bar{M}_{\\mathrm{w}})$ as well as dispersity $\\mathbf{\\eta}(\\mathcal{P})$ were determined using size exclusion chromatography (SEC), Agilent Technologies 1200 Series. The instrument was equipped with an Agilent degasser, an isocratic HPLC pump, an Agilent refractive index (RI) detector, and two PLgel $5~\\mu\\mathrm{m}$ MiniMIX-D columns conditioned at $35~^{\\circ}\\mathrm{C}$  \n\nChloroform $\\left(\\mathrm{CHCl}_{3}\\right)$ ) was used as the mobile phase at a flow rate of $0.3\\mathrm{mL}\\mathrm{min}^{-1}$ . The system was calibrated with polystyrene standards in a range from 500 to $\\dot{3}\\times10^{5}\\mathrm{g}\\mathrm{mol}^{-1}$ . Samples were dissolved in $\\mathrm{CHCl}_{3}$ $(2\\mathrm{\\mg\\mL^{-1}})$ and filtered through a $0.20\\ \\mu\\mathrm{m}$ syringe filter before analysis (twice in the case of hybrids). Number-average molecular weight $(\\overline{{M}}_{\\mathrm{n}})$ and weight-average molecular weight $(\\overline{{M}}_{\\mathrm{w}})$ were calculated using the Agilent ChemStation software.  \n\nThermal gravimetric analyses (TGA) were carried out with a Seiko EXSTAR 7200 TGA/DTA by introducing about $\\ensuremath{5^{-8}}\\ensuremath{\\mathrm{mg}}$ of sample in an alumina sample pan of $70~\\mu\\mathrm{L}$ . In a typical experiment, run was carried out at a standard rate of $10~{^\\circ}\\mathrm{C}/\\operatorname*{min}$ from 30 to $700~^{\\circ}\\mathrm{C}$ under nitrogen flow. $T_{\\mathrm{onset}}$ and $T_{\\mathrm{infl}}$ were determined by analyzing the TG curve (as the temperature of intercept of tangents before and after the degradation step) and DTG curve (as the maximum of the peak), respectively.  \n\nThe glass transition temperature $(T_{\\mathrm{g}})$ of hybrids was determined by differential scanning calorimetry (DSC) using a PerkinElmer DSC4000 equipped with intracooler and interfaced with Pyris software (version 9.0.2). The range of temperatures investigated was 40−180 $^{\\circ}\\mathrm{C}$ . Thermal scans were carried out on $\\mathrm{5-10~mg}$ samples in aluminum pans under nitrogen atmosphere. The instrument was calibrated by the standards In $\\mathrm{^{'}}T_{\\mathrm{m}}=156.6^{\\circ}\\mathrm{C},$ $\\Delta H_{\\mathrm{m}}=28.5\\mathrm{J/g)}$ and $\\mathrm{Pb}$ $T_{\\mathrm{m}}=327.5$ ${}^{\\circ}{\\bf C},$ $\\Delta H_{\\mathrm{m}}=23.03\\mathrm{J/g)}$ .  \n\nAtomic force microscopy (AFM) measurements were performed with a Bruker Dimension Icon AFM, in pick force mode. Data analysis was performed by WSxM software.27  \n\n$\\ensuremath{{}^{31}\\mathrm{\\overline{{P}}}}$ solid state NMR (SSNMR) experiments were carried out with a Varian InfinityPlus spectrometer working at Larmor frequencies of $400.34~\\mathrm{{\\fontfamily{qpl}{\\mathrm{{\\scriptsize{Mz}}}}}}$ and $162.07\\ \\mathrm{MHz}$ for $\\mathrm{^{1}H}$ and $^{31}\\mathrm{P}$ nuclei, respectively. Spectra were acquired using a $3.2\\mathrm{mm}$ probe head, exploiting the direct excitation (DE) pulse sequence, under high power decoupling from $^1\\mathrm{H}$ nuclei, using a recycle delay of $120\\mathrm{~s~}$ and accumulating a number of transients between 100 and 3000. All the experiments were carried out under magic angle spinning (MAS), with a frequency of $^{10\\mathrm{kHz},}$ using air as spinning gas, and at a temperature of $20~^{\\circ}\\mathrm{C}.$ $\\ensuremath{{}^{31}\\mathrm{P}}$ chemical shift scale was referred to the signal of $\\mathrm{H}_{3}\\mathrm{PO}_{4}$ $(85\\%)$ at $0\\ \\mathrm{ppm}$ .  \n\nbP and bPn Suspensions Preparation and Characterization. Black phosphorus (bP) and phosphorene $\\left(\\mathrm{bPn}\\right)$ suspension in DMSO (DMSO_ $\\boldsymbol{\\mathrm{bPn}}$ , $r_{\\mathrm{{H}}}~=~500~\\pm~23~\\mathrm{{nm})}$ were prepared as previously described,16 and TGA, XRD, and Raman spectroscopy results agreed with reported data.22 A compendium concerning the novel Raman analyses of bP is reported in the Supporting Information (Figure S1): the unexfoliated bP crystals show the three characteristic peaks of modes ${\\bf A}_{\\bf g}^{1}$ , $\\mathbf{B}_{2\\mathbf{g}},$ and ${\\mathrm{A}}_{\\mathrm{g}}^{2}$ with a shift in peak positions depending on the number of layers. In agreement with data already reported in the literature,14,16,17,28 the observation of sharper peaks, which were weakly shifted toward higher wavenumbers, was taken as evidence for crystalline, thin bP sheets.  \n\nMMA_bPn, NVP_bPn, and Sty_bPn suspensions were obtained by LPE in the presence of the sole monomer. In a typical procedure, ${\\sim}5$ mg of bP, carefully crushed in a mortar, was put in a test tube and then a weighted quantity of MMA, Sty, or NVP was added. The monomer bP suspension was sonicated for $90~\\mathrm{\\min}$ by using a Hielscher Ultrasonic Processor (UP220 St) instrument, equipped with Sonotrode (diameter: $2~\\mathrm{mm}$ ; $26\\pm\\mathrm{kHz}$ ). The amplitude of ultrasound wave was maintained constant at $50\\%$ with $P=7$ W. In all cases, an ice bath was used to avoid overheating of the system. The final MMA_bPn, $\\mathrm{{NVP\\_bPn}}$ , and Sty_bPn suspensions were then insufflated with $\\mathbf{N}_{2}$ for $15~\\mathrm{min}$ . All the suspensions were analyzed by DLS, showing $r_{\\mathrm{H}}$ values really close to that of DMSO_bPn. For example, the MMA_bPn suspension (having about $1\\%$ of $\\mathrm{\\overline{{bP}}}$ content) was characterized by $r_{\\mathrm{{H}}}=512\\pm58~\\mathrm{{nm}}$ .  \n\nHybrid Materials Preparation. Three different methodologies were employed (see Figure S2).  \n\nMethod A: Dispersion of DMSO_bPn Suspension in PMMA Solution. Into a $100~\\mathrm{mL}$ two-necked round-bottom flask, equipped with a magnetic stirrer and previously degassed, backfilled three times with nitrogen, and then left under nitrogen, $25~\\mathrm{mL}$ of $\\mathrm{CHCl}_{3}$ and $0.523\\mathrm{~g~}$ of PMMA (commercial product) were loaded. The solution was magnetically stirred for $10\\ \\mathrm{min}$ in a continuous stream of $\\Nu_{2}$ until the polymer was completely dissolved. Under a $\\mathbf{N}_{2}$ current, the DMSO_bPn suspension $(r_{\\mathrm{{H}}}=500\\pm23~\\mathrm{{nm})}$ was added dropwise. The mixture was left stirring under $\\mathbf{N}_{2}$ for $15\\ \\mathrm{min};$ and then, the mixing stopped. A DLS measurement of polymeric suspension provided a value of $r_{\\mathrm{{H}}}=894.3\\pm11.5\\ \\mathrm{{nm}}$ . The flask content, a yellow/brown solution, was precipitated (dropwise) into $400~\\mathrm{mL}$ of MeOH. The polymer was then filtered and dried under vacuum until a constant weight $(0.430\\textrm{g})$ was achieved. By considering that the DMSO_bPn suspension was prepared by using $5~\\mathrm{{mg}}$ of bP, the content of phosphorus derivative in the composite (entry PMMA_bP_A) was estimated as $1.0\\%$ wt on the basis of starting amount.  \n\nMethod B: LPE of bP in PMMA Solution. Five mg of $\\boldsymbol{\\mathrm{bP}}$ was put into a test tube; then, a polymer solution containing $0.513\\mathrm{g}$ of PMMA (commercial product) in $30~\\mathrm{mL}$ of a mixture of acetone/DMSO $(2/1)$ was added to the powder. The ultrasonication process was carried out for $3\\mathrm{h}.$ , by varying the amplitude of the ultrasound wave between $50\\%$ and $100\\%,$ , with a power of ${\\sf5-9~W}$ . A DLS measurement of polymeric suspension provided a value of $r_{\\mathrm{{H}}}=427.3\\pm96.4~\\mathrm{nm}$ . The collected dispersion with yellow-brown color was coprecipitated in $400~\\mathrm{mL}$ of MeOH. The solid fraction was then recovered via filtration and dried under vacuum until a constant weight was achieved. The content of phosphorus derivatives in the composite (entry PMMA_bP_B) was estimated as $1.0\\%$ wt on the basis of starting amount. The same treatment (solubilization and sonication) was applied to PMMA (commercial product) without adding the bP to recover a blank sample (entry PMMA_B_blank) used for comparison purposes.  \n\nMethod C: In Situ Radical Polymerization. A Schlenk tube (10 mL) equipped with a magnetic stirrer and previously degassed, backfilled three times with nitrogen, and then left under nitrogen was loaded with the MMA_bPn or Sty_bPn or NVP_bPn suspensions (previously prepared). A weighted amount of AIBN (2 wt $\\%$ with respect to the monomer) was added, and the tube was placed in an oil bath (temperature and time of polymerization depending of vinyl monomer used, as summarized in Table 1). The product was then dissolved in $\\mathrm{CHCl}_{3}$ and precipitated in an appropriate solvent to remove unreacted monomer and polymerization byproducts: MeOH was used for PMMA and PS, while $\\mathrm{Et}_{2}\\mathrm{O},$ for PNVP. After recovering via filtration, the resulting powder was dried under vacuum until a constant weight was achieved. The amount of phosphorus derivatives in each composite was determined on the basis of the polymerization yield (ranging from $85\\%$ to $60\\%$ ) and its starting amount. With the same experimental conditions, MMA, Sty, and NVP were polymerized to provide comparative samples obtained without bP (entries: PMMA_C_blank; PS_C_blank; PNVP_C_blank).  \n\nTable 1. In Situ Radical Polymerization Runs: Experimental Conditions and Final Composition of Composites   \n\n\n<html><body><table><tr><td colspan=\"5\">final content</td></tr><tr><td>entry</td><td>monomer (g)</td><td>bP (g)</td><td>time T (C) (min)</td><td>of P (wt %)a</td></tr><tr><td>PMMA_bP_C</td><td>MMA (0.94)</td><td>0.0055</td><td>70 180</td><td>0.8</td></tr><tr><td>PS_bP_C</td><td>Sty (0.91)</td><td>0.0053 80</td><td>180</td><td>0.8</td></tr><tr><td>PS_bP_C2</td><td>Sty (3.62)</td><td>0.0055 80</td><td>180</td><td>0.2</td></tr><tr><td>PNVP_bP_C</td><td>NVP (1.04)</td><td>0.0050 75</td><td>150</td><td>0.7</td></tr><tr><td>PNVP_bP_C2</td><td>NVP (4.16)</td><td>0.0063</td><td>75 150</td><td>0.3</td></tr></table></body></html>\n\naBy supposing that the whole phosphorus amount was maintained in the composite.  \n\nA schematic representation summarizing the different procedures is reported in Figure S2. In addition, a physical mixture between bP and PMMA (1 wt $\\%$ ) was prepared to be analyzed by $\\ensuremath{{}^{31}\\mathrm{P}}$ -SSNMR and XRD.  \n\nAll the samples were analyzed by SEC, DSC, and TGA and PMMAbased hybrids, by ${}^{31}\\mathrm{P}.$ -SSNMR. In addition, all the composites were even molded into films, by using a press Carver bench model 4386 ( $\\dot{\\boldsymbol{T}}$ $=180^{\\circ}\\mathrm{C},$ $10{-}20\\mathrm{kg/cm}^{2}.$ ), with constant and uniform thickness $=40-$  \n\n$90~\\mu\\mathrm{m}$ to be analyzed by XRD, Raman, and FTIR-ATR. Photodegradation of PMMA_bP_C and PMMA_C_blank was studied using a UV−vis camera (UvaCube400, 400 W, Hoenle) equipped with a $\\mathrm{Hg}$ lamp (high pressure mercury lamp with a power of 400 W: emittanc $\\dot{\\bar{z}}_{30-285}~=~15~\\mathrm{\\mW/cm}^{2}$ ; emittan $\\mathrm{ce}_{330-400}~=~11~\\mathrm{mW/cm}^{2};$ emittanc $\\mathrm{e}_{380-500}=35~\\mathrm{mW/cm^{2}})$ . The samples were irradiated for 250 min from one side. In addition, a solution of the sample PMMA_bP_C in anisole $(23\\mathrm{\\mg}/2\\mathrm{\\mL})$ ) was spin coated at 4000 rpm (rpm) for $1\\ \\mathrm{min},$ after an acceleration step at $500~\\mathrm{rpm}$ for ${\\boldsymbol{5}}\\ {\\boldsymbol{s}},$ and analyzed by AFM. The samples PNVP_bP_C and PS_bP_C were solubilized by water and anisole, respectively, and films provided by solution casting were analyzed by Raman.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# RESULTS AND DISCUSSION  \n\nPMMA-Based Hybrid Materials. The different methodologies used to prepare the hybrid material (schematized in Figure S2) can be summarized as follows: (i) embedding of the already exfoliated bP (by conventional LPE) in PMMA; (ii) exfoliation of bP by PMMA solution; (iii) LPE of bP by monomer (MMA, Sty, NVP) followed by in situ radical polymerization. These synthetic approaches were designed and realized with the dual objective of achieving a good dispersion of bP, i.e., obtaining thin flakes or few layers flakes and, at the same time, protecting them from the degradation that is known to occur when bP nanoflakes are exposed to air and light. The main target of the study was the achievement of a processable, soluble, and stable hybrid material that contains thin bP flakes, or a few layer flakes, whose structure can be preserved for long time.  \n\nThe structural and thermal properties of PMMA matrix in the hybrids were investigated by FTIR, Raman, SEC, TGA, and DSC (Figure 1 and Table 2). The FTIR and Raman spectra of the samples showed all the characteristic absorption bands of PMMA matrix, whose attributions are reported in Table S1.29 No differences in the FTIR spectra of composites with respect to the spectrum of commercial sample or blank experiment were highlighted (see Figure $^{\\mathrm{1A,}}$ as an example) suggesting that the different synthetic paths and the presence of bP or bPn did not cause significant variations in the chemical structure of PMMA. Notably, FTIR spectra did not show any additional absorption bands due to bP. Raman spectra (Figure 1B) confirmed the presence of PMMA showing all the main absorptions peaks of the matrix (Table S1), which were not changed by the presence of bP derivatives. In addition, these spectra showed distinct signals of bPn (between 300 and 500 $\\mathrm{{{cm}^{-1}}},$ ) whose intensities and Raman shifts depended on the methodology used for the preparation of the samples (as discussed later).  \n\nThe SEC analysis (Table 2) showed that the PMMA phase of the hybrids prepared by Method A and Method B has the same or similar $\\bar{M}_{\\mathrm{n}}$ with respect to its reference (i.e., PMMA and PMMA_B_blank, respectively) with only a weak decrease of $\\bar{M}_{\\mathrm{w}}$ for samples obtained by Method B. This result indicates a possible degradation of polymer chains induced by the prolonged sonication treatment. Conversely, the sample PMMA_bP_C, prepared by in situ radical polymerization, was characterized by a remarkably higher value of both the average molecular weights. This experimental evidence can be explained by the hindrance in movement of the growing macroradicals which inhibits the termination reactions and thus increases the length of polymer chains.30 This confinement effect confirms that the growth of PMMA macromolecules occurred near or onto the bPn surfaces or possibly between the layers of bP and promoted an effective embedding of flakes with the polymer chains.  \n\n![](images/11a27967bd035331deb9cdc5ab1795473354f0eadc2d73fe4a673523a6be7b81.jpg)  \nFigure 1. (A) FTIR spectra of commercial PMMA and of samples PMMA_C_blank and PMMA_bP_C. (B) Raman spectra of matrices (PMMA and PMMA_C_blank) and of hybrids obtained by different methods (dotted box highlights the bP signals and confirms their presence in all hybrids).  \n\nTable 2. Molecular Weight Evolution and Thermal Features of PMMA-Based Samples   \n\n\n<html><body><table><tr><td> sample</td><td>M (D)</td><td>Mw (D)</td><td>Tg (C)</td><td>(C)a Tonset</td><td>Tinn (°C)b</td></tr><tr><td>PMMA</td><td>52000</td><td>101000</td><td>105.0℃</td><td>264</td><td>290-387</td></tr><tr><td>PMMA_bP_A</td><td>56000</td><td>97000</td><td>115.6</td><td>279</td><td>294-394</td></tr><tr><td>PMMA_B_blank</td><td>57000</td><td>90000</td><td>108.7</td><td>267</td><td>285-390</td></tr><tr><td>PMMA bP B</td><td>49000</td><td>80000</td><td>115.1</td><td>280</td><td>294-395</td></tr><tr><td>PMMA_C_blank</td><td>45000</td><td>103000</td><td>120.6</td><td>272</td><td>287-381</td></tr><tr><td>PMMA_bP_C</td><td>58000</td><td>198000</td><td>121.0</td><td>269</td><td>293-372</td></tr><tr><td colspan=\"6\">aIntercept of tangents before and after degradation step. bFrom DTG curves as the maximum of the peak. ‘From technical sheet.</td></tr></table></body></html>  \n\nAFM analysis of films obtained by spin coating of PMMA_bP_C anisole solution corroborated the evidence of strong interactions and entanglement between polymer chains and bPn. PMMA fractions densely aggregated and formed a net around smaller particles that showed the characteristic Raman peaks of bP. An example of these hybrid PMMA/bP aggregates is reported in Figure 2; the “plateau” area visible in Figure 2a is $4\\ \\mathrm{nm}$ higher than the surrounding PMMA thin film and 4−5 $\\mu\\mathrm{m}$ wide (Figure 2d), while the bPn is inhomogeneous and up to $200\\ \\mathrm{\\nm\\high}$ , as shown in Figure 2e. Zooming in and rescaling the image to properly see the flake (Figure 2b), we can observe that the $1\\mu\\mathrm m$ bPn is indeed an aggregate of smaller structures. This inhomogeneity, as well as the height difference between the bP aggregate and the plateau, is even more evident from the 3D visualization (Figure 2c). Therefore, sample PMMA_bP_C actually contains a portion of PMMA strongly interacting with the bP flakes. It presumably grew up from the layers within the same flake and is characterized by higher molecular weight. Even if only a few literature examples of bP covalent functionalization are reported, we cannot completely exclude that bP sites (presumably the $\\mathrm{~\\bf~P~}$ apical atoms) are involved in MMA polymerization, by generating $\\scriptstyle\\mathrm{P-C}$ bonds.31 The reactivity of elemental white phosphorus with carboncentered radicals is well-known32 and its use as alkyl radical trap is well-documented;33 in addition, some weak hypothesis about the radical reaction of bP with aryl radicals (derived from diazonium compounds) was recently discussed as capable of generating P−C covalent bonds.34,35  \n\n![](images/ec4e9cfd80b14d9558e762a5a65d3664cdf8537a6bf92df92a6149bb0ea1e740.jpg)  \nFigure 2. AFM analysis of a film obtained by spin coating of PMMA_bP_C anisole solution. The film has a thickness of approximately $20\\ \\mathrm{nm},$ as measured by a stylus profilometer. Panel (a) shows a small aggregate of bP surrounded by a several micron-wide “plateau”. This “plateau” is composed of densely packed polymer chains, aggregated around the $\\boldsymbol{\\mathrm{bP}}$ structure. (b) Zoom-in taken in the region indicated by the square box in (a). It displays the bP structure, which appears as an aggregate of individual bP flakes. (c) 3D representation of the region of interest of (a), which allows one to appreciate the difference in height between the “plateau” and the bP. (d) Cross section of the “plateau” taken along the line shown in (a). The “plateau” is ${\\sim}4\\ \\mathrm{nm}$ higher than the surrounding area. (e) Cross section of the bP aggregate, along the line shown in (b), displays the height of the bP aggregate, up to approximately $200~\\mathrm{{nm}}$ , and its inhomogeneity.  \n\n![](images/a6489a9cf12af084325dcee506e9e05b22669b96b417e09ffc308f1c07c8ed97.jpg)  \nFigure 3. Magnified visual images of hybrids produced by Methods A, B, and $\\mathbf{C},$ collected by optical microscope and showing the particles’ distribution and their dimensions.  \n\n![](images/64d2b3389a57397e01a41e2c54371fe3de34ac2e1645934aa2999e2797c22876.jpg)  \nFigure 4. Representative images and Raman spectra collected in point indicated by letters (a), (b), and (c) of (A) sample PMMA_bP_B and (B) sample PMMA_bP_C; (C) enlargement of Raman spectra in the region of bP modes for PMMA_bP_C sample (dotted line is guide for the eyes).  \n\nAll hybrids showed an increase of $T_{\\mathrm{g}}$ value with respect to their blank experiment or reference (Table 2) suggesting a reinforcing effect due to nanofiller addition; however, this increment occurred with a really low extent for the run obtained by in situ polymerization (Method C) suggesting for this sample a finer and homogeneous dispersion of flakes. The same trend was observed for the TGA results. Notably, the composites provided by Methods A and B showed a certain improvement in their thermal stability with respect to both the onset and inflection temperatures, in agreement with results already22 PMMA_bP_C has a thermal behavior similar to that of blank sample, suggesting the formation of an interpenetrated phase in which the two components (polymer and filler) are really entangled at the molecular level without distinguishable effects in regards to bulk thermal properties (the TGA curves are reported in Figure S3).  \n\nThe optical microscopy coupled with Raman was used to investigate the morphology of the samples; the imaging of portions of each specimen showed a different flakes distribution, depending on the preparation method (Figure 3). PMMA_bP_A showed a good homogeneous distribution of tiny particles (below $1\\ \\mu\\mathrm{m},$ resembling the bPn and a really small amount of larger aggregates (see an example on the right of Figure 3A). Instead, the PMMA_bP_B sample seemed to be characterized by the presence of very large inclusions (Figure 3B), even if the measured $r_{\\mathrm{H}}$ of the polymeric suspension is comparable with that of DMSO_bPn (see Experimental  \n\nSection). Notably, a finer dispersion of bP was achieved in the case of PMMA_bP_C since tiny particles and flakes, homogeneously distributed, were observed and only a small fraction of larger aggregates (of several $\\mu\\mathrm{m}_{,}$ ) was found (see an example on the right of Figure 3C).  \n\nRaman spectra were collected in different portions of the samples to focus on the structure and distribution of flakes. A comparison of representative spectra collected for all the hybrids is reported in Figure S4. All the samples showed signals confirming the presence of bP, which suggest that most of the nanostructured material survived the methodology used for the hybrid synthesis, even if in the case of sample prepared by Method A not all the detected flakes exhibited the characteristic Raman peaks of bP structure. Similar behavior was observed for sample PMMA_bP_B for which only the large particles showed very intense signals attributable to bP; while in the case of sample PMMA_bP_C, almost all the observed flakes exhibited the $\\mathrm{{\\bar{A}_{g}}^{1}}$ , $\\mathbf{B}_{2\\mathrm{g}}^{{}},$ and $\\mathrm{A_{g}}^{\\overline{{2}}}$ modes.14,16,17,28 In addition, the spectrum of Raman active flakes of sample PMMA_bP_A showed a blueshift in peak positions (Figure S4), suggesting the presence of thinner flakes,9,28 in agreement with the morphological evidence.  \n\nInterestingly, from inspection of the structural features of flakes detected in samples provided by Methods B and $\\mathrm{c},$ it was found that the intensity of bP peaks compared to those of polymer was different and depended on the spot investigated. PMMA_bP_B showed a remarkable decrease of bP signal intensity by moving from the particle to the apparently neat polymer; moreover, Raman spectra of larger particles (several microns) did not evidence the typical polymer signals, according to poor efficiency in the bP embedding in the polymer matrix (Figure $^{4\\mathrm{A},}$ spectrum (a)). Instead, the spectra of PMMA_bP_C disclosed, in all the analyzed portions, the vibration modes of both the components, bP and polymer, with comparable relative intensity (Figure 4B). Smaller particles/ aggregates or apparently neat polymer portions were characterized by bP signals shifted toward higher frequency. This evident blue-shift of the ${\\mathrm{A}}_{\\mathrm{g}}^{2}$ mode (suggested as the most sensitive indicator of layer number9,36) and the decrease of intensity with respect to the reference PMMA band (see Figure 4C) confirmed for this sample the presence of almost homogeneously distributed thinner flakes (or bPn), consistent with the observations concerning the morphological features of the different hybrids discussed above. We speculate that the growth of polymer chains near or between the nanolayers, which is typical of the in situ polymerization technique, allows the moving away of bP layers and thus the obtainment of thinner flakes.  \n\nSolid state nuclear magnetic resonance (SSNMR) spectroscopy is at present one of the best techniques to characterize structural and dynamic properties of solid materials, over wide spatial and time ranges and independently of their amorphous or crystalline character.37 $\\ensuremath{^{31}\\mathrm{P}}$ -MAS spectra (with or without $\\mathrm{^{1}H}$ HPD) were recorded to characterize bPn after embedding in PMMA. In the literature, only a few examples of $^{31}\\mathrm{P}$ -MAS spectra of bP are reported38−40 while, to the best of our knowledge, these are the first spectra of hybrids materials containing bP. Figure 5 shows the $\\ensuremath{^{31}\\mathrm{P}}$ -MAS spectra of bP physically mixed with PMMA (see Experimental Section) used as reference sample and of PMMA hybrids, prepared by using the different methodologies.  \n\nThe spectrum of bP physically mixed with PMMA (Figure 5(a)) showed a signal at $18.5\\ \\mathrm{ppm}$ , consistent with the few bP  \n\n![](images/5135eaa85ded29ed91795e24be3c3396a13629e0f9e8f440993b4a5aae411aa0.jpg)  \nFigure 5. $^{31}\\mathrm{P}$ -MAS NMR spectra of (a) physical mixture between PMMA and bP, (b) PMMA_bP_B, (c) PMMA_bP_C, and (d) PMMA_bP_A. Differently from spectra $(\\boldsymbol{\\mathrm{b}})\\mathrm{-}(\\boldsymbol{\\mathrm{d}}).$ spectrum (a) was recorded without HPD from $\\mathrm{^{1}H}$ nuclei. The inset of each spectrum shows the fitting of the bP signal resonating at $18.5~\\mathrm{ppm}$ .  \n\nNMR spectral data reported in the literature.38−40 Moreover, two small signals were present at $0.8\\ \\mathrm{ppm}$ (singlet) and 7.5 ppm (doublet, with a $J_{\\mathrm{(P-H)}}=350~\\mathrm{Hz})$ , mainly ascribable to $\\mathrm{H}_{3}\\mathrm{PO}_{4}$ and ${\\mathrm{H}}_{3}{\\mathrm{PO}}_{3}$ species, respectively.40,41 These signals indicate that some oxidation effects occurred, even if to a small extent (the total area of $\\mathrm{H}_{3}\\mathrm{PO}_{4}$ and $\\mathrm{H}_{3}\\mathrm{PO}_{3}$ signals account for $6\\%$ and $3\\%$ , respectively, of the whole spectral area). The presence of oxidized species is likely due to the chemical adsorption of oxygen on the bP surface42 which was not protected, forming aging products.  \n\nAll the hybrids materials showed the signal of bP at ca. 18.5 ppm and several peaks in the 0−15 ppm spectral region, ascribable to oxidation products, mainly $\\mathrm{H}_{3}\\mathrm{PO}_{4}$ and $\\mathrm{H}_{3}\\mathrm{PO}_{3},$ but possibly also other phosphates and oxidized species.43,44 Moreover, in the spectra of PMMA_bP_B and PMMA_bP_C, weak signals were present in the region $^{-3}$ to $-20\\ \\mathrm{ppm}.$ , with a peak at $-11\\ \\mathrm{ppm},$ ascribable to pyrophosphate. For samples PMMA_bP_A and PMMA_bP_B, the intensity of the signals of the oxidized products was relatively $\\mathrm{\\high},$ about $75\\%$ and $71\\%$ of total spectral intensity, respectively, suggesting extensive degradation of bPn in the conditions used for the sample preparations (Methods A and B; see Figure S2) and in agreement with the observation that not all bP flakes in these samples were Raman active. Instead, the spectrum of the sample prepared by in situ polymerization, Method C (PMMA_bP_C), showed a higher intensity of the bP signal and a lower intensity of the signals due to the degradation products (about $68\\%$ and $32\\%$ , respectively). From these results, it appears evident that Method C better preserved the bPn structure. Conversely, Method A involved the use of previously exfoliated bP that was coprecipitated in a solvent after mixing with the polymer solution. Thin flakes easily underwent degradation/oxidation during the workup, particularly during the treatment with solvents upon prolonged sonication. Sample prepared by Method B was sonicated for a longer time $(3\\ \\mathrm{h})$ . Although this procedure was necessary to boost the bP exfoliation in the polymer solution, the fact that we could not operate under inert atmosphere rendered this methodology less suited to guarantee the complete bP structure preservation. Instead, the LPE in the MMA monomer carried out under milder conditions and the subsequent in situ radical polymerization provided the best results in terms of bPn structure stability. In addition, the presence of weak signals in the region 10 to $-20$ ppm could be ascribed to alkylphosphorus species originating from the reaction between organic radicals and bP or bPn.  \n\nRemarkably, in the spectrum of the physical mixture between PMMA and bP, the bP signal at $18.5\\mathrm{ppm}$ shows an asymmetric shape, observed also in the already reported bP spectra. Indeed, by exploiting a spectral fitting procedure, the signal at $18.5\\mathrm{\\ppm}$ could be deconvoluted in two peaks, the first with a chemical shift of $18{-}19\\ \\mathrm{\\ppm}$ (line width of $450{-}550\\ \\mathrm{\\Hz})$ and the second at $20{-}21~\\mathrm{ppm}$ (line width of $800{-}1000\\mathrm{Hz};$ see inset in Figure 5). The intensity ratio between these two peaks was about 60:40. Approximately the same result was obtained for PMMA_bP_C (inset of Figure 5), suggesting that the exfoliation degree did not substantially affect the chemical shift and the shape of the $^{31}\\mathrm{P}$ NMR signal.  \n\nThe bP NMR signal of PMMA_bP_A and PMMA_bP_B appears even more asymmetric, as confirmed by a 40:60 intensity ratio between the peaks at about 18−19 and 20−21 ppm, as determined from spectral fitting (insets of Figure 5). Considering that these two samples, even if exfoliated to a different extent, present a similarly high degree of oxidation, this result suggests that a large degradation could also affect the signal of nonoxidized phosphorus atoms, increasing the component at higher chemical shift.  \n\nX-ray diffraction analysis was used to characterize the crystalline forms of neat bP (mixed with PMMA) and after being dispersed in the hybrids. The typical XRD patterns collected at room temperature in the scanning range of $5^{\\circ}<2\\theta$ $<60^{\\circ}$ are reported in Figure 6. Broad bands at $2\\theta=13.8^{\\circ}$ , $30^{\\circ}.$ , and $41.6^{\\circ}$ were observed for all the samples, confirming the amorphous nature of polymer.45 The XRD pattern of the physical mixture PMMA/bB (Figure 6(a)), having composition similar to that of the hybrids, showed the typical bP diffraction peaks of (020), (040), and $\\left(060\\right),^{46}$ centered at $2\\theta$ : $16.90^{\\circ}.$ , $34.19^{\\circ}$ , and $52.34^{\\circ}$ , respectively. The same characteristic diffraction peaks were present in the XRD patterns of the hybrids. Moreover, it was evident that the intensity of the peaks associated with the crystalline fraction of bP along the $z$ direction was different, suggesting a different degree of order in this direction, likely meaning that the average number of piled layers was not the same and depended on the kind of sample. In fact, the preparation methodologies are responsible of the content of bP able to preserve its structure and of the content of exfoliated bP $\\left(\\mathrm{bPn}\\right)^{\\overline{{}}}$ whose nanoflakes theoretically should not be ordered and piled.46  \n\n![](images/19ef18700aae17fff0ee5ba1d147e8161834781f3a75b4a8dac7b060fd6959b7.jpg)  \nFigure 6. XRD patterns of a physical mixture between (a) PMMA and bP, (b) PMMA_bP_B, (c) PMMA_bP_C, and (d) PMMA_bP_A.  \n\nMore in detail, the sample PMMA_bP_B showed intense narrow peaks, as it can be seen by comparing the signal at $16.90^{\\circ}$ with the broad band associated with PMMA. Even if from the experimental evidence collected by $\\ensuremath{{}^{31}\\mathrm{P}}$ -MAS NMR analysis the preparation methodology used here (Method B) was probably not able to well preserve the bP structure (most of bP seemed to be oxidized), the “surviving” flakes maintained their crystallinity and orientation. The presence of large aggregates was, indeed, also proved by micro Raman analysis, confirming the poor effectiveness of the method in promoting an extensive exfoliation of bP. In other words, these results confirm the poor exfoliation degree of this sample. The sample PMMA_bP_A showed less intense peaks which resembled those already observed for bPn47,48 even if the content of nonoxidized bP with respect to the degraded portions, as evaluated by NMR, was similar to that of sample PMMA_bP_B. This result implies that Method A, starting from suspension of $\\mathsf{b P n}$ , provided composites with more exfoliated morphology, as suggested also by Raman results. In addition, by repeating the XRD analysis after 6 months (Figure S5), we obtained a completely superimposable curve, assessing that, once embedded into the PMMA, the bPn with a certain order degree is stable and the polymer is able to preserve its structure.22  \n\nThe sample PMMA_bP_C showed narrow peaks more intense than those of PMMA_bP_A but less intense than those of PMMA_bP_B. On the basis of its highly preserved bP content, assessed by SSNMR (the oxidized/degraded fraction is less than $1/3$ of those of hybrids obtained by Methods A and B), the XRD profile suggested nice output in terms of bP dispersion level and suitability of the Method C which can be stated to boost the bP exfoliation and at the same time to preserve the chemical nature and structure of bP nanoflakes.  \n\nThe stability upon exposure to air and light was also tested by repeating the Raman analysis after $_{6-10}$ months from sample preparation and even after prolonged solubilization of the sample in anisole. Raman spectra collected on different portions of each specimen (films obtained by compression molding or solution casting) clearly showed the characteristic modes of bP whose intensity and Raman shifts depended on the thickness of flakes: both thicker flakes and polymer portions without visible inclusions evidenced the bP peaks confirming that also thinner flakes $\\left(\\mathrm{bPn}\\right)$ were not fully etched nor chemically modified after long exposure of the hybrid to air and light (Figure S6).  \n\n![](images/11d9c4a829bd85893734d59ab25ae85f0b92832ecf55689565eb7751ab4c7927.jpg)  \nFigure 7. Raman spectra of PMMA_bP_C at different times of UV exposure (enlargements in the region of bP modes); curves labeled (a) are referred to visible flakes or aggregates; curves labeled (b) are referred to free/clean portions (without inclusions) of film.  \n\nTo better assess the bPn stability in ambient conditions, the photodegradation induced by UV light irradiation of samples produced by Method C was qualitatively studied. The polymer films of PMMA_C_blank and PMMA_bP_C samples were irradiated in air at room temperature with a UV−vis lamp at different times, and the resulting sample was analyzed by Raman and FTIR-ATR spectroscopies (Figures 7 and S7, respectively) following a recently reported similar approach.22,49 The UV light $\\left(280\\ \\mathrm{nm}\\right)$ was proved to cause the maximum degradation of mechanically exfoliated bP flakes (of $20-30~\\mathrm{~nm}$ thickness), followed by blue light, owing to generation of reactive oxygen species (ROS) participating in bP photo-oxidation.49 The formation of such species and the role of environmental factors on the photo-oxidation extent were already discussed in the literature, by proposing the bP nanoflakes degradation mechanism and the use of imidazonium salts as effective ROS quenchers.50−53  \n\nRaman spectra of PMMA_bP_C hybrid were recorded by visually heading toward a clean part of specimen (apparently without aggregates, curves labeled (b) in Figure 7) and toward a flake (curve (a) in Figure 7). After $250~\\mathrm{min}$ of exposure, the ATR spectra of both samples (blank run and hybrid) showed the characteristic vibration modes due to oxidation and degradation effects (Figure S7), i.e., absorptions in the region of OH, significant broadening of $\\scriptstyle{\\mathrm{C}}={\\mathrm{O}}$ stretching (see the inset in Figure S7) and loss of sharpness in the region of fingerprints due to multiple absorptions of oxidized species. In addition, a clear yellow toning for PMMA_C_blank confirmed the degradation effects (see films images before and after UV irradiation on the right of Figure S7).  \n\nThe Raman analysis (Figure 7) during time of exposure revealed a general loss of the spectra resolution as a consequence of polymer degradation. Even after the hybrid underwent a $250\\ \\mathrm{min}$ UV irradiation, the signals due to the presence of bPn (thinner flakes, curves (b)) were clearly observed, confirming the great stability of nanoflakes once incorporated in the PMMA.22,49  \n\nThese results confirm the effectiveness of the synthetic approach in preserving the bP nanoflakes structure. It is wellknown from the literature50−52 that bP damage is caused by ROS generated by UV light in the presence of oxygen. The polymer chains (PMMA) embedding the nanoflakes protected bPn from oxidation. This was demonstrated by the fact that the UV irradiation of hybrid material provoked the oxidation of PMMA (as clearly shown by ATR), but it had no effect on the bP (as shown by Raman), even by considering the signals attributed to thin flakes; thus, we can reasonably conclude that the photogenerated ROS were not able to access the bP surfaces owing to the PMMA sequestration.  \n\nPS- and PNVP-Based Hybrid Materials. In summary, the in situ radical polymerization after LPE of bP in MMA (Method C) was here shown as an effective method to provide hybrid PMMA-based materials containing bPn (by promoting the exfoliation of bP) and whose structure was preserved (i) during the preparation steps, (ii) after storage in ambient condition for prolonged time, (iii) owing to different thermal and solvent treatment, and (iv) even when subjected to UV aging. In addition, the procedure is simple if compared with other methods and does not involve extensive use of solvents and sonication. To test the feasibility of the method and the possibility to prepare hybrids with different polymers, the in situ radical polymerization of Sty and NVP was carried out (Table 1). Two different contents of bP were used for these runs: the hybrids were characterized by SEC, DSC, TGA, Raman, and FTIR-ATR spectroscopies, and the results were compared to those of their blank experiments (Table 3). In the case of PS hybrids, a bimodal shape of MW distribution curves was observed together with a certain increase of the $\\bar{M}_{\\mathrm{w}}$ values, presumably due to confinement of growing macroradicals, as previously discussed for a similar PMMA-based sample. These observations suggest that also Sty can establish interactions with bP layers, and such interactions are effective for bP exfoliation. In addition, no significant variation concerning the thermal features of all hybrids was observed with respect to blank experiments with the exception of the $T_{\\mathrm{g}}$ values which seemed to weakly increase depending on the bP content.  \n\nTable 3. Molecular Weight Evolution and Thermal Features of PS and PNVP-Based Samplesa   \n\n\n<html><body><table><tr><td colspan=\"4\"></td><td>T</td><td>(C)℃ Tinc</td></tr><tr><td>sample</td><td>M, (D) 25700</td><td>Mm (D) 56700</td><td>Tg (C) 100.7</td><td>374</td><td>418</td></tr><tr><td>PS_C_blank PS_bP_C</td><td>24600</td><td>85200</td><td>99.8</td><td>380</td><td>417</td></tr><tr><td>PS_bP_C2</td><td>21000</td><td>68100</td><td>100.2</td><td>375</td><td>414</td></tr><tr><td>PNVP_C_blank</td><td>nd</td><td>nd</td><td>160.0</td><td>410</td><td>440</td></tr><tr><td>PNVP_bP_C</td><td>nd</td><td>nd</td><td>166.3</td><td>410</td><td>440</td></tr><tr><td>PNVP_bP_C2</td><td>nd</td><td>nd</td><td>163.2</td><td>412</td><td>437</td></tr></table></body></html>\n\nand: not determined. bIntercept of tangents. cFrom DTG curves as the maximum of the peak.  \n\nBoth PS- and PNVP-based materials were analyzed as films obtained by compression molding. FT-IR spectra showed the vibration modes characteristic of the polymer matrices, whereas the Raman spectra evidenced the typical signature peaks of bP in addition to those of polymers (FTIR and Raman spectra and related attributions are reported in Figure S8 and Tables S2 and S3).54,55 Moreover, the Raman signals shape and shifts were in agreement with results previously discussed for PMMA-based hybrids. These data confirmed that the synthetic procedure is able to preserve the bP structure, even when different monomers are employed, and to obtain systems potentially suitable for designing devices, which are generally provided by more complex synthetic procedures.56  \n\nAfter storing the samples in ambient conditions for 6 months, the hybrids PS_bP_C and PNVP_bP_C were solubilized in anisole and water, respectively, and films were obtained by solution casting onto glass. They were carefully analyzed by Raman microscopy (Figure 8). Both polymers protected the bP flakes, and the Raman spectra collected in the different parts of the specimen showed the characteristic vibration modes of phosphorus flakes, visible everywhere, although with a different relative intensity. A fine morphology with a good distribution of the particles was found especially for the sample PNVP_bP_C, which was obtained by water casting. The microscopic images showed in this case only small and homogeneously dispersed inclusions. Interestingly, for all the inclusions, the Raman spectrum revealed the diagnostic peaks of bP even though the sample was treated with water without protection from air and light. This result definitely underlines the feasibility and the power of the method in stabilizing bPn as it is prepared and even after different manipulation.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# CONCLUSIONS  \n\nHybrid materials were obtained by dispersing black phosphorus nanoflakes in polymer matrices through different synthetic strategies with the aim of promoting the exfoliation of bP while protecting the generated nanostructures from oxidation. All the composites ensued processable and their films, obtained by compression molding, were analyzed by FTIR, Raman, $^{31}\\mathrm{{\\dot{P}}.}$ - SSNMR, XRD, SEC, TGA, and DSC to pinpoint the structural characteristics of both phases: the polymer matrix and the bPn. In addition, a deep investigation about the bPn stability, upon different treatments of prepared films (melt processing, solvent solubilization, and UV light irradiation), was performed. Raman, $^{31}\\mathrm{{P-SSNMR},}$ and XRD analyses evidenced that, depending on the preparation methodology, the hybrids were characterized by a different exfoliation degree and by a different content of bP oxidized species. The procedure comprising the liquid-phase exfoliation (LPE) in the vinyl monomer followed by in situ radical polymerization provided hybrid polymerbased materials with good dispersion of bP (particularly by using MMA and NVP) and protected bP nanoflakes. The monomer LPE seems capable of promoting the exfoliation of bP, and the following in situ polymerization encapsulates the nanoflakes, preserving their structure. By taking into account that, to-date, bPn are prepared in low quantities by mechanical exfoliation, this strategy seems to be a promising tool to easily provide larger amounts of exfoliated bP. In addition, by considering that the nanoflakes cannot survive for a long time in air, light, and humidity and that, once generated, bPn have to be passivated by polymer coating, this approach emerges as a new strategy to provide bPn already protected by enveloping the native nanostructures with polymer chains. Therefore, the methodology here realized is able to preserve the bPn structure not only from air and light exposure but also from thermal and solvent treatment.  \n\n![](images/6a9c6336374d76d17c2424a1f96dfbfd147f5f321c16ac34a03acd185ac2a458.jpg)  \nFigure 8. Visual imaging and Raman spectra of (A) PS_bP_C and (B) PNVP_bP_C, collected at different points of the specimen. Insets: pictures of films obtained on glasses by solution casting from anisole for hybrid $\\mathrm{PS}\\underline{{\\mathrm{bP}}}\\underline{{\\mathrm{C}}}$ and from water for PNVP_bP_C.  \n\nThis approach affords the opportunity to obtain scalable quantities of $\\mathsf{b P n}$ , opening the way for an easier design of (optoelectronic) devices. Moreover, since PMMA is the most used resist for electron beam lithography, solutions of the PMMA nanocomposites can be directly spin-coated without further processing, and the bPn within can be processed into devices without the need of a protective environment for fabrication.57",
+        "category": " Conclusions"
+    },
+    {
+        "id": 6,
+        "chunk": "# ASSOCIATED CONTENT",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# $\\otimes$ Supporting Information  \n\nThe Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.7b05298.  \n\nAdditional research data supporting this publication, including FTIR-ATR and Raman spectra of starting bP and prepared hybrids, Raman spectra of PMMA_bP_C hybrid after 6−10 months from preparation, FTIR-ATR spectra of PMMA_bP_C hybrid and related polymer matrix after UV aging, FT-IR and Raman peaks assignments of all polymers used, and schematic description of synthetic methodologies for hybrids preparation (PDF)",
+        "category": " References"
+    },
+    {
+        "id": 8,
+        "chunk": "# AUTHOR INFORMATION  \n\nCorresponding Author   \n$^*\\mathrm{E}$ -mail: passaglia@pi.iccom.cnr.it.   \nORCID   \nElisa Passaglia: 0000-0001-5006-2531   \nStefan Heun: 0000-0003-1989-5679   \nNotes   \nThe authors declare no competing financial interest.",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nThe European Research Council (ERC) and the National Research Council of Italy (CNR) are acknowledged for funding the work through the project PHOSFUN, an ERC Advanced Grant (Grant Agreement No. 670173), and the project “Ma.Po.Fun” (DCM.AD002.239).",
+        "category": " Acknowledgments"
+    },
+    {
+        "id": 10,
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H.; Field, M. ${\\mathrm{R}}.{\\mathrm{}}{\\mathrm{}}$ Ramanathan, R.; Singh, M.; Bansal, V.; Sriram, S.; Bhaskaran, M.; Walia, S. Degradation of Black Phosphorus is Contingent on UVBlue Light Exposure. NPJ. 2D Mater. Appl. 2017, 1, 18.   \n(50) Abellàn, G.; Wild, S.; Lloret, V.; Scheuschner, N.; Gillen, R.; Mundloch, U.; Maultzsch, J.; Varela, M.; Hauke, F.; Hirsch, A. Fundamental Insights into the Degradation and Stabilization of Thin Layer Black Phosphorus. J. Am. Chem. Soc. 2017, 139, 10432−10440. (51) Walia, S.; Sabri, Y.; Ahmed, T.; Field, M. R.; Ramanathan, R.; Arash, A.; Bhargava, S. K.; Sriram, S.; Bhaskaran, M.; Bansal, V.; Balendhran, S. Defining the Role of Humidity in the Ambient Degradation of Few-Layer Black Phosphorus. 2D Mater. 2017, 4 (1), 015025.   \n(52) Zhou, $\\mathrm{Q.;}$ Chen, $\\mathrm{Q.;}$ Tong, Y.; Wang, J. Light-Induced Ambient Degradation of Few-Layer Black Phosphorus: Mechanism and Protection. Angew. Chem., Int. Ed. 2016, 55, 11437−11441.   \n(53) Walia, S.; Balendhran, S.; Ahmed, T.; Singh, M.; El-Badawi, C.; Brennan, M. D.; Weerathunge, P.; Karim, M. N.; Rahman, F.; Rassell, A.; Duckworth, J.; Ramanathan, R.; Collis, G. E.; Lobo, C. J.; Toth, M.; Kotsakidis, J. C.; Weber, B.; Fuhrer, M.; Dominguez-Vera, J. M.; Spencer, M. J. S.; Aharonovich, I.; Sriram, S.; Bhaskaran, M.; Bansal, V. Ambient Protection of Few-Layer Black Phosphorus via Sequestration of reactive Oxygen Species. Adv. Mater. 2017, 29, 1700152.   \n(54) Liang, C. Y.; Krimm, S. Infrared Spectra of High Polymers. VI. J. Polym. Sci. 1958, 27, 241−254.   \n(55) Borodko, Y.; Habas, S. E.; Koebel, M.; Yang, P.; Frei, H.; Somorjai, G. A. Probing the Interaction of Poly(VinylPyrrolidone) with Platinum Nanocrystals by UV-Raman and FTIR. J. Phys. Chem. B 2006, 110, 23052−23059.  \n\n(56) Zhang, X.; Xie, H.; Liu, Z.; Tan, C.; Luo, Z.; Li, H.; Lin, J.; Sun, L.; Chen, W.; Xu, Z.; Xie, L.; Huang, W.; Zhang, H. Black Phosphorus Quantum Dots. Angew. Chem. 2015, 127, 3724−3728. (57) Telesio, F.; Passaglia, E.; Cicogna, F.; Costantino, F.; SerranoRuiz, M.; Peruzzini, M.; Heun, S. Hybrid 2D Black Phosphorus/ Polymer Materials: New Platforms for Device Fabrication; http:// arxiv.org/abs/1802.01103.",
+        "category": " References"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/preparation of antifog and antibacterial coatings by photopolymerization.json b/task2/task2-chunks/preparation of antifog and antibacterial coatings by photopolymerization.json
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+[
+    {
+        "id": 1,
+        "chunk": "# Preparation of antifog and antibacterial coatings by photopolymerization  \n\nRuifen Tanga, Atif Muhammadb, Jinliang Yanga and Jun Niea\\*  \n\nThis paper contains a kind of ultraviolet-cured antifogging and antibacterial coating. A quaternary ammonium salt (14QAS), which was synthesized in this paper, has been implemented as a monomer. The chemical structure of 14QAS has been confirmed by Fourier transform infrared spectroscopy and nuclear magnetic resonance. The nitrogen atom on the surface of the coatings with 14QAS was observed by X-ray photoelectron spectroscopy. The Surface wettability of the polymer film was studied by contact angle analysis, which confirmed the hydrophilicity of the coatings with low water contact angle $(\\sim25^{\\circ})$ . The antifog properties were evaluated under different conditions. The antibacterial activity of coatings with 14QAS reached $99.9\\%$ against S. aureus and E. coli. Copyright $\\mathfrak{O}$ 2014 John Wiley & Sons, Ltd.  \n\nKeywords: antifog; antibacterial; coating; photopolymerization; QAS",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 2,
+        "chunk": "# INTRODUCTION  \n\nNigh to dew point, water vapors condense into microscopic droplets to ensue fogging. Although fog itself is harmless, it can cause serious problems in transparent solid materials (such as optical devices, agricultural transparent plastic films, and translucent panels of solar cells) due to transparency and visibility drop.  \n\nTo avoid fogging phenomenon on transparent materials, several methods have been explored during the past decades. Among them, heating the materials, improving the air velocity, and using antifog coatings are very common. Heating could keep the temperature of materials higher than the dew point, to prevent condensation of water vapor, but it consumes lots of energy that cannot be ignored. Likewise, improving air velocity causes humidity fall at material surface that enhances water evaporation, but this method also consumes too much energy. Thus, antifogging coatings are most interesting due to their lesser energy cost and easily manageable nature.  \n\nAmong these coatings, superhydrophilic or superhydrophobic surfaces[1–5] had attracted a lot of attention, as they can spread water droplets flat or made them roll down from the surface. The disappearance of the droplets made these two kinds of coatings to be excellent antifog surfaces. Otherwise, these surfaces that often contain nanoparticles (such as ${\\mathsf{T i O}}_{2},$ $\\mathsf{S i O}_{2},$ and carbon nanotubes) will cause poor mechanical stability, short lifetimes, and the residual water film on the surface. Moreover, complicated procedure and higher cost are also major restrictions.  \n\nNow, day’s commercial coatings use surfactants, which reduce surface tension of water. So, the droplets wet the surface easily, and the antifog property is obtained. However, this kind of antifog coating cannot maintain its property for a long time due to surfactant discharge with condensed water. Researchers tried to increase lifetime of these coatings, and as a consequence, durable antifog coatings had been reported; e.g. Laura Introzzi[6] presented a new antifog coating made of pullulan for packaging applications. Nurxat Nurraje[7] demonstrated that hydrophilic polysaccharides such as chitosan, alginate, hyaluronic acid, and carboxymethyl cellulose could be used to produce long-lasting antifog coatings via layer-by-layer assembly technique. However, fixing the surfactants in the coatings is another way to produce long-lasting antifog coatings.  \n\nQuaternary ammonium salt (QAS) have been known and widely used for more than half a century to control microbial growth for a variety of applications such as biomedical devices, fabric treatment, hair rinses, and food products.[8] Surfaces coated with QAS-containing polymers have been shown to be very effective in killing a wide range of microorganisms such as Gram-positive and Gram-negative bacteria, yeasts, and molds.[9–11] Furthermore, QAS was also a kind of surfactant, and QAS-containing polymers may also have antifogging behavior.  \n\nIn this paper, a QAS (14QAS), which was synthesized in our lab, was used in the ultraviolet-cured antifog coatings. The results indicated that 14QAS could be preserved in the coatings to create long-time antifog. Moreover, an interesting pheromone was found in this study: the antibacterial property was also found in the cured coating films. Consequently, these coatings have a wide range of applications in daily life, such as bathroom mirrors, vehicle windscreens, room windows, children’s toys, and medical devices.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# EXPERIMENTAL",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# Materials  \n\nDimethylaminoethyl methacrylate (DMAEMA), 1-bromotetradecane (BTD), hydroxyethyl acrylate (HEA), and tetrahydrofuran were purchased from Sinopharm Group Chemical Reagent (Beijing, China). Poly (ethylene glycol) diacrylate 600 (PEGDA 600) and polyurethane  \n\n\\* Correspondence to: Jun Nie, State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China. E-mail: niejun@mail.buct.edu.cn   \na R. Tang, J. Yang, J. Nie State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China   \nb A. Muhammad Department of Applied Sciences and Technology, Politecnico di Torino, Corso duca degli Abruzzi-24, Torino-10124, Italy  \n\nacrylate (CN929) were given by Sartomer Company (Warrington, PA, USA) as a gift. 2-hydroxy-2-methylpropiophenone (1173) was obtained from Changzhou Runtec Chemical. The leveling agents were donated by BYK Additives & Instruments (Wesel, Germany).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# Synthesis  \n\nThe synthesis route of 14QAS was list in Scheme 1.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# Synthesis of 14QAS  \n\nDimethylaminoethyl methacrylate $\\beta1.49,\\ 0.25\\$ , BTD $(55.49,$ $0.2\\mathsf{m o l}.$ ), and tetrahydrofuran $(30\\mathsf{m}\\mathsf{l})$ were added into a $250\\mathrm{ml}$ three-neck round-bottomed flask equipped with condensator, desiccator, and mechanical stirrer. The mixture was stirred at $37^{\\circ}\\mathsf{C}$ for $24\\mathsf{h r}$ .  \n\nAfter the reaction, unreacted BTD and DMAEMA were removed by repeated washing for $1{-}2\\mathsf{m i n}$ with $5\\mathrm{-}7\\mathsf{m}|$ ether aliquots, discarding the ether supernatant after each wash. Residual ether was removed via gentle nitrogen stream, and the final product was dried for $24\\mathsf{h r}$ under vacuum in the dark. The yield of 14QAS under $37^{\\circ}\\mathsf{C}$ could be $33.7\\%$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# Preparation of the antifog coatings  \n\nFirstly, 14QAS and 1173 were dissolved in HEA and then mixed with PEGDA 600, CN929, and leveling agent. Secondly, the wire bar coater $(20\\upmu\\mathsf{m})$ was used to prepare the film on glass slides and irradiated for 3 min with a medium-pressure mercury lamp. The light intensity was detected by an ultraviolet light radiometer (Beijing Normal University, China), and the value was $20\\mathsf{m w/c m}^{2}$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# Characterization  \n\nThe $^1\\mathsf{H}$ nuclear magnetic resonance (NMR) spectra were carried out on a 400 MHz NMR instrument (Bruker Corporation, Germany) at $298\\mathsf{K}$ with $C D C\\mathsf{I}_{3}$ as solvent and TMS as internal standard.  \n\nThe IR spectra were measure on a Fourier transform infrared spectroscopy 5700 (Thermo Electro Corporation, Waltham, MA).  \n\nThe XPS spectra of the coatings were obtained by using a VG ESCALAB MKII X-ray photoelectron spectrometer (VG Scientific Ltd., UK) with Al $\\mathsf{K}a$ radiation to find out if there was any nitrogen atom on the surface of them. Survey spectra were recorded for $0{\\mathrm{-}}1350{\\mathrm{eV}}$ binding energy range.  \n\nContact angle (CA) was obtained with a VCA Optima CA measuring instrument (AST products, Inc.) with a drop size $1.0\\upmu\\up L$ of deionized water. Four samples of each formulation were prepared for this test. Four measurements were made on each sample. The final CA of each coating according to its own formulation was the average of its own data.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# Antifog tests  \n\nAntifog properties were evaluated by simulating real conditions of fogged materials: (a) hot-fog test, (b) cold-fog test, and (c) aspiration test.[7] In hot-fog test, the coated side of glass was exposed to steam of beaker containing $80^{\\circ}C$ water as compared with the cleaning glass. Then, two glass slides were placed on the top of written letters. The visibility of the letter at the bottom of the glass slide was evaluated for the degree of antifog. In coldfog test (b), the coated glasses were placed in a refrigerator $(4^{\\circ}\\mathsf{C})$ for 6 hr and then placed on the top of an Erlenmeyer flask containing steaming water. For comparison, the cleaning glass was also placed in the refrigerator $(4^{\\circ}\\mathsf{C})$ . In test (c), for quick evaluation of the antifog performance of the coatings, a simple aspirating / breathing test was conducted on the sample.  \n\n![](images/00fb2ff62fa90b7ea57d3eea710699783675150548f47d3d3e9568d0b40468e0.jpg)  \nScheme 1. Synthesis route of 14QAS.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# Mechanical property  \n\nSeveral methods were used to evaluate the mechanical properties of the films, including the following: (a) ISO15184 pencil hardness test and (b) pendulum hardness test.  \n\nIn the pencil hardness test, first, placed the coated substrate under the tip of a pencil, and then moved the pencil holder in one direction. The force applied to the pencil tip came from a 1 Kg static load. The scratched regions were evaluated by optical microscopy. The pencil hardness scale extends from 9H (good) to 6B (poor).  \n\nIn the pendulum hardness test, the pendulum hardness tester (BGD 508) supplied by BIUGED which follows ISO 1522. The pendulum angles were sat from $5^{\\circ}$ to $2^{\\circ},$ and the time of empty swing was $440\\pm6$ sec. The hardness was calculated with the following expression where $t$ is the time of swing on sample and $\\mathfrak{t}_{0}$ is the time of empty swing.  \n\n$$\n\\mathsf{X}=\\frac{\\mathsf{t}}{\\mathsf{t}_{0}}\n$$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# Antibacterial tests  \n\nAntibacterial properties of antifog coatings were quantitatively evaluated on E. coli (gram-negative) and S. aureus (grampositive) by using the experimental protocols as described by Tiller.[12] A $100\\mathrm{-\\upmuL}$ suspension of E. coli or S. aureus in $0.1\\mathsf{M}$ aqueous PBS buffer $\\mathsf{(p H7.0,~10~^{11}~c e l l s/m l)}$ was added to $50\\mathrm{ml}$ of yeast/dextrose broth in a sterile Erlenmeyer flask. With shaking at 200 rpm, the suspension was incubated for $8\\mathsf{h r}$ at $37^{\\circ}C$ Bacterial cells were separated by centrifugation (2700 rpm, $10\\mathrm{{min}})$ , washed, and suspended in distilled water.[13] This bacterial suspension had a concentration of ${10}^{6}/\\mathrm{ml}$ . The inoculated specimens were prepared following ISO22196-2007. Before preparing, every coating was soaked in water for $2\\mathsf{h r}$ to remove unreactive 14QAS. An uncoated slide was used as standard, and the number of viable colonies grown was used as reference. The coating that did not contain QAS was used as a sample to compare. The bacterial colonies were allowed to grow on the surface of the coatings. The antibacterial activity was then evaluated according to their antibacterial rates.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# RESULTS AND DISCUSSION",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# Synthesis  \n\n14QAS was prepared by the reaction of tertiary amine and bromoalkane. As shown in Table 1, the yield was first increased and then decreased with rising temperature, and the maximum yield was obtained at $35^{\\circ}\\mathsf{C}$ To get the optimal one for synthesis of 14QAS, the temperatures between $35^{\\circ}C$ and $40^{\\circ}\\mathsf{C}$ were also used. Finally, $37^{\\circ}\\mathsf{C}$ was found to be the temperature having the maximum yield $(35.4~\\%)$ .  \n\nAs shown in Figure 1, compared with the spectrum of DMAEMA, peaks of C–N $1299\\mathsf{c m}^{-1}$ and $1034(c m^{-1})$ and $C=C$ $(1635\\mathsf{c m}^{-1})$ are preserved in the spectrum of 14QAS after reaction while a new peak of $(C H_{2})_{n}$ $(\\mathsf{n}\\geq2)$ ) rocking vibration appears at $728{\\mathsf{c m}}^{-1}$ . Disappearance of C–Br $(1043\\mathsf{c m}^{-1})$ peak in 14QAS spectrum had backed up the reaction between DMAEMA and BTD.[14]  \n\n<html><body><table><tr><td colspan=\"6\">Table 1. The yield of 14QAS under different temperature</td></tr><tr><td rowspan=\"3\">Product</td><td colspan=\"4\">Yield under different temperature (%)</td></tr><tr><td>25℃</td><td>30℃ 35℃</td><td>40℃</td><td>45°℃</td></tr><tr><td>25.8</td><td>30.3</td><td>33.4 31.7</td><td>28.7</td></tr></table></body></html>  \n\n![](images/8db9fad7721a9ad0292a6da503293c0b17768e73e76e7970c2d445e780d4ed54.jpg)  \nFigure 1. Fourier transform infrared spectroscopy spectra of 14QAS, dimethylaminoethyl methacrylate, and bromotetradecane. This figure is available in colour online at wileyonlinelibrary.com/journal/pat  \n\n![](images/36a2a926f1656e41e773c3da6878908bb47f633af013d56cc835e8d1265f6b5c.jpg)  \nFigure 2. Nuclear magnetic resonance spectra of 14QAS and dimethylaminoethyl methacrylate. This figure is available in colour online at wileyonlinelibrary.com/journal/pat  \n\n$\\mathsf{\\Omega}^{1}\\mathsf{H}$ NMR was used as another method to identify the chemical structure of 14QAS. As shown in Fig. 2, peaks in the $^1\\mathsf{H}$ NMR spectrum of 14QAS $C D C\\mathsf{I}_{3}$ was used as the lock solvent) at  \n\n3.5 ppm $(-N^{+}\\mathrm{-}C H_{2}-)$ and 3.3 ppm $[(-N^{+}-(C\\Hat{1}_{3})_{2}]$ appeared with a complete disappearance of the dimethylamino protons at 2.2 ppm.[9]  \n\n$^1\\mathsf{H}$ (DMAEMA): 1.88[3H, s, $-C H_{3}];$ 2.2[6H, s, $(-N-(C H_{3})_{2}];$ 2.5 [2H, $ S,-C H_{2}-N-1];$ 4.18[2H, $S,\\mathrm{-CH}_{2}$ –COO–)]; 5.5–6.05[2H, s, $\\scriptstyle(=\\mathsf{C H}_{2})],$ $^1\\mathsf{H}$ (14QAS): 0.88[3H, $\\mathsf{t},(-\\mathsf{C}\\mathsf{H}_{3})],$ 1.25–1.34 [26H,m, $(-{\\mathsf{C H}}_{2})_{13}];$ 1.96[3H, s, $-C H_{3}];$ 3.3[6H, s, $(-N^{+}-(C H_{3})_{2}];$ 3.5[2H, s, $(-N^{+}-C H_{2}-)I;$ 4.17[2H,s,– $C H_{2}$ –COO–)]; $4.69[2mathsf{H},\\mathsf{S},-\\mathsf{C H}_{2}-\\mathsf{N}^{+}-)];$ 5.55–6.15[2H, s, $(=C H_{2})];$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 14,
+        "chunk": "# Contact angle analysis  \n\nIn Table 2 first set of experiments shows increase in CA that could be due to increase of HEA and decrease of PEGDA600 in coatings. Although there was no regularity in this change, yet results indicated that PEGDA600 was more hydrophilic than HEA. It must be the long chain of ethylene oxide in PEGDA 600 that led to those results. Second group of experiments displays association between CA and weight ratio between HEA and CN929. As observed clearly, CA increases with the increase of HEA and the decrease of CN929 in coatings, which could confirm that CN929 was more hydrophilic than HEA. Upon comparison of two sets of experiments for same content of HEA, the CAs in first group was always higher than the second. For this reason, PEGDA600 also confirmed to have higher hydrophilic property than CN929.  \n\nThus, it can be concluded that these three materials had different effects on hydrophilic property of the coating. Their hydrophilicity can be arranged as: $\\mathsf{P E G D A600>C N929>H E A}$ .  \n\nAfter examining the hydrophilic properties of the coatings without QAS, the QAS-contained coatings were explored. Thus, data of Table 3 were created. A significant decrease in CA was observed with 14QAS increase and HEA decrease. Hence, it could be concluded that 14QAS improves hydrophilicity of coatings. So, more 14QAS dissolved in HEA, more hydrophilic coatings will be.  \n\nTable 2. Average contact angles of coatings having different ratios of HEA and PEGDA600 or CN929 $(3\\%$ 1173)   \n\n\n<html><body><table><tr><td rowspan=\"2\">Code</td><td colspan=\"4\">The content of each component in coatings (wt. %)</td><td rowspan=\"2\">CA</td></tr><tr><td>14QAS</td><td>HEA</td><td>CN929</td><td>PEGDA600</td></tr><tr><td rowspan=\"6\">1 2 3 4 5</td><td>0</td><td>5</td><td>47</td><td>45</td><td>39.7</td></tr><tr><td></td><td>10</td><td></td><td>40</td><td>43.0</td></tr><tr><td></td><td>15</td><td></td><td>35</td><td>46.5</td></tr><tr><td></td><td>20</td><td></td><td>30</td><td>49.3</td></tr><tr><td>0</td><td>25</td><td></td><td>25</td><td>54.0</td></tr><tr><td>6</td><td>5</td><td>47</td><td>45</td><td>39.7</td></tr><tr><td>7</td><td></td><td>10</td><td>42</td><td></td><td>42.0</td></tr><tr><td>8</td><td></td><td>15</td><td>37</td><td></td><td>43.5</td></tr><tr><td>9</td><td></td><td>20</td><td>32</td><td></td><td>46.1</td></tr><tr><td>10</td><td></td><td>25</td><td>27</td><td></td><td>49.0</td></tr></table></body></html>  \n\nTable 3. Average contact angles of coatings having different ratios of 14QAS and HEA $(3\\%$ 1173)   \n\n\n<html><body><table><tr><td rowspan=\"2\">Code</td><td colspan=\"4\">The content of each component in coatings (wt%)</td><td rowspan=\"2\">CA</td></tr><tr><td>14QAS</td><td>HEA</td><td>CN929</td><td>PEGDA600</td></tr><tr><td>11</td><td>2.5</td><td>22.5</td><td>47</td><td>25</td><td>46.0</td></tr><tr><td>12</td><td>5</td><td>20</td><td></td><td></td><td>37.1</td></tr><tr><td>13</td><td>7.5</td><td>17.5</td><td></td><td></td><td>27.4</td></tr><tr><td>14</td><td>10</td><td>15</td><td></td><td></td><td>21.3</td></tr><tr><td>15</td><td>12.5</td><td>12.5</td><td></td><td></td><td>17.4</td></tr><tr><td>16</td><td>2.5</td><td>22.5</td><td>27</td><td>45</td><td>38.7</td></tr><tr><td>17</td><td>5</td><td>20</td><td></td><td></td><td>29.3</td></tr><tr><td>18</td><td>7.5</td><td>17.5</td><td></td><td></td><td>21.3</td></tr><tr><td>19</td><td>10</td><td>15</td><td></td><td></td><td>16.5</td></tr><tr><td>20</td><td>12.5</td><td>12.5</td><td></td><td></td><td>12.4</td></tr></table></body></html>  \n\nTable 4. Average contact angles of coatings with different HEA-14QAS $(3\\%$ 1173)   \n\n\n<html><body><table><tr><td rowspan=\"2\">Code</td><td colspan=\"4\">The content of each component in coatings (wt%)</td><td rowspan=\"2\">CA</td></tr><tr><td>14QAS</td><td>HEA</td><td>CN929</td><td>PEGDA600</td></tr><tr><td>21</td><td>2.5</td><td>2.5</td><td>47</td><td>45</td><td>31.3</td></tr><tr><td>22</td><td>5</td><td>5</td><td>42</td><td></td><td>24.1</td></tr><tr><td>23</td><td>7.5</td><td>7.5</td><td>37</td><td></td><td>19.3</td></tr><tr><td>24</td><td>10</td><td>10</td><td>32</td><td></td><td>15.4</td></tr><tr><td>25</td><td>12.5</td><td>12.5</td><td>27</td><td></td><td>12.4</td></tr><tr><td>26</td><td>2.5</td><td>2.5</td><td>47</td><td>45</td><td>31.3</td></tr><tr><td>27</td><td>5</td><td>5</td><td></td><td>40</td><td>27.4</td></tr><tr><td>28</td><td>7.5</td><td>7.5</td><td></td><td>35</td><td>24.3</td></tr><tr><td>29</td><td>10</td><td>10</td><td></td><td>30</td><td>21.6</td></tr><tr><td>30</td><td>12.5</td><td>12.5</td><td></td><td>25</td><td>19.4</td></tr></table></body></html>  \n\nAs described earlier that 14QAS, due to poor compatibility with PEGDA600 and CN929, should be dissolved in HEA first. Different mass contents of HEA-14QAS 1:1 solution were investigated in coatings, as shown in Table 4. Data shows that, by increasing mass content of HEA-14QAS solution, CA of water decreases.  \n\nUpon comparison of two sets of experiments, CA decreasing rates were different to each other. Evidently, the rate in first group was higher than in second group.  \n\nThe other side of the story is excellent hydrophilic properties also had disadvantages like defect of leveling properties. Hence, the desire to reduce the surface tension at the liquid/vapor interface, as low as possible, was created. In that regard, leveling agent was needed to obtain smooth surface. At the meantime, the leveling agent should have the least influence on the hydrophilic properties of the coatings. Keeping in mind all these factors, BYK 348 was chosen. The results from Table 5 indicated that the CA increased on average by almost $4{-}5^{\\circ}$ because of the participants of BYK 348.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# Antifog tests  \n\nTable 5 contains data for antifog tests of samples. As observed, only sample 35 has shown antifog properties (the bold and underlined words) where the other samples were all fogging during tests. These results were consistent with the hypothesis that the 14QAS could create a coating with antifogging capability.  \n\nAfter hot-fog test sample, 35 were dried at $40^{\\circ}C$ for $24\\mathsf{h r}$ under vacuum. Then, its antifog property was investigated again, through the hot-fog test. These two steps were repeated three times. Photos of these tests are shown in Fig. 3, demonstrating that these coatings still have excellent antifog property.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# Antibacterial properties  \n\nThe antibacterial activity of coatings with 14QAS against S. aureus and E. coli is shown in Table 5. For comparison, coatings without 14QAS are shown in Table 6 as reference. Coatings with 14QAS showed a sharp decrease in the count for viable colonies of both bacteria after $24\\mathsf{h r}$ . Furthermore, the antibacterial rate of coatings with 14QAS (not lower than $12.5\\mathrm{wt\\%}$ could reach $99.9\\%$ against S. aureus and $99.9\\%$ against E. coli (the bold and underlined numbers). Although coatings having 14QAS lower than $12.5~\\mathrm{wt\\%}$ did not show complete inhibition of gram-negative and grampositive, yet antibacterial activity rates were still higher than coatings without 14QAS. These results indicate that introduction of 14QAS endows coatings with excellent antibacterial properties.  \n\nTable 5. Average contact angles, antifog tests and antibacterial rates of the coatings contained $0.5\\%$ BYK348 $2.5\\%$ 1173)   \n\n\n<html><body><table><tr><td rowspan=\"2\">Sample</td><td colspan=\"4\"> The content of each component in coatings</td><td rowspan=\"2\">CA</td><td colspan=\"3\"></td><td colspan=\"2\">Antibacterial</td></tr><tr><td></td><td>(wt%)</td><td>PUA(CN929)</td><td>PEGDA600</td><td colspan=\"3\">Antifog tests</td><td>rate</td><td></td></tr><tr><td></td><td>14QAS</td><td>HEA</td><td></td><td></td><td></td><td>Hot-fog test </td><td>Cold-fog test</td><td>Aspiration test</td><td>S.aureus</td><td>E. coli</td></tr><tr><td>31 32</td><td>2.5</td><td>2.5</td><td>47</td><td>45</td><td>36.5</td><td>Fogging</td><td>Fogging</td><td>Fogging</td><td>97.4</td><td>97.2</td></tr><tr><td>33</td><td>5</td><td>5</td><td>42</td><td></td><td>28.1</td><td>Fogging</td><td>Fogging</td><td>Fogging</td><td>97.9</td><td>97.5</td></tr><tr><td>34</td><td>7.5 10</td><td>7.5</td><td>37</td><td></td><td>25.3</td><td>Fogging</td><td>Fogging</td><td>Fogging Fogging</td><td>98.1 98.5</td><td>97.9 98.4</td></tr><tr><td></td><td>12.5</td><td>10</td><td>32 27</td><td></td><td>22.3</td><td>Fogging Antifog</td><td>Fogging Antifog</td><td>Antifog</td><td>99.9</td><td>99.9</td></tr><tr><td>35</td><td>2.5</td><td>12.5</td><td>47</td><td>45</td><td>18.7</td><td>Fogging</td><td>Fogging</td><td>Fogging</td><td>97.5</td><td>97.2</td></tr><tr><td>36 37</td><td>5</td><td>2.5 5</td><td></td><td>40</td><td>36.5 31.7</td><td>Fogging</td><td>Fogging</td><td>Fogging</td><td>97.5</td><td>97.4</td></tr><tr><td>38</td><td>7.5</td><td>7.5</td><td></td><td>35</td><td>28.7</td><td>Fogging</td><td>Fogging</td><td>Fogging</td><td>97.9</td><td>98.1</td></tr><tr><td>39</td><td>10</td><td>10</td><td></td><td>30</td><td>26.3</td><td>Fogging</td><td>Fogging</td><td>Fogging</td><td>98.3</td><td>98.2</td></tr><tr><td>40</td><td>12.5</td><td>12.5</td><td></td><td>25</td><td>23.1</td><td>Fogging</td><td>Fogging</td><td>Fogging</td><td>98.4</td><td>98.4</td></tr></table></body></html>  \n\n![](images/480d94caf33c92249386b2c4ddb7b956193e85302267bf274545b06133863fc2.jpg)  \nFigure 3. Antifog photos of repeated hot-fog tests taken after being dried (a. once, b. twice, and c. triple). This figure is available in colour online at wileyonlinelibrary.com/journal/pat  \n\n<html><body><table><tr><td colspan=\"4\">Table 6. Antibacterial properties of coatings contained BYK348without14QAS</td></tr><tr><td rowspan=\"3\">Sample</td><td colspan=\"3\">The content of each component in</td><td rowspan=\"2\">S. E. aureus coli</td></tr><tr><td>14QAS</td><td>coatings (wt%) HEAPUA(CN929)PEGDA600</td></tr><tr><td>0 5 47</td><td></td><td></td><td>42.7</td></tr><tr><td>41 42</td><td>10</td><td></td><td>45 40</td><td>40.5 51.6 47.8</td></tr><tr><td>43</td><td>15</td><td></td><td>35</td><td>57.6 52.6</td></tr><tr><td>44</td><td>20</td><td></td><td>30</td><td>60.5</td></tr><tr><td></td><td></td><td></td><td></td><td>58.4</td></tr><tr><td>45</td><td>25</td><td></td><td>25</td><td>62.3 61.3</td></tr><tr><td>46</td><td>0 5</td><td>47</td><td>45</td><td>43.3 42.3</td></tr><tr><td>47</td><td>10</td><td>42</td><td>52.3</td><td>46.4</td></tr><tr><td>48</td><td>15</td><td>37</td><td>56.8</td><td>53.4</td></tr><tr><td>49</td><td>20</td><td>32</td><td>62.6</td><td>57.2</td></tr><tr><td>50</td><td>25</td><td>27</td><td></td><td>66.3 63.4</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# Surface properties  \n\nThe migratory aptitude was further supported by XPS analysis of the coatings. As shown, the integrated spectra Fig. 4A peak at $403\\mathrm{eV}$ represents nitrogen which conformed that surface of sample 35 contained N, while no signal for nitrogen element could be detected when running XPS to the other four samples, as shown in Fig. 4B. And because the only source of N in the coatings is 14QAS, it could be concluded that there were some quaternary ammonium groups on the surface of sample 35. The results of N element through those samples indicated that quaternary ammonium group had a good migratory ability in this system leading the aggregation of the 14QAS to the surface and only the 14QAS in sample 35 had migrated successfully.  \n\nThis phenomenon attributed to the high-surface tension of 14QAS. As an amphipathic molecule, 14QAS has a long carbon chain which is hydrophobic and the quaternary ammonium group which is hydrophilic. Thus, when 14QAS acted as a part of the coatings, the quaternary ammonium groups were rejected by other components. After that, they got their rudimentary energy to migrate to the surface. Otherwise, the viscosity of the coating system resisted this kind of migration. That is may be the reason that the N element only appeared on the surface of sample 35.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# Mechanical properties  \n\nThe results from the conventional coating characterization analyses are shown in Table 7. According to the pencil hardness test, CN929 and PEGDA600 all had pronounced positive effects on the scratch resistance because of their ability to form a network. On the contrary, the more HEA-14QAS in coatings, the worse pencil hardness of the coatings. Still, it can be found that the antifog coating (Sample 35) had pencil hardness approaching 3H, at which hardness the coatings had the ability to exhibit some damage and delamination.  \n\n![](images/8ef1a0c7b558bf52e7e470881a098c8e2b43035d666002dccc5d6e713ceb7755.jpg)  \nFigure 4. XPS spectra of Sample 31–35 (A, Sample 35; B, Sample 31-34). This figure is available in colour online at wileyonlinelibrary.com/journal/pa  \n\nTable 7. Mechanical Properties of coatings with changed components   \n\n\n<html><body><table><tr><td rowspan=\"2\">Code</td><td colspan=\"4\">The content of each component in coatings (wt%)</td><td rowspan=\"2\">Pencil</td><td rowspan=\"2\">Pendulum</td></tr><tr><td>14QAS</td><td>HEA</td><td>CN929</td><td>PEGDA600</td></tr><tr><td>1</td><td>0</td><td>5</td><td>47</td><td>45</td><td>4H</td><td>0.82</td></tr><tr><td>2</td><td></td><td>10</td><td></td><td>40</td><td>4H</td><td>0.78</td></tr><tr><td>3</td><td></td><td>15</td><td></td><td>35</td><td>4H</td><td>0.76</td></tr><tr><td>4</td><td></td><td>20</td><td></td><td>30</td><td>3H</td><td>0.74</td></tr><tr><td>5</td><td></td><td>25</td><td></td><td>25</td><td>3H</td><td>0.72</td></tr><tr><td>6</td><td>0</td><td>5</td><td>47</td><td>45</td><td>4H</td><td>0.82</td></tr><tr><td>7</td><td></td><td>10</td><td>42</td><td></td><td>4H</td><td>0.76</td></tr><tr><td>8</td><td></td><td>15</td><td>37</td><td></td><td>3H</td><td>0.72</td></tr><tr><td>9</td><td></td><td>20</td><td>32</td><td></td><td>3H</td><td>0.69</td></tr><tr><td>10</td><td></td><td>25</td><td>27</td><td></td><td>3H</td><td>0.65</td></tr><tr><td>31</td><td>2.5</td><td>2.5</td><td>47</td><td>45</td><td>4H</td><td>0.70</td></tr><tr><td>32</td><td>5</td><td>5</td><td>42</td><td></td><td>4H</td><td>0.64</td></tr><tr><td>33</td><td>7.5</td><td>7.5</td><td>37</td><td></td><td>3H</td><td>0.62</td></tr><tr><td>34</td><td>10</td><td>10</td><td>32</td><td></td><td>3H</td><td>0.60</td></tr><tr><td>35</td><td>12.5</td><td>12.5</td><td>27</td><td></td><td>3H</td><td>0.42</td></tr><tr><td>36</td><td>2.5</td><td>2.5</td><td>47</td><td>45</td><td>4H</td><td>0.70</td></tr><tr><td>37</td><td>5</td><td>5</td><td></td><td>40</td><td>4H</td><td>0.65</td></tr><tr><td>38</td><td>7.5</td><td>7.5</td><td></td><td>35</td><td>4H</td><td>0.62</td></tr><tr><td>39</td><td>10</td><td>10</td><td></td><td>30</td><td>3H</td><td>0.59</td></tr><tr><td>40</td><td>12.5</td><td>12.5</td><td></td><td>25</td><td>3H</td><td>0.55</td></tr></table></body></html>  \n\nThe results from the pendulum hardness test, which measured the surface hardness in combination with the surface friction, indicated that the coatings with lower content of HEA-14QAS gave rise to a higher number of pendulum swings which mean a harder surface. Especially, Sample 35 had the lowest data pendulum hardness. And the difference between Samples 35 and 34 was higher than anyone else. This phenomenon could also be explained by the migration of 14QAS in the systems. Because the long carbon chain was supported to the surface according to the movement of 14QAS, the surface could be more flexible than before.  \n\nThus, although HEA-14QAS gave rise to the antifog and antibacterial properties, it could decrease the hardness of the final coatings, which was necessary in practical application.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# CONCLUSION  \n\nThis work demonstrates that coatings contained enough QAS could exhibit excellent antifog and antibacterial properties under a variety of environmental challenges. With photopolymerized QAS, these antifog and antibacterial coatings can be used for a long time. CA studies also provided that the excellent hydrophilic capabilities of the coatings were associated with the mass content of QAS in HEA (HEMA)-QAS and the mass content of PEGDA in coatings.  \n\nThe persistent antifog and antibacterial property of this coating open up new possibilities for a wide range of applications, especially used in people’s daily life, such as on the mirrors of bathroom, the windscreens of car, the windows in baby room, and so on.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 20,
+        "chunk": "# REFERENCES  \n\n[1] C. Xiong, K. J. Balkus, Chem. Mater. 2005, 17, 5136–5140.   \n[2] I. Badge, S. Sethi, A. Dhinojwala, Langmuir 2011, 27, 14726–14731. [3] X. Gao, X. Yan, X. Yao, L. Xu, K. Zhang, J. Zhang, B. Yang, L. Jiang, Adv. Mater. 2007, 19, 2213 2217. [4] P. Chevallier, S. Turgeon, C. Sarra-Bournet, R. Turcotte, G. Laroche, ACS Appl. Mater. Interfaces 2011, 3, 750 758. [5] J. Seo, S. Lee, J. Lee, T. Lee, Mater. Interfaces 2011, 3, 4722 4729. [6] L. Introzzi, J. M. Fuentes-Alventosa, C. A. Cozzolino, S. Trabattoni, S. Tavazzi, C. L. Bianchi, A. Schiraldi, L. Piergiovanni, S. Farris, Appl. Mater. Interfaces 2012, 4, 3692–3700.   \n[7] N. Nuraje, R. Asmatulu, R. E. Cohen, M. F. Rubner, Langmuir 2011, 27(2), 782–791.   \n[8] P. Majumdar, E. Lee, N. Gubbins, D. A. Christianson, S. J. Stafslien, J. Daniels, L. VanderWal, J. Bahr, B. J. Chisholm, J. Comb. Chem. 2009, 11, 1115–1127.   \n[9] R. R. Pant, J. L. Buckley, P. A. Fulmer, J. H. Wynne, D. M. McCluskey, J. P. Phillips, J. Appl. Polym. Sci. 2008, 110, 3080–3086.   \n[10] G. Sauvet, W. Fortuniak, K. Kazmierski, J. J. Chojnowski, Polym. Sci., Part A: Polym. Chem. 2003, 41(19), 2939–2948.   \n[11] B. Gottenbos, H. C. van der Mei, F. Klatter, P. Nieuwenhuis, H. J. Busscher, Biomaterials 2002, 23(6), 1417–1423.   \n[12] J. C. Tiller, C. J. Liao, K. Lewis, A. M. Klibanov, Proc. Natl. Acad. Sci. 2001, 98(11), 5981–5985.   \n[13] M. J. Saif, J. Anwar, M. A. Munawar, Langmuir 2009, 25, 377–379.   \n[14] G. Lu, D. Wu, R. Fu. React. Funct. Polym. 2007, 67, 355–366.",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Light-regulated growth from dynamic swollen substrates for making rough surfaces  \n\nLulu Xue 1, Xinhong Xiong1, Baiju P. Krishnan1, Fatih Puza1, Sheng Wang 1, Yijun Zheng2✉ & Jiaxi Cui 1,3✉  \n\nNatural organic structures form via a growth mode in which nutrients are absorbed, transported, and integrated. In contrast, synthetic architectures are constructed through fundamentally different methods, such as assembling, molding, cutting, and printing. Here, we report a photoinduced strategy for regulating the localized growth of microstructures from the surface of a swollen dynamic substrate, by coupling photolysis, photopolymerization, and transesterification together. Photolysis is used to generate dissociable ionic groups to enhance the swelling ability that drives nutrient solutions containing polymerizable components into the irradiated region, photopolymerization converts polymerizable components into polymers, and transesterification incorporates newly formed polymers into the original network structure. Such light-regulated growth is spatially controllable and dose-dependent and allows fine modulation of the size, composition, and mechanical properties of the grown structures. We also demonstrate the application of this process in the preparation of microstructures on a surface and the restoration of large-scale surface damage.  \n\niving organisms are able to create various fascinating microstructures via a growth mode1. During the natural growth process, nutrients are absorbed into the body, transported inside and then integrated into the organisms under the directive of intrinsic code2,3. In contrast to this fully dynamic and open approach in nature, synthetic materials suffer from selforganized mechanisms to continuously incorporate external mass without compromising the material’s integrity. In this regard, fundamentally different methods, such as assembling4, molding5, cutting6, and printing7,8, have been utilized and applied to fabricate man-made substances. Recently, applying the concept of growth to design self-organized synthetic systems has become a powerful strategy to develop novel dynamic materials with different biofunctions9,10. For instance, Gong et al. reported a kind of self-growing hydrogel that responds to repetitive mechanical stress through mechanochemical transduction9. In transduction, the supplied monomers are incorporated into the original polymer network by mechano-generated radicals to self-strengthen the materials. Additionally, Johnson et al. developed a class of growable polymer gels by using trithiocarbonate iniferters as dynamic connectors10,11. The iniferters can incorporate monomer molecules entrapped in the gels to elongate the polymer segments between crosslinked points. By applying a similar approach, Kloxin and coworkers have developed covalently crosslinked polymer networks in which crosslinking reactions can be triggered to strengthen the material or heal damage in the material12. These reported studies indicate that the growth strategy is promising for the postvariation of material properties. Despite the progress in this field, a growth strategy has not yet been applied to create microstructures on the surface, e.g., to enable localized growth of a structure from a flat substrate. To this end, a set of mechanisms for not only molecular incorporation but also mass transport and homogenization of polymer composition should be combined in a single system.  \n\nMany stimuli, such as light13,14, strength15,16, temperature17, and moisture18, have been applied to selectively trigger chemical reactions for spatial functionalization. Among them, light is environmentally friendly, noncontact, and spatiotemporally controllable and therefore is widely used for lithography19, 3D printing20, robotic actuation21, cell migration22, self-healing23, switchable transitions24, etc. It has also been employed to initiate the incorporation of entrapped monomer molecules into a polymer matrix for material growth10–12,25. However, in these previous examples, photoinduced reactions were utilized to convert monomers/crosslinkers into polymers rather than to guide mass transport.  \n\nHerein, we report a photoregulated strategy to control localized growth of microstructures from the surface of swollen substrates. In our design, three kinds of reactions, namely, photolysis, photopolymerization, and transesterification, were coupled together to guide the transport of liquid components entrapped in the substrates, to convert the polymerizable components in the liquids into polymers, and to reconfigure newly formed and original polymers. As a result of these reactions, microstructures can grow directly from flat substrates without the requirement for any preprogramming. The developed light-induced growth approach is spatially controllable, dose-dependent, and multitriggerable and can be used to create various rough surfaces or restore large-scale surface damage.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Results  \n\nDesign and sample preparation. The detailed concept of lightinduced growth is demonstrated in Fig. 1. The growth starts from a swellable substrate composed of photoresponsive polymers crosslinked by ester-based linkers (Fig. 1a). The substrate can swell a solution consisting of monomer, crosslinker, photoinitiator, and transesterification catalyst, which is defined as the nutrient solution (Fig. 1b). Photolabile side groups are designed as promoters that can undergo photolytic reactions to generate dissociable ionic groups to enhance the swelling ability by expansion of the polymer networks to transport the nutrient solution into the irradiated region (Fig. 1c)26. This photoinduced mass transport is coupled with the photopolymerization of the monomer and crosslinker in the nutrient solution, leading to continuous swelling of the irradiation region and thus the formation of protrusions on the irradiated surface (Fig. 1d). During swelling, the original networks are stretched, which should prevent the nutrient solution from diffusing. A transesterification catalyst is thus designed to trigger an exchange reaction between original and newly formed networks to release such mechanical tension and to reconfigure the grown structure (Fig. 1e). We expect that such a coupling of three reactions could lead to an on-demand, localized growth of microstructures from material surfaces.  \n\nA material system of 4-hydroxybutyl acrylate (HBA), onitrobenzyl acrylate (NBA, Supplementary Fig. 1), and 1,6- hexanediol diacrylate (HDDA) was selected to demonstrate the design. HBA is a commercially available precursor for making polymer substrates with good monomer swelling ability, while NBA is a photolabile monomer (promoter) that can generate dissociable ionic $-\\mathrm{COO^{-}}$ groups to induce an increase in swelling ability27,28. The HDDA crosslinker has an ester linkage that can undergo a transesterification reaction with the hydroxyl group of HBA. Poly (HBA- $.c o$ -NBA) samples with different NBA molar fractions (0, 5, 10, 20, 35, and $50\\%$ ) were fabricated via photopolymerization under blue LED light $(460\\mathrm{nm},0.6\\mathrm{mW}\\mathrm{cm}^{-2})$ in the presence of Irgacure 819 (I-819, initiator). Under this irradiation condition, the NBA unit will not undergo photolysis since it does not absorb at this wavelength. This hypothesis was verified by irradiating an NBA solution under the same conditions (no visible change in either UV-Vis or $^1\\mathrm{H}$ NMR spectroscopy, Supplementary Fig. 2). After photopolymerization, unreacted components were washed with ethanol, and the obtained specimens were denoted as seed- $x_{i}$ where $x$ is the feeding molar fraction of the NBA. Both Fourier transform infrared (FTIR) spectroscopy and UV-Vis spectroscopy were used to characterize the chemical structure of the seeds. Typical IR signals assigned to the ${\\bf-N O}_{2}$ group of NBA units $(1528\\mathrm{cm}^{-1}$ : asym. $\\Nu{\\cal O}_{2}$ stretch; $1342\\mathrm{cm}^{-1}$ : sym. $\\mathrm{NO}_{2}$ stretch) and strong UV absorption from the nitrobenzyl group were observed (Supplementary Fig. 3), indicating the successful copolymerization of $o$ -nitrobenzyl ester units.  \n\nThe seeds showed an excellent swelling ability to the nutrient solution consisting of HBA (monomer), HDDA (crosslinker), I-819 (photoinitiator), and benzensulfonic acid (BZSA, transesterification catalyst). For example, an equilibrium swelling ratio of 4.6 was obtained for a seed- $20\\%$ sample with a thickness of $1.4\\mathrm{mm}$ (Supplementary Fig. 4). The polymerizable components, i.e., HBA and HDDA, entrapped in the polymer networks could undergo photopolymerization to integrate into the seeds under UV light irradiation ( $365\\mathrm{nm}$ , $10\\mathrm{mW}\\mathrm{cm}^{-2}$ , confirmed by the weight of the sample after removal of unreacted components by washing). UV light was also expected to trigger the photolytic reaction of the NBA unit (confirmed by the disappearance of $-\\mathrm{NO}_{2}$ peaks in the FTIR spectrum, Supplementary Fig. 5). It was noted that under our irradiation conditions, UV light could not trigger obvious chain scission of polymer networks except photolysis of NBA (Supplementary Fig. 6). In addition, the thermal effect generated by polymerization triggers transesterification reactions to release any polymerization-induced mechanical tension in such dynamic networks29–31.  \n\n![](images/c9b035ba8b323009ab23fb7f07cc6957277cdc09b1e9811d089cc1d769b3a994.jpg)  \nFig. 1 Schematic of light-induced growth from swollen substrates. a Growable seed made from 4-hydroxybutyl acrylate (HBA), o-nitrobenzyl acrylate (NBA, promoter), Irgacure 819 (I-819, photoinitiator) and 1,6-hexanediol diacrylate (HDDA). b Swollen seed. The mixture of HBA, HDDA, photoinitiator (I819), and transesterification catalyst (benzensulfonic acid (BZSA)) were used as the nutrient solution for swelling. c Swollen substrate under selective UV irradiation. Photolysis of NBA units generated dissociable ionic groups to induce liquid diffusion into the irradiated region. d New polymer network formed via photopolymerization. Liquid components diffused in, and the polymer chains in the original network were stretched. e The grown part was homogenized via transesterification reactions between the original and newly formed polymer networks.  \n\nLight-triggered localized growth. Figure 2a shows an image of light-induced growth of a pillar from the surface of a flat swollen seed- $20\\%$ . During UV irradiation, a regular structure slowly grew out from the irradiated region of the material surface, and the height of this pillar could reach up to $250\\upmu\\mathrm{m}$ during the testing time.  \n\nFigure 2b shows the growth process evaluated by the height of the grown pillar. The growth process of swollen seed- $20\\%$ was triggered by irradiation with either $365\\mathrm{nm}$ or $460\\mathrm{nm}$ light. Exposure to $365\\mathrm{nm}$ light triggered both polymerization and photolytic reactions, while $460\\mathrm{nm}$ light induced only polymerization. In this regard, the experiment with $460\\mathrm{nm}$ light could be used as a control to evaluate the contribution of the photolytic reaction. The irradiation intensity of both lights was the same $(10\\mathrm{mW}\\mathrm{cm}^{-2},$ ), and such a design was used to achieve similar photopolymerization effects (photopolymerization conversions reached their plateaus in $2\\mathrm{min}$ , Supplementary Fig. 7). Upon irradiation with $365\\mathrm{nm}$ light, the height of the grown structure increases rapidly in the first $5\\mathrm{{min}}$ $(75\\upmu\\mathrm{m})$ and reaches a plateau at a value of $250\\upmu\\mathrm{m}$ in $50\\mathrm{min}$ . The grown sample retains its shape after being stored in the dark overnight. In comparison, growth also occurs in the control sample, but the height of the grown structure at the plateau is significantly smaller $(70\\upmu\\mathrm{m})$ . We attributed the growth in the absence of a photolytic reaction to the fact that photopolymerization consumed the monomer and crosslinker in the nutrient solution to form new polymer networks in the irradiated region, followed by creation of a concentration gradient of the monomer and crosslinker to drive these components to diffuse into the irradiated region to participate in the polymerization. Such a polymerization-diffusion cycle led to the growth of the structure. However, this photolysis-absent growth is significantly slower than the photolysis-present growth, and the obtained structure is also notably smaller. The higher grown structure obtained in photolysis-present growth indicated that the photolytic reaction had generated an extra effect to accelerate the diffusion of the nutrient solution into the irradiated region. Since the photolytic reaction of NBA units generates carboxyl groups, we attributed the extra effect to the formation of dissociable ionic $-\\mathrm{COO^{-}}$ groups, which enhanced the swelling ability of the irradiated region by expansion of the polymer networks via electrostatic repulsion. In addition to having a smaller size, the grown structure is seriously distorted after being stored in the dark (Fig. 2b and Supplementary Fig. 8).  \n\n![](images/20afd3c65fc48566874969ebc33a810fe07f758419d8ddecb2452751e830e637.jpg)  \nFig. 2 Light-regulated growth from HBA-based substrates. a Time-dependent images (side view) of swollen substrates under UV irradiation $(10\\mathsf{m}\\mathsf{W}\\mathsf{c m}^{-2};$ . A photomask with a diameter of $500\\upmu\\mathrm{m}$ was used. The scale bar is $250\\upmu\\mathrm{m}$ . b The height of the grown microstructures (grown height) of different samples vs treatment time. The data were obtained from three independent measurements. Error bars are s.e.m. The dashed boxes show the typical profiles of the grown structures before and after being stored in the dark. c Zeta potential of linear poly(HBA-co-NBA) copolymers at different irradiation times. The polymer concentration was $2\\mathsf{m g}\\mathsf{m}\\mathsf{L}^{-1}.$ , and an LED lamp $\\langle10\\mathsf{m}\\mathsf{W}\\mathsf{c m}^{-2}\\rangle$ was used for irradiation. The inset shows the photolytic reaction of the NBA units. d Profiles of a swollen seed- $20\\%$ containing HB acetate, I-819, and BZSA under different conditions. Photomasks with a diameter of $5\\mathsf{m m}$ were used. e Typical profiles of the grown structures obtained from the swollen seed with (top) or without (bottom) transesterification catalyst BZSA. Fluorescent cross-section images of the grown structure obtained from a nondyed seed and dyed nutrient $(\\pmb{\\uparrow})$ and a dyed seed and nondyed nutrient $\\mathbf{\\sigma}(\\mathbf{g})$ . The substrates used in (a), (d), (e), $({\\pmb{\\mathscr{f}}})$ , and $\\mathbf{\\sigma}(\\mathbf{g})$ contain $20\\%$ promoter (seed- $20\\%$ ). PDIDA was used to dye the seed in $(\\pmb{\\uparrow})$ and the nutrient in $\\mathbf{\\sigma}(\\mathbf{g})$ with a concentration of $0.01\\mathrm{wt\\%}$ .  \n\nA growth process based on the polymerization-diffusion cycle was thus proposed: upon UV irradiation, photolysis of NBA units and polymerization of the monomer and crosslinker in the irradiated region generated the dissociable ionic group of $-\\mathrm{COO^{-}}$ and the concentration gradient of monomer and crosslinker, which significantly enhanced the swelling ability of the irradiated region. As a result of the enhanced swelling ability and lower concentrations of the monomer and crosslinker in the irradiated region, the nutrient solution diffused into the irradiated region to induce a polymerization-diffusion cycle. In this cycle, photopolymerization was significantly faster than the diffusion process (time for photopolymerization to reach its conversion plateau: ${\\sim}2\\mathrm{min}$ ; time for liquid molecules to diffuse into the seed to fully swell it: ${\\sim}4\\mathrm{h}$ without irradiation and ${\\sim}2\\mathrm{h}$ under irradiation; see Supplementary Figs. 7 and 9 for more detail). After irradiation, the generated concentration gradient still existed and continued driving the monomer and crosslinker (major liquid component of the nutrient solution) to diffuse into the grown structure to swell. This swelling distorted the grown structure of the photolysisabsent sample (swollen state, Supplementary Fig. 10). To confirm this, after the distorted grown structures were washed, considerable shrinkage was observed in the distorted sample. In addition, the obtained grown structures were stable in both the swollen and dried states (Supplementary Fig. 11).  \n\nWe studied the formation of the dissociable ionic group of $-\\mathrm{COO^{-}}$ by monitoring the zeta potential of a linear poly(HBA$c o$ -NBA) containing $20\\%$ NBA units ( $M n=8500$ , $P D I=1.16$ Supplementary Figs. 12 and 13) under UV illumination. As shown in Fig. 2c, the copolymer is almost neutral $(-1.8\\mathrm{mV})$ before irradiation. The potential value decreases sharply to $-27\\mathrm{mV}$ after $2\\mathrm{min}$ of UV irradiation, indicating the formation of dense negative species on the copolymer $\\bar{(-\\mathrm{COO^{-})}}$ . The species was assigned as a carboxyl ion, which was released from the NBA unit28. It was highly active and was ultimately neutralized into –COOH (thus a change from $-32\\mathrm{mV}$ to $-2\\mathrm{mV}$ in the zeta potential). To verify that the change in the zeta potential were caused by the dissociable ionic $-\\mathrm{COO^{-}}$ group rather than the photolytic product of the $o$ -nitrobenzyl moiety, we selected 2-nitrobenzyl alcohol as a control, a compound that can undergo a similar photolytic reaction but does not generate a carboxyl group. The zeta potential of the 2-nitrobenzyl alcohol solution did not change obviously under UV irradiation (Supplementary Fig. 14), indicating that the change in zeta potential of poly(HBA-co-NBA) should be attributed to the generation of dissociable $-\\mathrm{COO^{-}}$ . The formation of $-\\mathrm{COO^{-}}$ on the polymer segments induced an increase in swelling ability26, while the carboxyl groups reduced the swelling ability of the matrix to reduce the distortion effect. We proved this hypothesis by irradiating a control sample of seed- $20\\%$ swollen by a nonpolymerizable solution consisting of 4-hydroxybutyl acetate (HB acetate, Supplementary Fig. 1), I-819, and BZSA. Upon UV irradiation, a bulge forms on the irradiated region (Fig. 2d, Supplementary Fig. 15), indicating a swelling process. Since the liquid compositions were nonpolymerizable (lacking a polymerization-diffusion cycle to drive liquid diffusion), the driving force for swelling was attributed to chargeinduced electrostatic repulsion. Although a change of only ${\\sim}5\\upmu\\mathrm{m}$ in height was observed, such a change in the polymerizationdiffusion cycle could be amplified. To further confirm the contribution of photolysis to accelerate mass transport, we compared the diffusion rate of the nutrient solution in seed$20\\%$ under different conditions by a swelling method (Supplementary Fig. 16). The average rate of mass transport under irradiation conditions was significantly higher $(4.7\\times10^{-5}\\mathrm{cm}^{2}$ $\\begin{array}{r}{{\\mathsf s}^{-1},}\\end{array}$ ) than that without irradiation $(4.9\\dot{\\times}10^{-6}\\mathrm{cm}^{2}\\mathrm{s}^{-1})$ . After the transition of $-\\mathrm{COO^{-}}$ to $-\\mathrm{COOH}.$ the liquid composites diffused from the irradiated region, resulting in a cave surface. This result was consistent with the fact that irradiated seed- $20\\%$ showed lower swelling ability into the nutrient solution because of the formation of carboxyl side groups (Supplementary Fig. 4). The decrease in swelling ability favored the formation of nondistorted grown structures since the transport of the nutrient solution from the nonirradiated region to the irradiated region during storage was reduced (Fig. 2b).  \n\nTransesterification indeed occurred during light-induced growth. Under our irradiation conditions, the temperature of the irradiated region in a swollen seed- $20\\%$ sample increased to $62^{\\circ}\\mathrm{C}$ in the initial $1\\mathrm{min}$ (Supplementary Fig. 17), while that of swollen seed- $20\\%$ with nonpolymerizable liquids was unchanged even after $60\\mathrm{{min}}$ UV irradiation (Supplementary Fig. 18). At this temperature, the catalyst BZSA used in our system can induce efficient transesterification31. We studied the contribution of transesterification to the grown structure by a control sample without BZSA. In contrast to the flat surface of the grown structure observed in the typical sample, the surface of the grown structure obtained from the control sample was concave (Fig. 2e, Supplementary Fig. 19). During growth, since photopolymerization of the monomer and crosslinker in nutrient solution was significantly faster than the transport of nutrient solution, the growth rate was mainly dependent on the diffusion rate of the nutrient solution. In the control sample, the nutrient solution diffused into the irradiated region from outside and was integrated into the periphery via rapid polymerization; thus, fewer monomer and crosslinker molecules could diffuse and be integrated into the center, leading to an energy-unfavorable concave surface. In the presence of a transesterification catalyst, such an energy-unfavorable concave surface could be converted into an energy-favorable flat surface via transesterificationassociated reconfiguration (Fig. 1e and Supplementary Figs. 20 and 21)29. The transesterification was further proven by the significantly higher modulus of the grown structure of the control samples (Supplementary Fig. 22). Without transesterification, a double-network structure formed to stiffen the grown structure $(490\\mathrm{KPa})$ , while transesterification-induced homogenization reduced this stiffening effect $(380\\mathrm{KPa})^{32}$ .  \n\nThe composition of the grown structure was studied by confocal fluorescence spectroscopy. To enable imaging and detailed investigation of the swollen substrates, the nutrient solution was labeled by a fluorescent crosslinker, bis- $\\cdot N{\\mathrm{}},N^{\\prime}{-}6-$ hydroxyhexanol perylenetetracarboxylic diimide-acrylate (PDIDA, Supplementary Fig. 1). This crosslinker was stable under our irradiation conditions (Supplementary Fig. 23), and its diacrylate structure was expected to significantly decrease its relocalization possibility during transesterification-induced homogenization. Seed- $20\\%$ was soaked in a nutrient solution containing $0.01\\mathrm{wt\\%}$ PDIDA, followed by light-induced growth for $30\\mathrm{min}$ . After polymerization, the unreacted components were washed with ethanol $/\\mathrm{CHCl}_{3}$ solutions before being subjected to confocal imaging. Figure 2f shows the cross-section of the grown samples. Compared to the dark surroundings, a bright color was observed in the grown part, indicating that the monomer and crosslinker in the nutrient solution were integrated into the grown structure. The bright color extends to the bottom region of the seed, suggesting that the growth started inside the sample rather than simple polymerization from the surface of the sample. Complementary experiments were also conducted to assure the growth mechanism. Seed- $20\\%$ was dyed with $0.01\\mathrm{wt\\%}$ PDIDA and then grown from a nondyed nutrient solution (Fig. 2g). As expected, the grown region was still fluorescent but significantly diluted, indicating that the grown region was made from both original and newly formed networks. The fluorescence intensity of the surface of a newly grown structure was nearly the same as that observed in the nonirradiated region (Supplementary Fig. 24), indicating that nearly no growth occurred in the surface layer. This might be due to the evaporation of monomer molecules in this region or the lower swelling ability of the surface layer of the sample. In addition, the fluorescence intensity gradually increased from the top region to the bottom region. We attributed this finding to the gradual swelling of the networks. Based on the growth curves (Fig. 2b), the growth rate decreased with time due to consumption of the monomer. Therefore, the dilution effect in fluorescence decreased from top (early stage) to bottom (later stage) in the growth direction.  \n\n![](images/b42d696da2215bc1060746e6fcee2abbd976177d113e093eced30402ef3bee10.jpg)  \nFig. 3 Control of light-induced growth. a The height of the grown structures changes with irradiation conditions. The labels $\"\\mathrm{ON^{\\prime\\prime}}$ and $^{\\prime\\prime}{\\mathsf{O F F}}^{\\prime\\prime}$ indicate the state of UV light applied to the samples. b The profile of the grown structure obtained from first-cycle growth. A round photomask with a diameter of $5000\\upmu\\mathrm{m}$ was used. c The profile of the grown structure prepared from two-cycle growth. The grown sample in $(\\pmb{6})$ was used, and it was reswelled in nutrient solution for growth. A round photomask with a diameter of $1250\\upmu\\mathrm{m}$ was used, and irradiation was selectively applied to the grown region. d Modulus of the seed and the grown structures obtained from the nutrient solution with different crosslinker concentrations (x in Grown- $\\cdot x$ in the label). e The height of the grown structure obtained from the seed containing different NBA molar fractions. f The height of the grown structure made from different monomers. PPEGA/PBA: PEGA/BA-based seeds grew from PEGA/BA-based nutrient solution; PPEGA-PHBA: PEGA-based seeds grew from HBA-based nutrient solution. Seed- $20\\%$ was used in (a), (b), (d), and (f), and the data in (a), (d), (e), and (f) were obtained from three independent measurements. Error bars are s.e.m. The height values in (e) and $(\\pmb{\\uparrow})$ were collected at plateau states.  \n\nControl of growth. The light-induced growth was not only localized (Supplementary Figs. 25 and 26) but also temporally controllable. We employed seed- $20\\%$ to demonstrate this capability by switching the irradiation light. As shown in Fig. 3a, growth was triggered only by the implementation of irradiation. For example, the height of the grown structures increased to $25\\upmu\\mathrm{m}$ within the first min of activation, and the growth stopped when light was turned off. The growth was reinitiated by turning the light on. Such on-off modulation can extend until the growth reaches its plateau. In addition, several parameters, including the crosslinking degree of the seed, the diameter of the irradiation region, and the light intensity, were studied to modulate growth. Increasing the crosslinking degree of seed- $20\\%$ decreases its swelling ability as well as the height of the grown structure at the plateau state (Supplementary Fig. 27). Upon increasing the irradiation diameter, the growth height at the plateau state increased in the range from $266\\upmu\\mathrm{m}$ to $600\\upmu\\mathrm{m}$ but decreased in the range of ${>}600\\upmu\\mathrm{m}$ (Supplementary Fig. 28). We attributed the increase to the photopolymerization-induced thermal effect (elevation in temperature would accelerate the diffusion rate of liquid molecules and thus the growth). Considering thermal dissipation, increasing the irradiation diameter favored temperature elevation. On the other hand, increasing the diameter also elongated the diffusion distance and thus reduced the growth. This reducing effect became more obvious in the larger diameter range $({>}600\\upmu\\mathrm{m})$ . For a decrease in light intensity reduced the growth because of slower photolysis and polymerization reactions (Supplementary Fig. 29).  \n\nSequential growth was also possible. Figure 3b shows a sample with a grown pillar with a height of $180\\upmu\\mathrm{m}$ and a diameter of $5000\\upmu\\mathrm{m}$ . This grown sample can be swelled by the nutrient solution again and activated to grow in the grown region. Under the same irradiation conditions, a new pillar with a height of 110 $\\upmu\\mathrm{m}$ formed on the previously grown pillar (Fig. 3c). The lower height of second growth was attributed to the lower concentration of the promoter in the second photolysis step.  \n\nSince the grown structure was made from feed nutrient solutions and original polymers, its composition could be easily regulated by the nutrient solutions, which provided a powerful approach to control the mechanical properties of the grown structure. We demonstrated this concept by varying the crosslinker fraction in the nutrient solutions used to seed- $20\\%$ (made from $1\\mathrm{wt\\%}$ crosslinker, modulus: $370\\mathrm{KPa})$ . When a nutrient solution with a crosslinker concentration of $0.2\\mathrm{wt\\%}$ was used, a grown structure with a modulus of $280\\mathrm{KPa}$ was obtained. On the other hand, increasing the crosslinker concentration in the nutrient solutions enhanced the modulus of the grown structure. The E-moduli were even up to $1.5\\mathrm{MPa}$ when a crosslinker concentration of $10\\mathrm{wt\\%}$ was used in the nutrient solution (Fig. 3d). Notably, such a growth method to spatiotemporally change the modulus of the grown structures did not induce any interface issue since the newly formed structure was grown from inside the original materials.  \n\nThe promoter fraction in the seed was also expected to be an important parameter to control growth. In principle, increasing its fraction should enhance the driving force for liquid transport into the irradiation region but would also decrease the final swelling ratio of the irradiation region since both the NBA unit and its photolytic product reduced the material’s swellability to nutrient solutions. As shown in Fig. 3e, the height of the grown pillar in the plateau state increases with the fraction of promoters in the range of $<20\\%$ but decreases in the range of $35\\mathrm{-}50\\%$ .  \n\nThe concept of photoinduced growth could be applied to different material systems. We demonstrated this applicability with poly(ethylene glycol) methyl ether acrylate (PEGA), a hydrophilic monomer, and butyl acrylate (BA), a hydrophobic monomer (Supplementary Figs. 30 and 31). Figure 3f lists the growth heights of different material systems under the same growth conditions. The height of PEGA grown in the plateau state $(160\\upmu\\mathrm{m})$ is lower than that of HBA $(250\\upmu\\mathrm{m})$ . This was attributed to the significantly higher viscosity of PEGA $(90\\mathrm{cSt},$ $20^{\\circ}\\mathrm{C})^{33}$ than of HBA $(10.7\\:\\mathrm{cSt},2\\bar{0}^{\\circ}\\mathrm{C})$ . The higher viscosity led to a lower transport rate and thus less growth. The hypothesis was supported by the higher height $(300\\upmu\\mathrm{m})$ of the grown pillar made from BA, which has a lower viscosity (0.92 cSt, $20{}^{\\circ}\\mathrm{C}_{\\prime}$ ). Moreover, a hybrid system could also be created by varying the compositions of the nutrient solution. For example, we grew PEGA-based seeds in HBA-based nutrient solution. The grown pillar reached a height of up to $240\\upmu\\mathrm{m}$ and showed a modulus of $580\\mathrm{KPa}$ when the seed had a modulus of $220\\mathrm{KPa}$ (Supplementary Fig. 32). Based on these results, we concluded that the light-induced growth was fully controllable and allowed for fine variation in size, strength, and composition.  \n\nApplication demonstration. Localized growth of microstructures from a flat substrate implied a template-free method for making a patterning surface. Figure $_{4\\mathsf{a}-\\mathsf{e}}$ shows a tentative example. Upon UV illumination through a mask, a regular micropattern (diameter of $500\\upmu\\mathrm{m}$ ) grew from the flat surface of the swollen sample (Fig. 4a–d). The formed pillars were uniform, with a height of $250\\upmu\\mathrm{m}$ (Fig. 4e). In addition, direct writing with a UV laser was also possible (Supplementary Fig. 33)  \n\nThe growth could be used to restore large-scale surface damage at the millimeter level. Self-healing of extensive damage is extremely challenging since it not only involves molecular reconfiguration but also requires significant mass transport34. Although dynamic materials have been suggested to be self-healable, they mainly depend on the rebonding of matrices, which is normally useful in the recovery of microcracks and scratches35. It is difficult for them to restore large-scale surface damage at the millimeter level36. Since light-induced growth involves significant liquid transport, in situ polymerization, and reconfiguration, we assumed that it could be used to restore large-scale surface damage by guiding growth toward the damaged region. The promising demonstration of surface damage restore by the developed strategy is detailed in Fig. 4f– $\\mathbf{\\cdotk}$ Damage with a size of $0.60\\mathrm{\\cm}(l)\\times0.40\\mathrm{cm}(w)\\times0.22$ $\\mathrm{mm}\\left(h\\right)$ was tentatively created on a substrate made from seed- $20\\%$ . For a better comparison, we partially irradiated the damaged region and induced growth until it was flush with the undamaged part. It could be observed from the profile of the damaged zone that the irradiated region was regenerated, implying a powerful method to restore large-scale surface damage.  \n\n![](images/f29130dfb496e02d759d5b3cb2a59f2af8ac85d8af7e14b8c9573483852be239.jpg)  \nFig. 4 Application demonstration of light-induced growth. a–e Microstructure pattern grown from a flat substrate (scale bar: $8\\mathsf{m m}$ ): a swollen seed- $20\\%$ ; b formed microstructure. The dashed line highlights the irradiated zone. 3D profiles of the surfaces of the swollen seed- $20\\%$ (c) and the grown sample (d). e Surface profiles of the seed− $20\\%$ and the formed microstructure. The regions are highlighted by dotted lines in (c) and (d). The inset in e shows the SEM image of the growth pattern. Scale bar: $500\\upmu\\mathrm{m}$ . $\\pmb{\\ell}\\pmb{k}$ Restoration of large-scale surface damage by light-induced growth: f images of the swollen seed- $20\\%$ with damage of $0.60\\mathsf{c m}\\left(I\\right)\\times0.40\\mathsf{c m}\\left(w\\right)\\times0.22\\mathsf{m m}\\left(h\\right)$ then treated with UV light $\\mathbf{\\sigma}(\\pmb{\\mathsf{g}})$ . Top view of the 3D profile of the damaged swollen seed- $20\\%$ $\\mathbf{\\eta}(\\mathbf{h})$ and the grown swollen seed- $20\\%$ (i). Surface profiles of the damaged area before $\\mathfrak{G}$ and after $({\\bf k})$ healing. A photomask was used for UV irradiation, and the irradiation time was 30 min. The scale shows the height. The dashed lines in ${\\bf\\Pi}({\\bf h})$ and (i) highlight the positions used for the collection of the profile data.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 3,
+        "chunk": "# Discussion  \n\nWe have demonstrated a strategy for designing photoinduced growable materials. The strategy is based on coupling three kinds of reactions to achieve localized growth: photolysis to generate dissociable ionic groups to increase the swelling ability and drive the diffusion of a nutrient solution into the irradiated region, photopolymerization to convert the monomer and crosslinker in the nutrient solution into crosslinked polymers, and transesterification to homogenize the newly formed and original polymer networks. Such light-induced growth is spatially controllable and dose-dependent and allows fine modulation of the size, composition, and mechanical properties of the grown structure. The flexible tunability enables the creation of microstructures on surfaces and the restoration of large-scale surface damage. Although the methodology developed in this study was demonstrated on structured surfaces, the mechanistic insights gained regarding governing growth can be readily applied to change the bulk properties of materials in consideration of the capability of light to spatially trigger various reactions. We thus envision that its development will benefit areas such as self-healing materials and rough surfaces.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# Methods  \n\nChemicals and materials. 4-Hydroxybutyl acrylate (HBA) (TCI Deutschland GmbH), butyl acrylate (BA) $(99\\%$ , Sigma-Aldrich) and poly(ethylene glycol) methyl ether acrylate (PEGA) (average $M n=480\\mathrm{g}\\mathrm{mol}^{-1}$ , Sigma-Aldrich) were purified by passing through a column of neutral alumina to remove the inhibitors before being used. 2-Nitrobenzyl bromide $98\\%$ , Alfa Aesar), acrylic acid $(99\\%$ , Sigma-Aldrich), potassium carbonate $\\left(\\mathrm{K}_{2}\\mathrm{CO}_{3}\\right)$ ) $(99\\%$ , Alfa Aesar), 1,4-butanediol $(99\\%$ , Fluka), acetic acid $(99\\%$ , ABCR), bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (I-819) (Ciba), 1,6-hexanediol diacrylate (HDDA) $(99\\%$ , Alfa Aesar), sulfuric acid $\\mathrm{(H}_{2}\\mathrm{SO}_{4})$ $(95-98\\%$ , Sigma-Aldrich), benzenesulfonic acid (BZSA) $(98\\%$ , Sigma-Aldrich), 2-nitrobenzyl alcohol $(97\\%$ , Sigma-Aldrich), 3,4,9,10-perylenetetracarboxylic dianhydride $98\\%$ , Alfa-Aesar), acrylic chloride $(97\\%$ , SigmaAldrich), imidazole (ACS reagent, Sigma-Aldrich), triethylamine $(\\mathrm{Et}_{3}\\mathrm{N})$ $(99.5\\%$ , Sigma-Aldrich), sodium chloride $(99.9\\%$ , ABCR), sodium carbonate $\\left(\\mathrm{Na}_{2}\\mathrm{CO}_{3}\\right)$ $(99\\%$ , Sigma-Aldrich), sodium sulfate $\\left(\\mathrm{Na}_{2}\\mathrm{SO}_{4}\\right)$ ) $(99\\%$ , Sigma-Aldrich), 4-Cyano-4- (phenylcarbonothioylthio)pentanoic acid (CPADB, Sigma-Aldrich), and 6- aminohexanol $(95\\%$ , TCI Deutschland GmbH) were used as received. N,N-dimethylformamid (DMF) $(99.8\\%$ , anhydrous, Sigma-Aldrich), dichloromethane (DCM) $(99.8\\%$ , anhydrous, Sigma-Aldrich) and chloroform $(99.8\\%$ , anhydrous, Sigma-Aldrich) were used directly. Other solvents like petroleum ether and ethyl acetate were purchased from ABCR and used without any treatment. $^{2,2^{\\prime}}$ -Azobisisobutyronitrile (AIBN, $98\\%$ , Sigma-Aldrich) was purified by recrystallization from ethanol.  \n\nInstruments. $\\mathrm{{^{1}H}\\ N M R}$ and $^{13}\\mathrm{C}$ NMR spectroscopy of the products were obtained with a Bruker ${300}\\mathrm{MHz}$ nuclear magnetic resonance equipment using $\\mathrm{CDCl}_{3}$ and DMSO- $\\mathbf{\\delta}_{\\mathrm{d}6}$ as solvents. Mass spectra were carried out on an Agilent LC/MSD SL. The number-average molecular weight $(M n)$ and polydispersity index (Mw/Mn, PDI) of polymers were measured by a Agilent HPC 1100 gel permeation chromatography (GPC) system using a PSS-GRAM pre-column with a series of PMMA as standard samples. Ultraviolet-visible (UV-vis) spectroscopy were obtained from a Varian Cary 4000 UV-visible spectrophotometer. ESEM images were captured on a FEI ESEM Quanta 400 FEG. Attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy were recorded with a Bruker VERTEX 70v FTIR spectrometer. Fluorescent spectroscopy were conducted with a Hitachi F-7000 fluorescence spectrophotometer. Infrared camera (InfraTec GmbH, Germany) with VarioCAM HD head was used for  \n\nrecording the temperatures during the polymerization. Surface profile and 3D profile of the specimens were carried out on a SURFCOM 1500SD3. Optical microscope images were acquired from a Nikon ECLIPSE LV100ND. Zeta potential of linear polymers was obtained with a Malvern Zetasizer Nano ZSP. Fluorescent images were recorded on a $\\mathrm{LSM}880$ confocal, and ImageJ software was used to analyses the data. Primo experiments were conducted on a Total Internal Reflection Microscopy. Water contact angles of materials were collected by a OCA 20 instrument. Side view of self-growing microstructures on material surfaces was recorded in the OCA 20 machine. Column chromatography was performed using silica gel (215–400 mesh). UV $365\\mathrm{nm}$ and blue $460\\mathrm{nm}$ collimated LED light (Olympus BX & 1X, 1700 mA) was provided by THORLABS, of which intensity was set as $10\\mathrm{mW}\\mathrm{cm}^{-2}$ during the experiments. Blue light LED strip lamp $\\left(460\\mathrm{nm}\\right)$ with an intensity of $0.6\\dot{\\operatorname*{mW}}\\dot{<}\\dot{2}$ was obtained from amazon online and used to initiate the polymerizations. Elastic moduli of seed samples were measured on a universal testing machine (ZWICK 1446, Germany) with a load cell of $200\\mathrm{N}$ and crosshead velocity of $10\\mathrm{mm}\\mathrm{min}^{-1}$ and values were calculated in the linear elastic region of the stress-strain curves from 1 to $5\\%$ . Every measurement was conducted three times. The elastic moduli of seed- $0\\%$ and seed- $20\\%$ samples were measured by compression test with a load cell of $2\\ \\mathrm{KN}$ and velocity of $2\\mathrm{mm}\\mathrm{min}^{-1}$ . The values were calculated in the linear elastic region of the stress-strain curves from 0.1 to $0.5\\%$ . The elastic moduli of the growing structures were obtained by indentation experiments. The ASMEC indenter type is Berkovich equipped with a diamond tip. Samples were struck on the PEEK model before measurements. Indentations were carried out in the load-controlled mode, with an initial quadratic up to $20\\mathrm{mN}$ within $10~\\mathrm{s}$ a creep period of $5s$ , and a quadratic decrease of the force to $0.08\\mathrm{mN}$ within $5s$ . The results were collected by eight different areas for each sample and analyzed according to the Fast hardness and modulus measurements (ISO 14557). The fit range of the unloading curve is from 98 to $40\\%$ .  \n\nFabrication of seeds. Taking seed- $20\\%$ as an example: to a mixture of HBA $(80\\mathrm{mol\\%})\\$ and NBA $(20\\mathrm{mol\\%})\\$ ) were added HDDA (crosslinker, $1\\mathrm{wt\\%}$ ) and I-819 (photoinitiator, $1\\mathrm{wt\\%}^{\\cdot}$ ) to obtain the precursor. The precursor solution was coated on Teflon substrates and cured under blue light (intensity: $0.6\\mathrm{mW}\\mathrm{cm}^{-2}$ ) for $20\\mathrm{min}$ . The obtained substrate was immersed in ethanol, and the solution was changed every $^{8\\mathrm{h}}$ (3 times) to remove unreacted specimens. Then, it was dried to afford seed- $20\\%$ .  \n\nLight-induced growth. Seed- $20\\%$ was immersed in a nutrient solution containing HBA $(96\\mathrm{wt\\%})$ , HDDA $(1\\mathrm{wt\\%})$ ), I-819 $(1\\mathrm{wt\\%})$ and BZSA $(2\\mathrm{wt\\%})$ for $12\\mathrm{h}$ to obtain swollen samples. For growth, the swollen samples were subjected to UV light (intensity: $10\\mathrm{\\bar{m}W}\\mathrm{cm}^{-2}$ ) with a suitable photomask.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# Data availability  \n\nAll data used for this paper are available from the authors on request.  \n\nReceived: 8 August 2019; Accepted: 27 January 2020; Published online: 19 February 2020",
+        "category": " References"
+    },
+    {
+        "id": 6,
+        "chunk": "# References  \n\n1. Friml, J. Auxin transport - shaping the plant. Curr. Opin. Plant. Biol. 6, 7–12 (2003).   \n2. Trewavas, A. Green plants as intelligent organisms. Trends Plant. Sci. 10, 413–419 (2005).   \n3. Mann, S. Life as a nanoscale phenomenon. Angew. Chem. Int. Ed. 47, 5306–5320 (2008).   \n4. Glotzer, S. C. & Solomon, M. J. Anisotropy of building blocks and their assembly into complex structures. Nat. Mater. 6, 557–562 (2007).   \n5. Zhao, X., Xia, Y. & Whitesides, G. M. Fabrication of three-dimensional microstructures: microtransfer molding. Adv. Mater. 8, 837–840 (1996).   \n6. Bartholomeusz, D. A., Boutte, R. W. & Andrade, J. D. Xurography: rapid prototyping of microstructures using a cutting plotter. J. Microelectromech. Syst. 14, 1364–1374 (2005).   \n7. Hong, S. et al. 3D Printing of highly stretchable and tough hydrogels into complex, cellularized structures. Adv. Mater. 27, 4035–4040 (2015).   \n8. Gladman, A. S., Matsumoto, E. A., Nuzzo, R. G., Mahadevan, L. & Lewis, J. A. Biomimetic 4D printing. Nat. Mater. 15, 413–418 (2016).   \n9. Matsuda, T., Kawakami, R., Namba, R., Nakajima, T. & Gong, J. P. Mechanoresponsive self-growing hydrogels inspired by muscle training. Science 363, 504–508 (2019).   \n10. Chen, M. et al. Living additive manufacturing: transformation of parent gels into diversely functionalized daughter gels made possible by visible light photoredox catalysis. Acs. Cent. Sci. 3, 124–134 (2017).   \n11. Zhou, H. & Johnson, J. A. Photo-controlled growth of telechelic polymers and end-linked polymer gels. Angew. Chem. Int. Ed. 52, 2235–2238 (2013).   \n12. Gordon, M. B., French, J. M., Wagner, N. J. & Kloxin, C. J. Dynamic bonds in covalently crosslinked polymer networks for photoactivated strengthening and healing. Adv. Mater. 27, 8007–8010 (2015).   \n13. Zhao, H., Sterner, E. S., Coughlin, E. B. & Theato, P. o-Nitrobenzyl alcohol derivatives: opportunities in polymer and materials science. Macromolecules 45, 1723–1736 (2012).   \n14. Maruo, S., Nakamura, O. & Kawata, S. Three-dimensional microfabrication with two-photon-absorbed photopolymerization. Opt. Lett. 22, 132–134 (1997).   \n15. Chen, Y. et al. Mechanically induced chemiluminescence from polymers incorporating a 1,2-dioxetane unit in the main chain. Nat. Chem. 4, 559–562 (2012).   \n16. Ramirez, A. L. et al. Mechanochemical strengthening of a synthetic polymer in response to typically destructive shear forces. Nat. Chem. 5, 757–761 (2013).   \n17. Jin, C. Y., Li, Z., Williams, R. S., Lee, K. C. & Park, I. Localized temperature and chemical reaction control in nanoscale space by nanowire array. Nano. Lett. 11, 4818–4825 (2011).   \n18. Liu, Y. et al. Humidity- and photo-induced mechanical actuation of crosslinked liquid crystal polymers. Adv. Mater. 29, 1604792 (2017).   \n19. Du, X. et al. UV-triggered dopamine polymerization: control of polymerization, surface coating, and photopatterning. Adv. Mater. 26, 8029–8033 (2014).   \n20. Truby, R. L. & Lewis, J. A. Printing soft matter in three dimensions. Nature 540, 371–378 (2016).   \n21. Yu, H. & Ikeda, T. Photocontrollable liquid-crystalline actuators. Adv. Mater. 23, 2149–2180 (2011).   \n22. Kloxin, A. M., Kasko, A. M., Salinas, C. N. & Anseth, K. S. Photodegradable hydrogels for dynamic tuning of physical and chemical properties. Science 324, 59–63 (2009).   \n23. Habault, D., Zhang, H. & Zhao, Y. Light-triggered self-healing and shapememory polymers. Chem. Soc. Rev. 42, 7244–7256 (2013).   \n24. Zhou, H. et al. Photoswitching of glass transition temperatures of azobenzenecontaining polymers induces reversible solid-to-liquid transitions. Nat. Chem. 9, 145–151 (2017).   \n25. Cuthbert, J. et al. Transformable materials: structurally tailored and engineered macromolecular (STEM) gels by controlled radical polymerization. Macromolecules 51, 3808–3817 (2018).   \n26. Ono, T., Sugimoto, T., Shinkai, S. & Sada, K. Lipophilic polyelectrolyte gels as super-absorbent polymers for nonpolar organic solvents. Nat. Mater. 6, 429–433 (2007).   \n27. Pelliccioli, A. P. & Wirz, J. Photoremovable protecting groups: reaction mechanisms and applications. Photochem. Photobiol. Sci. 1, 441–458 (2002).   \n28. Cui, J., Miguel, V. S. & del Campo, A. Light-triggered multifunctionality at surfaces mediated by photolabile protecting groups. Macromol. Rapid. Commun. 34, 310–329 (2013).   \n29. Montarnal, D., Capelot, M., Tournilhac, F. & Leibler, L. Silica-like malleable materials from permanent organic networks. Science 334, 965–968 (2011).   \n30. Zou, W., Dong, J., Luo, Y., Zhao, Q. & Xie, T. Dynamic covalent polymer networks: from old chemistry to modern day innovations. Adv. Mater. 29, 1606100 (2017).   \n31. Self, J. L., Dolinski, N. D., Zayas, M. S., de Alaniz, J. R. & Bates, C. M. Bronsted-acid-catalyzed exchange in polyester dynamic covalent networks. Acs. Macro. Lett. 7, 817–821 (2018).   \n32. Ducrot, E., Chen, Y., Bulters, M., Sijbesma, R. P. & Creton, C. Toughening elastomers with sacrificial bonds and watching them break. Science 344, 186–189 (2014).   \n33. Jerome, F. S., Tseng, J. T. & Fan, L. T. Viscosities of aqueous glycol solutions. J. Chem. Eng. Data 13, 496 (1968).   \n34. By Martin, D., Hager, P. G., Christoph, Leyens, Sybrand van der, Zwaag & Schubert, A. U. S. Self-healing materials. Adv. Mater. 22, 5424–5430 (2010).   \n35. Chen, X. et al. A thermally re-mendable cross-linked polymeric material. Science 295, 1698–1702 (2002).   \n36. White JSM, S. R., Sottos, N. R., Krull, B. P., Cruz, W. A. Santa & Gergely, R. C. R. Restoration of large damage volumes in polymers. Science 344, 620–623 (2014).",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# Acknowledgements  \n\nThis work was supported by BMBF under the project of the Leibniz Research Cluster “Organic/synthetic multifunctional microproduction units—New ways to the development of the active ingredient” with award number 031A360D. Y.Z. acknowledge the support of starting funding of ShanghaiTech University while L.X. and X.X. acknowledge the support from the Chinese Scholarship Council (CSC).",
+        "category": " Acknowledgements"
+    },
+    {
+        "id": 8,
+        "chunk": "# Author contributions  \n\nJ.C. and Y. Z. conceived the concepts of the research. J.C. supervised the research. L.X. and J.C. designed the experiments. L.X., X.X., B.K., F.P., and S.W. performed the experiments. L.X., X.X., Y.Z. and J.C. analyzed the results; L.X., Y.Z. and J.C. wrote the paper. All authors commented on the paper.",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# Competing interests  \n\nThe authors declare no competing interests.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 10,
+        "chunk": "# Additional information  \n\nSupplementary information is available for this paper at https://doi.org/10.1038/s41467- 020-14807-x.  \n\nCorrespondence and requests for materials should be addressed to Y.Z. or J.C.  \n\nPeer review information Nature Communications thanks Kunpeng Cui, Jiang Xuesong and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Peer reviewer reports are available.  \n\nReprints and permission information is available at http://www.nature.com/reprints  \n\nPublisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.  \n\nOpen Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/ licenses/by/4.0/.  \n\n$\\circledcirc$ The Author(s) 2020",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# REVIEW ARTICLE OPEN Small data machine learning in materials science  \n\nPengcheng ${\\sf X}{\\sf u}^{1}$ , Xiaobo $\\mathbf{j}\\mathbf{i}^{2}$ , Minjie Li $\\textcircled{1}2$ and Wencong Lu 1,2,3✉  \n\nThis review discussed the dilemma of small data faced by materials machine learning. First, we analyzed the limitations brought by small data. Then, the workflow of materials machine learning has been introduced. Next, the methods of dealing with small data were introduced, including data extraction from publications, materials database construction, high-throughput computations and experiments from the data source level; modeling algorithms for small data and imbalanced learning from the algorithm level; active learning and transfer learning from the machine learning strategy level. Finally, the future directions for small data machine learning in materials science were proposed.  \n\nnpj Computational Materials  (2023) 9:42 ; https://doi.org/10.1038/s41524-023-01000-z",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# INTRODUCTION  \n\nAs an interdisciplinary subject covering computer science, mathematics, statistics and engineering, machine learning is dedicated to optimizing the performance of computer programs by using data or previous experience, which is also one of the important directions of artificial intelligence development1,2. In recent years, machine learning has been widely used in many fields such as finance, medical care, industry, and biology3–10. In 2011, the concept of material genome initiative (MGI) was proposed to shorten the material development cycle through computational tools, experimental facilities and digital data. Under the leadership of the MGI, machine learning has also become one of the important means for materials design and discovery11,12. The core of machine learning-assisted materials design and discovery lies in the construction of machine learning models with good performance through algorithms and materials data to achieve the accurate prediction of target properties for undetermined samples13. The constructed model could be further used to discover and design materials or explore the patterns and laws hidden behind the materials data. In the past decades, machine learning has become more and more developed and favored by researchers as a powerful tool to assist in the design and discovery of various materials, including alloys, perovskites, polymers, etc14–17. A lot of related studies have proved that compared with the trial-and-error method based on experiment and experience, machine learning can quickly obtain laws and trends from available data to guide the development of materials without understanding the underlying physical mechanism. Data is the cornerstone of a machine learning model, which directly determines the performance of the model from the source. It is widely accepted that we are in an era of big data where the data keep exploding all the time to allow machine learning to play such a big role. However, in the field of materials science, some questions about data are worth thinking deeply. Has the materials data really entered the era of big data? How much data can be considered big data? What is the difference between big data and small data?  \n\nSome statisticians consider the ‘big’ of big data refers to the scale of the data, including the amount of samples or the number of variables18. We believe that the definition standard of big data needs to be determined by combining the sample size and the number of variables. The amount of data needed should vary depending on the size of the space and the complexity of the target system. However, there are few specific quantitative indices about the data size to definite the big data, and there is also obscure to make a clear distinction between big data and small data. The concepts of big data and small data are relative rather than absolute. The small data discussed in this review focuses on the limited sample size. Some scholars believed that the data generally obtained from large-scale observations or instrumental analysis could be regarded as big data, mainly used for simple analysis of prediction; while the data derived from humanconducted experiments or subjectively collection could be regarded as small data, mainly used for complex analysis of the exploration and understanding of causal relationships18. From this point of view, although the development of materials synthesis and characterization as well as the data storage technology has led to the increase in the amount of materials data, most of the data used for materials machine learning still belong to the category of small data. An important development direction in materials machine learning is the interpretation of the relationship between descriptors and material properties, which can also be viewed as an exploration of causal relationships. However, the applications of the models depend on the accurate prediction ability of the model, so even for small data, there remain some requirements for the prediction ability of the model. The acquisition of materials data requires high experimental or computational costs, leading to the dilemma where researchers must make a choice between simple analysis of big data and complex analysis of small data within a limited cost in the process of data collection. If the goals of the research can be achieved with smaller data, most researchers tend to favor the collection of small samples under the controlled experimental conditions instead of large samples with the unknown origin19. The quality of the data trumps the quantity in the exploration and understanding of causal relationships. In addition, the uncertainty assessment of models constructed with small data is simpler than that of big data, and the conclusions drawn from small data will remind users to use more cautiously. The essence of working with small data is to consume fewer resources to get more information.  \n\nSmall data tend to cause the problems of imbalanced data and model over fitting or under fitting due to the small data scale and too high or too low feature dimensions, which has always been one of the pain points in materials machine learning. There are two ways to solve the problems caused by small data: One is from the data perspective, to increase the data size in the process of data collection. The other is from the machine learning perspective, to select a modeling algorithm suitable for small datasets or to improve the predictive accuracy of the model through machine learning strategies. As shown in Fig. 1, this review aims to introduce the general process of machine learningassisted materials design and discovery combined with the cutting-edge research achievements and summarize the methods of dealing with small data in the process. The methods of dealing with small data were introduced from the three levels, including data extraction from publications, materials database construction, high-throughput computations and experiments from the data source level; modeling algorithms for small data and imbalanced learning from the algorithm level; active learning and transfer learning from the machine learning strategy level. In addition, the future directions with challenges of small data in materials machine learning are also summarized.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# WORKFLOW OF MATERIALS MACHINE LEARNING  \n\nOne of the most direct goals of machine learning-assisted materials design and discovery is to apply the algorithms and materials data to construct models for the prediction of the material properties. As shown in Fig. 2, the workflow of materials machine learning includes data collection, feature engineering, model selection and evaluation, and model application20–23.  \n\nMaterials data are required to be collected after clarifying the research object and relevant properties. The data are generally divided into two parts: The target variable reflecting the property of the materials and the descriptor reflecting the information of the materials themselves. The data of target variable could be collected from published papers, materials databases, lab experiments, or first-principles calculations24. Although collecting data from the publications can access the latest research data, it also requires the huge cost to search for a large number of publications along with the data of mixed quality. Besides, even for the same property of the same materials with the same synthesis and characterization methods in different publications, there could still exist some inconsistency in the property values, which may bring the challenges of data uncertainty assessment and the complicated data preprocessing15. A large amount of data can be obtained from the materials databases in a short time. However, due to the cycle delay of the entry and check of the materials data, the data in the latest research could not be available from the materials databases. The quality of data obtained through experiments or calculations tend to be high because of the unification of experimental and computational conditions, but the cost of some materials such as alloys containing precious metal elements is too high to obtain a large amount of data through experiments. The emergence of firstprinciples calculations has made up for the limitations of experiments. The first-principles method is based on the quantum mechanics, in which the calculation process only requires the involved atomic species and the position coordinates to become one of the preferred methods for the design and exploration of materials25–27. But the calculation accuracy is also affected by the level of material systems and computer hardware. Descriptors can be divided into three scales from microscopic to macroscopic: element descriptors at the atomic scale; structural descriptors at the molecular scale; and process descriptors at the material scale. The element descriptors reflect the composition information of the materials. The acquisition of element descriptors requires the composed chemical elements of the materials and their stoichiometric ratios. Structural descriptors reflect not only compositional information, but also the 2D or 3D structural information of the materials, which can be generated by descriptor generation software or toolkits like Dragon, PaDEL, and RDkit28–31. Process descriptors do not reflect information about the materials themselves, but rather reflect the influence of experimental conditions in synthesis or characterization on the properties. In addition to the above three types of descriptors, generating descriptors based on domain knowledge to construct interpretable machine learning models is also one of the research hotspots in recent years. Lian et al.32 used machine learning based on domain knowledge to obtain descriptors from empirical formulas containing unknown parameters to predict the fatigue life (S-N curve) of different series of aluminum alloys. Compared with models constructed without domain knowledge, the model predicted ability was greatly improved. For materials data, we have been always insisting that every piece of data is precious and machine learning is able to fulfill its potential value. Descriptors generated from domain knowledge could assist machine learning algorithms to better capture the key information and improve the predicted accuracy of the model.  \n\n![](images/5fb3fb609d5a8ab50ab0495e7146e769e7d9ac5af991f1e4b7dcd24dc2602e04.jpg)  \nFig. 1 The power of small data in materials science. The dilemma of small data faced by materials machine learning and corresponding dealing methods.  \n\n![](images/10344ea9ea1abebf7f68fe304a4837334b64a3300c8b1110af89e22fbaeefefa.jpg)  \nFig. 2 The workflow of machine learning. The workflow of materials machine learning.  \n\nFeature engineering is an integral part of machine learning. Feature engineering refers to the selection of optimal descriptor subsets from the original descriptors with a series of engineered methods for modeling, including feature preprocessing, feature selection, dimensionality reduction, and feature combination. Data preprocessing aims to improve the quality of the incomplete, inconsistent, and unusable data. The specific methods include normalization or standardization to perform interval scaling on descriptor data, and convert data with units into data without units to unify data metrics by removing the influence of units to make data processing faster and more agile. For the missing values of the descriptors, the mean, median, before or after values can be used to fill in, or the data corresponding to the missing values can be directly deleted. Materials descriptors, especially those generated by software, tend to be high in the dimension and contain redundant information while describing materials information. The process of removing redundant descriptors is called feature selection. According to the relationship between the feature selection algorithms and modeling algorithms, the commonly used feature selection methods can be divided into filtered, wrapped and embedded33,34. In addition to the feature selection, the descriptors of the original high-dimensional space can also be reorganized to reduce the dimensionality by projecting the descriptors of the original high-dimensional space into the lowdimensional space, which is called dimensionality reduction35,36. The difference between dimensionality reduction and feature selection is that feature selection aims to remove and delete the redundant descriptors, while dimensionality reduction is to form descriptors through the reorganization of descriptors and does not retain any of the original descriptors. Common dimensionality reduction methods include principal component analysis (PCA) and linear discriminant analysis $(\\mathsf{L D A})^{37-39}$ . Feature combination could deal with the problem of under fitting caused by too low descriptor dimensions. The core of feature combination is to generate a lot of combined descriptors by combining the original descriptors with the simple mathematical operation for further feature selection and modeling. The Sure Independence Screening Sparsifying Operator (SISSO) is a compressed sensing-based data analysis method that can perform feature engineering transformations based on given descriptors to generate a large number of features, from which the optimal low-dimensional feature subset could be found40,41.  \n\nThere are various modeling algorithms to choose for either regression or classification tasks. For the same data, models constructed with different machine learning algorithms have different performance, which requires the evaluation of the modeling algorithms to select the optimal model without any under fitting and over fitting. The most used evaluation methods are $K$ -fold cross-validation (K-fold CV), leave-one-out crossvalidation (LOOCV), and leave-out method $42-44$ . $K\\cdot$ -fold CV randomly divides the original data into $\\boldsymbol{K}$ parts by nonrepetitive sampling and selects 1 part as the test set each time, while the remaining $\\kappa\\ –1$ parts are used as the training set for modeling. After repeating $\\boldsymbol{K}$ times, total $\\boldsymbol{K}$ models are obtained after training on each training set to test the performance with the corresponding test set. The average of the $K$ -group test set results is used as a performance indicator to evaluate the model performance under the $K$ -fold CV. LOOCV is a special case of $K\\cdot$ - fold CV, where $K$ is equal to the number of samples N. Therefore, for $N$ samples, there are N-1 samples selected each time to train the model, leaving one sample as the test set to evaluate the model. The leave-out method refers to dividing the original dataset $D$ into two mutually exclusive subsets S and $V.$ The training set S is used to train the model, while the test set V is set as the unknown data used to evaluate the generalization ability of the model. It should be noted that the K-fold CV and the leaveout method have certain requirements on the data size. Especially when the number of samples is less than 30, LOOCV is generally considered to be the most recommended evaluation method. In case the division of the dataset may have an impact on the performance of the model, the repeatability measure named y-scrambling can be used to further verify the stability of the model45,46. By randomly dividing the dataset into training set and test set for multiple times to evaluate the stability of the model, the problem of random fluctuations caused by dataset division can be avoided. After the evaluation method is determined, specific indicators are needed to quantify the performance of the model. For regression tasks, commonly used evaluation indicators include mean absolute error (MAE), mean relative error (MRE), root mean square error (RMSE), correlation coefficient (R), and the determination coefficient $({\\mathsf{R}}^{2})$ between the predicted value and the true value. For classification tasks, commonly used evaluation indicators include classification accuracy, true positive rate (TPR), false positive rate (FPR), recall rate, precision rate, etc. In model selection and evaluation, it is necessary to consider the influence of algorithm parameters on the model. The process of parameters optimization aims to adjust the model parameters to further improve the prediction ability of the model.  \n\nThe most basic function of a model is to predict the properties of the unknown materials. According to this function, the model can be applied to virtual screening, online server and theoretical discovery. Virtual screening refers to artificially generating a large number of virtual samples for the constructed models to predict properties and quickly screen out the materials that meet the requirements for further experimental or computational validation47,48. Virtual screening avoids the experience-based experiments to a certain extent and realizes the data-driven way to design and discover materials. However, the generated virtual samples often cannot cover the entire search space and huge computing resources are still consumed in the prediction of too many samples. The online server allow the constructed models to be imported into the back-end server and then the corresponding user interaction page is developed on the front-end49. Before researchers conduct experiments of the designed materials, the properties can be quickly obtained through model prediction once the user inputs the necessary information for unknown samples. The advantage of the online server lies in the sharing of models, where the models can be used anytime and anywhere with only electronic equipment and network. Both virtual screening and online server are the most intuitive applications of the model without any exploration of the laws and patterns contained in the materials data. While the theoretical discovery could explore the relationship between the important material descriptors and properties with the assistance of statistics and domain knowledge to better understand the nature of the materials properties and guide the design of materials. However, we should be cautious when using the rules mined from small datasets because the rules are only more suitable for small data and the generalization ability remains to be verified.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# INCREASE THE DATA SIZE BEFORE/IN THE DATA COLLECTION  \n\nIn this part, some methods for small data in materials machine learning before/in data collection will be introduced with the combination of cutting-edge and typical cases. As has been illustrated above, the materials data tend to be collected from publications, materials database, first-principles computations and experiments. Therefore, data extraction from publications, materials database constructions as well as high-throughput computations and experiments could help obtain the data size from the data source.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# Data extraction from publications  \n\nThe publications often contain data of the most cutting-edge studies. Most of the data collected from publications in the materials machine learning work rely more on the human resources to search and read publications for data collection. The most famous inorganic crystal database, the database of materials platform for data science (MPDS) created by the team of Villars, obtains the data by manual review of publications before entering the data into database15. Nevertheless, manually extracting data from publications is rather expensive and laborintensive. In addition, in the process of manual data collection, the bias of data caused by subjective factors would occur, leading to the situation where the data not conducive to modeling tend to be ignored or directly removed. The model construction in the bias of the data is extremely detrimental to the model applications. With the development of natural language processing (NLP) and text mining (TM) technology, the ideal of automatic data extraction from publications is expected to be realized50,51. The commonly used software and platform in TM could be available in Supplementary Table 1.  \n\nThe main steps of automatically extracting data from publications through NLP and TM technology include: (1) document retrieval and conversion into plain text; (2) text preprocessing, including sentence labeling and segmentation, text normalization, part-of-speech labeling and dependency parsing; (3) information retrieval; (4) data management52,53. The retrieval of documents mainly refers to the search of published papers in different journals. However, many journal papers are not open access and require plenty of money to subscribe. Besides, the format and layout of papers in different journals vary a lot, leading to the barriers in automatically data extraction. In addition to journal articles, documents such as conference papers, patents, technical reports, etc. also contain the required information. Documents in journals are mostly in the form of HTML or PDF files. The HTML can be parsed and marked up with programming tools, while the PDF files are complex in the form where the arrangement of text is interspersed with tables, figures and equations, which affects the accuracy of conversion to original text and increases the difficulty of extracting plain text from PDF files. In the process of converting PDF documents, errors often occur due to the superscripts and subscripts in chemical formulas or equations. Such errors require advanced optical character recognition (OCR) to avoid54. Creating an OCR for scientific texts is an area of active research in computer science and TM. The labeling and segmentation of sentences is the key step in information extraction to better understand the logical components in sentences. The labeling of sentences requires the explicit labeling criteria, usually marked with special symbols; while the segmentation of sentences aims to determine the boundaries in the text55. However, the complexity of materials terminology and non-standard naming conventions in academic papers often lead to labeling errors and over-segmentation of sentences, which would propagate along the TM process to affect the accuracies of results. Text normalization can be understood as stem extraction56. The same word usually has different existence in different tenses and voices. Extracting the stem of the word would help to reduce the complexity of language. Part-of-speech (POS) labeling refers to identifying and marking the grammatical properties of words, such as verbs, nouns, adjectives, etc., which is used to provide the language- and grammar-based lexical features to TM models57. But in scientific texts, the ambiguity caused by the context of words brings challenges to POS labeling and requires adjustments to the underlying NLP model. Dependency parsing could map linear sequences of sentence tokens to hierarchies by parsing the internal grammatical dependencies between words, which is highly sensitive to the accuracy of punctuation marks and word forms58. In scientific papers, to describe the objectivity of facts, the authors tend to use a lot of passive voice and past tense, resulting in that the general dependency parsing models cannot accurately capture the features of the sentences. Information retrieval (IR) refers to the use of NLP techniques to extract various types of data from the preprocessed text, of which the most common IR method is named entity recognition (NER), which classifies text tokens into specific categories59,60. In scientific texts, named entities can be technical terms as well as physicochemical parameters and properties. Chemical NER is a widely used IR method that usually involves the identification of chemical and materials terms in the text with early applications focusing on the extraction of drug and biochemical information61. Data in academic papers exist not only in text, but also in figures and tables that are embedded in the text. Extracting data from journal figures and tables requires both TM and image recognition techniques. The challenges to data retrieval caused by the format of figures and tables in academic papers include: (1) Figures and tables exist not only in text, but also in external links such as the supporting information. (2) The forms of figures and tables are very complex. For example, the figure could be mixed with a table; the figure could contain multiple sub-figures; and the table row and column could be merged. Although image recognition technology has been widely used in materials science, it is more used to explore the morphology and structure of the materials in figures through deep learning, rather than to separate the figures embedded in scientific texts.  \n\nAt present, manual data extraction from publications is still the mainstream. The ambiguity of materials naming standards, the complexity of the chemical formulas, the diversification of languages, and the professional terminology have all caused great challenges to apply NLP and TM technology to automatically extract data from publications. Although automated data extraction from publications is still in its infancy, TM and NLP may play a key role in enabling more data-driven materials research. Swain et al.62 has developed the toolkits called ChemDataExtractor for automatic extraction of chemical information from scientific publications. ChemDataExtractor provides a layout analysis tool for complex PDF files built on the PDFMiner framework to group text into headings, paragraphs and captions using the position of images and text characters. Besides, ChemDataExtractor could group text into headings, paragraphs and captions using image and text character positions. For text labeling and segmentation, ChemDataExtractor provides a sentence splitter using the Punkt algorithm based on Kiss and Strunk, which detects sentence boundaries through unsupervised learning of common abbreviations and sentence beginnings. The Punkt algorithm has been proved to be widely applicable to multiple languages and text domains, performing the best when trained on text from the target domain. For words derived from unannotated publications, Brown clustering is used to implement hierarchical clustering based on the context of word occurrence to improve the performance of lexical labeling and named entity recognition in various domains. The POS tagger of ChemDataExtractor is trained with a linear chain conditional random field (CRF) model using the orthant-wise limited-memory quasi-Newton (OWL-QN) method implemented in the CRFsuite framework. A CRF model-based recognizer combined with a dictionary-based recognizer and a regular expression-based recognizer are used for chemical named entity recognition. For chemical identifier disambiguation, the Hearst and Schwartz algorithms are used to detect the definition of chemical abbreviations and labels, which could generate a list of mappings between abbreviations and their corresponding full non-abbreviated names, merging the data defined for different identifiers into a single record for each chemical entity. In addition to extracting data from text, ChemDataExtractor can also parse tables to extract data. For tables where each row corresponds to a single chemical entity and each column describes the value of that entity’s attributes, ChemDataExtractor can extract information using a dedicated version of the natural language processing pipeline by treating each individual table cell as a short, highly formulaic sentence. Currently, the team has released ChemDataExtractor version 2.0, which retains all the features of ChemDataExtractor while providing a complete approach to ontology auto-population in the scientific domain63. ChemDataExtractor 2.0 supports extraction from publications from 155 papers as an evaluation set, using extracted data from each compound with 18 sets of nested crystallographic features, which generated an overall accuracy of $92.2\\%$ across 26 different journals, achieving the construction of a framework for seamless integration from publications to data-driven methods. Yukari et al.64 developed a web-based system called Starrydata2 to automatically extract numerical data from figures of scientific papers and the chemical composition of the corresponding samples. The visualization capabilities of Starrydata2 allow for the display of data files in a variety of formats, including line plots, heat maps, and multiple scatter plots. Starrydata2 has successfully collected experimental data from mapped figures of more than 11,500 samples of thermoelectric materials. The electronic structure differences of the parent compounds PbTe, PbSe, PbS, and SnTe were revealed by combining a partial experimental dataset of 434 rock salt-based thermoelectric materials with first-principles calculations. The evaluation of the electronic relaxation time $\\uptau_{\\mathrm{el}}$ by combining the computational and experimental data revealed that achieving a long $\\uptau_{\\mathrm{el}}$ is considered essential to improve the thermoelectric quality factor.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# Materials database construction  \n\nMaterials data have the characteristics of high reliability requirements, strong correlation, many influencing factors, complex acquisition process and wide distribution of data, which is one of the reasons for the dilemma of small data in materials science. The materials database could collect the fragmented materials data conveniently for users to store, update and retrieve large amounts of data more quickly, safely and accurately. In the design and discovery of materials with data-driven methods, the acquisition of the materials properties, the mechanisms under special conditions, materials performance improvement, materials selection and safety evaluation are all inseparable from the support of materials database platforms. Obtaining a large amount of materials data through databases for further analysis and knowledge mining is one of the important directions of materials machine learning. The most common way to use the data in the database is to be taken as the training set to train the machine learning model combined with the algorithms. In addition to the training set, the data in the database can also be used as a test set to evaluate the performance of the constructed model, or used as a candidate set in combination with the model to filter out the materials with the properties meeting the requirements. Many databases in recent years tend to have high-throughput computing frameworks, machine learning toolkits, and statistical analysis tools, which indirectly provide support for machine learning research.  \n\nThe commonly used materials databases are shown in Supplementary Table 2. According to the data types in the materials databases, materials data can be divided into computational and experimental data. Computational data refer to theoretical data on materials, usually derived from highperformance and high-throughput computations based on first principles. It should be noted that the computational data need to be combined with experimental data and empirical data to process and analyze large-scale materials data to be fully mined and utilized. Most of the experimental data mainly exist in the publications or the private database where the researchers could enter the data after the experimental synthesis and characterization. Both computational and experimental data could be automatically extracted from publications through NLP and TM techniques. The 35,675 solution-based databases of inorganic materials synthesis procedures were extracted from over 4 million publications using NLP, TM and machine learning by Ceder et al.65  \n\nEach of these procedures contains the basic synthesis information, including the parent ion, target materials, quantities, synthesis action and corresponding properties. The experts verified the completeness and accuracy of the data by randomly extracting data combined with domain knowledge. In addition, the diversity of the extracted data was further analyzed in relation to the spatial extent of the materials covered. The results of the analysis show that the common targets and their corresponding precursors in the dataset cover materials that have attracted extensive attention over the last two decades. The database contains a large-scale solution-based dataset of inorganic material synthesis procedures, providing a basis for testing and validating the existing empirical synthesis rules, improving prediction accuracy, and even mining rules to guide synthesis. For both the computational data and the experimental data, the most intractable difficulty in the construction of a material database is the evaluation and verification of data quality. Although there are many materials databases, each one has its own standards for the evaluation and verification of data quality, which are not uniform. Even though many scholars are working on developing material data standards, there is few specific standard for the evaluation and verification of materials data quality66. Therefore, it is necessary to learn the research experience of data quality evaluation in other fields, combining the characteristics of materials data to carry out research on the data quality evaluation methods, corresponding managements and applications. It can be found from Supplementary Table 2 that many materials databases are established according to the types of materials, but the classification of materials can be divided into many types according to the different standards. The obscure classification standards of materials also bring obstacles to the construction of material databases. Materials can be defined by their chemical composition and structure, while most databases use only chemical composition or chemical formula to identify materials, which could cause the situation where the materials of different structures are often indistinguishable. Xu et al. proposed the MatML, a specification designed for material information exchange, which uses chemical composition and processing conditions to describe materials, based on research experience on materials such as single crystals, ceramics, alloys, polymers, etc. and the basics of materials science67. Materials could be divided into four levels according to MatML in Fig. 3: chemical system, compound, substance and material. Chemical systems are the basis of all materials to represent one or more elements that make up a material. Compounds are the second level to identify materials at the molecular level. For most inorganic materials, a compound can be defined by the chemical formula. However, for organic or polymer materials, the molecular structure must be specified. The third level is substance, which determines the state of the compound such as gas, liquid or solid. For solid state, the crystal state and crystal structure should also be given. A substance should correspond to a phase in a phase diagram. The fourth level is the materials. To define a material, many types of information are required, such as the form, dimensions, microstructure, process conditions, etc. In addition, the polymer database is extremely limited in the materials databases, which may be due to the structural properties of polymer materials. Experimentally synthesized polymers are often rarely single entities. The same polymer material with different polymerization degrees leads to different molecular weight distributions, which has created great difficulty to the database construction. Also, the complex monomeric structures and sequences of polymers lead to the lack of standard naming rules. The challenges currently faced in the construction of polymer databases include appropriate descriptors, elements associated with properties, details of characterization, and sources of data68.  \n\n![](images/94ee0e1717e78a39ed91a07f1c69b362e8b124c4fc9a870834b0f3d6a126acdc.jpg)  \nFig. 3 The material identification system. Four-level material identification system67.  \n\nThe materials database has developed for decades to store the materials data, but the construction of the materials database still faces great challenges. Firstly, there are many scientific research institutions establishing the materials databases in the world, which leads to the fragmentation of materials databases and low utilization rate of the materials data due to the uneven data quality of the database. In addition, the materials database is still in the stage of simultaneous construction and use. The construction and maintenance of the database have been the long-term work, requiring a lot of capital and human resources as well as the professional supervision for the collection, update and maintenance of the data. Secondly, the lack of uniform and complete materials classification standards and data quality evaluation methods would lead to uneven data quality. Lastly, the sharing of the materials data is limited due to intellectual property issues. In the establishment of the materials databases, the management of the intellectual property rights of the data should be strengthened; the quality and sharing of the data in the database should also be improved69. Even though the construction of the material database faces many challenges, the rapid acquisition of data from the materials database has alleviate the problem of small data to become an important way of data collection for materials machine learning.",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# High-throughput computations and experiments  \n\nMaterials data are rather precious because of the high experimental and computational costs. But the presence of highthroughput technology makes it possible to obtain a large amount of high-quality data by experimental or computational methods in a short period of time. The concept of high-throughput stems from gene sequencing. The first-generation sequencing can only measure one sequence of one sample at a time to generate relatively small data, while high-throughput sequencing can measure a large number of samples at a time, resulting in data in the dozens of gigabytes even hundreds of gigabytes70,71. One of the characteristics of high-throughput lies in the ability of processing a lot of samples in a short time to obtain more data. With the development of first-principles, high-performance computers and materials preparation and characterization technologies, obtaining a large amount of high-quality materials data through high-throughput computations and experiments combined with machine learning to develop materials is also a solution to small data in materials machine learning.  \n\nFirst principles are the cornerstone of high-throughput computations, which enables accurate computation of various electronic structures and total energy-related properties under atomic structure, including the properties of thermodynamics, kinetics, electromagnetism, and mechanics72,73. The development of highperformance computer and computational simulation technology makes the first-principles-based high-throughput computations to screen materials a potential direction in the materials design and discovery. Prior to experimental design, high-throughput computations can be used to screen out the stable structures that meet the requirements. The commonly used high-throughput computation toolkits are shown in Supplementary table 3. The essence of materials design based on high-throughput computations is to apply the concepts of ‘blocks construction’ and ‘highthroughput screening’ in combinatorial chemistry to the computer simulation of materials. After determining the basic building blocks of composition through materials calculations, a large number of compounds are constructed to obtain the corresponding properties through high-throughput computations, where machine learning could integrate data, program, and materials calculation software to map the quantitative relationship models of material composition, structure, and properties to guide the design of materials. As shown in Fig. 4, the workflow of the materials screening by high-throughput computations is generally divided into five steps: the construction of the samples for highthroughput computations and screening; screening based on thermodynamic stability; preliminary screening based on basic descriptors with limited precision; specific screening based on high-precision descriptors; screening based on other conditions74. High-throughput computations use the density functional theory (DFT) methods to quantitatively or qualitatively calculate the relevant properties of a large number of initial input material structures for screening, while machine learning combines the data to construct models to explore the patterns and laws behind the data. Both high-throughput computations and machine learning could essentially extract valuable information from data.  \n\n![](images/9d0d608417ba1d5c0bcafe9fc8317634c1d924e343972de6b105c816956b7672.jpg)  \nFig. 4 The funnel model of high-throughput computational screening. The funnel type model of high-throughput computational screening74.  \n\n![](images/bcb62b5d0b68d7398c927e1a84e3db9ee5b1fe9bf4255c8abeba1caaf1eef5ca.jpg)  \nFig. 5 The process of materials design. a Traditional materials design process; b The high-throughput experiments schema of modern materials75.  \n\nHowever, high-throughput computations are more inclined to complete the specified work according to the set rules such as calculating the properties of materials according to first-principles methods, which do not have the generalization ability. While machine learning tends to perform the good generalization ability because of the decision-making nature of the modeling algorithms. Combining high-throughput computations with machine learning to fully take the advantages of the parameters standardization and large-scale of high-throughput to solve the problem of small data in machine learning is expected to further improve the efficiency of screening and development of materials.  \n\nHigh-throughput experiment, also known as high-throughput preparation and characterization technology, is an important part of $\\dot{\\mathsf{M G}}\\mathsf{I}^{75}$ . The core idea of high-throughput experiment is to change the original sequential iteration method into parallel or efficient serial experiments. Commonly used high-throughput preparation and characterization techniques are shown in Supplementary table 4. The high-throughput preparation of materials is also called the combined preparation of materials, which refers to the preparation of a large number of materials with different components in a short time by a certain experimental method. After the materials preparation, highthroughput characterization techniques are required to obtain sample information in a relatively short time for further experiments or detailed characterization. The materials design processes of traditional way and the high-throughput experiments are shown in Fig. $5^{75}$ . The traditional materials design includes the loop of experimental design, material synthesis/characterization, and materials property analysis. Compared with traditional methods, the materials design based on high-throughput experiments takes the database as the center of the loop, integrating the data collection, storage, management, and mining to make full use of data to promote the development and applications of materials. High-throughput experiments can rapidly accumulate a large amount of experimental data to facilitate the screening or optimize the applications of materials.  \n\nHigh-throughput computations and experiments have become significant methods to provide sufficient materials data for machine learning research. Hu et al.76 obtained 640 2D halide perovskites $\\mathsf{A}_{2}\\mathsf{B}\\mathsf{X}_{4}$ $\\mathsf{A}=\\mathsf{L i},$ , Na, K, Rb, Cs; $\\mathsf{B}=\\mathsf{G e}_{\\mathsf{\\Pi}}$ , Sn, $\\mathsf{P b};\\mathsf{X}=\\mathsf{F},$ Cl, Br, I) and corresponding adsorption energies with $\\mathsf{L i^{+}}$ , $Z n^{2+}$ , ${\\mathsf{K}}^{+}$ , ${\\mathsf{N a}}^{+}$ , $\\mathsf{A l}^{3+},\\mathsf{C a}^{2+},\\mathsf{M}\\mathsf{g}^{2+},$ and $\\mathsf{F}^{-}$ by using high-throughput computations. After filtering out 13 descriptors with the Pearson correlation coefficient, k-nearest neighbors (KNN), Kriging, Random Forest, Rpart, SVM, and XGBoost were adopted for modeling. The results revealed that XGBoost performed the highest prediction accuracy with the ${\\mathsf{R}}^{2}$ and RMSE of the training set being 0.998 and $0.128\\mathsf{e V}_{\\iota}$ respectively. After modeling, various methods were used to rank the importance of descriptors, and different ranking methods consistently showed the great importance of ionic adsorbent density on the adsorption energy of hybrid systems. After highthroughput screening, 5 candidates were screened from a virtual design space consisting of 11,976 ion/perovskite for DFT verification, which proved to be applicable to ion batteries. Hayashi et al.77 developed an open-source Python library named RadonPy for fully automated polymer property calculations using all-atom classical molecular dynamics (MD) simulations, and successfully performed high-throughput computations on more than 1,000 amorphous polymers with a wide range of thermo physical properties. Machine learning techniques were successfully applied to calibrate the bias and variance of MD calculations. 8 amorphous polymers with high thermal conductivity and the underlying mechanisms were identified after high-throughput screening by RadonPy. The construction of a database using RadonPy will rapidly yield a large amount of high-quality data on polymer properties to facilitate the development of polymer informatics. Zhao et al.78 explored the optimal stability conditions for organolead iodide perovskite cells using a high-throughput experiment-based robotic system and machine learning. The robotic system synthesized more than 1,400 perovskite battery samples under different material compositions, experimental conditions, test conditions, and measured the battery performance decay time as the battery stability standard. Taking the material composition, experimental conditions and test conditions as the descriptors, and the battery performance decay time as the target property, a gradient boosting tree model was constructed with the RMSE of the test set being $169\\mathsf{h}$ . According to the optimal experimental conditions obtained from the feature analysis and the optimal composition of the optimal organic lead-iodine perovskite $\\mathsf{M A}_{0.1}\\mathsf C\\mathsf s_{0.05}\\mathsf F\\mathsf A_{0.85}\\mathsf P\\mathsf b\\mathsf b_{3},$ a perovskite battery with the highest performance degradation time of more than $4000\\mathsf{h}$ was successfully synthesized, far exceeding the vast majority of reported battery devices. This work has obtained the effect of optimal experimental conditions on battery performance degradation through high-throughput experiments and machine learning analysis, which effectively promotes the progress of perovskite battery stability research.  \n\nBoth high-throughput computations and experiments in the above researches are providing the sufficient sample size for modeling. However, since high-throughput computations are developed based on first-principles calculations, the computational characterization also brings more potential application possibilities in combination with machine learning. Machine learning can also be used to improve the precision and accuracy of DFT calculations. James et al.79 trained a neural network called DeepMind21 (DM21) on molecular data and fictitious systems with fractional charges and spins to overcome systematic errors due to violations of the mathematical properties of exact generalized functions. DM21 provides a solution to the accuracy and precision problems associated with DFT calculations, demonstrating the success of combining DFT with modern machine learning methods. For different DFT computational data, it is often necessary to construct different machine learning models to ensure model accuracy. Developing machine learning models with general applicability to different DFT data is also one of the current research directions for combining machine learning with DFT computations. Takamoto et al.80 trained a generalized neural network potentials (NNPs) model called prefiring potentials (PFP) using 20 datasets of DFT calculations. PFP is capable of handling any combination of 45 elements and has general applicability in different application fields, including lithium diffusion in $\\mathsf{L i F e S O_{4}F}$ , molecular adsorption in metal-organic frameworks, anorder–disorder transition of $\\mathsf{C u-A u}$ alloys, and material discovery for a Fischer–Tropsch catalyst. PFP can greatly alleviate another limitation of atomic simulations caused by time and space scales. The combination of DFT and PFP or experiments using PFP-based screening will also accelerate the field of materials discovery.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# ALGORITHMS FOR SMALL DATA IN MODELING  \n\nIn the modeling process, some algorithms have good compatibility with small datasets and unbalanced data to obtain the ideal results. This part will introduce small data modeling algorithms and algorithms for dealing with imbalanced data.",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# Modeling algorithms for small data  \n\nThe performance of machine learning models is not only dependent on the quantity and quality of the data, but also highly dependent on the modeling algorithm. Some algorithms are well appropriate for modeling with small data. Combined with the case study of materials machine learning, algorithms suitable for modeling with small data include support vector machine, Gaussian process regression, random forest, gradient boosting decision tree, XGBoost and symbolic regression.  \n\nSupport vector machine (SVM) is a kernel-based algorithm. The kernel functions would efficiently complete the space transformation to convert the original nonlinear problem into a linear problem in a high-dimensional space and turn a linear inseparable problem in a low-dimensional space into linearly separable81. The basic principle of the SVM is to map the input vectors to a highdimensional space, finding an optimal hyperplane as the criterion for sample classification to achieve the best compromise between model complexity and learning ability to obtain the best robustness82. According to the machine learning tasks of classification and regression, SVM can also be called support vector classification (SVC) and support vector regression (SVR). The goal of SVC is to obtain the classification line of the largest edge hyperplane, where samples of different classes could be the farthest from each other. SVR uses the insensitive channel ε to deal with the trade-off between empirical risk and structural risk. The error is ignored when the predicted value $\\hat{y}_{\\mathrm{i}}$ satisfies $\\left|y_{\\mathrm{i}}{-}\\hat{y}_{\\mathrm{i}}\\right|\\leq\\varepsilon,$ otherwise the error is $|y_{\\mathrm{i}}-\\hat{y}_{\\mathrm{i}}|-\\varepsilon.$ In the empirical risk calculation, only the deviation is considered when it is greater than ε. The concept of “margin” in SVM has provided a structured description of data distribution, thereby reducing the requirements for data size and data distribution.  \n\nGaussian process regression (GPR) is a non-parametric method with Gaussian Process (GP) priors to perform regression analysis on data83. The model assumptions of GPR include regression residuals and Gaussian process priors. Without restricting the form of the kernel functions, GPR is theoretically a universal approximator for any objective function in the compact space. In addition, GPR could provide the posterior distribution of the predicted result with an analytical form when the regression residuals are normally distributed, which has proved that GPR is a probabilistic model with generalization ability and interpretability. As a non-parametric Gaussian process model, the complexity of GPR depends on the training data. Based on the characteristics of Gaussian process and the kernel functions, GPR is usually used for regression modeling of low-dimensional and small data.  \n\nRandom forest belongs to the Bagging type ensemble algorithm. By combining multiple weak classifiers, the final result is obtained by voting or average to improve the prediction accuracy and generalization performance of the overall model. A random forest consists of multiple decision trees and each tree in the forest jointly determines the final output of the model84. First, bootstrap sampling is applied to randomly select $k$ samples from the original training set with replacement to form training samples. Then, the models of $k$ decision trees are constructed for each of the $k$ samples to randomly combine to form the random forest. Finally, each record is voted to determine the final classification according to the $k$ classification results. For classification tasks, each decision tree in the random forest will give the final category, and finally the output category of each decision tree in the forest is comprehensively considered by voting. For regression tasks, random forest takes the average output of each decision tree as the final output.  \n\nGradient boosting decision tree (GBDT) is an iterative decision tree algorithm consisting of multiple decision trees that generate multiple weak learners in series85. By fitting the negative gradient of the loss function of the previous accumulated model of each weak learner, the accumulated model loss after adding the weak learner is reduced in the direction of the negative gradient. Each tree can make predictions on part of the data to get the final result by adding the conclusions of all the trees. Gradient boosting can be used for both classification and regression tasks.  \n\nXGBoost is an efficient system of Gradient Boosting, which realizes to form the tree with the difference between the result of the basic learner and the actual value to reduce the difference between the model value and the actual value to avoid over fitting86. When using classification and regression trees (CART) as the base classifier, XGBoost explicitly adds a regular term to control the complexity of the model, which is beneficial to prevent over fitting and improve the generalization ability of the model. GBDT only takes the first-order derivative information of the loss function during model training, while XGBoost performs secondorder Taylor expansion on the loss function to use both the firstorder and second-order derivatives at the same time. The traditional GBDT uses CART as the base classifier, while XGBoost supports multiple types of base classifiers, such as linear classifiers. Traditional GBDT uses all the data in each iteration, while XGBoost adopts a strategy similar to random forest, which supports sampling of data. The traditional GBDT is not designed to deal with missing values, while XGBoost can automatically learn the processing strategy of the missing values.  \n\nSymbolic regression is a genetic programming-based machine learning technique designed to identify an underlying mathematical expression87,88. It first builds a stochastic formula to represent the relationship between known independent and dependent variables to predict data. Each successive generation procedure evolves from the previous one, selecting the most suitable individuals from the population for genetic operations such as crossover, mutation and reproduction. The mathematical expression generated by symbolic regression is a combination of operator functions, variables and constants, which is essentially a combinatorial optimization process based on symbolic sets and intelligent algorithms. Currently, symbolic regression has been widely used in the field of materials machine learning to explore the relationship between important descriptors and material properties as well as to construct interpretable machine learning models.  \n\nSome of the works have proved that some algorithms have ideal performance in small data modeling. Weng et al.89 used symbolic regression to design a simple descriptor for describing and predicting the oxygen evolution reaction (OER) activity of oxide perovskite catalysts to rapidly identify oxide perovskite catalysts with improved OER activity. 18 known perovskite catalysts were first synthesized experimentally, 4 samples of each. Each sample was subjected to 3 OER tests under the same conditions and the reversible hydrogen electrode voltage $(V_{\\mathsf{R H E}})$ was measured at 5 different current densities, resulting in 1080 data points. The electronic parameters such as the number of $d$ electrons for TM ions, electronegativity values $\\mathsf{X}_{\\mathsf{A}}$ and $x_{B},$ valence states $\\mathsf{{\\Pi}}Q_{\\mathsf{A}},$ ionic radii $R_{\\mathsf{A}},$ the tolerance factor t and the octahedral factor $\\mu$ were combined with symbolic regression and hyper parametric grid search to generate about 8,640 mathematical formulas. After evaluating the accuracy and complexity of the generated formulas, the $9$ mathematical formulas at the Pareto front meet the criteria of high accuracy and low complexity, with the descriptor of μ/t being the best compromise between complexity and accuracy. The descriptor of $\\mu/t$ is able to reveal the pattern between the OER activity of oxide perovskite catalysts and the structural factors. Smaller $\\mu$ and larger t would lead to higher OER activity, so the use of large cations at the A-site and small cations at the B site of the perovskite structure enable further development of a large number of previously unexplored OER catalysts. After screening 3545 oxide perovskites in combination with virtual screening, 13 samples with minimum $\\mu/t$ values were selected for experimental validation. The experimental results show that 5 pure oxide perovskites possess OER activity, with $\\mathsf{C s}_{0.4}\\mathsf{L a}_{0.6}\\mathsf{M n}_{0.25}\\mathsf{C o}_{0.75}\\mathsf{O}_{3},$ $\\mathsf{C s}_{0.3}\\mathsf{L a}_{0.7}\\mathsf{N i O}_{3},$ $\\mathsf{S r N i}_{0.75}\\mathsf{C o}_{0.25}\\mathsf{O}_{3}$ and $\\mathsf{S r0}_{.25}\\mathsf{B a}_{0.75}\\mathsf{N i O}_{3}$ exhibiting OER activity exceeding that of oxide perovskite catalysts reported in the publications. Shi et al.90 collected 50 $A B O_{3}$ -type perovskites and corresponding experimental specific surface area (SSA) values from the publications as target property, 40 of which were used as training set and 10 as test set. The descriptors of atomic parameters and sol-gel process parameters are combined with genetic algorithm (GA) and SVR to select the optimal feature subset and construct the model for SSA prediction. The RMSE values of the training set and test set of the model are 3.745 and $1.794~\\mathsf{m}^{2}~\\mathsf{g}^{-1}$ , respectively, indicating the high prediction accuracy of the model. In addition, sensitivity analysis was used to analyze the quantitative impact of 5 important descriptors on SSA and 5 candidates with higher SSA were screened out by virtual screening. The author also developed a web server to realize real-time sharing of the model, laying a foundation for machine learning-assisted design of $A B O_{3}$ -type perovskites with high SSA. Lu et al.91 collected experimental interlayer spacing data for 85 layered double metal hydroxides from publications, 68 of which were used as training set and 17 as test set; and atomic parameters were collected from Lang’s handbook of chemistry as descriptors. The algorithms of GA combined with XGBoost, SVR and artificial neural network (ANN) were adopted to select features and construct the model. It is found that the XGBoost model with 6 descriptors performs the best. After randomly splitting the dataset 4 times, the average R of LOOCV and test set could reach 0.91 and 0.87, respectively. After parameters optimization, the LOOCV and test set R values of LOOCV are as high as 0.94 and 0.89. After virtual screening with the constructed model, $\\mathsf{C o}_{0.67}\\mathsf{F e}_{0.33}[\\mathsf{F e}(\\mathsf{C N})_{6}]_{0.11}\\bullet(\\mathsf{O H})_{2}$ with the interlayer spacing up to $12.4\\mathring{\\mathsf{A}}$ was screened out to applied to super capacitors.  \n\nIn addition to modeling algorithms for small data, our team have integrated various algorithms through ensemble learning to improve the predicted accuracy of the model constructed with small data. Chen et al.92 proposed a step-by-step design strategy based on small data to aid in the design of low melting point alloys. Ridge regression, XGBoost and SVR were applied to screen out three sets of optimal feature subsets and respectively constructed the melting point prediction models of low melting point alloys. After evaluating model performance with 10-fold CV, it was found that the performance of the three models was similar, and the R of the models were all higher than 0.94. In order to obtain a model with more stable prediction ability and higher accuracy, the R-X-S (Ridge regression-XGBoost-SVR) ensemble model was obtained through arithmetically integrating the three models by taken the average value. The R of the R-X-S model in the test set reached 0.990, which was higher than the highest single model. As shown in Fig. 6a, in order to further verify the generalization ability of the model, an external validation set was used to verify the four models, and the R of the four models were all higher than 0.97, which has proved that the R-X-S model has strong generalization compared with 0.968 of the original value in the publication. Besides, Lu et al.93 carried out a study on predicting the bandgaps for hybrid organic-inorganic perovskites (HOIPs) by using ensemble learning. The authors collected 1201 samples from the publications from 2009–2021, and generated 129 atomic descriptors, including atomic radius, atomic chemical potential, tolerance factor, tau factor, octahedral factor, etc. Then the various modeling algorithms were adopted to construct the models. And the top 4 models, involving CatBoost, XGBoost, LightGBM and gradient boosting machine (GBM) were selected as the sub-models for the ensemble learner namely, the weighted voting regressor (WVR). The WVR model complimented the weakness of each sub-model, and achieved a comprehensively superior performance than the sub-models. The ${\\mathsf{R}}^{2}$ and RMSE in LOOCV of WVR reached 0.95 and $0.079\\mathrm{eV}$ respectively, while the ${\\mathsf{R}}^{2}$ and RMSE in test set of WVR achieved 0.91 and $0.106\\mathrm{eV}$ respectively. Based on the ions collected from the formulas of the dataset, the authors constructed a gigantic material space compromising over $8.2\\times10^{18}$ combinations for exploring HOIP structures with suitable bandgaps. The proactive searching progress (PSP) method was developed to efficiently search the material compositions with expected bandgap values from the universal chemical space. As the result of PSP method shown in Fig. 6b, the 20,242, 733,848, 764,883, and 746,190 non- $\\mathsf{\\cdot P b}$ samples were designed for the HOIPs with the bandgaps of $1.20\\mathsf{e V}.$ , $1.34\\mathsf{e V},$ $1.70\\mathsf{e V}$ and $1.75\\mathsf{e V},$ respectively. To validate the searching result of PSP method as well as the predicting ability of the WVR model, the HOIP components of $\\mathsf{M A S n}_{\\times}\\mathsf{G e}_{1-\\times}|_{3}$ $(\\mathsf{x}=0.85$ , 0.74, 0.66) were synthesized and characterized as the experimental validation, where the average error between experiments and predictions was only $0.07\\:\\mathrm{eV}.$ The data in Lu’s work have reached up to 1201 and may be far from small data. But the constructed ensemble model with the superior performance to the sub-models indeed indicates that integrating various algorithms through ensemble learning could improve the predicted accuracy of the model.  \n\n![](images/fe678c0f52124805f3731d6e8e45c49c66ba72c484ebfa69f84b350affd543dc.jpg)  \nFig. 6 Ensemble models for small data modeling. a The calculated values in the publication, the experimental and predicted values of the validation set on different models92. b Bandgap distribution after iterations by ${\\mathsf{P S P}}^{93}$ .",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# Imbalanced learning algorithms  \n\nImbalanced learning algorithms aim to deal with the imbalanced data caused by the small data in the classification. Imbalanced learning is aimed at classification tasks, which is mainly manifested in that data size in different categories is unbalanced due to the limited samples in the minority class94. The minority samples of unbalanced data can be divided into absolutely and relatively few in terms of data size95. Absolutely few data refer to the data size of the minority class itself is rather scarce to lead to the limited information contained in data, which would be difficult for the classifier to capture the information of the minority class samples. Relatively few data mean that the minority class samples only occupy a small proportion compared with the majority class samples to blur the boundary of the minority class sample and reduce the recognition ability of the minority class samples. Traditional classification methods usually process data when the data size of each category is almost equal, but the data categories in materials science are often unbalanced.  \n\nImbalanced learning aims to deal with imbalanced data from two levels of data preprocessing and algorithm. The introduction of the commonly used imbalanced learning algorithms are available in Supplementary table 5. The most basic data preprocessing method is sampling, including undersampling, oversampling, and mixed sampling95. Undersampling balances the minority class by reducing the number of majority class samples, while oversampling by increasing the number of samples in the minority class to balance the data. Mixed sampling combines the oversampling and the undersampling to balance the data size of different categories. Algorithm-based imbalanced learning strategies include clustering algorithms, deep learning, cost-sensitive learning, and extreme learning machine $(\\mathsf{E L M})^{96}$ . The clustering algorithm could divide the samples in the space into different clusters, where the samples in the same cluster have similarities. After clustering the dataset, sampling the data according to representative samples such as cluster centers can effectively ensure the balance of the data size of different clusters. Deep learning uses the characteristics of algorithms to capture patterns in the imbalanced data to make classification and prediction more accuracy. Cost-sensitive learning guides the imbalanced learning process with the concept of ‘cost’. The optimization goal of the algorithm is to minimize the total cost of classification errors by focusing on the samples with higher error costs. ELM, as the basic classifier of the ensemble network, can guarantee the accuracy of a single network with the combination of the ensemble methods to well improve the classification performance of imbalanced datasets. Lu et al.97 collected an imbalanced formability dataset of experimental ${\\mathsf{H O I P s}},$ including $539\\mathsf{H O}\\mathsf{I P}$ and 24 non-HOIP samples. As shown in Fig. 7a, b, 9 different sampling methods including undersampling, oversampling and mixed sampling were introduced for unbalanced learning, while 10 different supervised and semi-supervised algorithms were used to select the best modeling algorithm to construct the model. After comparison, the mixed sampling method SMOTEENN has the best performance with the LOOCV accuracy and precision of the corresponding model have both reached $100\\%$ , and the accuracy of the test set has reached $95.5\\%$ . The LOOCV average accuracy of 100 random partitions and the average accuracy of the test set also exceeded $99.0\\%$ , respectively. The method of SHapley Additive exPlanations (SHAP) was used to extract and analyze important features of A-site atomic radius, A-site ionic radius, and tolerance factor to reveal the relationship with formability.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# MACHINE LEARNING STRATEGIES FOR SMALL DATA  \n\nMachine learning strategies including active learning and transfer learning have been shown to be effective methods of handling small datasets in materials science.  \n\n![](images/5dd3fab10c00c9894f764b84073db3ceb65e45cdecf3175fdfe2dc767a3374c1.jpg)  \nFig. 7 The accuracy and precision of imbalanced learning. a Accuracy and b precision metrics of various classification models in LOOCV based on different sampling methods97.  \n\n![](images/74e69ba180da7196cee85dfa1a6d8a0241b4ddb0ec35e1345d1695e15d49072a.jpg)  \nFig. 8 The workflows of active learning and transfer learning. The workflows of a active learning98 and b transfer learning17 in materia science.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# Active learning  \n\nActive learning, also known as adaptive learning, is one of the key technologies for solving small data problems. The core of active learning is to select the samples from a large number of unlabeled data for labeling to make the information in the small data represent the large unlabeled data as much as possible to realize the analysis and processing of big data under small data98. The active learning workflow consists of the following steps: (1) train the model based on the labeled training set; (2) use the model to evaluate the acquisition function in the pool of unlabeled samples; (3) label the data points with the highest acquisition function scores; (4) add the labeled data points to the training set to train the model. The learning steps of active training, scoring, labeling, and acquisition are repeated until the model reaches sufficient accuracy. In the materials design based on active learning shown in Fig. 8a, the machine learning model would be constructed to design or screen out the candidate materials for further experimental or computational validation99. Then the verified candidate samples are taken back to the training set for modeling. Active learning can continuously enlarge the data size and improve the accuracy of the model in the process to realize the two-way optimization of data and model to be applied widely in materials machine learning with small data.  \n\nThe core steps in the active learning workflow include the sampling, labeling, validation and evaluation of the significant samples from the unlabeled sample pool. The data sampling strategy used in the active learning process to filter out data points from the unlabeled sample pool is rather critical to improving the prediction accuracy of machine learning models. Common data sampling strategies include manual empirical sampling and Bayesian optimization sampling100. Manual empirical sampling refers to the manual labeling of data samples by experts using expertize and traditional experience, which highlights the importance of domain knowledge in machine learning. Bayesian optimization algorithms can automatically label the samples by using prior knowledge to approximate the posterior distribution of the unknown objective function. The basic idea of Bayesian optimization sampling is to balance the needs of ‘exploration’ and ‘exploitation’. The ‘exploitation’ samples the most likely optimal solution region based on the posterior distribution; while the ‘exploration’ is usually to obtain sampling points in areas with low sampling density in order to improve the prediction accuracy of the model and reduce the fluctuation of prediction values101. The ‘exploration’ strategy is preferred in the initial stage when data size is insufficient, and it is more focused on improving the model prediction accuracy. As the data size gradually increases and the model prediction accuracy improves, the strategy gradually shifts to the ‘exploitation’ strategy, focusing on finding the optimal target value. The acquisition function is one of the cores of Bayesian optimization, which is used to evaluate and filter the most informative sample points from the unlabeled samples to be back to the original training set to perform active learning. Common acquisition functions include upper confidence bound (UCB), probability of improvement (PI) and expected improvement (EI), and Thompson Sampling101. In materials science, validation and evaluation of the selected labeled samples are usually performed through experiments or first-principles calculations. Active learning is an iteration process. Even if the model constructed with the original small data is not ideal, the size of modeling data and model accuracy can be improved through the iteration of active learning. In addition, active learning also integrates machine learning well with experiments or firstprinciples calculations. The application of active learning in materials is no longer only in the theoretical stage, but combined with experiments or calculations through machine learning models to achieve the purpose of optimization.  \n\nIn recent years, active learning has been widely applied in materials machine learning with small data. Xue et al.102 collected 22 Ni-Ti-based shape memory alloys and the thermal hysteresis property. The algorithm of SVR combined with efficient global optimization (EGO) search was applied to construct the thermal hysteresis prediction model to design Ni-Ti-based shape memory alloys with low thermal hysteresis. Models were trained multiple times and cross-validated with initial alloy data. After the model construction, EGO was used to search for 4 samples with low thermal hysteresis from the 800,000 searched spaces for experiments. After experimental validation, the 4 samples were put back into the training set for modeling-search-experiment iteration. Of the 36 samples searched after 9 iterations, 14 samples have thermal hysteresis smaller than any of the 22 samples in the original dataset, with $\\mathsf{T i}_{50.0}\\mathsf{N i}_{46.7}\\mathsf{C u}_{0.8}\\mathsf{F e}_{2.3}\\mathsf{P d}_{0.2}$ having the smallest thermal hysteresis of 1.84 K. Zhao et al.101 developed an effective active learning model to describe the relationship between elemental composition and hardness of 6061-aluminum alloy by combining high-throughput experiments and Bayesian optimized sampling strategy. First, 32 6061-aluminum alloys with different composition ratios were prepared and characterized for hardness using a full-flow high-throughput alloy preparation and characterization system. 309 descriptors were constructed as initial features by elemental composition and alloy domain knowledge. After feature selection with variance, maximum information coefficient, weight coefficient, Pearson correlation coefficient, and sequence backward selection, the remaining 5 significant features were screened out for model construction. After comparing various algorithms, the SVR algorithm with kernel function of radial basis function was used to construct model to predict the hardness of aluminum alloys. Then, bootstrap was used to generate 1000 training datasets containing 32 samples by random sampling, and the above training datasets were used to obtain 1000 corresponding machine learning models for predicting the hardness of 33,600 candidates in the potential component space. Manual empirical sampling and Bayesian optimized sampling were used to select samples from the candidates for labeling and subsequent experiments, where the Bayesian sampling strategy specifically used 4 methods: the EGO algorithm, the knowledge gradient (KG) algorithm, the maximum hardness distribution method and the maximum error distribution method, each taking 4 data points and designing a total of 16 experimental alloy components for the next iteration of experiments at each step. The experimental data were returned to the initial dataset for further iterations of feature selection and model construction before convergence conditions were reached. After three iterations, the results showed that the adaptive sampling strategy of the Bayesian optimization algorithm could guide the experiments more effectively than manual empirical sampling, with a $63.03\\%$ reduction in MAE and a $53.85\\%$ reduction in RMSE. The hardness prediction RMSE of final model is $4.49\\mathsf{H V},$ which is close to the experimental error of 4.05 HV for the test sample. This work achieves the composition optimization of the hardness properties of 6061-aluminum alloy by the active learning strategy after Bayesian sampling optimization, which provides guidance for the design and performance optimization of other multi-alloy materials.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# Transfer learning  \n\nTransfer learning refers to the acquisition of knowledge in a given source domain and learning task to help improve the learning of the predictive model in the target domain103. Transfer learning can be divided into model-based transfer learning, relation-based transfer learning and sample-based transfer learning according to transfer methods104. The model-based transfer learning method is to improve the prediction accuracy by adjusting the parameters of the pre-trained model. Relation-based transfer learning utilizes relations for analogical transfer such as cooking according to a recipe can be compared to conducting a scientific experiment according to a report. The sample-based transfer learning method is to directly assign different weights to different samples to complete the transfer. As shown in Fig. 8b, in the materials filed, transfer learning generally refers to model-based transfer learning by serving the small data in the target domain from the big data in the source domain105. After using the materials big data of the source domain to construct the pre-trained model, the parameters of the pre-trained model are adjusted in combination with the small data of the target domain to improve the prediction accuracy of the model to the small data.  \n\nWu et al.106 developed a high-precision polymer thermal conductivity prediction model through transfer learning and Bayesian molecular design algorithm to screen out thousands of polymers with high thermal conductivity, of which 3 candidates were successfully synthesized and characterized after the experimental feasibility evaluation. A lot of polymer samples and the properties data were collected from the databases of PoLyInfo and QM9 to construct a pre-trained model107,108. After comparing different models, it was found that the pre-trained model of the heat capacity $\\mathsf{C}_{\\mathsf{v}}$ owned the highest prediction accuracy. Then, the parameters of the pre-trained model were adjusted to be transferred to the prediction of thermal conductivity by the 28 samples with thermal conductivity. The results showed that the MAE of the model after transfer learning reached 0.0204 W $(\\mathsf{m}\\cdot\\mathsf{k})^{-1}$ , which is $40\\%$ lower for directly trained models on each data point. Combined with Bayesian algorithm, a lot of repeating unit structures were designed for screening. Finally, 24 molecular structures were screened, of which 3 were successfully verified by experimental synthesis and characterization. The experimental results showed that the thermal conductivity of polymers assisted by transfer learning and Bayesian molecular design was higher than that of polymer materials in published papers. This research achievement also confirms that transfer learning and Bayesian molecular design can be successfully applied to the design and discovery of polymer materials. Lee et al.109 applied a crystal graph convolutional neural network (CGCNN) to a transfer learning model (TL-CGCNN) to improve the accuracy of material machine learning models with small data and quantitatively explored the effect of the sample size of the pre-trained and target models on the accuracy of the transfer learning model. The crystal structures and their corresponding bandgaps $E_{\\mathfrak{g}}$ and stratigraphic energies $\\Delta E_{f}$ were first collected from the Materials Project Database (MPD), a first-principles computational database. Then, three large datasets containing 10,000, 54,000, and 113,000 data, respectively, were used to train the pre-trained models in conjunction with the CGCNN. In addition, bulk modulus $(K_{\\mathsf{V R H}})_{i}$ , dielectric constant (εr) and quasiparticle bandgap $(\\mathsf{G W}\\mathbb{-}E_{\\mathsf{g}})$ data were also collected to confirm the robustness of CGCNN for more cases with insufficient data volume. The prediction accuracy of $E_{\\mathfrak{g}}$ and $\\Delta E_{f}$ from pretrained models with different sample sizes and comparison with conventional machine learning models reveals that the accuracy of TL-CGCNN models is much better than that of conventional machine learning models and the improvement of prediction ability is greater when the pre-trained models are trained with more data. The predictions of $K_{\\mathsf{V R H}},\\varepsilon_{\\mathsf{r}}$ and $\\mathsf{G W}_{\\mathsf{\\Phi}}\\mathsf{E}_{\\mathsf{g}}$ are also consistent with the above pattern and it is found that TL-CGCNN may be better for prediction model affected by small amount of data. The prediction of attributes in the target model by TLCGCNN becomes more accurate when the pre-trained model is trained with larger data and the high correlation between the pretrained model and the target model. Yamada et al.110 developed a pre-trained model library called XenonPy.MDL for transfer learning between different materials and their properties. The library has over 140,000 pre-trained models covering a wide range of materials including small molecules, polymers and inorganic crystalline materials. These pre-trained models are used to successfully span superior transferability between different materials and their properties, even beyond the different disciplines of materials science. This work provides a successful processing paradigm for small data materials machine learning using transfer learning and confirms the interconnectedness of almost all tasks in materials science, forging a bridge between small molecules and polymers, organic and inorganic materials. If the amount of collected target property data is very limited, but the amount of property data related to the target property is relatively abundant, transfer learning could be a very good choice.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# CONCLUSION AND OUTLOOK  \n\nIn this review, we discussed the dilemma of small data in materials machine learning and introduced the commonly used methods to deal with the small data machine learning from the aspects of data sources, algorithms, and machine learning strategies, including data extraction from publications, material database construction, high-throughput computations and experiments, small data modeling algorithms, imbalanced learning, active learning, and transfer learning. At present, the data size of most materials machine learning is still in the small data stage and will remain in the small data stage for a long time due to the inconsistency in the development progress, including the different types of materials, materials synthesis and characterization technology, materials classification and naming standards, database development technology, modeling algorithms and other factors. Therefore, handling small data modeling in materials machine learning is also one of the important directions. Here, we propose some future directions for further small data machine learning in materials science:  \n\n(1) Data management: In the past, data could be regarded as a series of apparent observations used to gain knowledge. But in the future, data would be more considered the information representing the results of complicated effects form multiple factors, which puts forward higher requirements for data management111. Data management includes the processes of data collection, storage, screening, labeling, annotation, augmentation, evaluation, ablation and virtualization, which is a long-term process and requires the efforts of scholars and governments around the world. In addition, the dataset tends to be fixed and the machine learning is only mainly on the specific dataset in the previous materials machine learning process. But now, data iteration has been becoming the focus and more efforts are concentrated on improving the model performance through iterative models such as active learning, which also requires a more systematic approach to data management112.  \n\n(2) Methods combination: This review introduced a variety of small data machine learning methods and strategies in materials science. These methods and strategies should be used in combination to pursue better model performance, such as the combination of experiments and calculations, active learning, and materials database construction to develop a materials development system that integrates machine learning, database, experiments and computations. Besides, these methods should be more attached to the material design philosophy. Most applications of model in this review tend to screen materials or use patterns discovered by models to design materials, which is called forward design. In the future, inverse design based on small datasets to deduce the composition and structure of materials according to the required properties is also one of the future development directions.  \n\n(3) Machine learning algorithms and strategies: In addition to materials data, machine learning algorithms and strategies are also important factors to determine the applications. This review introduced several modeling algorithms suitable for small datasets, but different algorithms are only suitable for the specific data, and there is no modeling algorithm that is generally applicable to small data. Therefore, more modeling algorithms suitable for small data still need to be developed. Similarly, machine learning strategies suitable for small data, including active learning and transfer learning, also have great potential for application and development.  \n\nThis development should take into account both data and algorithms, not only to establish a complete database or use the existing technologies to integrate materials data to increase the data size, but also to continuously develop small data modeling algorithms and machine learning strategies. In the future, machine learning will continue to occupy an increasingly important place in materials design and discovery. Especially for experimenters, this review would help better handle the precious and limited experimental data with machine learning methods to accelerate material design and discovery. A drop of water can refract the brilliance of the sun. Similarly, small materials data can also be used to explore mysterious and interesting patterns in the vast world of materials through machine learning.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 15,
+        "chunk": "# DATA AVAILABILITY  \n\nAll the data of the cases could be obtained from the corresponding references.",
+        "category": " References"
+    },
+    {
+        "id": 16,
+        "chunk": "# CODE AVAILABILITY  \n\nAll the code of the cases could be obtained from the corresponding references.  \n\nReceived: 22 September 2022; Accepted: 10 March 2023; Published online: 25 March 2023",
+        "category": " References"
+    },
+    {
+        "id": 17,
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Advances, challenges and opportunities in creating data for trustworthy AI. Nat. Mach. Intell. 4, 904 (2022).",
+        "category": " References"
+    },
+    {
+        "id": 18,
+        "chunk": "# ACKNOWLEDGEMENTS  \n\nThis work was supported by the National Natural Science Foundation of China (No. 52102140), Shanghai Pujiang Program (No.21PJD024), and the Key Research Project of Zhejiang Laboratory (No. 2021PE0AC02).",
+        "category": " References"
+    },
+    {
+        "id": 19,
+        "chunk": "# AUTHOR CONTRIBUTIONS  \n\nP.X. collected publications and completed the framework of the manuscript. X.J., M.L., and W.L. revised the manuscript.",
+        "category": " Abstract/Introduction/Materials and methods/Results and discussion/Conclusions/References \n\nThis text segment does not fit any of the provided categories; however, it is closest to a section that describes the contributions of the authors to the research paper, which is typically found in the acknowledgements or author contributions section. Since this is not one of the specified categories, I cannot classify it accordingly based on the available options."
+    },
+    {
+        "id": 20,
+        "chunk": "# COMPETING INTERESTS  \n\nThe authors declare no competing interests.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# ADDITIONAL INFORMATION  \n\nSupplementary information The online version contains supplementary material available at https://doi.org/10.1038/s41524-023-01000-z.  \n\nCorrespondence and requests for materials should be addressed to Minjie Li or Wencong Lu.  \n\nReprints and permission information is available at http://www.nature.com/ reprints  \n\nPublisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.  \n\nOpen Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http:// creativecommons.org/licenses/by/4.0/.",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# ARTICLE OPEN Machine learning assisted discovery of high-efficiency self-healing epoxy coating for corrosion protection  \n\nTong Liu1,2,3, Zhuoyao Chen1,2, Jingzhi Yang1,2, Lingwei $\\mathsf{M a}^{1,2,4}$ , Arjan Mol $\\textcircled{1}^{5}$ and Dawei Zhang $\\textcircled{10}^{1,2,4\\boxtimes}$  \n\nMachine learning is a powerful means for the rapid development of high-performance functional materials. In this study, we presented a machine learning workflow for predicting the corrosion resistance of a self-healing epoxy coating containing $Z|F-8@C{\\mathsf{a}}$ microfillers. The orthogonal Latin square method was used to investigate the effects of the molecular weight of the polyetheramine curing agent, molar ratio of polyetheramine to epoxy, molar content of the hydrogen bond unit (UPy-D400), and mass content of the solid microfillers $(\\boldsymbol{Z}|\\mathsf{F}-8@\\mathsf{C}\\mathsf{a}$ microfillers) on the low impedance modulus $(\\log\\vert Z\\vert_{0.01\\mapsto1z})$ values of the scratched coatings, generating 32 initial datasets. The machine learning workflow was divided into two stages: In stage I, five models were compared and the random forest (RF) model was selected for the active learning. After 5 cycles of active learning, the RF model achieved good prediction accuracy: coefficient of determination $(R^{2})=0.709$ , mean absolute percentage error $(\\mathsf{M A P E})=0.081$ , root mean square error $(\\mathsf{R M S E})=0.685\\ (\\mathsf{l g}(\\Omega\\cdot\\mathsf{c m}^{2}))$ . In stage II, the best coating formulation was identified by Bayesian optimization. Finally, the electrochemical impedance spectroscopy (EIS) results showed that compared with the intact coating $((4.63\\pm2.08)\\times10^{11}\\Omega{\\cdot}\\mathrm{cm}^{2})_{i}$ , the $|Z|_{0.01\\mathsf{H z}}$ value of the repaired coating was as high as $(4.40\\pm2.04)\\times10^{11}\\Omega{\\cdot}\\mathrm{cm}^{2}$ . Besides, the repaired coating showed minimal corrosion and $3.3\\%$ of adhesion loss after 60 days of neutral salt spray testing.  \n\nnpj Materials Degradation  (2024) 8:11 ; https://doi.org/10.1038/s41529-024-00427-z",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 2,
+        "chunk": "# INTRODUCTION  \n\nEpoxy (EP) resin is widely used in the field of corrosion protection because of strong adhesion properties, high corrosion resistance, excellent mechanical properties and low cost. However, cracks may arise inside or at the surface of the EP matrix during longterm service and reduce its corrosion protection performance with time, thus increasing potential safety hazards during its service life1. The application of self-healing coatings will be the most common and cost-effective method of improving the corrosion protection and thus the durability of metallic structures. A wide range of engineering structures from vehicles to aircrafts, from factories to house-hold equipment can be effectively protected via the self-healing coating systems. Recent efforts have focused on improving the durability of EP coatings in the presence of damage by granting them self-healing functions, which can be realized through intrinsic repair of the material matrix by reversible covalent bonds2 and noncovalent bonds3, or via extrinsic strategies depending on the release of healing agents4 and corrosion inhibitors5 into coating defects. In contrast to these extrinsic self-healing mechanisms, the intrinsic one endows the coating with the ability to simulate natural systems and repeated repairability. Such mechanisms are typically based on reversible covalent bonds via disulfide bonds6, Diels–Alder reactions7, and hydrazone bonds8, or non-covalent interactions via metal-ligand9 and hydrogen bonding10–12. Among these mechanisms, the most promising one is based on dynamic hydrogen bonds because of their high reversibility and mild repair conditions, in combination with their directional and tunable self-association properties13. As an indication of the self-healing ability of the coating, the lowfrequency impedance modulus, such as according to the electrochemical impedance spectroscopy (EIS) data measured at  \n\n$0.01\\mathsf{H z}\\ (|Z|_{0.01\\mathsf{H z}}),$ were extensively used to estimate the overall corrosion resistance of the test area14,15. A higher $|Z|_{0.01\\mathsf{H z}}$ value represents a higher barrier ability of the coating. Based on the previous studies16, in our view the design of an ideal self-healing corrosion protective coating should have the following main index: (1) The $|Z|_{0.01\\mathsf{H z}}$ value of the self-healed coating is nearly close to that of the intact coating; (2) excellent barrier ability, $|Z|_{0.01\\mathsf{H z}}$ value more than $10^{10}\\ \\Omega{\\cdot}\\mathsf{c m}^{2},$ ; (3) long-term stability in corrosive environments both before and after repair. For example, in a previous work by our group11, an intrinsic self-healing EP coating was developed by grafting 2-ureido-4[1H]-pyrimidinone (UPy) as a quadruple hydrogen bonding unit onto the backbones of an EP-matrix. The UPy/EP coating demonstrated high-efficient self-healing functionality within 5 min in $3.5\\ \\mathsf{w t}.\\%$ NaCl solution. The self-healed coating still had high $|Z|_{0.01\\mathsf{H z}}$ value of $4.8\\times10^{10}$ $\\scriptstyle\\Omega\\cdot\\mathsf{c m}^{2}$ even after 60 days of immersion in NaCl solution.  \n\nOften, the achievement of the target performance of selfhealing implies synergy between multiple components of the EP coating formulation, including different resins, curing agents, liquid/solid additives, etc. The conventional trial-and-error design strategy for coating formulation is time-consuming and laborintensive. Recently, machine learning methods have show to represent a promising option for materials design and optimization, especially for systems with complex properties or compositions17–21. For example, Haik et al.22 developed a machine learning model to predict the stress relaxation properties of EP matrix composites, based on a three-layer neural network model using initial stress, test temperature and operating time as input variables and stress relaxation behavior as output. The final model was obtained by training 9000 experimental data samples. This model can predict efficiently the time-dependent mechanical behavior of a viscoelastic or a viscoplastic material. Kan et al.23 constructed a molecular recognition model for predicting 2000 molecular descriptors from chemical structures using a gated graph neural network, and extracted 32-dimensional vectors representing 2000 molecular descriptors through the molecular recognition model to complete the dimension reduction. This 32- dimensional vector was used as the input value for the next Gaussian regression, and the machine learning model for predicting electrical conductivity was finally built by training a large amount of data. Typically, the establishment of an accurate machine learning requires vast training data, which is difficult to be obtained for polymer resin formation considering the heavy experimental workload in the synthesis and characterization24,25. Therefore, the construction of small sample datasets in the machine learning aspect of the research method has major implications for polymer design.  \n\n![](images/b30c9e8b421045d32d2843116104e013c2e0c650008ac7f46fc662d4cbd6c31c.jpg)  \nFig. 1 A machine learning workflow for performance optimization in self-healing EP composite coating. Four steps are involved in machine learning workflow, from a data acquisition, b active learning, c Bayesian optimization, and d experimental verification.  \n\nThe problem of machine learning under small sample data conditions $_{<1000}$ samples) has received much attention in recent years26,27. For the processing of small sample data, the most common methods are the neural-network-based methods28, hierarchical machine learning29, active-learning-based method30 and so on. For instance, Li et al.31 proposed a model combined with nearest neighbor interpolation (NNI), synthetic minority oversampling technique (SMOTE) and extreme gradient boosting (XGBoost) models to predict the abrasion of rubber composites with small samples. NNI and SMOTE are two classical models in image processing that aim at increasing the sample size and solving the problem of sample unevenness. Combining these two models, the original dataset was expanded from 23 to 710 samples. Finally, the abrasion was predicted by the XGBoost model to yield a better prediction accuracy $(\\mathsf{M S E}=0.001$ ). Similarly, active learning has been applied to discover EP adhesive strength30, polymer molecular dynamics32, high- $\\cdot\\tau_{g}$ polymers33,34 and among others from the small initial datasets.  \n\nHerein, we employed a machine learning framework to develop self-healing composite coatings for corrosion protection applications. A flowchart of the machine learning workflow is shown in Fig. 1. In the machine learning framework, active learning and Bayesian optimization to model and maximize the common logarithm of the low-frequency impedance modulus $(\\log\\lvert Z\\rvert_{0.01\\mapsto l z})$ obtained from EIS measurements for various scratched selfhealing EP composite coatings to improve its self-healing property. This coating formulation consists of an EP resin, polyetheramines, amino-terminated urea-pyrimidinone monomers (UPy-D400) and $Z|F-8@C{\\mathsf{a}}$ microfillers. The EP resin mixed with polyetheramine can react to form an EP-based polymer, and the UPy-D400 acts as a quadruple hydrogen bonding unit that can be grafted into the EP network to provide a self-healing function for the EP polymer via the self-association process; The ZIF- $\\boldsymbol{\\cdot}8@{\\mathsf{C}}\\mathsf{a}$ microfiller, which is an empty ${\\mathsf{C a C O}}_{3}$ carbonate microcontainer with ZIF-8 nanoparticles assembled on the surface, is incorporated as a model filler that can not only enhance the barrier property of EP coating, but also present a pH-sensitive response to release loaded substance (e.g., inhibitors) to achieve useful functions. For the machine learning process, four-parameter variables, molecular weights of polyetheramine, the molar ratio of polyetheramine to EP, UPy-D400 content, and $Z|F-8@C{\\mathsf{a}}$ content, were used as input, and the $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ value of the scratched coatings was used as output; 32 initial dataset were obtained from the preliminary experiment. Among the five common models, the model with the best accuracy was selected, and trained to achieve the best accuracy by active learning. Subsequently, the Bayesian optimization method was used to search for the scratched self-healing EP composite coating with an extremely high $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ value. Finally, the self-healing and corrosion protective properties of the optimal coating were verified by EIS and salt spray testing.  \n\nTable 1. Summary of variable parameters for coating formulation used at the active learning stage.   \n\n\n<html><body><table><tr><td rowspan=\"2\">Serial number</td><td colspan=\"3\">Variable parameter</td></tr><tr><td>MWc r (g·mol-1)</td><td>UPy-D400 content (mol%)</td><td>ZIF-8/Ca content (wt.%)</td></tr><tr><td>１ 2</td><td>230 0.55 400 0.70</td><td>5 10</td><td>5.5 7.0</td></tr><tr><td>3 4</td><td>2000 0.85 4000 1.00 20</td><td>15</td><td>8.5 10.0</td></tr><tr><td colspan=\"4\">Variable parameters include the molecular weight of polyetheramine curing agent, molar ratio of polyetheramine to EP (r), molar content of UPy- D400 and mass content of ZiF-8/Ca microfillers.</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# RESULTS AND DISCUSSION",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# Experimental results from the initial dataset  \n\nAs seen in Table 1, four parameters with four initial condition levels were set (total experimental conditions $=4^{4}=256$ sets).  \n\nTable 2. Experimental results of $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ values of scratched   \n\n\n<html><body><table><tr><td colspan=\"6\">coatings prepared under various conditions (32 initial dataset), the Ig|Zlo.01Hz values represent the average ± standard deviations.</td></tr><tr><td rowspan=\"2\">Serial number</td><td colspan=\"5\">Variable parameter</td></tr><tr><td>MWc (g·mol-1)</td><td>r</td><td>UPy-D400 content (mol%)</td><td>ZIF-8/Ca content (wt.%)</td><td>Measured Ig((Z//Ω2·cm²)</td></tr><tr><td>1</td><td>230</td><td>0.55 5</td><td></td><td>5.5</td><td>4.89 ± 0.72</td></tr><tr><td>２</td><td>230</td><td>0.70 10</td><td></td><td>8.5</td><td>5.12 ± 0.69</td></tr><tr><td>3</td><td>230</td><td>0.85 15</td><td></td><td>10.0</td><td>6.06 ± 0.22</td></tr><tr><td>4</td><td>230</td><td>1.00</td><td>20</td><td>7.0</td><td>8.91 ± 0.76</td></tr><tr><td>5</td><td>400</td><td>0.55</td><td>10</td><td>7.0</td><td>4.75 ± 0.83</td></tr><tr><td>６</td><td>400</td><td>0.70 5</td><td></td><td>10.0</td><td>5.39 ± 0.45</td></tr><tr><td>7</td><td>400</td><td>0.85 20</td><td></td><td>8.5</td><td>10.08 ± 0.72</td></tr><tr><td>8</td><td>400</td><td>1.00</td><td>15</td><td>5.5</td><td>10.55 ± 0.52</td></tr><tr><td>９</td><td>2000</td><td>0.55</td><td>15</td><td>8.5</td><td>8.35 ± 0.41</td></tr><tr><td>10</td><td>2000</td><td>0.70</td><td>20</td><td>5.5</td><td>10.05 ± 0.76</td></tr><tr><td>11</td><td>2000</td><td>0.85 5</td><td></td><td>7.0</td><td>9.12 ± 0.69</td></tr><tr><td>12</td><td>2000</td><td>1.00</td><td>10</td><td>10.0</td><td>7.23 ± 0.82</td></tr><tr><td>13</td><td>4000</td><td>0.55</td><td>20</td><td>10.0</td><td>8.94± 0.70</td></tr><tr><td>14</td><td>4000</td><td>0.70</td><td>15</td><td>7.0</td><td>8.04± 0.59</td></tr><tr><td>15</td><td>4000</td><td>0.85</td><td>10</td><td>5.5</td><td>8.43 ± 0.28</td></tr><tr><td>16</td><td>4000</td><td>1.00 5</td><td></td><td>8.5</td><td>6.44± 0.65</td></tr><tr><td>17</td><td>230</td><td>0.55</td><td>20</td><td>7.0</td><td>4.88 ± 0.70</td></tr><tr><td>18</td><td>230</td><td>0.70 5</td><td></td><td>5.5</td><td>4.93 ± 0.63</td></tr><tr><td>19</td><td>230</td><td>0.85</td><td>10</td><td>8.5</td><td>5.59 ± 0.69</td></tr><tr><td>20</td><td>230</td><td>1.00</td><td>15</td><td>10.0</td><td>7.97 ± 0.70</td></tr><tr><td>21</td><td>400</td><td>0.55</td><td>15</td><td>5.5</td><td>5.01 ± 0.81</td></tr><tr><td>22</td><td>400</td><td>0.70</td><td>10</td><td>7.0</td><td>7.31± 0.42</td></tr><tr><td>23</td><td>400</td><td>0.85 5</td><td></td><td>10.0</td><td>8.12 ± 0.62</td></tr><tr><td>24</td><td>400</td><td>1.00</td><td>20</td><td>8.5</td><td>10.87 ± 0.80</td></tr><tr><td>25</td><td>2000</td><td>0.55</td><td>10</td><td>10.0</td><td>6.14±0.75</td></tr><tr><td>26</td><td>2000</td><td>0.70</td><td>15</td><td>8.5</td><td>9.29 ± 0.62</td></tr><tr><td>27</td><td>2000</td><td>0.85</td><td>20</td><td>5.5</td><td>8.98 ± 0.74</td></tr><tr><td>28</td><td>2000</td><td>1.00 5</td><td></td><td>7.0</td><td>6.92 ± 0.70</td></tr><tr><td>29</td><td>4000</td><td>0.55</td><td>5</td><td>8.5</td><td>6.93 ± 0.62</td></tr><tr><td>30</td><td>4000</td><td>0.70</td><td>20</td><td>10.0</td><td>8.35± 0.52</td></tr><tr><td>31</td><td>4000</td><td>0.85</td><td>15</td><td>7.0</td><td>9.15 ± 0.66</td></tr><tr><td>32</td><td>4000</td><td>1.00</td><td>10</td><td>5.5</td><td>6.95 ± 0.79</td></tr></table></body></html>  \n\nFour parameter variables included the molecular weight of polyetheramine, molar ratio of polyetheramine to EP, the molar content of UPy-D400, and mass content of the $Z|F-8@C{\\mathsf{a}}$ microfillers. An initial 32 sets of experimental conditions were extracted from the 256 sets by orthogonal Latin square design method35. This is a method based on mathematical statistics and the orthogonality principle, which can achieve the equivalent results of a large number of comprehensive tests with the minimum number of tests. It selects a part of points which can represent the whole experiment according to the orthogonality of the experiments. And these selected points are uniformly distributed in the whole space36,37. Then, the coatings were prepared for EIS measurements according to these 32 conditions, the corresponding the low impedance modulus $(\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ value) of different scratched coatings was obtained. The reason for selecting $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ value as the output instead of using $|Z|_{0.01\\mathsf{H z}}$ value is to eliminate the undesirable effects caused by sample dataset with high variability.  \n\n![](images/dd6acf985492f5cdd9ce8b98401dd7d9683c552ef2ac68a73ab35ac1f3275469.jpg)  \nFig. 2 Distribution of $\\mathbf{\\|\\bigcirc\\|}Z\\mathbf{\\|_{0.01\\:\\mathsf{Hz}}}$ experimental values from the 32 initial dataset. This task aims to confirm the distribution of target property values under initial experimental conditions.  \n\nMeasurements of $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ experimental values of scratched coatings that comprise our initial dataset are reported in Table 2. Figure 2 shows the distribution of $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ experimental values. As shown in Fig. 2, the average $\\mathsf{l g}|\\boldsymbol{Z}|_{0.01\\mathsf{H z}}$ experimental values were widely distributed in the range of 4.75–10.87 $(\\mathsf{l}\\mathsf{g}(\\Omega\\cdot\\mathsf{c m}^{2}))$ . According to a previous experimental study11, the scratched coatings with different self-healing abilities are involved in this distribution, indicating that the selection of the initial preparation conditions using the orthogonal Latin square method is reasonable.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# Assessment and selection of an $\\mathbf{\\boldsymbol{\\mathsf{I}}}\\mathbf{\\boldsymbol{\\mathsf{g}}}|\\mathbf{\\boldsymbol{Z}}|_{0.01\\mathsf{H z}}$ values prediction model  \n\nNext step, different experimental conditions and corresponding $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ value of scratched coating were used as the input and output of the machine learning process, respectively, and five common machine learning models were trained using 32 initial datasets. A comparison of the predicted and measured $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ values for each model is shown in Fig. 3a, e. A black dashed straight line indicates equal measured and predicted values. A comparison of the accuracy of each model is shown in Fig. 3f. Compared with the other models, the RF model yielded the best accuracy in terms of a higher coefficient of determination $(R^{2})$ value, and lower mean absolute percentage error (MAPE) and root mean square error (RMSE) values. This may be due to its deeper layers of model structure than general machine learning models; RF models possessed a good processing ability for data with high variability38,39. Hence, the RF model was chosen to predict the $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ values in subsequent steps.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# Active learning and machine learning model performance  \n\nFor the active learning process, the RF model first predicted the lg| $Z|_{0.01\\mathsf{H z}}$ values of all $256\\textrm{--}32=224$ sets) possible experimental conditions from the 32 initial dataset. The predicted $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ values were ranked in descending order. The five top-ranked experimental conditions from 224 sets of conditions were selected as proposals for subsequent measurements to be performed in the laboratory. These five measurements were added to the initial 32 datasets. Then, the machine learning model for the prediction of the $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ values was trained again on this improved $(32+5)$ dataset. The new measurements were re-used in the RF model to improve the accuracy, as this can enhance the prediction accuracy for high-target performance samples in a targeted manner and improve the active learning efficiency. This process, from the prediction phase to the reuse phase, represents one cycle of active learning (see Table 3). This active learning process is repeated until the preliminary goal of the best accuracy of the machine learning model is achieved. In this study, the active learning cycle was stopped if all the evaluation indices (MAPE, RMSE and $R^{2}$ ) stopped increasing.  \n\n![](images/6737f76d82306573523c5d04f21d9340754bf45640eb689abcf5d0b4071b2ad5.jpg)  \nFig. 3 The selection of the best machine learning model. Distribution of predicted versus measured $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ values from successive test sets used in the 10-fold cross-validation using different machine learning models, a–e correspond to artificial neural network (ANN), linear regression (LR), support vector regression (SVR), decision tree (DT) and random forest (RF) model, respectively. f A comparison of the accuracy for each model, including $R^{2}$ , MAPE, and RMSE values.  \n\nFigures $_{4a-9}$ present scatter plots of the predicted versus measured $\\mathsf{l g}|Z|_{0.01\\mathsf{H z}}$ values from the initial dataset to the last cycle. The blue and red dots indicate existing and new measurements, respectively. The evolution of the corresponding $R^{2}$ , MAPE and RMSE values for each cycle is summarized in Fig. 4h, i. As shown in Figs. ${4a-g},$ the predicted and measured values gradually approached the black dashed straight line from the initial dataset to the last cycle, indicating that an increase in the dataset size resulted in predicted $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ values that are closer to measured $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ values. As the dataset size increased, $R^{2}$ clearly increased, and the MAPE and RMSE decreased gradually. After five active learning cycles, the $R^{2}$ , MAPE and RMSE values reached equilibrium, at this time, the active learning process was terminated. For the dataset of 62 samples, the RF model achieved $R^{2}$ , MAPE and RMSE values of 0.709, 0.081 and 0.685 $(\\mathsf{l g}(\\Omega\\cdot\\mathsf{c m}^{2}))$ , respectively. Compared to the accuracy of the initial dataset, improvements of $246\\%$ , $51\\%$ and $47\\%$ were achieved for $R^{2}$ , MAPE, and RMSE, respectively. In this case, $R^{2}$ was greater than 0.7 and both MAPE and RMSE were stabilized at a low level, indicating that the RF model reached acceptable accuracy. Therefore, the active learning procedure was stopped at this stage and the RF model was fixed based on the existing dataset.  \n\nIn addition, Table 3 lists the top-five proposed experiments for the five cycles of active learning with the corresponding predicted and measured $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ values. Several measured $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ values in Table 3 that were greater than 11.00 $(\\mathsf{l g}(\\Omega\\cdot\\mathsf{c m}^{2}))$ , which is greater than the highest value in the initial dataset, showed that the RF model allowed us to predict the experimental conditions of the coating with a potentially high self-healing ability. These additional data on high-performance self-healing coatings are beneficial for further maximization using Bayesian optimization. In addition, the proposed experiments required polyetheramine of molecular weights 400 and $2000\\ {\\mathsf{g}}{\\cdot}{\\mathsf{m o l}}^{-1}$ , with an $r$ value greater than 0.85, $10{-}20\\mathrm{mol}\\%$ of UPy-D400, and ZIF- $8@C a$ microfiller content in the full range. This provided the main guidance for refining the test conditions in the subsequent step.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# Bayesian optimization for screening optimal candidate  \n\nIn this step, three experimental conditions were refined: r values, molar ratio of UPy-D400, and microfiller content were varied from 0.85 to 1.00, 10 to $20\\mathrm{mol}\\%$ , and 5.5 to $10.0\\mathrm{~wt.\\%}$ , by increments of 0.1, $1\\mathrm{mol}\\%$ , and $0.1~\\mathrm{wt}.\\%$ , respectively. The molecular weights of the polyetheramine curing agents were fixed at 400 and $2000g\\cdot m{\\mathsf{o l}}^{-1}$ . Obviously, this search space for the coating formulation is vast, and the machine learning model has limited utility if it do not incorporate uncertainty and the expected improvement process. Since a machine learning model is built using a limited amount of training data, the selection of candidates using that model may be limited to a local search. Therefore, we speculate that Bayesian optimization may give better results because this optimization technique considers the uncertainty of the prediction and the balance between local and global search40.  \n\nBayesian optimization works on a surrogate model and evaluates a utility function41. The utility function uses the mean and standard deviation of the candidates estimated by the surrogate model. The utility function encodes a trade-off between the exploitation (candidate searching at points with high mean) and exploration (candidate searching at points with high uncertainty). Herein, we have used RF as the surrogate model and expected improvement (EI) as a utility function. The EI is defined as the following Eqs. (1)- $(2)^{42}$ :  \n\n$\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$   \n\n\n<html><body><table><tr><td>Tabie 3. Expenmenta</td><td></td><td colspan=\"5\">proposeacond</td></tr><tr><td rowspan=\"2\">Cycle</td><td rowspan=\"2\">Rank</td><td colspan=\"5\">Variable parameter</td></tr><tr><td>MWc (g·mol-1)</td><td>UPy-D400 content (mol%)</td><td>ZIF-8/Ca content (wt.%)</td><td>Predicted lg(Z|/s2·cm2)</td><td>Measured lg(Z|/s2·cm2)</td></tr><tr><td>Initial</td><td>1</td><td>400</td><td>1.00 20</td><td>5.5</td><td>10.49 ± 0.32</td><td>10.15 ± 0.30</td></tr><tr><td></td><td>2</td><td>400 1.00</td><td>20</td><td>7.0</td><td>9.96 ± 0.24</td><td>10.88 ± 0.44</td></tr><tr><td rowspan=\"7\">Cycle 1</td><td>3</td><td>400</td><td>0.85 10</td><td>5.5</td><td>9.71 ± 0.14</td><td>10.3 ± 0.41</td></tr><tr><td>4</td><td>2000 0.85</td><td>15</td><td>5.5</td><td>8.93 ± 0.29</td><td>8.35 ± 0.62</td></tr><tr><td>5</td><td>2000</td><td>0.85 20</td><td>8.5</td><td>9.33 ± 0.20</td><td>9.05 ± 0.75</td></tr><tr><td>1</td><td>400</td><td>0.85 20</td><td>7.0</td><td>10.14 ± 0.19</td><td>10.11 ± 0.44</td></tr><tr><td>2</td><td>400 1.00</td><td>20</td><td>10.0</td><td>9.88 ± 0.17</td><td>10.24 ± 0.13</td></tr><tr><td>3</td><td>400</td><td>1.00 15</td><td>7.0</td><td>9.52 ± 0.20</td><td>10.52 ± 0.46</td></tr><tr><td>4</td><td>2000</td><td>1.00 10</td><td>7.0</td><td>9.57± 0.18</td><td>8.23 ± 0.29</td></tr><tr><td rowspan=\"5\">Cycle 2</td><td>5</td><td>400</td><td>0.85 20</td><td>10.0</td><td>9.65 ± 0.17</td><td>9.52 ± 0.51</td></tr><tr><td>1</td><td>400</td><td>0.85 15</td><td>5.5</td><td>10.27 ± 0.21</td><td>10.08 ± 0.30</td></tr><tr><td>2</td><td>400</td><td>1.00 15</td><td>8.5</td><td>10.23 ± 0.25</td><td>11.03 ± 0.38</td></tr><tr><td>3</td><td>400</td><td>0.85 15</td><td>7.0</td><td>10.03 ± 0.15</td><td>10.76 ± 0.46</td></tr><tr><td>4</td><td>400</td><td>1.00 15</td><td>10.0</td><td>9.90 ± 0.20</td><td>9.63 ± 0.64</td></tr><tr><td rowspan=\"5\">Cycle 3</td><td>5</td><td>400</td><td>0.85 15</td><td>8.5</td><td>10.31 ± 0.12</td><td>10.26 ± 0.71</td></tr><tr><td>1</td><td>400</td><td>0.85 15</td><td>10.0</td><td>9.44± 0.24</td><td>10.25 ± 0.75</td></tr><tr><td>2</td><td>2000</td><td>0.85 15</td><td>7.0</td><td>9.12 ± 0.35</td><td>9.62 ± 0.54</td></tr><tr><td>3</td><td>2000</td><td>0.85 15</td><td>8.5</td><td>9.37 ± 0.36</td><td>9.94 ± 0.48</td></tr><tr><td>4</td><td>2000</td><td>1.00 15</td><td>5.5</td><td>8.91 ± 0.44</td><td>9.41 ± 0.38</td></tr><tr><td rowspan=\"5\">Cycle 4</td><td>5</td><td>2000</td><td>1.00 15</td><td>8.5</td><td>9.43± 0.18</td><td>9.22 ± 0.15</td></tr><tr><td>1</td><td>2000</td><td>0.85 15</td><td>10.0</td><td>9.40 ± 0.30</td><td>9.68 ± 0.80</td></tr><tr><td>2</td><td>2000</td><td>0.85 20</td><td>8.5</td><td>9.30 ± 0.25</td><td>9.03 ± 0.68</td></tr><tr><td>3</td><td>2000</td><td>1.00 15</td><td>10.0</td><td>9.30 ± 0.20</td><td>9.84± 0.51</td></tr><tr><td>4</td><td>2000</td><td>1.00 15</td><td>7.0</td><td>9.24 ± 0.22</td><td>9.10 ± 0.74</td></tr><tr><td rowspan=\"6\">Cycle 5</td><td>5</td><td>2000</td><td>1.00 20</td><td>8.5</td><td>9.00 ± 0.18</td><td>9.62 ± 0.48</td></tr><tr><td>1</td><td>2000</td><td>0.85 20</td><td>7.0</td><td>9.04± 0.10</td><td>9.18 ± 0.84</td></tr><tr><td>2</td><td>2000</td><td>0.85 20</td><td>10.0</td><td>9.28 ± 0.08</td><td>9.45 ± 0.54</td></tr><tr><td>3</td><td>2000</td><td>1.00 20</td><td>10.0</td><td>9.06 ± 0.15</td><td>9.21 ± 0.69</td></tr><tr><td>4</td><td>2000</td><td>1.00 20</td><td>5.5</td><td>8.99 ± 0.18</td><td>9.30 ± 0.50</td></tr><tr><td>5</td><td>2000</td><td>0.85 20</td><td>7.0</td><td>9.16 ± 0.20</td><td>9.09 ± 0.25</td></tr></table></body></html>\n\nInitial step: the top-five proposed experiments were obtained by a model trained on initial 32 samples in the range of remaining 224 untested experiments; Cycle 1: From the remaining 219 untested experiments, the another top-five proposed experiments were obtained by a model trained on 37 samples. Cycle $2\\sim5$ utilized the same method to obtain new proposed experiment and train the model.  \n\n$$\n\\mathsf{E I}(\\mathsf{x})=\\sigma(\\mathsf{x})[z\\Phi(z)+\\phi(z)]\n$$  \n\n$$\n{\\boldsymbol{\\ z}}=[\\mu(\\mathbf{x})-\\mathbf{f}(\\mathbf{x}^{+})-\\varepsilon]/\\sigma(\\mathbf{x})\n$$  \n\nwhere $E I(x)$ represents the expected improvement value for each coating formulation candidate. $\\mu$ and $\\sigma$ are the predicted output and standard deviation of the candidates obtained from the surrogate model, $f(x^{+})$ is the maximum value of the target material property observed in the training data set. $\\phi$ represents the cumulative distribution function and $\\phi$ is the probability distribution function assuming the target property values follows the normal distribution. The term ε regulates the amount of exploration, higher the value of ε more is the exploration. In this method, the largest EI value represents the most promising coating formulation candidate. Here, we use 1000 iterations for BO run, as this was sufficiently many to predict the optimal experimental conditions with high accuracy (see Data Availability section for where to access this code), and a series of experiments were conducted starting from rank 1 (Table 4). The new highest lg| $Z|_{0.01\\mathsf{H z}}$ values of $11.58\\pm0.28$ $(\\mathsf{l}\\mathsf{g}(\\Omega\\cdot\\mathsf{c m}^{2}))$ was observed, that is, $(4.40\\pm2.04)\\times10^{11}\\Omega{\\cdot}\\mathrm{cm}^{2}.$ This impedance modulus value was considerably high compared with those reported in previous studies on EP-based self-healing coating $11,43-\\dot{4}6$ , which reported a typical $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ value range of $7.48\\substack{-10.68}$ $(\\mathsf{l}\\mathsf{g}(\\Omega\\cdot\\mathsf{c m}^{2}))$ . The suggested experimental conditions from Bayesian optimization showed that a relatively low molecular weight of polyetheramine and a high molar ratio of polyetheramine to EP were promising conditions for achieving a high $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ value, whereas the molar ratio of UPy-D400 and microfillers content should be in the middle of their defined range. According to previous studies47,48, excessive amine addition improves the shape recovery rate of EP materials. The intrinsic self-repair process mentioned in this study is realized by a self-healing unit (hydrogen bond) selfassociation process on the premise that the damage can be physically closed. A high shape recovery rate is beneficial for the physical closure of scratched material surfaces11. Excess amine (excessive r value) leads to higher flexibility but lower mechanical strength of EP materials47, an optimum combination of high strength and good flexibility can be achieved by adjusting the $r$ value precisely through Bayesian optimization. The introduction of self-healing units and microfillers may also affect the various performance indicators of the coatings, which can balance each addition amount simultaneously to achieve a reasonable design for target property.  \n\n![](images/acdf10c6345288dfc1e83c6b642a845d2e17b535f644a8ef0fedb9062f37b5a9.jpg)  \nFig. 4 Active learning process. a–g Correlation scatter plots of predicted and measured $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ values using different datasets, including initial dataset and cycle 1-6 datasets. h, i Comparison of the accuracy $({\\cal R}^{2}$ , RMSE and MAPE value) of the RF model for different datasets.  \n\n<html><body><table><tr><td colspan=\"6\">Table 4. Proposed preparations of a composite coating at Bayesian optimization stage with the related experimental lg|Zlo.o1Hz values of scratched coatings.</td></tr><tr><td colspan=\"6\">Rank Variable parameter</td></tr><tr><td></td><td>MWc r (g·mol-1)</td><td>UPy content (mol%)</td><td>ZIF-8/Ca content (wt.%)</td><td>Predicted Ig(Z)/ Ω·cm²)</td><td>Measured lg(|Z|/Ω·cm²)</td></tr><tr><td>１</td><td>400 0.94</td><td>14</td><td>7.8</td><td>11.01</td><td>11.58±0.28</td></tr><tr><td>２</td><td>400 0.97</td><td>17</td><td>8.0</td><td>10.92</td><td>11.15 ± 0.65</td></tr><tr><td>3</td><td>400 1.00</td><td>16</td><td>8.0</td><td>10.92</td><td>10.98 ± 0.40</td></tr><tr><td>4</td><td>400 0.95</td><td>20</td><td>8.8</td><td>10.88</td><td>10.85 ± 0.74</td></tr><tr><td>５</td><td>400 1.00</td><td>16</td><td>7.4</td><td>10.88</td><td>10.90 ± 0.68</td></tr></table></body></html>  \n\nFigure 5 shows the distribution of $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ values of scratched coatings from the initial dataset, after the five active learning cycles, and after a Bayesian optimization process. The $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ values from the initial dataset were spread randomly from 4.75 to 10.87 $(\\mathsf{l}9(\\Omega\\cdot\\mathsf{c m}^{2}),$ . By comparison, all samples that followed an active learning cycle exhibited a high $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ value $(>8.23$ $(\\mathsf{l g}(\\Omega\\cdot\\mathsf{c m}^{2})))$ , and one sample from the Bayesian optimization dataset showed an exceptionally high $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ value. These results demonstrate the potential of our machine learning framework for the design and optimization of high-performance functional materials based on small sample conditions.  \n\nInterpretation of machine learning model for coating design EIS measurements were conducted on the scratched pure commercial EP and ZIF- ${\\cdot8@\\mathsf{C a}/\\mathsf{E P}}$ coatings and their corresponding intact coatings to study the self-healing and corrosion resistance properties. The $Z|\\mathsf{F}{-}8@\\mathsf{C a}/\\mathsf{E P}$ coating was prepared based on the best formulation selected by Bayesian optimization. Nyquist and Bode plots of the intact coatings were obtained by EIS after $30\\mathrm{min}$ of immersion in $3.5\\ \\mathsf{w t}.\\%$ NaCl solution (Fig. 6a–c). Figure 6d–i show the Nyquist and Bode plots of the steels with scratched coatings after immersion for 1, 15, 30 and $60~\\mathsf{d}$ . The as-used pure EP coating was prepared by mixing E51 with D400 polyetheramine curing agents at a molar ratio of 5:3. For the pure EP sample, the intact coating initially showed a high barrier property with large capacitive arc in the Nyquist plot (Fig. 6a) and the high $|Z|_{0.01\\mathsf{H z}}$ value $(3.98\\times10^{10}~\\Omega{\\cdot}\\mathsf{c m}^{\\hat{2}})$ in the Bode plot (Fig. 6b). The phase angles in the high frequencies $(10^{5}\\mathsf{H z})$ were close to $-90^{\\circ}$ which indicates the capacitive character of the coatings. In contrast to the intact pure EP coating, intact ZI $\\mathsf{F}{-}8@\\mathsf{C a}/\\mathsf{E P}$ coating exhibited a slightly larger capacitive arc in terms of Nyquist plot, and $|Z|_{0.01\\mathsf{H z}}$ value rose to $3.8\\dot{2}\\times10^{11}\\Omega{\\cdot}\\mathrm{cm}^{2}$ , indicating substantial improvement in the barrier property of the coating after the machine learning adjustment. The average and standard deviation of the $|Z|_{0.01\\mathsf{H z}}$ value for intact coating were calculated using six parallel samples, expressed as $(4.63\\pm2.08)\\times10^{11}\\Omega{\\cdot}\\mathrm{cm}^{2}$ .  \n\n![](images/e7c1bdabee074993eb6e101b9c0857235babbe2dbe22a74feb09ed1a3090a0be.jpg)  \nFig. 5 Comparison of the measured target performance for each machine learning stage. Distribution of measured $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ values from the initial dataset (blue), after active learning process (dark blue) and after Bayesian optimization (red).  \n\nIn terms of the scratched coatings, the capacitive arcs of the pure EP coating shrank and the $|Z|_{0.01\\mathsf{H z}}$ values declined gradually over the entire immersion time, demonstrating the continuous deterioration of the barrier property (Figs. 6d–e). Subsequently, for the phase diagrams in Fig. 6f, scratched pure EP showed two-time constants: one related to the charge transfer process at the coating/substrate interface $(10^{-2}-10^{\\bar{0}}\\mathsf{H z}).$ and the other related to the resistance increase by means of corrosion product formation in the artificial defect $(10^{1}-10^{5}\\mathsf{H z})^{49}$ . Compared with the Bode plots for pure EP coating, the Bode plots of the scratched coating showed approximately $-45^{\\circ}$ straight lines with $|Z|_{0.01\\mathsf{H z}}$ values in excess of $3.80\\times10^{11}\\quad\\Omega{\\cdot}\\mathrm{cm}^{2}$ at the beginning of immersion. The corresponding phase angles were $-900$ over the frequency range of $1\\dot{0}^{-1}-10^{\\bar{5}}\\mathsf{\\Pi}\\mathsf{\\dot{H}}z$ . This implies that during the immersion, a conductive pathway is not formed through the coating, which largely exhibits a capacitive behavior similar to that of an intact coating50. During the $60~\\mathsf{d}$ of immersion, the $|Z|_{0.01\\mathsf{H z}}$ values of the ZIF- ${\\cdot}8@{\\mathsf{C a/E P}}$ coating only slightly decreased from $3.80\\ \\times\\ 10^{11}\\ \\Omega{\\cdot}\\mathsf{c m}^{2}$ to $1.23\\times10^{11}\\Omega{\\cdot}\\mathrm{cm}^{2}.$ , confirming that the scratched ZIF-8@Ca/EP coating had been well repaired and possessed a satisfactory corrosion resistance.  \n\nAfter scratching, the pure EP and ZIF-8@Ca/EP coatings were subjected to salt spray tests following the ASTM B117/ D1654 standard. Figures 6b and 7a show the optical images of the coatings after exposure to the salt spray chamber for different periods. According to the visual assessment in Fig. 7a, green corrosion products were observed at the scratches of the pure EP coating within the 1 d of the salt spray test. After 60 d, large-scale coating delamination and corrosion products appeared in the scratched region, indicating that the scratched location of the pure EP coating was highly vulnerable to attack by corrosive species. Compared with pure EP, only slight scratch traces were observed at the scratched positions, and the $Z_{1}F{-}8@\\mathsf{C a}/\\mathsf{E P}$ coating did not show any signs of degradation (delamination, corrosion, or blistering) after 30 d (Fig. 7b). Furthermore, as the salt spray exposure time increased to $60~{\\mathsf{d}},$ only one slight corrosion spot was observed at the scratched site, indicating the corrosion of the scratched $Z|\\mathsf{F}{-}8@\\mathsf{C a}/\\mathsf{E P}$ coating could be controlled in a salt spray environment for a long time.  \n\nThe adhesion strength, an important indicator of coating properties, can be measured using a pull-off test. Figure 7d shows the adhesion strength/loss values of intact pure EP and $Z_{1}F_{-}8@C_{\\mathsf{a}}/$ EP coating before and after the 60 d salt spray test. The optical images of the remaining coatings following the pull-off test are presented in Fig. 7c. As shown in Fig. 7c, none of the samples exhibits cohesive failure. As shown in Fig. 7c, the dry adhesion strength of the $Z|\\mathsf{F}{-}8@\\mathsf{C a}/\\mathsf{E P}$ coatings (9.82 MPa) is higher than that of pure EP (4.70 MPa). This is because the introduction of branched-chain amines and UPy units enhanced the hydrogen bonding between the coating and the metal surface51. After salt spraying, the pure EP coating exhibited a considerable adhesion loss of $79.4\\%$ $(0.97\\mathsf{M P a})$ . In contrast, the ZIF-8@Ca/EP coating demonstrated not only the highest wet adhesion strength $(9.50\\mathsf{M P a})$ but also minimal adhesion loss $(3.3\\%)$ after a 60 d of salt spray test.  \n\nIn summary, the design of experimental techniques combined with an active learning and Bayesian optimization was proposed to predict and optimize the $\\mathsf{l g}|Z|_{0.01\\mathsf{H z}}$ values of scratched EP selfhealing coatings composed of different molecular weights of polyetheramine curing agent, molar ratios of polyetheramine to E51 EP resin, molar content of UPy-D400 and mass contents of ZIF$8@C a$ microfillers. The active learning process yielded the preferred experimental conditions to build a predictive RF model of $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ values with satisfactory accuracy $(R^{2}=0.709,\\mathsf{M A P E}=$ 0.081, $\\mathsf{R M S E}=0.685$ $(\\mathsf{l g}(\\Omega\\cdot\\mathsf{c m}^{2})))$ after five cycles of active learning. Then, an extremely high $\\mathsf{I g}|Z|_{0.01\\mathsf{H z}}$ values of 11.58 $(|Z|_{0.01\\mathsf{H z}}=3.80\\times10^{11}\\Omega{\\cdot}\\mathsf{c m}^{\\dot{2}})$ was achieved using the experimental conditions that were refined by Bayesian optimization. As confirmed by EIS, the $Z|\\mathsf{F}{-}8@\\mathsf{C a}/\\mathsf{E P}$ coating exhibited a great healing effect in barrier property (intact sample: $3.82\\times10^{11}\\Omega{\\cdot}\\mathrm{cm}^{2},$ repaired sample: $3.80\\times10^{11}~\\dot{\\Omega}{\\cdot}\\mathsf{c m}^{2})$ . In addition, in terms of the corrosion resistance after repair, the $Z|\\mathsf{F}{-}8@\\mathsf{C a}/\\mathsf{E P}$ coating exhibited slight corrosion after 60 d of the salt spray test, and the adhesion loss of the composite coating after the salt spray test was $3.3\\%$ which was considerably lower than that of the pure EP coating $(79.4\\%)$ .",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# METHODS",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# Materials  \n\nPolyetheramine curing agents with four different molecular weights (230, 400, 2000 and $4000\\mathsf{g}\\mathsf{m o l}^{-1}$ ) were sourced from the Aladdin Industrial Corporation. The E51 EP resin was sourced from Jiangsu Heli Resin Co., ltd. The ZIF- $8@C a$ microfillers and the UPy-D400 monomers were obtained using previously published methods11,51. The Q235 mild steel was used as the substrate.  \n\n![](images/d218b5017e8776b8d3b07db88a31a622234ce25382dea667c5df62f5f3e52805.jpg)  \nFig. 6 EIS characterizations of the different intact/scratched coatings. a Nyquist plots and b, c Bode plots of the intact pure EP and intact ZIF-8@Ca/EP coatings after 30 min of immersion in $3.5\\mathrm{\\:wt.}\\%$ NaCl solution. Nyquist plots and Bode plots of different d–f scratched pure EP and g–i scratched ZIF-8@Ca/EP coating during immersion in 3.5 wt. $\\%$ NaCl solution for $60~\\mathsf{d}$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# Preparation of coatings and EIS test  \n\nBased on the selected 32 experimental conditions, the preparation process of the self-healing EP coating containing $Z|F-8@C{\\mathsf{a}}$ microfillers $(\\boldsymbol{Z}|\\mathsf{F}{-}8@\\mathsf{C a}/\\mathsf{E P})$ is shown in Fig. 8. In each case, the ZIF-8@Ca microfillers were first mixed with the E51 EP resin under magnetic stirring. The polyetheramine curing agent and UPy-D400 were then added to the mixture using a mechanical agitator at 500 rpm for 10 min. Prior to the coating preparation, the steel specimens were wet-polished sequentially with 150-, 240- and 400-grit sandpapers, washed with ethanol and blow-dried in an ${\\sf N}_{2}$ atmosphere. The resulting mixture was applied to a steel piece using a bar coater. The coated samples were obtained by drying at room temperature for $48\\mathsf{h}$ . The final thickness of each of the dry films was approximately $85~{\\upmu\\mathrm{m}}$ .  \n\nEIS tests were performed to measure the low-frequency impedance $(|Z|_{0.011\\forall})$ values of the coated steel with/without an artificial scratch. Herein, all scratches of the EIS tests are made by a scalpel, and they are reproducible. The EIS results were obtained using a $3.5\\ \\mathsf{w t}.\\%$ NaCl solution and a CHI-660E electrochemical workstation with a three-electrode cell system comprising a coated steel substrate as a working electrode, a platinum plate electrode as a counter electrode and a saturated calomel electrode (SCE) as a reference electrode. The test parameters were set in the $10^{-2}{-}10^{5}\\mathsf{H z}$ range with a $0.02\\mathsf{V}$ root mean square amplitude. Prior to EIS measurements, artificial through-coating scratches (approximately $3\\mathsf{m m}$ in length and approximately $60\\upmu\\mathrm{m}$ in width) were made on the different coated steels using a scalpel. The measurements were conducted on the coated steels at least five times to ensure the reproducibility of the EIS results. In EIS results, the $|Z|_{0.01\\mathsf{H z}}$ value in the Bode plot usually represents the main performance index for the corrosion resistance of a coating, that is, a higher $|Z|_{0.01\\mathsf{H z}}$ value reflects a higher barrier property52. Therefore, this index was used to characterize the repair effect of the barrier properties of the coating after scratching.  \n\nTo further verify the self-healing and long-term anti-anticorrosion ability of the scratched composite coating after machine learning process, salt spray test was performed on the coatings via exposing the samples to salt spray for $60{\\mathrm{~d~}}$ in accordance with ASTM D1654.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# Data pre-processing, data splitting and machine learning models  \n\nData pre-processing and data splitting were performed and different machine learning models were simulated using the Python package scikit-learn (version 1.1.1). The four variable parameters (Table 4) in this study were standardized following a standard Gaussian distribution of a mean of 0 and a variance of $1^{53}$ . The purpose of normalization is to make the preprocessed data be limited to a certain range (e.g., [0,1] or [–1,1]), thus eliminating the undesirable effects caused by sample dataset with high variability. The validity and accuracy of all employed machine learning models were evaluated using k-fold cross-validation. In this step, the data were randomly arranged and divided into 10 groups. Nine groups were allocated for training purposes, and the remaining group was assigned to validate of the model. The average value was obtained by repeating the same process 10 times. To obtain the performance level of the model, the MAPE,  \n\n![](images/42c589ed5e004a3971035c311d43d7da737d0af26f34606ec4ab9c9cf2aa0780.jpg)  \nFig. 7 Salt spray analysis of the different intact/scratched coatings. a, b Optical images of the pure EP and ZIF- ${\\cdot}8@C\\mathsf{a}/\\mathsf{E P}$ coating. c Optical images of the pure EP and ZIF- ${\\pmb{8}}\\textcircled{\\circ}{\\mathsf{C a/E P}}$ coating after pull-off test at the end of salt spray test. d The adhesion strength values of the pure EP and ZIF-8@Ca/EP coating before and after 60 d of salt spray exposure, the adhesion strength values represent the average $\\pm$ standard deviations.  \n\n![](images/d0553c201e5d3aa235222ba35cdd22b5381b023f68b217f244eee7ab75931fd3.jpg)  \nFig. 8 Schematic illustration of the preparation process for self-healing EP composite coating. The coating formulation consists of the EP resin, polyetheramines, hydrogen bond unit (UPy-D400) and ZIF-8@Ca microfillers.  \n\nRMSE and $R^{2}$ were introduced to evaluate the k-fold crossvalidation, using the following Eqs. (3)-(5):54–56  \n\n$$\nM A P E=\\frac{1}{n}\\sum_{\\mathrm{i}=1}^{n}\\frac{|\\mathsf{y}_{\\mathrm{i}}-\\hat{\\mathsf{y}}_{\\mathrm{i}}|}{|\\mathsf{y}_{\\mathrm{i}}|}\n$$  \n\n$$\n{\\mathsf{R M S E}}={\\sqrt{{\\frac{1}{\\mathsf{n}}}\\sum_{\\mathrm{i=1}}^{\\mathsf{n}}{(\\mathsf{y}_{\\mathrm{i}}-{\\hat{\\mathsf{y}}}_{\\mathrm{i}})}^{2}}}\n$$  \n\n$$\n\\mathsf{R}^{2}=1-\\frac{\\sum_{\\mathrm{i=1}}^{\\mathrm{n}}(\\mathsf{y}_{\\mathrm{i}}-\\hat{\\mathsf{y}}_{\\mathrm{i}})^{2}}{\\sum_{\\mathrm{i=1}}^{\\mathrm{n}}(\\mathsf{y}_{\\mathrm{i}}-\\bar{\\mathsf{y}})^{2}}\n$$  \n\nwhere $\\mathsf{n}$ is the number of samples, and $y_{i}$ and $\\hat{y}_{i}$ are the experimental and predicted values of the ith sample, respectively.  \n\nThe accuracy of the machine learning model was accessed using its MAPE (MAPE value is in between 0 and 1, a value closer to 0 indicates greater accuracy57) and RMSE (a lower value of each indicates greater accuracy30) and $R^{2}$ (a value closer to 1 indicates greater accuracy; when the $R^{2}$ coefficient is greater than 0.7, the model represents acceptable accuracy58.)  \n\nFive machine learning models were applied as regression tools to the dataset: LR, ANN, SVR, DT and RF models. The machine learning methods are described in detail in the related reference59. The interested reader should refer to the Data Availability section for where to access our code used to run these algorithms.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# Bayesian optimization  \n\nBayesian optimization40 was used to determine the highest $\\mathsf{I g}\\vert\\boldsymbol{Z}\\vert_{0.01\\mathsf{H z}}$ values by refining the variable conditions from Table 1. Bayesian optimization was performed using the Python package GPyOpt.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# DATA AVAILABILITY  \n\nSource codes for this article are publicly available at https://github.com/ lt1037870521/manuscript-code-EP-Lt.  \n\nReceived: 11 June 2023; Accepted: 4 January 2024; Published online: 19 January 2024",
+        "category": " References"
+    },
+    {
+        "id": 14,
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Machine learning approach to ship fuel consumption: A case of container vessel. Transp. Res. D.-T. E. 84, 102389 (2020).   \n57. Chen, S., Cao, H., Ouyang, Q., Wu, X. & Qian, Q. ALDS: An active learning method for multi-source materials data screening and materials design. Mater. Des. 223,   \n111092 (2022).   \n58. Faraji Niri, M., Reynolds, C., Román Ramírez, L. A. A., Kendrick, E. & Marco, J. Systematic analysis of the impact of slurry coating on manufacture of Li-ion battery electrodes via explainable machine learning. Energy Storage Mater. 51,   \n223–238 (2022).  \n\n59. Bishop, C. M. & Nasrabadi, N. M. Pattern Recognition and Machine Learning. 4 (Springer), (2006).",
+        "category": " References"
+    },
+    {
+        "id": 15,
+        "chunk": "# ACKNOWLEDGEMENTS  \n\nThis work is supported by National Key R&D Program of China (2022YFB3808803).",
+        "category": " References"
+    },
+    {
+        "id": 16,
+        "chunk": "# AUTHOR CONTRIBUTIONS  \n\nT.L.: investigation, methodology, and writing—original draft. Z.C: investigation and methodology. J.Y.: investigation. L.M.: investigation. A.M.: writing—review and editing. D.Z.: supervision, conceptualization, methodology, and writing—review and editing.",
+        "category": " References"
+    },
+    {
+        "id": 17,
+        "chunk": "# COMPETING INTERESTS  \n\nThe authors declare no competing interests.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 18,
+        "chunk": "# ADDITIONAL INFORMATION  \n\nCorrespondence and requests for materials should be addressed to Dawei Zhang.  \n\nReprints and permission information is available at http://www.nature.com/ reprints  \n\nPublisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.  \n\nOpen Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http:// creativecommons.org/licenses/by/4.0/.  \n\n$\\circledcirc$ The Author(s) 2024",
+        "category": " References"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/synthesis of acrylate-based UV thermal dual-cure coatings for antifogging.json b/task2/task2-chunks/synthesis of acrylate-based UV thermal dual-cure coatings for antifogging.json
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@@ -0,0 +1,97 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Synthesis of acrylate-based UV/thermal dual-cure coatings for antifogging  \n\nBolong Yao, Haiping Zhao, Likui Wang, Yun Liu, Chunsen Zheng, Hongping Li, Changqing Sun  \n\n$\\circleddash$ American Coatings Association 2017  \n\nAbstract A dual-cure hydrophilic acrylate polymer was synthesized via radical polymerization with acrylic acid (AA), isophorone diisocyanate (IPDI), 2-acrylamide-2-methylpropane sulfonic acid (AMPS), hydroxyethyl acrylate (HEA), and 3-(trimethoxysilyl)propyl-2-methyl-2-methacrylate (MPS) as monomers, then used as prepolymer for antifog coating with tetraethylorthosilicate (TEOS) as a novel crosslinker. The prepolymer was mixed with crosslinking agent and photoinitiator to form coating formulas. The coating was characterized by nuclear magnetic resonance (NMR), Fourier-transform infrared (FTIR) spectroscopy, and contact angle measurements. The results indicated that the dosage of AMPS and TEOS had great influence on the antifog performance. With an increasing TEOS amount, the hardness, adhesion, water resistance, impact resistance, and thermal stability of the films were improved, at the expense of transparency; with increasing dosage of AMPS, the hydrophilicity of the film increased at the expense of water resistance. Optimum coating properties could be obtained when the amount of AMPS was $7\\%$ and that of TEOS was $5.5\\%$ . Scanning electron microscopy (SEM) and atomic force microscopy (AFM) results showed that some $\\mathrm{SiO}_{2}$ microspheres were formed and microphase separation occurred between the macromolecular segments, yielding the excellent coating properties.  \n\nKeywords TEOS, Antifogging, Dual cure, Acrylate",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# Introduction  \n\nTransparent substrates (such as glass) play an important role in daily life.1–4 Due to the high surface energy, condensation of droplets occurs when the temperature of the substrate surface is below the ambient water vapor dew point. These droplets lead to light refraction and scattering, causing transparent materials to become hazy, resulting in many problems and even causing serious harm.5 At present, there are two main methods to solve this problem: electric heating and antifog coating.6 Although the former method is effective, inconvenience and energy consumption limit its wide application. According to antifogging theory, two types of coatings have been researched: superhydrophobic and superhydrophilic.6 Superhydrophobic coatings mainly utilize the gravity of droplets to allow dew condensation to tumble down to achieve the antifogging effect.7–11 However, efficiency remains a major problem, and poor adhesion and mechanical properties such as hardness and scratch resistance also limit wide application of this method. These disadvantages can be overcome more easily when using superhydrophilic coatings, where water droplets on the surface of such coatings rapidly spread into a water film that does not scatter light.12–15 In this case, if dew condensation occurs, the surface can still remain optically clear. Rubner’s group16 adopted a layered self-assembly method to deposit $\\mathrm{SiO}_{2}^{-}$ nanoparticles and polyelectrolyte alternately to form a superhydrophilic porous film. The contact angle was less than $5^{\\circ}$ , with excellent antifogging performance. Also, Zoromba et al.17 developed an ultraviolet (UV)-curable urethane acrylate antifog coating. However, the majority of inorganic nanoparticles require complex preparation processes and they are difficult to coat, usually requiring sintering,18 while it is difficult to obtain a balance between hydrophilicity and water resistance when using organic polymers. The hydrophilicity of a surface mainly relies on various strongly hydrophilic groups, such as hydroxyl, carboxyl, and sulfonic acid.19 On such surfaces, water can penetrate and swell the film.  \n\nIn this work, acrylic ester was used as the main chain because of its good transparency. Hydrophilic monomer 2-acrylamide-2-methylpropane sulfonic acid (AMPS) was introduced to enhance the hydrophilicity of the film. The main chain of acrylic resin was modified with 3-(trimethoxysilyl)propyl-2-methyl-2- methacrylate (MPS), and tetraethylorthosilicate (TEOS) was used as a novel curing agent. The hydroxyl groups from MPS and TEOS, respectively, undergo a dehydration condensation reaction to generate a large number of Si–O–Si bonds20,21 under alkaline conditions. Because Si–O–Si bonds easily migrate to the coating surface during curing, a dense Si–O–Si network structure can form on the surface, giving the film excellent water resistance and mechanical properties. The film is ultimately cured by adding a photoinitiator and reactive diluents through the double bonds introduced into the main chain from halfblocked polyurethane. The other advantage of this approach is that use of tetraethylorthosilicate (TEOS) introduces a large number of hydroxyl groups. The formed $_{\\mathrm{Si-O-Si}}$ bonds with low surface tension bring the hydroxyl groups to the coating surface. This design ensures hydrophilicity and also imparts the coating with excellent mechanical properties and water resistance. Contact angle measurements, atomic force microscopy (AFM), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM) were applied to study the properties of films with different TEOS contents.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# Experimental",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# Materials  \n\nIsophorone diisocyanate (IPDI) was supplied by Bayer Co. Ltd. (Germany). 2-Acrylamido-2-methylpropane sulfonic acid (AMPS) was purchased from SongChuan Industrial Additives Co. Ltd. (ShanDong, China). Hydroxyethyl acrylate (HEA) and 3-(trimethoxysilyl)propyl-2-methyl-2-methacrylate (MPS) were supplied by Sigma-Aldrich Co. Ltd. (Shanghai, China). Trimethylol propane triacrylate (15EO-TMPTA), azobisisobutyronitrile (AIBN), acrylic acid (AA), leveling agent (3288), and tetraethylorthosilicate (TEOS) were purchased from Aladdin Reagent Co. Ltd. (Shanghai, China). Dibutyltin dilaurate (DBTDL), 4-methoxyphenol (MEHQ), $N\\mathrm{,}N$ -dimethylformamide (DMF), photoinitiator (1173), ammonia, acetone (ACE), deuterated dimethyl sulfoxide (DMSO), ethanol, anhydrous methanol, and isopropanol were all supplied by Sinopharm Chemical Reagent Co. Ltd. (Shanghai, China).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# Synthesis of prepolymer  \n\nAA and HEA had been pretreated to remove polymerization inhibitor. A series of acrylate copolymers (PAAMH) were synthesized via free-radical copolymerization. A mixture of AA, AMPS, HEA, MPS, and DMF was added into a dried $250\\mathrm{-mL}$ four-necked flask equipped with mechanical stirrer, condenser, ${\\bf N}_{2}$ catheters, and pressure-equalizing dropping funnel. The mixture was stirred at room temperature under ${\\bf N}_{2}$ protection and gradually heated to $80^{\\circ}\\mathrm{C}$ . AIBN 0 $3\\%$ of total monomer weight) was dissolved in a small amount of DMF, half of which was then added into the flask dropwise via the constant-pressure dropping funnel for $^{1\\mathrm{~h~}}$ at $80^{\\circ}\\mathrm{C}$ , and reacted for another $\\Bar{3}\\Bar{\\mathbf{h}}$ at $80^{\\circ}\\mathrm{C}$ . The remaining initiator was then added to the flask at the same dripping speed, and reacted for another $^{3\\mathrm{~h~}}$ .  \n\nNucleophilic addition of IPDI and HEA was employed to prepare an isocyanate-containing unsaturated monomer, IPHE. A mixture of IPDI, HEA, MEHQ, ACE, and DBTDL was added into a dried $250\\mathrm{-mL}$ four-necked flask equipped with mechanical stirrer, condenser, ${\\bf N}_{2}$ catheters, and pressure-equalizing dropping funnel, then gradually heated to $55^{\\circ}\\mathrm{C}$ and allowed to react for $2\\mathrm{~h~}$ . The isocyanate (NCO) content was monitored during the reaction using the standard dibutylamine backtitration method. Upon reaching the theoretical NCO value, the product was cooled to room temperature, transferred to another pressureequalizing dropping funnel, then added dropwise to the PAAMH. At the same time, additional catalyst DBTDL was added and reacted at $80^{\\circ}\\mathrm{C}$ for about $^{3\\mathrm{~h~}}$ until the NCO content reached another theoretical value. Reaction completion was confirmed by disappearance of the FTIR absorption peak at $22\\dot{7}0~\\mathrm{cm}^{-1}$ corresponding to stretching vibration of NCO group. During the above process, acetone was added to adjust the viscosity of the IPHE prepolymer. Finally, the acetone was removed to afford PAAMH-IH with $30~\\mathrm{wt\\%}$ solid content. The whole synthetic route is shown in Fig. 1. The compositions of all formulas used are presented in Table 1.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# Preparation of antifog coatings  \n\nPAAMH-IH was mixed with $3{\\mathrm{-}}4\\ \\mathrm{wt}\\%$ photoinitiator (Irgacure 1173), $0.3\\ \\mathrm{wt\\%}$ leveling agent 3288, and $25\\ \\mathrm{wt\\%}$ reactive diluents 15EO-TMPTA, and a certain amount of TEOS was introduced, as presented in Table 2. We chose 15EO-TMPTA as the reactive diluents to increase the double-bond content. The $\\mathrm{pH}$ value was adjusted to ${\\sim}13$ using aqueous ammonia (concentration ${\\sim}25\\%$ ), followed by quick stirring at room temperature. The solution was then coated on clean glass slides by dipping, and was then slowly dried at $50^{\\circ}\\mathrm{C}$ for $5\\mathrm{~h~}$ . The resulting films were heated in an oven at $70^{\\circ}\\mathrm{C}$ for another $2\\dot{\\mathrm{~h~}}$ . Finally, the films were irradiated using a 1200-W UV $(200-400~\\mathrm{nm})$ ) lamp for 30 s at room temperature.  \n\n![](images/20db17f7773114e92fe45dc31f7a587c22b2feab90e793c756ca97c2c7462469.jpg)  \nFig. 1: Synthesis and curing process of PAAMH-IH  \n\nTable 1: Components of PAAMH resin   \n\n\n<html><body><table><tr><td rowspan=\"2\">Sample</td><td colspan=\"6\">Content (g)</td><td rowspan=\"2\">W(AMPS) (%)℃</td></tr><tr><td>AA</td><td>HEAa</td><td>AMPS</td><td>MPS</td><td>HEAb</td><td>IPDI</td></tr><tr><td>PAAMH-IH-2%</td><td>10.00</td><td>6.00</td><td>0.72</td><td>2.00</td><td>6.00</td><td>11.50</td><td>2%</td></tr><tr><td>PAAMH-IH-4%</td><td>10.00</td><td>6.00</td><td>1.48</td><td>2.00</td><td>6.00</td><td>11.50</td><td>4%</td></tr><tr><td>PAAMH-IH-6%</td><td>10.00</td><td>6.00</td><td>2.26</td><td>2.00</td><td>6.00</td><td>11.50</td><td>6%</td></tr><tr><td>PAAMH-IH-8%</td><td>10.00</td><td>6.00</td><td>3.09</td><td>2.00</td><td>6.00</td><td>11.50</td><td>8%</td></tr><tr><td>PAAMH-IH-10%</td><td>10.00</td><td>6.00</td><td>3.94</td><td>2.00</td><td>6.00</td><td>11.50</td><td>10%</td></tr></table></body></html>\n\na Content of HEA on main chains; b Content of HEA on side chains; c Percentage of AMPS in total monomers  \n\nTable 2: Components of PAAMH-IH resin   \n\n\n<html><body><table><tr><td>Sample</td><td colspan=\"5\">Content (g)</td><td>W(TEOS) (%)</td></tr><tr><td></td><td>PAAMH-IH</td><td>TEOS</td><td>Ammonia</td><td>15EO-TMPTA</td><td>1173</td><td></td></tr><tr><td>PAAMH-IH-a</td><td>1.00</td><td>0.02</td><td>0.04</td><td>0.02</td><td>0.03</td><td>1.83%</td></tr><tr><td>PAAMH-IH-b</td><td>1.00</td><td>0.04</td><td>0.04</td><td>0.02</td><td>0.03</td><td>3.67%</td></tr><tr><td>PAAMH-IH-C</td><td>1.00</td><td>0.06</td><td>0.04</td><td>0.02</td><td>0.03</td><td>5.50%</td></tr><tr><td>PAAMH-IH-d</td><td>1.00</td><td>0.08</td><td>0.04</td><td>0.02</td><td>0.03</td><td>7.34%</td></tr><tr><td>PAAMH-IH-e</td><td>1.00</td><td>0.10</td><td>0.04</td><td>0.02</td><td>0.03</td><td>9.17%</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# Characterization  \n\nA Fourier-transform infrared spectrophotometer (FTLA2000-104, ABB Bomem of Canada) was used to confirm the chemical structure of IPHE, PAAMH, and PAAMH-IH. Purified product was dissolved in deuterated DMSO with tetramethylsilane (TMS) as internal standard. Then, $^1\\mathrm{H}$ and $^{13}\\mathrm{C}$ NMR spectra were recorded using a Bruker $500~\\mathrm{MHz}$ NMR (Avance III) to confirm the structure of PAAMH. Scanning electron microscopy (SEM, S4800, Hitachi) and atomic force microscopy (AFM, MultiMode 8, Bruker) were used to investigate the coating morphology. Samples were diluted to $15\\ \\mathrm{wt\\%}$ solid content with DMF, dripped onto a silicon wafer, and cured. The water resistance of the film was measured with reference to GB/T 1733- 1993 ‘‘determination of resistance to water of films.’’ Film hardness was measured with reference to GB/T 6739-2006 ‘‘paint and varnish pencil method to determine the hardness.’’ Adhesion was tested with reference to GB/T 9286-1998 ‘‘paint and varnish film crossgrid test.’’ Dried film (approximately $10\\ \\mathrm{cm}\\times5\\ \\mathrm{cm}$ ) was fixed on millimeter grid paper (grid: $1\\ \\mathrm{mm}\\ \\times\\ 1$ mm), and Scotch tape (3M, width $1.5\\ \\mathrm{cm}$ ) was pasted tightly onto the glass substrate. The number of grids covered by tape was recorded as $A_{0}$ . The tape was then pulled off quickly at angle of $180^{\\circ}$ , and the number of grids covered by the remaining film was recorded as $A$ . The adhesion22 of the film was then calculated as  \n\n$$\n{\\mathrm{Adhesion~}}(\\%)={\\frac{\\mathrm{A}}{\\mathrm{A}_{0}}}\\times100\n$$  \n\nThe test results were categorized into six grades, from 0 as the best to 6 as the worst. Impact strength was tested with reference to GB/T 1732-1993 ‘‘film impact resistance test.’’ Water absorption was investigated by immersing dried resin film (approximately $\\mathrm{{\\bar{1}}c m}\\times\\mathrm{{\\bar{1}}c m}$ , weight $M_{0.}$ ) into water for $\\bar{24}\\mathrm{{h}}$ . The film was then taken out of the water, and after the water on the surface had been removed using filter papers, the film was weighed immediately $(M_{1})$ . The water absorption22 of the film was then calculated as  \n\n![](images/2bdff3569060106486c1e62a19e9b240af0f35e36df2f1eac37dfc8418083e11.jpg)  \nFig. 2: FTIR spectra of (a) PAAMH-IH, (b) PAAMH, and (c) IPHE  \n\nWater absorption $(\\%)=\\frac{M_{\\mathrm{1}}-M_{\\mathrm{0}}}{M_{\\mathrm{0}}}\\times100.$  \n\nContact angles were tested using a DataPhysics OCA40 equipped with environmental chamber. Three drops of water were used for each measurement, and average contact angle values were recorded. Samples were prepared on transparent glass, with another, analogous glass used as background, and a doublebeam UV–Vis spectrophotometer (Beijing, TU-1901) was used to measure the transparency of the coating. Differential scanning calorimetry (DSC, Netzsch 204F1, Germany) measurements were carried out in the temperature range from $-20$ to $150^{\\circ}\\mathrm{C}$ under ${\\bf N}_{2}$ atmosphere at heating rate of $30^{\\circ}\\mathrm{C/min}$ . To test their antifog properties, different samples were held above hot water $({\\bar{8}}0^{\\circ}\\mathrm{C})$ for $15\\mathrm{~s~}$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# Results and discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# FTIR spectroscopy  \n\nThe FTIR spectra of IPHE, PAAMH, and PAAMHIH are shown in Fig. 2. Comparing spectra (a) and (c), the peaks at 1527 and $3360~\\mathrm{cm}^{-1}$ correspond to $-\\mathrm{\\mathbf{N}\\mathrm{\\mathbf{H}}}$ bending vibration and stretching vibration. The peak at $3300~\\mathrm{cm}^{-1}$ in spectrum (b) corresponds to hydroxyl absorption. As shown in Fig. 2, the absorption peak of $\\scriptstyle{\\mathrm{C=C}}$ stretching vibration at about $1640^{\\cdot}\\mathrm{cm}^{-1^{\\cdot}}$ disappeared from curve (b), indicating completion of the free-radical polymerization process. The reappearance of the $C{=}C$ absorption peak in curve (a) indicates successful introduction of IPHE. Comparing curves (c) and (a), the absorption peak of –NCO for IPHE at $2270~\\mathrm{{cm}^{-1}}$ disappeared from curve (a), indicating successful reaction of IPHE with PAAMH. Additionally, a strong absorption peak due to a sulfonic group was observed at about $11\\dot{7}0~\\mathrm{cm}^{-1}$ , suggesting successful introduction of AMPS. A weak absorption peak at $1020~\\mathrm{cm}^{-1}$ is attributed to $_{\\mathrm{Si-O-Si}}$ stretching, indicating successful introduction of MPS.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# $\\mathbf{\\nabla}^{I}H$ and $^{I3}C$ NMR analysis  \n\n$^1\\mathrm{H}$ and $^{13}\\mathrm{C}$ NMR techniques were employed to further confirm the structure of the prepolymer. The spectra for PAAMH are shown in Fig. 3, showing peaks for two methylene protons from the main chain $\\left(\\mathrm{-CH}_{2}\\mathrm{-}\\right)$ at $1.20~\\mathrm{ppm}$ and from two methyl protons $\\left(\\mathrm{CH}_{3^{-}}\\right)$ linking with acrylamide at 1.31 ppm. The signal for methylene $(-\\mathrm{CH}_{2}\\mathrm{-}\\mathrm{SO}_{3}\\mathrm{H})$ protons directly attached to sulfonic acid group appeared at $3.45~\\mathrm{ppm}$ . In combination with the FTIR spectra, the $^1\\mathrm{H}$ NMR spectrum further indicates introduction of AMPS. The signals at 4.08 and $1.44~\\mathrm{ppm}$ are due to two methylene protons directly connected with ester bond from both MPS and HEA. The signal for a methylene group (OH– $\\mathrm{CH}_{2^{-}}\\mathrm{\\rangle}$ ) proton directly connected to hydroxyl groups appears at $2.23~\\mathrm{ppm}$ , proving successful introduction of MPS and HEA.  \n\nThe $^{13}\\mathrm{C}$ NMR spectrum showed no peaks at $\\delta$ of $100{-}165~\\mathrm{ppm}$ , indicating no olefin. The saturated carbon $\\left(-\\mathrm{CH}_{2}\\mathrm{-CH}_{2}-\\right)$ absorption peak at $-2.1$ to $43\\ \\mathrm{ppm}$ further demonstrates that the AA, AMPS, MPS, and HEA double bonds were fully open. Both the $^1\\mathrm{H}$ and $^{13}\\mathrm{C}$ NMR spectra confirm synthesis of PAAMH.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# Water contact angle and water absorption of antifog coatings  \n\nFigure 4 shows the water contact angle (CA) and water absorption of the different PAAMH-IH prepolymers. Note that the CA decreased while the water absorption rose with increasing AMPS content. For AMPS content of $10\\%$ , the water absorption by the film reached $18.2\\%$ and the surface was swelled and tacky, thus being unusable. This result can mainly be attributed to the increasing sulfonic acid group content.19 Considering the balance between CA and water resistance, the optimum content of AMPS in the prepolymer was $^{6-}$ $8\\%$ . Regarding the dosage of curing agent (TEOS), all used prepolymer PAAMH-IH- $6\\%$ .",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# Transparency of antifog coatings  \n\nThe transparency of antifog coatings is crucial for their applications, as poor transparency limits their application in optical instruments.23 Figure 5 shows UV–Vis spectra of cured films with different TEOS contents (Table 2). With increasing TEOS content, the light transmission (at $700~\\mathrm{nm},$ ) reduced from above 95 to $85\\%$ , and the transparency was greatly affected. This is probably because, although most silanol (Si–OH) in the main chain reacted with MPS to form $_{\\mathrm{Si-O-Si}}$ bonds, a small amount of TEOS remained, forming $\\mathrm{SiO}_{2}$ nanoparticles, as shown in Figs. 6a–6c; all images show $\\mathrm{SiO}_{2}$ microspheres unevenly distributed on the coating surface, which reduced the transparency.  \n\n![](images/1548ae329b2259599394b665184184b8ecf5765127d5b2735e7a739be52e3462.jpg)  \nFig. 3: (a) $\\mathsf{\\Omega}^{1}\\mathsf{H}$ and (b) $\\boldsymbol{^{13}0}$ NMR spectra of PAAMH",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# Spreading time and contact angle  \n\nThe spreading time and CA of the PAAMH-IH films with different TEOS contents are shown in Fig. 7. As the TEOS content was increased from 1.83 to $9.17\\%$ , the CA decreased from $25.7^{\\circ}$ to $9.8^{\\circ}$ . This is mainly because TEOS formed hydroxyl groups on the coating surface, enhancing its hydrophilicity. During the crosslinking process, although some of the hydroxyl groups dehydrated and formed Si–O–Si bonds, there were still a large number of hydroxyl groups that failed to form $_{\\mathrm{Si-O-Si}}$ bonds. The formed Si–O–Si with low surface energy and poor compatibility easily migrates to the film surface during the curing process, taking hydroxyl groups to the film surface for microphase separation. According to curve (e) in Fig. 7, the TEOS content was higher than the other four groups, but the CA still showed an upward trend instead. Maybe more TEOS formed $\\mathrm{SiO}_{2}$ nanoparticles that were embedded into the film during curing, and the amount of hydroxyl groups that migrated to the surface decreased. Figure 7 shows that the spreading times on the coating (droplet volume $2~\\upmu\\mathrm{L}$ ) were very short, all being below $1500~\\mathrm{{\\bar{ms}}}$ .  \n\n![](images/39e44b4f1499c3c44f4b6f9e476a033bce03b85779baf2457bf57f75af5717ca.jpg)  \nFig. 4: Water contact angle and water absorption of PAAMH-IH  \n\n![](images/1aa8e4409436d1413f35dada428f4645874a6de34a615b3d3fa623ec8cdf1584.jpg)  \nFig. 5: Transparency of antifog coatings",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# AFM analysis of antifog coatings  \n\nFigure 8 shows AFM two-dimensional (2D) height maps and phase patterns for the PAAMH-IH films. The 2D height maps show that all the surfaces were smooth within a small range, all having average roughness $\\left(R_{\\mathrm{a}}\\right)$ close to 1.025. The coating flatness in regions without microspheres was still good. In general, lighter areas of AFM phase images correspond to hard segments while darker areas correspond to soft segments. The phase maps of the surfaces of the coatings in Fig. 8 show significant differences between light and dark, indicating distinct microphase separation. The gradual expansion of discontinuous dark areas from PAAMH-IH-a to PAAMH-IH-e indicates more obvious microphase separation with increasing TEOS dosage.  \n\n![](images/0b505386defe351df3af6025459beb4fcbbf030c130a2b25595582633f39beb9.jpg)  \nFig. 7: Water contact angle and spreading time for (a) PAAMH-IH-a, (b) PAAMH-IH-b, (c) PAAMH-IH-c, (d) PAAMHIH-d, and (e) PAAMH-IH-e  \n\n![](images/5a60459ab46e7ea86ba2e60dcad4bc4ca86621dd3856517809a45aa1b7a1e57a.jpg)  \nFig. 6: SEM images of PAAMH-IH coatings: (a) PAAMH-IH-a, (b) PAAMH-IH-c, and (c) PAAMH-IH-e  \n\n![](images/fc28cc497a08b5179b329d8f1862c215f3976cade6198b32dfe9870a4a86a220.jpg)  \nFig. 8: AFM images of PAAMH-IH, (a) PAAMH-IH-a, (b) PAAMH-IH-c, and (c) PAAMH-IH-e  \n\n![](images/fec1c7286f5f8242c802196c77b17d3d41c4dc169f3549418b40b7bc196750ac.jpg)  \nFig. 9: DSC curves of PAAMH-IH: (a) uncured, (b) thermally cured with TEOS, (c) UV cured, and (d) dual cured",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# DSC analysis  \n\nFigure 9 shows the DSC curves for PAAMH-IH. The curve for pure resin without curing is (a). Curve (b) is for the crosslinked film with just thermal curing with TEOS. Curve (c) is for the crosslinked film with just UV curing. Curve (d) is for the film with dual curing. Comparing (a) and (b), one finds that the glass transition temperature $(T_{\\mathrm{g}})$ of the film increased from 0.45 to $20.12^{\\circ}\\mathrm{C}$ , indicating the occurrence of the crosslinking reaction during film curing with formation of a crosslinked network structure. Comparing (a) and (c), the $T_{\\mathrm{g}}$ of the film rose from 0.45 to $73.62^{\\circ}\\mathrm{C}$ ， indicating that UV curing also occurred. Comparing (a), (b), (c), and (d), the gradually increasing $T_{\\mathrm{g}}$ confirms that a dual-curing reaction occurred.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# Mechanical performance and water resistance of coatings  \n\nTable 3 presents the film properties of the coatings with different TEOS content. The results in Table 3 show that all samples exhibited high pencil hardness, with the highest reaching 3H. This can be attributed to high crosslink density of the polymer and large cohesive energy of crosslinked molecules. According to the impact resistance results, with increasing TEOS content, the impact strength also increased. No cracking or peeling phenomena were observed on the surfaces after impact. The maximum impact strength reached $70\\ \\mathrm{cm}$ . The maximum adhesion grade of the film reached 0. This is because the silane coupling agent (MPS) in the main chain of PAAMH-IH reacted with hydroxyl groups on the glass substrate surface to form $\\dot{\\mathrm{Si-O-}}\\dot{\\mathrm{Si}}$ bonds. After soaking for $24\\mathrm{~h~}$ , none of the coatings showed whitening phenomenon, indicating excellent water resistance. These results demonstrate that the UV-cured coating with proper formula exhibited excellent coating performance.  \n\nTable 3: Effects of amount of TEOS on film properties   \n\n\n<html><body><table><tr><td>Test item</td><td colspan=\"5\">TEOS (wt%)</td></tr><tr><td></td><td>PAAMH-IH-a</td><td>PAAMH-IH-b</td><td>PAAMH-IH-c</td><td>PAAMH-IH-d</td><td>PAAMH-IH-e</td></tr><tr><td>Pencil hardness</td><td>2H</td><td>3H</td><td>3H</td><td>3H</td><td>3H</td></tr><tr><td>Adhesion grade</td><td>1</td><td>1</td><td>0</td><td>0</td><td>0</td></tr><tr><td>Water resistance</td><td>No whitening</td><td>No whitening</td><td>No whitening</td><td>No whitening</td><td>No whitening</td></tr><tr><td>Impact resistance (mm)</td><td>60</td><td>65</td><td>70</td><td>70</td><td>70</td></tr></table></body></html>  \n\n![](images/5502245c8788dd7482e17428fdbc2ef4e47d2053cfdd275234ee99323667b50e.jpg)  \nFig. 10: 1 Antifog property of coatings: (a) PAAMH-IH-a, (b) PAAMH-IH-b, (c) PAAMH-IH-c, (d) PAAMH-IH-d, (e) PAAMH-IH-e. 2 Comparison of transparency of films",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# Antifog property of coatings  \n\nThe antifog property of the coatings was tested, and the results are shown in Fig. 10-1. The transparency of the films is compared in Fig. 10-2. In each graph, the glass on the right is coated with PAAMH-IH antifog coating while the left side is left uncoated for reference. As shown by these pictures, the glass with antifog coating remained transparent while the uncoated glass became hazy due to water condensation. With increasing TEOS content, the transparency decreased, as shown in Fig. 10-2.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# Conclusions  \n\nA functional resin was successfully synthesized using IPDI, AMPS, HEA, MPS, and AA as raw materials. Mixing with TEOS as novel crosslinking agent enabled preparation of antifog coatings. DSC curves confirmed the crosslinking reaction between MPS and TEOS during film formation, resulting in a crosslinked network structure. AFM images revealed microphase separation on the coating surface with migration of Si– O–Si bonds to the surface of the coating, leading to good adhesion, hardness, and water resistance, compared with traditional antifog coatings.  \n\nVarious characterization techniques were applied to determine the optimum amounts of AMPS and TEOS. When the amount of AMPS was increased from 2 to $10\\%$ , the hydrophilicity of the coating increased, but the water absorption also increased, reaching a value of $18.2\\%$ , indicating poor water resistance. When the amount of TEOS was increased from 1.83 to $9.17\\%$ , the hardness, hydrophilicity, and water resistance increased, but the transparency decreased. Overall, the coating produced using $6{-}8\\%$ AMPS and $5.5\\%$ TEOS showed excellent antifog performance and mechanical properties.  \n\nAcknowledgments This work was financially supported by the Natural Science Foundation of China (No. 51302109) and Natural Science Foundation of Jiangsu Province (BK20130144).",
+        "category": " Conclusions"
+    },
+    {
+        "id": 19,
+        "chunk": "# References  \n\n1. Nuraje, N, Asmatulu, R, Cohen, RE, Rubner, MF, ‘‘Durable Antifog Films From Layer-by-Layer Molecularly Blended Hydrophilic Polysaccharides.’’ Langmuir, 27 (2) 782–791 (2011) 2. Thompson, CS, Fleming, RA, Zou, M, ‘‘Transparent Selfcleaning and Antifogging Silica Nanoparticle Films.’’ J. Sol. Energy Mater. Sol. Cells, 115 (10) 108–113 (2013)  \n\n3. Zhang, L, Qiao, ZA, Huo, Q, Sun, J, ‘‘Rapid and SubstrateIndependent Layer-by-Layer Fabrication of Antireflectionand Antifogging-Integrated Coatings.’’ J. Mater. Chem., 20 (29) 6125–6130 (2010)   \n4. Chevallier, P, Turgeon, S, Sarra-Bournet, C, Turcotte, R, Laroche, G, ‘‘Characterization of Multilayer Anti-fog Coatings.’’ J. Appl. Mater. Interfaces, 3 (3) 750–758 (2011)   \n5. Zhao, J, Ma, L, Millians, W, Wu, T, Ming, W, ‘‘DualFunctional Antifogging/Antimicrobial Polymer Coating.’’ J. Appl. Mater. Interfaces, 8 (13) 8737–8742 (2016)   \n6. Lee, DI, Son, BG, Bae IJ, ‘‘Anti-fog Heat Generating Glass System and Method For Controlling The Same.’’ US patent 8,870,394, 2014   \n7. Gao, XF, Yan, X, Yao, X, Liang, X, Kai, Z, Zhang, JH, Bai, Y, Lei, J, ‘‘The Dry-Style Antifogging Properties of Mosquito Compound Eyes and Artificial Analogues Prepared by Soft Lithography.’’ J. Adv. Mater., 19 (17) 2213– 2217 (2007)   \n8. Lee, H, Alcaraz, ML, Rubner, MF, Cohen, RE, ‘‘ZwitterWettability and Antifogging Coatings with Frost-resisting Capabilities.’’ ACS Nano, 7 (3) 2172–2185 (2013)   \n9. Wang, JJ, Wang, DS, Wang, J, Zhao, WL, Wang, CW, ‘‘High Transmittance and Superhydrophilicity of Porous $\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ Bi-layer Films without UV Irradiation.’’ J. Surf. Coat. Tech., 205 (12) 3596–3599 (2011)   \n10. Lai, YK, Tang, YX, Gong, JJ, Gong, DG, Chi, LF, Lin, CJ, ‘‘Transparent Superhydrophobic/Superhydrophilic $\\mathrm{TiO}_{2}$ - based Coatings for Self-cleaning and Anti-fogging.’’ J. Mater. Chem., 22 (15) 7420–7426 (2012)   \n11. Chen, Y, Zhang, YB, Shi, L, Jing, L, Xin, Y, Yang, TT, ‘‘Transparent Superhydrophobic/Superhydrophilic Coatings for Self-cleaning and Anti-fogging.’’ Appl. Phys. Lett., 101 (3) 033701-1–033701-4 (2012)   \n12. Han, J, Dou, Y, Wei, M, Evans, DG, Duan, X, ‘‘Antireflection/Antifogging Coatings Based on Nanoporous Films Derived from Layered Double Hydroxide.’’ Chem. Eng. J., 169 (1–3) 371–378 (2011)   \n13. Liu, XM, Xin, D, He, J, ‘‘Hierarchically Structured Porous Films of Silica Hollow Spheres via Layer-by-Layer Assembly and Their Superhydrophilic and Antifogging Properties.’’ ChemPhysChem, 9 (2) 305–309 (2008)   \n14. Zhang, L, Li, Y, Sun, J, Shen, J, ‘‘Mechanically Stable Antireflection and Antifogging Coatings Fabricated by the Layer-by-Layer Deposition Process and Postcalcination.’’ Langmuir, 24 (19) 10851–10857 (2006)   \n15. Miyauchi, M, Nakajima, A, Hashimoto, K, Watanabe, T, ‘‘A Highly Hydrophilic Thin Film Under $1\\ \\upmu\\mathrm{W}/\\mathrm{cm}^{2}$ UV Illumination.’’ J. Adv. Mater., 12 (24) 1923–1927 (2000)   \n16. Cebeci, FC, Wu, Z, Zhai, L, Cohen, RE, Rubner, MF, ‘‘Nanoporosity-driven Superhydrophilicity A Means to Create Multifunctional Antifogging Coatings.’’ Langmuir, 22 (6) 2856–2862 (2006)   \n17. Zoromba, MST, Preparation and Characterization of New Nanostructured Organic/Inorganic Composite Coatings for Anti-fog Applications. Clausthal University of Technology, D. Faculty of Natural and Material Sciences, ClausthalZellerfeld (2009)   \n18. Liu, XM, He, J, ‘‘Hierarchically Structured Superhydrophilic Coatings Fabricated by Self-assembling Raspberry-Like Silica Nanospheres.’’ J. Colloid Interface Sci., 314 (1) 341– 345 (2007)   \n19. Yuan, Y, Liu, R, Wang, C, Luo, J, Liu, X, ‘‘Synthesis of UVcurable Acrylate Polymer Containing Sulfonic Groups for Anti-fog Coatings.’’ J. Prog. Org. Coat., 77 (4) 785–789 (2014)   \n20. Wong, YJ, Zhu, L, Teo, WS, Tan, YW, Yang, Y, Wang, C, Chen, H, ‘‘Revisiting the Stober Method Inhomogeneity in Silica Shells.’’ J. Am. Chem. Soc., 133 (30) 11422–11425 (2011)   \n21. Liu, H, Li, HL, Ding, ZL, Fu, AP, Wang, HY, Guo, PZ, Yu, JQ, Wang, CG, Zhao, XS, ‘‘Preparation of Porous Hollow $\\mathrm{SiO}_{2}$ Spheres by A Modified Stober Process Using MF Microspheres as Templates.’’ J. Clust. Sci., 23 (2) 273–285 (2012)   \n22. Pi, P, Chen, X, Wen, X, Xu, S, Cheng, J, ‘‘Preparation and Characterization of Ambient-Temperature Self-crosslinkable Water-Soluble Acrylic Resin for PE Film Ink.’’ J. Coat. Technol. Res., 13 (1) 73–80 (2016)   \n23. Howarter, JA, Youngblood, JP, ‘‘Self-Cleaning and Next Generation Anti-Fog Surfaces and Coatings.’’ Macromol. Rapid Commun., 29 (6) 455–466 (2008)",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Spontaneous Pattern Formation Induced by Bénard−Marangoni Convection for Sol−Gel-Derived Titania Dip-Coating Films: Effect of Co-solvents with a High Surface Tension and Low Volatility  \n\nHiroaki Uchiyama,\\* Tadayuki Matsui, and Hiromitsu Kozuka Department of Chemistry and Materials Engineering, Kansai University, 3-3-35 Yamate-cho, Suita, Osaka 564-8680, Japan  \n\n\\*S Supporting Information  \n\n![](images/f64959150f10abd8eae7552c1651d664c8cf14e73e527048e531532b6614ab0d.jpg)  \n\nABSTRACT: Evaporation-driven surface tension gradient in the liquid layer often causes the convective flow, i.e., Bénard− Marangoni convection, resulting in the formation of cell-like patterns on the surface. Here, we prepared sol−gel-derived titania films from $\\mathrm{Ti}(\\mathrm{OC}_{3}\\mathrm{H}_{7}^{~i})_{4}$ solutions by dip coating and discussed the effect of the addition of co-solvents with a high surface tension and low volatility on the spontaneous pattern formation induced by Bénard−Marangoni convection. Propylene glycol (PG, with a surface tension of $38.6\\mathrm{\\dot{m}N\\ m^{-1}},$ ) and dipropylene glycol (DPG, with a surface tension of $33.9\\ \\mathrm{mN\\m^{-1}}$ ) were added to the coating solutions containing 2-propanol $(2\\mathrm{-Pr},$ with a surface tension of $22.9\\ \\mathrm{mN\\m^{-1}}$ ) for controlling the evaporationdriven surface tension gradient in the coating layer on a substrate. During dip coating at a substrate withdrawal speed of $50\\ \\mathrm{cm}$ $\\operatorname*{min}^{-1}$ in a thermostatic oven at $60\\ {}^{\\circ}{\\bf C},$ , linearly arranged cell-like patterns on a micrometer scale were spontaneously formed on the titania gel films, irrespective of the composition of coating solutions. Such surface patterns remained even after the heat treatment at 200 and $600^{\\circ}\\mathrm{C},$ where the densification and crystallization of the titania films progressed. The width and height of the cell-like patterns increased with increasing PG and DPG contents in the coating solutions, where the addition of PG resulted in the formation of cells with a larger height than DPG.",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# INTRODUCTION  \n\nSelf-assembly and self-organization triggered by solvent evaporation are very attractive techniques for making thinfilm materials with highly ordered surface patterns.1−15 Solvent evaporation from solutions containing non-volatile solutes (e.g., colloidal solutions, suspensions, and polymer solutions) often induces a convective flow in the solution layer, leading to the spontaneous assembly and organization of the solutes. “Marangoni effect” is widely known as an evaporation-driven convection phenomenon.16−22 Temperature or concentration gradients in the solution layer result from solvent evaporation, creating the local surface tension gradient. The evaporationdriven surface tension gradient leads to the convective flow of solutions, i.e., “Bénard−Marangoni convection”. The Bénard− Marangoni convection can be characterized by the Marangoni number, Ma, which is a measure of the occurrence tendency of convection, as described below21−23  \n\n$$\nM a=\\frac{-(\\partial\\gamma/\\partial T)H^{2}\\nabla T}{\\mu\\alpha}\n$$  \n\n$$\nM a=\\frac{-(\\partial\\gamma/\\partial C)H^{2}\\nabla C}{\\mu D}\n$$  \n\nwhere $\\partial\\gamma/\\partial T$ is the temperature derivative of the surface tension, $\\nabla T$ is the temperature gradient near the solution surface, $\\partial\\gamma/\\partial C$ is the concentration derivative of the surface tension, $\\nabla C$ is the concentration gradient near the solution surface, $H$ is the thickness of the solution layer, $D$ is the mass diffusivity of the component, and $\\mu$ and $\\alpha$ are the viscosity and thermal diffusivity of the solution, respectively. Generally, Bénard−Marangoni convection occurs when Ma is high; Ma increases with increasing temperature or concentration gradients near the solution surface, with increasing thicknesses of the solution layer, and with decreasing solution viscosities, as shown in eqs 1 and 2. When Bénard−Marangoni convection is activated, micrometer-scaled cell-like patterns (i.e., Bénard cells) often appear on the surface of the solution layer. Such pattern formation attributed to the “Marangoni effect” is commonly seen in many kinds of solutions and, thus, can be applicable as the self-assembly and self-organization techniques for thin-film materials.  \n\nThe spontaneous pattern formation induced by Bénard− Marangoni convection can be also found on sol−gel-derived inorganic and organic−inorganic hybrid films.2 35 The thickness variations of sol−gel coating films are reported to be caused by the Bénard−Marangoni convection.24,25,27 In the case of polymer films, the solvent depletion from the surface of the coating layer often creates solute-rich skins, providing the local surface tension gradient.36 Birnie et al. investigated the thickness variations in sol−gel-derived spin-coating films and suggested that the surface tension gradient as a result of the solute-rich skins leads to the lateral flow of solutions toward the higher surface tension area (i.e., solute-rich area) and then the skins become thicker with time, resulting in surface roughening.25 They also found that striation defects observed after the spin coating is attributed to the connection of cell-like Bénard−Marangoni convections along the radial solution flow on a spinning substrate.24 Our group has also observed the striation defects on alkoxide-derived spin-coating layers28−30 and, furthermore, found that the striations and cell-like patterns as a result of the Marangoni effect appeared even on a droplet of alkoxide solutions on a stationary substrate.28,34 Moreover, we have reported that the linearly arranged striations and celllike patterns were formed on sol−gel-derived dip-coating films,32,33,35 where the size and shape of the periodic patterns depend upon the substrate withdrawal speed,35 the viscosity of coating solutions,3 and the coating temperature (i.e., the temperature of substrates, solutions, and atmosphere).33 We attributed the highly ordered surface patterns on sol−gelcoating films to the fixing of the local surface elevation as a result of Bénard−Marangoni convection by the gelation of the coating layer.33,34 Figure 1 shows the schematic illustration of the pattern formation as a result of the Marangoni effect. The rapid solvent evaporation from the coating layer during the deposition process can lead to the evaporative concentration of the solutes and the cooling at the surface, which makes a locally higher surface tension area (Figure 1a), leading to the local surface elevation as a result of Bénard−Marangoni convection (Figure 1b). The surface elevation is fixed by the rapid gelation of the coating layer as a result of the solvent evaporation, resulting in the formation of periodic surface patterns.33 Such pattern formation accompanied by the fixing of the coating layer has also been reported in organic polymer films.37 The spontaneous pattern formation induced by Bénard−Marangoni convection in the sol−gel-coating process is expected as a novel fabrication technique of highly ordered surface patterns in metal oxide film materials, and thus, it is highly desirable to achieve the precise control of the size, shape, and arrangement of the patterns.  \n\nIn this work, we focused on the influence of the surface tension of solvents on the pattern formation induced by Bénard−Marangoni convection for sol−gel-derived metal oxide thin films. The surface tension is a definitely essential factor for Bénard−Marangoni convection, because the convection phenomenon is caused by the evaporation-driven surface tension gradient in the solution layer (Figure 1). The solvent selection strategy for preventing the thickness inhomogeneity on sol−gel-coating films as a result of the Marangoni effect has been discussed by Birnie et al., which suggests that the thickness inhomogeneity can be prevented by the addition of co-solvents that can reduce the surface tension gradient in the coating layer during solvent evaporation.24−26 When the lowvolatile co-solvent with a lower surface tension is added to the coating layer, the co-solvent is left together with the solutes during the evaporation of the major solvent. Birnie et al. proposed that such an evaporative concentration of the cosolvent with a lower surface tension causes the local decrease in the surface tension, which reduces the local surface tension gradient that is induced by the evaporative concentration of the solutes and the cooling of the coating layer, suppressing the occurrence of Bénard−Marangoni convection.24,25 Here, we attempted to use such a solvent selection strategy to enhance the evaporation-driven pattern formation on sol−gel-coating films. If the co-solvent with a higher surface tension and lower volatility exists in the evaporating coating layer, the co-solvent would remain there and enhance the local increase in the surface tension as a result of the evaporative loss of the major solvent, creating a higher surface tension gradient. The higher surface tension gradient would provide a stronger convective flow in the coating layer, resulting in the larger surface elevation. We prepared sol−gel-derived titania films by dip coating from $\\mathrm{Ti}(\\mathrm{OC}_{3}\\mathrm{H}_{7}{}^{i})_{4}$ solutions containing 2-propanol (2- $\\mathrm{Pr}_{\\mathbf{\\lambda}}$ ) as the major solvent and propylene glycol (PG) and dipropylene glycol (DPG) as the co-solvents. The PG and DPG contents were varied for controlling the surface tension gradient in the coating layer, and the effect of the co-solvents on the spontaneous pattern formation induced by Bénard− Marangoni convection was systematically discussed.  \n\n![](images/3cde97c7aaf8b0c2840fbfd062cb529537c6bd95e33465993444980b920fe437.jpg)  \nFigure 1. Schematic illustration of the pattern formation as a result of the Marangoni effect: (a) evaporation-driven surface tension gradient and (b) surface elevation.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2. EXPERIMENTAL SECTION  \n\n2.1. Materials. The starting materials were $\\mathrm{Ti}(\\mathrm{OC}_{3}\\mathrm{H}_{7}^{~i})_{4}$ (Wako Pure Chemical Industries, Osaka, Japan), nitric acid ${\\mathrm{(HNO}}_{3},$ 69 mass $\\%$ , Wako Pure Chemical Industries, Osaka, Japan), $2{\\cdot}\\mathrm{Pr}$ $(2\\mathrm{-}C_{3}\\mathrm{H}_{7}\\mathrm{OH},$ Wako Pure Chemical Industries), PG $\\mathrm{\\small{[CH_{3}C H(O H)C H_{2}O H_{3}}}$ , Wako Pure Chemical Industries], DPG $\\big[\\big(\\mathrm{HOC}_{3}\\mathrm{H}_{6}\\big)_{2}\\mathrm{O}_{\\cdot}$ , Wako Pure Chemical Industries], and ion-exchanged water $\\left(\\mathrm{H}_{2}\\mathrm{O}\\right)$ . The surface tension, viscosity, and boiling point of the solvents are listed in Table 1.  \n\nTable 1. Surface Tension, Viscosity, and Boiling Point of Solvents   \n\n\n<html><body><table><tr><td>solvent</td><td>surface tension (mN m-l)</td><td>viscosity (mPa s)</td><td> boiling point (°C)</td></tr><tr><td>2-Pr</td><td>22.9</td><td>1.77</td><td>82.4</td></tr><tr><td>PG</td><td>38.6</td><td>61.7</td><td>188.2</td></tr><tr><td>DPG</td><td>33.9</td><td>75.3</td><td>230.0</td></tr></table></body></html>  \n\n2.2. Preparation of Titania Films. The compositions of starting solutions are listed in Table 2. Starting solutions of molar compositions, $\\mathrm{Ti}(\\mathrm{OC_{3}H_{7}}^{i})_{4}/\\mathrm{H_{2}O}/\\mathrm{HNO_{3}}/\\mathrm{\\bar{2}}\\mathrm{-Pr}/\\mathrm{PG}$ or DPG $\\mathbf{\\Sigma}=\\mathbf{\\Sigma}$ $1{:}2{:}0.2{:}40{:}x$ or $y$ $\\dot{}_{x}$ or $y=0{-}1.50)$ , were prepared by the following procedure. First, $\\mathrm{Ti}(\\mathrm{OC}_{3}\\mathrm{H}_{7}{}^{i})_{4}$ was added in a half of the prescribed amount of $2{\\cdot}\\mathrm{Pr}$ . The remaining amount of $2{\\cdot}\\mathrm{Pr}$ was mixed with $_\\mathrm{H}_{2}\\mathrm{O}$ and ${\\mathrm{HNO}}_{3}$ . The solution containing 2-Pr, $\\mathrm{H}_{2}\\mathrm{O},$ , and ${\\mathrm{HNO}}_{3}$ was added dropwise to the $\\mathrm{Ti}(\\mathrm{OC}_{3}\\mathrm{H}_{7}^{~i})_{4}$ solution under stirring. The solutions were kept standing at room temperature in a sealed glass container for $30~\\mathrm{{min},}$ , and then PG or DPG was added under stirring. The solutions were, furthermore, kept standing at room temperature for $3\\mathrm{~h~}$ and served as coating solutions.  \n\nTitania gel films were deposited on Si(100) substrates $(20\\times40\\times$ $0.85\\ \\mathrm{mm},$ ) using a dip coater (portable dip coater DT-0001, SDI, Kyoto, Japan), where the substrates were withdrawn at $50.0\\ \\mathrm{cm\\min^{-1}}$ . The dip coating was performed in a thermostatic oven, as shown in Figure S1 of the Supporting Information. The coating temperature (i.e., the temperature of substrates, solutions, and atmosphere) was kept at $60~^{\\circ}\\mathrm{C},$ where the solutions and substrates were heated at the coating temperature for $30\\ \\mathrm{min}$ before the dip coating. After the deposition, the gel films were kept at $60~^{\\circ}\\bar{\\mathrm{{C}}}$ for $3~\\mathrm{min}$ in the thermostatic oven. Then, the gel films were heated at 200 or $600~^{\\circ}\\mathrm{C}$ for $10\\ \\mathrm{min}$ in air, where the films were transferred to an electric furnace held at the prescribed temperature.  \n\n2.3. Characterizations. The viscosity of the coating solutions was measured using an oscillating-type viscometer (VM-1G, Yamaichi Electronics, Tokyo, Japan). Microscopic observation of the film samples was made using an optical microscope (KH-1300, HiROX, Tokyo, Japan). The crystalline phases were identified by X-ray diffraction (XRD) measurement by ordinary $2\\theta/\\theta$ mode using an Xray diffractometer (model Rint 2550V, Rigaku, Tokyo, Japan) with Cu $\\mathrm{K}\\alpha$ radiation operated at $40\\ \\mathrm{kV}$ and $300~\\mathrm{{mA}}$ .  \n\nTwo-dimensional (2D) and three-dimensional (3D) surface profiles of the film samples were measured using a contact probe surface profilometer (SE-3500K31, Kosaka Laboratory, Tokyo, Japan). The measurement was conducted at the center of the films, as shown in Figure 2a. Surface roughness parameters, S (mean spacing of local peaks) and $R_{z}$ (ten point height of irregularities), were automatically calculated from the 2D profile (the definitions of S and $R_{z}$ are shown in Figure S2 of the Supporting Information). S and $R_{z}$ represent the width and height, respectively, of the surface patterns, as shown in Figure 2b.  \n\n![](images/0881e730f0ce99abc3c4246a6f2d33e117891bc4dc12c1f1acb51e25ab71f717.jpg)  \nFigure 2. (a) Schematic illustration of the test line and area employed in 2D and 3D surface roughness measurements and (b) definition of the film thickness and width and height of the surface pattern.  \n\nTable 2. Compositions and Viscosity of the Coating Solutions   \n\n\n<html><body><table><tr><td colspan=\"6\"> mole ratio</td><td colspan=\"2\">co-solvent volume per gram of Ti(OCH7)4 (mL)</td><td></td></tr><tr><td>Ti(OCH)4</td><td>HO</td><td>HNO3</td><td> isopropanol</td><td>PG (x)</td><td>DPG (y)</td><td> PG</td><td>DPG</td><td>viscosity (mPa s)</td></tr><tr><td>1</td><td>2</td><td>0.2</td><td>40</td><td>0</td><td>0</td><td>0</td><td>0</td><td>2.05</td></tr><tr><td>1</td><td>2</td><td>0.2</td><td>40</td><td>0.25</td><td></td><td>0.064</td><td></td><td>2.27</td></tr><tr><td>1</td><td>2</td><td>0.2</td><td>40</td><td>0.50</td><td></td><td>0.13</td><td></td><td>2.33</td></tr><tr><td>1</td><td>2</td><td>0.2</td><td>40</td><td>0.75</td><td></td><td>0.19</td><td></td><td>2.48</td></tr><tr><td>1</td><td>2</td><td>0.2</td><td>40</td><td>1.00</td><td></td><td>0.26</td><td></td><td>2.42</td></tr><tr><td>1</td><td>2</td><td>0.2</td><td>40</td><td>1.25</td><td></td><td>0.32</td><td></td><td>2.46</td></tr><tr><td>1</td><td>2</td><td>0.2</td><td>40</td><td>1.50</td><td></td><td>0.39</td><td></td><td>2.50</td></tr><tr><td>1</td><td>2</td><td>0.2</td><td>40</td><td></td><td>0.25</td><td></td><td>0.12</td><td>2.14</td></tr><tr><td>1</td><td>2</td><td>0.2</td><td>40</td><td></td><td>0.50</td><td></td><td>0.23</td><td>2.11</td></tr><tr><td>1</td><td>2</td><td>0.2</td><td>40</td><td></td><td>0.75</td><td></td><td>0.35</td><td>2.30</td></tr><tr><td>1</td><td>2</td><td>0.2</td><td>40</td><td></td><td>1.00</td><td></td><td>0.46</td><td>2.25</td></tr><tr><td>1</td><td>2</td><td>0.2</td><td>40</td><td></td><td>1.25</td><td></td><td>0.58</td><td>2.45</td></tr><tr><td>1</td><td>2</td><td>0.2</td><td>40</td><td></td><td>1.50</td><td></td><td>0.69</td><td>2.43</td></tr></table></body></html>  \n\nFilm thickness was measured by the profilometer (the definitions of the thickness are shown in Figure 2b). A part of the thin film was scraped off with a surgical knife immediately after the film deposition, and the level difference between the coated part and the scraped part was measured after drying.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# 3. RESULTS AND DISCUSSION  \n\n3.1. Preparation of Titania Films with Surface Patterns. Colorless, transparent $\\mathrm{Ti}(\\mathrm{OC}_{3}\\mathrm{H}_{7}{}^{i})_{4}$ solutions were obtained at room temperature, irrespective of PG and DPG contents $[\\mathrm{PG}/\\mathrm{Ti}(\\mathrm{OC}_{3}\\mathrm{\\bar{H}}_{7}{}^{i})_{4}$ mole ratio $(x)\\ =\\ 0{-}1.50,$ and $\\mathrm{DPG}/\\mathrm{Ti}(\\mathrm{OC}_{3}\\mathrm{H}_{7}{}^{i})_{4}$ mole ratio $\\left(y\\right)=0{-}1.50]$ . The viscosity of the coating solutions slightly increased with increasing PG and DPG contents, as shown in Table 2, which could be caused by the high viscosity of PG and DPG (Table 1).  \n\nTitania gel films were prepared from the coating solutions of $x$ or $y=0{-}1.50$ by dip coating at a substrate withdrawal speed of $5\\dot{0}\\ \\mathrm{cm\\min^{-1}}$ in a thermostatic oven at $60~^{\\circ}\\mathrm{C}$ . Crack-free, transparent gel films were obtained from all of the solutions. Figure 3 shows the optical micrographs of the as-deposited gel air, where the gel films were transferred to an electric furnace held at the prescribed temperature after dip coating. Crack-free, transparent titania films were basically obtained for all of the conditions, while a few small cracks were only occasionally observed on the surface after heating at $600^{\\circ}\\mathrm{C}.$ Anatase phases were detected in the XRD patterns of the titania films heated at $600^{\\circ}\\mathrm{C},$ irrespective of the addition of PG and DPG, while all of the films heated at $200~^{\\circ}\\mathrm{C}$ were composed of the amorphous phase (the XRD patterns are shown in Figure S3 of the Supporting Information).  \n\n![](images/d5391d3c6ffe98f2f191168aa54f390bfdf8e715a24eb09b5b9d321b3678c02b.jpg)  \n\nFigure 4 shows the dependence of the thickness upon the PG and DPG contents in the coating solutions for the heat-treated films. Cell-like patterns of $20-50~\\mu\\mathrm{m}$ in width were observed on the surface, irrespective of the composition of coating solutions, where the surface patterns were linearly arranged parallel to the substrate withdrawal direction. The formation of linearly arranged cell-like patterns during dip-coating agreed with our previous work,33,35 which could be attributed to Bénard−Marangoni convection triggered by solvent evaporation. During the dip coating at ${\\bf\\bar{60}}\\ {}^{\\circ}{\\bf C},$ $2{\\cdot}\\mathrm{Pr}$ as the major solvent of the coating solutions could rapidly evaporate from the coating layer on the substrate, leading to the evaporationdriven pattern formation on the surface. However, the gelation of the coating layers containing PG and DPG did not complete without the heat treatment as a result of the high boiling point of the co-solvents (Table 1). Thus, the thickness and surface roughness measurements with a contact probe surface profilometer could not be carried out for the as-deposited gel films, because the coating layers was scraped off by the contact probe during the measurements.  \n\n![](images/938ba24e6521b4ac367cd888b24ad67594a78261869efcc8a48a613d75bf4827.jpg)  \nFigure 3. Optical micrographs of the as-deposited gel films obtained (a) without co-solvents $\\dot{\\boldsymbol{x}}$ and $y=0$ ) and with (b) PG $\\stackrel{\\prime}{x}=0.75$ ) and (c) DPG $\\left(y=0.75\\right)$ , dried at $60~^{\\circ}\\mathrm{C}$ .   \nFigure 4. Dependence of film thickness upon PG and DPG volumes in the coating solutions for the titania films heated at 200 and $600^{\\circ}\\mathrm{C}$ ( $\\mathbf{\\Phi}_{x}$ or $y=0{-}\\mathrm{\\bar{1}}.50_{,}^{\\cdot}$ ). The error bars represent the standard deviations. The lines are a guide to the eye.  \n\nTo obtain rigid coating layers, we heated the as-deposited gel films. Heat-treated titania films were obtained from the gel films of $x$ or $y=0{-}1.50$ by heating at 200 or $600~^{\\circ}\\mathrm{C}$ for $10~\\mathrm{min}$ in titania films, where the co-solvent contents are described with the co-solvent volume per gram of $\\mathrm{Ti}(\\mathrm{OC}_{3}\\mathrm{H}_{7}^{~i})_{4}$ in the solutions (Table 2). Generally, the thickness of dip-coating layers is known to be influenced by the viscosity of the coating solutions. The higher viscosities suppress the downward flow of the coating solution on the substrate, resulting in the formation of thicker films. The thickness of the titania films heated at 200 $^{\\circ}\\mathrm{C}$ increased from ca. $150~\\mathrm{nm}$ ( $x$ or $y=0,$ ) to ca. $370~\\mathrm{nm}$ ( $\\overset{\\cdot}{x}=$ 1.50) and ca. $340~\\mathrm{nm}$ $(y=1.50)$ with increasing PG and DPG volumes, respectively. The slight increase in the thickness was also observed for the films heated at $600~^{\\circ}\\mathrm{C},$ where the thickness increased from ca. $110\\ \\mathrm{nm}$ ( $x$ or $y=0$ ) to ca. $140~\\mathrm{nm}$ $\\left(x=1.50\\right)$ and ca. $130~\\mathrm{nm}$ $\\left(y=1.50\\right)$ . The increase in the film thickness with rgw addition of PD and DPG could be caused by the higher viscosity of the coating solutions containing the cosolvents (Table 2). The solutions containing PG possessed higher viscosity than DPG, resulting in the slightly larger film thickness. Moreover, the heat treatment at higher temperatures resulted in a smaller thickness, which may be caused by the burning of organic species and the densification of the films.  \n\nFigure 5 shows the optical micrographs and 3D surface profiles of the titania films heated at $200~^{\\circ}\\mathrm{C}$ . Cell-like patterns of $20-50\\ \\mu\\mathrm{m}$ in width remained after the heat treatment at 200 $^{\\circ}\\mathrm{C}$ (Figure 5a), and the 3D surface profiles show that the center of the patterns was depressed (Figure 5b). The surface patterns became clear with the addition of the co-solvents, especially PG. Figure 6 shows the optical micrograph and 3D surface profile of the titania films obtained with PG $\\stackrel{\\prime}{x}=1.00\\stackrel{\\cdot}{,}$ ) after the heat treatment at $600~^{\\circ}\\mathrm{C}$ [the surface patterns of the films obtained without co-solvents ( $x$ and $y=0$ ) and with DPG $\\left(y=1.00\\right)$ after the heat treatment at $600~^{\\circ}\\mathrm{C}$ are shown in  \n\n![](images/7c085f7d4e26b70675a5f493712938d76e5a778083cb1cf512b6339a6e1ca4c1.jpg)  \nFigure 5. (a) Optical micrographs and (b) 3D surface profiles of the titania films obtained without co-solvents ( $x$ and $y=0$ ) and with PG $(x=1.00)\\$ ) and DPG $\\left(y=1.00\\right)$ , heated at $200~^{\\circ}\\mathrm{C}$ .  \n\n![](images/c86cbd3e5a1eb3c718a9a0067611eed0b6a064f2a24f5f8220b23bdeeab74832.jpg)  \nFigure 6. (a) Optical micrograph and (b) 3D surface profile of the titania films obtained with PG $\\mathit{\\check{x}}=1.00\\check{},$ , heated at $600~^{\\circ}\\mathrm{C}$ .  \n\nFigure S4 of the Supporting Information]. The cell-like patterns did not collapse even after the crystallization and densification of the films, while the height of the patterns after the heating at $600~^{\\circ}\\mathrm{C}$ was small in comparison to $200~^{\\circ}\\mathrm{C}$ (Figures $5\\mathbf{b}$ and $6\\ensuremath{\\mathbf{b}}$ ).  \n\n3.2. Influence of the Co-solvent Contents on the Size of Cell-like Patterns. The surface roughness parameters, S and $R_{z},$ of the heat-treated titania films were measured for the quantitative evaluation of the size of cell-like patterns, where S and $R_{z}$ represent the width and height, respectively, of the patterns (Figure 2b). Figure 7 shows the dependence of the width and height of the surface patterns on the PG and DPG volumes in the coating solutions for the heat-treated titania films. The width of the cell-like patterns monotonically increased with increasing the co-solvent volume (Figure 7a), which indicates the reduction of the number of convection cells per area. On the other hand, the height of the patterns increased with increasing the co-solvent volume up to ca. 0.30 mL and reduced with further addition of the co-solvents (Figure 7b). The initial increase in the height suggests the enhancement of evaporation-driven surface elevation by the addition of the co-solvents, despite the decrease in the number of convection cells. It should also be noted that no significant difference in the width between PG and DPG was observed (Figure 7a), while the titania films obtained with PG exhibited a larger height than DPG (Figure 7b).  \n\nThe decrease in the number of convection cells per area (i.e., the increase in the width of the cell-like patterns) with the addition of PG and DPG is deduced to be caused by the high boiling point and high viscosity of the co-solvents. The presence of the co-solvents with a high boiling point, i.e., low volatility, and high viscosity in the coating layer can inhibit the evaporation-driven convective phenomenon, which means the reduction of the frequency of the occurrence of Bénard−  \n\n![](images/47ba24de58433dbe91f64d06541fbbddecd3241785a49cf8225589b643b3e5a2.jpg)  \nFigure 7. Dependence of (a) width and (b) height of the surface patterns upon PG and DPG volumes in the coating solutions for the titania films heated at 200 and $600~^{\\circ}\\mathrm{C}$ ( $\\dot{\\boldsymbol{x}}$ or $y=0{-}1.50)$ . The error bars represent the standard deviations. The lines are a guide to the eye.  \n\nMarangoni convection. Thus, the addition of PG and DPG could decrease the number of the convection cells per area, leading to the formation of wider cell-like patterns. Because the boiling point of PG and DPG is high enough to disturb the occurrence of Bénard−Marangoni convection at $60~^{\\circ}\\mathrm{C}$ (the boiling point of PG, $188.2\\ ^{\\circ}\\mathrm{C};$ DPG, $230.0\\ ^{\\circ}\\mathrm{C})$ , PG and DPG could similarly influence the number of convection cells, providing the surface patterns with a similar width.  \n\nOn the other hand, the addition of small amounts of PG and DPG [below $0.30\\mathrm{mL}/\\mathrm{g}$ of $\\mathrm{Ti}(\\mathrm{OC}_{3}\\mathrm{H}_{7}{}^{i})_{4}]$ led to a larger surface elevation (Figure 7b), while the addition of the co-solvents reduced the number of convection cells. As shown in eqs 1 and 2, Bénard−Marangoni convection is activated with an increasing coating layer thickness. In fact, we have investigated the influence of the film thickness on the pattern formation induced by Bénard−Marangoni convection for sol−gel-derived titania films, where the height of cell-like patterns increased with increasing film thickness.35 In the present case, the addition of PG and DPG also resulted in the increase in the film thickness (Figure 4), and thus, the larger thickness of the coating layer may contribute to the increase in the height of the patterns.  \n\nHowever, the larger surface elevation observed in the present case cannot be explained only by the influence of the thickness. Figure 8 shows the ratio of the height of cell-like patterns to the thickness for the heat-treated titania films. The height/thickness ratio increased with an increasing co-solvent volume up to ca. $0.30~\\mathrm{mL}$ and reached 0.62 and 0.40 by the addition of PG and DPG, respectively. Table 3 shows the height/thickness ratio for the sol−gel-derived titania films reported in the present and previous works, the latter of which were all prepared without co-solvents. It is seen that the titania films obtained with PG and DPG exhibited a higher height/thickness ratio than that without the co-solvents, irrespective of the film thickness. These suggest that the surface elevation induced by Bénard− Marangoni convection is more strongly activated by the addition of the co-solvents, especially PG. The enhancement of the evaporation-driven surface elevation could be attributed to the higher surface tension gradient as a result of the addition of the co-solvents with a high surface tension and low volatility.  \n\n![](images/0616b67726677008fdea98b0a980a51b7030f1b4af23daf0fcacbc53dac9226e.jpg)  \nFigure 8. Dependence of the height/thickness ratio on PG and DPG volumes in the coating solutions for the titania films heated at 200 and $600~^{\\circ}\\mathrm{C}$ ( $x$ or $y=0{-}1.50\\rangle$ . The lines are a guide to the eye.  \n\nBénard−Marangoni convection may have resulted from the surface tension gradient in the coating layer as a result of the evaporation of $2{\\cdot}\\mathrm{Pr}$ during dip coating at $60\\ ^{\\circ}\\mathrm{C},$ where PG and DPG are thought to remain in the coating layer during the solvent evaporation, creating a much higher surface tension gradient. A higher surface tension gradient could provide a stronger convective flow of solutions, resulting in a larger surface elevation. The larger surface elevation provided by PG than that provided by DPG may be due to the higher surface tension of PG than that of DPG (Figure 7b and Table 3).  \n\nFurther addition of PG and DPG over $0.30~\\mathrm{mL}$ led to the decrease in the height (Figure 7b), where the height/thickness ratio became smaller than that of the films obtained without the co-solvents (Figure 8). Previously, we reported that the slow gelation of the coating layer leads to the disappearance of the surface patterns via solution flow before the completion of the gelation.30,34 The presence of the large amounts of co-solvents with low volatility is thought to suppress the gelation of the coating layer, resulting in the reduction of the height of cell-like patterns.  \n\n3.3. Influence of the Heating Temperature on the Size of Cell-like Patterns. The heat treatment at $600~^{\\circ}\\mathrm{C}$ resulted in the cell-like patterns with a smaller height than $200~^{\\circ}\\mathrm{C}$ (Figure 7b), which could be attributed to the densification of the films. However, the heat-treatment temperature did not influence the height/thickness ratio (Figure 8). On the other hand, the width did not depend upon the heat-treatment temperature (Figure 7a) because the films are contained by the substrate and not allowed to shrink in the in-plane direction.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# 4. CONCLUSION  \n\nSpontaneous pattern formation induced by Bénard−Marangoni convection was observed for the sol−gel-derived titania films prepared from $\\mathrm{Ti}(\\mathrm{OC}_{3}\\mathrm{H}_{7}^{~i})_{4}$ solutions, where micrometerscaled cell-like patterns were formed on the surface during dip coating. The height and width of the patterns were controlled by the addition of co-solvents with a high surface tension and low volatility. The width of the patterns increased with increasing PG and DPG contents, which could be attributed to the reduction of the number of convection cells. On the other hand, the addition of PG and DPG resulted in the increase in the height of the surface patterns, which was thought to be provided by the higher surface tension gradient in the coating layer generated during solvent evaporation and the consequent activation of the surface elevation via the convective flow of solutions. The surface patterns remained even after the heat treatment, and anatase thin films with periodic surface patterns could be obtained.  \n\nTable 3. Height/Thickness Ratio for the Pattern Formation Induced by Bénard−Marangoni Convection on Sol−Gel-Derived Titania Films   \n\n\n<html><body><table><tr><td>film </td><td> solvent</td><td> pattern height (nm)</td><td>thickness (nm)</td><td>height/thickness</td></tr><tr><td colspan=\"5\">Present Work, Heated at 200 °C</td></tr><tr><td>titania</td><td>2-Pr</td><td>42</td><td>148</td><td>0.28</td></tr><tr><td>titania</td><td>2-Pr + PG (0.26 mL of PG)</td><td>213</td><td>346</td><td>0.62</td></tr><tr><td>titania</td><td>2-Pr + DPG (0.35 mL of DPG)</td><td>130</td><td>322</td><td>0.40</td></tr><tr><td colspan=\"3\">Previous Work34 a</td><td></td><td></td></tr><tr><td>titania</td><td>2-Pr</td><td>49</td><td>140</td><td>0.35</td></tr><tr><td>titania-PVPb (Ti/PVP = 0.3)c</td><td>2-Pr</td><td>103</td><td>410</td><td>0.25</td></tr><tr><td>titania-PVPb (Ti/PVP = 0.7)c</td><td>2-Pr</td><td>145</td><td>460</td><td>0.32</td></tr></table></body></html>\n\naAll samples were dried at the coating temperature (without heating). $\\ensuremath{^b}\\ensuremath{\\operatorname{PVP}}=\\ensuremath{\\operatorname{poly}}$ (vinylpyrrolidone). cMole ratio.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 6,
+        "chunk": "# ASSOCIATED CONTENT",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# $\\otimes$ Supporting Information  \n\nThe Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.langmuir.5b02929.  \n\nSchematic illustration of our experimental methods (Figure S1), definitions of surface roughness parameters, including S (mean spacing of local peaks of the profile) and $R_{z}$ (ten point height of irregularities) (Figure S2), XRD patterns of heat-treated thin-film samples (Figure S3), and optical micrographs and 3D surface profiles of thin films heated at $600~^{\\circ}\\mathrm{C}$ (Figure S4) (PDF)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# AUTHOR INFORMATION",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# Corresponding Author  \n\n\\*Telephone: $+81$ -6-6368-1121, ext. 5638. Fax: +81-6-6388- 8797. E-mail: h_uchi@kansai-u.ac.jp.",
+        "category": " References"
+    },
+    {
+        "id": 10,
+        "chunk": "# Notes  \n\nThe authors declare no competing financial interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 11,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nThis work was financially supported by the Sumitomo Foundation Grant-in-Aid for Basic Science Research.",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# REFERENCES  \n\n(1) Adachi, E.; Dimitrov, A. S.; Nagayama, K. Stripe patterns formed on a glass-surface during droplet evaporation. Langmuir 1995, 11 (4), 1057−1060. (2) Brinker, C. J.; Lu, Y. F.; Sellinger, A.; Fan, H. Y. Evaporationinduced self-assembly: Nanostructures made easy. Adv. Mater. 1999, 11 (7), 579−585. (3) Brinker, C. J. Evaporation-induced self-assembly: Functional nanostructures made easy. MRS Bull. 2004, 29 (9), 631−640. (4) Chen, J.; Liao, W.-S.; Chen, X.; Yang, T.; Wark, S. E.; Son, D. H.; Batteas, J. D.; Cremer, P. S. Evaporation-Induced Assembly of Quantum Dots into Nanorings. ACS Nano 2009, 3 (1), 173−180. (5) Fan, F. $\\mathrm{Q.;}$ Stebe, K. J. Assembly of colloidal particles by evaporation on surfaces with patterned hydrophobicity. Langmuir 2004, 20 (8), 3062−3067. (6) Gibaud, A.; Grosso, D.; Smarsly, B.; Baptiste, A.; Bardeau, J. F.; Babonneau, F.; Doshi, D. A.; Chen, Z.; Brinker, C. J.; Sanchez, C. Evaporation-controlled self-assembly of silica surfactant mesophases. J. Phys. Chem. B 2003, 107 (25), 6114−6118. (7) Grosso, D.; Cagnol, F.; Soler-Illia, G.; Crepaldi, E. L.; Amenitsch, H.; Brunet-Bruneau, A.; Bourgeois, A.; Sanchez, C. Fundamentals of mesostructuring through evaporation-induced self-assembly. Adv. Funct. Mater. 2004, 14 (4), 309−322. (8) Hong, S. W.; Byun, M.; Lin, Z. Robust Self-Assembly of Highly Ordered Complex Structures by Controlled Evaporation of Confined Microfluids. Angew. Chem., Int. Ed. 2009, 48 (3), 512−516. (9) Lim, J. A.; Lee, W. H.; Lee, H. S.; Lee, J. H.; Park, Y. D.; Cho, K. Self-organization of ink-jet-printed triisopropylsilylethynyl pentacene via evaporation-induced flows in a drying droplet. Adv. Funct. Mater. 2008, 18 (2), 229−234. (10) Liu, S. T.; Zhu, T.; Hu, R. S.; Liu, Z. F. Evaporation-induced self-assembly of gold nanoparticles into a highly organized twodimensional array. Phys. Chem. Chem. Phys. 2002, 4 (24), 6059−6062. (11) Lu, Y. F.; Fan, H. Y.; Doke, N.; Loy, D. A.; Assink, R. A.; LaVan, D. A.; Brinker, C. J. Evaporation-induced self-assembly of hybrid bridged silsesquioxane film and particulate mesophases with integral organic functionality. J. Am. Chem. Soc. 2000, 122 (22), 5258−5261. (12) Ming, T.; Kou, X.; Chen, H.; Wang, T.; Tam, H.-L.; Cheah, K.- W.; Chen, J.-Y.; Wang, J. Ordered Gold Nanostructure Assemblies Formed By Droplet Evaporation. Angew. Chem., Int. Ed. 2008, 47 (50), 9685−9690.  \n\n(13) Xu, J.; Xia, J. F.; Hong, S. W.; Lin, Z. $\\mathrm{Q.;}$ Qiu, F.; Yang, Y. L. Self-assembly of gradient concentric rings via solvent evaporation from a capillary bridge. Phys. Rev. Lett. 2006, 96 (6), 066104.   \n(14) Yu, K.; Hurd, A. J.; Eisenberg, A.; Brinker, C. J. Syntheses of silica/polystyrene-block-poly(ethylene oxide) films with regular and reverse mesostructures of large characteristic length scales by solvent evaporation-induced self-assembly. Langmuir 2001, 17 (26), 7961− 7965.   \n(15) Zhang, C.; Zhang, X.; Zhang, X.; Fan, X.; Jie, J.; Chang, J. C.; Lee, C.-S.; Zhang, W.; Lee, S.-T. Facile one-step growth and patterning of aligned squaraine nanowires via evaporation-induced self-assembly. Adv. Mater. 2008, 20 (9), 1716−1720.   \n(16) Bénard, H. The cellular whirlpools in a liquid sheet transporting heat by convection in a permanent regime. Ann. Chim. Phys. 1901, 23, 62−101.   \n(17) Block, M. J. Surface tension as the cause of bénard cells and surface deformation in a liquid film. Nature 1956, 178 (4534), 650− 651.   \n(18) Jeffreys, H. The stability of a layer of fluid heated below. Philos. Mag. 1926, 2 (10), 833−844.   \n(19) Koschmieder, E. L.; Biggerstaff, M. I. Onset of surface-tensiondriven bénard convection. J. Fluid Mech. 1986, 167, 49−64.   \n(20) Rayleigh, L. On convection currents in a horizontal layer of fluid, when the higher temperature is on the under side. Philos. Mag. 1916, 32, 529−546.   \n(21) Zhang, N. L.; Chao, D. F. Mechanisms of convection instability in thin liquid layers induced by evaporation. Int. Commun. Heat Mass Transfer 1999, 26 (8), 1069−1080.   \n(22) de Gennes, P. G. Instabilities during the evaporation of a film: Non-glassy polymer $^+$ volatile solvent. Eur. Phys. J. E: Soft Matter Biol. Phys. 2001, 6, 421−424.   \n(23) Pearson, J. R. A. On convection cells induced by surface tension. J. Fluid Mech. 1958, 4 (5), 489−500.   \n(24) Birnie, D. P., III Rational solvent selection strategies to combat striation formation during spin coating of thin films. J. Mater. Res. 2001, 16 (4), 1145−1154.   \n(25) Birnie, D. P., III A Model for Drying Control Cosolvent Selection for Spin-Coating Uniformity: The Thin Film Limit. Langmuir 2013, 29 (29), 9072−9078.   \n(26) Birnie, D. P., III; Kaz, D. M.; Taylor, D. J. Surface tension evolution during early stages of drying of sol-gel coatings. J. Sol-Gel Sci. Technol. 2009, 49 (2), 233−237.   \n(27) Haas, D. E.; Birnie, D. P., III Evaluation of thermocapillary driving forces in the development of striations during the spin coating process. J. Mater. Sci. 2002, 37 (10), 2109−2116.   \n(28) Kozuka, H. On ceramic thin film formation from gels: Evolution of stress, cracks and radiative striations. J. Ceram. Soc. Jpn. 2003, 111 (9), 624−632.   \n(29) Kozuka, H.; Hirano, M. Radiative striations and surface roughness of alkoxide-derived spin coating films. J. Sol-Gel Sci. Technol. 2000, 19 (1−3), 501−504.   \n(30) Kozuka, H.; Ishikawa, Y.; Ashibe, N. Radiative striations of spincoating films: Surface roughness measurement and in-situ observation. J. Sol-Gel Sci. Technol. 2004, 31 (1−3), 245−248.   \n(31) Shibata, S.; Miyajima, K.; Yoshikawa, H.; Yano, T.; Yamane, M. Cellular patterns in organic-inorganic hybrid film. J. Sol-Gel Sci. Technol. 2000, 19 (1−3), 665−669.   \n(32) Uchiyama, H. Evaporation-driven self-organization of sol-gel dip-coating films. J. Ceram. Soc. Jpn. 2015, 123 (1438), 457−464. (33) Uchiyama, H.; Mantani, Y.; Kozuka, H. Spontaneous Formation of Linearly Arranged Microcraters on Sol-Gel-Derived Silica-Poly(vinylpyrrolidone) Hybrid Films Induced by Benard-Marangoni Convection. Langmuir 2012, 28 (27), 10177−10182.   \n(34) Uchiyama, H.; Miki, Y.; Mantani, Y.; Kozuka, H. Spontaneous Formation of Micrometer-Scaled Cell-like Patterns on AlkoxideDerived Silica Gels Induced by Benard-Marangoni Convections. J. Phys. Chem. C 2012, 116 (1), 939−946.   \n(35) Uchiyama, H.; Namba, W.; Kozuka, H. Spontaneous Formation of Linear Striations and Cell-like Patterns on Dip-Coating Titania Films Prepared from Alkoxide Solutions. Langmuir 2010, 26 (13), 11479−11484.   \n(36) de Gennes, P. G. Solvent evaporation of spin cast films: ″crust″ effects. Eur. Phys. J. E: Soft Matter Biol. Phys. 2002, 7, 31−34.   \n(37) Weh, L. Surface structures in thin polymer layers caused by coupling of diffusion-controlled Marangoni instability and local horizontal temperature gradient. Macromol. Mater. Eng. 2005, 290, 976−986.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "Historical perspective",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Water drop-surface interactions as the basis for the design of anti-fogging surfaces: Theory, practice, and applications trends  \n\nIván Rodríguez Durán a,b, Gaétan Laroche a,b,⁎  \n\na Laboratoire d'Ingénierie de Surface, Centre de Recherche sur les Matériaux Avancés, Département de Génie des Mines, de la Métallurgie et des Matériaux, Université Laval, 1065 Avenue de la médecine, Québec G1V 0A6, Canada b Centre de Recherche du Centre Hospitalier Universitaire de Québec, Hôpital St-François d'Assise, 10 rue de l'Espinay, Québec G1L 3L5, Canada",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# a r t i c l e i n f o",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# a b s t r a c t  \n\nAvailable online 24 November 2018  \n\nKeywords:   \nAnti-fogging surface   \nWater drop   \nFilmwise condensation Cassie-Baxter equation Self-healable coating Anti-bacterial activity  \n\nGlass- and polymer-based materials have become essential in the fabrication of a multitude of elements, including eyeglasses, automobile windshields, bathroom mirrors, greenhouses, and food packages, which unfortunately mist up under typical operating conditions. Far from being an innocuous phenomenon, the formation of minute water drops on the surface is detrimental to their optical properties (e.g., light-transmitting capability) and, in many cases, results in esthetical, hygienic, and safety concerns. In this context, it is therefore not surprising that research in the field of fog-resistant surfaces is gaining in popularity, particularly in recent years, in view of the growing number of studies focusing on this topic. This review addresses the most relevant advances released thus far on anti-fogging surfaces, with a particular focus on coating deposition, surface micro/nanostructuring, and surface functionalization. A brief explanation of how surfaces fog up and the main issues of interest linked to fogging phenomenon, including common problems, anti-fogging strategies, and wetting states are first presented. Anti-fogging mechanisms are then discussed in terms of the morphology of water drops, continuing with a description of the main fabrication techniques toward anti-fogging property. This review concludes with the current and the future perspectives on the utility of anti-fogging surfaces for several applications and some remaining challenges in this field.  \n\n$\\mathfrak{C}$ 2018 Elsevier B.V. All rights reserved.",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# Contents  \n\n1. Introduction 69   \n2. Wetting states of anti-fogging surfaces 70   \n2.1. Smooth surfaces . 70   \n2.1.1. Young's equation . 70   \n2.2. Rough surfaces . 71   \n2.2.1. Wenzel equation 71   \n2.2.2. Cassie-Baxter equation 71   \n2.3. The issue of line tension in micro/nano droplets and contact angle hysteresis . 71   \n3. How to prevent surfaces from fogging up: Anti-fogging strategies, mechanisms, and materials 72   \n3.1. (Super)hydrophilic anti-fogging surfaces: Spreading mechanism 72   \n3.2. (Super)hydrophobic anti-fogging surfaces: Rolling mechanism 74   \n3.3. Hydrophilic/oleophobic anti-fogging surfaces: Percolation mechanism . 74   \n4. Fabrication techniques toward anti-fogging property . 76   \n4.1. Bottom-up processing. 76   \n4.1.1. Dip-coating deposition 76   \n4.1.2. Spin-coating deposition . 78   \n4.1.3. Layer-by-layer deposition . 81   \n4.1.4. Physical and chemical vapor deposition 83   \n4.1.5. Electrochemical deposition 84   \n4.1.6. Others 84   \n4.2. Top-down processing. 84   \n4.2.1. Dry and wet etching methods . 84   \n4.2.2. Lithography . . 85   \n4.2.3. Template-assisted fabrication 86   \n4.3. Surface functionalization and related techniques 87   \n5. Application trends of anti-fogging surfaces 87   \n5.1. Food industry 87   \n5.2. Photovoltaic industry . 87   \n5.3. Medicine 88   \n5.4. Optical applications 88   \n6. Concluding remarks and outlook . 88   \nAcknowledgements 89   \nReferences 89",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 1. Introduction  \n\nFogging can be defined as the natural phenomenon ocurring when water vapor condenses on a solid surface whose temperature falls below the dew point of the surrounding air-water vapor mixture [1]. The dew point is the temperature at which water vapor in air must be cooled to reach saturation (relative humidity of $100\\%$ ) [2]. From a physical point of view, the conversion of water vapor into liquid water in the presence of a solid surface involves two main stages, namely, formation of minute droplets with radii exceeding a critical value or “heterogeneous nucleation” and drop growth [3]. Once water drops are formed on the surface, the extent of fogging will primarily depend on their contact angles. In general, the higher the contact angles, the more pronounced the effects of condensation [4]. The main reason for this lies in the fact that each droplet scatters the incident light in all directions because of the small radius of curvature at the water drop /air interface [5]. The interaction between light and water droplets explains to a large extent, why transparent materials become blurry when exposed to hot and humid environments. This feature of fogged surfaces is commonly referred to in the literature as “breath figures” [6–8].  \n\nThe fogging of surfaces has been shown to cause detrimental effects on sectors of activity as diverse as the medical, the automotive, or the photovoltaic. For example, the presence of condensation on optical elements such as mirrors, lenses, and prisms decreases the precision of microscopes and chromatographs [9,10]. In the automotive and aeronautic sectors (e.g., train, vehicle, and aircraft), the fogging of windshields is quite often linked to safety concerns as it severely reduces the driver's field of view [11–14]. Fogging has also been reported to impair the visual field of endoscopes during surgical procedures [15] and lower the energy-conversion efficiency of solar cells [16]. In the food industry, condensation on greenhouse claddings limits the crop yield [17,18] and reduces the visual appearance of packaged food, which is perceived by consumers as a lack of freshness and quality [19].  \n\nThus far, two anti-fogging strategies have amply demonstrated their effectiveness in preventing these situations from occurring. The first one aims at changing certain environmental parameters, such as temperature, relative humidity, and surrounding air flow to avoid or remove condensation. Rear windshields, chiller cabinets, or swimming pool windows equipped with heat elements, are some examples of how to get rid of fogging by simply changing the temperature. Typically, the heating equipment is a conductive coating that keeps surface temperature above the dew point upon application of a voltage [20]. Quite a number of papers on electrothermal coatings based on oxides such as $\\mathrm{In}_{2}{\\sf O}_{3}–\\mathrm{Sn}{\\sf O}_{2}$ [21] and graphene oxide [22,23], metals such as Ni, Ag, and Cu [24–26], and semimetals such as carbon nanotubes [27] and graphene [28], have been published in this regard. These materials make it possible to remove surface fog with minimal energy consumption [29].The improvement of air circulation is another well-known anti-fogging approach as it promotes water evaporation and diminishes the number of potential condensation points [30,31]. The way windshield defrosting/defogging systems operate is an obvious example [12,32,33]. In the same vein, both the incorporation of moist adsorbents [34] and purging with dry air or inert gas [35,36] have also proven to be successful in preventing condensation in dual-panel lens and doubleglazed windows, respectively.  \n\nThe second category of anti-fogging strategies focuses on changing the morphology of water drops by tuning the wetting characteristics of the surface. The wetting behavior of any material can be tailored by adjusting its surface features, such as the roughness or chemistry, either by direct modification or by depositing a coating of a distinct material on the surface. As detailed in the following sections, such practices have shown to be suitable to endow anti-fogging surfaces with additional features such as icing-delay, anti-reflective, anti-bacterial, or anti-fouling characteristics. Anti-fogging strategies pertaining to the direct modification of the substrate's surface features can in turn be divided into two families. The first one is based on the creation of functional groups different from those originally found on the surface (i.e., surface chemistry modification). In this case, bulk properties and surface topography remain virtually unchanged. On the contrary, the second family of anti-fogging strategies involves either enhancing surface roughness or “carving” surface nano/micro features with well-defined geometries, by means of “bottom-up” processing. Here, a rigorous control of the surface topography is crucial, as surface features exceeding $100\\mathrm{nm}$ have been shown to compromise the optical properties, mainly because of light scattering, and the resistance to scratching and wear [37,38]. On the other hand, the deposition of thin films by “top-down” processing has also proven to be as effective as “bottom-up” processing or surface treatments in endowing polymeric and ceramic substrates with the anti-fogging feature.  \n\nGiven the above-mentioned considerations, anti-fogging surfaces can be classified into four distinct groups according to their apparent contact angles (APCAs) [39]: more specifically, superhydrophilic, hydrophilic, superhydrophobic, and hydrophobic surfaces. Hydrophilic and superhydrophilic surfaces, with an APCA in the range of $10^{\\circ}<\\theta<$ $40{-}50^{\\circ}$ and $5^{\\circ}<\\theta<10^{\\circ}$ , respectively, are made of “water-loving” materials. According to Drelich and colleagues [40], complete drop spreading or “superhydrophilicity” is possible only in textured or/and structured surfaces (rough and/or porous) featuring a roughness factor, as defined by Wenzel equation, greater than one. Surfaces with water-attracting features cause water drops to spread over the surface, thus forming a thin water film that allows for incident light to pass through without being scattered. As a result, the surface remains optically clear, even under strong fogging conditions. A water contact angle of $90^{\\circ}$ has been conventionally adopted as the cut-off value to differentiate hydrophilic surfaces from those repelling water, i.e., (super)hydrophobic surfaces [41,42]. That said, it is widely accepted that surfaces with water contact angles above $40{-}50^{\\circ}$ [4,5,43] are not able to mitigate the effects of condensation despite being hydrophilic;  \n\nhence, the above-mentioned $10^{\\circ}<\\theta<40{-}50^{\\circ}$ range. Hydrophobic and superhydrophobic surfaces, with an APCA in the range of $90^{\\circ}<\\theta<$ $150^{\\circ}$ and $150^{\\circ}<\\theta<180^{\\circ}$ , respectively, are typically prepared by a two-step process consisting of surface micro-/nano-structuration, followed by the deposition of a water-repellent material. The term “superhydrophobic” refers to a nearly non-wettable state characterized by very low contact angle hysteresis and sliding angles $(<5\\AA-10\\mathrm{^\\circ})$ [44], and can formally be described by the “Cassie air-trapping” or a closely related wetting state [39,45]. Contrary to (super)hydrophilic surfaces, the application of water repellency for anti-fogging purposes appears to have attracted less interest within the scientific community. The fact that (super)hydrophobic surfaces must be tilted to remove condensation, and that the combination of water repellency with the anti-fogging performance calls for more complex and more timeconsuming manufacturing processes may account for this divergence.  \n\nA concise overview of common fogging concerns and the fundamental aspects of fogging occurrence are introduced in Section 1. On this basis, wetting states depicting the interaction of water drops with solid surfaces are presented in Section 2. Materials and anti-fogging mechanisms are described in Section 3. In Section 4, fabrication techniques toward anti-fogging property are discussed in detail and classified into “top-down” and “bottom-up” processing, and surface functionalization. Featured applications of anti-fogging surfaces in key sectors of activity such as the food and photovoltaic industries and medicine, are addressed in Section 5. Section 6 concludes with our personal standpoint based on remaining and forthcoming challenges, current trends, and potential promising breakthroughs in this field.",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2. Wetting states of anti-fogging surfaces  \n\nExperience shows that condensation of water vapor on a solid surface can occur according to two distinct modes, namely dropwise and filmwise condensation [46–48]. In dropwise condensation, which typically takes place on low energy surfaces, water drops are yielded with high or very high contact angles. Owing to this particular feature, the effects of fogging materialize, although the surface is not fully wetted. On the contrary, should condensation take place on a substrate with high energy surface, water drops will exhibit very low contact angles (filmwise condensation). Here, no fogging is observed, as a thin film of water, not greatly hindering light transmission, forms on the surface. As can be inferred from what Mother Nature shows us, the morphology of water drops determines whether the condensate will fog up the solid surface or not. With this in mind, surface chemistry and topography must both be properly adjusted to change water drops shape, and in this way, design surfaces simultaneously meeting suitable wetting behavior and anti-fogging requirements. As detailed in the following section, several wetting states have been proposed to explain the wettability of solid surfaces, considering surface chemistry and topography in a straightforward way, in terms of contact angles and surface roughness.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.1. Smooth surfaces",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.1.1. Young's equation  \n\nAs depicted in Fig. 1, water drops resting on a smooth surface can be characterized by the angle $\\theta_{0}$ between the surface and the tangent line drawn along the liquid/vapor interface from the point where solid, liquid, and vapor phases meet. In the early 19th century, Thomas Young [49] stated that the contact angle $\\theta_{0}$ is governed by the mechanical equilibrium resulting from surface tensions acting on the liquid drop/surface system, as follows:  \n\n$$\n\\mathbf{cos}\\pmb{\\theta_{0}}=\\frac{\\pmb{\\gamma_{S V}}-\\pmb{\\gamma_{S L}}}{\\pmb{\\gamma_{L V}}}\n$$  \n\nwhere $\\gamma_{S L},\\gamma_{S V},$ and $\\gamma_{L V}$ are the surface tensions solid/liquid, solid/vapor, and liquid/vapor, respectively, and $\\theta_{0}$ is the so-called “static contact angle”.  \n\nStrictly speaking, Eq. (1) does not appear in Young's publication “An essay on the cohesion of fluids” [49]; however, there are two statements contained in it, namely, for each combination of a solid and a fluid, there is an appropriate angle of contact between the surfaces of the fluid, exposed to the air, and the solid and We may therefore inquire into the conditions of equilibrium of the three forces acting on the angular particles, one in the direction of the surface of the fluid only, a second in that of the common surface of the solid and fluid, and the third in that of the exposed surface of the solid, which substantiate that the contact angle can be defined in terms of the surface tensions $\\gamma_{S L},\\gamma_{S V},$ and $\\gamma_{L V}.$ Although the use of surface tensions rather than forces, as stated by Young, has been a subject of debate [50], theoretical derivation of Eq. (1) has recently been proven using thermodynamic arguments [51–54]. Despite this, Young's equation (Eq. (1)) does not adequately reflect the complexity of wetting phenomena, as it applies strictly to atomically flat and chemically homogeneous surfaces that neither dissolve nor react when in contact with the liquid. With all these constraints, interpreting water contact angles measured on real surfaces, i.e., APCAs, calls for wetting states considering, not only surface chemistry (via surface tensions) but also surface roughness.  \n\n![](images/8db9ac63e7ace8844a6fa5cedd90b266d737c8e5c3bad009dbd0443d365ab5b6.jpg)  \nFig. 1. Microscopic view of a water drop showing surface tensions at liquid/vapor, liquid/solid, and solid/vapor interfaces and forces acting on water molecules (adhesive and cohesive forces). Surface tension is the energy required to increase the surface area of a given phase by a unit of area $(\\mathrm{J}\\mathrm{m}^{-2},$ ). $\\mathrm{F}_{\\mathrm{s}}= $ forces between water molecules at the drop surface, and $\\mathrm{F_{b}=}$ forces between water molecules within the bulk.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.2. Rough surfaces",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 2.2.1. Wenzel equation  \n\nFollowing observation of contact angles on real surfaces, Wenzel [55,56] proposed an alternative to Young's equation including the effect of surface roughness on the wetting behavior, as follows:  \n\n$$\n\\mathrm{cos}\\theta_{W}=R_{f}\\ \\mathrm{cos}\\theta_{0}\n$$  \n\nwhere $\\theta_{W}$ is the “apparent contact angle” or the contact angle measured on a rough surface, $R_{f}$ is the roughness factor, and $\\theta_{0}$ is the contact angle as described by Eq. (1). The roughness factor is defined as the ratio between the real surface area $A_{R}$ (for a given surface topography, i.e., peaks and valleys) and the geometric area resulting from the projection of the rough surface onto a hypothetical planar surface AP. Given that $A_{R}>A_{P},$ hydrophilicity and hydrophobicity are both enhanced with surface roughness. Indeed, an increase in roughness factor lowers $\\theta_{W}$ when $\\theta_{0}$ $\\angle90^{\\circ}$ yet enhances $\\theta_{W}$ when $\\theta_{0}>90^{\\circ}$ . Regardless of the hydrophilicity/ hydrophobicity of the surface, the wetting of a rough and chemically homogeneous surface results in a solid-water interface with no air trapped within, namely the Wenzel wetting state. (Fig. 2a).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 2.2.2. Cassie-Baxter equation  \n\nAs reported in the preceding paragraph, Wenzel state presumes that rough surfaces are fully wettable. Nevertheless, it has been shown that liquid drops can eventually break Wenzel's assumption, and not displace the air trapped into the cavities [57,58]. Cassie and Baxter addressed this issue by assuming that such surfaces are composed of two distinct features, one with a fractional area $\\varphi_{1}$ and Young's contact angle $\\theta_{1}$ , and the other, with a fractional area $\\varphi_{2}$ and Young's contact angle $\\theta_{2},$ , with $\\varphi_{1}+\\varphi_{2}=1$ . The apparent contact angle, which can be regarded as a weighted average of static contact angles for each fraction, is given by the Cassie-Baxter equation:  \n\n$$\n\\mathrm{cos}\\theta_{C B}=\\varphi_{1}\\mathrm{cos}\\theta_{1}+\\varphi_{2}\\mathrm{cos}\\theta_{2}\n$$  \n\nIn this case, two wetting scenarios are possible: Cassie air-trapping and Cassie impregnating sates. The first wetting state considers water drops lying on the top of protrusions of the solid surface and air trapped underneath them (Fig. 2b). This distinguishing feature of the Cassie airtrapping state has been attributed either to re-entrant geometries [59] or the combination of a hierarchical topography with a low surface energy material. On this basis, the first fraction $\\varphi_{1}$ corresponds to the solid/ liquid interface with a fractional area $\\varphi_{S L}$ and $\\theta_{1}=\\theta_{0}$ (flat protrusions), and the second one $\\varphi_{2}$ , to the liquid/vapor interface with a fractional area $\\varphi_{L V}=1\\ –\\varphi_{S L}$ and $\\theta_{2}=180^{\\circ}$ (full water repellency). In light of these boundary conditions, Eq. (3) thus becomes [60,61]:  \n\n$$\n\\mathrm{cos}\\theta_{C A}=-1+\\varphi_{S L}(\\mathrm{\\bf~cos}\\theta_{0}+1)\n$$  \n\nEq. (4) represents the so-called “Cassie air-trapping wetting state” (Fig. 2b). The resulting solid-water-air interface is a sine qua non for a superhydrophobic anti-fogging surface to operate optimally. The term “optimally” refers to the situation in which water drops leave the surface upon rolling leaving no remnants behind. Conversely, if the surface is impregnated by water (water displaces the air trapped in the cavities), Cassie-Baxter equation can be rewritten as follows:  \n\n$$\n\\mathrm{\\bfcos}\\theta_{C I}=1+\\varphi_{S L}(\\mathrm{\\bf~cos}\\theta_{0}-1)\n$$  \n\nEq. (5) represents the so-called “Cassie impregnating wetting state” (Fig. 2c) [45]. In both wetting states, $\\varphi_{S L}$ ranges from 0 to 1. When $\\varphi_{S L}=$ 1, the wetting behavior is described by Young's equation (flat surface), while $\\varphi_{S L}=0$ results in a non-wettable surface $\\m\\theta=180^{\\circ}$ ).  \n\n2.3. The issue of line tension in micro/nano droplets and contact angle hysteresis  \n\nAccording to Marmur [62], Wenzel and Cassie-Baxter equations do not adequately reflect the wetting behavior of real surfaces, as they are built on the assumption that the contact angle does not depend on the size of the drop. Although appropriate for water drops sufficiently large compared with surface features (roughness), these equations do not take into account the non-negligible effects of line tension in nano- and micro-scaled sessile droplets [63–65], which also form during condensation. Bearing this in mind, Bormashenko [66] recently reported a general formula describing the wetting behavior of rough surfaces including the effect of the tension line in minute droplets.  \n\nOn the other hand, for a specific system water drop/surface, the combination of the triad $\\gamma_{S V},\\gamma_{L V},$ and $\\gamma_{S L}$ with surface roughness must result in a unique contact angle. That said, the observed contact angles usually differ from those obtained using the above-mentioned equations, primarily because of the motion of the triple phase contact line (TPCL). The TPCL is defined as the imaginary circular line where solid, liquid, and vapor phases meet (see Fig. 2) [39]. A moving TPCL leads to a minimum value of the contact angle, or “receding angle” $\\theta_{r e c}$ and a maximum one, or “advancing angle” $\\theta_{a d\\nu},$ which can be assessed using two different methods, namely dynamic sessile drop method and tilting base method [41]. In the sessile drop method, a water droplet is dropped onto a horizontal surface from a syringe without losing contact with the needle. When water is removed from the drop, the contact angle decreases to a minimum value or the receding contact angle, $\\theta_{r e c},$ before TPCL moves inward (Fig. 3a). When liquid is added, TPCL reaches a stable state characterized by the advancing contact angle, $\\theta_{a d\\nu},$ that is, the contact angle measured just before TPCL moves outward (Fig. 3b). The difference between advancing and receding contact angles ( $\\Delta\\theta=$ $\\theta_{a d\\nu}-\\theta_{r e c})$ is called “contact angle hysteresis” (CAH) [44]. Adhesion hysteresis, chemical heterogeneities, and surface roughness have been reported as the main factors behind contact angle hysteresis [53,67–70]. Nevertheless, the pinning of the TPCL is probably the most important source of CAH, as observed in silicon wafers [69] and extruded polymer [70] films, known for being atomically smooth and free of chemical heterogeneities. In the tilting base method, a water droplet is placed on a horizontal surface as in the preceding method. The main difference here is that the angle between the surface and the horizontal plane is gradually tilted from $0^{\\circ}$ to a critical value $\\alpha,$ also known as “sliding angle” (SA), triggering drop motion (Fig. 3c) [71]. Accordingly, this method allows for the assessment of contact angles and CAH when water drops meet a tilted or a moving surface (i.e., dynamic wettability). As will be seen later in Section 3.2, the water contact angle (WCA), the contact angle hysteresis, and the sliding angle are key parameters requiring controlto design antifogging surfaces featuring rolling-mechanism.  \n\n![](images/88dfb500c65168210da6b325ecf9e7ca777f7d2e23e18234af0a29e54242d160.jpg)  \nFig. 2. Wetting regimes. (a) Wenzel state, (b) Cassie air-trapping state, and (c) Cassie impregnating state. Solid, liquid, and vapor phases meet in an imaginary circular line known as th “triple phase contact line” (TPCL).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3. How to prevent surfaces from fogging up: Anti-fogging strategies, mechanisms, and materials  \n\nAnti-fogging strategies explored thus far can be grouped into two broad categories. The first one aims at controlling the parameters external to the liquid/solid interface, that is, those involved in the nucleation of water drops , such as temperature, air flow, and relative humidity. This category of anti-fogging strategies is outside the scope of this review, as it does deserve further, more in-depth consideration. The second category of anti-fogging strategies focuses on changing the morphology of water drops either by directly tuning the substrate's surface features (chemistry and roughness) or by coating deposition. Compared to the first category, the elaboration of surfaces endowed with the anti-fogging feature has generated more interest, in light of the numerous papers published in the last ten years. According to the most recent literature, the way these surfaces combat fogging can be explained by three different mechanisms:",
+        "category": " Introduction"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.1. (Super)hydrophilic anti-fogging surfaces: Spreading mechanism  \n\nAnti-fogging surfaces featuring spreading mechanism are mostly coatings made from hydrophilic or “water-loving” materials. These materials interact with water drops causing them to spread across the surface, and thus form a scattering-free water film (Fig. 4). To date, there appears to be general agreement that wetted surfaces remain optically clear under aggressive fogging conditions, if the contact angle of water drops is ${<}40{-}50^{\\circ}$ [4,5,43]. Generally speaking, these coatings can be made either from polymers and inorganic materials or from a mixture of both (composite materials). Natural and synthetic polymers with pendant hydrophilic functionalities such as hydroxyl $(\\mathrm{OH}),$ carboxyl $(\\mathsf{C O O H}),$ ester $(\\mathsf{C O O R}),$ amino $\\begin{array}{r}{(\\overline{{(\\mathsf{N H}_{2})}},}\\end{array}$ amide $(\\mathrm{NHCOR}),$ sulfonic $(\\mathsf{S O}_{3}\\mathrm{H})$ , and dihydrogen phosphate groups $(\\mathrm{PO}_{4}\\mathrm{H}_{2}^{\\cdot}$ ) are commonly used in anti-fogging coatings. The potential applicability of natural polymers in fields impaired by fogging has been receiving increasing attention in recent years due to their unique features, including the possibility of covering thermally sensitive materials, as well as their non-toxic and environmentally friendly nature (Table 1). That said, features such as low-cost, tunable interaction with water drops, easy availability, and crosslinkable nature place synthetic polymers in direct competition with natural ones as anti-fogging materials (Table 2).  \n\nThe criterion of either being naturally-sourced or not, appears not to apply when considering inorganic materials. As a matter of fact, most of the studies reported thus far on inorganic coatings with anti-fogging performance consider more suitable to classify them, according to their response to light, into two groups. The first one comprises intrinsically hydrophilic and non-photoresponsive materials, such as $\\mathrm{SiO}_{2}$ $Z\\mathrm{r}0_{2}$ , $\\mathrm{In}_{2}\\mathrm{O}_{3}–\\mathrm{SnO}_{2}$ (ITO), $\\mathrm{MgO-Al_{2}O_{3}}$ , and graphene oxide, while the second one is integrated by materials becoming superhydrophilic upon exposure to UV light, such as $\\mathrm{TiO}_{2}$ , $Z_{\\mathrm{{nO}}}$ and ${\\mathrm{Bi}}_{2}{\\mathrm{O}}_{3}$ . These materials are typically covered with abundant hydroxyl (OH) groups per area unit. On the other hand, the combination of the photo-induced superhydrophilicity with the photocatalytic property allows for the use of $\\mathrm{TiO}_{2}$ -based materials in applications where self-cleaning and anti-fogging characteristics are required. Without going into detail, photocatalysis is basically a set of reactions whereby a dirty $\\mathrm{TiO}_{2}$ surface gets cleaned at room temperature. For this to occur, $\\mathrm{TiO}_{2}$ must absorb UV light to yield “reactive oxidizing species” (ROS), such as superoxide and hydroxyl radicals, that decompose organic pollutants into $\\mathsf{C O}_{2}$ and $\\mathrm{H}_{2}0$ [72]. Unfortunately, the fact that $\\mathrm{TiO}_{2}$ necessitates UV light to perform makes it challenging to design $\\mathrm{TiO}_{2}$ -based anti-fogging coatings for indoor applications. Indeed, when stored in a dark place, an UV-irradiated $\\mathrm{TiO}_{2}$ surface (superhydrophilic) experiences a conversion toward a more hydrophobic state, which is normally less effective in combating surface fog. To remedy this situation, a growing number of studies have focused efforts not only in enhancing the anti-fogging performance of $\\mathrm{TiO}_{2}$ in the absence of UV light, but also in broadening its photocatalytic response to visible and near-IR regions. Mixing with oxides, such as ${\\sf W O}_{3}$ , $z_{\\mathrm{nO}}$ , $\\mathrm{SiO}_{2}$ , $\\mathrm{ZnFe}_{2}{\\sf O}_{4}$ , and reduced graphene oxide [73–79]; doping with metals, such as Cu and $\\mathsf{A g}$ [80,81]; incorporating porogens, including PEG and cetyltrimethylammonium bromide (CTAB), coupled with a calcination treatment [82–86]; using “building blocks” with high surface-to-volume ratios (e.g., nanofibers, nanobelts, nanospheres) [87–93]; and increasing the surface roughness [94–98], have amply demonstrated to be suitable approaches to fabricate dual anti-fogging/self-cleaning $\\mathrm{TiO}_{2}$ -based films, with no need for UV light to perform.  \n\n![](images/ef60c78c21c4906784a3a3175fce50ab7511c8c7d029f367e36a9d587469e2d9.jpg)  \nFig. 3. Dynamic sessile drop method for the assessment of (a) receding and (b) advancing contact angles. (c) Tilting base method for the measurement of advancing and receding contact angles, and sliding angles. Adapted with permission from “Definitions for hydrophilicity, hydrophobicity, and superhydrophobicity: Getting the basics right”, Law, K.-Y., J. Phys. Chem. Lett., Volume 5, Issue 4, 2014, Pages 686-688. Copyright 2018, American Chemical Society.  \n\n![](images/3019c878adfc7c29254695599986b80d2940b1c55d83199b0b662ea7ab298254.jpg)  \nFig. 4. Illustration of the spreading mechanism. As water drops spread across the surface, total internal reflection (dashed red rays) becomes less prevalent while transmitted light (dashed green rays), increasingly less scattered, travels through the system water drop/surface. These surfaces are either hydrophilic $10^{\\circ}<\\Theta<40–50^{\\circ}.$ ) or superhydrophilic $(5^{\\circ}<\\Theta<10^{\\circ}$ .  \n\n![](images/64611d7c70e9d58f3487db7dd42502cdec4ccc311375d38586f075abf735e501.jpg)  \n\nTable 2 Repeating units of the main synthetic polymers used in anti-fogging formulations.   \n\n\n<html><body><table><tr><td>Family</td><td>Repeating unit</td><td>Anti-fogging polymer</td></tr><tr><td>Polyether</td><td></td><td>Poly (ethylene glycol) (PEG) (*) R=R=H Poly (ethyleneglycol dimethacrylate) (PEGDMA) (*) R=R Poly (ethyleneglycol methacrylate) (PEGMA) (*) R=H, R as in PEGDMA Poly (ethyleneglycol diacrylate) (PEGDA) (*)</td></tr><tr><td>Polyvinyl</td><td></td><td>R=R= Poly (vinyl alcohol) (PVA) (*) R=OH Poly (vinyl acetate) (PVAc) (***) R= Poly (vinyl-N-pyrrolidone) (PVP)(*)</td></tr><tr><td>Polyacrylates & Polyacrylamides</td><td></td><td>R= Poly (acrylic acid) (PAA)(*) R=OH Poly (2-hydroxyethyl acrylate) (PHEA)(*) OH R= Poly (acrylamide) (PAM)(*) R= NH Poly (methacrylic acid) (PMAA) (*)</td></tr><tr><td>Polymethacrylates</td><td></td><td>R=OH Poly (methyl methacrylate) (PMMA) (***) R=O-CH Poly (2-hydroxyethyl methacrylate) (PHEMA) (**) OH R= Poly (dimethylaminoethyl methacrylate) (PDMAEMA) (*) R</td></tr></table></body></html>\n\n\\*Water-soluble. \\*\\*Water-swellable. \\*\\*\\*Water-insoluble.  \n\nDespite not being implemented as widely as coating deposition, the direct modification of the substrate's surface features (chemistry and roughness) has amply proven its effectiveness in fabricating fogresistant surfaces featuring spreading mechanism. In this regard, the anti-fogging performance can be met either by modifying surface topography (Section 4.2) or by creating hydrophilic functionalities by means of surface treatments (Section 4.3).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3.2. (Super)hydrophobic anti-fogging surfaces: Rolling mechanism  \n\nContrary to those featuring spreading mechanism, surfaces with water-repellent characteristics must be tilted to a minimal angle $\\alpha$ (sliding angle) to roll off water drops, and thus avoid the effects of surface fog (Fig. 5). There is general agreement among the scientific community that surface features required for a superhydrophobic anti-fogging surface to perform optimally are high contact angles (CA) coupled with low CA hysteresis and low slides angles. Surfaces displaying these characteristics fall into one of the following wetting states: Wenzel, Cassie airtrapping, Cassie impregnating (with a single level of hierarchy of roughness), and Lotus-like (with a double level of hierarchy of roughness, that is micro and nanoscale roughness). The rose petal-like state has not been considered here as it usually displays high contact angle hysteresis. Cassie air-trapping and Lotus-like wetting states are suitable for antifogging purposes as water drops roll off the surface leaving no others behind. In contrast, Wenzel and Cassie impregnating wetting states do not meet anti-fogging requirements. Here, drops remaining entrapped into the surface features, after the tilting of the surface, can be detrimental to the anti-fogging performance, as they scatter light as larger water drops do. With this in mind, anti-fogging surfaces featuring rolling mechanism can be fabricatedby two different routes: the “two-step” and “three-step” routes. The “two-step” route (Fig. 6a), which is typically applied to ceramic substrates, is based on the deposition of “building units” followed by a treatment with a low surface energy material [99–103], while the “three-step” route (Fig. 6b) consists of surface microstructuring of a polymeric substrate by soft lithography (Section 4.2.2), followed by coating deposition and hydrophobization [104,105].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 3.3. Hydrophilic/oleophobic anti-fogging surfaces: Percolation mechanism  \n\nAnti-fogging surfaces featuring percolation mechanism are mainly coatings made of fluorosurfactants polymers, namely, perfluorinated polyethylene glycol polymers [106–113] (Fig. 7a) and perfluoropolyether polymers (Fig. 7b) [114,115], containing hydrophilic and oleophobic domains [116]. Due to this particular feature, these surfaces enable small molecules (e.g., water molecules) to penetrate the coating faster than do larger ones (e.g., hexadecane molecules). To date, two distinct mechanisms have been proposed to explain this striking behavior. The first one, at times referred to as the “flip-flop” mechanism, relies on the presence of “defects” of appropriate size in the coating [106,107,109,110,112,113]. In general, when fluorosurfactants are deposited on a substrate, perfluorinated chains are orientated outward (hydrophobic/oleophobic region) while polyethylene glycol- and hydroxyl-containing moieties are directed toward the surface (hydrophilic/oleophobic region). Considering that this configuration results in a low surface energy barrier repelling both oil and water drops, right-sized defects in the fluorinecontaining layer are thus necessary to enable water drops to permeate and reach the interface coating/substrate (Fig. 8). Another proposed mechanism accounting for the simultaneous hydrophilicity/oleophobicity relies on the rearrangement of polymer chains when in contact with water or any other polar liquid [114,115]. Contrary to the preceding mechanism, the presence of defects in the fluorine-containing region is no longer necessary. Here, when a water drop meets the surface, perfluorinated chains rapidly rearrange inducing the formation of “channels” that allow for small water molecules to permeate quickly toward the hydrophilic region, while blocking or slowing down the passage of larger oil molecules. As in the case of $\\mathrm{TiO}_{2}$ -based materials, surfaces with simultaneous hydrophilicity and oleophobicity are suitable for use in applications requiring anti-fogging performance with a certain degree of self-cleaning activity. Badyal's group [112] proposed a “switching parameter”, defined as the difference between oil (hexadecane) and water static contact angles, to quantitatively assess the percolation mechanism. The higher the “switching parameter,” the better these antifogging surfaces perform. In another study, Howarter et al. [109] demonstrated that an advancing WCA $<30^{\\circ}$ and a receding $0C A>67^{\\circ}$ , are necessary to meet simultaneous self-cleaning and anti-fogging properties. In either case, the strong affinity between water molecules and the surface enables water drops (the cleaning fluid) to wet the surface by displacing oily substances (the pollutant).  \n\n![](images/2a45f8e9b6fb984444dae03acaf28ed069df40902e761b806cb3019a5629e57c.jpg)  \nFig. 5. Illustration of the rolling mechanism. Upon elevation of one side of the surface, water drops roll off easily thus mitigating condensation effects. These surfaces are either hydrophobic $150^{\\circ}>\\Theta>90^{\\circ}$ ) or superhydrophobic $\\mathrm{(\\Theta)}=150^{\\circ},$ and exhibit very low CAH and SA.  \n\n![](images/0696dcb5fda52e9440e7783f762322a2deca47a7134ef41e31a1a6ae9d3179b0.jpg)  \nFig. 6. Routes toward water-repellency and anti-fogging performance. (a) The “two-step” route: deposition of a layer with high specific surface followed by hydrophobization. (i) Deposition of fly-eye bio-inspired ZnO nanostructures and treatment 1H, 1H, 2H, 2H-perfluor oxysilane TES) [99]; (ii) deposition of raspberry-like SiO2 nanospheres and hydrophobization with 1H,1H,2H,2H-p lan lion-like ZnO microspheres and subsequent treatment with heptadecafluorodecyltripro oxysilane (FAS-17) [101]; (iv nd hydrophobization with PFOTES [102]; (v) deposition of multiscale ommatidial arrays of a resin propyl polysilse with 1H,1H,2H,2H-heptadecafluorodecyl methacrylate (HDMA) [103]. (b) The “three-step” route: surface roughening, coatin osition terial. (i) Dome-like surfaces on PDMS covered with solid SiO2 nanoparticles and hydrophobization with fluoroalkylsilane molecules (FAS) [105]; (ii) ZnO nanohairs on poly (vinylidene difluoride) (PVDF) microratchets treated with FAS-17 [104]. WCA: water contact angle, CAH: contact angle hysteresis, SA: sliding angle. Figures reprinted with permission from references [99-105].  \n\n![](images/dc9be6c938a739845b26a530645791e06743f3df3d5c3fbd266872fbea0afec6.jpg)  \nFig. 7. Fluorocarbon surfactants used in anti-fogging surfaces featuring percolation mechanism. (a) Linear and “Y-shaped” perfluorinated polyethylene glycol oligomers. Hydrophilic and oleophobic components are separated in the polymer chain. Depending on the hydrophilic domain, these molecules can be anionic, cationic, non-ionic, or amphoteric. (b) Family of perfluoropolyether polymers (PFPE): hydrophilic and oleophobic domains cannot be distinguished in the backbone. Red: hydrophilic domain, blue: hydrophobic domain, purple: a polymerizable vinyl group.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 4. Fabrication techniques toward anti-fogging property  \n\nThe above-illustrated mechanisms highlight the fact that a judicious combination of surface topography and surface chemistry is key to developing surfaces with fogging resistance. Bearing this in mind, a plethora of fabrication techniques aimed at adjusting the wetting behavior of water drops on solid surfaces has been thus far applied. The following sections present the most widely used techniques for the preparation of anti-fogging materials. To be consistent with the notions outlined above, these techniques have been classified into three distinct categories: bottom-up and top-down processing, and surface functionalization.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# 4.1. Bottom-up processing  \n\nBottom-up processing involves the assembly of small “bricks” such as nanoparticles and polymers into more complex systems.",
+        "category": " Introduction"
+    },
+    {
+        "id": 19,
+        "chunk": "# 4.1.1. Dip-coating deposition  \n\nWhen vinyl/acrylic polymers such as PVA, PVP, and PAA, are used as starting materials, dip-coating deposition allows for the fabrication of anti-fogging coatings endowed with frost-resisting and even selfhealing features [117–120]. In PET and PC substrates (eyeglasses) covered with PVA-Nafion complexes prepared by Sun et al. [121] a minimum thickness of $61~\\mathrm{{nm}}$ was required to prevent fogging effects at room temperature, while a thickness of 247 nm was necessary to ensure transparency over boiling water (Fig. 9a). In addition to providing PC lenses free of frozen fog (Fig. 9b,c), PVA/Nafion films were also found to be self-healable (Fig. 9d,e). After five cycles of damage and healing tests, the transmittance of the coated PET fully recovered (Taverage $\\approx99\\%$ at $500\\mathrm{nm}$ ), as supported by the complete closing of the scratches (Fig. 9f,g). Although PEG-based coatings do not feature self-healability [122], hydrogels prepared by Molina et al. [123] using a PEG functionalized with 3-isocyanatopropyltriethoxysilane hold great promise for the manufacture of anti-fogging films with drug delivery capability, due to its water absorbing characteristics. Anti-fogging coatings made from an isosorbide-based epoxy resin, also exhibited potential applicability as drug delivery system due to the swelling capacity conferred by the epoxide groups [124]. Different research groups have recently developed fog-resistant films containing sulfonic and phosphonic groups, well known for their high water-absorbing characteristics and underwater oleophobicity [125–128]. Ezzat and colleagues [129] fabricated anti-fogging glasses with extreme wettability $(\\mathsf{W C A}<5^{\\circ}),$ by anchoring zwitterionic poly(sulfobetaine methacrylate) (pSBMA) and poly(sulfobetaine vinylimidazole) (pSBVI) polymer brushes, while Huang et al. [130] used silanized zwitterionic sulfobetaine silane (SBSi) for the same purpose (Fig. 10a). In the latter study, the coated glasses recovered up to $99\\%$ of the initial light transmission after being exposed to hot water, as well as cooled at $-20^{\\circ}C$ (Fig. ${10}\\mathsf{b},{\\mathsf{c}}^{\\cdot}$ ). This behavior was in agreement with the observed “see-through” property under different fogging scenarios (Fig. 10d,e). Furthermore, a SBSicoated stainless steel mesh selectively separated water from various oil/water mixtures and oil/water emulsions with high efficiency $(>$ $99.5\\%$ and $>98.2\\%$ , respectively) (Fig. 10f,g). Oil/water separation efficiencies $>99.5\\%$ were also observed in a stainless steel wire mesh coated with anti-fogging formulations based on phytic acid and ferric ions $(\\mathsf{F e}^{\\mathrm{III}})$ [131]; while fog-resistant coatings reported by Wu's group [132] were shown to not only repel oil underwater $(0C A>150^{\\circ}.$ ), but also to prevent bacterial adhesion (E. coli and S. aureus).  \n\n![](images/215a786c100b0dbd374f38858e083528cd3fa14c50def2d3a9bd87e3533500a9.jpg)  \nFig. 8. Illustration of the “flip-flop” mechanism. These surfaces eliminate the effects of condensation by allowing for water drops to permeate the coating while blocking or slowing down the passage of oily substances. Accordingly, oil contact angles (OCA) are greater than water contact angles (WCA). Adapted from “Bioinspired, roughness-induced, water and oil super philic and super-phobic coatings prepared by adaptable layer-by-layer technique”, Brown, P. S.; Bhushan, B.; Young, T.; et al., Sci. Rep., Volume 5, 2015, Page 14030. (Open access).  \n\n![](images/72bd13f6cf93968d3a1d135a63112fcc27884995a103e1dd123eb1a200dd8d81.jpg)  \nFig. 9. (a) Anti-fogging properties of a PVA-Nafion film with thickness of ${\\sim}247\\mathrm{nm}$ . This film was first conditioned in a - ${}^{-20^{\\circ}\\mathsf{C}}$ refrigerator for 1 h and then placed over boiling water $(\\sim50^{\\circ}\\mathsf C$ and \\~100% RH). (b) Pair of polycarbonate eyeglasses, with the left-hand lens coated with PVA-Nafion films and the right-hand one uncoated. (c) Eyeglasses after being conditioned at - ${\\cdot20^{\\circ}C}$ for 1 h and then exposed to an ambient environment of ${\\sim}20^{\\circ}\\mathsf C$ and $\\sim40\\%$ RH. (d) Digital images of the PVA-Nafion film on a glass substrate that heals scratches. (i) Film scratched with sandpaper and (ii) scratched film from panel i after healing in water for $5\\mathrm{{min}}$ . The scale bar is $1\\mathrm{cm}$ . (e) AFM images of the scratched PVA-Nafion film before (i) and after (ii) healing in water. (f,g) Changes in transmittance at $500\\ \\mathrm{nm}$ and Rrms roughness, respectively, of the PVA-Nafion film during five cycles of the scratching-healing process. Reprinted with permission from “Highly transparent and water-enabled healable antifogging and frost-resisting films based on poly(vinyl alcohol)-nafion complexes”, Li, Y.; Fang, X.; Wang, Y.; Ma, B.; and Sun, J., Chem. Mater., Volume 28, Issue 19, 2016, Pages 6975-6984. Copyright 2018, American Chemical Society.  \n\nBy combining the dip-coating deposition with the in situ nanopressing technique (Fig. 11a), Zhang and collaborators built on glass and PET samples bilayer configurations integrated either by solid silica nanoparticles $(\\mathsf{W C A}=33.1^{\\circ}$ ) [133] (Fig. 11b) or by hollow silica nanoparticles $(\\mathsf{W C A}=37.5^{\\circ})$ ) [134] (Fig. 11c) partly embedded in a thin film of thermally crosslinked PVA-PAA blends. The anti-reflective property observed in optimal SNSs-HSNs/(PVA-PAA) configurations resulted in better light transmittance $(\\mathrm{T_{average}}>93\\%$ in the visible range when compared with that of uncoated substrates $(\\mathrm{T_{average}}\\approx85{-}90\\%)$ . Coatings with anti-fogging activity can also be prepared by immobilizing inorganic nanoparticles (typically $\\mathrm{SiO}_{2}$ and $\\mathrm{TiO}_{2}$ ) either in a network of hydrophilic polymers on the substrate (e,g., PVA, PVP, and PEGMA [135], glycidoxypropyltrimethoxysilane [136] or a catechol-conjugated polymer [137]) or on the substrate by direct deposition using sol-gel [138] or aqueous solutions [139]. The use of mesoporous silica nanoparticles (MPSNPs) [140,141], hollow silica nanospheres (HSNs) [142], double-shell hollow nanospheres of $\\mathrm{SiO}_{2}/\\mathrm{TiO}_{2}$ (DSHNs) [143], and solid silica nanoparticles (SSNPs) [144], among otherbuilding blocks allows for the fabrication of anti-fogging films with hierarchical roughness featuring spreading mechanism (high specific surface). Coatings made up of SSNPs deposited on $\\mathsf{L a}(\\mathsf{O H})_{3}$ nanorods prepared by You and colleagues [145] have proven remarkable capacity to alleviate surface fog $(\\mathsf{W C A}\\approx0^{\\circ}$ ) and minimize light reflection under sun exposure. Cao et al. [146] employed very recently faujasitic nanozeolites (DZ) with an average size of $25-30~\\mathrm{nm}$ , as assembly units to prepare on glass samples coatings with anti-reflective/anti-fogging features, while Liu and colleagues [147] proposed a soft templating route combining in situ growth with a modified Stöber method to synthesize $\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ nanospheres directly on glass surfaces (Fig. 12a). Upon calcination ( $500^{\\circ}\\mathrm{C}$ for $^{2\\mathrm{h}}$ ), the resulting 500-nm-sized $\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ nanospheres conferred superhydrophilic property $(\\mathsf{W C A}=2^{\\circ}.$ ) suitable for anti-fogging purposes to glass samples (Fig. 12b,c).  \n\n![](images/3ba75bdc595a2f4e33f1237a5322e90206aeaf3c1cb0263e7e853ec0f0771fc3.jpg)  \nFig. 10. (a) Chemical structure of SBSi and the formation of SBSi coatings on the oxidized substrate. Light transmission through the samples of PMMA, bare glass, and SBSi-glass after the treatments of (b) hot or (c) freezing at $-20^{\\circ}\\mathsf C.$ (d) Water spray on samples of PMMA, bare glass, and SBSi-glass. (e) Anti-fogging test by treating the water steam to samples of PMMA, bare glass, and SBSi-glass. (f) Oil-water separation apparatus and images of oil-water mixtures, residues, and filtrates in vials before and after separation. The colors of organic fluids are original, without pigment added. (g) Optical images of the underwater-oil CA measurements for SBSi-glass performed with air bubbles, ether, toluene, hexane, gasoline, diesel, and soybean oil; and quantitative results of OCAs for bare and SBSi-glass samples. Reprinted with permission from “Surface modification for superhydrophilicity and underwater superoleophobicity: Applications in antifog”, Huang, K.-T.; Yeh, S.-B.; and Huang, C.-J., ACS Appl. Mater. Interfaces., Volume 7, Issue 38, 2015, Pages 21021-21029. Copyright 2018, American Chemical Society.  \n\nSeveral studies have proven, on the other hand, the feasibility of conferring anti-fogging performance to glass $(\\mathsf{W C A}<10^{\\circ}$ ) by depositing silica or titania sols by dip-coating, followed by calcination [148,149] in the absence or presence of porogens (e.g., PEG [150], CTAB [151]). The removal of residual carbon-containing groups/porogens upon calcination leads to an increase in surface roughness, which drive the surface toward a superhydrophilic state.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# 4.1.2. Spin-coating deposition  \n\nSpin-coating deposition makes it possible to prepare anti-fogging coatings based on semi-interpenetrating polymer networks (SIPNs) with frost-resistance [152] and even anti-bacterial/anti-viral activity [153]. For example, Zhao and colleagues [154] prepared SIPNs based on random copolymers of poly(DMAEMA-co-MMA) within a network of UV-cured PEGDMA with anti-fogging/anti-bacterial features. Partial quaternization of DMAEMA via SN2 (substitution nucleophilic bimolecular) (Fig. 13a) using 1-bromoundecane ( $5\\mathrm{mol}\\%$ in the copolymer, “SIPN-Q-5”) yielded coatings providing glass samples, not only with remarkable optical properties $(\\mathrm{T_{average}}>90\\%$ and capacity to prevent surface fog (Fig. 13b-e), but also with very high killing efficiency against E. coli and S. epidermidis (5-log reduction) (Fig. 13f). Nam et al. [155] developed a two-step process consisting of the deposition of functionalized PEG-containing polymers with pendent polymerizable norbornene (NB) groups by spin-coating, followed by immersion in a solution of Grubb's catalyst to fabricate optimal fog-resistant glasses $\\mathrm{(NB}\\leq30\\mathrm{mol}\\%$ ) with water-attracting features. Unlike SIPNs, no UV light nor heat was required to induce crosslinking. Anti-fogging composite coatings based on a bilayer configuration with enhanced mechanical properties can be fabricated by spin-coating deposition [156,157]. Films consisting of a bottom layer (“primer”) of colloidal $\\mathrm{SiO}_{2}$ ( $30\\mathrm{wt\\%})$ embedded in cross-linked network of dipentaethritol hexaacrylate, and a top layer containing HEMA and “Tween- ${\\cdot20}^{\\prime\\prime}$ have shown encouraging results (Fig. 14a) [158]. The addition of $10\\mathrm{wt\\%}$ of “Tween- ${\\cdot20\"}$ to the coating formulation, resulted in superhydrophilic coatings with fully adherence to  \n\n![](images/023d149dee67071e444dee3cdc6cfdf612e2e7eea3490eb1bb02b1db4f5bbc06.jpg)  \nFig. 11. (a) Schematic of the in situ nanopressing process. (b) SEM images of (i) SNs/polymer/PET, and (ii) ISNW20-SNs/polymer/PET, ISNW20: 20 washing cycles. (iii) Digital images exhibiting the antifogging property of blank (lower part) and ISNW20-SNs/polymer coated (upper part) PET, respectively; (iv) Transm ion spectra of blank PET, polymer/PET, SNs/ polymer/PET, ISN-SNs/polymer/PET, ISNW20-SNs/polymer/PET, and ISNW120-SNs/polymer/PET, respectively. (c) (i) SEM image of the 2HSNs/polymer thin film coated glass, (ii) TEM image of the HSNs. (iii) Digital images exhibiting the antifogging properties of 2HSNs/polymer coated glasses (up part) and blank glasses (lower part). (iv) Transmission spectra of blank glass and glasses coated, respectively, by polymer, 1HSNs/polymer, 2HSNs/polymer, and 3HSNs/polymer. The best anti-fogging configuration is shown in a red rectangle. Figures and graphics reprinted with permission from references [146-147].  \n\nPMMA substrates and long-lasting fog-free effect $(>~1$ year) (Fig. 14b).  \n\nAs in dip-coating deposition, the spin-coating process provides a facile way to build up inorganic coating on flat substrates, employing “building bricks” such as solid and hollow nanoparticles, microspheres, and nanorods, among others [159]. Here, the idea is to procure antifogging activity by designing surfaces endowed with hierarchical topography. With this goal in mind, Shan and colleagues [160] developed 400-nm-thick coatings made up of a thin film of $\\mathrm{Cu-Bi}_{2}0_{3}$ covered with MPSNPs, by combining the spin-coating technique with the sol-gel method. Anti-fogging $\\mathsf{M P S N P S}/\\mathsf{C u{-}B i_{2}O_{3}}$ films $\\mathrm{\\Cu}{:}\\mathrm{Bi}_{2}\\mathrm{O}_{3}$ molar ratio $\\c=$ 5) performed adequately when exposed to humid air after being cooled in a freezer $(-18^{\\circ}\\mathsf C)$ and were able to degrade methyl orange and stearic acid upon exposure to UV light ( $1\\mathrm{\\mw\\cm^{-2}}$ ). Mesoporous $\\mathrm{SiO_{2}/B i_{2}O_{3}/T i O_{2}}$ triple-layered thin films prepared on glass slides using a simple sol-gel/spin-coating approach showed similar results in terms of photocatalytic response and anti-fogging performance [161]. Silica- and titania-based coatings with enhanced wetting behavior can be prepared in ways other than those involving the deposition of building blocks. Similar to dip-coating deposition, particular emphasis has been placed on the in situ generation of nanopores upon calcination, for example, by using porogens [162] or surfactants [163]. Regardless of the adopted strategy, the principle is simple: the infiltration water drops into the nanoporous network drives the anti-fogging phenomenon (spreading mechanism). Alternatively, Budunoglu and collaborators [164] fabricated $135\\mathrm{-nm}$ -thick $\\mathrm{SiO}_{2}$ films with tunable porosity on glass samples using “ormosil” (organically modified silica) gels, which were prepared via hydrolysis and condensation of TEOS and methyltrimethoxysilane (MTMS). The pore size was tuned by changing the TEOS/MTMS volume ratio in the sol-gel mixture. A rational commitment between the “seethrough” property, mechanical durability, and optical clarity (Taverage $>95\\%$ , in the visible range) was met for a TEOS/MTMS volume ratio of 3:2. Despite the conceptual simplicity behind the spin-coating technique, the feasibility of fabricating anti-fogging coatings with hierarchical surface features similar to those observed in the compound eyes of insects have been recently demonstrated. For example, Sun and colleagues [99] designed fog-free surfaces by depositing on glass samples fly-eye bioinspired ZnO microspheres (Fig. 6ai). Following hydrophobization with 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane, coated glasses prevented water drops from accumulating on the surface when placed in an artificial fogging chamber for 2 min at a tilting angle of $10^{\\circ}$ ( $\\mathsf{W C A}=162.2^{\\circ}$ and $S A\\approx3^{\\circ}$ ). Zhang and collaborators [165] reported a straightforward method involving sol-gel process and spincoating deposition to produce films with moth compound eye-like features using a mixture of MPSNPs containing surfactants and $\\mathrm{SiO}_{2}$ sol. Finally, Li’s group [166] very recently reported on the fabrication of coatings with water- and oil-attracting features made of $\\mathrm{Cu}_{3}\\mathrm{SnS}_{4}$ , a ternary semiconductor. Following annealing in $\\mathsf{N}_{2}$ at $500^{\\circ}\\mathrm{C},$ , spin-coated glasses $\\mathrm{\\DeltaR_{rms}}=0.432\\mathrm{\\nm}\\mathrm{\\Omega}$ ) displayed superamphiphilicity, as revealed by a WCA and OCA below $1^{\\circ}$ , and a band-gap $(1.74\\ \\mathrm{eV})$ compatible with applications in the field of photovoltaic cells (see Section 5.2).  \n\n![](images/c52bef8c5d54cdd0a5e7c9314aa5fb2b4eb2d0cebcfc966ccfe700956c3dbc69.jpg)  \nFig. 12. (a) The in situ synthesis mechanism of $\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ nanospheres. (b) Contact angle of the blank substrate, substrate with $\\mathrm{SiO}_{2}$ particles, and substrate with $\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ nanospheres. (c) The anti-fogging property of the samples. “In situ growth of $\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ nanospheres on glass substrates via solution impregnation for antifogging”, Liu, F.; Shen, J.; Zhou, W.; Zhang, S.; and Wan, L., RSC Adv., Volume 7, Issue 26, 2017, Pages 15992-15996. Published by The Royal Society of Chemistry.  \n\n![](images/a815d24ca159b381a79807146077572424540a48f0fbec1de8d6e8216cdc98f5.jpg)  \nFig. 13. (a) Schematic illustration of partial quaternization of poly(DMAEMA-co-MMA). Photos of different samples: (b) control glass and (c) SIPN-Q-5, which were first stored at ${}-20^{\\circ}{\\mathsf{C}}$ for $30\\mathrm{min}$ and then exposed for 5 s to ambient lab conditions $(\\sim20^{\\circ}C$ , $50\\%$ RH). Light transmittance at normal incident angle for various samples: (d) as prepared and (e) 5 s under ambient condition $(\\sim20^{\\circ}C$ , $50\\%$ RH) after being stored at ${}^{-20^{\\circ}\\mathsf{C}}$ for $30\\mathrm{min.}$ . (f) Zone-of-inhibition test result of (a) SIPN-Q-5 and (b) SIPN-Q-10 in a cultured lawn of E. coli. “SIPN-Q-X”, X: x mol% in the copolymer of quaternized DMAEMA. Reprinted with permission from “Dual-functional antifogging/antimicrobial polymer coating”, Zhao, J.; Ma, L.; Millians, W.; Wu, T.; and Ming, W., ACS Appl. Mater. Interfaces., Volume 8, Issue 13, 2016, Pages 8737-8742. Copyright 2018, American Chemical Society.  \n\n![](images/e1b5e192824dc8a5ca6f134016b94fae3654607d7a469dcd7831f508cb0c0e99.jpg)  \nFig. 14. (a) Bilayered anti-fogging coating. (b) Steam anti-fogging tests of coatings in AF10 after 1 year in service. Reprinted with permission from “Preparation of water-resistant antifog hard coatings on plastic substrate”, Chang, C.-C.; Huang, F.-H.; Chang, H.-H.; Don, T.-M.; Chen, C.-C.; and Cheng, L.-P., Langmuir, Volume 28, Issue 49, 2012, Pages 17193-17201. Copyright 2018, American Chemical Society.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# 4.1.3. Layer-by-layer deposition  \n\nThe layer-by-layer (LbL) deposition is a straightforward coating technique suitable for the fabrication of anti-fogging coating based on multi-layer structures. This bottom-up approach involves sequential assembling of thin layers by dipping the sample into different solutions, followed by rinsing cycles. In general, the coating's robustness is ensured either by electrostatic interactions or by covalent and non-covalent interactions between adjacent layers, namely, hydrogen, hemiacetal, and ester bonds. In the last five years, various research groups have demonstrated that the incorporation of natural polymers, such as carboxymethyl cellulose (CMC), chitosan (CHI), and other polysaccharides [167–169]; and synthetic polymers, such as polyvinyl and polyacrylic compounds [170–174], into anti-fogging formulations can be successfully attained via LbL. For example, Spiroiu's group [175] fabricated anti-fogging layers with WCA exceeding $90^{\\circ}$ , based on selfassembled structures of CHI and sodium lauryl ether sulfate micelles, while Lee's group [176] developed zwitter-wettable coatings comprising a hydrophilic bottom layer of $(\\mathrm{CHI}/\\mathrm{CMC})_{30}$ capped with three hydrophobic (CHI/Nafion) bilayers $(\\mathsf{W C A}\\approx110^{\\circ}.$ ). As did Shibraen's and Cohen's groups [169,170], these research groups considered the water-absorbing characteristics of these coatings to account for the observed anti-fogging performance and, in some cases, the frosting delay capacity (percolation mechanism) [170,171]. Sun and colleagues [177] designed anti-fogging films with oil-repellent features via the assembly of hyaluronic acid (HA) and branched poly(ethylenimine) (bPEI) and subsequent hydrophobization with perfluorooctanesulfonic acid potassium salt (PFOS). It was found that glass and plastic lenses coated with PFOS- $({\\mathrm{HA}}/{\\mathrm{bPEI}})_{50}$ films were able to heal cuts of $80\\upmu\\mathrm{m}$ in width after $5\\mathrm{min}$ in water. Very recently, Shiratori et al. [178] demonstrated that films composed of multistacked layers of negatively charged PVA-PAA blends and positively charged PAH-PVA-PAA blends featured not only capacity to minimize fogging effects but also anti-reflective and antithrombogenic properties. The hierarchical topography observed in ((PAH-PVA-PAA)/(PVA-PAA)) $_{10}$ -coated glasses coupled with abundant OH groups per area unit translated to extreme wetting behavior (WCA $<5^{\\circ}.$ ) (Fig. 15a). Qualitative assessment of the anti-fogging performance revealed that ((PAH-PVA-PAA)/(PVA-PAA))10 coatings conferred noticeable visual characteristics to glasses when in contact with a moist environment at $35^{\\circ}\\mathsf{C}$ (Fig. 15b). Furthermore, the light transmission values $(\\mathrm{T}_{\\mathrm{average}}\\approx95\\%$ ) were greater than those of a bare glass (Taverage $\\approx91\\%$ , in $450\\mathrm{-}850~\\mathrm{nm}$ range) (Fig. 15c). In view of the FITR results, these anti-fogging coatings prevented the adhesion of fibrinogen, thus revealing a potential application as “anti-anticlotting” material (Fig. 15d,e).  \n\n![](images/4915658c313f57410863dfeb10d8e65095f99c9731d500d74c621e34c0ef5ec1.jpg)  \nFig. 15. (a) Scanning electron microscopy image of ((PAH-PVA-PAA)/(PVA-PAA))10 films. (b) Photography of a cooled glass slide with (left) and without (right) the coating in a highhumidity environment $(90\\%\\mathrm{RH})$ at $35^{\\circ}\\mathrm{C}$ after being cooled in a refrigerator to $<5^{\\circ}C.$ (c) Transmittance of films with different numbers of bilayers on glass substrates. Fourier transform infrared spectra of (d) bare silicon wafer substrate and fibrinogen and (e) ((PAH-PVA-PAA)/(PVA-PAA))10 films before and after contact with a fibrinogen solution. Reprinted with permission from “Antifibrinogen, antireflective, antifogging surfaces with biocompatible nano-ordered hierarchical texture fabricated by layer-by-layer selfassembly”, Manabe, K.; Matsuda, M.; Nakamura, C.; Takahashi, K.; Kyung, K. H.; and Shiratori, S., Chem. Mater.,Volume 29, Issue 11, 2017, Pages 4745-4753. Copyright 2018, American Chemical Society.  \n\n![](images/5cc6bbfd87b991d9f02a8f1477a9c07b4954a31330a9c5f1dd187f617c89cd93.jpg)  \nFig. 16. LbL strategies for the deposition of inorganic materials used in anti-fogging coatings. C: Carbon (template), MPSNPs: Mesoporous silica nanoparticles, NS: Nanosheets, PC: Polycarbonate (template), PDDA: Poly(diallyldimethylammonium chloride), PSS: sodium Poly(4-styrenesulfonate), SSNPs: Solid silica nanoparticles. Figures reprinted with permission from references [183,185,188,193].  \n\nRegarding inorganic anti-fogging layers, studies carried out by various research groups in the last seven years show that, solid and mesoporous $\\mathrm{SiO}_{2}$ nanoparticles, i.e., SSNPs and MPSNPs, can be assembled in three different ways [179–181]. The first one involves combining SSNPs with nanosheets (Fig. 16a). In this context, worthy of mention are the studies conducted by Byeon and colleagues [182,183], who designed coatings with luminescent/anti-fogging features by assembling nanosheets of RE-doped gadolinium hydroxides ( $\\boldsymbol{\\mathrm{RE}}=\\boldsymbol{\\mathrm{Eu}}$ , Tb, and Dy) with SSNPs. Following annealing at $500{-}600\\ ^{\\circ}\\mathrm{C},$ the resulting $(\\mathrm{Gd}_{2}\\mathrm{O}_{3}{\\mathrm{:RE/SSNPS}})_{\\mathrm{n}}$ coatings $\\mathbf{\\dot{\\zeta}}n=7\\mathbf{-}9$ , 30) prevented fogging via spreading mechanism $(\\mathsf{W C A}<5^{\\circ}).$ ). Depending on the dopant, the coated glasses featured efficient red (Eu), green (Tb), and blue (Dy) light emissions when illuminated with light of $254~\\mathrm{nm}$ . In a similar manner, stacking of reduced graphene oxide (RGO) nanosheets with nanoparticles of $\\mathrm{SiO}_{2}$ [184] or $\\mathrm{TiO}_{2}$ [77] has also been carried out to produce fog-resistant coatings with high specific surface area. The second way to prepare anti-fogging coatings with hierarchical porosity involves using “building blocks”, such as raspberry-like [100,185–187] and mulberry-like [89,188,189] nanospheres, which are synthesized prior to the deposition process by a judicious assembly of nanospheres (Fig. 16c,d,f,g). Many other research groups have followed a protocol similar to that depicted in Fig. 16c,d,f, to elaborate super wettable surfaces with hierarchical roughness, using only nanoparticles of $\\mathrm{SiO}_{2}$ [106,107,179,190], $\\mathrm{TiO}_{2}$ [74,88], $Z\\mathrm{r}0_{2}$ [191], $\\mathsf{A l}(0\\mathsf{H})_{3}\\mathsf{-M g}(0\\mathsf{H})_{2}$ as building units or PDDA‑sodium silicate complexes [192]. The third way to produce hierarchically rough anti-fogging surfaces is based on the assembly of mesoporous silica nanoparticles (MPSNPs) according to the protocol depicted in Fig. 16b [193–196]. On the other hand, several studies have shown that anti-fogging activity comparable to the one obtained these ways can be attained, without the need for calcination or annealing post-treatments [197,198] coupled, in some cases, with a reduction in the number of deposition cycles. For example, Sun and collaborators [199] evidenced that only three deposition cycles of MPSNPs $(\\sim50\\ \\mathrm{nm})$ ) alternating with PDDA sufficed to retain transparency when coated polycarbonate was exposed under very humid conditions. Analogously, Guo et al. [200] used the LbL assembly technique to produce fog-free films consisting of discrete layers of poly(ethylenimine) (PEI) and PSS containing clusters of calcium silicate hydrates (CSH). Interestingly, coatings integrated by multistacked layers of $z_{\\mathrm{{nO}}}$ nanoparticles (NP)/nano-flowers (NF) and PAA proved to not only be effective in eliminating the effects of condensation but also in blocking UV light [201] and killing bacteria [180]. Notable capacity to block UV light was also noticed in a multistack configuration consisting of discrete layers of PEI and CMC-modified $\\mathrm{TiO}_{2}$ nanoparticles recently prepared by Li and collaborators [202]. Further to this, $(\\mathrm{PEI}/\\mathrm{CMC@TiO_{2}})_{15}$ coatings were found to delay aging of PET substrates while conferring them anti-fogging performance, because of their superhydrophilic nature.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# 4.1.4. Physical and chemical vapor deposition  \n\nSputtering methods such as RF magnetron sputtering, and evaporation methods such as electron beam deposition has proven to be suitable to design nanostructured anti-fogging inorganic coatings, with high deposition rates, excellent adhesion, and uniformity [203,204]. For example, Kwak and colleagues [205] reported a two-step process to fabricate ZnO-based anti-fogging coatings consisting of the deposition of a $z_{\\mathrm{{nO}}}$ seed layer on glass samples by RF sputtering, and subsequent growth of ZnO nanorods using ammoniacal solutions of zinc nitrate hexahydrate. Because of a light transmission as high as bare glass $\\approx90\\%$ in the $400{-}700~\\mathrm{nm}$ range) and the ability to block light below $370\\mathrm{nm}$ as in [180,201,202], these surfaces hold promise for fenestration purposes. ITO nanorods prepared by RF magnetron sputtering, followed by in-air annealing at $250^{\\circ}\\mathrm{C}$ have shown to endow glass samples with satisfactory anti-fogging and self-cleaning properties [206] (Fig. 17a,b). Coatings met extreme wettability $(\\mathsf{W C A}<1^{\\circ}),$ with sputtering times $>40$ min, because of the increase in size of nanorods (Fig. 17c). No fogging was observed in the samples treated for $60\\mathrm{min}$ under an aggressive cold fog test a − $20~^{\\circ}\\mathrm{C}$ (Fig. 17d). Following functionalization with 2H-perfluorodecyltrichlorosilane, the asprepared surfaces were easy to clean, as a drop of green powder phosphor lying on the surface was easily removed when water was added, leaving no remnant. (Fig. 17b).  \n\nRF magnetron sputtering makes it possible to build multifunctional $\\mathrm{TiO}_{2}$ -based configurations showing tremendous potential in smart window applications, as observed in glasses covered with a $\\mathrm{TiO}_{2}$ (anatase)/ $\\mathsf{V O}_{2}$ (monoclinic) $\\slash\\mathrm{{IiO}}_{2}$ (rutile) tri-layered film [207] or with a multistacked $\\mathrm{TiO}_{2}$ (anatase) $/\\mathrm{Si}/\\mathrm{Ag(Cr)/TiN_{x}}$ structure [208]. Using electron beam evaporation, Eshaghi and collaborators [209] developed a multistack configuration consisting of discrete layers of $\\mathrm{SiO}_{2}$ and $\\mathrm{TiO}_{2}$ that proved to be effective in preventing condensation effects on glass. In the same vein, Palmisano and colleagues [210] demonstrated the feasibility of depositing smooth $\\mathrm{TiO}_{2}$ coatings with better anti-fogging and self-cleaning performances than the ones observed in a commercial anti-fogging glass (Pilkington Activ™ glass). Using the CVD technique on glass samples, Chen and collaborators [211] deposited $\\mathrm{SiO}_{2}$ coatings with a regular convex nipple structure employing ammonia-catalyzed sol-gel solutions of TEOS. Even though all of the treated samples remained fog-free when placed over hot water or cooled at $-18^{\\circ}C$ the best optical properties (Taverage $\\approx95\\%$ in the $400{-}800~\\mathrm{nm}$ range)  \n\n![](images/5eb92920379673a3ee9ecf2fe86c0bde48f04529b69219be5b206559d5a26f86.jpg)  \nFig. 17. Schematic illustration of the fabrication procedures for preparing a multifunctional ITO nanorod film: (a) superhydrophilic ITO nanorods $\\angle W C A<1^{\\circ}$ ) displaying anti-fogging behavior when exposed to a humid environment $(\\mathrm{RH}>80\\%)$ after storage at $-20\\ ^{\\circ}\\mathsf C,$ and (b) superhydrophobic ITO nanorods $(\\mathsf{W C A}=172.1^{\\circ}$ , $S\\mathbb{A}\\mathfrak{n}\\mathbb{0}^{\\circ}$ ) featuring self-cleaning activity. (c) WCA of the post-annealed ITO nanorod films on glass substrates as a function of the growth time. The insets show the water CAs of a bare glass substrate and of an ITO nanorod film grown on a glass substrate for $60~\\mathrm{{min}}$ . (d) Top- and side-view SEM images of the ITO nanorod film grown on a glass substrate for $60~\\mathrm{{min}}$ . Reproduced from “Fabrication and characterization of large-scale multifunctional transparent ITO nanorod films”, Park, H. K.; Yoon, S. W.; Chung, W. W.; Min, B. K.; and Do, Y. R., J. Mater. Chem. A, Volume 1, Issue 19, 2013, Pages 5860-5867. Copyright 2018, with permission of The Royal Society of Chemistry.  \n\n![](images/e099837ce7aa5f4217ab0eddea4e576098d67862b98e8286e65b849063ebcf8c.jpg)  \nFig. 18. (a) Schematic drawing of the synthesis and hydrogen-bond-driven stabilization of titanate nanobelts. (b) Schematic illustration of the electrophoretic deposition process to prepare a TNB/FAS film. (c) SEM image of the as-prepared superhydrophobic TNB/FAS film (2 min). The inset image shows water droplets on the transparent TNB/FAS film on ITO glass. (d) Time sequence of the self-cleaning process on the superhydrophobic coating with low water adhesion. (e) Water droplet on the superhydrophilic TiO2 film. (f) Photograph of an ITO substrate deposited with superhydrophilic coatings (bottom) and a control ITO substrate without any coating deposition (upper) taken from a refrigerator $(-4^{\\circ}C)$ to the humid laboratory air (ca. $50\\%$ RH). Reproduced from “Transparent superhydrophobic/superhydrophilic TiO2-based coatings for self-cleaning and anti-fogging”, Lai, Y.; Tang, Y.; Gong, J.; Gong, D.; Chi, L.; Lin, C.; Chen, Z.; Liu, M. J.; Zheng, Y. M.; Zhai, J.; et al., J. Mater. Chem., Volume 22, Issue 15, 2012, Pages 7420-7426. Copyright 2018, with permission of The Royal Society of Chemistry.  \n\nwere noticed in glasses treated for $^{10\\mathrm{h}}$ . Shoji et al. [212] prepared silicon resin thin films on PC substrates with tunable hydrophobic/hydrophilic features using a low-pressure RF plasma. When plasma polymerization was performed in $0_{2}/\\mathrm{HCOOH}$ atmosphere under a power input between 50 and $150\\mathrm{W}$ , the coated PC displayed extreme wettability $(\\mathsf{W C A}<5^{\\circ})$ ) and remained fog-free when exposed to steam, breath, and room conditions after cooling at lower temperature.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# 4.1.5. Electrochemical deposition  \n\nMeroni and colleagues [213] reported on the feasibility of an electrochemical method (potentiostatic deposition), similar to that employed by Patel et al. [214], to deposit several layers of $\\mathrm{TiO}_{2}$ on glass. Following application of $3.6~\\mathrm{V}$ for $60\\ s$ to a glass sample immersed in a $\\mathrm{TiO}_{2}$ sol, the resulting crack-free $\\mathrm{TiO}_{2}$ coatings were fully wettable but degraded transparency of glass substrates, as supported by the observed decrease in the average transmittance from $92\\%$ (uncoated glass) to approximately $75\\%$ in the visible region. In addition, the anti-fogging property was consistent with a decrease in WCA from 40 to $0^{\\circ}$ following exposure to UV light $(30\\mathrm{\\mW\\cm}^{-2}$ ). In contrast, $\\mathrm{TiO}_{2}$ coatings with nanofiber morphology fabricated by Tricoli's group [92] by electrospinning, displayed non-UV-activated anti-fogging features. Following thermal treatment at $500~^{\\circ}\\mathrm{C}$ , the resulting $\\mathrm{TiO}_{2}$ nanofibers of $200~\\mathrm{{nm}}$ in thickness provided glasses with excellent capacity to avoid blurry view when exposed to vapor, because of the great amount of hydroxyl on the surface (specific area $=106\\ \\mathrm{\\bar{m}}^{2}\\ \\mathrm{g}^{-1}$ , WCA $\\mathit{\\Theta}<10^{\\circ}$ ), as well as acceptable light transmission $(\\mathrm{T}_{\\mathrm{max}}~\\approx~93\\%)$ for incident light of 400 and $600\\ \\mathrm{nm}$ . Similarly, films composed of $\\mathrm{TiO}_{2}$ nanobelts were shown to be superhydrophilic with no previous UV exposure [93]. In this instance, titanate nanobelts (TNB), which were synthesized via a hydrothermal method, were deposited on ITO glass via electrophoretic deposition, and then functionalized with 1H,1H,2H, 2H-perfluorooctyltriethoxysilane (FAS) (Fig. 18a,b). When the functionalization time was 2 min, the resulting wetting behavior of the FAS-treated surfaces $(\\mathsf{W C A}\\approx156.2^{\\circ}$ and ${\\bf S}{\\bf A}\\approx8.6^{\\circ}$ ) led to the easy cleaning against yellow nitrogen-doped titanate powder (Fig. 18c,d). Upon calcination at $500~^{\\circ}\\mathrm{C},$ , a drastic shifting toward a super wettable state $(\\mathsf{W C A}\\approx0^{\\circ}$ ) was noticed, because of the removal of the hydrophobizing agent and the conversion of TNB into porous $\\mathrm{TiO}_{2}$ (anatase) (Fig. 18e). Under fogging conditions, the $\\mathrm{TiO}_{2}$ -coated glasses exhibited higher transmissivity than did uncoated ones (Fig. 18f).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# 4.1.6. Others  \n\nThe techniques mentioned above cover the most common bottomup approaches for producing anti-fogging surfaces; however, other not less important ones have not been addressed here. These include: solvent casting methods [215–217]; bar coating methods [218–223]; spray coating techniques [91,224–226]; and multi-step approaches [227,228].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 25,
+        "chunk": "# 4.2. Top-down processing  \n\nTop-down processing is based on the removal of material from a starting sample either to increase surface roughness or to create fine patterns, and thus drive the surface toward anti-fogging property.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 26,
+        "chunk": "# 4.2.1. Dry and wet etching methods  \n\nIn dry etching, the sample is subjected to either high energy particles (e.g., electrons, X-rays), ions, or both; while in wet etching, the sample is dipped in an acid or in an alkaline solution for a certain period of time to “carve” the surface. In wet etching, the surface morphology, the rate at which the material is removed, and the resulting optical properties can be tailored, by varying certain experimental parameters such as the temperature, the concentration of reactive species, and the etching time [229–231]. Bearing this in mind, He et al. [229] elaborated dual anti-fogging/anti-reflective glasses $(\\mathsf{W C A}=4.3^{\\circ}$ ), with nanoflake-like surface features using a liquid alkali etching ( $5\\mathrm{g}\\mathrm{L}^{-1}$ of NaOH, $85~^{\\circ}C.$ ). A similar approach was reported by Myoung and colleagues [230]. In this instance, glass samples with variable $w t\\%$ of $\\mathsf{N a}_{2}0$ were dipped in KOH solutions at $95^{\\circ}C$ for 4, 12, and $24\\mathrm{h}$ (Fig. 19a–c).  \n\nEven though hydrophilicity was shown to increase with the etching time, at least $^{4\\mathrm{~h~}}$ of etching treatment were required to obtain “A” glasses with resistance to fogging (Fig. 19d). Furthermore, this treatment increased the maximum transmittance of “A” glasses from $\\approx90$ to $97.7\\%$ (at $630\\ \\mathrm{nm}$ ) due to a concomitant variation in size of nanoflake-like structures (Fig. 19e). Aqueous ${\\mathsf{N a H C O}}_{3}$ solutions have also shown an ability to “chisel” glass surfaces to produce sponge-like structures with a notable capacity to alleviate fogging effects [231].  \n\n![](images/58c7a8cae1e52211a3b196609d76d35c5384473c1d5d05d33f34f9ff1445845f.jpg)  \nFig. 19. SEM images of glasses etched for different periods of time (4, 12, and 24 h): (a) glass “A” (27.42 wt% of $\\mathrm{\\tilde{Na}_{2}O}$ ), (b) glass “B” (24.08 wt% of $\\mathbf{\\dot{Na}}_{2}0$ ), and (c) glass $\"C\"$ (0.35 wt% of $\\mathrm{\\DeltaNa_{2}O}^{\\prime}$ . (d) Transmittance spectra of glass A before and after etching (KOH 1M) at different etching times, and (e) anti-fogging performance of etched $\"A\"$ glasses (4 h) when cooled at - ${}-10^{\\circ}{\\mathsf{C}}$ and exposed thereafter to steam (right: before etching and left: after etching). Reproduced from “A multifunctional nanoporous layer created on glass through a simple alkali corrosion process”, Xiong, J.; Das, S. N.; Kar, J. P.; Choi, J.-H.; and Myoung, J.-M., J. Mater. Chem. Volume 20, Issue 45, 2010, Pages 10246-10252. Copyright 2018, with permission of The Royal Society of Chemistry.  \n\nYao et al. [232] fabricated fog-free glasses in a sequential approach consisting in chemical dry etching using a $\\mathrm{H}_{2}\\mathrm{SiF}_{6}$ -containing vapor $(\\leq20~^{\\circ}\\mathrm{C})$ , annealing at $720^{\\circ}\\mathrm{C}$ for $135\\ s,$ and low-pressure $0_{2}$ plasma treatment for $25{\\mathrm{~min}}$ . On the other hand, etching can be used to “activate” surfaces prior to coating deposition. Here, the goal is to ensure the adherence of anti-fogging coatings on the substrate to prevent them from detaching when exposed to a humid environment or under normal cleaning practices. For example, Lam et al. [85] deposited $\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ bilayers on NaOH-etched and UVirradiated PC, while Yao and collaborators [233] dipped glasses, which were previously treated following the above-mentioned protocol [232], in a SSNPs solution $(20~\\mathrm{\\nm})$ to ensure the “seethrough” property. In another study, Di Mundo's group [234] conferred anti-fogging capability to PC films through a self-masked plasma etching and subsequent deposition of a superhydrophilic silica-like coating, using a low-pressure $\\ensuremath{\\mathrm{~\\textrm~{~~}~}}0_{2}/\\ensuremath{\\mathrm{Ar}}$ plasma fed with hexamethyldisiloxane (HMDSO).  \n\nEvidence shows that the above-illustrated etching methods do not allow for the design of surface structures with desired geometric order and well-defined shapes (e.g., subwavelength structures, SWSs). To overcome this drawback, reactive ion etching (RIE) has emerged as a promising tool due to its unique ability to etch with finer resolution, and higher aspect ratio than isotropic etching does [235]. For example, Lee and colleagues [236] tailored the wettability of borosilicate glass substrates by means of a self-masked RIE operating under controlled conditions, namely, $50\\mathrm{W}$ and $\\mathrm{CF}_{4}{:}0_{2}$ ratio of 4:1. When the etching time was $7\\mathrm{min}$ , the glasses became hydrophilic $(\\mathsf{W C A}=12.5^{\\circ}.$ ) in response to a concurrent formation of tapered SWSs with aspect ratios in the 1.5–2 range. Both the low WCA and the high surface energy $\\left(87.8~\\mathrm{mN}~\\mathrm{m}^{-1}\\right.$ ) substantiated the observed fog-free effect when the etched glasses were exposed to steam. Alternatively, Xu et al. [237] built up tapered conical structures (aspect ratio of 2.8) by reactive ion etching ( $100\\mathrm{W}$ and $\\mathrm{CHF}_{3}$ :Ar ratio $=2$ ), using a thin film of Ag nanoparticles as etching mask. As in the previous study, the judicious combination of the inherent hydrophilicity of $\\mathrm{SiO}_{2}$ with the nanohole egg-crate-like structure was behind the observed broadband optical transmissivity $(400-1400\\mathrm{nm}$ ) as well as the anti-fogging performance $(\\mathsf{W C A}\\approx0^{\\circ}$ ) of quartz slides. RIE in combination with bottom-up processing makes it possible to obtain nanostructured polymer-based anti-fogging coatings with outstanding optical performance. Of particular interest is the elegant strategy reported by Suh and collaborators [238] to fabricate super wettable glasses $(\\mathsf{W C A}<5^{\\circ})$ ). Their approach involved the deposition of an UV-curable polyurethane acrylate by rollpressing and subsequent self-masked RIE. Following the same idea, Sim et al. [239] elaborated anti-fogging layers with graded roughness (gradient-index anti-reflection coating, GIARC) using block copolymers of polystyrene (PS) and polydimethylsiloxane (PDMS) (i.e., PS-b-PDMS) as starting materials. Briefly, glass substrates were first coated with PSb-PDMS films and subjected thereafter to RIE to convert the copolymer into a nano-structured $\\mathrm{SiO}_{2}$ (Fig. 20a). Surface features such as roughness and porosity, as well as the optical properties of the resulting coating were found to depend on both the molecular weight of PDMS and its fraction in the copolymer (Fig. 20b,c). Optimized nanoporous silica films “SD55k” $\\mathrm{'}\\mathrm{f}_{\\mathrm{PDMS}}=9.1\\%$ , enabled an easy legibility of the letters behind the coated glasses when exposed to super-saturated water vapor at 90 $^{\\circ}{\\mathsf C}$ (Fig. 20d). This behavior was consistent with an average transmittance remaining almost unchanged at approximately $97\\%$ under the same conditions (Fig. 20e).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 27,
+        "chunk": "# 4.2.2. Lithography  \n\nThis top-down approach makes it possible to design subwavelength structures, SWSs ( $\\leq100~\\mathrm{{nm}}$ ) with excellent precision and accuracy using photons, electrons, or ions. Park et al. [37] applied the so-called “orthogonal interference lithography” to fabricate periodic square arrays of tapered SWSs on silica samples with an aspect ratio of 5.5 and packing densities $>10^{6}\\mathrm{mm}^{-2}$ . The resulting surfaces simultaneously met anti-fogging performance, with a WCA ${\\approx}0^{\\circ}$ , and minimal reflection over a wide range of incident angles (0 to $80^{\\circ}$ ) in the visible and near-IR wavelengths. Mao and collaborators [240] very recently reported on the potential applicability of “direct laser interference lithography” (DLIL) for the manufacture of anti-fogging eyeglasses. A square periodic array of inverted nanocones made of polyurethane acrylate, which was fabricated in a sequential approach consisting of DLIL, dry etching, and UV replication process, has also generated worthwhile results [241]. Due to the superhydrophilicity $(\\mathsf{W C A}\\approx0^{\\circ}$ ) conferred by the SWSs with an aspect ratio $\\approx4$ , no fogging was observed when the nanotextured glasses were placed over saturated steam. Moreover, such glasses displayed remarkable light transmission $\\mathrm{'T_{average}}>95\\%$ , incidence angle of $0^{\\circ}$ ) over the $350\\mathrm{-}1400\\mathrm{nm}$ range. In another study, Duan and colleagues [242] combined a sol-gel/dip-coating method with DLIL to design non-UV-activated anti-fogging $Z\\mathrm{r}0_{2}$ coatings with a grooved or a mastoideus surface. Soft lithography, on the other hand, allows for the preparation of polymer-based anti-fogging coatings with micro/ nanostructured surface features using mechanical procedures, such as stamping and molding. Zheng's group [104] fabricated anti-fogging surfaces with water-repellent and icing-delay characteristics by planting onto poly(vinylidene difluoride) microratchets, which were obtained by the heat-pressing pattern-transfer technique, nanohairs of ZnO (Fig. 6bii). Following hydrophobization with heptadecafluorodecyltripropoxysilane (FAS-17), water drops remained in a non-freezable state at $-5^{\\circ}\\mathsf{C}$ and rolled off the surface when exposed to breeze, because of the water-repellent properties of the surface $(\\mathsf{W C A}\\approx150^{\\circ}$ ). Epoxy micropillars arrays covered with $z_{\\mathrm{{nO}}}$ nanohairs fabricated by soft replication methods (“Bosch process”) and crystal-growth techniques have shown better results in terms of ice formation delay [102]. In this case, an icing delay time as high as 9839 s was noticed in the FAS-treated surfaces (an icing delay time of 7360 s at $-10^{\\circ}C$ was reported in the previous study), even though the contact angle was virtually the same $\\mathrm{^{\\prime}W C A}\\approx152^{\\circ}.$ ) (Fig. 6aiv).  \n\n![](images/80e592b40c5a6f5292ebf44a7dfa3d30afcd46dfed00873680ea8fa671540e43.jpg)  \nFig. 20. (a) Facile solution-based procedure for the preparation of the gradient-index anti-reflection coating (GIARC) based on Si-containing block copolymers. SEM images of a doublelayered GIARC consisting of (b) SD55k $\\mathrm{\\Delta}\\mathrm{\\cdot}\\mathrm{f_{PDMS}}=0.091$ ) and (c) SD43k $\\mathrm{^{\\prime}f_{P D M S}}=0.488\\mathrm{^{\\cdot}}$ . (d) Comparison of the anti-fogging properties of GIARC and a bare glass substrate. e) Changes in transmittance with the exposure time to water vapor. Reprinted from “Ultra-high optical transparency of robust, graded-index, and anti-fogging silica coating derived from Si-containing block copolymers”, Sim, D.; Choi, M.-J.; Hur, Y.; Nam, B.; Chae, G.; Park, J.; and Jung, Y., Adv. Opt. Mater. Volume 1, Issue 6, 2013, Pages 428-433. Copyright 2018, with permission from John Wiley and Sons.  \n\nAlthough lithography has great potential for the fabrication of intricate structures, surprisingly only a few research groups have focused their expertise toward developing anti-fogging films with topographical features similar to the ones found in insect's eyes [243–245]. For instance, moth eye-like nanostructures integrated by polydimethylsiloxane domes have been elaborated employing the lift-up softlithography technique (Fig. 6bi) [105]. Following deposition of SSNPs and subsequent treatment with monolayers of self-assembled fluoroalkylsilane (FAS), the resulting hydrophobicity $(\\mathsf{W C A}=155^{\\circ}$ and $S\\mathsf{A}=15^{\\circ}$ ) supported the rolling mechanism behind the observed anti-fogging activity. By means of sacrificial layer-mediated nanoimprinting (SLAN), Raut and collaborators [103] deposited on glass samples a moth eye-like structure made from a resin containing methacryloyloxypropyl polysilsesquioxane (Fig. 6av). Following treatment with 1H,1H,2H,2H-heptadecafluorodecyl methacrylate, optimal surfaces with ommatidial features of $20\\upmu\\mathrm{m}$ in diameter $(\\mathsf{W C A}\\approx151^{\\circ}$ and ${\\mathsf{C A H}}\\approx2^{\\circ}$ ) displayed very low average reflectance (ca. $4.8\\%$ ) and very fast transmittance recovery $(\\mathrm{T_{average}}=100\\%\\mathrm{in}\\approx10\\mathrm{s})$ ) after exposure to saturated steam. Without the need for hydrophobization posttreatments, moth eye-like nanostructures consisting in PMMA nanonipples covered with solid silica nanoparticles were also found to retain transparency under fogging conditions [246]. Despite an aspect ratio as low as 1, nanostructured surfaces reduced drastically glare and remained optically clear when exposed to moisture for $15~\\mathrm{min}$ due to their superhydrophilicity $(\\mathsf{W C A}=2^{\\circ}$ ).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 28,
+        "chunk": "# 4.2.3. Template-assisted fabrication  \n\nGenerally speaking, template-assisted fabrication involves two basic steps. An anti-fogging solution is deposited into a micro/nanoporous material (template), allowing the solvent to evaporate. Afterwards, the template is selectively removed, yielding micro/nanostructured arrays or freestanding 3D structures. Following this protocol, Han and collaborators [247] recently developed a relatively complex strategy to elaborate biologically-inspired anti-fogging films. Here, butterfly's wing scales were used as a template to produce a $\\mathrm{SiO}_{2}$ film with multiscale hierarchical pagoda structures. The hierarchical surface roughness resulting in the significantly high surface density of the hydrophilic OH groups, translated to extreme wetting behavior. Coated glass samples featured excellent anti-fogging activity, as supported by the observed optical transparency $(\\mathrm{T}_{\\mathrm{average}}\\approx95\\%)$ under aggressive fogging conditions. Using the colloidal templating method, Vogel et al. [248] demonstrated the feasibility of preparing a $\\mathrm{SiO}_{2}$ -based periodic array of nanopores with tunable re-entrant geometry. Regardless of the pore size and the opening angle, which were changed by adjusting the TEOS/EtOH ratio in the starting sol-gel solution, all of the coated glasses exhibited extreme wetting behavior $(\\mathsf{W C A}\\approx0^{\\circ}$ ) following calcination at $500~^{\\circ}\\mathrm{C}.$ $\\mathrm{SiO}_{2}$ layers prepared from colloidal particles of $200\\ \\mathrm{nm}$ in diameter imparted superior anti-fogging capacity to glass slides.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 29,
+        "chunk": "# 4.3. Surface functionalization and related techniques  \n\nIn addition to “top-down” and “bottom-up” processing, another way to confer anti-fogging performance to a given material consist in modifying its surface chemistry. Surface treatments such as plasma treatment [249] and ionic implantation [43] have amply demonstrated their effectiveness in conferring resistance to fogging to poorly wettable polymers such as polyethylene, polypropylene, and polyethylene terephthalate. The main reason for this relies on the formation of hydrophilic groups on the surface, such as OH, COOH, COH, CN, $\\mathsf{N H}_{2}$ , etc., wellknown for their favorable interaction with water drops (spreading mechanism) [250–252]. Worthy of mention are the studies conducted by Patel and collaborators [214,253], who prepared anti-fogging polyethylene terephthalate (PET) using low-pressure plasmas operating under a controlled $0_{2}$ gas atmosphere $(20\\ s c c m)$ ) (sccm: “standard cubic centimeters per minute). Following plasma treatment for $5\\mathrm{min}$ , PET films did become superhydrophilic (WCA went from 95 to $\\approx0^{\\circ}$ ) in response to a concurrent rise in the number of carbonyl-containing functionalities on the surface. Even though the plasma-treated PET retained transparency when placed over a cup of hot water, the hydrophilicity was found to degrade upon exposure to both dry and humid environments for 7 days. These authors also [214] conferred antifogging property to ITO glass, following application of $50\\mathrm{V}$ for $20\\mathrm{min}$ to an aqueous solution of ${\\mathrm{H}}_{2}{\\mathrm{SO}}_{4}$ were a ITO sample was immersed. These authors argued that the electrochemical oxidation of water yielded hydroxyl groups on the ITO surface, which explains why, WCA abruptly decreased from 80 to $0^{\\circ}$ . Although not prevented, hydrophilicity loss due to surface aging was slower than that observed with the plasma-treated PET films under the same fogging conditions. Alternatively, extremely wettable $(\\mathsf{W C A}<5^{\\circ})$ ) films of polydiethylene glycol bis(allylcarbonate) with resistance to fogging were prepared by implantation of $\\mathsf{A r}^{+}$ ions under very low $0_{2}$ pressure [43]. A pre-implantation treatment with $\\mathrm{He^{+}}$ ions was found to delay significantly the hydrophilicity loss, hence the occurrence of fogging. While the above-mentioned surface treatments hold great promise for the manufacture of agricultural and food packaging films with anti-fogging characteristics, the problem of surface aging remains unresolved. This fact may explain why the incorporation of surfactants appears to be gaining in popularity in this regard [254–256]. Surfactants are molecules consisting of two well-differentiated parts, namely, a hydrophobic tail and a hydrophilic head. In general the hydrophilic domain contains hydroxyl [257–263] or amine groups [264]. When incorporated to polymer formulations, these molecules migrate from the bulk to the film surface, where they dissolve in the condensed water, decreasing its surface energy. As a result, water drops wet evenly the surface and scattering events are mitigated [260]. According to Irustra [264] and Salmeron [265] the use of additives comes with two major problems. First, as long as a sufficient amount of surfactant dissolves in the condensate, the anti-fogging/ anti-dripping film will perform adequately; however, given that it takes a while for these molecules to migrate and dissolve in water, these films usually fog up when exposed to sudden temperature or humidity changes. Second, considering that surfactants are gradually washed away by the dripping water, the anti-fogging/anti-dripping performance deteriorates over time. Thus, controlling the migration rate of these molecules is crucial to retaining the anti-fogging performance long term. In general, the migration of surfactants can be slowed down if bonded to inorganic nanoparticles such as SSNPs [266–268] or if added to blends of hydrophilic grafted co-polymers with un-grafted ones [269]. To retain wetting features for longer periods of time, covalent grafting of “bulky” surfactants, also known as “graft copolymerization”, represents a feasible alternative to plasma and ionic implantation treatments, as well as the addition of surfactants per se[270,271]. The applicability of this surface treatment on low surface energy polymers is motivated by the fact that the steric hindrance prevents these molecules from hiding in the bulk, thus hampering surface aging. Voluminous surfactants such as monostearic acid monomaleic acid glycerol (MMGD), [272] glycerol monolauric acid monoitaconic acid diester (GLID) [273], trifluoroacetic acid allyl ester (TFAA) [274], maleic anhydride (MA) [275], or polyether pentaerythritol monomaleate (PPMM) [276] have been successfully grafted to the backbone of linear low-density polyethylene (LLDPE) without compromising its optical and mechanical properties.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 30,
+        "chunk": "# 5. Application trends of anti-fogging surfaces  \n\nIn sectors of activity such as the medical, the photovoltaic, or the horticultural, the use of surfaces endowed with anti-fogging performance is on the rise and under perpetual development. In this section, some of the most relevant applications of these surfaces are briefly presented.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 31,
+        "chunk": "# 5.1. Food industry  \n\nIn the horticultural sector, the presence of condensation inside greenhouses causes injury to produce (dripping water) [18,269] and favors the development of fungal diseases [254]. Further to this, the decline in sunlight passing through the greenhouse claddings due to the total internal reflection occurring at the water drop/air interface has also been reported to affect crop yield [4,5,277]. Far from being an irrelevant issue, the effects of condensation on light transmission have been studied extensively for ${>}20$ years. For instance, using different agricultural films, including polyethylene (PE), PE with IR-absorbing features, UV-stabilized PE, and double-layered PE films, Cemek and Demir [18] estimated an average loss in light transmittance between 5 and $17\\%$ for a 2-month testing period. Similar results were reported by Pearson and colleagues [278] (transmission $10s s\\approx13\\%$ and Geoola's group [279] (transmission $\\begin{array}{r}{\\mathrm{loss}=9\\mathrm{-}10\\%}\\end{array}$ ) with modified and unmodified PE films. In this context, the use of plastics containing anti-fogging/antidripping additives (Section 4.3) is more than welcome, as better light transmission translates to enhanced plant growth rates and more abundant crops. Commercial additives such as Atmer $\\cdot\\mathtt{m}_{A00}$ and Atmer $\\cdot\\mathrm{\\Delta}\\mathrm{m}_{103}$ (Uniquema Polymer Additives, Switzerland), Loxiol A4 Spezial (Emery Oleochemicals, Malaysia), Dyneon™ MM5935 EF (Dyneon LLC, USA), and AF0406PE (Tosaf, Israel) deliver proven anti-fogging/anti-dripping performance to the most commonly used cladding materials (e.g., PE, PP, PTFE, PVC, PS, and PC).  \n\nRegarding food packaging, plastic films used to pack freshly chopped meats or vegetables play two crucial roles: they help limit waste by displaying the content more attractively and provide protection, so that food remains safe to eat for a reasonable period of time. However, unless the package contains moisture absorbers (e.g., sorbitol, xylitol) or enables moisture to permeate, sudden changes in temperature results in a packed produce surrounded of condensation. Experience shows that consumers are less likely to purchase when the “seethrough” property is severely compromised. As in the case of greenhouse cladding materials, the incorporation of anti-fogging additives into polymeric films (e.g., PP [280–283], PTFE [284], LLDPE [254,285,286], and PLA [287]) represents the most cost-effective solution adopted thus far by the manufacturing sector to minimize the effects of condensation.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 32,
+        "chunk": "# 5.2. Photovoltaic industry  \n\nSolar cells are electrical devices made of semiconductors that generate voltage when exposed to light [288]. It is widely known that silicon is the leading material in solar cell production; however, its use comes with a major problem: ${>}30\\%$ of the incident light is reflected because of its high refractive index. In addition to this, dust accumulation has been reported to contribute up to another $10\\%$ to overall nonabsorbed light [289]. Surprisingly, compared to existing literature on anti-reflective coatings for solar cells, few studies have addressed the issue of condensation, even though the formation of surface fog adversely affects the energy conversion efficiency of these devices. Indeed, according to Lu et al. [138] the scattering phenomenon provoked by water drops decreases the amount of photons reaching the cell surface, hence the ratio between the number of collected carriers and the number of all the incident photons, namely, the quantum efficiency. A reasonable approach to address this problem involves the use of coatings made of highly porous $\\mathrm{SiO}_{2}$ . These surfaces reduce contaminant adsorption and enable water drops to wet the surface [16,138,142]. For example, after covering the photoanodes of a high-performance solidstate dye-sensitized solar cell with SSNPs, Park and collaborators [16] observed an improvement in the photovoltaic efficiency of $5.9\\%$ in the presence of condensation. These anti-fogging coatings endowed with anti-reflective characteristics would not only improve the optical properties of future transparent solar cells but also their photovoltaic conversion efficiency, by enhancing light harvesting. Dual anti-fogging/ anti-reflective coatings with self-cleaning property, have also shown to further improve the performance of solar cells. In general, these coatings are made of $\\mathrm{TiO}_{2}$ or $\\mathrm{SiO}_{2}/\\mathrm{TiO}_{2}$ mixtures [290–292]. In addition to featuring resistance to fogging, the cell surface is cleaned at room temperature as a result of the photocatalytic activity (ROS species) and the “sweeping” effect of water (photoinduced superhydrophilicity).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 33,
+        "chunk": "# 5.3. Medicine  \n\nIn light of the growing number of endoscopic procedures reported annually in developed countries (e.g., 15–20 millions in the US), it is an incontestable fact that camera-guided instruments have become indispensable surgeon's colleagues [293]. In these situations, where a sharply defined field of view is required for obvious reasons, surgeons must paradoxically struggle with the low-quality images provided by the endoscope camera. The root cause of the impaired surgeon's vision reflects the result of two factors acting together. namely, the soiling of endoscope lens caused by the physiological fluids, and the formation of surface fog induced by temperature and relative humidity differences between operating rooms and human body [294]. To recreate the view attained in an open surgery, surgeons are forced to periodically clean the lens in water or saline Unfortunately, constant intraoperative interruptions put the patient's health at risk, slow down the surgery's progress, and contribute to surgeon frustration. Indeed, several studies [295,296] have evidenced that an increase in the number of times that the endoscope is withdrawn led to the increases in both the estimated blood loss and the operative time. Longer operative times make financial costs for both hospital and patient skyrocket.  \n\nWithin this framework, the implementation of anti-fogging technology is key to ensuring a safe and a successful surgical procedure. Available strategies aimed at maintaining a clear operating field can be divided into four broad categories: endoscope lens warming, use of temporary anti-fogging coatings and modified endoscopes, and other defogging approaches [294]. Regarding those changing the morphology of water drops, anti-fogging strategies based on temporary coatings involve applying commercial solutions such as Covidien FRED [297–299], Betadine [300], Hibiscrub [297], and baby shampoo [297] on the endoscope lenses. FRED™ (Fog Reduction and Elimination Device) and Betadine™ are aqueous solutions: the first one contains isopropyl alcohol $(<15\\mathrm{wt\\%})$ and surfactants $(2\\mathrm{wt\\%})$ ; and the second one, well known for its antiseptic activity, contains povidone‑iodine $(10\\mathrm{wt\\%})$ . Cheaper alternatives such as the use of patients' saliva [301] or saline solutions [302], as well as rubbing the endoscope lens on viscera [303] have also proven to be suitable to mitigate fogging effects. Also, worthy of mention are the endoscopes incorporating lenses covered with permanent anti-fogging coatings. For instance, using the layer-by-layer assembly, Aizenberg and colleagues [293] coated a bronchoscope lens with solid silica nanoparticles embedded in a thermally cured polydimethylsiloxane resin. $100\\mathrm{-nm}$ -thick SSNPs/PDMS films endowed the lens with anti-fogging and blood-repelling characteristics. Ohdaira et al. [304,305] prepared $\\mathrm{TiO}_{2}$ -coated lenses using the spin-coating technique followed by silicone-sealing and post-treatment at $200^{\\circ}\\mathsf C$ for $10\\mathrm{min}$ . After $12{-}15\\mathrm{~h~}$ of exposure to UV light, the as-fabricated coatings displayed better anti-fogging performance than did heated or washed lenses [305], making it possible to perform surgery with no retraction of the laparoscope [304].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 34,
+        "chunk": "# 5.4. Optical applications  \n\nFrom swimmers to surgical technicians to mining workers, dealing with fogged eyeglasses can be a challenging task. Indeed, this frustrating phenomenon usually forces the person to focus on wiping eyeglasses dry or wait for them to defog, putting under certain circumstances her/his safety at risk [306–311]. Protective eyewear fogging experienced by construction workers when laboring outside illustrates one among many obvious paradigmatic examples of surface fog formation, as it encompasses all of the favorable conditions to induce water condensation, namely, transitions between warm and cool environments, worker exertion, and tight eyewear. Even tough Mother Nature dictates that the fogging of eyewear must occur, human intervention can efficiently prevent it. For example, the fogging of surgical goggles can be reduced by applying a temporary anti-fogging solution called “Body Glove Fog Away” [312]. Permanent coatings of $\\mathrm{TiO}_{2}$ have been very successful in preventing condensation on mirrors [313–316]. In the same vein, coatings based on cellulosic ethers, have also shown to confer notable anti-fogging capability to a plethora of elements, including visors and transparent shields, sports goggles, safety glasses, face shields, and surgical masks, among others [317,318].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 35,
+        "chunk": "# 6. Concluding remarks and outlook  \n\nAnti-fogging mechanisms and their link with recent progress in fabrication techniques toward anti-fogging property are discussed in length in this review. Anti-fogging surfaces with additional features such as self-healing, self-cleaning, and anti-bacterial properties as well as the main sectors of human activity making use of them, including food and photovoltaic industries and medical practice, are also addressed. Nevertheless, despite years of tremendous efforts and achievements made in the field of anti-fogging surfaces, some relevant challenges remain.  \n\nStandards applied in North America (e.g., CSA Z611-M86 [319] and ASTM F659–10/−06 [320,321]) and Europe (e.g., CEN EN 168 [322]) for guaranteeing (protective) eyeglasses to reliably perform under fogging conditions are quite limited and not necessarily adapted to everyday activities. In F659–10 and EN 168 standards, the sample is immersed in distilled water at room temperature $(23\\pm5^{\\circ}\\mathsf C)$ for $^{1\\mathrm{h}}$ and then placed over a water bath $(50.0\\pm0.5^{\\circ}\\mathrm{C})$ after being dried at room temperature ( $50\\%$ RH) for $\\geq12\\mathrm{~h~}$ . For a sample to be considered anti-fogging, the time required for the light transmittance to decrease to $80\\%$ of its initial value (non-fogged sample) must be lower than or equal to $30~\\mathsf{s}.$ In Z611-M86 standard, the sample is cooled at $-25~^{\\circ}C$ and exposed thereafter to ambient conditions ( $23^{\\circ}\\mathrm{C},$ $50\\%$ RH). Here, rather than measuring light transmission, the time it takes for a transparent substrate to defog is reported. The application of these standards is highly questionable when assessing fogging resistance of eyeglasses during day-to-day activities, for example, when taking a walk, when moving from a warm to a cold environment, when cooking in a steaming environment or even when breathing. In our opinion, developing a certification adapted to day-to-day activities would be certainly applauded.  \n\nAccording to Briscoe [5], Grosu [43], and Pieters [4] a WCA angle of ${<}40{-}50^{\\circ}$ is required for a surface to be anti-fogging; that said, several studies [111,114,119,121,152,172,176] disagree with this rule, as it is possible to prevent fogging effects despite WCA exceeding this cut-off value. The main reason for this lies in the fact that this rule only holds true for nonporous anti-fogging coatings whose surface features do not display time-dependent behavior. In addition to the contact angle, several factors related to fogging effects, such as the number and the size of water drops [99,109], surface rearrangement phenomena [170], as well as the capability of the coating to transport water molecules [175,176], must also be considered to establish a more robust antifogging criterion.  \n\nOn the other hand, designing of a “well-rounded” anti-fogging material is more than a simple adjustment in the morphology of water drops, as many other features, such as mechanical durability and optical properties, must also be considered. For example, the use of inorganic materials to elaborate anti-fogging coatings faces two major challenges, namely, the deposition on thermally sensitive materials and the problem of light reflection. Following coating deposition, it is standard practice to implement thermal treatments (e.g., calcination, annealing); however, high temperatures make it challenging to coat polymeric substrates because of thermal degradation concerns. In this regard, developing coating techniques adapted to thermally sensitive substrates would undoubtedly be welcome. Optical transparency is another critical parameter to consider when designing anti-fogging layers. The adjustment of the refractive indices of the coating and the substrate is of considerable relevance to minimize the reflection of light. This implies that the thickness of the coating must be equal to $\\lambda/4n_{c},$ where $\\uplambda$ is the wavelength of the incident light and $n_{c}$ is the refractive index of the coating [323]; and that the refractive index of the coating must be $n_{c}$ $={\\sqrt{n_{s}n_{a i r}}},$ where $n_{s}$ is the refractive index of the substrate and $n_{a i r}$ is the refractive index of the air $(n_{s}>n_{c})$ [324]. Simultaneously fulfilling these two design criteria is quite often more difficult than imagined.  \n\nDespite the plethora of materials and fabrications techniques employed thus far to design anti-fogging surfaces, bridging the gap between fundamental research and industry is a pending issue. Even though their large-scale fabrication is not particularly challenging, addressing the problem of mechanical durability is crucial to make it a reality. Experience shows that any surface is exposed to mechanical wear caused by rubbing during day-to-day use or by solvents under normal cleaning practices. In coated surfaces, temperature variations can lead to coating deformation or detachment because of the differences in thermal expansion coefficient between the coating and the substrate. Mechanical wear, temperature variations, and exposure to cleaning products may result in a deterioration of the anti-fogging performance over time. Thus, designing anti-fogging surfaces with abrasion resistance (e.g., durable self-healing properties) with optimal adherence to the substrate is key to ensuring a long service life once integrated in items, such as mirrors, eyeglasses, and home windows, that make our day-to-day living more comfortable.  \n\nAccording to recent studies, the future trend in this promising field points to unique anti-fogging surfaces exhibiting an optimal combination of features to cover a wide range of applications. For example, dual anti-fogging/anti-bacterial surfaces will likely be most welcome in endoscopic surgery, while anti-fogging surfaces endowed with selfhealing properties would find a niche of opportunity in swimming goggles, solar panels, or automobile windshields. Undoubtedly, anti-fogging surfaces would be welcomed in applications where a clear visualization of the liquid medium plays a crucial role. Such is the case, for example, with micro/nanofluidic devices and microreactors for chemical synthesis and cell culture. Another opportunity niche for anti-fogging surfaces can be found in fiber optics [325] as well as among amateur and professional photographers. We firmly believe that future development of anti-fogging technology will be based on two fundamental pillars, namely industrial research and the use of eco-friendly materials. Indeed, the development of less time-consuming and cost-effective fabrication techniques compatible with industrial manufacturing using anti-fogging materials coming from renewable sources is undoubtedly a pending issue. In conclusion, research focusing on fundamental aspects of anti-fogging surfaces is still necessary to make industrial and professional applications of anti-fogging technology a reality.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 36,
+        "chunk": "# Acknowledgements  \n\nThe authors thank Pascale Chevalier for her helpful advice concerning the redaction of this review. This work was supported by the Natural Sciences and Engineering Research Council (NSERC) of Canada (G.L), PRIMA-Québec (G.L) and the Centre Québécois sur les Matériaux Fonctionnels (CQMF) (G.L.).",
+        "category": " References"
+    },
+    {
+        "id": 37,
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F659–06 Standard specification for skier goggles and faceshields-Annex A1. Test method for fogging propeties. West Conshohocken, PA: ASTM International; 2004.   \n[322] CEN. EN 168 Personal eye protection, non-optical test methods. Brussels: Comité Européen de Normalisation (CEN); 2001.   \n[323] Chattopadhyay S, Huang YF, Jen YJ, Ganguly A, Chen KH, Chen LC. Anti-reflecting and photonic nanostructures. Mater Sci Eng R Reports 2010;69:1–35.   \n[324] Raut HK, Ganesh VA, Nair AS, Ramakrishna S. Anti-reflective coatings: a critical, indepth review. Energ Environ Sci 2011;4:3779–804.   \n[325] Kim R, Park C, Lee A, Moon J. Development of the noncontact temperature sensor using the infrared optical fiber coated with antifog solution. Sci Technol Nucl Install 2015;2015:1–4.",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# UV-curable waterborne polyurethane-acrylate: preparation, characterization and properties  \n\nHeping Xu, Fengxian Qiu ∗,  Yingying Wang, Wenling Wu, Dongya Yang, Qing Guo  \n\nSchool of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, China",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# a r t i c l e i n f o",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# a b s t r a c t  \n\nArticle history:   \nReceived 8 April 2011   \nReceived in revised form 28 July 2011   \nAccepted 25 August 2011   \nKeywords:   \nUV-curable   \nWaterborne polyurethane-acrylate   \nSolvent resistance   \nMechanical properties  \n\nThe waterborne polyurethane-acrylate (PUA) oligomer was firstly prepared based on isophorone diisocyanate (IPDI),  polyether polyol (NJ-210), dimethylol propionic acid  (DMPA) and  hydroxyethyl methyl acrylate (HEMA) via  in  situ  and  anionic self-emulsifying method. The UV-curable polyurethane-acrylate (UV-PUA) was obtained with oligomer, monomers (BA and TPGDA) and photoinitiator Darocur 1173. FT-IR, DSC  and  TGA  were  employed to  investigate the  structures and  thermal properties of  the  UV-PUA films. The  effects  of BA/TPGDA (R)  value, the  content of Darocur 1173 and  the  UV  curing  time  on  the performances were investigated. Some mechanical performances, solvent resistance and the gel content of UV-PUA films  were  measured. When the  ratio  of BA/TPGDA was  5/5,  the  UV-PUA film had  the  best solvent (water, alkali  and  ethanol) resistances. Besides, with the  ratio  of the  BA/TPGDA increasing, the  surface drying time increased. When the  content of  Darocur  1173 was $4\\%$ ,  the  gel  content  achieved the  maximum while the  surface  drying time  achieved the  minimum. The  obtained UV-curable polyurethane-acrylates are promising as oligomers for  UV-curable coatings, plastics, inks  and  adhesives.  \n\n$\\mathfrak{C}$ 2011 Elsevier B.V. All rights reserved.",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1. Introduction  \n\nPolyurethanes (PU) have been found in wide applications such as coatings and adhesives due to their unique properties, and great efforts have been made in chemistry and physics. Waterborne polyurethane (WPU) has been developed largely because of its excellent mechanical properties, fire resistance, low toxicity and lack of environmental hazard, but suffers from poor water and alkali resistance because of the hydrophilic group such as carboxyl group in their molecule chains. Compared with the polyurethane resin, polyacrylate-type products show an outstanding performance in the weatherability, water resistance, and solvent resistance, therefore there is a complementary role in the performance of polyurethane (PU) and polyacrylate (PA). Waterborne polyurethane-acrylate (WPUA) can obtain various properties and enhanced performance resulted from its specific segmented structure and modification with acrylate. And it can be satisfactorily applied in coatings for wood and automobiles, biologic materials, electronic materials, textiles, leather and printing inks [1–3].  \n\nRecently, environmental legislation is increasingly strict with coatings industry. The waterborne coatings using ultraviolet (UV)- curing technology have gained increasing interests due to their advantages such as less environmental pollution, low energy consumption, high chemical stability, cost efficient, high curing speed and very rapid curing even at ambient temperatures [4–7]. These environmental friendly products are used to reduce the volatile organic compounds (VOC) released to the atmosphere by solventborne systems and are expected to exhibit same performance as that of conventional solvent-borne systems [8–11]. The UV-curable WPUA coating has the features of instant drying, solvent-free formulations, reduced energy consumption, coating on heat sensitive substrate, low space and capital requirement for curing equipment [12–18]. The UV-curable coatings consist of oligomer, monomer and photoinitiator, so the coating film properties, such as hardness, abrasive resistance, flexibility and weatherability, mainly depend on the oligomer structure and its concentration in the formulation. Therefore, looking for more new structure and special property PUA would play the key role in the development of UV curable chemistry [19]. In the process of photo-polymerization, the content of the photoinitiator would determine the degree of the polymer curing [20]. Besides, the photoinitiated radical polymerization of acrylate resins, the presence of radical scavengers, the reactivity and viscosity of the acrylate formulation, the wavelength and intensity of the UV radiation all could affect the performance of the UV curing film. Studer et al. [21] comprehensively investigated the effect of all these UV curing parameters on acrylate conversion.  \n\nIn this work, the UV-PUA oligomer was prepared with isophorone diisocyanate (IPDI), polyether polyol (NJ-210), dimethylol propionic acid (DMPA), hydroxyethyl methyl acrylate (HEMA) via in situ and anionic self-emulsifying method; and the UV-PUA system was composed of the oligomer, photoinitiator Darocur 1173 and monomers (BA-TPGDA). The effects of the ratio of the BA/TPGDA, Darocur 1173 and the curing time on the performance of the UV-PUA films were investigated. The UV-PUA films were characterized and analyzed by Fourier transform infrared spectroscopy (FT-IR), Differential scanning calorimetry (DSC), solvent resistance, gel content and mechanical properties.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2. Experimental",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.1. Materials  \n\nPolyether polyols (NJ-210, $M n{=}1120\\mathrm{g/mol}_{\\cdot}^{\\cdot}$ ) was produced by Ningwu Chemical CO., Ltd., in Jurong, Jiangsu, China. Dimethylpropionic acid (DMPA) was produced by PERSTOP Co., in Helsingborg, Sweden. Isophorone diisocyanate (IPDI) was supplied by Rongrong Chemical Ltd., Shanghai, China. Hydroxyethyl methyl acrylate (HEMA) was provided by Yinlian Chemical Ltd., Wuxi, Jiangsu, China. Butyl acrylate (BA), triethylamine (TEA), acetone, dibutylbis (lauroyloxy) tin (DBLT), and N-methyl -2-pyrrolidone (NMP) were obtained from Sinopharm Chemical Reagent Co., Ltd., Shanghai, China. Tripropyleneglycol diacrylate (TPGDA) and Darocur 1173 were supplied from Mingda Macromolecule Science and Technology CO., Ltd., Suzhou, Jiangsu, China.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.2. Preparation of UV-PUA oligomer  \n\nA certain amounts of NJ-210 (10.802 g) and IPDI $(8.325{\\mathrm{g}})$ were added into a four-necked flask equipped with a mechanical stirrer, thermometer and reflux condenser. Then, DBLT was added as catalyst and the mixture was heated to $60^{\\circ}\\mathsf C$ and keeping the temperature for $2\\mathrm{h}$ to prepare the –NCO terminated prepolymer. Next, the above prepolymer was reacted with a certain amount of DMPA $(1.221\\mathrm{g})$ dissolved in small amount of NMP at $80{-}85^{\\circ}C$ for another $^{2\\mathrm{h}}$ , and the –NCO terminated prepolymer containing carboxyl group was obtained. Then the reactant was cooled down to $60^{\\circ}\\mathsf C$ HEMA $(4.875\\mathrm{g})$ was added into the system and reacted at $60^{\\circ}C$ for $^{5\\mathrm{h}}$ . When the temperature was cooled down to $40^{\\circ}\\mathsf C$ TEA were added into the flask subsequently and reacted at $40^{\\circ}C$ for $30\\mathrm{min}$ . The mixture was then dispersed into deionized water under vigorous stirring for $30\\mathrm{min}$ . The synthetic route of UV-PUA oligomer was shown in Fig. 1.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.3. Preparation of UV-PUA film  \n\nUV-PUA films were prepared by casting the newly synthesized oligomer, BA and TPGDA onto a poly (tetrafluoroethylene) drying at $65^{\\circ}\\mathsf{C}$ for $3\\ensuremath{\\mathrm{h}}$ . Because water was used as diluents in this system, it needed the flash-off step, where water was evaporated before UVcuring. During the water in the aqueous dispersion to be removed, physical entanglement occurred could be acquired because of the large molecular weight of the prepolymer [22–24].  Then, with the UV light that was produced by a lamp (main wave length: $365\\mathrm{nm}$ the power of the lamp: 1000 W, the UV energy per second: $1000\\mathrm{J}/s$ and the distance between the thin film samples and the center of UV lamp was $20\\mathrm{cm}$ ) irradiating, the Darocur 1173 was activated and the radicals could be produced. The formed radicals broke the acrylate double bond of the monomers and oligomers which resulted in crosslinking, then the UV-PUA film could be obtained. The waterborne UV-PUA film was cured through two-step process as shown in Fig. 2 and the photodissociation mechanism of Darocur 1173 was shown in Fig. 3.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.4. The hardness of UV-PUA films  \n\nThe hardness was measured with a sclerometer (KYLXA, Jiangdu Kaiyuan Test Machine Co., Ltd., Jiangdu, China);  \n\nmeasurements were done three times for each sample, and the average value was calculated.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.5. The tensile strength and elongation at break of UV-PUA composite films  \n\nTensile strength testing and elongation at break testing for all of the specimens were carried out on a tensile tester (KY-8000A, Jiangdu Kaiyuan Test Machine Co., Ltd., Jiangdu, China) at room temperature at a speed of $50\\mathrm{{mm}/\\mathrm{{min}}}$ . All measurements had an average of three runs. The dumbbell-type specimen was $30\\mathrm{mm}$ long at two ends, $0.2\\mathrm{mm}$ thick and $4\\mathrm{mm}$ wide at the neck.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 2.6. The water absorption (or swelling degree) of UV-PUA films  \n\nThe measurements of water absorption or swelling degree of the UV-PUA films were the same procedures. The procedures for these measurements were briefly described as follows. The PU or PUA films were cut into the size of $30\\mathrm{mm}\\times30\\mathrm{mm}$ and put into water, $5\\%\\mathsf{N a O H}$ and ethanol at $25^{\\circ}\\mathsf{C}$ after being weighted. $24\\mathrm{h}$ later, the film was taken out, rub dry by wiping off the surface water with a piece of filter paper, and then weighted again. The water absorption (or swelling degree), $\\omega$ , was calculated by as follows Eq. (1):  \n\n$$\n\\omega=\\frac{W_{2}-W_{1}}{W_{1}}\\times100\\%\n$$  \n\nwhere $W_{1}$ is the mass of the film before being put into the water, etc. $W_{2}$ is the mass of the film after being put into the water, etc.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# 2.7. The gel content of UV-PUA films  \n\nThe UV-PUA films were cut into the size of $2\\mathsf{c m}\\times2\\mathsf{c m}$ , then the sample was put into a solvent (acetone) for $48\\mathrm{h}$ , and dried for $^{72\\mathrm{h}}$ at $30^{\\circ}\\mathsf C$ to give a constant weight. The gel content was calculated according to the following formula (2):  \n\n$$\nG=\\frac{W}{W_{0}}\\times100\\%\n$$  \n\nwhere $W_{0}$ is the mass of the film before being put into the toluene.   \n$W$ is the mass of the film after being put into the toluene.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# 2.8. The surface drying time of UV-PUA films  \n\nPut the UV-curable emulsion (the water had been evaporated) under the UV lamp irradiating for a certain amount of time, then gently pressed the UV-curable film with finger. If there is no trace on the film, the time of the UV lamp irradiating was the surface drying time of UV-PUA films.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 14,
+        "chunk": "# 2.9. Structure characterization of the UV-PUA oligomer and the UV-PUA films  \n\nFT-IR spectrum of the UV-PUA film was obtained between 4000 and $400\\mathrm{cm}^{-1}$ with an FTIR spectrometer (AVATAR 360, Madison, Nicolet). A minimum of 32 scans was signal-averaged with a resolution of $2{\\mathrm{cm}}^{-1}$ in the $4000{-}400{\\mathrm{cm}}^{-1}$ ranges.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# 2.10. Thermal properties  \n\nDifferential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) of the UV-PUA film were performed on a Netzsch instrument (STA 449 C, Netzsch, Seligenstadt, Germany). The programmed heating range was from room temperature to $500^{\\circ}{\\mathsf C}$ at a heating rate of $10^{\\circ}C/\\operatorname*{min}$ under a nitrogen atmosphere. The measurement was taken with $_{6-10\\mathrm{mg}}$ samples. DSC and TG curves were recorded.  \n\n![](images/68d7d16bc5f5ca88da8190750e5a6e5e47275299a3c12d4b503c21c7664439bf.jpg)  \nFig. 1. The synthetic route of the UV-PUA oligomer.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 16,
+        "chunk": "# 3. Results and discussions",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 3.1. The effect of ratio of BA/TPGDA (R) on the properties of UV-PUA films  \n\nFixed the content of the Darocur 1173 $(3\\%)$ , NCO:OH ratio (2.0) and the weight of the PUA oligomer $(10.8{\\mathrm{g}})$ , a series of UV-PUA films were prepared through changing the R value. The proportion of the UV-curable was listed in Table 1.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# 3.1.1. The mechanical properties of UV-PUA films  \n\nThe mechanical properties for UV-PUA films were listed in Table 1. From Table 1: (1) With the increasing of TPGDA content, the hardness of the UV-PUA films increased gradually. This was because the polarity of the hard monomer TPGDA was familiar with the hard segment of PU. There have been hydrogen bonding and some compatibility between the PU and TPGDA phases in the systems. With the increasing of hard monomer content, the density of the hard segment in the molecular chains increased, the cross-linked degree improved because of the hydrogen bonding formation. At larger hard segment content, the phase of the hard segment exhibited higher impact strength, higher hardness. However, hardness became inferior beyond optimum concentration of acrylate. (2) With the ratio of BA/TPGDA decreasing, the tensile strength of the UV-PUA films firstly increased then decreased, while the elongation at break of the UV-PUA films firstly decreased then increased. When the BA/TPGDA was 5/5, the tensile strength reached the maximum.  \n\nTable 1 The effects of BA/TPGDA (R) on the properties of UV-PUA films.   \n\n\n<html><body><table><tr><td>Sample item</td><td>UV-PUA-1</td><td>UV-PUA-2</td><td>UV-PUA-3</td><td>UV-PUA-4</td><td>UV-PUA-5</td></tr><tr><td>BA/TPGDA (R)a</td><td>9/1</td><td>7/3</td><td>5/5</td><td>3/7</td><td>1/9</td></tr><tr><td>Hardness (Shore A)</td><td>86</td><td>89</td><td>91</td><td>92</td><td>94</td></tr><tr><td>Tensile strength (MPa)</td><td>1.57</td><td>2.32</td><td>2.98</td><td>2.46</td><td>2.28</td></tr><tr><td>Elongation at break (%)</td><td>98.54</td><td>89.23</td><td>86.76</td><td>90.07</td><td>92.02</td></tr><tr><td>Water absorption (%)</td><td>12.13</td><td>8.98</td><td>5.32</td><td>10.31</td><td>14.50</td></tr><tr><td>Swelling degree (%) (5% NaOH)</td><td>22.64</td><td>18.06</td><td>7.54</td><td>7.48</td><td>16.69</td></tr><tr><td>Swelling degree (%)(Ethanol)</td><td>46.57</td><td>32.18</td><td>15.42</td><td>23.61</td><td>28.06</td></tr></table></body></html>\n\na BA/TPGA was the percentage based on the whole monomers.  \n\n![](images/12d3c300acd0323d5178ceca35c8d62f061990b71f81de7e53dc5f2f4c53d036.jpg)  \nFig. 2. The cured process of the waterborne UV-PUA film.  \n\n3.1.2. The water absorption (or swelling degree) of UV-PUA films The water absorption or swelling degree of the PUA films was measured and the results were shown in Table 1. As shown in Table 1: (1) when waterborne UV-PUA emulsions are used as resins for coating and adhesives, the water resistance is an important property. The UV-PUA-3 film had the lowest water absorption showing that the UV-PUA-3 film had the best water resistance. Besides, the UV-PUA-3 film also had excellent alkalinity and ethanol resistance compared with other UV-PUA films. (2) When the ratio of BA/TPGDA was the same, the solvent resistance of UV-PUA film was that the water resistance was the best while the ethanol resistance was the worst.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 3.1.3. The gel content and the surface drying time of UV-PUA films  \n\nThe gel content and the surface drying time of UV-PUA films were shown in Fig. 4. With the ratio of BA/TPGDA increasing: (1) The gel content of UV-PUA films firstly increased then decreased When the BA/TPGDA was 5/5, the gel content was $89.68\\%$ , and reached the maximum. (2) The surface drying time of UV-PUA films decreased. Because the BA had a good dilute effect on the UV-PUA emulsion and reduced the viscosity of the system. On the one hand, the molecular motion ability of the UV-PUA emulsion enhanced and the $\\mathsf{C}{=}\\mathsf{C}$ quantity increased, on the other hand, oxygen could more easily spread to the system which consumed more and more free redical, so that the odds of the light polymerization would reduce, the UV-curing time would increase and the system even could not be fully cured [25].  \n\n![](images/2e619a23a57ca1d5aeaf973c4d8a60feca5009cc846a96a106972a17fd90e48d.jpg)  \nFig. 3. The photodissociation mechanism of Darocur 1173.  \n\n![](images/0bc802040e14ce395c97653c7a734c7bbcd77e23ce9c3b1b735a2ca9f01be4f6.jpg)  \nFig. 4. The gel content and the surface drying time of the UV-PUA films at the different ratio of BA/TPGDA.  \n\n3.1.4. Structure characterization of the UV-PUA film The structure of the UV-PUA film was characterized by FTIR as shown in Fig. 5. The spectral analysis was mainly used to check the completion of polymerization reaction, in terms of disappearance of the NCO band at $2270\\mathrm{cm}^{-1}$ illustrating the NCO had basically been reaction. Besides, the spectrum of UV-PUA film exhibited a strong absorption band at 3383 and $3378\\mathrm{cm}^{-1}$ , which should be ascribed to the hydrogen bonding between $\\mathsf{N{\\mathrm{-}}H}$ and carbonyl groups. It could be seen that there was a progressive change in the absorption pattern of $\\scriptstyle{\\mathsf{C}}=0$ stretching region at $1730\\mathrm{cm}^{-1}$ , which might be attributed to the presence of acrylate group. The absorption peak of $\\mathsf{C}{=}\\mathsf{C}$ usually at $1631\\mathrm{cm}^{-1}$ $\\scriptstyle\\left[=C\\right]$ and $1412\\mathrm{cm}^{-1}$ $\\scriptstyle(={\\mathsf{C H}}_{2})$ ), but after UV radiation, the spectrum of UV-PUA film the $\\mathsf{C}{=}\\mathsf{C}$ bond disappeared, which illustrated that the $\\mathsf{C}{=}\\mathsf{C}$ bond of the polyurethane chains has been polymerized.  \n\n![](images/4edeadccd03d0f8fca5294e24f3717dd935752f10f015a413d2f3050a24a9b5f.jpg)  \nFig. 5. The FT-IR spectrum of the UV-PUA film.  \n\n![](images/2661cbe1a8633bbecc13095dc28803eb928bce60d2a0d3e444921f95b32d0e8d.jpg)  \nFig. 6. The DSC curves of the UV-PUA films.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# 3.1.5. Thermal properties  \n\nThe DSC and TGA curves of the UV-PUA films were shown in Figs. 6 and 7. From Fig. 6, it can be seen that the hard segment glass transition temperature $(T_{g})$ appeared at $55.0\\substack{-58.0^{\\circ}C}$ in the DSC curves. Furthermore, an endothermic peak at $64.0\\substack{-68.0^{\\circ}C}$ in curves could be observed resulting from crystallization melting of the soft segment. From Fig. 7, the decomposition temperatures $(T_{d})$ of UV-PUA-4 film at $5\\%$ , $10\\%$ and $50\\%$ mass losses were $118^{\\circ}{\\mathsf{C}}$ , $152^{\\circ}\\mathsf C$ and $370^{\\circ}\\mathsf C$ respectively. The decomposition temperatures $(T_{d})$ of UV-PUA-3 film at $5\\%$ , $10\\%$ and $50\\%$ mass losses were $118^{\\circ}{\\mathsf{C}}$ , $150^{\\circ}\\mathsf C$ and $370^{\\circ}\\mathsf C$ respectively. The decomposition temperatures $\\left(T_{d}\\right)$ of UV-PUA-2 film at $5\\%$ , $10\\%$ and $50\\%$ mass losses were $118^{\\circ}{\\mathsf{C}}$ , $148^{\\circ}\\mathsf C$ and $362^{\\circ}\\mathsf{C}$ , respectively. The results indicated that the UV-PUA film had the good thermal properties.  \n\n![](images/3dea25e9102507ba10791e16afff121b406537f86f114b4315ffb3fe2f8113cf.jpg)  \nFig. 7. The TGA curves of the UV-PUA films.  \n\n![](images/2b9ba01b6cb26a2eb312c935c2386b37b15892d1be4d4f5aec70ca96bb2a03fd.jpg)  \nFig. 8. The gel content and the surface drying time of the UV-PUA films at the different content of the Darocur 1173.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# 3.2. The effect of the content of Darocur 1173 on the properties of UV-PUA films  \n\nFixed the ratio of the BA/TPGDA $\\left(R=5/5\\right)$ and the weight of the PUA oligomer $(10.8\\mathrm{g})$ , a series of UV-PUA films were prepared through changing the content of the Darocur 1173. The proportion of the UV-curable emulsion was listed in Table 2. The properties of UV-PUA films were systematically investigated.  \n\n3.2.1. The gel content and the surface drying time of UV-PUA films The gel content and the surface drying time of UV-PUA films were shown in Fig. 8. With the content of the Darocur 1173 increasing:  \n\n(1) The gel content of UV-PUA films firstly increased then decreasing. When the content of the Darocur 1173 was $4\\%$ the gel content was $92.54\\%$ and reached the maximum. It may be due to the absolutely curable velocity, which was decided by the forming velocity of the free radical on the surface of the coating. And according to the Larmbert–Beer’s law, the light intensity was degressive in the form of exponential function when the content of the photoinitiator increased. When the content of the photoinitiator was excessive, the photoinitiator closed to the surface of the coating would absorb the most part of the Ultra Voilet, the light flux reached to the interior would decrease sharply, the number of the free radical produced by the photoinitiator and the velocity of the UV curable reduced. Besides, the cured film on the surface coating might hinder the molecular movement at the bottom coating, so that the gel content reduced and the curing degree decreased [20]. (2) The surface drying time of UV-PUA films firstly decreased then increasing. If the content of the Darocur 1173 was low, the energy may not effectively be used, and the number of the generated free radicals was lower than the reaction required, thus the curing speed would be slower. With the content of the Darocur 1173 increasing, the number of the generated free radicalsc increased, the curing speed would be quicker. But if the content of the Darocur 1173 was higher than the reaction required, there would be excess free radicals generated which could easily coupling each other, then terminated the chain growth and the curing speed would be slow at last. So when the content of the Darocur 1173 was $4\\%$ , the surface drying time reached the minimum and the curing effect was the best.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# 3.2.2. The mechanical properties of UV-PUA films  \n\nThe mechanical properties for UV-PUA films were listed in Table 2. With the content of the Darocur 1173 increasing: (1) The hardness of the UV-PUA films had little changed. This was maybe due to the UV-PUA films had the same quality of the PUA Oligomer and monomers which were the same as the hard segment and soft segment. (2) The tensile strength of the UV-PUA films firstly increased then decreased while the elongation at break of the UVPUA films firstly decreased then increased. When the content of the Darocur 1173 was $4\\%$ , the tensile strength was $3.03\\mathrm{MPa}$ and reached the maximum.  \n\nTable 2 The effects of Darocur 1173 content on the properties of UV-PUA films $(R=5/5)$ .   \n\n\n<html><body><table><tr><td>Sample item</td><td>UV-PUA-6</td><td>UV-PUA-7</td><td>UV-PUA-3</td><td>UV-PUA-8</td><td>UV-PUA-9</td></tr><tr><td>Content of Darocur 1173 (%)a</td><td>1.0</td><td>2.0</td><td>3.0</td><td>4.0</td><td>5.0</td></tr><tr><td>Hardness (Shore A)</td><td>88</td><td>89</td><td>91</td><td>90</td><td>89</td></tr><tr><td>Tensile strength (MPa)</td><td>2.06</td><td>2.52</td><td>2.98</td><td>3.03</td><td>2.65</td></tr><tr><td>Elongation at break (%)</td><td>104.30</td><td>98.23</td><td>94.76</td><td>92.07</td><td>96.02</td></tr></table></body></html>\n\na The percentage based on the whole UV system.  \n\nTable 3 The effects of the curing time on the properties of UV-PUA films $\\left(R=5/5\\right)$ .   \n\n\n<html><body><table><tr><td>Sample item</td><td>UV-PUA-10</td><td>UV-PUA-11</td><td>UV-PUA-12</td><td>UV-PUA-13</td><td>UV-PUA-14</td><td>UV-PUA-15</td></tr><tr><td>Curing time (s)</td><td>10</td><td>20</td><td>30</td><td>40</td><td>50</td><td>60</td></tr><tr><td>Hardness (Shore A)</td><td>85</td><td>87</td><td>91</td><td>92</td><td>91</td><td>92</td></tr><tr><td>Tensile strength (MPa)</td><td>1.86</td><td>2.82</td><td>3.14</td><td>3.13</td><td>3.15</td><td>3.14</td></tr><tr><td>Elongation at break (%)</td><td>117.21</td><td>96.57</td><td>93.42</td><td>93.39</td><td>93.41</td><td>93.40</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# 3.3. The effect of the curing time on the properties of UV-PUA films  \n\nFixed the ratio of the BA/TPGDA $\\left(R=5/5\\right)$ , the content of the Darocur 1173 $(4\\%)$ and the weight of the PUA oligomer $(10.8\\mathrm{g})$ a series of UV-PUA films were prepared through changing the curing time. The proportion of the UV-curable emulsion was listed in Table 3. The properties of UV-PUA films were systematically investigated.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 24,
+        "chunk": "# 3.3.1. The effect of the curing time on the gel content of UV-PUA films  \n\nThe effect of the curing time on the gel content of UV-PUA films were shown in Fig. 9. At the UV-curable prophase, the gel content gradually increased with the UV curing time increasing. This was due to the dual bond was not opened entirely when the curing time was too short. When the curing time reached 30 s, the gel content increased slightly but changed not obvious if the curing time continued to be increased. Because when the curing time was $30s$ dual bond was opened entirely and the curing reaction basically completed. The curing degree basically remain unchanged even if prolong the curing time.  \n\n![](images/a9cc59dcf664a384b50d047a1ea75c95b354d20da345cb14c3d1fa40581d7105.jpg)  \nFig. 9. Effect of curing time on gel content of the UV-PUA films.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 25,
+        "chunk": "# 3.3.2. The effect of the curing time on the mechanical properties of UV-PUA films  \n\nThe mechanical properties for UV-PUA films were listed in Table 3. With the curing time increasing, the hardness and the tensile strength of the UV-PUA films firstly increased and subsequently had little changed while the elongation at break firstly decreased then changed little. Because, when the curing time was too short, the dual bond was not opened entirely. But when the curing time reached $30s$ , the dual bond of the UV-PUA system was opened entirely and the curing reaction basically completed. The curing degree basically remain unchanged even if prolong the curing time. So when the curing time surpassed 30 s, the hardness, the tensile strength and the elongation at break of the UV-PUA films had little changed.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 26,
+        "chunk": "# 4. Conclusion  \n\nThe waterborne UV-PUA emulsion was prepared using UV-PUA oligomer, the Darocur 1173 and the monomers composed of BA and TPGDA. The proportion of BA and TPGDA, the content of the Darocur 1173 and the curing time were important effects on the properties of the cured films. The experimental results indicated that the optimum irradiation time was $30{-}40s$ after the coatings being painted on a poly (tetrafluoroethylene) plate at room temperature, the ratio of the BA/TPGDA was 5/5, and initiator dosage was $4\\%(\\mathrm{wt}\\%)$ of the latex. Almost all the UV-PUA films have good hardness, solvent resistance and mechanical properties. It is hopeful that the UV-PUA dispersions can be applied to commercial use in different regions.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 27,
+        "chunk": "# Acknowledgement  \n\nThis project was supported by the Agricultural Independent Innovation of Jiangsu Province (CX(11)2032), Jiangsu Planned Projects for Postdoctoral Research Funds (1002033C) and Jiangsu Province Key Laboratory of Fine Petro-chemical Technology (213164).",
+        "category": " References"
+    },
+    {
+        "id": 28,
+        "chunk": "# References  \n\n[1] S.K. Lee, B.K. Kim, J. Colloid Interface Sci. 336 (208) (2009).   \n[2] M.M. Rahman, E.Y. Kim, J.Y. Kwon, H.J. Yoo, H.D. Kim, Int. J. Adhes. Adhes. 28 (47) (2007).   \n[3] H.T. Lee, S.Y. Wu, R.J. Jeng, Colloids Surf., A 276 (176) (2006).   \n[4] X. Kong, S.M. Li, J.Q. Qu, H.Q. Chen, J. Macromol. Sci. A 47 (368) (2010).   \n[5] A.K. Nanda, D.A. Wicks, S.A. Madbouly, J.U. Otaigbe, Macromolecules 39 (7037) (2006).   \n[6] M.  Tielemans, P. Roose, P.D. Groote, J.C. Vanovervelt, Prog. Org. Coat. 55 (128) (2006).   \n[7]  A. Asif, W.F. Shi, X.F. Shen, K.M. Nie, Polymer 46 (11066) (2005). [8] K. Johansson, M. Johansson, Prog. Org. Coat. 63 (155) (2008).   \n[9] U. Kästner, Colloids Surf., A 183–185 (805) (2001).   \n[10] A.J. Guenthner, D.M. Hess, J.J. Cash, Polymer 49 (5533) (2008).   \n[11] K. Wutticharoenwong, M.D. Soucek, Macromol. Mater. Eng. 293 (45) (2008).   \n[12] M.M. Rahman, W.K. Lee, J. Appl. Polym. Sci. 114 (3767) (2009).   \n[13] C. Sow, B. Riedl, P. Blanchet, Prog. Org. Coat. 67 (188) (2010).   \n[14] S.M. Cakic, J.V. Stamenkovic, D.M. Djordjevic, I.S. Ristic, Polym. Degrad. Stab. 94 (2015) (2009).   \n[15] H.D. Hwang, J.I. Moon, J.H. Choi, H.J. Kim, S.D. Kim, J.C. Park, J. Ind. Eng. Chem. 15  (381) (2009). [16] Z.L. Yang, D.A. Wicks, C.E. Hoyle, H.T. Pu, J.J. Yuan, D.C. Wan, Y.S. Liu, Polymer 50 (1717) (2009).   \n[17] V.D. Athawale, M.A. Kulkarni, J. Coat. Technol. Res. 7 (189) (2010).   \n[18] X. Cheng, Z. Huang, J. Liu, W. Shi, Prog. Org. Coat. 59 (284) (2007).   \n[19]  B.K. Kim, Y.H. Cho, J.S. Lee, Polymer 41 (1325) (2000).   \n[20] X.Y. Xiao, C.C. Hao, Colloids Surf., A 359 (82) (2010).   \n[21] K. Studer, C. Decker, E. Beck, R. Schwalm, Prog. Org. Coat. 48 (101) (2003).   \n[22] D.B. Otts, E. Heidenreich, M.W. Urban, Polymer 46 (8162) (2005).   \n[23] Y.U. Ahn, S.K. Lee, H.M. Jeong, B.K. Kim, Prog. Org. Coat. 60 (17) (2007).   \n[24] M.H. Lee, H.Y. Choi, K.Y. Jeong, J.W. Lee, T.W. Hwang, B.K. Kim, Polym. Degrad.   \nStab. 92 (1677) (2007).   \n[25] S. Katia, D. Christian, B. Erieh, S. Reinhold, Prog. Org. Coat. 48 (92) (2003).",
+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,72 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Robust UV-Curable Dual-Cross-Linked Coating with Increased Transparency, Long-Term Antifogging, and Efficient Antibacterial Performances  \n\nLina Zhang, Kai Feng,\\* Yizhe Liu, Fangrong Wu, Yubo Liu, Bo Yu, Xiaowei Pei, Lijia Liu, Chunhong Zhang, Yang Wu,\\* and Feng Zhou  \n\nCite This: ACS Appl. Polym. Mater. 2024, 6, 6645−6657",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# ACCESS  \n\nMetrics & More  \n\nArticle Recommendations s\\*ı Supporting Information  \n\nABSTRACT: Antifogging coatings are urgently needed in daily life. However, current research efforts seldom focus on enhancing the mechanical wear resistance of coatings or investigating their antifogging properties under wet and dry conditions. Herein, a robust dual-cross-linked polymeric antifogging coating was developed through the UV curing of poly[(methacryloxyethyl)dimethylheptylammonium bromide−acrylic acid] (pMDHAB− AA) and poly(ethylene glycol) diacrylate (PEGDA). Taking advantage of the dual-crosslinked structure and the delicate balance of hydrophilic−hydrophobic components in pMDHAB−AA, the coating presented durable antifogging performances, including longtime antifogging in hot vapor and numerous antifogging in an alternation of wetting and drying and robust mechanical wear resistance. In addition, based on the hygroscopic nature of the quaternary ammonium groups, the coating was endowed with oleophobicity underwater, an ultralow friction coefficient, and antibacterial and resistance-to-bacterialadhesion performances. More importantly, the antifogging coating plays a crucial role in enhancing substrate transparency by reducing the diffuse reflection. This prepared material addresses current concerns related to antifogging coatings and holds significant potential for applications in various fields, including optical glass, medical devices, agricultural films, etc.  \n\n![](images/908c3b95902fb2a7476412b99b9f85a6747540c787ad80ae6d33193b1e8e7375.jpg)  \n\nKEYWORDS: transparent, dual-cross-linked, multifunctional, antifogging, wear resistant",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# INTRODUCTION  \n\nTransparent substrates are widely used in both daily life and optical analysis instruments.1,2 However, unforeseen variations in the temperature and humidity lead to the condensation of water droplets on the transparent substrate surfaces and the formation of fog.3−5 The presence of fog droplets significantly degrades the light transmittance, which not only leads to considerable inconveniences in daily life but also poses numerous potential safety concerns.6−10 Besides, in agriculture, the formation of fog on greenhouse films will reduce the transmittance of light, seriously affecting plant photosynthesis and thereby decreasing the crop yields.11−13 In medical applications, such as endoscopic, laparoscopic, and medical goggles, the occurrence of fog can impair the operator’s vision, potentially hindering the normal course of operation. Therefore, the development of novel technologies or materials capable of effectively preventing or reducing fogging has garnered significant attention from a wide scope of researchers.7,14  \n\nCurrently, diverse strategies have been proposed by researchers to address the issue of fogging.3,9,15,16 The first strategy is manipulating both the ambient temperature and the surface temperature of the substrate to reduce the temperature difference, thereby achieving the goal of antifogging.8,17 However, this method has been significantly limited due to its high energy consumption and weak environmental adaptation.18,19 Another widely employed strategy is fabricating an antifogging coating.20−22 However, commonly prepared superhydrophilic or superhydrophobic antifogging coatings suffer from several drawbacks. For example, superhydrophilic materials like surfactants,10,23 hydrophilic polymer brushes,24,25 sol−gel coatings,26,27 etc., fail to maintain long-term antifogging properties and often exhibit poor mechanical properties. For superhydrophobic antifogging coating, tedious processes and intricate nanostructures are typically involved. The mechanical vulnerability of the nanostructured surface inevitably limits its practical application.28−30 Consequently, in recent years, amphiphilic coatings (e.g., polymer coatings with a combination of hydrophilic quaternary ammonium groups and hydrophobic chains) have received wide attention in antifogging applications due to their ability to control the hydrophilic/hydrophobic balance,31−35 while previously reported conventional amphiphilic coatings often neglected longterm antifogging effectiveness and abrasion resistance, which are critical concerns for practical antifogging coating applications.  \n\n![](images/9d0b04947eaae7dc926bf2e6f047429e194d19c268ca8370f8368d8509218da9.jpg)  \n\nHerein, we present a highly transparent multifunctional antifogging coating through a delicate hydrophilic/hydrophobic balance using a UV-assisted cross-linking method. The incorporation of quaternary ammonium groups renders the coating with excellent antibacterial, antistatic, oloephobicity performances underwater and upon thousands of friction cycles in both air and water without any influence of antifogging. The stability and wear resistance of the coating was attributed to the dual-cross-linked structure formed between the pMDHAB−AA−aziridine network and PEGDA network. In addition, the hygroscopicity and stability endowed the coating with a long-term antifogging ability. Importantly, the antifogging coating enhances the transparency of a polyolefin (PO) film by reducing diffuse reflection, thereby improving the photosynthetic efficiency of crops. Hence, there is a significant demand for the application of this novel multifunctional antifogging coating in practical scenarios.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# EXPERIMENTAL SECTION  \n\nMaterials. 2-(Dimethylamino)ethyl methacrylate (DMAEMA, $99\\%$ ), $^{2,2^{\\prime}}$ -azobis(2-methylpropionitrile) (AIBN, $98\\%$ ), 1-bromoheptane, pentaerythritol tris[3-(1-aziridinyl)propionate] (APA, $99\\%$ ), poly(ethylene glycol) diacrylate (PEGDA), and UV initiator 2- hydroxy- $\\cdot4^{\\prime}$ -(2-hydroxyethoxy)-2-methylpropiophenone $(98\\%)$ were purchased from Shanghai Macklin Biochemical Co., Ltd. AIBN was recrystallized from ethanol before use. Acrylic acid (AA, $>99\\%$ ) was purchased from Aladdin. Solvents, including dichloromethane, ethyl acetate, toluene, hexane, acetonitrile, and so forth, were obtained from Sinopharm Chemical Reagent Co., Ltd. $o$ -Xylene $(98\\%)$ was purchased from XiYa Chemical Technology (Shandong) Co., Ltd. Except for AIBN, all chemicals were used as received.  \n\nSynthesis of the Prepolymer pDMAEMA−AA Copolymer. The copolymer was synthesized through conventional free-radical polymerization using the following procedure. A total of $_{\\textrm{40}\\textrm{g}}$ of DMAEMA and ${4\\mathrm{g}}$ of AA were added to a $250~\\mathrm{mL}$ flask, followed by the addition of $\\boldsymbol{44}\\mathrm{~g~}$ of $o$ -xylene and $0.44\\mathrm{~g~}$ of AIBN (1 wt $\\%$ with respect to the total monomer mass) as the thermal initiator. The polymerization was conducted at $80~^{\\circ}\\mathrm{C}$ in an oil bath with magnetic stirring for $^{12\\mathrm{~h~}}$ . After the reaction was finished, the final copolymer was precipitated by hexane, and then the pure pDMAEMA−AA copolymer was obtained by washing three times with hexane and drying in a vacuum oven for $24\\mathrm{~h~}$ at $60~^{\\circ}\\mathrm{C}$ .  \n\nPreparation of Quaternary Ammonium Salt. Quaternary ammonium salt was prepared by quaternization of pDMAEMA−AA copolymer with 1-bromoheptane. A total of $_{4\\textrm{g}}$ of pDMAEMA−AA copolymer and $6.24~\\mathrm{g}$ of 1-bromoheptane were introduced to $30~\\mathrm{mL}$ of acetonitrile. Subsequently, the mixture underwent thorough stirring at $80~^{\\circ}\\mathrm{C}$ for $^{12\\mathrm{~h~}}$ to obtain a faint-yellow solution. Next, the solid residues were collected through vacuum rotary evaporation after the flask was cooled to room temperature. The resulting products were purified and washed with hexane three times to remove the monomer and impurity that remained unreacted. Finally, the product was dried in a vacuum oven at $60~^{\\circ}\\mathrm{C}$ for $^{24}\\mathrm{h},$ and then the pure quaternary ammonium copolymer (pMDHAB−AA) was acquired.  \n\nPreparation of the Dual-Cross-Linked pMDHAB−AA/PEGDA Coating and Single-Cross-Linked APA and PEGDA Coatings. Before the dual-cross-linked coating was prepared, the poly(ethylene terephthalate) (PET) film was ultrasonically cleaned with ethanol for $30\\ \\mathrm{min},$ , followed by drying in an oven. First, $1.2\\mathrm{~g~}$ of quaternary ammonium copolymer was dissolved in $\\textbf{8g}$ of deionized water at room temperature with magnetic stirring for $^{12\\mathrm{~h~}}$ . Then $0.236\\mathrm{~g~}$ of APA $\\big(}{}^{1}/}_{3}\\mathrm{mol}$ of the copolymer) was added, and the mixture was stirred for $^{2\\mathrm{h},}$ followed by the addition of $0.024\\ \\mathrm{g}$ of PEGDA (2.0 wt $\\%$ with respect to the copolymer) and $0.0024\\ \\mathrm{g}$ of 2-hydroxy- $\\cdot4^{\\prime}$ -(2- hydroxyethoxy)-2-methylpropiophenone (10 wt $\\%$ relative to PEGDA) with magnetic stirring for $^\\mathrm{~1~h~}$ to obtain a homogeneous solution. Then this solution was drop-coated on a clean PET film that was treated with oxygen plasma for $\\textsf{S m i n}$ to completely clean the surfaces and remove organic pollutants. Finally, the coating underwent UV curing using a lamp emitting light at $365~\\mathrm{nm}$ with a power of $300~\\mathrm{W}$ for $30\\ \\mathrm{min}$ , resulting in the formation of a UVcurable pMDHAB−AA coating. The single PEGDA coating was prepared using the same UV-curing method but without pMDHAB− AA and APA. For the single APA coating, the PEGDA and photoinitiator were not involved, and it was cured at room temperature for $24\\mathrm{~h~}$ .  \n\nCharacterization. The surface chemical compositions of the coating were characterized by X-ray photoelectron spectroscopy (XPS; Thermo Escalab 250XI). Fourier transform infrared (FTIR) spectroscopy was measured on a Nicolet IS 10 spectrometer for characterizing the functional groups of the synthesized copolymer in the range of $500{-}4000~\\mathrm{cm^{-1}}$ . $\\mathrm{^{1}H}^{\\cdot}$ NMR spectra were recorded on a Bruker AVANCE III 600 M instrument with deuterated dimethyl sulfoxide (DMSO- $d_{6.}$ ) as the solvent. The thermal stability was collected by thermogravimetric analysis (TGA; Netzsch STA 449 F5/ F3 Jupiter analyzer) from 20 to $800^{\\circ}\\mathrm{C}$ at a heating rate of $10~{^\\circ}\\mathrm{C}/\\operatorname*{min}$ under a $\\Nu_{2}$ atmosphere. The surface topography and thickness of the pDMAEMA−AA coating were observed by atomic force microscopy (AFM; Bruker Dension Icon) and field-emission scanning electron microscopy (SEM; Tescan, CLARA GHM). The coatings for SEM were sputter-coated for $180\\ s$ with gold to ensure the coatings had good conductivity. The elemental distribution on the coating surface was obtained by energy-dispersive spectroscopy (EDS). UV−vis spectrophotometry (UV-2600, GGC003) was tested to confirm the transparency of samples in the range of a visible-light wavelength from 400 to $800\\ \\mathrm{nm}$ . Water contact angles (WCAs) were recorded with 5 $\\mu\\mathrm{L}$ of deionized waterdrops. Microscopic images were collected on a research-level intelligent fully automatic inverted fluorescent metallographic microscope (DMi8A, GGC006).  \n\nAntifogging Test. The antifogging properties were conducted based on both hot-vapor and cold-warm conditions, separately. For the hot-vapor antifogging test, samples were placed over hot vapor (upon $5\\ {\\mathrm{cm}}\\ {\\mathrm{high}}$ ) with the coated surface facing down by placing it on a $250~\\mathrm{mL}$ glass beaker that contained hot water ( $\\sim60~^{\\circ}\\mathrm{C},$ $100\\%$ relative humidity), and the glass beaker was placed on a hot plate to maintain the temperature. Then digital photographs of the fogging behavior were taken at different time intervals. For the cold-warm antifogging test, samples were first stored in a freezer at $-20{}^{\\circ}\\mathrm{C}$ for 30 min and then transferred immediately to ambient conditions $(\\sim20$ ${}^{\\circ}{\\bf C},$ $55\\%$ relative humidity), and the transparencies of the samples were recorded after 5 s by a camera. In addition, light transmission data were collected on a UV−vis spectrophotometer in the wavelength region of $400{-}800~\\mathrm{nm}$ to quantitatively characterize the antifogging performances of the samples.  \n\nAntibacterial Test. Antibacterial tests were carried out according to a standard antibacterial susceptibility test protocol.36,37 Gramnegative Escherichia coli and Gram-positive Staphylococcus aureus were chosen as representative bacteria to test the antibacterial activity of the copolymer and the dual-cross-linked pMDHAB−AA coating. The minimum inhibitory concentrations (MICs) of the synthesized pMDHAB−AA copolymer were first determined. In this work, 4096 $\\mu\\mathrm{g}$ of the pMDHAB−AA copolymer was first dissolved in $2{\\mathrm{~mL~}}$ of Mueller−Hinton broth (MHB) and then diluted by a continuous 2- fold method to obtain a series of copolymer solutions with different concentrations. Bacteria were also diluted immediately to obtain a concentration of $1\\times10^{6}\\mathrm{CFU/mL}$ of the suspension with a decimal dilution method. A total of $100~\\mu\\mathrm{L}$ of copolymer solution with a certain concentration and $100~\\mu\\mathrm{L}$ of bacterial suspension ( $\\mathit{\\Omega}_{1\\times10^{6}}$ $\\mathrm{CFU/mL}$ ) were added to each well of a 96-well plate. A total of 200 $\\mu\\mathrm{L}$ of MHB was set as the negative control and $100\\mu\\mathrm{L}$ of MHB with  \n\n![](images/0caa1e79f2e7c510d3e36695ba4444fe4bd803c71ecf4fc436853843049213a2.jpg)  \nFigure 1. (a) Preparation process of the pMDHAB−AA copolymer. (b) FTIR spectrum of the pMDHAB−AA copolymer. (c) $^{1}\\mathrm{H}$ NMR spectrum of the quaternary ammonium polymer pMDHAB−AA. (d) Full XPS spectra of the PET and pMDHAB−AA copolymer. (e) Thermal weight loss of the pDMAEMA−AA and pMDHAB−AA copolymers.  \n\n$100\\mu\\mathrm{L}$ of bacterial suspension were used as the positive control. After the 96-well plate was incubated at $37^{\\circ}\\mathrm{C}$ for $24\\mathrm{h}$ with a speed of 100 rpm, the optical density (OD) at $600\\ \\mathrm{nm}$ of the microorganism solutions was recorded by an enzyme standard instrument. Each experiment was measured in triplicate. The bacterial growth inhibition rate was calculated by the following equation:  \n\n$$\n=\\frac{\\mathrm{OD}_{\\mathrm{positive\\control}}-\\mathrm{OD}_{\\mathrm{sample}}}{\\mathrm{OD}_{\\mathrm{positive\\control}}-\\mathrm{OD}_{\\mathrm{negative\\control}}}\\times100\n$$  \n\nA zone-of-inhibition test was conducted to determine the antibacterial ability of the dual-cross-linked pMDHAB−AA coating. Briefly, the bacterial suspension was diluted with pure MHB to obtain a concentration of approximately $1\\times10^{6}\\ \\mathrm{CFU/mL}$ . After dilution, the bacterial suspension $(100~\\mu\\mathrm{L})$ was carefully applied to a lysogeny broth (LB) culture plate uniformly, and then the dual-cross-linked pMDHAB−AA coatings with diameter of $\\sim1\\ \\mathrm{cm}$ were placed on the lawns, and the coating layer was in contact with the LB agar. After 24 h of incubation at $37^{\\circ}\\mathrm{C},$ the inhibition zone was recorded by a camera. As a comparison, the blank PET film was observed under the same conditions. Furthermore, the antibacterial ability of the dualcross-linked pMDHAB−AA coating was further evaluated using the spread plate method. The PET films and the coatings $(2\\ \\mathrm{cm}\\times2\\ \\mathrm{cm})$ were placed on a 24-well plate, then $200\\mu\\mathrm{L}$ of bacterial suspension (1 $\\times10^{6}\\mathrm{CFU/mL},$ ) was added, and the resulting solution was incubated in a shaker at $37^{\\circ}\\mathrm{C}$ at a speed of $100~\\mathrm{rpm}$ for $24\\mathrm{~h~}$ . After incubation, $30~\\mu\\mathrm{L}$ of bacterial suspension was plated onto sterile LB agar culture plates, and the plates were incubated at $37~^{\\circ}\\mathrm{C}$ for $24\\mathrm{~h~}$ . After that, growth of the bacteria was recorded by a camera. In addition, the morphology and adhesion of the bacteria were observed by SEM. Briefly, $500\\mu\\mathrm{L}$ of bacterial suspension was dropped onto the PET and dual-cross-linked pMDHAB−AA coating on a 24-well plate, respectively, and then incubated for $^\\textrm{\\scriptsize4h}$ at $37~^{\\circ}\\mathrm{C}$ in a shaker. The samples were washed with phosphate-buffered saline (PBS) gently to remove free-floating bacteria. After that, the bacteria were fixed with a mixture solution that consisted of $5\\mathrm{mL}$ of a $2.5\\%$ glutaraldehyde fixed solution, $20~\\mathrm{mL}$ of deionized water, and $25~\\mathrm{mL}$ of PBS at $4^{\\circ}\\mathrm{C}$ for $^{2\\mathrm{h},}$ followed by rinsing with PBS again. Then the PET and dual-crosslinked pMDHAB−AA coating with bacteria were dehydrated with a graded ethanol series (25, 50, 75, 95, and $100\\%$ ) in $15~\\mathrm{min}$ for each concentration and dried in air. Before imaging, the samples were sprayed with gold by an ion sputter coater (GVC-2000) for $180\\ s$ .  \n\n![](images/dd9efe977c02369564be9b1154aa14e146a963a9b152e40a94a3a98c00227fd0.jpg)  \nFigure 2. (a) Preparation process of the dual-cross-linked antifogging coating. (b) Visible transmittance spectra of the bare PET and dual-crosslinked pMDHAB−AA coating. (c) Surface SEM images, (d) AFM images, and (e) EDS analysis of the dual-cross-linked pMDHAB−AA coating.  \n\n![](images/b0fa2a3dfcc99ff07b71d97437d2a0665475916a79cfc5325e58c41c0a695a1f.jpg)  \nFigure 3. (a) Variation of the WCA values on the dual-cross-linked pMDHAB−AA coating surface in air for $1000\\ s$ . (b) Schematic diagram of hydrophobic−hydrophilic conversion of the dual-cross-linked pMDHAB−AA coating. (c) Contact angle of organic solvents on the dual-crosslinked pMDHAB−AA coating surface underwater.  \n\nFriction Test. The wear resistance of the dual-cross-linked pMDHAB−AA coating was measured by an alcohol rubber abrasion test machine (model 339) in air. As for the method, briefly, polyester cloth was used as the upper friction pair, and the bare PET films covered with the dual-cross-linked pMDHAB−AA coating were subjected to different reciprocating friction cycles under a load of $1\\mathrm{N}$ . Then the WCAs of the coating surface were measured after 0, 2000, 4000, 6000, 8000, 10000, and 12000 friction cycles, separately. To evaluate the performance stability after friction, the antifogging property of the dual-cross-linked pMDHAB−AA coating after 12000 friction cycles was tested. In addition, the wear resistance of the pMDHAB−AA coating was conducted on a conventional ball-on-desk reciprocating friction tester (TRB3 tribometer) in water surroundings, and the poly(dimethylsiloxane) (PDMS) hemisphere with a diameter of $6~\\mathrm{mm}$ was employed as an upper friction pair.38",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# RESULTS AND DISCUSSION  \n\nPreparation and Characterization of the Copolymer of pMDHAB−AA. The chemical reaction equation is shown in Figure 1a, and the preparation process of the pMDHAB− AA copolymer is as follows. Initially, pDMAEMA−AA was synthesized through a thermally triggered free-radical polymerization reaction involving DMAEMA and AA units. Then, the copolymer was quaternized by 1-bromoheptane to alter the hydrophobic/hydrophilic balance. The chemical structure of the pMDHAB−AA copolymer was confirmed by FTIR and $\\mathrm{^{1}H}$ NMR spectra. As shown in Figure 1b, the absorption peak at $1160.7~\\mathrm{{\\dot{cm}}^{-1}}$ corresponded to the $\\mathrm{C-N}$ stretching of the quaternary ammonium group, and the absorption peak at $\\bar{17}25.7\\ \\mathrm{cm}^{-1}$ is attributed to the $\\scriptstyle{\\mathrm{C}}={\\mathrm{O}}$ stretching vibration of the ester group. The peaks at 2933.8 and $2866.0\\ \\mathrm{cm^{-1}}$ signified the $\\mathrm{C-H}$ stretching vibration of the alkyl group. Moreover, the characteristic peaks at 3431.0 and $1637.\\dot{1}\\mathrm{{\\cm}^{\\bar{-}1}}$ resulted from the stretching and bending vibrations of water molecules, respectively. The peaks at 1385.7 and $922.9~\\mathrm{{cm}^{-1}}$ were attributed to the hydroxyl stretching vibration of AA. The chemical structure of the quaternary ammonium polymer was also analyzed and confirmed by the $\\mathrm{^{1}H}$ NMR spectrum (Figure 1c). The chemical shifts at $3.1-3.4~\\mathrm{ppm}$ were assigned to the methyl groups (b and $\\mathbf{b}^{\\prime}$ positions) from aminomethyl $[-\\mathrm{N}(\\mathrm{CH}_{3})_{2}]$ and quaternary ammonium $[-\\mathrm{N^{+}}(\\mathrm{CH}_{3})_{2}-$ $\\mathrm{\\DeltaC_{7}H_{15}B r^{-}]},$ , respectively. The chemical shifts at $3.74\\mathrm{-}4.55$ ppm were attributed to methylene protons (f and $\\mathbf{f^{\\prime}}$ positions) that bonded to the ester groups. Also, the chemical shift at 3.43−3.71 ppm was attributed to methylene protons (e position) that bonded to $-\\mathrm{N}^{+}(\\mathrm{CH}_{3})_{2}\\mathrm{-}\\mathrm{C}_{7}\\mathrm{H}_{15}\\mathrm{Br}^{-}$ . The full XPS spectrum was used to determine the chemical compositions of the PET and pMDHAB−AA copolymer (Figure 1d). Also, the fine spectra of Br and N of the PET and pMDHAB−AA copolymer are shown in Figure S1. As shown in the figure, the Br and N elements were observed at binding energies of 67 and $400~\\mathrm{eV}$ for the pMDHAB−AA copolymer, respectively. It can be seen that the N signal was divided into two peaks at 398 and $402\\ \\mathrm{eV}_{;}$ which can be attributed to the tertiary and protonated amino groups, separately. The results confirmed that the tertiary amino groups in the pMDHAB−AA copolymer were not protonated totally by 1-bromoheptane. Figures 1e and S2 illustrate that the onset decomposition temperature of the pMDHAB−AA copolymer decreased from 302 to $233~^{\\circ}\\mathrm{C}$ compared with that of the pDMAEMA−AA copolymer, which was similar to the thermal degradation profile of the reported quaternized polymers.31,39 The decrease in the thermal stability is attributed to the Hofmann elimination of quaternary ammonium salts, which produces an alkene, a tertiary amine, and a low-molecular-weight compound specific to the counterion.40 Overall, these results affirm the successful preparation of quaternary ammonium.  \n\n![](images/6bffc0672bc3cc355809115c0015ee995d257a4217bf307842c6b7283dcf47b3.jpg)  \nFigure 4. Photographs of the PET film covered with different cross-linked coatings containing bare (a) PET film, (b) PEGDA coating, (c) APA coating, and (d) dual-cross-linked pMDHAB−AA coating over hot water $({\\sim}60~^{\\circ}\\dot{\\mathrm{C}}$ , $100\\%$ relative humidity). Photographs of fog condensation of the PET film covered with the (e) dual-cross-linked pMDHAB−AA coating and (f) PET film, which were first stored at $-20~^{\\circ}\\mathrm{C}$ for $30~\\mathrm{min}$ and then exposed quickly to ambient laboratory conditions ${\\bf\\Pi}^{\\prime}{\\sim}20^{\\circ}{\\bf C},$ $55\\%$ relative humidity). $(\\mathbf{g})$ Optical microscopy images of the antifogging process on the pMDHAB−AA coating and PET film in $10~\\mathrm{min}$ upon hot water ( $\\sim60^{\\circ}\\mathrm{C}$ , $100\\%$ relative humidity). (h) Light transmittance of the PET film and coated PET film in ambient conditions $\\mathrm{\\Omega}^{\\sim20\\mathrm{\\Omega}^{\\circ}C}$ , $60\\%$ relative humidity) after being stored at $-20{}^{\\circ}\\mathrm{C}$ for $30\\mathrm{min}$ . The antifogging test of (i) a window and (j) safety goggles when entering indoors $(25~^{\\circ}\\mathrm{C})$ from cold outdoors $(-15^{\\circ}\\mathrm{C})$ .  \n\nPreparation and Characterizations of the Dual-CrossLinked Antifogging Coating. The preparation process of the dual-cross-linked pMDHAB−AA coating is shown in Figure 2a. In the coating system, the pMDHAB−AA copolymer was cross-linked by APA at room temperature to form one cross-linked network, and for a second cross-linked network, the PEGDA molecules were triggered by a photoinitiator to form another cross-linked network. As is wellknown, transparency is essential for an antifogging coating. Therefore, the visible-light transmittance of both the PET film and the dual-cross-linked pMDHAB−AA coating were measured in the wavelength range of $400{-}800\\ \\mathrm{nm}$ (Figure 2b). The transmittance values of the dual-cross-linked pMDHAB−AA coatings on the PET film $(84-90\\%)$ ) were slightly higher than those of the bare PET film $(81-87\\%)$ , indicating that the pMDHAB−AA coatings have an antireflection effect, which can mainly be attributed to the fine nanostructure on the coating surface. This nanostructure can change the propagation path of light and reduce the reflection and scattering of light on the coating surface, thereby increasing the transmittance.41 The surface morphology and thickness of the dual-cross-linked pMDHAB−AA coatings were exhibited by SEM. As shown in Figures 2c and S3, the coating surface was very smooth and had a thickness of $2.5\\mu\\mathrm{m}$ . The surface morphology of the coatings was further observed by AFM. As shown in Figure 2d, the root-mean-square roughness $R_{\\mathfrak{q}}$ value of the coating surface was $0.202\\ \\mathrm{\\nm},$ , whereas the ${\\bar{R}}_{\\mathrm{q}}$ value of the pure PET surface was $1.09\\ \\mathrm{nm}$ (Figure S4). The nanoscale roughness further confirmed that smooth surfaces were formed, which can facilitate optical transparency.42 In addition, an electron energy-dispersive spectrometer was also applied to analyze and confirm the chemical composition of the dual-cross-linked pMDHAB−AA coating surface. Figure 2e reveals that the coating surface mainly contains C, N, O, and Br elements with atomic ratios of $75.68\\%$ , $5.74\\%$ , $12.37\\%$ , and $6.21\\%$ , respectively. The appearance of the Br element illustrates that 1-bromoheptane is successfully introduced to the coating. Finally, the TGA curves of different cross-linked coatings are shown in Figure S5. The difference of the initial decomposition temperature proves that the dual-cross-linked coating (pMDHAB−AA coating) shows good thermal stability.  \n\nThe wettability of the coating surface was determined with a contact angle meter, and the change of the WCA on the coating surface with time was recorded within 1000 s. As shown in Figure 3a, the coating surface has a high WCA value of $100^{\\circ}$ initially, and with the extension of time, the WCA on the coating surface decreased gradually and decreased to $43^{\\circ}$ at  \n\n1000 s. This phenomenon was attributed to the rapid hydration of ionic chain segments on the coating surface. As shown in Figure 3, in air surroundings, the long alkyl chain segments tend to spread to the coating surface, and therefore the coating surface has a large WCA at first. However, the quaternary ammonium groups hydrated and migrated to the coating surface gradually when the coating was in contact with a water droplet. With the extension of time, the coating became hydrophilic, and the water droplets spread. Due to the final hydrophilic state, the coating surface exhibits excellent superoleophobicity underwater. Various oily liquid droplets, including $o$ -xylene, toluene, and dichloromethane, were selected as the representative solvents to investigate the contact angles on the dual-cross-linked pMDHAB−AA coating underwater. As shown in Figure 3c, the contact angles of these oily liquid droplets can exceed $150^{\\circ}$ on the coating surface underwater. In contrast, for the pure PET film surface underwater, the contact angles are below $90^{\\circ}$ . The results confirm that the coating exhibits excellent superoleophobic characteristics underwater, which can be attributed to the presence of the hydrophilic quaternary ammonium components, which can form a hydration layer on the coating surface to prevent the adhesion of oily liquid droplets.  \n\nAntifogging Performance. The antifogging performance of the dual-cross-linked pMDHAB−AA coating was evaluated by both hot-vapor and cold-warm methods. Herein, to confirm the long-term availability of the dual-cross-linked pMDHAB− AA coating, two kinds of single-cross-linked PEGDA and APA coatings also were prepared and verified by the hot-vapor method. Three kinds of coatings, including dual-cross-linked pMDHAB−AA coating, PEGDA coating, APA coating, and pure PET film, were exposed $3\\ \\mathrm{cm}$ above the hot water vapor $(\\sim60^{\\circ}\\mathrm{C},$ $100\\%$ relative humidity), and the surface states were recorded by a digital camera. Unsurprisingly, the pure PET film was covered by small fog droplets quickly, and the words below became blurred (Figure 4a and Movie S1). The transparency of the PEGDA coating was maintained for less than $24\\mathrm{~h~}$ (Figure 4b), and the transparency of the APA coating remained for less than $^{40\\mathrm{~h~}}$ (Figure 4c). However, as shown in Figure 4d and Movie S2, the dual-cross-linked pMDHAB−AA coating maintained high transparency for more than 20 days, and no obvious water droplets or water mist were seen, which can be attributed to the hydrophilic quaternary ammonium and the higher cross-linking density. At the beginning, the tiny fog droplets were absorbed in the pMDHAB−AA coating network. With the prolongation of time, the condensed fog drops formed a uniform water film on the coating surface, which can avoid or reduce light scattering and refraction. The obtain results suggest that the pMDHAB− AA coatings have the longest antifogging time. For the coldwarm method, the pMDHAB−AA coating and pure PET film were first stored at $-20~^{\\circ}\\mathrm{C}$ for $30~\\mathrm{min}$ and then exposed to ambient conditions ( ${\\bf\\Gamma}\\sim20\\mathrm{\\Omega}^{\\circ}{\\bf C},$ $55\\%$ relative humidity). As shown in Figure 4e, the dual-cross-linked pMDHAB−AA coating was transparent and the words below were clearly visible, whereas the pure PET film showed a visible fog layer and the words beneath could barely be read. The antifogging behavior of the coating was also investigated on a microscopic scale. As shown in Figure $^{4}\\mathrm{g},$ within the initial ${\\boldsymbol{\\mathsf{S}}}\\ {\\boldsymbol{\\mathsf{s}}},$ a large number of water droplets with a diameter of approximately 25 $\\mu\\mathrm{m}$ were generated on the bare PET film surface, and the water droplets gradually increased with the extension of time. In contrast, no water droplets could be observed on the pMDHAB−AA coating surface at any instant, which illustrates the remarkable antifogging ability. In addition, in order to quantitatively evaluate the antifogging performance of the pMDHAB−AA coating, the transmittances of both the pMDHAB−AA coating and pure PET film were measured using a visible spectrophotometer within the wavelength range of $400{-}800\\ \\mathrm{nm}$ . As shown in Figure $\\mathrm{4h}_{\\cdot}$ , in the cold-warm method, the transmittance of the PET film sharply decreased to about $36{-}48\\%$ from $84-90\\%$ because of the fog forming on the surface. As for the pMDHAB−AA coating, the transparency was still maintained, which showed the efficiency of suppressing fog formation.  \n\n![](images/c06853113e54dde7133d971376691f8601a83bf26dcbe811994a46069dd9c145.jpg)  \nFigure 5. (a) Schematic diagram of a greenhouse in a winter environment. (b) Transparency comparison between coated and uncoated PO films. (c) Light transmittance of the blank PO film and the film covered with the dual-cross-linked pMDHAB−AA coating. (d) Antifogging comparison of uncoated and coated PO films with the cold-warm method. (e) Antifogging performance test in a simulated winter environment. (f) Light transmittance of the dual-cross-linked pMDHAB−AA coating after repetitive dry−wet alternating antifog test cycles with the cold-warm method.  \n\nConsidering possible practical application situations, the pMDHAB−AA coating was coated on various transparent substrates such as a window and safety goggles without affecting their inherent optical transparency. The antifogging performances of a window and safety goggles that were covered with the pMDHAB−AA coating were checked by the cold-warm method. As shown in Figure 4i, the window model was used to verify the antifogging ability of the dual-crosslinked pMDHAB−AA coating in the case of a large temperature difference between inside and outside surroundings. This shows that the uncoated surface became opaque immediately, while the coated surface maintained visible clearness. In addition, when entering warm rooms $(25~^{\\circ}\\mathrm{C})$ from the cold outdoors $(-15^{\\circ}\\mathrm{C})$ , the pure goggle fogged up quickly, whereas the coated goggle remained highly transparent (Figure 4j). The above results show that the dual-cross-linked pMDHAB−AA coating can still maintain good transparency when the external environment changes, which proves its good practical value.  \n\nIt is universally acknowledged that fog on a greenhouse film affects the photosynthesis of crops and reduces vegetable yields; therefore, antifogging coatings are very important for use on agricultural greenhouses. As shown in Figure 5a, a greenhouse simulation experiment was used to further test the feasibility of coating on a greenhouse film. Figure 5b shows that the plant under the greenhouse PO film decorated with a coating is clearer than the blank PO film. The visible-light transmittance of the PO film increased from $81.1\\%$ to $91.0\\%$ after it was decorated with the antifogging coating (Figure 5c), which is more conducive to the transmission of sunlight and the growth of crops. Figure 5d shows the antifogging performance under the cold-warm test. As shown by the result, the plant outline under the blank film cannot be seen, while the plant under the coated film is still clear. The longterm antifogging performance of the coated film was determined under a simulation environment in an ice locker. A $-20~^{\\circ}\\mathrm{C}$ value of an ice locker simulated the outdoor temperature in winter, and the internal temperature of greenhouse was $25\\ ^{\\circ}\\mathrm{C},$ provided by a water bath. As shown in Figure 5e, the uncoated film became opaque immediately, and with increasing time, the condensed small fog drops became bigger and dropped due to its nonwettability. In contrast, the film covered with the dual-cross-linked pMDHAB−AA coating showed high optical transparency and was maintained for more than 20 days, which illustrates the long-term antifogging performance. Besides, the dry−wet alternating antifogging test was conducted with the cold-warm method and hot-vapor method to demonstrate the durability of the coating. Briefly, for the cold-warm method, the PO film covered with the dual-cross-linked pMDHAB−AA coating was first stored in a freezer at $-20{}^{\\circ}\\mathrm{C}$ for $30\\mathrm{min}$ , and then the PO film was taken out of the freezer and exposed to ambient conditions for ${\\boldsymbol{\\mathsf{S}}}{\\boldsymbol{\\mathsf{s}}},$ and the visible-light transmittance of the PO film was measured to judge its antifogging performance. For the hot-vapor method, the coating was exposed on hot water vapor $(60~^{\\circ}\\mathrm{C}_{\\mathrm{\\i}}$ , $100\\%$ relative humidity) for $\\textsf{S}\\operatorname*{min}$ , and the transmittance was collected using the same method. After the coatings were dried in air, the experiment was repeated many times. The light transmittance changes of the coated film with various cycles are summarized in Figures 5f and S6. It is easy to see that, after 10 cycles of the dry−wet alternating antifogging test, the transmittance of the coating has no significant changes, which proved that the stable antifogging property could be maintained on the surface after being repeated many times, clearly illustrating the excellent practical relevance of the coating for the desirable application. Beyond that, as shown in Figure S7, the transparency of the coating has not been affected, and there is no cracking on the surface of the coating after bending 100 times, which means that the prepared coating can be deposited on the flexible and foldable film.  \n\n![](images/f65e8dee0a76b2f14388f381bb66320cd8528913ebd140e2faa193e296ca2a4f.jpg)  \nFigure 6. Antibacterial property tests of the dual-cross-linked pMDHAB-AA coating. (a) Growth inhibition rates of pMDHAB−AA copolymers in aqueous solutions with a sequence of concentrations against S. aureus and E. coli. (b) Photographs of the zone-of-inhibition test results of the PET and dual-cross-linked pMDHAB−AA coating in a cultured lawn of S. aureus and E. coli. (c) Photographs of bacterial colonies of S. aureus and E. coli after incubation with the PET and dual-cross-linked pMDHAB−AA coating at $37^{\\circ}\\mathrm{C}$ for $24\\mathrm{h}.$ . (d) SEM images of S. aureus and $E$ . coli on the PET and dual-cross-linked pMDHAB−AA coating surfaces.  \n\nAntibacterial Performance. In addition to the higher transparency and outstanding antifogging performance of the transparent substrates, the antibacterial property is also highly needed for practical application situations.43,44 Generally speaking, quaternary ammonium salts have been widely used as antibacterial agents because of the antibacterial activity.45,46 In this sense, the antibacterial ability of the dual-cross-linked pMDHAB−AA coating was assessed with E. coli and S. aureus according to the following method.36,37,47 First, the MIC of the pMDHAB−AA copolymer was determined to evaluate the antibacterial ability. $\\mathrm{MIC}_{90}$ is defined as the lowest concentration that exhibited more than $90\\%$ inhibition of the bacterial growth.36 Figure 6a shows that the pMDHAB−AA copolymer had MIC values of $1024~\\mu\\mathrm{g/mL}$ toward both E. coli and S. aureus, which was seriously lower than the concentration required for the coating, manifesting the reasonable antibacterial activity. Then, the antibacterial property of the pMDHAB−AA coating was investigated by a zone-ofinhibition test. As shown in Figure 6b, the surroundings of the pure PET was covered with lots of bacterial colonies, whereas for the PET covered with the pMDHAB−AA coating, obvious inhibition zones were shown, which can be attributed to the migration of the quaternary ammonium components from the film to the surrounding agar. In addition, the spread plate method was used to further confirm the antibacterial performance of the coating. As shown in Figure 6c, a large number of bacteria were covered on an agar plate of the blank PET, whereas no bacteria could be observed on the coating plate, indicating the antibacterial activity of the prepared coating, which was in accordance with the zone-of-inhibition test results. At last, the antibacterial activity by observing the attachment of the bacteria on the coating surfaces was assessed via SEM. As shown in Figure 6d, significant quantities of bacteria adhered to the PET film surfaces, whereas in contrast, no bacterium can be observed on the dual-cross-linked pMDHAB−AA coating surfaces, which means that the cationic hydrated layer of the dual-cross-linked pMDHAB−AA coating also can prevent bacteria cell adhesion.  \n\n![](images/caa26a18e2f1a694fa915c34a5bf7451ad347cdd8212d2625e5d2df1c519dbb6.jpg)  \nFigure 7. (a) WCAs of the dual-cross-linked pMDHAB−AA coating after different friction cycles. (b) Antifogging performance of the coating after 12000 friction cycles. (c) Friction coefficients on the PET and dual-cross-linked pMDHAB−AA coating surfaces with different friction cycles (2N, $2\\ \\mathrm{Hz},$ against a PDMS ball in aqueous solution). (d) Changes of the friction coefficient on the dual-cross-linked pMDHAB−AA coating surface under different loads ( $2\\ \\mathrm{Hz},$ against a PDMS ball in aqueous solution).  \n\nWear-Resistance and Self-Lubrication Performances in Water. In addition to the antifogging performance, the wear-resistance performance of a coating is critical for achieving broad applications. To investigate the wearresistance performance of the dual-cross-linked pMDHAB− AA coating, the friction tests were conducted using an alcohol rubber abrasion test machine (model 339) in air. A polyester cloth was selected as the upper friction pair, and a $^\\textrm{\\scriptsize1N}$ force was applied to the coating in reciprocal friction mode. Figure 7a displays the variations in the initial WCA after different friction cycles. The results indicate a gradual decrease in the  \n\nWCA of the coating with an increasing number of friction cycles. However, even after 12000 friction cycles (Figure 7b), the coating maintained an excellent antifogging performance, which affirmed its superior wear resistance. The friction coefficients of the pure PET film and the film covered with the dual-cross-linked pMDHAB−AA coating were determined to reveal the self-lubrication performance in the surrounding water. As shown in Figure 7c, the friction coefficient of the PET film can reach up to 0.8, whereas the coating exhibits an impressively low and stable friction coefficient of 0.005 throughout the entire 25000 cycles. The distinct difference is attributed to the presence of the hydrophilic pMDHAB chains in the coating network, allowing water molecules to be absorbed and form a uniform hydration layer, and due to its dual-cross-linked network, the coating maintains stability throughout the entire friction cycle. Notably, Figure 7d shows the changes of the friction coefficient curves under different loadings. The friction coefficient has not increased and even reduced at high pressure, which declared a good load capacity under the water surroundings.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# CONCLUSIONS  \n\nIn summary, a highly transparent, antifogging, and antibacterial coating containing pMDHAB−AA and PEGDA dual-crosslinked networks was prepared via a UV-curing process. Based on the delicate hydrophilic/hydrophobic balance and the highly cross-linked structure, the resulting coating demonstrated an excellent long-lasting antifogging property in both hot-vapor and cold-warm conditions for 20 days. In addition, the quaternary ammonium groups of the pMDHAB units rendered the coating with a strong antibacterial property against Gram-positive S. aureus and Gram-negative E. coli. Based on the hygroscopicity of pMDHAB blocks and highly cross-linked structure of the coating network, the coating has oleophobicity underwater, an ultralow friction coefficient in water, and wear resistance. The overall results reported herein imply that the long-term antifogging coating with increased transparency and good antibacterial and abrasion resistance could be potentially applied in the field of medical devices, windows, greenhouse films, and so on.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 7,
+        "chunk": "# ASSOCIATED CONTENT",
+        "category": " References"
+    },
+    {
+        "id": 8,
+        "chunk": "# $\\bullet$ Supporting Information  \n\nThe Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsapm.4c00912.  \n\nXPS spectra of the PET and pMDHAB−AA copolymer, DTG curves of copolymers, cross-sectional SEM images of the coating, AFM image of PET, TGA and DTG curves of different cross-linked coatings, transmittance spectra of the coating, and optical microscopy images of the coating (PDF)  \n\nMovie S1 showing a hot-vapor fogging test on the bare PET surface (MP4)  \n\nMovie S2 showing a hot-vapor fogging test on the dualcross-linked pMDHAB−AA coating surface (MP4)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# AUTHOR INFORMATION",
+        "category": " References"
+    },
+    {
+        "id": 10,
+        "chunk": "# Corresponding Authors  \n\nYang Wu − Shandong Laboratory of Advanced Materials and Green Manufacturing, Yantai Zhongke Research Institute of Advanced Materials and Green Chemical Engineering, Yantai, Shandong 264006, P. R. China; State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, Gansu 730000, P. R. China; Qingdao Centre of Resource Chemistry and New Materials, Qingdao, Shandong 266100, P. R. China; $\\circledcirc$ orcid.org/0000-0002-4953-1801; Email: yangwu@licp.cas.cn   \nKai Feng − Shandong Laboratory of Advanced Materials and Green Manufacturing, Yantai Zhongke Research Institute of Advanced Materials and Green Chemical Engineering, Yantai, Shandong 264006, P. R. China; Email: kaifeng@ amgm.ac.cn",
+        "category": " References"
+    },
+    {
+        "id": 11,
+        "chunk": "# Authors  \n\nLina Zhang − Shandong Laboratory of Advanced Materials and Green Manufacturing, Yantai Zhongke Research Institute of Advanced Materials and Green Chemical Engineering, Yantai, Shandong 264006, P. R. China; Yantai Research Institute of Harbin Engineering University, Yantai, Shandong 264006, P. R. China Yizhe Liu − Shandong Laboratory of Advanced Materials and Green Manufacturing, Yantai Zhongke Research Institute of Advanced Materials and Green Chemical Engineering, Yantai, Shandong 264006, P. R. China; State Key Laboratory of Solid Lubrication, Lanzhou Institute of  \n\nChemical Physics, Chinese Academy of Sciences, Lanzhou, Gansu 730000, P. R. China   \nFangrong Wu − Shandong Laboratory of Advanced Materials and Green Manufacturing, Yantai Zhongke Research Institute of Advanced Materials and Green Chemical Engineering, Yantai, Shandong 264006, P. R. China   \nYubo Liu − Shandong Laboratory of Advanced Materials and Green Manufacturing, Yantai Zhongke Research Institute of Advanced Materials and Green Chemical Engineering, Yantai, Shandong 264006, P. R. China; State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, Gansu 730000, P. R. China   \nBo Yu − State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, Gansu 730000, P. R. China; $\\circledcirc$ orcid.org/0000- 0002-1635-0027   \nXiaowei Pei − Shandong Laboratory of Advanced Materials and Green Manufacturing, Yantai Zhongke Research Institute of Advanced Materials and Green Chemical Engineering, Yantai, Shandong 264006, P. R. China; State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, Gansu 730000, P. R. China   \nLijia Liu − Yantai Research Institute of Harbin Engineering University, Yantai, Shandong 264006, P. R. China; $\\circledcirc$ orcid.org/0000-0002-2181-747X   \nChunhong Zhang − Yantai Research Institute of Harbin Engineering University, Yantai, Shandong 264006, P. R. China; $\\circledcirc$ orcid.org/0000-0001-6068-8140   \nFeng Zhou − State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, Gansu 730000, P. R. China; $\\circledcirc$ orcid.org/0000-0001-7136-9233  \n\nComplete contact information is available at: https://pubs.acs.org/10.1021/acsapm.4c00912",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# Notes  \n\nThe authors declare no competing financial interest.",
+        "category": " References"
+    },
+    {
+        "id": 13,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nWe gratefully acknowledge support from the Key Research and Development Program in Shandong Province (SYS202203 and 2021CXGCDA02), the Shandong Provincial Natural Science Foundation (ZR2023QE089 and ZR2021ZD27), the National Natural Science Foundation of China−China Academy of Engineering Physics NSAF Joint Fund Project (U2030201), the Key Research and Development Program of Gansu (22YF7GA049), the Gansu Province Basic Research Innovation Group Project (22JR5RA093), and the Science Foundation for Distinguished Young Scholars of Gansu Province (23JRRA651).",
+        "category": " References"
+    },
+    {
+        "id": 14,
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+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Black Phosphorus/Polymers: Status and Challenges  \n\nYe Zhang, Chunyang Ma, Jianlei Xie, Hans Ågren,\\* and Han Zhang\\*  \n\nAs a newly emerged mono-elemental nanomaterial, black phosphorus (BP) has been widely investigated for its fascinating physical properties, including layer-dependent tunable band gap (0.3–1.5 eV), high ON/OFF ratio $(70^{4})$ , high carrier mobility $(70^{3}\\mathsf{c m}^{2}\\mathsf{V}^{-1}\\mathsf{s}^{-1})$ , excellent mechanical resistance, as well as special in-plane anisotropic optical, thermal, and vibrational characteristics. However, the instability caused by chemical degradation of its surface has posed a severe challenge for its further applications. A focused BP/polymer strategy has more recently been developed and implemented to hurdle this issue, so at present BP/polymers have been developed that exhibit enhanced stability, as well as outstanding optical, thermal, mechanical, and electrical properties. This has promoted researchers to further explore the potential applications of black phosphorous. In this review, the preparation processes and the key properties of BP/polymers are reviewed, followed by a detailed account of their diversified applications, including areas like optoelectronics, bio-medicine, and energy storage. Finally, in accordance with the current progress, the prospective challenges and future directions are highlighted and discussed.  \n\nhave still not been realized owing to the intrinsic lack of a band gap, something that has greatly limited its applications in the field of semiconductor devices.[2] Transition metal disulfides (TMDs) are a series of other extensively studied 2D vdW materials, especially the most famous one— $\\mathrm{MoS}_{2}$ , which possesses a similar structure to graphene and exhibits direct band gaps when its thickness is reduced to a monolayer.[3] However, due to its relatively low carrier mobility there is difficulty in meeting the preparation requirements of next-generation optoelectronic devices.[4]  \n\nPhosphorus, an abundant group V element on Earth, mainly exhibits three forms of allotropes: White phosphorus (WP), red phosphorus (RP), and black phosphorus (BP).[5] Among them, BP has the most stable structure and is insoluble in most solvents, it is non-flammable and has the lowest chemical reaction energy at normal temperature and pressure.[6]",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1. Introduction  \n\nFollowing the first successful exfoliation of graphene from graphite in the 20th century, 2D layered van der Waals (vdW) nanomaterials have aroused wide attention and led to a rapid development of 2D layered vdW-based devices owing to their fantastic structural and physical properties.[1] Nevertheless, despite extensive research, logic circuit switches using graphene  \n\nBP has been considered as a newly emerging star of 2D vdW semiconductor materials since its first appearance in 2014.[6c,7] The fascinating properties of BP are in principal determined by its unusual structure, geometric and electronic.[8] Figure  1a–c shows an atomic ball-stick schematic of a few-layer BP with typical fold structure due to the $\\displaystyle\\mathrm{sp}^{3}$ orbital hybridization, where special armchair- and zigzag-shapes can be observed along the $x\\cdot$ and $\\gamma$ -axial directions, respectively, resulting in an asymmetry of BP and in specific in-plane anisotropic characteristics of its optical, thermal, and electronical properties.[9] In particular, every $\\mathrm{\\DeltaP}$ atom is linked with two neighboring intraplane P atoms by covalent bonds, and every BP layer is stacked via weak vdW interactions. Comparing with the $220{-}350\\ \\mathrm{cm^{2}\\vee^{-1}\\ \\mathrm{s^{-1}}}$ hole mobilities of bulk BP, few-layer BP displays a hole mobility as high as $10^{3}\\ \\mathrm{cm}^{2}\\ \\mathrm{V}^{-1}\\ \\mathrm{s}^{-1}$ , which can match that of silicon (Si) at room temperature.[10] As shown in Figure  1d–f, BP has been proven to have a layer-dependent tunable direct-bandgap ranging from 0.3 (bulk) to $1.5\\ \\mathrm{eV}$ (monolayer), thereby exhibiting a wide optical absorption window of the solar spectrum that covers the ultraviolet (UV) to mid-infrared regime.[11] These extraordinary properties of BP give prospects for many new generation applications.  \n\nNevertheless, the degradation of the surface of BP is still a serious challenge that needs to be solved so as to effectively enhance the long-term stability of BP devices.[13] It follows that great efforts have been undertaken to bring light on the degradation mechanism of BP by experimental as well as theoretical research. Results of photooxidation of multilayer BP through AFM analysis and theoretical calculations are depicted in Figure  2.[14] The generally adopted degradation mechanism is the synergetic effect of light illumination, water, and oxygen. A three-step degradation process of BP has been presented, including the formation of superoxide, the formation of phosphate, and the breaking of the top layer. Finding appropriate strategies to slow down the degradation rate and improve the environmental stability of BP has thus become a long term pursuit for researchers. As shown in Figure 3 various technologies have been proposed to passivate BP, such as, surface functional modification,[15] adsorption of heavy metal cations,[16] introduction of stable protective layers,[8c,17] fluorination,[18] and incorporation with different polymers.[19]  \n\n![](images/452cb67bf8f487d368b729d8acb3e7425c2b903ad22f7786eea4674075efb6c0.jpg)  \nFigure 1.  a) Atomic ball-stick schematic of few-layer BP. b) Top view. c) Side view. d,e) Band structures of monolayer and bilayer BP calculated throug the HSE06 methods. f) The relationship of band gaps versus thickness of BP. a–c) Reproduced with permission.[8a] Copyright 2017, Royal Society of Chemistry. d–f) Reproduced with permission.[11d] Copyright 2014, Springer Nature.  \n\nThe development of BP passivation technologies has greatly improved the stability of BP. Among the reported passivation technologies, the incorporation of BP with polymers has been considered as the most promising strategy, ascribing to advantages like low cost, easy fabrication process, nontoxicity, and environmentally friendliness.[12d,22] Recently achieved progress in studies of BP/polymers indicates a great potential for applications of optoelectronic devices,[23] bio-medical therapy,[24] and energy storage.[25] Up to now, with the burgeoning of BP/ polymers, most of the current reported BP/polymer reviews have been focused on bio-medical applications, while a more comprehensive and a systematic summarization of their preparation methods, properties, and applications is urgently in demand, which could be beneficial for the further design of novel BP/polymers with high-performance. With this statement as starting point, we here first introduce various fabrication approaches and properties of BP/polymers. This is followed by a discussion of their multiple applications in optoelectronics, energy/information storage, flame retardancy, bio-medical, and other potential applications. Finally, an outlook of prospects, opportunities, and challenges of BP/polymers in the future is presented. We believe that this review can bring new significance to the development of BP/polymers.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2. Preparation of Black Phosphorus/Polymers  \n\nIn decades, polymers or named macromolecules have attracted an increasing research interest due to their rich advantages like easy fabrication and modification methods, low consumption, environmental friendliness, and flexibility in structure, which have been widely explored to combine with inorganic materials to form inorganic/polymers nanocomposites with some novel features, including enhanced mechanical, electronical, thermal, and stability properties.[26] Researchers have much utilized inorganic/polymers nanocomposites for applications in various fields such as catalysis, gas absorption, energy storage, environmental protection, and governance.[27]  \n\nBecause of the numerous active sites on the surface of BP and the easy fabrication and modification features of polymers, BP/polymer nanocomposites have been extensively investigated and can be prepared into various morphologies.[6a,25a,28] Additionally, BP has also been proved to be hydrophilic owing to its strong out of plane dipolar moment.[8a,8c,29] So far, lots of polymers, like PLGA, PU, PEG, PDA, PPy, PVA, and PANI, have been investigated to fabricate BP/polymer nanocomposites, where the components are connected with a relatively weak interaction including vdW forces, electrostatic binding, and hydrogen chemical bonds. To the best of our knowledge, the most adopted methods to prepare BP/polymers comprise solution casting (SC), polymerization methods (PMs), and spinning technology (ST) methods. Table 1 lists the preparation methods and applications of BP/polymer nanocomposites highlighted during the recent 6 years. It is noteworthy that the development of BP/polymer nanocomposites shows an increasing trend year by year and that the most adopted one is the solution casting (SC) method which covers over more than half of all the reported cases in the literature.  \n\n![](images/088610522d61879b1eab7055341f61ea41e50eab8feda1dd21dbe289f487e6da.jpg)  \nFigure 2.  a) AFM images of fresh BP and of BP placed for some days under ambient environment. b) The comparison of concentrations of $\\mathsf{P O}_{2}{}^{3-}$ , ${\\mathsf{P O}}_{3}^{3-}$ , and ${\\mathsf{P O}}_{4}^{3-}$ under ambient light. c) Mole fractions of ${\\mathsf{P O}}_{2}{}^{3-}$ , ${\\mathsf{P O}}_{3}{}^{3-}$ , and ${\\mathsf{P O}}_{4}^{3-}$ after different storage days. d) Oxidation kinetics of ${\\sf H}_{3}{\\sf P}{\\sf O}_{x}$ $\\left(_{x}=2,3\\right.$ , or 4) from the zigzag edge of BP. e) Theoretical degradation mechanism of BP under light illumination. a) Reproduced with permission.[13d] Copyright 2017, Springer Nature. b–d) Reproduced with permission.[20] Copyright 2018, American Chemistry Society. e) Reproduced with permission.[14b] Copyright 2016, Wiley-VCH.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2.1. Solution Casting  \n\nAs discussed above, SC has become one of the most important ways to prepare BP/polymer nanocomposites since its first appearance in 1995.[116] The interaction between BP and polymers is strong owing to the special polar nature of both constituents, leading to an enhanced flexibility of the obtained membranes.[41,56,74,117] In a typical procedure, specific amounts of polymers and BP are dissolved in solvents to form homogeneous solutions with the assistance of sonication or vigorous stirring as shown in Figure  4. The BP/polymer membranes with well-defined composition can subsequently be obtained through filtration and evaporation at high temperatures to remove the extra solvents. Li et  al. obtained a membrane via introducing BP into a PVA matrix[46] and could demonstrate that the so prepared BP/PVA membrane shows an excellent flexibility with a significantly enhanced discharge capacity. Zhang’s group reported coated BP quantum dots (BP QDs) with polyionic liquid poly(1-hexyl-3-vinylimidazolium) hexa­ fluorophosphate salt (PIL-TFSI), followed by mixing the coated BP with PVDF and dropped onto a clean ITO glass under $80^{\\circ}$ to remove the solvent for fabricating a PEC-type photodetector with long-term stability.[23a] $\\mathrm{~In~}2019$ , Wan and coworkers first prepared a BP/graphite hybrid, followed by mixing the hybrid with PANI to prepare a ternary membrane through filtration.[70]  \n\n![](images/86529de51502264c5d3dd77bce0e331296ba58214d9a7f5daada2bd357e6df67.jpg)  \nFigure 3.  a) h-BN and graphene encapsulated BP. b) PDI molecules adsorbed BP. c) The adsorption of ${\\mathsf{A}}{\\mathsf{g}}^{+}$ on the surface of BP. d) Fluorination of BP with $\\mathsf{F}_{2}$ . e) PU polymer incorporated BP. a) Reproduced with permission.[17a] Copyright 2015, American Chemistry Society. b–d) Reproduced with perm ission. $[75d,76a,78a]$ Copyright 2016–2018, Wiley-VCH. e) Reproduced with permission.[21] Copyright 2018, Elsevier Ltd.  \n\nDifferent from the above introduction of preparing membranes with a large amount of polymers, surface functional modification is another popular SC method to prepare BP/ polymer nanocomposites with appropriate polymer additives.[73] Taking advantage of the hydrophilic nature of BP, lots of hydrophilic polymers have been explored to modify BP via the SC method. For example, hydrophilic functionalized PEG is one of the most commonly used polymers to fabricate nanocomposites with BP attributes to its advantage like good biocompatibility and physiological stability in media.[43,62,89] $\\mathrm{In}2015$ , BP QDs were first surface modified with PEG- $\\mathrm{\\cdotNH}_{2}$ by Zhang et al.[31] and were then dissolved in deionized water (DW) and sonicated for $30~\\mathrm{min}$ , so obtaining a BP/PEG- $\\mathrm{\\cdotNH}_{2}$ nanocomposite that was treated by repeated centrifugation and water rinsing. The BP/PEG- $\\mathrm{\\cdotNH}_{2}$ nanocomposite exhibits non-toxicity and enhanced physiological stability, and was demonstrated to be a promising photothermal agent for cancer therapy. In 2017, these authors further proposed that $\\mathrm{BP/PEG{\\cdot}N H_{2}}$ also could be a robust delivery platform for cancer theranostics. Yang’s group prepared near-infrared region/reactive oxygen species $\\left(\\mathrm{NIR}\\right/$ ROS) response BP/polymers by grafting with pyrene modified poly (propylene sulfide) and PEG, which was proposed to serve as an effective immunoadjuvant carrier for cancer therapy.[84] There are also lots of other hydrophilic PEGs adopted to prepare BP/polymers like BP/PEG-FA,[83] BP/PEG- $\\mathrm{\\cdotNH}_{2}/\\mathrm{Sgc}8$ ,[80] BP/PEG- $\\ensuremath{\\mathrm{\\cdotNH}}_{2I}$ /RdB,[45] BP/PEG/PPy.[82] In addition to the most explored PEGs, some other hydrophilic polymers have also been developed to fabricate BP/polymer nanocomposites. For example, PLL was mixed with BP NSs for biosensors with good catalytic activity.[47] Besides that, BP has also been reported as a promising material for optical applications through SC met hods.[28,33,39,49,118] Yun and coworkers found that the usage of BP NSs with PVA as saturable absorbers (SAs) can provide dualwavelength vector soliton mode locking in an erbium-doped fiber laser.[37] PDDA was applied to incorporate BP NSs via electrostatic interaction in solution by Zhao et  al.[51] They claimed that the PDDA can not only passivate the lone-pair electrons of P but also enhance its dispersity in water, showing that the prepared BP/PDDA film is a promising candidate for applications in ultrafast optics. Zhang’s group prepared a BP/PIL nanocomposite by mixing BP with -(PIL-TFSI).[23a] The prepared BP/PIL exhibited good photo-response behaviors, as well as excellent self-healable capability.  \n\nTable 1.  Articles on BP/polymers published from 2015 to 2021.   \n\n\n<html><body><table><tr><td>Year</td><td>BP/polymer</td><td>Method</td><td>Application</td><td>Ref</td></tr><tr><td>2015</td><td>BP/PMMA</td><td>ST</td><td> Laser technology</td><td>[30] </td></tr><tr><td rowspan=\"5\">2016</td><td>BP/PEG-NH2</td><td>SC</td><td>PTT</td><td>[31] </td></tr><tr><td>BP/PVP</td><td>SC</td><td>Information storage</td><td>[32]</td></tr><tr><td>BP/PC</td><td>Thermal evaporation</td><td>Laser technology</td><td>[33] </td></tr><tr><td>BP/PEODT:PSS</td><td>SC</td><td>-</td><td>[34]</td></tr><tr><td>BP/PLGA</td><td>SC </td><td>PTT</td><td>[35] </td></tr><tr><td rowspan=\"5\">2017</td><td>BP/PEG</td><td>Mechanical milling</td><td>PA imaging, PTT</td><td>[24b]</td></tr><tr><td>UCNP-PAA/BP-PEG</td><td>SC</td><td>PDT</td><td>[36] </td></tr><tr><td>BP/PVA</td><td>SC</td><td>Laser technology</td><td>[37]</td></tr><tr><td>BP/PVA</td><td>SC </td><td>Laser technology</td><td>[38] </td></tr><tr><td>BP/PDMS</td><td>PM</td><td>Laser technology</td><td>[39]</td></tr><tr><td rowspan=\"16\">2018</td><td>BP/PMMA</td><td>ST</td><td>Ultrafast photonics</td><td>[40] </td></tr><tr><td>BP/PMMA</td><td>PM</td><td>Information storage</td><td>[4] </td></tr><tr><td>BP/PAH</td><td>SC</td><td>siRNA delivery, PTT</td><td>[42]</td></tr><tr><td>BP/PEG-CA</td><td>SC </td><td> Fluorescence imaging</td><td></td></tr><tr><td>BP/PEG</td><td>SC</td><td>Drug delivery, PTT</td><td>[43]</td></tr><tr><td>BP/PEG</td><td>SC</td><td></td><td>[44] </td></tr><tr><td>BP/PVA</td><td>SC</td><td>Fluorescence imaging, PDT/PTT Zinc-nickel battery</td><td>[45] </td></tr><tr><td>BP/PANI</td><td>Electrochemical deposition</td><td>Supercapacitor</td><td>[46]</td></tr><tr><td>BP/CNT/TPU</td><td>ST</td><td>Supercapacitor</td><td>[25b] </td></tr><tr><td>BP/PLL</td><td>SC</td><td>Biosensor</td><td>[25c]</td></tr><tr><td>BP/PPy</td><td></td><td></td><td>[47]</td></tr><tr><td>BP/PVA</td><td>SC SC</td><td>Electron-sensor</td><td>[48]</td></tr><tr><td>BP/PVA</td><td>SC</td><td>Laser technology Laser technology</td><td>[49]</td></tr><tr><td>BP/PDDA</td><td>SC </td><td>Laser technology</td><td>[50] </td></tr><tr><td>BP/PDMS</td><td></td><td></td><td>[5]</td></tr><tr><td>BP/PMMA</td><td>PM</td><td> Laser technology</td><td>[52] </td></tr><tr><td>BP/PMMA</td><td>SC</td><td>Laser technology</td><td>[53] </td></tr><tr><td>BP/PTFE</td><td>PM</td><td></td><td>[54]</td></tr><tr><td>BP/PEDOT:PSS</td><td>SC</td><td></td><td>[55] </td></tr><tr><td>BP/PLGA</td><td>SC</td><td></td><td>[56] </td></tr><tr><td>BP/PDDF</td><td>ST</td><td></td><td>[5]</td></tr><tr><td>BP/PU</td><td>PM</td><td>Information storage</td><td>[58] </td></tr><tr><td>BP/PU</td><td>SC </td><td> Flame retardancy</td><td>[59]</td></tr><tr><td>BP/PDLLA/PEG/PDLLA</td><td>SC </td><td>Shape memory</td><td>[21]</td></tr><tr><td>BP/Agarose</td><td>PM</td><td>PTT, antibacterial</td><td>[60]</td></tr><tr><td>BP/C-PEG</td><td>PM</td><td> Drug delivery</td><td>[24c] </td></tr><tr><td>BP/PDA/PEG</td><td>SC</td><td> Drug and siRNA delivery, photoimmunotherapy</td><td>[6] </td></tr><tr><td>BP/PVA</td><td>SC freeze drying</td><td>Drug and siRNA delivery, PTT</td><td>[62]</td></tr><tr><td>BP/PLGA</td><td></td><td>Drug delivery</td><td>[63]</td></tr><tr><td>BP/PLGA/PEI</td><td>SC</td><td>Drug delivery, bone regeneration</td><td>[64]</td></tr><tr><td>BP/PPMS-EPO</td><td>SC</td><td>Tumor radiosensitization</td><td>[65] </td></tr><tr><td>BP/PEI</td><td>SC</td><td>Antibacterial</td><td>[66] </td></tr><tr><td></td><td>Mechanical milling</td><td> Bio-imaging</td><td>[67] [68] </td></tr><tr><td></td><td>BP/PEI</td><td>SC PM</td><td>PDT</td></tr><tr><td>2019</td><td>BP/Cellulose hydrogel</td><td>PTT</td><td>[69]</td></tr><tr><td>BP/PPy</td><td>PM</td><td>Supercapacitor</td><td>[25d] </td></tr><tr><td>BP/G/PANI</td><td>SC</td><td>Na-ion battery</td><td>[70] </td></tr><tr><td>BP/PS/PAA</td><td>SC</td><td>Biosensor</td><td>[7]</td></tr></table></body></html>  \n\nTable 1. Continued.   \n\n\n<html><body><table><tr><td>Year</td><td>BP/polymer</td><td>Method</td><td>Application</td><td>Ref</td></tr><tr><td></td><td>BP/PP</td><td>SC</td><td>Biosensor</td><td>[72] </td></tr><tr><td></td><td>BP/PDDA</td><td>SC</td><td>Biosensor</td><td>[73]</td></tr><tr><td></td><td>BP/PVDF</td><td>SC</td><td>Photodetector</td><td>[23a] </td></tr><tr><td></td><td>BP/PVDF</td><td>SC</td><td></td><td>[74]</td></tr><tr><td></td><td>BP/PFCz-NH2</td><td>PM</td><td>Information storage</td><td>[75] </td></tr><tr><td></td><td>BP/PZN</td><td>PM</td><td>Flame retardancy</td><td>[76]</td></tr><tr><td></td><td>BP/PU</td><td>PM</td><td>Flame retardancy</td><td>[77]</td></tr><tr><td></td><td>BP/Pluronic F-127</td><td>Cold method</td><td>Drug delivery, PTT</td><td>[78]</td></tr><tr><td></td><td>BP/PLGA</td><td>SC</td><td>Drug delivery, PTT</td><td>[79]</td></tr><tr><td></td><td>BP/PEG</td><td>SC</td><td>Drug delivery, PTT</td><td>[80] </td></tr><tr><td></td><td>BP/PDA/PEG</td><td>SC</td><td>Drug delivery, PTT/PDT</td><td>[81] </td></tr><tr><td></td><td>BP/PPy</td><td>SC</td><td>PTT</td><td>[82]</td></tr><tr><td></td><td>BP/PEG-FA</td><td>SC</td><td>Drug delivery, PTT</td><td>[83] </td></tr><tr><td></td><td>BP/Pyrene-PEG</td><td>SC</td><td>PDT</td><td>[84]</td></tr><tr><td></td><td>BP/PCL</td><td>ST </td><td>Bone regeneration</td><td>[85] </td></tr><tr><td></td><td>BP/PEA/GelMA</td><td>PM</td><td>Bone regeneration</td><td>[86] </td></tr><tr><td></td><td>BP/PEG</td><td>SC</td><td>Drug delivery, PTT</td><td>[87]</td></tr><tr><td></td><td>BP/PCL</td><td>SC</td><td>Tissue regeneration</td><td>[88]</td></tr><tr><td></td><td>BP/PEG-FA/PAH</td><td>SC</td><td>Bio-imaging, PDT</td><td>[89]</td></tr><tr><td></td><td>BP/PHEA/PDMA</td><td>PM</td><td>Bone regeneration</td><td></td></tr><tr><td></td><td>BP/PEG</td><td>SC</td><td>PDT</td><td>[90] </td></tr><tr><td></td><td>BP/PDA</td><td>PM</td><td>PTT/PDT</td><td>[91] </td></tr><tr><td>2020</td><td>BP/PANI</td><td>PM</td><td>Na-ion battery</td><td>[92] </td></tr><tr><td>BP/PI</td><td></td><td>PM</td><td></td><td>[93]</td></tr><tr><td>BP/PU</td><td></td><td>SC</td><td>Flame retardancy</td><td>[94]</td></tr><tr><td>BP/PU</td><td></td><td></td><td>Flame retardancy</td><td>[95]</td></tr><tr><td>BP/EP</td><td></td><td>SC PM</td><td>Flame retardancy</td><td>[96] </td></tr><tr><td>BP/MCNT/EP</td><td></td><td>PM</td><td>Flame retardancy</td><td>[97]</td></tr><tr><td>BP/(CFSO3)3Er/EP</td><td></td><td>PM</td><td>Flame retardancy</td><td>[98] </td></tr><tr><td></td><td>BP/graphite oxide/EP</td><td>PM</td><td>Flame retardancy</td><td>[99]</td></tr><tr><td>BP/PVA/PDA</td><td></td><td>PM</td><td>Flame retardancy</td><td>[100] [101] </td></tr><tr><td>BP/PEI/PUA</td><td></td><td>PM</td><td>Flame retardancy</td><td>[102] </td></tr><tr><td></td><td>BP/COF</td><td>solvothermal</td><td> Flame retardancy</td><td></td></tr><tr><td></td><td>BP/PLLA/PEG/PLLA</td><td>SC</td><td>Drug delivery, PTT</td><td>[103] [104]</td></tr><tr><td></td><td>BP/PLGA</td><td>SC</td><td>PTT</td><td>[105] </td></tr><tr><td></td><td>BP/PLGA</td><td>PM</td><td>Rheumatoid arthritis therapy</td><td>[106]</td></tr><tr><td></td><td>BP/PLGA</td><td>Cryogenic environment</td><td>Drug delivery, PTT, bone generation</td><td>[107]</td></tr><tr><td></td><td>BP/PLL</td><td>SC</td><td>Cas13a/crRNA delivery</td><td>[108]</td></tr><tr><td></td><td>BP/PLCL/Laminin</td><td>ST</td><td>Neuritogenesis</td><td>[109]</td></tr><tr><td></td><td>BP/G/PANI</td><td>SC</td><td>Li-ion battery</td><td>[110] </td></tr><tr><td>2021 BP/TPU</td><td></td><td>PM</td><td>Flame retardancy</td><td>[11]</td></tr><tr><td>BP/graphene/TPU</td><td></td><td></td><td></td><td></td></tr><tr><td>BP/PEG</td><td></td><td>PM</td><td>Flame retardancy PDT/PTT/photoimmunotherapy</td><td>[112] </td></tr><tr><td>BP/Cys-PDSA</td><td></td><td>SC Nanoprecipitation</td><td>Bioimaging,drug delivery</td><td>[113] [114]</td></tr></table></body></html>\n\nPDT: Photodynamic therapy, PTT: Photothermal therapy, PAA: Polyacrylic acid, PANI: Polyaniline, PAH: Poly(allylamine hydrochloride), PC: Polycarbonate, PCL: Poly(ε- caprolactone), PDDA: Poly(diallyldimethylammonium chloride), PDDF: Poly[(1,4-diethynylbenzene)-alt-9,9-bis(4-diphenylaminophenyl)fluorene], PDLLA: Poly(d,l-lactide), PDMA: Poly(N,N-dimethyl acrylamide), PDMS: Polydimethylsiloxane, PDSA: Poly-(disulfide amide), PEA: Poly(ester amide)s, PEDOT:PSS: Poly(3,4-ethylenedioxythiophene): polystyrene sulfonate, PEG: Polyethylene glycol, PEI: Polyethylenimine, ${\\mathsf{P F C z}}{\\mathsf{-N H}}_{2}$ : Poly[(9,9-dioctyl-9H-fluorene)-alt-(4-(9H-carbazol-9-yl)aniline)], PHEA: poly(2-hydroxyethylacrylate), PI: Polyimide, PLCL: poly(L-lactide-co-ε-caprolactone), PLGA: Poly(lactic-co-glycolic acid), PLL: Poly-L-lysine, PLLA: Poly(L-lactide), PMMA: Poly (4-pyridonemethylstyrene), PP: Polypeptide, $\\mathsf{P P y}\\mathrm{:}$ Polypyrrole, PPMS-EPO: poly (4-pyridonemethylstyrene) endoperoxide, PTFE: Polytetrafluoroethylene, PU: Polyurethane, PVA: Poly(vinyl alcohol), PVDF: Polyvinylidene fluoride, PVP: Polyvinyl pyrrolidone, PZN: Polyphosphazene, TPU: Thermoplastic polyurethane.  \n\n![](images/10a0443a632c30c4bf32fbac60565f9bdca33334f0ef61edb50f2b4070d67650.jpg)  \nFigure 4.  a–c) Preparation of BP/polymers via SC methods. d,e) SEM and TEM images of prepared BP/PEG. f) Elements mapping of prepared BP/ polymers. a,b) Reproduced with permission.[19a,84] Copyright 2015 and 2018, Wiley-VCH. c) Reproduced with permission.[115] Copyright 2018, The Royal Society of Chemistry. d–f) Reproduced with permission.[72,79] Copyright 2017 and 2019, American Chemistry Society.  \n\nAnother most used SC method is the emulsion solvent evaporation method, often named as the oil-in-water emulsion solvent evaporation method.[64,71,72,105,107,119] In a typical procedure using this method, materials are first dispersed in organic solvents to form a homogeneous solution, which subsequently is added into an aqueous solution and sonicated to obtain the emulsion. Finally, the BP/polymer nanocomposites are obtained by centrifugation. For example, Chu et  al. first dissolved BP QDs and PLGA in dichloromethane (DCM), and added the mixture in PVA aqueous solution and stirred it overnight to remove residual DCM at room temperature. The BP/ PLGA suspension was first centrifuged for several minutes, and then the product was washed with deionized water.[35] They proved that such prepared BP/PLGA can prevent the rapid degradation of BP and give a highly efficient photothermal performance. Chen et al. first uniformly dispersed BP and PLGA in acetone through ultrasonication followed by dropping the organic phase in an aqueous solution. (PEI) polyetherimide was then transferred into the solution and stirred overnight to prepare a BP/PLGA/PEI nanocomposite for precise tumor radiosensitization.[65]",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2.2. Polymerization Method  \n\nPM is a mainly adopted strategy to prepare BP/polymer nanocomposites. Different from the traditional accurate controllable polymerization process through living radical polymerization, the BP/polymers are generally obtained by mixing BP with polymers and followed by a thermal or an UV curable process as shown in Figure  5. In addition, BP/polymer hydrogels are also inductive to PM.[69,90,120] For example, Yu’s group selected biocompatible and biodegradable PDLLA to load BP NSs.[60] The obtained BP/PDLLA hydrogel showed good temperature sensitivity and was demonstrated as a decent platform for postsurgical treatment of cancer. Zhang and coworkers fabricated a BP/polymer hydrogel by using agarose which is commonly considered as a harmless material for humans by the American Food and Drug Administration (FDA).[24c] Such a hydrogel represents a reversible hydrolysis and softening process, resulting in an accelerated release of anticancer drugs from the matrix to the surrounding under NIR light exposure. Wu et  al. first dispersed PPMS (PPMS-EPO) and BP NSs in DCM solution via ultrasound. The mixture was then dropped onto the surface of polished TiOH and a BP/PPMS (PPMS-EPO) film was fabricated by thermal curing in a vacuum oven.[66] The BP/PPMSEPO film exhibited an excellent antibacterial rate of $99.3\\%$ and $99.2\\%$ against Escherichia coli and Staphylococcus aureus after 10 min of irradiation, respectively. Apart from the above applications in biomedicine, BP/polymers, prepared by PM, are also widely employed in many other fields.[77,98] By using a one-pot polycondensation process of hexachlorocyclotriphosphazene and $^{4,4^{\\prime}}$ -diaminodiphenyl ether on the surface of BP NSs, a crosslinking PZN modified BP (BP-PZN) was prepared and further incorporated into an epoxy resin (EP) through thermal curing to prepare BP-PZN/EP nanocomposites for flame retardancy.[76] Gong et  al. choose melamine-formaldehyde (MF) to first modify the BP (BP-MF), then appropriate amounts of BP-MF and 4,4-diaminodiphenylmethane (DDM) were mixed in acetone and stirred for $10\\mathrm{min}$ . After that, EP was added into the mixture and kept stirring for another $30~\\mathrm{min}$ . Finally, the mixture was placed in a vacuum oven at $60~^{\\circ}\\mathrm{C}$ for $^{2\\mathrm{h}}$ to remove the acetone and cured at of 100 and $150~^{\\circ}\\mathrm{C}$ for 2h, respectively. The obtained nanocomposite (BP-MF/EP) showed a high char yield of $70.9\\%$ .[97]  \n\n![](images/2e083223e5824e9830e6db1a1e8116f3a2be2ef484db21053eefe05274028539.jpg)  \nFigure 5.  Preparation of BP/polymers via PM methods. a,b) Thermal polymerization. c,d) In situ polymerization. a,b,d) Reproduced with permission.[58,60,76] Copyright 2018–2019, Wiley-VCH. Reproduced with permission.[75] Copyright 2019, The Royal Society of Chemistry.  \n\nof wearable BP electronics.[25c] Bao and coworkers selected to prepare BP/PVA nanofibers through ST method, and found that BP/polymers possess fast carrier dynamics together with a modulation depth of $10.6\\%$ .[30] Zhang et  al. also demonstrated that BP/PMMA fibers show broadband nonlinear optical response ranging from 400 to $1930\\ \\mathrm{nm}$ , which paves the way for practical optoelectronic applications of BP.[40] Blaker’s group used PLAG to encapsulate BP to obtain BP/PLGA fibers, which was proved to be an ideal material to study the release rate of phosphate ions over an 8 week period.[57]",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.4. Other Methods",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.3. Spinning Technology  \n\nSpinning technology (ST) has been developed into a popular technology to prepare continuous nanofibers, which is another important way to prepare BP/polymer fibers. The core part of ST is the spinning fluid composed of BP and polymers passing through a spinneret nozzle, leading to the formation of a liquid jet, which may change into solid fibers rapidly after cooling or removing the solvents. The solution spinning is the most applied way to prepare BP/polymer fibers in order to maintain the microstructures and to obtain a well-dispersed solution of BP. In addition, the most used BP spinning fluids are those containing polymers with excellent fluidity, homogeneity, and large cohesion, so as to make sure the continuous spinning flow under the driving force. Chen et al. reported a flexible $\\mathsf{B P}/$ CNT/TPU supercapacitor with high energy density through a microfluidic ST, which may provide a way for fabrication  \n\nApart from the three mainly adopted methods, there are also many other effective strategies to fabricate BP/polymers. Zhang et  al. used the electrochemical deposition method to prepare BP/PPy films which can serve as promising flexible supercapacitors.[25b] Tang’s group obtained a BP/PVA nanocomposite through freeze drying, where the BP and PVA are connected with strong hydrogen bonding.[63] The nanocomposites showed a robust mechanical property and excellent controllable NIR-responsive drug delivery. BP/Pluronic F127 was also prepared via freeze drying and it was found that this compound can be used for synergistic photothermal-chemotherapy.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 3. Properties of Black Phosphorus/Polymers  \n\nSpecific nanocomposites are usually applied for specialized fields owing to their outstanding advantages of nanocomposites with specificity of properties. BP has been demonstrated to be a suitable nanomaterial to construct BP/polymers with various special properties, and the most conspicuous aspects are the improved optical absorption, superior mechanical strength, and robust environmental stability, which guarantee expansive applications of the BP/polymers.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 3.1. Optoelectronic Properties  \n\nThe optoelectronics properties of BP based nanocomposites can also be improved through functionalization with suitable polymers, enabling applications in fields such as tumor treatment, nonlinear optical properties, biomarker detection, electronic and optoelectronic devices.  \n\nFor example, the photothermal conversion efficiency is critical for nanomaterials to be used in PTT as photothermal agents. To enhance the photothermal conversion efficiency of BP NSs, PDA has been used to coat BP through a simple oxidative polymerization of dopamine in an alkaline environment. The photothermal conversion efficiency of the resulting $\\mathtt{B P}@\\operatorname{PDA}$ nanocapsules was increased due to the strong NIR absorbility of PDA. When irradiated with an $808~\\mathrm{nm}$ laser, enhanced heat generation was observed for these B $\\mathrm{\\cdotP}@\\mathrm{PDA}$ nanocapsules, so contributing to a better tumor PTT efficiency.[62]  \n\nThe changes in optical properties can also be used in detection of biomarkers. For instance, Zhou et  al. prepared a BP based fiber optic biosensor for detection of the cancer biomarker human neuron-specific enolase (NSE). Here, BP was coated on a fiber device with an in situ layer-by-layer method. Poly-L-lysine (PLL) was used for functionalization of the BP. Antibody recognizing NSE was then immobilized through PLL. Binding of the NSE by the antibody changed the local refractive index, enabling real-time detection of NSE with ultrahigh sensitivity.[121]  \n\nThe properties of electronic and optoelectronic devices can be further improved by functionalization with suitable polymers. For instance, the external quantum efficiency of $\\mathrm{Cs}\\mathrm{Pb}{\\mathrm{Br}}_{3}$ based perovskite light-emitting diodes (PeLEDs) can significantly increase from $0.7\\%$ to $2.8\\%$ by utilizing BP/polystyrene sulfonate as the hole injection layer in a PeLED stack.[122] Lee et  al. demonstrated a BP-based nonvolatile memory transistor by using PVDF-trifluoroethylene as the ferroelectric top gate insulator, which not only improved the stability of the transistors at ambient air, but also achieved high on/off ratios $_{(\\approx10^{5})}$ , high linear mobility values $(\\approx1159\\ \\mathrm{~cm^{2}~V^{-1}~s^{-1}})$ , and content memory properties with a 12 V window.[123]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3.2. Mechanical Properties  \n\nThe excellent mechanical properties have proven essential for applications of BP based nanocomposites in many fields. Incorporation of BP into different polymer matrices can lead to the formation of BP/polymers with enhanced mechanical properties, which can sustain the applicability of BP/polymers.  \n\nFor instance, Huang et  al. prepared a BP based hydrogel scaffold to enhance bone regeneration. The hydrogel scaffold was obtained through photo-crosslinking of gelatin methacrylamide, BP, and cationic arginine-based unsaturated PEAs. SEM images of the hydrogel without BP showed a macroporous sponge-like structure with a mean pore size of about $50~{\\upmu\\mathrm{m}}$ . Incorporation of BP NSs led to the formation of a hydrogel with thicker walls. Correspondingly, the compression modulus of the hydrogel was also increased upon BP NSs incorporation. Releasing of phosphate from the hydrogel showed feeble influence on the mechanical properties of the BP/hydrogel. Meanwhile, biomineralization and bone regeneration was accelerated by this hydrogel.[86] Yang et al. reported NIR light controlled drug delivery and release with PVA based BP hydrogels. BP NSs were functionalized with PDA first and subsequently incorporated into the PVA hydrogel through a freezing/thawing method. Through formation of strong hydrogen bonding interaction within the hydrogel, the PDA modified BP NSs functioned as physical cross-linkers for PVA chains to enhance the mechanical properties of the hydrogel. Both tensile and compression tests confirmed the enhanced mechanical properties of the PVA hydrogel incorporated with PDA modified BP NSs. With enhanced mechanical properties and excellent reactivity to NIR light, this hydrogel turned out as promising in bioapplications, like artificial articular cartilage and drug delivery agents.[63] Ni et al. also studied the enhanced mechanical properties of BP/PVA nanocomposites. The formation of saturated P-O bonds outside the BP NSs enhanced their stability in air. Meanwhile, the mechanical properties (strength, toughness, and modulus) of the composite was dramatically increased by the interaction between BP NSs and PVA.[115]  \n\nZhang and coworkers fabricated a self-standing BP/PPy nanocomposite film through a facile one-step electrodeposition route.[25b] The prepared film showed good flexibility thanks to the friction between the BP and the polymer matrix, leading to increased toughness, mechanical strength, and modulus. The film can be bent with a large angle ranging from $0^{\\circ}$ to $180^{\\circ}$ , and such a prepared film can still retain almost $90\\%$ of its original capacitive value after 200 times bending. Chen’s group reported a BP/CNT/TPU nanocomposite film for a high energy density flexible supercapacitor.[25c] The prepared flexible film showed excellent mechanical strength with a Young’s modulus of $313~\\mathrm{MPa}$ and break elongation of $17.96\\%$ , respectively, which can be cut into different shapes and bended, rotated, twisted, and folded for many cycles. Bonaccorso et  al. found that the BP/PMMA nanocomposite shows about $106\\%$ improvement in Young’s modulus compared to the bare polymer.[124] Cheng’s group reported that the BP/PVA nanocomposite shows a maximum tensile strength of $316.9\\pm12.1\\mathrm{{\\:MPa}}$ , which is about 1.9 times higher than that of pure PVA films with the addition of 3.11 wt% BP.[115]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3.3. Stability  \n\nThe relatively low stability in ambient conditions largely restricts the application of BP based nanomaterials. Oxygen and water have been considered to be the sources for the BP degradation. Detailed analysis of this process has shown that the reaction of oxygen with the surface of BP is the main cause of BP degradation.[125] The stability of BP NSs is also dramatically affected by light which can generate different kinds of reactive oxygen species (ROS) in the presence of oxygen and water. The reaction of ROS with the surface of BP results in the formation of $\\mathrm{P}_{x}\\mathrm{O}_{\\gamma}$ causing degradation of the BP NSs. It has been found that the ultraviolet part of the light spectrum is the main contributor to the degradation.[13d] Therefore, isolation of oxygen from BP has been the main strategy to enhance the stability of BP based nanomaterials by means of functionalization with suitable polymers. For example, PLGA is an FDA approved polymer with a degradation period spanning several months. The stability of BP QDs has been dramatically improved after incorporation into PLGA through the SC method. The size of the resulting BP QDs/PLGA nanospheres was about $100\\ \\mathrm{nm}$ . Through this strategy, the stability of BP QDs was effectively improved after incubation in phosphate-buffered saline (PBS) for 8 days, no dramatic loss of light absorbance and heat generation in response to $808~\\mathrm{nm}$ light irradiation was observed. After intravenous injection, the nanospheres were enriched in tumor tissues through an enhanced permeability and retention (EPR) effect. As a result, a more dramatic heat generation and tumor inhibition was achieved with these nanospheres after $808{\\mathrm{nm}}$ light irradiation.[126] PDA can also significantly improve the stability of BP based nanomaterials. As shown in ref. [62] after polymerization of dopamine, a layer of tight PDA could be coated on the surface of BP NSs. Both oxygen and water could be isolated from the internal BP NSs, resulting in enhanced stability. Both the size and the photothermal conversion of $\\mathtt{B P@}$ PDA could be maintained even after a long-term incubation at ambient conditions, enabling the utilization of these nanoconjugates in drug delivery and tumor treatment.[62]  \n\nThe instability of BP in physiological media also restricts its application in biomedical research. Because of the electron screening effect, pristine BP tends to aggregate and precipitate in media containing salts. Functionalization with polymers effectively improves the stability of BP based nanomaterials in physiological conditions. For example, Tao et al. utilized PEG- $\\cdot\\mathrm{NH}_{2}$ to coat BP NSs to enhance the stability in physiological media like PBS and cell culture media. $\\mathrm{PEG}\\mathrm{-NH}_{2}$ interacts with BP NSs mainly through electrostatics and when incubated in PBS or cell culture media, pristine BP NSs form aggregates with size up to about $1\\upmu\\mathrm{m}$ . This process was abolished by functionalization with PEG- $\\cdot\\mathrm{NH}_{2}$ , enabling a successful application of BP-PEG nanocomposites in tumor treatment.[44]  \n\nZhang et  al. reported that the modification of BP with PIL-TFSI can improve the environmental stability of BP.[23a] They found that the oxygen content in BP-based photodetectors (PDs) quickly increases from $5.5\\%$ to $49.1\\%$ while only about a $2.3\\%$ increase of oxygen content can be detected in a BP-PIL-TFSI-based PD after exposure in ambient air for 90 days. Additionally, Hu et al. also proved that the introduction of PIL can strongly enhance the environmental stability of BP. The BP-PIL-TFSI-based PD showed high flexibility, as well as great detectivity with almost no obvious deterioration in performance after $120\\mathrm{~h~}$ .[127] Cheng et  al. claimed that the PVA-coated BP nanocomposites present enhanced air-stability owing to the formation of outside saturated PO bonds.[115] Wen and coworkers applied PEDOT:PSS to coat BP; the obtained BP/PEDOT:PSS nanocomposite showed electrical conductivity as well as improved environmental stability in oxygen-rich water environments, which can offer a new opportunity for the practical applications of BP in electronics and optoelectronics.[128] Stable BP can also be obtained by sonication-assisted liquid-phase exfoliation (LPE) in the presence of MMA followed by radical polymerization.[129] Feng et  al. unveiled that PDDA can serve as hydrophilic ligands to improve the dispersity of BP in water and that BP/PDDA can maintain its properties even when exposed 15 days in both water and air.[51] Xu et  al. utilized an easy strategy to stabilize BP QDs by making a uniform BP/PMMA nanocomposite fiber film via the ST method, and found the same nonlinear optical properties for this compound as for fresh BP QDs.[40]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 4. Applications of Black Phosphorus/Polymers",
+        "category": " Introduction"
+    },
+    {
+        "id": 13,
+        "chunk": "# 4.1. Optoelectronic Applications  \n\nAs described above, BP/polymers can strongly enhance the stability of BP. Besides that, BP/polymers can also improve the optical, mechanical, electrical and thermal properties of BP, which can strengthen the applications of BP in various areas. In this section, we summarize the applications of BP/polymers in optoelectronics. Especially in laser technology, ultra-stable pulses can be readily achieved from pulsed lasers based on $\\mathsf{B P}/$ polymers with great stability in environments. The advances of BP/polymers in other optoelectronic applications like PDs, random access memories and light-emitting diodes (LEDs) are here also covered.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 4.1.1. Laser Applications  \n\nUltrashort pulses with high energy have a variety applications such as nonlinear microscopy,[130] micromachining,[131] frequency combs,[132] and in biological research.[133] Saturable absorbers (SAs), which act as optical switches to convert continues waves into pulses, play a significant role for laser cavities.[134] In general, SAs can be divided into fast SAs and slow SAs according to response time. Fast SAs, like nonlinear polarization evolution (NPE) devices and nonlinear optical loop mirrors (NOLM), which possess a nearly instantaneous response time with deep modulation depth, are appropriate to generate ultrashort pulses with high energy.[135] However, NPEs are sensitive to environmental perturbations and do not support self-starting mode-locked operations; NOLMs usually require accuracy control over the power splitting, which affects its practical application. In contrast, a self-starting and stable mode-locked operation can be achieved with slow SAs. With the development of materials science, the response time of slow SAs can reach the femtosecond regime, which is suitable for ultrashort pulse generation. Semiconductor saturable absorber mirrors (SESAMs) are the most common slow SAs in the market, which can be attributed to their outstanding saturable absorption performance,[136] whereas the sophisticated fabrication and packaging mechanism of SESAMs increase the cost.[137] In addition, SESAM only have a few tens of nanometer operation bandwidth (narrowband operation) in the NIR,[136c] which seriously hinders the applications of SESAM in the field of midinfrared lasers. Recently, 2D materials have shown promising applications in electronics and photonics.[1e,3d,138] Their excellent nonlinear optical absorption makes them suitable as SAs in laser systems. Graphene was the first demonstrated 2D material SAs in laser systems (fiber based,[139] solid state,[140] waveguide[141]) due to fast recovery time,[142] broad operation bandwidth,[143] and low cost fabrication. However, the output performance of the laser is seriously hindered due to the low modulation depth of graphene $(2.3\\%$ for monolayer[144,145]). Subsequently, a series of 2D materials with different properties, like topological insulators (TI),[146] TMDs,[147] MXenes,[148] and BP materials, have been demonstrated as SAs in laser systems. BP has joined the 2D family with layer dependent direct bandgaps from 0.3 to $1.5\\mathrm{eV},^{[149]}$ and so bridges the bandgap between zero-gap graphene and large-gap TMDs $(1{-}2\\ \\mathrm{eV})$ for near and mid-infrared photonics and optoelectronics. Even though BP has lots of merits, an inevitable issue is the poor stability of BP in environments. As discussed in this review, incorporation with different polymers can effectively slow down the degradation rate and improve the environmental stability of BP,[150] which paves the way for ultrafast laser systems based on BPSA. Here, we summarize the recent progress for BP/polymers acting as SAs used in ultrafast laser systems (Table 2).  \n\nXu et al. proved that the stability of BP QDs can be improved by fabricating BP QDs/PMMA composite nanofiber films via an electrospinning technique. The application of the Z-scan method could prove that BP QDs/PMMA can maintain outstanding nonlinear optical properties for three months. A 1.07 ps pulse duration at the central wavelength of 1567.6 nm can be achieved from Er-doped mode-locked fiber lasers based on BP QDs/PMMA as a SA.[40] Feng et  al. selected PDDA to adsorb on the surface of few layers through electrostatic interaction. The results exhibited that the PDDA not only enhances the environmental stability of BP, but also improves the dispersity of BP in water. Moreover, it allows PDDA-BP to stabilize in both air and water more than 15 days of exposure, as shown in Figure  6. Hence, ultra-stable pulses with 1.2 ps pulse duration at $1557.8~\\mathrm{nm}$ can be obtained from Er-doped PML fiber lasers using PDDA-BP SA (Figure 7).  \n\nQ-switching is another technique to achieve pulses with high energy. Wu et al. reported a PVA-BP based $635\\mathrm{nm}$ Q-switching $\\mathrm{Pr}^{3+}$ doped fiber laser, the pulse duration was 383 ns and the tunable pulse repetition rate ranging from 108.8 to $409.8\\mathrm{kHz}$ .[38] Liu et  al. achieved 283.91 nJ pulse energy from a BP/PMMA based fiber laser, which is the largest pulse energy among Q-switched fiber lasers with BP SA at $1.5~{\\upmu\\mathrm{m}}$ .[53] Mu et  al. demonstrated two fabrication approaches to produce BP/PMMA films, the schematics of the two methods (sandwiched method and the ST) are shown in Figure  8a and b, respectively. A Q-switching operation can be obtained once the pump power reaches $25{\\mathrm{~mW}},$ which is a low threshold compared with those of graphene[151] and TMDs based SAs.[152] The output performance is shown in Figure  8c–f. The output spectrum bandwidth is $1.5\\ \\mathrm{nm}$ at the central wavelength of $1561.9\\ \\mathrm{nm}$ (Figure  8c) and the pulse train interval is $42.5~{\\upmu\\mathrm{s}}$ , which corresponds to a $23.48\\mathrm{kHz}$ repetition rate (Figure 8d). The output pulse duration is $4.35~\\upmu\\mathrm{s}$ and the radio frequency (RF) spectrum is around 53 dB shown in Figure 8e,f, respectively.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 4.1.2. Other Optoelectronic Applications  \n\nIn addition to its wide application in laser systems, BP/polymers have great application potential also in other fields, such as, field-effect transistors (FET),[22b,153] random access memories,[154] LED,[122] high-capacity lithium ion batteries, and PDs.[155] By applying poly PIL-TFSI into encapsulated BP QDs, Zhang et  al. demonstrated photoelectrochemical-type photodetector applications. The stability of BP can be significantly enhanced. In addition, the BP PDs possess self-healing capability and the typical ON/OFF signals can still be detected after 50 cycles attributing to the self-healing property of PIL-TFSIs, as shown in Figure 9. Ricciardulli et al. denoted that by introducing BP as a hole injection layer in LED stacks, the output and efficiency of perovskite based LEDs can be enhanced by increasing the hole injection and morphology of the $\\mathrm{Cs}\\mathrm{Pb}{\\mathrm{Br}}_{3}$ structure.[122] Li et al. demonstrated an original passivation method in that using poly (2-hydroxyethyl methacrylate)-co-poly (styrene) (PHMA-co-PS) it could improve the electrical transport properties for BP transistors at high electric fields.[153b] By applying the PHMA-co-PS encapsulation technique, the breakdown characteristics of BP FETs could be greatly improved and the on/off ratios increased by one order and four orders of magnitude in room and cryogenic temperatures, respectively. Meanwhile, this encapsulation technique showed outstanding stability in air as well as compatibility with mainstream semiconductor device manufacturing, promoting a potential application of wafer-scale. Figure  10 exhibits output characteristics of unencapsulated and encapsulated BP devices at different temperatures. Figure 10d shows that the maximum drain current can reach $1.2\\mathrm{mA}\\upmu\\mathrm{m}^{-1}$ at $20~\\mathrm{K}$ in BP FETs with PHMA-co-PS.  \n\nTable 2.  Performance summary of ultrafast lasers based on BP/ploymer as SA.   \n\n\n<html><body><table><tr><td>Material type</td><td>Layers</td><td>Technology</td><td>Laser type/wavelength</td><td>Repetition rate</td><td>Time</td><td>Energy</td><td>Ref</td></tr><tr><td>BP/PMMA</td><td>4-25 nm</td><td>Q-switching</td><td>Er/1561.9</td><td>7.86-34.32 kHz</td><td>4.35-2.96 μs</td><td>194 nj</td><td>[30]</td></tr><tr><td>BP/PC</td><td>15</td><td>Q-switching</td><td>Er/1550</td><td>35.7-70.6 kHz</td><td>6.2-1.65 μs</td><td>25.2 n)</td><td>[33]</td></tr><tr><td>BP/PVA</td><td>-</td><td>Mode-locking</td><td>Er/1533, 1558</td><td>20.8214 MHz 20.8221 MHz</td><td>700 fs</td><td>0.07 nj</td><td>[37]</td></tr><tr><td>BP/PVA</td><td>3</td><td>Q-switching</td><td>Pr3+/635</td><td>108.8-409.8 kHz</td><td>1560-383 ns</td><td>27.6 nj</td><td>[38] </td></tr><tr><td>BP/PDMS</td><td>9-24</td><td>Q-switching</td><td>Er/1064.7</td><td>26-76 kHz</td><td>5.5-2.0 μs</td><td>17.8 n)</td><td>[39] </td></tr><tr><td>BP/PMMA</td><td>1-3</td><td>Mode-locking</td><td>Er/1567.6</td><td>11.01 MHz</td><td>1.07 ps</td><td></td><td>[40] </td></tr><tr><td>BP/PVA</td><td>7</td><td>Mode-locking</td><td>Er/1562</td><td>5.268 MHz</td><td>1.438 ps</td><td></td><td>[49] </td></tr><tr><td>BP/PVA</td><td>70-100 nm</td><td>Q-switching</td><td>Er/1567.8-1565.3</td><td>64.51-82.64 kHz</td><td>3.39-1.36 μs</td><td>148.63 nj</td><td>[50] </td></tr><tr><td>BP/PDDA</td><td>3-7</td><td>Mode-locking</td><td>Er/1557.8</td><td>6.317 MHz</td><td>1.2 ps</td><td></td><td>[51] </td></tr><tr><td>BP/PDMS</td><td>-</td><td>Mode-locking</td><td>Er/1559</td><td>13.8MHz</td><td>650 fs</td><td>1.70 mW</td><td>[52] </td></tr><tr><td>BP/PMMA</td><td></td><td>Q-switching</td><td>Er/1561.21-1564.16</td><td>10.35-30.10 kHz</td><td>25.01-2.98 μs</td><td>283.91 nj</td><td>[53]</td></tr></table></body></html>  \n\n![](images/f389f012770df966709252a92f59bcede99b25cf070c3bbe68e0b020a5a5e267.jpg)  \nFigure 6.  Experiment on the stability of exfoliated PDDA-BP NSs. a) AFM images of bilayer PDDA-BP-1 nanosheets at the special region exposure under ambient conditions after 1, 7, 10, and 15 days (scale bar, $3\\upmu\\mathrm{m})$ . AFM: atomic force microscope. b,c) Raman spectra evolution and XPS spectra of the P element in bilayer PDDA-BP NSs against the exposure time in air. XPS: X-ray photoelectron spectroscopy. d) Intensity ratio of the $\\mathsf{A}_{\\mathrm{g}}^{\\mathrm{~l~}}/\\mathsf{A}_{\\mathrm{g}}^{\\mathrm{~\\tiny~\\dot{2}~}}$ from Raman spectra of PDDA-BP-1 exposure under ambient conditions after 15 days; e) Intensity ratio of the $\\mathsf{P O}_{x}/2\\mathsf{p}_{3/2}$ as a function of exposure time from XPS. a–e) Reproduced with permission.[51] Copyright 2018, American Chemical Society.  \n\n![](images/613c723c43af9b3bd702975bc007806b7758aecd622e7f3cd3712aa8db4fe0db.jpg)  \nFigure 7.  a) Experimental set up of an Er-doped PML fiber laser using a BP-PVA SA. LD: Laser diode, WDM: Wavelength division multiplexer, EDF: Erbium-doped fiber, OC: Output coupler, ISO: Polarization insensitive isolator, SMF: Single-mode fiber, PC: Polarization controller. b) Nonlinear transmission of BP at $1.5\\upmu\\mathrm{m}$ . c) Output spectrum. d) Intensity autocorrelation fitted by sech2. e) Output pulse train. f) Radio frequency (RF) spectrum. Inset: Wideband RF spectrum of $600~\\mathsf{M H z}$ . a–f) Reproduced with permission.[51] Copyright 2018, American Chemical Society.  \n\n![](images/8349b5941ae187b12a7f5b71070929125849f0aef6dce6b6e82e178fe3916029.jpg)  \nFigure 8.  a) Fabrication process of sandwiched PMMA-BP-PMMA membranes. b) Diagrams exhibiting the fabrication of BP-PVP nanocomposite membranes by the electrospinning technique. c) Output spectrum. d) Output pulse train. e) Intensity autocorrelation. f) RF spectrum. Inset: Wideband RF spectrum of $780~\\mathsf{k H z}$ . a–f) Reproduced with permission.[30] Copyright 2015, Wiley-VCH.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 4.2. Bio-Applications  \n\nThe applicability of BP in biomedical fields has been widely investigated. With excellent photoelectronic properties, BP has been shown to be a promising candidate for bio-imaging and phototherapies, such as PTT and PDT.[156] The large surface area of BP NSs enables highly efficient drug loading and delivery. Meanwhile, the degradation of BP results in in situ formation of phosphate, which is an important raw material for bone regeneration. BP has also been applied for antibacterial treatment, for gene editing, and for neurodegenerative diseases, etc.[157] Functionalization of BP with suitable polymers has turned out critical for the successful application of BP in the biomedical field. The biocompatibility and stability of BP can be efficiently improved when coated with polymers such as PEG and PLGA. Meanwhile, polymer functionalization of BP provides moieties for further modification of the nanocomposites with targeting ligands and other functional groups, which are important for optimization of therapy efficiency and reduction of side effects.[62] Moreover, the incorporation of BP into certain polymers enables fabrication of various hydrogels and scaffolds with unique characteristics, suitable for applications in tissue engineering.[24c]  \n\n![](images/731a1a7b0f3eab40d4adb41e1ec8f4126e63869066487bf293914ce0c5cc4d75.jpg)  \nFigure 9.  Photo-response behavior of BP-PIL-based PDs. a) Linear sweep voltammetry (LSV) curve of BP-PIL. b) Photo-response behavior of the PD at $-0.6\\:\\vee$ in different concentration KOH solution. c) Photo-response behavior with different potential in $0.75~\\mathsf{m}$ KOH solution. d) Long-term stability test of BP-PIL-based PD. e) Photo-response behavior of the as-prepared PDs after different cycles of self-healing. f) $P_{\\mathsf{p h}}$ as the function of different self-healing cycles. a–f) Reproduced with permission.[23a] Copyright 2019, Wiley-VCH.  \n\n![](images/7bd565a7b7e27b868bddfc0b482f466bd848ef25a3a370aacdca6db5800c3a8b.jpg)  \nFigure 10.  a,b) Output properties of unencapsulated and encapsulated BP FETs with PHMA-co-PS at $300~\\mathsf{K}$ ( $\\boldsymbol{\\mathrm{V_{d}}}$ is from 0 to $-4\\lor$ ). c,d) Breakdown characteristics of the unencapsulated and encapsulated BP devices at $20~\\mathsf{K}$ $(V_{\\mathrm{g}}$ is from 2 to $-6\\mathsf{V}$ in steps of −1 V). a–d) Reproduced with permission.[153b] Copyright 2019, Wiley-VCH.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 4.2.1. Bio-Imaging  \n\nBio-imaging refers to the visualization of biological structures and processes through noninvasive strategies. With layer dependent fluorescence, high photothermal conversion efficiency and excellent loading capacity, BP based nanomaterials have attracted much interest in fluorescence imaging, photothermal imaging, and photoacoustic (PA) imaging.[156]  \n\nBecause of quantum size effects, layer dependent fluorescence has been detected with few layer BP based nanomaterials, suitable for fluorescent imaging of cells and tumors.[158] Meng et  al. measured by means of an LPE method the photoluminescence lifetime of BP nanoparticles with lateral size and thickness of 35 and $6\\mathrm{nm}$ , respectively. Photoluminescence emission at $690~\\mathrm{nm}$ was observed, the lifetime of which was shown to be 110.5 ps.[159] BP QDs fabricated with a pulsed laser ablation method also showed stable blue–violet photoluminescence emission with a quantum yield as high as $20.7\\%$ .[160] Because of the large surface area of BP, BP/polymers are also suitable for loading and delivery of fluorescent agents for bioimaging. Li et  al. reported the application of PEGylated BP QDs for loading of the fluorescent RdB molecule (Figure 11a). Functionalization with PEG improved the physiological stability and biocompatibility of the BP QDs (Figure  11c). Loading of RdB enabled efficient imaging of tumor cells (Figure  11d).[45] Deng et al. modified small BP nanoparticles with dextran and poly(ethyleneimine), which enabled further functionalization with folic acid (FA) and cyanine 7 (Cy7). The resultant BP nanoparticles showed excellent stability, biocompatibility and tumor targeting ability. Both PA imaging and NIR fluorescence imaging of tumors were realized with these nanoparticles, suitable for imaging guided diagnosis and treatment of tumor.[67]  \n\nWith excellent photothermal conversion efficiency, BP based nanomaterials are also ideal agents for photothermal imaging. When intravenously injected, they accumulate in tumor tissues through the EPR effect. Following NIR light irradiation, heat is generated in the tumor tissues and can be easily detected with a thermal imaging camera. Combinations with polymers enhance the physiological stability, tumor targeting efficiency or photothermal conversion efficiency of the BP based nanomaterials. For example, functionalization of BP NSs with PEG enhances the stability in physiological media. When an FA moiety is attached through PEG, enhanced retention of the nanocomposites in cervical cancer models has been observed, making it possible to improve the tumor specificity of photothermal imaging.[44] To enhance the photothermal conversion efficiency of BP NSs, Zeng et al. modified them with PDA. The stability of BP NSs in ambient environment was so dramatically enhanced through isolation of both oxygen and water by the PDA modification. Meanwhile, the tumor targeting efficiency of the nanocomposites could be enhanced through further modification of PDA through Michael addition or Schiff base reactions. With light adsorption of PDA, the photothermal conversion efficiency of the nanocomposites was also improved. All these processes contributed to better photothermal imaging and PTT mediated inhibition of breast cancer.[62]  \n\nPA imaging uses contrast agents to absorb energy from short laser pulses to generate thermo-elastic expansion, which is detected by ultrasonic transducers to show tissue structures with high temporal and spatial resolution, deep tissue penetrability and excellent sensitivity.[161] Contrast agents are critical for PA imaging. Because of their intense and stable signals, various nanomaterials, including BP/polymers, have been shown to be excellent contrast agents for PA imaging.[162] For instance, Sun et al. reported the application of PEGylated BP nanoparticles in PA imaging of tumors. High yield production of water-soluble and biocompatible BP/PEG conjugates was prepared with a one-pot solventless high energy mechanical milling method. High photothermal conversion efficiency and excellent photostability under NIR light irradiation was so observed with these nanoconjugates. Upon administration through intravenous injection, the nanoparticles accumulated in tumors through the EPR effect, enabling detection of tumors with PA imaging.[24b]  \n\n![](images/2c1e2fc77767b219b3244c2924ce53bbc65c0c58d1e56fb7f6ba7476ec5906f5.jpg)  \nFigure 11.  Loading of RdB with PEGylated BP QDs for cell imaging. a) Schematic illustration of the functionalization and RdB loading of BP QDs for imaging and tumor inhibition. b) TEM image of RdB/PEG-BP QDs. c) Biocompatibility of PEG-BP QDs detected with HepG2 cells. d) Fluorescence imaging of HepG2 and 4T1 cells with RdB/PEG-BP QDs. a–d) Reproduced with permission.[45] Copyright 2017, American Chemical Society.  \n\nTable 3.  Examples of BP/polymers applied in PTT of cancer.   \n\n\n<html><body><table><tr><td>Material type</td><td>Size/height [nm] </td><td>Laser</td><td>Model</td><td>Remarks</td><td>Ref.</td></tr><tr><td>BP/PEG</td><td>3.2 ± 1.0, 1.2 ± 0.6</td><td>808 nm, 2 W cm-2, 5 min</td><td>4T1 breast cancer</td><td>PA imaging guided PTT</td><td>[24b] </td></tr><tr><td>BP/PEG</td><td>2.6,1.5</td><td>808 nm, 1 W cm-2, 10 min</td><td>C6 glioma cells and MCF7 breast cancer cells</td><td>Excellent photothermal conversion efficiency and photostability</td><td>[31] </td></tr><tr><td>BP/PLGA</td><td>102.8 ± 35.7</td><td>808 nm, 1 W cm-2, 10 min</td><td>MCF7 breast cancer</td><td>Excellent stability and biodegradability</td><td>[126] </td></tr><tr><td>BP/PEG-FA/DOX</td><td>120,1-2</td><td>808 nm, 1.0 W cm-2, 10 min</td><td>HeLa cervical cancer</td><td>Tumor specific drug delivery and PTT</td><td>[44]</td></tr><tr><td>BP/PDLLA/PEG/PDLLA</td><td>/</td><td>808 nm, 0.5 W cm-2, 5 min</td><td>HeLa cervical cancer</td><td>Sprayable and biodegradable hydrogel for PTT and postsurgical treatment of cancer</td><td>[60] </td></tr><tr><td>BP/PDA/PEG-Apt</td><td>200-300,12.6</td><td>808 nm, 1.0 W cm-2, 10 min</td><td>MCF7 breast cancer</td><td>Enhanced stability and photothermal performance, relief of multidrug-resistance</td><td>[62]</td></tr><tr><td>BP-DEX/PEI-FA/Cy7</td><td>15-40, 1.6-4.3</td><td>808 nm, 1.5 W cm-2, 2 min</td><td>4T1 breast cancer</td><td>NIR Fluorescence imaging and PA imaging guided PTT</td><td>[67]</td></tr><tr><td>BP/cellulose hydrogel</td><td>一</td><td>808 nm, 1 W cm-2, 5 min</td><td>Huh7 hepatocellular carcinoma</td><td>Injectable hydrogel for PTT</td><td>[69]</td></tr><tr><td>BP/Pluronic F-127</td><td>一</td><td>808 nm, 2.0 W cm-2, 5 min</td><td>4Tl breast cancer</td><td>Thermo-sensitive hydrogel for drug delivery and PTT</td><td>[78]</td></tr><tr><td>BP/PLLA/PEG/PLLA</td><td>164.1 ± 14.8</td><td>808 nm, 1.0 W cm-2, 10 min</td><td>T47D breast cancer</td><td>Sensitization of tumor through downregulation of heat</td><td>[104]</td></tr><tr><td>BP/PLGA</td><td>165.5±55</td><td>808 nm, 1.0 W cm-2, 5 min</td><td>U251 glioma</td><td>shock protein 90 Mesenchymal stem cells mediated tumor targeting</td><td>[105]</td></tr></table></body></html>\n\nFA: Folic acid, DOX: Doxorubicin, DEX: Dextrin, Apt: Aptamer.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# 4.2.2. Tumor Treatment  \n\nBP/polymers have also been widely investigated for tumor treatment. Upon administration, these nanoparticles can accumulate in tumor tissue through the EPR effect. With excellent NIR light response, BP/polymers can be activated in deeper tissues, enabling non-invasive tumor treatment. When irradiated with light of suitable wavelength, either hyperthermia or ROS can be produced by BP, enabling PTT or PDT mediated tumor inhibition.[44,163] Benefitting from the extremely high surface areas of BP, BP/polymers are also idea carriers for loading and delivery of various cargos (drugs, nucleic acids, proteins, etc.) for combined tumor treatment.[164]  \n\nEspecially, conjugation of BP/polymers with various tumor targeting ligands (FA, Transferrin, polysaccharides, peptides, antibodies, and aptamers recognizing tumor specific surface makers) has enabled efficient tumor specific delivery of these nanomaterials and cargos. This widely applied strategy has largely enhanced the efficiency, tumor specificity and biocompatibility of the therapy.  \n\nPhotothermal Therapy: Traditional tumor therapies like radiotherapy, chemotherapy and surgery, face challenges of side effects, and tumor recurrence. In searching for new tumor therapies, nanomaterial-mediated PTT has drawn much attention recently. In PTT, nanomaterials with high photothermal conversion efficiency have been delivered into tumor tissues followed by irradiation with light of suitable wavelength for heating generation in situ that can kill tumor cells. Because of its non-invasiveness, high efficiency, and specificity, PTT has been extensively investigated in treatments of various tumors and several groups of nanomaterials with excellent photothermal conversion efficiency have been developed for usage in PTT of tumors.  \n\nBP/polymers are also prominent photothermal agents for PTT of tumors. Various polymers have been utilized in surface modification of BP NSs and BP QDs for PTT of several kinds of tumors. Incorporation of BP with suitable polymers has also enabled the preparation of hydrogels for intratumoral injection and postsurgical treatment (Table 3). In 2015, Sun et al. proved the potential of BP QDs as photothermal agents for tumor treatment. $28.4\\%$ photothermal conversion efficiency was observed with NIR light exposure of BP QDs, indicating their excellent photothermal performance. The photostability of BP QDs was also high. After functionalization of the BP QDs with PEG, the stability in physiological media was increased, enabling their usage in cell culture. BP/PEG nanocomposites showed excellent biocompatibility in several types of cells. Stimulation with NIR light led to efficient induction of cancer cell death through PTT.[31] Sun et al. furthermore investigated a high yield preparation of PEGylated BP nanoparticles with an one-pot solventless high energy mechanical milling technique. The BP/PEG nanocomposites obtained with this strategy were water-soluble and biocompatible. When exposed to NIR light, excellent photothermal conversion was observed, enabling complete ablation of tumors in vivo through PTT.[24b]  \n\nShao et al. loaded BP QDs into PLGA to prepare biodegradable BP QDs/PLGA nanospheres with an emulsion method (Figure  12a,b). This strategy protected the BP QDs from external water and oxygen and increased the photothermal stability of BP QDs (Figure  12c,d). The rate of degradation of the BP QDs was also controlled by the hydrophobic PLGA (Figure  12e). These nanospheres were highly biocompatible (Figure  12f). When injected intravenously, an excellent tumor targeting ability was observed (Figure 12g,h). Benefitting from the excellent photothermal conversion efficiency and stability of these nanospheres, heat generation in the tumor tissues was detected when irradiated with NIR light (Figure 12i). Excellent tumor inhibition efficiency was achieved, further revealing the potential of BP/polymers for PTT of tumors (Figure 12j).[126]  \n\nXing et  al. reported the preparation of injectable composite hydrogels with BP NSs and cellulose for PTT of tumors. The hydrogels were biocompatible and showed excellent photothermal conversion efficiency and flexibility, suitable for tumor ablation with PTT.[69]  \n\nBP/polymers are also used in PTT mediated postsurgical treatment of tumors. Through incorporation of BP NSs with a thermosensitive hydrogel [poly(oplactide)-poly(ethylene glycol)- poly(bplactide) (PDLLA-PEG-PDLLA: PLEL)], a $\\mathtt{B P}\\ @$ PLEL hydrogel was prepared with excellent biodegradability, biocompatibility, photothermal conversion efficiency, and possibility for NIR light-induced sol–gel transition. When sprayed and irradiated with NIR light, the hydrogel formed a gelled membrane on tumor surgery caused wounds. The residual tumor tissues were ablated by PTT. Meanwhile, bacteria were also killed by hyperthermia to prevent infection.[60]  \n\n![](images/6e0cd50b98e7c8bbcffa1cb5ef096e774471eadff9002f0f6f2340674c9ff8e5.jpg)  \nFigure 12.  BP QDs/PLGA nanospheres for PTT of tumor. a) TEM images of BP QDs. b) SEM images of BP QDs/PLGA nanospheres. c) Photothermal performance of BP QDs after storage in water for indicated times. d) Photothermal performance of BP QDs/PLGA nanopheres after storage in water for indicated times. e) SEM images of BP QDs/PLGA nanospheres after storage in PBS for indicated times. f) Viability of cells after incubation with BP QDs/PLGA nanospheres for $48\\mathrm{~h~}$ . g) Tumor retention of BP QDs/PLGA nanospheres after intravenous injection. h) Quantitative analysis of BP $\\mathsf{Q D s}/$ PLGA nanospheres in tumor and main organs. i) Changes of tumor temperature following intravenous injection and laser irradiation. j) Changes of tumor size after indicated treatments. a–j) Reproduced with permission.[126] Copyright 2016, Springer Nature.  \n\nTable 4.  Representative BP/polymers applied in PDT of cancer.   \n\n\n<html><body><table><tr><td>Material type</td><td>Size/height [nm] </td><td>Laser</td><td>Model</td><td>Remarks</td><td>Ref.</td></tr><tr><td>BP/PEG/PAA</td><td>197</td><td>808 nm, 1.44 W cm-2, 10 min </td><td>U14 cervical cancer</td><td>UCNP enabled highly efficient PDT with 808 nm laser</td><td>[36]</td></tr><tr><td>BP/PEG</td><td>2.5± 0.7, 1.3 ± 0.7</td><td>625 nm, 80 mW cm-2, 10 min </td><td>4T1 breast cancer</td><td>Fluorescence imaging guided PDT/PTT</td><td>[45] </td></tr><tr><td>BP/PEI/AuNPs</td><td>491.7 ± 4.9</td><td>670 nm,</td><td>HepG2 hepatocellular</td><td>Localized surface plasmon resonance enhanced PDT</td><td>[68]</td></tr><tr><td>BP/RhB-MnO-FITC</td><td>120,59.3</td><td>1 W cm-2, 5 min 660 nm,</td><td>carcinoma HeLa cervical cancer</td><td>Oxygen self-supply, microenvironment responsive</td><td>[89] </td></tr><tr><td>Apt-BMSF@Pt</td><td>52.3 ± 5.7</td><td>0.15 W cm-2,10 min 670 nm,</td><td>HepG2 hepatocellular</td><td>and bio-imaging guided PDT Hepatocellular carcinoma-specific, oxygen</td><td>[91] </td></tr><tr><td>BP/PDA-Ce6&TPP</td><td>213.9</td><td>0.1 W cm-2, 5 min 660 nm, 1 W cm-2, 10 min</td><td>carcinoma HeLa cervical cancer</td><td>self-compensate Mitochondria-targeting PTT/PDT</td><td>[92]</td></tr></table></body></html>\n\nUCNP: Upconversion nanoparticles, RhB: Rhodamine B, Ce6: Chlorin e6, TPP: Triphenyl phosphonium, BMSF: BPQD-hybridized mesoporous silica framework, FITC: Fluorescein isothiocyanate.  \n\nPhotodynamic Therapy: PDT is seen as a promising noninvasive tumor treatment strategy and has been widely investigated in recent years. During PDT, photosensitizers (PSs) are introduced into tumor tissues, followed by light exposure to stimulate production of ROS in the tissues. ROS produced in tumor cells leads to peroxidation of lipids, proteins and DNA, resulting in apoptosis, necrosis, or autophagy-mediated tumor cell death. Microvascular systems in tumor tissues can be damaged by ROS, leading to shortage of oxygen and nutrients in the tumor tissues. Interestingly, ROS mediated damages to tumor tissues in PDT also stimulate complex reactions to host immune systems, leading to long-term tumor inhibition.  \n\nAs a critical component of PDT, PSs can have dramatic impact on the therapeutic efficiency. Several generations of PSs have been developed for PDT. However, several drawbacks of traditional PSs, such as low photo-stability, high hydrophobicity, and lack of tumor specificity, have largely restricted the clinical applications of PDT. The recent introduction of nanomaterials in PDT have turned the situation around and have promoted the development of therapy.[165] Nanomaterials are ideal carriers for a traditional PS to enhance the photo-stability and tumor targeting efficiency. Several kinds of nanomaterials, such as, BP, can also catalyze the production of ROS in response to light stimulation, which renders them to be utilized as PSs in PDT.[165] When conjugated with different polymers, BP based nanocomposites with various functions are fabricated for PDT of cancer. Further modification of the polymers may enhance the targeting efficiency, ROS production and tumor inhibition efficiency of PDT (Table 4).  \n\nIn 2015, Wang et  al. reported the application of BP NSs as PS in PDT. Upon $660\\ \\mathrm{nm}$ laser exposure, singlet oxygen was generated with a quantum yield of about 0.91. In vitro and in vivo studies confirmed the therapeutic efficiency of BP NSs in PDT.[166] Chen et al. further confirmed the potential of BP NSs for applications in cancer treatments including PDT.[163] Guo et al. also reported the application of BP QDs in PDT.[167]  \n\nIn most cases of PDT applications, functionalization of BP with suitable polymers is required to increase the biocompatibility and reduce the side effects of the pristine BP. Li et al. reported the functionalization of BP QDs for combined PTT/PDT of cancer. The biocompatibility and physiological stability of BP QDs were improved after PEGylation, resulting in better combined therapeutic efficiency.[45] To further increase the singlet oxygen yields of BP NSs, Zhang et  al. integrated gold nanoparticles (AuNPs) with BP NSs with PEI as linker. The singlet oxygen generation of BP NSs in response to $670\\mathrm{nm}$ laser stimulation was dramatically enhanced by excitations of localized surface plasmon resonances, leading to more efficient suppression of tumor growth.[68] To increase the penetration depth of BP based PDT, Lv et al. combined upconversion nanoparticles with BP sheets. The BP sheets were functionalized with $\\mathrm{PEG}{\\cdot}\\mathrm{NH}_{2}$ to enhance the stability. Poly(acrylic acid) was used to modify upconversion nanoparticles. Then these two components were integrated through electrostatic interaction. The resulting nanocomposites catalyzed ROS production was obtained with high efficiency when irradiated with $808~\\mathrm{nm}$ NIR light, and showed excellent PDT effect both in vitro and in vivo.[36]  \n\nThe sensitivity of various organelles to ROS is quite different. Targeted delivery of PSs to organelles such as mitochondria has been proved to induce cancer cell death with higher efficiency. As the powerhouses of the cells, the normal structure and function of mitochondria is critical for cell survival. Meanwhile, mitochondria are also critical in regulation of apoptosis. ROS mediated damage of mitochondria has resulted in both shortage of energy and release of cytochrome C into cytosol, which triggered apoptosis of cancer cells. Yang et  al. reported the targeted delivery of BP nanosheet-based PS to mitochondria for PDT (Figure  13a). BP NSs were functionalized with PDA (Figure  13b), which enabled further ligation of the nanocomposite with both chlorin e6 (Ce6) and triphenyl phosphonium (TPP) through covalent bonds (Figure  13c). The resulting nanocomposite could generate both heat and ROS when exposed to a $660~\\mathrm{nm}$ laser, enabling synergistic PTT/PDT of tumor (Figure 13d,e). Upon administration, mitochondria-targeting was achieved with TPP (Figure 13f), resulting in ROS mediated damage of mitochondria following NIR light stimulation. Dramatically enhanced inhibition of cancer cell viability was realized with this nanocomposite (Figure 13g) and fluorescence imaging of tumors in vivo could then also be achieved (Figure  13h). A quite dramatic tumor inhibition was thus observed with this nanocomposite (Figure 13i).[92]  \n\n![](images/8a73e2a71a41ba4f1b5f3965d7f8b2d4ab89492752aaa2f4659d9d4369ada0ca.jpg)  \nFigure 13.  BP@PDA-Ce6&TPP nanosheets for mitochondria-targeting PTT/PDT of cancer. a) Schematics for the preparation and application of the nanocomposites. b) TEM image of $B P@\\mathsf{P D A}$ nanosheets. c) UV–vis–NIR spectra of the indicated nanosheets. d) Heat generation of ${\\mathsf{B P@P D A}}.$ Ce6&TPP nanosheets irradiated by $660\\ \\mathsf{n m}$ laser for 10 min. e) ROS generation of the indicated materials irradiated by $660\\ \\mathsf{n m}$ laser measured by absorbance decay of ABDA at $380~\\mathsf{n m}$ . f) Confocal fluorescence images of cells pre-treated with the indicated nanosheets and Mito-Tracker Green. g) Viability of HeLa cells exposed to a $660\\ \\mathsf{n m}$ laser for 5 min after incubation with the indicated nanomaterials. h) Fluorescence imaging of mice with tumor after injection of $\\mathsf{B P@}$ PDA-Ce6&TPP nanosheets. i) Tumor inhibition efficiency of $\\mathsf{B P@}$ PDA-Ce6&TPP nanosheets. a–i) Reproduced with permission.[92] Copyright 2019, The Royal Society of Chemistry.  \n\nConsidering the immune activation ability of PDT, it has been used to treat cancer in combination with immunotherapy. This combined strategy has been shown to be promising in inhibition of tumor metastasis and recurrence. BP nanoflakes coated by neutrophil membranes have been applied in activation of the immune system through PDT/PTT to inhibit lung metastasis of tumors.[168] Recently, Zhang et  al. prepared a BP/polymer based nano-regulator for activation of anti-tumor immune responses. PEGylated hyaluronic acid was coated on the surface of BP to enhance the stability, biocompatibility and targeting efficiency of the nanocomposite. Following the combined PDT/PTT with this nanocomposite, the tumor associated macrophage phenotype was altered from pro-tumor to anti-tumor. Through induction of immunogenic cell death and release of damage-associated molecular patterns, robust anti-tumor immune responses were evoked to inhibit both the original tumor and the metastatic tumor.[114]  \n\nDrug Delivery: As one of the most widely utilized tumor therapies, chemotherapy is both simple and cheap. However, systematically administered chemical drugs cause severe side effects to normal tissues, especially tissues with active cell division. Meanwhile, dramatic changes of drug concentration in the body largely promote the occurrence of side effects and reduces the tumor inhibition efficiency. Here tumor specific delivery and controlled release of chemical drugs can promote the therapeutic efficiency and safety of chemotherapy. Nanomaterials are ideal carriers for this purpose. With the large surface area and excellent NIR light responsiveness, BP based nanomaterials are recognized as promising agents for targeted delivery and light controlled release of chemotherapy drugs. When functionalized with different polymers, the physiological stability, tumor specificity, and therapeutic efficiency of BP based nanomaterials can be effectively improved.  \n\nTao et al. reported the delivery and controlled release of the chemotherapy drug doxorubicin (DOX) with PEGylated BP NSs (Figure 14a). BP NSs were first functionalized with PEG to enhance the stability and biocompatibility. When an FA moiety was attached through PEG, the tumor targeting efficiency of the nanocomposites was increased (Figure 14b,e,f). A DOX loading capacity up to $108\\%$ was observed, which is dramatically higher than for many other nanoparticle-based drug delivery systems (Figure 14c,d). In an acidic environment, the DOX release from PEGylated BP NSs was accelerated, making it possible for a tumor microenvironment promoted drug release. When irradiated with $808~\\mathrm{nm}$ NIR light, the DOX release was further increased, showing the potential to control drug release with NIR light. In in vitro systems, the viability of cancer cells was dramatically inhibited by this combined strategy. Meanwhile, the tumor inhibition efficiency was effectively improved with this strategy in tumor models (Figure $\\mathrm{14g)}$ .[44]  \n\nBP based hydrogels are also used for drug delivery. Qiu et al. reported the application of low-melting point agarose based BP hydrogels for tumor specific delivery and NIR light controlled release of DOX. When irradiated with $808~\\mathrm{nm}$ NIR light, the hydrogel softened and melted because of the generation of heat by BP NSs, leading to release of DOX specifically in tumor tissues. Importantly, the rate of DOX release could be precisely controlled through modulation of the NIR light and hydrogel composition. Meanwhile, this BP hydrogel was highly biocompatible and degradable. Efficient inhibition of both breast cancer and melanoma was achieved with this BP hydrogel.[24c] Yang et  al. prepared a composite hydrogel with PDA modified BP NSs (pBP) and PVA through a freezing/thawing approach. The hydrogel was biocompatible and showed excellent mechanical properties. Because of the photothermal conversion of pBP, ondemand drug release was achieved with this hydrogel through NIR light stimulation.[63]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 4.2.3. Bone Regeneration  \n\nDamage to bones is widely occurring in injuries and diseases such as tumors and osteitis. Currently, autografts, allografts and artificial bone scaffolds, are much used in the clinic for the treatment of bone injuries. However, autografts of bones often result in damage to normal bones. Furthermore, allografts of bones are limited by the risk of immunological rejection and disease transmission. It is often more convenient and safer to use artificial bone scaffolds for the repair of bone injuries. However, it is still challenging to fabricate artificial bone scaffolds with excellent biocompatibility, osteoinduction, and osteointegration with traditional materials. The recent development of nanomaterials provides new opportunities for the design of better bone substitutes for repair of bone injuries.[169]  \n\nBP/polymers are also excellent candidates for design of artificial bone substitutes for the repair of bone injuries and regeneration of bones.[169] Compared with nanomaterials such as graphene, BP/polymers are superior in that the degradation of BP results in the formation of phosphate anions in situ to provide raw materials for the regeneration and mineralization of bones. Besides, the excellent photothermal conversion efficiency, the ROS production ability and the drug loading capability of BP make it possible for modulation of bone regeneration processes through diverse strategies. Furthermore, modification of BP with different polymers can enhance the biocompatibility, stability, and bone targeting efficiency, all contributing to better therapy effects.[169]  \n\nAs a critical constituent of bone, phosphorus is required for bone regeneration. A variety of materials containing phosphorus have been shown to promote the mineralization and regeneration of bones. Interestingly, the degradation of BP results in in situ production of $\\mathrm{PO}_{4}{}^{3-}$ , which participates in bio-mineralization through capturing of $\\mathrm{Ca}^{2+}$ . Increased abundance of phosphate ions in bone-forming cells treated with BP NSs promotes the formation of mineral clusters on endoplasmic reticulum (ER) membrane. The mineral clusters are transported from ER to mitochondria before they are further transported to extracellular matrices for the initiation of biomineralization.[171] Taking advantage of this unique character, Huang et  al. reported the preparation of a BP nanosheetbased hydrogel scaffold for bone regeneration through photocrosslinking of gelatin methacrylamide, BP NSs and cationic arginine-based unsaturated poly(ester amide)s. The embedding of BP NSs improved the mechanical properties of the hydrogel and enabled a photo-induced phosphate release. The osteogenic differentiation of dental pulp stem cells was improved by this hydrogel, and enhanced bone regeneration was also observed in vivo with this hydrogel.[86]  \n\nBesides, the highly efficient photothermal conversion of BP may also contribute to bone regeneration as mild heat stimulation already has been shown to stimulate such regeneration. Based on such phenomenon, Tong et  al. designed an osteoimplant with PLGA coated BP NSs. When stimulated with low intensity and periodic NIR light, the mild photothermal conversion of the implant stimulated the expression of heat shock proteins in tissues, leading to enhanced osteogenesis.[172] Wang et  al. also reported the application of PLGA coated BP QDs in bone regeneration (Figure  15a). To enhance the targeting efficiency, a cell-specific aptamer was utilized for the functionalization of the nanocomposites to prepare bioinspired matrix vesicles (Figure  15b,e). The stability of BP QDs was enhanced after PLGA functionalization (Figure  15c,d). The local concentration of inorganic phosphate was increased by this targeted delivery strategy, resulting in enhanced bio-mineralization. Meanwhile, light stimulation of the matrix vesicles increased the temperature and stimulated the expression of alkaline phosphatase and heat shock proteins, both of which contributed to bone regeneration (Figure  15f–h). In vivo experiments confirmed the highly efficient bone targeting ability of the bioinspired matrix vesicles (Figure  15i). As a result, the bone regeneration in vivo after injury was dramatically improved with this strategy (Figure 15j).[170] Pan et al. reported the treatment of rheumatoid arthritis with a plateletrich plasma-chitosan thermoresponsive hydrogel incorporated with BP NSs. The hyperplastic synovial tissue in inflamed joints was removed by heat and ROS generated from BP NSs in response to NIR light stimulation. The phosphate released from BP NSs thus provided materials for osteanagenesis. Meanwhile, the friction between tissues was reduced by the hydrogel. All of these processes contributed to the observed therapy outcomes of the hydrogel.[106]  \n\n![](images/eefc7525a9d3cd375418b1110157482881d4511d98c20b9b51f591cd565238ef.jpg)  \nFigure 14.  BP-PEG nanocomposite for tumor specific delivery and NIR light controlled release of DOX. a) Schematics for the functionalization of BP NSs with PEG and DOX loading on the BP-PEG nanocomposite. b) STEM image and EDS mapping of BP-PEG-FA nanosheets. c) UV–vis–NIR spectra of BP-PEG/DOX nanosheets at indicated drug feeding ratios. d) Drug loading capacity of a BP-PEG nanocomposite at indicated drug feeding ratios. e) NIR imaging of tumor bearing mice injected with BP-PEG/Cy7 (G1) or BP-PEG-FA/Cy7 (G2). f) Distribution of BP-PEG/Cy7 (G1) or BP-PEG-FA/Cy7 (G2) in main organs and tumors of the injected mice. g) Tumor inhibition efficiency of the indicated treatments. a–g) Reproduced with permission.[44] Copyright 2017, Wiley-VCH.  \n\n![](images/4ce62180849f663ada58785f8da7b6cf46769387354328b1b2d028f7fd8e4a2a.jpg)  \nFigure 15.  Bioinspired BP-PLGA matrix vesicles (MVs) for bone regeneration. a) Overview of the application of the MVs for bone regeneration. b) Preparation of the MVs. c) SEM image of the MVs. d) Photothermal conversion of the MVs after storage in PBS for indicated times. e) Osteoblast targeting ability of the MVs. f) Alizarin Red staining of cells after indicated treatments. g) ALP expression after indicated treatments. h) Runx2 expression after indicated treatments. i) Bone targeting efficiency of the MVs. j) Bone regeneration after indicated treatments. a–j) Reproduced with permission.[170] Copyright 2019, Springer Nature.  \n\nMaking use of the excellent drug loading capability of BP NSs, BP/polymers have also been successfully applied in delivery of drugs for bone regeneration. Wang et  al. reported an NIR light triggered delivery of $\\mathrm{SrCl}_{2}$ with BP based microspheres for bone regeneration. PLGA was coated onto the surface of the nanocomposites to enhance the stability and biocompatibility. When irradiated with NIR light, the flawing of the PLGA shells resulted in a controlled release of ${\\mathrm{Sr}}^{2+}$ , enabling precise control of drug release locally at optimal time periods. As an element with characteristics similar to calcium, strontium enhances bone regeneration through induction of osteoblast differentiation and inhibition of osteoclast activation.  \n\nExcellent bone regeneration capacity was achieved in a rat femoral defect model.[64]  \n\nExtracellular matrices are also critical for bone regeneration and BP/polymers can be used for modulation of extracellular matrices to promote bone regeneration. For example, Wang et  al. reported the construction of nanoengineered hydrogels through the incorporation of BP NSs into double network hydrogels to mimic the extracellular matrix microenvironment for induction of bone regeneration. The formation of CaP crystal particles was induced by BP NSs. An extracellular matrix microenvironment suitable for the differentiation of osteogenic cells and regeneration of bones was formed with this hydrogel.[90]  \n\nBP/polymers are also promising materials for fabrication of scaffolds for bone regeneration. Yang et al. reported the preparation of 3D printed scaffolds reinforced by BP for combined therapy of osteosarcoma enabled by the photothermal effects of the BP NSs. Meanwhile, the bio-mineralization driven by phosphorus promoted the regeneration of bone in situ.[173] Lee et  al. reported the fabrication of BP-incorporated poly(e-caprolactone) and collagen (PCL/BP/Col) nanofiber matrices as bone tissue engineering scaffolds. With excellent biocompatibility, the nanofiber matrices promote the implant, cell division, and osteodifferentiation of preosteoblasts.[85] Liu et al. reported the preparation of 3D printed scaffolds composed of BP and graphene oxide (GO) nanosheets for bone regeneration. Positively charged poly(propylene fumarate) was used as scaffolds for the adsorption of BP/GO composites. The surface area of the scaffolds was thereby increased, which is suitable for the attachment of cells. The differentiation of osteoblasts was stimulated by phosphate released from the degraded BP NSs. Both bio-mineralization and osteogenesis was enhanced with these 3D scaffolds.[174]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# 4.2.4. Gene Knockdown  \n\nModulation of gene expression levels, especially down-regulation of gene expression, is important for studies of gene functions and treatment of diseases. One of the most widely used tools for knockdown of gene expression is to use small interfering RNA (siRNA). Traditionally, siRNA is introduced into cells with transfection reagents such as lipofectamine. However, lack of targeting ability and the potential for side effects restrict the clinical application of this strategy. Recently, several kinds of newly discovered nanomaterials have been successfully used in loading, targeted delivery and controlled release of siRNA for gene knockdown. BP/polymers are also promising for this purpose. Zeng et al. prepared BP NSs-based nanocapsules with PDA modification for siRNA delivery and gene knockdown (Figure 16a). To enhance the tumor targeting efficiency, an AS1411 aptamer was attached to the nanocapsule through chemical reactions with PDA. Both DOX and siRNA targeting P-gp were successfully loaded into this nanocapsule. The release of DOX could be regulated by both acid and NIR light (Figure  16e). Meanwhile, efficient delivery of the siRNA in tumor cells resulted in downregulation of the P-gp protein expression (Figure 16f). The tumor resistance to DOX through P-gp was thus relieved (Figure  16g), contributing to the good breast cancer inhibition effect of nanocapsules (Figure 16h).[62] Wang et  al. designed BP based nanocomposites for silencing of Survivin expression. BP NSs were coated with polyethyleneimine for delivery of siRNA targeting Survivin. Knocking down of Survivin expression with these nanocomposites suppressed the growth of tumors and enhanced the tumor inhibition efficiency of PTT.[175]  \n\nBesides, clustered regularly interspaced short palindromic repeats (CRISPR)/Cas9 and related systems are also widely applied in down-regulation of gene expression. In these systems, both Cas9 proteins and guiding RNA are delivered into cells for gene editing or mRNA splicing. Nanomaterials including BP/polymers have also been investigated as carriers for delivery of these components to modulate gene expression. For example, Zhou et  al. reported effective gene-editing with the CRISPR/Cas9 system loaded on BP nanosheets. To enhance the loading and nuclear targeting efficiency, three nuclear localization signals were engineered to the C-terminal of Cas9 protein. The nanocomposites were taken up by cells through membrane penetration and endocytosis pathways. The biodegradation of BP resulted in endosomal escape and cytosolic release of the Cas9 complexes, leading to highly efficient gene-editing.[176] Recently, Yue et al. prepared PLL-functionalized BP nanosheets for delivery of the CRISPR/Cas13a system into tumor cells. A crRNA was codelivered to knock down the expression of Mcl-1. After endocytosis and endosomal escape, a knocking down efficiency of $58.64\\%$ was achieved with this nanocomposite, enabling the application of this strategy in tumor treatment.[108]  \n\n![](images/31c3526613ddcb9d4d91f87c8fd843c16203e90dd01da0c645af394721fdfd0e.jpg)  \nFigure 16.  Knocking down of P-gp protein with a PDA-modified BP nanocapsule for tumor treatment. a) Schematics for the preparation of the nanocapsule for siRNA delivery and tumor treatment. b) TEM images of the nanocapsule. c) AFM images of the nanocapsule. d) Height profiles along the lines in (c). e) Release of drug from the nanocapsule in acid environment with or without NIR light stimulation. f) Knocking down of P-gp with the nanocapsule. g) Release of drug in MCF/ADR cells. h) Tumor inhibition efficiency of the nanocapsule irradiated with NIR light. a–h) Reproduced with permission.[62] Copyright 2018, Wiley-VCH.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# 4.2.5. Biosensors  \n\nBiosensors are devices used to detect the existence and concentration of certain substances in biological systems. With the ability to detect various biomarkers with high sensitivity, biosensors have become important tools for diagnosis of human diseases such as cancer and neurodegenerative disease. Like many other nanomaterials, BP/polymers have been widely investigated for applications in biosensing of biological components and disease markers.  \n\nThe excellent photoelectric properties and biocompatibility of BP ensure the sensitive detection of various biological components, while the functionalization with different polymers enhances the stability of BP. For instance, Kumar et  al. proved the encapsulation of BP NSs with polypeptide micelles for fabrication of biosensors. BP NSs were exfoliated with sonication in a polar solvent. They were subsequently encapsulated with micelles prepared with PEG and poly(phenyl isocyanidepeptide) based copolymer blocks. The stability and biocompatibility of BP NSs were improved by this strategy. Meanwhile, the electronic properties of BP NSs were not affected, enabling integration in devices for biosensing.[72]  \n\nBiosensors based on BP/polymers have been successfully applied in detection of various substances. For example, Zhao et  al. prepared a biosensor composed of PLL and BP nanoflakes. A water-phase exfoliation protocol was developed for the preparation of BP nanoflakes (Figure  17a,b). The PLL was subsequently coated on the nanoflakes via hydrophobic and electrostatic interaction. Finally, hemoglobin (Hb) was attached to this PLL-BP hybrid. The protein conformation and function of the Hb was maintained. Direct electron transfer between Hb and electrode was detected and a good reduction activity toward $\\mathrm{O}_{2}$ and $\\mathrm{H}_{2}\\mathrm{O}_{2}$ was so observed with this biosensor (Figure 17c,d). A linear dependence between the electrochemical response and $\\mathrm{H}_{2}\\mathrm{O}_{2}$ concentration was also revealed (Figure  17e).[47] Zhen et  al. reported the preparation of a biosensor with a nanocomposite consisting of an ionic liquid, poly(diallyldimethylammonium chloride) and BP. Hb was then immobilized onto this nanocomposite. Electrocatalytic activity toward nitrite reduction was detected with high sensitivity and stability.[73] Zhang et al. also reported the fabrication of a vitamin C biosensor made of BP QDs, polypyrrole and poly(3,4-ethylenedioxythiophene) nanorods. A linear relationship between the peak currents and vitamin C concentration ranging from 0.01 to $4\\mathrm{mm}$ was observed. The detection limit was shown to be $0.0033\\mathrm{~mm}$ . Successful detection of vitamin C was achieved with this biosensor with excellent reproducibility, stability, and selectivity.[48]  \n\n![](images/56f3e2c33261a31384e65cff80712032b0946c7568adecd722ec463417d46673.jpg)  \nFigure 17.  Preparation of a $H\\mathsf{b}@$ pLL-BP biosensor. a) TEM images of BP nanoflakes collected at different centrifugation speeds (Left, 3000 rpm. Right, $5000~\\mathsf{r p m})$ . b) Raman spectra of BP nanoflakes and bulk BP. c) Cyclic voltammogram of $H b@$ pLL-BP glassy carbon electrode (GCE) saturated with $\\mathsf{N}_{2}$ air or $\\mathsf{O}_{2}$ . d) Cyclic voltammogram of Hb@pLL-BP GCE saturated with ${\\sf N}_{2}$ with or without ${\\sf H}_{2}{\\sf O}_{2}$ . e) Cyclic voltammogram of Hb@pLL-BP GCE in PBS with ${\\sf H}_{2}{\\sf O}_{2}$ of different concentration. a–e) Reproduced with permission.[47] Copyright 2018, American Chemical Society.  \n\nBP/polymers based biosensors have also been investigated for detection of proteins. For example, Liu et  al. reported the detection of lysozyme with a BP QDs-based biosensor. This biosensor was based on anodic electrogenerated chemiluminescence generated from a reaction of BP QDs and $\\mathrm{{Ru(bpy)}}_{3}{}^{2+}$ . Styrene-acrylamide copolymer nanospheres were used for encapsulation of BP QDs to enhance its stability and provide functional amino groups for connection with DNA. The nanospheres were then immobilized onto an electrode coated with lysozyme aptamers through the DNA. The specific interaction between lysozyme and the aptamer led to release of the nanospheres and decrease of the electrogenerated chemiluminescence signal. This enabled the detection of lysozyme with high sensitivity and selectivity.[71]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# 4.3. Energy Storage Devices  \n\nIn recent decades, energy storage devices have developed rapidly, such as Li-ion batteries and supercapacitors, due to the available portable electronics and the gradually growing demands of electrical energy storage/supplying components with high-performance.[3f,177] In this respect, BP possesses splendid properties like light molecular weight, large interlayer spacing $(5.3\\mathring\\mathrm{\\A})$ , high theoretical capacity $(2596\\ \\mathrm{mA}\\mathrm{h}\\ \\mathrm{g}^{-1})$ , and good electrical conductivity $(\\approx300\\mathrm{~S~m^{-1}})$ , something that has made BP become a reliable electrode material for energy storage devices.[178] Recent advances have thus witnessed the applications of BP/polymers in alkali-ion batteries, supercapacitors, and nanogenerators.[12c,179]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# 4.3.1. Ions-Batteries  \n\nIon batteries, like ${\\mathrm{Li^{+}}}$ and $\\mathrm{{Na^{+}}}$ batteries, have been considered as clean and efficient candidates for fabricating energy storage devices in large-scale.[180] BP has attracted lots of interest thanks to its high theoretical capacity and low working potential. Additionally, theoretical investigations have revealed that the large interlayer spacing of BP endows a fast intercalation and diffusion of metal ions.[181] Zarbin et al. fabricated PANI coated BP cathodes for aqueous Na-ion batteries, which exhibit a specific capacity of $200~\\mathrm{{mA}}$ h $\\boldsymbol{\\mathrm{g}}^{-1}$ after 50 cycles in NaCl solution under ambient conditions.[93] Wan’s group reported a ternary nanocomposite consisting of BP, graphite, and PANI (BP-G/PANI) for working as anodes of Na-ion batteries (Figure 18a).[70] They demonstrated that the nanocomposites can effectively reduce the charge transfer resistance, and can supply an optimized ion pathway from electrolyte to PANI to BP-G and finally to BP. Besides, the PANI can also prevent BP from volume expansion, which can ensure a stable cycling performance of the battery. The as-prepared battery shows a high reversible gravimetric capacity of $1530~\\mathrm{mA}$ h $\\mathrm{g}^{-1}$ and a capacity retention of $520\\ \\mathrm{mA}\\ \\mathrm{h}^{-1}$ after 1000 cycles as shown in Figure 18b,c. Subsequently, Duan and et al. demonstrated that BP can be applied as the active anode for high-rate, high-capacity, Li storage with robust cycle performance.[110] They reported that graphitic carbon can generate covalent bonds with restrained edge reconstruction within the layered BP particles, which can prevent the reconstruction of edges and ensure a fast entry of the ${\\mathrm{Li^{+}}}$ ions. Li et  al. prepared a PVA gel-polymer coated BP electrolyte for a three-electrode flexible zinc–nickel battery.[46] In the BP/PVA electrolyte, PVA served as the matrix while BP served as the barrier for $\\mathrm{Zn(OH)_{4}}^{2+}$ . The battery exhibited the typical flexibility (Figure  18d–f) and an initial discharge capacity of $509.8\\mathrm{\\mA}\\mathrm{\\h\\g}^{-1}$ , which can retain at $212.8\\mathrm{\\mAh}$ $\\mathbf{g}^{-1}$ after 100 cycles.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# 4.3.2. Supercapacitors  \n\nAs reliable fast charging energy storage devices to narrow the gap between capacitor and battery and owing to their great potential as a physical charge storage at the electrolyte/electrode interface, supercapacitors have been conceived to provide a stable power output after almost infinite numbers of cycles at a large current density.[183] BP/polymers have been applied for supercapacitors with exciting results due to their large surface area and the stacking layers for efficient intercalation of ions, see Table  5 which shows the comparison of the performance of BP/polymers based rechargeable supercapacitors.[182,184] Figure  19a shows the preparation of a hybrid nanocomposite electrode composed of BP NSs and PANI $\\mathrm{\\langleBP/}$ PANI) by Pumera and coworkers. [25d] The BP/PANI electrode shows a specific capacitance of $354\\ensuremath{\\mathrm{~F~}}\\ensuremath{\\mathrm{g}}^{-1}$ as the current density of $0.3\\mathrm{~A~g^{-1}}$ . Zhang’s group developed a flexible laminated self-standing PPy/BP film through the one-step method of electrochemical deposition.[25b] The flexible film exhibited a low internal resistance with excellent charging/discharging cycles, with about $60\\%$ and $92\\%$ reserved capacitance under a high current density $(10\\mathrm{~A~g^{-1}})$ and different bending angles, respectively (Figure  19b–d). Chen et  al. assembled BP and CNT into non-woven fiber fabrics for a flexible supercapacitor through a microfluidic-spinning technique.[25c] The flexible supercapacitor possessed enhanced conduction, remarkable mechanical stability, and plentiful ion channels (pores $<1\\mathrm{nm}$ ). Figure 19e demonstrates the preparation and potential applications of a CNTs/BP-CNT nanocomposite supercapacitor. Benefiting from the above merits, the supercapacitor showed a large volumetric capacitance $(308.7\\mathrm{~F~}\\mathrm{cm}^{-3}.\\$ ), a high energy density $(96.5\\mathrm{~mW~h~}\\mathrm{cm}^{-3})$ ), and enhanced long cycle stability during deformation, indicating a great potential for the design of nextgeneration wearable electronics.  \n\n![](images/47b2d5ff776511b9bb97e459b4bd64d5abcbf24b15d995169a36c1e3b15a2043.jpg)  \nFigure 18.  a) Schematic illustration of BP-G and BP-G/PANI electrodes. b) Rate performance of BP-G/PANI electrode. c) Cycling stability of BP-G/PAN electrode. d–f) Digital photographs of flexible zinc-nickel battery. a–c) Reproduced with permission.[70] Copyright 2019, American Chemical Society. (d–f) Reproduced with permission.[46] Copyright 2018, Elsevier.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 25,
+        "chunk": "# 4.4. Flame Retardancy  \n\nFlame retardancy technology has been established to satisfy the demands of social security development in fire protection, production and life, and protection of people’s lives and property.[185] Flame retardants are a kind of special chemical additives applied to enhance the combustion performance of combustible and flammable materials and which are generally applied for the flame retardancy processing of various decoration materials.[186] The materials that contain flame retardants can effectively delay, prevent or even terminate the spread of flames as they come into contact with external fire sources, so as to achieve the effect of flame retardancy. Similarly to graphene, and as one of the most adopted additives in polymer nanocomposites, few-layer BP has been considered as a novel nanofiller for manufacturing flame retardants owing to its outstanding features like mechanical property, thermal stability, and characteristic dimension effects.[77,96–98]  \n\nBP/graphene composites were distributed in waterborne PUA $(\\mathrm{BP/G}@\\mathrm{WPUA})$ by Luo et al.[59] The cone calorimeter tests reveal that BP/G/WPU exhibits a lower peak heat release rate (PHRR) of $235.4\\mathrm{kW}\\mathrm{m}^{-2}$ and total heat release of 51.68 MJ $\\mathrm{m}^{-2}$ , respectively. Tan et al. reported a melamine-formaldehyde (MP) functionalized BP $(\\mathrm{BP}@\\mathrm{MF})$ with the adsorption energy of $-0.63\\ \\mathrm{eV},$ indicating a strong mutual adsorption between MF and BP.[97] The further epoxy resin (EP) incorporated ${\\mathrm{BP}}\\ @{\\mathrm{MF}}$ shows a residual char of $19.4\\%$ at $400~^{\\circ}\\mathrm{C}$ . Hu et  al. fabricated $\\mathrm{-NH}_{2}$ group abundant PZN functionalized BP NSs (BP/PZN) through polymerizing hexachlorocyclotriphosphazene and $^{4,4^{\\prime}}$ -diaminodiphenyl ether on BP NSs.[76] EP was further used to coat BP/PZN for investigating its flame retardancy properties. As shown in Figure 20a, BP plays a special role to promote the formation of char as it captures most of the free radicals. The unique layered structure of BP can act as a special physical barrier, which can effectively insulate both oxygen and heat during the combustion process. Calorimeter test results show that there are about $859.5~\\mathrm{kW~m}^{-2}$ and 60.8 MJ $\\mathrm{m}^{-2}$ in PHRR and THR in $2\\mathrm{wt\\%}$ BP/PZN@EP at around $450^{\\circ}\\mathrm{C}$ , respectively. Figure 20b shows photos of the external residues of pure EP and $\\mathrm{BP/PZN}@\\mathrm{EP}$ from top and side views. There are few residual chars that can be seen in the pure EP while the residual chars show a gradually increasing trend in both amount and size with the increased contents of BP. Table  6 lists the summary of the performance of BP as an additive for flame retardancy. It is found that a certain amount doping of BP has great potential for fabricating nanocomposites with high-performance.  \n\nTable 5.  The performance of BP/polymers based rechargeable supercapacitors.   \n\n\n<html><body><table><tr><td>Materials</td><td>Type</td><td>Potential</td><td>Capacitance</td><td>Capacity retention</td><td>Ref</td></tr><tr><td>BP/PPy</td><td></td><td>-0.2-0.8V</td><td>515 F g-1 (1 A g-1)</td><td>48% (1000 cycles)</td><td>[182]</td></tr><tr><td>BP/PPy</td><td>Flexible</td><td>-0.1-0.7 V</td><td>497.5 F g l (0.5 A g-l)</td><td>65% (10 000 cycles)</td><td>[25b]</td></tr><tr><td>BP/PANI</td><td></td><td>-0.4-0.6 V</td><td>354 F g-l (0.3 A g-l)</td><td>-</td><td>[25d] </td></tr><tr><td>BP/CNTs/TPU</td><td>Flexible</td><td>0-3V</td><td>308.7 F cm-3 (0.1 A cm-3)</td><td>97.4% (1000 cycles)</td><td>[25c]</td></tr></table></body></html>  \n\n![](images/ee70fdd287b2b74ddbc60f915f9ab1b012d48f46c2c9152f041f4d5855091310.jpg)  \nFigure 19.  a) Schematic of fabrication of BP/PANI nanocomposite electrode. b) Cyclic voltammetry (CV) curves and c) galvanostatic charging/discharging (GCD) curves of PPy/BP film. d) Flexible performance of PPy/BP film under different bending angles. e) Illustration of a flexible CNTs/BP-CNTs nanocomposite supercapacitor via the hot-pressing method and the potential for electronic applications. Reproduced with permission.[25b,25d] Copyright 2018, American Chemical Society. Reproduced with permission.[25c] Copyright 2018, Springer Nature.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 26,
+        "chunk": "# 4.5. Information Storage  \n\nThe accelerating development of the electronic information industry has promoted a lot of new technologies, including artificial intelligence, virtual reality, quantum information technology and so on, which has given rise to the fourth industrial revolution and a hastening of the end of the third. Thus, information storage has been considered as an essential area of social development. Resistive random access memories (RRAM), a newly emerged non-volatile technology with the advantages of simple structure and excellent data storage capacity has been widely explored for new-generation data storage applications in recent decades.[187]  \n\n![](images/ef1797e31dadaa3bf19211c468118d705b4ad9609b111b0615c2822ce9c6f522.jpg)  \nFigure 20.  a) Mechanism illustration of BP/PZN@EP composites. b) Digital photos of residue chars of pure EP and BP/PZN@EP from top and sid views. Reproduced with permission.[76] Copyright 2019, Wiley-VCH.  \n\nBP has been recognized as a promising material for fabricating information storage devices owing to its small switching bias window and high ON/OFF ratio which can effectively decrease the information misreading rate and unnecessary power consumption of memory devices. Peng et al. systematically investigated the memory characteristics of BP QD based resistive RRAMs through ex- and in situ control methods as shown in Figure 21a.[41] A large ON/OFF ratio of $3.0\\times10^{7}$ was found for the as-prepared memory device. Figure  21b shows a photograph and an illustration of BP/PVP-based memory devices by Zhang et  al.[32] The electronic and switching characteristics (Figure  21c) reveal the full electrically bistable behavior of the BP/PVP-based device. The high-resistance state (HRS) (OFF state) and low-resistance state (LRS, that is, ON state) represent the writing process as for typical digital memory devices. The device shows a high ON/OFF ratio of $6.0\\times10^{4}$ together with excellent stability for both the HRS and LRS, which demonstrated that the BP/PVP nanocomposite can serve as an electrically bistable material for flash memory devices. Chen et  al. reported an in situ synthesis of PDDF covalently functionalized BP for fabricating an RRAM device (Au/PDDF-g-BP/ITO).[58] The device exhibits a rewritable memory performance with a high ON/OFF ratio of $10^{4}$ and voltages of $+1.95$ and $-2.34\\mathrm{~V~}$ for turn on and off, respectively (Figure  21d–f). They further applied PFCz as the synthetic precursor to react with BP, and the as-prepared Al/PFCz-g-BP QDs/ITO device showed a large ON/OFF ratio of $10^{7}$ as well as low turn-on/off voltages of $-0.89/+1.95\\mathrm{~V}.$ Table  7 shows a comparison of memory performances of BP/polymers-based devices, suggesting that BP/polymers are promising candidates for RRAM devices.  \n\nTable 6.  Performance summary of flame retardants doped with BP.   \n\n\n<html><body><table><tr><td>Materials</td><td>BP content [wt%]</td><td>TPHRR[S]</td><td>PHRR</td><td>THR</td><td>Residual char [wt%]</td><td>Ref</td></tr><tr><td>BP/G@WPU</td><td>2.0</td><td>-</td><td>235.4 kW m-2</td><td>51.7 MJ m-2</td><td>12.5</td><td>[59] </td></tr><tr><td>BP/PZN@EP</td><td>2.0</td><td>149</td><td>859.5 kW m-2</td><td>60.8 MJ m-2</td><td>-</td><td>[76]</td></tr><tr><td>BP/EC@PUA</td><td>3.0</td><td>-</td><td>355.4Wg-l</td><td>34.9 k) gl</td><td>一</td><td>[77]</td></tr><tr><td>BP/TA@TPU</td><td>2.0</td><td></td><td>562.0 kW m-2</td><td>45.5 MJ m-2</td><td>9.7</td><td>[95] </td></tr><tr><td>BP/IL@TPU</td><td>1.5</td><td>一</td><td>700.0 W m-2</td><td>70.4 Mj m-2</td><td>6.3</td><td>[96] </td></tr><tr><td>BP/MF@EP</td><td>1.2</td><td>315</td><td>623.7 W g-l</td><td>34.6 k) g-l</td><td>19.4</td><td>[97]</td></tr><tr><td>BP/MCNTs@EP</td><td></td><td>120</td><td>988.6 kW m-2</td><td>63.5 MJ m-2</td><td>-</td><td>[98] </td></tr><tr><td>BP/(CFSO3)Er@EP</td><td>3.0</td><td>一</td><td>1450.0 kW m-2</td><td>65.7 MJ m-2</td><td>-</td><td>[99] </td></tr><tr><td>BP/graphene@ EP</td><td>2.0</td><td>-</td><td>1461.9 kW m-2</td><td>105.6 Mj m-2</td><td>48.0</td><td>[100] </td></tr><tr><td>BP/PVA@PDA</td><td>5.0</td><td></td><td>216.1 W g-l</td><td>34.2 k) g </td><td>5.4</td><td>[101] </td></tr><tr><td>BP/PEI@PUA</td><td>2.0</td><td></td><td>1158.0 kW m-2</td><td>71.0 MJ m-2</td><td>-</td><td>[102] </td></tr><tr><td>BP/COF@EP</td><td>2.0</td><td></td><td>796.7 kW m-2</td><td>74.9 MJ m-2</td><td>_</td><td>[103] </td></tr><tr><td>BP/TPU</td><td>2.0</td><td></td><td>507.0 kW m-2</td><td>52.0 MJ m-2</td><td>-</td><td>[111] </td></tr><tr><td>BP/graphene@TPU</td><td>0.9</td><td>二</td><td>1048.0 kW m-2</td><td>117.0 M) m-2</td><td>8.9</td><td>[112]</td></tr></table></body></html>\n\n$T_{\\mathsf{P H R R}}.$ : Time to PHRR.  \n\n![](images/be64a4c3b247c29f2cfb4ecad46abfd143d26aee44ea12b3be7cf384e8a53296.jpg)  \nFigure 21.  a) The preparation process of flexible BP/PMMA-based RRAMs. b) Illustration of BP/PVP-based memory device. c) The $1-V$ characteristics of a BP/PVP-based memory device. d) Effects of continuous read pulses on ON/OFF states current of the devices of $\\mathsf{I}.0\\mathsf{V}$ (pulse width $=70~\\mathrm{ms}$ , pulse period $=20~\\mathrm{ms}^{\\prime}$ ). e) $1-V$ curves of the devices. f) I–V curves of the device kept in ambient for over 90 days. a–f) Reproduced with permission.[32,41,58] Copyright 2019, Wiley-VCH.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 27,
+        "chunk": "# 4.6. Other Applications  \n\nApart from the above applications, BP/polymers have also been widely applied in other fields due to their excellent properties. Li and coworkers developed a washable skin touch-actuated textile-based triboelectric nanogenerator consisting of BP and hydrophobic cellulose oleoyl ester nanoparticles on a PET fabric as shown in Figure 22a.[188] Such a prepared device reveals excellent reliability together with high triboelectricity under extreme conditions like hard washing, severe deformation, and longterm exposure under ambient conditions. Zeng et al. obtained a BP NSs/PI for ceramic-based dielectrics, which showed good interfacial compatibility, a high-permittivity value of 8.6 at $100\\mathrm{Hz}$ , and a low dielectric loss value of 0.02.[94] Lin et al. found that the appropriate addition of BP NSs in PEDOT:PSS could significantly increase the electrical conductivity (Figure 22b).[34] Soon afterward, Jeon et  al. demonstrated that the doping of BP NSs, with $2\\mathrm{\\wt\\%}$ addition, in PEDOT:PSS exhibits a power factor of $36.2\\upmu\\mathrm{W}\\mathrm{m}^{-1}\\mathrm{K}^{-2}$ , which is about $109\\%$ higher than for the pure PEDOT:PSS film (Figure 22c,d).[56] BP NSs were incorporated with PLGA fibers through a solution blow spinning method, which exhibits tunable release rates of phosphate ions and presents a great potential for bone tissue engineering.[57] Qaiss et  al. claimed that the addition of BP NSs into PVDF could dramatically decrease the thermal stability, and shown that the electrical conductivity could be sharply increased from $3.3\\times10^{-14}$ to $5\\times10^{-11}\\mathrm{S}\\mathrm{cm}^{-1}.^{[74]}$ Luo and coworkers found that the coefficient of friction decreased from 0.117 to 0.046 due to the constantly supplied BP NSs into the contact area with phosphorus oxide and phosphoric acid on the counterpart surface (Figure 22e,f ).[55,189]  \n\nTable 7.  The memory performance comparisons of BP/polymers-based RRAM devices.   \n\n\n<html><body><table><tr><td>Materials</td><td>Memory effect</td><td>Cycles</td><td>ON/OFF ratio</td><td>Switch-on voltage/V</td><td>Stability/s</td><td>Ref.</td></tr><tr><td>BP/PVP</td><td>Rewritable</td><td></td><td>4.0 × 104</td><td>-1.20</td><td>10</td><td>[32]</td></tr><tr><td>BP/PMMA</td><td></td><td>100</td><td>3.0×106</td><td>-2.80</td><td>104</td><td>[4]</td></tr><tr><td>BP/g-PDDF</td><td></td><td>200</td><td>1.0 × 104</td><td>+1.95</td><td>104</td><td>[58] </td></tr><tr><td>BP/g-PFCz</td><td></td><td>600</td><td>1.3 ×10</td><td>-0.89</td><td>104</td><td>[75]</td></tr></table></body></html>  \n\n![](images/59b5e1e69d231272b588ba11c00884a07f81d7e203f1feeeffffeb95e0259ffc.jpg)  \nFigure 22.  a) The fabrication process of a textile BP/polymer nanogenerator. b) Thermoelectric parameters of BP/PEDOT: PSS file. c,d) Release dynamics of BP/PLGA nanocomposite. e) Coefficient of friction as a function of time for BP/PEFE. f) Dielectric loss of BP/PI nanocomposite. a) Reproduced with permission.[188] Copyright 2018, Springer Nature. b–d) Reproduced with permission.[56,57] Copyright 2018, American Chemical Society. e) Reproduced with permission.[55,74] Copyright 2018–2019, Elsevier.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 28,
+        "chunk": "# 5. Conclusion  \n\nSince the first appearance of few-layer black phosphorous (BP) in transistors in 2014, a large amount of attention has been attracted to explore its properties and applications. The special advantages of BP, like tunable band gap, high ON/ OFF ratio, and anisotropy in optical and thermal properties have made it stand out from other monoelemental nanomaterials. However, along with the research and development, the environmental instability of BP has been found to severely disturb its practical applications. This fact has triggered a number of strategies to improve the environmental stability of BP for its further use. In this review article, we have presented a comprehensive summary of recent progress on research of BP/polymer nanocomposites, including preparation methods, properties, and applications in the optical, biomedical, energy, information storage and flame retardancy sectors. Solution casting, polymerization methods and spinning technology methods are the three main categories of methods to fabricate BP/polymer nanocomposites among the various preparation methods. Benefiting from the encapsulation of different polymers, BP can be well protected in a polymer matrix and some properties can be significantly improved, such as optical absorption, mechanical strength, and environmental stability, which endow a further broad range of investigations of BP. For instance, functionalization of BP with various polymers has been shown to be effective for enhancing the stability of BP based nanomaterials in physiological conditions. More importantly, conjugation of BP with suitable polymers may also enhance the targeting specificity, drug loading efficiency, photo response, and the mechanical properties of BP based nanocomposites, thus significantly promoting the clinical applications of BP in these fields.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 29,
+        "chunk": "# 6. Challenges  \n\nDespite the above advantages of BP/polymers, there are still many challenges that call for attention. First of all, the preparation methods of BP/polymers should be further optimized, for example, obvious flaws of single crystalline methods are the complex and uncontrollable modification processes of BP. It is necessary to simplify the traditional preparation routes with precise additions of each component. Such precise modulations of BP/polymers with high targeting efficiency, bioimaging capability, and multimodal treatment ability are essential for theranostics of diseases, especially tumors. With proper design of BP/polymer based therapy strategies, the shortcomings of traditional therapy may be overcome. For example, chemotherapy is limited by side effects caused by systematic administration of drugs in a tumor treatment. Loading of chemotherapy drugs onto BP/PEG-FA nanosheets enables tumor targeted delivery and NIR light controlled release of drugs specifically in tumor tissues. Besides, a search for suitable polymers with good fluidity, homogeneity, and large cohesion to prepare BP/polymer spinning fluids is also necessary for the continuous spinning flow and fabricating devices with high-performance. Second, rational selection and utilization of polymers, including the type of polymers, the procedure of functionalization and the thickness of the polymers, is another important issue for improving the stability of BP/polymers. For example, the adjustable stability of BP/polymers is also important for their applications. BP/polymersbased photo electronics exhibits more stable signal output than pristine BP-based devices, which represents a practical aspect. Besides, BP/polymers with relatively high stability are beneficial for reducing the side-effects caused by nonspecific drug release from degradation of the drug carriers, and $\\mathsf{B P}/$ polymers with moderate stability are ideal to support bond regeneration through the sustained in situ supply of phosphorus. Third, BP based mode-lockers exhibit more potential advantages for mid-infrared ultrafast laser systems owing to that the direct bandgap reaches $0.3\\ \\mathrm{{\\eV}}.$ Nowadays, the poor stability can be effectively enhanced by BP/polymers, which will promote the development of BP/polymer mode-lockers in the mid-infrared region. Besides that, most of BP/polymers in ultrafast lasers are used for improving the stability, if the incorporation polymer can promote the properties of BPSA, such as increasing the modulation depth or reducing the response time, it will be useful for the ultrashort pulse generation. Therefore, more research is needed to explore $\\mathsf{B P}/$ polymer mode-lockers. Moreover, a comprehensive investigation of the biocompatibility of BP/polymers is still needed. Much research has been conducted to check the biocompatibility of various BP/polymer nanocomposites, especially those applied in biomedical research. Nevertheless, some of this research is still at its infancy. More comprehensive investigations on BP/polymer-induced acute and long-term effects in the body, especially on the immune, nervous and reproductive systems, is critical for the practical applications of these novel materials. Moreover, a systematic evaluation of the ecological impact of BP/polymers is also urgently needed. Moreover, BP/ polymers have also shown excellent applications in the fields of energy storage, flame retardancy and information storage. Studies on these aspects are ascending, and there are still many areas that need to be further improved. For example, a search for more matching polymers to prepare electrode materials with higher flexibility and stability would be significant for wearable devices. Last but not least, studies of the anisotropy of BP/polymers for their optical, thermal and mechanical properties, and the construction of multifunctional $\\mathsf{B P}/$ polymers constitute promising avenues for new-generation applications.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 30,
+        "chunk": "# Acknowledgements  \n\nY.Z., C.M., and J.X. contributed equally to this work. The research was financially supported by the National Natural Science Fund (Grant No. 61905157), Fund of University of South China (Grant No. 201RGC009), Postdoctoral Research Foundation of China (Grant No. 2020M672786), and the Natural Science Foundation of Guangdong Province (No. 2019A1515111060).",
+        "category": " Acknowledgements"
+    },
+    {
+        "id": 31,
+        "chunk": "# Conflict of Interest  \n\nThe authors declare no conflict of interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 32,
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Ed. 2014, 53, 5556; c) J. Gu, C. Liang, X. Zhao, B. Gan, H. Qiu, Y. Guo, X.  Yang, Q.  Zhang, D.  Wang, Compos. Sci. Technol. 2017, 139, 83; d) X.  Wang, E. N.  Kalali, J.  Wan, D.  Wang, Prog. Polym. Sci. 2017, 69, 22. [187]\t a) S. Liu, X. Chen, G. Liu, Polym. Int. 2020, https://doi.org/10.1002/ pi.6017; b) Q.  Zhao, Z.  Xie, Y.  Peng, K.  Wang, H.  Wang, X.  Li, H.  Wang, J.  Chen, H.  Zhang, X.  Yan, Mater. Horiz. 2020, 7, 1495. [188]\t J.  Xiong, P.  Cui, X.  Chen, J.  Wang, K.  Parida, M. F.  Lin, P. S.  Lee, Nat. Commun. 2018, 9, 4280. [189]\t Y. Lv, W. Wang, G. Xie, J. Luo, Tribol. Lett. 2018, 66, 61.  \n\n![](images/8153b6944183cb97778ef8470d13a4afd0a249ce2e48252b5cc44c64eb34dc32.jpg)  \n\nYe Zhang received his Ph.D. in applied chemistry at Soochow University in 2018. He is currently a professor in the School of Chemistry and Chemical Engineering at University of South China, Hengyang, China. His research interests focus on the development of novel two-dimensional materials and their derived nanodevices.  \n\n![](images/9e5205ed31c4c7445011a184e162ccaf07f7b4632d2e2233c4292b1afea829e6.jpg)  \n\nChunyang Ma gained his Ph.D. in electronic science and engineering from Jilin University, China. He is now a postdoctor in the Institute of Microscale Optoelectronics, Shenzhen University, China. His research interests concern the nonlinear optical properties of 2D materials and related applications in optoelectronic devices and ultrafast photonics.  \n\n![](images/3bfb3d0bed142c0f4d7f04f56c37be9305d4f8cb39a1d38aaa9e96ef8f030548.jpg)  \n\nJianlei Xie received his Ph.D. from School of Life Sciences at Tsinghua University in 2018. He is now a postdoctor in the Institute of Microscale Optoelectronics, Shenzhen University, China. His research interests focus on the biomedical application of nanomaterials.  \n\n![](images/26a6518765faff6f2ee3c3ec72b819ac28b3fa46b81ce89c567f87566beef8a8.jpg)  \n\nHans Ågren is professor at the Department  of Physics and Astronomy, Uppsala University. His research activities concern molecular/nano/bio photonics and electronics, computational nanoand bio-technology, being a mix of method development and problem-oriented applications.  \n\n![](images/22b713b512c656fb39c33294a7840e95f455088f4b096940948b8e07778660b8.jpg)  \n\nHan Zhang is currently a full professor in the College of Physics and Optoelectronic Engineering at Shenzhen University in China. He is interested in the development of novel two-dimensional materials and their applications in optoelectronics, bio-medicine, and energy storage.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Dual-Functional Antifogging/Antimicrobial Polymer Coating  \n\nJie Zhao,† Li Ma,‡ William Millians,† Tiehang Wu,§ and Weihua Ming\\*,† †Department of Chemistry, Georgia Southern University, P.O. Box 8064, Statesboro, Georgia 30460, United States ‡Department of Physics, Georgia Southern University, P.O. Box 8031, Statesboro, Georgia 30460, United States §Department of Biology, Georgia Southern University, P.O. Box 8042, Statesboro, Georgia 30460, United States  \n\nABSTRACT: Dual-functional antifogging/antimicrobial polymer coatings were prepared by forming a semi-interpenetrating polymer network (SIPN) of partially quaternized poly(2-(dimethylamino)- ethyl methacrylate-co-methyl methacrylate) and polymerized ethylene glycol dimethacrylate network. The excellent antifogging behavior of the smooth coating was mainly attributed to the hydrophilic/hydrophobic balance of the partially quaternized copolymer, while the covalently bonded, hydrophobic quaternary ammonium compound ( $5\\mathrm{mol}\\%$ in the copolymer) rendered the coating strongly antimicrobial, as demonstrated by the total kill against both Gram-positive Staphylococcus epidermidis and Gramnegative Escherichia coli. The antimicrobial action of the SIPN coating was based on contact killing, without leaching of bactericidal species, as revealed by a zone-of-inhibition test. This type of dual-functional coating may find unique applications where both antimicrobial and antifogging properties are desired.  \n\n![](images/5543a7319d3caadd82f3f032132be89b3e2a0dad6bc11d904d6e8e524126f5de.jpg)  \n\nKEYWORDS: functional coating, antifogging, antimicrobial, quaternary ammonium compound (QAC), semi-interpenetrating polymer network (SIPN)",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# INTRODUCTION  \n\nFogging can significantly reduce the clarity of a transparent substrate, resulting in not only inconvenience but also potential danger in daily life. Therefore, there has been great demand for effective antifogging surfaces1−5 that can be applied in windshield, eyeglass, camera lens, mirror, goggle, display device in analytical instrument, and so on. For medical procedures, such as laparoscopic6,7 and endoscopic ones,8,9 lens fogging is a common problem and may lead to sudden loss of vision for the operator and interruption of the procedure, potentially provoking complications.  \n\nAn extensively reported strategy to mitigate fogging problems is to apply a superhydrophilic coating, since condensing water vapor would form a very thin water layer on a superhydrophilic surface, leading to much reduced light scatterin g.10−20 However, complicated procedures were normally used to prepare superhydrophilic surfaces.10−17 It was recently suggested that dry antifogging could be obtained on a superhydrophobic surface,21 which has not yet been materialized. In addition, both superhydrophilic and superhydrophobic surfaces may suffer from mechanical vulnerability due to their microroughened surface.  \n\nOn the other hand, a surface does not have to be superhydrophilic to be effectively antifogging, and smooth antifogging coatings22−27 have been recently prepared by carefully balancing the hydrophilicity and hydrophobicity of a coating, such as an antifogging/self-cleaning coating with both perfluoroalkyl and poly(ethylene glycol) (PEG) segments22 and zwitter-wettable, antifogging coatings via layer-by-layer assembly involving PEG segments23 or a chitosan/cellulose complex.24 We recently developed a smooth antifogging coating based on a semi-interpenetrating polymer network (SIPN) comprising either a binary copolymer25 poly(2- (dimethylamino)ethyl methacrylate-co-methyl methacrylate) [poly(DMAEMA-co-MMA)] or a terpolymer26 containing DMAEMA segments and a network from polymerized ethylene glycol dimethacrylate (EGDMA). Different from a superhydrophilic antifogging surface, smooth coatings with a proper hydrophilic/hydrophobic balance can rapidly absorb water from the surrounding,23−26 not allowing the formation of discrete water droplets on the surface.  \n\nFor medical devices, a common way to prevent lens fogging is to apply an antifog solution, but it is only temporary and normally requires multiple applications during a medical procedure.6,8,9 Therefore, there is great need for more effective, permanent antifogging coatings for medical devices. Furthermore, it would be advantageous if the antifogging coating was also antimicrobial, which may help reduce, and even eliminate, potential pathogenic infection. There have been very few studies28,29 on coatings that are both antifogging and antimicrobial, one based on a superhydrophilic polymer− ${\\cdot\\mathrm{SiO}_{2}}$ nanocomposite28 and the other on a UV-cured coating;29",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# Scheme 1. Schematic Illustration of Partial Quaternization of Poly(DMAEMA-co-MMA)  \n\n![](images/f976feadfcb725d9021cc3b73f5585286bc30449941d46ebade124f1c8600d0a.jpg)  \n\nhowever, the combined antifogging and antimicrobial performance still needs major improvement.  \n\nIn this work, we describe a dual-functional antifogging/ antimicrobial coating based on a SIPN between the partially quaternized linear copolymer poly(DMAEMA-co-MMA)25 and polymerized EGDMA network. We envisaged that the incorporation of a proper amount of covalently bonded, hydrophobic quaternary ammonium compound (QAC) would render the SIPN coating highly antimicrobial, while the excellent antifogging property that originated from the binary copolymer poly(DMAEMA-co-MMA) was maintained. QACs, especially those with long hydrophobic tails, have been extensively incorporated into antimicrobial coatings30−42 due to their strong antimicrobial activity. The dual-functional SIPN coating can be obtained in three simple steps: (1) synthesis of poly(DMAEMA-co-MMA);25 (2) partial quaternization of poly(DMAEMA-co-MMA), leading to various QAC amounts in the copolymer; and (3) formation of SIPN coatings25,26 via photopolymerization of EGDMA in the presence of the partially quaternized copolymer.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# EXPERIMENTAL SECTION  \n\nMaterials. Monomers including 2-(dimethylamino)ethyl methacrylate (DMAEMA, $98\\%$ ) and ethylene glycol dimethacrylate (EGDMA, $99\\%$ ), and free radical initiators including azobis(isobutyronitrile) (AIBN, $99\\%$ ) and 2-hydroxy-4-(2-hydroxyethoxy)- 2- methylpropiophenone (HHMP, $98\\%$ ) were purchased from Aldrich. Methyl methacrylate (MMA, $99\\%$ ) and 1-bromoundecane were purchased from Alfa Aesar. Inhibitor was removed from MMA and EGDMA by passing them through an aluminum oxide column. Solvents including toluene, $n$ -hexane, acetonitrile, chloroform, acetone, and ethanol were purchased from Fisher and used as received.  \n\nSynthesis of Copolymer Poly(DMAEMA-co-MMA). The copolymer was prepared via a free radical solution polymerization25 as follows. Into a $250~\\mathrm{mL}$ flask were added $9.6~\\mathrm{g}$ of DMAEMA (0.6 mmol) and $2.0\\ \\mathrm{g}$ of MMA $\\left(0.2\\mathrm{\\mmol}\\right)$ , and toluene was added to obtain 10 wt $\\%$ solution, followed by the addition of $0.058\\ \\mathrm{g}$ of AIBN as the thermal initiator (0.5 wt $\\%$ with respect to the total monomer mass). After being purged by argon for $20~\\mathrm{{min};}$ , the polymerization was conducted at $70~^{\\circ}\\mathrm{C}$ for $^{24}\\mathrm{~h,~}$ and the final binary copolymer poly(DMAEMA- $c o$ -MMA) with $75\\mathrm{\\mol}\\mathrm{\\}\\%$ of DMAEMA segments, designated as B-75, was purified by repeated dissolution in chloroform and precipitation in hexane.  \n\nPartial Quaternization of Poly(DMAEMA-co-MMA). The partial quaternization of poly(DMAEMA-co-MMA) was carried out via its reaction with various amounts of 1-bromoundecane (Scheme 1). The binary copolymer B-75 $(1.0\\mathrm{g})$ and $_{0.063\\mathrm{~g~}}$ of 1-bromoundecane ( $5\\mathrm{\\mol\\}\\%$ with respect to the DMAEMA units in B-75) were first dissolved in $15\\ \\mathrm{mL}$ of acetonitrile in a $50~\\mathrm{mL}$ flask, followed by reaction at $70~^{\\circ}\\mathrm{C}$ for $24\\mathrm{~h~}$ . The product was then purified after dissolution in chloroform and precipitation in hexane and dried in a vacuum oven at $45~^{\\circ}\\mathrm{C}$ for $24\\mathrm{~h~}$ . The partially quaternized copolymer with a $95\\%$ yield was labeled as $\\mathbf{Q}{\\cdot}5,$ according to the molar fraction of the QAC unit in the final copolymer. Similarly, partially quaternized copolymers with higher QAC contents, $Q=7$ and $\\mathrm{Q}{\\cdot}10.$ , were synthesized. The molar percentage of three monomer units (QAC, DMAEMA, and MMA units) in the quaternized copolymers was determined by ${}^{1}\\mathrm{H}~\\mathrm{NMR},$ as listed in Table 1.  \n\nTable 1. Copolymer Composition (calculated from ${}^{1}\\mathbf{H}$ NMR) and Glass Transition Temperature ( $T_{\\mathrm{g}},$ determined by DSC) for B-75 and Partially Quaternized Copolymers   \n\n\n<html><body><table><tr><td>copolymer</td><td>molar composition QAC:DMAEMA:MMAa</td><td>Tg (C)</td></tr><tr><td>B-75</td><td>0:75.0:25.0</td><td>39.6</td></tr><tr><td>Q-5</td><td>4.7:71.9:23.4</td><td>43.5</td></tr><tr><td>Q-7</td><td>6.8:67.9:25.3</td><td>46.7</td></tr><tr><td>Q-10</td><td>10.3:64.6:25.1</td><td>56.8</td></tr></table></body></html>\n\naQAC refers to the quaternized DMAEMA unit.  \n\nSIPN Coating Preparation. Glass slides $(2.2\\times2.2~\\mathrm{cm}^{2}.$ ) were consecutively sonicated in acetone and ethanol for $30~\\mathrm{\\min}$ and followed by blow-drying with air. A copolymer (B-75, Q-5, $\\Q=7,$ or $\\mathsf{Q}_{-}$ $\\left.10,0.2\\ g\\right)$ , EGDMA (0.5 wt $\\%$ with respect to the copolymer, which is the optimal amount, as determined previously25), and HHMP (2.0 wt $\\%$ relative to EGDMA) were codissolved in $2~\\mathrm{mL}$ of toluene to obtain homogeneous solutions. The solution was spin-coated on a clean glass slide at $800~\\mathrm{rpm}$ for $15\\ \\mathrm{s}.$ . After that, the coating was cured under UV irradiation using HHMP as the photoinitiator in a UVP CL-1000 ultraviolet cross-linker apparatus $(365\\mathrm{nm},15\\mathrm{W})$ for $45\\ \\mathrm{min},$ and then dried in a vacuum oven at $70^{\\circ}\\mathrm{C}$ for $24\\mathrm{h}$ . The resulting SIPN coatings were labeled as SIPN-B-75, SIPN-Q-5, SIPN-Q-7, and SIPN-Q10, respectively, according to the copolymer used. These coatings were typically about $800\\ \\mathrm{nm}$ thick (determined by atom force microscopy), which was sufficient to ensure excellent antifogging performance.  \n\nFogging Test. A sample was first stored in a freezer at $-20{}^{\\circ}\\mathrm{C}$ for $30~\\mathrm{min}.$ , and photos were taken 5 s after the sample was exposed to ambient conditions ( $\\mathrm{\\Omega}\\sim20\\ {^\\circ}\\mathrm{C},$ $50\\%$ relative humidity). An antifogging experiment was also performed by holding the sample $5\\ \\mathrm{cm}$ above a hot water bath $(60~^{\\circ}\\mathrm{C})$ for $60\\ s$ . In addition, light transmission over the $400{\\mathrm{-}}700\\ \\mathrm{nm}$ range was collected on an Agilent 8453 UV−vis spectrophotometer during fogging tests. To help reveal the antifogging mechanism, evolution of water contact angles on all SIPN coatings was monitored on a Ramé-Hart 290 instrument (every $10\\mathrm{~s~}$ over a 600-s period) under ambient conditions.  \n\nAntimicrobial Test. Antimicrobial tests were performed according to standard antimicrobial susceptibility test protocols, as described in detail elsewhere.41 Escherichia coli (Carolina #155065A) and Staphylococcus epidermidis (Carolina #155556) were chosen as representative Gram-negative and Gram-positive bacteria, respectively. We also examined possible leaching of bactericidal species from the SIPN coating by using a typical zone of inhibition test.41  \n\nOther Measurements. The glass transition temperature $(T_{\\mathrm{g}})$ of copolymers was measured on a TA Instruments DSC Q100 instrument, over the range from $-50$ to $120~^{\\circ}\\mathrm{C}$ at a heating rate of $10~{^\\circ}\\mathrm{C}/\\operatorname*{min}$ . $\\mathrm{^{1}H}$ NMR spectra were collected on an Agilent $400~\\mathrm{{MHz}}$ instrument with $\\mathrm{CDCl}_{3}$ as the solvent, and $\\mathrm{^{1}H}$ chemical shifts were internally referenced to the tetramethylsilane (TMS) signal. The number-average molecular weight $\\left(M_{\\mathrm{n}}\\right)$ of polymer was determined by gel permeation chromatography (GPC), using a Waters 515 HPLC pump and an OPTILAB DSP interferometric refractometer (Wyatt  \n\n![](images/ba12c8525975bcbf6b2586527c2e6000e473a9a00f612123df300df903503199.jpg)  \nFigure 1. $\\mathrm{^{1}H}$ NMR spectra of copolymers: (A) B-75 and (B) Q-7.  \n\nTechnology) detector, with dimethylformamide (DMF) as the elute (flow rate $1\\ \\mathrm{mL}/\\mathrm{min},$ at room temperature), and was calibrated with polystyrene standards.  \n\nCoating thickness was estimated by atom force microscopy (AFM) on an NT-MDT NTEGRA Prima instrument in the semicontact mode with a gold-coated cantilever NSG 10. A razor blade inscribed through the coating on the glass, followed by AFM height analysis to estimate the coating thickness.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# RESULTS AND DISCUSSION  \n\nPreparation of Partially Quaternized Poly(DMAEMAco-MMA). We first synthesized the binary copolymer poly(DMAEMA-co-MMA), B-75, with the DMAEMA/MMA molar ratio of 75/25 by conventional free radical polymerization. It was previously determined that a DMAEMA/MMA molar ratio of $70/30$ in the binary copolymer led to the optimal hydrophobic/hydrophilic balance for optimal antifogging/ frost-resisting performance.25 In this study, we chose the DMAEMA/MMA molar ratio as $75/25$ in anticipation that the subsequent partial quaternization would alter the hydrophobic/ hydrophilic balance. The $M_{\\mathfrak{n}}$ of the copolymer B-75 was 31 000, with $M_{\\mathrm{w}}/M_{\\mathrm{n}}=2.1.$ , as determined from GPC. The DMAEMA/ MMA molar ratio in B-75 was confirmed by $\\mathrm{^{1}H}$ NMR (Figure 1A) to be 3:1, which was consistent with the feed ratio.  \n\nPartially quaternized poly(DMAEMA-co-MMA) was prepared by reacting the copolymer with 1-bromoundecane (Scheme 1). A typical NMR spectrum (for $Q=7,$ Figure 1B) clearly shows chemical shifts of various protons due to the partial quaternization, which allowed us to calculate the copolymer composition (Table 1). The partially quaternized copolymers were designated as $Q=5,Q=7,$ and $Q{\\cdot}10,$ according to the QAC molar percentage. A single glass transition temperature $(T_{\\mathrm{g}})$ , ranging from 40 to $57^{\\circ}\\mathrm{C}$ (Table 1), was observed for the copolymers. The observed single $T_{\\mathrm{g}}$ clearly indicated that different monomer units were randomly distributed in the copolymer, which would help ensure the optical transparency of the copolymer coating.25,26 In addition, the $T_{\\mathrm{g}}$ of the partially quaternized copolymer depended on the QAC content: a higher QAC content led to a higher $T_{\\mathrm{g}}$ for the copolymer. The partially quaternized copolymers and B-75 were subsequently used to prepare SIPN coatings.  \n\nAntifogging Performance of the SIPN Coating. We evaluated the antifogging performance of SIPN coatings by first storing them at $-20~^{\\circ}\\mathrm{C}$ in a freezer for $30\\ \\mathrm{min}$ and then examining their appearance 5 s after exposure to ambient conditions ${\\bf\\Gamma}\\cdot20\\ ^{\\circ}{\\bf C},$ , $50\\%$ relative humidity). Unsurprisingly, fog or frost on the surface (Figure 2b), which can be attributed to the hydrophilic DMAEMA segments in the copolymer that allowed water molecules from the surroundings to be rapidly absorbed23−26 into the SIPN coating and, possibly, to spread43 along the coating surface. Once inside the coating, water molecules are hydrogen-bonded to the network at a molecular level;23,25,44,45 w ater is thus nonfreezing, and no large lightscattering water domain would be formed. The SIPN coatings with different QAC contents (SIPN- $\\scriptstyle\\cdot\\mathrm{e}$ series) also demonstrated excellent antifogging performance (Figure $2{\\mathsf{c}}{\\mathsf{-}}{\\mathsf{e}})$ , despite that up to $10\\mathrm{\\mol\\}\\%$ of hydrophobic QAC had been incorporated into the coating.  \n\n![](images/cf53a7e06f7d6a7d0ce892ada62175820741bc8e2f6011b1dd4645797f72ddf6.jpg)  \nthe control glass fogged severely (Figure 2a). In contrast, SIPNB-75 demonstrated excellent antifogging property, showing no   \nFigure 2. Photos of different samples: (a) control glass and (b) SIPNB-75, (c) SIPN-Q-5, (d) SIPN-Q-7, and (e) SIPN-Q-10 coatings, which were first stored at $-20{}^{\\circ}\\mathrm{C}$ for $30\\mathrm{min}$ and then exposed for 5 s to ambient lab conditions $\\mathrm{\\Omega}^{\\sim}20\\ ^{\\circ}\\mathrm{C},$ $50\\%$ relative humidity).  \n\nTo evaluate antifogging property more quantitatively, the light transmission data over the $400{-}700~\\mathrm{\\nm}$ range were collected (Figure 3). Prior to the test, all SIPN coatings exhibited comparable light transmission (about $92\\%$ , Figure 3a) to the control glass, indicating that the effect of the SIPN coating on the light transmission was negligible. During the fogging test, the light transmission through the control glass reduced markedly to ${\\sim}15\\%$ , while all four SIPN coatings maintained high light transmission $(>91\\%$ , Figure 3b). It became apparent that the presence of up to $10\\mathrm{\\mol\\}\\%$ of the hydrophobic QAC units did not compromise the affinity of water for the quaternized copolymer, likely because the hydrophobic effect of the aliphatic tail was counterbalanced by the hydrophilic quaternary ammonium moiety.  \n\n![](images/abd0cdd6cd3c7d8147248b888b77ea671077899c4c707f28acf7f67be5361877.jpg)  \nFigure 3. Light transmittance at the normal incident angle for various samples: (a) as prepared and (b) 5 s under ambient condition $_{\\sim20}$ ${}^{\\circ}{\\bf C},$ $50\\%$ relative humidity) after being stored at $-20~^{\\circ}\\mathrm{C}$ for $30~\\mathrm{min}$ . The spikes in the spectra were due to background noise from the light bulb.  \n\nThe antifogging performance of the SIPN coatings was also evaluated against hot moist air by placing the samples $5\\ \\mathrm{cm}$ above a hot water bath $\\left(\\sim60~^{\\circ}\\mathrm{C}\\right)$ for 60 s. Again, the control glass fogged up immediately upon contact with hot water vapor, deteriorating the light transmission (Figure 4). For SIPN coatings, different antifogging performance was observed: both SIPN-Q-5 and SIPN-Q-7 demonstrated excellent antifogging property, as indicated by high light transmittance $(\\sim90\\%)$ , which was slightly higher than that of SIPN-B-75. In contrast, there was major reduction in the light transmission (from $92\\%$ to ${\\sim}82\\%$ ) for SIPN-Q-10. A major difference between these two antifogging tests was that the total amount of water to be absorbed by a coating in the test against hot moist air would be greater than the test under ambient conditions (for the sample being taken out of a freezer). Incorporation of a hydrophobic QAC into poly(DMAEMA-co-MMA) might slightly reduce the hydrophilicity, and thus the water-absorbing capability, of the copolymer. This hydrophilicity-reducing effect only became noticeable when the amount of the incorporated hydrophobic QAC was too high (as in SIPN-Q-10, on which slight fogging was observed against hot moist air since there was too much water to be absorbed). For SIPN coatings with lower amounts of QAC (SIPN-Q-5 and SIPN-Q-7), the presence of the hydrophobic QAC appeared to have very little effect on the overall hydrophilicity of the copolymer; thus, the excellent antifogging property of the coating (even against hot moist air) was maintained. It is worth noting that the introduction of a hydrophobic QAC also helped eliminate the lower critical solution temperature (LCST) effect that originated from the binary copolymer poly(DMAEMA- $_{\\cdot c o}$ -MMA), which led to relatively poor antifogging performance against hot moist air.25  \n\n![](images/727ac3d0ebdcd02fa54dc7ac07b65c3af629a8abe4e20fa6897ba7f0d41982b0.jpg)  \nFigure 4. Light transmission at the normal incident angle for various samples after 60-s exposure to hot moist air ( ${\\big/}{\\mathfrak{s}}\\mathrm{cm}$ above a $60~^{\\circ}\\mathrm{C}$ water bath) under ambient lab conditions $\\mathrm{\\sim}20^{\\circ}\\mathrm{C},$ $50\\%$ relative humidity). The spikes in the spectra were due to background noise from the light bulb.  \n\nTo help reveal the antifogging mechanism, time-dependent evolution of water contact angle (CA) on all SIPN coatings was monitored over a $600{\\cdot}s$ period under ambient conditions ${\\sim}20$ ${}^{\\circ}\\mathrm{C},$ $50\\%$ relative humidity). Unlike a typical superhydrophilic antifogging surface (CA approaching $0^{\\circ}$ ), all SIPN coatings exhibited initial water CAs well above ${60}^{\\circ}$ (Figure 5a), reinforcing the recent findings from us25,26 and others22−24,27 that an effective antifogging coating does not have to be superhydrophilic. A higher QAC content in the SIPN coating led to a greater initial water CA (Figure 5a), likely due to surface enrichment of long alkyl chains at the coating surface.41 During the 600-s time interval, the water CAs on all SIPN coatings decreased much more rapidly than on the control glass (due to water evaporation only), indicating that some water had likely diffused into the SIPN coating.  \n\n![](images/57bc63d15dd13df59a5f88c3d7f05e84276e9c2b3c055174b15e047eb32407ec.jpg)  \nFigure 5. (a) Evolution of water contact angle on various samples as a function of time. (b) Basal diameter change of the water droplet on various samples over the 600-s period, expressed as $\\Delta D/D_{0},$ where $\\Delta D$ $=D-D_{0}$ and $D_{0}$ and $D$ (shown in the inset) are the initial diameter (time zero) and the diameter at different times, respectively, of the basal area of the droplet.  \n\nWe also monitored the change in the basal diameter of a water droplet on the coating surface. While no obvious change in the basal diameter was observed on the control glass over the 600-s period, the droplet basal diameter increased on all SIPN coatings to various extents (Figure 5b), depending on the QAC content in the coating. SIPN-B-75 had the largest expansion in the droplet basal diameter $(15\\%)$ over the observation period, followed by SIPN-Q-5 $(13\\%)$ , SIPN-Q-7 $(11\\%)_{.}$ , and SIPN- $\\scriptstyle\\cdot\\mathrm{e}$ 10 $(7\\%)$ . These results again suggested that water had diffused23−26 into the SIPN coating, leading to the expansion of the droplet basal area on the coating surface. Water spreading along the coating surface may have also contributed to the basal area expansion.43 It should be pointed out that our SIPN coatings were quite smooth, as indicated by a typical root-mean-square (RMS) roughness of $2{-}3~\\mathrm{nm}$ over an area of $2\\times2\\ \\mu\\mathrm{m}^{2}$ from AFM measurements. In addition, AFM revealed that these coatings were not nanoporous either, so their water-imbibing ability was not nanoporosity-drivn10−13,15,17 but originated from the hydrophilic segment in the copolymer. Obviously, the incorporation of a higher amount of hydrophobic QAC led to a decrease in the waterabsorbing capability (less water expansion) of the SIPN coating, which is consistent with the antifogging performance of these SIPN coatings we discussed above. Too high an amount of QAC in the copolymer would definitely compromise the water-absorbing ability of the SIPN coating (as in the case of SIPN-Q-10) and, consequently, its antifogging performance against hot moist air in particular.  \n\nAntimicrobial Activity of SIPN Coating. We examined antimicrobial activities of SIPN coatings by using S. epidermidis and $E_{\\rightleftarrows}$ . coli as representative microorganisms. The reduction of the number of viable bacterial cells (log scale) as colony forming units (cfu) within $24{\\cdot}\\mathrm{h}$ incubation was recorded. As listed in Table 2, SIPN-B-75 demonstrated some antimicrobial activity against E. coli (3.6-log reduction) and S. epidermidis (2- log reduction), which may be attributed to the formation of temporary QAC between the tertiary amine in the DMAEMA units and water at neutral $\\mathrm{\\tt{pH}},$ , which is close to the $\\mathsf{p}K_{\\mathrm{a}}$ of PDMAEMA homopolymer.38,46 PDMAEMA homopolymer was found to be able to inhibit bacterial growth.38 More importantly, the introduction of permanent, hydrophobic QAC to the copolymer greatly enhanced the antimicrobial activity of the SIPN coating: all of the SIPN-Q coatings demonstrated superior bacteria-killing efficiency, all reaching 5-log reduction (total kill, Table 2) against both bacteria. Notably, the excellent antimicrobial property of the SIPN coating with the lowest QAC content (SIPN-Q-5) in our study clearly highlights that covalent binding of a small amount of hydrophobic QAC to the copolymer poly(DMAEMA-co-MMA) has allowed us to obtain very effective, dual-functional antifogging/antimicrobial coating. The interplay between the water-absorbing, hydrophilic DMAEMA segments and the bacteria-killing, hydrophobic QAC dictates the design of effective dual-functional coatings. Obviously, a high QAC content would enhance antimicrobial activity but might compromise antifogging behavior if too much QAC is incorporated into the copolymer. Both SIPN-Q-5 and SIPN-Q-7 have demonstrated excellent dual functions in this study.  \n\nTable 2. Bacterial Log Reduction after 24-h Incubation with Initial Bacterial Concentration of $\\mathbf{10^{5}}$ Bacteria/ $\\mathbf{\\Pi}_{\\mathbf{mL}}$ Treated with Various Samples $(2.2\\times2.2~\\mathrm{cm}^{2},$ )   \n\n\n<html><body><table><tr><td rowspan=\"2\"> sample</td><td colspan=\"2\">bacterial log reduction</td></tr><tr><td>E. coli</td><td>S. epidermidis</td></tr><tr><td>control glass</td><td>0.6</td><td>0.4</td></tr><tr><td>SIPN-B-75</td><td>3.6</td><td>2</td></tr><tr><td>SIPN-Q-5</td><td>5</td><td>5</td></tr><tr><td>SIPN-Q-7</td><td>5</td><td>5</td></tr><tr><td>SIPN-Q-10</td><td>5</td><td>5</td></tr></table></body></html>  \n\nIt is highly desirable for an antimicrobial coating not to leach out any bactericidal species; otherwise, released bactericidal species may not only become an environmental hazard but also trigger antibiotic resistance.47 We used the zone-of-inhibition test to examine possible leaching of bactericidal species from our dual-functional coating. As shown in Figure 6, E. coli proliferated right next to the two coatings (SIPN-Q-5 and SIPN-Q-10) examined, indicating that no bacterial inhibition zone existed, and therefore, no bactericidal QAC species had leached out of the SIPN coatings. Lack of a bacterial inhibition zone further suggested that the bactericidal action of our dualfunctional coating was based on contact killing, which can be attributed to the covalent bonding of QAC to the copolymer.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# CONCLUSIONS  \n\nIn summary, we have designed and prepared a dual-functional polymer coating with excellent antifogging/antimicrobial properties, on the basis of SIPN of partially quaternized poly(DMAEMA- $_{\\cdot c o}$ -MMA) and polymerized EGDMA network. The antifogging behavior originated primarily from the delicate hydrophilic/hydrophobic balance of the partially quaternized copolymer. Meanwhile, partial quaternization of the DMAEMA units led to covalently bonded hydrophobic QACs, rendering the coating strongly antimicrobial, as demonstrated by total kill against Gram-positive S. epidermidis and Gram-negative E. coli bacteria. This type of dual-functional coating may find unique applications where both antimicrobial and antifogging properties are desired, such as lenses in medical devices and transparent food-packaging materials.  \n\n![](images/3f62297011cf6a4b7c4e8108da973497fa22876e0c73a4f81e8b5100b0f577b5.jpg)  \nFigure 6. Zone-of-inhibition test result of (a) SIPN-Q-5 and (b) SIPN-Q-10 in a cultured lawn of E. coli.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 7,
+        "chunk": "# AUTHOR INFORMATION  \n\nCorresponding Author   \n$^{*}\\mathrm{E}$ -mail: wming@georgiasouthern.edu.   \nNotes   \nThe authors declare no competing financial interest.",
+        "category": " References"
+    },
+    {
+        "id": 8,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nFinancial support of this research at Georgia Southern University from USDA/NIFA (Award No. 2011-67022- 30229) is gratefully acknowledged.",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# REFERENCES  \n\n(1) Howarter, J. A.; Youngblood, J. P. Self-Cleaning and Anti-Fog Surfaces via Stimuli-Responsive Polymer Brushes. Adv. Mater. 2007, 19, 3838−3843.   \n(2) Li, Y.; Zhang, J.; Zhu, S.; Dong, H.; Jia, F.; Wang, Z.; Sun, Z.; Zhang, L.; Li, Y.; Li, H.; Xu, W.; Yang, B. Biomimetic Surfaces for High-Performance Optics. Adv. Mater. 2009, 21, 4731−4734.   \n(3) Zhang, L.; Qiao, Z.; Zheng, M.; Huo, $\\mathrm{Q.;}$ Sun, J. Rapid and Substrate-Independent Layer-by-layer Fabrication of Antireflection and Antifogging-Integrated Coatings. J. Mater. Chem. 2010, 20, 6125− 6130.   \n(4) Chevallier, P.; Turgeon, S.; Sarra-Bournet, C.; Turcotte, R.; Laroche, G. Characterization of Multilayer Anti-Fog Coatings. ACS Appl. Mater. Interfaces 2011, 3, 750−758.   \n(5) Introzzi, L.; Fuentes-Alventosa, J. M.; Cozzolino, C. A.; Trabattoni, S.; Tavazzi, S.; Bianchi, C. L.; Schiraldi, A.; Piergiovanni, L.; Farris, S. Wetting Enhancer” Pullulan Coating for Antifog Packaging Applications. ACS Appl. Mater. Interfaces 2012, 4, 3692− 3700.   \n(6) Lawrentschuk, N.; Fleshner, N. E.; Bolton, D. M. Laparoscopic Lens Fogging: a Review of Etiology and Methods to Maintain a Clear Visual Field. J. Endourol. 2010, 24, 905−913.   \n(7) Ohdaira, T.; Nagai, H.; Kayano, S.; Kazuhito, H. Antifogging Effects of a Socket-type Device with the Superhydrophilic, Titanium Doxide-Coated Glass for the Laparoscope. Surg. Endosc. 2007, 21, 333−338.   \n(8) Knauth, A.; Weiss, M.; Dave, M.; Frotzler, A.; Haas, A. Comparison of Antifog Methods in Endoscopy: What Really Helps. Anaesthesist 2012, 61, 1036−1044. (9) Nomura, K.; Oshima, H.; Yamauchi, D.; Kawase, T.; Katori, Y.; Hidaka, H. Ototoxic Effect of Ultrastop Antifog Solution Applied to the Guinea Pig Middle Ear. Otolaryngol.–Head Neck Surg. 2014, 151, 840−844.   \n(10) Lee, D.; Rubner, M. F.; Cohen, R. E. All-Nanoparticle Thin Film Coatings. 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A Multifunctional Nanoporous Layer Created on Glass through a Simple Alkali Corrosion Process. J. Mater. Chem. 2010, 20, 10246−10252. (16) Nuraje, N.; Asmatulu, ${\\mathrm{R}};$ Cohen, R. E.; Rubner, M. F. Durable Antifog Films from Layer-by-Layer Molecularly Blended Hydrophilic Polysaccharides. Langmuir 2011, 27, 782−791.   \n(17) Xu, L.; He, J. Antifogging and Antireflection Coatings Fabricated by Integrating Solid and Mesoporous Silica Nanoparticles without Any Post-Treatments. ACS Appl. Mater. Interfaces 2012, 4, 3293−3299.   \n(18) Wang, R.; Hashimoto, K.; Fujishima, A.; Chikuni, M.; Kojima, E.; Kitamura, A.; Shimohigoshi, M.; Watanabe, T. Light-Induced Amphiphilic Surfaces. Nature 1997, 388, 431−432.   \n(19) Miyauchi, M.; Nakajima, A.; Hashimoto, K.; Watanabe, T. A Highly Hydrophilic Thin Film Under 1 $\\mu\\mathrm{W}/\\mathrm{cm}^{2}$ UV Illumination. Adv. Mater. 2000, 12, 1923−1927.   \n(20) Lai, Y.; Tang, Y.; Gong, J.; Gong, D.; Chi, L.; Lin, C.; Chen, Z. 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One-step, Painting-like Coating Procedures to Make Surfaces Highly and Permanently Bactericidal. Biotechnol. Prog. 2006, 22, 584−589.   \n(32) Klibanov, A. M. Permanently Microbicidal Materials Coatings. J. Mater. Chem. 2007, 17, 2479−2482.   \n(33) Kenawy, E. R.; Worley, S. D.; Broughton, R. The Chemistry and Applications of Antimicrobial Polymers: A State-of-the-Art Review. Biomacromolecules 2007, 8, 1359−1384.   \n(34) Kurt, P.; Wood, L.; Ohman, D. E.; Wynne, K. J. Highly Effective Contact Antimicrobial Surfaces via Polymer Surface Modifiers. Langmuir 2007, 23, 4719−4723.   \n(35) Murata, H.; Koepsel, R. R.; Matyjaszewski, K.; Russell, A. J. Permanent, Non-leaching Antibacterial Surfaces−2: How High Density Cationic Surfaces Kill Bacterial Cells. Biomaterials 2007, 28, 4870−4879.   \n(36) Waschinski, C. J.; Zimmermann, J.; Salz, U.; Hutzler, R.; Sadowski, G.; Tiller, J. C. Design of Contact-active Antimicrobial Acrylate-based Materials Using Biocidal Macromers. Adv. Mater. 2008, 20, 104−108.   \n(37) Harney, M. B.; Pant, R. R.; Fulmer, P. A.; Wynne, J. H. Surface Self-concentrating Amphiphilic Quaternary Ammonium Biocides as Coating Additives. ACS Appl. Mater. Interfaces 2009, 1, 39−41. (38) Rawlinson, L.-A. B.; Ryan, S. M.; Mantovani, G.; Syrett, J. A.; Haddleton, D. M.; Brayden, D. J. Antibacterial Effects of Poly(2- (dimethylamino ethyl)methacrylate) against Selected Gram-Positive and Gram-Negative Bacteria. Biomacromolecules 2010, 11, 443−453. (39) Yagci, M. B.; Bolca, S.; Heuts, J. P. A.; Ming, W.; de With, G. Self-stratifying Antimicrobial Polyurethane Coatings. Prog. Org. Coat. 2011, 72, 305−314.   \n(40) Yagci, M. B.; Bolca, S.; Heuts, J. P. A.; Ming, W.; de With, G. Antimicrobial Polyurethane Coatings Based on Ionic Liquid Quaternary Ammonium Compounds. Prog. Org. Coat. 2011, 72, 343−347.   \n(41) Zhao, J.; Millians, W.; Tang, S.; Wu, T.; Zhu, L.; Ming, W. SelfStratified Antimicrobial Acrylic Coatings via One-Step UV Curing. ACS Appl. Mater. Interfaces 2015, 7, 18467−18472.   \n(42) Asri, L. A. T. W.; Crismaru, M.; Roest, S.; Chen, Y.; Ivashenko, O.; Rudolf, P.; Tiller, J. C.; van der Mei, H. C.; Loontjens, T. J. A.; Busscher, H. J. A Shape-Adaptive, Antibacterial-Coating of Immobilized Quaternary-ammonium Compounds Tethered on Hyperbranched Polyurea and Its Mechanism of Action. Adv. Funct. Mater. 2014, 24, 346−355.   \n(43) Farris, S.; Introzzi, L.; Biagioni, P.; Holz, T.; Schiraldi, A.; Piergiovanni, L. Wetting of Biopolymer Coatings: Contact Angle Kinetics and Image Analysis Investigation. Langmuir 2011, 27, 7563− 7574.   \n(44) Ohno, H.; Shibayama, M.; Tsuchida, E. DSC Analyses of Bound Water in the Microdomains of Interpolymer Complexes. Makromol. Chem. 1983, 184, 1017−1024.   \n(45) Salmerón Sanchez, M.; Gallego Ferrer, G.; Monleón Pradas, M.; Gómez Ribelles, J. L. Influence of the Hydrophobic Phase on the Thermal Transitions of Water Sorbed in a Polymer Hydrogel Based on Interpenetration of a Hydrophilic and a Hydrophobic Network. Macromolecules 2003, 36, 860−866.   \n(46) Butun, V.; Armes, S. P.; Billingham, N. C. Synthesis and Aqueous Solution Properties of Near-monodisperse Tertiary Amine Methacrylate Homopolymers and Diblock Copolymers. Polymer 2001, 42, 5993−6008.   \n(47) Sun, X.; Zhang, L.; Cao, Z.; Deng, Y.; Liu, L.; Fong, H.; Sun, Y. Electrospun Composite Nanofiber Fabrics Containing Uniformly Dispersed Antimicrobial Agents As an Innovative Type of Polymeric Materials with Superior Antimicrobial Efficacy. ACS Appl. Mater. Interfaces 2010, 2, 952−956.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# UV 固化单体及低聚物在塑胶基材上的附着力与化学结构之间关系的研究  \n\n张海清，陈正平 （湛新树脂上海有限公司，上海 200231）  \n\n摘　 要：测试了不同的单体和低聚物在 ABS 上的附着力；并从化学结构角度分析了造成附着力差异的原因。 指出化学结构是决定附着力的首要因素，而不是体积收缩；酯键和醚键分别起到增加附着力和降低附着力的作用。 提出了衡量附着力的 3 个概念：酯键密度（ $C_{\\mathrm{es}}$ ）、醚键密度（ $C_{\\mathrm{et}}$ ）和酯键醚键密度比（ $\\left(C_{\\mathrm{es}}/C_{\\mathrm{et}}\\right)$ 。 对于不含醚键的单体和低聚物，如果 $C_{\\mathrm{es}}\\gtrsim0.6\\%$ ，则可在 ABS 上获得良好的附着力。 对于含有醚键的单体和低聚物，需要 $C_{\\mathrm{es}}$ 和 $C_{\\mathrm{es}}/C_{\\mathrm{et}}$ 同时满足条件：只有 $C_{\\mathrm{es}}\\gtrsim0.6\\%$ ，并且 $C_{\\mathrm{es}}/C_{\\mathrm{et}}\\geqslant$ 4，才能获得良好的附着力。  \n\n关键词：附着力；体积收缩；化学结构；酯键；醚键；酯键密度；醚键密度；酯键醚键密度比中图分类号：TQ 637􀆰 83 文献标识码：A 文章编号：0253－4312（2017）06－0007－05",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# Study of Relationship between Adhesion and Chemical Structure of UV－Curable Monomers and Oligomers  \n\nZhang Haiqing，Chen Zhengping（Allnex Resins （Shanghai） Co．， Ltd．， Shanghai 200231， China）  \n\nAbstract：The adhesion of different monomers and oligomers on ABS substrate are tested and the testing results are analyzed from the view of chemical structure． It is revealed that chemical structure rather than volume shrinkage is the most important influential factor on ad⁃ hesion， and ester bonds can improve adhesion of monomers $\\&$ oligomers on ABS substrate while ether bonds reduce adhesion． Three concepts are provided to estimate adhesion： concen⁃ tration of ester bond $(C_{\\mathrm{es}})$ ， concentration of ether bond $(C_{\\mathrm{et}})$ and their ratio $(C_{\\mathrm{es}}/C_{\\mathrm{et}})$ ． For monomers and oligomers without ether bonds， they will show good adhesion on ABS if $C_{\\mathrm{es}}$ is not less than $0.6\\%$ ． For monomers and oligomers with ether bonds， they will show good adhe⁃ sion on ABS if $C_{\\mathrm{es}}$ is not less than $0.6\\%$ and $C_{\\mathrm{es}}/C_{\\mathrm{et}}$ is not less than 4 simultaneously．  \n\nKey Words：adhesion； volume shrinkage； chemical structure； ester bond； ether bond；concentration of ester bond； concentration of ether bond； $C_{\\mathrm{es}}/C_{\\mathrm{et}}$  \n\n涂料成分中，对附着力影响最大的就是成膜物质，即树脂（低聚物）和单体。 附着力的影响因素非常复杂，到目前为止，并没有一个完美的理论能够解释所有的附着力机理。 对附着力的解释只能“具体  \n\n情况具体分析”。  \n\nUV 涂料在塑料基材上的应用已经非常广泛，涉及到电子产品、汽车内外饰、化妆品包材等领域。 常用的塑胶基材有 ABS、 PC、 $\\mathrm{ABS}+\\mathrm{PC}$ 合 金、 PET、  \n\nPMMA 等。 其中， 附着力是备受关注的焦点问题。在已出版的 UV 涂料专业书籍中，对附着力与成膜物化学结构之间的关系解释较为笼统，缺乏衡量的概念与数据。 同时，大多都强调了“ 体积收缩” 的影响［1－3］：认为丙烯酸双键在聚合的过程中，由分子间的距离转变为分子内的距离，因而出现体积收缩，造成了内应力，最终影响了涂膜在基材上的附着力。 但实际上，这个解释与实践结果往往大相径庭，给从业者造成很大困惑。  \n\n本文测试了不同单体和低聚物在 ABS 基材上的附着力性能；探讨了其化学结构与附着力的关系；提出了一些新的观点，以供大家探讨、批评。",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# 1 实验部分",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1􀆰 1 实验原料与仪器  \n\n二缩三丙二醇二丙烯酸酯（TPGDA）、丙氧化的新戊二醇二丙烯酸酯 $\\left[\\mathrm{NPG}(\\mathrm{PO})_{2}\\mathrm{DA}_{-}^{-}$ 、三羟甲基丙烷三丙烯酸酯（TMPTA）、三（乙氧化）的三羟甲基丙烷三丙烯酸酯 $[\\mathrm{TMP(EO)_{3}T A}]$ 、丙氧化的甘油三丙烯酸酯［ $\\mathrm{{.GP(PO)_{3}T A}}^{\\cdot}$ 、季戊四醇三四丙烯酸酯（PE⁃TIA）、双季戊四醇五六丙烯酸酯（DPHA）：工业级，湛新树脂上海有限公司。  \n\nEBECRYL $^{\\mathfrak{e}}270$ （二官能度的脂肪族聚氨酯丙烯酸酯）、 $\\mathrm{.EBECRYL^{\\circledcirc}}210$ （二官能度的芳香族聚氨酯丙烯酸酯）、EBECRYL $\\textcircled{\\Theta}8807$ （二官能度的聚氨酯丙烯酸酯）、EBECRYL $\\textcircled{\\\"}4100$ （三官能度的脂肪族聚氨酯丙烯酸酯）、 $\\mathrm{\\cdot{EBECRYL^{\\circledcirc}4200}}$ （四官能度的聚氨酯丙烯酸酯）、EBECRYL $\\textcircled{\\Theta}8702$ （六官能度的聚氨酯丙烯酸酯）、EBECRYL $\\textcircled{8}8402$ （二 官 能 度 聚 氨 酯 丙 烯 酸 酯）、EBECRYL􀳏 8804 （ 二 官 能 度 聚 氨 酯 丙 烯 酸 酯）、EBECRYL􀳏 4513 （ 三 官 能 度 聚 氨 酯 丙 烯 酸 酯）、EBECRYL $\\mathfrak{e}_{1290}$ （六官能度的聚氨酯丙烯酸酯）、EBE⁃$\\operatorname{CRYL}^{\\circledast}$ 5129 （六 官 能 度 的 聚 氨 酯 丙 烯 酸 酯）、EBECRYL ${\\mathfrak{P}}800$ （ 四 官 能 度 聚 酯 丙 烯 酸 酯）、EBECRYL $^{\\mathfrak{B}}830$ （ 六 官 能 度 聚 酯 丙 烯 酸 酯）、EBECRYL $^{\\textregistered}837$ （ 超 支 化 的 聚 酯 丙 烯 酸 酯）、EBECRYL $\\mathfrak{B}_{350}$ （二官能度的有机硅改性丙烯酸酯）：工业级，湛新树脂上海有限公司。  \n\nEBECRYL $\\mathcal{\\circledcirc}11$ （二官能度聚醚丙烯酸酯）、EBE⁃$\\operatorname{CRYL}^{\\circledast}12$ （三官能度聚醚丙烯酸酯）、 $\\mathrm{EBECRYL}^{\\circledast}13$ （二官能度聚醚丙烯酸酯）； $\\mathrm{EBECRYL^{\\otimes}}600$ （标准双酚 A 型环氧丙烯酸酯，二官能度）、 $\\mathrm{EBECRYL}^{\\circledast}3708$ （酸酐改性双酚 A 环氧丙烯酸酯，二官能度）：工业级，湛新树脂上海有限公司，。  \n\nSR502，9－（乙氧化）三羟甲基丙烷三丙烯酸酯：工业级，沙多玛（广州）有限公司。  \n\n光引发剂 IRGACURE $\\textcircled{\\\"}184$ ：BASF 公司；醋酸丁酯：工业级，市售。  \n\n高速搅拌机：SFJ－400，上海现代环境工程技术有限公司；喷枪：日本阿耐思特岩田株式会社；烘箱：法国 BINDER 公司；履带式 UV 固化机：德国 IST 公司；涂层测厚仪： $\\mathrm{Qnix}4500$ ，德国尼克斯公司。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 1􀆰 2 实验过程",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 1􀆰 2􀆰 1 涂料的配制  \n\n按照表 1 依次配料， 然后用高速搅拌机在$800~\\mathrm{r/min}$ 的条件下搅拌 $15~\\mathrm{min}$ ，密封避光存放。  \n\n表1　 涂料配方Table 1　 Coating formulation  \n\n\n<html><body><table><tr><td>原料</td><td>m/g</td></tr><tr><td>单体或低聚物</td><td>100</td></tr><tr><td>EBECRYL?350</td><td>0. 2</td></tr><tr><td>IRGACURE?184</td><td>5</td></tr><tr><td>醋酸丁酯</td><td>0 ~ 100</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 1􀆰 2􀆰 2 喷涂与固化  \n\n将配好的涂料依次喷于 ABS 板上，置于烘箱闪干，然后通过履带式 UV 固化机固化。 漆膜厚度控制在 $10\\sim15~{\\upmu\\mathrm{m}}$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 1􀆰 2􀆰 3 划格法附着力测试  \n\n按照 GB ／ T 9286—1998 进行测试，0 级代表最好，5 级代表最差。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2 结果与讨论",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2􀆰 1 单体在 ABS 上的附着力  \n\n通常，单体在基材上的附着力应关注以下几点：（1）表面张力。 表面张力越低，对基材的润湿性越好，附着力越好。 （2）溶胀腐蚀。 如果单体对于基材有较强的渗透溶胀能力，则固化交联后，可在基材与涂层之间形成一层很薄的互穿网络结构，附着力会大大增强。 （3）体积收缩。 通常认为低官能度单体，交联密度低，体积收缩小，附着力较好；而高官能度单体的体积收缩大，内应力大，会降低附着力。 表 2 是几种常用单体的体积收缩率［2］及其在 ABS 上的附着力  \n\n实验数据。  \n\nTable 2　 Monomers􀆳 volume shrinkage and adhesion on ABS   \n\n\n<html><body><table><tr><td>项目</td><td>TPGDA</td><td>NPG( PO)DA</td><td>GP(PO) TA</td><td>TMP(EO)TA</td><td>TMPTA</td><td>PETIA</td><td>DPHA</td></tr><tr><td>体积收缩率/%</td><td>11.9</td><td>6.8</td><td>15.4</td><td>14.3</td><td>26</td><td></td><td></td></tr><tr><td>附着力/级</td><td>5</td><td>5</td><td>3</td><td>2</td><td>0</td><td>0</td><td>0</td></tr></table></body></html>  \n\n根据表 2 体积收缩率大小推断， $\\mathrm{{NPG}(P O)_{2}D A}$ 应该有最好的附着力，TPGDA 次之，TMPTA 的附着力最差。 但是实验测试的结果却有所出入。 此外，PETIA 和 DPHA 等体积收缩更高的单体却依然表现出足够好的附着力。  \n\n实际上，我们在讨论附着力的时候，往往忽视了化学结构对性能的决定性影响。 体积收缩固然对附着力有害，但是与化学结构相比，属于次要的因素。因此，在评判附着力的时候，首先要考虑的因素是产品的化学结构。  \n\n在常用的 UV 固化单体和低聚物中，一般都含有较多的酯键、氨酯键、醚键等基团。 在大量实验基础上，我们发现酯键和氨酯键对单体和低聚物在 ABS上的附着有促进作用，其作用远大于体积收缩带来的影响；而醚键则会降低附着力。 在此基础上，本文提出了酯键密度（ $C_{\\mathrm{es}}$ ）的概念，用来评估成膜物对 ABS基材的附着力。 计算公式如式（1）所示。  \n\n酯键密度 $\\mathbf{\\Sigma}=\\mathbf{\\Sigma}$ 每摩尔单体或低聚物中的酯键和氨酯键的物质的量／相对分子质量 $\\times100\\%$ 式（1）  \n\n上述几种单体的酯键密度如表3 所示。  \n\n表2　 不同单体的体积收缩率及其在 ABS 上的附着力  \n表3　 几种单体的酯键密度Table 3　 Concentration of ester bond $\\left\\langle C_{\\mathrm{es}}\\right\\rangle$ ） for monomers  \n\n\n<html><body><table><tr><td>项目</td><td>TPGDA</td><td>NPG(PO)DAGP(PO)TA|TMP(EO)TA</td><td></td><td></td><td>TMPTA</td><td>PETIA</td><td>DPHA</td></tr><tr><td>酯键密度/%</td><td>0.67</td><td>0.61</td><td>0.70</td><td>0.70</td><td>1.01</td><td>1.08</td><td>1.04</td></tr></table></body></html>  \n\n综合表2 和表 3 可见，随着酯键密度的增大，附着力逐渐增强。 TMPTA、PETIA、DPHA 都具有较高的酯 键 密 度， 其 附 着 力 优 秀； 而 TPGDA、 NPG －$(\\mathrm{PO})_{2}\\mathrm{DA}$ 的酯键密度低，附着力则差。  \n\n需要说明的是，多数单官能度单体由于固化速度慢，难以独立固化成膜，因此未被纳入评测。 而HDDA（己二醇二丙烯酸酯）由于具有对 ABS 很强的溶胀能力，也未参与讨论。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 2􀆰 2 低聚物在 ABS 上的附着力  \n\n在 ABS 基材上，应用最多的低聚物是聚氨酯丙烯酸酯（PUA），其次是聚酯丙烯酸酯（PEA）。 聚氨酯丙烯酸酯按照扩链单元又可分为聚醚类和聚酯类（包含聚己内酯和聚碳酸酯）。 由于聚酯的结构多样、类型繁杂，难以一一囊括评估。 本文仅选取了有代表性的几种。 而聚醚类则结构相对单一、种类较少，使用较多的是聚乙二醇醚、聚丙二醇醚和聚四氢呋喃。 本文选取的样本将这3 种结构全部包含在内。但是基于技术保密原因未进行一一对应说明。  \n\n表 4 是所选取的低聚物的相关特征数据及各低聚物在 ABS 上的附着力测试结果及低聚物的酯键密度。  \n\n由表4 可以看出，所有聚醚型的聚氨酯丙烯酸酯在 ABS 上均显示了较差的附着力，而这与官能度、玻璃化转变温度和体积收缩率没有直接的关系。 这些聚醚型的聚氨酯丙烯酸酯都具有一个共同的特点，就是酯键密度较低。 聚酯类的聚氨酯丙烯酸酯，随着酯键密度的不同而表现出不同的附着力。 酯键密度高，则附着力好。 未扩链的 EB1290 和 EB5129 尽管体积收缩较大，但均表现出优秀的附着力。 它们共同的特点是酯键密度很高。 所选的聚酯丙烯酸酯都因具有较高的酯键密度，附着力普遍较好。 上述实验结果说明“体积收缩” 并不是附着力的决定因素；而化学结构的特点即酯键密度才是决定因素。 当酯键密度＞$0.60\\%$ 时，低聚物都可以在 ABS 上获得良好的附着力。 需要说明的是由于低聚物的相对分子质量具有多分散性，实际相对分子质量与理论相对分子质量数值有偏差，造成酯键密度的计算值出现一定误差。 此  \n\n表4　 不同低聚物的特征数据Table 4　 Oligomers􀆳 characters  \n\n\n<html><body><table><tr><td>名称</td><td>结构组成</td><td>官能 度</td><td>理论 M,</td><td>℃ T/</td><td>伸长 率/%</td><td>体积收缩 率/%</td><td>附着 力/级</td><td>酯键 密度/%</td></tr><tr><td>EB210</td><td>聚醚类芳香族PUA</td><td>2</td><td>1 500</td><td>-19</td><td>64</td><td>5</td><td>５</td><td>0.27</td></tr><tr><td>EB270</td><td>聚醚类脂肪族PUA</td><td>2</td><td>1 500</td><td>-27</td><td>87</td><td>3</td><td>5</td><td>0.27</td></tr><tr><td>EB8807</td><td>聚醚类脂肪族PUA</td><td>2</td><td>1 300</td><td>32</td><td>54</td><td></td><td>5</td><td>0.3</td></tr><tr><td>EB4100</td><td>聚醚类脂肪族PUA</td><td>3</td><td>1 100</td><td>15</td><td>27</td><td><8</td><td>4</td><td>0.45</td></tr><tr><td>EB4200</td><td>聚醚类脂肪族PUA</td><td>4</td><td>1 500</td><td>10</td><td>15</td><td><8</td><td>５</td><td>0.4</td></tr><tr><td>EB8702</td><td>聚醚类脂肪族PUA</td><td>6</td><td>5 500</td><td>28</td><td>10</td><td></td><td>5</td><td>0.32</td></tr><tr><td>EB8402</td><td>聚酯类脂肪族PUA</td><td>2</td><td>1 000</td><td>14</td><td>90</td><td>1.5</td><td>5</td><td>0.45</td></tr><tr><td>EB8804</td><td>聚酯类脂肪族PUA</td><td>2</td><td>1 500</td><td>24</td><td>103</td><td><5</td><td>0</td><td>0.6</td></tr><tr><td>EB4513</td><td>聚酯类脂肪族PUA</td><td>3</td><td>1 400</td><td>10</td><td>30</td><td></td><td>0</td><td>0.65</td></tr><tr><td>EB1290</td><td>未扩链脂肪族PUA</td><td>6</td><td>900</td><td>69</td><td>2</td><td>~ 12</td><td>0</td><td>0.89</td></tr><tr><td>EB5129</td><td>未扩链脂肪族PUA</td><td>6</td><td>800</td><td>80</td><td>2</td><td>~ 12</td><td>0</td><td>１</td></tr><tr><td>EB800</td><td>聚酯丙烯酸酯</td><td>4</td><td>780</td><td></td><td></td><td></td><td>0</td><td>1.28</td></tr><tr><td>EB830</td><td>聚酯丙烯酸酯</td><td>6</td><td>6</td><td>60</td><td>4</td><td></td><td>0</td><td>0.87</td></tr><tr><td>EB837</td><td>超支化聚酯丙烯酸酯</td><td>6</td><td>2 700</td><td>100</td><td></td><td></td><td>0</td><td>0.63</td></tr></table></body></html>\n\n注：EB210 是 $\\mathrm{EBECRYL^{\\circledast}}210$ 的缩写，其他类同，下同。外，相对分子质量的多分散性也造成酯键分布的不均匀，会影响到测试结果。 但无论如何，随着酯键密度的升高，各种低聚物在ABS 上的附着力是随之提高的。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 2􀆰 3 醚键对附着力的影响  \n\n在自由基类光固化的单体和低聚物中，醚键是大量存在的。 例如，全部乙氧化和丙氧化的单体、全部双酚A 型环氧丙烯酸酯、全部的聚醚类的聚氨酯丙烯酸酯、全部的聚醚丙烯酸酯、部分的聚酯丙烯酸酯和聚酯扩链的聚氨酯丙烯酸酯。 本文选取了具有代表性的含醚键的单体和低聚物，考察了它们在 ABS 上的附着力。 需要说明的是，醚键仅仅是影响附着力的因素之一，而非全部。 读者在具体实践时请综合考虑。  \n\n为了进一步研究醚键和酯键对附着力的影响，本文定义了2 个新的概念，醚键密度（ $C_{\\mathrm{et}}$ ）和酯键醚键密度比（ $C_{\\mathrm{es}}/C_{\\mathrm{et}}^{\\mathrm{}}$ ），计算公式分别如式（2）、式（3）所示。  \n\n醚键密度 $\\mathbf{\\Sigma}=\\mathbf{\\Sigma}$ 每摩尔单体或低聚物中的醚键的物质的量／相对分子质量 $\\times100\\%$ 式（2）  \n\n酯键醚键密度比 $\\mathbf{\\Sigma}=\\mathbf{\\Sigma}$ 酯键密度／醚键密度 式（3）  \n\n表5 是3 种醚键含量不同的单体在 ABS 上的附着力。 当醚键密度从 TMPTA 的 $0\\%$ 增加到 SR502 的$1.3\\%$ ，附着力迅速从0 级下降到 5 级。 可推断，醚键对附着力是有明显负作用的。 当然，乙氧基链段的增加也降低了酯键密度，进而降低了附着力。  \n\n表5　 醚键与附着力的关系  \nTable 5　 Relationship between ether bond and adhesion   \n\n\n<html><body><table><tr><td>名称</td><td>结构组成</td><td>附着力/级</td><td>醚键密度/%</td><td>酯键密度/%</td><td>酯键醚键密度比</td></tr><tr><td>TMPTA</td><td>无醚键</td><td>0</td><td>0</td><td>1.01</td><td>8</td></tr><tr><td>TMP(EO)TA</td><td>分子中含3个醚键</td><td>2</td><td>0. 7</td><td>0. 7</td><td>1</td></tr><tr><td>SR502[TMP(EO）,TA]</td><td>分子中含9个醚键</td><td>５</td><td>1.3</td><td>0.43</td><td>0.33</td></tr></table></body></html>  \n\n为了进一步证明醚键对附着力的负作用，表 6 列举了更多含有醚键的单体和低聚物的相关数据。 除EB3708 之外，所有样本在 ABS 上均显示了较差的附着力，而这些样本都具有较高的醚键密度 $(>0.4\\%)$ 。对 比 TPGDA、 NPG （ PO ） $_{_{2}}\\mathrm{DA}$ 、 GP （ PO ） $_{3}\\mathrm{TA}$ 和  \n\nEB3708，虽然前三者的酯键密度比 EB3708 略高，但是因其醚键密度比 EB3708 高出更多，因此其附着力较差。 换言之，前三者的酯键醚键密度比远低于EB3708，故其附着力差于后者。  \n\n表6　 含有醚键的单体和低聚物的相关参数  \nTable 6　 Characters of monomers and oligomers with ether bonds   \n\n\n<html><body><table><tr><td>产品名称</td><td>结构组成</td><td>数均相对 分子质量</td><td>附着 力/级</td><td>醚键密 度/%</td><td>酯键密 度/%</td><td>酯键醚键 密度比</td></tr><tr><td>TPGDA</td><td>含2个醚键</td><td>300</td><td>５</td><td>0.67</td><td>0.67</td><td>1</td></tr><tr><td>NPG( PO)DA</td><td>含2个醚键</td><td>328</td><td>５</td><td>0.61</td><td>0.61</td><td>１</td></tr><tr><td>GP(PO)TA</td><td>含3个醚键</td><td>428</td><td>３</td><td>0.7</td><td>0. 7</td><td>1</td></tr><tr><td>EB12</td><td>三官能度聚醚丙烯 酸酯,含12个醚键</td><td>800</td><td>５</td><td>1.5</td><td>0.38</td><td>0. 25</td></tr><tr><td>EB11</td><td>二官能度聚醚丙烯 酸酯,含12个醚键</td><td>700</td><td>５</td><td>1.7</td><td>0.29</td><td>0.17</td></tr><tr><td>EB13</td><td>二官能度聚醚丙烯 酸酯,含8个醚键</td><td> 500</td><td>５</td><td>1.6</td><td>0. 4</td><td>0. 25</td></tr><tr><td>EB600</td><td>含2个醚键</td><td>500</td><td>5</td><td>0.4</td><td>0.4</td><td>1</td></tr><tr><td>EB3708</td><td>含2个醚键</td><td>1 400</td><td>0</td><td>0.14</td><td>0.57</td><td>4</td></tr><tr><td>EB270</td><td>含16个醚键</td><td>1 500</td><td>５</td><td>1.07</td><td>0.27</td><td>0.25</td></tr><tr><td>EB4100</td><td>含12个醚键</td><td>1 100</td><td>５</td><td>1.09</td><td>0. 45</td><td>0. 41</td></tr><tr><td>EB4200</td><td>含10个醚键</td><td>1 500</td><td>５</td><td>0.7</td><td>0.4</td><td>0.57</td></tr></table></body></html>  \n\n综合表4、表5 和表6，可得出如下结论：（1）化学结构中的酯键和醚键是影响附着力的关键因素；酯键可以提高附着力，而醚键则会降低附着力。 （2）在不含醚键的单体和低聚物中，如果酯键密度 $\\geqslant0.6\\%$ ，则可在 ABS 上获得良好的附着力。 （3）在含有醚键的单体和低聚物中，需要同时考虑酯键密度和酯键醚键密度比2 个因素，只有酯键密度 $\\geqslant0.6\\%$ 并且酯键醚键密度比 $\\geqslant4$ ，才能获得良好的附着力。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3　 结　 语  \n\n通过实验测试了不同的单体和低聚物在 ABS 上的附着力，并从化学结构的角度解释了引起附着力差异的影响因素，建立了衡量附着力的 3 个关键指标：酯键密度、醚键密度和酯键醚键比。 得出如下结论：（1）化学结构是决定附着力的首要因素，而体积收缩是次要的因素。 （2）化学结构中，酯键可以提高在  \n\nABS 上的附着力；而醚键则会降低附着力。 （3）在不含醚键的单体和低聚物中，如果酯键密度 $\\geqslant0.6\\%$ ，则可在 ABS 上获得良好的附着力。 （4）在含有醚键的单体和低聚物中，需要同时考虑酯键密度和酯键醚键密度比2 个因素。 只有酯键密度 $\\geqslant0.6\\%$ 并且酯键醚键密度比 $\\geqslant4$ ，才能获得良好的附着力。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 14,
+        "chunk": "# 参考文献  \n\n［1］ 陈用烈，曾兆华，杨建文．辐射固化材料及其应用［M］．北京：化学工业出版社，2003．  \n［2］ 魏杰，金养智．光固化涂料［M］．北京：化学工业出版社，2005．  \n［3］ 杨建文，曾兆华，陈用烈．光固化涂料及应用［M］．北京：化学工业出版社，2004．  \n\n收稿日期 2017－04－18（修改稿）",
+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,632 @@
+[
+    {
+        "id": 1,
+        "chunk": "# 博士学位论文  \n\n阳离子型纤维素衍生物的制备与性能  \n\n作者姓名： 程耀辉  \n指导教师： 张军 研究员 中国科学院化学研究所张金明副研究员 中国科学院化学研究所  \n学位类别： 工学博士  \n学科专业： 材料学  \n培养单位： 中国科学院化学研究所",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# 博士学位论文",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# 阳离子型纤维素衍生物的制备与性能  \n\n作者姓名： 程耀辉指导教师： 张军 研究员 中国科学院化学研究所张金明副研究员 中国科学院化学研究所学位类别： 工学博士学科专业： 材料学培养单位： 中国科学院化学研究所  \n\nA dissertation submitted to University of Chinese Academy of Sciences in partial fulfillment of the requirement for the degree of Doctor of Philosophy in Materials Science By Cheng Yaohui Supervisor: Professor Zhang Jun Associater Professor Zhang Jinming  \n\nInstitute of Chemistry Chinese Academy of Science June 2020",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 中国科学院大学",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# 研究生学位论文原创性声明  \n\n本人郑重声明：所呈交的学位论文是本人在导师的指导下独立进行研究工作所取得的成果。尽我所知，除文中已经注明引用的内容外，本论文不包含任何其他个人或集体已经发表或撰写过的研究成果。对论文所涉及的研究工作做出贡献的其他个人和集体，均已在文中以明确方式标明或致谢。  \n\n作者签名：程克翟皮早日期：21",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 中国科学院大学学位论文授权使用声明  \n\n本人完全了解并同意遵守中国科学院有关保存和使用学位论文的规定，即中国科学院有权保留送交学位论文的副本，允许该论文被查阅，可以按照学术研究公开原则和保护知识产权的原则公布该论文的全部或部分内容，可以采用影印、缩印或其他复制手段保存、汇编本学位论文。  \n\n涉密及延迟公开的学位论文在解密或延迟期后适用本声明。  \n\n作者签名：程光翟焊 导师签名： 张争日 期：702日 期：2021.5·25",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# 摘要  \n\n纤维素是一种来源广泛、可再生、可生物降解的天然高分子材料。海洋污染、土地污染越来越严重，纤维素被认为是未来可降解材料、化工、能源的重要原料之一。纤维素是高结晶度且分子内、分子间存在大量的氢键的高分子，因此其难溶解、不熔融，使其实际使用受限。近年来，纤维素新型溶剂被广泛研究，例如氢氧化钠/尿素体系和离子液体体系，使纤维素的化学改性和加工变得可行。其中，离子液体作为一种应用前景广阔的绿色溶剂，其蒸气压低、不易燃、稳定性高和容易回收再利用，为纤维素的绿色加工成型和功能化提供了广阔的前景。  \n\n为了扩展纤维素材料的功能及其应用领域，充分利用纤维素资源，本文以离子液体为溶剂，通过纤维素链上丰富的羟基进行衍生化，设计合成了新型阳离子化纤维素衍生物，进而结合聚集态微观调控，制备了具有各种功能性纤维素材料。本论文的主要研究成果如下：  \n\n1.阳离子型纤维素衍生物的合成与溶解性：提出一种制备阳离子型纤维素衍生物的方法：利用均相酯化反应，将2-氯丙酰氯通过化学键键合到纤维素链上，得到不同取代度的含氯纤维素衍生物；然后与三丁基麟、吡啶、1-甲基咪唑和1-乙烯基咪唑进行亲核取代反应；最后再进行阴离子交换，得到了不同取代度、不同阳离子和不同阴离子的阳离子型纤维素衍生物。通过对阳离子型纤维素衍生物的取代度和阴阳离子种类进行调控，可以得到水溶、醇溶等在常见溶剂中表现出不同溶解性的纤维素衍生物材料。不同溶解性样品可以应用到不同领域及场景中，例如水溶性样品可作为水溶性涂料，醇溶性样品可以应用于医药领域。更进一步地，含有乙烯基咪唑阳离子和Cl阴离子的阳离子纤维素衍生物cellulose-VimCl可以很好地分散蒙脱土；当蒙脱土的含量不低于 $30\\mathrm{wt\\%}$ 时，得到水溶性阻燃涂料。蒙脱土的引入显著地降低了纤维素材料的最大热释放速率、热释放总量和热释放能力，使得该纤维素基涂层材料表现出离火自熄效应。  \n\n2.利于 $\\mathbf{CO}_{2}$ 透过的阳离子型纤维素衍生物的制备与气体分离性能：基于上一章中的合成方法，将1-丁基咪唑引入到醋酸纤维素上，随后将氯离子（CI）阴离子交换为双三氟甲磺酰亚胺（TfN)阴离子，得到含有丁基咪唑阳离子和TfN阴离子的阳离子型醋酸纤维素CA-BimTfN。利用CA-BimTfN中离子化基团与自由离子液体静电吸引作用固载离子液体，制备了一系列复合不同种类离子液体的膜材料，用于气体分离。发现C1omimTfN离子液体的引入对复合膜的气体透过性能影响最大，显著地增大 $\\mathbf{CO}_{2}$ 气体的透过，而且能够保持 $\\mathrm{CO}_{2}/\\mathrm N_{2}$ 的选择性不低于24。增加CA-BimTfN/CiomimTfN复合膜中CiomimTfN 的含量， $\\mathrm{CO}_{2}$ 渗透系数可达91barrer，比纯醋酸纤维素提高了 $3800\\%$ 。同时，CA-BimTfN /CiomimTfN复合膜的拉伸强度保持在 $10\\mathrm{MPa}$ 以上，分解温度高于 $250^{\\circ}\\mathrm{C}$ ，保证了实际使用中对分离膜材料的力学性能和热稳定性的要求。  \n\n3.具有防雾、抗冰和自清洁性能的阳离子型纤维素衍生物的制备与性能：基于第二章中的合成方法，将1-丁基咪唑引入纤维素，然后将阴离子交换为全氟辛酸（PFO-）阴离子，制得阳离子纤维素衍生物Cellulose-BimPFO。通过控制取代度，改变羟基和BimPFO基团的比例，从而达到调控界面亲疏水性，得到可以形成界面水的疏水涂层材料，其表现出优异的防雾、抗冰和自清洁性能。由于离子化结构和保留部分纤维素羟基，该涂层在低湿度环境下可以吸附水汽形成均匀水膜，从而实现低湿度下防雾；当湿度增加时，由于PFO阴离子高的疏水性，该涂层材料表现出疏水性，促进水滴滚落，从而实现高湿度下防雾。由于很容易形成界面水，Cellulose-BimPFO涂层能够使水结冰温度降低至 $-30^{\\circ}\\mathsf{C}$ ， $-30^{\\circ}\\mathsf{C}$ 下冰粘附力降低至 $10\\mathrm{kPa}$ ， $-25^{\\circ}\\mathbf{C}$ 下的结冰时间超过 $2\\ensuremath{\\mathrm{h}}$ 。另外，由于Cellulose-BimPFO离子化结构，其对金黄色葡萄球菌具有 $97\\%$ 以上的杀菌率。由于 CelluloseBimPFO涂层高疏水性和低表面能，使其具有良好的耐水性、自清洁性和抗污性能。  \n\n4.具有紫外光和蓝光屏蔽性能的阳离子型纤维素衍生物的制备与性能：基于第二章中的合成方法，将1-丁基咪唑引入到醋酸纤维素上，随后与金属氯化盐$(\\mathbf{MCl_{x}}$ ）反应，得到含有1-丁基咪唑阳离子（ ${\\mathbf B}_{\\mathbf{um}}^{*}$ ）和金属氯化盐 $(\\mathbf{MCl_{x+1}}^{-})$ 阴离子的阳离子型醋酸纤维素 $\\mathbf{CA-BimMCl{x}_{+1}}$ 。其中， $\\displaystyle\\mathbf{Fe}^{3+}$ ， ${\\mathsf{C u}}^{2+}$ 等金属离子的引入，使得所得阳离子型醋酸纤维素 $\\mathbf{CA-BimMCl_{x+1}}$ 具有抗紫外光和抗蓝光性能。将不同比例的 $\\mathsf{F e}^{3+}$ 、 ${\\mathsf{C u}}^{2+}$ 同时络合时，可以得到对 $200{\\cdot}450\\ \\mathrm{nm}$ 波长光全吸收的膜材料。从而，通过调控金属离子含量得到具有抗紫外光及蓝光的薄膜。同时，所制备的膜可保持良好的透明度，最高在 $550\\mathrm{nm}$ 处具有 $75\\%$ 以上的透光率。膜的力学性能也能够保持在 ${55}\\mathbf{MPa}$ 以上以及 $230^{\\circ}\\mathrm{C}$ 以上的热分解温度，满足作为保护膜的实际使用。  \n\n关键词：纤维素，水溶性衍生物，气体分离，防雾，",
+        "category": " Abstract"
+    },
+    {
+        "id": 8,
+        "chunk": "# Abstract  \n\nCellulose is a natural polymer material with a wide range of sources, renewable and biodegradable. As marine pollution and land pollution become more and more serious, cellulose is considered to be one of the important raw materials for future degradable materials, chemicals, and energy. Cellulose is a polymer with high crystallinity and a large number of hydrogen bonds in and between molecules, so it is difficult to dissolve and does not melt, which limits its practical use. In recent years, new cellulose solvents have been extensively studied, such as sodium hydroxide/urea systems and ionic liquid systems, making the chemical modification and processing of cellulose feasible. Among them, as a green solvent with broad application prospects, ionic liquids have low vapor pressure, are not flammable, have high stability, and are easy to be recycled and reused, providing broad prospects for the green processing and functionalization of cellulose  \n\nIn order to expand the functions and application fields of cellulose materials and make full use of cellulose resources, this paper uses ionic liquid as a solvent to derivatize the cellulose chain through the abundant hydroxyl groups, and designs and synthesizes a new type of cationized cellulose derivative. Furthermore, combined with the micro-control of the aggregation state, various functional cellulose materials were prepared. The main research results of this paper are as follows:  \n\n1. Synthesis and solubility of cationic cellulose derivatives: A method for preparing cationic cellulose derivatives is proposed: using a homogeneous esterification reaction, 2-chloropropionyl chloride is chemically bonded to the cellulose chain, Obtain chlorine-containing cellulose derivatives with different degrees of substitution; then carry out nucleophilic substitution reaction with tributylphosphine, pyridine, 1- methylimidazole and 1-vinylimidazole; then carry out anion exchange to obtain different degrees of substitution, Cationic cellulose derivatives with different cations and different anions. By adjusting the degree of substitution of cationic cellulose derivatives and the types of anions and cations, it is possible to obtain cellulose derivative materials that exhibit different solubility in common solvents, such as watersoluble and alcohol-soluble. Different solubility samples can be applied to different fields and scenarios. For example, water-soluble samples can be used as water-soluble coatings, and alcohol-soluble samples can be used in the medical field. Furthermore, VimCl, a cationic cellulose derivative containing vinylimidazole cations and Cl-anions, can disperse montmorillonite well; when the content of montmorillonite is not less than $30~\\mathrm{wt\\%}$ 、 a water-soluble flame retardant coating is obtained. The introduction of montmorillonite significantly reduces the maximum heat release rate, total heat release and heat release capacity of the cellulose material, so that the cellulose-based coating material exhibits a self-extinguishing effect from the fire.  \n\n2. Preparation and gas separation performance of cationic cellulose derivatives that are conducive to $\\mathrm{CO}_{2}$ permeation: Based on the synthesis method in the previous chapter, l-butylimidazole is introduced into cellulose acetate, and then chloride ion (Cl) The anion is exchanged for bistrifluoromethanesulfonimide (TfN) anion to obtain cationic cellulose acetate CA-BimTfN containing butylimidazole cation and TfN-anion. Using the electrostatic attraction of the ionized groups in CA-BimTfN and the free ionic liquid to immobilize the ionic liquid, a series of composite membrane materials of different types of ionic liquids were prepared for gas separation. It is found that the introduction of $\\mathbf{C}_{10}\\mathbf{mimTf}_{2}\\mathbf{N}$ ionic liquid has the greatest impact on the gas permeability of the CA-BimTfN/C1omimTfN composite membrane, which significantly increases the $\\mathrm{CO}_{2}$ gas permeability, and can maintain the $\\mathbf{CO}_{2}/\\mathbf{N}_{2}$ selectivity not less than 24. By increasing the content of $\\mathbf{C}_{10}\\mathbf{\\dot{mimTf}}_{2}\\mathbf{N}$ in the CA-BimTfN/ClomimTfN composite membrane, the $\\mathbf{CO}_{2}$ permeability coefficient can reach 9l barrer, which is $3800\\%$ higher than pure cellulose acetate. At the same time, the tensile strength of the CABimTfN/CiomimTfN composite membrane is maintained above $10\\ \\mathrm{MPa}$ ， and the decomposition temperature is higher than $250~^{\\circ}\\mathrm{C}$ 。 which ensures the mechanical properties and thermal stability of the separation membrane material in actual use.  \n\n3. Preparation and performance of cationic cellulose derivatives with anti-fogging, antiicing and self-cleaning properties: Based on the synthesis method in Chapter 2, 1- butylimidazole is introduced into cellulose, and then the anions are exchanged for perfluorooctanoic acid (PFO) anion to prepare the cationic cellulose derivative Cellulose-BimPFO. By controlling the degree of substitution and changing the ratio of the hydroxyl group and the BimPFO group, the hydrophobicity of the interface can be adjusted to obtain a hydrophobic coating material that can form interface water, which exhibits excellent anti-fog, anti-icing and self-cleaning properties. Due to the ionized structure and retaining part of the cellulose hydroxyl group, the coating can absorb water vapor to form a uniform water film in a low humidity environment, thereby achieving anti-fogging under low humidity; when the humidity increases, due to the high hydrophobicity of PFO-anions, the The coating material exhibits hydrophobicity and promotes water droplets to roll off, thereby achieving anti-fogging under high humidity. Because of the easy formation of interfacial water, the Cellulose-BimPFO coating can reduce the freezing temperature of water to $\\mathbf{-30\\circC} $ the ice adhesion force at $-30\\ {^{\\circ}}\\mathrm{C}$ to $10\\mathrm{kPa}$ and the freezing time at $\\pmb{-25}\\circ_{\\mathbf{C}}$ for more than $2\\mathbf{h}$ In addition, due to the ionized structure of Cellulose-BimPFO, it has a bactericidal rate of more than $97\\%$ against Staphylococcus aureus. Due to the high hydrophobicity and low surface energy of Cellulose-BimPFO coating, it has good water resistance, self-cleaning and anti-fouling properties.  \n\n4. Preparation and performance of cationic cellulose derivatives with UV and blue shielding properties: Based on the synthesis method in Chapter 2, 1-butylimidazole is introduced onto cellulose acetate, and then combined with metal chloride (MClx) reaction to obtain cationic cellulose acetate $\\mathbf{CA-BimMCl{x}+1}$ containing 1-butyl-3- methylimidazole cation $(\\mathbf{Bim^{+}})$ and metal chloride $(\\mathbf{MCl_{x+1}}^{\\bullet})$ anion. Among them, the introduction of metal ions such as $\\mathsf{F e}^{3+}$ and ${\\mathsf{C u}}^{2+}$ makes the resulting cationic cellulose acetate $\\mathbf{CA-BimMCl{x}+1}$ have anti-ultraviolet and anti-blue light properties. When different proportions of $\\mathbb{F}e^{3+}$ and ${\\mathrm{Cu}}^{2+}$ are complexed at the same time, a film material that fully absorbs light with a wavelength of $200{-}450~\\mathrm{nm}$ can be obtained. Thus, a thin film with anti-ultraviolet and blue light can be obtained by adjusting the content of metal ions. At the same time, the prepared film can maintain good transparency, with a light transmittance of more than $75\\%$ at $550~\\mathrm{nm}$ . The mechanical properties of the membrane can also be maintained at a thermal decomposition temperature above 55 VII  \n\nMPa and $230^{\\circ}\\mathbf{C},$ which is sufficient to ensure practical use  \n\nKeywords: Cellulose, Water-soluble derivatives ,Gas separation, Anti-fogging.",
+        "category": " Abstract"
+    },
+    {
+        "id": 9,
+        "chunk": "# 目录  \n\n第1章 绪论.  \n\n1.1纤维素概况  \n1.1.1纤维素的来源 1  \n1.1.2纤维素的结构. 3  \n1.2纤维素溶剂体系. .4  \n1.2.1非水相非衍生化溶剂 .5  \n1.2.2衍生化溶剂 .6  \n1.3纤维素衍生化反应 7  \n1.3.1纤维素酯化反应 ..8  \n1.3.2纤维素醚化反应 .10  \n1.3.3纤维素氧化反应 .10  \n1.3.4纤维素高分子接枝反应 11  \n1.4离子型聚合物简介 .12  \n1.4.1离子型聚合物性质 .12  \n1.4.2离子型聚合物应用 .14  \n1.5防雾抗冰材料研究进展 .20  \n1.5.1防雾材料研究进展 .20  \n1.5.1.1超亲水防雾材料 .22  \n1.5.1.2超疏水防雾材料 .23  \n1.5.1.3两性离子-润湿防雾材料 .24  \n1.5.2防结冰材料的研究 .25  \n1.5.2.1亲水性防结冰材料 ..25  \n1.6本论文的研究目的和意义 .28",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# 第2章阳离子型纤维素衍生物的合成与溶解性 31  \n\n2.1引言. 31  \n2.2实验部分. 32  \n2.2.1原料和试剂 32  \n2.2.2阳离子型纤维素衍生物的合成 .33  \n2.2.2.1多种不同阳离子纤维素衍生物的合成. .33  \n2.2.2.2阻燃性水溶性纤维素衍生物合成 34  \n\n2.2.3测试和表征. 34 .3结果与讨论 35  \n\n2.3.1阳离子纤维素衍生物的合成 35  \n2.3.2阳离子纤维素衍生物的表征 .37  \n2.3.2阳离子纤维素衍生物的溶解性 38  \n\n2.3.2.1阳离子纤维素衍生物随取代度和阳离子基团溶解性变化（以  \n\nCell-C1 $\\scriptstyle{\\mathtt{D S}}=3.0$ 为原料) 38  \n\n2.3.2.2阳离子纤维素衍生物随取代度和阴离子基团溶解性变化（以  \n\nCell-Cl ${\\tt D S}{=}3.0$ 为原料) 42  \n2.3.2.3阳离子纤维素衍生物随取代度和阴离子基团溶解性变化（以  \nCell-C1 ${\\tt D S}{=}1.5$ 为原料) .44  \n2.3.3阻燃水溶性涂层 .46  \n2.3.3.1阻燃水溶性涂层基本表征 .46  \n2.3.3.2阻燃水溶性涂层燃烧实验 .47  \n2.3.3.3复合膜阻燃机理 .48  \n\n2.4本章小结 51",
+        "category": " Introduction"
+    },
+    {
+        "id": 11,
+        "chunk": "# 第3章利于 $\\mathbf{CO}_{2}$ 透过的阳离子型纤维素衍生物的制备与气体分离性",
+        "category": " Introduction"
+    },
+    {
+        "id": 12,
+        "chunk": "# 能 53  \n\n3.1 引言 53  \n3.2实验部分. .54  \n3.2.1原料和试剂 54  \n3.2.2醋酸纤维素衍生物合成. .54  \n3.2.3气体分离膜制备 55  \n3.2.4结构与性能表征. .55  \n3.3结果与讨论. .56  \n3.3.1醋酸纤维素阳离子衍生物合成及表征 ..56  \n3.3.2分离膜形貌表征 .59  \n3.4本章小结. ..67",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# 第4章具有防雾、抗冰和自清洁性能的阳离子型纤维素衍生物的制",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 备与性能 .67  \n\n4.1引言 .67  \n4.2实验部分. .68  \n4.2.1原料和试剂 .68  \n4.2.2疏水性阳离子纤维素衍生物合成 .69  \n4.2.3功能涂层膜制备 .69  \n4.2.4结构与性能表征. .70  \n4.3结果与讨论. .72  \n4.3.1样品合成及表征 ..72  \n4.3.2膜及涂层基本性质表征 ..75  \n4.3.3防雾性能表征. .76  \n4.3.4抗冰性能表征 .78  \n4.3.5耐水性、抗生物粘附性和自清洁表征表征： .81  \n4.4本章小结. .83",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# 第5章具有紫外光及蓝光屏蔽性能的阳离子型纤维素衍生物的制备  \n\n与性能. 85  \n\n5.1引言 85  \n\n5.2实验部分. 86  \n5.2.1原料和试剂 86  \n5.2.2样品合成 .86  \n5.2.3测试和表征 .87  \n5.3结果与讨论. .88  \n5.3.1样品合成及表征 .88  \n5.3.2膜紫外屏蔽性能表征 .89  \n5.3.2膜力学性能及热稳定性表征 .93  \n5.4本章小结. .96  \n第6章结论. .97  \n参考文献 99  \n致谢.. 121  \n作者简历及攻读学位期间发表的学术论文与研究成果 123",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 16,
+        "chunk": "# 第1章绪论",
+        "category": " Introduction"
+    },
+    {
+        "id": 17,
+        "chunk": "# 1.1纤维素概况  \n\n纤维素是由葡萄糖单元组成的可降解天然高分子材料，是自然界中最悠久的分布最广、储存量最大的一种多糖。纤维素是棉花、木材等植物细胞壁的主要成分，植物每年通过光合作用可以生产超过千亿吨的纤维素[2]。因此，可以说纤维素是一种储量丰富、来源广泛的可再生自然能源。人类很早就开始使用纤维素材料，比如最为大家熟知的纸张。而且，在第一次工业革命之前，纤维素一直是人类主要的能源和建筑材料来源。纤维素及其衍生物也是近代高分子科学诞生和发展时期的主要研究对象，有关纤维素的研究成果也对高分子科学的发展具有重大的贡献[3]。随着纤维素溶剂研究发展，纤维素及其衍生物应用领域也被进一步扩宽。目前，纤维素及其衍生物已经被广泛应用到包装材料、造纸、建筑、能源、化工、纺织、食品、医药等领域[4-i0]。由于合成高分子材料在自然界中降解慢，在其不当处置和使用过程中不可避免地造成了环境污染，威胁了人类健康及其它动植物的生命安全。因此，无毒无污染、生物相容性好、可生物降解的、价格低廉、易于改性的天然高分子纤维素及其衍生物在解决上述问题中，发挥着重要角色。有关纤维素的研究及应用对于发展绿色化学、改善生态环境、能源结构以及促进可持续发展都具有重要而深远的意义[11,12]。",
+        "category": " Introduction"
+    },
+    {
+        "id": 18,
+        "chunk": "# 1.1.1纤维素的来源  \n\n纤维素根据来源不同可分为两大类，即天然纤维素和人工合成纤维素。天然纤维素主要是通过植物光合作用产生的，是目前工业纤维素的主要来源[13]另外，一些动物例如，海鞘类动物、真菌、细菌和海洋藻类等生物体内也会产生纤维素。植物纤维素主要包括以下几大类：  \n\n棉花：是植物中纤维素含量最高、品质最佳和用量最大的天然纤维素资源，含量约 $95\\%$ 。棉花作为我们日常使用纺织原料，其纤维弹性好、质地柔软、强度高，可直接纺织制备各种各样的织物。此外，棉花也是制备纤维素浆料、纤维素衍生物、微晶纤维素、玻璃纸和黏胶纤维等的原料。  \n\n木材：纤维素含量为 $50\\%$ 左右，主要存在于植物细胞壁中，是为植物提供力学强度的组分[14]。木材分为硬木和软木两大类，硬木主要包括冷杉属、云杉属、松属、铁杉属和落叶松等在内的针叶树材；软木主要包括按木属、桦木属、杨木属和木属等在内的阔叶树材。纤维素化学工业和造纸业的主要原料也是木材纤维素。  \n\n草类：纤维素含量占比 $40\\text{\\textperthousand}$ ，在中国，草类资源丰富，也使其成为造纸业的主要原料之一。草类种类繁多，可分为禾本科亚科和竹亚科。其中，禾本亚科主要包括高梁秸秆、玉米秸秆、麦秆、稻草、龙须草、芦苇和甘蔗渣等，其中大部分是农业副产物。在我国，每年有接近10亿吨的农业废弃物，其中大多被填埋，焚烧等，未被高值化利用，造成浪费资源。农业废弃物的高值化利用，也可以进一步推动农业的发展。竹亚科主要包括楠竹、斑苦竹、毛竹和水竹等。其中，一些种类的竹子所含纤维素含量可达 $75\\%$ 以上。竹类生长周期短，产量巨大，其纤维素可以用来制备高质量溶解浆，同时可制备用于家居、服饰等领域的特殊性能的纤维。草类植物中，半纤维素含量较高，木质素较少，纤维短，灰分多。  \n\n韧皮类：主要包括黄麻、大麻、剑麻、苎麻和亚麻等。约含有 $40\\text{\\textperthousand}$ 的纤维素。通常具有优异的韧性和纤维强度，但数量较少，常用作高档纸张与纺织纤维的原料。  \n\n细菌纤维素：除了植物纤维素外，海洋中的海鞘类动物、水藻和真菌、细菌等的体内也可以合成出纤维素[15,16]。1866 年，英国科学家首次发现细菌纤维素，其是木醋杆菌所产生的代谢产物[17]。利用葡萄糖做碳源合成细菌纤维素的菌种主要包括土壤杆菌属、根瘤菌属和固氮菌属等。细菌纤维素具有与植物纤维素相同的化学组成和分子结构，但是细菌纤维素结晶度高、聚合度高、力学性能优异，此外透气透水性好和生物相容性优良，因此细菌纤维素已经广泛应用到人造皮肤精细化工、医药材料和组织培养等领域，是目前极具研究前景和发展前景的纤维素新材料[18,19]。  \n\n人工合成纤维素：主要有两种方法合成，即酶催化、葡萄糖衍生物的开环聚合。人工合成纤维素的聚合度一般较低，大概在20-50之间，但是合成纤维素纯度高、结晶度高，不含半纤维素，木素等杂质[20,21]。",
+        "category": " Introduction"
+    },
+    {
+        "id": 19,
+        "chunk": "# 1.1.2纤维素的结构",
+        "category": " Introduction"
+    },
+    {
+        "id": 20,
+        "chunk": "# 纤维素化学结构  \n\n1838年，法国化学家安塞尔梅·佩恩（AnselmePayen）描述了处理含有酸和氨的各种植物组织以及随后用水，乙醇和乙醚萃取得到残留的抗性纤维状固体，他通过元素分析确定分子式为 $\\mathrm{C_{6}H_{10}O_{5}}$ ，并观察与淀粉的异构现象。术语\"纤维素”在1839年国学院关于Payen工作的报告中首次使用，并将其命名为cellulose（纤维素)，由此纤维素的概念被第一次提出。在1932年，德国化学家赫尔曼施陶丁格（Hermann Staudinger）通过研究进一步确定了纤维素的化学结构[22]。  \n\n纤维素作为碳水化合物其分子结构由重复 $\\upbeta$ -D-吡喃葡萄糖通过在C4和C1碳原子（β-1,4-葡聚糖）上的OH之间缩醛共价连接的，原则上来讲纤维素是生物遗传形成的。因此，纤维素是一种大量的线性链状聚合物，具有较多的羟基（每个脱水葡萄糖（AGU）单元有三个）其以热力学上优选的 $^4{\\bf C}{\\bf l}$ 构象存在。两个相邻的结构单元定义纤维二糖。碳元素在分子式中占比为 $44.4\\%$ 、氢元素占比为$6.2\\%$ 、氧元素占比为 $49.4\\%^{[23]}$ 。所以，现在纤维素习惯用两个长度为 $1.3\\mathsf{n m}$ 的纤维二糖单元来表示其重复单元，如图1.1所示。其构象可分为六角船式构象、椅式构象两种，因为椅式构象具有较低的能量从而更加地稳定，因此通常以椅式构象存在。  \n\n![](images/0e0da1f0d15956465ccd5e1e4bd35ad08f1ce69964fb213c4359f101636ff606.jpg)  \n\n（b）Haworth结构式  \n\n纤维素的每个AGU单元上均含有分别位于2,3,6位的自由羟基，其中，2,3位上的羟基是仲羟基，6位上的羟基被称为伯羟基，其活性较高，且这三个羟基均是具有醇羟基的特性。纤维素结构中的可反应羟基，为纤维素化学改性提供了基础，可以使纤维素衍生化制备得到各功能化材料。纤维素是典型的\"缩聚型\"高分子，它的两个末端基性质不同，一端是仲醇羟基（C4-OH)，不具有还原性，另一端是半缩醛结构（C1-OH)，具有还原性。整个纤维素大分子呈现方向性且具有极性。  \n\n纤维素和聚合物中单体单元的数量通常以聚合度（DP）表示。不经过纯化的样品只能提供分子量平均值。平均值有几种形式，其中重均分子量Mw可以通过光散射直接测量获得。数均分子量Mn对计算端基或分散性很重要，纤维素材料的分子量及其分布因来源、生产工艺和处理而有较大的差异。纤维素作为一种天然高分子，其分子量大且具有多分散性。纤维素及其衍生物的分子量及分布会对纤维素材料的物理机械性能、溶解性能、粘度和流变性能等有直接影响，也是对纤维素材料生产和使用过程中降解、老化和各种化学反应的重要判断指标。因此，对纤维素分子量及其分布的测定对发展及应用纤维素材料都具有重要的意义。纤维素的分子量可以直接用聚合度（DP）计算得到，即分子量 $\\scriptstyle=162\\times\\mathbf{DP}$ 。对纤维素及衍生物的分子量及分布测量的方法主要有粘度法、体积排除色谱（即凝胶渗透色谱，GPC）和光散射法。其中，GPC是测量分子量的主要方法，由于纤维素难以溶解到常规有机溶剂中，因此多以先将纤维素衍生化，再溶解于有机溶剂，通过GPC 进行测定24]。但是，纤维素在衍生化过程中，不免发生降解，因此近年来也发展出离子液体或者离子液体和有机溶剂共溶剂体系直接将纤维素溶溶解，随后进行GPC 测定的方法[25]。",
+        "category": " Introduction"
+    },
+    {
+        "id": 21,
+        "chunk": "# 1.2纤维素溶剂体系  \n\n为什么溶解纤维素如此重要?以下原因可列举:1.再生和新型材料的制备如纤维(如纺织应用)和薄膜(如包装应用)，2.在均相溶液中生产有价值的纤维素衍生物(注意，典型的溶剂不能穿透纤维素内部的结晶区域，因此非均相改性只能限制在结晶区域表面)，3.使降解纤维素更有效(例如，重要的生物炼制)。  \n\n由于天然纤维素分子内及分子间氢键且其分子量和结晶度较高，因此使其不能溶解于水、稀酸、稀碱以及常见有机溶剂，也不能熔融，这使纤维素的应用及改性受到了一定的局限性。随着科学的进步，研究者也开发出了许多无毒、无污染的新型纤维素溶剂体系。可分为两大类：非衍生化溶剂和衍生化溶剂。  \n\n非衍生化溶剂只对纤维素进行物理溶解，不会改变其原来的化学结构。可以分为水相溶液和非水相溶液。  \n\n水相非衍生化溶剂主要包括质子酸和Lewis酸、金属盐络合物、无机金属盐水合物、碱/水溶液体系。  \n\n质子酸如HC1( $40-43\\%$ 、 ${\\bf{\\bar{H N O}}}_{3}$ （ $84\\%$ ）、 $\\mathbf{H}_{2}\\mathbf{S}\\mathbf{O}_{4}$ 1 $65-80\\%$ ）和 $\\mathrm{H}_{3}\\mathrm{PO}_{4}$ (73-$83\\%$ ）等可以溶解纤维素。目前在质子酸体系中，认为的溶解机理为纤维素在酸中发生部分质子化，以聚电解质形式溶解。该体系中，最常见的影响纤维素溶解的因素为酸的浓度及温度。但是，纤维素在质子酸中溶解的过程常伴随着降解。Lewis 酸主要是一些金属盐的水溶液。目前比较常用的体系为氯化锌水溶液，比如浓度 $64\\%$ 的氯化锌可以溶解纤维素。  \n\n金属络合物中包括铜乙二胺溶液、铜氨溶液、就是酸铁纳溶液等[]。纤维素可以在这些溶剂中达到分子级分散，因此一般用于纤维素分子量及分布的分析和表征。无机金属盐水合物中结构式为I $\\mathbf{\\sigma}_{\\mathrm{iX\\cdotH_{2}O(X}}$ 一般为 $\\mathrm{\\vec{r}_{\\ s h O_{3}^{-},C l O_{4}^{-},C H_{3}C O O^{-})}}$ 的金属锂盐水合物对纤维素的溶解能力较强。此体系溶解纤维素后可进行衍生化反应，例如酯化反应和醚化反应。  \n\n碱/水溶液中最典型的是 $\\mathrm{\\NaOH/H_{2}O}$ 溶液，碱浓度和温度对溶解能力影响最大，在温度为 $-20{\\sim}4~^{\\circ}C.$ 、NaOH浓度为 $6{\\sim}18~\\%$ （质量分数）时，对纤维素的溶解性最好[27]。此体系有一定的局限性，只对聚合物小于200 的微晶纤维素溶解效果较好。此外，在此体系中加入硫脲、尿素等构成三元体系，在低温下可溶解较高聚合度纤维素，且溶解速度较快[28,29]。",
+        "category": " Introduction"
+    },
+    {
+        "id": 22,
+        "chunk": "# 1.2.1非水相非衍生化溶剂  \n\n纤维素的非水相溶剂非衍生化溶剂通常分为三大类：单组分、双组分和三组分。在单组分中主要是N-烷基吡啶卤化物和叔胺盐的氧化物。其中，N-甲基吗啉-N-氧化物（NMMO）和N-乙基-吡啶氯盐对纤维素的溶解最有效。这类溶剂因常温下是固体其具有易爆性，因此常需要加入有机溶剂组成共溶剂体系。例如，N-乙基-吡啶氯盐可加入二甲基亚矾（DMSO）、NN-二甲基甲酰胺（DMF）、N-甲基-吡咯烷酮等溶剂，这些溶剂可以降低其熔点。目前，NMMO 溶解纤维素工艺很成熟，再生纤维素纤维也实现了规模化生产，例如有Lyocell、Newcell、Tencell、Cocel 等品牌。其中，Lyocell力学性能优良、光泽度好和手感柔软，被用于高档服饰面料或医用材料。NMMO工艺除了应用于纤维素溶解加工外，还可以用于纤维素的衍生化反应，但是NMMO体系存在着热稳定性差、纤维素溶液粘度高，因此，还需要优化NMMO体系。  \n\n多组分体系中，N,N-二甲基乙酰胺（DMAc）/LiCI是优良的纤维素结构分析和均相衍生化反应的溶剂。该体系可溶解较高分子量纤维素，形成的溶液为均相透明溶液，因此也可以用于核磁、质谱（MS）、凝胶渗透色谱（GPC）和动态光散射（DLS）等测试和表征。DMAc/LiCI体系化学稳定性好，可以用作酸酐或酰氯与纤维素反应的反应溶剂；同时也可以加入DMAP（4-二甲氨基吡啶）、DCC（1,3-二环己基二亚胺）、CDI（N,N-羰基二咪唑）等催化剂催化进行酯化反应。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 23,
+        "chunk": "# 1.2.2衍生化溶剂  \n\n典型的衍生化溶剂体系有 $\\mathrm{NaOH}/\\mathrm{CS}_{2}$ （黏胶法） $\\mathrm{DMF}/\\mathrm{N}_{2}\\mathrm{O}_{4}$ ， $\\mathrm{H}_{2}\\mathbf{S}\\mathbf{O}_{4/}$ /HCOOH、$\\bf C F_{3}C O O H$ （三氟乙酸，TFA）、ClCHCOOH（二氯乙酸）、DMSO/ $\\mathrm{(CH_{2}O)_{y}}$ （多聚甲醛）、 $\\mathrm{{DMF/ClSi(CH_{3})_{3}}}$ (三甲基氯硅烷)。除上述的溶剂外，近年来，一种完全由阴阳离子组成的物质—离子液体被广泛研究[30]。离子液体是在室温或接近室温（ $100^{\\circ}\\mathrm{C}$ 以下）时呈液态，也称为低温熔融盐，熔点在 $25^{\\circ}\\mathrm{C}$ 以下的称之为室温离子液体（Room temperature ionic liquids，RTILs）。离子液体具有蒸气压小，几乎不挥发的特点，是\"绿色溶剂\"3I],有望解决传统有机溶剂挥发造成的环境污染。离子液体化学稳定性和热稳定性好，不会被氧化，不易燃；对多数的有机和无机物质具有良好的溶解能力；液态温度广，范围可从低于或接近室温到 $300^{\\circ}\\mathrm{C}$ ；通过调节阴阳离子的结构就可以得到不同溶解性和极性的离子液体；电化学稳定性好且化学窗口宽，具有高的电导率；易回收，可多次循环利用；制备方法及设备简单。  \n\n离子液体通常按照阴阳离子分类。按照阳离子分类有：季铵盐类、咪唑类、 季鳞盐类、噻唑类、吡啶类、吡咯啉类等[32]；按照阴离子分类有：阴离子主要有：  \n\nCI、Br、I、 $\\mathrm{CH_{3}C O O^{-}}$ 、 $\\mathbf{NO_{3}}^{-}$ ， $\\mathrm{\\bfBF}_{4}\\mathrm{\\overline{{~}}}$ 、HPO4\"、 $\\mathrm{HSO}_{4}^{-}$ 、 $\\mathbf{PF_{6}}^{\\bullet}$ 、 $\\mathbf{CF_{3}C O O^{-}}$ 、 $\\mathrm{CF}_{3}{\\bf S}0_{3}^{-}$ 、$(\\mathbf{CF_{3}S O_{2}})_{2}\\mathbf{N}^{-}$ 、SbF6等等。影响离子液体溶解纤维素的主要因素有：离子液体结构、温度和时间、纤维素种类和聚合物等。在已有的离子液体中，1-烷基-3-甲基咪唑离子液体（如图1.2所示）对纤维素的溶解性较好，其中EMIMAc对纤维素溶解性能最好，溶解较快、溶液均一透明、溶液粘度相对较低。咪唑类离子液体是目前比较理想的纤维素衍生化反应介质[3]，纤维素在离子液体溶剂中，可以和酰氯或者酸酐进行酯化反应、酰化反应和醚化反应等，还可以进行磺酰化反应或者生物酶催化等反应。目前，离子液体是可以进行纤维素衍生化反应类型最多的溶剂体系，且反应过程中副反应较少、反应均一、离子液体回收容易。但是，目前离子液体的回收和纯化仍然是一个不可忽视的问题，易回收离子液体的开发和回收工艺的优化对于纤维素绿色加工意义重大[34]。  \n\n![](images/7f46c079cd7306e38dbb3101f2fe9ba2f590787e3271955dfb1a49ed4550b191.jpg)  \n图1.2常见的含有咪唑阳离子的离子液体种类  \n\nFigure 1.2 Common type of ionic liquid containing imidazole cationsommon types",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# 1.3纤维素衍生化反应  \n\n纤维素分子链上每个葡萄糖单元上均有三个羟基，因此可以进行多种衍生化反应如醚化反应、酯化反应、氧化还原反应及接枝共聚反应等，如图1.3所示。纤维素的衍生化反应可以是非均相和均相反应，例如纤维素纤维、纤维素纳米晶的表面修饰。均相反应例如离子液体体系、DMAc/LiCI体系中的酯化反应。通常来说，均相反应的反应效率更高，反应更为均一，产物也更为均一。纤维素的均相衍生化反应为丰富纤维素材料种类以及制备功能性纤维素提供了基础。纤维素通过衍生化后，提高了纤维素材料的性质，拓宽了纤维素材料的应用领域。例如纤维素酯已被广泛应用到纺丝、军工、涂料和烟草等领域中，纤维素醚被广泛应用到食品、化妆品、医药、石油钻探和混凝土等领域中作为重要的助剂，如增稠剂、表面活性剂和稳定剂等。  \n\n![](images/91d83ca060c8578951e24486a372b55c2e2689895a4f077168821ff561d11a74.jpg)  \n图1.3纤维素衍生化常见的反应类型  \nFigure1.3 Common reactions of cellulose derivatization",
+        "category": " Introduction"
+    },
+    {
+        "id": 25,
+        "chunk": "# 1.3.1纤维素酯化反应  \n\n纤维素是一种多羟基化合物，因此其最重要和常见的反应便是酯化反应。纤维素羟基可以和有机酸和无机酸反应生成纤维素酯，已经使用的如纤维素硝酸酯，这也是第一种合成出来的纤维素酯。到目前为止，已有纤维素醋酸酯、硝酸酯、醋酸丁酸混合酯和黄原酸酯等多种酯被合成出来，广泛应用到纤维、涂料和气体分离膜等领域中。纤维素有机酸酯类主要由三种合成方式，即纤维素与酰卤、酸酐、羧酸反应得到（如图1.3所示)。其中，酸酐和酰卤反应活性较高，与纤维素发生酯化反应时，反应速率较快，得到的纤维素酯取代度高，部分酯化反应可以得到全取代纤维素酯。羧酸的反应活性通常较低，因此反应时通常加入催化剂来提高反应活性，以得到较高取代度的纤维素酯[35]。  \n\n纤维素乙酸酯，也称为醋酸纤维素（CA)，是最早合成出来、应用最广泛的一类纤维素酯[36]。  \n\n工业中，生产醋酸纤维素时是将纤维素溶解于冰醋酸中，在催化剂的作用下与醋酸酐发生反应得到的，此方法较难得到低取代度纤维素，一般为高取代度纤维素酯，但是经过水解可以得到低取代度纤维素酯。工业上常用产品主要有二醋酸纤维素和三醋酸纤维素，二醋酸纤维素(CDA，取代度为2.5)可溶解于DMF、丙酮等有机溶剂中，通常被用来制备香烟过滤嘴、气体分离膜、涂料、人造丝、海水淡化膜和塑料制品。三醋酸纤维素（CTA，取代度大于2.8）可溶解于氯仿但不溶解于丙酮，通常用于纺丝、胶片片基、银锌电池隔膜等。目前，醋酸纤维素酯仍然是应用最广、产量最大的纤维素酯。除了醋酸纤维素外，常用的纤维素酯还有纤维素丙酸酯、乙酸丁酸混合酯、丁酸酯和纤维素苯甲酸酯。纤维素醋酸丁酸混合酯的性能较醋酸纤维素在溶解性、耐水性、柔韧性、耐候性和延展性等方面有所提高。由于纤维素醋酸丁酸酯具有优异的性能且无毒无害，作为添加剂，已经被广泛应用到塑料和涂料中。纤维素与酸酐同样可以制备纤维素有机酸酯，例如，通过将纤维素与丁二酸酐、马来酸酐和邻苯二甲酸酐等反应，可以得到有羧基或者双键的纤维素酯，可以进一步进行化学反应或者交联反应。  \n\n纤维素与异氰酸酯或者异硫氰酸酯反应可以制备纤维素氨基甲酸酯，这类反应效率高、无副反应、纤维素降解少[37-40]。将纤维素与对苯磺酰氯反应可以得到一种重要的纤维素衍生物—纤维素对苯磺酸酯[4il。将其与卤化钠（NaCI、NaBr、NaI)、重氮盐 $\\mathsf{N a N}_{3}$ 、氨基等化合物发生亲核取代反应，得到具有卤素、亚胺、叠氮等特殊取代基的衍生物[42]，可以进一步作为纤维素功能化反应的活性位点。此外，由于对苯磺酸基的空间位阻效应，取代反应具有区域选择性，主要是得到C6位置取代的衍生物[43]。  \n\n纤维素无机酸酯的种类较少，常见的有纤维素硝酸酯、纤维素硫酸酯、纤维素亚硝酸酯、纤维素硼酸酯及纤维素磷酸酯等。纤维素硝酸酯是最早合成的纤维素无机酸酯和纤维素衍生物，通常称为硝化纤维素。在工业上是将纤维素在$\\mathrm{HNO_{3}/H_{2}S O_{4}/H_{2}O}$ 三元体系中进行酯化反应制备，通过控制反应条件，可以得到不同取代度纤维素硝酸酯。纤维素亚硝酸酯是纤维素与 ${\\bf N_{2}O_{4}}$ 或亚硝酸化合物在绝干条件下反应得到。纤维素硫酸酯是用NMMO做溶剂，纤维素与 $\\mathbf{so}_{3}$ 或 $\\mathbf{H_{2}S O_{4}}$ 反应得到[44]。纤维素硫酸酯在取代度为0.2以上时，可转化为水溶性纤维素硫酸钠[45]。纤维素磷酸酯通常是利用 $\\mathrm{POCl_{3}}\\setminus\\mathrm{H_{3}P O_{4}}\\setminus\\mathrm{P_{2}O_{5}}$ 等试剂与纤维素反应得到。纤维素硼酸酯一般是利用纤维素与 $\\mathrm{{H_{3}B O_{4}}}$ 发生酯化反应或者 ${\\bf B}({\\bf O R})_{3}$ 发生酯交换得到，过程中可能会出现纤维素交联[46]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 26,
+        "chunk": "# 1.3.2纤维素醚化反应  \n\n纤维素醚也是广泛应用的一类纤维素衍生物，通常的制备方法是将纤维素与烷基卤化物或其他醚化试剂在碱性条件下发生醚化反应得到[47]。纤维素醚最早由suida报道，利用碱润胀维素后与硫酸二甲酯反应得到。纤维素醚的合成主要有三种方法：1.Williamson醚化反应;2.碱催化环氧加成反应;3.碱催化加成反应。  \n\n纤维素醚合成最常用的方法是Williamson醚化反应，例如羧甲基纤维素、甲基纤维素、乙基纤维素、丙基纤维素等是通过纤维素与对应取代基的卤化物在碱性条件下制备得到的。当取代基较小时，反应过程中取代基在AGU单元上的分布是没有规律的，当取代基体积较大时，醚化反应展现出区域选择性，如三甲氧基苯基氯甲烷，可用作纤维素选择性合成反应中的保护基团。  \n\n羟乙基纤维素、羟丙基纤维素则是通过碱催化环氧加成反应得到。反应过程中，环氧基团可以和纤维素链上的羟基反应，也可以和生成的纤维素醚上的羟基反应。除此之外，纤维素醚上的羟基还可以进一步发生酯化或醚化反应。  \n\n纤维素与丙烯酰胺[48发丙烯睛等含吸电子基团的分子通过Michael加成反应得到含氨基或者氰基的纤维素醚。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 27,
+        "chunk": "# 1.3.3纤维素氧化反应  \n\n在一定条件下控制纤维素的氧化反应，可以得到具有不同功能性的纤维素氧化产物[49]。常见的纤维素氧化产物如图1.4所示，在实际的氧化反应过程中可以得到各种氧化结构的氧化纤维素，其比例与反应温度、反应时间、氧化剂种类和体系的pH等因素有很大关系。需要注意的是，纤维素在氧化过程中会发生一定程度降解。纤维素的氧化反应也可用来制备纳米纤维素材料，纳米纤维素不仅环保生物相容又表现出纳米材料的独特特性。从纤维素纤维中制备纳米纤维素的一种典型方法是通过2,2,6,6-四甲基哌啶-1-氧基（TEMPO）氧化纤维素纸浆纤维，然后进行温和地剪切机械处理。木材纤维素纤维的快速氧化使纳米纤维在水中完全独立，在工业应用中显示出巨大的优势。近年来以丰富的可再生植物纤维为原料制备快速氧化纤维素纳米纤维素，使纤维素纳米纤维有了新的应用，如气体阻隔复合材料、气凝胶、组织工程、柔性电子、给药和超级电容等。  \n\n![](images/a4780a940a20851091e15b6394669f90f8978f207d98d659f4c2b9b4ea91bd67.jpg)  \n图1.4具有不同结构的氧化纤维素  \nFigure 1.4 Oxidized cellulose with different structure",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 28,
+        "chunk": "# 1.3.4纤维素高分子接枝反应  \n\n纤维素除了上述的酯化、醚化和氧化反应外，还可以进行高分子接枝方式来对纤维素性能进行改性或赋予纤维素新功能。纤维素高分子接枝反应包括\"graft-from”、“graft-to”、“graft-through\"等方式，这些方法中\"graft-from\"是主要的接枝策略。“graft-from\"中，侧链反应端基暴露，有利于后续单体的反应，因此易得到高分子量的产物，而且接枝密度可控。常见的\"graft-from\"反应有开环聚合、自由基聚合、活性自由基聚合反应和Suzuki偶联反应。  \n\n开环聚合用于纤维素接枝反应的环状单体有丙交酯、己内酯、唑啉等。典型的接枝反应如纤维素接枝PCL（poly(ε-caprolactone)，聚己内酯）[50]和聚乳酸（PLLA）[51，PLLA（poly-(L-lactide)）[51]，终止聚合反应采用极少量的盐酸即  \n\n可，因此可以控制接枝的分子量。  \n\n自由基聚合反应中，常用热引发剂如偶氮二异丁晴（AIBN）、过氧化二苯甲酰（BPO）来向纤维素链上引入巯基、黄原酸酯等自由基转移基团或双键，或者利用Fenton试剂（ $_{\\mathrm{H}_{2}\\mathrm{O}_{2}/\\mathrm{\\Fe}\\mathrm{Cl}_{2}}$ ）和过硫酸钾等处理纤维素，通过自由基转移获得接枝位点，引发乙烯、丙烯酸等单体聚合反应。纤维素重氮盐在紫外光或加热的条件下也可以生成自由基引发聚合物反应。  \n\n活性自由基聚合物法主要有可逆加成-断链转移活性自由基聚合（Reversibleaddition-fragmentation chain transfer，RAFT）、原子转移自由基聚合（Atom transferradical polymerisation，ATRP）和氮氧自由基活性聚合（Nitroxide-mediatedpolymerisation，NMP）等方法。纤维素的ATRP首先需要利用酯化、醚化或Click反应在纤维素上引入卤代烷基，随后在过渡金属催化下可以实现含双键单体的聚合反应。RAFT反应过程和ATRP类似，也是首先将RAFT试剂引入到纤维素链上，以硫代羰基硫结构较为常见[52]。通常以 AIBN 和 BPO 等催化剂以RAFT基团作为反应起点引发聚合反应。NMP方法需要用稳定好的氮氧自由基参加聚合，该聚合方法需要高温，单体有限，目前较为适用苯乙烯单体。  \n\n偶联聚合反应需引入炔基或溴苯等基团，在不同的钯(Pd)金属催化下实现，通常可获得共轭高分子接枝的纤维素衍生物，多用于传感或生物检测等领域。  \n\n除了上述酯化、醚化和氧化等反应外，点击化学也可以用于纤维素衍生物的制备。点击化学具有条件温和、无副产物、反应速度快和后处理简单等优点，可以较为准确地引入各种功能基团。常见的点击反应有琉基-烯（thio-ene）Michael加成反应和叠氮-炔（azide-alkyne）环加成反应[53]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 29,
+        "chunk": "# 1.4离子型聚合物简介",
+        "category": " Introduction"
+    },
+    {
+        "id": 30,
+        "chunk": "# 1.4.1离子型聚合物性质  \n\n离子型聚合物又可称为聚离子液体（PILs）是包含聚合物主链和离子液体（ILs）单体重复单元的聚电解质。离子液体具有优异的特性，例如可忽略的蒸汽压、热稳定性、不燃性、高离子电导率和宽的电化学稳定性窗口，其可通过高分子化转移到聚合物上形成离子型聚合物。此外，离子液体种类丰富且聚合物链段的可选择性丰富了聚离子液体性能拓宽了其应用，因此，近年来在高分子科学领域引起了广泛的关注[54-56]。通常，离子型聚合物具有以下几种性质：",
+        "category": " Introduction"
+    },
+    {
+        "id": 31,
+        "chunk": "# 可调离子电导率  \n\n离子电导率是PILs的重要特性，特别是将其应用于电化学和机电应用(准)固态电解质领域中时，离子电导率不可忽视。PILs通常是单离子导体，不像ILs或ILs/聚合物杂化物，它们的阴阳离子都可移动。而PILs中阴离子或阳离子通常是在聚合物骨架结构上，因此移动会受到限制，这也导致PILs的离子电导率通常比单体离子电导率低很多。这一特征主要是由于玻璃化转变温度显著升高和组成离子共价键后可移动离子数量减少所造成。此外，影响电导率的因素也包括聚合物结构、分子量和ILs 单体的化学性质[57,58]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 32,
+        "chunk": "# 可调溶解性  \n\nPILs功能化材料的结构与性能可以通过改变反离子（阴离子）类型得到控制，特别是，PILs通过简单的离子交换可以实现从亲水性到疏水性转换[59]。例如，用 TFSI或 $\\mathbf{PF_{6}}^{-}$ 替换卤离子，PILs 会变成疏水性，从而从水溶液中沉淀出来[60]。目前常见的疏水性阴离子有 ${\\bf C F}_{3}{\\bf S O}_{3}{\\bf\\Phi}^{\\bullet}$ 、( $\\mathbf{CF}_{3}\\mathbf{S}\\mathbf{0}_{2}$ ） $_{2\\mathbf{N}}\\mathbf{\\bar{\\Lambda}}$ 、( $\\mathbf{CF}_{3}\\mathbf{CF}_{2}\\mathbf{S}\\mathbf{O}_{2}$ ）2N、 $\\mathbf{PF_{6}}^{\\bullet}$ 、$\\mathsf{B F}_{4}\\overline{{\\mathsf{\\Omega}}}$ 、PFO，常见的亲水性阴离子有CI、Br、 $\\mathrm{NO}_{3}{}^{-}$ ， $\\mathrm{CH}_{3}\\mathbf{COO}^{\\cdot}$ 等。  \n\n许多离子液体单体具有吸湿性，其水溶性随着温度的升高是逐渐增大的。水分子中的氢和离子液体单体中杂原子孤电子对之间的氢键及分子间相互作用力是影响水和离子液体互溶性的关键因素[61l，因此离子液体的亲水性可以用来表示水和离子液体之间的氢键相互作用大小。研究发现，水分子倾向于与咪唑环上的H-2、H-4、H-5质子发生相互作用，但是此相互作用力较弱l62]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 33,
+        "chunk": "# 热稳定性  \n\n由于许多聚合物会在高温环境下使用，因此热稳定性很重要。由于PILs 结构丰富，因此其具有较宽广的热稳定温度（ $100{-}400^{\\circ}\\mathbf{C})$ 。通常聚合物分子链化学结构会影响TGA中的起始分解温度（ $:T_{\\mathrm{onset}})$ 。例如，芳香族PILs 的 $T_{\\mathrm{onset}}$ 一般比脂肪族PILs高。但是，双键在氧气存在下会氧化，因此当引入双键时，其热稳定性会下降。咪唑基PILs由于其共轭结构和空间位阻而增强了热稳定性;它们的Tonset一般比吡咯烷类高。与咪唑和吡咯烷类相比，胺基聚阳离子的热稳定性较低，但化学稳定性优于磷和硫基的聚离子液体[63]。阳离子中的取代基也会影响其热稳定性，通常热稳定性随取代基在阳离子中的长度增加而增加。但是聚合物主链与取代基之间的烷基间隔长度延长会导致热稳定性降低。阴离子类型同样会影响其热稳定性。常见的阴离子[64]稳定性由高到低： $\\mathrm{CF}_{3}\\mathbf{S}0_{3}\\mathrm{^{-}}$ （ $\\mathrm{CF}_{3}\\mathbf{S}0_{2}$ ）2N'V$\\mathrm{C_{12}H_{25}C_{6}H_{4}S O_{3}\\mathrm{^{-}>P F_{6}\\mathrm{^{-}>B r\\mathrm{^{-}>C_{16}H_{34}P O_{4}\\mathrm{^{-}\\mathrm{}\\mathrm{}\\Omega_{\\mathrm{{e}}}}}}}}$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 34,
+        "chunk": "# 化学和电化学性质  \n\n众所周知，PILs能够抵抗化学及电化学降解。但是，在极端环境中，仍会产生副反应，最常见的是结构重排和降解。例如：OH具有强亲核性，其存在会引起 PILs不稳定[65]，在高温及高浓度碱环境下，共价键连接的阳离子在阴离子交换膜中会因为OH攻击而发生降解。在碱环境下，相对于胺和磷阳离子聚电解质，咪唑阳离子上C2-或N3-取代基对其稳定性影响更大[66]。  \n\n离子液体的电化学窗口通常在 $2.5{\\sim}5.0\\mathbf{V}$ ，因此，具有不同阴阳离子对的PILs也有较宽的电化学窗口。通常，PILs的电化学窗口不低于相似结构的ILs单体，有些PILs甚至会展现出更高的电化学窗口。研究发现，吡咯烷基PILs比咪唑基 PILs具有更好的电化学稳定性，而且相比于具有非环或者不饱和环的季铵盐阳离子聚合物来说，其具有更宽的阴极分解电位[6]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 35,
+        "chunk": "# 1.4.2离子型聚合物应用  \n\n常用的合成离子型聚合物策略有三种：（1）离子液体单体直接聚合；（2）离子液体单体和聚合物单体分步聚合；（3）离子液体单体后修饰到聚合物链上。常用的聚合方法有自由基聚合 $^{\\ \\{68,69\\}}$ 、活性自由基聚合[70,71]、微波辅助、电子束辅助化学[72,73]和阳离子聚合[74,75]。  \n\nPILs基聚合物电解质和一般的非离子聚合物相比展现出更高的离子电导率$(10^{-3}\\mathbf{S}\\mathbf{cm^{-1}}$ ， $25^{\\circ}\\mathrm{C})$ 、更宽的电化学窗口（5V）、更高的热稳定 $(350^{\\circ}\\mathrm{C})$ 、不易燃性和更加优异的相容性，因此PILs被应用于各种电化学领域中如燃料电池、染料敏化太阳能电池、电池、超级电容器、电致变色器件和晶体管等领域中。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 36,
+        "chunk": "# PILs应用于燃料电池  \n\n燃料电池被认为是一种清洁的能源转换技术，它将燃料中储存的化学能转化为电能，而不排放任何有污染的化学物质。全氟磺酸膜是一种常见的燃料电池聚电解质膜，当水分充足时，其具有优异的机械性能、热性能及出色的导电性[%]。然而，由于水的蒸发和全氟磺酸膜与水之间的低亲和力，全氟磺酸膜在燃料电池中工作温度不超过 ${\\bf80}^{\\circ}{\\bf C}$ 。因此，用低挥发性的非水质子载体(如质子型ILs)代替14  \n\n水对于无水条件下的高温燃料电池特别有利[77]。通常，质子传导膜是将PILs复合到聚(偏氟乙烯-共聚-六氟丙烯)(PVDF)膜中制备，得到的聚合物电解质膜在高温下表现出高的离子导电性[78,79]。最近，Yan 通过微乳液聚合方式，制备的 PILs质子传导膜具有良好的热稳定性以及优良的机械性能[8]，可将该膜应用到燃料电池中。PILs中由于具有连接良好的纳米通道，因此在无水环境和 $\\mathbf{160^{\\circ}C}$ 温度下具有 $1\\times10^{-1}\\mathrm{S\\cm^{-1}}$ 的电导率，该PILs基膜结合了高质子电导率和优异的力学性能。然而，PILs膜在长期使用过程中，部分PILs会逐渐释放出来，导致膜无法继续使用。为了解决这个问题，Yan用聚苯乙烯/聚丙烯睛原位交联或PILs和二氧化硅纳米粒子（或介孔二氧化硅纳米球）原位交联的方式制备杂化膜，提高了 PILs质子传导膜的使用寿命及稳定性[81,82]。此外，适当的纳米粒子也可使膜中形成离子传输通道或者网络结构，可以显著提高膜的质子电导率，然而，过多的纳米粒子也会阻塞离子传输通道致使电导率下降。此外，介孔二氧化硅纳米球还能有效阻止PILs从复合膜中释放并且提高电导率。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 37,
+        "chunk": "# PILs应用于染料敏化太阳能电池  \n\n染料敏化太阳能电池（DSSCs）是由合适的电解液和光敏化（半导体）阳极接触组成的光电化学系统[8384]。为了避免有机溶剂电解液挥发及泄露，离子液体和高分子PILs因具有较高功率转换效率和稳定性高的特点被应用到DSSCs。PILs能够在电池系统中传输特定离子、提供极性环境，具有良好的机械耐久性。最早，咪唑基离子导电聚合物被作为凝胶剂应用到碘/碘化物基液体电解质中，相比于对应的液体电解质，凝胶功率转换效率超过了 $85\\%$ ，最大功率转换效率达到$5.73\\ \\%^{[85]}$ ，室温放置超过500天后，仍然可以展现出优异的电池稳定性。但是，此体系中仍然含有有机溶剂(VOC)。为了解决这个问题,Manc 将(P[BVIM][TFSI])即聚(1-丁基-3-乙烯基咪唑双(三氟甲磺酰)亚胺)溶解于ILs中，可构造无有机溶剂的ILs/PILs电解质，该体系中 ${\\bar{\\mathbf{I}}}_{3}{\\mathbf{\\overline{{\\Omega}}}}$ 扩散系数比P[BVIM][TFSI]基电解质高1.4倍，同时，该体系粘度比P[BVIM][TFSI]基电解质低 35 倍，作者认为体系中聚合物结构形成了ILs可自由移动的纳米通道，促进了 $\\mathbf{I}_{3}\\mathbf{\\overline{{\\Omega}}}$ 和 $\\boldsymbol{\\mathrm{\\Delta}}\\mathbf{r}$ 的移动，使得制备的染料电池在强度为 $100\\mathrm{mWcm^{-2}}$ 的光照下最大效率为 $4.4\\%^{[86]}$ 0  \n\n此外，PILs也可通过功能化，进一步提高染料电池的功率转换效率。例如可以通过制备双阳离子聚电解质[87]，使其具有更高热学稳定性、低波动性和高柔韧，而且在相同光照强度下，双阳离子聚电解质比单阳离子聚电解质具有更高的功率转换效率。另一种提高染料敏化电池性能的途径是添加纳米粒子，例如二氧化硅纳米离子和石墨烯等，纳米粒子不仅能够提高电解质电导率，同时可以有效提高电池的功率转换效率。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 38,
+        "chunk": "# PILs应用于超级电容器  \n\n用固态或准固态聚合物电解质取代液体电解质，可以避免严格的密封及外壳要求，是目前设计柔性和轻量化超级电容器最有前途的策略之一[88]。因此，PILs基电解质被认为是超级电容器理想的固态电解质[89]。目前，该领域研究较少。Marcilla课题组设计了一种聚丙基二烯二甲基铵（三氟甲磺酰基）酰亚胺和N-丁基N-甲基吡咯烷双（三氟甲基磺酰基）酰亚胺（[PYR14]-[TFSI]）聚合物作为固态电解质用于超级电容器[9]。我们知道，在组装超级电容器之前，电解液浸渍电极是提高碳-电解液接触的关键工艺。然而，此项工作中，由于电极/电解液界面性能较差，导致所制备的超级电容器性能较低，后来该课题组用吡咯基PILs作为聚电解质可以显著提高电容器比电容[9]。  \n\nPILs除了上述电化学领域应用外，也可用于制备功能材料或智能材料。例如热响应溶胶-凝胶转变材料 $\\tt{\\cdot}p H$ 引发制动器材料、光响应材料、溶剂响应材料、$\\mathbf{C}\\boldsymbol{0}_{2}$ 响应凝胶材料、催化剂及催化剂载体、 $\\mathbf{CO}_{2}$ 吸附分离材料等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 39,
+        "chunk": "# 热触发驱动PILs材料  \n\n热触发驱动PILs可以在临界温度下经历从可溶性状态(sol)到沉淀的可逆相变。链段/链段和链段/溶剂分子间相互作用的平衡状态会随着温度的变化而改变。响应行为取决于热响应聚合物链段本身性质，响应温度可以通过亲水基团和疏水基团组成进行调节[92]。比如，Wu 将温度响应共聚物（单体：1-乙烯基咪唑，异丙基丙烯酰胺，溴乙烷）接枝到溴化聚(2,6-二甲基-1,4-苯氧基)膜上，在LCST处，共聚物膜的大小能够显著发生变化[93]。LonoV 将四丁基磷苯乙烯磺酸盐([P4,4,4,4][SS])和三丁基己基磷3-磺丙基丙烯酸盐([P4,4,4,6][SPA])交联制备的热响应PILs水凝胶，其 LCST 会随着交联剂浓度增加而降低[94]。另外，Xiong 通过 RAFT 聚合将1-乙烯基-3丁基咪唑溴盐和异丙基丙烯酰胺共聚合，并通过阴离子交换，将溴离子变为D-丙氨酸和羧酸根阴离子的方式可制备—系列的PILs[95]所制备PILs 在乙睛中具有热响应性，其UCST可以从 $25.7\\mathrm{-}34.8~^{\\circ}\\mathrm{C}$ 之间变化。  \n\n而且，PILs/乙睛溶液也可以用作萃取相，萃取正己烷中生育酚的同系物，并可多次循环使用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 40,
+        "chunk": "# pH响应性PILs材料  \n\nYuan通过将咪唑型离子液体、丙烯酸、异丙基丙烯酰胺和内烯腈光交联便可制备pH响应性材料，所制备的PILs透明度主要由丙烯酸单体浓度和PILs阴离子疏水性决定，并且可以通过温度和 pH 值分别来控制。此外，PILs 也可以通过控制水溶液pH值或气体环境（NH／HC1）来达到形状可逆形变[%]。这种双响应的PILs膜，也可用作柔性驱动器。Yan将1-丁基-3-乙烯基咪唑溴盐（[BVIM][Br]）和丙烯晴光交联，通过离子交换将磺化阴离子染料如甲酚红、溴百里酚蓝、溴甲酚绿和甲基橙置换到该PILs中，可以得到可重复使用的pH 响应薄膜。所制备的膜均是透明、力学强度高、足够坚固、可以切割成任何想要的尺寸和形状的柔性膜。这些PILs膜的pH响应行为与小分子染料非常相似，并且在酸性和碱性的水溶液或有机溶液中都是可逆变化[97]。  \n\n![](images/3be2ecb3d5d08e9acc6f18c2ed8ff535772d9b6d007a7ea859d7710e6939df3b.jpg)  \n图1.5热响应和光响应PILs膜合成路线  \nFigure 1.5 Synthetic route of thermal response and light response PILs film",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 41,
+        "chunk": "# 光响应PILs材料  \n\n光响应性聚合物通常是含有一些光活性基团，如偶氮苯、螺苯吡喃、三苯甲烷或肉桂酰，这些基团在紫外光或可见光照射下可以发生可逆结构变化，使聚合物具有光响应性[98]。在紫外光照射下，这些功能基团可以改变大小和形状，或形成离子、两性离子等。因此，可以通过PILs和偶氮苯染料、甲基橙的离子自组装设计得到光响应聚合物，而且这些光响应聚合物在紫外光照射下便会形成高度有序的层状纳米结构[99]。  \n\n溶剂响应性PILs材料  \n\n最近有报道TFSI阴离子可以和 $\\upbeta$ -环糊精（ $\\upbeta$ -CD）形成主客体包合物，因此可以在水中观察到LCST相行为[100]。Yan 通过此主客体相互作用，也可以制备一种形状记忆PILs凝胶，此水凝胶在 $\\upbeta$ -CD水溶液中可以观察到快速溶胀和形状记忆行为，在水溶液中只能看到轻微溶胀。通过将3-氰甲基-1-乙烯基咪唑双(三氟甲磺酰)酰亚胺和丙烯酸共聚可制备丙酮响应性多孔PILs膜。由于离子液体种类繁多，不同溶剂和离子液体之间的相容性存在差别，因此通过不同离子液体制备的PILs驱动器可以实现在干燥或湿环境下，对多种有机溶剂均具有多重响应性。溶剂响应性来大都自于PILs中溶剂吸附梯度变化以及PILs膜开闭孔变化。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 42,
+        "chunk": "# $\\mathrm{CO}_{2}$ 响应性PILs材料  \n\n$\\mathrm{CO}_{2}$ 是生物细胞中关键代谢产物，具有良好的生物相容性及高的膜透过性。$\\mathrm{CO}_{2}$ 可以和一些基团例如胺基或者胱基反应，生成亲水性化合物，而用惰性气体（例如 $\\mathbf{N}_{2}$ 或Ar）吹扫或加热可以恢复到原来的基团，因此，可以用 $\\mathrm{CO}_{2}$ 作为触发开关，在没有其它副产物的情况下，产生可逆相变[Io1]。Yan 用咪唑型离子液体和2-(二甲基氨基)甲基丙烯酸乙酯（DMAEMA）、聚乙二醇丙烯酸作为交联剂共聚合成了一种 $\\mathrm{CO}_{2}$ 刺激响应凝胶，用 $\\mathrm{CO}_{2}$ 气体处理该凝胶时，PILs溶液可以变为透明稳定的凝胶，当用 $\\Nu_{2}$ 吹扫后，又可恢复到初始溶液状态[102]。  \n\n![](images/01226762f69d2333dcd66ab8cbe69cfb10e47775904d14141cd206bbf0de2bfb.jpg)  \n图1.6 $\\mathrm{CO}_{2}$ 响应性可逆相变材料  \nFigure1.6 $\\mathrm{CO}_{2}$ responsive reversible phase change material",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 43,
+        "chunk": "# PILs基抗菌材料  \n\n微生物感染是住院患者死亡和发病的主要原因之一。因此，开发细菌不易产生耐药性的高效抗菌材料已引起人们的广泛关注[103]。季铵、季鳞、吡啶、咪唑阳离子聚合物在抗菌材料中被广泛研究。当微生物接触到阳离子聚合物表面时，阳离子单元会吸附在细菌上，并穿透细胞膜，导致细胞死亡[4]，从而起到杀菌作用。  \n\n近年来，咪唑类PILs显示出普适性抗菌性。Yan通过原位光聚合得到咪唑型 PILs，随后将两种氨基酸（L-脯氨酸（Pro）和L-色氨酸（Trp)）通过阴离子置换，得到两种氨基酸阴离子型PILs膜。所得两种膜对金黄色葡萄球菌和大肠杆菌均有较高的抗菌活性，且细胞毒性低，血液相容性良好。所制备的膜中，由于阴离子协同作用，PILs-Trp 膜展现出最高的抗菌活性。此外，重复使用几次后，膜仍然能够保持高抗菌性[105]。通过在 $\\mathrm{TiO}_{2}$ 表面接枝高密度咪唑型聚合物刷，也可得到具有良好抗菌性和抗生物污染性材料，例如 Zhou 合成的 PILs-TiO2 纳米材料可以应用到从光照到黑暗环境下的各种抗菌环境[106]。通过对咪唑型阳离子聚合物抗菌性能的研究，人们发现，咪唑环上取代基及电荷密度对抗菌活性有显著影响，取代基中碳链较长或者电荷密度较大往往会有更好的抗菌性。此外阴离子对其抗菌性能和溶血反应也有着显著的影响[107]，Wang 通过研究以氯、青霉素G、醋酸盐、乳酸盐、三氟乙酸盐、苯甲酸盐、柠檬酸盐、丙二酸八种不同的阴离子系列季铵盐聚碳酸酯型抗菌性能及溶血性研究，发现三氟乙酸盐和苯甲酸盐的抗菌活性最高，溶血能力低于氯离子。",
+        "category": " Introduction"
+    },
+    {
+        "id": 44,
+        "chunk": "# PILs基气体分离材料  \n\n一些研究表明，PILs比相应的 ILs单体具有更高的二氧化碳吸附能力、更快地吸附和解吸附速率，这些优点使PILs成为具有吸引力和巨大前景的 $\\mathbf{CO}_{2}$ 分离材料[108,109]。基于 PILs 的气体分离膜可分为几种类型，即纯 PILs 膜、PILs共聚物膜和PILs-ILs复合膜。早期研究中，首先制备了基于咪唑型 PILs膜用于分离二氧化碳。Bara等制备了含有不同链长烷基取代基的PILs膜，研究了其气体分离性能，结果表明，气体渗透性和扩散系数随着烷基链长度的增加而增加，$\\mathrm{CO}_{2}/\\mathrm{N}_{2}$ 分离性能接近 Robeson 上限[0]。PILs 膜的分离性能遵循溶液扩散机制，可以通过增加自由体积和气体亲和性来增强，具有较长烷基取代基的 PILs膜具有较高的自由体积，有利于 $\\mathrm{CO}_{2}$ 扩散并且增强 $\\mathbf{CO}_{2}$ 渗透性。在咪唑基 PILs中引入极性基团（低聚（乙二醇）和睛)，可以提高 $\\mathrm{CO}_{2}/\\mathrm{N}_{2}$ 和 $\\mathrm{CO}_{2}/\\mathrm{CH}_{4}$ 的选择性，引入刚性基团有利于提高 $\\mathrm{CO}_{2}$ 渗透系数\"!]。离子液体单体是另一个影响$\\mathbf{CO}_{2}$ 渗透性的因素，通过调整PILs的结构可以得到具有更高分离性能气体分离膜。Kimet等制备了烷基咪唑功能化聚醚酮（Im-PEK）膜，由于其对 $\\mathrm{CO}_{2}$ 具有较高溶解度，因此使得 $\\mathrm{CO}_{2}/\\mathrm{N}_{2}$ 选择性高达 $66.1^{[112]}$ 。Rieger等以交联聚硅氧烷作为载体，制备了含有酚盐的 PILs 基复合膜，复合膜对 $\\mathrm{CO}_{2}$ 渗透性达到900Barrer. $\\mathrm{CO}_{2}/\\mathrm N_{2}$ 选择性为 $67.7^{[113]}$ 。将自由 ILs 添加到 PILs 膜中制备 PILs-ILs复合膜是分离 $\\mathrm{CO}_{2}$ 方法中有效的方法之一，自由ILs 能够促进 $\\mathrm{CO}_{2}$ 传输，增加其渗透性，同时复合膜能够保持稳定。Noble 首次将ILs引入到 PILs 膜中，发现 $\\mathrm{CO}_{2}$ 渗透性显著提高，当添加了 $20\\mathrm{mol\\%}$ 自由离子液体时， $\\mathrm{CO}_{2}$ 渗透性提高了 $400\\%$ ， $\\mathsf{C O}_{\\beth}/\\mathsf{N}_{2}$ 选择性提高了 $25\\%^{\\{114\\}}$ 。当在聚酰亚胺基 PILs 膜中添加了$50\\mathrm{\\m}\\%$ 自由离子液体时， $\\mathrm{CO}_{2}$ 渗透性提高了 $164\\ \\%^{\\mathrm{[115]}}$ 。将自由 ILs 阳离子含有不同基团例如烷基、氟代烷基、醚、晴基和硅氧烷等基团引入分离膜中，结果发现， $\\mathrm{CO}_{2}$ 渗透性增加，气体选择性几乎不变[116]。  \n\n综上，我们了解到PILs材料具有丰富的结构和性质可调性，离子液体单体、聚合物单体和阴阳离子类型等都丰富其种类、调控其性质和拓宽了其应用。其中，阴离子交换作为一种简单便捷的方式，可以提供 PILs及 PILs 衍生物材料更多的物理化学性质变化，例如将一些金属盐引入到阴离子中，可得到具有紫外或者蓝光屏蔽的PILs膜材料；将稀土金属离子引入到阴离子中，可以得到具有光或者热响应荧光变色PILs材料；将具有磁性的金属引入到阴离子中，可以得到磁性 PILs材料。随着对离子液体及聚离子液体的研究，更多的离子液体种类及功能化智能化PILs 材料会逐渐被大家认识。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 45,
+        "chunk": "# 1.5防雾抗冰材料研究进展",
+        "category": " Introduction"
+    },
+    {
+        "id": 46,
+        "chunk": "# 1.5.1防雾材料研究进展  \n\n雾化现象在材料表面非常普遍，给我们的日常生产或生活带来诸多不便甚至危险。例如，浴室玻璃、相机镜头、眼镜、镜子、护目镜，和其显示设备上，严重影响人们视线，导致一些危险发生[\"17-124]。当基板温度低于周围空气中露点温度时，其表面会形成雾。每个小水滴都会引起光的折射和反射，导致基材透明度明显变低。车辆挡风玻璃和后视镜起雾是导致交通事故频繁发生的主要原因之一。农业大棚起雾会影响植物新陈代谢，会在一定程度上损害农作物的产量和品质。  \n\n太阳能电池上起雾会严重影响其转换效率。食品包装袋上起雾则会影响食品美观，甚至会导致水果和蔬菜的腐烂。此外，医疗器械中形成的雾也会影响医院腹腔镜检查等顺利进行。雾在基体表面沉积也会造成一些严重问题，例如食品腐烂、金属锈蚀等。因此解决起雾问题将直接或间接产生巨大的经济和社会效益。  \n\n自然界中，动物或植物中存在着各种超浸润材料，例如蚊子复眼、苍蝇眼、飞蛾眼、蝴蝶翅膀、水腿和荷叶等，在我们制备防雾材料时，生物的这些结构带给了我们无限灵感和启发。  \n\n![](images/3793b648d0f0f8317a73f724fe7209fd2b24860fa5d90bacf3deef64baa3dddb.jpg)  \n图1.7仿生超浸润防雾材料  \nFigure 1.7 Bionic super infiltrating anti-fogging materials  \n\n目前关于防雾材料的研究主要集中在超浸润材料上主要有四大类：超亲水材料、超疏水材料、两亲性材料、超亲水/疏油材料[125]。",
+        "category": " Introduction"
+    },
+    {
+        "id": 47,
+        "chunk": "# 1.5.1.1超亲水防雾材料  \n\n水滴在超亲水表面上会迅速铺开形成伪膜，减少光的散射，使其能够保持透明性防止起雾现象发生，因此各种各样的超亲水材料被开发出来，应用到防雾领域中[126]。无化学修饰，Li通过一步电沉积便可制备出具有超亲水性能的 $\\mathrm{CeO}_{2}$ 膜，该膜具有优异的防雾效果[127]。同时，作者阐述了具有纳米结构超亲水表面防雾机理。另外， $\\mathrm{CeO}_{2}$ 膜表面具有海岛结构及微裂纹，通过毛细管效应也使水滴更加快速传播，也使 $\\mathrm{CeO}_{2}$ 膜同时表现出耐腐蚀性。Yuan利用纳米ZnO通过自组装方法制备了像花一样的层状纳米结构[128]，将此纳米结构修饰到玻璃上，玻璃可以展示出多功能超亲水和防雾性质。由具有类似树莓状层状结构的 $\\mathrm{TiO}_{2}$ 中空球组装成的膜同样具有超亲水性（接触角 $\\mathrm{CA}\\approx0^{\\circ}$ )，也可展现出优异的防雾效果，在没有紫外照射的情况下，可以保持长期稳定性[129]。Yao 通过将玻璃进行 ${\\mathrm{H}}_{2}{\\mathrm{SiF}}_{6}$ 基气相刻蚀，玻璃表面可实现超亲水，使具有优异的防雾性能[130]。通过简单的溅射沉积可以在玻璃表面制备出大面积的ITO纳米棒薄膜，其接触角可以达到 $1^{\\circ}$ 以下，可以使玻璃具有很好的防雾效果[131]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 48,
+        "chunk": "# 1.5.1.2超琉水防雾材料  \n\n超亲水材料可以起到很好的防雾效果，然而在高湿度环境下，过多的水仍会凝聚在其表面，导致其防雾性能下降。对于具有超疏水表面的基体来说，超疏水可减小水滴附着力，排斥宏观水，使表面保持干燥，从而减小对光的干扰，起到防雾效果，同时超疏水材料也具有抗冰性质[132.133]，因此，具有防雾和抗冰性质的超疏水材料引起越来越多的注意。  \n\nWen 将聚偏二氟乙烯(PVDF)聚合物与 ZnO 结合构建微/纳米结构(ZP-MN),可以制备出具有高静态水接触角的涂层[134]。类似毛发的纳米阵列能够捕捉空气进入其缝隙中，因此，可以使微纳结构表面具有高的水接触角，纳米毛的高纵横比显著降低了液滴与表面的接触面积，可以有效排斥水起到防雾效果。此外，水在涂层表面结冰后，几乎可以通过微风或者倾斜的方式滑落，随后，通过对不同液-固组分得到的不同纳米毛和微柱表面进行比较，得到了具有最佳效果的防雾抗冰涂层。  \n\n最近，微米级小液滴在固体表面的动态行为引起了广泛的关注，表面能和动能之间的转换驱动微滴运动在防雾、防结冰/防结霜等领域有重要应用。He将具有多层结构多孔铝表面浸入热水中，用FAS-17对其进行改性，改性后多孔铝表面可具有自脱除冷凝水的能力 $[135]$ ，随着浸入水中时间的增加，冷凝的微液滴在其表面附着力增强，液滴的自脱除效率降低。而且，只有当凝聚微滴半径比满足${\\bf R}_{1}{:}{\\bf R}_{2}{\\approx}1$ ，且表面粘附力为 $7.9\\mathrm{mJ}/\\mathrm{m}^{-2}$ 时，才可以发生液滴的自脱除。最近，通过在纳米超疏水表面引入微孔阵列，可实现凝结水滴自驱动跳跃，从而得到一种防雾/抗冰表面[136]。微滴的自驱动跳跃能力可以通过微孔大小来调节，而且，微孔阵列相比于纳米结构超疏水表面，增加了液-气界面面积，使得防雾效果更好。后来，受甲虫鞘翅特有的亲水/疏水结构启发，Thickett制备了聚乙烯醇（PVA）改性微/纳米结构的多孔铝表面，实现了水可控冷凝和水微滴自清除[137.138]。此结构中，超疏水介孔表面和吸附在微孔里的PVA协同作用增强了可控凝结和微液滴的高效自清除。然而作者同样发现并不是所有的微纳米结构表面都能实现微液滴的自驱动运动。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 49,
+        "chunk": "# 1.5.1.3两性离子-润湿防雾材料  \n\n最初，广泛报道的防雾材料通常是亲水或超亲水的，主要是由于它们能够明显地减少光散射，水在其表面快速扩散形成伪膜以使基体保持透光率[122,139-141]。但是，通常超亲水表面难以制备，且 $\\mathrm{TiO}_{2}$ 基超亲水材料往往需要紫外照射[142]。随后，超疏水干式防雾涂层发展起来，然而超疏水表面同样难以大规模制备。无论是超亲水或超疏水材料其表面的粗糙度均会导致其机械性能较差，例如通过刮擦等会破坏其表面粗糙度。通过水相中层层自组装（LbL）制备两性离子-润湿薄膜，其中包含纳米级疏水覆盖层，使水蒸气迅速扩散到下面的亲水层中，而不是在表面聚集形成液滴[143]，可以起到很好的防雾效果。已经证明，通过改变表面亲水链和疏水链比例，可以起到防雾效果。例如，Lee将聚乙烯醇（PVA）和聚丙烯酸（PAA）以及聚（乙二醇甲基醚）（PEG）通过氢键相互作用层层自组装制备了具有防雾和防结霜的功能材料[17]，PEG链段的存在增加了材料中非结晶水能力，使得该材料可以快速吸收并分散水，同时又具有疏水性。之后，Sanchez根据(二甲胺基）甲基丙烯酸乙酯(DMAEMA)和甲基丙烯酸甲酯(MMA)亲水性和疏水性之间的微妙的平衡，以及共聚物的水溶胀性和交联网络,设计了一种优异防雾性能的丙烯酸涂料[144]。防雾机理阐述如下：当潮湿空气中的水分子聚集在防雾涂层表面时，无论是在更暖和或者更寒冷的环境中，共聚物的亲水段都能迅速地将水分子吸走，导致涂层表面无法形成雾或结霜，水分子即使进入涂层中，依然可以保持不结冰状态。聚合物与水之间的强氢键作用阻止了使光产生散射的水域形成。但是，由于DMAEMA 基聚合物低的临界溶液温度（LCST)，在长时间暴露于沸腾的水蒸气中后，表面仍然出现雾气。为了消除二元共聚物中的DMAEMA链段的低临界溶液温度的影响，基于DMAEMA/NVP/MMA三元共聚物的半互穿聚合物网络（SIPN）涂料被制备出来[145]，当三者的比例为40/30/30时，体系展现出优异的防雾及防结霜性能。在以上研究基础上，将疏水性季铵盐化合物（QAC）引入SIPN涂料中，可将其应用在医疗器械防雾涂料领域{120]。QAC 的引入，不仅消除了涂料体系中LCST，保持了共聚物的整体防雾特性，而且使涂层具有较强的抗菌性。此外，Varanasi通过在水相中层层自组装，将壳聚糖和尼龙制备了一种具有纳米结构的防雾涂层，薄的疏水性覆盖层（壳聚糖/尼龙)具有高的水蒸气渗透性，使微滴能够迅速扩散到壳聚糖/羧甲基纤维素(CHI/CMC）的下层亲水性储层中，而不是使水滴在表面上成核和生长[146]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 50,
+        "chunk": "# 1.5.2防结冰材料的研究  \n\n冰和霜给人们的日常生活带来了不便。道路上的雪和冰使路面比平时更滑，经常导致交通事故。据报道，冬天 $40\\%$ 的交通事故与下雨、结冰或下雪有关[147,148]。机翼和飞机表面结冰可能会导致坠机事故。飞机在飞越云层或遇到冷雨时拦截过冷水滴，撞击的过冷水会迅速结冰，在基体表面形成冰聚积层。积冰会导致阻力增加，有时可能会导致飞机动力损失，造成撞机事故。输电线路和电力网络可能会因过量的冰积累导致变形甚至倒塌。风力涡轮发电机叶片上的冰会造成高达 $50\\%$ 的年产量损失。此外，冰箱和热交换器中霜和冰的积累导致热交换效率降低。因此，人们努力了解结冰机理，并广泛地研究了防结冰和除冰的方法，开发了各种防结冰和除冰的方法[149-152]。  \n\n传统的除冰方法包括机械除冰、加热融化以及加入一些可以降低熔点的物质如盐、甘油和醇类，由于机械除冰和加热融化会耗费大量的能源或者人力，盐类融雪剂对金属和混凝土等具有腐蚀性，甘油、醇类会污染水体和土壤等。所以开发持久耐用，环境友好型防冰表面是亟需解决的问题。",
+        "category": " Introduction"
+    },
+    {
+        "id": 51,
+        "chunk": "# 1.5.2.1亲水性防结冰材料  \n\n液体在浸润亲水性材料表面后，能够很好的铺展开来，根据固体表面分子和水分子之间的作用力不同，水在亲水性表面通常存在三种状态。紧挨着亲水性表面的水分子与表面具有较强的水合作用，这种分子称为“不结冰水”，其厚度通常为几个分子层厚，紧挨着\"不结冰水\"的水分子被称为\"键合水”，这些水分子的特点是在低于凝固点时也不会结冰，存在最外层的水分子称为\"自由水”，这部分水与本体水的性质相同的，在达到凝固点时便会结冰[153-158]。所以正因为亲水性材料表面自由水的存在，通常在低温下冷表面结冰结霜难以避免，为了防止“自由水\"在低温下凝固，我们通常会采取增加亲水性材料与水分子之间的氢键相互作用或者通过传统的\"盐效应\"达到控制冰晶生长的目的，从而使亲水性材料起到抑制结冰的效果。  \n\nLeiserowitz在1990 年首次研究了脂肪醇对于成核温度的影响[158]。最后研究结果表明，与能够有效防结冰的水溶性醇相比，长链脂肪醇单分散层可以在接近 $\\mathbf{0}~\\mathsf{^{o}C}$ 诱导冰成核，相应的具有较大疏水基团的脂肪酸和醇可以使冰点降低$12^{\\circ}\\mathbf{C}$ 左右。同时研究还发现，两性分子导致的凝固点降低不仅与单位表面积上的分子数有关，还与脂肪醇链的长度和奇偶性有关系。对 $\\mathbf{C_{n}H_{2n+1}O H}$ 同系物来说，当 $\\mathbf{n}$ 为奇数时，成核温度在 $0^{\\circ}\\mathrm{C}$ 左右，当 $\\textbf{n}$ 为偶数时，成核温度在最低是 $8~^{\\circ}\\mathbf{C}$ 。分析认为成核温度较高是因为定向排列的脂肪醇单分散层诱导了冰成核。  \n\nHighgate通过实验证明，亲水涂层可吸附大量的水，并且储存了一部分潜冷，可以使吸附的水在 ${\\boldsymbol{-20}}^{\\circ}{\\boldsymbol{\\mathrm{C}}}$ 不结冰 $[159]$ 。也有学者将乙二醇添加到高聚物中作为亲水表面，可以取得良好的抑霜效果，存在的问题是，连续三次重复实验后，涂层会失去作用。Okoroafo采用高聚物亲水表面进行长达两个小时的结霜实验测试，发现可使结霜速率和霜层的厚度减少 $10\\%-30\\%$ ，存在的问题是，这种聚合物网络吸收的水量存在着一个临界值，只有在这个临界值之下，聚合物网络中吸收的水分子才不结冰[160,161]。也有研究者发现，亲水性表面上霜层厚度确实比普通表面上要少，但在冷表面上结霜的密度会更大些，且随着相对湿度增大，亲水性涂层延缓结霜的能力也逐渐降低，霜层沉积后，表面上的霜层也减少了其抑制结霜的能力。同时，Shin 等人研究了不同涂层厚度对结霜的影响，结果表明，亲水性涂层越厚，其效果越明显，但没有分析亲水涂层厚度多大时效果最好，使其既能保证整体良好的导热性、涂层总耗为最小，且抑制结霜的效果最好[1621。Rault等发现当水被聚乙烯醇或聚乙烯吡咯烷酮的混合物吸收后，这些水分子中只有一部分可以结晶，并且不结晶水的比例与混合的比例相关[163]。作者分析原因为，在到达水的结冰温度之前，聚合物-水的无定形相已经凝固，使水难以凝固。后来，有学者研究了聚乙烯醇在抑制冰结晶方面的作用，并和I型抗冻蛋白进行对比，发现即使聚乙烯醇的浓度降低为 $10^{-7}\\mathrm{mol}\\mathrm{t}$ 时，冰晶大小也不会随时间发生变化，具有较强的抑制冰晶生长的效果，这也与I型抗冻蛋白的抑制冰晶生长效果相似[164]。除此之外，溶液中摩尔浓度、摩尔分子量和 PVA 的水解程度也会影响抑制冰晶生长的效果。后来有学者用钛酸异丙酯，三丙二醇和甘油制备得到化合物，随后用溶胶凝胶法使体系中缓慢释放异丙醇和甘油。由于异丙醇和甘油能够有效地降低冰点，因此，这种凝胶化学的方法可以用来做防结冰涂层，且减少冰的粘附。通过风洞测试发现，在 ${\\boldsymbol{-2}}{\\boldsymbol{\\circ}}_{\\mathbf{C}}$ 下，涂有涂层的表面上冰粘附较少，而没有涂层的钢表面粘附了大量的冰，因此可以该涂层具有良好的抗冰效果。  \n\n虽然亲水性涂层在抗冰材料研究中取得了一定的进展，但是疏水材料由于其较低的表面能，较高的成核壁垒，具有明显地延缓冰成核效果，因此，用疏水性材料表面作为抗冰材料被更广泛地研究。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 52,
+        "chunk": "# 1.5.2.2疏水性防结冰材料  \n\n根据Young方程，（超）疏水性材料表面由于其具有较低的表面能，水滴在光滑的疏水表面不能完全铺展，水滴与表面的接触面积较小，当水滴与表面的接触面积越小，直接降低了表面和水滴之间的热传导，延缓了水滴的凝固。  \n\nNakajima{160]等研究了过冷水在不同硅烷处理的硅基底上的凝固过程，通过对比照片分析后指出，不论是否存在亲水区域，过冷水滴首先在接触区域部分开始凝固；同时发现，过冷水滴在氟硅烷处理过的表面上的凝固点是比在光滑表面或硅烷处理后表面的要低，猜测原因是，氟硅烷和水分子之间的相互作用起到了关键作用。 $\\mathtt{G a o}^{[165]}$ 等采用经过有机硅烷进行处理的纳米 $\\mathbf{SiO}_{2}$ 与聚合物共混得到超疏水涂层，观察实验室和室外自然环境下涂层防结冰效果，发现两种情况下，涂层均具有良好的防结冰效果。通过研究还发现，纳米粒子的粒径大小也会影响抗冰效果，粒径越小，防结冰效果也越好。  \n\nKulinich[166]在不同条件下对多种超疏水表面的冰粘附力进行了测试，最后发现，在结冰/去冰循环后，材料表面的微纳米结构被破坏，材料的抗冰性能随之下降。且在高湿度环境下，其抗冰性能也会变差，原因是因水在超疏水结构的顶部和内部冷凝，结冰后会产生较大的冰粘附力。而且，在所测试的多种超疏水表面结构中，并非所有的表面均有抗冰性能。南京大学王庆军组[167]研究了超亲水-亲水-临界-疏水-超疏水五种铝片表面抗冰情况，分析发现在相对湿度为 $80\\%$ 温度在 ${\\bf-}10^{\\circ}{\\bf C}{\\bf-}40^{\\circ}{\\bf C}$ 范围内变化时，疏水和超疏水表面浸润性发生了变化，在表面受到外界污染时，超疏水的抗冰能力优于其它表面，也可以看出，表面结构是影响冰异相成核的关键因素之一。刘中良组对铜片进行超疏水处理后，在环境温度为 $18.4^{\\circ}\\mathrm{C}$ ，冷台温度为 ${\\bf-}10.1\\ \\mathrm{\\mathrm{\\Omega}^{\\circ}C}$ ，环境湿度为 $40\\%$ 的条件下，处理后的铜片可以有效地延缓表面结霜，且发现霜晶围绕一个中心沿着与表面平行方向生长，分析原因可能是水的强极性和电荷分布不均一造成的。何敏组[168]制备了纳米氧化锌超疏水结构，该材料在室温和低温下均展现出超疏水性能，在对其进行防结冰/霜性能进行了探究，结果显示冷凝液滴维持液态的时间随着纳米氧化锌生长时间的降低而增加，并用经典成核理论和传热理论进行了解释。经过实验也可以发现，低温下保持超疏水性对于抗冰效果的提高具有十分重要的意义。  \n\nJafari[169]对比较常见铝合金进行了研究，首先将铝合金进行阳极氧化处理得到粗糙的微米结构的氧化铝，随后在表面镀一层聚四氟乙烯薄膜，使整个表面具有类似鸟巢似的结构，且能够实现超疏水。光滑铝表面上冰粘附力是修饰后的表面粘附力的 3.5倍。通过 XPS 分析，作者认为表面的低表面能官能团和微观结构是使该表面具有低冰粘附力的主要因素。  \n\nCharpentier[i70]将电负性高分子接枝到不锈钢表面，并比较了高分子修饰后不锈钢、疏水化处理不锈钢和无后处理空白不锈钢样品，发现经过疏水化处理的不锈钢表面的结冰温度低于空白样品，主要是疏水不锈钢表面的水滴的接触面积远小于空白样品，惊奇地是，接枝了带负电高分子的结冰温度要比空白样品低 $7^{\\circ}\\mathrm{C}$ 以上，这种现象主要是由于接近带电表面晶体相降低导致的。Meuler[171」 等从冰粘附机理出发，研究了影响冰粘附力的主要因素。在钢片修饰了21种不同浸润性的涂层，并与空白钢片进行对比。通过分析22种不同表面上前进角、后退角、平衡接触角和冰粘附力的关系，最后发现，冰粘附力与粘附功具有较强的相关性，涂有全氟聚倍半硅氧烷的钢片表面的粘附力比空白钢片表面的粘附力低4.2倍以上。如果我们继续引入微纳结构或制备亲疏水相间的表面使得水滴结冰后处于Cassie-Baxter复合态，能够进一步降低粘附力。  \n\nVaranasi[172] 制备了一系列不同间距的超疏水PDMS 阵列，通过环境扫描电子显微镜控制初始腔内压力为 $100\\ \\mathrm{Pa},$ 维持表面的干燥状态，在- $.13\\ ^{\\circ}\\mathrm{C}$ 的条件下逐渐增大气压直至观察到霜的形成。最后发现结霜的位置没有任何空间取向性。通过测试不同间距PDMS阵列柱子冰粘附力，发现粘附力与PDMS总面积成线性关系。  \n\nAizenberg［173-176]课题组的工作克服了超疏水材料的不足，在微纳结构基底上引入低表面能液体，形成润滑层，当液滴接触表面时，此时的界面变成了复合的固体-润滑的液体-液体的界面，润滑的液体在多孔基底表面形成了类似荷叶效应里面的空气作用的连续膜，但是，这种润滑的液体是疏油的，且表面摩擦很小。可以有效降低冰点和冰粘附力。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 53,
+        "chunk": "# 1.6本论文的研究目的和意义  \n\n本论文围绕功能纤维素衍生物的结构设计、合成和应用进行探索，利用纤维素材料多羟基的特点，通过均相酯化反应和后续的亲核取代反应，合成了具有各种功能的阳离子纤维素衍生物探究不同种类及取代度阳离子聚合物溶解性，制得具有阻燃功能的水溶性涂料、具有 $\\mathbf{CO}_{2}$ 分离功能的阳离子型醋酸纤维素衍生物、具有防雾、抗冰和自清洁功能的疏水型阳离子纤维素衍生物、具有紫外及蓝光屏蔽的含金属离子阳离子纤维素衍生物等研究内容。  \n\n通过在离子液体溶液中均相酯化反应，制备了多种不同阳离子型纤维素衍生物。其中，水溶纤维素衍生物可作为涂料组分使用，有望解决传统有机溶剂污染环境及毒害人体的问题。同时，水溶性纤维素衍生物通过引入蒙脱土，可制备得到一种阻燃型涂料，有望应用于水溶性阻燃涂料中。此外，所得醇溶性样品可用于生物医药领域中。阳离子型纤维素衍生物气体分离膜可高效分离 $\\mathbf{CO}_{2}$ ，有望解决工业生产过程中排放 $\\mathbf{CO}_{2}$ 问题，不仅有利于保护环境还可以利用碳资源。具有防雾、抗冰和自清洁性能的阳离子型纤维素衍生物所制备的涂层在高低湿度下均具有防雾性能，同时具有强大的抗冰性能和抗污性能，有望应用于防雾和防结冰领域中。具有紫外光和蓝光屏蔽性能的阳离子型纤维素衍生物能够 $100\\%$ 屏蔽紫外光及蓝光，而且具有水溶-疏水性变化。其中，水溶性样品可作为添加剂应用到防护用品中，疏水性样品可应用到紫外或蓝光屏蔽膜中。",
+        "category": " Introduction"
+    },
+    {
+        "id": 54,
+        "chunk": "# 此页不缺内容",
+        "category": " Introduction"
+    },
+    {
+        "id": 55,
+        "chunk": "# 第2章阳离子型纤维素衍生物的合成与溶解性",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 56,
+        "chunk": "# 2.1引言  \n\n纤维素是地球中最丰富的再生生物聚合物，在地球上年产量约为 $5\\times10^{11}$ 公吨,纤维素在工业上大部分被用作造纸原料，仅约 $4\\%$ 用于化学生产[177]。而且，纤维素的羟基可以反应形成酯或适合不同理化性质的醚用于各种应用[178]。  \n\n通过对纤维素上羟基进行化学修饰，可得到各种性能纤维素酯，应用到不同领域中，例如涂料组分中，纤维素酯的添加改善了其很多性质，例如硬度、流平性、再溶解性、透明度和光泽性等[179]。混合纤维素衍生物具有常规纤维素酯的优点，但在不添加有机溶剂的情况下溶液粘度略有增加，因此，在作为涂料组分使用时，纤维素酯通常溶解于有机溶剂中，使得涂料中挥发性有机物(VOCs)的使用量增加，所以，开发水溶性涂料具有重要意义。目前，已有部分水溶性纤维素衍生物用于涂料、粘合剂、油漆和油墨中以减少挥发性有机化合物。除此之外，水溶性纤维素衍生物还被应用于油田、医药、表面活性剂、抗静电剂等领域中。  \n\n传统水溶性纤维素材料中多为纤维素醚，且其种类广、性能优良。最早的纤维素醚为乙基纤维素醚，随后羟乙基纤维素、甲基纤维素和羧甲基纤维素也实现工业化生产，这也使得纤维素醚的应用进一步被扩大。水溶性的单取代醋酸纤维素，也是一类较为重要的水溶性纤维素材料，在生物及医药材料等方面具有很好的应用前景。这类水溶性纤维素衍生物通常为非离子型和阴离子型衍生物，但目前对于阳离子型纤维素衍生物的制备及研究较少。  \n\n纤维素阳离子纤维素衍生物目前种类少，合成步骤较为繁杂[180-182]。例如，Groth[183]．首先将纤维素硅烷化，然后磺化，最后和（3-氯-2羟丙基）三甲基铵氯盐反应得到纤维素硫酸盐。刘春[184]等人提出了用微晶纤维素为原料合成6-脱氧N-磺酸和N-羧甲基化纤维素的步骤，包括微晶纤维素的苯甲酰化、还原性胺反应、LiAlH4还原叠氮基及最后 N-磺化或者 N-羧甲基化。Bohy[185]以氯化纤维素为中间体，得到了赖氨酸和谷氨酸功能化两性离子纤维素衍生物。并将其应用到水溶液中铀酰的吸附中。  \n\n随着纤维素溶解体系的发展，为纤维素衍生化提供了更多的机会。越来越多的纤维素功能材料被简单快捷地制备出来，进一步扩宽了纤维素材料在各个领域中的应用。例如近年来以离子液体为代表的一种新型纤维素溶剂，其不仅无毒无害、不易挥发和易回收，因此被广泛应用到纤维素研究领域中，同时也为纤维素的高值化利用提供了更多的机会和基础。  \n\n本章中，首先通过酯化反应将氯引入到纤维素中，随后将其和三丁基麟、吡啶、1-甲基咪唑和1-乙烯基咪唑等反应制备了多种阳离子纤维素衍生物，然后考察了取代度对其溶解性影响。随后，通过离子交换的方式，得到可被有机溶剂溶解的疏水型纤维素衍生物，进一步扩宽了阳离子纤维素衍生物种类和应用场景，比如，我们将水溶性纤维素衍生物作为表面活性剂用于分散蒙脱土，得到一种阻燃型纤维素水溶性涂料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 57,
+        "chunk": "# 2.2实验部分",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 58,
+        "chunk": "# 2.2.1原料和试剂  \n\n棉浆粕（CottonPulp)：山东恒联新材料有限公司提供，平均聚合度650。所用纤维素原料使用前在 $70^{\\circ}\\mathrm{C}$ 真空烘箱中干燥 $48\\ h$   \n2-氯丙烯酰氯（2-Chloropropionylchloride）:百灵威科技有限公司提供，纯度 $97\\%$ 直接使用。  \n1-烯丙基-3-甲基咪唑氯盐（1-Allyl-3-methylimidazole chloride，AmimCl)：实验室自己合成，其含水量不高于 $0.3\\%$ 。  \n三丁基麟（Tributyl phosphine）吡啶（pyridine）、1-甲基咪唑（1-Methylimidazole）、1-乙烯基咪唑（1-Allylimidazole)：百灵威科技有限公司提供，纯度 $98\\%$ ，直接使用。  \n蒙脱土（Montmorillonite）：比表面积 $240\\mathbf{m}^{2}/\\mathbf{g}$ ，北京伊诺凯科技有限公司，直接使用。  \n双三氟甲烷磺酰亚胺锂（bistrifluoromethanesulfonimidelithium salt）、六氟磷酸锂(Lithium Hexafluorophosphate）、四氟硼酸锂（Lithium Tetrafluoroborate）：百灵威科技有限公司提供，纯度 $98\\%$ ，直接使用。  \n油红（SudanII）、靛红（Isatin）：百灵威科技有限公司提供，纯度 $98\\%$ ，直接使用。  \n\n超纯水：Milli-Q，Millipore $0.22\\upmu\\mathrm{m}$ 6  \n\n氛代二甲基亚矾（DMSO- ${\\bf\\cdot d_{6}}$ )，百灵威科技有限公司提供，纯度 $99.8\\%$ ，直接使用。  \n\n其他化学药品均从北京国药化学试剂公司获得，试剂均为分析纯，使用前无需进一步提纯。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 59,
+        "chunk": "# 2.2.2阳离子型纤维素衍生物的合成",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 60,
+        "chunk": "# 2.2.2.1多种不同阳离子纤维素衍生物的合成  \n\n（1）不同取代度纤维素2-氯丙酸酯合成：  \n\n1g棉浆粕加入到 $\\mathbf{49}\\ \\mathbf{g}$ 离子液体AmimCl中，于 $80^{\\circ}\\mathbf{C}$ 油浴中剧烈搅拌溶解1h，溶解得到浓度为 $5\\%$ 的纤维素/离子液体溶液。将纤维素溶液置于 $\\mathbf{0}\\%$ 的冰水浴中，等温度稳定后，加入含有 $2.4\\ \\mathbf{g}$ 的2-氯丙酰氯，充分混合。随后，将其转移到 $40~^{\\circ}\\mathbf{C}$ 油浴中反应 $_{3\\ h}$ 。反应结束后加入乙醇和水使样品沉淀，然后使用砂芯漏斗抽滤，干燥。将干燥后的样品重新溶于二甲基亚矾中，使用 $\\mathbf{0.45\\upmum}$ 滤膜过滤，再次使用乙醇沉淀，抽滤、洗涤三次后，置于 ${\\bf80^{\\circ}C}$ 的真空烘箱中干燥，得到取代度为3.0的纤维素2-氯丙酸酯。控制不同投料比及反应时间可得不同取代度纤维素2-氯丙酸酯。  \n\n（2）不同类型阳离子纤维素衍生物合成：  \n\n取一定量上述纤维素2-氯丙酸酯，溶解于N,N-二甲基甲酰胺（DMF）中，加入一定量三丁基麟、吡啶、1-甲基咪唑、1-乙烯基咪唑，置于 ${\\bf80}^{\\circ}{\\bf C}$ 油浴中回流反应 $24\\mathrm{h}$ ，待反应结束后，加入丙酮使样品沉淀，然后使用砂芯漏斗抽滤三遍以上，真空干燥。将干燥后的样品重新溶于二甲基亚矾中，使用 $0.45\\upmu\\mathrm{m}$ 滤膜过滤，再次使用丙酮沉淀，砂芯漏斗抽滤、洗涤三次后，置于 ${\\bf80^{\\circ}C}$ 的真空烘箱中干燥。得到不同取代度，不同阳离子类型纤维素衍生物。  \n\n（3）不同阴离子的咪唑型阳离子纤维素衍生物合成：  \n\n将上述中咪唑型阳离子衍生物（ $(2.5\\ \\mathrm{mmol})$ ）溶于水中。然后，滴加LiTfN、LiBF4或LiPF6的饱和水溶液！ $(2.3\\mathrm{mmol})$ 。将反应体系在室温搅拌 $24\\mathbf{h}$ 。出现白色沉淀。过滤沉淀物，用去离子水洗涤三次，并在 ${\\bf80^{\\circ}C}$ 下真空干燥 $24\\mathrm{h}$ ，以获得不同阴离子型咪唑阳离子纤维素衍生物。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 61,
+        "chunk": "# 2.2.2.2阻燃性水溶性纤维素衍生物合成  \n\n（1）纤维素2-氯丙酸酯合成：  \n\n${\\mathfrak{l}}_{\\mathbf{\\deltag}}$ 棉浆粕加入到 ${\\bf49}{\\bf{g}}$ 离子液体AmimCl中，在 ${\\bf80}^{\\circ}{\\bf C}$ 油浴中剧烈搅拌溶解1h，配制成浓度为 $5\\%$ 的纤维素/离子液体溶液。将纤维素溶液置于 $0^{\\circ}\\mathrm{C}$ 的冰水浴中，等温度稳定后，加入含有 $2.4\\ \\mathsf{g}$ 的2-氯丙酰氯，充分混合。随后，将其转移到$40^{\\circ}\\mathrm{C}$ 油浴中反应 $_{3\\mathrm{h}}$ 。反应结束后加入乙醇使样品沉淀，抽滤，干燥。将干燥后的样品重新溶于二甲基亚矾中，使用 $0.45\\upmu\\mathrm{m}$ 滤膜过滤，再次使用乙醇沉淀，抽滤、洗涤三次后， $80^{\\circ}\\mathrm{C}$ 的真空烘箱干燥，得到取代度为3.0的纤维素纤维素2-氯丙酸酯。随后，按照上述步骤（2）制备水溶性纤维素衍生物。  \n\n（2）阻燃性水溶性纤维素膜制备：  \n\n所有膜均采用溶剂挥发法制备得到，具体如下：将所得水溶性纤维素酯融入水中，质量分数为 $10\\ \\mathrm{wt\\%}$ 。加入不同质量的蒙脱土，用细胞粉碎机超声 $40~\\mathrm{min}$ 随后将其倾倒在模具中，放置到 $80^{\\circ}\\mathrm{C}$ 热台上。放置 $2\\hbar$ 后，将膜转移。放置在真空烘箱中继续干燥 $24\\mathrm{h}$ o",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 62,
+        "chunk": "# 2.2.3测试和表征  \n\n（1）核磁共振 ${}^{1}\\mathrm{H}$ -NMR:  \n\n1H-NMR光谱均采用BrukerAV400核磁共振波谱仪测定。用气代DMSO来溶解样品，测试前加一滴氛代三氟乙酸将活泼氢移至低场。  \n\n（2）傅里叶变换红外光谱（FTIR）：  \n\n红外光谱采用Perkin-Elmer 公司的Thermo Nicolet 6700 傅里叶变换红外光谱仪测定，测试波数范围为 $650{\\cdot}4000\\ \\mathrm{cm^{-1}}$ ，分辨率为 $4\\mathrm{cm}^{-1}$ ，扫描次数16次。  \n\n（3）光电子能谱（XPS）：  \n\n样品光电子能谱测试在X射线光电子能谱仪ESCALab250Xi（ThermoFisher，USA）进行测试。  \n\n（4）光学照片：  \n\n光学照片均采用数码相机（SONY $\\mathtt{\\Gamma}\\mathtt{\\backslash}\\mathtt{\\Gamma}\\mathtt{\\backslash}\\mathtt{\\mathtt{\\backslash}\\mathtt{\\mathtt{\\backslash}\\mathtt{\\mathtt{\\backslash}\\mathtt{\\mathtt{\\backslash}\\mathtt{\\mathtt\\left/{\\backslash}\\mathtt{\\alpha}\\mathtt{\\backslash}\\mathtt{\\alpha}\\mathtt{\\backslash}\\mathtt{\\alpha}\\mathtt{\\left|\\alpha\\mathtt{\\backslash}\\mathtt{\\alpha}\\mathtt{\\left|\\alpha\\mathtt{\\backslash}\\mathtt\\alpha\\mathtt{\\left|\\alpha}\\mathtt{\\left|\\alpha\\mathtt{\\mathtt\\backslash}\\mathtt\\alpha\\mathtt{\\left|\\alpha}\\mathtt{\\left|\\alpha\\mathtt\\mathtt{\\backslash}\\alpha\\mathtt\\mathtt{\\left|\\alpha}\\mathtt\\mathtt{\\left|\\alpha}\\mathtt\\mathtt{\\left|\\alpha\\mathtt\\mathtt{\\left|\\alpha}\\mathtt\\mathtt{\\left|\\alpha\\mathtt\\mathtt{\\left|\\alpha}\\mathtt\\mathtt{\\left|\\alpha\\mathtt\\mathtt\\mathtt{\\left|\\alpha}\\mathtt\\mathtt{\\left|\\alpha\\mathtt\\mathtt\\mathtt{\\left|\\alpha}\\mathtt\\mathtt\\mathtt{\\left|\\alpha}\\mathtt\\mathtt\\mathtt{\\left|\\alpha\\mathtt}\\mathtt\\mathtt\\right|\\alpha}}}}}}}}}}}\\end{array}$ ，Japan）拍摄所得。  \n\n（5）热失重分析：  \n\n热重分析采用Perkin-ElmerPyris-1热分析仪测定样品在空气气氛下的热失重行为。称取样品质量 $3\\mathrm{mg}$ 左右，测试温度范围为 $50{-}700^{\\circ}\\mathrm{C}$ ，采用升温速率为  \n\n20℃/min。  \n\n（6）微型燃烧量热测试（MCC）：  \n\n样品MCC测试采用美国Govmark公司MCC-2型微型量热仪，根据标准ASTMD7309-2007进行测试。在氮气氛围下，约 $3\\mathrm{mg}$ 样品 $100^{\\circ}\\mathrm{C}$ 下恒温 $3\\mathrm{min}$ ，然后以1K/s的速度迅速升温至 $600~^{\\circ}\\mathrm{C}$ ，氮气流速度为 $80~\\mathrm{cm}^{3}/\\mathrm{min}$ 。裂解后的气流与氧气流（ $20~\\mathrm{cm}^{3}/\\mathrm{min}$ ）充分混合后进入 $900^{\\circ}\\mathrm{C}$ 燃烧炉中进行充分燃烧。  \n\n（7）扫描电镜分析：  \n\n样品形貌观察采用JEOL公司的JSM-6700F场发射扫描电子显微镜，观察前对样品表面进行喷金处理，增加样品导电性，采用加速电压为 $5.0\\mathbf{k}\\mathbf{V}$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 63,
+        "chunk": "# 2.3结果与讨论",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 64,
+        "chunk": "# 2.3.1阳离子纤维素衍生物的合成  \n\n![](images/d690a3f31a56ee622fc4461220cd2875edacd642962d29d6bd36264331834d2a.jpg)  \n图2.1阳离子纤维素衍生物的合成路线  \nFigure 2.1 Synthesis route of cationic cellulose derivatives  \n\n不同结构的水溶性阳离子纤维素衍生物反应过程如图2.1所示。首先在纤维素的AmimCI离子液体溶液中均相衍生化合成两种不同取代度的纤维素2-氯丙酸酯（Cell-C1)，分别为 ${\\mathrm{DS}}{=}1.5$ 和 $\\mathrm{DS}{=}3.0$ 。随后加入一定量三丁基麟、吡啶、1-甲基咪唑、1-乙烯基咪唑得到三种阳离子型纤维素衍生物。通过控制投料比、反应时间得到不同取代度三种阳离子型纤维素衍生物如下表所示。表2.1表示Cell-C1 $\\scriptstyle\\mathbf{D}\\mathbf{S}=3.0$ 时不同反应条件下对阳离子纤维素衍生物取代度影响。表2.2表示Cell-C1 ${\\bf D}{\\bf S}{=}1.5$ 时不同反应条件下对阳离子纤维素衍生物取代度影响。  \n\n表2.1以Cell-Cl $(\\mathbf{D}\\mathbf{S}=3.0)$ 为原料不同反应条件对阳离子纤维素衍生物取代度影响  \n\nTable 2.1 Effects of different reaction conditions on the degree of substitution of cationic cellulose derivatives using Cell-Cl ( ${\\bf\\langle D S{=}}3.0{\\bf\\rangle}$ ) as raw material   \n\n\n<html><body><table><tr><td>Base reagent</td><td>Molar ratio of Base reagent /Chloride</td><td>Temperature (°C)</td><td>Time (h)</td><td>DS</td></tr><tr><td></td><td>3:1</td><td>80</td><td>6</td><td>0.11</td></tr><tr><td>p一</td><td>3:1</td><td>80</td><td>12</td><td>0.32</td></tr><tr><td></td><td>3:1</td><td>80</td><td>24</td><td>0.71</td></tr><tr><td></td><td>6:1</td><td>80</td><td>12</td><td>1.42</td></tr><tr><td>(Cell-P-CI)</td><td>6:1</td><td>80</td><td>24</td><td>2.51</td></tr><tr><td rowspan=\"3\"></td><td>3:1</td><td>80</td><td>6</td><td>0.02</td></tr><tr><td>3:1</td><td>80</td><td>12</td><td>0.07</td></tr><tr><td>3:1</td><td>80</td><td>24</td><td>0.21</td></tr><tr><td rowspan=\"2\">(Cell-B-CI)</td><td>6:1</td><td>80</td><td>12</td><td>2.00</td></tr><tr><td>6:1</td><td>80</td><td>24</td><td>2.80</td></tr><tr><td>NN-</td><td>6:1</td><td>80</td><td>6</td><td>0.30</td></tr><tr><td>[</td><td>6:1</td><td>80</td><td>12</td><td>1.61</td></tr><tr><td>(Cell-M-CI)</td><td>6:1</td><td>80</td><td>24</td><td>2.01</td></tr></table></body></html>  \n\n表2.2以Cell-Cl $(\\mathrm{D}\\mathbf{S}=1.5)$ 为原料不同反应条件对阳离子纤维素衍生物取代度影响  \n\nTable 2.2 Effects of different reaction conditions on the degree of substitution of cationic cellulose derivatives using Cell-Cl $(\\mathbf{D}\\mathbf{S}=\\mathbf{i}.5)$ as raw material   \n\n\n<html><body><table><tr><td>Base reagent</td><td>Molar ratio of base reagent/Chloride</td><td>Temperature (C)</td><td>Time (b)</td><td>DS</td></tr><tr><td></td><td>3:1</td><td>80</td><td>6</td><td>0.21</td></tr><tr><td></td><td>3:1</td><td>80</td><td>12</td><td>0.50</td></tr><tr><td></td><td>3:1</td><td>80</td><td>24</td><td>0.91</td></tr><tr><td></td><td>6:1</td><td>80</td><td>12</td><td>1.00</td></tr><tr><td>{Cell-P-CI)</td><td>6:1</td><td>80</td><td>24</td><td>1.21</td></tr><tr><td></td><td>3:1</td><td>80</td><td>6</td><td>0.15</td></tr><tr><td>(Cell-B-CI)</td><td>3:1</td><td>80</td><td>12</td><td>0.31</td></tr><tr><td></td><td>6:1</td><td>80</td><td>24</td><td>0.84</td></tr><tr><td rowspan=\"3\">N^N- [</td><td>3:1</td><td>80</td><td>6</td><td>0.20</td></tr><tr><td>3:1</td><td>80</td><td>12</td><td>0.50</td></tr><tr><td>3:1</td><td>80</td><td>24</td><td>0.96</td></tr><tr><td rowspan=\"2\">(Cell-M-Cl)</td><td>6:1</td><td>80</td><td>12</td><td>1.21</td></tr><tr><td>6:1</td><td>80</td><td>24</td><td>1.40</td></tr></table></body></html>  \n\n从表2.1中可以看出，三丁基麟和纤维素2-氯丙酸酯（ $\\mathbf{\\hat{C}e l l-C l}\\mathbf{DS}=3.0)$ 更容易反应，在较低投料比和反应时间下，取代度较高。吡啶较三丁基麟、1-甲基咪唑和纤维素2-氯丙酸酯反应较难。同样在6:1的投料比下反应 $24\\mathrm{h}$ ，纤维素三丁基氯盐和纤维素1-甲基咪唑氯盐取代度分别可以达到2.51和2.0，而纤维素吡啶氯盐的取代度只能达到2.0。随着投料比增大或者反应时间延长，三种阳离子型纤维素衍生物的取代度均是增大的。而当取代度变化后 $\\mathbf{\\hat{C}e l l-C l}\\mathbf{DS}=1.5)$ ，纤维素2-氯丙酸酯和吡啶的反应相对于三丁基麟、1-甲基咪唑较容易反应，当投料比为6:1时，反应时间为 $24\\mathrm{~h~}$ ，其取代度可达1.4。同样的，随着投料比增大或者反应时间延长，三种阳离子型纤维素衍生物的取代度均是增大的。但是，在同样投料比和反应时间情况下， $\\mathrm{Cell-Cl}\\mathbf{D}\\mathbf{S}=1.5$ 时比 $\\mathrm{Cell-Cl}\\mathbf{D}\\mathbf{S}=3.0$ 的样品更容易和三丁基麟反应。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 65,
+        "chunk": "# 2.3.2阳离子纤维素衍生物的表征  \n\n在纤维素衍生物的核磁氢谱中如图2.2(a)所示， $0.9\\ \\mathsf{p p m}$ 和 $2.4\\ \\mathsf{p p m}$ 峰为三丁基麟上丁基的氢， $1.6\\mathrm{ppm}$ 峰为2-氯丙酰氯中甲基的氢， $2.5{-}5.5\\mathrm{ppm}$ 的峰为纤维素骨架和2-氯丙酰氯中次甲基中的氢。从图2.2(d)可以看出， $1735~\\mathrm{cm}^{-1}$ 处的峰为乙酰基中伸缩振动峰， $1216~\\mathrm{cm}^{-1}$ 处的峰为酯基中C-O-C 的反对称伸缩振动吸收峰， $2924~\\mathrm{cm^{-1}}$ 处的峰为丁基麟中丁基C-H振动峰，说明纤维素三丁基氯盐被成功合成。在图2.2（b）中， $8.2\\ \\mathsf{p p m}$ ， $\\mathbf{8.7ppm}$ 和 $9.2\\mathsf{p p m}$ 的峰为吡啶环上的氢， $1.6\\mathsf{p p m}$ 位移为2-氯丙酰氯中甲基的峰， $2.5{\\cdot}5.5\\mathsf{p p m}$ 位移为纤维素骨架上的峰。从图 2.2（e）可以看出， $1735~\\mathrm{cm^{-1}}$ 处的吸收峰为乙酰基中伸缩振动峰，$1216\\mathsf{c m}^{-1}$ 处的峰为酯基中C-O-C反对称伸缩振动吸收峰， $500{-}1600{\\mathrm{cm}}^{-1}$ 处为芳环伸缩振动峰，说明纤维素吡啶氯盐被成功合成。从图 2.2（c）可以看出，7.7ppm、 $7.8~\\mathsf{p p m}$ 和 $\\mathbf{9.4\\ppm}$ 处的峰是咪唑环上的氢， $2.5{-}5.5~\\mathrm{ppm}$ 峰为纤维素骨架上的氢、咪唑环上甲基和2-氯丙酰氯中次甲基的氢，其中 $3.9\\mathrm{ppm}$ 处的峰为咪唑环上甲基氢， $1.6\\mathsf{p p m}$ 位移为2-氯丙酰氯中甲基。从图2.2（f）可以看出，1735$\\mathbf{cm^{-1}}$ 处吸收峰为乙酰基中伸缩振动峰。 $1216~\\mathrm{cm^{-1}}$ 处的峰为酯基中C-O-C反对称伸缩振动吸收峰。1560、1470 和 $1165\\mathrm{cm}^{-1}$ 处峰与咪唑环相对应。说明纤维素1-甲基咪唑氯盐吡啶被成功合成出来。  \n\n![](images/17d5c026b21262c904e5a68d223e6d79c637dfe2d978e29fa70af979e30553f3.jpg)  \n图2.2阳离子纤维素衍生物的核磁氢谱和红外谱图（a）纤维素三丁基氯盐核磁氢谱图（b）纤维素吡啶氯盐核磁氢谱图（c）纤维素1-甲基咪唑氯盐核磁氢谱图（d）纤维素三丁基氯盐红外光谱图(e）纤维素吡啶氯盐核红外光谱图（f)纤维素1-甲基咪唑氯盐外光谱图  \n\nFigure 2.2 NMR spectra and FTIR of Cationic cellulose derivative (a) $^1\\mathrm{H}$ -NMRof cellulose tributylphosphonium chloride salt (b) $^1\\mathrm{H}$ -NMR of cellulose pyridinium chloride salt hydrogen (c) $^1\\mathrm{H}$ -NMR of 1 - methyl cellulose imidazolium chloride salt hydrogen (d) FTIR of cellulose tributyl phosphine chlorine salt (e) FTIR of cellulose pyridine chloride salt (f) FTIR of 1 - methyl cellulose imidazole chloride salt.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 66,
+        "chunk": "# 2.3.2阳离子纤维素衍生物的溶解性  \n\n通过控制反应条件，我们得到多类型和各种取代度纤维素衍生物，首先考察了其在水和常见有机溶剂（例如，甲醇、DMF等）中的溶解性变化。水溶性涂料越来越受到大家的重视，因此，我们首先重点关注样品的水溶性，从下面的表格中可以看出，不同类型纤维素衍生物展现出不同的溶解性。而且，纤维素2-氯丙酰氯酯取代度会影响纤维素衍生物溶解性。  \n\n2.3.2.1阳离子纤维素衍生物随取代度和阳离子基团溶解性变化（以Cell-CIDS$=3.0$ 为原料）  \n\n我们首先考察了当Cell-CIDS=3.0时，不同类型及取代度纤维素衍生物溶解性变化。从表2.3中可以看出，当纤维素三丁基氯盐取代度为0.71时可溶解到水中，此时，在甲醇中溶胀，当其取代度继续增大时， ${\\bf D5}{\\bf=}{\\bf l}.42$ 时，其样品可以溶解在水、甲醇、乙醇和吡啶中，小于此取代度的样品无法溶解在甲醇、乙醇、吡啶中。此外所有取代度样品无法溶解在异丙醇、四氢呋喃、氯仿和乙酸乙酯中，但均可溶解在DMF和DMSO中。  \n\nTable 2.3 Solubility of cellulose tributylphosphonium chloride salts   \n\n\n<html><body><table><tr><td rowspan=\"2\">Solvent Samples</td><td rowspan=\"2\">H0 Ethanol</td><td rowspan=\"2\"></td><td rowspan=\"2\">Methanol</td><td rowspan=\"2\">Isopropanol</td><td rowspan=\"2\">Ethyl acetate</td><td rowspan=\"2\">Chloroform</td><td rowspan=\"2\"> Pyridine</td><td rowspan=\"2\"> THF</td><td rowspan=\"2\">DMF</td><td rowspan=\"2\">DMSO</td></tr><tr><td></td></tr><tr><td>DS-0.02</td><td>·</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>+</td><td>+</td></tr><tr><td>DS-0.07</td><td>－</td><td>，</td><td>+</td><td></td><td>士</td><td>士</td><td>±</td><td></td><td>+</td><td>+</td></tr><tr><td>DS-0.21</td><td>+</td><td></td><td></td><td></td><td></td><td></td><td></td><td>，</td><td>+</td><td></td></tr><tr><td>DS=2.0</td><td>+</td><td>，；</td><td>+</td><td>+</td><td>±</td><td></td><td>+</td><td>－</td><td>+</td><td>+</td></tr><tr><td>DS=2.8</td><td>+</td><td></td><td>+</td><td>+</td><td>±</td><td>±</td><td>+</td><td></td><td>+</td><td>+</td></tr></table></body></html>\n\n注： $^+$ ，溶解；-，不溶解； $\\pm$ ，溶胀  \n\n而当纤维素吡啶氯盐 $\\scriptstyle\\mathbf{DS}=0.21$ 时可溶解在水中， $\\mathbf{D}\\mathbf{S}\\mathbf{=}0.07$ 时便可溶解在甲醇中， $\\scriptstyle\\mathbf{DS}=2.0$ 时开始溶解在异丙醇和吡啶中，在乙醇、乙酸乙酯、氯仿和四氢呋喃的溶剂中均不溶解。但在DMF 和DMSO中均可以溶解。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 67,
+        "chunk": "# 表2.4纤维素吡啶氯盐的溶解性  \n\n表2.3纤维素三丁基鳞氯盐的溶解性  \nTable 2.4 Solubility of cellulose pyridinium chloride salts   \n\n\n<html><body><table><tr><td>Solvent</td><td colspan=\"4\">H2O Ethanol</td><td rowspan=\"2\">Ethyi acetate</td><td rowspan=\"2\">Chloroform</td><td rowspan=\"2\"> Pyridine</td><td rowspan=\"2\">THF</td><td rowspan=\"2\">DMF</td><td rowspan=\"2\">DMSO</td></tr><tr><td>Samples</td><td></td><td></td><td>Methanol</td><td>Isopropanol</td></tr><tr><td>DS-0.11</td><td></td><td></td><td></td><td></td><td></td><td>·</td><td></td><td>－</td><td>+</td><td>+</td></tr><tr><td>DS-0.32</td><td></td><td></td><td>－</td><td></td><td></td><td></td><td></td><td></td><td>+</td><td>+</td></tr><tr><td>DS=0.71</td><td>+</td><td></td><td>，</td><td></td><td>，</td><td></td><td></td><td>，</td><td>+</td><td>+</td></tr><tr><td>DS=1.42</td><td>+</td><td>+</td><td>+</td><td>士</td><td>±</td><td>±</td><td>+</td><td></td><td>+</td><td>+</td></tr><tr><td>DS=2.51</td><td>+</td><td></td><td>+</td><td></td><td>±</td><td>±</td><td>+</td><td>·</td><td>+</td><td>+</td></tr></table></body></html>  \n\n当纤维素1-甲基咪唑氯盐 $\\scriptstyle\\mathbf{DS}=0.30$ 时，可溶解在水和甲醇中，当 $\\mathbf{DS}{=}2.01$ 时，可溶解在乙醇中，在异丙醇、乙酸乙酯、氯仿、吡啶和四氢呋喃等有机溶剂中均不溶解，在DMF和DMSO中所有样品均可溶解。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 68,
+        "chunk": "# 表2.5纤维素1-甲基咪唑氯盐的溶解性  \n\nTable 2.5 Solubility of cellulose 1- methylimidazolium chloride salts  \n\n<html><body><table><tr><td> Solveat</td><td colspan=\"6\">H0 Ethano!</td><td rowspan=\"2\">Chloroform</td><td rowspan=\"2\">Pyridine</td><td rowspan=\"2\">THF</td><td rowspan=\"2\">DMF</td><td rowspan=\"2\">DMSO</td></tr><tr><td>Samples</td><td></td><td></td><td></td><td>Methano! Isopropanol</td><td>Ethy! acetate</td><td></td></tr><tr><td>DS-0.30</td><td>+</td><td>±</td><td>+</td><td></td><td>·</td><td>·</td><td></td><td>·</td><td></td><td>+</td><td>+</td></tr><tr><td>DS=1.61</td><td>+</td><td></td><td>+</td><td>士</td><td>士</td><td>，</td><td></td><td></td><td></td><td>+</td><td>+</td></tr><tr><td>DS=2.01</td><td>+</td><td>+</td><td>+</td><td></td><td></td><td></td><td></td><td>，</td><td></td><td>+</td><td>+</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 69,
+        "chunk": "# 2.3.2.2阳离子纤维素衍生物随取代度和阳离子基团溶解性变化（以Cell-Cl${\\bf D S}{\\bf=}{\\bf1}.{\\bar{S}}$ 为原料)  \n\n当Cell-CI取代度也会影响其溶解性，我们考察了当Cell-CI ${\\bf D}{\\bf S}{\\bf=}{\\bf1}.{\\bf\\bar{\\Sigma}}$ 时纤维素衍生物在常见溶剂中的溶解性。从表2.6中可以看出，当Cell-Cl ${\\tt D S}{=}1.5$ 时纤维素三丁基氯盐 $\\scriptstyle\\mathbf{D}\\mathbf{S}=\\mathbf{0}.9$ 时，可以溶解在水、乙醇、异丙醇和吡啶中，但Cell-C1 $\\scriptstyle\\mathbf{D}\\mathbf{S}=3.0$ 时，纤维素三丁基氯盐 $\\ensuremath{\\mathbf{D}}\\ensuremath{\\mathbf{S}}=1.42$ 时，样品开始溶解于甲醇中，且始终无法完全溶解于异丙醇中。但当纤维素三丁基氯盐 $\\scriptstyle\\mathbf{DS}=\\mathbf{0}.2$ 时，便可溶解在甲醇中。当纤维素三丁基氯盐 $\\bf{D S}\\mathrm{=}1.0$ 时，可溶解到氯仿中。所有的样品均不溶解于乙酸乙酯和四氢呋喃中，但均溶解于DMF和DMSO中。  \n\n表2.6纤维素三丁基氯盐的溶解性  \nTable 2.6 Solubility of cellulose tributylphosphonium chloride salts   \n\n\n<html><body><table><tr><td rowspan=\"2\">Solveut ， Samples</td><td rowspan=\"2\">H0</td><td rowspan=\"2\">Ethanol</td><td rowspan=\"2\"> Methanol</td><td rowspan=\"2\">Isopropanol</td><td rowspan=\"2\">Ethyl ncetate</td><td rowspan=\"2\">Chloroform</td><td rowspan=\"2\"> Pyridine</td><td rowspan=\"2\">THF</td><td rowspan=\"2\">DMF</td><td rowspan=\"2\">DMSO</td></tr><tr><td></td></tr><tr><td>DS-0.2</td><td>·</td><td></td><td>+</td><td></td><td></td><td></td><td></td><td>←</td><td>+</td><td>+</td></tr><tr><td>DS-0.5</td><td>·</td><td>·</td><td>+</td><td></td><td>·</td><td>·</td><td></td><td></td><td>+</td><td>+</td></tr><tr><td>DS=0.9</td><td>+</td><td>+</td><td>+</td><td>+</td><td></td><td>±</td><td>+</td><td></td><td>+</td><td>+</td></tr><tr><td>DS=1.0</td><td>+</td><td>+</td><td>+</td><td>t</td><td>，</td><td>+</td><td>+</td><td></td><td>+</td><td>+</td></tr><tr><td>DS=1.2</td><td>+</td><td>+</td><td>+</td><td>+</td><td></td><td>+</td><td>+</td><td>·</td><td>+</td><td>+</td></tr></table></body></html>  \n\n当纤维素吡啶氯盐 $\\scriptstyle\\mathbf{DS}=0.31$ 时，其可以水溶，纤维素吡啶氯盐 $\\scriptstyle\\mathbf{DS}=0.15$ 时能够实现甲醇、氯仿和吡啶溶解。但是，当 $\\mathrm{\\cell{-}C l{\\ D S=}}3.0$ 时，只有当纤维素吡啶氯盐 ${\\bf D}{\\bf S}=2.0$ 及以上时才能够实现吡啶溶解，且一直不溶解与氯仿中。同时，所有的样品甲醇、异芮醇、乙酸乙酯和四氢呋喃等有机溶剂均无法溶解，但均可溶解于DMF 和DMSO 中。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 70,
+        "chunk": "# 表2.7纤维素吡啶氯盐的溶解性  \n\nTable 2.7 Solubility of cellulose pyridinium chloride salts   \n\n\n<html><body><table><tr><td>Solvent</td><td>HO</td><td>Ethanol</td><td>Methanol</td><td>Isopropanol</td><td>Ethyl</td><td>Chloroform</td><td>Pyridine</td><td>THF</td><td>DMF</td><td>DMSO</td></tr><tr><td>Samples DS=0.15</td><td></td><td></td><td>+</td><td></td><td>acetate</td><td>+</td><td>+</td><td></td><td>+</td><td>+</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>++</td><td></td></tr><tr><td>DS=0.314</td><td>++</td><td></td><td>++</td><td></td><td></td><td>++</td><td>++</td><td></td><td></td><td>++</td></tr></table></body></html>  \n\n当纤维素1-甲基咪唑氯盐 $\\scriptstyle\\mathrm{{DS=0.96}}$ 时，可实现水溶，且当维素1-甲基咪唑氯盐 $\\mathrm{DS}{=}0.2$ 时，甲醇可以很好地溶解样品。然而，这些样品不能在异丙醇、乙酸乙酯、氯仿、吡啶和四氢呋喃等溶剂中充分溶解，可以溶解于DMF和DMSO中。  \n\n表2.8纤维素1-甲基咪唑氯盐的溶解性  \nTable 2.8 Solubility of cellulose 1- methylimidazolium chloride salts   \n\n\n<html><body><table><tr><td>Solvent</td><td>HO</td><td>Ethanol</td><td>Methanol</td><td>Isopropanol</td><td>Ethyl</td><td>Chloroform</td><td>Pyridine</td><td>THF</td><td>DMF</td><td>DMSO</td></tr><tr><td>Samples DS=0.2</td><td></td><td></td><td>+</td><td></td><td>acetate</td><td></td><td></td><td>，</td><td>+</td><td>+</td></tr><tr><td>DS=0.5</td><td></td><td>，</td><td>+</td><td></td><td></td><td></td><td></td><td>，</td><td>+</td><td>+</td></tr><tr><td>DS=0.96</td><td>+</td><td></td><td>+</td><td></td><td></td><td></td><td></td><td></td><td>+</td><td>+</td></tr><tr><td>DS=1.21</td><td>+</td><td></td><td>+</td><td></td><td></td><td>，</td><td>+</td><td>+</td><td>+</td><td>+</td></tr><tr><td>DS=1.40</td><td>+</td><td></td><td>+</td><td></td><td></td><td></td><td></td><td></td><td>+</td><td>+</td></tr></table></body></html>  \n\n阳离子型纤维素衍生物具有可调水溶性变化，通过离子交换便可以实现从水溶到油溶的转变。而且水溶性涂料在日常使用过程中，可能会受到空气中水分、雨水等因素影响而无法正常使用。日常生活中所使用的水溶性涂料通常通过交联实现水溶-水不溶转变，我们通过CI转变成疏水离子来达到目的。因此，我们选取部分样品进行离子交换，考察其溶解性变化。  \n\n![](images/5833fb3e5db87d96023c055daf8d376f26d34775204187d8e3fbcbad1d420c7a.jpg)  \n图2.3疏水性阳离子纤维素衍生物红外光谱和光电子能谱图（a）纤维素1-甲基咪唑氯盐、纤维素1-甲基咪唑双三氟甲磺酰亚胺盐、纤维素1-甲基咪唑六氟化磷  \n\n盐、纤维素1-甲基咪唑四氟化硼盐红外光谱（b）纤维素1-甲基咪唑氯盐、纤维素1-甲基咪唑双三氟甲磺酰亚胺盐、纤维素1-甲基咪唑六氟化磷盐、纤维素1-甲基咪唑四氟化硼盐红外光谱光电子能谱图。  \n\nFigure 2.FTIR spectra and XPS of hydrophobic cationic cellulose derivatives (a) FTIR of Cellulose l-methylimidazolium chloride salt, cellulose 1- methylimidazolium bistrifluoromethyl sulfimide salt, cellulose 1- methylimidazolium phosphorus hexafluoride salt, cellulose 1-methylimidazolium boron tetrafluoride salt (b) XPS of Cellulose 1- methylimidazolium chloride, cellulose 1- methylimidazolium bistrifluoromethyl sulfimide salt, celulose l- methylimidazolium phosphate hexafluoride salt, cellulose l- methylimidazolium boron tetrafluoride salt .  \n\n从图2.3中FTIR谱图中出现新的 $865{-}1238\\mathrm{cm}^{-1}$ 处的峰可归于 $\\mathsf{B F}_{4}\\mathsf{^{-}}$ ，751-865$\\mathbf{cm^{-1}}$ 的峰可归于 $\\mathbb{P F}_{6}^{\\bullet}$ ， $915{\\cdot}1326~\\mathrm{cm}^{\\cdot}1$ 处的峰可归于TfN。此外，XPS 图中出现了F元素、P元素和B元素峰，也证明了我们成功将CI变成三种不同阴离子。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 71,
+        "chunk": "# 2.3.2.2阳离子纤维素衍生物随取代度和阴离子基团溶解性变化（以Cell-CI$\\scriptstyle\\mathbf{DS=}3.0$ 为原料)  \n\n表2.9纤维素三丁基麟双三氟甲磺酰亚胺盐、纤维素吡啶双三氟甲磺酰亚胺盐、纤维素1-甲基咪唑双三氟甲磺酰亚胺盐溶解性。  \n\nTable 2.9 Solubility of Cellulose tributylphosphonium bis trifluoromethyl sulfimide salt, cellulose pyridinium bistrifluoromethyl sulfimide salt, cellulose 1- methylimidazolium bistrifluoromethyl sulfimide salt  \n\n<html><body><table><tr><td>Solvent</td><td rowspan=\"2\">HO</td><td rowspan=\"2\">Ethanol</td><td rowspan=\"2\">Methanol</td><td rowspan=\"2\"> Isopropano!</td><td rowspan=\"2\">Ethyi acetate</td><td rowspan=\"2\">Chloroform</td><td rowspan=\"2\">Pyridine</td><td rowspan=\"2\">THF DMF</td><td rowspan=\"2\"></td><td rowspan=\"2\">DMSO</td></tr><tr><td>Sanpkes</td></tr><tr><td>Cel-P-TIN DS=2.51</td><td>·</td><td>+</td><td>+</td><td>·</td><td></td><td>·</td><td>+</td><td>■</td><td>+</td><td>+</td></tr><tr><td>Cell-B-Tr,N DS=2.81</td><td></td><td>+</td><td>+</td><td>+</td><td></td><td></td><td>+</td><td></td><td>+</td><td>+</td></tr><tr><td>Cel-M-TIN DS=2.01</td><td></td><td>+</td><td>+</td><td>+</td><td></td><td></td><td></td><td></td><td>+</td><td>+</td></tr></table></body></html>  \n\n我们选取部分样品进行离子交换，我们首先将CI转变为TfN考察了其溶解性变化。如表2.9所示，交换后纤维素三丁基麟双三氟甲磺酰亚胺盐、纤维素吡啶双三氟甲磺酰亚胺盐、纤维素1-甲基咪唑双三氟甲磺酰亚胺盐均不再水溶，但是样品依然保持了在甲醇、乙醇、异丙醇和吡啶中的溶解性。样品依然不能溶解于乙酸乙酯、氯仿和四氢呋喃中，但仍然可以溶解DMF和DMSO中，将CI转变为TfN后基本只改变了样品水溶性。  \n\n表2.10纤维素三丁基麟六氟化磷盐、纤维素吡啶六氟化磷盐、纤维素1-甲基咪唑六氟化磷盐溶解性  \n\nTable 2.10 Solubility of cellulose tributylphosphonium hexafluoride, cellulose pyridinium hexafluoride, and cellulose 1-methylimidazolium hexafluoride.   \n\n\n<html><body><table><tr><td>Solvent</td><td rowspan=\"2\">HO Ethanol</td><td rowspan=\"2\"></td><td rowspan=\"2\"> Methanol</td><td rowspan=\"2\">Isopropanol</td><td rowspan=\"2\">Ethyi Chloroform acetate</td><td rowspan=\"2\">Pyridine</td><td rowspan=\"2\">THF</td><td rowspan=\"2\"> DMF</td><td rowspan=\"2\">DMSO</td></tr><tr><td>Samples Cell-P-PF.</td><td></td></tr><tr><td>DS=2.51</td><td>1</td><td>一</td><td></td><td></td><td></td><td></td><td></td><td>1 +</td><td>+</td></tr><tr><td>Cell-B-PF. DS=2.81</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>+ +</td></tr><tr><td>Cell-M-PF. DS=2.01</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>+</td><td>+</td></tr></table></body></html>  \n\n我们将样品通过离子交换将CI变为 $\\mathbf{PF}_{6}\\mathbf{\\overline{{\\Omega}}}$ 后，进一步考察了其溶解性变化。从表2.10可以看出，除了DMF和DMSO可以溶解外，样品在水、甲醇、乙醇、异丙醇、乙酸乙酯、氯仿、吡啶、四氢呋喃中均不再溶解。离子交换后，不但改变了其水溶性，也改变了在其它溶剂中的溶解性。  \n\n表2.11纤维素三丁基麟四氟化硼盐、纤维素吡啶四氟化硼盐、纤维素1-甲基咪唑六四氟化硼盐溶解性  \n\nTable 2.11 Solubility of cellulose tributylphosphonium boron tetrafluoride, cellulose pyridinium boron tetrafluoride, and cellulose 1-methylimidazolium hexafluoride.  \n\n<html><body><table><tr><td colspan=\"2\">Solvent</td><td rowspan=\"2\">HO Ethanol</td><td rowspan=\"2\">Methanol</td><td rowspan=\"2\">Isopropanol</td><td rowspan=\"2\">Ethyt scetale</td><td rowspan=\"2\">Chlorofor m</td><td rowspan=\"2\"> Pyridine</td><td rowspan=\"2\"> THF</td><td rowspan=\"2\">DMF</td><td rowspan=\"2\">DMSO</td></tr><tr><td>Samples</td><td></td></tr><tr><td>Cell-P-BF. DS=2.51</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>+</td><td>+</td></tr><tr><td>Cell-B-BF, DS=2.81</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>+</td><td>+</td></tr><tr><td>Cell-M-BF. DS=2.01</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>+</td><td>+</td></tr></table></body></html>  \n\n从表2.11中我们发现，将样品通过离子交换将CI变为 $\\mathrm{BF}_{4}\\mathrm{^{-}}$ 后，也出现同样的情况，除了DMF和DMSO可以溶解，样品在水、甲醇、乙醇、异丙醇、乙酸乙酯、氯仿、吡啶、四氢呋喃中均不再溶解。离子交换后，不但改变了其水溶性，也改变了在其它溶剂中的溶解性。  \n\n2.3.2.3阳离子纤维素衍生物随取代度和阴离子基团溶解性变化（以Cell-CIDS $\\mathbf{\\Sigma}=$   \n1.5为原料)  \n\n随后我们将Cell-Cl $\\mathbf{DS}=\\mathbf{l}.5$ 的样品选取几个样品也同样进行了离子交换，进一步考察其溶解性变化规律。  \n\n表2.12纤维素三丁基麟双三氟甲磺酰亚胺盐、纤维素吡啶双三氟甲磺酰亚胺盐、纤维素1-甲基咪唑双三氟甲磺酰亚胺盐溶解性。  \n\nTable 2.12 Solubility of tributylphosphonium bistrifluoromethyl sulfimide salt, cellulose pyridinium bistrifluoromethyl sulfimide salt, cellulose l-methyl imidazolium bistrifluoromethyl sulfimide salt.  \n\n<html><body><table><tr><td>Solvent</td><td rowspan=\"2\">HO</td><td rowspan=\"2\">Ethanol</td><td rowspan=\"2\"> Methapol</td><td rowspan=\"2\">Isopropanol</td><td rowspan=\"2\">Ethyl acetate</td><td rowspan=\"2\">Chloroform</td><td rowspan=\"2\">Pyridine</td><td rowspan=\"2\">THF</td><td rowspan=\"2\">DMF</td><td rowspan=\"2\">DMSO</td></tr><tr><td>Samples Cell-P-TIN</td></tr><tr><td>DS=1.21</td><td>，</td><td></td><td>+</td><td>+</td><td>1</td><td></td><td></td><td>1</td><td>+</td><td>+</td></tr><tr><td>Cell-B-TI,N DS=0.84</td><td></td><td></td><td>+</td><td></td><td></td><td>+</td><td>+</td><td></td><td>+</td><td>+</td></tr><tr><td>Cell-M-TfN DS=1.4</td><td></td><td></td><td>+</td><td>I</td><td></td><td></td><td></td><td></td><td>+</td><td>+</td></tr></table></body></html>  \n\n我们选取了部分样品进行离子交换，首先将CI转变为TfN考察了其溶解性变化。如表2.12所示，样品均由水溶性转变为水不溶，纤维素三丁基麟双三氟甲磺酰亚胺盐依然能够在甲醇、乙醇和异丙醇中溶解。纤维素吡啶双三氟甲磺酰亚胺盐能够被甲醇、氯仿和吡啶溶解，纤维素1-甲基咪唑双三氟甲磺酰亚胺盐能够被甲醇溶解。DMF 和DMSO 依然能够充分溶解所有样品。  \n\n表2.13纤维素三丁基麟六氟化磷盐、纤维素吡啶六氟化磷盐、纤维素1-甲基咪唑六氟化磷盐溶解性  \n\nTable 2.13 solubility of cellulose tributylphosphonium hexafluoride, cellulose pyridinium hexafluoride, and cellulose l-methylimidazolium hexafluoride.  \n\n<html><body><table><tr><td>Solvent</td><td rowspan=\"3\">HO</td><td rowspan=\"3\">Ethsnol</td><td rowspan=\"3\">Methanol</td><td rowspan=\"3\">Isopropanol</td><td rowspan=\"3\">Ethyl</td><td rowspan=\"3\">Chloroform</td><td rowspan=\"3\">Pyridine</td><td rowspan=\"3\">THF</td><td rowspan=\"3\">DMF</td><td rowspan=\"3\">DMSO</td></tr><tr><td>Samples</td><td>acetate</td></tr><tr><td>Cell-P-PF.</td><td>-</td></tr><tr><td>DS=1.21</td><td>·</td><td>1</td><td></td><td></td><td></td><td></td><td>1</td><td></td><td>+</td><td>+</td></tr><tr><td>Cel-B-PF DS=0.84</td><td></td><td>■</td><td></td><td></td><td></td><td></td><td></td><td></td><td>+</td><td>+</td></tr><tr><td>Cell-M-PF. DS=1.4</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>+</td><td>+</td></tr></table></body></html>  \n\n我们将样品通过离子交换将CI变为 $\\mathbf{\\nabla}\\mathsf{P F}_{6}.$ 后，进一步考察了其溶解性变化。从表 2.13可以看出，除了DMF和 DMSO可以溶解，样品在水、甲醇、乙醇、异丙醇、乙酸乙酯、氯仿、吡啶、四氢呋喃中均不再溶解。离子交换后，不但改变了其水溶性，也改变了在其它溶剂中的溶解性。与Cell-Cl $\\mathrm{DS}=3.0$ 样品溶解性出现相同的现象。  \n\n表2.14纤维素三丁基麟四氟化硼盐、纤维素吡啶四氟化硼盐、纤维素1-甲基咪唑六四氟化硼盐溶解性  \n\nTable 2.14 solubility of cellulose tributylphosphonium boron tetrafluoride, cellulose pyridinium boron tetrafluoride, and cellulose 1-methylimidazolium hexafluoride.   \n\n\n<html><body><table><tr><td>Solvent</td><td rowspan=\"2\">HO</td><td rowspan=\"2\">Ethanol</td><td rowspan=\"2\">Methanol</td><td rowspan=\"2\">Isopropanol</td><td rowspan=\"2\">Ethyl acetate</td><td rowspan=\"2\">Chlorofor m</td><td rowspan=\"2\">Pyridine</td><td rowspan=\"2\">THF</td><td rowspan=\"2\">DMF</td><td rowspan=\"2\">DMSO</td></tr><tr><td>Samples</td></tr><tr><td>Cell-P-BF, DS=1.21</td><td>1</td><td></td><td>-</td><td></td><td></td><td></td><td></td><td>一</td><td>+</td><td>+</td></tr><tr><td>Cell-B-BF DS=0.84</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>-</td><td>+</td><td>+</td></tr><tr><td>Cell-M-BF4 DS=1.4</td><td>-</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>+</td><td>+</td></tr></table></body></html>  \n\n从表2.14中我们发现，将样品通过离子交换将C1变为 $\\operatorname{BF}_{4}{\\mathrm{:}}$ 后，也出现同样的情况，除了DMF和DMSO可以溶解，样品在水、甲醇、乙醇、异丙醇、乙酸乙酯、氯仿、吡啶、四氢呋喃中均不再溶解。离子交换后，不但改变了其水溶性，也改变了在其他溶剂中的溶解性。与 $\\mathrm{Cell-Cl~DS}=3.0$ 样品出现相同的现象。  \n\n为了更直观地观察离子交换后水溶性变化，我们分别用绿色和红色染料将涂层染色，然后用水冲洗。从图2.4中，可以看到水溶性样品在水冲洗1秒后，出现溶解，3秒后基本全溶。而交换成疏水离子后，水冲洗3秒后，依然不会溶解。所以，离子交换是一种简单高效地改变物质溶解性变化的方法。  \n\n![](images/aeb8d4b15b0e8e1c4c6c0be35802388c62d14b4988958969ee0dbd184bf6d272.jpg)  \n图2.4Cell-M-CI离子交换前后水溶性变化光学照片  \n\nFigure 2.4 Optical image of water solubility change before and after ion exchange",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 72,
+        "chunk": "# 2.3.3阻燃水溶性涂层",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 73,
+        "chunk": "# 2.3.3.1阻燃水溶性涂层基本表征  \n\n通过上述的方法，我们将N-乙烯基咪唑接枝到纤维素上，得到一种水溶性纤维素衍生物。  \n\n![](images/6c1e40a0f471d20b8fad3347ac05e09d8430646cc7e930919ed048a73f308786.jpg)  \n图2.5纤维素1-乙烯基咪唑氯盐表征(a)纤维素1-乙烯基咪唑氯盐核磁谱图(b)纤维素1-乙烯基咪唑氯盐红外光谱图  \n\nFigure 2.5 Characterization of cellulose 1-vinylimidazolium chloride salt (a) ${}^{1}\\mathrm{H}.$ -NMR of cellulose 1-vinylimidazole chloride salts (b) FTIR of cellulose 1-vinylimidazole chloride salts.  \n\n从图2.5中可以看出， $8.0\\ \\mathrm{ppm}$ ， $8.3~\\mathrm{ppm}$ 和 $9.6\\ \\mathrm{ppm}$ 处的峰对应1-乙烯基咪唑中咪唑环上的氢， $2.5\\substack{-6.0\\mathrm{ppm}}$ 对应于纤维素骨架上的氢、2-氯丙酰氯中次甲基氢和1-乙烯基咪唑中双键上的氢。 $1737~\\mathrm{cm^{-1}}$ 处的吸收峰为乙酰基中基伸缩振动峰， $1652~\\mathrm{cm^{-1}}$ 处的峰为双键峰， $1553~\\mathrm{cm^{-1}}$ ， $1451~\\mathrm{{cm}^{-1}}$ 的峰分别对应于咪唑环上 $\\scriptstyle\\mathbf{C}=\\mathbf{N}$ 和C-N。因此，我们得到了一种含有双键的水溶性纤维素衍生物。随后，将其溶解于水中，用于分散蒙脱土，即可得到水溶性阻燃纤维素涂层。从图2.6中可以看出，蒙脱土在涂层中分散均匀，没有出现明显团聚。  \n\n![](images/76f1c594d809d5fa6c7d35effdc69f84543e0323a6fc5ed9f7b517cdf71820d8.jpg)  \n图2.6Cell-VimCl/ $50\\mathrm{{wt\\%}}$ MMT膜SEM图（a）表面形貌（b）断面形貌（c）（d）Cell-VimCl/ $50\\mathrm{wt\\%}$ MMT溶液TEM图  \n\nFigure2.6 SEM image of $50\\mathrm{wt\\%}$ MMT membrane (a) surface morphology (b) section morphology (c) (d) TEM images of Cell-VimCl / $50\\mathrm{wt\\%}$ MMT solution",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 74,
+        "chunk": "# 2.3.3.2阻燃水溶性涂层燃烧实验  \n\n为了我们更加直观了解蒙脱土的引入对水溶性涂层阻燃性能的影响，我们对纯纤维素膜和含有不同含量蒙脱土涂层进行燃烧实验（图2.7)。从燃烧实验中可以直观地看出，未添加蒙脱土的纯纤维素在接触明火后会立即剧烈地燃烧，可以明显看到火焰，且燃烧后看不到碳残余产生。而添加了蒙脱土的涂层在离开酒精灯火焰后则会立即熄灭，涂层具有明显离火自熄性质，熄灭后，我们会看到明显的碳层残余。此实验直接地说明了蒙脱土的引入使纤维素衍生物材料具有优异的阻燃性质。  \n\n![](images/4565f1e4f14ca01cda8c4df6b298b5a3c8d9df0b9881e34f1c911df50d311e4c.jpg)  \n图2.7纤维素及Cell-VimCI/MMT膜的燃烧实验   \nFigure2.7 Snapshot photos of cellulose and Cell-VimCl / MMT membranes during the flammability test",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 75,
+        "chunk": "# 2.3.3.3复合膜阻燃机理  \n\n从上面燃烧实验可以看出引入蒙脱土后，涂层能够离火自熄，具有良好的阻燃性能。为了进一步测试涂层阻燃性能，分析其阻燃机理，我们对不同含量蒙脱土的涂层进行了空气热失重分析和微型燃烧量热分析。  \n\n热失重分析可以表征材料在受热过程中的降解现象，进而反应材料在燃烧时候的变化。图2.8是纤维素和不同含量蒙脱土涂层在空气气氛下TGA曲线和微分失重曲线。由热失重曲线可以看出，纯纤维素在较高的温度下开始快速降解，且最后没有碳残余，说明纯纤维素几乎没有阻燃性。而引入了蒙脱土的涂层在较低温度下开始降解，样品碳残量随着蒙脱土含量增大而增加，最大达到 $28\\%$ ，这说明蒙脱土的存在诱导了纤维素产生了大量碳残余。据文献报道，燃烧后碳残余量越多说明样品燃烧释放可燃气体的量越少，阻燃效果也越好。  \n\n材料开始分解温度能够在一定程度上反应其在高温时热稳定性，当引入蒙脱土后，涂层分解温度降低。原因是，含磷阻燃剂通常会在较低温度下分解，产生磷酸等酸性物质，从而引发纤维素脱水、交联、成碳，产生更多碳残余。由热失重积分曲线可以看出，涂层具有两个最大热失重速率峰值。其在 $250^{\\circ}\\mathrm{C}$ 左右快速热失重，从而形成阻隔层且在高温下能够催化纤维素成碳。因此，纤维素的阻燃性能得到了极大的提高。  \n\n![](images/e4adc93df336669dc3038f0bc2c34f05a1168b13c2a6bc89271c3b96ba174637.jpg)  \n图2.8纤维素、Cell-VimCl/ $30\\%$ MMT纤维素复合膜、Cell-VimCl/ $40\\%$ MMT纤维素复合膜、Cell-VimCl/ $50\\%$ MMT纤维素复合膜空气气氛下（a）热失重曲线和（b）热失重积分曲线  \nFigure 2.8（a）TGA curve and （b）DTG curve of cellulose, Cell-VimCl / $30\\%$ MMT composite membrane, Cell-VimCl / $40\\%$ MMT composite membrane and CellVimCl / $50\\%$ MMT composite membrane in air atmosphere  \n\n进一步，我们使用微型燃烧量热仪对纤维素和不同含量蒙脱土涂层进行燃烧性能测试。其热释放速率和详细数据如图2.9和表2.15所示。最大热释放速率（PHRR）代表材料在燃烧过程放热速率最大值，用来表示材料燃烧快慢。从图2.9中可以明显地看出，相对于纤维素，涂层的PHRR值有了大幅度下降。其中当MMT的含量为 $40\\%$ 时，其值下降到119.1（下降了 $79.3\\%$ )，说明此时膜具有很低的燃烧性。而当MMT含量为 $50\\%$ 时，PHRR值略有升高，说明阻燃剂也并非越多越好。  \n\n通常，阻燃剂（尤其是含磷阻燃剂）的存在会因为在低温下发生脱水反应而降低纤维素开始降解温度，这种脱水反应可以增加残碳量来降低基体的阻燃性能。从表2.15中可以看出，当引入MMT后，在低于纤维素开始分解温度时出现脱水反应峰，在较高温度时出现肩峰。随着MMT含量增加，肩峰逐渐变大并达到  \n\n$342.6^{\\circ}\\mathrm{C}$ 0  \n\n热释放能力（HRC）和热释放总量（THR）反映出材料在燃烧过程自身转化为热量的潜力。由表2.15中可以看到，相对于纯纤维素，复合膜的HRC和THR值均有大幅度降低，当MMT含量为 $50\\%$ 时，其THR值最小，可能是因为其残碳量较多。对于以凝聚相机理作用的阻燃剂，高的残碳量意味着较低的可燃气体的热释放。从热失重曲线中可以看出，随着MMT含量增加，其碳残量是增大的。这些结果都说明MMT的加入使纤维素的阻燃性能大大地提高。  \n\n![](images/e8eb916f33682e15313711602d999ab466f9021f4d8b0aa00b9771a5ddae393d.jpg)  \n图2.9纤维素、Cell-VimCl/ $30\\%$ MMT、Cell-VimCl / $40\\%$ MMT、Cell-VimCl/$50\\%$ MMT纤维素复合膜的热释放速率曲线  \n\nFigure 2.9 Hert release rate （HRR） curves of cellulose and Cell-VimCl/ $30\\%$ MMT、Cell-VimCl / $40\\%$ MMT、Cell-VimCl/ $50\\%$ MMT Composite membranes  \n\n表2.15纤维素、Cell-VimCl/ $30\\%$ MMT、Cell-VimCl / $40\\%$ MMT、Cell-VimCl/ $50\\%$ MMT复合膜的微型量热测试数据  \nTable 2.15 MCC data of cellulose and Cell-VimCl / $30\\%$ MMT、Cell-VimCl / $40\\%$ MMT、Cell-VimCl / $50\\%$ MMT Composite membranes  \n\n第2章阳离子型纤维素衍生物的合成与溶解性  \n\n\n<html><body><table><tr><td>Samples</td><td>PHRR (W/g)</td><td>Tmar-1 (℃)</td><td>Tmax-1 (C)</td><td>THR (KJ/g)</td><td>HRC (J/(g*K))</td></tr><tr><td>Cellulose</td><td>574.4</td><td>383.5</td><td></td><td>13.7</td><td>321</td></tr><tr><td>Cell-VimCl</td><td>142.9</td><td>233.3</td><td>316.0</td><td>8.1</td><td>80</td></tr><tr><td>30%MMT Cell-VimCl</td><td>119.1</td><td>248.5</td><td>337.3</td><td>7.3</td><td>66</td></tr><tr><td>40 % MMT Cell-VimCl</td><td></td><td></td><td>342.6</td><td></td><td></td></tr><tr><td>50%MMT</td><td>126.9</td><td>241.1</td><td></td><td>6.8</td><td>72</td></tr></table></body></html>  \n\n![](images/85add52227cab20e069e50e2d8f26dfa4169df02f015f0156ae4bae1a0c08c77.jpg)  \n图2.10Cell-VimCl/ $30\\%$ MMT复合膜燃烧后的残碳形貌图  \n\nFigure 2.10 SEM image of Cell-VimCl / $30\\%$ MMT Composite membrane after flammability test  \n\n随后，我们在扫描电镜下观察了膜燃烧后碳残余形貌。如图2.10所示，可以看到，碳层表面非常致密稳定，说明MMT的引入可以使纤维素快速脱水成碳，从而形成了致密不可燃的碳化层。碳化层的形成一方面阻止聚合物进一步热解，另一方面可以阻止内部热分解产生物进入气相参与进一步燃烧过程。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 76,
+        "chunk": "# 2.4本章小结  \n\n本章中，利用均相酯化反应，将2-氯丙酰氯键合到纤维素链上，得到不同取代度的含氯纤维素衍生物。通过亲核取代反应，将三丁基麟、吡啶、1-甲基咪唑和N-乙烯基咪唑引入到纤维素链上，得到了不同取代度、不同阳离子类型的阳离子型纤维素衍生物。通过对纤维素三丁基氯盐、纤维素吡啶氯盐和纤维素1-甲基咪唑取代度控制，可以得到水溶、醇溶或有机溶剂溶解的纤维素衍生物材料。具有不同溶解性样品可以应用到不同领域及场景中，例如水溶性样品可以应用到水溶性涂料中，醇溶性样品可以应该生物医药中。另外，所制备水溶性纤维素衍生物可以很好地分散蒙脱土，蒙脱土的引入可以使我们得到水溶性阻燃涂层。当蒙脱土含量为 $30\\mathrm{wt\\%}$ 时，即可起到优异的阻燃性能。蒙脱土地引入使纤维素涂层具有明显的离火自熄现象，显著地降低了纤维素材料的最大热释放速率、热释放总量和热释放能力。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 77,
+        "chunk": "# 第3章利于 $\\mathbf{CO_{2}}$ 透过的阳离子型纤维素衍生物的制备与气体分离性能",
+        "category": " Introduction"
+    },
+    {
+        "id": 78,
+        "chunk": "# 3.1 引言  \n\n作为主要的温室气体，大气和海洋中不断增加的二氧化碳不仅会导致全球变暖和气候变化，而且还会对某些植物和微生物的生长产生重大影响。另一方面，$\\mathbf{CO}_{2}$ 是一种丰富，易于获得且无毒的碳资源，已被用作生产化学品，燃料和聚合物的重要原料。因此，有效，简便，经济高效的分离和捕集二氧化碳对减少温室效应和利用这种碳资源具有重要意义[186-188]。  \n\n$\\mathbf{CO}_{2}$ 分离捕集技术主要包括醇胺水溶液吸附法、多孔固体吸附法和膜分离法[189-192]。其中，膜分离法以其经济性、高效和便捷等优点而被广泛使用[193]。例如，通过膜分离方法分离 $\\mathrm{CO}_{2}/\\mathrm{CH}_{4}$ 和 $\\mathbf{CO}_{2}/\\mathbf{N}_{2}$ 已有几十年的历史。由于其优异的可成型性和可调性，各种聚合物材料已被广泛用作气体分离膜，例如醋酸纤维素、硅橡胶、聚烯烃、聚酰亚胺、聚矾[194-196]。醋酸纤维素（CA）是第一种商业用气体分离膜材料。CA以天然纤维素为原料，具有良好的成膜性，高拉伸强度和出色的 $\\mathbf{CO_{2}}$ 选择性，因此在 $\\mathbf{CO_{2}}$ 分离领域中占有重要地位。然而，CA的 $\\mathbf{CO}_{2}$ 渗透系数不高，因此许多学者通过各种方法来改善气体分离性能。通过添加各种填料，例如沸石 $\\Upsilon^{[196]}$ 、二氧化硅[197]、多壁碳纳米管[198]、 $\\mathbf{NH_{2}}\\mathbf{-MIL-}53^{[199]}$ ， $\\bf N i F e_{2}O_{4}$ 和$\\mathrm{TiO}_{2}^{[200]}$ 、MOF- $5^{[201]}$ 和离子液体[202]（ILs）设计和制造了一系列基于CA 的混合基质膜。尽管可以改善 $\\mathbf{CO}_{2}$ 的渗透性或选择性，但由于相容性差，分布不均或容易浸出，其增量受到一定限制。因此，开发具有高气体分离性能，优异的稳定性，良好的机械性能，良好的耐久性，制备工艺简单和较低价格的高性能聚合物气体分离膜材料仍然具有重要的意义。  \n\n本章中，我们提出并证明了一种新的策略，可以有效、简单地制造用于促进$\\mathbf{CO_{2}}$ 渗透的纤维素基气体分离膜。首先，将1-丁基咪唑阳离子（[Bim]\\*）引入到CA中，得到两种新型的阳离子化纤维素酯，醋酸纤维素1-丁基咪唑氯盐CA-BimCI)和醋酸纤维素1-丁基咪唑双(三氟甲烷磺酰基)酰亚胺(CA-BimTfN)。然后，阳离子化纤维素酯通过强静电相互作用可以有效地固定各种游离ILs，从而制得均匀，高透明的具有高 $\\mathbf{CO}_{2}$ 透过性，高热稳定性和高机械性能的纤维素酯/ ILs复合膜。",
+        "category": " Introduction"
+    },
+    {
+        "id": 79,
+        "chunk": "# 3.2实验部分",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 80,
+        "chunk": "# 3.2.1原料和试剂  \n\n醋酸纤维素（CA)：四川普什醋酸纤维素有限公司提供，取代度 $\\scriptstyle\\mathbf{DS}=1.89$ ，所用纤维素原料在 $80^{\\circ}\\mathrm{C}$ 真空烘箱干燥 $24\\mathrm{h}$ 0  \n\n2-氯丙烯酰氯（2-Chloropropionylchloride）：百灵威科技有限公司提供，纯度 $97\\%$ ·直接使用。  \n\nN-丁基咪唑（1-butylimidazole)：百灵威科技有限公司提供，纯度 $98\\%$ ，直接使用。  \n\n双三氟甲磺酰亚胺锂盐（LiTfN)：北京伊诺凯科技有限公司提供，纯度 $98\\%$ 直接使用。  \n\n1-胺丙基-3-三甲基咪唑双三氟甲磺酰亚胺盐（APmimTfN)，1-丁基-3-三甲基咪唑醋酸盐（BmimAc），1-丁基-3-三甲基咪唑双三氟甲磺酰亚胺盐（C4mimTfN），1-己基-3-三甲基咪唑双三氟甲磺酰亚胺盐（C6mimTfN），1-辛基-3-三甲基咪唑双三氟甲磺酰亚胺盐（C8mimTfN）、1-癸基-3-三甲基咪唑双三氟甲磺酰亚胺盐(ClomimTfN)：中国科学院兰州化学物理研究所提供，纯度 $98\\%$ 以上，直接使用。  \n\n超纯水：Milli-Q，Millipore $0.22\\upmu\\mathrm{m}$ 0  \n\n其他化学药品均从北京国药化学试剂公司获得，试剂均为分析纯，使用前无需进一步提纯。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 81,
+        "chunk": "# 3.2.2醋酸纤维素衍生物合成  \n\n（1）醋酸纤维素2-氯丙酸酯（CA-C1）合成：  \n\n将CA（4.1mmol）溶解在N，N-二甲基甲酰胺（DMF）中。然后，在 $0^{\\circ}\\mathbf{C}$ 下将 $13.7\\ \\mathrm{mmol}$ 的2-氯丙酰氯添加到CA／DMF溶液中。随后转移到 $40^{\\circ}\\mathbf{C}$ 油浴中，反应3h。将所得均匀溶液加入乙醇中以终止反应，并用乙醇将沉淀物过滤，用乙醇洗涤三次，在真空烘箱中 ${\\bf80}^{\\circ}{\\bf C}$ 下干燥 $24\\mathbf{h}$ 以获得CA-Cl。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 82,
+        "chunk": "# （2）醋酸纤维素1-丁基咪唑氯盐（CA-BimCl）  \n\n将 CA-Cl（3.1mmol）溶解在DMF 中。随后，添加14.0mmol的1-丁基咪唑，并且反应在 ${\\bf80}~^{\\circ}{\\bf C}$ 油浴中进行 $24\\mathrm{h}$ 。将所得溶液加入乙醇中以终止反应。过滤沉淀物，用乙醇洗涤三次， ${\\bf80}^{\\circ}{\\bf C}$ 真空干燥 $24\\mathrm{h}$ ，得到CA-BimCl。  \n\n(3）醋酸纤维素1-丁基-3-三甲基咪唑双三氟甲磺酰亚胺盐（CA-BimTfN)  \n\n将CA-BimCl（2.5mmol）溶于水中。然后，滴加LiTfN的饱和水溶液（2.3mmol)。将反应体系在室温搅拌 $24\\mathrm{h}$ 。出现白色沉淀。过滤沉淀物，用去离子水洗涤三次，并在 $80^{\\circ}\\mathrm{C}$ 下真空干燥 $24\\mathrm{h}$ ，以获得CA-BimTfN。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 83,
+        "chunk": "# 3.2.3气体分离膜制备  \n\n通过溶液流延法制备CA-BimTfN/IL和CA/ILs膜。制备过程如下：将1.5g 的CA或CA-BimTfN溶解在 $13.5\\ \\mathbf{g}$ 的DMF中，以获得浓度为 $10\\mathrm{\\textperthousand}$ 的CA/DMF或CA-BimTfN/DMF溶液。然后，加入一定量的所需IL。然后将所得溶液流延到玻璃板上。在 $65~^{\\circ}\\mathrm{C}$ 的热台上蒸发溶剂。随后，成膜后并将其从玻璃基板剥离。在真空下于 $80~^{\\circ}\\mathrm{C}$ 进一步干燥 $24\\mathrm{h}$ ，获得 CA-BimTfN/ILs 和 CA/ ILs膜。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 84,
+        "chunk": "# 3.2.4结构与性能表征  \n\n（1）核磁共振 ${}^{1}\\mathrm{H}$ -NMR:  \n\n${}^{1}\\mathrm{H}.$ -NMR光谱均采用BrukerAV400核磁共振波谱仪测定。用DMSO- ${\\bf\\sigma}\\cdot{\\bf d}_{6}$ 为溶剂溶解样品，测试前加2-3滴气代三氟乙酸将活泼氢移至低场。  \n\n（2）傅里叶变换红外光谱（FTIR)：  \n\n红外光谱采用ThermoNicolet6700傅里叶变换红外光谱仪测定，波数范围$650–4000\\ \\mathrm{cm}^{-1}$ ，分辨率是 $4\\mathrm{cm}^{-1}$ ，扫描次数32次。  \n\n（3）X射线光电子能谱（XPS）：  \n\nXPS测试使用X射线光电子能谱仪ESCALab250Xi（ThermoFisher，USA）。  \n\n（4）紫外可见光谱分析：  \n\nUV-Vis光谱采用Perkin-ElmerLambda 35光谱仪测定，扫描范围 400-800nm。扫描速度为高速。  \n\n（5）热失重分析：  \n\n热重分析采用Perkin-ElmerPyris-1热分析仪测定样品在氮气气氛下的热失重行为。称取样品质量 $3\\mathrm{mg}$ 左右，温度范围 $50-750^{\\circ}\\mathrm{C}$ ，升温速率 $20\\ensuremath{\\mathrm{^\\circC/min}}$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 85,
+        "chunk": "# （6）扫描电镜分析：  \n\n样品形态采用JEOL公司的JSM-6700F场发射扫描电子显微镜观察，观察前对样品表面进行喷金，增加样品导电性，加速电压为 ${5.0\\mathbf{k}\\mathbf{V}}$ 。  \n\n（7）光学照片：  \n\n光学照片均采用数码相机（SONY $\\mathtt{\\Gamma}\\mathtt{\\backslash}\\mathtt{\\Gamma}\\mathtt{\\backslash}\\mathtt{\\Gamma}\\mathtt{\\backslash}$ ，Japan）拍摄所得。  \n\n（8）力学性能测试：  \n\n拉伸测试在万能试验机(Instron3365,INSTRON,USA)上进行，带有 5kn 的测压元件，十字头速度为 $2\\mathrm{mm}/\\mathrm{min}$ 。将试件切成 $10\\mathrm{mm}$ 宽、 $50\\mathrm{mm}$ 长的矩形条带（9）气体渗透系数测试：  \n\n采用兰光VAC-V2气体渗透仪进行测试。气体纯度 $0_{2}99.995\\%,\\mathrm{N}_{2}99.999\\%$ .$\\mathrm{CH_{4}}99.99\\%$ ，C $99.99\\%$ ， $\\mathrm{CO}_{2}99.999\\%$ 。将所制备的膜裁成直径为 $4\\mathrm{cm}$ 的圆片进行测试，其中有效测试面积为 $4.95\\mathrm{cm}^{2}$ 。测试腔置于循环水浴中，膜上腔压力为 $1\\mathsf{a t m}$ ，膜下腔抽真空 $12\\mathrm{h}$ ，依次对 $\\mathbf{O}_{2}$ ， $\\mathbf{N}_{2}$ ， $\\mathrm{CH}_{4}$ ，co， $\\mathbf{CO}_{2}$ 进行气体渗透性能测试。气体渗透系数 $(P$ ）可以通过下腔压力-时间曲线自动计算得到。理想气体选择系数 $\\mathbf{\\Pi}(\\mathfrak{a})$ 通过如下公式（3-1）计算得到。  \n\n$$\n{\\bf a_{\\alpha}}\\left({\\bf A}/{\\bf B}\\right)=P_{\\bf A}/P_{\\bf B}\n$$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 86,
+        "chunk": "# 3.3结果与讨论",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 87,
+        "chunk": "# 3.3.1醋酸纤维素阳离子衍生物合成及表征  \n\n纤维素是地球上最丰富的生物聚合物，具有许多吸引人的特性，例如可再生性，出色的可逆性，可完全生物降解性，出色的生物相容性，高的机械性能和结构可设计性。特别是，考虑到沿分子结构规则分布的羟基，可以在纤维素链中引入多个官能团，并得到各种各样的纤维素衍生物。  \n\n![](images/0c0a4ab9e3e1db7ad0714b13ce96922ec91b199b58615613625ef4b052a92a25.jpg)  \n\n图3.1两种阳离子型纤维素酯CA-BimCI和CA-BimTfN的合成途径和结构表征（a）合成路线（b） ${}^{1}\\mathrm{H}$ -NMR谱图（c）FTIR光谱图（d）XPS谱图。  \n\nFigure 3.1 Synthetic route and structure characterization of two cationized cellulose esters, CA-BmimCl and CA-BmimTfN（a） Synthetic route（b） ${}^{1}\\mathrm{H}\\cdot$ NMR spectra.  \n\n(c）FTIR spectra （d） XPS survey spectra.  \n\n利用纤维素出色的结构可设计性，一种新型的纤维素混合酯，醋酸纤维素2-氯丙酸酯（CA-Cl）通过均匀且可控的酯化过程合成得到（图3.1a)。在CA-CI的 $^1\\mathrm{H}$ NMR谱图中（图 $3.1\\ \\mathrm{b}$ ， $1.62\\ \\mathrm{ppm}$ 处的峰归因于2-氯丙酸酯中甲基的氢，在 $1.70{-}2.20~\\mathrm{ppm}$ 处的峰归因于醋酸纤维素中甲基的氢，而 $1.70\\ \\mathrm{ppm}$ 处的峰和$2.70{-}5.60~\\mathrm{ppm}$ 处的峰是纤维素骨架和2-氯丙酸酯中亚甲基的氢。根据纤维素骨架与2-氯丙酸酯的甲基氢积分面积比，计算出2-氯丙酸酯的DS（取代度)为0.90。然后，在CA-CI和1-丁基咪唑之间进行亲核取代反应后，获得了阳离子化纤维素衍生物CA-BimCl（图3.1a）。在CA-BimCl的 ${}^{1}\\mathrm{H}\\ \\mathrm{NMR}$ 谱图中（图3.2），在0.92、1.56、2.12和 $4.24~\\mathrm{ppm}$ 处的新峰归属于1-丁基咪唑（ $\\mathrm{Bim}$ ）基团的丁基的氢，7.85和 $9.34~\\mathrm{ppm}$ 处的峰归属于Bim基团的咪唑环上的氢。在CA-BimCl的FTIR光谱中（图3.1b），在1560、1470和 $1165\\mathrm{cm}^{-1}$ 处的新峰与咪唑特征峰相对应。在CA-BimCI的XPS谱图中（图3.1c)，有N峰和Cl峰。由此表明了阳离子化的CA-BimCl已经被成功合成。根据纤维素骨架与咪唑上氢的积分面积比，Bim 的DS为0.60。最后，通过阴离子交换步骤，制备了不溶于水可溶于有机溶剂的CA-BimTfN。在CA-BimTfN的FTIR光谱中（图3.1b)，在1327、1230、1192、1136和 $1056\\mathrm{cm}^{-1}$ 处的峰与[TfN] 阴离子特征峰相对应。在CA-BimTfN的XPS光谱中（图3.1c)，出现了元素F和元素S的新峰，表明已成功合成了阳离子化的CA-BimTfN。  \n\n![](images/8abdad8679d3c257cefadf6e79ac611c7984ac526dff0e0bfdc0aead9fd8e54d.jpg)  \n图3.2CA-BimClandCA-BimTfN核磁氢谱图  \nFigure.3.2 ${}^{1}\\mathrm{H}.$ -NMR spectra of CA-BimCl and CA-BimTfN.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 88,
+        "chunk": "# 3.3.2分离膜形貌表征  \n\n![](images/a25f5ab04929283d1b7f0719077f20134ed1cf330fbfae29e1ae4e5925879971.jpg)  \n图3.3CA-BimTfN／ILs膜的构建和形貌（a）用于 $\\mathrm{CO}_{2}/\\mathrm{N}_{2}$ 气体分离的CA-BimTfN/ILs膜示意图（b）CA-BimTfN/ILs膜的照片  \n\nFigure 3.3 Construction and morphology of CA-BmimTfN/ILs membranes. (a) Schematic diagram of CA-BimTfN/ILs membranes for $\\mathrm{CO}_{2}/\\mathrm{N}_{2}$ gas separation. (b) Photographs of CA-BimTfN/ILs membranes.  \n\n所得的阳离子化CA-BimTfN可以有效地固定各种IL，包括1-丁基-3-甲基咪唑乙酸盐（BmimAc)，1-（3-氨基丙基）-3-甲基咪唑双（三氟甲基磺酰基）酰亚胺（APmimTfN）和1-烷基-3-甲基咪唑双（三氟甲基磺酰基）酰亚胺(CnmimTfN， $\\mathrm{n}=4$ ，6，8,10)，通过强静电相互作用（图3.3a)。将获得的CA-BimTfN/ILs膜编码为 $\\textbf{\\em x}\\%\\mathbf{\\$ ，其中 $\\textbf{X\\%}$ 代表IL与CA-BimTfN的质量比。显然，所有CA-BimTfN/ILs膜都是高度透明的（图 $3.36$ 和3.4)，表明离子化的CA-BimTfN和ILs之间具有出色的相容性。  \n\n![](images/51c8af82e1a7dc018794ce0a890af13df684e395f4f036a08f18e0060310fc70.jpg)  \n图3.4CA-BimTfN/ $40\\%$ C1omimTfN膜光学照片  \n\n![](images/5e2cb11b060f75e310478ace261e28c8ed6463d26b469d05e4d94756182aeb40.jpg)  \nFigure 3.4 Photograph of CA-BmimTfN / $40\\%$ CiomimTfN membrane.   \n图3.5CA-BimTfN/C1omimTfN膜紫外可见光谱  \n\nFigure 3.5 UV-vis transmission spectra of CA-BmimTfN/C1omimTfN membranes.  \n\n它们在可见光区域的透光率高于 $70\\%$ ，尤其是CA-BimTfN/C1omimTfN，其透光率约为 $90\\%$ （图3.5)。从扫描电子显微镜（SEM）图像中可以明显看出，所有CA-BmimTfN/ILs膜均是均匀且光滑的（图3.6和3.7)。即使在含有大量ILs（例如 $140\\%\\mathrm{C_{10}m i m T f_{2}N}$ ）的CA-BimTfN/ILs膜中也没有相分离现象。相反，由于CA基质和ILs之间不存在相互作用，导致CA/ILs膜不均匀，并且具有明显的相分离现象（图3.8)。因此，在聚合物链上构建离子化功能团是制备具有优异相容性和抗迁移性的均质聚合物/ILs复合材料的简便有效策略。  \n\n![](images/24c1f6e4734c41586c3c3de5dcf556165a783065735bcb4587321519022e9c41.jpg)  \n图3.6CA-BimTfN/ILs 膜断面SEM图像。将CA-BimTfN/ILs膜命名为x%ILs，其中 $8\\%$ 代表ILs与CA-BimTfN的质量比。  \n\n![](images/5aafd3fbd73eb2ba7532e6e9a96915eb9e10e2f9d3d071aea10fc82bc3d861ab.jpg)  \nFigure 3.6 SEM images of the cross-section of CA-BimTfN/ILs membranes. The CABimTfN/ILs membranes are named as $\\textbf{X\\%}$ ILs,where $\\textbf{X\\%}$ represents the massratio of ILs to CA-BimTfN.   \n图3.7CA-BimTfN/C1omimTfN膜的SEM图  \n\nFigure3.7SEMimage ofCA-BimTfN/CiomimTfNmembranes.  \n\n![](images/ba28abcd9e985b4c953b649e19ed85e736eadf2c88affc95b8d1236249b2a8a7.jpg)  \n图3.8（a）CA/BimAc 膜(b)CA/C6mimTfN 膜(c)CA-BimTfN/BmimAc 膜(d)CA-BimTfN/C6mimTfN膜照片  \n\nFigure 3.8 Photographs of (a) CA / BmimAc membranes, (b) CA / C6mimTfN membranes, (c) CA-BimTfN / BmimAc membranes, (d) CA-BimTfN / C6mimTfN membranes.  \n\n由于ILs的具有多种结构，性能可调的特性，可忽略的蒸气压和优异的热稳定性，因此已经对其进行了广泛的研究以捕获 $\\mathrm{CO}_{2}$ 气体或制造气体分离膜。因此，我们制备的CA-BimTfN/ILs透明膜也可被用作气体分离膜。它们的气体分离特性已通过经典的压差法进行了检测。如表3.1所示，与CA膜相比，CA-BimTfN膜由于在纤维素链中引入了咪唑阳离子，因此对 $\\mathrm{CO}_{2}$ ， $\\mathrm{N}_{2}$ ， $\\mathrm{CH}_{4}$ ，CO和$\\mathrm{O}_{2}$ 的渗透性要高1-2倍。同时， $\\mathrm{O}_{2}/\\mathrm{N}_{2}$ ， $\\mathrm{CO}_{2}/\\mathrm{N}_{2}$ 和 $\\mathrm{CO}_{2}/\\mathrm{CH}_{4}$ 的渗透系数（ $P$ ）略有增加。对于CA-BimTfN/ILs膜，ILs的种类和含量对气体分离性能有不同的影响。BmimAc和APmimTfN对气体分离性能的影响可忽略不计或较差。所得的CA-BimTfN/BmimAc和CA-BimTfN/APmimTfN膜表现出较低的渗透性或选择性。如果使用C4mimTfN， $\\mathrm{C_{6}m i m T f_{2}N}$ ，CgmimTfN或 $\\mathrm{C_{10}m i m T f_{2}N}$ 则相应的CA-BimTfN／CnmimTfN膜对 $\\mathrm{CO}_{2}$ ， $\\mathrm{N}_{2}$ 、 $\\mathrm{CH}_{4}$ 、CO和 $\\mathbf{O}_{2}$ （尤其是对$\\mathrm{CO}_{2}$ ）的渗透性会显著提高。此外，随着阳离子上烷基链长的增加，CA-BimTfN/ $\\mathrm{C_{nmimTf}N}$ 膜的气体渗透性变得更好。另外，随着ILs含量的增加，气体渗透率也增加（图 $3.9\\mathrm{a}$ )。C1omimTfN/CA-BimTfN比例为 $140\\%$ 时表现出最高的 $\\mathrm{CO}_{2}$ 渗透性（91.1barrer），这比CA膜高38倍，比CA-BimTfN膜高17倍。同时， $\\mathrm{CO}_{2}/\\mathrm{N}_{2}$ 和 $\\mathrm{CO}_{2}$ /CO的渗透选择性分别保持在24和16左右（图 $3.9\\ \\mathrm{b}\\ \\AA\\cdot$ 。与以前的报道相比，CA-BimTfN/C1omimTfN膜对 $\\mathrm{CO}_{2}$ 具有更高的渗透性，并且它们对 $\\mathrm{CO}_{2}/\\mathrm{N}_{2}$ 和 $\\mathrm{CO}_{2}/\\mathrm{CH}_{4}$ 的气体分离特性更接近于罗伯逊上界（图3.9c和$3.9{\\dot{\\mathbf{d}}})$ a  \n\n表3.1CA，CA-BimTfN和CA-BimTfN/ILs膜的渗透系数及选择性。  \n\nTable 3.1 Gas permeability and permselectivity of CA, CA-BimTfN and CABimTfN/ILs membranes.   \n\n\n<html><body><table><tr><td rowspan=\"2\">Samples</td><td colspan=\"4\">Permeability (barrer)</td><td colspan=\"4\">Permselectivity (α)</td></tr><tr><td>CO2</td><td>N2</td><td>CH4</td><td>Co</td><td>0/N</td><td>CO/N</td><td>CO/C0</td><td>CO/CH4</td></tr><tr><td>CA</td><td>2.4</td><td>0.1</td><td>0.1</td><td>0.1 0.5</td><td>5.0</td><td>24.0</td><td>24.0</td><td>24.0</td></tr><tr><td>CA-BimTfN</td><td>5.5</td><td>0.2</td><td>0.2</td><td>0.3 1.2</td><td>6.0</td><td>27.5</td><td>18.3</td><td>27.5</td></tr><tr><td>40% BmimAc</td><td>1.7</td><td>0.3</td><td>0.4</td><td>0.3 0.5</td><td>1.7</td><td>5.7</td><td>5.7</td><td>4.2</td></tr><tr><td>40% APmimTfN</td><td>3.1</td><td>0.1</td><td>0.1</td><td>0.5 0.6</td><td>6.0</td><td>31.0</td><td>6.2</td><td>31.0</td></tr><tr><td>40% C4mimTfN</td><td>15.2</td><td>0.5</td><td>0.7</td><td>0.7 2.4</td><td>4.4</td><td>27.6</td><td>20.3</td><td>20.0</td></tr><tr><td>40% C6mimTfN</td><td>16.7</td><td>0.5</td><td>0.8</td><td>0.8 2.3</td><td>4.0</td><td>29.2</td><td>20.1</td><td>19.6</td></tr><tr><td>40% CgmimTfN</td><td>22.1</td><td>0.9</td><td>1.3</td><td>1.1 3.5</td><td>3.8</td><td>25.5</td><td>19.1</td><td>16.5</td></tr><tr><td>40% C1omimTfN</td><td>29.8</td><td>1.1</td><td>2.5</td><td>3.0 4.4</td><td>4.0</td><td>27.1</td><td>10.0</td><td>12.0</td></tr><tr><td>60% C1omimTfN</td><td>38.9</td><td>1.6</td><td>2.8</td><td>2.4 5.7</td><td>3.6</td><td>24.4</td><td>16.1</td><td>13.6</td></tr><tr><td>80% C1omimTfN</td><td>64.3</td><td>2.5</td><td>5.1</td><td>3.9 8.8</td><td>3.4</td><td>24.8</td><td>16.5</td><td>12.6</td></tr><tr><td>100% C1omimTfN</td><td>73.1</td><td>3.4</td><td>6.2</td><td>5.0 9.8</td><td>3.0</td><td>24.5</td><td>14.4</td><td>11.7</td></tr><tr><td>120% C1omimTfN</td><td>80.0</td><td>3.5</td><td>8.0</td><td>4.9 13.0</td><td>3.4</td><td>23.0</td><td>16.1</td><td>10.1</td></tr><tr><td>140% C1omimTfN</td><td>91.1</td><td>3.7</td><td>8.3</td><td>6.3 13.4</td><td>3.5</td><td>24.3</td><td>14.3</td><td>11.0</td></tr></table></body></html>  \n\n![](images/43eb123e07b302694a451edc718deba51241f9ef2b4ca952c0c74fd00c726f73.jpg)  \n\n图 $3.9~\\mathrm{CA}$ ，CA-BimTfN和CA-BimTfN／C1omimTfN膜的渗透系数及选择性。(a) $\\mathrm{CO}_{2}$ ， $\\mathrm{CH}_{4}$ 和 $\\mathrm{N}_{2}$ 的渗透性。（b）对 $\\mathrm{CO}_{2}/\\mathrm{N}_{2}$ 和 $\\mathrm{CO}_{2}/\\mathrm{CH}_{4}$ 的渗透选择性。（c）比较这项工作中的CA-BimTfN／CiomimTfN膜和其他改良CA膜之间的$\\mathrm{CO}_{2}/\\mathrm N_{2}$ 分离性能。（d）比较这项工作中的CA-BimTfN/CiomimTfN膜与其他改性的CA膜之间的 $\\mathrm{CO}_{2}/\\mathrm{CH}_{4}$ 分离性能。（RobesonUpperBound的数据（2008年)，来自文献。)  \n\nFigure 3.9 Gas permeability and permselectivity of CA, CA-BimTfN and CABimTfN/CiomimTfN membranes. (a) Permeability for $\\mathrm{CO}_{2}$ $\\mathrm{CH}_{4}$ and $\\mathrm{N}_{2}$ (b) Permselectivity for $\\mathrm{CO}_{2}/\\mathrm{N}_{2}$ and $\\mathrm{CO}_{2}/\\mathrm{CH}_{4}$ ：(c）Comparison of $\\mathrm{CO}_{2}/\\mathrm{N}_{2}$ separation performance between CA-BimTfN/CiomimTfN membrane in this work and other modified CA membranes. (d) Comparison of $\\mathrm{CO}_{2}/\\mathrm{CH}_{4}$ separation performance between CA-BimTfN/CiomimTfN membrane in this work and other modified CA membranes. (Data of Robeson Upper Bound (20o8) from literature .)  \n\n为了了解CA-BimTfN/C1omimTfN膜的高透气性机理，我们计算了不同分离膜对 $\\mathrm{CO}_{2}$ $\\mathrm{N}_{2}$ 和 $\\mathrm{CH}_{4}$ 的扩散系数（D）和溶解度系数（S)，如表3.2所示。在CA-BimTfN / $\\mathrm{C_{10}m i m T f_{2}N}$ 膜中，扩散系数明显高于CA和CA-BimTfN膜。此外，随着 $\\mathrm{C_{10}m i m T f_{2}N}$ 的含量增加，扩散系数急剧增加。例如，100%C1omimTfN的 $\\mathrm{CO}_{2}$ 扩散系数比CA高2个数量级。另外，添加 $\\mathrm{C_{10}m i m T f_{2}N}$ 后，溶解度系数略有降低。因此，添加的C1omimTfN显著提高了气体扩散速率，导致气体渗透  \n\n率显著提高。  \n\n表3.2CA，CA-BimTfN和CA-BimTfN/ILs膜的气体扩散系数（D）和溶解度系数（S）。  \n\nTable 3.2 Gas diffusion coefficient $(D)$ and solubility coefficient (S) of CA,CABmimTfN and CA-BmimTfN/ILs membranes.   \n\n\n<html><body><table><tr><td rowspan=\"2\">Samples</td><td colspan=\"3\">Diffusivity (cm²·s-l)</td><td colspan=\"3\">Solubility (cm(STP)/(cm²-cmHg)</td></tr><tr><td>CO2</td><td>N</td><td>CH4</td><td>CO2</td><td>N</td><td>CH4</td></tr><tr><td>CA</td><td>2.60E-09</td><td>4.90E-09</td><td>9.70E-10</td><td>0.1</td><td>1.90E-03</td><td>8.80E-03</td></tr><tr><td>CA-BimTfN</td><td>8.20E-09</td><td>3.80E-08</td><td>5.70E-09</td><td>6.70E-02</td><td>5.70E-04</td><td>4.00E-03</td></tr><tr><td>40%C1omimTfN</td><td>5.70E-08</td><td>5.70E-07</td><td>1.10E-07</td><td>2.60E-02</td><td>9.50E-05</td><td>2.10E-03</td></tr><tr><td>60%C1omimTfN</td><td>1.30E-07</td><td>9.40E-07</td><td>1.40E-07</td><td>3.10E-02</td><td>1.70E-04</td><td>2.20E-03</td></tr><tr><td>80% C1omimTfN</td><td>1.50E-07</td><td>3.70E-07</td><td>2.10E-07</td><td>4.40E-02</td><td>6.90E-04</td><td>2.40E-03</td></tr><tr><td>100%C1omimTfN</td><td>2.80E-07</td><td>2.20E-07</td><td>2.20E-07</td><td>2.50E-02</td><td>1.50E-03</td><td>2.90E-03</td></tr><tr><td>120%C1omimTfN</td><td>3.60E-07</td><td>6.00E-07</td><td>2.30E-07</td><td>2.20E-02</td><td>7.00E-04</td><td>3.40E-03</td></tr><tr><td>140%C1omimTfN</td><td>4.50E-07</td><td>6.10E-07</td><td>2.40E-07</td><td>2.00E-02</td><td>7.35E-04</td><td>3.40E-03</td></tr></table></body></html>  \n\n![](images/a3e5c1383c0f9303f450b15abe24778c032e44551e859f0181b8d391ef372f4f.jpg)  \n图3.10CA，CA-BimTfN和CA-BimTfN/ILs膜的力学性能和热稳定性（a）应力-应变曲线（b）TGA曲线。  \n\nFigure 3.10 Mechanical properties and thermal stability of CA, CA-BimTfN and CABimTfN / ILs membranes (a) Stress-strain curves (b) TGA curves.  \n\n在气体分离膜的实际应用中，良好的机械性能和高的热稳定性是必不可少的先决条件。CA-BimTfN膜具有 $50.5{\\scriptstyle\\pm4.4}\\mathrm{MPa}$ （兆帕斯卡）的高拉伸强度（图3.10a)。具有长烷基链的C1omimTfN具有增塑作用，因此所得的CA-BimTfN/C1omimTfN膜的拉伸强度降低，断裂伸长率提高。即使这样，CA-BimTfN/C1omimTfN膜仍具有良好的机械性能，拉伸强度为 $10{-}55~\\mathrm{MPa}$ ，断裂伸长率为$10-30\\%$ （图3.10a）。特别地，CA-BimTfN/C1omimTfN膜的拉伸强度可与商业聚烯烃膜（例如聚乙烯（PE）和聚丙烯（PP)）的拉伸强度相当，后者的拉伸强度范围为 $15{\\cdot}40\\mathrm{MPa}$ 。此外，在氮气气氛下，通过热重分析（TGA）分析了CA-BimTfN/C1omimTfN膜的热稳定性（图 $3.10\\mathrm{b}$ )。CA-BimTfN/C1omimTfN膜的起始分解温度（ $\\mathrm{T_{onset}}$ ）约为 $270~^{\\circ}\\mathrm{C}$ ，与CA相似。它们具有两个热降解过程，最大分解温度（ $\\mathrm{\\DeltaT_{max}}$ ）分别为 $290{-}305^{\\circ}\\mathrm{C}$ 和 $415{\\cdot}450^{\\circ}\\mathrm{C}$ （图3.11)。较低温度区域的热降解过程（称为\"过程1\"）源自CA聚合物链的降解，而较高温度的热降解过程（称为\"过程 $2^{,,}$ ）归因于BimTfN部分的分解和 $\\mathrm{C_{10}m i m T f_{2}N}$ 。这些结果证实了CA-BimTfN／C1omimTfN膜具有出色的热稳定性。这种具有高CO2渗透性，高透明性，良好的机械性能和高热稳定性的高性能CA-BimTfN/C1omimTfN膜在气体分离的实际应用中具有巨大的潜力。  \n\n![](images/8a14520c358f6f3f79ee1253f6fbc28f56288cf3a9ccd3d379b93d942f8c2270.jpg)  \n图3.11（a）CA和 $\\mathrm{C}_{10}\\mathrm{mimTf_{2}N}$ 热失重曲线（b）CA-BimTfN和CA-BimTfN/$\\mathrm{{C}_{10}\\mathrm{{mimTf_{2}N}}}$ 在氮气氛下的热失重积分曲线（DTG)。  \n\nFigure 3.11 Derivative thermogravimetric (DTG) curves of (a)TGA of CA and C1omimTfN, (b) DTG of CA-BimTfN and CA-BimTfN/C1omimTfN under nitrogen atmosphere.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 89,
+        "chunk": "# 3.4本章小结  \n\n本章中，我们提出了一种新的策略，可以有效、简单地制备纤维素基气体分离膜材料，该方法所制备的膜可以促进 $\\mathbf{CO}_{2}$ 的渗透，并很好地保持 $\\cos_{2}/\\Nu_{2}$ 选择性。首先，设计并合成了两种新型的含有1-丁基咪唑阳离子的离子化纤维素酯，CA-BimCl和CA-BimTfN。然后，利用强大的静电相互作用，离子化纤维素酯可以有效地固定各种ILs，包括BmimAc，APmimTfN和CnmimTfN（n=4、6、8、10)。结果，获得了均匀，高透明和热稳定的纤维素酯/ILs复合膜。当使用 $\\mathbf{C}_{10}\\mathbf{mimTf}_{2}\\mathbf{N}$ 时，由于 $\\mathbf{CO}_{2}$ 扩散速率显著增加，纤维素酯/ILs膜的$\\mathbf{CO}_{2}$ 渗透性显著提高。CA-BimTfN/C1omimTfN膜的 $\\mathbf{CO}_{2}$ 透过性最高，比CA膜高38倍，比CA-BimTfN膜高17倍。同时， $\\mathrm{CO}_{2}/\\mathrm{N}_{2}$ 的理想选择性保持在24左右。更重要的是，CA-BimTfN/CiomimTfN膜具有良好的机械性能，拉伸强度为 $10{-}55\\mathrm{MPa}$ ，断裂伸长率为 $10{-}30\\%$ 。这种简便的策略在制造高性能的 $\\mathbf{CO}_{2}$ 分离膜方面具有巨大潜力，有利于保护环境和利用碳资源",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 90,
+        "chunk": "# 第4章具有防雾、抗冰和自清洁性能的阳离子型纤维素衍生物的制备与性能",
+        "category": " Introduction"
+    },
+    {
+        "id": 91,
+        "chunk": "# 4.1引言  \n\n起雾、结冰是生活中常见现象。然而，雾和冰的形成会引起基底的光学透明性降低，导致眼镜、挡风玻璃和高价值光学器件使用过程中出现安全问题[20,203204]。同时冰的形成给交通运输或基础设施等带来严峻挑战，包括电网基础设施崩溃、风力发电叶片损害和交通事故等[205,206]。  \n\n现在已经有采用透明电热丝和对流干燥以降低温差和减小水汽来达到防雾效果[207-209]。然而，这些设备通常安装复杂，维护成本高，限制了其广泛使用。因为细小水滴可以在亲水涂层中可以迅速扩散铺展，因此利用（超）亲水性材料或者改性可以达到湿式防雾[208-210]，例如用阴离子、阳离子和两亲性聚电解质改性亲水材料可以增加防雾效果[2I，但是当水超过膜的容量时，其顶部的水仍会造成使光学性质显著变化。此外超亲水防雾涂层也会使金属膨胀、和基体难剥离和使金属表面腐蚀，这些问题通常由于吸附水分引起[212]。而且，由于超亲水材料具有高表面能，更容易受到有机物污染。另一种防雾方式是通过将涂层表面处理成（超)疏水，该涂层具有极高的水接触角（例如超疏水材料水接触角 ${>}150^{\\circ}.$ 通过排斥宏观可见的水滴来实现干式防雾[213-215]。但是，低湿度情况下及水凝结早期很难具有良好的防雾效果。最近，通过结合超亲水和超疏水材料制备zwitter-wettable膜[11,215,216],通常上层为疏水性物质，下层为亲水性物质，可以使zwitter-wettable膜在各种湿度环境下起到良好的防雾效果。这种策略往往需要亲水材料和疏水材料两种材料结合和较为复杂的制备过程，尚未有报道单一材料在不同湿度环境下均可起到优异的防雾效果的涂层。  \n\n冰的形成会给社会带来严重的经济、能源和安全问题。为了解决此问题，研究者开发了各种各样的防冰策略，制备各种各样的表面以抑制冰成核、减小冰粘附力[217-22]。例如，超疏水材料在抑制冰成核具有良好的效果，但是因其表面存在微纳结构并不能有效地进一步降低冰粘附力。目前，抗冰蛋白、防冻剂、聚电解质在抗冰领域中被广泛的研究[223-226]。其中，具有离子特异性的聚合物电解质刷，具有优异的调节冰成核性能。同时，研究发现，聚电解质可以与水发生极化，从而出现水合层，水合层的存在可以有效地减小冰粘附力[227]。例如，王健君组[228]通过仿天然抗冻蛋白，将疏水性聚二甲基硅氧烷（PDMS）接枝到亲水性的聚合物电解质刷中，得到了同时降低冰成核温度、冰传播、冰粘附的多功能水凝胶。然而，制备一种具有可实际使用，同时具有良好抗冰性能的材料仍然存在挑战。  \n\n本章通过在亲水性物质纤维素上引入亲水性阳离子基团，通过离子交换将阴离子交换为疏水性离子，得到一种新型离子化纤维素衍生物材料。纤维素链上有多个羟基，可以通过控制取代度调节亲水基团和疏水基团比例，以达到调节界面水目的，从而实现调节冰成核温度及冰粘附力。同时实现材料在高低湿度下均可防雾的目的。由于涂层材料的低表面能，也可实现良好的抗污效果，例如抗小球藻、抗蛋白粘附、自清洁等。材料中阴阳离子也使材料具有优异的抗菌性能。最终，我们得到了一种具有防雾、抗冰和自清洁功能的涂层材料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 92,
+        "chunk": "# 4.2实验部分",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 93,
+        "chunk": "# 4.2.1原料和试剂  \n\n棉浆粕（CottonPulp)：山东恒联新材料有限公司提供，聚合度 $\\scriptstyle\\mathbf{DP=650}$ ，所用纤维素原料在 ${\\bf80^{\\circ}C}$ 真空烘箱干燥 $24\\mathbf{h}$ 9  \n\n2-氯丙烯酰氯（2-Chloropropionylchloride）：百灵威科技有限公司提供，纯度 $97\\%$ 直接使用。  \n\nN-丁基咪唑（1-butylimidazole）：百灵威科技有限公司提供，纯度 $98\\%$ ，直接使用。  \n\n全氟辛酸钠（PFONa)：北京伊诺凯科技有限公司提供，纯度 $97\\%$ ，直接使用。离子液体 1-烯丙基-3-甲基咪唑氯盐（1-Allyl-3-methylimidazole chloride,AmimC1)：为实验室合成，含水量小于 $0.3\\%$ 0  \n\n超纯水：Milli-Q，Millipore ${\\ 0.22\\upmu\\mathrm{m}}$ 6  \n\n牛血清蛋白（AR）、The Micro $\\mathbf{BCA}^{\\mathrm{TM}}$ Protein assaykit：阿拉丁公司提供，纯度$98\\%$ ，直接使用。  \n\n藻种：普通小球藻（Chlorellasp），实验室保存。  \n\n小球藻培养基：BG11培养基，按配方配制完成后，将其分别置于高压灭菌锅中  \n\n$120^{\\circ}\\mathrm{C}$ 灭菌 $25\\mathrm{min}$ ，待其冷却后备用。  \n\n其他化学药品均从北京国药化学试剂公司获得，试剂均为分析纯，使用前无需进一步提纯。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 94,
+        "chunk": "# 4.2.2疏水性阳离子纤维素衍生物合成  \n\n（1）纤维素2-氯丙酸酯（Cellulose-C1）合成  \n\n取 $_{1\\mathrm{~g~}}$ 棉浆在 $ 80^{\\circ}\\mathrm{C}$ 下溶解于 $24\\:\\mathrm{g}\\:\\mathrm{AmimCl}$ 中，随后在冰水浴中加入 $2.4\\ \\ g\\ 2\\mathrm{-}$ 氯丙酰氯，成分混合均匀后，转移到 $40^{\\circ}\\mathrm{C}$ 油浴中反应2h。反应结束后加入乙醇终止反应，并用乙醇将样品沉淀，使用砂芯漏斗过滤、洗涤三次后，放置于 ${\\bf80}^{\\circ}{\\bf C}$ 真空烘箱中烘干。将干燥后的样品溶解于DMSO中，再次使用乙醇沉淀，过滤、洗涤三次，最后置于 $80~^{\\circ}\\mathrm{C}$ 的真空烘箱中干燥，得到不同取代度纤维素2-氯丙酸酯（Cellulose-C1)。  \n\n（2）纤维素1-丁基咪唑氯盐（Cellulose-BimCl）合成  \n\n将1gCellulose-Cl 溶解于DMF 中，加入 $2.5{\\mathrm{g}}N{\\mathrm{-}}$ 丁基咪唑反应于 $80^{\\circ}\\mathrm{C}$ 油浴中回流反应 $24\\mathrm{h}$ 。反应结束后，加入丙酮沉淀，使用砂芯漏斗过滤、洗涤三次后，放置于 ${\\bf80^{\\circ}C}$ 真空烘箱中烘干。将干燥后的样品溶解于DMSO中，再次使用丙酮沉淀，过滤、洗涤三次，最后置于 ${\\bf80}~\\mathrm{{^\\circC}}$ 的真空烘箱中干燥，得到不同取代度纤维素1-丁基-3-甲基咪唑氯盐（Cellulose-BimCI)。  \n\n（3）纤维素1-丁基咪唑全氟辛酸盐（Cellulose-BimPFO）合成  \n\n将 $_{\\mathrm{~1~g~}}$ Cellulose-BimCl 溶解到水中，加入 $2.7\\ \\mathbf{g}$ 全氟辛酸钠进行阴离子置换。置换 $12\\mathbf{h}$ 后，用超纯水洗涤至少3次，放入 ${\\bf80}^{\\circ}{\\bf C}$ 真空烘箱烘干。将干燥后的样品溶解于DMSO中，再次使用超纯水沉淀，过滤、洗涤三次，最后置于 $80^{\\circ}\\mathrm{C}$ 的真空烘箱中干燥，得到不同取代度纤维素1-丁基咪唑全氟辛酸盐（Cellulose-BimPFO).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 95,
+        "chunk": "# 4.2.3功能涂层膜制备  \n\n膜的制备采用溶剂挥发法，具体如下：将Cellulose-BimPFO溶解于DMF中，得到 $5-10~\\mathrm{wt}\\%$ 的溶液，然后将其倒入聚四氟乙烯模具中，放置在 ${80}^{\\circ}{\\bf C}$ 热台上4h，用水辅助将膜揭下。随后放置到 ${\\bf80}^{\\circ}{\\bf C}$ 真空烘箱中 $24\\mathrm{h}$ ，烘干以备测试。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 96,
+        "chunk": "# 4.2.4结构与性能表征  \n\n（1）核磁共振 ${}^{1}\\mathrm{H}.$ -NMR:  \n\n$^1\\mathrm{H}$ -NMR光谱均采用BrukerAV400核磁共振波谱仪进行测定。以氙代 DMSO为溶剂溶解样品，测试前滴加1-2滴氙代三氟乙酸将活泼氢移至低场。  \n\n（2）傅里叶变换红外光谱（FTIR)：  \n\n红外光谱采用 ThermoNicolet6700 傅里叶变换红外光谱仪测定，波数范围$650{\\cdot}4000\\ \\mathrm{cm^{-1}}$ ，分辨率是 $4\\ c m^{-1}$ ，扫描次数32次。  \n\n（3）X射线光电子能谱（XPS）：  \n\n样品光电子能谱测试均在X射线光电子能谱仪ESCALab250Xi（ThermoFisher，USA）上进行测试。  \n\n（4）紫外可见光谱分析：  \n\nUV-Vis 光谱采用Perkin-ElmerLambda35光谱仪测定，扫描范围 400-800nm。扫描速度为高速。  \n\n（5）扫描电镜分析：  \n\n样品形态采用JEOLJSM-6700F场发射扫描电子显微镜观察，观察前对样品表面进行喷金。  \n\n（6）光学照片：  \n\n光学图片用数码相机（SONY $\\mathbf{\\alpha}\\propto7$ ，Japan）拍摄所得。  \n\n（7）力学性能测试：  \n\n拉伸测试在万能试验机(Instron3365,INSTRON,USA)上进行，带有 5kn 的测压元件，十字头速度为 $2\\mathrm{mm}/\\mathrm{min}$ 。将试件切成 $10\\mathrm{mm}$ 宽、 $50\\mathrm{mm}$ 长的矩形条带",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 97,
+        "chunk": "# （8）接触角测试  \n\n静态接触角由液滴尺寸分析仪（DSA-100;Kru\"ss,Germany）测试得到。  \n\n（9）热失重分析（TGA)：  \n\n在 Perkin-Elmer Pyris1上，在氮气气氛下，以 $5^{\\circ}\\mathrm{C}~/~\\mathrm{min}$ 的恒定加热速率在40至 $120^{\\circ}\\mathbf{C}$ 的温度下进行分析。  \n\n（10）硬度测试：  \n\n邵氏A硬度按照GBT531.1-2008国家标准测试得到。  \n\n（11）冰成核温度 $(\\mathrm{T_{H}})$ 和冰成核延长时间 $(\\uptau)$ ！  \n\n冰成核温度 $(\\mathrm{T_{H}})$ 和冰成核延长时间（ $I_{\\mathrm{D}}$ ）通过光学显微镜和高速相机  \n\n（Phantomv7.3）测量得到。高速相机的分辨率为0.1毫秒（104帧/秒)。冷却过程由低温台（LinkamTHMS600）调节，冷却速度为 $5\\mathrm{^{\\circ}C/m i n}$ 。 $T_{\\mathsf{H}}$ 和 $\\tt t_{D}$ 的数据均由100及以上个水滴测试结果统计平均值得到。  \n\n（12）冰粘附力测试：  \n\n冰粘附强度是在结合XYMotionStage和力传感器的冷台上测试得到。每次冰粘附强度数据均取九次独立测量数据统计平均数。将氮气吹入封闭的样品池中，以最大程度地减少霜的影响。测试是在不同温度下水完全冻结进行的。使用的为方柱形水容器。  \n\n（13）抗菌性测试：采用振荡烧瓶试验方法，具体如下：  \n\n1）称取抗菌物样品 $\\mathbf{0.75g}$ 。  \n\n2）将 $\\mathbf{0.75\\g}$ 样品放入 $250~\\mathrm{ml}$ 的三角烧瓶中,分别加入 $70~\\mathrm{ml}$ PBS和 $5~\\mathrm{ml}$ 菌悬液，使菌悬液在PBS中的浓度为 $1{\\times}10^{4}\\mathrm{cfu/ml}{\\sim}5{\\times}10^{4}\\mathrm{cfu/ml}.$ .  \n\n3）将三角烧瓶固定于振荡摇床上，在作用温度为 $20^{\\circ}\\mathrm{C}\\sim25^{\\circ}\\mathrm{C}$ 的条件下，以$300~\\mathrm{r/min}$ 振摇 $2\\operatorname*{min}$ 。吸取 $1.0\\mathrm{ml}$ 用PBS作适当稀释，作为试验组震荡前样液。  \n\n4）将 $\\mathbf{0.75\\g}$ 样品放入上述含有 $70~\\mathrm{{mpBs}}$ 和 ${\\mathfrak{s}}_{\\mathbf{m}} $ 菌悬液的三角烧瓶中，然后将三角烧瓶固定于振荡摇床上，在作用温度为 $20^{\\circ}\\mathrm{C}{\\sim}25^{\\circ}\\mathrm{C}$ 的条件下，以300$\\mathbf{r}/\\mathrm{min}$ 振摇取 $0.5{\\mathrm{ml}}$ 振摇 $18\\mathrm{h}$ 。吸取 $1.0\\mathbf{m}\\mathbf{l}$ 样液，或用PBS作适当稀释后作为试验组振荡后样液。  \n\n5）分别吸取振荡前和振荡后样液各 $1.0\\ \\mathrm{ml}$ ，以琼脂倾注法接种平血，每个样液接种两个平Ⅲ，倾注营养琼脂培养基，于 $36^{\\circ}\\mathrm{C}$ 培养进行活菌计数。  \n\n6）试验同时设阴性对照和空白对照组。阴性对照样组以不含抗菌剂的石英砂代替抗菌样品外，其它操作程序均与试验组相同。空白对照组分别取 $5~\\mathrm{{ml}}$ 菌悬液和 $70\\mathrm{ml}\\mathrm{PBS}$ 加入 $250\\mathrm{ml}$ 三角烧瓶中,混匀,分别于振荡前和振荡后1h，各取 $1.0\\mathrm{ml}$ 菌悬液与PBS的混合液做适当稀释。按（5）进行活菌培养计数。  \n\n7）试验重复3次按下式计算抑菌率：  \n\n样本振荡前平均菌落数-样本振荡后平均菌落数 $\\times100\\%$ 抑菌率 $\\mathbf{\\tau}=\\mathbf{\\tau}$ 样本振荡前平均菌落数  \n\n（14）涂层抗微藻附着性能：  \n\n采用BG11培养基，采用文献报道的控制和培养方法在1L的鼓泡式玻璃柱状光生物反应器中进行培养。培养过程中，温度保持在 $25{\\pm}2\\ {}^{\\circ}{\\mathrm{C}},{\\mathrm{pH}}$ 值为 $7.8{\\pm}0.3\\$ 光源强度控制在 $200\\upmu\\mathrm{mol}/(\\mathrm{m}^{2}{\\cdot}\\mathrm{s})$ ，每天测量反应器内小球藻生长情况。将薄膜材料 $1\\mathrm{cm}\\times2\\mathrm{cm}$ 固定在玻璃片上，垂直浸泡在平板光生物反应器中。七天后取出，用PBS缓冲液漂洗薄膜材料以洗脱表面未被附着物质，显微镜拍照观察不同时间薄膜表面变化，利用UV-Vis分光光度计测定薄膜透光率。  \n\n（15）抗蛋白粘附性能：  \n\n抗蛋白粘附性能采用MicroBCA蛋白质分析试剂盒来测定薄膜浸泡与 $5\\mathrm{wt\\%}$ BSA溶液中 $2\\mathrm{h}$ 后其表面蛋白质吸附量得到。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 98,
+        "chunk": "# 4.3结果与讨论  \n\n![](images/2c74c4b364a14d7ffe1030dfb421b0a68a3d171589d298f4640fbc3c5011ba7d.jpg)  \n图4.1阳离子型纤维素衍生物材料在防雾抗冰领域及应用场景应用示意图。  \n\nFigure 4.1 Schematic diagram of cationic cellulose derivative materials in anti-fog and anti-ice fields and application scenarios.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 99,
+        "chunk": "# 4.3.1样品合成及表征  \n\n纤维素是一种可再生、可降解的生物高分子。纤维素含有丰富羟基，具有良好的力学性能，因此是功能材料的良好平台。近年来，用离子液体作为溶剂，进行纤维素改性被广泛研究。因此，我们利用纤维素结构可设计性，通过均相可控酯化过程合成了一种新型纤维素酯-纤维素2-氯丙酸酯（Cellulose-Cl)。核磁图中可以看出， $1.62~\\mathrm{ppm}$ 的峰归属于2-氯丙酰氯中甲基氢， $2.70{-}5.60~\\mathrm{ppm}$ 属于纤维素骨架峰及2-氯丙酰氯的次甲基峰（Figure4.2c）。Cellulose-Cl傅里叶变换红外光谱图（FTIR）中， $1750\\mathrm{cm}^{-1}$ 对应于纤维素2-氯丙酸酯中 $\\scriptstyle\\mathbf{C}=\\mathbf{O}$ 键（Figure 4.2d)。同时 Cellulose-Cl的光电子能谱中出现了Cl的峰（Figure $4.2\\tt{e}$ )。通过控制不同投料比和反应时间可得到不同取代度的纤维素 2-氯丙酸酯。随后将其和1-丁基咪唑通过亲核取代反应，得到不同取代度阳离子纤维素衍生物 Cellulose-BimCl。从核磁图中可以看出，新的0.92，1.56,2.12，和 $4.24~\\mathrm{ppm}$ 归属于1-丁基咪唑中的丁基的氢，另外两个新峰7.85和 $9.34\\mathrm{ppm}$ 归属于1-丁基咪唑中咪唑上的氢（Figure4.2c)。在傅里叶变换红外光谱图，在1560,1453和 $1165\\mathsf{c m}^{-1}$ 处的新峰归属于咪唑基团(Figure4.2d),光电子能谱图中也出现新的N元素峰(Figure4.2e)。最后通过离子交换得到不同取代度Cellulose-BimPFO。从傅里叶变换红外光谱图，新的1143，1171，1198和 $1680\\mathsf{c m}^{-1}$ 的峰为[PFO]阴离子特征峰（Figure4.2d)。Cellulose-BimPFO的光电子能谱中，出现新的F元素峰，也证明了Cellulose-BimPFO是成功合成的。聚合物中含有亲水性羟基及咪唑阳离子，可以吸收水汽，但是[PFO]阴离子为疏水性离子，因此我们得到了一种水可润湿的疏水材料。涂层中，亲水基团的存在，可以有效地吸收水分，因此，可以实现低湿度下防雾，而存在的疏水性阴离子有望使材料在高湿度下同样具有防雾的效果。同时，涂层中存在不同比例的亲疏水基团，因此也可以通过调节界面水，来降低冰成核温度及冰粘附力（Figure 4.2）。  \n\n![](images/cbe12cda37fe9341be76477a73ff1f81a488116a06f0fb06ae5a6d07c46b0ffb.jpg)  \n图4.2Cellulose-BimPFO合成路线图、防雾抗冰示意图及样品表征（a）Cellulose-BimPFO合成示意图（b）高低湿度下防雾机理及防冰示意图（c）Cellulose-Cl、Cellulose-BimCl、Cellulose-BimPFO 核磁氢谱图（d）Cellulose -Cl、Cellulose-BimCl、Cellulose-BimPFO傅里叶变换红外光谱图（e）Cellulose-Cl、Cellulose-BimCl、Cellulose-BimPFO光电子能谱图。  \n\nFigure 4.2 Cellulose -BimPFO synthesis route diagram, anti-fog and anti-icing diagram and sample characterization (a) Cellulose -BimPFO synthesis diagram (b) Anti-fog mechanism and anti-icing diagram under high and low humidity (c) Cotton-Cl, Cellulose -BimCl, Cellulose -BimPFO hydrogen nuclear magnetic spectrum (d) Cellulose -Cl, Cellulose -BimCl, Cellulose -BimPFO Fourier transform infrared spectrum (e） Cellulose-Cl, Cellulose -BimCl, Cellulose -BimPFO photoelectron spectroscopy.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 100,
+        "chunk": "# 4.3.2膜及涂层基本性质表征  \n\n作为防雾涂层使用，首先考虑的是涂层透明度。我们将不同取代度的涂层分别涂覆在载玻片上，通过光学照片，可以看到涂层具有很好的透明性（Figure4.3a)。通过紫外可见光光度计测试，在可见光范围内，透明度均可以保持在 $82\\%$ 以上（Figure4.3a)。此外，涂层也可以做成膜使用，膜可以保持优异的透明度和均一性（FigureS1)，而且其力学强度可以保持在 $10\\ \\mathrm{MPa}$ 以上（Figure $4.3\\ b$ ），可以满足日常使用。涂层使用过程中，不可避免会受到摩擦，要求涂层具有一定的硬度，从图中可以看出，我们所制备的涂层具有80以上邵氏A硬度，相当于生活中常见的聚氨酯硬度（Figure $4.3\\mathrm{~c~}$ )。同时由于疏水性阴离子，涂层具有高的静态水接触角，最高可达 $120^{\\circ}$ （Figure $4.3\\mathrm{~d~}$ )。因为[PFO]阴离子中含有氟元素，也使涂层具有极低表面能，最低为 $4.7~\\mathrm{mJ}/\\mathrm{m}^{2}$ （Figure4.3e)。这也为涂层具有防污效果提供了基础。同时，光电子能谱图显示随着角度的变大，F元素含量是逐渐减小的（Figure4.3f)，F元素的存在对冰粘附力大小起到了一定的作用。  \n\n![](images/7fb9389098bcb187619cfbe500ba0a3079eea2fcb35c7a82ce6f52e4907f0557.jpg)  \n\n图4.3涂层的性质（a）玻璃及不同取代度样品透光率（b）不同取代度膜的应力 应变曲线（c）不同取代度样品邵氏A硬度（d）纤维素及不同取代度涂层静态 水接触角（e）纤维素及不同取代度涂层表面能（f）不同角度F元素XPS曲线。 Figure 4.3 Coating properties (a): Glass and samples with different degrees of substitution light transmittance (b): Stress-strain curves of films with different degrees of substitution (c): samples with different degrees of substitution Shore A hardness (d): cellulose and Static water contact angle of coatings with different degrees of substitution (e): cellulose and surface energy of coatings with different degrees of substitution (f): XPS curves of F elements at different angles.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 101,
+        "chunk": "# 4.3.3防雾性能表征  \n\n（超）浸润材料已被广泛地应用到防雾领域中，但是，现在仍然存在制备困难或防雾效果不理想的情况。我们通过设计材料中亲疏水链段变化，得到了一种高低湿度下均适用的防雾涂层。首先观察了不同取代度样品防雾效果（Figure4.4a),在低湿度情况下，玻璃和取代度 ${\\bf D}{\\bf S}{=}2.9$ 的样品均会起雾（Figure4.4b，Figure4.5b)。显微镜下可以看到液滴明显地存在（Figure4.4a)。而在高湿度下，玻璃上会明显出现水珠（Figure4.4d)。而取代度 $\\scriptstyle\\mathbf{DS}=0.9$ 、2.3、2.9的样品在显微镜和肉眼下均没有看到液滴存在（Figure4.4a和 $4.5(a)$ 。因此，优选 $\\scriptstyle\\mathbf{DS}=2.3$ 的样品进行进一步考察。  \n\n没有涂层的玻璃，放置在热水汽上时，会立刻出现起雾现象（Figure4.4b)。在显微镜下可以明显看到水液滴存在（Figure4.4a 左)，随着水汽越来越多，显微镜下可以明显看到水珠的黑边（Figure 4.4a 右)。而在低湿度下，涂有涂层的玻璃(红色框内)未出现起雾现象，其透明度仍然可达到 $82\\%$ 以上。没有涂层的部分明显出现水雾，其透明度也下降到 $40\\%$ 以下（Figure4.4c）。在高湿度下，涂有涂层的玻璃（红色框内）仍然未出现起雾现象。而没有涂层的区域部分出现明显的水珠（Figure4.4d)。为证明低湿度下涂层防雾吸附了水分，分别将取代度Cellulose-BimPFO ${\\bf D}{\\bf S}{=}2.3$ 和 $\\scriptstyle\\mathbf{DS}=2.9$ 的涂层放置到水里 $2{\\ h}$ ，然后擦干涂层表面水，进行热重分析。Cellulose-BimPFO ${\\tt D S}{=}2.3$ 的涂层吸附了约 $7\\%$ 重量的水，而 Cellulose-BimPFO ${\\tt D S}{=}2.9$ 的样品几乎没吸水（Figure4.4f)。这些现象证明了吸附水汽能力在低湿度下防雾是十分关键的。  \n\n![](images/105d5e33fea100d0b4617defacd42dc30ad2fdeebcd9736bd998b8e5054fcaee.jpg)  \n\n图4.4防雾性能（a）玻璃及涂有不同取代度涂层的玻璃在低湿度和高湿度下显微镜照片（b）玻璃在热蒸气下光学照片（c）涂有Cellulose-BimPFO $\\mathrm{DS}{=}2.3$ 涂层及未有涂层的玻璃在低湿度下光学照片（d）涂有Cellulose-BimPFODS $\\scriptstyle:=2.3$ 涂层及未有涂层的玻璃在高湿度下光学照片（e）玻璃及涂有涂层玻璃起雾后透光率（f）涂层在浸泡水前后 ${\\bf N}_{2}$ 气氛下TGA曲线。  \n\nFigure 4.4 anti-fog performance (a) glass and painted with different substitution degree of coating glass microscope photos at low humidity and high humidity (b) glass optical images under the hot steam (c) coated with Cellulose-BimPFO $\\mathrm{DS}=2.3$ coating and no coating glass optical images under low humidity (d) coated with Cellulose-BimPFO $\\mathrm{DS}=2.3$ coating and no coating glass optical images in high humidity (e) and coated with the coating glass after the fog light transmittance (f) coating under $\\Nu_{2}$ atmosphere TGA curves before and after soakingin water.  \n\n![](images/a8d6b834462dd0ca28eeb31a2e24cbb0958e0c06c529cc0e5e2e9cbd8dca4f2d.jpg)  \n图4.5防雾性能（a）玻璃及涂有不同取代度涂层的玻璃在低湿度下防雾光学照片（b）Cellulose-BimPFO $\\mathrm{D}\\mathsf{S}_{}=2.9$ 低湿度下防雾光学照片（c）Cellulose-BimPFO${\\mathrm{DS}}{=}2.9$ 高湿度下防雾光学照片  \n\nFigure 4.5 Antifogging performance (a) Antifogging optical photos of glass and glass coated with different degree of substitution under low humidity (b) Antifogging optical photos of Cellulose - BimPFO $\\mathrm{D}\\mathsf{S}_{}{=}2.9$ under low humidity (c) Antifogging optical photos of Cellulose - BimPFO $\\mathrm{DS}{=}2.9$ under high humidity",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 102,
+        "chunk": "# 4.3.4抗冰性能表征  \n\n已有研究者研究了聚电解质中不同阴离子离子特异性对冰成核温度的影响，以及不同亲疏水链段对界面水的作用影响冰粘附力大小。对比不同阴离子后，发现[PFO]阴离子效果最佳。因此，我们选用[PFO]阴离子，合成不同取代度样品来调控涂层中亲疏水基团，从而达到调控界面水的目的。我们首先考察了不同取代度样品对冰成核温度的影响，发现，当Cellulose-BimPFO $\\scriptstyle\\mathrm{{DS=0.9}}$ 时，冰成核温度可以达到 ${\\bf-}27^{\\circ}{\\bf C}$ ，当Cellulose-BimPFO $\\mathrm{DS}{=}2.3$ 时，冰成核温度下降到 $.30^{\\circ}\\mathrm{C}$ （Figure 4.6a）。当Cellulose-BimPFO $\\mathrm{DS}{=}2.9$ 时，冰成核温度略有升高（Figure$4.6\\dot{\\mathsf{b}}\\dot{}$ 。而且，当温度在 $-25^{\\circ}\\mathrm{C}$ 时，Cellulose-BimPFO $\\mathrm{DS}{=}2.3$ 的涂层可使水的结冰时间达到 $7500\\mathrm{~s~}$ 。（Figure4.6c)。冰粘附力大小直接关系到防冰涂层日常使用。  \n\n随着取代度的增大，在 ${\\displaystyle-20~^{\\circ}C}$ 的冰粘附力呈现先下降后升高的趋势，Cellulose-BimPFO $\\mathrm{DS}{=}2.3$ 的样品粘附力最小，约 $26\\mathrm{{kPa}}$ 左右（Figure4.6d)。纯水核磁迟豫峰只有一个在 $2731\\mathrm{ms}$ 处，涂层中水在2697ms和 $71\\mathrm{ms}$ 处各有一个峰，核磁迟豫时间越小，也表示涂层中高分子和水作用力越强，因此我们认为该涂层中水存在着两种状态自由水和结合水，结合水的存在对于冰成核温度降低和冰粘附力减小具有一定的作用（Figure $4.6\\ensuremath{\\mathrm{h}},4.6\\ensuremath{\\mathrm{i}})$ 。而且，涂层重复30次使用后，其粘附力仍然能够保持在 $30\\mathrm{kPa}$ 左右（Figure $4.6\\mathrm{~e~}$ )。一般来说，随着温度的降低，冰粘附力会出现增大的现象，而当结冰温度下降到 $.30^{\\circ}\\mathrm{C}$ 及以下后，其粘附力反而略有下降，达到 $10\\mathrm{kPa}$ 左右（Figure $4.6\\:\\mathrm{f})$ 。因此，我们设计的涂层展现出强大的抗冰能力。  \n\n![](images/1a75c1b7df51b6af26d01ab46e02512e4d81ea59676b62884e59a05a1c0ceaed.jpg)  \n图4.6涂层抗冰性能（a）水滴在Cellulose-BimPFO $\\mathrm{DS}=2.3$ 涂层上不同温度下光学及显微镜照片（b）：硅片及不同取代度涂层水结冰温度（c）水在CelluloseBimPFO ${\\mathrm{DS}}{=}2.3$ 涂层上不同温度下延长结冰时间（d)：不同取代度涂层在 $\\cdot20^{\\circ}\\mathrm{C}$  \n\n下冰粘附力（e）Cellulose-BimPFO ${\\mathrm{DS}}{=}2.3$ 涂层在 $\\cdot20^{\\circ}\\mathrm{C}$ 下重复使用30次冰粘附力（f）Cellulose-BimPFO ${\\mathrm{DS}}{=}2.3$ 涂层在不同温度下冰粘附力。（g）Cellulose-BimPFO $\\mathrm{DS}=2.3$ 及Cellulose-BimPFO $\\mathrm{DS}=2.9$ 浸泡水后 $\\mathbf{N}_{2}$ 氛围下TGA曲线(h）Cellulose-BimPFODS $=2.3$ 样品DSC曲线（i）纯水及Cellulose-BimPFODS$=2.3$ 样品中水核磁迟豫曲线  \n\nFigure 4.6 ice coating properties (a) water droplets under different temperature on the Cellulose-BimPFO $\\mathrm{DS}=2.3$ coating and optical microscope photos (b）silicon coating and the different substitution degree water freeze temperature (c) water under different temperature on the Cellulose-BimPFO $\\mathrm{DS}=2.3$ coating ice extended time (d) : different substitution degree under - $20~^{\\circ}\\mathrm{C}$ ice coating adhesion strength (e) the Cellulose-BimPFO $\\mathrm{DS}=2.3$ coating in 30 repeated use 5 to $20~^{\\circ}\\mathrm{C}$ ice adhesion force (f) $\\mathrm{DS}=2.3$ coating adhesion of ice at different temperatures.(g) Cellulose-BimPFO ${\\mathrm{DS}}=2.3$ and DS $=2.9$ TGA curve (h) Cellulose-BimPFO DS $=2.3$ DSC curve of the sample (I) pure water and Cellulose-BimPFO DS $=2.3$ NMR delay curve of water in the sample.  \n\n![](images/2dc94a2eabf2095078c3ab798df287a2e64b28cf5ca2da1e6ecc23506ed07bd3.jpg)  \n图4.7涂层形貌表征：（a）（c）（e）分别为Cellulose-BimPFO $\\mathrm{D}\\mathsf{S}{=}0.9$ 、1.9、2.3涂层表面电镜扫描图（b）（d）（f）分别为Cellulose-BimPFO $\\mathrm{DS}{=}0.9$ 、1.9、2.3涂层断面电镜扫描图  \n\nFigure 4.7 Characterization of coating morphology :(a), (c) and (e) SEM images of  \n\nCellulose -BimPFO $\\scriptstyle\\mathbf{D}\\mathbf{S}=0.9$ ,1.9 and 2.3, respectively; (b), (d) and (f) SEM images of Cellulose -BimPFO ${\\sf D}{\\sf S}{=}0.9$ , 1.9 and 2.3, respectively",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 103,
+        "chunk": "# 4.3.5耐水性、抗生物粘附性和自清洁表征：  \n\n涂层在使用过程中不免会受到环境影响或污染。例如，当涂层在潜艇中使用过程中，海水及藻类的附着会影响涂层的使用，再如，医疗器械中的内窥镜、探头等在使用过程中会受到蛋白质等物质的粘附。因此，也要求涂层具有良好的抗生物粘附性和耐水性。首先从涂层的扫描电镜图中可以看出，膜的表面和断面均没有出现任何的缺陷，均是光滑致密的（Figure4.7)。随后，我们选取小球藻为代表考察了涂层表面抗微藻性能，将涂层和小球藻共培养七天后，显微镜下可以看到，随着取代度增大，涂层疏水性增大，其表面能减小，小球藻数量越来越少（Figure4.8a)。涂层的透明度也逐渐升高，Cellulose-BimPFO $\\mathbf{DS}=2.3$ 的涂层透明度仍能够保持在 $82\\%$ 以上（Figure4.8b)。而且，将涂层放置在水及海水中2个月后，涂层始终能够保持完整（Figure4.8f)。同时，随着F元素增加其表面能下降，Cellulose -BimPFO ${\\bf D S}{\\bf=}2.3$ 的样品对蛋白质的粘附也只有 $0.35~\\upmu\\mathrm{g}/\\mathrm{cm}^{2}$ ( Figure $4.8{\\mathrm{~c}})$ 。此外，涂层材料由于具有低的表面能所以表现出自清洁性能，涂层被沙土污染后，用水也能够轻松冲洗掉。同时，也能够避免牛奶、泥水等污染。涂层中因具有阴阳离子，因此也具有良好的杀菌性（Figure $\\pmb{4.8\\up g}$ )。Cellulose-BimPFO ${\\bf D}{\\bf S}{=}2.3$ 的涂层具有对金黄色葡萄球菌 $97.8\\ \\%$ 杀菌率（Figure $4.8\\mathrm{~d~}$ .Figure $4.8\\mathsf{e}$ )。这也为该涂层在医疗器械防雾中的使用提供了基础。  \n\n![](images/ee701ad496727948efbd53fe4c86b0f2f3f7c4897d007840574a02d4a29f5db8.jpg)  \n图4.8涂层抗污性能表征（a）小球藻在纤维素及不同取代度涂层生长七天后显微镜照片（b）小球藻在纤维素及不同取代度涂层生长七天后透光率（c）不同取代度涂层蛋白质吸附量（d）金黄色葡萄球菌在纤维素膜及不同取代度样品培养光学照片（e）不同取代度涂层金黄色葡萄球菌抑菌率（f）不同取代度涂层在水及海水中浸泡2个月后的光学照片（g）涂层自清洁性能。  \n\nFigure 4.8 Characterization of coating fouling resistance (a) chlorella growth in seven days in the cellulose and the different substitution degree coating microscope photos (b) chlorella growth in seven days in the cellulose and the different substitution degree coating coating light transmittance (c) different substitution degree of protein adsorption (d) staphylococcus aureus in cellulose membrane and training samples with different substitution degree optical images (e) with different degree of substitution rate of staphylococcus aureus antibacterial coating (f) with different degree of substitution coating in the water and seawater immersion after 2 months of optical images (g) coating self-cleaning performance.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 104,
+        "chunk": "# 4.4本章小结  \n\n通过均相衍生化方法，我们制备了一种新型阳离子纤维素衍生物Cellulose-BimPFO。通过控制取代度，改变羟基和BimPFO 基团的比例，可以调控Cellulose-BimPFO的亲疏水性得到具有水润湿性的疏水材料。亲水性羟基和阳离子基团的存在使得涂层可以吸收低水汽，形成界面水，使涂层在低湿度环境中具有防雾性能，疏水性基团使整个涂层呈现疏水性和低表面能，在高湿度环境中可以排斥宏观水滴，使涂层在高湿度环境中具有防雾性能。Cellulose-BimPFO中羟基及阴阳离子对涂层中界面水具有调节作用，使水滴在涂层表面成核温度降低，最低可达$\\mathbf{-}30^{\\circ}\\mathbf{C}$ 。涂层对冰的冰粘附力有效地降低，最低可达 $10\\mathbf{kPa}$ 。经过循环实验，证明涂层具有良好的循环使用稳定性。由于涂层的低表面能和具有疏水性结构，其展现出良好的耐水性、防生物粘附性和自清洁性。Cellulose-BimPFO具有良好的成膜性，所制备的膜具有 $10\\mathbf{MPa}$ 以上的拉伸强度，因此可作为膜材料单独使用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 105,
+        "chunk": "# 此页不缺内容",
+        "category": " Introduction"
+    },
+    {
+        "id": 106,
+        "chunk": "# 第5章具有紫外光及蓝光屏蔽性能的阳离子型纤维素衍生物的制备与性能",
+        "category": " Introduction"
+    },
+    {
+        "id": 107,
+        "chunk": "# 5.1引言  \n\n紫外线（UV）是太阳光中重要的组成部分，能量约占阳光总能量的 $6\\%$ 。在过去的几十年中，随着社会的发展二氧化碳排放量急剧增加，环境污染加剧，臭氧层被破坏，导致照射到地球上紫外线增加，过多的紫外线会导致代谢紊乱、体内 DNA受损、皮肤衰老、神经和内分泌系统紊乱。此外，UVR对有机物有害，特别是对UV敏感的产品，例如食物、药物，因此迫切需要开发防紫外线材料。  \n\n紫外屏蔽剂可以分为吸收型、反射型两种。常见吸收型屏蔽剂有：木质素、水杨酸酯类、苯酮类、苯并三唑类、取代丙烯腈类、三嗪类和受阻胺类等。常见反射型紫外屏蔽剂有：钛白粉、滑石粉、陶土粉、氧化锌、碳点、 $\\mathbf{TiO}_{2}$ 、Fe2O3、$\\mathbf{SiO}_{2}$ 等。  \n\n近年来，已经有大量关于天然聚合物抗紫外线聚合物膜的报道，例如：纤维素、壳聚糖、淀粉、藻酸盐、明胶或其组合，为了使这些膜具有抗紫外性能，通常需添加无机紫外线屏蔽剂，例如 $\\mathrm{TiO}_{2}$ 、 $\\mathrm{Fe}_{2}\\mathrm{O}_{3}$ ， $\\mathbf{SiO}_{2}$ 和ZnO等。有学者通过压力挤出脱水的方式制备了纳米纤维素 $\\scriptstyle-Z_{\\mathrm{nO}}$ 复合膜，作者通过比较片状纳米 ZnO和带状纳米 ZnO 抗紫外效果，发现片状 $z_{\\boldsymbol{\\mathrm{n0}}}$ 的紫外屏蔽效果比带状更优异[229]。此外，CNC-木质素和CNF-木质素复合膜因木质素的存在，也可以具有紫外屏蔽效果这些无机紫外屏蔽剂通常具有高的紫外线防护系数[230]。此外，镧系元素也是有效的紫外线吸收剂，例如将 $\\mathrm{Eu(TTA)}_{3}(\\mathrm{H}_{2}0)_{2}$ 接枝到纳米纤维素可制备具有优异紫外吸收的纳米纸 但是无机紫外屏蔽剂通常在膜中分布不均匀，将具有紫外吸收官能团化合物通过化学反应引入到聚合物上，可以使聚合物具有紫外屏蔽效果，也可以解决紫外屏蔽剂分布不均一的问题。  \n\n本章中通过均相衍生法，制备了一种醋酸纤维素1-丁基咪唑氯盐，将氯化铁、氯化铜、氯化钴和氯化镍等通过络合的方式引入到醋酸纤维素上制备了一种对紫外屏蔽和蓝光具有屏蔽作用的材料。其制得膜具有透明性、优异的力学性能和热稳定性，因此，可以应用到个人防护用品和紫外蓝光屏蔽保护膜领域  \n\n中。",
+        "category": " Introduction"
+    },
+    {
+        "id": 108,
+        "chunk": "# 5.2实验部分",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 109,
+        "chunk": "# 5.2.1原料和试剂  \n\n醋酸纤维素（CA)：四川普什醋酸纤维素有限公司提供，取代度 ${\\bf D}{\\bf S}{=}1.89$ ，所用纤维素原料在 ${\\bf80}^{\\circ}{\\bf C}$ 真空烘箱干燥 $24\\mathbf{h}$ 。  \n\n2-氯丙烯酰氯（2-Chloropropionylchloride）：百灵威科技有限公司提供，纯度 $97\\%$ 直接使用。  \n\nN-丁基咪唑（1-butylimidazole)：百灵威科技有限公司提供，纯度 $98\\%$ ，直接使用。  \n\n双三氟甲磺酰亚胺锂盐（LiTfN)：北京伊诺凯科技有限公司提供，纯度 $98\\%$ 直接使用。  \n\n六水氯化铁 $({\\bf F e C l_{3}}{\\cdot}6{\\bf H}_{2}{\\bf O})$ ，氯化铜（ $\\operatorname{CuCl}_{2}.$ ，氯化铝 $(A l C l_{3})$ ，氯化钙（ $(\\mathbf{CaCl}_{2})$ ，氯化钴（ $(\\mathbf{CoCl}_{2})$ )，氯化镍 $\\mathrm{(NiCl}_{2}\\mathrm{)}$ ，氯化锌（ $\\scriptstyle\\left(Z_{\\mathrm{nCl}_{2}}\\right)$ ，氯化锑 $(\\mathsf{s b C l}_{3})$ )：北京伊诺凯科技有限公司提供，纯度 $98\\%$ ，直接使用。  \n\n超纯水：Milli-Q，Millipore $0.22\\upmu\\mathrm{m}$ 。  \n\n其他化学药品均从北京国药化学试剂公司获得，试剂均为分析纯，使用前无需进一步提纯。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 110,
+        "chunk": "# 5.2.2样品合成  \n\n（1）醋酸纤维素2-氯丙酸酯（CA-CI）合成：  \n\n将CA（4.1mmol）溶解在N，N-二甲基甲酰胺（DMF）中。然后，在 $\\mathbf{0}\\circ\\mathbf{C}$ 下将 $13.7\\ \\mathrm{mmol}$ 的2-氯丙酰氯添加到CA／DMF溶液中。随后转移到 $40\\ {^\\circ}\\mathrm{C}$ 油浴中，反应 ${\\mathfrak{3}}\\mathbf{h}.$ 。将所得均匀溶液加入乙醇中以终止反应，并用乙醇将沉淀物过滤，用乙醇洗涤三次，在真空烘箱中 $\\mathbf{80}^{\\circ}\\mathbf{C}$ 干燥 $24\\mathbf{h}$ 以获得 CA-Cl。  \n\n(2）醋酸纤维素1-丁基咪唑氯盐（CA-BimCI)  \n\n将 CA-Cl（3.1mmol）溶解在DMF中。随后，添加 $14.0\\mathrm{mmol}$ 的1-丁基咪唑，并且反应在 ${\\bf80}~^{\\circ}{\\bf C}$ 油浴中进行 $24\\mathrm{~h~}$ 。将所得溶液加入乙醇中以终止反应。过滤沉淀物，用乙醇洗涤三次， ${\\bf80}^{\\circ}{\\bf C}$ 真空干燥 $24\\mathrm{h}$ ，得到CA-BimCl。  \n\n（3）醋酸纤维素1-丁基咪唑氯化金属盐（CA-BimX）  \n\n将 CA-BimCI ( $\\cdot2.5\\ \\mathrm{mmol}$ ）溶于水中。然后，滴加一定量的所需金属氯化盐的的和水溶液。将反应体系在室温搅拌 $12\\textbf{h}$ 。用超纯水透析2天，冻干。冻干后在${\\bf80}~^{\\circ}{\\bf C}$ 下真空干燥 $24\\mathrm{~h~}$ ，以获得CA-BimX。X代表金属盐氯化物阴离子，例如FeCl4 .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 111,
+        "chunk": "# 5.2.3测试和表征  \n\n（1）核磁共振 ${}^{1}\\mathbf{H}.$ -NMR:  \n\nH-NMR光谱均采用BrukerAV400核磁共振波谱仪测定。用氙代DMSO来 溶解样品，测试前加一滴氙代三氟乙酸将活泼氢移至低场。  \n\n（2）傅里叶变换红外光谱（FTIR)：  \n\n红外光谱采用Perkin-Elmer公司的ThermoNicolet6700傅里叶变换红外光谱仪测定，测试波数范围为 $650{-}4000\\ \\mathrm{cm^{-1}}$ ，分辨率为 $4\\mathrm{cm}^{-1}$ ，扫描次数16次。  \n\n（3）光电子能谱（XPS）：  \n\n样品光电子能谱测试在X射线光电子能谱仪ESCALab250Xi(ThermoFisher，USA）进行测试。  \n\n（4）光学照片：光学照片均采用数码相机（SONYα7，Japan）拍摄所得。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 112,
+        "chunk": "# （5）热失重分析：  \n\n热重分析采用Perkin-ElmerPyris-1热分析仪测定样品在氮气气氛下的热失重行为。测试样品质量为 $3\\ m g$ 左右，测试温度范围为 $100-700~^{\\circ}\\mathrm{C}$ ，采用升温速率为 $20^{\\circ}\\mathrm{C}/\\operatorname*{min}$ 0  \n\n（6）扫描电镜分析：  \n\n样品形态采用JEOL公司的JSM-6700F场发射扫描电子显微镜观察，观察前对样品表面进行喷金，增加样品导电性，加速电压为 $\\mathbf{5.0\\mathbf{k}V}$ 。  \n\n（7）力学性能测试：  \n\n拉伸测试在万能试验机(Instron3365,INSTRON，USA)上进行，带有 $5~\\mathbf{k}\\mathbf{n}$ 的测压元件，十字头速度为 $2\\mathrm{{mm}/\\mathrm{{min}}}$ 。将试件切成 $10\\mathrm{mm}$ 宽、 ${50}\\mathrm{mm}$ 长的矩形条带。  \n\n（8）紫外可见光谱分析：  \n\nUV-Vis光谱采用Perkin-ElmerLambda35光谱仪测定，扫描范围400-800nm。扫描速度为高速。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 113,
+        "chunk": "# 5.3结果与讨论",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 114,
+        "chunk": "# 5.3.1样品合成及表征  \n\n![](images/9552b8e683f2a88f6b5dcd886e98f3f101898c507e95c08fcc35171396f227ab.jpg)  \n图5.1CA-BimMClx+1合成路线  \nFigure 5.1 Synthesis route of CA-BimMClx+1  \n\n利用纤维素结构可设计性，一种新型的纤维素混合酯-纤维素醋酸纤维素2-氯丙酸酯（CA-C1）通过均匀且可控的酯化过程合成得到（图5.1)。在CA-CI的$^1\\mathrm{H}$ NMR谱图中（图 $5.2\\mathrm{~a~})$ ，在 $1.62\\ \\mathrm{ppm}$ 处的峰归因于2-氯丙酸酯甲基氢，在$1.70{-}2.20~\\mathrm{ppm}$ 处的峰为醋酸纤维素中甲基的氢，而在 $1.70\\ \\mathrm{ppm}$ 处的峰和2.70-$5.60~\\mathrm{ppm}$ 处的峰是纤维素骨架和2-氯丙酸酯的亚甲基的氢。根据纤维素骨架与2-氯丙酸酯的甲基氢积分面积比，计算出2-氯丙酸酯的DS（取代度）为0.90。然后，在CA-CI和1-丁基咪唑之间进行亲核取代反应后，获得了阳离子化纤维素衍生物CA-BimCl（图5.1）。在CA-BimCI的 $^1\\mathrm{H}$ NMR谱图中（图5.2），在0.92、1.56、2.12和 $4.24~\\mathrm{ppm}$ 处的新峰归属于1-丁基咪唑（Bim）基团中丁基的氢，7.85和 $9.34~\\mathrm{ppm}$ 处的峰为Bim基团上咪唑的氢。在CA-BimCl的FTIR光谱中（图 $5.26$ )，在1560、1470和 $1165\\mathrm{cm}^{-1}$ 处的峰与咪唑环特征峰相对应。在CA-BimCI的XPS谱图中（图 $5.3\\mathrm{~c~})$ ，有N元素的峰和C1元素的峰。由此表明了阳离子化的CA-BimCI已经被成功合成。  \n\n![](images/ca5df2f49c4abbb8d316eb7645d4815df115c91932d6c06119deaec64c9d8ad9.jpg)  \n图5.2两种纤维素酯CA-CI和CA-BimCI的结构表征（a）H-NMR谱图（b）FTIR光谱图（c）XPS谱图  \n\nFigure 5.2 Structural characterization of two cellulose esters CA-Cl and CA-BmimCl(a) ${}^{1}\\mathrm{H}$ -NMR spectra（b） FTIR spectrogram（c） XPS spectra.  \n\n![](images/965e2840168128e8f74433dbef3d34f2372b5633748468f6af7559d1346a520f.jpg)  \n图5.3CA-Bim[FeCl4]0.075[CuCl3]0.925光电子能谱图 Figure 5.3 XPS of CA-Bim[FeCl4]0.075[CuCl3]0.925",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 115,
+        "chunk": "# 5.3.2膜紫外屏蔽性能表征  \n\n目前紫外屏蔽剂通常含有木质素、水杨酸酯类、苯酮类、苯并三唑类、取代丙烯腈类、三嗪类和受阻胺类等。无机的纳米钛白粉、滑石粉、陶土粉、氧化锌、碳点、 $\\mathrm{TiO}_{2}$ 、 $\\mathrm{Fe}_{2}\\mathrm{O}_{3}$ 和 $\\mathrm{SiO}_{2}$ 等，也常作为紫外屏蔽添加剂，但是现在仍然存在着制备成本高、透明度低或紫外屏蔽效果不够理想的问题。已有文献报道金属离子可以起到紫外屏蔽效果，我们通过简单的离子络合，将金属离子络合引入到纤维素链上，首先考察一些金属离子对紫外光的屏蔽效果如图5.4所示。  \n\n![](images/53dbf1dac61e445b62ad83efa6533d7f9b0b3af9a47f05dffb16e1441a74bcff.jpg)  \n图5.4CA-BimMClx+1膜的紫外屏蔽效果  \nFigure5.4 UV shieldingeffect ofCA-Bim $\\mathrm{{MCl}_{x+1}}$ films  \n\n所使用金属离子中， $\\mathrm{Fe}^{3+}$ 对紫外屏蔽的效果最佳， $200{-}380\\mathrm{nm}$ 紫外区可以达到 $100\\%$ 吸收， $380{-}400~\\mathrm{nm}$ 的紫外区域可以达到 $98\\%$ 吸收。其在可见光范围$550\\mathrm{nm}$ 也能够具有 $70\\%$ 左右的透光率。金属CA-BimCuCl紫外屏蔽效果最差，只能吸收 $240\\mathrm{nm}$ 以下的紫外区。其他金属离子例如CA-BimZnCl、CA-BimNiCl、CA-BimCoCl、CA-BimCaCl、CA-BimAlCl和CA-BimSbCl都吸收 $350~\\mathrm{nm}$ 以下波段。考虑到CA-BimFeCl4有极好的紫外屏蔽效果，而含CA-BimCuCl膜在更宽波长范围内可以保持良好的透明性，因此我们选取这两种离子进一步地考察，我们通过调控这两种离子的比例，期望找到一种高透明度高紫外屏蔽的膜材料。  \n\n![](images/b2c7ae1cc8bdbb83e2d28958c4c5cc100da4c1e5d99ff1a4fc7dc4bea4edf4a3.jpg)  \n图5.5不同 $\\mathrm{Fe}^{3+}/\\mathrm{Cu}^{2+}$ 比例 $\\mathrm{CA}{\\mathrm{-BimMCl_{x+1}}}$ 和纯CA膜紫外屏蔽效果 Figure 5.5 UV shielding effect of different $\\mathrm{Fe}^{3+}\\mathrm{Cu}^{2+}$ ratios CA-BimM $\\mathbf{\\hat{C}}\\mathbf{l}_{\\mathbf{x}+1}$ and pure CA film  \n\n![](images/4323eb926ce5b39833d5154759ae0aa78890f42fb23750692dde683cf49b3a3f.jpg)  \n图5.6（a）护手霜掺杂CA-Bim[FeCl4]0.075[CuCl3]0.925样品前后透光率变化，（b）离子交换后CA-Bim[FeCl4]0.075[CuCl3]0.925样品透光率变化  \n\nFigure 5.6 (a) Changes in light transmittance before and after hand cream doping with CA-Bim[FeCl4]o.075[CuCl3]0.925mol ${\\mathrm{Cu}}^{2+}$ sample; (b) Changes in light transmittance of CA-Bim[FeCl4]0.075[CuCl3]o.925ssample after ion exchange  \n\n从图5.4和图5.5中可以看出，纯醋酸纤维素吸收 $250\\mathrm{nm}$ 波长以下区域，当添加 $\\mathrm{Fe}^{3+}$ 后，膜可以很好地屏蔽紫外区域。随着 $\\mathrm{Fe}^{3+}$ 含量增加， $\\mathrm{Cu}^{2+}$ 含量减少，可屏蔽波长逐渐变大，当 $\\mathrm{Fe}^{3+}/$ $\\mathrm{Cu}^{2+}$ 含量均为 $0.5~\\mathrm{mol}$ 时，膜可以屏蔽 $450~\\mathrm{nm}$ 以下波段，不仅吸收了全波段紫外区域，还屏蔽了蓝光区域，对 $450\\mathrm{nm}-500\\mathrm{nm}$ 的蓝光区域吸收率可达 $95.4\\ \\%$ 。而CA-Bim[FeCl4]o.075[CuCl3]0.925 膜可以 $100\\%$ 屏蔽 $380\\mathrm{nm}$ 以下波长区域。此时，在 $550\\mathrm{nm}$ 处仍然具有 $80\\%$ 透光率。在此摩尔比下所制备的膜不仅具有优异的紫外屏蔽效果，同时保持优良透明性，可将其应用到防护用品中。从图5.6中可以看出，护手霜在掺杂了CA-Bim[FeCl4]0.075[CuCl3]0.925样品后， $300{-}400~\\mathrm{{nm}}$ 波长的紫外区域可以 $100\\%$ 被屏蔽，因此当样品水溶性时，可作为防晒护肤品中的添加剂使用。将CA-Bim[FeCl4]0.075[CuCl3]0.925放置于含有的LiTfN水溶液中进行离子置换后，可实现水溶-疏水转变，但此时并未改变原来的紫外屏蔽效果。  \n\n![](images/dec215070d0636255f522739978022d7889ad50d397ed66f263a3e3cf92248e8.jpg)  \n图5.7具有不同金属含量C $\\mathbf{\\hat{A}}\\mathbf{-BimMCl}_{\\mathbf{x}+1}$ 膜的紫外屏蔽效果  \nFigure 5.7 UV shielding effect of CA-BimMClx+ifilms with different metal content  \n\n为了更加直观地说明紫外屏蔽的效果，我们选用紫外波长 $365~\\mathrm{{nm}}$ 来进一步考察膜紫外屏蔽效果。我们将其放置到100元人民币防伪标志处，未修饰的醋酸纤维素在UV-365nm照射下能够明显地看到“100”防伪字样，在 $365~\\mathrm{{nm}}$ 的紫外灯照射下，“100”防伪字样能够被CA-Bim[FeCl4]o.075[CuCl3]0.925 的膜遮挡住，显示出其优良的抗紫外性能。同时，我们能够清楚地看到人民币的其他地方，也展现出其良好透明性。然而，随着 $\\mathsf{F e}^{3+}$ 的含量增加，膜透明性有所减小。膜紫外屏蔽性能略有增加。  \n\n紫外线可分为三种类型：UVA射线（ $320\\mathrm{nm}{\\cdot}400\\mathrm{nm})$ 、UVB射线（ $280\\mathrm{nm}-$ $320\\mathbf{nm}$ ）和UVC射线（不到达地球表面)。其中，UVA和UVB射线通常肉眼看不到，长时间暴露在这两种光线下都会对皮肤造成巨大伤害，例如：它们能够破坏皮肤胶原蛋白、导致皮肤过早老化、产生细纹或者皱纹甚至导致癌症。因此，需要我们的防晒材料能够尽量将两种射线都屏蔽掉，而且通常通过UVA和UVB的透光率（通过文献报道公式计算）来体现其抗紫外效果。  \n\n表5.1CA-BimMClx+1膜材料UVA、UVB和可见光及蓝光波段透过率  \n\nTable 5.1 The transmittance of ultraviolet A, ultraviolet B, and visible and blue light of the CA-BimMClx+1films   \n\n\n<html><body><table><tr><td>Sample</td><td>550nm (%)</td><td>UVA (%)</td><td>UVB (%)</td><td>400-450nm (%)</td></tr><tr><td>CA</td><td>90</td><td>89</td><td>85</td><td>100</td></tr><tr><td>CA-BimMCl+1</td><td></td><td></td><td></td><td></td></tr><tr><td>0.075 mol Fe3+/0.925 mol Cu²+ 0.1 mol Fe3+/0.9 mol Cu2+</td><td>79</td><td>0.01</td><td>0</td><td>30</td></tr><tr><td> 0.33 mol Fe3+/0.66 mol Cu2+</td><td>72 61</td><td>0.01</td><td>0</td><td>38</td></tr><tr><td> 0.5 mol Fe3+/0.5 mol Cu2+</td><td>60</td><td>0 0</td><td>1 0</td><td>20</td></tr><tr><td>0.5 mol Fe3+</td><td>60</td><td>0</td><td></td><td>0 18</td></tr><tr><td>1 mol Fe3+</td><td>59</td><td>0</td><td>0</td><td>20</td></tr><tr><td>1 mol Cu2+</td><td>89</td><td>60</td><td>10</td><td>60</td></tr></table></body></html>  \n\n纯醋酸纤维素几乎没有紫外吸收，当引入 $0.075\\mathrm{mol}\\mathrm{Fe}^{3+}$ 和 $0.925\\mathrm{mol}\\mathrm{Cu}^{2+}$ 时可阻挡 $99.9\\%$ 的UVA射线和 $100\\%$ 的UVB射线，同时在可见光 $550\\mathrm{nm}$ 下具有 $79\\%$ 的透光率。随着 $\\mathrm{Fe}^{3+}$ 含量的增大，膜对UVA和UVB能够基本保持 $100\\%$ 的屏蔽，但是在可见光波长 $550\\ \\mathrm{nm}$ 下透明度有一定的减小。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 116,
+        "chunk": "# 5.3.2膜力学性能及热稳定性表征  \n\n作为膜材料使用，首先膜本身不允许有缺陷，因此我们采用溶剂挥发制备膜材料后，用扫描电镜观察了其表面和断面形貌。从膜的扫描电镜图中可以看出，膜的断面和表面均是致密无缺陷，这也为膜具有良好的力学性能及紫外屏蔽性能  \n\n打下了基础。  \n\n![](images/d64f5eaffe9a0e4d112bbf668a7098b36c131b88d978bf411b8b801960b2f1da.jpg)  \n图 ${\\bf5.8}\\mathrm{CA-BimMCl_{x+l}}$ 膜的断面和表面SEM图  \n\nFigure 5.8 SEM images of cross section and surface of the CA-BimMClx+ifilm醋酸纤维素因其具有优异的力学性能，被广泛应用于香烟过滤嘴、眼镜框架、液晶显示的偏光片等。醋酸纤维素经过化学修饰后，拉伸强度始终能够保持55MPa以上，杨氏模量保持 $2.0\\mathrm{GPa}$ 以上，使其能够满足日常生活需求。  \n\n![](images/137f19af98e7b51398bd7b23580b10edb4fe98680c3f1b62838c0b39137d1a15.jpg)  \n图 ${\\bf5.9\\ C A-B i m M C l_{x+l}}$ 膜的应力-应变曲线  \nFigure 5.9 Stress-strain curves of films with CA-BimMClx+1  \n\n表5.2CA-BimMClx+1膜的力学性能(拉伸强度、杨氏模量和断裂应变)  \n\nTable 5.2 Mechanical properties (Tensile strength, Young's modulus and Strain at break) filmswith( $\\mathrm{\\DeltaT_{A-BimMCl_{x+1}}}$ films  \n\n<html><body><table><tr><td>Sample</td><td>Tensile strength (MPa)</td><td>Young'modulus (GPa)</td><td>Strain at break (%)</td></tr><tr><td>CA-BimClx+1</td><td></td><td></td><td></td></tr><tr><td>1mol Cu²+</td><td>59±3.1</td><td>2.7±1.3</td><td>3.4±1.1</td></tr><tr><td>0.1molFe3+/0.9molCu²+</td><td>61±2.0</td><td>2.1±1.1</td><td>6.0±2.1</td></tr><tr><td>0.5molFe3+</td><td>61±2.5</td><td>1.9±1.6</td><td>5.6±1.3</td></tr><tr><td>1molFe3+</td><td>59±3.0</td><td>2.5±0.9</td><td>4.1±1.5</td></tr><tr><td>0.33molFe3+/0.66molCu2+</td><td>61±2.3</td><td>2.2±1.1</td><td>7.3±1.0</td></tr><tr><td>0.5molFe3+/0.5molCu2+</td><td>56±4.0</td><td>2.0±1.5</td><td>9.6±2.0</td></tr></table></body></html>  \n\n热稳定性对于纤维素材料的开发与应用是一个重要的性能，同时如果将其应用到高温领域，良好的热稳定性必不可少。因此，我们在氮气气氛下，对所制得的膜进行热失重分析，由图5.10a所示。  \n\n![](images/889fc50e84ce669917a9fc77f479478eb34c0bcb6ded3364fdebc9c771e01410.jpg)  \n图5.10（a）CA-BimMClx+1膜的TGA和（b）DTG曲线Figure 5.10 (a)TGA and （b）DTG curves of CA-BimMClx+1films  \n\n所制备膜起始分解温度（Tonset）约为 $240^{\\circ}\\mathrm{C}$ ，与CA相似。它们具有一个热降解过程，最大分解温度（Tmax）分别为 $250{-}305^{\\circ}\\mathrm{C}$ 之间（图 $5.10\\mathrm{~b~}$ )。此温度区域的热降解过程源自CA聚合物链降解。因此，这种高透明性、高紫外屏蔽、力学性能优异及高热稳定性的膜在实际使用中具有巨大的潜力。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 117,
+        "chunk": "# 5.4本章小结  \n\n在本章中，通过将醋酸纤维素均相衍生化，引入阴阳离子结构，得到一种新型纤维素酯。采用络合方式在醋酸纤维素上引入不同金属氯化物阴离子，可得到具有抗紫外及蓝光屏蔽的膜。首先将多种金属氯化物通过络合方式引入到纤维素上，考察了含有 $\\mathrm{Fe}^{3+}$ 、 ${\\mathrm{Cu}}^{2+}$ 、 $Z\\mathrm{n}^{2+}$ ： $\\mathrm{Al}^{3+}$ ， ${\\mathrm{Co}}^{2+}$ ， $\\mathrm{Ni}^{2+}$ 等离子的膜在 $200{-}800\\mathrm{nm}$ 波长范围内的透过率，发现CA-BimFeCl4可以起到优异紫外屏蔽性能，CA-BimCuCl可吸收部分蓝光区域，因此，调控 $\\mathrm{Fe}^{3+}/\\mathrm{Cu}^{2+}$ 在膜中的比例，可以得到$200{-}450\\mathrm{nm}$ 波长全吸收的纤维素膜。此外，所制备的纤维素膜在 $550\\mathrm{nm}$ 的可见光波长下，能够保持 $75\\%$ 以上透明度。离子交换可得到不同溶解性样品，其中水溶性样品可作为防晒添加剂，能够有效地增加紫外屏蔽，疏水性型材料可作为紫外屏蔽膜使用。膜的拉伸强度均可保持在 $55\\mathrm{MPa}$ 以上，热分解温度在 $230^{\\circ}\\mathrm{C}$ 以上，使其具有足够的力学轻度和热稳定性，足以满足实际使用需求。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 118,
+        "chunk": "# 第6章结论  \n\n纤维素一直被当做为能源、化学及化工的重要原料，又因其在自然界中分布广泛、储量巨大、可再生，因此进行了广泛的研究。由于纤维素自身存在大量的分子内及分子间氢键和高结晶度，使得天然纤维素不熔融，且难以被常见试剂所溶解，导致其加工和使用困难，限制了其应用。近年来，随着纤维素溶解体系的研究，多种溶解纤维素的溶剂出现，使纤维素的加工及化学改性变得可行。例如氢氧化钠/尿素和离子液体都是能够实现快速溶解纤维素的体系。其中，离子液体作为一种绿色溶剂，其本身不挥发、不易燃、稳定性高、易回收，为纤维素的绿色加工和功能衍生化提供了广阔的前景。  \n\n为了实现纤维素的高值化利用、拓宽纤维素材料的应用领域，本文以离子液体为溶剂，通过纤维素上丰富的羟基进行化学改性，设计合成了阳离子型纤维素衍生物，并通过简单的离子交换得到多种功能性纤维素衍生物。目前取得主要研究结论如下：  \n\n1.阳离子型纤维素衍生物的合成与溶解性：通过均相衍生化制备了多种阳离子型纤维素衍生物，首先将2-氯丙酰氯通过化学键键合到纤维素链上，得到不同取代度的含氯纤维素衍生物；然后与三丁基麟、吡啶、1-甲基咪唑和1-乙烯基咪唑进行亲核取代反应；最后再进行阴离子交换，得到了不同取代度、不同阳离子和不同阴离子的阳离子型纤维素衍生物。阴离子为CI时，三丁基麟、吡啶和1-甲基咪唑取代度达到一定值后可实现水溶，当将CI置换为TfzN、 $\\mathbf{BF}_{4}^{*}$ 和 $\\mathbf{PF_{6}^{*}}$ 后可实现水溶-水不溶转变，或者醇溶-醇不溶转变。更进一步地，我们可将含有双键的阳离子引入到纤维素中，制备得到纤维素乙烯基咪唑氯盐Cell-VimCl。Cell-VimCl可分散蒙脱土，当蒙脱土的含量不低于 $30\\mathrm{wt\\%}$ 时，得到水溶性阻燃涂料。蒙脱土的引入显著地降低了纤维素材料的最大热释放速率、热释放总量和热释放能力，使纤维素涂层具有优异的阻燃性能。  \n\n2.利于 $\\mathbf{CO}_{2}$ 透过的阳离子型纤维素衍生物的制备与气体分离性能：我们将1-丁基咪唑引入到醋酸纤维素上，随后将氯离子（CI）阴离子交换为双三氟甲磺酰亚胺（TfN）阴离子，得到含有丁基咪唑阳离子和TfN-阴离子的阳离子型醋酸纤维素CA-BimTfN。阳离子化醋酸纤维素可有效地增加 $\\mathbf{CO_{2}}$ 透过，同时利用CA-BimTfN中离子化基团增加了其和自由离子液体的相容性，因此我们制备了一系列复合不同种类离子液体的膜材料，用于 $\\mathbf{CO}_{2}$ 气体分离。考察了不同种类离子液体后，发现 $\\mathbf{C_{l0}m i m T f_{2}N}$ 离子液体的引入对CA-BimTfN/ILs复合膜的气体透过性能影响最大，显著地增大 $\\mathbf{CO_{2}}$ 气体的透过，而且能够保持 $\\mathbf{CO}_{2}/\\mathbf{N}_{2}$ 的选择性不低于24。当复合膜中C1omimTfN的含量增大到 $140\\%$ 时， $\\mathbf{CO}_{2}$ 渗透系数可达91barrer，比纯醋酸纤维素提高了 $3800\\%$ 。同时，CA-BimTfN/C1omimTfN复合膜的拉伸强度保持在 $10\\mathrm{MPa}$ 以上，分解温度高于 $250^{\\circ}\\mathbf{C}$ ，保证了实际使用中对分离膜材料的力学性能和热稳定性的要求。  \n\n3.具有防雾、抗冰和自清洁性能的阳离子型纤维素衍生物的制备与性能：我们将1-丁基咪唑引入纤维素中，然后将CI交换为较强疏水能力的全氟辛酸(PFO)阴离子，制得阳离子纤维素衍生物Cellulose-BimPFO。通过控制取代度，改变羟基和BimPFO基团的比例，从而达到调控界面亲疏水性，得到可以形成界面水的疏水涂层材料，其表现出优异的防雾、抗冰和自清洁性能。由于离子化结构和保留部分纤维素羟基，该涂层在低湿度环境下可以吸附水汽形成均匀水膜，从而实现低湿度下防雾；当湿度增加时，由于PFO阴离子高的疏水性，该涂层材料表现出疏水性，促进水滴滚落，从而实现高湿度下防雾。由于很容易形成界面水，Cellulose-BimPFO涂层能够使水结冰温度降低至 $\\mathtt{-30^{\\circ}C}$ ， $\\boldsymbol{-30}^{\\circ}\\boldsymbol{\\mathrm{C}}$ 下冰粘附力降低至 $10\\mathrm{\\textmu{}P a}$ ， $-25^{\\circ}\\mathbf{C}$ 下的结冰时间超过 $2\\hbar$ 。另外，涂层其对金黄色葡萄球菌具有$97\\%$ 以上的杀菌率。由于涂层高疏水性和低表面能，使其具有良好的耐水性、自清洁性和抗生物粘附性能。可将其应用到日常生活（比如，眼镜、汽车玻璃、飞机玻璃等）中或者内窥镜等需要防雾场景中，同时涂层强大的抗冰能力，也使其可应用到需要防结冰场景中，比如空调外机、风电叶片等。  \n\n4.具有紫外光和蓝光屏蔽性能的阳离子型纤维素衍生物的制备与性能：我们将1-丁基咪唑引入到醋酸纤维素上，随后与金属氯化盐 $(\\mathbf{MCl_{x}})$ ）反应，得到含有1-丁基咪唑阳离子（ $:\\mathbf{Bim^{+}})$ 和金属氯化盐 $(\\mathbf{MCl_{x+1}}^{-})$ 阴离子的阳离子型醋酸纤维素 $\\mathbf{CA-BimMCl{x}+1}$ 。通过比较不同金属离子紫外吸收性能，发现 $\\mathbf{Fe}^{3+}$ 的引入可以使膜具有很好地吸收紫外线性能， ${\\bf C u^{2+}}$ 引入可以使膜吸收部分蓝光区域，因此，$\\mathbf{Fe^{3+}}$ 、 ${\\mathsf{C u}}^{2+}$ 等金属离子的引入，使得所得阳离子型醋酸纤维素 $\\mathbf{CA-BimMCl_{x+l}}$ 具有抗紫外光和抗蓝光性能。将不同比例的 $\\mathsf{F e}^{3+}$ $\\mathsf{C u}^{2+}$ 同时络合时，可以得到对200-$450\\mathrm{nm}$ 波长光全吸收的膜材料。从而，通过调控 $\\mathsf{F e}^{3+}$ ， ${\\mathrm{Cu}}^{2+}$ 两种离子含量得到具有抗紫外光及蓝光的薄膜。同时，所制备的膜具有良好的透明度，最高在 $\\mathfrak{s s o}\\mathfrak{n}\\mathbf{m}$ 处具有 $75\\%$ 以上的透光率。膜的力学性能也能够保持在 ${\\mathfrak{s s m p}}_{\\mathbf{a}}$ 以上以及 $230^{\\circ}\\mathrm{C}$ 以上的热分解温度，满足作为保护膜的实际使用需求。  \n\n参考文献 [1] Klemm D, Heublein B, Fink H P, et al. 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Universal antifogging and antimicrobial thin coating based on dopamine-containing glycopolymers [J].ACS Applied Material& Interfaces, 2020, 12(24): 27632- 27639.  \n\n[211]Bai S, Li X H, Zhang R C, et al. Enhancing antifogging/frost-resisting performances of amphiphilic coatings via cationic, zwitterionic or anionic polyelectrolytes [J]. Chemical Engineering Journal, 2019, 357(6):667-677.  \n\n[212]Chen W, Fadeev A Y, Hsieh M C, et al. Ultrahydrophobic and ultralyophobic surfaces: Some comments and examples [J]. Langmuir, 1999, 15(10): 3395-3399.  \n\n[213]Mouterde T, Lehoucq G, Xavier S, et al. Antifogging abilities of model nanotextures [J] Nature Materials, 2017, 16(6): $658–+$  \n\n[214]Raut H K, Dinachali S S, Loke Y C, et al. Multiscale ommatidial arrays with broadband and omnidirectional antireflection and antifogging properties by  sacrificial layer mediated nanoimprinting [J].ACS Nano, 2015, 9(2): 1305-1314.  \n\n[215]Gao X F,Yan X, Yao X, et al.The dry-style antifogging properties of mosquito compound eyes and artificial analogues prepared by soft lithography [J]. Advanced Materials, 2007, 19(17): 2213- +.  \n\n[216]Yoon J, Ryu M, Kim H, et al. Wet-style superhydrophobic antifogging coatings for optical sensors [J]. Advanced Materials, 2020, 32(34).  \n\n[217]Golovin K, Tuteja A. A predictive framework for the design and fabrication of icephobic polymers [J]. Science Advances, 2017, 3(9): 9.  \n\n[218]He Z W, Xiao S B, Gao H J, et al. Multiscale crack initiator promoted super-low ice adhesion surfaces [J]. Soft Matter, 2017, 13(37): 6562-6528.  \n\n[219]Irajizad P, Al-Bayati A, Eslami B, et al. Stress-localized durable icephobic surfaces [J] Materials Horizons, 2019, 6(4): 758-766.  \n\n[220]Wang Y L, Yao X, Wu S W, et al. Bioinspired solid organogel materials with a regenerable sacrificial alkane surface layer [J]. Advanced Materials, 2017, 29(26): 7.  \n\n[221]Golovin K, Kobaku S P R, Lee D H, et al. Designing durable icephobic surfaces [J]. Science Advances, 2016, 2(3): 12.  \n\n[222]Dou R M, Chen J, Zhang Y F, et al. Anti-icing coating with an aqueous lubricating layer [J] ACS Applied Materials & Interfaces, 2014, 6(10): 6998-7003.  \n\n[223]Koshio K, Waku T, Hagiwara Y. Ice-phobic glass-substrate surfaces coated with polypeptides inspired by antifreeze protein [J]. International Journal of Refrigeration-Revue International Du Froid, 2020, 114(2):201-209.  \n\n[224]Liu Z Q, He Z Y, Lv J Y, et al. Ion-specific ice propagation behavior on polyelectrolyte brush surfaces [J]. RSC Advances, 2017, 7(2): 840-844.  \n\n[225]Wang F, Xiao S B, Zhuo Y Z, et al. Liquid layer generators for excellent icephobicity at extremely low temperatures [J]. Mater Horizons, 2019, 6(10): 2063-72.  \n\n[226]Guo Q, He Z Y, Jin Y K, et al. Tuning ice nucleation and propagation with counterions on multilayer hydrogels [J]. Langmuir, 2018, 34(40): 11986-11991.  \n\n[227]Chen J, Dou R M, Cui D P, et al. Robust prototypical anti-icing coatings with a self-lubricating liquid water layer between ice and substrate [J]. ACS Applied Materials &Interfaces, 2013, 5(10): 4026-4030.  \n\n[228]He ZY, Wu C Y, Hua M T, et al. Bioinspired multifunctional anti-icing hydrogel [J]. Matter, 2020, 2(3): 723-734.  \n\n[229]Liu H Q, Hu D C, Chen X J, et al. Surface engineering of nanoparticles for highly efficient UV-shielding composites [J]. Polymer Advanced Technology, 2020,32(1):1-11. 116  \n\n[230]Bai Y, ZHAO Y, Li Y, et al. UV-shielding alginate films croslinked with $\\mathsf{F e}^{3+}$ containing EDTA[J]. Carbohydrate Polymers 2020, 239.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 119,
+        "chunk": "# 此页不缺内容",
+        "category": " Introduction"
+    },
+    {
+        "id": 120,
+        "chunk": "# 此页不缺内容",
+        "category": " Introduction"
+    },
+    {
+        "id": 121,
+        "chunk": "# 此页不缺内容",
+        "category": " Introduction"
+    },
+    {
+        "id": 122,
+        "chunk": "# 致谢  \n\n行文至此，意味着在化学所的五年学习生活即将结束了，窗外日光弹指过，席间花影坐前移，2015年9月我在化学所做本科毕业设计的场景依旧历历在目，那时对化学所充满了好奇和憧憬。转眼间，六年过去了，也到了和化学所道别的时候。在化学所六年的生活使我收获了很多，认识了很多科研前辈，结识了很多优秀的朋友。科研并非一帆风顺，在困难的时候我有幸得到各位老师和同学的帮助。在此，我要向所有曾经帮助过我的老师和同学们致以最诚挚的谢意！  \n\n首先感谢的是我的导师张军研究员。感谢张老师给予我加入化学所工程塑料实验室的机会，张老师为我们提供了良好的科研条件和轻松的科研氛围，同时为我在科研的道路上指明了方向。我从科研小白到获得博士学位，离不开张老师的鼓励和辛勤指导。张老师性格开朗、为人和善幽默为我们在为人处事方面做出了榜样。同时，张老师在科研方面思维活跃、严谨治学为我们在科研方面做出了榜样。  \n\n非常感谢张金明副研究员，张老师文献积累丰厚，科研想法多，无论是在实验设计还是论文撰写都给予了悉心的帮助。在实验出现困难时，也能够及时帮助我们解决问题。在此，再次向张金明老师表达诚挚的谢意。  \n\n感谢化学所绿色印刷实验室贺志远老师在防结冰领域对我的指导和帮助。贺老师思维活跃、治学严谨高效。同时贺老师在数据分析及测试方面给予了我很大的帮助，再次向贺志远老师表达谢意。  \n\n感谢课题组何嘉松研究员，何老师知识渊博、兢业业的工作作风让我们感受到了老一辈科学家科研精神。感谢武进副研究员、余坚副研究员、宋广杰助理研究员、田卫国副研究员在科研和生活上的帮助和指导。  \n\n感谢化学所工程塑料实验室的陈士娟老师、李革老师等以及中国科学院化学研究所核磁测试中心向俊锋、武宁宁、侯可悦等老师，在核磁测试方面给予的特别帮助。  \n\n感谢已毕业的丁美春、袁斌、丰哗、万纪强、陈张彦、贾若男、杨田田、李锦阳、靳坤峰等师姐或师兄在科研和生活上提供的帮助。感谢米勤勇、张晓程、尹春春、刘宗喜、卢洪超、许如梦、张鑫、周彦、温超俊、季欣、夏征豪、尤晶璇、高学信、刁怀玲、徐展、王逸蓉等同学的帮助。  \n\n最后，特别感谢我的家人，感谢他们一直以来对我的支持和关心。特别感谢吴佳欣同学对我的理解和支持。  \n\n再次向所有给予我帮助和关心的人致以最真挚的谢意！  \n\n程耀辉2021年5月",
+        "category": " Conclusions"
+    },
+    {
+        "id": 123,
+        "chunk": "# 作者简历及攻读学位期间发表的学术论文与研究成果",
+        "category": " References"
+    },
+    {
+        "id": 124,
+        "chunk": "# 作者简历：  \n\n2012年9月-2016年6月，在湘潭大学化学学院获得工学学士学位  \n2016年9月-至今，在中国科学院化学研究所攻读工学博士学位  \n\n获奖情况：  \n\n中国科学院化学研究所\"青年科学奖特别优秀奖\"中国科学院化学研究所\"金建青年科学奖\"",
+        "category": " References"
+    },
+    {
+        "id": 125,
+        "chunk": "# 已发表的学术论文：  \n\n1. Cheng YH, Zhang X, Zhang J, et al. Immobilization of Ionic Liquids with a New Cellulose Ester Containing Imidazolium Cation for High-Performance $\\mathbf{CO_{2}}$ Separation Membranes [J]. Macromolecular Rapid Communications, 2020, 42.  \n\n2.Zhou Y, Zhang XC, Zhang JM, Cheng YH, Zhang J, et al. Molecular weight characterization of cellulose using ionic liquids. [J]. Polymer testing, 2021,93.",
+        "category": " References"
+    },
+    {
+        "id": 126,
+        "chunk": "# 申请的专利：  \n\n1．张金明，程耀辉，贺志远，张军，王健君，离子型多糖衍生物用作防冰涂层材料的应用。2021104833936.  \n2．张金明，程耀辉，张军，张鑫，尤晶璇，离子型多糖衍生物用作防雾涂层材料的应用。2021104817806.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Kinetic studies of polyurethane polymerization with Raman spectroscopy  \n\nShane Parnell, K. Min\\*, M. Cakmak  \n\nDepartment of Polymer Engineering, University of Akron, Akron, OH 44325-0301, USA  \n\nReceived 18 September 2002; received in revised form 4 April 2003; accepted 22 May 2003",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Abstract  \n\nIn this study, the polymerization kinetics of an uncatalyzed polyester based thermoplastic polyurethane formulation was characterized with Raman spectroscopy. Measuring the normalized scattering intensity of a band originating from the TPU diisocyanate, conversion was calculated as a function of time. Kinetic parameters obtained from these experiments correlated well with those obtained from analogous calorimetric experiments and with literature values. It was concluded that Raman spectroscopy is a powerful tool for characterizing the polymerization kinetics of polyurethanes in situ.  \n\n$\\circledcirc$ 2003 Elsevier Ltd. All rights reserved.  \n\nKeywords: Raman spectroscopy; Polyurethane; Kinetics",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# 1. Introduction  \n\nA large number of characterization methods have been used to monitor the kinetics of polymerization reactions. Kamal [1] and Mussati [2] have given extensive reviews. These methods fall into two groups: indirect methods, which measure a physical property that can be functionally related to the extent of reaction, and direct methods, which measure the concentration of reactant or product species. Rheometry and thermal methods fall into the first group while titration and spectroscopy belong to the second.  \n\nOf the indirect thermal methods used to monitor the polymerization kinetics of polyurethanes, differential scanning calorimetry [3,4] (DSC) and adiabatic temperature rise [5–9] (ATR) have the advantage that they are simple. However, given the fact that urethane systems are mixing activated, DSC can only follow slow polyurethane reactions. ATR on the other hand, can follow fast polyurethane reactions. Nonetheless, ATR is still an indirect method and many assumptions have to be made to relate heat evolution to extent of reaction.  \n\nOf the direct methods used to monitor the polymerization kinetics of polyurethanes, spectroscopic techniques have the advantage that they can measure extent of reaction directly, are capable of monitoring fast reactions, and can monitor several chemical changes at once. However, the versatility of infrared (IR) spectroscopy is limited due to sample preparation requirements [6]. Even with the use of attenuated total reflectance techniques, IR spectroscopy is still limited in that special sample cells must be constructed [10]. In contrast, Raman spectroscopy has several advantages. These advantages include minimal required sampling volume, the ability to utilize glass and other closed containers for sample cells, and larger frequency ranges for spectral observation on one instrument. However, the first and foremost advantage in Raman spectroscopy is sample preparation. Since the Raman effect is a scattering process, samples of any shape or size can be examined. Moreover, Raman spectroscopy measurements can be conducted remotely using inexpensive, communications grade, fused-silica optical fibers. A theoretical background and mathematical treatment of Raman scattering have been developed by Grasselli [11] and Koenig [12].  \n\nThese advantageous characteristics make Raman spectroscopy particularly useful for the in situ characterization of polymerization reactions where the removal of samples for off-line characterization is not always possible or practical. Since thermoplastic polyurethanes (TPUs) are produced continuously via reactive extrusion, the value of a versatile on-line characterization technique such as Raman spectroscopy becomes evident. The objective of this study is to characterize the kinetics of TPU polymerization in situ with Raman spectroscopy. More specifically, Raman spectroscopy will be used to acquire conversion versus time data from the polymerization of an uncatalyzed polyester based TPU formulation. Kinetics parameters extracted from such data will be compared to those obtained from analogous DSC experiments and literature values.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2. Experimental",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2.1. Materials  \n\nThe soft segment of the TPU used throughout this study was a hydroxyl terminated poly(butylene adipate) (PBA) oligomer supplied by Bayer. This diol had a number average molecular weight of approximately $2000\\mathrm{g/mol}$ . The hard segments of the TPU were derived from $^{4,4^{\\prime}}$ -diphenylmethane diisocyanate (MDI) and 1,4-butanediol (BDO). MDI was supplied by Bayer while BDO was supplied by ARCO chemical company.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.2. Sample preparation  \n\nIn preparation for TPU synthesis, PBA was melted and dried under a vacuum at $100^{\\circ}\\mathrm{C}$ for a minimum of $4\\mathrm{h}$ while BDO was dried over type 3A molecular sieves at room temperature for at least 2 weeks prior to synthesis. MDI was used as received but was stored under a vacuum at $0^{\\circ}\\mathrm{C}$ until required for synthesis.  \n\nThe TPU was synthesized with a relatively low hard segment content, corresponding to equimolar quantities of PBA and BDO. Keeping the stoichiometric ratio of hydroxyl to isocyanate functionality at unity, the TPU contained $76.84\\%$ PBA, $3.536\\%$ BDO, and $19.62\\%$ MDI by mass (based on PBA with an equivalent number average molecular weight of $979.1\\mathrm{g/mol})$ . Regardless of the polymerization environment, the ‘one-shot’ process was always the preferred route of TPU synthesis.  \n\nIn this procedure, dewatered PBA (heated to $100^{\\circ}\\mathrm{C})$ , BDO (at room temperature), and MDI (at room temperature) were gravimetrically metered into a $500\\mathrm{ml}$ polypropylene beaker and vigorously hand mixed for $15\\mathrm{~s~}$ Having thoroughly mixed all TPU reactants, samples were removed and prepared for immediate kinetic analysis.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.3. Raman spectroscopy measurements  \n\nA Kaiser Optical Systems Series 5000 Holoprobe Raman spectrometer was used to measure the kinetics of TPU polymerization. Equipped with a thermoelectrically cooled charge coupled device (CCD) detector, the system was capable of collecting spectra over a Raman shift spectral range of approximately $300{-}3300\\mathrm{cm}^{-1}$ . A $100~\\mathrm{{mW}}$ $785\\mathrm{nm}$ GaAlAs diode laser was used as the excitation radiation source.  \n\nUsing a $180^{\\circ}$ backscattering Raman measurement geometry, TPU reactant mixture samples approximately  \n\n$1.0\\mathrm{mm}$ in thickness were sandwiched between fused quartz cover slips and placed in a hot stage preheated to a specific isothermal polymerization temperature. Upon aligning the aperture of the hot stage, and thus the sample, with the focused Raman laser beam, a 30-s exposure time was used to generate a spectrum every $30~\\mathrm{s}$ . These isothermal experiments were terminated after $60\\mathrm{min}$ . Isothermal polymerization temperatures of 100, 120, 140, and $160^{\\circ}\\mathrm{C}$ were used to evaluate all kinetic parameters.  \n\nIn preparation for quantitative analysis, all Raman spectra were processed with several chemometric spectral manipulation techniques using Grams/386 software from Galactic Industries Corp. In order to remove Raleigh/fluorescence induced background scattering, a best-fit, fourth order, polynomial baseline was subtracted from all spectra. Because Raman spectroscopy is a single beam method and because the number of scattering sites can never be known in the analysis of solids, all Raman spectra were normalized with respect to an internal standard. To this end, peak intensity of the $1612\\mathrm{cm}^{-1}$ band was used. This band was the result of aromatic ring breathing/stretching vibrational modes present in the phenylene groups of MDI.  \n\nPeak height was used as a measure of peak intensity in this study. Although peak areas are most desirable, measurements can only be made in this way when the signal-to-noise (S/N) is very high, and the baseline is well defined. Small errors have a disproportionate effect on the final result using this method because all points in the spectral peak are given equal weight in the calculation. In contrast to peak area measurements, peak height measurements usually give the best results unless there is a significant change in peak shape with concentration. If such measurements are made at a peak’s maximum, the point of optimum S/N is used reducing errors attributed to random noise. However, since this type of measurement is sensitive to high frequency noise, all Raman signals were filtered accordingly.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.4. Calorimetric measurements  \n\nA Thermal Advantage 2920 modulated differential scanning calorimeter operating in the isothermal mode was also used to measure the kinetics of TPU polymerization. In conducting these experiments, TPU reactant mixture samples were carefully weighed to $10\\pm2\\mathrm{mg}$ and sealed in aluminum hermetic pans and lids. Upon placing a sealed sample into the DSC preheated to a specific isothermal temperature, heat flow resulting from the exothermic TPU polymerization reaction was measured as a function of time. After $60\\mathrm{min}$ of isothermal polymerization, samples were immediately quenched to $0^{\\circ}\\mathrm{C}$ at a cooling rate of $-100\\mathrm{^{\\circ}C/m i n}$ and then subjected to a temperature scan from 0 to $200^{\\circ}\\mathrm{C}$ at a heating rate of $20\\ \\mathrm{{^circC/min}}$ . This temperature scan was performed in an effort to quantify any residual heat of reaction not evolved in the previous isothermal scan and to ensure complete TPU polymerization. Isothermal polymerization temperatures of 100, 120, 140, and $160^{\\circ}\\mathrm{C}$ were used to evaluate all kinetic parameters.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 3. Results and discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3.1. TPU conversion from Raman spectroscopy  \n\nQuantitative kinetic analysis of a reacting system with Raman spectroscopy is based on measuring changes in peak intensity of bands belonging to characteristic reactant or product functional groups during the reaction period. Therefore, to elucidate which bands may be suitable for kinetic measurements on the TPU formulation investigated in this study, Fig. 1 shows partial Raman spectra of an uncatalyzed TPU reactant mixture after 1 min, $30\\mathrm{min}$ , and $12\\mathrm{h}$ $\\langle\\alpha\\cong1\\rangle$ of polymerization at $120^{\\circ}\\mathrm{C}$ . Tentative band assignments are made from reference to earlier Raman studies of polyesters [13–16], isocyanates [15,16], and urethanes [15,16] and are listed in Table 1. In principal, Raman scattering intensities of isocyanate (asymmetric stretch at $2275~\\mathrm{{cm}^{-1}}$ and symmetric stretch at $14\\dot{4}5~\\mathrm{cm}^{-1};$ ), hydroxyl, and urethane $(\\mathrm{N-H}$ stretch, amide I at ca. $1\\dot{7}32\\mathrm{cm}^{-1}$ , amide $\\mathrm{II}$ at ca. $1530\\mathrm{cm}^{-1}$ , and amide III at ca. $1303\\mathrm{cm}^{-1},$ ) functional groups can all be used to determine the kinetics of polymerization for this particular TPU formulation. However, bands resulting from hydroxyl and urethane $\\mathrm{\\DeltaN-H}$ stretching vibrations cannot be used for quantitative kinetic analysis since they are too small or fall outside of the Raman shift spectral range (ca. $300-$ $3300\\mathrm{cm}^{-1}.$ ) accessible in these experiments. Bands resulting from amide I vibrations in urethane linkages produced during TPU polymerization could be used for quantitative analysis, but these bands overlap those from carbonyl stretching vibrations present in the ester groups of PBA. This coupled with complications arising from H-bonding and low S/N ratios render quantitative measurements on bands from urethane amide I vibrations very difficult. Bands originating from urethane amide II and amide III vibrations are viable candidates for quantitative measurements, but they also suffer from multi-peak overlap and/or low S/N ratios.  \n\n![](images/4b47818368219717a2977c3c5aeba2f5cd1e5531ea98e4892e2034c738d0a0c3.jpg)  \nFig. 1. Partial Raman spectra of the TPU reactant mixture polymerized at $120^{\\circ}\\mathrm{C}$ for $1\\mathrm{min}$ , $30\\mathrm{min}$ , and $12\\mathrm{h}$ .  \n\nTable 1 Tentative band assignments in the partial Raman spectra of TPU reactive mixture polymerized at $120^{\\circ}\\mathrm{C}$   \n\n\n<html><body><table><tr><td>Raman shift (cm-1)</td><td>Assignment</td></tr><tr><td>2275</td><td>Vassym.(N=C=O)</td></tr><tr><td>1732</td><td>Ester v(C=O), urethane amide I v(C=O)</td></tr><tr><td>1612</td><td>v(Ar)</td></tr><tr><td>1530</td><td>v(Ar), Urethane amide II: v(C-N)+ S(N-H)</td></tr><tr><td>1445</td><td>Vsym.(N=C=O),8(CH)</td></tr><tr><td>1303</td><td>8(CH), urethane amide III?</td></tr><tr><td>1251</td><td>Urethane amide IlI?</td></tr><tr><td>1185</td><td>Urethane amide?</td></tr></table></body></html>  \n\nOf particular interest in Fig. 1 are the asymmetric and symmetric isocyanate stretching vibrations of MDI. Both of these bands noticeably decrease in intensity with polymerization time. Very strong in IR spectra, band intensity of the asymmetric isocyanate stretching vibration is quite weak in Raman spectra. This fact is clearly shown in Fig. 1 where this band is barely discernable from the baseline at a Raman shift of $2275~\\mathrm{{cm}^{-1}}$ . With such a low $\\mathsf{S}/\\mathsf{N}$ , this band could not be used for kinetic analysis. The symmetric isocyanate stretching vibration can be observed as a medium intensity band at approximately $1445~\\mathrm{{cm}^{-1}}$ . Unfortunately, there is considerably overlap of this band with other bands resulting from $\\mathrm{CH}_{2}$ bending vibrations present in all reactants of the TPU formulation. Therefore, this band was not particularly tractable for kinetic analysis either.  \n\nAs shown in Fig. 1, a band at $1530\\mathrm{cm}^{-1}$ is similar to the isocyanate asymmetric and symmetric stretching vibrations in that its intensity decreases with increasing polymerization time. At room temperature, this band is clearly present in both the Raman and IR spectra of pure MDI as shown in  \n\n![](images/d916e6cbbe6944e5bd6c7abed792f99feea172101593ad274e08ef5fe7a6d431.jpg)  \nFig. 2. Raman and IR spectra of pure MDI at room temperature.  \n\nFig. 2. A careful review of the literature suggests that this band arises from para $^{4,4^{\\prime}}$ -isomer) disubstituted phenylene ring vibrations in MDI [17]. Other studies involving band assignment in the Raman and IR spectra of phenyl isocyanate suggest that this band represents one of thirty fundamental $\\scriptstyle{\\mathbf{C}}-{\\mathbf{C}}$ stretching vibrational modes present in the phenyl groups of monosubstituted benzenes [18,19]. Of the 30 fundamental frequencies for $\\mathrm{C_{6}H_{5}–X}$ type molecules, six vibrations are dependent on the mass of X. It is speculated that an analogous vibration is responsible for the $1\\bar{5}30\\mathrm{cm}^{-1}$ band in the phenylene rings of MDI. Regardless, peak intensity of the $15\\bar{3}0\\mathrm{cm}^{-1}$ band, hereon out termed the MDI band, was assumed directly proportional to the concentration of MDI, and thus isocyanate groups, not yet polymerized. Therefore, it was used for determining the polymerization kinetics of this TPU formulation.  \n\nAssuming peak height of the MDI band is a suitable measure of peak intensity, and thus concentration, the relationship between TPU conversion and MDI band peak height can be expressed as  \n\n$$\n\\alpha(t)=\\frac{I_{0}-I(t)}{I_{0}}\n$$  \n\nwhere $\\alpha(t)$ is the time-dependent TPU conversion, $I(t)$ ; the time dependent peak height of the MDI band, and $I_{0}$ is the peak height of this band at zero conversion. Because of the former assumption and the fact that all Raman spectra were normalized with respect to a conversion independent vibrational mode in MDI itself, a method of external calibration was not used in this study.  \n\nThe step growth polymerization of this TPU formulation results in the formation of urethane linkages. These urethane linkages in turn contain $\\mathrm{C-N}$ stretching and $\\mathrm{\\DeltaN-H}$ bending vibrations that are Raman active. Unfortunately, these amide II vibrational modes generate scattering at a Raman shift of approximately $1530\\mathrm{cm}^{-1}$ . Shown in Fig. 1 after $12\\mathrm{h}$ of polymerization time at $120^{\\circ}\\mathrm{C}$ $\\langle\\alpha\\cong1\\rangle$ Þ; these vibrations generate weak yet significant bands in the Raman spectrum of fully polymerized TPU. As a result, Eq. (1) must be modified to account for a growing amide II band at approximately the same Raman shift as the MDI band.  \n\nAssuming peak height of the $1530\\mathrm{cm}^{-1}$ band is a time dependent sum of both MDI and amide II bands and that peak height of the latter band is directly proportionally to conversion, peak height of the MDI band can be written as  \n\n$$\nI(t)=S(t)-A_{\\infty}\\alpha(t)\n$$  \n\nwhere $S(t)$ represents the experimentally measured, timedependent peak height of the composite $1530\\mathrm{cm}^{-1}$ band and $A_{\\infty}$ is peak height of the amide $\\mathrm{II}$ band at complete conversion. Substituting Eq. (2) into Eq. (1) results in  \n\n$$\n\\alpha(t)=\\frac{I_{0}-[S(t)-A_{\\infty}\\alpha(t)]}{I_{0}}\n$$  \n\nAfter realizing that $I_{0}$ equals the composite $1530\\mathrm{cm}^{-1}$ band at zero conversion (ca. 0.40), $S_{0}$ ; and $A_{\\infty}$ equals the composite $1530\\mathrm{cm}^{-1}$ band at complete conversion (ca. 0.12), $S_{\\infty}$ ; Eq. (3) can be rearranged and solved for conversion. This expression  \n\n$$\n\\alpha(t)=\\frac{S_{0}-S(t)}{S_{0}-S_{\\infty}}\n$$  \n\nwas used to calculate TPU conversion data from Raman spectra acquired over the course of an experiment.  \n\nThe symbols in Fig. 3 show conversion versus polymerization time profiles calculated from Eq. (4) applied to chemometrically processed Raman spectra of uncatalyzed TPU reactant mixtures polymerized at various temperatures. As expected, higher polymerization temperatures result in higher conversion rates and final conversions after $30\\mathrm{min}$ of polymerization time. The scattering of data points in Fig. 3 is due to noise in Raman spectra and to errors introduced into the calculation method (i.e. baseline subtraction, normalization, peak height measurement), which are usually inevitable in the quantitative analysis of Raman spectra, especially in kinetic studies.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3.2. TPU conversion from calorimetry  \n\nAfter completing a temperature scan on a particular sample, TPU conversion versus time data was extracted from the corresponding isothermal scan through application of the proper energy balance. Assuming a constant enthalpic heat of reaction, no significant interference from side reactions, and heat evolved during polymerization was proportional to the extent of polymerization, conversion as a function of time was calculated from  \n\n$$\n\\alpha(t)=\\frac{\\Delta H_{\\mathrm{l}}+\\Delta H(t)}{-(\\Delta H_{\\mathrm{rxn.}})}\n$$  \n\nwhere $\\Delta H_{\\mathrm{l}}$ is the molar enthalpic heat of reaction lost during sample preparation, sample loading, and DSC stabilization, $\\Delta H(t)$ ; the time dependent TPU polymerization exotherm measured in an isothermal scan, and $\\Delta H_{\\mathrm{rxn.}}$ is the total molar enthalpic heat of reaction for TPU step growth polyaddition which was assumed constant for all isothermal polymerization temperatures. $\\Delta H_{\\mathrm{l}}$ was calculated from the relation  \n\n![](images/e502365281a190ff367ad74cd6c2603b0c9bedc2fb293c90da715f5b3973038a.jpg)  \nFig. 3. Experimental and predicted isothermal Raman conversion versus time profiles for the TPU reactant mixture polymerized at different temperatures.  \n\n$$\nH_{1}=-(\\Delta H_{\\mathrm{rxn.}})-\\Delta H_{\\mathrm{t}}-\\Delta H_{\\mathrm{r}}\n$$  \n\nwhere $\\Delta H_{\\mathrm{t}}$ is the total TPU polymerization exotherm measured in an isothermal scan and $\\Delta H_{\\mathrm{r}}$ is the residual molar enthalpic heat of reaction measured in subsequent temperature scan experiments.  \n\nSince TPU step growth polymerization is mixing activated and thus starts with sample preparation, sample loading, and DSC stabilization, DSC was not able to measure exothermic heat flow from the entire course of reaction. Therefore, $\\Delta H_{\\mathrm{rxn}}$ : was measured from independent ATR experiments. In these experiments, the temperature rise of a highly catalyzed, bulk TPU polymerization was followed under quasi-adiabatic conditions. A combination of short total reaction times, fast rate of temperature rise during the major portion of the reaction, and slow heat loss due to low thermal conductivity of the TPU itself ensured that reaction conditions were close to adiabatic. In relating maximum temperature rise to the molar enthalpic heat of reaction for this TPU formulation, $\\Delta H_{\\mathrm{rxn.}}$ ; the following assumptions were made: the TPU reactant mixture was homogeneous, the polymerization was not limited by diffusion, there were no other heat sources other than the polymerization reaction, and density and $\\Delta H_{\\mathrm{rxn.}}$ : were constant. Under these assumptions, the overall energy balance for a single irreversible polymerization reaction, excluding heat loss is  \n\n$$\nC_{p}\\frac{\\mathrm{d}T}{\\mathrm{d}t}=-(\\Delta H_{\\mathrm{rxn.}})\\frac{\\mathrm{d}\\alpha}{\\mathrm{d}t}[\\mathrm{NCO}]_{0}\n$$  \n\nwhere $C_{p}$ is the heat capacity per unit mass, $T$ the experimentally measured temperature, $\\alpha$ the conversion, and $[\\mathrm{NCO}]_{0}$ is initial isocyanate molality.  \n\nIf we eliminate time from both sides of Eq. (7) and assume $\\alpha\\to1$ ; we can integrate the resulting differential equation to solve for $\\Delta H_{\\mathrm{rxn.}}$ as a function of maximum temperature rise. Hence,  \n\n$$\n-(\\Delta H_{\\mathrm{rxn.}})=\\frac{1}{[\\mathrm{NCO}]_{0}}\\int_{T_{0}}^{T_{\\mathrm{f}}}C_{p}(T)\\mathrm{d}T\n$$  \n\nwhere $T_{0}$ and $T_{\\mathrm{f}}$ are initial and final TPU reactant mixture temperatures, respectively. If $C_{p}(T)$ is assumed to be a linear function of temperature and changes very little with conversion from monomer to polymer as is the case for amorphous polymers [20], simple weight average additivity of TPU reactant heat capacities can be used to calculate $C_{p}(T)$ : Using data obtained from Steinle et al. [7], the $C_{p}(T)$ relation used for the TPU reactant mixture formulation in this study was  \n\n$$\nC_{p}(T)=0.9634+0.002776T\n$$  \n\nIn Eq. (9), $T$ is in Kelvin to obtain $C_{p}$ values in $\\mathrm{kJ/kg~K}$ . For the catalyzed TPU formulations investigated here, the average ATR was approximately $67^{\\circ}\\mathrm{C}$ . This leads to an average $\\Delta H_{\\mathrm{rxn.}}$ of $-90\\mathrm{kJ/mol}$ equiv. isocyanate, which is in excellent agreement with the value obtained by other investigators [5 – 9] studying similar systems.  \n\nThe symbols in Fig. 4 show conversion versus polymerization time profiles calculated from Eq. (5) applied to isothermal DSC scans of uncatalyzed TPU reactant mixtures polymerized at various temperatures. Overall, conversion versus polymerization time profiles obtained from calorimetry correlated reasonably well with those obtained from Raman spectroscopy obtained at the same isothermal polymerization temperature (Fig. 3).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3.3. Kinetic parameter determination  \n\nElemental kinetic mechanisms describing urethane formation from active hydrogen bearing compounds and isocyanates are not well understood. Due to the complexities of urethane reaction mechanisms, most studies have adopted the following Arrhenius type, phenomenological rate law with success [21].  \n\n$$\n\\frac{\\mathrm{d}[\\mathrm{NCO}]}{\\mathrm{d}t}=-k[\\mathrm{NCO}]^{a}[\\mathrm{OH}]^{b}\n$$  \n\nwhere  \n\n$$\nk=A\\ {\\mathrm{e}}^{-E_{\\mathrm{a}}/R T}\n$$  \n\nIn Eq. (10), $k$ is the rate constant and $\\boldsymbol{[\\mathrm{NCO}]}$ and $\\mathrm{[OH]}$ are the concentrations of isocyanate and active hydrogen bearing compounds, respectively. Similarly, the exponents $a$ and $b$ represent the order of reaction with respect to isocyanate and active hydrogen bearing compounds, respectively. As shown in Eq. (11), $k$ is most often expressed with Arrhenius type temperature dependence where $A$ is a frequency factor, $E_{\\mathrm{a}}$ is activation energy, $R$ is the universal gas constant, and $T$ is temperature in Kelvin. It should be noted that Eq. (10) is not a mechanistic model. It has only one rate constant with a single activation energy to express a multitude of reaction mechanisms and rates of reaction.  \n\nIf we assume the urethane reaction is run at equal stoichiometry (i.e. $[\\mathbf{C}]=[\\mathrm{NCO}]=[\\mathrm{OH}])$ ) and express concentration in terms of conversion (i.e.  \n\n![](images/92a94bc12040f8637f38ba0b080da846a7e3d9052f107c10604231837c56cbe2.jpg)  \nFig. 4. Experimental and predicted isothermal DSC conversion versus time profiles for the TPU reactant mixture polymerized at different temperatures.  \n\n$[\\mathbf{C}]=[\\mathbf{C}]_{0}(1-\\alpha))$ , Eq. (10) can be rewritten as  \n\n$$\n{\\frac{\\mathrm{d}\\alpha}{\\mathrm{d}t}}=k[\\mathbf{C}]_{0}^{n-1}(1-\\alpha)^{n}\n$$  \n\nwhere $[\\mathrm{Cl}_{0}$ is equal to initial isocyanate or active hydrogen bearing compound concentration and $n=a+b$ is the overall order of reaction.  \n\nIn order to calculate kinetic parameters for this TPU formulation polymerized at different temperatures, the data in Figs. 3 and 4 was fitted to the kinetic rate law model described by Eqs. (11) and (12) with least squares linear regression techniques. In determining the kinetic parameters $k$ and $n$ from the spectral data, significant data scatter eliminated the possibility of reliably evaluating da=dt: Therefore, the differential equation described by Eq. (12) was solved via the separation of variables technique and rearranged into the following form  \n\n$$\n-\\frac{(1-\\alpha)^{-n+1}}{-n+1}=-\\frac{1}{-n+1}+k[\\mathbb{C}]_{0}^{n-1}t\n$$  \n\nThe left-hand side of Eq. (13) was then calculated from the conversion data in Fig. 3 and plotted versus respective polymerization time for different values of $n$ : The value of $n$ resulting in linear curves, which corresponded to the overall order of reaction, was found to be 1.7 for all four polymerization temperatures investigated. The resulting curves calculated with $n=1.7$ ; which have slopes equal to $k[\\mathbf{C}]_{0}^{n-1}$ and $y$ -intercepts equal to $-1/(-n+1)$ ; are shown in Fig. 5. Using least squares linear regression, each curve was fitted with a regression line and a value of $k$ was found for each polymerization temperature.  \n\nIn determining the kinetic parameters $k$ and $n$ from the calorimetric data, log–log plots of da=dt versus $(1-\\alpha)$ were constructed from the conversion data in Fig. 4 and are shown in Fig. 6. Using least squares linear regression, the linear portion of each curve was fitted with a regression line and a value of $n$ and $k$ was found for each polymerization temperature. Regardless of polymerization temperature, an overall order of reaction of 1.7 afforded the best fit to all the data.  \n\nIt should be noted that only the Arrhenius controlled conversion regime (i.e linear portion) of the curves in Figs. 5 and 6 were fitted with a regression line. Past a critical conversion, which increases with temperature, hard segment phase separation from the reactant mixture results in diffusion controlled kinetics and hence a deviation from the kinetic model described by Eqs. (11) and (12). This is especially evident in Fig. 6 at $100^{\\circ}\\mathrm{C}$ . Such an effect could significantly influence the TPU polymerization exotherm and thus introduce errors into the calculation of conversion from Eq. (5).  \n\n![](images/17a758fdd7ac2950e94131c2a1ee25fb939d5a59e19aaab77d7869a3d8251444.jpg)  \nFig. 5. Plots of Raman $-\\{(1-\\alpha)^{-n+1}\\}/(-n+1)$ versus time for the TPU reactant mixture polymerized at different temperatures.  \n\n![](images/6c71f80f684063d91091054e90dcac24e4f869d6e6262b0dca21282214eb6c68.jpg)  \nFig. 6. log–log plots of DSC conversion rate versus conversion remaining for the TPU reactant mixture polymerized at different temperatures.  \n\nNext, values of $k$ from the linear regression analyses in Figs. 5 and 6 were used to calculate the Arrhenius kinetic parameters $A$ and $E_{\\mathrm{a}}$ from both the spectral and calorimetric data, respectively. Assuming the kinetic rate law model given by Eq. (12) is valid and $n$ remains constant throughout the entire reaction, a semi-ln plot of $k$ versus $1/T$ should yield a straight line with slope equal to $-E_{\\mathrm{a}}/R$ and $y.$ - intercept equal to ln A : Indeed, as shown in Fig. 7, values of $k$ obtained from the two sets of data do form linear curves when plotted versus $1/T$ and almost coincide showing that the two different measurement techniques yielded similar results. The Arrhenius parameters $A$ and $E_{\\mathrm{a}}$ were evaluated from the least squares linear regression lines also shown in Fig. 7. Table 2 lists all kinetic parameters calculated for the step growth polymerization of this TPU formulation and Figs. 3 and 4 show the corresponding model predictions.  \n\n![](images/025852f3a7ed036ff4545b3f6703156fcff4159c1622deecc6b1378fb8454b12.jpg)  \nFig. 7. Evaluation of $A$ and $E_{\\mathrm{a}}/R$ from semi-ln plot of Raman and DSC $k$ versus $1/T$ data for TPU reactant mixtures polymerized at different temperatures.  \n\nTable 2 Listing of kinetic parameters obtained from TPU investigated in this study ${\\bf d}[{\\bf C}]/{\\bf d}t=-A\\ {\\bf e}^{-E_{\\mathrm{a}}/R T}[{\\bf C}]^{n}$   \n\n\n<html><body><table><tr><td>Characterization technique</td><td>A (mole NCO-0.7/kg solution-0.7 s)</td><td>Ea (J/mol)</td><td>n</td></tr><tr><td>Raman</td><td>6.02 × 102 ± 1.62·102</td><td>3.87 × 104 ± 5.73 × 103</td><td>1.7</td></tr><tr><td>DSC</td><td>9.92 × 10² ± 1.18 × 102</td><td>3.87 × 104 ± 2.74 × 103</td><td>1.7</td></tr></table></body></html>\n\nNote: $[\\mathrm{C}]{=}[\\mathrm{NCO}]{=}[\\mathrm{OH}]$ has units of mole/kg.  \n\nIn summary, both Raman spectroscopy and DSC yielded similar results when used to measure the kinetics of TPU polymerization. Both measurement techniques yielded 1.7 for the overall order of reaction, $n$ : This is in agreement with almost all urethane reaction kinetic data in the literature, where $n$ varies from 1 to 2 [9,21]. For example, using isothermal and non-isothermal DSC, Hager et al. [3] calculated $n$ to be 2.0 while Hernandez-Sanchez and VeraGraziano [4] calculated $n$ to be 1.63, respectively. Utilizing the ATR measurement technique, Lipshitz and Macosko [5] calculated $n$ to be 1.5 while Camargo et al. [8] calculated $n$ to be 1.4.  \n\nThe activation energy, $E_{\\mathrm{a}}$ ; calculated from both measurement techniques was approximately $3.9\\times10^{4}\\mathrm{J/mol}$ , which is general agreement with the literature. For example, Hager et al. [3] calculated $E_{\\mathrm{a}}$ to be $4.1\\times10^{4}\\mathrm{J/mol}$ with isothermal DSC and Camargo [9] calculated $E_{\\mathrm{a}}$ to be approximately be $5.5\\times10^{4}\\mathrm{J/mol}$ with ATR. Incidentally, values of $E_{\\mathrm{a}}$ closer to that obtained by Camargo [9] are obtained from both measurement techniques if the $100^{\\circ}\\mathrm{C}$ data in Fig. 7 is not included. As previously discussed, it is probable that micro-phase separation results in a significant deviation from Arrhenius controlled reaction kinetics at this temperature. A deviation from the kinetic model described by Eqs. (11) and (12) caused by urethane bond thermal dissociation is also possible. Several publications [22–24] have shown that this process starts at $150-160^{\\circ}\\mathrm{C}$ and becomes significant at $190-200\\ {^{\\circ}}\\mathrm{C}$ . In this study, it is assumed that such depolymerization is insignificant at all of the temperatures investigated. Given the linearity of the data in Fig. 7 at 120, 140, and $160^{\\circ}\\mathrm{C}$ , this assumption appears reasonable.  \n\nThe frequency factor, $A$ ; obtained from DSC is approximately $50\\%$ larger than that obtained from Raman spectroscopy. While both are in general agreement with literature values for uncatayzed TPU systems [3], this disparity probably results from errors introduced into the calculation of conversion (i.e. baseline subtraction and normalization in Raman spectroscopy and the calculation of $\\Delta H_{\\mathrm{rxn.}}$ in DSC) from both measurement techniques. Another probable source for this difference comes from the fact that Raman spectroscopy is a direct (i.e. measures reactant concentration) technique while DSC is an indirect (i.e. measures heat evolution) technique. Differences in measurement technique sample geometry and preparation could also be significant. Regardless, kinetic parameters obtained from both measurement techniques agreed favorably with classical literature values [3–9] proving that Raman spectroscopy is a useful method for characterizing the kinetics of polyurethane polymerization.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 4. Conclusions  \n\nPeak intensity of a band in MDI was assumed proportional to isocyanate concentration and thus conversion in the polymerization of this TPU formulation. Given the capability to calculate conversion from Raman spectra acquired over the course of an experiment, conversion versus time data was collected from the isothermal polymerization of this TPU formulation at different temperatures. Such data was modeled with an Arrhenius type, phenomenological rate law with success. Kinetic parameters agreed reasonably well with those obtained from analogous calorimetric measurements and with literature values. Since the Raman effect is a scattering process, sample preparation is relatively simple compared to other spectroscopic techniques. Hence, it can be concluded that Raman spectroscopy is a powerful tool for characterizing the polymerization kinetics of polyurethanes in situ.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 14,
+        "chunk": "# References  \n\n[1] Kamal MR. Polym Engng Sci 1974;14:231.   \n[2] Mussatti FG. PhD Thesis, University of Minnesota; 1975.   \n[3] Hager SL, McRury TB, Gerkin RM, Critchfield FE. Urethane block copolymers: kinetics of formation and phase development, urethane chemistry and applications. ACS Symposium Series 172, Washington, DC: American Chemical Society; 1981.   \n[4] Hernandez-Sanchez F, Vera-Graziano R. J Appl Polym Sci 1992;46: 571.   \n[5] Lipshitz SD, Macosko CW. J Appl Polym Sci 1977;21:2029.   \n[6] Richter EB, Macosko CW. Polym Engng Sci 1978;18(13):1012.   \n[7] Steinle EC, Critchfield FE, Castro JM, Macosko CW. J Appl Polym Sci 1980;25:2317.   \n[8] Camargo RE, Gonzalez VM, Macosko CW, Tirrell M. Bulk polymerization kinetics by the adiabatic reactor method. Second International Conference on Reactive Processing of Polymers, Pittsburgh; 1982.   \n[9] Camargo RE. PhD Thesis, University of Minnesota; 1984.   \n[10] Bras W, Derbyshire GE, Bogg D, Cooke J, Elwell MJ, Komanschek BU, Naylor S, Ryan AJ. Science 1995;267:996.   \n[11] Grasselli JG, Bulkin BJ. Analytical Raman spectroscopy. New York: Wiley; 1991.   \n[12] Koenig JL. Spectroscopy of polymers, 2nd ed. New York: Elsevier; 1999.   \n[13] Cassanas G, Kister G, Fabregue E, Morssli M, Bardet L. Spectrochim Acta 1993;49A(2):271.   \n[14] Kister G, Cassanas G, Fabregue E, Bardet L. Eur Polym J 1992; 28(10):1273.   \n[15] Dollish FR, Fateley WG, Bentley FF. Characteristic Raman frequencies of organic compounds. New York: Wiley; 1974.   \n[16] Socrates G. Infrared and Raman characteristic group frequencies. New York: Wiley; 2001.   \n[17] Mushkin YI, Smirnova NF, Tsigin BM, Finkel’shtein AI. J Appl Spectrosc 1971;15:1623.   \n[18] Whiffen DH. J Chem Soc 1956;1350.   \n[19] Stephenson CV, Coburn Jr WC, Wilcox WS. Spectrochim Acta 1961; 17:933.   \n[20] Van Krevelen DW. Properties of Polymers, 2nd ed. New York: Elsevier; 1976.   \n[21] Macosko CW. RIM fundamentals of reaction injection molding. New York: Hanser; 1989.   \n[22] Yang WP, Macosko CW, Wellinghoff ST. Polymer 1986;27:1235.   \n[23] Joel D, Hauser A. Die Angewandte Makromolekulare Chemie 1994; 217:191.   \n[24] Hentschel T, Munstedt H. Polymer 2001;42:3195.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "Published in final edited form as: ExpertOpinDrugDiscov. 2010 December ; 5(12): 1205–1220. doi:10.1517/17460441.2010.524924.",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# Exploiting PubChem for Virtual Screening",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# Xiang-Qun Xie\\*  \n\nDepartment of Pharmaceutical Sciences, School of Pharmacy; Drug Discovery Institute/ Pittsburgh Molecular Library Screening Center (PMLSC); Pittsburgh Chemical Methodologies & Library Development (PCMLD) Center; Departments of Computational Biology and Structural Biology; University of Pittsburgh, Pittsburgh, PA 15260, USA",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# Abstract  \n\nImportance of the field—PubChem is a public molecular information repository, a scientific showcase of the NIH Roadmap Initiative. The PubChem database holds over 27 million records of unique chemical structures of compounds (CID) derived from nearly 70 million substance depositions (SID), and contains more than 449,000 bioassay records with over thousands of in vitro biochemical and cell-based screening bioassays established, with targeting more than 7000 proteins and genes linking to over 1.8 million of substances.  \n\nAreas covered in this review—This review builds on recent PubChem-related computational chemistry research reported by other authors while providing readers with an overview of the PubChem database, focusing on its increasing role in cheminformatics, virtual screening and toxicity prediction modeling.  \n\nWhat the reader will gain—These publicly available datasets in PubChem provide great opportunities for scientists to perform cheminformatics and virtual screening research for computer-aided drug design. However, the high volume and complexity of the datasets, in particular the bioassay-associated false positives/negatives and highly imbalanced datasets in PubChem, also creates major challenges. Several approaches regarding the modeling of PubChem datasets and development of virtual screening models for bioactivity and toxicity predictions are also reviewed.  \n\nTake home message—Novel data-mining cheminformatics tools and virtual screening algorithms are being developed and used to retrieve, annotate and analyze the large-scale and highly complex PubChem biological screening data for drug design.",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# Keywords  \n\nPubChem; cheminformatics; data-mining; virtual screening; toxicity; polypharmacology",
+        "category": " Abstract"
+    },
+    {
+        "id": 6,
+        "chunk": "# 1. Introduction  \n\nPubChem is a scientific showcase of the Molecular Libraries Program (MLP), a US National Institutes of Health (NIH) Roadmap Initiative (http://mli.nih.gov/mli/) that aims to enhance chemical biology efforts through high-throughput screening (HTS) so as to identify small molecule probes effective at modulating a given biological process or disease. The PubChem database (http://PubChem.ncbi.nlm.nih.gov) was constructed in 2004 to facilitate information exchange and data sharing among the ten NIH-funded centers of the Molecular Libraries Screening Centers Network (MLSCN), which later was transformed to Molecular  \n\nLibraries Probe Production Centers Network (MLPCN) in 2008. The MLPCN is composed of three different types of centers, i.e., Comprehensive Centers, Specialized Screening Centers and Specialized Chemistry Centers1.  \n\nAlong with comprehensive online information on small molecule chemical structures and corresponding biological activity data, the PubChem database has now grown into a powerful public molecular information resource with online data analysis and subsetting tools to facilitate high-throughput/high-content screening (HTS/HCS) of small molecules that modulate the bioactivity of various targets. Maintained by the National Center for Biotechnological Information $(\\mathrm{NCBI})^{2}$ , the PubChem database system consists of three primary relational databases: Substance (substance ID or SID), Compound (compound ID or CID) and Bioassay (assay ID or AID), which correspond to the three major query functions as shown in Figure 1. As of July 2010, the PubChem Substance database contains 69,170,468 entries of mixtures, extracts, complexes and uncharacterized substances; the PubChem Compound database contains 27,443,646 records of unique chemical structure compounds derived from the substance depositions; and the PubChem Bioassay database has 449,401 records. These data records were deposited by screening centers funded by the NIH Molecular Library Program, academic institutions, and industrial research organizations as illustrated in Figure 1A. The update list is referred to see the PubChem substance and bioassay data source information website 3.  \n\nAs PubChem continues to grow rapidly in the data collections as well as online data-mining analysis capability, research opportunities also emerge for the scientific community to exploit the available structural and biological data to enhance understanding and investigating the structure activity relationships (SAR), pharmacology, metabolism and toxicology profiles of target compounds, both in vitro and in silico. In the meantime, novel data-mining cheminformatics tools and virtual screening algorithms are being developed and used to retrieve, annotate and analyze the large-scale and highly complex PubChem biological screening data.  \n\nSince PubChem was launched, there has been rapidly increasing the number of research publications using PubChem chemical library and bioassay data for cheminformatics datamining studies, virtual screening, SAR, in silico design, and on the like (Figure 2). The numbers of the PubChem-related research publications quickly increased from only a total of 32 PubChem-related articles in 2005 to 119 in 2009. A total of 459 PubChem-related articles have been published as of July 2010. Figure 2 provides a brief look at all 459 research publications (405 journal articles and 52 meeting abstracts) published where the word “PubChem” is used as a query. The associated research subjects were also used to survey the PubChem-related research fields. Until July 2010, there have been approximately 68 publications related to computational studies of PubChem data in the interested fields related to cheminformatics, data annotation, virtual screening and toxicity prediction research studies. There have also been a few PubChem review publications for which the reader is referred to the detailed reports on the PubChem database platform 4-6, chemical probe identities 7, 8, bioassay resources and bioactivity results 4, 9. The focus of this present review article is to give readers a most recent review of the PubChem database and the published PubChem library data-mining and virtual screening/in silico design research studies.",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2. PubChem dataset collections  \n\nCurrently (July, 2010), the PubChem databases hold records for over 69 million substances (SID) containing 27 million unique chemical structures (or CID records) and 449,401 bioassays (AID). More than1.8 millions of these substances and 1.5 millions of compounds have bioactivity data in at least one of the thousands in vitro biochemical and cell-based screening assays, targeting more than 7,000 proteins and genes. The millions of compound records and bioassay data collections provide great opportunities for drug discovery research. They also, however, create a major challenge for scientists for the development of cheminformatics tools and modeling algorithms that are suitable to handle such high volumef of PubChem compound and bioactivity datasets for virtual screening and in silico drug design.  \n\nOver the past few years, PubChem developer teams, cheminformatics research centers and many researchers from academic institutes and industries have developed a variety of online tools to access and analyze the PubChem Compound and Bioassay data records, including online search, FTP, and automated access to the data through the Entrez Utilities 10. Several review and research articles 4, 6, 11-14 have reported the current cheminformatics tools available to annotate and mine PubChem database via integrating PubChem with transcriptomic, proteomic and metabolomic datasets and ultimately translate chemical genomics screening data into information that will be benefit biomedical scientists and clinician who do not have extensive training in cheminformatics. The following sections cover the PubChem data sources and download information as well as how to construct high-quality structurally diverse compound libraries from PubChem database for virtual screening studies.",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.1. PubChem data sources and download formats  \n\nFor computational chemistry, one of the important steps is to obtain reliable datasets for computer modeling studies, which requires an understanding of the biological targets within the data and knowledge of the data source. The PubChem Bioassay datasets available for cheminformatics modeling studies were deposited by NIH-funded screening centers with data records of 3.95 million substance counts $(79.3\\%$ of the total substance counts) and 2315 bioassay counts $0.5\\%$ of total bioassay counts) 1, by European Bioinformatics Institute (ChEMBL) with data records of 551,496 substance counts ( $11\\%$ counts) and 446,639 bioassay counts $(99.4\\%)$ 15, and also contributed by more than 40 of US agencies and various academic institutions and individual research laboratories (Figure 1).  \n\nSpecifically, human tumor cell line screening data were deposited from the Developmental Therapeutic Program (DTP) 16 at the US National Cancer Institute (NCI), toxicology data from the DSSTox 17 program at the US Environmental Protection Agency (EPA), neurobiology and anticonvulsant data from the US National Institute of Neurological Disorders and Stroke (NINDS), Approved Drug Screening Program (ADSP) and the US National Institute of Mental Health (NIMH) Psychoactive Drug Screening Program (PDSP), high-throughput screening results from ChemBank 18, and target profiling and phenotypic assays from commercial vendors. In addition, a variety literature-extracted ligand-protein binding and bioactivity data are from the BindingDB 19, the IUPHAR 20, and the PDBBind 21 projects etc.  \n\nTo date, PubChem BioAssay has biological activity data for more than millions of unique small molecule chemical structures and tens of thousands of siRNA probes annotated for several thousand different protein and gene targets from thousands of biochemical and cellbased bioassays. For a given PubChem Bioassay, all related data objects are stored in ASN.1 format (gzipped) and also available in XML and CSV file formats under Microsoft SQL relational database server with optimal database architecture for efficient storage, tracking and fast retrieval of large-scale biological test results. PubChem BioAssay datasets can be downloaded free via the PubChem FTP site 22. Assay data table and descriptions can also be retrieved and downloaded through a programmatic interface using the PubChem Power User Gateway (PUG/SOAP) facilities 4, 23. The various query functions are available for searches of compounds, substances, or bioactivity data information using either text or structure queries. Text searches include compound names, molecular formulas, keywords, descriptors or MeSH terms, etc. Structure searches include identity or similarity search as well as substructure or superstructure query with online structure-drawing tool, or using SMILES, SMARTS or InChI as a structure identifier (Figure 1). Users can search using any combination of Entrez and PubChem search tools, and then download data for further analyses and computational studies.  \n\nThe various download export formats for chemical structures include SDF, SMILES, XML, InChI, images and ASN.1. Note that ASN.1 (Abstract Syntax Notation One) is a binary format. NCBI utilizes a textural description translated from ASN.1 as the PubChem native archive data format that is both computer and human readable 6. All other data formats (such as SDF) are converted from the original ASN.1. SDF file format is the industry standard 24 for conveyance of chemical structure information. SDF format, however, does not provide all aspects of the ASN.1 data and may not contain all archived information in ASN.1 data format. For the extensive description of PubChem data structure systems as well as annotation and analysis tools that link phenotypic outcome to the chemical structures of molecules screened, the reader is referred to the comprehensive description articles published by S. Bryant and NCBI scientists 4-6, 25. Furthermore, the quantitative assessment of the PubChem and other public databases as well as commercial databases of bioactive compounds was reported in a recent review 26.  \n\nIn addition to the full records of PubChem compound library, several laboratories have developed cheminformatics tools to generated structurally diverse or 3D shape diverse sublibraries from the large PubChem database 27-29. These subset libraries are much smaller but representative to the parent library, showing minimum similarity and redundancy. Xie et al. at the Pittsburgh Molecular Library Screening Center (PMLSC) reported their studies on data-mined PubChem using a chemistry space based compound profiling algorithm to create a representative subset of compounds from PubChem 27. The total number of compounds was reduced to 540,000 from approximately 5.3 million to make in silico or in vitro screening of PubChem more manageable 27. In addition, 3D shape topology diversity 28, 29 and scaffold topology diversity 30 analyses were also applied to modeling PubChem chemical library, which are reviewed below.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.2. PubChem representative subsets  \n\nPubChem as a valuable public molecular information resource repository has attracted many cheminformaticians and biologists to carry out in silico or in vitro high throughput screening (HTS) to identify novel hits with new chemical scaffolds and high affinity but low toxicity. One of the challenges for the scientists is to handle the multiple millions of compounds. It may be unrealistic to conduct direct HTS experiments to screen multi-millions of compounds in PubChem for each biological target on a weekly or monthly basis. For example, the NIH MLP only requires MLPCN comprehensive centers to perform 20 assays per year for screening about 300,000 compounds and then deposit the screening data into the PubChem database. Of course, modern HTS technologies can now screen millions of compounds more quickly and cheaply at costs much less than earlier HTS methods31 However, at screening rates of 300,000 compounds/week, it may still be a challenge for an academic institution to support on a weekly basis without the major funding support to cover the costs of HTS programs and resources as well as the assays development. Overcoming these limitations requires innovative approaches, either through development of fast and low-cost HTS experiments or by employing a cheminformatics approach to taper down the large compound library without losing its information of original molecular properties as well as structural diversity. A few of such representative sub libraries have been reported as discussed below.  \n\nExpert Opin Drug Discov. Author manuscript; available in PMC 2011 December 1.  \n\n2.2.1. Structurally-diverse representative subsets from PubChem—Xie et al. 27 have established a computational method of building representative sub-libraries from large PubChem compound database by combining a partitioning cell-based BCUT metric algorithm with pair-wise 2D fingerprint similarity search as illustrated in Figure 3. In their studies, they applied the established diversity analysis method to generate a representative sublibrary with $\\sim10\\%$ of the size of the parent compound library. Their results show the new subset has minimum similarity and redundancy, but greater structural diversity, and no loss of the molecular properties based upon distribution analyses of HB donor/acceptors, rotatable bonds, hydrophobes, MW, and logP, relative to the parent library PubChem 27. The generated representative subset (rePubChem) is made available to the cheminformatics community through former PMLSC websites.  \n\nXie's laboratory has further developed the representative subset selection algorithm into a compound library profiling (CLP) method, and applied it to perform diversity analysis of newly synthesized cyclic ether compound library in comparison to the existing PMLSC compound collection and the PubChem database32, and also to characterize the diversity attributes of the synthesized bicyclic $\\upbeta$ -benzyloxy and $\\upbeta$ -hydroxy amide library in comparison to NIH small molecular repository (SMR) to which these new compounds are deposited 33. In these publications, the developed compound library profiling (CLP) algorithms provides valuable cheminformatics data mining tools to evaluate whether the newly synthesized compounds contribute to increase the diversity value of the existing NIH SMR compound libraries or commercial chemical library. It is anticipated that these methods and compound subsets will be valuable to a broad scientific community interested in acquiring/synthesizing structure-diverse compounds for efficient drug screening, and for more general applications requiring representative virtual compound libraries.  \n\nAdditionally, Xie et al have applied the BCUT-based chemistry-space matrix calculation algorithm established above to build target-focused sub-libraries based on the few known active leads identified by PMLSC HTS experiments. Such a knowledge-based “cherrypicking” approach used a few known active compounds (or the corresponding chemistry-space matrices) to select additional compounds that have similar chemical-space matrices, and then cluster them to build target-focused sub-libraries. In these studies, the unbiased modeling of PMLSC datasets has demonstrated that the clustered libraries generated by this approach have hit rates remarkably better than classical HTS experiments as shown in Figure 4 (unpublished data). 3D diversity matrix plot shows the parent library (green dots: 65K compounds distributed to PMLSC from DPI) (Discovery Partners International, BioFocus Inc) and a generated sublibrary (targeting West Nile Virus NS2bNS3 Proteinase, NS2B) (blue dots: 220 compounds), computed by chemistry-space BCUT metrics diversity analysis approach 27. As shown in Figure 4, the focused library (220 compounds) (blue dots) were generated based on the two compounds known to bind NS2B (yellow dots) that were originally identified from a representative subset of 9013 compounds (above). There are 11 hits (red dots) in the focused library that match 11 of the 15 hits from HTS experiments on the full 65K compound library. The focused library thus gives a $5\\%$ (11/220) hit rate, which is 250 times higher than the $0.02\\%$ (15/65k) hit rate of the initial HTS experiments. In addition, the focused subset provides a concentrated subset for the secondary HTS experimental screening to further examine any possible false negative hits.  \n\n2.2.2. Other diverse sublibraries from PubChem—In addition to the chemistry space matrix compound profiling algorithm to mine PubChem library above, Fontaine et al. reported a 3D shape fingerprint similarity selection method using ROCS shape overlay comparison algorithm to mine PubChem database 28. In their studies, approximately 1.04 million PubChem compounds were obtained with filtering criteria: heavy atoms $^{<28}$ ,  \n\nrotatable bonds $^{<6.}$ , and removing the structures with incomplete stereochemistry, ionized forms. Then, a set of a few thousands diverse structures was generated using 3D shape Tanimoto similarity (Tc) values of 0.75, and also analyzed under different 3D shape Tc values of 0.8 and 0.85. These calculated shape diverse subsets cover entirely the 3D shape space of the conformers of the 1.04 million PubChem compounds. Similar work 29 was also reported for assessment of conformational space of PubChem compounds by using conformation generation program Omega 34 and regression equation prediction as a function of RMSD.  \n\nThe advantage of the above 3D shape overlap subset library selection methods is that it allows visualization of the superimposed compounds and a better understanding of the compound similarity. For millions or billions of conformers, however, 3D alignmentbased shape similarity searches in comparing with 3D shape fingerprint similarity method demands substantial computing capabilities and modeling resources in addition to the precomputation requirements.  \n\nFurthermore, Wester and Oprea have reported their work using scaffold topologies to model various datasets from PubChem and DSSTox for toxicity studies 30. In their studies, they compared the results of different algorithms including the ring scaffold topology distribution in comparing to coarser-grained classification against several databases, including ChemNavigator (commercial chemicals), DNP (the Dictionary of Natural Products), WOMBAT (medicinal chemistry compounds with known bioactivity), and two subsets “active” from PubChem and DSSTox (toxic compounds) as well as GDB11 (General Database of Chemical Space of virtual small organic molecules with major atoms less than 11 or MW less than $160{\\bar{\\mathrm{Da}}})^{35}$ . The topological results show that nearly $34$ of the scaffolds of toxic substances have two or less rings but $25\\%$ of DSStox and $4\\%$ of the PubChem actives do not contain rings (note: the DDSTOX chemical-index files have now been deposited into PubChem under “PubChem Substance”). The maximum topological diversity is observed in PubChem and $55\\%$ of PubChem's have less or equal to 8 ring size topologies.  \n\nIn general, the subset chemical library will allow biologists and computational chemists to efficiently screen the sets of compounds that are small enough to be tractable, yet representative of the full set. Hits obtained from such a representative library can then be used to rationally parse the parent library, and generate a compound cluster or focus (similar compounds or analogs) for further bioassay validation, resulting in the rapid development of informative structure-activity relationships (SAR). The basic idea underlying the diverse subset selection strategy is based on a central premise of medicinal chemistry that structurally similar molecules have similar physicochemical properties and possibly similar biological activities, which premise has been enunciated in many computational chemistry and similarity-based virtual screening drug design studies.36-38 Of course, very similar molecules may in some cases possess very different activities, so called activity cliff that is defined as the ratio of the difference in activity of two compounds to their distance of separation in a given chemical space. The detailed discussions of outliers or activity cliffs are beyond this review but available in literature 39, 40.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3. PubChem Benchmark Datasets and Virtual Screening Models",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3.1. Opportunities and challenges of modeling PubChem library  \n\nThere are many successful virtual screening methods reported for chemical probes or drug leads discovery, either based on ligand pharmacophores or receptor docking approaches 41-45. However, one of the basic preconditions to develop virtual screening approach for a drug target or conduct in silico validation studies is to ensure the availability of reliable bioassay datasets. The dataset is often randomly divided into training set and  \n\ntesting set, each may consist of known numbers of active and inactive data. The known datasets are used to assess the virtual screening methods according to their capability to separate the actives from inactive in the final ranking, or calculate the enrichment factor of the different in silico methods. Thus, dataset selection and model training/validation are another important step for virtual screening in addition to construct high-quality structurally diverse compound library as reviewed in the previous section.  \n\nAs discussed above, the PubChem bioassay collection has rich data information. It provides great opportunities and also challenges for computational studies to reveal relationships between chemical structures and biological activities in order to assist virtual screening and computer-aided drug design. A common exercise for dataset extraction from PubChem is to first extract all bioassays that have defined the specific protein targets from PubChem and then extract the datasets that were screened by primary bioassays and also confirmed by secondary dose-response bioassays (Ki or EC50).  \n\nHowever, like other HTS/HCS screening experiments, the PubChem bioassay data may also suffer from the experimental noise and artifacts, such as false positives or false negatives. For example, bioassays are prone to a range of artifact caused by unspecific binding activity of the screened chemical compounds, such as off-target or cytotoxic effects in cell-based receptor bioassays 46. Thus, cautions should be taken when extracting bioactivity data from PubChem for computational studies. Usually, the secondary and confirmatory bioactivity data should be used in the computer modeling. In addition, the datasets extracted from PubChem or from the literature may also suffer from issues of compound analogues bias that are often prone to over-representation of certain scaffolds or chemical entities 47. The analog bias issue may cause overoptimistic estimates of virtual screening performance.  \n\nThus, it is essential and important to have trust-worthy bioactivity datasets extracted from PubChem in order to develop reliable predictive models for virtual screening and method development in terms of performance assessment and algorithm validation.  \n\nWhile PubChem curators do check assay depositions, however there is no way to completely avoid erroneous data in PubChem as HTS data is prone to experimental noise. To deal with these complications of the large bioassay data in PubChem, several research laboratories have developed various cheminformatics tools and filtering methods to construct so called benchmark datasets by careful selection of the raw data sets from PubChem. These subsets will be great value for library design and virtual screening method development and validation. These reported studies include: developing predictive decision tree models from HTS data in PubChem 48, data mining PubChem using support vector machine (SVM) for inhibitor or ligand classifications 49-54 and aggregator identification 55, establishing GPU accelerated SVM for mining HTS data 56, and developing naïve Bayesian predictive models from PubChem Bioassay datasets 13. Figure 5 illustrates a Web-interfaced machine learning algorithm based ligand activity predictor and function classifier that were developed by Xie et al to predict active/inactive ligands and agonist/antagonist of 5HT1A using naïve Bayesian and SVM algorithms, respectively 57. The prediction models were constructed from over 1600 of known 5HT1A ligand datasets from the PubChem database (data source from GLIDA 58). These established data-mining algorithms provide valuable statistical approaches to mine large bioassay datasets for virtual screening. Ideally, with the high volume biological data from PubChem, cheminformaticians and computational chemists/ biologists can use the unbiased datasets to develop and evaluate in silico drug design algorithms and methods for the best virtual screening performance across a range of datasets from PubChem. A few examples of the extracted PubChem datasets and cheminformatics studies are discussed below.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3.2. Benchmarking of the PubChem datasets and virtual screening models  \n\nRoherr and Baumann 59 have reported their cheminformatics research work on developing the maximum unbiased validation (MUV) datasets for virtual screening. The work was based on PubChem bioassay data by using refined K nearest neighbor (KNN) analysis algorithm. In their studies, all datasets and the chemical space samples were encoded by “simple” descriptors that are a vectorized form of the respective counts of all atoms in each molecule. The descriptors include the number of H-bonding acceptors and H-bond donors, the logP, the number of chiral centers and the number of ring systems 59. Subsequently, a workflow of topological optimization using MUV dataset design strategies, monitored by refined nearest neighbor analysis functions, was established to generate corresponding datasets of actives and inactives from PubChem. From the bioactivity data available in PubChem BioAssay, 18 subsets of bioactivity data, which were primarily screened and then confirmed by dose response assays, were extracted against 18 pharmaceutically relevant targets, and each dataset consists of 30 actives and 15000 inactives. The authors concluded that these benchmarked datasets are unbiased with regard to analogue bias and artificial enrichment, which can be used to maximize the unbiased validation of virtual screening methods. Their benchmarked unbiased datasets generated from PubChem and the associated statistics analysis tools are available for download at author's website 59.  \n\nFurthermore, Chen and Wild 13 have generated a Bayesian predictive models using 1133 bioassays in 2008 from the PubChem database. Using their workflow built by Pipeline Pilot package 14, the naïve Bayesian predictive model was built with the FCFP_6 circular substructural fingerprints 60 and the molecular descriptors encoded structural features and properties, including molecular weight, logP, number of H-bond acceptor and donors, the number of rotatable bonds. The developed models were accessed using Leave-One-Out validation (or internal validation) and the rational division of training and testing datasets validation (external validation) 61. Their studies showed that these predictive models are reasonably accurate by identifying high number of hits with the enrichment factor 3.6 and 5.7, which is much better than either similarity search or random screening. It is a good practice to build the predictive models using a rich and diverse compound datasets to ensure the development of a generalizable model with better accuracy. The variability in the accuracy $(\\mathrm{ROCV}=0.582\\mathrm{-}0.995$ , mean 0.881) is, however, still greater than that for models built using traditional QSAR data $\\operatorname{ROCV}=0.985{-}0.998$ , mean 0.992)13. Thus, future work is necessary to improve the accuracy of predictive model by introducing a more diverse inactive set as baseline.  \n\nAdditional machine learning algorithm was also applied to mine PubChem datasets. Weis et al. 49 established a support vector machine (SVM)-based classification algorithm to screen and identify the Factor XIa inhibitors from over 12 million compounds in PubChem database. In their studies, a support vector machine (SVM) classifier was trained to develop a predictive model using the Signature molecular descriptor on Factor XIa inhibitor HTS data. The resulting model had a 10-fold cross-validation accuracy. To further evaluate compounds identified as active by the SVM, docking studies were performed using AutoDock to generate a focused subset of compounds predicted to be active. It is anticipated that the established data mining technique for factor XIa inhibitor identification could also be applied to other bioassays in PubChem for identification of chemical probes.  \n\nAs shown above, machine learning and statistical inference have provided alternative solution to model millions PubChem datasets and to develop predictive models for virtual screening. While these methods still need improvement, they do demonstrate robustness and predicting power to handle large amount of datasets from PubChem.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3.3. Virtual Screening based on the imbalanced bioassay data in PubChem  \n\nIn addition to the given very large, high volume and complicated datasets mentioned above, another challenge to mining PubChem for virtual screening is the highly imbalanced nature of the PubChem data with only a small number of active compounds compared to inactive compounds. To deal with this issue, Bryant et al. reported a method for mining these highly imbalanced HTS data in PubChem51. In their work, the granular support vector machine $(\\mathrm{g}\\mathrm{SVM})$ repetitive under sampling method (gSVM-RUS) 62 and PubChem fingerprints 63 were used to build predictive models using the luciferase inhibition bioassay data that has the imbalanced ratio of active/inactive (1/377). The best predictive model developed showed hit rate of recognizing the active and inactive compounds at the accuracies of $86.6\\%$ and $88.9\\%$ with a total accuracy of $87.7\\%$ by cross-validation test and blind test, respectively. Their results demonstrated the robustness of the gSVM-RUS based predictive model in efficiently computing the highly imbalanced HTS data. It is anticipate that the developed gSVM-RUS algorithm may also help HTS assays such as luciferase-based HTS to develop a computational model to screen and identify potential interference compounds for the HTS assays.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 4. PubChem Toxicology Prediction Modeling",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# 4.1. Challenges for modeling of limited toxicity data from PubChem  \n\nIdentification of hits or leads from HTS or virtual screening approaches is important first step. However, many screened compounds entering clinical studies do not survive through the numerous hurdles as a good pharmacological lead to be a drug on the market. Among many causes for attrition that have been studied, it has been noted that earlier attention to compound quality related to physical chemistry, drug metabolism and pharmacokinetics (DMPK), and toxicology/safety is necessary and important. In PubChem bioassay collection, cell viability studies as an indication of general cellular toxicity were also carried out using HTS cell proliferation experiments by measuring ATP concentration 64. The study attempts to correlate generic cell-proliferation to chemical features by analysis of cell proliferation results from different cell lines. Ideally, the development of predictive cellular toxicity models would be useful cheminformatics tools to mine the PubChem data in order to reliably predict compounds whether they are toxic or not. Here, the reviewer would like to point out that such generic cell proliferation assays do not address any specific mechanisms or targets involved in toxicity. It only gain some mechanistic insights by analysis of cell proliferation results from different cell lines in attempts to correlate generic cell proliferation to chemical features 65.  \n\nFor modeling PubChem data for toxicology and pharmacology studies, there are several ADME/Tox databases available free or commercial on the web that can be used to facilitate computational toxicology model building and assistant drug design 66. A number of computational toxicology approaches has been developed and reported to predict whether a compounds that are toxic or have poor ADME properties, including linear regression models 67, neural networks models 68, Kohonen maps prediction model 69, Bayesian models 70, expert system models 71, QSAR models 72, target fishing technique 70 and Prediction of Activity Spectra for Substances (PASS) 73, and public sources for toxicity data review 17. These toxicology prediction methods are similar in nature but use a variety of molecular descriptors to derive predictive models either to predict LD50 values quantitatively or to perform classification of toxic or not toxic qualitatively. Here, the reviewer should point out that the PubChem toxicity data are still limited on certain species or specific classes of compounds; in particular it is still a challenge to identify toxic compounds in the absence of knowledge of toxicity mechanisms. Some of these related studies are reviewed below.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 4.2. Cell toxicity predictive models from PubChem  \n\nGuha and Schuere investigated various aspects for developing computational models to predict cell toxicity based on cell proliferation screening data in PubChem 65. Based on the captured features in the datasets, several predictive models were generated to evaluate cellbased screening results and were used to identify and eliminate potentially undesired compounds. In addition, they explored the feasibility of utilizing cell proliferation data to predict animal toxicity using the datasets from PubChem and MDL databases. In their studies, human T cell (Jurkat) proliferation data were extracted from PubChem using Assay ID: AID's 364, 463 and 464, including over 60,000 data points with primary percent inhibition measured at $4{\\mathrm{uM}}$ and about 800 IC50 data points. To investigate the generality of the workflow established, the cell proliferation quantitative HTS (qHTS) IC50 data points for 1334 compounds against 13 cell lines were extracted from various PubChem BioAssay collection (AID's). For a given cell line, a criteria was set that compounds with a pIC50 greater than the cutoff are labeled as toxic and those below as non-toxic.  \n\nTo correlate the in vitro toxic prediction with the animal toxicity datasets, authors extracted the acute animal toxicity datasets from the Registry of Toxic Effects of Chemical Substances (RTECS) available through the MDL Toxicity Database (2006.2), including 103,041 chemical structures for 154,019 LD50 $(\\mathrm{mg/kg})$ data points (oral, intravenous, intraperitoneal, subcutaneous). A cutoff of LD50 was selected such that any molecule having a measured pLD50 of two standard deviations greater than the mean value was classified as toxic and the rest as non-toxic. To identify toxicity-indication structural pattern and derive the predictive models, Guha and Schurer used the BCI 1,052-bit structural descriptors as structural fingerprints, CATS2D descriptors as topological pharmacophoric fingerprints, and Molconn-Z real-value holistic descriptor for all three of the datasets mentioned above. Their work showed that the models generated exhibit reasonably good predictive performance on these highly imbalanced datasets from PubChem and MDL, with accuracy rates ranging from 56 to $80\\%$ . According to their data, simple structural descriptors, binary fingerprints or topological pharmacophores, do not appear to allow for a consistent discrimination between toxic and non-toxic classes. This is particularly true when comparing cell-based and animal toxicity.  \n\nAdditional toxicity prediction models were also reported using PubChem datasets and DSSTox database. Edelstein et al. 74 extracted three datasets from the DSSTox database and integrated the information from PubChem and ChemBank for development of predictive toxicology models. Their studies showed that the correlated toxicology modeling can improve predictive performance over using chemical structure alone in a statistically significant way. Zhu et al. 75 also reported their work of modeling cell viability assay data to improve the prediction accuracy of conventional QSAR models of animal carcinogenicity. Their studies concluded that combining NTP-HTS profiles with conventional chemical descriptors could considerably improve the predictive power of computational approaches in toxicology.  \n\nClearly, given no target information, modeling toxicity is complicated because of the multiple mechanisms and biological targets by which a compound may inhibit cell proliferation. Thus, it is recommended that specific mechanism related descriptors should be included, such as a variety of physicochemical descriptors (clogP, polar surface area, Hbonding, charge etc.) and bioactivity-based descriptors (biological descriptors76, target protein interaction descriptors derived from proteomics and gene expression 77, metabolism descriptors 78). These mechanism-related descriptors can help to understand specific mechanisms and possible interactions of a toxicant that may have with a biological systems.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 4.3. Cardiac toxicity prediction models from PubChem  \n\nAnother reported toxicology virtual screening study is the cardiac toxicity prediction model development. Li et al. have published their work on cardiac toxicity classification model using a combination of SVM and GRIND descriptors, and tested the model on a large set of hERG bioassay data from PubChem (AID:376) 50. Cardiac toxicity of drugs is a major concern in drug discovery. It often requires elimination or filtering out potential hERG channel inhibitors in an early stage of drug discovery process. In their studies, a large set of compounds (1948 compounds) with hERG activity was extracted from PubChem bioassay database (AID:376), containing 248 active and 1700 inactive compounds. Initially, docking studies were carried out using 561 molecules (495 from the training set and 66 from the testing set) on a constructed hERG homology model. Then, a binary classification prediction models were generated based on the 495 compounds using pharmacophore-based GRidIndependent Descriptors (GRIND) with a SVM classifier in order to discriminate between the hERG blockers and nonblockers. According to their studies, the models achieve an overall accuracy up to $94\\%$ with a Matthews coefficient correlation (MCC) of 0.86 $F$ - measure of 0.90 for blockers and 0.95 for nonblockers) 35. The models were also applied to a testing dataset of 66 compounds, showing $72\\%$ of the set was correctly predicted $F.$ - measure of 0.86 and 0.34 for blockers and nonblockers, respectively). Finally, authors also evaluated the model on a large set of hERG bioassay data in PubChem, showing $73\\%$ accuracy ( $F$ -measure of 0.30 and 0.83 for blockers and nonblockers, respectively) and $10\\%$ improvement in the prediction of blockers compared to other methods. They concluded that the generated models based on GRIND descriptors and SVM classifier can be useful to filter potential hERG channel inhibitors.  \n\nIn general, it is expected that the PubChem biological categorization of datasets is growing rapidly and it will become a valuable resources to advance the complicated pharmacology and toxicity prediction. In addition, more ADME data will be available from physicalchemical and ADMET in vitro assays either in the public and commercial databases or pharma companies' in-house databases. The current public toxicity databases are: DrugBank 79 $\\mathord{>}4800$ drug entries related to over 2500 non-redundant target proteins), Environmental Protection Agency's (EPA) Distributed Structure-Searchable Toxicity (DSSTox) Database 80 (over 10,000 unique chemicals), new EPA Aggregated Computational Toxicology Resource (ACToR) database 81 (over 300 chemicals pertaining to environmental toxicology). The commercial preclinical ADME/Tox databases include: Symyx database (metabolite and toxicity data) 82, Aureus AurSCOPE $\\textcircled{8}$ ADME/DDI database 83(drug-drug interaction and metabolic properties of drugs), PharmaPendium online resource 84 (FDA approved drug data and EMEA EPAR approval documents). These databases in combining with datasets from PubChem will provide rich molecular toxicology information for cheminformatics and virtual screening.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# 5. PubChem across-target polypharmacology network modeling  \n\nOne of the important features of the PubChem data collection is that it reports the activity of compounds across multiple Bioassays, which allows to mining across-target bioactivity and study polypharmacological behaviors in the PubChem collection via cross-assay analysis studies. An example is given in Figure 6 to show that a PubChem Heatmap and clustering graphs displaying the cannabinoid ligand CP55940, a known analgesics and immunosuppressive agent, together with their biological test results that were obtained from HTS experiments against a group of related protein Targets. The compound CID104895, a stereoisomer of CP55940, is a a known potent GPCR ligand that has nanomolar binding affinity to cannabinoid receptors. As shown Figure 6, the compound CID104895 also shows across-target bioactivities to the other GPCRs proteins, including weak binding (green color: $10\\mathrm{-}100\\mathrm{uM}$ range) to neuropeptide S receptor isoform A (target identification,  \n\nGI#46395496: a G-protein coupled receptor for asthma susceptibility) and relative strong binding (yellow color $0.1\\mathrm{-}1\\mathrm{uM})$ ) to thyroid simulating hormone receptor (target identification, GI#38016895: another GPCR). The across-target multiple bioactivity data were measured by NIH NCGC using PubChem BioAssays AID1461 and AID926, respectively. More studies were reported on using PubChem data and online analysis tools to survey selectivity and across-target bioactivities of small molecules as discussed below.  \n\nChen et al. reported their modeling studies using PubChem as a data source to establish polypharmacology networks 85 in order to address the issue of high attrition rates arising from lack of efficacy and high toxicity. In their work, sets of data were extracted from PubChem bioassays collection, containing 602 bioassays for 506,190 distinct compounds, of which 90,290 compounds were active in at least one assays. The assays represented 258 unique protein targets, and each target was tested in multiple assays, whereas the assays that did not have an associated target were ignored. Then, authors derived a network representation of these assays collection and applied a bipartite mapping between the assays network and various biological pathways network as well as artificial drug-target network. The results demonstrated that mapping to a drug-target network can be allowed to prioritize new selective compounds, whereas mapping to other biological networks can be used to observe interesting target pairs detected in PubChem cross-assay analyses and the corresponding compounds in the context of biological systems.  \n\nAnother similar cross-assay analysis study was reported by Han et al 9 regarding a datamining survey of across-target bioactivity results of small molecules in PubChem. In their report, two alternative target-grouping approaches were used to examine a compound's across-target bioactivity against 588,918 compounds under 660 bioassays. The established non-redundant target-based compound analysis methods revealed compounds that are selectively active against groups of protein targets that have identical or similar sequences. The target clustering analyses identified compounds that are bioactive across unrelated targets. One of such target compounds studied is myricetin (PubChem CID:5281672), or a flavonoid commonly found in natural food source. The compound was identified by PubChem across-target analysis as an inhibitor of multiple target proteins such as aldehyde dehydrogenase, Leishmania mexicana Pyruvate Kinase, Cytochrome P450, Stress-activated protein kinase and human RNase H, with a strong potency $(\\mathrm{IC50}<10\\mathrm{uM})$ ).  \n\nClearly, PubChem provide bioactivity report via launching Entrez Bioassay Summary for scientists to examine and compare biological outcomes across multiple biological tests, which allows to view all active compounds across each BioAssay. The reviewer believe that data-mining analyses of bioactivity profile across a wide range of biological targets in PubChem provides promising statistical models to evaluate target specificity of promiscuous compounds for their selectivity and across-target properties. The systematic studies of polypharmacological behaviors in the PubChem collection via cross-assay analyseswill also offer better understanding of the biological mechanisms of ligand and protein interactions.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 6. Expert Opinion  \n\nIn the reviewer's opinion, PubChem is a powerful small molecule information repository and has valuable features and multiple functions with advantages over other available public or commercial databases of bioactivity data. First, all compound structures, bioassay conditions and experimental readouts are publicly accessible online. Second, most of the compound collections tested in each bioassay were already pre-selected for maximizing structural diversity and acquisition of the “druglike” properties. Third, all tested compounds, including both actives and inactives for each bioassay are archived in the database and available for structure-activity analyses. Most importantly, millions of unique small molecule chemical  \n\nstructures and tens of thousands of siRNA probes were biologically annotated by millions of biological activity outcomes. In PubChem, these compounds were measured using thousands biochemical and cell-based bioassays for different protein and gene targets. In addition, PubChem Substance, Compound, and BioAssay databases are fully integrated within NCBI's Entrez data retrieval system 86. With the PubChem Power User Gateway (PUG) programmatic interface 23 and the Entrez Programming Utilities (eUtils) 10, one can perform automated chemogenomics analysis of the tested compounds and their bioactivities by correlating with the target proteins or DNA information87 as well as other database resources25.  \n\nHowever, PubChem data also suffers from the typical tendency of HTS/HCS assays for false positives and negatives as well as many highly imbalanced datasets. Cautions should be taken in utilizing these datasets as it may affect the virtual screening baseline noise and deviate the virtual screening prediction accuracy. It is also noticeable that PubChem toxicity HTS data is still limited to certain species or specific classes of compounds although more in vitro cellular toxicity data are becoming available in PubChem. Thus, it is still challenging to identifying toxic compounds in the absence of knowledge of toxicity mechanisms. It should be also noted that the in contrast to animal toxicity studies, the generic cell proliferation assays do not address any specific mechanisms or targets involved in toxicity. The cell-based toxicity studies, however, can be very cost-effective and suitable for highthroughput screening.  \n\nTaken all together, PubChem datasets can be used as a rich source to aid developing predictive models for cheminformatics and virtual screening for in silico drug design studies as reviewed above. Of course, one will not expect the accuracy to be as high as for highquality experimental sets. On the other hand, it is always recommended to make sure that models are built using a rich enough diversity of compounds for a generalizable model to be derived. It is also notable that the reported machine-learning derived models, as reviewed above, would be appropriate for virtual screening (or pre-screening) in order to reduce the number of compounds that need to be experimentally screened from large datasets like PubChem, but not for prediction on small sets that require very high levels of accuracy. Overall, the public accessibility to such HTS/HCS assay data is particularly valuable to the scientific community, since this kind of critical information needed by drug discovery research is typically held by pharmaceutical companies. The open-access and informationrich repository will make PubChem an even more valuable and powerful public resource for cheminformatics data-mining and virtual screening as well as biomedical and drug discovery research in the future.  \n\nArticle highlights box  \n\n• PubChem is a database of chemical molecules, a component of NIH's Molecular Libraries Roadmap Initiative.   \n• PubChem provides information on the biological activities of small molecules from a multitude of depositors. Currently, it has 69,170,468 entries of substances (SID), 27,443,646 records of unique chemical structure compounds (CID), and 449,401 records of Bioassays (AID).   \n• Multiple million records of PubChem datasets provide great opportunities and also challenges for developing cheminformatics tools and modeling algorithms that are suitable to handle high volumes of PubChem compound and bioactivity records for virtual screening and in silico drug design.   \n• As other HTS/HCS, PubChem bioactivity data may also suffer from the experimental noise and artifacts, such as false positives or false negatives. It is important to have confirmatory bioactivity datasets extracted from PubChem in order to develop reliable predictive models for virtual screening method development and validation   \nNovel data-mining cheminformatics tools and virtual screening algorithms are being developed and used to retrieve, annotate and analyze the large-scale and highly complex PubChem bioactivity data in order to facilitate computer-aided drug design.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# Acknowledgments  \n\nThe author would like to thank Dr. Billy Day for reading this manuscript.  \n\nDeclaration of Interest: XQ Xie has received funding support for his laboratory from the NIH (R01DA025612 and P50 GM067082).",
+        "category": " References"
+    },
+    {
+        "id": 21,
+        "chunk": "# 7. Annotated bibliography  \n\nPapers of special note have been highlighted as either of interests (\\*) or of considerable interest $(^{**})$ to readers.  \n\n1. MLPCN. Molecular Libraries Probe Production Centers Network (MLPCN), NIH Molecular Libraries Program (MLP). cited; Available from: http://mli.nih.gov/mli/mlpcn/mlpcn/   \n2. NCBI. NIH, National Center for Biotechnological Information (NCBI). cited; Available from: http://www.ncbi.nlm.nih.gov/   \n3. PubChem-Sources. PubChem Substance and Bioassay data source information website. cited; Available from: http://pubchem.ncbi.nlm.nih.gov///sources/   \n$4^{**}$ . Wang Y, Bolton E, Dracheva S, Karapetyan K, Shoemaker BA, Suzek TO, et al. An overview of the PubChem BioAssay resource. Nucleic Acids Res. 2010 Jan; 38(Database issue):D255–66. [PubMed: 19933261]   \n$5^{**}$ . Wang Y, Xiao J, Suzek TO, Zhang J, Wang J, Bryant SH. PubChem: a public information system for analyzing bioactivities of small molecules. Nucleic Acids Res. 2009 Jul 1; 37(Web Server issue):W623–33. [PubMed: 19498078]   \n$6^{*}$ . Bolton EE, Wang Y, Thiessen PA, Bryant SH. PubChem: Integrated platform of small molecules and biological activities. Annu Rep Comput Chem. 2008; 4:217–41.   \n7. Huryn DM, Cosford NDP. The molecular libraries screening center network (MLSCN): identifying chemical probes of biological systems. Annu Rep Med Chem. 2007; 42:401–16.   \n8. Oprea TI, Bologa CG, Boyer S, Curpan RF, Glen RC, Hopkins AL, et al. A crowdsourcing evaluation of the NIH chemical probes. Nat Chem Biol. 2009 Jul; 5(7):441–7. [PubMed: 19536101]   \n9\\*. Han L, Wang Y, Bryant SH. A survey of across-target bioactivity results of small molecules in PubChem. Bioinformatics. 2009 Sep 1; 25(17):2251–5. [PubMed: 19549631]   \n10. Entrez. NIH NCBI Entrez Programming Utilities (eUtils). cited; Available from: www.ncbi.nlm.nih.gov/entrez/query/static/eutils_help.html   \n11. Rosania GR, Crippen G, Woolf P, States D, Shedden K. 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Symyx. Symyx' Metabolite and Toxicity database. cited; Available from: http://www.symyx.com/products/databases/bioactivity/index.jsp   \n83. Aureus-AurSCOPE-ADME/DDI. Aureus AurSCOPE $\\textcircled{8}$ ADME/DDI databse provides the drugdrug interaction and metabolic properties of drugs. 2010. cited; Available from: http://www.aureus-pharma.com/Pages/Products/Aurscope_DDI.php   \n84. PharmaPendium. PharmaPendium online resource from Elsevier enables to search all FDA/CDER/ FOI archived FDA drug approval review data as well as an EMEA EPAR approval document database. 2010. cited; Available from: www.pharmapendium.com   \n85. Chen B, Wild D, Guha R. PubChem as a Source of Polypharmacology. Journal of Chemical Information and Modeling. 2009; 49(9):2044. [PubMed: 19708682]   \n86. Schuler GD, Epstein JA, Ohkawa H, Kans JA. Entrez: molecular biology database and retrieval system. Methods in Enzymology. 1996; 266:141–62. Computer Methods for Macromolecular Sequence Analysis. [PubMed: 8743683]   \n87. Zhou Y, Zhou B, Chen K, Yan SF, King FJ, Jiang S, et al. Large-Scale Annotation of SmallMolecule Libraries Using Public Databases. Journal of Chemical Information and Modeling. 2007; 47(4):1386. [PubMed: 17608408]  \n\n![](images/dee45dfd0aa1d6cf651558f16d386fe8d65cdbb86217ed41ebbda4965709c7be.jpg)  \nFigure 1. Brief overview of the PubChem Database system (A) The BioAssay data depositor list, including by NIH Molecular Libraries Probe Production Centers Network (MLPCN) and former Molecular Library Screening Centers Network (MLSCN) as well as other sources. (B) The PubChem database search window with online structure drawing/clustering, 3D view and data analysis tools, and the links to other databases as well as PubMed literature. (C) The query Output window (CID, SID and AID) and the files upload and download formats and tools  \n\n![](images/501b677c25a2986bdb5e7794b76caff0a18f26cdc8e9b8839389111f23dcc614.jpg)  \nFigure 2. A literature survey of the research publications related to PubChem and the key research fields from 2005 to 2010  \n\nThe insert table shows that the total number of the PubChem publication increases almost linearly from 2005 to now (The results were searched from SciFinder database).  \n\n![](images/04a46beef824020e7d2e22ecb71bc42fe7e5c10caf665c5c8eb8d18ea02926b3.jpg)  \nFigure 3. 3D chemistry-space matrix plot of a representative sublibrary (green dots) created from the parent library PubChem database (red dots) by using the Diversity Analysis method based BCUT metrics calculation.  \n\n![](images/c6adeeac060c636e5d2b48eb6754257a596765aa59c136d68b42594655644f3d.jpg)  \nFigure 4. 3D matrix plot of the NS2B-focused sub-library (blue dots: 220 compounds) selected from the parent library (green dots: 65K compounds from PMLSC)  \n\nThe focused subset was generated based on the two known NS2B-active leads (yellow dots) from the representative subsets (9013 compounds) by diversity analysis approach using cellbased chemistry-space BCUT metrics calculation. The focused library gives $5\\%$ hit rate (red dots: 11), which 250 times better than HTS experiments.  \n\n![](images/9829b674d7767837be7b36c62865835081a9e344994caa0957d27e1ca369da64.jpg)  \nFigure 5. Web-interfaced 5HT1A ligand activity and function prediction server Input widow has online upload or structure drawing functions, four fingerprint generators and choice of prediction algorithms. Backend in server has built in file format conversion as well as naïve Bayecian classifer for ligand activity prediction and SVM classifier for ligand function prediction functions. Output window displays the result of query compound AZD7371 (PubChem CID 3055171), showing that the compound is predicted to be an active 5HT1A ligand with antagonistic function to the 5HT1A receptor. The prediction models were modeled from known 1600 of 5HT1A ligands from PubChem database (GLIDA depositor).  \n\n![](images/189fdf2b70e10044d2ff166dac202cd6931a270e603269c9fbfe468c3f941deb.jpg)  \nPage 24  \n\nFigure 6.   \nA graph of PubChem Heatmap and BioAssay Cluster showing three isomers of the compound CP55940 and the correspondent biological test results across multiple targets that were measured from HTS experiments against a group of related protein targets. The three stereoisomers are represented as PubChem Compound identifier ‘CID’ and the structures at the right sides of heatmap. The three compounds were searched based on 2D structure similarity showing a similarity value of 1.0 (displayed at the left side of the heatmap), indicating they are identical structure but stereoisomers. Bioassay Clusters of the 11 assays (represented as PubChem BioAssay identifier ‘AID’) were derived based on the sequence similarity of the tested protein targets, where the GenBank identifiers of the corresponding protein targets (gi#) are listed at the bottom of the heatmap view. Each cell in the Heatmap represents an individual activity outcome of a small molecule for the corresponding target, with ‘active’ results denoted by red, yellow or green color, and ‘inactive’ results denoted by blue color.",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Exploring Material Design Space with a Deep-Learning Guided Genetic Algorithm  \n\nKuan-Lin Chen # Department of Chemical and Biomolecular Engineering, Johns Hopkins University, Baltimore, MD, USA",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Rebecca Schulman #  \n\nDepartment of Chemical and Biomolecular Engineering,   \nJohns Hopkins University, Baltimore, MD, USA   \nDepartment of Computer Science, Johns Hopkins University, Baltimore, MD, USA   \nDepartment of Chemistry, Johns Hopkins University, Baltimore, MD, USA",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# Abstract  \n\nDesigning complex, dynamic yet multi-functional materials and devices is challenging because the design spaces for these materials have numerous interdependent and often conflicting constraints. Taking inspiration from advances in artificial intelligence and their applications in material discovery, we propose a computational method for designing metamorphic DNA-co-polymerized hydrogel structures. The method consists of a coarse-grained simulation and a deep learning-guided optimization system for exploring the immense design space of these structures. Here, we develop a simple numeric simulation of DNA-co-polymerized hydrogel shape change and seek to find designs for structured hydrogels that can fold into the shapes of different Arabic numerals in different actuation states. We train a convolutional neural network to classify and score the geometric outputs of the coarse-grained simulation to provide autonomous feedback for design optimization. We then construct a genetic algorithm that generates and selects large batches of material designs that compete with one another to evolve and converge on optimal objective-matching designs. We show that we are able to explore the large design space and learn important parameters and traits. We identify vital relationships between the material scale size and the range of shape change that can be achieved by individual domains and we elucidate trade-offs between different design parameters. Finally, we discover material designs capable of transforming into multiple different digits in different actuation states.  \n\n2012 ACM Subject Classification Computing methodologies $\\rightarrow$ Artificial intelligence; Computing methodologies $\\rightarrow$ Modeling and simulation  \n\nKeywords and phrases Machine Learning, Deep Learning, Computational Material Design, MultiObjective Optimization, DNA Nanotechnology  \n\nDigital Object Identifier 10.4230/LIPIcs.DNA.2022.4  \n\nSupplementary Material Software (Source Code): https://github.com/charliecharlie29/DeepLearning-Guided-Genetic-Algorithm archived at swh:1:dir:b857ed74a5167e203a399609e9eb71bbad7cb091  \n\nFunding This research is supported by Department of Energy under Grant No.DE-SC0010426 and by National Science Foundation under Grant No.EFRI-1830893 and by Army Research Office under Grant No.W911NF2010057.  \n\nAcknowledgements We would like to thank the Maryland Advanced Research Computing Center (MARCC) for providing cloud computing GPU services.",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# Introduction",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# Combinatorial Metamorphic Materials  \n\nThe structure of a device determines its function. It is interesting to ask how we might manufacture combinatorial metamorphic devices that can take on many different forms and functions in response to a wide range of triggers. As metamorphic devices are capable of achieving a wide range of potential functions, they allow users to choose a function fit for a particular task and to alter the shape of the device to access that function. Because one such structure could be transformed into a large set of target devices, a single metamorphic structure can be stored or carried in place of a large set of traditional devices. These reasons make metamorphic devices more flexible and versatile than their traditional counterparts. These advantages have stimulated researchers from a range of communities to explore the design and construction of metamorphic devices[1, 3, 17, 21] for applications such as soft robotics[10, 21] and even quantum computing[5].",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# DNA-co-polymerized Hydrogels as Metamorphic Materials  \n\nHere we consider a means to construct metamorphic devices in which specific biochemical cues, DNA sequences, trigger the shape change of specific hydrogel domains[2]. Each hydrogel domain contains DNA crosslinks that allow the material to expand into swollen state upon activating the domain with a specific DNA sequence (growing actuators) and contract into shrunken state upon de-activation with another DNA trigger (shrinking actuators). To understand how we might use these types of materials to create metamorphic structures, we ask how to design material structures from 4 sets of the following active materials: hydrogels with a specific set of DNA crosslinks, growing actuators and shrinking actuators (Figure 1). Using multistage photolithography[2, 8, 18] to assemble these materials should allow us fabricate metamorphic devices that react to biomolecular signals with high specificity.  \n\n![](images/b8cd1abae652127249601d4e59e1bfa899d9b8464e2081faac718e374dbc9248.jpg)  \nFigure 1 DNA-co-polymerized hydrogel. A set of 4 different materials that can be enlarged and contracted by DNA signal. Exposure to its shrinking signals prompts a material to enter its shrunken state, while exposure to its growing signal prompts a material to enter its swollen state. The signals are orthogonal (each affects only its target material and not others). Each material’s expanded and shrunken states are of somewhat different sizes.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# Metamorphic Multi-state Digit Transformer  \n\nDNA-co-polymerized hydrogels whose size can be bidirectionally controlled by DNA signals bring forth the possibility of building complex metamorphic materials. To explore this concept, we seek to investigate whether it would be possible to use the materials in Figure 1 to design a metamorphic digit transformer. We ask how one might build metamorphic devices using the 4 active materials with orthogonal DNA actuation systems and a passive material without a DNA actuation system. Each actuator system drives a specific domain into swollen state upon activation, and shrunken state when inactive. As a result, the device is multi-stable and has 16 possible states ( $2^{4}=16$ ) when all DNA actuators are used. Our goal is to find a design where as many of its final outputs as possible resemble the shape of different digits from 0 to 9. We consider concatenated segments of bilayer hydrogel segments as a design space. The overall outline of this process is shown in Figure 2. Because these devices must be fabricated using multistage photolithography, the resulting designs must be consistent with this mode of fabrication, which imposes physical limits on the design space. Each bilayer segment will typically be on order $500\\mu\\mathrm{m}$ in height and 250µm in width. In order for the curvature of the resulting structures to be governed by curvature along the lengthwise, segmented axis, the overall length of the structure must be significantly longer than either the structure’s width or height. Lithography also limits the sizes of the segments to be between 50µm and $5000\\mu\\mathrm{m}$ , below which size resolution becomes difficult to control, and above which would require a larger light source and mask. Moreover, we want to limit the number of distinct fabrication steps required, as difficulties such as alignment, device lift-off, and transfer increase rapidly with the number of fabrication steps.  \n\n![](images/bf18b41575093190d19f6d129dcfa6b3f1dcb9a05ebf5fb51f5bc6db2ddc765d.jpg)  \nFigure 2 Building a metamorphic digit transformer from DNA-co-polymerized hydrogels. A metamorphic digit transformer is a stack of bilayers of DNA-co-polymerized hydrogels. The digit transformer would be able to change its shape into the shape of different digits upon the activation of different biochemical actuation programs, which switch the conformation of the structure between one of multiple stable states.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# Machine Learning and Genetic Algorithm for Material Discovery  \n\nFinding a design for a structure with a large number of different forms is a challenge. This challenge increases as the number of design objectives (i.e. stable states) increases, and tighter physical and manufacturing limits are imposed. The design space, consisting of the types, arrangements, and lengths of hydrogel segments is too large to search through via trial and error, and the conflicting nature of the constraints also makes structured design methods challenging to consider. Inspired by how machine learning and artificial intelligence techniques have been transformative in different areas of material design and discovery[9, 11, 14, 20], we seek to design digit transformer devices by developing a computational material discovery method. The method we describe mimics Darwinian evolution[4, 19] (through the use of a genetic algorithm) and combines numeric simulation[15] with state-of-the-art machinelearning models[16]. The resulting system simulates and autonomously evolves generations of material design variants in-silico to find designs for devices that satisfy the multiple design objectives[7] we created (Figure 2).",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# Methods",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.1 Material Simulation  \n\nTo develop a geometric simulation platform for our DNA-co-polymerized hydrogel, we considered predicted values of changes in contour length ( $\\Delta$ L) and radii of curvature (RoC) during the expansion and contraction of bilayers consisting of different combinations of actuator types. The simulation of the material starts with defining a straight bilayer structured hydrogel with specified length and actuator pattern. We then look up the different values for RoC and $\\Delta\\mathrm{L}$ given the target actuated state. The final folded shape is then calculated using the segment length, derived RoC and $\\Delta\\mathrm{L}$ for each segment (Figure 3, top). We assume there is little stress along the horizontal axis and that the shape of the resulting structure is achieved by a linear “stack” of different segments then concatenate with one another to form a smooth curve (Figure 3, bottom).  \n\n![](images/06b863863991858b73a63f6952a0cec2313f2507b79855bd28af905697c32ef6.jpg)  \n$\\sqcup$ Figure 3 Simulation of DNA-co-polymerized bilayer hydrogel segment(s). The shape of a folded single segment is determined by the segment’s length and the two types of actuators that make up the segment and their actuation states (expanded or contracted), as the states determine the overall values for the change in radius of curvature and contour length. Here, the bilayer studied has system I (blue) in its contracted state in the bottom segment and system II (pink) in its expanded state in the top segment. In a device with multiple segments, simulation is done with the assumption that there exists little stress between the segments so that the final conformation is the integrated sum of each single segment simulated independently.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 2.2 Simulation of Device Curving  \n\nTo construct a simulated “device,” we create a list of segment lengths and a matrix of actuator types and their states. This design is encoded as a list $S$ of segment lengths and a list $P$ that encodes the actuator pattern (top then bottom) within each segment.  \n\n$$\n\\begin{array}{l}{S=\\{L_{1},L_{2},...,L_{n}\\}}\\\\ {P=\\{\\{X_{11},X_{12},...,X_{1n}\\},\\{X_{21},X_{22},...,X_{2n}\\}\\}}\\end{array}\n$$  \n\nwhere  \n\n$$\nX\\in\\{0,1,2,3,4\\}\n$$  \n\nwith 0 representing the passive system and 1 to 4 representing the 4 active materials.  \n\nA device’s design is determined by simulating the curving of the device in all 16 possible states (where each of the four actuator types is in each of the two distinct states). An example of the possible states of a typical design is shown in Figure 4.  \n\n![](images/59e3f7aef5e7039815d99dff2240b175ebd13bca189cb7221df47433a21d68af.jpg)  \nFigure 4 Example of a simulation of a device’s curving in each of its 16 states. Shown are the input design and a map of the predicted output shapes. In the input section, different colors represent different actuators and the length of each bilayer segment is shown to the segment’s right. The output diagrams show the predicted device shapes of all 16 possible actuation states. The label above each image specifies the actuator state (S2 designates system II, and so on, while ON designates the swollen state and OFF designates the shrunken state). For scoring purpose, the shapes are plotted in 28-by-28-pixels-images that are treated with a Gaussian blur filter ( $\\sigma=1$ ).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# 2.3 Deep Learning Model for Design Selection  \n\nTo efficiently automate the scoring and selection process for design optimization, we train a convolutional neural network (CNN) classifier[13] to distinguish the digit-similarity of the predicted geometric outputs. We use the Tensorflow library and train the model using a combinatory dataset consisting of the MNIST dataset[6] and an artificial dataset. We label twenty-four thousand images generated with the simulation platform manually to build an artificial dataset and add an additional class (class “10”) for images that do not look digit-like and instead look like random squiggles. This additional class helps the model recognize bad shapes and images that the hydrogel device most often bends into. We train a sequential convolutional neural network consisting of two 2D convolutional layers (with 30 and 15 filters) with 2D max-pooling layers following each convolutional layer, and three fully connected layers (with 128, 50, and 11 nodes) and train on the combinatory data-set. The relu activation is used in all layers except for the final classification layer, where the softmax function is used. We used the adam optimizer[12] with categorical cross-entropy loss function and trained for 50 epochs. This model is then used to score and select ideal outputs that resemble digits. During the scoring and selection process, we rotate the images to explore the full potential of the designs.  \n\n![](images/f5bbbeee6ef876d5561225b30416a3cdb0502cb9b2ec6ec3b5036c0363784b27.jpg)  \nFigure 5 Example of design output scoring and selection. After the simulation, 16 images are generated and scored by the CNN to determine whether each represents a digit or not. Note that the final classification layer of the CNN model has 11 nodes where the first 10 represent the score (or probability) of resemblance to digit from 0 to 9. The 11-th value represents the value of resemblance to non-digit-like images. We use the max value of each class to represent the result of each image and discard the result if the 11-th value is the maximum - meaning the CNN model determines that this image is highly unlikely to represent any digits. Thus, only images with “max digit probability” are selected after the scoring and selection process of the CNN model.(Note that notations for simulated outputs are same as shown in Figure 4.)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# 2.4 Genetic Algorithm  \n\nWe develop a genetic algorithm to evolve the material designs autonomously. The algorithm works by initiating a large batch of random designs with a fixed population size. At each iteration, the whole population is simulated and scored with the convolutional neural network(CNN) and a multi-objective loss function to determine the fitness score of each design.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 14,
+        "chunk": "# 2.4.1 Loss Function - Fitness Evaluation  \n\nWe tried a variety of different loss function to track and optimize design:",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# Fitness Evaluation on Digit Quality Alone  \n\nWe initially started the algorithm based on a simple loss function where only the digit quality is tracked and scored. This, however, leads to issues where designs that form a wide range of “mediocre digits” cannot compete with designs that form only a few number of “perfect digits”, and we lose these designs throughout the evolution trajectory. While it is more likely for these “mediocre designs” to evolve and grow into designs that can fold into all digits, this loss function reduces the survival chance for them and thus are not ideal for the search.  \n\n$$\nf i t n e s s=\\sum_{i=0}^{9}l o g(1-V_{i})\n$$  \n\nwhere  \n\n$V_{i}$ : the score of each digits where $i\\in\\{0,1,2,...,10\\}$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# Fitness Evaluation on Digit Diversity and Quality  \n\nMoving forward, we improved the loss function so that we evaluate the performance based on the diversity of the digits formed as well as the quality of different digits. The diversity is evaluated with $\\alpha$ , where we count how many digits a design formed. To calculate $\\alpha$ for each design, we iterate through the classification results of the outputs and count how many of them are classified as digits (with softmax-ed classification value ranging from $0$ to $9$ ). $\\alpha$ is the number of non-repeating digits formed. The quality of different digits is evaluated and stored in the list $V$ , and $V_{i}=0$ when the ith digit is not found. With this method we are more likely to find better designs and this loss function is used throughout the rest of the paper.  \n\n$$\nf i t n e s s=\\sum_{i=0}^{9}l o g(1.0001-V_{i})\\cdot\\alpha\n$$  \n\nwhere:  \n\n$V_{i}$ : the score of each digits where $i\\in\\{0,1,2,...,10\\}$ $\\alpha$ : diversity coefficient, the number of digits formed",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 17,
+        "chunk": "# 2.4.2 Mutation Function  \n\nOnce the whole population is scored, the population is then sorted according to the calculated fitness and 80% of the population is eliminated. The survivor designs are then delivered to a mutation function where we use the single-parent-mutation method to preserve the gene of each design and produce offspring. Each survivor design produces four offspring and sent with their offspring to the next generation to compete. This way the size of the population remains fixed throughout the evolution process. The iteration cycle continues until we reach the maximum generation limit.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# Mutation Function - Vanilla Form  \n\nMutation function is where we determine how the genetic information of the parent design is passed down to the offspring. The gene $G$ in our designs consists of two matrices, the segment list $S$ and the actuator pattern matrix $P$ , such that $G=G(S,P)$ . In the vanilla form of the mutation function, we randomly update either the $S$ or $P$ to mutate the genetic information, where each has a $50\\%$ chance of mutation. For the $S$ -mutation offspring, we randomly assign new $S$ while preserving the $P$ . For the $P$ -mutation offspring, we randomly swap out $50\\%$ of the genes within the pattern while preserving the $S$ . Note that instead of swapping out all the genes, only $50\\%$ of them are mutated to ensure enough of the genetic information is maintained.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 19,
+        "chunk": "# Mutation Function - With Fabrication Limit  \n\nAdditionally, we use a more advanced mutation function that accounts for the fabrication complexity to ensure that the converging designs are within reasonable physical limits. The form of the function looks pretty similar to the vanilla form above except for additional fabrication step calculation. We define the fabrication steps as the steps needed to pattern these gels with the photolithography setup. The steps needed depends on the sum of different actuators on each side of the gel. For example, if we have a design that has actuator [1, 2, 1, 3, 1] on the one side and [4, 2, 2, 4, 2] on the other, it takes 3 steps to pattern the first side given 3 different actuators used and 2 steps on the other. The total fabrication steps would be five to pattern these devices. The new mutation function now calculates the steps needed when the $P$ is updated and rejects the $P$ if it exceeds the maximum step allowed. The function would then reassign $P$ and check and iterate until it converges on a new $P$ that satisfies the fabrication limit.  \n\nListing 1 Pseudo-code of the deep-learning guided genetic algorithm.   \n\n\n<html><body><table><tr><td>initialize first generation of designs</td></tr><tr><td>for i in range(generation_limit):</td></tr><tr><td>fitness scoring with CNN model and loss function</td></tr><tr><td>eliminate 80% of the population</td></tr><tr><td></td></tr><tr><td>mutate survivors and generate descendants</td></tr></table></body></html>  \n\nFinally, we select the top 5 survivor designs to be the optimum converged designs in each evolution tree.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 20,
+        "chunk": "# 2.5 Search Evaluation  \n\nAt the end of every evolution tree, the 5 final converged designs are saved and manually scored for an objective scoring; this is to mediate the possibility of false-positives from the convolutional neural net and to assure that the final outputs are digit-like to both machines and human. Figure 6 shows an example of the evaluation process, where each image gets a score of 1 (labeled with a green box) if it looks like a perfect digit, 0.5 (labeled with a blue box) if it looks similar but not perfect and 0 if unrecognizable. This is used as the final subjective-matrix to ensure the convergence of the model is reasonable.  \n\n![](images/c5476d6749c69863b12c400d6d6690327564f3c1769948732a9c49a8b1668a31.jpg)  \nFigure 6 Example of manual(human-scored) evaluation. All converged outputs are manually scored to provide a final score for each design. In the example, the design forms 5 perfect digits (marked in green), 1 recognizable digit (marked in blue) and is unable to form other digits (marked in red). The final score is thus $1\\mathrm{~x~5~+~}0.5\\mathrm{~x~1=~5.5~}$ .",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# 3 Results and Discussions  \n\nWe then deployed the algorithm on the search for an optimal design. During the search, we seek to explore the parameter space and learn the effect of different hyper-parameters including - degree of freedom, design scale, search duration, and fabrication limit on the ability to find optimal design. As the searching process itself is stochastic and no independent event is repeatable, we evaluate the search of each condition with 3 separate evolution trees and aggregate the information to avoid an independent event being an outlier. After the search, all converged designs are manually scored to assure the accuracy of evaluation. The distribution of final scores is used as a final metric, along with the loss trajectory, to help us determine whether a condition is ideal or not.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# 3.1 Degree of Freedom: Number of Segments  \n\nWe first seek to learn the effect of how the number of segments affects the material’s ability in finding digit transformer designs. During the search, we fixed the parameter of the total length to be roughly $8000\\mu\\mathrm{m}$ and the search duration to be 100 generations. We ran the search of different segment lengths from 2 to 100 with 3 separate evolution trees for each condition. The result of the loss trajectory is shown in Figure 7 as an objective matrix to evaluate the effect of different segment numbers from the machine’s perspective. The manually scored results of the converged designs of each condition are shown in Figure 8 as a subjective matrix for evaluation.  \n\n![](images/4b65a336d25f81bb41389830227003abeec8d32344dcc4a7538993cbb75f834d.jpg)  \nFigure 7 Loss trajectory of search on different segment number.  \n\nThe number of segments is analogous to the degree of freedom of the system. More segments means there are more knobs to tune during the search and, theoretically speaking, better performance of the algorithm. The result, however, shows that this is only true within a certain extent. There exists a sweet-spot, and exceeding this region actually impales the ability to find good designs, as shown in Figure 8. We believe that this is because we are also increasing the complexity of the problem when we raise the number of segments used in the search, and after a certain amount of freedom is introduced, the benefit of having more knobs is out-weighted by the increase in complexity. Currently, our method and algorithm are unable to find good designs when the system is too complex. From this we learn the importance of maintaining the balance between degree of freedom and problem complexity when we are solving a problem with models.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# 3.2 Design Scale  \n\nNext we seek to learn the effect of the design scale on search performance. During the search, we fixed the parameter of number of segments used to 12 and the search duration to 100 generations. We ran the search of different total length scale from $800\\mu\\mathrm{m}$ to $80,000\\mu\\mathrm{m}$ with 3 separate evolution trees for each condition. The result of the loss trajectory is shown in Figure 9 as an objective matrix to evaluate the effect of different segment numbers from the machine’s perspective. The manually scored results of the converged designs of each condition are shown in Figure 10 as a subjective matrix for evaluation.  \n\n![](images/c8341ff00776fecd6bbb878a45963d2808ba06129483feffb3cf27a5cc201ae8.jpg)  \nFigure 8 Score distribution of search on different segment number.  \n\n![](images/f3ba874e7b43cf137ea9def52b2a6513ce087b20c16470adf89e018e05c17d8e.jpg)  \nFigure 9 Loss trajectory of search on different length scale.  \n\nDuring the search, we learned that the length scale played an important role in the performance and that there also exists a sweet spot in the length scale when searching for an optimal design. We found out that when the length scale of the material is too small, the devices are unable to bend into large angles as the folding power the actuators provide is not enough. This limits the outputs of the devices to be simply straight or slightly bent 1s, and stops the algorithm from finding interesting designs. This is why the short length scale condition $(800\\mu\\mathrm{m}$ ) only get score 1s in Figure 10, and we can see the algorithm is unable to optimize anything at all inspecting the loss trajectory in Figure 9. The search only starts becoming interesting and meaningful when the scale is large enough at $4,000\\mu\\mathrm{m}$ , but the performance starts to decrease again when the scale becomes too large. This is because the devices are also more likely to misfold into undesired “random squiggles” when they are too long, which also corresponds to the folding power the actuators provide and the problem we are trying to solve. With this search we are able to locate the ideal length range for our devices given our actuator power and our target objectives.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# 3.3 Search Duration  \n\nAnother parameter we changed during the search is the duration of the evolution. We fixed the parameter of number of segments used to be 12, the length scale to be $8,000\\mu\\mathrm{m}$ , and search duration to be 150 generations with 3 separate evolution trees. We harvest and save the top 5 designs every 30 generations so we can track the manual scores at different evolution stages. The result of the loss trajectory is shown in Figure 11 as an objective matrix to evaluate the effect of different segment numbers from the machine’s perspective. The manually scored results of the converged designs of each condition are shown in Figure 12 as a subjective matrix for evaluation.  \n\n![](images/6166cbf1593b47ce195075228a2436c38b0a4f579a2f391b1583cb3239dcfe40.jpg)  \nFigure 10 Score distribution of search on different length scale.  \n\n![](images/59537ecf45f58aef06fd04ba193d6b2865fe380563f8551f8028835ce9d51dae.jpg)  \nFigure 11 Loss trajectory of search on different search duration.  \n\nHere, we learn that designs start becoming meaningful quite early in the search, this makes sense as the algorithm is programmed to preserve all good designs found along the evolution path. The search also starts converging toward the minimum at around 90 to 120 generations, which is also why we set most search durations to 100 in other conditions. A more interesting point, however, is that we do not want the search to go on infinitely either. While the loss stopped decreasing after a certain amount of generations passed, we also observed a decrease in “gene diversity” when the search became too long. Here, we define “genes” $G(S,P)$ as the component that makes up the design input - the segment list $S$ and pattern matrix $P$ . We found out that as the search becomes too long, the genes especially in $P$ start to become less diverse, with many survivors sharing similar $P$ and the search process becoming a randomized $S$ swapping search with little optimization going on. Moving forward, it may be helpful in future searches to add a gene diversity evaluation tracker within the search and program the mutation rate to change adaptively in response to the gene diversity.  \n\n![](images/2e04c77f5e8bc3b8d6b608ad6f2f1b4d56c9319572a2d6612fc4535686a9f372.jpg)  \nFigure 12 score distribution of search on different search duration.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 25,
+        "chunk": "# 3.4 Fabrication Limit  \n\nFinally, we investigated how fabrication limit affects the search performance, as it is also vital that the designs found should not exceed the physical patterning limit. Currently, we are imposing a 6 step limitation on the search, as exceeding this value increases the difficulty patterning the devices. During the search, we fixed the length scale to be $8,000\\mu\\mathrm{m}$ and search duration to be 100 generations with 3 separate evolution trees for the two conditions - 6-segment designs and 12-segment designs. We compared the results with the same conditions shown above to learn how fabrication limit affects the search performance.  \n\n![](images/94b2877779e3dcf3302259b94040ab0438f5f6ce5350be0ab5a722803f48b6f4.jpg)  \nFigure 13 Loss trajectory of search on different fabrication limit.  \n\nWe showed that the fabrication limit imposed does not drastically change the behavior or the performance of the search in our given conditions. While the limit does slightly decrease the performance of the optimal designs for the 12-segment search, we do think it is still possible to find a design that can fold into all digits given more evolution trees deployed for a wider and larger search. It is therefore encouraging that we now have a computational material discovery method that can autonomously learn and evolve the material designing process while considering real-world physical limitations.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 26,
+        "chunk": "# 4 Conclusion  \n\nHere, we demonstrate the development of a computational material discovery method for a multi-stable soft material with orthogonal actuators and automate the multi-objective optimization process with a genetic algorithm and integration of a deep-learning model. We show that we are able to efficiently explore the large parameter space and learn the effect of different variables. We also show that we can impose real-world physical constraints to discover reasonable designs.  \n\n![](images/7d4d55dffda6ee68e5a09aeab7156a5e77289b7cb8e690698d55dc3c895587b3.jpg)  \nFigure 14 Score distribution of search on different fabrication limit.  \n\nIn future work, one could expand the dimension of the simulation platform to handle more complex material actuation simulation. Building on this structure, it could also be possible to develop an advanced discovery platform that can optimize the functions of DNA-actuated hydrogel designs for tasks such as building locomotive robots.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 27,
+        "chunk": "# References  \n\n1 Dhiraj Bhatia, Christian Wunder, and Ludger Johannes. Self-assembled, programmable dna nanodevices for biological and biomedical applications. ChemBioChem, 22(5):763–778, 2021.   \n2 Angelo Cangialosi, ChangKyu Yoon, Jiayu Liu, Qi Huang, Jingkai Guo, Thao D. Nguyen, David H. Gracias, and Rebecca Schulman. Dna sequence–directed shape change of photopatterned hydrogels via high-degree swelling. Science, 357(6356):1126–1130, 2017. doi: 10.1126/science.aan3925.   \n3 VF Cardoso, C Ribeiro, and S Lanceros-Mendez. Metamorphic biomaterials. Bioinspired Materials for Medical Applications, pages 69–99, 2017.   \n4 N. Chakraborti. Genetic algorithms in materials design and processing. International Materials Reviews, 49(3-4):246–260, 2004. doi:10.1179/095066004225021909.   \n5 Peter W Deelman, Lisa F Edge, and Clayton A Jackson. Metamorphic materials for quantum computing. MRS Bulletin, 41(3):224–230, 2016.   \n6 Li Deng. The mnist database of handwritten digit images for machine learning research [best of the web]. IEEE signal processing magazine, 29(6):141–142, 2012.   \n7 Abhijith M Gopakumar, Prasanna V Balachandran, Dezhen Xue, James E Gubernatis, and Turab Lookman. Multi-objective optimization for materials discovery via adaptive design. Scientific reports, 8(1):1–12, 2018.   \n8 Mustapha Jamal, Sachin S Kadam, Rui Xiao, Faraz Jivan, Tzia-Ming Onn, Rohan Fernandes, Thao D Nguyen, and David H Gracias. Bio-origami hydrogel scaffolds composed of photocrosslinked peg bilayers. Advanced healthcare materials, 2(8):1142–1150, 2013.   \n9 Paul C Jennings, Steen Lysgaard, Jens Strabo Hummelshøj, Tejs Vegge, and Thomas Bligaard. Genetic algorithms for computational materials discovery accelerated by machine learning. NPJ Computational Materials, 5(1):1–6, 2019.   \n10 Michał Joachimczak, Reiji Suzuki, and Takaya Arita. Artificial metamorphosis: Evolutionary design of transforming, soft-bodied robots. Artificial life, 22(3):271–298, 2016.   \n11 Yongfei Juan, Yongbing Dai, Yang Yang, and Jiao Zhang. Accelerating materials discovery using machine learning. Journal of Materials Science & Technology, 79:178–190, 2021. doi: 10.1016/j.jmst.2020.12.010.   \n12 Diederik P Kingma and Jimmy Ba. Adam: A method for stochastic optimization. arXiv preprint, 2014. arXiv:1412.6980.   \n13 Y. Lecun, L. Bottou, Y. Bengio, and P. Haffner. Gradient-based learning applied to document recognition. Proceedings of the IEEE, 86(11):2278–2324, 1998. doi:10.1109/5.726791.   \n14 Yue Liu, Tianlu Zhao, Wangwei Ju, and Siqi Shi. Materials discovery and design using machine learning. Journal of Materiomics, 3(3):159–177, 2017. doi:10.1016/j.jmat.2017.08.002.   \n15 Arun Mannodi-Kanakkithodi and Maria KY Chan. Computational data-driven materials discovery. Trends in Chemistry, 3(2):79–82, 2021.   \n16 Tarak K. Patra, Venkatesh Meenakshisundaram, Jui-Hsiang Hung, and David S. Simmons. Neural-network-biased genetic algorithms for materials design: Evolutionary algorithms that learn. ACS Combinatorial Science, 19(2):96–107, 2017. doi:10.1021/acscombsci.6b00136.   \n17 Anjali Rajwar, Sumit Kharbanda, Arun Richard Chandrasekaran, Sharad Gupta, and Dhiraj Bhatia. Designer, programmable 3d dna nanodevices to probe biological systems. ACS Applied Bio Materials, 3(11):7265–7277, 2020.   \n18 Ruohong Shi, Joshua Fern, Weinan Xu, Sisi Jia, Qi Huang, Gayatri Pahapale, Rebecca Schulman, and David H Gracias. Multicomponent dna polymerization motor gels. Small, 16(37):2002946, 2020.   \n19 Changwon Suh, Clyde Fare, James A Warren, and Edward O Pyzer-Knapp. Evolving the materials genome: How machine learning is fueling the next generation of materials discovery. Annual Review of Materials Research, 50:1–25, 2020.   \n20 Rama Vasudevan, Ghanshyam Pilania, and Prasanna V Balachandran. Machine learning for materials design and discovery, 2021.   \n21 Zhi Zhao, Chao Wang, Hao Yan, and Yan Liu. Soft robotics programmed with double crosslinking dna hydrogels. Advanced Functional Materials, 29(45):1905911, 2019.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Article Long-Term Antifogging Coating Based on Black Phosphorus Hybrid Super-Hydrophilic Polymer Hetero-Network  \n\nLie ${\\mathbf{W}}{\\mathbf{u}}^{1,2}(\\mathbb{D}),$ , Yihong Kang 1, Yuhao Deng 1, Fan Yang 1,\\*, Rui He 1,\\* and Xue-Feng $\\Upsilon\\mathfrak{u}^{1,2,3,*\\oplus}$  \n\n1 Materials Interfaces Center, Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, China   \n2 University of Chinese Academy of Sciences, Beijing 100049, China   \n3 Hubei Three Gorges Laboratory, Yichang 443007, China   \n\\* Correspondence: fan.yang1@siat.ac.cn (F.Y.); rui.he1@siat.ac.cn (R.H.); xf.yu@siat.ac.cn (X.-F.Y.) Citation: Wu, L.; Kang, Y.; Deng, Y.; Yang, F.; He, R.; Yu, X.-F. Long-Term Antifogging Coating Based on Black Phosphorus Hybrid   \nSuper-Hydrophilic Polymer   \nHetero-Network. Nanomaterials 2023, 13, 86. https://doi.org/10.3390/ nano13010086  \n\nAcademic Editor: Sergei Kulinich  \n\nReceived: 26 November 2022   \nRevised: 20 December 2022   \nAccepted: 22 December 2022   \nPublished: 24 December 2022  \n\nCopyright: $\\circledcirc$ 2022 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/).  \n\nAbstract: The antifogging coating based on super-hydrophilic polymer is regarded as the most promising strategy to avoid fogging but suffers from short-term effectiveness due to antifogging failure induced by water invasion. In this study, a black phosphorus nanosheets (BPs) hybrid polymer hetero-network coating (PUA/PAHS/BPs HN) was prepared by UV curing for the first time to achieve long-term antifogging performance. The polymer hetero-network (HN) structure was composed of two novel cross-linked acrylic resin and polyurethane acrylate. Different from physical blending, a covalent P-C bond between BPs and polymer is generated by UV initiated free radical reaction, resulting in BPs firmly embedded in the polymer HN structure. The BPs enriched on the coating surface by UV regulating migration prevent permeation of water towards the inside of the coating through its own good water-based lubricity and water absorption capacity. Compared with the nonhybrid polymer HN, PUA/PAHS/BPs HN not only has higher hardness and better friction resistance properties, but also exhibits superior water resistance and longer antifogging duration. Since water invasion was greatly reduced by BPs, the PUA/PAHS/BPs HN coating maintained antifogging duration for $60~\\mathrm{{min}}$ under a $60~^{\\circ}C$ water vapor test and still maintained long-term antifogging performance after being immersed in water for 5 days.  \n\nKeywords: black phosphorus; hybrid; polymer; hetero-network; coating; long-term antifogging",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1. Introduction  \n\nWhen saturated water vapor condenses on a surface with a temperature lower than the dew point of the vapor, fog forms as tiny droplets that can scatter visible light [1–3]. For those transparent materials, surface fogging greatly reduces light transmittance, resulting in undesirable failure when applied in optical-related fields. For example, surface fog largely impacts the precision of optical and analytical instruments, such as infrared microscopes and clinical laparoscopy [4].  \n\nMany strategies, referring to super-hydrophobic and super-hydrophilic surfaces, have been developed for effective antifogging. Super-hydrophobic surfaces eliminate the effect of fog droplets by rolling down from the surface, but the light transmission tends to be compromised by the surface’s own micro/nano-structured roughness [4–7]. Different from super-hydrophobic surfaces, the antifogging coating based on super-hydrophilic polymer avoids fogging by quickly spreading fog droplets into a continuous water film, so as to effectively prevent the light scattering. Therefore, in the field of antifogging, superhydrophilic surfaces are easier, more reliable and more promising than super-hydrophobic surfaces [8–12]. However, as the water film on a super-hydrophilic surface grows to a certain thickness, polymer-based coatings suffer from loss of water-soluble components and swelling-induced peeling and cracking, which results in the antifogging failure of the coatings [13]. Therefore, polymer-based coatings are usually limited to short-term antifogging effectiveness due to their insufficient water resistance capability. To improve the water resistance of polymer-based coatings, some water-resistant organics such as hydrophobic components are usually added into the coatings. Unfortunately, these organics usually weaken the hydrophilicity of the coating, resulting in a decline in its antifogging ability. To date, it is still a huge challenge to balance the hydrophilicity and water resistance of polymer-based coatings [14].  \n\nGenerally, hydrophilic inorganic nanomaterials are able to absorb and store water without swelling, thus bringing a new strategy to regulate the balance between the hydrophilicity and water resistance of polymer-based coatings [15]. To improve the comprehensive properties of these organic–inorganic composites, more strategies for regulating compatibility, dispersion and stability of inorganic nanomaterials in the polymer-based coatings are required [16]. As a new hydrophilic two-dimensional inorganic nanomaterial [17,18], black phosphorus (BP) can improve the wear resistance and drainage capacity of the coating due to its excellent water-based lubrication performance [19–21]. On the other hand, BP possesses excellent compatibility with hydrophilic polymers, leading to universally good stability of the BP/polymer complex materials [22,23]. Unfortunately, the combination mode of BP with polymer reported at present is mostly weak physical blending rather than strong chemical combination [24–27], which greatly affects various performance attributes of BP-based polymer coatings. Therefore, although the BP-based polymer coating is a promising material for antifogging, some huge challenges, especially the chemical combination and microstructure regulation between BP and polymer, still need to be overcome.  \n\nIn this study, a long-term antifogging coating based on BP nanosheets (BPs) hybrid super-hydrophilic polymer hetero-network (HN) was designed and prepared by construction of P-C bond under UV curing. The polymer hetero-network (HN) structure [28,29] was composed of two novel cross-linked compounds, acrylic resin and polyurethane acrylate. Different from physical blending, a covalent P-C bond between BPs and polymer is generated by UV-initiated free radical reaction, resulting in BPs firmly embedded in the polymer HN structure. The BPs enriched on the coating surface by UV regulating migration can effectively prevent the permeation of water towards the inside of the coating through its own good water-based lubricity and water absorption capacity.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2. Materials and Methods",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2.1. Materials  \n\nThe BP crystals were obtained from Mophos (www.Mophos.cn, Yichang, China). Polyethylene glycol 2000 (PEG 2000), 4-methoxyphenol (MeHQ, AR, $99.0\\%$ ), butylated hydroxytoluene (BHT), $>99.0\\%$ (GC)), dibutyltin dilaurate (DBTDL, $95\\%$ ), N-Methyl pyrrolidone (NMP), isophorone diisocyanate (IPDI, $99\\%$ ), pentaerythritol triacrylate (PETA, $96\\%$ ), ethyl acetate $(99.0\\%$ , GC), acrylic acid (AA, $>99.7\\%$ , GC), 2-hydroxyethyl methacrylate (HEMA, $99\\%$ ), sulfobetaine methacrylate (SBMA), azodiisobutyronitrile (AIBN, $99\\%$ ) and diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide (TPO, $97\\%$ ) were purchased from Aladdin Chemical Reagent Co., Ltd. (Shanghai China). All chemical regents were directly used without any further purification.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2.2. Instruments  \n\nThe physicochemical properties of materials were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), optical microscopy, Raman scattering microscopy, $\\mathsf{X}$ -ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy and $^1\\mathrm{H}$ nuclear magnetic resonance spectroscopy $({}^{1}\\mathrm{HNMR})$ .  \n\nThe mechanical properties of coatings were characterized by mechanical instruments. The adhesion strength, hardness and friction resistance of coatings were measured on a direct pull tensile force machine, pencil hardness tester and ball disc friction tester, respectively.  \n\nThe hydrophilicity of coatings was measured by the water contact angle (WCA) tester, and the antifogging performance of the coatings was tested through a thermostatic water bath.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.3. Methods",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.3.1. Preparation of Materials  \n\nSynthesis of polyurethane acrylate (PUA): $_{2\\mathrm{~g~}}$ PEG 2000, 6 mg MeHQ, $3\\mathrm{mg}$ BHT and $3\\mathrm{mg}$ DBTDL were dissolved in $20~\\mathrm{ml}$ ethyl acetate to obtain the dropping solution. A $444\\mathrm{mg}$ amount of IPDI was put into a three-port flask, and then the dropping solution was added to the three-port flask for $2\\mathrm{h}$ at room temperature under the stirring speed of $200\\mathrm{rpm}$ . The reaction was carried out at $40^{\\circ}C$ for $6\\mathrm{h},$ and then $500\\mathrm{mg}$ PETA was added to continue the reaction for $^{3\\mathrm{h}}$ at $80^{\\circ}C$ . After filtration and solvent evaporation, the residue was dried in a vacuum to yield a colorless oil.  \n\nSynthesis of P(AA-HEMA-SBMA) acrylic resin (PAHS): In a three-port flask, $3.6\\mathrm{g}$ AA, $6.5\\:\\mathrm{g}$ HEMA, $14\\mathrm{g}$ SBMA and $24\\mathrm{mg}$ AIBN were dissolved in $30\\mathrm{ml}$ ethyl acetate, and the reaction was carried out at $80~^{\\circ}C$ for $6\\mathrm{{h}}$ . After filtration and solvent evaporation, the residue was dried in a vacuum to yield a white powder.  \n\nSynthesis of black phosphorus nanosheets $(B P s)$ : The BPs were prepared by a liquid exfoliation method reported by our group. In brief, $10~\\mathrm{mg}$ of the bulk BP crystal was dispersed in $10~\\mathrm{mL}$ NMP and sonicated for $6\\mathrm{{h}}$ with an ultrasonic frequency of $19{-}25\\mathrm{kHz}$ (2 s ON and 4 s OFF; 1800 W; $6{}^{\\circ}\\mathrm{C}\\mathrm{\\cdot}$ ). The dispersion was centrifuged for $15\\mathrm{min}$ at $7000\\mathrm{rpm},$ and the collected supernatant was centrifuged for $15\\mathrm{min}$ at $12000\\mathrm{rpm}$ for further use.  \n\nSynthesis of super-hydrophilic polymer hetero-network coating $(P U A/P A H S H N)$ : The UVcurable solution was prepared by dissolving the photo initiator TPO and the obtained PUA, PAHS in 2-propanol with about $40\\%$ total solid content. The UV-curable solution was spin-coated on a plastic substrate, and then followed by UV irradiation (broadband, $400\\mathrm{mj}/\\mathrm{cm}^{2})$ to obtain a cured PUA/PAHS/BPs HN coating.  \n\nSynthesis of BPs hybrid super-hydrophilic polymer hetero-network coating (PUA/PAHS/BPs HN): The UV-curable solution was prepared by dissolving the photo initiator TPO and the obtained PUA, PAHS, BPs in 2-propanol with about $40\\%$ total solid content. The UV-curable solution was spin-coated on a plastic substrate, and then followed by UV irradiation (broadband, $400\\mathrm{\\mj/cm}^{2},$ ) to obtain a cured PUA/PAHS HN coating.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.3.2. Physicochemical Properties of Materials  \n\nCharacterization: SEM images were acquired from a Zeiss SUPRATM 55 SAPPHIRE (Oberkochen, Germany) field-emission scanning electron microscope. The SEM images were used to analyze the morphology of materials. The preparation method for samples was to take part of the UV- cured coating and paste it onto the sample table through conductive resin. The cross-section samples were pasted onto the cross-section sample table after freezing extraction. The AFM images were acquired from the Bruker Icon (Karlsruhe, Germany) atomic force microscope and were used to analyze the morphology of materials by detecting the atomic force between the sample and the probe. The samples were dispersed in EtOH and then dropped onto Si substrates for investigation. FTIR spectra were collected in a wavenumber range of $4000{\\mathrm{-}}400{\\mathrm{cm}}^{-1}$ on a Thermo Nicolet IS5 instrument (Waltham, MA, USA). The FTIR spectra were used to analyze the molecular structure of materials through functional group recognition. The preparation method for samples was KBr tableting. Raman scattering was conducted on a Horiba Jobin-Yvon Lab Ram HR VIS high-resolution confocal Raman microscope (Paris, France) equipped with a $633\\mathrm{nm}$ laser. The Raman FTIR spectra were used to analyze the structure of materials by Raman peak recognition. The samples were dispersed in EtOH and then dropped onto Si substrates for investigation. The $^1\\bar{\\mathrm{H}}$ NMR spectroscopy was performed on the Bruker Advance DRX-300 spectrometer (Karlsruhe, Germany) at $25^{\\circ}C$ and was used to analyze the structure of materials by NMR peak recognition. The samples were dissolved in deuterium reagent and then put into the nuclear magnetic tube. XPS spectra were obtained from a  \n\nThermo Escalab $250\\mathrm{{Xi}}$ spectrometer (Waltham, MA, USA) equipped with an $x$ -ray source producing Al $\\operatorname{K}\\alpha$ radiation $(1486.6\\mathrm{eV})$ . The XPS spectra were used to analyze the surface elements of materials. The samples were dispersed in EtOH and then dropped onto Si substrates for investigation.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.3.3. Performance Testing of Materials  \n\nMeasurement of mechanical properties of coatings: The adhesion strength of coatings was measured on a BGD500 direct pull tensile force machine by a pull-off test. The pull-off test was classified as a near to surface, partially destructive method that was able to measure the maximum tensile strength of the coatings. The hardness of the UV-cured coatings was measured by industrial pencil hardness tests (JIS K5400) on a QHQ-A pencil hardness tester. The tip of the pencil is placed on the coated substrate and scratched over the film. The hardness designation of the pencil that just fails to cut the film is the pencil hardness of the film. The lubrication performance of coatings was evaluated by coefficient of friction tests. The friction tests were completed using an MS-T3001 ball disc friction tester. A GG15 ball with a diameter of $6\\mathrm{mm}$ was a fixed friction, pair and the coating to be tested is a rotary disc.  \n\nThe friction coefficient was recorded in real time by the equipment system.  \n\nMeasurement of antifogging performance of coatings: The antifogging performance of coatings was evaluated by three methods. The first method was the hot water vapor test. The samples were held above a water bath containing $60^{\\circ}C$ water, and the distance between the samples and water surface was $5\\mathrm{cm}$ . The antifogging performance was measured by observing the fogging of coated substrates. The second method was to measure the hydrophilicity of coatings by testing the WCA. A $6~{\\upmu\\mathrm{L}}$ drop of water was placed onto the surface of the coating, and the WCA was analyzed by the image of water spreading. The third method was to investigate the light transmission over the $300{-}800\\mathrm{nm}$ wavelength range using a UV-Vis spectrophotometer during fogging tests.  \n\nMeasurement of antifogging cycle of coatings: The antifogging cycle tests were carried on a $60~^{\\circ}C$ water bath. The sample was first exposed to hot water vapor $(60~^{\\circ}\\mathrm{C})$ for $15\\mathrm{min}$ (denoted as the wet state). Then, the sample was dried at $40~^{\\circ}\\mathrm{C}$ for $^{4\\mathrm{h}}$ (denoted as the dry state). One cycle was completed, and the next cycle was carried out according to this method.  \n\nMeasurement of high and low temperature cycling resistance of coating: Placing the sample in a high and low temperature box, the program was set as follows: cool down to $-20^{\\circ}\\mathrm{C},$ keep the temperature at $-20^{\\circ}C$ for ${12\\mathrm{h}},$ and then raise the temperature to $80~^{\\circ}C,$ keep the temperature at $80~^{\\circ}C$ for ${12\\mathrm{h}},$ and the rate of temperature rise and fall is $1\\mathrm{{}^{\\circ}C/m i n}$ . One cycle was completed, and the next cycle was carried out according to this method. The antifogging performance of the coatings was evaluated after 10 cycles.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3. Results and Discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3.1. Material Synthesis and Characterization  \n\nThe polymer HN consisted of polyurethane acrylate (PUA) and acrylic resin (poly (acrylic acid (AA)-2-hydroxyethyl methacrylate (HEMA)-sulfobetaine methacrylate (SBMA), short for PAHS)), prepared by UV-initiated cross-linking. Both polymers have outstanding hydrophilicity and prominent adhesion on plastic substrates [11,30]. The UV-curable six functional PUA was prepared by polymerization of polyethylene glycol (PEG) with diisocyanate and end-capping with pentaerythritol triacrylate (PETA) (Supporting Information, Figure S1). PAHS was obtained by radical polymerization of three hydrophilic monomers AA, HEMA, SBMA, which contained generous hydrophilic groups (Figure S2). The $^1\\mathrm{H}$ nuclear magnetic resonance $\\cdot^{1}\\mathrm{HNMR})$ spectra and the Fourier transform infrared (FTIR) spectra of PUA and PAHS illustrated the successful synthesis of the two polymers (Figure S3–S5).  \n\nThe BP nanosheets (BPs) were obtained by a liquid exfoliation method reported by our group [31]. The scanning electron microscope (SEM) image (Figure S6) shows BPs about $200{-}300\\mathrm{nm}$ in size. The UV-curable solution prepared by dissolving the as-obtained PUA, PAHS, BPs and photootoiniintitaitaotroirnisnoslvolevnetnwt aws asspisnp-icno-actoeadteodn aonplasptilcastuicb sturabtset ranted iarnraddiirartaediatbeyd UbyV UtoV tsoynstyhnetshizeesiztehethBePBsPshyhbyrbirdidpoploylymerer HN coattiing (denoted  as PUA/PAHS//BBPsP s HN)N.).AsAshsohwonwin  iFnigFuirgeur1ea 1tah,ethyebhriydbirziadtizoant iofnBoPfs BanPsd tahnedctrhoessc-lrionsksliingkionfgPUofAPaUnAd PaAndHSPAocHcSuroreccdusrirmedu tsainmeuoltuaslnyeouunsdleyruUnVdierraUdiVatiiroran.diTahtieopn. tTohieniptihaottor ipnritoidatuocrepdrfordeuecreadifrcealesrtaodicnailtisattoeipniotliyatmeepriozlyatmioenrizoaftiaocrnyolfa taecrgyrloautepsgraonudpsgaenedrgateinoenr aotfioPnoCf bPo-nCdsb,otnhdus,etmhubsededminbge dBdPisnign tBhPespion ythme rpoHlyNmsterucHtuNres.tIrnucatdudriet. In oatdhdeitgioenetroa tiohen gofenPe-rCatbiondosf, tPh-eCibntoenrdacst,itohnesibnetterwaecetinoPn satboetmws eaendPhyatdorompshailnicdghryodurpospahlisloicegnrhoaunpcsesatlshoe estnahbailnitcyesotfhBePsst.abPilUitAy/PofABHPSs/.BPUs AH/NPAshHoSw/eBdPsnoHtNonslhyolwoendg-tneortmonsltyabliolintgy-tbeurtmalsstaobhiliigtyh bmuetcahlasonihciaglhstrmencghtahnidcuale  sttoretnhgetchrdosuselitnoktihnegcorfospsolilnykminergs.ofWpholeynmwerast.erWvhaepnorwcaotenrdveanspeodr con tdhensuerdfaocnetohfePsuUrAfa/cPeAoHf SP/UBPAs/PHANH, Sa/hBePmsi-HwNi,c kainhegmpih-ewnicokminegnopnheonccoumrerendononoctchuerrheydodnrotphheilhiycdrroupghiliscurfoaucgeh( Fsiugrufarcee1(bF)ig[3u2r]e. 1Tbh)e[3h2y].brTihdiezhatyibornidoifzaBtiPosninocfrBeaPseidnctrheaseudrftahce sruorufgachenreossu,gwhnhiecssh  mwahidcehthmeadweatehreswparteeardspmroeraedrmapoirdelryaopindtlhyeosnutrhfaecseurofatcheeocfotahteincgo,atihnugs, trheaulsizrienalgiztihnegetffhecteifvfecatinvteifaongtgiifnoggpienrgfopremrfaonrcmeaonfcPeUofAP/PUAH/SP/ABHPsS/HBNP.s HN.  \n\n![](images/a0fac85a11bc2673496e716195b4babf334aab305a87b842bfc6967257a2eb02.jpg)  \nFigure  1.  Schemattiic diiaagrraamofofdedseisgingnofoBfPBhPyhbyribdr ipdolpyolmyermeHrNHcNoactionagtifnogr feoffrecetffiveectaivnteifaongtigfionggpinergfpoerrmfoarnmcea.n(cae).S(ya)ntShyensitsheofs iPsUofAP/UPA/HPSA/BHPSs/BHPNs .H(bN) .A(nbt)ifAongtgiifnog gminecghamneicshma noifsPmUoAf/PUAAH/SP/ABHPsS/HBPNs.  \n\nThe SEM images of PUA/PAHS HN and PUA/PAHS/BPs HN are shown in Figure 2a,b, respeTcthiev eSlEy.MT hiemnaegtesworfkPsUtrAu/cPtuAreHfSorHmNe danbdy tPhUeAcr/oPsAs-HliSn/kBiPnsg oHfNPaUrAe sahnodwPnAiHnSFhigaudrae d2ia,bm, erteesrpeofctaivbeoluyt. $300{-}500\\mathrm{nm}$ ,k swtirtuhctmuircerofonr-smcealdebhyoltehedicaromsest-leirnakindgaobfoPutU $70\\%$ pdoProAsiHtyS. Thhaed amodriaphmoeltoegryofofatbhoeutne3t0w0–o5rk00stnrumc,tuwriethremiacirnoend-sbcalsiechalollyeudniachmaentgeredanwditahbtohueta7d0d%itiponrofosBitPys.. hTehemcoropshs-osleocgtyionf tShEeMneitmwaogrek sotfruPcUtuAre/PreAmHaSi/neBdPsbaHsiNcalilny FuingcuhraenSg7edshwoitwhs ihtse gaododidt ohnomofoBgePns.eiTthyeacnrdostsi-gsehct iconmSbEinMatiimonagewiotfhPtUheA/sPuAbsHtrSa/tBePs.s HTNhe nAFigMurdei aSg7rsahmowofs iPtsUgAo/oPdAhHoSm/oBgPesnHeitNysahnodwteigdhtthcatoBmPbsinwateiroenrewliathivtehley seuvebsntlryatdeis.trTibhueteAdFiMn tdhieagcroatminogf (Figure S8). The FTIR peaks of PUA at $3000{-}3100\\ \\mathrm{cm}^{-1}$ and $1650\\mathrm{cm}^{-1}$ were attributed t(oF gCu–rHe aS8n)d. ${\\mathrm{C}}{=}{\\mathrm{C}},$ TreIsRppecetaikvseloyf (PFiUgAuraets320c0a0–n3d10S09).cmC−1o amnpdar1e6d50wcitmh 1PwUeAr,etahtet $\\mathrm{{C-H}}$ adntdo $C{=}C$ peaks of PUA/PAHS/BPs HN disappeared, and some new peaks such as those at $10\\bar{3}9\\ \\mathrm{cm}^{-1}$ and $1240~\\mathrm{cm}^{-1}$ associated with the characteristic peak of PAHS and BPs, respectiv−1ely, appeared. 1This result shows that the free radical polymerization of $C{=}C$ and the hybridization of BPs were realized synchronously. High-resolution XPS (HR-XPS) spectra of PUA/PAHS/BPs HN were acquired and analyzed (Figures 2d,e and S10). As shown by the C 1s XPS spectrum, $\\mathrm{P-C},\\mathrm{C-O},$ and $C{=}0$ peaks at 284.1, 286.1, and $288.4\\mathrm{eV},$ respectively, confirmed the existence of P-C bonding and carbon oxygen covalent bonding of the polymers. The $\\mathrm{~P~}2\\mathrm{p}$ spectrum showed the $\\mathrm{P}2\\mathsf{p}_{3/2}$ and $\\mathrm{P}2\\mathrm{p}_{1/2}$ doublets at 129.6 and $130.5\\mathrm{eV},$ respectively, characteristic of crystalline BP. In addition, the broad peak at $133.3\\mathrm{eV}$ corresponded to P-C covalent bonds, corroborating chemical binding between BP aPnUdAPUbyAfbreyef reaedricaadlicraelarcetiaoctni.oCn.oCmopmarpeadrewditwhitPhUPAU/AP/APHAS HSNH,Nt ,htehReaRmaamnasnpsepcetrcturmumofof PUA/PAHS/BPss HNsshoowsst thhreree prroominineentntppeaeaksksofofBBPsP srerlealtaetdedtotoA $\\mathbf{A}_{\\mathrm{~g~}}^{1}$ a3t $361\\mathrm{{cm}^{-1}}$ ,g $\\mathsf{B}_{2\\mathrm{g}}$ a4t $438\\mathrm{cm}^{-1}$ danAd2 $\\mathrm{A}_{\\mathrm{~g~}}^{2}$ 4a6t $466\\thinspace\\mathrm{cm}^{-1}$ ,s presctpievcetliyve[l3y3[],33i]n,diincdaitcinatginpgrepsrersveartviaotnioonfoBfPBsPstsrturcutcutruere during hybridization (Figure 2f).. Thesserressultltss impllyyssuccceessfsuflulpprerepparartaitoinonofofthteh e HNN structure  and hybridization of BPs.  \n\n![](images/5b89d4e5bec727956e1df97ebc9ab6863434498404b1fcaf7ed315dcb99ba3db.jpg)  \nFigure  2.. Characterization  of BPs hybriid pollymeerr HNccooataitninggaannddnnoonnhyhbyrbirdidpoploylymemrerHHNNcocaotiantign.g. ((a)) SEMiimage of  PUA/PAHS HN..  ( b) SEM iimage offPUA//PPAHS/SB/PBsPsHHN.N(.c)(cF)TFITRIsRpsepctercatroafoPfAPHASH,S, PUA,,  PUA/PAHS HNaannddPPUA/AP/APHASH/BSP/sBPHsN.H(Nd.)  (Hd)R-HXRP-SXCPS1sCsp1escstrpuecmtroufmPUofA/PUAH/SP/BAPHsSH/BN.Ps (He)N.H(eR)-XHPRS-XPS2pP s2pescptreuctmruomf  oPfUPAU/PA/PHAS/HBSP/sBHPsN.H(Nf). (Rf)aRmamn asnpsecptercatroafoPf UPUA/AP/APHASHSHNHNanadnd PUA/PAHS/BPs HN.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3..2. Mechanical pProperties offcCoaotaitningsgs  \n\nThe  mechanical  properties  of  PUA/PAHS  HN  and  PUA /PAHS/B/PBsPsHNNwererefufrutrhtehrer evalluated.. Compared with PUA/PAHS HN,, the  pencil  hardness  of  PUA/PAHS/B/PBsPs HNN iincreased from HB to 3H, which illustratestthatt BPsiimprroveedtthee haarrdnesessofofthtehecocaotaitnigng ((Fiigure 3a). Meanwhile, the WCA of PUA/PAHS//BBPsP s HNNdedcerceraesaesdedwiwtihththteh einicnrceraesaeseinin BPs contten t, iindiicattiing tthatttthe iinttrroducttiion offBPssiimprroveed ttheerorouugghhnnesessofofththeecocaotaitn-g. Tinhge siTmheulstiamneulotuasnieomupsroivmepmroevnetmofernotuogfhrnoeusgshaneds sharndnhesasrdthnreosusgthrBoPusghyBbPrisdhizyabtriiodnizwa-as btieonefiwcaisa lbteontehfiecisaclrtaotctheresscirsatacnhcre soifstahnecceoaftitnhge.cSoianticnega.dSihnecseioandshterseinogntshtroefntghtehcofathineg dceotaetrinmginedseitesrpmeienliensg irtesistpaeneclien,gpulrle-soifsftadnche,siopnusllt-roefnfgtahdtehsetsi onf PsUtrAe/nPgtAhHSt/esBtPss HofN aPnUdAP/UPA/HPS/ABHPSs HN oandpoPlyUeAt/hPylAenHeSteHreNpohtnhpaloaltye(tPhyElTe)n,eptoelryecparhbthoanlatte((PCE)T, )p, oploylmyceatrh-yl bmoenthataecr(yPlCa)t,ep(oPlMymMetAh)yalnmdetahcraycrloylnaiteri(leP-MbuMtaAd)ieaned- satcyryelnoeniterirlpe-oblyutmaedrie(nAe-BsSt)yrweneere epre-rfpoorlmyemde.rA(lAl sBuS)bswtrearte spewrefroer tmraend.spAalrlesnutbasntrdatsemsowotehreptlratensp(sairzen $50\\mathrm{mm}\\times50\\mathrm{mm},$ tehsic(ksinzess $3\\mathrm{mm}^{\\cdot}$ )m,  a×n5d0thmemt,hitchkicnkenssesosf3thme cmo),ataingdstohbettahiincekdneosnstohfetdhieffceoreatnitnsgusbostbrtatiensedwaosn $50~{\\upmu\\mathrm{m}}$ f-by df erfeanutlts.uAbstrsahtoeswnw aisn  5F0igμumreb3yb,dtehfaeualtd.hAesisohnoswtrneingtFhigoufrPeU3bA,/thPeAaHdSheHsiNonwstarsebnegthweoefn $1.7{-}3.5\\mathrm{MPa}$ ,HillNuswtraastibnetgwteheant t1.o7p–o3l.o5gMicPala eilnltuasntrgalteinmgetnht atntodpcolvoagliecanltebnotanndgilnegmweinthasnudbsctoravtaelsenotfbponlydimnegrwHitNh smuabdstertahtescofatpionlgyfimremr lHyNadmhaerde otnhedcifofaetriengt fpirlamsltiycasduhbesrteraotnesd[i2f-8]. Tfehre nitntprloadstuictisounbsotrfatBePss f2u8]r.thTehreeinthraondcuecdt tohneoafdBhPesifounr hoefrtheenhcaonactiendgt,hienadidchaetisinogntohfat hthyeb rciodaitziantigo,ninodficBaPtsinigmtphraotvhesytbhriedtiozaptoilongiocfalBePnstiamngplreomvesn thbettwoepeolnopgioclaylmeenrtsa.nTghlemcoeenftficbietnwt eoefnfrpicotliyomne(rCs.OTFh)econetfifnicuiendttof fdreictlionne (wCitOhF)thceonitnicnrueeadsetoindeBcPlisnceowntitehnt.heCioncmrpearsed iwnitBhPtshceonHteNntc.oCatoinmgpawrietdhowuithBtPhse, tHhNe cCoOatFinogf wPiUthAo/uPtABPHsS, t/hBePsCOHFNofdPecUreAa/sPeAdHbSy/ $68\\%$ , inHdNicdateicnrgeatsheadt sbuycc6e8ss%f,uilnhdyicbartiidnigzathioatnsoufcBcePssfgurelahtlybirimdipzraotvieodn tohfeBlPusbrgircietaytloyfitmheprcovateidng (Figure 3c). Benefiting from the lubrication of BPs, the WCA of PUA/PAHS/BPs HN did not rise significantly after 1000 friction test cycles, showing its excellent friction resistance property (Figure 3d). These results indicate that the hybridization of BPs can effectively improve the hardness, roughness, adhesion strength and friction resistance of polymer HN.  \n\n![](images/a656091653c1a971bff54c6dfdf54892c77eb8a3e01c03ecab7074bcad947428.jpg)  \nFigure  3. Mechanical properties of BPs hybrid polymer HN coating and nonhybrid polymer HN coating. (a) Pencil hardness offPUA/PAHS/BPs HN with different BPs conttentt. Inset: WCA of PUA/PAHS/BBPPss HN witihthdidfiffefrernetntBPBsPscocnotnetnet.nt(.b()bA)dAhdeshieosniosntrsetnregtnhgtohf oPfUPAU/PA/HPAS/HBSPs/ BHPNs  aHnNd and PUA/PAHS on PET, PC, PMMA and PBS substrates. (c) Coefficient of friction (COF) curve of PUA/PAHS/BPs HN with different BPs content. Inset: schematic diagram of ball disc friction tests. (d) WCA of the PUA/PAHS/BPs HN and PUA/PAHS HN under different friction cycle tests.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3.3 Antifogging Pperformances of cCoattiings  \n\nWhen  BPs conttentt offtthe HN coattiing wasslleessstthaan $6\\mathrm{wt\\%}$ %, ,PPUA//PAHS/BPs HN  had a lliight ttransmittance higher than $90\\%$ ((Fiigure S11)). Considering the transmittance and mechanical properties of the coating, we chose to add $6\\mathrm{wt\\%}$ BPs into the HN coating thereafter. The susttaiined anttiiffoggiing peerrfforrmaancceeooff PUA/ PAHS/BPs HN was evaluated by  the $60^{\\circ}C$ hot water vapor test for $60\\mathrm{min}$ . Compared with bare PMMA slide, the PMMA slide coated with PUA/PAHSS/B/PBsPsHHNNprpersesnetnetdeadsauspuepr-ehr-yhdyrodrpohpilhicilsitcasttea(teW $(\\mathrm{W}{\\bf C}\\mathbf{A}=8^{\\circ}$ ) ahnad haalidghatlitrgahntstrmaitntsamncitet ahnigcehehritghaenr t9h0a%n $90\\%$ tohvee3r0t0h–e8 $300{-}800~\\mathrm{nm}$ ewnagvtehleranngtghe ruandger u60ndmeir $60\\mathrm{min}$ cuonutsinaunotiufsogagnitinfgogtegsitn(gFtiegsutr(eFi4ga)u.reTh4ea)o.pTtihcealopthicoatlogprhaoptohgsrianpFhisgiunr eFi4gbusrheo4wb sthaotwthtehactotahtedc oPatMeMd APMsliMdeAdsilidneodtifdognowt fhoegn ewxhpeonsedxptosheodt two ahtoetr vwapteor  v(6a0po°rC $(60~^{\\circ}\\mathrm{C})$ fmori $60~\\mathrm{{min}}$ , twhehiblearteheP bMaMreAPsMlidMeAfosgligdedfeovgegne idnetvhenfirns thme nfiurstte.mTihneuste. Tsuhletse nredsicualtse itnhdaitctahte tBhPasththyeb rBidPspholybrmiedrpHolNy cmoeartiHngNpcosasteisnsgespossusetasisnesedsuasnttaiifnoegdgiangtiafboigligtiyn.gInabaidlidtiy-. Itinoand, dPitUioAn/,PPAUHAS/BPAsHS/NBoPns PHMNMonAPslMidMesArselimdaeisnredmhaiignheldyhtirgahnlsyptaraenstp(aorpetnicta(lotprtaicnasltrmaitntsamncitetaonvceer 9o0v%er) $90\\%$ )ngdsuerivnegn sweevte–ndrwyecty–cdlreys ocfyaclnetsi ofggaintgiftoegstgsi,nigl tuessttrsa, inllguistsrlaotingitesr lmonagn-dtesrtmablaenadntsitfaobglge nagntipfeorgfogrinmganpcer f(oFrigmuarnec4ec)(.FiTgoufruer $\\mathsf{4c}\\mathbf{\\bar{\\Psi}}$ )e.r Tnoalfyuzrethtehre ainfalluyeznecethoef iBnPflsueoncetohfeBPasn toifnotghgeinagn tipfoergfgoirnmg apnecrfeoromf atnhce  ocfotahtiencgo,atsiunsgt,asinuestdainaentdi faongtigfiong itnegstsestosf oPfUPAU/PAA/PHASHSNHaNndanPdUPAU/PA/PHAS/HBSP/sBHPsNHwNithwidtihffedrifefnetrethnitctkhnicesksnessweesrewecroencdounctdeudc.teAds. tAhsethinecirnecarseasien  icnocaotiantigngthtihcikcnkensesscocouludld delelaayy watter invasion,,  thicker PUA/PAHS HN yielded antifogging performance for a longer duration (Figure 4d). Unfortunately, it was still difficult to maintain $60\\mathrm{min}$ antifogging duration with the PUA/PAHS HN even with increased thickness. In contrast to the PUA/PAHS HN, the PUA/PAHS/BPs HNs with $5\\upmu\\mathrm{m},20\\upmu\\mathrm{m}$ and $50~{\\upmu\\mathrm{m}}$ thicknesses were able to maintain over $90\\%$ light transmittance when exposed to hot water vapor $(60^{\\circ}\\mathrm{C})$ for $60\\mathrm{min}$ . The optical photographs in Figure 4e s4heoswhtohwat haant iafontgifgoinggipnegrfpoer fmoarnmcaenocfePofUPAU/AP/APHAS HSNHdNedcleicnliendeadftaefrtebrebineignigmimemresresdeidn winatewraftoer f1odra1y,dany,dacnodmcpolemtepllye tfealiylefda ialfetderaf5tedra5ysd. aHyso.wHeovewr,etvheer,PthUeAP/UPA/HPSA/HBSP/sBHPsNHstNill mstaiillntmaianinetdailnoendg -ltoenrgm-taerntmifoagntgiifnoggaibniglitaybielivteyneavfetenrabfteirngb eiimngmiermsemderisnedwianterwfaotrer5fdora y5s. Tdhaeysse. rTehseusletsredseulmtso ndsetrmaotenstthrae eo uthtsetaonutdsitnagndwinatgerwraetesirsrteasnicsteaancnedalnodngl-otnegr-mteramntiafnotgifgoign-g pgeirnfgormpaenrfcoeromfaPncUeA/oPfAHPSU/AB/PsAHSN/.BTPos fuHrtNh.er sTtoudfyutrhtehesrt absitliutdyyof tPhUe As/tPabAilHitSy/BoPfs HPNU,Ai/tsPAhyHdSr/oBpPsh ilHicNit,yitswhaysdtreostpehdi iacfiteyrwloasngte-tseterdmaeftxeprolsounrge-tteormhuexmpiodsuaire. ToheumWiCdAa ro.f PTUhAe /WPCAAHSo/f BPUsAH/PNAoHnS/dBifPfserHenNt sounbdsitfrfaetresntdisdubnsottrartiesse  sdigdnifiotcarinstelysiagftneifriceaxnptloysuarfetetro aeirxpforsu6rewteoeakisr (fFoirg6urwe e4efk),s (wFhiigluerteh4e ),WwChAi eofthPeUWAC/PAAoHf SPUHAN/PrAosHeSsiHgnNi fircoasentsliygnaifftie-r ecxapnotlsyuraeftteor aeixrpfosrur1ewtoe eakir. Ionr a1dwdieteiko.nI,nPaUdAdi/tiPoAn,HPSU/BA/PsAHNS/hBaPds bHeNtt ehrahdibgehttaenrdhilgohw teanmdpleorawttuerempceyrcalitnurgerceyscilsitnagncrestishtancPe tUhAa/nPAUHAS/PHANHS( FHigNu(rFe gSu1r2e),Ss1u2)g,gseusgtignesg tnhgathtahte htyhberihdyibzraitdiioznatoifonBPosf eBnPhsaencheadntcheed thertmhearlmstalbsitliatbyiloitfyHofN.HTNh.eTseherses rueltsuilltlsuislltruasterattheathtahte BtPhsehByPbsrihdybproildypmoelryHmeNrcHoaNticnogathiansgehxacselelexncte llweanterw-raetseirs-traenstisatanndt antidf oagntgifnoggpienrgfopremrfaonrc-e anmdanocuetsatnadndoiuntgstsatnadbilnitgy,s tahbuilsitayc,htiheuvsinagchitisevliong-itserlomnag-nteifromggaintigfocgagpianbgilictayp.  \n\n![](images/cf779cc0d3fe4fbe0dd30d9fb1309a8f41ae52022433379804bc43f416b1b64d.jpg)  \nFFiiggurree4.4.Anttiiffoggiing  performances of BPs hybrid polymer HN coattiing and nonhybrriid pollymeerr HN ccooataiting.g.((a))The averrage ttrransmiitttance offPUA/PAHS/BPss HN--ccoaatteed PMMAaanddbbaraere PMMA (t(rtarannsspparaerentntaannddssmootohthplpaltaetse,s,siszize $75\\times25\\:\\mathrm{mm}.$ ,tthicickneesss $3\\mathrm{mm}$ ) wheenneexxpoosseeddttoo hoot t wataetrervvaapoorr $(60\\ ^{\\circ}\\mathrm{C})$ for $60\\mathrm{min}$ . Inset: WCA of PUA/PAHS/BPs HN-coated PMMA $(8^{\\circ})$ and bare PMMA $(73^{\\circ})$ . (b) Optical photographs of a bare PMMA slide and a PMMA slide coated with PUA/PAHS/BPs HN when exposed to hot water vapor $(60~^{\\circ}C)$ for $1\\mathrm{min}$ and $60~\\mathrm{{min}}$ . (c) The average transmittagnracephosfoaf tPhMe PMAMslAidsel dcoeastheodwwai tghooPdUfAie/ldPAofHvSis/ioBnPdsuHrinNgdaunrtifnog gciyncglicteastntaiftoerg gsienvgentewstest. Trhye ocpytcilceasl p(hdo)toTghraephasveorfatghee tPraMnsMmAittsalindce  shofowPaMgMoAod sfiliedledsofcovaistieodn dwuitrhingPUanAt/ifPoAgHgiSngHteNst afntder sePvUeAn/PwAetH–dS/rByPcsycHleNs,. r(eds)pTechteivaevleyr,awgiethtrvaanrsyminitgtathnicekonfesPsMwMheAnselixdpeos ecdoattoehdotwiwthatPerUvAa/pPorA(H60S°HC)N aonvderPtUimAe/.P(Ae)HASn/tiBfPosg gHinNg,  breshpaevcitoirvoelfy,PMwitMhAvsalriydiensg( trhaincskpnaersesntwahnedn semxpootshedpltaotehso,tsiwzeat5e0r vmamp×or $(60\\ ^{\\circ}\\mathrm{C})$ ,otvheircktinmeses. 3(em) mA)ntciofaotgegdi nwgitbhePhUavAi/oPrAofHPSMHMNAansdliPdeUsA(/trPaAnHspS/a6rewnt%anBdPsmHoNo,trhespleactteisv,esliyz,e $50\\mathrm{mm}\\times50\\mathrm{mm}$ , thickness $3\\mathrm{mm}$ ) coated with PUA/PAHS HN and PUA/PAHS/ $6\\mathrm{wt\\%}$ BPs HN, respectively, after being immersed in water for different periods of time. (f) WCA of PUA/PAHS/BPs HN on PET, PC, PMMA and PBS substrates after exposure to air for 1, 2, 3, 4, 5 and 6 weeks, respectively.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.4. Long-Term Antifogging Mechanism of Coatings  \n\nBased on these results, the long-term antifogging mechanism of PUA/PAHS/BPs HN is proposed in Figure 5a. Due to the different surface tensions of BPs and organic polymers, solvent evaporation drives Bénard Marangoni convection during the process of  \n\nUsuVrfcaucreinmga[k3e4]i.t BdiPfsfitceunltdftor  mwiagtreartteotopewnaertdrsattehteocwoartidnsgthseurifnasciededuofe thoeBcéonatirndg,Mpareavnegnot-ni ciongvaenctifong,girnesguflatilnugreiin tdhuecegdenbeyrawtiatoenr ionfvamsiicorno.stTroucvteurirfeyathnids aisnscuremaspetidonr,ouWgChAnetses so,n thmeicsruorsfcaocpei. oDbuse rtvoaetixocnesllaentdwatter-bpaesnedtrlautibornictiteystsanofd PwUatAe/rPaAbHsSo/rBptPisonHcNapwaecrietyc,oBnP-s odnutchteds.uWrfiatchethmeaiknecrietadseififincuUltVfcourriwnagtteirmteo, tpheeneWtrCatAe otfotwhaerdHsNthcoeaitninsigddeeocfretahse cdofartoinmg, p2r3e°vteon t8in°,gianndtiicfaotgingignignfcarielausredinrdoucgehdnebsyswofa tehreincovatsinogns. TdourvienrgifyUtVh icsuarsisnugm(Fpitigounr,eW5bC).A teOsptst,icmalicmriocsrcospciocpoicbsoebrsveartviaotniosnaonfdthweacteora tpinegnesturraftaicoen(taebstosutof1PμUmAt/hiPcAk)HbSe/fBorPesaHndNafwtere cUonVdcucrtiendg. wWaisthfutrhteheirncroenadseucitnedU.VThceurminicgrtoismcoe,pitchephWotCogAraopf hthseofHPNUcAo/aPtiAnHgSd/BecPrseaHsNed firnomF $23^{\\circ}$ eto5 $8^{\\circ}$ s,hinodwictahtiant gBiPnscrmeiagsreadterodutgohwnaersdssotfhtehecocaotaitninggsudrfuarciengduUriVncgurUinVgc(uFriignugr,er5eb-). Osuplttiicnagl imnicernorsicohpmicenotbosferBvPastion tohfethseurcfoactei.nTghseusrefarcesu(altbsopurt $1\\upmu\\mathrm{m}$ atthiBcék)n abredforMeaaranndgaofnteir UcoVncvuercitniognwoafsBfuPrstahnerdcponldyumcetresd.ocTchuerrmeidc rionstchoipsisctupdhyo.toTghreaipmhsprofo vPeUmAe/ntPAofHhSy/dBrPosphHilNici-n Fiitgyuisreat5tcrisbhuotewdtthoathBePinscmreiagsreatiendctoatwinargdrsotuhgehcnoeastsi nafgtesruerfnarcicehdmuerintgofUBVPsc uorni tnhge, rseusrufaltcien.g inToe fnurircthemreantaolfyzBePtshoenwtahtersurerfsaisctea.nTcheeosfePreUsAu/ltPsApHroSv/eBPthsaHt BNé,nitasrdwaMtear apnergmoneiacboilnitvyecwtiaosn otfesBtPesdanafdteprolybeminergs oicmcumrerresdeidn tihnis swtautdery. fTohre i5mpdraoyvs.emTehnet ofwhatyedrropehnileitcriattyioisnatrtaritbeutoefd tPoUthAe/PinAcrHeSa/sBePisnHcoNatdinecgreraosuegdhnweitshs atfhteradendirtiicohnmoefntBPosf cBoPnsteont tahnedsuprfoamceo. oTon foufrther amnalsyszreatihoeofwaPtUerArteosisPtAanHcSe(oFfigPuUreA5/dP).ATHhSe/cBrPosslHinNk,iintgs dweantseirtypeorfmpoelaybimlietrys iwnacsretaesetedd afwtietrhbtehiengadi dmitmioernseofd iPnUwAactoerntfeonrt,5 rdeasyusl.t Tngheinwatdere npsenretHraNtisotnrurcatueroefaPnUdAlo/wPAerHwS/atBePrs HpeNnedtercartieoanserdatew.iItnh  athdediatidodni,titohen ionftrBoPdsucotinotne notf aBnPds cpornotrmiobtuitoendotfotbhleo cmkiansgs trhateiopeorfmPeUa-A ttoioPnAoHf Sw(aFtiegr,utrheu5sde)n. hTahnec cnrgostshleinwkaitnegr rdesnistitayncoefopfoPlyUmAe/rPsAiHncSr/eBaPsedHNwiitnhatheuamdiditeino-n ovfirPoUnAmecnotn.tent, resulting in a denser HN structure and lower water penetration rate. In additiTohne, athbeovien trreosdulutcstidoenmofnsBtPrastceothnterliobnugt-etdertmo balnoticfkoigngintghepeprefrormeatnicoenmofecwhatneirs,mthoufs etnhheapnrcoipnogstehdecwoatienrgr.esistance of PUA/PAHS/BPs HN in a humid environment.  \n\n![](images/a4d497e4073a54918d80903b24e881eea1c4d10b87b5c149ab4ea3ff109fdb78.jpg)  \nFiigurre 5. (a) Schematiticc diaiaggraramofoflolnogn-gte-tremrmanatinftoifgogigngginmg emcheacnhiasnmisomf PofUPA/UPA/HPSA/BHPSs/HBPNs. (Hb)N. (b) WCA of PUA/PAHS/BPs HN with different UV curing times. (c) Microscopic photographs of PUA/PAHS/BPs HN before and after UV curing. (d) Water penetration rate of PUA/PAHS/BPs HN with different BPs content and mass ratio of PUA to PAHS.  \n\nThe above results demonstrate the long-term antifogging performance mechanism of the proposed coating.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 4. Conclusions  \n\nIn summary, for the first time, a BPs hybrid super-hydrophilic polymer HN coating (PUA/PAHS/BPs HN) was prepared by UV curing for long-term antifogging performance. Different from physical blending, covalent P-C bonds between BPs and polymer were generated by UV-initiated free radical reaction, resulting in BPs firmly embedded in the polymer HN structure. The BPs enriched on the coating surface by UV regulating migration can effectively prevent the permeation of water towards the inside of the coating through its own good water-based lubricity and water absorption capacity. Compared with nonhybrid polymer HN, PUA/PAHS/BPs HN not only has higher hardness and better friction resistance properties, but also exhibits superior water resistance and longer antifogging duration. Since water invasion is greatly reduced by BPs, PUA/PAHS/BPs HN maintained 60 min antifogging duration under the $60~^{\\circ}C$ water vapor test and still maintained long-term antifogging performance after being immersed in water for 5 days. After exposure to air for 6 weeks, the antifogging performance of PUA/PAHS/BPs HN did not decline, showing its outstanding stability. This study provides not only a method for fabricating BP hybrid polymer materials through the generation of P–C bonds induced by free radical reaction, but also a new way for regulating the directional enrichment of BP towards the surface of a composite structure, which presents new approaches for long-term antifogging in humid environments.  \n\nSupplementary Materials: The following supporting information can be downloaded at: https: //www.mdpi.com/article/10.3390/nano13010086/s1, instruments; Figures S1 and S2: Schematic diagram of synthesis of PUA and PAHS; Figures S3 and S4: 1 H NMR spectra of PUA and PAHS; Figure S5: FTIR spectrum of (a) PUA; (b) PAHS; Figure S6: SEM image of BPs; Figure S7: Crosssectional SEM image of PUA/PAHS/BPs HN; Figure S8: AFM image of PUA/PAHS/BPs HN; Figure S9: FTIR spectrum of (a) PUA/PAHS HN; (b) PUA/PAHS/BPs HN; Figure S10: XPS spectrum of PUA/PAHS/BPs HN; Figure S11: Transmission spectra of PUA/PAHS/BPs HN with (a) $0{-}6~\\mathrm{wt\\%}$ BPs; (b) $8–18\\mathrm{wt\\%}$ BPs; Figure S12: Transmission spectra of PUA/PAHS/BPs HN during high and low temperature cycles.  \n\nAuthor Contributions: Project administration, X.-F.Y., R.H. and F.Y.; conceptualization, X.-F.Y., R.H., F.Y. and L.W.; funding acquisition, X.-F.Y., R.H. and F.Y.; investigation, L.W., Y.K. and Y.D.; methodology, L.W.; visualization, L.W.; writing—original draft, L.W.; writing—review and editing, X.-F.Y., R.H., F.Y. and L.W. All authors have read and agreed to the published version of the manuscript.  \n\nFunding: This study was supported by Guangdong Basic and Applied Basic Research Foundation (2020B1515120040); Shenzhen Basic Research Foundation (JCYJ20200109115408041); Guangdong Basic and Applied Basic Research Foundation (2020A1515110831); Shenzhen Science and Technology Program (Grant No. RCJC20200714114435061).  \n\nData Availability Statement: The data presented in this study are available on request from the corresponding author.  \n\nConflicts of Interest: The authors declare no conflict of interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 16,
+        "chunk": "# References  \n\n1. Han, Z.; Feng, X.; Guo, Z.; Niu, S.; Ren, L. Flourishing bioinspired antifogging materials with superwettability: Progresses and challenges. Adv. Mater. 2018, 30, 1704652. [CrossRef] [PubMed]   \n2. Zhao, J.; Ma, L.; Millians, W.; Wu, T.; Ming, W. Dual-functional antifogging/antimicrobial polymer coating. ACS Appl. Mater. Interfaces 2016, 8, 8737–8742. [CrossRef] [PubMed]   \n3. Lee, H.; Alcaraz, M.L.; Rubner, M.F.; Cohen, R.E. Zwitter-wettability and antifogging coatings with frost-resisting capabilities. ACS Nano 2013, 7, 2172–2185. [CrossRef] [PubMed]   \n4. Yoon, J.; Ryu, M.; Kim, H.; Ahn, G.N.; Yim, S.J.; Kim, D.P.; Lee, H. Wet-style superhydrophobic antifogging coatings for optical Sensors. Adv. Mater. 2020, 32, 2002710. [CrossRef] [PubMed]   \n5. Sun, Z.; Liao, T.; Liu, K.; Jiang, L.; Kim, J.H.; Dou, S.X. Fly-eye inspired superhydrophobic anti-fogging inorganic nanostructures. Small 2014, 10, 3001–3006. [CrossRef] [PubMed]   \n6. 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Tang, G.; Su, F.; Xu, X.; Chu, P.K. 2D black phosphorus dotted with silver nanoparticles: An excellent lubricant additive for tribological applications. Chem. Eng. J. 2020, 392, 123631. [CrossRef]   \n21. Wang, Q.; Hou, T.; Wang, W.; Zhang, G.; Gao, Y.; Wang, K. Tribological behavior of black phosphorus nanosheets as water-based lubrication additives. Friction 2022, 10, 374–387. [CrossRef]   \n22. Zhang, Y.; Mu, C.; Xie, J.; Ågren, H.; Zhang, H. Black phosphorus/polymers: Status and challenges. Adv. Mater. 2021, 33, 2100113. [CrossRef] [PubMed]   \n23. Qiu, S.; Zhou, Y.; Zhou, X.; Zhang, T.; Wang, C.; Yuen, R.K.; Hu, W.; Hu, Y. Air-Stable Polyphosphazene-Functionalized Few-Layer Black Phosphorene for Flame Retardancy of Epoxy Resins. Small 2019, 15, 1805175. [CrossRef] [PubMed]   \n24. Xie, H.; Shao, J.; Ma, Y.; Wang, J.; Huang, H.; Yang, N.; Wang, H.; Ruan, C.; Luo, Y.; Wang, Q.Q.; et al. 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Huang, H.; Gao, M.; Kang, Y.; Li, J.; Wang, J.; Wu, L.; Chu, P.K.; Huang, Y.; Ibarra, M.R.; Yu, X.-F. Rapid and scalable production of high-quality phosphorene by plasma-liquid technology. Chem. Commun. 2020, 56, 221–224. [CrossRef]   \n34. Wei, Z.; Wang, Y.; Cai, C.; Zhang, Y.; Guo, S.; Fu, Y.; Tan, S.C. Dual-network liquid metal hydrogel with integrated solar-driven evaporation, multi-sensory applications, and electricity generation via enhanced light absorption and bénard-marangoni effect. Adv. Funct. Mater. 2022, 32, 2206287. [CrossRef]  \n\nDisclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,77 @@
+[
+    {
+        "id": 1,
+        "chunk": "# 自然 机器智能",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# 大规模化学语言表征捕捉分子结构和特性  \n\n收到：2022 年 4 月 18 日  \n\n接受：接受： 2022 年 11 月 3 日  \n\nJerret Ross , Brian Belgodere, Vijil Chenthamarakshan , Inkit Padhi, Youssef Mroueh & Payel  \n\n在线出版：2022 年 12 月 21 日",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# 检查更新  \n\n基于机器学习的模型可以准确、快速地预测分子性质，这在药物发现和材料设计方面具有重要意义。各种有监督的机器学习模型都表现出了良好的性能，但广阔的化学空间和有限的性质标签使得有监督的学习具有挑战性。最近，基于无监督变换器的语言模型在大量无标签语料库上进行了预训练，在许多下游自然语言处理任务中取得了一流的成果。受这一发展的启发，我们提出了通过训练高效的变换器编码器模型 MoLFormer 获得的分子嵌入。  \n\n位置嵌入。该模型采用线性注意机制，并结合高度分布式训练，对来自PubChem 和 ZINC 数据集的 11 亿个无标签分子的 SMILES 序列进行了训练。我们的研究表明，在来自十个基准数据集的多个下游任务上，学习到的分子表示优于现有的基准，包括监督和自我监督图神经网络和语言模型。它们在另外两个数据集上的表现也很有竞争力。进一步的分析，特别是通过注意力的视角，表明 MoLFormer  \n\n在化学 SMILES 基础上进行的训练确实可以学习分子内原子之间的空间关系。这些结果提供了令人鼓舞的证据，证明大规模分子语言模型可以捕捉到足够的化学和结构信息来预测各种不同的分子特性，包括量子化学特性。  \n\n机器学习（ML）已成为预测分子性质的一种极具吸引力的高效计算方法，对药物发现和材料工程具有重要意义。分子的 ML 模型可以直接根据预定义的化学描述符（如无监督分子指纹(1)）或几何特征（如库仑矩阵(2)）的手工衍生衍生物进行训练。然而，最近的 ML 模型侧重于从编码连接性的自然图谱中自动学习特征。  \n\n或分子结构的行注释，如流行的 SMILES3（简化分子输入行输入系统）表示法。SMILES 通过对分子图进行深度优先的前序生成树遍历，为每个原子、键、树遍历判定和断裂循环生成符号，从而定义了分子的字符串表示法。因此，生成的字符串对应于分子图生成树的扁平化。在 SMILES 上学习已被广泛用于  \n\n![](images/61b588554868f7b6b3cb4b02609903fea7a008b0c518affebb356d5a2546982d.jpg)  \n图 1|  MoLFormer 管道概览。基于变压器神经网络的模型是以自我监督的方式，在与来自 PubChem 和 ZINC（两个公共化学数据库）的大量化学分子对应的 SMILES 序列上进行训练的。MoLFormer 的设计采用了高效的线性注意机制和相对位置嵌入，目的是学习有意义的、压缩的化学表达式。  \n\n分子特性预测4-7，因为 SMILES 通常比包括图形在内的其他结构表示方法更为简洁。此外，SMILES 字符串还明确表示了有意义的子结构，如分支、环状结构和手性信息，而图形表示法则没有这些信息。  \n\n然而，SMILES 语法既复杂又有限制性；适当字符集上的大多数序列  \n\n都不属于定义明确的分子。目前存在其他基于字符串的表示法，如SMARTS8 和 SELFIES9。比较这些替代表示法与 SMILES 的优势是一个活跃的研究领域。例如，参考文献10 着重研究了学习表示空间上分子优化任  \n务，结果表明就优化能力和采样效率而言，SMILES 与 SELFIES 相比没有明显的不足，尤其是当语言模型更先进时。不过，人们认为基于字符串的表征不具有拓扑意识，而基于图形的表征具有拓扑意识。由于这些限制，深度化学语言模型可能会侧重于学习分子字符串的语法，而不是分子  \n图的隐含拓扑结构。因此，虽然基于字符串的深度神经网络已被用于预测分子性质5(-)(7)(,)(11)，但它们的性能通常比图神经网络（GNN）12及其变体13(-)(21)要好。图神经网络框架一般可被视为 \"信息传递\"，其中包括本地邻域信息聚合，以及根据图的连接结构在不同粒度级别（例如节点、边或整  \n个图）上进行信息更新。用于分子特性预测的 GNN 和语言模型的监督训练面临的一个挑战是标记数据的稀缺。分子的标签注释通常成本高昂，  \n而需要注释的可信化学物质的空间大得惊人（ $10^{60}$ 到 $10^{(100)}$ ）(22)，这使得问题更加复杂。在这种情况下，就需要进行分子表征学习，以便在无监  \n督/自我监督的下将其推广到各种性质预测任务中。基于转换器的大型基  \n础模型2324最近取得了成功，该模型采用了学习与任务无关的语言表征的方法，通过在大型无标签语料库上进行预训练获得，随后利用该表征对感兴趣的下游任务进行微调。  \n\n到其他领域。  \n\n用于预测分子性质的预训练语言模型（25）和 GNNs（26）最近才开始出现。然而，在由数 $+$ 亿分子组成的大型语料库上训练的预训练语言模型在多大程度上能够在各种下游任务中捕捉到分子-属性关系仍有待探索。  \n\n分子。然后，通过对特定任务的数据进行微调，使这一基础模型适用于不同的下游分子特性预测任务。通过使用 MoLFormer 编码恢复分子相似性，以及分析给定的原子间空间距离和注意力值之间的对应关系，进一步测试了该模型的代表性。  \n\n朝着这个方向，我们在此提出了分子 SMILES 转换器模型，称为MoLFormer（分子语言转换器）。我们将性能最好的 MoLFormer 变体命名为 MoLFormer-XL。MoLFormer-XL 是在一个包含 11 亿个分子的大型语料库（图 1）中使用高效的线性注意机制训练出来的。结果表明，在预测包括量子力学性质在内的各种分子时，经过预训练的分子 SMILES 变换器编码器与现有的有监督或无监督语言模型和 GNN 基线相比具有很强的竞争力0  \n\n我们的主要贡献如下  \n\n• 我们利用相对有限的硬件资源（最多 16 个 V100 图形处理器（GPU））在超过十亿个分子上训练了大规模高效分子语言模型转换器MoLFormer）。我们的可扩展性和速度提升归功于高效的线性时间关注、批次的自适应分级以及 PyTorch Lightning 和 NCCL 提供的开源并行化。利用分批和线性注意的组合，我们能够实现每个 GPU1,600 个分子的批次规模。使用 16 个 GPU，我们需要 208 小时才能完成 MoLFormer-XL 的四次预训练。要在相同的时间内完成训练，如果不使用分级和线性注意，每个 GPU 只能处理不到 50 个分子，需要超过 1000 个 GPU 才能完成任务。  \n\n• 我们探讨了绝对位置嵌入和相对位置嵌入在表示分子 SMILES 时的区别。我们还为最近提出的相对位置 RoFormer27 提供了一种新的、高效和准确的线性注意近似方法。  \n• 我们对来自 MoleculeNet28 的十个基准数据集的若干分类和回归任务进行了广泛的实验和消融研究，这些数据集涵盖了小分子化学物质的量子力学、物理、生物物理和生理特性预测。  \n• 我们的研究结果提供了令人鼓舞的证据，证明 MoLFormer 表示法能够准确捕捉足够的化学和结构信息，从而预测各种化学特性。此外，MoLFormer 的性能优于从精确的图拓扑信息和其他信息（例如键距）中学习的最先进的 GNN，或者与之相当。  \n• 我们进一步分析表明，MoLFormer 可以仅从 SMILES 注释中捕捉分子内的子结构以及原子间的空间距离。  \n\n![](images/6026d0b8bdefb9cb112647c1a61896f5f0f3b7720ac4c9f63c6ebc6ae9aad771.jpg)  \n图 2|  绝对嵌入和旋转嵌入的训练损失和验证损失比较。a,b, 使用旋转（相对）和绝对位置嵌入的线性注意力 MoLFormer 的训练损失（a）和验证损失（b）。  \n\n![](images/c4386b90071a5579f572fa056fc13b66489904409a8a3b80df1e765e2e7d7778.jpg)  \n步骤  \n\n在 PubChem 上。我们发现，旋转式和绝对式 MoLFormer 都有优美的训练曲线。与使用绝对位置嵌入的 MoLFormer 相比，我们的旋转线性注意力MoLFormer 的训练和验证损失更低。  \n\n本研究探讨了预先训练好的化学语言模型在预测从量子化学到生理学的广泛下游分子特性方面的表征能力。特别是，仅从 SMILES 字符串预测量子化学性质并非易事，因为这些性质在很大程度上取决于精确的三维（3D）分子几何信息，而这些信息被视为特权信息，一般无法获得。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# 结果和讨论",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# MoLFormer 框架  \n\n如图 1 所示，MoLFormer 的目标是从大规模化学 SMILES 数据中学习通用分子表征，然后在各种下游分子性质预测任务中评估该表征。，MoLFormer 模型使用屏蔽语言模型框架29,30 开发，该框架在训练过程中随机屏蔽 SMILES 序列中一定比例的标记，然后预测这些标记。因此，屏蔽语言模型利用了自我监督，实现了上下文学习。为了实现更好的语境学习和更快的训练，我们使用了旋转位置嵌入（27）而不是绝对位置嵌入，同时还使用了线性注意（31）（关于模型结构和训练的更多细节，请参见方法和补充信息）。如图 2 所示，与绝对嵌入相比，使用旋转嵌入进行预训练时，我们发现训练损失行为的稳定性更高，收敛速度更快。为了证明预训练 MoLFormer 作为通用的、与任务无关的分子表示法的有效性，我们在来自 MoleculeNet28 的大量具有挑战性的分类和回归任务中对其适应性能进行了基准测试。有关基准数据集的详细信息，请参见补充章节 C。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# MoLFormer 嵌入的推导  \n\n我们通过从编码器模型中提取最后一个隐藏状态的所有嵌入值的平均值，对化学 SMILES 进行编码。由此产生的嵌入值将用于所有下游任务。下游任务本身可分为两类，第一类称为冻结任务，第二类称为微调任务。冻结设置的定义是为每个任务训练一个完全连接的模型，同时保持编码器嵌入固定不变。第二类是微调，包括针对每个下游任务联合微调编码器模型和全连接模型的权重。冻结策略的理想配置和超参数是通过网格搜索发现的，如补充表 1 所述。对于微调后的  \n\n在策略上，我们使用了一个两层全连接网络，其隐藏维度为 768（与编码器嵌入相匹配），中间有滤除（设置为 0.1）和高斯误差线性单元层，最后还有一个用于回归任务的单一输出维度。  \n\nMoLFormer嵌入式在下游任务中的性能 我们评估了MoLFormer嵌入式的性能，并在MoleculeNet基准28的六项分类任务和五项回归任务中将其与现有基线进行了比较，讨论如下。我们将在由 ${\\approx}11$ 亿个分子（来自 PubChem和 ZINC 的所有分子）组成的整个训练集上经过预训练的 MoLFormer 称为MoLFormer-XL。除非另有说明，MoLFormer-XL 使用旋转位置嵌入进行线性注意训练，报告的性能是模型在下游任务中微调后的性能（详见方法）。为了预测下游任务中的各种适当关系，我们按照上一节所述对模型进行了微调。我们使用 MoleculeNet 基准为所有任务定义的训练、验证和测试数据（补充章节 C）。  \n\n分类任务。我们从 Mol- eculeNet 基准中选择了六项分类任务与 MoLFormer-XL 进行比较，共有九条基准线，其中四条是监督基准线，五条是自我监督基准线。监督基线包括根据分子指纹训练的浅层 ML 模型（表 1 中的 RF 和 SVM）和图神经网络。在预训练/自我监督基线中，Hu 等人32 在分子图上预训练了一个图同构网络（GNN，在聚合中使用多层感知器和节点特征加权和），其中包括参与聚合的边缘特征。N-gram graph33使用了一种简单的无监督分子表示法，首先将节点嵌入图中，然后通过将顶点嵌入集合到图中的短路径来构建图的紧凑。MolCLR26是一种基于图同构网络的自监督学习框架，它使用对比损失34,35。GraphMVP-C 是参考文献 36 中提出的图形多视图预训练框架。36 中提出的图形多视图预训练框架，利用二维拓扑结构和三维几何视图之间的对应性和一致性进行自监督学习。我们还考虑了其他三个几何感知GNN 基线，一个是监督式（DimeNet37），两个是自监督式（GeomGCL36 和GEM38）。ChemBERTa25 是在一个较小的化学数据集上训练的预训练分子语言模型。表 1 记录了 MoLFormer 与这些基线在六个分类基准上的性能比较，使用的是 MoleculeNet  \n\n表 1| 微调后的 MOLFORMER 与现有的监督和预训练/自我监督基线在多个分类基准上的比较  \n\n\n<html><body><table><tr><td></td><td>BBBP 1</td><td>Tox21 12</td><td>临床毒理学2艾滋病毒</td><td>1</td><td>BACE1</td><td>SIDER 27</td></tr><tr><td>射频</td><td>71.4</td><td>76.9</td><td>71.3</td><td>78.1</td><td>86.7</td><td>68.4</td></tr><tr><td> SVM</td><td>72.9</td><td>81.8</td><td>66.9</td><td>79.2</td><td>86.2</td><td>68.2</td></tr><tr><td>MGCN56</td><td>85.0</td><td>70.7</td><td>63.4</td><td>73.8</td><td>73.4</td><td>55.2</td></tr><tr><td>D-MPNN57</td><td>71.2</td><td>68.9</td><td>90.5</td><td>75.0</td><td>85.3</td><td>63.2</td></tr><tr><td>DimeNet37</td><td>－</td><td>78.0</td><td>76.0</td><td></td><td></td><td>61.5</td></tr><tr><td>Hu (32)</td><td>70.8</td><td>78.7</td><td>78.9</td><td>80.2</td><td>85.9</td><td>65.2</td></tr><tr><td>N-gram33</td><td>91.2</td><td>76.9</td><td>85.5</td><td>83.0</td><td>87.6</td><td>63.2</td></tr><tr><td>MolCLR26</td><td>73.6</td><td>79.8</td><td>93.2</td><td>80.6</td><td>89.0</td><td>68.0</td></tr><tr><td>GraphMVP-C36</td><td>72.4</td><td>74.4</td><td>77.5</td><td>77.0</td><td>81.2</td><td>63.9</td></tr><tr><td>GeomGCL36</td><td>-</td><td>85.0</td><td>91.9</td><td></td><td>-</td><td>64.8</td></tr><tr><td>创业板38</td><td>72.4</td><td>78.1</td><td>90.1</td><td>80.6</td><td>85.6</td><td>67.2</td></tr><tr><td>化学ERTa25</td><td>64.3 93.7</td><td>84.7</td><td>90.6</td><td>62.2</td><td>-</td><td></td></tr></table></body></html>\n\n粗体表示表现最好的模型。所有模型都是通过支架分割的接收者操作特征曲线下面积进行评估的。基线性能采用文献 25、26、36 中的数据。25、26、36，\"-\"表示没有报告相应任务的数值。  \n\n脚手架数据分割。在六项基准测试中，MoLFormer-XL 在三项（BBBP、ClinTox 和 SIDER）测试中的表现优于所有基准，在另外三项（ $\\bar{\\mathsf{T o x}}21$ 、HIV 和 BACE）测试中紧随其后。  \n\n回归任务。接下来，我们在 MoleculeNet 中难度更大的回归任务上对MoLFormer-XL 进行了评估。我们在表 2 中报告了我们在 QM9、QM8、ESOL、FreeSolv 和 Lipophilicity 这五个回归基准上的表现（另见补充章节 D 和E）。其中，QM9 和 QM8 涉及多个量子化学指标的预测，这在无法获取特定三维几何信息的情况下具有挑战性。在这些任务中，我们再次使用了参考文献 28 中建议的训练、验证和测试拆分方法。我们考虑的基线是分子图卷积网络（GC，一种在线性变换前利用节点及其邻域的均值池的GNN）39、殷勤 FP（A-FP）模型40 和一种学习边缘特征（如成对原子间距离）的 MPNN 变体18。结果表明，MoLFormer-XL 经过特定任务的微调后，在所有五项任务中表现都优于现有的有监督 GNN 基线，特别是 GC、A-FP 和 MPNN（针对 QM8 和 QM9 采用键距增强）。补充表 7 进一步显示，在三个物理属性回归基准上，MoLFormer 的表现优于几何感知 GNN（DimeNet、GeomGCL 和 GEM）。这些结果，再加上 MoLFormer-XL 在分类基准上的表现，证实了它的通用性。  \n\n进一步了解 QM9。补充表 9 进一步比较了 MoLFormer-XL 在 QM9 原子化能量和焓（根据参考原子修正的内能/焓，以电子伏特为单位）预测任务上的表现，以及 SchNet41 和 Dimenet37 这两个超视觉 3D GNN 的表现。仅在SMILES 上训练的 MoLFormer-XL 在所有四项任务中的表现都优于这两个模型。然而，SchNet 和 DimeNet 直接对三维进行编码，并采用专门的架构对量子进行建模，但它们仅分别以大约 8 倍和大约 10 倍的优势胜过 MoLFormer-XL。这一结果以及表 1 和表 2 再次证明了从 SMILES 等现成信息中学习通用分子表示法的能力、  \n\n表 2 微调后的 MOLFORMER 和其他有监督 GNN 基线在 QM9、QM8、ESOL、FreeSolv 和亲脂性回归基准上的表现  \n\n\n<html><body><table><tr><td></td><td>QM9</td><td>QM8</td><td>ESOL</td><td colspan=\"2\">FreeSolv亲脂性</td></tr><tr><td>GC</td><td>4.3536</td><td>0.0148</td><td>0.970</td><td>1.40</td><td>0.655</td></tr><tr><td>A-FP</td><td>2.6355</td><td>0.0282</td><td>0.5030</td><td>0.736</td><td>0.578</td></tr><tr><td>MPNN</td><td>3.1898</td><td>0.0143</td><td>0.58</td><td>1.150</td><td>0.7190</td></tr><tr><td>M LF</td><td>-XL 1.5894</td><td>0.0102</td><td>0.2787</td><td>0.2308</td><td>0.5289</td></tr></table></body></html>\n\n对于 QM9 和 QM8，我们报告的是平均 MAE，其余任务报告的是均方根误差。基准性能来自参考文献。28,40.粗体表示表现最好的模型。  \n\n同时证实了特权几何信息在量子化学能量预测中的关键作用。此外，这次比较的结果为未来的研究打开了大门，其目标是估计 MoLFormer 中几何意识的出现（见后面的章节），或如何通过添加部分或完整的三维几何信息来进一步增强仅有 SMILES 的 MoLFormer 的表现力。  \n\n烧蚀研究。在本节中，我们将讨论 MoLFormer-XL 的几种不同消融情况，以深入了解其令人印象深刻的性能。我们进行的消融大致可分为以下三类：(1)预训练数据和模型深度的大小和性质的影响，(2) 对下游数据和模型进行微调（冻结）和微调（微调）后的结果。  \n(3) 绝对位置嵌入和旋转位置嵌入的影响。  \n\n数据/ 模型大小。首先，我们研究了预训练数据集的大小如何影响MoLFormer-XL 在 MoleculeNet 基准的几个下游任务上的性能。为此，我们选择了 PubChem 和 ZINC 数据集的三种不同加权组合，特别是由 $10\\%$ 的 ZINC 和 $10\\%$ 的 PubChem 组成的数据集、由 $100\\%$ 的 PubChem 和 $10\\%$ 的 ZINC 组成的数据集，以及由 $100\\%$ 的 ZINC 分子和 $0\\%$ 的 PubChem 组成的数据集。我们还通过在完整的 ZINC 和 PubChem 数据集上预训练一个名为 MoLFormer-Base 的六层模型来研究模型深度的影响。所有模型都使用旋转嵌入和线性注意进行预训练，然后与 MoLFormer-XL 进行比较。相同的学习率、数据分割、优化等都用于预训练和微调。扩展数据表 1 和表 2总结了这些结果。虽然 MoLFormer-XL 的平均表现更好，但我们报告了两个有趣的观察结果。首先，在第二大数据集 $100\\%$ ZINC 上进行预训练的模型的表现一直比其他所有预训练模型差。仅在 ZINC 数据集上训练的模型表现不佳的一个可能原因是，ZINC 数据集包含的词汇量比所有其他数据集组合要小得多，而且分子更短，分子长度的差异很小。另一个值得关注的问题是，当 MoLFormer-XL 落后时，其差距也非常小（见表 2 中ESOL、QM8 和 FreeSolv 基准的性能）。扩展数据表 1 和表 2 进一步显示，在大多数任务中，MoLFormer-Base 性能都低于 MoLFormer-XL，这意味着更深层次的模型有助于学习。  \n\n微调与冻结。扩展数据 表 3 进一步总结了使用 QM9 基准进行的其余两项消融实验。为了简单起见，我们发现在所有预训练数据集上，微调消融实验比冻结实验取得了令人信服的胜利，因此我们选择只对所有其他基准进行微调。这些结果为 MoLFormer 的神经和数据扩展行为提供了经验见解。  \n\n表 3| MOLFORMER 模型与原子间空间距离图和注意力图之间余弦相似性的比较，针对 QM9 测试集中 7 806 个分子的三种不同距离类别  \n\n\n<html><body><table><tr><td>距离类别</td><td>请注意</td><td>1</td><td>3</td><td>5</td><td>7</td><td>9</td><td>11</td></tr><tr><td rowspan=\"2\">短</td><td>完整(√旋转式)</td><td>0.615</td><td>0.604</td><td>0.603</td><td>0.615</td><td>0.601</td><td>0.598</td></tr><tr><td>线性(√旋转)</td><td>0.596</td><td>0.597</td><td>0.602</td><td>0.597</td><td>0.600</td><td>0.594</td></tr><tr><td rowspan=\"2\">中型</td><td>完整(√旋转式)</td><td>0.716</td><td>0.724</td><td>0.724</td><td>0.716</td><td>0.727</td><td>0.727</td></tr><tr><td>线性(√旋转）</td><td>0.729</td><td>0.728</td><td>0.724</td><td>0.727</td><td>0.726</td><td>0.730</td></tr><tr><td rowspan=\"2\">长</td><td>完整(√旋转式)</td><td>0.204</td><td>0.207</td><td>0.208</td><td>0.205</td><td>0.208</td><td>0.210</td></tr><tr><td>线性(√旋转）</td><td>0.211</td><td>0.210</td><td>0.210</td><td>0.211</td><td>0.209</td><td>0.210</td></tr></table></body></html>\n\n短距离、中距离和长距离类别的原子间距离范围分别为、2-4 和 4-10 Å。粗体表示表现最好的模型。  \n\n位置嵌入。扩展数据表 3 收集了位置嵌入消减结果，结果表明，在较小的数据集上，使用旋转嵌入和微调的 MoLFormer 落后于绝对位置嵌入模型，但当数据集规模超过 10 亿个分子时，MoLFormer 则胜出。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 深入了解 MoLFormer  \n\n分子相似性恢复。接下来，我们分析了在分子指纹上使用谷本距离（一种常用的化学物质间成对测量方法）估算的成对相似度与在 MoLFormer-XL 嵌入上使用欧氏距离估算的成对相似度之间的相关性。我们还进一步研究了一对分子的最大公共子图中的原子数与它们在嵌入空间中的相应欧氏距离之间的相关性，这些分子是从 PubChem 中随机挑选出来的。扩展数据表 4 对结果进行了总结，结果表明与 ChemBERTa 相比，MoLFormer-XL 嵌入与已知分子相似性度量的相关性更好。这些结果表明，MoLFormer 嵌入对化学结构相似性具有参考价值。  \n\n注意力分析。最后，我们检查了 MoLFormer-XL 的平均集合注意力矩阵，以探索蕴含的化学信息。，我们利用注意力值与 QM9 测试集中分子内原子间空间距离之间的余弦相似性。空间距离是从 QM9 基准（28）中提供的相应能量最小化几何图形中获得的。在整个 PubChem $^+$ ZINC 数据集上，MoLFormer-XL 与经过全神贯注和旋转嵌入训练的 MoL Former 变体进行了比较。请注意，这里的 MoLFormer 模型没有针对 QM9 数据集进行微调。在 QM9 下游任务中，全神贯注的冻结 MoLFormer 显示出更高的平均绝对误差（ ${\\mathrm{.}}M A E\\geq12$ ）；在内能（ $\\upsilon$ 和 $U_{0}\\overbrace{\\mathbf{\\Omega}}$ ）、焓 $\\left(\\boldsymbol{H}\\right)$ ）和自由能（G）方面的表现尤其糟糕。我们分别列出了三类不同原子间空间距离的注意力结果--短距离（ $.\\leq2\\mathring{\\mathsf{A}}$ ；主要反映分子中典型的共价键，C-C 单键距离为 1.5）、中距离（2-4）和长距离（ $\\geq4)$ ）--并在表 3 中进行了总结。有趣的是，MoLFormer 中的线性注意力或完全注意力（以及旋转位置嵌入）与短原子间距和中等原子间距的相似性很强，而与长原子间距的相似性较弱（约 0.2）。这是一个有趣的观察结果，表明 MoL Former 能够捕捉 SMILES序列中不一定相邻的原子标记之间的空间关系。与全神贯注的MoLFormer 相比，在 MoLFormer-XL 中观察到的注意力更符合中距离和长距离。这一观察结果表明，使用线性注意力的 MoLFormer-XL 事实上能更有效地捕捉原子之间的空间关系。  \n\n图 3 进一步阐述了这一点，显示了 MoLFormer-XL 中间注意层的平均学习注意系数和旋转位置嵌入。不同原子标记对之间的注意力与原子对之间的共价键连通性和三维距离进行了比较（所有层中相同分子的完整注意力矩阵见补充图 5 和 6）。我们从 QM9 测试集中选择了注意力值与中程空间距离具有高度余弦相似性的两个分子进行可视化。目测结果表明，中间旋转注意力层上的头部聚集与共价键模式非常吻合，同时也捕捉到了分子内非键原子间空间关系的特征。这些注意力分析结果表明，MoLFormer-XL 能够在很大程度上从相应的 SMILES 序列中恢复分子结构信息。这种能力可能源于对大量化学SMILES语料的预训练，这也使得MoLFormer-XL能够学习化学物质的基本属性，包括结构信息和从量子化学到生理学的各种下游属性。最近的蛋白质序列建模工作也报告了类似的观察结果42,43。这证实了通过大规模数据预训练的化学语言模型所学习到的表征中出现了结构和各种属性信息。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 结论  \n\n在这项工作中，我们探索了无监督大规模预训练分子语言模型在各种分子特性预测任务中的威力。与图不同，SMILES 等分子语言并不明确编码分子拓扑结构。然而，通过在大规模语料库上进行精心设计的自监督训练，并采用富有表现力的架构（如具有线性注意机制的基于上下文转换器的语言模型）和并行化训练协议，我们的 MoLFormer 可以高效地学习隐含的丰富结构-属性关系信息。  \n\n具体来说，MoLFormer 在各种分子回归和分类基准上的表现都优于现有的基于图的基准线。这项工作验证了大规模自监督预训练分子语言模型在预测从量子化学到生理学整个范围的分子特性方面的能力。此外，通过分析所学到的关注点，我们证明了在 SMILES 序列上训练的 MoLFormer 确实能够意识到分子内的原子间关系，甚至超越了二维拓扑结构。最后，在大规模学习方面，我们展示了MoLFormer对计算资源的高效和环境友好型利用，将执行训练所需的GPU数量减少了60（1000对16）。  \n\nMoLFormer 有助于更快地对不同靶点的分子进行硅学筛选，这对材料设计和药物发现应用非常重要，并能产生积极的社会影响。然而，应该注意的是，滥用这种技术而不  \n\n![](images/4a852df430ae581fcacffea07a82daae05e0a71eba055b10be9fbfb50a8b0d35.jpg)  \n\nCC1(C)C(C)(O)C1(C)O\"a）和 \"CC(C)C(C)(C)O\"b） 注意图（范0围.02从 0 到 1；只显示 色环绕部分）中程三维距0.01离。与组成原子映射的标记 0 0  \n\n在湿实验室进行适当的实验和科学验证可能会产生有害影响。此外，有研究表明，准确的属性预测模型（，用于预测毒性）和生成模型可用于设计分子（44）。这就强调了需要一个负责任的框架  \n\n围绕使用这些新兴的强大技术。此外，本研究还要求进一步探索MoLFormer 直接从化学语言中学习分子结构信息的表征能力，并可将其扩展到本中所研究的小分子有机物之外。  \n\n未来的工作还将通过采用更大的模型和更多的训练数据、使用改进的和/或特定领域的自我监督任务以及使用其他基于字符串的表示方法（如SELFIES(9)）来改进 MoLFormer。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 9,
+        "chunk": "# 方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 型号详情  \n\n由于我们的目标是在利用相对有限的硬件资源的同时，高效率、高效益地训练化学 SMILES 的大规模屏蔽语言模型，因此我们利用了基于变压器的神经网络（23）。变压器通过一系列自注意和前馈连接交替的区块处理输入。它们通过位置嵌入（称为绝对位置嵌入）对序列中的位置进行编码。因此，位置 $m$ 上的输入特征会与相应的绝对位置嵌入连接起来。自我注意使网络能够构建包含整个序列上下文的复杂表征。注意机制会将序列中的特征转化为查询 $(q)$ 、键 $(k)$ 和值 $(v)$ 表示。这些表征会在 $m$ 处产生如下的注意力输出：  \n\n$$\n\\begin{array}{r l}&{\\sum_{n\\ {\\bf{\\epsilon}}^{n}}^{N}\\exp\\left(\\langle q_{\\mathrm{~,~}k}\\rangle\\right)\\psi\\ }\\\\ {\\langle Q,K,V=}&{\\ \\frac{n\\imath=}{\\sum_{n=1}^{N}\\exp\\left(\\langle q_{m}\\mathrm{~,~}k_{\\langle n}\\rangle\\right)}}\\end{array}\n$$  \n\n其中，Q、 $\\boldsymbol{\\kappa}$ 和 $v$ 分别为查询、键和值。vanilla transformer23 架构的一个众所周知的计算瓶颈是，注意力机制的计算成本与序列长度成二次方关系。线性复杂度注意力模型31(,)(45) 利用核近似和随机特征近似变体解决了这一问题。这促使我们设计出了 MoLFormer，它采用了基于变压器的编码器和线性注意（31）。带有线性注意的 MoLFormer 每层由 12 个层级和 12 个注意头组成，隐藏状态大小为 768。线性注意选择了广义特征图31（详见补充章节 A.1.1）。  \n\n如上所述，在转换器结构中，（化学）序列不同位置的标记之间的依赖关系是在位置编码的监督下建模的。参考文献 23 的开创性工作研究了绝对位置嵌入，以编码标记在序列中的位置。最近的工作46(-)(48)表明，使用标记间的相对位置嵌入可以提高性能。RoFormer27引入了旋转位置嵌入，通过对查询和位于 $m$ 处的键进行与位置相关的旋转 ${\\sf R}_{m}$ 来增强相对编码。  \n\n为了利用线性变换器进行旋转嵌入，参考文献 27 提出了以下近似方法：  \n\n$$\n\\begin{array}{r l}{\\sum^{N}}&{{}\\left\\langle R\\phi\\left(q\\right)\\ ,\\ R\\phi\\left(k\\right)\\right\\rangle v}\\end{array}\n$$  \n\n$$\n\\begin{array}{r l}{\\mathbf{\\Phi}_{m}\\left(\\boldsymbol{Q},\\boldsymbol{K},\\boldsymbol{V}=\\mathrm{~\\cfrac~{\\gamma\\left(\\boldsymbol{~\\Omega~}\\right)~=~\\gamma~}{~\\frac{\\gamma~\\left(\\boldsymbol{~\\Omega~}\\right)~=~\\gamma~\\left(\\boldsymbol{~\\Omega~}\\right)~=~\\gamma~\\left(\\boldsymbol{~\\Omega~}\\right)~=~\\gamma~\\left(\\boldsymbol{~\\Omega~}\\right)~=~\\gamma~\\left(\\boldsymbol{~\\Omega~}\\right)~}~}}&{}\\end{array}\n$$  \n\n其中， $j$ 是随机特征图。  \n\n在对这种线性 RoFormer 进行初步实验后，我们发现它的性能比绝对位置模型差。我们对 RoFormer 提出了以下修改建议，我们发现它比原始RoFormer 训练效果更佳（训练损失下降得更快、更低），而且比使用绝对嵌入的模型性能更好：  \n\n$$\n\\begin{array}{r l}{\\left(Q,K,V=\\right.}&{{}\\sum_{n=1}^{N}\\left.\\mathcal{\\hat{V}}\\left(R q_{n m}\\right)\\right.,\\phi\\left(R_{n}k_{n\\right)}\\right\\rangle v_{\\leftn{\\left(n\\right)}}}\\end{array}\n$$  \n\n与参考文献 27 相比，我们用 $\\phi$ 旋转原始密钥和查询，而不是转换后的密钥和查询。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 数据集和标记化  \n\n我们将 PubChem 数据集49 和 ZINC 数据集50 以不同比例组合在一起，构建了多个数据集用于预训练。PubChem 数据集包含 1.11 亿个分子，而更大的ZINC 数据集包含超过 10 亿个分子。为了构建词汇表，我们使用了参考文献51 中的标记符。51.利用 RDKit（http://www.rdkit.org）将 PubChem 和 ZINC中的所有分子转换为规范格式，然后进行标记化。从输出结果中提取的所有独特标记为我们提供了一个包含 2357 个标记和 5 个特殊标记的词汇表，因此词汇表标记总数为 2362 个，这些标记用于本文所考虑的所有预训练模型，与预训练数据集的大小无关。说，在词汇量固定的情况下，所有模型都具有相同的嵌入能力。但是，预训练时所使用的唯一标记可能只包含模型词汇量的一个子集。分子的标记后序列长度从 1 到刚刚超过 2000 个标记不等。我们决定将序列长度范围限制在 1 token  \n到 202 个标记，包括特殊标记，以减少计算时间。  \n由于我们数据集中 $99.4\\%$ 以上的分子包含少于 202 个标记，因此我们假设，删除多于 202 个标记的分子对预训练的负面影响很小。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# 大规模训练和并行化  \n\n在预训练中，我们使用了参考文献 30 中定义的屏蔽语言模型方法。30.最初，我们会选择 $15\\%$ 的标记词进行去噪处理。从中随机抽取 $80\\%$ 的标记替换为[MASK]标记，随机抽取 $10\\%$ 的标记替换为随机标记，其余 $10\\%$ 的标记保持不变。对整个 PubChem $^+$ ZINC 数据集进行了四个历元的训练，固定学习率为 $1.6\\times10^{-4}$ ，每个 GPU 的批量大小为 ,600 个分子，通过InfiniBand 结构连接两台服务器上的总共 16 个 GPU。值得注意的是，随着使用的 GPU 数量的增加我们发现学习率必须提高 8 倍。  \n\n为了将我们的训练扩展到大型数据集（10 亿多个数据点），我们依赖于按序列长度对迷你批进行自适应分级，以及通过分布式训练实现并行化（详见补充章节 A）。通过使用线性注意和分桶，我们将所需的GPU 数量从没有分桶的二次注意的大约 1000 台减少到 16 台（参考文献52-55）。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# 数据可用性  \n\n用 于 模 型 预 训 练 和 基 准 任 务 微 调 的 数 据 可 从https://github.com/IBM/molformer 网站获取。",
+        "category": " References"
+    },
+    {
+        "id": 14,
+        "chunk": "# 代码可用性  \n\n用于 MoLFormer 训练和微调的 Python 代码，以及 Python用于 MoLFormer 注意力可视化的笔记本，以及实例  \n\n预训练模型的数据可在 https://github.com/IBM/mol- former 网站查阅。如有其他疑问，请联系通讯作者。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# 参考资料  \n\n1. Rogers, D. & Hahn, M. Extended-connectivity fingerprints.J. Chem.Inf.Model.50, 742-754 (2010).   \n2. Rupp, M., Tkatchenko, A., Müller, K.-R. & Von Lilienfeld, O. A. Fast and accurate modeling of molecular atomization energies with machine learning.Phys.108, 058301 (2012).   \n3. Weininger, D. SMILES, a chemical language and information system.1.方法和编码规则介绍。J. Chem.Inf.28, 31-36 (1988).28, 31-36 (1988).   \n4. Goh, G. B.、Hodas, N. O.、Siegel, C. & Vishnu, A. SMILES2Vec: an SMILE",
+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,87 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Large-scale chemical language representations capture molecular structure and properties  \n\nReceived: 18 April 2022  \n\nAccepted: 3 November 2022  \n\nPublished online: 21 December 2022",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# Check for updates  \n\nJerret Ross      , Brian Belgodere, Vijil Chenthamarakshan    , Inkit Padhi, Youssef Mroueh     & Payel Das  \n\nModels based on machine learning can enable accurate and fast molecular property predictions, which is of interest in drug discovery and material design. Various supervised machine learning models have demonstrated promising performance, but the vast chemical space and the limited availability of property labels make supervised learning challenging. Recently, unsupervised transformer-based language models pretrained on a large unlabelled corpus have produced state-of-the-art results in many downstream natural language processing tasks. Inspired by this development, we present molecular embeddings obtained by training an efficient transformer encoder model, MoLFormer, which uses rotary positional embeddings. This model employs a linear attention mechanism, coupled with highly distributed training, on SMILES sequences of 1.1 billion unlabelled molecules from the PubChem and ZINC datasets. We show that the learned molecular representation outperforms existing baselines, including supervised and self-supervised graph neural networks and language models, on several downstream tasks from ten benchmark datasets. They perform competitively on two others. Further analyses, specifically through the lens of attention, demonstrate that MoLFormer trained on chemical SMILES indeed learns the spatial relationships between atoms within a molecule. These results provide encouraging evidence that large-scale molecular language models can capture sufficient chemical and structural information to predict various distinct molecular properties, including quantum-chemical properties.  \n\nMachine learning (ML) has emerged as an appealing, computationally efficient approach for predicting molecular properties, with implications in drug discovery and material engineering. ML models for molecules can be trained directly on predefined chemical descriptors, such as unsupervised molecular fingerprints1, or hand-derived derivatives of geometric features such as a Coulomb matrix2. However, more recent ML models have focused on automatically learning the features either from the natural graphs that encode the connectivity information or from the line annotations of molecular structures, such as the popular SMILES3 (simplified molecular-input line-entry system) representation. SMILES defines a character string representation of a molecule by performing a depth-first preorder spanning tree traversal of the molecular graph, generating symbols for each atom, bond, tree-traversal decision and broken cycle. Therefore, the resulting character string corresponds to a flattening of a spanning tree of the molecular graph. Learning on SMILES has been widely adopted for molecular property prediction4–7 as SMILES is generally more compact than other methods of representing structure, including graphs. Additionally, meaningful substructures such as branches, cyclic structures and chirality information are explicitly represented in SMILES strings, which is not the case for the graph representation.  \n\n![](images/740f822739144e2a6693af447c3a8e2eac5608fc261f85455b17a63845c49003.jpg)  \nFig. 1 | Overview of MoLFormer pipeline. The transformer neural network based model is trained on the SMILES sequences corresponding to a large collection of chemical molecules from PubChem and ZINC, two public chemical databases, in a self-supervised fashion. MoLFormer was designed with an efficient linear attention mechanism and relative positional embeddings, with the goal of learning a meaningful and compressed representation of chemical  \n\nHowever, the SMILES grammar is complex and restrictive; most sequences over the appropriate character set do not belong to well defined molecules. Alternative string-based representations exist, such as SMARTS8 and SELFIES9. Comparing benefits of these alternative representations with respect to SMILES is an active area of research. For example, ref. 10, focusing on molecular optimization tasks on the learned representation space, suggested no obvious shortcoming of SMILES with respect to SELFIES in terms of optimization ability and sample efficiency, particularly when the language model is more advanced. Nevertheless, string-based representations are thought to not be topologically aware, while graphs are. Due to these limitations, deep chemical language models may focus on learning the grammar of molecular strings and not the implicit topological structure of the molecular graphs. Accordingly, while string-based deep neural nets have been employed in predicting molecular properties5–7,11, they are typically outperformed by graph neural networks (GNNs)12 and their variants13–21. GNN frameworks can be generally viewed as ‘message passing’, which includes local neighbourhood information aggregation and information updates across different levels of granularity, for example, nodes, edges or the full graph, according to the graph’s connectivity structure.  \n\nOne challenge with supervised training of GNNs and language models for molecular property prediction is the scarcity of labelled data. Label annotation of molecules is typically expensive and this problem is compounded by the fact that the size of the space consisting of plausible chemicals in need of annotation is astronomically large $(10^{60}\\mathrm{to}10^{100})^{22},$ . Such a scenario creates the need for molecular representation learning that can be generalizable to various property prediction tasks in an un-/self-supervised setting. The recent success of large transformer-based23 foundation models24, using the paradigm of learning a task-agnostic language representation, obtained by pretraining on large unlabelled corpora and subsequently using it for fine-tuning on downstream tasks of interest, has been extended to other domains.  \n\nPretrained language models25 and GNNs26 for predicting molecular properties have only recently started to emerge. However, to what extent pretrained language models, trained on a large corpus of billions of molecules, are able to capture the molecule–property relationships across various downstream tasks remains unexplored.  \n\nmolecules. This foundation model was then adapted to different downstream molecular property prediction tasks via fine-tuning on task-specific data. The representative power was further tested by recovering molecular similarity using the MoLFormer encodings, as well as by analysing the correspondence between the interatomic spatial distance and attention value for a given molecule.  \n\nTowards this direction, here we present molecular SMILES transformer models referred to as MoLFormer (molecular language transformer). We name our best performing MoLFormer variant MoLFormer-XL. MoLFormer-XL was obtained using an efficient linear attention mechanism trained on a large corpus of 1.1 billion molecules (Fig. 1). Results show that pretrained transformer encoders of molecular SMILES perform competitively with existing supervised or unsupervised language model and GNN baselines in predicting a wide variety of molecular properties, including quantum-mechanical properties.  \n\nOur main contributions are the following.  \n\n• We train a large-scale and efficient molecular language model transformer (MoLFormer) on over a billion molecules, with relatively limited hardware resources (up to 16 V100 graphics processing units (GPUs)). We owe our scalability and speedups to efficient linear time attention, adaptive bucketing of batches, and open-source parallelization provided in PyTorch Lightning and NCCL. With the combination of bucketing and linear attention we are able to achieve a batch size of 1,600 molecules per GPU. Using 16 GPUs we need $208\\mathsf{h}$ to complete four epochs of pretraining for MoLFormer-XL. To complete training in the same amount of time without bucketing and linear attention we would be limited to fewer than 50 molecules per GPU and require over 1,000 GPUs for the task.   \n• We explore the difference between absolute and relative position embeddings in representing molecular SMILES. We also provide a new, efficient and accurate linear attention approximation of the recently proposed relative position RoFormer27. We perform extensive experimentation and ablation studies on several classification and regression tasks from ten benchmark datasets, covering quantum-mechanical, physical, biophysical and physiological property prediction of small-molecule chemicals from MoleculeNet28. Our results provide encouraging evidence that MoLFormer representations can accurately capture sufficient chemical and structural information to predict a diverse range of chemical properties. Furthermore, the performance of MolFormer is either better than or on a par with state-of-the-art GNNs that learn from precise graph topology information and beyond (for example, bond distances). We provide further analyses to demonstrate that MoLFormer can  \n\ncapture substructures, as well as spatial interatomic distances within a molecule, from SMILES annotations only.  \n\n![](images/bf0d3a17ad09ddd01e952d68eaaf2bca04c869bc4255c44ec4d7224efdd07a52.jpg)  \nFig. 2 | Comparison of training and validation losses for absolute and rotary embeddings. a,b, Training (a) and validation (b) losses of our linear attention MoLFormer with rotary (relative) and absolute position embeddings   \non PubChem. We see that both rotary and absolute MoLFormer have graceful training curves. Our rotary linear attention MoLFormer leads to lower training and validation losses than MoLFormer with absolute position embeddings.  \n\nThe present study explores the representational power of pretrained chemical language models in predicting a broad range of downstream molecular properties from quantum chemical to physiological. In particular, predicting quantum-chemical properties from SMILES strings alone is non-trivial, as those properties are largely dependent on the accurate three-dimensional (3D) molecular geometric information, which is considered privileged information and not available in general.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# Results and discussion MoLFormer framework  \n\nThe goal of MoLFormer is to learn a universal molecular representation from large-scale chemical SMILES data and then evaluate the representation on various downstream molecular property prediction tasks, as shown in Fig. 1. To do so, the MoLFormer model is developed using the masked language model framework29,30, which randomly masks a certain percentage of tokens within a SMILES sequence during training and then predicts these tokens. The masked language modelling thus exploits self-supervision and enables contextual learning. To allow better contextual learning and faster training, rotary positional embedding27 was used instead of absolute positional embedding, along with linear attention31 (see Methods and Supplementary Information for further details of model architecture and training). We saw increased stability and faster convergence in training loss behaviour when pretraining using rotary embeddings, compared with absolute embeddings, as observed in Fig. 2. To demonstrate the effectiveness of the pretrained MoLFormer as a universal and task-agnostic molecular representation, we benchmarked its adaptation performance on numerous challenging classification and regression tasks from MoleculeNet28. Details of the benchmark datasets can be found in Supplementary Section C.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# Derivation of MoLFormer embeddings  \n\nWe encode a chemical SMILES by extracting the mean of all embeddings of the last hidden state from the encoder model. The resulting embedding is used for all downstream tasks. The downstream tasks themselves can be divided into two categories, the first category being called frozen and the second fine-tuned. The frozen setting is defined by training a fully connected model for each task, while keeping the encoder embeddings fixed. The second setting, fine-tuned, involves fine-tuning the weights of the encoder model jointly with the fully connected model for each downstream task. The ideal configuration and hyperparameters for the frozen strategy are discovered through a grid search as described in Supplementary Table 1. For the fine-tuned strategy, we use a two-layer fully connected network with a hidden dimension of 768 (matching the encoder embedding) with dropout (set to 0.1) and Gaussian error linear unit layers in between, on top of a final single output dimension for regression tasks.  \n\nPerformance of MoLFormer embeddings on downstream tasks We evaluate the performance of MoLFormer embeddings and compare them with existing baselines on six classification and five regression tasks from the MoleculeNet benchmark28, as discussed below. We refer to MoLFormer that has been pretrained on the entire training set comprised of ${\\bf\\tilde{\\tau}}{\\approx}1.1$ billion molecules (all molecules from both PubChem and ZINC) as MoLFormer-XL. Unless stated otherwise, MoLFormer-XL is trained with linear attention using rotary positional embeddings and the performance reported is that of the model fine-tuned on the downstream task (see Methods for details). To predict various properties on the downstream tasks we fined-tuned the model as described in the previous section. We use the training, validation and testing data split as defined by the MoleculeNet benchmark for all tasks (Supplementary Section C).  \n\nClassification tasks. We choose six classification tasks from the MoleculeNet benchmark with nine total baselines, four supervised and five self-supervised, for comparison against MoLFormer-XL. The supervised baselines consist of shallow ML models trained on molecular fingerprints (RF and SVM in Table 1) and graph neural nets. Among the pretrained/self-supervised baselines, Hu et al.32 pretrain a graph isomorphism network (a GNN that uses a multilayer perceptron and weighted sum of node features in the aggregation) on molecular graphs that includes edge features involved in aggregation. The N-gram graph33 uses a simple unsupervised representation for molecules by first embedding the nodes in a graph and then constructing a compact representation of the graph by assembling the vertex embeddings in short walks in the graph. MolCLR26 is a self-supervised learning framework based on a graph isomorphism network, which uses contrastive loss34,35. GraphMVP-C is the graph multiview pretraining framework proposed in ref. 36, where self-supervised learning is performed by leveraging the correspondence and consistency between two-dimensional topological structures and 3D geometric views. We have considered three other geometry-aware GNN baselines, one supervised (DimeNet37), and two self-supervised (GeomGCL36 and GEM38). ChemBERTa25 is a pretrained molecular language model trained on a smaller chemical dataset. Table 1 documents the performance comparison of MoLFormer with these baselines on six classification benchmarks using the MoleculeNet scaffold data splits. MoLFormer-XL outperforms all baselines in three (BBBP, ClinTox and SIDER) out of six benchmarks and comes a close second in the other three (Tox21, HIV and BACE).  \n\nTable 1 | Comparison of fine-tuned MoLFormer with existing supervised and pretrained/self-supervised baselines on multiple classification benchmarks   \n\n\n<html><body><table><tr><td></td><td>BBBP1 Tox21 12</td><td>ClinTox 2</td><td>HIV1</td><td>BACE1</td><td>SIDER 27</td></tr><tr><td>RF 71.4</td><td>76.9</td><td>71.3</td><td>78.1</td><td>86.7</td><td>68.4</td></tr><tr><td>SVM 72.9</td><td>81.8</td><td>66.9</td><td>79.2</td><td>86.2</td><td>68.2</td></tr><tr><td>MGCN56 85.0</td><td>70.7</td><td>63.4</td><td>73.8</td><td>73.4</td><td>55.2</td></tr><tr><td>D-MPNN57 71.2</td><td>68.9</td><td>90.5</td><td>75.0</td><td>85.3</td><td>63.2</td></tr><tr><td>DimeNet37 一</td><td>78.0</td><td>76.0</td><td>一</td><td>一</td><td>61.5</td></tr><tr><td>Hu et al.32 70.8</td><td>78.7</td><td>78.9</td><td>80.2</td><td>85.9</td><td>65.2</td></tr><tr><td>N-gram33 91.2</td><td>76.9</td><td>85.5</td><td>83.0</td><td>87.6</td><td>63.2</td></tr><tr><td>MolCLR26 73.6</td><td>79.8</td><td>93.2</td><td>80.6</td><td>89.0</td><td>68.0</td></tr><tr><td>GraphMVP-C36 72.4</td><td>74.4</td><td>77.5</td><td>77.0</td><td>81.2</td><td>63.9</td></tr><tr><td>GeomGCL36 一</td><td>85.0</td><td>91.9</td><td>一</td><td>一</td><td>64.8</td></tr><tr><td>GEM38 72.4</td><td>78.1</td><td>90.1</td><td>80.6</td><td>85.6</td><td>67.2</td></tr><tr><td>ChemBERTa25</td><td>64.3 一</td><td>90.6</td><td>62.2</td><td></td><td>一</td></tr><tr><td>MOLFORMER-XL</td><td>93.7 84.7</td><td>94.8</td><td>82.2</td><td>88.21</td><td>69.0</td></tr></table></body></html>\n\nBold indicates the top-performing model. All models were evaluated using the area under the receiver operating characteristic curve on scaffold splits. Baseline performances are adopted from refs. 25, 26,36, ‘—’ signifies that the values were not reported for the corresponding task.  \n\nRegression tasks. Next, we evaluate MoLFormer-XL on more challenging regression tasks from MoleculeNet. We report our performance on five regression benchmarks, namely QM9, QM8, ESOL, FreeSolv and Lipophilicity, in Table 2 (see also Supplementary Sections D and E). In particular, QM9 and QM8 involve prediction of several quantum-chemical measures, which is considered challenging without having access to privileged 3D geometric information. Again we use the train, validation and test split as suggested in ref. 28 for these tasks. The baselines considered are a molecular graph convolutional network (GC, a GNN that utilizes a mean pooling over the node and its neighbours before the linear transformation)39, the attentive FP (A-FP) model40 and an MPNN variant18 that learns edge features such as pairwise interatomic distances. Results show that MoLFormer-XL upon task-specific fine-tuning outperforms the existing supervised GNN baselines, specifically GC, A-FP and MPNN (augmented with bond distances for QM8 and QM9), on all five tasks. Supplementary Table 7 further shows MoLFormer outperforming geometry-aware GNNs (DimeNet, GeomGCL and GEM) on three physical property regression benchmarks. These results, combined with MoLFormer-XL performance on the classification benchmarks, confirm its generalizability.  \n\nA closer look at QM9. Supplementary Table 9 further compares MoLFormer-XL performance on the QM9 atomization energies and enthalpy (internal energy/enthalpy corrected for reference atomic energy, in electronvolts) prediction tasks with two exemplary supervised 3D GNNs, SchNet41 and Dimenet37. MoLFormer-XL trained on SMILES alone is outperformed by both these models in all of the four tasks. However, SchNet and DimeNet, which directly encode 3D information with specialized architecture for modelling quantum interactions, beat MoLFormer-XL only by roughly a factor of 8 and by roughly a factor of 10, respectively. This result, along with Tables 1 and 2, reinstates the power of learning a universal molecular representation from readily available information, such as SMILES, at a broader scale, while confirming the crucial role of privileged geometric information for quantum-chemical energy prediction. Further, results from this comparison open the door for future investigations with the goal of estimating emergence of geometric awareness in MoLFormer (see later sections) or how the expressiveness of SMILES-only MoLFormer can be further enhanced by adding partial or complete 3D geometric information.  \n\nTable 2 | Performance of fine-tuned MoLFormer and other supervised GNN baselines on QM9, QM8, ESOL, FreeSolv and Lipophilicity regression benchmarks   \n\n\n<html><body><table><tr><td>QM9</td><td>QM8</td><td>ESOL</td><td>FreeSolv</td><td>Lipophilicity</td></tr><tr><td>GC 4.3536</td><td>0.0148</td><td>0.970</td><td>1.40</td><td>0.655</td></tr><tr><td>A-FP 2.6355</td><td>0.0282</td><td>0.5030</td><td>0.736</td><td>0.578</td></tr><tr><td>MPNN 3.1898</td><td>0.0143</td><td>0.58</td><td>1.150</td><td>0.7190</td></tr><tr><td>MOLFORMER-XL 1.5894</td><td>0.0102</td><td>0.2787</td><td>0.2308</td><td>0.5289</td></tr></table></body></html>\n\nFor QM9 and QM8, we report average MAE, while root-mean-square error is reported for the remaining tasks. Baseline performances are taken from refs. 28,40. Bold indicates the top-performing model.  \n\nAblation studies. In this section we discuss several different ablations of MoLFormer-XL in an attempt to provide insights into its impressive performance. The ablations we performed can be broadly divided into the following three categories: (1) the effect of size and the nature of the pretraining data and model depth, (2) the results without (frozen) and with (fine-tuned) model fine-tuning on the downstream data and (3) the effect of absolute and rotary positional embeddings.  \n\nData/model size. First we investigate how pretraining dataset size affects the performance of MoLFormer-XL on several downstream tasks from the MoleculeNet benchmark. To accomplish this we chose three different weighted combinations of the PubChem and ZINC datasets, specifically a set consisting of $10\\%$ of ZINC and $10\\%$ of PubChem, another with $100\\%$ of PubChem mixed with $10\\%$ of ZINC, and then one with $100\\%$ of ZINC molecules and $0\\%$ of PubChem. We also investigate the influence of model depth by pretraining a six-layer model, named MoLFormer-Base, on the complete ZINC and PubChem dataset. All models are pretrained with rotary embeddings and linear attention and then compared with MoLFormer-XL. Identical learning rates, data splits, optimization and so on are used for pretraining and fine-tuning. Extended Data Tables 1 and 2 summarize these results. While MoLFormer-XL performs better on average, we report two interesting observations. The first is that the model that is pretrained on the second biggest dataset, $100\\%$ ZINC, consistently performs worse than all other pretrained models. A possible explanation for the poor performance of the model trained on only ZINC is that the ZINC dataset consists of a much smaller vocabulary than all other dataset combinations, as well as much shorter molecules with little variance with respect to molecule length. The other point of interest is that when MoLFormer-XL falls behind it is only by a very small margin (see performance on ESOL, QM8 and FreeSolv benchmarks in Table 2). Extended Data Tables 1 and 2 further show that MoLFormer-Base has a weaker performance than MoLFormer-XL in the majority of tasks, implying that a deeper model helps in learning.  \n\nFine-tuned versus frozen. Extended Data Table 3 further summarizes the two remaining ablation experiments using the QM9 benchmark. For simplicity we observe that the fine-tuned ablation experiments achieve such a convincing win over the frozen experiments on all pretraining dataset sizes that we opted to only investigate fine-tuning for all other benchmarks. These results provide empirical insights into the neural and data scaling behaviour of MoLFormer.  \n\nTable 3 | Comparison of MoLFormer models with respect to cosine similarity between the interatomic spatial distance map and the attention map, across three different distance categories for 7,806 molecules from the QM9 test set   \n\n\n<html><body><table><tr><td>Distance category</td><td>Attention</td><td>1</td><td>3</td><td>5</td><td>7</td><td>9</td><td>11</td></tr><tr><td rowspan=\"2\">Short</td><td>Full (√rotary)</td><td>0.615</td><td>0.604</td><td>0.603</td><td>0.615</td><td>0.601</td><td>0.598</td></tr><tr><td>Linear (√rotary)</td><td>0.596</td><td>0.597</td><td>0.602</td><td>0.597</td><td>0.600</td><td>0.594</td></tr><tr><td rowspan=\"2\"> Medium</td><td>Full (√rotary)</td><td>0.716</td><td>0.724</td><td>0.724</td><td>0.716</td><td>0.727</td><td>0.727</td></tr><tr><td>Linear (√ rotary)</td><td>0.729</td><td>0.728</td><td>0.724</td><td>0.727</td><td>0.726</td><td>0.730</td></tr><tr><td rowspan=\"2\">Long</td><td>Full (/ rotary)</td><td>0.204</td><td>0.207</td><td>0.208</td><td>0.205</td><td>0.208</td><td>0.210</td></tr><tr><td>Linear (√ rotary)</td><td>0.211</td><td>0.210</td><td>0.210</td><td>0.211</td><td>0.209</td><td>0.210</td></tr></table></body></html>\n\nShort, medium and long distance categories are defined with interatomic distances in the range of ≤2, 2–4 and 4–10 Å, respectively. Bold indicates the top-performing model.  \n\nPosition embeddings. The positional embedding ablation results are collected in Extended Data Table 3, which show that MoLFormer with rotary embeddings and fine-tuning is behind the absolute positional embedding model for the smaller datasets, but then wins as the dataset size passes 1 billion molecules.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# Insights into MoLFormer  \n\nMolecular similarity recovery. Next, we analysed the correlation between pairwise similarities estimated using the Tanimoto distance, a popular measure of pairwise distance between chemicals, on the molecular fingerprints and those estimated using the Euclidean distance on the MoLFormer-XL embeddings. We further looked into the correlation between the number of atoms in the maximum common subgraph of a pair of molecules with their corresponding Euclidean distance in the embedding space for a set of random molecules picked from PubChem. The results are summarized in Extended Data Table 4 and show that MoLFormer-XL embeddings are better correlated with known molecule similarity measures when compared with ChemBERTa. These results are suggestive of MoLFormer embeddings being informative about chemical structure similarity.  \n\nAttention analyses. Finally, we inspect the average-pooled attention matrices of MoLFormer-XL to explore the chemical information embedded in them. For this purpose, we utilize the cosine similarities between attention values and the spatial distances between atoms within a molecule from the QM9 test set. Spatial distances are obtained from the corresponding energy-minimized geometries provided within the QM9 benchmark28. MoLFormer-XL is compared with a MoLFormer variant trained with full attention and rotary embeddings on the entire PubChem $+Z I N C$ dataset. Note that the MoLFormer models here are not fine-tuned for the QM9 dataset. The frozen MoLFormer with full attention shows a much higher average mean absolute error $(\\mathsf{M A E}\\geq12),$ ) on QM9 downstream tasks; performance is particularly worse on internal energies (U and $U_{0})$ , enthalpy $(H)$ and free energy $(G)$ . We present attention results separately for three different categories of interatomic spatial distances—short $(\\leq2\\mathring\\mathbf{A}$ ; mostly reflective of typical covalent bonds in the molecule, the C–C single-bond distance being $1.5\\mathring\\mathrm{A}$ ), medium $(2\\substack{-4\\mathring{\\mathbf{A}}})$ and long $(\\geq4{\\mathring{\\mathbf{A}}})$ —and summarize them in Table 3. Interestingly, attentions in MoLFormer with linear or full attention (and rotary positional embeddings) show strong similarity with interatomic distances in both the short and medium categories, while revealing a weak (around 0.2) similarity with longer interatomic distances. This is an interesting observation, indicating that MoLFormer is able to capture spatial relations between atomic tokens that are not necessarily neighbours in the SMILES sequence. The observed attentions in MoLFormer-XL are slightly more in line with medium and long-range distances, when compared with MoLFormer with full attention. This observation suggests that MoLFormer-XL, with linear attention, does in fact capture spatial relations between atoms more effectively.  \n\nFigure 3 further elaborates this point, showing the average learned attention coefficients in an intermediate attention layer of MoLFormer-XL with rotary positional embeddings. Attentions between different pairs of atomic tokens are compared with the corresponding covalent bond connectivity and 3D distances between atom pairs (complete attention matrices for the same molecules across all layers are shown in Supplementary Figs. 5 and 6). We chose two molecules from the QM9 test set whose attention values show a high cosine similarity with the medium-range spatial distances for this visualization. Visual inspection indicates that an aggregation of heads on the intermediate rotary attention layer corresponds well to the covalent bonding pattern, while also capturing the signature of the spatial relations between non-bonded atoms within a molecule. These attention analysis results suggest that MoLFormer-XL is able to recover molecular structural information from corresponding SMILES sequence to a great extent. This capability probably stems from pretraining on a large corpus of chemical SMILES, which also allows MoLFormer-XL to learn fundamental properties of chemicals, including structural information and various downstream properties, ranging from quantum chemical to physiological. A similar observation has been reported in recent work on protein sequence modelling42,43. This is confirmation that structural and diverse property information emerges in the representation learned by a chemical language model pretrained on large-scale data.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# Conclusion  \n\nIn this work, we have explored the power of unsupervised large-scale pretrained molecular language models in various molecular property prediction tasks. Unlike graphs, molecular languages such as SMILES do not explicitly encode molecular topology. However, with well designed self-supervised training on a large-scale corpus and with an expressive architecture, such as a contextualized transformer-based language model with a linear attention mechanism, and a parallelized training protocol, our MoLFormer can efficiently learn implicit rich structure– property relationship information.  \n\nSpecifically, MoLFormer outperforms existing graph-based baselines on a wide variety of molecular regression and classification benchmarks. This work validates the power of large-scale self-supervised pretrained molecular language models in predicting molecular properties across the entire range from quantum chemical to physiological. Further, by analysing the learned attentions, we show that MoLFormer trained on SMILES sequences is indeed aware of interatomic relations within a molecule, even beyond the two-dimensional topology. Finally, at the large-scale learning end, we showcase with MoLFormer an efficient and environment-friendly use of computational resources, reducing the number of GPUs needed to perform the training by a factor of 60 (1,000 versus 16).  \n\nMoLFormer has immediate potential for faster in silico screening of molecules across diverse targets, which is important for material design and drug discovery applications with positive societal impact. However, it should be noted that misuse of such technology without for clarity), comprised of the average-pooled heads of an intermediate attention layer, exhibits awareness of both covalent bond connectivity and interatomic long-range spatial relationship. The linear attention variant captures (encircled in red) the medium-range 3D distance better than does its counterpart.  \n\n![](images/8842a23a177de08443c4bbe7b3a00a9b3f8a2a77b911318058fcc6a47454f7da.jpg)  \nFig. 3 | a,b, Visualization of the learned attention map (using either full or linear attention) under rotary embedding and corresponding molecular structure (bond connectivity and 3D distance in Angstrom) for two random molecules: ‘CC1(C)C(C)(O)C1(C)O’ (a) and ‘CC(C)C(C)(C)O’ (b). The attention map (ranging from 0 to 1; only tokens that map to constituent atoms are shown  \n\na proper experimental and scientific validation in a wet lab can have harmful implications. Further, it has been shown that accurate property prediction models (for example, for predicting toxicity) along with generative models can be exploited for designing highly toxic molecules44. This highlights the need for a responsible framework around the use of these emerging powerful technologies. In addition, the present work calls for further exploration of the representational power of MoLFormer in the context of its ability to learn structural molecular information directly from chemical language, and can be extended beyond the small organic molecules studied in this work.  \n\nFuture work will also aim to improve MoLFormer by employing larger models and more training data, using improved and/or domain-specific self-supervised tasks, and using other string-based representations such as SELFIES9.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 7,
+        "chunk": "# Methods",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# Model details  \n\nAs we aim to train a large-scale masked language model of chemical SMILES efficiently and effectively, while utilizing relatively limited hardware resources, we leverage transformer-based neural nets23. Transformers process inputs through a series of blocks alternating between self-attention and feedforward connections. They encode the position in the sequence via a positional embedding, termed the absolute positional embedding. The input feature at a position $m$ is therefore concatenated with its corresponding absolute position embedding. Self-attention enables the network to construct complex representations that incorporate context from across the sequence. Attention mechanisms transform the features in the sequence into queries $(q)$ , keys $(k)$ and value $(\\upsilon)$ representations. These representations produce the output of the attention at $m$ as follows:  \n\n$$\n\\mathsf{A t t e n t i o n}_{m}\\left(Q,K,V\\right)=\\frac{\\sum_{n=1}^{N}\\exp\\left(\\left\\langle q_{m},k_{n}\\right\\rangle\\right)\\upsilon_{n}}{\\sum_{n=1}^{N}\\exp\\left(\\left\\langle q_{m},k_{n}\\right\\rangle\\right)}\n$$  \n\nwhere $Q,K$ and V are the query, key and value respectively. A well known computational bottleneck of the vanilla transformer23 architecture is that the attention mechanism suffers from a quadratic computational cost with respect to the sequence length. Linear complexity attention models31,45 have tackled this issue utilizing kernel approximations and random feature approximation variants. This led us to design MoLFormer, which utilizes an encoder based on a transformer with linear attention31. MoLFormer with linear attention consists of 12 layers and 12 attention heads per layer, and has a hidden state size of 768. A generalized feature map31 for the linear attention was chosen (see Supplementary Section A.1.1 for details).  \n\nAs mentioned above, in a transformer architecture the dependence between tokens at different positions of a (chemical) sequence is modelled under the supervision of position encoding. The seminal work of ref. 23 investigated absolute position embeddings to encode the position of a token in the sequence. More recent work46–48 showed that use of relative position embeddings between tokens results in improved performance. Rotary position embeddings were introduced in RoFormer27 as a means to enhance the relative encoding via position-dependent rotations $R_{m}$ of the query and the keys at m. These rotations can be efficiently implemented as pointwise multiplications and do not result in a marked computational increase.  \n\nTo leverage rotary embeddings with linear transformers, the use of the following approximation was proposed in ref. 27:  \n\n$$\n\\mathsf{A t t e n t i o n}_{m}\\left(Q,K,V\\right)=\\frac{\\sum_{n=1}^{N}\\left\\langle R_{m}\\phi\\left(q_{m}\\right),R_{n}\\phi\\left(k_{n}\\right)\\right\\rangle v_{n}}{\\sum_{n=1}^{N}\\left\\langle\\phi\\left(q_{m}\\right),\\phi\\left(k_{n}\\right)\\right\\rangle}\n$$  \n\nwhere $\\phi$ is a random feature map.  \n\nAfter preliminary experimentation with this linear RoFormer, we found that it performed worse than its absolute position counterpart. We propose the following modification to RoFormer that we found to train more gracefully (the training loss falls faster and lower) than the original RoFormer, as well as observing better performance than the model using absolute embeddings:  \n\n$$\n{\\sf A t t e n t i o n}_{m}\\left(Q,K,V\\right)=\\frac{\\sum_{n=1}^{N}\\left\\langle\\phi\\left(R_{m}q_{m}\\right),\\phi\\left(R_{n}k_{n}\\right)\\right\\rangle v_{n}}{\\sum_{n=1}^{N}\\left\\langle\\phi\\left(R_{m}q_{m}\\right),\\phi\\left(R_{n}k_{n}\\right)\\right\\rangle}.\n$$  \n\nWhen compared with ref. 27 we rotate the original keys and queries instead of the transformed ones with $\\phi$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# Datasets and tokenization  \n\nWe constructed several datasets for pretraining by combining the PubChem49 and $\\mathbf{\\Delta}Z\\mathbf{I}\\mathbf{N}\\mathbf{C}^{50}$ datasets with varying proportions from each. The PubChem dataset consists of 111 million molecules, while the much larger ZINC dataset contains over 1 billion molecules. To construct a vocabulary, we utilize the tokenizer from ref. 51. All molecules from both PubChem and ZINC are converted to a canonical format utilizing RDKit (http://www.rdkit.org) then tokenized. All unique tokens extracted from the resulting output give us a vocabulary of 2,357 tokens plus 5 special tokens, resulting in a total of 2,362 vocabulary tokens, which are used for all pretrained models considered in this paper, irrespective of pretraining dataset size. In other words, all models have the same embedding capacity with a fixed vocabulary size. However, the unique tokens on which they are pretrained might only contain a subset of the model vocabulary capacity. The post-tokenization sequence length of the molecules ranges from 1 to just over 2,000 tokens. We decided to restrict the sequence length range from 1 token to 202 tokens, inclusive of special tokens, to reduce computation time. Since over $99.4\\%$ of all molecules from our dataset contain fewer than 202 tokens, we hypothesize that the removal of molecules with more than 202 tokens would be of minimal negative impact on pretraining.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# Large-scale training and parallelization  \n\nFor pretraining we use the masked language model method defined in ref. 30. Initially $15\\%$ of the tokens are selected for possible denoising. From this selection, $80\\%$ of the tokens will be randomly selected and replaced with the [MASK] token, $10\\%$ of the tokens will be randomly selected to be replaced with a random token and the remaining $10\\%$ of the tokens will be unchanged. Training was performed for four epochs through the entire PubChem $+Z I N C$ dataset with a fixed learning rate of $1.6\\times10^{-4}$ and a batch size of 1,600 molecules per GPU on a total of 16 GPUs over two servers connected via InfiniBand fabric. It should be noted that as the number of GPUs utilized increased we found an increase in learning rate was necessary by up to a factor of 8.  \n\nTo scale our training to large datasets (1 billion $^+$ data points), we relied on adaptive bucketing of minibatches by sequence length, as well as parallelization via distributed training (see Supplementary Section A for details). Using linear attention and bucketing allowed us to reduce the number of GPUs needed from roughly 1,000 for quadratic attention with no bucketing to 16 (refs. 52–55).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# Data availability  \n\nData for model pretraining and fine-tuning on benchmark tasks are available at https://github.com/IBM/molformer.",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# Code availability  \n\nPython codes for MoLFormer training and fine-tuning, and Python notebooks for MoLFormer attention visualization, as well as instances of pretrained models, are available at https://github.com/IBM/molformer. For other enquiries contact the corresponding authors.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# References  \n\n1. Rogers, D. & Hahn, M. Extended-connectivity fingerprints. J. Chem. Inf. Model. 50, 742–754 (2010).   \n2. Rupp, M., Tkatchenko, A., Müller, K.-R. & Von Lilienfeld, O. A. Fast and accurate modeling of molecular atomization energies with machine learning. Phys. Rev. Lett. 108, 058301 (2012).   \n3. Weininger, D. SMILES, a chemical language and information system. 1. Introduction to methodology and encoding rules. J. Chem. Inf. Comput. Sci. 28, 31–36 (1988).   \n4. Goh, G. B., Hodas, N. O., Siegel, C. & Vishnu, A. SMILES2Vec: an interpretable general-purpose deep neural network for predicting   \n5. Öztürk, H., Özgür, A. & Ozkirimli, E. DeepDTA: deep drug–target binding affinity prediction. Bioinformatics 34, i821–i829 (2018).   \n6. Paul, A. et al. CheMixNet: mixed DNN architectures for predicting chemical properties using multiple molecular representations. 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Intell. 4, 127–134 (2022).   \n39.\t Altae-Tran, H., Ramsundar, B., Pappu, A. S. & Pande, V. Low data drug discovery with one-shot learning. ACS Cent. Sci. 3, 283–293 (2017).   \n40.\t Xiong, Z. et al. Pushing the boundaries of molecular representation for drug discovery with the graph attention mechanism. J. Med. Chem. 63, 8749–8760 (2019).   \n41.\t Schütt, K. et al. SchNet: a continuous-filter convolutional neural network for modeling quantum interactions. Adv. Neural Inf. Process. Syst. 992–1002 (Curran Associates Inc., 2017).   \n42.\t Rives, A. et al. Biological structure and function emerge from scaling unsupervised learning to 250 million protein sequences. Proc. Natl. Acad. Sci. USA 118, e2016239118 (2021).   \n43.\t Vig, J. et al. BERTology meets biology: interpreting attention in protein language models. In 9th International Conference on Learning Representations (OpenReview.net, 2021).   \n44.\t Urbina, F., Lentzos, F., Invernizzi, C. & Ekins, S. Dual use of artificial-intelligence-powered drug discovery. Nat. Mach. Intell. 4, 189–191 (2022).   \n45.\t Choromanski, K. et al. Rethinking attention with Performers. In Proc. 9th International Conference on Learning Representations (OpenReview.net, 2021).   \n46.\t Shaw, P., Uszkoreit, J. & Vaswani, A. Self-attention with relative position representations. In Proc. NAACL-HLT 464–468 (Association for Computational Linguistics, 2018).   \n47.\t Raffel, C. et al. Exploring the limits of transfer learning with a unified text-to-text transformer. J. Mach. Learn. Res. 21, 1–67 (2020).   \n48.\t Ke, G., He, D. & Liu, T.-Y. Rethinking positional encoding in language pre-training. In 9th International Conference on Learning Representations (OpenReview.net, 2021).   \n49.\t Kim, S. et al. PubChem 2019 update: improved access to chemical data. Nucleic Acids Res. 47, D1102–D1109 (2018).   \n50.\t Irwin, J. J. & Shoichet, B. K. ZINC—a free database of commercially available compounds for virtual screening. J. Chem. Inf. Model. 45, 177–182 (2005).   \n51.\t Schwaller, P. et al. Molecular transformer: a model for uncertainty-calibrated chemical reaction prediction. ACS Cent. Sci. 5, 1572–1583 (2019).   \n52.\t Beltagy, I., Peters, M. E. & Cohan, A. Longformer: the long-document transformer. Preprint at https://arxiv.org/ abs/2004.05150 (2020).   \n53.\t Kitaev, N., Kaiser, L. & Levskaya, A. Reformer: the efficient transformer. In 8th International Conference on Learning Representations (OpenReview.net, 2020).   \n54.\t Wang, S., Li, B. Z., Khabsa, M., Fang, H. & Ma, H. Linformer: self-attention with linear complexity. Preprint at https://arxiv.org/ abs/2006.04768 (2020).   \n55.\t You, Y. et al. Large batch optimization for deep learning: training BERT in 76 minutes. In 8th International Conference on Learning Representations (OpenReview.net, 2020).   \n56.\t Lu, C. et al. Molecular property prediction: a multilevel quantum interactions modeling perspective. Proc. AAAI 33, 1052–1060 (2019).   \n57.\t Yang, K. et al. Analyzing learned molecular representations for property prediction. J. Chem. Inf. Model. 59, 3370–3388 (2019).",
+        "category": " References"
+    },
+    {
+        "id": 14,
+        "chunk": "# Acknowledgement  \n\nWe thank IBM Research for supporting this work.",
+        "category": " References"
+    },
+    {
+        "id": 15,
+        "chunk": "# Author contributions  \n\nAll authors conceived the project, developed the MoLFormer framework and designed experiments. J.R., B.B., V.C. and I.P. performed model training, fine-tuning and inference experiments. I.P.  \n\nand P.D. performed attention map analyses. All authors analysed the results and wrote the paper.",
+        "category": " Abstract"
+    },
+    {
+        "id": 16,
+        "chunk": "# Competing interests  \n\nThe authors declare no competing interests.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# Additional information  \n\nExtended data is available for this paper at https://doi.org/10.1038/ s42256-022-00580-7.  \n\nSupplementary information The online version contains supplementary material available at https://doi.org/10.1038/s42256- 022-00580-7.  \n\nCorrespondence and requests for materials should be addressed to Jerret Ross or Payel Das.  \n\nPeer review information Nature Machine Intelligence thanks the anonymous reviewers for their contribution to the peer review of this work.  \n\nReprints and permissions information is available at www.nature.com/reprints.  \n\nPublisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.  \n\nSpringer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.  \n\n$\\circledcirc$ The Author(s), under exclusive licence to Springer Nature Limited 2022  \n\nExtended Data Table 1 | Comparison of MOLFORMER-XL with fine-tuned MOLFORMER models that are either of smaller size or pretrained on smaller datasets on BBBP, HIV, Sider, Clintox, Tox21 and BACE classification benchmarks   \n\n\n<html><body><table><tr><td>Dataset</td><td>BBBP</td><td>HIV</td><td>BACE</td><td>SIDER</td><td>Clintox</td><td>Tox21</td></tr><tr><td>10% ZINC + 10% PubChem</td><td>91.5</td><td>81.3</td><td>86.6</td><td>68.9</td><td>94.6</td><td>84.5</td></tr><tr><td>10% ZINC + 100% PubChem</td><td>92.2</td><td>79.2</td><td>86.3</td><td>69.0</td><td>94.7</td><td>84.5</td></tr><tr><td>100% ZINC</td><td>89.9</td><td>78.4</td><td>87.7</td><td>66.8</td><td>82.2</td><td>83.2</td></tr><tr><td>MoLFORMER-Base</td><td>90.9</td><td>77.7</td><td>82.8</td><td>64.8</td><td>61.3</td><td>43.2</td></tr><tr><td>MoLFORMER-XL</td><td>93.7</td><td>82.2</td><td>88.2</td><td>69.0</td><td>94.8</td><td>84.7</td></tr></table></body></html>  \n\nExtended Data Table 2 | Performance comparison of fine-tuned MOLFORMER-XL with fine-tuned MOLFORMER models are either of smaller size or pretrained on smaller datasets on QM9 (avg MAE), QM8 (avg MAE), ESOL (RMSE), FreeSolv (RMSE), and Lipophilicity (RMSE) regression benchmarks   \n\n\n<html><body><table><tr><td>Dataset</td><td>QM9</td><td>QM8</td><td>ESOL</td><td>FreeSolv</td><td>Lipophilicity</td></tr><tr><td>10% Zinc + 10% Pub</td><td>1.7754</td><td>0.0108</td><td>0.3295</td><td>0.2221</td><td>0.5472</td></tr><tr><td>10% Zinc + 100% Pub</td><td>1.9093</td><td>0.0102</td><td>0.2775</td><td>0.2050</td><td>0.5331</td></tr><tr><td>100% Zinc</td><td>1.9403</td><td>0.0124</td><td>0.3023</td><td>0.2981</td><td>0.5440</td></tr><tr><td>MoLFORMER-Base</td><td>2.2500</td><td>0.0111</td><td>0.2798</td><td>0.2596</td><td>0.6492</td></tr><tr><td>MoLFORMER-XL</td><td>1.5984</td><td>0.0102</td><td>0.2787</td><td>0.2308</td><td>0.5298</td></tr></table></body></html>  \n\nExtended Data Table 3 | Comparison of different MOLFORMER variants on QM9 test set, in terms of average MAE and average standard MAE. Variants considered are MOLFORMER pretrained using QM9 only, PubChem only, and PubChem+ZINC dataset. The variants with and without fine-tuning on downstream task are compared, as well as models with, $\\mathbf{\\Omega}({\\check{\\mathbf{\\Omega}}})$ )Rotary, and without, (×)Rotary, rotary embeddings. Our best candidate variant (for Supplementary Table 8) is chosen based on the average MAE (Mean Absolute Error) score, lower is better   \n\n\n<html><body><table><tr><td>Pre-training Data → Dataset Size →</td><td colspan=\"3\">QM9 Only 111 ×103</td><td colspan=\"3\">PubChem Only 111 × 106</td><td colspan=\"3\">PubChem+ZINC > 1.1 × 109</td></tr><tr><td>Measure↓</td><td>Frozen ×Rotary</td><td>Fine-tuned × Rotary</td><td>Fine-tuned √Rotary</td><td>Frozen × Rotary</td><td>Fine-tuned × Rotary</td><td>Fine-tuned √ Rotary</td><td>Frozen × Rotary</td><td>Fine-tuned ×Rotary</td><td>Fine-tuned √Rotary</td></tr><tr><td>Avg MAE</td><td>8.3808</td><td>2.4621</td><td>2.6604</td><td>8.2600</td><td>2.9680</td><td>3.3990</td><td>2.5497</td><td>1.8620</td><td>1.5894</td></tr><tr><td>Avg std MAE</td><td>0.2390</td><td>0.0843</td><td>0.0937</td><td>0.2447</td><td>0.0801</td><td>0.1355</td><td>0.0978</td><td>0.0611</td><td>0.0567</td></tr></table></body></html>  \n\nExtended Data Table 4 | Correlation with structural similarity metrics on 10000 randomly selected pairs of molecules from the PubChem dataset. Reported correlations are between (1) the pairwise similarities estimated using molecular Fingerprints and those using MOLFORMER-XL (or ChemBERTa) embeddings and (2) the number of atoms in the maximum common subgraph (MCS) of two molecules and their corresponding Euclidean distance in the embedding space   \n\n\n<html><body><table><tr><td>Correlation</td><td>ChemBERTa</td><td>MoLFORMER-XL</td></tr><tr><td>Fingerprint</td><td>0.48</td><td>0.64</td></tr><tr><td>MCS</td><td>-0.44</td><td>-0.60</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# From Generalist to Specialist: A Survey of Large Language Models for Chemistry  \n\nYang Han1,2 Ziping Wan2 Lu Chen1,2∗ Kai $\\mathbf{Y}\\mathbf{u}^{1,2}$ Xin Chen2\\*   \n$^1\\mathrm{X}$ -LANCE Lab, Department of Computer Science and Engineering MoE Key Lab of Artificial Intelligence, SJTU AI Institute Shanghai Jiao Tong University, Shanghai, China 2Suzhou Laboratory, Suzhou, China   \n{csyanghan,chenlusz}@sjtu.edu.cn,mail.xinchen@gmail.com",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# Abstract  \n\nLarge Language Models (LLMs) have significantly transformed our daily life and established a new paradigm in natural language processing (NLP). However, the predominant pretraining of LLMs on extensive web-based texts remains insufficient for advanced scientific discovery, particularly in chemistry. The scarcity of specialized chemistry data, coupled with the complexity of multi-modal data such as 2D graph, 3D structure and spectrum, present distinct challenges. Although several studies have reviewed Pretrained Language Models (PLMs) in chemistry, there is a conspicuous absence of a systematic survey specifically focused on chemistry-oriented LLMs. In this paper, we outline methodologies for incorporating domain-specific chemistry knowledge and multi-modal information into LLMs, we also conceptualize chemistry LLMs as agents using chemistry tools and investigate their potential to accelerate scientific research. Additionally, we conclude the existing benchmarks to evaluate chemistry ability of LLMs. Finally, we critically examine the current challenges and identify promising directions for future research. Through this comprehensive survey, we aim to assist researchers in staying at the forefront of developments in chemistry LLMs and to inspire innovative applications in the field. 1",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# 1 Introduction  \n\nRecent years have witnessed remarkable advancements in daily life driven by LLMs. Competitive models like GPT-4 (Achiam et al., 2023) and Claude (Anthropic, 2024) have demonstrated exceptional abilities across diverse tasks, often matching or surpassing human-level performance, marking significant progress toward Artificial General Intelligence (AGI, Bubeck et al. (2023)). In scientific domains, LLMs have been applied to handle tasks involving natural language and various scientific data (e.g., molecules, proteins, DNA), showing promising results (Fang et al., 2023). Among these, chemistry LLMs, further tailored for chemical applications via additional training or advanced prompt engineering, have garnered significant attention. Before the advent of LLMs, there are lots of notable efforts towards chemistry, such as MolT5 (Edwards et al., 2022), Text2Mol (Edwards et al., 2021), MoMu (Su et al., 2022), Text+Chem T5 (Christofidellis et al., 2023). However, these models are built on PLMs like BERT (Devlin, 2018) and T5 (Raffel et al., 2020), requiring fine-tuning for specific tasks and lacking emergent abilities (Wei et al., 2022a), such as Chain-ofThought (CoT, Wei et al. (2022b)) reasoning and tool-using capabilities (Qin et al., 2023). Existing reviews (Xiao et al., 2024; Liao et al., 2024; Pei et al., 2024a) have already discussed those PLMs in chemistry, such as Liao et al. (2024), which emphasize molecule encoding methods and pretraining objectives. More related works are discussed in the Appendix A. In contrast, our survey focuses on generative models with Transformer decoder architectures (Vaswani et al., 2017), addressing key challenges of general LLMs and reviewing existing approaches to adapt them for chemistry-specific tasks and applications.  \n\n![](images/12235449972361fd6ca4f5d38858ff57c3df46c4f5303e73c119007704ac3276.jpg)  \nFigure 1: Three common errors in general LLMs arising from the key challenges.  \n\nGeneral LLMs, such as the GPT (Ouyang et al., 2022; Achiam et al., 2023) and LLaMA series (Touvron et al., 2023a,b), have demonstrated impressive performance. However, they tend to underperform on chemistry-related tasks as shown in Figure 1. We identify three key challenges contributing to these limitations.  \n\nChallenge 1: domain knowledge is not enough. Most LLMs are pre-trained with the objective of predicting the next token based on web data sourced from the internet (Ouyang et al., 2022), as demonstrated by open-source models like LLaMa series (Touvron et al., 2023a,b). While some chemistry-related data exist within these datasets, the quantity is minimal, and there is a lack of data specifically tailored for chemistry. This deficiency extends to other crucial steps in the development of LLMs, such as supervised fine-tuning (SFT) and reinforcement learning from human feedback (RLHF, Christiano et al. (2017); Stiennon et al. (2020)).  \n\nChallenge 2: multi-modal data is not perceived. Chemistry encompasses various modalities, including 1D sequences (Krenn et al., 2020), 2D molecular graphs (Duvenaud et al., 2015; Xu et al., 2018; Liu et al., 2019), and 3D structures (Schütt et al., 2018; Satorras et al., 2021; Atz et al., 2021). Additionally, there are numerous chemical spectra, such as Nuclear Magnetic Resonance (NMR, Simpson et al. (2012)), Liquid ChromatographyTandem Mass Spectrometry (LC-MS, Seger (2012); Dührkop et al. (2015); Litsa et al. (2023)), and Infrared Spectroscopy (IR, Alberts et al. (2023)). These spectra contain substantial information that LLMs currently fail to fully exploit.  \n\nChallenge 3: chemistry tools are not utilized. Due to the core design of LLMs, they often struggle with retaining up-to-date knowledge and performing specific chemistry operations (Castro Nascimento and Pimentel, 2023; Schick et al., 2024). On the other hand, there are numerous powerful chemistry tools, such as the structure knowledge retrieval (PubChem (Kim et al., 2019), OPTIMADE (Evans et al., 2024)), and various expert-designed artificial intelligence systems tailored to address specific problems like reaction prediction (Pesciullesi et al., 2020), retrosynthesis planning (Segler et al., 2018) and so on. The absence of integration with these chemistry tools significantly hinders the performance of LLMs in the field of chemistry.  \n\nIn this survey, we critically review current efforts addressing the three key challenges outlined in Figure 2. Additionally, we review the existing benchmarks used to evaluate the performance of chemistry LLMs and offer suggestions for future research directions. To the best of our knowledge, this is the first systematic survey reviewing existing approaches for transferring general LLMs to chemistry-specific LLMs in decoder architecture.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2 Domain Knowledge  \n\nPre-training, SFT and RLHF have been the de facto way to enhance domain knowledge of LLMs. We will detail those methods in the following sections.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2.1 Pre-training  \n\nThe natural of LLMs lay in language modeling, given a set of examples $(x_{1},x_{2},...,x_{n})$ each composed of variable length sequences of symbols $(s_{1},s_{2},..,s_{m})$ , language model is framed as a unsupervised distribution estimation and the joint probabilities over symbols can be formulated (Radford et al., 2019):  \n\n$$\np(x)=\\prod_{i=1}^{n}p(s_{n}|s_{1},...,s_{n-1}),\n$$  \n\nself-attention architectures like the Transformer can be applied to compute these conditional probabilities. Training on a large-scale corpus in this manner enables LLMs to capture rich language representations, refering to pre-training.  \n\nContinue pre-training is prefered given the existence of advanced foundation models like LLaMA (Touvron et al., 2023a,b) and Galactica (Taylor et al., 2022), which already contain some basic chemistry knowledge. In contrast, pretraining from scratch is cost-prohibitive. Chemistry knowledge is typically encoded in specific languages, such as the Simplified Molecular-Input Line-Entry System (SMILES) (Weininger, 1988), which represents 3D structures as flattened sequences while preserving most structural information. Other representations include molecular formulas, SELFIES (Krenn et al., 2020), International Union of Pure and Applied Chemistry (IUPAC) names, and the Chemical Identifier (InChI) (Heller et al., 2013). To enhance foundation models with domain-specific chemistry knowledge, it is necessary to gather pre-training corpora in these chemical languages and apply continued pre-training.  \n\n![](images/e27db081228c2da1fddf0710e5b2d6dd5a896e53ec40ed196fdad2cbfbab5d9c.jpg)  \nFigure 2: Taxonomy of currect approachs for transfering general LLMs to specialized chemistry LLMs.  \n\nThe volume of pre-training data required for chemistry LLMs is immense, making it difficult to obtain and, in some cases, restricted by copyright. To the best of our knowledge, ChemDFM (Zhao et al., 2024b) is the sole chemistry LLM specifically pre-trained on a chemical corpus. ChemDFM’s training data comprises 34 billion tokens from 3.9 million chemical papers collected online before January 2022 and 49 million tokens from 1.4 thousand chemistry books sourced from LibreTexts2 and Gold Books3. Through pre-training on this chemical text, ChemDFM can acquire a solid understanding of chemistry and emerge as the top open-source model (Feng et al., 2024). Another T5-based chemistry LM, Nach0 (Livne et al., 2024), collects 13 million abstracts from PubMed, 119K patent descriptions from the USPTO, and incorporates approximately 100 million documents from ZINC.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.2 SFT  \n\nPre-training on large corpus with next token prediction does not align well with users’ objective, as users expect models to \"follow their instructions helpfully and safely\" (Zhang et al., 2023b). SFT effectively aligns LLMs with user expectations by training them on datasets consisting of (INSTRUCTION, OUTPUT) pairs, where INSTRUCTION refers to specific chemistry tasks and OUTPUT represents the desired responses. Given the variety of chemistry tasks in the SFT dataset, it can be further categorized as follows:  \n\n1. Multi-task SFT: We categorize commonly used chemistry tasks into four types: SMILES understanding, reaction understanding, notation alignment and chemistry-related QA, as detailed in Appendix B. The most significant distinction among different SFT models (Yu et al., 2024; Fang et al., 2023; Zhao et al., 2024b; Zhang et al., 2024a) lie in their data sources and the volume of data used, and the detailed data distribution is shown in Appendix B. The total dataset volume ranges from 1.5M to 3M, although Zhang et al. (2024a) does not provide exact figures, it is likely of a similar magnitude. The distribution of tasks within the SFT dataset determines the model’s chemistry capabilities, as identified by (Feng et al., 2024). Zhao et al. (2024b); Zhang et al. (2024a) focus more on chemistryrelated QA, gathering major data from sources such as chemistry exams and existing datasets, which enhances the model’s ability to answer user questions more naturally.  \n\n2. Task-specific SFT: Task-specific finetuning of LLMs has demonstrated effective prediction performances, often surpassing traditional machine learning models, particularly in low-data scenarios(Jablonka et al., 2024). Jablonka et al. (2024) finetune GPT-3 for classification, regression, and inverse design tasks, achieving competitive results in three case studies (polymers, metal-organic frameworks, and photoswitches). More recently, Liu et al. (2024d) propose hybrid instruction tuning on more than 1000 property tasks with LLaMA2- 7b-chat (Touvron et al., 2023b), reporting up to a $16.6\\%$ average improvement over leading LLM baselines across all classification tasks. Additionally, Chen et al. (2023) also fine-tune LLaMA2-7B-chat with 13,878 pieces of structured material knowledge data to predict inorganic material synthesis pathways.  \n\nIn addition to these chemistry tasks, chemical text mining is also a crucial foundation in chemical research, as much scientific knowledge is dispersed across the text, tables, and figures in millions of academic papers (Dagdelen et al., 2024). Dagdelen et al. (2024) focus on joint named entity recognition and relation extraction, enabling the generation of simple English sentences or more structured formats, such as JSON object, from individual sentences or entire paragraphs. Zhang et al. (2024c) extend these efforts to more chemical text mining tasks, achieving the best performance across all tasks, with exact accuracy ranging from $69\\%$ to $95\\%$ using minimal annotated data.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.3 RLHF  \n\nWhile pre-training and SFT provide chemistry LLMs with domain-specific knowledge and enable them to perform specific tasks, these models are still prone to hallucination. RLHF is the most effective method to alleviate hallucinations and build a truthful, helpful and harmless LLM (Ouyang et al., 2022). There are many detail algorithms to utilize human feedback, such as PPO (Schulman et al., 2017), DPO (Rafailov et al., 2024). Beyond human feedback, other methods for collecting preference feedback include AI feedback (Lee et al., 2023; Bai et al., 2022) and environment feedback (Cao et al., 2024; Dong et al., 2024).  \n\nExisting research on human alignment for chemistry LLMs primarily focuses on molecular generation tasks. Fang et al. (2024b) first pre-trains LLM on SELFIES (Krenn et al., 2020), enabling the generation of syntactically correct molecules; however, the model also produces undesirable molecules, referred as molecular hallucinations. To mitigate these hallucinations and better align with actual chemical contexts, they apply a rank loss (Liu et al., 2022) by assigning higher probabilities to molecule candidates with desired properties. Zholus et al. (2024) finetunes a GPT-based model for 3D molecular design, and utlizes external feedback from docking software using REINFORCE algorithm (Williams, 1992). Hu et al. (2024) further investigates multiple GPT agents to generate desirable molecules in diverse directions, with the reward function estimated by docking software. The objective is to maximize the average reward while simultaneously improving molecular diversity.  \n\nAI and environment feedback are the most commonly used rewards for chemistry LLMs, as the more valuable human feedback is often unavailable due to the need for strong domain knowledge and the lack of effective tools to collect chemistryspecific feedback. Hu et al. (2024) design a Pythonbased open-source graphical user interface (GUI) to explore and evaluate molecules, and capture chemist’s implicit knowledge and preferences more efficiently. This tool provides a promising approach for collecting chemistry-specific feedback to better align chemistry LLMs with human expertise.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 3 Multi-Modal Data  \n\nDomain knowledge training is a standard approach for developing domain-specific LLMs, as demonstrated in fields like geoscience (Deng et al., 2024), law (Zhou et al., 2024), and medicine (Zhang et al., 2023a). However, chemical data is highly fragmented across multiple modalities (Mirza et al., 2024), such as 2D graphs, 3D structures, and spectra, as shown in Figure 3, which cannot be directly processed by vanilla LLMs. Inspired by recent advances in multi-modal and vision LLMs (Liu et al., 2024a; Li et al., 2024a; Huang et al., 2024a), numerous studies have focused on integrating chemical modalities with vanilla LLMs through the design of alignment components. We provide a comprehensive review of these works based on the modalities they support: 1D Sequences, 2D Graphs, 3D Structures, and Other Modalities.",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 3.1 1D Sequences  \n\nSMILES (Weininger, 1988) is a widely used molecular representation, but it is generally processed as text using a byte-pair encoding tokenizer (Sennrich, 2015), which fails to capture its inherent chemical information. To address this limitation, MolX (Le et al., 2024) treats SMILES as a distinct modality and proposes a pre-trained BERTlike (Devlin, 2018) SMILES encoder to extract features, which are then aligned with other modalities through projection. MoleculeGPT (Zhang et al., 2023c) also adapt ChemBerta (Ahmad et al., 2022) for SMILES encoding. However, SMILES lacks robustness and does not fully capture spatial information, leading to the development of other 1D sequence representations, such as SELFIES (Krenn et al., 2020), IUPAC names, molecular fingerprints (Morgan, 1965), and InChI (Heller et al., 2013). These 1D sequences are generally processed similarly to text but can be further refined using specialized encoders, such as SELFormer (Yüksel et al., 2023) for SELFIES and variational autoencoders (VAE, Kingma (2013)) for molecular fingerprints.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3.2 2D Graphs  \n\nCompared to 1D sequences, 2D graphs offer a more intuitive representation of molecular structures and chemical bonds. To process 2D graphs, an encoder is required to convert them into vector representations, followed by a projector to align these vectors with LLMs. Graph neural networks (GNNs, Hu et al. (2019); Xiao et al. (2022)) are widely used as 2D graph encoders and have been adopted by most multimodal chemistry LLMs (Liu et al., 2024e; Li et al., 2024b; Zhang et al., 2023c; Le et al., 2024; Zhang et al., 2024e). For instance, MolTC (Fang et al., 2024a) train two GNNbased encoders and representation projectors by freezing the LLM and backpropagating the generation loss. InstructMol(Cao et al., 2023) employs MoleculeSTM’s graph encoder (Liu et al., 2023a), which is trained through molecular-textual contrastive learning. MolCA (Liu et al., 2023b) utilze a more expressive GNN model - Graph isomorphism network (GIN, Hu et al. (2019)), which pre-trained on 2 million molecules from the ZINC15 (Sterling and Irwin, 2015). HIGHT(Chen et al., 2024b) further introduce a hierarchical graph tokenizer which em Vector Quantized-Variational AutoEncoder (VQVAE, (Zang et al., 2023)) to extract highorder structural information and then feed them into LLMs.  \n\nThere are various projectors to map graph features into the LLM embedding space, such as crossattention (Alayrac et al., 2022), Q-Former (Li et al., 2023), position-aware vision language adapters (Bai et al., 2023), and light-weight Multi-layer Perceptron (MLP). Q-Former is the most widely adopted projector (Liu et al., 2023b; Fang et al., 2024a; Zhang et al., 2023c), maintaining a set of learnable query tokens to interact with the graph encoder and extract features. However, InstructMol (Cao et al., 2023) argues that Q-Former requires a large number of paired data for pretraining, making alignment inefficient, and instead employs a lightweight MLP for alignment. DeCo (Yao et al., 2024) also find that Q-Former tends to lose finegrained visual attributes and spatial locality in visual LLMs.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3.3 3D Structures  \n\nThe 3D structures of molecules is crucial because it contains spatial information essential for understanding molecular dynamics, protein-ligand interactions, enzymatic functions, and other biomolecular phenomena (Li et al., 2024d). Unlike 1D sequences or 2D graphs, 3D structures provide a complete geometric representation of the molecule, allowing models to take into account the threedimensional arrangement of atoms and the distances between them. MolLM (Tang et al., 2024) and Uni-Mol (Zhou et al., 2023) demotarte performance enhancement in downstream tasks when incorporating 3D information. 3D-MoLM (Li et al., 2024d) utilizes Uni-Mol (Zhou et al., 2023) to encode 3D conformations generated from SMILES and employs Q-Former (Li et al., 2023) for crossmodal alignment. This approach outperforms baseline models that rely on 1D or 2D molecular perceptions in tasks such as molecule-text retrieval, molecule captioning, and open-text question answering, particularly when addressing 3Ddependent properties. In contrast, 3D-MolT5 (Pei et al., 2024b) contends that the modality alignment approach employed by 3D-MoLM (Li et al., 2024d) is inefficient and introduces a specialized 3D vocabulary to train 1D, 3D, and text modalities within a unified architecture, demonstrating significant improvements over 3D-MoLM (Li et al., 2024d) in various downstream tasks.  \n\n![](images/c57b3a0230a7f5f18666acc974724e5e7c79e9f1fe0877ff143223f4c31a5c09.jpg)  \nFigure 3: For example, the compound $C_{8}H_{11}N O$ can be represented across various modalities. 1D sequeues include SMILES, IUPAC name and so on. Molecular structure consist of 2D graphs and 3D structures, 2D graphs encompass three matrices: atomic features, atom connection, chemical bonds features, 3D strutures compromise the coordinate of every atom. Other modalities consist of mass spectra, images, and so on.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3.4 Other Modalities  \n\n2D graphs or 3D structures generated by RDKit are often represented as matrices, which are not humanreadable. In contrast, chemical images are more intuitive and frequently used to represent chemical structures in a human-friendly format. At the same time, numerous efficient image algorithms, such as the Vision Transformer (ViT) (Dosovitskiy, 2020) and Swin Transformer (Liu et al., 2021), can be directly employed as modality encoders. GITMol (Liu et al., 2024c) utilizes Swin Transformer (Liu et al., 2021) from SwinOCSR for image ecoding, and adopt cross-attention for modal alignment. ChemVLM (Li et al., 2024c) adopts InternViT-6B (Chen et al., 2024d) as the vision encoder, following the LLaVA (Liu et al., 2024a) architecture in the \"ViT-MLP-LLM\" style. Additionally, ChemVLM introduces three new chemical image datasets — ChemOCR, MMCR-Bench, and MMChemBench, However, these datasets are not open-source at this time. To facilitate future research on chemical images, we provide a summary of existing chemical image datasets in Appendix C.  \n\nAnother important chemistry-specific modality is spectral , which can be obtained through simulations (CFMID 4.0, Wang et al. (2021)) and experiments. This data is rich in structural information and plays a vital role in determining molecular structures. For example, MSNovelist (Stravs et al., 2022) utilizes an encoder-decoder neural network to generate molecular structures de novo from tandem mass spectrometry, but its accuracy is less than $50\\%$ . Comprehensive exploration of the diverse information embedded in these spectral modalities is crucial for advancing research in this domain.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 4 Chemistry Tools  \n\nAlthough domian knowledge training and multimodal enhancement can encode a certain amount of domain-specific knowledge into LLMs, it is constrained by scalability and intrinsic memory capacity (Chiang et al., 2024). In this section, We emphasize improving the capability of LLMs to tackle complex chemistry and embodied problems through the use of chemistry tools, such as operating experimental equipment for scientific research. We categorize these chemistry tools into three types: structured knowledge retrieval, machine learning (ML) models, and embodied robots.",
+        "category": " Introduction"
+    },
+    {
+        "id": 14,
+        "chunk": "# 4.1 Structured Knowledge Retrieval  \n\nStructured knowledge retrieval, or retrievalaugmented generation (RAG, (Lewis et al., 2020)), has been proposed to alleviate hallucinations in both chemistry-specific and general LLMs (Xu et al., 2024). The key component of knowledge retrieval is the knowledge source, and the retrieval method is typically determined by the source. We categorize common knowledge sources as follows:  \n\n1. Database: There are many famous chemistry database, such as, Materials Project (MP, Jain et al. (2013)), OPTIMADE (Evans et al.,  \n\n2024). These databases cannot be accessed through direct web searches; instead, data retrieval requires following specific API documentation. LLaMP (Chiang et al., 2024) design hierarchical ReAct (Yao et al., 2022) agents that can dynamically and recursively interact with MP to ground LLMs on highfidelity materials informatics.  \n\n2. Scientific Literature: Peer-reviewed research articles are the most accurate and authoritative data source, and there are many Scholarly engines can help us find the related papers. Zheng et al. (2023) propose to use ChatGPT for text mining the synthesis conditions of metal-organic frameworks (MOFs) and develop a ChatGPT Chemistry Assistant (CCA) chatbot base on the systhesis dataset and bibliographic context (such as authors and DOI), to alleviate hallucinatory errors.  \n\n3. Knowledge Graph: A knowledge graph is a structured representation that allows for complex queries and provides insights that traditional databases cannot easily offer (Ye et al., 2024). Liu et al. (2024b) propose KG-driven Knowledge Injection (DRAK-K) by retrieving the top- $\\mathbf{\\nabla}\\cdot\\mathbf{k}$ most relevant pieces of knowledge and transforming the related knowledge into structured background context for LLMs.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 4.2 ML Models  \n\nLLMs are prone to worse than existing ML baselines (Guo et al., 2023) in reaction-related tasks, and this tasks are difficult to be solved by knowledge retriveal. On the other hand, LLMs can interact with various tools (APIs) to accomplish complex tasks (Qin et al., 2023) in ReAct (Yao et al., 2022) style , and we can boost chemistry LLMs performance with SOTA ML models. ChemCrow (M. Bran et al., 2024) design reacttion tool set consist of NameRXN, ReactionPredict and ReactionPlanner provied by RXN4Chemistry API from IBM Research, and plan the syntheses of an insect repellent and three organocatalysts. ChatChemTS (Ishida et al., 2024) develop a user frendly chatbot named ChatChemTS which utilize AI-based molecule generators such as ChemTSv2 (Ishida et al., 2023) for molecular design. ChatMOF (Kang and Kim, 2024) foucs on generating new metal organic frameworks (MOFs, Kitagawa et al. (2014)) which are useful in many chemical applications due to large porosity, high surface area,and exceptional tunability (Deng et al., 2012), and they also predict the properties of generated MOFs. They adopt MOFTransformer (Kang et al., 2023) for the universal prediction of MOF properties and genetic algorithm (Park et al., 2022) to generate new MOFs, and achieve high accuracy of $95.7\\%$ for predicting, and $87.5\\%$ for generating tasks with GPT-4.  \n\nML models can also help discover new catalyst by just giving feedback, ChemReasoner (Sprueill et al., 2024) use atomistic graph neural networks (GNNs) trained from quantum chemistry simulations for structure-based scoring, the GNNs are used to yeild reward and drive LLM towards catalysts with specific properties. This novel idea suggest that ML models not only can be used as tools aid in specific task, but also can be used as feeback to guide and stimulate the LLMs to fulfill the tasks by themselfs.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 4.3 Embodied Robots  \n\nChemistry experiments are often resoure- and laborintensive, and automated experiments canattain higher throughput and precision (Tom et al., 2024). However, the discovery of new material requires not only automation but autonomy—the ability of an experimental agent to interpret data and make decisions based on it (Szymanski et al., 2023), where LLMs are excellent at planing and reasoning, showing promise of sought-after system that autonomously designs and executes scientific experiments (Boiko et al., 2023).  \n\nCoscientist (Boiko et al., 2023) is a GPT-4 driven AI system which can autonomously designs, plans and performs complex experiments, it demonstrate the versatility and performance across six tasks. CLAIRify (Yoshikawa et al., 2023) also leverage robots and LLM to automate chemistry experiments, and they pay more attention to how to generate syntactically valid programs in a data-scarce domain-specific language that incorporates environmental constraints. ORGANA (Darvish et al., 2024) further extend CLAIRify with visual perception of the environment and support complex experiments between multiple robots.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 5 Benchmarks  \n\nBenchmarks are essential for evaluating the performance of chemistry LLMs on chemistry-related tasks and can be broadly categorized into two categories: science benchmarks and moleculespecific benchmarks. Chemistry is a subset of science, and existing science benchmarks evaluate LLMs’ ability to solve scientific problems, including those related to chemistry. Existing science benchmarks, such as SciQ (Welbl et al., 2017), SciCode (Tian et al., 2024), ScienceQA (Lu et al., 2022), AGIEval (Zhong et al., 2023), SciEval (Sun et al., 2024), SciBench (Wang et al., 2023), and VisScience(Jiang et al., 2024), typically cover a wide range of scientific disciplines, including biology, earth science, physics, chemistry, and even social science. Although these science benchmarks include chemistry-related tasks, they are not specifically designed for chemistry and fail to address many chemistry-specific problems.  \n\nIn contrast, molecule-specific benchmarks are designed to assess knowledge in molecule-related sciences (e.g., chemistry, materials science, biochemistry). ChemLLMBench (Guo et al., 2023) first adapts traditional chemistry tasks to a language model setting, evaluating the performance of contemporary LLMs in zero-shot and few-shot prompts. SciKnowEval (Feng et al., 2024) expands the chemistry domain to molecules by introducing a large dataset of 50,000 problems that assess various LLM abilities, including knowledge coverage, reflection and reasoning, and application. MassSpecGym (Bushuiev et al., 2024) focuses on characterization techniques, such as Tandem Mass Spectrometry (MS/MS), and evaluates the ability of LLMs to elucidate molecular structures from MS/MS data. Notably, there are several other important chemistry benchmarks, including ScholarChemQA (Chen et al., 2024a), SCIASSESS (Cai et al., 2024), SciKnowEval (Feng et al., 2024), ChemEVal (Huang et al., 2024b), Alberts et al. (2024), and MolPuzzles (Guo et al., 2024). Due to page limitations, we provide a brief overview of these benchmarks in Table 3.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# 6 Future Directions  \n\nAlthough current approaches have made steady progress towards chemistry LLMs, there remains significant room for improvement. Future research directions can be categorized into three main aspects: data, model, and application.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 19,
+        "chunk": "# 6.1 Data  \n\nData Diversity Training data is the foundation of LLMs. However, most existing datasets are built from pre-existing sources, such as MoleculeNet (Wu et al., 2018), and cover a limited range of chemistry tasks. Future work should aim to create more diverse and comprehensive datasets to enhance the training of chemistry LLMs and broaden their capabilities.  \n\nCoT Reasoning Chain-of-Thought (CoT, Wei et al. (2022b) ) reasoning is one of the most notable emergent abilities of LLMs, involving the generation of a sequence of intermediate steps leading to the final answer. However, existing chemistry LLMs often lack this critical reasoning capability due to simple training instruction pairs. Developing training data with explicit reasoning paths to effectively elicit the CoT ability in chemistry LLMs is a crucial direction for future research.  \n\nChemical Modality As described in Section 3.4, many chemistry-specific spectra are not yet fully exploited in in chemistry LLMs. However, these spectra contain rich structural information that can be valuable for various chemical tasks. For example, tandem mass spectrometry (MS/MS) can provide detailed insights into the molecular structure, allowing for the identification and characterization of compounds and elucidation of reaction mechanisms.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# 6.2 Model  \n\nMulti-Modal Alignment Most works towards multi-modal chemistry LLMs always invole a single pair of modalities, limiting their representations ability. Align multiple N $(\\geq3)$ ) modalities is a promising direction as different modalites are complementary and can provide more comprehensive understanding of chemistry molecules.  \n\nRLXF RLHF is a crucial step in training powerful LLMs. Although obtaining human feedback is challenging, especially in chemistry where data annotation requires specialized domain knowledg, we can leverage advanced LLMs as assistants to guide this process. Additionally, we can also utilize results from professional chemistry software as a form of reward to align chemistry LLMs.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# 6.3 Application  \n\nResearch Assistants Chemistry LLMs have the potential to serve as powerful research assistants, aiding chemists by automating routine tasks such as literature review, data analysis, and hypothesis generation. For future development, these models can be designed to understand complex scientific queries, provide insights from vast amounts of chemical literature, suggest experimental protocols, and even propose novel research directions.  \n\nAutomated Experimentation Automated experimentation is another promising direction for advancing chemistry LLMs. Integrating these models with automated laboratory systems can enable them to not only predict molecular properties or suggest potential chemical reactions but also design, execute, and analyze experiments in real-time. Future research should explore how chemistry LLMs can be trained and aligned to interact with automated experimental setups, ensuring reliability, safety, and compliance with scientific standards.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# 7 Conclusion  \n\nIn this survey, we systematically investigate the current approaches to adapting general LLMs for chemistry LLMs. We highlight key challenges, including domain knowledge, multi-modal data, and the integration of chemistry-specific tools, and review existing efforts to address these challenges. While significant progress has been made, achieving chemical general intelligence remains a distant goal, and we identify promising future directions. We hope this survey will inspire further innovative research in the field.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 23,
+        "chunk": "# Limitations  \n\nIn this paper, a comprehensive review of existing methods for constructing chemistry-focused LLMs is presented, with an emphasis on three key aspects for enhancing general LLMs: domain-specific knowledge, multi-modal data, and chemistry tools. This survey aims to provide researchers with a concise understanding of chemistry LLMs and suggest potential directions for future research. However, certain limitations may be present.  \n\nReferences. Due to page limitations and the rapid development of the field, we may not include all relevant references and detailed technical information. However, we strive to keep our work up-to-date on our GitHub repository.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 24,
+        "chunk": "# Acknowledgements  \n\nI would like to express my gratitude to the anonymous reviewers for their meticulous and diligent review efforts. This work was supported by National Science and Technology Major Project (Grant  \n\nNo. 2023ZD0120703), National Natural Science Foundation of China (Grant Nos. 92370206, U23B2057, 62120106006), and Shanghai Municipal Science and Technology Major Project (Grant No. 2021SHZDZX0102).  \n\nReferences   \nJosh Achiam, Steven Adler, Sandhini Agarwal, Lama Ahmad, Ilge Akkaya, Florencia Leoni Aleman, Diogo Almeida, Janko Altenschmidt, Sam Altman, Shyamal Anadkat, et al. 2023. Gpt-4 technical report. arXiv preprint arXiv:2303.08774.   \nWalid Ahmad, Elana Simon, Seyone Chithrananda, Gabriel Grand, and Bharath Ramsundar. 2022. 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+        "category": " References"
+    },
+    {
+        "id": 25,
+        "chunk": "# A Related Work  \n\nThe intersection of LLMs and chemistry is an urgent and rapidly growing field. Numerous works and reviews have addressed this topic, which can be broadly categorized into:",
+        "category": " Introduction"
+    },
+    {
+        "id": 26,
+        "chunk": "# A.1 General Science  \n\nSeveral surveys focus on general science, including chemistry. Zhang et al. (2024d) explore LLM applications across mathematics, physics, biology, medicine, geography, geology, environmental science, and chemistry. However, the broad scope limits the depth of discussion on chemistry-specific LLMs. Zhang et al. (2024b) focus more on the chemical domain but still include biological LLMs and BERT-style models, without discussing the emergent applications of chemistry-specific agents.",
+        "category": " Introduction"
+    },
+    {
+        "id": 27,
+        "chunk": "# A.2 Chemistry-Specific Surveys  \n\nChemistry’s significance has drawn considerable attention, leading to various efforts summarizing current trends. Xia et al. (2022) review Chemical Pre-trained Models (CPMs) based on GNNs or Transformers but focus little on LLMs. Janakarajan et al. (2024) emphasize the role of language models in molecular discovery but offer limited insights on training chemistry-specific LLMs. Liao et al. (2024) concentrate on molecule encoding and pretraining objectives, while Pei et al. (2024a) discuss progress from a multi-modal perspective, neglecting LLMs’ tool-using potential. Ramos et al. (2024) review chemistry LLM agent applications in literature analysis, experiment planning, and hypothesis generation, but overlook multi-modal capabilities. Notably, these surveys categorize BERTstyle LMs as LLMs, despite their need for taskspecific fine-tuning and lack of emergent abilities.",
+        "category": " Introduction"
+    },
+    {
+        "id": 28,
+        "chunk": "# B SFT Tasks Description  \n\nThe most frequently used chemistry tasks for SFT and their description are shown in Table 1. In accordance with the task division presented in Table 1, we illustrate in Figure 4 the data distribution of the commonly used SFT dataset.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 29,
+        "chunk": "# C Molecule Image Dataset  \n\nWe describe the existing molecule image dataset in Table 2.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 30,
+        "chunk": "# D Benchmarks  \n\nWe briefly introduce the existing benchmarks in Table 3, covering aspects such as subject, task type, dynamics, source, and modality.  \n\n<html><body><table><tr><td>Type</td><td>Chemistry Tasks</td><td>Description</td></tr><tr><td rowspan=\"3\">SMILES Understanding</td><td>Molecule description</td><td>Given a molecule SMILES, generating text descrip tion illuminating the structure, properties ,biological activity, and applications.</td></tr><tr><td>Text-based molecule design</td><td>Inverse task of molecule description, given a text description, generating the molecule SMILES.</td></tr><tr><td>Molecular property prediction</td><td>Molecular property prediction focus on drawn from Mquantum mechanics properties of molecules drawn from MoleculeNet.</td></tr><tr><td rowspan=\"3\">Reaction Understanding</td><td>Reagent prediction</td><td>Reagent prediction generate suitable catalysts, sol- vents, or ancillary substances required for a specific chemical reaction.</td></tr><tr><td>Forward reaction prediction</td><td>Forward reaction prediction generate probable prod- uct(s) of a chemical reaction.</td></tr><tr><td>Retrosynthesis</td><td>Inverse task of forward reaction prediction, generate the synthesis routes and precursor molecules given target molecule.</td></tr><tr><td rowspan=\"2\">Notation Alignment</td><td>SMILES and IUPAC names</td><td>Given SMILES, generate IUPAC name, and reverse transformation.</td></tr><tr><td> SMILES and Formulas</td><td>Given SMILES, generate formulas, and reverse trans- formation.</td></tr><tr><td>Chemistry-Related QA</td><td>QA</td><td>Chemical QA extracted from existing dataset or exam.</td></tr></table></body></html>  \n\n![](images/9a46e005c871ece12900c7ef49e1acc5686bec2371917fe0aa95594707a89599.jpg)  \nTable 1: The most frequently used chemistry tasks for SFT.   \nFigure 4: The compositional structure of representative SFT dataset. The definition of tasks above the the horizontal lines is shown in Table 1, the source and size of the different tasks are indicated below the horizontal lines, and percentages on the pie charts are present to show the difference of different dataset.  \n\nTable 2: Overview of molecular image datasets, categorized into synthetic and realistic groups with details on their scale and descriptions. Synthetic datasets are primarily RDKit-generated or derived from large collections, while realistic datasets include handwritten and reaction images. Some datasets are closed-source or only provide evaluation data.   \n\n\n<html><body><table><tr><td></td><td>Dataset</td><td> scale</td><td>Description</td></tr><tr><td rowspan=\"5\">Synthetic</td><td>USPTO-680K (Chen et al., 2024c)</td><td>680K</td><td>Multiple molecular formulas in one image</td></tr><tr><td>USPTO-30K (Morin et al., 2023)</td><td>30K</td><td>10K without bbreviation groups; 10K has superatomic groups; 10K is larger than 70 atoms</td></tr><tr><td>MolGrapher-Synthetic-300K (Morin et al., 2023)</td><td>300K</td><td>Rdkit generation</td></tr><tr><td>img2Mol (Clevert et al., 2021)</td><td>41K</td><td>Rdkit generation</td></tr><tr><td> MMChemOCR (Li et al., 2024c)</td><td>1K</td><td>closed source</td></tr><tr><td>MMCR-bench (Li et al., 2024c)</td><td>1K</td><td>closed source</td></tr><tr><td rowspan=\"4\">Realistic</td><td>MMChemBench (Li et al., 2024c)</td><td>700</td><td>closed source</td></tr><tr><td>MolNexTR test data (Chen et al., 2024c)</td><td>18K</td><td>5088 handwritten molecular images</td></tr><tr><td>RxnScribe (Qian et al., 2023)</td><td>1413</td><td>4 forms of reaction images</td></tr><tr><td>OpenChemIED (Fan et al., 2024)</td><td>254</td><td>Only eval data is open source</td></tr><tr><td></td><td>ReactionDataExtractor 2.0 (Wilary and Cole, 2023)</td><td>517</td><td>Only eval data is open source</td></tr></table></body></html>  \n\nTable 3: A brief introduction to the existing benchmarks. \"MCQ\" refers to Multi-Choice Questions, while \"DA\" denotes Direct-Answer tasks. \"Samples\" refers to the number of test set examples. The \"Spectra\" modality is distinctive, as spectra can be represented either as images or text.   \n\n\n<html><body><table><tr><td>Dataset</td><td>Subject</td><td>Task Type</td><td>Samples</td><td>Modality</td><td>Source</td></tr><tr><td>SciQ (Welbl et al., 2017)</td><td>Bio, Chem, Earth, Phy</td><td>MCQ,DA</td><td>1000</td><td>Text</td><td>CK-12, OpenStax</td></tr><tr><td>SciCode (Tian et al., 2024)</td><td>Math, Phy, Chem,</td><td>DA</td><td>338</td><td>Text</td><td>Research Paper</td></tr><tr><td>ScienceQA (Lu et al., 2022)</td><td>Bio, Mat Natural, Social and</td><td>MCQ</td><td>4,241</td><td>Image, Text</td><td>School Curricula</td></tr><tr><td>AGIEval (Zhong et al., 2023)</td><td>Language Science Bio, Chem, Phy, Math,</td><td>MCQ,DA</td><td>8.062</td><td>Text</td><td>Human Exam</td></tr><tr><td>SciEval (Sun et al., 2024)</td><td>Law, at el. Bio, Chem, Phy</td><td>MCQ,DA</td><td>15901</td><td>Text</td><td>Socratic QA , MedQA,</td></tr><tr><td>SciBench (Wang et al., 2023)</td><td>Chem, Math, Phy</td><td>DA</td><td>789</td><td> Image, Text</td><td>PubMedQA TextBook</td></tr><tr><td>VisScience (Jiang et al., 2024)</td><td>Math, Chem, Phy</td><td>MCQ,DA</td><td>3000</td><td>Image,Text</td><td>K12 education</td></tr><tr><td>ChemLLMBench (Guo et al.,2023)</td><td>Chem</td><td>DA</td><td>800</td><td>Text</td><td>PubChem, MoleculeNet,</td></tr><tr><td>SciKnowEval (Feng et al.,2024)</td><td>Bio, Chem</td><td>MCQ, DA</td><td>50.048</td><td>Text</td><td>USPTO, ChEBI,Suzuki Literatures, Existing QAs,</td></tr><tr><td>MassSpecGym (Bushuiev et al., 2024)</td><td>Chem</td><td>DA</td><td>17,556</td><td>Spectra(Text)</td><td>Databases MoNA, MassBank,</td></tr><tr><td>ScholarChemQA (Chen et al., 2024a)</td><td>Chem</td><td>MCQ</td><td>500</td><td>Text</td><td>GNPS,In-House Database Paper</td></tr><tr><td>SciAssess (Cai et al., 2024)</td><td>Mat, Bio, Drug</td><td>MCQ,DA</td><td>14,721</td><td>Image, Text</td><td>Existing benchmarks,</td></tr><tr><td>ChemEVal (Huang et al., 2024b)</td><td>Chem</td><td>DA</td><td>840</td><td>Text</td><td>Papers Open-Source Data</td></tr><tr><td>MolPuzzles (Guo et al., 2024)</td><td>Chem</td><td>DA</td><td>19891</td><td>Spectra(Image)</td><td>Textbook</td></tr><tr><td>Alberts et al. (2024)</td><td>Chem</td><td>DA</td><td>79K</td><td>Spectra(Text)</td><td>USPTO</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Research AI in Chemical EngineeringÐReview",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Toward Next-Generation Heterogeneous Catalysts: Empowering Surface Reactivity Prediction with Machine Learning  \n\nXinyan Liu \\*, Hong-Jie Peng  \n\nInstitute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 611731, China",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# A R t i c L E i N F o",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# A b s t R A c t  \n\nArticle history:   \nReceived 5 January 2023   \nRevised 27 May 2023   \nAccepted 17 July 2023   \nAvailable online 5 January 2024  \n\nKeywords:   \nMachine learning   \nHeterogeneous catalysis   \nChemisorption   \nTheoretical simulation   \nMaterials design   \nHigh-throughput screening  \n\nHeterogeneous catalysis remains at the core of various bulk chemical manufacturing and energy conversion processes, and its revolution necessitates the hunt for new materials with ideal catalytic activities and economic feasibility. Computational high-throughput screening presents a viable solution to this challenge, as machine learning (ML) has demonstrated its great potential in accelerating such processes by providing satisfactory estimations of surface reactivity with relatively low-cost information. This review focuses on recent progress in applying ML in adsorption energy prediction, which predominantly quantifies the catalytic potential of a solid catalyst. ML models that leverage inputs from different categories and exhibit various levels of complexity are classified and discussed. At the end of the review, an outlook on the current challenges and future opportunities of ML-assisted catalyst screening is supplied. We believe that this review summarizes major achievements in accelerating catalyst discovery through ML and can inspire researchers to further devise novel strategies to accelerate materials design and, ultimately, reshape the chemical industry and energy landscape.  \n\n$\\circledcirc$ 2024 THE AUTHORS. Published by Elsevier LTD on behalf of Chinese Academy of Engineering and Higher Education Press Limited Company. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# 1. Introduction  \n\nPositioned at the heart of the chemical industry, catalytic reactions are involved in the processes of over $80\\%$ of all manufactured products [1]. Among various catalysis scenarios, heterogeneous catalysis using solid catalysts receives exceptional attention due to its high scalability for bulk manufacturing and its outstanding advantages in product separation and catalyst recycling [2,3]. Contemporary industrialized heterogeneous catalytic processes, such as methane reforming [4], ammonia synthesis [5], hydrocarbon cracking [6], and a variety of selective hydrogenation/dehydrogenation reactions [7–10], are mostly thermochemical and usually require high-temperature and/or high-pressure conditions to shift the chemical equilibria and modulate the reaction rates. Moreover, these conventional processes rely heavily on the use of fossil resources as reactants and for energy inputs, as well as on precious metals (e.g., Pt, Pd, Ru, and Rh) as catalysts, thereby deviating from the goal of global sustainability [11,12]. Therefore, it is imperative to design new catalytic reactions and processes that are more energetically efficient, environmentally friendly, and economically favorable. Along with the continuous advancement of human civilization, the journey to hunt for such processes and corresponding key materials never ceases.  \n\nThe rapid development of renewable energy technology, such as photovoltaics, has spurred this journey by enabling large-scale and low-cost ‘‘greenº electricity generation [11,13]. To better utilize surplus electricity, one of the most well-known initiatives is to replace fossil–fuel-derived ‘‘greyº hydrogen with ‘‘greenº hydrogen, the production of which relies on key technology such as electrochemical water splitting [14,15]. Similar concepts of green electricity-to-chemical energy conversion have also been implemented in carbon dioxide reduction reactions $(\\mathsf{C O}_{2}\\mathsf{R R})$ [16–22] and ammonia electrosynthesis [23–26]. In turn, renewably synthesized hydrogen, carbon-containing fuels, and ammonia are attractive feeds for fuel cells/engines or raw materials for the chemical industry, aiding to close the fossil-resource-free loops of carbon and nitrogen. The rational design of highly efficient and earthabundant catalytic materials plays a central role in achieving this goal, prior to subsequent reaction engineering and scaling up. Unfortunately, current catalytic materials are still far from satisfactory in terms of efficiency and/or scalability [27–30]. Innovations in next-generation catalyst design are therefore in high demand.  \n\nThe design, optimization, and further development of novel catalytic materials traditionally rely on Edisonian trial-and-error processes in Fig. 1 (Scheme 1). However, the efficiency of such processes is limited, as it usually takes decades to discover and commercialize a new catalyst. Furthermore, as it is impossible to exhaust allÐor even the majorityÐof the abundant candidate space of both compositions and structures, a more efficient methodology to navigate through this space remains indispensable. In fact, the flourishing of computational methods and theoretical modeling (e.g., density functional theory (DFT) calculations) has enabled another path that can replace tedious experimental exploration in Fig. 1 (Scheme 2) [31–34]. It has been revealed that the surface reaction rates on a solid catalyst can be correlated to the surface bond energies of adsorbed species presented in the reaction network (including transition states (TSs)), which are accessible through state-of-the-art computations [34–36]. Thus, it is possible to conduct ‘‘virtualº experiments on computers to assess the catalytic activity of a material by calculating the relevant energies. When reaction rates are reformulated as functions of only one or two descriptor(s), the high-dimensional problem of searching for candidates with desirable catalytic performance can be further collapsed to the hunt for catalysts exhibiting optimal descriptor values, where the descriptor is often a physical or chemical property that can be calculated or measured [36]. This so-called descriptor-based approach opens up new possibilities for the high-throughput computational screening of undiscovered catalysts. Among various electronic and geometric descriptors, the adsorption energies of surface species are frequently adopted, as $\\textcircled{1}$ they can be obtained via computations and $\\textcircled{2}$ the calculation results can be verified through accurate calorimetric experiments [37]. More importantly, the adsorption-energy-based activity map can be viewed as a quantitative implementation of the classical Sabatier principle, providing a rational understanding of trends in heterogeneous catalysis [38]. Although establishing activity maps helps to expedite the discovery of novel catalysts, acquiring energetic descriptors through modeling is still computationally demanding on a large scale, especially considering the enormous compositional and/or structural heterogeneities when searching for multicomponent and/or multisite catalytic materials. To explore the vast material space for heterogeneous catalyst screening, it is therefore vital to develop ways to obtain surface adsorption strengths more efficiently and effectively.  \n\n![](images/006d64419e29d97f7818d9d68cfb233aa868a769c1dd455a0bf8e198dcca4d3c.jpg)  \nFig. 1. Schematic illustration of three common schemes for catalyst screening. Scheme 1 refers to a conventional Edisonian trial-and-error process, where potential candidates (numbered $N_{\\mathrm{E}}{\\mathrm{.}}$ are selected for synthesis, characterization, and performance evaluation. Based on the results, new candidates may need to be reselected from the material space. Scheme 2 represents a conventional computational descriptor-based approach, where surface reactivities of more materials (numbered $N_{\\mathrm{T}},$ where $N_{\\mathrm{T}}$ may be orders of magnitude larger than $N_{\\mathrm{E}},$ are evaluated through simulation. Potential candidates are screened based on a further combination with an activity map established from theoretical trends such as scaling relations. Compared with Scheme 1, far fewer potential candidates are subjected to experimental validation. Scheme 3 refers to a machine learning (ML)-aided approach, where the large-body simulations in Scheme 2 are replaced with predictions from ML models. The outcome understandings can be utilized to re-improve the model and theoretical understanding. Dashed arrows in the figure represent processes that are time-consuming or resource-intensive, while solid arrows refer to those that are relatively fast and cheap.  \n\nOver the past decades, the rapid development of computer science and artificial intelligence (AI), along with the establishment of comprehensive databases, has enabled numerous possibilities for applying AI in chemistry and materials sciences for experiments, characterizations, and modeling [39–54]. Incorporating advanced machine learning (ML) models in catalyst design and screening makes it possible to directly predict the surface reactivity from fewer or less computationally expensive properties, with huge potential for improvements in cost and accuracy in Fig. 1 (Scheme 3). Consequently, the acceleration of the entire screening process can be envisioned. In addition, unveiling hidden patterns and correlations through ML offers alternative opportunities to further our physical understanding of catalytic systems and obtain fresh perspectives on catalyst design [55]. In this case, the application of ML for adsorption energy prediction and high-throughput catalyst screening, while still in its infancy, has already demonstrated its huge potential in enabling a paradigm shift in the discovery of new materials for emerging catalytic processes. Thus, summarizing the latest advances in ML-empowered highthroughput catalyst screening and proposing promising directions remains beneficial and necessary for future research.  \n\nUnlike the existing reviews covering the many aspects of ML application in catalysis research [56–66], this review has a particular focus on the data-driven prediction of adsorption energies, as the surface reactivity dominantly quantifies the catalytic potential of a solid catalyst. In addition, we highlight efforts to combine ML models with experimental exploration. In this review, we first categorize ML models according to the inputs adoptedÐnamely, ab initio or non-ab initio featuresÐand discuss related research progress in two consecutive sections. In each section, works targeting systems with different levels of complexity are summarized, along with the physical understandings these works might supply. Next, ML-guided experimental catalyst discovery is showcased, based on either the ML model’s predictive power or interpretable insights. Finally, we provide an outlook on current challenges and future opportunities in ML-assisted catalyst screening. As this is a focus review, we do not discuss the general principles and common models of ML, or the application of ML in other aspects of catalysis research such as high-throughput experimentation and ML-accelerated theoretical modeling; detailed information on these topics is already available in other reviews [57–61].",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2. ML with ab initio features",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.1. Features based on calculated adsorption energies",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.1.1. Adsorption scaling relations  \n\nAs discussed in the previous section, the idea of highthroughput screening can be realized, with the availability of material descriptors (e.g., adsorption energy and electronic structure) through ab initio calculations and the proposal of the descriptor-based approach. The main idea of this approach is the dimension reduction brought by so-called scaling relations, which projects reaction energetics onto a few properties [35,36,38]. In brief, it has been found that the adsorption energies of different adsorbates that bind to the surface through the same atom(s) tend to scale with each other, usually in a linear fashion. The foundation of this scaling relation lies in the d-band model initially proposed by Hammer and Nørskov [67] to explain the noblest properties of gold among the transition metals, which is now a wellestablished and widely recognized quantitative theory for catalysis after years of continuous research and development [68]. In the d-band theory, the chemisorption abilities of transition metal surfaces can be well described by the energy distribution of the d-band of the corresponding metal surfaces, which is mostly quantified using the average energy of the bandÐnamely, the d-band center. The adsorption of similar species on these surfaces therefore tends to correlate when the species’ adsorption energies rely only on the adsorbate valence and metallic d-band properties. Given the ubiquity of chemical bond formation between transition metal sites and adsorbates in heterogeneous catalysis, such a relation has been found to hold across a broad range of materials.  \n\nIn a foundational work, Abild-Pedersen et al. [69] found that the adsorption energies of hydrogen-containing molecules, $\\mathsf{A H}_{x},$ correlated linearly with the adsorption energy of atom A $\\overset{\\cdot}{\\boldsymbol{A}}=\\overset{\\cdot}{\\boldsymbol{C}}$ , N, O, and S). The mean absolute error (MAE) was reported to be only $0.13\\ \\mathrm{eV}$ when such linear relations were applied to describe the adsorption strengths of hydrogenated species over a range of pure metals. The successful prediction of the adsorption energies of hydrogenated species based on their atomic counterparts simplifies the estimation of the reaction energies of dehydrogenation and hydrogenation reactions, and can also be established in other more sophisticated reactions. For example, Chowdhury et al. [70] investigated the adsorption energies of surface species involved in the decarboxylation and decarbonylation of propionic acid over eight flat monometallic transition-metal surfaces (the (111) surfaces of Ni, Pt, Pd, Ru, Rh, Re, Cu, and $\\mathsf{A g}$ ). They found that multivariate linear scaling relations with a combination of descriptors (i.e., the adsorption energies of ${\\mathrm{CHCHCO}}^{*}$ , $\\mathsf{O H}^{*}$ , and $C^{*}$ , where \\* refers to the adsorbed species) yielded exceptionally accurate results, with a MAE of $0.12\\ \\mathrm{eV}$ , which could not be outperformed by any other nonlinear models. It is only when the training dataset is incomplete (i.e., contains a random subset of adsorption energies) that kernel-based nonlinear ML models start to become superior. Although this comparison accentuates the effectiveness of linear scaling relations in rationalizing a complete and large dataset, it also points out the inadequacy of linear models in predicting adsorption energies from a limited dataset.  \n\nWhile scaling relations are generally an effective and efficient way to largely reduce the reaction intermediate space to a few descriptors, several challenges remain when applying scaling relations in high-throughput catalyst screening. First, scaling relations usually only apply to similar adsorbates that bind through the same atom, with accuracies limited to around $0.1\\mathrm{-}0.2\\ \\mathrm{eV}$ . Second, stemming from the d-band theory, scaling relations work quite well for pure and alloyed transition metals; however, although a variety of scaling relations have been successfully established for inorganic compounds such as oxides, some of these apply only to limited systems with specificities in either composition or crystal structure [71,72]. Third, for complex reactions involving large organic molecules (e.g., alkanes containing more than three carbon atoms), the possibilities of single descriptors or descriptor pairs start to explode, interfering with the determination of a good catalyst, as the as-constructed activity maps are highly dependent on the chosen descriptor(s). For example, Wang et al. [73] showcased the importance of descriptor engineering with a selective propane dehydrogenation reaction to propylene. They found that the adoption of both ${\\mathrm{CH}}_{3}{\\mathrm{CHCH}}_{2}^{*}$ and $\\mathrm{CH}_{3}\\mathrm{CH}_{2}\\mathrm{CH}^{*}$ bindings as descriptors not only resulted in an overall MAE lower than $0.09\\mathrm{eV}$ for all scaling relations but also enabled the greatest differentiation of elemental metals. Nevertheless, the use of such an approach to determine descriptors often requires the input of external knowledge (e.g., $\\mathrm{CH}_{3}\\mathrm{CHCH}_{2}^{*}$ as the selectivity-determining species in the above showcased reaction). Developing strategies that do not rely on significant domain input or human intuition is therefore highly desirable.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.1.2. Improving scaling relations through ML  \n\nGiven the challenges outlined above, numerous efforts have been devoted to improving scaling relations. In this regard, Mamun et al. [74] proposed a Bayesian framework to extend the single descriptor linear scaling relation to a multi-descriptor linear regression model. Bayesian information criteria (BIC) were adopted as the model evidence to select the best model, providing a statistical rationalization of the descriptor selection regarding how many and which descriptors should be employed to yield the best bias-variance trade-off (Fig. 2(a)). In an attempt to further improve the prediction accuracy, the researchers also leveraged Gaussian process regression (GPR) to predict the residual of the selected model (i.e., residual learning; Fig. 2(b)). When applied to the (111) or (100) facet of 2035 binary alloy materials in their $\\mathsf{A}_{1}$ , $\\mathtt{L1}_{0}$ , and $\\mathbf{L}1_{2}$ Strukturbericht designation and six typical hydrogen-containing adsorbates $\\mathrm{^{CH^{*}}}$ , $\\mathrm{CH}_{2}^{*}$ , ${\\mathrm{CH}}_{3}{}^{*}$ , $\\boldsymbol{\\mathrm{OH}^{*}}$ , $\\mathsf{N H}^{*}$ , and $\\mathrm{SH^{*}}.$ , the as-devised framework demonstrated an impressive performance, with a test MAE of $0.1\\mathrm{eV}$ , which is very comparable with standard DFT error. This is a promising example of how ML can improve model fidelity and yield more accurate adsorption energy predictions than conventional linear scaling relations.  \n\nSimilarly, García-Muelas and López [75] reported the application of a statistical principle component analysis (PCA) and principle component regression (PCR) model to the DFT-computed adsorption strengths of 71 $\\mathsf{C}_{1}\\mathsf{-C}_{2}$ species on 12 close-packed metal surfaces (Cu, Ag, Au, Ni, Pd, Pt, Rh, Ir, Ru, Os, Zn, and Cd). As a common method for dimension reduction in unsupervised learning, PCA revealed that the majority of the thermochemistry of a given metal can be sufficiently estimated with two principal components (PCs) constructed from the formation energies of three predictors $(0^{*},0\\mathrm{H}^{*}$ , and ${\\mathrm{CCHOH}}^{*}$ ). One component presents the affinity of a metal to form covalent bonds with an intermediate, while the other describes the ionicity of the metal–adsorbate bond (Figs. 2(c) and (d)). The inclusion of the second component was found to be the key in extending the adsorbate thermochemistry predictions on transition metals to beyond conventional d-band theory, especially for adsorbates or metals with almost-filled valence shells or d-bands. A later PCR further confirmed this finding, exhibiting an MAE of $0.12\\mathrm{eV}$ on the validation set. This model was also applied to single-atom and near-surface alloy systems. With a minimum of DFT energy evaluations (around 1800), a full set of 31 000 formation energies were predicted with high accuracy $\\mathrm{(MAE=0.19~eV}.$ ). The high predictive power of statistical learning based on PCA/PCR was thereby demonstrated.  \n\n![](images/1186e024790259ee878a732474f4444e7d2478c86e07e0b30dca8c85e9bc3156.jpg)  \nFig. 2. ML models applied to improve upon scaling relations. (a) BIC plotted against the number of parameters (# of descriptors) used for $\\mathsf{N H}^{*}$ for a synthetic dataset containing 100 data points. The red line connects the minimum of each descriptor (the BIC envelope), while the blue star indicates the best model (with the lowest BIC value). (b) Parity plot showing residual learning using scaling relation model-predicted chemisorption energies of $\\mathsf{N H}^{*}$ $\\cdot\\Delta E_{\\mathrm{GP}})$ plotted against the DFT-computed chemisorption energies $(\\Delta E_{\\mathrm{DFT}})$ for the testing set. The uncertainty in the prediction is shown with the color bar on the right. RMSE: root-mean-square error. (c) Descriptors $(t_{i1},t_{i2})$ from PCA for metals. (d) Descriptors $(w_{1j},w_{2j})$ from PCA for adsorbates. The color scale in part (d) measures the robustness of each species being a predictor; those marked in brown are more suitable predictors and those marked in yellow are the least suitable. $i_{j}.$ : a dimensionless value quantifying the relative contribution of specie $-j$ -related descriptors to prediction error. (a, b) Reproduced from Ref. [74] with permission; (c, d) reproduced from Ref. [75] with permission.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.1.3. Estimating activation energies through ML  \n\nThe theoretical justification of estimating the activity of a solid catalyst through its adsorption energies relies on the existence of the Brønsted–Evans–Polanyi (BEP) relation, which states that the activation energy of an elementary step is positively correlated with its reaction energy [76]. There are cases, however, in which the linear BEP relations fail to capture the catalytic trend [77– 79]. Thus, it remains more desirable yet challenging to directly predict activation energies and assess the influence brought by other parameters besides reaction energy. Based on an open-access database, CatApp [80], which contains a set of DFT-calculated reaction energies and activation energies for a large number of elementary steps on single-crystal metal surfaces, including those with low symmetry such as stepped (211) surfaces, Takahashi and Miyazato [81] attempted to implement ML algorithms in conventional BEP relations in order to improve the accuracy in predicting activation energies. In addition to reaction energies, other features describing the catalyst, surface plane, reactants, and product were considered in nonlinear models such as random forest and support vector regression, resulting in better accuracy than linear models.  \n\nSimilarly, Artrith et al. [82] demonstrated an MAE of $0.20\\ \\mathrm{eV}$ (lower than an MAE of $0.35\\mathrm{eV}$ through BEP approximation) when predicting the TS energies of various C–C and C–O scission steps involved in ethanol reforming, using a set of ab initio (e.g., reaction energies) and non-ab initio (e.g., electronegativity and nearest– neighbor distance of chemical species) features in the ML model. The TS energies predicted in this model were further adopted as features in a second model based on a smaller experimental database, enabling the direct prediction of ethanol reforming activity/ selectivity without the need to know detailed reaction mechanisms or establish theoretical activity/selectivity volcano maps. These works provide methods for the rapid estimation of activation energy, although their transferability to catalysts beyond transition metals/alloys and to reactions beyond thermochemical reactions requires further demonstration.  \n\nIn sum, this subsection focused on improvements upon the traditional linear scaling relations that have been extensively relied on in conventional catalyst screening. One obvious advantage of the approaches discussed above lies in their physical rationality, as the theoretical foundation of linear scaling relations is fairly solid. However, these approaches all utilize features related to adsorption energies, which require DFT relaxations and are expensive to obtain. Furthermore, the adsorption energy is already an overall reflection of many geometric and electronic structural factors, whose contributions are challenging to understand and disentangle from a fundamental perspective. Therefore, it is still desirable to incorporate features that are formulated directly from the material electronic structure for adsorption energy prediction, which is discussed in the next subsection.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 2.2. Features based on calculated electronic structure properties  \n\nAside from the adsorption energies of some basic species, the ab initio electronic structure properties can also be calculated and employed as informative features for the ML-enabled estimation of adsorption energies. In this section, we discuss works that leverage electronic structure features, which not only present stronger potential for generalization but could also lead to physical understandings of specific heterogeneous catalytic processes.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 2.2.1. Formulated electronic structure properties  \n\nThe incorporation of domain knowledge, such as the d-band theory, can help researchers identify and formulate suitable electronic structure properties as feature inputs. Along this line, the Ma et al. [83] and Li et al. [84] evaluated several characteristics of the d-band distribution and the local Pauling electronegativity, which reflects the delocalized sp-states, as features in neural network (NN) models to predict ${\\mathsf{C O}}^{*}$ binding energies on (100)- and (111)-terminated multi-metallic alloys for $C O_{2}\\mathrm{RR}$ catalyst screening (Fig. 3(a)). The root-mean-square errors (RMSEs) for the predictions were approximately $0.1{-}0.2\\ \\mathrm{eV}$ , depending on the surface models. Similarly, with a target space holding various C–, N–, and O–containing adsorbates over different facets ((100), (111), and (211) of 11 transition metals with an face-centered cubic (fcc) bulk structure, including Co, Rh, Ir, Ni, Pd, Pt, Ru, Os, Cu, Ag, and Au), Praveen and Comas-Vives [85] devised a single ML model capable of predicting the adsorption strengths of multiple adsorbates simultaneously. With features related to the properties of the active sites, the elements involved in direct bonding, and electronic structure properties obtained from DFT calculations of free adsorbates and clean metal surfaces, the researchers trained an extreme gradient boosting (XGBoost) regressor that remained effective for adsorption energy prediction, with MAEs for the training and testing sets of 0.074 and $0.174\\ \\mathrm{eV}$ respectively.  \n\nA more important aspect of leveraging electronic features in ML-based adsorption energy prediction is to assist in the identification of the most influential features. Understanding why these features are important can prevent researchers from taking MLbased analyses at face value and allow for the identification of the principle factors determining surface catalytic chemistry, as well as potential ways to tailor better catalysts. The study by Praveen and Comas-Vives [85] mentioned above suggests that the most important features are electronic properties, primarily from the adsorbate and then from the metal, according to their feature importance analysis. Aside from feature importance ranking, a Bayesian learning approach (called Bayeschem) has been proposed to bridge the complexity of electronic descriptors [86]. Built upon the well-established d-band theory and a Newns– Anderson-type Hamiltonian for capturing the essential physics of chemisorption processes, a model optimized with pristine transition-metal data demonstrated impressive prediction accuracies $(\\sim0.1\\mathrm{-}0.2\\ \\mathrm{eV})$ and uncertainty quantifications for adsorbates such as $0^{*}$ and ${\\mathsf{O H}}^{*}$ at a diverse range of atomically tailored metal sites. More importantly, insights into the orbital-wise nature of chemical bonding at adsorption sites with ${\\mathsf{d}}{\\mathsf{\\Omega}}$ -state characteristics ranging from bulk-like semi-elliptic bands to free-atom-like discrete energy levels can be naturally drawn from the model.  \n\nBeyond pure metallic systems, ML methods have also been found to be efficient in describing the reactivity of metal compound catalysts. For example, Göltl et al. [87] adopted an ML genetic algorithm (GA) to analyze the correlation between various DFT-calculated electronic structure properties and ${\\mathsf{C O}}^{*}/{\\mathsf{N O}}^{*}$ adsorption strengths on transition metal sites (Cu, Ni, Co, and Fe) in zeolites (SSZ-13 and mordenite). Through this analysis, the position of the s orbital, the number of valence electrons of the active site, and the highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap of the adsorbate were found to be the most important electronic descriptors. Moreover, this work pointed out the importance of capturing site reconstruction in adsorption prediction. Similarly, molecular-orbital-based analysis was performed to quantify the interactions between a variety of small molecules and the surfaces of group 13 metal oxides [88]. The HOMO energies of the adsorbates and the surface energies of the oxide surfaces were identified as two major factors governing the solid–adsorbate interactions in such systems.  \n\nThe application of ML-based predictive models has also been extended to the screening of single-atom catalysts (SACs)  \n\n![](images/5b766a2c1424c28d6b095dff5e3df60dc2d4dec4c379625282ff1a5109c1dd37.jpg)  \nFig. 3. ML models with features manually crafted from electronic structures. (a) Normalized sensitivity coefficient obtained by analyzing the network response to perturbations of input features. (b) Example of sure independence screening and sparsifying operator adsorption energy prediction for C at a hexagonal close packed (hcp)-s site of an IrRu alloy using a data-driven descriptor. The tabulated primary features are calculated as averages over the three metal atoms (two Ir atoms and one Ru atom) making up the IrRu hcp-s site. The shown fitting coefficients are specific for C. The definition of variables can be found in Ref. [93]. Part (a) reproduced from Ref. [83] with permission; Part (b) reproduced from Ref. [93] with permission.  \n\n[89–91]. In this regard, Chen et al. [92] constructed a comprehensive dataset comprising 1060 atomically dispersed metal/nonmetal co-doped graphene systems as model carbon-supported SACs for ${\\mathsf{C O}}_{2}{\\mathsf{R R}},$ as well as an ML model based on XGBoost and simple features, revealing that the Pauling electronegativity and covalent radius of central metal atoms are more important features than the metal d-electron number. These understandings obtained for zeolites, oxides, or SACs are generally quite different from those gained from transition metals, highlighting the great opportunities to leverage ML to disclose unique catalytic chemistry beyond transition metals.  \n\nIn addition to the identification of the main factors affecting the interactions between adsorbates and surfaces, ML models exhibit the capability to construct new descriptors from explicit expressions of these influential factors. For example, Andersen et al. [93] proposed so-called ‘‘data-drivenº descriptors, whose predictive power was shown to extend over a wide range of adsorbates, multi-metallic transition metal surfaces, and facets. Identified using the recently developed compressed sensing method sure independence screening and sparsifying operator (SISSO), the descriptors are expressed as nonlinear functions of the intrinsic properties of the clean catalyst surface, including the coordination numbers and d-band moments (Fig. 3(b)). The good agreement between DFT-calculated and SISSO-predicted adsorption strengths demonstrates the effectiveness of new descriptors over scaling relations, as well as the possibility of extending them to broader material spaces.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 2.2.2. Raw electronic structure properties  \n\nWhile the aforementioned works adopt statistical features computed from electronic structure properties such as the d-band center or width, it is also possible to construct frameworks that directly digest raw electronic structural data such as the density of states (DOS). For example, Fung et al. [94] leveraged the DOS of catalytic surfaces for adsorption prediction, using the same dataset reported by Mamun et al. [74]. Unlike the previous work by Mamun et al. [74], Fung et al. [94] additionally computed the DOS of the surfaces. A convolutional neural network (CNN) model, which has been widely utilized in image processing and characterization, was adopted to automatically extract information from the raw DOS data without the need for external knowledge (Fig. 4(a)), yielding a low test MAE on the order of $0.1\\ \\mathrm{eV}.$ In addition, with the incorporation of domain knowledge, the as-devised model (referred to as ‘‘DOSnetº) supplied physically meaningful guidance through occlusion sensitivity analyses, by which the energetic responses to perturbations on electronic structures could be well estimated. This CNN-aided framework can thus potentially accelerate the discovery of new catalysts by enabling the exploration of an electronic structure space without adsorption energy calculations. As only a single calculation is required for each catalytic surface, DOSnet will exhibit even greater potential in computational savings and high-throughput screening when investigating surfaces containing a large quantity of unique adsorption sites (e.g., highentropy alloy (HEA) surfaces).  \n\nIn an attempt to obtain more interpretable features and descriptors, further engineering of DOS can be performed. For example, an automated framework was proposed to obtain accurate and interpretable descriptors of chemical activity for metal alloys and oxides using unsupervised ML (Fig. 4(b)) [95]. PCA was first adopted to identify a lower dimension basis of the DOS matrix, which consisted of PC descriptors. Models leveraging different featuresÐnamely, the traditional electronic descriptors, the full DOS, and $10~\\mathsf{P C}$ descriptors with top scoresÐwere compared for $C^{*}$ , $0^{*}$ , $\\mathsf{N}^{*}$ , and $\\mathsf{H}^{*}$ adsorption energy predictions on layered alloys; the PC-based models exhibited the most accurate results, with RMSEs smaller than those of the other two models by a factor of about two. In addition to prediction accuracies, this model is endowed with physical interpretability via the signal reconstruction of electronic-structure patterns captured by PC descriptors; thus, it provides suggestions on potential design motifs for future catalysts and establishes a link between the material’s geometric and catalytic properties.  \n\nThe importance and indispensable role of electronic structurerelated features in adsorption prediction is clearly demonstrated by the works discussed above. In addition to providing great predictive power, these features make nontrivial contributions to the model interpretability, through which fundamental understandings of the most influential electronic structural factors can be acquired and consequent objective catalyst design can be further enabled. However, the computational burden is a major concern in these approaches, as obtaining ab initio features can be expensive, especially in large systems. Realizing accurate adsorption prediction with only non-ab initio features is more appealing, in this sense. Such approaches are discussed in the following section.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3. ML with non-ab initio features  \n\nThe central role of electronic structures in determining adsorbate–surface interactions makes it natural to include related features for adsorption energy predictions. However, acquiring these features often requires ab initio calculations, especially for unexplored new materials that cannot be found in existing databases. The resulting increase of the computational cost is obviously undesirable, especially given the aim for high-throughput screening in a material space with unlimited possibilities of crystallographic orientations, surface compositions, and binding sites (e.g., HEAs and high-entropy metal compounds). Therefore, there has been a strong tendency to realize adsorption predictions using only lowcost features that do not require new ab initio calculations. For example, Toyao et al. [96] were the first to adopt 12 readily available elemental properties (EPs; e.g., surface energy, melting point, and group in the periodic table) as features in ML models for predicting the adsorption energies of $\\mathrm{CH}_{4}$ -related species $\\mathrm{^CH_{3}^{*}}$ , ${\\mathsf{C H}}_{2}^{*}$ , $\\mathrm{CH^{*}}$ , $C^{*}$ , and $\\mathsf{H}^{*}$ ) on copper $(\\mathsf{C u})$ -based alloys, realizing decent accuracy with MAEs $<0.3\\ \\mathrm{eV}$ . Once non-ab initio features are further rationally engineered to yield better model performance, we can anticipate a boost in new catalyst discovery, as time-consuming DFT calculations will no longer be heavily relied on.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3.1. Physically inspired non-ab initio features  \n\nThe implication of well-established theory in a predictive model is a general strategy when engineering simple, non-ab initio features with physical rationality. Aiming to predict $C0^{*}$ binding energies on alloys, Noh et al. [97] proposed a framework leveraging active learning (AL) and kernel ridge regression. More specifically, they adopted the d-band width calculated from linear muffin-tin orbital (LMTO) theory to account for the local coordination environment and the geometric mean of electronegativity to describe adsorbate renormalization. Demonstrated mostly on the (100) facets of subsurface alloy systems in an fcc bulk structure (Fig. 5(a)), the automated framework yields an impressive prediction MAE of only $0.05\\ \\mathrm{eV}$ when only adopting LMTO-derived features, which instills confidence in applying this model to screen for ideal subsurface alloys to catalyze $C0_{2}\\tt R R$ (Fig. 5(b)).  \n\nLeveraging tree-based models, Esterhuizen et al. [98] proposed a generalized additive model (iGAM) to investigate perturbations brought by strain or the ligand effect (Figs. 5(c)–(e)). The chemisorption of species representative of both electron-rich ( $\\mathrm{\\Phi_{oH}*}$ and ${\\mathsf{C l}}^{*}$ ) and electron-poorer $\\cdot\\mathrm{~o}^{*}$ and $S^{*}$ ) adsorbates on the (111) facets of subsurface metal alloys were focused on. Aside from its superior predictive capabilities (in general, with training RMSEs $<0.032\\mathrm{eV}$ and testing $\\mathrm{RMSES}<0.065\\mathrm{eV}.$ ), the iGAM model can provide further information, as it forces the model fit through construction to be a linear combination of different functions, where each function is only dependent on one feature of interest. In this case, the chemisorption strength was found to be impacted by three crucial site-related features: the strain in the surface layer, the number of d-electrons in the ligand metal, and the size of the ligand atom.  \n\n![](images/a9c66733a3b044f5d900c1edeaae4c5e36acbd544c83470cff50420e25d2238a.jpg)  \nFig. 4. ML models with features automatically formulated from DOS. (a) General schematic of the DOSnet model. The site-projected DOS of a surface atom serves as the input (light blue), which goes through a series of convolutional layers (green), followed by fully connected layers (red), and a final output layer. For additional atoms, the same convolutional layers are used with shared weights before being merged with the fully connected layers. Conv: convolutional and Fc: fully connected. (b) Workflow for automating electronic-structure descriptor identification using PCA. PCA identifies a lower dimensional basis (i.e., the PCs) of a DOS matrix to yield PC score descriptors. The electronic-structure effects captured in each descriptor can be analyzed and interpreted by reconstructing the DOS from the descriptors. Part (a) reproduced from Ref. [94] with permission; part (b) reproduced from Ref. [95] with permission.  \n\nOther than the manually selected features, new features can be constructed through ML. For example, the SISSO method was found to be effective in assembling initial features whose values are readily available in existing databases into new combinations, thereby either enlarging the feature space for chemisorption prediction on different metal alloys [99] or deriving more accurate descriptors for Pt-based oxygen reduction reaction (ORR) catalysts [100]. Insights on the critical physical concepts that control the chemisorption process on metal surfaces can also be further extracted.  \n\n![](images/036164d3bbef1b5f1e8bab772d388b059e8f6d1c7dc15a405e2c09b3702ff70d.jpg)  \nFig. 5. ML models built with non-ab initio features targeted at simple facets. (a) Three subsurface alloy models (i) $\\mathbf{\\boldsymbol{X}}@\\mathbf{\\boldsymbol{M}}$ (ii) $\\mathbf{M}{-}\\mathbf{X}@\\mathbf{M}$ , and (iii) $\\mathrm{\\bfM}_{3}\\mathrm{\\bfX}@\\mathrm{\\bfM}$ , where the blue and black balls denote M and X metals, respectively. (b) The performance of various ML models with different descriptors: without an ab initio d-band center and with a $\\mathsf{d}$ -band center. (c) The functions that make-up iGAM models to predict the target property, $y$ are ensembles of decision trees. (d) An elbow plot for a $k$ -medoids clustering analysis combined with silhouette coefficient analysis is used to select the optimal number of clusters. (e) The nine features considered are positively and negatively correlated to various degrees, based on the Pearson correlation coefficient. The definition of variables can be found in Refs. [97,98]. Parts (a, b) reproduced from Ref. [97] with permission; Parts (c–e) reproduced from Ref. [98] with permission.  \n\nIn the above work, the features were mostly formulated using known theories or domain knowledge. However, an inverse approach can be used based on previous theoretical models. For example, based on a unified empirical model [101] that correlates adsorption strength with a few electronic structure parameters including the d-band center, the number of p electrons, and the matrix coupling element between the adsorbate and the metal states, Montemore et al. [102] first predicted these parameters using ML and then derived the adsorption energies of a broad range of species (C, N, O, OH, H, S, K, and F) on flat metal and alloy surfaces with the predicted parameters as inputs to the empirical model, achieving an MAE of $0.29\\ \\mathrm{eV}.$ . Given the large ranges of the adsorbates and surfaces in this study, this model can be deemed to be general and reusable. Nevertheless, through a comparison between the two approaches, we note that these physically inspired models may present the dilemma of lower model accuracy or less generalizability, and such a balance often depends on how well the established theory works with the target chemical space.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 3.2. Enhanced representation of surfaces and molecules  \n\nThe works described above mostly focus on a single or a few adsorption sites, along with simple adsorbates. This might be sufficient for describing the activities of simple flat facets such as (111) and (100), which exhibit relatively high symmetry. However, as has been well established in many catalytic reactions, steppedlike surfaces are much more reactive and make major contributions to the overall activities [103,104]. Modeling catalytic reactions on these surfaces presents greater challenges, due to the broken surface symmetry and the resulting increase in surface heterogeneity. To accommodate various possible binding sites, traditional screening typically relies on the introduction of geometric descriptors [105,106] or the establishment of multiple site-specific activity maps [107,108]. On the other hand, emerging catalytic applications such as biomass [109,110] and plastic valorization [111,112] often require the description of interactions between large molecules and catalytic surfaces. Explicitly obtaining either the site-specific structure-activity relationships or the surface adsorption/reaction energetics involving large molecules adds up to a heavy computational burden. In this regard, ML is extremely suitable for overcoming this hurdle, once the enhanced representation of complex surfaces, molecules, or catalytic systems under more realistic conditions is implemented.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 3.2.1. Enhanced representation of complex surfaces  \n\nAs mentioned above, a prediction on stepped alloy surfaces serves as an example of a scenario in which the increased structural diversity of the catalytic surfaces must be considered. This scenario can be rather simple if the host metal remains unchanged, such as when predicting $\\mathsf{H}^{*}$ adsorption on stepped silver $(\\mathsf{A g})$ alloys. An ML model yielded an MAE as low as $0.014\\mathrm{eV}$ while only using non-ab initio features relative to the dopant atoms, without deliberate consideration of local geometric variations [113]. However, ML cannot work well with appropriate surface representation if the alloy composition is more variable. Saxena et al. [114] compared several ML models in predicting $C^{*}$ and $0^{*}$ binding energies on the (211) surfaces of $\\mathsf{A}_{3}\\mathsf{B}$ alloys with some common non-ab initio feature inputs, obtaining RMSEs of $0.31{-}0.38\\ \\mathrm{eV}$ depending on the surface termination and the adsorbate. However, the vast number of site possibilities on a (211) surface were not considered, leading to a prediction accuracy that was incomparable with those of the aforementioned models on simpler surfaces. Taking a step further, our group focused on the (211) surfaces of binary $\\mathbf{L}1_{2}$ -type alloys across 37 common metal and metalloid elements with sitespecific binding configurations, generating a rich library of site motifs and yielding a comprehensive dataset containing about 2000 adsorption energies [115]. With the inclusion of only low cost, non-ab initio features encoding both the electronic structure properties and the coordinate-based geometric information of the surface sites, our models demonstrated satisfactory prediction accuracies, with test MAEs of 0.14 and $\\phantom{-}0.18\\mathrm{eV}$ for $C^{*}$ and $0^{*}$ binding, respectively. Furthermore, interpretable physical insights could be extracted from the feature importance distributions and Kullback–Leibler divergence analysis, showing the most probable structural and compositional characteristics of an ideal alloy catalyst for a specific reaction. The proposed models were further validated through DFT calculations and microkinetics modeling, with low-temperature methanol synthesis as a test reaction and a $\\mathrm{Cu}_{3}\\mathrm{Pd}$ alloy as a promising candidate identified by ML. In principle, due to its simplicity, the use of this model as a rapid screening tool prior to any detailed theoretical or experimental investigations is readily applicable to other reactions that are well described by $C^{*}$ and $0^{*}$ binding strengths. Other coordinate-based geometric representations, such as the generalized coordination number, have also been found to be effective in improving the prediction accuracy of ML models based on non-ab initio electronic structure features [116–118].  \n\nThe above examples tend to focus on a system consisting of only one or two elements; however, it is also beneficial to realize effective adsorption evaluation across a broader spectrum of elements. Thus, prediction on HEA surfaces serves as another example of a scenario in which compositional heterogeneity plays an interesting role. For example, Batchelor et al. [119] explored HEAs composed of five elements (Ir, Pd, Pt, Rh, and Ru) as candidate catalysts for ORR, in which the adsorption strengths of $0^{*}$ and $\\boldsymbol{\\mathrm{OH^{*}}}$ were targeted. The researchers constructed a very simple linear model that leveraged parameterizations based solely on the nearest–neighbor compositions to the binding sites. Three and five types of atomic zones in (111)-type HEAs were classified for ${\\mathsf{O H}}^{*}$ and $0^{*}$ adsorption, respectively (Fig. 6(a)). By adopting the adsorption energies on a random subset of available binding sites as the training set, the model exhibited impressive prediction accuracy, with RMSEs of 0.063 and $0.076{\\mathrm{~eV}}$ for $\\boldsymbol{\\mathrm{OH^{*}}}$ and $0^{*}$ adsorption, respectively, on other possible sites. More importantly, the as-developed model was then applied to optimize the HEA composition, offering a design platform for the discovery of novel alloys by promoting sites with exceptional catalytic activities (Fig. 6(b)).  \n\nA similar concept of site representation was adopted for screening bimetallic or HEA catalysts for either ${\\mathsf{C O}}_{2}$ hydrogenation to methanol [120] or the hydrogen evolution reaction (HER) [121]. The use of distance-based descriptors as an alternative to the nearest–neighbor information was found to contribute to the accurate prediction of $\\mathsf{H}^{*}$ adsorption on multi-metallic surfaces [122]. Nevertheless, the prediction of multi-metallic or HEA catalysts is mainly limited to (111) or (100) model surfaces at present. Accurate predictive models capable of encompassing both structural and compositional variations (e.g., HEA catalysts with non-ideal flat surfaces) are still lacking and require future development.  \n\nThe coordinate-based representation method further enables the AL-based fully automated theoretical framework to guide the DFT calculations of desirable energetic descriptors, as demonstrated by Tran and Ulissi [123]. More specifically, these researchers proposed a fingerprinting method to represent the adsorption site numerically (Fig. 6(c)). This method describes each element type coordinated with the adsorbates using a vector of four numbers: the atomic number; the Pauling electronegativity; the number of atoms of the element coordinated with the adsorbate, as determined by the Voronoi tessellation; and the median adsorption energy between the adsorbate and the pure element $(\\Delta E)$ . Having enumerated all possible binding sites over 1499 different intermetallic combinations across 31 elements, the researchers were able to identify 54 candidates with surfaces having nearoptimal $C0^{*}$ binding for electrochemical ${\\mathsf{C O}}_{2}{\\mathsf{R R}}$ and 102 candidates with ideal $\\mathsf{H}^{*}$ binding for the HER (Figs. 6(d) and (e)). The prediction MAEs were reported to be 0.29 and $0.24~\\mathrm{eV}$ for ${\\mathsf{C O}}^{*}$ and $\\mathsf{H}^{*}$ , respectively. This proposed framework is a successful example of combining flexibility, automation, and ML guidance to enable holistic analyses across numerous adsorption sites, surfaces, and material spaces and the consequent acceleration of theoretical discovery. It should be noted that, although the AL framework basically adopted non-ab initio features (except for $\\Delta E$ , additional DFT calculations were iteratively performed to verify the prediction and generate new DFT data for model retraining.  \n\nCompared with coordinate-based methods, graph-based deep learning (DL) methods have advantages in high-level feature representations [124]. With the same dataset as that used in Ref. [123], Back et al. [125] demonstrated lower MAEs of $0.15\\ \\mathrm{eV}$ with CNNs that were built on top of the graph representation and used only initial structures as inputs. Even more impressive prediction accuracies (i.e., test MAEs of 0.116 and $0.085\\mathrm{eV}$ for ${\\mathsf{C O}}^{*}$ and $\\mathsf{H}^{*}$ binding, respectively) were achieved with an ensemble of crystal graph CNNs (CGCNNs) and a labeling method representing the binding site atoms of the unrelaxed bare surface geometry [126]. The site labeling method (Fig. 7(a)) enables the complete removal of DFTbased surface relaxation by generating unrelaxed surface structures from relaxed bulk structures that are computationally cheaper or even readily available in open-sourced databases such as Ref. [127]. In principle, such a universal method can be applied to any DL-based adsorption prediction model without modification. These works demonstrate that the combination of a novel site description method and advanced ML algorithms provides a viable solution for the high-throughput prediction of complex catalytic surfaces, significantly extending the searching space from singlecrystal model catalysts to more practical ones.  \n\n![](images/5fd739c26b178c28a59db7df66967edfe82e8d921b079b11afe830ba5b1ab2d5.jpg)  \nFig. 6. ML models with a coordination-based method for representing complex surfaces. (a) Parameterization of the surface configurations using nearest–neighbors for $^*\\mathrm{OH}$ on-top and $^*0$ fcc hollow-site binding. (b) Activities (As) of reengineered compositions of the HEA IrPdPtRhRu; distribution of adsorption energies for $\\mathrm{Ir}_{20}\\mathrm{Pd}_{20}\\mathrm{Pt}_{20}\\mathrm{Rh}_{20}\\mathrm{Ru}_{20}$ $\\mathrm{Ir_{10.2}P d_{32.0}P t_{9.3}R h_{19.6}R u_{28.9}}$ , $\\mathrm{Pd}_{81.7}\\mathrm{Ru}_{18.3}$ and $\\mathrm{Ir}_{17.5}\\mathrm{Pt}_{82.5}$ (global maximum activity). $\\Delta E_{\\mathrm{pred}}$ : predicted adsorption energy. (c) Fingerprint of the coordination site, where the adsorption sites are reduced to numerical representationsÐnamely, fingerprintsÐand these fingerprints are used as model features. Z: the atomic number of the element; $\\chi$ : the Pauling electronegativity of the element, CN: the number of atoms of the element coordinated with the adsorbate, $\\Delta E$ : the median adsorption energy between the adsorbate and the pure element. (d) A t-distributed stochastic neighbor embedding visualization of all the adsorption sites simulated with DFT, where the adsorption energy values are in units of eV. $\\Delta E_{\\mathrm{H}}$ : H adsorption energy. (e) Normalized distribution of low-coverage $\\mathsf{H}^{*}$ adsorption values calculated by the DFT workflow; dashed lines indicate the $0.1\\ \\mathrm{eV}$ range around the optimal $\\boldsymbol{\\mathrm{H^{*}}}$ adsorption value of $-0.27\\ \\mathrm{eV}$ . Parts (a, b) reproduced from Ref. [119] with permission; Parts (d, e) reproduced from Ref. [123] with permission.  \n\nWhen combined with different ML methods or modules, graph-based representations also provide a promising strategy for increasing the interpretability of features extracted from electronic structure properties such as DOS. Wang et al. [128] directly infused the famous d-band theory into DL, obtaining a framework capable of suppling physical insights from learned data by design. This so-called theory-infused NN (TinNet) approach contains two sequential components: a convolutional-NN-based regression module that encodes the atomic and electronic structural information from the raw data; and a theory module that takes outputs from the regression module and predicts the adsorption properties of a metal site (Fig. 7(b)). The effectiveness of TinNet was demonstrated with representative simple adsorbates such as $\\mathrm{OH^{*}}$ and $0^{*}$ . With an MAE of $0.118\\mathrm{eV}$ , the prediction performance was among the best in comparison with existing models or algorithms such as GPR [74], Bayeschem [86], DOSnet [94], and CGCNN. In addition to having a prediction performance on par with purely datadriven ML methods, TinNet allows for the decomposition of d-contributed adsorption energy into Pauli repulsion and orbital hybridization, a detailed analysis of which sheds light on potential paths to tailor novel motifs with desired catalytic properties.  \n\n![](images/9864dfbe3ebfeab62fa11adcb18bbaec9e202dedd0eb2d7ec8baf33f9239841e.jpg)  \nFig. 7. ML models with a graph-based method to represent complex surfaces. (a) Creation of the labeled-site representation for training and its application to real systems. For training, a covalent radius is used to identify the interaction between the surface and the adsorbate in the relaxed geometry; then, the binding-site atoms in the unrelaxed surface geometry are substituted with their pseudoelement counterpart. For applications, surface atoms of the unrelaxed surface geometry are identified by alpha shape, and top, bridge, and hollow sites are identified using graph theory. Specifically, $d$ refers to the distance between atom i and $j$ whereas $d_{\\mathrm{cov1}}$ and $d_{\\mathrm{cov}2}$ refer to the covalent radii of atom i and $j$ , respectively. (b) Schematic illustration of the TinNet. Information flows from the graphical representation of a given adsorbate–substrate system to the adsorption energy, the projected DOS onto the adsorbate frontier orbital(s), and the d-band momen s of the adsorption site. Circles and squares in the regression module represent neurons and feature maps, respectively. The definition of variables can be found in Ref. [126,128]. Part (a) reproduced from Ref. [126] with permission; Part (b) reproduced from Ref. [128] with permission.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# 3.2.2. Enhanced representation of complex molecules  \n\nSince the interaction between surfaces and molecules plays a central role in heterogeneous catalysis, the numbers of both possible adsorption configurations and possible reaction pathways increase drastically when the target reactions involve larger molecules. Thus, the explicit calculation of all adsorption energies can be very resource- and time-consuming. As has been wellestablished and demonstrated in general molecular ML for organic synthesis or drug discovery, many molecular representation methods have been directly implemented in predictive ML models for catalysis [129–133]. For example, Li et al. [134] compared different combinations of methods, including EP [96] and Coulomb matrix [129] representations for surfaces, as well as extended connectivity fingerprint (ECFP) [130], spectral London Axilrod–Teller–Muto (SLATM) [131], and bags-of-bonds (BOB) [132] representations for adsorbates, and found that the EP $^+$ SLATM combination yielded the lowest MAE of approximately $0.18\\mathrm{eV}$ for 68 adsorbates on four low-index metal facets $\\mathsf{\\Gamma}(\\mathbf{u}(111)$ , Pt(111), $\\mathsf{P d}(111)$ , and ${\\mathrm{Ru}}(0001))$ . The researchers further extended the simple surfaces to broader transition metal/alloy surfaces and made a change in various representation methods [123,126,133] by replacing the atomic number with the elemental group and periods, thereby achieving an MAE of about $0.05\\mathrm{eV}$ for $\\mathsf{H}^{*}$ binding prediction and MAEs of about $0.1\\ \\mathrm{eV}$ for other strong binding adsorbates $(\\mathsf C^{*},\\mathsf N^{*},0^{*}$ , and $S^{*}$ ) [135]. Using molecular fingerprints based on simplified molecular input line entry system (SMILES) notation (Fig. 8(a)) [136,137], Chowdhury et al. [137] constructed multiple filter-based NN models to extrapolate from a $\\mathsf{C}_{4}$ dataset to a $\\mathsf C_{2}/\\mathsf C_{3}$ dataset on Pt(111), where $C_{2^{-}}C_{4}$ refer to species made up of two to four carbon atoms. The SMILES-based representation was demonstrated to lower the extrapolation MAE by approximately $20\\%$ compared with coordinate-based ones. Similar feature engineering has also helped to predict and compare the adsorption energies of ring and chain species on metal surfaces [138]. Both works demonstrate the effectiveness of SMILES notation in encoding complex molecular structures in predictive ML models.  \n\nSimilar to surface representation, graph-based methods enable enhanced and efficient molecular representation due to their conveniently readable and extendable data structure. For example, various graph-based methods such as graph NN (GNN) have been employed to represent up to $315\\ C_{1}/\\mathsf C_{2}$ surface intermediates and TSs on Rh(111) for syngas-to-ethanol conversion [139]. The best RMSE and MAE for adsorption energy prediction were found to be 0.19 and $0.15\\ \\mathrm{~eV}$ , respectively, and the error for activation energy prediction was lower than those of conventional BEP relations. Very recently, the superiority of GNN in representing complex molecules was substantiated by Pablo-García et al. [140], who demonstrated the construction of a well-balanced chemically diverse dataset and a new GNN architecture called graph-based adsorption on a metal energy (GAME)–neural network (Net) (Fig. 8(b)). Their dataset is very comprehensive, containing closed-shell $\\mathsf{C}_{1-4}$ molecules with functional groups including N, O, S, and $C_{6-10}$ aromatic rings (3315 entries). The optimal adsorption configuration and position of all the molecules were explored through DFT calculations after extensive sampling. Only the lowest energy configurations were included in the dataset. A molecule adsorbed on a closed-pack metal surface was further represented as an integral graph to train GAME–Net, consisting of fully connected layers, convolutional layers, and a pooling layer. The strong predictive power of GAME–Net was demonstrated by a low MAE of $0.18\\ \\mathrm{eV}$ on the test set and six orders of magnitude less time consumed compared with DFT. The model could even be directly adopted to predict larger plastic and biomass molecules with up to 30 heteroatoms, which were not presented in the initial dataset for training, yielding an MAE of $0.016\\mathrm{eV}$ per atom that showed the model’s promising accuracy. Although this model still has a few limitations, such as the requirement of highly symmetric surfaces (i.e., only close-packed pure metal is considered) and neglect of lateral effects, the simplicity and generality of this model make it a useful tool for the fast screening of catalytic materials for unique applications that cannot be easily simulated by traditional methods such as DFT.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 3.2.3. Enhanced representation of catalytic systems under more realistic conditions  \n\nWhile the above works focus on model catalytic systems such as single-crystal surfaces with low coverage of adsorbates, efforts to leverage ML in order to better describe and predict more practical catalytic systems also benefit from enhanced representation. For example, the importance of accurate surface representation is further demonstrated by the prediction of practical catalytic materials beyond single-crystal model surfaces, such as nanoparticles (NPs) and small clusters. With a focus on describing the catalytic NO decomposition performance of RhAu alloy NPs (Fig. 9(a)), Jinnouchi and Asahi [141] proposed a universal ML scheme to investigate reaction activities based on local atomic configurations. To evaluate the structural similarities, the researchers adopted a socalled smooth overlap atomic position (SOAP) similarity kernel, which consists of overlap integrals between three-dimensional (3D) atomic distributions within a cutoff radius from different surface sites. The success of this model demonstrates the fact that the adsorbate binding is rather local and the prediction accuracy can be systematically improved by increasing the number of DFT data to cover all possible local structures. Similar conclusions were drawn when a research group combined SOAP descriptors with ML models to predict $\\mathsf{H}^{*}$ adsorption on a variety of $\\mathsf{M o S}_{2}$ and Cu–Au nanoclusters [142].  \n\nAdvanced local structure representation can then be assembled using various global structure generation methods into ML pipelines for predicting structurally diverse practical catalytic systems. Chen et al. [143] devised an NN model to identify the active sites on gold (Au) NPs and dealloyed $\\mathsf{A u}_{3}\\mathsf{F e}$ NPs for $C O_{2}\\mathrm{RR}$ to CO. The researchers focused on a performance indicator called the $a$ -value, which can be expressed as $a\\ =\\ \\Delta E_{\\mathrm{CO}}\\ -\\ 1.4423\\Delta E_{\\mathrm{HOCO}},$ where $\\Delta E_{\\mathrm C0}$ and $\\Delta E_{\\mathrm{HOCO}}$ represent the adsorption energy of CO and the surface carboxyl $(\\mathrm{HOCO^{*}})$ , respectively. Both energies can be obtained by means of quantum mechanics (QM). Using a developed force field for reactive systems called ReaxFF [144], the researchers first constructed a $10\\mathrm{nm}$ Au NP, which contained more than 10 000 surfaces sites. Then, features based on the interatomic distances between the Au atoms were leveraged to describe the extremely irregular and disordered Au surfaces, with RMSEs of approximately 0.05 and $0.06\\ \\mathrm{eV}$ for the $\\Delta E_{\\mathsf{C O}}$ and $\\Delta E_{\\mathrm{HOCO}}$ predictions, respectively. The catalytic activity of the whole surface was further mapped to illustrate the desirable site geometries of the NPs (Fig. 9(b)) and guide the design of high-performance electrocatalysts for ${\\mathrm{CO}}_{2}{\\mathrm{RR}}.$ A similar ML-QM-ReaxFF framework was applied to study ${\\mathsf{C O}}_{2}{\\mathsf{R R}}$ on Au NPs while considering solvation effects and roughened Cu surfaces, demonstrating the good versatility of this strategy [145,146].  \n\nDifferent site representation and initial structure generation methods can be considered to further modify the workflow. By leveraging the fingerprint labeling method [126], Gu et al. [147] integrated the force field, DFT, ML, and kinetic Monte Carlo in an end-to-end multiscale simulation framework to elucidate the alkaline HER kinetics of jagged platinum $\\left(\\mathrm{Pt}\\right)$ nanowires. This framework not only achieved a high prediction accuracy for $\\mathsf{H}^{*}$ adsorption energies, with an MA $\\mathrm{~E~<~}0.05\\mathrm{~\\eV}$ , but also offered insights into the autobifunctional alkaline HER mechanism. It also suggested structure motifs of highly active Pt catalysts for alkaline HER. Similarly focusing on HER catalysts but with an amorphous system, Zhang et al. [148] adopted a GA optimization method implemented in the universal structure predictor evolutionary Xtallography code to obtain over 600 amorphous surface structures of ${\\mathrm{Ni}}_{2}{\\mathrm{P}}.$ . Non-ab initio features relying only on the local chemical environment were utilized to predict the frozen adsorption energies of $\\boldsymbol{\\mathrm{H}}^{*}$ , with an $\\mathrm{RMSE}<0.1$ eV. However, we note that the $\\mathsf{H}^{*}$ adsorption energy consists of a frozen term and a relaxation term. The prediction of the latter, which accounts for the energy change upon site and surface deformation, still requires ab initio features, in accordance with prior discussions on the zeolite system [87].  \n\n![](images/3d3b4da66008320927e8e121ea62d796dcdce78aacf52aa89c3ff5c0d70a69c3.jpg)  \nFig. 8. ML models with enhanced representation of complex molecules. (a) SMILES-based molecular fingerprint for the surface species $\\mathrm{CH}_{3}\\mathrm{CHCOO}$ . Here, ${\\sf C}_{0}$ denotes a saturated carbon. $\\mathsf C_{1},\\mathsf C_{2}$ , and ${{C}_{3}}$ denote carbon atoms with one, two, and three free valences, respectively. Similarly, $0_{0}$ is a saturated oxygen, whereas $0_{1}$ is an oxygen atom with one free valence. (b) Schematic illustration of the workflow for GAME–Net. (b–i)–(b–iv) Starting from the DFT functional group (FG) dataset containing small adsorbates, the sample adsorption systems are transformed to their corresponding graph representation to train the proposed GNN architecture. BM: big molecules. The final purpose is to use GAME–Net to estimate the adsorption energy of big molecules $C_{<23}$ on metal surfaces present in the big molecule dataset, thus avoiding the use of computationally expensive DFT calculations. Here $E_{\\{i,$ GNN} refers to the GNN-predicted proxy energy of a molecule i adsorbed on a surface. Part (a) reproduced from Ref. [137] with permission; Part (b) reproduced from Ref. [140] with permission.  \n\nAnother aspect of practical catalytic complexity stems from lateral effects such as adsorbate–adsorbate interactions and solvation. Explicitly accounting for these effects in ab initio simulations, however, is often extremely computationally demanding. For example, to identify the most optimal binding configuration on a surface at high coverages normally requires the enumeration of all possible binding configurations and then acquiring the energy of each configuration using DFT calculations. The exploration of such a large space of atomistic configurations could take orders of magnitude more time than a single calculation at a low coverage. To address this challenge, the Greeley group developed an ML-based surrogate model, named the adsorbate chemical environment-based–graph convolution neural network (ACE–GCN), to replace expensive DFT calculations in determining the atomistic configurations of high-coverage catalytic surfaces (Fig. 9(c)) [149]. This model was based on the SurfGraph algorithm, which allows for the conversion of atomistic configurations to undirected graph representations [150]. The graph representations were further split into subgraphs for featurization and model training. This splitting into subgraphs is the key in explicitly accounting for the local environment of the adsorbate so that subtle atomistic interplay such as adsorbate–adsorbate interaction can be accurately captured. Illustrated by $\\boldsymbol{\\mathrm{OH^{*}}}$ adsorption on a stepped Pt(221) surface, the ACE–GCN not only enabled the use of a mixed training dataset (high-coverage data obtained on both Pt(221) and Pt(100) surfaces) to improve the model’s reliability in ranking the most likely adsorption configurations but also successfully identified energetically favorable and unfavorable high-coverage (corresponding to $1/2$ monolayer) ${\\mathsf{O H}}^{*}$ adsorption configurations on $\\mathsf{P t}(221)$ with $96\\%$ fewer DFT relaxations (Fig. 9(d)).  \n\n![](images/c88d1da07961a2bd1b4e70ab1b9169452ddeb33cdec26ac8103a134e69073400.jpg)  \nFig. 9. ML models with an enhanced representation of catalytic systems under more realistic conditions. (a) Atomic distributions and binding energies $(E_{\\mathrm{{b}}})$ of N, O, and NO with the surface sites on a $\\begin{array}{r}{\\mathbb{R}\\mathrm{h}_{1-x}\\mathrm{Au}_{x}\\mathrm{NP}}\\end{array}$ with $x=0.19$ and $d=5{\\mathrm{nm}}$ (x refers to the atomic fraction of Au in the NP and d refers to the diameter of the NP). (b) $a$ -value mapping and catalytic activity visualization for a dealloyed Au surface. Each single site is given an $a$ -value based on NN prediction. These $a$ -values are then mapped back on the particle to visualize the catalytic activity of the whole surface. As indicated in the color bar, the red sites are inactive, while the blue sites are active. ‘‘Surface defectº and ‘‘Step under 111º sites are highlighted as two representative highly active sites, corresponding to surface $\\mathsf{A u}(111)$ atoms with one or two missing atoms around the center site and undercoordinated $\\mathsf{A u}(111)$ atoms near to steps, respectively. (c) An ACE–GCN algorithm used to encode and train high-coverage adsorbate configurations. (d) Screening highcoverage $\\mathsf{O H}^{*}$ configurations on $\\mathsf{P t}(221)$ : (left) scatter plots for the average ${\\mathsf{O H}}^{*}$ binding energies of unrelaxed configurations, as predicted by ACE–GCN, with respect to DFTrelaxed energies of the corresponding structures. Among all configurations (N refers to the number of configurations), 213 out of 5855 configurations remain undissociated after DFT relaxation. A representative area of the chemical space relevant for unstable and stable configurations is depicted on the scatter plots, marked as ‘‘(i)º and ‘‘(ii)º; (right) representative stable and unstable atomic configurations from the (i) and (ii) regions depicted in the scatter plots. Part (a) reproduced from Ref. [141] with permission; Part (b) reproduced from Ref. [143] with permission; Parts (c, d) reproduced from Ref. [149] with permission.  \n\nThe rigorous description of catalytic systems embracing both the complexities originating from nanostructured catalysts and realistic reaction conditions is rarely reported, except for a very recent study by Cao and Mueller [151], who adopted a machinelearned cluster expansion method to map ORR activity on Pt–Ni alloy nanoparticles. Nevertheless, it is definitely a promising direction to accelerate the in situ theoretical description of practical catalytic systems using ML and advanced representation methods.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# 4. ML-guided experimental catalyst discovery  \n\nAn accurate estimation of the adsorbate binding strength helps lay the foundation for efficient high-throughput catalyst screening and catalyst design, the effectiveness of whichÐof courseÐstill requires experimental validation. In this section, we present a few examples of the successful development of highly active catalysts under ML guidance to further demonstrate the significance of ML methods in accelerating experimental catalyst discovery.  \n\nFor example, Zhong et al. [152] adopted the AL framework discussed above [123] to investigate CO adsorption strengths on alloy surfaces. Based on insights obtained from a scaling-derived volcano map, which indicated that the optimal CO binding for $C0_{2}\\tt R R$ should be around 0.67 eV [107], the researchers examined a wide range of alloys to identify the ideal catalysts that exhibit adsorption strengths around that value. As illustrated by its tdistributed stochastic neighbor embedding (t-SNE) diagram [153], the Cu–Al alloy presents multiple sites and surface orientations with near-optimal CO binding, demonstrating its great potential for efficient and selective $C O_{2}\\mathrm{RR}$ catalysis. This was later confirmed with a synthesized $\\mathsf{C u\\mathrm{-}A l}$ catalyst, which efficiently reduces ${\\mathsf{C O}}_{2}$ to ethylene with the highest reported Faradaic efficiency of over $80\\%$ . Similarly, ML has been verified to be effective in designing alloy catalysts for nitrogen-related chemistries such as ammonia oxidation. For example, adopting the aforementioned TinNet framework [128], Pillai et al. [154] explored the immense design space of ternary Pt alloy nanostructures (Figs. 10(a) and (b)). With a training dataset of ab initio data, concurrent predictions of site reactivity, surface stability, and catalyst synthesizability descriptors can be realized. An AL workflow showed $\\mathrm{Pt}_{3}\\mathrm{Ru}-\\mathrm{M}$ $\\mathrm{T}\\mathrm{M}=\\mathrm{Fe}$ , Co, or Ni) alloys to be promising iridium (Ir)-free candidates, and their catalytic potential was confirmed by the corresponding experimentally synthesized nanocubes, which exhibited higher activities than state-of-the-art Pt catalysts and its bimetallic alloy counterparts (Figs. 10(c) and (d)). The great potential of ML in guiding and accelerating the experimental exploration of catalysts in a vast chemical space such as that of a multi-metallic system was thereby established.  \n\nIn addition to its use in high-throughput screening, ML’s attractive capability to supply valuable physical insights for experimental catalyst design has been established. Along this line, Zhai et al. [155] devised an NN model correlating the ORR activity of perovskite oxides to nine ionic descriptors including the ionic Lewis acid strength (ISA) on A- and B-sites, which was later confirmed to be the most influential feature according to the feature importance ranking. Tuning the ISAs of perovskites is therefore suggested as a viable approach for optimizing perovskites’ ORR activity. Experimental characterization has revealed that decreased A-site and increased B-site ISAs can considerably improve the surface exchange kinetics of perovskite oxides. Based on this premise, four perovskite oxides were synthesized, whose superior catalytic performance substantiated the effectiveness of ML-derived catalyst design principles. Similarly, machine-learned insights through Bayeschem [86] were found to be effective in discovering novel catalysts for the electrochemical nitrate reduction reaction $(\\mathsf{N O}_{3}\\mathsf{R R})$ that break the adsorption-energy scaling limitations posed by conventional catalysts [156]. More specifically, Bayeschem was used to determine that the non-scaling behavior originated from site-specific Pauli repulsion interactions of the metal ${\\mathsf{d}}$ -states with the adsorbate frontier orbitals and could be realized on (100)-type sites, where $^*\\mathrm{N}$ and ${^*{\\mathsf{N O}}_{3}}$ exhibited different orbital overlap degrees with subsurface metal atoms. As a result, tuning the subsurface elements in ordered B2 intermetallics became a rational strategy to optimize the ${\\tt N O}_{3}{\\tt R R}$ performance. This strategy was further verified by synthesizing and testing monodisperse ordered B2 CuPd nanocubes with (100)-like surface orientations, which displayed a high Faradaic efficiency of $92.5\\%$ for ${\\tt N O}_{3}{\\tt R R}$ to ammonia and improved ammonia yield rates more than Cu or Pd. This success in translating machine-learned insights into rational experimental catalyst design principles sheds light on ML-guided new catalyst discovery aside from direct computational high-throughput screening.  \n\n![](images/83b1bde2d0a9a3ec579a107c2974f1c05ebcd6caf34839185837d5a0121a3b37.jpg)  \nFig. 10. ML-guided experimental catalyst discovery. (a) An AL workflow for accelerating catalytic materials discovery. (b) The ammonia oxidation reaction activity map at 0.3 V vs a reversible hydrogen electrode (RHE) with solid markers showing promising ternary Pt alloy electrocatalysts predicted from the workflow. $\\Delta E_{*\\ensuremath{\\mathrm{N}_{\\mathrm{b}}}}$ : nitrogen adsorption at bridge site, $\\Delta E_{*\\ensuremath{\\mathrm{N}_{\\mathrm{h}}}}$ : nitrogen adsorption at hollow site. The activity is quantified using turnover frequency of $\\mathsf{N}_{2}$ $\\left\\langle\\mathrm{TOF}_{\\mathrm{N}_{2}}\\right\\rangle$ . (c) High-angle annular dark-field scanning transmission election microscope image and the corresponding energy dispersive spectroscopic elemental mapping of Pt, Ru, and Co. (d) Electrocatalytic performance testing of Pt, $\\mathrm{Pt}_{3}\\mathrm{Ir}$ , $\\mathrm{Pt}_{3}\\mathrm{R}\\mathbf{u}$ , and $\\mathrm{Pt}_{3}\\mathrm{Ru}_{1/2}\\mathrm{Co}_{1/2}$ nanocubes via cyclic voltammetry with a rotating speed of $900\\mathrm{r}{\\cdot}\\mathrm{min}^{-1}$ in Ar-saturated $\\mathrm{1.0\\mol{\\cdot}L^{-1}\\ K O H+0.1\\ m o l{\\cdot}L^{-1}\\ N H_{3}}$ under ambient conditions. The measured current density was normalized to the mass of Pt (i.e. A $\\mathrm{g}_{\\mathrm{Pt}}^{-1}$ ) in Pt-based electrocatalysts. Reproduced from Ref. [154] with permission.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# 5. Summary and outlook  \n\nThe search for efficient catalysts for the next-generation chemical industry will continue to be a research hotspot for decades to come. As a rising field that is still in its infancy, ML-aided surface reactivity evaluation has already demonstrated its huge potential to enable a paradigm shift in high-throughput catalyst screening. Considering the progress that has already been achieved, we point out two major propellants (Fig. 11) in the development of ML models for adsorption energy prediction:  \n\n(1) The construction and curation of datasets. Rather than generating a completely new set of training data points from scratch, many works leverage datasets from previous papers or public data repositories to devise novel models for binding strength prediction. For example, the datasets reported in Refs. [74,84,93,123] have been widely adopted in other works, which present fresh perspectives by tackling these published data from a different angle. Public data repositories such as CatApp [80] and Catalysis-Hub.org [157] maintained by the SUNCAT center at the Stanford Linear Accelerator Center (SLAC) have also been frequently used. The reuse of the same dataset for the demonstration of different ML models enables objective performance comparison, where the establishment of appropriate benchmarks encourages the development of more accurate and robust models. With the aim of constructing extensive datasets for heterogeneous catalysis, Fundamental AI Research at Meta AI (originally Facebook AI) and Carnegie Mellon University’s Department of Chemical Engineering launched the Open Catalyst (OC) project in 2020. Its original dataset, OC2020, consists of 1.28 million DFT relaxations ${\\sim}260$ million single-point evaluations), spanning across 55 elements, 82 adsorbates, and unary/binary/ternary inorganic materials [158]. The release of such a large-scale dataset is undoubtedly beneficial in attracting broader interests and gathering the research community together to address open challenges in developing generalizable ML models for catalysis discovery [159].  \n\n(2) The implementation and improvement of matter representation. As demonstrated in Section 3.2, ML model accuracy is largely dependent on an appropriate representation of surfaces and molecules, whose role becomes even more predominant when modeling the catalytic activities of structurally or compositionally complex systems such as nanoparticles and HEAs. Given the ubiquity of site diversity that results from likely catalyst reconstruction under realistic conditions, it is therefore crucial to rationalize and optimize matter representation. DL-based approaches have recently exhibited great potential in sophisticated matter representation [124–126,140,150,160]. Their representations are more expressive than hand-crafted ones and are expected to be compatible with large-scale datasets, as revealed by a comparative study on the OC2020 dataset [159].  \n\nDespite the impressive achievements that have been made so far, accessing adsorption strengths directly through ML still presents the following nontrivial challenges (Fig. 11):  \n\n(1) Generalizability. As many previous works have mostly focused on systems based on specific chemistries and material compositions (e.g., predominantly metal alloys) with limited demonstration of their generalizability, it remains a ‘‘holy grailº task in this field to develop a universal model that can operate across the abundant space of materials and molecular adsorbates. Similar to AI/ML model optimization in other fields, a model’s predictive capability generally improves as the amount of data increases. Unfortunately, this improvement is not as simple and scalable. As revealed by the OC team [158] using current baseline models, the scaling between the dataset size and model performance is more difficult for catalysis datasets than for datasets of organic small molecules and inorganic materials. Innovations in ML models are therefore greatly needed to overcome this hurdle.  \n\n![](images/f5c3fabaa8e81930576896d9994a8a8a6de4300ebcaa640d0ce4a20c63b57778.jpg)  \nFig. 11. Two major propellants and five future challenges in developing ML-assisted approaches for adsorption energy prediction.  \n\n(2) Efficiency. Given access to large-scale datasets, the next task is to enhance model efficiency. This usually relies on the utilization of low-cost features (e.g., using only the graphic information of initial atomistic structures, as in OC2020 tasks [158]) and the improvement of prediction accuracy. As the ultimate goal is to identify materials with desirable properties within an almost unlimited candidate space, the adoption of computationally costly information is not preferable. On the other hand, the prediction accuracy of ML models remains essential, since inadequate results eventually lead to a waste of time and resources, which diminishes the goal of accelerated material screening. Unfortunately, reducing the cost and improving the accuracy often result in a dilemma, as demonstrated by the comparison between models using ab initio and non-ab initio features. It is therefore vital to carefully and delicately balance these two demands.  \n\n(3) Complexity. Despite the desirable efforts that have been made to predict adsorption energies for species involved in complicated reaction networks or on complex catalytic surfaces, training datasets are mostly obtained on idealized surfaces with simple assumptions such as a high vacuum, low adsorbate coverage, and single surface species. These approximations, however, can be too crude and may deviate substantially from the actual reaction conditions, especially for the electrocatalytic reactions used in a wide swath of future clean-energy-related applications. In addition to some common complexities introduced by, for example, species co-adsorption or adsorbate–adsorbate interaction [107,161], these electrocatalytic reactions embrace additional complications stemming from the inherent electrochemical interfaces, which can lead to profound solvation and charge separation effects [162–164]. The prediction results of ML models will not be as useful and impactful if these complexities cannot be well captured, despite the potentially satisfactory prediction accuracies such models might be able to achieve [149].  \n\n(4) Reliability. The energetic data in most current databases are obtained through generalized gradient approximation (GGA)-level DFT computation. Consequently, the accuracies of ML models built upon these data are also restricted to such a level. More sophisticated methods such as meta-GGA or hybrid functionals are capable of supplying more reliable results, but they usually induce an enormous computation burden at the same time, making it impractical to construct datasets with these methods. In addition, some systemsÐsuch as those with spin polarization or strong electron correlation (e.g., magnetic 3D metal oxides)Ðrequire the delicate tuning of DFT parameters to yield physically sensible results, presenting another hurdle in the formulation of large-scale datasets. For example, the OC2020 dataset simply considers no spin polarization for all systems [158]. This inconsistency in computational methods introduces additional uncertainties when adopting databases from different sources. The uncertainty quantification, in this case, remains necessary. Developing reliable methods to accelerate high-precision DFT simulations or to provide accurate DFT surrogates is another valuable direction, in which ML has already demonstrated its great potential [165–169]. A discussion on this aspect, however, lies beyond the scope of this review.  \n\n(5) Interpretability. Improving a model’s interpretability helps to better exploit its predictive power. Other than merely obtaining a few promising candidates, it is also of paramount significance to acquire fresh understandings and new principles to aid in the design of better catalysts through objective optimization. Most previous works have adopted pure data-driven approaches, which yield impressively low prediction errors but provide limited interpretability. Post-training analysis is therefore a common yet effective way to extract more physical insights from such models. Alternatively, it is even more ideal to intentionally weave mechanistic understandings into the ML framework, in which case the physical rationality of the model can be automatically ensured and the model’s interpretability will come naturally. More importantly, merging interpretability into ML models can help to partially address the reliability concern, as experts can try to rationalize the derived interpretations and compare them with known physics [55].  \n\nWe note that the above challenges can be highly entangled, and that there might not be a single ideal ML model capable of overcoming all obstacles simultaneously. Alternatively, we envision a hierarchical workflow to leverage multiple ML models with unique superiorities in different aspects, while the overall mission of highthroughput screening could be decomposed into a sequential task consisting of steps with different requirements for accuracy, complexity, and scalability. For example, pure data-driven ML models can first be employed to rapidly navigate through the vast material space with simple assumptions and compromised prediction accuracies. Given appropriate uncertainty quantification, it would still be possible to locate the subspace enclosing possible promising candidates. Next, highly reliable prediction and knowledge extraction could be enabled by focusing on this specific subspace while utilizing ML models that accommodate smaller datasets, leverage more accurate computational methods, compile more realistic approximations, and exhibit greater interpretability. Finally, the obtained physical insights could be further applied to reexamine the entire material space in an attempt to search for potential missing candidates that align well with the extracted patterns. In sum, despite the many challenges presented by the application of ML for surface reactivity prediction and high-throughput catalyst screening, we believe that this remains an extremely promising field with great potential to improve computational science, accelerate materials design, and ultimately reshape the future chemical industry and energy landscape.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 22,
+        "chunk": "# Acknowledgment  \n\nThis work was supported by the National Natural Science Foundation of China (22109020 and 22109082).",
+        "category": " References"
+    },
+    {
+        "id": 23,
+        "chunk": "# Compliance with ethics guidelines  \n\nXinyan Liu and Hong-Jie Peng declare that they have no conflict of interest or financial conflicts to disclose.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# References  \n\n[1] Catlow CR, Davidson M, Hardacre C, Hutchings GJ. Catalysis making the world a better place. Philos Trans R Soc A Eng Sci 2016;374(2061):20150089.   \n[2] Schlögl R. Heterogeneous catalysis. Angew Chem Int Ed Engl 2015;54 (11):3465–520.   \n[3] Wang AQ, Li J, Zhang T. Heterogeneous single-atom catalysis. Nat Rev Chem 2018;2(6):65–81.   \n[4] Rostrup-Nielsen JR, Sehested J, Nørskov JK. Hydrogen and synthesis gas by steam- and ${\\mathsf{C O}}_{2}$ reforming. Adv Catal 2002;47:65–139.   \n[5] Wang QR, Guo JP, Chen P. Recent progress towards mild-condition ammonia synthesis. J Energy Chem 2019;36:25–36. [6] Vogt ETC, Weckhuysen BM. Fluid catalytic cracking: recent developments on the grand old lady of zeolite catalysis. Chem Soc Rev 2015;44(20):7342–70.   \n[7] Jiang X, Nie X, Guo X, Song C, Chen JGG. Recent advances in carbon dioxide hydrogenation to methanol via heterogeneous catalysis. 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Amorphous catalysis: machine learning driven high-throughput screening of superior active site for hydrogen evolution reaction. J Phys Chem C 2020;124(19):10483–94.   \n[149] Ghanekar PG, Deshpande S, Greeley J. Adsorbate chemical environmentbased machine learning framework for heterogeneous catalysis. Nat Commun 2022;13(1):5788.   \n[150] Deshpande S, Maxson T, Greeley J. Graph theory approach to determine configurations of multidentate and high coverage adsorbates for heterogeneous catalysis. npj Comput Mater 2020;6(1):79.   \n[151] Cao L, Mueller T. Catalytic activity maps for alloy nanoparticles. J Am Chem Soc 2023;145(13):7352–60.   \n[152] Zhong M, Tran K, Min Y, Wang C, Wang Z, Dinh CT, et al. Accelerated discovery of ${\\mathsf{C O}}_{2}$ electrocatalysts using active machine learning. Nature 2020;581(7807):178–83.   \n[153] Van der Maaten L. Accelerating t-SNE using tree-based algorithms. 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Open catalyst 2020 (OC20) dataset and community challenges. ACS Catal 2021;11 (10):6059–72.   \n[159] Kolluru A, Shuaibi M, Palizhati A, Shoghi N, Das A, Wood B, et al. Open challenges in developing generalizable large-scale machine-learning models for catalyst discovery. ACS Catal 2022;12(14):8572–81.   \n[160] Chen C, Ye WK, Zuo YX, Zheng C, Ong SP. Graph networks as a universal machine learning framework for molecules and crystals. Chem Mater 2019;31(9):3564–72.   \n[161] Yang N, Medford AJ, Liu X, Studt F, Bligaard T, Bent SF, et al. Intrinsic selectivity and structure sensitivity of rhodium catalysts for $C_{2+}$ oxygenate production. J Am Chem Soc 2016;138(11):3705–14.   \n[162] Sundararaman R, Vigil-Fowler D, Schwarz K. Improving the accuracy of atomistic simulations of the electrochemical interface. Chem Rev 2022;122 (12):10651–74.   \n[163] Liu X, Schlexer P, Xiao J, Ji Y, Wang L, Sandberg RB, et al. pH effects on the electrochemical reduction of $\\mathrm{CO}_{2}$ towards $C_{2}$ products on stepped copper. Nat Commun 2019;10(1):32.   \n[164] Peng HJ, Tang MT, Halldin Stenlid J, Liu $\\mathbf{\\boldsymbol{x}},$ Abild-Pedersen F. Trends in oxygenate/hydrocarbon selectivity for electrochemical $\\mathrm{CO}_{2}$ reduction to $C_{2}$ products. Nat Commun 2022;13(1):1399.   \n[165] Faber FA, Hutchison L, Huang B, Gilmer J, Schoenholz SS, Dahl GE, et al. Prediction errors of molecular machine learning models lower than hybrid DFT error. J Chem Theory Comput 2017;13(11):5255–64.   \n[166] Bogojeski M, Vogt-Maranto L, Tuckerman ME, Müller KR, Burke K. Quantum chemical accuracy from density functional approximations via machine learning. Nat Commun 2020;11(1):5223.   \n[167] Bisbo MK, Hammer B. Efficient global structure optimization with a machinelearned surrogate model. Phys Rev Lett 2020;124(8):086102.   \n[168] Behler J. First principles neural network potentials for reactive simulations of large molecular and condensed systems. Angew Chem Int Ed Engl 2017;56 (42):12828–40.   \n[169] Friederich P, Häse F, Proppe J, Aspuru-Guzik A. Machine-learned potentials for next-generation matter simulations. Nat Mater 2021;20(6):750–61.",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Prediction of coating thickness for polyelectrolyte multilayers via machine learning  \n\nVarvara Gribova1,2,5, Anastasiia Navalikhina4,5, Oleksandr Lysenko4, Cynthia Calligaro3, Eloïse Lebaudy1,2, Lucie Deiber3, Bernard Senger1,2, Philippe Lavalle $1,2,3\\&$ Nihal Engin Vrana3\\*  \n\nLayer-by-layer (LbL) deposition method of polyelectrolytes is a versatile way of developing functional nanoscale coatings. Even though the mechanisms of LbL film development are well-established, currently there are no predictive models that can link film components with their final properties. The current health crisis has shown the importance of accelerated development of biomedical solutions such as antiviral coatings, and the implementation of machine learning methodologies for coating development can enable achieving this. In this work, using literature data and newly generated experimental results, we first analyzed the relative impact of 23 coating parameters on the coating thickness. Next, a predictive model has been developed using aforementioned parameters and molecular descriptors of polymers from the DeepChem library. Model performance was limited because of insufficient number of data points in the training set, due to the scarce availability of data in the literature. Despite this limitation, we demonstrate, for the first time, utilization of machine learning for prediction of LbL coating properties. It can decrease the time necessary to obtain functional coating with desired properties, as well as decrease experimental costs and enable the fast first response to crisis situations (such as pandemics) where coatings can positively contribute. Besides coating thickness, which was selected as an output value in this study, machine learning approach can be potentially used to predict functional properties of multilayer coatings, e.g. biocompatibility, cell adhesive, antibacterial, antiviral or anti-inflammatory properties.  \n\nLayer-by-layer (LbL) coating is a method for surface modification based on the electrostatic interactions between two ­polyelectrolytes1,2. Such coating is developed thanks to successive deposition of polycations and polyanions onto the surface of a material, and by performing a rinsing step after each deposition. This method is very versatile as a large number of polyelectrolytes can be used, making it possible to adapt the coating for a particular application. Different methods can be used for the build-up of LbL coatings, such as dip-coating, spin-coating, and ­spraying3,4. The most used method and perhaps the easiest one is dip-coating, but it is also more timeconsuming compared to spin-coating for ­instance .  \n\nLbL coatings are used for multiple biomedical applications, in particular, because natural polyelectrolytes presenting good biocompatibility can be used for LbL film build-up. It is possible to develop antibacterial surfaces, smart healing materials, and coatings for tissue engineering. Moreover, LbL coatings can be used for loading drugs or other bioactive molecules, which allows their local ­delivery6–9. Non-biomedical LbL applications include construction of gas barrier ­films10, optical fiber ­sensing11, and many electrochemical ­systems12.  \n\nHowever, the empirical manner of polycation/polyanion selection is an impediment on rapid new coating development. First, the formation of the coatings can be very long, if many layers are required, and for thick films, the method can become fastidious. Secondly, the thickness of the different coatings is difficult to control, as it depends on different parameters such as temperature, pH, ionic strength, and ­others5.  \n\nMoreover, there remain difficulties in understanding how interactions between polymers occur, as they are mostly multifactorial. Thus, LbL coatings growth can be different (in most cases linear or exponential, at least up to a given number of layers deposited) depending on polymers’ properties and on diffusion between ­layers13. Experimentally, different methods are used to evaluate LbL film thickness: quartz crystal microbalance with dissipation monitoring (QCM-D) can be used to follow step-by-step polyelectrolyte deposition with high accuracy. Other methods such as atomic force microscopy (AFM), confocal microscopy or ellipsometry can also be ­used14,15. However, these different methods do not use the same approach of thickness determination, and for the same LbL film, the results obtained by different techniques can differ.  \n\n![](images/c65b9137596e1f83cdec1a7acc775395440dcb176eb8a9627cf476f849fd9721.jpg)  \nFigure 1.   Workflow for coating thickness prediction using supervised machine learning approach.  \n\nAs a result, and despite the progress made in the field, the data accumulated over the years do not provide predictive capacities on how a given couple of polymers will form an LbL film, which also decreases the rate of advance in the field. In this work, we hypothesize that using the current state-of-the-art data science techniques, we can determine how different parameters affect coating thickness and predict the thickness of the new coatings. To do so, we used historical and generated data for predictive model development using machine learning.  \n\nMachine learning is an approach which uses algorithms that improve upon training on large datasets and is able to find complex patterns, make predictions and decisions. In this work, we used two training datasets: one comprising the data extracted from literature (several thickness determination methods) and another containing experimental data produced in our laboratory (thickness determination by QCM-D).  \n\nIn the first part of the work, the most important parameters influencing coating buildup were determined. In the second part, a thickness predictive model was built using the training set, and its performance was evaluated. Finally, we validated the model on LbLs which were not in the training set, and were able to predict the coating thickness (Fig. 1). To our knowledge, this is the first time that machine learning approach has been used for LbL coating thickness prediction.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Results and discussion  \n\nData collection.  The first step of the work consisted in data collection from the literature, which represents the first dataset. It should be stated that currently in the literature no established database is available related to LbL coating thickness, and the available experimental data is relatively scarce compared to the number of LbL related articles. The second dataset was based on the QCM-D experiments done in the laboratory. For the data extracted from the literature, different ways of thickness calculation/estimation were used, such as AFM, ellipsometry, confocal microscopy. Coating thickness determined by these methods may differ, but due to the limited amount of the available data, we selected to include all the data regardless of the thickness measurement method. All the results extracted from the literature, as well as obtained in the laboratory, were entered in the tables describing different parameters (Table S1). Of note, all the multilayers used in the study were prepared by dip-coating or a similar technique (simple polymer solution deposition on the substrate followed by adsorption time and rinsing). Thus, the coating preparation method was not among the parameters influencing thickness.  \n\nInfluence of different construction parameters on coating thickness.  As a first step, distribution of the thickness values in the coatings made of different polymers was studied (Fig. 2). The results show that for polycations, the coatings made of poly(L-lysine) (PLL) have the greatest thickness median values with large interquartile range (IQR), which overlaps the thickness distribution of chitosan (CHI)-made coatings (Fig. 2A). In Fig. 2B, coatings having poly(L-glutamic acid) (PGA) have the greatest thickness median value with IQR overlapping with hyaluronic acid (HA)-containing coatings thickness distribution. The large thickness distribution of the LbL films containing the aforementioned polymers is probably due to the high frequency of their utilization and therefore to the wide variety of molecular weights (MW) that have been used.  \n\nNext, linear relationships between the coating thickness and different parameters were evaluated using the Pearson correlation, and non-linear relationships were analyzed with the predictive power score (PPS) method (Fig. 3). The PPS allows seeing non-symmetrical relationships between variables: features located on the $\\mathbf{x}$ -axis are independent variables (influencers), and features on the y-axis are dependent variables (influenced by $\\mathbf{x}$ -features).  \n\nThe results show that concentrations of polymers and the number of bilayers in the coating have a strong positive linear relationship with the resulting thickness (Fig. 3A), while polyanion molecular weight and buffer properties have some non-linear relationships with this property (Fig. 3B). The effect of concentration and the number of bilayers are intuitive, however, their relative importance in an overall tendency sense cannot be extracted from a single or few types of LbL films, which is the currently common practice. Similarly, the discrepancy between the relative importance of polyanion (PA) MW and polycation (PC) MW is also not evident.  \n\nOne of the most important features which have strong linear relationships with the coating thickness is the number of bilayers in the coating (Fig. 3).  \n\nAs stated above, this dependency is largely obvious, and therefore, the data had to be unified by this number. For this, we decided to calculate the thickness at eight bilayers for each coating in the literature-generated data using the growth function (Eq. 1).  \n\n![](images/8115581c2a8d6bcb00f5570dd814793e3e90a5eeb6b568b438b1fe223b57324a.jpg)  \nFigure 2.   Boxplots showing the distribution of the thickness values in the coatings made of different polymers. (A) Thickness depending on polycations. (B) Thickness depending on polyanions. COL: collagen, PEI: polyethylenimine, PLL: poly(L-lysine), PAH: poly(allylamine hydrochloride), CHI: chitosan, glyc-CHI: glycol-chitosan, PDADMA: poly(diallyldimethylammonium chloride), PAR: poly(L-arginine), PTEMC: poly(trimethylammonium ethyl methacrylate chloride), HA: hyaluronic acid, ALG: alginate, PGA: poly(Lglutamic acid), CSA: chondroitin sulfate, FUC: fucoidan, PSS: poly(styrene sulfonate), PCBS: poly[1-[4-(3- carboxy-4-hydroxyphenylazo)benzenesulfonamido]-1,2-ethanediyl, sodium salt, CARlambda: $\\lambda$ -carrageenan, CARkappa: κ-carrageenan, PSSMA: poly(4-styrenesulfonic acid-co-maleic acid), PAA: poly(acrylic acid), DEX: dextran, HEP: heparin.  \n\n![](images/040985755a993e86a1b238657f737469d2bc3a02d865f6754779a2f91bb78d4f.jpg)  \nFigure 3.   Pearson correlation (A) and Predictive Power Scores (PPS) (B) calculated for the final thickness of the coating and coating features. The first seven Pearson correlations are statistically significant $(p\\leq0.05)$ . Only features having $\\mathrm{PPS}>0.001$ with the target value are included. Full names of polymer features are provided in SI Table S3.  \n\n![](images/9a77ae42405d0dcec041e92186086b8a63e0a8732a6380f2979f840c82eaee81.jpg)  \nFigure 4.   Pearson correlation (A) and Predictive Power Scores (PPS) (B) calculated for the thickness of the 8-bilayered coating and coating features. The first three and the last Pearson correlations are statistically significant $(p\\leq0.05)$ . Only features having $\\mathrm{PPS}>0.001$ with the target value are included. Full names of polymer features are provided in SI Table S3.  \n\nTable 1.   Performance of the constructed models measured as root-mean-square error (RMSE, nm) for three data sets. QSPR: quantitative structure–property relationship, SVR: support vector regression.   \n\n\n<html><body><table><tr><td>RMSE (nm)</td><td>QSPR Bagging regressor</td><td>QSPR SVR</td><td>Bagging regressor</td></tr><tr><td>Training set</td><td>46.7</td><td>76</td><td>50.9</td></tr><tr><td>Test set</td><td>68.7</td><td>113.8</td><td>73.8</td></tr><tr><td>Validation set</td><td>74.7</td><td>123.1</td><td>226.6</td></tr></table></body></html>  \n\nThe growth function, describing changes in coating thickness $d$ with the number of layers, $N_{:}$ has three coefficients, $a_{0},a$ , and $b$ , which vary depending on the ­coatings16,17. In this function parameter, $b$ defines function curvature: for $b\\geq0.05$ , the growth is exponential, for $b<0.05$ , it is nearly linear.  \n\n$$\nd=a_{0}+a*e^{b N}\n$$  \n\nWe extracted data on the dynamics of each coating growth from the original research papers. Then we used these data to calculate coefficients of growth function. Having these coefficients, we defined the thickness of coatings having eight bilayers $(\\Nu=16)$ ). With this, we created a new target value, the thickness of the 8-bilayer coating, which was not dependent on the number of bilayers.  \n\nIn this configuration, the type of polyanion, its concentration and its molecular weight were found to positively influence the thickness of the coating, while the charge density of polyanion negatively correlated with the coating thickness (Fig. 4A). Three features (on the $\\mathbf{x}$ -axis) contributed to the coating thickness (on the y-axis) (Fig. 4B): type of polyanion, polyanion unit molecular weight, and resulting molecular weight. The reason why polyanion characteristics appear more important than those of polycation can be explained by pH values at which polyelectrolyte multilayers were built $\\mathrm{\\Phi_{\\mathrm{pH}}}$ values are close to the pKa of the acid groups).  \n\nCoating thickness predictions.  After the determination of the most influential parameters, the next step was the build-up of a predictive model. We constructed a Bagging Regressor ­model18 to make predictions about coating thickness using ten features from the original data set: presence of HA, presence of poly(styrene sulfonate) (PSS), resulting MW of the polycation and of the polyanion, unit MW of the polycation and of the polyanion, concentration of polycation and concentration of polyanion, the concentration of $\\mathrm{\\DeltaNaCl}$ , and charge density of polyanion. Two quantitative structure–property relationship (QSPR) regression models were constructed using the selected features, Bagging Regressor and support vector regression (SVR) (Table 1).  \n\nThese models have smaller root-mean-square error (RMSE) values for the validation set than the Bagging Regressor constructed using the original dataset features. This fact indicates their greater potential for generalization. The model performance was evaluated with RMSE values calculated for the training set, test set, and validation set. All the models were fivefold cross-validated. All metrics are mean values for scores from different folds from cross-validation.  \n\n![](images/3f1946252150454d75d803ce1c54dd32bfaa72161f28ade67d11eab0fa6bd94f.jpg)  \nFigure 5.   (A) Schematic presentation of the model building process. (B) Correlation between RDKit descriptors and thickness of the coating. Only descriptors with ${\\bf r}\\ge0.25$ are shown. All coefficients are statistically significant $(p\\leq0.05)$ .  \n\nHowever, we encountered a classical Machine Learning challenge: overfitting, when the model makes good predictions for the instances it was built on (training set), but fails to “generalize”, i.e. make good predictions for the unseen items (validation and test sets). Therefore, the large gap between training and test/validation error values is the major sign of overfitting. This is the case for the Bagging Regressor constructed on the original data set features. As we can see, this model generates a large RMSE value for the validation set, which is 4 times larger than the error for the training set. From here, we conclude that polymers as specific chemical entities are not good features by themselves, and generating numerical features that describe the chemical properties of polymers can improve the model performance.  \n\nTo get features of a molecule, firstly we had to get information about its structure, which is commonly represented in simplified molecular-input line-entry system (SMILES) format, available in the PubChem database. This information is further used to predict molecular features by deep learning pre-trained models available in the DeepChem library.  \n\nFor each polycation and polyanion, 123 molecular descriptors were generated, therefore each coating in the dataset was characterized by 246 molecular descriptors. Many molecular features have a moderate correlation with the thickness of the coating, so we assume that they can be used to predict this target value (Fig. 5). Mostly, molecular descriptors with high correlations with the coating thickness are related to polyanions, not polycations; this is in line with the observations in the previous section.  \n\nIn the next step, we combined features generated by DeepChem and numerical features of the polymers from the original data set. After that, we performed feature elimination with the recursive feature elimination (RFE) algorithm leaving ten features that will be used by the models. These features are MW of the polycation, MW of the polyanion, NaCl concentration, six polyanion RDKit descriptors (MinAbsEStateIndex, FpDensityMorgan3, BalabanJ, PEOE_VSA8, VSA_EState2, VSA_EState6), and one polycation descriptor Kappa1. The most significant molecular descriptors demonstrate the importance of the topological features of the polyanions (such as Balaban distance connectivity index (BalabanJ) and also polycations (Kappa1) in the formation of the supramolecular LbL assemblies in addition to the electrostatic interactions which are described by molecular operation environment (MOE) type electrotopological descriptors. Descriptors related to van der Walls forces and also partial charges underline the highly intricate nature of the LbL film formation at molecular level.  \n\n<html><body><table><tr><td>Film</td><td>Ground truth, thickness (nm)</td><td>Predicted thickness, QSPR RFE/Bagging</td><td>Predicted thickness, QSPR RFE/SVR</td><td> Predicted thickness, RFE/Bagging</td></tr><tr><td>PAR30/DEX40</td><td>51.30</td><td>68.55</td><td>43.86</td><td>308.61</td></tr><tr><td>CHI50/DEX5</td><td>42.70</td><td>62.02</td><td>91.45</td><td>265.33</td></tr><tr><td>CHI50/FUC</td><td>123.00</td><td>125.84</td><td>197.79</td><td>274.23</td></tr><tr><td>CHI50/CARiota</td><td>109.30</td><td>161.07</td><td>232.98</td><td>278.50</td></tr><tr><td>PAR30/CARiota_1</td><td>65.80</td><td>146.22</td><td>279.71</td><td>322.28</td></tr><tr><td>PAR30/PSS0.2</td><td>7.80</td><td>97.00</td><td>126.70</td><td>285.69</td></tr><tr><td>PAR30/PSS4</td><td>31.50</td><td>97.00</td><td>126.89</td><td>288.20</td></tr><tr><td>PAR30/DEX20</td><td>46.00</td><td>62.74</td><td>42.77</td><td>308.61</td></tr><tr><td>CHI30/HA108</td><td>162.80</td><td>308.23</td><td>285.14</td><td>335.13</td></tr><tr><td>CHI20/HA108</td><td>218.20</td><td>306.78</td><td>287.21</td><td>335.13</td></tr><tr><td>PAR30/CARiota_2</td><td>45.90</td><td>146.22</td><td>279.71</td><td>322.28</td></tr></table></body></html>  \n\n![](images/436fc8f04a22a5f82b41601b19aca9cbfaa60167343f84256ee30be344178b8f.jpg)  \nTable 2.   The thickness of the coatings predicted with three models and thickness determined experimentally (ground truth).   \nFigure 6.   (A) Real (ground truth) and predicted thickness of coatings in the validation data set. (B) Relative errors for predictions made with the best of constructed models (QSPR RFE/Bagging).  \n\nAs the last step, in order to further test the generalization capacity of the final model, we have tested polymers which were not in the training set that are described solely by molecular descriptors.  \n\nIn this configuration, we observed more inaccurate predictions (Table 2, Fig. 6). However, this could be expected, given the size of the training dataset. As we can see, the best results are obtained with the use of the QSPR RFE/Bagging regressor. It can predict the thickness of the coating better than two other models. We can also see that predictions of QSPR models are better than for the model RFE/Bagging constructed with original features, which predicts almost constant thickness values for all coatings $(302\\pm25~\\mathrm{nm})$ . Predictions of QSPR models are correlating, and there are four coatings for which both regressors failed to predict thickness correctly (relative error $>100\\%$ ): PAR30/PSS0.2, PAR30/CARiota_2, PAR30/PSS4, PAR30/CARiota_1 (Fig. 6B).  \n\nTwo other coatings, that have inaccurate predictions, contain CARiota polymer which was not in the dataset during training. The fact that the model fails to make predictions for the coatings which are made of unseen polymers confirms the assumption the generalization is not complete. It is interesting that despite this, there is one coating with CARiota for which relative error is small $(47\\%)$ , and the model was able to make an accurate prediction in this case.  \n\nBelow, we discuss some of the possible reasons that may have caused large errors in the predictions made by the best of the constructed models, QSPR RFE/Bagging. For the PAR30/PSS0.2 and PAR30/PSS4, a large error may be caused by the too low molecular weight of the PSS polyanion compared to the one that the model has seen in the training set. The smallest polyanion in the dataset used for training was DEX with $\\mathrm{MW}{=}7.2\\mathrm{kDa}$ , hereas in the validation set we have coatings where PSS has lower MW values (0.2 and $4\\mathrm{kDa}$ ). Moreover, in the training set, PSS MW was greater than in the validation set $(60-70\\mathrm{kDa})$ , so the combination of polyanion/MW of polyanion is new to the model. Because the model has made inaccurate predictions for the kind of polymers that it did not see during training, we assume that it can not generalize well and this is the reason for the prediction failures.  \n\nIn the end, we observe that the model makes acceptable predictions for the coatings made of combinations of polymers that were present in the data set (like CHI/FUC, CHI/HA, and PAR/DEX). However, it fails to do so for the unseen polymers tested, due to the lack of extensive training data. We believe that the model potentially can be improved by generating and using more data for training. More data points will cover more chemical parameters, and the dependencies between features and thickness will be more informative and will have more predicting power.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 3,
+        "chunk": "# Conclusions and perspectives  \n\nIn this work, we analyzed how different parameters such as polymer molecular weight, concentration, etc. affect LbL film thickness. After the determination of the most influential parameters, we used machine learning approach to verify if we can predict coating thickness from different parameters. We found that construction parameters alone were insufficient to build a robust model for thickness prediction because of the overfitting. To overcome this problem, we hypothetized that generating numerical features that describe the chemical properties of polymers can improve the model performance. Thus, we analysed the relationship between 123 molecular descriptors and the coating thickness, and found that molecular features had a moderate correlation with the thickness of the coating. Finally, we combined molecular descriptors and numerical features of the polymers from the original data set to build new models, and these models had better performance for the validation set than the model constructed using the original dataset features, which indicates their greater potential for generalization.  \n\nIn conclusion, the generalization capacities of an algorithmic model predicting coating thickness can be improved by delving into the determining properties of the polymers in the context of LbL film formation dynamics. Harnessing the available data science techniques in biomaterial design and development such as multifunctional coatings will decrease lead time, empirical experimental load and also establish relationships between structure and function, which are otherwise hard to guess or estimate. The ultimate goal is to be able to predict coating functionalities based on polymer structure and buildup conditions, to develop innovative coatings for different applications.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 4,
+        "chunk": "# Materials and methods  \n\nMaterials.  Alginate (ALG), $\\lambda$ -carrageenan (CARlambda), $\\upkappa$ -carrageenan (CARkappa), ι-carrageenan (CARiota), chitosan $\\mathrm{\\DeltaMw}=50$ and $100\\mathrm{kDa}$ ; CHI50 and CHI100), chondroitin sulfate (CSA), dextran $(\\mathrm{Mw}=5$ , 7.2, 20, 40 and $500~\\mathrm{kDa}$ ; denoted respectively DEX5, DEX7, DEX20, DEX40 and DEX500), fucoidan (FUC), heparin (HEP), poly (styrene sulfonate) (0.2, 4.2, 15, 29, 70, 80, 145 and $2070\\mathrm{kDa}$ denoted respectively PSS02, PSS4, PSS15, PSS29, PSS70, PSS80, PSS145, PSS2600) were purchased from Sigma Aldrich, France. Chitosan (Mw $=20$ , 30 and $250\\mathrm{kDa}$ ; CHI20, CHI30 and CHI250) were purchased from Glentham Life Sciences, United Kingdom. Hyaluronic acid $(\\mathrm{Mw}=29\\$ , 108, 823 and $2670\\mathrm{kDa}$ , HA29, HA108, HA823 and HA2670) were purchased from Lifecore Biomedical, USA. Poly(L-arginine) with 30 residues of arginine (PAR30) was purchased from Alamanda Polymers, USA.  \n\nData collection.  To collect the data from the literature, we searched articles describing LbL film buildup using PubMed website and Google Scholar (keywords: LbL, polyelectrolyte, film, thickness). In total, 31 articles were found. Among them, only articles specifying the parameters of the film buildup, as well as film thickness, in the text and/or in the figures, were selected. Thus, 19 articles were used in this ­study16,19–36.  \n\nThe second dataset consisted of experimental data produced in the laboratory using QCM (Q-Sense, Sweden). For this, a $\\mathrm{SiO}_{2}$ coated-crystal was excited at different resonance frequencies (fundamental frequency, third, fifth, and seventh overtones), and changes in frequency and dissipation were measured during the successive deposition of polymers and rinsing steps (Fig. 7A).  \n\nBefore each experiment, the crystal was cleaned for $30\\mathrm{min}$ with $2\\%$ Hellmanex, then rinsed with water. The final cleaning was done with 1 M HCl for $10~\\mathrm{min}$ , then rinsed with water. Poly(L-arginine) with chains composed of 30 arginine units (PAR30) and chitosan with different molecule weights (20, 30, 50, 100 and $250\\mathrm{kDa}$ (respectively CHI20, CHI30, CHI50, CHI100 and CHI250) were used as polycations. For the films constructed with PAR30 as polycation, a Tris $10\\mathrm{mM}/\\mathrm{NaCl}0.15\\mathrm{M}$ at $\\mathrm{pH}7.4$ buffer was used for the preparation of solutions and for rinsing steps. For the films constructed using chitosan as polycation, a buffer consisting of sodium acetate $70\\mathrm{\\mM/NaCl\\bar{8}0\\bar{m M}}$ at pH5 was used. Buffers were filtered with $0.2\\mathrm{-}\\upmu\\mathrm{m}$ filters. Twenty-eight different polymers were used as polyanions (see Materials part). QCM-D experiments were performed as described ­previously37. Briefly, polyanions and polycations used for the experiment were prepared at $0.5~\\mathrm{mg~mL^{-1}}$ in acetate or Tris/ $\\mathrm{\\DeltaNaCl}$ buffers, as explained above. Polycations were first adsorbed to the surface for $5\\mathrm{{min}}$ . A rinsing step was performed using the buffer for $5\\mathrm{min}$ after each polyelectrolyte deposition, and 8 bilayers were constructed on the $\\mathrm{SiO}_{2}$ -coated crystal with a flow rate of $250\\upmu\\mathrm{L}\\operatorname*{min}^{-1}$ .  \n\nSauerbrey’s equation gives the relation between the mass deposited on the vibrating crystal per unit area and the change of resonance frequency when the deposit behaves like a stiff coating of the crystal, i.e. when the deposit changes only the mass of the crystal. This is, however, generally not the case when a polyelectrolyte film is built up by successive depositions of polycations and polyanions from solutions. Indeed, on the one hand, the film is a viscoelastic body and on the other hand, the film is in contact with the solution. For both reasons, not only the change in frequency is measured but also the dissipation related to the characteristic damping time of the crystal vibration (Fig. 7B). If the normalized frequency shifts, $\\Delta f_{\\nu}/\\nu,$ corresponding to different overtone numbers are equal to $-m/C,$ i.e. are independent of $\\upnu,$ Sauerbrey’s equation stays valid. If this is not the case, a more sophisticated formalism ought to be ­used38. In this approach, the film is characterized by its elasticity, $\\upmu,$ its viscosity, ${\\mathfrak{n}},$ its density, $\\uprho,$ and its thickness, d. In the present study, the frequency shift and the dissipation corresponding to the overtones $\\upnu=3$ , 5 and 7, i.e. for excitation frequencies of about 15, 25 and $35\\mathrm{{MHz}}$ , have been processed to extract the thickness of the film at the end of the build-up (examples of film growth are shown in Fig. 7C). Hereafter, all thickness results are given for $\\uprho=1\\ \\mathrm{g}\\ \\mathrm{cm}^{-3}$ .  \n\n![](images/48a7328d96f986ace6b65205e341574c983a59c8d5588b0b81a1d1b21abfdc53.jpg)  \nFigure 7.   Film thickness determination by QCM-D. (A) Polyelectrolytes (chitosan, CHI, and hyaluronic acid, HA) are deposited on the crystal, where they form a multilayer film. (B) Growth of the film is followed by the measurements of the frequency and the dissipation variations with respect to the crystal in contact with the buffer solution only. As an example, the figure shows the measurements corresponding to the third overtone. (C) Film growth depending on polyanion.  \n\nData analysis.  The data set (Table S1), used for analysis and model construction, had 76 data points which were obtained by literature search (43 points) and experiments (33 points). The validation set used to evaluate model performance had 11 points, all generated by experiments (Table S2).  \n\nIn the original data set, each data point represents one coating with 23 features and one target value (resulting coating thickness). The features are the type of polycation (PC) and type of polyanion (PA), type of ending polymer, PC unit molecular weight (MW) and PA unit MW, total PC and PA MWs, the concentration of PC and the concentration of PA, polycation $\\mathrm{\\pH}$ and polyanion $\\mathrm{\\DeltapH}$ , the charge density of PC and charge density of PA, presence of carboxyl groups, presence of sulfonate groups, presence of sulfate groups, crosslinking method, bilayer deposition time, type of buffer, buffer concentration, the concentration of KCl, the concentration of $\\mathrm{\\MgCl}_{2}$ , and the concentration of NaCl (Table S3).  \n\nRelationships between features and target value were evaluated with the Pearson correlation coefficient and Predictive Power ­Score39. Statistical significance of the Pearson correlation coefficient was checked using confidence intervals for $\\textstyle P=0.05$ after Fisher’s Z-transformation.  \n\nThree regression models were built to predict coating thickness: one based on features from the original data set, and two Quantitative Structure–Property Relationships (QSPR-type) models based on the RDKit molecular descriptors. To build QSPR models, firstly the SMILES (simplified molecular-input line-entry system) representations of molecules were obtained from the PubChem database. Then, for each polymer SMILES, 123 molecular descriptors were generated using RDKit Descriptors from DeepChem ­library4  \n\nFeatures, that are further used to build models, were selected from original feature space and from molecular descriptors space with the Recursive Feature Elimination method having Random Forest as the basis. Finally, two methods were used to construct three coating thickness prediction models: Bagging Regression, QSPR Bagging Regression, and QSPR Support Vector Regression (SVR). All the described methods are implemented in the scikit-learn ­library22.  \n\nReceived: 29 March 2021; Accepted: 6 September 2021   \nPublished online: 21 September 2021",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# References  \n\n1.\t Decher, G. Fuzzy nanoassemblies: Toward layered polymeric multicomposites. Science 277, 5 (1997). 2.\t Decher, G. & Hong, J. D. Buildup of ultrathin multilayer films by a self-assembly process: II. Consecutive adsorption of anionic and cationic bipolar amphiphiles and polyelectrolytes on charged surfaces. Ber. Bunsenges. Phys. Chem. 95, 4 (1991). 3.\t Richardson, J. J. et al. Innovation in layer-by-layer assembly. Chem. Rev. 116, 14828–14867 (2016).   \n4.\t Zhao, S. et al. The future of layer-by-layer assembly: A tribute to ACS nano associate editor Helmuth Möhwald. ACS Nano 13, 6151–6169 (2019).   \n5.\t Campbell, J. & Vikulina, A. S. Layer-by-layer assemblies of biopolymers: Build-up, mechanical stability and molecular dynamics. Polymers (Basel) 12, 1949 (2020).   \n6.\t Boudou, T., Crouzier, T., Ren, K., Blin, G. & Picart, C. Multiple functionalities of polyelectrolyte multilayer films: New biomedical applications. Adv. Mater. 22, 441–467 (2010). 7.\t de Avila, E. D. et al. Anti-bacterial efficacy via drug-delivery system from layer-by-layer coating for percutaneous dental implant components. Appl. Surf. Sci. 488, 194–204 (2019).   \n8.\t Gribova, V., Auzely-Velty, R. & Picart, C. Polyelectrolyte multilayer assemblies on materials surfaces: From cell adhesion to tissue engineering. Chem. Mater. 24, 854–869 (2012).   \n9.\t Pahal, S., Gakhar, R., Raichur, A. M. & Varma, M. M. Polyelectrolyte multilayers for bio-applications: Recent advancements. IET Nanobiotechnol. 11, 903–908 (2017).   \n10.\t Priolo, M. A., Holder, K. M., Guin, T. & Grunlan, J. C. Recent advances in gas barrier thin films via layer-by-layer assembly of polymers and platelets. Macromol. Rapid Commun. 36, 866–879 (2015).   \n11. Rivero, P. J., Goicoechea, J. & Arregui, F. J. Layer-by-layer nano-assembly: A powerful tool for optical fiber sensing applications. Sensors 19, 683 (2019).   \n12.\t Lutkenhaus, J. L. & Hammond, P. T. Electrochemically enabled polyelectrolyte multilayer devices: From fuel cells to sensors. Soft Matter 3, 804–816 (2007).   \n13.\t Picart, C. et al. Molecular basis for the explanation of the exponential growth of polyelectrolyte multilayers. PNAS 99, 4 (2002).   \n14.\t Abtahi, S. M. et al. Micropollutant rejection of annealed polyelectrolyte multilayer based nanofiltration membranes for treatment of conventionally-treated municipal wastewater. Sep. Purif. Technol. 209, 470–481 (2019).   \n15.\t Richert, L. et al. Improvement of stability and cell adhesion properties of polyelectrolyte multilayer films by chemical cross-linking. Biomacromol 5, 10 (2004).   \n16.\t Boulmedais, F. et al. Buildup of exponentially growing multilayer polypeptide films with internal secondary structure. Langmuir 19, 440–445 (2003).   \n17.\t Müller, M. The anomalous influence of polyelectrolyte concentration on the deposition and nanostructure of poly(ethyleneimine)/ poly(acrylic acid) multilayers. Molecules 24, 2141 (2019).   \n18.\t Pedregosa, F. et al. Scikit-learn: Machine learning in python. J. Mach. Learn. Res. 12, 2825–2830 (2011).   \n19.\t Boudou, T., Crouzier, T., Auzély-Velty, R., Glinel, K. & Picart, C. Internal composition versus the mechanical properties of polyelectrolyte multilayer films: The influence of chemical cross-linking. Langmuir 25, 13809–13819 (2009).   \n20.\t Abtahi, S. M., Ilyas, S., Joannis Cassan, C., Albasi, C. & de Vos, W. M. Micropollutants removal from secondary-treated municipal wastewater using weak polyelectrolyte multilayer based nanofiltration membranes. J. Membr. Sci. 548, 654–666 (2018).   \n21.\t Alves, N. M., Picart, C. & Mano, J. F. Self assembling and crosslinking of polyelectrolyte multilayer films of chitosan and alginate studied by QCM and IR spectroscopy. Macromol. Biosci. 9, 776–785 (2009).   \n22.\t Benbow, N. L. et al. Odd-even effects on hydration of natural polyelectrolyte multilayers: An in situ synchrotron FTIR microspectroscopy study. J. Colloid Interface Sci. 553, 720–733 (2019).   \n23.\t Buron, C. C. et al. Surface morphology and thickness of a multilayer film composed of strong and weak polyelectrolytes: Effect of the number of adsorbed layers, concentration and type of salts. Thin Solid Films 517, 2611–2617 (2009).   \n24.\t Crouzier, T. & Picart, C. Ion Pairing and hydration in polyelectrolyte multilayer films containing polysaccharides. Biomacromol 10, 433–442 (2009).   \n25.\t Czerwieniec, B., Strawski, M., Granicka, L. H. & Szklarczyk, M. AFM study of adhesion and interactions between polyelectrolyte bilayers assembly. Colloids Surf. A 555, 465–472 (2018).   \n26.\t Elzḃieciak, M. et al. Influence of pH on the structure of multilayer films composed of strong and weak polyelectrolytes. Langmuir 25, 3255–3259 (2009).   \n27.\t Elżbieciak-Wodka, M., Kolasińska-Sojka, M. & Warszyński, P. Effect of mono- and divalent ions on the formation and permeability of polyelectrolyte multilayer films. J. Electroanal. Chem. 789, 123–132 (2017).   \n28.\t Fernández, R., Ocando, C., Fernandes, S. C. M., Eceiza, A. & Tercjak, A. Optically active multilayer films based on chitosan and an azopolymer. Biomacromol 15, 1399–1407 (2014).   \n29.\t Hillberg, A. L., Holmes, C. A. & Tabrizian, M. Effect of genipin cross-linking on the cellular adhesion properties of layer-by-layer assembled polyelectrolyte films. Biomaterials 30, 4463–4470 (2009).   \n30.\t Holmes, C. A. & Tabrizian, M. Enhanced MC3T3 preosteoblast viability and adhesion on polyelectrolyte multilayer films composed of glycol-modified chitosan and hyaluronic acid. J. Biomed. Mater. Res. Part A 100A, 518–526 (2012).   \n31.\t Ngankam, A. P., Mao, G. & Van Tassel, P. R. Fibronectin adsorption onto polyelectrolyte multilayer films. Langmuir 20, 3362–3370 (2004).   \n32.\t Picart, C. et al. Primary cell adhesion on RGD-functionalized and covalently crosslinked thin polyelectrolyte multilayer films. Adv. Func. Mater. 15, 83–94 (2005).   \n33.\t Strawski, M., Granicka, L. H. & Szklarczyk, M. Redox properties of polyelectrolyte multilayer modified electrodes: A significant effect of the interactions between the polyelectrolyte layers in the films. Electrochim. Acta 226, 121–131 (2017).   \n34.\t Tjipto, E., Quinn, J. F. & Caruso, F. Assembly of multilayer films from polyelectrolytes containing weak and strong acid moieties. Langmuir 21, 8785–8792 (2005).   \n35.\t Trybała, A., Szyk-Warszyńska, L. & Warszyński, P. The effect of anchoring PEI layer on the build-up of polyelectrolyte multilayer films at homogeneous and heterogeneous surfaces. Colloids Surf. A 343, 127–132 (2009).   \n36.\t Zhang, J. et al. Natural polyelectrolyte films based on layer-by layer deposition of collagen and hyaluronic acid. Biomaterials 26,   \n3353–3361 (2005).   \n37.\t Mutschler, A. et al. Unexpected bactericidal activity of poly(arginine)/hyaluronan nanolayered coatings. Chem. Mater. 28, 8700–   \n8709 (2016).   \n38.\t Voinova, M. V., Rodahl, M., Jonson, M. & Kasemo, B. Viscoelastic acoustic response of layered polymer films at fluid-solid interfaces: continuum mechanics approach. Phys. Scr. 59, 391–396 (1999).   \n39.\t Wetschoreck, F., Krabel, T. & Krishnamurthy, S. 8080labs/ppscore: Zenodo Release (Version 1.1.2) (Zenodo, 2020).   \n40.\t Ramsundar, B. et al. Deep Learning for the Life Sciences (O’Reilly Media, 2019).",
+        "category": " References"
+    },
+    {
+        "id": 6,
+        "chunk": "# Acknowledgements  \n\nThis project received funding from the European Union’s Horizon 2020 PANBioRA research and innovation program under Grant Agreement No. 760921, from ANR TerminAnion and Bourse Frenchtech Emergence grant.",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# Author contributions  \n\nP.L. and N.E.V. conceived the experiments; C.C., E.L. and L.D. conducted the experiments; V.G., A.N., O.L. and B.S. analyzed the results. All authors reviewed the manuscript. A.N.’s new affiliation is Eagle Genomics Ltd., Cambridge, UK.",
+        "category": " Abstract"
+    },
+    {
+        "id": 8,
+        "chunk": "# Competing interests  \n\nNihal Engin Vrana is the majority shareholder of SPARTHA Medical which is a coating development company. Philippe Lavalle is a shareholder of SPARTHA Medical and Cynthia Calligaro is a full-time employee of SPARTHA Medical. The article does not contain any information about SPARTHA products. Anastasiia Navalikhina and Oleksandr Lysenko are employees of Preste, a Data Science company. They provided impartial data analysis. Varvara Gribova, Bernard Senger, Lucie Deiber, Eloise Lebaudy have no conflict of interest.",
+        "category": " Abstract"
+    },
+    {
+        "id": 9,
+        "chunk": "# Additional information  \n\nSupplementary Information The online version contains supplementary material available at https://​doi.​org/ 10.​1038/​s41598-​021-​98170-x.  \n\nCorrespondence and requests for materials should be addressed to N.E.V.  \n\nReprints and permissions information is available at www.nature.com/reprints.  \n\nPublisher’s note  Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.  \n\nOpen Access   This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://​creat​iveco​mmons.​org/​licen​ses/​by/4.​0/.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,17 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Design of self-assembly dipeptide hydrogels and machine learning via their chemical features  \n\nFei Lia,1, Jinsong Hana,1, Tian Caob, William Lamc, Baoer Fand, Wen Tangd, Sijie Chena, Kin Lam Fokc,2, and Linxian $\\mathsf{L i}^{\\mathsf{a},2}$ aMing Wai Lau Centre for Reparative Medicine, Karolinska Institutet, Hong Kong; bDepartment of Computer Science, The University of North Carolina at Chapel Hill, Chapel Hill, NC 27599; cSchool of Biomedical Sciences, Faculty of Medicine, The Chinese University of Hong Kong, Hong Kong; and dSouth China Advanced Institute for Soft Matter Science and Technology, South China University of Technology, Guangzhou 510640, China  \n\nEdited by Robert Langer, Massachusetts Institute of Technology, Cambridge, MA, and approved April 23, 2019 (received for review February 26, 2019)  \n\nHydrogels that are self-assembled by peptides have attracted great interest for biomedical applications. However, the link between chemical structures of peptides and their corresponding hydrogel properties is still unclear. Here, we showed a combinational approach to generate a structurally diverse hydrogel library with more than 2,000 peptides and evaluated their corresponding properties. We used a quantitative structure–property relationship to calculate their chemical features reflecting the topological and physicochemical properties, and applied machine learning to predict the self-assembly behavior. We observed that the stiffness of hydrogels is correlated with the diameter and cross-linking degree of the nanofiber. Importantly, we demonstrated that the hydrogels support cell proliferation in culture, suggesting the biocompatibility of the hydrogel. The combinatorial hydrogel library and the machine learning approach we developed linked the chemical structures with their self-assembly behavior and can accelerate the design of novel peptide structures for biomedical use.  \n\nself-assembly | dipeptide hydrogels | machine learning  \n\nydrogels that are cross-linked by three-dimensional networks Hof modified molecules can maintain a large amount of water without dissolving its own chemical structure, which is very similar to natural tissue. As a result of favorable biocompatibility, hydrogels have great potential in biomedical applications such as drug delivery, tissue engineering, sensing, and cell encapsulation (1–7). In the past few years, considerable attention has been directed toward the design of peptide-based hydrogels in particular, not only because of their favorable features such as easy synthesis, decoration, biodegradability, and high compatibility, but also due to their wide applications in the biological and medical fields (8– 14). However, to the best of our knowledge, the prediction and design of peptide-based hydrogels is still challenging, which limits our research choices on peptide-based hydrogels (15, 16). Therefore, the design strategy for hydrogels based on peptides is of great significance. Our aim is to reveal the relationship between molecular structure and hydrogel behavior, which can help us to predict and design peptide hydrogels with new chemical structures. There are approaches using molecular dynamics simulation to model the self-assembly behavior of peptides into different types of nanostructures, including nanofibers, which can subsequently form hydrogels (17–19). However, it is difficult to evaluate the actual prediction accuracy of the molecular dynamics simulation methods because only a few positive peptides were selected and synthesized to test whether they could form a hydrogel. Additionally, the current reported synthetic method on 9- fluorenylmethyloxycarbonyl (Fmoc)-peptide is limited to the traditional peptide synthesis method, involving step-by-step protection and deprotection. Since a high-throughput peptide generation method is not available, our first motive is to develop a simple and fast method to generate a library with thousands of peptidelike molecules and then test their abilities to form a hydrogel. Using a rational complexation behavior from either a carboxylic acid or metal ions (20, 21), we plan to design chemical structures that can form a hydrogel at neutral pH without any carboxylic acid groups and divalent or trivalent metal ions. Next, the structure–property relationship between the chemical structures of peptides and their self-assembly properties can be examined by introducing different chemical groups (other than carboxylic acids) into this peptide library.  \n\nDeep learning or machine learning has been successfully applied to medical applications with accurate prediction; for example, in the diagnosis of pathology images (22–24). However, there are only a few reports on their application in the design of organic materials, and typical prediction accuracy is lower than $50\\%$ (25). Most of the work using machine learning for materials design is reported in the field of energy, but reports on their usage for biomaterials design are very limited. To our best knowledge, this is the first time that combinatorial chemistry and machine learning have been used to predict the self-assembly behavior of hydrogels. In this work, our second motive is to develop a machine learning method to link the chemical features of peptides with their self-assembly properties and to predict the gel formation ability based on the two-dimensional chemical structure.  \n\nIn this work, we developed a peptidelike chemical library based on a Ugi four-component reaction for screening the compounds that can form hydrogels. Selected hydrogels were characterized with a rheometer and transmission electron microscopy (TEM) and were further cultured with an adherent cell line. We generated the chemical features of the whole chemical library and developed the machine learning method to recognize these chemical features and predict whether a chemical structure can form a hydrogel at neutral pH without any divalent or trivalent metal ions. We also summarize the relationship between the molecular structure and gelation property.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Significance  \n\nHydrogels maintain great potential for biomedical applications. However, predicting whether a chemical can form a hydrogel simply based on its chemical structure remains challenging. In this study, we developed a combinational approach to obtain a structurally diverse hydrogel library with over 2,000 peptides as a training dataset for machine learning. We calculated their chemical features, including topological and physicochemical properties, and utilized machine learning methods to predict the self-assembly behavior.  \n\nAuthor contributions: F.L., J.H., and L.L. designed research; F.L., J.H., W.L., B.F., W.T., K.L.F., and L.L. performed research; F.L. and J.H. contributed new reagents/analytic tools; F.L., J.H., T.C., S.C., K.L.F., and L.L. analyzed data; and F.L., J.H., T.C., W.L., W.T., S.C., K.L.F., and L.L. wrote the paper.  \n\nPeptide-based hydrogels are usually formed based on the response of the carboxylic acid group toward the metal ions. In this paper, we built a peptide-based library without a carboxylic acid group. For the construction of a comprehensive chemical library as a testing pool, we used 31 monomers, including 8 amines, 8 aldehydes/ketones, 12 Fmoc-amino acids, and 3 isocyanides to synthesize 2,304 compounds via the Ugi reaction as shown in Fig. 1. The reaction was verified via mass spectrometry (MS) (SI Appendix, Figs. S30–S125) and $^1\\mathrm{H}$ NMR (SI Appendix, Figs. S126–S135) of 96 selected compounds. After the completion of the reactions, organic solvents were removed and phosphate buffered saline (PBS) solution was added to the reaction system. The solution was heated up to $80~^{\\circ}\\mathrm{C}$ and then cooled to room temperature to form hydrogels, as shown in Fig. $2E$ . Structure– property relationships of 81 hydrogels (Fig. 2 $A{-}D$ and $G$ ) demonstrate that monomers A12, B7, C6, and D3 were the most possible gelling-like structures to form hydrogels (Fig. $2A{-}D_{\\cdot}^{\\cdot}$ ). We also studied the effect of the potential parameters on hydrogel properties, such as the numbers of hydrogen bond acceptors (nHBAcc) and donors (nHBDon), the number of basic groups (nBase), and the Ghose–Crippen LogKow (ALogP), as shown in Fig. $2H{-}K$ . The results demonstrated that compounds with lower nHBAcc, moderate nHBDon, no nBase, and higher ALogP had stronger abilities to generate hydrogels. However, these features are not enough to predict whether a compound can form a hydrogel with a new chemical structure.  \n\nMachine learning-based artificial intelligence (AI) has proved to be useful for the prediction of human perception by employing a large number of psychophysical datasets (26, 27). However, the prediction for the formation of hydrogels is still challenging. Herein, machine learning was employed to explore the relationship between the molecular skeleton and hydrogel properties for the guidance of designing hydrogels.  \n\nFirst, 2,304 separate chemical structures were produced based on the monomers by the Ugi reaction for the construction of a combinatorial library. Second, PaDEL-Descriptor (28) was employed for the calculation of molecular descriptors and fingerprints from the chemical library that contains all 2,304 structures; ${\\sim}7,163,136$ effective structural parameters (3,109 structural parameters per molecule) were obtained according to the calculation.  \n\nNext, data points were processed with machine learning algorithms (Fig. $2F$ ). We formulated our question as a binary classification problem (i.e., given the structural parameters for each chemical structure): whether a hydrogel can be formed or not. This problem is challenging because our data are highly imbalanced. Only less than $4\\%$ (81/2,304) of the chemical structures can form hydrogels. To mitigate the class-imbalance problem, we introduced data resampling as a preprocessing step.  \n\n![](images/c68651e20e08a552b4ba203bd3b99e1b1e87227ab456bbd0abe298f82061a48e.jpg)  \nFig. 1. Substrates for the construction of the hydrogel library.  \n\n![](images/71ca0e5ed80a28c0483f29773721cc9ac9ef8f9b114e94681fee827990d3675a.jpg)  \nFig. 2. From screening to the rational design of hydrogels. Statistical data of monomers Fmoc-amino acids (A), amines (B), aldehydes or ketones (C), and isocyanides (D) that formed gels. $(E)$ Method for the preparation of hydrogels. $(F)$ Design of machine learning methods. (G) Screening results of hydrogels (red, gel formed; gray, solution state). $(H-K)$ Correlation between hydrogel percentages with nHBAcc $(H)$ , nHBDon (I), nBase $(J)$ , and ALogP (K).  \n\nData resampling is a common approach to handle imbalanced data. We used three common resampling approaches in our models: random oversampling (RO), synthetic minority oversampling technique (SMOTE), and adaptive synthetic sampling (ADASYN). RO is a naïve resampling approach which oversamples the minority class. The sampling strategy generates new samples by randomly sampling with replacement from the available samples. After RO resampling, there are multiple duplicated samples for certain data points. SMOTE is a synthetic sampling method which generates new samples from existing data points. For a given data point in the minority class, SMOTE generates a new sample as a linear combination between the data point and one of its nearest neighbors from the same class (Fig. 3B). ADASYN is an improved version of SMOTE. In ADASYN, the distribution of the minority class is considered in the sampling.  \n\nAfter data resampling, we applied multiple classification models to our data. We applied an extensive list of classification algorithms, from the linear classifiers such as logistic regression, to the nonlinear classifiers such as a neural network. After tuning the hyperparameters for each algorithm, we found three algorithms shown to possess the best prediction abilities (random forest, gradient boosting, and logistic regression; Fig. $3A$ and $C-$ $E$ ), with gradient boosting being superior to the other two algorithms. We illustrate the precision–recall (PR) curves and receiver operating characteristic (ROC) curves for different methods in Fig. 3. As our data are highly imbalanced (only $4\\%$ of the data can form hydrogels), we focused on precision and recall here. Precision is the ratio of correct results to predicted results, while recall is the fraction of correct results in the predicted positive samples. Our methods can achieve precisions of $54\\%$ , $57\\%$ , and $6\\Bar{2}\\%$ for random forest, logistic regression, and gradient boosting, respectively, at the $50\\%$ recall. Moreover, feature importance was calculated and the top 20 descriptors were obtained from the best three machine learning algorithms (Fig. 4). The results indicated that the descriptors monomer1 (Fmoc-amino acids),  \n\n![](images/2f69bb5c788d7ade14024ab274426788f2d233c97e9347f7880ce8a29b8f46e8.jpg)  \nFig. 3. Machine learning algorithms for gel prediction. (A) Example of random forest and gradient boosting algorithms. (B) Illustration of SMOTE and ADASYN oversampling algorithms. (C–E) PR curve and ROC curve calculated from the random forest model (C), the gradient boosting model $(D)$ , and the logistic regression model (E).  \n\nSpMax1_Bhi (largest absolute of Burden modified eigenvalue), and SpMin1_Bhi (smallest absolute of Burden modified eigenvalue) contribute most to the formation of molecular hydrogels.  \n\nThe hydrogels with diversified functional groups can exhibit different mechanical properties, which is important for controlled drug release and tissue engineering (29–32). We selected typical hydrogels from our algorithm with good temperatureresponsive properties to study their rheological properties. As shown in Fig. 5A (also see $S I$ Appendix, Figs. S1–S11), the frequency-dependent oscillatory rheology $\\mathit{\\check{\\gamma}}_{0}=0.5\\%$ , 0.1 to 100 rad $\\ensuremath{\\mathbf{\\bar{s}}}^{-1}$ ) of selected hydrogels had certified hydrogel-like behavior, where $\\mathbf{G}^{\\prime}$ was regnant in the whole process. Meanwhile, different chemical structures showed a variety of rheological properties. Hydrogels 19/PBS, 10/PBS, 21/PBS, 20/PBS, and ${\\bf64}/$ PBS were selected based on the gradual increase of $\\mathbf{G}^{\\prime}$ and $\\mathbf{G}^{\\prime\\prime}$ values. They displayed a different value of storage and loss of oscillatory shear modulus $\\mathbf{\\bar{G}^{\\prime}}$ and $\\mathbf{G}^{\\prime\\prime}$ ). These results reflected their distinction on hardness and elasticity of hydrogels, demonstrating that the peptidelike molecules with multiple functional groups can lead to the difference in rheological behavior. Meanwhile, the mechanical properties (such as elasticity and viscosity) of substrates can influence the morphology, proliferation, and differentiation of stem cells. The increase of $\\mathbf{G}^{\\prime}$ (elastic modulus) and $\\mathbf{G}^{\\prime\\prime}$ (viscous modulus) from compounds 19 to 64 demonstrated that these hydrogels owned a large range of mechanical properties that have potential application in stem cell research (33–35). These results also indicated that a series of hydrogels with different rheological behaviors could be largely obtained via a combinatorial approach.  \n\nSince the microstructure of hydrogels can influence their rheological behavior, TEM experiments were performed to characterize their morphology. As shown in Fig. $5B$ , these compounds in PBS solution exhibited an entangled fibrous network, which is ascribed to the supramolecular self-assembly of these compounds in PBS solution, leading to the formation of hydrogels. Interestingly, consistent with $\\mathbf{G}^{\\prime}$ and $\\mathbf{G^{\\prime\\prime}}$ , it was easily observed that the density of nanofibers gradually increased from the 19/PBS hydrogel to the 10/PBS and 21/PBS hydrogels. Meanwhile, in corroboration with their rheological behavior, an increase in the density and the diameter of nanofiber was observed from the 21/PBS hydrogel to the 20/PBS and 64/PBS hydrogels. These results suggest that compounds with different functional groups exhibit differential self-assembly abilities and differentiated morphologies, which in turn leads to their distinct rheological properties.  \n\n![](images/b4e9fe0f401788f23fe6bfc0e2f89bd41146d015527ec9e2c9b0c8a606b6e453.jpg)  \nFig. 5. (A) Frequency-dependent $(\\gamma_{0}=0.5\\%$ , $25^{\\circ}\\mathsf{C})$ oscillatory shear rheology (Insets: photographs of hydrogels and chemical structures of compounds 19, 10, 21, 20, and 64, from left to right). (Magnification: $5\\times$ .) (B) TEM pictures of compound 19/PBS, 10/PBS, 21/PBS, 20/PBS, and 64/PBS hydrogels (from left to right). (Scale bar: $1~{\\upmu\\mathrm{m}}$ .)  \n\n![](images/99b958d6c10b3c5e9f4805f4729e34c8f3c7d59b79fd7841879ccb64e07333ca.jpg)  \n\nFinally, we tested the ability of hydrogels to support the culture of TM4 cells, an adherent mouse Sertoli cell line with epithelial cell morphology. We labeled the cell body with CellTracker Green, and the cell nucleus with Hoechst 33342, to visualize the potential changes in cell morphology. As shown in Fig. 6, at day 1 after seeding, a subpopulation of cells in hydrogel 10- and 79- coated dishes demonstrated classical epithelial morphologies, whereas another subpopulation formed small cell clusters. Both hydrogels 10 and 79 support the proliferation of cells as indicated by the increase in cell number from day 1 to day 3 after seeding, suggesting the biocompatibility of these hydrogels.  \n\nIn conclusion, we have utilized a combinatorial approach to establish a chemical library and a screen for hydrogel behavior. This approach is highly efficient, allowing high-throughput design and prediction to obtain hydrogels with novel chemical structures and controlled physical properties. We have developed a machine learning approach to study the correlation between chemical features and the ability to form hydrogels of the peptidelike molecules. The machine learning revealed that the structure descriptors based on quantum chemistry exhibit a high correlation with gelling behavior. Importantly, we further showed that the hydrogels designed by this approach can be used in biomedical application such as cell culture. We envision that our combinatorial approach and machine learning method can be used as the design and prediction tools for peptide hydrogels with a controlled physical property for biomedical applications, such as drug delivery and tissue engineering.  \n\n![](images/1433b149482d715a65e4b7eb72ec88f7dc8cb055dd49d475ad8056cbefeb2039.jpg)  \nFig. 4. Feature importance (top-20 descriptors) from machine learning algorithms for gel prediction. (A–C) Top 20 parameters related to gel formation calculated from random forest algorithm (A), gradient boosting algorithm (B), and logistic regression $(C)$ .   \nFig. 6. Morphologies of cells cultured on AI-designed hydrogels. Representative images showing the morphologies of TM4 cells on indicated hydrogels at day 1 (Left) and day 3 (Right) after seeding. Uncoated glassbottom dish was used as a control. The cell body was stained with CellTracker Green 5-chloromethylfluorescein diacetate (CMFDA, green) and the nucleus was stained with Hoechst 33342 (blue). (Magnification: $100\\times.$ )  \n\n1. B. Balakrishnan, R. Banerjee, Biopolymer-based hydrogels for cartilage tissue engineering. Chem. Rev. 111, 4453–4474 (2011).   \n2. T. E. Brown, K. S. Anseth, Spatiotemporal hydrogel biomaterials for regenerative medicine. Chem. Soc. Rev. 46, 6532–6552 (2017).   \n3. M. Choi et al., Light-guiding hydrogels for cell-based sensing and optogenetic synthesis in vivo. Nat. Photonics 7, 987–994 (2013).   \n4. J. Li, D. J. Mooney, Designing hydrogels for controlled drug delivery. Nat. Rev. Mater.   \n1, 16071 (2016).   \n5. L. Li, B. Yan, J. Yang, L. Chen, H. Zeng, Novel mussel-inspired injectable self-healing hydrogel with anti-biofouling property. Adv. Mater. 27, 1294–1299 (2015).   \n6. Y. Li, J. Rodrigues, H. Tomás, Injectable and biodegradable hydrogels: Gelation, biodegradation and biomedical applications. Chem. Soc. Rev. 41, 2193–2221 (2012).   \n7. L. Yu, J. Ding, Injectable hydrogels as unique biomedical materials. Chem. Soc. Rev. 37,   \n1473–1481 (2008).   \n8. E. F. Banwell et al., Rational design and application of responsive alpha-helical peptide hydrogels. Nat. Mater. 8, 596–600 (2009).   \n9. J. Kisiday et al., Self-assembling peptide hydrogel fosters chondrocyte extracellular matrix production and cell division: Implications for cartilage tissue repair. Proc. Natl. Acad. Sci. U.S.A. 99, 9996–10001 (2002).   \n10. Z. Luo et al., A powerful $\\mathsf{C D8^{+}}$ T-cell stimulating D-tetra-peptide hydrogel as a very promising vaccine adjuvant. Adv. Mater. 29, 1601776 (2017).   \n11. M. P. Lutolf, J. A. Hubbell, Synthetic biomaterials as instructive extracellular microenvironments for morphogenesis in tissue engineering. Nat. Biotechnol. 23, 47–55 (2005).   \n12. C. M. Madl et al., Maintenance of neural progenitor cell stemness in 3D hydrogels requires matrix remodelling. Nat. Mater. 16, 1233–1242 (2017).   \n13. A. N. Moore, J. D. Hartgerink, Self-assembling multidomain peptide nanofibers for delivery of bioactive molecules and tissue regeneration. Acc. Chem. Res. 50, 714–722 (2017).   \n14. C. Yan, D. J. Pochan, Rheological properties of peptide-based hydrogels for biomedical and other applications. Chem. Soc. Rev. 39, 3528–3540 (2010).   \n15. P. W. Frederix et al., Exploring the sequence space for (tri-)peptide self-assembly to design and discover new hydrogels. Nat. Chem. 7, 30–37 (2015).   \n16. R. G. Weiss, The past, present, and future of molecular gels. What is the status of the field, and where is it going? J. Am. Chem. Soc. 136, 7519–7530 (2014).   \n17. O. S. Lee, V. Cho, G. C. Schatz, Modeling the self-assembly of peptide amphiphiles into fibers using coarse-grained molecular dynamics. Nano Lett. 12, 4907–4913 (2012).   \n18. O. S. Lee, S. I. Stupp, G. C. Schatz, Atomistic molecular dynamics simulations of peptide amphiphile self-assembly into cylindrical nanofibers. J. Am. Chem. Soc. 133, 3677–3683 (2011).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 3,
+        "chunk": "# Materials and Methods  \n\nMaterials and methods are detailed in SI Appendix.  \n\nACKNOWLEDGMENTS. This project was supported by start-up funds from Ming Wai Lau Centre for Reparative Medicine, Karolinska Institutet; the National Natural Science Foundation of China (Grant 81771639); the Research Grants Council of Hong Kong (Grants 14127316 and 14129316); and start-up funds from the Lo Kwee Seong Foundation.  \n\n19. P. W. Frederix, R. V. Ulijn, N. T. Hunt, T. Tuttle, Virtual screening for dipeptide aggregation: Toward predictive tools for peptide self-assembly. J. Phys. Chem. Lett. 2, 2380–2384 (2011).   \n20. X. Du, J. Zhou, J. Shi, B. Xu, Supramolecular hydrogelators and hydrogels: From soft matter to molecular biomaterials. Chem. Rev. 115, 13165–13307 (2015).   \n21. R. Zou et al., Peptide self-assembly triggered by metal ions. Chem. Soc. Rev. 44, 5200–   \n5219 (2015).   \n22. R. C. Deo, Machine learning in medicine. Circulation 132, 1920–1930 (2015).   \n23. B. Ehteshami Bejnordi et al.; The CAMELYON16 Consortium, Diagnostic assessment of deep learning algorithms for detection of lymph node metastases in women with breast cancer. JAMA 318, 2199–2210 (2017).   \n24. D. S. Kermany et al., Identifying medical diagnoses and treatable diseases by imagebased deep learning. Cell 172, 1122–1131.e9 (2018).   \n25. S. Nagasawa, E. Al-Naamani, A. Saeki, Computer-aided screening of conjugated polymers for organic solar cell: Classification by random forest. J. Phys. Chem. Lett. 9, 2639–2646 (2018).   \n26. A. Keller et al.; DREAM Olfaction Prediction Consortium, Predicting human olfactory perception from chemical features of odor molecules. Science 355, 820–826 (2017).   \n27. E. Poivet et al., Functional odor classification through a medicinal chemistry approach. Sci. Adv. 4, eaao6086 (2018).   \n28. C. W. Yap, PaDEL-descriptor: An open source software to calculate molecular descriptors and fingerprints. J. Comput. Chem. 32, 1466–1474 (2011).   \n29. J. A. Burdick, W. L. Murphy, Moving from static to dynamic complexity in hydrogel design. Nat. Commun. 3, 1269 (2012).   \n30. G. Camci-Unal, N. Annabi, M. R. Dokmeci, R. Liao, A. Khademhosseini, Hydrogels for cardiac tissue engineering. NPG Asia Mater. 6, e99 (2014).   \n31. T. R. Hoare, D. S. Kohane, Hydrogels in drug delivery: Progress and challenges. Polymer 49, 1993–2007 (2008).   \n32. D. Seliktar, Designing cell-compatible hydrogels for biomedical applications. Science   \n336, 1124–1128 (2012).   \n33. A. Banerjee et al., The influence of hydrogel modulus on the proliferation and differentiation of encapsulated neural stem cells. Biomaterials 30, 4695–4699 (2009).   \n34. E. E. Charrier, K. Pogoda, R. G. Wells, P. A. Janmey, Control of cell morphology and differentiation by substrates with independently tunable elasticity and viscous dissipation. Nat. Commun. 9, 449 (2018).   \n35. A. J. Engler, S. Sen, H. L. Sweeney, D. E. Discher, Matrix elasticity directs stem cell lineage specification. Cell 126, 677–689 (2006).",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# 涂料溶剂的介绍",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# 一、涂料中溶剂的组成  \n\n由于涂料对溶剂的要求比较苛刻，考虑到挥发速率、溶解性以及成本等多种因素，单一溶剂很难满足涂料的使用要求，涂料用溶剂一般为混合溶剂，由三大部分组成，即真溶剂、助溶剂和稀释剂。一般来说，混合溶剂的组成是由其施工工艺条件所控制的，如涂料干燥温度和干燥时间等。通常室温下物理干燥的涂料，其混合溶剂的组成为 $45\\%$ 低沸点溶剂、 $45\\%$ 中等沸点溶剂和 $10\\%$ 高沸点溶剂。  \n\n配方中真溶剂与惰性溶剂的比例要合适，这样才能得到透明无光雾的涂膜。低沸点的溶荆加速干燥，而中等沸点和高沸点的溶剂保证涂膜的成膜无缺陷。烘干漆、烘烤磁漆和卷材涂料的施工温度相对较高，故其溶剂的组成中高沸点溶剂含量相应也要高，仅含少量的易挥发溶剂，因为易挥发溶剂会使涂料在烘烤过程中“沸腾”。  \n\n在漆料中，溶剂的性质也依赖于树脂的类型。为了获得快干、低溶剂残留的涂膜，混合溶剂的溶解度参数及其氢键参数必须位于树脂溶解度范围的边界部分。另一方面，混合溶剂的这些参数又必须与树脂的参数相近，以保证涂料获得满意的流动性。要找到这么一个切合实际的平衡点是很困难的，需要做大量的实验。根据溶解度参数理论，选择的混合溶剂中，非溶剂比真溶剂更易挥发，则对加速干燥是很有利的。真溶剂在涂膜中较后挥发，可增加涂料的流动性。也就是说，随溶剂的挥发，混合溶剂的溶解度参数应从树脂溶解度的边界区域迁移向中心区。不过，应该注意，在溶剂的挥发过程中，固体浓度的不断增加，涂料温度的增加或降低都会改变树脂的溶解区域。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 3,
+        "chunk": "# 二、涂料中溶剂的作用  \n\n溶剂在涂料中的作用往往不为人们所重视，认为它是挥发组分，最后不会留在涂膜中，所以对涂膜的质量不会产生很大的影响。其实不然，各种溶剂的溶解力及挥发速率等因素对于涂料的生产、贮存、施工等方面，以及涂膜的光泽度、附着力、表面状态等多方面性能都有极大的影响。溶剂在涂料中所起的作用如下。  \n\n$\\textcircled{1}$ 溶剂可以溶解并稀释涂料中的成膜物质，降低涂料的黏度，便于涂刷或喷、浸、淋等工艺。  \n\n涂料的黏度主要与树脂的性质、溶剂的组成、树脂的浓度、颜料浓度以及温度有关。在同系物溶剂中，涂料的黏度通常随溶剂分子量的升高而升高。由于溶剂分子量的升高降低了溶剂的溶剂化能力，所以说涂料黏度与溶剂化能为有关似乎很合理。但对不是同系物的一系列的溶剂比较表明，溶剂黏度与溶剂化能力无关。树脂溶液的黏度是由多种树脂一溶剂之间的相互作用力所决定的，也受溶剂本身的黏度、树脂分子的非卷曲程度、树脂的分子量、溶剂与树脂分子间的氢键、溶剂分子之间的氢键等的影响。也就是说，涂料的黏度并不是当混合溶剂的参数值落在树脂溶解区域的中心时才为最低，因为树脂分子在其溶解度区域中心为高度伸展的（体积为最大）。溶剂的溶解度参数如果正好位于该区域中心，则配制的涂料黏度特别高。为了获得低黏度的涂料，可使用溶剂的添加剂，调整溶剂的溶解度参数值，使其位于树脂的溶解度区域边界，但如果超出边界的话，溶液会变得浑浊，黏度也会突然上升。含有醇类溶剂的涂料或含羟基树脂的黏度可以通过加少量非溶剂而降低（200 号溶剂油）。在这个稀释过程中，氢键明显遭到破坏。  \n\n涂料在垂直面上的流挂现象可以通过使用能形成氢键的溶剂，以及使涂料具有触变性而加以解决。  \n\n根据 Arrhenius 方程： $1/\\mathrm{\\n{=}A e{\\mathrm{-}}E/R T}$ 涂料的黏度随温度升高而降低，其中 A、E 为材料常数。  \n\n在不同的应用条件下，涂料需有不同的黏度。低黏度的涂料适于喷涂和浸涂，高黏度的涂料适于浇涂、辊涂、热喷涂。正确选择溶剂可以优化涂料的性质。  \n\n$\\textcircled{2}$ 增加涂料贮存的稳定性，防止成膜物质发生胶结。同时，加入溶剂后会使桶内充满溶剂的蒸汽，可减少漆表面结皮。  \n\n$\\textcircled{3}$ 会使涂膜流平性良好。可避免漆膜太厚、过薄或涂刷性能不好而产生的刷痕和起皱等弊病。  \n\n$\\textcircled{4}$ 溶剂加入涂料中，可提高涂料对被涂物表面的润湿性和渗透性增强涂层的附着力。此外，溶剂的使用还可以在一定程度上降低涂料的成本。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# 三、涂料中溶剂选择原则  \n\n一般对涂料所用的溶剂有如下几点要求。  \n\n(1)溶解度 溶解度是指溶剂把溶质分散和溶解的能力。所用的溶剂对主要的成膜物质应该有很好的溶解性，应有比较强的降低黏度的能力，能固体或黏稠液体变成可以喷涂或刷涂的稀薄液体，在挥发过程中不应该出观某一成膜物质不溶析出的现象。  \n\n(2)挥发速率 溶剂的挥发速率必须适应涂膜的形成，尤其是对于一些挥发性的漆类，溶剂的挥发速率直接影响到漆膜干燥速率的快慢、施工的难易和漆膜质量等。  \n\n此外，溶剂的化学性质必须稳定，与涂料各组分无化学反应，同时毒性要小，安全性能要高，并且来源充分、价格便宜等。  \n\n配制混合溶剂，并不是任意选几种溶剂在一起就行了，而是有一定规律可循的。一般来说，混合溶剂配方设计的主导思想是获得 对树脂的溶解性、溶剂的挥发速度、各种溶剂之间关系等因素的平衡。  \n\n在设计涂料配方工作时，对于选择合适的溶剂，需要遵循以下几个原则。",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 1．极性相似原则  \n\n即极性相近的物质可以互溶，极性大的溶质易溶于极性大的溶剂，而极性小的溶质易溶于极性小的溶剂中。可根据物质的极性，初步确定选择什么溶剂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2．溶剂化原则  \n\n溶剂化是指高分子链段和溶剂分子间的作用力，它使溶剂将高分子链段分离开。因此，溶剂和高分子链必须产生溶剂化作用，从而使高聚物溶解。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 3．溶解度参数相近原则  \n\n任何一种高分子化合物都是靠分子间作用力使大分子聚集在一起的，衡量这种作用能力大小的叫内聚能，单位体积内聚能为内聚能密度，内聚能密度的平方根定义为溶解参数。溶解参数可作为选择溶剂的参考指标，对于非极性高分子材料或极性不很强的高分子材料，当其溶解度参数与某一溶剂的溶解度参数相等或相差不超过 $\\pm1.5$ ，该聚合物便可溶于溶剂中，否则不溶。高聚物和溶剂的溶解度参数可以测定或计算出来，如环氧树脂的溶解参数为 $\\delta=$ $9.7{\\sim}10.9$ 。选择溶剂除了单一溶剂外，还可以使用混合溶剂。有时，两种溶剂单独都不能溶解的聚合物，如将两种溶剂按一定的比例混合起来，却能使同一聚合物溶解。混舍溶剂具有协同效应，可作为一种选择溶剂的方法。确定混合溶剂的比例，可按下式进行计算，使混合溶剂的溶解度参数接近聚合物的溶解参数，再由实验最后确定。  \n\n式中， 为第ί种溶剂的体积分数； 为第ί种溶剂的溶解参数。常用溶剂的溶解度参数见表 3-1 和表 3-2。  \n\n<html><body><table><tr><td>溶剂</td><td></td><td>8 i/(J/cm3)1/2</td><td>溶剂</td><td></td><td>8 i/(J/cm3)1/2</td></tr><tr><td>正戊烷</td><td></td><td>14.42</td><td></td><td>环己醇</td><td>23. 32</td></tr><tr><td>异 戊</td><td>烷</td><td>14. 42(13. 81)</td><td>甲</td><td>醇</td><td>29. 67</td></tr><tr><td>正 己</td><td>烷</td><td>14.</td><td>94 乙</td><td>醇</td><td>25. 98</td></tr><tr><td>环</td><td>己 烷</td><td>16.</td><td>78 正</td><td>丙 醇</td><td>24. 35</td></tr><tr><td>正</td><td>庚 烷</td><td>15.</td><td>24 正</td><td>丁 醇</td><td>23. 32</td></tr><tr><td>正</td><td>辛 烷</td><td>15.</td><td>45 正</td><td>戊 醇</td><td>22. 30 ~ 21. 59</td></tr><tr><td>正</td><td>丁 烷</td><td>13.</td><td>50 异</td><td>丁 醇</td><td>21. 89(22. 51)</td></tr><tr><td>环</td><td>戊 烷</td><td>16.</td><td>82 丙</td><td>酮</td><td>20. 46(20. 05)</td></tr><tr><td>二</td><td>氯甲烷</td><td>19. 85(20.</td><td>54) 甲</td><td>乙 酮</td><td>19. 03</td></tr><tr><td>氯</td><td>仿</td><td>19.</td><td>03 环</td><td>己 酮</td><td>20. 26</td></tr><tr><td>正 甲</td><td>丙 苯</td><td>17.</td><td>70 甲</td><td>酸甲酯</td><td>21. 89</td></tr><tr><td>苯</td><td>苯</td><td>18.</td><td>21 甲</td><td>酸 乙 酯</td><td>19. 23(19. 74)</td></tr><tr><td>邻</td><td></td><td>18.</td><td>72 乙</td><td>酸 甲酯</td><td>19. 44</td></tr><tr><td>间</td><td>二 甲苯</td><td>18.</td><td>41 乙 酸</td><td>乙 酯</td><td>18. 62</td></tr><tr><td></td><td>二 甲苯</td><td>18.</td><td>00 水</td><td>二 烯</td><td>47. 88</td></tr><tr><td>对 二</td><td>甲苯</td><td>17.</td><td>90 丁</td><td></td><td>13. 91</td></tr><tr><td>乙 乙</td><td>苯 醇</td><td>18. 32. 12 (29.</td><td>00 丁</td><td>二 醛 醚</td><td>18. 41</td></tr><tr><td colspan=\"2\">二 丙三醇</td><td>33.76</td><td>05) 乙 四氯化碳</td><td></td><td>15. 75 17.60</td></tr></table></body></html>  \n\n表 3-2 常用溶剂的溶解度参数δί  \n\n\n<html><body><table><tr><td>溶剂</td><td>82/(J/cm3）</td></tr><tr><td>1/2 溶剂 12. 69</td><td>a2/(J/cm3)1/2 18. 62(26. 19</td></tr><tr><td>聚四氯乙烯 聚 乙烯 15. 75 ～</td><td>聚甲基丙烯酸甲</td></tr><tr><td>16. 98 酯</td><td>）</td></tr><tr><td>聚异丁烯 15. 96-16. 57 聚碳酸酯 聚偏二氯乙烯</td><td>19. 44～ 20. 05</td></tr><tr><td>20. 26 ～ 24. 96</td><td>聚丙烯酸甲酯 19. 85～ 21.18</td></tr><tr><td>聚丙烯 16. 57 ～ 16.</td><td>78 聚对苯二甲酸乙二醇 21. 89(19. 85)</td></tr><tr><td>聚丁二烯 16. 57 ～ 17. 60</td><td>酯 19. 85</td></tr><tr><td>氯化丙 烯 15. 34 ～ 20. 26</td><td>聚乙基丙烯酸酯 20. 46</td></tr><tr><td>苯乙 烯 17. 39-19. 03 聚氨基甲酸酯</td><td>19. 85～ 22. 51</td></tr><tr><td>氯 乙 烯 19. 23 ～ 19. 85</td><td>环氧树脂 23. 53</td></tr><tr><td>氯 碘化聚乙烯 16. 37 ～ 20. 46 酚醛树脂</td><td>14. 94 ~ 15. 55</td></tr><tr><td>天 然 橡胶 16. 16(16. 67)</td><td>聚二甲基硅氧烷 19. 23</td></tr><tr><td>丁 睛 橡 腔 19. 44(18. 93)</td><td>聚硅氧烷 ZI. 69 21. 89) （</td></tr><tr><td>氯 丁 橡 胶 16. 78 ～ 18. 82</td><td>聚甲基丙烯腈 25. 57～ 31.51</td></tr><tr><td>苯 橡 胶 16. 57 ～ 17. 60</td><td>聚丙烯腈 21. 48(23. 53) 22. 30～ 23. 32</td></tr><tr><td>丁 聚 硫 橡 胶 18. 41</td><td>～ 19. 23 二硝基纤维素 15. 57 醋酸纤维素 20. 87～ 22. 51</td></tr></table></body></html>  \n\n<html><body><table><tr><td>聚乙酸乙烯酯</td><td>19. 23(22. 51)</td><td>聚甲醛 基乙烯醇 尼龙66</td><td>47.</td><td>88(25. 78) 27.83</td></tr></table></body></html>  \n\n溶剂对高分子的溶解能力，可由配制一定浓度溶液的溶解速率、黏度以及此溶液对非溶剂的容忍度（稀释比值）等几个方面表示。稀释比值是指可以容忍非溶剂的最高份数，超过此值，溶解力将完全丧失。  \n\n4．确定适当的溶剂挥发速率  \n\n溶剂是挥发性液体，在施工过程中首先接触到的是涂层干燥快慢问题，这和溶剂的挥发速率有关。混合溶剂的挥发总速率可以表示为  \n\n式中， 为第ί种溶剂的体积分数； 为ί溶剂的活度系数； $R_{i0}$ 为ί溶剂的挥发速率。  \n\n施工过程中往往希望涂层干燥得快一些，但干燥得过快，会影响涂层的流平、光泽等指标。干得慢些可以保证涂层流平，防止涂层表观出现一些弊病，如橘皮、泛白等。溶剂挥发速率决定于溶剂本身的沸点、分子量、分子结构。一般认为低沸点的物质，挥发快，饱和蒸气压高。低沸点溶剂是指沸点在 $100^{\\circ}\\mathrm{C}$ 以下的溶剂，中沸点溶剂是指 $110{\\sim}145^{\\circ}\\mathrm{C}$ 之间的溶剂，高沸点溶剂是指 $145{\\sim}170^{\\circ}\\mathrm{C}$ 之间的溶剂，在 $170^{\\circ}\\mathrm{C}$ 以上的溶剂则为特高沸点溶剂。溶剂的挥发速率有两种表示方法：一种是以单位质量乙醚挥发时间为 l，其他溶剂单位质量与乙醚挥发时间之比为该溶剂的挥发速率；第二种方法是以一定时间内乙酸丁酯挥发的质量为 100，将其他溶剂在相同的时间内所挥发昀质量与之相比来表示。  \n\n在具体选择溶剂的过程中，就是低沸点、中沸点的用量要多，而高沸点溶剂用量要少。高沸点溶剂主要用于调节涂料的干燥时间，使涂料有充分时间流平，避免涂层在干燥过程中产生弊病。  \n\n涂料的黏度：不挥发组分的品种、规格、数量，尤其是树脂的分子量，影响着涂料的黏度。溶剂对黏度有较大的影响，溶剂的溶解能力大，则溶液的黏度低；溶解能力差，黏度高。  \n\n混合溶剂的挥发速率：混合溶剂的挥发速率影响涂层干燥时间，也影响涂层的表观。如果溶剂挥发过快，导致涂层的黏度增 大，流动性降低，会严重影响涂层的流平性，从而导致涂膜不平滑，出现橘皮现象。为了得到光洁平整的涂膜，不能片面追求快干,而应有一定比例的慢挥发溶剂以保证流平性。但若片面追求流平，在最终阶段少量的溶剂仍残留在涂层里，也会造成涂层不干、发黏、发软，附着力也受到影响，导致附着力降低。为避免这种现象发生，要控制高沸点溶剂的用量，使其不残留在涂膜里。常用溶剂的性质见表 3-3。  \n\n表 3-3 常用溶剂的性能  \n\n\n<html><body><table><tr><td>溶剂名称</td><td>密度 /(g/cm3)</td><td>/℃</td><td>沸点 速率</td><td>挥发 闪点 / ℃</td></tr><tr><td>丙 酮</td><td>0.79</td><td>56</td><td>9．44</td><td>-18</td></tr><tr><td>丁 酮</td><td>0. 81</td><td>80</td><td>5. 72</td><td>-7</td></tr><tr><td>甲基异丁基酮</td><td>0. 83</td><td>116</td><td>1. 64</td><td>13</td></tr><tr><td>环 誠己酮</td><td>0. 95</td><td>156</td><td>0. 25</td><td>43</td></tr><tr><td>乙 酸丁酯</td><td>0. 88</td><td>125</td><td>1. 00</td><td>23</td></tr><tr><td>乙 酸乙酯</td><td>0. 90</td><td>77</td><td>4. 80</td><td>-4. 4</td></tr></table></body></html>  \n\n<html><body><table><tr><td>丁 乙 甲 二 200 号溶剂油</td><td rowspan=\"8\">81 79 90 87</td><td>118</td><td>0. 36</td><td>35</td></tr><tr><td>醇 0. 醇 0.</td><td>79 2.</td><td>53 12</td></tr><tr><td>丙二醇乙醚 0.</td><td>132 0.</td><td>43</td></tr><tr><td>苯 0.</td><td>49 111 2. 14</td><td>4.4</td></tr><tr><td>甲苯 0.</td><td>138 ～ 144 0. 73</td><td>17 ～ 25</td></tr><tr><td>87</td><td>-0. 18</td><td></td></tr><tr><td>0.80</td><td>145～200</td><td>≥38</td></tr></table></body></html>  \n\n5．溶剂平衡  \n\n混合溶剂由真溶剂、助溶剂以及稀释剂三类组分组成，这三类组分又有快挥发、中挥发和慢挥发之别。当一种混合溶剂配成后，由于这些原料挥发的速卒不同，总是挥发快的原料首先逸出。自开始喷涂后，溶剂的成分就开始变化，怎样变化才理想，需根据以下的原则进行平衡。  \n\n(1)溶剂的挥发应均衡。混合溶剂的蒸馏曲线应呈平缓上升，否则将引起多种涂膜的表面缺陷，致使涂膜产生应力影响涂膜的寿命。因此，在配方中应考虑不同组分的挥发速率，快、中、慢的组分用量要平衡。例如，配方中，如果快挥发和慢挥发使用溶剂量较大，而没有适量中挥发溶剂加以平衡，必然是前阶段溶剂挥发较快，后阶段溶剂挥发较慢，这样的配方缺点较大。  \n\n(2)真溶剂、助溶剂及稀释剂的比例平衡。真溶剂、助溶剂以及稀释剂对涂料的黏度影响很大，较高含量的稀释剂或助溶剂都会提高涂料的黏度。在挥发过程中，随着不挥发含量的逐渐增加，涂料的黏度增大，假如此时，真溶剂大量挥发则稀释剂的比例相对增大，就会促使涂料突然变稠而丧失了流动性，引起气泡、橘皮等涂膜缺陷。另外，溶剂的主要作用是在干燥成膜之前，保持全部的不挥发组分处于溶液状态，不使其中任何一种组分不溶析出，否则造成涂膜连续相破坏以及表面粗糙失光等现象。为了防止干燥过程中出现沉淀析出，必须根据不同挥发速率加以平衡，以达到残余在涂膜中的溶剂能保持不低于原来的溶剂比例。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 四、几种涂料溶剂选择",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 1．高固体分涂料中溶剂的选择  \n\n在高固体分涂料中，使用少量的助溶剂可以降低涂料黏度，减少放气，改善流动性。乙酸乙酯以及丁醇是用于降低黏度的两种主要溶剂。乙二醇醚和乙酸乙二醇醚酯的混合溶剂也可以改善流动性和降低放气。  \n\n用于高固体分涂料的溶剂选择不能依据溶解度参数理论，因为高固体分树脂具有较低的平均分子量，除了不溶于 200 号溶剂油外，溶于所有的溶剂。所以在溶解度参数一氢键参数图上没有办法确定树脂的溶解度区域边界，也就没有足够的糟确度来估计溶剂对树脂溶解度相互作用的影响。  \n\n通常，溶剂本身的低黏度可大大降低高固体分涂料的黏度。必须使用有高溶剂化能力的高沸点溶剂来获得良好的流动性。另外，由于低表面张力的涂料喷涂时容易断裂和雾化，所以应尽可能选择低表面张力的溶剂来得到低表面张力的高固体分涂料，以使涂料获得满意的喷涂效果。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2．水性涂料中溶剂的选择  \n\n在乳胶漆中，溶剂的作用主要是帮助分散的树脂粒子在水蒸发掉后聚集成膜。过去经常使用乙二醇醚或乙二醇醚酯，现在广泛使用 Texanol（2，2，4-三甲基-1，3-戊二醇单异丁酸酯）溶剂，因为它是丙烯酸类和乙烯基树脂非常有效的成膜助剂，且不溶于水。Texanol 使用量通常大约为固体树脂的 $10\\%$ 。200 号溶剂油经常用  \n\n作苯丙涂料的成膜助剂。  \n\n除了成膜助剂外，也使用二元醇，像乙二醇或丙二醇来控制湿边时间和流动性。在水性有光乳胶漆中，建议颜料应该在二元醇溶剂中而不是在水中分散，这样有助于把絮凝降低到最小程度，最大限度地提高光泽。二元醇的使用量一般占涂料总量的 $2\\%\\sim5\\%$ 。  \n\n水性涂料含有 $2\\%\\sim15\\%$ 的助溶剂，具体的量由树脂所决定。这些助溶剂与水混溶或在树脂存在下，可以任意比与水混溶。最重要的助溶剂如下。  \n\n(1)乙二醇醚类。包括异丙基乙二醇、丙基乙二醇、丁基乙二醇、异丁基乙二醇、丁基二乙二醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-异丙氧基-2-丙醇、1-丙氧基-2-丙醇、1-丁氧基-2-丙醇。  \n\n(2)醇类。包括乙醇、丙醇、异丙醇、丁醇、异丁醇、仲丁醇、叔丁醇。  \n\n丁醇本身并不能与水以任意比混溶，但在树脂存在下，它可与水以任意比混合。在水性涂料中，丁醇是比乙二醇醚更有效的溶剂，但其缺点是有刺激性气味。在水性涂料中的助溶剂会促使树脂与水的溶解，降低在水稀释过程中出现的最大黏度，改善涂料的流动性，右助于无缺陷涂膜表面的生成。  \n\n助溶剂和成膜助剂也用作乳胶漆的流动助剂，丙二醇不仅作为溶剂使用，它的吸湿性可以保证涂膜中有足够高的水含量，以利于在表面形成光滑涂膜。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3．气干型涂料中溶剂的选择  \n\n通常，长油度醇酸漆溶解在脂肪烃，如 200 号溶剂油中，外加 $1\\%\\sim2\\%$ 的双戊烯以防结皮。室内墙面漆，如蛋壳醇酸有光漆，使用低气味的脂肪烃溶剂，外加极少量的芳烃溶剂。用作金属的装饰底漆——短油度醇酸漆，常使用高芳烃含量的溶剂来提高溶解度和快干性。某些快干的醇酸漆可以全部用芳烃溶剂如二甲苯来稀释。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# 4．交联和烘烤漆中溶剂的选择  \n\n最佳共混溶剂的选择，主要受树脂体系、施工方法和固化条件的影响。可供选择替换的溶剂种类非常之多，故不可能给出任何普适建议。清漆体系所使用的溶剂必须对树脂有足够的溶剂化能力，并且在溶剂快速蒸出阶段，仍能溶解树脂。对于一个体系使用什么样的溶剂，必须从树脂和溶剂供应商处获得指导。在用多异氰酸酯交联的体系中，非常重要的一点就是不能使用含羟基或混有水的溶剂，因为它们会与-NCO 基反应。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# 5．厚膜涂料和多涂漆溶剂的选择  \n\n采用无气喷涂施工的耐腐蚀涂料体系，常以乙烯基树脂如氯乙烯共聚物作为基料。这种涂料为了获得较高的涂层厚度，通常需多道施工，每涂的干燥时间较短。故要求涂料的溶剂必须能迅速从涂料中挥发，涂料体系要保证快干，流动性好。这些性质只有通过精确协调溶剂各个组分而获得。在多涂漆中，选择面漆的溶剂必须注意底漆绝不能被向内迁移的溶剂溶胀，发生咬底。一般可选用中等强度的真溶剂（如醇和乙二醇醚）、稀释剂和非溶剂。  \n\n6．发白、光泽、流动性与溶剂的选择  \n\n当溶剂从涂料中挥发的时候，涂料的表层温度会下降。在较高湿度下，当涂料的表面温度低于露点时，水会冷凝，在涂膜表面形成白雾及泛白。如果涂料的溶剂中有吸水性溶剂如乙醇或乙醇酗存在，则水会被吸收，并在涂料中均匀分布，随着溶剂中其他组分的挥发而挥发，泛白不太会出现。如果涂料含有能与水形成共沸的溶剂如芳香烃或丁醇，则泛白现象可完全消除。  \n\n涂料干燥后的涂膜应该光滑、平整，而不应有涂料粒子在表面的集结。在涂膜形成过程中，如果真溶剂是最后挥发掉的，则涂料的光泽可以得到提高。乙二醇醚，由于特别有利于涂料的流动，故对光泽的提高很有益处。不好的涂料流动性会导致许多涂膜缺陷，像结皮、蜂窝状孔洞和鱼眼。这些缺陷要归因于物理因素，即溶剂挥发过程中涂料表面张力的变化和涂膜中涡流生成的协同作用。溶剂的快速挥发引起涂膜表面张力增加幅度远大于涂膜内部。使用慢速挥发、对树脂溶解能力强的溶剂可以阻止涂膜中涡流的产生。添 加能降低表面张力的组分，如润湿剂或硅油，也有良好的效果。  \n\n7．力学性能、残留溶剂与溶剂的选择由于以下一些原因，溶剂极大地影响着涂料的力学性能。  \n\n$\\textcircled{1}$ 溶剂通过对树脂分子的有序排列或阻止其有序化而影响涂膜的分子结构；  \n\n$\\textcircled{2}$ 溶剂在某种程度上会影响多组分漆的反应，起内增塑效应；  \n\n$\\textcircled{3}$ 残留溶剂在涂膜中起外增塑效应。  \n\n例如，乙二醇醚对聚酯树脂与三聚氰胺甲醛树脂固化体系有增塑作用，一些三聚氰胺树脂的官能团明显地被乙二醇醚所封闭。通过气相色谱和放射指示剂研究已经证实在共聚物涂料中，溶剂对涂膜发生增塑效应。干燥、固化了的涂膜对溶剂吸收程度各不一样。  \n\n二氯甲烷几乎可以溶胀所有的涂膜，有很好的除去涂料的作用。芳香族烃类溶剂对于用三聚氰胺树脂固化的聚酯烘烤磁漆的溶胀作用依赖于聚酯树脂的单体组成和烘烤后的交联度。",
+        "category": " Results and discussion"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,5677 @@
+[
+    {
+        "id": 1,
+        "chunk": "# COATINGS TECHNOLOGY 涂料工艺  \n\n第四版 上册  \n\n![](images/a1e1cf2b2a69bce6538fb2d70823bed3570489c571ee0c4239ffdd96e299cecb.jpg)",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# COATINGS TECHNOLOGY 涂料工艺  \n\n![](images/84147c8527a9561b787bd9a966564d63f769af404b74fd1575c1179043c9ebfe.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# COATINGS TECHNOLOGY",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 涂料工艺  \n\n第四版 上册  \n\n刘登良主编  \n\n《涂料工艺》第四版在保持第三版基本结构的基础上，从市场经济条件下对涂料技术发展和管理的要求出发进行修订。全书共分五篇：导论、涂料原材料、涂料各论、涂料的制造过程控制、涂装过程控制。涂料原材料篇尽量引入新观念、新材料、新原理和新标准，力求在与国际接轨的同时而又兼顾我国是发展中国家的现实，坚持先进性、实用性和经济性的统一。涂料各论篇按用途进行编写，涵盖涂料的基本品种，力求反映其现代技术水平，除提供实用的基础配方外重点讲述配方原理。涂料的制造过程控制篇介绍了涂料生产设备、涂料工厂设计、原料与产品的标准和检验，更加强调法规要求。涂装过程控制篇增加了涂料涂装工艺一体化的理念，强调了涂装现场管理和技术服务的重要性。  \n\n全书从涂料的基础知识、基本理论、原材料和产品性能要求和检测标准、配方原理、涂料生产过程控制、涂装工艺要求、涂装技术服务和涂装缺陷控制等方面对涂料工艺进行系统和全面的论述，帮助涂料行业从业人员树立涂料工艺的整体观，为涂料技术创新拓展思路。同时新版力求保持第三版实用性特点，所列配方翔实可靠，并标明原材料规格和供应商。本书可供涂料和涂装行业的工程技术人员、管理人员和技师阅读，也可作为大专院校相关专业师生的参考书。",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 图书在版编目（CIP）数据  \n\n涂料工艺/刘登良主编.—4版.—北京：化学工业出版社，2009.12ISBN 978-7-122-06676-3  \n\nI．涂ⅡI．刘Ⅲ涂料-工艺学ITQ630.1中国版本图书馆CIP数据核字（2009）第165727号责任编辑：顾南君 文字编辑：冯国庆、王琪、向东、咎景岩、林丹、李玥责任校对：宋夏 装帧设计：张辉  \n\n出版发行：化学工业出版社（北京市东城区青年湖南街13号 邮政编码100011)  \n印刷：北京永鑫印刷有限责任公司  \n装 订：三河市万龙印装有限公司  \n787mm×1092mm1/16印张129字数3428千字 2010年1月北京第4版第1次印刷  \n\n购书咨询：010-64518888（传真：010-64519686） 售后服务：010-64518899网址：http://www.cip. com. cn凡购买本书，如有缺损质量问题，本社销售中心负责调换。",
+        "category": " References"
+    },
+    {
+        "id": 6,
+        "chunk": "# 涂料工艺编委会  \n\n主编刘登良  \n\n编委 (按拼音排序)洪啸吟李荣俊 刘登良 刘国杰 刘会成 钱伯荣沈浩石玉梅 王 健 叶汉慈 虞兆年  \n编写人员 (按拼音排序)蔡国强 陈苹 戴蓉晖 杜长森 杜玲玲 杜阳方达经 冯俊忠 龚 骏 黄 安 黄徽波 金晓鸿赖华 李桂宁 李华刚 李继华 李荣俊 李少香李兴仁 林 安 林绍基 林雪南 林宣益 刘登良刘国杰 刘 红 刘会成 刘林生 刘宪文 刘新刘志刚 吕仕铭 罗先平 马赫 马宏 孟军锋孟庆昂 潘元奇 钱捷 钱叶苗 邱星林 任卫东史春晖 史英冀 宋志荣 孙凌云 唐 峰 唐海英田育廉 汪盛藻 王华进 王健 王利群 王庆生吴伟卿 吴智慧 谢劲 谢晓芳 徐锋 杨建文杨其岳 叶汉慈 易海瑞 虞兆年 袁林森 张纯名张剑秋 赵君 赵琪慧 曾光明 周琼辉 周志朱红朱洪 朱龙观 祝家洵  \n支持单位 (排名不分先后)中国涂料工业协会海洋化工研究院 中海油常州涂料化工研究院 格北京红学限公限公司 众 碧陕西宝塔山油漆股份有限公司 中中远关西涂料化工有限公司中华制漆（深圳）有限公司  \n\n《涂料工艺》自1970年问世，历经 $1992\\sim1996$ 年改版为6个分册，1997年再改为第三版的合订两册。《涂料工艺》第二版于1997年获第八届全国优秀科技图书二等奖；于1998年获国家石油和化学工业局科技进步二等奖。作为涂料行业集体智慧的结晶和权威的专著哺育了两代涂料专业技术和管理人员，功不可没。但是，对涂料工艺的认识基本上还处在计划经济的思维体系和框架中。最近十几年来，在改革开放和国民经济快速稳定增长，以及中国成为“世界制造基地”，在经济全球化和市场国际化的推动下，中国涂料行业的发展进入了快车道。从20世纪90年代的100万吨/年猛增至2008年的600多万吨/年，中国已成为世界第一大涂料生产和消费国。世界排名前二十位的跨国公司都已进入中国市场并完成了本地化生产的战略布局，成为中国涂料行业重要组成部分。再加上大批原材料、涂料设备和检测仪器供应商的进驻，中国涂料行业的技术发展水平、产品结构和管理水平迅速与国际接轨，融入国际化竞争的大环境。与此同时，在涂料研发和生产工艺控制中，ISO9001质量管理体系、ISO14001环境管理体系、ISO-18000安全和职业健康管理体系等先进的管理理念在行业中实践了十多年。而可持续发展的科学发展观对行业的技术发展方向提出更高的要求：节能、减排、省资源、安全和环保，以及日益从紧的法律法规。涂料行业与涂装行业紧密结合，为用户提供满意的服务和最终效果，实现由涂料制造业向“加工服务业”转变的理念将推动涂料行业技术迈向新的台阶。此外，新版中还引入技术经济的观念。作为工艺学，处理好技术发展的先进性、实用性、可行性、经济性和可靠性-风险分析等之间的关系，并适当地介绍现代技术研发R&D的项目管理的基础要求，以提高研发的效率和效益。以上所述正是《涂料工艺》第四版编写的宗旨。  \n\n在整体结构保持第三版基本框架的基础上，按新的涂料分类标准GB/T2705—2003向国际标准靠拢，全书分为五篇：导论—涂料基础知识和原理、涂料工艺范畴；原材料篇—介绍了成膜物、颜料、分散介质和助剂；涂料各论篇—按用途叙述，充实内容、拓展领域：涂料制造过程控制篇-—涂料原材料、中间体和成品检测与质量控制，突出法律和法规的要求，补充现代质量管理体系；涂装过程控制篇—突出涂料涂装一体化的理念、涂装现场管理和技术服务。帮助工程技术人员建立系统的涂料工艺观—从原材料控制、涂料配方设计理论、涂料生产工艺、涂料性能检测至涂装工艺研发和涂装技术服务体系等。  \n\n本次改版工作得到中国涂料工业协会全力支持。以中涂协专家委员会为基础，动员了七$^+$ 多位专家参与写作，力求从国际化视野反映我国目前涂料行业的技术水平，并对未来国际化竞争环境下涂料工艺的发展趋势加以阐述。同时聘请涂料行业的资深专家担任编委对各篇进行把关，其具体分工如下：虞兆年和洪啸吟负责原材料树脂、分散介质的审定，钱伯容负责颜填料、助剂、卷材涂料的审定，石玉梅负责建筑涂料的审定，叶汉慈负责不饱和树脂、木器涂料和塑料涂料的审定，沈浩负责涂料原材料和产品检验、涂料生产设备、工厂设计的审定，刘国杰负责有机硅树脂、航空航天涂料的审定，刘会成负责集装箱涂料、涂装过程控制篇的审定，王健和李荣俊负责海洋涂料和重防腐涂料的审定，刘登良负责导论编写及其余部分的审定并通审全稿。希望广大读者一如既往地支持《涂料工艺》新版发行，多提宝贵意见，以利于不断改进，办成精品，保持其在涂料行业的权威地位，为推动中国涂料行业的发展继续做贡献。  \n\n海洋化工研究院、中海油常州涂料化工研究院、江苏兰陵化工集团有限公司等对编委会的工作提供大力支持，在此表示衷心感谢！  \n\n《涂料工艺》编委会2009年9月",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 第一章涂料、涂层及涂料工艺的范畴…1",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "#  \n\n第一节涂料及涂层的功能和应用. 1  \n一、保护作用 -涂层的基本功能.  \n二、装饰作用 2  \n三、功能作用 2  \n第二节涂料的组成和分类. 3  \n一、涂料的基础成分 3  \n二、涂料的分类  \n第三节涂料的附着 8  \n一、附着力的本质及影响附着力的因素……8  \n二、提高涂层附着力的技术途径 12  \n第四节涂料的成膜及控制因素 ..... ▪▪▪11 12  \n一、与成膜过程有关的基本概念· ▪13  \n二、物理方式——溶剂挥发成膜 \\* 13  \n三、聚合物分散体系的成膜 14  \n四、化学方式成膜 ▪……14  \n第五节涂料工艺的范畴 16  \n第六节涂料开发、生产和服务过程的管理 18  \n一、质量管理体系 18  \n二、环境管理 19  \n\n第二章涂料工艺的发展 20  \n第一节涂料.．发展的推动力.……20一、经济发展的需求是涂料行业和涂料工艺进步的原动力 .….20二、科学和技术进步是涂料工艺发展的推动.．． .…20三、涂料工艺与涂装．艺相互促．21四、符合可持续发展战略和法律法规要求….21  \n第二节涂料工艺的发展 ..21、应用基础研究是创新和发展的基石…22二、涂料原材料的发展 ·三、涂料产品的结构调整 .23  \n四、涂料和涂层性能检测方法的科学化和标准化. ▪23  \n五、涂料工艺与涂装工艺的发展密切结合、相互促进.… .23  \n六、环境友好型涂料成为涂料工艺发展的主流 24  \n七、生产流程和管理创新促进高效、安全和环保涂料生产 24  \n参考文献 25",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "#",
+        "category": "ase provide the text segment you'd like me to analyze."
+    },
+    {
+        "id": 10,
+        "chunk": "# 第二篇涂料原材料",
+        "category": " Introduction"
+    },
+    {
+        "id": 11,
+        "chunk": "# 第一章涂料成膜物树脂 26",
+        "category": " Introduction"
+    },
+    {
+        "id": 12,
+        "chunk": "# 第一节松香树脂 吴伟卿26  \n\n一、原料 26  \n二、松香树脂生产设备 ·28  \n三、松香树脂的质量指标 …29  \n四、松香树脂分类与合成 29  \n五、松香树脂的应用 ▪33  \n\n第二节醇酸树脂 田育廉35  \n\n、概述 35  \n二、醇酸树脂的分类 35  \n三、醇酸树脂的有关化学反应与相关理论…36  \n四、醇酸树脂的性质和配方计算 39  \n五、醇酸树脂的制造 52  \n六、醇酸树脂的应用 68  \n七、醇酸树脂的改性 71  \n八、醇酸树脂的发展趋势 ·102",
+        "category": " Introduction"
+    },
+    {
+        "id": 13,
+        "chunk": "# 第三节酚醛树脂…张剑秋伟卿108  \n\n概述 108",
+        "category": " Introduction"
+    },
+    {
+        "id": 14,
+        "chunk": "# 二、原料 109",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# 三、酚醛树脂合成的基本化学反应…111  \n\n四、酚醛树脂 113  \n五、酚醛树脂的应用 119",
+        "category": " Introduction"
+    },
+    {
+        "id": 16,
+        "chunk": "# 第四节 氨基树脂… 吴伟卿120  \n\n、概述 120  \n二、氨基树脂所用的原料 121  \n三、氨基树脂的分类 125  \n四、氨基树脂的合成 125  \n五、氨基树脂的生产设备 146  \n六、涂膜固化反应 147  \n七、氨基树脂的应用 149  \n八、氨基树脂生产和使用时的VOC 157",
+        "category": " Introduction"
+    },
+    {
+        "id": 17,
+        "chunk": "# 第五节饱和聚酯树脂··.吴伟卿张剑秋158  \n\n概述 158  \n、聚酯树脂所用的原料 159  \n三、聚酯树脂合成的基本化学反应 162  \n四、聚酯树脂的生产工艺 168  \n五、饱和聚酯树脂的分类与制备 171  \n六、饱和聚酯树脂的应用 185",
+        "category": " References"
+    },
+    {
+        "id": 18,
+        "chunk": "# 第六节丙烯酸树脂…蔡国强朱龙观188  \n\n、概述 188  \n二、溶剂型丙烯酸树脂…· 190  \n三、水溶性丙烯酸树脂 236  \n四、丙烯酸乳液 243  \n五、辐射固化丙烯酸酯涂料.. 254",
+        "category": " References"
+    },
+    {
+        "id": 19,
+        "chunk": "# 第七节环氧树脂与涂料…·…虞兆年258  \n\n一、概况. 258  \n二、环氧树脂的特性指标和牌号· 263  \n三、环氧树脂的制造.· 266  \n四、环氧树脂的固化剂 ·275  \n五、胺固化环氧树脂漆. 280  \n六、水性环氧树脂漆. .297  \n七、环氧树脂的分析方法 302",
+        "category": " Introduction"
+    },
+    {
+        "id": 20,
+        "chunk": "# 第八节聚氨酯与涂料… 虞兆年302  \n\n、概况 302  \n二、化学原理 305  \n三、制漆工艺 329  \n四、安全、计算 378",
+        "category": " References"
+    },
+    {
+        "id": 21,
+        "chunk": "# 第九节聚脲树脂 黄微波386  \n\n、概述 386  \n二、聚脲树脂所用原料 387  \n三、聚脲化学反应原理 407  \n四、喷涂聚脲弹性体结构与性能的关系 ·413  \n五、喷涂聚脲弹性体的性能 419  \n六、底材处理与施工工艺 424",
+        "category": " Introduction"
+    },
+    {
+        "id": 22,
+        "chunk": "# 七、安全防护 428",
+        "category": " Introduction"
+    },
+    {
+        "id": 23,
+        "chunk": "# 第十节氯化聚烯烃树脂及  \n\n应用... 王华进赵 君429  \n、氯化橡胶· 429  \n二、氯磺化聚乙烯.· 433  \n三、过氯乙烯… 434  \n四、高氯化聚乙烯树脂 ·435  \n五、氯醚树脂 436  \n六、其他的氯化聚烯烃树脂 438",
+        "category": " References"
+    },
+    {
+        "id": 24,
+        "chunk": "# 第十一节硝酸纤维素…·…·…·林雪南邱星林438  \n\n、概述 438  \n二、硝酸纤维素的生产工艺 438  \n三、硝酸纤维素的分类及应用· 439  \n四、硝酸纤维素的溶解 ·443  \n五、硝酸纤维素的运输、贮存和应用的安全  \n问题.… 445",
+        "category": " Introduction"
+    },
+    {
+        "id": 25,
+        "chunk": "# 第十二节有机硅树脂涂料…．刘国杰446  \n\n概述 446   \n、有机硅功能与专用性树脂涂料 447   \n三、氟化基团改性有机硅涂料 451   \n四、有机硅高固体分涂料 459   \n五、辐射固化有机硅涂料 465   \n六、有机硅乳胶树脂涂料 471",
+        "category": " Introduction"
+    },
+    {
+        "id": 26,
+        "chunk": "# 第十三节氟碳树脂.… \\*\\* \\*+\\* 刘宪文476  \n\n、常用氟化物单体. 479  \n二、溶剂型氟碳树脂 480  \n三、水性氟碳树脂· 487  \n四、粉末氟碳树脂 492  \n参考文献.… 498",
+        "category": " References"
+    },
+    {
+        "id": 27,
+        "chunk": "# 第二章颜料与填料…吕仕铭杜长森504",
+        "category": " Introduction"
+    },
+    {
+        "id": 28,
+        "chunk": "# 第一节颜料与填料的概述. ▪▪504  \n\n一、颜料与填料的定义 504  \n二、颜料与填料的作用 ·504  \n三、颜料与填料的分类· 505",
+        "category": " Introduction"
+    },
+    {
+        "id": 29,
+        "chunk": "# 第二节 颜料的特性和指标… 505  \n\n、颜料基本性能…· .506  \n二、颜料标准及检验方法· 513  \n三、颜料的特性…· 513",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 30,
+        "chunk": "# 第三节．.料与填料．各……·4  \n\n、无机颜料 514  \n二、有机颜料 524  \n三、填料（体质颜料） 537  \n四、特种功能颜料 541",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 31,
+        "chunk": "# 第四节着色与配色原理-色彩学.550",
+        "category": " References"
+    },
+    {
+        "id": 32,
+        "chunk": "# 一、色彩学的意义 550  \n\n二、颜色基本概念 550  \n三、色彩基本理论 551  \n四、同色异谱颜色 556  \n五、颜色的测量 556",
+        "category": " References"
+    },
+    {
+        "id": 33,
+        "chunk": "# 第五节色浆和电脑调色 .▪557  \n\n、色浆（颜料制备物） 557  \n二、配色 561",
+        "category": " References"
+    },
+    {
+        "id": 34,
+        "chunk": "# 第六节颜料和填料的发展趋势· .▪564  \n\n、开发高性能颜料品种 564  \n二、颜料表面处理 564  \n三、颜料与填料的超微粉碎或纳米化 565  \n四、颜料与填料的剂型化 565  \n五、颜料与填料的环保化 565  \n考文献 565",
+        "category": " References"
+    },
+    {
+        "id": 35,
+        "chunk": "# 第三章分散介质和溶剂.刘完文567  \n\n第一节概述. 567  \n第二节水的主要特性· 567  \n第三节有机溶剂的主要特性指标及应用.568  \n、溶解力 569  \n二、黏度. 584  \n三、挥发速率 587  \n四、表面张力 596  \n五、电阻率 597  \n六、毒性和安全性 599",
+        "category": " Introduction"
+    },
+    {
+        "id": 36,
+        "chunk": "# 第四节活性分散介质· 610  \n\n一、无溶剂环氧涂料用.活性稀释剂.610  \n二、聚氨酯涂料用活性稀释剂 612  \n三、光固化涂料用活性稀释剂.. 612  \n四、活性稀释剂的毒性. 617  \n五、活性稀释剂的贮存和运输.…· .618",
+        "category": " Introduction"
+    },
+    {
+        "id": 37,
+        "chunk": "# 第五节涂料常用有机溶剂.. 618  \n\n、脂肪烃类溶剂 618   \n二、芳香烃类溶剂 619",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 38,
+        "chunk": "#  \n\n二、帖薄类溶剂 623  \n四、醇类溶剂 623  \n五、酮类溶剂 625  \n六、酯类溶剂.· .627  \n七、醇醚及醚酯类溶剂 629  \n八、取代经类溶.…· .·631  \n九、其他溶剂.… .632  \n第六节有关环保法规 633  \n一、国外涂料工业环保发展历程.. .633  \n二、我国涂料工业环境保护现状 636  \n第七节发展趋势.… 637  \n参考文献 638",
+        "category": " References"
+    },
+    {
+        "id": 39,
+        "chunk": "# 第四章 助剂 640  \n\n第一节助剂的分类、作用及整体匹配性. 杨其岳640一、涂料助剂的作用及分类 640二、涂料助剂应用．整体匹配性643",
+        "category": " Introduction"
+    },
+    {
+        "id": 40,
+        "chunk": "# 第二节助剂各论 645  \n\n、润湿分散剂. 杨其岳645   \n二、流平和防流挂剂. 杨其岳654   \n三、防沉剂. 林宣益664   \n四、消泡剂…. 林宜益666   \n五、消光剂··· 杨其岳674   \n六、防浮色发花剂 杨其岳677   \n七、增稠剂… 林宣益683   \n八、催干剂和防结皮剂. 林宜益688   \n九、防腐剂.、、防霉剂和防藻剂.．林宣益696   \n十、光稳定剂. ·杨建文703   \n十一、成膜助剂… 林宣益707   \n十二、乳化剂.… ·林宣益713   \n十三、特种功能添加.. 林宣益718   \n考文献… 林宣益719",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 41,
+        "chunk": "#",
+        "category": "ovide the text segment about hydrophilic polymers for analysis."
+    },
+    {
+        "id": 42,
+        "chunk": "# 第三篇涂料各论",
+        "category": " Introduction"
+    },
+    {
+        "id": 43,
+        "chunk": "# 第一章 建筑涂料 720",
+        "category": " Introduction"
+    },
+    {
+        "id": 44,
+        "chunk": "# 第一节乳胶漆 林宣益720  \n\n一、乳胶漆概述· 720  \n二、乳胶漆的组成.· 723  \n三、乳胶漆的配方设计 727  \n四、乳胶漆的生产 747  \n五、乳胶漆的品种. .….759  \n六、乳胶漆的成膜机理和涂膜结构· …766  \n七、外墙保护理· 769  \n八、乳胶漆性能评价.· 771  \n九、乳胶漆的进展 ..777  \n十、乳胶漆的涂 787  \n第二节溶剂型建筑涂料…．徐峰799  \n一、定义、种类与性能特征. .▪.799  \n二、丙烯酸酯类和丙烯酸酯-聚酯类外墙  \n涂料. .81  \n三、有机硅建筑涂料… 803  \n四、聚氨酯类外墙涂料和氟树脂建筑  \n涂料 804  \n五、金属光泽外墙涂料. .…806  \n六、溶剂型耐酸雨涂料 .807  \n七、溶剂型涂料生产技术 ·808  \n八、技术性能指标. ·810  \n九、普通涂装的溶剂型建筑涂料施工  \n．…· ·813  \n十、氟树脂涂料仿铝板涂层施工技术·814  \n十一、应用与发展展望· 816  \n官三节无机建筑涂. 徐 峰817  \n一、定义、种类与性能特征 817  \n二、无机建筑涂料的应用及发展.. 818  \n三、无机建筑涂料的基料· 819  \n四、外墙无机建筑涂料的配制要点及生产  \n技术分析.. …821  \n五、外墙无机建筑涂料的技术性能要求…826  \n六、无机外墙建筑涂料.施．技.826  \n官四节建筑防水涂料… 徐 峰828  \n一、概述.. 828  \n二、聚氨酯防水涂料. .▪829  \n三、聚合物水泥防水涂料 .836  \n四、聚合物乳液防水涂料. 840  \n五、渗透结晶型防水涂料. 841  \n第五节其他功能型建筑涂料……….…·徐峰843  \n、概述... .▪843  \n二、抗菌、防霉涂料 ·843  \n三、可改善空气质量的内墙涂料. .845  \n四、保温隔热涂料 .846  \n参考文献… ▪851  \n第二章汽车涂料.. + \\*\\*\\* 汪盛藻852  \n第一节底漆及电泳底漆 ·852  \n\n、浸涂及自泳底漆 853  \n二、电泳底漆 855",
+        "category": " Introduction"
+    },
+    {
+        "id": 45,
+        "chunk": "# 第二节中间涂料 866  \n\n一、原料 868  \n二、几类中间涂料· 871  \n三、中间涂料的技术标准 872",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 46,
+        "chunk": "# 第三节 面漆 872  \n\n一、色浆 874  \n二、本色漆.… 883  \n三、金属闪光底色漆. 895  \n四、罩光清漆… 900  \n五、汽车面漆标准.· 907",
+        "category": " References"
+    },
+    {
+        "id": 47,
+        "chunk": "# 第四节底盘抗石击涂料 908  \n\n、PVC塑溶胶 908  \n二、聚酯型 909",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 48,
+        "chunk": "# 第五节汽车修补涂料 909  \n\n一、汽车修补涂料面漆系统的基本构成………909  \n二、辅料· -921  \n三、汽车修补涂料系统及计算机配色·…·….936",
+        "category": " References"
+    },
+    {
+        "id": 49,
+        "chunk": "# 第六节汽车涂料的涂装工艺. ▪937  \n\n、汽车原厂漆 938  \n二、汽车修补涂料 949",
+        "category": " References"
+    },
+    {
+        "id": 50,
+        "chunk": "# 第七节汽车涂料性能检验与漆膜缺陷···964  \n\n一、原漆性能检验 964  \n二、涂层性能检验· 973  \n三、漆膜缺陷、起因及解决措施 976",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 51,
+        "chunk": "# 第八节发展和展望 986  \n\n、阴极电泳底漆 987  \n二、中间涂料 988  \n三、底色漆…· 988  \n四、罩光清漆… ·988  \n五、汽车修补漆. ▪989",
+        "category": " Introduction"
+    },
+    {
+        "id": 52,
+        "chunk": "# 缩略语 989",
+        "category": " References"
+    },
+    {
+        "id": 53,
+        "chunk": "# 参考文献 990",
+        "category": " References"
+    },
+    {
+        "id": 54,
+        "chunk": "# 第一篇导论",
+        "category": " Introduction"
+    },
+    {
+        "id": 55,
+        "chunk": "# 第一章",
+        "category": " Introduction"
+    },
+    {
+        "id": 56,
+        "chunk": "# 涂料、涂层及涂料工艺的范畴",
+        "category": " Introduction"
+    },
+    {
+        "id": 57,
+        "chunk": "# 第一节涂料及涂层的功能和应用  \n\n我国使用天然大漆的历史可追溯至2000多年前的西汉时期，但是涂料作为化工产品的生产仅有100多年，直到20世纪初涂料用的主要成膜物树脂还来源于植物油（包括合成醇酸树脂）、沥青及煤焦油等天然产物，而且以溶剂型液态产品供应市场，俗称“油漆”，并沿用至今，对应于英文paint。近代涂料通常对应于coatings，不仅意味着使用更为广泛的合成材料作为成膜物树脂，而且实质上包含将不同形态的涂料通过涂装过程coatings转变成涂层材料而发挥其功能。严格来讲，涂料公司生产的涂料产品只是“半成品”，只有涂层或涂膜才是满足用户需求的最终产品。从这个意义上讲，涂料应称为涂层材料，涂料行业不完全是制造业，某种意义上，应归属于“加工服务业”。涂料和涂装是不可分割的整体，涂料生产商有责任帮助用户选择适用的涂料和配套体系，同时指导用户正确涂装和使用涂料，直到获得满足用户需求的涂层。  \n\n广义上讲，涂层材料包括无机和金属涂层（例如热喷涂，等离子喷涂铝、锌及耐高温贵金属合金涂层，电镀和高真空金属镀膜，无机富锌涂层等）；有机涂层，以有机聚合物为成膜物的涂层材料是市场上涂料的主体；近年来正在发展的有机-无机杂化涂层材料，例如以sol-gel法制备的有机改性硅氧烷杂化树脂材料等。所有的涂层材料都必须采用适当的涂装设备和涂装工艺将其转变成适用的涂层或涂膜。本书主要讨论有机涂料，适当涉及以无机成膜物、有机-无机杂化树脂为主的特种涂料。  \n\n涂料形成的涂层对被涂装的底材——金属、木材、混凝土、塑料、皮革、纸张、玻璃等具有保护、装饰和功能化的作用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 58,
+        "chunk": "# 一、保护作用———涂层的基本功能  \n\n暴露在大气环境中的物体会遭受多种腐蚀因素的侵蚀。氧、水和电解质、酸雨、盐雾等引起金属电化腐蚀，紫外线引起塑料、木材和纸张降解，空气中的二氧化碳和酸雨导致混凝土风化变质，微生物及代谢产物对所有底材具有很大的破坏作用，并污损其外观。  \n\n接触各种腐蚀介质的容器内壁（油罐，溶剂贮罐，水、酸、碱、盐等贮运设施，油、气、水等管道)，污水处理池，海港设施等常年处于侵蚀状态，最为典型的是船舶及沿海设施处于十分严酷的腐蚀环境，涂层防腐是延长其使用期最基本的要求。涂层能够隔离和屏蔽腐蚀介质与底材作用，或者通过特殊添加剂延缓腐蚀而达到保护底材的目的。家具和塑料制品经常接触洗涤剂、酒精、醋等腐蚀介质，也需要适当的保护。  \n\n所有的产品和设备经常受到各种机械冲击、划伤、狂风暴雨的冲刷、风沙的磨损等，均需要涂层进行保护。",
+        "category": " Introduction"
+    },
+    {
+        "id": 59,
+        "chunk": "# 二、装饰作用  \n\n涂层可以充分改变底材的外观，赋予其绚丽灿烂的色彩、不同的光泽、丰富的质感、表面花纹等美术和装饰效果，满足用户日益多样化和个性化的需求。汽车、塑料、家具、仪器仪表、皮革和高级纸张等高装饰性涂层往往是产品附加值的重要组成部分。涂料的性能和涂装工艺的结合是达到预定装饰效果的基础。",
+        "category": " Introduction"
+    },
+    {
+        "id": 60,
+        "chunk": "# 三、功能作用  \n\n保护和装饰本身也是一类功能，这里所指的是特种功能——特种涂层材料的功能，集中体现在与国防军工相关的应用领域。例如，电磁屏蔽，吸收雷达波，吸收声呐波，吸收和反射红外线等隐形和伪装涂层，太阳热反射或吸收涂层，舰船防污涂层，防火涂层，耐高温涂层 $(200\\sim2000^{\\circ})$ ，隔热绝热、烧蚀涂层，阻尼降噪声涂层，甲板防滑、防结冰涂层，自清洁热反射船壳涂层等。市场对特种功能涂料的需求越来越多，例如，建筑涂料中的屋顶防水、隔热、热反射涂料，内墙用的防水、防虫、防霉涂料等。  \n\n不同的底材，被涂产品的使用环境、使用要求、性价比不同，对涂层材料的性能要求侧重点不同，它们均体现在涂料性能的技术指标上，与保护作用相关的如耐水性、耐油性、耐化学介质性、耐盐雾性、耐湿热性、耐人工和大气老化性等；与装饰性有关的如光泽、透明度、硬度、耐划伤性、色差、雾影等。特种涂层都有特殊的功能指标及测试方法，技术指标的确定可以采用或参考已颁布的各种标准（国际标准、国家标准、行业标准、企业标准、与用户的协议或合同标准等)。市场经济条件下，用户需求更加多样化和个性化，更重要的是与用户充分沟通，尽可能准确辨识和把握用户的需求，从而采用更合理指标。但是，测试方法必须标准化，必须采用ISO、ASTM或国家标准方法进行涂层性能检测。  \n\n涂层发挥其作用的基础是具备一定的物理机械性能。涂层的强度（压缩、拉伸、断裂等)、柔韧性、耐冲击性、硬度、弹性、耐高低温循环性、耐磨性和耐划伤性等也是不可缺少的性能要求。  \n\n涂料必须经过涂装成膜是涂料发挥功能的前提，因此与施工、涂装和成膜相关的涂料性能要求也至关重要。其中包括以下几点。 Q  \n\n$\\textcircled{1}$ 涂料对底材润湿和渗透性；涂料与底材及涂层之间的附着力，与涂装间隔相关的可重涂性、涂装间隔时间；干燥时间（表干、硬干等）等。  \n\n$\\textcircled{2}$ 涂料的流变性及对涂装工艺的适应性，这对于在线涂装的OEM涂料尤其重要，涂料施工流平、防流挂、干燥时间控制是成膜关键。  \n\n$\\textcircled{3}$ 涂层配套体系和涂层厚度、单位面积涂料量控制和优化。  \n\n$\\textcircled{4}$ 涂料施工性能对施工环境的适应性。环境的温度、湿度、通风条件及底材清洁度等对涂料成膜具有重要影响。  \n\n涂料产品本身，液体涂料或粉末涂料应保证出厂性能指标，如固体含量、颜色、分散稳定性、贮存稳定性（剪切、冻融循环、定期贮存）等。俗称涂料的“开罐性能”—液体涂料呈现良好的流动性和分散性。  \n\n在市场日益规范，法律法规更加严格的环境下，满足环保要求、安全要求是涂料产品进入市场的许可证。  \n\n当然，在激烈的市场竞争条件下，技术经济指标一—产品的性价比也是不可忽视的因素。  \n\n此外，单一涂层使用并不多，主要是以配套体系为主—底漆、中间层和面漆等。涂装配套体系设计也是涂料工艺的重要内容，它一般体现为各种涂装规范和标准。  \n\n综上所述，涂料的研发、选用、涂装过程涉及多种复杂甚至矛盾的性能要求因素，这是一个不断优化的过程，需要从整体上去把握和平衡各种性能要求，从而达到较好的结果。  \n\n涂料行业在我国属于精细化工领域，专业上与胶黏剂、油墨相近。涂层无处不在，大至飞机、船舶、车辆、建筑物、桥梁，小至玩具、文具，如同人要穿衣服一样，几乎所有的物体都需要涂层保护。随着我国国民经济的快速稳定的发展，涂料行业以高于国家GDP增长速度的增速发展，据不完全统计，2008年我国涂料总产量达到638万吨，仅次于美国居世界第二位。但是，人均涂料消费水平远远低于发达国家，随着国民经济发展和人民消费水平提高，中国涂料市场具有巨大的发展潜力。中国加人WTO后，市场国际化和经济全球化，成为“世界制造基地”，为中国涂料行业发展提供了巨大的空间和机遇。与此同时，在中国涂料市场的竞争中体现得特别明显，世界排名前十位的涂料跨国公司均已进入中国。国外先进的技术和产品、管理理念和制度对中国涂料行业的技术进步和管理水平提升具有重大的推动作用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 61,
+        "chunk": "# 第二节涂料的组成和分类  \n\n涂料是由成膜物、分散介质、颜填料及助剂组成的复杂的多相分散体系，涂料的各种组分在形成涂层过程中发挥其作用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 62,
+        "chunk": "# 一、涂料的基础成分",
+        "category": " Introduction"
+    },
+    {
+        "id": 63,
+        "chunk": "# 1.成膜物  \n\n也称树脂，黏合剂或基料。它将所有涂料组分黏结在一起形成整体均一的涂层或涂膜，同时对底材或底涂层发挥润湿、渗透和相互作用而产生必要的附着力，并基本满足涂层的性能要求（清漆或透明的涂层主要由成膜物组成)，因此成膜物是涂料的基础成分。  \n\n涂料成膜是十分复杂的过程，下节将详细讨论。绝大多数涂料都是由液态湿膜转变为固体涂层（粉末涂料也是先熔化成液态，成膜后冷却固化）。有机成膜物树脂的化学组成和结构、分子量大小及分布，溶解度参数，极性及极性基团的结构和分布，交联反应型树脂的活性基团的含量及分布，玻璃化温度T等基本性质直接决定了涂层的性能，而且与液体分散体系的分散稳定性、流变特性乃至成膜的整体均一性密切相关。选择适当的成膜物并充分了解其特性是开发涂料新产品关键的第一步。  \n\n近半个多世纪以来，化学工业和材料科学的迅猛发展，成膜物树脂产品层出不穷，推动涂料行业的不断升级。成膜物习惯上可按如下方式分类。  \n\n(1）按有机、无机分类  \n\n$\\textcircled{1}$ 有机成膜物天然和合成聚合物，化学改性的天然树脂等，它们是涂料的主体一构成有机涂层材料。  \n\n$\\textcircled{2}$ 无机成膜物以聚合硅酸盐或磷酸盐为黏合剂主体，例如高模数硅酸钾、硅酸锂、聚合磷酸锌等。  \n\n$\\textcircled{3}$ 有机-无机杂化树脂近十几年发展起来的新型树脂成膜物，以硅、钛溶胶改性有机聚合物，具有纳米结构的成膜物体系为代表，还有环氧改性的聚合磷酸盐等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 64,
+        "chunk": "# (2）按热塑性、热固性分类  \n\n$\\Phi$ 热塑性（thermoplastic）树脂成膜物分子量较大的天然或合成的聚合物树脂，例如聚合改性松香、沥青、虫胶、硝基纤维素、醋酸丁酸纤维素CAB、氯化橡胶等天然及化学改性树脂，丙烯酸、氯磺化聚乙烯、过氯乙烯、高氯化聚乙烯及聚丙烯等合成氯化聚烯烃树脂、聚乙烯缩甲醛、聚醋酸乙烯、聚醋酸乙烯-乙烯树脂等合成线型聚合物树脂等。通常将它们溶解在适当溶剂体系中配成树脂溶液制备涂料，通过溶剂蒸发后固化成膜。树脂的化学结构成膜前后基本不变（物理状态，分子缠绕等可能有变化)。热塑性树脂的玻璃化温度$T_{*}$ 控制在室温以上，不能太高，树脂发脆，达到 $T_{*}$ 后树脂呈橡胶态发黏。其特点为涂层可熔、可溶。热塑性树脂的溶解度有限，很难制备高固体分涂料，VOC（有机挥发物）含量比较高，难以符合环保法规要求，将会越来越限制其应用范围。但是热塑性溶剂涂料具有单组分、快干、施工对环境条件变化不敏感、涂层装饰效果好等优点，仍占有相当大的市场份额。  \n\n$\\textcircled{2}$ 热固性（thermoseting）或交联型树脂它们是分子量较低、带有一定数量的可参加交联成膜反应的基团的低聚物（oligomer）树脂，在成膜过程中与外加固化剂反应交联成膜（环氧、聚氨酯、不饱和聚酯及聚脲涂料等)，或者吸收空气中氧与醇酸树脂不饱和键氧化交联，或者吸收湿气的单组分聚氨酯交联，以及空气中二氧化碳与硅酸盐反应为基础的无机树脂成膜机理，还有常温下情性，高温烘烤反应成膜的氨基树脂，粉末涂料中的环氧、环氧聚酯、聚酯树脂等。反应交联形成三维网状、分子量趋于无穷大的体型聚合物，生成的涂层不溶、不熔，比热塑性涂层具有更高的机械强度、更好的保护和装饰性能。热固性树脂大量应用于高性能工业涂料和特种功能涂料领域。由于热固性树脂分子量相对较低，并且可以溶解于可参与交联反应的活性溶剂，因此可加工成高固体含量、低VOC及无溶剂型涂料，也是环境友好型（environment-friendly）涂料发展方向之一。大多数反应型树脂与固化剂分别包装，使用前混合，存在施工使用期问题，而且固化成膜过程与施工环境关系很大，对涂装控制要求较高。  \n\n(3）按分散方式分类  \n\n$\\textcircled{1}$ 水分散型树脂—乳液（latex）以建筑乳胶涂料的基础乳液（纯丙烯酸、苯乙烯丙烯酸、醋酸乙烯-丙烯酸、EVA等乳液）为代表，它们用乙烯基类单体经乳液聚合工艺制备，以水为分散介质，VOC较低，为分子量较大的热塑性树脂。在水分蒸发过程中树脂乳胶粒子聚结，搭接后成膜。涂层由于亲水乳化剂或亲水基团存在，其耐水性不如相应的溶剂型树脂涂层。乳液也可经树脂溶解于溶剂后外加乳化剂经机械分散后脱溶剂的工艺制备，称为后乳化工艺。近年来采用将亲水基团（一COOH、一 $\\mathrm{OCH}_{2}\\mathrm{CH}_{2}$ 一等）引入树脂结构中制备可自乳化的树脂。同时热固性树脂乳液在工业涂料中的应用发展很快。乳液的稳定性、水稀释性、耐电解质性、剪切及冻融稳定性、流变特性、抗起泡性及成膜性等对制备涂料和成膜过程至关重要。乳液的形态及粒子大小和分布决定其稳定性和流变特性。一般乳液平均粒度 $0.5\\sim1\\mu\\mathrm{m}$ ，微乳（microemulsion）小于 $100\\mathrm{nm}$ ，即纳米乳液呈半透明带蓝、黄荧光状态。  \n\n②水可稀释型树脂（water-reducibe）通常先将单体溶解在亲水性较高的溶剂—丙二醇醚、丙酮、丁醇、N-甲基吡咯烷酮等中进行聚合反应，然后进行中和，并用水稀释。它们的VOC比相应的溶剂型涂料低，但比乳液型涂料高。  \n\n③有机分散型树脂将树脂溶解在强溶剂中，再加脂肪烃在特种表面活性剂存在下稀释而成的有机乳液。它们的成膜性优于水乳液，而且主体分散介质为低毒的脂肪烃，可制备VOC较低的涂料。这类成膜物体系正在开发之中。  \n\n④气-固分散型树脂以粉末涂料为代表。树脂具有较高的软化点，与颜料和助剂加工粉碎成一定粒度的细粉，经静电喷涂于加热的底材上熔化交联成膜。粉末涂料为环境友好型涂料的代表之一，几乎无VOC。  \n\n（4）按树脂成膜物的化学结构和来源分类我国涂料行业一直采用这种分类法，并写入国家标准，共17大类：油脂、天然树脂、酚醛树脂、沥青、醇酸树脂、氨基树脂、硝基纤维素、纤维素酯、纤维素醚、过氯乙烯树脂、烯类树脂、丙烯酸树脂、聚酯树脂、环氧树脂、聚氨酯树脂、元素有机化合物、橡胶及其他。但是，近年来成膜物树脂发展很快，上述分类已不能反映现实，本书在尊重历史和习惯的同时，尽可能与国际接轨，介绍更多、更新的成膜物树脂。  \n\n现代涂料工艺配方中采用单一成膜物树脂的不多，往往将几种树脂共混改性以提高涂料性能。因此，树脂的混溶性成为人们关注的重点，以此保证形成均一的涂层。但是，不同的树脂并非一定要在涂料中保持均一混溶状态。为了制备单组分热固性涂料，可以将树脂和固化剂做成互不相溶的两个相，在成膜时借助加热或其他方式使二者混溶反应成膜。还有正在发展的一涂分层涂料，其树脂混合物或在涂料中混溶，在交联成膜过程中发生分相和分层；或者是混合的互不相溶的稳定分散相，成膜时一相向涂层表面迁移，一相朝底材迁移，发生分相成膜。",
+        "category": " Introduction"
+    },
+    {
+        "id": 65,
+        "chunk": "# 2.颜料和填料  \n\n颜料是色漆或有色涂层的必要组分。颜料赋予涂层色彩、着色力、遮盖力，增加机械强度，具有耐介质性、耐光性、耐候性、耐热性等。颜料以微细固体粉末分散在成膜物中，颜料的细度与粒度分布、晶型、吸油度、表面物理化学活性等，直接与其着色力、遮盖力，与树脂相互作用、分散稳定性、流变特性紧密相关。化学结构相同，但来源（天然或合成）不同，或生产工艺，甚至批次不同，颜料的上述性能指标可能有差别，这往往导致配色中的色差。  \n\n颤料的品种很多，大体上可分为如下几种。  \n\n(1）着色颜料二氧化钛（钛白)、立德粉为代表的白色颜料，炭黑、氧化铁黑等黑色颜料，以及无机和有机黄色、红色、蓝色、绿色等颜料。有机颜料的着色力、鲜艳度及装饰效果优于无机颜料，但其耐候性、耐热性、耐光性等不如无机颜料。  \n\n(2）体质颜料或填料它们以天然或合成的复合硅酸盐（滑石粉、高岭土、硅藻土、硅灰石、云母粉、石英砂等）、碳酸钙、硫酸钙、硫酸钡等为代表，细度范围 $200\\sim1200$ 目的产品均有，而且也有经过不同表面处理以适应溶剂型或水性涂料的产品。一般填料遮盖力和着色力较差，主要起填充、补强作用，同时也降低成本。但是，随着新改性的体质颜料出现，人们对它们与成膜物树脂相互作用认识的深入，体质颜料在涂层中的作用将重新定位。  \n\n(3）功能性颜料它们除了着色、填充等基本性能外，主要赋予涂层特种功能，种类繁多。其中防腐、防锈颜料为一大类，它们是金属防腐底涂层的必要成分，通过牺牲阳极、金属表面钝化、缓蚀、屏蔽等作用防止金属底材腐蚀。给予涂层特殊装饰效果的金属闪光颜料、珠光颜料、纳米改性随角异色颜料等。其他的防海生物附着的防污颜料，导电颜料，热敏、气敏颜料，电磁波吸收剂，防火、阻燃填料等结合各种特殊功能涂层的要求就不一一枚举了。  \n\n尽管颜料种类很多，上述分类及特征并非绝对的，往往一种颜料兼有多种功能。例如，绢云母一般归类填料，但其具有良好的紫外线屏蔽功能，也兼有一定的遮盖力；云母氧化铁是熟知的防锈颜料，同时又是高耐候的面涂颜料。充分认识和全面把握各种颜料的性能，发挥其技术和经济潜能还有很多工作要做。而且绝大多数情况下都是几种颜色混合使用，优化颜料组合保证涂料的分散稳定性、合理流变性及良好的成膜性需要做大量的筛选和优化工作。  \n\n颜料必须均匀地分散在分散介质中成为稳定的分散体才能发挥功能。因此，颜料的分散及分散稳定性至关重要。固体颜料粉末是多分散的颜料初级晶体的聚集体（粒度 $\\ 0.1\\sim$ $100\\mathrm{nm})$ ，在分散过程中借助机械剪切力将聚集体打开，同时发生与分散介质和成膜物之间（往往在分散、润湿助剂存在的条件下）的相互作用—润湿、分散、稳定过程，形成具有一定流变特性的稳定分散体系。颜料的分散性是颜料的重要特性之一，它与颜料的晶型、粒子大小及粒度分布有关。更重要的是其表面特性—表面张力、极性基团及活性、表面改性的程度以及含水量等。颜料的表面活性决定其与成膜物、助剂及分散介质之间的相互作用程度。通常无机颜料具有高表面张力和极性中心，而有机颜料表面张力低；有机溶剂表面张力为 $(30{\\sim}40)\\times10^{-3}\\mathrm{N/m}$ ，而水为 ${\\overline{{76\\times10}}}^{-3}\\mathrm{{N}}{\\overline{{/\\mathrm{{m}}}}}$ ，它们与不同颜料的相互作用完全不同。成膜物的分子大小不同，化学结构不同，它们与颜料的相互作用也不同，再加上助剂的结构和作用原理的差别，优化分散体系需要做大量的工作，这将在涂料制造工艺中详细研讨。  \n\n透明清漆和涂层往往采用醇溶性或油溶性-——溶于有机溶剂的染料作为着色剂。通常染料的耐热性和耐光性不如颜料。近年来纳米分散的颜料用于透明涂层着色日益受到人们的重视。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 66,
+        "chunk": "# 3.分散介质  \n\n涂料作为分散体系（液-液、液-固、气-固、固-固)，分散介质的作用是确保分散体系的稳定性、流变性，同时在施工和成膜过程中起重要作用。溶剂型液体涂料中的分散介质一般称为溶剂，它们首先将成膜物树脂溶解成适合配方要求的溶液，涂料制备过程中调节产品的黏度及流变特性，在涂装过程中调节施工黏度和控制成膜速率及流变特性，这类溶剂又称稀料或稀释剂。溶剂的作用是多方面的，在热固性涂料中，溶剂的极性、亲质子性等对交联反应速率起调节作用。因此全面了解溶剂的溶解力、挥发性、黏度、表面活性、电性能（静电喷涂）等对选择正确的溶剂十分重要。传统的溶剂型涂料成膜后溶剂不留存于涂层中，挥发到大气中成为污染源之一，而且绝大多数有机溶剂都有毒性，易燃易爆。因此，了解溶剂的毒性和安全性是必要的，发达国家的产品说明中要求提供材料的卫生安全数据MSDS。随着VOC和HAPS（有害空气污染物）法规要求日益严格，对涂料中溶剂的用量和种类限制是涂料工艺面临的巨大挑战之一。高固体和无溶剂液体涂料，包括光固化涂料为降低VOC主要采用反应型或活性溶剂，它们参与交联成膜不挥发到大气环境中。但是，它们仍然具有一定的蒸气压，如接触皮肤会引起炎症。  \n\n水乳和有机分散系中分散介质为水或溶解力较弱的脂肪烃。它们通常不溶解成膜物树脂，成膜后挥发到大气中。树脂借助乳化剂和分散剂以超细液滴分散在介质中，在水等分散介质蒸发过程中通过毛细管作用凝聚，聚结成膜。对于热塑性的聚合物乳液往往将借助于成膜助剂—高沸点有机溶剂成膜。因此，虽然分散介质是环境友好的，但成膜助剂的种类和用量仍然受到法规限制。在标准条件下，温度23℃，相对湿度50%，乳胶涂料的干燥速率可能高于溶剂型涂料，这是因为成膜物不溶于水，没有分散介质遗留在涂层中。但是水性涂料的干性受环境条件（温度、相对湿度、通风等）的影响比溶剂型涂料大，因此对施工工艺的要求更高。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 67,
+        "chunk": "# 4.助剂  \n\n助剂，又称涂料辅助材料，其开发和应用是现代涂料工艺的重大技术成就之一。它们用量很少，在现代涂料的制备、贮运和涂装过程中对保证涂料和涂装性能起到重要的作用。水性及高性能、高装饰涂料中的助剂是不可或缺的组分。助剂在涂料成膜后一般留在涂层中成为其组分之一，所以在认识其主要功能的同时还应注意其对最终涂层的负面影响。例如，乳化剂是乳液不可缺少的成分，但残留涂层中的乳化剂的迁移性和亲水性势必影响涂层耐水性和附着力。  \n\n（1）助剂种类繁多，通常按助剂的功能分类润湿、分散剂，乳化剂，消泡剂，流平剂，防沉、防流挂剂，催干剂，固化剂及催化剂，增塑剂，防霉剂，平光剂，增稠剂，阻燃剂，导静电剂，紫外线吸收剂，热稳定剂，防结皮剂，以及用量较大的增塑剂，乳胶涂料的成膜助剂，防冻剂，防霉剂等。  \n\n(2）也有按其在涂料制备和涂装过程的作用分类  \n\n$\\Phi$ 涂料生产过程调节涂料性能助剂润湿、分散剂，乳化剂，消泡剂，流变调节剂——增稠剂、防流挂剂等。  \n\n$\\textcircled{2}$ 保证涂料贮存运输过程性能稳定性的助剂防沉淀剂，防结皮剂，防霉剂，防浮色、分色剂等。  \n\n$\\textcircled{3}$ 调整涂料施工涂装，改善成膜性的助剂流平剂、消光剂、防流挂剂、成膜助剂、固化剂及催干剂等。  \n\n$\\textcircled{4}$ 改进涂层特殊性能，提高耐久性的助剂紫外线吸收剂、热稳定剂、防霉剂、耐划伤剂、憎水或亲水处理剂等。  \n\n迄今为止，助剂的作用原理并不十分清楚，而且往往多种助剂在一种涂料中使用，由于助剂的结构和理化性质不同，而且大多数助剂都是不同类型的表面活性剂，它们在一起可能起协同作用，也可能起拮抗作用。此外，助剂与成膜物树脂、颜料及分散介质之间也存在复杂的相互作用，因此选择正确的助剂组合需要助剂供应商与配方师共同努力，进行大量的筛选工作。  \n\n还应注意，助剂不是万能的，涂料或涂层出现缺陷主要还是主体材料的问题或涂装工艺的不足，用尽可能少的助剂制备符合用户要求的涂料是合格配方师的基本要求。",
+        "category": " Introduction"
+    },
+    {
+        "id": 68,
+        "chunk": "# 二、涂料的分类  \n\n近代涂料经过100多年的发展，种类特别繁杂，由于地域和国家民族文化差异，涂料命名、专业用语至今难以统一。涂料分类方式很多，我国1981年颁布国家标准GB2705—1981，1992年又进行了修订和增补GB2705—1992。分类主要依据成膜物，涂料全名由成膜物名称代码、基本名称、涂料特征和用途、型号等组成。其中涂料采用习惯叫法-—漆，例如底涂与底漆，面涂与面漆。为了适应与国际接轨和市场经济的要求，新颁布的标准·GB2705—2003主要采用以涂料市场和用途为基础的分类法，同时对原分类法进行适当简化。主要包括如下几大类。  \n\n(1）建筑涂料建筑外墙面、内墙面涂料，防水涂料，地坪涂料，建筑防火涂料，功能涂料等。（2）工业涂料汽车涂料，木器涂料，铁路公路车辆涂料，轻工涂料（自行车、家用电器、仪表、塑料及纸张涂料等），防腐涂料（桥梁、管道、集装箱、耐高温涂料等）。  \n\n（3）其他涂料及辅助材料等。  \n\n以上几大类涂料中每一类中又按主要成膜体系细分，如建筑涂料分为合成乳液墙面涂料和溶剂型涂料两类。  \n\n新的涂料名称 $\\c=$ 颜色或颜料名 $^+$ 成膜物名 $^+$ 基本名称。省略代码要求，适应市场中企业自行编号状况。目前市场中还有习惯沿用的其他分类法，例如以下几种。  \n\n（1）按成膜方式分挥发型涂料、热熔型涂料、热塑性或热固性涂料。  \n\n(2）按包装分单组分涂料、双组分涂料。  \n\n(3）按涂装方法分刷涂、辊涂、喷涂、浸涂、淋涂、幕涂、电泳涂料等。  \n\n(4）按配套要求分腻子、着色剂、底漆、中间层、面涂与面漆（包括透明漆、色漆、罩光面漆)。  \n\n(5）按涂层光泽和艺术效果分高光、有光、半光、亚光、无光涂料。锤纹、橘纹、浮雕涂料等。  \n\n(6）按涂层功能及具体使用对象分蒸馏釜耐高温涂料、电子车间导静电地坪涂料等。这种名称再加上涂料公司的产品代码是目前市场上最通行的做法，既突出产品的特征，又便于用户理解并兼顾习惯和通行标准的要求。",
+        "category": " Introduction"
+    },
+    {
+        "id": 69,
+        "chunk": "# 第三节涂料的附着  \n\n涂层与底材，配套涂层之间良好的附着力是涂料发挥功能的基础。涂层的附着力与底材的特性（金属、木材、玻璃、混凝土和砖石、塑料和橡胶以及底涂层等），包括机械强度、多孔性、表面张力、含水量、表面清洁度、粗糙度等密切相关；同时涂料对底材的润湿、渗透性，以及涂料与底材的相互作用强度也至关重要；还有涂料在成膜过程中及在使用环境中产生的各种应力都对涂层附着力带来不利的影响，甚至导致涂层剥离或开裂等涂层缺陷和失效。涂料附着力的产生和发展与涂料成膜过程息息相关，因此必须全面了解和认识附着和成膜原理。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 70,
+        "chunk": "# 一、附着力的本质及影响附着力的因素  \n\n尽管附着力的重要性早为人所知，而且人们采用现代仪器分析手段进行了大量的基础研究，但是令人遗憾的是，对附着力本质的科学认识尚不充分，所提出的各种假说缺乏统一的基础。现在讨论的主要是经验的总结和似乎合理的推论。附着力是涂料与底材或涂层之间的界面相互作用力，在一定的条件下保持界面不分离，宏观上就是在涂层上施加垂直的拉力至涂层剥离时的拉力代表附着力。这也是拉开法测定涂层附着力的理论基础。还有划格、划圈、胶带粘贴和拉开等测定附着力的方法，它们作用力的方式和方向不同，测试结果缺乏可比性。",
+        "category": " Introduction"
+    },
+    {
+        "id": 71,
+        "chunk": "# 1.底材的表面处理  \n\n涂料对底材附着的基础是涂料充分地润湿底材，涂料的表面张力必须小于底材的表面张力。最大的涂料铺展要求涂料与底材的接触角为 $0^{\\circ}$ ，即自由铺展。同时涂料对粗糙或多孔底材表面进行渗透并取代表面吸附的空气和湿气，并完成填充过程。涂料的施工黏度，以及成膜过程中黏度的变化和成膜物的分子大小对润湿和渗透过程起决定性的作用。而界面之间的相互作用力来自分子间的作用力（范德华力）、氢键、金属与成膜物功能团之间的整合力以及化学键结合等。由于底材种类和表面结构不同，涂料与底材之间的相互作用非常复杂，很难界定以哪些力为主。另外，底材的表面粗糙度对于涂层的机械锚固作用的贡献也不可忽视。  \n\n除了OEM（原装设备制造）涂装线或控制条件下的酸洗、磷化或喷砂可能对底材进行达到一定标准的预处理外，许多现场施工面对底材的清洁度和表面状况千差万别，因此涂装前底材预处理十分必要。  \n\n(1）金属底材的预处理和涂料附着用量最大的金属底材是钢材，包括不锈钢、镀锌板(热浸或热喷锌)，还有各种铝合金、铜合金底材等。金属底材的机械强度高，坚硬致密，热膨胀率较高，热导率、电导率高，以及很高的表面活性（清洁的金属表面张力高达数百达因每厘米)。实际涂装中遇到的底材表面却是千差万别。钢材表面会氧化或电化腐蚀生成氧化铁，新轧钢板存在四氧化三铁层，它们会导致下层钢进一步腐蚀。而铝和锌表面生成较为致密的氧化层，从而有更好的保护作用，但一旦机械破损或化学介质侵蚀氧化层脱离后会引起进一步的腐蚀。大气环境中各种污染物—灰尘、油脂、润滑油、表面活性剂等吸附在金属表面形成弱介质层，它们必须在涂装前除去。通常OEM（原装设备制造）涂装线前面有底材处理线，即清洁和化学钝化处理流程。钢材经脱脂、除油、除锈、清洗后进入以磷酸盐为主的磷化槽。在特殊配方处理液中，钢材表面转化为磷酸铁/磷酸亚铁层，并与磷酸锌形成由不同晶体组成的具有一定防腐性能和促进涂料附着的钝化层。以前使用铬酸盐处理液，虽然防腐效果更佳，但是由于重金属铬污染环境，在发达国家已经被禁用。磷化钝化层对涂层附着力的促进作用的机理尚未搞清楚，至少高表面张力的无机表面及可渗透的晶体结构有利于涂料的润湿、渗透和附着。  \n\n由于大气污染，尤其是酸雨和沿海地区盐雾腐蚀的加剧，使得铝合金表面采用涂料保护日益普遍。通常铝合金表面有致密氧化铝层，但表面抛光后导致涂层附着困难。虽然普遍采用含铬酸盐的底漆对附着力有改进作用，但仍不理想。迄今为止，大多数铝材处理仍使用铬酸盐为主的处理液，正在开发无铬、无氰化物的铝钝化层。已开发出有机-无机杂化纳米结构铝合金处理层。它由硅酸乙酯预聚物与含氨基的硅烷偶联剂处理铝合金表面，它们水解聚合为硅溶胶，其中硅羟基与铝水合物缩水形成化学键结合，而氨基功能团可与环氧封闭层形成化学交联，从而生成以纳米二氧化硅为主体，与底材和封闭层化学结合的高性能涂层，配合聚氨酯面涂层其总体性能优于传统的铬酸盐底涂加环氧中间层和聚氨酯面涂。  \n\n镀锌钢板通常表面光洁，属于难附着的底材。在汽车厂内通常经过磷化处理可以改进与电泳底漆的附着力。在现场涂装条件下也可采用特殊的磷化液进行表面处理，或者用磷酸锌底漆以改进附着力。不锈钢是最难进行表面处理的金属底材之一。既难氧化也难转化的不锈钢表面，可以采用打磨或浅喷砂方法提高表面粗糙度以改进涂料附着力。正在发展的活性烷氧基硅烷处理剂也有希望对不锈钢表面处理发挥作用。  \n\n在现场施工和设施维护保养作业的情况下，最常用、最有效的预处理金属底材的方法是喷砂。采用适当的磨料和施工工艺达到一定的标准要求，例如，美国腐蚀防护协会SSPC，瑞典船级社 $\\mathbf{S}_{\\mathbf{a}}$ ，或ISO标准。近年来由于环保法规日益严格，湿喷砂和高压水除锈等表面处理技术发展很快。但是，它们很容易引起底材表面“闪蚀”，对涂料的附着和防腐产生负面影响。同时许多结构不允许采用喷砂工艺，只能用机动工具或手工进行表面处理，其清洁度和表面粗糙度难以达到喷砂处理的标准，近年来低处理表面用涂料（surface-tolerantcoatings）发展很快。低处理表面指带一定程度的锈、湿气、油污等干扰涂料附着和引起后续腐蚀的弱介质表面。通过涂料配方调整，改进其与底材的附着力，后面有关章节将会详细介绍。  \n\n(2）木材的表面处理和涂料附着木底材比金属底材的结构和表面状态复杂得多。天然木材主要由纤维素、木质素、天然树脂、多糖及蛋白质等组成。由于树种、生长环境乃至部位不同，其结构、成分组成、致密程度（多孔性和密度）、含水量、表面张力、内聚强度等差别很大。富含羟基的纤维素结构提供高极性和形成氢键结合力基础。但是高的含水量在涂层“呼吸性”不足的条件下将破坏涂层的附着力。在保证涂料对底材的润湿前提下，表面的多孔性有利于涂料的渗透填充而促进涂料的附着，同时填充多孔粗糙的表面也是涂层装饰性的要求。  \n\n从软木到硬木，其致密性、密度和内聚强度差别很大，它们与涂层的刚性匹配很重要。涂层在成膜过程中及使用环境变化时产生的应力如果不能适当耗散，它可能引起附着缺陷。  \n\n还有用合成树脂与木屑、锯末等加工而成的人造板、层压板、颗粒板等底材，它们的表面状态更加接近于塑料底材。  \n\n木材子或结疤是富含松脂的部位，涂料难以附着，也不挂色。应预先用松节油和溶剂处理，或者采用碱液处理。木材预先干燥并保持合理水分含量后，通常采用砂纸打磨达到要求的平整度，必要时经过氧化氢或次氯酸钠溶液漂白。再经过底涂、上色等过程进行表面处理。不同材质及涂装配套和要求不同，其底材处理工艺也不同。  \n\n(3）混凝土底材预处理和表面附着混凝土结构无论是民用建筑，还是工业地坪、道路和桥梁等的涂层保护，近年来发展迅速。混凝土是水泥、砂石填充料与水经充分的水化反应形成的以水合硅酸盐为主体的结构材料。其中以钢筋增强的称为钢筋混凝土，是应用量最大的结构材料。混凝土的表面特征为高碱性，多孔性和高含水率 $(<10\\%)$ ，低机械强度，吸收空气中二氧化碳产生的碳化层、抹浆层等弱介质层，以及混凝土上各种油污、灰尘和风化层等不利于涂料附着。新浇筑的混凝土表面还可能存在脱模剂，而且表面过于光滑而不利于附着，必须进行表面预处理。最常用、最有效的方法是浅喷砂处理，在除去表面弱介质层的同时达到一定的粗糙度要求。也有采用稀酸 $(1\\%\\sim5\\%Z$ 酸或盐酸）对其表面进行处理的工艺，但应注意一定要用清水彻底清洗掉残留的酸，否则会引起涂层附着失效。机械加工车间、机库等被油脂严重污染的混凝土地面，经喷砂处理后还应用洗涤剂彻底除油并采用低处理表面用涂料封闭才能达到适当的附着要求。清洁混凝土表面是高表面张力的无机表面，对溶剂型和水性成膜物—丙烯酸树脂、环氧、聚氨酯、氯化聚烯烃、聚脲、不饱和聚酯等成膜物具有良好的附着力。  \n\n混凝土涂层附着失效往往与混凝土的含水率及蒸汽压变化有关。一旦涂层内外蒸汽压失衡，附着界面的蒸汽压力超过附着力就会导致涂层剥离。因此，涂层应当具有一定的“呼吸性”以防止该缺陷。另外，混凝土中含有相当数量的水溶性无机盐，它们是产生渗透压起泡和脱层的主要原因，所以对混凝土表面进行适当的封闭是必要的。但是，要处理好涂层封闭性和“呼吸性”之间的合理平衡，避免产生附着缺陷。  \n\n（4）涂层在塑料底材上的附着塑料属于聚合物底材，包括热塑性、热固性塑料，化学结构、分子量大小和构型、结晶程度等不同的各种塑料，是表面状况最具多样性的底材之一。从某种意义上讲，树脂纤维板和旧的有机涂层表面可以归于塑料底材范围。  \n\n与其他底材相比，塑料底材最突出的特征为表面能低，一般为 $\\left(15\\sim40\\right)\\times10^{-3}\\mathrm{N}/\\mathrm{m}$ 例如，聚乙烯（PE)、聚丙烯（PP）属于典型的难附着底材。塑料表面机械强度低，有韧性，不适宜喷砂、打磨。一般而言，塑料不耐温，Tg在100℃左右。塑料底材预处理的主要目的在于提高其表面张力达到涂料可充分润湿的要求。电晕、等离子、化学氧化、紫外线照射等方法可促进其表面氧化，产生羧基、—C一O基等极性基团，而表面活性剂处理可对其表面改性从而改进对涂料的附着。  \n\n塑料制品的表面往往存在各种脱模剂等弱介质层，它们干扰涂料的润湿和附着。溶剂清洗是比较有效的方法，但受到环保法规的限制。现在越来越多地采用水性洗涤剂与适当磨料相结合的方法，以达到清洁和产生粗糙度的双重目的。  \n\n涂料的溶剂体系在促进塑料底材附着方面起着十分重要的作用。对于热塑性塑料底材具有一定溶胀能力的溶剂体系的选择是涂料配方设计中必须考虑的关键因素之一。溶胀的塑料表面有利于与成膜物大分子之间的互相缠绕而促进涂层附着。  \n\nPP、PE等低表面能、难附着底材的涂装在预处理技术发展的同时，近年来开发出以改性氯化聚烯烃、特殊丙烯酸树脂为代表的附着力促进剂。它们的作用原理尚不十分清楚，由于底材状况变化较多，通常经实验进行筛选。  \n\n目前塑料涂料绝大多数是VOC高的溶剂型涂料，未来将受到严格限制。对于高表面张力的水性涂料而言，对塑料底材的润湿是首要难题，而紫外光固化涂层的快速固化产生的应力对附着力的不利影响也是开发环境友好型塑料涂料面临的挑战。  \n\n在施工中经常碰到在已有涂层上涂装，即产生层间附着力的要求。热塑性涂层只要配套相似的成膜物树脂体系和具有一定溶胀能力的溶剂体系的涂料均可保证良好的层间附着。对于环氧、聚氨酯等热固性涂层，尤其是交联密度高和光洁的涂层表面再涂装将会导致重涂困难。虽然重涂前对其打磨增加粗糙度是有效的方法，但费时费工，增加成本。为了满足可重涂性要求，最好是产格控制重涂间隔时间，在底涂层尚未完成交联反应前涂装面层，所谓的“湿碰湿”涂装，底层中尚未反应的官能团还可能与面层产生共价键结合而提高层间附着力。还可以尽量提高底涂层的颜料体积浓度PVC，达到半光或无光的效果，通过提高表面粗糙度而促进附着。另外，也有在底涂层的成膜物树脂结构中引入可被某些溶剂溶胀的成分，例如烃改性的环氧涂料，它们即使充分固化后仍能被面漆中的强溶剂适当溶胀。但是，涂层的其他性能可能受到影响。  \n\n其他的玻璃、纸张、纺织品、皮革等底材都各有特点，就不在此一一讨论了。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 72,
+        "chunk": "# 2.影响涂层附着力的主要因素  \n\n前面重点叙述了不同底材特征，包括它们的化学结构和组成，表面性能，清洁度，多孔性，粗糙度等与涂料附着相关的因素。而涂料对底材的润湿、渗透、填充能力是涂料的成膜物和活性颜料与底材相互作用的基础，其中涂料黏度或流动性、细度、固化时间是关键参数。涂料与底材相互作用过程是与成膜过程同时完成的。这是一个动力学控制过程，涂装工艺及环境条件的变化都对此过程产生直接的影响。迄今为止，仅限于按照标准方法，在标准条件下测定某种涂料在指定的底材上的附着力。由于方法自身的限制，包括制板程序等，测试结果并不完全代表工业涂装后涂层的附着力。近年来在现场涂装开始使用可现场监测的仪器和方法，例如手提式拉开法附着力测试仪。  \n\n涂层的附着力在使用过程中，受环境因素的影响实际上是不断变化的。Funke在研究涂层防腐性能时提出，除了涂层低透氧率、透水率——屏蔽性之外，“湿附着力”起着十分重要的作用。这是最早将附着力概念扩展到使用条件下加以科学认识的开拓性工作。涂层的湿附着力尚无标准的测试方法。通常将样板浸水一定时间后，擦干用划格和胶带拉开方法进行评价。具有良好湿附着力的涂层在浸水条件下，渗透至界面的水不能取代成膜物与底材的结合，也不能引起水解或皂化而破坏涂层的附着力。这个概念对于浸渍使用的涂层（水、盐水、溶剂等化学介质）防腐性能评估很有价值。  \n\n涂层在特殊使用环境中受到冷热交变、湿度剧变引起的体积变化、外力冲击等产生的各种应力，它们是涂层失效的主要原因之一，而失效的重要表现之一就是涂层附着力降低，乃至消失。许多特种涂料性能往往要求测定其在特定老化循环程序后的附着力降低程度。所以涂料配方师应具备从涂料开发、生产、涂装、使用全过程中认识和把握涂层附着力的概念的能力，将附着力缺陷降低到最低水平。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 73,
+        "chunk": "# 二、提高涂层附着力的技术途径  \n\n涂层附着力主要包括底漆对底材的附着和涂层之间的层间力，它们既有区别又相互联系，必须达到相互匹配。  \n\n底材按标准方法进行表面处理达到必要的清洁度、粗糙度标准以满足涂装要求，这是大规模OEM流水线作业的基本模式。然而许多涂装须现场完成，或产品批量小不值得采用喷砂或磷化等表面处理方法，于是出现“低处理表面”（在一定程度上带锈、带油和带湿涂装）的要求，需求低处理表面用通用型涂料。国外一般称为Surface-Tolerant Coatings。由于可省去费时费工的喷砂处理，代之以手工或机械清理，可节省施工时间和费用。目前许多大公司有此类产品。但是应该注意如何界定“带锈、带油、带湿”标准，因为涂料只具备一定的承受限度。  \n\n还有所谓的“难粘底材”，即低表面能底材。目前大量使用聚乙烯（PE)、聚丙烯(PP)、尼龙等塑料材料等。由此衍生出系列的附着力促进剂产品。其中包括氯化聚烯烃、不含氯附着力促进剂等，它们在塑料涂料中将详细叙述。还有一类“难附着底材”指光洁度很高的金属表面一—不锈钢、铝合金、热浸锌板等。它们涂装前不允许喷砂或拉毛处理，简单清洁后采用偶联剂或有机-无机杂化附着力促进底涂处理。  \n\n涂层之间的“层间附着”在某种意义上理解类似塑料底材上的附着，但影响因素更为复杂，尤其是与涂装工艺关系十分密切。在涂装间隔越来越短，乃至湿碰湿涂装条件下，人们对层间附着力的认识还很不够，评价方法跟不上。至少目前对重涂间隔和涂料的“可重涂性”在很多涂装标准中有了明确的要求。尤其是涉及环氧、聚氨酯等热固性涂料配套体系，往往超过一定重涂间隔后，面涂层或中间涂层出现附着力缺陷和层间剥离。目前在一些防腐涂装规范或技术条件中要求涂料的可重涂性大于15天。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 74,
+        "chunk": "# 第四节涂料的成膜及控制因素  \n\n涂料的成膜就是将涂料（液体或粉末）转变成连续完整涂层的过程，它是通过选择适当的涂装方法，按照严格的施工工艺完成的复杂的物理化学过程。成膜过程的控制决定了涂层的质量和性能。粉末涂料经静电喷涂、热喷涂、流化床喷涂后加热使粉末熔化成膜并交联成膜，其过程将在粉末涂料中专门讨论。本节主要讨论液体涂料的成膜。不同的成膜物的成膜机理不同，同时与涂料的组成有关。而且成膜过程受成膜条件-—温度、湿度、通风、膜厚、时间等影响，决定了涂装方法和涂装工艺的选择。通常将成膜物分为物理成膜方式——成膜前后其化学结构不发生变化（热塑性树脂溶剂蒸发或热熔成膜，非交联乳液成膜)，以及化学成膜方式—成膜物经化学反应交联成三维大分子成膜。事实上现代涂料很多都是多种成膜方式的结合，例如，溶剂型双组分环氧或聚氨酯涂料的成膜就是物理和化学方式的结合。自交联丙烯酸乳液先物理成膜后化学交联。特别应强调成膜过程中存在动力学控制，多组分相容混合，扩散控制等因素，它们直接影响成膜的质量。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 75,
+        "chunk": "# 一、与成膜过程有关的基本概念",
+        "category": " Introduction"
+    },
+    {
+        "id": 76,
+        "chunk": "# 1.黏度  \n\n液体涂料流变特性的宏观指标。涂料的流变性不同，其测定方法和表示参数也不同。一般要保证涂料良好的润湿、流平性、防流挂性，其施工黏度根据涂装方法不同，在高剪切下应为 $0.05{\\sim}1\\mathrm{{Pa}}\\cdot\\mathbf{s}.$ 液体涂料成膜就是将低黏度的液体“湿膜”转变成固体“干膜”，俗称干燥过程。成膜过程中涂层的黏度逐步增大，Burrell等认为黏度大于 $10^{3}\\mathrm{Pa}\\cdot\\mathrm{~s~}$ 时达到手触干，而要达到抗粘连的要求其黏度约大于 $10^{7}\\mathrm{Pa}\\cdot\\mathrm{s}$ 、热塑性成膜物的涂层黏度变化取决于溶剂挥发速率及其玻璃化温度，反应交联成膜物的情况复杂得多，下面将详细讨论。黏度的变化直接反映涂层内自由体积的变化，即聚合物链的迁移自由度，它又与成膜质量息息相关。调整适当的施工黏度，严格控制成膜条件，保证成膜过程中黏度正常增长是涂装工艺的基本要求之一。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 77,
+        "chunk": "# 2.干燥时间  \n\n是液体涂料转变成固态涂层经历的时间。我国的标准［GB/T1728—1979（1989)］将其划分为表面干燥、实际干燥和完全干燥三个阶段，即表干、实干和硬干。实际上只测定表干和实干，硬干耗时太长，除有特殊要求一般不测试。美国ASTMD1640—95将干燥过程分为八个阶段：指触干、不粘尘干、指压干、干至可触、硬干、干透、干可重涂、干至无压痕。涂层的干燥时间受干燥条件的制约，常温干燥标准条件为 $23\\%$ 、相对湿度 $50\\%_{3}$ 高温烘烤都有相应的温度范围。溶剂挥发型成膜过程的干燥时间与通风条件直接相关。涂层的厚度也是重要的因素，必须确定干膜和湿膜厚，否则干燥时间毫无意义。溶剂型涂料往往通过溶剂体系的调整来实现干燥时间的控制，而反应交联型成膜过程还应控制反应动力学，其交联干燥程度往往通过其耐溶剂溶胀性或耐溶剂擦洗性做直观和快速判断。可以采用红外、核磁共振、差热分析等仪器分析方法监测其反应交联程度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 78,
+        "chunk": "# 3.成膜物的玻璃化温度 $\\pmb{T_{\\imath}}$ 和最低成膜温度MFT  \n\n反应交联型成膜物都是小分子低聚物， $T_{*}$ 很低，交联后的大分子随着交联密度的增加$T_{\\mathrm{~g~}}$ 增高至 $100^{\\circ}\\mathrm{C}$ 以上。热塑性的成膜物具有一定的玻璃化温度，常温条件下成膜物的 $T_{\\kappa}$ 必须高于 $25\\Upsilon$ 以上才能形成有一定强度的涂层。但是，在温度 $T_{\\mathrm{{s}}}$ 以上不可能成膜。只有在远低于温度 ${{T}_{\\mathrm{*}}}$ 下涂料才具备必要的流动性和成膜性。溶剂和增塑剂，乳液聚合物中的成膜助剂可以降低成膜温度，涂料成膜后溶剂和成膜助剂挥发，成膜物逐步接近其 $T_{*}$ 值，即固化成膜，增塑剂留在涂层中。成膜物 $T_{\\mathrm{{s}}}$ 是与涂层物理机械性能有关的特征参数，可以用标准方法测定。而最低成膜温度是与成膜过程控制相关的参数，它可以按要求在较大范围内调整。 为",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 79,
+        "chunk": "# 二、物理方式—溶剂挥发成膜  \n\n传统的热塑性溶剂型涂料，例如氯化聚烯烃、硝基纤维素、丙烯酸树脂、CAB和聚乙烯醇缩甲醛等成膜物溶解于一定的溶剂体系制备成小于 $50\\%$ 固体分的涂料，涂装后经溶剂挥发固化成膜。事实上，成膜过程比想象的复杂得多。溶剂挥发引起的涂料流变特性的变化与流平和防流挂性平衡，溶剂滞留对涂层性能乃至涂层的结构均有重大影响。  \n\n聚合物大分子，通常线型结构的分子在溶液中以线团缠绕形态存在，在溶解力不同的溶剂中其形态不同。当溶剂蒸发时，聚合物分子线团移动程度降低，尤其是使用强溶剂与弱溶剂混合体系时，不同溶剂蒸发速率之差必然影响大分子线团及相互缠绕的形态，从而导致涂层结构和性能差别。  \n\n一般认为，溶剂蒸发分为两个阶段。第一阶段即成膜开始时，成膜物大分子对溶剂蒸发影响较小，主要决定于溶剂的蒸气压或溶剂的相对挥发速率。随着溶剂蒸发，涂膜黏度增加到一定程度，自由体积减小，溶剂从涂层中扩散至表面受阻，溶剂蒸发由涂层表面挥发控制转变为扩散控制，挥发速率显著变慢，即为第二阶段。此阶段可能持续很长时间，例如，某些氯化聚烯烃涂层2年后仍然有 $2\\%\\sim3\\%$ 的残留溶剂，称为溶剂滞留。事实上它们转变为增塑剂了。扩散速率取决于自由体积，其最重要的影响因素是 $T$ 和 $T_{\\mathrm{~s~}}$ 。干燥温度 $T$ 高于${T_{\\mathrm{~g~}}}$ ，则扩散控制不起作用；若 $\\textstyle T_{*}$ 高于 $T$ ，则溶剂挥发受控于扩散速率。所以要将溶剂从涂层中彻底清除，必须在高于成膜物温度 $T_{\\mathrm{s}}$ 下烘烤。尽管近年来对溶剂挥发模型的定量化处理做了不少的工作，但至今尚未取得满意的结果。溶解力和相对挥发速率不同的混合溶剂体系的蒸发速率控制及对成膜质量的影响更加复杂，目前只能通过实践确定。  \n\n高固体分涂料中溶剂比常规涂料低得多，其溶剂蒸发速率对涂层流挂性的影响更加重要。一般而言，高固体分涂料溶剂挥发更慢，不仅由于大多采用高压无气喷涂施工而雾化损失少，而且主要由扩散控制溶剂挥发。高固体分涂料主要是化学成膜，交联引起涂膜黏度增大，自由体积减小也是重要影响因素。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 80,
+        "chunk": "# 三、聚合物分散体系的成膜  \n\n聚合物分散体系包括以水为分散介质的乳液，以及非水分散的有机溶胶等，聚合物不溶于介质，以微粒状态稳定分散在分散介质中。成膜时分散介质挥发，在毛细管作用力和表面张力推动下，乳液粒子紧密堆集，并且发生形变，粒子壳层破裂，粒子之间界面逐步消失，聚合物分子链相互渗透和缠绕，从而形成连续均一的涂膜。乳液成膜机理曾进行很多研究，提出几个理论，有的划分三个阶段，也有的提出四个阶段，多少有点武断。时至今日成膜的动力是以毛细管作用力，还是表面能降低为主仍在争议之中。  \n\n涂层良好的物理机械性能和耐沾污性要求成膜物有高于常温的 $T_{\\mathrm{s}}$ ，而成膜需要尽可能低的最低成膜温度MFT。这个矛盾目前是采用成膜助剂来解决的。它们是一类对成膜物溶解力强的高沸点溶剂，成膜后缓慢蒸发。不同的成膜物应选择不同的助剂组合，其效率差别较大。亲水性强的聚合物可吸水溶胀，水可作为成膜助剂，最多可降低 $T_{\\mathrm{s}}$ 5℃。  \n\n但是成膜助剂是乳液聚合物中VOC的主要组成部分，随着环保法规日趋严格，开发超低VOC或零VOC乳液成为重要方向。近年来，采用高 $T_{*}$ 为核、低 $T_{\\mathrm{s}}$ 为壳的核-壳结构乳液，或不同 $\\boldsymbol{T}_{\\mathrm{s}}$ 乳液混拼；采用纳米颜料增强低 $T_{*}$ 乳液；合成低 $T_{\\mathrm{s}}$ 乳液，成膜时发生交联固化提高涂层 $\\boldsymbol{T}_{8}$ 等多种方法制备低VOC乳液，取得相当大的进展。其中以液体环氧和醇酸作为活性成膜助剂与丙烯酸单体采用杂化乳液聚合工艺制备的超低VOC乳液具有环境友好和性能优势。  \n\n乳液成膜过程中涉及乳化剂的迁移，即小分子乳化剂成膜过程及成膜后向底材和涂层表面两个界面迁移，对涂层的附着力、耐水性、耐沾污性带来不利影响。开发无皂乳液（不用乳化剂)，以及采用可聚合乳化剂和非迁移型聚合物乳化剂的工作正在展开，还有很多问题有待解决。 ov",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 81,
+        "chunk": "# 四、化学方式成膜  \n\n成膜物在成膜过程中发生化学反应，分子间交联生成具有三维结构体型大分子的连续涂层称为化学方式成膜。可能发生交联的化学反应几乎包括成膜物中所有化学反应，根据成膜条件和施工工艺的不同要求，有常温固化、加热固化、紫外光固化型，也有单组分和双组分成膜方式。而交联基团和成膜物结构、交联密度的设计则按照最终涂层性能和施工工艺要求变化多端。通常，经化学方式成膜的涂层综合性能优于物理方式成膜的涂层。这类成膜物常称为热固性树脂，除粉末涂料外，它们都是低分子量的低聚物，施工黏度低，随着交联密度增大，黏度增大，自由体积减小， $T_{\\mathrm{s}}$ 增大，直至生成连续均一的固体涂层。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 82,
+        "chunk": "# 1.单组分热固性成膜物体系  \n\n单组分涂料施工便利，省工、省时、省料，很受市场欢迎。醇酸及改性醇酸、环氧酯氨酯油即聚氨酯改性醇酸等通过吸收空气中的氧引起不饱和脂肪侧链氧化交联是典型代表。单组分湿气固化聚氨酯吸收空气中的水，与成膜物中过剩的—NCO反应生成聚脲聚氨酯涂层。高模数硅酸钾、硅酸锂吸收空气中二氧化碳转变为硅醇发生缩水交联等是常温固化交联型。以三聚氰胺甲醛树脂与含羟基、羧基的丙烯酸、醇酸、环氧、聚酯组成的氨基树脂成膜物体系是高温烘烤固化的典型。还有封闭异氰酸酯成膜物体系，它们在常温下足够稳定，加热并在催化剂作用下释放出—NCO快速反应交联成膜。反应交联型的粉末涂料也可以归入单组分涂料。  \n\n开发这类涂料最大的技术挑战在于确保生产、贮运相当期限内产品的稳定性，采取各种措施将交联反应抑制到可接受的限度；同时保证在成膜过程中足够快和充分的反应交联。近年来在开发水性丙烯酸自交联型乳液和涂料过程中，采用羟甲基丙烯酰胺、含羰基丙烯酸单体、不饱和硅氧烷等功能单体改性等多种手段，它们将在以后各章节中详细讨论。",
+        "category": " Introduction"
+    },
+    {
+        "id": 83,
+        "chunk": "# 2.自由基聚合反应成膜  \n\n以不饱和聚酯、丙烯酸或烯丙基化的环氧、聚氨酯、聚酯低聚物及环氧化合物与活性稀释剂等组成的成膜物在自由基引发剂作用下，或者紫外线、电子束等高能光束引发光敏剂分解产生的自由基或活性离子作用下发生聚合交联成膜，整个过程在几秒至几分钟内完成。成膜过程几乎没有有机溶剂挥发，环境友好和节能，这是目前涂料行业发展最快的领域之一。自由基引发剂一般与不饱和聚酯分开包装，为双组分；而光固化涂料是单包装。空气中的氧对聚合反应具有阻滞作用，必须解决氧阻问题。  \n\n具有挥发性和刺激性的活性稀释剂对职业安全和健康的评估尚待完成。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 84,
+        "chunk": "# 3.双组分涂料的成膜过程  \n\n环氧树脂与胺固化剂，聚合物多元醇或多元胺与多异氰酸酯固化剂之间发生加成聚合交联成膜，它们都是双组分包装，使用前按比例混合，涂装成膜。双组分涂料一般不存在贮存稳定性，但是异氰酸酯固化剂对湿气敏感，生产、包装贮存时要加小心。  \n\n影响双组分涂料成膜过程的因素很多，首先是双组分的混合和混溶性。例如，环氧树脂与低分子量的脂肪多胺、脂环多胺的分子结构和分子大小差别较大，混溶性差影响混合和扩散效率，混合后需放置一定时间称为“熟化”期。环氧预聚物固化剂或腰果酚酚醛胺固化剂与环氧树脂的混溶性好得多。溶剂体系的选择对改进双组分混溶性同样重要，当然溶剂的极性、电负性、亲质子性对交联反应的影响也应考虑。双组分的比例不应差别太大，配方时应适当调整以便提高混合效率。  \n\n功能团之间的反应速率主要受反应动力学控制和成膜物扩散速率双重控制。动力学因素主要是反应物浓度和反应速率常数，而反应速率常数又与反应温度密切相关。与小分子之间的反应不同，聚合物分子链上官能团是按一定结构分布的，它们的反应活性受立体构型等影响有差别，而且聚合链要有必要的移动性将反应基团配合到一起，所以成膜物的扩散速率至关重要。当扩散速率大于反应速率时（反应开始并且低黏度态)，反应受动力学控制。随着交联密度增加，涂膜黏度增大，自由体积减小，扩散速率逐步减小低于动态反应速率，成膜过程变成扩散控制。一旦涂膜的T。高于室温，扩散已不可能，反应实际中止。这就是为什么有的室温固化涂层需要几周乃至数月才能彻底固化。其中温度对两种控制因素都有重要影响。根据不同的成膜条件，适当控制成膜反应速率，避免成膜初期黏度增长过快对保证成膜质量非常重要。双组分混合后黏度增长至无法施工的时间称为施工适用期（potlife)。这是涂料重要的施工性能参数，也与环境条件有关。水性双组分涂料的成膜过程更加复杂。两种乳液粒子的混合，成膜过程中聚结、混溶、反应等存在更多的控制因素。如果在双组分尚未混溶好之前发生反应，则不可能得到高质量的涂层。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 85,
+        "chunk": "# 4.非均相一涂分层成膜过程  \n\n传统的涂料工艺要求成膜物形成均相的连续的涂层，而且不同涂层通过分层涂装和配套完成。20世纪90年代初开始开发一道涂装形成两层以上涂层的涂料，可以大大节省施工时间和费用。这类涂料应满足几个前提条件：不同的成膜物彼此不相溶，或者成膜前以稳定的分散体系共存，或者在成膜过程中发生分相，例如，环氧-漆酚体系成膜时环氧固化与漆酚分相，后者迁移至涂层表面后再发生氧化交联，分相过程有足够的时间，还有合理的分相迁移的推动力，密度、表面张力梯度等。一涂分层成膜技术处于发展阶段，前景看好。  \n\n在特种涂层材料的开发中发现非均相成膜结构涂层在表面活性、电磁性能、声学性能以及力学性能等方面具有特殊的表现。例如，由憎水-亲水部分组成并呈现仿生海岛结构的表面具有很好的防止海生物附着的功能。  \n\n还有正在发展的自组装涂层，它们自身组成就是多相体系，在成膜过程中经自组装形成分相结构。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 86,
+        "chunk": "# 第五节涂料工艺的范畴  \n\n传统对涂料工艺的认识主要集中在成膜物化学方面，而且配方师着重于以经验为基础的配方的调整。科学界和技术界对涂料科学的复杂性认识和重视程度不足，科学院所和大专院校涉足涂料行业和涂料应用基础研究的很少，与精细化工其他领域相比，人们对涂料的科学理解相对滞后。涂料作为复杂的分散体系，涉及有机化学、无机化学、物理化学、高分子化学和工艺学、界面物理学、界面化学、流变学、材料力学、成膜反应动力学等学科，而每一种特种功能涂料的开发包括多学科领域的交叉。正是由于涂料成分的多样性、可变性决定了常规的配方筛选方法难以胜任如此庞大艰巨的任务，形成配方师的技艺胜于科学的局面。现代涂料工艺应建立在对从涂料开发至满足用户需求的涂层的全过程认识基础上，以技术创新适应激烈的市场竞争，涂料涂装整体解决方案，以技术经济为引导的系统观念。涂料技术应贯穿在涂料开发、生产制造、涂装服务、涂层维护和质量保障的全过程中，忽视任何一个环节都会违背现代质量和技术管理的要求。  \n\n现代涂料工艺至少应包括如下内容。",
+        "category": " Introduction"
+    },
+    {
+        "id": 87,
+        "chunk": "# 1.涂料原材料的开发和质量控制  \n\n涂料的成膜物、溶剂、颜料和助剂品种繁多，最近欧盟REACH法规要求注册的化学品中与涂料相关的近万种，而且还在迅速发展。原材料的开发依托于整个基础化工行业，并朝着专业化方向发展。除了少数专用的树脂、颜料和助剂外，涂料厂都采用外购，而且普遍采用全球采购的模式运行。  \n\n在高性能、环境友好和可持续发展目标的推动下，涂料原材料的开发非常活跃，新材料和新产品层出不穷。高性能水性成膜物、高固含量成膜物、紫外光固化和粉末树脂、氟硅树脂以及纳米材料等新材料在涂料行业应用日益增多。在新产品开发过程中应特别强调其工艺的可靠性、产品质量的稳定性和适用性，不必过分追求个别指标的高性能，同时强化产品的技术服务。许多跨国公司的原材料供应商具有成熟的经验。  \n\n原材料供应商的资质认证和管理、原材料进货标准和检验方法的制定是涂料生产质量控制的第一关。尤其是颜填料的细度及其分布、吸油度、分散性等各批次之间都可能存在差别，必要时应打小样验证。",
+        "category": " Introduction"
+    },
+    {
+        "id": 88,
+        "chunk": "# 2.基础配方和配方设计  \n\n配方是涂料生产的基础。前面谈到涂料应满足多方面的性能要求和符合法律法规，同时面对如此多的原材料可选择性，而目前尚无处理如此复杂体系的科学实验设计方法，配方师大多从经验积累的一些基础配方出发，结合对涂料的基本科学理解采用“差试”方法，在有限的时间内对已有的配方进行调整满足用户的基本要求。随着人们对涂料科学认识的深入和研究方法的改进将会逐步减小盲目性和经验性。  \n\n准确认识和把握用户对涂料技术性能、施工性能、性价比以及法规要求是配方设计的前提，基础配方和配方原理是基础。要记住配方总是要不断改进的（用户需求多样化、个性化和原材料不断变化)，配方的管理是动态的。没有最好的配方和产品，只有适合用户需求的产品。配方设计就是一个不断优化或选优的过程。涂料合理的分散性和流变性控制，成膜速率和成膜性控制，原材料的选择和配比等是重要的配方参数。特别须强调的是各种成分在复杂体系中的交互影响，应更多地采用科学的数理统计实验方法和数据分析方法。  \n\n色漆配方设计中正确认识和把握颜料体积浓度PVC的概念非常重要。当涂层PVC超过临界颜料体积浓度CPVC时，涂层的物理机械性能和保护性能将发生突变。理论上讲，PVC与颜料粒子的形状和堆积方式有关，例如，均一的球形粒子呈正方形排列时的PVC为$54\\%$ ，而呈菱形填充时为 $72\\%$ 。实际情况要复杂得多，首先，颜料的晶型多样化，其中片状颜料可能达到最大限度的空间填充；其次，颜料的粒度分布对其PVC影响很大；颜料与成膜物的相互作用及吸附层厚度等都与涂层的PVC相关，目前尚无系统的理论处理。特殊的超CPVC涂层，例如，富锌涂层、导电和雷达波隐身涂层等要求高电导率、磁导率，成膜物不能全部包覆颜料表面。  \n\n涂料往往是配套使用的，涂层配套体系的设计和评价应该是产品设计开发的重要组成部分。涂料产品有限，而适应不同需求的配套体系却无限。涂料的层间附着力和可重涂性已成为涂料必须考虑的性能指标。",
+        "category": " Introduction"
+    },
+    {
+        "id": 89,
+        "chunk": "# 3.涂料制造工艺和设备  \n\n涂料生产包括混合、分散、过滤、包装、检验、贮存等过程的管理和控制。近年来各种设备朝高效、节能的方向发展，制漆工艺更加精细，尤其是电脑配色和色浆工艺的推广不仅提高了生产效率和产品质量，而且缩短了生产周期，加快了对市场的反馈，增强了公司的竞争力。 ?  \n\n涂料生产工艺规程，产品标准是以国家标准、行业标准、企业标准以及用户协议标准制定的，检验方法的标准化，安全和环境管理等是产品质量的基本保障。在市场经济条件下，国家标准和行业标准更着重于符合法律法规的强制性标准，技术要求主要体现在符合用户需求的企业标准和合同标准中。例如项目招标中所列的技术要求。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 90,
+        "chunk": "# 4.涂装工艺和技术服务  \n\n用户需要的最终产品不是涂料而是涂层，涂料供应商有责任帮助和解决用户在使用涂料中遇到的问题，保证涂装质量。涂料出厂检验指标都是在标准条件下按标准方法测试的，与实际涂装环境和涂装工艺存在差别，现场涂装的涂层质量必须依靠有效的技术服务和管理加以保证。  \n\n在船舶、汽车、家具等涂料应用领域十分重视涂装技术服务。俗话说：“三分涂料，七分涂装”。从产品说明书的编写、施工工艺的制定，到现场服务人员的培训、资质认定，以及现场服务工作程序等都比较规范。牢固地树立服务的理念至关重要，在了解用户需求时就应帮助他们选择适用的涂料和配套体系，进行涂装设计。",
+        "category": " Introduction"
+    },
+    {
+        "id": 91,
+        "chunk": "# 5.涂料、涂装缺陷和涂层失效分析  \n\n涂料生产和贮存过程中可能发生分散不良引起的分色、浮色、起泡、沉底、分层等涂料缺陷；涂装过程中发生刷痕、流平不良、流挂、气泡、针孔、露地、起皱、裂纹等涂装缺陷；而这些缺陷最终导致涂层在使用过程中提前失效。对涂料缺陷及涂层失效原因的分析，认识和提出合理的解决办法对保障涂层质量非常重要。随着仪器分析技术的发展，人们对涂料、涂装缺陷和涂层失效原因的科学理解进一步深入，有助于预防它们的发生。",
+        "category": " Introduction"
+    },
+    {
+        "id": 92,
+        "chunk": "# 6.涂料原材料、涂料产品和涂层性能的检测方法和标准化  \n\n涂料产品和涂层性能指标可能因其用途不同，要求各异。但是，它们的检测方法必须统一和标准化。我国制定的国家标准GB已经逐步与国际通用的美国ASTM标准和国际标准化组织的ISO标准接轨。  \n\n受涂料科学发展水平的限制，目前许多检测方法尚不够完善。聚合物树脂溶液和液体涂料的黏度测定根据其流变性不同采用流出法、落球法、旋转黏度计、斯托默旋转黏度计等不同方法，它们的测试结果不存在相关性。涂层的耐久性（例如耐候性、耐盐雾性与防腐性等）至今尚未找出其测试结果与自然老化之间密切相关性。涂层耐酸雨性，各种特种功能涂料的特殊功能测定方法都在建立和发展中，有待标准化。  \n\n产品标准和标准方法制定的政策性和科学性很强，需要做大量的基础研究工作。我国的标准制定和管理基本沿袭计划经济的模式，属于政府行为。以国家标准化委员会和原政府部门管辖的行业标准化委员会进行监管。现有的许多标准不适应市场经济的要求，正在进行清理。按国际惯例，行业标准的制定主要依托行业协会，而标准方法应由国家统一管理。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 93,
+        "chunk": "# 第六节涂料开发、生产和服务过程的管理",
+        "category": " Introduction"
+    },
+    {
+        "id": 94,
+        "chunk": "# 一、质量管理体系  \n\n计划经济时代的国营大中型涂料企业一贯重视产品质量管理，1960年以后实施的全面质量管理TQ对提高企业管理水平起到很大的推动作用。民营企业大都借鉴国营企业的管理制度。1995年以后我国开始推行ISO-9000系列质量保证体系，包括ISO-9001—1994年版设计、开发、生产和服务质量保证体系，以及不包括产品开发的ISO-9002质量保证体系，以期与国际接轨。20世纪90年代末，国内绝大多数涂料企业实现贯标和认证。从2001年开始又开展了ISO-9001一2000年版产品设计、开发、生产和服务质量管理体系的换版和认证。它更加突出了顾客第一，持续改进，系统和过程管理的理念，强调了管理者的职责和员工全员参与质量管理的重要性和主体意识。该体系是现代质量管理实践的科学总结，具有普遍性和适用性。  \n\n在企业质量方针和质量目标激励下，从用户需求出发，对产品设计开发，原材料供应商控制，生产，检验，贮存运输，用户服务至涂装全过程进行监控，通过完整的制度、工作程序和质量记录进行保证，从而达到预防和减少不合格品的目的。整个管理体系具有自我完善、持续改进的要求，体现了不断管理和制度创新的内涵。技术和工艺的发展与管理紧密相关，质量管理是技术创新和发展的基础和保障。市场要求企业不断地开发高质量、高性能、性价比好的产品满足市场不断变化、多样化和个性化的需求。",
+        "category": " Introduction"
+    },
+    {
+        "id": 95,
+        "chunk": "# 二、环境管理  \n\n按照可持续发展战略和科学发展观的要求，经济发展必须与环境保护和生态改良同步，绝对不能以牺牲环境作为代价。涂料生产和涂装过程中涉及许多危害环境的因素。溶剂型涂料中的有机溶剂—有机挥发物（VOC)，其中苯、甲苯和二甲苯、卤代烃等对人体和环境危害很大，有害空气污染物（HAPS）破坏大气臭氧层，欧美国家对VOC和HAPS的限制排放的法规日趋严格。涂料原材料中含铅、铬、砷、汞等有毒有害重金属也逐步禁用，至2008年全球将禁止在船底防污涂料中使用三丁基锡防污剂。在涂料生产过程中的粉尘、噪声、废水、废气、废弃物等，涂装和底材表面处理过程中喷砂粉尘、噪声，有害废涂层，挥发的VOC等都是环境污染因素，必须加以控制。  \n\nISO-14001环境管理体系的认证已经在中国涂料行业推行。根据国家颁布的有关环境保护、三废排放、化工生产中有毒有害物质管理的法律法规，国家对室内装饰材料的相关标准，正逐步与国际相应法规接轨。确定涂料生产和涂装过程，乃至废弃涂层的主要环境因素，制定环境管理方针和目标，采用与ISO-9001质量管理体系相似的程序和制度对产品开发、生产和服务全过程进行控制。为了方便管理，通常将ISO-9001质量管理体系和ISO-14001环境管理体系文件进行整合，认证机构一次进行两个体系的认证。  \n\n从2004年开始我国将贯彻ISO-14020系列环境标志产品认证，以及职业健康和安全管理认证等，在此就不详细介绍了。所有法规和管理要求对涂料行业的技术创新和涂料工艺的发展提出更高的要求。开发环境友好型涂料是发展的重要方向。低污染和高效率的湿喷砂、高压水、空泡清理等环保表面处理设备和技术将越来越受到重视。",
+        "category": " Introduction"
+    },
+    {
+        "id": 96,
+        "chunk": "# 涂料工艺的发展",
+        "category": " Introduction"
+    },
+    {
+        "id": 97,
+        "chunk": "# 第一节涂料工艺发展的推动力",
+        "category": " Introduction"
+    },
+    {
+        "id": 98,
+        "chunk": "# 一、经济发展的需求是涂料行业和涂料工艺进步的原动力  \n\n涂料对底材的保护、装饰功能早已为人所知，人类使用天然树脂成膜制备和使用涂料的历史可追溯到7000多年前。中国的大漆和桐油装饰的漆器在2000多年前的汉朝就已达到相当高的水平，后来传人日本，成为传统漆器工艺品。天然沥青、阿拉伯胶、蜂蜡等曾被古埃及、古希腊、古印度等作为成膜物制备涂料。由于生产力发展的限制，古代涂料主要用于木材、竹器的装饰和保护，涂料用量和生产长期处于手工作坊形态。欧洲工业革命以后，人类生产力空前解放，大量钢铁材料的应用对防腐涂料的性能和用量提出前所未有的要求，汽车工业的发展要求配套高装饰和高性能的汽车涂料，房地产业的兴旺刺激了建筑涂料的发展等，与此同时化学工业的发展为涂料提供了新型成膜物和原材料，至19世纪末在欧美涂料行业初步成型。世界排名前五十位的跨国涂料公司中许多都创立于那个年代。第二次世界大战后的半个世纪是世界经济快速发展期，也是涂料行业跨越式发展和逐步成熟期。建筑涂料、工业涂料和特种功能涂料上千种涂料产品涵盖了国民经济各个部门，进入千家万户，包括木材、金属、混凝土、玻璃、纺织品、纸张等各种底材。据统计，1996年全球涂料产量达2300万吨，2005年我国涂料产量达380万吨，美国600万吨。近十年来，我国涂料以高于国家GDP增长速度的增速快速发展，尤其是经济发达的珠江三角洲和长江三角洲占有全国涂料产量的 $70\\%$ 。我国目前人均消费涂料量不足发达国家的1/10，涂料行业具有巨大的发展空间。快速增长和变化的市场，日趋多样化和个性化的市场需求永远是涂料工艺进步的原动力。",
+        "category": " Introduction"
+    },
+    {
+        "id": 99,
+        "chunk": "# 二、科学和技术进步是涂料工艺发展的推动力  \n\n近代有机化学、高分子化学、物理化学和材料科学的发展为科学认识涂料奠定了理论基础。聚合物工艺学迅猛发展为涂料行业提供了品种齐全的合成高性能成膜物，从常规的醇酸、酚醛、环氧、聚氨酯、乙烯基树脂、聚酯到有机硅、氟碳树脂等，而且新的功能树脂还在不断涌现。无机化学、表面化学和表面物理学以及无机工艺学的进展为涂料行业提供了高性能、高分散性的颜料和填料。有机合成工艺学的技术发展推出高着色力、耐高温、耐候、耐介质的有机颜料。而助剂的开发和应用是涂料工艺发展的里程碑之一，极大地改进了涂料和涂层的性能。因此，新材料科学的发展推动和引导涂料行业向高性能、高装饰和功能化方向前进。  \n\n人们对涂料体系流变学、涂料附着机理、涂料成膜机理和反应动力学、涂层失效机理和评价方法等应用基础研究的不懈努力也不断加深对涂料工艺学的科学理解，同时将推进涂料技术进步。",
+        "category": " Introduction"
+    },
+    {
+        "id": 100,
+        "chunk": "# 三、涂料工艺与涂装工艺相互促进  \n\n通常将涂料开发和制备技术称为涂料工艺，属于精细化工领域；涂料施工应用和涂装称为涂装工艺，属于工程领域。从提供高质量涂层，服务用户的现代涂料涂装整体观出发，涂料工艺与涂装工艺的发展紧密相关。涂料必须具备必要的施工性能以满足施工工艺的要求，尤其是OEM流水线涂装，涂装性能某种意义上甚至比技术性能更重要。工业和特种涂料涂装行业历来高度重视涂装工艺的研发。  \n\n涂装工艺的革新和发展极大地驱动涂料工艺的技术进步。卷材涂装线的速度由每分钟几十米提高至100m/min以上，要求卷材涂料具有更快的干燥速率。汽车涂装工艺调整和对高质量涂层的要求促进了厚膜型阴极电泳漆的发展。家具制造和涂装工艺的革新拓展了紫外光固化涂料的应用范围。造船工艺整体改革促使船舶涂装在造船总成本和制造周期所占比重大幅度上升，对低处理表面涂料的需求迫切。还有高压水除锈工艺的推广催生了配套的防闪蚀涂料的开发应用等。正在研发的新型涂装工艺需要同步开发配套涂料。  \n\n相应的环境友好型水性工业涂料、紫外光固化涂料、粉末涂料、无溶剂涂料以及聚脲喷涂弹性体等的应用与相应的涂装设备开发、涂装工艺和涂装线设计紧密结合，相互促进。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 101,
+        "chunk": "# 四、符合可持续发展战略和法律法规要求  \n\n可持续发展战略要求社会经济与环境协调发展，绝对不能以牺牲环境作为代价。同时要求最大限度地合理使用资源，促使资源的循环使用。涂料产品作为消耗品，尤其是传统的低固体分溶剂型涂料面临巨大的挑战，必须彻底地变革才可能符合可持续发展战略的要求。节省资源、提高效率是发展的基本要求。采用高效率静电喷涂、高压无气喷涂减少废弃物，单层或厚膜涂装节约原材料。制漆、涂装、成膜全过程中开发节能工艺，例如降低成膜温度、提高分散效率等。其中开发应用可再生的天然资源，例如植物油和醇酸再度引起人们的重视。  \n\n环境友好型涂料的开发随着环保法规日趋严格已成为涂料工艺发展的主流方向。履行蒙特利尔保护大气臭氧层国际公约，斯德哥尔摩禁止使用永久性化学污染物公约，国际海事组织禁止生产和使用三丁基锡船底防污涂料等国际公约，VOC、HAPS法规，对甲醛、氨、放射性物质放射量限制，以及重金属含量的限制成为开发高性能、高装饰和功能化涂料的前提。必须在强化科学发展观的同时，大力宣传和提倡科学消费观，不要片面追求涂料的高性能。  \n\n涂料及涂层在涂装过程中的废弃物的处理在发达国家都有严格的法规，不能对环境造成污染。这就要求从涂料开发就应将无害化的要求置于重要位置。开发生物可降解的成膜物，选择无毒颜料，适当回收和处置表面处理产生的有害旧涂层（含铅，含有机锡的防腐、防污涂层等）也是人们面临的挑战。",
+        "category": " Introduction"
+    },
+    {
+        "id": 102,
+        "chunk": "# 第二节涂料工艺的发展  \n\n与发达国家相比，我国的涂料行业相对不够成熟，涂料市场不够规范。但是，在国民经济快速发展的拉动下，未来十几年我国涂料行业将步入发展“快车道”。我国加入WTO后进一步加快了涂料市场全球化和与国际接轨的步伐，大批外企的进人大大缩短了我国涂料行业在工艺水平和管理水平上与它们的差距。信息技术的发展促进了行业内外的沟通，事实上我国涂料行业已经进入国际化竞争环境。因此涂料工艺的发展必须以提高行业的全球整体竞争力为出发点。2006年中国涂料工业协会组织行业专家制定了“十一五”涂料行业科技创新和发展规划，其要点如下。",
+        "category": " Introduction"
+    },
+    {
+        "id": 103,
+        "chunk": "# 一、应用基础研究是创新和发展的基石  \n\n受涂料体系的复杂性制约，基础和应用基础研究相对薄弱，投入资源不足，致使涂料科学的发展滞后于涂料工艺和应用技术的发展的要求。迄今为止，人们对涂料的科学理解还不够深入，这将制约涂料工艺，尤其是技术创新和核心技术的发展。涂料配方的科学筛选和评价方法，配方原理，涂层耐久性评价方法，涂层附着和失效机理，涂料流变学，涂料固化机理和反应动力学，成膜物结构的分子设计，颜料表面改性、表面物理学和表面化学，人们对底材与底涂层、涂层间、颜料与成膜物、涂装表面与介质等界面之间的相互作用的本质的认识不够深入和系统。以及助剂的作用机理和结构设计等诸多课题需要认真加以研究和解决。  \n\n树脂和材料改性涉及的相容性，成膜过程中相分离，杂化树脂及多重或复合固化机理及反应动力学的研究等对高性能树脂成膜物的开发具有促进作用。  \n\n科学原理的探索和思考是科技创新之源泉，创造条件并鼓励研发人员开展新原理的研究，例如以下几个方面。  \n\n$\\textcircled{1}$ 界面化学和界面物理学及分散原理。  \n$\\textcircled{2}$ 仿生防污，减阻机理，导电防腐和防污机理。  \n$\\textcircled{3}$ 新型抗沾污建筑涂料及原理研究。  \n$\\textcircled{4}$ 极端腐蚀环境中长效高性能防腐涂料及新防腐原理研究。  \n$\\textcircled{5}$ 能够达到修旧如旧目标的文物保护涂料和保护原理。  \n$\\textcircled{6}$ 纳米材料改性涂料原理，纳米分散方法和状态表征，作用机理及评价方法的研究。",
+        "category": " Introduction"
+    },
+    {
+        "id": 104,
+        "chunk": "# 二、涂料原材料的发展  \n\n在市场开放和行业集约度日趋集中的条件下，原材料供应商的产品研发和供应更加专业化，更贴近市场的需求。供应商的技术服务更加完善，并且不同品种供应商联手以实现互相促进。  \n\n颜料和填料表面处理工艺和功能化将进一步发展，超细分散和纳米改性材料的应用日益普遍，在开发高性能和功能颜料的同时，强调符合环保法规的要求，大力发展清洁生产工艺，减少和避免环境污染。逐步限制和禁用含铅、铬、镉等有害重金属颜料的生产和使用，并加快相关法规的制定。适应不同用途的电脑配色技术和色浆工艺也是制漆工艺的重要发展方向。颜料行业今后十年将面临激烈的国际化竞争，面对跨国公司在中国市场的扩张，行业的集约度和结构，产品结构调整和质量提升，生产工艺的创新等涉及核心竞争力的领域将会加速发展。  \n\n成膜物的研发从来就是涂料工艺发展最重要、最活跃的领域。配合环境友好型的水性涂料、无溶剂和高固体分涂料，紫外光固化涂料和粉末涂料发展所需求的新型成膜物将不断进入市场。特种涂层配套的功能高分子材料——导电、智能高分子材料，吸收和透波树脂，耐高温树脂，耐极端腐蚀环境的成膜物等；有机-无机杂化成膜物等高性能和功能成膜物；水性工业涂料—汽车漆、水性防腐涂料，水性木器和塑料涂料，水性集装箱涂料等配套的水性树脂，它们的技术性能和涂装工艺性的匹配；高固体分涂料成膜物分子设计及流变性能控制；具有自组装性能的复合树脂体系；超支化树脂及高固体分涂料；非—NCO聚氨酯树脂和原料；粉末，水性氟碳树脂；适应不同用途和施工工艺的聚脲树脂及原材料；有机-无机杂化高固体分、高性能树脂成膜物；通用型成膜物的合成工艺、性能提升等将进一步发展。适合高性能要求的汽车罩面装饰效果的多功能复合树脂成膜物的开发将引起人们的关注。粉末涂料树脂，塑料和木器用低温成膜粉末树脂，符合VOC和HAPS法规要求的安全环保溶剂的开发和应用会更加受到重视。至少目前溶剂型涂料在高性能和装饰涂料市场还占有相当大的市场份额。其中大力推广VOC、HAPS法规允许使用的脂肪烃、乙醇、丙酮、丙二醇醚、乙酸叔丁酯等溶剂，控制其VOC量，同时在室内环境中重视溶剂的气味及持续时间对人员健康的影响。加强对天然或可再生溶剂—脂肪酸甲酯、松节油等的综合利用和应用开发。  \n\n助剂的多功能化，助剂的作用机理，助剂体系的协同作用和高性能助剂品种的开发也是涂料行业发展的重要方面。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 105,
+        "chunk": "# 三、涂料产品的结构调整  \n\n国民经济的快速发展对涂料的质量和品种提出更高的要求，为涂料提供了更加广阔的应用领域。以可持续发展战略为引导，涂料产品的开发将进入新时代。除了满足多样化、个性化和快速变化的市场对产品性能需求外，更加重视法律法规的要求。开发涂料新产品就是产品性能、质量、价格、服务和法规要求之间进行优化和平衡的过程。在准确识别用户需求基础上开发出满足其用途的产品就是最佳的选择。同时应引导市场，确立科学的消费观，强化环保和安全意识。除传统的钢铁、木材等底材之外，混凝土、纺织品、纸张、塑料、玻璃、橡胶等底材用的涂料将进一步发展，而且对装饰性、功能性提出更高的要求。家庭装饰涂料随着人们生活水平的提高，逐步升华为生活方式的组成部分，即时尚涂装——性能和美学的结合。混凝土结构（建筑、桥梁、水利工程、沿海设施等）的重防腐涂层配套体系及钢筋防腐涂层的开发和应用日益引起人们的重视。高性能的卷材涂料在家电行业中替代粉末涂料，达到节能和高效目的。涂料工程师对涂料技术创新的追求将永无止境。",
+        "category": " Introduction"
+    },
+    {
+        "id": 106,
+        "chunk": "# 四、涂料和涂层性能检测方法的科学化和标准化  \n\n耗时长、费用高的耐候性、防腐性等涂层耐久性测试评价方法的研究和标准化将进一步加强。评价模型的选择，加速实验方法的可靠性、可信度，实验数据与现场实验的相关性等在现代计算机技术和仪器分析技术的支撑下必将取得突破性进展。 “  \n\n特种功能涂料的性能检测方法，以及性能随使用年限变化评估方法的研究，例如，防火涂料耐火性与大气老化时间的关系，耐高温涂料防腐性、耐久性评价方法等应深入研究。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 107,
+        "chunk": "# 五、涂料工艺与涂装工艺的发展密切结合、相互促进  \n\n汽车涂装工艺正朝高效、节能方向发展，经济涂装、生态涂装工艺成为主流，正朝底涂无铅化、高泳透和低加热减量方向发展；加快中涂水性化，罩光漆高固体分和粉末涂料应用研究，新水性汽车涂料，水性集装箱涂料涂装线的建设为水性工业涂料的应用开辟道路。船舶涂料涂装中为简化配套底涂料的品种，提高劳动生产率正在开发多用途的通用底漆。  \n\n不同行业的涂料涂装规范和工程验收标准的编制和颁布实施步伐将加快。迄今为止，我国已颁布船舶、靓船、油气管道、钻井平台、汽车、铁路车辆和钢桥梁、石油化工厂钢结构等行业涂装规范。即将颁布石油贮罐、火力发电厂地下钢结构等行业涂装规范等。这将突出为满足用户需求，提供整体解决方案的理念。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 108,
+        "chunk": "# 六、环境友好型涂料成为涂料工艺发展的主流  \n\n近三十年来，我国涂料行业在改革开放的推动下，法规意识和环保意识增强，尤其是跨国公司进人中国市场促进产品结构发生巨大的变化。环境友好型的水性乳胶建筑涂料已占有$70\\%$ 的市场份额。粉末涂料依托电冰箱、洗衣机、电风扇等家电行业，2005年达到20多万吨规模。紫外光固化涂料在木地板、缝纫机面板、钢琴等高装饰性涂装领域得到广泛的应用。高固体分防腐涂料、家具涂料、醇酸磁漆在溶剂型涂料中所占的份额稳步上升。无溶剂环氧防腐涂料、喷涂聚脲弹性体在工程中的应用已经起步。  \n\n但是，与发达国家的市场和产品结构相比还存在相当大的差距。首先是环保法规的制定和环境指标的确定相对滞后，许多工作在2001年前后为进入WTO做准备而开展，同时工业基础和经济发展水平及行业的技术发展基础和巨大的地区发展不平衡等制约了环境友好型涂料的发展。  \n\n坚持可持续发展、保护环境、注重职业健康和安全是涂料工艺发展的根本要求。因此，开发环境友好的水性涂料、紫外光固化和电子束固化涂料、高固体分和无溶剂型涂料、粉末涂料等环境友好型涂料成为涂料工艺发展的主流方向。其中，涂料技术和涂装工艺的发展紧密结合是前提。仅仅考虑开发水性涂料适应原来的溶剂型涂料的涂装线是不现实的。  \n\n同时，环境友好型涂料的几个领域可能互相渗透，技术集成而形成新的方向。例如，为减轻活性稀释剂的刺激性开发水分散型的紫外光固化涂料、粉末紫外光固化涂料等，还有水性粉末涂料正在发展之中。此外，为适应多重需求和涂装工艺，复合固化体系的开发将成为关注的重点。将化学交联与紫外光固化相结合解决复杂形状产品的涂装，无溶剂聚脲快速固化与聚氨酯后固化相结合的高装饰性耐划伤涂料等。今后其重点发展方向如下。  \n\n$\\Phi$ 加快水性汽车涂料、水性防腐涂料、水性木器和塑料涂料等工业涂料发展的步伐。制定适应市场需求的产品标准，优化性价比，加快涂装工艺和标准开发，开展涂装工技能培训，促进产品进入市场。开发常温固化，单组分和双组分，低温和高温烘烤，以及适合不同需求的产品线。  \n\n$\\textcircled{2}$ 紫外光固化进一步开发高性能、耐黄变的脂肪族丙烯酸聚氨酯树脂、环氧系列紫外光固化树脂。开展适合复杂形状加工的复合固化机理的研究，高颜基比和厚涂层适用的光敏体系和固化机理。更加安全和低黏度、低挥发性的活性稀释剂，乃至水分散型的紫外光固化体系走向实用化。应用范围扩大到纸加工、卷材、塑料等。  \n\n$\\textcircled{3}$ 粉末涂料朝汽车、木器加工、塑料、卷材等领域拓展，新型的低温固化树脂和交联体系，高装饰性和薄层涂装成为主要的研发方向。在保持高生产率的同时，节能也是重要的目标。  \n\n$\\textcircled{4}$ 目前传统的醇酸调合漆在溶剂型涂料中占有最大的份额，提升高固体分涂料的比重，及相关的低黏度树脂和催干体系的开发十分重要。高固体分防腐涂料，木器和塑料涂料，及配套的涂装工艺的开发将深人开展。无溶剂环氧、聚氨酯防腐涂料及涂装工艺， $100\\%$ 喷涂聚脲，不饱和聚酯地坪涂料等无溶剂体系开始在工程中应用。随着配套原材料和涂装设备工艺的完善，它们将占有更大的份额。 9八",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 109,
+        "chunk": "# 七、生产流程和管理创新促进高效、安全和环保涂料生产  \n\n随着颜料行业提供多品种、超细粉碎、经功能性表面处理的颜填料，高效分散设备的研发和使用，色浆工艺和电脑配色系统、工厂和零售终端的日益普及，现代物流管理和ERP管理系统的实施等，涂料生产和管理过程将更加高效、简单和可靠。未来的乳胶漆和醇酸通  \n\n用性涂料的生产厂简化为基础色浆的加工厂，在实现零库存的目标下，集装箱和高速公路成为原料及成品仓库，而零售店成为配色车间和产品终端。  \n\n在工业涂料和特种功能涂料领域，专业化和为用户提供完整的涂料及涂装解决方案成为竞争力的核心。从材料创新至产品创新，应用开发和涂装工艺，直至完善的技术服务体系的建立，涵盖了涂料工艺的系统内容，即流程和系统的创新将成为主流。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 110,
+        "chunk": "# 参考文献  \n\n[1]涂料工艺编委会，涂料工艺、第3版、北京：化学工业出版社，1997.  \n[2] [美］ZenoW．威克斯等，有机涂料科学和技术，经良，姜英涛等译，北京：化学工业出版社，2002.  \n[3] Parsons P, Waldie J M, Surfac Co oatings Australia; Southwood Press Pty Limited, 1987,[4] 中国涂料 $\\cdot+-\\sqrt{2}^{\\ast}$ 科技创新发展纲要，中国涂料，2006，12.  \n[5] 中国涂料工 $^{\\ast}+-\\kappa^{\\ast}$ 发展规划思路．中国涂料，2005，10.  \n[6] 中国涂料工 刘登良主编. 中国涂料工业年鉴，2002—2007.  \n[7] 刘登良编著 工业出版社，2001.  \n[8] 刘登良编著 海洋涂料与 装技术 北京 化学工业出版社，2002.  \n[9] 刘登良编著 深层失效分析方法和 工作程序 北京：化学工业出版社，2004.  \n[10] 马庆麟主编，涂料工业手册，北京：化学工业出版社，2001.  \n\n第二篇",
+        "category": " References"
+    },
+    {
+        "id": 111,
+        "chunk": "# 涂料成膜物树脂",
+        "category": " Introduction"
+    },
+    {
+        "id": 112,
+        "chunk": "# 第一节松香树脂  \n\n松香是一种来源广泛可再生的天然树脂，主要来源于松树，割开松树后，收集到的油状物，即为松脂，主要由树脂酸和烃组成，还含有少量杂质与水分。其成分因树种、产地、采脂方法等而有所不同，松脂经加工处理后可得到松香，松树能在恶劣环境中生长，有利于综合利用。随着煤炭、石油等一次性资源的逐渐枯竭，可再生松香的重要性必然上升，我国是松香生产大国，年产量约70万吨，怎样充分利用优势资源，是值得进行深人研究的课题。  \n\n松香主要由各种树脂酸组成，树脂酸含有三环骨架结构，含有两个双键和一个羧基两种活性中心，通过与羧基的酯化、中和及与双键的加成、氢化、歧化、聚合等，可改变松香的理化性能，拓展其应用领域，这些经过改性的产物，统称为改性松香树脂，在涂料、油墨、胶黏剂等行业有广泛应用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 113,
+        "chunk": "# 一、原料  \n\n改性松香树脂生产过程中，除使用松香外，根据不同的改性工艺，还需使用其他原料，比较常见的有：多元醇（主要有甘油、季戊四醇)、醛类（主要有甲醛）、多元酸（主要有顺丁烯二酸酐）、酚类（主要有苯酚、双酚A、对叔丁酚）、催化剂（主要有次磷酸、乌洛托品、氧化锌）等，这里主要针对松香和催化剂做一些介绍。 双数",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 114,
+        "chunk": "# 1.松香  \n\n松香按其来源可分为三类：脂松香（由松脂经蒸馏得到)、木松香（松树干和根切碎后，用溶剂萃取得到）、浮油（妥尔油）松香（由减压蒸馏纸浆厂的副产品松浆油得到）。我国以脂松香为主，发达国家因造纸业的发展和环保的严格控制，加上劳动力成本的原因，脂松香产量最少，浮油松香产量最大。但由于生产浮油松香和木松香的原料来源日渐减少，就需要  \n\n脂松香来满足市场需求。  \n\n树脂酸有多种同分异构体，可分为两类：①枞酸型酸，主要有枞酸、新枞酸、长叶松酸、脱氢枞酸、左旋海松酸等；②海松酸型酸，主要有海松酸、右旋海松酸、异右旋海松酸等，所占含量因松树产地、种类、松香加工工艺的差异而不同。树脂酸的主要异构体结构如下。  \n\n![](images/c793ca8bed67997c4c95c6c1473ac28571bd7e0ff2b5622ba7462e8bde9c202e.jpg)  \n\n共轭双键具有较高的化学活性，在松香中，含有共轭双键的树脂酸占总量 $70\\%$ 以上，因此这类树脂酸的化学反应研究最多；共轭双键树脂酸含量高的松香，有利于进行加成反应。  \n\n生产松香树脂时，酯化反应温度一般要达到 $270^{\\circ}\\mathrm{C}$ ，树脂酸在此温度下易分解，生成松脂烃与二氧化碳。  \n\n![](images/2b7c9f5dc545f89c18c518ad2b902ab0dbd7d7121238a111622f1dc034ed8f5b.jpg)  \n\n松脂烃为黏稠状液体，树脂若含有松脂烃会使树脂软化点下降，使得漆膜硬度下降，干燥缓慢，耐水性变差，因此松香树脂生产的最后阶段，都有一段时间的减压维持阶段，来达到尽可能减少树脂中松脂烃含量的目的。  \n\n我国的松香（脂松香）国家标准为GB8145—1987《脂松香》，见表2-1-1。  \n\n表2-1-1松香（脂松香）国家标准  \n\n\n<html><body><table><tr><td rowspan=\"2\">项目</td><td colspan=\"6\">指 标</td></tr><tr><td>特级</td><td>一级</td><td>二级</td><td>三级</td><td>四级</td><td>五级</td></tr><tr><td>外观</td><td colspan=\"6\"></td></tr><tr><td rowspan=\"2\">颜色</td><td>微黄 黄</td><td></td><td>透 明体 黄色</td><td>深黄</td><td>黄棕</td><td>黄红</td></tr><tr><td colspan=\"6\">符合松香色级玻璃标准色块的要求</td></tr><tr><td>软化点(环球法）/C ≥</td><td colspan=\"2\">76</td><td colspan=\"2\">75</td><td colspan=\"2\">74</td></tr><tr><td>酸值/（mgKOH/g）</td><td colspan=\"2\">166</td><td colspan=\"2\">165</td><td colspan=\"2\">164</td></tr><tr><td>不皂化物量/% ≤</td><td colspan=\"2\">5</td><td colspan=\"2\">5</td><td colspan=\"2\">6</td></tr><tr><td>乙醇不溶物/% ≤#</td><td colspan=\"2\">0.03</td><td colspan=\"2\">0.03</td><td colspan=\"2\">0.04</td></tr><tr><td>灰分/% ≤</td><td colspan=\"2\">0.02</td><td colspan=\"2\">0.03</td><td colspan=\"2\">0.04</td></tr></table></body></html>  \n\n国内现行的松香分级方法，是以松香的色泽来区分的，简单的色泽分级不能适应用户的要求；不同类型松香制品对松香的具体要求是不同的，如含有共轭双键树脂酸比例大的松香，容易进行加成反应，有利于松香顺酐树脂的合成。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 115,
+        "chunk": "# 2.催化剂  \n\n改性松香树脂中常用的树脂品种是：多元醇酯、顺酐多元醇酯和酚醛树脂。由于酚醛树脂中含有醒式结构和游离酚，酯化反应并非影响色泽的主要因素，缩合反应起主导作用，主要采用不用或少用六亚甲基四胺的办法来适当降低色泽。相关内容在本书酚醛树脂中叙述。  \n\n松香的羧基处在叔碳位置上，空间位阻大，反应活化能高，酯化反应要在长时间（6～10h)、高温（约 $270^{\\circ}\\mathrm{C}$ ）反应，为加快酯化反应速度，需要加入合适的催化剂。早前生产松香树脂，通常使用金属氧化物（氧化锌、氧化镁等）作为酯化反应催化剂，但生产得到的树脂色泽较深，一般都在10号（Fe-Co）以上，松香改性酚醛树脂的色泽要达到12号。随着对松香酯化反应的研究进展，松香酯化反应的催化剂开始向酸催化、亚磷酸类和硫酚系列发展，国外在20世纪80年代初期开始采用新型催化剂，我国在20世纪90年代中期开始在工业化生产中大规模采用。  \n\n（1）酸催化常用的有对甲苯磺酸、次磷酸等，国内多采用次磷酸，其工艺技术成熟，但反应时会生成有毒气体 $\\mathbf{PH}_{3}$ ，对环境产生一定影响；使用次磷酸要注意加入温度，过高时极易发生燃烧现象。  \n\n(2）亚磷酸盐、亚磷酸胺和亚磷酸酯类常用有金属的 $\\mathrm{[Na_{2}P O_{3}}$ 、 $(\\mathrm{NH}_{4})_{2}\\mathrm{PO}_{3}\\mathrm{\\cdot}$ 、一苯基二异辛酸酯、亚磷酸三（2,4-二叔丁苯基）酯（168）、三壬苯基亚磷酸酯（TNPP)等，与酸催化比，单独使用时，减色效果要差一些。  \n\n(3）硫酚系列化合物和低聚物常用的有4，4-二（6-叔丁基-间甲苯基）硫酚（300）等。与前两类相比，可加快酯化反应速度，减少不溶物的产生，但单独使用这一类催化剂，容易出现树脂外观透明，但苯中清浑浊的现象。  \n\n目前采用的几类酯化反应催化剂，单独使用都有局限性，会出现： $\\Phi$ 松香树脂不透明；$\\textcircled{2}$ 树脂透明但有细小不溶物； $\\textcircled{3}$ 树脂透明、苯中清浑浊。为解决上述问题，一般采取两种或两种以上不同类型的催化剂进行配合。  \n\n从多元醇分子结构上看，甘油含有一个仲羟基，而季戊四醇与三羟甲基丙烷全部为伯羟基，甘油羟基全部接在分子主链上，而季戊四醇与三羟甲基丙烷羟基全部接在分子支链上，由于支链对羟基的影响，甘油空间位阻明显大于季戊四醇与三羟甲基丙烷，酯化反应活化能高，酯化反应活化能：甘油酯>季戊四醇酯>三羟甲基丙烷酯；羟基接在主链上的甘油酯化反应控制要求高，控制不当容易出现树脂不透明，或树脂透明但苯中清浑浊的现象。松香顺酐甘油酯，由于树脂结构中顺酐的影响，反应活化能降低，酯化反应顺利进行，容易得到合格的松香顺酐甘油酯。  \n\n综合各种因素并通过试验确认，生产松香甘油酯，选择亚磷酸酯类的168与硫酚系列的300配合；生产松香季戊四醇酯，选择酸性催化剂中的次磷酸与硫酚系列的300配合；生产松香顺酐甘油酯，选择酸性催化剂中的次磷酸与硫酚系列的300配合；生产松香顺酐季戊四醇酯，选择酸性催化剂中的次磷酸与亚磷酸酯类的一苯基二异辛酸酯配合。确定了复配催化剂的组合后，还要根据生产实际，通过试验来确认催化剂复配比例，以达到降低色泽的效果。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 116,
+        "chunk": "# 二、松香树脂生产设备  \n\n松香改性树脂的生产，以前一般采用直接火加热形式，现在已很少采用这种方式，目前大都采用高温导热油循环加热的形式。反应釜采用不锈钢制作，使用浆式搅拌（附刮沫器)，配备直冷凝器、横冷凝器（附分水器)、高位槽、泄爆口、真空泵和造粒机（或切片机）等附件。用不锈钢保温球阀保证底部出料时顺畅，为加快出料速度，可用蒸汽或情性气体压料，出料后立即用蒸汽降温，避免内壁沾附料过热变深，影响下一批色泽。反应釜内壁沾附料难以避免，有可能会污染影响下一批料，可抛光反应釜内壁，减少摩擦系数，使树脂不易黏附。  \n\n不同类型松香树脂，对附件的要求是不同的；如生产松香钙皂时，可不用冷凝器，但其他品种是需要的。用高位槽滴加丙烯酸单体和分水器来维持回流，是丙烯酸改性松香树脂需要的，其他品种可以不用，因此生产设备，应根据所生产松香树脂的类型来建设。  \n\n改性松香树脂生产的设备简图如图2-1-1所示。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 117,
+        "chunk": "# 三、松香树脂的质量指标  \n\n![](images/2535d57e90e1204ec226aecb9af3b3841e1d641ce848efc1b4cd9ea2e3a55b53.jpg)  \n图2-1-1改性松香树脂生产设备1-反应釜；2-吸风机；3—高位槽；4-直冷凝器；5—横冷凝器；6一分水器  \n\n松香树脂常规指标主要是色泽、酸值、软化点、溶解性、外观等五项，油墨用的松香酚醛树脂还有亚麻油中黏度及正庚烷值两项指标。  \n\n由于原料来源的差异、生产工艺的不同，会出现检验结果相近，但树脂分子量和分子量分布相差较大，这说明目前的这些指标，未能完全体现树脂的性能情况。不少国外松香树脂，除了常规的产品指标外，还出现黏度指标；油墨用松香改性酚醛树脂一般也采用油中黏度的方式，其他树脂一般采用溶剂溶解后的黏度，液体的二元醇酯一般直接测旋转黏度。对常规指标相同的同一品种不同批次树脂进行检测，结果显示黏度和分子量及分子量分布体现出很大的相关性，如果树脂建立黏度指标，可更好地满足用户要求，提高产品的品质。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 118,
+        "chunk": "# 四、松香树脂分类与合成  \n\n松香的羧基处在叔碳结构上，空间位阻大，反应活化能高，与羧基的酯化反应一般要在高温、适当的催化剂下才能顺利进行，根据生产松香树脂使用的原料和工艺路线，可将改性松香树脂分成五类。",
+        "category": " Introduction"
+    },
+    {
+        "id": 119,
+        "chunk": "# 1.松香皂  \n\n树脂酸具有一元羧酸特征，可进行一系列羧基反应；和金属氧化物或氢氧化物在高温下中和，生成树脂酸的金属盐，也称松香皂。常用的松香皂是松香钙皂（又称石灰松香)。松香钙皂透明度较差，若在生产时加人少量碳酸锂，可改善成品的透明度。  \n\n$$\n2C_{19}\\mathrm{H_{29}C O O H+C a(O H)_{2}}=(C_{19}\\mathrm{H_{29}C O O)_{2}C a+2H_{2}O}\n$$  \n\n生产注意事项：加石灰前应开启防爆管，防止加石灰时突然溢锅；维持温度不宜超过$230\\mathrm{\\mathfrak{C}}$ ，过高容易造成树脂胶结，若发现树脂有结锅的趋势，可立即投入少量松香来避免结锅；要尽量使用新制得的熟石灰。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 120,
+        "chunk": "# 配方实例：100石灰松香操作规程  \n\n配方松香  \n\n成品指标  \n酸值/（mgKOH/g)  \n操作工艺  \n\n≤100 软化点（环球法）/C  \n\n①吸人熔化后的松香，开动搅拌；在160℃以下，均匀地加入熟石灰，加完后维持1h。  \n$\\textcircled{2}$ 维持结束，升温到约 $220^{\\circ}\\mathrm{C}$ 后维持1h。  \n$\\textcircled{3}$ 取样，进行终点控制（软化点、酸值)；若酸值未到则继续维持反应。  \n$\\textcircled{4}$ 合格后，放料、冷却、包装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 121,
+        "chunk": "# 2.松香多元醇酯  \n\n涂料和黏合剂中采用多元醇与松香进行酯化，生成多元醇酯，最常用的是松香甘油酯和松香季戊四醇酯，主要用于生产黏合剂、硝基漆、油墨等。1，3-丙二醇酯是高黏性液体树脂，能与弹性体及其他树脂相容，可作为增黏树脂使用，主要用于生产高黏结力、高弹性的热熔胶和压敏胶，也可用作硝基漆增塑剂。乙二醇酯为固体树脂，软化点约 $60\\sim65\\mathrm{{C}}$ ，可用作黏合剂和增塑剂。在松香产地生产改性松香树脂，可将未冷却成型的液态松香直接投入树脂反应釜，然后升温到一定温度，并减压维持一段时间，脱除松香含有的氧化松香、松节油与其他杂质，然后降温，再用多元醇酯化，由于多了一步精制松香的工序，若使用特级松香生产，可得到1号（Fe-Co）色的松香多元醇酯，产品的灰分也很低，可用于食品行业。  \n\n在松香多元醇酯中，最常用的是甘油酯和季戊四醇酯，其软化点大小为：季戊四醇酯>甘油酯>三羟酯，配制成清漆季戊四醇酯硬度高、干燥快，若生产黏合剂则甘油酯黏结强度好。由于松香酸中羧基活化能大，因此反应要使用适当的催化剂才可顺利进行。生产多元醇酯的化学反应如下：  \n\n生产注意事项：加甘油时必须注意泡沫上升情况，加入速度及升温应作适当控制，以免突然溢锅；加季戊四醇时要缓慢均匀加人反应釜中部，以免季戊四醇不能及时溶化黏于锅壁而产生焦化；减压时，真空应逐渐开大，以免树脂溢出；取样时若酸值过高，应补加多元醇。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 122,
+        "chunk": "# 配方实例：138松香甘油醋操作规程  \n\n<html><body><table><tr><td>配方 松香</td><td></td><td>5000kg 甘油 168抗氧剂</td><td></td><td>560kg</td></tr><tr><td>300抗氧剂 成品指标</td><td></td><td>5.0kg</td><td></td><td>5.0kg</td></tr><tr><td>外观</td><td></td><td>透明固体 色泽（Fe-Co)</td><td></td><td>≤5</td></tr><tr><td>酸值/(mgKOH/g)</td><td></td><td>≤10 软化点/℃</td><td></td><td>≥85</td></tr><tr><td>苯中清</td><td></td><td>清</td><td></td><td></td></tr></table></body></html>  \n\n操作工艺  \n\n$\\Phi$ 吸进松香、开动搅拌，投入甘油（加料时应注意泡沫上升情况，防止溢锅)，同时开启横、直冷凝器冷却水。然后在140℃以下，加人300与168抗氧剂。  \n\n$\\textcircled{2}$ 维持 $15\\mathrm{min}$ ，升温至 $200\\mathrm{\\textperthousand}$ 后，维持1h。  \n$\\textcircled{3}$ 维持结束，升温到 $270^{\\circ}\\mathrm{C}$ 后维持6h，关闭直冷凝器冷却水，在维持温度下抽真空2h。  \n$\\textcircled{4}$ 取样，进行终点控制（软化点、酸值)；若酸值未到则继续维持反应。  \n$\\textcircled{5}$ 合格后，放料、冷却、包装。  \n\n配方实例：145松香季戊四醇酯操作规程  \n\n<html><body><table><tr><td colspan=\"3\">配方</td></tr><tr><td>松香</td><td>5000kg</td><td>季戊四醇</td><td>575kg</td></tr><tr><td>次磷酸</td><td>2.5kg</td><td>300抗氧剂</td><td>2.5kg</td></tr><tr><td>成品指标</td><td></td><td></td><td></td></tr><tr><td>外观</td><td>透明固体</td><td>酸值/（mgKOH/g)</td><td>≤25</td></tr><tr><td>色泽（Fe-Co)</td><td>≤5</td><td>苯中清</td><td>清</td></tr><tr><td>软化点（环球法）/℃</td><td>≥85</td><td></td><td></td></tr></table></body></html>  \n\n操作工艺  \n\n$\\Phi$ 投入熔化后松香，开动搅拌；在 $100^{\\circ}\\mathrm{C}$ 以下，加入次磷酸和300抗氧剂，维持0.5h，然后升温到约 $180\\mathrm{^c}$ 投入季戊四醇，加料时应注意泡沫上升情况，防止溢锅。  \n\n$\\textcircled{2}$ 打开直冷凝器、横冷凝器冷却水，升温到约 $200^{\\circ}\\mathrm{C}$ 后维持 $_{1\\sim2\\mathrm{h}}$ 。  \n$\\textcircled{3}$ 维持结束，升温到270℃维持 $6\\sim10\\mathrm{h}$ ，关直冷凝器冷却水，并在维持温度下减压2h。  \n$\\textcircled{4}$ 取样，进行终点控制（软化点、酸值)；若酸值未到则继续维持反应。  \n$\\textcircled{5}$ 合格后，放料、冷却、包装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 123,
+        "chunk": "# 3.松香酚醛树脂  \n\n甲醛和酚类的缩合产物与松香加成后，并与多元醇酯化改性而成的合成树脂。松香酚醛树脂将在本书酚醛树脂章节中专门介绍，这里予以省略。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 124,
+        "chunk": "# 4.松香顺酐多元醇酯  \n\n松香和顺酐经加成反应形成高酸值三元酸，由于反应后共轭双键消失，化学性质稳定，氧化反应倾向降低，造纸行业可作为施胶剂使用。加成时若顺丁烯二酸酐含量高，多元醇酯化后的软化点高、油溶性差，产品没有实际使用价值。生产不同用途的松香顺酐多元醇酯，需要选择不同用量的顺酐和酯化多元醇。水性或醇溶性油墨用的松香顺酐多元醇酯，树脂酸值较大，顺酐比例自然要高很多。松香顺酐多元醇酯主要用于硝基漆、塑料油墨、电化铝等行业。  \n\n松香所含树脂酸中，左旋海松酸共轭双键在同一环上，有利加成反应进行；除左旋海松酸常温下可加成外，其他树脂酸只有在一定的条件下，异构化为左旋海松酸后，再进行加成，高温下，其他树脂酸与左旋海松酸处于动态平衡，左旋海松酸不断被顺酐消耗，又不断的生成。  \n\n![](images/1217ef28cbf974a06857801dfddf77bc4d9f76ac854a1e09b9d5f0b7f97e9a3d.jpg)  \n松香顺酐甘油酯反应示意式  \n\n生产注意事项：顺酐应迅速加入、如有结块，应事先粉碎后再投，如与顺酐升华蒸气接触，立即用水冲洗；加季戊四醇要缓慢均匀加入反应釜中部，以免不能及时溶化黏于锅壁产生焦化；加甘油必须注意泡沫上升情况，加入速度，升温应适当控制，以免突然溢锅。  \n\n配方实例：422松香顺酐甘油醋操作规程  \n\n\n<html><body><table><tr><td>配方</td><td></td><td></td><td></td></tr><tr><td>松香</td><td>4500kg</td><td>300抗氧剂</td><td>7.0kg</td></tr><tr><td>次磷酸</td><td>2.5kg</td><td>甘油</td><td>830kg</td></tr><tr><td>顺酐</td><td>500kg</td><td></td><td></td></tr><tr><td>成品指标</td><td></td><td></td><td></td></tr><tr><td>外观</td><td>透明固体</td><td>色泽(Fe-Co)</td><td>≤5</td></tr><tr><td>酸值/(mgKOH/g)</td><td>≤30</td><td>软化点/C</td><td>≥128</td></tr><tr><td>苯中清</td><td>清</td><td></td><td></td></tr></table></body></html>  \n\n操作工艺  \n\n$\\Phi$ 吸进松香、开动揽拌，在 $150^{\\circ}\\mathrm{C}$ 以下，迅速加入顺酐，温度会自升，并维持1.0h；打开直冷凝器、横冷凝器冷却水，缓慢加人甘油；加料时应注意泡沫上升情况，防止溢锅。  \n\n$\\textcircled{2}$ 加人甘油，不要升温，在 $140^{\\circ}\\mathrm{C}$ 以下，加入次磷酸和300抗氧剂；然后升温至$200^{\\circ}\\mathrm{C}$ ，并在 $200^{\\circ}\\mathrm{C}$ 维持 $2.0\\mathrm{h}$ 费  \n\n$\\textcircled{3}$ 维持结束，升温到 $270\\Upsilon$ 维持4.0h，关闭直冷凝器冷却水，然后抽真空2h。  \n\n$\\textcircled{4}$ 取样，进行终点控制（软化点、酸值），$\\textcircled{5}$ 合格后，放料、冷却、包装。  \n\n配方实例：424松香顺酐季戊四醇酯操作规程  \n\n<html><body><table><tr><td>配方</td><td></td><td></td><td></td></tr><tr><td>松香</td><td>4700kg</td><td>一苯基二异辛酸酯</td><td>5kg</td></tr><tr><td>次磷酸</td><td>5kg</td><td>季戊四醇</td><td>685kg</td></tr><tr><td>顺酐</td><td>155kg</td><td></td><td></td></tr><tr><td>成品指标</td><td></td><td></td><td></td></tr><tr><td>外观</td><td>透明固体</td><td>色泽(Fe-Co)</td><td>≤6</td></tr><tr><td>酸值/（mgKOH/g)</td><td>≤16</td><td>软化点/C</td><td>≥120</td></tr><tr><td>苯中清</td><td>清</td><td></td><td></td></tr></table></body></html>  \n\n操作工艺  \n\n$\\textcircled{1}$ 吸进松香、放去真空，开动搅拌；在 $150\\mathrm{^c}$ 以下，迅速加人顺酐及次磷酸、一苯基二异辛酸酯；温度会自然上升，维持0.5h后，升温到 $200^{\\circ}\\mathrm{C}$ 维持1.0h。  \n\n$\\textcircled{2}$ 打开直冷凝器、横冷凝器冷却水，加入季戊四醇；加料时应注意均匀加入，防止溢锅。  \n\n$\\textcircled{3}$ 加完后维持1.0h，升温到 $270^{\\circ}\\mathrm{C}$ 维持8.0h，关闭直冷凝器冷却水，然后抽真空4.0h。  \n\n$\\textcircled{4}$ 取样，进行终点控制（软化点、酸值）。  \n$\\textcircled{5}$ 合格后，放料、冷却、包装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 125,
+        "chunk": "# 5.丙烯酸改性松香树脂  \n\n松香、顺酐、乙二醇在一定温度与条件下进行酯化反应，然后在引发剂的作用下与丙烯酸单体进行共聚反应，最后得到丙烯酸改性的松香顺酐树脂，属热塑性树脂，可冷却造粒、也可用溶剂溶解。通过顺酐、乙二醇比例的调整，更可通过丙烯酸单体种类和改性程度的调整，得到多种不同应用性能的丙烯酸改性松香树脂。  \n\n为提高产品的性能，反应后期要将未反应的多元醇从产物中除去，因此选择乙二醇或1,3-丙二醇等能与后加入的二甲苯形成共沸的多元醇。松香、顺酐和多元醇酯化反应的同时，松香与顺酐的加成反应也使双键减少，若采取熔融酯化，由于温度高，反应物浓度大，松香与顺酐加成反应倾向大，消耗双键过多，难以保证酯化产物与丙烯酸单体加成顺利进行，因此采用溶剂法进行酯化反应，为加快反应，要加入酯化催化剂。  \n\n(1）工艺路线和基本原理  \n\n![](images/820dcde196241e562719aeefefe81ec24d4a491da4a6e84451f59bf9a684239c.jpg)  \n\n(2）生产注意事项滴加乙二醇和丙烯酸单体时应控制好滴加速度及温度，切忌温度波动大和速度不均匀；回流脱水时，要确保水和残余乙二醇顺利脱尽；若生产固体成品，脱溶剂前要消耗掉补加的引发剂（注意引发剂在反应温度下半衰期)，溶剂要降温后减压脱。  \n\n配方实例：丙烯酸改性松香树脂操作规程  \n\n\n<html><body><table><tr><td>配方</td><td>2700kg</td><td></td><td></td></tr><tr><td>松香</td><td rowspan=\"4\">620kg ①16kg②4kg 250kg</td><td>顺酐</td><td>415kg</td></tr><tr><td>乙二醇</td><td>甲苯</td><td>190kg</td></tr><tr><td>过氧化二叔丁基 二甲苯</td><td>TNPP</td><td>2kg</td></tr><tr><td></td><td>甲甲酯</td><td>1200kg</td></tr><tr><td>苯乙烯</td><td colspan=\"3\">2000kg</td></tr><tr><td>成品指标</td><td colspan=\"3\">透明固体</td></tr><tr><td>外观</td><td></td><td>色泽(Fe-Co)</td><td>≤5 100~120</td></tr><tr><td>酸值/(mgKOH/g)</td><td>≤25</td><td>软化点(环球法)/C</td><td></td></tr><tr><td>苯中清</td><td colspan=\"3\">清</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 126,
+        "chunk": "# 操作工艺  \n\n$\\textcircled{1}$ 投入熔化后的松香，开动搅拌；在150℃以下，迅速加入顺酐、TNPP和二甲苯；等温度稳定后维持在 $180{\\sim}185\\bar{\\mathrm{C}}$  \n\n$\\textcircled{2}$ 滴加乙二醇，控制滴加温度 $180{\\sim}185\\mathrm{\\bar{C}}$ ，滴加时间 $_{2\\sim3\\mathrm{h}}$ α  \n\n$\\textcircled{3}$ 滴加完成后，在 $180\\sim185^{\\circ}\\mathrm{C}$ 维持反应，并取样测酸值，等酸值 $\\leqslant50$ 后，结束维持。  \n\n$\\textcircled{4}$ 加人二甲苯，回流，脱出酯化反应生成水和残留的乙二醇。  \n\n$\\textcircled{5}$ 滴加混合好的甲甲酯、苯乙烯、过氧化二叔丁基 $\\textcircled{1}$ ，控制滴加温度 $135\\sim140^{\\circ}{\\mathrm{C}}$ ，滴加时间 $8\\mathrm{\\sim}10\\mathrm{h}$ 费  \n\n$\\textcircled{6}$ 滴加完成后，在 $135{\\sim}140^{\\circ}\\mathrm{C}$ 维持 $2\\mathord{\\sim}4\\mathrm{h}$ ，补加过氧化二叔丁基 $\\textcircled{2}$ ，继续维持反应并取样，直至反应到规定的黏度为止。  \n\n$\\textcircled{7}$ 减压脱尽溶剂后，冷却后造粒包装或加人适当的溶剂，稀释到规定的浓度后包装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 127,
+        "chunk": "# 五、松香树脂的应用  \n\n改性松香树脂主要有松香皂、松香多元醇酯、松香酚醛树脂、松香顺酐多元醇酯、丙烯酸改性松香树脂五大类，不同的类别，树脂分子结构差异很大，性能也不同，应用的领域也不同。",
+        "category": " Introduction"
+    },
+    {
+        "id": 128,
+        "chunk": "# 1.松香皂  \n\n最常用的松香皂产品是松香钙皂（亦称石灰松香)。是最简单的改性松香树脂，可作为底漆用树脂，目前单独制漆已很少采用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 129,
+        "chunk": "# 2.松香多元醇酯  \n\n最常用的是甘油酯和季戊四醇酯，甘油酯主要用于生产热熔胶、压敏胶，也有用于生产硝基漆；季戊四醇酯主要用于生产热熔胶、压敏胶，也有用于生产热熔标线漆。特性黏结力好、与石蜡与橡胶的混溶性好，涂膜硬度高。  \n\n丙二醇酯和乙二醇是高黏性液体树脂，与弹性体及其他树脂有良好的相容性，可作为增黏性树脂使用，用于生产热熔胶和压敏胶，也可用作硝基漆的增塑剂。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 130,
+        "chunk": "# 3.松香酚醛树脂  \n\n最常用的是采用苯酚的酚醛树脂，主要用于生产酚醛漆和酚醛胶黏剂，目前国内生产此类酚醛树脂，采用的缩合反应催化剂有六亚甲基四胺和熟石灰，采用前者，成品颜色约12号，采用后者成品颜色约10号，用于生产酚醛漆时，二者相差不大，但用于生产酚醛胶黏剂时，使用六亚甲基四胺的酚醛树脂，胶黏剂性能要好些。  \n\n采用双酚A、叔丁基苯酚的酚醛树脂主要用于生产胶印油墨。为进一步提高树脂的性能，采用辛基酚、壬基酚、十二烷基酚等碳链较长烷基酚生产树脂，使得树脂具有更好的溶解性、较大的黏度、较高的分子量，提高与颜料润湿分散性，使胶印油墨可大量使用脂肪烃矿物油，改善流平性和光泽。  \n\n配方实例：酚醛调合漆配方实例  \n\n\n<html><body><table><tr><td colspan=\"4\">50%白酚醛调合浆：</td></tr><tr><td>原料名称</td><td>用量/kg</td><td>原料名称</td><td>用量/kg</td></tr><tr><td>酚醛漆料</td><td>434</td><td>超细高岭土</td><td>92</td></tr><tr><td>B101钛白粉</td><td>58</td><td>200*溶剂</td><td>66</td></tr><tr><td>立德粉</td><td>350</td><td></td><td></td></tr><tr><td colspan=\"4\">白色酚醛调合漆：</td></tr><tr><td>原料名称</td><td>用量/kg</td><td>原料名称</td><td>用量/kg</td></tr><tr><td>50%白酚醛调合浆</td><td>800</td><td>催干剂</td><td>8</td></tr><tr><td>酚醛漆料</td><td>178</td><td>200*溶剂</td><td>2</td></tr><tr><td>群青调合浆</td><td>2</td><td></td><td></td></tr><tr><td colspan=\"4\">20%黑酚醛调合浆：</td></tr><tr><td>原料名称</td><td>用量/kg</td><td>原料名称</td><td>用量/kg</td></tr><tr><td>酚醛漆料</td><td>590</td><td>超细高岭土</td><td>140</td></tr><tr><td>中色素发黑</td><td>60</td><td>200*溶剂</td><td>200</td></tr><tr><td>催干剂</td><td>10</td><td></td><td></td></tr><tr><td colspan=\"4\">黑色酚醛调合漆：</td></tr><tr><td>原料名称</td><td>用量/kg</td><td>原料名称</td><td>用量/kg</td></tr><tr><td>20%黑酚醛调合浆</td><td>500</td><td>催干剂</td><td>35</td></tr><tr><td>酚醛漆料</td><td>455</td><td>200*溶剂</td><td>10</td></tr></table></body></html>\n\n注：酚醛漆料由210酚醛树脂与桐油等干性油熬炼而成。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 131,
+        "chunk": "# 4.松香顺酐多元醇酯  \n\n松香和顺酐加成后，共轭双键消失，化学性质稳定，氧化变色倾向降低，可以应用于造纸、油墨、黏合剂、绝缘材料等场合。造纸工业可用作强化施胶剂。采用多元醇酯化，大幅度降低了产物的酸值，酯化产物软化点提高，拓展了产品的应用。 MP  \n\n酯化选用的多元醇不同，顺酐加成量的不同，产品性能就会不同，应用领域也不同，这类树脂主要用于热熔标线漆、硝基漆等，在塑料油墨、水可洗油墨、电化铝等行业也有应用。  \n\n配方实例：热熔型道路标线漆（白）配方实例  \n\n\n<html><body><table><tr><td>原料名称</td><td>用量/kg</td><td>原料名称</td><td>用量/kg</td></tr><tr><td>石油树脂</td><td>150</td><td>424树脂</td><td>150</td></tr><tr><td>EVA胶</td><td>25</td><td>石蜡</td><td>30</td></tr><tr><td>200*溶剂</td><td>13</td><td>增塑剂</td><td>12</td></tr><tr><td>配漆(白)：</td><td></td><td></td><td></td></tr><tr><td>原料名称</td><td>用量/kg</td><td>原料名称</td><td>用量/kg</td></tr><tr><td>混合料</td><td>380</td><td>体质颜料</td><td>380</td></tr><tr><td>钛白粉</td><td>100</td><td>玻璃微珠</td><td>16</td></tr></table></body></html>\n\n注：增塑剂采用低分子量无溶剂醇酸树脂，也有采用二丁酯或二辛酯。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 132,
+        "chunk": "# 5.丙烯酸改性松香树脂  \n\n此类树脂可冷却造粒，也可用溶剂溶解。可用于生产热熔涂料和溶剂型涂料，在水泥、沥青、工程塑料、木材等基材上附着力突出、硬度大、耐磨性和柔韧性好。可用于道路标志漆、塑料漆、木器漆等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 133,
+        "chunk": "# 第二节醇酸树脂",
+        "category": " Introduction"
+    },
+    {
+        "id": 134,
+        "chunk": "# 一、概述  \n\n从1927年醇酸树脂问世以来，至今已有80多年的历史。它的出现打破了以干性油和天然树脂为传统涂料的生产工艺，使涂料生产走上了现代化学合成的工业化道路，开创了涂料生产的新纪元。  \n\n我国生产醇酸树脂也有60多年的历史。几十年来，醇酸树脂已成为我国涂料工业中最重要的合成树脂之一。自20世纪80年代以来，我国醇酸树脂不仅产量稳定提高，而且品种、质量、生产工艺、规模及基础理论的研究都有很大提高，与国外同类产品差距越来越小。  \n\n醇酸树脂是以多元醇、多元酸（一般）经脂肪酸（或油）改性共缩聚而成的线型聚酯，分子结构是以多元醇的酯为主链、以脂肪酸酯为侧链。在工艺上，20世纪60年代以前，醇酸树脂生产基本上采用熔融法，60年代以后溶剂法在我国涂料行业得到广泛应用，到80年代末，醇酸树脂开始实现商品化，生产规模大型化，很多企业的反应釜都达到12m以上，而脂肪酸法生产工艺也得以普及。目前醇酸树脂油度越来越短、颜色越来越浅、固体分越来越高、品种越来越多。这一时期是我国醇酸树脂快速发展时期。21世纪以来，由于能源和环境保护问题，对醇酸树脂的发展提出新的课题，高固体分、低VOC、水性化醇酸树脂方面的研究，受到各国涂料界普遍重视。  \n\n涂料行业很多合成树脂原料基本来源于石油化工，而醇酸树脂最基础原料之一是植物油。随着科学技术的发展，如能实现醇酸树脂的水性化或高固体分化，以脂肪酸酯等为活性稀释剂，依靠这些可再生资源，醇酸树脂今后还将会得到更大的发展。",
+        "category": " Introduction"
+    },
+    {
+        "id": 135,
+        "chunk": "# 二、醇酸树脂的分类  \n\n由于醇酸树脂的组分和性能可在很大范围内调整，所以醇酸树脂的品种很多。例如：在  \n\n醇酸树脂配方设计时，可选择不同的多元醇、多元酸；变化醇和酸的官能度之比及调整支化度；醇酸树脂分子上又具有羟基、羧基、双键和酯基，为醇酸树脂的化学改性提供了基础。醇酸树脂分子上还具有极性的主链和非极性的侧链，又可进行物理改性。  \n\n油度不仅是醇酸树脂一个重要指标，而且醇酸树脂命名和分类也常用油度这一概念。油度通常以OL表示。醇酸树脂按含油多少（或含苯二甲酸酐）分为极长、长、中、短等几种油度。可根据油度和油的种类称谓醇酸树脂，如长油度豆油醇酸树脂、短油度椰子油醇酸树脂等。  \n\n如用脂肪酸为原料，则脂肪酸质量×1.04代替油质量（当使用十八碳脂肪酸时)。系数1.04不能作为所有植物油酸与三甘油酯换算。醇酸树脂的质量是多元酸的质量、多元醇的质量和油脂或脂肪酸的质量之和，减酯化时所产生水的量。按油度分类，见表2-1-2。  \n\n表2-1-2油度分类  \n\n\n<html><body><table><tr><td>油度</td><td>油量/%</td><td>苯二甲酸酐/%</td><td>油度</td><td>油量/%</td><td>苯二甲酸酐/%</td></tr><tr><td>短</td><td>35~40</td><td>>35</td><td>长</td><td>56~70</td><td>20~30</td></tr><tr><td>中</td><td>45~55</td><td>30~35</td><td>极长</td><td>>70</td><td><20</td></tr></table></body></html>\n\n注：在各种文献中按油度分类界限有所差别.  \n\n除以油度分类外，还可分为氧化型和非氧化型醇酸，改性和未改性醇酸等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 136,
+        "chunk": "# 三、醇酸树脂的有关化学反应与相关理论  \n\n醇酸树脂的有关化学反应包括酯化反应、醇解反应、酸解反应、酯交换反应、醚化反应、不饱和脂肪酸的加成反应、不饱和脂肪酸与其他化学物的加成反应、缩聚反应。其中酯化反应、醇解反应、加成反应、缩聚反应尤为重要。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 137,
+        "chunk": "# 1.醇解反应  \n\n油（即甘油三脂肪酸酯）与醇共热（加入催化剂或不加入催化剂)，因有过量的羟基存在，就发生羧基重新分配现象。醇酸树脂生产中常用的多元醇如甘油、季戊四醇等。由于羧基重新分配的缘故，随多元醇用量、反应条件的变化，生成产物为不同数量比的油、甘油一酸酯、甘油二酸酯的混合物。其他多元醇与油反应也得到类似的结果。油不能直接用于醇酸树脂的制造，所以必须经过醇解这一步骤，使之成为不完全酯，能溶解于苯二甲酸酐与甘油的混合物，形成均相反应。醇解反应对醇酸树脂的制造和改性极为重要。  \n\n醇解反应通常是在较高的温度和催化剂的作用下进行的，常用的催化剂有黄丹、氢氧化锂等。  \n\n![](images/f8a233515c434a85a70894ac64eb4a655e95c0670ec6e2fd15692c6f73ca9008.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 138,
+        "chunk": "# 2.加成反应  \n\n干性油或半干性油含有数目不等的双键或共轭双键，因此醇酸树脂制造中，在加热条件下，就有可能发生加成反应。若油的不饱和双键位于分子中间，产物大致为二聚体。加成反应表现为体系的黏度增高。由于桐油脂肪酸含三个共轭双键，加成反应剧烈，不宜单独用来制造醇酸树脂。亚麻油、豆油结构中有隔离双键，因此制造醇酸树脂较多地使用豆油、亚麻油。  \n\n不饱和双键还可以和顺丁烯二酸酐、烯烃基化合物、酚-甲醛缩合物进行加成反应。在一般醇酸树脂生产中，可加少量的顺酐以提高黏度；也可以利用双键和顺酐加成反应以实现醇酸树脂的水性化；或用苯乙烯单体改性醇酸树脂，提高其干性和耐水性；用丙烯酸酯等单体和醇酸树脂接枝或改性，以满足市场对醇酸树脂漆的各种特殊性能的要求。  \n\n(1）油的二聚化反应：  \n\n(2）与顺丁烯二酸酐的加成反应顺丁烯二酸酐与不饱和脂肪酸会发生加成反应。$\\Phi$ 与含有共轭双键的脂肪酸形成下述的加成物：  \n\n![](images/35d475ff74902e7d79748fa019ade26a4f5ddfb8326cb3743b74e0d15b1bd91e.jpg)  \n\n$\\textcircled{2}$ 非共轭双键的脂肪酸与顺酐形成下述的加成物：  \n\nHC—CH R—CH -CH—CH—CH—CH—R'—COOH+ O— -0 R—CH—CHCH-CH—CH-R'-COOH 0 CH—CH ， -0  \n\n$\\textcircled{3}$ 只有一个双键的脂肪酸与顺酐形成下述的加成物：  \n\n(3）不饱和脂肪酸与酚-甲醛缩合物的加成反应不饱和脂肪酸与酚-甲醛缩合物可发生加成反应，其反应非常复杂，被认为是属于色满（chromantype）结构。引进酚醛树脂结构可以改进醇酸树脂漆的耐水性与耐化学药品性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 139,
+        "chunk": "# 3.酸解反应  \n\n油和其他的有机酸共热反应，与醇解相似，有过量的羧基存在，将产生羟基重分配现象。酸解法多在间苯二甲酸制造醇酸树脂时使用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 140,
+        "chunk": "# 4.醚化反应  \n\n两个羟基缩合脱除一个分子的水，使原来两个含羟基的化合物以醚键连接起来称为醚化。  \n\n![](images/5003c6415d68a4545519951c5b1a5d7a3cae9666f0348bc8aa857079db974e1a.jpg)  \n\n在醇酸树脂制造中反应温度为 $200{\\sim}250\\Upsilon$ 并有酸、碱存在，不同的多元醇可有不同程度的醚化反应。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 141,
+        "chunk": "# 5.酯化反应  \n\n酯化反应是制造醇酸树脂最主要的化学反应。是醇分子中羟基上的氢原子与酸分子上的氢氧基团缩合生成水与酯。  \n\n$$\n\\underset{\\mathrm{R}-\\mathrm{C}+\\mathrm{OH}+\\mathrm{H}+\\mathrm{H}^{+}\\mathrm{C}}{\\overset{^{\\mathrm{O}}}{\\quad}}\\mathrm{o}\n$$  \n\n酯化反应是可逆的，要使酯化反应完全，必须将副产物—一水引出体系，这是醇酸树脂生产工艺的关键之一。酯化在常温下进行缓慢，通常醇酸树脂酯化温度在 $180\\sim240^{\\circ}\\mathrm{C}$ 之间，酯化速率和程度与酸和醇的结构有关。伯醇反应快且有最高的平衡值；仲醇较慢；叔醇反应最慢、产率也低。催化剂可以加快酯化速率，但不能改变酯化程度。芳香酸或酸酐与醇也能发生酯化，生成酯。在催化的情况下酸酐与一个醇（羟基）反应生成半酯，此为放热反应。第二个羧基与醇反应则需较高的温度。在生产醇酸树脂时绝大多数选用苯二甲酸酐，它和多元醇形成半酯时是放热反应，反应温度较低。  \n\n![](images/971e03f3ef0815c6101bbb49ae46ede23d851d9e18d2eb637a36b6c9ad148476.jpg)  \n\n间苯二甲酸或对苯二甲酸的酯化不像邻苯二甲酸酐那样容易，需要较高的温度。间苯二甲酸代替邻苯二甲酸酐制造醇酸树脂时，其官能度应按大于邻苯二甲酸酐考虑。对苯二甲酸制造醇酸树脂较邻苯二甲酸、间苯二甲酸，有更好的热稳定性，但对苯二甲酸很少用来制造一般醇酸树脂。三元芳香酸，如偏苯三甲酸（1,2,4-苯三甲酸）所制的醇酸树脂比相同油度的邻苯二甲酸、间苯二甲酸制的干燥快而硬度高。调整偏苯三甲酸在醇酸树脂中的用量，可制得含有剩余羧基的醇酸树脂，中和成铵盐，可制成水性醇酸树脂。均苯三甲酸（1,3,5-苯三甲酸）因无邻位，可制得高热稳定性的醇酸树脂。同样可制成水性醇酸树脂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 142,
+        "chunk": "# 6.缩聚反应  \n\n缩聚是一种或几种两个以上官能团的单体，化合成聚合物同时析出低分子副产物。合成醇酸树脂是醇和酸之间发生缩聚反应，同时产生水。也就是说，醇酸树脂是由多元醇、多元酸（一般）经脂肪酸改性共缩聚而成的线型聚酯。  \n\n在了解缩聚反应之前，首先要明确“官能团”和“官能度”的概念。官能团是决定化合物化学特性的原子或原子团，如—COOH、-OH、—NCO、—C—C—等。官能度是在特定的反应条件下，单体中具有反应能力的活性基团数。如甘油有3个羟基，官能度是3；苯二甲酸酐有两个羧基，官能度是2；乙烯有一对双键，官能度是2。如果参加缩合的反应物单体分子都有两个官能团，有相同的反应能力，而且数量相等，则产生缩聚反应。如二元酸分子与二元醇分子的缩合、脱水反应如下：  \n\n$$\n\\mathrm{HOOC-R-COOH+HO-R^{\\prime}-O H\\underset{\\sideset{}{'}\\mathrm{~\\rightleftarrows~}}{\\mathrm{HOOC-R-COOR^{\\prime}-O H+H_{2}O}}}\n$$  \n\n所得的酯分子的两端仍有羧基与羟基，其官能度仍然是2，可再进行反应。连续反应将形成聚酯分子链。说明缩聚反应是逐步反应，分子量随反应时间而逐渐增大。  \n\n缩聚反应分为两类：线型（二向）缩聚反应和体型（三向）缩聚反应。",
+        "category": " Introduction"
+    },
+    {
+        "id": 143,
+        "chunk": "# 四、醇酸树脂的性质和配方计算",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 144,
+        "chunk": "# （一）醇酸树脂的性质",
+        "category": " Introduction"
+    },
+    {
+        "id": 145,
+        "chunk": "# 1.油的品种对醇酸树脂性能的影响  \n\n用来制造醇酸树脂的油，通常按碘值分为干性油、半干性油和不干性油。碘值是指$100_{\\mathsf{E}}$ 油中，使双键饱和所需碘的克数。碘值大于 $140\\mathbf{g}\\mathbf{I}_{2}/100\\mathbf{g}$ 的为干性油，碘值介于 $140\\sim$ $125g\\mathrm{I}_{2}/100g$ 之间的为半干性油，碘值小于 $125\\mathbf{g}\\mathbf{I}_{2}/100\\mathbf{g}$ 的为不干性油。虽然碘值可作为质量控制的规格，但不很有用。它可能会对干性油的定义或反应性的判断产生误导。ZenoW.威克斯在《有机涂料科学和技术》一书中引人干性指数的概念。",
+        "category": " Introduction"
+    },
+    {
+        "id": 146,
+        "chunk": "# 干性指数 ${\\tt=}1\\times{\\tt}$ 亚油酸（%） $+2\\times$ 亚麻酸（%  \n\n当非共轭油的干性指数大于70时即为干性油。例如，亚麻油的脂肪酸的组成中，亚油酸占 $16\\%$ ，亚麻酸占 $52\\%$ ，其干性指数为120；大豆油的脂肪酸的组成中，亚油酸占$51\\%$ ，亚麻酸占 $9\\%$ ，其干性指数为69，所以，亚麻油是干性油，而大豆油是半干性油（常见油的脂肪酸的组成见“油基树脂漆”一章）。这里起干燥作用的活性基团是二烯丙基 $(\\mathrm{-CH-CHCH_{2}C H-C H-})$ ，在每个亚油酸或亚麻酸分子上分别有 $_{1\\sim2}$ 个二烯丙基，判断干燥能力大小的通用准则是，干性与每个分子中所含二烯丙基的平均值有关。如果这个值大于2.2，即为干性油。如果低于2.2，即为半干性油。半干性油和不干性油之间无明显界限。这个准则也适于合成干性油和天然油。因为二烯丙基所在的位置，即交联的位置，所以很容易将每个分子的烯丙基的平均数与三甘油酯或合成干性油的平均官能度 $\\bar{f}_{\\mathrm{~s~}}$ 联系起来。 ?  \n\n在非共轭干性油中，被两个双键相连的烯丙基激活的亚甲基，与仅有一个双键的烯甲基的亚甲基相比，其反应活性更强。这一论断可通过甘油三油酸酯、甘油三亚油酸酯、甘油三亚麻酸酯的自动氧化合成反应相对速率的差异来加以证实。它们的速率比为 $1:120:330$ 。  \n\n这三种三酸酯的二烯丙基数目（f）分别为0、3、6，理论碘值依次为 $86{\\bf g}\\mathrm{I}_{2}/100{\\bf g}$ 。$173\\mathbf{g}\\mathrm{I}_{2}/100\\mathbf{g}$ 和 $262g\\mathrm{I}_{2}/100\\mathrm{g}$ 。自动氧化的速率与双键间二烯丙基的数目 $\\cdot{\\bar{f}}_{\\mathfrak{n}}$ ）的关系比碘值更密切。亚麻油的为3.6，属干性油；大豆油的。为2.07，属半干性油。干性油的 $\\scriptstyle{\\overline{{f_{n}}}}$ 越高，那么暴露于空气中越耐溶剂，交联漆膜的速率越快。  \n\n习惯上称碘值 $130\\mathbf{g}\\mathbf{I}_{2}/100\\mathbf{g}$ 以上的油为干性油，用来制造室温自干的醇酸树脂。碘值高的油制成的醇酸树脂不仅干得快，而且硬度高、光泽较高。亚麻油醇酸树脂干燥快，但易于黄变。桐油因 $90\\%$ 的脂肪酸含共轭三烯，反应快，不宜单独用来制造醇酸树脂。梓油是我国的特产，其干性接近亚麻油，也用于制造干性醇酸树脂。豆油和豆油脂肪酸，虽然碘值较低，但制造醇酸树脂可得到较满意的干性且不易泛黄，故适于做白色及浅色漆。季戊四醇的官能度高于甘油，制造醇酸树脂可以提高干性。  \n\n麻油是不干性油，但含有约 $85\\%$ 的麻酸(12-羟基十八碳烯-9-酸)，在 $260^{\\circ}\\mathrm{C}$ 以上及酸性催化剂存在下，分子上的羟基和邻近碳原子上的氢原子结合而脱去一分子水。这样每个麻酸分子增加了一个双键，而且 $20\\%\\sim30\\%$ 为共轭双键。  \n\n![](images/6e17c1cc0502d6e1419f7d1a99c2e161a3dcac35c91c211234aeaf266bdd443f.jpg)  \n\n脱水后的麻油变成干性油，碘值虽不高，但含有共轭双键的比例较大，干得较快。不过有发黏的毛病，其泛黄性略逊于豆油。脱水麻油可制成干性醇酸树脂。麻油不经脱水$(200\\Upsilon)$ 低温酯化）可制成不干性醇酸树脂。如果未脱水麻油在生产时脱水和酯化同时进行，也可以制得干性醇酸树脂。  \n\n关于用麻油生产醇酸树脂问题，麻油虽然是一种油脂，但结构上又是一种羟基脂肪酸形成的油脂，它可直接与多元酸酯化形成醇酸树脂，从而表现出一种多元醇的性质。一般其脂肪酸组成中有 $87\\%$ 带有一OH的麻油酸，从理论上与检测分析数据，可以推算它作为多元醇的—OH官能度约为2.75。现在市售麻油羟基值往往偏低，例如，羟基值 $150\\mathrm{mgKOH/g}$ 的工业麻油，可以估计麻油含量在 $90\\%$ 左右，其名义官能度为2.5。在生产醇酸树脂时，麻油被当成一种多元醇（不用醇解)，但在配方计算时却把它等同于普通油脂，忽略它的一OH。因而配方计算不能实际反映工艺特点与产品的性质。关于麻油醇酸树脂的配方计算，将在后面再讨论。油类对醇酸树脂性能的影响见表2-1-3。  \n\n表2-1-3油类对醇酸树脂性能的影响   \n\n\n<html><body><table><tr><td rowspan=\"2\">油或脂肪酸</td><td rowspan=\"2\">碘值/（gIz/100g)</td><td colspan=\"4\">漆膜性能</td></tr><tr><td>干率</td><td>保色性</td><td></td><td>保光性</td></tr><tr><td>桐油 亚麻油</td><td>160~165 170~190</td><td rowspan=\"6\">↑</td><td rowspan=\"6\"></td><td rowspan=\"6\"></td><td rowspan=\"6\"></td><td rowspan=\"6\"></td></tr><tr><td>脱水麻油</td><td>125~144</td></tr><tr><td>豆油</td><td>130~140</td></tr><tr><td>松浆油酸</td><td>125~150</td></tr><tr><td>棉籽油</td><td>110</td></tr><tr><td>花生油</td><td>108</td></tr><tr><td>麻油</td><td>85</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>椰子油</td><td>8</td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>\n\n$\\Phi$ 表中箭头方向表示性能改进趋势。  \n\n用不干性油如麻油、椰子油、月桂酸及中、短碳链的合成脂肪酸，制成不干性醇酸树脂，并和其他树脂合用，用氨基树脂或聚氨酯交联或作增塑剂等用。除正规的油以外，几乎所有的油（甘油三脂肪酸酯）都能制成醇酸树脂。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 147,
+        "chunk": "# 2.油度（脂肪酸含量）对醇酸树脂性能的影响  \n\n$\\Phi$ 醇酸树脂油度划分及对醇酸树脂性能的影响前已介绍油度的计算公式。醇酸树脂油度分为短、中、长、超长油度。我国涂料行业的习惯分类见表2-1-4。  \n\n表2-1-4我国涂料行业的习惯分类  \n\n\n<html><body><table><tr><td>油度</td><td>油度值/%</td><td>苯二甲酸酐/%</td><td>油度</td><td>油度值/%</td><td>苯二甲酸酐/%</td></tr><tr><td>短油度</td><td>35~45</td><td>>35</td><td>长油度</td><td>56~70</td><td>20~30</td></tr><tr><td>中油度</td><td>46~55</td><td>30~35</td><td>超长油度</td><td>>70</td><td><20</td></tr></table></body></html>  \n\n油度决定醇酸树脂的很多性能。油度为0（即 $100\\%$ 的聚酯）是硬而脆的玻璃状物，油是低黏度液体，醇酸树脂介于两者之间。醇酸树脂随油度长短溶于脂肪烃、脂肪烃与芳香烃混合物和芳香烃溶剂。这是因为醇酸树脂以聚酯为主链，脂肪酸为侧链，主链属极性，侧链属非极性。中、长油度的醇酸树脂脂肪酸侧链较多，脂肪酸基可以在非极性溶剂中任意舒展得到很好溶解。在极性溶剂中，醇酸树脂的主链能很好舒展，因而也得到很好溶解。  \n\n油度（脂肪酸含量）对醇酸树脂性能的影响见表2-1-5。  \n\n表2-1-5油度（脂肪酸含量）对醇酸树脂性能的影响   \n\n\n<html><body><table><tr><td rowspan=\"3\">树脂性质</td><td colspan=\"5\">油 度</td></tr><tr><td>30%</td><td>40%</td><td>50%</td><td>60%</td><td>70%</td></tr><tr><td colspan=\"5\">芳香烃溶剂 混合溶剂 脂肪烃溶剂</td></tr><tr><td>溶剂 脂肪烃溶剂容忍度</td><td colspan=\"5\"></td></tr><tr><td>醇容忍度 黏度</td><td colspan=\"5\"></td></tr><tr><td>溶解度</td><td colspan=\"5\"></td></tr><tr><td>漆膜凝定时间</td><td colspan=\"5\"></td></tr><tr><td>自干时间</td><td colspan=\"5\"></td></tr><tr><td>漆膜硬度</td><td colspan=\"5\"></td></tr><tr><td>树脂玻璃化湿度（Tg）</td><td colspan=\"5\"></td></tr><tr><td>刷涂性</td><td colspan=\"5\"></td></tr><tr><td>流平性、流挂性</td><td colspan=\"5\"></td></tr><tr><td>漆膜原始光泽</td><td colspan=\"5\"></td></tr><tr><td>保光性</td><td colspan=\"5\"></td></tr><tr><td>保色性</td><td colspan=\"5\"></td></tr><tr><td>漆膜泛黄性</td><td colspan=\"5\"></td></tr><tr><td>户外耐候性</td><td colspan=\"5\"></td></tr><tr><td></td><td colspan=\"5\"></td></tr><tr><td>贮存稳定性 耐水性</td><td colspan=\"5\"></td></tr></table></body></html>\n\n注：表中箭头方向表示性能改进趋势。  \n\n在选择常温自干醇酸树脂时都希望双键尽量多些，又希望聚酯部分适度。为了氧化交联性强、硬度大，常温自干醇酸树脂的油度可在 $50\\%$ 左右。  \n\n醇酸树脂的油度不同，它们所含的低分子物的数量也不同。对 $43\\%\\sim70\\%$ 油度的亚麻油醇酸树脂进行苯萃取试验证明，油度为 $48\\%\\sim53\\%$ 的醇酸树脂低分子较少，漆膜硬度也以 $48\\%$ 油度最高。所以中油度醇酸树脂大量用于涂料工业，既可以用于常温自干，又可以  \n\n烘干。缺点是刷涂性稍差。  \n\n醇酸树脂的黄变性来源于脂肪酸部分，尤其是亚麻油。油度减少变色情况减轻。醇酸树脂漆漆膜的硬度及耐久性与干燥方式有关。常温自干醇酸树脂完全是空气氧化作用，没有进一步缩合作用，所以在一定限度内，含油较多者干率与耐久性较好。烘干醇酸树脂漆漆膜除氧化外还可能有进一步聚合作用，所以漆膜的硬度及耐久性以油度较短者较好。刷涂性随油度的增加而改善，结合干率及耐久性以油度 $60\\%\\sim65\\%$ 为宜。醇酸树脂有残留的未反应的羟基和羧基，所以耐水性较差，烘干较自干好。  \n\n醇酸树脂可用半干性油制得，并能较快地干燥，这是醇酸树脂的特点。由于中、长油度醇酸树脂分子量较大，每个分子结构上比油含有更多的脂肪酸基，总的不饱和度大大提高，官能团提高，所以用豆油、松浆油酸等碘值不高的油或脂肪酸，也能制造干性较好的醇酸树脂。提高温度可使脂肪酸自动氧化加速，因而催干剂用量很少。醇酸树脂漆可以烘干，没有诱导期形成碳-碳链，漆膜比常温干燥者耐久性好。用于烘漆的醇酸树脂的油度一般为 $40\\%\\sim50\\%$  \n\n原来油度的定义是植物油（或脂肪酸）用量在醇酸树脂中的含量，但随着醇酸树脂的原料、品种、规格的日益多样化，对油度的表征意义也应有所扩展。醇酸分子中侧链不完全是植物油或脂肪酸而可能是其他的一元酸。那么油度的定义变为醇酸树脂分子中侧链质量占醇酸树脂总质量的百分数， $O L_{\\ell}$  \n\n$\\textcircled{2}$ 醇酸树脂油度和其溶度参数的关系溶度参数法是高聚物选择良溶剂重要的方法，也与附着力有密切关系。而油度是醇酸树脂的一个重要参数。因此有必要研究油度和溶度参数的相关性。但醇酸树脂和聚酯等合成树脂相比，其分子量低，其主要溶剂仍然是脂肪烃。  \n\n由于要建立描述溶度参数和油度的关联式，需要测定许多不同油度的溶度参数。工作量很大，而且一些理想化的醇酸树脂实际上很难制备。但不论是溶度参数及其分量，还是摩尔体积，都可以根据重复单元的分子结构按照基团加合法计算。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 148,
+        "chunk": "# 3.醇酸树脂分子上的羧基、羟基对漆膜性能的影响  \n\n这些极性基团使醇酸树脂漆膜有良好的附着力，羧基提供对颜料的润湿力。羟基与羧基同时还结合钙催干剂形成共价化合物，促进漆膜的初干和实干。羧基可由酸值来确定，一般自干醇酸树脂的酸值在 $10\\mathrm{mgKOH/g}$ 左右，否则酯化程度太低，分子量小，且与碱性颜料反应性过强易发生胶化。用于氨基漆的醇酸树脂，羧基有催化作用，而且参与反应，可根据需要设定一定的酸值。水性醇酸树脂为取得水溶性，也要保留一定的酸值与羟基。  \n\n有人做过醇酸树脂羟基值对漆膜性能影响的试验。结果见表2-1-6、表2-1-7。醇酸树脂的漆膜硬度及拉伸强度随羟基值的增大而降低。说明同样油度的醇酸树脂，不论制造方法与黏度如何，其漆膜耐候性、硬度、拉伸强度、低分子物含量（丙酮萃取物量）均与羟基含量有关，同样调整甘油过量数量，也影响醇酸树脂的分子量分布。所以在生产工艺可行及树脂贮存性良好的情况下，多元醇不要过量太多。  \n\n表2-1-6不同羟基值醇酸树脂的干率  \n\n\n<html><body><table><tr><td>醇酸树脂的羟基值/(mgKOH/g)</td><td>指触干/h</td><td>不粘尘干/h</td><td>干硬/h</td></tr><tr><td>30</td><td>1.5</td><td>2</td><td>13</td></tr><tr><td>40</td><td>1.5</td><td>3</td><td>15 P</td></tr><tr><td>50</td><td>1.5</td><td>3.5</td><td>15</td></tr><tr><td>75</td><td>2</td><td>6</td><td>16</td></tr><tr><td>100</td><td>2</td><td>12</td><td>21</td></tr></table></body></html>\n\n注： $75\\mu\\mathrm{m}$ 制膜器涂在玻璃板上，温度23℃、相对湿度43%下测定。  \n\n表2-1-7不同羟基值醇酸树脂的漆膜硬度  \n\n\n<html><body><table><tr><td rowspan=\"2\">醇酸树脂的羟基值 /(mgKOH/g)</td><td colspan=\"6\">斯氏（Sward hardness）硬度</td></tr><tr><td>干1天</td><td>于2天</td><td>干5天</td><td>干7天</td><td>干14天</td><td>干30天</td></tr><tr><td>30</td><td>6</td><td>9</td><td>10</td><td>12</td><td>16</td><td>24</td></tr><tr><td>40</td><td>6</td><td>12</td><td>12</td><td>14</td><td>18</td><td>24</td></tr><tr><td>50</td><td>5</td><td>11</td><td>14</td><td>14</td><td>18</td><td>26</td></tr><tr><td>75</td><td>7</td><td>12</td><td>12</td><td>16</td><td>22</td><td>28</td></tr><tr><td>100</td><td>4</td><td>10</td><td>14</td><td>18</td><td>22</td><td>29</td></tr></table></body></html>  \n\n如果以 $50\\%$ 的亚麻油醇酸树脂为例，并通过调整季戊四醇与新戊二醇的比例调整羟基值，而保持多元醇与多元酸的摩尔比不变，羟基值控制在 $30{\\sim}100\\mathrm{mgKOH/g}$ 。试验证明，增加羟基值可以增加黏度，提高耐汽油性，并与氨基树脂的固化好，常温干燥有较高的硬度；但耐水性差；反之，低羟基值的醇酸树脂则干燥快，有较好的弹性与耐水性。如果用该树脂制成色漆（以白色为例)，则KU黏度随羟基值的增加而增大；光泽度和硬度则随羟基值的增大而提高；结皮性随羟基值的增大而减轻；保光性随羟基值的增大而降低；反之，干燥时间则随羟基值的增大而延长；羟基值增加而耐擦洗性下降。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 149,
+        "chunk": "# 4.“有效用”的羟基起着影响醇酸树脂性能的作用  \n\n醇酸树脂分子上留有一些活性基团，例如，羟基、羧基，但醇酸树脂分子上所有的理论基团数（此处指羟基）不等于“有效用”基团。当醇酸树脂与氨基树脂反应时，共缩聚是通过醇酸树脂分子上的羟基完成的，因分子位阻作用，起作用的仅仅是“有效用”的羟基，而不是理论上的全部羟基。羟基对醇酸树脂性能影响很大，如羟基可以增加水性醇酸树脂的稳定性。其重要性甚至超过羧基。在平均官能度大于2和缩聚程度较高的情况下，“有效用”的羟基的含量不一定与理论羟基含量一致。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 150,
+        "chunk": "# 5.醇酸树脂的特性黏度  \n\n高分子物的分子量可通过测量黏度来推算。特性黏度通常是由测定不同浓度的黏度 $\\eta$ 算出 $\\eta_{\\mathrm{sp}}$ （增比黏度）和 $\\eta_{t}$ (相对黏度)，然后用 $\\eta_{\\mathrm{sp}}/c$ 对 $\\textit{\\textbf{c}}$ （浓度）作图，或 $\\ln{\\eta_{t}}/c$ 对 $\\boldsymbol{c}$ 作图，外推得[n]。  \n\n（1）特性黏度与聚合度的关系醇酸树脂的数均聚合度（ ${\\bar{X}}_{\\mathfrak{p}}$ ）可按下式计算：  \n\n$$\n\\displaystyle\\bar{X}_{\\mathrm{r}}=\\frac{1}{1-P_{\\mathrm{A}}}\n$$  \n\n$P_{\\Lambda}$ 为酸反应程度，可由滴定法求得。特性黏度与聚合度的关系为：  \n\n$$\n[\\eta]=K X_{\\mathrm{~n~}}^{*}\n$$  \n\n(2）不同级分的特性黏度与分子量分布合成树脂的分子量分布非常宽，醇酸树脂也是如此。以分级沉淀法分成不同级分。然后测定各级分的特性黏度。观察各特性黏度，发现聚合度高的醇酸树脂含有极高分子量级分，而且分子量分布更宽。所以对每个醇酸树脂的树脂-溶剂系统的特性黏度的测定也是一个跟踪合成进展、确定最佳点的方法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 151,
+        "chunk": "# 6.醇酸树脂的分级分离  \n\n醇酸树脂是一种复杂的混合物，由不同分子量、不同形状、不同极性程度的分子组成，可将它分离为不同级分进行研究。可用不同的溶剂进行分级，极性溶剂将按极性程度分离，非极性溶剂将按分子量大小、形状分离。在深冷下醇酸树脂各级分的溶解度不同，所以也可以用冷冻法分离。表2-1-8是 $70\\%$ 油度亚麻油醇酸树脂分级的结果。  \n\n表2-1-870%油度亚麻油醇酸树脂以苯-甲醇分级的结果   \n\n\n<html><body><table><tr><td>项目</td><td>质量分数</td><td>/(mgKOH/)</td><td>(m基H/B)</td><td>油度</td><td>数均分子量</td><td>重均分子量</td></tr><tr><td>原树脂</td><td>一</td><td>17.2</td><td>47.6</td><td>70</td><td>1940</td><td>59000</td></tr><tr><td>级分1</td><td>23.2</td><td>40.8</td><td>28.9</td><td>69</td><td>1030</td><td>7900</td></tr><tr><td>级分2</td><td>14.1</td><td>17.1</td><td>28.9</td><td>74</td><td>1500</td><td>8000</td></tr><tr><td>级分3</td><td>22.5</td><td>16.2</td><td>26.1</td><td>70</td><td>2540</td><td>22000</td></tr><tr><td>级分4</td><td>11.7</td><td>8.7</td><td>26.5</td><td>69</td><td>8500</td><td>46000</td></tr><tr><td>级分5</td><td>7.7</td><td>8.6</td><td>34.6</td><td>69</td><td>9800</td><td>49000</td></tr><tr><td>级分6</td><td>14.3</td><td>8.7</td><td>49.4</td><td>68</td><td>17000</td><td>400000</td></tr><tr><td>级分7</td><td>6.5</td><td>8.2</td><td>41.1</td><td>67</td><td>35000</td><td>含有微胶粒</td></tr></table></body></html>  \n\n虽然这一醇酸树脂被分为7个级分，但每个级分仍然是非常不均匀的多分散体。  \n\n通过分级分离可知醇酸树脂是一种非常复杂的混合物，不同的级分都对漆膜产生不同的影响。生产醇酸树脂的重要工作之一在于增加性能优良的级分，减少性能不良的级分，改进提高醇酸树脂的产品质量。  \n\n表2-1-8中的级分7中含有微胶粒，Moore推测“微胶粒”可促进醇酸树脂干燥。  \n\n如果用两个不同聚合度的醇酸树脂做试验：一个醇酸树脂 $D P$ 为10；另一个 $D P$ 为34。高 $_{D P}$ 的醇酸树脂以不同比例加人低 $D P$ 的醇酸树脂中，如果加高 $_{D P}$ 的醇酸树脂仅 $20\\%$ 就使低 $D P$ 的醇酸树脂的干燥时间缩短为原来的 $15\\%$ 。继续增加高DP的醇酸树脂，则相对提高不大。按Flory理论，酯化反应开始产生微胶粒即是凝胶点，因此在工业生产醇酸树脂时，要酯化反应到接近凝胶点，即制造大量的成核胶粒；苯乙烯改性醇酸树脂干燥快，除挥发干燥外，也是由于其氧化部分构成胶体粒子；高聚物法合成醇酸树脂也是先生成高分子预聚物，然后再补加脂肪酸，也是引入成核效应。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 152,
+        "chunk": "# 7.合成工艺与醇酸树脂性质的关系  \n\n（1）混合甘油酯的成分、醇酸树脂的分子量分布与微胶粒假说醇酸树脂的性质受合成工艺的影响，如甘油和油比例、反应温度、催化剂、时间、脂肪酸的种类等，都会影响醇酸树脂的分子量分布。为使每批醇酸树脂的生产都有重复性，就必须要求： $\\Phi$ 生产工艺条件完全相同； $\\textcircled{2}$ 甘油与油反应后的化学成分达到一致。  \n\n(2）醇解物的甘油酯成分对氨基醇酸烘漆的影响为提高氨基烘漆的耐候性和耐过烘烤性，通常采用饱和脂肪酸醇酸树脂，并缩短油度。由于油度缩短，体系的官能度增高，其复杂性加大。若采用醇解法生产醇酸树脂，醇解物含有甘油一亚油酸酯、甘油二亚油酸酯、甘油三亚油酸酯和游离甘油。醇解物的成分会影响醇酸树脂的分子量分布，所以醇酸树脂虽然配方相同，但由于醇解物的成分不同，所得的醇酸树脂也不同。醇解法和脂肪酸法不同，后者在酯化反应中，脂肪酸、多元醇、二元酸同时起反应，所得的醇酸树脂的分子量分布和醇解法不同，因为酯交换反应相对非常慢。  \n\n(3）关于麻油醇酸树脂与氢化麻油醇酸树脂麻油的脂肪酸主要是12-羟基十八碳烯-9-酸，氢化麻油为12-羟基十八碳酸。用麻油生产醇酸树脂其特点是： $\\textcircled{1}$ 可与甘油、苯二甲酸酐融合成均相，不必先醇解，在反应过程中有很大程度的醇解作用，分子量分布与以前的醇酸树脂有所不同； $\\textcircled{2}$ 麻油酸上的羟基与甘油的羟基竞相反应，随着醇解反应程度不同，导致不同分子结构和分子量分布； $\\textcircled{3}$ 重要的是醇酸树脂制造都希望醇解达到尽可能高的甘油一酸酯含量，但在工业生产麻油醇酸树脂时，都采取用油直接反应，而免去醇  \n\n解阶段。  \n\n（4）脂肪酸法与脂肪酸甘油一酸酯法的比较醇酸树脂合成主要有三种方法：脂肪酸法、醇解法、脂肪酸甘油一酸酯法。后者是脂肪酸先与甘油反应，然后再与苯二甲酸酐反应。醇解法和脂肪酸甘油一酸酯法制得的醇酸树脂及其漆膜，较软、较黏；树脂对脂肪烃溶剂容忍度高，且黏度低；制得的清漆漆膜干燥较慢而且较黏；酯化速率较低，且胶化时酸值较高。试验证明，不同的合成方法，如脂肪酸法与脂肪酸甘油一酸酯法，会影响树脂的分子量分布、漆膜玻璃化温度及交联度，在树脂合成时，影响凝胶化时的酯化程度。  \n\n(5）醇酸树脂合成时酯化温度控制程序对分子量分布的影响日本某公司生产月桂酸醇酸树脂时，生产方法采用两种：第一种是先在 $170\\%$ 保温酯化1h，然后再升温到 $230\\mathrm{\\mathfrak{C}}$ 保持酯化；第二种是直接升温到 $230^{\\circ}\\mathrm{C}$ 保持酯化，然后观察两种生产方法对分子量分布的影响。采用分级的方法，测定其分子量。结果表明，第二种方法生产醇酸树脂分子量分布更宽。由于醇酸树脂合成工艺的变化对醇酸树脂的结构和分子量分布的影响很大，在实际生产中以酸值、黏度、颜色来进行控制是不能表示树脂的结构和分子量分布的意义的。为生产均一、恒定质量的醇酸树脂，必须建立严格的原料考核与精确的、不能随意改动的工艺规程。  \n\n(6）醇酸树脂的凝胶色谱（GPC）分析法采取分级沉淀等方法测定醇酸树脂的分子量分布，步骤非常烦琐，需时很长。1964年，Moore研究出凝胶色谱法，使聚合物的分级分离和分子量分布的测定得到突破性的进展。用这一方法测定只需几十分钟，比较准确，用样品量也少。  \n\n用GPC法测定高聚物的分子量分布和经典方法的结果是一致的，但速度快，采用高效凝胶色谱法来测定试样的分子量分布只需 $20\\mathrm{{min}}$ 左右。如果联结上电子计算机做数据处理，就可以立即得到分子量分布的数据。现在GPC法已用于涂料用合成树脂。1966年，DavidG.Lesini介绍了用GPC法对醇酸树脂进行分级和测定分子量分布，认为GPC法对多分散度的树脂是一个良好的分析方法。张泉福等以高效色谱柱对醇酸树脂的分子量分布做了广泛而深入的研究。  \n\n对我国某厂生产的几个典型的醇酸树脂在生产中的酯化反应阶段连续取样进行测定，并讨论醇酸树脂在酯化合成各阶段的分子量及分子量分布的变化规律与反应程度和黏度的关系，还讨论了分子量分布与分子量的关系。醇酸树脂分子量按低 $(M{<}1300)$ 、中（ $_{1300<}$ $M<10^{5}$ 、高 $(M{>}10^{5}$ ）分为三个区段，并列出其百分含量。酯化初期低分子物较多，高分子物较少。随酯化程度的提高，高分子成分增加，但直至反应终点，始终存留有低分子物。因此醇酸树脂最终产物分子量分布是非常宽的。 25  \n\n对于一定的醇酸树脂配方，分子量参数随酸值下降及反应程度增大而增大。在酯化前期酸值下降迅速，反应程度很快达到 $80\\%$ 以上，而 $\\boldsymbol{M_{\\mathrm{w}}}$ ， $M_{\\mathfrak{n}}$ 、分散度d及黏度 $\\eta$ 随反应慢慢平稳增长。反映了酸与醇之间的小分子酯化反应；在酯化后期 $\\eta$ 和 $M_{\\mathfrak{n}}$ 急剧上升，d也随之很快增大。在GPC谱图 $\\scriptstyle t_{\\tau}$ 约 $15.8\\mathrm{min}$ 处已可见 $M{>}370000$ 的高分子物产生，该阶段是大分子之间的聚酯化反应，是决定产物分子量分布和性能的重要阶段。试验表明，在缩聚中 $\\boldsymbol{M}_{\\mathbf{w}}$ 增长比 $M_{\\mathfrak{n}}$ 快得多，在凝胶点下分子量趋于无限大的是重均分子量而不是数均分子量； $\\eta$ 随$\\ensuremath{M_{\\mathrm{w}}}$ 的变化更灵敏；目前生产中采用加氏管控制酯化终点，实质上反映了 $\\boldsymbol{M_{\\mathrm{w}}}$ 。油度越短、羟基过量越大，其分子量分布越窄。张泉福等还对国内几个著名品牌的醇酸树脂做了GPC分析，分短油度、中油度、长油度三种类型，列出其 $M_{\\ast}$ ， $M_{\\mathrm{{s}}}$ 及其分子量分布等（表2-1-9)，供参考。  \n\n表2-1-9几个典型醇酸树脂分子量参数测定值   \n\n\n<html><body><table><tr><td colspan=\"2\">品种</td><td>批号</td><td>M</td><td>M</td><td>分散度d</td><td colspan=\"3\">>1X10<1</td><td rowspan=\"2\">MNpe</td><td rowspan=\"2\"></td><td rowspan=\"2\"></td></tr><tr><td colspan=\"3\"></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td rowspan=\"8\">短油度醇酸 酸</td><td>1</td><td>12-2</td><td>4520 5520</td><td>1340 1500</td><td>3.37 3.67</td><td>4.0 8.8</td><td>69.0 68.3</td><td>27.0 23.0</td><td>1810 1880</td><td>3.8 4.1</td><td>26.5</td></tr><tr><td></td><td>12.3 2-5</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>3.6</td><td>30.7</td></tr><tr><td></td><td></td><td>26600</td><td>2520</td><td>10.6</td><td>5.8</td><td>78</td><td>16.2</td><td>2530</td><td></td><td>17.5</td></tr><tr><td>2</td><td>5-2</td><td>34500</td><td>2850</td><td>13.5</td><td>10.83</td><td>76.2</td><td>14.3</td><td>1950</td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>138</td><td>11000</td><td>1950</td><td>5.64</td><td>0.9</td><td>79.9</td><td>19.2</td><td>2400</td><td></td><td></td></tr><tr><td>3</td><td>139</td><td>18000</td><td>2200</td><td>8.18</td><td>2.7</td><td>80.0</td><td>17.3</td><td>2220</td><td></td><td></td></tr><tr><td></td><td>140 3-1</td><td>17800</td><td>2300</td><td>7.74</td><td>2.2</td><td>81. 4</td><td>16.4 11.4</td><td>2410</td><td></td><td></td></tr><tr><td>4 5</td><td>3-2</td><td>44300 38760</td><td>3720 2090</td><td>11.7 4.2</td><td>13.1 10.0</td><td>75.5 77.8</td><td>12.2</td><td>1760 1780</td><td></td><td></td></tr><tr><td rowspan=\"12\">酸</td><td></td><td>1</td><td>93700</td><td>3080</td><td>30.4</td><td>27.7</td><td>54.6</td><td>17.7</td><td>2080</td><td></td><td></td></tr><tr><td>6 2-1</td><td>71900</td><td></td><td>4610</td><td>15.6</td><td>23.3</td><td>67.7</td><td>9. 0</td><td>1970</td><td></td><td></td></tr><tr><td>7 3-1</td><td>67800</td><td>4220</td><td>16.1</td><td></td><td></td><td></td><td></td><td>2610</td><td>4.5</td><td>21.5</td></tr><tr><td>1-1</td><td>47000</td><td></td><td></td><td></td><td>23.8 14.1</td><td>67.8 75.6</td><td>8.4 10.3</td><td>1860</td><td></td><td></td></tr><tr><td></td><td></td><td>4080</td><td>11.5</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>34900</td><td>3450</td><td>19. 1</td><td>1.9</td><td>78. 1</td><td></td><td>1.0</td><td>1600</td><td>4.9</td><td></td></tr><tr><td></td><td>5-2</td><td>42600</td><td>3080</td><td>11.2</td><td>11.4</td><td>74.8</td><td>13. 8</td><td>2250</td><td>4.4</td><td></td></tr><tr><td></td><td>3-1</td><td>54800</td><td>3720</td><td>14.7</td><td>19.1</td><td>71. 2</td><td>9.7</td><td>2310</td><td>4.8</td><td>15.3</td></tr><tr><td>9</td><td>3-3</td><td>51500</td><td>3420</td><td>15.1</td><td>17.7</td><td>72.4</td><td>9.9</td><td>2340</td><td>4.6</td><td>14.1</td></tr><tr><td></td><td>3-6</td><td>54600</td><td></td><td>14.6</td><td>17.9</td><td>72.5</td><td>9.6</td><td>2290</td><td>4.7</td><td>15.2</td></tr><tr><td></td><td>4-1</td><td>35300</td><td>3740 3460</td><td>10.2</td><td>10.3</td><td>78.2</td><td>11.5</td><td>2290</td><td>3.8</td><td>14.6</td></tr><tr><td></td><td>日进</td><td>54000</td><td>3700</td><td>14.7</td><td>17.2</td><td>75.3</td><td>7.5</td><td>1840</td><td></td><td></td></tr><tr><td rowspan=\"9\">长油度静酸 酸</td><td>98</td><td></td><td>45500</td><td>3120</td><td>14.6</td><td>12.5</td><td>76.0</td><td>11.5</td><td>2560</td><td></td><td></td></tr><tr><td>10 99</td><td></td><td>47600</td><td>3260</td><td>14.6</td><td>13.2</td><td>76.3</td><td>10.5</td><td>2560</td><td></td><td></td></tr><tr><td>144</td><td>56400</td><td>3660</td><td>15.4</td><td>18.1</td><td></td><td>72.8</td><td>9.2</td><td>2580</td><td></td><td></td></tr><tr><td>0-1 11</td><td>57200</td><td></td><td>4030</td><td>14.2</td><td>17.4</td><td>72.8</td><td>9.8</td><td>1730</td><td></td><td></td></tr><tr><td>0-2</td><td>48500</td><td></td><td>3880</td><td>12.5</td><td>14.1</td><td>74.8</td><td>11. 1</td><td>1730</td><td></td><td></td></tr><tr><td>5-1</td><td>69100</td><td></td><td>4000</td><td>17.3</td><td>24.2</td><td>67.1</td><td>8.7</td><td>2780</td><td>2.5</td><td>28.3</td></tr><tr><td>5-2 12</td><td>62700</td><td>3820</td><td></td><td>16.4</td><td>21.5</td><td>69.4</td><td>9.1</td><td>2800</td><td>2.3</td><td>26.5</td></tr><tr><td>5-3</td><td>77300</td><td>4260</td><td>18.1</td><td></td><td>26.6</td><td>65.8</td><td>7.6</td><td>2730</td><td>2.6</td><td>44.9</td></tr><tr><td>5-4 3-1</td><td>75000 70500</td><td>4170</td><td></td><td>18.0</td><td>25.4 22.8</td><td>66.1 64.8</td><td>8.5 12.4</td><td>2580 2563</td><td>2.3 4.0</td><td>44.4 37.9</td></tr><tr><td>13</td><td>3-2</td><td>71400</td><td>3390 3260</td><td>20.9 21.9</td><td>23.0</td><td>65.2</td><td>11.8</td><td>2610</td><td>4.3</td><td>51.4</td></tr><tr><td></td><td></td><td></td><td>4390</td><td>21.4</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>14</td><td>1</td><td>93800</td><td></td><td></td><td></td><td>28.3</td><td>62.9</td><td>9.2</td><td>2080</td><td></td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 153,
+        "chunk": "# （二）醇酸树脂配方计算  \n\n醇酸树脂是一种复杂的聚合物，要求在合成时，反应尽量完全而又不至于凝胶。制造工艺稳定，并且满足制漆要求。醇酸树脂配方计算只是根据理论的推导作为起点，还要经过试验反复修正，并在生产实践中不断完善配方。目前人们进行醇酸树脂配方计算，仍基于Carothers方程。  \n\n$$\nP_{8}={\\frac{m_{0}}{e_{\\mathrm{A}}}}\n$$  \n\n是一个重要的公式，可以改写为：  \n\n$$\nK=\\frac{m_{0}}{e_{\\mathsf{A}}}\n$$  \n\n式中 $\\boldsymbol{e}_{\\mathsf{A}}$ —酸的总当量数；$m_{0}$ —总摩尔数；$P_{8}$ —胶化时酯化程度；$\\kappa$ 醇酸常数。  \n\n$\\scriptstyle K=1$ 是理想常数，即酯化反应可达标 $100\\%$ 。Carothers方程计算的数值偏高，而且任何醇酸树脂配方也不可能设计到恰是凝胶点，但加一些安全系数是必要的。不同的原料和油度长短都有其独立的“工作常数”，根据 $\\kappa$ 值来比较、分析配方，推测是否早期凝胶化。大于工作常数则树脂分子量将过小，性能不能令人满意。两者之差不要超过0.05。  \n\n$\\kappa$ 值在配方的应用只适合于溶剂法，因为溶剂法生产醇酸树脂时醇和酸的损失都很少，基本保持它们之间的比例不变。对醇酸树脂常数经验地做以下调整见表2-1-10。  \n\n表2-1-10 醇酸树脂常数的调整（理论 $\\scriptstyle K=1)$   \n\n\n<html><body><table><tr><td>原 料</td><td>K值调整数</td><td>原 料</td><td>K值调整数</td></tr><tr><td>一元酸（脂肪酸） 豆油酸、亚麻油酸、红花油酸、松浆油酸</td><td rowspan=\"4\">不调整 减0.01 减0.03 加0.02 作二官能酸考虑</td><td>二元酸 苯二甲酸酐</td><td>加0.01</td></tr><tr><td>月桂酸、椰子油酸 松香</td><td>间苯二甲酸</td><td>加0.05</td></tr><tr><td>脱水麻油酸 桐油酸</td><td>多元醇 甘油、乙二醇、季戊四醇 三羟甲基乙烷、三羟甲基丙烷</td><td>不调整 减0.01</td></tr><tr><td></td><td>醇酸树脂酸值（AN）</td><td>减（AN—8）X0.0025</td></tr></table></body></html>\n\n注：一般醇酸树脂的制备都酯化至酸值在8mgKOH/g左右，如欲制高酸值醇酸树脂，可在高于酸值 $8\\mathrm{mgKOH/g}$ 后每4个单位减K值0.01.  \n\n生产醇酸树脂时需要一个恰当的配方以达到所要求的酯化程度、羟值和酸值。在设计醇酸树脂配方时，有三个条件必须确定： $\\textcircled{1}$ 用什么油、油度为多少； $\\textcircled{2}\\kappa$ 值为多少； $\\textcircled{3}$ 多元醇过量多少。油与油度为已知， $\\kappa$ 值按下列公式计算：  \n\n$$\nK{=}\\frac{m_{0}}{e_{\\mathrm{A}}}{=}\\frac{e_{\\mathrm{A_{1}}}+e_{\\mathrm{A_{2}}}/2+e_{\\mathrm{A_{1}}}/3+r e_{\\mathrm{A_{2}}}/x}{e_{\\mathrm{A_{1}}}+e_{\\mathrm{A_{2}}}}\n$$  \n\n式中 $e_{\\Lambda_{1}}$ —油的当量数；  \n\n$\\boldsymbol{e}_{\\mathsf{A}_{\\tau}}$ —苯二甲酸酐的当量数；—多元醇对苯二甲酸酐的比值；x—多元醇的官能度。  \n\nr值可由公式计算而得：  \n\n$$\nr=[K(e_{\\mathrm{A}_{1}}+e_{\\mathrm{A}_{2}})-e_{\\mathrm{A}_{1}}-e_{\\mathrm{A}_{2}}/2-e_{\\mathrm{A}_{1}}/3]\\frac{x}{e_{\\mathrm{A}_{2}}}\n$$  \n\n设每次配方计算都以苯二甲酸酐为 $\\scriptstyle1\\mathrm{mol}$ ，即 $e_{h_{z}}$ 为2，则：  \n\n$$\nr=\\left[e_{\\Lambda_{1}}\\left(K-\\frac{4}{3}\\right)+2K-1\\right]\\frac{x}{2}\n$$  \n\n如多元醇为甘油， $\\scriptstyle K=1$ 则：  \n\n$$\nr{=}\\frac{3}{2}{-}\\frac{e_{\\mathrm{A_{1}}}}{2}\n$$  \n\n如多元醇为季戊四醇， $\\scriptstyle K=1$ 则：  \n\n$$\nr{=}2{-}\\frac{2}{3}e_{\\mathrm{A_{1}}}\n$$  \n\n关于醇酸树脂的计算，近来有人做了进一步研究，提出一些新观点。把油脂的mo、cA、eB列为两项，G-表示甘油，F表示脂肪酸，举例见表2-1-11(a)、（b)。  \n\n表2-1-11（a）614短油度豆油醇酸树脂   \n\n\n<html><body><table><tr><td>序号</td><td>原料名称</td><td>缩写</td><td>质量分数/%</td><td>mo</td><td>cA</td><td></td></tr><tr><td>1</td><td>豆油</td><td></td><td>31.5</td><td>G0. 036</td><td></td><td>0.108</td></tr><tr><td></td><td>一缩二乙二醇</td><td></td><td></td><td>F0.108</td><td>0.108</td><td>0.047</td></tr><tr><td>2 3</td><td></td><td>DEG</td><td>2.5</td><td>0.024 0.073</td><td></td><td>0.218</td></tr><tr><td></td><td>甘油</td><td>GL</td><td>6.7</td><td></td><td></td><td></td></tr><tr><td>4 5</td><td>氢氧化锂</td><td></td><td>0.019</td><td></td><td></td><td></td></tr><tr><td></td><td>甘油</td><td>GL</td><td>3.3</td><td>0.036</td><td></td><td>0.108</td></tr><tr><td>6</td><td>季戊四醇</td><td>PE</td><td>12.5</td><td>0.085</td><td></td><td>0.353</td></tr><tr><td>7 8</td><td>苯甲酸</td><td>BA</td><td>12.0</td><td>0.098</td><td>0.098</td><td></td></tr><tr><td>合计</td><td>琴酐</td><td>PA</td><td>31.5</td><td>0.213</td><td>0.426</td><td></td></tr><tr><td></td><td>脱水</td><td></td><td>100.0 5.60</td><td>0.673 Wr94.40</td><td>0.632</td><td>0.834</td></tr></table></body></html>  \n\n表2-1-11（b）FA142\\*短油度豆油脂肪酸醇酸树脂   \n\n\n<html><body><table><tr><td>序号</td><td>原料名称</td><td>缩写</td><td>质量分数/%</td><td>m</td><td>A</td><td>eB</td></tr><tr><td>1</td><td>豆油脂肪酸</td><td></td><td>30.0</td><td>0.110</td><td>0.110</td><td></td></tr><tr><td></td><td></td><td></td><td></td><td>F0.108</td><td>0.108</td><td></td></tr><tr><td>2</td><td>甘油</td><td>GL</td><td>7.0</td><td>0.076</td><td></td><td>0.228</td></tr><tr><td>3</td><td>季戊四醇</td><td>PE</td><td>17.5.</td><td>0. 118</td><td></td><td>0.494</td></tr><tr><td>4</td><td>松香</td><td>R</td><td>11. 0</td><td>0.033</td><td>0.033</td><td></td></tr><tr><td>5</td><td>苯甲酸</td><td>BA</td><td>9.5</td><td>0.078</td><td>0.078</td><td></td></tr><tr><td>6</td><td>苯酐</td><td>PA</td><td>25.0</td><td>0.169</td><td>0.338</td><td></td></tr><tr><td>合计</td><td></td><td></td><td>100.0</td><td>0.584</td><td>0.559</td><td>0.722</td></tr><tr><td></td><td>脱水</td><td></td><td>7.0</td><td>Wr93.0</td><td></td><td></td></tr></table></body></html>  \n\n在表2-1-11(a）配方中，一缩二乙二醇（DEG）是聚酯的构成部分，是极性的，但它又是软组分；在表2-1-11(b）配方中，松香（R）是弱极性的，但它又是刚性的，这和豆油脂肪酸相近。两个配方中都有苯甲酸（BA）的情况和松香相近。所以 $O L_{t}$ 或 $_{O L}$ 就不能确切地表征树脂的弱极性与柔性成分的比例。为此有必要扩展 $O L_{t}$ 或 $_{O L}$ 的含意，提出表征刚柔性与极性的新“油度”：“柔性组分含量” $O L_{\\tau}$ 与 $O L_{\\mathrm{j}}$ “弱极性组分”。上述A、B两个树脂的有关参数见下表。  \n\n<html><body><table><tr><td>参数</td><td>A树脂</td><td>B树脂</td></tr><tr><td>OL (OL)</td><td></td><td>93.0 30.0=32.2%</td></tr><tr><td>OL,</td><td>94.40 31.5+2.536.0%</td><td>30.0 93. 0 =32. 2%</td></tr><tr><td>OL</td><td>94.40 31.5+12.0=46.1%</td><td>93.0 30.0+11.0+9.5= 54.3%</td></tr></table></body></html>  \n\n借助 $O L_{\\tau}$ 与 $O L_{\\mathrm{j}}$ 的引人，来深入地了解树脂B，单从 $O L_{i}$ 看，油度很短，但由于有大量的松香和苯甲酸，OL高达 $54.3\\%$ ，所以树脂的极性不高，可溶性好，流平刷涂性也好。所以 $O L_{\\tau}$ 与 $O L_{\\mathrm{j}}$ 的引人，对于已有配方的解析和新配方的设计都是有用的。  \n\n按照传统的计算方法举例如下。  \n\n【例】计算一个 $55\\%$ 油度亚麻油醇酸树脂的配方。 $\\kappa$ 值为1，多元醇为甘油。  \n\n解：按式r=  \n\n$$\n0.55={\\frac{293e_{\\mathrm{A_{1}}}}{130+293e_{\\mathrm{A_{1}}}+\\left({\\frac{3}{2}}-{\\frac{e_{\\mathrm{A_{1}}}}{2}}\\right)2\\times31}}\n$$  \n\n$$\ne_{\\mathsf{A}_{1}}=0.824\n$$  \n\n树脂配方为：  \n\n亚麻油 $0.824\\times293=241.4$ 甘油 $(3-e_{\\Lambda_{1}})\\times31=67.46$ 苯二甲酸酐 $2\\times74=148.00$ 配方分析见表2-1-12。  \n\n表2-1-12配方分析  \n\n\n<html><body><table><tr><td>组分</td><td>加料量/kg</td><td>A</td><td></td><td>mo</td><td>树脂成分/%</td></tr><tr><td>亚麻油</td><td>241.4</td><td>0. 824</td><td></td><td>0.824</td><td>55.00</td></tr><tr><td>甘油(油内)</td><td></td><td></td><td>0.824</td><td>0.275</td><td></td></tr><tr><td>甘油</td><td>67.5</td><td></td><td>2.176</td><td>0.725</td><td>15.38</td></tr><tr><td>苯二甲酸酐</td><td>148.0</td><td>2.000</td><td></td><td>1.000</td><td>33.72</td></tr><tr><td>总计</td><td>456.9</td><td>2.824</td><td>3.000</td><td>2. 824</td><td>104.10</td></tr><tr><td>理论出水量</td><td>18.0</td><td></td><td></td><td></td><td>4.10</td></tr><tr><td>醇酸树脂的量</td><td>438.9</td><td></td><td></td><td></td><td>100.00</td></tr></table></body></html>  \n\n$$\nR={\\frac{3.000}{2.824}}=1.\\ 062\\qquadr={\\frac{2.176}{2}}=1.\\ 088\\qquadK={\\frac{m_{0}}{e_{\\mathrm{A}}}}={\\frac{2.\\ 824}{2.\\ 824}}=1\n$$  \n\n这样简单的 $\\scriptstyle K=1$ 的甘油醇酸树脂可由再简化的公式，令 $e_{\\Lambda_{t}}=2$ 直接算出：  \n\n$$\ne_{\\mathsf{A}_{1}}={\\frac{293-262\\times\\hat{\\eta}\\oplus\\hat{\\eta}\\oplus\\hat{\\xi}}{223\\times\\hat{\\eta}\\oplus\\hat{\\eta}\\oplus\\hat{\\xi}}}.\n$$  \n\n【例】计算一个脂肪酸含量为 $62\\%$ 的豆油脂肪酸醇酸树脂的配方。设 $\\scriptstyle K=1$ ，季戊四醇的当量值为34.5。  \n\n解：令 $e_{A_{2}}=2$  \n\n$$\n\\displaystyle{\\begin{array}{l}{{\\displaystyle{K=\\frac{e_{\\mathsf{A}_{1}}+e_{\\mathsf{A}_{1}}/4+e_{\\mathsf{A}_{2}}/2+r e_{\\mathsf{A}_{2}}/4}{e_{\\mathsf{A}_{1}}+e_{\\mathsf{A}_{2}}}}}\\\\ {{\\displaystyle{1=\\frac{\\left(1+\\frac{1}{4}\\right)e_{\\mathsf{A}_{1}}+1+\\frac{1}{2}r}{e_{\\mathsf{A}_{1}}+2}}}}\\\\ {{\\displaystyle{\\frac{1}{4}e_{\\mathsf{A}_{1}}=1-\\frac{1}{2}r}}}\\end{array}}\n$$  \n\n$$\n0.62={\\frac{280e_{\\mathrm{A_{1}}}}{280e_{\\mathrm{A_{1}}}+e_{\\mathrm{A_{1}}}\\times34.5-e_{\\mathrm{A_{1}}}\\times18+e_{\\mathrm{A_{2}}}\\times74+r(e_{\\mathrm{A_{2}}}\\times34.5)-e_{\\mathrm{A_{2}}}\\times9}}\n$$  \n\n$$\n0.62={\\cfrac{280e_{\\mathrm{A_{1}}}}{280e_{\\mathrm{A_{1}}}+e_{\\mathrm{A_{1}}}\\times34.5-e_{\\mathrm{A_{1}}}\\times18+2\\times74+\\left(2-{\\frac{1}{2}}e_{\\mathrm{A_{1}}}\\right)\\times2\\times34.5-2\\times9}}\n$$  \n\n$$\n\\begin{array}{c}{0.62{=}\\displaystyle\\frac{280e_{A_{1}}}{262e_{A_{1}}+268}}\\\\ {e_{\\mathrm{A}_{1}}{=}\\displaystyle\\frac{268\\times0.62}{280{-}262\\times0.62}}\\\\ {e_{\\mathrm{A}_{1}}{=}1.413}\\end{array}\n$$  \n\n树脂配方为：  \n\n豆油脂肪酸 $1.413\\times280=395.$ 6苯二甲酸酐 $2\\times74=148.$ 0季戊四醇 $4\\times43.5=138.0$ 配方解析见表2-1-13。  \n\n表2-1-13配方解析  \n\n\n<html><body><table><tr><td>组分</td><td>加料量/kg</td><td>A</td><td>eB</td><td>me</td><td>树脂成分/%</td></tr><tr><td>豆油脂肪酸</td><td>395.6</td><td>1.413</td><td></td><td>1.413</td><td>61.99</td></tr><tr><td>季戊四醇</td><td>138.0</td><td></td><td>4</td><td>1. 000</td><td>21.62</td></tr><tr><td>苯二甲酸酐</td><td>148.0</td><td>2.000</td><td></td><td>1. 000</td><td>23.19</td></tr><tr><td>总计</td><td>681.6</td><td>3.413</td><td></td><td>3.413</td><td>106.80</td></tr><tr><td>理论出水量</td><td>43.4</td><td></td><td></td><td></td><td>6.80</td></tr><tr><td>醇酸树脂得量</td><td>638.2</td><td></td><td></td><td></td><td>100.00</td></tr></table></body></html>  \n\n$$\nK={\\frac{3.413}{3.413}}=1.\\ 000\\qquadK={\\frac{4}{3.413}}=1.\\ 172\n$$  \n\n对麻油醇酸树脂的配方的计算提出一个新的观点。季戊四醇是醇酸树脂最常用多元醇，季戊四醇（PE）的官能度问题，不同的看法是：由于工业季戊四醇并非纯品，它由单季戊四醇（MPE）和二季戊四醇（DPE）组成，单季戊四醇是四元醇，羟基当量为34.0，二季戊四醇是六元醇，羟基当量为42.33。一般涂料用季戊四醇是单季戊四醇和二季戊四醇的混合物，单季戊四醇占 $86\\%$ (质量)，二季戊四醇占 $12\\%$ 左右。工业季戊四醇的羟基当量在35. $5\\%$ 左右。平均官能度 $f$ 在4.15左右。所以在醇酸树脂的配方计算时，不应当把季戊四醇的官能度视为4.0，工业季戊四醇的官能度定为4.15更符合实际。在工艺实践中，如果只把麻油当成普通油脂，把它的组成部分分为甘油（G）和脂肪酸（F）两个基团，这样就忽略了它的一OH的存在。而实际工艺上，麻油可以不经过醇解，把它作为多元醇直接进行酯化。在直接酯化法的工艺中，麻油中的酯键并无变化，只是脂肪链上的一OH进行了反应。麻油醇酸树脂常用于氨基漆的成分或聚氨酯漆的羟基组分，一OH的存在对这两类树脂是十分重要的，所以麻油脂肪链上的一OH在配方设计中应得到反映。修正的办法是，在麻油基团分解时，除G（相表示甘油）、F（相表示脂肪酸）两项外，增加“H”项。而相应于直接酯化法（以及半酯化法）工艺，则可以称为麻油醇酸树脂的配方计算的“聚酯式”。  \n\n【例】麻油醇酸树脂配方的计算。  \n\n解：下面举例说明，配方中的麻油规格为羟基值 $165\\mathrm{mgKOH/g}$ ，平均官能度以2.75计。  \n\n40. $1\\%$ 、29.8%和78.4%油度醇酸树脂见表2-1-14～表2-1-16。  \n\n表2-1-1440.1%油度菌麻油甘油苯酐醇酸树脂   \n\n\n<html><body><table><tr><td rowspan=\"2\">序号</td><td rowspan=\"2\">配方</td><td rowspan=\"2\">质量分数 /%</td><td colspan=\"3\">醇解式</td><td colspan=\"3\">聚酯式</td></tr><tr><td>mo</td><td>eA</td><td></td><td>me</td><td>eA</td><td></td></tr><tr><td>1</td><td>麗麻油</td><td>38.05</td><td>G0. 041 F0.122</td><td>0.122</td><td>0.122</td><td>0.041</td><td></td><td>0.112</td></tr><tr><td></td><td></td><td></td><td>H</td><td></td><td>0.112</td><td></td><td></td><td></td></tr><tr><td>2</td><td>甘油98%</td><td>22.43</td><td>0.239</td><td></td><td>0.717</td><td>0.239</td><td></td><td>0.717</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>3</td><td>苯酐</td><td>39.52</td><td>0.267</td><td>0.534</td><td></td><td>0.267</td><td>0.534</td><td></td></tr><tr><td></td><td>合计</td><td>100</td><td>0.669</td><td>0.656</td><td>0.951</td><td>0.547</td><td>0.534</td><td>0.829</td></tr></table></body></html>  \n\n配方参数：  \n\n$$\nK_{2}=\\frac{0.547}{0.534}=1.024\n$$  \n\n$$\nR_{2}=r_{2}=\\frac{0.829}{0.534}=1.552\n$$  \n\n$$\nr_{1}=\\frac{0.717}{0.534}=1.343\n$$  \n\n表2-1-1529.8%油度麻油甘油苯酐苯甲酸醇酸树脂   \n\n\n<html><body><table><tr><td rowspan=\"2\">序号</td><td rowspan=\"2\">配方</td><td rowspan=\"2\">质量分数 /%</td><td colspan=\"3\">醇解式</td><td colspan=\"3\">聚酯式</td></tr><tr><td>mo</td><td>CA</td><td>eB</td><td>mo</td><td>A</td><td></td></tr><tr><td>1</td><td>麗麻油</td><td>28.0</td><td>G0.030 F0.090</td><td>0. 090</td><td>0.090</td><td>0.030</td><td></td><td>0.082</td></tr><tr><td></td><td></td><td></td><td>H</td><td></td><td>0.082</td><td></td><td></td><td></td></tr><tr><td>2</td><td>甘油</td><td>25.0</td><td>0.272</td><td></td><td>0.815</td><td>0.272</td><td></td><td>0.815</td></tr><tr><td>3</td><td>苯酐</td><td>41. 0</td><td>0.277</td><td>0.544</td><td></td><td>0.277</td><td>0. 554</td><td></td></tr><tr><td>4</td><td>苯甲酸</td><td>6.0</td><td>0.049</td><td>0.049</td><td></td><td></td><td>0.049</td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>0. 049</td><td></td><td></td></tr><tr><td></td><td>合计</td><td>100</td><td>0.718</td><td>0.698</td><td>0.987</td><td>0.628</td><td>0.603</td><td>0.897</td></tr></table></body></html>  \n\n配方参数：  \n\n$$\nK_{1}=\\frac{0.718}{0.693}=1.036\n$$  \n\n$$\nK_{2}={\\frac{0.628}{0.603}}=1.041\n$$  \n\n$$\nR_{2}=r_{2}=\\frac{0.897}{0.603}=1.488\n$$  \n\n表2-1-1678.4%油度葡麻油季戊四醇苯酐醇酸树脂   \n\n\n<html><body><table><tr><td rowspan=\"2\">序号</td><td rowspan=\"2\">配方</td><td rowspan=\"2\">质量分数</td><td colspan=\"3\"></td><td colspan=\"3\"></td></tr><tr><td>mo</td><td>静式</td><td>eB</td><td>mo</td><td>式</td><td>eB</td></tr><tr><td>1</td><td>麻油</td><td>73.2</td><td>GO. 078 H</td><td>0. 235</td><td>0.235 0.215</td><td>0.078</td><td></td><td>0.215</td></tr></table></body></html>  \n\n配方参数：  \n\n$$\nK_{1}=\\frac{0.495}{0.471}=1.051\\qquadK_{2}=\\frac{0.26}{0.236}=1.102\n$$  \n\n$$\nR_{1}=\\frac{0.713}{0.471}=1.513R_{2}=r_{2}=\\frac{0.478}{0.236}=2.205\n$$  \n\n$$\nr_{1}=\\frac{0.263}{0.236}=1.114\\qquad\\mathrm{OH}{\\%}:4.203\n$$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 154,
+        "chunk": "# 五、醇酸树脂的制造",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 155,
+        "chunk": "# （一）醇酸树脂的原料  \n\n醇酸树脂的主要原料是多元醇、多元酸、植物油（脂肪酸），在生产过程中还需加少量助剂，并用适当溶剂兑稀成液体树脂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 156,
+        "chunk": "# 1.多元醇  \n\n通式为ROH（R是烃基)，系由饱和烃类分子上一个氢原子为羟基所取代而构成。由于羟基取代的烃类分子上的氢原子的位置不同，可以生成三类不同的醇：  \n\n$\\textcircled{1}$ 伯醇连接羟基的碳原子上有两个氢原子；  \n$\\textcircled{2}$ 仲醇连接羟基的碳原子上有一个氢原子；  \n$\\textcircled{3}$ 叔醇连接羟基的碳原子上没有氢原子。  \n\n如丁醇可有以下三种结构：  \n\n$$\n\\begin{array}{r l}{\\mathrm{CH}_{3}\\mathrm{-CH}_{2}\\mathrm{-CH}_{2}\\mathrm{-CH}_{2}\\mathrm{-OH}}&{\\qquad\\begin{array}{c c}{\\mathrm{H}}&{\\qquad\\mathrm{CH}_{3}}\\\\ {\\mathrm{CH}_{3}\\mathrm{-CH}_{2}\\mathrm{-C\\mathrm{-}C H}_{3}}&{\\qquad\\mathrm{CH}_{3}\\mathrm{-CH}_{3}}\\\\ {\\mathrm{OH}}&{\\qquad\\mathrm{OH}}\\end{array}}\\end{array}\n$$  \n\n正丁醇（伯醇）  \n\n仲丁醇   \n叔丁醇  \n\n三种醇的化学反应活性不同。在与有机酸酯化时，伯醇反应最容易、最快；仲醇较伯醇稍难、稍慢；叔醇则反应甚难，而且易于在酸存在下脱水醚化。  \n\n烷烃分子有一个以上的碳原子，其氢原子被羟基取代，这种多羟基化合物称为多元醇。几个羟基称为“几元”。表2-1-17为与制备醇酸树脂有关的多元醇的物性。  \n\n表2-1-17常用多元醇的物性  \n\n\n<html><body><table><tr><td>多元醇</td><td>当量值</td><td>状态</td><td>熔点/C</td><td>沸点/C</td><td>相对密度</td></tr><tr><td>二元醇</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>乙二醇</td><td>31.0</td><td>液</td><td></td><td>198</td><td>1.12</td></tr><tr><td>1,3-丁二醇</td><td>45.0</td><td>液</td><td></td><td>205</td><td>1. 01</td></tr><tr><td>新戊(基)二醇</td><td>52.1</td><td>固</td><td>125</td><td>204</td><td>1.06</td></tr><tr><td>二乙二醇</td><td>67.1</td><td>液</td><td></td><td>232</td><td>1.02</td></tr><tr><td>三元醇</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>甘油</td><td>30.7</td><td>液</td><td>17.9</td><td>290</td><td>1.26</td></tr><tr><td>甘油(99%)</td><td>31.0</td><td>液</td><td></td><td></td><td></td></tr><tr><td>甘油(95%)</td><td>32.3</td><td></td><td></td><td></td><td></td></tr><tr><td>三羟甲基丙烷</td><td>44.7</td><td>固</td><td>60</td><td>295</td><td>1.14</td></tr><tr><td>四元醇 季戊四醇</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>34.0 35.1</td><td>固</td><td>262</td><td></td><td>1.38</td></tr><tr><td>六元醇</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>二季戊四醇 [C(CHOH)CH]O</td><td>42.4 43.5</td><td>固</td><td>222</td><td></td><td>1.37</td></tr></table></body></html>\n\n$\\Phi$ 一般工业品的当量值。醇酸树脂一章中出现的当量值有特殊的意义，在计算醇酸树脂配方时是有用的数值。它是指与一个羟基（当量值为17）化合时所需的质量。",
+        "category": " Introduction"
+    },
+    {
+        "id": 157,
+        "chunk": "# 2.有机酸与多元酸  \n\n含有羧基的有机化合物称为有机酸。羧基基团具有活性，能离解成离子。含有一个以上的羧基者为多元酸。与醇酸树脂制造有关的有机酸与多元酸列于表2-1-18。  \n\n表2-1-18与醇酸树脂制造有关的有机酸与多元酸的物性  \n\n\n<html><body><table><tr><td>有机酸</td><td>当量值</td><td>熔点/℃</td><td>沸点/℃</td><td>相对密度</td></tr><tr><td>一元酸</td><td></td><td></td><td></td><td></td></tr><tr><td>松香（酸值165mgKOH/g）</td><td>340</td><td>65</td><td>249</td><td>1.07 1.27</td></tr><tr><td>苯甲酸</td><td>122.1</td><td>122</td><td></td><td></td></tr><tr><td>对叔丁基苯甲酸</td><td>178.1</td><td>165</td><td></td><td>1.15</td></tr><tr><td>合成脂肪酸</td><td></td><td></td><td></td><td></td></tr><tr><td>低碳酸（酸值360~385mgKOH/g）</td><td></td><td></td><td></td><td></td></tr><tr><td>中碳酸（酸值220~240mgKOH/g）</td><td></td><td></td><td></td><td></td></tr><tr><td>2-乙基已酸</td><td>144.2</td><td></td><td>230</td><td>0.91</td></tr><tr><td>月桂酸（十二烷酸）</td><td>200.3</td><td>45</td><td>300</td><td>0.88</td></tr><tr><td>辛酸</td><td>144.2</td><td></td><td>240</td><td>0.91</td></tr><tr><td>癸酸</td><td>172.3</td><td>32</td><td>270</td><td>0.90</td></tr><tr><td>椰子油脂肪酸</td><td>205</td><td></td><td></td><td>0.88</td></tr><tr><td>油酸</td><td>282.5</td><td></td><td></td><td>0.90</td></tr><tr><td>亚油酸</td><td>280.4</td><td></td><td></td><td>0.90</td></tr><tr><td>亚麻酸</td><td>278.4</td><td></td><td></td><td>0.91</td></tr><tr><td>麻油酸</td><td>297</td><td></td><td></td><td>0.94</td></tr><tr><td>脱水麻油酸</td><td>280</td><td></td><td></td><td>0.90</td></tr><tr><td>松浆油酸</td><td></td><td></td><td></td><td></td></tr><tr><td>酸值为195mgKOH/g</td><td>288</td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td>0.90</td></tr><tr><td>酸值为192mgKOH/g</td><td>292</td><td></td><td></td><td>0.90</td></tr><tr><td>二元酸</td><td></td><td></td><td></td><td></td></tr><tr><td>己二酸</td><td>73.1</td><td>152</td><td></td><td>1.37</td></tr><tr><td>富马酸</td><td>58</td><td>升华</td><td></td><td>1.63</td></tr><tr><td>顺丁烯二酸酐</td><td>49</td><td>55</td><td>200</td><td>1.47</td></tr><tr><td>苯二甲酸酐</td><td>74.1</td><td>131</td><td>284</td><td>1.52</td></tr><tr><td>间苯二甲酸</td><td>83.1</td><td>354</td><td></td><td>1.54</td></tr><tr><td>癸二酸</td><td>101.1</td><td>135</td><td></td><td>1.11</td></tr><tr><td>三元酸</td><td></td><td></td><td></td><td></td></tr><tr><td>偏苯三甲酸</td><td>70.</td><td>216</td><td></td><td></td></tr><tr><td></td><td>64</td><td>165</td><td></td><td>1.56</td></tr><tr><td>偏苯三甲酸酐</td><td></td><td></td><td></td><td>1.55</td></tr><tr><td>四元酸 均苯四甲酸酐</td><td>54.5</td><td>286</td><td>400</td><td>1.68</td></tr></table></body></html>\n\n$\\Phi$ 合成脂肪酸系混合酸，酸值是一个馏分的平均值。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 158,
+        "chunk": "# 3.油类 (甘油三脂肪酸酯)  \n\n醇酸树脂也可采用酯交换的方法直接使用油。常用油类的品种和物化性能见表2-1-19。  \n\n表2-1-19常用油类的品种和物化性能  \n\n\n<html><body><table><tr><td>品种</td><td>当量值</td><td>状态</td><td>碘值（韦氏）</td><td>相对密度</td></tr><tr><td>椰子油</td><td>218</td><td>固</td><td>7.5~16.5</td><td>0.92</td></tr><tr><td>麻油</td><td>310</td><td>液</td><td>80~90</td><td>0.96</td></tr><tr><td>棉籽油</td><td>289</td><td>液</td><td>99~113</td><td>0.92</td></tr><tr><td>豆油</td><td>293</td><td>液</td><td>130~140</td><td>0.92</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>品种</td><td>当量值</td><td>状态</td><td>碘值(韦氏) /(glz/100g)</td><td>相对密度</td></tr><tr><td>脱水麻油</td><td>293</td><td>液</td><td>125~140</td><td>0.94</td></tr><tr><td>亚麻油</td><td>293</td><td>液</td><td>170~200</td><td>0.93</td></tr><tr><td>梓油</td><td>293</td><td>液</td><td>170~187</td><td>0.93</td></tr><tr><td>桐油</td><td>293</td><td>液</td><td>160~165</td><td>0.94</td></tr><tr><td>葵花油</td><td>293</td><td>液</td><td>124~140</td><td>0.92</td></tr><tr><td>红花油</td><td>293</td><td>液</td><td>130~150</td><td>0.92</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 159,
+        "chunk": "# 4.溶剂、助剂  \n\n（1）溶剂除水性醇酸树脂外，自产或商品醇酸树脂，大部分是溶剂型醇酸树脂。有机溶剂在醇酸树脂成分中，占有很大比例，真正的高固体分醇酸树脂还比较少。所以溶剂对醇酸树脂性能、用途以及生产工艺与施工应用，甚至安全和劳动保护都有很大影响。大力发展水性醇酸树脂和高固体分醇酸树脂，减少醇酸树脂的有机溶剂的排放，降低醇酸树脂的VOC的含量，仍然是涂料工业的发展方向。  \n\n200#油漆溶剂油，是醇酸树脂使用最多、最广的一种溶剂。 $200^{\\sharp}$ 油漆溶剂油来源于石油化工，是由 $\\mathbf{C}_{4}{\\sim}\\mathbf{C}_{11}$ 的烷烃、烯烃、环烷烃和少量的芳香烃组成的混合油，主要成分是戊烷、已烷、庚烷和辛烷。沸程范围 $145\\sim200\\mathrm{{C}}$ ，很少一部分可达到 $210^{\\circ}\\mathrm{C}$ 。长油度醇酸树脂可以全部用 $200^{*}$ 油漆溶剂溶解；中油度醇酸树脂则需要用少量的芳香烃和200#油漆溶剂油配合兑稀；而短油度醇酸树脂则不溶于 $200^{\\sharp}$ 油漆溶剂油。  \n\n根据醇酸树脂的油度和用途来选择溶剂，常用于醇酸树脂生产的溶剂还有甲苯、二甲苯、重芳香烃、高沸点芳香烃、正丁醇和异丁醇、乙酸酯等。  \n\n(2）醇酸树脂及醇酸树脂漆用助剂醇酸树脂制造过程中，常用助剂有醇解催化剂（油脂为原料）、酯化催化剂、减色剂等。20世纪90年代，国产酯化催化剂如506催化剂、AC-1催化剂等，进口的ATO化学的催化剂都有较广泛的应用。水性醇酸树脂生产过程还需加乳化剂等多种的助剂。  \n\n醇酸树脂漆特别是氧化（干燥）型醇酸漆必须加催干剂、防结皮剂。醇酸树脂制漆用的分散剂、防沉剂等和其他合成树脂漆所用助剂相似，只是醇酸树脂漆对颜、填料有较好的润湿性，相对而言，助剂应用较少。其中催干剂和防结皮剂在氧化干燥醇酸漆应用非常广泛。  \n\n(3）催干剂DIN55901催干剂的定义：催干剂在溶液中也称干料，是可溶于有机溶剂和基料的金属有机化合物，化学上它们属皂类，将它们加入不饱和油或基料中，能显著缩短固化时间。所谓固化是指涂层转变成固体状态。 2  \n\n催干剂都是金属皂类，其有机酸部分主要有环烷酸、2-乙基己酸、松浆油酸，还有松香、亚油酸等。传统的催干剂在“油性漆”和“涂料助剂”两章中已做过介绍。国内涂料工业对催干剂应用趋势之一是由多品种到少品种，甚至只加一种复合催干剂。稀土催干剂已得到普遍应用，铅类催干剂趋于淘汰。国外对催干剂的研究十分活跃，尤其用于水性醇酸和高固体分醇酸漆的催干剂。从某种意义上说，催干剂的研究及其进展代表了醇酸树脂漆的发展方向。  \n\n传统的催干剂根据其催干过程中的作用分为两类：一类为主催干剂，以多种氧化态存在，而不进行还原反应的金属皂；钻、锰、钒和铈均属主催干剂；另一类为助催干剂，只以一种氧化态存在的金属皂，并且只有和主催干剂并用时才有催化作用，铁、锌、钡和锶属此类。还有一类催干剂称为协同催干剂（co-ordination driers)，也称配位体聚合催干剂。催化干燥作用是基于漆基中的羟基或羧基的反应，这类催干剂称为协同催干剂，如锆（Zr)，锆催干剂本身成为漆膜的一部分。  \n\n水性涂料的催干剂，本质上水性和溶剂型气干基料具有相同的干燥机理，然而干燥性能却很不一样。除了溶剂组成不同外，水性涂料中基料体系会产生各种各样的干燥缺陷，如干燥时间长、干性下降、实干不好和硬度较差。  \n\n水会使基料水解，导致干性下降。水也会减缓对氧的吸收，从而使自氧化过程减缓。水还会影响催干剂的稳定性，作为强配位体，水可和钻等金属离子络合，生成钻的络合物具有较弱的氧化电势（潜能)，因而钻作为自氧化催化剂的作用降低，而且该复合物不稳定。补偿由于水解导致催千剂损失的实用方法是加人较多的主催干剂钴或锰。  \n\n国内水性催干剂市场几乎是空白，上海涂料有限公司技术中心开发出双酮络合物水性催干剂，即：  \n\n![](images/61a743342fb8ed0f174085c8c714109f289d8b6441808252c98319f13487a301.jpg)  \n\n羧酸盐金属皂经乳化后在水性体系中的混溶性很好，但当水性体系 $\\mathsf{p H}{\\mathsf{>}}7$ 时，金属离子会水解，引起树脂“失干”。经菲咯啉、联吡啶络合的催干剂能很好地抑制金属离子的水解，但菲咯啉、联吡啶的价格昂贵。双酮络合物水性催干剂因其耐水解性、催干性和经济实用性，而成为一种新型水性催干剂。以特定长链羧酸酯与短链的甲基酮为原料，用醇钠为催化剂，自制双酮络合剂，对金属钴、锆、铈、锰、铁、锌、镁、钙进行络合，得到系列催干剂。这些催干剂既能溶解于水性体系，又能溶解在溶剂体系中。  \n\n高固体分醇酸树脂漆应用的催干剂：高固体分是减少VOC有效途径之一。但普通催干剂都含大量溶剂，不能满足高固体分醇酸树脂漆的要求，这类催于剂已经问世，这方面国内研究较少。  \n\n(4）防结皮剂醇酸树脂漆，尤其氧化干燥型醇酸树脂漆，在使用和贮存过程中会发生结皮。结皮现象不但造成大量的损耗，而且影响漆膜外观，产生粗粒、粗糙等缺陷，所以气干型醇酸树脂漆，往往加入防结皮剂。防结皮剂主要是两类化合物：一类是酚类抗结皮剂；另一类是类抗结皮剂。应用较广泛的是类抗结皮剂，如甲乙酮、丁醛、环已酮。在醇酸树脂漆及环氧酯漆中多使用甲乙酮。  \n\n具有—C一NOH的化合物都称为类。类抗结皮机理有三个方面：抗氧化作用，类化合物易氧化，能阻止漆的氧化聚合成膜；溶解作用，液态的类化合物为强溶剂，能延迟胶凝体的形成而产生抗结皮作用；络合作用，能和催干剂的金属部分形成络合物，从而使催干剂失去催干性，而延迟结皮。在成膜过程中类挥发而络合物趋向分解，而催干剂又恢复催干作用。  \n\n甲乙酮结构式如下：  \n\n$$\n\\mathrm{CH}_{3}{-}\\mathrm{C-NOH} \n$$  \n\n无色透明液体，沸点 $151{\\sim}155\\mathrm{^c}$ ，闪点 $52\\%$ ，相对密度0.908。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 160,
+        "chunk": "# （二）制造醇酸树脂的方法  \n\n制造醇酸树脂有四种基本方法，脂肪酸法、脂肪酸-油法、油稀释法、醇解法，其中脂  \n\n肪酸法和醇解法是最主要的方法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 161,
+        "chunk": "# 1.脂肪酸法制造醇酸树脂  \n\n由于油脂化工的进步，油脂分解成纯度很高的各种脂肪酸，这不仅为脂肪酸法生产醇酸树脂提供了充足的原料，而且大大提高了醇酸树脂的质量。为醇酸树脂的商品化、生产大型化打下基础，使得醇酸树脂的用途更广泛，例如现在的木器漆，较传统的醇酸清漆质量上升一个档次。从而促进了我国涂料工业的发展。  \n\n脂肪酸法制造醇酸树脂可以直接将多元醇与多元酸、脂肪酸进行酯化生产。因为脂肪酸对多元醇、苯二甲酸酐可起溶解作用，即酯化是在均相体系完成的。脂肪酸法又可分为以下几种。  \n\n(1）常规法将全部反应物同时加入反应釜内，在不断地揽拌下升温，在规定温度$(200{\\sim}250\\Upsilon)$ ）下保持酯化，中间不断地定期测定酸值与黏度，直至达到规定要求时停止加热，将树脂溶解成溶液、过滤净化。  \n\n(2）高聚物法在理论上往往认为，不论投料顺序如何，由于酯交换作用的关系，同一配方最终都将得到一个平衡结构的产物，实际并不如此。多元醇不同位置的羟基、脂肪酸的羧基、苯二甲酸酐的酐基、苯二甲酸酐形成半酯的羧基，它们之间的反应活性不同，而且形成的酯结构之间的酯交换非常缓慢、轻微，因此制造醇酸树脂时，不同的原料加人顺序不同，生产的最终产物的结构也不一样，所以原料加入顺序对生产工艺是非常重要的。配方的讨论只涉及了合适的配量，至于这个醇酸树脂如何化学结合成最好的组成，则是制造工艺的问题了。  \n\nKraft提出了高聚物法制造醇酸树脂工艺，其方法为： $\\textcircled{1}$ 先将全部多元醇、苯二甲酸酐与一部分脂肪酸反应至低酸值，制成高分子量链状成分。 $\\textcircled{2}$ 然后加入其余量的脂肪酸再反应成为低酸值树脂。制成的树脂黏度较常规者为高，颜色较浅，漆膜干率与耐碱性有所提高。此法对松浆油酸长油度醇酸树脂改进较多。  \n\n【例】豆油脂肪酸醇酸树脂。  \n\n配方：苯二甲酸酐：季戊四醇：豆油脂肪酸 $=1.07:1:1.5$ （摩尔比）  \n\n如果采用常规法：   \n豆油脂肪酸 58.6kg 苯二甲酸酐 21.6kg   \n季戊四醇（过量10%） 19.8kg  \n\n一起加入反应釜，搅拌、升温，以溶剂法酯化至酸值 $10\\mathrm{mgKOH/g}$ 以下。  \n\n如果采用高聚物法：  \n\n豆油脂肪酸（58.6×70%） 41.0kg 苯二甲酸酐 21. 6kg 季戊四醇 19.8kg  \n\n以上三种原料先在 $230\\mathrm{\\bar{C}}$ 酯化至酸值 $\\boldsymbol{7.05K O H/g}$ ，再加入豆油脂肪酸（ $58.6\\times30\\%$ $17.6\\mathrm{kg}$ ，继续酯化 $(230^{\\circ}\\mathsf{C}).$ ）至酸值 $9\\mathrm{{mgKOH/g}}$ 以下。  \n\n常规法与高聚物法所制醇酸树脂性能比较见表2-1-20。  \n\n表2-1-20常规法与高聚物法所制醇酸树脂性能比较   \n\n\n<html><body><table><tr><td>项目</td><td>常规法</td><td>高聚物法</td><td>项目</td><td>常规法</td><td>高聚物法</td></tr><tr><td>总酶化时间（230C）/min</td><td>250</td><td>300</td><td>千28天</td><td>14</td><td>20</td></tr><tr><td>黏度(60%200°油漆溶剂，加氏管）/s</td><td>5(N)</td><td>33(Z)</td><td>浸冷水（恢复时间）/h</td><td>立刻</td><td>0.05</td></tr><tr><td>颜色（加氏色度）/号</td><td>4</td><td>4</td><td>浸热水（恢复时间）/h</td><td>0.25</td><td>0.25</td></tr><tr><td>室温干燥（湿膜75μm，加0.3%</td><td>80</td><td>15</td><td>浸30%NaOH溶液</td><td></td><td></td></tr><tr><td>Pb,0.03%Co)凝定/min</td><td></td><td></td><td>开始侵蚀/h</td><td>0.25</td><td>0.42</td></tr><tr><td>指触干/min</td><td>190</td><td>70</td><td>剥落/h</td><td>2</td><td>48</td></tr><tr><td>斯氏硬度(Sward)</td><td></td><td></td><td>浸1%海水</td><td></td><td></td></tr><tr><td>干1天</td><td>10</td><td>10</td><td>开始侵蚀/h</td><td>0.25</td><td>1.25</td></tr><tr><td>干7天</td><td>12</td><td>16</td><td>剥落/h</td><td>24</td><td>96</td></tr></table></body></html>  \n\n【例】松浆油酸制醇酸树脂漆干燥较慢，但用以下方法可以改进。  \n\n配方：苯二甲酸酐：季戊四醇：松浆油酸=1.038：1：1.41（摩尔比）；油度65.5%季戊四醇 20. 55kg(0. 142mol) 苯二甲酸酐松浆油酸 34. 7kg(0. 121mol)  \n\n21. 70kg(0. 146mol)  \n\n以上三者先一起在反应釜内以溶剂法酯化至酸值为 $\\mathrm{7mgKOH/g}$ ，再加人松浆油酸23.05kg（0.080mol），继续在 $230\\mathrm{\\Upsilon}$ 酯化至酸值达 ${\\mathrm{7}}{\\mathrm{mgKOH/g}}$ 以下。制成 $50\\%$ 石油油漆溶剂油溶液，黏度为加氏 $\\mathbf{v}{\\sim}\\mathbf{Y}$ 。加人 $0.5\\%\\mathrm{Pb}$ 、0.05%Co（金属量）催干剂后漆膜干率可超过相同脂肪酸含量的豆油醇酸树脂。  \n\n如何选定脂肪酸的分批比例可参考表2-1-21。  \n\n表2-1-21第一阶段脂肪酸加量对树脂性能的影响  \n\n\n<html><body><table><tr><td rowspan=\"2\">性能</td><td colspan=\"6\">第一阶段脂肪酸加量</td></tr><tr><td>100%</td><td>80%</td><td>70%</td><td>65%</td><td>63%</td><td>60%</td></tr><tr><td>开始酸值/（mgKOH/g）</td><td></td><td>9.2</td><td>8.1</td><td>6.7</td><td>8</td><td>8.9</td></tr><tr><td>最后酸值（固体）/（mgKOH/g）</td><td>5.7</td><td>5.7</td><td>6.1</td><td>7</td><td>7.4</td><td>8.4</td></tr><tr><td>50%石油油漆溶剂油溶液黏度（加氏）</td><td>B</td><td>D</td><td>D</td><td>S</td><td>Q</td><td>V</td></tr><tr><td>颜色（加氏色度）/号</td><td>6-</td><td>6+</td><td>6一</td><td>5-</td><td>5-</td><td></td></tr><tr><td>室温干燥</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>凝定/h</td><td>3.15</td><td>3.15</td><td>3.15</td><td>1.31</td><td>1.31</td><td>②</td></tr><tr><td>指压干/h</td><td>6.45</td><td>4.3</td><td>4.44</td><td>4.21</td><td>4.16</td><td>一</td></tr><tr><td>斯氏硬度（Sward)</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>干1天</td><td>14</td><td>16</td><td>14</td><td>14</td><td>14</td><td>一</td></tr><tr><td>干7天</td><td>18</td><td>20</td><td>18</td><td>18</td><td>16</td><td>一</td></tr><tr><td>浸3%NaOH溶液</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>开始侵蚀/min</td><td>19</td><td>19</td><td>7</td><td>26</td><td>21</td><td></td></tr><tr><td>剥落/h</td><td>1</td><td>55min</td><td>5imin</td><td>1.5</td><td>1. 88</td><td>一</td></tr><tr><td>洪干</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>斯氏硬度（Sward）</td><td>12</td><td>12</td><td>10</td><td>10</td><td>10</td><td>一</td></tr><tr><td>浸3%NaOH溶液</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>开始侵蚀/min</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td><td></td></tr><tr><td>剥落/h</td><td>1.92</td><td>6.33</td><td>14.33</td><td>44</td><td>70</td><td>二</td></tr></table></body></html>\n\n$\\Phi$ 配方为：苯二甲酸酐：季戊四醇：松浆油酸=1.035：1：1.41（摩尔比）；第一阶段酯化温度230℃，第二阶段酯化温度245C，②有胶粒，未测定，  \n\n第一阶段的酯化达到的酸值，即酯化程度，影响制成的醇酸树脂的干率（表2-1-22）。  \n\n表2-1-22第一阶段的酶化程度对醇酸树脂干率的影响  \n\n\n<html><body><table><tr><td rowspan=\"2\">性 能</td><td colspan=\"4\">第一阶段酯化脂肪酸用量</td></tr><tr><td>60%</td><td>60%</td><td>60%</td><td>60%</td></tr><tr><td>开始酸值/（mgKOH/g）</td><td>8.9</td><td>10.8</td><td>15.5</td><td>19.2</td></tr><tr><td>最后酸值/（mgKOH/g）</td><td>8.4</td><td>5.2</td><td>7.3</td><td>4.1</td></tr><tr><td>50%油漆溶剂油溶液黏度（加氏）</td><td>V</td><td>P+</td><td>M+</td><td>E+</td></tr><tr><td>颜色（加氏色度）/号</td><td>5+</td><td>6+</td><td>7+</td><td>8+</td></tr><tr><td>干燥时间</td><td></td><td></td><td></td><td></td></tr><tr><td>凝定/min</td><td>?</td><td>50</td><td>50</td><td>60</td></tr><tr><td>指压干/h</td><td>②</td><td>4.08</td><td>4.5</td><td>8</td></tr></table></body></html>\n\n$\\Phi$ 配方为：苯二甲酸酐：季戊四醇：脂肪酸 $\\c=$ 1. 035·1 ：1.41（摩尔比）；油度65.5%。②十号表示上限。③有胶粒，未测定。  \n\n高聚物法的目的是先构成高分子量链状物以提高醇酸树脂的分子量，改善醇酸树脂的性能。Kraft对高聚物法醇酸树脂进行分级分离。表2-1-22为分子量分布及不同级分的性能。  \n\n(3）酯化过程中脂肪酸的聚合在醇酸树脂制造的酯化过程中，因所用的脂肪酸不同，有时也有热聚合发生（二聚化)。热聚合反应速率与油（脂肪酸）的种类有关。脂肪酸的聚合温度与其原始油相同。二聚化的发生相当于增加二元酸。所以酯化温度要随油的种类和油度而变动。聚合快的油类、油度短的配方温度要低些（如 $200\\sim210^{\\circ}\\mathrm{C};$ ，生产工艺选溶剂法。  \n\n脂肪酸法的优点如下。  \n\n$\\boldsymbol{\\Phi}$ 因为使用的是脂肪酸，不含甘油，所以可以制含有甘油的醇酸树脂，也可以制不含甘油的醇酸树脂。  \n\n$\\textcircled{2}$ 脂肪酸由油分解而得，可以进行分离、精馏、选取其中需要的脂肪酸而排除不需要的脂肪酸。如可以使用纯亚油酸，而不使用亚麻酸以减弱黄变性，弃去饱和脂肪酸以提高碘值等，这是使用原料油所不能做到的。  \n\n$\\textcircled{3}$ 生产上可以分步加脂肪酸进行酯化，用原料油只能一次全部投入不能改变。  \n\n脂肪酸法的缺点如下。  \n\n$\\Phi$ 较直接使用油增加了工序、提高了成本。  \n$\\textcircled{2}$ 脂肪酸有腐蚀性，需要有耐腐蚀的设备。  \n$\\textcircled{3}$ 脂肪酸熔点较高，需有保温装置以保证其处于液体状态。  \n$\\textcircled{4}$ 贮存期间脂肪酸的颜色易变深。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 162,
+        "chunk": "# 2.醇解法制造醇酸树脂  \n\n因为油在加热的情况下不能溶解甘油和苯二甲酸酐，也不能形成均相，所以应采取有效步骤改变这种状态使之成为均相，然后再进行化学反应。这种方法就是制造醇酸树脂最常用的醇解法。  \n\n在工艺中首先表现为在醇解温度下的均相化，也就是“热透明”，进一步才是完成醇解。如应用几种醇之间以及醇解物之间的共溶效应，来促进体系均相化，从而也促进醇解。例如，一缩二乙二醇（DEG）本身可以看成介于油脂和甘油之间的溶剂，又易于醇解，在油脂和甘油体系中加入少量的一缩二乙二醇，可以加速体系的热透明，更快地完成醇解。至于一缩二乙二醇的加量，当然还要考虑树脂的性能的需求。在有甘油、一缩二乙二醇的豆油醇酸树脂的配方中，在醇解时，甘油、一缩二乙二醇和豆油三者可以一起加人，醇解很快。在实验室，升温至 $240\\%$ ，5min即可热透明，并完成醇解。若不加一缩二乙二醇，则要$20\\mathrm{{min}}$ 。要注意一缩二乙二醇的沸点低，在醇解温度下易于挥发。新戊二醇（NGE）等二元醇也有促进油和甘油的醇解作用。  \n\n醇解工序是以油脂为原料制造醇酸树脂中非常重要的步骤，它影响醇酸树脂的分子结构和分子量的分布。醇解的目的是制成甘油的不完全脂肪酸酯，主要是甘油一酸酯。实质上是一个改性的二元醇。用来制造醇酸树脂的油必须经过精制，特别要经过碱漂以除去蛋白质、磷脂等杂质，还要洗净残余的碱以免影响催化作用和颜色。  \n\n油（甘油三酸酯）与甘油在 $200{\\sim}250^{\\circ}\\mathrm{C}$ 和催化剂存在下，发生脂肪酸的再分配作用。  \n\n(1）醇解在油与甘油的混溶相中进行醇解反应发生在油与甘油的混溶相中。油、甘油、催化剂三者之间的比例为 $1:(0,2{\\sim}0,4):(0,04{\\sim}0.2)$ （质量比)，工艺操作是先把油加入反应釜中，再加入甘油和催化剂。催化剂和油反应生成皂，一方面帮助反应，另一方面帮助甘油混溶于油相中。在情性气体保护下，加热至 $200\\sim250^{\\circ}\\mathrm{C}$ 。最后将达到一个“平衡点”，游离的甘油与结合的甘油的量不再变化。高温增加了甘油与油的混溶性，有利于反应的进行。没有参加反应的甘油另成一相。豆油、亚麻油、梓油、桐油、红花油等分子量都和棉籽油相近，和甘油的混溶度相差不多。椰子油分子量较小，则和甘油混溶度相对大得多。混溶度是随温度增加而增加，醇解程度与甘油量和反应温度有关，催化剂只加速醇解反应。  \n\n醇解反应与酯化反应相似，在均相之中形成平衡状态的混合物，所得到的是甘油一酸酯、甘油二酸酯、油和游离甘油的混合物。通过醇解反应希望得到更多的甘油一酸酯，又分为α-甘油一酸酯和 $\\beta$ 甘油一酸酯，a-甘油一酸酯可以用过碘酸法测量出来。由于醇解反应是个可逆反应，它服从质量定律，甘油量增加，可使甘油一酸酯的量增加，但此时游离甘油量也增加。在实际生产时，甘油量的多少不是可以随意增加的，它取决于要生产的醇酸树脂的油度，亦即苯二甲酸酐的用量。当醇解反应完成后，稍稍降温到规定加苯二甲酸酐的温度即可加苯二甲酸酐进行酯化。如果需冷却保存，醇解向逆向进行，甘油或其他醇也将部分析出。可以在醇解温度下，加入些磷酸破坏催化剂，则可使物料成分不变。  \n\n(2）在不加催化剂时醇解反应即使在高温下也进行得很慢，醇解程度很低，所以醇解反应需加入催化剂。常用的醇解催化剂有氧化钙（也可用氢氧化钙、环烷酸钙）、氧化铅（也可用环烷酸铅)、氢氧化锂。钙、铅、锂三种催化剂对油在不同温度下进行的醇解反应的结果表明，催化剂可使醇解速率与深度大为提高，但催化剂的用量应控制在一个限度内，过多的催化剂将会造成酯化工序完成后，过滤困难而降低漆膜的耐候性。钙和铅催化剂都易使树脂发浑。另外，过多地增加催化剂的浓度，并不能增加醇解速率和提高甘油一酸酯的含量，况且铅是一种对人体有害的重金属。CaO在低温与低浓度时效率较高，LiOH是效率最高的催化剂，PbO是三者中效率最后一位。  \n\n在醇酸树脂制造中可能有醇的醚化反应发生，生产过程中的酯化出水量多于理论酯化出水量及甘油所含的游离水的总和。多余的水是由于发生了醚化，醚化主要发生在醇解阶段。  \n\n（3）影响醇解反应的外界因素  \n\n$\\Phi$ 油未精制好，含有脂肪酸等杂质，将消耗催化剂而使醇解缓慢，而且反应程度降低。  \n\n$\\textcircled{2}$ 空气中的氧，生产醇酸树脂时，通常在惰性气体保护下进行，以防止氧化致使油氧化聚合及颜色变深。氧化也不利于醇解反应的进行。  \n\n$\\textcircled{3}$ 不同的油类的碘值不同，碘值大的油类，其醇解深度相对较大。甘油一酸酯的收率较高，是由于甘油在不饱和度高的油内溶解度较大的缘故。  \n\n$\\textcircled{4}$ “过量”甘油对甘油一酸酯生成有影响。在固定的条件下，即固定的催化剂用量和固定的温度下，试验证明，增加过量的甘油并不能提高醇解反应的速率。  \n\n(4）醇解反应程度与醇酸树脂性质的关系用醇解法生产醇酸树脂时要求：第一，油经过醇解反应后可以与苯二甲酸酐成均相反应；第二，醇解反应进行到最大深度，甘油二酸酯、甘油三酸酯和游离甘油尽量减少。因为醇解物的成分对以后酯化制成的醇酸树脂结构与分子量分布极其重要。有人曾用萃取法、色谱分离法等方法试图分析醇解物的成分，但都不够理想。Tawn以硅胶为吸收体，用氯仿与丙酮分级流出法来分离醇解物，取得较好的效果。  \n\n虽然醇解反应达到一定程度后，即可与苯二甲酸酐成均相反应，但醇解深度不同，所制得的醇酸树脂的漆膜性能也是有很大差别的，因此醇解反应必须达到很大的深度。  \n\n在醇解时油和甘油摩尔比相同，催化剂不同，所得的醇解物中甘油一酸酯含量基本相同，但甘油二酸酯、甘油三酸酯的含量则不同，这也会影响醇酸树脂的漆膜性能。  \n\n另外，温度对醇解反应也有影响，200℃反应太慢， $260^{\\circ}\\mathrm{C}$ 有分解和聚合。从生产来看，反应时间越短越好；从技术角度来看，没有副反应而且达到平衡状态最好。在一般条件下工业生产，油和甘油的反应并没有达到平衡状态。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 163,
+        "chunk": "# （5）醇解程度的测定  \n\n$\\Phi$ 醇（甲醇或乙醇）容忍度测定法这是一种粗略的测定法。随着醇解反应的进行，油逐步转变为甘油一酸酯、甘油二酸酯，极性增大。甘油一酸酯越多，与醇的混溶度越大。具体测试步骤是：取 $_{1\\tt g}$ （或1mL）醇解物，在 $25\\mathrm{{C}}$ 以无水甲醇或 $95\\%$ 的乙醇（也可规定其他浓度）滴定至浑浊不消失为终点。滴定速度会影响滴定结果，慢滴有利于得到偏高一些的数值。此法是目前生产中最普遍使用的方法，但此法不能确切地表示甘油一酸酯的含量。  \n\n$\\textcircled{2}$ 发浑点法醇解物在较高的温度溶于乙醇中，温度下降会析出。随醇解物中甘油一酸酯的含量的增加，醇解物在乙醇中的溶解度将增加，其析出的温度将降低，利用这一特性来测量醇解程度。做法是在试管中放5mL乙醇，加 $_{2\\mathrm{mL}}$ 热醇解物，立即将一个 $100^{\\circ}\\mathrm{C}$ 刻度的温度计插入试管中，并揽动醇解物，使其均匀地冷却，注意醇解物溶液变浑时的温度。  \n\n$\\textcircled{3}$ 电导率测定醇解程度在生产醇酸树脂时，还可以采用测定醇解物的电阻变化的方法。在 $80^{\\circ}\\mathrm{C}$ ，亚麻油的电阻率为甘油的6000倍。在醇解过程中由于亚麻油与甘油的反应，甘油部分酯的成分增大，电阻率迅速下降，逐渐达到一个恒定的最低值。我国自行研发的醇解仪在涂料行业推广应用，取得较好的效果。  \n\n一般认为电阻达到最低值，并保持不变时，即醇解反应达到平衡，其实并不如此。开始电阻达到最低时，是因高温甘油溶于油内增大了电导率。以后醇解逐渐进行，成分不断变化。从醇解物可与苯二甲酸酐的融合性试验得到证明，此时并不是醇解反应达到平衡。  \n\n至今在生产时还没有一个科学、快捷的指示醇解物成分的控制方法。所以对醇解反应要综合考虑，如醇解物成分分析、醇酸树脂颜色及发浑问题、生产条件（温度、时间、催化剂、反应物的摩尔比），把试验和生产结合起来，以找出醇解反应平衡点，生产出理想的醇酸树脂。  \n\n(6）季戊四醇醇解问题季戊四醇是制造醇酸树脂的主要多元醇，近年来季戊四醇在醇酸树脂制造中用量已超过甘油的用量。季戊四醇是一个含有四个伯羟基的四元醇，外观是白色结晶，纯季戊四醇的熔点为 $263\\Upsilon$ ，微溶于水。前面已提到工业品季戊四醇含有不同程度的二季戊四醇，平均羟基当量为 $35.5\\%$ ，平均羟基官能度为4.15。杂质以灰分表示，灰分过高会影响醇解反应。国内季戊四醇I型或Ⅱ型标准规定，一级品灰分含量都在0.1%以下，而德国某公司季戊四醇灰分（以 $\\mathbf{CaO}$ 计) $\\leqslant0.002\\%\\sim0.004\\%$ 。季戊四醇含有钙的甲酸盐，少量能引起醇酸树脂浑浊；钠的甲酸盐则易使醇酸树脂颜色变深。钠、钙的硫酸盐会成为小粒沉于釜底。未处理净的硫酸会影响醇解。少量二季戊四醇的存在使季戊四醇的熔点降低、醇解稍快、酯化时黏度上升稍快，对成品性能没有明显的影响。  \n\n季戊四醇作为多元醇制造醇酸树脂时，由于较甘油的官能度大，而且结构对称，制得的醇酸树脂较同类型、相近油度的甘油醇酸树脂结构紧密、黏度较大、干燥较快、漆膜硬度较高，但柔韧性较低，光泽和保光性较好，耐热性、耐黄变性较好，耐化学药品性、耐水性、户外耐久性较好。 me  \n\n用季戊四醇进行醇解反应较甘油复杂。因油的组成中原没有季戊四醇，醇解物是油的脂肪酸重新分配于两种多元醇，其组成状况还不完全清楚。以摩尔比 $1:1$ 的油和季戊四醇为例，反应如下：  \n\n$$\n\\begin{array}{r l}&{\\begin{array}{c c}{0}\\\\ {0}\\\\ {\\mathrm{H}_{1}C-0-C_{-\\mathbf{R}}^{-0}}\\\\ {\\mathrm{H}_{2}}\\end{array}\\overset{\\overset{\\mathrm{O}}{\\longrightarrow}}}&{\\begin{array}{c c}{0}\\\\ {0}\\\\ {\\mathrm{CH}_{2}}\\\\ {0}\\end{array}}&{\\begin{array}{c c}{\\mathrm{H}_{1}C-0\\mathrm{H}}\\\\ {\\mathrm{H}_{1}-C-0-C_{-\\mathbf{R}}^{-0}}\\\\ {0}\\end{array}}&{\\mathrm{H}_{1}C-0\\mathrm{-}\\begin{array}{c c}{0}\\\\ {\\mathrm{CH}_{2}}\\\\ {\\mathrm{CH}_{3}}\\end{array}}\\\\ {\\mathrm{H}_{1}C-0-C_{-\\mathbf{R}}^{-0}}\\\\ {\\mathrm{H}_{2}}\\end{array}}&{\\begin{array}{c c}{\\mathrm{H}_{2}\\mathrm{CH}}\\\\ {\\mathrm{H}_{3}}\\\\ {\\mathrm{OH}}\\end{array}}&{\\begin{array}{r l}{\\mathrm{H}_{1}\\mathrm{C-O-Ch}^{-0}}\\\\ {\\mathrm{CH}_{3}}\\end{array}}&{\\begin{array}{c c}{0}\\\\ {\\mathrm{H}_{2}\\mathrm{CH}}\\\\ {\\mathrm{H}_{3}}\\end{array}}\\\\ {\\begin{array}{r l}{\\mathrm{H}_{1}\\mathrm{C-O-Ch}^{-0}}\\\\ {\\mathrm{CH}_{3}}\\end{array}}&{\\begin{array}{r l}{0}\\\\ {\\mathrm{CH}_{3}}\\end{array}}\\\\ {\\begin{array}{r l}{\\mathrm{H}_{1}\\mathrm{C-O-Ch}^{-0}}\\\\ {\\mathrm{CH}_{3}}\\end{array}}&{\\begin{array}{r l}{0}\\\\ {0}\\\\ {\\mathrm{H}_{3}}\\end{array}}\\end{array}\n$$  \n\n季戊四醇不同于甘油，它是固体而且熔点很高，醇解时要加入催化剂，所需温度也比较高，为 $230{\\sim}250\\%$ 。一般将油与催化剂先混合，在情性气体的保护下升温到醇解温度，在不断地搅拌下将季戊四醇分批加人。也可将季戊四醇全部加人油中，然后搅拌升温。此法可使树脂颜色浅些，可避免在加人季戊四醇时带人空气产生氧化。但必须搅拌良好，否则季戊四醇将粘在釜底炭化。在实验室用反应瓶观察季戊四醇醇解过程可以看到，季戊四醇先形成一个“壳”粘在瓶壁上，有些季戊四醇还升华到反应器上部。在反应进行中，“壳”渐渐熔化，升华的季戊四醇渐渐被回流的油所冲下。此时还不透明，因为有的季戊四醇还悬浮于反应混合物中。未反应的油与所形成的少量的不完全酯也不相混溶，随着反应程度的加深，形成的不完全酯多了，两相混合，季戊四醇也完全溶解，整个体系变得透明，此时称为热透明阶段。冷却仍有固体物析出，反应物变浑。继续保持醇解向深度进展，其醇解进程可通过测醇容忍度与电阻变化来观察。  \n\n试验证明，从测量电导率的变化与甲醇容忍度、未反应的季戊四醇的含量的变化是一致的，但季戊四醇醇解反应因季戊四醇和油的摩尔比不同及季戊四醇规格不同，甚至含不同无机杂质，其电导率的曲线表现都不同。电导率的变化与甲醇容忍度、未反应的季戊四醇的含量，都不能说明醇解反应是否达到平衡。所以醇解反应的控制要结合最终制出的醇酸树脂来确定反应应控制哪个阶段工时最省、产品性能最佳。  \n\n现在国内生产季戊四醇醇酸树脂还是采用测量醇容忍度的方法。  \n\n表2-1-23不同的油度在不同反应时间所达到的容忍度  \n\n\n<html><body><table><tr><td>油度/%</td><td>80</td><td>70</td><td>65</td><td>62</td><td>56</td></tr><tr><td>时间/min</td><td>40</td><td>40</td><td>30</td><td>30</td><td>20</td></tr><tr><td>甲醇容忍度</td><td>0.5</td><td>1</td><td>2</td><td>2.75</td><td>3.35</td></tr></table></body></html>  \n\n$\\Phi$ 说明油度不同其醇解反应与容忍度数值不同，油度短醇解反应快，甲醇容忍度大(表2-1-23)。  \n\n$\\textcircled{2}$ 季戊四醇醇解反应比较复杂，醇容忍度作为观察醇解反应程度的指标仅是相对的，并不能说明其内部变化。醇容忍度值由醇解反应开始时上升，当达到一个较高数值后，又开始下降（比甘油显著)，下降幅度比较大。醇容忍度降低可能是由于季戊四醇发生醚化。长时间的醇解，不但醇容忍度降低，而且在酯化阶段黏度上升也较快（表2-1-24）。  \n\n表2-1-24230℃醇解反应保持期间醇容忍度的变化  \n\n\n<html><body><table><tr><td>时间/min</td><td>10</td><td>30</td><td>60</td><td>90</td><td>120</td><td>180</td><td>240</td></tr><tr><td>容忍度（95%乙醇）</td><td>5.6</td><td>5.6</td><td>5.6</td><td>5.0</td><td>4.6</td><td>4.0</td><td>3.6</td></tr><tr><td>容忍度（20℃）</td><td>2.3</td><td>2.6</td><td>2.3</td><td>2.15</td><td>2.15</td><td>2.15</td><td>2.0</td></tr></table></body></html>\n\n$\\Phi$ 亚麻油·季戊四醇 $\\mathbf{\\sigma}=$ 1 11.3 (摩尔比）.②亚麻油·季戊四醇=11（摩尔比）。  \n\n(7）醇解法生产醇酸树脂，在醇解反应完成后，其酯化阶段和脂肪酸法相同醇解物稍稍降温至 $180\\sim200^{\\circ}\\mathrm{C}$ 即可加入苯酐，再升温至 $200\\sim250\\Upsilon$ 进行酯化反应。酯化反应中控制好反应条件，定时取样，测定酸值与黏度。当酸值与黏度达到规定要求时，降温、兑稀、调整黏度、过滤、包装。  \n\n（8）对醇解反应的新认识经过对季戊四醇醇解过程的观察，有的专家提出醇解反应中的介质效应及不同活性的多元醇的递进醇解的新概念。  \n\n$\\Phi$ 介质效应油脂与多元醇进行醇解反应的产物—多元醇的脂肪酸不完全酯，作为醇解反应的介质，可进而促进醇解反应的进行，这种作用称为介质效应。  \n\n$\\textcircled{2}$ 递进醇解由于不同多元醇的结构、官能度、分子极性、分子量等差别，其醇解的难易程度不一。如几种多元醇一起参与醇解，易醇解的多元醇先醇解，其形成的不完全酯为以后的醇解反应提供了良好的介质，从而使整个醇解反应得以迅速完成，称为递进醇解。如一些短油度醇酸树脂，以容易醇解的一缩二乙二醇（DBE)、三羟甲基丙烷（TMP）先行与甘油、季戊四醇构成递进醇解，大大加快了整个醇解反应的进行。  \n\n高羟值短油度或超短油度的醇酸树脂在醇解阶段节制多元醇的投入量，安排一部分多元醇直接参与酯化，有利于节能增效并提高树脂的质量。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 164,
+        "chunk": "# 3.脂肪酸-油法制醇酸树脂  \n\n将脂肪酸、油、多元醇、多元酸（苯二甲酸酐）一同加入反应釜中，升温至 $210\\sim$ $280^{\\circ}\\mathrm{C}$ 保持酯化至达到规定要求。此法制得的醇酸树脂较醇解法制得的面干快而干透慢。而油的用量必须有一个正确的比例，否则将产生胶粒。有人认为，在有油脂（简记为O）又有脂肪酸（简记为F）的 $\\mathrm{O/F}$ 体系的醇解， $\\mathrm{{O/F}}$ 体系的醇解的核心问题是形成以F的单甘油酯为代表的不完全多元醇酯体系。 $\\mathrm{O}/\\mathrm{F}$ 体系的醇解，必然是油的酯交换和脂肪酸的酯化两个反应的综合。脂肪酸的酯化形成的单甘油酯，又为油和甘油相溶创造了环境条件，促进油的醇解。试验表明，在以不同比例的亚麻油/亚麻油酸混合物与甘油在不同的催化条件下，进行醇解反应，把油的酯交换和脂肪酸的酯化结合起来，才能更好地完成O/F体系的醇解。$z_{\\mathrm{nO}}$ 不是酯交换的良好催化剂，但对酯化有良好催化作用；LiOH是典型的酯交换催化剂，对酯化没有明显的作用。对 $\\mathrm{{_{O/F}}}$ 体系来说， $z_{\\mathrm{nO}}$ 和LiOH的配合，才能取得最佳效果。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 165,
+        "chunk": "# （三）醇酸树脂的生产工艺",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 166,
+        "chunk": "# 1.醇酸树脂的酯化工艺  \n\n脂肪酸法或醇解法生产醇酸树脂酯化工艺上都是采用溶剂法脱水。因为醇酸树脂最基本的化学反应是酯化反应，反应产生的水必须及时除去，酯化反应才得以深度进行。熔融法靠不断通入情性气体以帮助搅拌，排出酯化反应产生的水汽和防止反应物氧化。而溶剂法是利用有机溶剂作为共沸液体带出水帮助酯化。  \n\nE酯化阶段加人反应物量的 $3\\%\\sim5\\%$ 的溶剂（主要是二甲苯)。脂肪酸法制醇酸树脂时，在投人多元酸、多元醇、脂肪酸的同时加入溶剂，升温进行酯化，共沸脱水。醇解法生产醇酸树脂是在完成醇解反应加完苯酐后，加回流二甲苯。溶剂法反应温度比较容易控制，通过增减溶剂量来进行调节（表2-1-25）。  \n\n表2-1-25用量与沸点的关系  \n\n\n<html><body><table><tr><td>溶剂</td><td>用量/%</td><td>沸点/℃</td></tr><tr><td>二甲苯</td><td>3</td><td>251~260</td></tr><tr><td>二甲苯</td><td>4</td><td>246~251</td></tr><tr><td>二甲苯</td><td>7</td><td>204~210</td></tr></table></body></html>  \n\n溶剂法生产醇酸树脂，在反应釜上装有蒸汽加热的分馏柱，柱内装有填料。这个设备有利于含有低沸点成分的配方，如含有苯甲酸（沸点 $249\\Upsilon$ 、乙二醇（沸点 $^{198^{*}\\mathrm{C})}$ ，如果没装分馏柱则损失太大。  \n\n另一个优点是有利于溶剂和水的分离，加快酯化反应的进行。分馏柱用蒸汽加热，可使酯化生成的水蒸出，而其他醇和酸、部分溶剂回流回收。  \n\n注意经冷凝器回到反应釜内的二甲苯温度不可过高，这是因为在较高的温度下，水在二甲苯中的溶解度将增大（表2-1-26)。  \n\n表2-1-26水在二甲苯中的溶解度  \n\n\n<html><body><table><tr><td>温度/℃</td><td>25</td><td>40</td><td>55</td><td>70</td></tr><tr><td>溶解度/(g/100mL)0.018</td><td></td><td>0.06</td><td>0.090</td><td>0.118</td></tr></table></body></html>  \n\n表2-1-27苯二甲酸酐在二甲苯中的溶解度  \n\n\n<html><body><table><tr><td>温度/℃</td><td>10</td><td>25</td><td>40</td><td>55</td><td>70</td></tr><tr><td>溶解度/(g/100mL)</td><td></td><td></td><td></td><td></td><td>0.881.502.604.255.85</td></tr></table></body></html>  \n\n如果带回反应釜的水增多，不利于酯化反应的进行。特别是在酯化反应的后期出水很少，二甲苯带回的水将延长反应时间。反之，低温会使苯酐在二甲苯中的溶解度下降，有造成冷凝器被堵塞的危险(表2-1-27)。返回反应釜的二甲苯应控制在 $25\\sim40^{\\circ}C$ 。反应生成的水，应收集计量，以便了解酯化反应进行程度。  \n\n醇酸树脂的酯化工艺的改进：传统的酯化流程为蒸出管→冷凝器→分水器→反应釜。如采用改进工艺则由填料塔→回流冷凝器→分水器→填料塔 $\\rightarrow$ 反应釜，最后回到反应釜的二甲苯温度为 $110{\\sim}125\\Upsilon$ ，高于二甲苯-水的共沸温度 $92\\%$ 。由于回到反应釜的二甲苯温度高，含水少，甚至不含水，这样既节约能源，又缩短脱水时间。按试验装置测算，整个酯化过程节柴油率为 $47.3\\%$ ，整个醇解和酯化流程节柴油率为 $23.6\\%$ ，每吨醇酸树脂节柴油14. $2\\mathrm{ls}_{\\mathrm{g}}$ 。虽然建填料塔一次性投入较大，但是节能效果明显，还是值得推广的。  \n\n溶剂法与熔融法相比有以下优点。  \n\n$\\Phi$ 树脂颜色较浅且比较均匀。  \n$\\textcircled{2}$ 收率较高，因无苯二甲酸和多元醇的损失，多元醇、多元酸的比例保持基本不变。  \n$\\textcircled{3}$ 酯化温度比较低，酯化反应周期比较短。  \n$\\textcircled{4}$ 温度容易控制。  \n$\\textcircled{5}$ 反应釜容易清洗。  \n熔融法已基本不用，仅个别醇酸树脂如间苯二甲酸醇酸树脂还采用熔融法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 167,
+        "chunk": "# 2.醇酸树脂的生产设备  \n\n醇酸树脂的反应温度通常为 $200\\sim250^{\\circ}\\mathrm{C}$ ，在涂料行业中，醇酸树脂属高温合成树脂。醇酸树脂的生产设施中最重要的设备是反应釜。我国从20世纪80年代从国外引进多套 $6\\sim$ $12\\mathrm{m^{3}}$ 大型醇酸树脂反应釜及 $60{\\sim}200\\ 251{\\sim}837J/\\mathbf{h}$ 热媒锅炉。现在我国 $12{\\mathrm{m}}^{3}$ 以上大型醇酸树脂反应釜已很普遍，并已国产化，最大的反应釜甚至达到 $50\\mathrm{m}^{3}$ 。一些专业醇酸树脂生产厂家，采用先进的DCS集散自动控制系统，醇酸树脂生产的自动化程度大大提高。反应釜上配备搅拌器、通入情性气体的装置、分馏柱、冷凝器、油水分离器、温度计和记录仪、自动取样器、人孔、液体原料加人管路、取样装置、打沫器、真空装置等。  \n\n随着醇酸树脂反应釜大型化，其加热方式都是采用热导油加热。大型化反应釜和热导油加热有助于提高热能利用率及醇酸树脂的质量。传统的直接火加热，热效率在 $40\\%$ 左右，引进热媒锅炉热效率达到 $80\\%$ 以上。直接火加热每吨醇酸树脂耗柴油平均 $60\\mathbf{kg}$ ，热媒锅炉加热每吨醇酸树脂耗柴油平均 $40\\mathbf{kg}$ ，节约1/3。在反应釜上有热导油进出口。热导油通过安在反应釜壁上“半管”加热，而且加热分为 $2{\\sim}3$ 个独立的区域，既可自控，又可冷却，安全而又无过热问题，使物料受热均匀，颜色较浅。以揽拌器搅拌使物料充分混合均匀，对于溶剂法生产醇酸树脂回流二甲苯带水更为重要。揽拌叶片的直径为反应釜直径的 $35\\%\\sim$ $60\\%$ ，透平叶片线速度 $185{\\sim}250\\mathrm{m/min},$  \n\n(1）分馏柱以 $4\\mathrm{m}^{3}$ 反应釜为例，分馏柱为 $\\mathsf{31m m}\\times2\\mathsf{100m m}$ 顶部有加热-冷却盘管，盘管是由 $1.27\\mathrm{{cm}\\ (1/2\\mathrm{{in})}}$ 不锈钢管制成的双环形，表面积为 $\\scriptstyle1\\div8m^{2}$ ，自动控制供汽或水。柱内填充 $1.905\\mathrm{cm}(3/4\\mathrm{in})$ 拉希格环（Rashig)，填充高度在 $\\mathbf{1m}$ 左右。反应开始时出水较多，分馏柱顶部温度保持在 $100{\\sim}105\\mathrm{\\textperthousand}$ 以减少损失，特别是减少低沸点物的损失。此时二甲苯回流量并不大，约 $2.5{\\sim}3.5\\mathrm{kg/min}$ ? $\\mathrm{4m^{3}}$ 反应釜)。釜温可以增减二甲苯量。在反应接近完成时出水量大减，回流二甲苯量可增至 $11{\\sim}14\\mathrm{kg/min}$ C $\\mathrm{4m^{3}}$ 反应釜)，分馏柱顶部温度可提高至 $125\\mathrm{{C}}$ 。蒸馏冷凝器的温度也要降低以利于最后分水。  \n\n(2)蒸馏冷凝器为列管式，管外通水冷却， $4{\\mathrm{m}}^{3}$ 容积的反应釜冷却面积至少为 $18\\mathrm m^{2}$ 。  \n\n(3）油水分离器溶剂法生产醇酸树脂需要油水分离器。由冷凝器凝缩并冷却的水和溶剂，流入分离器中，分成两层，上层为溶剂，溢回反应釜中，下层为水，也自动溢流收集到接收器中。在溶剂回到反应釜的管路上，装有流量计，以测量回流速度。在反应釜上还有温度计口、取样口、回流二甲苯入口等。  \n\n(4）稀释罐其容积至少为反应釜的2倍。装有透平式搅拌，稀释时如有溶剂蒸气，可由冷凝器凝缩回来。罐内有盘管加热或冷却。稀释罐应装有重衡传感器，直接读出罐内物料的质量。稀释罐区必须具备防火安全措施。  \n\n(5）过滤净化设备过滤设备种类很多，常用的有水平或立式平板过滤器。可将硅藻土（助滤剂）约 $0.2\\%$ 分散于树脂内或少量树脂内，在过滤时在滤布（纸）上形成“滤衣”，既可助滤，又防止滤孔堵塞降低过滤速率。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 168,
+        "chunk": "# 3.生产工艺举例  \n\n溶剂法生产醇酸树脂如下。  \n\n【例】豆油醇酸树脂  \n\n$62\\%$ 油度豆油季戊四醇醇酸树脂见表2-1-28。  \n\n表2-1-2862%油度豆油季戊四醇醇酸树脂   \n\n\n<html><body><table><tr><td>配方</td><td>投料量/kg</td><td>投料比/%</td><td>当量值</td><td>eA</td><td>eB</td><td>官能度</td><td>m</td></tr><tr><td>豆油（双漂）</td><td>1250.0</td><td>57.42</td><td>293</td><td>4.26</td><td></td><td>1</td><td>4.26</td></tr><tr><td>季戊四醇（工业品）</td><td>327.0</td><td>15.02</td><td>35.5</td><td></td><td>9.21</td><td>4</td><td>2.30</td></tr><tr><td>苯二酸酐</td><td>600.0</td><td>27.56</td><td>74.0</td><td>8.11</td><td></td><td>2</td><td>4.05</td></tr><tr><td>甘油(油内)</td><td></td><td></td><td></td><td></td><td>4.26</td><td>3</td><td>1.42</td></tr><tr><td>合计</td><td>2177.0</td><td>100.00</td><td></td><td>12.37</td><td>13.47</td><td></td><td>12.02</td></tr></table></body></html>  \n\n氧化铅： $0.52\\mathrm{kg}$  \n\n多元醇过量 $R{=}\\frac{13.47}{12.37}{=}1.089\\qquadr{=}\\frac{9.21}{8.11}{=}1.136$  \n\n$$\nK=\\frac{m_{0}}{e_{\\mathsf{A}}}=\\frac{12.03}{12.37}=0.973\n$$  \n\n油度：62%  \n规格要求：  \n黏度(25℃，加氏管)/s酸值/(mgKOH/g)  \n生产工艺如下。  \n\n7\\~9 不挥发分/% ≤15  \n\n$\\Phi$ 将豆油加人反应釜中，升温，通人 $\\mathrm{CO}_{2}$ ，搅拌，在 $45\\mathrm{\\sim}55\\mathrm{min}$ 内升温到 $120\\Upsilon$ ，停止搅拌，加人氧化铅，开始搅拌。  \n\n②升温到220℃分批加入季戊四醇，再继续升温到240℃，保温醇解，至取样测定95%乙醇容忍度（25℃）为5作为醇解终点。在醇解时准备好油水分离器中垫底二甲苯及回流二甲苯。  \n\n③降温到220℃加人苯二甲酸酐，加完停止通人CO2，立即加入总加料量5%的二甲苯（约 $108\\mathbf{kg})$ 。  \n\n④继续升温到200C保温1h，升温到220℃保温2h，测酸值、黏度（黏度测定：样品 $:200^{\\#}$ 油漆溶剂油 $=10:7.3$ ，以加氏管测定)。接近终点时每隔0.5h测一次。当黏度达到7s，酸值达到 $18\\mathrm{mgKOH/g}$ 以下时，立即停止加热，抽入或放人稀释罐进行冷却。当温度降到 $150^{\\circ}\\mathrm{C}$ 以下，加人 $200^{\\sharp}$ 油漆溶剂油 $1567\\mathbf{kg}$ 溶解成醇酸树脂溶液，再冷却至 $60\\Upsilon$ 以下过滤。  \n\n【例】椰子油醇酸树脂 短油度椰子油醇酸树脂见表2-1-29。  \n\n表2-1-29短油度椰子油醇酸树脂   \n\n\n<html><body><table><tr><td>配方</td><td>投料量/kg</td><td>投料比/%</td><td>当量值</td><td>A</td><td>B</td><td>官能度</td><td>mo</td></tr><tr><td>椰子油（单源)</td><td>648</td><td>36.00</td><td>218</td><td>2.97</td><td></td><td>1</td><td>2.97</td></tr><tr><td>甘油，95%(第一份)</td><td>304</td><td>16.89</td><td>30.7</td><td></td><td>9.41</td><td>3</td><td>3.14</td></tr><tr><td>甘油，95%（第二份）</td><td>98</td><td>5.44</td><td>30.7</td><td></td><td>3.03</td><td>3</td><td>1.01</td></tr><tr><td>苯二甲酸酐</td><td>750</td><td>41.67</td><td>74</td><td>10.13</td><td></td><td>2</td><td>5.06</td></tr><tr><td>甘油(油内)</td><td></td><td></td><td></td><td></td><td>2.97</td><td>3</td><td>0.99</td></tr><tr><td>合计</td><td>1800</td><td>100.00</td><td></td><td>13.10</td><td>15.41</td><td></td><td>13.17</td></tr></table></body></html>  \n\n氧化铅： $0.13\\mathrm{kg}$ 油度： $38\\%$  \n\n$$\nR={\\frac{15.41}{13.10}}=1.176\\qquadr={\\frac{12.44}{10.13}}=1.228\\qquadK={\\frac{m_{0}}{e_{\\mathrm{A}}}}={\\frac{13.17}{13.10}}=1.005\n$$  \n\n规格要求：黏度（25℃，加氏管）/s酸值/(mgKOH/g)生产工艺如下。  \n\n13\\~25 不挥发分/% ≤17  \n\n$\\textcircled{1}$ 先将椰子油、第一份甘油加入反应釜中，升温，同时通人 $\\mathrm{CO}_{2}$ ，到 $120^{\\circ}\\mathrm{C}$ 时停止搅拌加人氧化铅，继续揽拌。  \n\n$\\textcircled{2}$ 在2h内升温到 $230^{\\circ}\\mathrm{C}$ ，保持醇解至无水甲醇容忍度 $(25^{\\circ}\\mathrm{C}$ ）达到5为醇解终点。  \n\n$\\textcircled{3}$ 降温到 $220\\Upsilon$ ，在 $20\\mathrm{{min}}$ 内加完苯二甲酸酐。  \n\n$\\textcircled{4}$ 停止通入 $\\mathrm{CO}_{2}$ ，从油水分离器加人总投料量 $6\\%$ 的二甲苯（ $_{\\mathrm{108kg)}}$ ，升温。  \n\n$\\textcircled{5}$ 在2h内升温到 $195\\sim200^{\\circ}\\mathrm{C}$ ，保持1h，加人第二份甘油，继续酯化  \n\n$\\textcircled{6}$ 保持1h后，开始测酸值、黏度（样品：二甲苯 $=12:6.9$ ，在 $25\\mathrm{{T}}$ 以加氏管测定）。当黏度达到10s时停止加热，立即抽出或放出至稀释罐，冷却至 $110^{\\circ}\\mathrm{C}$ 以下，加人甲苯$804\\mathbf{kg}$ ，溶解成醇酸树脂溶液，再冷却过滤。  \n\n【例】61%油度豆油脂肪酸树脂  \n\n大多数醇酸树脂是以苯酐生产的，而只要是醇酸树脂就有一定的酸值。由于苯酐的第二个羧基，即半酯化开环后释放出来的一COOH，其反应活性比第一个羧基低，也比脂肪酸、苯甲酸低，后两者空间位阻都小于苯酐的第二个羧基，只是松香的空间位阻大于苯酐的第二个羧基，所以一般来说，醇酸树脂的酸值是苯酐的第二个羧基未完全反应的表现。也就是说，那一部分未完全反应的苯酐，只起到一元酸的作用。在计算设计终点 $A V\\geqslant0$ 的醇酸树脂配方时，应把苯酐分为一元酸和二元酸两部分来处理。以 $\\kappa_{\\mathrm{*}}$ 代表理论 $\\kappa$ 值，以 $K_{\\mathfrak{p}}$ 代表实际醇酸常数。  \n\n试以61%油度豆油脂肪酸树脂为例，做配方分析。  \n\n产品设计固体分： $50\\%$ ；固体树脂酸值： $12\\mathrm{mgKOH/g}$ ? $50\\%$ 的液体树脂为 $24m g$ $\\operatorname{KOH}/\\mathbf{g})$ ，只起到一元酸作用的苯酐数量近似计算值为： $(24/56100)\\times96.6\\times148=$ 6.12份。  \n\n61%油度豆油脂肪酸树脂见表2-1-30。  \n\n表2-1-3061%油度豆油脂肪酸树脂  \n\n\n<html><body><table><tr><td>配方</td><td>质量分数/%</td><td>mo</td><td>eA</td><td></td></tr><tr><td>豆油</td><td>58.24</td><td>G0.066</td><td></td><td>0.199</td></tr><tr><td>季戊四醇</td><td>13.82</td><td>F0.199 0.094</td><td>0.199</td><td>0.390</td></tr><tr><td>苯酐</td><td></td><td></td><td></td><td></td></tr><tr><td>I二元酸</td><td>21.82</td><td>0.147</td><td>0.295</td><td></td></tr><tr><td>Ⅱ一元酸</td><td>6.12</td><td>0.41</td><td>0.41</td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td>合计</td><td>100.00</td><td>0.548</td><td>0.535</td><td>0.589</td></tr></table></body></html>  \n\n脱水量： $0.147\\times18{=}2.65$ -理论树脂产量：97.35计算反应终点(固体树脂)：  \n\n$$\nA V=\\frac{0.041\\times56100}{97.35}=23.8\\qquadK_{\\mathrm{p}}=\\frac{0.548}{0.535}=1.024\n$$  \n\n$$\nR{=}1.099\\qquadr{=}1.158\n$$  \n\n习惯计算方法：  \n\n脱水量 $0.189\\times18=3.40$ ，树脂理论得量96.60。  \n\n$$\n\\begin{array}{c}{{K_{\\mathrm{t}}{=}\\frac{0.548}{0.577}{=}0.950}}\\\\ {{{}}}\\\\ {{R{=}1.020~r{=}1.029}}\\\\ {{{}}}\\\\ {{K_{\\mathrm{p}}{>}K_{\\mathrm{t}}}}\\end{array}\n$$  \n\n$K_{\\mathrm{t}}=0.950$ ，似乎工艺不安全，但由于终点 $\\ A V$ 为 $24$ ， $K_{\\circ}=1.024$ ，所以工艺是安全的，按照这种方法，配方参数 $R,\\ r$ 和羟基值都有提高。  \n\n如果配方设计中有较多的松香，树脂最后的酸值可认为是未反应的松香，应把松香分为反应和未反应两部分计算。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 169,
+        "chunk": "# 4.醇酸树脂生产的质量控制  \n\n(1）酸值与黏度酸值与黏度是醇酸树脂生产中质量控制的主要技术指标。在生产过程中不断、定期地取样测定酸值与黏度，它反映反应釜内反应进行的情况。  \n\n$\\Phi$ 酸值是指中和1g试样所需的氢氧化钾的毫克数，标志着酯化反应的速率和程度。制造醇酸树脂希望分子量高，酸值低，即酯化反应要完全。控制酸值要比凝胶化时高 $2\\sim$ $5\\mathrm{{mgKOH/g}}$ ，这样的树脂（常温、自干型）制得的漆膜性能与稳定性都比较好。大多数醇酸树脂的酸值都控制在 $10\\mathrm{mgKOH/g}$ 以下，对不同的醇酸树脂另做规定。  \n\n②黏度表示醇酸树脂的缩聚程度与分子量的增长。现场测定的方法是将固体树脂溶于一定数量的指定溶剂，在规定的温度下以加氏管测定。加氏管有两种表示方法：一种是与装有标准黏度液体的并行比较，以加氏管规定的英文字母表示黏度档次；另一种用时间s表示黏度。标准的加氏管可以和绝对黏度对应换算。  \n\n$\\textcircled{3}$ 酸值-黏度关系以黏度的对数值和酸值对反应时间作图2-1-2，这个曲线可以直观地反映反应进行情况。从实验室制得的树脂的反应曲线与在生产时制得的反应曲线两者比较，可以看出实验室与大型生产的差别。同一配方、相同工艺、相同原料生产时所得的曲线应是一致的。在理论上酸值联系着数均分子量，黏度联系着重均分子量。实际上每一个配方与特定工艺都有其自身的变化曲线，而不是一个标准的变化曲线。  \n\n![](images/935a3ce3b2ca2fa7bfd235470de57fc0a71c6a5706746e23ca0eef679b1dab55.jpg)  \n图2-1-2酸值、黏度与生产时间的关系  \n\n另外，将酸值对黏度的倒数作图可得直线（图2-1-3)。由直线的走向可观察配方、工艺是否合理。延长直线可以外推到凝胶时的酸值，所以是生产控制的有力工具。对于油度小于45%的配方来说，这种推测方法更有用。因为短油度者反应快，现场测定酸值、黏度需时较  \n\n![](images/e3b0eb91972104d160689c2f843fbfd9e5cfa2e07378db6e9d44dbaceb18804e.jpg)  \n图2-1-3酸值对黏度的倒数作图外推凝胶化时酸值1—反应不完全；2-设计适当的配方；3一不适用的高分子结构  \n\n长，不易控制。  \n\n(2）固化时间有的醇酸树脂反应过快，测酸值、黏度法来不及控制，则采取测固化时间法。就是将一块特制钢板加热到 $200^{\\circ}\\mathrm{C}$ ，滴一滴树脂于钢板上，记录树脂胶化时间。固化时间在10s左右的树脂是不稳定的，生产时终点控制一般不要小于 $10\\mathrm{s}$ 身  \n\n(3）颜色醇酸树脂要求颜色很浅，而很多厂家做不到，原因是原料不净、设备材料不良、操作带入杂质、空气氧化等诸多因素的影响。树脂颜色深浅将影响漆的色泽，特别是白色、浅色漆；有的还将影响漆膜的耐久性。  \n\n(4）化学分析在实验室做醇酸树脂的分析一般包括分离与分析。测定醇酸树脂所含游离酸、羟基含量、不皂化物、多元酸种类、多元醇种类、脂肪酸种类和是否有其他改性剂如松香、苯乙烯、丙烯酸类、酚醛树脂、氨基树脂等。先以红外吸收光谱定性地进行测定，可大量简化以后的分析工作。特别是可以先鉴定出是否为苯二甲酸或其他多元酸所制得的醇酸树脂，是否含有酚醛、氨基、苯乙烯等改性剂。分离方法为将醇酸树脂以乙醇、氢氧化钾皂化，这样可将多元酸作为钾盐分离出来、滤出。脂肪酸在滤液中，稀释、酸化，以溶剂（石油醚或苯）萃取出来。多元醇存留在残留溶液中，分析方法可用经典的容量法、重量法、色谱法等。采用纸色谱、薄层色谱、气相色谱等来分离、分析，可大大简化分析工作。 小  \n\n现在醇酸树脂是一种原料，也是一种商品，对醇酸树脂技术指标做快速分析是很必要的。已有一种醇酸树脂的植物油的成分快速分析法，采用PEG20M毛细管柱色谱质谱联用仪，对醇酸树脂水解甲酯化产物进行色谱和质谱分析，结果表明，植物油脂肪酸同分异构体得到较好的快速分离。总离子流图的分析时间在 $10\\mathrm{{min}}$ 内，可用于醇酸树脂的工业快速分析。例如，对大豆油醇酸树脂水解甲酯化产物中脂肪酸峰面积与大豆油组分文献值的对比(表2-1-31)。  \n\n表2-1-31大豆油醇酸树脂水解甲酯化产物中脂肪酸峰面积与大豆油组分文献值的对比单位：%  \n\n\n<html><body><table><tr><td>组分</td><td>棕榈酸</td><td>硬脂酸</td><td>油酸</td><td>亚油酸</td><td>亚麻油酸</td><td>花生酸</td></tr><tr><td>大豆油</td><td>11</td><td>4</td><td>25</td><td>51</td><td>9</td><td>量中</td></tr><tr><td>水解产物</td><td>26.99</td><td>10.34</td><td>23.06</td><td>33.56</td><td>4.43</td><td>0.96</td></tr></table></body></html>  \n\n(5）醇酸树脂的规格在醇酸树脂生产中，主要控制酸值、黏度及颜色，用同一配方、相同的原料、相同的生产条件所生产的醇酸树脂都应控制到相同的指标，以保持产品的稳定性。但醇酸树脂的规格不限于生产控制指标，尤其是醇酸树脂已经商品化，更应向用户提供完整的产品规格。商品醇酸树脂的规格包括：牌号（或型号)、油品、油度、苯二甲酸酐、多元醇、颜色、酸值、黏度、固体分及兑稀溶剂名称等规格。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 170,
+        "chunk": "# 六、醇酸树脂的应用  \n\n醇酸树脂是涂料工业用途最广的合成树脂之一。醇酸树脂作为成膜物质可以制成清漆、色漆，既可制成通用性漆，也可以生产工业专用漆。按照醇酸树脂的油品和油度的不同，可概括为三种用途。  \n\n$\\Phi$ 干性油醇酸树脂，在空气中自动氧化成膜，可制成各种清漆、色漆及各种类型涂料，成为涂料工业中很重要的一大类涂料。  \n\n$\\textcircled{2}$ 和氨基树脂配合，制成氨基醇酸烘漆；与脲醛树脂合用，以酸催化做家具漆；也可和多异氰酸酯一起，制成双组分聚氨酯涂料。  \n\n$\\textcircled{3}$ 醇酸树脂作为增塑剂与热塑性树脂合用，如硝基漆、乙基纤维素、氯化橡胶、过氯乙烯树脂等合用，以改进挥发性涂料的性能。",
+        "category": " Introduction"
+    },
+    {
+        "id": 171,
+        "chunk": "# 1.醇酸树脂的种类及用途  \n\n(1）干性油短油度醇酸树脂短油度醇酸树脂，含油 $30\\%\\sim40\\%$ ，含苯二甲酸酐大于 $35\\%$ 。所用的油通常有亚麻油、桐油（部分）、豆油、梓油、脱水麻油等干性油或它们的脂肪酸。这类醇酸树脂黏度比较高，需用芳香烃溶剂如二甲苯溶解，制成漆后，宜喷涂或漫涂；既可自动氧化干燥，也可烘干成膜；漆膜有较好的光泽、较高的硬度、保光性和保色性及户外耐久性较好。可用于汽车、玩具、机器零件等金属制品。既可做底漆，也可做面漆。还可与氨基树脂混合制成烘漆；也可与脲醛树脂合用，以酸为催化剂做成自干漆。  \n\n(2）干性中油度醇酸树脂干性中油度醇酸树脂，含油 $46\\%\\sim55\\%$ ，含苯二甲酸酐$30\\%\\approx35\\%$ ，是最常用的一类醇酸树脂。由干性油、甘油（或季戊四醇)、苯二甲酸酐制成。由季戊四醇取代部分或全部甘油制得的醇酸树脂，结构紧密而且官能度高，油度稍长，比甘油制得的漆膜干率与耐久性都好。62%左右油度的季戊四醇醇酸树脂与 $55\\%$ 左右油度的甘油醇酸树脂可相互代用。  \n\n用干性油中油度醇酸树脂制出的漆可以刷涂、喷涂或辊涂。漆膜干燥快，有很好的光泽、柔韧性和耐候性。可以制成自干或烘干的清漆、底漆、磁漆、腻子等。施工于金属、木材及其他材质上，如汽车修补漆、卡车漆、家具漆、农机漆及水线以上的船舶漆等其他机械或建筑用漆。  \n\n(3）不干性油醇酸树脂不干性油醇酸树脂用椰子油、麻油、壬酸、月桂酸、叔碳酸以及其他饱和脂肪酸和中、低碳合成脂肪酸等制成。不论短油度不干性油醇酸树脂，还是中油度麻油醇酸树脂，由于极性较大，必须用芳香烃溶剂。  \n\n$\\textcircled{1}$ 用于硝基漆的不干性油醇酸树脂中、短油度的不干性油醇酸树脂用于硝基漆作增  \n\n塑剂。其作用如下。  \n\na.增加漆膜的附着力。因为硝基纤维素本身的附着力很差，醇酸树脂比增塑剂更能增加硝基漆的附着力，而漆膜的硬度降低并不明显，且加量大可达到与硝基纤维素相同的量。b.提高硝基漆的光泽。硝基纤维素单独制漆，光泽很低，如加入醇酸树脂可以大幅度提高硝基漆的光泽。c.增加硝基漆的丰满度。d.加入醇酸树脂可以提高硝基漆的固体分，且不增加黏度，从而也增加一次漆膜的厚度。e.防止漆膜收缩。因为硝基纤维素制得的漆膜随溶剂的挥发，漆膜将收缩，若加入醇酸树脂可防止硝基漆漆膜的收缩。  \n\nf.提高硝基漆的耐候性。用醇酸树脂取代松香酯，从而大大提高了硝基漆的耐候性。  \n\n用椰子油、麻油、壬酸、月桂酸所制得的短油度甘油或季戊四醇醇酸树脂，都可用于硝基漆，但椰子油季戊四醇醇酸树脂以较长油度而达到与甘油者相同的硬度，而前者的黏度低，使硝基漆具有较高的固体分、较好的耐水性、耐醇性、抛光性及柔韧性。其他不干性油的季戊四醇醇酸树脂也具备这些优点。  \n\n$\\textcircled{2}$ 用于氨基醇酸漆的不干性油醇酸树脂醇酸树脂上的游离羟基与羧基可与氨基分子上的羟基、烷氧基起缩合反应。少量的氨基树脂（ $3\\%$ 左右）可改善自干醇酸树脂漆的起皱性，较多的氨基树脂（如为醇酸树脂的 $1/5{\\sim}1/2)$ ，则需烘干。氨基树脂起交联固化作用，而醇酸树脂则起提供缩聚基团和增塑、增加附着力的作用。氨基醇酸漆比醇酸树脂漆有更好的硬度、耐碱性、户外耐久性。  \n\n![](images/f5dd895baddf18735a0b9f271f869f176a2eb1a84a5e1a126e75a59ea785c131.jpg)  \n\n短油度的不干性油醇酸树脂-氨基树脂烘漆可得到硬而坚韧的漆膜，具有良好的保光性、保色性、户外耐久性和一定的抗潮性、耐溶剂性与耐中等强度的酸、碱溶液的能力。中油度的不干性油醇酸树脂硬度相对低一些，但有相对较好的柔韧性和力学性能。短油度醇酸-氨基漆主要用于汽车、电冰箱、金属制品、玩具等，这类用途要求漆膜力学性能良好，保光、保色、耐污染、耐油、耐洗涤剂，长期使用而能保持漆膜完好。目前醇酸-氨基漆是主要的汽车面漆品种之一。该漆的醇酸树脂部分为短油度饱和脂肪酸（油）醇酸树脂或无油醇酸树脂。醇酸树脂的类型和质量对醇酸-氨基漆的性能影响很大，两者的极性、官能度要相适应，才会有良好的融合性和共缩合性。如果含有未反应的苯二甲酸酐或酸值过高，将使漆膜发暗。  \n\n(4）长油度醇酸树脂长油度醇酸树脂，油度为 $60\\%\\sim70\\%$ ，苯二甲酸酐含量20%～$30\\%$ 。长油度醇酸树脂的漆膜有好的干燥性能，漆膜有弹性，有良好的光泽、保色性与耐候性，但硬度、抗磨损性略比中油度者差。长油度醇酸树脂的突出优点是易于涂刷施工，流平性好，因此可用于钢结构和户内外建筑涂料、船舶涂料、氯化橡胶涂料，也可用以增强油基树脂漆和乳胶漆。 五营  \n\n(5）极长油度醇酸树脂极长油度醇酸树脂，油度大于 $70\\%$ ，苯二甲酸酐含量小于$20\\%$ 。溶于脂肪烃溶剂，可与油基树脂漆混合。此种树脂干燥慢，但有良好的涂刷性与耐候性，主要用于油墨，也可作调色基料，户外房屋用漆或增强乳胶漆。  \n\n![](images/c060f355664a9d9a6c7f9a87ebac6d0ff4976429a92a4fed4424d0323db76717.jpg)  \n图2-1-4PVC与附着力的关系 150%；2—55%；3—60%；4—66%  \n\n（6）醇酸树脂色漆的颜料体积浓度（PVC）及对漆膜力学性能的影响不同油度的醇酸树脂分别制成的清漆，干燥时间随油度的降低而缩短，附着力、拉伸强度等力学性能则随油度的降低而增强。不同油度的醇酸树脂分别以不同PVC $(0\\sim60\\%$ ）制成色漆，在碳钢板上制得厚度为$35\\sim40\\mu\\mathrm{m}$ 漆膜，干燥7天，测定漆膜在碳钢板上的附着力，则PVC与附着力的关系如图2-1-4所示。  \n\n由图2-1-4可以看出，油度的下降。聚合物分子上的极性基团如羟基、羧基和酯基增加，这些基团提供了漆膜的附着力。油度增加，漆膜在干燥过程中交联密度增加，导致内应力增加和漆膜收缩，因而附着力下降。加人颜料可以提高附着力。树脂不同，达到某一颜料体积浓度时，附着力达到最高值，越过此点，颜料再多加，则附着力下降。上述 $66\\%$ 。 $60\\%$ $55\\%$ ， $50\\%$ 油度的四种醇酸树脂和氧化铁红制成的色漆，其最大附着力及CPVC见表2-1-32。  \n\n表2-1-32四种色漆最大附着力及CPVC   \n\n\n<html><body><table><tr><td>油度/%</td><td>66</td><td>60</td><td>55</td><td>50</td></tr><tr><td>CPVC/%</td><td>45</td><td>38</td><td>30</td><td>25</td></tr><tr><td>附着力（最大值）/MPa</td><td>24.51</td><td>30.40</td><td>32.36</td><td>35.30</td></tr></table></body></html>  \n\n高于或低于CPVC则附着力急剧下降，但此CPVC值低于按吸“醇酸树脂”量法测得的CPVC值。氧化铁红醇酸树脂漆，虽在CPVC时达到最高值，但漆膜的拉伸强度与坚韧度很差，正确选择颜料的用量以达到漆膜的各项性能都符合要求。",
+        "category": " Introduction"
+    },
+    {
+        "id": 172,
+        "chunk": "# 2.醇酸树脂漆的品种  \n\n现代涂料工业发展不断出现一些新的合成树脂，但醇酸树脂漆仍占有不可替代的重要地位。这是由于醇酸树脂漆品种多、用途广，从利用可再生资源和环境保护意义上讲，醇酸树脂漆仍有很大发展空间。  \n\n醇酸树脂漆的品种有清漆、磁漆、调合漆、底漆、二道底漆、防锈漆、腻子等品种。按漆膜光泽又分为高光、亚光、无光等。设计醇酸树脂漆的配方时应注意如下几点。  \n\n$\\textcircled{1}$ 清漆清漆由中油度或长油度亚麻油、豆油醇酸树脂溶于适当的溶剂，加入催干剂，过滤净化制成。醇酸清漆一般不用铅催干剂，因为醇酸树脂中游离的苯二甲酸酐能结合铅盐析出，从而使清漆发浑。醇酸清漆中应加入防结皮剂，松节油也有防结皮作用。  \n\n$\\textcircled{2}$ 色漆色漆配方设计的重点是成膜物质和颜、填料的体积比。我国涂料企业习惯于按质量比计算设计配方。实际在漆膜中，各组分是按相互占据的体积影响着漆膜的性能。在设计醇酸树脂色漆配方时，在注意树脂、颜料、溶剂、助剂这些成分的质量分数的同时，还需考虑到该配方的PVC值。PVC与漆膜光泽粗略对应关系为：PVC $3\\%\\sim20\\%$ ，有光磁漆；PVC $40\\%\\sim55\\%$ ，光泽度 $20\\%\\sim30\\%$ ；PVC $55\\%\\sim60\\%$ ，光泽度5%以下。  \n\n在醇酸树脂色漆中，醇酸磁漆是非常成熟、应用很广的一种面漆。它的PVC较低，般为 $3\\%\\sim20\\%$ ，不加或加极少量的填料，这也是与醇酸调合漆的主要差别。醇酸磁漆具有良好的装饰性和户外耐久性，既可常温干燥，也可烘干，既是一种通用的民用漆，也可制成各种工业漆，如卡车、农机、建筑机械用漆。在醇酸磁漆的基础上，通过增大PVC或加入消光剂可以生产出亚光或无光漆。传统的C04-64醇酸半光漆的光泽度（30士10)%，PVC为30%～40%，而C04-83醇酸无光磁漆的光泽度<10%，PVC为40%～50%。  \n\n其他醇酸色漆，如长油度醇酸色漆，醇酸树脂质量分数在70%以上，颜料分较低，PVC在 $10\\%$ 左右。  \n\n醇酸底漆，如铁红醇酸底漆，通常用中油度醇酸树脂，质量分数在35%左右，PVC在40%左右。  \n\n醇酸二道底漆，特点是颜料少而填料多，应用于底漆之上，以填充底漆的孔隙，PVC为 $45\\%\\sim50\\%$ 费  \n\n醇酸腻子，刮涂施工，以滑石粉、碳酸钙等填料为主，PVC在 $70\\%$ 以上。  \n\n水性醇酸树脂漆、醇酸树脂和其他树脂制备的硝基漆、氨基漆等，在其他章节叙述。",
+        "category": " Introduction"
+    },
+    {
+        "id": 173,
+        "chunk": "# 七、醇酸树脂的改性",
+        "category": " Introduction"
+    },
+    {
+        "id": 174,
+        "chunk": "# 1.新材料的应用  \n\n随着新材料的发展和市场对新产品的需求，醇酸树脂的品种更加多样化。新材料的应用主要是多元醇和多元酸的改换。  \n\n（1）多元醇如三羟甲基丙烷、乙二醇、一缩二乙二醇、新戊二醇等。  \n\n$\\Phi$ 三羟甲基丙烷有三个伯羟基，一个烃基支链，可增加醇酸树脂在烃类溶剂中的溶解度。三羟甲基丙烷原先主要用于聚氨酯涂料，用于醇酸树脂可采取三种方式：a.保持苯二甲酸酐不变；b.保持油度不变；c.三羟甲基丙烷与甘油按等量置换。三羟甲基丙烷制成的醇酸树脂烘漆有以下优点：烘干时间较短，漆膜硬度较大，漆膜耐碱性、保光性、保色性、耐烘烤性较好，但抗冲击性比甘油醇酸树脂差。  \n\n$\\textcircled{2}$ 乙二醇和一缩二乙二醇、新戊二醇都是二元醇，若与高官能度的多元醇合用，可以调节平均官能度。如与季戊四醇合用，按摩尔比 $1:1$ 时其平均官能度为3。乙二醇能调节季戊四醇的官能度，可代替甘油制作短油度醇酸树脂，基本维持油度和苯二甲酸酐含量不变，产品性能不低于甘油制作者。但乙二醇沸点低（198℃），所以在醇酸树脂生产时应采取蒸汽保温回流分馏柱。脂肪酸法生产醇酸树脂，如采用乙二醇，配料多加 $4\\%\\sim6\\%$ 的二甲苯。  \n\n另外，某些端羟基聚合物作为多元醇，用于醇酸树脂的生产，可提高醇酸树脂的某些性能。例如，端羟基聚丁二烯改性醇酸树脂可以使醇酸树脂漆的双摆硬度达到0.7以上。端羟基聚丁二烯（hydroyl-terminated polybutadiene）结构式如下：  \n\n它是一种以丁二烯为主链结构，带有羟基官能团的遥爪型预聚物。常温下为淡黄色透明液体，常温下密度为 $0.89\\sim0.92g/\\mathrm{cm}^{3}$ 。用此树脂分别制成清漆和色漆，各项力学性能合格，硬度达到0.7，有较大幅度提高。该树脂适于制作要求硬度高、耐油性好、平滑、有光泽的工程机械漆。  \n\n(2）多元酸  \n\n$\\Phi$ 松浆油酸松浆油酸来自松木造纸的废料，工艺不同，分馏出的松浆油酸的成分也不同。要求松香含量越少越好，最好不超过 $0.3\\%$ ，一般在 $0.1\\%$ 左右。松浆油酸的成分和豆油脂肪酸接近，可以制成自干性醇酸树脂。因为不含亚麻酸，所以黄变性甚低，适于制作白漆、浅色漆，可以自干与烘干。松浆油酸更适宜采用高聚物法制造醇酸树脂。  \n\n$\\textcircled{2}$ 间苯二甲酸间苯二甲酸在酯化时表现出官能度大于苯二甲酸酐。在处理配方时，其 $\\kappa$ 值应有所增加，如1.05。间苯二甲酸在酯化时表现与苯二甲酸酐不同，它的熔点高，在脂肪酸和甘油中不溶解，开始酯化很慢，所以酯化需用高温（如 $245\\sim260\\Upsilon.$ 。还可以用酸解法，其温度要在 $280^{\\circ}\\mathrm{C}$ 以上。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 175,
+        "chunk": "# 2.改性醇酸树脂  \n\n改性醇酸树脂是指经过化学反应构成的新的醇酸树脂。醇酸树脂经过改性效果可归纳见表2-1-33。  \n\n表2-1-33 醇酸树脂改性效果  \n\n\n<html><body><table><tr><td>改性剂</td><td>优 点</td><td>缺 点</td></tr><tr><td>松香与松香酯</td><td>快干，易剧涂，增加硬度，增加附着力</td><td>用量过多时易黄变，耐候性下降</td></tr><tr><td>苯甲酸、对叔丁基苯甲酸</td><td>调整醇酸树脂能度、增加硬度，快干，改进</td><td>溶解度与柔韧性降低</td></tr><tr><td>酚醛树脂</td><td>增加硬度，提高耐水性、耐碱性、耐溶剂性及 耐化学药品性</td><td>黄变性高，稳定性差</td></tr><tr><td>乙烯单体[苯乙烯、甲基丙烯酸 （酯）]</td><td>快干，改善光泽、颜色，提高耐候性（甲基丙 烯酸酯），提高耐水性（苯乙烯）</td><td>耐溶剂性差，耐候性降低（苯乙烯改 性）</td></tr><tr><td>有机硅（指少量有机硅改性）</td><td>提高防潮性，提高耐候性</td><td>降低耐溶剂性，改性过多干燥困难</td></tr><tr><td>多异氰酸酯（芳香族、脂肪族）</td><td>性提高干率，提耐水性，提高附着力，高耐磨分劳族异氨酸酶易黄变、粉化，双组</td><td></td></tr></table></body></html>  \n\n本章不讨论醇酸树脂与其他合成树脂如硝酸纤维素、过氯乙烯树脂、氯化橡胶等的合用。  \n\n(1）松香改性醇酸树脂松香的主要成分为松香酸，是链终止剂，可以把它简单作为一元酸来使用。因松香分子体积和空间位阻很大，所以可以减缓体系的胶化。配方设计时 $\\kappa$ 值要减小一些。松香可使醇酸树脂更容易溶于脂肪烃溶剂，增加漆膜的附着力，减少漆膜起皱，提高漆膜的耐水性、耐碱性和光泽度，降低黏度。漆膜释放溶剂较快，干率提高，干透加快。但松香本身含有共轭双键，不耐老化，用量过多影响耐候性，还会引起变色、发脆，所以应根据需要来确定用量。  \n\n松香及其酯类常用来生产醇酸调合漆。近几年来，我国豆油脚脂肪酸资源丰富。大豆油脚，先加酸进行酸化，然后在催化剂的存在下高压水解。使油脚中的油脂和磷脂完全水解。脂肪酸、醇进入油相，为粗脂肪酸；甘油、肌醇、磷酸盐、胆碱、乙醇胺等磷酸组分进入水相。粗脂肪酸经减压蒸馏制得工业豆油脚脂肪酸，其规格为：酸值 $195{\\sim}205\\mathrm{mgKOH/g}$ 碘值 $110{\\sim}120\\mathbf{g}\\mathrm{I}_{2}/100\\mathbf{g}$ ；色泽（铁钻比色计） $2{\\sim}4$ 号；凝固点 $24\\sim32\\ensuremath{\\mathrm{\\DeltaC}}$ ；豆油脚脂肪酸含$1+3=99\\%$ 。用豆油脚脂肪酸生产醇酸树脂，既充分利用可再生资源，又降低了生产成本。用松香改性豆油脚脂肪酸醇酸树脂的目的是：提高其干性（豆油脚脂肪酸的碘值较低)，并改善其极性和溶解性，以制备分子量适中的醇酸树脂。鉴于豆油脚脂肪酸在涂料行业应用比较广，所以这种松香改性豆油脚脂肪酸醇酸树脂具有一定代表性。  \n\n现把这种树脂作为松香改性醇酸树脂的一个例子加以介绍。  \n\n【例】利用豆油脚脂肪酸-松香-苯酐，采用脂肪酸法制备松香改性醇酸树脂。由于豆油脚脂肪酸是半干性脂肪酸，用松香调整其分子官能度，并改善其干性。松香和豆油脚脂肪酸之间的比例，计算配比结果为：豆油脚脂肪酸：松香 $=72:28$ 9  \n\n松香、豆油酸进料配比见表2-1-34。甘油（醇）配比量的选择见表2-1-35。  \n\n表2-1-34松香、豆油酸进料配比  \n\n\n<html><body><table><tr><td>品 名</td><td>分子量M</td><td>碘值/（mgKOH/g）</td><td></td><td>分子官能度f松香加入量%</td><td>豆油脂肪酸加入量/%</td></tr><tr><td>亚麻油酸</td><td>280</td><td></td><td>175</td><td>3.86</td><td></td><td></td></tr><tr><td>豆油脚酸</td><td></td><td>311.67</td><td>138</td><td>3.04</td><td></td><td>72</td></tr><tr><td>松香</td><td></td><td>330</td><td>220</td><td>5.72</td><td>28</td><td></td></tr></table></body></html>  \n\n表2-1-35甘油（醇）配比量的选择  \n\n\n<html><body><table><tr><td>甘油（醇）超量范围（R)</td><td>1.05</td><td>1.06</td><td>1.10</td><td>1.15</td><td>1. 20</td></tr><tr><td>平均官能度</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td></tr><tr><td>有效官能度</td><td>2.86</td><td>2.83</td><td>2.73</td><td>2.6</td><td>2.5</td></tr></table></body></html>  \n\n油度 $63\\%$ ，选择甘油过量， $R=1.053$ ，树脂产量为 $100\\mathbf{kg}$ ，酯化出水 $6.81\\mathrm{kg}$ 。原料配比如下： $m_{\\Lambda}$ 为一元酸用量； $m_{\\mathrm{B}}$ 为松香用量； $m\\mathrm{c}$ 为豆油酸用量； $m_{\\mathrm{D}}$ 为苯酐用量； $m_{\\mathrm{E}}$ 为甘油用量； $E_{\\mathrm{B}}$ 为松香酯化当量，330； $E_{\\mathrm{C}}$ 为豆油酸酯化当量，311.67。  \n\n其中： $\\scriptstyle{E}$ 为酯化当量， $E_{\\mathrm{B}}=330$ $E_{\\mathrm{C}}=311,67$ $E_{\\mathrm{D}}=74$ . $E_{\\mathrm{E}}{=}18.55$ $E_{\\mathrm{{F}}}=18$ 要  \n\n下标：A表示一元酸；B表示松香；C表示豆油脚脂肪酸；D表示苯酐；E表示甘油；F表示水。  \n\n$$\n\\lceil\\boxed{\\mathrm{H}\\boxplus\\mathrm{L}}=\\frac{E_{\\mathrm{D}}\\bigg[100-(R E_{\\mathrm{E}}+E_{\\mathrm{C}}-E_{\\mathrm{F}})\\frac{W_{\\mathrm{C}}}{E_{\\mathrm{C}}}+(R E_{\\mathrm{E}}+E_{\\mathrm{B}}+E_{\\mathrm{F}})\\frac{W_{\\mathrm{B}}}{E_{\\mathrm{B}}}\\bigg]}{R E_{\\mathrm{E}}+E_{\\mathrm{D}}-9}\n$$  \n\n其中： $m_{\\mathrm{F}}=100+18{\\frac{m_{\\mathrm{C}}}{E_{\\mathrm{C}}}}+18{\\frac{m_{\\mathrm{B}}}{E_{\\mathrm{B}}}}+9{\\frac{m_{\\mathrm{D}}}{E_{\\mathrm{D}}}}$  \n\n原材料规格与配方见表2-1-36。  \n\n表2-1-36原材料规格与配方   \n\n\n<html><body><table><tr><td>序号</td><td>原料</td><td>规 格</td><td>用量/%</td></tr><tr><td>1</td><td>豆油脂肪酸</td><td>棕色黏液体；碘值（韦氏法）120～140glz/100g；酸值175~180mgKOH/g；水</td><td>24~54</td></tr><tr><td>2</td><td>松香</td><td>抽出反应中性 滴水法1级</td><td>0.10</td></tr><tr><td>3</td><td>苯二甲酸酐</td><td>99.2%</td><td>15.77</td></tr><tr><td>4</td><td>顺丁烯二酸酐</td><td>99.2%</td><td>0.31</td></tr><tr><td>5</td><td>甘油</td><td>99.9%</td><td>10.64</td></tr><tr><td>6</td><td>二甲苯</td><td>工业</td><td>3.07</td></tr><tr><td></td><td>松香水</td><td>工业</td><td>35.57</td></tr></table></body></html>  \n\n脂肪酸法制备工艺如下。  \n\n$\\Phi$ 将豆油脚脂肪酸、松香、苯酐、顺丁烯二酸酐、甘油及回流二甲苯加入酯化釜中，升温至 $150^{\\circ}\\mathrm{C}$ ，开动搅拌，升温至 $175{\\sim}180\\ensuremath{\\mathrm{^{\\circ}C}}$ ，恒温回流1h。  \n\n$\\textcircled{2}$ 继续升温到 $200{\\sim}230\\Upsilon$ ，回流酯化，待黏度、酸值合格后，抽人反应釜中。  \n\n$\\textcircled{3}$ 降温到 $160^{\\circ}\\mathrm{C}$ 兑稀，在 $80^{\\circ}C$ 过滤。  \n\n选用顺丁烯二酸酐作为催化剂，加快豆油脚脂肪酸的酯化速率，其用量为投料的 $0.5\\%$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 176,
+        "chunk": "# 产品规格：  \n\n<html><body><table><tr><td>黏度（涂-4杯）/s</td><td>90~150</td><td>固体分/% 57~67</td></tr><tr><td>酸值/（mgKOH/g）</td><td>11~15</td></tr></table></body></html>\n\n采用凝胶渗透法测定醇酸树脂分子量分布见表2-1-37。  \n\n表2-1-37醇酸树脂分子量分布  \n\n\n<html><body><table><tr><td>项目</td><td>总数</td><td>分数 M</td><td>分质量M.</td><td>分子盘 M.</td><td>分量M.</td><td>M/M</td><td>M/M</td></tr><tr><td>数值</td><td>16472</td><td>2361. 01</td><td>15641. 6</td><td>51892.2</td><td>12051. 2</td><td>6.62496</td><td>21.9</td></tr></table></body></html>  \n\n(2）苯甲酸改性醇酸树脂近年来常采用苯甲酸或对叔丁基苯甲酸代替部分脂肪酸来制造醇酸树脂。苯甲酸是一元酸，分子量较小，而且有一个苯环结构，引入醇酸树脂结构之后可使漆膜快干、光泽度高、硬度大，耐水性、耐盐雾性、保光性、耐候性均好，耐溶剂性比改性苯乙烯好，不怕咬底；但较脆，耐冲击性与弯曲性比未改性者差。它与其他醇酸树脂或氨基树脂的混溶性也很好，可以拼用，先以未改性者研磨色浆，再与改性者合并。与氨基树脂合用可以快干，同时还可减少氨基树脂的用量。  \n\n苯甲酸是一元酸，配方处理简单，按一般原则取代一定当量比例的脂肪酸（一般取代30%左右；若 $50\\%$ 则树脂漆膜过脆)，所制醇酸树脂都是中、短油度醇酸树脂。配制成各种磁漆，漆膜坚固、美观、耐久，用于卡车、拖拉机、机械部件等物品涂装。  \n\n制造工艺如下：将豆油脂肪酸、多元醇、苯二甲酸酐、苯甲酸全部加入反应釜中，通人$\\mathrm{CO}_{2}$ ，升温至 $150\\mathrm{^c}$ 保持0.5h；升温到 $180^{\\circ}\\mathrm{C}$ 保持2h，升温到 $230^{\\circ}\\mathrm{C}$ 以溶剂法 (加入二甲苯)酯化。保持到酸值小于 $10\\mathrm{mgKOH/g}$ ，以 $200^{\\sharp}$ 油漆溶剂油溶解成 $50\\%$ 树脂溶液。  \n\n表2-1-38、表2-1-39为苯甲酸、对叔丁基苯甲酸改性醇酸树脂与未改性醇酸树脂配方及 漆膜性能比较。  \n\n表2-1-38苯甲酸、对叔丁基苯甲酸改性醇酸树脂与未改性醇酸树脂配方比较   \n\n\n<html><body><table><tr><td>配 方</td><td>苯甲酸改性</td><td>对叔丁基苯甲酸改性</td><td>未改性</td></tr><tr><td>苯二甲酸酐/%</td><td>35.6</td><td>34.7</td><td>33.1</td></tr><tr><td>豆油脂肪酸/%</td><td>41.2</td><td>40.1</td><td>50.9</td></tr><tr><td>季戊四醇/%</td><td>17.5</td><td>17.0</td><td>16.2</td></tr><tr><td>乙二醇/%</td><td>7.7</td><td>7.5</td><td>7.2</td></tr><tr><td>苯甲酸/%</td><td>5.9</td><td>一</td><td>一</td></tr><tr><td>对叔丁基苯甲酸/%</td><td>一</td><td>8.4</td><td>一</td></tr><tr><td>黏度（按1：1,溶于200*油漆溶剂油，25℃，加氏管）/s</td><td>9.0</td><td>3.3</td><td>3</td></tr><tr><td>颜色(铁钻比色计)/号</td><td>5~6</td><td>5~6</td><td>5~6</td></tr><tr><td>酸值/（mgKOH/g）</td><td>9.7</td><td>9.4</td><td>9.9</td></tr></table></body></html>  \n\n表2-1-39改性醇酸树脂与未改性醇酸树脂漆膜性能比较   \n\n\n<html><body><table><tr><td>漆膜性能</td><td>未改性</td><td>苯甲酸改性</td><td>对叔丁基苯甲酸改性</td></tr><tr><td>清漆（0.5%Pb，0.05%Co），常温干 全干/h</td><td>12 20</td><td>7,8~5.8 30~40</td><td>/</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>漆膜性能</td><td>未改性</td><td>苯甲酸改性</td><td>对叔丁基苯甲酸改性</td></tr><tr><td>耐水性</td><td>无变化</td><td>无变化</td><td>0</td></tr><tr><td>耐3%NaOH溶液，剥蚀时间/h</td><td>0.33</td><td>2.33</td><td>0</td></tr><tr><td>色漆(0.5%Pb，0.05%Co)，常温</td><td>一</td><td>一</td><td></td></tr><tr><td>全干/h</td><td>9.00</td><td>6.75</td><td>0</td></tr><tr><td>斯氏硬度(干14天)</td><td>24</td><td>30</td><td>0</td></tr><tr><td>耐热水</td><td>无变化</td><td>无变化</td><td>0</td></tr><tr><td>耐冷水</td><td>无变化</td><td>无变化</td><td>0</td></tr><tr><td>耐3%NaOH溶液，剥蚀时间/h</td><td>1.00</td><td>3.00</td><td>+</td></tr><tr><td>光泽度/%</td><td>90</td><td>91</td><td>0</td></tr><tr><td>保光性(老化器100h）/%</td><td>68</td><td>74.5</td><td>+</td></tr><tr><td>色漆（0.02%Mn），105C，0.5h烘干</td><td></td><td></td><td></td></tr><tr><td>斯氏硬度</td><td>18</td><td>30~40</td><td>一</td></tr><tr><td>耐热水</td><td>无变化</td><td>无变化</td><td>0</td></tr><tr><td>耐冷水</td><td>无变化</td><td>无变化</td><td>0</td></tr><tr><td>耐3%NaOH溶液，剥蚀时间/h</td><td>5,50</td><td>7,41~8,00</td><td>+</td></tr><tr><td>光泽度/%</td><td>89</td><td>89</td><td>。0</td></tr><tr><td>保光性(老化器100h）/%</td><td>94.6</td><td>92.1~95.5</td><td>0</td></tr><tr><td>原始颜色</td><td>6.6</td><td>5.1~6,8</td><td>+</td></tr><tr><td>保色性（老化器100h）</td><td>4.2</td><td>1,9 ~3, 8</td><td>+</td></tr><tr><td>光泽度（多烘1h）/%</td><td>92.3</td><td>87,4~89.0</td><td>+</td></tr><tr><td>颜色（烘前）</td><td>6.5</td><td>4,8~6,1</td><td>+</td></tr><tr><td>颜色（烘1h后）</td><td>14.1</td><td>11.0~12.5</td><td>+</td></tr></table></body></html>\n\n$\\Phi$ 色漆配方：二氧化钛·成膜物 $^{=1}$ 1.$\\textcircled{2}$ 此栏数值相比于苯甲酸改性： $^+$ 表示比苯甲酸改性者优；一表示比之较劣；0表示相等。  \n\n(3）酚醛树脂改性醇酸树脂以酚醛树脂改性醇酸树脂，它们之间的化学反应过程尚不完全清楚。酸性催化剂制成的酚醛树脂（线型酚醛树脂）与松香改性酚醛树脂、醇酸树脂很容易融合，可以提高干率与耐水性，但将使耐候性降低，而酚醛树脂并没有与醇酸树脂结合进入醇酸树脂的结构之中。酚醛树脂耐候性不良，引入松香使耐候性进一步降低。用碱性催化剂制成的热固性酚醛树脂本身固化过快，不能得到满意的结果。于是采用对位取代的酚（如对叔丁基苯酚）以碱性催化剂制成低分子量的缩合物，这样的酚醛树脂有较好的油溶性并易与各种醇酸树脂反应。改性时用量一般为 $5\\%$ ，最多不能超过 $20\\%$ 。虽然用量不大，但能明显地改进漆膜的抗水性、抗酸性、抗碱性、抗烃类溶剂性等，耐候性没有显著降低，黏度比未改性前增加很多。  \n\n酚醛树脂中有酚醇结构，在加热情况下脱水生成亚甲基，它能与油中的不饱和双键发生加成反应，所以改性的同时也降低了油的不饱和度。酚醇还可以在酸存在下与羟基发生醚化反应。  \n\n酚醛树脂可在醇酸树脂制造的后期加人。醇酸树脂已酯化完毕，降温至 $200^{\\circ}C$ 时将对叔丁基苯酚甲醛树脂的碎块加入。不能加得过快，因为加入酚醛树脂后会起沫。加完升温至$200{\\sim}240^{\\circ}\\mathrm{C}$ ，保持至黏度达到要求，停止反应，溶解成醇酸树脂溶液。注意加酚醛树脂后黏度上升得很快，需要小心操作。  \n\n(4）无油醇酸树脂无油醇酸树脂即不含脂肪酸的醇酸树脂，也即涂料用聚酯。它不以脂肪酸来改性，而从其他方面来平衡醇酸树脂的结构以满足制作涂料的要求。如使用一元酸（主要为对叔丁基苯甲酸）、二元醇来调整官能度；使用脂肪族长链二元酸（如己二酸）以调整柔韧性；使用带支链的三元醇（三羟甲基丙烷或乙烷)、二元醇（新戊二醇及其他带支链的二元醇）以提高溶解性、混溶性。这样可制成低反应活性（含游离羟基较少）和高反应活性（含游离羟基较多）的无油醇酸树脂。前者与硝酸纤维素合用，后者与氨基树脂合用，用于制作烘漆。  \n\n无油醇酸树脂改进了常规不干性油醇酸树脂氨基烘漆的缺点。如附着力、稳定性、柔韧性、硬度、光泽及在高达 $200^{\\circ}\\mathrm{C}$ 过度烘烤中的保色性。在相同柔韧度的情况下，无油醇酸树脂氨基漆可较常规者硬度高一倍，另外，特别是漆层之间的附着力非常强。  \n\n表2-1-40低反应活性无油醇酸树脂配方  \n\n\n<html><body><table><tr><td>原 料</td><td>当 量</td><td>原 料</td><td>当 量</td></tr><tr><td></td><td>2.29 11.46 基</td><td>对友二甲胶</td><td></td></tr><tr><td>三新基丙烷</td><td></td><td></td><td></td></tr><tr><td></td><td>9.17 /</td><td></td><td></td></tr></table></body></html>  \n\n无油醇酸树脂主要用于氨基烘漆，用于汽车、机器设备、家用电器、金属家具，也用于卷材涂料等。  \n\n$\\textcircled{1}$ 低反应活性的无油醇酸树脂表2-1-40为低反应活性无油醇酸树脂配方。树脂的结构与制造方法有关，可采取高聚物法，如先不加三羟甲基丙烷与一元酸，使二官能度反应物先反应，促进链的增长，最后再加三羟甲基丙烷与一元酸进行反应，使支链处于主链的末端。或开始时保持一部分三羟基甲基丙烷以限制链上的支链度。一元酸总是在最后阶段加入，使树脂的链能尽量地增长至最大链长。按配方先酯化反应至酸值为 $20\\mathrm{mgKOH/g}$ $(220\\%$ ，约8h)，后加己二酸与一元酸再酯化至酸值为 $2.4\\mathrm{{mgKOH/g}}$ 。该树脂可用于制作纤维素漆，也可与氨基树脂合用制作烘漆。  \n\n与醋酸丁酸纤维素合用制作再流平闪光漆配方（质量分数）／%  \n\n\n<html><body><table><tr><td>半秒醋酸丁酸纤维素</td><td>52</td><td>溶剂[甲苯：乙醇：乙酸乙酯：异丁醇丁基乙二醇</td></tr><tr><td>无油醇酸树脂（70%）</td><td>43.3</td><td>醚=44+1313+19 +11(质量比)]</td></tr><tr><td>铝粉</td><td>2.2</td><td></td></tr><tr><td></td><td></td><td></td></tr><tr><td>菁蓝色浆（60%)</td><td>2.5</td><td></td></tr></table></body></html>  \n\n磷化钢板涂两道环氧底漆， $140^{\\circ}\\mathrm{C}$ 烘 $30\\mathrm{min}$ ，用 $400^{\\sharp}$ 砂纸湿磨，再涂上面漆，厚度约为$50\\mu\\mathrm{m}$ 。漆膜光泽和耐久性极好，开始光泽度 ${^{\\mathrm{60}^{\\circ}}}$ ）为 $90\\%$ ，于佛罗里达州曝晒2年后仍可保持光泽度为 $75\\%$ 。  \n\n$\\textcircled{2}$ 高反应活性的无油醇酸树脂羟基值为 $40{\\sim}200\\mathrm{mgKOH/g}$ ，常与氨基树脂合用。有较高含量的二元醇、三元醇，就有较多的游离羟基与氨基树脂缩合，可示意如下：  \n\n![](images/043c170d4274d0415bace13460f21a314f6c8f1c87a5911bf88080d4a96a74cf.jpg)  \n\n能用的二元醇品种很多，它们对光泽、硬度、柔韧性等方面的影响不大，但从耐洗涤剂、抗沾污性、耐过度烘烤性、热稳定性等方面综合考虑还是新戊二醇最佳。  \n\n己二酸或壬二酸的用量影响着抗沾污性与柔韧性，用量低，抗沾污性好，用量高，则柔韧性好。抗沾污性在家用电器方面较重要，柔韧性则在工业部件上非常重要。表2-1-41介绍美国几个著名公司高活性无油醇酸树脂的配方与漆的性能。  \n\n表2-1-41高性能无油醇酸树脂的配方与漆的性能  \n\n\n<html><body><table><tr><td>项目</td><td colspan=\"2\">Amoco Chemicals</td><td colspan=\"2\">Union Carbide Corp</td><td colspan=\"3\">Eastman Chemical Products Inc.</td><td colspan=\"2\">Trojan Powder Company</td><td colspan=\"2\">Amoco Chemicals</td></tr><tr><td></td><td></td><td></td><td>一</td><td></td><td></td><td>一</td><td></td><td>11.64</td><td>11. 8</td><td></td><td></td></tr><tr><td>无油醇酸树脂 三羟甲基乙烷</td><td>12.2</td><td>一 12.42</td><td>14</td><td>14</td><td>一 12.5</td><td>6.6</td><td>6.6</td><td>一</td><td>一</td><td>一 8.3</td><td>一 10.1</td></tr><tr><td></td><td></td><td>19.26</td><td></td><td></td><td></td><td>一</td><td>一</td><td></td><td>18.8</td><td></td><td>15.7</td></tr><tr><td>三羟甲基丙烷</td><td>19.0 一</td><td>一</td><td></td><td>一</td><td>14.6 一</td><td>28.0</td><td>28.0</td><td>18.4 一</td><td></td><td>12. 8</td><td>一</td></tr><tr><td>新戊二醇</td><td></td><td>一</td><td>一 29</td><td>一 29</td><td></td><td>一</td><td></td><td></td><td>一</td><td>一</td><td>一</td></tr><tr><td>三甲基戊二醇酯二醇-204</td><td></td><td>13.56</td><td>/</td><td></td><td>13.6</td><td></td><td>13.6</td><td>一 6.94</td><td>一</td><td></td><td></td></tr><tr><td>己二酸 间苯二甲酸</td><td>6.7 30.3</td><td>23.1</td><td>34.8</td><td>一 34.8</td><td></td><td>13.6 19.35</td><td>19.35</td><td></td><td>14.1</td><td>一</td><td>一 24.4</td></tr><tr><td>对叔丁基苯甲酸</td><td>一</td><td>-</td><td>一</td><td>一</td><td>19.4 8.3</td><td>一</td><td></td><td>31.6</td><td>24.0</td><td>4.5</td><td></td></tr><tr><td>苯基满二酸（PIDA)</td><td></td><td></td><td></td><td>一</td><td></td><td></td><td></td><td></td><td>%</td><td></td><td>一</td></tr><tr><td>二甲苯</td><td>一</td><td>一 36</td><td>一</td><td>一</td><td>一 36</td><td>一</td><td></td><td>一</td><td>一</td><td>40</td><td>16.5</td></tr><tr><td>乙二醇单丁醚</td><td>36 4</td><td>4</td><td>一</td><td></td><td>4</td><td>36</td><td>36 4</td><td>36</td><td>36</td><td>36</td><td>36</td></tr><tr><td>乙基苯</td><td></td><td>一</td><td>7.7</td><td>7.7</td><td>一</td><td>4 一</td><td>一</td><td>一</td><td>一</td><td>4</td><td>4</td></tr><tr><td>乙酸异丁酯</td><td>一</td><td>一</td><td>22.1</td><td>22.1</td><td></td><td></td><td></td><td>一</td><td>一</td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td>一</td><td>一</td><td>一</td><td>一</td><td>一</td><td>一</td><td></td></tr><tr><td>丁醇</td><td>一</td><td>一</td><td>一</td><td>一</td><td>一</td><td>一</td><td>一</td><td>4</td><td>4</td><td></td><td>/</td></tr><tr><td>出水</td><td>8.2</td><td>8.34</td><td>7.6</td><td>-7.6</td><td>8.4</td><td>7.55</td><td>7.55</td><td>8.58</td><td>8.7</td><td>-5.6</td><td>6.7</td></tr><tr><td>净总得量/%</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td></tr><tr><td>羟基超量/%</td><td>43</td><td>38.7</td><td>43</td><td>43</td><td>20</td><td>20</td><td>20 Plaskom</td><td>37</td><td>37</td><td>31.6</td><td>32.5</td></tr><tr><td>氨基系统(牌号)</td><td colspan=\"2\">Cymei 248-8</td><td></td><td colspan=\"2\">Cymel 30 </td><td colspan=\"2\">Cymel 300</td><td colspan=\"2\">Cye 31</td><td colspan=\"2\">Cymel 2488</td></tr><tr><td>催化剂</td><td>无</td><td>无</td><td>Cyzac 1010</td><td>Cyzac 1010</td><td>Cyzae 1010</td><td>Cyzac 1010</td><td>Cyzae 1010</td><td>Cyzac 1010</td><td>Cyzac 1010</td><td>无</td><td>无</td></tr><tr><td>醇酸！氨基（质量比）</td><td></td><td>75 1 2575  25</td><td></td><td>一</td><td>80  20</td><td>85 + 15</td><td>85  15</td><td>一</td><td>一</td><td>80 + 2085 + 15</td><td></td></tr><tr><td>颜料：成膜物(质量比）</td><td></td><td>0. 91 ± 1|0. 91 ± 1</td><td>19.3@</td><td>19.4</td><td></td><td></td><td>0. 66 ± 10. 66 ± 10.66 ± 1</td><td>一</td><td></td><td>0. 9 ± 10. 9 ± 1</td><td></td></tr><tr><td>不挥发分/%</td><td>55</td><td>55</td><td>67</td><td>71</td><td>60</td><td>60</td><td>60</td><td>50.8</td><td>50.8</td><td>55</td><td>58</td></tr><tr><td>黏度（福特-4杯）</td><td>一</td><td>一</td><td>140</td><td>148</td><td>一</td><td>一</td><td>一</td><td></td><td>一</td><td></td><td>一</td></tr><tr><td>烘干（30min）/C</td><td>149</td><td>149</td><td>177</td><td>177</td><td>177</td><td>177</td><td>177</td><td>149</td><td>149</td><td>一</td><td>一</td></tr><tr><td>60°光泽度/%</td><td>84</td><td>88</td><td>90</td><td>90+</td><td>100</td><td>90</td><td>97</td><td>一</td><td></td><td>93</td><td>93</td></tr><tr><td>铅笔硬度</td><td>2H</td><td>2H</td><td></td><td></td><td>6H</td><td>2H</td><td>H</td><td>一</td><td></td><td>3H</td><td>2H</td></tr><tr><td>正面冲击/N·m</td><td>1.70</td><td>7.91</td><td>3. 39</td><td></td><td>13.5611.30@</td><td>11.30@</td><td>11.30</td><td>9.04</td><td>6.78</td><td>2.26</td><td>7.91</td></tr><tr><td>反面冲击/N·m</td><td>0.23</td><td>3.96</td><td>2.26</td><td>16.95</td><td>7.91</td><td>11.30@</td><td>7.91@</td><td>3.96</td><td>2.26</td><td>0</td><td>2.26</td></tr><tr><td>锥形轴棒弯曲</td><td>P.</td><td>VG</td><td>P</td><td>E</td><td>E</td><td>E</td><td>E</td><td></td><td>一</td><td>P</td><td>E</td></tr><tr><td>过度烘烤稳定性（60°光</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>泽度>/%</td><td>60</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>4h,230°℃ 16h,162℃</td><td>一</td><td>72 一</td><td>一</td><td>一</td><td>85</td><td>85</td><td>一 78</td><td>一</td><td></td><td>88</td><td>88</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>项目</td><td colspan=\"2\">Amoco Chemicals</td><td colspan=\"2\">Union Carbide Corp</td><td colspan=\"3\">Eastman Chemical Produets Ine.</td><td colspan=\"2\">Trojan Powder Company</td><td colspan=\"2\">Amoco Chemicals</td></tr><tr><td>耐沽污性/h 芥末</td><td>0.5</td><td>0.5</td><td>24</td><td>24</td><td>24</td><td>24</td><td>24</td><td>一</td><td>一</td><td>24</td><td>24</td></tr><tr><td></td><td>（150°C℃）（150°C） E</td><td>F</td><td>E</td><td>E</td><td>P</td><td>F</td><td>P</td><td>一</td><td>一</td><td>E</td><td>一</td></tr><tr><td>碘</td><td>VG</td><td>P</td><td></td><td></td><td>E</td><td>F</td><td>P</td><td>一</td><td>一</td><td>E</td><td>一</td></tr><tr><td>黑墨水</td><td>VG</td><td>F</td><td>E</td><td>E</td><td>E</td><td>E</td><td>E</td><td>一</td><td></td><td>G</td><td>一</td></tr><tr><td>玉米油-油酸</td><td>一</td><td>一</td><td>一</td><td>一</td><td>E</td><td>P</td><td>P</td><td>一</td><td></td><td>一</td><td>一</td></tr><tr><td>口红</td><td>E</td><td>E</td><td>一</td><td>一</td><td>一</td><td>一</td><td>一</td><td>一</td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>耐溶剂性</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>二甲苯</td><td>E</td><td>F</td><td>一</td><td>一</td><td>一</td><td>一</td><td>一</td><td>一</td><td>一</td><td>E</td><td>一</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>丙酮，1h</td><td>一</td><td>一</td><td>E</td><td>E</td><td></td><td>一</td><td>一</td><td>一</td><td>-</td><td>E</td><td>一</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>甲基乙基甲酮，擦50次</td><td>一</td><td>一</td><td>E</td><td>E</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>\n\n$\\Phi$ 三甲基戊二醇酯二醇-204结构式为 $\\mathrm{HOCH_{2}C(C H_{3})_{2}C H_{2}O O C C(C H_{3})_{2}C H_{2}O H},$ $\\oslash$ 按体积比。$\\textcircled{3}$ Bomderite 1000钢板。$\\textcircled{4}$ 20°Bomderite 37钢板。$\\textcircled{5}$ E表示优；VG表示很好；G表示好；F表示可；P表示劣。$\\textcircled{6}$ 24h试验。  \n\n每个公司两个配方，第一个为高耐沾污性配方，第二个为高柔韧性配方。这些公司彼此并无联系，表内数据不能对比评价，但它们提供了高性能涂料的技术线索，很有参考价值。  \n\n不仅无油醇酸树脂的成分与合成工艺影响漆的性能，氨基树脂的选择也非常重要，因为很多丁醇醚化的三聚氰胺甲醛树脂商品有着不同的聚合度、不同的烷氧基化程度、不同量的羟甲基和不同的残留氨基氢原子。这些因素影响氨基树脂与醇酸树脂的融合性、本身的自聚性和与醇酸树脂的共缩聚性。自聚和与醇酸树脂的共缩聚是竞相进行的，氨基树脂自聚如下：  \n\n![](images/e28848506cb64c348acf9b69b10e39f3f14b98106f470edfc77c40b937ce9d35.jpg)  \n\n则减少与醇酸树脂的缩聚。虽然自聚也可以增加漆膜硬度和耐化学药品性，但将很大程度地降低柔韧性与光泽度。使用六甲氧亚甲基三聚氰胺可以得到较好的柔韧性，因为它基本上没有自聚。只有在 $150^{\\circ}\\mathrm{C}$ 以上，有酸催化剂存在下才会有自聚发生。  \n\n表中所述的氨基树脂只有商品牌号，不能确知其成分。Cymel300则是已熟知的六甲氧亚甲基三聚氰胺。  \n\n在施工时须控制流平性及消除缩孔。为此设备必须非常清洁，被涂表面也必须清洁。有机硅助剂可以控制流平性。加入树脂的 $10\\%\\sim20\\%$ 醋酸丁酸纤维素（EAB-551-0.2），作为增稠剂可以消除缩孔。  \n\n无油醇酸树脂的配方中都有对叔丁基苯甲酸以提高溶解性、混溶性；间苯二甲酸的添加可减少苯二甲酸酐内酯的形成，有利于链的增长。表2-1-42介绍三个配方，分别为：树脂A 含对叔丁基苯甲酸和间苯二甲酸；树脂B只含间苯二甲酸，不含对叔丁基苯甲酸；树脂C两者皆不含，以苯二甲酸酐代替间苯二甲酸。经比较树脂A性能最好。  \n\n反应釜装有蒸汽保温分馏柱。树脂A含有一元酸（对叔丁基苯甲酸)，可采用高聚物法。先将除对叔丁基苯甲酸以外的原材料加人反应釜中，用1h的时间升温至 $180^{\\circ}\\mathrm{C}$ 。升温的同时通入情性气体和进行搅拌，保持1h内升温至 $205\\mathrm{^q}$ ，保持1h内升温至 $220^{\\circ}\\mathrm{C}$ 。酯化至出水量达到理论的 $75\\%$ ，降温至 $150\\mathrm{^{\\circ}C}$ ，加对叔丁基苯甲酸，升温至 $205^{\\circ}\\mathrm{C}$ ，保持 $30\\mathrm{{min}}$ .再升温至 $230^{\\circ}\\mathrm{C}$ ，保持至黏度合格，降温至 $150^{\\circ}\\mathrm{C}$ ，加入二甲苯与乙二醇单丁醚（ $_9:1)$ 混合溶剂制成 $60\\%$ 溶液。  \n\n表2-1-42醇酸树脂配方与性能  \n\n\n<html><body><table><tr><td>组成与性能</td><td>树脂A</td><td>树脂B</td><td>树脂C</td></tr><tr><td>组成/% 三羟甲基丙烷（当量）</td><td>6.0</td><td>5.75</td><td></td></tr><tr><td>三羟甲基乙烷 新戊二醇 己二酸</td><td>一 6.0 4.0</td><td>一 6.75 4.0</td><td>5.375 7.125 3,00</td></tr><tr><td>间苯二甲酸 苯二甲酸酐</td><td>5.0 一</td><td>6.00 一</td><td>一 7.00</td></tr><tr><td>对叔丁基苯甲酸</td><td>1.0</td><td>二</td><td></td></tr><tr><td></td><td></td><td></td><td>一-</td></tr><tr><td>树脂性质</td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td>酸值/(mgKOH/g)</td><td>16</td><td>22</td><td>40</td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td>加氏黏度（50%二甲苯溶液，25℃）/s</td><td>W</td><td>W</td><td>Z</td></tr><tr><td>羟基过量/%</td><td>20</td><td>25</td><td>25</td></tr><tr><td>漆膜性能</td><td></td><td></td><td></td></tr><tr><td>Tukon硬度</td><td>17.4</td><td>19.6</td><td>25.9</td></tr><tr><td>60°光泽度/%</td><td>94</td><td>90</td><td></td></tr><tr><td></td><td></td><td></td><td>85</td></tr><tr><td>反面冲击/N·cm</td><td>490.3</td><td>686.42</td><td>49.03</td></tr><tr><td>柔韧性/cm</td><td>0.635</td><td>0.635</td><td>0. 635</td></tr><tr><td>附着力（划格）/MPa</td><td>10</td><td>7</td><td>9</td></tr><tr><td>烘干后，再在177℃烘16h</td><td>白，光泽好</td><td>白，光泽尚可</td><td>淡黄，光泽低</td></tr></table></body></html>  \n\n树脂B不含一元酸，可以将全部原料一次加人反应釜中。用1h升温至 $180^{\\circ}\\mathrm{C}$ ，升温同时通入情性气体和进行搅拌，再以1h升温至 $205\\mathrm{{C}}$ ，保持1h，再以1h升温至 $230\\Upsilon$ ，保持至酸值达到 $25\\mathrm{mgKOH/g}$ ，降温至 $150^{\\circ}\\mathrm{C}$ 以二甲苯与乙二醇单丁醚 $(9:1)$ 混合溶剂溶成$60\\%$ 溶液。  \n\n树脂C不含间苯二甲酸，制法与一般脂肪酸法相同。  \n\n(5）水性醇酸树脂近年来水性醇酸树脂的技术有很大的发展，它节省大量的有机溶剂，既节约资源，又减轻环境污染，还减小火灾的危险。水性醇酸树脂可制成在水中可分散型与水溶型的树脂。  \n\n$\\Phi$ 水中可分散型醇酸树脂最早英国ICI公司申请了将醇酸树脂乳化于干酪素溶液中制成有光泽的醇酸树脂漆的专利。1950年美国PPG公司首先申请了将聚乙二醇引入醇酸树脂的分子结构中，可使醇酸树脂具有水中自分散性的专利，此后此项课题研究者较多，屡有专利发表。聚乙二醇的脂肪酸酯可制成广泛范围的表面活性剂，属非离子型，不受 $\\mathsf{p H}$ 与无机盐的影响。  \n\n聚乙二醇酯可依其亲水的氧乙烯基与憎水的脂肪酸基在分子中的比例分为三类。如以H表示亲水基团，L代表憎水基团， $\\scriptstyle{\\mathrm{H}}=\\mathbf{L}$ 时则此脂肪酸对水与油都有相近的溶解度； $\\mathbf{H}>$ L时则主要为油溶。油溶型虽然不溶于水，但它往往可以分散于水形成稳定的乳液。将聚乙二醇引人醇酸树脂分子结构之中可形成类似非离子型表面活性剂的结构而具有水中自分  \n\n散性。  \n\n![](images/a849d9e3d900a554f1f945e0a49807a11e85783337aef02e88d8041808be1e7c.jpg)  \n亲水部分  \n\n几个应注意的影响因素如下。  \n\na.聚乙二醇用量大，醇酸树脂分散性强，但引起漆膜发黏。所以只要能使分散体稳定，聚乙二醇量应尽量低。  \n\nb.其他原料的类型与数量影响亲水、憎水基团的比例，所以也影响分散性。例如增加油度降低分散性，原因是憎水基团增多。  \n\nc.溶剂的作用，两性溶剂（可溶于水与烃类）有很大作用，它可降低分散粒度，提高分散体稳定性，同时可减少聚乙二醇在醇酸树脂中的比例，因此可提高漆膜硬度与耐水性。溶剂的效果可进行以下试验：在揽拌下向含有分散不良的树脂的水中慢慢加入溶剂（水与树脂之比为 $1:1)$ ，溶剂缓缓增加，树脂由粗颗粒变成均匀白色圆粒乳液，颗粒继续变小至$0.5\\mu\\mathrm{m}$ 以下，再变成半透明直至最后透明。溶剂用量随溶剂的种类、树脂的种类而异。一般情况正丁醇和乙二醇单丁醚较好。虽然聚乙二醇改性醇酸树脂可以自分散，但加入少量溶剂有很大好处。如上述苯乙烯和聚乙二醇醇酸树脂的 $50\\%$ 水混合物加入树脂量 $10\\%$ 的乙二醇单丁醚，黏度为 $2\\mathrm{d}\\mathsf{P a}\\cdot\\mathsf{s}$ ，粒度 $0.5\\sim1\\mu\\mathrm{m}$ 。可耐多次冻融循环，稀释至固体分为 $10\\%$ 没有析出。不加溶剂，只把树脂加入水中加热，或树脂以氨或胺中和，同样都可以制成相同颗粒的乳液，但稀释不稳定。  \n\n制备醇酸水分散体乳液，转相乳化的操作有两种方法：a.温度转相法（phaseinversiontemperature，PIT)，即先将乳化剂与树脂均匀混合，然后在高于PIT温度条件下，滴加水制成油包水乳液，再降低至PIT温度以下而转相成水包油乳液；b.转相乳化点法（emul-sion inversionpoint，EIP)，即先将乳化剂与树脂均匀混合，然后滴加水制成油包水乳液，提高水的含量而转相成水包油乳液。醇酸树脂的乳化一般采用EIP法，因为该法有如下优点：尽可能降低乳胶粒的尺寸、窄的粒径分布、泡沫少、操作容易、更低的乳化剂用量及良好的稳定性等。  \n\na.工艺参数的确定如乳化剂对醇酸树脂乳液稳定性的影响，乳化剂需要与树脂有相匹配的亲水亲油平衡（RHLB)。用于醇酸树脂乳化的乳化剂有离子型乳化剂（大多数为阴离子）或非离子型乳化剂。经过筛选非离子型乳化剂A和阴离子型乳化剂B按 $35:65$ 的比例混合使用，总用量为 $8\\%$ ，制得稳定的醇酸树脂乳液。  \n\nb.搅拌转速及方式对乳液性能的影响合适的乳化机械不仅可提高乳化的效率，还可以制得更微细的分散颗粒从而提高乳液的稳定性。将水分散在树脂中，重要的是揽拌的模式而不是速度，使整个物料混合均匀而不能有死角。常用的是锚式搅拌桨，它与釜底和釜壁间隙小，转速为 $3000\\tau/\\mathrm{{min}}$ 票  \n\nc.乳化温度对乳液性能的影响乳化温度也是制备稳定乳液的一个关键因素。EIP法是在W/O乳液形成后继续提高水的含量到转相成O/W乳液。转相时的水/油称为乳液转相点（EIP)，用非离子型乳化剂时，EIP与温度有关。用离子型乳化剂时，EIP与温度无关。  \n\n用含聚乙二醇链段的离子型乳化剂时，EIP也受温度影响，但可以利用此影响来提高必要的操作温度。水体积分数和温度与相的关系如图2-1-5所示。  \n\n图中描述了转相时水相体积分数与温度的关系。图中有一个很宽的滞后区，这会使转相后的乳液有不同的固含量。在接近温度转相点（PIT）时界面张力极小，用EIP法可制得分散良好的O/W乳液。由于在PIT前后，体系的电导、黏度和界面张力均有突变，可用电导率仪测得PIT，在比它稍低的温度（ $70^{\\circ}\\mathrm{C}$ ）下进行EIP法乳化，可得到分散良好的O/W乳液。采用EIP法制成的稳定的醇酸树脂乳液，其成膜性能与油性醇酸树脂相当。  \n\n![](images/c4dda85311a65a11194ab621cdfe7d19617c00cab2bc8b7b7006f3d36e87642b.jpg)  \n图2-1-5水体积分数和温度与相的关系  \n\n水分散的醇酸漆比乳胶漆有本质上的优越性，乳胶漆的聚合物是热塑性的，必须加成膜助剂来降低颗粒黏度，以获得良好的成膜品质。而水分散的醇酸漆的颗粒黏度低，能很好地聚结、融合和链段的相互扩散；氧化交联速率很慢，因而不干扰成膜品质，所以漆膜的整体性好。水性醇酸漆的缺点，主要是贮存稳定性差，贮存后的干性失落较大。醇酸树脂含有易水解的酯键，水还能与催干剂中的金属离子配合，降低了催干剂的效果。  \n\n改性醇酸树脂可按照一般制色漆方法制成色漆。水分散性漆有较好的贮存性，虽贮存略有增稠，但稍稀释就能施工，而且性能良好。改变配方和制造方法可制成不同品种树脂和漆。  \n\n$\\textcircled{2}$ 水可分散性醇酸树脂水性醇酸树脂大多是阴离子型。使树脂具有侧链羟基的方法有多种。  \n\n![](images/33862fdf26750b1165df1fa2fdf3041875d4451b420c27e5cc32deb4b3060801.jpg)  \n\na.使醇酸树脂脂肪酸的不饱和双键与含羟基烯类单体（甲基丙烯酸、丙烯酸）共聚。此法含有丙烯酸的自聚物，可与醇酸树脂在水中共溶，但漆膜不透明或浑浊。  \n\nb.使用2,2-二羟甲基丙酸（DMPA) $\\mathrm{CH}_{3}{\\mathrm{-C}}(\\mathrm{CH}_{2}\\mathrm{OH})_{2}{\\mathrm{-COOH}}$ 。有两个羟甲基可以在酯化中参加反应形成链状结构，而其羧基却由于位阻效应不参加合成树脂的酯化反应，这样在合成醇酸树脂时起到二元醇的作用而且提供侧链羧基，可惜此原料来源还不多。  \n\nc.使用偏苯三甲酸酐或均四苯甲酸酐。偏苯三甲酸酐（TMA）有三个羧基，其中两个羧基形成酐与苯二甲酸酐相似，第三个羧基与间苯二甲酸、对苯二甲酸的第二个羧基相似，结构式如下：  \n\n![](images/f0b8040db38df3aacde5b5a42611f40f470e14cae1ea5d58bc9479198f4516aa.jpg)  \n\n偏苯三甲酸酐酯化反应速率比间苯二甲酸或对苯二甲酸快，介于邻苯二甲酸酐与顺丁烯二酸酐之间，顺序为：对苯二甲酸<间苯二甲酸<邻苯二甲酸酐<偏苯三甲酸酐<顺丁烯二酸酐。偏苯三甲酸酐或均四苯甲酸酐的官能度很高，如果与其他多元醇、多元酸一起在高温下进行酯化必将导致胶化。水可分散性醇酸树脂的制造方法与-般溶剂型醇酸树脂有所不同。先将偏苯三甲酸酐以外的原材料进行酯化，至酸值达到10mgKOH/g以下，制成预聚酯再加偏苯三甲酸酐在 $160{\\sim}170^{\\circ}\\mathrm{C}$ 反应。此时偏苯三甲酸酐的酐基具有活性可以开环反应，而其另-羧基并不反应，形成带有侧链羧基的醇酸树脂，经氨或胺中和后先溶于助溶剂中，然后分散于水中。加入催化剂可以干燥。结构式如下：  \n\n![](images/c28cb4b70bd6191e031f9654a240c2dc2fd157caaa1fae106fcced3f62ed9404.jpg)  \n\\~代表脂肪酸基  \n\n如为不饱和脂肪酸（如亚麻油脂肪酸)，则水可分散性醇酸树脂可以空气氧化自干；如为无油或饱和脂肪酸，则醇酸树脂可以氨基树脂烘烤固化。此时醇酸树脂含羟基较多，所以固化也通过两个树脂之间的酯化反应完成。均四苯甲酸酐有两个酐基，即使在低温下也要凝胶化，所以用量要谨慎。  \n\n下述为溶剂型与水可分散性醇酸树脂的比较。   \n水可分散性醇酸树脂与常规醇酸树脂的比较见表2-1-43。  \n\n表2-1-43水可分散性醇酸树脂与常规醇酸树脂的比较   \n\n\n<html><body><table><tr><td>项目</td><td>常规中油度亚麻 油醇酸树脂</td><td>水可分散性中 油度亚麻油 醇酸树脂</td><td>项目</td><td>常规中油度亚麻 油醇酸树脂</td><td>水可分散性中 油度亚麻油 醇酸树脂</td></tr><tr><td>组分/%</td><td></td><td></td><td>油漆溶剂油</td><td>140</td><td>一</td></tr><tr><td>碱源亚麻油</td><td>550</td><td>一</td><td>水</td><td>一</td><td>485</td></tr><tr><td>亚麻油脂肪酸</td><td>一</td><td>456</td><td>氨水(28%)</td><td></td><td>25</td></tr><tr><td>三羟甲基丙烷</td><td>179</td><td>277</td><td>环烷酸钴(6%)</td><td>3</td><td>4</td></tr><tr><td>氧化铅</td><td>0.2</td><td>一</td><td>环烷酸铅（24%)</td><td>4</td><td></td></tr><tr><td>间苯二甲酸</td><td>294</td><td>264</td><td>环烷酸锰(6%)</td><td>一</td><td>2</td></tr><tr><td>偏苯三甲酸酐</td><td>一</td><td>87</td><td>活性剂Active-8</td><td>一</td><td>1</td></tr><tr><td>苯甲酸</td><td>48</td><td>一</td><td>防结皮剂</td><td>1</td><td></td></tr><tr><td>合计</td><td>1071.2</td><td>1084</td><td>性质</td><td></td><td></td></tr><tr><td>反应出水</td><td>-71.2</td><td>-84</td><td>开始pH</td><td>一</td><td>7.5~8.5</td></tr><tr><td>树脂得量</td><td>1000.0</td><td>1000.0</td><td>不挥发分/%</td><td>56</td><td>42</td></tr><tr><td>性质</td><td></td><td></td><td>黏度（福特-4杯）/s</td><td>35~40</td><td>40~50</td></tr><tr><td>酸值（固体）/(mgKOH/g)</td><td>11~13</td><td>55~60</td><td>颜料·成膜物质</td><td>0.8  1.0</td><td>0.8~1.0</td></tr><tr><td>颜色（加氏）</td><td>6~8</td><td>6~8</td><td>漆膜性能</td><td></td><td></td></tr><tr><td>不挥发分/%</td><td>50</td><td>80</td><td>指触干/h</td><td>1.5</td><td>0.5</td></tr><tr><td>挥发分</td><td>油漆溶剂</td><td>丙基丙二醇</td><td>指压干/h</td><td>3.4</td><td>4.0</td></tr><tr><td>凝胶化点(200℃)/s</td><td>18~22</td><td>18~22</td><td>干硬/h</td><td>5.0</td><td>5.0</td></tr><tr><td>制白磁漆</td><td></td><td></td><td>铅笔硬度，干1天</td><td>5B</td><td>5B</td></tr><tr><td>配方</td><td></td><td></td><td>铅笔硬度，干7天</td><td>B</td><td>HB</td></tr><tr><td>二氧化钛</td><td>244</td><td>192</td><td></td><td></td><td></td></tr><tr><td>醇酸树脂</td><td>560(50%)</td><td>321(80%)</td><td></td><td></td><td></td></tr></table></body></html>\n\n①Active-8为1，10-菲咯啉溶液（溶于50%正丁醇中），为助催干剂。  \n\na.原料变动的影响三羟甲基丙烷、三羟甲基乙烷效果相同；但甘油制成的醇酸树脂稳定性不佳。在二元酸方面，间苯二甲酸较好，邻苯二甲酸酐使醇酸树脂分子量降低，干燥时间长且硬度较低。用间苯二甲酸的醇酸树脂虽然附着力较苯酐稍差，但硬度、耐冲击性、耐水性都有所提高。如用顺丁烯二酸酐改性，可与不饱和脂肪酸加成，增加了漆膜的交联度，提高硬度，降低吸水率。但顺丁烯二酸酐的用量不宜超过 $10\\%$ ，以 $6\\%$ （质量分数）最佳。  \n\n豆油脂肪酸和苯甲酸的摩尔比为 $1:1$ ，水接触角为 $96.3^{\\circ}$ ，耐水性较好。  \n\nb.中和剂与助溶剂的影响以亚麻油脂肪酸和亚麻酸制作为例，见表2-1-44、表2-1-45。挥发性低的胺作为中和剂时干燥慢；助溶剂应有好的溶解性，挥发性大者，干燥快。  \n\n表2-1-44中和剂的影响  \n\n\n<html><body><table><tr><td rowspan=\"2\">中和剂</td><td rowspan=\"2\">脂肪酸</td><td rowspan=\"2\">指触法/min</td><td rowspan=\"2\">指压法/h</td><td rowspan=\"2\">干硬/h</td><td colspan=\"2\">铅笔硬度</td></tr><tr><td>干1天</td><td>干7天</td></tr><tr><td rowspan=\"2\">NHOH</td><td rowspan=\"2\">亚麻油脂肪酸 亚油酸</td><td>25</td><td>4</td><td>6</td><td>5B</td><td>HB</td></tr><tr><td>25</td><td>4</td><td>6</td><td>5B</td><td>HB</td></tr><tr><td rowspan=\"2\">兰乙胺</td><td rowspan=\"2\">亚麻油脂肪酸</td><td>3.35</td><td>55</td><td></td><td></td><td></td></tr><tr><td></td><td></td><td>1010</td><td>BB</td><td>HB</td></tr><tr><td rowspan=\"2\">二甲基乙醇胺</td><td rowspan=\"2\">亚麻油脂肪酸 亚油酸</td><td>45</td><td></td><td></td><td></td><td></td></tr><tr><td>45</td><td>7 7</td><td>14 14</td><td>5B 5B</td><td>2B 2B</td></tr></table></body></html>  \n\n表2-1-45助溶剂的影响  \n\n\n<html><body><table><tr><td rowspan=\"2\">助溶剂</td><td rowspan=\"2\">脂肪酸</td><td rowspan=\"2\">指触法/min</td><td rowspan=\"2\">指压法/h</td><td rowspan=\"2\">干硬/h</td><td colspan=\"2\">铅笔硬度</td></tr><tr><td>干1天</td><td>干7天</td></tr><tr><td rowspan=\"2\">乙二醇单丁醚</td><td rowspan=\"2\">亚麻油脂肪酸 亚油酸</td><td>25</td><td>4</td><td>6</td><td>5B</td><td>HB</td></tr><tr><td>25</td><td>4</td><td>6</td><td>5B</td><td>HB</td></tr><tr><td rowspan=\"2\">丙二醇单甲醚</td><td rowspan=\"2\">亚麻油脂肪酸 亚油酸</td><td>20</td><td>1.5</td><td>4</td><td>5B</td><td>HB</td></tr><tr><td>20</td><td>1.5</td><td>4</td><td>5B</td><td>HB</td></tr><tr><td rowspan=\"2\">丙二醇单丙醚</td><td rowspan=\"2\">亚麻油脂肪酸 亚油酸</td><td>20</td><td>1.5</td><td>4</td><td></td><td></td></tr><tr><td>20</td><td>1.5</td><td>4</td><td>5B 5B</td><td>HB HB</td></tr></table></body></html>\n\n① NHOH中和,  \n\nc.油度变化的影响将前面油度 $50\\%$ 的水可分散性醇酸树脂改为油度为 $40\\%$ 。短油度水性醇酸树脂，树脂以 $\\mathbf{NH}_{4}\\mathbf{OH}$ 为中和剂，以丙基丙二醇醚为助溶剂。可见缩短油度改进了干率与硬度，但需要脂肪酸有较高的不饱和度，如亚油酸、亚麻油脂肪酸。豆油脂肪酸则对干率的改进不多。  \n\n【例】 $40\\%$ 油度水可分散性醇酸树脂氨基漆  \n\n水性醇酸树脂的合成分成两步：缩聚反应与水性化。缩聚反应是将苯酐、月桂酸、间苯二甲酸、三羟甲基丙烷及二甲苯，加入四口瓶中并通氮气保护，加热升温至 $140\\%$ ，慢速揽拌，1h升温至 $180^{\\circ}\\mathrm{C}$ 保温约1h，继续升温到 $230\\Upsilon$ ，1h后测酸值，当酸值降至小于$10\\mathrm{mgKOH/g}$ 时，蒸发溶剂，降温至 $170\\%$ ，加入偏苯三甲酸酐，酸值控制在 $50\\sim$ $60\\mathrm{{mgKOH/g}}$ ，停止反应降温至 $120\\mathsf{C}$ 。  \n\n水性化：按 $85\\%$ 固含量加入乙二醇单丁醚溶解，继续降温至 $70^{\\circ}\\mathrm{C}$ ，按羧基 $80\\%$ 的物质的量加人二甲基乙醇胺，中和1h；按 $50\\%$ 固含量加入蒸馏水，搅拌0.5h，过滤得水性醇酸树脂。  \n\n水性醇酸树脂的技术指标见表2-1-46。  \n\n表2-1-46水性醇酸树脂的技术指标  \n\n\n<html><body><table><tr><td>项 目</td><td>技术指标</td><td>项 目</td><td>技术指标</td></tr><tr><td>外观</td><td>淡黄色透明液体，无可见杂质</td><td>黏度（涂-4杯）/s</td><td>100~150</td></tr><tr><td>固含量/% pH</td><td>50 7.5~8.5</td><td>油度/%</td><td>40</td></tr></table></body></html>  \n\n制漆工艺：将HMMM加入计量好的水中，搅拌下依次加入除增稠剂以外的助剂、钛白粉混合均匀，加入水分散性醇酸树脂，研磨至 $20\\mu\\mathrm{m}$ 以下，过滤后，加增稠剂调整黏度。烘烤条件是 $180^{\\circ}\\mathrm{C}$ ， $30\\mathrm{min}$ 营  \n\n原材料的选择：偏苯三甲酸酐与苯酐之比为 $^\\textrm{\\scriptsize1:3}$ （摩尔比）；三羟甲基丙烷有三个伯羟基，活性大，反应平稳，烷基支链对酯基的屏蔽作用，提高了树脂的水解稳定性；水性化单体选择偏苯三甲酸酐，其用量可根据最终酸值的要求计算或优化；研究发现油度以 $40\\%$ 为好，此时的羟值约为 $120\\mathrm{mgKOH/g}$ ；最终酸值控制在 $50{\\sim}60\\mathrm{mgKOH/g}$ 较好；此试验的水性醇酸树脂和HMMM的质量比为 $1:0.3$ ；水性涂料体系助剂的选择和用量非常重要，应优选并确定最佳用量。  \n\n【例】自干水可分散性醇酸树脂涂料  \n\n自干水可分散性醇酸树脂合成工艺：按配方将亚麻油酸、苯甲酸、三羟甲基丙烷、间苯二甲酸、顺丁烯二酸酐和回流二甲苯投入反应釜中，升温到 $180^{\\circ}\\mathrm{C}$ 保温1h；当出水量变慢时，以 $10\\%$ 的升温速度均匀升温到 $230^{\\circ}\\mathrm{C}$ 左右保温酯化，至酸值不大于 $12\\mathrm{mgKOH/g}$ \\*冷却降温至 $170^{\\circ}\\mathrm{C}$ 时，加入偏苯三甲酸酐，在 $170{\\sim}180\\mathrm{\\textperthousand}$ 保温至酸值 $50{\\sim}55\\mathrm{mgKOH/g}$ ；降温真空抽去回流二甲苯，冷却后加入乙二醇单丁醚兑稀备用。  \n\n水性醇酸树脂涂料主要技术指标见表2-1-47。  \n\n表2-1-47水性醇酸树脂涂料主要技术指标  \n\n\n<html><body><table><tr><td>项 目</td><td>检测结果</td><td>目 项</td><td>检测结果</td></tr><tr><td>黏度[（涂-4杯，（25±1）℃）]/s</td><td>72</td><td>附着力（划圈法）/级</td><td>1</td></tr><tr><td>表干/min</td><td>40</td><td>耐盐水性</td><td>48h不起泡、不生锈</td></tr><tr><td>实千/h</td><td>15</td><td>耐盐雾性</td><td>240h不起泡、不生锈</td></tr><tr><td>硬度（摆杆）</td><td>0.45</td><td></td><td></td></tr></table></body></html>  \n\n分析与讨论：综合考虑油度以 $45\\%\\sim50\\%$ 较好；苯甲酸的用量为 $4\\%\\sim7\\%$ ；顺丁烯二酸酐用量不宜超过 $10\\%$ ；确定树脂的酸值为 $50{\\sim}55\\mathrm{mgKOH/g}$ ，用氨或胺中和能溶于水且漆膜有较好的性能。  \n\n$\\textcircled{3}$ 水性醇酸树脂的配方设计及实验优化水性醇酸树脂的配方设计是在溶剂型醇酸树脂配方基础上，结合水性化的具体条件设计出来的，主要适于成盐法合成水性醇酸树脂。在水性醇酸树脂的配方设计中，醇酸树脂常数 $\\kappa$ 、油度OL和醇超量 $\\boldsymbol{r}$ 是三个重要的工艺参数。树脂的最终酸值AN可用来检验该体系所得的醇酸树脂具有水溶性。  \n\n醇酸树脂常数 $\\kappa$ 表示树脂凝胶时间的酯化程度。  \n\n$$\nK=\\frac{n_{0}}{n(\\mathrm{\\boldmath~A~})}=1\\quad.\n$$  \n\n式中 $n_{0}$ —体系中酸和醇的总物质的量；  \n\nn（A）—酸总物质的量。  \n\n$\\scriptstyle K=1$ 意味着理论上酯化反应可以进行到 $100\\%$ $K{>}1$ 意味着理论上该醇酸树脂体系不会发生凝胶化； $\\kappa{<}1$ 则过早凝胶。通常的醇酸树脂体系采用的 $\\kappa$ 在 $_{1\\sim1.05}$ 之间。油度 $O L$ 表示不饱和脂肪油（酸）在所得树脂产量中所占的质量百分比。  \n\n脂肪油（脂肪酸） $\\scriptstyle\\displaystyle\\mathop{=}\\frac{O L}{1-O L}$ （多元醇用量十多元酸用量一理论生成的水）  \n\n醇超量 $\\boldsymbol{r}$ 是醇酸树脂原料中多元醇羟基对多元酸羧基过量的物质的量比，设 $R$ 为多元醇羟基对多元酸羧基的物质的量比，则：  \n\n$$\nr=R-1{=}\\frac{n({\\mathrm{-OH}})}{n({\\mathrm{-COOH}})}{-}1\n$$  \n\n树脂的最终酸值 $_{A N}$ 主要由偏苯三甲酸酐中不参与反应的第三个羧基提供，另外还包括酯化反应中未反应的羧基。AN一般控制在 $40{\\sim}70\\mathrm{mgKOH/g},$ 瓶  \n\n设 $n_{\\mathrm{Al}}$ 表示油的物质的量， $n_{A2}$ 表示二元酸的物质的量， $n_{A3}$ 为偏苯三甲酸酐的物质的量， $M_{\\mathrm{od}}$ 为油的摩尔质量，R为羟基与羧基的物质的量比， $_x$ 为多元醇的官能度， $\\scriptstyle{\\pmb{\\mathscr{p}}}$ 为酯化反应程度，则有以下几项。  \n\n$$\n\\begin{array}{r l r}{\\lefteqn{K=n_{0}/n(\\mathrm{A})=(n_{\\mathrm{Al}}+n_{\\mathrm{A2}}+3n_{\\mathrm{Al}}+2R n_{\\mathrm{A2}}/x)/(2n_{\\mathrm{A2}}+3n_{\\mathrm{Al}})}}\\\\ &{}&{R=\\left[K(2n_{\\mathrm{A2}}+3n_{\\mathrm{Al}})-n_{\\mathrm{Al}}n_{\\mathrm{A2}}-3n_{\\mathrm{Al}}\\right]x/2n_{\\mathrm{A2}}}\\end{array}\n$$  \n\n若配方中多元酸用量 $n_{A2}=1\\mathrm{mol}$ ，则：  \n\n$$\nR{=}[n_{\\mathrm{A1}}(3K{-}4){+}2K{-}1]x/2n_{\\mathrm{A2}}\n$$  \n\n若多元醇为三元醇，则 $\\scriptstyle x=3$ ，当 $\\scriptstyle K=1$ 时，可得；  \n\n$$\nR{=}3/2(1{-}n_{\\mathrm{Al}})\n$$  \n\n若多元醇为四元醇，则 $\\scriptstyle x=4$ ，当 $\\scriptstyle K=1$ 时，可得：  \n\n$$\nR{=}2(1{-}n_{\\mathrm{Al}})\n$$  \n\nb.油度 $O L{=}(n_{\\mathrm{A1}}M_{\\mathrm{oil}})$ /树脂理论产量  \n\n式（7)得：式（8）  \n\n$$\n\\begin{array}{c}{{A N/\\mathrm{O}^{2-}=\\bigl[n_{\\mathrm{A}3}+2R n_{\\mathrm{A}2}\\times(1-p)\\bigr]\\times56100/(n_{\\mathrm{A}1}\\times M_{\\mathrm{oil}})}}\\\\ {{n_{\\mathrm{A}3}=\\displaystyle\\frac{1}{56100}\\times\\frac{A N}{O L}\\times n_{\\mathrm{A}1}\\times M_{\\mathrm{oil}}-2n_{\\mathrm{A}1}\\times(1-p)}}\\end{array}\n$$  \n\n则  \n\n设nA2=1mol，则nA356100×L $n_{A3}=\\frac{1}{56100}\\times\\frac{A N}{O L}\\times n_{\\mathrm{Al}}\\times M_{\\mathrm{oil}}-2\\times(1-p)$  \n\n最终酸值可以根据水分散性的要求自己设定；在溶剂型醇酸树脂的合成中，短油度的反应程度 $\\pmb{\\mathscr{p}}$ 一般为0.85，中油度一般为0.9，长油度一般为0.95。这样，对于原料确定，已知油度的醇酸树脂，就可以根据以上 $\\kappa$ 值、油度 $_{O L}$ 和酸值 $A V$ 三个方程，计算出水性醇酸树脂的理论配方。  \n\n如果采用熔融聚合成盐法，按以上理论配方合成水性醇酸树脂，则性能很差。经多次试验， $40\\%$ 油度的麻油合成醇酸树脂，醇超量在 $25\\%$ ，PA/TMA $=5$ 时，配方的综合性能较好。调整后的配方见表2-1-48。  \n\n表2-1-48调整后的配方  \n\n\n<html><body><table><tr><td colspan=\"2\">成分</td><td>加料量/g</td><td>n(A)/mol</td><td>n(G)/mol</td><td>no/mol</td><td>树脂成分/%</td></tr><tr><td rowspan=\"2\">麻油脂肪酸部分</td><td>甘油部分</td><td rowspan=\"2\">166.01</td><td>0.537</td><td>0.179</td><td>0.179</td><td>40</td></tr><tr><td>111.67 123.28</td><td>1.667</td><td>2.500</td><td>0.537 0.833 0.833</td><td>26.91 29.70</td></tr></table></body></html>  \n\n$\\textcircled{4}$ 水性醇酸树脂水解稳定性的研究进展水性醇酸树脂的一个缺点是由于它的主链中的酯键易水解，贮存稳定性不好。鉴于此，涂料行业探索“核-壳”醇酸树脂技术，使用丙烯酸聚合物包覆醇酸。试验表明，提高壳聚合物的含量，水解率明显降低。然而，通过这个方法完全阻止水解却不大可能。降低酯键水解最有效的办法是在它的周围制造一个憎水的环境，使水分子难以进入酯键中。研究表明，通过使用仲醇和叔醇可以大大降低水解率。W．威克斯在《有机涂料科学和技术》一书中也提到使用仲醇提高水性醇酸树脂的稳定性。  \n\n![](images/e62edb343e0b3995f11750571e75ac5133445e3fee3c13dc577accb0ad327f88.jpg)  \n伯羟基形成的酶易水解  \n\n![](images/266cf6553318e03ba199824b8f3a8c6aa0837d1ff30286e98b71dad20d5cb147.jpg)  \n仲、叔羟基形成的酯阻碍水解  \n\n虽然使用叔醇会赋予醇酸最好的水解稳定性，然而仲醇易得，并且与酸易反应。用仲醇对其测试的结果显示，随仲醇基成分的增加，酯键的水解率相应下降  \n\n![](images/2f4ade464daf39f21ae059398e49fc90b82c9994cc47d723dbc9e892bd122be6.jpg)  \n图2-1-6仲羟基的含量对酯键水解的影响  \n\n2-1-6)。通过在“核-壳”形态的醇酸树脂合成中，引人仲醇的酯结构，可制备具有优异贮存稳定性的水性醇酸树脂。这种新型树脂制备的涂料在加热贮存数周后，各项性能均没下降，并且比传统的溶剂型醇酸涂料的性能好。在兼有传统的醇酸体系高光泽外观和优异流平性的同时，此种新型树脂与传统的水稀释性醇酸树脂相比，还有更低的VOC、更好的黏度稳定性和水解稳定性。这为水稀释性醇酸树脂的发展提供了新的途径。  \n\n(6）苯乙烯改性醇酸树脂醇酸树脂的漆膜有良好的耐候性、附着力，但干燥慢，耐水性、耐化学药品性差。聚苯乙烯树脂具有优良的耐水性、耐化学药品性、电绝缘性。如以苯乙烯单体来改性醇酸树脂将使醇酸树脂兼有两种材料的特性。聚苯乙烯不溶于油及醇酸树脂，但苯乙烯单体则易与含共轭双键的脂肪酸共聚，反应甚快，而与非共轭双键的脂肪酸反应则共聚很慢，反应程度很低。例如：苯乙烯与桐油很快地共聚、胶化；与脱水麻油（含共轭双键 $25\\%$ 左右）共聚较慢；与亚麻油、豆油（无共轭双键）则共聚极慢，苯乙烯将自聚成聚苯乙烯而与油分离。在共聚反应时几个反应可能同时发生，即自聚与共聚，以反应最快的为主反应。一般认为苯乙烯自己先聚合，使链增长至一定的程度，增长的聚苯乙烯链又与油的脂肪酸上的不饱和基相联结；也可能这个增长的聚苯乙烯链与两个油的脂肪酸基相联结。共聚机理是以苯乙烯与共轭双键的狄尔斯-阿尔德(Diels-Alder）反应为基础，其反应主要为1，4及1，2加成，以1，4为主。如引发剂为过氧化苯甲酰，先分解：  \n\n![](images/a19cdeee3099c1d03b8c1da561baa90046f8f7e634c6e5bbe460e67907308af3.jpg)  \n\n引发苯乙烯单体：  \n\n![](images/99e5b9c59ac730a7c1d1fb0818e8fb5bfacd811662fed6fa64e8e5ca82947f68.jpg)  \n\n![](images/5fdba07c71a418f28b20d7d99a6a150c5c4f56a2ae70de753d9bb2d0fac22956.jpg)  \n\n桐油脂肪酸与苯乙烯的共聚物中，苯乙烯与桐油脂肪酸的摩尔比平均为 $4.75:1$ ，上式为1，4加成。对于脱水麻油也是1，4加成。因为脱水麻油脂肪酸内有 $25\\%$ 左右的脂肪酸为共轭双键。桐油脂肪酸 $90\\%$ 以上具有共轭双键结构，所以共聚胶化很快。亚麻油脂肪酸、豆油脂肪酸无共轭双键则共聚困难。人们也可以看到在共聚的同时消耗了脂肪酸的双键，亦即降低了脂肪酸的不饱和度，影响以后的氧化聚合的交联程度。  \n\n在生产苯乙烯改性醇酸树脂时，可采取两种方法：一种为先以苯乙烯改性原料，即改性脂肪酸和醇解后的油再制成醇酸树脂；另一种为先制好醇酸树脂，然后再以苯乙烯改性。一般多采用后者，因易于控制，产品性能好。按后一方法制的苯乙烯改性醇酸树脂，又按脂肪酸分为两类：一类是含有共双键的脂肪酸，此方法有双键的损耗；另一类是不含共轭双键的脂肪酸，如亚麻油、豆油等，加入一些顺丁烯二酸酐，以顺丁烯二酸的双键与苯乙烯共聚。  \n\n聚苯乙烯与油、醇酸树脂都不融合，所以在苯乙烯自聚之前至少要把一部分苯乙烯结合到醇酸树脂结构中去，这样可以增加对小分子量的聚苯乙烯的溶解性。共聚效果好的标志为完全透明，不浑浊。  \n\n共聚前的醇酸树脂的分子量不能制得过大，要酯化程度稍低，酸值稍大，否则将在共聚过程中胶化或贮存时不稳定。  \n\n$\\Phi$ 共轭双键脂肪酸的油用含共轭双键脂肪酸的油，制苯乙烯改性醇酸树脂。设计配方时不需使含共轭双键的油的用量过大，应用其他油类将其冲淡，如豆油与脱水麻油 $3:1$ (质量比)。 $\\kappa$ 值也要大一些，可用到1.04，因苯乙烯改性后黏度要增加很多。  \n\n配方（质量分数）/%  \n\n豆油 45.5 苯二甲酸酐 23.0   \n脱水麻油 15. 5 季戊四醇 修 16.0  \n\n酯化时酸值不要过低， $15\\mathrm{mgKOH/g}$ 即可。如果要用大量的含共轭双键的油，则 $\\kappa$ 值还要增大，以免黏度过大或胶化。  \n\n配方（质量分数）/%  \n\n<html><body><table><tr><td>脱水麻油</td><td>60.0 甘油</td><td></td><td>14.3</td></tr><tr><td>苯二甲酸酐</td><td>25.7 K</td><td></td><td>1.09</td></tr></table></body></html>  \n\n表2-1-49是苯乙烯改性亚麻油、桐油醇酸树脂的配方和性能举例。  \n\n在实验室内苯乙烯改性的操作可以在装有温度计、搅拌器、取样管、回流冷凝器等的三口瓶内进行。先将醇酸树脂、二甲苯加入三口瓶内，升温，搅拌，至反应物产生回流。将二叔丁基过氧化物（苯乙烯量的 $2.5\\%$ ）溶于新蒸馏的苯乙烯中，自回流冷凝器的上口滴人反应器中。在1h内加完，保持回流，回流温度逐渐升到 $150\\mathrm{^c}$ 保持不变。在此期间，不断取样测转化率。测定方法为取样在 $150^{\\circ}\\mathrm{C}$ 通风烘箱中烘 $30\\mathrm{{min}}$ ，测其残留物的质量。此质量与理论苯乙烯100%聚合时应有的质量的比值，即为转化率。保持6h后再滴人为苯乙烯量的$0.5\\%$ 的二叔丁基过氧化物二甲苯溶液，继续保持至转化率达到 $95\\%$ 以上。表2-1-50为苯乙烯改性醇酸树脂。  \n\n表2-1-49亚麻油、桐油醇酸树脂配方和性能  \n\n\n<html><body><table><tr><td>项 目</td><td>醇酸树脂-1</td><td>醇酸树脂-2</td><td>项 目</td><td>醇酸树脂-1</td><td>醇酸树脂-2</td></tr><tr><td>配方/% 亚麻油 桐油 季戊四醇</td><td>570.0 30.0 140.0</td><td>563.0 29.0 140.0 0.5</td><td>时间/min 酯化 温度/C</td><td>75</td><td>80</td></tr></table></body></html>  \n\n表2-1-50苯乙烯改性醇酸树脂  \n\n\n<html><body><table><tr><td>项 目</td><td>醇酸树脂-1醇酸树脂-2</td><td></td><td>项目</td><td>醇酸树脂-1</td><td>醇酸树脂-2</td></tr><tr><td>配方/%</td><td></td><td></td><td>颜色（铁钻比色计）/号</td><td>7</td><td>7</td></tr><tr><td>醇酸树脂</td><td>200</td><td>200</td><td>酸值/（mgKOH/g)</td><td>9.0</td><td>8.7</td></tr><tr><td>苯乙烯</td><td>133</td><td>133</td><td>反应时间/转化率</td><td>3. 25h/73.4%1.85h/28.2%</td><td></td></tr><tr><td>二甲</td><td>222</td><td>222</td><td></td><td>5. 85h/80.2%5.50h/86.2%</td><td></td></tr><tr><td>二叔丁基过氧化物</td><td>3.99</td><td>3.99</td><td></td><td>7. 10h/87.0%8.40h/93.3%</td><td></td></tr><tr><td>反应终止时黏度（加氏管，25℃）/s</td><td>68~90</td><td>19~26</td><td>改性树脂中苯乙烯含量/%</td><td>36.70</td><td>38.2</td></tr><tr><td>黏度（50%不挥发分）/s</td><td>19</td><td>8</td><td></td><td></td><td></td></tr></table></body></html>\n\n①二叔丁基过氧化物系苯乙烯量的3%，第一小时先加2.5%，6h后再加0.5%.  \n\n以上两个醇酸树脂溶液加人 $0.03\\%$ Co催干剂，涂成漆膜在 $25\\mathrm{{C}}$ 干燥，性能见表2-1-51。  \n\n表2-1-51苯乙烯改性醇酸树脂的性能  \n\n\n<html><body><table><tr><td>项 目</td><td>醇酸树脂-1</td><td>醇酸树脂-2</td><td>项 目</td><td>醇酸树脂-1</td><td>醇酸树脂-2</td></tr><tr><td>干燥时间</td><td></td><td></td><td>干硬/min</td><td>44</td><td>48</td></tr><tr><td>凝定/min</td><td>9</td><td>12</td><td>弯曲试验（干15天后）/min</td><td>3</td><td>3</td></tr><tr><td>表干/min</td><td>14</td><td>14</td><td>斯氏硬度（干15天后）</td><td>44</td><td>44</td></tr></table></body></html>  \n\n增加苯乙烯的用量将使硬度、干率提高，也使漆膜发脆。改变苯乙烯用量对醇酸树脂的影响见表2-1-52。  \n\n表2-1-52苯乙烯含量对改性醇酸树脂性能的影响   \n\n\n<html><body><table><tr><td>苯乙烯含量/%</td><td>黏度（50%二甲苯溶剂，25℃）/s</td><td>干硬时间/min</td><td>斯氏硬度（干15天）</td><td>弯曲试验</td></tr><tr><td>47.6</td><td>21</td><td>14</td><td>58</td><td>脆裂</td></tr><tr><td>36.7</td><td>19</td><td>44</td><td>44</td><td>3mm，合格</td></tr><tr><td>29.8</td><td>16</td><td>295</td><td>38</td><td>3mm，合格</td></tr></table></body></html>  \n\n聚苯乙烯系热塑性，同时降低了氧化交联的官能度，因此苯乙烯改性醇酸树脂漆膜对溶剂敏感，敏感程度随苯乙烯含量下降而下降。聚苯乙烯的耐水性与耐碱性好，因此赋予改性醇酸树脂漆膜以较好的耐水性与耐碱性。由于共聚消耗了一部分双键，因此改性醇酸树脂的氧化交联度降低，其程度随苯乙烯含量的增加而增加。在干率方面随苯乙烯含量增加，干燥时间短。对干燥后的漆膜进行苯萃取发现，改性醇酸树脂比未改性者苯萃取量大，苯乙烯含量较高者可萃取量也较大。如果用苯乙烯改性醇酸树脂作为底漆，必须使底漆充分交联干透，否则涂刷面会引起咬底。  \n\n$\\textcircled{2}$ 用顺丁烯二酸酐制苯乙烯改性醇酸树脂顺丁烯二酸酐制苯乙烯改性醇酸树脂的优点是：a.可不用含共轭双键的油类，使用亚麻油、豆油及其他油类；b.共聚不消耗不饱和双键。顺丁烯二酸酐在制造醇酸树脂时酯化反应与其他二元酸相同，但本身具有双键可以与苯乙烯共聚。制造醇酸树脂时不能使用含有共轭双键的脂肪酸或油，否则将与顺丁烯二酸酐起加成反应，减弱与苯乙烯聚合的能力，而且在酯化时还将引起胶化。顺丁烯二酸酐的用量较灵敏，过少则双键量不够，产品发浑，或不能共聚，过多则聚合过度以至于胶化。对苯二甲酸酐制醇酸树脂而言，最适宜的量为一个醇酸树脂分子有 $1/3$ 个顺丁烯二酸酐官能度。换言之，即三个醇酸树脂分子具有一个顺丁烯二酸双键，这样可得到均匀透明的苯乙烯改性醇酸树脂。计算方法如下。  \n\n设在缩合反应中每消失一个羧基（酯化)，同时在总摩尔数中也消失1mol，于是在反应到 $\\scriptstyle{\\pmb{\\mathscr{p}}}$ 程度时， $F_{\\mathsf{m A}}$ 可写成：  \n\n$$\nF_{\\mathsf{r e A}}={\\frac{m_{\\mathsf{r e A}}}{m_{0}-(\\phi_{\\mathsf{A}})}}\n$$  \n\n如反应程度 $\\scriptstyle{\\pmb{\\mathscr{p}}}$ 以酸值来表示，则：  \n\n$$\n\\scriptstyle{\\pmb{\\rlap/}{\\hat{\\imath}}}={\\frac{A N_{0}-A N}{A N_{0}}}=1-{\\frac{A N}{A N_{0}}}\n$$  \n\n将上两式合并解 $F_{m\\wedge}$ 得：  \n\n$$\nm_{\\mathrm{reA}}=F_{\\mathrm{reA}}\\left(m_{0}e_{\\mathrm{A}}+{\\frac{e_{\\mathrm{A}}A N}{A N_{0}}}\\right)\n$$  \n\n上式还可改写成：  \n\n$$\nm_{\\mathrm{mA}}=F_{\\mathrm{mA}}\\displaystyle\\epsilon_{\\mathrm{A}}\\left[(K{-}1)+\\frac{A N}{A N_{\\mathrm{0}}}\\right]\n$$  \n\n式中 $m_{0}$ -—反应物总摩尔数；  \n\n$\\scriptstyle m_{\\mathrm{InA}}$ 1 -顺丁烯二酸酐摩尔数；$\\boldsymbol{e}_{\\mathsf{A}}$ E -计算的总当量数；  \n$A N_{0}$ 一反应起始时的酸值(计算值)；  \nAN- 反应至 $\\boldsymbol{\\mathscr{p}}$ 程度时，测得的醇酸树脂的酸值；  \n$F_{\\mathrm{mA}}$ 一 反应至 $\\boldsymbol{\\mathscr{p}}$ 程度时醇酸树脂的顺丁烯二酸酐官能度，即每摩尔醇酸树脂的平均顺丁烯二酸酐基；p—反应程度。款次到的酸值1  \n\n醇酸树脂欲在酸值 $10\\mathrm{mgKOH/g}$ 。 $20\\mathrm{mgKOH/g}$ 时，用苯乙烯改性，则顺丁烯二酸酐用 量的计算见表2-1-53。 o  \n\n表2-1-53豆油醇酸树脂   \n\n\n<html><body><table><tr><td>组分</td><td>加料量/g</td><td>当量值</td><td></td><td></td><td>官能度</td><td>m</td></tr><tr><td>豆油脂肪酸</td><td>840</td><td>280</td><td>3.00</td><td>一</td><td>1</td><td>3</td></tr><tr><td>苯二甲酸酐</td><td>444</td><td>74</td><td>6.00</td><td>一</td><td>2</td><td>3</td></tr><tr><td>甘油(98%)</td><td>300</td><td>31.2</td><td>一</td><td>9.60</td><td>3</td><td>3.2</td></tr><tr><td>合计</td><td>1584</td><td></td><td>9.00</td><td></td><td></td><td>9.20</td></tr></table></body></html>  \n\n$$\nR{=}\\frac{9.60}{9.00}{=}1.07\\qquadK{=}\\frac{9.20}{9.00}{=}1.02\n$$  \n\n酸值为 $10\\mathrm{{mgKOH/g}}$ 时顺丁烯二酸酐的用量为：  \n\n$$\n1/3\\times9\\times{\\Big[}1.021-1+{\\frac{10}{319}}{\\Big]}{\\Big=}0.15{\\bmod{}}\n$$  \n\n酸值为 $20\\mathrm{{mgKOH/g}}$ 时顺丁烯二酸酐的用量为：  \n\n$$\n1/3\\times9\\times{\\Big[}1.021-1+{\\frac{20}{319}}{\\Big]}=0.25{\\bmod{}}\n$$  \n\n计算之后，苯二甲酸酐的量中要减去相当于顺丁烯二酸酐摩尔数的苯二甲酸酐。表2-1-54为酸值分别为 $10\\mathrm{mgKOH/g}$ 。 $20\\mathrm{mgKOH/g}$ 时配方。  \n\n表2-1-54顺丁烤二酸酐醇酸树脂配方   \n\n\n<html><body><table><tr><td rowspan=\"2\">原 料</td><td colspan=\"2\">酸值10mgKOH/g</td><td colspan=\"2\">酸值20mgKOH/g</td></tr><tr><td>加料量/g</td><td>摩尔数/mol</td><td>加料量/g</td><td>摩尔数/mol</td></tr><tr><td>豆油脂肪酸</td><td>840</td><td>3.00</td><td>840</td><td>3.00</td></tr><tr><td>甘油(98%)</td><td>300</td><td>3.20</td><td>300</td><td>3.20</td></tr><tr><td>苯二甲酸酐</td><td>422</td><td>2.85</td><td>407</td><td>2.75</td></tr><tr><td>顺丁烯二酸酐</td><td>14.7</td><td>0.15</td><td>24.5</td><td>0.25</td></tr></table></body></html>  \n\n醇酸树脂的制备可用溶剂法在 $200\\mathrm{\\bar{C}}$ 酯化，约用 $8\\%$ 的二甲苯为回流溶剂，反应11.5h，酸值为 $10\\mathrm{mgKOH/g}$ （固体树脂)，顺丁烯二酸酐的官能度为0.325。苯乙烯改性如下：  \n\n醇酸树脂（含8%溶剂）  \n\n苯乙烯  \n\n反应装置与以前相同，将以上混合物加热至 $125\\mathrm{{^{\\circ}C}}$ ，并每隔1h加异丙苯过氧化氢$\\mathrm{1.45mL}$ （约 $1.5\\mathbf{g})$ 。共加六次，并使聚合反应放热，使回流温度升至 $145\\sim150^{\\circ}\\mathrm{C}$ ，保持回流至第六次引发剂加完，转化率可达 $95\\%$ 。再加入 $145\\mathrm{g}$ 二甲苯，可调整不挥发分至 $65\\%$ 即完毕。  \n\n![](images/a13548761ca694af92d2e5bb29da97ae8b8c9eaba8dde61bab619796a6a718ef.jpg)  \n\n醇酸树脂的改性可通过改变醇酸树脂的配方，调整苯乙烯用量，选用不同的引发剂，选用不同的加苯乙烯与引发剂的方式，制出多种苯乙烯改性醇酸树脂。  \n\n其通性为：a.降低了耐烃类溶剂性，但有涂第二道被稍强溶剂如二甲苯咬起的缺点，因此两道漆间的时间要相隔很近；b.耐水性、耐碱性、干率、硬度都有很大的提高；c.降低了柔韧性与耐候性。苯乙烯改性醇酸树脂可以与颜料配合，制作快干、耐潮、光亮、美观的室内用防护与装饰磁漆、农机用漆。苯乙烯改性醇酸树脂与未改性醇酸树脂不能融合，故不能相并使用；但可加氨基树脂烘烤固化，制作快干、高硬度磁漆。  \n\n（7）丙烯酸（酯）改性醇酸树脂用丙烯酸酯，主要是甲基丙烯酸酯改性醇酸树脂，干燥快，保色性与耐候性都有很大提高。丙烯酸改性醇酸树脂除了氧化干燥成膜外，还可以与氨基树脂或多异氰酸酯树脂进行交联成膜，拓宽了醇酸树脂的应用领域。 m  \n\n改性的方法可分为共聚法与酯化法。  \n\n$\\textcircled{1}$ 共聚法丙烯酸酯单体与苯乙烯单体相同，可以共聚的方法改性醇酸树脂。同样需要带有共轭双键的脂肪酸。其加成也是1，4或1，2加成。例如一个油度为 $40\\%$ 的醇酸树脂进行共聚改性试验。豆油与脱水麻油的用量分别为： $100:0$ . $70:30$ . $50:50$ ；30：70； $0:100$ ，以二叔丁基过氧化物为引发剂与相当于醇酸树脂量 $40\\%$ 的甲基丙烯酸甲酯共聚。 $100\\%$ 豆油者极浑并有结晶物，结晶物系单体自聚物；脱水麻油 $30\\%$ 者共聚后发浑但无结晶物； $50\\%$ 者共聚后依然发浑但制的漆膜是透明的，说明脱水麻油的量不能少于总油量的 $50\\%$  \n\n共聚方法：反应装置与苯乙烯共聚改性醇酸树脂相同。将醇酸树脂加人三口瓶内，搅拌，升温至 $125\\mathrm{{\\circ}}$ 保持 $15\\mathrm{min}$ ，自冷凝器上口滴加甲基丙烯酸甲酯与过氧化二苯甲酰以等量的二甲苯制成的溶液。加完保持回流至转化率达 $95\\%$ 以上，停止反应。真空蒸出未反应的单体和二甲苯，再与二甲苯溶解成 $50\\%$ 固体含量溶液。改性醇酸树脂加颜料与催干剂用于制造各种自干型丙烯酸改性醇酸树脂磁漆。  \n\n$\\textcircled{2}$ 酯化法共聚法制丙烯酸改性醇酸树脂，必须使用含共轭双键的脂肪酸或油类，其他油类特别是饱和脂肪酸制成的醇酸树脂则不能共聚改性。而且共聚改性的醇酸树脂是一个自聚与共聚的混合物，成分不均匀，保色性与烘烤不变色性差。采用酯化法则可以用酯化方法将醇酸树脂用丙烯酸酯改性，而不受油及其他成分的限制。酯化法为先制出分子量较小的聚丙烯酸酯，它们含有羟基、环氧基、羧基，可以与醇酸树脂上的羧基或羟基酯化反应而达到改性的目的。干性油制成的改性醇酸树脂有极好的自干性，因为没有不饱和度的损耗。而且抗再涂二道咬起性也比共聚法制者好。丙烯酸改性醇酸树脂-氨基烘漆作汽车面漆有极好的户外耐久性。丙烯酸酯用量可达 $30\\%$ ，过多将发脆。  \n\n改性方法为先制分子量较低的含有活性官能团的聚（甲基）丙烯酸酯，即（甲基)丙烯酸酯与带活性官能团的（甲基）丙烯酸单体。如甲基丙烯酸缩水甘油酯提供环氧基，甲基丙烯酸羟乙酯提供羟基，甲基丙烯酸提供羧基以及顺丁烯二酸酐提供羧基等单体的共聚物。官能团量过多容易在酯化时胶化，一般用量为总原料量的4%～6%（摩尔分数)。环氧基者可在150℃低温酯化，但单体价格太贵，而且来源也不充足；含羟基者单体也稍贵而且反应较慢。所以实际生产多采用含羧基的聚丙烯酸酯。如使用含羧基聚丙烯酸酯与醇酸树脂直接反应，醇酸树脂本身残留的羧基与羟基也竞相反应（温度 $220\\%$ )，反应难以控制。聚丙烯酸酯与醇酸树脂的缩合程度，可取样滴在玻璃板上看是否透明来观察，但达到透明点的时间与成胶点很接近。因此较好的方法为用“甘油-酸酯法”，即与甘油（或其他多元醇）先行醇解；再将含羧基的聚丙烯酸酯与它进行酯化反应；然后加苯二甲酸酐、甘油(或其他多元醇)，继续酯化制成改性醇酸树脂。此法较成功，产品质量较好。可以下图简示：  \n\n![](images/f106902457b3f855157811bcbacb1371aec87ded894068c48f1d5afdba8c0de6.jpg)  \n\n制备举例：  \n\na.自干型丙烯酸改性醇酸树脂  \n\n【例】  \n\n聚丙烯酸酯配方（质量分数）／%  \n\n<html><body><table><tr><td>甲基丙烯酸甲酯</td><td>384</td><td>过氧化二苯甲酰 8</td></tr><tr><td>甲基丙烯酸</td><td>16</td><td></td></tr></table></body></html>  \n\n将过氧化二苯甲酰溶于以上两单体的混合物中。将混合单体滴加到加热回流与单体总量相等的二甲苯中，以4h加完。继续回流2h。得到共聚物固体分为 $47\\%$ ，加氏黏度Y。  \n\n改性醇酸树脂配方（质量分数）／%  \n\n\n<html><body><table><tr><td>豆油</td><td>747</td><td>聚丙烯酸酯（固体）</td><td>300</td></tr><tr><td>季戊四醇</td><td>172</td><td>苯二甲酸酐</td><td>316</td></tr><tr><td>环 （12%）</td><td colspan=\"3\">2.5</td></tr></table></body></html>  \n\n豆油、季戊四醇与环烷酸铅在 $245\\mathrm{^q}$ 进行醇解至3倍 $95\\%$ 乙醇。冷却，加人聚丙烯酸酯，升温蒸出一部分二甲苯，保持在 $220\\Upsilon$ 酯化至酸值约为 $2\\mathrm{mgKOH/g}$ ，冷却，加入苯二甲酸酐。在 $220\\Upsilon$ 继续酯化。酯化完毕以油漆溶剂油溶解。固体分为 $58.5\\%$ ，加氏黏度V，酸值19. $8\\mathrm{mgKOH/g}$  \n\n此树脂加催干剂按油量的 $0.1\\%0$ 、0. $7\\%96\\%$ (以金属计)。放置过夜，涂膜检测，湿膜厚 $100\\mu\\mathrm{m}$ ，干率2.5h，可涂二道时间为0.5h，清漆的石油溶剂容忍度为 $12\\mathrm{mL}/10\\mathrm{g}$ 。涂第二道咬起问题与油含量有关，油量少则交联度低易被咬起。此配方采取油度 $50\\%$ ，丙烯酸酯 $20\\%$ ，聚酯 $30\\%$ ，来减少咬起并平衡其柔韧性与附着力。此树脂可制各种磁漆。  \n\n据报道，采用单甘油酯法，即先合成含一定量羧基的分子量低的丙烯酸预聚物，然后再与单甘油酯反应，再加入二元酸进一步酯化，合成出表干快、硬度高的自干型丙烯酸改性醇酸树脂。并对影响树脂性能的多种因素进行了探讨。对丙烯酸改性醇酸树脂进行红外线表征。影响自干型丙烯酸改性醇酸树脂性能的因素如下。  \n\n第一，丙烯酸预聚物分子量大小及其分布是控制改性醇酸树脂的关键。分子量过大，后续的酯化反应容易凝胶化；分子量太小，树脂快干但保色、保光等漆膜性能达不到要求。丙烯酸预聚物分子量一般控制在 $3000{\\sim}3500$ 。分子量分布过宽，说明预聚物中单体含量较高，酯化反应过程中有一定量的单体的自聚体产生，这将影响树脂的透明度。  \n\n第二，植物油的选择及油度的影响。采用亚麻油（干性油）与豆油（半干性油）相混合，使树脂具有合适的交联密度。适宜的油度为 $55\\%\\sim60\\%$ 身  \n\n第三，丙烯酸树脂改性量的影响，大量试验表明，适宜的丙烯酸树脂改性量为$20\\%\\sim30\\%$ 9  \n\n第四，第一步酯化反应的程度在一定程度上反映了丙烯酸酯预聚物的接枝率。第一步酯化反应的程度可以通过酯化反应过程中酸值的变化来确定，酸值的变化对表干时间影响不大，而对漆膜的硬度和耐冲击性影响大，酸值在 $5\\mathrm{{\\sim}10m g K O H/g}$ 较好。但当第一步酯化反应的酸值小于 $20\\mathrm{mgKOH/g}$ 时，黏度急剧增大，而最终树脂的酸值也很难降到 $20\\mathrm{mgKOH/\\mathrm{g}}$ 以下。  \n\n自干型丙烯酸改性醇酸树脂清漆的表干为1h，实干为5h，硬度达到0.7，均有较大提高。【例】用丙烯酸改性快干醇酸树脂制成磁漆和底漆也取得较好的效果。自干型丙烯酸改性醇酸树脂性能的合成也是采用酯化法。参考配方见表2-1-55。 76  \n\n表2-1-55 丙烯酸改性醇酸树脂配方   \n\n\n<html><body><table><tr><td>原料名称</td><td>规格</td><td>质量分数/%</td><td>原料名称</td><td>规格</td><td>质量分数/%</td></tr><tr><td>豆油酸</td><td>工业级</td><td>20~25</td><td>苯甲酸</td><td>工业级</td><td>1~4</td></tr><tr><td>季戊四醇</td><td>工业级</td><td>8~12</td><td>催化剂</td><td>试剂级</td><td>0.05~0.10</td></tr><tr><td>丙烯酸共聚物</td><td>自制</td><td>15~30</td><td>二甲苯</td><td>工业级</td><td>16.92~36.98</td></tr><tr><td>苯酐</td><td>工业级</td><td>10~14</td><td></td><td></td><td></td></tr></table></body></html>  \n\n丙烯酸改性醇酸树脂性能的技术指标：  \n\n\n<html><body><table><tr><td>外现</td><td>淡黄清澈透明</td><td>酸值/（mgKOH/g)</td></tr><tr><td>颜色（Fe-Co)/号</td><td>≤8</td><td>固体分/%</td></tr><tr><td></td><td>20~40</td><td></td></tr></table></body></html>  \n\n在共聚物的分子中，用甲基丙烯酸引入羧基。经过试验，确定 $\\alpha$ 甲基丙烯酸用量为$2.5\\%\\sim4\\%$ 。用十二烷基硫醇作为链转移基，其用量为 $0.05\\%\\sim0.10\\%$ 。丙烯酸共聚物用量占丙烯酸改性醇酸树脂的 $25\\%$ ，是既经济性能又好的比例。  \n\n改性醇酸树脂中加人催化剂，反应时间由12h可缩短至 $6\\sim7\\mathrm{h}$ ，催化剂用量为 $0.05\\%\\sim$ $0.10\\%$ 。制成底漆和磁漆后，表干约 $15\\mathrm{min}$ ，实干为15h，而快干磁漆的表干则为 $0,5\\sim1\\mathrm{h}$ 实干为 $6\\sim8\\mathrm{h}$ ，硬度和耐水性都有较大提高。  \n\nb.丙烯酸改性醇酸树脂氨基烘漆丙烯酸改性醇酸树脂氨基烘漆具有醇酸树脂氨基烘漆的附着力，还具有丙烯酸树脂的耐久性与可打磨性。  \n\n·丙烯酸酯预聚物为调节聚丙烯酸酯的硬度与柔韧性，丙烯酸酯单体可有不同的配比。  \n\n·改性醇酸树脂改性醇酸树脂由丙烯酸酯预聚物40份、氢化麻油31份、甘油9.5份、苯二甲酸酐19.5份制成。先将氢化麻油与总量 $63\\%$ 的甘油混合加热，在 $150^{\\circ}\\mathrm{C}$ 加入环烷酸铅（油量的 $0.1\\%)$ ，升温至 $200^{\\circ}\\mathrm{C}$ ，保持1h。冷却至 $180^{\\circ}\\mathrm{C}$ 加入丙烯酸酯预聚物。升温至 $220^{\\circ}\\mathrm{C}$ （中间脱出溶剂）以溶剂法酯化反应至酸值小于 $3\\mathrm{mgKOH/g}$ C $\\mathbf{A}\\mathbf{V}_{1}$ )。降温至约$180^{\\circ}\\mathrm{C}$ 加苯二甲酸酐和所余的 $33\\%$ 的甘油，继续在 $220\\Upsilon$ 酯化至要求的酸值（ $\\mathbf{AV}_{2}$ ）与黏度。  \n\n(8）有机硅改性醇酸树脂所谓的有机硅改性醇酸树脂是指用少量有机硅树脂与醇酸树脂共缩聚而得的改性醇酸树脂。即使用含有一定羟基的醇酸树脂和分子量低的有机硅中间体按照一定的工艺进行接枝反应。 $\\textcircled{1}$ 有机硅在树脂中的含量一般不超过 $30\\%$ 。有机硅加人量过多将影响干性及耐烃类溶剂性。改性后的醇酸树脂仍然用于原来的各种磁漆。有机硅改性醇酸树脂漆为单组分自干漆，施工方便。 $\\textcircled{2}$ 应注意合成有机硅树脂的单体组成（R/Si值）及合成的有机硅树脂的规格。 $\\textcircled{3}$ 醇酸树脂的结构中要有足够的游离羟基以备与有机硅树脂共缩聚。以少量醇酸（聚酯）树脂和有机硅树脂共缩聚以改进有机硅树脂的干率、附着力等性能者不同，后者需烘干，专用于高温、电绝缘等方面。  \n\n因为有机硅树脂具有耐紫外线性、强僧水性，所以将有机硅树脂引入醇酸树脂的结构中，将使醇酸树脂漆膜的保光性、抗粉化性、保色性、耐候性有很大的改进，提高了醇酸树脂的户外使用价值。可用于户外钢结构件和器具的耐久性涂料，如船壳漆、桥梁漆等。以有机硅改性醇酸树脂制舰船涂料，取得了很好的效果。耐5%的 $\\mathbf{NaOH}$ 溶液，30天漆膜不起泡、不脱落；耐中性盐雾1000h；与普通醇酸、氯化橡胶、丙烯酸改性醇酸相比，耐候性均有很大提高。普通醇酸、丙烯酸改性醇酸耐紫外线老化265h后，光泽度急剧下降，有机硅改性醇酸树脂耐紫外线老化则为 $500{\\sim}1000\\mathrm{h}$ ，特别是当有机硅含量达到 $25\\%\\sim30\\%$ 时，漆膜耐紫外线老化性能超过美国军标要求。  \n\n有机硅改性醇酸树脂接枝上的有机硅的含量及分子量分布，采用的分析方法有薄层色谱(TLC)、凝胶渗透色谱（GPC)、红外光谱（FTIR)、核磁共振（NMR）等，对有机硅接枝含量有了较精确的分析。 O  \n\n用于改性的有机硅树脂等都是分子量较低的，最好能与醇酸树脂融合。与醇酸树脂共缩聚有两种方法。一种是有机硅单体先制成硅醇再与醇酸树脂上的羟基共缩聚。硅醇的结构式如下：  \n\n![](images/7acbf18137701fce6b2f20e3603c78e08b9a85afdd876e3457bfc24ce6c9a471.jpg)  \n\n与醇酸树脂的缩聚反应：  \n\n![](images/2c77ab9000596f6f31573ad326e9613b14b668bc00093c3782ff638b9a0bb380.jpg)  \n\n反应时将醇酸树脂与硅醇加在一起（加溶剂）在 $200^{\\circ}\\mathrm{C}$ 左右共热缩合，至完全融合，黏度合格即得。在缩聚时同时有两个反应发生。一个为：  \n\n另一个为：  \n\n$$\n{\\begin{array}{r l}&{{\\dot{\\gamma}}_{\\mathrm{si-OH~+~HO-Cos}}={\\frac{B R!}{\\Delta t}}\\cdot{\\dot{\\gamma}}_{\\mathrm{si-O-Co}+H_{2}\\mathrm{O}}}\\\\ &{}\\\\ &{{\\dot{\\gamma}}_{\\mathrm{si-OH~+~HO-Sim}}={\\frac{B R!}{\\Delta t}}\\cdot{\\dot{\\gamma}}_{\\mathrm{si-O-Si=+H}_{2}\\mathrm{O}}}\\end{array}}\n$$  \n\n增加醇酸树脂的羟基有利于反应1；增加情性溶剂有利于反应2。增加酸值或提高温度可使反应加快但不能改变反应的比例。另一方法是含甲氧基或乙氧基的聚硅烷与醇酸树脂上的羟基缩合。甲氧基硅烷结构式如下：  \n\n![](images/f81b258b7050633689b827ce2dd13294a645897da2b5e9fd9570ceeec8812b97.jpg)  \n\n与醇酸树脂的缩聚反应：  \n\n![](images/bdd72d479c282eacfd557a12be22bca1887dafbc2112a2a957f1da03b2e982a9.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 177,
+        "chunk": "# 【例】改性醇酸树脂合成  \n\n$\\Phi$ 30%有机硅长油度豆油季戊四醇醇酸树脂",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 178,
+        "chunk": "# a.硅醇规格  \n\n<html><body><table><tr><td>a.硅爵规格</td><td></td><td></td><td></td></tr><tr><td>固体分/%</td><td>80</td><td>黏度（加氏，25℃）</td><td>L~V</td></tr><tr><td>溶剂</td><td>二甲苯</td><td>相对密度（25℃）</td><td>1.13</td></tr><tr><td>羟基含量/%</td><td>5~6</td><td>颜色（加氏）</td><td>≤1</td></tr><tr><td>b.豆油季戊四醇醇酸树脂A</td><td></td><td></td><td></td></tr><tr><td>配方/%</td><td></td><td></td><td></td></tr><tr><td>豆油脂肪酸</td><td>58.80</td><td>三苯基亚磷酯</td><td>0.25</td></tr><tr><td>苯二甲酸酐</td><td>21. 10</td><td>二甲萃</td><td>3.00</td></tr><tr><td>季戊四醇</td><td>20.10</td><td></td><td></td></tr></table></body></html>  \n\n设备与溶剂法生产醇酸树脂相同。将配方中原材料都加入反应釜中；在情性气体的保护下升温、搅拌；在 $230\\sim250\\Upsilon$ 回流酯化反应；酸值达到 $5\\sim10\\mathrm{mgKOH/g}$ ，黏度（ $25\\mathrm{{C}}$ ，$60\\%$ 固体分于 $200^{\\sharp}$ 油漆溶剂油中）达到加氏 $J{\\sim}\\mathbb{L}$ 时停止反应，以油漆溶剂油溶解，制成66%固体分溶液。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 179,
+        "chunk": "# c.有机硅改性醇酸  \n\n配方/%  \n\n<html><body><table><tr><td></td><td></td><td></td></tr><tr><td>硅醇（75%不挥发分）</td><td></td><td></td></tr><tr><td>醇酸树脂A（66%不挥发分）</td><td>图休配比</td><td>比</td></tr></table></body></html>  \n\n将配方中原料加入反应釜中，升温至回流温度 $(173\\mathrm{\\sim}175^{\\circ}\\mathrm{C}$ ）并共沸分水。反应至加氏黏度（60%固体分于油漆溶剂油中）达到V～X时停止反应，用油漆溶剂油溶解，制成固体分为 $60\\%$ 的溶液。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 180,
+        "chunk": "# d.灰色半光磁漆  \n\n<html><body><table><tr><td colspan=\"4\">配方/%</td></tr><tr><td>二氧化钛</td><td>16.3</td><td>辛酸钻/6%</td><td>0.3</td></tr><tr><td>炭黑</td><td>0.3</td><td>环烷酸锰/6%</td><td>0.2</td></tr><tr><td>石棉粉</td><td>21.4</td><td>环烷酸钙/5%</td><td>0.3</td></tr><tr><td>卵磷脂</td><td>1.0</td><td>防结皮剂</td><td>0.1</td></tr><tr><td>悬浮助机硅改性醇酸树脂 A</td><td>45.5</td><td>硅油溶液/%</td><td>100.</td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td>200*油漆溶剂油</td><td>14.2</td><td></td><td></td></tr></table></body></html>  \n\n先混合悬浮助剂和 $30\\%$ 有机硅改性醇酸树脂A；再加入二氧化钛、炭黑、石棉粉、卵磷脂混合并分散至细度在 $30\\mu\\mathrm{m}$ 以下；加上述配方的其余原料混合，包装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 181,
+        "chunk": "# 磁漆性能  \n\n<html><body><table><tr><td>不挥发分（按质量）/%</td><td>67.4</td><td>60°光泽度/%</td><td>35~45</td></tr><tr><td>不挥发分（按体积)/%</td><td>47.4</td><td>干率/h</td><td>2</td></tr><tr><td>PVC/% 黏度/KU</td><td>36.3</td><td>指触干</td><td>8</td></tr><tr><td>②30%有机硅短油度脱水麻油醇酸树脂</td><td>70~80</td><td>干硬</td><td></td></tr><tr><td colspan=\"4\">a.脱水麻油醇酸树脂B</td></tr><tr><td>配方/%</td><td></td><td></td><td></td></tr><tr><td></td><td>32.7</td><td>顺丁烯二酸酐</td><td>0.25</td></tr><tr><td>三羟甲基乙烷</td><td>36.7</td><td>二甲苯</td><td>3.00</td></tr><tr><td>苯二甲酸酐</td><td></td><td></td><td></td></tr><tr><td>脱水麻油酸</td><td>30.6</td><td></td><td></td></tr></table></body></html>  \n\n将配方中全部原料装入溶剂法反应釜，在共沸脱水下升温至 $250\\mathrm{\\bar{C}}$ 。反应至固体树脂酸值达到 $9{\\sim}12\\mathrm{mgKOH/g}$ ，加氏黏度（ $60\\%$ 于二甲苯中）为 ${Z_{1}}\\mathrm{\\sim}{Z_{3}}$ ，并在 $200^{\\circ}\\mathrm{C}$ 热盘上胶化，时间为 $19\\sim22{\\mathrm{s}}$ 。以二甲苯溶解成 $68\\%\\sim69$ %溶液。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 182,
+        "chunk": "# b.有机硅改性醇酸树脂  \n\n配方/%  \n\n<html><body><table><tr><td></td><td>按固体质量配比</td><td>按溶液质量配比</td></tr><tr><td rowspan=\"2\">硅醇(80%，同树脂B)</td><td>30</td><td>26.9</td></tr><tr><td></td><td></td></tr><tr><td rowspan=\"2\">醇酸树脂B(68.5%)</td><td>100</td><td>13.0</td></tr><tr><td></td><td></td></tr></table></body></html>  \n\n在溶剂法反应釜中加入配方中硅醇和醇酸树脂并加热至回流以共沸脱水。于 $200^{\\circ}\\mathrm{C}$ 热盘上反应至固化时间为11s，加氏黏度（60%二甲苯中）为 ${Z_{1}}\\sim{Z_{2}}$ 。以二甲苯溶解，制成60%溶液。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 183,
+        "chunk": "# c.灰色有光快千有机硅醇酸树脂漆  \n\n<html><body><table><tr><td colspan=\"3\">配方/%</td></tr><tr><td>二氧化伙</td><td>26.66</td><td>分散助剂</td></tr><tr><td>氧化铁红</td><td>0.20</td><td>悬浮助剂</td></tr><tr><td>炭黑</td><td>0.22</td><td>润湿助剂</td></tr><tr><td>铬黄</td><td>1.01 二甲苯</td><td></td></tr><tr><td>30%有机硅改性醇酸树脂B</td><td>26.21</td><td>14.06</td></tr></table></body></html>  \n\n把上述组分混合，分散至细度达 $20\\mu\\mathrm m$ ，加下列组分：  \n\n<html><body><table><tr><td>30%有机硅改性醇酸树脂B</td><td>24.97</td><td>防结皮剂</td><td>0.06</td></tr><tr><td></td><td>5. 31</td><td rowspan=\"3\">助催干剂</td><td>1.02</td></tr><tr><td>环宽酸钻（6%)</td><td></td><td></td></tr><tr><td>环烷酸钙（5%)</td><td>0.56</td><td></td></tr><tr><td>磁漆性能</td><td></td><td></td><td></td></tr><tr><td>不挥发分（按质量）/%</td><td>59.8</td><td>黏度/KU</td><td>75~85</td></tr><tr><td>不挥发分(按体积)/%</td><td>42.5</td><td>60°光泽度/%</td><td>≥75</td></tr><tr><td>PVC/%</td><td>21.4</td><td>干率/h</td><td>2~3</td></tr></table></body></html>\n\n催干剂的选用以钙、钻配合为好；铅催干剂对性能有降低的作用。  \n\n有机硅改性后的醇酸树脂漆对耐候性、户外耐久性有很大的提高，特别是在保光性、抗粉化性等方面。因此用于防护性底漆上作为面漆，如火车车皮、卡车修补、桥梁等涂饰。  \n\n$\\textcircled{3}$ 丙硅豆油醇酸树脂的合成  \n\na.简介醇酸树脂广泛地应用于室外涂料的基料，未经改性的醇酸树脂，在热带地区气候由于紫外线照射、热波动、高温和风引起的盐雾，在 $10\\sim12$ 个月时就会明显的粉化、褪色和失光。文献中已经报道了一些用不同的单体，例如乙烯基、丙烯酸、硅丙烷等来改性醇酸树脂的方法。有机硅豆油醇酸树脂，与豆油醇酸树脂相比，它显示出了很好的耐候性。保光性是室外涂料的一项重要特性，据报道，醇酸树脂与丙烯酸酯反应也能提高这项性能。在目前的研究中，在树脂结构中含有有机硅和丙烯酸单元的醇酸树脂已经合成，这种类型改性树脂期望能得到这两种结构单元在抗紫外线和保光性方面的优势。合成的改性醇酸树脂的性能比得上现有用在涂料配方中的有机硅醇酸树脂。  \n\n由豆油醇酸树脂、有机硅中间体及甲基丙烯酸-2-羟乙酯（HEMA）合成的聚合物用于长效室外涂料的基料组分。实际上硅丙单体（SAM）是由端羟基有机硅与HEMA制备的，用不同含量的SAM合成新型的豆油醇酸树脂。与有机硅改性醇酸树脂相比，硅丙豆油醇酸树脂制得的清漆漆膜具有良好的力学性能和室外耐久性。  \n\nb.试验  \n\n·原材料未经任何提纯的甲基丙烯酸-2-羟乙酯（HEMA，兰卡斯脱)、端羟基硅氧烷（Z-6018，道康宁）及钛酸四异丙酯（TPT）应用于当前的研究中。从印度Jayant榨油厂得到的环烷酸铅、豆油、季戊四醇、邻苯二甲酸酐及从印度Loba化学有限公司得到辛酸钻已被用于当前的试验研究中。  \n\n·合成分为硅丙单体（SAM）的合成；豆油醇酸树脂的合成；硅丙豆油醇酸树脂的合成。  \n\n![](images/62737d6ee9b2af0b8e628aeca6a20423f1afab92c48eb1871968deb3ceadaa20.jpg)  \n\n![](images/2564d67b63a239afa5b51b515e24abe101a06044f5e2f51d1245d627aca06074.jpg)  \n硅丙单体-豆油醇酸树脂  \n\nc.结论将甲基丙烯酸-2-羟乙基通过化学反应加入硅丙豆油醇酸树脂中能提高醇酸树脂的力学性能和保光特性。通过C-NMR分析和FTIR测量证实HEMA 和有机硅中间体反应形成的SAM随后与豆油醇酸树脂之间存在反应。加入 $30\\%$ SAM的豆油醇酸树脂已经证实比加入 $10\\%$ 和 $20\\%$ SAM的树脂具有更好的耐候性。还可以证明 $30\\%$ 硅丙豆油醇酸树脂的拉伸强度比有机硅豆油醇酸树脂更高，这为SAM豆油醇酸树脂提供更多的韧性范围。总体来说，相比有机硅豆油醇酸树脂， $30\\%$ 的硅丙豆油醇酸树脂为长效涂料配方提供了一种基料。  \n\n（9）异氰酸酯改性醇酸树脂氨基甲酸酯改性醇酸也称氨酯醇酸。应用较多的是TDI，它部分地代替苯酐。氨酯醇酸是由异氰酸酯与植物油醇解后的单甘油酯反应而成的。在工艺的末期加入醇，确保没有N一C一O的残留。氨酯醇酸比制造它们的干性油干得快，因为它们有较高的平均官能度。TDI的芳香环的刚性也促进干燥，提高了树脂的 $T_{\\mathrm{*}}$ 。氨酯醇酸优于醇酸涂料的两个主要优点是优良的耐磨损性和耐水解性，缺点是低劣的保色性（用TDI)。脂肪族二异氰酸酯制造的氨酯醇酸保色性较好，但价格贵且 $T_{\\mathrm{s}}$ 低。  \n\n$\\textcircled{1}$ TDI改性醇酸树脂醇酸树脂都不同程度地含游离羟基，特别是中、短油度醇酸树脂，都可以与多异氰酸酯反应改性。常用的多异氰酸酯芳香族有甲苯二异氰酸酯与三羟甲基丙烷的加成物。现举例说明。原料及配方见表2-1-56。  \n\n表2-1-56原料及配方  \n\n\n<html><body><table><tr><td>原料及名称</td><td>质量分数/%</td><td>原料及名称</td><td>质量分数/%</td></tr><tr><td>植物油（双源，工业品）</td><td>20~30</td><td>TDI(工业品）</td><td>5~10</td></tr><tr><td>季戊四醇（工业品）</td><td>4~7</td><td>200*溶剂汽油（工业品）</td><td>30~40</td></tr><tr><td>催化剂（化学纯）</td><td>适量</td><td>二甲苯(工业品)</td><td>4~10</td></tr><tr><td>苯酐（工业品）</td><td>5~10</td><td>丁醇（工业品）</td><td>2~5</td></tr></table></body></html>  \n\n合成工艺：将植物油、多元醇升温至 $120^{\\circ}\\mathrm{C}$ 加LiOH，在 $240\\Upsilon$ 保温醇解至终点。降温加苯酐和回流二甲苯进行酯化至达到要求指标。用 $200^{\\circ}$ 溶剂汽油兑稀备用。降温至 $40^{\\circ}\\mathrm{C}$ 左右，滴加混合好的二甲苯、TDI溶液。加完后在 $60^{\\circ}\\mathrm{C}$ 保温1h，然后在 $90\\Upsilon$ 保温至合格。黏度合格后，降温至 $60\\ensuremath{\\mathbb{C}}$ ，加人丁醇，搅拌0.5h，过滤包装。 格  \n\n主要技术指标：黏度（涂-4杯，25℃）/s固体含量/%  \n\n讨论：  \n\na.TDI/苯酐摩尔比过低则没有体现改性的作用，过高则反应后期不易控制。TDI/苯酐摩尔比控制在 $(2\\sim3):1$ 较合适。  \n\n·TDI的滴加方式用先兑稀而后滴加的方法，先将酯化产物用 $200^{\\circ}$ 溶剂汽油兑稀，然后滴加TDI和二甲苯的混合液，滴加速度为 $50\\sim100$ 滴 $\\mathrm{\\dot{\\min}}$ 。这样反应比较平稳而性能稳定。  \n\n·反应温度的控制TDI改性醇酸树脂的合成过程分两步进行。第一步先合成分子量低的醇酸树脂，在此反应中，即醇解反应控制在 $240^{\\circ}\\mathrm{C}$ ，酯化温度控制在 $210^{\\circ}\\mathrm{C}$ 为宜。第二步是TDI与醇酸树脂的一OH的反应，此反应属放热反应。温度高于 $100^{\\circ}\\mathrm{C}$ 时，异氰酸酯与氨基甲酸酯反应生成脲基甲酸酯支链而引起树脂胶化。因此，滴加反应阶段，控制温度不高于$60^{\\circ}\\mathrm{C}$ ，滴加完以后，反应温度为 $90\\mathrm{\\sim}100\\mathrm{\\textC}$  \n\nb.—NCO/—OH摩尔比的影响如果—NCO/—OH摩尔比大于1，树脂不稳定；如果—NCO/一OH摩尔比小于1，树脂残余的一OH基多，耐水性下降。为此选择—NCO/一OH摩尔比的理论值等于1。  \n\nc.稳定剂加人量对树脂贮存性的影响尽管在配方工艺理论上—NCO/—OH摩尔比为$1:1$ ，但实际反应不可能达到 $100\\%$ ，最后仍不可避免地存在未反应的一NCO，它的存在对树脂的稳定性以及涂料的性能产生不良影响。因此在反应结束后加入醇类以封闭—NCO。当TDI/苯酐摩尔比控制在 $(2{\\sim}3):1$ ，—NCO/一OH摩尔比的理论值等于1，稳定剂丁醇的加入量为 $3\\%$ 泰  \n\nd.TDI改性醇酸树脂的干性探讨TDI改性醇酸树脂的结构中含有植物油的不饱和双键和氨酯键，在空气中氧化干燥除发生双键的氧化聚合外，氨酯键之间还可能形成氢键，对漆膜干性和硬度也有贡献。用TDI改性醇酸树脂制成的清漆和磁漆的面干在0.5h，实干在4h左右，硬度在0.5以上，说明TDI改性后对醇酸树脂漆的干性、硬度以及耐水性都有明显提高。  \n\n甲基-3,5,5-三甲基环已烷异氰酸酯（IPDI），  \n\n![](images/5c2ba64bdfdfa4c41beab0b740997eb157989dbb741f033d0f885a248ae7a31f.jpg)  \n\n$\\textcircled{2}$ IPDI改性醇酸树脂适于作常温自干型醇酸树脂改性剂的多异氰酸酯是异佛尔酮二异氰酸酯和3-异氰酸酯的聚合体，其结构式基本为三聚体。因为是脂肪族异氰酸酯，所以有极好的不黄变性与耐候性。固体分为 $70\\%$ 时一NCO的含量约为 $12\\%$ 。它溶于芳香烃溶剂或芳香烃与脂肪烃混合溶剂，如二甲苯与油漆溶剂油 $(1:1)$ ）的混合溶剂油中。适用于改性醇酸树脂，最好用于中油度醇酸树脂。加入IPDI（三聚体）可有以下改进： $\\textcircled{1}$ 可缩短表干时间至原来的 $1/3$ ，约为 $20\\mathrm{{min}}$ $\\textcircled{2}$ 干硬快，增加硬度与耐油性； $\\textcircled{3}$ 提高耐候性。因此增加了该漆的使用范围，宜于作户外用漆。  \n\n(10）高固体分醇酸树脂漆醇酸树脂漆一般含 $40\\%$ 左右溶剂，施工后挥发到大气之中，既污染环境，又浪费大量有机原料，于是人们重视研制含溶剂很少（高固体分）的醇酸树脂漆。人们对高固体分醇酸树脂漆做了很多研究，但至今还没有达到满意的结果。提高醇酸树脂漆的固体分途径很多，但也各有不足。  \n\n$\\Phi$ 提高醇酸树脂固体分的途径溶剂的改变可以稍微提高固体分。脂肪烃（含芳香烃较少)，能促进分子间的氢键，特别是羧酸之间和羟基之间的缔合，从而提高黏度。使用一些氢键受体溶剂如酯或醇，相同的固体分会使黏度显著下降。同样醇酸树脂结构上的极性官能团的浓度也会影响醇酸树脂溶液的黏度。羟基与羧基是氢键供体，酯基与羧基是受体，这些基团浓度增高时引起分子之间的力增大而黏度上升。加少量低分子量醇类、酮类，虽然它们的溶解度参数和树脂相差很远，但它们作为氢键供体或受体可使黏  \n\n度降低。  \n\n增加固体分的另一个途径是降低分子量。提高油度、减少二元酸/多元醇的比例，这可以轻易完成，但会增加干燥时间。  \n\n制造窄分子量分布的树脂，可增加固体分。例如接近醇酸熬炼的终点，添加一个酯交换催化剂，会给出一个更均匀的分子量分布和更低黏度的醇酸树脂。为了研究分子量效应，使用二环已基碳化二亚胺（DCC)，它可低温酯化，合成有很窄分子量分布的模型树脂。以低温法可制出模型醇酸树脂，没有副反应，分子量较低，分子量分布（PDI）较窄，结构较均匀，黏度较常规法制者为低。但低温法固体分提高的幅度仅为 $2\\%\\sim10\\%$ 。虽不是工业生产法，但按此法可制出模型醇酸树脂。单纯以降低分子量来制高固体分自干型醇酸树脂漆尚行不通，应另辟途径。  \n\n高固体分醇酸树脂漆的关键是黏度，可修改配方以制取低分子量的醇酸树脂来降低黏度。但要牺牲醇酸树脂的性能。醇酸树脂的平均分子量不能低于一定水平，否则影响漆膜的性能。分子量分布对醇酸树脂的黏度影响很大。醇酸树脂按GPC分析有极宽的分子量分布，其中按质量的分子量比数均分子量 $(M_{\\mathfrak{n}}$ ）要大100倍以上。高分子量的部分被认为是成膜部分，而低分子量的部分则起溶剂与增塑剂的作用。  \n\n制造方法的不同也影响分子量分布。醇酸树脂溶液的黏度取决于高分子量部分，存有一定数量的高分子量馏分（约为 $100\\times M_{\\mathrm{s}}$ 以上）将使溶液黏度大为增加。分子量分布的宽度也影响溶液的黏度，分子量分布很窄则树脂溶液的黏度较低，溶液的固体分较高。脂肪酸的不饱和程度对黏度也有影响，不饱和一C一C一越多黏度越低。  \n\n在醇酸树脂制造的同时有一些副反应，如醚化、酯交换、不饱和脂肪酸之间的交联、酯化时形成内酯合环等。酯化增加多元醇的官能度，使黏度增高。虽然有情性气体防止氧化，但酯化在 $200^{\\circ}\\mathrm{C}$ 以上高温进行，脂肪酸的交联难以避免。  \n\n$\\textcircled{2}$ 活性溶剂稀释醇酸树脂漆为争取醇酸树脂有较高的固体分以减少溶剂的挥发和提高醇酸树脂漆的使用率，曾试用活性稀释剂。它一方面起溶剂作用，另一方面在漆膜固化时，特别是在室温干燥时，转化于漆膜整体之中，成为漆膜的一部分。这种活性稀释剂必须是挥发性很低、低毒、低臭并与大多数树脂可融合；同时还要价格合理，所得漆膜应具有厚涂层性，有良好的力学强度和耐介质性。但至今还没有找到能完全取代溶剂的活性稀释剂。  \n\n20世纪80年代初D.B.Larson与W.D.Emons提出甲基丙烯酸二环戊烯氧乙基酯(dicyclopententyoxyethyl methacrylate)。美国 Rohm and Hass Company 商品名 QM-657,结构式如下。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 184,
+        "chunk": "# 产品规格：  \n\n<html><body><table><tr><td>外观</td><td>透明液体</td><td>折射率(22℃）</td></tr><tr><td>颜色(APHA)</td><td>100~300</td><td>沸点(101.3kPa)/C</td></tr><tr><td>黏度(25C)/dPa·s</td><td>0. 15~0.19</td><td>溶解度参数</td></tr><tr><td>密度（25C）/(g/cm）</td><td>1. 064</td><td>闪点（片斯基-马丁闭杯）/℃</td></tr><tr><td>固化膜硬度(努氏)</td><td>15</td><td>玻璃化混度（均聚物）/C</td></tr><tr><td>固化收缩率/%</td><td>8.7</td><td>阻聚剂（对苯二酚）/（mg/L）</td></tr></table></body></html>  \n\nQM-657的合成是先由乙二醇与环戊二烯在强酸下反应，然后与甲基丙烯酸甲酯进行酯交换制得。沸点高，毒性低，适于作活性稀释剂。  \n\n![](images/4d6859b0a2874d62df91584e6dc9644baae9c417edee079474cf207e29b3fab8.jpg)  \n\nQM-657分子上有丙烯酸双键和烯丙基双键，在有普通金属催干剂与氧存在下可成为自由基源，不仅可自聚成固体分，也可与不饱和性树脂如干性油醇酸树脂、不饱和聚酯、多官能团丙烯酸聚酯共聚。QM-657单体在无催干剂存在下很稳定，如有催干剂（如钴)，两天之内自行完成固化。但加入少量甲基、乙基酮可以配制成含钴催干剂而且非常稳定的产品。可能是因为甲基、乙基酮与Co催干剂构成复合物，降低了Co催干剂的活性。QM-657可代替部分溶剂制高固体分醇酸树脂。  \n\n在有些情况下，使用最佳化的树脂和活性稀释剂，能配制VOC含量为 $280\\sim350\\mathbf{g}/\\mathrm{L}$ 的气干和烘干醇酸涂料。只有在施工和涂膜上作些牺牲才能配制250g/LVOC含量。  \n\n在提高醇酸树脂漆的固体分时，还有一个因素不可忽视，即催干剂中的溶剂问题。用不饱和高沸点脂肪酸酯作为活性稀释剂代替普通溶剂，在高固体分醇酸树脂漆中得到应用。这种活性稀释剂含有短链油酸及亚油酸的脂肪酸酯，以及少量棕榈酸酯和硬脂酸酯。这种活性稀释剂显示出很低的蒸气压，沸点在 $280^{\\circ}\\mathrm{C}$ 以上，闪点高于 $170^{\\circ}\\mathrm{C}$ ，本书将在催干剂一节讨论。  \n\n（11）触变性醇酸树脂漆“触变”这个名词是用来描述由于剪切（如搅拌）而产生的黏度可逆的现象。醇酸树脂经过处理可具有触变性，制成触变性涂料。触变性漆的优点为：在漆刷上不滴落；在垂直面施工不流挂；颜料悬浮性好；刷涂性好；改善发花性颜料，有较好的遮盖力。  \n\n黏度不受外力影响的液体为理想液体或牛顿液体。水、有机溶剂和某些低黏度树脂溶液 等可视为牛顿液体。  \n\n$\\Phi$ 塑性流动某些液体在大于一定的剪切应力（屈服值）作用之后方能流动，而且是按牛顿液体流动，其剪切应力对剪切速率所作的图是不通过原点的直线。一般磁漆多属于此类。  \n\n$\\textcircled{2}$ 假塑性流动假塑性流动是混合性的流动。在高剪切速率时像塑性流动；在低剪切速率时像牛顿流动。其变化是逐渐没有明显界限，表现为剪切应力增加黏度下降，剪切应力对剪切速率作图是一个凹面向上的曲线，其斜率取决于剪切应力，但不服从公式 $\\scriptstyle\\eta={\\frac{\\rho}{\\gamma}}$ 。许多高颜料分色漆属于此类。  \n\n$\\textcircled{3}$ 膨胀流动与假塑性流动相反，前者增加剪切应力，黏度下降；膨胀流动则是增加剪切应力，黏度反而升高。剪切应力对剪切速率作图也是一条曲线，但是凹面向下。此种现象在涂料中很少见。 Ar 9  \n\n$\\textcircled{4}$ 触变性流动对以上三种流动来说，所加剪切速率不论是递增还是递减，测得快或慢，其黏度曲线总是同样的一条曲线。但触变性流动以剪切速率递增与剪切速率递减测定的黏度曲线则不同，形成两条曲线。两条曲线之间的面积谓之触变环，表示触变性大小。图2-1-7为各种液体流动，图2-1-8为触变性流动。 9八  \n\n触变性漆表现为在静止时黏度很高，甚至为胶冻状；在受剪切作用时，如搅拌或刷子刷涂，黏度降低形成低黏度液体；剪切停止，如停止揽拌或刷完，黏度又逐渐增高，恢复到原来的黏度。中间有一个滞后期，它们形成两条曲线，此种滞后现象有利于刷后流平。  \n\n不要将触变与假稠相混淆，颜料体积浓度很高形成假塑性流动，漆曲线只有一条，没有滞后期，刷痕很重。  \n\n![](images/243a8f496cb4081b1f0a5383f861ff86e46b3f79cb7d68ae5194253049af7700.jpg)  \n图2-1-7各种液体流动  \n\n![](images/c0f9fcbc0bc9a024e85bd65c9d6351cf771551a005d606a549e18e84d37ec897.jpg)  \n图2-1-8触变性流动  \n\na.触变性醇酸树脂漆的制备触变性醇酸树脂漆料是由醇酸树脂与聚酰胺树脂反应制得的。所用的聚酰胺树脂是不饱和脂肪酸的二聚酸与二元胺的缩合物。二聚酸的结构式如下：  \n\n例如，德国Schering公司的三种触变性醇酸树脂的聚酰胺树脂，其规格如下：  \n\n\n<html><body><table><tr><td>Ertelon</td><td>934</td><td>935</td><td>900</td></tr><tr><td>相对密度</td><td>0.98</td><td>0.98</td><td>0.98</td></tr><tr><td>酸值/（mgKOH/g)</td><td>≤7.0</td><td>≤7.0</td><td>7.0</td></tr><tr><td>胶值/（mgKOH/g)</td><td>≤7.0</td><td>≤7.0</td><td>7.0</td></tr><tr><td>颜色（加氏）</td><td>≤10.0</td><td>≤10.0</td><td>10.0</td></tr><tr><td>软化点（环球法）/C</td><td>105~115</td><td>110~120</td><td>180~190</td></tr></table></body></html>  \n\n前两种用于改性长、中油度醇酸树脂，改性的醇酸树脂，溶于 $200^{\\circ}$ 油漆溶剂油；后者用于改性短油度醇酸树脂，溶于芳香烃溶剂。  \n\nb.熔融法改性醇酸树脂将醇酸树脂在情性气体下搅拌，加热至需要的温度，加入需要量的聚酰胺树脂，保持温度恒定。定期取样溶于 $200^{\\#}$ 油漆溶剂油 $40\\%$ ，测定触变性。触变性开始时增长，至一最大点又开始下降。聚酰胺树脂是不溶于 $200^{\\sharp}$ 油漆溶剂油与芳香烃溶剂的，随改性反应的进展，反应物逐渐溶解透明，达到透明时谓之“透明点”。  \n\nc.容积法改性醇酸树脂一般改性都以熔融法进行，但也可以溶剂法进行。在 $185\\mathrm{^Y}$ 即石油油漆溶剂的沸点反应，反应时间较长。  \n\nd.触变性醇酸树脂的应用触变性醇酸有两种用途：一种是自己作为漆料制触变性漆；另一种是作为其他漆的改性剂增加在罐内表观黏度、防止颜料沉底、改进施工性。以触变性漆料制触变性漆，视要求不同而掌握其改性程度。如用量最大的建筑漆并不需要很高的胶化性，只需一定程度的改性，如用 $2\\%\\sim4\\%$ 聚酰胺树脂改性，使颜料不沉底、刷涂性好、不流挂即可。如果要求一次涂厚度 $1250\\mu\\mathrm{m}$ 的红丹底漆，则要制成很高胶化性的漆料。触变性漆料还可制富锌漆，有良好的罐内稳定性。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 185,
+        "chunk": "# (12）其他类型的改性醇酸树脂漆  \n\n$\\Phi$ 醇酸树脂由于价格较低、加工性能好，可改性的研究领域非常广如环氧磷酸酯复合改性醇酸树脂可在卷材涂料背涂应用。由于在醇酸树脂中引入环氧基团，改善了漆膜与底材的附着力，在醇酸树脂中加入磷酸酯，促进了漆膜和底面形成磷化膜，提高了涂层的防腐能力。用红外谱图分析，醇酸树脂的主链上接枝有环氧基团和磷酸酯基团。改性醇酸树脂的平均分子量为4441，数均分子量为3808，质均分子量为19206，分子量分布系数为5.04引用的主要单体材料是工业级环氧烷基酯和异丙基三（二辛基焦磷酸酯）磷酸酯。  \n\n![](images/deb2528115e67be5e56a64bb39375c68d243e6ace52949d0af9c3a689e8df38a.jpg)  \n\n$\\textcircled{2}$ 关于利用废料生产醇酸树脂在工程塑料、合成树脂以及纺织和服装业有一种数量很大的废料，即涤纶—对苯二甲酸乙二醇酯（PET)，用来生产改性醇酸树脂已得到广泛应用，对发展循环经济也是有益的。一般用多元醇进行降解，也可将聚酯片和一元酸在250～270℃降解。降温到 $100^{\\circ}\\mathrm{C}$ 以下加人多元醇和催化剂进行酯化。其他原料还有松香、二甘醇、季戊四醇等。涤纶废料的用量为 $15\\%\\sim25\\%$ ，催化剂可选用氧化锌，用量为$0.05\\%\\sim0.08\\%$ 、若用二丁基氧化锡，用量为 $0.02\\%\\sim0.08\\%$ 曲",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 186,
+        "chunk": "# 八、醇酸树脂的发展趋势  \n\n我国以油脂为原料的涂料产量在行业总产量中占有很大的比重，其中醇酸树脂漆占大部分。以油脂为原料开发环境友好型涂料及环境友好型催干剂，是涂料技术发展的前沿，植物油是可再生资源，扩大涂料用非食用油在我国有很大潜力。因此，从涂料行业可持续发展的角度来看，醇酸树脂漆发展空间是很大的。我国对于环境友好型醇酸树脂及环境友好型催干剂的研究，与国外的差距很大。现代醇酸树脂的发展要求降低VOC排放量，以适应环保要求。欧盟涂料产品指令要求达到的VOC限定量，第二阶段（2010年开始）为 ${300}\\mathrm{g/L}$ (溶剂型体系)。对于传统的醇酸光泽涂料，在满足欧盟VOC指令方面面临的问题是：当溶剂含量降到 $300_{8}/\\mathrm{L}$ 时，黏度变得很高，产品难以接受。如果将分子量降低，同时增加油含量，可获得可接受的黏度，但可能出现流挂、干燥慢、抗粘连性差、黄变。开发高固体分醇酸体系是趋向于这种需要的一种可行方法。而随着水性醇酸树脂体系和水乳化预复合催干剂的发展，人们现在已能制造出性能达到溶剂型涂料要求的水性（醇酸）涂料。不论自干性高固体分醇酸体系还是水性醇酸树脂体系，新型催干剂都是必须研究的问题之一。而开发高固体分醇酸漆，有一个重要途径是关于活性稀释剂的研究。",
+        "category": " Introduction"
+    },
+    {
+        "id": 187,
+        "chunk": "# 1.催干剂问题  \n\n对于气干性醇酸树脂漆，催干剂的作用是至关重要的。Stewart检验了35种作为催干剂不同的皂，其中只有10种化合物对干燥过程中具有一定程度的加速作用，可以看到钴性能最佳，而锰相对较差，很多金属都有负面性能，如毒性、稀有、放射性、无活性等，而不适合作为催干剂。国外对醇酸树脂的发展，如高固体分醇酸树脂和醇酸树脂水性化的研究，都是和催干剂的研究相关的。  \n\n(1）高固体分醇酸体系用催干剂催干剂中加人溶剂的目的是提供一种液态产品，这样便于加工和应用，但催干剂中的溶剂带来固体分的下降。同时催干剂溶液中含有少量的芳香烃，这些挥发性有机物VOC，成为发展高固体分的障碍。 天  \n\n$\\Phi$ 活性脂肪酸酯催干剂参与基料反应的零VOC的活性稀释剂是达到高固体分醇酸体系的有效方法。这种新的催干剂是溶于不饱和高沸点的脂肪酸酯这种活性稀释剂中，这种“溶剂”中含大量的短链油酸和亚油酸的脂肪酸酯以及少量的棕榈酸酯和硬脂酸酯。这种活性稀释剂蒸气压很低，沸点在280℃以上，闪点高于 $170^{\\circ}\\mathrm{C}$ ，不属于毒性分类范围。这种活性稀释剂催干剂的特点是：a.不含芳香族溶剂；b.是可生物降解的无害溶剂；c.不含挥发性成分，因此无VOC排放；d.允许最高可能的固体分含量；e.与传统的溶剂型干料相比  \n\n有同样的活性；f.提供适宜的性价比。  \n\n这种零VOC的催干剂，提供了重要的生态和经济优势。通过这种方式人们可以降低配方中的VOC含量而增加固体分，而又不影响其他性能，如干燥性等。  \n\n它具有健康和安全优势。非常高的沸点的脂肪酸酯类意味着不会发生吸人蒸气的危险，使用这种催干剂不需要按照废气标准或使用复杂的通风系统；由于高闪点，使得空气和溶剂混合构成潜在爆炸性降低，在使用、贮存、运输产品过程中更为方便；脂肪酸酯类溶剂也不会导致亚急性和慢性中毒症状；它们也能很快完全地降解，并溶于土壤和水中。  \n\n用于催干剂产品的溶剂分类见表2-1-57。  \n\n表2-1-57用于催干剂产品的溶剂分类  \n\n\n<html><body><table><tr><td>项 目</td><td>200溶剂汽油</td><td>二甲苯</td><td>脱芳香烃200</td><td>脂肪族开链烷烃</td><td>脂肪烃酯类</td></tr><tr><td>芳香烃含量/%</td><td>15.20</td><td>100</td><td><1</td><td><0.01</td><td>一</td></tr><tr><td>分类</td><td>Xu/R65</td><td>Xu/R10-20</td><td>Xu/R65</td><td>Xu/R65</td><td></td></tr><tr><td>闪点/C</td><td>>65</td><td>32</td><td>>65</td><td>>65</td><td>>170</td></tr><tr><td>VBF</td><td>AI</td><td>AI</td><td>A</td><td>A</td><td>一</td></tr><tr><td>空气质量控制技术规范</td><td>类</td><td>Ⅱ类</td><td>类</td><td>类</td><td>一</td></tr><tr><td>蒸气压</td><td>5Pa/37.8C</td><td>5Pa/37.8C</td><td>5Pa/37.8°C</td><td>5Pa/37.8°C</td><td>二</td></tr><tr><td>皮肤接触过敏</td><td>可能</td><td>有</td><td>可能</td><td>没有</td><td>没有</td></tr></table></body></html>  \n\n由于这种溶于活性稀释剂的新型催干剂的使用量急剧上升，在建筑涂料和工业漆中都有应用，成为内外墙建筑涂料以及酯基印刷油墨不可缺少的部分。  \n\n·高固体分锰基复合催干剂：Borcherb、DryVpo237。它溶于活性稀释剂，零VOC，用于高固体分涂料，这种产品含有一种特殊协同作用的金属化合物，它们同时含有主催干剂和辅助催干剂时，成为全能催干剂。  \n\n·高固体分体系的锰基单一金属催干剂：Borcherb、DryVpo410和DryVP0411 HS。这是通过改性羧酸链配合金属和混合有机整合剂来完成的DryVP0411HS，是溶于脂肪酸酯活性稀释剂，并用于高固体分体系的，用于水性体系的正在开发中，和其他无钻主催干剂相比，共用之处是它们高的催干能力和很少的添加比例。  \n\n调漆时还加人不同催干剂和防结皮剂0.4%丁酮（MEKO)。涂料做好后静止24h进行性能测试。干燥时间按ASTMD5895在标准条件下以干燥时间记录仪测定，漆涂在玻璃上，湿膜厚度 $100\\mu\\mathrm{m}$ ，对照样品：钻/锆/钙催干剂（0.1%钴、0.5%锆%、0.2%钙，均以固体计）总添加量 $3.3\\%$  \n\n$\\textcircled{2}$ 快干无钻高固体分醇酸漆的新的固化机理以硫基/烯类单体化学的高固体分醇酸体系快速干燥，是以硫醇树脂和醇酸树脂合成为基础，通过可见光引发剂和无钻金属催干剂，而得到的快干高固体分醇酸漆。  \n\n氧化还原干燥在醇酸漆中应用很广泛，在较低的温度 $(5\\sim10^{\\circ}\\mathrm{C}$ ）下氧化交联非常慢。  \n\n硫基/烯类单体化学的机理是逐步聚合的反应机理：一个硫醇自由基加硫到不饱和碳链上，产生一个碳自由基能从硫醇中夺取一个氢原子，从而聚合继续进行。硫基/烯类单体聚合物的一个独特性是它不受氧抑制作用的影响，就硫醇聚合而言，过氧自由基仍然能从硫醇中夺取一个新的氢原子，产生硫基自由基，使得聚合继续进行，硫基/烯类单体在有氧存在下更活泼，使得它在桃干燥涂料中应用更广。硫基/烯类单体反应遵循逐步聚合机理，假定这个机理有两个聚合阶段。阶段一为硫基/烯类单体与高固体分醇酸树脂中脂肪酸单元的快速反应；阶段二是醇酸通过生成和分解过氧化氢自由基的标准氧化干燥反应。形成最终的化学品，不受氧的抑制。  \n\n(2）水性醇酸体系的催干剂水性涂料的组成和传统的石油溶剂稀释的醇酸漆有很大的不同，尤其在溶剂、基料和中和剂使用等方面都有很大的差别。而且水性涂料的干燥过程，伴随着由极性向非极性转变，为了适应这些特殊要求，有必要对干燥体系的组成和金属浓度等方面进行调整。在大多数情况下，水性氧化干燥涂料的基料是由醇酸树脂乳液或高度胶体分散的醇酸树脂组成的，及以物理干燥的聚合物分散体。通过水分以及仍存在漆膜中溶剂和中和剂的挥发达到物理干燥，接下来醇酸树脂发生氧化聚合与溶剂体系相同，并被催干剂大大加速。  \n\n由于水和中和剂的特性，水性涂料的干燥过程会发生水相向溶剂相的转变，这会对催干剂产生显著影响。  \n\n在水性涂料中，加入催干剂会导致如下问题：初期干燥不良，贮存过程中催干剂的抑制，催干剂与树脂的不相容。表面缺陷，胶体体系下降，光泽度较低等。  \n\n由于水性醇酸体系和水乳化预配合复合催干剂的发展，现在已经能够制造出性能达到溶剂型涂料的水性涂料。  \n\n在水性涂料中配位体用于增加催干剂活性和避免干燥下降。采用使主催干剂具有水乳化能力配位体的又一优点是，不仅提高乳化效果，而且催干剂和水性涂料的相容性显著提高。这种干料标记如下：WEBC（水可乳化)，FSC（水不可乳化）的预络合干料。  \n\n(3）水性催干剂的螯合配位体羧酸钴是最有效的金属催干剂，钻与钻盐被报道有致癌和遗传毒性，在立法的压力下迫使涂料制造商寻找替代钻的金属催干剂，异辛酸锰与异辛酸钴相比，仅有辅助催干行为，但通过加人2,2-双吡啶（bpy)，异辛酸锰的催干能力能明显提高，但遗憾的是即使加入少量bpy，漆膜的白度和硬度也会受到很大影响。所以必须寻求比bpy更好的其他的整合配位体。两种新的整合配位体2-氨基甲基吡啶（amp）和2-羟甲基吡啶（hmp）在提高异辛酸锰干性方面优于或至少相当于 $^{2,2^{\\prime}}$ -双吡啶。  \n\n实验采用 $2\\%$ （体积）亚油酸乙酯（EL）的水乳液，用于水性醇酸漆的催干剂是Saslserro（新西兰Delden）提供的Nuoden Mn9（9%异辛酸锰，并含有表面活性剂)。  \n\n实验结果证明hmp 和amp 两种配位体对异辛酸锰催干剂能使诱导期和反应速率比 bpy更好。用FTIR时间分辨描述证明了这一点。用 SEC和GC-MS（气相色谱-质谱法）也证明了这一点。在水性体系中amp比hmp有更好的效果，在反应中表现的活性与实际醇酸漆干性一致。  \n\n缺点是仍解决不了锰催干剂的泛黄性，硬度也不够理想，amp和hmp加到醇酸乳液中会产生絮凝。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 188,
+        "chunk": "# 2.高固体分醇酸树脂用的活性稀释剂  \n\n活性稀释剂（RD）必须符合下列条件。  \n·低挥发性（沸点 ${>}300\\mathbb{C}$ 。  \n·适当的反应速率，与醇酸树脂干燥速率相当。  \n·可聚合的，与亚麻油可进行均聚或共聚。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 189,
+        "chunk": "# 3.醇酸乳胶漆的性能、问题及解决的办法  \n\n(1）醇酸乳胶漆的稳定性醇酸乳胶漆，其稳定性主要受基料和颜料颗粒间渗透及静电排斥所影响。基料分散体的流变性可以采用增稠剂来调节，这类增稠剂的憎水性聚合物链段与亲水性聚合物链段要适当搭配。醇酸乳胶漆的成膜性能，取决于成膜过程，主要参数有黏度、混溶性以及基料的交联能力。醇酸乳胶漆的干性稳定性通过选择合适的催干剂来解决。  \n\n，醇酸乳液是醇酸树脂在水中的分散体，该体系的稳定性持续到涂料开始成膜。过去人们普遍认为，静电排斥法适合于水性体系，而空间位阻排斥法较适合于有机溶剂体系；但最近这种意见已经发生改变，在水性体系中采用空间位阻排斥法则更普遍了。醇酸乳液是采用非离子型乳化剂来确保其空间位阻排斥作用的。位阻排斥与静电排斥相比，优点是受离子存在影响很小，缺点是需要较大用量的非离子型乳化剂来达到最大的稳定性。而近来醇酸乳液稳定性更好一些，它是通过小颗粒与静电及空间位阻排斥两方面作用来实现稳定性。给予颜料颗粒与乳液液滴以相同的稳定性的聚合物分散剂，在漆的贮存过程中不会产生颜料或乳液的沉淀或絮凝。最终漆膜的性能，如光泽、硬度、干性、颜色等均很优良。  \n\n满足醇酸乳液稳定性的分散剂的物理化学的基本要求如下。  \n\n·该聚合物被牢固地吸附在颜料颗粒表面上。  \n·它使颜料带上负电荷。  \n·位阻排斥的类型与乳液液滴位阻排斥类型相同。  \n·在漆膜形成的过程中（由亲水性的变为憎水性的)，确保胶体稳定。  \n\n该分散剂是完全水溶性的，不含有机溶剂，也不含憎水链段。由于不含增水链段，使分子中不具备较多润湿剂所含的皂的结构，因此该分散剂的稳泡倾向较小。由于这种分散剂有很多锚固点结构，所以浮游于水相中的游离分散剂是很少的。  \n\n进一步改进分散剂的方面是使它在最终漆膜中起到增塑剂的作用。要开发这样的游离分散剂，在湿膜中它是水溶的（提供空间位阻作用)，当成膜时，它转变为憎水链段结构并能参与到醇酸树脂同氧的交联反应，变成憎水网络的一部分。  \n\n(2）醇酸乳胶漆的流变性水分散体系，它的黏度在整个切变速率范围内都太低，在刷涂施工高剪切速率下黏度太低，所以得到的漆膜很薄。有较好的流平性和消泡性，但易发生流挂。用缔合型增稠剂增稠的乳胶漆有很多缺点，其黏度的增长效应更加依赖体积固体分，所以最好的乳胶漆增稠剂是一种只要漆膜湿态时，几乎是完全水溶的聚合物。一旦物理成膜，并接着发生氧化干燥，增稠剂的亲水部分则必须马上变成憎水的，以消除漆膜对水的影响，理想的这种增稠剂可以构筑到醇酸漆氧化干燥形成的网络中去。在这种情况下，增稠剂就不会表现出一点热塑性。这种具有“响应性”的体系目前正在开发，而具有“响应性”的乳化剂已经商品化了。  \n\n（3）醇酸乳液漆干燥性醇酸乳液漆在施工后必须经过两个过程，即物理成膜与经氧化干燥加成交联，以后和溶剂型醇酸的交联过程是一样的。在贮存过程中要加甲乙酮防止漆在贮罐中的交联。在醇酸乳胶漆中，醇酸树脂被封在液滴中，因此从理论上讲，醇酸树脂同罐中的空气并不接触。实际上，为防止在贮存时因温度高至 $50^{\\circ}\\mathrm{C}$ 时出现结皮，加人防结皮剂也是必要的。当醇酸乳液的胶体足够好时，局部的聚结和加成交联作用可以防止。新近开发的醇酸乳胶漆已没必要加防结皮剂，人们发现酮型防结皮剂对醇酸乳胶漆在较高温度贮存的干燥稳定性有不良影响。厉在水中，特别是在高温下所发生的反应，正是合成时应防止的反应。在水中分解，接着羟基胺与钴络合而失去其催干活性。所以结论是在醇酸乳液的胶体稳定性很好时，在该漆中应避免使用酮作防结皮剂。  \n\n用于溶剂型醇酸漆的催干剂并不十分适合醇酸乳胶漆，因此，主要催干剂供应商，Vi-anova、Servo、Jager、OMG和Borchers的产品，或多或少可以看成传统的金属催干剂的乳液形式。用于醇酸乳液氧化干燥的理想催干剂应该是憎水性的，以便它能保留在醇酸相中，能防止由于水解、吸附或同其他助剂形成络合物，使催干剂性能下降。  \n\n（4）成膜性醇酸乳液的成膜过程在某些方面和丙烯酸分散体的成膜过程相似，如成膜第一阶段水的蒸发，醇酸液滴的彼此接触，并发生醇酸链的部分界面扩散，但两者又有很大差别。水包油乳液经过一个亚稳态均匀体阶段，变成油包水乳液。这个过程用醇酸乳液清漆涂在一个玻璃板上，就可以很容易观察到这四个不同的阶段：水包油乳液一亚稳过渡态一油包水乳液一醇酸。  \n\n醇酸树脂黏度低，不能阻止相转变，这一点和丙烯酸分散体不同。发生相转变后，水分继续蒸发，漆膜变得透明起来。醇酸乳液形成连续的漆膜的临界点比丙烯酸分散体要低，是因为醇酸树脂有较宽的混溶范围和较低的黏度，甚至低温下也是如此。醇酸乳液的成膜过程同丙烯酸分散体的成膜过程的主要区别是，在醇酸乳液的情况下，基料液滴之间原界面在几秒内就可以消失。  \n\n丙烯酸分散体和醇酸乳液的优点比较见表2-1-58。  \n\n表2-1-58丙烯酸分散体和醇酸乳液的优点比较  \n\n\n<html><body><table><tr><td>丙烯酸分散体</td><td>醇酸乳液</td></tr><tr><td>1.快干物理性干燥</td><td>1.没有共溶剂</td></tr><tr><td>2.耐久</td><td>2.没有聚结剂</td></tr><tr><td>抗黄变</td><td>3.抗粘连</td></tr><tr><td>耐水解</td><td>4.可打磨</td></tr><tr><td>耐紫外线</td><td>5.光泽好</td></tr><tr><td>3.稳定的柔韧性</td><td>6.对底材渗透好</td></tr><tr><td></td><td>7.漆膜的低透过性</td></tr></table></body></html>  \n\n(5）欧盟2010年VOC法规对醇酸光泽涂料的影响满足欧盟VOC法规，是将其转化为水体系，这种制备光泽涂料的方法带来的问题如下。·货架稳定性。·黄变。·耐水性和耐化学品性。  \n\n柏斯托精细化学品公司已推出一类气干性表面活性剂，将脂肪酸和表面活性剂结合到单个分子中，在干燥时，脂肪酸部分会与已分散醇酸中的脂肪酸发生相互反应，这样就减少了表面活性剂的迁移。表面活性剂的迁移会吸受水分而导致光泽度变低或者发白。Croda 公司发表了应用非迁移表面活性剂克服这些问题的报道。所有的表面活性剂具有一个不饱和的主链，能参与氧化固化反应的过程。  \n\n将丙烯酸和醇酸结合起来似乎是克服使用单一聚合物面临问题的合理途径。巴斯夫公司和Nuplex树脂公司报道了通过降低表面硬度提高单一丙烯酸聚合物光泽度水平的丙烯酸/醇酸复合乳液技术进展。涂膜的垂直切割TEM图像说明乳胶漆的表面上有一些颜料暴露在外，而在溶剂型醇酸涂料中颜料会被树脂的表面层完全包覆。  \n\n通过使用一层透明的表面涂层也可以获得乳胶漆光泽涂料的相同效果，这在汽车工业中很普遍，但是建议装饰涂料用户额外使用一个涂层实际上是不现实的。新型丙烯酸/醇酸乳液通过将醇酸组分迁移到表面形成一个透明涂层也实现了相同的效果。新型的基料可以用于配制光泽度达 $70\\%$ $20^{\\circ}$ ）的涂料，相比较而言，典型的丙烯酸光泽涂料的光泽度为40%～$60\\%(20^{\\circ})$ ，典型的溶剂型醇酸涂料的光泽度为 $70\\%\\sim85\\%(20^{\\circ})$ 要 人  \n\n纽佩斯树脂公司也在开发丙烯酸/醇酸复合技术，以获得比传统丙烯酸更长的开放时间。开放时间的定义是一个时间过程，该过程中湿涂膜的涂料缺陷可以得到修复而不会留下刷痕。  \n\n纽佩斯树脂公司开发的技术在固化过程中涉及相的转化。通过相转化实现的成膜，不同于胶膜的聚集，其固化的阶段和溶剂型涂料的最后固化阶段相似。在相转化点，体系从水包油相转化成油包水相，此后水分开始蒸发。聚合物的形态包括一个聚氨酯-丙烯酸核以及一个与其相连的相转化的醇酸部分。聚氨酯的引入是为了获得更好的力学性能。用这种技术可能使开放时间达10～20min，通过应用水溶性溶剂如一缩二乙二醇和乙二醇单醚还可以进一步延长开放时间。  \n\n当配制复杂体系的时候，配方中需加人的其他组分需要仔细选择以便获得最优化的性能，例如，分散剂对于开放时间有很重要的影响，而且推荐结合应用两种缔合性增稠剂，可获得流动性、抗流挂和流平性的适当平衡。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 190,
+        "chunk": "# 4.纳米材料改性醇酸涂料  \n\n近几年来，纳米复合材料已在涂料中得到应用。纳米复合涂料指的是将纳米粒子用于涂料中获得某些特殊功能的涂料。一方面纳米复合涂料在常规的力学性能如附着力、耐冲击性、柔韧性方面得到提高，另一方面有可能提高涂料的耐老化性、耐腐蚀性、抗辐射性。此外纳米复合涂料还可能呈现出某些特殊功能，如自清洁、抗静电、隐身吸波、阻燃等性能。但纳米材料在涂料中不易分散，易发生一次团聚的问题。  \n\n在纳米 $\\mathrm{{SiO_{2}}}$ 改性醇酸涂料中，采用KH-570硅烷偶联剂和超分散剂，并以机械分散为主、超声波分散为辅的方法进行改性和分散。经过一系列筛选试验，使纳米 $\\mathrm{siO}_{2}$ 改性醇酸涂料的性能有明显提高。  \n\n纳米有机防腐涂料原理如下。  \n\n$\\textcircled{1}$ 体积效应纳米粒子尺寸，一般为 $\\mathbf{1}\\sim\\mathbf{100}~\\mathrm{nm}$ 。固化后的漆膜的微观结构是一个高分子网状结构。一般常规涂料的成膜物质“结构孔”的微孔 $(10^{-7}\\sim10^{-5}\\mathrm{cm})$ ，如果在成膜物质中含有纳米粉体材料，正好填充了有机涂层无法避免的“结构孔”（孔径在 $1\\mathrm{{nm}}$ 以上)，这是常规涂层无法实现的。因为这些“结构孔”被纳米材料所填充，所以可防止各种腐蚀性介质的渗透。  \n\n$\\textcircled{2}$ 表面效应纳米材料的巨大的比表面积和表面能，对涂层最直接的效应，就是大大提高了被保护金属和涂层之间的不饱和键的结合程度。即由纳米粒子的表面活性在涂层-金属界面发生一系列化学作用而形成涂层和金属表面无明显界面。在纳米涂层中，所形成的涂层-基体金属表面的结合力，远远大于腐蚀电化学反应物对涂层与金属表面的扩张力，使电解液和氧所形成电化学反应，在涂层-基体金属表面失去向四周延伸的空间。  \n\n$\\textcircled{3}$ 光学效应纳米材料的光学效应能有效地抵御紫外线照射对有机高分子涂层的降解作用，而使涂层的防魔寿命得到延长。  \n\n纳米 $\\mathrm{SiO}_{2}$ 为白色鳞片粉末，比表面积为 $640\\mathrm{m}^{2}/\\mathrm{g}$ ，粒度为 $10\\mathrm{\\sim}20\\mathrm{nm}$ 。试验方案采用正交试验。分散方法如下：  \n\n![](images/e8523519f882bd928edab4beb2034e47af846292e07ac13b1d743dc86a376a6e.jpg)  \n\n经过正交试验极差分析，纳米 $\\mathrm{SiO}_{2}$ 的最佳用量为 $3\\%\\sim4\\%$ ；超分散剂最佳用量为 $2\\%$ 分散时间为 $60\\mathrm{{min}}$ ，KH-570的用量为 $1\\%$ 。此时纳米材料改性醇酸涂料的硬度最高，耐水性、耐碱性也明显提高。其中纳米 $\\mathrm{\\SiO}_{2}$ 的用量对漆膜性能影响最显著。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 191,
+        "chunk": "# 5.超支化聚合物改性醇酸树脂  \n\n超支化聚合物的初步理论是Flory在1953年提出的。1987年DuPont公司的 $\\mathrm{\\sfKim}$ 申请了第一个专利，1990年 $\\mathrm{\\Kim}$ 报道了超支化聚合物的合成与表征方法。现在很多世界著名公司如IBM公司、DuPont公司、Dow化学工业公司和Perstorp公司都投入巨资开展该领域的研究，并已在合成、表征理论研究方面取得很大进展。  \n\n超支化聚合物是一类新型的具有三维立体结构高度支化的合成高分子，许多具有近似分子量和窄分子量分布的支化结构从核向四周延伸。它和线型聚合物不同，具有高官能度，球形对称三维结构，分子间、分子内不发生链缠结的结构特点。其结构紧密性赋予了特殊的物理性质和化学性质，如高溶解性、低黏度、高流变性等，使超支化聚合物在很多领域，都有广阔的开发前景。在涂料中，作为成膜物的黏度改性剂、引发剂、交联固化剂等，改善涂料的流变性，降低VOC含量及提高漆膜的性能。采用端基为羟基的超支化聚合物代替醇酸树脂中的多元醇，可以对醇酸树脂进行改性。·  \n\n超支化聚合物的合成与醇酸树脂的改性，首先将多元醇、二羟甲基丙酸、催化剂对甲基苯磺酸按设计配方加入反应器，用二甲苯回流，一定时间后减压蒸馏脱去溶剂和水，得到超支化聚合物。在醇酸树脂的合成过程中，以超支化聚合物代替多元醇与脂肪酸和苯酐等单体反应，升温到 $200\\Upsilon$ ，用二甲苯回流。反应达到一定酸值后，降温兑稀。超支化聚合物改性后的醇酸树脂比商业树脂的摆杆硬度高，与固化剂TDI加成物和三聚体的相容性好。改性后的醇酸树脂的其他特殊性能还有待进一步研究。  \n\n在醇酸树脂合成中，试图将超支化聚合物的一些特殊性质和结构赋予醇酸树脂，除了利用它可以提高反应活性和降低黏度外，期待所合成的具有高度支化结构的醇酸树脂在应用黏度下的配方中有更高的固含量，在溶剂型高固体分涂料中有着广泛的应用前景。  \n\n结语：  \n\n由2010年1月1日开始实施的VOC含量限定新法规将给欧洲甚至世界涂料市场带来重大的影响，因为届时在欧洲将不可能再应用传统醇酸技术。原材料供应商和涂料生产商正在实验室开展大量的工作以便开发可行的解决方案。目前受到关注的主要技术为： $\\textcircled{1}$ 丙烯酸和丙烯酸聚氨酯共聚物； $\\textcircled{2}$ 醇酸乳液和水稀释醇酸； $\\textcircled{3}$ 丙烯酸/醇酸复合乳液； $\\textcircled{4}$ 高固体分醇酸树脂。  \n\n最后，在竞争中获胜的技术必须能够最准确地反映目标市场的需求。根据采购标准，终端用户可按照早期涂装经验中新配方涂料是否能为满足其期望而决定接受还是拒绝该产品。因此，对于新型的光泽涂料，具有可接受的施工性能（开放时间）和外观性能（光泽、流动性和成膜性能）比后期评估的力学性能更为重要。  \n\n如果力学性能为次要，那么就需要对在顺序加料聚合方面投入众多努力以及应用昂贵的聚氨酯化学品提出疑问。如果目标是符合欧盟指令，那么零VOC涂料的需求也值得怀疑，因为VOC 的水平已经只占传统醇酸光泽涂料VOC水平的一小部分。  \n\n如果每升涂料的价格对于终端用户而言非常重要，那么高固体分醇酸就将处于劣势，因为使用昂贵的反应性稀释剂将使成本急剧提高。高固体分醇酸的另一个劣势是其在进一步降低VOC含量方面存在固有的限制。着色剂的加入可能带来额外的问题。  \n\n最终，获胜的技术不仅只会优化单一的性能，而是会使所有的性能参数表现良好，这就为原材料供应商和涂料配方师共同设定了一个极具难度的挑战。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 192,
+        "chunk": "# 第三节酚醛树脂",
+        "category": " Introduction"
+    },
+    {
+        "id": 193,
+        "chunk": "# 一、概述  \n\n酚醛树脂作为世界上最早发现及应用的合成树脂，有着相对低廉的价格和简单的合成工艺，但酚醛树脂有良好的耐热性、电绝缘性和阻燃性，因而广泛应用于涂料、胶黏剂、复合材料等领域。随着社会经济的快速发展，人们对酚醛树脂的性能要求也愈来愈高，如航空航天等尖端技术领域，对酚醛复合材料的耐热、防腐等提出了更高的要求，要求酚醛树脂行业能在新技术开发和应用上取得进展，生产出满足各种应用性能的新型酚醛复合材料。  \n\n酚醛树脂是由醛类和酚类在酸性或碱性条件下，通过缩合反应得到的合成树脂，小分子量酚醛树脂可溶于水中，伴随着缩合反应进行，树脂聚合程度上升，酚醛树脂的分子量也增大，树脂的水溶性逐渐下降，有机溶剂中的溶解性会上升，若缩合反应继续进行，会逐步生成固体的酚醛树脂。  \n\n酚的羟基与苯环直接相连接，酚羟基中氧原子的未共用电子对与苯环上的大 $\\pi$ 电子构成共轭体系产生电子的离域作用，使电子向苯环方向转移，导致苯环上电子云密度增加，特别是邻、对位增加的更多。因此苯环容易发生亲电取代反应，取代基主要是酚羟基的邻、对位。利用羰基化合物（醛类）与酚羟基邻位或对位的氢原子发生缩合生成酚羟基苯甲醇，进一步缩合下去，最终可形成高分子产品—酚醛树脂。酚与醛的摩尔比对酚醛树脂结构起决定作用，醛的用量多，有利于酚羟基的邻、对位都引入羟甲基，使缩合反应可以继续进行下去。  \n\n当醛与酚的摩尔比小于1时，平均每个酚分子结构上形成的羟甲基不到一个，使分子间的缩合反应难以持续进行，不能形成热固性酚醛树脂；当醛与酚的摩尔比大于1时，平均每个酚分子结构上形成的羟甲基超过一个，使分子间的缩合反应可以继续进行；当醛与酚的摩尔比大于等于2时，平均每个酚分子成结构上形成的羟甲基也大于等于2个，从理论上说，若不设法中止反应，分子间的缩合反应可以无限进行。因此，醛与酚的摩尔比对酚醛树脂的形成非常关键，一般酚醛树脂所采用的醛与酚摩尔比在 $1{\\sim}2$ 之间，不同酚具有不同官能度，所形成的酚醛树脂性能和用途也不尽相同。  \n\n利用亚甲基（—CHz—）将酚连接组成的酚醛树脂，结构中含有苯环，树脂刚性大、柔韧性较差；若羟甲基进一步固化，会形成由C—C键构成、结构紧密的网状结构，它对于各种化学物质较为稳定，因此酚醛涂料的防腐蚀性能较好，其特点是耐酸性突出，但由于分子结构中有大量极性酚羟基，容易和碱反应生成酚盐，所以耐碱性较差。酚醛缩合物既可成为独立的纯酚醛树脂，也可通过改性来改进酚醛树脂的性能，从而扩展酚醛树脂的适用范围。  \n\n火灾产生的有毒烟雾已成为火灾事故的最大危害因素，开发低烟无毒的建筑材料能够很好地缓解这一问题，由于酚醛树脂强度大、固定碳率高、高温可形成牢固的碳-碳结构，耐火性能突出，与各种有机物和石墨的结合性好，可用于含碳耐火材料的结合剂。用以加工的酚醛材料不加阻燃剂，也具有较好的阻燃性，同时也具有良好的低烟雾性。可以预计，酚醛复合材料在大型建筑、隧道、交通工具等防火要求高的场合应用会愈来愈广。",
+        "category": " Introduction"
+    },
+    {
+        "id": 194,
+        "chunk": "# 二、原料  \n\n合成酚醛树脂最基本的原料是醛和酚，产品工艺中若涉及萃取步骤的，还要使用能将酚醛树脂溶解的溶剂，若生产改性酚醛树脂，需要使用改性酚醛树脂所涉及的原料等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 195,
+        "chunk": "# 1.醛  \n\n分子结构中含有羰基官能团，且基与一个氢原子和一个烃基（或氢原子）相连的化合物称为醛；与两个烃基相连的基化合物称为酮。根据与羰基相连的烃基不同，分为脂肪族醛、脂环族醛、芳香族醛，由烃基是否饱和可分为饱和醛、不饱和醛，由醛所含羰基的数目可分为一元醛、二元醛等。常用醛的物理常数见表2-1-59。  \n\n表2-1-59常用醛的物理常数  \n\n\n<html><body><table><tr><td>名 称</td><td>结构式</td><td>熔点/C</td><td>沸点/℃</td><td>密度D</td></tr><tr><td>甲醛</td><td>HCHO</td><td>92</td><td>21</td><td>0.815</td></tr><tr><td>乙醛</td><td>CHCHO</td><td>123</td><td>20.8</td><td>0.780</td></tr><tr><td>丙醛</td><td>CHCHCHO</td><td>-81</td><td>48.8</td><td>0.807</td></tr><tr><td>丙烯醛</td><td>CHz—CHCHO</td><td>87</td><td>52.7</td><td>0.841</td></tr><tr><td>丁醛</td><td>CH(CHz)CHO</td><td>99</td><td>75</td><td>0.817</td></tr><tr><td>2-丁烯醛</td><td>CHCH—CHCHO</td><td>76.5</td><td>104</td><td>0.857</td></tr><tr><td>戊醛</td><td>CH(CHz)CHO</td><td>91. 5</td><td>103.4</td><td>0. 819</td></tr><tr><td>苯甲醛</td><td>CHCHO</td><td>55</td><td>179</td><td>1. 050</td></tr></table></body></html>  \n\n醛羰基中的氧原子可以与水形成氢键，低碳链的醛如甲醛、乙醛等都可以与水混溶，随着碳链的增长，水中溶解性逐渐减小， $\\mathbf{C}_{5}$ 以上的醛水中溶解性已很低或不溶于水。目前生产涂料用酚醛树脂，一般都采用最简单的醛一—甲醛，其他醛类很少采用。甲醛在常温下是气体，因此工业生产采用甲醛的水溶液，常规含量为 $37\\%$ 。  \n\n考虑到甲醛水溶液含有大量水分，会产生较大的污染源，近年来，开始出现采用多聚甲醛生产酚醛树脂，但酚醛树脂利润较低，而多聚甲醛成本较高，因而进展不大。",
+        "category": " Introduction"
+    },
+    {
+        "id": 196,
+        "chunk": "# 2.酚  \n\n羟基直接与芳环相连的化合物称为酚，根据芳环上所连羟基的数目可分为一元酚和多元酚，由于分子中饱和羟基，其物理性质与醇相似，沸点、熔点较相应的烃高，能溶于乙醇、乙醚等有机溶剂中，除少量烷基酚为液体，大部分酚为结晶固体，酚还具有较强腐蚀性。  \n\n酚的分子结构中含有直接相连的羟基与芳环，相互之间有较大的干扰和影响，因此酚分子上羟基与芳环的化学性质，与醇、芳烃的化学性质虽具有共性，但更重要的是它们具有与醇和芳烃不同的特性。酚分子苯环的邻、对位容易发生亲电取代反应，合成酚醛树脂主要就是利用这一特性反应来完成的。常用酚的物理常数见表2-1-60。  \n\n表2-1-60常用酚的物理常数  \n\n\n<html><body><table><tr><td>名 称</td><td>分子式</td><td>熔点/C</td><td>沸点/C</td><td>水溶性/(g/100g)</td></tr><tr><td>苯酪</td><td>CHO</td><td>40.8</td><td>181.8</td><td>8热水</td></tr><tr><td>邻甲酚</td><td>CHO</td><td>30.5</td><td>191</td><td>2.5</td></tr><tr><td>间甲酚</td><td>CHO</td><td>11. 9</td><td>202.2</td><td>2.6</td></tr><tr><td>对甲酚</td><td>C,HO</td><td>34.5</td><td>201.8</td><td>2.3</td></tr><tr><td>a-蔡酚</td><td>CoHO</td><td>94</td><td>279</td><td></td></tr><tr><td>对苯二酚</td><td>CHO</td><td>170</td><td>286.2</td><td>8</td></tr><tr><td>对权丁酚</td><td>CoHO</td><td>98.4</td><td>239.7</td><td>一</td></tr><tr><td>对叔辛酚</td><td>CHO</td><td>83.5</td><td>276</td><td>一</td></tr><tr><td>对壬基酚</td><td>CisHO</td><td>一</td><td>315</td><td>一</td></tr><tr><td>对苯基酚</td><td>CHoO</td><td>161.5</td><td>一</td><td></td></tr><tr><td>双酚A</td><td>C1s HO</td><td>157.3</td><td>251</td><td>一</td></tr></table></body></html>\n\n酚类的品种较多，但并不是所有的酚都会用于生产酚醛树脂，应根据拟生产酚醛树脂的  \n\n特性和要求，选择合适的酚类进行配合，目前涂料行业用酚醛树脂中较常用的酚有：苯酚、双酚A、对苯基苯酚、对叔丁酚、对壬基酚、十二烷基酚等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 197,
+        "chunk": "# 3.其他  \n\n酚醛树脂的合成是由酚与醛在酸性或碱性条件下进行的，因此除最基本的醛与酚外，还需要酸性或碱性催化剂。目前最常用碱性催化剂有熟石灰（氢氧化钙）、液碱（ $30\\%$ 氢氧化钠)、乌洛托品（六亚甲基四胺）等；目前最常用酸性催化剂有盐酸（ $30\\%)$ 、草酸等。  \n\n为保证生产的酚醛树脂的品质，在一些纯酚醛树脂的生产工艺中，常使用甲苯等溶剂，对酚醛树脂进行萃取，使树脂溶解其中，然后利用甲苯与水不相容的特性，进行水洗，以去除所夹带的杂质，提高树脂质量。  \n\n若生产改性酚醛树脂，要使用改性剂，如生产松香改性酚醛树脂要使用松香与酚醛产物进行加成反应，然后还要与多元醇酯化（常用甘油、季戊四醇等)；生产酚醛醚化浆应根据要求使用丁醇或乙醇与酚醛产物进行醚化反应，以完成改性的目的。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 198,
+        "chunk": "# 三、酚醛树脂合成的基本化学反应  \n\n酚类和醛类的缩聚产物通称酚醛树脂，它是最早合成的一大类热固性树脂。1909 年L.H.Backeland首先合成了有应用价值的酚醛树脂合成体系，从此开始了酚醛树脂的工业化生产。",
+        "category": " Introduction"
+    },
+    {
+        "id": 199,
+        "chunk": "# 1.合成酚醛树脂的条件  \n\n酚醛树脂是由酚类（苯酚、对叔丁基酚、二甲酚等）和醛类（甲醛、乙醛、糠醛等）在酸或碱等催化下合成的体型结构的缩聚物。  \n\n(1）单体的官能度及原料选择为了能生成体形结构的聚合物，必须有支化交联点，即体系中至少一种单体有三个反应活性点（官能度)，由于醛类（生产中主要使用甲醛）作为二官能度的单体参与缩聚反应，所用的酚类一般要求有三个可反应的官能团（官能度)。酚分子中的羟基和芳环是直接相连接的，彼此间有较大的影响。其中的氧原子容易与苯环大 $\\pi$ 共轭，使苯环上的电子云密度增加，特别是邻、对位增加得更多。因此苯环容易发生亲电取代反应，并且取代基主要在酚羟基的邻、对位，因此它有三个活性点，可视作三官能度的单体。间甲酚和3,5-二甲酚也具有三个活性点。而对甲酚和邻甲酚只有两个活性点，在一般情况下难以形成体型结构的聚合物。  \n\n(2）体系的平均官能度和加料方式当体系中某单体具有三个官能度时，大分子便可向三个方向生长，得到三维网状结构的体型聚合物。这种类型的聚合物具有高强度和耐热、耐腐蚀的特性。但是不能溶解和熔融，难以加工使用。因此，如果单体中含有多官能度单体，生产实践中一般只制备低分子量的聚合物，称为低聚物，成型使用时再进一步交联反应。  \n\n如何制备含有三个官能度以上单体的缩聚物是一个重要的问题，因为这种缩聚反应如果控制不当，进行到一定程度时，反应体系的黏度会突然增加，形成不溶不熔的凝胶，这种现象称为凝胶化，出现凝胶时的反应程度 $(\\boldsymbol{\\phi}_{\\mathrm{c}})$ ）称凝胶点。碱催化条件下的酚醛树脂缩聚反应容易产生凝胶，防止出现凝胶具有特别重要的意义。  \n\n关于凝胶点的预测，有很多方法，其中Carothers方程式（2-1-11）最为简便。  \n\n出现凝胶时的反应程度 $\\pmb{\\mathscr{p}}_{\\mathrm{c}}=2/f$ 定义体系的平均官能度 $f=$ 参与反应的官能团数/总单体分子数  \n\n假如有两种官能团A和 $B$ 个数不相等，且 $B{>}A$ 。那么，参与反应的官能团数为2A，原因是A和B逐一反应后，多余的 $B$ 成为不能参与反应的官能团。  \n\n因为，官能团个数 $\\c=$ 单体分子数 $\\times$ 该单体官能度  \n\n$A{=}N_{\\Lambda}f_{\\Lambda}$ $B{=}N_{\\mathrm{{B}}}f_{\\mathrm{{B}}}$  \n\n所以，平均官能度 $f{=}2A/(N_{\\mathrm{A}}{+}N_{\\mathrm{B}}){=}2N_{\\mathrm{A}}{\\times}f_{\\mathrm{A}}/(N_{\\mathrm{A}}{+}N_{\\mathrm{B}})$  \n\n表2-1-61是常用酚醛树脂配方及其平均官能度、凝胶点的计算举例。配方1预测最大反应为 $83\\%$ 。而配方2则不存在凝胶点（反应程度 $>100\\%)$ 。值得注意的是：在类似配方2这样不会产生凝胶的体系，要注意加料方式，即官能团个数比较少的组分（这里为甲醛）往苯酚中滴加才能避免凝胶，若反向滴加，反应活性较大时容易产生凝胶。例如，当苯酚滴加到 $60\\%$ 时，即为配方3，计算得到 $\\pmb{\\mathscr{p}}_{\\mathrm{c}}=0,83$ @  \n\n表2-1-61酚醛树脂配方及其平均官能度计算  \n\n\n<html><body><table><tr><td rowspan=\"2\">项 目</td><td colspan=\"2\">配方1（催化：pH>7）</td><td colspan=\"2\">配方2（催化：pH<3）</td><td colspan=\"2\">配方3</td></tr><tr><td>单体分子数</td><td>官能度</td><td>单体分子数</td><td>官能度</td><td>单体分子数</td><td>官能度</td></tr><tr><td>苯酚</td><td>1</td><td>3</td><td>1</td><td>3</td><td>1×60%</td><td>3</td></tr><tr><td>甲醛</td><td>1.5</td><td>2</td><td>0.9</td><td>2</td><td>0.9</td><td>2</td></tr><tr><td>苯酚官能团个数</td><td colspan=\"2\">1X3=3</td><td colspan=\"2\">1×3=3</td><td colspan=\"2\">0.6×3=1.8</td></tr><tr><td>甲醛官能团个数</td><td colspan=\"2\">1. 5X2=3</td><td colspan=\"2\">0.9×2=1.8</td><td colspan=\"2\">0. 9X2=1.8</td></tr><tr><td>总单体数</td><td colspan=\"2\">1+1.5 =2. 5</td><td colspan=\"2\">1+0. 9 =1. 9</td><td colspan=\"2\">0.6+0.9=1.5</td></tr><tr><td>参与反应官能团数</td><td colspan=\"2\">2×3. 0=6. 0</td><td colspan=\"2\">2X1.8=3. 6</td><td colspan=\"2\">2X1.8=3. 6</td></tr><tr><td>平均官能度</td><td colspan=\"2\">f=2×3. 0/(1+1.5)=2.4</td><td colspan=\"2\">f=2×1. 8/(1+0. 9) =1. 89</td><td colspan=\"2\">f=2×1.8/(0. 6+0.9)=2. 4</td></tr><tr><td>凝胶点</td><td colspan=\"2\">p=2/f=0.83</td><td colspan=\"2\">P=2/f=1.06</td><td colspan=\"2\">p=2/f=0.83</td></tr></table></body></html>  \n\n(3）反应介质及其酸碱性酚醛树脂合成必须有酸或碱催化。实验发现， $\\mathrm{pH}=3\\sim3.1$ 称为“中性点”，甲醛和苯酚的混合物在中性点加热至沸腾也不发生反应，若加人酸使$\\mathsf{p H}{<}3$ ，或加入碱使 $\\mathsf{p H}{\\mathsf{>}}3$ ，则反应立刻发生。  \n\n在酸或碱催化下，甲醛和苯酚缩聚反应的特点是反应的平衡常数很大（ $K=4000$ ，缩聚反应的速度受排除反应副产物水的影响不大，甚至在水溶液中合成酚醛树脂也能顺利进行。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 200,
+        "chunk": "# 2.热固性酚醛树脂的合成原理 $\\mathrm{\\langlepH>7}$ 一  \n\n热固性酚醛树脂，是控制合成反应至一定条件后得到的树脂，如果合成反应程度不加限制，缩聚反应一直进行到底，它将形成不溶不熔的具有三维网状结构的体型树脂。一般合成阶段在树脂处于可溶可熔的A阶就停止反应，成型加工时再加热固化。  \n\n(1）反应历程苯酚（碱催化)→酚钠（负离子）→邻、对位电负性大大增加→甲醛$\\mathrm{(CH_{2}-O)}$ 上的碳在酚钠邻、对位取代加成→质子转移 $\\mathbf{\\Psi}\\to$ 生成邻、对位的羟甲基苯酚 $\\mathbf{\\rightarrow}$ 继续与甲醛加成生成多羟甲基苯酚→同时羟甲基苯酚之间缩合（或羟甲基苯酚与苯酚邻、对位缩合)→聚合产物  \n\n(2）动力学在加成反应中，酚羟基的对位活性比邻位大 $(1.07:1)$ ，对羟甲基苯酚再加成的活性将降低 $40\\%$ 。但反应中苯酚有两个邻位，而且邻羟甲基苯酚再加成的活性是提高的。因此易于形成多羟甲基苯酚，造成体系中甲醛紧缺，游离酚含量居高不下。  \n\n缩聚反应主要通过对位的羟甲基进行，分子中留下较多的邻位羟甲基。产物中苯酚部分主要由次甲基连接。虽然两个羟甲基相互缩聚可以生成甲醚键（—CH—O- $\\mathbf{\\boldsymbol{C}}\\mathbf{\\boldsymbol{H}}_{2}-\\mathbf{\\beta})$ ，但在碱性条件下容易分解逸出甲醛，又生成次甲基键 $\\begin{array}{r l}{(-\\mathrm{CH}_{2}-)}\\end{array}$  \n\n在碱性条件下，加成反应比缩聚反应快，所以降低反应温度有利于加成反应，同时也容易控制产品在可溶可熔的A阶。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 201,
+        "chunk": "# 3.热塑性酚醛树脂的合成原理 $(\\mathrm{pH}<3)$  \n\n热塑性酚醛树脂，在合成中得到的是线型结构，必须在进一步的成型过程中加入固化剂，它才能获得三维网状结构。  \n\n(1）反应历程甲醛 (酸催化、水分子)→生成 $\\mathrm{CH}_{2}\\mathrm{OH}\\mathrm{-}$ 主要在苯酚对位亲电取代→生成对位的羟甲基苯酚→快速与游离苯酚缩合（主要在对位）→二酚基甲烷→在酚基邻位继续加成→线型聚合产物  \n\n(2）动力学在强酸性条件 $\\mathrm{(pH<3}$ ）下，缩聚反应的速率大体上正比于氢质子（酸）的浓度。缩聚比加成快5倍，如果甲醛分子的个数不比苯酚多的话，可合成线型酚醛树脂，它是热塑性的，分子内不含羟基。例如，当甲醛/苯酚为0.8，数均分子量 $M_{\\mathrm{n}}{\\approx}500$ 时，平均每个分子链中大约含有五个苯环，产物是可溶可熔的，须加入六亚甲基四胺等才能固化使用。  \n\n若甲醛过量，可导致支化，甚至凝胶。二酚基甲烷和甲醛反应的速度大致与苯酚相同。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 202,
+        "chunk": "# 4.高邻位酚醛树脂的合成原理 $\\mathrm{(pH}=4\\sim7)$  \n\n高邻位酚醛树脂，在合成中使用锰、钻等金属碱盐作催化剂，得到苯酚部分主要通过邻位连接的热塑性树脂。固化速度快，最终产品热刚性好。  \n\n(1）反应历程甲醛(水分子)→甲二醇 $^+$ 二阶金属离子（催化剂)→与苯酚氧原子整合，并在邻位亲电取代→生成邻羟甲基苯酚 $^+$ 二阶金属离子 (催化剂)→继续与游离苯酚氧原子整合，并在邻位亲电取代→形成 $_{o,o^{\\prime}}$ -二羟基二苯基甲烷→高邻位线型聚合产物  \n\n(2）动力学可用的催化剂中，锰、钴、镉、铬最为有效，其次可以用镁和铅，铜、镍的氢氧化物也很有效。二阶金属离子在反应历程中，与酚羟基形成整合物，因此优先生成邻位加成的o， $\\bullet^{\\prime}$ -二羟基二苯基甲烷。0， $o^{\\prime}$ -二羟基二苯基甲烷在异构体中活性最大（表2-1-62)，由此扩展而成的高邻位酚醛树脂固化比一般的热塑性酚醛树脂快 $2{\\sim}3$ 倍。  \n\n表2-1-62二羟基二苯基甲烷异构体的反应活性  \n\n\n<html><body><table><tr><td>异构体</td><td>凝胶时间/8</td><td>异构体</td><td>凝胶时间/s</td></tr><tr><td>0，0-二羟基二苯基甲烷</td><td>60</td><td>p，p-二羟基二苯基甲烷</td><td>175</td></tr><tr><td>o,p二羟基二苯基甲烷</td><td>240</td><td></td><td></td></tr></table></body></html>\n\n①固化剂：15%六亚甲基四胺，温度160℃。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 203,
+        "chunk": "# 四、酚醛树脂",
+        "category": " Introduction"
+    },
+    {
+        "id": 204,
+        "chunk": "# 1.酚醛树脂分类  \n\n酚醛树脂是开发应用较早的一类树脂，如酚醛调合漆长时间占据了人们的日常生活，其中就使用松香改性酚（苯酚）醛树脂，胶印油墨中使用松香改性酚（双酚A、对叔丁酚）醛树脂，酚醛胶黏剂中使用纯酚（对叔丁酚）醛树脂等。酚醛缩合物可作为独立的纯酚醛树脂使用，也可用其他化合物改性来调整酚醛树脂原有的性能特点，从而拓展酚醛树脂用途。  \n\n由酚醛树脂的分子结构特征按以下两类划分是比较适宜的。  \n\n第一类，纯酚醛树脂：在催化剂的作用下，通过酚（常用的是对叔丁酚、苯酚等）与醛（最常用的是甲醛）的缩合反应，可产生满足各种性能需要的酚醛树脂。  \n\n第二类，改性酚醛树脂：酚醛树脂结构中的酚羟基在树脂合成中通常不参与反应，因此酚醛树脂中存在大量酚羟基，酚羟基和亚甲基容易被氧化，致使颜色变深，使材料的性能发生变化，采用化学反应引入除酚、醛之外的其他成分，接入到酚醛树脂的分子链上，起到保护酚羟基或亚甲基、改善和突出某种性能的目的。通常由松香改性、醇改性、环氧改性、醇酸改性等。目前应用较多的是松香改性酚醛树脂、醇类（主要为丁醇）醚化酚醛树脂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 205,
+        "chunk": "# 2.生产工艺和工艺过程  \n\n酚醛树脂合成最重要工艺过程是酚醛缩合，这是不同类型酚醛树脂共同点，与其他涂料用合成树脂不同的是，目前酚醛树脂在涂料行业中，改性酚醛树脂的用量要大于纯酚醛树脂，其中使用最大的是松香改性酚醛树脂。同样是酚醛树脂，不同的类型，其生产工艺相差很大，尤其在改性酚醛树脂上更为明显，不同的改性剂，改性工艺完全是两回事。  \n\n(1）纯酚醛树脂酚基的对位被烃基取代后，酚由三官能度成为二官能度，缩合反应的反应程度更容易控制，而且烃基取代酚制得的树脂具有更好的性能，涂料行业通常用于合成纯酚醛树脂，如对叔丁基酚、对苯基酚和对叔辛基酚等。  \n\n合成的工艺路线如下：在碱性或酸性条件下，烃基取代酚与甲醛缩合反应达到一定程度后，终止反应，缩合产物经水洗后，采用先常压、后减压的方法脱去反应水，中控合格后出料。  \n\n在碱性条件下酚醛缩合生成热固性纯酚醛树脂，根据其特性，主要用于生产重防腐蚀涂料、酚醛胶黏剂等；使用时可利用酸性催化或加热使之交联固化。在酸性条件下酚醛缩合生成热塑性纯酚醛树脂，根据其特性，也可用于生产防腐蚀涂料、黏合剂、橡胶添加剂等；使用时可利用碱性催化或加热使之交联固化。  \n\n![](images/fb4dbe18670e63f7ac10123a52d23d446b384763bcb5593443585118ba12f06f.jpg)  \n\n(2）松香改性酚醛树脂甲醛和酚在碱性条件下缩合后，再与松香进行加成，并与多元醇酯化可得到松香改性酚醛树脂。由于松香特有的结构特征，用松香改性使酚醛树脂与颜料润湿分散性有很大改善，可广泛用于制造酚醛调和漆与平版胶印油墨。松香改性苯酚酚醛树脂主要用于生产酚醛调和漆，而来用烷基取代酚的松香改性酚醛树脂主要用于生产平版胶印油墨。  \n\n要进一步提高松香改性酚醛树脂性能，目前主要采用改变酚类结构的方法，即使采用碳链较长的烷基酚如辛基酚（POP)、壬基酚（PNP)、十二烷基酚（PDDP）等，可使树脂具有良好的脂肪烃溶剂溶解性（正庚烷值)、较高的黏度与分子量；用于制造的印刷油墨可使用高沸点脂肪烃溶剂，有利于减少高速印刷时产生的飞墨，提高涂层的流平性和光泽，改善颜料的润湿分散性。  \n\n由于酚基对位取代基的增大，影响缩合反应进行，取代基碳链越长，树脂亚麻油黏度越低，但正庚烷值越高；因此若用对壬基酚或十二烷基酚生产酚醛树脂，由于分子量难以增大，油中黏度难做高，通过加入适量顺酐、引入高支链化结构，并采用较高的酚醛比例，才能得到合适的酚醛树脂。  \n\n烷基取代基的结构对缩合的反应性、树脂的软化点、油溶性有较大影响。酚与醛的结构、摩尔比，酚醛在整个体系中的比例，反应体系的酸碱性、催化剂的选择、对松香酚醛树脂的性能有极大影响，从而应用在不同领域。涂料行业将松香改性酚醛树脂应用于酚醛调合漆与重防腐涂料，能取得良好的性能；但随着行业的发展与涂料品种的性能提升，及市场对成本的要求，目前松香改性苯酚甲醛树脂使用量较以前已下降较多。  \n\n要得到合适的松香改性酚醛树脂，若采用不同分子结构的酚与多元醇，酚醛在树脂体系中的比例也不同，随着酚醛比例的上升，树脂的软化点、耐酸碱性、耐水性都有所提高，但油溶性和脂肪烃溶剂溶解性会下降。如使用苯酚的树脂，酚醛比例约为 $14\\%\\sim15\\%$ ；使用双酚A的树脂，酚醛比例约为 $15\\%\\sim16\\%$ ；使用辛基酚、壬基酚的树脂，酚醛比例约为$28\\%\\sim30\\%$ ，使用十二烷基酚的树脂，酚醛含量约为 $32\\%\\sim35\\%$ 。生产松香酚醛树脂可采用一步法或二步法，二步法生产树脂色泽较浅，但工艺设备多，控制要求高，酚醛浆贮存期短、易报废，目前松香酚醛树脂生产，大部分都采用一步法生产。  \n\n在酸性介质中，酚与甲醛产生的酚醇很容易进一步缩合成分子量更高的缩合物，有可能完全胶化或不溶于松香；在碱性介质中，反应平稳，容易控制，生成的树脂软化点也高，因此松香改性酚醛树脂一般都采用碱性催化剂，使用一步法生产松香酚醛树脂时，常用的催化剂是乌洛托品，在生产浅色松香（苯）酚醛树脂时，也有采用氢氧化钙作催化剂的。  \n\n不同的酚具有不同的官能度，在实际生产中最终采用的酚与醛摩尔比就不同；采用苯酚的酚醛树脂，其酚与醛的摩尔比--般为 $1:(1.5{\\sim}1.7)$ ；采用（叔丁酚、辛基酚、壬基酚)的酚醛树脂，其酚与醛的摩尔比一般为 $1:(2.5{\\sim}3.0)$ ；采用双酚A的酚醛树脂，其酚与醛的摩尔比一般为 $1:(5.2{\\sim}5.4)$ 。  \n\n工艺路线及基本原理：  \n\n![](images/b876a0f353294261cbd1531dfef9d9fc95b0368dd95feb5811015b1500d171e0.jpg)  \n\n(3）酚醛醚化浆（醇醚化酚醛树脂）为改善酚醛树脂的韧性、溶剂溶解性及其他物理性能，可采用醚化的方法对酚醛树脂进行改性，醚化后的酚醛树脂由于降低了极性，使得树脂更容易溶解于芳烃溶剂中，改善了树脂的柔韧性，从而扩大树脂的应用领域。用低碳链醇醚化酚醛树脂，对树脂性能的改善作用不大，一般采用丁醇、乙二醇、丙三醇、聚乙烯醇等改性酚醛树脂，得到各种不同用途的醇醚化酚醛树脂。  \n\n合成的工艺路线如下：在碱性条件下，酚与甲醛缩合反应达到一定程度后，中止反应并调整到酸性，经水洗后，加人丁醇，进行回流脱水反应，反应完成后，脱出过量丁醇，中控合格后出料。酚醛醚化浆可用糖瓷反应釜生产，制造纯酚醛树脂的反应釜可通用。  \n\n涂料行业常用的丁醇来改性酚醛树脂，制得热固性酚醛醚化浆，可提高酚醛树脂的溶剂溶解性，与环氧树脂配合，交联成膜，主要用于耐腐蚀漆。  \n\n工艺路线及基本原理：  \n\n![](images/725a3adb2d3b754db6c1a9590e458d5b822654cce8d9527d9ae2d521341f572c.jpg)  \n\n（4）其他类型的改性酚醛树脂除了上述常见的改性酚醛树脂外，为了适应不断发展的应用需求，也有采用其他化学组分来对酚醛树脂改性，从而达到改善或突出性能的目的，较为常见的还有下列改性酚醛树脂。  \n\n硼（钼）改性酚醛树脂：利用酚醛树脂的羟基与硼（钼）酸进行酯化反应，从而将硼（钼）元素引入酚醛树脂的结构，硼（钼）改性酚醛树脂具有更为优异的耐热性、瞬间耐高温性和加工性，有良好的芳烃类溶剂溶解性，主要应用于耐高温材料、摩擦材料，航空航天领域可作为耐烧蚀材料使用。 X  \n\n环氧改性酚醛树脂：环氧树脂中的环氧基和酚醛树脂中的酚羟基进行醚化反应、环氧树脂中的环氧基及羟基和酚醛树脂中的羟甲基进行缩合开环反应，从而交联形成体型结构的环氧改性酚醛树脂(也有称为酚醛改性环氧树脂)，改性后树脂兼有酚醛树脂与环氧树脂的良好性能，大大拓展了其应用领域和范围。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 206,
+        "chunk": "# 3.生产设备  \n\n生产酚醛树脂的主要设备是反应釜，但针对不同类型的酚醛树脂，如纯酚醛树脂与改性酚醛树脂等，由于生产工艺的差异，为满足不同的工艺要求，相应的配套装置是不同的。  \n\n松香改性酚醛树脂由于酯化反应温度高达270℃，因而目前一般采用高温导热油循环加热的形式，为满足对加热的要求，反应釜的内置盘管与夹套都通导热油，反应釜采用不锈钢制作，使用浆式搅拌器（附刮沫器)，配有直冷凝器、横冷凝器（附分水器）、真空泵等，采用底部出料方式，可根据需要对成品进行造粒或切片后，即可包装。  \n\n与松香改性酚醛树脂相比，纯酚醛树脂的反应温度不高，回收溶剂阶段的温度最高也不超过 $130^{\\circ}\\mathrm{C}$ ，采用饱和蒸汽加热的形式可满足工艺的要求，不需要内置盘管，反应釜的夹套可通蒸汽与冷却水，根据工艺控制要求进行冷热切换。酚醛缩合与回收溶剂后的出料一般在两个反应釜内分别操作，酚类有较强的腐蚀性，因此对反应釜材质有相应要求，缩合反应釜可采用糖瓷或不锈钢反应釜，回收溶剂后的出采用不锈钢反应釜，两个反应釜都需配备横冷凝器（附分水器），出料到放料盘中，冷却后包装。  \n\n生产酚醛醚化浆，缩合反应完成后，调整酸性、加人丁醇即进入醚化反应，最终成品树脂以一定固体分的酚醛丁醇溶液出现，整个工艺可在单釜内完成。专业生产酚醛树脂的单位，可用生产纯酚醛树脂的缩合反应釜来完成丁醚化酚醛树脂的生产操作。只要安排好生产计划，没必要专门设置生产酚醛醚化浆的设备。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 207,
+        "chunk": "# 4、配方实例  \n\n配方1：210松香改性苯酚甲醛树脂  \n\n(1）配方  \n\na.210松香改性酚醛树脂  \n\n松香 4500kg 甲醛 700kg甘油 410kg H促进剂 25kg苯酚 540kg 氧化锌 7kgb.浅色210松香改性酚醛树脂（亦称2210或210-10松香改性酚醛树脂）松香 4500kg 甲醛 840kg甘油 390kg 氧化镁 5.2kg苯酚 570kg 氧化锌 7.6kg(2）质量标准外观 透明 色泽(Fe-Co)210 ≤12苯中清 清 2210(或210-10) ≤10酸值/（mgKOH/g) ≤20 软化点 135\\~150°C  \n\n(3）操作  \n\n$\\Phi$ 吸进松香，放去真空，开动搅拌，加人苯酚、氧化锌、氧化镁、H促进剂，加料时应均匀地加人，防止溢锅。  \n\n$\\textcircled{2}$ 当温度下降至 $110^{\\circ}\\mathrm{C}$ 以下时，打开直冷凝器冷却水，可逐渐加入甲醛，加人速度以不溢锅为原则；加完甲醛后在温度 $98\\mathrm{\\sim}102\\mathrm{\\textC}$ 维持3.5h。 力  \n\n$\\textcircled{3}$ 维持毕，关闭直冷凝器冷却水，开横冷凝器冷却水；同时升温脱水（升温时注意液面情况，防止溢锅），温度逐渐上升。  \n\n$\\textcircled{4}$ 当温度升至约 $220^{\\circ}\\mathrm{C}$ 时，打开直冷凝器冷却水，逐渐加入甘油，加完后升温；升温至$265\\%$ ，并保温维持4h。关闭直冷凝器冷却水，保持原温度并抽真空1h。  \n\n$\\textcircled{5}$ 取样，进行终点控制（软化点、酸值)；若终点未到则继续维持减压反应，若维持过程中酸值下降慢，难以达到产品的酸值，则应补加一定量甘油后继续维持，至酸值达到为止。  \n\n$\\textcircled{6}$ 合格后，放料冷却后包装。  \n\n配方2：2116松香改性双酚A甲醛树脂  \n\n(1）配方  \n\n松香 3500kg 氧化锌 10kg甘油 375kg 甲醛 720kg双酚A 375kg  \n\n(2）质量标准  \n\n外观 透明 酸值/(mgKOH/g) ≤18软化点/C 151\\~162 黏度（35C)/mPa · s 1300\\~2000色泽（Fe-Co) ≤12 苯中清 清  \n\n(3）操作  \n\n$\\Phi$ 吸进松香、放去真空，开动搅拌后，加入双酚A、氧化锌，加料时应均匀地加人，防止溢锅。  \n\n$\\textcircled{2}$ 当温度下降至 $110^{\\circ}\\mathrm{C}$ 以下时，打开直冷凝器冷却水，可逐渐加入甲醛，加入速度以不溢锅为原则；加完甲醛后在温度 $98{\\sim}102\\mathrm{\\textC}$ 维持4h。  \n\n$\\textcircled{3}$ 维持毕，关闭直冷凝器冷却水，开横冷凝器冷却水；同时升温脱水（升温时要注意液面情况，防止溢锅)，逐渐升温至 $(175\\pm2)\\uptau$ ，维持0.5h后升温。  \n\n$\\textcircled{4}$ 当温度升至约 $220^{\\circ}\\mathrm{C}$ 时，打开直冷凝器冷却水，逐渐加入甘油，加完后升温；升温至$265\\mathrm{{^\\circ}C}$ ，在 $265\\sim270\\Upsilon$ 维持4h。  \n\n$\\textcircled{5}$ 取样，进行终点控制（软化点、酸值、黏度）。  \n\n$\\textcircled{6}$ 若软化点、酸值未到则继续维持反应；在软化点、酸值接近合格时，可开启真空，在减压下维持反应；有利于加快反应进程，缩短反应时间。  \n\n$\\textcircled{7}$ 及格后，放料冷却后包装。  \n\n配方3：2118松香改性双酚A甲醛树脂  \n\n(1）配方  \n\n松香 3500kg 氧化锌 10kg季虎四醇 425kg 甲醛 750kg双酚A 400kg  \n\n(2）质量标准  \n\n外观 透明 酸值/（mgKOH/g) ≤20软化点/C 157\\~165 黏度（35C）/mPa · s 2000\\~3500色泽（Fe-Co) ≤12 苯中清 清  \n\n(3）操作  \n\n$\\Phi$ 吸进松香、放去真空，开动搅拌后，加人双酚A、氧化锌，加料时应均匀地加入，防止溢锅。  \n\n$\\textcircled{2}$ 当温度下降至 $110^{\\circ}\\mathrm{C}$ 以下时，打开直冷凝器冷却水，可逐渐加入甲醛，加入速度以不溢锅为原则；加完甲醛后在温度 $98{\\sim}102\\mathrm{{C}}$ 维持7h。  \n\n$\\textcircled{3}$ 维持毕，关闭直冷凝器冷却水，开横冷凝器冷却水；同时升温脱水（升温时要注意液面情况，防止溢锅)，逐渐升温至 $(200\\pm2)^{\\circ}\\mathrm{C}$ 维持1h后升温。  \n\n$\\textcircled{4}$ 当温度升至约 $220\\Upsilon$ 时，打开直冷凝器冷却水，逐渐加人季戊四醇，加完后升温；升温至 $265^{\\circ}\\mathrm{C}$ ，在 $265\\sim270\\ensuremath{\\mathrm{~c~}}$ 维持7h。  \n\n$\\textcircled{5}$ 取样，进行终点控制（软化点、酸值、黏度)。  \n\n$\\textcircled{6}$ 若软化点、酸值未到则继续维持反应；在软化点、酸值接近合格时，可开启真空，在减压下维持反应；有利于加快反应进程，缩短反应时间。  \n\n$\\textcircled{7}$ 及格后，放料冷却后包装。  \n\n配方4：2135松香改性叔丁酚甲醛树脂  \n\n(1）配方  \n\n松香 2800kg 叔丁酚 775kg季戊四醇 320kg 轻质氧化 6kg甲醛 1180kg 甘油 50kgH促进剂 2kg  \n\n(2）质量标准  \n\n外观 透明 酸值/（mgKOH/g) ≤22软化点/C 165\\~175 黏度（35C)/mPa \\* s 2000\\~3500色泽(Fe-Co) ≤12 苯中清 清  \n\n(3）操作  \n\n$\\Phi$ 吸进松香、放去真空，开动搅拌后，加入叔丁酚、轻质氧化镁、 $\\mathbf{H}$ 促进剂；加料时应均匀地加人，防止溢锅。  \n\n$\\textcircled{2}$ 当温度下降至 $110^{\\circ}\\mathrm{C}$ 以下时，打开直冷凝器冷却水，可逐渐加入甲醛，加入速度以不溢锅为原则；加完甲醛后在温度 $98\\mathord{\\sim}102\\Upsilon$ 维持6h。  \n\n$\\textcircled{3}$ 维持毕，关闭直冷凝器冷却水，开横冷凝器冷却水；同时升温脱水（升温时要注意液面情况，防止溢锅)，逐渐升温至 $(200\\pm2)\\Upsilon$ 维持1.0h后升温。  \n\n$\\textcircled{4}$ 当温度升至约 $220\\mathrm{{\\circ}}$ 时，打开直冷凝器冷却水，逐渐加人甘油、季戊四醇，加完后升温；升温至 $265\\%$ ，在 $265\\sim270^{\\circ}\\mathrm{C}$ 维持5h。  \n\n$\\textcircled{5}$ 取样，进行终点控制（软化点、酸值、黏度）。  \n\n$\\textcircled{6}$ 若软化点、酸值未到则继续维持反应；在软化点、酸值接近合格时，可开启真空，在减压下维持反应；有利于加快反应进程，缩短反应时间。  \n\n$\\textcircled{7}$ 及格后，放料冷却后包装。  \n\n配方5：2402纯酚醛树脂  \n\n(1）配方  \n\n叔丁酚 500kg 甲苯 700kg冰乙酸 6kg 熟石灰 3kg甲醛 550kg 草酸 少量(2）质量标准外观 透明 色泽（Fe-Co) ≤8软化点/C 85\\~110 苯中清 清  \n\n(3）操作  \n\n$\\Phi$ 先将甲醛投入反应锅，开搅拌后投人叔丁酚、熟石灰，打开分水器下与反应釜的联通阀，升温直至回流。  \n\n$\\textcircled{2}$ 回流（温度约 $100{\\sim}105\\mathrm{\\textperthousand}$ ）1h后，取样，用 $20\\%$ 水冲洗样品后，观察样品反应程度是否到达（一般要1.5h)。  \n\n$\\textcircled{3}$ 反应结束后，加入冰醋酸（pH调整到3～4）中止反应，然后加入甲苯搅拌 $15\\mathrm{{min}}$ 后静置，0.5h后分水。  \n\n$\\textcircled{4}$ 加人清水，搅拌 $15\\mathrm{min}$ 后静置，0.5h后分水；重复进行四次。每次加水时要注意液面情况，防止溢锅，水洗后，溶液体系 $\\mathfrak{p H}$ 应接近中性。  \n\n$\\textcircled{5}$ 将物料打入脱苯锅，进行减压蒸馏；先减压脱水（起始回流温度约 $60\\mathrm{{C}}$ )，到水基本脱清（此时约 $80\\%$ ，开始减压脱甲苯。  \n\n$\\textcircled{6}$ 随着甲苯脱出，反应釜内物料逐渐增厚，温度也同步上升；当反应釜中心出现鼓泡时（温度 $115{\\sim}120\\%$ )，取样并用手捏揉，观察是否到达终点；在接近终点时，若颜色呈棕红色，根据深浅加入适量草酸，进行还原脱色（由于草酸含结晶水，加入后一定要注意将水脱净，否则会影响树脂透明度）。  \n\n$\\textcircled{7}$ 取样，反应到达终点后放料，冷却后粉碎包装。  \n\n（4）注意事项  \n\n若水洗过程中，出现静置后分层不好，可适量补加甲苯，减小树脂层密度，帮助分层。配方6：284酚醛醚化浆  \n\n(1）配方  \n\n甲酚 800kg 10%磷酸 12kg 5%盐酸 250kg 10%液碱 170kg 甲醛 1050kg 丁醇 1100kg  \n\n(2）质量标准  \n\n固体分 48%\\~52% 苯中清（14甲苯)干性(150°C) ≤45min 涂4黏度（25C）  \n\n透明 20\\~30s  \n\n(3）操作  \n\n$\\textcircled{1}$ 将甲酚、液碱投入反应釜，开动搅拌将物料混合均匀。  \n\n$\\textcircled{2}$ 加人甲醛，然后加热，注意反应放热，控制反应温度在 $70\\sim75\\mathrm{{^{\\circ}C}}$ ，维持0.5h后开始取样测发浑点，发浑点控制在 $25\\sim35\\mathrm{^{\\circ}C}$ 为宜。  \n\n$\\textcircled{3}$ 到发浑点后冷却，逐步加入盐酸调节 $\\mathfrak{p H}$ 到 $6,0\\sim6.5$ ，并尽量控制 $\\mathsf{p H}$ 接近上限。  \n\n$\\textcircled{4}$ 静置0.5h后吸去上层水，再用清水洗涤，重复进行四次，每次加水时要注意液面情况，防止满锅。水洗时，若出现分层不好，可用少量冷水冲一下。  \n\n$\\textcircled{5}$ 加入丁醇将物料溶解，再用磷酸调节 $\\mathsf{p H}$ 到 $5{\\sim}6$ 要  \n\n$\\textcircled{6}$ 升温至回流并脱水，随着水分脱出，温度逐渐上升，当釜内温度升到105℃以上，水分已很少时，取样测苯中清。  \n\n$\\textcircled{7}$ 苯中清后，开始回流蒸出丁醇，脱到一定程度后，开始取样：要求控制涂4黏度$(25^{\\circ})$ > $24\\sim26\\mathrm{s}$ 费  \n\n$\\textcircled{8}$ 达到要求后，冷却过滤包装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 208,
+        "chunk": "# 五、酚醛树脂的应用  \n\n酚醛树脂是最早投入实际应用的合成树脂，作为一种高分子化合物，具有： $\\textcircled{1}$ 分子量较大； $\\textcircled{2}$ 分子量分布宽； $\\textcircled{3}$ 分子结构多变，有热固性的，也有热塑性的；可形成线型结构树脂，也可形成支链型结构树脂； $\\textcircled{4}$ 酚醛树脂具有良好的加工性能； $\\textcircled{5}$ 生产酚醛树脂工艺简单等特点。酚醛树脂交联固化后的特性，能满足多种应用要求，因此在工业上得到广泛的应用，如生产酚醛膜塑料和酚醛复合材料用胶黏剂，生产酚醛层压材料用浸胶，生产酚醛泡沫塑料、保温材料、阻燃材料等酚醛特种材料，生产酚醛涂料、油墨和胶黏剂，酚醛树脂基纤维增强塑料还可用于生产酚醛玻璃钢制品。  \n\n涂料行业以酚醛树脂为主要树脂与干性油配合制漆，使涂料在硬度、光泽、干性、耐水性、耐腐蚀性、电绝缘性等有良好表现。可广泛应用于木器、建筑、电气等方面。但酚醛树脂漆耐候性较差，不宜用于生产浅色漆与白漆。目前主要使用纯酚醛树脂、松香改性酚醛树脂、醇醚化酚醛树脂等。 三",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 209,
+        "chunk": "# 1.纯酚醛树脂漆  \n\n纯酚醛树脂漆有良好耐水性、耐酸性、耐溶剂性和电绝缘性能，可生产底漆、磁漆、清  \n\n漆等品种，施工方便。还可生产分散型酚醛树脂漆，这是一种附着力佳，漆膜耐久性好、耐磨性好、防潮性能突出的酚醛树脂漆。",
+        "category": " Introduction"
+    },
+    {
+        "id": 210,
+        "chunk": "# 2.松香改性酚醛树脂漆  \n\n是目前用量最大、品种最多的酚醛树脂漆，酚醛树脂与桐油等干性油炼制后与颜料、溶剂、助剂等组成，漆膜硬度高、干燥迅速、漆膜耐久、耐腐蚀、绝缘性能好，产品价格低。缺点是漆膜易泛黄。主要用于建筑、机械、船舶和绝缘材料等行业。",
+        "category": " Introduction"
+    },
+    {
+        "id": 211,
+        "chunk": "# 3.醇醚化酚醛树脂漆  \n\n主要为丁醇醚化酚醛树脂，可溶于芳烃类溶剂。单独制漆，漆膜耐水、耐酸性较好，但涂膜较脆，需高温交联。为改善这种情况，一般与其他树脂配合使用，若与环氧树脂配合，涂膜柔韧好，耐腐蚀性好，可用于罐头涂料和防腐蚀要求高的行业。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 212,
+        "chunk": "# 第四节氨基树脂",
+        "category": " Introduction"
+    },
+    {
+        "id": 213,
+        "chunk": "# 一、概述  \n\n本节涉及的涂料用氨基树脂，是以氨基化合物（含一 $\\cdot\\mathrm{NH}_{2}$ 官能团）与醛类（主要为甲醛）经缩聚反应得到的（含一 $\\mathrm{\\cdotCH}_{2}\\mathrm{OH}$ 官能团）产物，再与脂肪族一元醇部分醚化或全部醚化得到的产物，能与多种类型树脂交联成膜、并有良好混溶性的树脂，涂料行业将其列为氨基树脂。  \n\n氨基树脂是一种多官能度的聚合物，作为漆膜若单独用氨基树脂，得到的涂膜附着力差、硬度高、涂膜发脆，没有应用价值。氨基树脂容易与带有羟基、羧基、酰氨基的聚合物反应，因此可作为大部分涂料基体树脂，如醇酸树脂、丙烯酸树脂、饱和聚酯树脂、环氧树脂、环氧酯等树脂的交联剂，交联成膜后得到有韧性三维网状结构的涂膜，根据氨基树脂及基体树脂的不同，所得的涂膜也各有特点。  \n\n用氨基树脂作交联剂的涂膜具有优良的光泽、保色性、硬度、耐化学性、耐水及耐候性等，因此，氨基树脂漆广泛地应用于汽车、工程机械、钢制家具、家用电器和金属预涂等领域。氨基树脂漆在酸催化剂作用下，可大幅度降低烘烤温度，这种性能可用于二液型木材涂料和汽车修补涂料。  \n\n氨基树脂作为涂料行业的主要交联剂已有六十多年，它与工业涂料的发展密切相关，丁醇改性的脲醛树脂于20世纪30年代发明，开创了氨基醇酸烤漆的应用；40年代初，三聚氰胺甲醛树脂被发明，生产出了综合性能更优异的氨基漆，使氨基树脂在涂料行业飞速发展；60年代发明了苯代三聚氰胺甲醛树脂，以它作为交联剂获得的涂膜，具有优异的耐化学性和初期光泽，从而拓展了氨基涂料的应用。  \n\n60年代合成出单体型的六甲氧基三聚氰胺交联剂（HMMM)，并通过四十多年的发展，奠定了在涂料用树脂中的重要作用，70年代发展出部分甲醚化三聚氰胺甲醛树脂，与丁醚化树脂相比，反应活性大、交联反应温度低、与基体树脂有更好的相容性、树脂具有一定的水溶性，因此可用于生产水性涂料和溶剂型低温快干涂料。  \n\n各种类型的氨基树脂生产中，醛类化合物一般采用甲醛，为使反应顺利进行，甲醛都是过量的，因此反应过程中会排出一定量的含醛废水（同时含有醇类等有机物)，成品的氨基树脂中也会含有少量的游离醛，甲醛有相当的毒性，对人体有强烈的刺激作用，卫生部制订的《高毒物品目录》将甲醛归为高毒物品的一种，因此氨基树脂生产和使用过程中可能产生的危害，应引起重视。全部或部分采用多聚甲醛可大幅度减少氨基树脂生产中产生的废水，又可改善氨基树脂的品质，从而达到降低污染的目的。采用合适的工艺，降低氨基树脂的游离醛，可减少氨基漆固化时甲醛的排放，从而改善施工条件。  \n\n为了避免和减少涂料施工过程中有机溶剂（VOC）对环境造成的影响，近年来高固体分涂料和水性涂料发展很快，从而带动了甲醚化氨基树脂的应用，目前在卷材涂料、低温快干涂料、水性涂料中有各类甲醚化树脂的应用。甲醚化树脂与丁醚化树脂相比，生产工艺复杂，单釜产量低，生产成本高，因此目前在涂料行业中，仍然是丁醚化氨基树脂最为常用，但甲醚化树脂的应用呈现增长态势，前景广阔。",
+        "category": " Introduction"
+    },
+    {
+        "id": 214,
+        "chunk": "# 二、氨基树脂所用的原料  \n\n合成氨基树脂，最基本的原料是氨基化合物（主要为尿素、三聚氰胺、苯代三聚氰胺等)、醛类（主要为各种规格的甲醛)、醇类（主要为脂肪族一元醇，如甲醇、丁醇、异丁醇、乙醇、异丙醇等)，为使反应生成水顺利脱除，--般采用二甲苯作为带水剂来帮助脱水。合成氨基树脂的各种反应要在酸性或碱性条件下进行，需要调整反应时的 $\\mathsf{p H}$ ，为降低和保证树脂的色泽，有时需要轻质碳酸镁来脱色。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 215,
+        "chunk": "# 1.氨基化合物  \n\n含有氨基 $(\\mathrm{-NH_{2}}$ ）的化合物就是氨基化合物。氨基是氨分子（ $\\mathrm{NH}_{3}$ ）中去掉一个氢原子形成的基团，氨基化合物可看成是 $\\mathrm{NH_{3}}$ 的衍生物，即 $\\mathrm{NH}_{3}$ 中的氢原子被烃基取代的衍生物。胺类可根据烃基的性质分为脂芳族胺和芳香族胺，也可根据分子中氨基的数目分为一元胺、二元胺、三元胺等，合成氨基树脂所使用的氨基化合物都属于二元胺以上的多元胺。常用氨基化合物的参数见表2-1-63。  \n\n表2-1-63常用氨基化合物的参数  \n\n\n<html><body><table><tr><td rowspan=\"2\">项 目</td><td colspan=\"4\">工业级优等品</td></tr><tr><td>尿素</td><td>三聚氰胺</td><td>苯代三聚氰胺</td><td>甲代三聚氰胺</td></tr><tr><td>外观</td><td>白色颗粒</td><td>白色结晶粉末</td><td>白色晶体状粉末</td><td>白色晶体状粉末</td></tr><tr><td>总氮（N)(以干基计）/%≥</td><td>46.5</td><td></td><td></td><td></td></tr><tr><td>含量（升华法）/% ≥</td><td></td><td>99. 8</td><td></td><td></td></tr><tr><td>缩二脲/%</td><td>0.5</td><td></td><td></td><td></td></tr><tr><td>水分/% ≤</td><td>0.3</td><td>0.1</td><td>0.2</td><td>0.2</td></tr><tr><td>灰分/% ≤#</td><td></td><td>0.03</td><td>0.05</td><td>0.1</td></tr><tr><td>铁(Fe)/% ≤</td><td>0.0005</td><td></td><td></td><td></td></tr><tr><td>游离氨（NH）/% ##</td><td>0.01</td><td></td><td></td><td></td></tr><tr><td>硫酸盐（SO）/% ≤</td><td>0.005</td><td></td><td></td><td></td></tr><tr><td>水不溶物/% ##</td><td>0.005</td><td></td><td></td><td></td></tr><tr><td>熔点/C</td><td>132.6</td><td></td><td>224~228</td><td>272~276</td></tr><tr><td>甲醛溶解性（80℃/10min）</td><td></td><td>全溶</td><td>全溶</td><td>全溶</td></tr><tr><td>Pt-Co色泽（甲醛溶液）≤</td><td></td><td>20</td><td>30</td><td>40</td></tr><tr><td>游离碱/% ≤</td><td></td><td>0.02</td><td>0.05</td><td>0.1</td></tr></table></body></html>  \n\n尿素，又称脲、碳酰胺，相当于碳酸的二酰胺，相对分子质量60.06，结构式NH产 ，密度 $1.335{\\mathrm{g}}/{\\mathrm{cm}}^{3}$ 。熔点132.7℃，溶于水、低碳醇，不溶于乙醚、氯仿。是弱NH碱性物质，可与酸作用生成盐。在高温下可进行缩合反应，生成缩二脲、缩三脲和三聚氰酸。尿素加热至 $160^{\\circ}\\mathrm{C}$ 会分解，产生氨气同时变为氰酸，工业上采用液氨和二氧化碳，在高温、高压下来合成尿素。尿素是最早在氨基树脂中应用的氨基化合物。  \n\n三聚氰胺，简称三胺，学名2,4,6-三氨基-1，3，5-三嗪、1,3,5-三嗪-2，4，6-三胺，俗称蜜胺。是一种三嗪类含氮杂环有机化合物，重要的氮杂环有机化工原料，相对分子质量  \n\nNHz126.12，结构式 N N ，密度 $1.573\\mathrm{g}/\\mathrm{cm}^{3}$ 0 $16\\%$ ，熔点354℃（分解），升华温度HN N NH  \n\n$300^{\\circ}\\mathrm{C}$ 。比热容 $1.473\\mathrm{kJ}/(\\mathbf{kg}\\cdot\\mathsf{C})$ 。溶于热水，微溶于冷水，极微溶于热乙醇，不溶于醚、苯和四氯化碳，可溶于甲醇、甲醛、乙酸、热乙二醇、甘油、吡啶等。低毒。一般情况下较稳定，但高温下可能会分解放出氰化物，同时放出氮气，因此可作阻燃剂，此外三聚氰胺还可以作减水剂、甲醛清洁剂等。  \n\n三聚氰胺早期合成使用双氰胺法：由电石（ $\\mathbf{CaC}_{2}$ ）制备氰胺化钙（ $\\mathrm{CaCN}_{2})$ ，氰胺化钙水解后二聚生成双氰胺，再加热分解制备三聚氰胺，该工艺生产成本高，目前已被淘汰。目前采用尿素法合成三聚氰胺。尿素以氨气为载体，在催化剂作用下，于 $380\\sim400^{\\circ}\\mathrm{C}$ 反应，先分解生成氰酸，并进一步缩合生成三聚氰胺。  \n\n生成的三聚氰胺气体经冷却捕集后得粗品，然后经溶解，除去杂质，重结晶得成品。  \n\n按照反应条件不同，三聚氰胺合成工艺又可分为高压法（ ${\\cdot}7{\\sim}10\\ensuremath{\\mathrm{MPa}}$ ， $370\\sim450\\ensuremath{\\uptau}$ ，液相)、低压法 $(0,5{\\sim}1\\mathrm{{MPa}}$ ， $380\\sim440^{\\circ}\\mathrm{C}$ ，液相）和常压法 $(<0.3\\ensuremath{\\mathrm{MPa}}$ ， $390^{\\circ}\\mathrm{C}$ ，气相）三类。国外三聚氰胺生产企业采用高压法、低压法和常压法三种工艺都有，我国三聚氰胺生产企业一般采用半干式常压法工艺，以尿素为原料，0.1MPa以下，约 $390\\Upsilon$ 时，生成三聚氰胺。  \n\n苯代三聚氰胺，俗称苯鸟粪胺、BG三聚氰胺，学名2,4二氨基-6-苯基-1,3,5-三嗪，相  \n\n对分子质量187.22，结构式是苯基置换三聚氰胺一个氨基的化合物，与三聚氰胺性质类似，相对密度1.40（25℃/4℃)，常温下不溶于水中，沸水中可溶解 $1g/100g$ 。由于结构中带有一个苯环，生产出的氨基树脂交联剂，可给涂膜更好的光泽、更高的硬度、更好的耐化学性，与基体树脂有更好的混溶性。  \n\n![](images/ae620670d6455bad18c205cbee08d8995e3ccfc1968eb1bbf7751d4b97b6a716.jpg)  \n\n![](images/693de9ac07049d9a20f585c8cda072de260d867dde0da1ddfa57b114a85ca25b.jpg)  \n苯代三聚氰胺合成反应式  \n\n在碱性（氢氧化钾）条件下，以丁醇或丙二醇甲醚作溶剂，采用双氰胺和苯甲睛合成，经洗涤和干燥后得到苯代三聚氰胺成品。采用丙二醇甲醚作溶剂比采用丁醇作溶剂，苯代三聚氰胺得率可高 $1\\%\\sim2\\%$ ，但考虑溶剂回收工艺水平与溶剂损耗，由于丁醇价格低于丙二醇甲醚，目前国内苯代三聚氰胺生产企业都采用丁醇作溶剂。合成使用的苯甲睛国内采用甲  \n\n苯胺氧化工艺来生产。  \n\n甲代三聚氰胺，别名乙酰胍胺、AG三聚氰胺，学名2，4二氨基-6-甲基-1，3,5-三嗪或  \n\n6-甲基-1，3，5-三嗪-2，4二胺，相对分子质量125.13，结构式  \n\n![](images/e33160c9c2272c24ed089a499c667d8b87fc43d6c9f2493dd357631d55e36edd.jpg)  \n\n是甲基置换三聚  \n\n氰胺一个氨基的化合物，与三聚氰胺性质类似，其闪点 ${>}270\\%$ ，因此在通常条件下相当稳定，甲代三聚氰胺能溶于水。它是一种应用广泛的特殊化学中间体，可以和苯代三聚氰胺以一定比例搭配，生产丁醇醚化、甲醇醚化的甲醛树脂，所得到的氨基树脂交联剂，与适当的基体树脂配合，可形成耐久性很好的涂膜。  \n\n![](images/d1a61873b64b27fdabeaa004754d0c668fac6b3e95788d4ba054158ae0875446.jpg)  \n甲代三聚氰胺合成反应式  \n\n甲代三聚氰胺：在碱性条件下，以丁醇作溶剂，采用双氰胺和乙睛合成，经洗涤和干燥后可得到成品，由于产品在水中有一定溶解性，其后处理工艺与苯代三聚氰胺后处理工艺相比复杂很多，目前国内只有江苏启东一家企业已投入工业化生产。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 216,
+        "chunk": "# 2.醛类  \n\n0分子结构中羰基（-C—）官能团与一个氢原子和一个烃基相连或与两个氢原子相连的0化合物称为醛（醛基—C--H），甲醛分子中羰基的两端都与氢原子相连，比其他醛更活泼，有更大的反应性，因此合成氨基树脂采用最简单的脂肪族醛——甲醛，结构式为 H-C-H， $\\underset{{\\mathrm{H\\mathrm{-}\\mathrm{\\bar{C}-H}}}}{\\underbrace{0}}$ 相对分子质量为30.03。甲醛采用甲醇氧化脱氢的工艺生产，纯甲醛常温下是无色有特殊的刺激气味气体，熔点 $-92\\tau$ ，沸点 $-19\\mathbb{C}$ ，与空气混合能形成爆炸混合物，爆炸极限为$7\\%\\sim73\\%$ 。甲醛在常温下会自聚成三聚甲醛， $60\\%$ ～65%的甲醛水溶液用硫酸催化、在煮沸条件下，也可得到三聚甲醛。  \n\n![](images/1a8ae5cf9110040e9e0f009c4f0c28c9e7c690e782f7f7cfafce36fc68cf34c2.jpg)  \n三聚甲醛合成反应式  \n\n甲醛易溶于水，一般以不同浓度的水溶液保存，方便使用，甲醛水溶液（俗称福尔马林）低温下容易聚合产生白色沉淀，少量甲醇的存在可减缓聚合反应的发生，因此市售的福尔马林中都含有一定量的甲醇。几种形式甲醛的性质见表2-1-64。 限 七  \n\n表2-1-64几种形式甲醛的性质  \n\n\n<html><body><table><tr><td>项目</td><td>37%甲醛水溶液</td><td>50%甲醛水溶液</td><td>多聚甲醛</td><td>甲醛丁醇溶液</td></tr><tr><td>采用标准</td><td>GB/T 90091998</td><td>ASTM D 237384</td><td></td><td></td></tr><tr><td>外观</td><td>透明</td><td>透明</td><td>白色</td><td>透明</td></tr><tr><td>甲醛含量/%</td><td>37. 0~37.4</td><td>49.75~50.5</td><td>91~93或≥95</td><td>39.5~40.5</td></tr><tr><td>甲醇含量/%</td><td>供需双方协商</td><td>≤1.5%</td><td></td><td></td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>项目</td><td>37%甲醛水溶液</td><td>50%甲醛水溶液</td><td>多聚甲醛</td><td>甲醛丁醇溶液</td></tr><tr><td>酸度（以甲酸计）</td><td>≤0.02%</td><td>0.05%</td><td></td><td></td></tr><tr><td>色度（Pt-Co）</td><td>≤10</td><td>≤10</td><td></td><td>≤10</td></tr><tr><td>密度Po/(g/cm)</td><td>1. 075~1. 114</td><td>1. 1470 ~1. 1520</td><td></td><td></td></tr><tr><td>铁含量/%</td><td>≤0.0001</td><td>≤0.0001</td><td>≤0.0001</td><td>≤0.0001</td></tr></table></body></html>  \n\n合成涂料用氨基树脂时，生产时需要将原料中带入的水分（主要为甲醛）与反应生成水脱去，因此使用甲醛水溶液生产氨基树脂将产生大量废水，以生产常规的丁醚化三聚氰胺甲醛树脂582-2为例，每生产1t树脂，将产生废水约 $600\\sim650\\mathbf{kg}$ ，对环境造成很大压力。  \n\n采用多聚甲醛合成氨基树脂，虽然工艺技术要求高，但成品树脂品质高，又可减少原料中带入的水分，从而减少废水总量。由于原料成本有一定上升，而且不同产地聚合甲醛，解聚的工艺条件又有差异，对生产工艺的制定影响较大，目前国内氨基树脂市场利润很薄、各地环保工作的力度又有差异，因此目前的氨基树脂生产还是以采用甲醛水溶液为主。采用甲醛丁醇溶液生产氨基树脂，也是很好的选择，但国内甲醛丁醇溶液尚未形成规模化生产，会使产品成本上升过高，目前无法大量应用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 217,
+        "chunk": "# 3.醇类和二甲苯  \n\n氨基化合物与甲醛反应的产物含有大量羟甲基，有较强极性，不溶于有机溶剂，与其他类型树脂混溶性极差，无法配合使用，因此涂料用氨基树脂需要用醇类改性，醚化后的氨基树脂能溶于有机溶剂，与匹配的树脂交联反应，形成有应用价值的涂膜。醚化采用脂肪族一元醇，可以采用甲醇、乙醇、异丙醇、正丁醇、异丁醇等，目前涂料行业采用最多的是甲醇、正丁醇、异丁醇。常用脂肪族一元醇参数见表2-1-65。  \n\n表2-1-65常用脂肪族一元醇参数  \n\n\n<html><body><table><tr><td rowspan=\"2\">项 目</td><td colspan=\"5\">工业级优等品</td></tr><tr><td>异丙醇</td><td>正丁醇</td><td>异丁醇</td><td>甲醇</td><td>无水乙醇</td></tr><tr><td>外观</td><td>透明液体</td><td>透明液体</td><td>透明液体</td><td>透明液体</td><td>透明液体</td></tr><tr><td>色度（Pt-Co)</td><td>≤ 5</td><td>10</td><td>10</td><td>5</td><td>5</td></tr><tr><td>密度（20℃）/(g/cm²）</td><td>0.784~0.786</td><td>0.809~0.811</td><td>0.801~0.803</td><td>0.791~0.792</td><td>0.789~0.790</td></tr><tr><td>纯度/%</td><td>99.7</td><td>99.5</td><td>99. 3</td><td>99.5</td><td>99.7</td></tr><tr><td>水分/% ≤</td><td>0.15</td><td>0.1</td><td>0.15</td><td>0.1</td><td>0.2</td></tr><tr><td>融含量（以乙酸计）/% ≤</td><td>0.002</td><td>0.003</td><td>0. 003</td><td>0.0015</td><td>0.002</td></tr><tr><td>蒸发残渣/% ≤</td><td>0.002</td><td>0.003</td><td>0. 004</td><td>0.001</td><td>0.0025</td></tr><tr><td>沸程（在101325Pa下） 初馏点/C</td><td></td><td></td><td></td><td></td><td>78.0</td></tr><tr><td>干点/C ≤</td><td>81.8 82.8</td><td>117.0 118.0</td><td>107.0 108.4</td><td>64.0 65.0</td><td>79.0</td></tr></table></body></html>  \n\n二甲苯不溶于水，与水分层，在氨基树脂的生产中作为带水剂使用，在反应过程中，溶剂与水共沸，通过冷凝器回到分水器内中，二甲苯的存在很容易使水与溶剂分层，上层的溶剂回进反应釜，水分可脱去，从而达到了将反应水带出反应釜的目的，起到了带水剂（脱水剂）的作用。石油混合二甲苯参数见表2-1-66。  \n\n表2-1-66石油混合二甲苯参数  \n\n\n<html><body><table><tr><td rowspan=\"2\">项 目</td><td colspan=\"2\">工业级优等品</td></tr><tr><td>3℃混合二甲苯</td><td>5℃混合二甲苯</td></tr><tr><td>外观</td><td>透明液体</td><td>透明液体</td></tr><tr><td>色度（Pt-Co）</td><td>20</td><td>20</td></tr><tr><td>密度（20C）/（g/cm）</td><td>0.862~0.868</td><td>0.860~0.870</td></tr><tr><td>总硫含量/（mg/kg） ≤</td><td>3</td><td>3</td></tr><tr><td>蒸发残渣/（mg/100mL） ≤</td><td>5</td><td>5</td></tr><tr><td>沸程（在101325Pa下）</td><td></td><td></td></tr><tr><td>初馏点/C 干点/ ≤</td><td>137.5 141.6</td><td>137</td></tr><tr><td>总馏程范围/℃C ≤</td><td>3</td><td>143 5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 218,
+        "chunk": "# 三、氨基树脂的分类  \n\n涂料用氨基树脂的分类方法主要有两种，-是按采用氨基化合物的不同来区分，采用三聚氰胺的称为三聚氰胺甲醛树脂，采用尿素的称为尿素甲醛树脂（简称脲醛树脂)，采用苯代三聚氰胺的称为苯代三聚氰胺甲醛树脂，采用甲代三聚氰胺的称为甲基三聚氰胺甲醛树脂，几种氨基化合物混合使用的，称为共聚树脂。  \n\n二是按醚化时采用醇类的不同来区分，主要有：丁醚化氨基树脂（采用正丁醇醚化，根据醚化程度的差异，可分为高醚化程度与低醚化程度)，异丁醚化氨基树脂（采用异丁醇醚化，根据醚化程度的差异，也分为高醚化程度与低醚化程度)，甲醚化氨基树脂（采用甲醇醚化，根据醚化程度的差异，可分为高甲醚化与部分甲醚化)，混合醚化氨基树脂（一般采用甲醇与正丁醇混合醚化，正丁醇与异丁醇混合醚化，也有采用甲醇与乙醇混合醚化的)。  \n\n氨基树脂的分类可用如下示意表示：  \n\n![](images/c9b338128e83224a14fa61afc07e10d7754264669f8ad63f77527331bf032d57.jpg)  \n\n从氨基树脂的结构上看：丁醇醚化的氨基树脂主要属于部分烷基化类型的树脂，这一类树脂羟甲基含量较高，醚化程度相对较低，属于目前最常用的氨基树脂。甲醇醚化的氨基树脂可分为：聚合型部分烷基化氨基树脂、聚合型高亚氨基高烷基化氨基树脂、单体型高烷基化氨基树脂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 219,
+        "chunk": "# 四、氨基树脂的合成",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 220,
+        "chunk": "# 1.丁醇醚化氨基树脂  \n\n(1）正丁醇醚化脲醛树脂脲醛树脂是最早发明及投入使用的丁醚化氨基树脂，在氨基醇酸烤漆体系中有广泛应用，但以脲醛树脂为交联剂的烤漆耐候性、耐水性相对较差，随着三聚氰胺甲醛树脂发明，涂膜性能得到很大的改善。由于脲醛树脂采用的氨基化合物-——尿素其价格远低于其他氨基化合物，因此脲醛树脂价格低廉，具有较大的成本优势，常规的氨基-醇酸烤漆中还有一定的应用，主要用于底漆和室内用漆。  \n\n近年来，国内预涂卷材市场得到飞速发展，全国各地方各种规模的卷材流水线有数百条，也引发了卷材涂料行业的高速发展。作为直接涂在预处理层上的底漆，主要为面漆提供基础和提高卷材的防腐蚀性，目前主要采用的：丁醚化脲醛树脂-高分子量环氧树脂的配方体系，极大地推动了脲醛树脂的应用。  \n\n$\\Phi$ 脲醛树脂特点  \n\na.是成本最低的丁醚化氨基树脂，生产工艺也无特殊要求。  \n\nb.脲醛树脂结构中的羰基含有极性氧原子，对基材有良好附着力，可用于底漆，也可用于中间涂层，提高面漆与底漆的层间结合力。  \n\nc.加人酸催化剂后，可常温交联，因此可生产常温固化涂料。  \n\nd.与其他氨基化合物相比，尿素反应性高，脲醛树脂活性大，因此丁醚化脲醛树脂的储存稳定性相对较差。  \n\n$\\textcircled{2}$ 反应机理尿素与甲醛的等摩尔比、其在反应物中的浓度、反应体系的酸碱性(pH)、反应温度、反应时间等条件的变化，都会对脲醛树脂的反应进程与结果造成影响。  \n\na.加成反应（羟甲基反应）尿素和甲醛的加成反应可在酸性或碱性条件下进行，脲醛树脂合成时的加成反应是在碱性条件下进行的。在弱碱性和一定温度下，尿素和甲醛不同的等摩尔比，通过加成反应可生成单羟甲基脲，也可生成二羟甲基脲。  \n\n![](images/c4df6f1a9558ad5c5319a2b212415abd83d8c037c373cfe0da9ae69c87764871.jpg)  \n\nb.缩聚反应羟甲基脲在酸性条件下，可与尿素的酰氨基或羟甲基缩合，生成亚甲基键。  \n\n![](images/624c00d747928780867d1afda3bcf5ccbb61cf469f9f664df1515cca1a1c8671.jpg)  \n\n从基团的反应活性上看，尿素中的酰氨基比单羟甲基脲中的酰氨基活性大，单羟甲基脲中的羟甲基比二羟甲基脲中的羟甲基活性大。低聚合度的羟甲基脲具有水溶性，不溶于有机溶剂，继续缩聚可形成支链型结构，可用于塑料、黏合剂、织物整理剂等行业。  \n\nc.醚化反应尿素甲醛反应的产物羟甲基脲含有大量羟甲基，有较强极性，不溶于有机溶剂，与基体树脂混溶性差，无法匹配，因此要用醇类改性。醚化后的脲醛树脂溶于有机溶剂，与基体树脂交联反应，形成有应用价值的涂膜。  \n\n醚化采用脂肪族一元醇，若以甲醇醚化，树脂分子中将引入甲氧基，与丁醇醚化形成的含丁氧基的树脂相比，甲醚化树脂具有一定的水溶性，可作为水性涂料的交联剂，部分甲醚化的脲醛树脂，可用于水性超薄型钢结构防火涂料，用于溶剂型涂料可作为低温烘烤涂料的交联剂。丁醇醚化后的树脂不具有水溶性，但在有机溶剂中有良好的溶解性，作为交联剂使用时，其固化交联速度要高于部分甲醚化的树脂。与甲醚化树脂的生产相比，丁醚化树脂的生产没有大量的醇类（甲醇）需要回收，生产工艺相对简单，生产成本低，与溶剂型的基体树脂匹配时，混溶性好，涂膜性能能满足要求，因此目前还是丁醚化氨基树脂的用量大。  \n\n为了保证丁醇对羟甲基脲的醚化反应顺利进行，需要使用过量的丁醇，醚化需要弱酸性的条件，反应结束后，过量的丁醇可留在体系中，作为溶剂使用，以控制树脂达到一定固体含量，方便使用，若要提高固含量也可以脱出一部分溶剂。  \n\n在弱酸性下，醚化反应和缩聚反应是同时进行的：  \n\n$\\textcircled{3}$ 反应工艺尿素分子中有两个氨基，每个氨基有两个氢原子，由于空间位阻等原因，不可能与甲醛完全反应，据测定，每个氨基对甲醛的官能度约为1.2。在丁醇中，尿素和甲醛在碱性条件下进行羟甲基反应，然后将反应体系调节到酸性，进行醚化反应和缩聚反应，通过控制酸性的强弱和丁醇过量程度，可以控制好醚化反应和缩聚反应的反应倾向和程度，羟甲基脲的醚化反应较慢，因此与其他氨基树脂的生产相比，醚化时酸性催化剂的用量要大得多。  \n\n随着醚化反应进行，脲醛树脂在脂肪烃溶剂中的溶解性会增加，实际生产中利用这个原理，通过测定脂肪烃溶剂的容忍度来控制醚化程度。与其他氨基树脂不同的是，由于树脂极性的缘故，脲醛树脂在脂肪烃溶剂的溶解性较差，与 $200^{\\sharp}$ 溶剂的容忍度很低，生产中采用$200^{\\sharp}$ 溶剂与二甲苯 $1:1$ 混合，再去测定脲醛树脂的容忍度。  \n\na.容忍度的测定玻璃烧杯 $\\scriptstyle:100\\mathrm{mL})$ ；托盘天平或电子天平（感量 $_{0,1_{8})}$ ；测试试剂[200\"溶剂汽油：二甲苯 $=1:1$ （质量）混合]。  \n\nb.测定方法称取树脂约 ${\\begin{array}{l}{38}\\end{array}}(G)$ 于玻璃烧杯中，用滴管将 $200^{\\sharp}$ 溶剂汽油逐步滴入试样内，不断搅拌，至试样显示乳浊并在15s内不消失时，即为终点，称取总重量（W)。1g脲醛树脂可容忍混合溶剂的量（g）即为容忍度，容忍度 $=(W-G)/G_{\\circ}$  \n\n$\\textcircled{4}$ 配方实例578-1脲醛树脂  \n\n配方：  \n\n<html><body><table><tr><td>尿素</td><td>700kg 2000kg</td><td>NaOH(10%) 二甲苯</td></tr><tr><td>丁醇 甲醛</td><td>2250kg</td><td>390kg 7~11kg</td></tr><tr><td>指标：</td><td></td><td>苯酐</td></tr><tr><td>外观</td><td>透明</td><td>T-4黏度(25C)</td></tr><tr><td>色泽（Fe-Co)</td><td>≤1</td><td>苯中清</td></tr><tr><td>团体分</td><td>(60±2)%</td><td>容忍度（二甲苯1200*溶剂=111)</td></tr><tr><td>酸值/(mgKOH/g)</td><td>≤2</td><td></td></tr></table></body></html>  \n\n操作：  \n\na.先投入甲醛，以 $10\\%\\ \\mathrm{NaOH}$ 调节 $\\mathsf{p H}$ 至8，然后投人尿素，再调整 $\\mathsf{p H}$ 至8。  \n\nb.升温至 $40\\sim50\\ensuremath{\\mathrm{~\\circ~}}$ 维持，待溶液透明后，投人丁醇，升温至回流，全回流约 $0.5\\mathrm{h}$ .  \n\nc.投入二甲苯与溶剂（无溶剂时不投)，再加入苯酐，继续升温至回流，全回流1.5h。  \n\nd.关闭蒸汽、停止搅拌，静止1h后，从反应锅底部分去废水。  \n\ne.开揽拌并升温至回流，开始回流脱水；随着水分逐渐脱去，温度会逐渐上升，并在$102{\\sim}103^{\\circ}\\mathrm{C}$ 时取样测试（容忍度、黏度）。此时测试结果一般为（25℃）；  \n\nT-4黏度 18\\~28s 容忍度 1 :(2\\~3)浑若容忍度偏高，脱溶剂要快（过分高时，可考虑减压脱溶剂）。  \n\nf.不断脱出溶剂，并进行终点控制，要求达到：  \n\nT-4黏度(25C） 70\\~90s 苯中清 容忍度 1: (3\\~8)浑  \n\n清  \n\ng.达到要求后，冷却到 $80^{\\circ}\\mathrm{C}$ 以下（若树脂颜色偏深，可加入适量轻质碳酸镁脱色，一般加人量在 $300\\sim500g)$ ，过滤包装。  \n\n(2）正丁醇醚化三聚氰胺甲醛树脂--个三聚氰胺分子上含有三个氨基，与尿素相比，多了一个氨基，用以合成氨基树脂。与丁醚化的脲醛树脂相比，交联度大，而且三聚氰胺是杂环化合物，与其他基体树脂匹配时，其交联速度，固化后涂膜的综合性能都优于脲醛树脂。因此三聚氰胺甲醛树脂发明后，很快就占据了大部分原有脲醛树脂的市场。  \n\n$\\textcircled{1}$ 三聚氰胺甲醛树脂特点  \n\na.是目前最常用的丁醚化氨基树脂，生产工艺也无特殊要求。  \n\nb.三聚氰胺甲醛树脂结构中含有杂环，交联密度有大，主要用于面漆，有良好的装饰性能。  \n\nc.能与很多基体树脂，如醇酸、环氧和丙烯酸等配合，得到性能优良的涂膜。  \n\nd.与脲醛树脂相比，丁醚化后的三聚氰胺甲醛树脂性能稳定，贮存稳定性良好  \n\n$\\textcircled{2}$ 反应机理氨基树脂生产工艺有一步法和二步法两种。一步法；在弱酸性的条件下，羟甲基化反应、醚化反应及缩聚反应同时进行，一步完成。一步法工艺简单、但 $\\mathfrak{p H}$ 控制严格，使三种反应均衡的进行，一步法生产的树脂稳定性稍差，目前一般采用二步法生产工艺。二步法：先在弱碱性条件下进行羟甲基反应，然后在酸性条件下进行醚化反应和缩聚反应。  \n\n三聚氰胺甲醛的等摩尔比、其在反应物中的浓度、反应体系的酸碱性（pH)、反应温度、反应时间等条件的变化，都会对三聚氰胺甲醛树脂的反应进程与结果造成影响。  \n\na.加成反应（羟甲基反应）一个三聚氰胺分子上有三个一 $\\cdot\\Nu\\mathrm{H}_{2}$ ，六个活泼氢，在酸性或碱性条件下反应，有 $1{\\sim}6$ 个甲醛分子可与之发生羟甲基反应，生产相应的羟甲基三聚氰胺，羟甲基反应进程与反应物浓度与比例、反应时的酸碱性、反应温度、反应时间等关联。在弱碱性条件下，生成的羟甲基三聚氰胺稳定，因此，三聚氰胺甲醛树脂合成时的加成反应是在碱性条件下进行的。  \n\n![](images/8c2244222e6def0c61f4320aa173e64c3c38bc087b1c1671df4a78c985b2ac0a.jpg)  \n\n![](images/6905b6aa7b317a32500de2617c16243d48d398b5187ddbc11b511ee10a89e53c.jpg)  \n\n若一个三嗪环上生成的羟甲基数超过三个，需要有过量的甲醛投入才有可能形成，反应为可逆的，在一定条件下未反应的甲醛与已反应的甲醛形成动态平衡，甲醛过量的越多，三嗪环上生成的羟甲基数也越多。反应时间对羟甲基反应也影响很大，若时间太短，羟甲基化进行的不好，不利于醚化反应的进行，若时间过长，羟甲基之间缩合反应倾向会大幅增加，达到一定程度可能引起凝胶。涂料用氨基树脂一个三嗪环上生成的羟甲基数一般为 $4{\\sim}5$ 个。  \n\nb.缩聚反应多羟甲基三聚氰胺进一步缩聚反应可使分子量增大，缩聚反应分为两种方式进行。  \n\n三嗪环氨基上未反应的氢与另一三嗪环上的羟甲基进行反应，形成亚甲基。  \n\n$$\n-\\mathrm{CH_{2}O H}+\\mathrm{\\HN}\\setminus\\leftrightharpoons-\\mathrm{CH_{2}}\\mathrm{-N}\\setminus\\leftrightharpoons\\mathrm{H_{2}O}\n$$  \n\n两个三嗪环上的羟甲基之间进行缩合反应，形成醚键，然后脱去一个甲醛后也形成亚甲基。  \n\n$$\n\\begin{array}{r l}{-\\mathrm{CH}_{2}\\mathrm{OH}+\\mathrm{HOH}_{2}\\mathrm{C}-\\dotsc}&{-\\mathrm{CH}_{2}\\mathrm{OCH}_{2}-+\\mathrm{H}_{2}\\mathrm{O}}\\\\ {-\\mathrm{CH}_{2}\\mathrm{OCH}_{2}-\\stackrel{\\bigtriangleup}{\\longrightarrow}-\\mathrm{CH}_{2}-+\\mathrm{HCH}\\mathrm{O}}\\end{array}\n$$  \n\n两个三嗪环之间的反应，一个是一步反应生成亚甲基键，另一个二步反应生成亚甲基键，羟甲基少的三嗪环上含有未反应的氢原子多，因此，缩聚反应速率高，羟甲基多的三嗪环上含有未反应的氢原子少，缩聚反应进行的就慢。  \n\nc.醚化反应三聚氰胺甲醛反应的产物多羟甲基三聚氰胺的低聚物含有大量羟甲基，有较强极性，不溶于有机溶剂，与基体树脂混溶性差，用醇类改性可改进分子的极性，形成丁氧基，三嗪环上基团的类型和数量不同，氨基树脂的性能也不相同。  \n\n羟甲基和丁氧基的变化对树脂性能的影响见表2-1-67。  \n\n表2-1-67羟甲基 $(-\\mathrm{CH}_{\\bar{z}}\\mathrm{OH})$ 和丁氧基 $(\\mathrm{-CH_{2}O C_{4}H_{9}})$ 的变化对树脂性能的影响  \n\n\n<html><body><table><tr><td>项 目</td><td>容忍度</td><td>混溶性</td><td>黏度</td><td>反应性</td></tr><tr><td>羟甲基↑</td><td>↑</td><td></td><td>↓</td><td>↑</td></tr><tr><td>醚化度↑</td><td>↑↑</td><td>↑↑</td><td>↓</td><td></td></tr><tr><td>分子量↑</td><td></td><td></td><td>↑↑</td><td></td></tr></table></body></html>  \n\n羟甲基化反应和醚化反应进程对最终产品性能影响都很大，其中醚化反应影响更大，醚化反应后，得到了性能稳定的氨基树脂，并与基体树脂有良好的混溶性。丁醇醚化氨基树脂易溶于有机溶剂，不溶于水，而甲醇醚化氨基树脂有较广的溶解范围，既可溶于水，也可溶  \n\n于有机溶剂。  \n\n为使丁醇与多羟甲基三聚氰胺的醚化反应顺利进行，需要使用过量的丁醇，井在弱酸性的条件下进行醚化反应，同时还发生羟甲基之间的缩合反应。若反应时间过短，树脂醚化度低、分子量小、稳定性差；若反应时间过长，树脂分子量过大，分水时易沉淀，影响分水操作。过量的丁醇反应后可留在体系中，作为溶剂使用，以控制树脂固体含量，要提高固含量可以脱出一部分溶剂。  \n\n在弱酸性下，多羟甲基三聚氰胺醚化反应和缩聚反应是同时进行的：  \n\n![](images/dfbee660af422b2c2de6dc4f3be22ad527ddcb355bad89ec3a29851e2fbeafa2.jpg)  \n\n$\\textcircled{3}$ 反应工艺合成丁醚化三聚氰胺甲醛树脂的工艺较为简单，目前一般采用二步法、分水的工艺进行，整个生产过程可分为四个步骤。  \n\na.反应采用全回流（不脱水）进行羟甲基反应及醚化反应。  \n\n三聚氰胺、甲醛、丁醇，在弱碱性条件下进行羟甲基反应，反应进行到一定程度，形成稳定的水溶性的多羟甲基三聚氰胺，加入酸性催化剂，将反应体系转入酸性，在弱酸性条件下进行醚化反应和缩聚反应，反应物随着极性的降低水溶性逐渐降低，体系呈浑浊状。整个反应过程在全回流（不脱水）状态下进行，工艺控制简单。  \n\nb.脱水采用先静置分水、后常压脱水的工艺。  \n\n通常采用的工业甲醛含量只有 $37\\%$ ，另外63%是水，原料中引入的水量很大，再加上进行醚化反应和缩聚反应的同时，又有水生成，采用静置分水办法，可一次性快速去除大量的水，同时水溶性小分子等杂质通过分水被去除，对树脂透明度的提高有所帮助。  \n\n通过静置，浑浊的体系分为两层，上层为树脂溶液，下层为水层，通过反应釜底部的视孔将水层放出掉，然后再采取回流脱水的方法脱出剩余的水分。丁醚化氨基树脂生产产生的废水约含 $7\\%\\sim8\\%$ 丁醇、 $4\\%\\sim5\\%$ 甲醛和其他杂质，一般采取蒸馏的方法先回收丁醇，回收丁醇后的废水再用其他方法处理，目前国内有将此废水套用到工业甲醛的生产中，比较合理。  \n\nc.脱溶剂常压脱出溶剂（主要成分丁醇、二甲苯、水)，进行中控测试。  \n\n为保证醚化反应顺利进行，需要采用过量的丁醇，因此，脱水完成后，需要脱出一定量的溶剂，使树脂控制在一定的指标范围内。一般在常压状态下，回流脱出溶剂，若脱溶剂前中控容忍度偏大，也可采用减压的方式脱出溶剂，脱溶剂量由脱溶剂后中控测试结果进行增减。脱出的溶剂下次生产时可套用，其成分大致为：丁醇 $70\\%$ 、二甲苯 $20\\%$ 、水 $10\\%$ +d.后处理利用过滤设备去除树脂中杂质，使树脂清澈透明。  \n\n如果树脂中小分子的水溶性的杂质过多，贮存过程中会有絮凝状物析出，过滤后又会析出，影响树脂的透明度。为解决这一问题，可采取水洗的方法，将水溶性杂质去除，方法如下：往待处理的树脂中加入树脂总量 $20\\%$ 丁醇、 $5\\%$ 二甲苯、 $75\\%$ 水，加热回流一段时间后，静置分水后，再脱水、脱溶剂，并调整到树脂指标后，过滤包装。  \n\n采用这一方法会加大丁醇的损耗，又导致废水的增加，随着技术的进步，三聚氰胺等原料质量的提高，再加上氨基树脂生产工艺的日渐成熟，目前正常生产中已不采用水洗的工艺，也能保证产品质量达到要求。  \n\n要得到清激透明的树脂，还需要经过过滤这一步骤，用以去除树脂中的各种杂质。目前一般采用 $\\pmb{\\gamma}$ 过滤机，助滤剂采用硅藻土，若过滤前树脂色泽不佳，可在树脂中适当加些轻质碳酸镁，然后在 $70\\sim80^{\\circ}C$ 维持一段时间进行脱色，然后过滤，过滤温度以 $70\\sim$ $80^{\\circ}\\mathrm{C}$ 为好。  \n\n丁醚化三聚氰胺甲醛树脂测试容忍度，直接采用 $200^{\\sharp}$ 溶剂进行，容忍度反映的是树脂在脂肪烃溶剂中的溶解性，不同批次 $200^{\\circ}$ 溶剂的芳香烃含量是不同的，用于测试同一树脂结果就不同，为避免这一状况，一般采用芳香烃含量 $9\\%\\sim11\\%$ 的 $200^{\\sharp}$ 溶剂去测试氨基树脂的容忍度。  \n\n$\\textcircled{4}$ 配方实例低容忍度的582-2氨基树脂  \n\n配方：  \n\n<html><body><table><tr><td>三聚氰胺</td><td>600kg</td><td>轻质碳酸镁</td><td>2.1kg</td></tr><tr><td>丁醇</td><td>2130kg</td><td>二甲苯</td><td>360kg</td></tr><tr><td>甲醛</td><td>2430kg</td><td>苯酐</td><td>1.9kg</td></tr><tr><td>指标：</td><td></td><td></td><td></td></tr><tr><td>外观</td><td>透明</td><td>T-4黏度(25℃)</td><td>60~100s</td></tr><tr><td>色泽(Fe-Co)</td><td>≤1</td><td>苯中清</td><td>清</td></tr><tr><td>固体分</td><td>(60±2)%</td><td>容忍度（200溶剂）</td><td>1+(2~7)浑</td></tr><tr><td>酸值/（mgKOH/g）</td><td>≤1</td><td></td><td></td></tr></table></body></html>  \n\n操作：  \n\na.先投入丁醇、二甲苯、溶剂（无溶剂时不投)，然后加三聚氰胺和轻质碳酸镁，再投人甲醛；逐渐升温，当温度达到 $80^{\\circ}\\mathrm{C}$ 时，停止加热，维持0.5h，再升温至回流。  \n\nb.全回流反应（约 $92\\%$ ）2.5h，关闭蒸汽、等回流停止后关搅拌。  \nc.加苯酐后开揽拌加热，并继续保持全回流反应1.5h。  \nd.关闭蒸汽、停止揽拌，静止1h后，从反应锅底部分去废水。  \n\ne.开搅拌，升温至回流，开始脱水，注意控制脱水速度；随着水分逐渐脱去，温度会逐渐上升，约 $100{\\sim}101\\Upsilon$ 时取样第一次中控，整个回流脱水阶段一般控制在 $4\\sim5\\mathrm{h}$  \n\nf.中控测试（容忍度、黏度)。此时测试结果一般为 $(25\\Upsilon)$ \\*  \n\nT-4黏度 25\\~30s 容忍度 1:(2\\~3)浑g.不断脱出溶剂，并进行终点控制，要求达到：  \n\nT-4黏度（25°C) 70\\~90s 苯中清 清容忍度 1:(3\\~6)浑  \n\n若容忍度偏高，脱溶剂要快（过分高时，可考虑减压脱溶剂）。  \n\nh.达到要求后，冷却到 $80^{\\circ}\\mathrm{C}$ 以下（若树脂颜色偏深，可加入适量轻质碳酸镁脱色，一般加入量在 $300\\sim500_{8})$ ，过滤包装。  \n\n$\\textcircled{5}$ 配方实例高容忍度的590-3氨基树脂  \n\n<html><body><table><tr><td>三聚氰胺 丁醇</td><td>600kg 2250kg</td><td>轻质碳酸镁 二甲苯</td></tr><tr><td>甲醛</td><td>2430kg 苯酐</td><td>360kg 2. 4kg</td></tr><tr><td>指标：</td><td></td><td></td></tr><tr><td>外观</td><td>透明</td><td>T-4黏度(25℃)</td></tr><tr><td>色泽（Fe-Co)</td><td>≤1</td><td>苯中清</td></tr><tr><td>固体分 酸值/(mgKOH/g)</td><td>(60±2)% ≤1</td><td>容忍度(200\"溶剂)</td></tr></table></body></html>  \n\n操作：  \n\na.先投入丁醇、二甲苯、溶剂（无溶剂时不投)，然后加三聚氰胺和轻质碳酸镁，再投入甲醛；逐渐升温，当温度达到 $80^{\\circ}\\mathrm{C}$ 时，停止加热，维持 $1.0\\mathrm{{h}}$ ，再升温至回流。  \n\nb.全回流反应（约 $92\\%$ ）2.5h，关闭蒸汽、等回流停止后关搅拌。  \nc.加苯酐后开搅拌加热，并继续保持全回流反应1.5h。  \nd.关闭蒸汽、停止揽拌，静止1h后，从反应锅底部分去废水。  \n\ne.开搅拌，升温至回流，开始脱水，注意控制脱水速度；随着水分逐渐脱去，温度会逐渐上升，约 $105{\\sim}106^{\\circ}\\mathrm{C}$ 时取样第一次中控，整个回流脱水阶段一般控制在 $4.0\\sim5.0\\mathrm{b}$  \n\nf.中控测试（容忍度、黏度）。此时测试结果一般为（25℃）：  \n\nT-4黏度 20\\~30s 容忍度g.不断脱出溶剂，并进行终点控制，要求达到：  \n\nT-4黏度(25C) 60\\~70s 苯中清 容忍度 1 : (12\\~18)浑  \n\n清  \n\nh.达到要求后，冷却到 $80^{\\circ}\\mathrm{C}$ 以下（为避免容忍度的突变，590-3氨基树脂一般不允许加轻质碳酸镁脱色)，过滤包装。  \n\n(3）正丁醇醚化苯代三聚氰胺甲醛树脂苯代三聚氰胺是三聚氰胺分子中一个氨基被苯环取代后产物，苯代三聚氰胺分子中含有两个氨基，与三聚氰胺和尿素相比，反应活性介于二者之间。丁醚化苯代三聚氰胺甲醛树脂的反应机理与丁醚化三聚氰胺甲醛树脂的反应机理基本相同。  \n\n本产品是丁醇醚化的苯代三聚氰胺甲醛树脂在丁醇中的溶液，主要用于氨基醇酸烘漆、印刷油墨和软管滚涂油墨的生产。  \n\n$\\textcircled{1}$ 苯代三聚氰胺甲醛树脂特点  \n\na.树脂结构中含有苯环，故制得的树脂耐热性增加，制得涂膜初期光泽高、硬度高、丰满度好，有优良的抗化学性。b.树脂结构中含有苯环，降低了官能度，因此，涂料的交联速率降低，固化的条件要高于三聚氰胺树脂。c.树脂结构中含有苯环，降低了分子的极性，增加了树脂在有机溶剂中的溶解性，能与饱和聚酯树脂混溶，与基体树脂混溶性优于三聚氰胺树脂。 “  \n\nd.树脂结构中含有苯环，交联后涂膜的耐候性不如三聚氰胺树脂。  \n\n$\\textcircled{2}$ 反应机理先在碱性条件下进行羟甲基反应，然后在酸性条件下进行醚化反应和缩聚反应。  \n\n苯代三聚氰胺甲醛的等摩尔比、反应时的浓度、体系的酸碱性（pH)、反应温度、反应时间等条件的变化，都会对苯代三聚氰胺甲醛树脂的反应进程与结果造成影响。  \n\na.加成反应（羟甲基反应）一个苯代三聚氰胺分子上有两个一 $\\cdot\\mathrm{NH}_{2}$ ，四个活泼氢，在酸性或碱性条件下进行，有 $1{\\sim}4$ 个甲醛分子可与之发生羟甲基反应，生产相应的羟甲基苯代三聚氰胺，加成反应是在碱性条件下进行的。由于苯环的存在，降低了树脂极性，使羟甲基化产物不溶于水。苯代三聚氰胺甲醛树脂的一个三嗪环上生成的羟甲基数一般为 $2{\\sim}3$ 个。  \n\n![](images/dde1275d42c050044a8750888e9ffb9e12f6664129af8268b38fbb30baf0f915.jpg)  \n\nb.缩聚反应多羟甲基苯代三聚氰胺进一步缩聚反应可使分子量增大，缩聚反应分为两种方式进行。  \n\n三嗪环氨基上未反应的氢与另一三嗪环上的羟甲基进行反应，形成亚甲基。  \n\n$$\n-\\mathrm{CH_{2}O H}+\\mathrm{\\HN}\\setminus\\sqrt{\\frac{\\d}{\\d t}}=-\\mathrm{CH_{2}}-\\mathrm{N}\\setminus\\sqrt{\\frac{\\d}{\\d t}}+\\mathrm{H_{2}O}\n$$  \n\n两个三嗪环上的羟甲基之间进行缩合反应，形成醚键，然后脱去一个甲醛后也形成亚甲基。  \n\n$$\n\\begin{array}{r l}{-\\mathrm{CH}_{2}\\mathrm{OH}+\\mathrm{HOH}_{2}\\mathrm{C}-\\overbrace{\\mathrm{\\Gamma}\\cdots\\mathrm{~}}^{\\Delta}-\\mathrm{CH}_{2}\\mathrm{OCH}_{2}-+\\mathrm{H}_{2}\\mathrm{O}}&{}\\\\ {-\\mathrm{CH}_{2}\\mathrm{OCH}_{2}-\\overbrace{\\mathrm{\\Gamma}\\cdots\\mathrm{~}}^{\\Delta}-\\mathrm{CH}_{2}-+\\mathrm{HCH}\\mathrm{O}}\\end{array}\n$$  \n\nc.醚化反应多羟甲基苯代三聚氰胺需要用醇改性后，才能用于生产涂料，为使丁醇与多羟甲基三聚氰胺的醚化反应顺利进行，需要使用过量的丁醇，并在弱酸性的条件下进行醚化反应，同时还发生羟甲基之间的缩合反应，过量丁醇反应后部分留在体系中，另一部分则蒸馏脱出体系。  \n\n$\\textcircled{3}$ 反应工艺合成丁醚化苯代三聚氰胺甲醛树脂的工艺采用二步法工艺进行，整个生产过程可分为四个步骤。  \n\na.反应采用全回流（不脱水）进行羟甲基反应及醚化反应。  \n\n苯代三聚氰胺、甲醛、丁醇、在碱性条件下进行羟甲基反应，反应进行到一定程度，加入酸性催化剂，将反应体系转入酸性，在弱酸性条件下进行醚化反应和缩聚反应。  \n\nb.脱水采用先静置分水、后常压脱水的工艺。  \n\n与三聚氰胺树脂相比，由于树脂结构中多了苯环，树脂溶液密度变大，与水的密度更接近，使浑浊体系通过静置分为两相的时间变长，若生产过程中操作不当或原料有差异，极易导致分水操作无法完成，而被迫采用脱水的方法继续生产，因此在生产中要做到操作规范。  \n\n为避免这一状况，也有采用全脱水的工艺：刚达到回流时，即开始脱水，脱水达到一定量后，加人酸性催化剂，继续脱水，直至水基本脱尽后，脱溶剂至结束。此工艺的好处是没有分水这一步骤，工时相对较短，但一些小分子水溶性杂质不能通过分水被带出体系，少了一个去除杂质的途径，有可能对最后的过滤操作造成困难。  \n\nc.脱溶剂常压脱出溶剂（主要成分丁醇、二甲苯、水)，进行中控测试。  \n\n为保证醚化反应顺利进行，采用过量的丁醇，因此，脱水完成后，需要脱出一定量的溶剂，使树脂控制在一定的指标范围内，一般在常压状态下，回流脱出溶剂。  \n\nd.后处理利用过滤设备去除树脂中杂质，使树脂清澈透明。  \n\n(4）正丁醇醚化共聚树脂三聚氰胺树脂是目前应用最广泛的氨基交联剂。与苯代三聚氰胺树脂比：与基体树脂的混溶性、涂膜的初期光泽、抗水性、耐化学性都有差距，但耐候性好、原料来源广、产品成本低；与脲醛树脂相比：产品成本高、附着力有差距，但耐候性、抗水性、光泽等涂膜综合性能好。因此，三大类氨基树脂，各有其长短处，也有其最适宜应用的场合。  \n\n为避免氨基树脂在应用中可能遇到的问题，采用共聚方法，使氨基树脂结构中含有两种氨基化合物，从而使产品兼具多种树脂的长处，得到综合性能平衡、优异的树脂，更好的满足市场需求。  \n\n$\\Phi$ 共聚树脂特点  \n\na.以少量尿素替代部分三聚氰胺，可提高涂膜的附着力和干性、并降低成本，若替代量过多，会影响涂膜耐候性与干性。  \n\nb.以苯代三聚氰胺替代部分三聚氰胺，可改善氨基树脂与饱和聚酯树脂等基体树脂的混溶性，明显改善涂膜的初期光泽、抗水性、耐化学性，但氨基树脂的成本上升，耐候性有所下降。  \n\nc.以甲代三聚氰胺替代部分苯代三聚氰胺，可改善氨基树脂的耐候性、柔韧性，与其他共聚树脂相比，两种氨基化合物官能度相同，反应活性接近，树脂贮存稳定性好。避免了氨基化合物竞聚率不同，而产生的共聚树脂工艺难控制、树脂品质不稳定。  \n\n$\\textcircled{2}$ 反应机理先在碱性条件下进行羟甲基反应，然后在酸性条件下进行醚化反应和缩聚反应。  \n\n控制好竞聚率不同的各种氨基化合物与甲醛的反应，以使反应均衡的进行，保证树脂稳定。  \n\n氨基化合物的比例、反应物浓度、反应的酸碱性、反应温度、反应时间，都会对共聚树脂反应进程与结果造成影响。  \n\n$\\textcircled{3}$ 反应工艺丁醚化共聚树脂采用二步法进行，整个生产工艺与合成丁醚化苯代三聚氰胺树脂相同。  \n\n$\\textcircled{4}$ 配方实例苯代三聚氰胺与三聚氰胺共聚的树脂  \n\n配方：  \n\n<html><body><table><tr><td rowspan=\"3\">三聚氰胺 丁醇 苯代三聚氰胺</td><td rowspan=\"3\">600kg 2700kg 225kg</td><td>甲醛</td><td rowspan=\"3\">1800kg 12kg</td></tr><tr><td>苯甲酸</td></tr><tr><td>二甲苯</td></tr><tr><td>液碱</td><td>适量</td><td></td><td>500kg</td></tr><tr><td>指标：</td><td></td><td></td><td></td></tr><tr><td>外观</td><td>透明</td><td>T-4黏度（25C）</td><td>70~1108</td></tr><tr><td>色泽(Fe-Co)</td><td>≤1</td><td>苯中清</td><td>清</td></tr><tr><td>固体分</td><td>(50±2)% ≤1</td><td>容忍度（200*溶剂)</td><td>1 · (5~10)浑</td></tr><tr><td>酸值/（mgKOH/g）</td><td></td><td></td><td></td></tr></table></body></html>  \n\n操作：  \n\na.先投入甲醛与苯代三聚氰胺，用液碱调节pH到 $8\\pm0.1$ b.投入丁醇、二甲苯、溶剂（无溶剂时不投）及三聚氰胺；逐渐升温，并在80～85℃  \n维持1.0h，然后升温至回流。c.回流脱水反应，并记录出水量；当出水达到 $570\\mathbf{kg}$ 时，关闭蒸汽、等回流停止后关  \n搅拌。d.加苯甲酸后开搅拌维持 $15\\mathrm{{min}}$ ，加热并继续保持回流脱水，控制脱水速度。e.水分逐渐脱去，温度会逐渐上升，等水分基本脱尽（约 $107\\sim108^{\\circ}\\mathrm{C};$ ，开始脱溶剂。f.不断脱出溶剂，并进行中控测试（容忍度、黏度)。此时测试结果--般为（25C）：T-4黏度（25C） 80\\~100s萃中清 创 8清  \n\n容忍度 1·(6\\~9)浑  \n\ng.达到要求后，冷却到 $80\\Upsilon$ 以下（若树脂颜色偏深，可加入适量轻质碳酸镁脱色，般加人量在 $300{\\sim}500_{8})$ ，过滤包装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 221,
+        "chunk": "# 2.异丁醇醚化氨基树脂  \n\n采用异丁醇醚化的氨基树脂与相应的正丁醇醚化的氨基树脂相比：干性优于正丁醇醚化的树脂，通常情况下异丁醇价格低于正丁醇，因此异丁醇醚化的树脂成本低，异丁醇的醚化反应速度要低于正丁醇，因此酸性催化剂用量要大些。目前国内异丁醇醚化氨基树脂规模生产的是：异丁醇醚化三聚氰胺甲醛树脂和异丁醇醚化三聚氰胺和尿素共聚树脂。  \n\n（1）异丁醇醚化三聚氰胺甲醛树脂以异丁醇作为醚化醇类与溶剂时，由于异丁醇沸点比正丁醇低近 $10^{\\circ}\\mathrm{C}$ ，三聚氰胺与甲醛羟甲基化反应温度低，对反应造成影响，羟甲基化程度低，未反应活泼氢多，对进一步的醚化反应也会造成影响，为弥补反应温度低造成的影响，一般采取适当延长反应时间的办法来解决。  \n\n$\\Phi$ 异丁醇醚化三聚氰胺甲醛树脂特点  \n与正丁醇醚化的树脂相比：  \na.相同含量与容忍度情况下，树脂黏度要高；  \nb.生产反应工时长；  \nc.低温固化时，反应活性高于正丁醇醚化树脂；  \nd.相同黏度与容忍度时，异丁醇醚化树脂聚合程度要低。  \n\n$\\textcircled{2}$ 反应机理采用二步法生产工艺。先在弱碱性条件下进行羟甲基反应，然后在酸性条件下进行醚化反应和缩聚反应，与正丁醇醚化氨基树脂反应机理相同。  \n\n$\\textcircled{3}$ 反应工艺异丁醇醚化三聚氰胺树脂采用二步法进行，整个生产工艺与正丁醇醚化三聚氰胺树脂相同。  \n\n$\\textcircled{4}$ 配方实例低容忍度的585-1氨基树脂  \n\n配方：  \n\n<html><body><table><tr><td>三聚氰胺</td><td>600kg 2200kg</td><td>轻质碳酸镁</td><td>2.1kg 360kg</td></tr><tr><td>异丁醇</td><td></td><td>二甲苯</td><td>2.3kg</td></tr><tr><td>甲醛</td><td>2450kg</td><td>苯酐</td><td></td></tr><tr><td>指标：</td><td></td><td></td><td></td></tr><tr><td>外观</td><td>透明</td><td>T-4黏度（25C)</td><td>100~150s</td></tr><tr><td>色泽(Fe-Co)</td><td>≤1</td><td>苯中清</td><td>清</td></tr><tr><td>固体分</td><td>(60±2)%</td><td>容忍度（200溶剂）</td><td>11 (3~10)浑</td></tr><tr><td>酸值/（mgKOH/g）</td><td>≤1</td><td></td><td></td></tr></table></body></html>  \n\n操作：  \n\na.先投入异丁醇、二甲苯、溶剂（无溶剂时不投)，然后加三聚氰胺和轻质碳酸镁，再投入甲醛；逐渐升温，当温度达到 $80^{\\circ}\\mathrm{C}$ 时，停止加热，维持1.0h，再升温至回流。  \n\nb.全回流反应（约 $92\\%$ ）3.0h后，关闭蒸汽，等回流停止后关搅拌。  \nc.加苯酐后开搅拌加热，并继续保持全回流反应2.0h。  \nd.关闭蒸汽、停止搅拌，静止1h后，从反应锅底部分去废水。  \n\ne.开搅拌，升温至回流，开始脱水，注意控制脱水速度；随着水分逐渐脱去，温度会逐渐上升，约 $100{\\sim}101\\mathrm{\\mathfrak{C}}$ 时取样第一次中控，整个回流脱水阶段一般控制在 $4\\mathord{\\sim}5\\mathrm{h}$ 。  \n\nf.中控测试（容忍度、黏度)。此时测试结果一般为（25℃）：  \n\nT-4黏度 30\\~40s 容忍度 1:(2\\~3）浑g.不断脱出溶剂，并进行终点控制，要求达到：  \n\nT-4黏度（25C) 110\\~140s 苯中清 容忍度 11(4\\~9)浑  \n\n清  \n\n若容忍度偏高，脱溶剂要快（过分高时，可考虑减压脱溶剂）。  \n\nh.达到要求后，冷却到 $80^{\\circ}\\mathrm{C}$ 以下（若树脂颜色偏深，可加入适量轻质碳酸镁脱色，一般加人量在 $300\\sim500\\mathrm{g})$ ，过滤包装。  \n\n$\\textcircled{5}$ 配方实例高容忍度的585-2氨基树脂  \n\n配方：  \n\n三聚氰胺 600kg 轻质碳酸镁 2.1kg异丁醇 2300kg 二甲苯 360kg甲醛 2450kg 苯酐 2.6kg  \n\n指标：  \n\n外观 透明 T-4黏度（25C） 90\\~140s 色泽（Fe-Co) $\\leqslant1$ 苯中清 清 固体分 (60±2)% 容忍度（200\\*溶剂） 1 : (10\\~20)浑 酸值/（mgKOH/g) ≤1  \n\n操作：  \n\na.先投入异丁醇、二甲苯、溶剂（无溶剂时不投)，然后加三聚氰胺和轻质碳酸镁，再投入甲醛；逐渐升温，当温度达到 $80^{\\circ}\\mathrm{C}$ 时，停止加热，维持1.0h，再升温至回流。  \n\nb.全回流反应（约 $92\\mathbb{C}$ ）3.0h后，关闭蒸汽，等回流停止后关搅拌。  \nc.加苯酐后开揽拌加热，并继续保持全回流反应2.0h。  \nd.关闭蒸汽、停止搅拌，静止1h后，从反应锅底部分去废水。  \n\ne.开搅拌，升温至回流，开始脱水，注意控制脱水速度；随着水分逐渐脱去，温度会逐渐上升，约 $103{\\sim}104\\mathrm{C}$ 时取样第一次中控，整个回流脱水阶段一般控制在 $4\\sim5\\mathrm{h}$ ·  \n\nf.中控测试（容忍度、黏度）。此时测试结果一般为（25C）：  \n\nT-4黏度 30\\~40s 容忍度 11(5\\~8)浑g.不断脱出溶剂，并进行终点控制，要求达到：  \n\nT-4黏度(25°C) 100\\~130s 苯中清 容忍度 1 · (12\\~18)浑  \n\n清  \n\n若容忍度偏高，脱溶剂要快（过分高时，可考虑减压脱溶剂）。  \n\nh.达到要求后，冷却到 $80^{\\circ}\\mathrm{C}$ 以下（为避免容忍度的突变，585-2氨基树脂一般不允许加轻质碳酸镁脱色），过滤包装。  \n\n(2）异丁醇醚化三聚氰胺与尿素共聚树脂正丁醇醚化三聚氰胺树脂作为氨基树脂中重要的品种，应用很广，不同的应用领域对氨基树脂的要求是有差异的，为了降低成本，并满足一些低端用户的要求，目前国内部分氨基树脂生产单位，以异丁醇作为改性用的醇，尿素与三聚氰胺共聚生产氨基树脂，其产品表观质量指标与正丁醇醚化的582-2相同，只是容忍度数值接近582-2氨基树脂的下限。  \n\n$\\Phi$ 异丁醇醚化共聚树脂特点  \n\na.成本比正丁醇醚化的582-2要低（与1t正丁醇与异丁醇差价相近）。  \nb.用于生产氨基烤漆，耐候性低于582-2氨基树脂。  \nc.生产氨基烤漆时，干性比582-2氨基树脂好。  \n\nd.贮存稳定性低于正丁醇醚化的582-2氨基树脂与异丁醇醚化的585-1氨基树脂。  \n\n$\\textcircled{2}$ 反应机理采用二步法生产工艺。先在弱碱性条件下进行羟甲基反应，然后在酸性条件下进行醚化反应和缩聚反应，与一般氨基树脂反应机理相同。  \n\n$\\textcircled{3}$ 反应工艺异丁醇醚化共聚树脂采用二步法进行，整个生产工艺与正丁醇醚化三聚氰胺树脂相同。  \n\n$\\textcircled{4}$ 配方实例异丁醇醚化共聚树脂  \n\n配方：  \n\n三聚氰胺 175kg 甲醛 2200kg 异丁醇 2100kg 二甲苯 360kg 尿素 425kg 苯酐 2.3kg 轻质碳酸镁 2. 0kg   \n指标：   \n外观 透明 固体分 (60±2)% 色泽（Fe-Co) ≤1 酸值/（mgKOH/g) ≤1  \n\nT-4黏度（25C）  \n\n60\\~100s 容忍度（200\\*溶剂）  \n\n1· (2\\~7)浑 苯中清  \n\n清  \n\n操作：  \n\na.先投入异丁醇、二甲苯、溶剂（无溶剂时不投)，然后加三聚氰胺、尿素和轻质碳酸镁，再投入甲醛；逐渐升温，当温度达到 $80^{\\circ}\\Upsilon$ 时，停止加热，维持1.0h，再升温至回流。  \n\nb.全回流反应（约 $92\\%$ ）2.5h后，关闭蒸汽，等回流停止后关搅拌。  \n\nc.加苯酐后开搅拌加热，并继续保持全回流反应2.0h。  \n\nd.关闭蒸汽、停止揽拌，静止1h后，从反应锅底部分去废水  \n\ne.开搅拌，升温至回流，开始脱水，注意控制脱水速度；随着水分逐渐脱去，温度会逐渐上升，约 $100{\\sim}101\\%$ 时取样第一次中控，整个回流脱水阶段一般控制在 $4\\sim5\\mathrm{h}$ .  \n\nf.中控测试（容忍度、黏度)。此时测试结果一般为 $(25\\mathrm{^{\\circ}C})$ \\*T-4黏度 20\\~30s 容忍度 1+(2\\~3)浑g.不断脱出溶剂，并进行终点控制，要求达到：  \n\nT-4黏度（25C） 70\\~90s 苯中清 容忍度 1+ (2\\~6)浑  \n\n清  \n\n若容忍度偏高，脱溶剂要快（过分高时，可考虑减压脱溶剂）。  \n\nh.达到要求后，冷却到 $80^{\\circ}\\mathrm{C}$ 以下（若树脂颜色偏深，可加入适量轻质碳酸镁脱色，一般加入量在 $300\\sim500g)$ ，过滤包装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 222,
+        "chunk": "# 3.甲醇醚化氨基树脂  \n\n是指甲醇醚化生成的氨基树脂，以氨基化合物不同可分为甲醚化脲醛树脂、甲醚化三聚氰胺树脂、甲醚化苯代三聚氰胺树脂、甲醚化尿素三聚氰胺共缩聚树脂等。按照树脂结构不同可分为三类。  \n\n$\\Phi$ 部分甲醚化氨基树脂未醚化的羟甲基较多、醚化程度较低、树脂分子量较大、水溶性较好，可用于水溶性氨基漆的交联剂及低温氨基漆的交联剂。属于聚合型部分烷基化类型。  \n\n$\\textcircled{2}$ 高亚氨基、高甲醚化氨基树脂未醚化的羟甲基较少、有一定量亚氨基存在、醚化程度相对较高、树脂分子量相对低些。属于聚合型高亚氨基高烷基化类型。  \n\n$\\textcircled{3}$ 低亚氨基、高甲醚化氨基树脂未醚化的羟甲基很少、亚氨基很少、醚化程度更高、树脂分子量更低（基本上是单体)。属于单体型高烷基化类型。  \n\n甲醚化氨基树脂中产量最大，应用范围最广的是高甲醚化三聚氰胺树脂（HMMM)，它属于单体型高烷基化的三聚氰胺树脂，主要应用于卷材涂料行业。  \n\n$\\Phi$ 反应机理合成甲醚化氨基树脂的反应可分为两步。第一步：氨基化合物与过量的甲醛在碱性条件下进行羟甲基化反应，生成氨基化合物的羟甲基产物；第二步：羟甲基产物在酸性条件下与过量甲醇进行醚化反应。甲醚化氨基树脂合成需要上述两个反应，但同时还有缩聚反应发生，使分子量增大。  \n\n羟甲基化程度、醚化程度及缩聚程度，与甲醛及甲醇的配比、反应温度、反应时间、$\\mathsf{p H}$ 等密切相关。按不同规格和工艺的甲醚化氨基树脂生产方式，羟甲基化和醚化的二步反应可以两个反应釜中分开进行，也可在一个反应釜中分段进行。 M  \n\n以甲醚化三聚氰胺树脂的合成为例，反应示意如下。  \n\na.加成反应（羟甲基反应）三聚氰胺与甲醛的加成反应，是在碱性条件下进行的，甲醛和三聚氰胺不同的等分子比，可以生成含羟甲基数不同的羟甲基三聚氰胺，与甲醇进行醚化反应，从而得到不同醚化程度、不同规格的甲醚化三聚氰胺树脂。若甲醛过量到一定程度，理论上可形成6个羟甲基。  \n\n表2-1-68甲醛用量对羟甲基反应影响  \n\n\n<html><body><table><tr><td rowspan=\"3\">每三环数</td><td colspan=\"7\">甲醛/三聚氰胺（等分子比）</td></tr><tr><td>11</td><td>112</td><td>1·3</td><td>1 4</td><td>1+5</td><td>1•6</td><td>1·7 1+ 8</td></tr><tr><td>0. 9</td><td>1.7</td><td>2.9</td><td>3.7</td><td>4.6</td><td>5.3</td><td>5.7 5.9</td></tr></table></body></html>  \n\n从表2-1-68可以看出，甲醛用量越高，每个三嗪环结合的羟甲基数也就越大，要得到六羟甲基三聚氰胺，甲醛与三聚氰胺的等分子比，必须在 $1:8$ 以上，考虑到生产中可能存在的不确定因素，可放大到 $1:10$ 以上。  \n\n羟甲基反应是在碱性条件下进行的， $\\mathsf{p H}$ 小于7.5时，反应缓慢，而且羟甲基之间容易缩聚， $\\mathsf{p H}$ 大于9.5时，反应过快，多羟甲基产物很快结晶，反应不完全。因此 $\\mathsf{p H}$ 控制在$8.0\\sim9.0$ 较为适宜，实际生产一般控制为 $8,8\\sim9.0$ 之间。  \n\n当温度低于 $50\\mathrm{{^{*}C}}$ 时，三聚氰胺在甲醛中溶解很慢，影响羟甲基反应，但温度高于 $70\\Upsilon$ 时，已形成的多羟甲基三聚氰胺分子之间容易缩聚成聚合物，影响醚化反应，羟甲基化反应温度一般选择在 $55\\sim65\\Upsilon$ 。  \n\n![](images/a2efcbe017080fd9178f912b3a1e2dac6edc9ec63b4cf4a9f88f5ed363c7299c.jpg)  \n\nb.缩聚反应多羟甲基三聚氰胺进一步缩聚反应可使分子量增大，缩聚反应分为两种方式进行。  \n\n三嗪环氨基上未反应活泼氢与另一三嗪环上的羟甲基进行反应，一步反应形成亚甲基键。  \n\n$$\n-C H_{2}O H+H N\\uparrow=-C H_{2}-N\\uparrow+H_{2}O\n$$  \n\n两个三嗪环上羟甲基进行缩合反应，形成醚键，再脱去一个甲醛，二步反应形成亚甲基键。  \n\n$$\n\\mathrm{-CH_{2}O H+H O H_{2}C-\\bullet-C H_{2}O C H_{2}-+H_{2}O}\n$$  \n\n含羟甲基少的三嗪环上含未反应氢原子多，缩聚反应速率高，羟甲基多的三嗪环上含有未反应的氢原子少，缩聚反应进行的慢。为增加树脂水溶性和减少多聚体生成，生产中要尽可能使羟甲基化反应完成后再进行醚化反应，否则容易生成白色针状的多聚体，影响醚化反应的进行。  \n\nc.醚化反应甲醇与多羟甲基三聚氰胺的醚化反应是在酸性条件下进行，为使醚化反应顺利进行，使用过量的甲醇参与反应，在酸性条件下，多羟甲基三聚氰胺醚化反应和缩聚反应是同时进行的，六羟甲基三聚氰胺与过量甲醇完全醚化可生成六甲氧基甲基三聚氰胺树脂（HMMM)，图示如下：  \n\n![](images/04c15ae5b8c18e0a63e2d1bd974f4a23e10731cfd3085ced5a024d7bacc506d5.jpg)  \n\n六甲氧基甲基三聚氰胺，简称HMMM或 $\\mathrm{HM}_{3}$ ，它是六官能度的单体化合物，纯的$\\mathrm{HM}_{3}$ 是白色针状晶体，熔点 $55\\mathrm{{C}}$ ，水中溶解度为 $10\\%$ (25℃)、 $15\\%$ 1 $40\\mathsf{C}$ )，可溶于大部分有机溶剂，有良好的热稳定性。合成HMMM采用：先在碱性条件下三聚氰胺与过量甲醛进行羟甲基化反应，得到晶体状六羟甲基三聚氰胺（HMM)，去除水分和未反应甲醛，然后在酸性条件下和过量甲醇反应，得到六甲氧基甲基三聚氰胺（HMMM)。  \n\n由于合成氨基树脂发生的羟甲基化反应、醚化反应、缩聚反应是可逆反应，反应的影响因素又很多，因此，工业上难以制得纯净的 $\\bf{H M}_{3}$ ，只能得到不同反应程度的混合物，其成分因反应条件和工艺配方的变化而有所不同。  \n\n$\\textcircled{2}$ 配方实例六甲氧基甲基三聚氰胺（HMMM）  \n\n第一步：合成六羟甲基三聚氰胺（HMM）  \n\n配方：  \n\n三聚氰胺去离子水  \n\n600kg 甲醛   \n500kg 10%NaOH  \n\n3860kg调节pH用操作：  \n\na.先投入甲醛、去离子水，第一次调节pH，用 $10\\%\\mathrm{{NaOH}}$ 调节pH为 $8.8\\sim9.0$ 费  \n\nb.加入三聚氰胺，逐步升温至约 $50\\Upsilon$ 停止升温，温度因放热而自升，要勤取样，认真观察反应变化状况，它是一个由浑浊逐渐变清，再由清变浑浊的过程，若不注意，三聚氰胺溶解、体系变清的现象就无法观察到。维持反应控制在 $60\\sim65\\mathrm{^{\\circ}C}$ 时进行。  \n\nc.体系透明后，第二次调节 $\\mathsf{p H}$ ，用 $10\\%\\mathrm{{NaOH}}$ 调节，控制 $\\mathsf{p H}$ 为 $8.8\\sim9.0$ 变d.于 $60\\sim65\\mathrm{^{\\circ}C}$ 维持至结晶析出，继续维持 $3.56$ 章  \n\ne.冷却，出料至放料盘，分离出水分和未反应甲醛后，低温（要低于熔点）干燥至固体分 $390\\%$ ，备用。  \n\n第二步：合成六甲氧基甲基三聚氰胺（HMMM)  \n\n<html><body><table><tr><td colspan=\"3\">配方：</td><td rowspan=\"2\"></td></tr><tr><td>HMM</td><td>1200kg（100%）要根据HMM含量</td><td>甲醇</td></tr><tr><td></td><td>折算后得出实际投入量</td><td>10%NaOH、盐酸</td><td>2500kg 调节pH用</td></tr><tr><td>指标：</td><td></td><td></td><td></td></tr><tr><td>外观</td><td>透明</td><td>黏度（25℃）</td><td>1500~5000mPs·s</td></tr><tr><td>色泽(Fe-Co)</td><td>≤1</td><td>游离醛</td><td>≤0.5%</td></tr><tr><td>固体分</td><td>≥98.0%</td><td></td><td></td></tr></table></body></html>  \n\n操作：  \n\na.先投入甲醇，第一次调节 $\\mathsf{p H}$ ，用盐酸调节，要求控制 $\\mathsf{p H}$ 为 $1.8\\sim2.0,$  \n\nb.加人HMM后升温，升温至约 $40^{\\circ}\\mathrm{C}$ ，并于 $40\\sim45\\Upsilon$ 维持，HMM溶解透明后，第二次调节 $\\mathsf{p H}$ ，用盐酸调节，要求控制 $\\mathsf{p H}$ 为 $2,5{\\sim}2,8$ 森  \n\nc.维持醚化反应1.0h；第三次调节 $\\mathsf{p H}$ ，用 $10\\%\\mathrm{NaOH}$ 调节，控制 $\\mathsf{p H}$ 为8 $\\therefore8\\sim9.0$ 叠  \n\nd.打开真空泵，减压条件下脱出过量甲醇和水分，并控制釜内温度 ${\\leqslant}60\\mathsf{\\bar{C}}$ （真空度≥$-0.09\\mathbf{MPa})$  \n\ne.脱到无甲醇馏出为止，结束。  \n\nf.无溶剂的HMMM过滤除盐极其不便，而且蜡状的成品使用也极其不方便，因此，可采用丁醇等溶剂稀释到一定固体分后，再过滤除盐。  \n\n(1）甲醇醚化脲醛树脂目前投入使用的甲醚化脲醛树脂都属于部分甲醚化（聚合型部分烷基化）的氨基树脂，具有良好的水溶性、溶剂溶解性，配合适当的基体树脂制成的涂膜具有快干性、良好的附着力。  \n\n工业品有两种型号：一种有相对高的聚合程度，分子量较大，树脂采用芳烃溶剂与脂肪族醇（常用丁醇、异丁醇或异丙醇）的混合物为溶剂，主要用于短油度醇酸树脂配合，干性较快，涂膜有良好的光泽、耐冲击性。一种有相对低的聚合程度，分子量较小，涂膜的干性相对较慢，但与醇酸、环氧和饱和聚酯等有良好的混溶性，也可作为水性防火涂料的主要成膜物质。  \n\n$\\Phi$ 部分甲醚化脲醛树脂特点  \n\na.水溶性极佳，优于部分甲醚化的三聚氰胺甲醛树脂。  \nb.涂膜有良好的光泽、耐冲击性。  \nc.与很多基体树脂，如醇酸、环氧和饱和聚酯等有良好的混溶性。  \nd.与脲醛树脂相比，丁醚化后的三聚氰胺甲醛树脂性能稳定，贮存稳定性良好。  \n$\\textcircled{2}$ 反应工艺合成部分甲醚化脲醛树脂的工艺的生产过程可分为四个步骤。  \n\na.羟甲基化反应采用全回流（不脱水）进行羟甲基反应。  \n\n三聚氰胺、甲醛在碱性条件下进行羟甲基反应，反应进行到一定程度，形成多羟甲基三聚氰胺。若采用多聚甲醛，参与反应前要先进行解聚，然后才能羟甲基化反应。不同产地的多聚甲醛聚合度有差异，表面处理情况也不同，多聚甲醛溶解透明，并不表示已完成解聚，要保证充分的解聚时间以完成解聚，否则可能引起胶结。  \n\nb.醚化反应采用二次醚化的方式保证醚化反应的进程。  \n\n为保证醚化反应的进程，采用二次醚化的方式来进行醚化反应，第一次醚化：有较高的羟甲基含量，醚化反应速率相对较高，在相对较弱的酸性下，也能顺利进行醚化反应。第二次醚化：醚化反应进行到一定程度后，已消耗了大量的羟甲基，醚化反应速率下降，采取提高反应体系酸性的方法来加快反应速率，从而保证醚化反应顺利进行。  \n\nc.回收甲醇减压脱出甲醇(主要成分甲醇、水)。  \n\n为保证醚化反应顺利进行，需要采用过量的甲醇，反应完成后，需要脱出未参与反应的甲醇、醚化反应生成水、原料中带入的水分。回收甲醇的操作一般在减压状态下进行，需要生产装置有良好的密封性能，减少泄漏，以保证较高的真空度，并在适当的温度下进行，若真空度低，只能以提高温度来保证回收甲醇顺利完成，温度上升，会引起缩聚程度的上升，树脂水溶性的下降，因此必须保证一定的真空度。脱出的回收甲醇经过精馏提纯后，以后生产时可使用。  \n\nd.后处理利用过滤设备去除树脂中杂质，使树脂清澈透明。  \n\n脱出甲醇后，树脂要用溶剂稀释到一定含量，然后经过过滤这一步骤，用以去除树脂中的各种杂质，目前一般采用丫过滤机，助滤剂采用硅藻土，若过滤前树脂色泽不佳，可适当加些轻质碳酸镁，然后维持一段时间进行脱色，最后过滤。  \n\n$\\textcircled{3}$ 配方实例部分甲醚化脲醛树脂  \n\n配方：  \n\n<html><body><table><tr><td>甲醇</td><td>2500kg 调节pH用</td><td>多聚甲醛（91%～93%)</td><td>1700kg</td></tr><tr><td>液碱、乙酸酐、盐酸 指标：</td><td></td><td></td><td></td></tr><tr><td>外观</td><td>透明</td><td>T-4黏度（25℃）</td><td>280~350s</td></tr><tr><td>色泽（Fe-Co)</td><td>≤</td><td>水溶性</td><td>≥1(树脂）8(水)</td></tr><tr><td>固体分</td><td>(70±2)%</td><td></td><td></td></tr></table></body></html>  \n\n操作：  \n\na.先投入甲醇与多聚甲醛，第一次调节pH，用液碱调节要求控制pH为 $8.8\\sim9.0$ ，务必调节准确。  \n\nb.缓慢升温，温度到达 $45\\sim50\\Upsilon$ 时维持，聚甲醛溶解透明后，维持1h，然后加人尿素，并逐渐升温到回流。并在回流温度下维持 $0.5\\mathrm{h}$ 费  \n\nc.第二次调节pH，用乙酸酐调节，控制 $\\mathsf{p H}$ 为 $5,0{\\sim}5.2\\$ ，然后维持回流反应 $2\\mathrm{h}$  \n\nd.冷却到35℃以下，第三次调节 $\\mathsf{p H}$ ，用盐酸调节要求控制锅内物料 $\\mathsf{p H}$ 为 $1.9{\\sim}2.1\\$ 务必调节准确（反应物在盐酸作用下，物料会逐渐透明)；调节后维持 $^\\mathrm{1h}$  \n\ne.第四次调节 $\\mathfrak{p H}$ ，用液碱调节，要求控制 $\\mathfrak{p H}$ 为 $8,8\\sim9.0$  \n\nf.打开真空泵，在减压条件下将过量的甲醇和反应生成水脱出，要适当控制锅内温度（不超过 $75\\mathrm{\\bar{C}}$ 。。  \n\ng.当将过量的甲醇和反应生成水脱完后，加入丁醇，搅拌均匀后（若树脂颜色偏深，可加人适量轻质碳酸镁脱色，一般加入量在 $300{\\sim}500\\mathbf{g})$ ，过滤包装。  \n\n(2）部分甲醇醚化三聚氰胺甲醛树脂从树脂结构上讲，作为氨基交联剂使用时，参与反应的甲氧基甲基与羟甲基，与目前使用量最大的部分丁醚化三聚氰胺树脂（582-2、590-3）结构类似，与基体树脂的羟基进行缩聚反应时，自身也会发生缩聚反应。  \n\n与丁醚化三聚氰胺树脂相比，它与醇酸树脂、饱和聚酯树脂、环氧树脂、羟基丙烯酸树脂等具有更好的混溶性，使用部分甲醚化树脂还可降低涂膜的烘烤温度，有较好的耐化学性；树脂还具有一定的水溶性，可用于生产水性烤漆。  \n\n部分甲醚化三聚氰胺树脂在工业上投入应用，主要有两个方面：一是生产溶剂型烤漆，二是生产水性烤漆。为改善涂膜的耐水性，目前市场供应的树脂分别侧重溶剂漆和水性漆两种方向，侧重溶剂型漆用途的聚合度稍大。树脂不具有水溶性或水溶性很差；侧重水性漆用途的聚合度稍小些，并具有良好的水溶性。两种型号满足不同的应用需求。  \n\n$\\Phi$ 部分甲醚化三聚氰胺甲醛树脂特点  \n\na.与部分丁醚化三聚氰胺树脂相比，具有快干性、水溶性及更好的耐化学性。  \nb.与部分甲醚化脲醛树脂相比，涂膜有更好的光泽、丰满度。  \nc.与很多基体树脂：醇酸、环氧、羟基丙烯酸和饱和聚酯等具有良好混溶性。  \nd.与部分甲醚化脲醛树脂相比，具有更好的耐候性和贮存稳定性。  \n$\\textcircled{2}$ 反应工艺合成部分甲醚化三聚氰胺甲醛树脂的工艺的生产过程可分为四个步骤。  \n\na.羟甲基化反应采用碱性条件下进行羟甲基反应。  \n\n三聚氰胺、甲醛在碱性下进行羟甲基反应，反应进行到一定程度，形成多羟甲基三聚氰胺。有采用液体工业甲醛，也有采用多聚甲醛，更有混合使用的，全部采用液状工业甲醛，由于含大量水分，反应物浓度较低，对羟甲基化、醚化、缩聚反应的进程造成影响，树脂的黏度会上升，水溶性会下降。从生产工艺和树脂性能上看，混合采用甲醛还是可行的。  \n\nb.醚化反应采用酸性条件下进行醚化反应。  \n\n要注意观测三聚氰胺溶解透明，及时进行下一步操作。过高的醚化反应温度，能加快醚化反应速率、缩短醚化反应时间，但过快的醚化反应速率，不利于醚化反应进程，不利于树脂产品的稳定，因此，根据产品的要求，设定合理的醚化反应温度区间，以保证醚化反应顺利进行。  \n\nc.回收甲醇减压脱出甲醇（主要成分甲醇、水)。  \n\n反应完成后，回收甲醇的操作是在减压状态下进行的，反应釜良好的密封性能，使用足够排气量的真空泵，适当的回收温度，可以保证回收甲醇顺利完成，若真空不足，会使回收温度上升，从而引起缩聚程度的上升，必须保证足够真空度。回收甲醇经过精馏提纯后，以后生产时可使用。  \n\nd.后处理利用过滤设备去除树脂中杂质，使树脂清澈透明。  \n\n脱出甲醇后，树脂稀释到规定含量，再用过滤来去除树脂中的各种杂质，目前一般采用$\\pmb{\\gamma}$ 过滤机，助滤剂采用硅藻土，若过滤前树脂色泽不佳，可适当加些轻质碳酸镁，然后维持一段时间进行脱色，最后过滤。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 223,
+        "chunk": "# $\\textcircled{3}$ 配方实例部分甲醚化三聚氰胺甲醛树脂  \n\n配方：  \n\n三聚氰胺 700kg 丁醇 850kg 甲醇 ①550kg ②2700kg 甲醛 1080kg 多聚甲醛(91%\\~93%) 425kg 液碱、盐酸 调节pH用 指标： 外观 透明 固体分 (60±2)% 色泽（Fe-Co) ≤ T-4黏度(25C) 40\\~70s  \n\n操作：  \n\na.先投入甲醛、甲醇 $\\textcircled{1}$ ，第一次调节 $\\mathfrak{p H}$ ，用液碱调节要求控制 $\\mathfrak{p H}$ 为 $8,8\\sim9.0$ b.加人多聚甲醛后升温，升温度到约 $70\\Upsilon$ 时停止升温，放热自升，并维持温度75～$80\\Upsilon$ ，多聚甲醛溶解透明后，维持1.0h；维持结束后，冷却降温至 $35\\mathrm{{C}}$ 以下。  \n\nc.第二次调节 $\\mathtt{p H}$ ，用液碱调节，控制釜内物料 $\\mathsf{p H}$ 为 $8.5{\\sim}8.8$  \n\nd.加入三聚氰胺，逐步升温至约 $50\\Upsilon$ 停止升温，温度因放热而自升，要勤取样，认真观察反应变化状况，它是一个由浑浊逐渐变清，再由清变浑浊的过程，若不注意，三聚氰胺溶解、体系变清的现象就无法观察到。维持反应控制在 $58{\\sim}63^{\\circ}\\mathrm{C}$ 时进行。  \n\ne.反应物全部溶解后，继续维持 $30\\mathrm{\\sim}45\\mathrm{min}$ ，加人甲醇 $\\textcircled{2}$ ，第三次调节 $\\mathbf{\\Pi}_{\\mathbf{pH}}$ ，用盐酸调节，控制釜内物料 $\\mathfrak{p H}$ 为 $4.8\\sim5.0$ ，同时控制温度 $45\\sim50\\ensuremath{\\mathrm{^circ}}\\mathrm{C}$ （温度不得超过 $50\\%$ ，否则会使醚化反应时间过短，从而影响醚化反应进程)。  \n\nf.反应物在盐酸作用下，物料逐渐透明，待完全透明后，维持 $30\\mathrm{{min}}$ ，第四次调节 $\\mathbf{pH}$ 用液碱调节 $\\mathsf{p H}$ ，要求控制 $8.8\\sim9.0$ 9  \n\ng.打开真空泵，在减压条件下将过量的甲醇和反应生成水脱出，要适当控制锅内温度（不超过 $75\\Upsilon)$  \n\nh.当将过量的甲醇和反应生成水脱完后，加人丁醇，搅拌均匀后（若树脂颜色偏深，可加入适量轻质碳酸镁脱色，一般加入量在 $300\\sim500g)$ ，过滤包装。  \n\n(3）低亚氨基、高甲醚化氨基树脂此类高甲醚化树脂结构中未醚化的羟甲基很少、亚氨基很少，从树脂结构上讲，基本上是单体，六甲氧基三聚氰胺（HMMM）属于这类树脂。由于合成HMMM的反应复杂，甲醇、甲醛等原料消耗极大，工业生产又受很多因素影响，事实上要得到纯粹的HMMM很难。另外，HMMM外观呈白色晶体状，用以制漆也有很多不便，目前涂料行业极少使用纯粹的HMMM。  \n\n目前大规模应用的是液体状的低亚氨基、高甲醚化氨基树脂，与HMMM相比，分子结构中含有少量的羟甲基和亚氨基，甲醚化程度稍低，分子量稍大。用作交联剂时，固化温度要高于常用的丁醚化氨基树脂，为改善固化条件，通常情况下，还需加入有机酸催化剂。  \n\n$\\Phi$ 低亚氨基、高甲醚化氨基树脂特点  \n\na.不含溶剂，有利于制作高固体分涂料，减少有机溶剂的使用量。  \nb.与部分甲醚化三聚氰胺树脂相比，具有极佳的柔韧性，但固化温度要高。  \nc.与配套使用的基体树脂，如羟基丙烯酸和饱和聚酯等具有良好的混溶性。  \nd.与其他氨基树脂相比，硬度和柔韧性能很好地平衡。  \n$\\textcircled{2}$ 反应工艺合成部分甲醚化三聚氰胺甲醛树脂的工艺的生产过程可分为四个步骤。  \n\na.羟甲基化反应采用碱性条件下进行羟甲基反应。  \n\n三聚氰胺、甲醛（一般混合采用液体工业甲醛与多聚甲醛）在碱性下进行羟甲基反应，反应进行到一定程度，形成多羟甲基三聚氰胺，用酸性催化剂将体系调整为酸性后，即可进行醚化反应。HMMM合成时，是将羟甲基产物HMM取出，分离水分和未反应甲醛并且干燥后，再进行醚化反应。  \n\nb.醚化反应采用二次醚化的方式保证醚化反应的进程。  \n\n为保证醚化反应的进程，可采用二次醚化的方式来进行醚化反应。第一次醚化：醚化反应进行到一定程度后，已消耗了大量的羟甲基，体系酸性也减弱，醚化反应速率下降，采取补加甲醇、增加甲醇浓度，继续调整体系酸性的方法来加快反应速率，从而保证醚化反应顺利进行。  \n\nc.回收甲醇减压脱出甲醇（主要成分甲醇、水）。  \n\n反应完成后，回收甲醇的操作是在减压状态下进行，反应釜良好的密封性能、足够的真空度，可以保证回收甲醇顺利完成（若真空不足，会使回收温度上升，从而引起缩聚程度的上升)。回收甲醇经过精馏提纯后，以后生产时可使用。  \n\nd.后处理利用过滤设备去除树脂中杂质，使树脂清澈透明。  \n\n脱出甲醇后，用过滤来去除树脂中的各种杂质，目前一般采用 $\\boldsymbol{\\gamma}$ 过滤机，助滤剂采用硅藻土，若过滤前树脂色泽不佳，可适当加些轻质碳酸镁，然后维持一段时间进行脱色，最后过滤。  \n\n$\\textcircled{3}$ 配方实例低亚氨基、高甲醚化氨基树脂  \n\n配方：  \n\n<html><body><table><tr><td>三聚氰胺</td><td></td><td>650kg 1600kg</td><td>液碱、盐酸</td><td>调节pH用 850kg</td></tr><tr><td>甲醇</td><td>①1600kg</td><td>②1000kg 1290kg</td><td>甲醛</td><td></td></tr><tr><td colspan=\"5\">多聚甲醛（91%~93%)</td></tr><tr><td colspan=\"2\">指标：</td><td>透明</td><td>黏度（25℃）</td><td>1500~5000mPa•s</td></tr><tr><td colspan=\"2\">外观</td><td>≤1</td><td>游离醛</td><td>≤0.5%</td></tr><tr><td colspan=\"2\">色泽(Fe-Co)</td><td></td><td></td><td></td></tr><tr><td colspan=\"2\">固体分</td><td>≥98.0%</td><td></td><td></td></tr></table></body></html>  \n\n操作：  \n\na.先投入甲醛、甲醇 $\\mathfrak{D}$ ，第一次调节 $\\mathsf{p H}$ ，用液碱调节要求控制 $\\mathsf{p H}$ 为 $8.8\\sim9.0$ Kb.加入多聚甲醛后升温，升温度到约 $70\\Upsilon$ 时停止升温，放热自升，并维持温度75～$80^{*}\\mathsf{C}$ ，多聚甲醛溶解透明后，维持1.0h；维持结束后，冷却降温至 $35\\mathrm{{C}}$ 以下。  \n\nc.第二次调节 $\\mathfrak{p H}$ ，用液碱调节，控制釜内物料 $\\mathfrak{p H}$ 为 $8.8\\sim9.0$ 0  \n\nd.加入三聚氰胺，逐步升温至约 $50\\%$ 停止升温，温度因放热而自升，要勤取样，认真观察反应变化状况，它是一个由浑浊逐渐变清，再由清变浑浊的过程，若不注意，三聚氰胺溶解、体系变清的现象就无法观察到。维持反应控制在 $58\\sim63^{\\circ}C$ 时进行。  \n\ne.反应物全部溶解后，继续维持3.5h，加入甲醇 $\\textcircled{2}$ ，第三次调节 $\\mathsf{p H}$ ，用盐酸调节，控制釜内物料 $\\mathsf{p H}$ 为 $2,0{\\sim}2,2$ ，同时控制温度 $50\\sim55\\Upsilon$  \n\nf.反应物在盐酸作用下，物料逐渐透明，待完全透明后，维持1.5h，第四次调节 $\\mathsf{p H}$ .用液碱调节 $\\mathfrak{p H}$ ，要求控制 $9.8\\sim10.0\\$ a  \n\ng.打开真空泵，减压条件下脱出未反应甲醇和水分，并控制釜内温度 $\\leqslant75\\bar{\\mathsf{C}}$ h.加入甲醇 $\\textcircled{3}$ ，用盐酸第五次调节 $\\mathsf{p H}$ ，控制 $\\mathrm{pH}\\ 2.0{\\sim}2.2$ ，升温到 $60^{\\circ}\\mathrm{C}$ 醚化1.51i.第六次调节 $\\mathsf{p H}$ ，用液碱调节，控制 $\\mathbf{pH}~9.8\\sim10.0\\$ ，过滤除盐。  \n\nj.除盐后，物料投入釜内，减压下脱出未反应甲醇和水分，并控制釜内温度 $\\leqslant100^{\\circ}\\mathrm{C}$ （真空度 $\\geqslant-0.09\\mathbf{M}\\mathbf{P}\\mathrm{a})$ ，回收完成后，过滤包装。  \n\n(4）高亚氨基、高甲醚化氨基树脂此类高甲醚化树脂分子结构中，三嗪环的氨基上有一定量亚氨基存在，醚化反应完全，未醚化的羟甲基较少，再经过缩聚反应，结构中羟甲基含量极低，与部分烷基化的氨基树脂结构类似，能与基体树脂进行类似的交联反应，也能进行自缩聚反应。此类氨基树脂与含羧基、羟基、酰氨基的基体树脂进行交联反应时，基体树脂的酸性可催化交联反应，若加入有机酸作酸催化剂可加速交联反应。  \n\n树脂中亚氨基的存在，当其作为交联使用时，可较快的固化交联。当交联温度小于$120^{\\circ}C$ 时，自缩聚反应速率要高于交联反应速率，从而使涂膜硬而脆，韧性极差；当交联温度大于 $150^{\\circ}\\mathrm{C}$ 时，交联反应速率加快，因而能得到性能优异的涂膜。而且此类氨基树脂交联时，释放出的甲醛相对较少，即使厚涂层施工也不易产生缩孔。  \n\n此类氨基树脂分子量比部分甲醚化氨基树脂要低，但比低亚氨基、高甲醚化氨基树脂要高，易与芳烃溶剂、脂肪族一元醇及水相容，适宜作高固体分涂料的交联剂，也可用于卷材涂料的交联剂。三种三聚氰胺甲醛树脂对比见表2-1-69。  \n\n表2-1-69三种三聚氰胺甲醛树脂对比  \n\n\n<html><body><table><tr><td>项目</td><td>部分丁醚化树脂</td><td>部分甲醚化树脂</td><td>高亚氨基甲醚化树脂</td></tr><tr><td>外观</td><td>无色透明</td><td>无色透明</td><td>无色透明</td></tr><tr><td>分子量</td><td>较高</td><td>中</td><td>较低</td></tr><tr><td>主要反应基团</td><td>羟甲基、丁氧基</td><td>羟甲基、甲氧基</td><td>亚氨基、甲氧基</td></tr><tr><td>交联反应催化剂</td><td>有机酸性催化剂</td><td>一</td><td>有机酸性催化剂</td></tr><tr><td>溶解性</td><td>溶有机溶剂、不溶水</td><td>溶于部分醇及水</td><td>溶于醇、芳烃、水</td></tr><tr><td>应用范围</td><td>溶剂型涂料</td><td>溶剂型涂料、水性涂料、卷材涂料高固体涂料、卷材涂料</td><td></td></tr></table></body></html>  \n\n(5）甲醚化苯代三聚氰胺甲醛树脂目前在涂料行业应用的甲醚化苯代三聚氰胺甲醛树脂大都属于高甲醚化氨基树脂，其合成反应机理与甲醚化三聚氰胺甲醛树脂相似。  \n\n由于使用苯代三聚氰胺，因而每个三嗪环上都有一个苯环，使这类树脂在脂肪烃溶剂、芳烃溶剂、脂肪族一元醇中有良好的溶剂溶解性，与基体树脂有更好的混溶性，用于生产溶剂性涂料、高固体分涂料、水性涂料、卷材涂料等。苯环的存在使涂膜具有优异的耐化学性、抗沾污性，可应用于易拉罐内壁涂等。与适当的基体树脂配合，还具有优异的电泳性能，可用于生产电泳涂料。  \n\n$\\Phi$ 甲醚化苯代三聚氰胺甲醛树脂特点  \n\na.与甲醚化三聚氰胺树脂相比，具有更好的硬度与初期光泽，但交联温度要高。  \nb.与甲醚化三聚氰胺树脂相比，具有更好的耐化学性、抗沾污性。  \nc.与甲醚化三聚氰胺树脂相比，与基体树脂具有更好的混溶性。  \nd.与甲醚化三聚氰胺树脂相比，成本更高。  \n\n$\\textcircled{2}$ 反应工艺合成甲醚化苯代三聚氰胺甲醛树脂的工艺与合成甲醚化三聚氰胺树脂相似。  \n\na.羟甲基化反应采用碱性条件下进行羟甲基反应。  \n\n多聚甲醛解聚后与苯代三聚氰胺在碱性下进行羟甲基反应，反应进行到一定程度，形成多羟甲基苯代三聚氰胺。  \n\nb.醚化反应采用酸性条件下进行醚化反应。  \n\n为保证醚化反应的进程，采用过量的甲醇进行醚化反应，与甲醚化三聚氰胺树脂相比，醚化反应的温度要高一些。  \n\nc.回收甲醇减压脱出甲醇（主要成分甲醇、水）。  \n\n反应完成后，回收甲醇的操作是在减压状态下进行的，要保持反应釜良好的密封性能、足够的真空度，从而保证回收甲醇顺利完成。回收甲醇经过精馏提纯后，以后生产时可使用。  \n\nd.后处理利用过滤设备去除树脂中杂质，使树脂清澈透明。  \n\n脱出甲醇后，用过滤来去除树脂中的各种杂质，目前一般采用过滤机，助滤剂采用硅藻土，若过滤前树脂色泽不佳，可适当加些轻质碳酸镁，然后维持一段时间进行脱色，最后过滤。  \n\n$\\textcircled{3}$ 配方实例 甲醚化苯代三聚氰胺甲醛树脂  \n\n配方：  \n\n<html><body><table><tr><td>苯代三聚氰胺 甲醇</td><td>800kg ①700kg ②2600kg</td><td>多聚甲醛（91%~93%） 液碱、盐酸</td><td>590kg 调节pH用</td></tr><tr><td>指标：</td><td></td><td></td><td></td></tr><tr><td>外观</td><td>透明</td><td>黏度（25C）</td><td>3000~5000mPa * s</td></tr><tr><td>色泽（Fe-Co)</td><td>≤1</td><td>游离醛</td><td>≤0.5%</td></tr><tr><td>固体分</td><td>≥98.0%</td><td></td><td></td></tr></table></body></html>  \n\n操作：  \n\na.先投入多聚甲醛、甲醇 $\\mathbb{O}$ ，第一次调节pH，用液碱调节要求控制pH为 $8.8\\sim9.0$ ab.升温度到约 $70\\mathrm{{^{*}C}}$ 时停止升温，放热自升，并维持温度 $75\\sim80\\Upsilon$ ，多聚甲醛溶解透明后，维持1.0h；维持结束后，冷却降温至 $50^{\\circ}\\mathrm{C}$ 以下。  \n\nc.第二次调节 $\\mathfrak{p H}$ ，用液碱调节，控制釜内物料 $\\mathfrak{p H}$ 为 $8,8\\sim9.0,$ 。  \n\nd.加入苯代三聚氰胺，逐步升温至约 $55\\mathrm{{^{q}C}}$ 停止升温，温度因放热而自升，要勤取样，认真观察反应变化状况，它是一个由浑浊逐渐变清，再由清变浑浊的过程，若不注意，苯代三聚氰胺溶解、体系变清的现象就无法观察到。维持反应控制在 $68\\sim72^{\\circ}C$ 时进行。  \n\ne.反应物全部溶解后，继续维持 $2.0\\mathrm{h}$ ，加入甲醇 $\\textcircled{2}$ ，第三次调节 $\\mathsf{p H}$ ，用盐酸调节，控制釜内物料 $\\mathbf{pH}$ 为 $1.5{\\sim}2.0$ ，同时控制温度 $50\\sim55\\Upsilon$ 。  \n\nf.反应物在盐酸作用下，物料逐渐透明，待完全透明后，维持1.5h，第四次调节pH，用液碱调节 $\\mathbf{pH}$ ，要求控制 $8,8\\sim9,0$ 0  \n\ng.打开真空泵，减压条件下脱出未反应甲醇和水分，并控制釜内温度 $\\leqslant75\\mathtt{C}$ （真空度≥$-0.09\\mathbf{MPa};$ ，回收完成后，过滤包装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 224,
+        "chunk": "# 4.混合醚化氨基树脂  \n\n为适应层出不穷的涂膜性能对氨基树脂的要求，发展出混合醚化的氨基树脂，主要为甲醇与丁醇混合醚化的三聚氰胺甲醛树脂、异丁醇与丁醇混合醚化的三聚氰胺甲醛树脂，使树脂能兼有不同醇类醚化的氨基树脂特点，满足不同的生产需要。  \n\n(1）混合醚化三聚氰胺甲醛树脂特点主要特性介于单独使用各种醇类醚化的氨基树脂之间。  \n\n(2）反应机理采用二步法生产工艺。先在弱碱性条件下进行羟甲基反应，然后在酸性条件下进行醚化反应和缩聚反应，与正丁醇醚化氨基树脂反应机理相同。  \n\n(3）反应工艺混合醚化三聚氰胺树脂采用二步法进行，整个生产工艺与正丁醇醚化三聚氰胺树脂相同。  \n\n（4）配方实例正异丁醇混合醚化氨基树脂  \n\n配方：  \n\n<html><body><table><tr><td>三聚氰胺 异丁醇</td><td>600kg 1300kg</td><td>正丁醇 苯酐</td><td>1100kg 2.5kg</td></tr><tr><td>轻质碳酸镁</td><td>2. 3kg</td><td>二甲苯</td><td>360kg</td></tr><tr><td>甲醛</td><td>2450kg</td><td></td><td></td></tr><tr><td>指标：</td><td></td><td></td><td></td></tr><tr><td></td><td>透明</td><td>T-4黏度（25℃）</td><td>100~150s</td></tr><tr><td>外观</td><td>≤1</td><td>苯中清</td><td>清</td></tr><tr><td>色泽（Fe-Co)</td><td></td><td>容忍度（200*溶剂）</td><td>1· (5～10)浑</td></tr><tr><td>固体分 酸值/（mgKOH/g）</td><td>(65±2)% ≤1</td><td></td><td></td></tr></table></body></html>  \n\n操作：  \n\n$\\Phi$ 先投人正丁醇、异丁醇、二甲苯、溶剂（无溶剂时不投)，然后加三聚氰胺和轻质碳酸镁，再投入甲醛；逐渐升温，当温度达到 $80^{\\circ}\\mathrm{C}$ 时，停止加热，维持1.0h，再升温至回流。  \n\n$\\textcircled{2}$ 全回流反应（约 $92\\mathrm{^\\circC}$ ）2.5h，关闭蒸汽，等回流停止后关揽拌。  \n\n$\\textcircled{3}$ 加苯酐后开搅拌加热，并继续保持全回流反应1.5h。  \n\n$\\textcircled{4}$ 关闭蒸汽、停止搅拌，静止1h后，从反应锅底部分去废水。  \n\n$\\textcircled{5}$ 开搅拌，升温至回流，开始脱水，注意控制脱水速度；随着水分逐渐脱去，温度会逐渐上升，约 $100{\\sim}101\\%$ 时取样第一次中控，整个回流脱水阶段一般控制在 $4\\sim5\\mathrm{h}$ 。  \n\n$\\textcircled{6}$ 中控测试（容忍度、黏度)。此时测试结果一般为 $(25\\mathrm{{T}})$ \\*\\*  \n\nT-4黏度 30\\~40s 容忍度 1:(2\\~3)浑  \n\n$\\textcircled{7}$ 不断脱出溶剂，并进行终点控制，要求达到：  \n\nT-4黏度(25C） 110\\~140s 苯中清 清 容忍度 1 (6\\~9)浑  \n\n若容忍度偏高，脱溶剂要快（过分高时，可考虑减压脱溶剂）。  \n\n$\\textcircled{8}$ 达到要求后，冷却到 $80\\mathrm{\\bar{C}}$ 以下（若树脂颜色偏深，可加入适量轻质碳酸镁脱色，一般加入量在 $300\\sim500\\mathbf{g})$ ，过滤包装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 225,
+        "chunk": "# 五、氨基树脂的生产设备  \n\n生产氨基树脂的主要设备有反应釜、真空泵、压滤机，根据工艺特点，一般采用单釜间隙式生产工艺。以反应釜为主，配套有直冷凝器（若不配，可直接安装立管)、横冷凝器、分水器、压滤机。氨基树脂生产设备简图如图2-1-9所示。  \n\n氨基树脂反应过程中，有需要加热的工序，也有需要冷却的工序，反应进行到某一阶段，需要降温来快速减缓反应速度，以便进入另一阶段操作，若不能及时降温，会影响整个反应进程，所以必须选用合适的加热和冷却方式。氨基树脂反应温度，一般最高不超过$120^{\\circ}\\mathrm{C}$ ，采用饱和蒸汽加热的方式可满足生产工艺的要求。  \n\n常见的是有夹套（或半管）反应釜，蒸汽和冷却水都从夹套进出，根据工艺需要进行切换，也有采用内置盘管、外部夹套的形式，一般夹套通蒸汽而内置盘管通冷却水。反应釜内搅拌的作用是保证参与反应的物料充分混合，使反应体系成为均相，氨基树脂在生产时黏度不大，通常采用桨式搅拌器或锚式搅拌器。  \n\n氨基树脂生产过程中产生盐分，还有原料中可能带人的机械杂质，这些都要通过过滤去除，目前一般采用垂直网板式过滤机（行业内一般称为过滤机）过滤。为保证过滤效果，避免一些机械杂质对不锈钢丝网造成影响，可在反应釜和过滤机之间安装袋式过滤的装置（内置不锈钢丝网)，分离掉比较大的固体颗粒，以避免损坏过滤机。  \n\n氨基树脂生产过程中，有很长的回流反应过程，若设置直冷凝器，上半部设置成冷凝器，经过分水器的回流溶剂从冷凝器上进入，下半部设置为有一定数量填充料的分馏柱，上半部分流出的冷凝液，流到下半部分放置了填充料的分馏柱内，进行传质和传热，有利于共沸液的分离，减少热量消耗，但不少生产氨基树脂企业不设置直冷凝器。与其他涂料用树脂的生产相比，氨基反应釜横冷凝器面积配置较高，一般每1m体积至少配置6～7m面积横冷凝器，足够的横冷凝器面积可减少反应与回收溶剂过程中的溶剂损耗，降低消耗。  \n\n冷凝器下的分水器，收集冷凝下来的反应水和溶剂共沸物，由于互溶性有限，可依靠密度不同分层，上层溶剂，经回流管重新进人反应釜，水则从分水器底部排出。考虑到氨基树脂出水量较大，为简化和均衡操作，可利用密度和液位的原理，安装自动脱水装置，在脱水阶段从自动脱水装置脱水，可避免定时或不定时脱水的麻烦，也保证了操作的均衡与稳定。  \n\n![](images/2a395046a449f0bd66c6423ef134899953d289eb6dd963ecdef7703e111fb47c.jpg)  \n图2-1-9氨基树脂生产设备简图1—反应釜；2—直冷凝器；3-横冷凝器；4-分水器",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 226,
+        "chunk": "# 六、涂膜固化反应  \n\n氨基漆涂膜固化时，与氨基交联反应的基团一般是：羟基（一OH)、羧基（一COOH)、$(~{\\bf-}{\\bf C O}{\\bf-N H}_{2})$ $(\\mathrm{\\Sigma^{-cH-CH_{2}}}$ 存在两种以上的基团。氨基树脂参与反应的基团主要是羟甲基（—N—CHzOH)、亚氨基(—NH)、烷氧基甲基（—N—CHOR）三种基团。  \n\n氨基树脂中的烷氧基甲基是主要的交联基团，与基体树脂的羟基之间进行醚交换反应是主要的固化反应，需要在一定温度下完成交联反应固化成膜，羟甲基之间既会自缩聚，也能与基体树脂发生交联。羟甲基的反应性比烷氧基甲基大，亚氨基主要是自缩聚基团，容易与羟甲基自聚，也能进行双烯加成反应。  \n\n部分烷基化氨基树脂结构中主要含有烷氧基甲基和羟甲基。  \n\n高亚氨基、高醚化氨基树脂结构中主要含有烷氧基甲基和亚氨基。  \n\n低亚氨基、高醚化氨基树脂结构中主要含有烷氧基甲基和极少量的亚氨基、羟甲基。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 227,
+        "chunk": "# 1.酸催化反应  \n\n氨基树脂与基体树脂所含羟基、羧基、酰氨基进行共缩聚反应，这是交联时的主要反应，羧基对交联时的反应起催化作用，对氨基树脂的自缩聚反应也有催化作用，而基体树脂本身在涂膜中起增塑作用。  \n\n氨基树脂结构中的羟甲基、烷氧基甲基与基体树脂结构中的羟基交联反应。  \n\n氨基树脂结构中的羟甲基、亚氨基之间发生自缩聚反应。  \n\n提高交联固化温度、加大酸催化剂用量后，也能与羧基发生反应。  \n\n$$\n\\begin{array}{r}{\\begin{array}{r l}&{\\mathrm{~\\gamma_{NCH}}_{\\mathrm{{t}O H\\mathrm{~+HOOC}\\mathrm{-}R^{\\prime}}}\\underline{{\\underline{{\\mathrm{H}^{+}}}}}}\\end{array}\\sum_{i}^{\\mathrm{{NCH}_{1}O\\mathrm{-}\\ensuremath{C}\\mathrm{-}R^{\\prime}\\mathrm{{\\sigma}+H_{2}O}}}\\mathrm{{NCH}}_{i}0\\mathrm{{-}}\\begin{array}{l}{\\mathrm{{V}}}\\\\ {\\mathrm{{C}\\mathrm{-}R^{\\prime}\\mathrm{{\\sigma}+H_{2}O}}}\\end{array}}\\\\ &{\\mathrm{~\\gamma_{NCH}}_{\\mathrm{{t}O R\\mathrm{~+HOOC}\\mathrm{-}R^{\\prime}}}\\underline{{\\mathrm{H}^{+}}}\\begin{array}{l}{\\mathrm{{V}}}\\\\ {\\mathrm{{NCH}_{2}O\\mathrm{{-}}\\ensuremath{C}\\mathrm{-}R^{\\prime}\\mathrm{{\\sigma}+R O H}}}\\end{array}\n$$  \n\n氨基树脂结构中的羟甲基与基体树脂结构中的酰氨基交联反应。  \n\n氨基树脂结构中的羟甲基、烷氧基甲基与环氧基的交联反应。  \n\n氨基树脂结构中的羟甲基、烷氧基甲基、亚氨基之间也有可能发生自缩聚反应。  \n\n$$\n\\begin{array}{r}{\\underset{\\r{\\rightharpoondown}}{\\underbrace{\\sum\\mathrm{NCH}_{2}\\mathrm{OR}}}+\\mathrm{HN}\\underset{\\rightharpoondown}{\\overbrace{\\left(\\frac{\\mathrm{H}^{+}}{\\rightharpoondown}\\right)}}\\underset{\\rightharpoondown}{\\underbrace{\\sum\\mathrm{N-CH}_{2}-\\mathrm{N}}}\\underset{\\rightharpoondown}{\\underbrace{\\lnot}}+\\mathrm{HOH}}\\\\ {\\underset{\\rightharpoondown}{\\sum\\mathrm{NCH}_{1}\\mathrm{OR}}+\\mathrm{HOCH}_{2}-\\underset{\\rightharpoondown}{\\ r}\\underset{\\rightharpoondown}{\\underbrace{\\frac{\\mathrm{H}^{+}}{\\ r s}}}\\underset{\\rightharpoonup}{\\underbrace{\\sum\\mathrm{N-CH}_{2}-\\mathrm{N}}}\\underset{\\rightharpoondown}{\\underbrace{\\lnot}}+\\mathrm{HOH}+\\mathrm{H}_{2}\\mathrm{O}}\\\\ {\\underset{\\rightharpoondown}{\\sum\\mathrm{NCH}_{1}\\mathrm{OR}}+\\mathrm{ROCH}_{2}-\\underset{\\rightharpoondown}{\\rightharpoonup}\\underset{\\rightharpoonup}{\\underbrace{\\frac{\\mathrm{H}^{+}}{\\ r s}}}\\underset{\\rightharpoonup}{\\underbrace{\\sum\\mathrm{N-CH}_{2}-\\mathrm{N}}}\\underset{\\rightharpoonup}{\\underbrace{\\lnot}}+\\mathrm{H}_{2}\\underset{\\rightharpoonup}{\\underbrace{\\binom{2}{\\ r s}}}}\\end{array}\n$$  \n\n外加酸催化剂，可促进氨基树脂与基体树脂的交联反应，但必须选择合适的酸催化剂；若在通常的贮存条件下，采用的酸催化剂已开始释放酸性，氨基漆的贮存稳定性等势必受到影响，如采用涂装前加入的方式，可能造成使用量的不确定性，影响氨基漆的性能。  \n\n可以采用具有潜伏性特点的潜酸催化剂或称封闭型催化剂，即在通常的贮存条件下，酸催化剂不释放酸性，保持稳定，在交联固化的条件下，迅速释放酸性，从而促进氨基树脂与基体树脂的交联反应，这一类型的酸催化剂可称为潜催化剂。 A O  \n\n目前卷材涂料中通常使用的封闭型酸催化剂为对甲苯磺酸吡啶盐，对甲苯磺酸作为有机强酸，有很高的酸性，不宜直接用于氨基漆中，采用有机强碱（高挥发性的有机胺，如吡啶等）与对甲苯磺酸形成胺盐，在氨基漆交联固化的烘烤条件下，封闭剂挥发，又释放出酸性，从而起到酸催化剂作用，采用不同的封闭剂形成的酸催化剂，所需的解封温度是不同的。对甲苯磺酸极性较大，用于酸催化剂，会影响涂膜耐水性，目前通常采用极性较低的磺酸，如二壬基萘磺酸、二壬基萘二磺酸、十二烷基苯磺酸等，目前市场上有多种封闭好的酸催化剂可供选择，不必自己封闭。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 228,
+        "chunk": "# 2.双烯加成反应  \n\n醚化三聚氰胺树脂中的羟甲基和烷氧基甲基在酸性条件下，容易成为亚氨基。  \n\n亚氨基与基体树脂中的共轭双键进行双烯加成反应。  \n\n![](images/7b16f6f64544177411404fc0243e1f9d5694a4fd02926f715255234b032b4a03.jpg)  \n\n大多数干性油醇酸树脂中含有共轭双键，亚油酸与亚麻油酸中存在的双键在酸性条件下，通过异构化成为共轭双键，这些树脂均能通过双烯加成反应，增加涂膜的交联密度，但氨基的交联反应还是以酸催化的共聚和自聚为主，双烯加成反应为次。  \n\n从醚化氨基树脂可进行的交联反应看，能与大部分基体树脂进行交联，从而改善涂膜性能，不同的氨基树脂，所含的官能团有所差异，对基体树脂的反应活性不同。采用亚氨基含量高的氨基树脂作交联剂，能提高涂膜硬度，采用高醚化氨基树脂，能提高涂膜柔韧性，因此不同用途的烤漆，应选择不同类型的氨基树脂作交联剂。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 229,
+        "chunk": "# 七、氨基树脂的应用  \n\n涂料行业中，醚化的氨基树脂主要作为交联剂，与基体树脂交联成膜，选择不同的基体树脂，得到不同的漆膜性能，应用于不同的领域；同样的基体树脂，配以不同的氨基树脂，也会得到不同的涂膜性能。不同的应用领域，基体树脂（醇酸树脂、饱和聚酯树脂、羟基丙烯酸树脂、环氧树脂等）要选择相适应的氨基树脂来配合。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 230,
+        "chunk": "# 1.氨基-醇酸  \n\n氨基树脂与醇酸树脂匹配生产的烤漆，是涂料行业应用最早、最普遍的烤漆，形成的涂膜有良好的硬度、光泽、耐酸碱性、耐水性和耐候性，应用于汽车、自行车、洗衣机、缝纫机、小型家电、灯具外饰等轻工产品的涂装，采用合适的消光粉或体质颜料，氨基-醇酸烤漆还可制成哑光漆和半光漆。常用的氨基-醇酸属于溶剂性体系，用部分甲醚化氨基树脂配合水性醇酸树脂，可生产水性氨基-醇酸烤漆。  \n\n中、长油度醇酸树脂主要用于生产自干性醇酸磁漆，应用于氨基-醇酸烤漆体系的，通常采用短油度醇酸树脂，短油度醇酸树脂要保证生产稳定，一般需要相对较高的醇超量，树脂羟值也相对高些，从而有利于氨基树脂交联，涂膜硬度高。但羟值过大，会影响涂膜的抗水性。采用低醚化度的三聚氰胺树脂，配合中油度干性油醇酸树脂，用二甲苯稀释，可生产电机、电器用氨基绝缘漆。",
+        "category": " Introduction"
+    },
+    {
+        "id": 231,
+        "chunk": "# (1）氨基-344-2（短油度豆油醇酸树脂）烤漆  \n\n氨基清漆配方见表2-1-70。  \n\n表2-1-70 氨基清漆配方  \n\n\n<html><body><table><tr><td>原料名称</td><td>用量/kg</td><td>原料名称</td><td>用量/kg</td></tr><tr><td>344-2</td><td>320</td><td>二甲苯</td><td>30</td></tr><tr><td>582-2</td><td>118.5</td><td>1%甲基硅油</td><td>1.5</td></tr><tr><td>丁醇</td><td>30</td><td></td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>原料 名 称</td><td>用量/kg</td><td>原 料名 称</td><td>用量/kg</td></tr><tr><td>40%白浆</td><td>625</td><td>二甲苯</td><td>20</td></tr><tr><td>344-2</td><td>155</td><td>35%群青浆</td><td>2</td></tr><tr><td>590-3</td><td>175</td><td>1%甲基硅油</td><td>3</td></tr><tr><td>丁醇</td><td>20</td><td></td><td></td></tr></table></body></html>\n\n注：40%白浆组成为40%钛白粉、58%344-2、2%二甲萃。35%群青浆组成为35%群青、63%344-2、2%二甲苯。  \n\n配方实例：344-2醇酸树脂  \n\n\n<html><body><table><tr><td colspan=\"4\"></td></tr><tr><td>配方： 豆油</td><td>1051kg</td><td>顺酐</td><td>15kg</td></tr><tr><td>苯酐</td><td>1000kg</td><td>对稀二甲苯</td><td>1781kg</td></tr><tr><td>回流二甲苯</td><td>170kg</td><td>氢氧化锂</td><td>0.5kg</td></tr><tr><td>甘油</td><td>566kg</td><td>次磷酸</td><td>2.5kg</td></tr><tr><td colspan=\"4\">指标：</td></tr><tr><td>外观</td><td>透明</td><td>T-4黏度（25℃）</td><td>200~400s</td></tr><tr><td>酸值/（mgKOH/g)</td><td>≤11</td><td>色泽(Fe-Co)</td><td>≤5</td></tr><tr><td>固体分</td><td>(55±2)%</td><td></td><td></td></tr></table></body></html>  \n\n操作：  \n\n$\\textcircled{1}$ 将豆油、甘油投人反应釜，开揽拌加入氢氧化锂，加热升温，并在240～250℃醇解维持。  \n\n$\\textcircled{2}$ 醇解1h后，取样测试醇解是否完成，测试方法（样品：无水甲醇 $=1:3$ 清/室温)，一般醇解时间不超过3h。  \n\n$\\textcircled{3}$ 醇解到终点后，冷却到 $180^{\\circ}\\mathrm{C}$ 以下，加入苯酐、顺酐、次磷酸（与少量甘油混匀后加人）及回流二甲苯，打开直冷凝器及横冷凝器冷却水，升温至回流，进行酯化反应。  \n\n$\\textcircled{4}$ 酯化1h后，关闭直冷凝器冷却水，注意控制脱水及升温速度，最高酯化温度 $\\leqslant220\\mathtt{C}$ a  \n$\\textcircled{5}$ 酯化反应2h后，开始取样测黏度、酸值。中控取样11. $\\tau_{\\mathbf{{g}}}$ 样品 $+8,3\\mathbf{g}$ 二甲苯要求控制加氏黏度 $(25\\Upsilon)$ ） $15\\sim$ 19s酸值/（mgKOH/g) ${\\leqslant}11$  \n\n$\\textcircled{6}$ 酯化反应达到规定要求后，冷却到 $180^{\\circ}\\mathrm{C}$ 以下放料到对稀锅中（对稀锅中先加入部分对稀二甲苯)；反应锅中加入剩余对稀二甲苯，洗锅后放入对稀锅中，揽拌均匀、复测调整黏度。符合要求后过滤包装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 232,
+        "chunk": "# （2）氨基-3150（中油度麻油醇酸树脂）烤漆  \n\n氨基清漆配方见表2-1-72。  \n\n表2-1-71氨基白漆配方  \n表2-1-72氨基清漆配方  \n\n\n<html><body><table><tr><td>原料名称</td><td>用量/kg</td><td>原料名称</td><td>用量/kg</td></tr><tr><td>3150</td><td>510</td><td>二甲苯</td><td>72</td></tr><tr><td>582-2</td><td>340</td><td>1%甲基硅油</td><td>3</td></tr><tr><td>丁醇</td><td>75</td><td></td><td></td></tr></table></body></html>  \n\n配方：  \n\n配方实例：3150醇酸树脂  \n\n\n<html><body><table><tr><td>麻油</td><td>1280kg</td><td>回流二甲苯</td><td>210kg</td></tr><tr><td>次磷酸</td><td>2.5kg</td><td>苯酐</td><td>1500kg 915kg</td></tr><tr><td>甘油</td><td>520kg</td><td>对稀二甲苯</td><td></td></tr><tr><td>指标：</td><td></td><td></td><td></td></tr><tr><td>外观</td><td>透明</td><td>T-4黏度（25C）</td><td>300~600s</td></tr><tr><td>酸值/(mgKOH/g) 固体分</td><td>≤15 (60±2)%</td><td>色泽（Fe-Co)</td><td>≤3</td></tr></table></body></html>  \n\n操作：  \n\n$\\textcircled{1}$ 先将麻油、甘油投入反应锅，开搅拌加入苯酐、顺酐、次磷酸（与少量甘油混匀后加人）；加热升温并在 $150{\\sim}165\\mathrm{^{\\circ}C}$ 维持1h。  \n\n$\\textcircled{2}$ 升温到 $195{\\sim}205\\mathrm{\\textperthousand}$ 维持反应，维持到取样合格后冷却（取样在玻璃上，冷至室温后要达到透明，一般要 $1\\sim2\\mathrm{h})$ ，同时分去分水器中水。  \n\n$\\textcircled{3}$ 冷却到 $160^{\\circ}\\mathrm{C}$ 以下，加回流二甲苯，打开直冷凝器及横冷凝器冷却水，升温至回流；酯化反应1h后，关闭直冷凝器冷却水。  \n\n$\\textcircled{4}$ 注意控制脱水及升温速度，最高酯化温度 $\\leqslant205\\mathtt{C}$ 。在实际控制时，当酸值符合要求时，黏度接近下限最理想，控制时应根据黏度上升情况，来放分水器中水，以免温度过高，黏度上升过快。  \n\n$\\textcircled{5}$ 酯化反应2h后，开始取样测黏度、酸值。  \n\n中控取样 12. $\\gamma_{\\mathbf{{g}}}$ 样品 $+7.38$ 二甲苯  \n\n要求控制  \n\n加氏黏度 $(25\\Upsilon$ > $18\\sim22\\mathrm{s}$ 酸值 $\\leqslant15$  \n\n$\\textcircled{6}$ 酯化反应达到规定要求后，冷却到 $180^{\\circ}\\mathrm{C}$ 以下放料到对稀锅中（对稀锅中先加入部分对稀二甲苯)；反应锅中加入剩余对稀二甲苯，洗锅后放入对稀锅中，搅拌均匀、复测调整黏度。符合要求后过滤包装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 233,
+        "chunk": "# (3）氨基-343-3（短油度桐亚油醇酸树脂）烤漆  \n\n氨基锤纹漆配方见表2-1-73。  \n\n配方实例：343-3醇酸树脂  \n\n\n<html><body><table><tr><td>原料名称</td><td>用量/kg</td><td>原料名称</td><td>用量/kg</td></tr><tr><td>343-3</td><td>803</td><td>二甲苯</td><td>10</td></tr><tr><td>582-2</td><td>129</td><td>非浮型银浆</td><td>25</td></tr><tr><td>丁醇</td><td>33</td><td></td><td></td></tr></table></body></html>  \n\n表2-1-73 氨基锤纹漆配方  \n\n\n<html><body><table><tr><td>桐油 氢氧化锂</td><td>110kg 0.4kg</td><td>苯酐 对稀二甲苯</td><td>1050kg 2370kg</td></tr><tr><td>回流二甲苯</td><td>260kg</td><td>甘油</td><td>580kg</td></tr><tr><td>亚麻油</td><td>1040kg</td><td></td><td></td></tr><tr><td>指标：</td><td></td><td></td><td></td></tr><tr><td>外观</td><td>透明</td><td>T-4黏度(25℃)</td><td>200~300s</td></tr><tr><td>酸值/（mgKOH/g) 固体分</td><td>≤12 (50±2)%</td><td>色泽(Fe-Co)</td><td>≤13</td></tr></table></body></html>  \n\n配方：  \n\n操作：  \n\n$\\Phi$ 将桐油、亚麻油、甘油投入反应釜，开搅拌加入氢氧化锂，加热升温，并在 $240\\sim$ $250^{\\circ}\\mathrm{C}$ 醇解维持。  \n\n$\\textcircled{2}$ 醇解1h后，取样测试醇解是否完成，测试方法（样品：无水甲醇 $=1:3$ 清/室温)，一般醇解时间不超过 $^{3\\mathrm{h}}$ 9  \n\n$\\textcircled{3}$ 醇解到终点后，冷却到 $180\\mathrm{{\\textperthousand}}$ 以下，加人苯酐及回流二甲苯，打开直冷凝器及横冷凝器冷却水，升温至回流，进行酯化反应。  \n\n$\\textcircled{4}$ 酯化1h后，关闭直冷凝器冷却水，注意控制脱水及升温速度，最高酯化温度≤200℃。  \n\n$\\textcircled{5}$ 酯化反应2h后，开始取样测黏度、酸值。  \n\n中控取样 11. $0_{8}$ 样品 $+9.0{\\mathrm{g}}$ 二甲苯  \n\n要求控制  \n\n加氏黏度（25℃） 10\\~11s酸值 $\\leqslant11$  \n\n$\\textcircled{6}$ 酯化反应达到规定要求后，冷却到 $180^{\\circ}\\mathrm{C}$ 以下放料到对稀锅中（对稀锅中先加入部分对稀二甲苯)；反应锅中加入剩余对稀二甲苯，洗锅后放入对稀锅中，搅拌均匀、复测调整黏度。符合要求后过滤包装。  \n\n(4）氨基-合成脂肪酸改性醇酸树脂烤漆使用植物油合成的醇酸树脂通常都有较高的色泽，不利于生产颜色要求高、色彩纯正的浅色漆，而且大部分用于生产氨基烤漆的醇酸树脂使用的动植物油都含有一定量的不饱和键，容易被氧化，涂膜的耐黄变性不理想，限制了产品的应用。  \n\n用合成脂肪酸替代植物油来生产醇酸树脂，配合适宜的抗氧剂，可得到色泽接近水白色的树脂，树脂结构中又不含不饱和键，可用于对耐候性要求高、颜色鲜艳的场合，若用来生产罩光漆，能得到良好的装饰效果。氨基-醇酸烤漆的氨醇比通常为 $1:(2\\sim3)$ ，用来罩光的高光漆涂膜柔韧性要求不高，但要求很高的光泽，氨基用量要高了许多，氨醇比可达到$(1,5{\\sim}2,5)\\mathrel{\\ s}1,$  \n\n配方实例：合成脂肪酸改性醇酸树脂  \n\n\n<html><body><table><tr><td>配方：</td><td></td><td></td><td></td></tr><tr><td>十六酸</td><td>550kg</td><td>苯甲酸</td><td>202kg</td></tr><tr><td>三羟</td><td>925kg</td><td>兑稀二甲苯</td><td>1790kg</td></tr><tr><td>回流二甲苯</td><td>180kg</td><td>苯酐</td><td>950kg</td></tr><tr><td>顺酐</td><td>35kg</td><td>次磷酸</td><td>3. 0kg</td></tr><tr><td>指标：</td><td></td><td></td><td></td></tr><tr><td>外观</td><td>透明</td><td>T-4黏度(25C)</td><td>300~360s</td></tr><tr><td>酸值/(mgKOH/g)</td><td>≤10</td><td></td><td>≤1</td></tr><tr><td>固体分</td><td>(56±1)%</td><td>色泽(Fe-Co)</td><td></td></tr></table></body></html>  \n\n操作：  \n\n$\\Phi$ 将十六酸、顺酐、苯酐、三羟、苯甲酸、次磷酸、回流二甲苯投入反应锅，加热到能揽拌时开揽拌；同时打开直冷凝器及横冷凝器冷却水。  \n\n$\\textcircled{2}$ 逐步升温至回流进行酯化反应，注意控制脱水及升温速度，酯化反应 $^\\mathrm{1h}$ 后，关闭直冷凝器冷却水，并继续进行反应，最高酯化温度≤220℃。  \n\n$\\textcircled{3}$ 酯化反应3h后，开始取样测黏度、酸值。中控取样11.9g样品 $+8.1\\mathrm{g}$ 二甲苯要求控制  \n\n加氏黏度 $(25\\%$ >  \n\n酸值  \n\n$\\textcircled{4}$ 酯化反应达到规定要求后，冷却到 $180^{\\circ}\\mathrm{C}$ 以下放料到对稀锅中（对稀锅中先加入部分对稀二甲苯)；反应锅中加人剩余对稀二甲苯，洗锅后放人对稀锅中，揽拌均匀、复测调整黏度。符合要求后过滤包装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 234,
+        "chunk": "# 2.快干氨基-醇酸  \n\n常规的氨基-醇酸烤漆的烘烤条件为：温度 $120{\\sim}150^{\\circ}\\mathrm{C}$ 、时间 $60\\sim120\\mathrm{{min}}$ ，相对较高的温度和较长的时间，对树脂体系的耐烘烤、颜填料的耐温性都提出了相应的要求，若能在更低温度、更短时间内得到有同样装饰效果的涂膜，会有不错的应用前景。  \n\n要降低涂膜的烘烤温度与时间可采用如下方法： $\\textcircled{1}$ 在氨基-醇酸的烘漆体系中，加入酸催化剂； $\\textcircled{2}$ 用部分甲醚化氨基树脂代替部分丁醚氨基树脂； $\\textcircled{3}$ 以特制的快干醇酸树脂代替常规醇酸树脂。  \n\n外加酸催化剂的方便之处是在不改变涂料配方的前提下，改变固化条件，但要控制好酸催化剂的类型和用量，否则极易干扰涂墨性能，并影响涂料的贮存稳定性。采用脲醛树脂匹配合适的醇酸树脂，施工前加入一定量的酸催化剂，涂膜不烘烤也可交联固化，这种酸催化的氨基-醇酸体系可常温固化，因而可用作木器漆。  \n\n使用部分甲醚化氨基树脂作为交联剂，也可以改变烘烤条件，但成本与价格比丁醚化氨基要高出不少，需要平衡和估算产品的成本压力，采用部分甲醚化氨基树脂作交联剂，涂膜柔韧性比使用丁醚化氨基树脂稍差，因此，相对应的醇酸树脂要作出适当调整。  \n\n对醇酸树脂做一些调整，也能改变烘烤条件，可采取如下方法： $\\textcircled{1}$ 设计高酸值的醇酸树脂，保留较多的羧基，涂膜固化时，起酸催化的作用，达到降低温度和缩短时间的目的。不少颜料本身偏碱性，若醇酸树脂酸值过高，无法匹配，使这一类树脂的应用受到局限。 $\\textcircled{2}$ 采用其他原料，如丙烯酸硬单体、甲苯二异氰酸酯等对醇酸树脂进行改性，从而得到改性醇酸树脂，再与丁醚化氨基树脂交联，也可达到降低烘烤温度、缩短烘烤时间的目的。但改性树脂的生产工艺较为复杂，技术要求高，况且醇酸树脂改性后，成本也会增加，对产品应用会有影响。  \n\n以下是高酸值快干醇酸树脂与丙烯酸改性醇酸树脂配方示例。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 235,
+        "chunk": "# 配方实例：快干醇酸树脂  \n\n<html><body><table><tr><td colspan=\"5\"></td></tr><tr><td>配方： 十六酸</td><td>625kg</td><td>苯甲酸</td><td rowspan=\"2\"></td><td rowspan=\"2\">175kg</td></tr><tr><td>苯酐</td><td>1010kg</td><td>兑稀二甲苯</td></tr><tr><td>回流二甲苯</td><td>200kg</td><td>三羟</td><td rowspan=\"2\"></td><td rowspan=\"2\">2260kg 280kg</td></tr><tr><td>甘油</td><td>530kg</td><td>次磷酸</td></tr><tr><td>指标：</td><td></td><td></td><td rowspan=\"2\"></td><td rowspan=\"2\">3.0kg</td></tr><tr><td>外观</td><td>透明</td><td>T-4黏度（25C）</td></tr><tr><td>酸值/（mgKOH/g)</td><td>20~25</td><td>色泽(Fe-Co)</td><td rowspan=\"2\"></td><td rowspan=\"2\">250~350s ≤</td></tr><tr><td>固体分</td><td>(50±2)%</td><td></td></tr></table></body></html>  \n\n操作：  \n\n$\\Phi$ 将十六酸、甘油、苯酐、三羟、苯甲酸、次磷酸、回流二甲苯投入反应锅，加热到能揽拌时开揽拌；同时打开直冷凝器及横冷凝器冷却水。  \n\n$\\textcircled{2}$ 逐步升温至回流，进行酯化反应；注意液面情况，泡沫可能较高，要防止溢锅，放出回流出水。  \n\n③注意控制脱水及升温速度，酯化反应1h后，关闭直冷凝器冷却水，并继续进行反应，最高酯化温度 $\\leqslant200\\mathtt{{T}}$ 。  \n\n$\\textcircled{4}$ 维持酯化反应3h后，开始取样测固体酸值（不兑稀）；控制酸值 $25\\sim30$ 9  \n\n$\\textcircled{5}$ 冷却到 $170\\Upsilon$ 以下；打开倒门，快速投入偏苯三酸酐，升温，控制回流温度 $\\leqslant180\\Upsilon$  \n\n$\\textcircled{6}$ 酯化反应0.5h后，开始取样测黏度、酸值。  \n\n中控取样 11. $0\\mathbf{g}$ 样品 $+9,0{\\tt g}$ 二甲苯  \n\n要求控制  \n\n加氏黏度（25℃） 15\\~19s酸值 20\\~25  \n\n$\\textcircled{7}$ 酯化反应达到规定要求后，冷却到 $180\\mathrm{{\\textperthousand}}$ 以下放料到对稀锅中（对稀锅中先加人部分对稀二甲苯)；反应锅中加入剩余对稀二甲苯，洗锅后放入对稀锅中，搅拌均匀、复测调整黏度。符合要求后过滤包装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 236,
+        "chunk": "# 配方实例：丙烯酸改性醇酸树脂  \n\n<html><body><table><tr><td colspan=\"4\">预聚物配方：</td></tr><tr><td>月桂酸</td><td>700kg</td><td>次磷酸</td><td>3.0kg</td></tr><tr><td>顺酐</td><td>85kg</td><td>兑稀二甲苯</td><td>1640kg</td></tr><tr><td>回流二甲苯</td><td>200kg</td><td>苯酐</td><td>920kg</td></tr><tr><td>三羟</td><td>1250kg</td><td></td><td></td></tr><tr><td>指标：</td><td></td><td></td><td></td></tr><tr><td>外观</td><td>透明</td><td>T-4黏度（25C）</td><td>50~70s</td></tr><tr><td>酸值/(mgKOH/g)</td><td>4~6</td><td>色泽（Fe-Co)</td><td>≤1</td></tr><tr><td>固体分</td><td>(62±2)%</td><td></td><td></td></tr></table></body></html>  \n\n操作：  \n\n$\\textcircled{1}$ 将月桂酸、苯酐、三羟、顺酐、次磷酸、回流二甲苯投入反应锅，加热到能搅拌时开搅拌；同时打开直冷凝器及横冷凝器冷却水。  \n\n$\\textcircled{2}$ 逐步升温至回流，进行酯化反应；注意液面情况，泡沫可能较高，要防止溢锅，放出回流出水。  \n\n$\\textcircled{3}$ 注意控制脱水及升温速度，酯化反应 $\\ensuremath{\\mathrm{~\\textrm~{~~}~}}\\ensuremath{\\mathrm{1h}}$ 后，关闭直冷凝器冷却水，并继续进行反应，最高酯化温度 $\\leqslant220\\Upsilon$ #  \n\n$\\textcircled{4}$ 维持酯化反应3h后，开始取样测固体酸值（不对稀）；  \n\n酸值 7\\~10  \n\n$\\textcircled{5}$ 达到规定要求后，冷却到 $180^{\\circ}\\mathrm{C}$ 以下放料到对稀锅中（对稀锅中先加人部分对稀二甲苯)；反应锅中加入剩余对稀二甲苯，洗锅后放入对稀锅中，搅拌均匀、复测调整黏度。符合要求后过滤包装。  \n\n改性树脂配方：  \n\n<html><body><table><tr><td>预聚物</td><td>3400kg 675kg</td><td>丙烯酸丁酯 羟丙酯</td><td>495kg 200kg</td></tr><tr><td>甲甲酯 α-甲基苯乙烯</td><td>10kg</td><td>过氧化苯甲酰（BPO)</td><td>①70kg ②15kg</td></tr><tr><td>指标：</td><td></td><td></td><td></td></tr><tr><td>外观</td><td>透明</td><td>加氏黏度（25℃）</td><td>20~25s</td></tr><tr><td></td><td>4~6</td><td>色泽（Fe-Co)</td><td>≤1</td></tr><tr><td>酸值/（mgKOH/g) 固体分</td><td>（70±2)%</td><td></td><td></td></tr></table></body></html>  \n\n操作：  \n\n$\\Phi$ 将丙烯酸丁酯、甲甲酯、羟丙酯、 $\\mathtt{B P O}\\mathbb{O}$ 、a-甲基苯乙烯投入滴加槽，搅拌均匀后，  \n\n待滴加用。  \n\n$\\textcircled{2}$ 将预聚物投人反应釜，升温至约 $130^{\\circ}\\mathrm{C}$ 开始滴加单体，同时打开直冷凝器冷却水，控制滴加温度 $(130\\pm2)^{\\circ}\\mathrm{C}$ ；滴加时间控制为 $(75\\pm15)\\mathrm{min}$ ，不可过快或过慢。  \n\n$\\textcircled{3}$ 滴加完毕，在 $(130\\pm2)\\tau$ 维持 $1.0\\mathbf{h}$ ，补加BPO。  \n$\\textcircled{4}$ 加完BPO后，升温至回流；回流1h后开始取样黏度。  \n\n要求控制  \n\n加氏黏度（25℃） 20\\~25s  \n\n$\\textcircled{5}$ 反应达到要求后，冷却到 $100^{\\circ}\\mathrm{C}$ 以下放料到对稀锅中；揽拌均匀后复测黏度，符合要求后过滤包装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 237,
+        "chunk": "# 3.氨基-聚酯  \n\n聚酯树脂是由多元醇与多元酸合成的线型结构高聚物，树脂结构中含有羟基与羧基，能与氨基树脂交联，得到性能优异的涂膜，由于各种不同结构的多元醇与多元酸，能合成出适应多种不同涂膜性能要求的树脂，因此，氨基-饱和聚酯烘漆体系能适应多种场合的装饰要求。  \n\n目前这一烘漆体系，主要应用在发展迅速的卷材涂料行业，所生产的面漆、背面漆、底漆等，都有采用氨基-饱和聚酯烘漆体系的，使用高温短时间的交联成膜，板温通常为$190\\sim230\\ensuremath{\\mathrm{^{\\circ}C}}$ 之间，烘烤时间通常为 $45\\sim90{\\mathrm{s}},$ 费  \n\n以下为快速线海蓝面漆配方，供参考。  \n\n<html><body><table><tr><td>献菁蓝浆：</td><td></td><td></td><td></td></tr><tr><td>原料名称</td><td>用量/kg</td><td>原料名称</td><td>用量/kg</td></tr><tr><td>酸菁蓝</td><td>100</td><td>气相二氧化硅</td><td>2</td></tr><tr><td>聚酯树脂</td><td>725</td><td>DBE</td><td>70</td></tr><tr><td>BYKP104S</td><td>2</td><td>S-100</td><td>100</td></tr><tr><td>流平剂</td><td>1</td><td></td><td></td></tr><tr><td>白聚酯浆：</td><td></td><td></td><td></td></tr><tr><td>原料名称</td><td>用量/kg</td><td>原料名称</td><td>用量/kg</td></tr><tr><td>聚酯树脂</td><td>410</td><td>气相二氧化硅</td><td>1.5</td></tr><tr><td>金红型钛白粉</td><td>502</td><td>乙二醇丁醚</td><td>43</td></tr><tr><td>流平剂</td><td>1.5</td><td>S-100</td><td>42</td></tr><tr><td>消光剂浆：</td><td></td><td></td><td></td></tr><tr><td>原料名称</td><td>用量/kg</td><td>原料名称</td><td>用量/kg</td></tr><tr><td>聚酯树脂</td><td>450</td><td>S-100</td><td>360</td></tr><tr><td>气相二氧化硅</td><td>190</td><td></td><td></td></tr><tr><td>海蓝浆落料：</td><td></td><td></td><td></td></tr><tr><td>原料名称</td><td>用量/kg</td><td>原料名称</td><td>用量/kg</td></tr><tr><td>酸菁蓝浆</td><td>537</td><td>流平剂</td><td>2</td></tr><tr><td>聚酯树脂</td><td>135</td><td>气相二氧化硅</td><td>4</td></tr><tr><td>中黄粉</td><td>5.7</td><td>BYKP104S</td><td>2</td></tr><tr><td>柠黄粉</td><td>15.3</td><td>DBE</td><td>14</td></tr><tr><td>金红型钛白粉</td><td>280</td><td>S-100</td><td>5</td></tr><tr><td>海蓝配漆：</td><td></td><td></td><td></td></tr><tr><td>原料名称</td><td>用量/kg</td><td>原料名称</td><td>用量/kg</td></tr><tr><td>高甲醚化氨基</td><td>159</td><td>铁红浆</td><td>8.3</td></tr><tr><td>聚酯树脂</td><td></td><td>白聚酶浆</td><td>31</td></tr><tr><td>海蓝浆</td><td>351 1000</td><td>水固紫浆</td><td>1</td></tr></table></body></html>  \n\n<html><body><table><tr><td>原料名称</td><td>用量/kg</td><td>原料名称</td><td>用量/kg</td></tr><tr><td>消光剂浆</td><td>330</td><td>流平剂</td><td>2</td></tr><tr><td>15%磷酸丁醇</td><td>31</td><td>醋酸丁酯</td><td>52</td></tr><tr><td>配方实例：饱和聚酯树脂</td><td></td><td></td><td></td></tr><tr><td>配方：</td><td></td><td></td><td></td></tr><tr><td>新戊二醇</td><td>2380kg</td><td>对苯二甲酸</td><td>300kg</td></tr><tr><td>己二酸</td><td>600kg</td><td>单丁基氧化锡</td><td>3.0kg</td></tr><tr><td>回流二甲苯</td><td>270kg</td><td>乙二醇丁醚</td><td>490kg</td></tr><tr><td>间苯二甲酸</td><td>1500kg</td><td>100溶剂</td><td>805kg</td></tr><tr><td>偏苯三酸酐</td><td>500kg</td><td>150溶剂</td><td>1500kg</td></tr><tr><td>指标：</td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td>15~20s</td></tr><tr><td>固体分 色泽（Fe-Co)</td><td>58%~62% ≤1</td><td>加氏黏度（25℃） 酸值/(mgKOH/g)</td><td>2~5</td></tr></table></body></html>  \n\n操作：  \n\n①新戊二醇、间苯二甲酸、对苯二甲酸、偏苯三酸酐、己二酸投入反应釜，通氮气、升温。  \n\n$\\textcircled{2}$ 加热到能搅拌时，开动搅拌，投入单丁基氧化锡，打开直冷凝与横冷凝冷却水，反应出水后，停止通氮气。  \n\n$\\textcircled{3}$ 逐步升温，控制气相温度 $\\leqslant105\\mathrm{\\leqslant}$ ，釜内温度最高 $\\leqslant235\\mathrm{\\ttC}$ ▪  \n\n$\\textcircled{4}$ 当釜内温度到达 $230^{\\circ}\\mathrm{C}$ 后，取样在玻璃上，冷却到室温后，要达到透明，透明后维持$30{\\sim}45\\mathrm{min}$ 。冷却到 $180\\mathrm{^{\\circ}C}$ 以下，加人二甲苯。  \n\n$\\textcircled{5}$ 关闭直冷凝冷却水，边脱水边升温进行回流酯化反应，控制反应温度 $\\leqslant220\\mathtt{C}$ $\\textcircled{6}$ 回流反应1h后，进行中控，检验黏度、酸值（注意反应后阶段黏度上升趋势)。  \n\n取样比例12. $\\tau_{\\mathrm{{g}}}$ 样品 $+7.38$ 稀释溶剂要求控制加氏黏度 $(25^{\\circ}\\mathrm{C}$ ) $15\\sim20\\mathrm{s}$ 酸值/ $(\\mathrm{mgKOH/g})$ 2\\~5  \n\n$\\textcircled{7}$ 中控符合要求后，冷却到 $180^{\\circ}\\mathrm{C}$ 以下，放料到对稀釜中（对稀釜中先加入部分对稀溶剂)；反应釜中加入剩余的对稀溶剂，回流一段时间后放入对稀釜中，搅拌均匀后复测黏度，达到要求后过滤包装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 238,
+        "chunk": "# 4.氨基-丙烯酸树脂  \n\n丙烯酸树脂是由丙烯酸酯类、甲基丙烯酸酯类及其他烯类单体共聚组成的树脂，不同的单体组合可得到性能各异的树脂，满足各种需要。与氨基树脂匹配使用的丙烯酸树脂，树脂结构中含有羟基和羧基官能团，与氨基树脂交联成膜，主要应用于汽车、摩托车、卷铝、油墨等行业，涂膜有良好的丰满度、光泽、硬度、耐候性、耐化学性等。以下为卷铝涂料面漆配方。  \n\n轧浆：  \n\n<html><body><table><tr><td>原料名称</td><td>用量/kg</td><td>原料名称 紫红粉</td></tr><tr><td>羟基丙烯酸树脂</td><td>500</td><td></td></tr><tr><td>金红型钛白粉</td><td>45</td><td></td></tr><tr><td>中铬黄</td><td>180</td><td>二甲苯 S-150#</td></tr><tr><td>钼铬红</td><td>30</td><td>丁醇</td></tr><tr><td>配漆：</td><td></td><td></td></tr><tr><td>原料名称</td><td>用量/kg</td><td>原料名称</td></tr><tr><td>582-2</td><td>115</td><td>附着力促进剂</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 239,
+        "chunk": "# 配方实例：羟基丙烯酸树脂  \n\n<html><body><table><tr><td>配方：</td><td></td><td></td><td rowspan=\"5\">620kg ①2070kg 2660kg</td></tr><tr><td>苯乙烯</td><td>700kg</td><td>丙烯酸异辛酯</td></tr><tr><td>丙烯酸羟丙酯</td><td>420kg</td><td>二甲苯 丙丁酯</td></tr><tr><td>BPO</td><td>②7kg 3.5kg</td><td>690kg</td></tr><tr><td>甲甲酯</td><td>280kg 丙烯酸</td><td>52kg</td></tr><tr><td>指标：</td><td></td><td></td><td></td></tr><tr><td>固体分</td><td>48%~52%</td><td>加氏黏度（25C）</td><td>20~25s</td></tr><tr><td>色泽（Fe-Co)</td><td>≤1</td><td>酸值/（mgKOH/g)</td><td>≤9</td></tr></table></body></html>  \n\n操作：  \n\n$\\Phi$ 将全部单体投人滴加槽，并加人 $\\mathtt{B P O}\\mathbb{O}$ ，搅拌均匀后，待滴加用。  \n\n$\\textcircled{2}$ 将二甲苯 $\\Phi$ 投入反应釜，升温至 $85^{\\circ}\\mathrm{C}$ ，打开直冷凝器冷却水，开始滴加单体，滴加速度要控制均匀，滴加时间约 $4.0{\\sim}4.5\\mathrm{h}$ ，滴加温度 $85\\sim90^{\\circ}C$  \n\n$\\textcircled{3}$ 滴加完毕后，于 $85\\sim90^{\\circ}C$ 维持2.0h；补加 $\\mathtt{B P O}\\rVert$ ，同温维持1.0h。  \n\n$\\textcircled{4}$ 补加 $\\mathtt{B P O}\\odot$ ，同温维持 $1.0\\mathbf{h}$ ，取样观测黏度。  \n\n$\\textcircled{5}$ 关闭直冷凝器冷却水，同时打开横冷凝器冷却水，升温至回流，维持回流1.0h。  \n\n$\\textcircled{6}$ 进行中控，检验黏度。  \n\n取样比例 17. $5g$ 样品 $+2.5{\\mathrm{g}}$ 二甲苯要求控制加氏黏度（ $25\\mathrm{{C}}$ > $20\\sim25\\mathrm{s}$  \n\n$\\textcircled{7}$ 中控符合要求后，冷却到 $100\\mathrm{{^{\\circ}C}}$ 以下，加入二甲苯 $\\textcircled{2}$ ，搅拌均匀后复测黏度，达到要求后过滤包装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 240,
+        "chunk": "# 5.氨基-环氧树脂  \n\n环氧树脂是热塑性的，分子结构中的环氧基与氨基树脂中的羟甲基及烷氧基交联，形成了性能优异的涂膜，有很好的应用价值。涂膜有良好的耐盐雾性、耐水性，又有良好的附着力、硬度，但耐候、耐黄变性较差，因此，氨基-环氧烘漆体系适用于生产底漆。目前应用较为广泛的是卷钢涂料底漆中采用的脲醛树脂与环氧树脂固化体系。以下为卷铜环氧底漆配方。  \n\n<html><body><table><tr><td>原料名称</td><td>用量/kg</td><td>原料名称</td><td>用量/kg</td></tr><tr><td>50%609环氧溶液</td><td>441</td><td>DBE</td><td>7</td></tr><tr><td>锌黄粉</td><td>89</td><td>大豆磷酯</td><td>6.5</td></tr><tr><td>锡铬黄粉</td><td>18</td><td>乙二醇丁醚</td><td>163</td></tr><tr><td>锐钛型钛白粉</td><td>224</td><td>醋酸丁酯</td><td>17: 5</td></tr><tr><td>超细滑石粉</td><td>34</td><td></td><td>1000</td></tr><tr><td>配漆：</td><td></td><td></td><td></td></tr><tr><td>原料名称</td><td>用量/kg</td><td>原料名称</td><td>用量/kg</td></tr><tr><td>环氧底漆浆</td><td>1000</td><td>醋酸丁酯</td><td>74</td></tr><tr><td>50%609环氧溶液</td><td>612</td><td>乙二醇丁醚</td><td>86</td></tr><tr><td>丁醚化脲醛树脂</td><td>79</td><td>环已酮</td><td>29</td></tr><tr><td>15%磷酸丁醇</td><td>7</td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 241,
+        "chunk": "# 八、氨基树脂生产和使用时的VOC  \n\n溶剂型涂料生产中，稀释剂大多用二甲苯、甲苯、丁醇、 $200^{\\circ}$ 汽油等有机溶剂。合成树脂生产也会采用易挥发的甲醛、醇类、酯类等为原料，即使整个过程是在封闭系统中进行，考虑到原料和设备等各种因素，生产、施工环境中有毒害的气体挥发，VOC的污染还是在所难免。近年来，涂料的生产和施工过程中，挥发性有机物（VOC）产生的环境污染问题，引起人们的重视。低VOC、低污染涂料（如水性涂料、高固体分涂料、粉末涂料）已成为涂料行业主要发展方向，随着高固体分涂料及水性涂料的发展，甲醚化氨基树脂得到了迅速发展。  \n\n生产氨基树脂时，甲醛和醇是过量的，因此生产过程中排出的废水中，含有醇类、二甲苯和甲醛等有机物，其污染源是反应生成水和原料甲醛中带入的水，废水总量远远超过其他合成树脂。氨基树脂在涂料应用中，具有很重要的地位，因此要尽可能从工艺上减少氨基树脂生产中产生的污染，缓解对环境造成的压力。氨基树脂废水可采用先蒸馏脱醇，使废水$\\mathrm{COD}_{\\mathrm{cr}}$ 大幅下降，然后将含醛废水用于生产工业甲醛，既使废水中的少量甲醛得到充分利用，又解决了废水的排放问题。生产酚醛树脂的企业，可将含酚废水与脱醇后的含醛废水以一定比例混合，利用酚醛缩合反应，来达到降低 $\\mathrm{COD}_{e\\tau}$ 目的。  \n\n氨基树脂在涂料行业主要用于生产氨基烤漆，涂装时产生的主要污染物是：树脂所含有的有机溶剂和少量游离甲醛，在高温交联成膜时挥发，如何进行回收或处理，是涂装工艺要解决的问题。目前预涂卷材的生产线中，采用烧的方法来处理排出的含有机溶剂的废气，但大部分常规氨基烤漆涂装施工时，并没有相应的处理装置，所产生的废气大都直接排放，造成污染。若能结合实际涂装条件，可采取活性吸附、焚烧处理、高空排放、冷凝收集、生化处理等方法进行应对，以减少排放量。  \n\n我国1997年1月1日开始实施新的GB8978—1996《污水综合排放标准》和GB16297—1996《大气污染物综合排放标准》，对造成水污染和大气污染的各种挥发性有毒有害物质都作了限值规定。要降低或消除污染，必须改进工艺、从配方着手。如：适当降低投料温度、使用无毒低挥发性原料、采用计算机控制操作减少人为失误、采用先进生产设备来替代原有设备、使生产尽可能在无泄漏无污染系统中进行等，这些对于有效控制污染是有必要的。  \n\n为了避免和减少涂料施工过程中有机溶剂（VOC）对环境造成的影响，近年来高固体分涂料和水性涂料发展很快，从而带动了甲醚化氨基树脂的应用，目前在卷材涂料、低温快干涂料、水性涂料中有各类甲醚化树脂的应用。甲醚化树脂与丁醚化树脂相比，生产工艺复杂，单釜产量低，生产成本高，因此目前在涂料行业中，仍然是丁醚化氨基树脂最为常用，但甲醚化树脂的应用呈现增长态势，前景广阔。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 242,
+        "chunk": "# 第五节饱和聚酯树脂",
+        "category": " Introduction"
+    },
+    {
+        "id": 243,
+        "chunk": "# 一、概述  \n\n本节涉及的是涂料用聚酯树脂，采用多元醇与多元酸经酯化反应得到的高分子物，与不饱和聚酯相对应的是分子结构中不含非芳烃的不饱和键，习惯上称为聚酯树脂。 9  \n\n饱和聚酯树脂是一种线性结构的热塑性高聚物，涂料行业的实际应用中，需要与另一类树脂（氨基树脂、聚氨酯树脂等）配合，交联成膜。饱和聚酯树脂与醇酸树脂结构类似，发展的渊源又深，在涂料用树脂的分类上，称其无油醇酸树脂，属于醇酸树脂的特例。  \n\n1847年Berzelius 用甘油和酒石酸通过化学反应合成最早的聚酯树脂，1901年WatsonSmith 采用邻苯二甲酸酐与甘油制成了无油醇酸树脂，即聚酯树脂，1929 年 Kienle用甘油和苯酐反应并用不饱和脂肪酸改性合成了最早的醇酸树脂，从而迎来了醇酸树脂在涂料行业的应用，并得到了飞速发展。随着合成树脂行业的不断发展与进步，饱和聚酯树脂与涂料也在不断研究与发展中，20世纪60年代后期，出现了工业化生产的涂料用饱和聚酯树脂与饱和聚酯涂料。  \n\n多年来，为适应市场需要，有不少特殊多元醇、多元酸及功能性树脂被开发成功，使饱和聚酯树脂的原料来源极为丰富，大量各种性能的聚酯树脂品种得到应用，从而满足不同应用领域对涂料提出的性能要求，在家电、汽车、罐头等行业得到广泛应用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 244,
+        "chunk": "# 二、聚酯树脂所用的原料  \n\n合成饱和聚酯树脂最基本的原料是多元醇与多元酸，为保证树脂生产和加工的正常进行，需要使用溶剂来帮助脱水和稀释，工业生产为达到缩短工时的目的，需要使用催化剂来加快反应速度，为降低和保证树脂的色泽，需要抗氧剂的帮助。生产改性饱和聚酯需要相应的改性剂，如合成脂肪酸、环氧树脂、有机硅材料、丙烯酸单体或树脂等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 245,
+        "chunk": "# 1.多元醇  \n\n多元醇是指分子中含有多个与脂肪族碳链直接相连羟基（一OH）的化合物，其化学性质主要由羟基官能团决定，同时也受到烃基一定的影响。由于羟基所连接的碳原子性质不同，如伯碳、仲碳、叔碳，这些羟基又可分为伯羟基、仲羟基、叔羟基。脂肪族碳链所处烃基的不同结构特征将会对羟基的反应活性产生不同的影响，以伯羟基反应活性最高，而叔羟基反应活性最低。因此在选择多元醇时，要根据树脂的性能要求选择一些合适的多元醇进行配合，使聚酯树脂达到所要求的性能。  \n\n饱和聚酯树脂生产过程中，一般选用有一定烃基结构的、含有伯羟基的多元醇。环状的烃基结构，如对苯二甲酸与1，4-环己烷二甲醇，都能为聚合物提供硬度，但有脂肪族环状结构的1，4-环己烷二甲醇，又具有柔韧性、耐候性和耐黄变优势。直链的烃基结构，如1,6-已二醇的长碳链结构，使树脂的弯曲性好、柔韧性好、耐水性好。一些含有大支链烃基结构的多元醇（如羟基新戊酸羟基新戊酯、2-丁基-2-乙基-1，3-丙二醇等）往往能为树脂提供很好的应用性能，从而满足高性能涂料的应用要求。常用多元醇的参数见表2-1-74。  \n\n表2-1-74常用多元醇的参数  \n\n\n<html><body><table><tr><td>原料名称</td><td>简称</td><td>状态</td><td>分子量</td><td>熔点/C</td><td>羟基含量/%</td></tr><tr><td>新戊二醇</td><td>NPG</td><td>团</td><td>104.2</td><td>124~126</td><td>≥30.0</td></tr><tr><td>季戊四醇</td><td>PENT</td><td>固</td><td>136.1</td><td>261~262</td><td>≥48.30</td></tr><tr><td>三羟甲基丙烧</td><td>TMP</td><td>固</td><td>134.1</td><td>57~59</td><td>37.5~38.2</td></tr><tr><td>1,4-环已烷二甲醇</td><td>CHDM</td><td>固</td><td>144.2</td><td>42~44</td><td>≥23.5</td></tr><tr><td>1.6-已二醇</td><td>HDO</td><td>固</td><td>118.2</td><td>41~42</td><td>≥28.5</td></tr><tr><td>羟基叔戊酸新戊二醇酯</td><td>HPHP</td><td>固</td><td>189.2</td><td>49.5~50.5</td><td>≥16.3</td></tr><tr><td>乙基丁基丙二醇</td><td>BEPD</td><td>固</td><td>161. 0</td><td>42~44</td><td>≥21.0</td></tr><tr><td>2.2,4-三甲基-1，3-戊二醇</td><td>TMPD</td><td>固</td><td>146.2</td><td>46~55</td><td>≥23.0</td></tr><tr><td>甲基丙二醇</td><td>MPD</td><td>液</td><td>90.2</td><td>-91</td><td>≥37.5</td></tr></table></body></html>  \n\n设计聚酯树脂配方时，若要满足性能的要求，应综合考虑树脂柔韧性、硬度、弯曲等性能的平衡，并结合成本因素，一般选用两种或两种以上的多元醇。",
+        "category": " Introduction"
+    },
+    {
+        "id": 246,
+        "chunk": "# 2.多元酸  \n\n多元酸指分子中含有多个与烃基直接相连羧基 $\\big\\cdot\\begin{array}{c}{{0}}\\\\ {{-\\stackrel{1}{\\mathrm{c}}-\\mathrm{o}\\mathrm{\\bf{H}}}}\\end{array}$ 0H）的化合物，根据烃基种类，可分为脂肪族酸（如己二酸)、脂环族酸（如1,4-环己烷二羧酸）和芳香族酸（如间苯二甲酸)，根据烃基是否含不饱和键，可分为饱和羧酸和不饱和羧酸。其化学性质，主要由羧基官能团决定，但烃基的结构特征对多元酸羧基的反应也产生影响，不同的烃基结构，会赋予聚酯树脂不同的性能，因此配方设计时，要选择含适宜的烃基结构多元酸来配合聚酯树脂所要求的性能。  \n\n多元酸的化学反应主要发生在羧基上，合成饱和聚酯树脂主要是利用羧基与多元醇中的羟基进行酯化反应。烃基结构为脂肪族碳链的多元酸（如己二酸）能为涂膜提供韧性；烃基结构为苯环的多元酸（如间苯二甲酸、邻苯二甲酸酐）能为涂膜提供硬度；脂环结构的多元酸（如1,4-环己烷二羧酸）既可取得韧性和硬度平衡，又有良好的耐候性。根据合成树脂所要求的性能，调整好各种多元酸的比例，以取得所要求的树脂性能，最常用的多元酸是己二酸、间苯二甲酸、邻苯二甲酸酐等。常用多元酸的参数见表2-1-75。  \n\n表2-1-75常用多元酸的参数  \n\n\n<html><body><table><tr><td>原料名称</td><td>简称</td><td>状态</td><td>分子量</td><td>相对密度</td><td>熔点/C</td><td>酸值</td></tr><tr><td>己二酸</td><td>AD</td><td>固</td><td>146.15</td><td>1. 360</td><td>153~154</td><td>768</td></tr><tr><td>间苯二甲酸</td><td>IPA</td><td>固</td><td>166.18</td><td>1. 507</td><td>345~347</td><td>676</td></tr><tr><td>对苯二甲酸</td><td>PTA</td><td>固</td><td>166.13</td><td>1.510</td><td>>300℃升华</td><td>676</td></tr><tr><td>偏苯三酸酐</td><td>TMA</td><td>固</td><td>192.13</td><td>1. 680</td><td>165~167</td><td>876</td></tr><tr><td>1,4-环己烷二甲酸</td><td>CHDA</td><td>固</td><td>172.1</td><td>1. 380</td><td>164~167</td><td>652</td></tr><tr><td>邻苯二甲酸酐</td><td>PA</td><td>固</td><td>148. 2</td><td>1. 520</td><td>131</td><td>758</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 247,
+        "chunk": "# 3.溶剂  \n\n用于溶解和稀释树脂，使体系形成稳定的均相，能单独溶解树脂的称为溶剂，不能单独溶解树脂，但能与溶剂配合将树脂稀释成溶液的称为稀释剂。同一物质对不同树脂的溶解性并不相同，因此有时属于溶剂，有时会属于稀释剂。在涂料行业内，习惯上并不严格区分溶剂与稀释剂，而是统称为溶剂。  \n\n聚酯树脂生产中溶剂所起的作用为，一是带水（脱水)，在回流脱水阶段与水共沸，将水带出来；二是溶解与稀释树脂作用。  \n\n聚酯树脂生产中有回流脱水的过程，溶剂与水共沸，然后在分水器内将酯化反应生成的水分去，而溶剂又回流进反应釜，从而达到了将反应水带出反应釜的目的，起到了带水剂（脱水剂）的作用。需要选择与水不溶且沸点合适的溶剂，一般选择沸点比回流温度低 $30\\sim$ $60\\mathsf{C}$ 的溶剂为宜，使用量约为 $5\\%\\sim6\\%$ 投料量，最常用的是二甲苯，若要求树脂中不含苯类溶剂，可采用100#重芳烃溶剂，若要求树脂中不含芳烃类溶剂，可采用脂肪烃的D40溶剂。 人  \n\n反应完成后，要用溶剂稀释，才能过滤包装，溶剂对树脂的溶解性会影响树脂溶液均匀性、黏度和贮存稳定性等，因此选择溶剂要了解溶剂溶解性、挥发性、安全性、价格等参数。为满足各方要求，在生产中采用各类溶剂混合的办法来平衡。合适的溶剂体系应具备：$\\textcircled{1}$ 溶解性； $\\textcircled{2}$ 容易挥发，无不挥发残留物； $\\textcircled{3}$ 低毒性、低闪点； $\\textcircled{4}$ 易与其他溶剂配合。  \n\n溶剂可分为含氧溶剂与不含氧溶剂，含氧溶剂的溶解性好，大部分树脂都能溶解其中，主要有：①醇醚类溶剂，目前常用的醇醚类溶剂有乙二醇醚类和丙二醇醚类；②酯类溶剂，目前采用DBE（三种二元酸二甲酯的混合物）和高碳醇醋酸酯（醋酸己酯、醋酸庚酯等）等居多；③酮类溶剂，一般与其他溶剂混合使用，选择沸点较高的异佛尔酮、环己酮等酮类溶剂； $\\textcircled{4}$ 醇类溶剂，主要与其他溶剂配合使用，有丁醇和异丁醇等。  \n\n不含氧溶剂一般不能单独溶解树脂（属于稀释剂)，需要与含氧溶剂配合使用达到理想的溶解能力，主要有：①重芳烃溶剂，与含氧溶剂配合使用，主要有100\\*重芳烃溶剂（主要成分C）与150重芳烃溶剂（主要成分Co）；②芳烃溶剂，常用的是二甲苯，主要作为回流溶剂使用，也有作为稀释剂用。饱和聚酯生产中常用溶剂的参数见表2-1-76。  \n\n表2-1-76饱和聚酯生产中常用溶剂的参数  \n\n\n<html><body><table><tr><td>名 称</td><td>外观</td><td>密度/（g/cm）</td><td>沸点/℃</td><td>闪点/℃</td><td>挥发速率</td></tr><tr><td>乙二醇丁醚</td><td>无色透明</td><td>0.9015</td><td>170.6</td><td>61.1</td><td>10</td></tr><tr><td>环己酮</td><td>无色透明</td><td>0.947</td><td>155.6</td><td>54</td><td>25</td></tr><tr><td>异氟尔酮</td><td>无色透明</td><td>0.923</td><td>215.2</td><td>96</td><td>3</td></tr><tr><td>醋酸丁酯</td><td>无色透明</td><td>0.8826</td><td>126.3</td><td>33</td><td>100</td></tr><tr><td>DBE(MADE)</td><td>无色透明</td><td>1.085~1.095</td><td>190~226</td><td>100</td><td>3</td></tr><tr><td>正丁醇</td><td>无色透明</td><td>0.8109</td><td>117.7</td><td>35</td><td>45</td></tr><tr><td>醋酸己酶</td><td>无色透明</td><td>0.875</td><td>162~176</td><td>54</td><td>16</td></tr><tr><td>醋酸庚酶</td><td>无色透明</td><td>0.874</td><td>176~200</td><td>66</td><td>，</td></tr><tr><td>二甲苯</td><td>无色透明</td><td>0.860</td><td>137~141</td><td>28</td><td>68</td></tr><tr><td>100*溶剂</td><td>无色透明</td><td>0.865~0.880</td><td>155~185</td><td>44</td><td>19</td></tr><tr><td>150溶剂</td><td>无色透明</td><td>0. 875~0.890</td><td>180 ~210</td><td>63</td><td>4</td></tr><tr><td>D40溶剂</td><td>无色透明</td><td>0.770</td><td>164~192</td><td>43</td><td>12</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 248,
+        "chunk": "# 4.催化剂和抗氧剂  \n\n工业化生产饱和聚酯树脂，需要在一定时间内完成，而不同的多元酸和多元醇其反应活性是不同的，若配方体系中有一些反应活性较低的原料（如对苯二甲酸等)，酯化反应速度将很慢，即达到反应要求的酸值、黏度需要的时间很长，从技术经济角度就很不划算，失去了实际应用的价值，为了缩短反应工时，需要使用催化剂来达到目的。  \n\n一个化学反应由于局外物质的参与而使起反应速率发生变化，这种局外的物质称为催化剂。催化剂与反应物接触，并参与化学反应过程，但反应之后，又退出反应体系，并不参与到反应最终的产物中去。催化剂所以能改变化学反应速率是因为，催化剂的参与改变了化学反应的途径和机理，催化剂可以是一种化合物，也可以是由几种化合物组成的一个体系。  \n\n选择催化剂，主要考虑两个方面的作用。 $\\textcircled{1}$ 加快反应速率：有些原料的反应活性较小，使用催化剂可加快反应速率，将生产工时缩短在合理范围内。 $\\textcircled{2}$ 使反应定向进行：在进行我们所希望的化学反应同时，往往还有副反应发生，反应的进程、产品的质量造成影响，利用催化剂的选择性，引导反应的进行，从而达到控制反应的目的。  \n\n选择的催化剂应符合： $\\textcircled{1}$ 接近中性，对设备无腐蚀作用； $\\textcircled{2}$ 催化剂不参与到反应产物中，但残留在体系之中，要考虑其与聚酯树脂相容性，不能影响最终产品质量； $\\textcircled{3}$ 能明显缩短酯化反应时间，但要在可控的范围内； $\\textcircled{4}$ 选择性要好，能使反应向酯化反应方向进行，减少多元醇间的脱水及氧化等副反应； $\\textcircled{5}$ 反应生成水不会使其失效； $\\textcircled{6}$ 选定某种催化剂后，一般不宜轻易更换，不同企业生产的同一类型催化剂会有一些差异，没有通过试验，不可直接  \n\n替代，以免造成生产控制的困难。  \n\n目前国内外酯化反应催化剂采用的大多数是有机锡化合物。一般采用的是丁基氧化锡或丁基氧化锡的衍生物，是一类抗水解、加入量少、催化活性高的酯化反应催化剂。目前国内常用有以下几种。  \n\n(1）二丁基二月桂酸锡浅黄色或无色油状液体，低温成白色结晶体，溶于甲苯、乙醇、丙酮等有机溶剂，不溶于水，锡含量 $17\\%\\sim19\\%$ ，一般使用量为反应物的 $0.20\\%\\sim0.25\\%$ 西  \n\n(2）单丁基氧化锡白色粉末，不溶于水和大部分有机溶剂，单溶于强碱和矿物酸中，锡含量 $356\\%$ ，一般使用量为反应物的 $0.05\\%\\sim0.10\\%$ 。  \n\n目前的市场价格，单丁基氧化锡约为二丁基二月桂酸锡一倍。单丁基氧化锡在使用量为二丁基二月桂酸锡 $_{1/3\\sim1/2}$ 的情况下，其酯化反应时间可比使用二丁基二月桂酸锡缩短 $1/4{\\sim}1/3$ 。有机锡有毒，使用需注意，其中：丁基二月桂酸酯毒性稍低。  \n\n生产过程中，可以根据聚酯树脂的生产状况，选择合适催化剂，并确定加入量，一般情况下，以选择单丁基氧化锡为主。  \n\n我们通常指的催化剂是加快反应速率的物质，但实际上有减缓反应速率的催化剂。生产、贮存和使用过程中，由于温度的变化、与光和空气接触，可能导致树脂的色泽变深、贮存稳定性下降、结构和性能上发生变化等，为延缓这一过程，使用抗氧剂是比较常见的。抗氧剂是一类能抑制或减缓高分子材料氧化反应速率的物质，是减缓氧化反应的催化剂。我们合成树脂行业习惯上将这一类减缓反应速率物质单列，并称之为抗氧剂。  \n\n抗氧剂是一种可降低氧化速率，进而减缓聚合物老化的化学助剂，通常只要加人微小的抗氧剂就非常有效。树脂合成中引入催化剂主要起： $\\textcircled{1}$ 减缓氧化反应速率，可达到降低树脂色泽的目的； $\\textcircled{2}$ 提高树脂贮存稳定性，实际上也提高了涂料的稳定性。  \n\n目前饱和聚酯树脂使用的抗氧剂类型如下。  \n\n(1）酸性抗氧剂主要有硼酸、亚磷酸、次磷酸等，以次磷酸的效果要好些。次磷酸抗氧效果明显，价格相对低廉，但次磷酸酸性较强，要考虑对设备材质的抗腐蚀性。  \n\n(2）亚磷酸酯类常用的有亚磷酸三苯酯、亚磷酸三（2，4-二叔丁苯基）酯（168）、三壬苯基亚磷酸酯（TNPP）等，具有分解过氧化物产生结构稳定物质的作用，有抗氧效果。  \n\n从实际生产情况看，将亚磷酸酯类抗氧剂、酸性抗氧剂单独或复配使用，效果理想。  \n选择聚酯树脂抗氧剂要注意以下几点。  \n\n$\\Phi$ 使用抗氧剂后的减色效果上，小试和车间生产会有差异，需要仔细确认。  \n\n$\\textcircled{2}$ 抗氧剂最后会残留在体系之中，因此需要考虑与聚酯树脂相容性，即不能影响最终树脂性能。如生产389-9大豆油醇酸树脂，若加入次磷酸，树脂色泽可≤4（Fe-Co），但会影响磁漆的干性；生产344-2大豆油醇酸树脂，若加入次磷酸，树脂色泽可 $\\leqslant4$ (Fe-Co)，但会对树脂的压滤造成影响。  \n\n$\\textcircled{3}$ 若同时使用催化剂与抗氧剂，要考虑催化剂与抗氧剂的性能是否相互抵触，如单丁基氧化锡和次磷酸若同时使用时，会影响聚酯树脂的透明度，导致涂膜光泽下降。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 249,
+        "chunk": "# 三、聚酯树脂合成的基本化学反应  \n\n聚酯树脂通常由二元醇、三元醇和二元酸、三元酸等混合物通过缩聚反应制得，一般是低分子量、无定形、含有支链可交联的聚合物。多元醇过量得到端羟基的聚酯树脂，可以用氨基树脂或多异氰酸酯进行交联。多元酸过量得到端羧酸基的聚酯树脂，可以用氨基树脂或环氧化合物进行交联，我们着重讨论端羟基的聚酯树脂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 250,
+        "chunk": "# 1.酯化反应  \n\n能够形成酯基的有机合成反应称为酯化反应。酯化反应通常指醇或酚和含氧酸类作用生成酯和水的过程，也就是在醇或酚羟基的氧原子上引人酰基的过程，亦可称为O酰化反应。酯化的方法很多，其化学反应通式为：  \n\n式（2-1-1）中RCOZ为酰化剂，可以根据实际需要选用羧酸、羧酸酐、酰氯等作为酰化剂。常用酰化剂活性顺序：酰氯 $>$ 酸酐 $>$ 酰胺 $>$ 酯 $>$ 羧酸。羟基活性顺序：伯羟基>仲羟基>叔羟基。聚酯树脂生产中，需要使用三官能团多元醇时，一般采用三羟甲基丙烷而不用甘油，其原因在于保证所有羟基都是伯羟基，活性一致，而且活性比较高。酰化剂及其反应见表2-1-77。非羟基化合物酯化反应见表2-1-78。  \n\n表2-1-77酰化剂及其反应  \n\n\n<html><body><table><tr><td>酰化剂</td><td>化学反应</td><td>酰化剂</td><td>化学 反应</td></tr><tr><td>羧酸</td><td>R'OH+RCOOH →RCOOR'+HO</td><td></td><td>R'OH+RCN+ HO- →RCOOR'+ NH</td></tr><tr><td>羧酸酐</td><td>R'OH+(RCO)O →RCOOR'+RCOOH</td><td>酰胺</td><td>R'OH+RCONHz →RCOOR'+NH</td></tr><tr><td>酰氧</td><td>R'OH+ RCOCI → RCOOR’+ HCI</td><td>烯酮</td><td>R'OH+CH = CO- +CHCOO R'</td></tr><tr><td>酯</td><td>R'OH+RCOOR\" →RCOOR'+HOR\"</td><td>丽</td><td>R'OH+ RCOCCl →RCOOR'+CHC</td></tr></table></body></html>  \n\n表2-1-78非羟基化合物酯化反应  \n\n\n<html><body><table><tr><td>主要试剂</td><td>化 学 反 应</td></tr><tr><td>炔、酸</td><td>CH=CH+ RCOOH- →RCOOCH=CH</td></tr><tr><td>醚、一氧化碳</td><td>CHO CH + CO—→CHCOOCH</td></tr><tr><td>醛、丙二酸单酯</td><td>RCHO+ HOOCCHCOOR'-—→ RCH=CHCOOR'</td></tr><tr><td>酯、酸</td><td>R\"COOR' + RCOOH—→ RCOOR'+ R\"COOH</td></tr><tr><td>酯、酯</td><td>R\"COOR'+RCOOR\"→RCOOR'+RCOOR\"\"</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 251,
+        "chunk": "# 2.缩聚与逐步聚合  \n\n通过酯化反应，利用各个单体（简单单元、小分子试剂）上固有的多个官能团（例如羟基和羧基）进行反应，连接成高分子聚合物（聚酯树脂)。由于类似的聚合反应与小分子缩合反应相同，称为缩合聚合。缩聚反应的研究表明：反应体系中分子是逐步进行聚合的，即每一步反应的速率和活化能大致相同。所以，根据反应动力学，大多数缩聚反应以及合成聚酯的反应都属于逐步聚合，可以利用逐步聚合所揭示的机理特征和规律性，指导如何控制聚酯树脂合成的聚合速率、分子量等重要指标。",
+        "category": " Introduction"
+    },
+    {
+        "id": 252,
+        "chunk": "# 3.官能团等活性概念  \n\n在逐步聚合反应早期，大部分单体很快聚合成二、三、四聚体等低聚物，短期内转化率就很高。低聚物继续相互反应，分子量缓慢增加，转化率很高 $(>98\\%)$ 时，分子量（聚合度）才达到较高的数值，如图2-1-10所示。  \n\n在逐步聚合的全过程中，体系由单体和分子量递增的一系列中间产物所组成，中间产物任何两分子间都能反应。所以使用官能团的反应程度（p）来描述反应深度。  \n\n![](images/0b7957ae078a61f415f4990ca93d7da7bbb52c8a25a15b6a4cc02cd8b50641f0.jpg)  \n图2-1-10聚合度与反应程度的关系  \n\n设： $t_{0}$ 时体系中的官能团总数为 $N_{0}$ . $\\mathbf{\\chi}_{t}$ 时体系中的官能团总数为 $N$ n则： $\\scriptstyle{p=}$ 已反应的官能团数/起始官能团数 $=(N_{0}-N)/N_{0}=1-N/N_{0}$  \n\n当二元醇和二元酸进行聚合反应时，由于产物聚酯也是两个官能团，所以平均每个大分子中的单体数 $x_{*}$ （定义为聚合度）与 $\\boldsymbol{\\mathscr{p}}$ （反应程度）的关系为：  \n\n式（2-1-14）与图2-1-10是一致的。  \n\n使用官能团的反应程度（）来描述反应的深度，就会考虑到官能团的活性与分子量的关系。目前的研究水平以为官能团是等活性的，其理由如下。  \n\n表2-1-79羧酸系列与乙醇的酯化速率常数  \n\n\n<html><body><table><tr><td></td><td>H(CH2)xCO0</td><td>(CH)(COOH)</td><td></td><td>H(CH).CO0H</td><td>(CH)(CO0H)</td></tr><tr><td>1</td><td>22.1</td><td></td><td>8</td><td>7.5</td><td></td></tr><tr><td>2</td><td>15.3</td><td>6.0</td><td>9</td><td>7.4</td><td></td></tr><tr><td>3</td><td>7.5</td><td>8.7</td><td>11</td><td>7.6</td><td></td></tr><tr><td>4</td><td>7.5</td><td>8.4</td><td>13</td><td>7.5</td><td></td></tr><tr><td>5</td><td>7.4</td><td>7.8</td><td>15</td><td>7.7</td><td></td></tr><tr><td>6</td><td></td><td>7.3</td><td>17</td><td>7.7</td><td></td></tr></table></body></html>  \n\n$\\Phi$ 用一元酸系列和乙醇的酯化研究表明（表2-1-79）， $\\scriptstyle n=1\\sim3$ 时，速率常数确实在迅速降低。但诱导效应只能沿碳链传递 $_{1\\sim2}$ 个原子，对羧基的活化作用也只限于 $n{=}1\\sim$ 2。 $\\scriptstyle n=3\\sim17$ 时，速率常数趋向定值。二元酸系列与乙醇的酯化情况也相似，并与一元酸的酯化速率常数相近。  \n\n$\\textcircled{2}$ 体系黏度愈大，则分子链的移动愈困难，但端基活性并不取决于整个大分子质心的平移，而与端基链段的活动有关。大分子链构象（空间形态）改变，链段活动以及端基相遇的速率要比质心平移速率高得多，而且两链段一旦靠近，适当的黏度反而不利于分开，有利于持续碰撞，因此产生了等活性现象。  \n\n当然，官能团等活性概念还有待于进一步深化。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 253,
+        "chunk": "# 4.反应速率（时间和温度）  \n\n以羧酸和醇的聚酯化反应为例，属于酸催化反应，羧酸先质子化，然后质子化种与醇反应成酯，应用等活性概念，反应式可简化为：  \n\n生产实践中，在减压条件下，及时排除副产物水，使反应不可逆。而且外加强酸（常数）催化，反应向聚酯化方向移动，形成聚酯树脂。根据质量作用定律，得：  \n\n$$\n\\scriptstyle{\\frac{-\\mathsf{d}[\\mathrm{COOH}]}{\\mathsf{d}t}}=k[\\mathrm{COOH}][\\mathrm{OH}]\n$$  \n\n若两种官能团浓度相等，式（2-1-15）可简单地写成：  \n\n$$\n-\\mathrm{d}c/\\mathrm{d}t=k c^{2}\n$$  \n\n式（2-1-16）积分，得：  \n\n$$\n1/c-1/c_{0}=k t\n$$  \n\n式（2-1-17）中 $c_{0}$ 为一种官能团的起始浓度； $\\boldsymbol{\\mathscr{c}}$ 表述了 $\\mathbf{\\Psi}_{t}$ 时体系中反应物的浓度。即反应速率方程。  \n\n聚合反应从热力学角度衡量，总是放热反应，但聚酯反应聚合热不大（10～25kJ/mol)，而活化能较大（40～100kJ/mol)，反应需要在较高温度下进行，低的聚合热难以弥补高温体系的热损失，另外，排除缩合出来的小分子也引起热量损失，所以生产是在不断供热的条件下进行的。  \n\n温度影响的定量描述，测取不同温度下的k值确定，或者使用阿累纽斯方程讨论。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 254,
+        "chunk": "# 5.分子量  \n\n聚酯树脂大量用作涂料，材料的基本要求是强度，聚合物强度随分子量的变化如图  \n\n2-1-11。A点是初具强度的最低分子量，A点以上的强度则随分子量而迅速增加，到临界点B以后，强度的增加逐渐减慢； $c$ 点以后，强度不再显著增加，过高分子量反而会影响涂料的工艺性能。在平均分子量相同的情况下，较宽的分子量分布，会有较好的工艺性能，而强度可能下降。合成影响分子量的因素主要有平衡常数、反应程度、官能团摩尔比。  \n\n（1）平衡常数聚酯合成的平衡常数很小（ $\\scriptstyle K=$ 4)，对于线型产物，必须要在高真空 $\\mathrm{:<}70\\mathrm{{Pa})}$ ，充分脱去残留水分 $\\left(<4\\times10^{-4}\\mathrm{mol/L}\\right)$ 的条件下，才能获得有用的产品。  \n\n![](images/29eed34fa060cd44815282a8ea794beb9b757476518cf7bee0a15635d0106d1d.jpg)  \n图2-1-11聚合物强度-分子量关系  \n\n(2）反应程度反应程度对分子量影响由式（3）定量表述。由于 $N_{0}/N{=}c_{0}/c$ ，将(2-1-14）代人式(2-1-17），得：  \n\n$$\nX_{n}=k c_{0}t+1\n$$  \n\n式（2-1-18）说明聚酯分子量（聚合度）在两种官能团等摩尔数的条件下，可以随着反应时间而不断增加。  \n\n（3）官能团的摩尔比由于原料的含量，计量和投料误差，以及脱羧等副反应的发生，生产实践总在两种官能团非等摩尔数的条件下操作进行。  \n\n设 ${N_{s}}$ ， $N_{\\mathfrak{b}}$ 分别为两种官能团（a和b）的数量，规定官能团的摩尔比 $r{=}N_{\\bullet}/N_{\\ b}{\\leqslant}1$ 即b官能团过量。如果a的反应程度为 $\\scriptstyle{\\pmb{\\mathscr{p}}}$ ，因为（a和b）成对反应，所以（a和b）的官能团残留总数为 $\\mathrm{(}N_{*}\\mathrm{+}N_{\\mathrm{b}}\\mathrm{-}2p N_{*})$ 。在单体和每个大分子都是2个官能度的情况下（若有3个官能度，则大分子端基不断增加直至凝胶)，可得：  \n\n$$\nX_{n}=\\frac{\\mathrm{a}4+3\\mathrm{b}}{\\mathrm{a}\\times4+7\\cdot1\\cdot5\\times4\\times4}=\\frac{N_{0}}{N}=\\frac{N_{*}+N_{\\mathrm{b}}}{N_{\\mathrm{a}}+N_{\\mathrm{b}}-2\\phi N_{\\mathrm{a}}}=\\frac{1+r}{1+r-2r\\phi}\n$$  \n\n当 $r{=}1$ 时，式(2-1-19）还原为式(2-1-20)。当 $r{<}1$ ，而反应完全时（ $\\scriptstyle{p=1}.$ ，则式(2-1-19）简化为  \n\n$$\nX_{n}{=}\\frac{1{+}r}{1-r}\n$$  \n\n由上式，可以方便地计算出一定摩尔比条件下的分子量上限。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 255,
+        "chunk": "# 6.体型聚合物强度与凝胶点  \n\n聚合物在外力作用下的破坏，往往由克服分子之间作用力引起，即分子之间发生滑移。如果分子之间具有键合，强度将大大提高。分子之间具有键合的聚合物是三维网状结构的，称为体型聚合物。体型聚合物是不溶不熔的热固性材料，为了方便成型加工，从单体到体型聚合物制品的整个生产过程，可以分为合成和成型两个阶段，树脂或预聚物合成既要保证一定的分子量，又必须严格防止因凝胶而影响后续成型加工。  \n\n(1）线型树脂用线型高分子聚合方法合成，然后在成型时加人过氧化物引发剂或者辐射产生游离基合成体型聚合物。线型树脂结构中，有叔碳结构的比较容易产生游离基。  \n\n(2）微凝胶一般使用三官能团以上的多种单体逐步聚合而成，使用乳液聚合或者反相乳液聚合的方法，控制微相颗粒尺寸，合成微凝胶。微凝胶可以提高聚合物强度等性能。微凝胶的研究引起很多关注，其理论和实践结果，将会促进聚酯树脂及其产品的进一步发展。  \n\n(3）结构预聚许多体型聚合物先合成基团结构比较清楚的进行了分子设计的预聚物，具有特定的端基或侧基，结构预聚物本身一般不能交联固化，成型时，须另外加入催化剂或其他反应性物质。  \n\n（4）无规预聚多官能度（若 ${>}2$ 个官能度）体系进行缩聚时，先形成支化，进一步反应，则交联成体型聚合物。合成中控制其反应程度在支链型预聚物阶段，可溶可塑化。体系中含有尚可反应的基团，预聚物基团是无规则分布的。可以在成型阶段进一步受热反应，交联固化成体型聚合物。  \n\n多官能度单体聚合到某一反应程度，开始交联，黏度暴增，体系中气泡很难上升，出现了不溶不熔的凝胶。体系中出现凝胶时的临界反应程度，定义为凝胶点 $(\\phi_{\\mathrm{{c}}})$ 。凝胶相当于许多线型大分子交联成一整体，各个线型大分子不能再发生相对位移。凝胶点的预测和控制很重要。预聚合成时，如超过凝胶点，产品将固化在聚合釜内报废。  \n\n凝胶点预测主要使用著名的Carothers方程，试推导如下。  \n\n$\\textcircled{1}$ 平均官能度（f)  \n\n表2-1-80是两个聚酯配方及其平均官能度计算举例。其中，因为羟基和羧基的反应是一对一进行的，多余官能团无法参加反应，所以，参与反应的官能团数按照羟基数或者羧基数中比较小的官能团数两倍计算。  \n\n表2-1-80聚酯配方及其平均官能度计算  \n\n\n<html><body><table><tr><td rowspan=\"2\">项 目</td><td colspan=\"2\">配方1</td><td colspan=\"2\">配方2</td></tr><tr><td>单体分子数</td><td>官能团数</td><td>单体分子数</td><td>官能团数</td></tr><tr><td>三羟甲基丙烷</td><td></td><td></td><td>1.9</td><td>5.7</td></tr><tr><td>新戊二醇</td><td>1.5</td><td>3.0</td><td>3.6</td><td>7.2</td></tr><tr><td>间苯二甲酸</td><td>0.9</td><td>1.8</td><td>3.0</td><td>6.0</td></tr><tr><td>己二酸</td><td>0.3</td><td>0.6</td><td>2.0</td><td>4.0</td></tr><tr><td>偏苯三酸酐</td><td>0.3</td><td>0.9</td><td></td><td></td></tr><tr><td>羟基数</td><td colspan=\"2\">3.0</td><td colspan=\"2\">5.7+7.2</td></tr><tr><td>酸基数</td><td colspan=\"2\">1. 8 +0.6+ 0. 9</td><td colspan=\"2\">6.0+4.0</td></tr><tr><td>总单体数</td><td colspan=\"2\">1.5+0.9+0.3+0.3</td><td colspan=\"2\">1.9+3.6+3.0+2.0</td></tr><tr><td>参与反应的官能团数</td><td colspan=\"2\">2X3.0</td><td colspan=\"2\">2X10.0</td></tr><tr><td>平均官能度</td><td colspan=\"2\">f=2×3. 0/(1.5+0. 9+0.3+0. 3)</td><td colspan=\"2\">f=2×10. 0/(1.9+3. 6+3. 0+2. 0)</td></tr></table></body></html>\n\n$\\textcircled{2}$ Carothers方程设体系中起始分子数为 $\\scriptstyle A_{0}$ ，则起始官能团数为 $A_{0}f_{\\ast}$ 令 $\\mathbf{\\chi}_{t}$ 时体系中  \n\n分子数为A，则凝胶点以前反应的官能团数为2X（Ao一A)。系数2代表体系中每减少一个分子，必有两个官能团反应（成键)。则：  \n\n$$\n\\hat{\\boldsymbol{p}}=\\frac{\\Xi\\vert\\Xi\\vert\\vert\\ddot{\\mathcal{U}}\\vert\\vert\\hat{\\mathcal{U}}\\vert\\hat{\\mathcal{G}}\\vert\\vert\\hat{\\mathcal{G}}\\vert\\vert\\ddot{\\mathcal{H}}\\vert}{\\vert\\widehat{\\Xi}\\vert\\vert\\hat{\\mathcal{G}}\\vert\\vert\\ddot{\\Xi}\\vert\\vert\\hat{\\mathcal{G}}\\vert\\vert\\hat{\\mathcal{H}}\\vert}=2\\frac{A_{0}-A}{A_{0}f}\n$$  \n\n因为聚合度 $\\scriptstyle{X_{n}=}$ 单体总数/大分子个数 ${=}A_{0}/A$ ，代入上式，则得  \n\n$$\n\\scriptstyle{p=\\left({\\frac{2}{f}}\\right)\\left(1-{\\frac{1}{X_{n}}}\\right)}\n$$  \n\n发生凝胶点时，考虑 $\\scriptstyle{X_{\\#}}$ 趋向于无穷大，则凝胶时的临界反应程度 $\\scriptstyle{\\mathtt{p}}_{\\mathtt{e}}$ 为  \n\n$$\n\\scriptstyle\\mathtt{\\mathtt{p}_{\\mathtt{e}}=}{\\frac{2}{f}}\n$$  \n\n由于式（2-1-22）中的 $\\scriptstyle{X_{\\mathfrak{n}}}$ 都是有限值，并非无穷大。所以由式（2-1-23）计算所得到的临界反应程度往往偏大。如果使用实验测定具体体系凝胶时的 $\\scriptstyle{X_{n}}$ 参数校正，则式（2-1-22）计算结果与真实值相近。不仅如此，式（2-1-23）非常简洁，具有重要的理论指导意义，例如，当 $f{\\leqslant}2$ 时， $\\rho_{\\mathrm{e}}\\geqslant100\\%$ ，即体系不会发生凝胶。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 256,
+        "chunk": "# 7.聚合实施方法  \n\n逐步聚合重点要考虑官能团摩尔比和反应程度问题，以保证聚合达到一定的分子量。  \n\n(1）熔融聚合反应在单体和聚合物熔点温度以上进行。经济，产物纯净。主要问题是反应温度比较高。要求产品有较高的热稳定性。脱羧等副反应容易造成非等摩尔比，影响分子量。随着反应体系中聚合物分子量的提高，黏度增加。缩合小分子的脱除可能需要抽真空。  \n\n(2）溶液聚合行业内我们习惯称之为回流聚合，反应在适当的溶剂中进行，反应平稳而副反应少。缩合小分子可以和溶剂共沸脱除。由于使用溶剂，体系中反应物浓度下降。溶剂会引起污染和成本增加。  \n\n(3）界面聚合反应在两种溶剂的界面进行。要求单体有极高的反应活性。特点是反应对官能团摩尔比没有要求。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 257,
+        "chunk": "# 8.立体因子  \n\n聚酯容易合成，单体也很丰富，因而性能具有很大的可调性，然而酯基不耐水。聚合时，二元醇中以新戊二醇较为理想，与乙二醇比较，可以大大改善树脂的耐水性能，它们的结构示意如图2-1-12。  \n\n![](images/570853610d89fe100d57dd4d1a0ad9d35493a34af55217233c70b29dd0e2dc08.jpg)  \n图2-1-12新戊二醇聚酯和乙二醇聚酯的结构  \n\n将其结构中羰基上的氧作为起点，逐次将原子标上位数，数出6位和7位的原子数，然后按式（2-1-24）计算立体因子：  \n\n新戊二醇6位和7位的原子数分别为3个和9个，立体因子为21；而乙二醇的聚酯只有  \n\n3个6位原子和1个7位原子，立体因子为13。根据6，7位经验规律，立体因子值愈高，水解稳定性愈好。因此，新戊二醇聚酯的耐水性远超过乙二醇。同理，如果使用支化的二元醇，则水解稳定性将大大提高。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 258,
+        "chunk": "# 四、聚酯树脂的生产工艺",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 259,
+        "chunk": "# 1.生产工艺和工艺过程  \n\n聚酯树脂合成常用的新戊二醇、甲基丙二醇等多元醇，升华温度较低，若反应起始时采取熔融酯化的工艺，没有沸腾的溶剂，直冷凝器中的气相温度可通过控制冷却水来控制，可减少多元醇的升华损失，避免不必要的原料消耗。若反应起始就采用将回流溶剂与多元醇、多元酸同时投入的工艺，在回流反应时，溶剂处于沸腾的状态，气相温度较高，且受沸腾溶剂的影响，难以下降，多元醇很容易升华而损耗，影响了与多元酸反应状况，难以得到清澈透明的树脂。要解决这个问题，只有增加多元醇的投料量才有可能，这势必增加聚酯树脂的原料成本，从技术经济的角度看，极不合理。  \n\n多元醇分子链上的羟基与多元酸分子链上的羧基，需要到达一定温度，才会发生酯化反应。不同烃基结构的多元酸与多元醇反应活性不同，发生反应的温度也不同，饱和聚酯树脂合成中常用的多元酸为对苯二甲酸和间苯二甲酸等，与多元醇的起始反应温度都高于苯酐。刚开始酯化反应时，有大量的反应水生成，再加上回流溶剂的存在，会降低整个体系的温度，反应温度很可能达不到羟基与羧基发生反应所需的适宜温度，反应无法顺利进行，若采用先不加溶剂熔融反应工艺，反应温度高，这个问题就不存在了。因此目前聚酯树脂合成一般采用先熔融反应、再加溶剂回流反应的工艺。  \n\n合成聚酯树脂所采用的各种结构不同的多元酸，与多于醇反应的竞聚率不同，因此与多元醇反应时，竞聚率高的多元酸与多元醇反应快，而竞聚率低的多元酸与多元醇反应慢，难以顺利的接到聚酯分子链上。当然多元酸的反应活性与多元酸所占比例也有关系。  \n\n为得到均衡的树脂分子链，保证树脂有优异的性能，根据树脂所采用的多元酸的情况，为保证竞聚率低的多元酸与多元醇的充分反应，一般可采用将竞聚率高的多元酸后投料（二次投入）的方式，这样刚开始反应时，没有竞聚率高的多元酸参与竞争，可保证竞聚率低的多元酸与多元醇反应顺利进行，反应到达一定程度后再加入反应性强的多元酸，可得到分子链结构分布适宜的饱和聚酯树脂。  \n\n根据配方中多元酸反应活性的差异情况，多元酸可采用一次投料或二次投料，使用对苯二甲酸的配方，多元酸大多采用二次投料。  \n\n（1）熔融（聚合）反应熔融反应是指无溶剂状态下进行酯化反应与缩聚反应，生产饱和聚酯树脂时，起始投料时，回流溶剂并不投入，多元醇、多样化升温熔化后成为均相，体系在无溶剂的熔融状态下反应，等熔融反应进行到一定阶段后，聚酯树脂达到一定分子量后，再加人回流溶剂进行回流反应阶段，直至反应达到要求。  \n\n(2）回流（聚合）反应回流反应是指在有回流溶剂（最常用的是二甲苯）存在的情况下，进行酯化反应与缩聚反应。熔融反应达到一定分子量后，加人回流溶剂，反应进入回流反应阶段。由于树脂合成的反应为可逆反应，若采用全部熔融反应的工艺，没有回流溶剂沸腾的帮助，反应生成的水从反应物中分离比较困难，对于反应的进程不利，会影响反应产物的品质、延长聚酯树脂达到规定要求的时间。  \n\n加入回流溶剂后，由于溶剂的沸腾，整个反应体系——反应釜、冷凝器、分水器等形成一个循环，反应生成的水通过回流溶剂的循环，从反应系统中分离出来，使可逆反应可以顺利的向正反应方向移动，有利于反应进程。由于溶剂的存在，反应物流动性好，容易成为均匀的液相，反应温度及聚酯树脂的黏度容易控制，反应进展顺利，树脂质量可以得到保证。  \n\n(3）生产工艺过程饱和聚酯树脂的生产由几个相对独立的单元操作所组成，一般可分为以下几个单元操作，投料、反应、中控、稀释、压滤。  \n\n$\\textcircled{1}$ 投料开始生产的第一步，这个步骤最重要是：投料准确；按工艺要求的顺序投料。同样的配方不同的投料次序会对产品造成影响，多元醇和多元酸熔点各异、熔化快慢不同，最合适的次序是将容易熔化的多元醇分为两份分别投在反应釜底部和上部，多元酸投在物料的中间，升温时多元醇与多元酸可尽快融合为均相，使反应顺利进行。  \n\n$\\textcircled{2}$ 反应树脂合成牵涉到的化学反应是酯化反应和缩聚反应，反应工艺、反应温度、催化剂的类型都对反应进程有影响。从反应控制上看，要及时将反应水从反应釜中脱出，使反应朝我们控制的方向进行，避免副反应的发生。  \n\n$\\textcircled{3}$ 中控通过取样后的检验来衡量反应是否达到了规定的要求，这一过程要求取样后用来稀释的溶剂，与生产时对稀溶剂成分完全相同，以保证测试准确。样品溶解时，溶剂会挥发，溶解后应复称，减少的分量用稀释溶剂补足，可提高测试的准确性。  \n\n$\\textcircled{4}$ 稀释反应达到终点后，放料到对稀釜中稀释，另外，反应釜中应加人部分强溶剂洗锅，将黏附在反应釜内壁的树脂洗下，这一步骤的要求是揽拌均匀。  \n\n$\\textcircled{5}$ 压滤原料引入与反应产生的杂质都留在树脂体系中，但聚酯树脂加工的涂料都有细度要求，因此要用过滤的方法将树脂中的杂质滤掉，保证树脂产品清澈透明。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 260,
+        "chunk": "# 2.反应控制  \n\n饱和聚酯树脂的生产过程有多个单元操作组成，每个单元操作承担的功能不同，对产品质量影响程度也不同，如何按工艺要求控制好反应，将直接影响到树脂的品质与性能。如果我们将反应这一单元操作继续细分，可分为熔融反应和回流反应两个阶段。  \n\n针对两个不同的反应阶段，各有工艺操作目标，工业生产会提出不同的控制要求，以达到生产出符合应用性能要求的树脂。  \n\n熔融酯化：多元醇、多元酸、催化剂投入反应釜后，在无溶剂状态下，逐步升温熔化，变频搅拌先慢速启动，视熔化情况加速，完全融化形成统一均相后，继续升温，进入熔融反应阶段。这是整个工艺最关键的阶段，有几个关键工序要注意。  \n\n(1）气相温度的控制在熔融反应的温度下，总有些易升华的原料会升华损耗，若升华量的加大，气相温度会升得很快，显然，控制好气相温度是减少升华的必然措施，但气相温度与反应釜釜内温度是有关联的，气相温度控制的越低，会导致釜内温度无法升高，从而对反应造成影响。考虑到起始反应时，原料浓度高，升华倾向大，反应剧烈，开始生成的反应水从反应釜内脱出，也会对升华有帮助，因此起始反应时的气相温度应控制的低一些。而随着反应进行，树脂分子逐渐形成，原料浓度逐渐降低，升华倾向逐渐减少，反应水也逐渐减少，此时，气相温度可控制的高些。如果将熔融反应气相温度的控制分为三段，建议按如下温度分别控制， $99\\sim102\\Upsilon$ ， $102{\\sim}105\\Upsilon$ ， $105{\\sim}108\\Upsilon$  \n\n（2）釜内熔融反应温度的控制工艺文件会设置一个熔融反应允许的最高温度，反应温度过低会直接影响反应进程，温度过高会使反应速度过快，导致气相温度失控，这个温度要通过小试验证，平衡各方因素，确认合适熔融温度。一般将最高允许温度设置为比适宜的熔融反应温度高 $^{\\mathfrak{s c}}$ ，实际生产时，随着反应水脱出，釜内温度会逐渐上升，整个釜内温度的变化控制趋势与气相温度的控制趋势是同步的。  \n\n(3）情性气体（ $\\mathrm{CO}_{2}$ 或 $\\mathbf{N}_{2}$ ）的保护反应釜与大气通过平衡管（放空管）连通，维持压力平衡，保证熔融反应在常压下进行。熔融反应开始前，已有较高的温度，反应物与大气直接接触，易产生氧化聚合反应，造成物料色泽变深。为避免这种情况，可在投料完毕后，升温同时通入情性气体，利用惰性气体来隔绝反应物与空气的接触，防止氧化的发生，直到熔融酯化发生，反应水生成，由水蒸气来起隔绝空气作用时，才停止通入情性气体。为保证隔绝空气效果，通入情性气体前，反应釜先抽真空，以尽量排除空气，然后再通入情性气体。  \n\n回流酯化：如果全部采用熔融反应的工艺，随着酯化反应进行，聚酯树脂分子量逐渐上升，体系的黏度也日益上涨，反应生成水要从体系中脱出，也变得愈发困难；而且在无溶剂状态下，随着树脂分子量和黏度上升，液相反应的进行也越来越难，反应的中间控制也难以进行。  \n\n若在熔融反应进行到一定程度后，加人一定量的与水不相溶的溶剂，与水共沸时，较为容易的将酯化反应生成水带出了反应釜，有利于酯化反应的进行；溶剂的存在使中间控制相对容易进行，体系的黏度有一定程度下降，有利于液相反应继续进行。在这个工艺阶段，需要注意以下问题。  \n\n$\\Phi$ 进入回流反应后，随着反应进行，反应生成水被带出反应釜，体系的温度会逐渐上升，温度高低能影响反应速度的快慢，因此要设定最高反应温度。这与回流溶剂的加人量有很大关联，回流溶剂量大，在共沸状态下体系温度受溶剂影响难以升得很高；回流溶剂量小，溶剂的干扰少，在共沸状态下体系温度容易升高。因此要根据反应工时、控制情况、加热状况等来设计好工艺最高控制温度，以利于生产正常进行。  \n\n$\\textcircled{2}$ 树脂的最终成型，离不开中间控制，这关系到树脂生产能否达到规定的要求。在反应后期，取样后，按生产使用的溶剂种类、稀释比例加入溶剂并揽均匀，一般测试黏度和酸值，观测是否达到工艺控制的指标。这一步骤关键的是，取样后的测试一定要准确无误，否则后患无穷。  \n\n![](images/af85a497f345ddad987a70fad574e8a40814b9bdb84e7d0f8aee226b5a53a92a.jpg)  \n图2-1-13聚酯树脂生产设备简图1—反应釜；2—直冷凝器；3-横冷凝器；4—分水器",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 261,
+        "chunk": "# 3.生产设备  \n\n生产饱和聚酯树脂的主要设备有反应釜、稀释釜、压滤机，根据工艺特点，采用单釜间隙式生产工艺。以反应釜为主，配套有直冷凝器、横冷凝器、分水器、压滤机及稀释釜。聚酯树脂生产设备如图2-1-13所示。  \n\n在聚酯树脂反应过程中，有需要加热的工序，也有需要冷却的工序，从工艺控制上说，要求加热与冷却的速度都要快，以减少过程时间，尽快达到工艺控制要求。根据工艺的要求，一般采用间接加热方式，配置高温导热油炉，采用适当的燃料，将导热油加热，依靠循环供热系统强制循环，达到加热反应釜内物料目的。  \n\n反应釜可采用夹套通导热油、内置盘管通冷却水方式，也可采用夹套内进冷却水、内置盘管通导热油的方式。加热和冷却设置方式，对加热和冷却效果有一定影响，聚酯树脂生产过程中，需要冷却的工序有： $\\textcircled{1}$ 反应结束后的中止反应； $\\textcircled{2}$ 熔融反应向回流反应转换时的冷却。无论采用何种方式，都能满足工艺要求。  \n\n主要考虑的是工艺对加热的要求，生产开始时，要尽快将多元醇、多元酸熔化并形成均相，使反应顺利进行。采用夹套加热方式，热量通过反应釜壁传递给釜内的物料外围，再逐渐向内传递；而采用内置盘管方式加热，盘管处于物料中，热量传递要快，物料容易熔化。  \n\n因此生产时采用内置盘管加热、外部夹套或半管冷却的方式更好。若生产一些后阶段黏度上升很快，需要及时冷却来中止反应的聚酯树脂，可考虑采用内置盘管冷却的方式。  \n\n不同聚酯树脂由于分子量、黏度等有较大差距，同样的搅拌很难适应不同工艺状况，若有多个反应釜生产树脂，宜采用不同的搅拌形式，来适应不同的工艺要求。多元醇、多元酸熔化需要过程，为防止开始时过快转速对搅拌造成损坏，搅拌电机应采用变频电机。常用的桨式搅拌器有单层式或双层式，一般采用倾斜安装，可产生一定轴向液流，搅拌效果较好，适应树脂黏度或分子量不很大的品种。若合成高分子量、高黏度的线型聚酯，反应后阶段黏度很大，斜桨式搅拌难以使釜内物料形成均相，产生中控黏度与对稀后黏度的较大偏差，影响生产正常进行。  \n\n为解决高黏度聚酯树脂生产中出现的后阶段物料不均匀状况，采用结合旋桨式搅拌器和框式搅拌器特点的复合搅拌器是很好的方法。由三片花瓣形桨叶组成的旋桨式搅拌器外，加上平置的有一定宽度的框组成，框外沿基本接近反应釜内的浸入式盘管，一般安装在反应釜简身与下封头接口略下一些的水平面上。与常用的旋桨式搅拌不同的是，桨叶采用将轴向液流向上扫的形式安装，比将轴向液流向下扫的安装形式效果要好。  \n\n目前树脂生产企业，液体树脂过滤一般都采用垂直网板式过滤机（行业内一般称为 $\\pmb{\\gamma}$ 过滤机)，为保证过滤效果，避免一些机械杂质对不锈钢丝网造成影响，可在反应釜和过滤机之间安装袋式过滤的装置（内置不锈钢丝网)，分离掉比较大的固体颗粒，以避免损坏过滤机。  \n\n考虑饱和聚酯树脂生产特点和工艺操作要求，聚酯树脂反应釜的直冷凝器，上半部设置成冷凝器，经过分水器的回流溶剂从冷凝器上进入，下半部设置为有一定数量填充料的分馏柱，上半部分流出的冷凝液，流到下半部分放置了填充料的分馏柱内，进行传质和传热，有利于共沸液的分离，加快酯化反应，减少热量消耗，减少升华引起的原料损失，避免因升华造成的冷凝器堵塞。  \n\n在直冷凝器与横冷凝器连接处，应安装监控温度计来显示气相温度、控制升华情况。考虑到有些树脂合成时，分馏柱中的填充料会造成沸腾困难，可在蒸出管的下部开手孔，必要时，可将填充料从手孔处取出。  \n\n冷凝器下的分水器，用于收集冷凝下来的反应水和回流溶剂共沸物，依靠各自密度不同进行分层，上层回流溶剂，经回流管重新进入反应釜，水则从分水器底部排出。一般分水器为立式圆筒状贮罐，顶部采用平顶或椭圆形封头，底部为锥形结构。分水器中部有两个对称圆形视镜，一个放置视镜灯，一个供观察使用，为方便观测，视镜中心部位与回流管低点等高，保持分水器液面高度处于圆形视镜的中间部位。  \n\n分水器进来的水和溶剂共沸物直接落在液面上，可能发生未充分沉淀，即走近路从回流管返回反应釜。回流溶剂中夹带过多的水，会对聚酯树脂的酯化反应造成不良影响，使反应有向逆反应方向进行的倾向。为使溶剂在分水器中有充足的时间沉降分层，且不直落在液面上，可通过一个漏斗将引冷凝液引至液面下一定深度，延长了回流溶剂在分水器内停留时间，有利于水与溶剂分离。分水器的容积以略大于反应釜内酯化反应所能产生的水量为宜。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 262,
+        "chunk": "# 五、饱和聚酯树脂的分类与制备",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 263,
+        "chunk": "# 1.饱和聚酯树脂分类  \n\n饱和聚酯树脂是树脂行业非常重要的一大类产品，在人们的日常工作和生活中应用很广，如纤维用聚酯、薄膜用聚酯、塑料用聚酯等用量都很大。涂料用饱和聚酯树脂仅仅是其中用量较少的一种，常见的涂料用树脂主要有松香树脂、氨基树脂、环氧树脂、醇酸树脂、异氰酸树脂，不饱和聚酯树脂、丙烯酸树脂、酚醛树脂、乙烯类树脂等，还有近年来发展迅速的有机硅树脂和氟树脂。  \n\n涂料用树脂的分类时，饱和聚酯树脂在涂料行业内的研发与应用很少，因此未将饱和聚酯树脂列为一个大类，而从其结构特点及产品的发展应用看，与醇酸树脂有千丝万缕关系，只是不含动植物油脂，因此将其归为特殊的醇酸树脂——无油醇酸树脂。按分子量大小可分为高分子量、中等分子量和小分子量三类，从涂料用饱和聚酯的产品研发和实际应用分析，由树脂的分子结构按以下三类划分是比较适宜的。  \n\n第一类，直链结构的饱和聚酯树脂。若使用直链结构的二元醇与二元酸（如新戊二醇、1,6-己二醇、甲基丙二醇、间苯二甲酸、己二酸等)，可得到直链结构饱和聚酯树脂，如果采用的二元酸和二元醇中不含芳香烃结构，可得到脂肪烃直链结构的饱和聚酯树脂。高分子量直链结构的饱和聚酯树脂柔韧好、附着力好，可用于卷材涂料底漆。  \n\n第二类，网状结构的饱和聚酯树脂。若使用了三官能团或三官能团以上结构多元酸或多元醇（如三羟甲基丙烷、偏苯三酸酐等)，会在支链上发生反应，产生含网状结构的饱和聚酯树脂。中等分子量网状结构的饱和聚酯树脂活性高、综合性能突出，可用于卷材涂料面漆和背面漆。  \n\n第三类，改性饱和聚酯树脂。采用化学反应引入除多元醇、多元酸之外的其他成分，来达到改善和突出某种性能的目的，由此产生改性聚酯树脂。目前应用比较多的是环氧改性、丙烯酸改性、有机硅改性饱和聚酯树脂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 264,
+        "chunk": "# 2.饱和聚酯树脂配方设计  \n\n多元醇与多元酸合成的聚酯树脂并不是纯粹、可用化学结构式准确描述的化合物，而是由各种不同分子量的树脂分子混合而成的高分子聚集物，树脂的数均与重均分子量、分子量分布的宽窄、离散度（重均分子量/数均分子量）、活性基团（羟基、羧基等）的不同，产生了不同应用性能、适应不同需要的树脂。这些参数的变化，与所采用多元醇、多元酸的品种和用量、酯化反应条件和方式、反应的控制等密切相关。如何控制和调整这些因素，是配方设计需要关注的重点。  \n\n如果把配方设计这项工作进一步分解的话，可由以下几个步骤构成： $\\textcircled{1}$ 设计依据； $\\textcircled{2}$ 原料选择； $\\textcircled{3}$ 设计依据； $\\textcircled{4}$ 配方估算； $\\textcircled{5}$ 生产调整。  \n\n(1）设计依据作为涂料中的主要成膜物质，涂料的性能主要由树脂来体现，因此，进行配方设计前，首先根据掌握的各种信息，必须要了解要生产的树脂所应用涂料使用在什么场合；有什么性能要求；涂料生产企业对树脂的成本有何要求，这些都是配方设计的前提，然后才能进行基础配方设计。不同用途的涂料，要求不同性能的树脂来匹配，树脂的分子结构也有差异，采用的原料也有不同。  \n\n要求柔韧好的树脂，树脂的结构应采用直链的分子结构为宜，选用的原料应是长链多元醇、多元酸为主。对硬度要求高的树脂，树脂的结构以体型结构、含刚性基团的为宜，选用容易形成体系结构的多官能团原料（三官能团和三官能团以上）、含苯环的原料来配合。以卷材涂料用聚酯树脂为例：对用于面漆、背面漆、底漆的树脂，要求肯定各不相同的。  \n\n因此，树脂的性能、用途、分子结构、所采用的合成工艺，相互关联并相互影响。聚酯涂料的用途，饱和聚酯所要达到的性能将决定树脂的结构与组成，有什么结构就有什么性能，也决定了最终具有什么用途。上述这些设计开发时需要考虑的问题，就是饱和聚酯树脂配方设计的依据。  \n\n(2）原料选择常用的饱和聚酯树脂是含端羟基官能团的聚酯树脂，通过与异氰酸酯、氨基树脂等树脂交联固化成膜。决定树脂性能的关键因素是所使用的多元醇和多元酸的特性，不同的原料对树脂性能提供不同的贡献，选择原料要从满足涂膜性能要求，选择相应的、能对树脂所要求性能有帮助的原料，一般从官能度、硬度、柔韧性、成本等多方面来考虑选择原料。  \n\n选择原料和确定配方时要了解所用原料的特性和它们的反应机理，才能进行好配方设计，并掌握它们之间反应速率的相异，确定试验工艺。含苯环的原料能为树脂提供硬度；使用三官能团及以上的多元醇或多元酸，有利于形成具有网状结构的聚合物，也具有较高硬度；但快速增长的网状结构，易造成树脂黏度增加过快，甚至引起树脂胶化，因此要适当控制三官能团及以上原料用量。  \n\n配方设计时要考虑： $\\textcircled{1}$ 二元醇升华损耗； $\\textcircled{2}$ 反应完成后，过量羟基的封端可控制树脂分子链的增长，为交联固化保留了活性基团。因此必须有适当的醇超量。常见的多元醇和多元醇见表2-1-81。  \n\n表2-1-81常见的多元醇和多元酸  \n\n\n<html><body><table><tr><td>类别</td><td>名 称</td><td>官能度</td><td>当量</td><td>特点</td></tr><tr><td rowspan=\"11\">多 元 醇</td><td>新戊二醇</td><td>2</td><td>52</td><td>硬度</td></tr><tr><td>甲基丙二醇</td><td>2</td><td>45</td><td>溶解性</td></tr><tr><td>1,4-丁二醇</td><td>2</td><td>45</td><td>韧性</td></tr><tr><td>1.6-已二醇</td><td>2</td><td>59</td><td>韧性</td></tr><tr><td>1,4-环已烷二甲醇</td><td>2</td><td>88</td><td>硬度、耐候性</td></tr><tr><td>羟基特戊酸新成戊二醇酯</td><td>2</td><td>102</td><td>韧性、硬度</td></tr><tr><td>乙基丁基丙二醇</td><td>2</td><td>80</td><td>韧性、硬度</td></tr><tr><td>2,2,4-三甲基-1,3-戊二醇</td><td>2</td><td>73</td><td>硬度</td></tr><tr><td>三羟甲基丙烷</td><td>3</td><td>44.7</td><td>韧性、硬度</td></tr><tr><td>季戊四醇</td><td>4</td><td>34</td><td>硬度</td></tr><tr><td rowspan=\"7\">间苯二甲酸 对苯二甲酸 多 苯酐 元</td><td></td><td>2</td><td>83</td><td>硬度、耐候性</td></tr><tr><td></td><td>2</td><td>83</td><td>硬度、溶解性</td></tr><tr><td></td><td>2</td><td>74</td><td>硬度</td></tr><tr><td>己二酸</td><td>2</td><td>73</td><td>韧性</td></tr><tr><td>奎二酸</td><td>2</td><td>101</td><td>韧性</td></tr><tr><td>四氢苯酐</td><td>2</td><td>76</td><td>耐候性、硬度</td></tr><tr><td>偏苯三酸酐</td><td>3</td><td>64</td><td>硬度</td></tr></table></body></html>  \n\n(3）设计依据饱和聚酯树脂是由不同分子量的树脂分子组成的混合物，从理论上讲很难精确的计算配方，只能根据前人的总结和传授、加上自己的实践来进行设计推算。通过树脂试验与应用试验来矫正起始的配方设计，完善树脂的性能，满足涂料的要求，从而丰富自己的配方设计经验，逐步提高自己的设计水平。配方设计前，要尽可能将要求具体化，掌握的信息越多，设计出的基础配方偏差就越小，产品开发周期就越短些。 A  \n\n官能度是产品分子所含官能团的数目，而聚酯树脂是各种分子量的树脂分子聚集物，很难精确计算，但从使用的原料可以计算出理论平均官能度作为参考。从理论上说，平均官能度为2的配方体系不会胶化，若有3官能团或以上的原料存在，理论平均官能度大于2，试验时应注意反应情况。卷材涂料用饱和聚酯树脂，面漆用树脂分子量相对小些，醇超量稍大些，平均官能度一般为 $2.05{\\sim}2.10$ ；底漆用树脂分子量相对大些，醇超量稍小些，平均官能度一般为 $2.0{\\sim}2.05$ 身  \n\n在设计配方时，醇超量是聚酯配方设计时要考虑的重要参数，它牵涉生产工艺的稳定，其数值的大小能影响树脂官能度和分子量，而这些指标影响活性基团（羟基）含量和树脂的性能。不同的用途，醇超量的设置也不相同，用于卷材涂料面漆的饱和聚酯树脂，醇超量一般为 $1.15{\\sim}1.25$ ，用于卷材涂料底漆的饱和聚酯树脂，醇超量一般为 $1.05{\\sim}1.10$ ，这些参数会影响树脂的性能。醇超量可表述如下：  \n\n$$\nR{=}\\frac{e_{\\mathrm{B}}}{e_{\\mathrm{A}}}\n$$  \n\n式中R—醇超量；A——配方中多元醇当量数；$e_{\\mathrm{B}}$ 一配方中多元酸当量数。  \n\n配方设计时，还有一个重要参数必须考虑—工作常数，它表示了树脂达到胶化状态时的反应程度，配方设计时一般都设计为大于1，以保证树脂从理论上不会胶化。工作常数可表述如下：  \n\n$$\nK{=}\\frac{m_{0}}{e_{\\mathrm{A}}}\n$$  \n\n式中 $\\kappa$ —工作常数；$m_{0}$ -—配方中多元醇与多元酸的总摩尔数；eA—配方中多元酸当量数。  \n\n$\\Phi$ 树脂的羟值（一OH）羟值是饱和聚酯树脂的关键参数，这是因为树脂中的羟基要与氨基树脂或异氰酸酯树脂交联。羟值的大小、分布情况、种类是影响交联情况的关键因素。从实际生产的饱和聚酯树脂分析羟值大小，用于制备卷材快速线面漆的树脂羟值一般在$60{\\sim}80\\mathrm{mgKOH/g}$ ，用于制备卷材低速线面漆和背面漆的树脂羟值一般在 $45{\\sim}65\\mathrm{mgKOH/g}$ 用于制备卷材涂料底漆的树脂羟值一般在 $5\\mathrm{\\sim}20\\mathrm{mgKOH/g}$ 。考虑到反应过程中多元醇的升华损耗等，理论设计时的羟值应大于上述推荐的实测羟值。大量的树脂生产积累了理论羟值与实测羟值的偏差，一般实测羟值/理论羟值 $\\approx70\\%\\sim80\\%$ ，若升华损耗小些，实测羟值/理论羟值 $>80\\%$ ，若升华损耗大些，实测羟值/理论羟值 $1<70\\%$ @  \n\n从羟基分布来看，分子链两端的羟基具有更高的反应活性。从羟基的种类分析，伯羟基具有更高的反应活性。根据树脂的应用方向，合理设计树脂的羟值，是我们在设计配方时要考虑的问题。  \n\n$\\textcircled{2}$ 树脂的分子量（ $M_{\\mathrm{s}}$ ）树脂分子量的大小、分布情况是影响涂料性能的一大因素。低分子量的树脂能够提供高的涂膜硬度和高的反应活性，但在韧性方面则稍显不足；相同分子量的树脂的离散度愈大，溶剂稀释性就愈差，黏度愈高，反之树脂黏度愈小。高分子量的树脂具有突出的韧性和附着力，在反应活性方面则有所欠缺。一般来说，使用在面漆中的饱和聚酯其数均分子量一般在10000以内（其中快速线上使用的树脂分子量略低一些，低速线上使用的树脂分子量略高一些），而用于底漆的饱和聚酯树脂分子量一般在10000以上（用于底漆的高分子量线型聚酯树脂分子量一般可达15000以上）。  \n\n$\\textcircled{3}$ 树脂的玻璃化温度（ $T_{\\mathrm{g}})$ 树脂的玻璃化温度是影响涂料韧性、硬度、耐划伤性的关键因素。高的玻璃化温度能赋予涂膜较好的硬度和耐划伤性，较低的玻璃化温度能为树脂提供抗冲击性。一般来说玻璃化温度在 $20\\sim40\\Upsilon$ 的树脂用于生产卷材涂料，其中，面漆所用的树脂玻璃化温度较底漆用树脂稍高，这是因为面漆要考虑涂膜的硬度和耐划伤性，而底漆  \n\n柔韧性则较为关键。  \n\n(4）配方估算配方设计依据是我们估算配方的依据。除此以外，原料的性能、特点及相关理化数据也是我们估算配方的依据。另外，工艺条件情况在估算配方时也要考虑，比如加热方式、冷却效果、搅拌情况对估算配方都有一定程度的影响。下面举例对此加以说明。  \n\n设计一个用于卷材涂料面漆（快速线）的饱和聚酯树脂。  \n\n$\\Phi$ 指标要求含量要求 $60\\%$ ，酸值要求 ${\\leqslant}6\\mathrm{mgKOH/g}$ ，分子量要求 $5000{\\sim}7000$  \n\n$\\textcircled{2}$ 原料的确定根据卷材涂料快速线耐候性、柔韧性和硬度的要求，根据不同原料对树脂性能的贡献，首先确定合成树脂需要的原料。  \n\n新戊二醇：无 $\\beta$ 位氢原子，耐候性好。  \n\n甲基丙二醇：溶解性好，价格相对低廉。  \n\n间苯二甲酸：羧基位阻小，有利于提高分子量、耐候性好。  \n\n己二酸：具有较长的无支链的直链结构，分子链旋转角度大，柔韧性与耐候性好。  \n\n苯酐：溶解性好，价格相对低廉、也有利于硬度。  \n\n偏苯三酸酐：形成体型缩聚产物，能提高交联密度，有利于硬度和耐MEK擦洗。  \n\n催化剂：单丁基氧化锡。  \n\n回流与对稀溶剂：回流脱水与调整树脂含量、黏度用。  \n\n$\\textcircled{3}$ 树脂参数的确定按前文提供的经验数据，羟值取中间值 ${70\\mathrm{mgKOH/g}}$ ，按实测羟值/理论羟值 $\\approx70\\%\\sim80\\%$ 经验值，理论羟值按 $90{\\sim}100\\mathrm{mgKOH/g}$ 计，平均官能度按2.075计，醇超量按1.20计。  \n\n$\\textcircled{4}$ 配方的确定整个配方多元酸的当量按1.0计，则多元醇当量按1.2计。根据快速线用聚酯树脂柔韧性和硬度平衡性方面的要求，初定己二酸用量为酸总量的 $15\\%$ ，按0.15计；根据树脂平均官能团2.075的设计，初定偏苯三酸酐用量为总量的 $10\\%$ ，按0.22计；考虑到间苯二甲酸与苯酐的性能和特点，确定间苯二甲酸用量应大于苯酐，还剩下的多元酸当量中，间苯二甲酸用 $60\\%$ 约0.37，苯酐用 $40\\%$ 约0.26。综合考虑成本等原因，新戊二醇用2/3约0.8，MPD用1/3约0.4。  \n\n根据上述测算结果，再按事先设定的理论羟值、平均官能度等对配方微调，具体配方见表2-1-82（按 $10\\mathrm{m}^{3}$ 反应釜计)。  \n\n表2-1-82配方（kg）估算结果  \n\n\n<html><body><table><tr><td>新戊二醇</td><td>2560</td><td>MPD</td><td>1150</td><td>间苯二甲酸</td><td>1920</td></tr><tr><td>苯酐</td><td>1280</td><td>己二酸</td><td>640</td><td>偏苯</td><td>880</td></tr><tr><td>单丁基氧化锡</td><td>5</td><td>回流二甲苯</td><td>440</td><td>对稀溶剂</td><td>4640</td></tr><tr><td>总酸当量A</td><td>62. 9331</td><td>总醇当量eB</td><td>74.8024</td><td>总摩尔数mo</td><td>66.5758</td></tr><tr><td>平均官能度</td><td>2.07</td><td>工作常数K</td><td>1. 0579</td><td>理论羟值</td><td>95.39</td></tr><tr><td>醇超量</td><td>1. 1886</td><td></td><td></td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 265,
+        "chunk": "# 3.饱和聚酯树脂配方实例  \n\n确定了配方和生产工艺，车间的任务就是严格按照技术部门下达的工艺文件组织生产。从工业化生产的实际情况看，影响产品质量的重要原因在于工艺控制水平，这又涉及操作工的操作技能、工作态度、设备的完好情况等。工艺文件是产品开发试验成果与车间生产实践的有机结合，从生产到试验、再从试验到生产，才能保证工艺文件的合理性与可操作性，以下几个配方实例供参考。  \n\n配方：  \n\n配方1：可用于快速线卷材面漆的聚酯配方（kg）实例  \n\n\n<html><body><table><tr><td>新戊二醇</td><td>3800</td><td>单丁基氧化锡</td><td>5.0</td></tr><tr><td>己二酸</td><td>960</td><td>乙二醇丁醚</td><td>780</td></tr><tr><td>回流二甲苯</td><td>430</td><td>100*溶剂</td><td>1300</td></tr><tr><td>间苯二甲酸</td><td>2400</td><td>150*溶剂</td><td>2400</td></tr><tr><td>偏苯三酸酐</td><td>800</td><td></td><td></td></tr><tr><td>对苯二甲酸</td><td>480</td><td></td><td></td></tr><tr><td>指标：</td><td></td><td></td><td></td></tr><tr><td></td><td>58%~62%</td><td>加氏黏度（25℃）</td><td>15~20s</td></tr><tr><td>固体分 色泽（Fe-Co)</td><td>≤1</td><td>酸值/（mgKOH/g）</td><td>2~5</td></tr></table></body></html>  \n\n操作：  \n\n$\\Phi$ 新戊二醇、间苯二甲酸、对苯二甲酸、偏苯三酸酐、己二酸投人反应釜，通氮气、升温。$\\textcircled{2}$ 加热到能搅拌时，开动搅拌，投入单丁基氧化锡，打开直冷凝与横冷凝冷却水，反应出水后，停止通氮气。  \n\n$\\textcircled{3}$ 逐步升温，控制气相温度 $\\leqslant105\\Upsilon$ ，釜内温度最高为 $235^{\\circ}C$  \n\n$\\textcircled{4}$ 当釜内温度到达 $230^{\\circ}\\mathrm{C}$ 后，取样在玻璃上，冷却到室温后，要达到透明，透明后维持$30{\\sim}45\\operatorname*{min}$ 。冷却到 $180^{\\circ}\\mathrm{C}$ 以下，加人二甲苯。  \n\n$\\textcircled{5}$ 关闭直冷凝冷却水，边脱水边升温进行回流酯化反应，控制反应温度 $\\leqslant220\\mathsf{C}$ ▪$\\textcircled{6}$ 回流反应1h后，进行中控，检验黏度、酸值（注意反应后阶段黏度上升趋势）。  \n\n取样比例12.7g样品 $+7.3g$ 稀释溶剂要求控制加氏黏度 $(25^{\\circ})$ ） $15\\sim20{\\mathrm{s}}$ 酸值/（mgKOH/g）2～5  \n\n$\\textcircled{7}$ 中控符合要求后，冷却到 $180^{\\circ}\\mathrm{C}$ 以下，放料到对稀釜中（对稀釜中先加人部分对稀溶剂)；反应釜中加入剩余的对稀溶剂，回流一段时间后放入对稀釜中，搅拌均匀后复测黏度，达到要求后过滤包装。  \n\n配方2：0T弯卷材面漆的聚酯配方（kg）实例  \n\n<html><body><table><tr><td colspan=\"4\"></td></tr><tr><td>配方： 新戊二醇</td><td>2080</td><td>己二酸</td><td>1320</td></tr><tr><td>BEPD</td><td>630</td><td>回流二甲苯</td><td>250</td></tr><tr><td>单丁基氧化锡</td><td>5.0</td><td>150*溶剂</td><td>3200</td></tr><tr><td>乙二醇丁醚</td><td>780</td><td>1,6-己二醇</td><td>240</td></tr><tr><td>三羟甲基丙烧</td><td>240</td><td>间苯二甲酸</td><td>2760</td></tr><tr><td>指标：</td><td></td><td></td><td></td></tr><tr><td>固体分</td><td>58%~62%</td><td>加氏黏度(25℃)</td><td></td></tr><tr><td>色泽（Fe-Co)</td><td>≤1</td><td>酸值/(mgKOH/g)</td><td>25~35s 2~6</td></tr></table></body></html>  \n\n操作：  \n\n$\\Phi$ 新戊二醇、间苯二甲酸、三羟甲基丙烷、1，6-己二醇、BEPD投入反应釜，通氮气、升温。  \n\n$\\textcircled{2}$ 加热到能搅拌时，开动搅拌，投入单丁基氧化锡，打开直冷凝与横冷凝冷却水，反应出水后，停止通氮气。  \n\n$\\textcircled{3}$ 继续缓慢升温，气相温度按如下要求控制：  \n\n第1小时，气相温度 $102{\\sim}105\\mathrm{^c}$ \\*第 $2{\\sim}3$ 小时，气相温度 $108{\\sim}112^{\\circ}\\mathrm{C}$ \\*\\*.第4小时，气相温度 $105{\\sim}108\\%$ 。  \n\n釜内按如下要求控制：  \n\n前1.5小时，釜内温度 $\\leqslant190\\mathsf{\\tau}$ 后2.5小时，釜内温度 $190{\\sim}210^{\\circ}\\mathrm{C}$  \n\n$\\textcircled{4}$ 熔融酯化反应4h后，取样在玻璃上，冷却到室温后，要达到透明，透明后维持 $30\\sim$ 45min。冷却到 $170^{\\circ}\\mathrm{C}$ 以下，加入已二酸和二甲苯。  \n\n$\\textcircled{5}$ 关闭直冷凝冷却水，边脱水边升温，进行回流酯化反应，控制反应温度 $\\leqslant220\\tau$ $\\textcircled{6}$ 回流反应2h后，进行中控，检验黏度、酸值（注意反应后阶段黏度上升趋势)。  \n\n取样比例 $12.7_{8}$ 样品 $+7.38$ 稀释溶剂要求控制加氏黏度（ $25\\mathrm{{C}}$ ） $25\\sim35\\mathrm{s}$ 酸值/ $\\mathbf{\\dot{\\Omega}}_{\\mathrm{mgKOH/g}}$ 0 $2{\\sim}6$  \n\n$\\textcircled{7}$ 中控规定要求后，冷却到 $180^{\\circ}\\mathrm{C}$ 以下，放料到对稀釜中（对稀釜中先加入部分150#溶剂)；反应釜中加人剩余 $150^{*}$ 溶剂，回流一段时间后，放人对稀釜中，搅拌 $0.5\\sim1.0\\mathrm{h}$ 后，加人乙二醇丁醚，搅拌均匀后复测黏度，达到要求后过滤包装。  \n\n配方3：可用于慢速线卷材面漆的聚醋配方（kg）实例  \n\n<html><body><table><tr><td colspan=\"4\"></td></tr><tr><td>配方： MPD</td><td>2880</td><td>苯酐</td><td>3150</td></tr><tr><td>己二酸</td><td>760</td><td>150*溶剂</td><td>3320</td></tr><tr><td>回流二甲苯</td><td>380</td><td>间苯二甲酸</td><td>975</td></tr><tr><td>乙二醇丁醚</td><td>1230</td><td>单丁基氧化锡</td><td>5.0</td></tr><tr><td>季虎四醇</td><td>380</td><td></td><td></td></tr><tr><td>指标：</td><td></td><td></td><td></td></tr><tr><td>固体分</td><td>58%~62%</td><td>加氏黏度（25℃）</td><td>20~30s</td></tr><tr><td>色泽（Fe-Co)</td><td>≤1</td><td>酸值/（mgKOH/g)</td><td>3~8</td></tr></table></body></html>  \n\n操作：  \n\n$\\textcircled{1}$ MPD、季戊四醇、苯酐、间苯二甲酸、己二酸投人反应釜，通氮气、升温。  \n\n$\\textcircled{2}$ 加热到能搅拌时，开动搅拌，投入单丁基氧化锡，打开直冷凝与横冷凝冷却水，反应出水后，停止通氮气。  \n\n$\\textcircled{3}$ 继续缓慢升温，控制气相温度 $\\leqslant105\\mathrm{{c}}$ ，釜内温度最高为 $200\\Upsilon$ 要  \n\n$\\textcircled{4}$ 熔融酯化反应3h后，取样在玻璃上，冷却到室温后，要达到透明，透明后维持 $30\\sim$ $45\\mathrm{{min}}$ 。冷却到 $180^{\\circ}\\mathrm{C}$ 以下，加人二甲苯。  \n\n$\\textcircled{5}$ 关闭直冷凝冷却水，边升温边脱水，进行回流酯化反应，控制反应温度 $\\leqslant200\\mathtt{C}$ 要$\\textcircled{6}$ 回流反应2h后，进行中控，检验黏度、酸值（注意反应后阶段黏度上升趋势）。  \n\n取样比例 $12.7\\mathbf{g}$ 样品 $+7.3g$ 稀释溶剂要求控制加氏黏度（ $25\\%$ ） $20\\sim30\\mathrm{s}$ 酸值/（mgKOH/g）3\\~8  \n\n$\\textcircled{7}$ 中控符合要求后，冷却到 $180^{\\circ}\\mathrm{C}$ 以下，放料到对稀釜中（对稀釜中先加人部分对稀溶剂)；反应釜中加人剩余对稀溶剂，回流一段时间后，放入对稀釜中，搅拌均匀后复测黏度，达到要求后过滤包装。 C配方4：用于生产聚酯聚氨酯卷材底漆的聚酯配方（kg）实例指标：固体分 58%\\~62% 加氏黏度（25℃） 15\\~25s色泽（Fe-Co) ≤1 酸值/(mgKOH/g) 2\\~6  \n\n<html><body><table><tr><td colspan=\"3\">配方：</td></tr><tr><td>MPD</td><td>2890</td><td>回流二甲苯</td></tr><tr><td>单丁基氧化锡</td><td>6.0 丁醇</td><td></td></tr><tr><td>环己酮</td><td>970</td><td>间苯二甲酸</td></tr><tr><td>苯酐</td><td>2500 100*溶剂</td><td>2300 2920</td></tr></table></body></html>  \n\n操作：  \n\n$\\textcircled{1}$ MPD、间苯二甲酸、苯酐投入反应釜，通氮气、升温。  \n\n$\\textcircled{2}$ 加热到能搅拌时，开动揽拌，投入单丁基氧化锡，打开直冷凝与横冷凝冷却水，反应出水后，停止通氮气。  \n\n$\\textcircled{3}$ 继续缓慢升温，气相温度按如下要求控制：  \n\n第 $_{1\\sim3}$ 小时，气相温度 $95{\\sim}98\\%$ 第 $4{\\sim}5$ 小时，气相温度 $98{\\sim}102\\Upsilon$ 第 $6{\\sim}7$ 小时，气相温度 $102{\\sim}105\\Upsilon$ 釜内温度要求 $\\mathfrak{s}220\\mathfrak{c}$ ，一般熔融反应 $6\\sim7\\mathrm{h}$ ，可达到透明。  \n\n$\\textcircled{4}$ 熔融酯化反映5h后，取样在玻璃上，冷却至室温后，要达到透明，透明后维持 $30\\sim$ $45\\mathrm{{min}}$ 。冷却到 $180^{\\circ}\\mathrm{C}$ 以下，加人二甲苯。  \n\n$\\textcircled{5}$ 关闭直冷凝冷却水，边升温边脱水，进行回流酯化反应，控制反应温度 $\\leqslant200^{\\circ}\\mathrm{C}$ $\\textcircled{6}$ 回流反应1h后，进行中控，检验黏度、酸值（注意反应后阶段黏度上升趋势）。  \n\n取样比例 $13.0\\mathbf{g}$ 样品 $+7.08$ 稀释溶剂要求控制加氏黏度 $(25\\Upsilon)$ ） $\\phantom{+}15\\sim25\\mathrm{s}$ 酸值/（mgKOH/g）2～6  \n\n$\\textcircled{7}$ 中控符合要求后，冷却到 $180^{\\circ}\\mathrm{C}$ 以下，放料到对稀釜中（对稀釜中先加人部分对稀溶剂)；反应釜中加人剩余对稀溶剂，回流一段时间后，放人对稀釜中，搅拌均匀后复测黏度，达到要求后过滤包装。  \n\n配方5：用于生产卷材底漆的线性高分子量聚酯配方（kg）实例  \n\n<html><body><table><tr><td colspan=\"4\">配方：</td></tr><tr><td>新戊二醇</td><td>1500</td><td>己二酸</td><td>1230</td></tr><tr><td>1,6-已二醇</td><td>420</td><td>回流二甲苯</td><td>440</td></tr><tr><td>单丁基氧化锡</td><td>7.0</td><td>150*溶剂</td><td>4680</td></tr><tr><td>环已酮</td><td>1150</td><td>三羟甲基丙烷</td><td>90</td></tr><tr><td>MPD</td><td>440</td><td>间苯二甲酸</td><td>2380</td></tr><tr><td>指标：</td><td></td><td></td><td></td></tr><tr><td></td><td>43%~47%</td><td>加氏黏度（25℃）</td><td>25~30s</td></tr><tr><td>固体分 色泽（Fe-Co)</td><td>≤1</td><td>酸值/（mgKOH/g)</td><td>3~8</td></tr></table></body></html>  \n\n操作：  \n\n$\\textcircled{1}$ 新戊二醇、MPD、间苯二甲酸、1，6-己二醇、三羟甲基丙烷投人反应釜，通氮气、升温。  \n\n$\\textcircled{2}$ 中控符合要求后，停止加热，慢慢放入高位槽事先备好的部分环已酮，充分搅拌后放料到对稀釜中（对稀釜中先加人部分 $150^{*}$ 溶剂)；反应釜中加入剩余的对稀溶剂，回流一段时间后，放入对稀釜中，搅拌均匀后复测黏度，要求达到： 9八  \n\n加氏黏度（25℃） 26\\~29s符合要求后过滤包装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 266,
+        "chunk": "# 4.粉末涂料用聚酯树脂  \n\n粉末涂料是20世纪后半叶开始发展起来的，无溶剂污染的涂料品种，一般以粉末状态涂装并形成涂层，综合性能优良，目前大规模应用的粉末涂料以热固性为主，热塑性的应用相对较少。粉末涂料发展初期，采用双酚A环氧体系的较多，随着发展也有采用丙烯酸树脂体系、聚氨酯树脂体系等，但由于性能、价格、环保等方面原因，近年来采用聚酯树脂体系上升很快，涂层兼有环氧、丙烯酸、聚氨酯粉末涂料的长处，有良好的装饰性、耐候性，适用于户外耐候性要求高的场合。  \n\n粉末涂料的贮存稳定性、交联时的粉末流动性、固化后的涂膜性能，都与采用的树脂体系有关，饱和聚酯树脂是粉末涂料采用的一种树脂体系。与生产溶剂型涂料的饱和聚酯树脂采用端羟基结构树脂不同的是，生产聚酯粉末涂料采用端羧基结构的树脂，可使用异氰脲酸三缩水甘油酯（TGIC）通过开环式加成反应与聚酯树脂交联，形成硬度高、耐候、耐腐蚀的热固性聚合物网络。  \n\n![](images/ba8e84a98e2baf1d87bb8101c7bdcd6789e9a9eccf7f703ab9de0cea904156b2.jpg)  \n聚酯-TGIC聚酯粉末涂料固化反应式  \n\n聚酯/TGIC体系的粉末涂料，TGIC有一定毒性，对皮肤有刺激作用，一些欧美国家开始限制使用，因而开发了其他类型的同化交联方式，其中以 $\\beta$ 羟烷基酰胺（HAA）通过酯化反应与聚酯树脂交联的方式较为普遍。HAA的反应活性比TGIC大，因此固化温度低、用量小，用HAA的涂料贮存稳定性好，但涂料耐候性、耐热性差些，固化交联时有低分子化合物放出，涂层易出现针孔等，需要根据粉末涂料要求选择合适的固化体系。  \n\n![](images/6c25754a55ea677f271f60d95076e6bc9c86e526547b37532c1cabeed40e9f86.jpg)  \n聚酯-HAA聚酯粉末涂料固化反应式  \n\n端羟基饱和聚酯树脂采用多异氰酸酯加成物交联，也可生产粉末涂料，但习惯上将其划入聚氨酯粉末涂料。  \n\n将饱和聚酯树脂、固化剂、颜填料按比例混合后，由研磨设备粉碎后，经熔融挤出、粉碎过筛，可得到聚酯粉末涂料。聚酯粉末涂料生产工艺流程如下。  \n\n![](images/8a834c9455c45d4e587593621305bee06eaf0b89f5307d3b86dd853e2c03d43b.jpg)  \n\n粉末涂料贮存过程中，要保持自由流动的细分散状态，但交联固化前的一定温度范围内必须熔融，保证充分及时的流动，涂装时可形成性能优异的涂膜。聚酯组分玻璃化温度C $T_{\\mathrm{g}}$ ）必须高于粉末涂料贮存温度，否则会使细分散状态的颗粒聚集、结块，影响施工。聚酯组分的 $T_{\\mathrm{*}}$ ，与粉末涂料贮存稳定性、熔融黏度有很大关联， $T_{\\mathrm{s}}$ 大小主要与所采用原料结构相关，含苯环或高支链化结构的多元醇和多元酸用量大，树脂的 $T_{\\mathrm{s}}$ 就高，线型直链结构的多元醇和多元酸用量大，树脂的 $T_{\\mathrm{s}}$ 就小；综合评估， $T_{*}$ 设计成 $55\\sim65^{\\circ}C$ 较为合适。远高于生产溶剂型涂料所用端羟基聚酯树脂的 $T_{\\mathrm{*}}$ ，考虑所选多元醇与多元酸的结构，酯化反应催化剂的加入量要相对多一些。  \n\n考虑到工业生产中检验项目测试的难易程度，目前针对固体聚酯树脂建立比较容易检测的项目—软化点，其实测数据比树脂的 $T_{\\mathrm{s}}$ 值要高，一般高出约 $40\\%$ 。树脂的软化点与分子量存在近似的递增线性关系，树脂分子量大小对粉末涂料生产时的粉碎情况、粉末涂料结晶性产生直接影响。分子量增大时，聚酯树脂的强度和硬度也增大，树脂粉碎为细分散状态的难度增大，若分子量过大，细分散后的涂料熔融难、流动性差；分子量减小时，聚酯树脂的软化点下降，粉末涂料生产利贮存过程中，结块倾向增大，若分子量过小，粉末涂料生产困难、贮存稳定性差。根据应用需要，数均分子量确定为 $2000{\\sim}4000$ 较为合适。  \n\n粉末涂料用饱和聚酯树脂是端羧基结构的，因而配方设计为多元酸过量，从聚酯树脂合成原理可以知道，多元酸过量的树脂反应到一定程度后会胶化，因此必须在到达此反应程度前中止反应进程。生产中为避免胶化这一状况发生，采取将部分多元酸后投，先合成端羟基聚酯树脂，即起始投料时，部分多元酸（一般是三官能团多元酸）不投入，使得开始反应仍能保持多元醇过量，等反应到一定程度（生产中以酸值来控制)，再加入起始投料时留出来的多元酸，继续反应一段时间，达到规定的指标后，结束反应，并加入添加剂（主要是固化交联促进剂等)，搅拌均匀，在熔融状态下由切片机制成聚酯薄片。根据粉末涂料的生产需要，控制聚酯树脂酸值 $50{\\sim}80\\mathrm{mgKOH/g}$ 较为合适。 Wr  \n\n由粉末涂料用聚酯树脂 $100\\%$ 固体分的特点，合成时宜采用熔融酯化的工艺，便于反应终止后的成型。与溶剂型端羟基聚酯树脂合成相比，采用全熔融的酯化工艺，没有回流酯化过程，不用回流溶剂，为使酯化反应水及时从反应釜中被移走，可往反应釜底部通入情性气体，将酯化反应水从反应物料中赶出，达到帮助脱水的目的。因此，增加通往反应釜底部，用来通入情性气体的管道后，生产溶剂型端羟基饱和聚酯树脂的反应釜可用于生产粉末涂料用端羧基饱和聚酯树脂。 0 a",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 267,
+        "chunk": "# 5.水溶性聚酯树脂  \n\n在当今社会环境下，涂料应当向无污染、低污染的方向发展，习惯上称为环境友好型涂料，主要涵盖无溶剂及高固体分涂料、水性涂料、粉末涂料和辐射固化涂料等。与粉末涂料和辐射固化涂料相比，水性涂料由于不需要特殊涂装设备，适用面大，有利于推广应用，水性涂料主要有水分散性涂料、水乳化涂料与水溶性涂料等，目前建筑装潢行业广泛的应用乳胶漆，属于水分散性涂料。水溶性聚酯树脂可与水溶性氨基树脂配合生产水性烘漆，也可与亲水性多异氰酸酯配合生产双组分水性自干性漆，可用于金属和木器表面的装饰与保护，涂膜光泽高、附着力强、丰满度好、耐冲击性优良等。  \n\n要使得原本不溶于水的聚酯树脂能“溶于水”，需要在聚酯树脂分子链上引入可溶于水的基团，使树脂分子溶于水，从而得到水溶性聚酯树脂。目前采取先合成酸值相对较高（一般约为 $40{\\sim}60\\mathrm{mgKOH}/g)$ 的树脂，溶解于助溶剂中（一般采用醇醚类溶剂或醇类溶剂)，然后有机胺与羧基中和反应生成水溶性的铵盐，完成了将水溶性基团引人聚酯分子链的目的。通过控制树脂酸值，来控制水溶性的铵盐，调整好树脂的“水溶性”，满足涂料的性能要求。  \n\n水溶性聚酯树脂具有相对较高的酸值，为保证交联反应后的涂膜性能，又必须有合适的羟值，配方体系的醇超量不会很高，设计配方时，要注意多元醇、多元酸之间的比例。为防止合成过程中发生胶化，可采取与合成粉末涂料用端羧基聚酯树脂同样的工艺，即预留部分多元酸后加，使开始反应时多元醇过量的多些，保证反应的稳定，等反应到一定程度后，加预留的多元酸，继续反应一段时间，再用有机胺中和。  \n\n可用的有机胺有乙二胺、三乙胺、乙醇胺、二乙醇胺等，考虑醇胺含有的羟基对水溶性有帮助，一般选用醇胺，目前最常用的是二乙醇胺。若中和反应程度不到，形成的铵盐不$\\scriptstyle{\\mathfrak{B}}$ ，树脂水溶性下降，体系稳定性也下降；若中和反应程度过大，体系易增稠，要达到涂料施工黏度，必须增加水的添加量，会降低体系固体分，影响涂膜丰满度。一般中和时控制体系的 $\\mathbf{pH}$ 为 ${7}{\\sim}8$ 京  \n\n树脂的相对分子量的大小，影响着树脂的性能，是合成树脂时必须要控制的重要指标。水溶性聚酯涂料是以交联固化后来形成涂膜的，若分子量过小，需要较高的交联树脂用量来保证涂膜性能，使涂料的成本增加，而且贮存稳定性会下降。若分子量过大，树脂的黏度增大，需要较大的助溶剂用量来溶解树脂，增加了有机溶剂用量，增加了涂料的VOC。  \n\n水性氨基树脂可选用全甲醚化或部分甲醚化三聚氰胺树脂，一般来讲，采用全甲醚化三聚氰胺甲醛树脂（HMMM)，涂装时的烘烤温度要高些，涂膜的硬度低些，但涂膜柔韧性好；采用部分甲醚化三聚氰胺甲醛树脂（HMM)，涂装时的烘烤温度可低些，涂膜的硬度高些，但涂膜柔韧性要差些。我们要根据涂膜的性能和涂装条件，来选择合适的交联树脂。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 268,
+        "chunk": "# 6.改性饱和聚酯树脂  \n\n由于分子结构的差异，涂料用树脂性能和应用领域有较大不同，采用改性的方法，将多元醇、多元酸之外的成分引入聚酯分子链，调整树脂分子链的组成，来改善和突出某些性能，得到综合性能优良的改性聚酯，满足日益发展的高性能涂料要求。有不少单体或树脂可用于改性，本章主要涉及使用环氧、合成脂肪酸、丙烯酸、有机硅等改性聚酯树脂，用于改性的单体或树脂，有各不相同的分子结构，所含的活性基团也不同，需要被改性的聚酯提供能与之反应的活性基团，以达到对聚酯树脂进行改性的目的。  \n\n$\\Phi$ 若聚酯树脂用丙烯酸单体来改性，聚酯树脂要提供活性基团（一般可在合成聚酯树脂时引入含双键的原料，如顺酐或衣康酸等)，与丙烯单体中的双键进行自由基聚合反应，从而完成对聚酯的改性。  \n\n$\\textcircled{2}$ 若聚酯树脂用丙烯酸树脂来改性，聚酯树脂要提供活性基团（羟基）与丙烯酸树脂中的羧基进行酯化反应，从而完成对聚酯的改性。  \n\n③若聚酯树脂用有机硅树脂来改性，聚酯树脂要提供活性基团（羟基)，与有机硅树脂中的羟基进行缩合反应，从而完成对聚酯的改性。  \n\n$\\textcircled{4}$ 若聚酯树脂用合成脂肪酸来改性，合成脂肪酸与多元醇、多元酸进行酯化反应时，合成脂肪酸也参与其中，接枝到了聚酯的分子链上，得到了脂肪酸改性聚酯树脂。  \n\n$\\textcircled{5}$ 若聚酯树脂用环氧树脂来改性，多元醇与多元酸进行酯化酯时，环氧树脂链端的环氧基开环形成羟基，参与了酯化反应，接枝到了聚酯的分子链上，得到了环氧改性聚酯树脂。  \n\n(1）环氧改性目前环氧改性聚酯树脂，一般采用固体状的双酚A型环氧树脂。在一定条件下，环氧树脂分子链两边的环氧基开环，形成羟基，被作为含羟基的多元醇，在合成环氧改性聚酯树脂时，与多元醇、多元酸同时投料，在聚酯分子主链上接枝了环氧树脂分子，使改性树脂同时具有环氧树脂和聚酯树脂优良的特性。聚酯树脂用环氧改性后提高了涂膜对底材的附着力、耐化学性、耐碱耐热性等，大大拓展了改性聚酯树脂涂料的应用范围。  \n\n环氧树脂中的环氧基开环形成羟基，才能与多元酸发生酯化反应，但环氧基开环有一定的条件，若改性反应不顺利（因为环氧树脂溶解性较差)，未反应的环氧树脂，容易造成改性聚酯的透明性下降。用不同型号的环氧树脂改性，其反应速率也不相同，因而接枝方式、最大改性量、反应条件等，都因为采用不同环氧树脂而有所不同，改性聚酯性能也有所差异。  \n\n环氧树脂一般选用双酚A型环氧树脂，常用的是609、604、6101等牌号。环氧树脂分子量大，与多元酸的反应活性低，工艺控制困难，容易造成改性后的树脂透明度差，因此改性量不可过大。环氧树脂分子量小，环氧基开环形成的羟基与多元酸的反应活性大，反应也容易进行，一般会在熔融反应完成后，与回流溶剂一起投入；但由于环氧树脂分子量小，对改性聚酯的性能改善不如分子量大的环氧树脂。  \n\n以卷材涂料底漆为例，环氧底漆一般采用大分子量609环氧树脂，用脲醛树脂固化，环氧体系硬度高、耐腐蚀性好、附着力好，但柔韧性低、T弯较差。聚酯底漆采用饱和聚酯树脂为主，可用甲醚化氨基树脂或封闭型聚氨酯来交联，聚酯体系柔韧性、T弯好，但硬度、附着力、耐腐蚀性比环氧体系要差。综合了环氧树脂与聚酯树脂特点的环氧改性聚酯，可生产出综合性能平衡、优良，适应多种底材，应用广泛的卷材涂料底漆。  \n\n配方6：环氧改性聚酯配方（kg）实例  \n\n<html><body><table><tr><td colspan=\"5\">配方：</td></tr><tr><td>MPD</td><td>2440</td><td>1,6-己二醇</td><td></td><td>300</td></tr><tr><td>己二酸</td><td>900</td><td>乙二醇丁醚</td><td></td><td>840</td></tr><tr><td>回流二甲苯</td><td>400</td><td>609环氧树脂</td><td></td><td>350</td></tr><tr><td>150*溶剂</td><td>5200</td><td>单丁基氧化锡</td><td></td><td>4.0</td></tr><tr><td>间苯二甲酸</td><td>3500</td><td></td><td></td><td></td></tr><tr><td>指标：</td><td></td><td></td><td></td><td></td></tr><tr><td>固体分</td><td>48%~52%</td><td>加氏黏度（25℃）</td><td></td><td>20~30s</td></tr><tr><td>色泽（Fe-Co)</td><td>≤3</td><td>酸值/（mgKOH/g)</td><td></td><td>3~8</td></tr></table></body></html>  \n\n操作：  \n\n$\\Phi$ MPD、间苯二甲酸、1，6-己二醇、609环氧树脂投入反应釜，通氮气、升温。  \n\n$\\textcircled{2}$ 加热到能搅拌时，开动搅拌，投入单丁基氧化锡，打开直冷凝与横冷凝冷却水，反应出水后，停止通氮气。  \n\n$\\textcircled{3}$ 继续缓慢升温，气相温度按如下要求控制：  \n\n气相温度 $100{\\sim}105\\Upsilon$  \n\n釜内温度一般控制 $180\\sim210^{\\circ}\\mathrm{C}$ $_{(\\leqslant215\\mathsf{T})}$ ，一般熔融反应 $4\\sim5\\mathrm{h}$ 后，可达到透明。  \n\n$\\textcircled{4}$ 熔融酯化反应3h后，取样在玻璃上，冷却到室温后，要达到透明，透明后维持30～45min。冷却到 $170^{\\circ}\\mathrm{C}$ 以下，加入己二酸和二甲苯。  \n\n$\\textcircled{5}$ 关闭直冷凝冷却水，升温脱水进行回流酯化反应，控制反应温度 $1\\leqslant200\\mathtt{C}$ $\\textcircled{6}$ 回流反应1h后，进行中控，检验黏度、酸值（注意反应后阶段黏度上升趋势）。  \n\n取样比例 $10.6\\mathbf{g}$ 样品+9.4g稀释溶剂要求控制加氏黏度 $25\\Upsilon$ ） $20\\sim30{\\mathrm{s}}$ 酸值/（mgKOH/g） $3{\\sim}8$  \n\n$\\textcircled{7}$ 中控符合要求后，冷却到 $180^{\\circ}\\mathrm{C}$ 以下，放料到兑稀釜中（兑稀釜中先加入部分兑稀溶剂)；反应釜中加人剩余兑稀溶剂，回流一段时间后，放入兑稀釜中，搅拌均匀后复测黏度，达到要求后过滤包装。  \n\n(2）脂肪酸改性改性聚酯树脂所用的脂肪酸，从聚酯树脂的应用看，含有不饱和键，对涂膜性能没有益处，因此使用烃基碳链上不含不饱和键的饱和脂肪酸。目前采用长碳链的脂肪酸，都是人工合成的，因此也称为合成脂肪酸。通过羟基与羧基间的反应，将脂肪酸的碳链引入聚酯树脂分子链上， $\\textcircled{1}$ 改善聚酯树脂与其他树脂的混溶性，扩大了应用领域； $\\textcircled{2}$ 以卷材涂料面漆为例，板温一般为 $224\\sim232^{\\circ}\\mathrm{C}$ ，温度较高，采用改性聚酯树脂后，可降低烘烤温度； $\\textcircled{3}$ 合成脂肪酸的价格比较低廉，用于改性聚酯树脂，可降低树脂成本。  \n\n合成脂肪酸是一元酸，接入树脂主链后，不能继续提供活性基团，有链封闭剂的作用，用量过大，会影响饱和聚酯树脂分子链的增长，用量过小，起不到改善性能的作用。不同合成脂肪酸碳链长度不同，羧基的含量不同，同样用于改性，反应活性也不同，最终树脂的贮存稳定性不同，并非所有规格都能用于改性，要从性能与工艺要求来选择碳链长度合适的合成脂肪酸用于改性，并确定改性比例，这是改性聚酯树脂成功的关键，综合各种因素，目前一般采用月桂酸（十二酸）来改性饱和聚酯树脂。  \n\n配方7：合成脂肪酸改性聚酯配方（kg）实例  \n\n\n<html><body><table><tr><td colspan=\"4\">配方：</td></tr><tr><td>月桂酸</td><td>2080</td><td>回流二甲苯</td><td>400</td></tr><tr><td>次磷酸</td><td>8</td><td>乙二醇丁醚</td><td>290</td></tr><tr><td>100*溶剂</td><td>3680</td><td>甘油</td><td>2050</td></tr><tr><td>苯酐</td><td>2960</td><td></td><td></td></tr><tr><td>指标：</td><td></td><td></td><td></td></tr><tr><td>固体分</td><td>58%~62%</td><td>加氏黏度（25℃）</td><td>30~40s</td></tr><tr><td>色泽（Fe-Co)</td><td>≤1</td><td>酸值/（mgKOH/g)</td><td>3~8</td></tr></table></body></html>  \n\n操作：  \n\n$\\Phi$ 月桂酸、甘油、苯酐、次磷酸投入反应锅后，通氮气、升温。  \n\n$\\textcircled{2}$ 加热到能搅拌时，开动搅拌，打开直冷凝与横冷凝冷却水，反应出水后，停止通氮气。  \n\n$\\textcircled{3}$ 继续缓慢升温，气相温度按如下要求控制：气相温度 $100{\\sim}105\\Upsilon$ 釜内温度一般控制 $180{\\sim}205\\Upsilon(\\leqslant210^{\\circ}\\mathsf{C})$ ，一般熔融反应 $_{4\\sim5\\mathrm{h}}$ 后，可达到透明。  \n\n$\\textcircled{4}$ 熔融酯化反应3h后，取样在玻璃上，冷却到室温后，要达到透明，透明后维持 $15\\sim$ $30\\mathrm{min}$ 。冷却到 $180^{\\circ}\\mathrm{C}$ 以下，加入二甲苯。  \n\n$\\textcircled{5}$ 关闭直冷凝冷却水，升温脱水进行回流酯化反应，控制反应温度 ${\\leqslant}220\\mathsf{C}$ 。  \n\n$\\textcircled{6}$ 回流反应1h后，进行中控，检验黏度、酸值（注意反应后阶段黏度上升趋势）。  \n\n取样比例 $12,6\\mathbf{g}$ 样品 $+7.48$ 稀释溶剂要求控制加氏黏度（25℃） $30\\sim40{\\mathrm{s}}$ 酸值/ $(\\mathrm{mgKOH/g})$ 3\\~8  \n\n$\\textcircled{7}$ 中控符合要求后，冷却到 $180^{\\circ}\\mathrm{C}$ 以下，放料到兑稀釜中（兑稀釜中先加入部分兑稀溶剂)；反应釜中加入剩余兑稀溶剂，回流一段时间后，放入兑稀釜中，搅拌均匀后复测黏度，达到要求后过滤包装。  \n\n(3）丙烯酸改性丙烯酸酯类改性饱和聚酯树脂是在聚酯树脂分子链上接枝丙烯酸酯类，起到分子内增塑作用，调整树脂分子链结构，使改性后聚酯具有丙烯酸树脂的优点，因此，丙烯酸酯的改性量与改性树脂性能密切相关，丙烯酸酯类的选择对改性聚酯树脂性能也有很大影响。  \n\n丙烯酸酯类改性聚酯时，经常采用高 $\\boldsymbol{T}_{\\kappa}$ 的甲基丙烯酸酯类单体。若改性量过小，无法体现树脂被改性后的特点，未达到改善和突出某些性能的目的；若改性量大，丙烯酸树脂的特性容易体现，但聚酯树脂的特点被掩盖了，且涂膜容易变脆，柔韧性不好；若采用含高支链结构的丙烯酸酯类，如甲基丙烯酸月桂酸酯、甲基丙烯酸异冰片酯等，利用高支链来增加分子链韧性，即使改性量大些，也能得到柔韧性和硬度高度平衡的涂膜。因此在设计树脂配方时，应选用结构合适的单体来改善聚酯树脂的应用性能。  \n\n丙烯酸改性聚酯树脂主要有两种工艺路线。  \n\n第一种工艺路线是接枝共聚的工艺，采用多元醇、多元酸、不饱和二元酸（常用的有衣康酸和顺丁烯二酸酐）来合成能提供足够活性基团的低分子量聚酯树脂。一定温度下，滴加丙烯酸酯类及引发剂（常用过氧化二叔丁基，温度 $135{\\sim}140^{\\circ}\\mathrm{C}$ 时半衰期约3h)，丙烯酸酯类中的双键与聚酯树脂中的双键进行自由基聚合反应，得到了一种兼有饱和聚酯树脂和丙烯酸树脂综合性能的产品。  \n\n第二种工艺路线是酯化反应的工艺，采用丙烯类单体，在引发剂作用下，合成含有一定羧基的丙烯酸树脂，同时用多元醇、多元酸合成含有羟基与羧基的低分子量聚酯，然后丙烯酸树脂与低分子量聚酯进行酯化反应，从而得到兼有聚酯树脂和丙烯酸树脂特点、性能优异的改性聚酯。由于先合成两种半成品，然后进行酯化反应，只要控制好两个半成品分子量大小、使用比例，容易得到分布均匀的改性聚酯。  \n\n采用不同工艺路线生产得到的改性聚酯树脂，产品性能和操作工艺有所差异，接枝共聚的工艺生产控制相对容易、改性的聚酯与颜料润湿分散性更好些；酯化反应的工艺生产控制相对复杂，但所得改性聚酯生产的涂料光泽、流平性好。开发产品究竟选择怎样的工艺路线，要从工艺控制情况和用户的性能要求来选择。  \n\n饱和聚酯树脂用丙烯酸酯类改性后， $\\Phi$ 能与丁醚化氨基在内的大部分氨基树脂相配合，可根据顾客对涂膜性能与施工条件的要求，扩大氨基树脂的选择范围，拓展了改性聚酯树脂的应用领域； $\\textcircled{2}$ 能改善聚酯树脂对颜料的润湿分散性，若用于生产高档油墨，可改善聚酯对颜料的润湿分散性，生产出高品质的印刷油墨； $\\textcircled{3}$ 聚氨酯聚酯涂料中，使用丙烯酸改性聚酯树脂，可取得更好的涂膜流平性和光泽。  \n\n（4）有机硅改性有机硅树脂是以Si—O—Si为主链的元素有机聚合物，具有高度交联结构的热固性聚硅氧烷体系。有机硅树脂体系中的 $\\mathbb{R}^{1}$ ， $\\scriptstyle\\mathbb{R}^{2}$ 是与硅相连的烷基，可根据性能要求引入各种官能团来改善润湿分散性、耐热性、硬度等性能，常见的是甲基、乙基、丙基、苯基等。硅树脂分子链间作用力较小，因此加工性差、耐溶剂性不好、固化温度高，饱和聚酯树脂丰满度好、耐溶剂性好、硬度高、加工性能好，但耐水性差，两种树脂特性正好互补。若将有机硅树脂接枝到聚酯树脂的分子链上，就能得到具有两类树脂的特性、综合性能平衡的有机硅改性聚酯树脂。  \n\n有机硅改性聚酯树脂，一般采用硅烷（含硅氧基Si—OR或硅羟基Si—OH）与聚酯树脂（含羟基一OH）进行缩合反应来合成，如图2-1-14所示。  \n\n![](images/0bdefc3889451b9a8920ced25108bb178a806ad0c6d88f59d22c351566f61df7.jpg)  \n图2-1-14有机硅改性聚酯树脂合成反应示意  \n\n硅改性树脂的性能处于有机硅树脂与聚酯树脂之间，有机硅含量增加，性能向有机硅树脂倾斜，但产品成本高；若聚酯树脂含量高，就没有有机硅树脂性能，产品的电绝缘性、耐候性、耐热性就下降，因此要根据产品性能要求，设计合适的改性比例。  \n\n有机硅改性聚酯生产，一般采取先合成含羟基的聚酯树脂，再加人含有羟基的有机硅树脂，不同树脂的羟基间进行缩合反应，在反应时利用回流溶剂将缩合反应生成的水带出，使得缩合反应正常进行，反应达到规定的要求后，即可兑稀、过滤、包装。生产时要注意以下几点。  \n\n$\\textcircled{1}$ 聚酯树脂的生产和控制，涂料对涂膜的要求，主要依靠能够提供适宜性能的合成树脂来满足，聚酯分子链的结构、分子量分布等，会对改性树脂的性能造成影响。合成聚酯树脂若采用直链结构的多元醇和多元酸，改性聚酯树脂的柔韧性更好些，若采用含苯环结构的多元酸等，改性聚酯树脂的硬度会更好些，与其他树脂的混溶性也会更好。  \n\n$\\textcircled{2}$ 有机硅树脂预聚物的结构与组成，决定了硅树脂的产品性能与要求，进入聚酯树脂的分子链后，将影响硅改性聚酯树脂的性能，最终影响涂料的涂膜性能。要求有较高的耐热性，应选择侧链为苯基的有机硅树脂来改性；若要求有更高的抗水性、耐候性，应选择侧链为乙基、丙基等长链烷基的有机硅树脂来改性。  \n\n$\\textcircled{3}$ 从有机硅改性聚酯树脂的工艺控制上看，聚酯树脂达到一定分子量后，才能加人有机硅树脂，通过缩合反应完成接枝聚合。聚酯树脂反应程度，对改性树脂的形成非常关键，它直接影响到缩合反应的进行，并将影响产品的性能。应通过试验确定聚酯树脂反应程度，确保改性顺利进行。 Y  \n\n有机硅改性聚酯树脂具有良好的加工性能，生产的涂料具有优良的耐候性、抗腐蚀性、阻燃性、耐温性、电绝缘性及柔韧性，对基材附着力好、干燥快，不易粉化。有机硅改性聚酯树脂尽管成本要高一些，但比有机硅树脂、有机氟树脂要低很多，而且综合性能优异，有不亚于纯有机硅树脂、有机氟树脂的良好性能，有很好的市场前景。目前主要应用于高性能卷材涂料、绝缘涂料、重防腐涂料、耐高温涂料等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 269,
+        "chunk": "# 六、饱和聚酯树脂的应用  \n\n饱和聚酯树脂是涂料行业近年来发展迅速的树脂品种，与合适的交联剂配合形成综合性能优异的涂膜，有良好的户外耐候性和保光保色性，有较高的硬度、良好的韧性与附着力。与氨基或聚氨酯配套主要用于卷材涂料、汽车涂料，与环氧树脂配套主要用于生产粉末  \n\n涂料。  \n\n预涂卷材以冷轧钢板、镀锌钢板、铝板及其他金属板材为基板，厚度在0.1～0.5mm之间，经表面清洗、预处理后，经涂料涂装，烘烤成膜形成的复合材料。目前以辊涂方式进行涂装的居多，按卷材涂料所涂布的位置，习惯上可分为三类。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 270,
+        "chunk": "# 1.面漆  \n\n涂布在底漆上，与大气直接接触要求最高的涂层称为面漆。国内绝大多数卷材涂料生产商采用聚酯树脂作卷材涂料面漆的基体树脂，它通过选择合适的原料和合理的设计配方来平衡卷材面漆的各个要求。从分子结构上看，树脂结构中脂肪族和芳香族的合理搭配能够平衡涂料韧性和硬度的要求，分子中大量的酯基既为涂料提供了良好的附着力，也为涂料提供了韧性，这些结构上的特点是饱和聚酯树脂在卷材面漆中大量应用的保证。聚酯树脂可以和氨基树脂交联固化形成韧性和硬度平衡性好的涂膜，也可以选择封闭型聚氨酯作交联剂得到柔韧性和耐久性更好的涂膜。面漆通常采用的树脂体系有：氨基树脂-饱和聚酯体系、封闭型聚氨酯-饱和聚酯体系、氨基树脂-改性聚酯体系、氨基树脂-丙烯酸树脂体系等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 271,
+        "chunk": "# 2.背面漆  \n\n涂布在处理过的金属卷材背面的涂料，一般不涂底漆，也可以涂装约 $5\\mu\\mathrm{m}$ 的底漆后再涂背面漆，主要起保护作用。它要求不高，但是相对于底漆，它对耐候性、柔韧性和硬度有一定的要求。在被用于生产夹心板时，背面漆形成的涂层能否与夹心材料（常用聚氨酯发泡材料）很好的粘接，是评价背面漆性能的关键指标。通常采用的树脂体系有：氨基树脂-饱和聚酯体系、氨基树脂-环氧树脂体系等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 272,
+        "chunk": "# 3.底漆  \n\n直接涂布于预处理层之上的涂料称为底漆，需要考虑附着力、干性及成本，并具有适当的柔韧性和硬度。对耐候性、耐酸碱性、耐洗刷性无特别高的要求，主要为面漆提供基础和提高卷材的防腐蚀性。通常采用的树脂体系有：丁醚化脲醛树脂-环氧树脂体系、封闭型聚氨酯-饱和聚酯体系、高甲醚化氨基树脂-饱和聚酯体系等。  \n\n上述按涂布位置分类的方法对于铝箔用卷铝涂料来讲不恰当，铝箔上的卷铝涂料通常采用单涂层涂装工艺，一般没有底漆、面漆之分。目前市场此类用途的卷铝涂料，主要采用的树脂体系：氨基树脂-丙烯酸树脂体系、氨基树脂-合成脂肪酸改性聚酯树脂体系、氨基树脂-聚酯体系等。  \n\n卷材涂料与-般涂料不同，其客户有一定的针对性，在生产涂料过程中，一定要了解不同用户的要求。不同卷材流水线的状况不同，对涂膜性能、涂装工艺、施工条件等的要求各不相同，只有了解到客户要求，才能在生产涂料时有针对性的调整，对不同的用户要有相应的涂料配方，避免因用户的差异造成的影响。  \n\n卷材涂料的生产要经过一定工序，研磨分散是生产卷材涂料的第一道工序，调漆是生产卷材涂料的第二道工序，原料投人顺序是有一定要求的，一些原料在调漆时加人，一些原料在研磨分散时加人，研磨分散的要求、调漆的过程都是必须关注的。实际生产中，首先关注的是卷材涂料配方，同样的树脂体系，不同的配方组合，能生产出不同性能的涂料，卷材涂料的性能是设计配方时要注重的问题。  \n\n在设计卷材涂料配方时要综合考虑几个因素：原料的选择、各成分的比例、卷材流水线的条件等，以下提供几个卷材涂料配方供参考。  \n\n配方8：聚酯底漆  \n\n\n<html><body><table><tr><td>原料名称 用量/kg</td></tr><tr><td>配方4树脂 250</td></tr><tr><td>B101 60</td></tr><tr><td>锌铬黄 25</td></tr><tr><td>超细滑石粉 7.5</td></tr><tr><td>DBE 15</td></tr><tr><td>乙二醇丁醚 20</td></tr><tr><td>S-100溶剂 30</td></tr></table></body></html>  \n\n配方9：环氧改性聚酯底漆  \n\n\n<html><body><table><tr><td>原料名称 用量/kg</td></tr><tr><td>配方6树脂 300</td></tr><tr><td>R930 60</td></tr><tr><td>超细滑石粉 7.5</td></tr><tr><td>德铬黄 25</td></tr><tr><td>硫酸锌 15</td></tr><tr><td>DBE 20</td></tr><tr><td>乙二醇丁醚 25</td></tr></table></body></html>  \n\n<html><body><table><tr><td>原料名称 用量/kg</td></tr><tr><td>BYKP104S 1. 0</td></tr><tr><td>747 20</td></tr><tr><td>BL3175 10</td></tr><tr><td>20%1051 2.0</td></tr><tr><td>ADP 15</td></tr><tr><td>455.5</td></tr></table></body></html>  \n\n配方10：可用于快速线的海蓝面漆  \n\n\n<html><body><table><tr><td>原料名称 用量/kg</td></tr><tr><td>配方1树脂 260</td></tr><tr><td>R930 70</td></tr><tr><td>BS献菁 17.5</td></tr><tr><td>耐高温黄粉 0.5</td></tr><tr><td>蜡粉 1.5</td></tr><tr><td>醋酸丁酯 10</td></tr><tr><td>DBE 15</td></tr></table></body></html>  \n\n<html><body><table><tr><td>原料名称 用量/kg</td></tr><tr><td>S-100*溶剂 25</td></tr><tr><td>S-150*溶剂 20</td></tr><tr><td>904S 1. 0</td></tr><tr><td>747 25</td></tr><tr><td>20%1051 2.5</td></tr><tr><td>ADP 15</td></tr><tr><td>541</td></tr></table></body></html>  \n\n配方11：慢速线用低成本海蓝面漆  \n\n\n<html><body><table><tr><td>原料名称 用量/kg</td></tr><tr><td>配方7树脂 275</td></tr><tr><td>R930 60</td></tr><tr><td>BS菁蓝 15</td></tr><tr><td>超细高岭土 25</td></tr><tr><td>硫酸钡 10</td></tr><tr><td>丁醇 10</td></tr><tr><td>乙二醇丁醚 15</td></tr><tr><td>DBE 20</td></tr></table></body></html>  \n\n<html><body><table><tr><td>原料名称 用量/kg</td></tr><tr><td>乙二醇丁醚 20</td></tr><tr><td>S-150*溶剂 30</td></tr><tr><td>904S 2</td></tr><tr><td>747 30</td></tr><tr><td>20%1051 3.0</td></tr><tr><td>3777(或BYK310) 1. 0</td></tr><tr><td>460.5</td></tr></table></body></html>  \n\n<html><body><table><tr><td>原料名称 用量/kg</td></tr><tr><td>S-150*溶剂 35</td></tr><tr><td>904S 1.5</td></tr><tr><td>747 35</td></tr><tr><td>717 10</td></tr><tr><td>20%1051 5.0</td></tr><tr><td>3777(或BYK310) 1. 0</td></tr><tr><td>∑ 508.5</td></tr></table></body></html>  \n\n配方12：淡黄环氧底漆  \n\n\n<html><body><table><tr><td>原料名称 用量/kg</td></tr><tr><td>50%609环氧溶液 115</td></tr><tr><td>B101 57.5</td></tr><tr><td>锌黄粉 23</td></tr><tr><td>锶铬黄粉 4.5</td></tr><tr><td>超细滑石粉 8.8</td></tr><tr><td>DBE 6.0</td></tr><tr><td>大豆磷脂 1.6</td></tr><tr><td>乙二醇丁醚 45</td></tr></table></body></html>  \n\n<html><body><table><tr><td>原料名称 用量/kg</td></tr><tr><td>50%609环氟溶液 156</td></tr><tr><td>578-1氨基树脂 20</td></tr><tr><td>8%磷酸丁醇溶液 4.0</td></tr><tr><td>酰酸丁酯 15.3</td></tr><tr><td>乙二醇丁醚 19.4</td></tr><tr><td>环已酮 7.5</td></tr><tr><td>483.6</td></tr></table></body></html>  \n\n配方13：T弯可达 $\\mathbf{0}{\\sim}\\mathbf{1}\\mathbf{T}$ 的海蓝面漆  \n\n\n<html><body><table><tr><td>原料名称</td></tr><tr><td>用量/kg 配方2树脂 270</td></tr><tr><td>R930 70</td></tr><tr><td>BS献菁蓝 17.5</td></tr><tr><td>耐高温黄粉 0.5</td></tr><tr><td>消光粉 10. 0</td></tr><tr><td>蜡粉 1. 0</td></tr><tr><td>醋酸丁酯 15</td></tr><tr><td>乙二醇丁醚 30</td></tr></table></body></html>  \n\n<html><body><table><tr><td>原料名称 用量/kg</td></tr><tr><td>S-100溶剂 20</td></tr><tr><td>S-150*溶剂 35</td></tr><tr><td>BYKP104S 1. 0</td></tr><tr><td>747 15</td></tr><tr><td>717 7.5</td></tr><tr><td>20%1051 3.0</td></tr><tr><td>3777(或BYK310) 1. 0</td></tr><tr><td>496.5</td></tr></table></body></html>  \n\n配方14：环氧改性聚酯背面漆  \n\n\n<html><body><table><tr><td>原料名称 用量/kg</td></tr><tr><td>配方6树脂 250</td></tr><tr><td>B101 125</td></tr><tr><td>超细滑石粉 10</td></tr><tr><td>超细高岭土 30</td></tr><tr><td>黄粉 0.5</td></tr><tr><td>铁红 1.0</td></tr><tr><td>碳黑</td></tr><tr><td>适量 DBE 15</td></tr><tr><td>S-100*溶剂 30</td></tr></table></body></html>  \n\n<html><body><table><tr><td>原料名称 用量/kg</td></tr><tr><td>S-150\"溶剂 15</td></tr><tr><td>BYK110 1.5</td></tr><tr><td>747 15</td></tr><tr><td>578-1 40</td></tr><tr><td>10%磷酸 3.0</td></tr><tr><td>20%1051 3.6</td></tr><tr><td>ADP 15</td></tr><tr><td>554.6</td></tr></table></body></html>  \n\n配方15：可用于慢速线的海蓝面漆  \n\n\n<html><body><table><tr><td>原料名称 用量/kg</td></tr><tr><td>配方3树脂 270</td></tr><tr><td>R930 75</td></tr><tr><td>BS酸菁蓝 16</td></tr><tr><td>耐高温黄粉 0.5</td></tr><tr><td>消光粉 7.5</td></tr><tr><td>醋酸丁酯 15</td></tr><tr><td>DBE 10</td></tr><tr><td>乙二醇丁醚</td></tr><tr><td>25 S-100溶剂 25</td></tr></table></body></html>  \n\n<html><body><table><tr><td>原料名称 用量/kg</td></tr><tr><td>S-150*溶剂 30</td></tr><tr><td>BYKP104S 1.5</td></tr><tr><td>BYK163 1.5</td></tr><tr><td>747 40</td></tr><tr><td>20%1051 2.5</td></tr><tr><td>3777(或BYK310) 1. 0</td></tr><tr><td>BYK354 2.0</td></tr><tr><td>Z 522.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 273,
+        "chunk": "# 一、概述  \n\n丙烯酸树脂由丙烯酸酯类或甲基丙烯酸酯类及其他烯属单体（图2-1-15）共聚而成。通过选用不同的丙烯酸树脂、不同的颜料、助剂、溶剂及交联剂，可合成类型多样、性能各异和应用广泛的丙烯酸涂料。  \n\n![](images/8f27c23d0a7a32cac6111dbf123e5edd73e033fbee0fcaa36a12fa56388791c2.jpg)  \n图2-1-15用于丙烯酸树脂合成的主要单体结构  \n\n丙烯酸涂料是20世纪50年代开始发展起来的涂料品种，而丙烯酸酯单体早在1843年就已发现。1927年Rohm&Hass公司开始了丙烯酸酯的工业生产。1932～1934年，英、美等国逐步发展了甲基丙烯酸酯的工业化生产，1937年ICI公司实现甲基丙烯酸甲酯的工业化生产。50年代初期，美国DuPont公司开始研究聚丙烯酸酯漆并成功试用于汽车涂装。由于乙炔法（Reppe）合成丙烯酸酯的工业化生产获得成功，为聚丙烯酸酯提供了丰富的原料资源，使得丙烯酸酯涂料得到不断发展。到60年代末，丙烯氧化制造丙烯酸取得成功，进一步降低了原料成本。目前世界各大公司所生产的丙烯酸酯多数采用丙烯氧化方法，少数厂家仍采用改进了的Reppe法生产，甲基丙烯酸酯则一般采用丙酮氰醇法生产。2005年全球酯化级丙烯酸生产能力达到412.1万吨/a，丙烯酸酯生产能力373.4万吨/a。  \n\n我国的丙烯酸涂料研究始于60年代，80年代开始工业化过程。1984年，北京东方化工厂从日本触媒引进丙烯两步氧化技术及成套设备建成了我国第一套大型丙烯酸酯生产装置。90年代初吉林石化电石厂和上海高桥石化先后引进日本三菱化学技术，建成了两套装置。  \n\n丙烯酸类单体由于具有碳链双键和酯基的独特结构，共聚形成的丙烯酸树脂对光的主吸收峰处于太阳光谱范围之外，所以制得的丙烯酸涂料具有优异的耐光性及耐候性能。丙烯酸涂料有如下显著的特点。  \n\n$\\Phi$ 色浅、透明、水白、透明性好。  \n\n$\\textcircled{2}$ 耐候性：户外曝晒耐久性强，耐紫外光照射，不易分解或变黄，能长期保持原有的光泽及色泽。  \n\n$\\textcircled{3}$ 耐热性：在170℃下不分解、不变色，在 $230^{\\circ}\\mathrm{C}$ 左右或更高的温度下仍不变色。  \n\n$\\textcircled{4}$ 耐化学品性：有较好的耐酸、碱、盐、油脂、洗涤剂等化学品的沾污及腐蚀性能。  \n\n$\\textcircled{5}$ 优异施工性能：由于酯基的存在，能防止丙烯酸涂料结晶，多变的酯基还能改善有不同介质中的溶解性以及各种树脂的混溶性。  \n\n由于优越的耐光性能与耐户外老化性能，丙烯酸涂料最大的市场为轿车漆。此外，轻工、家用电器、金属家具、铝制品、卷材工业、仪器仪表、建筑、纺织品、塑料制品、木制品、造纸等工业均有广泛应用。  \n\n丙烯酸涂料种类繁多，目前通常分成溶剂型丙烯酸涂料、水性丙烯酸涂料和无溶剂丙烯酸涂料等，它们的主要用途见表2-1-83。  \n\n表2-1-83丙烯酸涂料品种及主要用途  \n\n\n<html><body><table><tr><td colspan=\"2\">涂料品种</td><td>主要用途</td></tr><tr><td rowspan=\"7\">溶剂型丙烯酸涂料</td><td>热塑性丙烯酸涂料</td><td>塑料用涂料、汽车修补漆、建筑外墙涂料</td></tr><tr><td>热固性丙烯酸涂料</td><td>依据固化剂的不同有不同的应用</td></tr><tr><td>羟基丙烯酸涂料</td><td>氨基树脂为固化剂，烘烤交联，主要用于汽车面漆、家用电 器、五金工具等 多异氰酸酯为固化剂，常温干燥，主要用于汽车面漆及修</td></tr><tr><td>环氧丙烯酸涂料</td><td>补漆，塑料、外墙、机器等面 多元酸、多元胺固化，常温或烘烤，用于罐头涂料</td></tr><tr><td>胺酸丙烯酸涂料</td><td>环氧或氨基树脂为固化剂，烘烤交联，主要用于罐头涂料</td></tr><tr><td>N-羟甲基丙烯酰胺涂料</td><td></td></tr><tr><td>水稀释型丙烯酸涂料</td><td>氨基树脂为固化剂，烘烤交联，主要用于金属底材 汽车电冰涂料、家用电器涂料、皮革涂料</td></tr><tr><td rowspan=\"2\">水性丙烯 酸涂料</td><td></td><td></td></tr><tr><td>乳液型丙烯酸涂料</td><td>建筑内外墙涂料、木器涂料</td></tr><tr><td rowspan=\"2\">无溶剂型 丙烯酸涂料</td><td>紫外光固化丙烯酸涂料</td><td>木器漆、纸张涂料、光纤涂料</td></tr><tr><td>丙烯酸粉末涂料</td><td>家用电器涂料、铝材轮毂涂料</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 274,
+        "chunk": "# 二、溶剂型丙烯酸树脂",
+        "category": " Introduction"
+    },
+    {
+        "id": 275,
+        "chunk": "# 1.树脂合成所用原材料  \n\n溶剂型丙烯酸树脂合成所用的原材料主要有四大类：单体、引发剂、溶剂和链转移剂，下面分别讨论。  \n\n(1）单体  \n\n$\\Phi$ 单体的分类与物理性质丙烯酸树脂合成所采用的单体主要有丙烯酸酯和甲基丙烯酸酯及其他含有乙烯基团的单体等。最常见的单体有丙烯酸、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸羟乙酯等。丙烯酸酯类按分子结构与应用可分为通用型丙烯酸酯和特种丙烯酸酯，像丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸-2-乙基已酯都有大规模工业化装置生产，属于通用丙烯酸酯；而丙烯酸异丁酯、丙烯酸羟乙酯、丙烯酸羟丙酯等生产规模相对较小，属于特种丙烯酸酯。它们的一些物理性能如分子量、折射率、沸点、相对密度、均聚体的玻璃化温度等列入表2-1-84中。  \n\n表2-1-84丙烯酸酶单体的物理性质及均聚物的玻璃化温度  \n\n\n<html><body><table><tr><td>名称及英文缩写</td><td></td><td>分子量折射率（25C）</td><td>沸点/C</td><td>相对密度（25C)</td><td>玻璃化混度T/K</td></tr><tr><td>丙烯酸（AA)</td><td>72.06</td><td>1.4185</td><td>141.6</td><td>1. 045</td><td>379</td></tr><tr><td>丙烯酸甲酯（MA)</td><td>86.09</td><td>1.401</td><td>80.3</td><td>0.950</td><td>281</td></tr><tr><td>丙烯酸乙酯（EA)</td><td>100.12</td><td>1.404</td><td>100</td><td>0. 917</td><td>251</td></tr><tr><td>丙烯酸丁酯(n-BA)</td><td>128.17</td><td>1.416</td><td>147.4</td><td>0.894</td><td>219</td></tr><tr><td>丙烯酸异丁酯(i-BA)</td><td>128.17</td><td>1.412</td><td>62(6. 7kPs)</td><td>0.884</td><td>249</td></tr><tr><td>丙烯酸-2-乙基已酯（EHA)</td><td>184.27</td><td>1.433</td><td>213.5</td><td>0.881</td><td>203</td></tr><tr><td>丙烯酸正辛酯</td><td>184.27</td><td>一</td><td>222</td><td>一</td><td>258</td></tr><tr><td>丙烯酸-β羟乙酶（β-HEA)</td><td>116.06</td><td>1.446</td><td>82(0. 7kPa)</td><td>1. 104</td><td>258</td></tr><tr><td>丙烯酸-β羟丙酯（β-HPA)</td><td></td><td>130.081. 445(20°C)</td><td>77(0. 7kPa)</td><td>1.057</td><td>266</td></tr><tr><td>丙烯酸缩水甘油酯（GA)</td><td>128.12</td><td>1.449</td><td>57(0. 3kPa)</td><td>1.107</td><td></td></tr><tr><td>丙烯酸异冰片酶(IBOA)</td><td>208.30</td><td>1. 504</td><td></td><td>0.984</td><td>363~373</td></tr><tr><td>甲基丙烯酸（MAA)</td><td>86.10</td><td>1.4288</td><td>163</td><td>1. 015</td><td>458</td></tr><tr><td>甲基丙烯酸甲酯（MMA)</td><td>100.12</td><td>1.4118</td><td>101</td><td>0.940</td><td>378</td></tr><tr><td>甲基丙烯酸乙酯（EMA)</td><td>114.15</td><td>1.4115</td><td>117</td><td>0.911</td><td>338</td></tr><tr><td>甲基丙烯酸异丙酯（i-PMA)</td><td>128.18</td><td>一</td><td>120</td><td>5</td><td>354</td></tr><tr><td>甲基丙烯酸正丁酯(π-BMA)</td><td>142.20</td><td>1.4220</td><td>163</td><td>0.889</td><td>295</td></tr><tr><td>甲基丙烯酸异丁酯（i-BMA)</td><td>142.20</td><td>1.4172</td><td>155</td><td>0.882</td><td>326</td></tr><tr><td>甲基丙烯酸己酶(π-HMA)</td><td>170.30</td><td>1.4920</td><td>184</td><td>0.880</td><td>268</td></tr><tr><td>甲基丙烯酸月桂酯（LMA)</td><td>254</td><td>1.444</td><td>160(0. 9kPa)</td><td>0.866</td><td>208</td></tr><tr><td>甲基丙烯酸十八酯</td><td>338.6</td><td>1.450</td><td>205(0. 7kPa)</td><td>0.858</td><td>311</td></tr><tr><td>甲基丙烯酸-β-羟乙酯（β-HEMA)</td><td>130.08</td><td>1. 4517</td><td>95(1. 333kPa)</td><td>1.079</td><td>328</td></tr><tr><td>甲基丙烯酸-β-羟丙酯（β-HPMA）</td><td>144.1</td><td>1.446</td><td>96(1. 333kPa)</td><td>1. 027</td><td>299</td></tr><tr><td>甲基丙烯酸缩水甘油酯（GMA)</td><td>142.15</td><td>1.4482</td><td>75(1.333kPa)</td><td>1.073</td><td>319</td></tr><tr><td>甲基丙烯酸异冰片酯（IBOMA)</td><td>222.33</td><td>1.475</td><td>117(0. 93kPa)</td><td>0.985</td><td>约411</td></tr></table></body></html>\n\n注：对于单体的一些物理性质，不同的书籍与文献有的差异甚大。  \n\n根据在树脂中的作用及对涂膜的贡献，丙烯酸类单体可以分为软单体和硬单体。软单体，例如丙烯酸甲酯、丙烯酸丁酯、丙烯酸-2-乙基己酯等。硬单体，例如甲基丙烯酸甲酯、甲基丙烯酸丁酯、苯乙烯和丙烯腈等。  \n\n丙烯酸类单体的分子中含有某些活性基因，如羟基、羧基、环氧基、氨基等，称为功能性单体。功能性单体可分为以下几类。  \n\na.含羧基单体，有丙烯酸、甲基丙烯酸、丁烯酸等。b.含羟基单体，有丙烯酸羟丙酯、丙烯酸羟乙酯、甲基丙烯酸羟丙酯、甲基丙烯酸羟乙酯、丙烯酸羟丁酯、甲基丙烯酸羟丁酯等。c.含环氧基单体，有丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯等。d.含叔氨基单体，有丙烯酸二甲氨基丙酯、丙烯酸二乙氨基丙酯、丙烯酸二甲氨基乙酯、甲基丙烯酸二甲氨基丙酯、甲基丙烯酸二乙氨基丙酯、甲基丙烯酸二甲氨基乙酯等。e.含酰氨基单体，有丙烯酸胺、N-羟甲基丙烯酸胺等。f.酯基碳链上含不饱和双键单体，有丙烯酸烯丙酯、甲基丙烯酸烯丙酯等。g.含杂环单体，有丙烯酸四氢呋喃甲酯、甲基丙烯酸四氢呋喃甲酯、丙烯酸乙氧化双环戊二烯酯等。h.含其他元素单体，有丙烯酸-2-氰基乙酯、丙烯酸羟乙基磷酸酯、丙烯酸氟烷基酯等。$\\textcircled{2}$ 单体与树脂性能关系丙烯酸涂料的涂膜性能主要取决于丙烯酸树脂合成用单体的结构与配比，表2-1-85～表2-1-88列出了丙烯酸酯单体在聚合物中的作用，对于配方的设计有一定的参考作用。  \n\n表2-1-85单体在树脂中的作用  \n\n\n<html><body><table><tr><td>单 体</td><td>在树脂中的作用</td></tr><tr><td>苯乙烯、丙烯腈、丙烯酸、甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯 酸异冰片酯</td><td>提高硬度、附着力，提高抗污染性</td></tr><tr><td>丙烯膀、丙烯酸、丙烯酰胺</td><td>提高耐油、耐溶剂性</td></tr><tr><td>丙烯酸乙酯、丙烯酸丁酯、丙烯酸-2-乙基己酯、丙烯酸十八烷基酯</td><td>提高柔顺性</td></tr><tr><td>丙烯酸十二烷基酯、丙烯酸十八烷基酯、苯乙烯</td><td>提高耐水性</td></tr><tr><td>甲基丙烯酰胺、丙烯腊</td><td>提高耐磨性、抗划伤性</td></tr><tr><td>甲基丙烯酸酯</td><td>提高耐候性、透明性</td></tr><tr><td>丙烯酸、甲基丙烯酸、丙烯酰胺、甲基丙烯酰胺、羟甲基丙烯酰胺、 丙烯酸羟乙酯、甲基丙烯酸缩水甘油酯</td><td>提高硬度、附着力、耐水性、耐油性、涂膜强度等</td></tr><tr><td>甲基丙烯酸芳香酯</td><td>增加光泽、提高鲜映性</td></tr></table></body></html>  \n\n表2-1-86苯乙烯与甲基丙烯酸甲酯物理性能比较  \n\n\n<html><body><table><tr><td>物理性能</td><td>苯乙烯</td><td>甲基丙烯酸甲酯</td><td>物理性能</td><td>苯乙烯</td><td>甲基丙烯酸甲酯</td></tr><tr><td>硬度</td><td>商</td><td>极高</td><td>耐光性</td><td>低</td><td>优</td></tr><tr><td>耐湿性</td><td>良好</td><td>低</td><td>保光性</td><td>尚好</td><td>优</td></tr><tr><td>耐污染性</td><td>良好</td><td>尚好</td><td>稀释性</td><td>良好</td><td>不好</td></tr></table></body></html>  \n\n表2-1-87丙烯酸乙酯、丙烯酸丁酯和丙烯酸异丁酯的性能比较  \n\n\n<html><body><table><tr><td>物理性能</td><td>比较</td><td>物理性能</td><td>比较</td></tr><tr><td>硬度</td><td>异丁酯-乙酯>丁酯</td><td>伸长率</td><td>异丁酯=乙酯<丁酯</td></tr><tr><td>增塑效果</td><td>异丁酯=乙酯<丁酯</td><td>耐芳烃性</td><td>异丁酯=丁酯<乙酯</td></tr><tr><td>拉伸强度</td><td>异丁酯=乙酯>丁酯</td><td>耐碱性</td><td>异丁酯=丁酯>乙酯</td></tr><tr><td>耐水性</td><td>异丁酯=丁酯>乙酯</td><td></td><td></td></tr></table></body></html>  \n\n表2-1-88各类聚合物涂层物理性能  \n\n\n<html><body><table><tr><td>物理性能</td><td>甲基丙烯酸甲酯</td><td>甲基丙烯酸丁酯</td><td>丙烯酸乙酯</td><td>丙烯酸丁酯</td><td>丙烯酸-2-乙基已酯</td></tr><tr><td>黏性</td><td>没有</td><td>稍软，有塑性</td><td>有</td><td>黏</td><td>极黏</td></tr><tr><td>硬度</td><td>硬</td><td>低</td><td>软、有塑性</td><td>很软</td><td>很软，无塑性</td></tr><tr><td>拉伸强度</td><td>高</td><td>低</td><td>低</td><td>很低</td><td>异常低</td></tr><tr><td>伸长率</td><td>低</td><td>高</td><td>很高</td><td>异常高</td><td></td></tr><tr><td>附着力</td><td>低</td><td>良好</td><td>优良</td><td>还好</td><td>低</td></tr><tr><td>耐溶剂性</td><td>耐汽油好</td><td>良好</td><td>很好</td><td>还好</td><td>低</td></tr><tr><td>耐湿热性</td><td>低</td><td>优</td><td>劣</td><td>一般</td><td>优</td></tr><tr><td>保光性</td><td>优</td><td>很好</td><td>良好</td><td>尚可</td><td>劣</td></tr><tr><td>抗冷冻性</td><td>很坏</td><td>低</td><td>坏</td><td>良好</td><td>优</td></tr><tr><td>抗紫外线</td><td>优</td><td>很好</td><td>尚可</td><td>良好</td><td>良好</td></tr></table></body></html>  \n\n除了表中列举的相应关系外，我们补充说明讨论如下。  \n\na.耐候性丙烯酸酯含有叔氢原子，而甲基丙烯酸酯不含叔氢原子，因此甲基丙烯酸脂对光和氧的作用较丙烯酸酯稳定，耐候性也优于丙烯酸酯类。  \n\n在各种异构体丙烯酸酯中，叔碳是最稳定的，异丁酯不如正丁酯稳定。因为异丁基上叔碳原子上的氢原子容易被提取，聚合时易产生分支，也较易光老化。同样，丙烯酸2-乙基已基酯也存在同样的问题。  \n\n丙烯酸酯和甲基丙烯酸酯均不含共轭双键，因此它们的耐候性优于苯乙烯。将甲基丙烯酸甲酯与苯乙烯比较，苯乙烯赋予漆膜光泽、丰满度和鲜映度；甲基丙烯酸甲酯赋予漆膜耐候性和透明性。由于苯乙烯价格较丙烯酸酯类单体便宜，在配方设计时，常用一些苯乙烯单体代替甲基丙烯酸甲酯。但在苯乙烯中，与苯环相连的碳原子容易被氧化，引起主链断裂生成发色基团，因此含苯乙烯单体多的丙烯酸树脂容易发黄、保色性也要差。  \n\n苯乙烯的含量对其最终产品的耐候性影响极大，在使用时，要正确地把握好它的用量范围。一般情况下，在用作汽车之类对户外耐候性、装饰性要求较高的场合，丙烯酸类共聚物中苯乙烯的含量不得高于 $15\\%$ 垂  \n\nb.漆膜硬度漆膜的硬度与单体均聚物的玻璃化温度有密切关系，一般玻璃化温度越高，漆膜的硬度越高；反之，则越柔软。定性上，均聚物的玻璃化温度与其单体结构有如下的规律。  \n\n(a）聚甲基丙烯酸酯的 $T_{\\mathrm{s}}$ 一般比相应的聚丙烯酸酯高，原因在于聚甲基丙烯酸酯中a-甲基的存在使碳-碳链的旋转位阻增大，刚性增强，从而玻璃化温度较高。  \n\n（b）对于聚合物烷基异构体，一般异构化程度越高， $\\boldsymbol{T_{\\mathrm{s}}}$ 越高。例如聚丙烯酸丁酯有四个酯基异构体：正丁酯、异丁酯、仲丁酯和叔丁酯，它们的脆化温度（使聚合物在冲击载荷作用下变为脆性破坏的温度，称为脆化温度。脆化温度是聚合物能够正常使用的温度下限，低于脆化温度的聚合物丧失其柔韧性，性脆易折，无法正常工作）分别为：一45℃、$-24\\tt C$ 、-10℃和40℃。  \n\n(c）聚合物的玻璃化温度随烷基碳原子数的变化而变化。对于聚甲基丙烯酸酯，其脆化温度随着烷基碳原子数的增加而下降，但以十二碳酯为最低，然而又重新升高。聚丙烯酸酯的脆化温度的最低点是八碳酯。  \n\n(d）聚苯乙烯的 $T_{*}$ 为 $100^{\\circ}\\mathrm{C}$ 与聚甲基丙烯酸甲酯相近，因此用苯乙烯代替部分甲基丙烯酸甲酯，漆膜硬度相近，但延展性会变差。  \n\n涂膜的硬度与树脂的玻璃化温度密切相关，在单体组成相同时，树脂的玻璃化温度与树脂的分子量有关，一般分子量越大， $T_{\\mathrm{s}}$ 越高，但分子量超过一定值时， $T_{\\mathrm{*}}$ 趋于恒定，参见图2-1-16。  \n\nc.伸长率和拉伸强度树脂的拉伸强度会随着烷基碳链的增长而下降，但伸长率则会大幅度增长。聚丙烯酸酯的拉伸强度比聚甲基丙烯酸酯小，但伸长率则要高许多。一般而言，聚甲基丙烯酸甲酯的拉伸强度可达到50～77MPa水平，弯曲强度可达到90～130MPa，而其断裂伸长率仅 $2\\%\\sim3\\%$ 。侧基长度对聚合物性能的影响见表2-1-89。  \n\n![](images/af875baa328a3fc3b040973bf2c11390ed7276abd0734a7f8a80260817cae83e.jpg)  \n图2-1-16分子量与玻璃化温度关系  \n\n表2-1-89侧基长度对聚合物性能的影响  \n\n\n<html><body><table><tr><td>聚合物</td><td>拉伸强度/MPa</td><td>断裂伸长率/%</td><td>聚合物</td><td>拉伸强度/MPa</td><td>断裂伸长率/%</td></tr><tr><td>聚丙烯酸甲酯</td><td>6.93</td><td>750</td><td>聚甲基丙烯酸甲酯</td><td>68.9</td><td>1</td></tr><tr><td>聚丙烯酸乙酯</td><td>0.23</td><td>1800</td><td>聚甲基丙烯酸乙酯</td><td>37.2</td><td>25</td></tr><tr><td>聚丙烯酸丁酯</td><td>0.02</td><td>2000</td><td>聚甲基丙烯酸丁酯</td><td>3.44</td><td>300</td></tr></table></body></html>  \n\nd.耐介质性能丙烯酸酯类单体其侧基可以有不同的功能基团，导致其极性及溶解性差异较大。  \n\n树脂的耐水性与侧基碳数的多少有很大关系。丙烯酸酯的主链是不会被水解的，但其侧链上许多酯基则有较大的水解性。酯基碳链越长，极性越小，亲水性越小，耐汽油性变差，但耐水性变好；酯基碳链越短，极性越大，耐汽油性越好，但耐水性越差。甲基丙烯酸酯类单体的耐水性比丙烯酸酯类单体好。  \n\n聚丙烯酸酯含有叔氢原子，反应活性高，因此，其水解稳定性比聚甲基丙烯酸酯差。  \n\n丙烯酸正丁酯、异丁酯和叔丁酯玻璃化温度相差很远，化学性能也差别很大，异丁酯的耐水性优于正丁酯，而叔丁酯对酸水解十分敏感。  \n\n树脂的耐酸雨性能是大家所关心的问题。从单体的角度看，一般说来丙烯酸酯单体中高碳酯（4个碳原子以上）比低碳酯有利；（甲基）丙烯酸环烷酯、芳烃酯比直链烃有利；叔碳酸缩水甘油酯等改性丙烯酸树脂也能明显提高耐酸雨性；羟基单体中（甲基）丙烯酸羟丙酯比（甲基）丙烯酸羟乙酯有利；苯乙烯、甲基苯乙烯比丙烯酸单体为好。  \n\ne.单体功能基的作用若在树脂中引人功能基团，可以进一步改进树脂的性能。引人极性较大的羟基、羧基、氰基等可以不同程度地改进树脂的附着力、耐汽油性及耐溶剂性。但要注意引入功能基的种类和数量要与树脂的应用相结合。若引入过多的羟基或羧基往往会降低树脂的耐水性；过多的氰基则会降低树脂的溶解性。  \n\n此外，含叔氨基丙烯酸类聚合物可赋予聚合物良好的混溶性能，使该品种的丙烯酸类聚合物可与绝大多数涂料用合成树脂混溶，利用该类树脂的这一特征，可把它用作所谓“通用色浆”的研磨树脂等。  \n\n表2-1-90给出了丙烯酸树脂与其他树脂的相容性。根据极性相似相容原理，若丙烯酸树脂的极性与被混合树脂极性相似时，容易混溶。一般来说，用硬单体合成的树脂其相容性不如软单体合成的树脂好，但在配方中引入部分苯乙烯对改进树脂的相容性有增进作用。  \n\n表2-1-90丙烯酸树脂与其他树脂的相容性  \n\n\n<html><body><table><tr><td>其他树脂</td><td>硬丙烯酸树脂</td><td>软丙烯酸树脂</td><td>其他树脂</td><td>硬丙烯酸树脂</td><td>软丙烯酸树脂</td></tr><tr><td>醋丁纤维</td><td>部分相容</td><td>相容</td><td>氯醋共聚体</td><td>部分相容</td><td>相容</td></tr><tr><td>硝化棉</td><td>部分相容</td><td>相容</td><td>氯化橡胶</td><td>不相容</td><td>不相容</td></tr><tr><td>乙基纤维</td><td>不相容</td><td>不相容</td><td>丙烯酸改性醇酸</td><td>不相容</td><td>相容</td></tr><tr><td>聚氯乙烯</td><td>相容</td><td>相容</td><td></td><td></td><td></td></tr></table></body></html>  \n\n$\\textcircled{3}$ 阻聚剂丙烯酸酯类单体在强光照射下及受热情况下很容易发生聚合反应，若不加阻聚剂只能在 $10\\Upsilon$ 以下的环境贮存数个星期，因此为了方便贮存及运输，单体中往往加入一定量的阻聚剂来防止单体聚合。最常用的阻聚剂是酚类化合物，但它们必须在有氧存在下才能发挥作用。目前较常用的酚类阻聚剂是对甲氧基苯酚。对甲氧基苯酚阻聚剂的用量比用对苯二酚少些（用量常可少至 $10\\mathrm{{\\sim}30m g/k g)}$ ，聚合反应时诱导期较短，可很快消失阻聚作用，聚合反应的重现性好；在碱性条件下，这种阻聚剂不会出现着色现象。在单体含水分等杂质少的情况下，用量可少些，但当有活性官能团取代的单体时，用量要多些。在丙烯酸酯或甲基丙烯酸酯连续蒸馏过程中，如注入氧气仍不能阻止聚合时，则可预先加对苯二酚和苯，两者配合使用时阻聚效果特别好。  \n\n除酚类阻聚剂外，还有吩噻嗪、亚甲基蓝、对羟基二苯胺、N， $N^{\\prime}$ 二苯基对苯二胺、2,5-二叔丁基氢醒等，后几种常在高温情况下应用。  \n\n含适量对甲氧基苯酚的单体在进行聚合反应时一般不必除去，原因是在不长的诱导期后，聚合反应能正常进行；在必须除去对苯二酚或对甲氧基苯酚等阻聚剂时，可以使用蒸馏法、碱洗法或离子交换树脂法等。  \n\n$\\textcircled{4}$ 单体贮存在丙烯酸酯单体贮存过程中，应着重注意：防火防爆，防聚合，防毒。由于绝大多数单体系低毒或微毒，所以防火、防爆以及防聚合是贮运中的关键。丙烯酸酯单体可以桶装运，也可以槽装运，所有单体均应使用不透光的桶包装；贮槽可用低碳钢或铝制造，贮槽应安装温度报警、通风装置、干燥器，以及配备各种工艺管道及装置以保持空气流通、防止潮气及水分进入，保证安全。丙烯酸酯单体常用200L铁桶装运，酸类单体使用的铁桶内部衬以聚乙烯，防止酸的腐蚀。桶装单体应避免阳光直接照射，如在户外存放应搭建凉棚遮阳。放置单体的建筑物应符合防火防爆安全规定。苯乙烯和甲基丙烯酸甲酯容易聚合，存放时间短，贮存时应加以注意。气候寒冷时，丙烯酸及其甲基丙烯酸应在 $16\\sim24^{\\circ}C$ 存放，防止结晶；若发生结晶，结晶体中不含阻聚剂及氧气，容易聚合。  \n\n$\\textcircled{5}$ 单体的检验工业生产的丙烯酸酯单体常常含有少量杂质或阻聚剂，因此丙烯酸酯的含量一般达不到 $99\\%$ ，某些杂质如水分、聚合物等含量超过一定标准会影响成品树脂的品质，应该加以严格控制。  \n\n单体检验是制造丙烯酸树脂前的重要步骤，直接影响到树脂制造的质量。单体的检验一般包括纯度、酸值、阻聚剂以及单体中聚合物的测定，可采用仪器分析或化学分析方法等。  \n\na.纯度的测定丙烯酸酯的纯度可用全酯值或不饱和度来表示，全酯值包括丙烯酸酯以及其他酯的含量，因此如果原料中含有其他饱和羧酸酯时，应该用不饱和度数来复验。  \n\n·方法1——全酯值测定法。皂化值的测定：准确称量 $0.5\\sim3.08$ 试样放在锥形瓶中，并加入50mL0.5mol/LKOH乙醇溶液，在锥形瓶上安装上回流冷凝器，缓缓加热使溶液沸腾1h；将锥形瓶冷却到室温，用酚类指示剂及 $0.5\\mathrm{{mol/L}}$ 盐酸水溶液滴定至粉红色消失为止。  \n\n计算公式： 皂化值=（A-B)X0.5×56.05m  \n\n式中 $\\boldsymbol{A}$ —空白试验盐酸耗用量，mL；$B$ —加入试样盐酸耗用量，mL；$m$ 试样质量，mg。  \n\n·方法2——-全不饱和度分析法。全不饱和度的分析原理如下：丙烯酸酯与吗啉反应会生成叔胺：  \n\n过量的吗啉与醋酐反应生成酰化物。  \n\n生成的叔胺在非水溶液中例如乙二醇甲醚溶剂中用高氯酸滴定。  \n\n0.5mol/L高氯酸乙二醇甲醚溶液配制。将 $40\\mathrm{mL}70\\%\\sim72\\%$ 的高氯酸加入装有 ${\\mathsf{50m L}}$ 乙二醇甲醚的 $1000\\mathrm{mL}$ 容量瓶中，用乙二醇甲醚稀释到刻度，摇匀；将 $1,2_{\\mathsf{E}}$ 三羟甲基氨基甲烷溶于纯水作为标准溶液；用 $1\\%$ 的溴甲酚氯的甲醇溶液做指示剂标定。  \n\n百里酚蓝、二甲苯蓝混合指示剂的配制。称取 $0,3{\\bf g}$ 百里酚蓝和 $0.08\\mathbf{g}$ 二甲苯蓝溶于$100\\mathrm{mL}$ 二甲基甲酰胺备用。  \n\n实验方法：用量简分别量取 $10\\mathrm{mL}$ 吗啉并加人到试样瓶与空白瓶中，称取 $_{1\\sim48}$ 试样加入到瓶中（精确到 $0.1\\mathrm{m}g)$ ，混合均匀；在各瓶中加人无水甲醇 $10\\mathrm{mL}$ ，室温放置 $10\\mathrm{{min}}$ ，再用量简向各瓶中分别加入 ${\\mathsf{50m L}}$ 乙二醇甲醚，边搅拌边用量筒在各瓶中加人 $_{20\\mathrm{mL}}$ 精制的醋酐，冷却至室温；各瓶中加人混合指示剂 $6\\sim8$ 滴，用 $0.5\\mathrm{{mol/L}}$ 高氯酸乙二醇甲醚溶液滴定至绿色消失为终点。  \n\n全不饱和度(质量分数)=(A-B)X0.5X0.1×M式中 $\\boldsymbol{A}$ —试样所消耗的高氯酸体积，mL；B-—空白所消耗的高氯酸体积，mL；$M$ ——酯单体的分子量；$m$ -试样质量，g。  \n\n上述方法适于分析丙烯酸酯；如要分析甲基丙烯酸酯及酸类单体时，则用醋酸作为催化剂，分析操作时称样 $1.3\\sim1.5\\mathrm{g}$ ，不加甲醇而改为加人 $50\\%$ 的醋酸水溶液 $7\\mathrm{mL}$ ，然后在$(98\\pm2)0$ 水浴中保温半小时，冷却后按以上例子类似步骤进行操作。  \n\n丙烯酸含量(质量分数)=(A-B)X0.5X7.206 m  \n\n式中符号意义与上式相同。  \n\nb.酸值测定称 $_{10\\sim15g}$ 试样放入锥形瓶中，用移液管加人 $_{100\\mathrm{mL}}$ $80\\sim90^{\\circ}C$ 蒸馏水，加盖并摇匀，放置2h，过滤并置于锥形瓶。用移液管吸取 $25\\mathrm{mL}$ 滤液放入另一锥形瓶中，加酚指示剂 $2{\\sim}3$ 滴，用 $0.04\\mathrm{mol/L}$ 氢氧化钠-乙醇溶液滴定，直至试液呈粉红色，10s内不消失为滴定终点。  \n\n酸值计算公式为：  \n\n式中K—酸值， $\\mathrm{mg\\KOH/g}$ $N$ —氢氧化钠-乙醇溶液浓度，mol/L；V—滴定氢氧化钠-乙醇溶液体积，mL;G—试样质量，g。  \n\n测定时两次平行试验结果之差与平均值之比应小于 $3\\%$  \n\nc.对甲氧基苯酚含量的测定在酸性条件下对甲氧基苯酚与亚硝酸盐生成黄色的亚硝基化合物，这种化合物在 $405\\mathrm{nm}$ 波长时有最大吸光度，不过为避免亚硝酸所造成的背景干扰，一般在 $420\\mathrm{nm}$ 波长处进行测定。  \n\n操作时将试样溶于二甲基甲酰胺中，用亚硝酸及盐酸进行处理，生成亚硝基化合物，然后在 $420\\mathrm{nm}$ 波长下进行比色分析。丙烯酸丁酯及丙烯酸-2-乙基已酯在二甲基甲酰胺中溶解度很小，可用氯仿将对甲氧基苯酚萃取出来，再进行亚硝化及比色测定。  \n\nd.单体的气相色谱法分析利用气相色谱仪可以分析各种单体的纯度以及甲酸酯、醋酸酯、醛、醇等各种杂质的含量，通过标准曲线的绘制或色谱分析资料查阅等，对丙烯酸酯进行纯度分析。目前在中等规模的树脂合成厂利用气相色谱对丙烯酸酯进行纯度检验是一项常规工作。  \n\ne.单体中聚合物的测定由于单体会发生聚合，因此单体中或多或少有聚合物存在，单体中聚合物的测定可利用聚合物在某些溶剂中不溶解产生浑浊来加以判断。检验单体中聚合物时选用的溶剂可参见表2-1-91。  \n\n表2-1-91检验单体中聚合物时选用的溶剂  \n\n\n<html><body><table><tr><td>单 体</td><td>溶剂</td><td>单体</td><td>效置时间</td></tr><tr><td>丙烯酸甲酶、丙烯酸乙酯</td><td>醋酸-水(体积比1：1)</td><td>2·98</td><td>5</td></tr><tr><td>丙烯酸丁酯</td><td>甲醇</td><td>2· 98</td><td>5</td></tr><tr><td>丙烯酸-2-乙基己酯</td><td>甲醇</td><td>3·10</td><td></td></tr><tr><td>甲基丙烯酸甲酯、甲基丙烯酸乙酶、甲基丙烯酸丁酶、甲基丙烯酸月桂酯</td><td>甲醇</td><td>2·98</td><td>5</td></tr><tr><td>甲基丙烯酸</td><td>25%氯化钠水溶液</td><td>10·10</td><td>15</td></tr><tr><td>苯乙烯</td><td>甲醇</td><td>1:5</td><td>5</td></tr></table></body></html>  \n\n$\\textcircled{6}$ 单体的毒性毒性通常用急性毒性、亚慢性毒性、慢性毒性、致突变作用、致癌作用、生殖发育毒性等来综合评价。  \n\n丙烯酸和甲基丙烯酸对眼睛腐蚀严重，吞食时尽管较温和，但它可能严重烧伤肠道及损伤消化系统。丙烯酸的蒸气对眼睛、黏膜和皮肤都有刺激作用；而甲基丙烯酸仅适度地刺激眼睛，对鼻、喉、皮肤稍有刺激性影响，高浓度接触可能引起肺部病变，可引起肺、肝、肾的慢性损伤。  \n\n丙烯酸酯类单体属于微毒至中毒性。关于慢性口服毒性，用狗和兔做长期非致死剂量的给药试验证明，丙烯酸酯单体无积累作用。在吞人、与眼黏膜接触或通过皮肤吸收时，实验证明液体丙烯酸甲酯及乙酯属中毒类，眼角膜特别敏感易受损伤；高级酯的毒性较温和；甲基丙烯酸甲酯属低毒类，但对皮肤的敏感性较强，接触时间长可致麻醉作用。  \n\n丙烯酸甲酯及乙酯的蒸气有催泪及刺激黏膜的作用，即使空气中的浓度低至 $50\\sim$  \n\n70mg/m时，长时期作用也会造成不良后果，如角膜损伤以及嗜睡、头痛、恶心等神经系统中毒症状；高浓度接触严重者可因肺水肿而死亡。丙烯酸甲酯误服急性中毒者，会出现口腔、胃、食管腐蚀症状，并有虚脱、呼吸困难等；丙烯酸乙酯误服强烈刺激口腔和消化道，可出现头晕、呼吸困难和神经过敏。  \n\n官能团取代的酯类毒性较大，例如丙烯酸羟丙酯的毒性大于丙烯酸乙酯而接近于丙烯酸甲酯；甲基丙烯酸羟丙酯的毒性较低，接近高级酯类。羟基酯应用很广，目前国内各生产厂对羟基酯的毒性无足够的认识，防范不够，应引起重视。丙烯酸缩水甘油酯是丙烯酸酯类单体中毒性最大的，1%的稀溶液也会严重地损伤眼膜，其蒸气会灼伤眼睛，接触皮肤时将有严重刺激或灼伤，吸入其蒸气尽管不是极大量，有时也是致命的。由于丙烯酸缩水甘油酯在生产中使用有明显增加趋势，因此丙烯酸缩水甘油酯的容器上应该有毒品警告标志。甲基丙烯酸缩水甘油酯的毒性稍低，与丙烯酸乙酯相似，有时会引起皮炎或过敏。  \n\n氨基烷基取代酯兼有胺及丙烯酸化合物的毒性，既有口服毒性，又会对眼睛和皮肤造成灼伤；其甲基丙烯酸酯的毒性稍低。  \n\n车间中容许的丙烯酸酯类单体最高浓度见表2-1-92。  \n\n表2-1-92车间中容许的丙烯酸酯类单体最高浓度  \n\n\n<html><body><table><tr><td>物质名称</td><td>最高容许浓度/（mg/m）</td><td>物质名称</td><td>最高容许浓度/（mg/m）</td></tr><tr><td>丙烯酸</td><td>6</td><td>丙烯酸正丁酯</td><td>10</td></tr><tr><td>丙烯睛</td><td>2</td><td>丙烯酸乙酶</td><td>10</td></tr><tr><td>丙烯酸甲酯</td><td>20</td><td>甲基丙烯酸</td><td>20</td></tr><tr><td>甲基丙烯酸甲酯</td><td>30</td><td>a-氰基丙烯酸甲酯</td><td></td></tr><tr><td>甲基丙烯酸环氧丙酯</td><td>5</td><td>苯乙烯</td><td>40</td></tr><tr><td>顺丁烯二酸酐</td><td>1</td><td>丙烯酰胺</td><td>0.3(皮）</td></tr><tr><td>丙烯酸异丁酯</td><td>10</td><td></td><td></td></tr></table></body></html>  \n\n(2）引发剂引发剂的分解速率常用半衰期即引发剂分解到起始浓度的一半所需要的时间来表示。常见的引发剂以及在一定温度下的半衰期列入表2-1-93。  \n\n表2-1-93一些引发剂的半衰期和最佳使用温度  \n\n\n<html><body><table><tr><td>引发剂</td><td>温度/℃</td><td>半衰期</td><td>最佳温度范围/℃C</td></tr><tr><td rowspan=\"4\">偶氮二异丁晴</td><td>64</td><td>10h</td><td rowspan=\"4\">75~90</td></tr><tr><td>82</td><td>60min</td></tr><tr><td>100</td><td>6min</td></tr><tr><td>120</td><td>1min</td></tr><tr><td rowspan=\"4\">过氧化苯甲酰</td><td>80</td><td>4h</td><td rowspan=\"4\">90~100</td></tr><tr><td>90</td><td>1.25h</td></tr><tr><td>100</td><td>25min</td></tr><tr><td>110</td><td>8.5min</td></tr><tr><td rowspan=\"4\">叔丁基过氧化新戊酰</td><td>60</td><td>6h</td><td rowspan=\"4\">P 70~80</td></tr><tr><td>70</td><td>1. 25h</td></tr><tr><td>80</td><td>20min</td></tr><tr><td>90</td><td>9min</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>引发剂</td><td>温度/C</td><td>半衰期</td><td>最佳温度范围/C</td></tr><tr><td rowspan=\"5\">叔丁基过氧化苯甲酰</td><td>110</td><td>5.5h</td><td rowspan=\"5\">115~130</td></tr><tr><td>120</td><td>1.75h</td></tr><tr><td>130</td><td>35min</td></tr><tr><td>140</td><td>12min</td></tr><tr><td>150</td><td>4.5min</td></tr><tr><td rowspan=\"4\">过氧化二叔丁基</td><td>130</td><td>6h</td><td rowspan=\"4\">140~150</td></tr><tr><td>140</td><td>2h</td></tr><tr><td>150</td><td>40min</td></tr><tr><td>160</td><td>15min</td></tr></table></body></html>  \n\n引发剂的分解反应式如下：  \n\n偶氮二异丁晴  \n\n$$\n\\frac{R}{R-\\underset{i}{C}-N-N-\\underset{i}{C}-R}=\\underset{C N}{C}+N\n$$  \n\n过氧化苯甲酰  \n\n过氧化叔丁基苯甲酰  \n\n过氧化二叔丁基  \n\n$$\n\\begin{array}{r}{\\begin{array}{c c c c}{\\mathrm{CH_{3}}}&{\\mathrm{CH_{3}}}&{\\mathrm{CH_{3}}}\\\\ {\\downarrow}&{\\downarrow}&{}\\\\ {\\mathrm{H_{3}C-C-O-O-C-C H_{3}}}&{\\longrightarrow}&{2\\mathrm{H_{3}C-C-O^{*}}}\\\\ {\\downarrow}&{\\downarrow}&{}&{\\downarrow}\\\\ {\\mathrm{CH_{3}}}&{\\mathrm{CH_{3}}}&{}&{\\mathrm{CH_{3}}}\\end{array}}\\end{array}\n$$  \n\n叔丁基过氧化氢  \n\n$$\n\\mathrm{\\Delta_{H_{3}C-\\stackrel{j}{C-}-0-j-O H}^{C H_{3}}-\\Delta_{H_{3}C-\\stackrel{j}{C-}-O}^{C H_{3}}+O H}\\cdot\n$$  \n\n常用的引发剂有两大类：有机过氧化物和偶氮化合物。有机过氧化物品种繁多，热分解活性范围很宽，在不同的聚合温度均能找到合适活性的品种，同时多数为液体，也有固态。固体类引发剂也能较好地溶解在丙烯酸单体或溶剂中。所以，有机过氧化物引发剂是主要的自由基聚合引发剂，约占引发剂总量的 $90\\%$ 左右。常用的有机过氧化物引发剂有以下几种。  \n\n$\\Phi$ 酰类如过氧化乙酰、过氧化月桂酰、过氧化苯甲酰。$\\textcircled{2}$ 醚类如过氧化二叔丁基醚、过氧化二叔戊基醚、过氧化二异丙苯醚。$\\textcircled{3}$ 酯类如过氧化乙酸叔丁酯、过氧化苯甲酸叔丁酯、过氧化苯甲酸叔戊酯、过氧化2-乙基己酸叔丁酯、过氧化-2-乙基己酸叔戊酯。  \n\n$\\textcircled{4}$ 酮类如过氧化甲乙酮、过氧化环已酮。  \n\n$\\textcircled{5}$ 过氧化氢类如叔丁基过氧化氢、异丙苯基过氧化氢。  \n\n适用于丙烯酸溶液聚合的偶氮化合物引发剂多为晴类偶氮化合物，常用的有偶氮二异丁睛（AIBN)、2,2-偶氮二（甲基丁晴)、2,2-偶氮（2,4-二甲基戊睛）等。  \n\n不同的引发剂有不同的分解温度和半衰期。在确定的反应体系中，引发剂的分解温度过高或半衰期过长会造成聚合反应的时间过长，不利于生产。反之，引发剂的分解温度过低或半衰期过短，单位时间内产生自由基的数量过多，反应速度加快。由于自由基聚合反应是一个放热反应，因而会导致反应温度难以控制而产生爆聚或过早停止反应。  \n\n在选择引发剂时，应考虑引发剂的引发效率，以BPO和ABIN为例：引发剂分解生成的自由基并非全部参与链增长反应，因为部分引发剂自由基可能发生相互结合的副反应生成一种新的化合物，从而使部分引发剂失效。  \n\n偶氮系引发剂分解后产生弱夺氢反应能力的选择性自由基。这类自由基的活性较低，不太容易发生向溶剂链转移之类的副反应，所以相对比较简单，如偶氮二异丁睛的副反应如下：  \n\n$$\n\\begin{array}{r l}&{\\mathrm{CH_{3}}}\\\\ &{\\mathrm{~\\begin{array}{l}{{\\mathrm{CH_{3}}}}\\\\ {{\\mathrm{2CH_{3}}-{\\mathrm{C-N\\cdot}}}\\\\ {{\\mathrm{~\\left[~{\\begin{array}{l}{{C-N}\\end{array}}-\\right.}}\\\\ {{\\mathrm{~\\left.~{C}~}\\right]}}\\end{array}}}\\end{array}}}\\end{array}\\begin{array}{r l}{\\mathrm{CH_{3}\\thinspace C H_{3}}}\\\\ {{\\mathrm{~\\left.~{CH_{3}}-{\\mathrm{~{C-CH_{3}}}}\\right.}}}\\end{array}\n$$  \n\n偶氮类引发剂的热解，生成自由基的反应较简单，不发生诱导分解，在不同溶剂中的分解速率常数相差不大，均呈一级反应，所以在某些诱导分解作用较明显的溶剂中，带氨基的官能团单体中，或用硫醇为链转移剂时，采用偶氮引发剂能取得更好的效果。  \n\n有机过氧化物的情况就稍微复杂一些，它们除了相互间结合的副反应外还可能发生诱导分解反应， $\\mathbf{C}_{6}\\mathbf{H}_{5}\\mathbf{COO}\\cdot$ 和 $\\mathbf{C}_{6}\\mathbf{H}_{5}$ ·这两种自由基自身以及相互间都可能发生结合反应。这些结合反应一部分使自由基还原成过氧化苯甲酰，一部分则生成了新的稳定化合物。  \n\n另外，自由基 $\\mathbf{C_{6}H_{5}}$ ·还能使过氧化苯甲酰发生以下诱导反应：  \n\n显而易见，这些可能发生的副反应在消耗了自由基的同时，也在一定程度上减缓了自由基生成的速率，降低了引发效率。  \n\nBPO分解的自由基很容易进攻聚合物，提取氢原子，因此，由BPO引发的聚合物分支较多，在制备高固体丙烯酸树脂时应避免使用。AIBN分解的自由基则不易夺取氢原子。此外，BPO可在聚合物端基中引人可吸收紫外线的苯环，ABIN在聚合物端基中引人$(\\mathrm{CH}_{3})_{3}$ ，因此，ABIN的耐候、保光、保色性能比BPO好。  \n\n同一种引发剂在不同的溶剂中有不同的分解速率。在使用量和温度相同的情况下，其半衰期一般有如下的规律： ?  \n\n醇>醚>脂肪烃>芳烃 $>$ 高卤素溶剂  \n\n同一种引发剂在不同的单体中其半衰期也有较大的差异，例如在 $80\\Upsilon$ ，二氧六环为溶剂时，过氧化二苯甲酰对苯乙烯、甲基丙烯酸甲酯的半衰期分别为4.6h和5h，而对醋酸乙烯和顺丁烯二酸酐的半衰期分别为0.57h和 $1.50\\mathrm{h}$ 。  \n\n引发剂大多为易爆易燃物品，遇热、还原剂、强碱强酸和金属杂质时都可能加速分解，产生爆炸等现象，因此在贮存和使用时要引起注意。  \n\n引发剂的生产厂家常在产品（如BPO引发剂）中加人 $30\\%$ 左右的水分以确保贮存和运输的安全。使用时应将水分除去，但不可烘烤，较方便可行的方法是称量后溶于二甲苯，静置澄清后分出水分，再计算出溶液中引发剂的实际用量。对于偶氮二异丁睛，如贮存温度太高或时间太久会产生少量不溶物，如遇此现象，使用前可用乙醇溶解，重结晶净化后使用。  \n\n(3）溶剂和链调节剂溶剂是丙烯酸树脂的重要组成部分。良溶剂可使树脂清澈透明，黏度降低，树脂及其涂料的成膜性能好。  \n\n溶剂对树脂的溶解能力可参考溶解度参数8。丙烯酸树脂的8一般在 $8.5{\\sim}11$ 之间，根据相似相溶原理，甲苯、二甲苯、醇类、酯类、酮类等是常用的溶剂。更准确的推测可根据溶剂和树脂的三维溶解度参数。此外，选择时应考虑溶剂的成本、挥发速度、毒性等。  \n\n为了得到较高固体分和低黏度的树脂，常采用链转移剂。常见的有十二烷基硫醇、2-硫基乙醇、3-硫基丙醇、巯基丙酸、硫基戊酸、巯基琥珀酸、3-硫基丙酸-2-羟乙酯等。通常，在键调节剂中，随碳链的增长，链调节功能增强，到十二碳时达到最大值。碳链进一步增长链调节功能反而下降。此外，选用不同的链调节剂虽然可制得表观黏度相近的树脂，但分子量分布范围不尽相同。制漆以后漆膜的丰满度也有差异。就漆膜的丰满度来说，以十二烷基硫醇做链调节剂为最佳。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 276,
+        "chunk": "# 2.丙烯酸酯聚合  \n\n(1）自由基溶液聚合机理单体在溶液状态下通过自由基聚合反应合成的丙烯酸树脂是溶剂型丙烯酸酯树脂。自由基聚合是个不可逆的连锁反应，其反应过程包括链的引发、链的增长和链的终止3个阶段，这3个阶段的反应中有着较复杂的理论，在有关的高分子书籍中已有详述。与反应机理相对应的聚合反应经历四个时期（见图2-1-17)。  \n\n![](images/b86f7cf4f761a9624735c30703a46aaf2d2731ab1aaf2492394553db461bbf0f.jpg)  \n图2-1-17聚合反应的四个时期  \n\n$\\textcircled{1}$ 诱导期由于反应物中有阻聚剂或可能有阻聚作用的杂质及氧气存在，引发剂分解所产生的初级自由基会被它们所终止而生成低分子化合物，所以这段时间内实际上聚合反应没有开始，称之为诱导期。随阻聚杂质的多少，诱导期可长可短，如果希望缩短诱导期加快聚合速度就必须严格控制原料的阻聚杂质含量，使之减少至最低量。此外，已知氧气阻聚作用很大，要缩短诱导期，就应在反应系统中通人氮气等情性气体以驱除含氧的空气。  \n\n$\\textcircled{2}$ 聚合初期及聚合中期当反应体系中阻聚杂质与初级自由基反应尽后，诱导期结束，继续产生的新自由基与单体的引发聚合开始，聚合反应进入初期，此时称为等速阶段。转化率达到接近 $20\\%$ 时，其聚合速度自动加快，这时为聚合中期。由于反应放热，此时往往出现反应温度自然上升现象。为了保证安全生产，防止冲锅溢料以及保证质量的稳定，应仔细地控制温度，开启夹套冷水排除热量。丙烯酸树脂的工业生产中为了防止聚合中期大量放热所引起的冲料或暴聚，常采用慢速滴加单体的投料方法，这样可以控制反应时的单体浓度，滴加速度控制恰当时可以减缓放热及黏度突增现象，同时延长其聚合速度加快的历程，使滴人的单体可以较均匀地快速聚合。  \n\n$\\textcircled{3}$ 聚合后期聚合中期之后，一大半单体已经转化，反应物的黏度大大提高，单体的浓度迅速下降，链自由基的活动受到高黏度的阻滞而减缓，所以聚合速度明显下降。此时新的自由基也越来越少，常需补加引发剂才能达到较高的转化率，称之为聚合后期。  \n\n(2）影响丙烯酸树脂聚合反应的因素从溶液聚合反应的机理看出：反应温度、单体种类和浓度、引发剂种类和浓度以及杂质等条件对聚合物反应均有一定的影响。根据自由基聚合动力学研究结果，聚合反应的数均聚合度 $\\scriptstyle{X_{\\pi}}$ 按下式规律变化：  \n\n$$\nX_{n}=\\frac{K_{\\mathrm{p}}}{2(f K_{\\mathrm{d}}K_{\\mathrm{e}})^{1/2}}\\frac{[\\mathbf{M}]}{[\\mathbf{I}]^{1/2}}\n$$  \n\n式中 $\\kappa_{\\circ}$ ， $\\kappa_{\\mathrm{d}}$ ， $\\kappa_{\\mathrm{e}}$ ----增长速率常数、引发速率常数和终止速率常数；  \n\n$f$ —引发效率；  \n\n[M]，[I]—单体浓度和引发剂浓度。  \n\n速率常数 $\\kappa$ （K分别代表 $\\kappa_{\\ast}$ ， $\\kappa_{d}$ ， $\\kappa_{\\ast}$ ）与温度的关系遵守阿累尼乌斯方程： $\\kappa=$ $A{\\mathrm{e}}^{-E/(R T)}$ ，式中 $A$ 为频率因子； $\\scriptstyle{E}$ 为反应活化能； $R$ 为气体常数； $\\boldsymbol{\\tau}$ 为热力学温度。  \n\n$\\Phi$ 温度影响因素丙烯酸树脂合成的反应温度一般控制在 $80\\sim160^{\\circ}C$ 较为适宜，但如何确定某一种聚合反应的反应温度，应根据引发剂的类型和溶剂的沸点温度来确定。一般的原则是：理想的反应温度为溶剂的沸点温度，因为在溶剂的回流状态下进行聚合，反应容易控制，得到树脂也较为理想。但由于某种需要，选择的引发剂分解温度明显低于溶剂回流温度时，就要调整反应温度。例如选用偶氮二异丁腈引发剂，这种引发剂分解温度较低，聚合反应温度可适当降低到 $110{\\sim}120\\Upsilon$ 之间。另外，为防止空气中氧气对聚合反应的阻聚，需采用情性气体如氮气进行保护。  \n\n聚合反应温度的高低，直接影响树脂的分子量。在固定其他条件时，反应温度愈高，引发剂分解愈快，单位时间内生成的自由基愈多，聚合速度愈快，聚合度愈低，相应的树脂分子量也愈低。反之，反应温度愈低，合成得到的丙烯酸树脂的分子量愈大。因此，在实际合成中可采用控制温度的办法来调节丙烯酸树脂的分子量。  \n\n聚合温度与引发剂的选择有关。如从反应温度的角度来选择引发剂，在一次投量的情况下，一般选择半衰期为反应总时间 $^{1/3}$ 的引发剂为好。此时，单体转化率比较高，而且树脂中残留的引发剂量较少。如果引发剂与单体同时滴加，聚合反应温度一般选择在半衰期为 $10\\sim$ $60\\mathrm{{min}}$ 为好，单体转化率可达 $98\\%$ 以上，树脂中残留的引发剂量一般可低于加入引发剂量的 $1\\%$ .  \n\n聚合反应温度对聚合物分子量分布有一定的影响，提高聚合反应的温度，明显提高溶剂的链转移系数，平均分子量降低，生成的共聚物的组成分布更均一。  \n\n从实际生产的角度考虑，温度的升高应在一个合理范围内，若温度升得过高则会使聚合反应产生的热不易排除，生产难以控制。而且温度过高，易引起聚合物的支化、交联度增加，从而导致树脂中出现不溶颗粒，树脂质量不易控制。反应温度过低，反应前的诱导期延长，聚合反应的初期转化率低，但进入中期后聚合加快，放热激烈，反应体系温度会迅速升高，溶剂大量气化，有时夹套中冷却水来不及降温而导致冲锅溢料。  \n\n此外，聚合反应温度对聚合物颜色有一定的影响。一般情况下丙烯酸树脂的颜色APHA应该低于50。如果单体或溶剂自身是易变色的基团，或混有易变色的杂质，在高温下更会使树脂颜色加深。所以，聚合反应温度也不是越高越好。  \n\n$\\textcircled{2}$ 单体影响因素单体的品种和用量可根据被合成的树脂性质来决定。在聚合体系中，单体的一般用量控制在40%～75%之间。聚合反应是放热反应，因此为了控制聚合反应，一般采取滴加方式加人单体。  \n\n滴加速度决定树脂分子量的大小及树脂结构。匀速滴加单体可使树脂分子量分布较为均匀；慢慢滴加使滴加时间较长时，树脂分子量会降低，分子结构趋于均匀；滴加时间较短，滴加速度加快时，树脂分子量会增大，分子量分布变宽，分子结构均匀度较差。生产实践证明，一般单体滴加时间控制在 $2{\\sim}4\\mathrm{h}$ 为宜。  \n\n混合单体在较低的加料速度、较高的引发剂浓度和温度下，加入到反应器中的物料瞬间发生反应，反应器中的单体浓度低，即处于所谓的“饥饿”或“半饥饿”状态，所以在此条件下单体的聚合行为不同于一般的间歇反应器中的聚合行为。很多研究表明，饥饿加料法是控制聚合物分子量及其分布的有效方法。但在实际生产中，加料速度太慢会降低生产率，延长劳动时间。  \n\n单体浓度大小对树脂分子量的影响特别明显。单体浓度大时合成出的树脂分子量也大；反之则小。在溶液聚合中，往往通过调节单体浓度来控制树脂的分子量大小及分布。一般来说，反应体系中溶剂用量少时，单体浓度大，合成出树脂的分子量也大；溶剂用量多时，单体浓度小，合成出树脂的分子量也小，而且不易产生凝胶效应、支化和交联反应，保证聚合物性能稳定。在实际生产中，为了得到具有较高分子量的树脂，采用二步法加入溶剂：单体先在少量溶剂中聚合，完毕后，再补加溶剂。采用补加溶剂的方法不仅可得到较理想的树脂分子量，还可缩短聚合反应的时间。  \n\n单体的分子结构对聚合度也有影响。随着取代烷基碳原子数的增加，聚合愈趋困难，聚合度相应降低。除了聚合物外，单体的结构还影响其反应能力及聚合速率，这和单体是否对称及共轭程度等有关。一些常用单体聚合速率的顺序如下：  \n\n氯乙烯 $>$ 醋酸乙烯>丙烯腈>甲基丙烯酸甲酯>苯乙烯>丁二烯。  \n\n单体的纯度对聚合有很大的影响，因为许多杂质的作用与分子量调节剂、缓聚剂、阻聚剂差不多，对聚合速率和分子量均有影响。实践证明单体纯度越高越有利于聚合反应。  \n\n$\\textcircled{3}$ 引发剂在聚合反应过程中，若仅以光和热来引发丙烯酸酯聚合速率太慢，需要加入引发剂加速链引发反应，因此引发速率对聚合速率有决定性影响。在一定温度下，可认为聚合速率主要由引发速率决定。在许多情况下，聚合速率与引发剂浓度平方根成正比。  \n\n引发剂的用量对树脂的分子量、黏度及转化率产生影响。一般来说，引发剂的用量越高，树脂的分子量及黏度会越低。一般规律是分子量与引发剂用量的平方根成反比。在溶液聚合反应时，如要得到较高的分子量的树脂，引发剂用量可低些，一般可控制在 $0.2\\%\\sim$ 0.5%范围内；如要得到较低分子量树脂，引发剂用量可高些，一般可控制在 $0.6\\%\\sim2\\%$ 范围内，最高时可达 $4\\%\\sim5\\%$ 。引发剂用量过大会在生产过程中涉及热量的排除问题以及会影响聚合物的力学性能、热稳定性以及抗老化性能等。  \n\n不同品种，活性氧或氮的含量是不同的，评价引发剂对分子量、黏度、转化率等的影响时，应该采用相同的活性氧含量和分解速率。  \n\n引发剂的种类对分子量分布影响较大。如前所述，偶氮睛类引发剂分解成活性自由基后，副反应较有机过氧化物少得多，所以所得聚合物的分子量分布相对较窄，所得聚合物的黏度也相对较低。  \n\n有机过氧化物引发剂的分解过程相对复杂，如叔丁基过氧化物分解生成的自由基的活性较高，具有较强的夺氢反应能力，容易参与一些结合反应之类的副反应，使分子量分布趋宽。而叔戊基过氧化物分解生成的自由基活性较低，此自由基不太容易向溶剂转移生成小分子，使分子量分布趋窄，系统黏度下降等。在相同配方、聚合反应工艺的条件下，通过引发剂的选择可以在一定程度上改变聚合物的某些性能。  \n\n引发剂的加入方式对树脂分子量有很大影响。一般均采用滴加方法加入引发剂。目前有两种滴加形式：一种是引发剂和反应单体先混合均匀，一起匀速滴加到反应体系中；另一种是引发剂和单体以不同滴加速度分别滴加到反应体系中。两种滴加方法各有利。前一种在工业生产上使用起来较为方便，缺点是可能有部分引发剂在未来得及引发单体时就消失，降低了引发剂引发单体的效率，也增加了成本。后一种方法可通过调节引发剂滴加速度充分引发单体聚合，可以较为完全地引发聚合，缺点是生产装置较复杂，操作有一定的难度。因此，采用何种滴加方式应视生产条件而定。  \n\n在树脂合成中，投料方式是一个影响因素，在制备大分子量的热塑性丙烯酸树脂时，溶剂、单体和引发剂等一次投人反应并在反应温度下，引发剂分解半衰期为1h以上，使引发剂缓慢分解，制备较高分子量的聚合物。而合成热固性丙烯酸树脂时，多数情况是采用单体和引发剂同时滴加的工艺，使整个聚合过程中单体和引发剂的浓度能基本保持稳定。  \n\n利用引发剂进行聚合反应，在反应经过一段时间后，活性自由基浓度已降低到极点，部分单体未被引发聚合，如果此时终止聚合反应，所得到的树脂转化率较低，仅在 $70\\%\\sim$ $80\\%$ 之间，自由单体含量较高，而丙烯酸酯类单体一般都有特殊臭味，影响到丙烯酸树脂的质量。为了提高产品转化率，降低自由单体含量，往往在单体滴加完毕后的 $_{1\\sim2\\mathrm{h}}$ 后再补加$0.1\\%\\sim0.2\\%$ 的引发剂。补加引发剂也采取滴加方法，一般是将引发剂与反应用溶剂混合在一起。用 $_{1\\sim2\\mathrm{h}}$ 匀速补加，补加完毕后在经过 $_{1\\sim2\\mathrm{h}}$ 即可终止聚合反应。利用补加引发剂的方法，产品的转化率可达到 $96\\%$ 以上，如果反应控制得好，转化率可达到 $100\\%$ 。补加的引发剂种类可与反应主体用引发剂是同一种，也可以不同，可根据引发剂性质决定。如果是过氧化物，两种引发剂可以是同一种；但如果使用偶氮二异丁睛，由于引发剂在溶剂中溶解性较差，就不能用作补加引发剂。考虑到产品的稳定性，一般都是用偶氮二异丁睛作主体反应用引发剂，补加引发剂则选用过氧化物，但此时应考虑到过氧化物引发剂的分解温度较高，因此补加过程中应适当提高补加时的反应温度。  \n\n$\\textcircled{4}$ 阻聚剂和氧气活性较小的阻聚剂称为缓聚剂，表2-1-94列出了添加剂对聚合反应的影响。  \n\n表2-1-94添加剂对聚合反应和聚合度的影响  \n\n\n<html><body><table><tr><td>添加剂</td><td>对聚合速率的影响</td><td>对聚合度的影响</td></tr><tr><td>一般溶剂或链调节剂</td><td>没有</td><td>降低</td></tr><tr><td>调节剂</td><td>没有</td><td>剧降</td></tr><tr><td>缓聚剂</td><td>降低</td><td>降低</td></tr><tr><td>阻聚剂</td><td>剧降</td><td>剧降</td></tr></table></body></html>  \n\n在聚合反应中，阻聚作用的发生来源有两种。一种是单体中的阻聚剂，在使用前未处理或处理不干净；另一种是空气中的氧。前者在生产过程中容易引起人们的注意，也较容易解决。目前市购原料大多使用对甲氧基苯酚类阻聚剂，该阻聚剂受热分解，使用时可不必除去，它的存在只增加了聚合反应的诱导期，对整个聚合反应影响不大。但后者较容易被人们忽视，空气中氧的阻聚作用在聚合反应温度较低时，作用比较明显。氧气的存在，会导致聚合物的分子量小，黏度低，反应诱导期延长，反应速率减慢，反应转化率降低等现象。具体的反应机理为：  \n\n即反应生成的活性自由基很容易与空气中的氧结合生成一种新的过氧化物，降低了反应体系中自由基的浓度。不过研究发现，在高温下一般氧的阻聚作用表现不出来，这可能是因为生成的过氧化物在高温下分解产生新的自由基，仍可使单体聚合：  \n\n为了防止在聚合反应过程中氧的阻聚作用发生，尤其是聚合温度低于溶剂沸点的情况下，在生产过程中应吹入氮气用以隔绝空气；但应注意，吹氮气后树脂分子量会增大，此时应适当增加引发剂用量来平衡树脂的分子量。例如，在聚苯乙烯合成时，常温下在空气介质中，苯乙烯的聚合度为2000；在氮气的保护下，其聚合度为6000。吹氮气还有一个优点是合成出的树脂颜色很浅，星水白色。如果在生产过程中现有设备不具备吹氮气条件，进行溶液聚合时，反应温度应控制在溶剂介质回流温度内。  \n\n$\\textcircled{5}$ 溶剂和链调节剂溶剂的选择在丙烯酸树脂合成中是十分重要的，溶剂的选择首先应考虑是单体和聚合物的良溶剂。在不同溶解能力的溶剂中，聚合物链分子的形态是有差别的。在良溶剂中，聚合物链呈舒展状，树脂溶液清澈透明；反之，聚合物链将紧缩而卷曲，树脂溶液浑浊甚至析出。  \n\n溶剂对丙烯酸酯单体的溶解能力与单体的结构有关，低级醇构成的丙烯酸酯能溶于芳烃、酯类、酮类和氯代烃等，但不溶或微溶于脂肪烃、醚类和醇类。四碳以上醇构成的丙烯酸酯可以溶于脂肪烃中。  \n\n溶剂应对引发剂不产生诱导分解作用，同时对引发剂具有良好的溶解性。过氧化物引发剂在各类溶剂中的分解速率按下述次序增大：芳烃、烷烃、酯类、醚类、醇类、胺类等。表2-1-95列举了溶剂对过氧化苯甲酰分解速率的影响。  \n\n表2-1-95溶剂对过氧化苯甲酰分解速率的影响（80℃）  \n\n\n<html><body><table><tr><td rowspan=\"2\">溶剂品种</td><td colspan=\"3\">分解速率/%</td></tr><tr><td>10min</td><td>1h</td><td>4h</td></tr><tr><td>氯仿</td><td></td><td>14.5</td><td>43.7</td></tr><tr><td>乙苯</td><td></td><td>15.0</td><td>45.5</td></tr><tr><td>苯</td><td></td><td>15.5</td><td>50.4</td></tr><tr><td>甲苯</td><td></td><td>17.4</td><td>49.5</td></tr><tr><td>苯乙始</td><td></td><td>19.0</td><td></td></tr><tr><td>丙酮</td><td></td><td>28.0</td><td>71.8</td></tr><tr><td>环已烧</td><td></td><td>51.0</td><td>84.3</td></tr><tr><td>醋酸乙酯</td><td></td><td>53.5</td><td>85.2</td></tr><tr><td>二氧六环</td><td></td><td>82.3</td><td></td></tr><tr><td>乙醇</td><td>81.8</td><td></td><td></td></tr><tr><td>异丙醇</td><td>95.1</td><td></td><td></td></tr><tr><td>叔丁醇</td><td>16.2</td><td></td><td></td></tr><tr><td>正丁醇</td><td>34.8</td><td></td><td></td></tr><tr><td>苯胺、三乙胺</td><td>爆炸式分解</td><td></td><td></td></tr></table></body></html>  \n\n由表2-1-95可知：胺类化合物对引发剂分解速率的影响很大，哪怕少量的胺类化合物也有影响，这可能与它们形成氧化还原体系有关。在单体中引入带氨基官能团的单体，多数改用偶氮类引发剂。醇、醚化合物对引发剂分解速率的影响也比较大，特别是醇类在过氧化物引发的聚合反应中应尽量避免，否则将得不到预期的反应结果，甚至导致反应失败。例如用乙醇作溶剂时，由于BPO极快的分解速率，使引发反应的笼蔽效应大大增强，引发效率急剧下降，从而使反应转化率极低，导致反应失败。所以在溶液聚合反应中，考虑引发剂分解速度时，必须了解溶剂的影响，它不仅影响引发剂分解速率，同时还影响引发剂的引发效率。  \n\n考虑溶剂的链转移反应常数对聚合反应的影响，高链转移常数的溶剂会使聚合物分子量降低，可根据对聚合物分子量的要求来选择合适的溶剂。  \n\n溶剂的选择对树脂的分子量和黏度有一定的影响。一定的溶剂有-一定的链转移常数，在聚合反应链增长过程中带有自由基的聚合物分子可能向溶剂转移自由基而使聚合物链终止反应。溶剂的链转移参数越大，树脂的分子量及黏度就越低；反之，则越高。它们的相关式可表示如下：  \n\n$$\n{\\frac{1}{X_{n}}}={\\frac{1}{(X_{n})_{0}}}+C_{s}\\ {\\frac{[\\mathbf{S}]}{[\\mathbf{M}]}}\n$$  \n\n式中 $X_{n}$ ， $(X_{n})_{0}$ . ${C_{\\mathrm{s}}}$ —聚合度、无溶剂时的聚合度及溶剂链转移常数；  \n\n[S]、[M]—溶剂浓度和单体浓度。  \n\n溶剂的链转移常数与其结构有关，对于芳烃， $c_{\\mathrm{s}}$ 一般有：异丙基苯 $>$ 乙苯 $>$ 甲苯 $>$ 叔丁基苯>苯。  \n\n而对于醇类，则 $c_{*}$ 有如下关系： $\\mathrm{R_{2}C H O H{>}R C H_{2}O H{>}C H_{3}O H_{\\circ}}$  \n\n例如在MMA/BA/HPMA/AIBN体系中在其他因素固定的情况下考察四组溶剂苯/醋酸丁酯，甲苯/醋酸丁酯，乙苯/醋酸丁酯，异丙苯/醋酸丁酯获得的聚合物的分子量分别为86800，79500，70500，58600。这是由于异丙苯的链转移常数最大的缘故。  \n\n一般溶剂的链转移常数在 $10^{-5}\\sim10^{-4}$ 之间，对分子量不会有很大的影响，但在溶剂聚合时溶剂占 $30\\%\\sim60\\%$ ，特别在反应后期，溶剂的浓度大大超过单体的浓度时，溶剂的链转移作用是不容忽视的。  \n\n溶剂的选择还要考虑到树脂的制漆过程和涂料的施工工艺。在聚合过程中由溶液的回流和冷凝来控制聚合热量使聚合反应较为平稳地进行，一般溶剂在聚合反应体系中的含量至少在 $30\\%\\sim40\\%$ ，以确保体系黏度较低、搅拌和热量传递效果良好。  \n\n链调节剂如十二烷基硫醇、巯基乙醇等具有较大的链转移常数，可以终止正在增长的链反应。链调节剂用量越高，分子量越小，黏度越低。  \n\n研究表明，以3-硫基丙酸为链转移剂时获得最低的分子量和最窄的分子量分布。采用含有官能团的引发剂和链转移剂，有利于合成遥爪聚合物。如采用4，4-偶氮（4-氰基戊酰）和链转移剂硫基乙醇，可以使 $30\\%$ 的大分子链含有两个端羟基，这样只需加人少量的官能团。以钻为基础的链转移剂，能在很低浓度下产生高链转移效应，使合成丙烯酸聚合物的分子量低且分子量分布较狭窄。  \n\n$\\textcircled{6}$ 分子量分布和共聚物的组成在一个共聚反应中，往往同时选用几种单体进行共聚，由于单体结构特征各异，导致在共聚体系中相对反应活性各有差异。在一个反应体系中如果每一个反应的反应速率常数相近，则单体进行无规共聚，分子链结构为无规分布；如果反应速率常数差别较大，开始形成的分子链含很多的活泼单体单元，反应后期形成的分子链则含有较多的活泼性差的单体单元。作为涂料用丙烯酸树脂，树脂结构越均匀，一般其性能越好。因此在进行单体选用时，每种单体间的相对反应活性都要考虑，以便通过对聚合工艺的调整，合成出理想的、符合设计要求的树脂。  \n\n现在简单以二元共聚体系为例，讨论在聚合体系中两种单体间的相对活性。  \n\n在二元共聚体系中，两种单体存在四种反应形式：  \n\n$\\mathbf{M}_{1}+\\mathbf{M}_{1}$ -→M M 速率 $R_{11}$ $\\mathbf{M}_{1}+\\mathbf{M}_{2}$ · → M M 速率 $R_{12}$ Mz+M→ MM 速率 $R_{21}$ M+M→ MM 速率Rz2  \n\n两种单体的相对反应速率为：Y=R/R12，Y=Rz2/Rz1，其物理意义是表示以M单体为端基的自由基与 $\\mathbb{M}_{1}$ ， $\\mathbf{M}_{2}$ 两种单体反应速率比； $\\gamma_{2}$ 表示以 $\\mathbf{M}_{2}$ 单体为端基的自由基与 $\\mathbf{M}_{2}$ ， $\\mathbf{M}_{1}$ 两种单体反应速率比。通过对 $\\gamma$ 的分析评价可以确定两种单体的相对反应性，存在以下4种形式。  \n\na.>1，>1：说明两种单体在共聚体系中，利于自聚反应，这是不希望的反应。b. $\\gamma_{1}<1$ . $\\gamma_{2}<1$ ：说明两种单体在共聚体系中，利于共聚反应，值比1小得多，共聚得越好，这是希望的反应。c. $\\begin{array}{r}{\\gamma_{1}=\\gamma_{2}=1}\\end{array}$ 时，说明两种单体在共聚体系中，自聚和共聚的机会相等，这也是不希望的反应。d $\\begin{array}{r}{\\pmb{\\gamma}_{1}=\\pmb{\\gamma}_{2}=0}\\end{array}$ 时，说明两种单体在聚合体系中，只进行共聚反应，这是一种理想的状态。  \n\n表2-1-96常见单体的相对反应性  \n\n\n<html><body><table><tr><td>M单体</td><td>M单体</td><td></td><td>T</td></tr><tr><td rowspan=\"6\">苯乙烯</td><td>丙烯酸丁酯</td><td>0.4572</td><td>0.0797</td></tr><tr><td>甲基丙烯酸甲酯</td><td>0.5174</td><td>0.4579</td></tr><tr><td>甲基丙烯酸丁酯</td><td>0.4495</td><td>0.3999</td></tr><tr><td>丙烯酸羟乙酯</td><td>0.3643</td><td>0.3070</td></tr><tr><td>丙烯酸</td><td>0.2476</td><td>0.3433</td></tr><tr><td>甲基丙烯酸</td><td>0.1340</td><td>0.9118</td></tr><tr><td rowspan=\"5\">丙烯酸丁酯</td><td>甲基丙烯酸甲酯</td><td>0.3662</td><td>1. 8594</td></tr><tr><td>甲基丙烯酸丁酯</td><td>0.3886</td><td>1. 9837</td></tr><tr><td>丙烯酸羟乙酯</td><td>0.8588</td><td>2.0755</td></tr><tr><td>丙烯酸</td><td>0.3437</td><td>2.7336</td></tr><tr><td>甲基丙烯酸</td><td>0.1494</td><td>5.8357</td></tr><tr><td rowspan=\"4\">甲基丙烯酸甲酯</td><td>甲基丙烯酸丁酯</td><td>0.9914</td><td>0.9965</td></tr><tr><td>丙烯酸羟乙酯</td><td>0.9853</td><td>0.9383</td></tr><tr><td>丙烯酸</td><td>0.7461</td><td>1.1688</td></tr><tr><td>甲基丙烯酸</td><td>0. 3495</td><td>2.6879</td></tr><tr><td rowspan=\"3\">甲基丙烯酸丁酯</td><td>丙烯酸羟乙酶</td><td>1. 0127</td><td>0.9594</td></tr><tr><td>丙烯酸</td><td>0.7744</td><td></td></tr><tr><td>甲基丙烯酸</td><td></td><td>1.2069</td></tr><tr><td rowspan=\"2\">丙烯酸羟乙酯</td><td>丙烯酸</td><td>0.3580 0.7765</td><td>2.7091 1.2774</td></tr><tr><td>甲基丙烯酸</td><td>0.3517</td><td></td></tr><tr><td>丙烯酸</td><td>甲基丙烯酸</td><td>0.4481</td><td>2.8406 2.1998</td></tr></table></body></html>  \n\n表2-1-96中列出了几种常见单体的竞聚率值。根据表中数据，可以归纳出4点。  \n\na.苯乙烯反应活性很大，不论端基自由基是何种单体，都能与之进行共聚反应。  \n\nb.丙烯酸丁酯在聚合反应中有选择地进行共聚，只有当端基自由基为本身时，才能与其他单体共聚，而本身难以与其他单体自由基共聚。  \n\nc.甲基丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸羟乙酯这3种单体在共聚体系中，都表现出选择性共聚。尤其当甲基丙烯酸丁酯与丙烯酸羟乙酯共聚时，只能是甲基丙烯酸丁酯共聚到丙烯酸羟乙酯上，反过来则不能发生共聚反应。  \n\nd.值得注意的是，丙烯酸或甲基丙烯酸在共聚中表现出特殊反应性，本身不但容易与其他单体共聚，而且也容易发生自聚反应，而这种自聚反应是不希望发生的反应。  \n\n通过上述分析讨论，在选定单体进行树脂合成时，一定要调整聚合工艺，才能使合成的树脂结构较均匀，否则树脂的性能达不到预期的设计效果。  \n\n在工业上，改善共聚物组成分布的方法有： $\\textcircled{1}$ 在单体转化率比较低时，终止反应，生成共聚物的组成会均匀些，但单体的回收太复杂，不经济； $\\textcircled{2}$ 按单体的竞聚率，计算分批投料量的比例，但当共聚物单体组成比较多，如 $4{\\sim}6$ 个不同单体时，计算太复杂。  \n\n现在，聚合中常常采取以下三种方法来控制聚合物链结构。  \n\na.增加聚合反应的温度竞聚率是两单体与同一种自由基的反应速率常数的比值，反应速率慢的往往反应的活化能大，根据Arrhenius方程式，活化能愈大，反应速率受温度的影响愈大。通常单体的活性比为 $50{\\sim}60\\Upsilon$ 测定，如果将反应温度提高到 $140^{\\circ}\\mathrm{C}$ 以上，低活性单体的反应速率常数增加更快，也就是说，升高同样的温度，低活性单体的反应速率常数增加得更快，因此高低活性单体的活性相差减小，聚合单元的分布变得均匀。这种效应也可称之为聚合反应的“温度拉平效应”。醋酸乙烯在 $60^{\\circ}C$ 时几乎不能与丙烯酸酯单体共聚，但当将反应温度提高到 $160^{\\circ}\\mathrm{C}$ 以上时，叔碳酸乙烯酯也有可能与丙烯酸酯单体共聚合，只是需要将它与溶剂一起先加入反应器，而后滴加丙烯酸酯单体，可制得均一、透明的丙烯酸酯树脂。在高温条件下聚合，与其他丙烯酸酯单体的活性更接近。  \n\nb.采用单体的饥饿滴加方式如果聚合反应很快，单体的供应跟不上，那么活性低的单体也会及时聚合到聚合物的链段之中，这样也就强迫活性低的单体与活性高的单体可以均匀地聚合在聚合物长链之中，这也是实际反应之中常常采用的方法。如上述，采用同时滴加单体混合物和引发剂，使滴入的单体在引发剂的引发下，很快发生聚合，同时又及时补充新单体，单体混合物组成会很快建立平衡。单体混合物的组成稳定了，生成共聚物的组成也会比较均一。  \n\n对于像丙烯酸或甲基丙烯酸这样的单体，在使用时往往采用分批投料的方法来控制自聚反应。开始时酸的含量较低，逐渐增加其含量。这样合成出的树脂，初始聚合物的酸含量与最终聚合物中的含酸平均值容易符合配方的比例，树脂结构组成比较均匀。  \n\nc.加人不能均聚的单体如果一种单体不能均聚，那么它就可以很好地与其他单体共聚，从而可以得到需要的共聚产物。  \n\n树脂分子量分布的宽窄对漆膜的性能有较大的影响。可以用重均分子量 $M_{\\mathbf{w}}$ 和数均分子量 $M_{\\mathfrak{n}}$ 的比值 $M_{\\mathrm{w}}/M_{n}$ 来表示。 $M_{\\mathrm{w}}/M_{\\mathrm{p}}$ 值越大，分子量分布越宽； $M_{\\ast}/M_{\\ast}$ 值越小，分子量分布越窄。从涂料性能来看，分子量分布窄，性能稳定。对于常规的热固性丙烯酸树脂，由于在成膜过程中树脂将进一步交联，对 $M_{\\infty}/M_{\\Re}$ 值要求低一些；但对于热塑性丙烯酸树脂以及高固体分丙烯酸树脂， $M_{\\mathrm{w}}/M_{\\mathrm{n}}$ 值大，会明显地影响漆膜的硬度、耐候性、耐水、耐碱和耐溶剂等性能。  \n\n在树脂合成过程中，要保持工艺的稳定性；工艺稳定性包括稳定的温度、单体均匀、滴加匀速等，这些是保证分子量分布窄的重要因素。  \n\n$\\textcircled{7}$ 树脂的聚合度对性能的影响树脂的聚合度或分子量对树脂的性能具有很大的影响。分子量高，则聚合物的拉伸强度、弹性、延伸率等力学性能优越；但分子量太高时，聚合物具有溶解性差、施工性能差、施工固体分低等缺点，例如聚丙烯酸乙酯，随着聚合度的增加，其玻璃化温度也增加，分子量小时呈油状，为黏性液体，随着分子量的增加，逐渐强韧起来，近似橡胶状，但达到 $10000{\\sim}20000$ 时，再增加下去， $T_{\\ast}$ 和物性都变化不大。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 277,
+        "chunk": "# 3.丙烯酸树脂生产工艺和安全生产  \n\n(1）生产工艺目前工业上所用的丙烯酸树脂多数是间歇式反应釜生产的。反应釜除夹套可通蒸汽和冷水外，还应带有盘管，以便迅速带走反应热，大釜还应设计防爆聚的安全膜。  \n\n丙烯酸树脂生产设备主要有：反应釜、冷凝器、分水器、高位槽、过滤器、热煤炉、压缩空气系统、真空系统。以及配套的物料输送装置、计量装置等。  \n\n![](images/bd2d714b98dd7ffefe41e226806af21aa2687fbf8ec322a744f2dee830758145.jpg)  \n图2-1-18设有两个高位槽的丙烯酸类树脂生产工艺流程1，2—高位槽；3，4—流量计；5-冷凝器：6—分水器：7—反应釜  \n\n流程的示意图如图2-1-18所示。  \n\n一般的操作步骤如下。  \n\n$\\Phi$ 按工艺配方，将规定数量的单体通过不锈钢过滤器过滤后，加入单体配置器中，待混合均匀后，放置待用。  \n\n$\\textcircled{2}$ 将引发剂投入引发剂配制器中，用少量聚合溶剂溶解，过滤待用。如系BPO等含水过氧化物，则应除去水分。  \n\n$\\textcircled{3}$ 空釜时，先打开氮气（或二氧化碳）通管，赶走釜内空气。然后按配方规定加入溶剂。有时，可先加人部分单体和引发剂。  \n\n$\\textcircled{4}$ 继续通情性气体，开动搅拌，打开蒸汽阀加热，并打开回流加热和冷却两个冷凝器的冷却水，待升到离规定的反应温度前$20\\sim30\\ensuremath{\\mathrm{~c~}}$ 时（可视具体情况而定）即可关闭蒸汽，待其慢慢自升到反应温度。  \n\n$\\textcircled{5}$ 开始加入单体和引发剂溶液，一般在 $2\\sim4\\mathrm{h}$ 内加完，但应视反应热的除去情况而稍加调整。单体和引发剂的加人速度应均衡，在此期间温度也要保持恒定。  \n\n$\\textcircled{6}$ 加完单体和引发剂后，保温 $1.5\\sim2\\mathrm{h}$ ，追加第一次引发剂（可溶于溶剂中一次投人)，再追加第二次引发剂，继续保温到转化率和黏度达到规定指标。整个反应时间约在$6\\sim15\\mathrm{h}$ 完成，视品种配方不同而异。  \n\n$\\textcircled{7}$ 反应完成后，可加热升温蒸出少部分溶剂，借以脱除自由单体。然后，补加新鲜溶剂以调整固体含量。这样可减少成品中丙烯酸酯单体的气味。但蒸出部分的利用，必须在小心试验后才可做原料加人下一釜聚合。  \n\n$\\textcircled{8}$ 冷却后，出料。  \n\n操作中应注意以下事项。  \n\n$\\Phi$ 单体和引发剂加入速度不可太快，以免引起冲料。  \n\n$\\textcircled{2}$ 反应温度要控制好，如由于单体的加人而使温度下降过多时，要停止加人单体，慢慢地小心升温到反应温度再继续加料，否则，会造成未反应的单体在反应釜中积累，紧接而来的就是剧烈聚合和冲料。 1(2）质量控制对于一般的溶剂型丙烯酸树脂，可通过测定下列项目来进行质量控制。  \n\n$\\Phi$ 固体含量称取一定数量的树脂，于规定的适当温度下（视溶剂品种而定）烘烤一定的时间，再称量，即可计算出固体分。如用二甲苯-丁醇为聚合溶剂，可于 $120\\Upsilon$ ，烘两个小时测定。对于高固体低黏度的树脂按上述条件测定结果往往偏低，经验表明此时可将温度降低至 $105\\%$ ，烘烤4h。严格地说，测定固体含量应烘到恒重为止，但工业上用前述方法已足够了。  \n\n②黏度般用涂-1和涂-4黏度计测定。如果黏度很大，可用落球法测定。也可使用加氏管测定，树脂的黏度对漆膜的物理性能及光泽、丰满度等都会带来很大影响，要小心控制。  \n\n$\\textcircled{3}$ 色泽采用常见的铁-钴比色或铂-钻比色都可以，一般丙烯酸树脂色泽都很浅。呈水白色或微黄色。  \n\n$\\textcircled{4}$ 酸值采用一般氢氧化钾乙醇溶液滴定，用酚作指示剂。  \n\n$\\textcircled{5}$ 分子量分布如具备仪器条件，或对要求较高的产品，可以做一下凝胶渗透色谱分析，它的分子量分布可以很快测定，通过与标准样对比，可以了解聚合反应进行的情况。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 278,
+        "chunk": "# (3)安全生产  \n\n$\\textcircled{1}$ 防火、防爆低级丙烯酸酯及甲基丙烯酸酯类的闪点较低，属易燃液体，有些单体与空气在一定比例下形成爆炸混合物，遇火可能引起爆炸。表2-1-97列举了部分单体的爆炸极限。  \n\n表2-1-97单体的爆炸极限   \n\n\n<html><body><table><tr><td rowspan=\"2\">单体</td><td colspan=\"2\">爆炸极限（对空气容量）/%（体积）</td><td rowspan=\"2\">单体</td><td colspan=\"2\">爆炸极限（对空气容量）/%（体积）</td></tr><tr><td>上限</td><td>下限</td><td>上限</td><td>下限</td></tr><tr><td>丙烯酸甲酯</td><td>2.8</td><td>25.0</td><td>甲基丙烯酸甲酯</td><td>2.12</td><td>12.5</td></tr><tr><td>丙烯酸乙酯</td><td>1. 8</td><td>饱和</td><td>甲基丙烯酸乙酯</td><td>1.8</td><td>饱和</td></tr><tr><td>萃乙烯</td><td>1.1</td><td>6.1</td><td></td><td></td><td></td></tr></table></body></html>  \n\n有些单体如丙烯酸丁酯及丙烯酸虽然在标准状态下（ $25\\mathrm{{C}}$ 及 $101,325\\mathrm{{kPa})}$ ，其饱和蒸气压浓度低于爆炸极限的下限值，但在温度足够高或压力降低时，还会形成爆炸混合物。  \n\n在贮运及操作过程中要排除一切可能产生的火花、明火的因素。阻火器、避雷针、接地装置、防止静电的贮槽中的浸深管等装置都是必要的，并应定期检查其可靠性。  \n\n$\\textcircled{2}$ 防护对可能接触单体的职工要进行系统的教育，使之认识到丙烯酸酯在防火、防爆、防毒各方面的重要性及防护知识。由于丙烯酸酯刺激眼睛，应坚持戴防护眼镜操作。丙烯酸酯会刺激或灼伤皮肤，当衣服手套上沾上单体时应立即更换，洗净后才能穿，皮肤上直接接触丙烯酸酯后应用大量清水冲洗，然后用肥皂洗净。如有较重刺激、灼伤、腐蚀或中毒现象时应立即治疗。  \n\n车间及仓库应通风。管道、泵、容器等应严格管理防止渗漏以保持蒸气浓度不超过允许浓度。  \n\n凡有丙烯酸酯的污水不可直接排人市政污水管，必须处理后才能排放。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 279,
+        "chunk": "# 4.溶剂型丙烯酸树脂合成  \n\n(1）丙烯酸树脂配方的设计及有关计算丙烯酸树脂及涂料的应用范围十分广泛，从底材来分，可应用于金属如铁、铝、铜、锌等金属和合金，塑料如ABS、HIPS、PS、PC等，水泥板，胶木，玻璃钢，玻璃，木材，皮革等；从产品来分，可应用于飞机、汽车、自行车、机器、家用电器、玩具、家具、建筑等的表面装饰。因此，在设计配方时首先要考虑树脂的应用对象。  \n\n一般的程序如下。  \n\n$\\textcircled{1}$ 确定树脂的类型是热塑性的还是热固性的。  \n$\\textcircled{2}$ 确定树脂用来制造何种涂料。  \n$\\textcircled{3}$ 确定树脂聚合方法。  \n\n④确定设计的树脂和涂料应达到的主要技术指标及施工性能。  \n\n$\\textcircled{5}$ 根据涂料产品特性来选择单体。  \n\n$\\textcircled{6}$ 对选择的单体互相间反应性加以论证，选择有利于共聚反应的单体。  \n\n$\\textcircled{7}$ 确定聚合工艺条件。  \n\n$\\textcircled{8}$ 模拟单体配比，进行树脂合成。  \n\n$\\textcircled{9}$ 根据模拟单体配比合成的结果，对单体配比进行反复调整。  \n\n$\\textcircled{10}$ 确定合成树脂工艺规程，包括聚合方法，树脂配方，聚合工艺，树脂质量指标等。  \n\n在按上述程序对某一产品进行设计时，单体的选择及使用是很关键的设计步骤，这种设计的合理性一是通过分析计算加以验证；二是要依靠大量的实验加以分析评价。  \n\n上面是树脂合成的一般过程，对树脂的评价一般包括固体分、黏度、酸值、羟基含量、平均分子量以及重均分子量 $M_{\\ w}$ 和数均分子量 $M_{\\mathfrak{n}}$ 的比值 ${M_{\\mathrm{w}}}/{M_{\\mathrm{n}}}$ 等。树脂的上述指标仅仅反映一个方面，一个树脂要真正成为一个产品，还要重视它的应用评价，即评价由该树脂和相应的溶剂、助剂、颜料、固化剂等做成的涂料包括清漆和色漆的性能。通过其涂料的性能可以知道在一定条件下，该树脂所呈现的耐候性、光泽、丰满度、硬度、附着力、干性以及各种耐介质等性能以及它的施工性能。考虑到很多物件的涂装是多层涂装，如汽车的涂装有底涂、中涂、面涂、罩光，在评价树脂时要考虑该树脂与其他树脂的配套性。此外，在喷涂物件出现次品需要返工时还要考虑涂料的返工性能。  \n\n根据单体结构特征及聚合反应机理，可以认为丙烯酸树脂在聚合反应过程中，反应只在乙烯基双键上进行，而单体侧链基无论是非极性还是极性都不参与反应。根据上述推定，我们可根据树脂单体组成，在合成树脂前计算出有关树脂的某些特征值，便于修改树脂配方，指导实验，对树脂进行检测分析，确定树脂性能指标。  \n\n丙烯酸树脂的特征值一般包括分子量、玻璃化温度、极性、亚甲基含量、酸值、羟基含量、固体含量等七个指标。其中除树脂分子量难以用简单的计算方法外，其余都可通过简单计算得到，结果与实验测定基本符合。  \n\n下面通过配方（表2-1-98）为例进行计算。  \n\n表2-1-98树脂单体组成  \n\n\n<html><body><table><tr><td rowspan=\"2\">单体</td><td colspan=\"2\">组成</td><td rowspan=\"2\">均聚体T/K</td><td rowspan=\"2\">均聚体</td><td rowspan=\"2\">亚甲基含量/%</td></tr><tr><td>%</td><td>mol</td></tr><tr><td>苯乙烯</td><td>20. 0</td><td>0.1923</td><td>373</td><td>9.3</td><td>。</td></tr><tr><td>丙烯酸丁酯</td><td>5.0</td><td>0.0391</td><td>219</td><td>8.7</td><td>32.8</td></tr><tr><td>甲基丙烯酸甲酯</td><td>20.0</td><td>0. 2000</td><td>378</td><td>9.5</td><td>0</td></tr><tr><td>甲基丙烯酸丁酯</td><td>40.0</td><td>0.2817</td><td>295</td><td>8.7</td><td>29.5</td></tr><tr><td>丙烯酸羟乙酯</td><td>10.0</td><td>0.0862</td><td>258</td><td>10.6</td><td>12.1</td></tr><tr><td>甲基丙烯酸</td><td>5.0</td><td>0.0581</td><td>458</td><td>13.1</td><td>。</td></tr><tr><td>合计</td><td>100.0</td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n$\\textcircled{1}$ 玻璃化温度均聚物的玻璃化温度可从表2-1-98查得，共聚物的 $T_{*}$ 可从配方中的单体均聚物的玻璃化温度利用FOX方程式近似求得。  \n\n$$\n1/T_{g}{=}\\Sigma w_{i}/T_{g i}\n$$  \n\n式中 $T_{*}$ —共聚物的玻璃化温度，K；  \n\n$\\boldsymbol{w}_{i}$ —不同单体的质量分数；  \n\n$T_{s},$ —单体i均聚物所得的聚合物的玻璃化温度。  \n\n利用上式计算所得的聚合物的玻璃化温度为 $44.99$  \n\n通过计算，可预测所设计配方树脂的 $T_{\\mathrm{s}}$ 值，分析评价合成树脂的机械强度。树脂的 $\\boldsymbol{T_{\\mathrm{s}}}$ 值高时，其力学性能好，树脂的 $T_{\\mathrm{s}}$ 低时，其力学性能较差，但弹性较好。同时还可通过上述计算，剖析某一树脂中单体组成。也可根据树脂特征值设计配方进行原料代用。  \n\n$\\textcircled{2}$ 极性（SP）的计算计算SP的公式为：  \n\n$$\nS P{=}\\Sigma\\delta_{i}w_{i}\n$$  \n\n式中SP-——树脂的极性；  \n\n$\\widehat{\\vartheta}_{i}$ \\* $\\boldsymbol{w}_{i}$ —树脂组成中单体均聚物的极性及单体的百分组成。  \n\n由上式计算出该合成树脂的SP值为9.39。  \n\n利用上述计算，可预测所设计配方SP值，初步了解树脂的极性。在进行树脂稀释或与其他树脂拼用时可根据此计算，按极性相似者互溶的原理选择各种稀释用溶剂及拼用树脂。  \n\n$\\textcircled{3}$ 亚甲基（ $\\mathrm{CH}_{2}$ ，%）含量的计算计算公式为：  \n\n$$\n\\mathrm{CH}_{2}\\%{=}\\Sigma(m_{i}/100)\\mathrm{CH}_{2}\\%_{i}\n$$  \n\n式中 $m_{i}$ —树脂组成中单体均聚物的含量；  \n\n$\\mathrm{CH}_{2}\\%_{i}$ —树脂组成单体均聚物亚甲基的含量。  \n\n由上式计算出合成树脂的亚甲基含量为 $14.65\\%$  \n\n利用上述计算，可分析评价树脂中侧链酯基含量。可用此方法剖析某一树脂中单体的组成。  \n\n$\\textcircled{4}$ 酸值的计算在合成涂料用丙烯酸或甲基丙烯酸的主要目的是为了增加树脂的极性，羧基本身并不参与聚合反应。因此树脂合成前后，在其组成中总的含酸平均量是一定的。这样我们可通过计算事先确定出所设计配方的含酸量。  \n\n酸值 $(\\mathrm{mgKOH/g}$ 树脂）的表示方法：  \n\n酸值 $=~(N M_{\\mathrm{KOH}}/100)\\times1000$ 式中 $N$ —羧酸的百分摩尔数；$M_{\\mathsf{K O H}}$ —氢氧化钾分子量。  \n\n该树脂酸值计算为：酸值 $=(0.\\ 0581\\times56.\\ 1/100)\\times1000=32.\\ 59\\mathrm{mgKOH/g}$  \n\n$\\textcircled{5}$ 羟基含量 $(\\mathrm{-OH\\%}$ ）的计算在合成丙烯酸树脂时，引进羟基的主要目的是为固化成膜提供交联基团，羟基本身并不参与聚合反应。在树脂合成前后，其组成中羟基含量是不变的。通过计算，我们可事先确定所设计配方的羟基含量。羟基含量计算方法如下：  \n\n$$\n-\\mathrm{OH}\\%=N M_{\\mathrm{OH}}\n$$  \n\n式中 $N$ ——树脂配方中羟基摩尔数；  \n\n$M_{0\\mathrm{H}}$ 一羟基的分子量。  \n\n该树脂的羟基含量为一 $\\scriptstyle\\mathrm{{OH}}\\%=0,0862\\times17=1.46$  \n\n(2）热塑性丙烯酸树脂热塑性丙烯酸树脂在成膜过程中不发生进一步交联，这类树脂不含有羟基、环氧基等可参与交联反应的活性基团。这类树脂中，大多以甲基丙烯酸酯类单体为主，也含有丙烯酸丁酯、苯乙烯等单体。它的分子量较大，一般在 $75000{\\sim}120000$ 之间。在施工黏度下，其施工固体分一般在 $10\\%\\sim25\\%$ 。热塑性丙烯酸树脂分子量增加，漆膜力学性能也会提高，但树脂溶液的黏度提高会导致施工固体分下降；分子量太高，树脂溶解性变差，喷涂时会出现拉丝现象；分子量太低，漆膜的物理性能往往不好。因此，为了保持漆膜的性能，树脂的分子量分布要尽可能窄，一般 $M_{\\ast}/M_{\\ast}$ 控制在 $2.1{\\sim}2.3$ 为宜，若大于或等于 $4{\\sim}5$ 时，就不能使用。因此在合成时要严格控制反应条件，尽量使聚合过程保持恒定的温度、引发剂浓度、单体浓度和溶剂浓度等。  \n\n热塑性丙烯酸树脂具有可熔可溶、良好的保光、保色性能，耐水、耐化学品性能，干燥快、施工方便，易于重涂和返工。制备铝粉漆时，铝粉的白度好、定位性好；用作清漆时，只要溶剂挥发就可以达到干燥目的。和热固性丙烯酸树脂相比，热塑性丙烯酸树脂的涂膜厚度及丰满度较差；对温度的敏感性较差；树脂的玻璃化温度提高时，涂膜易开裂；玻璃化温度低时，树脂遇热易软化及发黏。由于涂料助剂目前发展十分快速，树脂的许多不足之处如颜料的分散性、喷涂时溶剂的释放性、膜的流展性等可以通过添加助剂来调控。  \n\n热塑性丙烯酸树脂可与其他成膜物如硝基纤维素、醋丁纤维素、过氯乙烯等拼用来进一步提高和改善涂膜性能。对于这类热塑性丙烯酸树脂，分子量可稍低些。  \n\n在实际应用中，常用硝酸纤维素来改性丙烯酸树脂，添加量没有明显的限制，可根据实际需要而定，一般在 $2\\%\\sim20\\%$ 。研究发现，硝酸纤维素能明显改善涂膜的热敏感性、溶剂释放性、流展性、硬度、耐溶剂性能、耐湿热性能，防止涂膜开裂和浮色，能提高涂膜的抛光打磨性能；在金属闪光漆中，硝酸纤维素能提高铝粉的定位性，增加铝粉的白度，提高装饰效果。但是，用硝酸纤维素改性后的热塑性丙烯酸树脂，施工时涂料的固体分下降，涂膜的光泽、延展性以及保光、保色性能、耐候性均下降。  \n\n醋丁纤维素也常用来与热塑性丙烯酸树脂拼用以改善涂膜性能，醋丁纤维素与热塑性丙烯酸树脂拼用，涂料的耐候性、保光性能优良。喷涂性、溶剂释放性好，可防止开裂；并减少色漆中浮色。在金属漆中，加入醋丁纤维素后铝粉的定位性提高，效果一般比硝基纤维素要好。但缺点是价格高，树脂的相容性差，对溶剂溶解性能要求提高。  \n\n热塑性丙烯酸树脂的柔韧性可以通过加入少量的增塑剂如邻苯二甲酸二丁酯等来改善，加入增塑剂改性后，涂膜的光泽、伸长率会提高，而硬度、耐汽油性、耐湿性等会下降；加人含有氨基的单体如甲基丙烯酸二甲基氨基乙酯等可以改善涂膜的附着力。在实际应用中也通过拼用少量的环氧树脂以改善树脂的柔韧性和对金属底材的附着力；在浅色漆中，环氧树脂的易黄变性应引起注意。  \n\n过氯乙烯树脂与丙烯酸树脂有极好的相容性，与之拼用后涂料的户外耐候性很优良；对热敏感性能明显改善，对流展性、施工性能及溶剂释放性均有改进，但效果不如纤维索酯。拼用时要注意过氯乙烯树脂不宜使用醇类溶剂；过氯乙烯用量稍大时黏度增高明显，易出现拉丝现象。 2  \n\n热塑性丙烯酸树脂在汽车、机械、电器、建筑等领域应用广泛，要根据树脂的应用对象，从理论和实践两方面加以考虑来选择何种树脂较为适合。一般来说，单纯的聚甲基丙烯酸甲酯玻璃化温度太高，涂膜太脆，对底材或底漆的附着力差，溶剂不易挥发尽，因此不会选用纯聚甲基丙烯酸甲酯来配制涂料，但可用丙烯酸乙酯、丙烯酸丁酯等单体通过共聚来降低玻璃化温度，改善涂膜的脆性和脱溶剂能力、增加附着力；还可通过引进丙烯睛类高极性的单体提高涂料的耐溶剂性；也可用少量含极性基团的单体如（甲基）丙烯酸、（甲基）丙烯酸羟乙（丙）酯等来改善涂膜的附着力、对颜料的分散性以及提高涂膜的稳定性。若在树脂制造中加入适量的丙烯酸异冰片酯或甲基丙烯酸异冰片酯能显著提高树脂的硬度、耐醇性和耐热性，并能提供较好的柔顺性。  \n\n下面举例说明热塑性丙烯酸树脂的配方、合成工艺及应用。  \n\n配方1  \n\n<html><body><table><tr><td>原料名称</td><td>用量/%</td><td>原料名称</td><td>用量/%</td></tr><tr><td>丙烯酸丁酯</td><td>6.0</td><td>甲基丙烯酸丁酯</td><td>30.0</td></tr><tr><td>甲基丙烯酸</td><td>1. 5</td><td>过氧化苯甲酰</td><td>(0.4+0. 15)</td></tr><tr><td>甲基丙烯酸甲酯</td><td>12.5</td><td>醋酸丁酯</td><td>50</td></tr></table></body></html>  \n\n制造工艺：将溶剂醋酸丁酯按配方量的 $90\\%$ 加到反应釜中，然后加热升温到 $110^{\\circ}\\mathrm{C}$ ；将100%的混合单体及0.4%的过氧化苯甲酰事先混合好，用 $2.5\\sim3\\mathrm{h}$ 均匀滴加到反应系统中，滴加完毕后，再将反应温度调整到回流状态，在回流温度下保温2h；将剩余的 $10\\%$ 醋酸丁酯与0.15%的过氧化苯甲酰事先混合好，再用 $_{1\\sim2\\mathrm{h}}$ 的匀速补滴加到烧瓶中深化聚合。当转化率达 $95\\%$ 以上时即可降温出料。  \n\n该树脂具有较好的柔韧性、耐寒性、耐湿热及耐候等性能。和过氯乙烯树脂拼用所制成的磁漆，可用于桥梁等表面的装饰；如将上述树脂配方中的甲基丙烯酸的用量减少（酸值降低)，该树脂可用作轿车金属修补漆；为了增加铝粉的定位性和涂膜的干性，可拼用部分醋丁纤维素；在配方中可加入部分高极性的丙烯睛，以提高树脂的耐油性；加入部分丙烯酸乙酯以提高树脂的耐寒性、耐溶剂性及附着力等。  \n\n热塑性丙烯酸树脂在建筑涂料中的应用十分广泛。由于是户外涂料，对其耐候性要求很高，因此，在配方中尽可能少用苯乙烯单体，多用带甲基的丙烯酸酯单体，如甲基丙烯酸丁酯等。树脂合成中在确保质量的前提下，成本是优先考虑的问题，对于耐候性要求不太高的场合，即可用苯乙烯代替甲基丙烯酸甲酯。溶剂一般要求挥发比较慢，可用一些芳香油溶剂。树脂的玻璃化温度一般控制在 $10\\mathrm{\\sim}40\\mathrm{\\top}$  \n\n配方2  \n\n\n<html><body><table><tr><td>原料名称</td><td>用量/%</td><td>原料名称</td><td>用量/%</td></tr><tr><td>甲基丙烯酸</td><td>1.5</td><td>过氧化苯甲酰</td><td>(0. 4+0. 15)</td></tr><tr><td>丙烯酸丁酯</td><td>7.0</td><td>甲苯</td><td>25</td></tr><tr><td>甲基丙烯酸甲酯</td><td>20.5</td><td>醋酸丁酯</td><td>25</td></tr><tr><td>苯乙烯</td><td>20.5</td><td></td><td></td></tr></table></body></html>  \n\n制造工艺：合成方法、步骤与配方1相似。  \n\n热塑性丙烯酸树脂在塑料表面的涂装应用很多，最普遍的是ABS塑料。上述配方树脂通过硝化棉的改性，制成的涂料在ABS塑料上有良好的附着力和硬度，而且可耐汽油、乙醇等溶剂的擦洗。  \n\n在涂料的实际应用中，涂层在很多情况下是复合层，即底漆-中涂-面漆（或清漆），为了达到施工、成本及装饰效果最佳，底漆或中涂采用单组分热塑性丙烯酸树脂体系，为面漆采用双组分聚氨酯体系，但两者往往存在层间结合力的问题。通常的解决办法是在合成热塑性丙烯酸树脂时加人少量的含羟基单体（羟基含量一般在 $0.3\\%\\sim0.7\\%)$ ，  \n\n(3）热固性丙烯酸酯涂料热固性丙烯酸树脂是指在树脂中带有一定的官能团（例如羟基等)，在制漆时通过和加入的三聚氰胺树脂、环氧树脂、异氰酸酯等中的官能团反应形成网状结构。热固性丙烯酸树脂的分子量一般低于30000，在 $10000{\\sim}20000$ 之间，控制 $M_{\\mathrm{w}}/$ $M_{\\mathfrak{n}}$ 在 $2.3{\\sim}3.3$ 。通过高固体树脂的合成工艺，树脂的分子量可低至2000。因此在施工黏度下，涂料的固体分可达 $30\\%\\sim70\\%$ 。使用时黏度较低，分子本身和交联聚合物的官能度大于2，官能单体的含量在分子骨架中占 $5\\%\\sim25\\%$ 。热固性丙烯酸涂料有优越的丰满度、硬度、光泽、耐溶剂性、耐候性，在高温烘烤时不变色、不泛黄，具有优异的保色性能。  \n\n$\\Phi$ 热固性树脂官能团及交联剂热固性丙烯酸树脂所含的官能团参见如下。  \n\n![](images/f6b938e9ec2b8f91386fcbdac754fbeef3f02940a0491864e8124b0e3c2a13ee.jpg)  \n\n热固性丙烯酸树脂的交联是通过聚合物链上的功能基团来进行的，所以聚合物链上的功能基团是决定采用何种交联途径的先决条件。通常的反应有如下几类。  \n\na.丙烯酸树脂中的羧基与氨基树脂交联b.丙烯酸树脂中的羧基与环氧树脂交联  \n\n$$\n\\begin{array}{c}{{\\longrightarrow}}\\\\ {{{\\mathrm{CH}}_{\\imath}\\mathrm{~-CH-CH}_{\\imath}\\mathrm{~-~\\thinspace}\\mathrm{~H}_{0}\\mathrm{~-~\\thinspace}\\displaystyle\\left.\\begin{array}{c}{{0}}\\\\ {{1}}\\\\ {{0}}\\end{array}\\right|\\longrightarrow~{\\displaystyle-c H_{\\imath}\\mathrm{-~\\largeCH-CH}_{\\imath}\\mathrm{--}0-c\\right\\}~.}}\\\\ {{{\\mathrm{OH}}}}\\end{array}\n$$  \n\n固化温度较高，一般在 $170^{\\circ}\\mathrm{C}$ 左右，加入适量的碱作催化剂时，固化温度可降至 $150\\Upsilon$ 其涂膜光亮丰满、硬度高，尤其是耐污染、耐磨性好和附着力极好，但其涂膜的保色性稍差。  \n\nc.丙烯酸树脂中的羟基与氨基树脂交联  \n\n$$\nN-C H_{2}O R+H O\\rightarrow\\rightarrow C N-C H_{2}-O\\rightarrow+R O H\\uparrow\n$$  \n\n最为常用的氨基树脂有两种，一种是完全甲醚化（也可丁醚化）的，在强酸催化下，该类体系可以在 $125{\\sim}135\\mathrm{\\textperthousand}$ 下 $30\\mathrm{{min}}$ 内体系可完全固化；另一种是部分羟甲基化的，该交联剂的活性较高，在弱酸性催化剂催化下， $110{\\sim}115^{\\circ}\\mathrm{C}$ 下 $30\\mathrm{{min}}$ 内体系可完全固化。  \n\nd.丙烯酸树脂中的羟基与环氧树脂交联  \n\n$$\n\\mathrm{~\\longrightarrow~CH_{2}-C H-C H_{2}~+~H O-}\\Bigg\\{\\mathrm{~\\longrightarrow~\\zeta~\\longrightarrow~CH_{2}-C H-C H_{2}-O-}\\Bigg\\}\n$$  \n\n芳香族环氧与羟基没有足够的反应活性，但脂肪族环氧在适当的催化剂作用下可与羟基进行反应，在 $120\\%$ 下可以交联成膜，涂料性能优异。  \n\ne.丙烯酸树脂中的羟基与异氰酸酯交联  \n\n异氰酸酯与羟基可在常温下进行反应，涂膜丰满，光泽高，耐磨耐刮伤性好，耐水、耐溶剂和耐化学腐蚀性好。若采用HDI三聚体或缩二脲这类脂肪族异氰酸酯为固化剂，其耐候耐热性、保色保光性和柔韧性极好。  \n\nf.丙烯酸树脂中的环氧基与氨基交联  \n\n胺与环氧基反应的影响因素较多，它们的反应可以在室温下进行，也可在较低的温度下进行，也可在较高的温度下进行，这与多胺的结构有直接的关系。  \n\ng.丙烯酸树脂中的环氧基自身交联  \n\nh.丙烯酸树脂中的酰氨基与氨基树脂交联  \n\ni.丙烯酸树脂中的 $N\\mathrm{.}$ 羟甲基与尿素交联  \n\nj.丙烯酸树脂中的 $N_{\\sun}$ 羟甲基自身交联  \n\n$$\n2)-N-C H_{2}-O H\\xrightarrow[<110C^{\\circ}]{}\\left\\{\\substack{N-C H_{2}-O-C H_{2}-N-1}\\left\\{\\begin{array}{l}{{\\mathrm{~}}}\\\\ {{\\mathrm{~>~I~}0C^{\\circ}}}\\end{array}\\right.\\left\\{\\begin{array}{l}{N-C H_{2}-N-1}\\\\ {N-C H_{2}-N-1}\\end{array}\\right\\}\\left\\}\\right.\n$$  \n\n目前热固性丙烯酸涂料有丙烯酸-氨基烘烤型涂料、丙烯酸-聚氨酯涂料、含环氧基丙烯酸酯类涂料、含羧基丙烯酸酯类涂料、丙烯酸改性醇酸类涂料和含硅氧烷基丙烯酸酯类涂料等。在这里着重讨论含羟基的丙烯酸树脂。  \n\n$\\textcircled{2}$ 羟基丙烯酸树脂与氨基树脂的交联这类烘漆的主要交联反应为丙烯酸树脂中的羟基及羧基与氨基树脂中的烷氧基反应，反应温度一般在 $100{\\sim}140^{\\circ}\\mathrm{C}$ 。此类氨基树脂固化的丙烯酸热固性树脂具有较好的硬度、耐候性、保光性、保色性、耐化学品性等，在汽车、摩托车、自行车、五金等工业上应用十分广泛。  \n\n这类树脂可能的反应为：  \n\na.  \n\nb.  \n\nc.  \n\n$$\n\\begin{array}{r l}&{\\qquad\\Bigl|\\lambda^{-\\mathbf{cq}_{k}-\\mathbf{cq}_{k}+\\mathbf{c}}+\\Bigr|\\coth\\frac{\\mathrm{st}^{-\\mathbf{k}}}{2}\\Bigr\\rangle-\\mathrm{crat}-\\frac{\\mathrm{st}^{+}}{2}+\\mathrm{ct}\\mathrm{d}\\mathbf{,}\\qquad}\\\\ &{\\qquad\\quad\\times-\\mathrm{cR}_{k}-\\mathrm{crat}_{k}+\\Bigr|-\\mathrm{con}\\mathbf{u}\\frac{\\mathrm{st}^{+}}{2}\\Bigr\\rangle-\\sum\\mathrm{cR}_{k}-\\mathrm{con}-\\frac{\\mathrm{c}_{k}^{0}}{2}+\\frac{\\mathrm{cR}_{k}\\mathrm{d}\\mathbf{,}}{2}}\\\\ &{\\qquad\\quad\\times-\\mathrm{cR}_{k}-\\mathrm{coc}_{k}\\mathbf{u}_{k}+\\Bigr|\\coth\\frac{\\mathrm{st}^{+}}{2}\\Bigr\\rangle-\\sum\\mathrm{cR}_{k}-\\mathrm{con}\\frac{\\mathrm{st}^{+}}{2}+\\mathrm{ch}\\mathrm{d}\\mathbf{,}\\qquad}\\\\ &{\\qquad\\quad\\times-\\mathrm{cut}_{k}-\\mathrm{coc}_{k}\\mathbf{u}_{k}+\\Bigr[\\coth\\frac{\\mathrm{st}^{+}}{2}\\Bigr\\rangle-\\sum\\mathrm{cR}_{k}-\\mathrm{con}-\\frac{\\mathrm{cut}^{+}}{2}+\\mathrm{cupt}}\\\\ &{\\qquad\\quad\\times-\\mathrm{cut}_{k}-\\mathrm{con}+\\left\\{\\begin{array}{r r r r r}{\\mathrm{cut}_{k}}&{\\mathrm{surce}_{k}}&{\\mathrm{con}-\\mathrm{cut}_{k}}\\\\ {\\mathrm{con}\\mathbf{u}_{k}}&{\\mathrm{con}-\\mathrm{cut}_{k}-\\mathrm{con}-\\mathrm{cut}_{k}}\\end{array}\\right\\}+\\mathbf{u}_{k}\\mathrm{d}\\mathbf{,}}\\\\ &{\\qquad\\quad\\times-\\mathrm{cut}_{k}-\\mathrm{con}+\\left\\{\\begin{array}{r r r r}{1+\\mathrm{cut}_{k}}&{\\mathrm{con}}&{\\mathrm{cut}_{k}}\\end{array}\\right\\}}\\\\ &{\\qquad\\quad\\times-\\mathrm{cut}_{-}-\\mathrm{out}+\\mathrm{con}\\mathbf{u}_{k}\\to\\sum\\mathrm{cut}_{-}\\mathrm{cut}_{-}\\mathrm{con}\\frac{\\mathrm{cut}_{k}}{2}+\\mathrm{cut}_{0}}\\\\ &{\\qquad\\times-\\mathrm{cut}_{-}-\\mathrm{out}+\\mathrm{con}\\mathbf{u}_{k}\\to \n$$  \n\nd.  \n\ng  \n\n$$\n\\begin{array}{r l}&{\\qquad\\mathrm{{N-CH}}_{2}\\mathrm{{OH}}+\\mathrm{{\\displaystyle\\sum}}\\mathrm{{N-CH}}_{2}{\\mathrm{OH}}\\overset{{\\mathrm{H}}{\\rightharpoonup}}{\\rightharpoonup}\\mathrm{{N-CH}}_{2}\\mathrm{{-N}}{\\leftharpoons}+\\mathrm{{CH}}_{2}\\mathrm{{O+H}}_{2}\\mathrm{{O}}}\\\\ &{\\qquad\\mathrm{{N-CH}}_{1}{\\mathrm{OH}}+\\mathrm{{\\displaystyle\\sum}}\\mathrm{{N-CH}}_{2}{\\mathrm{OH}}\\overset{{\\mathrm{OH}}{\\rightharpoonup}}{\\rightharpoonup}\\mathrm{{N-CH}}_{2}\\mathrm{{-O-CH}}_{1}\\mathrm{{-N}}{\\bigg(}\\mathrm{{+H}}_{\\bar{\\tau}}\\mathrm{{O}}}\\\\ &{\\qquad\\mathrm{{N-CH}}_{2}{\\mathrm{OH}}+\\mathrm{{\\displaystyle\\sum}}\\mathrm{{NH}}\\overset{{\\mathrm{H}}{\\rightharpoonup}}{\\rightharpoonup}\\mathrm{{N-CH}}_{2}\\mathrm{{-N}}{\\bigg(}\\mathrm{{+H}}_{\\bar{\\tau}}\\mathrm{{O}}}\\end{array}\n$$  \n\n其中，a. ${\\sim}\\mathrm{d}.$ 的反应为主要反应。  \n\n丙烯酸树脂中提供的交联基团主要是羟基（一OH)，其类型有伯羟基和仲羟基两类。丙烯酸羟乙酯（HEA)、甲基丙烯酸羟乙酯（HEMA）中的羟基属于伯羟基，甲基丙烯酸羟丙酯（HPMA)、丙烯酸羟丙酯（HPA）中的羟基属于仲羟基。实验发现，伯羟基的反应活性比仲羟基大。用HPMA代替HEMA的热固性丙烯酸树脂与三聚氰胺-甲醛树脂反应，达到一定的交联密度需要提高 $10\\sim20\\Upsilon$ 的烘烤温度。商品级的HEMA和HEA中含有少量的双酯，在HEMA中含乙二醇二甲基丙烯酸酯。单酯和双酯因沸点接近难以完全分离，因此在配方中，羟基单体量大时会使树脂分子量偏高，分布偏宽，甚至会出现凝胶。在HPMA中，双酯的含量一般较低，是以仲羟基占主导的异构体混合物。由于HPMA含有叔碳氢原子，因此其抗氧化性低于HEMA。  \n\n将含羟乙酯类单体的丙烯酸类树脂用于丙烯酸-氨基系统中，应注意此类涂料的贮存期将非常有限，一般在 $2{\\sim}3$ 个月，超过这段时间涂料在贮存过程中将逐渐增稠，严重时甚至凝胶。  \n\n热固性丙烯酸树脂中经常带有一定数量的羧基，它能与氨基树脂交联，具有一定的催化作用，也能减少涂料中颜料的絮凝。目前在市场上树脂的酸值一般在 $2{\\sim}30\\mathrm{mg}~\\mathrm{KOH/g}$ 之间，酸值小，有利于金属漆配制，漆中的闪光粉在贮存时不容易变暗，但固化速率会变慢；酸值高有利于树脂的颜料分散性，固化速度也会提高。  \n\n氨基树脂的品种与用量对烘烤漆的性能、固化速度等有明显的影响，氨基树脂是醚化了的三聚氰胺甲醛树脂。最活泼又最容易交联反应的基团为羟甲基；亚氨基的存在能增进氨基树脂分子间的交联反应，烷氧甲基中无论甲醇或丁醇醚树脂的交联反应活性均低于羟甲基，完全醚化的品种中，烷基链较长时其活性低于短的，丁氧甲基的反应温度要比甲氧甲基高$30^{\\circ}\\mathrm{C}$ 左右才能达到相仿的交联转化程度。但如果氨基树脂是部分烷基化而具有一定比例羟甲基时，其反应速度将明显高于任何完全醚化的品种。烷基化部分无论是甲氧基或丁氧基都不会明显地影响反应活性。二者具有相似的反应曲线。高甲氧基化［如六甲氧基甲基三聚氰胺(HMMM)］而基本不含羟甲基的三聚氰胺树脂排除了c.～i.7种反应的可能性，不存在氨基树脂内部的自缩聚，只有氨基树脂与丙烯酸树脂之间的交联反应，反应活性大大降低，应用此类氨基树脂时就必须大大提高反应温度或延长反应时间，常要求在 $160^{\\circ}\\mathrm{C}$ 或更高的温度下烘干或采用强酸催化剂来降低固化温度，而含一定比例羟甲基的部分醚化的品种则可以在$120{\\sim}130^{\\circ}\\mathrm{C}$ 下与丙烯酸树脂交联固化。  \n\n高羟基化、高醚化的三聚氰胺甲醛树脂是高固体分的重要方向之一，树脂一般聚合度小于2，自身固体分在 $90\\%$ 以上；产品贮存稳定性好；有很好的平衡硬度和弹性等物理性能。  \n\n用甲醇醚化的产品活性大、硬度高、耐溶剂好及较好的户外耐久性；用丁醇部分代替甲醇或全部用丁醇醚化，产品有很高的疏水性、黏度低、层间附着力强，表面张力低，易润湿底材、流平性好。  \n\n醚化程度高，产品稳定性好，黏度低，活性低。  \n\n三聚氰胺环聚合度增加，分子的官能度增大，涂层的柔韧性、层间的附着力提高，减少发生缩孔的可能性，减少高温烘烤时树脂的挥发。  \n\n考虑到氨基丙烯酸涂料的实际应用，羟基丙烯酸树脂与氨基树脂的交联速度常是考虑的问题，尤其是高羟甲基化、高醚化的三聚氰胺甲醛树脂，它是高固体分涂料重要品种，经充分交联能得到性能优异的涂层，但烘烤温度较高。在应用时常要加入酸性催化剂。酸性催化剂的选择对烘烤温度，烘烤时间，涂膜性能以及涂料储存时间影响非常明显。目前使用广泛的有两种潜催化剂：一种为离子型，由磺酸与胺生成离子键，是可逆的；另一种为非离子型，封闭剂与磺酸以共价键结合，反应是不可逆的。  \n\n第一种最普遍的是磺酸胺盐，中性，在氨基丙烯酸涂料中起催化作用，涂料贮存期间是稳定的。在涂料固化过程中磺酸胺盐分解生成胺和磺酸，胺随着溶剂溢出涂层，使反应向左移动，生成的磺酸催化氨基丙烯酸涂层固化反应。由于反应是可逆的，生成磺酸的速率取决于胺在涂层中的迁移和挥发速率，一般胺的碱性越强，潜催化的分解速率和生成的胺在涂层中迁移速率越慢，贮存越稳定。胺的沸点低，挥发速率快，利于生成磺酸。挥发速率太快，在涂层中形成浓度梯度太大，使涂层表面固化交联速率大于底部固化交联速率，涂层表面易出现起皱等病态。  \n\n第二种主要有环氧化合物封闭的磺酸化合物。催化效果接近对甲苯磺酸，贮存基本稳定。如采用对甲苯磺酸与叔碳酸缩水甘油酯的加成物，与基料有很好的混溶性，得到的涂层外观明显优于离子型潜催化剂，耐化学性能也有所提高。  \n\n在丙烯酸氨基涂料中，通常拼入其他树脂进行改性以提高某一方面的性能，例如，通过加入环氧树脂以提高对金属底材的附着力，提高涂膜的柔韧性，耐盐雾性能；通过加入聚酯以提高涂膜的丰满度及柔韧性；通过加人醋丁纤维素以提高金属漆中的铝粉排列定位性；通过拼入醇酸树脂以降低成本以及提高涂膜的丰满度。  \n\n用于与氨基树脂交联的丙烯酸树脂的玻璃化温度较低，一般为 $-10\\sim30\\ensuremath{\\mathsf{C}}$ ，视氨基树脂的不同而不同。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 280,
+        "chunk": "# 热固性丙烯酸树脂配方及合成方法举例如下。  \n\n配方1合成工艺：  \n\n<html><body><table><tr><td>原料</td><td>用量/%</td><td>原料</td><td>用量/%</td></tr><tr><td>甲基丙烯酸</td><td>2</td><td>苯乙烯</td><td>10</td></tr><tr><td>甲基丙烯酸甲酯</td><td>22</td><td>过氧化苯甲酰（BPO）</td><td>2</td></tr><tr><td>甲基丙烯酸羟丙酯</td><td>18</td><td>二甲苯</td><td>38</td></tr><tr><td>丙烯酸丁酯</td><td>8</td><td></td><td></td></tr></table></body></html>  \n\na.将配方中二甲苯总量的75%投入装有滴液漏斗、球形冷凝器、分水器和温度计的四口反应瓶中，加热升温至回流温度。  \n\nb.预先将单体混匀后，置于滴液漏斗里；再将配方中 $90\\%$ 的引发剂BPO和 $20\\%$ 的二甲苯溶解并均匀混合。  \n\nc.当反应瓶回流后，开始同时滴加混合单体和引发剂，在4h左右滴完。  \n\nd.回流保温1h，再补加剩余的 $10\\%$ 引发剂和 $5\\%$ 溶剂的混合液。  \n\ne.继续回流保温2h，测定树脂指标，合格后降温、过滤、出料。  \n\n技术指标：  \n\n<html><body><table><tr><td>外观</td><td>无色或微黄透明液体</td><td>固体分/%</td><td>59~61</td></tr><tr><td>颜色（Fe-Co法）/号</td><td>≤2</td><td>酸值/（mgKOH/g）</td><td>8~13</td></tr><tr><td>黏度（加氏管，25℃）/s</td><td>25~50</td><td></td><td></td></tr></table></body></html>  \n\n该树脂与丁醇改性三聚氰胺甲醛树脂，以质量比 $3.5:1$ 混合，加人流平剂、溶剂等后制成丙烯酸烘干清漆；或加入颜料、分散剂、丁醇改性三聚氰胺甲醛树脂交联剂、流平剂、润湿剂和溶剂制成色漆。  \n\n配方2  \n\n<html><body><table><tr><td>原料</td><td>用量/g</td><td>原料</td><td>用量/g</td></tr><tr><td>1芳烃（150~180C）</td><td>308</td><td>6苯乙烯</td><td>220</td></tr><tr><td>2丁醇</td><td>22</td><td>7过氧化二叔丁基</td><td>11</td></tr><tr><td>3丙烯酸</td><td>14</td><td>8芳烃</td><td>97</td></tr><tr><td>4甲基丙烯酸-2-乙基已酯</td><td>177</td><td>9丁醇</td><td>23</td></tr><tr><td>5甲基丙烯酸羟乙酯</td><td>128</td><td></td><td></td></tr></table></body></html>  \n\n操作工艺：组分 $_{1\\sim2}$ 加入反应瓶，通氮气，搅拌，加热至 $146\\sim148^{\\circ}\\mathrm{C}$ ，在5h内均匀滴加组分 $3{\\sim}6$ ，滴加完毕后，并再分别保温 $5\\mathord{\\sim}6\\mathrm{h}$ ，降温，加入组分 $\\scriptstyle8\\sim9$ @  \n\n<html><body><table><tr><td colspan=\"3\">技术指标：</td></tr><tr><td>固体分/%</td><td>55.3 羟值/（mg KOH/g)</td><td>102</td></tr><tr><td>酸值/（mgKOH/g）</td><td>20.4 黏度（25℃）/mPa·s</td><td>1950</td></tr></table></body></html>  \n\n该树脂与丁醚化氨基树脂交联，可得到耐酸性能良好的涂层。  \n\n对于低温快干丙烯酸树脂，可选用伯羟基的单体如丙烯酸羟乙酯、甲基丙烯酸羟乙酯，并适当加大丙烯酸或甲基丙烯酸的量，调整引发剂的用量。合成出的树脂与氨基树脂组成的烘漆在 $100\\mathrm{^{\\circ}C}$ 烘烤 $30\\mathrm{{min}}$ 能得到理想的涂膜性能。  \n\n对于用于烘漆的丙烯酸树脂，除了硬度、附着力外，其耐水性和耐盐雾性往往是重点。要提高这方面的性能，除了考虑单体的性能外，涂膜交联密度高、分子量分布窄、羟基官能团在高分子中的分布均匀性是关键，要避免因工艺及竞聚率等原因生成部分不含官能团的热塑性丙烯酸聚合物。  \n\n$\\textcircled{3}$ 羟基丙烯酸树脂与异氰酸酯的交联由羟基丙烯酸树脂和多异氰酸酯（即丙烯酸聚氨酯漆）交联，可常温干燥或低温（通常为 $60\\sim80^{\\circ}\\mathrm{C}$ ）烘烤，涂膜丰满，光泽高，鲜映度好，有良好的物理性能，耐候性好，耐介质（如水、酸、盐、碱、酒精、油、苯类、酯类等）优越，因此，该类涂料在飞机、汽车、摩托车、建筑等户外表面装饰应用广泛。在机械、电器、家具等方面也有良好的用途。  \n\n这类涂料的主要反应为：  \n\n![](images/ecd48b414637f8c71c14d23cf5e979e27c1a24380ee1126f096b8b341ab2007b.jpg)  \n\n这类丙烯酸树脂的玻璃化温度一般在 $10\\sim60\\ensuremath{\\mathbb{C}}$ ，比用于烘漆的树脂的 $T_{\\ast}$ 高。  \n\n多异氰酸酯的选择对涂膜的性能影响十分明显。异氰酸酯固化剂分为两大类，一类是芳香族异氰酸酯固化剂，在光和氧的作用下，苯环打开，异氰酸酯基直接与苯环形成对苯醒型，而对苯醒含有发色基团，故呈黄色。因此，以芳香族异氰酸酯为原料的聚氨酯漆易变黄，只能用在底层或中间层或室内颜色较深的涂层。另一类是脂肪族异氰酸酯固化剂如德国拜尔的DesmodurN75、HDI三聚体3390以及德国Huse公司异氟尔酮三聚体T1890等，这类固化剂组成的聚氨酯漆在耐黄变、耐化学性能、耐候性、丰满度等方面具有优越的性能。  \n\n羟基丙烯酸树脂中的—OH基团与固化剂中的—NCO基团的配比对涂膜的性能有较大的影响。在一般情况下，[一OH］与[—NCO]的比例在 $1:(1.1\\sim1.4)\\$ ）为宜。如[—OH]:[—NCO] $<1$ ，则涂膜固化不完全，干燥时间慢，耐水及耐化学品性能差；[—OH]：[—NCO]>1.4，则涂膜易发脆，有裂纹，而且使产品成本上升。由于树脂及固化剂的内在结构差异较大，最适合的比例范围应通过实验来确定。  \n\n为了缩短涂膜干燥时间，增加涂膜硬度，需添加催干剂来加速—NCO和--OH的反应。常用聚氨酯催化剂一般有三类：叔胺类、有机锌化合物和有机锡化合物。叔胺类催干剂使用期短，对涂膜的耐候性有不利的影响；锌催干剂是一种助催干剂，能保持涂膜较长开放时间，使涂膜彻底干燥，但其用量较大，涂膜表干时间较长，对生产不利；有机锡化合物能与异氰酸酯和羟基化合物形成配合物，使异氰酸根和羟基相互作用接近，使反应容易进行，同时减少氨酯键裂解的不利反应，对涂膜耐候性有一定的稳定作用。因此在配方中，常采用有机锡作催干剂。  \n\n下面举例说明配方与合成方法。  \n\n<html><body><table><tr><td>配力：</td><td>用量/%</td><td>原料名称</td><td>用量/%</td></tr><tr><td>原料名称 苯乙烯</td><td>8</td><td>丙烯酸丁酯</td><td>16.7</td></tr><tr><td>甲基丙烯酸</td><td>0.3</td><td>BPO</td><td>1.6+0.4</td></tr><tr><td></td><td>20</td><td>二甲苯</td><td>32</td></tr><tr><td>甲基丙烯酸甲酯 甲基丙烯酸羟乙酯</td><td>13</td><td>丙二醇甲醚酷酸酯</td><td>8</td></tr></table></body></html>  \n\n制造工艺：将处理好的单体、部分引发剂投入到高位槽混合均匀。将配方中溶剂的90%投人反应签，升温到回流温度，开始滴加混合单体，控制滴加速度，使其在 $3\\sim4\\mathrm{h}$ 内将高位槽中的混合单体滴完。保温1h后，滴加剩余的引发剂（先将引发剂用于留下的 $10\\%$ 溶剂中)，控制在 $30\\mathrm{{min}}$ 左右滴完。然后再保温至黏度、固体分合格后，冷却、过滤，包装。  \n\n技术指标：  \n\n<html><body><table><tr><td>外观</td><td>无色或微黄透明液体</td><td>固体分/%</td><td>59~61</td></tr><tr><td>颜色（Fe-Co法）/号</td><td>≤1</td><td>酸值/（mgKOH/g）</td><td>2~6</td></tr><tr><td>黏度（加氏管，25℃）/s</td><td>25~50</td><td>羟基含量（100%固体分）/%</td><td>2.8</td></tr></table></body></html>  \n\n该树脂与脂肪族异氰酸酯固化剂拼用，具有良好的硬度、干性、力学性能，耐候及耐介质性能，曾被用于防腐工程、外墙面漆和汽车面漆，经过十年跟踪考察，性能良好。（）  \n\n根据涂料的性能要求和应用场合，树脂配方可以有很大变动，羟基酯品种及含量、树脂的玻璃化温度、各种单体的种类和配比对树脂的性能影响较大。  \n\n对于和脂肪族异氰酸酯交联，伯羟基反应快，仲羟基反应慢，对于TDI三羟甲基丙烷加成物，两者的差距不甚明显。  \n\n配方中苯乙烯含量偏高可能会缩短涂料的使用时间，尤其是缩二脲异氰酸酯固化剂，如拜尔N-75固化剂。此外，含有羟乙酯的树脂的活化期也比较短，尤其是高温季节，这类问题比较突出，在配方设计时应给予重视。  \n\n羟基丙烯酸类涂料主要依靠交联反应成膜，故其树脂的玻璃化温度范围略低于热塑性丙烯酸类树脂。在丙烯酸-聚氨酯系统中采用的羟基丙烯酸类树脂的玻璃化温度范围应参照所采用的固化剂的性能，如采用芳香族异氰酸酯类三聚体为固化剂时，玻璃化温度可设计得低一些 $(-20\\sim20^{\\circ}\\mathsf{C})$ ，而采用脂肪族异氰酸酯类固化剂时，则可以设计得高一些$(20\\sim60\\Upsilon)$ 。  \n\n表2-1-99羟基丙烯酸类树脂 $\\pmb{T_{\\parallel}}$ 对漆膜性能的影响  \n\n\n<html><body><table><tr><td>T/C</td><td>表干时间/min</td><td>附着力/级</td><td>柔顺性/mm</td><td>铅笔硬度/H</td><td>冲击性/cm</td></tr><tr><td>33</td><td>30</td><td>2</td><td>>5</td><td>2~3</td><td><50</td></tr><tr><td>20</td><td>30</td><td>2</td><td>3</td><td>2~3</td><td><50</td></tr><tr><td>2</td><td>25</td><td>1</td><td>3</td><td>2~3</td><td><50</td></tr><tr><td>13</td><td>13</td><td>1</td><td>1</td><td>2</td><td>≥50（正反）</td></tr><tr><td>-20</td><td>10</td><td>1</td><td>1</td><td>2</td><td>≥50(正反)</td></tr></table></body></html>\n\n注：采用TDI三聚体为困化剂，羟基丙烯酸类树脂 $\\mathrm{TDI}\\equiv\\Re\\{*=2,5\\ :\\ 1,$  \n\n从表2-1-99中所列的数据可知，羟基丙烯酸类树脂在与TDI三聚体之类芳香族异氰酸酯类三聚体匹配时，丙烯酸类树脂的玻璃化温度范围小于 $0\\%$ 时，可得到比较理想的漆膜综合性能。由此可见，在设计树脂配方选择单体及其配比时，应根据不同使用场合、涂料系统中的其他成分等综合审定，然后按照FOX公式进行聚合物的 $T_{*}$ 估算，看其是否符合上述框定的范围。  \n\n考虑到涂料的层间附着力，仲羟基可能比伯羟基更好些。在配方设计时可考虑伯羟基单体和仲羟基单体混合使用，比例可在 $(7:3)\\sim(5:5)$ 之间。当然，涂层间的附着力还可以从助剂、溶剂、施工条件、用其他树脂拼用等方面加以考虑。  \n\n树脂的羟基含量一般在 $1.0\\%\\sim6.0\\%$ 之间，多数在 $3.0\\%$ 左右；羟基含量增大，漆膜的硬度、附着力、抗冲击、耐磨性、耐水性及耐溶剂性均有所提高，但树脂的黏度也会急剧上升，柔韧性下降。目前汽车面漆普遍关注的抗划伤性能与树脂的交联密度和 $T_{\\mathrm{s}}$ 成正比关系。  \n\n树脂的酸值一般设计在 $2{\\sim}15\\mathrm{mg}\\mathrm{KOH/g}$ 之间。酸值高可提高漆膜的附着力、树脂的颜料分散性、树脂与多异氰酸酯的混溶性以及加快固化反应，但酸值太高会造成树脂的黏度明显上升，涂料活化期缩短。羧基与—NCO基团反应释放的二氧化碳可能会导致涂膜表面产生气泡或针孔。  \n\n树脂分子量太高时，加入多异氰酸酯固化剂后，其使用寿命明显缩短，在夏季气温较高时常会导致不能适应施工周期的弊病。由于交联后的涂膜分子量将大大增加，树脂的分子量可以设计偏低一些，不必担心其物理性能。  \n\n考虑到和异氰酸酯交联，树脂中的溶剂一般不含有水、醇、酸等物质，在树脂合成时应加以注意。  \n\n配方中使用的硬单体一般为苯乙烯和甲基丙烯酸甲酯。若要进一步提高树脂的耐候性，可用侧链体积大的环烷基丙烯酸酯代替甲基丙烯酸甲酯，例如用甲基丙烯酸环己酯(CHMA)，它的 $T_{\\ast}$ 为 $83^{\\circ}\\mathrm{C}$ ，CHMA的侧链碳原子较多，其吸湿性比甲基丙烯酸甲酯小得多，耐候性也有大幅度的提高。此外，含CHMA树脂的光泽、鲜映度比含甲基丙烯酸甲酯的树脂优异。  \n\n研究表明，在树脂配方中加人CarduraE10（叔碳酸缩水甘油酯）可以使最终的涂料在加工性等多方面性能有所提高：在反应的初始阶段作为活性溶剂，能够得到高固体分树脂；CarduraE10的大型叔碳结构能够降低涂料黏度，达到施工黏度时有高的丰满度及低的VOC；CarduraEl0的空间位阻效应及疏水性使树脂具有很好的耐酸性。  \n\n④带羧基丙烯酸树脂与环氧化合物交联与环氧树脂交联固化的丙烯酸树脂漆常具有环氧树脂漆所具有的附着力、耐化学药品、耐沾污优良等特点，户外耐久性不及羟基氨基型优良。但上述特点使它在另一些应用领域有较大市场及发展，如洗衣机、电冰箱、食品及化工厂的仪表装备、车辆及电梯的内部装饰等场合均能更好地发挥其特点。  \n\n此类涂料要求较高的烘烤固化温度，制造涂料时常加入适当的催化剂，一般是叔胺化合物，可以使固化温度由大于 $170\\Upsilon$ 降到 $150^{\\circ}\\mathrm{C}$ α  \n\n一般文献推荐的酸含量 $10\\%\\sim15\\%$ （酸值 $_{77\\sim117}$ ）使树脂有足够的交联度。含酸量低于 $^{7}$ 时各方面性能均不理想，高于15时，黏度及硬度均大大提高，而其他物理性能并没有进一步提高。  \n\n丙烯酸树脂与环氧树脂的混溶性有一定限度。大分子量环氧树脂（E-06或E-03）基本上不能与丙烯酸树脂相混溶，E-12的混溶性也有限，所以一般常选用分子量900（E-20）以下的环氧树脂。为了确保相当的交联度，丙烯酸树脂有较高的酸含量，并要求所有的羧基均能与环氧基交联反应，故一般环氧树脂的用量按羧基含量的当量计算，宜加入等当量的环氧基。  \n\n文献上的配方中常采用分子量在 $350{\\sim}470$ （E-51或E-42）的环氧树脂，一般选用环氧当量182（即相当于E-51）的环氧树脂作为交联剂，尽管环氧树脂的分子量较小，对其物理机械性能并无明显影响，仍具有优良的附着力及弹性。  \n\n也有文献采用E-12或E-06等较大分子量环氧树脂者，但均采用远低于等当量的环氧基，并在制造工艺中先把环氧树脂通过酯化反应与丙烯酸树脂结合，才能解决混溶性问题而获得透明的实用树脂。  \n\n$\\textcircled{5}$ 带酰氨基树脂自交联或与其他树脂交联酰氨基团在酸催化剂存在下与甲醛缩合成羟甲基再进一步与丁醇醚化成丁氧甲基，在加热烘烤条件下丁氧甲基基团之间可以自交联，也可以与环氧树脂、氨基树脂等交联。  \n\n酰胺基团交联的丙烯酸酯涂料以其优良的附着力、抗擦伤性及耐碱性、耐沾污性著称，当它与环氧树脂拼和应用时，这些性能更为突出，但其抗大气老化性能低于羟基交联型的，故一般不用于户外。此类型涂料的固化烘烤温度要求 $170\\sim180^{\\circ}\\mathrm{C}$ ，加人酸性催化剂后，可以降低至 $150\\mathrm{^{\\circ}C}$  \n\n目前官能单体丁氧甲基丙烯酸胺及羟甲基丙烯酸胺均有市售产品，应用此种单体时，树脂合成工艺可以完全按一般溶液共聚合树脂工艺进行，但由于这些官能单体售价较高，而在共聚过程中甲醛缩合及丁醇醚化的工艺简单，可以在已参加共聚合丙烯酸胺侧链的酰胺基团上进行，而丙烯酸酰胺的原料价格远较羟甲基化的低廉，所以生产上常采用丙烯酰胺参加共聚，同时在树脂合成过程中进行甲醛缩合及丁醇醚化反应，制成的树脂质量很好。  \n\n人们常利用这类型树脂的耐化学药品性及耐沾污性能，用苯乙烯为其主要硬单体，并加有少量不饱和羧酸单体，它有助于甲醛与酰胺基团的缩合及以后树脂的交联固化。  \n\n酰胺型聚合物，不管有无催化剂存在，在受热的情况下都易于自行交联。当在聚合物中有少量丙烯酸或顺丁烯二酸存在时，即成为内部催化自交联型。以 $0.5\\%$ 的对二甲苯磺酸作为催化剂时，固化温度可降低 $10\\Upsilon$ 。但仅以这些树脂进行物理的混合和固化时，由于固化不够充分，耐碱性不强，还缺乏诸如罐头漆之类所要求的极高的耐曲折性、耐热水性。为了消除这些缺点，可以将环氧树脂结合到聚合物分子以形成一种新型树脂。  \n\n使环氧树脂与丙烯酰胺在溶剂中反应，形成在末端持有可聚合双键的新单体。把上述新单体与苯乙烯、丙烯酸酯、丙烯酸（甲基丙烯酸）等乙烯基单体共聚。按此操作就可得到在同一分子中具有两个以上反应性官能团，在常温下稳定，而受热时则迅速进行热固化反应的树脂。  \n\n(4）改性丙烯酸树脂对丙烯酸树脂进行改性，可以获得特别要求的性能。改性方法主要有三种。第一种是树脂混合，即使用两种不同类型的树脂进行物理混合。该方法在某种程度上有一定的局限性，因为不同类型的树脂在很多情况下相互不混溶。第二种方法是固化法，采用新的固化机理把两种或多种不同官能度类型的树脂混合使用。方法需要全新的固化技术，这样与其相关的施工方法及操作问题也受到了限制。第三种方法是树脂改性，即把主要树脂同改性树脂或单体反应，以保留树脂原有的优点，弥补它的不足之处。该方法比较容易操作，可避免混合树脂的麻烦。  \n\n$\\Phi$ 用氯化聚丙烯（CPP）树脂改性丙烯酸树脂聚丙烯（PP）产量大，成本低，加工方便，被广泛地运用于农业、工业、国防和日用品方面。但由于聚丙烯为烃类聚合物，极性低，结晶化程度高，表面涂装困难较大。丙烯酸树脂虽然用途很广，但在极性较低的底材如PP塑料上附着力较差。通过用CPP改性后的丙烯酸树脂在聚丙烯塑料上附着力良好，可用于用PP塑料制成的汽车保险杠、内饰件等产品的底漆，效果良好。  \n\na.原料甲基丙烯酸甲酯、甲基丙烯酸丁酯、苯乙烯、甲基丙烯酸、丙烯酸丁酯、CPP等，过氧化苯甲酰，甲苯，甲基异丁基酮。  \n\nb.合成方法在反应釜内加人CPP及 $70\\%$ 溶剂加热至 $100^{\\circ}\\mathrm{C}$ ，搅拌至完全溶解。将100%的混合单体及 $70\\%$ 的BPO事先混合好，用4h均匀加到反应系统进行聚合反应。滴加完毕后，保温1h，然后将剩余 $30\\%$ 的溶剂与 $30\\%$ 的BPO事先混合好，分别补加三次，每次保温 $2\\mathrm{h}$ 。整个反应温度保持在 $100{\\sim}110^{\\circ}\\mathrm{C}$ 之间。  \n\n目前市售的CPP产品中氯的含量在 $23\\%\\sim65\\%$ 之间，氯的含量高，在PP上的附着力会下降，反之附着力会提高，但CPP与丙烯酸树脂的混溶性会下降。经验表明：用于改性的CPP的氯含量选择在 $28\\%\\sim32\\%$ ，用量占单体的 $4\\%\\sim20\\%$ a  \n\n一般认为，涂层能在PP塑料上附着，是由于有两种作用的存在。一种是物理机械作用，PP塑料制品表面具有均匀的微观粗糙结构，涂料喷涂到这种微观粗糙表面后，在液体状态时就能侵入微观粗糙的“孔”中，干燥后涂料发生交联，漆膜就像钉子一样“钉”在PP塑料制品上，这就是机械锚合锁扣效应。另一种就是化学键作用，经试验证明，PP分子中含有一定的极性基团，由于受涂料中溶剂的侵蚀，这些极性基团被激活，与涂料中的一些极性基团形成化学键，随着涂料的固化，二者发生交联。同时，涂料中的溶剂的侵蚀也使PP塑料表面产生凹坑，从而也为机械锚合锁扣效应创造了条件。由此表明，涂层在PP塑料上附着是物理和化学两种效应共同作用的结果，附着力是由涂层与PP塑料间物理机械结合及极性基团间的化学键合产生的。  \n\n$\\textcircled{2}$ 聚酯改性丙烯酸树脂聚酯树脂漆膜丰满，耐冲击性强，用聚酯来改性丙烯酸树脂可提高丙烯酸树脂的丰满度。目前在大型客车、中巴车等面漆中常在丙烯酸聚氨酯漆中拼用$10\\%\\sim30\\%$ 的聚酯以使漆膜更加丰满，装饰效果更好。  \n\n用聚酯改性丙烯酸树脂常用两种方法；一种是合成具有一定酸值的聚酯和羟基丙烯酸树脂在 $160\\sim240^{\\circ}\\mathrm{C}$ 之间进行接枝反应，其主要反应是羟基和羧基的反应。或者先合成聚酯，然后与丙烯酸单体进行聚合反应。第二种方法是合成含有一定双键的聚酯，然后和丙烯酸酯单体一起进行自由基聚合反应。  \n\n配方及工艺举例如下。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 281,
+        "chunk": "# a.丙烯酸预聚物（质量份）  \n\n<html><body><table><tr><td>丙烯酸β羟丙酯</td><td>4.6</td><td>BPO</td></tr><tr><td>丙烯酸丁酯</td><td>22.0 链转移剂</td><td>2.2 0.2</td></tr><tr><td>苯乙烯</td><td>27.0 二甲苯</td><td>40.0</td></tr><tr><td>丙烯酸</td><td>4.0</td><td></td></tr></table></body></html>  \n\n合成工艺：将全部单体、链转移剂和配方中 $70\\%$ 的BPO在高位槽中混合均匀。在反应釜内，投人溶剂和 $30\\%$ 的混合单体，搅拌升温至回流温度（约 $120^{\\circ}\\mathrm{C})$ ，保温 $30\\mathrm{min}$ ，滴加混合单体，于3h左右滴完，并保温1h，补加剩余的BPO，继续回流保温2h，测定树脂的技术指标合格后，降温出料备用。  \n\n丙烯酸聚合物的技术指标  \n\n<html><body><table><tr><td>外观</td><td>无色或微黄透明液体</td><td>固体分/%</td><td>59~61</td></tr><tr><td>颜色（Fe-Co）/号</td><td>≤2</td><td>酸值/（mgKOH/g)</td><td>30~32</td></tr><tr><td>黏度/mPa·s</td><td>1900~2000</td><td></td><td></td></tr><tr><td>b.聚酯预聚物（质量份）</td><td></td><td></td><td></td></tr><tr><td>新戊二醇</td><td>31.6</td><td>邻苯二甲酸酐</td><td>27.0</td></tr><tr><td>三羟甲基丙烷</td><td>15.0</td><td>二甲苯</td><td>3.0</td></tr><tr><td>己二酸</td><td>26.4</td><td></td><td></td></tr></table></body></html>  \n\n合成工艺：在反应釜内投放所有物料及回流溶剂，搅拌升温至 $160^{\\circ}\\mathrm{C}$ ，保温3h，通氮气并逐步脱水至 $235\\mathrm{{T}}$ ，酯化直到酸值 $\\leqslant15\\mathrm{mgKOH/g}$ ，黏度（醋酸丁酯稀释至 $60\\%$ 固含量）$30\\sim50\\mathrm{s}$ 为终点。  \n\nc.丙烯酸-聚酯复合树脂的制备将聚酯预聚物与丙烯酸预聚物按 $1.5:1$ 投入反应釜内，升温（脱溶剂）至 $200^{\\circ}\\mathrm{C}$ ，酯化至酸值 ${<}15\\mathrm{mgKOH/g}$ ，黏度（醋酸丁酯稀释至 $60\\%$ 固体分） $50\\sim80{\\mathrm{s}}$ 为终点。在加入混合溶剂（二甲苯/醋酸丁酯 $=2:1$ ）兑稀至固含量59%～$61\\%$ ，降温过滤出料。其质量技术指标为：  \n\n<html><body><table><tr><td>外观</td><td>微黄透明液体</td><td>固体分/%</td><td>59~61</td></tr><tr><td>颜色（FeCo）/号</td><td>≤</td><td>酸值/（mgKOH/g)</td><td>≤15</td></tr><tr><td>黏度</td><td>50~80</td><td></td><td></td></tr></table></body></html>  \n\n$\\textcircled{3}$ 环氧改性丙烯酸树脂用环氧树脂改性丙烯酸树脂可以改善丙烯酸树脂在金属上的附着力以及各种耐介质性能。此外，丙烯酸环氧树脂具有良好的辐射固化能力，因此成为辐射固化涂料中的重要一员。  \n\n环氧树脂改性丙烯酸树脂的主要反应为环氧树脂中的环氧基与丙烯酸树脂中的羧基进行反应：  \n\n![](images/c287dba9f1d68563a7aea4bb98f204a8d2ed527016b577704531849352038d48.jpg)  \n\n文献对环氧树脂和丙烯酸反应生成环氧丙烯酸树脂做过详细的研究。该反应是在一定温度且有催化剂的存在下，环氧基和丙烯酸开环酯化的过程。反应过程中，丙烯酸活性单体也有可能发生自身的聚合反应。因此，反应温度、催化剂种类及其用量，以及合适的阻聚剂用量等都是影响合成的主要因素，而且这些因素之间有着一定的交互作用。  \n\n例如，E-51环氧树脂的分子链两端各有一个可以与甲基丙烯酸或丙烯酸反应的环氧基团，反应程度可以用反应物的酸值大小来表征。反应条件为：环氧树脂E-51为 $100\\mathbf{g}$ ，甲基丙烯酸 $48g$ 或丙烯酸 $36{\\bf g}$ ，反应温度为 $110^{\\circ}\\mathrm{C}$ ，阻聚剂对苯二酚 $0,38$ ，催化剂N，N-二乙基苯胺 $0,2\\mathbf{g}$ 。酸值随反应时间的结果如表2-1-100所示，从表中结果可以看出，在反应6h后反应物的酸值基本稳定。  \n\n表2-1-100甲基丙烯酸或丙烯酸酸值随时间的变化  \n\n\n<html><body><table><tr><td>时间/h</td><td>1</td><td>2</td><td>3</td><td>4</td><td>5</td><td>6</td><td>7</td><td>8</td></tr><tr><td>酸值I/(mgKOH/g)</td><td>196.10</td><td>77.85</td><td>53.14</td><td>46.38</td><td>42.15</td><td>40.59</td><td>40.30</td><td>40.10</td></tr><tr><td>酸值IⅡ/(mgKOH/g)</td><td>205.31</td><td>82.40</td><td>57.28</td><td>49.82</td><td>44. 15</td><td>39.45</td><td>39.25</td><td>39.10</td></tr></table></body></html>\n\n注：酸值I为甲基丙烯酸酸值随反应时间的变化；酸值Ⅱ为丙烯酸酸值随反应时间的变化。  \n\n研究表明：温度是环氧丙烯酸树脂合成反应中极其重要的一个影响因素。当反应温度小于 $80\\ensuremath{\\uptau}$ 时，即使反应时间长达十几小时，反应转化率依然小于 $80\\%$ ；当反应温度较高时，在短时间内转化率即可达到较好的程度，但反应后期容易出现凝胶。  \n\n环氧树脂中环氧基开环与丙烯酸发生酯化反应，受催化剂种类及其用量的影响很大。不同的催化剂，催化效率不同，在四丁基溴化铵、N,N-二甲基苯胺、三乙醇胺三个催化剂中，催化效率依次为：N，N-二甲基苯胺 $>$ 四丁基溴化铵>三乙醇胺。随着催化剂用量的增加，反应达到终点的时间缩短，转化率提高。但是随着催化剂用量的增加反应产物颜色加深，这可能是由于催化剂在较高温度下长时间受热而发黄的缘故。  \n\n在环氧树脂和丙烯酸反应的过程中，由于反应的温度较高，为防止丙烯酸和环氧丙烯酸自身的热聚合，反应体系中需加入适量的阻聚剂。以对苯二酚为例，研究发现：随着阻聚剂用量的增加，合成反应的转化率提高，但产物的颜色加深。推测其原因可能是：阻聚剂的用量影响了氧气对催化剂的氧化程度，从而提高了有效催化剂的含量。由于反应是在空气氛围下进行的，氧气对阻聚剂和催化剂都有氧化作用，因此当阻聚剂用量增加时，很可能会在一定程度上减小氧气对催化剂的氧化程度，从而使反应转化率提高。但是在较高的温度下，酚类阻聚剂因氧化而显色，会使合成产物的颜色加深。  \n\n双酚A型环氧树脂是应用最多的一类环氧树脂，其主链中含有脂族烃基和醚键，以及活泼的环氧基，其耐腐蚀性和力学性能优良。考虑到改性树脂的物理机械性能和玻璃化温度，选用一定分子量的环氧树脂，并考虑环氧基与丙烯酸的活泼氢发生开环反应，产生羟基引起耐水性差的问题，故选样环氧树脂的环氧值受到限制。经试验，选择分子量 $1000\\sim$ 2000、环氧值 $0.1{\\sim}0.2$ 的环氧树脂较为合适。  \n\n$\\textcircled{4}$ 有机硅改性丙烯酸树脂涂料用有机硅树脂以Si—O—Si为主链。由于Si一O键的键能大于普通有机高聚物中C一C键的键能，因此，有机硅树脂具有良好的耐热性、耐臭氧、紫外光老化性；而且，由于表面张力小，水及其他污物不易附着，所以有机硅树脂具有良好的防潮性、抗水和水汽性。但有机硅树脂存在以下缺点：因固化温度较高（150～$200^{\\circ}\\mathrm{C}$ 、固化时间较长，所以大面积施工不方便；对底层的附着力差、耐有机溶剂性差、温度较高时涂膜的机械强度不好、价格较贵等。通过改性可以弥补这些缺点。常用来改性的树脂有：醇酸树脂、聚酯树脂、环氧树脂、丙烯酸树脂、聚氨酯树脂、酚醛树脂等。  \n\n丙烯酸树脂的改性技术 $20\\%$ 以上与有机硅有关。经有机硅改性的丙烯酸涂料比未改性的丙烯酸涂料具有更优异的耐候性、保光性、抗粉化性、抗污性和对无机材料表面的附着力，适于作户外装饰用耐候性涂料。用有机硅对丙烯酸树脂进行改性的方法主要分为冷拼法和化学法。冷拼法操作简便，但化学法效果较好，目前大多采用化学法改性。化学法改性按反应机理又分为：缩聚法、自由基聚合法和硅氢加成法。按反应原料形态分为：有机硅预聚体-丙烯酸酯预聚体法、有机硅预聚体-丙烯酸酯单体法、有机硅单体-丙烯酸酯单体法、有机硅单体-丙烯酸酯预聚体法。  \n\na.有机硅预聚体-丙烯酸酯预聚体法以有机硅预聚体和丙烯酸酯预聚体为原料进行的化学法改性根据树脂中所含活性基团的不同，又分为缩聚法和硅氢加成法，其中缩聚法较为常用。缩聚法是通过丙烯酸树脂中的活性官能团（主要是羟基）与有机硅预聚体中的羟基、烷氧基（主要是甲氧基、乙氧基）进行缩聚反应将有机硅链引入丙烯酸树脂中。这种方法的主要特点是工艺比较简单。  \n\n硅氢加成法是通过含活泼氢的有机硅烷或有机硅氧烷与带有不饱和双键的丙烯酸酯树脂进行硅氢加成反应而将有机硅链引入丙烯酸树脂中。该反应条件温和、产率高，被广泛用于合成各种含硅高聚物，但用在涂料领域还不久。  \n\nb.有机硅预聚体-丙烯酸酯单体法在以有机硅预聚体和丙烯酸酯单体为原料进行的化学法改性中，有机硅预聚体中通常既含有硅羟基，又含有不饱和双键；其不饱和双键可在引发剂存在下与丙烯酸酯单体进行自由基聚合，得到接枝改性的聚有机硅氧烷。c.有机硅单体-丙烯酸酯预聚体法该方法是以含有活性官能团的有机硅烷为固化剂，使其与丙烯酸树脂上的活性基团反应，交联成硅丙树脂。d.有机硅单体-丙烯酸酯单体法该方法是通过在丙烯酸树脂的合成中，再接加入含不饱和双键的有机硅烷或有机硅氧烷，从而在丙烯酸树脂侧链引入有机硅烷或硅氧烷，基本形式为 $\\mathbb{R}^{1}\\operatorname{Si}(\\mathrm{OR})_{x}$ ? $\\mathbf{R}^{1}=$ 聚合物骨架， $\\scriptstyle\\mathbf{R}=$ 甲基或烷基)。  \n\n可选择的有机硅烷有： $\\gamma$ 甲基丙烯酰氧丙基三甲氧基硅烷（TMSPM)、乙烯基三乙氧基硅烷、乙烯基三甲氧硅烷等。其中，TMSPM最为常用，其结构为：  \n\n![](images/864780d45bcc8a96dbe25164a2c85474df812284a8f9787ad42aeddb90d2aa91.jpg)  \n\n以下是用TMSPM改性的两个实例。  \n\n<html><body><table><tr><td>实例一</td><td></td><td></td><td></td></tr><tr><td>配方 组分</td><td>质量份</td><td></td><td>质量份</td></tr><tr><td>1甲基丙烯酸甲酯</td><td>18.1</td><td>组分 7丙烯酸</td><td>0.20</td></tr><tr><td></td><td></td><td></td><td>28.00</td></tr><tr><td>2丙烯酸丁酯</td><td>8.00</td><td>8甲苯</td><td></td></tr><tr><td>3甲基丙烯酸丁酯</td><td>5.00</td><td>9偶氮二异丁腊</td><td>0.80</td></tr><tr><td>4丙烯酸羟丙酯 5苯乙烯</td><td>11.20</td><td>10偶氮二异丁晴</td><td>0.20 3.00</td></tr><tr><td>6甲基丙烯酰氧丙基三甲氧基硅烷</td><td>14.50 2.00</td><td>11甲苯 12二甲苯</td><td>8.00</td></tr></table></body></html>  \n\n工艺：将组分 $1{\\sim}7$ 全部单体和9混合均匀，备用。将组分8投入到三口瓶中，加热$75\\mathrm{{^{\\circ}C}}$ ，稳定 $10\\mathrm{{min}}$ 左右。在3h内均匀滴加单体混合溶液，滴完后保温1h，补加组分10和11，保温8h，加人12兑稀，降温、出料。 P  \n\n技术指标：不挥发分/%颜色（Fe-Co）/号  \n\n250\\~300  \n\n按上述配方、工艺制得的树脂与异氰酸酯固化剂配合配制的涂料喷涂于玻璃表面，可获得良好的附着，而无需专用底漆。  \n\n<html><body><table><tr><td>实例二</td><td></td><td></td><td></td></tr><tr><td>部分1</td><td>用量/g</td><td></td><td>用量/g</td></tr><tr><td>组分</td><td></td><td>组分 正丁醇</td><td>524.9</td></tr><tr><td>芳烃（solvesso 100)</td><td>1049.8</td><td></td><td></td></tr><tr><td>部分2</td><td></td><td>组分</td><td></td></tr><tr><td>组分</td><td>用量/g</td><td></td><td>用量/g</td></tr><tr><td>苯乙烯</td><td>923.8</td><td>Y-甲基丙烯酰丙基三甲氧基硅烷</td><td>231. 0</td></tr><tr><td>2-乙基己酯丙烯酸酯</td><td>706.7</td><td>ABIN</td><td>332.6</td></tr><tr><td>甲基丙烯酸羟乙酯</td><td>1479.1</td><td>芳烃（solvesso 100) 正丁醇</td><td>1417. 2 182.7</td></tr><tr><td>甲基丙烯酸异丁酯</td><td>1071.6</td><td></td><td></td></tr><tr><td>部分3 组分</td><td></td><td>组分</td><td></td></tr><tr><td>全氟烷基丙烯酸酯</td><td>用量/g 69.3</td><td></td><td>用量/g 138.6</td></tr><tr><td>ABIN</td><td>32.3</td><td>-甲基丙烯酰丙基三甲氧基硅烷 芳烃（solvesso 100）</td><td>69.3</td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td>部分4</td><td>用量/g</td><td>组分</td><td></td></tr><tr><td>组分 ABIN</td><td>36.9</td><td></td><td>用量/g</td></tr><tr><td>芳烃（solvesso 100)</td><td>210</td><td>正丁醇</td><td>105.0</td></tr></table></body></html>  \n\n总量：8579.8  \n\n工艺：将部分1加入反应瓶，开动搅拌，加热至回流温度。部分2混合后在 $240\\mathrm{min}$ 滴加完毕，滴加期间温度控制在回流温度。部分3混合后，部分2同时滴加，时间为 $230\\mathrm{min}$ 票部分2滴加完后半小时补加部分4，反应在回流温度下保持 $60\\mathrm{{min}}$ ，冷却至室温。  \n\n技术指标黏度（加氏管)：J；平均分子量：2565；分散度：1.6。  \n\n该树脂可用于汽车的底漆或面漆，可改善泥土对汽车的附着力，使汽车更容易清洗  \n\n$\\textcircled{5}$ Cardura E10改性丙烯酸树脂Cardura E10又称叔碳酸缩水甘油酯（1,1-二甲基-1庚基羧酸基缩水甘油酯)，其结构式如下：  \n\n![](images/ba095074065a0f1d5fd23c0a91b6c59934d0cfc2d0fa429d70a074318053dbfd.jpg)  \n\nCarduraE10的环氧基具有较高的反应活性，可以和水、氢气、羟基、酚基、硫醇、羧基、氨基、酮基等多种基团反应。通过和羧基、羟基的反应，CarduraE10可以对丙烯酸树脂进行改性。 Y  \n\n利用丙烯酸共聚物分子上的羧基与CarduraE10上环氧基开环反应，连接上CarduraE10，同时释放出羟基：  \n\n![](images/e15293dc03ee31a583e08ea25a189955bcc9f50c455a9c0d859cedb9bb85c4d8.jpg)  \n\n将CarduraE10分子引入丙烯酸树脂中，其优点主要表现在以下几点。  \n\na.在改性反应后，产物中含有伯羟基和仲羟基，这些羟基可与丙烯酸树脂进一步交联。同时伯羟基的存在，使交联反应保持足够的活性，而部分仲羟基的存在，又使涂料具有合适的使用期。  \n\nb.由于CarduraE10分子带有一个非常大的烷基基因，所以使丙烯酸树脂具有更好的憎水性，同时由于其立体位阻效应，给丙烯酸树脂带来极好耐候性能以及耐水解、耐酸碱性能，涂膜更加柔韧、光亮。  \n\nc.由于环氧基较高的活性，使CarduraE10分子与聚合物链的反应较为温和，这就避免了许多副反应，使最终的聚合物分子量较低，分子量分布较窄，为制备高性能的涂料提供了较好的基础。  \n\nd.CarduraE10引人到聚合物中，相当于引人了一个双极性结构单元，其中高度支化的叔碳酸酯部分与烷烃相容性较好，而甘油酯和羟基部分具有较高的极性，可以与其他极性分子形成氢键。这就增进了改性的聚合物树脂与涂料的极性和非极性组分溶剂、填料和助剂的相容性，从而扩大了树脂的使用范围。  \n\nCarduraE10对丙烯酸树脂进行改性，主要有以下三种方法。  \n\na.首先制备Cardura E10 和丙烯酸单体的加成物ACE和MACE。然后与丙烯酸酯单体共聚合制备E10改性的丙烯酸树脂。制备ACE、MACE的反应式如图2-1-19所示。  \n\n![](images/3795c290a192359bbfce95170651af58e6914e4f6af165e48d24a9aa515ec564.jpg)  \n图2-1-19酯化过程中羟基的形成  \n\n上述单体的制备方法可简单描述为：在氮气保护的反应瓶中，加入等摩尔的（甲基）丙烯酸单体和CarduraEl0、适量的辛酸亚锡催化剂和自由基聚合阻聚剂，在 $120\\Upsilon$ 下反应3h，停止反应后除阻聚剂，即得到上述描述的单体。  \n\n用上述获得的单体，与其他丙烯酸酯单体或苯乙烯共聚，即可得到所需要的树脂。b.首先制备含羟基的丙烯酸酯聚合物，然后把CarduraE10接枝到已合成好的聚合物  \n链上，完成CarduraEl0对聚合物的改性。聚合物链上的羧基可以全部或部分与CarduraE10反应，从而得到不同性能的改性丙烯  \n酸树脂。c.让自由基聚合反应和羧基与CarduraE10的反应同时进行，这样可以大大节约制备时间。由于反应情况比较复杂，下面的一些情况应予以注意。a.由于酸性单体在聚合反应前后与CarduraE10 的反应活性有明显的差异，这样会导致  \n聚合物链结构的巨大差异，从而影响聚合物的性能。b.溶剂的选择也必须注意，酮类溶剂不能使用，因为它能与CarduraE10反应，最好  \n的溶剂是二甲苯，可以避免树脂的变色。醋酸丁酯、甲基异丁基甲醇、乙二醇丁醚可以作为  \n该类树脂的稀释剂。c.为了减少树脂的变色，含苯环的自由基引发剂尽量避免使用，最好使用过氧化二叔  \n丁酯和过氧化二叔戊酯。d.为了增加羧基和环氧基的反应程度，加入催化剂是一个很好的选择，因为在 $160^{\\circ}\\mathrm{C}$ 的  \n\n反应情况下，自由基反应速率很快，而酯化反应的速率相对就慢一些。  \n\ne.氧气的存在会使合成的树脂变色，所以制备时应先用氮气吹扫反应釜。另外，在含Cardura E10的体系中，大量使用甲基丙烯酸甲酯会使树脂轻微变黄，但使用苯乙烯却不会变黄，以下举例说明。  \n\n<html><body><table><tr><td>组分</td><td>树脂1/g</td><td>树脂2/g</td><td>树脂3/g</td></tr><tr><td>Cardura E10</td><td>20</td><td>16</td><td>20</td></tr><tr><td>MAA</td><td>6.8</td><td>5.4</td><td>6.8</td></tr><tr><td>HEMA</td><td>8.5</td><td>24</td><td>28</td></tr><tr><td>St</td><td>30</td><td>25</td><td>25</td></tr><tr><td>MMA</td><td>34.7</td><td>30</td><td>20.2</td></tr></table></body></html>  \n\n树脂性能  \n\n\n<html><body><table><tr><td>羟基含量/%</td><td>2.4</td><td>4.2</td><td>5.0</td></tr><tr><td>T/C</td><td>60</td><td>62</td><td>72</td></tr><tr><td>M/(g/mol)</td><td>2577</td><td>2456</td><td>2616</td></tr><tr><td>M/M</td><td>1.6</td><td>1.8</td><td>1.7</td></tr><tr><td>黏度（22. 3C)/mPa •s</td><td>2553</td><td>3600</td><td>2500</td></tr><tr><td>固体分/%</td><td>66.3</td><td>66.9</td><td>70.0</td></tr><tr><td>颜色（Pt/Co)</td><td>61</td><td>58</td><td>63</td></tr><tr><td>酸值/（mgKOH/g固体）</td><td>6.4</td><td>4.8</td><td>4.8</td></tr></table></body></html>  \n\n上述三个树脂与DesmodurN3600固化剂配合，能得到较为满意的结果。树脂2在硬度和柔韧性方面表现优越的综合性能，有很好的耐酸性。树脂1有很好的耐酸性，硬度和柔韧性适中，羟基含量较低，成本下降。树脂3硬度很高，但耐酸性能有所下降。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 282,
+        "chunk": "# 合成实例  \n\n<html><body><table><tr><td colspan=\"3\">部分1</td><td rowspan=\"2\">用量/g</td></tr><tr><td>组分</td><td>用量/g</td><td>组分</td></tr><tr><td>Cardura E10</td><td>250</td><td>二甲苯</td><td>27.7</td></tr><tr><td>部分2</td><td></td><td></td><td></td></tr><tr><td>组分</td><td>用量/g</td><td>组分</td><td>用量/g</td></tr><tr><td>丙烯酸</td><td>72</td><td>甲基丙烯酸甲酯</td><td>198. 0</td></tr><tr><td>甲基丙烯酸羟丙酯</td><td>180.0</td><td>二新丁基过氧化物</td><td>40</td></tr><tr><td>苯乙烯</td><td>300.0</td><td></td><td></td></tr><tr><td>部分3</td><td></td><td></td><td></td></tr><tr><td>组分</td><td>用量/g</td><td></td><td></td></tr><tr><td>二新丁基过氧化物</td><td>10</td><td></td><td></td></tr></table></body></html>  \n\n工艺：将部分1放人反应釜，搅拌，氮气保护，加热至 $165^{\\circ}\\mathrm{C}$ 。部分2在6h内均匀滴加，温度保持165℃，搅拌，氮气保护，滴加完毕后加入部分3继续反应1h，冷却至$100\\%$ ，用醋酸丁酯调整固体分至 $50\\%$ 。  \n\n技术指标：平均分子量分布系数  \n\n$\\textcircled{6}$ 己内酯及碳酸酯改性丙烯酸树脂已内酯改性的丙烯酸树脂具有更快的固化速度和更好的柔韧性。因为己内酯的羟基比一般的丙烯酸酯单体的羟基活性更高，同时己内酯的加入使丙烯酸酯含羟基的侧链变长，涂膜交联点的柔韧性增加，成功解决涂膜刚性和柔韧性的矛盾。合成的树脂具有高固体分，低黏度的特点。  \n\n己内酯对丙烯酸酯的改性可通过两种方法，一种是先制备丙烯酸树脂，然后利用丙烯酸树脂中的羟基引发己内酯开环，得到己内酯改性的丙烯酸树脂。其反应途径为：  \n\n![](images/0fd9c2afd61005cb2290c35c5865ba0e97f31e9ea7c2bcca69a12c077f79bde0.jpg)  \n\n另一条合成路线为先制备己内酯改性丙烯酸酯单体，如用己内酯单体直接与甲基丙烯酸酯羟乙酯或羟丙酯反应，获得结构明确的含羟基的单体。其反应途径为：  \n\n式中，R为乙基或丙基，n为1，2，3，  \n\n利用丙烯酸类聚合物上的羟基与己内酯进行酯交换开环反应的技术路线又可细分为先聚合后开环以及聚合反应与开环反应同时进行的两种方法。其中聚合反应与开环反应同时进行的技术路线已经实现工业化生产。  \n\n碳酸酯也可用于改性热固性丙烯酸树脂，其涂料具有非常优异的环境腐蚀能力以及耐擦伤、耐刮伤能力。  \n\n碳酸酯有五元环和六元环两类，基本结构式为：  \n\n![](images/8a24737b86cbf5de4fb2f8ce8034ee33b52f1f0cddc7f87063ff506b2f97f859.jpg)  \n\n碳酸酯与羟基的反应在有机酸的催化作用下，碳酸酯很容易被羟基开环，具体反应式：  \n\n![](images/82963d93a4d3b92b5ae84add06093fc2095ec9d52045b9fc3b7e0466d85b48a4.jpg)  \n\n碳酸酯改性丙烯酸酯单体 碳酸酯改性丙烯酸酯树脂  \n\n![](images/a422e67288084b845ddcfb5c92418b3dbfa20ea252313bef262fbbbeb8d0fe3d.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 283,
+        "chunk": "# 5.高固体分丙烯酸酯涂料  \n\n高固体分涂料具有节省涂料生产和使用中的溶剂、低污染、涂膜厚、丰满度高、装饰效果良好等优点，因此受到人们的日益重视。对于高固体分涂料，一般公认的施工固体分应大于 $70\\%$ 。高固体分涂料比溶剂型涂料的施工固体分能提高 $20\\%\\sim30\\%$ 。若固体分含量超过$80\\%$ ，可称为超高固体分涂料。  \n\n树脂的固体分（SC）与黏度 $(\\eta)$ 、平均分子量（M）存在如下关系：  \n\n![](images/89e4690044e3d18c383ff7415862fcbdb3774a60141b23aa85b13c8fe13377e6.jpg)  \n图2-1-20log，平均分子量和固体分之间的线性关系  \n\n不同树脂的关系参见图2-1-20。  \n\n图2-1-21给出了固体分一定的情况下，树脂黏度与平均分子量的关系。  \n\n图2-1-22给出了在一定的黏度下，平均分子量与固体分的关系。  \n\n在设计高固体分丙烯酸涂料时除要考虑一般溶剂型丙烯酸涂料的各种因素外，实现基料的低黏度化和引人活性稀释剂提高固体分是要考虑的两个重要方面。聚合物的黏度与其分子量大小及分布有关。在固定的浓度下，溶液的黏度随聚合物分子量的降低而降低，其数均分子量需低至 $2000\\sim6000$ 时，才能使固体分达到 $70\\%$ 左右而黏度不太高。  \n\n此外，每个高分子链有两个以上的羟基才能保证与多异氰酸酯交联成体型大分子，以保证涂膜的质量。我们可以  \n\n简单分析一下在确定的配方和数均分子量下，每个分子所含的羟基数。树脂的配方为$\\mathbf{MMA}:\\mathrm{St}:\\mathrm{HEMA}:\\mathrm{BA}:\\mathbf{MA}=20:8:13:16.7:0.3$ ，在数均分子量为1000时，每个分子平均含有1.7个羟基；数均分子量为1500时，为2.5个。但若分子量分布不均匀，每个分子平均有2.5个羟基并不意味着每个分子都有 $2\\sim3$ 个羟基，有些分子可能有3个以上的羟基，而有些只有一个或不含羟基。对于不含羟基的分子不能参加交联反应，它只能作为增塑剂或溶剂，在高温下可挥发掉；只含一个羟基的分子则起终止交联反应的作用。因此，在配方设计和合成时，既要保证含羟基单体的数量，又要保证一定的分子量，在合成时要求树脂的分子量分布要均匀。要满足上述条件，在配方设计中，含羟基的活性官能团单体的用量是理论需要量的3倍甚至更高。  \n\n![](images/e9d13a8ef2665ffd2a0f58cdaaaa7c72fb356c2cc1550a1b88df72430ce4866a.jpg)  \n图2-1-21平均分子量与黏度关系（固体分65%）  \n\n![](images/a90e94fae0b2ada002e9627799b15f0dd80ac426b2bc80cd95a1080d7fe96f63.jpg)  \n图2-1-22平均分子量与固体分关系（黏度固定为 $50\\mathrm{{m}P a\\bullet s)}$  \n\n此外，聚合物分子量的多分散性也会影响树脂的黏度。在高固体分涂料中，要求合成分子量较低的低聚物，它们的分子量有一定的分散性。分子量的分散性通常用分子量分布系数d来表示。  \n\n$$\nd=M_{\\mathrm{w}}/M_{\\mathrm{s}}\n$$  \n\n对于平均分子量相同的聚合物来说，其分子量分布不同，它们的黏度也不同。通常分子量分布系数d越小，涂膜的性能越好，其黏度也越小。聚合物的黏度和其重均分子量M之间的关系：  \n\n$$\n\\eta{=}K M_{\\ast}^{x}{=}K d^{x}M_{\\ast}^{x}\n$$  \n\n式中K，x—与体系性质有关的常数。  \n\n对于高固体分的低聚物，x值较低，一般在1～2之间。树脂分子量的分布对黏度影响  \n\n十分明显。图2-1-23给出了黏度、分子量及分子量分布系数的关系。  \n\n获得性能优异的高固体分丙烯酸酯涂料的关键是制造低分子量、低黏度、官能团分布均匀的丙烯酸树脂，因此在配方设计中以下因素需要仔细考虑。  \n\n(1）选用合适的引发剂影响丙烯酸高固体分树脂的分子量和聚合效率的  \n\n![](images/42943640df2e3a19c5f290f717b7b26d035e195f719964b36eb54c4316db9301.jpg)  \n图2-1-23分子量、分子量分布对丙烯酸树脂黏度的影响  \n\n主要因素有引发剂浓度、引发剂类型和所产生的自由基、引发剂分解速率、聚合反应温度、溶剂类型、单体组成和滴加速度等，因此引发剂在高固体丙烯酸树脂自由基合成中起着重要作用。  \n\n偶氮睛引发剂使羟基丙烯酸树脂获得窄分子量分布。偶氮睛引发剂分解可产生夺氢反应能力弱的自由基，减少自由基向溶剂转移而生产过小的分子，减少非官能团或单官能团的二聚体或多聚体，改进涂膜性能；但偶氮类产品在颜色、溶解性、效率和反应温度方面有局限。  \n\n叔丁基过氧化物一般不宜用于高固体分丙烯酸树脂的合成，叔丁基过氧化物能分解产生的自由基活性高，并且产生夺氢反应，使分子量分布趋宽。  \n\n叔戊基过氧化物能分解产生能量小、夺氢能力比传统有机过氧化物弱的自由基，在合成高固体分丙烯酸树脂中可以表现出如下优点：引发温度宽 $(103\\sim145\\Upsilon)$ ；不带氧键可合成透彻度高、低颜色及低残留单体的树脂；溶解性强的液体；自由基分解效率高，但这类引发剂价格较高。  \n\n高固体分涂料聚合用新戊基过氧化物见表2-1-101。  \n\n表2-1-101高固体分涂料聚合用新戊基过氧化物  \n\n\n<html><body><table><tr><td rowspan=\"2\">化学品名称</td><td colspan=\"3\">半衰期湿度/C</td></tr><tr><td>10h</td><td>1h</td><td>15min</td></tr><tr><td>过氧化2-乙基已酸新戊酯(1.575)</td><td>75</td><td>92</td><td>103</td></tr><tr><td>1,1-二(过氧化新戊基)环已烷(L531)</td><td>93</td><td>112</td><td>124</td></tr><tr><td>过苯甲酸新戊酶(TAPB)</td><td>100</td><td>122</td><td>135</td></tr><tr><td>过氧化醋酸新戊酯（L555)</td><td>100</td><td>120</td><td>134</td></tr><tr><td>2,2-二（新戊基过氧化物）丙烷（L553)</td><td>108</td><td>128</td><td>142</td></tr><tr><td>丁酸-3,3-二（过氧化新戊基)乙酶（L533）</td><td>112</td><td>132</td><td>145</td></tr><tr><td>二新戊基过氧化物(DTAP)</td><td>123</td><td>145</td><td>157</td></tr></table></body></html>  \n\n引发剂的浓度越大，树脂的黏度越低。一般引发剂浓度可达 $4\\%$ 或更高。在聚合反应中，高用量的引发剂在严格的温度和浓度的控制下，可使树脂的多分散性降至最低。但引发剂的浓度过大不仅会提高成本，降低固含量，增加生产上的不安全因素，而且会导致分解产物量的增多，从而影响产品的耐久性及气味。  \n\n新丁基过氧化物裂解形成新丁氧基自由基， $\\beta$ 裂解反应慢且主要引发物是新丁氧基目由基，如果发生 $\\beta$ 裂解则是为甲基自由基。这两种基团都是反应性高、容易夺氢的。另一方面，叔戊基过氧化物裂解形成新戊氧基自由基。 $\\beta$ 裂解反应几乎是瞬间的不断产生丙酮和乙基自由基。乙基自由基是主要的引发物，并相对地稳定使夺氢作用降至最低。降低夺氢作用倾向导致较少长支化链的产生，给予分子量、分子量分布和黏度较好控制。  \n\n下面举例进行说明。  \n\n甲基丙烯酸甲酯 $40\\%$ ，丙烯酸丁酯 $25\\%$ ，丙烯酸羟乙酯 $25\\%$ ，苯乙烯 $7.5\\%$ ，甲基丙烯酸 $2.5\\%$ 。溶液中单体和溶剂的比例为 $3.7:1$ O $80\\%$ 的理论固含量)。所使用的溶剂为ExxonChemical公司的“Aromatic100”。  \n\n所有的有机过氧化物估计在 $15\\mathrm{min}$ 半衰期温度和相等活性 $[0]=0.42$ （等摩尔）按重量计，每100份单体的用量时进行，偶氮引发剂是按新戊基过氧化物在 $15\\mathrm{{min}}$ 半衰期温度和等同活性[N]下估计的。  \n\n工艺：聚合反应在通氮配有隔套搅拌器、温度计和回流冷凝管的2L玻璃反应釜中进行。单体混合后加入引发剂，用5个小时在规定的温度下计量滴入有溶剂的反应釜中。单体和引发剂滴加完毕后，聚合反应再继续1h。  \n\n表2-1-102将新戊基过氧化物与新丁基过氧化物的同系物相比较，新戊基过氧化物产生的分子量较低，分子量分布较狭窄，溶液黏度较低。分子量性质的改进与所用有机过氧化物结构有直接关系，说明了自由基类型重要。  \n\n表2-1-102高固体分丙烯酸树脂的分子量和黏度（新戊基过氧化物）  \n\n\n<html><body><table><tr><td>引发剂</td><td>聚合温度/℃</td><td>M.</td><td>M/M</td><td>黏度/mPa·s</td></tr><tr><td>DTAP</td><td>157</td><td>2500</td><td>1.81</td><td>1500</td></tr><tr><td>DTBP</td><td>162</td><td>3200</td><td>2.60</td><td>3200</td></tr><tr><td>L533</td><td>145</td><td>2800</td><td>2.90</td><td>2500</td></tr><tr><td>L233</td><td>147</td><td>3700</td><td>2.30</td><td>5200</td></tr><tr><td>L531</td><td>124</td><td>4600</td><td>2.41</td><td>9300</td></tr><tr><td>L331</td><td>128</td><td>5300</td><td>3.20</td><td>15200</td></tr></table></body></html>\n\n注：L531—1,1-二-（新戊基过氧化）环已烧；L331—1,1-二-（新丁基过氧化）环己烷；L533-3,3-二-（新戊基过氧化）丁酸乙酯；L233—3,3-二-（新丁基过氧化）丁酸乙酯。  \n\n表2-1-103比较了不同温度下由新戊基过氧化物与双偶氮甲基丁晴所生产的丙烯酸高固体涂料树脂溶液黏度与分子量、分子量分布。结果显示，用新戊基过氧化物比用偶氮睛的分子量、分子量分布和溶液黏度低。此外，新戊基过氧化物合成树脂的残留单体（在 $0.3\\%\\sim0.8\\%)$ 低于双偶氮化合物（在 $1.2\\%\\sim1.5\\%)$ ，树脂色泽按APHA（美国公共卫生协会氯铂酸钾法标准溶液）（ $20\\sim29\\$ ）比较也低于双偶氮化合物$(53\\sim84)$ 。  \n\n表2-1-103高固体丙烯酸树脂的分子量和黏度（双偶氮甲基丁晴）  \n\n\n<html><body><table><tr><td>引发剂</td><td>聚合温度</td><td>M.</td><td>M/M</td><td>黏度/mPa * s</td></tr><tr><td rowspan=\"5\">双偶氮甲基丁腩</td><td>157</td><td>2800</td><td>2.00</td><td>2800</td></tr><tr><td>145</td><td>3400</td><td>2.04</td><td>4900</td></tr><tr><td>134</td><td>3700</td><td>2. 04</td><td>5000</td></tr><tr><td>124</td><td>4800</td><td>2.15</td><td>10300</td></tr><tr><td>103</td><td>6600</td><td>2.41</td><td>25000</td></tr></table></body></html>  \n\n(2）提高合成温度有资料表明，聚合反应的活化能约为 $40\\mathrm{kJ/mol}$ ，反应温度每提高$10\\mathsf{\\tau}$ ，分子量约下降 $40\\%$ 。因此，反应温度对分子量影响十分明显。  \n\n一般反应温度越高，分子量越小。但树脂合成温度应和引发剂的半衰期相匹配。不同温度下丙烯酸单体在某一溶剂中聚合的链转移常数不同；在同一温度下，不同的溶剂也有不同的链转移常数。有些溶剂如CCl等在较高温度下控制分子量的能力较强，但温度较高，会使反应难以控制，且聚合中会出现链支化反应。  \n\n（3）选择适当的溶剂虽然高固体分丙烯酸酯涂料的固体分达到 $60\\%\\sim70\\%$ ，有的甚至超过 $80\\%$ ，但仍需要一定量的溶剂。高固体分丙烯酸树脂合成温度一般较高，因此要求溶剂有较高的沸点，还要求选用的溶剂溶解力强、降低黏度效果好、毒性小、来源广、成本低等。  \n\n由于随着聚合温度的升高，链转移剂的能力减弱，溶剂的链转移能力增强，选择溶剂时应考虑其链转移系数。研究表明，溶剂分子中含有活泼氢原子数或卤素原子数越多（如烷基芳烃，高沸点醚及苄醇)，转移反应越易发生。  \n\n溶剂对高分子成膜物质的溶解能力和溶液中氢键的形成情况对黏度有明显的影响。当溶剂的溶解参数和聚合物的溶解参数相近或相等时，溶剂的溶解能力最强。良溶剂时的聚合物的链段充分舒展，聚合物分子的自由度增大，从而使得溶液的黏度降低。表2-1-104为一个固体分为89.5%的丙烯酸树脂（溶剂为二甲苯）用不同溶剂稀释到固体分为 $55\\%$ 时的黏度。此外，聚合物溶液含有大量的羧基和羟基，易形成氢键，黏度可能很高，因此加一些酮类溶剂可使溶剂黏度明显下降。因为酮类溶剂不提供氢键，是氢键的受体，能转移聚合物链之间的氢键作用力。  \n\n表2-1-104溶剂对树脂的溶解能力（25℃）  \n\n\n<html><body><table><tr><td>溶剂</td><td>黏度/mPa·s</td><td>溶剂</td><td>黏度/mPa·s</td></tr><tr><td>丁酮</td><td>80</td><td>乙二醇乙醚酯酸酯</td><td>920</td></tr><tr><td>酷酸乙酯</td><td>250</td><td>四甲苯</td><td>3480</td></tr><tr><td>甲苯</td><td>430</td><td>异丙醇</td><td>1650</td></tr><tr><td>醋酸丁酯</td><td>310</td><td>乙二醇单丁醚</td><td>2250</td></tr></table></body></html>  \n\n(4）采用链转移剂链转移剂通过链自由基的转移来调节平均分子量，并使分子量的分布趋于狭窄。使用羟基硫醇链转移剂不仅能降低分子量及使分子量分布狭窄，还能为聚合物的端基提供羟基。这类化合物主要有2-硫基乙醇、3-硫基丙醇、3-硫基丙酸-2-羟乙酯等。这类含羟基硫醇合成出来的树脂的每一个分子链上至少有一个羟基，从而降低交联固化后自由基链末端的数量，使得涂膜性能更好。用氨基树脂交联的试验表明，含疏基硫醇对涂膜的硬度及耐溶剂性明显优于使用不含羟基的硫醇涂膜。但硫醇用量大会使得涂膜的耐水性、耐候性等变差，且单体转化率低，残余硫醇的气味往往为用户所讨厌，还会在涂料中产生光不稳定性。表2-1-105所示为3-硫基丙醇用量与聚合物分子量及溶液黏度的关系。  \n\n表2-1-1053-殖基丙醇用量与聚合物分子量及溶液黏度的关系  \n\n\n<html><body><table><tr><td>硫基丙醇用量</td><td>M.</td><td>M</td><td>M/M</td><td>黏度（23.9℃）/mPa * s</td></tr><tr><td>0</td><td>20900</td><td>11400</td><td>1.9</td><td>19400</td></tr><tr><td>1.3</td><td>10800</td><td>6000</td><td>1. 8</td><td>3850</td></tr><tr><td>2.6</td><td>7200</td><td>4300</td><td>1.7</td><td>1875</td></tr><tr><td>3.9</td><td>5700</td><td>3500</td><td>1. 6</td><td>1300</td></tr><tr><td>5.2</td><td>4400</td><td>3000</td><td>1.5</td><td>720</td></tr><tr><td>6.6</td><td>3600</td><td>2400</td><td>1. 5</td><td>460</td></tr><tr><td>7.9</td><td>3100</td><td>2200</td><td>1.4</td><td>300</td></tr></table></body></html>  \n\n(5）玻璃化温度树脂的玻璃化温度越低，分子链的流动性越高，溶液的黏度也越低。  \n\n玻璃化温度对温度的影响可以用自由体积的变化来解释。玻璃化温度降低，单位体积中分子间空隙即自由体积增加，使链段的运动更加容易，体系黏度降低。玻璃化温度和分子量间的关系可用下面的经验公式来描述：  \n\n$$\n\\ln\\eta{=}27.6{-}\\frac{40.2\\times(T{-}T_{g})}{51.6{-}(T{-}T_{g})}\n$$  \n\n式中T—测定黏度时的温度。  \n\n对于用低聚物的高固体分涂料，可以用上式来估算黏度和玻璃化温度的关系。对于分子量相同的聚合物，其玻璃化温度越低，聚合物的黏度就越小，这显然对制备高固体分涂料有利。  \n\n研究表明，大幅度降低聚合物的 $T_{\\mathrm{s}}$ 可提高丙烯酸树脂 $10\\%$ 的体积固体分。然而，双组分丙烯酸聚氨酯涂料大都是在室温或低温固化，丙烯酸树脂成分对于干燥速度、固化速度和最终硬度所起的作用是关键性的，所以较低的 $T_{\\mathrm{s}}$ 势必会影响涂膜的上述性质。  \n\n具有4个或更多个碳原子支化烷基（特别是叔烷基）的单体（表2-1-106)，具有和甲基丙烯酸甲酯或苯乙烯类似的很高的玻璃化温度，但极性低，耐久性较好。  \n\n表2-1-106带支化烷基或环烷基的单体  \n\n\n<html><body><table><tr><td>单体名称</td><td>烷基</td><td>均物的</td><td>单体名称</td><td>烷基</td><td>均物的</td></tr><tr><td>甲基丙烯酸环已基酯（CHMA)</td><td>C</td><td>83</td><td>甲基丙烯酸叔丁基环已基酯（TBCHMA）</td><td>C1</td><td>98</td></tr><tr><td>甲基丙烯酸三甲环已基酯（TMCHMA)</td><td>C</td><td>98</td><td>甲基丙烯酸异冰片酯（IBOMA）</td><td>C1</td><td>170</td></tr></table></body></html>  \n\n![](images/b52b5b0036af660af979e33be9cd5bd62a7c4773dd437dc57d27f79858be57b7.jpg)  \n\n试验还表明，在恒定的 $T_{\\mathrm{s}}$ ， $M_{\\mathrm{w}}$ 、官能团和固含量下，在丙烯酸树脂配方中加人甲基丙烯酸环型酯单体（表2-1-106）能有效降低树脂的黏度但不降低性能，并且黏度随着单体添加量的增加而下降。  \n\n表2-1-107给出了MMA、IBOMA、TMCHMA以及CHMA在单体中的不同比例（在合成时，溶剂为醋酸丁酯，引发剂为过氧化乙基已酸叔丁酯）对树脂性能的影响。  \n\n表2-1-107支化烷烃的单体用量对树脂性能的影响  \n\n\n<html><body><table><tr><td>单体</td><td></td><td>百分比/%MMA/%</td><td>BA/%</td><td>HEMA/%MAA/%</td><td></td><td>M</td><td>M</td><td>D</td><td>黏度/mPa·s</td></tr><tr><td rowspan=\"4\">IBMA</td><td>。</td><td>57</td><td>20</td><td>20</td><td>3</td><td>2670</td><td>7470</td><td>2.8</td><td>94500</td></tr><tr><td>20</td><td>37</td><td>20</td><td>20</td><td>3</td><td>2360</td><td>6760</td><td>2.9</td><td>75500</td></tr><tr><td>25</td><td>32</td><td>20</td><td>20</td><td>3</td><td>2320</td><td>6340</td><td>2.7</td><td>68800</td></tr><tr><td>30</td><td>27</td><td>20</td><td>20</td><td>3</td><td>2210</td><td>6140</td><td>2.8</td><td>54100</td></tr><tr><td rowspan=\"3\">TMCHMA</td><td>20</td><td>37</td><td>20</td><td>20</td><td>3</td><td>2990</td><td>7110</td><td>2.4</td><td>42800</td></tr><tr><td>25</td><td>32</td><td>20</td><td>20</td><td></td><td>3000</td><td>7080</td><td>2.4</td><td>35700</td></tr><tr><td>30</td><td>27</td><td>20</td><td>20</td><td>3</td><td>2870</td><td>6660</td><td>2.3</td><td>25200</td></tr><tr><td rowspan=\"3\">CHMA</td><td>20</td><td>37</td><td>20</td><td>20</td><td>3</td><td>3450</td><td>8000</td><td>2.3</td><td>10300</td></tr><tr><td>25</td><td>32</td><td>20</td><td>20</td><td>3</td><td>3420</td><td>8000</td><td>2.3</td><td>72500</td></tr><tr><td>30</td><td>27</td><td>20</td><td>20</td><td>3</td><td>2240</td><td>7700</td><td>2.3</td><td>63500</td></tr></table></body></html>  \n\n可以看到，各种环形单体对黏度降低都有明显的作用。其次序为：TMCHMA $>$ IBMA>CHMA。  \n\n目前，在实际应用中，IBMA单体最为普遍。IBMA是一种将硬度和柔顺性能极好体现出的优异单体，由于其特有的分子结构特点，使其聚合物具有优异的高光性、鲜映性、耐擦伤性、耐介质性和耐候性，其吸湿性明显低于甲基丙烯酸甲酯。而且，加有IBMA的丙烯酸树脂与聚酯、醇酸以及许多挥发性漆的成膜物质都有好的相容性。  \n\n(6）官能团极性为了降低聚合物的黏度，需要考虑单体中官能团的极性。官能团的极性低，可使链与链之间的氢键作用降低；相互作用减小，高聚物的黏度降低。如MMA赋予聚合物高极性和链刚性，使聚合物溶液的黏度增大，因此在高固体分树脂的合成中其用量需要严格控制。又如，不同的羟基单体的黏度也有差异，如丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酸羟丁酯的黏度依次降低。羧基官能团的含量增加会引起溶液黏度的显著提高。  \n\n通过降低官能团极性来合成高固体分树脂的一个成功例子是，采用硅氧烷预先封闭羟基（甲基）丙烯酸单体中的羟基。利用硅氧烷对丙烯酸低聚物中的羟基进行封闭，可以制备出性能良好的高固体分丙烯酸汽车用面漆。被封闭的羟基可以在催化剂或水分作用下解封释放出羟甲基和硅烷基。由于羟基被极性很低的硅氧基封闭，含羟基的丙烯酸低聚物极性降低，黏度比含有未封闭羟基的丙烯酸低聚物要小得多，可以将固体含量提高 $20\\%$ 。  \n\n(7）引入CarduraE组分制备高固体分丙烯酸树脂近来对含十碳的叔碳酸缩水甘油酯（CarduraE10）单体加人到树脂合成配方中的作用研究发现，CarduraE10含量越高，越有利于提高固体分、聚合物溶解黏度也越低。  \n\n此外，也可使用由CarduraE10与多元醇进行醚化开环反应，制备出CarduraE10醚类活性稀释剂参见表2-1-108。  \n\n表2-1-108CarduraE10类活性稀释剂以及它们的性能指标  \n\n\n<html><body><table><tr><td>化合物</td><td>结 构</td><td>M</td><td>M/M</td><td>黏度/mPa·s</td></tr><tr><td>三甲羟基丙烷单加成物</td><td>1 CH 0 0 OH HO HO</td><td>502</td><td>1.05</td><td>25</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>化合物</td><td>结 构</td><td>M</td><td>M/M</td><td>黏度/mPa·s</td></tr><tr><td>新戊二醇单加成物</td><td>9 HO CH OH RR' 6</td><td>400</td><td>1.02</td><td>3.2</td></tr><tr><td>新戊二醇双加成物</td><td>HC 1 # CH RM OH OH R²R</td><td>700</td><td>1.08</td><td>4.8</td></tr></table></body></html>  \n\n(8）使用带羟基的引发剂有文献报道，采用带羟基的功能引发剂如过氧化二羟甲基异丁酰 $\\mathrm{\\small{[HOCH_{2}C(C H_{3})_{2}O C O O C O C(C H_{3})_{2}C H_{2}O H]}}$ ，合成出固体分为 $85\\%$ 的羟基丙烯酸树脂。在施工黏度下（涂-4杯，20s)，固体分在 $60\\%$ 以上。从某种程度上缓解了树脂低分子量和羟基均匀分布的矛盾。  \n\n(9）基团转移聚合反应利用基团转移聚合反应可制备高固体低分子量的丙烯酸聚合物。其特点是分子量分布窄小，分散度 $M_{\\ast}/M_{\\ast}$ 可降低至1.2以下。聚合反应对丙烯酸聚合物结构的控制十分严格，分子上官能团的分布可以很窄。 →  \n\n（10）有机硅聚合物黏度低，在喷涂施工条件下，其固含量可达 $100\\%$ ，并且具有优良的耐久性和抗酸雨性能。利用有机硅（聚二苯基甲基氢硅烷）的SiH基和含烷烯基的丙烯酸低聚物的双键发生氢化硅烷化反应，可得到耐久性和抗酸雨性能优异的涂膜，这是开发高固含量、高性能的丙烯酸汽车涂料的一个新途径。  \n\n(11）高固体分丙烯酸树脂配方举例下面是高固体分低黏度的羟基丙烯酸树脂合成实例，该树脂与拜尔N-3390室温或 $60\\ensuremath{\\mathsf{T}}$ 固化，在硬度、干性、丰满度、鲜映性、耐候性、颜料分散性等方面表现优越的性能。曾用于公交大巴面漆6年，光泽保持良好。  \n\n配方  \n\n<html><body><table><tr><td>组成</td><td>用量/g</td><td>组成</td><td></td><td>用量/g</td></tr><tr><td>1二甲苯</td><td></td><td>24</td><td>7</td><td>甲基丙烯酸丁酯</td><td>85</td></tr><tr><td></td><td>2 PMA</td><td>60</td><td>8</td><td>二新戊基过氧化物</td><td>12</td></tr><tr><td></td><td>3苯乙烯</td><td>227</td><td>9</td><td>Cardura E10</td><td>75</td></tr><tr><td>4IBMA</td><td></td><td>103</td><td></td><td>10二新戊基过氧化物</td><td>2</td></tr><tr><td></td><td>53-硫基丙酸</td><td>30</td><td></td><td>11二甲苯</td><td>20</td></tr><tr><td></td><td>6甲基丙烯酸羟乙酯</td><td>164</td><td></td><td></td><td></td></tr></table></body></html>  \n\n合成工艺：  \n\n将配方中的1、2投人反应釜作底料，通氮气，升温回流；开始滴加 $3{\\sim}8$ 混合单体（8单体和其他单体分开滴加)，并在4h左右均匀滴加完毕。保温回流 $45\\mathrm{{min}}$ 加人材料10。保温回流 $45\\mathrm{min}$ 开始第一次补加9、10；继续保温回流1h开始第二次补加；再保温1.5h，温度降至 $80^{\\circ}\\mathrm{C}$ ，出料、过滤、包装。  \n\n技术指标固体分/% 69.7 酸值/(mgKOH/g)黏度（格式管，25℃）/s 16 羟基含量（固体）/%",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 284,
+        "chunk": "# 三、水性丙烯酸树脂  \n\n以水为溶剂或分散介质的涂料称为水性涂料。根据主要成膜物在水中的稳定状态，至少可以将水基型丙烯酸酯涂料分为：乳液型丙烯酸酯涂料，水乳化型丙烯酸酯涂料和水溶性丙烯酸酯涂料。从严格意义上讲，以水为溶剂的涂料才叫水溶性涂料，也就是生产水溶性涂料的树脂是以分子状态溶于水中而形成的溶液 $(<0,01\\mu\\mathrm{m})$ ，但这种真正的水溶性树脂很少作为涂料的主要成膜物质，一般用于保护胶或增稠剂等。涂料中用做主要成膜物的水溶性树脂实际上是可稀释型，是树脂聚集体在水中的分散体 $(0,01\\sim0.1\\mu\\mathrm{m})$ ，属于胶体范围，由于分散微粒极细，分散体呈透明状，因此也有将该类树脂误称为“水溶性”树脂的。乳液涂料是以乳胶为基料的水性涂料，乳胶是通过乳液聚合而合成的固体树脂微粒在水中的分散体$(0,01\\sim1\\mu\\mathrm{m})$ 。液态的聚合物或溶于有机溶剂而成为溶液的聚合物，在水中经乳化剂乳化而成为乳化液，以这种乳液为基料的水性涂料叫做水乳化涂料，这种乳化液不同于乳胶，它是一种液体在另一种液体连续相中的分散体。  \n\n水性涂料的名称有些混乱、同一种形态的涂料有多种说法，例如有把乳胶和乳液混用的，也有把水乳化涂料叫做水稀释性涂料、水分散涂料，有人还把水稀释性涂料归类为乳胶涂料，但从严格上讲水稀释性涂料不能称为乳胶涂料等。因此在阅读文献时要注意区分。  \n\n水性涂料的显著特征是以水为溶剂或分散介质、树脂作为分散相的涂料；由于以水代替了有机溶剂，它有利于环境保护和防止火灾。特别在建筑涂料中，世界发达国家的水性涂料已在逐步取代溶剂型涂料，水性涂料占建筑涂料份额的 $70\\%$ 以上。当然，水性涂料并非一点有机溶剂都没有，但真正意义上的水性涂料，有机溶剂含量是很低的，完全用水稀释，几乎不存在安全隐患，而且器具清洗方便。其附着力、耐水性、防腐性、外观、施工性等都很优异，长期稳定性也非常好，适合流水线浸涂施工。  \n\n在水性涂料中应用最多的是丙烯酸酯类。其在使用中显示出以下优良性能：防腐、耐碱、耐水、成膜性好、保色性佳、无污染等，并且容易配成施工性良好的涂料，涂装工作环境好，使用安全。  \n\n水可稀释型丙烯酸酯涂料采用具有活性可交联官能团的共聚树脂制成，多系热固性涂料，用于涂料的水性树脂的分子量一般为 $2000\\sim100000$ ；单组分树脂的分子量一般为2000～10000，双组分体系用树脂分子量一般为 $5000\\sim35000$ 。水性涂料的应用领域主要为建筑涂料和工业涂料。以丙烯酸酯类为基料的水性涂料根据其用途或特点可分为如下几类：(a）水性防腐涂料；（b）水性防锈涂料；（c）水性外墙涂料；（d）水性木器涂料；（e）水性纸品上光涂料；（f）水性路标涂料；（g）水性印刷油墨涂料等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 285,
+        "chunk": "# 1.水可稀释型丙烯酸树脂的组成与原材料  \n\n水可稀释型丙烯酸树脂的制备通过溶液聚合实现，在制备时可以选择含有羧基、磺酸基、醚键等官能团的不饱和单体与丙烯酸酯单体共聚后，用有机胺或氨水中和成盐，再溶解于水而获得水溶性丙烯酸树脂。若在体系中引入含羟基单体，则可以制成水性热固性丙烯酸树脂；与氨基树脂、多异氰酸酯配合，可分别制备水性单组分丙烯酸氨基树脂涂料和水性双组分丙烯酸聚氨酯涂料，这样制得的树脂由于提高了交联密度，涂料性能可与溶剂型丙烯酸树脂相比。  \n\n水可稀释型丙烯酸树脂实际在水中溶解度很小，树脂以粒子的形式分散在水相中。有人对含羟基丙烯酸树脂的水溶性规律进行了研究，发现羟基单体用量增加，水溶性增加；中和度越大，水溶性越好；羟基单体的用量对水溶性的影响比羧酸单体的影响小。  \n\n水可稀释型丙烯酸树脂的组成可以归纳于表2-1-109中。  \n\n表2-1-109水溶性丙烯酸树脂的组成  \n\n\n<html><body><table><tr><td>组成</td><td colspan=\"2\">常用品种</td><td>作 用</td></tr><tr><td rowspan=\"2\">单体</td><td>组成单体</td><td>丙烯酸乙酯、丙烯酸丁酯、丙烯酸乙基己酯、甲基丙 烯酸甲酯、苯乙烯等</td><td>调整基础树脂的硬度、柔顺性及 耐大气等物理性能</td></tr><tr><td>官能单体</td><td>丙烯酸、丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸、 甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、顺丁烯二酸 酐等</td><td>提供亲水基团及水溶性并为树脂 固化提供交联反应基团</td></tr><tr><td>中和剂</td><td colspan=\"2\">氨水、二甲基乙醇胺、N-乙基吗啉、2-二甲氨基-2-甲基丙醇、2-氨基-2- 甲基丙醇等</td><td>中和树脂上的羧基，成盐，提供树 脂水溶性</td></tr><tr><td>助溶剂</td><td colspan=\"2\">乙二醇乙醚、乙二醇丁醚、丙二醇乙醚、丙二醇丁醚、仲丁醇、异丙醇等</td><td>提供偶联效率及增溶作用，调整 黏度、流平性等施工性能</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 286,
+        "chunk": "# 2.聚合方法及机理  \n\n水可稀释性丙烯酸树脂的合成与溶剂型的基本相同，只是溶剂型丙烯酸树脂的聚合反应在制漆的溶剂中直接进行而水稀释性丙烯酸树脂不能在水中进行聚合反应，而是在助溶剂中进行，水则是在成盐时加人的。通常使树脂水性化有两条途径：（a）成盐方法：共聚形成丙烯酸树脂后，加入胺中和，将聚合物主链上所含的羧基或氨基经碱或酸中和反应形成盐类，从而具有水溶性：（b）醇解法：丙烯酸树脂在溶液中共聚后，进行水解，使聚合物具有水溶性。成盐法是最常使用获得水性丙烯酸树脂的方法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 287,
+        "chunk": "# 3.影响聚合反应的因素  \n\n丙烯酸树脂配方的关键是选用单体，通过单体的组合来满足涂膜特性的技术要求，但羚基含量、玻璃化温度也是很重要的因素。  \n\n(1）羧基含量羧基经胺中和成盐是树脂水溶的主要途径，所以羧基含量的多少直接影响到树脂的可溶性及黏度的变化。一般含羧基聚合物的酸值设计为 $30{\\sim}150\\mathrm{mgKOH/g}$ ，酸值越高，水溶性越好，但会导致涂膜的耐水性变差。有人以一系列树脂固体含量为 $10\\%$ （质量分数）、分子量4500、中和度 $100\\%$ 的无规共聚物树脂进行研究发现：树脂的水溶性随着树脂中羧基的含量的增加而增加，当含羧基的单体含量为 $10\\%\\sim12\\%$ 时，树脂临界水溶；但过高的羧基含量导致并不需要的高水溶性，会引起涂膜性能下降；实践证明在含丙烯酸$10\\%\\sim20\\%$ ，树脂的酸值在 $50\\sim100\\$ 并含有一定比例的羟基酯的共聚树脂，已具有足够的水溶性、足够的交联官能团度及良好的物理性能。  \n\n(2）玻璃化温度水溶性涂料在施工烘烤中比溶剂型涂料容易爆泡，特别是在希望得到较厚的涂膜和晾干时间较短的施工线上，爆泡问题更为突出。这个缺点也限制了水溶性涂料的应用。已有研究者发现，共聚物的玻璃化温度是水溶性丙烯酸酯漆涂膜爆泡的主要因素，此种水溶性漆无论用水或溶剂稀释都有此共同现象。试验中配制了5种不同的共聚物，分别有着不同的玻璃化温度，见表2-1-110。  \n\n表2-1-110不同树脂配方的物理数据  \n\n\n<html><body><table><tr><td>共聚物</td><td>重均分子量</td><td>数均分子量</td><td>M/M</td><td>酸值/（mgKOH/g)</td><td>50%溶液黏度/Pa·s</td><td>T/℃</td></tr><tr><td>1</td><td>51800</td><td>15600</td><td>3.32</td><td>53</td><td>1.94</td><td>28</td></tr><tr><td>2</td><td>108300</td><td>14200</td><td>7.63</td><td>52</td><td>5.29</td><td>-13</td></tr><tr><td>3</td><td>64600</td><td>14000</td><td>4.61</td><td>55</td><td>2.27</td><td>-8</td></tr><tr><td>4</td><td>73100</td><td>15100</td><td>4. 84</td><td>55</td><td>28.1</td><td>14</td></tr><tr><td>5</td><td>61100</td><td>16800</td><td>3.64</td><td>54</td><td>127.3</td><td>32</td></tr></table></body></html>  \n\n5种树脂中加入甲氧基三聚氰胺甲醛树脂作为交联剂，并用金红石型钛白粉及对甲苯磺酸为催化剂制成白色磁漆，分别用水及溶剂稀释后喷涂在样板上，测定其涂膜不爆泡的最大膜厚（临界干膜厚度)，发现在标准条件下的不爆泡的干膜厚度基本上随着玻璃化温度的上升而下降，同时发现水稀释树脂的不爆泡干膜厚度远较溶剂稀释型树脂为低。爆泡的临界干膜厚度见表2-1-111。  \n\n表2-1-111不同T下树的临界干膜厚度  \n\n\n<html><body><table><tr><td rowspan=\"2\">共聚物</td><td rowspan=\"2\">玻璃化温度 T/C</td><td colspan=\"2\">临界干膜厚度/μm</td><td rowspan=\"2\">共聚物</td><td rowspan=\"2\">玻璃化温度 T/C</td><td colspan=\"2\">临界干膜厚度/μm</td></tr><tr><td>水稀释</td><td>溶剂稀释</td><td>水稀释</td><td>溶剂稀释</td></tr><tr><td>1</td><td>28</td><td>50</td><td>≥120</td><td>4</td><td>14</td><td>10</td><td>55</td></tr><tr><td>2</td><td>13</td><td>30</td><td>70~95</td><td>5</td><td>32</td><td>5</td><td>25</td></tr><tr><td>3</td><td>-8</td><td>20</td><td>70~95</td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n从以上实验看出，玻璃化温度与爆泡有着相当密切的关系，高玻璃化温度的树脂远较低玻璃化温度的树脂容易爆泡，而且水稀释的树脂又远较溶剂稀释的树脂容易爆泡。还应指出，共聚物的玻璃化温度影响第二阶段挥发的自由体积，而自由体积又影响挥发分从涂膜中扩散出来的速率。当然，玻璃化温度也绝对不是爆泡的唯一因素；涂膜的厚度、晾干的时间、机械搅拌生成的气泡等都是引起爆泡的因素。  \n\n(3）助溶剂助溶剂不仅对溶解性及黏度起着调节、平衡的作用，同时还对整个涂料体系的混溶性、润湿性及成膜过程的流变性起着极大的作用。  \n\n有机助溶剂对涂料的喷涂施工及流变性能的影响非常大。要得到一个具有理想的物理性能、光泽及平整度的涂膜，就必须使胺中和了的树脂能很好地溶解在水及有机助溶剂的混合物中，并保持互容性直至烘干为止。实践证明，水溶性丙烯酸树脂漆中效果最好并最常用的助溶剂为醇醚类溶剂和醇类溶剂。20世纪70年代至80年代初，较多文献主要介绍采用乙二醇乙醚类溶剂，但经很多环境保护及工业卫生单位的反复试验，证明乙二醇乙醚等溶剂除对血液及淋巴系统有影响外，还能严重损害动物的生殖机能，导致胎儿中毒、畸胎等后果。所以，20世纪80年代中期以后，世界各国先后对乙二醇乙醚类溶剂作出了警告、限制或禁用的条令，使用量逐年减少。同时，对照试验证明丙二醇醚不存在相类似的病理学变化，因此目前很多厂商采用丙二醇醚来取代乙二醇醚类溶剂，但仍有部分厂商使用乙二醇醚类溶剂。  \n\n$\\textcircled{1}$ 助溶剂对黏度的影响某树脂用二甲基乙醇胺100%中和并用乙二醇一丁醚：水为不同比例的溶剂进行稀释，研究发现：用 $100\\%Z$ 二醇一丁醚为溶剂进行稀释的曲线基本为一直线随固体分的下降而下降；其他曲线因乙二醇一丁醚含量降低，其黏度与不挥发分间的关系成为非线性，例如乙二醇一丁醚：水为 $10:90$ 溶剂的曲线及纯乙二醇一丁醚为溶剂的曲线在固体分为30%时，其黏度相差高达约300倍；而固体分为 $15\\%$ 时，两者黏度相等；固体分低于 $1\\%$ 时，黏度反而低于纯乙二醇一丁醚体系。若使用叔丁醇或1-丙二醇丙醚为助溶剂时实验结果类似。由此看出，树脂在稀释过程中，助溶剂含量高的树脂其黏度下降速度较助溶剂含量低的树脂为慢，到达某一个固体含量的转折点后，含水量高的树脂的黏度反而较含助溶剂含量高的树脂为低。 Y  \n\n$\\textcircled{2}$ 施工应用中的溶剂挥发水溶性丙烯酸体系的黏度变化与助溶剂和水的比例及不挥发分高低有密切的关联。在施工应用过程中，以上两个条件在不断变化，水的挥发速率与施工现场空气的相对湿度又有着密切的联系。表2-1-112和表2-1-113说明两种相对湿度条件  \n\n下，在 $23\\Upsilon$ 喷涂施工过程中溶剂的挥发情况。  \n\n表2-1-112在45%相对湿度下喷涂施工时溶剂挥发情况（干膜厚 $20\\mu\\mathrm m^{*}$   \n\n\n<html><body><table><tr><td colspan=\"2\">施工过程</td><td>稀释至喷涂</td><td>喷后瞬间</td><td>喷后5min</td><td>喷后10min</td><td>喷后15min</td></tr><tr><td colspan=\"2\">不挥发物/g</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td></tr><tr><td rowspan=\"2\">挥发物/g</td><td>水</td><td>169</td><td>119</td><td>102</td><td>88</td><td>76</td></tr><tr><td>乙二醇一丁醚</td><td>40</td><td>35</td><td>33</td><td>32</td><td>31</td></tr><tr><td colspan=\"2\">不挥发分/%</td><td>32</td><td>39</td><td>43</td><td>45</td><td>48</td></tr></table></body></html>  \n\n表2-1-113在 $60\\%$ 相对湿度下喷涂施工时溶剂挥发情况（干膜厚 $28\\mu\\mathrm m$   \n\n\n<html><body><table><tr><td colspan=\"2\">施工过程</td><td>稀释至喷涂</td><td>喷后瞬间</td><td>喷后5min</td><td>喷后10min</td><td>喷后15min</td></tr><tr><td colspan=\"2\">不挥发物/g</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td></tr><tr><td rowspan=\"3\">挥发物/g</td><td>水</td><td>161</td><td>132</td><td>123</td><td>112</td><td>104</td></tr><tr><td>乙二醇一丁醚</td><td>20</td><td>16</td><td>16</td><td>15</td><td>14</td></tr><tr><td>仲丁醇</td><td>20</td><td>3</td><td>0. 9</td><td>0.2</td><td></td></tr><tr><td colspan=\"2\">不挥发分/%</td><td>33</td><td>40</td><td>42</td><td>44</td><td>46</td></tr></table></body></html>  \n\n相对湿度为 $45\\%$ ，在喷涂过程中挥发掉 $100\\times(169-119)/169$ 份水，计算为 $29.6\\%$ 的水；相对湿度为 $60\\%$ ，喷涂过程中水仅挥发掉 $100\\times{(161-132)}/{161}=18.0\\%$ ，这说明较高的相对湿度降低了水的挥发。如果不补充易挥发的仲丁醇作为补偿，则喷在样板上涂层的不挥发分及黏度均会太低而导致流挂，补加了仲丁醇之后，可以看到表2-1-112 和表2-1-113中喷在样板上涂层中不挥发分含量为相接近的 $39\\%$ 及 $40\\%$ 。另外，必须注意的是，黏度并不是完全取决于不挥发分含量，尽管两者在喷后瞬间时的不挥发分相当接近，但前者的流挂倾向远远高于后者，这主要是由于表2-1-112残留挥发物中的助溶剂含量为$100\\times35/(119+35)=22.7\\%$ ，而表2-6-45中则 $100\\times{(16+3)}/{(132+16+3)}=$ $12.6\\%$ 。前者虽然助溶剂仅多 $10\\%$ 左右，但黏度将会数倍低于后者，从防止流挂的要求来看，显然是后者的情况较为有利。  \n\n通常加入醇醚溶剂来延缓挥发以改进流平性，但水溶性丙烯酸酯漆中，流平性一般不成问题，而流挂现象则常引起麻烦，所以与乙二醇一丁醚同时使用一些挥发较快的溶剂，例如仲丁醇既补偿在潮湿气候下水分挥发少的份数，也可以大大降低助溶剂与水的比例而达到防止流挂的作用。采取这一措施时应注意到水性漆中可能出现的快挥发溶剂所带来的爆泡问题，挥发较慢的溶剂能减少爆泡倾向，两者用量应注意平衡。还有试验证明：（a）助溶剂的挥发与相对湿度有关，在相对湿度较高时 $(75\\%)$ ，随着喷后时间的延长，漆膜中未挥发掉的挥发分中，乙二醇丁醚的含量在不断下降；在相对湿度较低时（ $55\\%$ 或低于 $55\\%$ ，随着喷后时间的延长，其含量在不断增加；而在 $65\\%$ 相对湿度时，其含量几乎始终不变，这种情况下的相对湿度被称之为临界相对湿度（CRH)。无论在CRH之上或之下，助溶剂的含量变化均不大。（b）相同配方但不同分子量的树脂间，流挂倾向有所不同，在剪切率为$1{\\bf s}^{-1}$ 时，分子量为82000的树脂在低于 $60\\%$ 的相对湿度下就不流挂了，而分子量为42000的树脂则在低于 $50\\%$ 的相对湿度下才不流挂，此时二者的黏度均约为 $5\\mathrm{Pa}\\cdot\\mathbf{s}$ h  \n\n由此可以看出，控制施工场所的相对湿度在 $30\\%\\sim70\\%$ 是关键，再通过调整助溶剂与水的比例就可以很好地控制水性丙烯酸酯漆的流挂问题。  \n\n(4）胺的增溶作用水溶性丙烯酸酯涂料中使用胺中和侧链上的羧基成盐而能提供水可稀释型性能，不同的胺对涂料的黏度变化、贮存稳定性、漆膜固化等有影响。  \n\n$\\Phi$ 漆膜性能使用不同胺中和对漆膜性能影响的实验如下：用6种不同的胺作成盐增溶剂，使用相同的树脂制成白色水溶性丙烯酸酯涂料，胺的用量按树脂中酸含量的中和程度$100\\%$ 的等当量计算，涂料稀释至福特4号杯 $60{\\mathrm{s}}$ 的黏度，然后喷涂于经磷化处理不打底的钢板上，晾干 $30\\mathrm{{min}}$ ， $175\\mathrm{^{\\circ}C}$ 下烘 $20\\mathrm{{min}}$ ，干膜厚度 $30\\sim32\\mu\\mathrm{m}$ 。表2-1-114是使用不同胺时白色涂料的黏度，表2-1-115是在 $175\\mathrm{^{\\circ}C}$ 下烘 $20\\mathrm{{min}}$ 后不打底钢板上的漆膜性能。  \n\n表2-1-114使用不同胺中和的白色涂料黏度  \n\n\n<html><body><table><tr><td>胺</td><td>原始黏度/Pa·s</td><td>5个星期后黏度/Pa·s</td><td>稀释至喷涂黏度（福特杯60s） /（g水/100g涂料）</td></tr><tr><td>氨</td><td>16</td><td>11. 2</td><td>16</td></tr><tr><td>三乙基胺</td><td>2.6</td><td>2.1</td><td>10</td></tr><tr><td>N.N-二甲基乙醇胺</td><td>11</td><td>11.5</td><td>23</td></tr><tr><td>N-乙基吗啉</td><td>14.7</td><td>14.1</td><td>19</td></tr><tr><td>2-N,N-二甲基氨基-2-甲基丙醇</td><td>8.7</td><td>10</td><td>23</td></tr><tr><td>2-氨基-2-甲基丙醇</td><td>14.7</td><td>16.2</td><td>26</td></tr></table></body></html>  \n\n表2-1-115无底漆样板上白漆（175℃烘 $20\\mathrm{{min}^{\\prime}}$ 的性能  \n\n\n<html><body><table><tr><td>胺</td><td>60°光泽</td><td>Tukon硬度</td><td></td><td>锥形轴棒弯曲/cm抗洗涤剂性能/级</td><td>盐雾试验/级</td></tr><tr><td>氨</td><td>70</td><td>23.3</td><td>2.5</td><td>2</td><td>3</td></tr><tr><td>三乙基胺</td><td>3.5</td><td>表面粗糙不能测</td><td>5</td><td>1</td><td>2</td></tr><tr><td>N,N-二甲基乙醇胺</td><td>87</td><td>17.8</td><td>2</td><td>3</td><td>3</td></tr><tr><td>N-乙基吗啉</td><td>89</td><td>23.0</td><td></td><td>1</td><td>1</td></tr><tr><td>2-N,N-二甲基氨基-2-甲基丙醇</td><td>89</td><td>19.7</td><td>2</td><td>4</td><td>4</td></tr><tr><td>2-氨基-2-甲基丙醇</td><td>85</td><td>23.7</td><td>10</td><td>1</td><td>1</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 中和程度与 $\\mathsf{p H}$ 按树脂的酸含量用胺中和的百分数称之为中和程度(EN)，在水溶性丙烯酸酯树脂中，EN在 $60\\sim100$ 之间常能获得水溶性的效果，一般极少中和至 $100\\%$ 较常用的中和程度在 $70\\%\\sim85\\%$ 之间。中和程度越高涂料的黏度将会越大，所以达到足够的水溶性及贮存稳定性要求后，没有必要进一步中和至 $100\\%$ ，以免徒然降低应用时的固体分。实验发现，即使中和程度仅为 $50\\%$ 或更低时，树脂的 $\\mathsf{p H}$ 总是大于7的；当使用 $N,N-$ 二甲基乙醇胺或2-氨基-2-甲基丙醇为中和剂，中和程度达 $65\\%$ 以上时， $\\mathsf{p H}$ 常大于8；有时使用上述两种胺中和时，以 $\\mathbf{pH}8.5$ 为中和程度的标准线，这一点可用滴定法求得，共聚物溶于叔丁醇：水 $=30:70$ 的混合物中，用同一混合物溶解所选用的胺来滴定至 $\\mathrm{pH}=8.5$ 。  \n\n$\\textcircled{3}$ 胺碱性强度的影响每种胺由于结构与链长的不同有其不同的碱性，碱性强度常用$\\mathsf{p K}_{*}$ 表达，常用胺的 $\\mathsf{p}K_{\\ast}$ 如表2-1-116所示。  \n\n表2-1-116一些胺的pK，值  \n\n\n<html><body><table><tr><td>胺</td><td>pK(20C)</td><td></td><td>pK,(20C)</td></tr><tr><td>氨</td><td>9.4</td><td>N-乙基吗啉</td><td>7.78</td></tr><tr><td>三乙基胺</td><td>10.88</td><td>2-N，N-二甲基氨基-2-甲基丙醇</td><td>10.20</td></tr><tr><td>N,N-二甲基乙醇胺</td><td>9.31</td><td>2-氨基-2-甲基丙醇</td><td>9.85</td></tr></table></body></html>  \n\n用碱性强的胺中和的树脂在用水稀释之前具有很高的黏度，黏度出现交叉现象，当稀释至低浓度时，黏度随着浓度的下降迅速下降，即重复出现稀释初期黏度随着碱强度而变化的现象。  \n\n④贮存稳定性水性丙烯酸酯涂料必定使用氨基甲醛树脂为交联剂，胺的应用可以起着对氨基树脂自缩聚的稳定作用。不同羟甲基化或甲醚化程度对氨基树脂在贮存期间的自缩聚有不同的影响。完全醚化的六甲氧甲基氨基树脂在 $\\mathfrak{p H}$ 为 ${7\\sim}10$ 的碱性条件下非常稳定，不论使用什么胺都可以。有人研究以后认为，六甲氧甲基氨基树脂-丙烯酸型涂料用2-氨基-2-甲基丙醇中和时，最好中和至 $\\mathbf{EN}=90$ 或更高；而在部分甲醚化氨基树脂涂料中使用叔胺更可靠，并且丙烯酸酯树脂应选用低酸值的品种。  \n\n胺对水溶性丙烯酸树脂的水解稳定性亦有好处，在较高温度下贮存的水溶性丙烯酸涂料， $\\mathsf{p H}$ 可以无变化而黏度则有所下降时，加人一些胺可以恢复其原有黏度。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 288,
+        "chunk": "# 4.水性丙烯酸树脂合成及应用  \n\n水溶性丙烯酸树脂配方见表2-1-117。  \n\n表2-1-117水溶性丙烯酸树脂配方  \n\n\n<html><body><table><tr><td>物质名称</td><td>质量分数/%</td><td>物质名称</td><td>质量分数/%</td></tr><tr><td>丙烯酸</td><td>8.4</td><td>甲基丙烯酸甲酯</td><td>40.8</td></tr><tr><td>丙烯酸丁酯</td><td>40.8</td><td>甲基丙烯酸羟乙酯</td><td>10</td></tr></table></body></html>  \n\n制造工艺：称取配方量（质量份）混合单体，加人单体量1. $2\\%$ 的偶氮二异丁晴引发剂，在氮气保护下将混合单体于2.5h内慢慢滴入丙二醇醚类溶剂（单体：溶剂的质量比为 $_2:1)$ ，继续在101℃左右保温1h，再加入总质量 $20\\%$ 的丙二醇醚类溶剂，然后升温蒸出过量的溶剂，至固体分浓缩至 $75\\%$ ，树脂的酸值为62，降温、过滤、出料。  \n\n制成的溶剂型树脂内含有少量助溶剂，其成盐及水化的过程一般不是在合成反应完毕后马上进行，因为如果该批量树脂是用以制造色漆的话，则“水溶性”的树脂对颜料的润湿分散性能是远远不如溶剂型树脂的。正常的工艺是必须先用溶剂型树脂研磨色浆，然后再加胺、加水进行成盐及水性化的处理。胺及水的用量会影响树脂的黏度、形态及应用性能等多种因素。  \n\n水性丙烯酸树脂可以通过改性获得，也可以通过复合配方技术获得。有文献对环氧/叔胺/丙烯酸树脂三元复合体系进行了研究。  \n\n$\\textcircled{1}$ 复合水性丙烯酸树脂配方设计选择环氧树脂、丙烯酸类树脂（丙烯酸、甲基丙烯酸、苯乙烯、丙烯酸酯类等单体共聚物)，N，N-二甲基乙醇胺。从制备涂料样品的配比三角图的非凝胶区域选择6种不同配比，研究原料配比和涂料性能的关系。  \n\n$\\textcircled{2}$ 复合水性树脂合成在 $1000\\mathrm{mL}$ 的四口瓶中，分别装有冷凝管，温度计，机械搅拌器。按表2-1-118中的具体配方量加入丙烯酸树脂溶液和环氧树脂溶液，在搅拌条件下，用甘油浴加热到 $95\\mathrm{^{\\circ}C}$ . $1\\sim2\\mathrm{min}$ 内加入配方量的N，N-二甲基乙醇胺，恒温反应，体系黏度逐渐增大，逐渐由浑浊变为透明的淡黄色，经1.5h后，黏度保持恒定，取样测环氧值为零，结束反应。 北馆 K  \n\n$\\textcircled{3}$ 经性能测试表明 $^{1\\sharp}$ 产品涂膜性能远较其他树脂性能优异，可以达到工业溶剂型防腐漆水平。 $^{5^{\\ast}}$ 与 $6^{\\circ}$ 产品涂膜性能相当，在耐盐水试验42h后，只出现不明显的锈斑； $2^{*}$ ·$3^{\\sharp}$ 和 $4^{\\sharp}$ 产品在 $42\\mathrm{h}$ 时，有明显锈斑。从研究结果可以总结如下：（a）胺的含量高比例。  \n\n表2-1-118复合水性树脂的合成配方  \n\n\n<html><body><table><tr><td>样品 编号</td><td>环氧树脂量</td><td>胺量 (0. 6mmol/mL)/mL(10mmol/mL)/mL</td><td>丙烯酸树脂 （2.22mmol/g）/g</td><td>/%</td><td>固含量（质量分数）环氧占固形物的 质量分数/%</td><td>胺占固形物的 质量分数/%</td></tr><tr><td>1</td><td>245</td><td>32.78</td><td>276</td><td>43.8</td><td>50.8</td><td>5.4</td></tr><tr><td>2</td><td>139.5</td><td>38.9</td><td>322.5</td><td>41. 9</td><td>33.5</td><td>7.0</td></tr><tr><td>3</td><td>146.8</td><td>18.86</td><td>340</td><td>43.6</td><td>33.4</td><td>3.4</td></tr><tr><td>4</td><td>76.7</td><td>10.1</td><td>413.6</td><td>43. 3</td><td>17.7</td><td>1.8</td></tr><tr><td>5</td><td>141.3</td><td>8.5</td><td>350.9</td><td>44.3</td><td>31. 9</td><td>1.5</td></tr><tr><td>6*</td><td>191.3</td><td>16.7</td><td>298.5</td><td>44.4</td><td>42.7</td><td>3.0</td></tr></table></body></html>  \n\n$2^{\\sharp}$ 实验点的胺摩尔分数是环氧基团的4倍以上，由于环氧和丙烯酸树脂复合生成的酯化产物较少，样品的质均分子量不大，直接配制成涂料性能不太好。因为有较多的环氧和胺生成季铵阳离子型化合物，反而适合作为高分子型乳化剂，进一步进行乳液聚合反应。（b）丙烯酸树脂含量高比例。 $4^{\\sharp}$ 实验点中丙烯酸树脂中羧基大大过量，是环氧基的20倍，此时，胺和丙烯酸树脂发生酸碱反应，体系中游离的叔胺很少，胺只起催化剂作用，环氧基团多数和丙烯酸树脂中的羧基酯化，形成酯化接枝大分子，季铵型环氧化合物很少，造成 $4^{\\circ}$ 比2#甚至比 ${3^{*}}$ 样品的质均分子量还高。但复合产物中引入的环氧链段较少，无法充分发挥环氧树脂的优势，虽然4\\*样品在硬度、耐水性方面显示出复合的优势，但耐腐蚀性能接近于单纯的丙烯酸树脂。样品清漆基本性能见表2-1-119。  \n\n表2-1-119样品清漆基本性能测试  \n\n\n<html><body><table><tr><td>实验样品编号</td><td>涂膜厚度/μm</td><td>铅笔硬度/H</td><td>光泽（60°)</td><td>耐盐水性/h</td></tr><tr><td>1</td><td>19.4</td><td>>6</td><td>142.5</td><td>>240</td></tr><tr><td>2</td><td>15.6</td><td>>6</td><td>149. 6</td><td>18</td></tr><tr><td>3</td><td>22.1</td><td>>6</td><td>154.3</td><td>24</td></tr><tr><td>4</td><td>40.5</td><td>>6</td><td>101.3</td><td>36</td></tr><tr><td>5</td><td>32.8</td><td>>6</td><td>154. 2</td><td>42</td></tr><tr><td>6</td><td>24.6</td><td>>6</td><td>155.6</td><td>42</td></tr><tr><td>对比样-1</td><td>61.0</td><td>HB</td><td>109.4</td><td><18</td></tr><tr><td>对比样-2</td><td>19.2</td><td>>6</td><td>160.0</td><td>36</td></tr></table></body></html>\n\n注；对比样-1为可交联的丙烯酸酯类乳液；对比样-2为自由基接枝的环氧丙烯酸复合乳液。  \n\n$\\textcircled{4}$ 环氧含量高比例 $2^{*}$ 和 $4^{\\#}$ 配方不是合适的防水、防锈涂料配方，作为涂料用复合水性树脂，丙烯酸树脂/环氧在 $_{3\\sim10}$ 倍以内，胺/环氧在 $1{\\sim}3$ 倍以内，是较好的配方条件。在此范围内，丙烯酸树脂相对环氧过量越少，涂膜性能越好，如 $1^{\\#}$ 样品比 $^{3^{\\sharp}}$ 样品的丙烯酸树脂过量少， $1^{\\sharp}$ 样品膜性能大大好于 ${3^{*}}$ 。同样，胺相对环氧比例越少，如 ${}_{3^{\\sharp}}$ 和 ${5^{\\sharp}}$ 样品，$5^{\\sharp}$ 胺的比例少于 ${3^{\\sharp}}$ · $^{5\\ast}$ 的膜性能好于3#。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 289,
+        "chunk": "# 四、丙烯酸乳液  \n\n在1953年之前，丙烯酸乳胶漆还没有在建筑涂料领域中应用；而50年后的21世纪它已经成为全球最流行的墙面涂料。丙烯酸乳胶漆之所以能得到迅速发展，主要是因为其干燥快速，容易操作和施工，易清理；人们对油性涂料健康和环境认识的进一步提高，使乳胶漆的应用越来越广泛。目前乳液涂料不仅在建筑领域占主导地位，也在迅速向工业涂料和维护  \n\n涂料领域扩展。",
+        "category": " Introduction"
+    },
+    {
+        "id": 290,
+        "chunk": "# 1.概述  \n\n（1）丙烯酸乳胶漆的诞生1953年Rohm&Haas公司推出了第一代 $100\\%$ 纯丙烯酸乳液RhoplexAC-33，它由丙烯酸酯和甲基丙烯酸合成。基于丙烯酸乳液的水性涂料沿袭了其他非丙烯酸水性涂料的特点，快干、低气味和容易清洗，同时丙烯酸乳液也为涂料生产企业带来了其他优势。纯丙烯酸RhoplexAC-33乳液的涂膜更耐久，比丁苯橡胶和聚乙烯醇有更高的耐碱性。油性醇酸树脂漆能提供高光的涂膜，涂膜表面光滑，且附着力很好，在外墙涂料和装饰漆中得到了广泛应用；而当时的RhoplexAC-33则仅仅局限于内墙的涂装。醇酸树脂漆的耐碱性很差，尤其是新砖石墙面基材上，RhoplexAC-33的表现则较好，且砖石墙面基材对附着力的要求比木头基材低，因此RhoplexAC-33成为在此领域中应用的首选。",
+        "category": " Introduction"
+    },
+    {
+        "id": 291,
+        "chunk": "# (2）丙烯酸酯乳液的特点  \n\n$\\textcircled{1}$ 性能佳、功能多样、品种齐全。乳液涂料对水泥、混凝土等建筑基材的炭化和固化能起到很好的保护作用。还可以做成多种特种功能的涂料，例如弹性涂料、防水涂料、防火涂料、防霉涂料等。  \n\n$\\textcircled{2}$ 色彩丰富，造型美观。在众多的建筑装饰材料中，乳液涂料的颜色最为丰富多彩，造型美观大方。  \n\n$\\textcircled{3}$ 自重轻、易施工、造价低。自重轻，就不必为涂层考虑加固基础地基；施工方便、灵活，无论基材的几何形状如何复杂，一般都能进行施工；涂料施工周期短，造价相对较低。  \n\n$\\textcircled{4}$ 重涂方便。不需要对旧涂层作很费工或很费钱的处理，就可以进行重涂。  \n\n$\\textcircled{5}$ 污染低。涂料的生产不需要高能耗、也不产生无用的废料。乳液涂料本身无毒、不燃、不污染环境、不对人的健康造成危害，因此丙烯酸酯乳液涂料称为环境友好型涂料产品。  \n\n丙烯酸酯乳液具有优异的耐候性、耐酸碱性和耐腐蚀性，但它存在着耐水性和附着性差及低温变脆、高温变黏等缺点，限制了其应用。近年来随着聚合理论和合成技术的不断完善和发展，以及人们对环境友好的绿色化工产品的需求愈来愈高，丙烯酸酯乳液的改性受到了广泛的重视和长足的发展。  \n\n(3）乳液涂料的基本组成乳液涂料由合成树脂乳液、颜料和填料、助剂、水等组成。  \n\n$\\textcircled{1}$ 合成树脂乳液合成树脂乳液是涂料的基料，是乳液涂料的主要成膜物质之一，在涂料中起黏胶剂的作用。涂料及其涂膜的几乎全部性能都与之相关。选择合适的合成树脂乳液的基料是十分关键的。a.涂层的性能总是与聚合物的分子量有关，分子量愈高，涂层理化性能愈好。对于非反应型的基料，为了保证涂层质量，分子量必须做得很高。几十乃至几百万分子量的高聚物只有做成乳液，才能获得较低的黏度，达到应用要求。b.合成树脂乳液可以做成许许多多的品种，因此选择合适的基料来满足供不同性能要求和成本档次的涂料产品。  \n\n丙烯酸酯乳液涂料按聚合物的组成可以分为：苯乙烯-丙烯酸酯共聚乳液、丙烯酸酯-叔碳酸乙烯酯共聚乳液、有机硅-丙烯酸酯共聚乳液、全丙烯酸酯共聚乳液等。按涂膜特征可分为热塑性乳液、热固性乳液和弹性乳液等。按粒子电荷性质可以分为阴离子型乳液、阳离子型乳液和非离子型乳液。按用途可以分为内用乳液、外用乳液和专用乳液。  \n\n对合成树脂乳液的要求：a.外观应为胶质细腻，无粗粒子及机械杂质、色泽浅。b.应具有实用意义的固体含量，一般而言，固体含量较高者黏结能力较强；反之，相反。c.pH和黏度应在批次间无明显差异。d.低的残余单体含量，越小越好，通常的规定不大于0.5%（质量)。e.适宜的最低成膜温度（MFT）和玻璃化温度（Tg）。f.较好的颜料亲和力和对基材的附着力。g·优良的化学稳定性、机械稳定性和稀释稳定性。h.优良的低温稳定性，低的涂膜吸水性，优良的耐老化性能。  \n\n合成树脂乳液的性能：a.合成树脂乳液是环境友好型产品，不污染环境，不危害人体健康。b.聚合物分子量高达数十万至上百万，物理性能较好。c.体系的黏度较低。d.乳液在形成涂膜过程中需要经过粒子聚集、变和凝合的历程，因此乳液的成膜有一个最低成膜温度（MFT)。乳液对基材的渗透性远不如溶液型聚合物。e.乳液是一个准稳定体系，需在一定的条件下，包括乳化剂、保护胶体、pH、温度、电解质和外加剪切力等适宜的条件下，才能在较长的时间内贮存，否则会产生破乳。f.聚合工艺的不同会对乳液的性能有明显影响。  \n\n在丙烯酸酯链上引人羧基可赋予聚合物乳液以稳定性、增稠性，并提供交联点，加入交联单体可提高乳液聚合物的耐水性、耐磨性、拉伸强度、硬度、附着强度、耐溶剂性和耐蚀性等。合成聚丙烯酸酯乳液过程中，单体分散于水中而出现了单体相和水相，表面活性剂存在于两相之间，起到降低两相间界面张力的作用。表面活性剂对生产稳定乳液的物理性质有重要影响，决定着乳液的粒度。因此，当进行聚合时，要根据单体的组成对表面活性剂进行选择，进行充分的搅拌。选择了适当的表面活性剂，就应能得到稳定的乳液聚合物。  \n\n阴离子和非离子型表面活性剂在丙烯酸酯乳液聚合中得到了广泛的应用，非离子型表面活性剂对电解质等的化学稳定性良好，但使聚合速度减慢，而且乳化力弱，聚合中易生成凝块。阴离子型表面活性剂化学稳定性不那么好，但与非离子型比较，有生成乳液粒度小、乳液机械稳定好，聚合中不太容易生成凝块的优点。因此在使用阴离子型表面活性剂时，易得到浓度高而稳定的乳液。阳离子型表面活性剂则应用有限。在乳液聚合多数情形下，总是把阴离子和非离子型两种表面活性剂拼合使用，有效地发挥两者特点。  \n\n添加缓冲剂可以调节 $\\mathsf{p H}$ ，使之维持在适合反应的 $\\mathrm{pH}=4\\sim5$ 之间。反应时通过共聚物的水解，pH有降低的情况发生。所添加的缓冲剂有碳酸氢钠、磷酸氢二钠等盐；在使用酸性单体时，一般应追加缓冲剂。  \n\n在某些乳液聚合体系中，为有效控制乳胶粒尺寸、尺寸分布以及乳液稳定，常需加入水溶性保护胶；它们通过与聚合物粒子表面接触，把聚合物包围起来而起到防止凝聚作用。但这种保护胶会增加聚合物膜的亲水性，因此要尽可能地降低使用浓度。代表性的保护胶有：羟乙基纤维素、淀粉、明胶、甲基纤维素、聚乙烯醇、聚丙烯酸钠、阿拉伯胶等。保护胶的机能与表面活性剂有类似之处，在聚合开始前或聚合终了后都可以加人。一般来说，保护胶用量和品种的选择，要取决于表面活性剂的种类，关键是要保持两者之间的平衡。乳液的单体组成与浓度，对保护胶的选择也有很大的影响。对于丙烯酸酯乳液而言，较好的保护胶是聚丙烯酸钠、苯乙烯-丙烯酸的共聚物的钠盐、苯乙烯顺丁烯二酸酐共聚物的钠盐、双异丁烯-马来酸二钠共聚物等，它们除了用作保护胶外，还可用作涂料中颜料及其他的添加剂的分散剂。  \n\n$\\textcircled{2}$ 颜料和填料颜料和填料是乳液涂料主要成膜物质之一。在无光乳液涂料中，颜料和填料是用量最大的组分（除水外)。颜料主要提供遮盖力和色彩，并保持较长时间内不会丧失这种功能；填料的作用是提供粒度分布和对比率，以便改善施工性能，提高颜料的遮盖效率和增强涂层理化性能。乳液涂料中的颜填料的选择基本与溶剂型涂料体系一样，但丙烯酸乳液聚合物的 $\\mathsf{p H}$ 一般在 $\\scriptstyle7\\sim9$ 之间，因此在配制建筑用内外墙乳胶漆时，若墙体为水泥砂浆制品（碱性基材表面)，那么颜料应选择碱性为好，否则颜色不稳定，墙面容易出现发  \n\n花、不均匀退色和变色等现象。  \n\n③助剂乳液涂料的配方特点之一是虽然绝对添加量不是很多，但应用的助剂品种较多。这是因为乳液涂料的介质是水，水的张力大，极性大，蒸发热高，因而造成许多缺陷；许多在溶剂型涂料中没有的问题，在乳液涂料中会表现得十分严重，如流变性能、泡沫、低温成膜、霉变等。克服这些缺陷主要是通过添加助剂来解决的，因此在乳液涂料中使用了多种助剂。由此可见，助剂是乳液涂料必不可少的原料，它主要满足乳液涂料在生产、贮运和施工期间的工艺操作要求，支持涂膜达到设计目标的指标。一且形成涂层，助剂就完成了自己的使命，最好能够较快地逸出涂层，残留在涂层内的助剂应尽量不对涂层构成负面影响。  \n\n在乳液涂料配方中使用的助剂包括：颜料润湿分散剂、 $\\mathsf{p H}$ 调节剂、消泡剂、流变改性剂、增稠剂、杀菌防腐剂、助成膜剂、防霉抗藻剂、抗冻剂、触变剂、紫外线吸收剂等。当然，这些助剂并不是每个配方都必须加入的，而是根据配方设计师的意愿和实际情况加以选用。一般情形下，分散剂、增稠剂和防霉剂是必须添加的。  \n\n$\\textcircled{4}$ 水水是乳液涂料的分散介质，占乳液涂料总量的 $35\\%\\sim50\\%$ 。乳液涂料以水为分散介质占了很多优势，如生产、使用的安全和方便，贮运的安全性，环境保护的要求，劳动保护要求，来源丰富和价格便宜等。看起来水比较简单，在使用中应没有什么问题，但其实不然，水中如含有电解质（尤其是多价金属离子)，就会影响乳液涂料的稳定性；假如水中含有微生物，乳液涂料就有霉变的危险等，因此水的问题要引起足够重视。在工业生产中乳液聚合应使用蒸馏水或去离子水，氯化钠的含量在 $0.05\\mathrm{mg/L}$ 以下，水的电导值控制在$\\boldsymbol{10}\\mathrm{{mS}}$ 以下。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 292,
+        "chunk": "# 2.所用原材料  \n\n(1）单体在工业生产中制造丙烯酸酯聚合物乳液常用的单体有：丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸-2-乙基己酯、丙烯酸异丁酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯等。除了丙烯酸酯均聚或共聚制造丙烯酸酯乳液以外，为了赋予乳液聚合物所要求的性能，常常要和其他单体共聚，制成丙烯酸酯共聚物乳液，常用的共聚单体有醋酸乙烯酯、苯乙烯、丙烯腈、顺丁烯二酸二丁酯、偏二氯乙烯、氯乙烯、丁二烯、乙烯等。在很多情形下还要加入功能单体（甲基）丙烯酸、马来酸、富马酸、衣康酸、（甲基）丙烯酰胺、丁烯酸等以及交联单体（甲基）丙烯酸羟乙酯、（甲基）丙烯酸羟丙酯、羟甲基丙烯酰胺、双（甲基）丙烯酸乙二醇酯、双（甲基）丙烯酸丁二醇酯、三羟甲基丙烷三丙烯酸酯、二乙烯基苯、用亚麻仁油和桐油等改性的醇酸树脂等。含羟基单体及交联单体的加入量一般为单体总量的 $1.5\\%\\sim5\\%$ 。不同的单体将赋予乳液聚合物不同的性能。  \n\n(2）引发剂引发剂是乳液聚合中的重要组分。依据反应体系的差异可以选择水溶性引发剂或油溶性引发剂；也可按自由基生成体系的差异选择热分解型和氧化还原型引发剂。最为普遍使用的发生自由基的引发剂为水溶性的、经热分解的过硫酸钾、过硫酸铵、过氧化氢、过氧化氢衍生物以及水溶性的偶氮化合物等。使用浓度一般在 $0.01\\%\\sim0.2\\%$ 之间。应用最多的氧化还原型引发剂有：过硫酸体系和氯酸盐-亚硫酸氢盐体系等，水溶性氧化还原引发剂系统由氧化剂和还原剂组成，由于可在低温下进行，故可制得高分子量聚合物。  \n\n(3）乳化剂用作聚合的乳化剂按亲水基团的性质有四类：非离子型、阴离子型、阳离子型和两性乳化剂。目前生产中使用的乳化剂大多为阴离子型乳化剂和非离子型乳化剂相结合。乳化剂的用量一般为单体总量的 $2\\%\\sim5\\%$  \n\n(4）中和剂树脂品种的不同，选用的中和剂也不同，阴离子型水性树脂使用碱性中和剂，如氨水、胺类；阳离子型水性树脂使用有机酸类中和剂，例如甲酸、乙酸和乳酸等。  \n\n（5）助溶剂常用的助溶剂主要为醇类溶剂，例如乙醇、异丙醇、正丁醇、叔丁醇、仲丁醇、丙二醇单乙醚等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 293,
+        "chunk": "# 3.聚合方法及机理  \n\n（1）丙烯酸乳液聚合反应的三个阶段  \n\n第1阶段：乳胶粒生成阶段。在乳化剂和少量单体存在的水分散体系中，胶束的数量远比单体液滴的数量多，因此水溶性引发剂在水相中引发聚合反应。水中单体浓度低，形成的单体自由基也会进入到增溶胶束中去生长。增溶胶束就成了单体-聚合物的乳胶粒。这个阶段结束时，胶束消失，全部形成了乳胶粒。  \n\n第2阶段：匀速聚合阶段。这一阶段是从第一阶段末直到单体液滴消失为止，是聚合过程中极重要的阶段。在这个阶段中可以认为已经生成的乳胶粒数是不变的，而且只有单体的液滴存在。乳胶粒中单体浓度也可以认为是恒定的。引发剂在粒子中的终止占优势，水相中的终止可以略去不计，自由基的脱吸速度极小与吸附速率相比可以忽略处理。  \n\n第3阶段：降速阶段。这是从单体液滴消失后到反应结束的阶段，约占总转化率的$50\\%$ 。在第3阶段初期，乳胶粒中的单体的浓度下降很慢；而乳胶粒的体积不但不减小，还随着转化率增大而增大。这是因为单体液滴尽管消失了，但乳胶粒仍然能从水相吸收溶解的单体。当溶解在水相中的单体被耗尽时，乳胶粒中单体的浓度就随着转化率的增大而逐渐降低；随着转化率的增大，乳胶粒中单体的浓度才开始较快地下降，同时因为聚合物比单体密度大，所以乳胶粒的体积将随着转化率的增大而稍有收缩。在此阶段，乳胶粒内单体的浓度不断下降，由于黏度增加、终止速率减慢，会出现自动加速现象；随着转化率的提高，在乳胶粒内部中聚合物的浓度越来越大，大分子链彼此缠结在一起，致使乳胶粒内部黏度越来越高，自由基链扩散阻力越来越大，发生凝胶效应，会造成聚合反应速率的增大、分子量增大、分子量分布变宽。  \n\n(2）核壳乳液聚合和无皂乳液聚合方法  \n\n$\\Phi$ 核壳乳液聚合核壳乳液聚合方法是预先用乳液聚合法制得高分子乳液粒子，以此做种核，再用与其同类或不同种类的单体在粒子内聚合，使粒子增长肥大的方法。在进行核壳乳液聚合时，随着粒子的逐渐增厚长大，为确保其稳定性，往往需要加入一些乳化剂。但是，此时需要特别注意乳化剂的加入量，若不严格控制乳化剂的加入量，则超过种核粒子的表面饱和吸附量的过剩乳化剂，将在水相中形成新的胶束，期望的核壳聚合便有可能在核粒子以外的新生态胶束中重新开始，而产生新的乳胶粒子。  \n\n通常情况下，核壳复合高分子乳液粒子，总是设计成核层为硬质聚合物，壳层为软质聚合物的结构形式。如为了提高丙烯酸乙酯（EA）-丙烯酸（AA）共聚乳液的离子型交联薄膜的机械强度，导人硬单体甲基丙烯酸甲酯（MMA)，经共聚将MMA组分导人后几乎看不出什么效果；相反，以聚甲基丙烯酸甲酯作核进行EA组分和AA组分的核-壳乳液共聚，所制得的乳液则由于MMA组分的导入，漆膜的强度明显提高。  \n\n苯乙烯和丙烯酸乙酯（EA）共聚乳液的组分同乳液的最低成膜温度（MFT）之间有线性关系，即随着苯乙烯量的增加，MFT呈直线增加。以聚丙烯酸乙酯（PEA）为核，将苯乙烯进行核-壳乳液聚合，即使苯乙烯量增加到 $70\\%$ ，其乳液仍然能在 $-6\\%$ 充分成膜。尽管进行的是以PEA为核的苯乙烯的核-壳乳液聚合，其结果却得到了核层为聚苯乙烯的富集芯层、壳层为聚丙烯酸乙酯分子富集层的核-壳乳液，在该粒子中产生了相转变。其原因可能为聚丙烯酸乙酯分子比聚苯乙烯分子对水有着更大的亲和力。Khan等研究了包含聚丙烯酸正丁酯-甲基丙烯酸甲酯-甲基丙烯酸共聚核结构和聚苯乙烯-丙烯睛，聚丙烯酸丁酯-甲基丙烯酸甲酯壳结构的系列核-壳乳液，合成方法为半连续法。结果表明，具有不同共聚物比例的壳对性质有较大影响，以苯乙烯/丙烯睛60/40的比例为最佳。  \n\n$\\textcircled{2}$ 无皂乳液聚合法无皂乳液聚合是指不加乳化剂或加入微量乳化剂的乳液聚合过程，即以水溶性低聚物为乳化剂，可使用的低聚物有顺丁烯二酸化聚丁二烯、顺丁烯二酸化醇酸、顺丁烯二酸化油，也可以用有聚合性表面活性剂进行共聚，如丙烯酸磺基丙醇酯、对苯乙烯磺酸钠等。在水性介质中先加少量亲水的丙烯酸或甲基丙烯酸酯单体进行聚合，形成粒径为 $100\\sim200\\mathrm{nm}$ 的聚合物粒子。然后，再加入憎水性单体进行聚合。憎水性单体在前述聚合物粒子表面上选择吸附，聚合就在这里发生。成核单体虽相对于憎水单体量的约 $0.5\\%\\sim$ $2\\%$ ，但利用此法可制得粒度为 $0.08\\sim0.4\\mu\\mathrm{m}$ 、分布窄、不含乳化剂和稳定剂的乳液。表2-1-120中是一个聚合配方，硫酸铜是为促进聚合而添加的。  \n\n表2-1-120无皂乳液配方   \n\n\n<html><body><table><tr><td>原 料</td><td>质量比</td><td>原 料</td><td>质量比</td></tr><tr><td>甲基丙烯酸甲酯</td><td>5</td><td>过硫酸钾(0.005mol/L)</td><td>0.4</td></tr><tr><td>硫酸钢(0.01mol/L)</td><td>7.5</td><td>硫代硫酸钠(0.005mol/L)</td><td>0.37</td></tr><tr><td>水</td><td>250</td><td>苯乙烯</td><td>120</td></tr></table></body></html>  \n\n上述配方在 $60^{\\circ}\\mathsf{C}$ ， $\\mathrm{pH}=3\\sim4$ 的条件下，数分钟内聚合完成。生成的聚合物粒径为$104\\mathrm{nm}$ 。然后，添加苯乙烯，大约用5h完成聚合，得到单体：水相 $=1:2$ 的乳液。粒度为 $287\\mathrm{nm}$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 294,
+        "chunk": "# 4.影响聚合反应的因素  \n\n在乳液聚合中，乳化剂、引发剂、反应温度、反应均匀性和电解质等都对乳液聚合的过程、产量和品质产生重要影响。  \n\n（1）乳化剂乳化剂的种类和浓度对乳胶粒直径、数量、分子量、聚合反应速率和乳液的稳定性均有明显的影响。对于正常的乳液聚合，乳化剂的浓度在合理范围内，乳化剂浓度越大，胶束数目越多，按胶束机理生成的乳胶粒数目也越多，乳胶粒数目越大，乳胶粒直径就越小。对于不同种类的乳化剂，其特性参数临界胶束浓度（CMC)、聚集数及单体的增溶度等各不相同。当乳化剂用量和其他条件相等，临界胶束浓度值越小、聚集数越大或增溶度越大的乳化剂成核概率也大，所生成的乳胶粒多，即乳胶粒数目越大，乳胶粒直径越小，反应速率越大，聚合物分子量越大。  \n\n（2）引发剂当引发剂的浓度增大时，自由基生成速率增大，链终止的速率也增大，聚合物的平均分子量降低。同时，当引发剂浓度和自由基生成速率增大时，水相中自由基浓度增大，这将导致在聚合反应第一阶段自由基由水相向胶束中扩散速率增大，成核速率增大，也会导致水相中按低聚物机理成核速率增大，此两种情况均引起乳胶粒数目增大，直径减小及聚合反应速率增大。  \n\n(3）反应温度在乳液聚合过程中，反应温度高时，引发剂分解速率常数大，当引发剂速率一定时，自由基生成速率亦大，使乳液粒中链终止速率增大，聚合物平均分子量降低。同时，当反应温度升高，会导致乳胶粒数目增大，平均直径减小；乳液布朗运动加剧，乳胶粒之间碰撞和发生聚结的速率增大，致使乳液的稳定性降低；同时，乳胶粒表面上的水化层减薄，导致乳液稳定性下降。尤其当温度升高到等于或大于乳化剂的浊点时，乳化剂失去了稳定作用，导致破乳。  \n\n(4）搅拌影响搅拌在乳液聚合过程中的重要作用在于把单体分散成单体珠滴，并且有利于传热。搅拌强度太高时，容易使乳液粒数目减少，乳液粒直径增大，聚合反应速率降低，还会导致乳液凝胶、破乳。因此，在乳液聚合过程中应适度搅拌。  \n\n(5）电解质影响电解质的含量和种类直接影响乳液聚合体系的稳定性。有人认为体系中只要含电解质，其稳定性就会下降，甚至产生凝聚。但当电解质含量少时，它不但不会使聚合物乳液稳定性下降，反而会提高它的稳定性。这是因为有少量电解质时，在盐析作用下，乳化剂临界胶束浓度值降低。  \n\n(6）凝胶现象凝胶现象就是在乳液聚合过程中，聚合物乳液局部胶体稳定性差而引起的乳胶粒的聚结，形成宏观或微观的凝聚物。在搅拌下，这些凝聚物可以分散在乳液中，可以用沉降法或过滤法去除，微观凝胶颗粒的存在会使乳液的蓝光减弱，颜色发白，细腻感消失，外观粗糙。有时在乳液聚合过程中，整个体系失去稳定性，产生大量凝胶，甚至完全凝胶，使产品报废。另外一种情况，凝聚物沉积在反应器壁面、顶盖、挡板、搅拌轴、搅拌叶轮、内部散热器、温度计套管等反应釜内部构件上，越积越多，形成粘釜和挂胶，影响聚合物乳液的产品质量。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 295,
+        "chunk": "# 5.丙烯酸乳液的合成工艺  \n\n(1）生产工艺乳液聚合工艺有以下多种：间歇工艺、连续工艺、半连续工艺、补加乳化剂工艺和种子乳液聚合工艺等。不同的聚合工艺对合成乳液的生产成本、质量和生产效益等均产生影响。  \n\n由于丙烯酸酯单体聚合反应放热量大，凝胶效应出现得早，很难采用间歇乳液聚合工艺进行生产，否则常会发生事故，也为产品质量带来不良影响。同时聚丙烯酸酯及其共聚物乳液一般用作涂料、黏合剂、浸渍剂、特种橡胶等，用于各行各业，其品种繁多，配方与生产工艺各异，大多为精细化工产品，产量都不是特别大，故很少采用连续操作。目前进行的丙烯酸酯乳液聚合一般采用半连续工艺。  \n\n(2）乳胶漆生产以年产1万吨乳胶漆为例，需要的主要原材料、工艺过程、设备和三废处理如下。  \n\n$\\Phi$ 产品类型与主要原材料以生产丙烯酸外墙涂料2500t、内墙涂料7500t计算，需要的主要原材料为：纯丙乳液750t；苯丙乳液2000t；金红石型钛白粉600t；锐钛型钛白粉800t；填料3000t；各种助剂500t；色浆40t等。  \n\n$\\textcircled{2}$ 主要生产设备颜料混合罐6个；高速搅拌机3台；砂磨机3台；乳液配制罐2个；调漆罐、过滤机、输送泵、灌装机、调色机等。  \n\n$\\textcircled{3}$ 一般生产工艺将计量过的水加入到与高速搅拌机配套的混合物配料罐中，加人配方量的分散剂、湿润剂、部分增稠剂、消泡剂、杀菌剂等助剂，低速下搅拌混合均匀，然后加入颜料、填料等，待颜填料润湿后提高搅拌速度，在高速下使粉体混合均匀。  \n\n用齿轮泵将混合均匀的浆料送入砂磨机中，进行研磨，直到细度符合要求。  \n\n将配方量的乳液送入基料配制罐，边揽拌边加入各种助剂：成膜助剂、部分消泡剂、杀菌剂等，充分混合均匀，过滤加人调漆罐。  \n\n将乳液基料送入调漆罐后开动搅拌，边搅拌边加入细度合格的研磨色浆。  \n\n乳液基料与色浆按配方量加入完毕后，搅拌 $15\\mathrm{\\sim}30\\mathrm{min}$ ，混合均匀后调色，加入剩余增稠剂，补加配方水，合格后，出料包装。  \n\n$\\textcircled{4}$ 三废处理生产废水每天估计约排放10t，利用污水沉降池与污水处理排放系统处理。  \n\n(3）质量控制乳液质量的控制是通过对其性能的测试、合成严格按工艺配方和流程进行。通常测试的项目如下。 $\\textcircled{1}$ 外观：乳白色黏稠液体。 $\\textcircled{2}$ 固含量：测定方法为在已准确称量的瓶中，称取一定量的样品，放人 $1100$ 的烘箱中至恒重，则固含量 $(\\%)=$ 恒重后样品质量/样品湿 $\\pi\\times100\\%$ 。 $\\textcircled{3}$ 黏度。 $\\textcircled{4}\\mathrm{pH}$ ：可以用 $\\mathsf{p H}$ 试纸或pH计测定。乳液聚合时的pH一般在 $4{\\sim}6$ ，出厂时为减少泡沫以及用户使用方便，一般加入了氨水，此时 $\\mathbf{pH}$ 一般在 $8\\sim9$ 。$\\textcircled{5}$ 最低成膜温度：可以采用温度梯度板、温度计等来测量。 $\\textcircled{6}$ 钙离子稳定性测量。 $\\textcircled{7}$ 耐水性。将乳液均匀地涂布在玻璃板上，让其干燥后，把玻璃板浸水24h，若有涂膜缓慢发白，干燥后仍能附着在玻璃板上，涂料的耐水性较好；若不发白，耐水性很好。 $\\textcircled{8}$ 残余单体测量：用气相色谱测定。  \n\n(4）安全生产在丙烯酸乳液生产中操作人员必须遵守劳动纪律，按照安全操作规程操作。操作人员上岗操作之前要戴好必要的劳动安全防护用品，做到认真交接班、仔细检查设备、物料以及安全设施等。在生产过程中要集中注意力、精心操作，严格按工艺操作规程以及岗位安全责任制度操作。对于搅拌设备、研磨设备等传动设备在处于运转状态时，不可接触转动等部件、防止物品落入容器，不许可对设备进行检修与清洁工作。对于生产设备的检查要落实安全责任措施，进人容器检修，必须申请得到批准、带好防护用具、进行安全隔绝、通风、规定时间安全检修、专人监护并坚守岗位和有救护与抢救措施等。设备要彻底检查，一切完备与安全后才能启用。严防火灾，配备足够的消防器材，人人均会使用。用电要防止触电事故。生产完成要先清洗、检查设备和工具，离开前切断水、电、气。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 296,
+        "chunk": "# 6.丙烯酸乳液的合成及应用  \n\n丙烯酸乳液涂料就成膜物质来说，分为三种：一种是纯丙型涂料，它以丙烯酸共聚乳液为成膜物质，其性能最好，但价格较高。第二种是苯丙型，是以苯乙烯与丙烯酸类单体的共聚乳液为成膜物质。第三种是乙丙型，是以醋酸乙烯与丙烯酸单体的共聚乳液为成膜物质。后两者的成本比纯丙型低。根据使用要求，丙烯酸涂料有内墙和外墙涂料两种，它们又分为有光、平光和无光三种。因为纯丙烯酸类乳液的价格较高，所以丙烯酸类墙面涂料以共聚型为主。  \n\n(1）苯丙乳液涂料苯丙外墙和内墙涂料都以苯丙乳液为基料，但填料比例不同，配合剂也不同。外墙涂料性能要求较高，因而填料比例低些，还需配合一些特殊的添加剂，但价格较高。苯丙乳液涂料的最低成膜温度较高，施工温度一般不得低于 $10^{\\circ}\\mathrm{C}$ 。苯丙有光乳液涂料可用于门窗涂装，涂膜坚韧牢固，光泽适度。平光涂料和无光涂料用于墙面，使墙面显得柔和平整。苯丙乳液为苯乙烯和丙烯酸酯共聚物乳液，典型配方见表2-1-121。  \n\n表2-1-121苯丙乳液配方  \n\n\n<html><body><table><tr><td colspan=\"2\">组 分</td><td colspan=\"4\">用量（质量比）</td></tr><tr><td colspan=\"2\">苯乙烯</td><td>一</td><td>2</td><td>3</td><td>4</td></tr><tr><td rowspan=\"6\">单体</td><td></td><td>23</td><td>23</td><td>35</td><td>30</td></tr><tr><td>丙烯酸</td><td></td><td>一</td><td>1</td><td></td></tr><tr><td>丙烯酸丁酯</td><td>23</td><td>23</td><td></td><td>10</td></tr><tr><td>丙烯酸异辛酶</td><td></td><td></td><td>11</td><td>7</td></tr><tr><td>甲基丙烯酸</td><td>0.5</td><td></td><td></td><td>0.5</td></tr><tr><td>甲基丙烯酸甲酯</td><td>2</td><td></td><td></td><td></td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td colspan=\"2\">组 分</td><td colspan=\"4\">用量（质量比）</td></tr><tr><td rowspan=\"2\"></td><td></td><td>1</td><td>2</td><td>3</td><td>4</td></tr><tr><td>OP-10</td><td></td><td>2.5</td><td>1.5</td><td>2.0</td></tr><tr><td rowspan=\"3\">乳化剂</td><td>K12</td><td></td><td>1</td><td>1</td><td>1</td></tr><tr><td>MS-1</td><td>2.4</td><td></td><td></td><td></td></tr><tr><td>聚甲基丙烯酸钠</td><td>1.4</td><td></td><td></td><td></td></tr><tr><td rowspan=\"3\">保护胶体 分散剂</td><td>聚丙烯酸钠</td><td></td><td>1</td><td>1. 5</td><td></td></tr><tr><td>聚苯乙烯-顺丁烯二酸酐共聚钠盐</td><td></td><td></td><td></td><td>1.5</td></tr><tr><td>水</td><td>48.8</td><td>49.5</td><td>49</td><td>49</td></tr><tr><td>引发剂</td><td>过硫酸钾、过硫酸铵</td><td>0.24</td><td>0.24</td><td>0.24</td><td>0.24</td></tr><tr><td>缓冲剂</td><td>小苏打、磷酸氢二钠</td><td>0.22</td><td>0.22</td><td>0.22</td><td>0.22</td></tr></table></body></html>  \n\n生产工艺：将乳化剂溶解于水中，加入混合单体，在激烈搅拌下进行乳化。然后把乳化液的1/5投人反应釜中，加人 $_{1/2}$ 的引发剂，升温到 $70\\sim72\\Upsilon$ ，保温至物料呈蓝色，此时会出现一个放热高峰，温度可能升至 $80^{\\circ}\\mathrm{C}$ 以上。待温度下降后开始滴加混合乳化液，滴加速度以控制釜内温度稳定为准，单体乳液滴加完后，升温至 $95\\mathrm{^\\circC}$ ，保温 $30\\mathrm{min}$ ，再抽真空除去未反应单体，最后冷却，加入氨水调 $\\mathbf{\\pH}$ 至 $8{\\sim}9$ ，出料。  \n\n(2）乙丙乳液涂料（或醋丙乳液）醋丙乳液是以醋酸乙烯与丙烯酸单体共聚成的乳液。与苯丙乳液涂料相比乙丙乳液涂料的耐水性较差，但成本较低。配方中MS-1为兼有阴离子型和非离子型乳化剂特性的乳化剂，是最适合于乙丙乳液聚合体系的乳化剂。典型的配方见表2-1-122。  \n\n表2-1-122乙丙乳液配方  \n\n\n<html><body><table><tr><td colspan=\"2\">组 分</td><td colspan=\"4\">用量（质量比）</td></tr><tr><td colspan=\"2\"></td><td>1</td><td>2</td><td>3</td><td>4</td></tr><tr><td rowspan=\"6\">单体</td><td>醋酸乙烯酯</td><td>81</td><td>90</td><td>85</td><td>75</td></tr><tr><td>丙烯酸丁酯</td><td>10</td><td></td><td></td><td>23</td></tr><tr><td>丙烯酸异辛酯</td><td></td><td>10</td><td>13</td><td></td></tr><tr><td>甲基丙烯酸</td><td>0.6</td><td></td><td></td><td>2</td></tr><tr><td>丙烯酸</td><td></td><td>0.5</td><td>2</td><td></td></tr><tr><td>甲基丙烯酸甲酯</td><td>8.4</td><td></td><td>11</td><td></td></tr><tr><td rowspan=\"3\">乳化剂</td><td>OP-10</td><td>1. 0</td><td>2</td><td>1</td><td>3</td></tr><tr><td>K12</td><td></td><td>0.5</td><td></td><td>1</td></tr><tr><td>MS-1</td><td>2.0</td><td></td><td>2</td><td></td></tr><tr><td rowspan=\"2\">保护胶体</td><td>聚甲基丙烯酸钠</td><td></td><td></td><td></td><td>1</td></tr><tr><td>聚乙烯醇</td><td></td><td>3</td><td></td><td></td></tr><tr><td>分散剂</td><td>水</td><td>120</td><td>120</td><td>120</td><td>120</td></tr><tr><td>引发剂</td><td>过硫酸钾、过硫酸铵</td><td>0.5</td><td>0.4</td><td>0.4</td><td>0.4</td></tr><tr><td>缓冲剂</td><td>小苏打、磷酸氢二钠</td><td>0.4</td><td>0.3</td><td>0.3</td><td>0.3</td></tr></table></body></html>\n\n生产工艺：首先将规定量的水和乳化剂加人反应釜中，升温至 $65\\mathrm{{C}}$ ，把甲基丙烯酸一  \n\n次性投人反应体系，然后将混合单体的 $15\\%$ 加入到釜中，充分乳化后，把 $25\\%$ 的引发剂和缓冲剂加入签内，升温到75℃进行聚合，当冷凝器中无明显回流时，将其余的混合单体、引发剂溶液及缓冲剂溶液在 $4\\sim4.5\\mathrm{h}$ 内滴加完毕。保温 $30\\mathrm{min}$ ，将物料冷却至 $45\\mathrm{{C}}$ ，即可过滤、出料包装。  \n\n(3）纯丙乳液纯丙乳液是纯粹用丙烯酸系和甲基丙烯酸系单体所制成的共聚物乳液，典型配方实例见表2-1-123。  \n\n表2-1-123 纯丙乳液配方  \n\n\n<html><body><table><tr><td colspan=\"2\">组 分</td><td colspan=\"4\">用量（质量比）</td></tr><tr><td colspan=\"2\"></td><td>1</td><td>2</td><td>3</td><td>4</td></tr><tr><td rowspan=\"6\">单体</td><td>丙烯酸丁酯</td><td>65</td><td>23</td><td></td><td>10</td></tr><tr><td>丙烯酸乙酶</td><td></td><td>23</td><td>35</td><td>30</td></tr><tr><td>甲基丙烯酸甲酯</td><td>33</td><td></td><td></td><td></td></tr><tr><td>丙烯酸甲酯</td><td></td><td></td><td></td><td>0.5</td></tr><tr><td>丙烯酸</td><td>2</td><td>1</td><td>1</td><td></td></tr><tr><td>丙烯酸异辛酯</td><td></td><td></td><td>11</td><td></td></tr><tr><td rowspan=\"3\">乳化剂</td><td>OP-10</td><td></td><td>2.5</td><td>2.5</td><td>2.5</td></tr><tr><td>K12</td><td></td><td>1</td><td>1</td><td>1</td></tr><tr><td>烷基苯聚醚磺酸钠</td><td>3</td><td></td><td></td><td></td></tr><tr><td>分散剂</td><td>水</td><td>125</td><td>49.5</td><td>49</td><td>49</td></tr><tr><td>引发剂</td><td>过硫酸钾、过硫酸铵</td><td>0.4</td><td>0.24</td><td>0.24</td><td>0.24</td></tr><tr><td>缓冲剂</td><td>小苏打、磷酸氢二钠</td><td>0.3</td><td>0.22</td><td>0.22</td><td>0.22</td></tr></table></body></html>  \n\n（4）有机硅氧烷改性丙烯酸酯乳液有机硅改性丙烯酸酯可以制备各种性能优异的建筑涂料，以该树脂为主要成膜物的硅丙涂料具有优越的耐候性、耐水性、耐光照、抗粉化、耐沾污性，成本则比氟改性丙烯酸乳液低，因此非常适于户外装饰用涂料。由于聚硅氧烷分子主链结构的Si-O键能很高，比C—C和C-O键高，分子体积大，内聚能密度低，因此具有良好的耐高低温性能、疏水性、透气性和耐候性；有机硅氧烷分子因其结构特性，使它具有低表面张力、特殊的柔顺性和化学情性等特点。用有机硅氧烷对丙烯酸酯类乳液进行改性，能有效地结合有机硅与丙烯酸树脂各自的优点。有机硅氧烷对丙烯酸酯乳液的改性方法一般分为两种：物理方法和化学改性法。  \n\n$\\Phi$ 物理共混方法物理共混法比较简单但能使产物性能得到较大改善，将有机硅乳液或分散液直接加人到丙烯酸酯乳液中，两种乳液不发生化学反应。例如采用半连续乳液聚合的方法，将八硝苯基笼型硅倍半氧烷（ONPS）掺混人（甲基）丙烯酸酯乳液中，结果发现：当ONPS的加人量低达3%时，丙烯酸树脂的玻璃化温度明显提高，乳液涂膜的拉伸强度大幅上升，但断裂伸长率略有下降。  \n\n有机硅丙烯酸酯共混乳液的稳定性一般较差，容易发生分层，贮存期短。共混乳液的形态及物理性质主要由混合的两种聚合物的相容性决定，而相容性的好坏与各组分的浓度、相间的界面张力、聚合物的分子量和迁移能力等多种因素相关。有人提出可采用两种方法来改善共混乳液的混溶性：一是加人增溶剂降低两相间的表面张力；二是加入交联剂降低聚硅氧烷的分子迁移率。  \n\n$\\textcircled{2}$ 化学改性法通过化学反应使有机硅氧烷单体和丙烯酸酯单体之间形成化学键，可明显改善两者之间的相容性。引入硅氧烷的丙烯酸酯体系具有聚硅氧烷-聚丙烯酸酯简单物理共混所没有的优良性能。  \n\n由于硅丙乳液体系制备困难和具有不稳定性，其研究进展较慢。主要研究方向有两类：一是用含羟基的丙烯酯类单体与有机硅氧烷（或硅醇）接枝缩聚；二是用含乙烯基官能团的有机硅单体或预聚体与丙烯酸酯类单体加成共聚。这两类聚合方法中有机硅的引入量都在10%左右（占聚合物的质量分数)，对涂料性能的改善十分有限（一般有机硅的引入量低于 $15\\%$ ，对性能的改善是有限的)。现有的硅丙乳液大多采用含双键的有机硅单体或聚硅氧烷与丙烯酸酯类单体加成共聚制得。其合成方法按加料方式不同有以下多种：一次加料法，预乳化全连续法，预乳化部分连续法，非预乳化全连续法，种子乳液法，单体乳液滴加法，引发剂滴加法。不同方法制备共聚物乳液时，聚合反应速率、对粒径的影响规律及胶膜的性能都有差异。其中种子乳液法和预乳化部分连续法所得乳液具有良好的相容性、稳定性、粒径分布均匀，乳胶成膜性好。近年来，有关聚硅氧烷/丙烯酸酯乳液共聚的研究逐渐增多，而且随着乳液聚合技术的不断创新，许多新的乳液聚合方法也运用到有机硅丙烯酸酯共聚乳液中。  \n\n常见的有机硅单体有有机硅乙烯基活性单体和具有环状结构的有机硅烷单体。有机硅乙烯基单体或带活性乙烯基的聚硅烷单体与丙烯酸酯共聚，能获得稳定的有机硅丙烯酸酯乳液。下面是一个有机硅改性的硅丙乳液的配方与合成。  \n\n配方中使用的主要材料为：甲基丙烯酸甲酯（MMA)，丙烯酸丁酯（BA)，α-甲基丙烯酸（MAA)，过硫酸铵（APS)，十二烷基硫酸钠（SDS)，反应性乳化剂（LatemulS180A)，助乳化剂（十六烷HD)，乙烯基三乙氧基硅烷（VTES)， $\\gamma$ 甲基丙烯酰氧丙基三甲氧基硅烷（MPMS)，羟基硅油等。  \n\n制造工艺：按表2-1-124中的配方，将乳化剂（SDS和LatemulS-180）溶解在去离子水中，制得水溶液；聚合单体、助乳化剂、有机硅单体等混合制得油溶液。在冰水浴中混合水溶液和油溶液，均匀搅拌 (预乳化) $2\\mathrm{{min}}$ ，再超声 $15\\mathrm{{min}}$ ，得到细乳液，超声完毕后将细乳液倒人四颈夹套釜中，在此之前夹套釜需先通氮排去釜中的空气。在氮气保护下，搅拌$10\\mathrm{{min}}$ 后，恒温水浴加热到 $60^{\\circ}\\mathrm{C}$ 。加入引发剂开始反应，反应时间为3h。  \n\n表2-1-124有机硅改性丙烯酸酯乳液配方  \n\n\n<html><body><table><tr><td>组分名称</td><td>质量含量/%</td><td>组分名称</td><td>质量含量/%</td></tr><tr><td>去离子水</td><td>80</td><td>SDS</td><td>MMA/BA总用量的2</td></tr><tr><td>MMA/BA</td><td>20(MMA : BA=51 + 49)</td><td>Latemul S-180</td><td>MMA/BA总用量的4.5</td></tr><tr><td>MAA</td><td>MMA/BA 总用量的1</td><td>APS</td><td>去离子水的0.375</td></tr><tr><td>MPMS或VTES</td><td>MMA/BA 总用量的1.5</td><td>助乳化剂</td><td>MMA/BA总用量的2</td></tr><tr><td>羟基硅油</td><td>MMA/BA总用量的10～30</td><td></td><td></td></tr></table></body></html>  \n\n（5）有机氟改性丙烯酸乳液由于C—F键能大于Si—O与C—C键能，且氟原子有优异的物理化学特性，因此有机氟改性有助于提高乳液的综合性能。  \n\n有机氟改性乳液的合成工艺如下：采用过氧化物热分解引发体系及半连续方式加料。称取 $75g$ 去离子水，与乳化剂、丙烯酸类单体混合，强力揽拌使之乳化成预乳化液。将过硫酸铵溶人适量水中制成引发剂溶液，预留 $5g$ 引发剂溶液备用。在装有回流冷凝器、搅拌器和分压漏斗的四颈瓶中加入1/5的预乳化液，水浴加热至 $80^{\\circ}\\mathrm{C}$ ，然后加入 $8g$ 引发剂溶液，搅拌使之反应。待反应器中液体由白色变为蓝色说明聚合反应开始，此时开始滴加预乳化液和引发剂溶液。当预乳化液剩余1/3时将称取的有机氟单体混入预乳化液中，然后滴入反应器内，整个滴加时间控制在 $_{3\\sim4\\mathrm{h}}$ 。当全部预乳化液滴完后，一次性加人预留的引发剂溶液，并在原温度下保温反应1h，然后降温至 $40^{\\circ}\\mathsf{C}$ 以下，用氨水调节 $\\mathsf{p H}$ 至 $\\scriptstyle7\\sim8$ ，过滤出料。  \n\n乳液性能：从性能测试表明，氟单体甲基丙烯酸氟烷基酯的加入能显著影响乳液涂膜的吸水率，涂膜的吸水率随着氟含量的增加而逐渐降低，但随着氟单体用量的增加，吸水率会回升，因此需要选择一个合适的加入量。氟单体的加入量与吸水率有关外，还显著影响涂膜水接触角，未进行氟改性的纯丙乳胶膜接触角小于 $90^{\\circ}$ ，但氟改性以后的乳胶膜对水接触角大于$90^{\\circ}$ ，且随着氟单体的增加而增大，其原因是氟单体与丙烯酸类单体共聚，在聚合物主链上引入氟烷基侧链，氟烷基在乳液成膜过程中优先向外表面迁移，从而造成氟元素在表面的富集，大大降低了膜表面能，使水不能湿润涂膜。由此可见，氟改性能获得乳液较优异的憎水性能。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 297,
+        "chunk": "# 五、辐射固化丙烯酸酯涂料  \n\n辐射固化涂料［包括紫外光（UV）固化和电子束（EB）固化】从20世纪60年代问世，这种涂料品种由于符合现代环境保护的发展要求，因此十分受涂料界重视，应用时，以紫外光或电子束为能源对涂层中的活性成分激发而生成自由基，从而引发聚合。辐射固化涂料几乎无溶剂，减少了对大气污染、节省能源、固化速率快，特别适于不能受热的基材的涂装。辐射固化技术按辐射光源和溶剂类型可以分为紫外光固化技术、非紫外光固化技术、油性光固化技术、水性光固化技术，最常用的是紫外光固化。辐射固化技术产品中 $80\\%$ 以上是紫外线固化技术，其成品不仅有液态型，还有粉末型、水分散剂型等。辐射固化涂料的快速发展需要克服以下一些障碍。  \n\n$\\textcircled{1}$ 辐射固化过程大多系自由基聚合反应，反应易受氧气阻聚，所以最好在隔绝氧气的条件下进行。  \n\n$\\textcircled{2}$ 紫外光固化型涂料作为清漆效果较好，但色漆中因加有颜料，紫外光不易透入漆层，所以尚未能获得较满意的固化效果。  \n\n$\\textcircled{3}$ 电子束固化型涂料需要用低能大功率电子加速器来产生电子束，这种设备投入较高，同时生产应用过程中射线防护问题也是安全生产需要关注的。  \n\n1946年美国Inmont公司获得第一个紫外光固化油墨专利，1968年紫外光固化涂料首先由德国拜耳公司开发成功并推向市场。辐射固化型涂料虽然在科研单位已取得大量成果，但在实际应用上与溶剂型及水性涂料相比在产量上有非常巨大的差距。下面对辐射固化型涂料的特点进行介绍。",
+        "category": " Introduction"
+    },
+    {
+        "id": 298,
+        "chunk": "# 1.辐射固化丙烯酸酯涂料的特点  \n\n（1）辐射固化型涂料的优点  \n\n$\\Phi$ 节约能源，不需要高温烘烤，固化成膜所消耗的紫外光或电子束仅在瞬间，所以生产过程中只消耗极少的电力。不同的文献介绍的耗能效果有极大的差异，一般认为紫外固化的电耗约为烘干型漆的1/5，而电子束固化又比紫外光固化更低一倍左右。  \n\n$\\textcircled{2}$ 无溶剂或溶剂用量很低。此类涂料的主要成膜物为不挥发的丙烯酸酯类，其稀释剂为可参与交联聚合反应的活性烯属单体，一经辐射聚合，全部组成成分均转化为体型分子的固体漆膜，其有机挥发物仅为涂饰过程中极少量的活性稀释剂在聚合前的挥发，故可称为100%固体分的无溶剂漆，对空气的污染程度极低，无溶剂爆炸危险。  \n\n$\\textcircled{3}$ 固化速率快，一般是零点几秒到十秒，大大缩短操作工时；适于高速生产线，生产效率高。  \n\n$\\textcircled{4}$ 漆膜性能好，丰满度及光泽尤其突出，具有良好的抗摩擦、抗溶剂、抗污染性能。  \n\n$\\textcircled{5}$ 对热敏感的材料具有较好的施工性能。  \n\n(2）辐射固化型涂料的缺点  \n\n$\\textcircled{1}$ 电子束固化设备投资大。  \n$\\textcircled{2}$ 对几何形状复杂的构件固化困难。  \n$\\textcircled{3}$ 加有颜料的色漆应用紫外光固化工艺尚有一定的困难。",
+        "category": " Introduction"
+    },
+    {
+        "id": 299,
+        "chunk": "# 2.辐射固化型丙烯酸醋涂料的组成  \n\n辐射固化型丙烯酸酯涂料与其他类型的涂料相似，主要由预聚物、光引发剂、活性稀释剂（特定单体)、稳定剂和颜填料等组成。  \n\n(1）预聚物预聚物是主要成膜物质，在整个体系中占有相当大比重，对涂膜的性能起决定性的影响。这类树脂含有C一C不饱和双键并具有低分子量，主要有不饱和聚酯和丙烯酸化的或甲基丙烯酸化的树脂如环氧丙烯酸酯、聚氨酯丙烯酸酯、多烯硫醇体系、聚醚丙烯酸酯、丙烯酸化聚丙烯酸酯等。固化速度快是这类树脂的特点，并能应用于各种辐射固化涂料与油墨的调配，其缺点是固化膜脆性大、柔顺性差。此类树脂中亦可加或不加活性稀释剂参与成膜时的聚合反应。  \n\n(2）活性稀释剂亦称单体活性稀释剂在光固化涂料中有重要应用，上述树脂的黏度较大，需要活性稀释剂来调节黏度、改善施工性能。选用活性稀释剂时应该考虑：稀释剂的黏度、溶解性、稀释能力、挥发性、气味、毒性、对光引发剂的活性、官能度、均聚物和共聚物的玻璃化温度等。光固化涂料在聚合反应时，一般会产生总体积收缩，在使用某些活性稀释剂时会导致更严重的体积收缩，这种收缩严重影响固化膜对基材的附着力，这一点必须引起重视。活性稀释剂可分为单官能度活性稀释剂和多官能度活性稀释剂。单官能度活性稀释剂主要起稀释功能，例如丙烯酸丁酯、丙烯酸羟乙酯等；多官能度活性稀释剂主要包括二官能度、三官能度、四官能度和五官能度等。  \n\n活性稀释剂在反应前起着溶剂作用，在聚合后成为涂膜的组分，因此正确选择一种活性稀释剂就成为确保涂膜质量的一个重要因素。早期的产品中多采用多官能丙烯酸酯单体如三羟甲基丙烷三丙烯酸酯（TMPTA)、季戊四醇三丙烯酸酯（PETA）、新戊二醇二丙烯酸酯(NPGDA）等，此类产品由于活性官能团较多，所以固化反应快，稀释效果好，但交联密度大、膜层易脆裂、体积收缩大、附着力不好，而且多官能单体对皮肤有刺激等不良作用。较理想的多官能单体应具有以下各方面的特点：低黏度；高反应速率；多官能团；稀释率好；溶解性好；颜料润湿性好；成膜性好；表面张力低；色泽水白；低毒性；对皮肤及眼睛刺激性小；气味小；不易雾化；膜层性能（拉伸强度、耐磨损性、延展性、耐溶剂性、光泽）良好；挥发速度适宜，不宜太快以免固化前大量挥发。  \n\n最近研究发现，在体系中加入少量含氟稀释剂，聚合时将富集在涂膜表面，可以大大提高涂膜的疏水性、耐化学品性能和抗划伤性。  \n\n(3）光引发剂光引发剂是光固化涂料的重要组成部分，是决定涂料固化程度和固化速度的主要因素。引发剂能吸收紫外光，经过化学变化可以产生能引发聚合能力的活性中间体。一般光引发剂在涂料中的浓度较低，但光引发剂是辐射固化涂料的主要组分之一，对UV固化涂料的灵敏度起决定作用。光引发剂主要分为两类：自由基光引发剂和阳离子光引发剂。丙烯酸酯涂料体系中只能使用自由基光引发剂。在自由基光引发基中，主要有两种类型：单分子分解型光引发剂，引发剂受光激发后，引发剂分子发生分解，引发聚合反应；双分子反应型光引发剂，通过夺氢反应，形成自由基，引发聚合反应。  \n\n对光引发剂的要求：a.在辐射光源的光谱范围内，具有较高的吸光效率；b.具有较高的自由基量子效率；c.在树脂基体中具有良好的溶解性；d.具有长时间的保存性能，无色、放置过程中不变黄；e.引发剂本身或其光化学反应的产物不对固化后树脂材料产生不良影响；f.无气味、毒性低；g.尽可能价廉易得、成本低。  \n\n常用的光敏引发剂主要有以下几种。  \n\n$\\textcircled{1}$ 单分子分解型安息香及其醚类安息香类光引发剂是最早商业化的单分子分解型光引发剂，它生成苯甲酰自由基和苯甲醚自由基，这两种自由基都可以引发丙烯酸类单体聚合。  \n\n![](images/7d24595e199e4d523461a32b741520a1fbfddd82d8ff6e44dd79ba63656fc1ab.jpg)  \n\n由于苯甲醚碳上的氢原子比较活泼，因此早期的安息香醚引发剂稳定性较差；目前推出的是硫杂葱酮、安息香双甲醚等光引发剂，但安息香双甲醚会使涂料黄变。  \n\n$\\textcircled{2}$ a-酰酯类通过紫外光照射也能分解出两种自由基进行聚合引发。  \n\n![](images/afc4698563d94b6245a4e149329275d5a7805af1f3ea2a0e71e718981e134fa7.jpg)  \n\n$\\textcircled{3}$ 二苯甲酮衍生物二苯酮及其衍生物属于提氢型光引发剂，在光作用下，激发态的二苯酮可以从一个氢原子给予体上夺取氢原子，生成自由基引发聚合反应。  \n\n![](images/d1cfe6991e3f8eb88197851940feb0f17cb9f4279bd3745933cfd2232807f0ea.jpg)  \n\n$\\textcircled{4}$ 新型光引发剂一般光固化涂料是用紫外光源，但近年来已开发了利用可见光甚至近红外光的新型光引发剂，例如樟脑光引发剂，在 $470\\mathrm{nm}$ 有最大吸收，与氢原子给予体配合在蓝光下可以产生活泼自由基，引发聚合反应；氟化二苯基二茂铁和双 (无氟化苯基)二茂铁的吸收波长已延伸到 $520\\mathrm{nm}$ ，在可见光区内有较大的吸收，应用于引发丙烯酸酯的可见光聚合反应非常有效；又例如，利用高分子型光引发剂能避免未光解的光引发剂不在漆膜中残留、提高引发剂与树脂的相容性、不产生气味、提供无毒环境。水溶性光引发剂是努力发展的一类新引发剂，在普通引发剂基础上，引入铵盐或磺酸盐官能团，使其与水相溶，但目前水溶性光引发剂聚合反应效率不高，固化后涂膜耐水性不良，需要进一步加以改进。  \n\n（4）助剂为确保光固化涂料中各组分的相对稳定性，在光敏树脂合成过程中，需要加入相应的助剂，例如加入流平剂用于改善流动性；抗氧剂可用于改善涂膜稳定性能；热阻聚剂可以延长光敏树脂的有效期等。在使用助剂时，应选用能参加固化反应的活性助剂。不过由于大部分普通助剂不参与光固化反应而留在固化膜中，带来针孔、反黏等漆膜病。  \n\n光固化涂料的固化受到许多因素的影响，例如温度、湿度、活性增塑剂、亲水基团、中和剂、光强度、空气中氧等因素的影响。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 300,
+        "chunk": "# 3.辐射固化型丙烯酸酯涂料举例  \n\n光固化涂料用途广泛，可以应用于木器涂料、塑料涂料、金属涂料以及纸张涂料等。  \n\n（1）环氧丙烯酸酯环氧丙烯酸酯在UV固化涂料中是最为常见、应用最为广泛的预聚物，其配方见表2-1-125。  \n\n表2-1-125环氧丙烯酸醋配方  \n\n\n<html><body><table><tr><td>组分名称</td><td>质量份数</td><td>组分名称</td><td>质量份数</td></tr><tr><td>环氧树脂</td><td>100</td><td>三乙胺</td><td>0.2</td></tr><tr><td>丙烯酸</td><td>32</td><td>对苯二酚</td><td>少量</td></tr></table></body></html>  \n\n合成工艺：在带有搅拌、回流冷凝器和加热系统的反应釜中加入环氧树脂，缓慢升温到$100\\Upsilon$ ，以三乙胺为催化剂，缓慢滴加丙烯酸，并控制反应温度在 $120\\mathrm{\\textperthousand}$ 以下，滴加完毕以后，反应 $2\\mathord{\\sim}4\\mathrm{h}$ ，取样测定至酸值10以下，降温、出料、包装待用。  \n\n(2）紫外光固化纸张罩光涂料光固化纸张罩光涂料，具有高光泽度、高固化速度，不具有刺激性气味单体，特别适于彩色包装纸、课本、书刊封面的表面装饰等。紫外光固化纸张罩光涂料配方见表2-1-126。  \n\n表2-1-126紫外光固化纸张罩光涂料配方  \n\n\n<html><body><table><tr><td>组分名称</td><td>质量份数</td><td>组分名称</td><td>质量份数</td></tr><tr><td>环氧丙烯酸酯</td><td>30~45</td><td>丙烯酸氨基酶</td><td>5~10</td></tr><tr><td>丙烯酸羟乙醋</td><td>55~40</td><td>助剂（流平剂、消泡剂等）</td><td>0.1~1</td></tr><tr><td>二苯甲酮</td><td>2~5</td><td></td><td></td></tr></table></body></html>  \n\n制造工艺：将配方中的原料搅拌均匀、过滤即可。根据不同的上光剂，应选用合适的稀释剂来调节黏度；根据不同的光固化速度调节光引发剂的用量；根据涂层柔顺性的不同要求，调节各种稀释剂的比例。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 301,
+        "chunk": "# 4.光固化涂料未来的发展方向  \n\n水性光固化涂料是未来一个方向。由于光固化涂料组分中使用的活性稀释剂仍含有机挥发物，有不同程度的毒性和刺激性；在一些多孔性基材上稀释剂容易扩散到孔隙中而不能固化、使被涂物长期有异味，而且稀释剂会强烈影响固化膜的性质。紫外光固化水性涂料使用水稀释剂，从而避免反应性稀释剂的毒性和刺激性。因此可以添加水和增稠剂调节体系的流变性和黏度，从而使涂料不含挥发性有机物，不易燃，生产安全，涂布设备容易清洗，可以得到超薄固化膜。UV水性固化涂料还能有效地解决传统固化涂料的硬度和柔韧性这对矛盾。水性光固化材料的低聚物是高分子量的水性分散体，其黏度与高分子的分子量无关，只与固含量有关，因而在水性光固化材料中可以使用高分子量的低聚物，又不用低分子量的活性稀释剂，从而克服了高硬度和高柔韧性不能兼顾的矛盾。  \n\n紫外光固化粉末涂料也是一个重要发展方向。传统的热固化粉末涂料要求在 $180\\sim$ $200\\Upsilon$ 下固化 $15\\mathrm{\\sim}30\\mathrm{min}$ ，这就限制了它在热敏基材中的应用。目前正迅速发展的、熔点在$100{\\sim}120^{\\circ}\\mathrm{C}$ 的紫外光固化粉末涂层解决了这个问题。紫外光固化粉末涂料具有粉末涂料和光固化涂料的优点，不仅可以在金属上使用，也可以在塑料和木制品及其他对热敏感的部件上使用，大大扩大了粉末涂料的使用范围，而且在今后的发展中，辐射固化在汽车上使用潜力最大，应该是努力开发的一个方向。  \n\nUV固化纳米涂料是一种集紫外光固化绿色技术与新兴纳米技术为一体从而赋予涂料某种新性能或者对其某种性能有明显提高而得到的涂料。由于纳米材料的表面活性相当高，如何将其分散到涂料基体中，是纳米材料在涂料中应用的主要技术关键。对紫外光固化纳米复合涂层的制备更是如此，因为紫外光固化体系的黏度较高，因此在传统制备方法的基础上，通常配合物理分散、化学分散和电化学方法进行UV固化纳米复合涂层的制备。  \n\n随着新的UV固化体系研究的不断深入，纳米技术在涂料工业中的应用，以及UV固化涂料新产品的不断开发，UV固化涂料将广泛应用于传统涂料的各个领域，并将积极推动涂料工业的绿色化和环境友好化。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 302,
+        "chunk": "# 第七节环氧树脂与涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 303,
+        "chunk": "# 一、概况  \n\n由碳-碳-氧三原子组成的环称为环氧基团。此基团的英文名称较多：epoxy、epoxide、oxinane glycidyl group.  \n\n以上的glycidyl基称为缩水甘油基，在环氧树脂化学中常常出现：  \n\n![](images/3becabc147fb5a2fb985f7c22fd2af5c58207ff75ca22168e7361411d809beff.jpg)  \n\n以环氧树脂为主要成膜物质的涂料称为环氧树脂涂料。含有两个或两个以上环氧基团的树脂属于环氧树脂。环氧基团具有高度活泼性，使环氧树脂能与多种类型固化剂发生交联反应形成三维网状结构的高聚物。",
+        "category": " Introduction"
+    },
+    {
+        "id": 304,
+        "chunk": "# 1.树脂分类  \n\n环氧树脂可分为两大类。  \n\n（1）缩水甘油类大多用环氧氯丙烷与多元酚或多元醇反应而得。（2）非缩水甘油类用过醋酸等氧化剂与碳-碳双键反应而得。在环氧树脂中，缩水甘油衍生物有以下3类。  \n$\\textcircled{1}$ 缩水甘油醚（glycidylether）  \n\n![](images/40d02d9aa7d5de85abe47a835d6aee426606eeb96db1c672df7de2960e4f1d5a.jpg)  \n\n大多数主要的环氧树脂属于此类。  \n\n$\\textcircled{2}$ 缩水甘油酯（glycidylester）  \n\n![](images/a61e5f12bc6f0be64259195eda92ac033c090a3cd680401c5604070d874b5638.jpg)  \n\n最典型的代表是粉末涂料中的TGIC（异氰尿酸三缩水甘油酯，triglcidylisocyanurate）。  \n\n![](images/02d88cd3dff3e62172177a4a54f1826f96555a5c54f6d246dcaba10b2efb67ed.jpg)  \n\n$\\textcircled{3}$ 缩水甘油胺由多元胺与环氧氯丙烷反应而得，涂料中不常用。非缩水甘油类的环氧树脂是由氧化剂与环烯烃或聚丁二烯等碳-碳双键反应而得，例如：  \n\n![](images/bc56fd47f9b2b977d463a10c60de7247d08bd6628296a5e71c748983da24da05.jpg)  \n\n此类树脂产量颇少，近年来用于辐射固化的阳离子聚合涂料，性能良好。  \n\n在所有环氧树脂中，产量最大，最具代表性的是由二酚基丙烷（diphenylolpropane）习称双酚A（bisphenolA，缩写BPA）与环氧氯丙烷（epichlorohydrim缩写ECH）缩合而成的树脂。  \n\n![](images/6be7330d5780677e8a28927db5fd1e20c4ba4b267a82b90db89e380eb835dedc.jpg)  \n\n上示意式是代表最小分子量的二缩水甘油醚（BPADG)。工业生产按投料比不同，产得一系列分子量较大的树脂，其通式为：  \n\n![](images/34895a479dc1b2b4c5092e020ce53e668c933b749bbe8908d6f6d919a12f6396.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 305,
+        "chunk": "# 2.环氧树脂发展史  \n\n回顾发展史可以使我们了解环氧树脂的发展历程，与我国环氧树脂生产的关系，既便于读者了解，又足以启迪改进和创新。  \n\n1934年德国I.G.Farben公司的P.Schlack发现了双环氧化合物可以与胺反应，生成高分子量的胺。  \n\n1938年瑞士Gebr.deTrey公司的PierreCastan发现环氧化合物可以固化，生成低收缩率的塑料而取得瑞士专利，主要用作齿科材料。随后Ciba公司购得Gebr.deTrey公司技术而开发环氧树脂用于黏合剂、浇注灌封材料等。  \n\n同时，美国的Devoe $8.$ Raynolds公司的SylvanO.Greenlee等致力于开发新型多元醇，以制备高性能涂料。在美国壳牌Shell公司提供环氧氯丙烷合作下，也制成了环氧树脂。在1948年美国Shell公司生产的环氧树脂，按不同分子量，主要有下列一些品种：Epon828（在欧洲商品名为Epikote）； $\\mathtt{E p o n834}$ ；Epon 1001；Epon 1004；Epon 1007；Epon 1009。  \n\nCiba 公司生产的牌号为Araldite，其后美国陶氏Dow化学公司也生产环氧树脂，称为  \n\nDER (Dow Epoxy Resin)。  \n\n以上三家公司是当年全球最大的环氧树脂制造企业。现今除Dow公司继续生产外，壳牌公司的环氧树脂转由Hexion公司生产，商品名保持Epon，Epikote。Ciba公司的环氧树脂转由美国Huntsman公司生产，商品名Araldite树脂及Aradur固化剂。现Huntsman的环氧部分也售给Hexion。随着近年来科技发展，环氧树脂的用途除涂料外，大量应用于电子工业包封、层压板、黏合剂等，我国已成为全球消耗环氧树脂最大的市场。中国台湾的南亚公司是生产环氧树脂的全球大企业。无锡树脂厂、岳阳石化厂环氧树脂厂、上海树脂厂等和张家港Dow公司、广州宏昌公司都生产环氧树脂。后者是引进日本东都公司技术，其液体环氧树脂牌号尾数与Epon相近：  \n\n<html><body><table><tr><td>宏昌</td><td>GELR</td><td>128</td><td>壳牌</td><td>Epon</td><td>828</td></tr><tr><td></td><td>GELR</td><td>134</td><td></td><td>Epon</td><td>834</td></tr></table></body></html>  \n\n环氧树脂发展至今已历时60年，产量不断增加，质量不断提高，新品种不断涌现，涂料工业所用的环氧树脂约占其总产量近一半，制得众多的高性能涂料，例如全世界每年生产几千万辆汽车，汽车的阴极电沉积底漆主要用环氧树脂制成，粉末涂料不论是纯环氧、或环氧/聚酯，或TGIC系均耗用大量环氧树脂，食品罐及软饮料罐内壁涂料、船舶及重防腐蚀涂料、工业地坪涂料、绝缘漆等均以环氧树脂为主要成分。  \n\n其中环氧树脂的品种构成是：  \n\n双酚A环氧树脂 81.76% 脂肪族环氧树脂 1.10%澳化环氧树脂 12.15% 其他 2.20%酚醛环氧树脂 2.76%",
+        "category": " Introduction"
+    },
+    {
+        "id": 306,
+        "chunk": "# 3.环氧树脂漆的性能  \n\n环氧树脂本身是热塑性的半制品，是环氧树脂漆的原料，要使环氧树脂漆具有优良性能，必须将环氧树脂与固化剂或脂肪酸进行反应，交联而成为网状结构的大分子。环氧树脂漆种类很多，也各有特点，下面概括介绍环氧树脂漆的优点。  \n\n$\\Phi$ 漆膜对金属（钢、铝等）、陶瓷、玻璃、混凝土、木材等极性底材，均有优良的附着力。因为环氧树脂漆有许多羟基及醚键，能与底材吸引。而且环氧固化时体积收缩率低（仅$2\\%$ 左右)，不像不饱和聚酯在固化时体积收缩率高达 $11\\%$ ，产生内应力而损及附着力。W.J.Bailey等研究发现环氧树脂固化时收缩率低的理由：通常含双键单体未聚合时的间距较长（如苯乙烯单体之间)，一旦聚合，生成共价键，间距缩短，体积收缩，所以不饱和聚酯的收缩率高。但是开环聚合则不同，因为聚合的原子间原先已由共价键连接，所以聚合后体积变化不大。  \n\n$\\textcircled{2}$ 抗化学品性能优良，因树脂中仅有烃基及醚键，没有酯键，所以耐碱性尤其突出。一般的油脂系或醇酸防锈底漆，在金属腐蚀时阴极部位呈碱性，会被皂化破坏。环氧树脂漆耐碱而且附着力好，故大量用作防腐蚀底漆，例如汽车的阴极电沉积底漆等。又因环氧树脂漆固化后呈三维网状结构，又能耐油类等浸渍，大量应用于油槽、油轮、飞机的整体油箱内壁衬里等。  \n\n$\\textcircled{3}$ 与热固性酚醛树脂涂料相比较，环氧树脂漆含芳环而坚硬，但有醚键便于分子链的旋转，具有一定的韧性，不像酚醛树脂很脆（因其交联间距比环氧树脂短)。环氧树脂交联间距长，便于内旋转。  \n\n酚醛 环氧  \n\n![](images/051632f00c453568213810013c20eae942a4d6ba3f2edf700de7250ec7ca8425.jpg)  \n\n![](images/21854f645ec155897f5df4855dfb9f0b9a023bbf1b0b6697d3347b5c467fec55.jpg)  \n\n上述结构示意图是以最小的环氧树脂为例，若用分子量较高的环氧树脂，则交联点间距更长。  \n\n$\\textcircled{4}$ 环氧树脂对湿面有一定的润湿力。  \n\n![](images/708d582b9fc85e9d56bcf4d4c0877dc944dc0e0c7024e02e22cf65f60932bb81.jpg)  \n\n尤其在使用聚酰胺树脂作固化剂时，可制成水下施工涂料，能排挤物面的水而涂布，用于水下结构的抢修和水下结构的防腐蚀施工。  \n\n$\\textcircled{5}$ 环氧树脂本身的分子量不高，能与各种固化剂配合制造无溶剂、高固体、粉末涂料及水性涂料，符合近年的环保要求，并能获得厚膜涂层。  \n\n$\\textcircled{6}$ 环氧树脂含有环氧基及羟基两种活泼基团，能与多元胺、聚酰胺树脂、酚醛树脂、氨基树脂、多异氰酸酯等配合，制成许多种涂料，既可常温干燥，也可高温烘烤，以满足不同的施工要求。  \n\n$\\textcircled{7}$ 环氧树脂具有优良的电绝缘性质，用于浇注密封、浸溃漆等。  \n\n环氧树脂漆具有很多优点，但也存在不足之处。  \n\n$\\Phi$ 光老化性差环氧树脂中含有芳香醚键，漆膜经日光（紫外线）照射后易降解断链， 所以户外耐候性较差。  \n\n![](images/73728397f82201aed0959726d5806b189dc08741adc34dcde34871327e9d80cb.jpg)  \n\n所以通常的双酚A系及双酚F系环氧树脂不耐户外日晒，漆膜易失去光泽，然后粉化，不宜用作户外的面漆。  \n\n以上所述是指双酚A或双酚F缩水甘油醚环氧树脂，若是缩水甘油酯环氧树脂（例如TGIC）则户外耐久性极为优良。  \n\n$\\textcircled{2}$ 低温固化性差环氧树脂一般需在 $10\\%$ 以上固化，在 $10^{\\circ}\\mathrm{C}$ 以下则反应缓慢而困难，对于大型物体如船舶、桥梁、港湾、油槽等寒季施工实为不便。虽可加些促进剂，或用多异氰酸酯作固化剂，但毕竟是弱点。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 307,
+        "chunk": "# 4.环氧树脂的反应  \n\n环氧树脂含有环氧基及仲羟基，能进行许多反应。环氧基是三元环，环的键角约为${60}^{\\circ}$ ，比通常的四面体碳的109.5°键角，或开链醚的二价氧的 $110^{\\circ}\\Cplus$ 角小得多，按AdolfvonBaeyer 的张力理论是不稳定的，会发生开环反应。它的氧原子的电负性高，使碳原子呈正  \n\n电性，易受亲核试剂进攻。  \n\n![](images/134a44c1aa8d5d9b0de2245644d48214da60edcc789f97c06f5e5b399dfecbfa.jpg)  \n\n(1）环氧基与伯胺反应  \n\n(2）环氧基与仲胺反应  \n\n以上的环氧基与胺的加成反应是二级亲核反应 $\\mathrm{\\sfs}_{\\mathrm{\\scriptscriptstyleN}2}$ ，是环氧涂料中最重要的反应。伯胺的反应速率比仲胺快，脂肪胺的反应速率比芳香胺快，且受催化剂和溶剂的影响。需指出的是胺的每一个氢原子与一个环氧基反应。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 308,
+        "chunk": "# （3）环氧基与羧酸反应  \n\n$$\n\\underset{0}{\\longrightarrow}\\underset{0}{\\mathrm{CH\\_CH}}_{\\tau}+\\underset{0\\mathrm{H}}{\\mathrm{RCOOH}}\\longrightarrow\\underset{0\\mathrm{H}}{\\longrightarrow}\\underset{0\\mathrm{H}}{\\longrightarrow}\\underset{\\mathrm{CH}}{\\mathrm{CH\\_CH}}\\longrightarrow\\underset{\\mathrm{C\\_R}}{\\overset{0}{\\longrightarrow}}\n$$  \n\n此反应在“混合型”粉末涂料中广泛应用，产量占粉末涂料之冠。配方中往往含有少量碱性的咪唑，以催化羧基与环氧基反应。  \n\n(碱)  \n\n$$\n{\\bf B}+{\\bf R C O O H}\\Longleftarrow\\bf B H^{+}+{\\bf R C O O^{-}}\n$$  \n\nRCOO-是强亲核试剂  \n\n此类碱B催化剂，典型的如2-苯基咪唑  \n\n![](images/5e8e72bc1952e4f0906f9a96ef7f67e19f42f3be6e90f62a5cf6d2516b9c37bd.jpg)  \n\n类似促进羧基与环氧基反应的催化剂，还常用二甲基苄胺。  \n\n(4）环氧基与羟基反应常温下环氧基与羟基反应极慢。在制造多元醇缩水甘油醚时，环氧氯丙烷与多元醇以路易斯酸如三氟化硼乙醚配合物催化开环，然后再以 $\\mathrm{\\DeltaNaOH}$ 闭环，制得活性稀释剂。  \n\n(5）环氧基与碱及叔胺环氧基与碱或叔胺，在加温下会自行缩聚成醚，并胶结。  \n\n笔者在1956年在实验室试制601环氧树脂时，最后洗涤除盐时，未将碱洗净，待升温脱水时，树脂胶结。  \n\n(6）环氧树脂与酚羟基反应  \n\n此反应在制造管道粉末涂料及以扩链工艺制造高分子量环氧树脂中很普遍。  \n\n(7）环氧基与硫基反应  \n\n反应时常加DMP-30催化。  \n\n(8）环氧基与无机酸反应  \n\n此反应可用以测定环氧基的含量，亦可用作聚氯乙烯的稳定剂，以吸除氯化氢阻缓聚氯乙烯降解。  \n\n（9）环氧基与异氰酸酯反应，生成唑烷酮  \n\n此反应用以制备耐高温产品。  \n\n(10）环氧树脂的仲羟基与酚醛树脂、氨基树脂的羟甲基或烷氧基高温固化，制造烤漆。  \n\n（11）仲羟基与异氰酸酯反应生成氨酯  \n\n(12）仲羟基与硅醇（silanol）或其烷氧基缩合  \n\n（13）仲羟基与脂肪酸反应，制造环氧酯  \n\n$$\nH C=O H+R C O O H=H C-O-C-R+H_{2}O\\uparrow\n$$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 309,
+        "chunk": "# 二、环氧树脂的特性指标和牌号  \n\n环氧树脂有多种型号，各具有不同性能，其特性指标表征各自性质。",
+        "category": " Introduction"
+    },
+    {
+        "id": 310,
+        "chunk": "# 1.环氧树脂的特性指标  \n\n（1）环氧基的指标这是环氧树脂最重要的特性指标，表征树脂分子中环氧基的含量，曾有多种表达方式：  \n\n$\\textcircled{1}$ 环氧值A（epoxy value)；  \n$\\textcircled{2}$ 环氧指数B（epoxyindex)；  \n$\\textcircled{3}$ 环氧当量 $c$ (epoxy equivalent);  \n$\\textcircled{4}$ 环氧基质量百分率 $D$ 中  \n$\\textcircled{5}$ 环氧基中的氧的质量百分率 $E_{\\circ}$   \n以上④两种方式前苏联曾有采用，现较为少用。  \n\n$\\textcircled{1}$ 是早期采用的方式，可参见本文的环氧树脂发展史一节，可见早期Shell公司的产品均以此方式表示，称之为环氧值，是指 $100\\mathbf{g}$ 环氧树脂中含有的环氧基摩尔数。我国自1958年以来采用此方式，沿用迄今。现Shell公司所产环氧树脂则已兼用环氧当量表示，偶尔也用mmol/kg表示。现Shell公司的环氧树脂已改由Hexion公司生产。  \n\n$\\textcircled{2}$ 环氧指数是Ciba公司所采用，表示每 $1\\mathbf{k}\\mathbf{g}$ 环氧树脂中所含环氧基的摩尔数。相比之下，现今国际上均采用国际计量系统（SI单位，我国称之为法定计量单位)，应采用 $\\mathbf{k}\\mathbf{g}$ mol的计量单位，则环氧指数应比环氧值更合适，环氧指数的数值比环氧值大10倍。  \n\n$\\textcircled{3}$ 环氧当量是指含有1mol环氧基的树脂的质量。确切些的名称常称为“环氧当量重量”（E.E.W.epoxy equivalentweight），更确切者称之为环氧当量质量（epoxy equivalentmass）现今许多公司常以环氧当量采用最广泛。Hexion公司、Dow 公司、Huntsman公司以及日本东都公司的环氧树脂产品均以此表示之。  \n\n下面为3种表示方式的相互换算公式：  \n\n环氧当量=环氧指数 即 $C{=}\\frac{1000}{B}$ 环氧当量 $=\\frac{100}{\\mathfrak{F}\\sharp\\mathfrak{A}(1\\sharp\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm{f\\mathrm{f}\\mathrm{f}\\mathrm{f}\\mathrm\\mathrm{f}\\mathrm{f}\\mathrm{f\\mathrm{f}\\mathrm\\mathrm{f}\\mathrm{f}\\mathrm\\mathrm{f\\mathrm{f}\\mathrm\\mathrm{f}\\mathrm\\mathrm{f\\mathrm{f}\\mathrm\\mathrm{f}\\mathrm\\mathrm{f\\mathrm\\mathrm{f}\\mathrm\\mathrm{f\\mathrm\\mathrm{f}\\mathrm\\mathrm\\mathrm{f\\mathrm\\mathrm{f}\\mathrm\\mathrm\\mathrm{f\\mathrm\\mathrm\\mathrm{f\\mathrm\\mathrm\\mathrm{f\\mathrm\\mathrm\\mathrm\\mathrm{f}\\mathrm\\mathrm\\mathrm{f\\mathrm\\mathrm\\mathrm\\mathrm{f\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm{f\\mathrm\\mathrm\\mathrm\\\\mathrm\\mathrm{f\\mathrm\\mathrm\\mathrm\\\\\\mathrm\\mathrm{f\\mathrm\\mathrm\\mathrm\\mathrm\\\\\\\\mathrm\\\\\\mathrm\\\\\\mathrm\\\\mathrm\\\\\\}}{f\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm{f\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm{f\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm{f\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\mathrm\\$ 即 $C{=}\\frac{100}{A}$  \n\n(2）羟基含量双酚A系环氧树脂的分子量愈大，则其羟基含量愈高，能与酚醛树脂、氨基树脂或多异氰酸酯交联，其羟基含量的表达方式也有3种：  \n\n$\\Phi$ 原先Shell公司的羟基值 $F$ C $100{\\bf g}$ 树脂所含羟基摩尔数）；  \n$\\textcircled{2}$ 原Ciba公司的羟基值 $G$ （每 ${\\bf k}_{\\mathrm{E}}$ 树脂所含羟基摩尔数)；  \n$\\textcircled{3}$ 羟基当量 $H$ 是指含有1mol羟基的树脂的克数。  \n三者的换算可参见前面环氧当量、环氧值的换算。  \n\n(3）酯化当量此是制造环氧酯时实用的数值，是指酯化1mol单羧酸（ $60g$ 醋酸或$280\\phantom{18}\\mathrm{{gC}_{18}}$ 脂肪酸）所需环氧树脂的克数。  \n\n环氧树脂中羟基和环氧基都能与羧酸进行酯化反应。酯化当量可表示树脂中羟基和环氧基的总含量。酯化当量应由化学分析测定，一般通过羟基值和环氧值可计算出近似值：  \n\n从上式中可见，在酯化反应时一个环氧基相当于2个羟基。  \n\n（4）软化点在规定的条件下，测得树脂的软化温度。  \n\n环氧树脂的软化点可以表示树脂的分子量大小，软化点高的分子量大，软化点低的分子量小。环氧树脂可按软化点不同分为：  \n\n低分子量环氧树脂 软化点<50℃ 聚合度<2   \n中分子量环氧树脂 软化点50\\~95℃ 聚合度2\\~5   \n高分子量环氧树脂 软化点 $>$ 100C 聚合度>5  \n\n在环氧树脂制造过程中可控制软化点，使产品质量一致，使用单位也可以参照软化点来控制黏度。软化点和分子量之间关系见图2-1-24。  \n\n![](images/e735fc024a7a06d5bb4ab606520d7871189ef6d43ecc142476906396d8c550ce.jpg)  \n图2-1-24环氧树脂软化点与分子量的关系  \n\n(5）氯值环氧树脂中所含氯的摩尔数（包括有机氯及无机氯)，称为氯值。有机氯来自制造环氧树脂时未充分闭环而残留者，称为易水解氧。  \n\n$$\n\\begin{array}{r l r}{\\underset{\\mathrm{OH}}{\\longrightarrow}}&{\\underset{\\mathrm{CH}}{\\longrightarrow}}&{\\underset{\\mathrm{CH}}{\\longrightarrow}}\\end{array}\\begin{array}{r}{\\longrightarrow}&{\\longrightarrow}\\\\ {\\underset{\\mathrm{OH}}{\\longrightarrow}}&{\\underset{\\mathrm{NaOH}}{\\longrightarrow}}\\end{array}\\begin{array}{r}{0}\\longrightarrow\\mathrm{CH}_{2}-\\mathrm{CH}-\\mathrm{CH}_{2}\\ +\\mathrm{NaCl}+\\mathrm{H}_{2}\\mathrm{O}}\\\\ &{}&{\\underset{\\mathrm{O}}{\\longrightarrow}}\\end{array}\n$$  \n\n无机氯来自制造环氧树脂时未洗涤充分而残留的氯化钠。两者均有损于固化物的电性能，也不利于耐腐蚀性。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 311,
+        "chunk": "# 2.国产环氧树脂的牌号及规格  \n\n表2-1-127为国产环氧树脂的牌号及规格，表2-1-128为烯烃类环氧化物的牌号及规格。  \n\n表2-1-127 国产环氧树脂的牌号及规格  \n\n\n<html><body><table><tr><td rowspan=\"2\">旧牌号</td><td rowspan=\"2\">国家统一型号</td><td colspan=\"5\">规 格</td></tr><tr><td>软化点/C （或黏度/Pa·s)</td><td>环氧值 /(eq/100g)</td><td>有机氟 /(mol/100g)</td><td>无机氮 /(mol/100g)</td><td>挥发分 /%</td></tr><tr><td colspan=\"6\">双酚A</td></tr><tr><td>616</td><td>E-55</td><td>(6~8)</td><td>0.55~0.56</td><td>≤0.02</td><td>≤0.001</td><td>≤2</td></tr><tr><td>618</td><td>E-51</td><td>(<2.5)</td><td>0.48~0.54</td><td>≤0.02</td><td>≤0.001</td><td>≤2</td></tr><tr><td>619</td><td></td><td>液体</td><td>0.48</td><td>≤0.02</td><td>≤0.005</td><td>≤2.5</td></tr><tr><td>6101</td><td>E-44</td><td>12~20</td><td>0.41~0.47</td><td>≤0.02</td><td>≤0.001</td><td>≤1</td></tr><tr><td>634</td><td>E-42</td><td>21~27</td><td>0.38~0.45</td><td>≤0.02</td><td>≤0.001</td><td>≤</td></tr><tr><td></td><td>E-39-D</td><td>24~28</td><td>0.38~0.41</td><td>≤0.01</td><td>≤0.001</td><td>≤0.5</td></tr><tr><td>637</td><td>E-35</td><td>20~35</td><td>0.30~0.40</td><td>≤0.02</td><td>≤0.005</td><td>≤1</td></tr><tr><td>638</td><td>E-31</td><td>40~55</td><td>0.23~0.38</td><td>≤0.02</td><td>≤0.005</td><td>≤1</td></tr><tr><td>601</td><td>E-20</td><td>64~76</td><td>0.18~0.22</td><td>≤0.02</td><td>≤0.001</td><td>≤1</td></tr><tr><td>603</td><td>E-14</td><td>78~85</td><td>0.10~0.18</td><td>≤0.02</td><td>≤0.005</td><td>≤1</td></tr><tr><td>604</td><td>E-12</td><td>85~95</td><td>0.09~0.14</td><td>≤0.02</td><td>≤0.001</td><td>≤1</td></tr><tr><td>607</td><td>E-06</td><td>110~135</td><td>0.04~0.07</td><td></td><td></td><td></td></tr><tr><td>609</td><td>E-03</td><td>135~155</td><td>0.02~0.045</td><td></td><td></td><td></td></tr></table></body></html>  \n\n续表  \n\n<html><body><table><tr><td rowspan=\"2\">旧牌号</td><td rowspan=\"2\">国家统一型号</td><td colspan=\"5\">规 格</td></tr><tr><td>软化点/C （或黏度/Pa·s)</td><td>环氧值 /(eq/100g)</td><td>有机氯 /(mol/100g)</td><td>无机氯 /(mol/100g)</td><td>挥发分 /%</td></tr><tr><td colspan=\"7\">Novolac环氧</td></tr><tr><td></td><td>F-51</td><td>(≤2.5)</td><td>0.48~0.54</td><td>≤0.02</td><td>≤0.001</td><td>≤2</td></tr><tr><td>648</td><td>F-46</td><td>≤70</td><td>0.44~0.48</td><td>≤0.08</td><td>≤0.005</td><td>≤2</td></tr><tr><td>644</td><td>F-44</td><td>≤40</td><td>≤0.44</td><td>≤0.1</td><td>≤0.005</td><td>≤2</td></tr><tr><td colspan=\"7\">TGIC</td></tr><tr><td>695</td><td>A-95</td><td>90~95</td><td>0.90~0.95</td><td></td><td></td><td></td></tr><tr><td colspan=\"7\">丙三醇环氧</td></tr><tr><td>662</td><td>B-63</td><td>（≤0.3）</td><td>0.55~0.71</td><td></td><td>≤0.005</td><td></td></tr></table></body></html>  \n\n表2-1-128烯烃类环氧化物的牌号及规格  \n\n\n<html><body><table><tr><td rowspan=\"2\">国家</td><td rowspan=\"2\">旧称</td><td colspan=\"7\"></td></tr><tr><td>外观</td><td>环</td><td>相对</td><td></td><td>新度（20℃</td><td>点</td><td>折射十</td></tr><tr><td>H-71</td><td>6201</td><td>淡黄色液体</td><td>0.62~0.67</td><td>1. 121</td><td>三</td><td><2000</td><td>185(400Pa)</td><td>一</td></tr><tr><td>R-122</td><td>6207</td><td>白色结晶</td><td>1.22</td><td>1.331</td><td>184</td><td>一</td><td>一</td><td>一</td></tr><tr><td>W-95</td><td>6300</td><td>白色固体</td><td>≥0.95</td><td>1.153</td><td>55</td><td>一</td><td>一</td><td>一</td></tr><tr><td>W-95</td><td>6400</td><td>琥珀色液体</td><td>≥0.95</td><td>1.153</td><td>一</td><td></td><td>二</td><td>一</td></tr><tr><td>YJ-118</td><td>6269</td><td>液体</td><td>1.16~1.19</td><td>1.0326</td><td>一</td><td>8.4</td><td>242</td><td>1.4682</td></tr><tr><td>Y-132</td><td>6206</td><td>液体</td><td>1.29~1.35</td><td>1.0986</td><td></td><td>7.7</td><td>227</td><td>1.4787</td></tr><tr><td>D-17</td><td>62000</td><td>琥珀色黏性液体</td><td>0.162~0.186</td><td>0.9012</td><td>一</td><td>碘值180</td><td>一</td><td>基</td></tr></table></body></html>\n\n①H—3,4-环氧基-6-甲基环已甲酸。R一二氧化双环戊二烯。W-二氧化双环戊二烯醚。YJ—二甲基代二氧化乙烯基环己烯；Y—二氧化乙烯基环已烯。D—聚丁二烯环氧树脂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 312,
+        "chunk": "# 三、环氧树脂的制造",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 313,
+        "chunk": "# 1.双酚A及环氧氯丙烷  \n\n双酚A环氧树脂的基础原料，来源于石油化工的丙烯，丙烯可合成环氧氯丙烷。  \n\nH CHCI—CH—CH 0  \n\n丙烯与苯化合而得异丙苯，异丙苯经氧化而得异丙苯过氧化氢，由此而得苯酚和丙酮：  \n\n![](images/1bfafdbddb3febf1bc44eff83147720c50296ef7d26f611a17f9d425c5bfeceb.jpg)  \n\n苯酚和丙酮缩合而得二酚基丙烷，习惯称为双酚A。其A字来源于丙酮（Acetone）的A。  \n\n![](images/5c03fb8bbeb2850cbe664d42721504f39f12d3350c8edce27f719c5c6ec59c73.jpg)  \n\n因此国际上大规模生产环氧树脂的企业很多来自石油化工业，例如Shell公司和Dow公司。它们不仅出售许多牌号的环氧树脂，也出售环氧氯丙烷和双酚A。下面介绍 Shell公司生产的环氧氯丙烷的规格。  \n\n<html><body><table><tr><td>纯度</td><td>至少99%</td><td>水分</td><td>最大0.10%</td></tr><tr><td>d</td><td>1. 181~1. 184</td><td>蒸馏范围</td><td>113. 0~118. 0°C</td></tr><tr><td></td><td>1. 1762~1. 1792</td><td>（纯品沸点</td><td>116. 2°C)</td></tr><tr><td>颜色（Pt-Co）</td><td colspan=\"3\">最大15</td></tr></table></body></html>  \n\n制造环氧氯丙烷，除了以丙烯为原料外，也可用甘油为原料，现法国Solvay公司，与Diester公司合作，后者用菜籽油制造生物柴油，有副产品甘油。Solvay公司将甘油与HCI反应，制得二氯丙醇，再与 $\\mathsf{N a O H}$ 反应，制得环氧氯丙烷。该公司在法国Tavaux生产基地建设1万吨/年环氧氯丙烷装置，定于2007年上半年投产，称之为Epicerol工艺，（来源自Epichloro hydrin 和Glycerol)。陶氏公司是全球最大的环氧树脂生产企业，在我国江苏省张家港设有工厂。陶氏公司在该地将首次使用陶氏专有的甘油转环氧氯丙烷技术，规模为15万吨/年，预计于 $2009\\sim2010$ 年间投产。  \n\n$$\n\\begin{array}{l c c l l}{{\\mathrm{CH}_{2}\\mathrm{OH}}}&{{}}&{{\\mathrm{CH}_{2}\\mathrm{C1}}}&{{}}&{{\\mathrm{CH}_{1}}}\\\\ {{\\downarrow}}&{{\\downarrow\\mathrm{CH}}}&{{}}&{{\\downarrow\\mathrm{HCH}}}&{{}}\\\\ {{\\mathrm{CHOH}}}&{{\\xrightarrow{\\mathrm{HCl.}}}}&{{\\begin{array}{l l l l}{{\\mathrm{CHOH}}}&{{\\xrightarrow{\\mathrm{NaOH}}}}&{{}}&{{\\mathrm{CH}}}\\end{array}}{\\mathrm{O}}}\\\\ {{\\downarrow}}&{{}}&{{\\downarrow\\mathrm{H}_{1}\\mathrm{Cl}}}&{{}}&{{\\mathrm{CH}_{1}\\mathrm{Cl}}}\\end{array}\n$$  \n\n商品的双酚A有两种等级：  \n\n$\\Phi$ 树脂级纯度稍低，供制环氧树脂用；   \n$\\textcircled{2}$ 聚碳级纯度高，供制造聚碳酸酯塑料用。  \n\n双酚A是白色片状物，分子量为228，沸点220℃（533.3Pa)，冻点156.5℃，d为1.195，每 $100\\mathbf{g}$ 水中 $25\\%$ ）溶解0.1g以下。兹举若干商品规格如下。  \n\n树脂级双酚A：  \n\nDow公司 Rhodia 公司冻点 最低154.0°℃ 155.5°C游离酚 最高0.15% ≤600mg/L(600ppm)铁 最高0.8mg/L(0. 8ppm） 2mg/L(2ppm)颜色APHA 最高100（50%溶液） 50(50%溶液）  \n\n<html><body><table><tr><td></td><td>三井东压</td><td>联合碳化 物公司</td><td>Rhodia 公司</td><td>Dow公司 （Parabis级）</td></tr><tr><td>冻点/℃</td><td>156.7</td><td>156.5</td><td>156.5</td><td>156.5</td></tr><tr><td>游离酚/（mg/L)</td><td>≤10</td><td>56</td><td>≤200</td><td>最高0.02%</td></tr><tr><td>铁/(mg/L)</td><td>0.3</td><td>0.3</td><td>1</td><td>最高0.5</td></tr><tr><td>色泽</td><td>7</td><td>35</td><td>40</td><td>最高20</td></tr><tr><td>浸碱色泽</td><td></td><td></td><td></td><td>最高50</td></tr><tr><td>三荤酚（trisphenol）含量/%</td><td></td><td></td><td></td><td>最高0.2</td></tr><tr><td>邻、对(o.p)异构体含量/%</td><td></td><td></td><td></td><td>最高0.25</td></tr></table></body></html>  \n\n双酚A和环氧氯丙烷都是二官能度化合物，所以合成所得的树脂是线型结构，聚合度一般在 $0\\sim14$ 。由于分子量、分子量分布以及化学结构的不同，故其生产方法也有差别。  \n\n环氧树脂是由双酚A、过量的环氧氯丙烷及 $\\mathbf{NaOH}$ 反应而成。因为双酚A和环氧氯丙烷均为二官能度，为使其分子两端均成环氧基，所以环氧氯丙烷必须过量，反应式示意如下：  \n\n![](images/a0785ecb78ef6c1502b049092b6fbb0ff638e1a2a7bd8e5c512d59d611e76b90.jpg)  \n（双缩水甘油醚）  \n\n依此进一步反应，最后的树脂通式为：  \n\n![](images/b9cd129b35be04b40ec13973897077e7ca61b103682faeb091ede733be11e2b5.jpg)  \n\n上式中 $\\scriptstyle n$ 平均值的大小取决于投料时环氧氯丙烷Epichlorohydrin（ECH）与双酚ABisphenolA（BPA）的比例，比例大则 $\\scriptstyle n$ 值小。按上列化学结构式，则结合在树脂分子中的比例为BPA=π+1° 3  \n\n从上面反应式可见，双酚A不是直接与环氧氯丙烷反应，而是先与碱生成苯氧基离子。与环氧基的反应是亲核的 $\\mathbf{S}_{\\mathrm{N}}2$ 反应，苯氧基离子是更强的亲核试剂，易进攻环氧基上的位阻较小的碳原子（a)： 54  \n\n但也有极少量进攻在仲碳原子（β）上：  \n\n![](images/cfba79e2b0bd6ee6cf13d60eb2ec36cbc73e46facdab09e6f360dd331bbdde85.jpg)  \n\n如此生成了不能闭环的含有机氯的端基，降低了环氧树脂的官能度，并有损电性能，  \n\n![](images/4522df1c240eab3e238caaf25c1dc2c5ff1998275c1ce98291302dab6a7f686b.jpg)  \n\n此外，在制造操作过程中往往有少量的环氧基水解破坏而生成二元醇（约 $2\\%$ ，也降低环氧树脂的官能度（理论上应该 $\\scriptstyle f=2$ ，实际工业产品 $\\scriptstyle f=1,9$ 左右)。  \n\n![](images/40f4bb48e90b5157df9ebab28a7bd437833f966e72cfa4968b98ce8c2701e2ec.jpg)  \n\n下面介绍不同牌号环氧树脂的 $n$ 值及其相应的环氧当量值和软化点。  \n\n<html><body><table><tr><td>树脂</td><td>n值</td><td>环氧当量</td><td>软化点/C</td></tr><tr><td>Epon828或DER331</td><td>0.13</td><td>190</td><td>液态</td></tr><tr><td>Epon1001</td><td>2</td><td>500</td><td>65~75</td></tr><tr><td>Epon1004</td><td>5.5</td><td>950</td><td>95~105</td></tr><tr><td>Epon1007</td><td>14.4</td><td>2250</td><td>125~135</td></tr><tr><td>Epon1009</td><td>16</td><td>3250</td><td>145~155</td></tr></table></body></html>  \n\n以上的n值是树脂的平均值，实际上树脂是不同分子量聚合物的混合物。以下为Dow公司的3种液态树脂经高效液相色谱分析的数据。  \n\n<html><body><table><tr><td></td><td>DER332</td><td>DER330</td><td>DER331</td></tr><tr><td>平均分子量</td><td>345</td><td>363</td><td>366</td></tr><tr><td>环氧当量</td><td>172</td><td>176</td><td>182</td></tr><tr><td>黏度（25C）/mPa·s</td><td>6500</td><td>9023</td><td>11560</td></tr><tr><td>=0类树脂</td><td>98~99</td><td>92~93</td><td>92</td></tr><tr><td>n=1类树脂</td><td>0.76</td><td>6.2</td><td>6.6</td></tr><tr><td>=2类树脂</td><td>0.03</td><td>0.35</td><td>0.42</td></tr></table></body></html>  \n\n$\\textcircled{1}$ 液体双酚A型环氧树脂制造液体环氧树脂（例如Dow公司的D.E.R，331）乃是用途广泛的基础树脂，既可用于电子工业的包封和黏合剂，又可用扩链工艺（Advance-ment)，使液体树脂与双酚A进一步反应，制造分子量较高的固体环氧树脂。  \n\n文献介绍的三段反应法，是因为 $\\mathbf{NaOH}$ 在促使ECH和BPA化合的同时，也使ECH水解损耗，三段反应法使环氧氯丙烷单耗低 $(550{\\sim}570\\mathbf{kg}/\\mathrm{t})$ ，产品质量好，典型生产示例。  \n\n将双酚A和环氧氯丙烷按 $1:(3\\sim5)$ ）（质量比）的比例加入反应釜中，升温至 $50\\sim$ $80^{\\circ}\\mathrm{C}$ 溶解，控制釜温为 $60\\sim70^{\\circ}{\\mathrm{C}}$ ，分几次加入约为酚羟基当量 $0.08{\\sim}0.1$ 当量的液碱（1)，常压反应 $4\\mathord{\\sim}6\\mathrm{h}$ ，控制釜内真空度为 $0.075\\sim0.085\\mathbf{MPa}$ ，温度 $60\\sim70\\Upsilon$ 于 $_{3\\sim5\\mathrm{h}}$ 滴加完约为酚羟基当量 $0.8\\sim0.9$ 的碱（2） $(\\geqslant48.5\\%)$ ，维持回流反应 $_{3\\sim6\\mathrm{h}}$ ，回收过量的环氧氯丙烷，加入溶剂溶解，再加人约为酚羟基当量 $0.08{\\sim}0.1$ 的液碱（3） $(10\\%\\sim20\\%$ ）进行精制反应，通过水洗、回流、脱溶剂等一系列后处理工序得到成品树脂：  \n\n环氧值/(eq/100g) 0.51\\~0.53 黏度（25C） 4000\\~9000mPa·s 易皂化氯 100\\~200mg/L  \n\n$\\textcircled{2}$ E-44环氧树脂的制造  \n\n配比：  \n\n双酚A 1. 0kgmol NaOH(30%水溶液） ①1.435kgmol环氧氟丙烷 2. 7kgmol ②0.775kgmol苯（或甲苯） 适量  \n\n操作：  \n\n把双酚A投入溶解釜中，加人环氧氯丙烷，开动搅拌，用蒸汽加温至 $70\\%$ 溶解。溶解后将物料送至反应釜中，在搅拌下于 $50\\sim55\\mathrm{{C}}$ ，4h内滴加完第一份碱溶液，在 $55\\sim60^{\\circ}C$ 下继续维持反应4h。前阶段反应结束后减压回收过量的环氧氯丙烷 $85\\mathrm{{T}}$ ，21.33kPa)，冷凝  \n\n收集后重新利用。  \n\n回收结束后加人苯溶解，搅拌加热至 $70\\Upsilon$ 。然后在68～73℃情况下，于1h内滴加第二份碱溶液，在 $68{\\sim}73^{\\circ}\\mathrm{C}$ 继续反应 $^{3\\mathrm{h}}$ ，然后冷却静置分层，将上层树脂苯溶液移至回流脱水釜，下层的盐脚尚可加苯再萃取一次后放掉。在回流脱水釜中回流至蒸出的苯清晰无水时止，冷却、静置、过滤后送至脱苯釜脱苯，先常压脱苯至液温达 $110^{\\circ}\\mathrm{C}$ 以上，然后减压脱苯，至液温 $140{\\sim}143^{\\circ}\\mathrm{C}$ 无液体馏出时，出料包装。  \n\n早期Shell公司的E.C.Shokal等所述制造低分子量液体环氧树脂的方法与上述不同，介绍如下。  \n\n投料：  \n\n双酚A 5130g(22. 5mol) 水环氧氯丙烷 20815g(225mol) NaOH  \n\n104g   \n1880g  \n\n操作：  \n\n双酚A、环氧氯丙烷和水投人反应釜并升温， $\\mathbf{NaOH}$ 的量为每摩尔双酚A投入NaOH$\\scriptstyle2,04{\\mathrm{mol}}$ ，即过量 $2\\%$ 。首先加人 $300\\mathbf{g}\\mathbf{NaOH}$ ，反应放热，需冷却釜壁。逐步再加入 $\\mathbf{NaOH}$ 维持温度在 $90\\mathrm{\\sim}100\\mathrm{\\textperthousand}$ 间。缩合完毕后，蒸馏回收多余的环氧氯丙烷（减压至 $6.67\\mathrm{kPa}$ ，升温至 $150^{\\circ}\\mathrm{C}$ 为止)。此蒸馏回收的得率很重要，冷凝器宜用低温的冷冻液以降低环氧氯丙烷逸失。将苯投入反应釜以溶解树脂，过滤以除去生成的盐，盐渣可再用苯冲洗以提高树脂得率，将苯溶液合并蒸馏，回收苯即得环氧树脂，软化点为 $9\\mathbb{C}$  \n\n采用二步法制造低分子量环氧树脂，降低环氧氯丙烷的消耗，缩短工时：  \n\n![](images/38db299f8de235359bfd2cd6d8a55b0e960df23c1ab3c6a7c9f8d13bce1ed06d.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 314,
+        "chunk": "# 2.中分子量环氧树脂的制造工艺  \n\n中分子量环氧树脂是指类似于我国的601、604的品种，有两种制造工艺：  \n\n$\\textcircled{1}$ 一步法又称糖法（taffy process);   \n$\\textcircled{2}$ 二步法又称扩链法（advancement process)。  \n\n早期只有一步法，其产物在后阶段水洗时很黏稠，像是“太妃糖”，故俗称taffyprocess，其产物的聚合度n有奇数，也有偶数。二步法是后期开发的工艺，其产物的聚合度 $\\boldsymbol{n}$ 主要为偶数。二步法的工艺是将低分子量的环氧树脂与双酚A反应扩链而得中分子量或高分子量环氧树脂。此方法开发原因之一是国外制造环氧树脂与国内不同。国内往往低分子量液体环氧树脂比固体树脂的售价贵。国外则工艺先进，回收环氧氯丙烷完善，使单耗低，故液体树脂的售价低，因此首先大规模生产低分子量的环氧树脂(规模效益好)，再按需要配入不同量的双酚A扩链，制得一系列的环氧树脂。现今中及高分子量环氧树脂大多采用扩链法生产。  \n\n兹举例介绍一步法制造工艺。  \n\n![](images/e1d58618e7eef215715c65eba9b2e5633bad2206682d0766fa3f0565bf372156.jpg)  \n\n配比（以E-12为例）：  \n\n双酚A 1kgmol NaOH(30 %) 环氧氯丙烷 1. 145kgmol  \n\n1. 185kgmol操作：  \n\n将双酚A和 $\\mathbf{NaOH}$ 溶液投入溶解釜中，搅拌加热至 $70^{\\circ}\\mathrm{C}$ 使双酚A完全溶解，趁热过滤，滤液放人反应釜中冷却至 $47^{\\circ}C$ 时一次加入环氧氯丙烷，然后缓缓升温至 $80^{\\circ}\\mathrm{C}$ 。在 $80\\sim$ $85^{\\circ}C$ 反应1h，然后在 $85\\sim95\\mathrm{^{\\circ}C}$ 维持至软化点合格为止。加水降温，将废液水放掉，再用热水洗涤多次，至中性和无盐，最后用去离子水洗涤。先在常压脱水，液温升至 $115\\%$ 以上时，减压至21.33kPa，逐步升温至 $135\\sim140^{\\circ}\\mathrm{C}$ 。脱水完毕，出料冷却，即得固体环氧树脂。此法操作时必须将树脂的碱性洗净。若残留微量碱，往往在最后脱水阶段引起釜中树脂胶结。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 315,
+        "chunk": "# 3.扩链法制中、高分子量环氧树脂  \n\n此法是用低分子量环氧树脂的环氧基，在加温和催化剂作用下，与双酚A的酚羟基反应而扩链。根据加人双酚A量的多少，可制得中分子量或高分子量环氧树脂。此法现广泛采用。此法的要点是选择合适的催化剂例如三苯基磷类衍生物，它必须具有优良的选择性，使环氧基与酚羟基反应，而不与中等分子量环氧树脂中的仲羟基反应，以制得线型的较高分子量的树脂。此法的另一要点是每批投料的环氧树脂的氯含量低，并必须精确分析其环氧基含量，然后计算所需加双酚A之量。反应一旦引发，发热剧烈，反应釜必须有足够的冷却面积和冷却能力。  \n\n现在国外环氧树脂制造公司（如Hexion公司、Dow公司）有售专供扩链用的低分子量环氧树脂，其中已预先加入适量的催化剂。涂料工厂可用此树脂自行与双酚A反应，制得所需的中或高分子量环氧树脂。例如Dow公司出售的DER343（环氧当量 $192\\sim203)$ ·Hexion公司的Epon829H，即预含选择性的催化剂。  \n\n兹举例介绍此法制备中、高分子量环氧树脂的工艺。  \n\n反应釜装有良好的冷凝器、冷水夹套及蛇管以吸收反应热。将低分子量环氧树脂（预含催化剂）及双酚A投入反应釜，通氮气，加热至 $110\\sim120^{\\circ}\\mathrm{C}$ ，此时放热反应开始，控制釜温至177℃左右。注意用冷却水控制反应，使之不超过 $193^{\\circ}\\mathrm{C}$ 以免催化剂失效。在 $177^{\\circ}C$ 所需保温的时间，取决于制得的环氧树脂的分子量：  \n\n环氧当量在1500以下 保持45min环氧当量在1500以上 保持90\\~120min  \n\n笔者在大反应釜操作中观察到反应很剧烈，必须有足够的冷却。投入的环氧树脂的环氧当量必须是新近分析测定者。双酚A用量计算公式：  \n\n$$\n\\pmb{W}=\\frac{E_{\\mathrm{v}}1-E_{\\mathrm{v}}2}{0.8771+E_{\\mathrm{v}}2}\\pmb{Q}\n$$  \n\n式中W—双酚A用量，kg；$\\boldsymbol{Q}$ ——液体环氧树脂投料，kg；$E_{\\mathrm{v}}1.$ —基础树脂环氧值；${{E}_{\\mathrm{v}}}2$ —成品树脂环氧值。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 316,
+        "chunk": "# 另例扩链法如下：  \n\nE-51环氧树脂 248. 6g双酚A 94.4g乙基三苯基磷碘化物(ethyl triphenyl phosphonium iodide) 0.21g渐渐升温至 $170^{\\circ}\\mathrm{C}$ 发生反应，保温。制成的环氧树脂的环氧当量为693。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 317,
+        "chunk": "# 4.线型环氧树脂的制造工艺  \n\n环氧树脂的分子量随着二酚基丙烷和环氧氯丙烷的摩尔比的变化而变化。一般说来，环氧氯丙烷过量越多，分子量越小。当制取分子量达数万的环氧树脂时，必须采用等摩尔比。  \n\n以 $N a O H$ 作催化剂，比例略微过量，分批滴入以防反应过快，影响分子量分布的均匀性。先进行溶液聚合，采用乙醇作反应介质，原始单体得以均匀混合，并有助于反应温度的控制。随着反应进行分子量增大，树脂在乙醇中溶解度逐步降低，这时转入混合溶剂进行乳液聚合过程，以乙醇、丁醇和甲苯的混合溶剂作最后反应阶段的反应介质。当反应达到一定程度后，滴加苯酚封去环氧端基，使分子链增长告终。  \n\n配比：  \n\n<html><body><table><tr><td>原料</td><td>规格</td><td>数量/kg</td></tr><tr><td>二酚基丙烧</td><td>精制，熔点155℃以上</td><td>11. 414</td></tr><tr><td>环氧氯丙烷</td><td>精制，馏程112～117°℃</td><td>4.626</td></tr><tr><td>乙醇</td><td>95%工业品</td><td>13.50</td></tr><tr><td>氢氧化钠</td><td>20%工业品</td><td>①10.00</td></tr><tr><td></td><td>20%工业品</td><td>②1.50</td></tr><tr><td>苯酚</td><td>100%工业品</td><td>0.46</td></tr><tr><td>混合溶剂</td><td>甲苯1丁醇=211</td><td>40.00</td></tr><tr><td>环己酮</td><td>工业品</td><td>5.00</td></tr></table></body></html>  \n\n工艺过程：  \n\n先将二酚基丙烷、环氧氯丙烷溶解于乙醇中，滴加第一份氢氧化钠溶液，室温搅拌16h，再加第二份氢氧化钠，升温回流，在 $80^{\\circ}\\mathrm{C}$ 反应半小时，加 $5\\mathbf{k}\\mathbf{g}$ 混合溶剂。每隔半小时加混合溶剂 $2.5\\mathrm{kg1}$ 次，共加3次。回流4h后，加苯酚，再加混合溶剂 $5\\mathbf{k}_{\\mathbf{g}}$ ，继续回流1.5h，再加冷水 $10\\mathbf{kg}$ 。弃去下层废液。树脂用热水洗涤，洗到 $\\mathrm{pH}=7\\sim7.5$ 为止。加入余量的混合溶剂。真空回流脱水，水脱尽后加环已酮。过滤，即为成品。  \n\n<html><body><table><tr><td>末余件：</td><td></td><td></td><td></td></tr><tr><td>外观</td><td>透明到微浑液体</td><td>黏度（25℃，涂-4杯)</td><td>100~130s</td></tr><tr><td>固体含量</td><td>25%±2%</td><td>色泽（铁钻法）</td><td>3以下</td></tr></table></body></html>  \n\n除了双酚A之外，尚有其他多元酚可制造环氧树脂，例如双酚F。  \n\n双酚F是由苯酚和甲醛缩合而成，取甲醛（formaldehyde）字头F，故称为双酚F，有3种异构体的混合物：  \n\n![](images/ce684bd198026a782e21f58a489c630e7519c5ad30d8839550f7b560738d84c0.jpg)  \n\n用双酚F与环氧氯丙烷制得的环氧树脂，因其亚甲基比双酚A的亚丙基易于旋转，故黏度较低，适合作无溶剂涂料。人们早期单独用双酚A制造最低分子量的环氧树脂（双缩水甘油醚)，因为太纯，容易结晶，不便使用，必须加温熔化后使用。掺入若干量的双酚F环氧树脂之后，降低了纯度，不易结晶，黏度也较低，便于配制高性能无溶剂漆。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 318,
+        "chunk": "# 5.双酚F环氧树脂  \n\n可能有3种异构体双酚F环氧树脂：  \n\n![](images/aa18796d23f96d9717873bcb7bda7bb7a98bfb32a577f39f1af9df47b3febde0.jpg)  \n\n下面介绍一些典型的双酚F环氧树脂的性能指标，供参考。  \n\nCiba公司的GY-281：  \n\n环氧当量 158\\~172 黏度（25℃） 5000\\~7000mPa \\* s  \n\n开发双酚F环氧树脂的目的是，双酚A型液体环氧树脂的黏度高 $(25\\mathrm{{^{q}C}}$ 达 $12000\\mathrm{{mPa}\\cdot\\mathrm{{s})}}$ .应用于无溶剂涂料，尤以应用于电子工业的浇注包封，很不方便。制造商作了努力以降低双酚A环氧树脂黏度，如陶氏公司：  \n\n环氧当量 黏度（25C）/mPa • sD. E. R. 331 182\\~192 11000\\~14000 基础树脂D. E. R. 330 176\\~183 7000\\~10000 低黏度树脂D. E. R. 332 171\\~175 4000\\~6000 它是纯的双酚A的二缩水甘油醚而双酚F环氧树脂，因其亚甲基比双酚A的亚丙基容易旋转，黏度较低，如：  \n\nD. E. R. 345168\\~175 3500\\~4500mPa \\* s  \n\n降低黏度，即降低树脂分子量，接近于双酚A或双酚F的二缩水甘油醚，寒冷时会出现结晶问题。纯的双酚A二缩水甘油醚的熔点约 $42\\Upsilon$ ，双酚F的二缩水甘油醚熔点约$55\\mathrm{^c}$ ，使用很不方便。所以D.E.R.331基础树脂，故意制成分子量分布较宽，以避免结晶出现。另一种避免结晶的方法是，将双酚A环氧树脂与双酚F环氧树脂混合，例如D.E.R.351即是双酚A树脂与双酚F树脂50/50的混合物，其环氧当量为 $169\\sim181$ ，黏度$(25^{\\circ}\\mathbb{C}$ ）为 $4500{\\sim}6500\\mathrm{mPa}\\cdot\\mathrm{s}$ ，不会结晶。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 319,
+        "chunk": "# 6.诺伏勒克环氧树脂  \n\n人们用虫胶（Shellac）溶于酒精制成涂料，以涂饰木器及钢琴。后来用苯酚与少量甲醛在酸性缩合，制得热塑性酚醛树脂，以代替天然的虫胶，溶于酒精制漆，称为Novolac，诺伏勒克Novo表示新，Lac指漆。  \n\n诺伏勒克环氧树脂是由苯酚或邻甲酚与甲醛反应制得诺伏勒克，再与环氧氯丙烷反应而成，其特点是每分子的环氧官能度大于2，可使涂料的交联密度大，其耐热性和耐化学药品性高于双酚A型环氧树脂，但涂膜较脆，附着力稍低，并往往需较高的固化温度，故常与双酚A环氧树脂合用，或用双酚A环氧树脂作底漆，诺伏勒克环氧树脂作中涂层及面漆。其示意式如下，有两种苯酚型和邻甲酚型：  \n\n![](images/31299e53b58f799c9d31f545665a6e8232ce625e8ac34e7d5d3a77ef7653f863.jpg)  \n\n其典型的商品树脂性质如下所示：  \n\n\n<html><body><table><tr><td>Dow公司</td><td>环氧当量</td><td>黏度/mPa • s</td><td>官能度</td></tr><tr><td>DEN431</td><td>172~179</td><td>1100~1700 (52C)</td><td>2.2</td></tr><tr><td>DEN438</td><td>176~181</td><td>20000~50000(52C)</td><td>3.6</td></tr><tr><td>DEN439</td><td>191~210</td><td>半固体</td><td>3.8</td></tr><tr><td>Ciba公司</td><td></td><td></td><td></td></tr><tr><td>PY-307-1</td><td>165~170</td><td>30000~50000(25C）</td><td>2.3</td></tr><tr><td>GY-1180</td><td>175~182</td><td>20000~50000（53C）</td><td>3.6</td></tr></table></body></html>  \n\nDow公司的DEN表示DowEpoxyNovolac。  \n\n下面介绍环脂族环氧树脂的制造。  \n\n最典型代表的是3，4-环氧基-6-甲基环已烷甲酸 $3^{\\prime}$ 1 $4^{\\prime}$ -环氧基-6-甲基环己烷甲酯，我国牌号为H-71，陶氏公司牌号UVR6110，供制造紫外光固化的阳离子固化型涂料。  \n\n合成路线：  \n\n![](images/52926076a2c7db6b5c6dc5293c254736b6b1d45054a32c3693bfa09703165019.jpg)  \n\n性能：  \n\n![](images/b73339ecf37265cca4b2ffb8d7ffd1a59e287b7df58bda2179a1e5dddb673c9e.jpg)  \n\n本品为黏稠液体，可溶于苯、甲苯、四氯化碳、乙醇、乙醚。  \n\n此涂料特点是光固化时不受空气阻聚，收缩较低，故附着力好，需用三芳基硫六氟磷 酸盐为光引发剂，价很贵。 oA",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 320,
+        "chunk": "# 7.环氧树脂的进展  \n\n前面较多介绍了双酚A系的几种典型树脂。它们自20世纪50年代工业化生产以来，经过历年不断改进，产品的品质更纯净，颜色更浅淡，分子量分布更狭窄，品种牌号更多。  \n\n$\\textcircled{1}$ 品种多例如Dow公司在661型和664型之间增加了一些品种，以满足不同需要：  \n\nDER661 环氧当量500\\~560 DER663U 环氧当量730～820   \nDER662 环氧当量575\\~685 DER664、664U 环氧当量875\\~955  \n\n日本东都公司产环氧树脂也有类似情况：  \n\nYD-011 环氧当量450\\~500 YD-013 环氧当量800～900  \nYD-012 环氧当量600～700 YD-014 环氧当量900～1000  \n\n②产品规格狭窄东都公司某些高级牌号树脂的环氧当量范围很窄，例如： YD-7011 环氧当量480\\~500 YD-7014 环氧当量940\\~960  \n\n$\\textcircled{3}$ 含氯量低为了适应电气绝缘（以及阴极电泳漆）用途的环氧树脂，其含氯量限制得很低。Ciba、Dow、东都公司等均有优级产品，例如Dow公司的两种环氧树脂：  \n\n<html><body><table><tr><td></td><td>DER331</td><td>DER361</td></tr><tr><td></td><td>（标准商品）</td><td>（低氧级）</td></tr><tr><td>环氧当量</td><td>182~190</td><td>186~190</td></tr><tr><td>易水解</td><td>(200~300)×105</td><td>50 ×10~</td></tr></table></body></html>  \n\n$\\textcircled{4}$ 色泽浅在20世纪50年代，环氧树脂的色泽较深，其 $40\\%$ 溶液的色泽，例如Epikote828、834、1001均为8档（Gardner加氏）。至80年代降为3档，近年来各公司产品约为1档，其中Dow公司产品则颜色更浅，改采用APHA色度，例如662E、663UE、664E、664UE的色泽均极浅。  \n\n回顾1948年壳牌推出的Epon树脂仅6种，今则全球生产数十种不同性质品种，有溴化阻燃、二聚酸改性、脂环族辐射固化、水性环氧树脂等，供不同要求。有些黏稠半固体环氧树脂使用时倾倒麻烦，则制成溶液以利投料，而且固体环氧树脂制成片状以便投料溶解。下面是陶氏环氧树脂色泽的浅淡。  \n\nDow环氧树脂D.E.R.331是该公司的基础液体树脂，规格如下。  \n\nE.E.W环氧当量 182\\~192 易水解氯 500ppm(最大)环氧基含量/（mmol/kg） 5200\\~5500 游离环氧氯丙烷 5ppm(最大)即相当于环氧值 0.52\\~0.55/100g 色泽(Pt-Co) 75(最大)环氧基质量 22.4\\~22. 6% 贮藏期 24月黏度（25C） 11000\\~14000mPa \\* s  \n\n此外市上还有氢化双酚A型环氧树脂，其软化点在 $80\\sim105^{\\circ}$ 之间，环氧当量600～1100之间，可制粉末涂料，具有良好的户外耐久性。  \n\n现Hexion集团是全球最大的环氧树脂生产企业，陶氏公司居其次，第三为我国台湾省的南亚塑胶公司，是全球三强。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 321,
+        "chunk": "# 四、环氧树脂的固化剂  \n\n前面章节已介绍环氧树脂可有许多反应。环氧树脂本身是热塑性，分子量不高，必须与固化剂交联成三维高分子膜，才成为优良的涂料。许多生产环氧树脂的大型石油化工公司，如Dow公司、前壳牌公司，生产固化剂的品种不多，现Huntsman公司生产一系列很多固化剂品种，其他有些专门公司生产近百种固化剂。兹就环氧涂料常用的固化剂介绍如下。",
+        "category": " Introduction"
+    },
+    {
+        "id": 322,
+        "chunk": "# 1.脂肪族多元胺类固化剂  \n\n脂肪族多元胺能在常温下固化，固化速度快、黏度低，可用以配制常温下固化的无溶剂或高固体涂料，表2-1-129介绍涂料工业常用的脂肪族多元胺固化剂。  \n\n脂肪族多元胺类固化剂（尤其是其中分子量低者）有以下不足之处。  \n\n$\\textcircled{1}$ 固化时放热量大，一次配漆不能太多，施工时限短。  \n$\\textcircled{2}$ 活泼氢当量很低，配漆称量必须准确，过量或不足会影响性能。  \n\n表2-1-129常用的脂肪族多元胺固化剂  \n\n\n<html><body><table><tr><td>品 名</td><td>分子式</td><td>分子量数</td><td></td><td></td><td></td></tr><tr><td>乙二胺</td><td>HN—(CH)—NH</td><td>60</td><td>4</td><td>15</td><td></td></tr><tr><td>二亚乙基三胺</td><td>HN—(CH)NH(CH)NHz</td><td>103</td><td>5</td><td>20.6</td><td>5.5~8.5</td></tr><tr><td>三亚乙基四胺</td><td>HN(CHNH)CHNH</td><td>150</td><td>6</td><td>24.3</td><td>19.5~22.5</td></tr><tr><td>四亚乙基五胺</td><td>HN(CHNH)CHNHz</td><td>201</td><td>7</td><td>27.1</td><td>55</td></tr><tr><td>己二胺</td><td>HzN(CH)NHz</td><td>116</td><td>4</td><td>29</td><td></td></tr><tr><td></td><td>CH CH HN—CHC—CH—CH—(CH)—NH CH: CH HzN—CH-CH—CH C- (CH)—NH CH CH</td><td>158.3</td><td>4</td><td>39.6</td><td>5. 6(20℃)</td></tr></table></body></html>\n\n$\\Phi$ 活泼氢当量为分子量/活泼氢原子数。活泼氢当量取决于商品胺的纯度，一般略高于此值。  \n\n③有一定蒸气压，有臭味及刺激性（尤其是乙二胺、二亚乙基三胺)，影响工人健康。分子量较高者如三甲基己二胺的蒸气压较低，在 $50\\mathrm{{^circC}}$ 时为小于 $10^{5}\\mathrm{Pa}$ ，三亚乙基四胺在$20\\Upsilon$ 时为小于 $133\\mathrm{{Pa}}$ 。  \n\n$\\textcircled{4}$ 有吸潮性，不利于在低温高湿下施工；又因其碱性会吸收空气中的 $\\mathrm{CO}_{2}$ ，易生成氨基甲酸盐，析出于涂膜表面而损及外观，并影响层间附着力。  \n\n$\\textcircled{5}$ 高度极性（水溶性)，往往使它们与环氧树脂的混溶性欠佳，易引起涂膜缩孔、橘皮、泛白等病，所以施工时两个组分配合后须待熟化片刻后才应用，使部分胺与环氧树脂结合生成中间体，使两相互相混溶。  \n\n因此，在环氧涂料中脂肪族多元胺的使用不如聚酰胺或胺加成物广泛，须将其改性后使用。  \n\n此系脂肪胺是在常温固化的环氧漆中应用，它们由二氯乙烷与氨反应而得到混合多元胺，再分馏得各组分：  \n\n$\\mathrm{ClCH_{2}C H_{2}C l+N H_{3}}\\mathrm{\\longrightarrow~H_{2}N\\mathrm{-CH_{2}C H_{2}N H_{2}(1,2\\cdot Z\\mathrm{=}\\emptyset\\})}$ $\\mathrm{H_{2}N C H_{2}C H_{2}N H C H_{2}C H_{2}N H_{2}}\\mathrm{(=)}$ 亚乙基三胺）$\\mathrm{H_{2}N C H_{2}C H_{2}N H C H_{2}C H_{2}N H C H_{2}C H_{2}N H_{2}}$ （三亚乙基四胺）$\\mathrm{H}_{2}\\mathrm{N}\\cdot(\\mathrm{CH}_{2}\\mathrm{CH}_{2}\\mathrm{NH})_{4}\\cdot\\mathrm{CH}_{2}\\mathrm{CH}_{2}\\mathrm{NH}_{2}$ （四亚乙基五胺）  \n\n有时商业上，常习称它们为二乙烯三胺、三乙烯四胺。实际上并无乙烯双键，来源于英语 ethylene可译为亚乙基一 $\\mathbf{CH_{2}C H_{2}}-$ 。  \n\n除了上述的脂肪多元胺之外，美国Huntsman公司生产的聚醚二胺或聚醚三胺也可用作  \n环氧树脂固化剂，它的两端是氨基，中间是聚环氧丙烷，其特性是使涂膜富有挠曲性，而且  \n黏度低，共有22个品种，供不同用途。德国BASF公司也生产类似聚醚二胺（D230，  \nD400，D2000）和聚醚三胺（T403)，还有脂环胺：异佛尔酮二胺（IPDA)，熔点 $10\\Upsilon$ ，分  \n子量170.3，以及 $^{4,4^{\\prime}.}$ 二氨基二环己基甲烷，分子量210.3；熔点33.5～44℃；以及 $^{4,4^{\\prime}}$ 二  \n氨基二苯基甲烷，熔点 $89\\sim91^{\\circ}\\mathrm{C}$ ，分子量198.3。还有2-甲基咪唑CH；（片状），熔H  \n\n点 $136{\\sim}138^{\\circ}\\mathrm{C}$ ，分子量82.1，应用于环氧粉末涂料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 323,
+        "chunk": "# 2.脂肪胺加成物类固化剂  \n\n它是将脂肪族多元胺与少量环氧树脂反应而成。用此种胺加成物时涂膜不易吸潮泛白，臭味小，配漆后不必经熟化可直接使用。例如用乙二胺与低（或中）分子量环氧树脂反应示意式（后面将详细叙述制法）如下：  \n\n![](images/b0ae7687b1d7aef467dd82319f4cf242395f89c95c04b87bbabf5404b18eac42.jpg)  \n\nDow公司用二亚乙基三胺与液体低分子量环氧树脂反应制得加成物，下面为该加成物的性能规格。  \n\n活泼氢当量  \n\n黏度（25℃）  \n\nAnchor公司将1001树脂与乙二胺加成，制得牌号为870，含游离胺 $1\\%$ 以下，胺氢当量为245的固体，软化点约 $110^{\\circ}\\mathrm{C}$ 。此类提纯的加成物（isolatedadduct）的毒性低，涂膜性能好，不需要熟化期，可用于饮用水槽的内壁涂料等。  \n\n上述的活泼氢当量或胺氢当量，例如二亚乙基三胺，经盐酸滴定分析共有三个胺氮原子的胺值，但仅有5个活泼氢可与环氧基反应，故常以胺氢当量（amine hydrogen equivalentweightAHEW）或HEW表示。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 324,
+        "chunk": "# 3.酰氨基胺类固化剂（amidoamine）  \n\n酰氨基胺是用植物油脂肪酸（或塔油）与多元胺缩合而成，含有酰氨基及氨基：  \n\n上式中有3个氨基活泼氢原子，可与环氧基反应。它固化涂料时对环境湿度不敏感，并对物面有良好的润湿性。  \n\n制造时若升高温度则脱水成为咪唑啉，黏度降低，是其优点。  \n\n![](images/ff438a22584373dca5cf9c799e7e3659dcfbe09fe832772aa2d9085455e4b370.jpg)  \n\n商品的酰氨基胺中往往含有若干咪唑啉。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 325,
+        "chunk": "# 4.氨基聚酰胺树脂固化剂（polyamideresin）  \n\n氨基聚酰胺树脂不是简单的化合物，而是黏稠的树脂，含有游离的氨基，能与环氧树脂固化，性质优良，应用广泛。它由不饱和脂肪酸加热聚合成为二聚酸，再与多元胺缩合而成，它是环氧涂料中应用最广泛的固化剂，后有详述。  \n\n![](images/f0e40d3fff652d239fd67ac769a22d32c8cfe44989287f213eec91c08c3e7f60.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 326,
+        "chunk": "# 5.环脂胺类固化剂  \n\n环脂胺类色泽浅淡，保色性好，黏度低是其特点，但反应迟缓，往往与其他固化剂拼用，或加促进剂，或制成加成物，或需加热固化。典型的如BASF公司的LarominC260：  \n\n![](images/03349a9e07d0e2ab884799737c9b57ae96fcce79fed48eae2241ccfc39ca1100.jpg)  \n\n它是液体，密度0.945，胺氢当量60。  \n\n还有双（4-氨基环己基）甲烷，是固体，熔点 $40\\Upsilon$ 。  \n\nDegussa公司的异佛尔酮二胺IPDA  \n\n![](images/8387207d881f9ca8ed2e5d8dc0c39d889532506cd667fba9254aa0170ebef19f.jpg)  \n\n胺氢当量42.6；熔点 $10^{\\circ}\\mathrm{C}$ ；无色液体，黏度（ $20\\%$ ） $18\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$ 9",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 327,
+        "chunk": "# 6.芳香胺类固化剂  \n\n芳香胺有 $_{4,4^{'}}$ -二氨基二苯甲烷和间苯二胺。  \n\n![](images/a6f70ad1f809279601df4a06c1cbb8c497708eec8a498dc1eac4a2bbcecbb989.jpg)  \n\n![](images/9ea1336ce16d5813d14d9d12e9fc5eafd579b94c079bb1a8409c0c903d211edf.jpg)  \n（4，4'-二氨基二苯甲烷）  \n\n活泼氢当量 50 熔点 86℃ 活泼氢当量 27 熔点 63℃  \n\n以上两种芳香胺的熔点太高，使用不方便，常有将两者混合， $(6:4)$ ）制成低共熔混合物（eutectic mixture)，如 Shell公司的 ${}^{*}z$ 固化剂”，Anchor公司的Ancaminel482，其活泼氢当量为37，在 $25\\mathrm{{T}}$ 时的黏度为 $900\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$ ，呈液态。  \n\n芳香胺与环氧基反应活性较弱，因为其第四对电子已部分地与苯环共享，其碱性常数$k_{\\mathrm{b}}$ 很小。一般的脂肪胺的 $k_{\\mathrm{b}}$ 值约为 $10^{-3}\\sim10^{-4}$ ，而苯胺的 $k_{\\mathrm{b}}$ 值仅为 $4,2\\times10^{-10}$ 8  \n\n$$\n\\mathrm{RNH}_{2}+\\mathrm{H}_{2}\\mathrm{O}\\longrightarrow\\mathrm{RNH}_{3}{^+}+\\mathrm{OH}^{-}\n$$  \n\n![](images/fc3a5a2b9c9fa54bf909f271cb3dbd4fd9cba8b54821397e05f37a424a1f336e.jpg)  \n间苯二胺  \n\n$$\nk_{\\mathrm{b}}=\\frac{\\left[\\mathrm{RNH_{3}}+\\right]\\ \\left[\\mathrm{OH^{-}}\\right]}{\\left[\\mathrm{RNH_{2}}\\right]}\n$$  \n\n以上两种是最常用的芳香胺，前者习称DDM是英文diaminodiphenylmethane的缩写，有时也称methylenedianiline。间苯二胺习称MPDA。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 328,
+        "chunk": "# 7.芳脂胺类固化剂  \n\n芳脂胺类有间苯二亚甲基二胺（xylylenediamine，XDA)，其性质介于脂肪胺及芳香胺之间，我国苏州曾生产。",
+        "category": " Introduction"
+    },
+    {
+        "id": 329,
+        "chunk": "# 8.曼尼期碱类固化剂  \n\n曼尼期（Mannich）碱是经曼尼期反应而合成的，由酚（或酮）、甲醛及胺三者缩合而得，它的固化特点是即使在低温、潮湿环境下也能固化。制法示意如下：  \n\n分子中有酚羟基，能促进固化。我国涂料工厂也制造此类固化剂，习惯称为“酚醛胺”，常用于寒季需快速固化的环氧树脂漆。  \n\n采用相同的曼尼期反应，但不加多元胺，而加入单官能的二甲胺，则产品是叔胺：  \n\n![](images/b6cc3bb21efe3adfdeeea1884b9dd09c3729b4220b4b7b61d0a46aeb0eb801c2.jpg)  \n\n分子中既有酚羟基又有叔氨基，有催化作用。  \n\n最典型的是称为DMP-30的固化剂，分子式如下所述：  \n\n![](images/e9678cef22fe4df1ccfc52976e9c40672257ecb5f4757676b410aaa2f80ce6d3.jpg)  \n\n它是叔胺，其氨基上没有活泼氢原子，不能与环氧基结合，但是它是强催化剂，能促进聚酰胺、硫醇等与环氧基交联。它还能单独促进环氧树脂自身的环氧基之间互相开环交联。Anchoc公司类似商品名K-54的色泽（加氏管）为6，密度（ $25\\Upsilon$ ） $0.97g/\\mathrm{cm}^{3}$ ，黏度$(25\\Upsilon$ ）为 $230\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$  \n\n我国三木公司等生产的T-31即是酚醛胺固化剂。  \n\n近二十年来开发成功的另一类酚醛胺固化剂是用腰果壳油制得的腰果酚。  \n\n![](images/95fce6b238ef0da03ed2cabe9804d11147bf2c9cb8c94af1102957bef5072d77.jpg)  \n\n用此酚与甲醛及多元胺反应，美国Cardolite公司制造了一系列酚醛胺固化剂，因腰果酚含有十五碳侧键，起内增韧效果，并降低了表面能，可在潮的微锈面施工，可用于船舶等防腐蚀涂料。典型的如Cardolite2041固化剂：  \n\n胶值/(mgKOH/g) 250 颜色（加氏管） 活泼氢当量 150 固体含量 黏度（25℃） 400mPa \\* s  \n\n近年我国工厂有类似产品。",
+        "category": " Introduction"
+    },
+    {
+        "id": 330,
+        "chunk": "# 9.酮亚胺类固化剂  \n\n酮亚胺是由酮（例如甲基异丁基酮、甲基乙基酮等）与多元胺缩合脱水而成。施工时双组分并合涂布后吸收潮气，还原成多元胺，使环氧树脂固化。未吸潮之前它没有活泼氢原  \n\n子，不会与环氧基反应，故施工时限较长，国外称之为半潜固化剂。又因为它分子中没有活泼氢原子，分子间不能形成氢键，故黏度低，利于制造高固体涂料。  \n\n$$\n\\begin{array}{r}{\\mathrm{{C}\\mathrm{{H}_{3}}}}\\\\ {\\mathrm{{2}}}\\\\ {\\mathrm{{C_{\\mathrm{{f}}}\\mathrm{{H_{5}}}}}}\\end{array}\\overset{\\mathrm{{C}\\mathrm{{{H}_{3}}}}}{\\longrightarrow}\\mathrm{{C-0}}~+~\\mathrm{{H_{2}N-(C\\mathrm{{H_{1}})_{6}-N\\mathrm{H_{2}}}}}\\longmapsto\\begin{array}{l}{\\mathrm{{H_{5}C}}}\\\\ {\\mathrm{{H_{5}C_{\\mathrm{{c}}}}}}\\\\ {\\mathrm{{H_{5}C_{\\mathrm{{c}}}}}}\\end{array}\n$$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 331,
+        "chunk": "# 10.双氰胺类固化剂  \n\n$$\n\\begin{array}{c}{{\\displaystyle\\mathsf{N H}}}\\\\ {{\\displaystyle{\\mathsf{H}}_{\\imath}{\\bf N}{\\bf-}{\\bar{\\bf c}}{\\bf-}{\\bf N H C N}}\\longrightarrow2{\\bf H}_{\\imath}{\\bf N-}{\\bf C-}{\\bf N}}}\\end{array}\n$$  \n\n双氰胺在 $145{\\sim}165\\mathrm{\\textperthousand}$ 能使环氧树脂在 $30\\mathrm{{min}}$ 内固化。但在常温下双氰胺则是相当稳定的。将双氰胺充分粉碎成极细粉末，分散在液体树脂内，其贮存稳定性可达6个月。双氰胺在常温下是固体，可与固体树脂共同粉碎，制成粉末涂料，贮存稳定性良好。使用量为100份E-12树脂用 $2.5{\\sim}4$ 份双氰胺，固化条件为在 $145\\sim180^{\\circ}\\mathrm{C}$ 下烘半小时。商品的双氰胺固化剂有加少量促进剂（如2-甲基咪唑或2-苯基咪唑）以降低烘温，缩短时间，称为“加速双氰胺”，此外尚有“取代双氰胺”。  \n\n![](images/b08c1d93ddba7befbf726b4a1924483d50390a41e2a8a6a62e7befaafb1769ae.jpg)  \n\n它与环氧树脂混溶性好，漆膜光亮。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 332,
+        "chunk": "# 五、胺固化环氧树脂漆",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 333,
+        "chunk": "# 1.环氧树脂涂料的分类  \n\n(1）双组分常温干燥涂料(环氧基反应)  \n溶剂型涂料 环氧沥青涂料  \n多元胺固化环氧涂料 多异氰酸酯固化环氧涂料（羟基反应）  \n加成物固化环氧涂料 环氧酯涂料  \n聚酰胺固化环氧涂料 无溶剂涂料  \n(2）单组分烘干涂料  \n环氧酚醛涂料 羧基反应：混合型，TGIC型  \n环氧氨基涂料 双氰胺固化  \n环氧/封闭多异氰酸酯涂料 酚醛固化  \n环氧粉末涂料  \n\n(3）水性环氧涂料环氧树脂是分子量较低的热塑性树脂，不能形成合用的涂膜，即使是分子量稍高的E-12、E-06，其溶液涂布干燥后，其膜稍受弯曲，即出现细裂的“银纹”(Craging)，且不耐溶剂侵蚀。所以环氧树脂必须与固化剂反应，形成三维的大分子，才能生成良好的涂膜。但环氧树脂与固化剂混合后，发生反应，涂料黏度不断上升，经数小时或隔夜，变成黏稠不能使用而报废，所以商品的环氧漆必须与固化剂分开包装，临使用之前才混合，再施工涂装。其混合后可施工的时限，国外习称Potlife，指在配料小罐中的双组分混合后的寿期，本章称之为施工时限。",
+        "category": " Introduction"
+    },
+    {
+        "id": 334,
+        "chunk": "# 2.多元胺固化环氧树脂漆  \n\n早期的涂料工业缺乏经验，很多采用脂肪族多元胺以固化环氧树脂，例如乙二胺、二乙烯三胺，三乙烯四胺。其中乙二胺很少单独使用，因为水溶性高，且有些乙二胺商品是$80\\%$ 水溶液，所以仅以它为原料制造加成物。多元胺的优点是黏度低，有利于制造无溶剂或高固体涂料。但脂肪族多元胺反应发热高，施工时限短，常改用环脂族或芳香族多元胺配制无溶剂涂料。  \n\n除了上述的二乙烯三胺等外，上海也有造漆厂曾用过己二胺，但它是固体，使用不方便。也用过间苯二甲胺，可作环氧树脂固化剂。  \n\n![](images/2025541fa9df4cf5223b193f12a7eb52c4e1ceec47a48ea79b413bd2c9c4bed1.jpg)  \n\n$\\Phi$ 溶剂型双组分环氧漆，常选用E-20（国内俗称601）环氧树脂，因为它对溶剂要求不高，能溶解于芳烃和丁醇 $(4:1)$ ）的混合物中，而且它是固体树脂，待涂层溶剂挥发后，涂膜即能凝定，有利于干燥，涂料工艺上称为“挥发干”。它的两个环氧基团有一定距离间隔，涂膜有良好的柔韧性。但若制造无溶剂或高固体涂料，则选用低分子量的树脂。  \n\n$\\textcircled{2}$ 配方例中的脲醛树脂是涂膜的流平剂，也可选用其他如BYK等的流平剂。  \n\n$\\textcircled{3}$ 溶剂中不可含有酯类，以免与胺类固化剂发生反应（氨解）。  \n\n$\\textcircled{4}$ 配方的计算，一般是每个环氧当量配合一个胺氢当量的固化剂，可在此比例附近适当调节求最优化以满足不同要求。  \n\n简单配方示例如下。  \n\n<html><body><table><tr><td>(1）清漆</td><td></td><td></td></tr><tr><td>甲组分</td><td>乙组分 二乙烯三胺</td><td>3.0g</td></tr><tr><td>环氧树脂（E-20）</td><td>50.0g 丁醇</td><td>3.5g</td></tr><tr><td>脲醛树脂（60%），流平剂</td><td>2.5g</td><td></td></tr><tr><td>甲乙酯</td><td>10.0g 二甲苯</td><td>3.5g</td></tr><tr><td>甲基异丁基酮</td><td>15.0g</td><td></td></tr><tr><td>(2）白漆</td><td>乙组分</td><td></td></tr><tr><td>甲组分</td><td></td><td></td></tr><tr><td>环氧树脂（E-20)</td><td>29.90g</td><td>已二</td></tr><tr><td>滑石粉</td><td>4.95g</td><td></td></tr><tr><td>脲醛树脂（60%）</td><td>1. 85g</td><td></td></tr><tr><td>钛白</td><td>36.60g</td><td></td></tr><tr><td>溶剂（甲苯/丁醇41）</td><td>24.00g</td><td></td></tr></table></body></html>  \n\n以上涂料，涂布后经数小时初步干燥，但须经七天后才充分交联固化，达到优良的性能。双组分混合后黏度逐渐上升，其施工时限取决于固体含量（溶剂多则冲稀了反应基团浓度，吸收反应热施工时限长些)，酮类溶剂阻缓反应速度，会与胺形成氢键。  \n\n以上介绍的环氧涂料的溶剂，常用的是芳香烃、酮类、醇、醚醇的混合物，唯一例外是醋酸叔丁酯，因位阻几乎不氨解。 买  \n\n![](images/1805e1408834d84ae3e20a6367b36f72016d1daa74ef435bb0c7e1c1ead98250.jpg)  \n\nHanren提出三维溶解参数，上述溶剂溶解参数见表2-1-130。  \n\n表2-1-130溶剂的溶解参数  \n\n\n<html><body><table><tr><td>溶剂</td><td>总参数</td><td></td><td></td><td></td></tr><tr><td>甲苯</td><td>18.2</td><td>18.0</td><td>1.4</td><td>2.0</td></tr><tr><td>邻二甲苯</td><td>18.0</td><td>17.0</td><td>1.4</td><td>3.1</td></tr><tr><td>丁酮</td><td>19.0</td><td>16.0</td><td>9.0</td><td>5.1</td></tr><tr><td>甲基异丁酮</td><td>17.0</td><td>15.3</td><td>6.1</td><td>4.1</td></tr><tr><td>正丁醇</td><td>23.1</td><td>16.0</td><td>5.7</td><td>15.8</td></tr><tr><td>乙二醇丁醚</td><td>20.9</td><td>16.0</td><td>5.1</td><td>12.3</td></tr></table></body></html>  \n\n混合溶剂的参数可近似地以下式估计：  \n\n式中个别溶剂的体积分数。  \n\n但环氧树脂商品系列中，分子量差别很大，从最低的E-51到最高的E-03，溶解性有差别。E-51可溶解于芳香烃中，E-03树脂的分子量高，羟基含量也多，其分子间相互作用力也强，必须有酮类等强溶剂才能克服树脂分子间作用力。而中等分子量的E-20 树脂，一般用芳香烃加少量丁醇也能溶解，所以Hansen的溶解参数，对于环氧树脂，尚须考虑树脂的分子量。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 335,
+        "chunk": "# 3.加成物固化环氧涂料  \n\n采用多元胺作固化剂，有不少缺点，其挥发毒性，寒湿条件下施工涂膜会泛白，引起层间剥离等病，因此改用加成物固化剂，即将多元胺与少量环氧树脂或单环氧化合物加成，成为分子量较大（不易挥发）和较疏水的固化剂。制造加成物有两种方法。  \n\n（1）现场配制的加成物制备简便，但质量较低，例如：  \n\n环氧树脂E-20 32.6g 正丁醇 30.0g 二乙烯三胺 7.4g 二甲苯 30.0g  \n\n将环氧树脂和胺分别溶解于溶剂中，在胺溶液中在揽拌下逐渐加入环氧树脂溶液，加毕搅拌3h。此产物的固体分为 $40\\%$  \n\n配漆的配比，（固体分)：  \n\n环氧树脂E-20 100g 加成物（固体计） 30\\~35g",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 336,
+        "chunk": "# (2）提净的胺加成物  \n\n乙二胺（75%) 52kg 二甲苯 56kg 丁醇 56kg 环氯树脂E-20 110kg  \n\n把乙二胺、丁醇、二甲苯置入反应釜，搅拌，慢慢地加入环氧树脂，加毕后，密闭反应釜，加热回流反应 $2\\sim3\\ensuremath{\\mathrm{h}}$ ，然后减压蒸出溶剂和过量的乙二胺，达到终点（产物的软化点约$96\\%$ ）降温出釜。 or  \n\n<html><body><table><tr><td>甲组分</td><td></td><td></td><td></td></tr><tr><td>环氧树脂E-20</td><td>50.0g</td><td>混合溶剂</td><td>47.5g</td></tr><tr><td>脲醛树脂（60%）</td><td>2.5g</td><td></td><td>二</td></tr><tr><td>乙组分</td><td></td><td></td><td></td></tr><tr><td>提净胺固化剂</td><td>20.0g</td><td>混合溶剂</td><td>20.0g</td></tr></table></body></html>  \n\n此提净的胺加成物是经过减压蒸馏，所含游离胺很少，所以配漆时双组分混合后，不必等候即可施工，涂膜也不易泛白。涂料中加人钛白，应用于船舶的饮水舱（potable watertank）效果良好。  \n\n此胺加成物的示意式：  \n\n$$\n\\begin{array}{l}{{\\mathrm{CH}}_{2}{\\mathrm{-NH}}{\\mathrm{-CH}}_{2}{\\mathrm{-CH}}{\\mathrm{-CH}}{\\mathrm{-CH}}{\\mathrm{-R}}{\\mathrm{7CH}}{\\mathrm{-CH}}{\\mathrm{-CH}}_{2}{\\mathrm{-NH}}{\\mathrm{-CH}}_{2}}\\\\ {\\stackrel{\\mathrm{i}}{\\mathrm{CH}}_{2}\\qquad{\\mathrm{OH}}\\qquad{\\mathrm{OH}}\\qquad{\\mathrm{CH}}_{2}}\\\\ {\\stackrel{\\mathrm{i}}{\\mathrm{NH}}_{2}\\qquad{\\mathrm{NH}}_{2}}\\end{array}\n$$  \n\n除了用环氧树脂（上式中的R）与胺反应制造加成物外，也可用单环氧化合物，例如丁基缩水甘油醚与二乙烯三胺加成：  \n\n市上出售的商品都是提净的胺加成物(应注明其胺氢当量)。现场配制的加成物都是自行配制，其性能不及提净加成物。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 337,
+        "chunk": "# 4.聚酰胺固化环氧树脂漆  \n\n涂料工业的聚酰胺指含有活泼氨基的聚酰胺树脂，是在双组分环氧涂料中广泛应用的固化剂。它是继加成物之后，由美国GeneralMills公司在20世纪60年代开发成功的。商品名为Versamid，amid指amide 酰胺，Versa 指versatile“能泛用”。现今由Cognis公司生产，类似产品很多，我国也有生产。  \n\n早期GeneralMills用大豆油脂肪酸在高压釜聚合，制得二聚酸Dimer acid。现今大多用松浆油酸聚合。  \n\n![](images/65d3434fb13b7239a19c5e37fe2638f30edbeb29fcc8e2cea7de3f3b0fa5b043.jpg)  \n二聚酸  \n\n此类二聚酸在国外均由专门工厂大量生产出售，我国也有生产二聚酸(华生化工厂)。UnionCamp公司产品示例见表2-1-131。  \n\n表2-1-131 UnionCamp公司产品  \n\n\n<html><body><table><tr><td>产品 编号</td><td>酸值 /(mgKOH/g)</td><td>皂化值 /(mgKOH/g)</td><td>色泽 (加氏管)</td><td>单羧酸 /%</td><td>二聚酸 /%</td><td>三聚酸 /%</td><td>运动粘度 /(10~*m²/s)</td></tr><tr><td>14号</td><td>196</td><td>201</td><td></td><td>0.4</td><td>96</td><td>3</td><td>71</td></tr><tr><td>18号</td><td>194</td><td>201</td><td></td><td>0.8</td><td>86</td><td>14</td><td>90</td></tr></table></body></html>  \n\n从表2-1-131可见，14号的酸值高，色泽浅淡，二聚体含量高，是优质产品。在聚合过程中若温度太高会发生脱羧反应，使酸值降低，产生不皂化物，不能与多元胺缩合。  \n\n用二聚酸与多元胺（如二乙烯三胺）缩合成聚酰胺：HOOC-E\\~\\~}-COOH+2HNCH—N—-CHNH—  \n\n![](images/66b3da7d05e0a4d90dd1a8915811bd8393836c8549dd7a7d56b495a6a3368d05.jpg)  \n\n下列是商品Versamid的性质。  \n\n$\\Phi$ Versamid 100号  \n\n<html><body><table><tr><td>肢值</td><td>85～95mgKOH/g</td><td>色泽（加氏）</td><td>最高9</td></tr><tr><td>每含1mol活泼氢的克数</td><td>525g</td><td>相对密度（25℃）</td><td>0.97</td></tr><tr><td>黏度（120C)</td><td>3~5Pa·s</td><td></td><td></td></tr><tr><td colspan=\"4\">与环氧（601型）配比：</td></tr><tr><td colspan=\"4\">求最高T(DSC法）时应为环氧：Versamid100 号=100：100</td></tr><tr><td>施工时限（60%固体分）</td><td>16h</td><td>实干（25℃)</td><td>48h</td></tr><tr><td>表干（25℃)</td><td>1.5h</td><td></td><td></td></tr><tr><td colspan=\"4\">②Versamid 115号</td></tr><tr><td>胺值</td><td>230~246mgKOH/g</td><td>色泽（加氏）</td><td>最高8</td></tr><tr><td>每含1mol活泼氢的克数</td><td>198g</td><td>相对密度(25C)</td><td>0.97</td></tr><tr><td>黏度（75℃）</td><td>3. 1~4. 5Pa • s</td><td></td><td></td></tr><tr><td colspan=\"4\">与环氧配比（828型液体环氧）：</td></tr><tr><td colspan=\"4\">求最高T(DSC法）时应为环氧：Versamid115号=100+104</td></tr><tr><td>T</td><td>62℃</td><td>表干(25℃)</td><td>4.25h</td></tr><tr><td>施工时限（60%固体分）</td><td>4h</td><td>实干</td><td>6h</td></tr><tr><td colspan=\"4\">③Versamid 125号</td></tr><tr><td>胺值</td><td>330~360mgKOH/g</td><td>色泽(加氏）</td><td>最高8</td></tr><tr><td>每含1mol活泼氮的克数</td><td>103g</td><td>相对密度（25℃）</td><td>0.97</td></tr><tr><td colspan=\"4\">黏度（75℃）</td></tr><tr><td colspan=\"4\">与环氧（828型）配比：</td></tr><tr><td colspan=\"4\">求最高T（DSC法）时应为环氧：Versamid125号=100：54</td></tr><tr><td>T</td><td>84C 2h</td><td>实干</td><td>12h</td></tr><tr><td>施工时限（60%固体分）</td><td></td><td>胶化时间（200g量，25C）</td><td>2.15h</td></tr><tr><td>表干</td><td>5h</td><td></td><td></td></tr><tr><td colspan=\"4\">④Versamid 140号</td></tr><tr><td>胺值</td><td>370~400mgKOH/g</td><td>色泽（加氏）</td><td>最高8</td></tr><tr><td>每含1mol活泼氢的克数</td><td>97g 8~12Pa • s</td><td>相对密度（25℃）</td><td>0.96</td></tr><tr><td colspan=\"4\">黏度（25℃）</td></tr><tr><td colspan=\"4\">与环氧配比（828型液体环氧）： 求最高T（DSC法）时应为环氧：Versamid140号=100·51</td></tr><tr><td colspan=\"4\"></td></tr><tr><td>T</td><td>93C</td><td>表干（25℃）</td><td>6.5h</td></tr><tr><td>施工时限（60%固体分）</td><td>3. 5h</td><td>实于(25C)</td><td>12h</td></tr></table></body></html>  \n\n在前面示意式中共有2个伯氨基，2个仲氨基，共有6个活泼氢原子。酰氨基不参加反应。胺值较高牌号的树脂则用三乙烯四胺作原料。  \n\n由于二聚脂肪酸的长链起到内增塑作用，使涂膜具有韧性。涂膜有酰氨基、羟基等，故附着力优良，而且其结构的一端有极性的氨基，另一端有非极性长链烃基，相似于典型的表面活性剂，故在潮湿表面有能附着并置换水膜的能力，甚至可用作水下施工涂料。  \n\n聚酰胺树脂是黏稠的树脂，不溶于水，不同于水溶性的胺类固化剂（如二亚乙基三胺）。后者与环氧树脂配漆时必须称量准确，太少则固化不足，太多则不利于抗水性，而聚酰胺与环氧的配比可在一定范围内变动而获得所需的性能。由于具有上述优点，聚酰胺树脂广泛应用于一般的环氧维护防腐蚀漆。但是它的干燥速率较慢，寒冷温度下更困难，必须酌加DMP-30等催干剂，其抗溶剂，抗化学品性亦稍逊于脂肪胺类固化剂，因为交联密度较低。  \n\n一般的溶剂型环氧涂料，常采用E-20环氧树脂和类似Versamid115的固化剂，应用广泛。有些大型民航飞机蒙皮，是采用含铬酸锶的环氧聚酰胺底漆，上罩脂肪族聚氨酯面漆。新开发的水性环氧漆也常与溶剂型环氧/聚酰胺涂料作参比标准，以证明水性环氧漆已达到溶剂型环氧漆的性能。此类涂料广泛应用作常温干燥的防腐蚀底漆等。对于公交车等大型车辆的环氧底漆则可采用强制干燥（ForcedDry）在60～80℃烘干，不仅缩短工时，提高产量，而且大大提高涂层性能。表2-1-132为聚酰胺环氧树脂漆配方（质量份）。  \n\n表2-1-132 聚酰胺环氧树脂漆配方  \n\n\n<html><body><table><tr><td></td><td>原料</td><td></td><td>（喷）</td><td>清漆</td></tr><tr><td rowspan=\"6\">甲组分</td><td>环氧树脂E-20</td><td>12</td><td>33</td><td>50</td></tr><tr><td>混合溶剂</td><td>40</td><td>34</td><td>50</td></tr><tr><td>氧化铁红</td><td>38</td><td></td><td></td></tr><tr><td>锌黄</td><td>8</td><td></td><td></td></tr><tr><td>云母粉</td><td>2</td><td></td><td></td></tr><tr><td>钛白(金红石)</td><td></td><td>33</td><td></td></tr><tr><td rowspan=\"4\">乙组分</td><td>合计</td><td>100</td><td>100</td><td>100</td></tr><tr><td>聚酰胺（胺值200）</td><td>4.2</td><td>11. 5</td><td>17.5</td></tr><tr><td>混合溶剂</td><td>4.2</td><td>11.5</td><td>17.5</td></tr><tr><td>合计</td><td>8.4</td><td>23.0</td><td>35.0</td></tr></table></body></html>  \n\n上述环氧树脂与聚酰胺的比例约为 $3:1$ ，实际上聚酰胺树脂的胺值仅表示其碱性氮原子的浓度，并不反映其所含活泼氢原子的数量，所以环氧树脂与聚酰胺树脂的配比可按产品的技术要求而变动。  \n\n聚酰胺树脂的胺值是指其在用HCI滴定时所含碱性氮原子的量，用以控制每批制造产品的质量稳定。但氮原子可能为伯胺（含两个活泼氢）或仲胺（仅含一个活泼氢)，所以其胺氢当量不同于胺值。配制环氧涂料时应按每个环氧基团配一个活泼氢，并可略予调动以求最优化。配漆时可用Versamid100、115、125，其中115应用较多。开林造漆厂用自制的650树脂，下面仅是示例。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 338,
+        "chunk": "# $\\Phi$ 环氧铁红底漆  \n\n<html><body><table><tr><td>甲组分</td><td></td><td></td><td></td></tr><tr><td>环氧树脂E-20(50%溶液)</td><td>43.7g</td><td>滑石粉</td><td>12.8g</td></tr><tr><td>氧化铁红</td><td>16.6g</td><td></td><td></td></tr><tr><td>乙组分</td><td></td><td></td><td></td></tr><tr><td>100号聚酰胺</td><td>15.4g</td><td>丁醇</td><td>2.4g</td></tr><tr><td>甲乙酮</td><td>3.5g</td><td>二甲苯</td><td>5.6g</td></tr><tr><td>②环氧富锌底漆</td><td></td><td></td><td></td></tr><tr><td>甲组分</td><td></td><td></td><td></td></tr><tr><td>环氧树脂E-20（75%溶液）</td><td>61g</td><td>丙二醇甲醚</td><td>30g</td></tr><tr><td>甲基异丁基酯</td><td>30g</td><td>膨润土（Bentone27）</td><td>10g</td></tr><tr><td>二甲苯</td><td>30g</td><td>锌粉</td><td>920g</td></tr><tr><td>乙组分</td><td></td><td></td><td>7</td></tr><tr><td>聚酰胺115号（60%溶液）</td><td>41g</td><td>丙二醇甲醚</td><td>27g</td></tr><tr><td>甲基异丁基酮</td><td>22g</td><td>二甲萃</td><td>23g</td></tr></table></body></html>  \n\n此配方涂料PVC为 $65.8\\%$ ，溶剂中的醇羟基能促进固化，酮能与胺形成氢键，阻缓固化（延长施工时限)，不可用酯类溶剂，以免被碱性胺所氨解，丙二醇甲醚水溶性大，若太多残留涂膜中会影响耐水性。乙二醇乙醚不可用，因会引起致畸之弊。  \n\n典型的聚酰胺环氧树脂漆配方（质量份）见表2-1-133、表2-1-134举例。  \n\n表2-1-133 聚酰胺环氧树脂漆配方（一）  \n\n\n<html><body><table><tr><td>原 料</td><td>底漆</td><td>琪色）</td><td>原料</td><td>底漆</td><td>(色）</td></tr><tr><td>成分一：</td><td></td><td></td><td>E-20环氧树脂</td><td>17.18</td><td>36.35</td></tr><tr><td>柠檬铬黄</td><td>12.12</td><td>一</td><td>30%丁醇、70%二甲苯混合溶剂</td><td>17.18</td><td>36.35</td></tr><tr><td>锌铬黄</td><td>9.92</td><td>一</td><td>硅油溶液（1%）</td><td></td><td>0.50</td></tr><tr><td>氧化锌</td><td>7.45</td><td>一</td><td>合计</td><td>72.07</td><td>100</td></tr><tr><td>滑石粉（325目）</td><td>2.72</td><td>一</td><td>成分二：</td><td></td><td></td></tr><tr><td>铝粉浆（固体60%）</td><td>5.50</td><td></td><td>聚酰胺树脂（胺值200）</td><td>11.5</td><td>20</td></tr><tr><td>钛白粉（金红石型）</td><td>一</td><td>26.40</td><td>30%丁醇、70%二甲苯混合溶剂</td><td>11.5</td><td>20</td></tr><tr><td>酸菁蓝</td><td>一</td><td>0.40</td><td>合计</td><td>23.0</td><td>40</td></tr></table></body></html>  \n\n附着力（划圈法） $2\\sqrt{\\alpha}$ 耐人造海水腐蚀 浸6个月涂膜无明显变化 弯曲试验 $3\\mathrm{mm}$ 耐湿热性（42℃±1℃，相对 6个月后涂膜颜 冲击强度 490.3N · cm 湿度95%） 色发花，无气泡  \n\n按上述配方制得聚酰胺环氧树脂漆的性能：  \n\n\n<html><body><table><tr><td>原料</td><td></td><td>）</td><td>（）</td><td>原料</td><td></td><td>（喷）</td><td>（）</td></tr><tr><td>成分一： 环氧树脂</td><td>12</td><td>33</td><td>50</td><td>钛白（金红石型） 合计</td><td>一 100</td><td>33 100</td><td>一</td></tr><tr><td>（环氧当量500）</td><td></td><td></td><td></td><td></td><td></td><td></td><td>100</td></tr><tr><td>混合溶剂</td><td>40(A)</td><td>34(A)</td><td>50(B)</td><td>成分二：</td><td></td><td></td><td></td></tr><tr><td>氧化铁红</td><td>38</td><td>一</td><td>一</td><td>聚酰胺（胺值200）</td><td>4.2</td><td>11.5</td><td>17.5</td></tr><tr><td>锌黄</td><td>8</td><td>一</td><td>一</td><td>混合溶剂</td><td>4. 2(C)</td><td>11. 5(C)</td><td>17.5(D)</td></tr><tr><td>云母粉</td><td>2</td><td>一</td><td></td><td>合计</td><td>8.4</td><td>23.0</td><td>35.0</td></tr></table></body></html>  \n\n一般的聚酰胺树脂常含有些游离的脂肪族多元胺，在寒冷气候下涂装时会与空气中的CO2反应生成盐，使涂膜发雾，影响层间附着力，所以后来又开发了聚酰胺加成物（poly-amide adduct)，是将聚酰胺树脂与少量环氧树脂反应，减少游离胺，则双组分混合后不必熟化，并能在寒冷气候下施工，减少成盐之。国外典型商品例如Huntsman 公司的 Ara-dur 450，Cognis公司的Versamid224、225、226、228、229、280六种，Air Products 公司也生产了7种聚酰胺加成物。  \n\n表2-1-134聚酰胺环氧树脂漆配方（二）  \n\n\n<html><body><table><tr><td>E-20环氧树脂（75%溶液) 双酚A/F液体环氧树脂</td><td>17.8g 13.4g</td><td>磷酸锌系防锈颜料 滑石粉</td><td>7.3g 24.5g</td></tr><tr><td>消泡剂BYK057</td><td>0.5g</td><td>BaSO</td><td>9.6g</td></tr><tr><td>FeO</td><td>4. 9g</td><td></td><td></td></tr><tr><td>乙组分</td><td></td><td></td><td></td></tr><tr><td>固化剂450</td><td>11.1g</td><td>涂料的PVC</td><td>约29%</td></tr><tr><td>芳香羟溶剂 混合后涂料的固体含量</td><td>5.3g 约85%（质量分数）</td><td>涂料的VOC</td><td>约250g/L</td></tr></table></body></html>  \n\n此Aradur450聚酰胺加成物型固化剂，它的活泼氢当量AHEW为115，与环氧树脂可配制高固体涂料，示例如下：",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 339,
+        "chunk": "# 甲组分",
+        "category": " Introduction"
+    },
+    {
+        "id": 340,
+        "chunk": "# 5.环氧沥青涂料  \n\n环氧沥青涂料是一种广泛应用的防腐蚀涂料。环氧涂料中配人煤焦沥青有下列特点：  \n\n$\\textcircled{1}$ 提高了抗水性；  \n$\\textcircled{2}$ 降低了成本，提高了固体含量；  \n$\\textcircled{3}$ 对除锈不够充分的钢铁表面，其适应性比纯环氧涂料较好些。  \n\n此类涂料附着力好，耐水浸渍，不能做浅色漆，涂膜受日光长期照射时会失光、龟裂，不宜用于受日晒表面，常用于水下结构，户内结构等，开林造漆厂用于南浦大桥的箱形结构的内壁。如必须着色，则用氧化铁红、炭黑等颜料，有助于耐日晒，遮蔽日光。  \n\n配制环氧沥青漆所用的环氧树脂大多选用E-42（即Epon834DER337等类似产品）较宜，因其分子量低，可制成高固体厚膜，对溶剂的溶解力要求亦较低，混溶性亦较好。但分子量太低的Epon828型近似纯的双酚A缩水甘油醚，分子中缺少羟基，不能催化环氧基与胺的反应，漆的固化较慢，若用E-20则固体含量低，溶剂要求较高。  \n\n我国选用软化点约 $50\\mathrm{{^Y}}$ 左右的煤焦沥青，但因其来源性质差异，必须与环氧树脂配合良好者选用之。国外称此类涂料为焦油环氧（Tarepoxy)。若选用普通焦油，其中挥发分较多，日久会从涂膜中逸失。煤焦沥青中含有苯并芘等有毒害物质，以往环氧沥青涂料大量涂布于船舶的压载水舱内壁，现已国际上禁用，因船航行到港后，排出舱水，会将苯并等污染港湾。  \n\n涂料配方中环氧树脂与沥青的比例，以 $1:1$ 配制，则漆的性能较好。若采用 $1:2$ 配制，则性能稍差些，但成本降低，而且沥青多的漆，较能适应除锈不彻底的表面，故用于防腐蚀要求稍低的场合。  \n\n欧伯兴介绍了日本规格JISK5664焦油环氧树脂涂料，分为1型、2型，实质反映其中含环氧树脂的多少：  \n\n耐烃类浸渍 耐NaOH(50g/t)浸渍  \n\n1型 耐（石油醚：甲苯为8112)48h无异状 168h无异状  \n\n2型   \n耐煤油168h无异状   \n120h无异状  \n\n从以上两个型号比较可看出，耐烃类浸渍，石油醚溶解力比煤油强，再加上 $20\\%$ 芳烃甲苯，其溶解力比煤油强得多，实质上限定1型涂膜中必须有足够的环氧树脂。在耐 $\\mathbf{NaOH}$ 浸渍方面，因焦油中常含酚类，不耐碱，所以1型耐碱时间长，即限制其不可含沥青太多（表2-1-135)。  \n\n表2-1-135环氧沥青漆配方 单位：质量份  \n\n\n<html><body><table><tr><td>原料</td><td>底漆</td><td>中层漆</td><td>面漆</td><td>清漆</td><td>原料</td><td>底漆</td><td>中层漆</td><td>面漆</td><td>清漆</td></tr><tr><td>组分一</td><td></td><td></td><td></td><td></td><td>组分二</td><td>2.8</td><td></td><td></td><td></td></tr><tr><td>环氧树脂（E-20) 滑石粉</td><td>11.3</td><td>11.2 31.5</td><td>19.6 15.8</td><td>28.0 一</td><td>聚酰胺（胺值300) 二甲萃</td><td>2.8</td><td>2.8 2.8</td><td>4.9 4.9</td><td>7.0 7.0</td></tr><tr><td>氧化铁红</td><td>30.2 11.3</td><td>10.5</td><td>5.2</td><td></td><td>配比</td><td></td><td></td><td></td><td></td></tr><tr><td>四碱式锌铬黄</td><td>7.5</td><td></td><td>一</td><td>一</td><td>环氧/沥青（质量比）</td><td>1.7/1</td><td>0.8/1</td><td>0.8/1</td><td>0.8/1</td></tr><tr><td>煤焦沥青</td><td>6.7</td><td>14.0</td><td>24.5</td><td>35.0 25.1 23</td><td>环氧/聚酰胺（质量比）</td><td>4/1</td><td>4/1</td><td>4/1</td><td>4/1</td></tr></table></body></html>\n\n$\\Phi$ 混合溶剂组成为：甲苯1环己酮二甲苯·醋酸丁酯=43121.  \n\n以上表中的配方，是环氧树脂与煤焦沥青混合作为一个组分，另一组分是胺类固化剂。国外也有推荐将环氧树脂作为一个组分，另一组分是沥青加固化剂，笔者见进口涂料有此种组合方法。其理由是煤焦沥青的成分复杂，取决于焦化时煤的种类和焦化条件，往往含有胺、酚等，可能与环氧树脂反应。选用沥青是否合用，须将其与环氧树脂混合后测其黏度，隔数星期后再测黏度，如明显上升则表示发生了反应。以下是Dow公司推荐的配方示例。  \n\n<html><body><table><tr><td>甲组分：</td><td></td><td></td><td></td></tr><tr><td>环氧树脂DER337（接近于我国的E-42）</td><td>283.5g</td><td>气相二氧化硅（增厚作用）</td><td>6.7g</td></tr><tr><td>(0%整减)</td><td></td><td>二甲</td><td>57. 68</td></tr><tr><td></td><td>250.0g</td><td></td><td></td></tr><tr><td>乙组分：</td><td></td><td></td><td></td></tr><tr><td></td><td>39.08</td><td>二甲苯</td><td>436.0</td></tr><tr><td>煤乙基三酸</td><td></td><td></td><td></td></tr><tr><td>正丁醇</td><td>33.5g</td><td></td><td></td></tr></table></body></html>  \n\n可见沥青是与固化剂混合作为一个组分。配方中的二亚乙基三胺可用等摩尔的聚酰胺树脂或酚醛胺代替。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 341,
+        "chunk": "# 6.环氧酚醛胺、环氧异氰酸酯涂料  \n\n上述的双组分涂料，在常温下固化良好，一般在7天后已大部固化，有些聚酰胺固化稍慢，须加DMP-30等催化。  \n\n但在实际应用施工时，往往环境温度较低，酚醛胺或多异氰酸酯即是供低温时用的固化剂。  \n\n酚醛胺中含有酚羟基，能促进胺与环氧基反应。  \n\n![](images/a0e01b7170a35269501102bf72d39eb1306a754bbc557c8fa5ff4815443d7253.jpg)  \n\n另一种低温固化剂是多异氰酸酯。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 342,
+        "chunk": "# 7.多异氰酸酯固化环氧树脂漆  \n\n高分子量的环氧树脂的仲羟基与多异氰酸酯的交联反应，在室温或较低温度下即可进行。因此可以制成常温干型涂料。干燥的涂膜具有优越的耐水性、耐溶剂性、耐化学品性和柔韧性。可用于涂装耐水设备或化工设备等。  \n\n多异氰酸酯的异氰酸基和环氧树脂的羟基反应生成聚氨基甲酸酯，而使涂膜固化，其反应如下式所示：  \n\n![](images/265c375a2a3266601577e9172d577282f92295da3b6fe79da21d52abe7d48617.jpg)  \n\n异氰酸酯固化环氧树脂漆一般是双组分的。环氧树脂、溶剂（色漆应加颜料）为一个组分；多异氰酸酯为另一个组分。适用的环氧树脂为分子量1400以上的。固化剂一般用二异氰酸酯和多元醇的加成物。  \n\n多异氰酸酯环氧磁漆配方（质量份）如下。  \n\n<html><body><table><tr><td colspan=\"3\">组分一：</td></tr><tr><td>钛白</td><td>34.0</td><td rowspan=\"3\">环己酮 丙二醇甲醚酯酸酯</td></tr><tr><td>环氧树脂（E-03）</td><td>21.0</td></tr><tr><td>环己酮树脂（流平助剂之用）</td><td>2.0 二甲苯</td></tr><tr><td>组分二：</td><td></td><td>10.75</td></tr><tr><td>TDI加成物（75%）</td><td>18.0</td><td></td></tr><tr><td colspan=\"3\">TDI加成物是甲苯二异氰酸酯和三羟甲基丙烷的加成物，其主要规格：</td></tr><tr><td>固体含量（醋酸乙酯溶液）</td><td></td><td>0.5%以下</td></tr><tr><td>异氰酸基含量</td><td>75%±1% 13.0%±0.5%</td><td>游离甲苯二异氰酸酯</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 343,
+        "chunk": "# 配比：  \n\n组分一  \n\n表2-1-136为用多异氰酸酯固化及用聚酰胺固化的环氧树脂性能比较。  \n\n表2-1-136用多异氰酸酯固化及用聚酰胺固化环氧树脂性能  \n\n\n<html><body><table><tr><td>环氧树脂</td><td>E-03型</td><td>E-20型</td><td>环氧树脂</td><td>E-03型</td><td>E-20型</td></tr><tr><td>固化剂</td><td>TDI/TMP加成物</td><td>聚酰胺（115)</td><td>固化剂</td><td>TDI/TMP加成物</td><td>聚酰胺（*115)</td></tr><tr><td>硬度（摆杆Persoz)/s</td><td></td><td></td><td>杯突试验/mm</td><td></td><td></td></tr><tr><td>20°C,1d</td><td>190</td><td>158</td><td>20°C.7d后</td><td>8.0~8.2</td><td>8.7~8.6</td></tr><tr><td>20℃C,7d</td><td>355</td><td>330</td><td>60°C,180min后</td><td>9.0</td><td>8.3~8.7</td></tr><tr><td>60°C,3h</td><td>355</td><td>387</td><td>120°C,90min后</td><td>5.1~5.5</td><td>8.0~8.4</td></tr><tr><td>120°C,90min</td><td>405</td><td>390</td><td></td><td></td><td></td></tr></table></body></html>  \n\n从表2-1-136可见，用多异氰酸酯固化的环氧树脂，经高温 $(120^{\\circ}\\mathrm{C}$ ）处理后，其伸展性有所下降。  \n\n表2-1-137为用多异氰酸酯固化及用聚酰胺固化的环氧树脂漆涂膜的抗沸水性$98\\%$ ，4h)。  \n\n表2-1-137用多异氰酸酯及用聚酰胺固化的环氧树脂漆的抗沸水性  \n\n\n<html><body><table><tr><td>固化条件</td><td>多异氰酸酯固化</td><td>聚酰胺固化</td><td>固化条件</td><td>多异氰酸酶固化</td><td>聚酰胺固化</td></tr><tr><td>20℃,7d</td><td>无泡~微泡/失光</td><td>严重起泡/失光</td><td>120°C,90min</td><td>无泡/失光</td><td>严重起泡/失光</td></tr><tr><td>60°C,180min</td><td>无泡/失光</td><td>微泡/失光</td><td>150°C.60min</td><td>无泡/不失光</td><td>严重起泡/失光</td></tr></table></body></html>  \n\n表2-1-138为用多异氰酸酯固化及用聚酰胺固化的环氧树脂漆涂膜的抗溶剂性能比较（浸入二甲苯/丁醇混合物两天）。  \n\n表2-1-138用多异氰酸酯及用聚酰胺固化的环氧树脂漆的抗溶剂性  \n\n\n<html><body><table><tr><td>固化条件</td><td>多异氰酸酯固化</td><td>聚酰胺固化</td><td>固化条件</td><td>多异氰酸酯固化</td><td>聚酰胺固化</td></tr><tr><td>20C,10d</td><td>15个月后破坏</td><td>3个月后破坏</td><td>120°C,90min</td><td>良好</td><td>3个月后破坏</td></tr><tr><td>60°C,180min</td><td>3个月后破坏</td><td>3个月后破坏</td><td>150°C,60min</td><td>良好</td><td>3个月后破坏</td></tr></table></body></html>  \n\n从表2-1-138可见，多异氰酸酯固化的环氧树脂的耐溶剂性优于聚酰胺固化的环氧树脂（当然，若改变环氧树脂的分子量及固化剂也可提高耐溶剂性)。上述结果是由于高分子量的环氧树脂，往往每分子中含有 $10{\\sim}15$ 个羟基，经多异氰酸酯固化，交联密度大。但每个环氧树脂分子中仅含两个环氧基供聚酰胺交联，交联密度较低。因此，多异氰酸酯固化的环氧树脂漆涂膜交联密度高，而对金属的附着力较低，经弯曲易剥落，尤其在光滑的铝板等表面，不及环氧/聚酰胺涂料。在寒冷气候施工，则多异氰酸酯的固化速度比聚酰胺的快，而且耐酸性也优于聚酰胺固化的涂膜。  \n\n除了上述方式固化之外，尚有一种方式是用二乙醇胺（或二异丙醇胺）先与环氧树脂反应，则环氧基会开环生成较多羟基，而胺的氮原子更具有催化作用，促进异氰酸基与羟基反应：  \n\n![](images/13dbfc0bd7276245e73b41b6f10f05a285d0bc87ecbc81c10dffbbe2d96cd4b8.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 344,
+        "chunk": "# 8.环氧酯涂料  \n\n环氧酯是环氧树脂与植物油脂肪酸反应酯化而成，实质上视环氧树脂作为优质的多元醇，故产品稍类似于醇酸树脂。它是单组分的，贮存稳定性好，有烘干型的，也有常温干型的，烘干温度也较低（约 $120\\Upsilon$ )，施工方便。环氧酯漆可以由不同品种的脂肪酸以不同的配比与环氧树脂反应制得，因而涂膜性能是多样的。环氧酯可溶于价廉的烃类溶剂中，成本较低。环氧酯与其他树脂混溶性较好，如与氨基树脂或酚醛树脂并用，可制成性能不同的烘干型漆，因环氧酯中含有酯基，故耐碱性较弱。但比醇酸树脂漆的耐碱性好。环氧酯可以制成清漆、磁漆、底漆和腻子等。  \n\n环氧酯漆用途很广，是目前我国环氧树脂涂料中生产较大的一种。如各种金属底漆、化工厂室外设备防腐蚀漆等。环氧酯底漆对铁、铝金属有很好的附着力，大量用于拖拉机或其他设备打底。近年来我国水稀释性环氧酯底漆应用于阳极电泳涂漆工艺中。  \n\n(1）酯化反应脂肪酸的羧基与环氧树脂的环氧基和羟基发生酯化反应，生成环氧酯。以无机碱或有机碱作催化剂，反应可加速进行。  \n\n环氧基比羟基活泼，所以羧基与环氧基反应先发生，称为加成酯化，并无水析出。其次是羟基与羧基发生反应，反应过程如下式：  \n\n除了上述酯化反应外，环氧基和羟基还可能发生醚化反应，脂肪酸的双键还有聚合反应。  \n\n(2）酯化程度环氧酯的酯化程度的表示方法有两种，一种是以酯化物所用脂肪酸的酯化当量数表示。如 $40\\%$ 酯化脱水麻油酸环氧酯；一种是以酯化物所含脂肪酸的含量百分比来表示，如 $40\\%$ 脱水麻油酸环氧酯。两种表示方法以第一种较为确切通用。酯化当量与脂肪酸百分含量之间的关系如表2-1-139所示。  \n\n表2-1-139 化当量与脂肪酸百分含量的关系  \n\n\n<html><body><table><tr><td>环氧树脂酯化当量数</td><td>脂肪酸/mol</td><td>脂肪酸占酯化物比例/%</td></tr><tr><td>1. 0</td><td>0.3~0.5</td><td>32~44</td></tr><tr><td>1. 0</td><td>0.5~0.7</td><td>44~53</td></tr><tr><td>1.0</td><td>0.7~0.9</td><td>53~59</td></tr></table></body></html>  \n\n在制备环氧酯时，通常是将环氧树脂部分地酯化，因为这样可以更多地保留环氧树脂的特性。环氧酯的酯化程度一般在 $40\\%\\sim80\\%$ 。具体的酯化程度则应根据涂膜的性能要求决定。一般说来，制备空气干燥的环氧酯时，酯化程度在 $50\\%$ 以上，使环氧酯中含有足够的脂肪酸双键，以便进行氧化聚合而干燥。制备烘干的环氧酯时，酯化程度可在 $50\\%$ 以下。通过酯化物中的剩余羟基和并用树脂中活泼基团进行交联，而使涂膜干燥。  \n\n环氧酯的性能与脂肪酸用量有密切关系，当脂肪酸用量增加时，黏度、硬度降低，对溶  \n\n剂的溶解性增加，刷涂性、流平性改善。干燥速度以中油度最好，一般室外耐久性也较好。  \n但环氧酯涂料中因含大量醚键，耐晒性不如醇酸树脂漆好。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 345,
+        "chunk": "# (3）原料的选择  \n\n$\\Phi$ 环氧树脂适于酯化的环氧树脂分子量有：900、1400和2900。常用的环氧树脂规格见表2-1-140。  \n\n表2-1-140用于酯化的环氧树脂规格  \n\n\n<html><body><table><tr><td>树脂型号</td><td>环氧值</td><td>酯化当量（约）</td><td>平均分子量（约）</td></tr><tr><td>E-20(1 601)</td><td>0.18~0.22</td><td>130</td><td>900</td></tr><tr><td>E-12(旧604)</td><td>0.09~0.14</td><td>175</td><td>1400</td></tr><tr><td>E-06(旧607)</td><td>0.04~0.07</td><td>190</td><td>2900</td></tr></table></body></html>  \n\n通常如果环氧树脂的分子量大，其酯化物的耐化学品性能高。但是树脂中羟基较多，在加热酯化时，酯化物黏度上升快，在制造时操作控制困难。制成的清漆黏度大，与其他树脂的混溶性不好。通常以E-12（604型）树脂采用最普遍。国外的Epon1004、Dow公司的DER664中均预加有酯化的催化剂。  \n\n$\\textcircled{2}$ 脂肪酸制造常温干型环氧酯时，主要选用干性油脂肪酸，如亚麻油酸、桐油酸等。制造烘干型环氧酯时，常选用脱水麻油酸、椰子油酸等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 346,
+        "chunk": "# （4）环氧酯漆的配制  \n\n$\\Phi$ 环氧酯漆配方的拟定主要是改变所用脂肪酸的品种和配比，以满足涂料性能要求。通常，配制常温干燥漆时，应采用干性油脂肪酸，酯化程度以 $60\\%\\sim90\\%$ 为宜。同时应加入催干剂使涂膜进行氧化聚合干燥，催干剂常用环烷酸钴，金属钴用量为环氧酯不挥发分的$0.04\\%$ 左右。不宜使用铅催干剂，因短期贮存即会产生沉淀。配制烘干型漆时，宜采用不干性油脂肪酸，酯化当量在0.5以下。催干剂可不用或少量使用，金属钴用量为清漆不挥发分的 $0.005\\%\\sim0.01\\%$ 。常与氨基树脂并用（不超过 $40\\%$ ）制成耐化学品性好的、颜色浅的漆。脱水麻油酸的环氧酯（ $40\\%$ 酯化，习称为D-4）常用于烘干漆。  \n\n环氧酯清漆加入颜料、体质颜料等可以制成磁漆、底漆和腻子等品种，对颜料选用无特殊要求。  \n\n$\\textcircled{2}$ 配方计算 $50\\%$ 酯化的亚麻油酸环氧酯的配方计算见表2-1-141。  \n\n表2-1-14150%酯化的亚麻油酸环氧醋的配方   \n\n\n<html><body><table><tr><td>原料</td><td>每摩尔的质量/g</td><td>摩尔比</td><td>实用质量/g</td><td>质量/%</td></tr><tr><td>E-12环氧树脂</td><td>175</td><td>1. 0</td><td>175</td><td>55.6</td></tr><tr><td>亚麻油酸 合计</td><td>280</td><td>0.5</td><td>140 315</td><td>44.4 100.0</td></tr></table></body></html>  \n\n表2-1-142为环氧酯配方举例，表2-1-143为环氧酯氨基底漆配方。  \n\n表2-1-142环氧酯配方举例 单位：质量份   \n\n\n<html><body><table><tr><td>原料</td><td>A 长油度</td><td>B. 中油度</td><td>C 中油度</td><td>D 短油度</td><td>E 中油度</td></tr><tr><td>E-12环氧树脂</td><td>43.5</td><td>50.7</td><td>50</td><td>60</td><td>50</td></tr><tr><td>亚麻油酸</td><td>56.6</td><td>49.3</td><td></td><td></td><td></td></tr><tr><td>脱水麻油酸</td><td></td><td></td><td>40</td><td>40</td><td></td></tr><tr><td>桐油酸</td><td></td><td></td><td>10</td><td></td><td>10</td></tr><tr><td>梓油酸</td><td></td><td></td><td></td><td></td><td>40</td></tr><tr><td>酯化程度</td><td>0.82</td><td>0.6</td><td>0.6</td><td>0.4</td><td>0.6</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>原料</td><td>长油度</td><td>中度</td><td>中油度</td><td>短油度</td><td>中油度</td></tr><tr><td>200号油漆溶剂油</td><td>100</td><td></td><td></td><td></td><td></td></tr><tr><td>二甲苯</td><td></td><td>100</td><td>100</td><td>100</td><td>100</td></tr><tr><td>不挥发分/%</td><td>50</td><td>50</td><td>50</td><td>50</td><td>50</td></tr><tr><td>酸值（固体）</td><td>7~10</td><td><3</td><td><5</td><td><5</td><td><8</td></tr><tr><td>黏度 （气泡法,25℃)/s</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>（涂-4,25°℃）/s</td><td>7~13 一</td><td>6~9 一</td><td><8 一</td><td><6 一</td><td>一 200~400</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td>干性底辣和自成供干糖自干或烘干底干</td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>应用范围</td><td></td><td></td><td></td><td></td><td>自干底漆腻子</td></tr></table></body></html>  \n\n环氧酯氨基底漆性能：  \n\n\n<html><body><table><tr><td>干燥时间（120C）</td><td>1h</td><td>弯曲试验</td><td>1mm</td></tr><tr><td>硬度</td><td>0.4</td><td>耐水性(50蒸馏水)</td><td>8h不起泡</td></tr><tr><td>冲击强度</td><td>490.3N·</td><td></td><td></td></tr></table></body></html>  \n\n表2-1-143中所述铁红环氧底漆适用于钢铁；锌黄环氧底漆适用于铝和铝合金表面打底。表中配方含有少量丁醚化三聚氰胺树脂是某造漆厂欲将此底漆作为既可常温干燥，又可烘烤干的涂料。若除去三聚氰胺树脂，则常温干燥会快些，因为三聚氰胺树脂在常温不会干燥。用作烤漆则氨基树脂又太少。  \n\n表2-1-143环氧酯氨基底漆配方 单位：质量份  \n\n\n<html><body><table><tr><td rowspan=\"2\">原料</td><td rowspan=\"2\">环氧底漆</td><td rowspan=\"2\">烘干铁红 烘干锌黄 环氧底漆</td><td rowspan=\"2\"></td><td rowspan=\"2\">烘干铁红 环氧底漆</td><td rowspan=\"2\">烘干锌黄 环氧底漆</td></tr><tr><td>原料</td></tr><tr><td>铁红</td><td>9.9</td><td>一</td><td>丁醇醚化三聚氰胺甲醛树脂</td><td>4.6</td><td></td><td>5</td></tr><tr><td>锌黄</td><td>6.65</td><td>20</td><td>(50%)</td><td></td><td></td><td></td></tr><tr><td>氧化锌</td><td>4.13</td><td>7</td><td></td><td>环烷酸钻（Co3%)</td><td>0.6</td><td>0.2</td></tr><tr><td>氧化铅</td><td>0.14</td><td>一</td><td></td><td>环烷酸钙（Ca2%)</td><td>0.6</td><td>2</td></tr><tr><td>滑石粉</td><td>8.25</td><td></td><td>3</td><td>环烷酸锌（Zn3%)</td><td>一</td><td>1</td></tr><tr><td>轻体碳酸钙</td><td>一</td><td></td><td>5 二甲苯</td><td></td><td>23.73</td><td>6.8</td></tr><tr><td>40%酯化的脱水麻油酸环氧酯 (50%)</td><td>41.4</td><td>50</td><td>合计</td><td></td><td>100.0</td><td>100.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 347,
+        "chunk": "# $\\textcircled{3}$ 环氧酯炼制工艺举例  \n\nE-12环氧树脂 300kg 二甲苯(回流用) 30kg 脱水葛麻油酸 200kg 二甲苯（稀释用） 470kg  \n\n操作：  \n\n将树脂、脱水麻油酸、回流二甲苯，催化剂 $z_{\\mathrm{nO}}$ （为环氧酯量的 $0.1\\%$ 投人釜中，升温至 $150^{\\circ}\\mathrm{C}$ 树脂熔化后，开动搅拌，升温至 $200\\sim205\\mathrm{^\\circC}$ ，保温酯化约 $2\\mathrm{h}$ ，开始取样，测黏度和酸值。  \n\n当酸值降到5以下时，停止加热，立即冷却降温，将酯化物抽入对稀罐中降温至 $130^{\\circ}\\mathrm{C}$ 以下，加入二甲苯稀释，至 $60^{\\circ}\\mathrm{C}$ 以下，过滤，贮存备用。  \n\n质量指标 酸值（固体） 5mgKOH/g黏度（25℃，气泡法）6s以下",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 348,
+        "chunk": "# 9.无溶剂环氧涂料  \n\n无溶剂环氧涂料是随着人们对VOC挥发性有机化合物的严重关注而发展的品种，以保护环境和工人健康，避免火灾危险，其涂膜很厚不必多道施工。  \n\n制造无溶剂环氧涂料最大的难点如下。  \n\n$\\textcircled{1}$ 环氧树脂的黏度高，典型的液体环氧树脂E-51（或如DER331，Epon828）黏度约为$12000\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$ ，即使采用双酚A/双酚F混合环氧树脂，其黏度仍约为 $6000\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$ ，而普通制漆用的亚麻油的黏度约仅为 $50\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$  \n\n$\\textcircled{2}$ 无溶剂涂料中，当环氧树脂与胺交联反应至某程度达到 $T_{*}$ 近于环境常温时，反应不易继续进行。而在溶剂型涂料中，由于残留涂膜中溶剂的溶剂化作用，降低 ${T_{\\mathrm{*}}}$ ，有利于反应继续固化。  \n\n$\\textcircled{3}$ 涂料中的环氧基和氨基浓度高，反应发热量没有溶剂冲稀并带走热量，所以须注意其调配批量（mixingbatch size)，有些胺类反应迅猛发热高，只能小批量调配，或施工时限短促，须用双口喷枪。  \n\n$\\textcircled{4}$ 低分子量树脂中，两个环氧基因位置较近，交联密度高，涂膜较脆不耐冲击。  \n\n$\\textcircled{5}$ 液体低分子环氧树脂中没有羟基，不能催化反应，需加入水杨酸等催化剂。  \n\n制造无溶剂环氧涂料，降低黏度的措施除选择低黏度的环氧树脂外，尚可加入不挥发的稀释剂，也有用常规的邻苯二甲酸酯等，但它们仅是混合在涂膜中并未结合，会被溶剂或油类萃出。所以较多是采用含有环氧基的活性稀释剂，在固化时参加反应，成为固化涂膜的一部分，在一般情况下，活性稀释剂的用量相当于树脂重量的 $15\\%$ 以下，以免涂膜性能下降太多。若采用二元醇（例如丁二醇）的二缩水甘油醚，虽尚可保持交联程度和力学性能，但抗水性下降。  \n\n常用的商品活性稀释剂示于表2-1-144。这些活性稀释剂往往对人体皮肤有刺激性，使用时必须注意劳动保护。  \n\n表2-1-144常用活性稀释剂  \n\n\n<html><body><table><tr><td>名 称</td><td>环氧当量</td><td>黏度（25℃） /mPa·s</td><td>密度/(g/cm）</td><td>CAS登记号</td></tr><tr><td>甲苯基缩水甘油醚</td><td>170~179</td><td>约8</td><td>1.08</td><td>2210-79-9</td></tr><tr><td>苯基缩水甘油醚</td><td>155~170</td><td>4~7</td><td>1.10</td><td>122-60-1</td></tr><tr><td>丁基缩水甘油醚</td><td>145 ~155</td><td>1~3</td><td>0.92</td><td>2426-08-6</td></tr><tr><td>烯丙基缩水甘油醚</td><td>约114</td><td>1.2</td><td></td><td></td></tr><tr><td>异辛基缩水甘油醚</td><td>215~230</td><td>2~15</td><td>0.89</td><td>2461-15-6</td></tr><tr><td>对叔丁苯基缩水甘油醚</td><td>220~240</td><td>20~40</td><td>1.02</td><td>3101-60-8</td></tr><tr><td>新戊二醇二缩水甘油醚</td><td>135~145</td><td>15~35</td><td>1. 04</td><td>17557-23-2</td></tr><tr><td>1,4-丁二醇二缩水甘油醚</td><td>120~140</td><td>15~20</td><td>1.10</td><td>2425-79-8</td></tr><tr><td>叔碳酸缩水甘油酯（CarduraE10）</td><td>240~265</td><td>5~20</td><td></td><td></td></tr></table></body></html>  \n\n从表2-1-144中可见，它们黏度较低，其中苯基、甲苯基、对叔丁苯基团保色性稍差。应用活性稀释剂时，固化剂用量须相应增加。  \n\n降低该涂料黏度的另一措施是选择低黏度的固化剂。普通的脂肪族多元胺虽黏度低，但施工时限短，发热量大，不方便，而环脂族胺的反应性稍缓，常被介绍用作固化剂，如异佛尔酮二胺以及LaromineC260（BASF公司）。  \n\n![](images/de5dce38677724f5b9cd635eec1441b480936ffdf2342875fada3bb6897e73ec.jpg)  \n（1）无溶剂涂料配方示例  \n\n第一步：先配固化剂溶液。  \n\n<html><body><table><tr><td>异佛尔酮二胺（Deguss8公司） 苯甲醇</td><td>100g 88g</td><td>水杨酸</td><td>12g</td></tr><tr><td colspan=\"4\">所得溶液黏度（20℃）为48mPa·s</td></tr><tr><td>第二步：制漆。</td><td></td><td></td><td></td></tr><tr><td>甲组分 环氧树脂(E-51)</td><td>100g</td><td>硫酸钡</td><td>120g</td></tr><tr><td>钛白</td><td>4g</td><td>石英砂(0.1~0.3mm)</td><td>240g</td></tr><tr><td></td><td>2g</td><td></td><td></td></tr><tr><td>着色颜料</td><td></td><td></td><td></td></tr><tr><td>乙组分</td><td></td><td></td><td></td></tr><tr><td>固化剂溶液</td><td>4.5g</td><td></td><td></td></tr></table></body></html>  \n\n说明：  \n\n$\\Phi$ 先将水杨酸溶解于苯甲醇，再加入异佛尔酮二胺，苯甲醇作为水杨酸的溶剂，又作为环氧树脂涂膜中的增塑剂，留在涂膜中赋予-定弹性，水杨酸是固化催化剂。  \n\n$\\textcircled{2}$ 环脂胺固化的涂层保色性较好，若用芳香胺类固化剂，如Huntsman公司的Aradur830/850则易变色，但耐化学品性优良。  \n\n$\\textcircled{3}$ 涂膜很厚，少量颜料即可遮盖，填料选吸油量低者，如石英砂。涂料中若填料少者$[1:(1\\sim3)]$ ，在地坪漆中称为自流平（selfleveling)，填料很多者 $[1:(3\\sim7)_{.}^{-}$ 1不能流平称为砂浆。石英砂选粒状无破碎者。石英砂可选配采其粗、中、细组合，则填充更密实。  \n\n$\\textcircled{4}$ 上述的异佛尔酮二胺固化剂溶液（共 $\\mathbf{200g}$ ）在搅拌下逐滴加入 $\\scriptstyle20_{\\mathbf{g}}\\ \\mathbf{E}\\ –51$ 环氧树脂（此时稍有发热），加完后继续揽拌2h，制成“现场加成物”in situadduct固化剂，它在低温阴湿环境下施工，不会与空气中 $\\mathrm{CO}_{2}$ 及潮气反应，生成氨基甲酸盐浮于涂层表面，涂膜发雾。而且加成物与环氧树脂的混溶性得到改善。  \n\n陶氏公司D.H.Klein等配制的固化剂有：  \n\nIPDA 45g 水杨酸 31   \nIPDA加成物 10g 苯甲醇 42  \n\n共 $100{\\bf g}$ ，AHEW约86，黏度为 $90\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$ 。用 $86g$ 此固化剂，可配合等当量的环氧树脂，如 $190\\mathbf{g}$ 的D.E.R.331。  \n\n（2）另一种无溶剂环氧涂料示例（芳香胺固化）  \n\n第一步，先制备促进剂（苯乙烯苯酚），  \n\n苯酚 30.1g 苯(溶剂) 33.3g 苯乙烯 41.3g 对甲苯磺酸 0.1g  \n\n升温至 $95\\mathrm{\\sim}100\\mathrm{\\textperthousand}$ 左右，回流 $2\\sim3\\mathrm{h}$ ，进行Friedel-Craft反应，苯乙烯加成至苯酚上，生成苯乙烯苯酚，冷却至 $50\\Upsilon$ ，加人 $13.6\\phantom{1}_{8}$ 碳酸氢钠以中和磺酸，过滤，常压蒸除苯，再减压蒸馏 $(175\\sim180\\%/4\\mathrm{{kPa})}$ 得棕色黏稠液体。 3  \n\n第二步：配制芳香胺固化剂。  \n\n间苯二酚 4.8g 苯乙烯苯酚（见上） 2 8.0g4,4-二氨基二苯甲烷 3.2g  \n\n第三步：轧漆浆 (三辊机)  \n\n环氧树脂（E-44) 50.0g 灯黑 1. 0g 邻苯二甲酸二丁酯 8.0g 重晶石粉 50.0g TiOz 20.0g 滑石粉 5.0g  \n\n将上述芳香胺固化剂与环氧浆拌匀即可剧涂。此涂料的固化剂虽是芳香胺，但因有苯酚促进，在室温下也能固化成膜。此涂料耐磨、耐水、耐化学品，且拌和后反应热不明显，可较大的批量调配，而普通无溶剂环氧涂料，一旦拌入固化剂后常反应发热，缩短施工时限，因而只可小批量拌和后施工，此涂料的芳香胺固化剂会使涂膜稍泛黄。  \n\n无溶剂环氧漆在国内较多的用途是混凝土地坪和狭窄贮槽的内壁等。数十年来，我国工厂都是混凝土地坪。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 349,
+        "chunk": "# 10.单组分烘干涂料  \n\n（1）酚醛树脂固化的环氧树脂漆  \n\n$\\Phi$ 酚醛树脂固化的环氧树脂漆酚醛树脂固化的环氧树脂漆，是环氧树脂漆中耐腐蚀性很好的一种。涂膜具有优良的耐酸碱性、耐溶剂性、耐热性。但涂膜颜色很深，不能做浅色漆。  \n\n环氧酚醛漆主要用于涂装罐头、包装桶、贮罐、管道的内壁、石油化工设备换热器涂料等。  \n\n$\\textcircled{2}$ 环氧树脂的选择以选用高分子量（ $2900\\sim4000$ ）的环氧树脂为宜。这类树脂含羟基较多，羟基官能度较大，与酚醛树脂的羟甲基或烷氧基反应时，固化较快。高分子量环氧树脂具有较长的分子链，可提高涂膜的弹性。与酚醛树脂并用后可同时兼具耐酸性和耐碱性等优良性能。  \n\n$\\textcircled{3}$ 酚醛树脂的选择与用量以丁醇醚化酚醛树脂较宜，如新华树脂厂的284树脂和丁醇醚化二酚基丙烷甲醛树脂均可与环氧树脂混溶，进行固化。  \n\n丁醇醚化二酚基丙烷甲醛树脂与环氧树脂并用时，可制得机械强度高和耐化学品性好的涂料。而且漆的贮存稳定性较好。酚醛树脂的用量为清漆总不挥发分的25%～35%。  \n\n$\\textcircled{4}$ 流平剂环氧酚醛漆施工时，涂膜有时发生橘皮等病，可以加人流平剂解决。如用清漆不挥发分 $2\\%\\sim3\\%$ 的脲醛树脂液，也可以加少量的 $1\\%$ 硅油溶液或 $1\\%$ 的聚乙烯醇缩丁醛。  \n\n$\\textcircled{5}$ 酸催化剂的使用为了提高环氧酚醛漆的固化速率，常加人少量的酸来催化。常用的是磷酸，用量为清漆总不挥发分的 $1\\%\\sim2\\%$ 。但这种催化剂的加入大大缩短了漆的贮存期限。最近多采用潜催化剂，这种催化剂在高温时才裂解起催化作用。如对甲苯磺酸的吗啉盐就是一例。用量为清漆总不挥发分的 $0.5\\%$ 左右。使用催化剂后固化温度一般可由 $200\\mathrm{\\textperthousand}$ 降低到 $150\\mathrm{^{\\circ}C}$ 左右。  \n\n$\\textcircled{6}$ 环氧酚醛漆的烘干多道施工可以提高漆膜性能和减少针孔等病。但应注意掌握烘烤温度，中间层烘烤过度，将引起层间附着力不好。中间层烘烤不足，将不能把溶剂除净，则最后一道烘干时会造成涂膜起泡。一般可采用以下烘干条件，中间层烘干温度 $90\\sim$ 150℃、烘烤 $10\\mathrm{\\sim}30\\mathrm{min}$ ，最后一道烘干温度 $180^{\\circ}\\mathrm{C}$ 、烘烤 $60\\mathrm{{min}}$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 350,
+        "chunk": "# $\\textcircled{7}$ 环氧酚醛漆配方",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 351,
+        "chunk": "# a.耐酸碱腐蚀环氧酚醛清漆  \n\n<html><body><table><tr><td>配比(质量份)： 环氧树脂(E-06)</td><td>30 二甲苯</td><td></td></tr><tr><td>环己酮</td><td>15</td><td>40%二酚基丙烷甲醛树脂液</td></tr><tr><td>二丙酮醇</td><td>15</td><td></td></tr><tr><td>性能：</td><td></td><td></td></tr><tr><td>冲击强度</td><td>490.3N·cm</td><td>耐酸碱性</td></tr><tr><td>弯曲试验</td><td>1mm</td><td>常温HSO，10%~15%</td></tr><tr><td>耐有机溶剂性</td><td></td><td>常温NaOH,10%~20%</td></tr><tr><td>丙酮</td><td>浸9d漆膜起泡</td><td>沸腾HSO20%</td></tr><tr><td>纯苯</td><td>浸9d漆膜不变</td><td>沸腾NaOH,10%</td></tr><tr><td>丁醇</td><td>浸9d漆膜不变</td><td>DDT、石灰硫黄合剂，硫 浸44d漆膜不变</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 352,
+        "chunk": "# b.丁醇醚化二酚基丙烷甲醛树脂的制备  \n\n配比（质量份）：  \n\n双酚A 16.7 HSO (53%) 13. 0   \n甲醛(36%) 31.5 苯酐 0.4   \nNaOH(33%) 17.7 丁醇 20.0  \n\n工艺：  \n\n甲醛与双酚A在 $\\mathbf{NaOH}$ 存在下于 $40^{\\circ}\\mathrm{C}$ 反应，产物以 $\\mathrm{H}_{2}\\mathrm{SO}_{4}$ 中和水洗，加入苯酐、丁醇使之醚化，再经脱水（终点控制沸点 $^{120\\Upsilon}$ ）过滤即得成品，其不挥发分为 $50\\%\\pm2\\%$ 黏度 $(25^{\\circ}\\mathbb{C}$ ，涂-4杯）为 $60\\sim75\\mathrm{s}$ 。  \n\n在耐腐蚀的环氧涂料中，一种是双组分胺固化涂料，常温干燥而涂膜厚，但弹性不甚高，供船舶及港湾等钢结构重防腐蚀等用途。另一种是本节所述酚醛树脂交联的环氧涂料。它不仅耐腐蚀性好，而且挠性好，但必须高温烘烤，涂膜薄，涂于金属薄板上烤干后可耐“后加工”(postforming)，供罐、桶等内壁衬里用，用量甚大。近年来，某些食品罐头在发展深冲的两片罐以取代常规的3片罐，对内壁涂料的延展性提出更高的要求。Dow公司的Massingill等开发了环氧磷酸酯涂料，是将高分子量环氧树脂与浓磷酸反应，然后加水在高温高压下反应，产物除含有环氧树脂的磷酸单酯外，尚含有许多端二羟基树脂及少量游离磷酸。  \n\n下式为环氧磷酸酯制备的示意式：  \n\n![](images/af6b385f9ea1e34105b89bbc3adb4550c16ba43369e17ea674bb87046861cd04.jpg)  \n\n产物成分举例如下：  \n\n环氧磷酸单酯 .26% 游离HPO 0.1%以下端二羟基树脂 52%  \n\n环氧磷酸酯烘漆与常规的高分子量环氧烘漆相比，有如下优点。  \n\na.更好的挠曲性特别适用于罐头内壁及底漆。这是因为常规的环氧树脂的交联基团是树脂链中间的仲羟基，反应活性低而有位阻，其树脂端的环氧基与酚醛或氨基树脂的羟甲基或烷氧基反应迟钝，不易扩链而提高弹性。  \n\n环氧磷酸酯的分子端含有多量伯羟基（上例中可见 $52\\%$ 组分含伯羟基)，反应活性高，且无位阻，是遥爪聚合物（telechelic polymer），能与交联剂的羟甲基或烷氧基优先反应，使树脂链增加长度，提高挠性。  \n\nb.提高附着力涂膜的干附着力和湿附着力均优于常规的环氧烘漆。因为其磷酸酯基按Fowkes的解说：附着力是由于酸-碱间的作用。底板金属表面的氢氧化物呈弱碱性，涂膜中磷酸基与它相互作用，提高了附着力。常规环氧烘涂膜的附着力来自其仲羟基与底材间的氢键。在湿态时，当水透过漆膜到达底材时，水与金属表面间形成的氢键超过仲羟基的氢键而能置换之，湿附着力大为下降。但磷酸基与底材形成的氢键强于水的氢键，水不能置换，使环氧磷酸酯涂膜在湿态下仍保持较佳的附着力。Massinglill采用T形板剥离法，将试样在 $90^{\\circ}\\mathsf{C}$ 水中浸4天后，用Instron仪器拉开，测定附着力，结果是环氧磷酸酯涂膜的湿附着力比常规的环氧烘漆提高6倍。  \n\n罐头内壁涂料配方举例如下。  \n\n<html><body><table><tr><td>环氧磷酸酯</td><td>40g(固体计）</td><td>丁氧基酚醛树脂</td><td>10g(固体计）</td></tr><tr><td>硅树脂(流平助剂)</td><td>0.2g</td><td>醚醇溶剂</td><td>约50g</td></tr></table></body></html>  \n\n环氧酚醛烤漆应用于石油化工厂的许多换热器，获得良好实效，漆中添加氧化铬绿填充，可提高传热系数，我国石化厂中用量很大。一般烘四道，最后一道高温烘烤，膜总厚度$180\\sim200\\mu\\mathrm{m}$ 9  \n\n上述是用酚醛树脂固化高分子量环氧树脂，具有很高的耐蚀性。若耐腐蚀性要求稍低的场合，为了降低成本，笔者试过用短油度的环氧酯，以丁氧基酚醛树脂高温交联，也可获得优良的涂膜，而且不必用强溶剂，只需芳烃即可溶解，涂膜平整无需流平助剂。  \n\n(2）氨基树脂固化环氧树脂漆环氧氨基漆也具有较好的耐化学品性，但比环氧酚醛漆差些。涂膜的柔韧性很好，颜色浅、光泽强。适于涂装医疗器械、仪器设备、金属或塑料表面罩光等。  \n\n适用的环氧树脂分子量为2900和3750。  \n\n丁醇醚化脲醛树脂与环氧树脂有很好的混溶性。丁醇醚化三聚氰胺甲醛树脂和环氧树脂可混溶。三聚氰胺甲醛树脂具有更好的光泽和硬度。  \n\n环氧树脂与氨基树脂的配比（质量比）在 $70:30$ 时漆的性能最好。当环氧树脂比例增加时，涂膜的柔韧性和附着力提高。如增加氨基树脂的比例时，涂膜的硬度和抗溶剂性提高。氨基树脂的使用比例在 $30\\%$ 以下时，则烘烤温度需提高很多。  \n\n在不用酸催化剂时，烘烤条件为 $190\\sim205\\mathrm{^c}$ 、烘 $30\\mathrm{{min}}$ 。由于有些氨基树脂中含有酸，烘烤温度可降低。如加人清漆总不挥发分 $0.5\\%$ 的对甲苯磺酸吗啉盐，烘烤温度可降低为$150^{\\circ}\\mathrm{C}$ ，烘 $30\\mathrm{min}$  \n\n环氧氨基漆配方（质量份）举例见表2-1-145。  \n\n表2-1-145环氧氨基漆配方  \n\n\n<html><body><table><tr><td>原 料</td><td>清漆</td><td>磁漆</td><td>原 料</td><td>清漆</td><td>磁漆</td></tr><tr><td>钛白(金红石型）</td><td>一</td><td>29.4</td><td>二丙酮醇</td><td>26.0</td><td>17.6</td></tr><tr><td>环氧树脂</td><td>28.0</td><td>20.6</td><td>二甲苯</td><td>26.0</td><td>17.7</td></tr><tr><td>60%丁醇醚化脲醛树脂</td><td>20.0</td><td>14.7</td><td></td><td></td><td></td></tr></table></body></html>\n\n注：环氧树脂：脲醛树脂-70：30。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 353,
+        "chunk": "# 性能：  \n\n$205\\%$ 、烘 $20\\mathrm{min}$ 后涂膜的耐化学品性、光泽、硬度均好。  \n\n近十几年来我国卷材涂料发展很快，大多是环氧树脂/脲醛树脂底漆，聚酯树脂/甲醚化三聚氰胺为面漆。该体系在测试T弯时，往往底漆占相当关键。环氧树脂为609，脲醛树脂的量约为环氧树脂量的 $1/6\\sim1/5$ 。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 354,
+        "chunk": "# 11.环氧粉末涂料  \n\n粉末涂料不含溶剂，不污染大气，较不易引起火灾。而且粉末涂料不需底漆，一次施工即可获得较厚的耐蚀厚的漆膜。但粉末涂料须高温烘烤，限用于不太大且耐烘烤的物体上。在热固性粉末涂料中，环氧粉末涂料应用最早，产量最广，我国发展最快，几乎占全球首位。本书粉末涂料章节中，专门分类介绍环氧粉末涂料的制造和应用，故本章从略。",
+        "category": " Introduction"
+    },
+    {
+        "id": 355,
+        "chunk": "# 六、水性环氧树脂漆  \n\n随着人们对环境保护的关注，环氧涂料除了以粉末及无溶剂形态出现外，也开发了水性涂料。实用的有烘干型的阴极电沉积漆CED、阳极电沉积漆AED，均以环氧树脂为主要基料。此外，软饮料的两片罐内壁衬里涂料，以Glidden公司（ICI公司所属）开发的水性丙烯酸接枝的环氧涂料最为成功，现已广泛应用。实用中常温固化型者大多是双组分水乳化涂料。一个组分为低分子量的环氧树脂，其环氧当量约180～190，黏度（25℃）为6000～$8000\\mathrm{{mPa}\\cdot\\ s;}$ 另一组分为聚酰胺，例如Ciba公司的HZ-340，为 $50\\%$ 水溶液，黏度 $25\\%$ >$13000{\\sim}23000\\mathbf{m}\\mathbf{Pa}\\cdot\\mathbf{s}$ ，色泽（加氏） ${\\leqslant}14$ ，含活泼胺 $2.7{\\sim}3.$ 1mol/kg。通常水性涂料的施工时限较短。常规溶剂型双组分涂料的施工时限，常测定其黏度上升而不易施工的时间；但水性双组分环氧涂料的施工时限，常受制于涂膜的光泽，超过时限则涂膜失去光泽，时限很短。Anchor公司的S.Darwen不用聚酰胺而用胺加成物为固化剂，制得的水性环氧涂料不仅施工时限延长，而且涂膜防腐蚀性能可接近于溶剂型的固体环氧树脂/聚酰胺涂料。  \n\n作为示例，举Ciba公司介绍的水性环氧漆的配方如下：  \n\n\n<html><body><table><tr><td>Araldite PY 340-2</td><td>1000g</td><td>去离子水</td><td>1745g</td></tr><tr><td>固化剂HZ3982</td><td>990g</td><td>该漆施工时限（光泽下降不超过10%时）</td><td>3h</td></tr><tr><td>TiO</td><td>1122g</td><td>不沾尘干燥</td><td>7h</td></tr></table></body></html>  \n\n以上AralditePY340-2是双酚A/双酚F型环氧树脂，内含有非离子乳化剂，其黏度$(25^{\\circ})$ ）为 $6000{\\sim}8000\\mathrm{mPa}\\cdot\\textbf{s}$ ，环氧指数为 $5.5\\sim5.8\\mathrm{eq}/\\mathrm{kg}.$ 固化剂是多元胺的水溶液，固体含量为 $80\\%$ ，挥发分为 $20\\%$ ，是水与异丙醇的混合物 $(3:1)$ ，含异佛尔酮二胺及间苯二甲二胺等，活泼氢当量175，黏度 $(25\\mathsf{C}$ ）为 $11000{\\sim}15000\\mathrm{mPa}\\cdot\\mathrm{s}.$  \n\n配制方法：将 $\\mathrm{\\TiO_{2}}$ 分散于环氧树脂中，然后在搅拌下缓慢加水使乳化（但若操作温度太低或太高，或揽拌剪切太剧烈，则乳液会不稳定)。以此作为一个组分，另一组分为固化剂，施工前调和之。  \n\n制造双组分水性环氧涂料，一般分为1型和2型，或称为第1代和第2代，再进一步改进者，则称为第3代。最早第1代是采用液体环氧树，因它便于乳化，固化剂则较多是采用聚酰胺树脂，加以极少量醋酸使成盐而变成水溶液，使用时此胺盐既是固化剂又是乳化剂，在充分搅拌下使液体环氧树脂乳化。各生产公司稍有些差别，但均属于1型，一般只用于混凝土墙面或地坪底漆，因亲水性高，且含醋酸，不能用于金属底材。兹录数家公司配方供参考。  \n\n德国UPPC公司水性环氧涂料（现UPPC被Dow公司收购）采用液体环氧树脂Pol-ypox E411，EEW 190。  \n\n采用固化剂是Polypox1H7005W，是聚酰胺加成物的商品，含游离胺1%以下，不含溶剂，能溶解于水，黏度 $25\\Upsilon$ ）约为 $15000\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$ 票  \n\n它的性能：  \n\n<html><body><table><tr><td>腰值约</td><td>200</td><td>0℃会冻结，加温至40℃复原，贮藏期1年</td><td></td></tr><tr><td>胺氢当量</td><td>220g/eq</td><td>颜色（加氏管）</td><td>≤6</td></tr><tr><td>白色有光水性环氧漆配方： 甲组分：</td><td></td><td></td><td></td></tr><tr><td>固化剂1H7005W</td><td>23.0g</td><td>BaSO</td><td>22.0g</td></tr><tr><td>去离子水</td><td>12.0g</td><td>去离子水</td><td>24.8g</td></tr><tr><td>BYK024（消泡剂）</td><td>0.2g</td><td>小计共</td><td>100.0g</td></tr><tr><td>TiO</td><td>18.0g</td><td></td><td></td></tr><tr><td>乙组分：</td><td></td><td></td><td></td></tr><tr><td>环氧树脂E411</td><td>21.0g</td><td></td><td></td></tr><tr><td>搅拌混合后</td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td>PVC</td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td>施工时限</td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td>24%</td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td>60min</td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td>62.9%</td><td>光泽(60°)%</td><td></td></tr><tr><td>固体分</td><td></td><td></td><td>88</td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n可见，施工时限很短，超过时限其连续相水的黏度稍有上升，而搅拌乳化的颗粒逐步固化不易聚结Coaleace而光泽下降，一般以光泽下降 $10\\%$ 即作为时限。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 356,
+        "chunk": "# （1）白色无光水性环氧漆配方  \n\n<html><body><table><tr><td colspan=\"4\">甲组分</td></tr><tr><td>固化剂1H7005W</td><td>17.4g</td><td>BaSO</td><td>29.0g</td></tr><tr><td>去离子水</td><td>22.5g</td><td>滑石粉（特细）</td><td>10.7g</td></tr><tr><td>Disperbyk 190（分散剂）</td><td>0.2g</td><td>去离子水</td><td>10.5g</td></tr><tr><td>BYK 024消泡剂</td><td>0.2g</td><td>小计共</td><td>100.0g</td></tr><tr><td>TiO2</td><td>9.5g</td><td></td><td></td></tr><tr><td>乙组分</td><td></td><td></td><td></td></tr><tr><td>环氧树脂E411</td><td>15.8g</td><td></td><td></td></tr><tr><td>搅拌混合后</td><td></td><td></td><td></td></tr><tr><td>施工时限</td><td>60min</td><td>PVC</td><td>35.6%</td></tr><tr><td>光泽（60°）%</td><td>10</td><td>固体分</td><td>66.1%</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 357,
+        "chunk": "# (2）水性环氧地坪涂料配方  \n\n固化剂采用Polypoxw804，它的胺值约290，黏度（25℃）约 $5500\\mathrm{mPa}\\cdot\\mathrm{~s~}$ ，胺氢当量175。甲组分  \n\n<html><body><table><tr><td>固化剂W804</td><td>120g</td><td>BsSOt</td><td>300g</td></tr><tr><td>去离子水</td><td>63g</td><td>石英砂(0.06~0.25mm)</td><td>450g</td></tr><tr><td>消泡剂</td><td>5g</td><td>去离子水</td><td>32g</td></tr><tr><td>TiO</td><td>30g</td><td>小计共</td><td>1000g</td></tr><tr><td>乙组分</td><td></td><td></td><td></td></tr><tr><td>环氧树脂E411</td><td>140g</td><td></td><td></td></tr></table></body></html>\n\n将乙组分混入甲组分中，搅拌 $3\\mathrm{min}$ 以上。  \n\n混合后施工时限约 $50\\mathrm{{min}}$ ，固体分约 $70\\%$ ，密度 $25\\%$ ）为 $1.138/\\mathrm{cm}^{3}$ ，涂布浇于地坪上，括成 $3\\mathrm{mm}$ 湿膜，用有刺滚子消泡并滚平。此水性涂料的优点是可直接涂于新筑的混凝土面上，而溶剂型环氧涂料必须待混凝土养护28天以后才可涂布。  \n\nAnchor公司生产水性固化剂Casamid是聚酰胺，并不含醋酸而配方中含少量溶剂，示例如下。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 358,
+        "chunk": "# (3）半光地坪涂料  \n\n<html><body><table><tr><td colspan=\"5\">甲组分</td></tr><tr><td>Casamid 360</td><td>19.8g</td><td>分散助剂</td><td>0.4g</td></tr><tr><td>异丙醇</td><td>1. 8g</td><td>滑石粉</td><td>9.8g</td></tr><tr><td>丙二醇甲醚</td><td>1.8g</td><td>重晶石粉</td><td>15.0g</td></tr><tr><td>去离子水</td><td>26.0g</td><td>清泡剂BYK031</td><td>0.4g</td></tr><tr><td>TiO</td><td>9.9g</td><td></td><td></td></tr><tr><td>乙组分</td><td></td><td></td><td></td></tr><tr><td>液体环氧树脂（EEW190）</td><td>15.1g</td><td></td><td></td></tr><tr><td>搅拌混合后</td><td></td><td></td><td></td></tr><tr><td>施工时限（20C）</td><td>2h</td><td>VOC</td><td>49g/L.</td></tr><tr><td>光泽（60°)</td><td>51%</td><td>耐磨性（CS17,1000转，1kg）</td><td>90mg</td></tr><tr><td>（4）平光墙面漆</td><td></td><td></td><td></td></tr><tr><td>甲组分</td><td></td><td></td><td></td></tr><tr><td>Casamid 362</td><td>20.8g</td><td>TiO</td><td>10.5g</td></tr><tr><td>异丙醇</td><td>6.3g</td><td>滑石粉</td><td>21.0g</td></tr><tr><td>水</td><td>25.0g</td><td>消泡剂BYK 031</td><td>0.4g</td></tr><tr><td>乙组分</td><td></td><td></td><td></td></tr><tr><td>液体环氧树脂</td><td>16.0g</td><td></td><td></td></tr></table></body></html>  \n\n以上Casamid362是将Casamid360通以 $\\mathrm{CO_{2}}$ 形成碳酸盐，使固化反应稍慢延长施工时限。以上液体环氧树脂是双酚 $\\mathbf{A}/\\mathbf{F}$ 混合树脂，环氧当量EEW190，并含有活性稀释剂${\\bf C}_{12}\\sim{\\bf C}_{14}$ 失水甘油醚。  \n\n搅拌甲、乙组分后：  \n\n施工时限（20℃） 3.5h  \n光泽 (60°) 20%  \nE.Almeida等介绍水性环氧涂料，用于钢铁防腐蚀，配方是：  \n底漆 料 (环氧+聚酰胺） 6.98)膜摩 75μm  \n中涂层基料 (环氧+聚酰胺) 24.0g云母氧化铁 43.0g膜厚 85μm  \n面层 基料 (环氧+聚酰胺) 云母氧化铁 24.08膜厚100μm总厚度260μm  \n\n此涂层用于葡萄牙的Sineo地区，当地的环境是：  \n\n冷轧钢腐蚀率 388μm/年 SO沉积率 22.6mg/(m²·天)氯化物沉积率 151. 8mg/(m·天） 湿润时间 5107h/年经海边天然暴晒两年，结果良好，经盐雾试验1000h，结果良好。  \n\n第2代水性环氧涂料的不同点是采用固体环氧树脂（E-20，601）的乳化分散体，含有水溶性助溶剂，以取代第一代的液体环氧树脂，也采取憎水性的胺加成物的水分散体，以取代水溶性聚酰胺。这种固体分散体涂层，待水分和助溶剂挥发后即可初步指触干（因为树脂本身是固体，不像液体环氧树脂必须反应固化到一定程度后才指触干)，国外称之为“Lac-quer dry挥发干”。固体环氧树脂的两个环氧基距离较远，交联密度适中，漆膜耐冲击。漆膜中缺少亲水组分，所以耐水性较好，不仅可用于混凝土墙面、地坪，也可用于钢铁防锈，涂料的施工时限也较第1代涂料长。但此涂料是树脂的分散体，必须考虑两个问题：①乳化剂； $\\textcircled{2}$ 聚结成膜（Coalesce)。  \n\n普通乳化剂在成膜后残留在涂膜中，是薄弱环节，有许多专利文献介绍，合成特殊的乳化剂，其结构近似于环氧树脂，成膜后混溶于涂膜中。该涂料中必须含有少量溶剂，以助树脂的颗粒聚结成膜，这不同于第1代涂料，示例如下。  \n\n甲组分  \n\n<html><body><table><tr><td>E-20环氧树脂分散体（55%固体分）</td><td>330. 0g</td><td>FeO</td><td></td><td>71.1g</td></tr><tr><td>二丙酮醇</td><td>7.0g</td><td>防锈颜料</td><td></td><td>100.0g</td></tr><tr><td>消泡剂</td><td>3.5g</td><td>磁土</td><td></td><td>71.1g</td></tr><tr><td>水</td><td>60.0g</td><td>BaSO</td><td></td><td>71.1g</td></tr><tr><td>硅灰石</td><td>106.7g</td><td>水磨云母粉</td><td></td><td>7.5g</td></tr><tr><td colspan=\"5\">以上组分经高速揽拌后进行调稀： 加入E-20环氧树脂分散体（55%）</td></tr><tr><td>水（预热至40℃，缓慢加人）</td><td></td><td></td><td>小计</td><td>140.7g 14.2g 989.2g</td></tr><tr><td>乙组分</td><td></td><td></td><td></td><td></td></tr><tr><td>胺加成物（60%）</td><td></td><td></td><td></td><td>60.0g</td></tr><tr><td>水</td><td></td><td></td><td>小计</td><td>110.0g</td></tr><tr><td>搅拌混合后：</td><td></td><td></td><td></td><td>170.0g</td></tr><tr><td>涂料施工时限</td><td>8h</td><td>耐甲乙酮擦拭</td><td></td><td></td></tr><tr><td>耐盐雾</td><td>1600h</td><td></td><td></td><td>100次</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 359,
+        "chunk": "# 美国Hexion公司的第2代水性环氧涂料配方如下。  \n\n甲组分  \n环氧分散体EPI-REZ3520-WY-551（近似601环氧，55%） 510.5g乙组分  \n固化剂EPI-CURE8537-WY-60 155.4g 消泡剂 4.0g乙二醇丁醚 7.5g TiO: 250.0g将以上投料高速分散再加水 149.8g",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 360,
+        "chunk": "# 甲、乙组分充分搅拌混合后：  \n\nVOC 180g/L 铅笔硬度 2H 施工时限 >6h 耐盐雾 24天/7M 光泽(60°) 100%  \n\n甲、乙组分的配比可按需调整，若多加环氧组分，则耐盐雾、耐潮性提高，若多加固化剂，则耐溶剂性提高。  \n\nHexion公司为了进一步提高第2代涂料性能，推出了该公司第3代产品，采用中等分子量的多官能度环氧树脂（普通双酚A环氧树脂仅有2官能度），以及多官能度的固化剂，示例如下。  \n\n<html><body><table><tr><td>力 EPI-REZ 5522-WY-55(55%)</td><td>330.0g</td><td>消泡剂</td><td></td><td>3.5g</td></tr><tr><td>二丙酮醇</td><td>7.0g</td><td>水</td><td></td><td>60.0g</td></tr><tr><td>将以上揽匀，加人：</td><td></td><td></td><td></td><td></td></tr><tr><td>硅灰石</td><td>106.7g</td><td>硅酸铝</td><td></td><td>71.1g</td></tr><tr><td>FeOs</td><td>71.1g</td><td>BaSO</td><td></td><td>71.1g</td></tr><tr><td>防腐蚀颜料</td><td>100.0g</td><td>水磨云母粉</td><td></td><td>7.5g</td></tr><tr><td>将以上高速分散，再加入：</td><td></td><td></td><td></td><td></td></tr><tr><td>EPI-REZ 5522-WY-55(55%)</td><td></td><td></td><td></td><td>147.0g</td></tr><tr><td>水</td><td></td><td></td><td>小计</td><td>14.2g 989.2g</td></tr><tr><td>乙组分</td><td></td><td></td><td></td><td></td></tr><tr><td>EPI-CURE 固化剂8290-Y-60</td><td></td><td></td><td></td><td></td></tr><tr><td>水</td><td></td><td></td><td></td><td>60.0g</td></tr><tr><td></td><td></td><td></td><td>小计</td><td>110.0g 170.0g</td></tr><tr><td>双组分混合后，稍加水至黏度大</td><td>(60~70KU)</td><td></td><td></td><td></td></tr><tr><td>VOC</td><td>160g/L</td><td>MEK擦拭</td><td></td><td>100次</td></tr><tr><td>PVC</td><td>35.8%</td><td>盐雾通过</td><td></td><td>1560h</td></tr><tr><td></td><td>1. 75h</td><td>潮湿试验通过</td><td></td><td>1100h</td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td>指触干</td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td>干透</td><td>8.0h</td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n陶氏公司的D.H.Klein和K.Jorg研究了水性环氧涂料。他们配制了第1代水溶性的胺加成物固化剂EH-1和环氧较多的增水性加成物EH-2，以及他们配制的EH-3固化剂「由聚 (亚甲基环已胺) $70\\%$ 和苯甲醇 $30\\%$ 混合而成]。 9八  \n\n![](images/fb041b3e79cf056b9ba692f4e52f1f16129bd82dff2a540c5457063577a7f556.jpg)  \n\n其氨基结合于仲碳原子上，反应性较缓，使其接触分散体中的环氧树脂颗粒，不致过早在表面局部固化，阻碍以后固化剂透人。苯甲醇既帮助成膜，且增韧漆膜。  \n\n固化后其羟基又促进固化反应。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 361,
+        "chunk": "# 三种固化剂成膜后性能比较如下：  \n\n<html><body><table><tr><td></td><td>EH-1</td><td>EH-2</td><td>EH-3</td></tr><tr><td>潮湿试验7天（10分最好）</td><td>0</td><td>5</td><td>7</td></tr><tr><td>盐雾试验</td><td>350天</td><td>500天</td><td>1000天</td></tr><tr><td>潮湿后恢复24h，再试划格剥离残留</td><td>0%</td><td>99%</td><td>99%</td></tr><tr><td>光泽(85°)%</td><td>40</td><td>50</td><td>90</td></tr><tr><td>硬度Persoz/s</td><td>68</td><td>76</td><td>111</td></tr></table></body></html>  \n\nAir ProductsCo.（空气产品公司）生产的固体环氧树脂的水性乳液，商品名AncarezAR550，是用固体环氧树脂（EEW715）分散于水中（不含有机溶剂)，重量固体分为$55\\%$ ，外观乳白色，成膜后透明有光泽，黏度（25℃）为 $100\\mathrm{{mPa}\\cdot\\mathrm{{\\s}}}$ ，乳液的环氧当量为1300。  \n\n该公司推荐的水性固化剂Anquawhite性质如下：  \n\n它是树脂状胺的分散体，呈白色，它与上述环氧树脂分散体配合，涂膜光亮而施工时限较长。  \n\n<html><body><table><tr><td>固体分（重量）树脂状胺</td><td>55%</td><td>黏度（25℃）</td><td>200mPa * s</td></tr><tr><td>水</td><td>41%</td><td>胺值</td><td>100</td></tr><tr><td>丙二醇甲醚</td><td>4%</td><td>胺氢当量</td><td>350</td></tr></table></body></html>  \n\n前述的水性环氧涂料，大多是双组分的常温固化涂料，通过环氧基团与胺氢反应而交联。印度的C.J.Patel等研究了阴极电沉积漆。普通的阴极电沉积漆是以环氧树脂为主体，用封闭异氰酸酯交联。但在烘烤时封闭剂会挥发，污染烘道生成积渣，且异氰酸酯有毒。烘烤时漆膜收缩，漆膜失重。Patel等开发的水性阴极电沉积漆不用异氰酸酯，而是在其体系中引入叔胺，在 $220^{\\circ}\\mathrm{C}$ 高温烘烤时，会催化环氧基团间自聚交联，涂膜性能优良，且烘烤时涂膜几乎没有失重损耗。  \n\n此外尚有Glidden 公司开发的用丙烯酸类单体接枝于环氧树脂制得水性树脂，用甲醚化三聚氰胺固化，用于二片铝罐内壁涂料，内装啤酒、可乐、果汁等。我国方允之、都绍萍等也试制并经急性毒性和致突变试验合格，耐4%醋酸及 $65\\%Z$ 醇和正已烷。  \n\n我国周文涛、王兆安等介绍制备Ⅱ型水性环氧涂料的方法，其漆膜耐盐水通过168h。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 362,
+        "chunk": "# 七、环氧树脂的分析方法  \n\n环氧树脂的分析方法，包括环氧值、羟值、酯化当量、胺值、双酚A环氧树脂的定性分析、固体环氧树脂软化点的测定、环氧基的红外吸收峰等。具体分析方法，在本版涂料工艺中并入专门章节进行具体详细介绍，故在本节中从略。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 363,
+        "chunk": "# 第八节聚氨酯与涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 364,
+        "chunk": "# 一、概况  \n\n聚氨酯漆即聚氨基甲酸酯漆，是指在其漆膜中含有相当数量的氨酯键（一的涂料。  \n\n聚氨酯漆的树脂与其他树脂（如聚酯、聚醚等）不同。在聚酯树脂中除了烃基外只含有酯键，在聚醚中只含有醚键，但是在聚氨酯树脂中除了氨酯键以外，尚可含有许多酯键、醚键、脲键、脲基甲酸酯键、异氰脲酸酯键、油脂的不饱和双键，以及丙烯酸酯成分等，有时丙烯酸酯的数量甚至超过氨酯键，然而习惯上仍总称为聚氨酯漆，实际上近似嵌段共聚合物。  \n\n氨基甲酸（NHCOOH）不稳定，实际上不能游离存在。它的铵盐虽然存在，但亦不稳定，在湿空气中分解。只有氨基甲酸酯 $\\scriptstyle\\mathbf{\\prime}_{\\mathbf{NH}_{2}\\mathbf{COOR}}$ ）是稳定的。  \n\n聚氨酯漆的树脂不像丙烯酸漆那样，由丙烯酸酯单体聚合而成。聚氨酯漆的树脂并非由氨基甲酸酯单体聚合而成，却由多异氰酸酯（主要原料是二异氰酸酯）与多元醇结合而成。  \n\nH—O—C=N 氰酸(烯醇式） R—N-C—O 异氰酸酯H—N=C—0 异氰酸（酮式） OCN—R—NCO 二异氰酸酯  \n\n0 OH HOCN—R—NCO+nHO—R'—OH—→ R—N—C—O—R'—O-C-N}。除了上述反应外，制备氨基甲酸酯的方法还有以下几种。  \n\n$\\textcircled{1}$ 氯甲酸酯与胺反应$\\textcircled{2}$ 氨基甲酰氯与醇反应$\\textcircled{3}$ 醇与脲加热反应  \n\n$$\n\\begin{array}{r}{\\underset{\\substack{\\mathrm{H}_{2}N=\\mathrm{C}-\\mathrm{NH}_{2}\\mathrm{~\\tiny~+ROH}\\mathrm{~\\tiny~\\stackrel{\\bigtriangleup~}{\\longrightarrow~}~(H N C O+N H_{3}+R O H)~}}}{0}\\underset{\\substack{\\longrightarrow\\mathrm{~H}_{2}N=\\mathrm{C}-\\mathrm{OR}\\mathrm{~\\tiny~+NH}_{3}}}{0}}\\end{array}\n$$  \n\n但是在工业上具有实用价值的还是1937年OttoBayer等所研究的异氰酸酯与醇加成的路线。现在工业上所生产的聚氨酯高聚物的主要原料是多异氰酸酯，其涂膜固化时不论形成氨酯键或含有些脲键，均归属聚氨酯漆。在德国工业标准中有各种涂料树脂，如醇酸、丙烯酸、环氧树脂等，却没有聚氨酯树脂，只有多异氰酸酯树脂（DIN53185)，所以多异氰酸酯是聚氨酯漆的基础。  \n\n二异氰酸酯与多元醇生成高聚物的过程，既不是缩合，也不是聚合，而是在两者之间，称为逐步加成聚合。在此反应中，一个分子中的活性氢原子转移到另一个分子中去：  \n\n逐步加成聚合反应除了上述氢原子转移的特点之外，它与普通缩聚反应不同之处是没有副产物析出（例如酯化反应有水生成)，因而在反应过程中并不需抽除副产物以促使平衡的转化。它的工业产品在固化过程中也没有副产物分离出来（例如酚醛树脂固化时分出的水和甲醛)，因而体积收缩较少，并可制无溶剂涂料。而且缩合反应需加温（吸热）以促进酯化等，逐步加成聚合则是放热反应，必须引起注意。它一般是不可逆的，这也是与缩聚反应不同之处，例如醇酸树脂在反应釜中若接近胶凝时，尚可加人甘油抢救，而聚氨酯若发生胶凝则难以抢救。  \n\n逐步加成聚合反应与普通连锁反应不同之处是，它在链增长的过程中不是依靠能量的传递，而且它的每步产物本身是稳定的，虽隔了长时间后尚可继续反应。连锁反应都是C—C原子间结合成键，而逐步加成聚合的高聚物链中大多杂有氧、氮、硫等原子。  \n\n20世纪30年代后期，继美国制成了尼龙纤维之后，德国经过大量系统的研究，于1941年制成了由己二异氰酸酯与丁二醇反应而成的聚氨酯纤维，当时性能不佳，经以后几十年研究开发，制成了弹性纤维，在我国称为氨纶。聚氨酯高聚物可以应用于黏合剂、涂料、泡沫塑料、橡胶、纺织、皮革等，尤其作为泡沫塑料，在50年代逐渐获得推广和发展，成为聚氨酯高聚物中最主要的用途。  \n\n聚氨酯漆具有许多优良特点。  \n\n$\\Phi$ 氨酯键的特点是在高聚物分子之间能形成非环及/或环形的氢键：  \n\n![](images/b1568f93074193be2be852d044fc36c5bc5104a7582fad227c1ed9d5525b8a0d.jpg)  \n非环氢键  \n\n![](images/06384984fba629f130ff070cae802c1a27522b3795b2cfee7f178176846d9371.jpg)  \n环形氢键  \n\n在外力作用下，氢键可分离而吸收外来的能量（每摩尔吸收 $20\\sim25\\ensuremath{\\mathrm{kJ}})$ 。当外力除去后又可重新再形成氢键。如此的氢键裂开，又再形成的可逆重复，使聚氨酯漆膜具有高度机械耐磨性和韧性。与其他类涂料相比，在相同硬度条件下，由于氢键的作用，聚氨酯漆膜的断裂伸长率最高，所以广泛用作地板漆、甲板漆等。  \n\n$\\textcircled{2}$ 涂料中有些品种（如环氧、氯化橡胶等）保护功能好而装饰性稍差；有些品种（如硝基漆等）则装饰性好而保护功能差。然而聚氨酯漆兼具保护和装饰性，可用于高级木器、钢琴、大型客机等的涂装。  \n\n$\\textcircled{3}$ 涂膜附着力强。聚氨酯像环氧一样，可配制成优良的黏合剂。因而涂膜对多种物面（金属、木材、橡胶、混凝土、某些塑料等）均有优良的附着力。笔者的经验认为：对某些金属表面，聚氨酯漆的附着力稍逊于环氧树脂漆；但对于橡胶则聚氨酯漆超过环氧树脂漆。  \n\n$\\textcircled{4}$ 涂膜的弹性可根据需要而调节其成分配比，可从极坚硬的调节到极柔韧的弹性涂层，而一般涂料如环氧、不饱和聚酯、氨基醇酸等只能制成刚性涂层，难以赋予高弹性。  \n\n$\\textcircled{5}$ 涂膜具有优良的耐化学药品性，耐酸、碱、盐液、石油产品，因而可作钻井平台、船舶、化工厂的维护涂料、石油贮罐的内壁衬里等。  \n\n$\\textcircled{6}$ 能在高温烘干，也能在低温固化。在典型的常温固化涂料：环氧、聚氨酯、不饱和聚酯3类中，环氧及不饱和聚酯在 $10\\Upsilon$ 以下就难以固化，只有聚氨酯在 $0\\%$ 也能正常固化，因此能施工的季节长。因为它在常温能迅速固化，所以对大型工程如大型油罐、大型飞机等可以常温施工而获得优于普通烘烤漆的效果。  \n\n$\\textcircled{7}$ 聚氨酯漆可制成耐一40℃低温的品种。也可制成耐高温绝缘漆，性能接近于聚酰亚胺。  \n\n$\\textcircled{8}$ 聚氨酯漆涂覆的电磁线，可以不需刮漆，能在熔融的焊锡中自动上锡，特别适用于电讯器材和仪表的装配。  \n\n$\\textcircled{9}$ 它可与聚酯、聚醚、环氧、醇酸、聚丙烯酸酯、醋酸丁酸纤维素、氯乙烯醋酸乙烯共聚树脂、沥青、干性油等配合制漆，可根据不同的要求制成许多品种。  \n\n$\\textcircled{10}$ 可制成溶剂型、液态无溶剂型、粉末、水性、单罐装、两罐装等多种形态，满足不同需要。  \n\n由于具有上述优良性能，聚氨酯漆在国防、基建、化工防腐、车辆、飞机、木器、电气绝缘等各方面都得到广泛的应用，新品种不断涌现极有发展前途。但它的价格较贵些，目前大多用于对性能要求较高的场所。有些聚氨酯漆中含有相当多的游离异氰酸酯，吸人人体有碍健康，必须抽除游离的二异氰酸酯，并加强通风。含异氰酸酯基的漆很活泼，遇水或潮气会胶凝，因此贮存时必须密闭。施工操作不慎易引起层间剥离、起小泡等病。总之，聚氨酯漆可获得高质量的涂层，但其性质较为敏感，所以制造和施工时必须严格遵守操作规程。",
+        "category": " Introduction"
+    },
+    {
+        "id": 365,
+        "chunk": "# 二、化学原理",
+        "category": " Introduction"
+    },
+    {
+        "id": 366,
+        "chunk": "# 1.异氰酸酯的制备方法  \n\nWurtz于1849年首先用有机硫酸酯和氰酸钾合成了异氰酸酯。  \n\n尚有其他制备异氰酸酯的方法，但是现今在工业上实际大量采用的是1884年亨切尔（Hentschel）提出的伯胺盐光气化法。  \n\n光气要纯，不可含氯，否则会发生副反应，影响产品纯度：  \n\n![](images/6117841a632fbbac502be0777ed46db98556eee4fba55a18513c9cab2ad2d728.jpg)  \n\n(1）甲苯二异氰酸酯聚氨酯漆中最常用的原料是甲苯二异氰酸酯（TDI)，有两种异构体。  \n\n![](images/769b7f704e8ceb95893ef1c414709677e18619e623b6ef6495777b5384c71c72.jpg)  \n\n它是由甲苯经硝化成二硝基甲苯，还原成二氨基甲苯，再光气化而成。由于制造甲苯二胺的工艺不同，可得3种不同的产物，见图2-1-25。  \n\n![](images/d0f178e475610f5798fd77326e57d5a4959610632bbc83ed0fcd15f2f9a62420.jpg)  \n图2-1-25甲苯二胺的制造  \n\n由图2-1-25可见，用此3种甲苯二胺产物，经光气化可制得3种不同的TDI商品，一种为2，4体；一种为 $80\\%$ 的2，4体和 $20\\%$ 的2，6体的混合物；另一种为 $65\\%$ 的2，4体和35%的2，6体的混合物。由上述甲苯二胺的制造过程可见80/20混合物最简便，所以80/20TDI供应和使用最普遍。工业产品的3种TDI的规格见表2-1-146。  \n\n表2-1-146甲苯二异氰酸酯的规格  \n\n\n<html><body><table><tr><td>指标规格</td><td>65/35</td><td>80/20</td><td>2.4体</td><td>指标 规格</td><td>65/35</td><td>80/20</td><td>2.4体</td></tr><tr><td>2.4体含量/%</td><td>65±2</td><td>80±2</td><td>≥97.5</td><td>101kPa</td><td>246~247</td><td>246~247</td><td>246~247</td></tr><tr><td>2.6体含量/%</td><td>35±2</td><td>20±2</td><td>≤2.5</td><td>折射率</td><td>1.5666</td><td>1. 5663</td><td>1. 5654</td></tr><tr><td>纯度/%</td><td>99.5</td><td>99.5</td><td>99.5</td><td>密度（20℃)/(g/mL)</td><td>1.22</td><td>1.22</td><td>1.22</td></tr><tr><td>凝固温度/°C</td><td>4.0~6.0</td><td>12. 5~14.5</td><td>≥21</td><td>黏度（25C)/mPa•s</td><td>约3</td><td>约3</td><td>约3</td></tr><tr><td>沸点/C</td><td></td><td></td><td></td><td>总氯量/% ≤</td><td>0.1</td><td>0.1</td><td>0.1</td></tr><tr><td>0. 67kPa</td><td>106~107</td><td>106~107</td><td>106~107</td><td>水解氯/%</td><td>0.01</td><td>0.01</td><td>0. 01</td></tr><tr><td>1. 3kPa</td><td>120</td><td>120</td><td>120</td><td>闪点/℃</td><td>127</td><td>127</td><td>127</td></tr><tr><td>2.1kPa</td><td>131</td><td>131</td><td>131</td><td>外观</td><td colspan=\"3\">透明，无色到微黄色的液体</td></tr></table></body></html>  \n\n以上3种商品在涂料工业中均可应用。2,4体TDI4位的NCO远比2位的NCO活泼，利用活性的差别，较易制造预聚物。65/35TDI的活性较低，但凝固点也低，冷天不需熔融，较为方便。80/20TDI的供应最多、最普遍，如无特殊注明，一般购到商品大多是80/20的混合物。  \n\n制造聚氨酯高聚物，常选用甲苯二异氰酸酯有以下几个原因。  \n\n$\\textcircled{1}$ 甲苯的硝化速率比苯快得多 $(24:1)$ ，即二硝基甲苯比二硝基苯易于生产。  \n\n$\\textcircled{2}$ 甲苯二胺是芳香族胺，比脂肪族胺容易光气化制造二异氰酸酯。  \n\n$\\textcircled{3}$ 因为它是芳香族异氰酸酯，反应活性高，利于制造泡沫塑料、涂料等，  \n\n$\\textcircled{4}$ 由于甲基的位阻影响，4位NCO的活性比2位NCO高，用它制造预聚物时便于控制，并使它黏度较低。  \n\n我国甘肃省白银化工、沧州大化等已生产TDI。  \n\nTDI的制造工艺是将甲苯二胺溶解于二氯化苯中，将光气通入此液相溶液中，前期是低温光气化，后期再升温光气化，如此可提高得率。最近拜耳公司改进成功，在后期的光气化中采用气相反应，可节约溶剂 $80\\%$ ，降低能耗 $40\\%$ ，装置尺寸大大减小，从而使投资节省 $20\\%$ 。  \n\n(2）二苯甲烷二异氰酸酯二苯甲烷二异氰酸酯（MDI）是由苯胺与甲醛缩合而成二氨基二苯甲烷（MDA)，再光气化而成：  \n\n![](images/c9872bd18f26ef14f6c9cdf9f35c4cc7338e7df4c7ac590d32f9191acc213844.jpg)  \n\n它是固体，其 $^{4,4^{\\prime}}$ 异构体的熔点为 $39.5\\mathrm{^{\\circ}C}$ ，其 $_{4,2^{\\prime}}$ 异构体的熔点为34.5℃，2，2异构体的熔点为46. $5\\mathtt{C}$ 。典型的工业产品的性质见表2-1-147所述。  \n\n表2-1-147典型工业产品性质  \n\n\n<html><body><table><tr><td>指标</td><td>规格</td><td>指标</td><td>规格</td></tr><tr><td>分子量</td><td>250.1</td><td>沸点（0.67kPa)</td><td>190°℃</td></tr><tr><td>NCO当量</td><td>125.05</td><td>(0. 7kPa)</td><td>196°℃</td></tr><tr><td>纯度</td><td>≥99.5%（烟台产品99.6%）</td><td>(2kPa)</td><td>215~217℃</td></tr><tr><td>凝固温度</td><td>≥38.0C（烟台产品≥38.1℃）</td><td>折射率</td><td>1.5906</td></tr><tr><td>颜色APHA</td><td>（烟台产品≤70）</td><td>闪点（开杯）</td><td>201℃</td></tr><tr><td>相对密度（50℃/4C）</td><td>1. 183</td><td>总氯量</td><td>≤0.1%</td></tr><tr><td>外观</td><td>白到黄色片状，并趋于粘在一起</td><td>水解氯</td><td></td></tr><tr><td></td><td></td><td>环己烷中不溶物</td><td>≤0.05% 0.7%以下</td></tr></table></body></html>  \n\nDow公司纯4， $4^{\\prime}\\mathrm{MDI}$ 产品规格：  \n\n异氰酸酯当量 125.5 相对密度（43C） 1. 180NCO含量（质量） 33.5% 蒸气压（43℃） 1. 33×10Pa黏度（43C） 5mPa \\* s  \n\n贮存稳定性（清激熔融液，无需过滤）  \n\n—20C >6个月 43°C  \n\nMDI酯在涂料中的使用量比甲苯二异氰酸酯少，有以下几个原因。  \n\n①MDI是固体，不便于管道输送和投料。  \n\n②MDI的两个NCO基的反应活性相同，制造预聚物较为困难些，产品的分子量分布宽。  \n\n③MDI在贮藏过程中不稳定，自身会二聚，需冷冻贮存和运输，很不方便。经过二聚则MDI的纯度随着时间（以及温度）而下降，同时其在环己烷中的不溶解分也上升，见图2-1-26。  \n\n![](images/41473b5da106918b703be445d8236293d30534fb47765d4f0f42e35d52b1448e.jpg)  \n图2-1-26MDI在贮藏过程中纯度、凝固点和环已烷中不溶解分的变化  \n\n$\\textcircled{4}$ MDI涂料的泛黄比TDI更严重。  \n\n但是MDI涂料也有如下优点。  \n\n$\\Phi$ 游离MDI的蒸气压远比TDI低，故毒性较低。  \n\n② MDI的对称结构，使其漆膜的强度、耐磨性、弹性均优于TDI涂料，而且干燥迅速，国外颇多用于潮气固化的地板漆、防腐蚀底漆、弹性涂料。  \n\nMDI在全球产量远比TDI大。我国万华公司在烟台和宁波的产能达36万吨/年。  \n\n(3）聚合MDI它称为PolymericMDI，也称为PAPI多亚甲基多苯基多异氰酸酯。  \n\n![](images/53647edf9cb435b132f29c3f1646c763621bdd70614c169c4fe4698907b15f09.jpg)  \n\nPAPI产品规格见表2-1-148。  \n\n表2-1-148 PAPI产品规格  \n\n\n<html><body><table><tr><td>指 标</td><td>规格</td><td>指 标</td><td>规格</td></tr><tr><td>NCO含量 黏度（20℃) 酸值 挥发分（100°℃/2.7kPa，半小时）</td><td>29%~32% 250~450mPa • s 0. 2mgKOH/g以下 0.4%以下 218C</td><td>相对密度（25℃） 平均分子量(冰点下降法） 水解氯 总氧</td><td>1. 2 300~400 0.3%以下 0.8%以下</td></tr></table></body></html>  \n\n我国烟台万华厂生产的聚合MDI，厂标YH03-86规格见表2-1-149。  \n\n表2-1-149烟台万华生产的聚合MDI规格  \n\n\n<html><body><table><tr><td>指 标</td><td>牌号MR</td><td>牌号C-MDI</td></tr><tr><td>NCO含量</td><td>30.0%~32.0%</td><td>≥31.0%</td></tr><tr><td>酸分（以HCI计)</td><td>≤0.2%</td><td>≤0.1%</td></tr><tr><td>黏度（25C）</td><td>0.1~0. 2Pa * s</td><td>≤0.1Pa• s</td></tr><tr><td>相对密度（d）</td><td>1. 23~1. 24</td><td>1.20~1.24</td></tr><tr><td>凝固点</td><td><10</td><td><20°℃</td></tr><tr><td>外观</td><td>棕色液体</td><td>棕色液体或土黄色结晶</td></tr></table></body></html>  \n\n(4）已二异氰酸酯己二异氰酸酯（HDI）由己二胺通光气而制得，是脂肪族二异氰酸酯中最重要的单体。结构式为： $\\mathrm{OCNCH_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}N C O}$ .其工业产品的规格见表2-1-150。  \n\n表2-1-150 HDI工业产品规格  \n\n\n<html><body><table><tr><td>指标</td><td>规格</td><td>指标</td><td>规格</td></tr><tr><td>分子量</td><td>168.2</td><td>熔点</td><td>67°℃</td></tr><tr><td>NCO当量</td><td>84.1</td><td>沸点(6.7Pa)</td><td>80~85°C</td></tr><tr><td>纯度</td><td>≥99.5%</td><td>(40Pa)</td><td>96~110°C</td></tr><tr><td>密度（20/4C）</td><td>1. 05g/mL</td><td>(0. 13kPa)</td><td>92~96°C</td></tr><tr><td>折射率</td><td>1.4501</td><td>(0. 36kPa)</td><td>101~103°C</td></tr><tr><td></td><td>1. 4530</td><td>(0. 67kPa)</td><td>112°C</td></tr><tr><td>总氯量</td><td>≤0.1%</td><td>(1. 33kPa)</td><td>120~125C</td></tr><tr><td>水解氯</td><td>≤0.01%</td><td>(1. 60kPa)</td><td>130°C</td></tr><tr><td>闪点</td><td>130℃</td><td>(2. 80kPa)</td><td>140~142C</td></tr><tr><td>蒸气压20℃</td><td>0.22Pa</td><td></td><td></td></tr></table></body></html>  \n\n以上沸点数据采自不同文献，容有差异，供参考。  \n\n(5）异佛尔酮二异氰酸酯在脂肪族二异氰酸酯中，除了HDI外，异佛尔酮二异氰酸酯（IPDI）也很重要。它是由丙酮三聚制成异佛尔酮，再与氢氰酸反应，制成氰化异佛尔酮，经还原再与光气反应而成：  \n\n![](images/56d46ebb6c94ae45deb0cf033f0bb94f279bc9bb5f0f334ac7ec8b081fa7dabc.jpg)  \n\nIPDI的工业产品是含顺式和反式异构体的混合物：  \n\n![](images/2975a4923054e1a19918cbf82ae5580609657a6d9e09ee62b520350b9f377fcd.jpg)  \n\n![](images/83dce791c95887d110c0d56c76ec00136d6ce39a413910d56743968567660401.jpg)  \n\nIPDI产品的规格见表2-1-151。  \n\n工业产品的纯度至少为 $99.5\\%$ ，NCO含量至少为 $37.5\\%$ ，最高的水解氯含量为$0.02\\%$ ，总氯量最高为 $0.04\\%$  \n\n表2-1-151 IPDI产品规格  \n\n\n<html><body><table><tr><td>指标</td><td>规格</td><td>指标</td><td></td><td>规格</td></tr><tr><td>分子量</td><td></td><td>222.3</td><td>闪点(闭杯）</td><td>155°℃</td></tr><tr><td>NCO当量</td><td></td><td>111.1</td><td>自燃点</td><td>430°C</td></tr><tr><td>NCO含量</td><td></td><td>37.8%</td><td>热分解温度</td><td>260℃以上</td></tr><tr><td>密度（20C）</td><td></td><td>1. 058g/mL</td><td>黏度（20C）</td><td>15mPa * s</td></tr><tr><td>折射率</td><td></td><td>1.4829</td><td>熔点</td><td>约—60°C</td></tr><tr><td></td><td></td><td>1.4844</td><td>沸点(1. 99kPa)</td><td>158°C</td></tr><tr><td>蒸气压（20C) （50℃)</td><td></td><td>90mPa 0. 9Pa</td><td>(1. 33kPa)</td><td>153°C</td></tr></table></body></html>  \n\n(6）三甲基己二异氰酸酯三甲基己二异氰酸酯（TMDI）也是由丙酮衍生而得，有两种异构体 $(50:50)$ \\*\\*  \n\nTMDI产品的规格见表2-1-152。  \n\n表2-1-152 TMDI产品规格  \n\n\n<html><body><table><tr><td>指 标</td><td>规格</td><td>指</td><td>标</td><td>规格</td></tr><tr><td>分子量</td><td></td><td>210.3</td><td>黏度（20℃）</td><td>5mPa·s</td></tr><tr><td>NCO含量</td><td></td><td>40%</td><td>沸点(0.13kPa)</td><td>144~148°C</td></tr><tr><td>NCO当量</td><td></td><td>105.1</td><td>蒸气压（20C)</td><td>0. 09Pa</td></tr><tr><td>相对密度</td><td></td><td>1.012</td><td>闪点</td><td>136°C</td></tr><tr><td>折射率</td><td></td><td>1.460~1. 461</td><td>熔点</td><td>-80</td></tr></table></body></html>  \n\nTMDI有3个甲基，所以与其他树脂的混溶性好，水解稳定性好，弹性好。但它的价格较贵，应用量不甚广。  \n\n(7）二环己基甲烷二异氰酸酯二环己基甲烷二异氰酸酯（HMDI）是将二氨基二苯甲烷用钉催化剂，在 $190\\Upsilon$ ， $35\\ensuremath{\\mathrm{MPa}}$ 压力下氢化，再光气化而得，原先由DuPont公司生产，现归属Bayer 公司称为DesmodurW：  \n\n制造HMDI的原料是二氨基二环己基甲烷，它是顺式-反式的混合物，工业生产上有将反式-反式异构体分离出来，用以制造Qiana纤维。余下的胺含顺式和反式混合物，经光气化制得液体HMDI混合物。因用副产余下的胺，故较为经济。  \n\n![](images/9342f0dec24a01cddff2cb31310fc733b858f637388f23e923256067fcb0ee02.jpg)  \n\n反式，反式的两个NCO基距离较远，故涂膜的挠性较好且有结晶性。HMDI又常称为$\\mathsf{H}_{12}\\mathsf{M D I}$ 或 PICM、SMDI、RMDI等，但以HMDI较为常见。它应用于光固化地板漆、皮革漆、织物涂料、玻瓶粉末涂料等。其工业产品4，4'异构体用气相色谱分析，含有下列组分：  \n\n<html><body><table><tr><td>反式，反式</td><td>22.7%</td><td>黏度（25℃)</td><td>(30±10)mPa * s</td></tr><tr><td>顺式，反式</td><td>62.2%</td><td>(50℃)</td><td>(12±4)mPa *s</td></tr><tr><td>顺式，顺式</td><td>15.1%</td><td>酸度</td><td>最高0.005%</td></tr><tr><td>相对密度d</td><td>1.07±0.02</td><td>闪点（Tag，闭杯）</td><td>202C</td></tr></table></body></html>  \n\n工业产品的规格见表2-1-153。  \n\n表2-1-153 HMDI工业产品规格  \n\n\n<html><body><table><tr><td>指 标</td><td>规格</td><td>指 标</td><td>规格</td></tr><tr><td>NCO含量</td><td>最低31.8%</td><td>熔融范围</td><td>19~23°C</td></tr><tr><td>水解氯（拜耳法）</td><td>≤0.0015%</td><td>蒸气压（ASTM323)25°C</td><td>约0.1Pa</td></tr><tr><td>纯度（拜耳，气相谐法）</td><td>≥99.3%</td><td>125°C</td><td>约1.33Pa</td></tr><tr><td>Hazen色度（DIN-53409）</td><td>≤35</td><td></td><td></td></tr></table></body></html>  \n\n(8）苯二亚甲基二异氰酸酯苯二亚甲基二异氰酸酯（XDI）是由二甲苯（普通为 $71\\%$ 间二甲苯、 $29\\%$ 对二甲苯的混合物）与氨氧化制得苯二甲晴，加氢还原成苯二甲胺，再光气化而成，其物理常数见表2-1-154。XDI虽含苯环，但苯环与异氰酸酯基之间有亚甲基间隔，因而性质接近于脂肪族异氰酸酯，一般习惯上常并入脂肪族异氰酸酯类来考虑。它的反应性和干燥性比HDI快，但泛黄性和保光性比HDI稍逊，比TDI则优越。  \n\n表2-1-154苯二亚甲基二异氰酸酯产品规格  \n\n\n<html><body><table><tr><td>项</td><td>目</td><td>间XDI</td><td>对XDI</td><td>工业产品</td></tr><tr><td>化学式</td><td></td><td>CHNCO CHNCO</td><td>CHNCO CHNCO</td><td>间XDI70%~75% 对XDI30%~25%</td></tr><tr><td colspan=\"2\">分子量 凝固点/℃ 沸点/C</td><td>7.2</td><td>45~46 165 (1. 60kPa)</td><td>无色透明液体 188.19 5.6 140(0. 27~0.4kPa)</td></tr><tr><td colspan=\"2\">密度/(g/cm²）</td><td>159~162(1. 60kPa) 126(0. 13kPa)</td><td>129~138 (0. 199~0. 359kPa)</td><td>151(0. 8kPa) 161(1. 3kPa) 167(1. 6kPa) 1.202(20°℃)</td></tr></table></body></html>  \n\n![](images/6c3ac71b12d81b1e2b962d673024297f626cae6c7c4badf8dd183d7a60d44291.jpg)  \n\nXDI的异氰酸基与芳环之间有亚甲基隔开而呈一定的脂肪性，但亚甲基处在苯环的a位，易被紫外线等老化，美国Cytec公司开发了四甲基苯二亚甲基二异氰酸酯，将XDI的两个亚甲基上的氢原子均以甲基取代。  \n\n（9）四甲基苯二亚甲基二异氰酸酯（TMXDI）四甲基苯二亚甲基二异氰酸酯结构如下所示（现试用于PUD水性分散体）。  \n\n![](images/b4e0511eb52d9db9df136ee2e05ccaef87c42a2817abb4cf91a76d6629523324.jpg)  \n\n此甲基取代了氢原子以后，提高了耐紫外线老化性，提高了水解稳定性，减弱了氢键作用，使延伸率增加，而且由于甲基的屏蔽影响，使NCO的反应性减弱，便于制造水性聚氨酯涂料。TMXDI产品规格见表2-1-155。  \n\n表2-1-155 TMXDI产品规格  \n\n\n<html><body><table><tr><td>指标</td><td>规格</td><td>指 标</td><td>规格</td></tr><tr><td>分子量</td><td>244.3</td><td>黏度（0℃）</td><td>25mPa + s</td></tr><tr><td>NCO含量（理论值）</td><td>34.4%</td><td>(20℃)</td><td>9mPa • s</td></tr><tr><td>当量</td><td>122.1</td><td>自燃点</td><td>450°C</td></tr><tr><td>总氯量</td><td><50mg/L</td><td>闪点(闭杯)</td><td>93°C</td></tr><tr><td>熔点</td><td>-10℃</td><td>相对密度</td><td>1.05</td></tr><tr><td>沸点(0.39kPa)</td><td>150°C</td><td>外观</td><td>无色液体</td></tr><tr><td>蒸气压（25℃）</td><td>0.39Pa</td><td></td><td></td></tr></table></body></html>  \n\n为了提高XDI的耐曝晒性，也可将苯二甲胺氢化成为环己烷二甲胺，再光气化得两种异构体；不是芳脂族而是脂肪族二异氰酸酯：  \n\n![](images/c7e131dc951a058a3a73a65a4cbe3df8c60f3a4daafafb093f816d4d9781df1c.jpg)  \n\n(10）甲基苯乙烯异氰酸酯（TMI）美国Cytec公司尚开发了新的单体，既有乙烯基双键官能团，又有异氰酸酯官能团，结构式如下：  \n\n![](images/0e3d160a8f96874bdd9c454f49ec95b4b0b1f6551bd729751b67c6545fa649e3.jpg)  \n(m，间位)  \n\n此单体既可与其他乙烯基单体共聚，残留有NCO基供进一步交联，也可先以NCO基与其他含羟基组分加成，残留乙烯基，供进一步聚合。此单体工业产品的性质如下：  \n\n分子量 201. 26 含稳定剂BHT(二权丁基对羟基甲苯) 50mg/L理论NCO含量 20.9% 均聚体的T 146°C沸点（常压） 270°C 黏度（27℃） 3mPa • s蒸气压（100℃） 0. 26kPa 密度 1. 01g/mL  \n\nDuPont公司还述及类似单体：  \n\n(11）六氢甲苯二异氰酸酯（HTDI）六氢甲苯二异氰酸酯是将甲苯二胺在氨存在下用钉催化剂在 $25\\ensuremath{\\mathrm{MPa}}$ 压力下氢化，再光气化而得，其沸点（0.13kPa）为 $87\\sim90\\ensuremath{\\uptau}$ 或127～129℃(1.6kPa)。  \n\n![](images/1035370b6db2ad68b97c6aff9a11632e997c50b347c7ab8ae79dbdc00b691108.jpg)  \n\n以上叙述的都是二异氰酸酯。在制造聚氨酯漆之中，有时尚用一种单异氰酸酯-甲苯磺酰异氰酸酯：  \n\n![](images/6e774ba0f649e2b9b2fabf4c4263b7ca99d6ce6164ae2903ae669d2f77e79214.jpg)  \n\n表2-1-156介绍工业常用的异氰酸酯。  \n\n表2-1-156涂料工业常用的异氰酸酯  \n\n\n<html><body><table><tr><td>品 种</td><td>简称</td><td>当量</td><td>沸 点</td></tr><tr><td>甲苯二异氰酸酯</td><td>TDI</td><td>87</td><td>106~107C(0. 67kPa)</td></tr><tr><td>二苯甲烷二异氰酸酯</td><td>MDI</td><td>125</td><td>190°C(0. 67kPa)</td></tr><tr><td>多亚甲基多苯基多异氰酸酯</td><td>PAPI</td><td>约137</td><td></td></tr><tr><td>己二异氰酸酯</td><td>HDI</td><td>84</td><td>112°C(0. 67kPa)</td></tr><tr><td>苯二亚甲基二异氰酸酯</td><td>XDI</td><td>94</td><td>151C (0. 80kPa)</td></tr><tr><td>四甲基苯二亚甲基二异氰酸酯</td><td>TMXD1</td><td>122.1</td><td>150°C (0. 39kPa)</td></tr><tr><td>二环已基甲烷二异氰酸酯</td><td>HMDI</td><td>131</td><td>160~165C(0.11kPa)</td></tr><tr><td>异佛尔酮二异氰酸酯</td><td>IPDI</td><td>126</td><td>153°C (1. 33kPs)</td></tr><tr><td>三甲基己二异氰酸酯</td><td>TMDI</td><td>105</td><td>144°C (1. 33kPa)</td></tr><tr><td>六氢甲苯二异氰酸酯</td><td>HTDI</td><td>90.1</td><td>87~90°C(0.13kPa)</td></tr><tr><td></td><td></td><td></td><td>127~129℃(1.6kPa)</td></tr><tr><td>甲基苯乙烯异氰酸酯</td><td>TMI</td><td>201.26</td><td>100°℃(0.27kPa)</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 367,
+        "chunk": "# 2.异氰酸酯的反应  \n\n异氰酸酯 $\\scriptstyle\\mathbf{R-N-C-O}$ 具有两个杂积累双键，非常活泼，极易与其他含活泼氢原子的化合物反应，它本身可以聚合。它的电子分布与R基有关。  \n\nNCO基上的氧原子和氮原子均呈电负性。俄国S.E.Entelis和O.V.Nesterov研究其偶极矩数据得知，NCO基中的氮原子比氧原子的电负性更大。碳原子的电子密度最低，呈正电性，所以NCO基在反应时亲电子性的，易被亲核试剂所进攻。",
+        "category": " Introduction"
+    },
+    {
+        "id": 368,
+        "chunk": "# （1）异氰酸酯与醇反应  \n\n在上式中氧原子的电子密度高，吸引氢原子而成羟基，但是不饱和碳原子上的羟基不稳定，重排成为氨基甲酸酯。这是在聚氨酯漆领域中最重要的反应，对于制造加成物、预聚物、封闭物、氨酯油等，以及双组分漆的固化都起着主要的作用。  \n\n此反应是剧烈的放热反应，例如己二异氰酸酯与丁二醇的反应热为218kJ/mol。因此制漆时要注意放热反应。必要时减缓投料速度，或用夹套冷却。笔者的经验，在某次生产投料后，突然因故障断电，搅拌器无法转动散热，造成局部过热而胶结，足见反应之热烈。  \n\n(2）异氰酸酯与水反应除了上述NCO基与OH基反应外，异氰酸酯基尚能与水反应生成不稳定的氨基甲酸，随即分解成胺而放出二氧化碳。  \n\n$$\n\\mathrm{R{\\mathrm{-}}N{\\mathrm{-}}C{\\mathrm{-}}O\\ +H_{2}O\\ {\\stackrel{\\otimes}{\\ }}{\\left(\\begin{array}{l}{\\mathrm{\\Pi_{R\\mathrm{-}\\mathrm{N-}\\mathrm{COOH}}}}\\end{array}\\right)}}{\\mathrm{\\longrightarrow}}\\ \\mathrm{R{\\mathrm{-}}N H_{\\mathrm{\\ell}}\\ +C O_{2}\\ \\uparrow}\n$$  \n\n(3）异氰酸酯与胺反应生成脲  \n\n以上第一、第二两个反应在聚氨酯漆中也很重要。潮气固化型聚氨酯漆就是通过上述两个反应固化成膜的。在制漆时若所用的原料或半制品含水，则会发生上述反应而胶凝。若成品含水则在漆罐中会产生二氧化碳而鼓气，涂料含水则涂膜会产生小泡。  \n\n(4）异氰酸酯与脲反应在高温下异氰酸酯与脲反应生成缩二脲，典型的如广泛应用的HDI缩二脲。  \n\n$$\n\\begin{array}{r l r}&{}&{\\mathrm{NH(CH_{2})_{4}N C O}}\\\\ &{}&{\\mathrm{NH(CH_{2})_{4}N C O}}\\\\ &{}&{\\mathrm{NH(CH_{2})_{4}N C O}}\\\\ &{}&{\\mathrm{OCN(CH_{2})_{4}N C O+H_{2}O\\_{2}^{\\frac{96\\mathrm{C}}{-\\mathrm{CO_{2}}}\\cdot\\mathrm{{OCN(CH_{2})_{4}N H_{2}}}\\frac{H_{101}}{96\\mathrm{C}}\\begin{array}{l l l}{\\mathrm{I}}&{\\mathrm{{I}}}&{\\mathrm{{I}}}\\\\ {\\mathrm{SiDU_{2}}}&{\\mathrm{N(CH_{2})_{4}N C O}}&{\\mathrm{{I}}}\\\\ {\\mathrm{NH(CH_{2})_{4}N C O}}&{\\mathrm{C-0}}&{\\mathrm{C-0}}\\end{array}}}\\end{array}\n$$  \n\n(5）异氰酸酯与氨基甲酸酯反应异氰酸酯在高温（ $100^{\\circ}\\mathrm{C}$ 以上）或在催化作用下也能与氨基甲酸酯反应，生成脲基甲酸酯。  \n\n此反应说明：一般制造聚氨酯漆的温度均在 $100^{\\circ}\\mathrm{C}$ 以下，以防生成脲基甲酸酯支链而胶凝，也说明聚氨酯漆经烘烤后的交联密度高，比常温固化者耐化学品性好，就是因为除氨酯键外，尚形成了脲基甲酸酯键。  \n\n(6）异氰酸酯与羧酸反应异氰酸酯与羧酸反应生成脲胺并释放出二氧化碳，但此反应较慢。  \n\n（7）异氰酸酯与酰胺反应异氰酸酯也能与酰胺反应生成酰基脲。  \n\n异氰酸酯与芳酰胺反应，会生成胱（amidine）。  \n\n![](images/a846c3b2a9235c871b15dd3fab696bea375866e40fc1754f0bd07fd1e09dea0a.jpg)  \n\n（8）异氰酸酯的高温催化反应异氰酸酯在催化及高温下能生成碳化二亚胺。  \n\n一般的温度范围约 $140{\\sim}200\\%$ ，催化剂如1-乙基-3-甲基-3-磷二烯的氧化物（1-ethyl-3-methyl-3-phospholeneoxide)，结构式如下所述。  \n\n![](images/4b881153f6c18ae1e66ad339de8f80b42cf6304bfe0847127cc8a4b7a80f0c23.jpg)  \n\n（9）异氰酸酯与酸酐反应  \n\n![](images/48c752f07efb7820b8d85511ef0b5bdd0c4bc396c1355fd3d5fd29546f08e699.jpg)  \n\n异氰酸酯与酸酐反应生成酰亚胺。二异氰酸酯与二苯甲酮四羧酸二酐反应可制备耐高温树脂。  \n\n![](images/55b9f3ee54c903e068933907c50537d278c303a37ba5378b94194e78acf9d41f.jpg)  \n\n（10）异氰酸酯与环氧基反应  \n\n![](images/77077c01eba2452cb339ba647e3b21b70e3b0ef030f2cf8125ef577d4d03e0b2.jpg)  \n\n异氰酸酯与环氧基反应生成唑烷。例如二环氧化合物与二异氰酸酯反应，生成聚嘧唑烷酮耐高温树脂（polyoxazolidines）。  \n\n![](images/1506afd42e253af68550a4ffc6437b4d508be0896526b8f812f12ef2d9868032.jpg)  \n\n（11）芳香族二胺与氯代醋酸乙酯、异氰酸酯反应芳香族二胺与氯代醋酸乙酯反应，再与二异氰酸酯反应，可制成耐高温的聚乙内酰脲（polyhydantoin）。  \n\n![](images/450ca273550b77eb3e4a70ec8bab46b87e1837bffa91c0861a37044ac151201e.jpg)  \n\n![](images/6c2112dddbcf147170aa23b50d2542c59dae06a31f41c7d845b8a970a829bf0c.jpg)  \n\n异氰酸酯与 $\\alpha$ 羟基羧酸反应亦可制得含乙内酰脲（hydantoin）的耐热涂料，用作漆包线漆。  \n\n(12）异氰酸酯二聚体除了上述反应之外，异氰酸酯尚能本身聚合。异氰酸酯较易形成二聚体脲二酮（uretdione）。  \n\n此二聚作用是一个可逆反应，二聚体在高温时可分解。在没有催化剂存在下，2,4-甲苯二异氰酸酯的二聚体在 $150^{\\circ}\\mathrm{C}$ 开始分解，在175℃完全分解。IPDI的二聚体可用作粉末涂料的固化剂，在高温下分解使聚酯固化。HDI的二聚体用以制备高固体涂料。  \n\n（13）异氰酸酯自聚成三聚体在催化剂作用下，异氰酸酯会聚合成三聚体，称为异氰脲酸酯（isocyanurate)，它性质稳定，涂膜具有快干、耐温、耐候性较好的特性。  \n\n三聚作用是不可逆的，三聚体在 $150\\sim200\\mathrm{\\textperthousand}$ 稳定不分解。三烷基麟和叔胺、碱性羧酸盐等都是三聚作用的催化剂。单独芳香族异氰酸酯可制得三聚体，典型的如Desmodur IL是TDI的三聚体，脂肪族的三聚体如HDI三聚体（Desmodur3390）和IPDI三聚体如Bayer公司的Z4470，以及不同异氰酸酯的共聚体如TDI-HDI的共聚体（DesmodurHL）和MDI $^+$ TDI共聚的三聚体（用醋酸钠作催化剂）。  \n\n上述有关异氰酸酯的各种反应对聚氨酯漆都有重要意义，将在以后分别叙述。但是从上述许多反应可以看出：异氰酸酯的反应非常复杂，有些反应可同时进行。  \n\n多异氰酸酯与多元醇反应形成聚氨酯，如情况正常，大略可按Carothers公式的官能度来估计产物的平均聚合度。若原料中含水分（颜料、溶剂中的水分），或含有催化性的杂质，或操作温度错误，或投料次序不当，则虽然按计算比例投料，仍可引起副反应而发生胶凝，因此必须充分注意对原料、中间体的检验，投料准确，并遵守操作规程。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 369,
+        "chunk": "# 3.异氰酸酯的反应性  \n\n因为异氰酸酯的反应是在带正电荷的碳原子上的亲核反应，所以吸电子基能促进异氰酸酯的活性，斥电子基能降低异氰酸酯的活性。苯异氰酸酯上取代了不同基团之后，它与醇的  \n\n相对反应性就不同。  \n\n\n<html><body><table><tr><td>结构式</td><td>取代基</td><td>反应性</td><td>结构式</td><td>取代基</td><td>反应性</td></tr><tr><td>OCN- -NO NCO</td><td>对硝基</td><td>>35</td><td>OCN-</td><td>不取代</td><td>1(作为参比标准)</td></tr><tr><td>OCN-</td><td>间异氰酸基</td><td>6</td><td>OCN- CH</td><td>对甲基</td><td>0.5</td></tr><tr><td>NHCOOR OCN-</td><td>间氨酯基</td><td>2</td><td>HC OCN</td><td>邻甲基</td><td>0.08</td></tr></table></body></html>  \n\n因为硝基吸电子而使苯异氰酸酯的反应性显著提高，对甲基斥电子而使反应性下降，邻甲基除斥电子外，更因空间位阻而使反应性大为下降。间位取代了的异氰酸基使反应性提高；即使间异氰酸基反应成为氨酯基，它的反应活性较之未取代的苯异氰酸酯仍快一倍，因此二异氰酸酯的反应性比苯异氰酸酯高。见表2-1-157。  \n\n表2-1-157异氰酸酯的反应速率  \n\n\n<html><body><table><tr><td>品种</td><td>反应速率常数 k/[μL/(mol • s)]</td><td>相对反应 速率</td><td>品种</td><td>反应速率常数 k/[μL/(mol • s)]</td><td>相对反应 速率</td></tr><tr><td>NCO</td><td>2.5</td><td>1</td><td>NCO HC NCO</td><td>2.5</td><td>1</td></tr><tr><td>NCO HC- -NCO</td><td>10.7</td><td>4</td><td></td><td></td><td></td></tr></table></body></html>  \n\n商品出售的甲苯磺酰异氰酸酯 $\\mathrm{\\bf{H}}_{3}\\mathrm{\\bf{C}}-\\bigcup_{\\mathrm{-}}\\mathrm{\\bf{so}}_{\\imath}\\mathrm{\\bf{v}}\\mathrm{\\bf{c}}0$ ，因磺酰基的强吸电子性，提高了相邻的NCO基的反应活性，超过了常用的芳香族异氰酸酯。  \n\n用己二酸与一缩乙二醇制得聚酯，取 $0.2\\mathrm{mol}$ 聚酯与0.02mol的2，4-TDI在氯苯中反应，于不同温度求其反应速率常数，结果见表2-1-158。  \n\n表2-1-158异氰酸醋基的反应速率（2，4-TDI）  \n\n\n<html><body><table><tr><td rowspan=\"2\">异氰酸酯</td><td colspan=\"4\">反应速率常数k/[L/(mol·s)]</td></tr><tr><td>29℃</td><td>49℃</td><td>72℃</td><td>100℃</td></tr><tr><td>2-NCO基</td><td>5.7X10§</td><td>1. 8X10§</td><td>7.2X105</td><td>3.2×10-</td></tr><tr><td>4-NCO基</td><td>4.5×105</td><td>1. 2X10</td><td>3.4X10-</td><td>8.5X10-5</td></tr><tr><td>相差倍数</td><td>7.9</td><td>6.7</td><td>4.7</td><td>2.7</td></tr></table></body></html>  \n\n从表2-1-158可见：4位NCO基和2位NCO基的反应性有相当大差距，但温度升高则两者的差距缩小，遵循一般化学反应因温升而速率差距缩小的规律。制造聚氨酯涂料常利用TDI的对位和邻位NCO两者的反应性的差距，使对位NCO基优先反应成为加成物、预聚体，留下邻位NCO基供涂膜固化。相对差距越大，产品的分子量分布越均匀，与其他树脂的混溶性越好，涂膜光亮透明，漆的贮藏稳定性也较佳。  \n\n涂料工业中常用的二异氰酸酯与聚醚的仲羟基的反应速率（ $70^{\\circ}\\mathrm{C}$ ）见表2-1-159及表2-1-160 $30^{\\circ}\\mathrm{C}$ ，甲苯中)。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 370,
+        "chunk": "# 表2-1-159异氰酸酯的相对反应速率  \n\n<html><body><table><tr><td rowspan=\"2\">品种</td><td colspan=\"2\">相对反应速率</td><td rowspan=\"2\">品种</td><td colspan=\"2\">相对反应速率</td></tr><tr><td>k1</td><td>k</td><td>k1</td><td>k</td></tr><tr><td>TDI(80/20)</td><td>353</td><td>32</td><td>HDI</td><td>1</td><td>0.5</td></tr><tr><td>XDI(1,3)</td><td>23.2</td><td>21</td><td></td><td></td><td></td></tr></table></body></html>  \n\n表2-1-160异氰酸酯的相对反应速率  \n\n\n<html><body><table><tr><td rowspan=\"2\">品种</td><td colspan=\"2\">相对反应速率（甲苯中，30℃）</td><td rowspan=\"2\">晶种</td><td colspan=\"2\">相对反应速率（甲苯中，30℃）</td></tr><tr><td>第一个NCO基</td><td>第二个NCO基</td><td>第一个NCO基</td><td>第二个NCO基</td></tr><tr><td>TDI(2,4)</td><td>42</td><td>1. 7</td><td rowspan=\"2\">XDI(1,4)</td><td>2.5</td><td>1.3</td></tr><tr><td>XDI(1,3)</td><td>2.8</td><td>1.1</td><td></td><td></td></tr></table></body></html>  \n\n从以上两表可以看出以下3点。  \n\n$\\Phi$ 芳香族异氰酸酯的反应速率远比脂肪族快。  \n\n$\\textcircled{2}$ 芳脂族XDI的反应速率比脂肪族HDI快。  \n\n$\\textcircled{3}$ TDI的 $k_{1}$ $k_{2}$ 差距很大。因为甲基对2位NCO基的空间位阻大，故它较4位NCO基的反应速率慢。但HDI、XDI所有的两个NCO基反应速率差距很小，这在制造预聚物时会引起产物分子量分布不均匀，须加以注意并采取措施，即投料时提高NCO：OH的比例，最后将多余过量的二异氰酸酯回收，以获得分子量低而较均匀的产品。图2-1-27为各种异氰酸酯反应速率的比较。  \n\n将4种二异氰酸酯与辛醇在 $80^{\\circ}\\mathrm{C}$ 反应，按 $1:10$ 摩尔比进行反应（醇大大过量)，表2-1-161数字表示已转化的异氰酸酯的百分率 $(\\%)$  \n\n表2-1-1614种二异氰酸酯与辛醇的反应  \n\n\n<html><body><table><tr><td>反应时间/min</td><td>TDI</td><td>HDI</td><td>HMDI</td><td>IPDI</td></tr><tr><td>5</td><td>90</td><td>23</td><td>23</td><td>10</td></tr><tr><td>30</td><td>99</td><td>79</td><td>74</td><td>60</td></tr><tr><td>90</td><td>100</td><td>99</td><td>99</td><td>91</td></tr></table></body></html>  \n\n以上数据表明，芳香族异氰酸酯反应迅速，脂肪族异氰酸酯反应速率慢，IPDI最慢。从图2-1-27可见HDI、XDI的反应速率与时间呈线性关系，而TDI则在反应达一半以上时曲线转折平坦，说明在4位NCO基反应完毕后，2位的反应速率较为缓慢，这种特性便于制造预聚物时的控制，产品均匀而稳定。反之像XDI、HDI制预聚物时必须过量投料。  \n\n异氰酸酯与醇的反应，常可认为是二级反应：  \n\n速率=k[RNCO](R'OH]  \n\n上式中 $k$ 为在该温度下该反应体系的总表观速率常数。但经过动力学研究，认为实际情况更为复杂。在某些场合，认为是三级反应：  \n\n速率 $\\underline{{\\underline{{\\mathbf{\\Pi}}}}}=$ k[RNCO](R'OH]²即在反应中是两个醇分子在起作用。可以按以下反  \n\n![](images/3545385da15b197b22fbe9c0630ae3d460dd696e68e8cdb1d6fb8775e8eec63a.jpg)  \n图2-1-27各种异氰酸酯的相对反应速率1—MDI; 2—TDI; 3—XDI; 4—HDI,TMDI; 5—HMDI、HTDI、IPDI  \n\n应机理来解释：  \n\n![](images/3682a3c953520a9a0c632425bf61f81b67d78247426bcf59a7d491f470ea9ce6.jpg)  \n\n此中间体促成质子从氧原子转移到氮原子。  \n\n![](images/eacd5d523ac590bdff81802bdb76423d0df2a00b9223ae93983397f8a772773a.jpg)  \n\n此机理说明：双组分聚氨酯漆在反应至后期时，所余羟基浓度已很低，由于反应速率与羟基浓度的平方成正比，因此速率很慢，须使用催化剂或升高温度。  \n\n佐藤研究了各种异氰酸酯与甲醇反应的动力学，认为该反应属自动催化，对于脂肪族异氰酸酯自动催化更为重要。  \n\nHC对于IPDI HC NCO(仲），它有一个伯 NCO基和一个仲 NCO，按常规推想，它HC CHNCO(伯）  \n\n与羟基反应，应该是伯NCO基更活泼，但实践证明，在不加催化剂的条件下，仲NCO基在 $20\\ensuremath{\\uptau}$ 与正丁醇的反应速率比伯NCO基快5.5倍，若加入0.075%二月桂酸二丁基锡催化，$20\\Upsilon$ 时仲NCO基比伯NCO基快11.5倍。但若加人 $0.4\\%$ 三亚乙基二胺（DABCO）催化，则伯NCO基比仲NCO基反应速率快。所以一切动力学的研究结果必须注明反应的各种条件。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 371,
+        "chunk": "# 4.活性氢组分的反应性  \n\n活性氢组分的亲核性愈大，则与异氰酸酯的反应性愈高。因此斥电子基提高活性氢组分的反应性，吸电子基降低反应性。在一般情况下可列表如下：  \n\n![](images/2603d55e46a5fe09c892b5caec62c434c2ad800992540db702c5a6801f69b8b1.jpg)  \n\n伯醇、仲醇、叔醇与苯异氰酸酯反应的相对反应速率约为 $1.0:0.3:(0.003\\sim0.007)$ ，因此制造聚氨酯涂料的三元醇常采用三羟甲基丙烷 (本章中简称TMP) $\\mathrm{CH_{3}C H_{2}C}$ $\\mathrm{\\langleCH_{2}O H\\rangle_{3}}$ 费而很少用甘油，就是因为它具有3个伯羟基，使反应迅速而完全。因此，丙烯酸羟乙酯的反应比丙烯酸羟丙酯快。同理，在某些双组分聚氨酯漆中，羟基组分的溶剂中含有二丙酮醇。此溶剂虽含羟基，但因是叔醇，反应速率很低而无妨：  \n\n在80℃时（一般的制造加成物或预聚物的温度)，按NCO：OH=1：1，以二氧六环为溶剂，比较苯异氰酸酯与几种活性氢组分反应的相对反应速率如下：  \n\n苯氨基甲酸丁酯CHsNHCOOCH; 1（氨酯） 二苯脲CHsNHCONHCHs 80（芳脲）N-乙酸苯胺CHCONHCHs 16(酰胺) 水HO 98(水)丁酸 CHCHCHCOOH 26(羧酸） 丁醇 CH;CHCHCHOH 460(伯醇）  \n\n可见在80℃制漆反应时，异氰酸酯与伯羟基的反应速率很大，比与已生成的氨酯键反应的反应速率高460倍，即生成脲基甲酸酯的副反应的可能性并不大，但仍须防止其他杂质或太高的温度引起副反应而支化胶凝。  \n\n上述的伯醇、仲醇，若含有醚键（即醚醇)，则其反应速率降低：  \n\n$$\n\\begin{array}{r}{\\mathrm{RCH_{2}O H{>}R_{2}C H O H{>}R O C H_{2}C H_{2}O H{>}\\ R O C H_{2}-C O H}}\\\\ {\\downarrow}\\\\ {\\mathrm{CH_{3}}}\\end{array}\n$$  \n\n这是因为醚醇的羟基可与另一分子醚醇的氧原子形成氢键。一般聚醚的羟基与异氰酸酯反应速率要比聚酯小。对于聚氨酯沥青漆常因施工时限太短，故采用聚醚以隆低后应速度  \n\n潮气固化型聚氨酯漆的成膜，第一步是异氰酸酯与水反应，是比较缓慢地生成胺，此不仅因速率小，而且水与预聚物（憎水性）并不相溶，必须经界面扩散进入。生成胺后，胺与异氰酸酯的反应性极强，迅速形成脲，即第二步很快。  \n\n异氰酸酯与脂肪胺的反应非常迅猛，仅用在聚脲涂料及弹性聚氨酯热塑性涂料制造中，作为高分子的扩链剂以求得良好的物理性能。此外，胺与酮反应制成酮亚胺，作为潜固化剂，可与多异氰酸酯配漆，施工后涂膜吸收空气中潮气，渐渐放出胺而生成脲键，不致太剧烈。  \n\n芳香胺的反应性稍低。弹性聚氨酯漆所常用的固化剂4,4'-二氨基-3,3'-二氯二苯甲烷(简称MOCA)，由于它的对称芳环结构的刚性和它生成的脲键的氢键吸引力，使高聚物具有很高的机械强度。邻位取代氯原子的空间位阻和吸电子效应，降低了氨基的反应速率，使双组分漆有足够的施工时限，并形成结构规整的聚氨酯-聚脲高聚物。但MOCA有致癌的危险，经Ames试验呈阳性，有致畸的危险，必须慎用，并注意劳动保护，安全操作。  \n\n![](images/bdb27c9a361842af44d0fa54364a158d02f5aef92755035dbfae4482daf0f29f.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 372,
+        "chunk": "# 5.氨酯键的反应和聚氨酯漆的泛黄  \n\n氨酯键中有个氢原子，使高分子链间形成氢键而具有良好的耐磨性、硬度和韧性，可制成弹性涂料。但是它具有一定的活性，化学上称之为不稳定氢原子，因而能引起下列反应_  \n\n（1）氨酯与另一个异氰酸酯基反应，生成脲基甲酸酯，前节已介绍。因此在制造加成物或预聚物时，若温度过高，会生成脲基甲酸酯而黏度上升、胶结。同理，聚氨酯漆在高温烘烤时，也会生成脲基甲酸酯键，提高交联密度。  \n\n（2）氨酯键的热裂解，这是一个很重要的反应，在聚氨酯漆的领域内与以下情况有关。  \n\n①封闭型单组分聚氨酯漆的固化。例如聚氨酯漆包线漆、聚氨酯粉末涂料、阴极电沉积漆等的固化。  \n\n以下反应式反映了聚氨酯漆包线涂层的易焊锡特性。  \n\n②氨酯键的热稳定性。即裂解温度的高低取决于氨酯键邻近基团的影响、封闭剂的类型、催化剂的存在，以及羟基组分的影响。氨酯键的裂解温度见表2-1-162。  \n\n表2-1-162氨酯键的裂解温度  \n\n\n<html><body><table><tr><td>品 种</td><td>裂解温度/C</td><td>品 种</td><td>裂解温度/C</td></tr><tr><td>芳族Ar—NHCOO--Ar(酚封闭）</td><td>120</td><td>芳族Ar—NHCOO—R(醇封闭)</td><td>200</td></tr><tr><td>正烷族R—NHCOO--Ar(酚封闭）</td><td>180</td><td>正烷族R—NHCOO—R(醇封闭）</td><td>250</td></tr></table></body></html>  \n\n从表2-1-162数据可见，脂肪族氨酯键的热裂解温度要比芳香族高。醇封闭者比酚封闭者裂解温度高。一般工业上酚封闭的聚氨酯漆包线在 $360\\Upsilon$ 焊锡浴中数秒钟内即分解而镀上焊锡。己内酰胺封闭者与苯酚的裂解温度相近，丁酮封闭者的裂解温度较低，丙二酸二乙酯封闭者的裂解温度更低。加入二月桂酸二丁基锡等催化剂也能降低裂解温度，促进与羟基组分交联。  \n\n(3）氨酯键在碱或酸的作用下会逐渐水解，但水解速率比酯键慢得多。其耐酸催化的水 解稳定性优于碱催化的水解。脂肪族氨酯键耐碱的稳定性优于芳香族氨酯键。  \n\n$$\n\\mathrm{RNHCOOR^{\\prime}+H_{2}O\\frac{\\partial O H^{-}}{\\partial\\Omega^{+}}\\mathrm{RNH_{2}+C O_{2}+R^{\\prime}O H}}\n$$  \n\n键的水解稳定性序列如下：  \n\n![](images/174643a6326ab99f43f350b664078ce3f196ed8c16d5cb62e5c34b6b3b04e11d.jpg)  \n\n（4）较弱的氨酯（例如芳香族异氰酸酯与苯酚制得的氨酯）可以被脂肪胺或脂肪醇所取代。此取代反应相仿于一般酯键的氨解和醇解。实用上苯酚封闭的预聚物可与脂肪胺配合，获得常温固化的密封剂，氨酯键转化为脲键。  \n\n弹性聚氨酯挥发型涂料的溶剂中不可含有伯醇，以免贮藏中醇解反应使高聚物降解变质。  \n\n（5）氨酯在高温下分解为胺和烯烃而断链。  \n\n$$\n-N H C O O C H_{2}C H_{2}\\xlongequal{\\Delta}-N H_{2}+C O_{2}+C H_{2}=C H_{2}\\rightarrow C H_{2}\n$$  \n\n上式中若为芳胺则易泛黄。  \n\n(6）氨酯的光老化。  \n\n![](images/7072bd6c5fb137a0f0681d132099f69dc823f411c3c4a7aa33ee1c93998ed7b4.jpg)  \n\n氨酯受紫外线照射后分解生成胺。芳香胺氧化后生成发色团。MDI氧化后生成双醒酰亚胺，泛黄比TDI的单醒更严重。脂肪族氨酯键比芳香族氨酯键稳定，而且即使分解成为脂肪胺，也不像芳香胺容易变色，因为没有苯环共轭作为助色团，脂肪胺又不易氧化，因而不泛黄。芳脂族的XDI虽有芳环，但氨酯键不直接连接于芳环，中间隔有亚甲基，阻止共轭的形成，所以也不会泛黄。  \n\n同样用芳香族TDI做原料，制成氨酯化合物（即加成物等）的变色比三聚体要强烈，原因如下。  \n\n![](images/0bb72ed0da4225ffbb4fca40460881bba03b0ec364b6f647592cf27ce940588e.jpg)  \n\n$\\Phi$ 叔氮原子（a）上没有氢原子，并且被三聚的异氰脲酸酯环所稳定，在（a）处不会裂解。  \n\n$\\textcircled{2}$ 即使在（b）处裂解，叔氮原子（a）阻止形成强力的助色团醒结构。  \n\nVanderVen和Geurink研究了不同结构的氨酯键（脂肪族多异氰酸酯/丙烯酸树脂）在工老化机碳弧灯（照射 $17\\mathrm{min}$ ，淋水 $3\\mathrm{{min}}$ ）2500h后的测试结果。  \n\n$\\Phi$ 涂膜中含苯乙烯会泛黄而老化。$\\textcircled{2}$ 甲基丙烯酸羟乙酯耐老化性优于甲基丙烯酸羟丙酯。$\\textcircled{3}$ 环脂族多异氰酸酯（IPDI三聚体）的耐人工老化性优于脂肪族多异氰酸酯（HDI三聚体）。图2-1-28中，A为HDI三聚体/含羟丙酯的丙烯酸树脂，B为HDI三聚体/含羟乙酯的丙烯酸树脂， $c$ 为IPDI三聚体的失重曲线。失重多者，涂膜收缩易开裂。  \n\n图2-1-29是几种不同异氰酸酯涂层在老化仪照射下变色的情况。  \n\n以上两图均是人工老化仪照射的结果仅供参考。按笔者经验，与天然日光曝晒可能有差距。例如用短波长的汞灯照射，环脂族的六氢苯酐比芳香族苯酐明显优越，但天然日光曝晒则差别并不大。  \n\n![](images/e96079f07d9ca934f6127fc1a7a1acd10ded6255ac0bbc57e10984ddd54bfd0b.jpg)  \n图2-1-28不同结构的氨酯键的老化失重  \n\n![](images/3b0411fdfa757cae57d20ead9842933cd4d5cbcc41dca910fff7918ff965881e.jpg)  \n图2-1-29二异氰酸酯涂层的变色性 $(\\mathrm{NCO}/\\mathrm{OH}=1)$ 1MDI; 2—TDI; 3—XDI; 4—HDI, TMDI; 5—HMDI, HTDI, IPDI",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 373,
+        "chunk": "# 6.催化剂  \n\n聚氨酯涂料不论在造漆或施工固化过程中，要能够恰当地控制异氰酸酯的反应。对于聚  \n\n![](images/083490c528b26c7833c7d10d49590878e5af1e2a52e85c440a71e762a70d653f.jpg)  \n图2-1-30异氰酸基与 $\\mathrm{H}_{\\mathrm{:}}\\mathrm{O}$ 的反应速率  \n\n1一三亚乙基二胺；2-三乙胺；3—二月桂酸二丁基锡；4—辛酸亚锡图中三亚乙基二胺是指1,4-二氮杂（2,2,2）双环辛烷CH—CH1N—CH—CH—N,CH--CH其N原子因无空间位阻影响，故其催化效力比三乙胺强。  \n\n氨酯漆，微量的催化剂可降低活化能，促进异氰酸酯的反应，并引导反应沿着预期的方向进行。  \n\n聚氨酯漆中常用的催化剂有以下几种。  \n\n$\\Phi$ 叔胺类如甲基二乙醇胺、二甲基乙醇胺、三亚乙基二胺、N，N-二甲基环己胺、N-甲基吗啉等。  \n\n$\\textcircled{2}$ 金属化合物如二月桂酸二丁基锡、二醋酸二丁基锡、辛酸亚锡、环烷酸锌、环烷酸钴、环烷酸铅。  \n\n$\\textcircled{3}$ 有机麟 如三丁基麟、三乙基麟。  \n\n上述甲基二乙醇胺、二甲基乙醇胺都含有羟基，除了催化作用外，尚能与异氰酸酯基反应，本身结合在涂膜中，不会被萃取出来。其中甲基二乙醇胺具有两个官能度，能参与涂膜交联，常采用于催化潮气固化聚氨酯漆中。催化剂对异氰酸基与 $\\mathrm{H}_{2}\\mathrm{O}$ 的反应速率的影响见图2-1-30。  \n\n关于异氰酸酯的催化反应，可分下列几方面考虑。  \n\n$\\textcircled{1}$ 芳香族异氰酸酯与羟基的反应ArNCO+R'OH—→ArNHCOOR  \n$\\textcircled{2}$ 脂肪族异氰酸酯与羟基的反应RNCO+R'OH—→RNHCOOR'  \n$\\textcircled{3}$ 异氰酸酯与水的反应RNCO+ HO→RNH+COzRNCO+RNH -→→ RNHCONHR  \n\n$\\textcircled{4}$ 三聚反应  \n\n![](images/103311b227844ca195521e4b0ee2afe48a16fb3ccfd0cadf4c119690efc9a274.jpg)  \n\n$\\textcircled{5}$ 形成脲基甲酸酯和缩二脲",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 374,
+        "chunk": "# $\\textcircled{6}$ 氨酯键的裂解  \n\n各种催化剂对上述的6种反应都有不同程度的影响，但是各有其主要的作用范围，二月桂酸二丁基锡、辛酸亚锡对NCO/ROH型反应的催化能力比叔胺强得多，但对于NCO/$\\mathbf{H}_{2}\\mathbf{O}$ 型反应则以胺类较佳，可见表2-1-163和图2-1-30。  \n\n表2-1-163异氰酸基与羟基的反应速率  \n\n\n<html><body><table><tr><td>催化剂品种</td><td>苯异氰酸酯与聚丙二醇在甲 苯中30C反应达到50% 反应的时间/min</td><td>催化剂品种</td><td>苯异氰酸酯与聚丙二醇在甲 苯中30C反应达到50% 反应的时间/min</td></tr><tr><td>无催化剂</td><td>>1600（慢）</td><td>辛酸亚锡</td><td>5（快）</td></tr><tr><td>三亚乙基二胺 二月桂酸二丁基锡</td><td>100(较慢） 46</td><td>环烷酸铅</td><td>6(快）</td></tr></table></body></html>  \n\n因此在制造聚氨酯预聚物过程中，有时可加入少量的锡催化剂，以引导异氰酸酯与羟基反应使生成线型的氨酯化合物，若加入胺催化剂容易引起支化，在釜中胶凝。  \n\n但对于潮气固化型聚氨酯漆，寒天施工时异氰酸酯与潮气反应，加胺的催干作用却比锡强得多。  \n\n表2-1-164介绍的是催化剂对芳香族异氰酸酯的作用。对于脂肪族异氰酸酯，由于它同羟基反应力弱，就必须依赖催化剂的作用，才能使涂膜迅速固化。用三元醇和环氧丙烷制得的聚醚，在 $70\\%$ 与3种异氰酸酯反应的情况见表2-1-164。  \n\n表2-1-164各种催化剂的作用情况  \n\n\n<html><body><table><tr><td rowspan=\"3\">催化剂</td><td colspan=\"3\">NCO/OH=111密封后胶凝时间/min</td><td rowspan=\"3\">催化剂</td><td colspan=\"3\">NCO/OH=1:1密封后胶凝时间/min</td></tr><tr><td>TDI</td><td>XDI</td><td>HDI</td><td>TDI</td><td>XDI</td><td>HDI</td></tr><tr><td>无催化剂</td><td>>240</td><td>>240</td><td>>240</td><td>邻苯基苯酚钠</td><td>4</td><td>6</td><td>3</td></tr><tr><td>三乙胺</td><td>120</td><td>>240</td><td>>240</td><td>油酸钾</td><td>10</td><td>8</td><td>3</td></tr><tr><td>三亚乙基二胺</td><td>4</td><td>80</td><td>>240</td><td>三氯化铁</td><td>6</td><td>0.5</td><td>0.5</td></tr><tr><td>辛酸亚锡</td><td>4</td><td>3</td><td>4</td><td>环烷酸锌</td><td>60</td><td>6</td><td>10</td></tr><tr><td>二月桂酸二丁基锡</td><td>6</td><td>3</td><td>3</td><td>辛酸钴</td><td>12</td><td>4</td><td>4</td></tr><tr><td>辛酸铅</td><td>2</td><td>1</td><td>2</td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n从表2-1-164的 $_\\mathrm{NCO/OH}$ 反应情况可以看出，叔胺对芳香族TDI有显著的催化作用，但对脂肪族HDI的催化作用极弱。反之，金属化合物对芳香族或脂肪族异氰酸酯都有强烈的催化作用。其中环烷酸锌对芳香族的催化作用弱，对脂肪族的作用却很强，因此对于HDI缩二脲型多异氰酸酯，常用锌作双组分漆的催干剂，因为它的毒性较二月桂酸二丁基  \n\n锡低，而且施工时限也比锡长。  \n\n因为通常探讨异氰酸酯的催化研究，有上述凝胶试验，以及以NCO基消失的二丁胺滴定的动力学两种方法。Britain和Gemeinhardt两人也做了凝胶试验法，用五种二异氰酸酯与聚酯三元醇反应，温度为 $70^{\\circ}\\mathrm{C}$ ，催化剂重量为 $1\\%$ ，混合物的固体含量为 $70\\%$ ，对多种催化剂作筛选试验，摘录部分结果列于表2-1-165中。  \n\n表2-1-165催化剂与凝胶时间关系  \n\n\n<html><body><table><tr><td rowspan=\"2\">催化剂</td><td colspan=\"5\">凝 胶 时 间/min</td></tr><tr><td>HDI</td><td>IPDI</td><td>HMDI</td><td>MDI</td><td>TDI</td></tr><tr><td>辛酸亚锡</td><td>8</td><td>90</td><td>15</td><td>4</td><td>10</td></tr><tr><td>DBTDL</td><td>2</td><td>15</td><td>5</td><td><1</td><td>5</td></tr><tr><td>钴催干剂（6%）</td><td>10</td><td>120</td><td>90</td><td>5</td><td>25</td></tr><tr><td>铅催干剂（24%）</td><td>15</td><td>25</td><td>20</td><td>3</td><td>10</td></tr><tr><td>辛酸锌</td><td>30</td><td>120</td><td>120</td><td>30</td><td>90</td></tr><tr><td>顺丁烯二酸二丁基锡（DBTM)</td><td>1</td><td>6</td><td>3</td><td>1</td><td>4</td></tr><tr><td>二醋酸二丁基锡</td><td>1</td><td>5</td><td>2</td><td><1</td><td>60</td></tr><tr><td>DABCO</td><td>25</td><td>30</td><td>40</td><td><1</td><td>1</td></tr><tr><td>DBTDL 和 DABCO(1 + 1)</td><td>1</td><td>7</td><td>3</td><td><1</td><td>1</td></tr><tr><td>二氯化二甲基锡（DMTDC)</td><td>1</td><td>6</td><td>2</td><td>1</td><td>4</td></tr><tr><td>环烷酸亚锡</td><td>40</td><td>240</td><td>150</td><td>8</td><td>30</td></tr></table></body></html>  \n\n从以上结果也可得出以下结论$\\Phi$ 芳香族异氰酸酯反应较快。  \n\n$\\textcircled{2}$ 脂肪族中HDI比HMDI及IPDI反应快些。  \n\n$\\textcircled{3}$ 辛酸亚锡比二丁基锡类反应慢，而环烷酸亚锡更慢。  \n\n$\\textcircled{4}$ DABCO加DBTDL的混合物比单纯的DABCO或单纯的DBTDL快，表示有增效作用。  \n\n$\\textcircled{5}$ 对HMDI而言，DMTDC比DBTDL的催化剂作用快，因为同样加人 $1\\%$ 质量份，DMTDC 的分子量小，锡的含量高。  \n\n以上是学术性的探讨，在预先设定的条件下的结果示例。实际制造涂料时，尚须考虑到各有关因素，通过系列实际试验才能选出合适的品种和浓度。  \n\n环烷酸铅除了强力促进NCO/OH、 $\\mathrm{NCO}/\\mathrm{H}_{2}\\mathrm{O}$ 反应以外，尚能生成脲基甲酸酯和引起NCO基的三聚作用，见表2-1-166。  \n\n表2-1-166 催化剂对苯异氰酸酯三聚作用的影响  \n\n\n<html><body><table><tr><td>催化剂</td><td>金度</td><td>）/%</td><td>催化剂</td><td>金属浓</td><td>（节三温后）/%</td></tr><tr><td>环烷酸铅</td><td>7.7×10-5</td><td>100</td><td>环烷酸锰</td><td>3.9X10-5</td><td>5</td></tr><tr><td>环烷酸钻</td><td>6.1×10s</td><td>100</td><td>环烷酸锌</td><td>5.5X10-5</td><td>0</td></tr><tr><td>环烷酸铁</td><td>4.6X105</td><td>10</td><td></td><td></td><td></td></tr></table></body></html>  \n\n除了铅以外，三烷基麟、强碱、碱性盐、钴、铁、叔胺等均能促进三聚体的形成。  \n\n通常有意识地加入微量催化剂以促使反应达到预期的效果。但有时往往也无意识地带进少量的杂质而引起强烈的催化作用，造成事故，其中要注意的有以下几点。  \n\n$\\textcircled{1}$ 聚醚中残存的微量碱性。  \n$\\textcircled{2}$ 某些颜料中残存的微量水溶性金属盐等。  \n$\\textcircled{3}$ 某些国产粗质环氧树脂中残存微量的碱性。  \n$\\textcircled{4}$ 某些国产三羟甲基丙烷以及季戊四醇中残存微量碱性。  \n\n因为这些化学品都是经由醇醛缩合及卡尼柴罗反应两步合成，均在碱性条件下生成，若精制不慎易残留微量碱性。  \n\n例如用聚丙二醇（分子量2000）46g，甘油/环氧丙烷聚醚（分子量3000）31g及TDI(80/20) $23\\mathbf{g}$ ，在 $90\\mathrm{{^{c}}}$ 反应2h制得预聚物，然后加入 $_{1g}$ 不同的催化剂和 $_{9g}$ 二氧六环（溶剂)，封于试管内，在 $70\\Upsilon$ 观察胶凝时间，结果见表2-1-167。  \n\n表2-1-167催化剂对预聚物胶凝时间的影响  \n\n\n<html><body><table><tr><td>催化剂</td><td>胶凝时间/min</td><td>催化剂</td><td>胶凝时间/min</td></tr><tr><td>酚钠</td><td>立即胶凝</td><td>三氯化铁</td><td>60</td></tr><tr><td>环烷酸铅（37%Pb)</td><td>18</td><td>二月桂酸二丁基锡</td><td>>240</td></tr><tr><td>辛酸铁（6%Fe）</td><td>16</td><td></td><td></td></tr></table></body></html>  \n\n从表2-1-167可见，碱性的酚钠具有强烈催化作用，而铁皂或水溶性铁盐催化胶凝的速率也比二月桂酸二丁基锡快得多。因此对含微量水溶性盐的颜料如铁蓝、锌黄等必须慎重，对铁质反应釜、容器等也须细心管理，避免腐蚀的锈液或铁皂混人漆中，影响稳定性。  \n\n酸、碱性的催化作用：在酸性条件下，异氰酸酯主要与羟基反应，生成氨酯预聚物；在碱性条件下，除了与羟基反应外，还与脲、氨酯反应生成缩二脲和脲基甲酸酯，自身还会三聚，生成三聚异氰酸酯而胶凝。酸、碱性的催化作用可见图2-1-31。  \n\n图2-1-31中可见：碱性增加则各种反应速率增加，酸性中仅形成氨酯，但尚须考虑空间位阻的影响。例如在苯异氰酸酯/丁醇反应体系中，比较两种胺的催化作用：  \n\n![](images/b2063488867dcc026b1b867ce0a2f80e48d070118a433d37d44d8587e8dd384b.jpg)  \n图2-1-31酸、碱性对异氰酸酯反应的影响  \n\n<html><body><table><tr><td></td><td>pK,</td><td>相对反应速率</td></tr><tr><td>三乙胺</td><td>10.8</td><td>0.9</td></tr><tr><td>三亚乙基二胺</td><td>8.2</td><td>3.3</td></tr></table></body></html>  \n\n虽然三乙胺的碱性比三亚乙基二胺强，但后者的两个氮原子都在端处，位阻小，催化作用更强。这种空间位阻的影响在锡催化剂中也存在。对于有位阻的异氰酸酯（例如四甲基苯二亚甲基二异氰酸酯TMXDI)，则二醋酸二甲基锡的催化作用优于二月桂酸二丁基锡。  \n\n![](images/702d0664c7ee1faa22b100ce3641e4dbea74455bb042d81f57eec77629a847d1.jpg)  \n\n日本的Nakamichi和Ishidoya研究了HDI缩二脲和羟基丙烯酸树脂间涂膜的反应动力学，认为是二级反应，且速率常数与温度之间关系符合Arrhenius公式。速率 $\\c=$ k[R—NCO)(R'OH]  \n\n但也有文献认为，羟基除了参与反应以外，尚有催化作用，而成为三级反应。  \n\n佐藤研究了多种异氰酸酯与甲醇的反应（无催化剂)，可以下式表示：  \n\n$$\n\\begin{array}{r l}&{\\qquad\\mathrm{R-N-C-O}+\\mathrm{R^{\\prime}O H}\\xrightarrow{k_{1}}\\mathrm{R-\\bar{N}-C-O}(\\Phi\\|\\tilde{\\mathbf{f}}\\|\\tilde{\\mathbf{f}}\\|)}\\\\ &{\\qquad\\quad\\overset{\\mathrm{O^{+}}}{\\longrightarrow}}\\\\ &{\\qquad\\mathrm{H^{\\prime}~}\\qquad\\mathrm{R^{\\prime}}}\\\\ &{\\qquad\\mathrm{R-\\bar{N}-C-O}+\\mathrm{R^{\\prime}O H}\\xrightarrow{k_{2}}\\mathrm{R-NH-C-OR^{\\prime}~}+\\mathrm{R^{\\prime}O H}}\\\\ &{\\qquad\\overset{\\mathrm{O^{+}}}{\\longrightarrow}}\\\\ &{\\qquad\\mathrm{H^{\\prime}~}\\qquad\\mathrm{R^{\\prime}~}}\\end{array}\n$$  \n\n$$\n{\\frac{\\mathrm{d}x}{\\mathrm{d}t}}{=}k_{1}(a-x)(b-x)^{2}{+}k_{2}x(a-x)(b-x)\n$$  \n\n式中x——生成的氨酯的浓度；α—原始异氰酸酯浓度；$\\boldsymbol{b}$ —原始甲醇浓度；$k_{1}$ —生成中间产物的速率常数；$k_{2}$ 一 生成的氨酯引起的自动催化的速率常数。  \n\n在Nakamichi和Ishidoya的研究中，发现对HDI缩二脲/丙烯酸树脂反应中即使没有锡催化剂，树脂的羧酸表现出强烈的催化作用。我国刘启新试验结果也证明酸值的催化作用。当丙烯酸树脂中丙烯酸含量超过 $2\\%$ 时，涂料的施工时限很短， $30\\mathrm{{min}}$ 内就胶化。对于没有酸值的树脂，二月桂酸二丁基锡具有良好的催化作用，但对于有酸值 $.A V{=}7.8$ ）的树脂，锡的催化效果下降。经碳弧灯加速老化试验，发现锡催化剂会降低涂膜的保光性。因此对缩二脲/丙烯酸体系，既然单纯羧酸 $\\scriptstyle(A V=7,8$ ）能快速催干，可不必加锡催化剂，以免降低耐候性。高桥等和Osawa等也证实了痕量的锡化合物会促进聚氨酯树脂的降解。  \n\n胺催化作用的机理，可用下式表示：  \n\n$$\n\\begin{array}{r l}&{\\xrightarrow{\\mathbb{R}\\mathrm{-}\\hat{\\mathbb{N}}\\mathrm{-}\\mathbb{C}\\mathrm{-}0}0\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad}\\\\ &{\\xrightarrow{\\mathbb{R}_{3}\\mathrm{\\tiny{N}}}\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad}\\\\ &{\\xrightarrow{\\mathbb{I}}\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad}\\end{array}\n$$  \n\n即胺促进了羟基中的质子的转移，因为胺的碱性强。欲证明上述胺的作用，Farkas等用硫基乙醇与异氰酸酯反应，其中硫基带酸性，而羟基的碱性较强，优先与NCO反应：  \n\n若加人叔胺催化剂，则胺的碱性促进了酸性SH基的质子转移，产品为：  \n\n关于锡的催化机理是锡化合物与羟基生成了络合物而促进了反应。Entelis和Nesterov、VanderWeij等都作了报道，但迄今仍未普遍接受。锡与胺两者相加，有增效催化作用，其机理可参见文献（K.N. Edwards，Am. Chem. Soc.A. C.S. Symporium Series，1981，172，393.）。  \n\n在我国涂料工业的生产实践中，原料中微量碱性往往是引起胶凝的主要原因。上海、天津、杭州造漆厂均因遭过胶凝而进行了研究，结论是微量碱性物质的存在（例如三羟甲基丙烷中残存的甲酸钠达 $300\\mathrm{mg/L}$ 即会使产品胶化，且使产品色深不合格，必须控制在 $\\scriptstyle50\\log/$ L以下)。此外醇解催化剂环烷酸钙太多也会引起胶化，这些都是预聚物成胶的常见原因，应选用纯度高的三羟甲基丙烷、季戊四醇等。  \n\n消除微量碱的影响可加入少量的酸性中和剂，我国涂料工业中常加入些磷酸（约$0.3\\%$ ，效果颇好。其他也可加苯甲酰氯、邻硝基苯甲酰氯等，其醇解产生的盐酸可中和碱性杂质。例如聚丙二醇（分子量2000）与TDI反应（NCO/OH $\\mathbf{I}=3:2$ ）制造预聚物时，所含的可水解氯与胶凝的影响可见表2-1-168。  \n\n表2-1-168水解氯对胶凝的影响  \n\n\n<html><body><table><tr><td>编号</td><td>TDI中的水解氯</td><td>添加物</td><td>总水解氯/%</td><td>结果</td></tr><tr><td>1</td><td>0.01</td><td></td><td>0.01</td><td>正常反应</td></tr><tr><td>2</td><td>0.005</td><td></td><td>0.005</td><td>43min胶结</td></tr><tr><td>3</td><td>0.001</td><td></td><td>0.001</td><td>16min 胶结</td></tr><tr><td>4</td><td>0.001</td><td>己二酰氯</td><td>0.01</td><td>正常反应</td></tr></table></body></html>  \n\n为了消除铅、麟等物质的影响，除了加入酰氯以外，可加入磷酸、硫酸二甲酯、对甲苯磺酸甲酯，或加人能螯合金属的酸（例如柠檬酸)，可消除铅的作用。  \n\n聚氨酯漆的催化剂常用二月桂酸二丁基锡或辛酸锌。试验结果认为，在光照射下锡促进涂膜降解老化，而锌则影响小。图2-1-32是以不同的乙酰丙酮金属化合物，作为MDI-聚酯所成聚氨酯漆的催化剂，其涂膜经光老化后引起的拉伸强度的下降。可见$\\mathrm{Co^{2+}}$ $\\mathrm{Co^{3+}}$ 、Cu、Ti、Sn均明显促进老化，而 $Z_{\\mathrm{{n}}}$ 、Al和Ni几乎无影响。  \n\n对于HMDI聚氨酯膜的耐潮性，与其反应时所加催化剂也有影响：  \n\n![](images/26d43a7d4988df3da2150df5a9e6f9db1a95b126e2ffe901ede2623cef000c93.jpg)  \n图2-1-32聚氨酯涂膜加人各种乙酰丙酮化合物，光照前后拉伸强度比较金属含量为0.5%（质量），1kgf/cm²=9.806N/cm²口光照前50后  \n\n<html><body><table><tr><td>催化剂</td><td>原始拉伸强度/MPa</td><td>在95%相对湿度下/MPa</td><td></td></tr><tr><td></td><td></td><td>一星期后</td><td>两星期后</td></tr><tr><td>DMTDC DBTDL</td><td>16.89 13.10</td><td>13.10 3.10</td><td>5.52 1.38</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 375,
+        "chunk": "# 7.溶剂  \n\n聚氨酯漆的溶剂选择，除了考虑溶解力，挥发速率等溶剂的共性以外，还需考虑漆中含NCO基的特性，故要注意以下两方面。  \n\n$\\textcircled{1}$ 溶剂不含能够与NCO基反应的物质，使漆变质。  \n\n$\\textcircled{2}$ 溶剂对NCO基的反应性的影响。  \n\n以上第一点是容易理解的。所以醇、醚醇类溶剂都不可采用。烃类溶剂虽然稳定，但溶解力低，常与其他溶剂合用。酯类溶剂采用最多。例如醋酸乙酯和醋酸丁酯，以往还常用醋酸溶纤剂（乙二醇乙醚醋酸酯)，它的溶解力强，挥发速率适宜，最为合用。但20年前发现乙二醇醚类溶剂对人体有一定毒性，会使生育后代致畸变，所以国外的化工公司如Bayer 均改用丙二醇甲醚醋酸酯，商品名常称MPA（methoxy propylacetate，甲氧基醋酸丙酯)，无生育致畸之患，它是醚酯。  \n\n$$\n\\begin{array}{c}{{\\mathrm{CH_{3}}}}\\\\ {{\\mathrm{H_{3}C-O-C H_{3}-C H-O-C-C H_{3}}}}\\end{array}\\begin{array}{c c}{{\\mathrm{MPA}}}\\\\ {{\\mathrm{MPA}}}\\end{array}\n$$  \n\n酮类溶剂也可用，例如甲基异丁基酮、甲基戊基酮、环已酮等，后者以往国内应用！  \n\n多，虽溶解力强，但臭味较大。而且酮类可使聚氨酯漆色泽变深。  \n\n二丙酮醇由两个丙酮分子结合而成，虽具有羟基，但属叔羟基，与NCO基反应性极低，配漆时若用于乙组分（羟基组分）中无显著影响。  \n\n![](images/73cbfe3190e0fa3c04474a2ea3437442831687fa1b1fbe535b13f8f737ee07ac.jpg)  \n\n普通的工业级溶剂外观虽然透明，但实际上多少含些水分，这是因为溶剂和水分之间具有一定的溶解度，可见表2-1-169。  \n\n表2-1-169水在100g溶剂中的溶解度  \n\n\n<html><body><table><tr><td>溶剂</td><td>溶解度/g</td><td>溶剂</td><td>溶解度/g</td><td>溶剂</td><td>溶解度/g</td><td>溶剂</td><td>溶解度/g</td></tr><tr><td>丙酮</td><td>全溶</td><td>醋酸乙醋</td><td>3. 01(20°C)</td><td>环己酮</td><td>8.7(20°C)</td><td>醋酸丁酯</td><td>1. 37(20°C)</td></tr><tr><td>丁酮</td><td>35.6(23C)</td><td>甲基异丁酮</td><td>1.9(25°C)</td><td>醋酸溶纤剂</td><td>6.5(20C)</td><td></td><td>0.06(23C)</td></tr></table></body></html>  \n\n溶剂中所含水分带到多异氰酸酯组分中会引起胶凝，使漆罐鼓胀，在涂膜中引起小泡和针孔，每1分子的水与1分子的异氰酸酯反应生成胺：  \n\n胺再与1分子异氰酸酯反应，生成脲：  \n\n并且，所生成的脲还能以一定的速率（芳脲约为伯醇的1/6，脂肪脲则比伯醇还快）与异氰酸酯反应，生成缩二脲，因此溶剂所含水分不仅会引起生成脲和缩二脲的支链，而且同时消耗了不少的异氰酸酯。即 $\\scriptstyle1\\mathrm{molff}_{2}0$ 消耗1mol以上的TDI，即 $18{\\tt g}$ 水消耗 $174_{\\mathrm{B}}$ 以上的甲苯二异氰酸酯，换言之，1份水要消耗10份的TDI，使投料配比失常，支化增加，迅速胶凝。因此，不论在树脂制造过程中，或稀释过程中都必须用无水的溶剂。  \n\n酯类溶剂，除了水分以外，还必须尽量减少游离的酸和醇的含量，以免与NCO基反应。所谓“氨酯级溶剂”就是指含杂质极少，可供聚氨酯漆用的溶剂，它们的纯度比一般工业品高，检验它是否合用的标准是抽样与过量的苯异氰酸酯反应，再用二丁胺分析残留的苯异氰酸酯量。消耗苯异氰酸酯多者不宜用，它表示酯中所含水、醇和酸三者消耗异氰酸酯的总值，以“异氰酸酯当量”表示之。“异氰酸酯当量”是指消耗1molNCO基所需溶剂的克数，数值愈大，稳定性愈好。表2-1-170介绍3种“氨酯级”酯的数据，可供参考，一般“异氰酸酯当量”低于2500以下者不合格。  \n\n表2-1-170“氨酯级”酯的数据  \n\n\n<html><body><table><tr><td>溶剂</td><td>纯度/%</td><td>沸程/℃C</td><td>异氰酸酯当量</td></tr><tr><td>酰酸乙酯</td><td>99.5</td><td>76.0~78.0</td><td>5600</td></tr><tr><td>醋酸丁酶</td><td>99.5</td><td>122.5~128. 0</td><td>3000</td></tr><tr><td>醋酸溶纤剂</td><td>99.0</td><td>150~160</td><td>5000</td></tr></table></body></html>  \n\n美国材料测试协会ASTMD3545有用气相色谱法测定酯类溶剂的纯度及所含醇量的方法。D3726为氨酯级醋酸丁酯的规格。D3727为氨酯级醋酸乙酯的规格。D3729为相应的甲乙酮的规格。用化学滴定法测定溶剂的“异氰酸酯当量”的方法可参见美国杂志。  \n\n关于第二点，溶剂对NCO基反应速率的影响，以苯异氰酸酯与甲醇在 $20\\%$ 下反应为例，列于表2-1-171。  \n\n表2-1-171溶剂对NCO基反应速率的影响  \n\n\n<html><body><table><tr><td>溶剂</td><td>k/[mL/(mol • s)]</td><td>溶剂</td><td>k/[mL/(mol • s)]</td></tr><tr><td>甲苯</td><td>0.12</td><td>甲乙酯</td><td>0.005</td></tr><tr><td>硝基苯</td><td>0.045</td><td>二氧六环</td><td>0.003</td></tr><tr><td>醋酸丁酯</td><td>0.018</td><td>丙烯睛</td><td>0. 00017</td></tr></table></body></html>  \n\n从表2-1-171可见，溶剂的极性愈大，则NCO/OH的反应愈慢，甲苯与甲乙酮之间相差24倍，这是因为溶剂分子极性大则能与醇的羟基形成氢键而缔合，使反应缓慢。  \n\n对聚氨酯漆来讲，在制造树脂过程中，若用烃类溶剂（如二甲苯）则反应速率比酯、酮类快。在双组分配漆后，则酯、酮类溶剂的施工期限可长些。经涂布后，则溶剂挥发而影响相差不大。同理，在造漆时宜选用氨酯级的溶剂以保证贮存稳定性，但在施工期间的临时少量稀释，往往可用些普通级溶剂，因溶剂在涂布后迅速挥发，影响不大。  \n\n除了化学反应的影响以外，溶剂的表面张力对聚氨酯漆的成膜也有关系。聚氨酯漆如配制不良或施工失宜，涂膜往往产生微小的气泡，损害美观和保护力。尤其以潮气固化型更需注意。经研究表明，涂料的表面张力超过 $35\\mathrm{mN/m}$ ，就不易起泡。各种溶剂的表面张力不同，所以溶剂与涂膜起泡也有关系。几种常用溶剂的表面张力值如下所述：  \n\n<html><body><table><tr><td>环己酮</td><td>38. 1mN/m</td><td>醋酸丁酯</td><td>27.6~28.9mN/m</td></tr><tr><td>二甲苯</td><td>32.8mN/m</td><td>甲基异丁酮</td><td>25.4mN/m</td></tr><tr><td>醋酸溶纤剂</td><td>31. 8~32.7mN/m</td><td>醋酸乙酶</td><td>23. 9~24. 3mN/m</td></tr><tr><td>甲苯</td><td>30mN/m</td><td></td><td></td></tr></table></body></html>  \n\n此等溶剂配入树脂基料之后，因树脂的表面张力高，所以溶液的表面张力也较高些。将潮气固化型聚氨酯树脂用不同品种的溶剂，配成不同不挥发分含量的清漆，测得的表面张力有明显的差异，可见表2-1-172。  \n\n表2-1-172溶剂对聚氨酯漆表面张力的关系 单位：mN/m  \n\n\n<html><body><table><tr><td></td><td rowspan=\"3\">环己酮</td><td rowspan=\"3\">二甲苯</td><td rowspan=\"3\">醋酸溶纤剂</td><td rowspan=\"3\">醋酸丁酯</td></tr><tr><td>溶剂 不挥发分含量/%</td><td></td></tr><tr><td>60</td><td>37.9</td></tr><tr><td colspan=\"2\">50</td><td>40.4</td><td>34.7</td><td>37.8 37.9</td><td>33.3 33.4</td></tr><tr><td colspan=\"2\">40</td><td>42.3 42.0</td><td>35.5</td><td>35.9</td><td>32.1</td></tr></table></body></html>  \n\n对于热塑性挥发型弹性聚氨酯涂料的溶剂，不可含伯醇，只可含仲醇或叔醇，以免使氨酯键断裂降解：",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 376,
+        "chunk": "# 三、制漆工艺",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 377,
+        "chunk": "# 1.聚氨酯漆的分类  \n\n异氰酸酯有高度反应活性，选用不同品种的异氰酸酯与不同的聚酯、丙烯酸树脂、聚醚或其他树脂配用，可制出许多品种的聚氨酯漆。以往颇多采用美国ASTM的分类法，早期分为5类的溶剂型涂料，见表2-1-173。德国Bayer公司的W.Wieczarrek在Ullmann化学工业大全的涂料篇中的分类又略有不同。  \n\n后来ASTM又增添了第六类，是溶剂挥发型聚氨酯漆。它是经充分扩链，分子量大的弹性聚氨酯树脂的有机溶液。因已充分反应，故不含游离异氰酸酯，涂布后干燥迅速，施工时限长，弹性良好，但因无交联，所以抗化学药品性稍低，其弹性涂料主要用于皮革、织物、磁带、橡胶等。近年因环境保护，限止VOC，又发展了水性聚氨酯涂料，其中分为水性聚氨酯分散体PUD和水性双组分2K聚氨酯涂料。  \n\n表2-1-173 ASTM聚氨酯漆分类   \n\n\n<html><body><table><tr><td rowspan=\"2\">品 性 质种</td><td colspan=\"3\">单 组 分</td><td colspan=\"2\">双 组 分</td></tr><tr><td>氨酯</td><td>封闭型</td><td>潮气固化</td><td>催化固化</td><td>羟基固化</td></tr><tr><td>固化条件 游离异氰酸酶</td><td>氧固化 无 常规 0.5~3.0 尚好</td><td>热烘烤氨酯 交换 无 常规 高温烘烤 优昇 长 漆包线漆等</td><td>NCO+HO- →聚脲 较多 困难，采取特殊操作 按湿度大小，约数小时 良好到优异 约1d 地板漆、耐腐蚀涂料</td><td>-NCO+HO+胺 聚脲及异氰脲酸酯 较多 困难，采取特殊操作 约0.5~4. 0 良好到优异 数小时 地板漆、耐腐蚀涂料</td><td>-NCO +—OH NHCOO— 较少 羟基组分分散颜料 2.0~8.0 优异 约8h 各种用途</td></tr></table></body></html>  \n\n表2-1-173所述“施工时限”是指双组分涂料在施工前混合后的可以使用的时限，太久则黏度上升、性能下降，甚至胶化而不能使用。英美等国普遍以“PotLife”表示之，我国往往译为“活化期”，会与化学中“活化能”等概念混滑而不确切。本书中概称之为“施工时限”。表2-1-174为Wieczorrek的分类。  \n\n表2-1-174 Wieczorrek分类  \n\n\n<html><body><table><tr><td colspan=\"2\">单组分 1.氨酶油或氨酯醇酸，氧固化</td><td>溶剂型</td><td>单组分 6.挥发型（水性）物理干燥或加三聚氰</td><td>含水</td></tr><tr><td colspan=\"2\">2.潮气固化</td><td>溶剂型</td><td>胺树脂固化 7.用唑烷作潮气固化剂</td><td>溶剂型</td></tr><tr><td>3.封闭型</td><td>须烘烤</td><td>溶剂型、无溶剂、粉</td><td>双组分</td><td></td></tr><tr><td>4.微胶囊</td><td>须烘烤</td><td>末 无溶剂</td><td>8.羟基固化</td><td>溶剂型、无溶剂、水</td></tr><tr><td>5.挥发型</td><td>物理干燥</td><td>溶剂型</td><td>9.加人酮亚胺，遇潮生成胺与NCO 反应</td><td>性 溶剂型</td></tr></table></body></html>  \n\n本书为了便于介绍，分类如下： $\\textcircled{1}$ 氨酯油、氨酯醇酸； $\\textcircled{2}$ 双组分（NCO/OH型）；$\\textcircled{3}$ 封闭型（溶剂型、无溶剂、粉末)； $\\textcircled{4}$ 潮气固化型； $\\textcircled{5}$ 催化固化型； $\\textcircled{6}$ 聚氨酯沥青； $\\textcircled{7}$ 聚氨酯弹性涂料； $\\textcircled{8}$ 水性聚氨酯漆。 6以上分类中，又可按所用异氰酸酯品种的不同，分为芳香族和脂肪族聚氨酯漆。",
+        "category": " Introduction"
+    },
+    {
+        "id": 378,
+        "chunk": "# 2.氨酯油  \n\n氨酯油是先将干性油与多元醇进行酯交换，再与二异氰酸酯反应，加人钻、铅、锰等催干剂，以油脂的不饱和双键在空气中干燥的涂料。它的结构和计算方法和醇酸树脂相似，但反应温度比醇酸树脂为低，示意如下：  \n\n![](images/9da62c34990d6d728fa3d8ddcdbcdfca5da5c18c9c2cd9355073891647785b3a.jpg)  \n\n氨酯油比醇酸树脂快干、硬度高，耐磨性好、抗水、抗弱碱性好，这主要是因为氨酯键之间可形成氢键，所以结膜快而硬，而醇酸的酯键间不能形成氢键，分子间的内聚力较低。  \n\n![](images/5bc37af4af7f30f39f984ffcc068a769b71192d5677926e8da2e1ce8ec4691f0.jpg)  \n\n氨酯油涂膜的性能不及含NCO基的双组分或单组分潮气固化聚氨酯漆，但因为氨酯油中不含游离的异氰酸酯基，所以它的贮存稳定性良好，施工时限长，制造色漆的手续简单，施工应用方便，价格较低，也没有因含异氰酸酯引起中毒的问题，所以适用于要求比醇酸漆的耐磨性较好，干性较快，抗弱碱性较好，而价格比含NCO基的双组分或单组分潮气固化聚氨酯漆为廉的场合。氨酯油的润湿性稍低于醇酸。在美国的DIY涂料市场，氨酯油用量很大。  \n\n用芳香族二异氰酸酯制得的氨酯油比醇酸容易泛黄，用脂肪族二异氰酸酯制得的氨酯油与醇酸的泛黄性相似。  \n\n制造方法是将干性油、多元醇、催化剂（ $4\\%$ 环烷酸钙，加入量为油量的 $0.1\\%\\sim$ $0.3\\%$ ，不宜用黄丹，否则黏度上升太快）加入反应釜，在 $230\\sim250\\Upsilon$ 间醇解 $\\mathbf{1}\\sim\\mathbf{2}\\mathbf{h}$ ，待醇解符合指标后（以甲醇容忍度测定之)，加入溶剂共沸脱水，在 $50\\mathrm{^c}$ 滴加入二异氰酸酯，搅拌半小时后，升温至 $80\\sim90^{\\circ}C$ ，并加人催化剂（二月桂酸二丁基锡，为不挥发分总量的$0.02\\%)$ ，待充分反应，异氰酸酯基完全消失（以二丁胺法测定）后，加入少量醇（作为稳定剂，以防残留NCO基，在贮存时引起胶凝）及溶剂，过滤，加入抗结皮剂及催干剂。  \n\n一般投料NCO/OH比例在 $0.9\\sim1.0$ 之间，太高则成品不稳定，太低则残留羟基多，抗水性差，所以必须准确称量。一般氨酯油的油度较长，为 $60\\%\\sim70\\%$ ，用亚麻油等。若配方的不挥发分中含TDI较多，超过 $26\\%$ 以上时，需用芳烃溶剂，含TDI低者可用石油系溶剂，示例见表2-1-175。 格  \n\n表2-1-175 含TDI低的配方  \n\n\n<html><body><table><tr><td>项目</td><td>质量/g</td><td>当量</td><td colspan=\"2\">当量数</td><td>官能度</td><td>摩尔数</td></tr><tr><td>碱漂亚麻油</td><td>1756</td><td>293</td><td>6.0 ：</td><td></td><td>1</td><td>6.0</td></tr><tr><td>季戊四醇</td><td>288</td><td>36</td><td></td><td>8.0</td><td>4</td><td>2.0</td></tr><tr><td>环烷酸钙（4%Ca)</td><td>8</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>甲苯二异氰酸酯</td><td>626</td><td>87</td><td>7.2</td><td></td><td>2</td><td>3.6</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>项目</td><td>质量/g</td><td>当量</td><td>当量数</td><td>官能度</td><td>摩尔数</td></tr><tr><td>中所含剂油（1)</td><td></td><td></td><td>. 6.0</td><td>3</td><td>2.0</td></tr><tr><td></td><td>2000</td><td></td><td></td><td></td><td></td></tr><tr><td>二甲苯</td><td>160</td><td></td><td></td><td></td><td></td></tr><tr><td>200号油漆溶剂油（2)</td><td>450</td><td></td><td></td><td></td><td></td></tr><tr><td>二月桂酸二丁基锡</td><td>2</td><td></td><td></td><td></td><td></td></tr><tr><td>丁醇（蒸过脱水）</td><td>60</td><td></td><td></td><td></td><td></td></tr><tr><td>总量</td><td>5350</td><td></td><td></td><td></td><td>13.6</td></tr></table></body></html>  \n\n平均有效官能度 $=\\frac{(6,0+7.2)\\times2}{13.6}=1.94$  \n\n$$\n\\mathrm{NCO/OH}{=}\\frac{7.2}{8.0}{=}0.9\n$$  \n\n操作：将亚麻油、季戊四醇、环烷酸钙在 $240^{\\circ}\\mathrm{C}$ 醇解约1h，使甲醇容忍度达到1：2。冷却至 $180^{\\circ}\\mathrm{C}$ ，加人第一批200号油漆溶剂油和二甲苯，搅匀，升温回流脱除微量水分，冷却至 $40\\%$ 以下。将甲苯二异氰酸酯与第二批200号油漆溶剂油预先混合，在半小时内经漏斗渐渐加人，同时不断搅拌并通入氮气。加毕后加入锡催化剂，升温至 $95\\%$ ·保温、抽样，待黏度达加氏管5s左右（约需 $2\\sim3\\mathrm{h})$ ，冷却至 $60^{\\circ}\\mathrm{C}$ ，加人丁醇使与残存的NCO基反应，以免成品日后黏度上升。过滤，冷却后加入0.1%丁酮抗结皮剂搅匀，再加入催干剂（按不挥发分计 $0.3\\%$ 金属铅， $0.03\\%$ 金属钴）即可装罐。此漆干燥迅速。其涂膜经7天后测之，坚韧耐磨，可供作地板清漆、金属底漆，以及塑料件真空镀铝前的“底油”等。漆的不挥发分约为 $50\\%$ ，其中含亚麻油 $65.6\\%$ ，含甲苯二异氰酸酯23.4%。  \n\n另一种配料的氨酯油如下：  \n\n\n<html><body><table><tr><td>亚麻油（碱源）</td><td>67.2g</td><td>季戊四醇（工业级）</td><td>4.9g</td></tr><tr><td>甘油(99%)</td><td>4.2g</td><td></td><td></td></tr><tr><td>醇解如前所述，加人下列组分：</td><td></td><td>催干剂（含6%钴）</td><td></td></tr><tr><td>TDI(80/20)</td><td>23.7g</td><td></td><td>0.5g</td></tr><tr><td>溶剂汽油</td><td>90g</td><td>（含6%锆）</td><td>1.6g</td></tr><tr><td>二甲苯 黏度（加氏管）</td><td>10g C</td><td>NCO/OH比</td><td>0.94</td></tr></table></body></html>  \n\n操作法可参见前述。若工业级季戊四醇含碱性杂质太多，则在加入TDI之前，宜酌加 少量磷酸中和之。  \n\n有时为了降低成本，减少TDI用量，可制造氨酯醇酸，即从前述配方中减少一半TDI量，1.8mol苯酐替代之。先将亚麻油与季戊四醇进行酯交换，达到甲醇容忍度后，再加入苯酐充分酯化后，按前述配方操作，加溶剂充分脱水，然后渐加入TDI，使之与剩余的羟基反应。所获氨酯醇酸，快干而坚硬，一星期后可打磨。我国天津、上海等生产TDI改性醇酸，烟台生产MDI改性醇酸，效果颇好。此外，也可将氨酯油冷拼入醇酸中，以提高干性。  \n\n若所加二异氰酸酯不是芳香族的TDI、MDI，而是环脂族的IPDI或芳脂族的XDI，则泛黄性可以改善。例如： $220\\mathbf{g}$ 红花油（我国新疆有产）（0.25mol）与 $_{348}$ 季戊四醇$(0,25\\mathrm{mol})$ 在 $235\\mathrm{{T}}$ 醇解，通入氮气，以辛酸钙为催化剂，约 $50\\mathrm{min}$ 后达甲醇容忍度透明，加人 $37g$ 苯酐酯化 $(0,25\\mathrm{mol})$ ，在 $235\\mathrm{{T}}$ 约3h后酸值降至2.7，加人XDI，以 $_{0.63g}$ 二月桂酸二丁基锡为催化剂，在 $100\\mathrm{\\textperthousand}$ 反应约2.5h，操作可参阅前述。催干剂为 $0.2\\%$ 环烷酸铅、0.02%环烷酸钴。本例中的红花油，较不易泛黄，因为它的成分中所含十八碳三烯酸含量仅$0.2\\%$ ，而豆油含此酸 $2.2\\%$ ，亚麻油含34.1%之多，故容易泛黄。  \n\n表2-1-176是将某较短油度醇酸与相似的氨酯醇酸配制成金属底漆，涂成50μm干膜的性能比较。  \n\n表2-1-176某较短油度醇酸与相似氨酯醇酸配制的金属底漆涂成50μm干膜的性能  \n\n\n<html><body><table><tr><td>性 能</td><td>氨酯醇酸</td><td>醇酸</td><td>性</td><td>氨酯醇酸</td><td>醇酸</td></tr><tr><td>硬度（Konig摆杆，7d后）/s</td><td>80</td><td>38</td><td>铝板（14d后）</td><td>优</td><td>中</td></tr><tr><td>Erichsen杯突（7d后）/mm</td><td>3.5</td><td>2.0</td><td>石击试验（7d后）</td><td>良</td><td>可</td></tr><tr><td>附着力（划格法，DIN，53151）</td><td></td><td></td><td>喷丸试验（DIN53154）</td><td>6000丸</td><td>3700丸</td></tr><tr><td>钢板（14d后）</td><td>优</td><td>良～中</td><td>抗水性（1d后，水迹）</td><td>良</td><td>劣</td></tr></table></body></html>  \n\n可见氨酯改性的醇酸，既硬又韧，耐石击、耐水，适用作车辆及工业产品底漆、内用的工业产品的面漆、浸渍底漆等。  \n\n氨酯油的催干剂也是常规的钻、锰、铅等金属皂，举以下配方示例：  \n\n氨酯油（48.5%不挥发分） $70\\pmb{\\mathrm{\\Pi}}$ 丁酮肪 石油溶剂 17g  \n\n表2-1-177为加人不同催干剂的效果（均在3h内硬干）。  \n\n表2-1-177不同催干剂的效果  \n\n\n<html><body><table><tr><td>催干剂</td><td>A</td><td>B</td><td>C</td><td>D</td><td>E</td><td>F</td><td>G</td></tr><tr><td>钻（金属）</td><td>0.02</td><td></td><td>0.01</td><td>0.02</td><td>0. 04</td><td>0.03</td><td>0.02</td></tr><tr><td>锰（金属）</td><td></td><td>0. 02</td><td>0.01</td><td>0.02</td><td></td><td></td><td>0.02</td></tr><tr><td>铅（金属）</td><td>0.10</td><td>0. 10</td><td>0.20</td><td></td><td>0.40</td><td></td><td>0.40</td></tr><tr><td>钙（金属）</td><td></td><td></td><td></td><td></td><td>0.04</td><td></td><td></td></tr><tr><td>锌（金属）</td><td></td><td></td><td></td><td>0.02</td><td></td><td></td><td></td></tr><tr><td>一周后涂膜（sward）硬度</td><td>27</td><td>20</td><td>24</td><td>24</td><td>30</td><td>32</td><td>30</td></tr><tr><td>两月后涂膜（sward）硬度</td><td>40</td><td>34</td><td>38</td><td>32</td><td>34</td><td>38</td><td>38</td></tr><tr><td>浸水后涂膜</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>光泽</td><td>好</td><td>好</td><td>好</td><td>发白</td><td>好</td><td>好</td><td>好</td></tr><tr><td>附着力</td><td>可</td><td>差</td><td>好</td><td>很好</td><td>差</td><td>差</td><td>可</td></tr><tr><td>恢复1h后</td><td>脆</td><td>很脆</td><td>微</td><td>很好</td><td></td><td></td><td></td></tr></table></body></html>\n\n$\\Phi$ 催干剂添加量为质量份。  \n\n表2-1-177数据说明，氨酯油系涂膜的性质，不仅与其树脂的投料及操作有关，且与其催干剂、溶剂等有关。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 379,
+        "chunk": "# 3.双组分聚氨酯漆（NCO/OH型）  \n\n双组分聚氨酯漆分为甲、乙两组分，分别贮存。甲组分含有异氰酸酯基，乙组分一般含有羟基。使用前将甲乙两组分混合涂布，使异氰酸酯基与羟基反应，形成聚氨酯高聚物。这类双组分聚氨酯漆是所有聚氨酯漆中应用最广泛，调节适应性宽，最具代表性的品种。文献中常称为2K涂料（来自德文2kompomenten，双组分），又常见称为DD涂料（来自Bayer公司产品名称Desmodur/Desmophen，其中dur来自拉丁字duruo为硬化剂之意，Desmo来自希腊字，意为带子，起联结作用)。关于此两个组分的称谓，日本等称羟基组分为主剂，因含颜料等而体积大而重，称异氰酸酯组分为硬化剂。我们本书中则称异氰酸酯部分为甲组分，羟基部分为乙组分，因为在聚氨酯漆的调配及计算中，习惯上采用 $\\operatorname{NCO}:\\operatorname{OH}$ 之比，即NCO组分在先。此含NCO组分称之为多异氰酸酯polyisocyanate，指含有3个或3个以上NCO基的低聚物，起扩链和交联作用。羟基组分常称之为多元醇polyol，指含有多个羟基的齐聚物，但必须与甘油、季戊四醇等简单多元醇的polyol区分开来。  \n\n（1）多异氰酸酯组分多异氰酸酯组分应具备以下条件。  \n$\\Phi$ 良好的溶解性以及与其他树脂的混溶性。  \n\n$\\textcircled{2}$ 与羟基组分拼和后，施工时限较长。  \n\n$\\textcircled{3}$ 足够的官能度和反应活性，NCO含量高。  \n\n$\\textcircled{4}$ 贮存稳定性长。  \n\n$\\textcircled{5}$ 低毒。  \n\n直接采用挥发性的二异氰酸酯（如TDI、HDI等）配制涂料，则异氰酸酯挥发到空气中，危害工人健康，而且官能团只有两个，分子量又小，不能迅速固化。所以必须把它加工成低挥发性的低聚物，使二异氰酸酯或与其他多元醇结合，或本身聚合起来。  \n\n加工成为不挥发的多异氰酸酯的工艺有3种。  \n\n$\\Phi$ 二异氰酸酯与多元醇（例如三羟甲基丙烷等）加成，生成以氨酯键联结的多异氰酸酯，常称为加成物（adduct）。  \n\n$\\textcircled{2}$ 二异氰酸酯与水等反应，形成缩二脲型多异氰酸酯，典型的如HDI缩二脲多异氰酸酯，在我国广泛应用。  \n\n$\\textcircled{3}$ 二异氰酸酯聚合，成为三聚异氰酸酯，化学名称为异氰脲酸酯isocyanurate的多异氰酸酯。一般的二聚体不稳定，较少用于涂料工业生产。IPDI以及HDI的二聚体有工业产品，IPDI作粉末涂料的固化剂，经烘烤解聚而起交联作用。HDI的二聚体用作高固体涂料中的活性稀释剂。  \n\n兹将3种不同工艺分述如下。  \n\n$\\Phi$ 加成物型最常用的是3分子TDI与1分子三羟甲基丙烷（TMP）的加成物。因为TDI的4位NCO的活性比2位高，所以容易制造。  \n\n![](images/0fd6717b7fb52bcacb7021b83731e6edb25cecc08f2a05757d64f6add32c40fe.jpg)  \n\n以上仅是示意式，实际产品有分子量分布，含有比上式分子量更高者。早期工业产品尚含有相当多的游离TDI，后经改进，将游离TDI降低至0.7%以下（按固体分计)。这类加成物是双组分聚氨酯漆中常用的多异氰酸酯，广泛用作木器漆、耐腐蚀漆、地板漆等，产量大、用途广。  \n\n这种加成物的制备工艺各厂略有差异，一般是将TDI投人反应釜（也有投人一部分经脱水的溶剂)，搅拌升温至 $60^{\\circ}\\mathrm{C}$ ，将熔融的三羟甲基丙烷（或加醋酸乙酯等溶剂)，渐渐加人，使其充分反应，在 $60\\sim70\\ensuremath{\\uptau}$ 保温3h（用二丁胺法滴定，可测得NCO含量已趋稳定)，加入其余溶剂，保温揽匀，冷却出料装罐。  \n\n以下是我国某厂早期简便的操作示例。  \n\n投料：  \n\n<html><body><table><tr><td>原料 三羟甲基丙烷</td><td>规格</td><td>摩尔比 1</td><td>投料量/kg 44.67</td><td>百分比/% 9.64</td></tr><tr><td>甲苯二异氰酸酯</td><td>98%</td><td>3.2</td><td>189.02</td><td>40.75</td></tr><tr><td>环己酮</td><td></td><td></td><td>25.40</td><td>5.47</td></tr><tr><td>醋酸丁酯</td><td>一级工业品</td><td></td><td>108.70</td><td>23.45</td></tr><tr><td>二甲苯</td><td>CaCl处理品</td><td></td><td>96.00</td><td>20.69</td></tr><tr><td></td><td></td><td></td><td>(15.0)</td><td></td></tr><tr><td>循环用纯苯（脱水用）</td><td>工业品</td><td></td><td></td><td>100.00</td></tr></table></body></html>  \n\n操作：  \n\n先将三羟甲基丙烷、环己酮和纯苯一起投入釜中，开动搅拌，升温至 $80^{*}\\mathrm{C}$ 停止搅拌。继续升温至 $140^{\\circ}\\mathrm{C}$ ，蒸出苯水混合物，补加损失的环已酮量后，即得三羟甲基丙烷环已酮溶液。降温备用。  \n\n将甲苯二异氰酸酯和二甲苯全部投入反应釜中，再加入9/10量的醋酸丁酯于反应釜中，开动搅拌，升温至 $40\\Upsilon$ ，在此温度下徐徐加入三羟甲基丙烷环已酮溶液，加料时控制反应釜内温度，若升温太快，可以停止加料，使反应温度维持在 $40\\sim50\\ensuremath{\\mathrm{\\:{C}}}$ ，最后全部加完后，加人 $1/10$ 量的醋酸丁酯，升温至 $75\\%$ ，在 $(75\\pm2)\\gamma$ 下保温2h后取样测定其NCO含量和不挥发分，当NCO含量为 $8\\%\\sim9.5\\%$ ，不挥发分为 $50\\%\\pm$ $2\\%$ 时为合格，然后出釜过滤，包装。  \n\n此产品中尚含很多的游离甲苯二异氰酸酯，施工时有害于工人健康。为了降低游离的二异氰酸酯的含量，可以采用3种方法。  \n\na.薄膜蒸发法上述加成物粗制品，若单凭简单蒸馏欲除去游离TDI，则必须将整个粗制品长时间高温加热，但异氰酸酯在 $100\\Upsilon$ 以上易生成脲基甲酸酯，而在 $150\\mathrm{^c}$ 以上更甚，使产品变质，可是游离TDI却仍残留很多。采用薄膜蒸发法可使受热时间缩短，蒸发面积大，游离的TDI蒸出快（图2-1-33)。目前薄膜蒸发法是制造加成物脱除游离二异氰酸酯最常用的工艺，国外自20世纪50年代后期采用此法使产品游离TDI降至$0.7\\%$ 以下。我国目前也在开发中。  \n\n将加成物粗制品送入降膜式薄膜蒸发塔，由塔的上部被旋转的刮板刮成薄膜徐缓流下，塔内减压达0. $11\\mathbf{kPa}$ ，塔的夹套分为数段，按工艺要求以0.8～1.4MPa的蒸汽加热（亦可用其他加热介质)，塔内各段温度按工艺要求，为160～200℃。游离的TDI蒸出，冷凝回收。提净的加成物流至塔底排出，约含游离TDI0.7%以下。配成 $75\\%$ 溶液后则含量为 $0.5\\%$ 以下。有些工艺为了促使微量 TDI从加成物中蒸出，可在塔底通人二氯化苯蒸气。蒸出每份TDI约需通入0.02份二氯化苯。其他工艺则采用第二次短程内蒸发法，又称为分子蒸馏，第二次用内冷式短程蒸发器则可提高蒸除效率。  \n\n![](images/4eb831f2106995fc0f258fa48128880600bafa37e52a06e8c8eb265ed8d18a2f.jpg)  \n图2-1-33薄膜蒸发示意图  \n\nb.溶剂萃取法此法适用于萃取沸点高、蒸气压低的二异氰酸酯。因为TDI、HDI均有一定的蒸气压，易于用薄膜蒸发除去，而像MDI、IPDI等蒸气压低难以蒸除的二异氰酸酯，则可用溶剂萃取法，例如 Bayer 公司提及用萃取法以提去IPDI。此法是用混合烃加入到加成物粗制品中，游离的二异氰酸酯能溶解于混合烃，而加成物不溶解而析出于底层。分去上层混合烃，再加新鲜混合烃，搅拌洗数次以萃取游离二异氰酸酯，以得提净的产品。此法不需薄膜蒸发塔和真空设备，也不需高压蒸汽，一般工厂容易投产。但是需多次洗提，手续稍烦，并必须注意消防安全，效率也不高，实用不多。  \n\n操作示例：将3.5molTDI及200g醋酸乙酯投人反应器，搅拌、升温至60C，渐渐滴加1mol熔融的三羟甲基丙烷，由于反应放热，要注意维持温度，如温度高可减缓加料速度或夹套冷却。加毕在75℃维持3h左右，使之充分反应。加入3倍量的萃取溶剂（可用石油烃与芳烃的混合物，例如沸程80～120℃的石油烃加20%甲苯)，反应器中的物料分为两层。分出上层液，留下的树脂层再以混合溶剂洗提5次，每次分出的上层液随即同时蒸馏，循环回收溶剂，供下一次洗提，余下的TDI及少量树脂状加成物可并入下一批投料。在反应器中的下层树脂，减压蒸除少量残留的萃取溶剂后，加入醋酸乙酯（或其他溶剂）以配成所需溶液。含游离TDI的量经多次萃洗可明显降低。上述投料比采用3.5molTDI，则产品黏度低而稳定，如用 $3\\mathrm{{mol}}$ ，则产品黏度高而稳定性差。上述混合烃中，石油烃溶解力低，使树脂析出，芳烃溶解力较大，使树脂层软。在洗涤时如树脂层黏稠不易洗，可提高温度或芳烃含量，使树脂层软而易洗，若不易分层析出，可提高石油烃含量。  \n\n一般的TDI加成物的工业产品性质如下：  \n\n\n<html><body><table><tr><td>不挥发分</td><td>75%±1%</td><td>密度（20C）</td><td>1. 17g/mL</td></tr><tr><td>溶剂</td><td>酯酸乙酯或丙二醇甲醚</td><td>黏度（20℃）</td><td>2.5Pa*s左右</td></tr><tr><td></td><td>醋酸酯：二甲苯=1:1</td><td></td><td>（普通规格）</td></tr><tr><td>NCO含量</td><td>13.0%±0.5%</td><td></td><td>0.7Pa·s左右</td></tr><tr><td>游离TDI含量</td><td>0.5%以下</td><td></td><td>（低黏度规格）</td></tr><tr><td>密闭贮存期</td><td>1～2年</td><td>外观</td><td>微黄澄清液</td></tr></table></body></html>  \n\n除了上述 $75\\%$ 溶液外，为适应各种需要，也有配成 $67\\%$ 溶液、60%溶液、50%溶液等。  \n\n在制造过程中，一般加人些醋酸乙酯等溶剂，也有不加溶剂，单使TDI与熔融的三羟甲基丙烷反应。加入溶剂可使反应物均匀，利于传出反应热，并能将溅于釜壁的三羟甲基丙烷小粒冲洗回液相中而均匀反应，避免在釜壁产生不溶的小颗粒，可避免过滤和洗釜的麻烦。但是加入溶剂后则回收溶剂工作较为困难，混在石油烃中不易分离回收。  \n\n制造TDI与三羟甲基丙烷的加成物的一个控制因素是TDI与三羟甲基丙烷之间的摩尔比。比例高则产品的分子量低，分子量分布均匀，与其他树脂的混溶性较好，黏度较低，贮存稳定性较好，但比例太高，则回收萃取游离TDI工作较烦。  \n\n另一个重要因素是TDI的规格。例如对于2，4体的TDI及80/20的TDI曾作过对比，用TDI及三羟甲基丙烷按 $_3:1$ 摩尔比在溶剂中于 $40\\%$ 反应，溶剂占总重的 $40\\%$ ，由2/3的醋酸溶纤剂及1/3的甲苯所组成。产品性质如下：  \n\n2,4体的TDI所得产品：含游离TDI3.3% 80/20的TDI所得产品：含谢离TDI5.7%  \n\n我国涂料工业生产此类TDI/TMP加成物已历时20余年，近年来各厂不断改进，例如上海新华树脂厂为了改进该产品色泽，研究了TDI与多元醇的比例，使树脂中游离TDI降至最小值，以免其受热泛黄，选择合适的抗氧剂，减少使用易被氧化的溶剂，降低了反应温度，结果产品色泽从原先的8挡（加氏管）降低至2挡以下，有些抽样色泽接近水，为无色透明。  \n\nc.三聚法为了降低加成物中游离单体，尚可采用三聚法。加催化剂于加成物的粗产品中，则所含游离TDI的4位上的NCO基优先三聚成树脂状不挥发物，而达到降低游离TDI的效果。示例如下：将TDI（65/35）1274g及醋酸丁酯 $500\\mathbf{g}$ 投入反应器，搅拌并升温至 $^{50^{*}\\mathrm{C}}$ ，另外将三羟甲基丙烷 $160\\mathbf{g}$ 及1,3-丁二醇 $66{\\bf g}$ 预先加温混合，逐渐滴入反应器，在1h内加完，NCO/OH投料比约为 $3:1$ 。在 $50\\sim60\\ensuremath{\\uptau}$ 反应搅拌5h，待反应完毕，再添加醋酸丁酯 $1000g$ 稀释之。此混合物含NCO基13. $1\\%$ ，游离的TDI达 $12.5\\%$ 。对此混合物加人 $_{9g}$ 三正丁基麟，在室温搅拌，黏度徐徐上升。经 $6\\sim7$ 天后，NCO基含量为 $7.2\\%\\sim$ $7.5\\%$ ，而挥发性的游离TDI含量则下降到 $0.2\\%\\sim0.3\\%$ ，此时加入 $18\\mathbf{g}$ 苯甲酰氯，加温至$100\\mathrm{^{\\circ}C}$ 保持片刻，使聚合反应中止，即得稳定溶液。  \n\n除了TDI以外，苯二亚甲基二异氰酸酯（XDI)、异佛尔酮二异氰酸酯（IPDI）等都有加成物的产品，具有不泛黄的优点。  \n\nXDI的两个NCO基的反应活性很接近，因此制造加成物较为麻烦，若投料的摩尔比接近 $3:1$ 时则产品的混溶性极劣，说明如下：2mol的TDI（2,4体）与1mol的二元醇（例如1，4-丁二醇）在低温反应时，由于4位与2位的活性差异，所得产品基本上是下式低分子  \n\n量化合物：  \n\n![](images/5d1e5927b855c62b044498301ee8f5bdb76414e37b22bd34f160a7b87af86110.jpg)  \n\n但若某种二异氰酸酯（以I表示之)，它的两个NCO基是对称而具有相同的活性，它与二元醇（G）按 ${\\mathfrak{z}}:1$ 比例反应时，产品并不是单纯的上式低分子量加成物，而是复杂的混合物，分子量分布极不均匀。按Flory的概率统计 $N_{\\mathfrak{n}}{=}N_{\\mathfrak{t}}P^{\\mathfrak{n}-1}$ (1-P)：  \n\n<html><body><table><tr><td>分子</td><td>摩尔分数</td><td>分子</td></tr><tr><td>I</td><td>0.50</td><td>IGIGIGI</td></tr><tr><td>1-G-1</td><td>0.25</td><td>I-GIG—IG—IGI</td></tr><tr><td>1-G—I-G-I</td><td>0.125</td><td></td></tr></table></body></html>  \n\n若与三元醇反应，则分子量分布更复杂，因此对于像HDI、XDI、HMDI等两个NCO基活性相同的二异氰酸酯与三羟甲基丙烷反应，若单按 $3:1$ 摩尔比投料，产品分子量分布大、稳定性差、黏度高、混溶性差，涂膜甚至发浑不透明。必须提高摩尔比，才能获得满意的产品，示例如下。  \n\n投料：  \n\nXDI  \n\n![](images/9339a977464af423b994f514b8de415f6d0858f42f66c665ee88fdc3aff0dbf8.jpg)  \n\n操作：将XDI投入反应器，搅拌，在氮气流下升温至 $60^{\\circ}\\mathrm{C}$ ，滴加熔融的三羟甲基丙烷，升温至 $70^{\\circ}\\mathrm{C}$ 保持2h，再用混合烃萃取多余单体（见前）数次，制得 $75\\%$ 的醋酸乙酯溶液。回收的过量XDI并人下次投料。  \n\n产品的胺当量为370，即含NCO基 $11.4\\%$ ，与聚酯、丙烯酸酯树脂等混溶性良好。它的甲苯容忍度为240，如采用 $3:1$ 摩尔比，则产品的甲苯容忍度仅为10，不能与聚酯混溶。  \n\n甲苯容忍度测法：取样品 $_{2g}$ C $75\\%$ 醋酸乙酯溶液）置入试管，从滴管滴加甲苯，直至发浑为终点。  \n\nXDI加成物工业产品的性质如下：  \n\n<html><body><table><tr><td>胺当量</td><td>370</td><td>稀释率/%</td><td></td></tr><tr><td>NCO含量</td><td>11.4%左右</td><td>甲苯</td><td>200</td></tr><tr><td>溶剂</td><td>醋酸乙酯</td><td>醋酸乙酯（或丁酯）</td><td>>1000</td></tr><tr><td>不挥发分</td><td>75%</td><td>醋酸溶纤剂</td><td>>1000</td></tr><tr><td>黏度（25℃，加氏管）</td><td>2. 65s</td><td>甲基异丁酮</td><td>>1000</td></tr><tr><td>色泽（铁钻比色法）</td><td>1</td><td>石油溶剂</td><td>不溶</td></tr><tr><td>相对密度（d）</td><td>1.15</td><td></td><td></td></tr></table></body></html>  \n\n$\\textcircled{2}$ 缩二脲多异氰酸酯典型的工业产品例子是由3mol的HDI和lmol水所反应生成的具有三官能度的多异氰酸酯。示意式如下，实际产品则尚含些聚合度更高的组分。  \n\n![](images/aa943e16d72d979c58a91a7e05a06388bbbd09ceb6ae77494c78d33925d6cd26.jpg)  \n\n此多异氰酸酯不会泛黄，耐候性很好，可以与聚酯或聚丙烯酸酯配套，制造常温固化户外用漆，如飞机漆、火车漆、大型客车漆等，以及用于建筑外墙、海上平台上层漆等。我国目前以进口为主，典型的如Bayer公司的N-75，性质如下：  \n\n不挥发分 75%±1% NCO含量 约16.5%溶剂 酯酸乙酯（也有是丙二醇甲醚 黏度（23℃） 225mPa•s醋酸酯：二甲苯=1:1) 色泽（铁钻法） 1胺当量 约1.15  \n\n游离HDI含量：新品为 $0.5\\%$ ，久贮后会上升至 $0.9\\%$  \n\n上述N-75为常用品种。近年各国对环境保护日益重视，限制溶剂释放，因此另有一种工业产品是不含溶剂的缩二脲多异氰酸酯，供制造高固体或无溶剂涂料，典型的如Bayer公司的N-3200，其性质如下：  \n\n不挥发分 100% 黏度（23C） 2500\\~3000mPa\\* sNCO含量 23% 游离HDI含量 0.7%（久贮升至1.2%）胺当量 183 熔融温度 约19°C  \n\n缩二脲多异氰酸酯的制备： $2560\\mathrm{g}(15.2\\mathrm{mol})$ 的HDI投入反应器，搅拌、升温到 $97\\sim$ $99^{\\circ}\\mathrm{C}$ ，在6h内逐渐加人水56g（3.1mol)，升温到 $130{\\sim}140^{\\circ}\\mathrm{C}$ ，保持 $3\\sim4\\mathrm{h}$ ，冷却，过滤除去少量的聚脲。滤液经薄膜蒸发回收过量的己二异氰酸酯，得缩二脲的透明黏稠液 $11758$ .  \n\n![](images/aa0f3978b176fd79521fb0fab170322d17542978aec73c88520b4f707ed994cb.jpg)  \n图2-1-34 HDI缩二脲的凝胶色谱图  \n\n固体分含NCO基 $20.79\\%$ ，加人溶剂稀释至所需固体量。  \n\n以上是一种示例，实际上工业制造方法的专利报道极多，其要旨是减少聚脲的生成，有不加水而用蒸气者，有用胺者，有用三甲基醋酸者，有用溶剂将水溶入使反应均匀者，不胜枚举。例如日本专利所述：将 $\\mathrm{\\HDI1512g}$ 、水 $18g$ 溶于 $350\\mathrm{g}$ 的乙二醇甲醚醋酸酯，在 $160^{\\circ}\\mathrm{C}$ 反应1h。然后经薄膜蒸发回收HDI及溶剂，得HDI缩二脲，其NCO含量为23. $7\\%$ ，黏度 $(25^{\\circ}\\mathbb{C}$ ）为 $1200\\mathrm{{mPa}}$ ·s，游离 $H D I0.2\\%$ 费  \n\n图2-1-34是商品（ $100\\%$ 固体分HDI缩二脲，DesmodurN-100）的凝胶色谱图，表征其分子量分布。可见其中主要是3个HDI单元的产品，但可见极少量含两个单元，以及稍多的较高聚合度的产物。  \n\n$\\textcircled{3}$ “三聚体”型多异氰酸酯（isocyanurate polyisocyanate）习惯上称为“三聚体”，实际上是不同聚合度的混合物，化学结构上称为异氰脲酸酯，由三个RNCO组成六环，故称为三聚体 Trimer。  \n\n![](images/4cb17185c36a13f65f9b33e3c537226fffc791d7f7506aeda22b2638ba695119.jpg)  \n异氰脲酸  \n\n典型的TDI工业产品的结构式示意如下：  \n\n![](images/1931c6d9482d00a4f9e3f1222f68fdeb51bdadf128b039468cee472d2e68957d.jpg)  \n\n上式由5molTDI聚合而成。工业产品为 $50\\%$ 醋酸丁酯溶液，约含NCO基 $8\\%$ 左右，游离 TDI0.7%以下，黏度 $(25^{\\circ})$ ）约 $600\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$ ，其涂膜泛黄性比氨酯型加成物好些，干燥迅速，主要用作木材清漆，涂膜硬，配合乙组分后的施工时限较短。  \n\na.混合三聚体类似的产品尚有TDI/MDI混合三聚体，还有TDI/HDI混合三聚体，结构式示意如下：  \n\n![](images/51152bae0cd3743d121c76667f54f0478719b321adea2919780c978bb8ea3734.jpg)  \n\n上面示意式是由3分子甲苯二异氰酸酯和2分子己二异氰酸酯组成。它是 $60\\%$ 的醋酸丁酯溶液，约含NCO基 $10.5\\%$ ，干燥迅速，泛黄性较弱，耐候性好，既可作清漆，也可制色漆，用于木材连续涂装等。  \n\n制法示例：投料TDI（2,4体) $170\\mathbf{g}$ ，HDI330g混合（摩尔比为脂肪族二异氰酸酯：芳香族二异氰酸酯为 $2:1)$ ，升温至 $60\\mathrm{\\Upsilon}$ ，加人 $0.125{\\mathrm{g}}$ 三正丁基麟催化剂使之三聚，并略予冷却。约4.5h后，NCO含量由原始的49. $3\\%$ 下降至 $36\\%$ ，加入约0.1g对甲苯磺酸甲酯，$0,1_{\\mathbf{B}}$ 硫酸二甲酯，加温至 $100^{\\circ}\\mathrm{C}$ ，保持片刻使聚合反应停止。粗产物通过薄膜蒸发器$(0,11\\mathrm{{kPa}}$ ，加热介质如热煤油或蒸汽，保温 $180{\\sim}190\\mathrm{\\textperthousand}$ ）以除去游离未结合的二异氰酸酯。获得约 $186\\mathbf{g}$ 脆而浅黄色树脂，含NCO基 $19.8\\%$ ，溶解于酯类溶剂成 $67\\%$ 溶液，黏度$20\\Upsilon$ ）为 $725\\mathrm{{mPa}\\cdot\\mathrm{{s},}}$ 蒸馏回收的二异氰酸酯共 $285_{8}$ ，回收液以折射率分析，含HDI约$89\\%$ ，含TDI约 $10\\%\\sim12\\%$ 。在三聚体中，脂肪族成分约占 $40\\%$  \n\n按上列的化学式：  \n\nNCO含量 推算值19.6% 实测值19.8% 分子量 推算值858 实测值850\\~870 含脂肪族异氰酸酯成分 推算值39.2% 实测值42%  \n\n红外光谱分析值：吸收峰4. $4\\mu\\mathrm{m}$ 5. $_{9h m}$ 7. $\\upsigma_{\\mu\\mathrm{{m}}}$ ，其中4.4μm表示端基的NCO基，5.9μm及7.0m表示三聚异氰酸酯的特征吸收峰。  \n\n三聚反应的催化剂，除了上述三丁基麟外，还可用其他三烷基麟，但芳基麟无效。尚可用叔胺（如五甲基二亚乙基三胺)，叔胺加苯基缩水甘油醚效果更好。环烷酸铅、碱性的钾盐或钠盐（如酰亚胺钾、醋酸钾、碳酸钠、苯甲酸钠等）以及曼尼期碱等。抑制剂除上述两种外，尚可用苯甲酰氯。氯化氢（通入醋酸乙酯的饱和液）、磷酸等。  \n\n这种混合三聚体的保色性、保光性都很好，加速曝晒试验结果如下：  \n\nTDI加成物 约350h开始粉化 HDI缩二脲 约3000h开始粉化TDI三聚异氰酸酯 约600h开始粉化 TDI/HDI三聚异氰酸酶 约2500h开始粉化  \n\n另一种TDI三聚体的简便制备法是，将 $55g\\mathrm{TDI}$ (2,4体）和 $45g$ 醋酸丁酯投入反应烧瓶，按TDI的质量加入 $0.1\\%$ 的醋酸锂，升温至 $100\\sim110\\ensuremath{\\uptau}$ 。保持 $10\\sim13\\mathrm{h}$ ，至溶液所含NCO基降至 $8\\%\\sim9\\%$ 为止。所得产品与聚酯配漆干燥迅速，含游离TDI约 $2\\%\\sim3\\%$ ，溶液中所含三聚体的分子量约 $1100{\\sim}1200$  \n\nb.HDI三聚体HDI的多异氰酸酯多年来以缩二脲形态被广泛采用，性能优良，实绩甚好。近年来则又发展了HDI“三聚体”，严格名称是HDI异氰尿酸酯（Isocyanurate)，实际上是HDI三聚体、五聚体、七聚体的混合物，以三聚体占多，商业上简称为“三聚体”，具有优良性能，采用量与日俱增，与缩二脲相比有下列优点。  \n\n![](images/9d8dc4b8dd379ebe147600655332afe2fd3980c5dcd4eb6a9cf8630251f94dd4.jpg)  \n异氰尿酸  \n\n·三聚体多异氰酸酯的黏度比缩二脲低，有利于少用溶剂，制高固体涂料，降低大气污染，有利于环境保护。黏度低的原因是其分子间不能形成氢键（不含活泼氢原子)。  \n\n![](images/98cafbef52e8b14a48b18bdea83fd009cf224f60307c3da5cc18d1ab5c4670e6.jpg)  \n\n而缩二脲（或氨酯加成物）多异氰酸酯分子间可形成氢键，互相吸引使黏度增高，示意如下：  \n\n![](images/b3d2255be0bfdf151b15004e4d9f92a6ca955b58cbd4a908071fb7b53df2583f.jpg)  \n\n例如典型的工业产品的黏度比较 $(25\\mathbb{C})$ ：HDI缩二脲（100%固体分） (9000±2000)mPa \\*s HDI三聚体（100%固体分） (2500±500)mPa \\* 8  \n\n·三聚体的异氰脲酸酯环很稳定，不易变质，黏度久贮后变化不大，而缩二脲久贮后黏度会上升，其所含游离HDI的量也会增高。图2-1-35、图2-1-36是Rhodia公司介绍新鲜制成的缩二脲漆贮存6个月后黏度出现上升，而新鲜制成的三聚体漆贮存6个月后黏度几乎没有变化。  \n\n![](images/dbe3f5a65b99983e9bfdfc9bcb76a6cca94cfa58a2469c7794411199c5484a28.jpg)  \n图2-1-35在23℃室温时丙烯酸/缩二脲清漆的黏度变化1—新鲜缩二脲；2一已贮存6个月的缩二脲  \n\n![](images/4f3a2c42bf251492821ae445172628e886cdba2a52e67e8da1ccd9b5251d507d.jpg)  \n图2-1-36在23℃室温，丙烯酸/三聚体清漆的黏度变化1—新鲜的三聚体；2—已贮存6个月的三聚体  \n\n拜耳公司的HDI缩二脲，商品名叫DesmodurN75，三聚体商品名叫Desmodur N3390，N是指德文NichtVergelbend不泛黄。  \n\n日本旭化成株式会社介绍试验结果：将三聚体与缩二脲样品（固体分相同）分别密闭于容器中，经 $140^{\\circ}\\mathrm{C}$ 加热1h后测其游离HDI含量的增加值：  \n\n三聚体 0.1% 缩二脲 0.65%  \n\n·三聚体的耐候保光性高于缩二脲，这是Bayer公司在美国的子公司Miles公司的Luthra的长期曝晒试验结果，不论是含羟基聚酯或含羟基丙烯酸树脂，均有相似规律。  \n\nRhodia公司将丙烯酸树脂分别与三聚体及缩二脲配白漆，经QUV（荧光凝露）加速试验，涂膜的保光性如图2-1-37所示，可见三聚体略优。  \n\n![](images/0e5a38f3e3d3c234b093346199be658d6dc352b0a5eaa61abe7c7031088a3dc4.jpg)  \n图2-1-37丙烯酸/三聚体白漆与丙 烯酸/缩二脲白漆保光性能比较  \n\n![](images/e974ca4ad71711b173c76d7abf06b2dee351c83561be1bfc476c3ced6afc5032.jpg)  \n图2-1-38HDI三聚体凝胶色谱图  \n\n·三聚体涂料的施工时限稍长，从图2-1-37、图2-1-38中可见：经7.5h后，三聚体涂料的黏度约 $700\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$ ，而缩二脲涂料的黏度已达 $\\begin{array}{r l}{{1100}\\mathrm{{mPa}}\\cdot}\\end{array}$ s以上。  \n\n·三聚体涂料的硬度稍高，韧性与附着力与缩二脲相近。  \n\nHDI三聚体的制法示例：将 $1000\\mathsf{g H D I}$ 投入四口烧瓶中，加人 $300\\mathbf{g}$ 二甲苯，升温至$60\\ensuremath{\\mathtt{c}}$ ，在搅拌下将 $0,3g$ 催化剂辛酸四甲基铵盐分为4份，每30分钟加人1份。加毕在 $60\\ensuremath{\\mathbb{C}}$  \n\n继续反应4h，测NCO含量（用滴定法或测折射率)，至HDI有 $21\\%$ 转化为异氰脲酸时，加人 $0,2_{8}$ 磷酸使反应停止。再在$90\\mathrm{\\textperthousand}$ 保持1h，冷却至室温使催化剂四甲基铵磷酸盐结晶析出，过滤除去后经降膜式薄膜蒸发两次，第一次为0.11kPa160℃，第二次为13Pa160℃以回收溶剂及未反应之HDI单体。产品为微黄色透明液，收量为 $210\\mathbf{g}$ ，黏度（ $25\\mathrm{\\Upsilon}$ ）为 $1300\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$ NCO含量 $23.5\\%$ ，二聚体（脲二酮）含量低至 $1\\%$ 以下，游离 $\\mathrm{HDI}0.2\\%$ ，其分子量分布经凝胶色谱分析，结果如图2-1-38所示。  \n\n从图2-1-38可见，产品主要是三聚体，含少量多聚体。  \n\n![](images/2c635b7e952646cb88654afec7a8041967f22d668319675992b19d5a64980415.jpg)  \n图2-1-39 HDI三聚体红外光谱分析$2270\\mathrm{cm}^{-1}$ 处为NCO吸收峰； $1460\\mathrm{cm}^{-1}$ 处为三聚环吸收峰； $1700\\mathrm{cm}^{-1}$ 处为 $-c=0$ 基吸收峰； $3000\\mathrm{cm}^{-1}$ 附近为 $\\mathbf{C}-\\mathbf{H}$ 伸缩； $750c m^{-1}$ 附近为C-H弯曲  \n\n其红外光谱分析如图2-1-39所示。  \n\n典型的HDI三聚体工业产品（例如拜耳公司Desmodur3390）性质如下：  \n\n固体含量（醋酸丁酯/芳烃1：1） 90% 游离二异氰酸酯 <0.15%NCO含量 20%±1% 黏度（25℃） 550±150mPa \\* sNCO当量 约210g 密度（25C) 1. 120kg/L色泽(APHA) <60 闪点 41°C  \n\nc.IPDI三聚体IPDI也可制成三聚体型的多异氰酸酯，具有优良的耐候保光性，不泛黄，其特点是溶解性优良，能溶于烃类溶剂中，能与醇酸及大多数树脂混溶，效果良好，其示意式如下：  \n\n![](images/e8f0900a8ec70688666e16e098c66bd06ee2450b0bf7e7a805f2475fdd6f3bd4.jpg)  \n\n从上式可见，分子中有很多六元环，其结构较刚硬，故与其配伍之羟基组分以较柔韧者为宜。典型的工业产品规格如下：  \n\n固体含量 70%±1% IPDI单体含量 0.5%NCO含量 12% ±0.3% 贮存稳定性 12个月  \n\n商品的黏度取决于所用的溶剂：  \n\n醋酸丁酯 23C时黏度为（900±250)mPa • s 醋酸丁酯/芳烃（1:2） 23℃时黏度为（1700 $\\pm$ 400)mPa \\* s 烃类溶剂 23℃时黏度为（4000 $\\pm$ 600)mPa • s  \n\n商品也有不含溶剂的100%固体的三聚体出售，其NCO含量为 $17.3\\%\\pm0.3\\%$ ，软化点为 $100{\\sim}115\\bar{\\uptau}$ ，其优点为不含溶剂便于运输，缺点为需热熔溶解，操作不便，故工业上采用 $70\\%$ 溶液者较多。  \n\nIPDI三聚的催化剂常是碱性的，例如欧洲专利介绍催化剂是邻苯二甲酸单羟乙酯的碱土金属盐。  \n\n据报道三聚催化剂是DABCO与环氧丙烷的混合物（质量比为 $\\mathbf{\\zeta}_{1}:\\mathbf{\\zeta}_{2})$ 。催化剂的量为IPDI的 $0.5\\%$ 。在 $120\\Upsilon$ 保持3h，待约 $50\\%$ 的NCO基三聚后（控制法为测其折射率、黏度、NCO含量)，此时NCO含量降至约 $28.4\\%$ ，降温至 $40^{\\circ}\\mathrm{C}$ ，通氮气半小时，NCO降至28. $2\\%$ ，经薄膜蒸发去除游离IPDI。三聚体含NCO的理论值为 $18.9\\%$ ，实测产品含$16\\%\\sim18\\%$  \n\n除了上述三聚体品种外，国外尚有IPDI/TDI的三聚体，以及MDI/TDI的三聚体；后者商品性质如下：  \n\n固体分 (51±1)% 颜色（加氏） ≤1 溶剂 醋酸异丁酯 闪点(ISO1523) 17°℃ 黏度（25C，加氏） F\\~J NCO (7.98 ±0.1)% 黏度（25℃） (200±50)mPa \\* s 当量 531 密度（20℃） 1. 065g/cma 游离TDI单体 ≤0.7%  \n\n(2）多羟基树脂能与异氰酸酯反应的基团除了羟基以外，还有氨基等，但在聚氨酯漆的实际生产中，绝大多数还是采用含羟基的化合物。小分子的多元醇（例如三羟甲基丙烷等）只可作为制造预聚物或加成物，或制造聚酯树脂的原料，不能单独成为双组分漆中的乙组分，这是因为： $\\Phi$ 它是水溶性物质，与甲组分不能混合，两相互斥，造成缩孔，颜料絮凝； $\\textcircled{2}$ 分子量太小，结膜时间太长，即使结膜，内应力也大； $\\textcircled{3}$ 吸水性大，成膜过程中要吸潮，涂膜发白。所以必须将这些多元醇化合成分子量较大而疏水性的树脂。  \n\n作为双组分漆用的多羟基树脂，一般有： $\\Phi$ 聚酯； $\\textcircled{2}$ 丙烯酸树脂； $\\textcircled{3}$ 聚醚； $\\textcircled{4}$ 环氧树脂； $\\textcircled{5}$ 篦麻油或其加工产品（氧化麻油、甘油醇解物)； $\\textcircled{6}$ 其他树脂，如聚碳酸酯以及含羟基的氯醋共聚体，醋酸丁酸纤维素等。  \n\n$\\Phi$ 聚酯聚酯是与多异氰酸酯配制涂料最早使用的树脂。将二元酸（常用己二酸、苯酐、间苯二甲酸、对苯二甲酸等）与过量的多元醇（三羟甲基丙烷、新戊二醇、一缩乙二醇、1,3-丁二醇等）酯化，按不同配比可制得一系列的含羟基聚酯。因为支化主要靠三元醇的羟基，所以为了干燥迅速，大多采用三羟甲基丙烷，耐热可用THEIC异氰脲酸三羟乙酯，甘油含仲羟基，采用较少。如三元醇用量多，游离羟基多，则与甲组分并合后的涂膜交联密度高，涂膜坚硬而耐化学品强；如二元醇多，三元醇少，且游离羟基少，则与甲组分并合后的涂膜柔韧，富有挠性。如涂料要求耐热，则多元酸可用对苯二甲酸、偏苯三酸酐。要求弹性高则可用己二酸、壬二酸、癸二酸等，根据原料供应和成品性能而适当调节。也可为了提高对颜料的润湿性、流平性、丰满度、耐水性，用醇酸树脂代替聚酯，但其改性油不宜含不饱和双键，以免氧化生成过氧化物，促使氨酯键的降解、泛黄而降低耐候性。一般可用壬酸或月桂酸，以脂肪酸法合成醇酸树脂，因醇过量而留有适当数量的羟基。用己内酯聚合，以多元醇为引发剂可制得多羟基聚酯。它与多异氰酸酯配成涂料的耐候性比普通的聚酯好。这是因为普通聚酯在制造过程中由于羟基之间脱水而存在一些醚键(耐候性降低)。而己内酯的聚酯纯粹是酯键，而且酸值低、色泽浅、黏度低，游离的羧基、羟基少，所以水解稳定性比一般的聚酯好。  \n\n![](images/d1bfc78b8ef6d73f9beb020d097a2f18fc181113c2813c31ce35fb5217486b8a.jpg)  \n\n与其他羟基组分相比，聚酯形成的涂膜耐候性好、不泛黄、耐溶剂、耐热性好。与丙烯酸树脂相比，聚酯的分子量低，固体分高，其涂膜的挠性较好，因为其酯键上的氧原子容易旋转，而丙烯酸树脂的碳-碳键较不易旋转： or 9  \n\n由于同样道理，丙烯酸/聚氨酯漆的硬度比相应的聚酯高，表干性也比聚酯好，可见图2-1-40、图2-1-41。  \n\n聚酯与聚醚相比，醚键比酯键更易旋转，所以聚醚的玻璃转化温度低，因而其涂膜的耐寒性好，耐碱性水解，黏度低。但是耐油性、耐水性、机械强度、干燥性、与NCO的反应速率均不及聚酯，所以在涂料中聚酯的应用量远超过聚醚。制造聚酯的反应温度一般是在达到 $160^{\\circ}\\mathrm{C}$ 之后，渐渐升温至 $200^{\\circ}\\mathrm{C}$ 左右，维持至酸值达4以下，羟值符合指标即可停止。投料中有二元醇，沸点较低，故不可骤然升温以免二元醇蒸出。现今的反应釜盖的上部，常具有直管，它的上端联结斜冷凝器及分水器。直管中装有不锈钢填料圈，管上端有分凝器，保持蒸气出口温度在 $100{\\sim}105^{\\circ}\\mathrm{C}$ 之间，使酯化水逸出，而二元醇回流入反应釜。在此酯化脱水操作过程中，测蒸出的酯化水层的折射率。水在常温的折射率应该为1.33左右。若折射率明显地超过此值，即表示有多元醇随水蒸出。因此制造聚酯时必须遵守操作规程，并经常分析废水的折射率及树脂的酸值。  \n\n![](images/17f23368f42dbd0eef64377d13f425becda78414882c5134a88d2498e80eacb7.jpg)  \n图2-1-40聚酯漆和丙烯酸涂膜硬度比较1一丙烯酸配方（有催化剂）；2-聚酯配方（有催化剂）  \n\n![](images/36d7b48a7c820c7b7c4203324cedd8fe128cbf79fb84335aed4b958938968813.jpg)  \n图2-1-41聚酯漆和丙烯酸涂膜表干时间比较1-聚酯配方（有催化剂）；2-丙烯酸配方（未加催化剂）  \n\n根据需要，可以调节投料以制得不同支化度、分子量和羟基含量的聚酯，配漆时可选择一种或数种聚酯并用。为了示例，选择Bayer公司若干典型的聚酯供参考（表2-1-178)。  \n\n表2-1-178Bayer公司若干典型聚酯  \n\n\n<html><body><table><tr><td>Desmophen聚酯</td><td>固体含量/%</td><td>OH/%(约)</td><td>当量</td><td>高聚物结构</td></tr><tr><td>650</td><td>65(MPA)</td><td>5.2</td><td>327</td><td>分支</td></tr><tr><td>651</td><td>67(MPA + X=1 • 1)</td><td>5.4</td><td>315</td><td>分支</td></tr><tr><td>670</td><td>100</td><td>4.3</td><td>395</td><td>稍分支</td></tr><tr><td>680</td><td>70(BuAc)</td><td>2.2</td><td>800</td><td>分支</td></tr><tr><td>690</td><td>70(MPA)</td><td>1.3</td><td>1300</td><td>分支</td></tr><tr><td>800</td><td>100</td><td>8.6</td><td>198</td><td>分支</td></tr><tr><td>1100</td><td>100</td><td>6.5</td><td>262</td><td>分支</td></tr><tr><td>1200</td><td>100</td><td>5.0</td><td>340</td><td>稍分支</td></tr><tr><td>1300</td><td>100</td><td>4.0</td><td>425</td><td>分支</td></tr><tr><td>1700</td><td>100</td><td>1.3</td><td>1308</td><td>线型</td></tr><tr><td>R181</td><td></td><td>1.8</td><td>944</td><td></td></tr><tr><td></td><td>100</td><td></td><td></td><td>稍分支</td></tr></table></body></html>\n\n$\\Phi$ MPA为溶剂甲氧基醋酸丙酯（或称丙二醇甲醚醋酸酯)，X为二甲苯，BuAc为醋酸丁酯。 $\\textcircled{2}$ RD181为支链脂肪酸改性聚酶。 C",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 380,
+        "chunk": "# 现列举文献中若干聚酯的投料配比，供参考。  \n\n<html><body><table><tr><td colspan=\"3\">800号聚酯：</td></tr><tr><td>苯酐</td><td>0.5mol</td><td>三羟甲基丙烷</td></tr><tr><td>己二酸</td><td>2. 5mol</td><td>4.0~4.1mol</td></tr><tr><td>1100号聚酯：</td><td></td><td></td></tr><tr><td>己二酸</td><td>3mol</td><td>三羟甲基丙烷 2mol</td></tr><tr><td>1,4-丁二醇</td><td>2mol</td><td></td></tr><tr><td>1200号聚酯：</td><td></td><td></td></tr><tr><td>己二酸</td><td>3mol</td><td>三羟甲基丙烷 1mol</td></tr><tr><td>1,3-丁二醇</td><td>3mol</td><td></td></tr></table></body></html>  \n\n1600号聚酯：  \n\n己二酸 3mol 三羟甲基丙烷 0.6mol 一缩乙二醇 2. 82mol  \n\n2200号聚酯（弹性涂料用）：  \n\n己二酸 3mol 三羟甲基丙烷 0. 29mol 一缩乙二醇 2. 91mol  \n\n下面介绍一种麻油醇酸，含羟基 $3.4\\%\\sim4.8\\%$ ，中等支化度，价廉而实用，通用范围较广，是天津油漆厂的147号树脂，其配方如下：  \n\n麻油（土源） 51.1kg 苯酐 32. 3kg甘油(98%) 16.6kg 二甲苯 100. 0kg  \n\n制造聚酯的原料可以一次投料，也可分两次加人，例如：  \n\n苯酐 74.0kg 三羟甲基丙烷(2) 54. 2kg 三羟甲基丙烷（1) 27.1kg 月桂酸 40. 0kg  \n\n此树脂因基本上甚少双键，故泛黄性、耐候性均优于上述麻油醇酸。  \n\n操作：将苯酐及 $27.1\\mathrm{kg}$ 三羟甲基丙烷投入反应釜，在 $180\\sim200^{\\circ}\\mathrm{C}$ 酯化，通入二氧化碳以带除水分，待酸值降到220左右，加入第二批三羟甲基丙烷 $54,2\\mathbf{k}\\mathbf{g}$ 及月桂酸，继续酯化至酸值达3.5左右。产品是浅黄色固体，软化点 $37\\sim42\\ensuremath{\\mathrm{\\DeltaC}}$ ，羟基当量为310。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 381,
+        "chunk": "# 硬性聚酯配方：  \n\n苯酐 3. 0mol 301g 二甲苯(回流脱水用) 三羟甲基丙烷 3. 5mol 315g  \n\n60g  \n\n操作：逐渐升温至 $200^{\\circ}\\mathrm{C}$ ，维持此温度使酯化至酸值10以下，减压蒸除低分子量挥发物，用MPA、醋酸丁酯和二甲苯混合溶剂稀释成 $50\\%$ 溶液，其溶液羟值为 $145\\sim150$ 。此聚酯可供与HDI的缩二脲配漆，具有优良的耐候性。因其固体分的羟基含量高，涂膜的交联密度高，故抗溶剂性好，若用于飞机蒙皮可耐磷酸酯液压油（Skydrol）的侵损。文献介绍含脂肪酸的聚酯，其黏度低而固体含量较高：  \n\n己二酸 2mol 三羟甲基丙烧 2mol 一缩丙二醇 1mol 椰子油脂肪酸 1mol  \n\n所得产品的羟值为220。  \n\n除了上述聚酯外，尚有聚碳酸酯-聚酯型多元醇，耐热性、耐碱性等均较普通聚酯好，但价格较贵，用量较少。  \n\n$\\textcircled{2}$ 丙烯酸树脂含羟基的丙烯酸树脂与脂肪族多异氰酸酯配合，可制得性能优良的聚氨酯漆，其用途逐年上升，大量用作汽车的修补漆、高级外墙漆、海上钻井等平台的上层结构面漆等。  \n\n丙烯酸树脂耐候性优良，干燥快，因为它不吸收 $300\\mathrm{nm}$ 以上的紫外线及可见光，其主链的碳-碳键耐水解。含羟基丙烯酸树脂与多异氰酸酯交联的涂膜，比单纯的丙烯酸树脂固体含量高，耐溶剂，而且力学性能提高。  \n\n<html><body><table><tr><td colspan=\"2\">Erichsen 杯突/mm</td><td>Taber膨耗/mg</td></tr><tr><td>丙烯酸涂膜</td><td>0。？</td><td>62</td></tr><tr><td>丙烯酸/HD1缩二脲</td><td>8.9</td><td>30</td></tr></table></body></html>  \n\n我国南方地区气候炎热而潮湿，单纯的热塑性丙烯酸外墙涂料往往易沾尘，不雅观。以少量脂肪族多异氰酯交联的丙烯酸涂料则大有改善。  \n\n关于丙烯酸树脂的制造方法，本分册的丙烯酸漆一章中已有详述，下面仅是示例。  \n\n甲基丙烯酸羟乙酯 19.15g 偶氮二异丁晴 3.87g丙烯酸乙酯 38.82g MPA（甲氧基醋酸丙酯） 152.24g甲基丙烯酸丁酯 38.82g  \n\n上述配方在 $85\\Upsilon$ 反应5h。产品含羟基 $2.5\\%$ ，固体含量为 $40\\%$ ，黏度约 $2.5\\sim$ $3.0\\mathrm{cm}^{2}/\\mathrm{s}$ ，尚可加人硫醇等转链剂使聚合时分子量分布较为均匀，或采用高温聚合以降低黏度。配漆所用的多异氰酸酯，以往颇多用HDI缩二脲，现则转向，大多用HDI三聚体（如Desmodur 3390，TolonateHDT90），因为其耐候性更好，而且黏度低，固体含量较高。  \n\n此类涂料用于汽车漆者很多，可参见许多文献。  \n\nHoechst公司制备供汽车修补漆的丙烯酸树脂的方法如下，供参考：  \n\n二甲苯 310g 叙碳酸缩水甘油酯 180\\*叔碳酸缩水甘油酯有工业产品，如Shell公司的CarduraE10，其经验式为C3HzO，平均环氧当量为245将两者加热至 $142^{\\circ}\\mathrm{C}$ ，再配单体混合物，在3h 内将它均匀加入到下述溶液中：  \n\n甲基丙烯酸甲酯 145g 苯乙烯 195g甲基丙烯酸羟乙酯 135g 丙烯酸 57g叔十二硫醇 6g(链转移剂） 二叔丁基过氧化物 15g  \n\n在 $135^{\\circ}\\mathrm{C}$ 聚合 $4\\sim5\\mathrm{h}$ ，产品的固体含量约 $70\\%$ ，若以MPA 溶剂稀释至 $50\\%$ ，则黏度$(25^{\\circ})$ ，涂-4杯）约130s，含羟基 $4.24\\%$ (按固体计)，酸值为10。固体的软化点为 $70\\sim$ $72^{\\circ}C$ 。将上述丙烯酸树脂 $64.68$ ，加HDI缩二脲 $35.48\\$ (均按固体计算)，并加入必需的各色颜料，可制得优良的汽车修补漆，喷涂至（干膜）厚度 $45\\sim50\\mu\\mathrm{m}$ ，可在 $40\\mathrm{{min}}$ 内常温干燥，具有优良的性能，在美国Florida曝晒18个月后，光泽仅下降 $8\\%\\sim10\\%$ 。上述配方中含苯乙烯，其苯环的α位氢原子易被氧化而夺去，影响耐候性，若含量高会使清涂膜经曝晒开裂。上述叔碳酸改性可降低树脂极性，改进耐水性及涂料流动性。  \n\n一般供制聚氨酯漆的丙烯酸树脂的羟基约在 $2.5\\%\\sim4.5\\%$ 之间，典型的如Bayer 公司的产品。下面摘录几种以供参考：  \n\nA165（固体含量 $65\\%$ ，BuAc : $\\mathbf{X}{=}1:1)$ 固体含羟基 $2.6\\%$  \n\nA265（固体含量 $65\\%$ ，BuAc）固体含羟基3.4%  \n\nA 870（固体含量 $70\\%$ ，BuAc）固体含羟基 $4.3\\%$  \n\n其中羟基含量高者制汽车漆、火车漆；含量低者制外墙涂料等。我国武昌黄鹤楼、南昌滕王阁等名胜古迹的涂装均用HDI缩二脲/丙烯酸涂料，效果良好。  \n\n制造含羟基丙烯酸树脂的重要单体是羟基丙烯酸酯，常用者共有4种：甲基丙烯酸羟乙酯（HEMA)、甲基丙烯酸羟丙酯（HPMA)、丙烯酸羟乙酯（HEA）和丙烯酸羟丙酯(HPA)，各有优缺点，可供选用。  \n\nHEMA含羟基13.07%，聚合物的T45°℃ HEA 含羟基14.65%，聚合物的T4℃ HPMA含羟基11.08%，聚合物的T62℃ HPA 含羟基13.07%，聚合物的T16°℃  \n\n羟乙酯含伯羟基，反应速度快。羟丙酯中的1/3为伯羟基，2/3为仲羟基，反应速度较慢。甲基丙烯酸酯的抗水性、耐候性、硬度较高。丙烯酸酯的黏度较低，涂料的固体分高。此类丙烯酸酯的质量指标中尚须注意其双酯的含量，若双酯含量高，涂料会有凝胶小粒并引起缩孔。而且羟基丙烯酸酯有缓慢少量转化为双酯的反应倾向：  \n\n$$\n\\begin{array}{r l}&{\\mathrm{2CH_{2}{=}C H}\\mathrm{~\\small~\\displaystyle~\\frac~{\\partial~s}{\\partial~t}~}\\mathrm{CH_{2}{=}C H}\\mathrm{CH}}\\\\ &{\\quad\\quad\\quad\\quad\\mathrm{COOCH_{2}C H_{2}O H}\\mathrm{COCH}\\mathrm{CH_{2}C H_{2}O O C}}\\end{array}\\overset{\\mathrm{CH{=}C H_{2}}}{\\mathrm{COOCH_{2}C H_{2}O O C}}+\\mathrm{HOH_{2}C C H_{2}O H}}\\end{array}\n$$  \n\n此反应尤以羟乙酯（HEMA，HEA）比羟丙酯多些。表2-1-179是Dow化学公司产品的规格，供参考，注意其双酯含量。  \n\n表2-1-179Dow化学公司产品的规格  \n\n\n<html><body><table><tr><td>指标</td><td>HEA</td><td>HPA</td><td>指标</td><td>HEA</td><td>HPA</td></tr><tr><td>纯度/%</td><td>最小97.5</td><td>最小97.0</td><td>环氧乙烷/（mg/L）</td><td>最大10</td><td>环氧丙烷10</td></tr><tr><td>其他酶类/% 酸(作为丙烯酸)/%</td><td>最大1.5 最大0.98</td><td>最大1.8 最大0.98</td><td>双酶/% MEHQ/(mg/L)(对</td><td>最大0.3</td><td>最大0.2</td></tr><tr><td></td><td></td><td></td><td></td><td>350~650</td><td>350~650</td></tr><tr><td>水分/%</td><td>最大0.15</td><td>最大0.2</td><td>甲氧基苯酚）</td><td></td><td></td></tr><tr><td></td><td></td><td></td><td>色泽（APHA)</td><td>最大30</td><td>最大50</td></tr></table></body></html>  \n\n除了上述羟乙酯、羟丙酯之外，尚有丙烯酸羟丁酯，例如BASF公司生产的BDMA：  \n\n![](images/e33247b276311822c3c43aaae19deb1e85f0e91123422af931db744666c1e423.jpg)  \n\n羟丁酯的4个亚甲基，除了可提高溶解性和混溶性，有利于涂膜的丰满度外，主要是其较长的支链便于旋转，利于端羟基的活动，更易与NCO基碰撞反应，即使在较低环境温度下，或与 $T_{\\ast}$ 较高的多异氰酸酯（例如IPDI的三聚体），均能充分反应。  \n\n有些聚氨酯漆配方采用聚丙烯酸树脂和聚酯树脂合用，例如固化剂为HDI三聚体，羟基组分为80%丙烯酸树脂、 $20\\%$ 聚酯树脂。聚酯能提高固体含量，并且润湿性好，是研磨颜料的优良介质。  \n\n$\\textcircled{3}$ 聚醚聚醚的耐碱性、耐寒性、柔挠性优良，可用于防腐蚀涂料混凝土面涂料等。聚醚的主要用途在泡沫塑料。随着石油化工的发展，提供了环氧丙烷等原料，使其产量扩大、成本降低。在聚氨酯涂料中，聚醚因黏度低，可制无溶剂涂料等。但涂料中聚醚用量较少。  \n\n聚醚是端羟基的低聚物，链中的许多烃基以醚键联结。因为醚键的存在，在紫外线照射下易氧化成为过氧化物，涂膜降解，倒光粉化，所以宜用于室内抗化学腐蚀涂料、耐油涂料、地板漆等，若用于户外则需添加颜料屏蔽保护。氧分子是双基（diradical·O—O·），会与C—H键反应，聚醚中的叔碳与氢的键—CH—CH—O—，因键能低，很易被氧化：  \n\n聚醚是用1，2-环氧化合物或四氢呋喃，以多元醇或胺为引发剂加聚而成。  \n\n1,2-环氧化合物有3种： $\\textcircled{1}$ 环氧乙烷； $\\textcircled{2}$ 环氧丙烷； $\\textcircled{3}$ 缩水甘油醚类。其中以环氧丙烷最重要。环氧乙烷加聚物的吸水性太高，降低涂料性能。缩水甘油醚成本高，仅用于特殊需要的场合。  \n\n多元醇有： $\\textcircled{1}$ 二元醇类； $\\textcircled{2}$ 甘油、三羟甲基丙烷、已烷三醇等三元醇等； $\\textcircled{3}$ 季戊四醇等四元醇类； $\\textcircled{4}$ 山梨醇等六元醇等。  \n\n胺类如乙二胺。  \n\n根据引发剂所含活性氢原子的数目，可制得不同官能度的聚醚。用二元醇制得二官能度的聚醚，用三元醇得三官能度的聚醚。用乙二胺可制得四官能度的碱性聚醚，由于它有叔氮原子存在，对NCO反应具有催化作用，可供配快干的双组分聚氨酯漆。  \n\n用环氧丙烷制得聚醚的羟基，大多是仲羟基，较少是伯羟基，所以反应性较弱。  \n\n环氧丙烷的加聚用碱催化，如产品聚醚中碱残留量高则在以后的NCO反应中有催化作用，易引起胶凝。如残留碱性极微，可用少量酰氯作稳定剂来中和。聚醚由专门工厂生产，一般涂料工厂只是选用。选用考虑的因素是：官能度和聚合度。聚合度愈大则羟基间的距离愈远，羟值愈低，与异氰酸酯反应的成品的挠性愈高，但耐溶剂性下降。  \n\n聚氨酯涂料中常将低分子量聚醚与二异氰酸酯反应，以提高分子量，制得氨酯聚醚，NCO/OH的比例小于1，示意如下：  \n\n![](images/3563b7f5bc3578a13cd3e800116dabc298537cedd4c33dfc506190deb1426e3d.jpg)  \n\n由lmolTDI与 $2\\mathrm{mol}$ 低分子量二元聚醚制得， $\\mathrm{NCO/OH}{=}0.5$ 。此TDI扩链的聚醚与长度相近的纯聚醚二元醇相比较，虽分子量近似，但扩链聚醚的涂膜强度较高。这可以从分子内聚能的差别来理解：  \n\n-0- 醚键 分子内聚能4.19kJ/mol -0001 酯健 分子内聚能12.14kJ/mol —NHCOO— 氨酯键 分子内聚能35.46kJ/mol  \n\n所以聚酯比聚醚的强度大，黏度高。而氨酯之间能形成氢键，强度更高。链节中嵌人氨酯键，内聚力提高，使涂膜强韧。  \n\n其他扩链的示意如下：  \n\n![](images/33daaaf632f72342250a09c28b5d3234ddd4a0af18b8fd7ca87ca42db9fc5d58.jpg)  \n\n制造工艺是将聚醚和异氰酸酯加入反应釜，通氮气渐渐升温，待放热反应停止后升温至$80\\sim90^{\\circ}{\\mathsf{C}}$ ，加人 $0.02\\%$ 的辛酸亚锡或二月桂酸二丁基锡作为催化剂。  \n\n以上两例是中性的氨酯聚醚，反应性缓和，可进一步与过量的二异氰酸酯制造预聚物。亦可作为双组分涂料，但需酌加催化剂。  \n\n若用含胺的聚醚，则反应迅速，可作为双组分涂料，不需加催化剂。如欲将它进一步与过量的二异氰酸酯反应制造预聚物，则稳定性很差（仅 $12\\sim24\\mathrm{h})$  \n\n![](images/32f473fe81191b937ed85beafa99a7dc12285da14a283ac6faecdf6f0fcc92af.jpg)  \n\n一般的氨酯聚醚的分子量约为 $1000{\\sim}3000$ 。兹择某些产品介绍如下。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 382,
+        "chunk": "# a.二羟基聚氧化丙醚  \n\n![](images/e5afec5d746a0cd454e4a6a40d1ba5e991e3bf7c6942d184a5d557b4ac5d47b8.jpg)  \n\n质量指标（表2-1-180）。  \n\n表2-1-180二羟基聚氧化丙醚质量指标  \n\n\n<html><body><table><tr><td>牌号</td><td>分子量</td><td>羟值 /(mg KOH/g)</td><td>酸值 /(mg KOH/g)</td><td>不饱和双键 /(mmol/g)</td><td>水分 /%</td></tr><tr><td>N-204</td><td>400 ±40</td><td>280±20</td><td><0.15</td><td></td><td><0.10</td></tr><tr><td>N-210</td><td>1000±100</td><td>100±10</td><td><0.15</td><td></td><td><0.10</td></tr><tr><td>N-215</td><td>1500 ±100</td><td>70±10</td><td><0.15</td><td></td><td><0.10</td></tr><tr><td>N-220</td><td>2000±100</td><td>56±4</td><td><0.15</td><td><0.07</td><td><0.10</td></tr><tr><td>N-235</td><td>3000±4000</td><td>37~28</td><td><0.15</td><td><0. 07</td><td><0.10</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 383,
+        "chunk": "# b.三羟基聚氧化丙醚  \n\n质量指标（表2-1-181）。  \n\n表2-1-181三羟基聚氧化丙醚质量指标   \n\n\n<html><body><table><tr><td>号 牌</td><td>分子量</td><td>/(mg KOH/g)</td><td>/(mg KOH/g)</td><td>不他和双键</td><td>水分</td></tr><tr><td>N-303</td><td>350±50</td><td>480±50</td><td><0.10</td><td></td><td><0.1</td></tr><tr><td>N-330</td><td>3000±200</td><td>56±4</td><td><0.10</td><td><0.07</td><td><0.1</td></tr></table></body></html>  \n\nc.四羟丙基乙二胺牌号N-403，结构式如下：  \n\n![](images/a8fa18c321e1d00fcbf5c1a06a45378b5578c909f2677b3f4514abb8e0f34c94.jpg)  \n\n质量指标（表2-1-182）。  \n\n表2-1-182四羟丙基乙二腰质量指标  \n\n\n<html><body><table><tr><td>指 标</td><td>规 格</td><td>指标</td><td>格 规</td></tr><tr><td>外观 分子量</td><td>淡黄色黏稠状透明液体 294</td><td>水分 羟值</td><td><0.2% 770mgKOH/g</td></tr></table></body></html>  \n\nd.二羟基聚四氢呋喃氧化丙醚（弹性体用）（表2-1-183）。  \n\n表2-1-183二羟基聚四氢味喘氧化丙醚质量指标  \n\n\n<html><body><table><tr><td>牌号</td><td>分子量</td><td>/(mg KOH/g)</td><td>(mg kOH/g)</td><td>水分</td></tr><tr><td>Ng 220</td><td>2000 ±100</td><td>56±4</td><td><0.20</td><td><0.10</td></tr><tr><td>Ng-235</td><td>3000 ±4000</td><td>37~28</td><td><0.20</td><td><0.10</td></tr></table></body></html>  \n\n国外许多化学公司生产聚醚。Dow化学公司在我国宁波生产聚醚。DuPont公司生产的聚四氢呋喃二元醇，商品名为Terathane1000，分子量约1021，羟值109。Bayer公司生产供涂料用的聚醚介绍如下（均为 $100\\%$ 固体分）：  \n\n250U 含羟基22.0% 当量77 线型，密封剂   \n550U 含羟基11.0% 当量162 分支，无溶剂防蚀漆   \n900U 含羟基8.8% 当量193 分支，防蚀漆   \n1600U 含羟基3.4% 当量500 线型，混凝土漆   \n1900U 含羟基1.7% 当量1000 线型，弹性涂料   \n1915U 含羟基1.1% 当量1545 分支  \n\n$\\textcircled{4}$ 聚碳酸酯多元醇聚碳酸酯涂膜的性能优良，与聚酯比较：  \n\n![](images/4015c4489ecf7c890c53d98515f1d4177becee76d5731af4777088f6ddd987d6.jpg)  \n\n聚碳酸酯的抗水解性比聚酯好得多，但价较贵，在涂料中应用不多，拜耳公司的DesmophenC1200，即含碳酸键。日本旭化成公司的PCDL1000是聚碳酸酯二元醇。  \n\n$\\textcircled{5}$ 环氧树脂环氧树脂具有仲羟基和环氧基，仲羟基可以与异氰酸酯反应。  \n\n![](images/d29e2f960985a4f2ea7480ffe12b9f4318def19653e1070620397c21fe7082c4.jpg)  \n\n用环氧树脂作为含羟基组分，则涂膜的附着力、抗碱性等均有提高，适宜作耐化学品、耐盐水的涂料。如尿素造粒塔所用的聚氨酯漆中就有环氧树脂的产品，具有优良的化学稳定性。但是环氧树脂中的醚键，不耐户外曝晒。  \n\n在制造单组分聚氨酯漆时，若采用固体的环氧树脂（E-20，E-12等），必须注意树脂中是否有催化性杂质，例如在“怡糖法（taffyprocess)”制环氧树脂时，若残留微量未洗净的酚钠，或在“扩链法（advancementprocess）”制环氧树脂时，若残留微量未除净的胺等，遇到异氰酸酯均有催化作用，能引起反应釜中胶凝。这些杂质往往可用漂土将树脂溶液过滤除去之。低分子量的液体环氧树脂杂质较少，无需处理。  \n\n采用环氧树脂作为羟基组分，一般可有3种方式。  \n\na.单纯使用环氧树脂作多元醇，配人漆中。例如有些潜水艇外壳涂料用含环氧树脂的双组分聚氨酯漆，可在寒冷潮湿环境下施工，效果很好，这种用法只有羟基参加反应，环氧基未结合。  \n\nb.用酸性树脂的羧基，使环氧基开环，生成羟基。  \n\nc.与醇胺或胺反应，生成多元醇。  \n\n![](images/0baf8d17ab12b9084b1b0de57d1f384de2bc575d085200dbe2781f1f90f0d131.jpg)  \n\n而且因有叔氮原子的存在，可加速NCO与OH间的反应。  \n\n$\\textcircled{6}$ 麻油麻油是脂肪酸的三甘油酯。脂肪酸中 $90\\%$ 是麻油酸（9-烯基-12-羟基十八酸，结构式如下)，还有 $10\\%$ 是不含羟基的油酸和亚油酸。  \n\n麻油的羟值约为163，即含羟基4. $94\\%$ ；羟基当量345。  \n\n按羟值推算，可认为麻油是含 $70\\%$ 三官能度和 $30\\%$ 二官能度的物质。其组分中长链非极性的脂肪酸赋予涂膜良好的抗水性和可挠性，并且因为价廉而来源丰富，所以广泛应用于聚氨酯漆中，或直接使用，或经吹气，或与甘油经酯交换后制漆。可以制双组分漆，也可与异氰酸酯反应制成预聚物，再配制单组分或双组分漆。有些聚氨酯涂膜经长期浸水后容易起泡，用麻油配制的聚氨酯漆就大有改善，是因为长链脂肪酸的疏水作用。  \n\n麻油大多用于制造含羟基醇酸树脂等，也可配以填料等制造木面的填眼漆等。  \n\n以上介绍的是常规的羟基组分，性能更优越的是氟碳系的羟基组分。日本的永井昌宪等用QUV人工老化仪，对比了氟碳系聚氨酯与常规聚氨酯的老化性能，经5000h后氟碳系老化仅为常规系的1/4。  \n\n(3）配漆配制双组分聚氨酯漆，包括选择3种组分和确定NCO/OH比。  \n\n3种组分是多异氰酸酯、多羟基树脂、颜料和助剂等。  \n\n$\\Phi$ 多异氰酸酯类型的选择  \n\nTDI氨酯加成物：价廉，最常用，性质全面，但泛黄。  \n\nTDI三聚体型：干性快，但施工时限短，供快干木器清漆之用，不宜作色漆，因颜料润湿性差。它与某些树脂混溶性差，光泽低。但因光泽低可节约消光剂用量。  \n\nMDI液化体：蒸气压低、毒性较低，适用作无溶剂防腐蚀涂料等，泛黄严重。  \n\nTDI/HDI三聚体型：干性快，施工时限短，泛黄性和耐候性较TDI系佳，清漆、瓷漆均可采用。  \n\nHDI缩二脲：不泛黄、保光泽，制户外用高级涂料，成本较贵。  \n\nHDI三聚体：不泛黄，保光耐候性比缩二脲更好，可制户外高级涂料。它的黏度低，固体含量高，稳定性好。  \n\nIPDI三聚体：不泛黄，保光耐候性好。它的溶解性好，能与许多树脂混溶。它性较脆，羟基组分须软些。它的 $T_{\\mathrm{s}}$ 高，涂膜物理干性快，但充分交联不快。  \n\nIPDI氨酯加成物：也具有不泛黄及保光性。耐候性略低于三聚体，涂料厂易于自制而价较廉些。  \n\n此外，尚有用麻油醇酸与过量的TDI制成预聚物，也可与含羟基麻油醇酸配合，再外加松香季戊四醇酯，制造木器漆，价格低廉，在我国华东地区产量很大，习称685涂料。  \n\n为了比较脂肪族与芳香族聚氨酯漆的保光性，Potter等用聚酯加TiOz，PVC为10%，以不同异氰酸酯比例，将漆层在美国Florida45°向南曝晒了24个月后，测定其60°光泽，结果如下：  \n\nTDI/TMP加成物含量0% HDI缩二脉100% 光泽保持75% TDI/TMP加成物含量20% HDI缩二脲80% 光泽保持35% TDI/TMP加成物含量10% HDI缩二脲90% 光泽保持45% TDI/TMP加成物含量40% HDI缩二脲60% 光泽保持<20%  \n\n$\\textcircled{2}$ 多羟基树脂的选择耐户外曝晒以丙烯酸树脂为佳，它几乎不吸收紫外线，而且主链的碳-碳键能耐水解的降解，所以聚氨酯清漆均采用丙烯酸树脂。但是加入颜料制成单色漆（solid color)，则聚酯与丙烯酸耐候性相差不大，可能因聚酯对颜料的润湿性较好。耐低温可用聚醚。耐化学腐蚀可选环氧、聚醚、含羟基氯醋共聚体。耐油可选用羟基较高的聚酯。聚酯的支化程度、聚醚的聚合度、丙烯酸树脂的内增塑程度、羟基含量等都能调节涂膜的柔韧性和硬度。聚酯中芳环含量多则提高其抗化学性。耐高温可选用对苯二甲酸聚酯。上述各组分又可互相并合调节。  \n\n除了上述羟基树脂外，尚有过氯乙烯、硝酸纤维素、醋酸丁酸纤维素，加入羟基树脂中，可加速聚氨酯漆的表干不沾尘，并可改善缩孔等弊病。但硝酸纤维素加入芳香族聚氨酯漆中，因硝酸基的氧化性，会使氨酯键氧化，使涂膜泛黄严重，只可用于深色木器漆。加人脂肪族聚氨酯漆中则泛黄不明显。普通硝酸纤维素为防止爆燃，含有乙醇或丁醇润湿，会与  \n\n![](images/5de50750b5e7c39bf3c9ea9a4956c2cc5055dc3309e789e4cd460c90ada26a86.jpg)  \n图2-1-42双组分聚氨酯清漆的交联程度与耐溶剂的关系干燥：120°℃/30min，再在室温放置6天  \n\n异氰酸酯反应，必须轧成漆片后配漆。  \n\n$\\textcircled{3}$ 颜料及助剂的选择（详见后述章节）。  \n\n$\\textcircled{4}$ NCO/OH比例双组分聚氨酯漆的制造技术之一是确定恰当的NCO/OH比例（习称NCO index)。按常规，往往设定 $\\mathbf{NCO}/\\mathbf{OH}=1$ ，使1个NCO基与1个OH基反应生成氨酯。但实际情况要通过试验研究，以确定恰当的比例，满足性能的要求。若多异氰酸酯加入太少，不足与羟基反应，则涂膜交联度较低，抗溶剂性、抗化学品、抗水性下降，甚至涂膜发软。若多异氰酸酯加入太多，则多余的NCO基吸收空气中潮气转化成脲，增加交联密度，提高抗溶剂性、抗化学品性，漆的施工时限较长，多余NCO太多时，涂膜较脆。图2-1-42～图2-1-44是Bayer公司S.Gunther研究某脂肪族聚氨酯涂料NCO/OH比例对性能影响的示例。  \n\n![](images/cb29fcd40878e47651f46d2acc5a94cb4ce0c600d5f04e943c4ec5f17202a9dc.jpg)  \n图2-1-43双组分聚氨酯清涂膜的摆杆硬度与交联程度关系干燥：120°C/30min，再在室温放置6d  \n\n![](images/bb2ddad8bc4652f15611b3c5c45347de8f13d32dd1a8cdd9e3a53c6866f74c53.jpg)  \n图2-1-44双组分聚氨酯清漆的施工时限与交联程度关系  \n\n图2-1-42表示涂膜浸溶剂后被溶出失重的情况，NCO/OH低则溶出多。图2-1-43表示涂膜硬度与NCO/OH比例的关系。图2-1-44表示NCO/OH与涂料的施工时限的关系，NCO太少则施工时限短。  \n\n一般双组分聚氨酯涂料的NCO/OH比例大多采用略高于1的数值，例如 $1.05\\sim$ 1.10。Bishop研究了双组分聚氨酯漆在室温下干燥情况，发现在 $97\\%$ 相对湿度下仅有1/3的异氰酸酯转化为氨酯(红外光谱分析)，2/3生成了脲，这表明与空气中潮气发生了反应。日本坪田实等研究了双组分聚氨酯漆在不同湿度及不同温度下的固化行为，他们选用Bayer公司的HDI缩二脲N-75及3种含羟基丙烯酸树脂（羟值分别为25、50及75.5)，在相对湿度为 $0.55\\%$ \\* $95\\%\\sim97;$ 6以及温度为 $20\\%$ $70\\%$ 下反应，以红外光谱观察吸收峰。  \n\nNCO 吸收峰波数2280cm\\~1 氨酶键 吸收峰波数1730cm1   \n脲健 吸收峰波数1650cm CH:键（参比） 吸收峰波数2930cm-1  \n\n测定NCO吸收峰消失前后吸光度之比：  \n\n表2-1-184为不同温度和湿度下双组分聚氨酯涂料的固化行为。  \n\n表2-1-184在不同温度和湿度下的固化行为  \n\n\n<html><body><table><tr><td>温度 /C</td><td>相对湿度 /%</td><td>氨酯键 /%</td><td>脲健 /%</td><td>2个月后 NCO余量/%</td><td>温度 /C</td><td>相对湿度 /%</td><td>氨酯键 /%</td><td>脲键 /%</td><td>2个月后 NCO余量/%</td></tr><tr><td>20</td><td>0</td><td>55</td><td>8</td><td>30</td><td>70</td><td>0</td><td>85</td><td>15</td><td>0</td></tr><tr><td>20</td><td>55</td><td>41</td><td>50</td><td>8</td><td>70</td><td>95</td><td>20</td><td>80</td><td>0</td></tr><tr><td>20</td><td>97</td><td>11</td><td>85</td><td>0</td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n低湿条件下生成氨酯键较多，涂膜的弹性模量、拉伸强度、 $T_{\\mathrm{s}}$ 、断裂伸长率均比高湿条件下（生成脲键多）的涂膜要高。高湿条件下涂膜浸人溶剂的溶失量多，这是因为NCO与潮气反应，至使许多丙烯酸树脂的羟基未能反应，交联点减少，分子量降低，未反应的丙烯酸树脂被溶出。扫描电子显微镜观察发现：低湿度下形成的涂膜致密强韧，而高湿度下形成的涂膜粗而脆弱，全体有无数微泡，由 $\\mathrm{CO}_{2}$ 形成的多孔质。我国地域广大，西北干旱、东南潮湿，必须研究适宜的NCO/OH的比例。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 384,
+        "chunk": "# 4.聚氨酯漆的助剂  \n\n(1）防缩孔剂双组分聚氨酯漆的两个组分的分子量往往不高，多属低聚物（oli-gomer)，极性高，对微量油污敏感。两组分间的表面张力往往有些差异。涂布后因分子量不高，涂膜凝定（set）慢，仍呈易流动的液态，此时因表面张力之差（梯度）的驱动力，易引起缩孔，必须加入防缩孔剂。常用的防缩孔剂可分为两类：一类为热塑性树脂，对聚氨酯漆的混溶性较低。典型的如醋酸丁酸纤维素，例如Eastman化学公司的CAB381-0.5或CAB551-0.2，其作用在于它在聚氨酯湿涂膜的两个组分中均呈很低混溶性，降低了两个组分的表面张力差，从而改善缩孔之。除了醋酸丁酸纤维素外，尚可用硝酸纤维素、聚醋酸乙烯、聚乙烯醇缩丁醛、氯醋共聚体VAGH等。其中硝酸纤维素虽有良好的流平作用，但其硝基的氧化性会使芳香族聚氨酯漆泛黄，用于脂肪族聚氨酯漆中则无泛黄之。所以聚氨酯漆中以采用醋酸丁酸纤维素较为普遍，除上述的两种CAB以外，我国无锡化工研究所的CDS35-1也可用。美国Monsanto 公司的Modaflow 等也有类似  \n\n作用。  \n\n另一类的防缩孔助剂的作用机理不同，它往往含有机硅化合物，能降低聚氨酯漆的表面张力。因为一般涂装的通则，要求底材（如钢板等）的表面张力大于涂料的表面张力，以便涂料展布。若底材上不净，沾有微量油污，聚氨酯涂料的表面张力高于底材的表面张力，则涂料不易展布而缩孔。此类助剂典型的如BYK306。也可将此类助剂与CAB合用调节。  \n\n(2）消泡剂聚氨酯漆常有起泡之，需添加消泡助剂。通常分为非硅的树脂系及有机硅系助剂。树脂系是热塑性共聚树脂，例如乙烯基异丁醚和丙烯酸酯的共聚体等，其特性是与聚氨酯漆不相容，而能将存在于涂膜中的小气泡表面层破坏，使小气泡逐渐并成大气泡。则按Stoke定律，气泡上升的速度与其直径成平方比例，气泡越大，上升越快，升至涂膜表面。若聚氨酯漆涂于木材表面，消泡剂可消除木材缝隙的空气气泡。所以这类消泡剂常称之为消空气剂（Airrelease agent)，典型的如 $\\mathtt{B Y K052}$ 或Acronal700L等。相容性更低者如BYK053，则消泡力更高，但涂膜的清晰度稍下降。反之，相容性较高者如BYK051，虽消泡力稍弱些，但涂膜清晰度较好，宜用于清漆。  \n\n有机硅系消泡剂也有使涂膜消除气泡的功能，气泡一旦升至表面，由于有机硅体系的表面张力很低，能在泡的表面展布，而使泡破裂，虽具有优良的消泡能力，但会使以后涂覆的漆层附着力降低。所以，有机硅系消泡剂适用于面漆，而树脂系消泡剂宜用于底漆中，不会损及层间附着力。在某些配方中，可同时酌加两种消泡剂，树脂系者（尤其在厚膜漆中）促使气泡浮至表面，硅系者则使气泡破坏。薄涂层则选用一种消泡剂即可。  \n\n(3）催化剂催化剂对异氰酸酯反应的影响，在化学篇中已有详述，以下是一些较常用的商品催化剂，供参考。  \n\n$\\Phi$ 二月桂酸二丁基锡，简称DBTDL或DBTL，来自英文名dibutyl tin dilaurate，典型的如美国M&T化学公司产品，编号为T-12。  \n\n$\\textcircled{2}$ 二醋酸二丁基锡（dibutyltindiacetate)，M&-T化学公司编号为T-1，它与DBTDL的差别在于醋酸基比月桂酸基的体积小，所以对于有位阻的NCO基（例如TMXDI）则它的催化功效比DBTDL强。二醋酸二甲基锡则体积更小。  \n\n$\\textcircled{3}$ 辛酸亚锡（Stannousoctoate)，M&T公司商品名为T-9。以上几种锡催化剂均会降低涂膜的耐候性。  \n\n$\\textcircled{4}$ 三亚乙基二胺（triethylene diamine)，化学名简称DABCO，是Air Products Corp.所属Houdry化学公司的产品名。  \n\n$\\textcircled{5}$ DABCO33LV是三亚乙基二胺溶于一缩丙二醇的33%溶液。  \n\n![](images/07d195db7ddb6a93968676efedb4f2c0f85d662a8f131eec2d9c6212d47e8af1.jpg)  \n\n$\\textcircled{6}$ 环烷酸锌或辛酸锌，用于脂肪族聚氨酯漆，其毒性低于DBTDL，且施工时限亦比DBTDL稍长，用量约为基料的0. $2\\%$  \n\n$\\textcircled{7}$ 叔胺，如Desmosapid PP是Borcher 公司产品。  \n\n双组分聚氨酯涂料的催干剂需要选择优化，例如HDI缩二脲与651聚酯配成涂料，其催干剂的选择见表2-1-185（NCO/ $\\mathrm{{OH}=1.(}$ ；固含量 $40\\%$ 。  \n\n表2-1-185 催干剂的比较  \n\n\n<html><body><table><tr><td>项 目</td><td></td><td>空白</td><td>PP 0.3%</td><td>PP 0.5%</td><td>锡 0.02%</td><td>锌 0.2%</td></tr><tr><td>黏度/s</td><td>0h</td><td>14</td><td>14</td><td>14</td><td>14</td><td>14</td></tr><tr><td>DIN4号杯2h</td><td></td><td>15</td><td>16</td><td>17</td><td>胶化</td><td>32</td></tr><tr><td></td><td>4h</td><td>16</td><td>18</td><td>26</td><td></td><td>胶化</td></tr><tr><td>6h</td><td></td><td>17</td><td>62</td><td>胶化</td><td></td><td></td></tr><tr><td>干燥(指压干）/h</td><td></td><td>>8</td><td>5.0</td><td>4.6</td><td>5.0</td><td>6~7</td></tr><tr><td>硬度Konig/s</td><td>1天</td><td>22</td><td>110</td><td>67</td><td>22</td><td>24</td></tr><tr><td></td><td>3天</td><td>196</td><td>120</td><td>87</td><td>54</td><td>68</td></tr><tr><td></td><td>7天</td><td>215</td><td>145</td><td>107</td><td>87</td><td>94</td></tr></table></body></html>  \n\n从上列比较可见，选用 $0.3\\%$ DesmosapidPP最为合宜，DBTDL胶化太快。以上仅是示例，按各种要求而优选。  \n\n(4）光稳定剂脂肪族聚氨酯清漆大量应用于车辆等，受太阳紫外光照射容易开裂剥落，必须添加光稳定剂，包括两种组分，一种是紫外光吸收剂，另一种是受阻胺（HALS)，二者配合可延长清漆寿命。光稳定剂品种很多，聚氨酯清漆中最常用者是Ciba公司的紫外光吸收剂Tinuvin1130和受阻胺Tinuvin 292。Tinuvin1130是苯并三唑化合物。能吸收紫外光的能量，使转化为一般的热能。  \n\n![](images/b0cf7ceb96995c7cc1568af593cf0d72abe260e4e35141906d88451d1bf34c6a.jpg)  \n\n它是黄色黏稠液体，能溶于有机溶剂中，密度为 $1.178/\\mathrm{cm}^{3}$ 。  \n\nTinuvin 292受阻胺光稳定剂简称HALS（Hinderd Amine Light Stabilizer），能捕获涂膜老化的游离基，以终止链式分解。  \n\n![](images/c16ec238b0fed1f49f89737556332de012f36ce9b2203f8fbf26958b4774451d.jpg)  \n\n它是淡黄色液体，在 $0^{\\circ}\\mathrm{C}$ 下储存会结晶，稍热后即返成液体。密度 $0.99g/\\mathrm{cm}^{3}$ ，可溶于有机溶剂。  \n\n（5）吸潮剂聚氨酯涂料中的多异氰酸酯会与水反应，产生脲和二氧化碳，使涂料罐鼓胀，涂膜起泡，黏度上升直至胶化。所以必须控制涂料所含水分，尤其是制造潮气固化漆及无溶剂漆时，必须消除颜料、溶剂等所带人的水分。采用的各种吸潮剂（moisture scaven-ger）如下。 小  \n\n$\\Phi$ 甲苯磺酰异氰酸酯HC— —SONCO甲苯磺酰异氰酸酯的反应活性因磺酰基的吸电子性而能反应迅速，超过一般的二异氰酸酯，能优先与水分反应而脱除，而且它是单官能化合物，不会导致黏度上升或胶化。但是它的蒸气压较高，具有一定毒性，配漆时若加入过量，其游离部分不利于劳动保护。  \n\n工业产品性质如下：  \n\n<html><body><table><tr><td>纯度</td><td>96%以上</td><td>凝固点</td><td>2C</td></tr><tr><td>密度（25℃）</td><td>1. 29g/cma</td><td>颜色（APHA)</td><td>≤30</td></tr><tr><td>沸点(0.13kPa)</td><td>99C</td><td>闪点（ISO1523）</td><td>145C</td></tr></table></body></html>  \n\n一般每 $20\\upkappa$ 可吸除 $_{1g}$ 水。  \n\n$\\textcircled{2}$ 原甲酸乙酯  \n\n它能与水反应产生醇。醇虽会消耗一部分NCO基，但避免了涂膜起泡等之弊。  \n\n$\\textcircled{3}$ 分子筛，或其在麻油中的浆。  \n\n$\\textcircled{4}$ 无水硫酸铝。  \n\n$\\textcircled{5}$ 唑烷，例如由甲基异丁基酮与醇胺缩合而成的唑烷具有良好的脱水功能：  \n\n![](images/6fd49465323d0b05a4268913522027e501ee236d46810faa2c7a85cfea236d23.jpg)  \n\n与其他吸潮剂相比：分子筛并不是与水反应而仅是吸收，水分仍留在该体系内，并有可能以后释出，甚至最终引致胶化。与甲苯磺酰异氰酸酯相比，唑烷的毒性低，搬运和使用较为方便。每1份水加入 $18\\sim22$ 份唑烷，同时加入二月桂酸二丁基锡催化剂，搅拌 $1\\sim$ 2h，待水含量下降至令人满意程度，将研磨浆料降温至 $80\\ensuremath{\\mathrm{\\tau}}$ 以下，投人其余部分完成配方。例如某潮气固化聚氨酯漆的吸潮剂试验结果：  \n\n<html><body><table><tr><td></td><td>哆唑烷</td><td>甲苯磺酰异氰酸酯</td><td>分子筛</td></tr><tr><td>原</td><td></td><td>0.20%水分</td><td>0. 05% 水.23%分</td></tr><tr><td></td><td>0.32%水分</td><td></td><td></td></tr></table></body></html>  \n\n以上虽强调了除水的重要性（尤其对于无溶剂漆及潮气固化单组分漆)，但一般溶剂型双组分漆的微量水分，在不影响涂膜起泡的条件下，不必加入吸潮剂。聚氨酯漆若丝毫不含水往往干性稍慢。所以在羟基组分中微量水（如颜料带入等）会与异氰酸酯反应生成胺，胺具有催化作用，使干性较快。  \n\n其他类的涂料助剂，如颜料润湿分散剂、流平剂、流变剂、防擦伤剂等，与其他种类的涂料相类似，不另重复。  \n\n应用于闪光金属色罩光清漆的双组分聚氨酯清漆示例：  \n\n\n<html><body><table><tr><td>丙烯酸树脂A870（70%固体）</td><td>48.38g</td><td>固化剂Desmodur N 3390</td><td>18.14g</td></tr><tr><td>BYK331(50%溶液)</td><td>0.30g</td><td>以上 NCO/OH=1.0</td><td></td></tr><tr><td>Tinuvin292（50%溶液）</td><td>1.00g</td><td>固体分</td><td>52%</td></tr><tr><td>Tinuvin1130(50%溶液）</td><td>2.01g</td><td>指压干(T-3)</td><td>7h</td></tr><tr><td>DBTDL(1%溶液)</td><td>1.51g</td><td>干膜厚度</td><td>45μm</td></tr><tr><td>溶剂(MPA + Xylene : BuAc=1 : 1  1)</td><td>28.66g</td><td>摆干硬度（konig）7天后</td><td>198s</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 385,
+        "chunk": "# 5.封闭型聚氨酯漆  \n\n封闭型聚氨酯漆的成膜物质与前述的双组分聚氨酯漆相似，是由多异氰酸酯及多羟基树脂两部分组成。所不同之处是，多异氰酸酯已被苯酚或其他单官能的含活泼氢原子的物质所  \n\n封闭，因此两部分可以合装而不反应，成为单组分涂料，具有极良好的贮存稳定性。  \n\n苯酚封闭：  \n\n$$\n\\lim\\limits_{R\\rightarrow\\infty}(-\\infty+\\infty-1)\\rightarrow\\limits_{\\infty}\\stackrel{\\mathrm{~H~}^{0}}{\\rightarrow\\infty}-0=0\n$$  \n\n己内酰胺封闭：  \n\n$$\n\\begin{array}{r}{\\underset{\\stackrel{\\mathrm{C\\_{\\itCH_{2}},\\ldots\\mathrm{CH_{2}}}}{\\mathrm{R-\\itN-\\mathrm{C-0}+\\mathrm{~\\it~HN}}}}{\\overset{\\mathrm{0}}{\\mathrm{I}}}}\\underset{\\mathrm{CH_{2}-C H_{2}-C H_{2}}}{\\longrightarrow}\\underset{\\mathrm{R-\\itN-\\mathrm{C-\\mathrm{N-\\itC-\\mathrm{N}}}}}{\\overset{\\mathrm{0}}{\\mathrm{I}}}\\underset{\\mathrm{CH_{2}-C H_{2}-C H_{2}}}{\\overset{\\mathrm{1}}{\\mathrm{I}}}}\\end{array}\n$$  \n\n丙二酸酯封闭：  \n\n$$\n{\\begin{array}{c}{{\\mathrm{COOR^{\\prime}}}}\\\\ {{\\mathrm{R-N-C-O}}+{\\mathrm{\\Pi}}+{\\mathrm{\\Pi}}}\\\\ {{\\mathrm{\\Pi}}}\\end{array}}{\\overset{\\mathrm{COOR^{\\prime}}}{\\operatorname{Chener}}}\\quad{\\longrightarrow}\\quad{\\begin{array}{l}{{\\mathrm{\\Pi}}_{\\mathrm{H}}^{\\mathrm{~O_\\mathrm{~\\tiny~COOR^{\\prime}~}}}}\\\\ {{\\mathrm{R-N-C-CH}}}\\\\ {{\\mathrm{\\Pi}}}\\end{array}}\n$$  \n\n在加温下则氨酯键裂解生成异氰酸酯，再与多羟基树脂反应而成膜。  \n\n$$\n\\begin{array}{r}{\\mathsf{R N H C O O C}_{4}\\mathsf{H}_{5}\\overset{\\Delta}{\\longrightarrow}\\mathsf{R N}\\longrightarrow\\mathsf{C}\\longrightarrow0+\\mathsf{C}_{4}\\mathsf{H}_{5}\\mathrm{OH}\\mathrel{\\uparrow}}\\end{array}\n$$  \n\n因此，封闭型聚氨酯漆的成膜就是利用不同结构的氨酯键的热稳定性的差异，以较稳定的氨酯键来取代较弱的氨酯键。  \n\n$$\n\\begin{array}{r}{\\underset{\\mathbf{RNC}\\longrightarrow\\mathbf{OAr}\\mathrm{~+~}\\mathbf{R^{\\prime}O H}}{\\mathbf{H}\\downarrow}\\mathrm{~-~}}\\end{array}\\overset{()}{\\mathbf{H}\\longrightarrow}\\left[\\begin{array}{c}{0}\\\\ {\\underset{\\mathbf{R}\\longrightarrow\\mathbf{\\Gamma}\\mathrm{~-~}\\mathbf{N}\\mathrm{~-~}\\mathbf{C}\\mathrm{-}\\mathbf{OAr}}}\\\\ {\\underset{\\mathbf{R^{\\prime}}\\longrightarrow\\mathbf{OH}}{\\mathbf{H}\\Psi}}\\end{array}\\right]\\mathop{\\longleftrightarrow}\\mathrm{~\\underset{\\mathbf{R}\\longrightarrow\\mathbf{N}\\mathrm{~-~}\\mathbf{C}\\mathrm{-}\\mathbf{OR^{\\prime}}\\Psi}{\\mathbf{H}\\ W}~+~}\\mathbf{ArOH}\\mathrm{~\\dagger~}}\\end{array}\n$$  \n\n文献介绍的封闭剂很多，但是芳香族聚氨酯漆实际生产中所采用的主要还是苯酚或甲酚，脂肪族聚氨酯漆则不用酚以免变色，主要采用己内酰胺等（用于粉末涂料等)，也采用丁酮用于工业产品涂料以降低烘烤温度。例如，对于己二异氰酸酯的封闭剂曾研究过很多品种，择要介绍如表2-1-186。  \n\n表2-1-186HDI封闭氨酯化合物的裂解温度  \n\n\n<html><body><table><tr><td>封闭剂</td><td>化学式</td><td>裂解温度/C</td><td>封闭剂</td><td>化学式</td><td>裂解温度/C</td></tr><tr><td>己内酰胺</td><td>(CH)s—CONH</td><td>160</td><td>邻苯二酚 丙二酸二乙酯</td><td>1,2-CH(OH)z CHOOCCHCOOCHs</td><td>160 130~140</td></tr><tr><td>苯酚</td><td>CHOH</td><td>160</td><td>乙酰丙酮</td><td>CHCOCHCOCH</td><td>140~150</td></tr><tr><td>间硝基苯酚</td><td>m- NO—CHOH</td><td>130</td><td>乙酰醋酸乙酯</td><td>CHOOCCHCOCH</td><td>140~150</td></tr><tr><td>对氯苯酚</td><td>CI—CH—OH</td><td>130</td><td></td><td></td><td></td></tr></table></body></html>  \n\n近年开发了二甲基吡唑，裂解温度很低。  \n\n裂解的温度受下列因素所影响。  \n\n$\\textcircled{1}$ 异氰酸酯的电负性大，则温度下降。  \n\n$\\textcircled{2}$ 封闭剂的电负性大，则温度下降。  \n\n$\\textcircled{3}$ 催化剂，如二月桂酸二丁基锡、辛酸亚锡、叔胺或钙、锶的羧酸盐均能降低裂解温度。  \n\n被封闭的多异氰酸酯组分，工业上较多的是：  \n\n$\\Phi$ 氨酯加成物型；  \n$\\textcircled{2}$ 三聚异氰酸酯型。  \n\n除了上述两种封闭的多异氰酸酯以外，也有己内酰胺封闭的HDI缩二脲及其他多异氰酸酯，如异辛醇封闭的芳香族异氰酸酯可应用于阴极电泳漆，苯酚封闭的弹性多异氰酸酯应用于密封剂（sealant）等。下面叙述工业产品的典型例子。  \n\n$\\textcircled{1}$ 苯酚封闭TDI加成物，由3molTDI与 $\\scriptstyle1\\ m\\circ1$ 三羟甲基丙烷加成，再以3mol（或略过量）的苯酚或甲酚封闭。  \n\n![](images/81702cc2a3f79dec6ccd771d4de003297a61601515e6d43066db38d665262239.jpg)  \n\n制法是将苯酚溶于醋酸乙酯中，将TDI/三羟甲基丙烷加成物的溶液，按当量加入混匀（或苯酚稍过量 $2\\%\\sim5\\%)$ 。溶液加热至 $100^{\\circ}\\mathrm{C}$ ，保持数小时（或可加入少量叔胺以促进反应)，抽样以丙酮稀释，到加入苯胺而无沉淀析出时，表示异氰酸酯已封闭完成，即可停止。蒸除溶剂，产品是固体，软化点 $120{\\sim}130\\%$ ，含 $12\\%\\sim13\\%$ 有效NCO基，是封闭型中常用的交联剂。  \n\n$\\textcircled{2}$ 苯酚封闭的TDI三聚异氰酸酯型，因含稳定的三聚异氰酸酯环，比上述苯酚封闭的TDI加成物的耐热性高，可先由3molTDI与3mol苯酚在 $150^{\\circ}\\mathrm{C}$ 反应，在TDI的4位上生成氨酯：  \n\n![](images/d2b03ceefb62b33d2a15ea64012e6f9643baae08824b9fa0af2f5c5707db3352.jpg)  \n\n再将上述氨酯在 $160^{\\circ}\\mathrm{C}$ 加热，并加入催化剂使其三聚而成。产品全溶于醋酸乙酯、丙酮等。  \n\n![](images/c4c3cf6383d6e4adfc098e86bf72798bd0d322d7ab62cbbca080db3ced316e1a.jpg)  \n\n封闭型聚氨酯漆的应用优点是单组分、施工烘烤不需改动设备，涂膜性能与双组分漆相同，可广泛调节。其缺点是常需高温烘烤，不能用于木材、塑料上，封闭剂在烘烤后挥发，污染大气，而且封闭剂（如己内酰胺、丁酮等）消失，也是浪费。  \n\n封闭型聚氨酯漆的主要应用场所如下： $\\textcircled{1}$ 电绝缘漆； $\\textcircled{2}$ 粉末涂料； $\\textcircled{3}$ 阴极电沉积漆(CED)； $\\textcircled{4}$ 卷材涂料； $\\textcircled{5}$ 汽车耐冲击底漆； $\\textcircled{6}$ 密封剂，环氧增韧剂。  \n\n(1）电绝缘漆封闭型聚氨酯漆用作电绝缘漆是由于其优良的绝缘性、耐溶剂性、耐水性、力学性能。一般的电工材料如铜、铝、砂钢片等均能耐烘烤，而且聚氨酯漆涂成的漆包线大多具有“自焊锡”的特点，在高温下氨酯键降解，裸露出铜、铝线，不必刮除漆层，易于焊锡，称为可焊锡漆包线漆（solderablewireenamel)。一般介绍的配方是：  \n\n苯酚封闭的TDI加成物 32.45 混合甲酚 20.4   \n豪酯（含羟基12%） 15.45 丙二醇甲醚醋酸酯 17.4   \n辛酸亚锡 0.1 甲苯 11.9   \n聚酰胺树脂· 2.4  \n\n·这里的聚酰胺树脂并非环氧树脂固化剂的油脂型聚酰胺，而是普通的热塑性聚酰胺树脂。  \n\n我国常州涂料研究院开发了MDI封闭型聚氨酯漆包线漆，制成漆包线的主要技术指标如下：  \n\n<html><body><table><tr><td>外观</td><td>光滑均匀</td><td>焊锡试验，375℃C</td><td>≤4s</td></tr><tr><td>涂膜厚度</td><td>0. 032~0. 043mm</td><td>室温击穿电压</td><td>≥3500V</td></tr><tr><td>柔韧性</td><td>1d不裂</td><td>涂膜连续性</td><td></td></tr><tr><td>热冲击(130℃C±5℃,0.5h)</td><td>1d不裂</td><td>常态</td><td>≤2孔(JIS 3210)</td></tr><tr><td>软化击穿</td><td>170°℃,2mm内不击穿</td><td>盐水针孔(3%)</td><td>≤5孔(盐水法）</td></tr><tr><td>单向刮漆/N</td><td>最小≥3.5,平均≥4.1 ≥2H</td><td>盐水针孔(5%)</td><td>≤3孔</td></tr><tr><td colspan=\"4\">耐溶剂性</td></tr></table></body></html>  \n\n(2）粉末涂料（见本书第三篇第八章）  \n\n(3）阴极电沉积漆阴极电沉积漆与阳极电沉积漆相比有许多优点，现在各国汽车制造厂均采用阴极电沉积漆作为底漆，其中最典型的是美国的PPG公司和BASF公司的产品，其主链是环氧树脂用胺开环，烘烤时用封闭异氰酸酯固化，举例如下仅供理解。  \n\n$\\Phi$ 反应瓶中加人 $174\\ensuremath{\\mathrm{gTDI}}$ （80/20)，搅拌通入氮气，升温至 $60^{\\circ}\\mathrm{C}$ ，在2h内滴加 $90g$ 二乙二醇乙醚，加毕在 $60^{\\circ}\\mathrm{C}$ 保持 $2\\mathrm{h}$ ，制成半封闭的TDI。  \n\n$\\textcircled{2}$ 另一反应瓶中加人 $500\\mathbf{g}$ 双酚A环氧树脂（Shell-1001）和 $100g$ 甲苯，升温至 $80\\sim$ $100^{\\circ}\\mathrm{C}$ 使溶解，在搅拌下滴加 $73g$ 二乙胺，再升温至 $120^{\\circ}\\mathrm{C}$ ，保持2h使充分开环。加入 $280\\mathbf{g}$ 脱水麻油酸及甲苯，采用溶剂法，在 $200\\Upsilon$ 酯化5h，减压蒸除甲苯，冷却至 $100\\Upsilon$ ，加$300\\mathbf{g}$ 醋酸丁酯，搅匀，保持 $100\\%$ 在 $1\\sim1.5\\mathrm{h}$ 内滴加上述 $\\textcircled{1}264\\mathbf{g}$ 半封闭的TDI，加毕在$120^{\\circ}\\mathrm{C}$ 保持2h，冷却至 $50\\sim60\\Upsilon$ ，加入醋酸 $60_{8}$ 及去离子水 $1550_{B}$ ，得乳液基料（固体含量为 $37\\%)$ 。  \n\n配漆：上述乳液基料，加炭黑及皂、去离子水等。  \n\n加去离子水 $264_{\\mathrm{{B}}}$ ，漆液之固体含量为 $13\\%$ ， $\\mathsf{p H}$ 为5. $5{\\sim}6$ 。现今该类漆常制成黑色。  \n\n(4）卷材涂料卷材涂料具有生产效率高，涂装时挥发的溶剂可集中作为能源燃烧而不污染大气，涂装的卷材（钢或铝）可后加工弯曲（postforming）而涂膜不裂，使最终用户（如建筑板材和家用电器厂等）不必在厂中设涂漆车间，避免火灾及管理之麻烦。常用的底漆是高分子量环氧树脂加脲醛树脂和铬酸锶。若用封闭的TDI加成物与羟基树脂作底漆，则涂膜弯曲性提高。常用的卷材面漆是聚酯/三聚氰胺体系。封闭聚氨酯漆也可做卷材涂料。它是脂肪族，具有优良的弹性和耐候性。以下示例是一种商售的以羟基封闭的脂肪族IPDI多异氰酸酯：  \n\n<html><body><table><tr><td>固体含量</td><td>60%</td><td>密度（25℃）</td><td>1.05g/cma</td></tr><tr><td>组成</td><td>饱和聚酯及上述IPDI多异氰酸酸</td><td rowspan=\"3\">烘干时间（0.8mm铝片）</td><td>180℃3min</td></tr><tr><td>溶剂</td><td>MPA/200号煤焦溶剂（1：2）</td><td>200℃2.5min</td></tr><tr><td>黏度（25C）</td><td>(1. 7±0. 3)Pa •s</td><td>2501min</td></tr><tr><td>色泽（加氏）2</td><td></td><td></td><td>300℃45s</td></tr></table></body></html>  \n\n以上烘干时间的温度是指烘箱温度，并不是PMT（最高的金属板温度)。卷材涂料的配",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 386,
+        "chunk": "# 方示例如下：  \n\n<html><body><table><tr><td>上述封闭聚氨酯树脂</td><td>59.0g</td><td>200号煤焦溶剂</td><td>8.0g</td></tr><tr><td>TiO（金红石）(PVC=19%）</td><td>27.8g</td><td>流平剂Byketol Special</td><td>1. 0g</td></tr><tr><td>MPA溶剂</td><td>4. 0g</td><td>氟碳表面助剂FC430(3M公司）</td><td>0. 1~0.2g</td></tr><tr><td colspan=\"4\">以上涂料烘烤后性能（涂膜25m）如下：</td></tr><tr><td>摆干硬度（Konig）</td><td>170s</td><td>T夸（取决于底材及其预处理）</td><td>0~1</td></tr><tr><td>布氏硬度（Buchholz)</td><td>111</td><td>附着力（划格，DIN53151)</td><td>0</td></tr><tr><td>铅笔硬度</td><td>H</td><td>光泽（ASTMD 523)</td><td>20°70~75</td></tr><tr><td>杯突试验（Erichsen）</td><td>>10mm</td><td></td><td>60*85~90</td></tr><tr><td>反冲</td><td>>9.04N·m</td><td></td><td></td></tr></table></body></html>  \n\n以上可见，聚氨酯卷材涂料的突出优点是其T弯曲试验的性能优秀，耐候性也优良。但它的烘烤必须控制准确，不足则涂膜软，过度则—NHCOO—键易裂解。  \n\nBayer公司的Mirgel开发的封闭HDI多异氰酸酯BL3175与聚酯配合也可制成韧而耐久的卷材涂料，在我国实效良好。它是丁酮封闭的HDI三聚体，含封闭NCO11.1%，固体分 $75\\%$ α  \n\n(5）汽车耐石击底漆现在汽车的车速提高，为了抵抗小石飞击，一般在车底有聚氯乙烯的塑溶胶厚涂层，而车身下侧部的二道底漆（primer surfacer)，往往也含有封闭聚氨酯，具有缓冲石击的功效。通常二道底漆的基料大多由聚酯及三聚氰胺树脂所组成，耐冲击性有限，若将-部分三聚氰胺树脂用封闭多异氰酸酯取代，则耐冲击性提高。图2-1-45、图2-1-46是Bayer公司试验用封闭的HDI多异氰酸酯取代一部分三聚氰胺，烘干后涂膜的耐冲击性的曲线，可见性能大为提高，烘烤时若按基料固体分加人1%二月桂酸二丁基锡，则可降低烘温，在 $140^{\\circ}\\mathrm{C}$ 约 $30\\mathrm{{min}}$ 即可。  \n\n![](images/0d54126abcc85101c2aa6cb20da8a25c1981cbf3ef8db154dfcdccff16da9f82.jpg)  \n图2-1-45添加封闭的HDI多异 氰酸酯后涂膜的耐冲击性 ①氨基树脂质量；②封闭聚氨酯 （DesmodurBL3175）质量；③聚酯质量； 11bf + in=4. 44822N · cm,  \n\n![](images/98828b96a2862c87c04c710289afacb5517f41c5bd65f86c000848c1f0c32be7.jpg)  \n图2-1-46 催化剂对烘烤温度的影响1一无催化剂；2一按树脂固体分加1%催化剂  \n\n近年来封闭聚氨酯研究的重点是以各种封闭剂降低烘烤温度，举例如下。  \n\n丁酮  \n\n![](images/5211d75f3385cb99b38a419792c9717a75177f351ca066f8b324813d387b4b3c.jpg)  \n\n![](images/23bee28a5f1e50aaab8d00d490914d2be70a53d7310545a83561ea4f34cb2432.jpg)  \n\n人们做了不少研究，用热失重分析TGA，用动态力学分析DMA等比较各种封闭剂的解封反应，但工业实践上必须根据实际应用来判断。当封闭聚氨酯与羟基组配合，用热失重分析比较几种封闭剂的开始解封的温度是：  \n\n己内酰胺 177C 3,5-二甲基吡唑 167C 丁酮 157°C 二异丙胺 140°C  \n\n但用动态力学分析，含1%二月桂酸二丁基锡催化的几种封闭异氰酸酯开始与羟基交取的温度是：  \n\n工业实践上，已内酰胺、丁酮、二异丙胺是大量应用的封闭剂，因为价格不贵，而3,5-二甲基吡唑及丙二酸二乙酯则较贵。例如拜耳公司通用的HDI系的Desmodur BL3175含NCO11.1%是用丁酮封闭的，BL表示封闭Blocked。  \n\n(6）密封剂、环氧增韧剂环氧树脂在常温下能与多元胺固化，但涂膜硬而脆，弹性较低。若加入若干弹性较好的封闭多异氰酸酯，则此3个组分之间发生反应，多元胺既与环氧基反应，同时也与封闭多异氰酸酯反应生成脲，置换出来的封闭剂（例如甲酚）则残留在涂膜中，使成弹性冻胶状密封剂。  \n\n$$\n\\begin{array}{r}{\\mathbb{R}_{n\\sim-\\infty}\\underline{{\\mathrm{CH}}}_{2}+\\mathbb{H}_{2}\\mathbb{N}_{\\sim\\mathrm{out}}\\mathbb{N}_{\\mathbb{H}_{2}}\\ +\\begin{array}{c}{0}\\\\ {\\big\\{\\begin{array}{c}{\\mathbb{H}}\\\\ {\\mathbb{H}}\\end{array}\\right.}\\\\ {\\mathbb{N}_{\\sim\\mathrm{out}}\\mathbb{C}\\mathbb{H}_{2}-\\mathbb{N}_{\\sim\\mathrm{out}}\\mathbb{H}_{2}}\\end{array}+\\frac{1}{\\mathrm{Aroce}(-1)\\sim\\mathbb{R}_{\\sim\\mathrm{out}}^{\\nu}}\\mathbb{R}^{\\nu}\\longrightarrow\\mathbb{R}_{n\\sim\\mathrm{out}}\\underline{{\\mathrm{~H~}}}_{2}\\mathbb{H}_{n\\sim\\mathrm{out}}\\mathbb{H}^{\\nu}\\longrightarrow\\mathbb{R}^{\\nu}+\\mathrm{AroH}}\\end{array}\n$$  \n\nZenoWicks，Jr和其子D.A.Wicks对于封闭异氰酸酯的化学，作了详尽的述评。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 387,
+        "chunk": "# 6.潮气固化聚氨酯漆  \n\n潮气固化聚氨酯漆是含NCO端基的预聚物，通过与空气中潮气反应生成脲键而固化成膜。这种漆的优点是既具有聚氨酯漆的优良性能，又有单罐装涂料的施工方便的特点，不像双组分漆必须临时调配，在规定时限内用完，若调配得太多，则多余部分次日将胶结报废。配料的麻烦，从技术上看来，似乎非常简单，没必要费力气去制造单罐装涂料。但据笔者多年参与两罐装型涂料（环氧或聚氨酯）的大规模现场施工实践，工地上人多手杂，往往不配备秤等计量器具，若配料管理偶一失慎不准，或粗心的施工人员甚至仅将其中的单一组分涂在构件上，酿成大规模返工，非常狼独。而单罐装潮气固化聚氨酯漆则是在造漆厂内严格制造检验，不必临时调配，可避免此类事故。但是潮气固化型也有些不足之处。  \n\n$\\textcircled{1}$ 干燥速率受空气中湿度影响，湿度太低就干得慢。冬季受到温度低和绝对湿度低的双重影响，因此对寒冬气候适应性不及双组分漆，届时须酌加催干剂。  \n\n$\\textcircled{2}$ 加颜料制色漆较为麻烦。  \n\n$\\textcircled{3}$ 施工时每道漆之间的间隔时间不可太长，以免影响层间附着力。  \n\n$\\textcircled{4}$ 此漆成膜时形成脲键，同时产生许多 $\\mathrm{co}_{2}$ ，所以涂膜不宜涂得太厚，不利于 $\\mathrm{CO}_{2}$ 的逸出。  \n\n潮气固化涂料除单组分使施工方便外，尚有另一特点是其机械耐磨性往往比双组分聚氨酯漆好。例如Huls公司用IPDI制成潮气固化清漆，也用IPDI制成双组分聚氨酯清漆，比较两者的力学性能如下：  \n\n<html><body><table><tr><td></td><td>潮气固化清漆</td><td>双组分清漆</td></tr><tr><td>硬度（Konig）/s</td><td>50</td><td>60</td></tr><tr><td>断裂伸长/%</td><td>300</td><td>215</td></tr><tr><td>拉伸强度/MPa</td><td>48</td><td>30</td></tr></table></body></html>  \n\n涂膜抵抗机械破坏磨损的性能往往与其应力-应变曲线下所包覆的总面积有关，表征其破裂能量。从上面数据可见，潮气固化清漆的应力 $(48\\mathrm{N}/\\mathrm{mm}^{2}$ ）与应变（ $300\\%$ ）均较高，所以潮气固化聚氨酯涂料常用作地板清漆。  \n\n以下是美国所产10种不同类型的聚氨酯清漆的硬度及耐磨性的数据：  \n\n\n<html><body><table><tr><td>类型</td><td>Sward 硬度</td><td>耐磨性（失重）/mg (Taber仪，1000g， 1000次)</td><td>类型</td><td>Sward 硬度</td><td>耐磨性(失重)/mg (Taber仪，1000g，</td></tr><tr><td>氨酯油</td><td>30</td><td>45</td><td>双组分B(芳香族)</td><td>50</td><td>1000次) 65</td></tr><tr><td>潮气固化A(芳香族)</td><td>26</td><td>10</td><td>双组分C(芳香族）</td><td>52</td><td>75</td></tr><tr><td>潮气固化B(芳香族）</td><td>36</td><td>20</td><td>双组分D(脂肪族）</td><td>40</td><td>40</td></tr><tr><td>潮气固化C(芳香族)</td><td>40</td><td>20</td><td>双组分E(脂肪族）</td><td>40</td><td>40</td></tr><tr><td>双组分A（芳香族）</td><td>46</td><td>73</td><td>双组分F(脂肪族）</td><td>15</td><td>10</td></tr></table></body></html>  \n\n上述数据是用Taber仪测得，可能与实际耐磨性稍有差距，但可初步看出：  \n\n$\\Phi$ 潮气固化聚氨酯漆的耐磨性优于双组分聚氨酯漆；  \n$\\textcircled{2}.$ 涂膜硬度较低者，耐磨性较好。  \n制造预聚物潮气固化漆要考虑下列因素。  \n\n$\\textcircled{1}$ 分子量要足够大，不需再加人其他配伍剂就能单独迅速干燥，并有满意的力学性能。这就是预聚物与前述双组分漆的加成物不同之处。加成物的分子量低，必须加入配伍剂才能获得良好力学性能。  \n\n$\\textcircled{2}$ 交联密度高则涂膜抗溶剂性、抗药品性提高，交联密度低则挠性提高。  \n\n$\\textcircled{3}$ 在同等的交联密度下，增加聚合物中氨酯基含量则涂膜的硬度和韧性提高。  \n\n制造预聚物一般有3种方法。  \n\n$\\textcircled{1}$ 用分子量较大的聚酯或聚醚（其中可含氨酯键）与二异氰酸酯反应，NCO/OH为2以上，即把原有较复杂的大分子用异氰酸酯封端。  \n\n$\\textcircled{2}$ 将二异氰酸酯与分子量较低的二元或三元的聚醚反应，NCO/OH低于2，一般在$1.2{\\sim}1.8$ 之间。就是说，由于NCO/OH低于2，在以异氰酸酯封端的同时，使预聚物的分子量提高，聚醚链段中嵌入氨酯键，提高机械强度，并保证迅速干燥。聚醚的羟基大多是仲羟基，作为双组分漆则在常温下干性稍慢。若把它加工成潮气固化预聚物，可在反应釜中加温，使仲羟基充分反应，留出端基NCO可潮气固化。涂膜中没有酯键，耐碱性高，适用作耐腐蚀漆、耐磨地板漆等。但聚醚不耐户外紫外线，容易氧化降解，需加人紫外线吸收剂或抗氧剂。  \n\n第一种制造预聚物的方法举例如下：这是以聚酯和环氧树脂的混合物为基础，用过量的甲苯二异氰酸酯封端的预聚物。聚酯由己二酸、三羟甲基丙烷、一缩乙二醇缩合，并溶于溶剂制成溶液，不挥发分 $47\\%$ ，含羟基 $3.6\\%$ 左右。  \n\n第一步：制备聚酯，配方（质量百分数）及操作  \n\n己二酸 一缩乙二醇 三羟甲基丙烷  \n\n10.5%  \n\n将己二酸、一缩乙二醇、三羟甲基丙烷投入反应釜，通 $\\mathrm{CO}_{2}$ ，渐渐升温至 $150\\mathrm{^c}$ ，再以每小时 $10\\%$ 的速度缓慢升温至 $210^{\\circ}\\mathrm{C}$ ，保持至酸值5以下，冷却至 $140^{\\circ}\\mathrm{C}$ ，加人环己酮及甲苯，搅拌半小时，过滤贮存。  \n\n第二步：制备环氧树脂溶液  \n\nE-12环氧树脂  \n\n甲苯  \n\n将环氧树脂和溶剂投入不锈钢反应釜升温溶解，开动揽拌，升温至回流，以充分溶解并除净微量水分，冷却。  \n\n第三步：制备预聚物  \n\nE-12环氧树脂液（25%） 35.2kg HgPO (85%) 0.05kg 聚酯液（含羟基3.6%） 35.2kg  \n\n将上述溶液投人反应釜，加热至 $123^{\\circ}\\mathrm{C}$ 开始有水共沸脱出，逐渐升温至 $142^{\\circ}\\mathbb{C}$ ，脱水基本完成，冷却至 $40^{\\circ}\\mathrm{C}$ ，再加人：  \n\nTDI 27.5kg  \n\n搅拌 $30\\mathrm{{min}}$ 后，缓慢升温至 $90\\%$ ，保温3h，加入醋酸丁酸纤维素（5%溶液）1.9kg，冷却至 $40^{\\circ}\\mathrm{C}$ 出料包装。  \n\n第二种制造法，用聚醚制造预聚物的方法按投料品种和配比，按操作工艺都可以有许多变化调节，以满足对成品各种不同的要求，以下仅是示例。  \n\n![](images/7e2753c39997e19e8a9cfdee4dfe11f4460dcec0ae3d8c63f20b8b205ba08a6f.jpg)  \n\n投料：  \n\n聚醚N303 2mol TDI 聚醚N204 1mol  \n\n操作：将聚醚N303投入反应釜，加人 $5\\%$ 苯脱水，冷却至 $35\\mathrm{^{\\circ}C}$ ，加人TDI，通氮气，搅拌，升温至 $60\\sim70^{\\circ}C$ 反应，加人 $10\\%$ 甲苯以调节黏度，然后加人二元聚醚N204（预先用苯脱水)，升温至 $80\\sim90^{\\circ}\\mathrm{C}$ ，保持 $2\\sim3\\mathrm{h}$ ，终点可抽样以二丁胺测NCO基含量决定之。然后加人溶剂、流平剂（醋酸丁酸纤维素，占全重的 $0.5\\%$ ，预先配成溶液）、抗氧剂（二叔丁基对甲酚，为全重的 $0.9\\%$ ，因为聚醚不耐氧化)，包装密封。产品的NCO基含量（不挥发分计）为7%左右。  \n\n投料的NCO/OH比为1.5。  \n\n除了上例所述全部用聚醚外，也可用聚醚与多元醇的混合物（如三羟甲基丙烷)，加入小分子的多元醇则增加氨酯键密度，提高涂膜强度，举例如下。  \n\n投料：  \n\n<html><body><table><tr><td>三元聚醚</td><td>3mol 9mol</td><td>三羟甲基丙烷 1mol</td></tr><tr><td>TDI(2,4体)</td></tr><tr><td></td></tr><tr><td></td></tr></table></body></html>  \n\n以上NCO/OH比为 $18/9+3=1.$ 5  \n\n操作：加人聚醚、醋酸丁酯及苯，蒸出苯使脱水，于此聚醚液加人TDI，自然升温至$60^{\\circ}\\mathrm{C}$ ，必要时可微热或冷却，以环己酮、醋酸丁酯为溶剂，保温 $3\\mathord{\\sim}4\\mathrm{h}$ 使充分反应之后，降温至 $40\\Upsilon$ 以下，加人三羟甲基丙烷（预先用苯脱水)，升温至 $70\\Upsilon$ ，维持3～4h，直至规定之NCO值，稀释出料。  \n\n必须指出：以上采用的聚醚中往往尚残留微量的碱，会导致产品的黏度或在制造过程中，或在贮存期间逐渐上升而胶凝。遇到这类情况，可在制备预聚物时酌情加入少量的磷酸或苯甲酰氯 $(0.03\\%\\sim0.1\\%)$ ，以消除碱的影响。  \n\n以上制得的预聚物中尚含有相当多的游离二异氰酸酯，有碍健康。可加入少量的三丁基麟，在室温处理数日后，再以对甲苯磺酸甲酯、硫酸二甲酯等抑制，则游离的二异氰酸酯含量可降至 $0.5\\%$ 以下，并酌添溶剂调节至所需黏度。具体操作可参见加成物部分。  \n\n还可制造潮气固化的聚氨酯色漆、聚氨酯富锌底漆、聚氨酯云母氧化铁涂料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 388,
+        "chunk": "# 7.预聚物催化固化聚氨酯漆  \n\n预聚物催化固化聚氨酯漆的结构基本上与前述潮气固化型相似，与潮气固化型差别之处是其本身干燥较慢，施工时需加胺等催干剂以促进干燥，典型的是加少量甲基二乙醇胺。  \n\n![](images/1e841c62e99efd14ce2bd21abc085f817964bc4078bc43e2ac6469983d105f64.jpg)  \n\n其两个羟基均能与预聚物的NCO基交联，而叔氮原子又有催干作用。例如一种催化固化的预聚物用作体育馆地板漆，实效良好。  \n\n预聚物：  \n\n葛麻油(土漂) 26.88kg 环烷酸钙（4%Ca) 0.05kg甘油 1.97kg以上投料在240℃醇解2h后，降温在 $40^{\\circ}\\mathrm{C}$ 以下，加人：TDI 21.0kg 二甲苯(已脱水） 43.7kg二甲苯（留洗加料斗） 6.3kg在 $80^{\\circ}\\mathrm{C}$ 充分反应后，黏度达加氏管 $2\\sim3{\\mathrm{s}}$ ，冷却出料。催化剂溶液：甲基二乙醇胺 0. 5kg 二甲苯 9.5kg配漆比例，施工前把两组分混合：预聚物（甲组分） 1000g 催化剂溶液（乙组分） 26g以上制备预聚物的投料的NCO/OH为 $1.7/1$ ，如需消光，可酌加消光剂如Syloid ED5C等。除了麻油的醇解物以外，也可用聚醚制预聚物。下述是一种廉价的催化固化聚氨酯漆。第一步：制造醇酸树脂。投料：麻油  \n\n苯酐 102. 6kg 稀释用二甲苯 560.0kg 回流用二甲苯 30. 0kg  \n\n操作：在 $210^{\\circ}\\mathrm{C}$ 酯化至酸值5以下，压人对稀釜中稀释搅匀，冷却至 $40\\mathcal{C}$ 出料，得醇酸树脂液，不挥发分 $50\\%$ 左右，羟基含量 $1.7\\%$ 。  \n\n第二步：制预聚物。  \n\n麻油醇酸（50%，即上述醇酸树脂） 520kg 二甲苯 50kgTDI(80/20) 90kg 甲苯 40kg  \n\n操作：将醇酸树脂及溶剂投入 $\\bf{l m^{3}}$ 糖瓷或不锈钢反应釜（带夹套)，升温回流以驱除树脂中及反应釜壁所吸附微量水分至分水器，冷却至 $40\\%$ ，加人TDI，搅拌半小时，使与醇酸树脂的羟基反应，逐渐升温至 $80\\Upsilon$ ，保持 $2\\sim4\\mathrm{h}$ （最后也可酌加少量DBTL催化)。此时NCO值及黏度均趋稳定（涂-4杯 $35\\sim65{\\mathrm{s)}}$ ，即可冷却至 $40\\%$ 装罐(为甲组分)。此漆本身干燥缓慢，须在施工时加 $0.2\\%$ 甲基二乙醇胺（乙组分）。施工时限约数小时，此时除NCO基与羟基交联外，叔胺能催化NCO与潮气反应而固化。  \n\n类似的麻油预聚物涂料，在我国华东地区广泛用作木器漆。它是在1968年5月由上海家具涂料厂所开发，所以取名为“685清漆”。685清漆分为两个组分，甲组分是含NCO基的麻油/甘油预聚物，乙组分是麻油醇酸，并加入顺丁烯二酸改性松香季戊四醇酯，以提高抛光性及固体含量。甲、乙两组分并非按NCO/OH化学当量计算，而是甲组分过量甚多，所以其性质是：部分地是羟基固化，部分地是潮气固化。即使漆工配甲：乙的比例不准，亦能固化。因其价廉，销量甚广，但与国外木器用聚氨酯漆相比，则差距甚大。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 389,
+        "chunk": "# 8.聚氨酯漆用的颜料和色漆的制造  \n\n对于氨酯油，因为已不含异氰酸酯基，其性质与醇酸树脂相近，可根据需要选用一般的颜料。  \n\n对于含有异氰酸酯基的聚氨酯漆，因对颜料有起反应的可能，应该选用合适的颜料。  \n\n一般颜料表面都吸附着一定量的水分，遇异氰酸酯基则反应生成聚脲，同时产生二氧化碳。若颜料含水分多，在潮气固化型涂料的贮存期间会引起胶凝和鼓罐。对于双组分漆，则施工时在涂膜中产生小气泡，影响涂层质量。  \n\n某些颜料除吸附水分外，尚含有某些成分能对异氰酸酯的反应起催化作用。例如碱性的红丹、氧化锌、碳氮化铅、铬橘黄；还有含水溶性成分的锌黄、铁盐以及某些槽法炭黑等，制漆时必须慎重试验后选用，以免影响贮藏稳定性或缩短双组分漆的施工时限。一般推荐的颜料有以下几种。  \n\n白色：钛白以及立德粉。  \n\n红色：铁红、镉红，某些钼铬红，若干有机颜料，如红、喹吖啉酮红等。  \n\n橙色：镉橙，某些有机橙。  \n\n黄色：铁黄、镉黄、有机黄颜料。普通铅铬黄经试验也可用于双组分漆，笔者经验铅铬黄用于脂肪族聚氮酯漆，具有优良耐候保光性。  \n\n绿色：氧化铬绿、酥菁绿。  \n\n蓝色：酞菁蓝（NCNF型较佳）、群青。  \n\n黑色：铁黑、灯黑、炉法炭黑（某些槽法炭黑须经试验后才可用）、石墨可提高涂层的导电性，以导泄静电。  \n\n体质颜料：滑石粉、重晶石粉、沉淀硫酸钡、陶土、云母粉、碳酸钙、硅藻土、气相二氧化硅、沉淀硅胶消光剂等。  \n\n有些颜料虽会促进异氰酸酯基反应，但若将其分散于双组分的羟基组分中，配制合宜，则也可用。例如氧化锌能抗紫外线，兼有防霉效果。锌黄和锶黄对轻金属有优良的防腐蚀作用，实际上应用颇多；但对潮气固化型漆，则必须慎重选用。  \n\n制造氨酯油色漆的工艺与制造常规的醇酸色漆相仿。制造双组分聚氨酯漆时，将颜料分散在含羟基组分中作为一个组分，将多异氰酸酯作为另一组分，使用时互相配合。制造潮气固化型色漆时，因树脂中含有游离的异氰酸酯基，能与颜料的水分反应，若仍用常规工艺，则产品胶凝、鼓罐，不能贮存。为了克服此困难，可采用两种方法。  \n\n(1）异氰酸酯除水法即用单体的异氰酸酯预先与颜料及溶剂反应，脱除其所含水分，然后加入含NCO基的预聚物树脂充分研磨分散。此方法又可有两种工艺。  \n\n$\\Phi$ 球磨法将颜料、溶剂投入球磨中。预先用KarlFischer法测其所含水量，计算出所需 NCO基量，投入所需量之MDI或甲苯磺酰异氰酸酯 $H_{3}C\\rightleftharpoons S O_{2}N C O$ ，在球磨机中滚动分散，不时放 $\\mathbf{CO}_{2}$ 气，待颜料溶剂所含水分完全消除，然后加入预聚物，充分研细后出料。此法需多次放气，很不方便，且球磨机换色也很困难，出料后球磨中残留漆浆中含NCO基，一旦胶凝在球磨机中，则甚为麻烦。以上所制得产品可贮藏6个月无变化。如不用异氰酸酯预先处理，则产品7天后胶化。  \n\na.预聚体多异氰酸酯（61%） 32. 90kg g.云母氧化铁 14.58kg b.甲苯磺酰异氰酸酯 1.67kg h.冲稀铝粉浆 6.75kg c.消泡剂（10%溶液） 0. 21kg i.200号芳烃溶剂 8.22kg d.膨润土浆（10%） $69\\mathbf{k}_{B}$ j.原甲酸三乙酯 0. 85kg e.滑石粉（细） 22.03kg 总计 100.00 f.丙二醇甲醚醋酸酯 4. 11kg  \n\n操作：将a. $\\mathrm{\\simd.}$ 投入高速分散机搅匀 $\\mathrm{5}\\mathrm{min}$ ，然后加人e ${\\sim}\\mathbf{f}$ ，以 $\\mathrm{13m/s}$ 线速度搅拌$15\\mathrm{min}$ ，使滑石粉充分分散，再加人云母氧化铁，以 $\\tau_{\\mathrm{{m}/{s}}}$ 线速度搅拌 $\\mathrm{5}\\mathrm{min}$ ，加入冲稀的铝粉浆，以 $4\\mathrm{{m}/\\mathrm{{s}}}$ 的慢速搅拌 $\\mathsf{5m i n}$ ，停止。于漆浆上浇以200号芳烃溶剂和原甲酸三乙酯，静置过夜，次日搅拌均匀，装罐。此法中的甲苯磺酰异氰酸酯的反应活性高，优先与水分反应，虽与预聚体的NCO共存，仍能制得贮藏性好的产品。配方中的铝粉浆经预先搅拌冲稀，以便于分散：  \n\n商售铝粉浆（含铝粉65%） 66.6kg 200号芳烃溶剂 33. 4kg  \n\n配方中的膨润土浆是制成预胶（Pregel）：  \n\n膨润土（Bentone34，国产品亦可） 10kg 二甲苯 85kg  \n\n两者拌匀后，再加人活化剂拌匀：  \n\n活化剂 5kg 成为胶，总计 100kg  \n\n以上活化剂不可用甲醇以免与NCO反应，可用BYK公司的Anti-terraU。国产的碳酸丙烯酯亦可代用。  \n\n(2）共沸脱水法此法是笔者等于20世纪60年代后期制造潮气固化聚氨酯色漆时所开发，是将颜料与含羟基树脂（中间产品）预先研磨分散，连同全部溶剂一起加人反应釜中共沸脱水、冷却，加入二异氰酸酯，使与羟基树脂反应成潮气固化预聚物，可得稳定的色漆，而不需KarlFischer测定水含量，也不需加入甲苯磺酰异氰酸酯，成本低而贮藏稳定性良好。配方示例如下：  \n\n麻油醇酸（含羟基1.4%，见前） 686kg TDI 134kg 色浆 257kg 二甲苯 76kg 甲 63kg   \n操作：先研磨色浆  \n\n<html><body><table><tr><td>钛白 铁黄</td><td>71.2% 1.2%</td><td>麻油醇酸（羟基1.4%，50%固体分）</td><td>27.6%</td></tr></table></body></html>  \n\n铁黄  \n\n1.2%  \n\n把色浆加入反应釜（以夹套塘瓷釜为宜，有些不锈钢釜内壁不光滑，不易清洗)，加人醇酸树脂搅拌均匀，再加入二甲苯和甲苯，搅拌升温，至 $128^{\\circ}\\mathrm{C}$ 左右开始回流脱水，约经$_{1\\sim2\\mathrm{h}}$ 后脱净，分水器视孔中无水滴下，冷却至 $40\\Upsilon$ ，加入TDI，搅拌半小时，逐渐升温至$70\\%$ ，保温，升温至 $100^{\\circ}\\mathrm{C}$ 保温 $2\\mathord{\\sim}4\\mathrm{h}$ ，测黏度涂-4杯 $(25^{\\circ}\\mathsf{C}$ ）为 $40\\sim50\\mathrm{s}$ ，冷却到 $40^{\\circ}\\mathrm{C}$ ，过筛并同时装罐。产品贮藏稳定性良好。使用时加入0.1%甲基二乙醇胺催干。  \n\n若干聚氨酯漆配方示例，供参考。  \n\n$\\textcircled{1}$ 黑色聚氨酯瓷漆（双组分）  \n\n<html><body><table><tr><td>聚酯（181号，脂肪酸改性，75%溶液） 特黑（6号，Deguss8)</td><td>18.4g 2.3g</td><td>分散剂(Disperbyk 161) 醋酸丁酯</td><td>2.3g 5.0g</td></tr><tr><td>将以上组分混合研细，然后调稀，加料：</td><td></td><td></td><td></td></tr><tr><td>聚酯181号(75%)</td><td>26.5g</td><td>二甲苯</td><td>15.0g</td></tr><tr><td>消泡剂BYK 141</td><td>0.3g</td><td>MPA溶剂</td><td>9.0g</td></tr><tr><td>流平剂BYK306</td><td>0.3g</td><td>醋酸丁酯</td><td>16.9g 总计100.0g</td></tr><tr><td>高沸点流平溶剂Byketol-OK</td><td>4.0g</td><td>固化剂：TDI/TMP 加成物（75%) 醋酸丁酯</td><td>32.0g 18.0g</td></tr><tr><td>②白色聚氨酯瓷漆（双组分）</td><td></td><td></td><td>总计50.0g</td></tr><tr><td>聚酯181号（75%)</td><td>16.4g</td><td>分散剂Disperbyk 110</td><td>1. 1g</td></tr><tr><td>TiO(金红石)</td><td>27.5g</td><td>MPA溶剂</td><td></td></tr><tr><td>将以上组分研磨后，调稀，加料：</td><td></td><td></td><td>10.0g</td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td>聚酯181号(75%)</td><td>5.5g</td><td>固化剂：HDI缩二脲(75%)</td><td>8.2g</td></tr><tr><td>醋酸丁酯</td><td>18.5g</td><td>TDI/HDI三聚体（60%）</td><td>8.2g</td></tr><tr><td>流平助剂BYK331</td><td>0.3g</td><td></td><td>总计100.0g</td></tr><tr><td>消泡剂BYK141</td><td>0.3g</td><td></td><td></td></tr><tr><td>高沸点流平溶剂Byketol-OK</td><td>4.0g</td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 390,
+        "chunk": "# 以上固化剂亦可用等当量之HDI三聚体代替之。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 391,
+        "chunk": "# $\\textcircled{3}$ 木器打磨底漆（特点是快干而易于打磨）  \n\n聚酯1300号 54.0g 消泡剂BYK 052 0.3g 硝化棉片 1.5g 固化剂 硬脂酸锌 4.0g TDI三聚体（50%） 30.0g 分散剂BYK P 104 0.4g 醋酸丁酯 20.0g 酸酸乙酯 19.08 总计150.0g 甲苯 16.3g 9  \n\n操作：先溶解硝化棉片于部分溶剂中；硬脂酸锌及P104分散于聚酯中；混合硝化棉溶液和聚酯溶液。  \n\n说明：普通硝化棉商品含有 $35\\%$ 醇以资安全，但醇会与NCO反应，所以改用硝化棉片。硬脂酸锌使涂膜易于打磨，但不易分散在树脂液中，往往尚附有空气未润湿，隔夜将在涂料面上浮有许多气泡。加入P104可助排除空气。硬脂酸锌的商品，各厂略有不同，必须选用。某些牌号会使施工时限缩短。涂料中加人硬脂酸锌后会稍呈混浊，但涂膜干燥经打磨后仍透明，木纹清晰。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 392,
+        "chunk": "# 9.聚氨酯沥青漆  \n\n聚氨酯沥青漆是继环氧沥青漆之后较新的品种，由煤焦沥青与聚氨酯树脂所组成。煤焦沥青价廉而抗水性优良，含聚氨酯树脂后提高了耐油性，改善了热塑和冷裂的缺点。对于水利工程、原油贮罐、港湾码头、船舶、管道及一般化工腐蚀等都可采用。与环氧沥青漆对比，主要的差异见表2-1-187。  \n\n表2-1-187环氧沥青漆与聚氨酯沥青漆的比较  \n\n\n<html><body><table><tr><td>性 能</td><td>环氧沥青漆</td><td>聚氨酯沥青漆</td></tr><tr><td>施工温度</td><td>要求10℃以上</td><td>0℃也可固化</td></tr><tr><td>施工时限</td><td>较长，一般可用24h</td><td>较短，4~8h内用完</td></tr><tr><td>贮存稳定性</td><td>较好，不易变质</td><td>较差，必须密闭以免胶凝</td></tr><tr><td>干性</td><td>稍慢</td><td>较快</td></tr><tr><td>涂膜耐寒性</td><td>较脆</td><td>较好</td></tr><tr><td>制造过程</td><td>简单</td><td>较复杂，沥青和溶剂要脱水</td></tr><tr><td>施工意外适应性</td><td>较好</td><td>涂层未干前遇雨易起泡</td></tr><tr><td>耐碱性</td><td>好</td><td>尚好 好</td></tr><tr><td>耐酸性</td><td>尚好</td><td></td></tr></table></body></html>  \n\n从表2-1-187可见两者最主要的差别在于施工温度，环氧沥青漆虽性能良好，但在寒冬季节难以固化。因此船舶漆制造厂常生产“冬用型环氧沥青漆”，即其固化剂不是用胺类，而是用多异氰酸酯，便于冬季施工，以求不影响造船周期。  \n\n煤焦沥青含有许多稠环和杂环化合物，呈芳香性，与聚氨酯及环氧树脂混溶性好。用Zerewitinoff分析法可测出煤焦沥青含活泼氢约 $0.8\\%\\sim1\\%$ （各地区产品差异很大)，有酚基、醇基及氨基、亚氨基等，它们能与NCO基反应，而且氨基等又能催化NCO基反应，所以有些聚氨酯沥青漆在双组分拼和后，往往施工时限很短促。  \n\n聚氨酯沥青漆可制成双组分和单组分潮气固化型两种，双组分的涂层性能很好，较便于制造，所以工业产品以双组分型较多。单组分潮气固化聚氨酯沥青漆对其原料煤焦沥青和溶剂的脱水要求很高。双组分漆中的甲组分是含NCO基的芳香族多异氰酸酯预聚物，乙组分是煤焦沥青和多羟基树脂（聚醚、聚酯、环氧等)。如需耐户外曝晒，可加人铝粉、铁红等颜料以屏蔽紫外线的透入。制备时要注意在沥青搅拌下逐渐把多羟基树脂加入沥青中。若次序颠倒，则沥青容易析出，降低涂层的性能。此外，需注意对不同规格的煤焦沥青要试验筛选，由于其含氮、硫等元素，往往催化作用有差异，需挑选合用的品种。在沥青和羟基的乙组分中可加入分子筛及原甲酸乙酯等吸潮剂，以吸除微量水分。一般溶剂型聚氨酯沥青涂层的厚度约为 $80\\mu\\mathrm{m}$ 。无溶剂型的聚氨酯沥青漆的涂膜厚度可达 $400\\mu\\mathrm{m}$ ，可用液化的MDI（如Bayer 公司的DesmodurVL）或PAPI，但须仔细除去微量的水分，并加消泡助剂。  \n\n聚氨酯沥青漆中虽含大量沥青，但施工间隔期仍需接近，超过3天以上容易层间剥离，此时底层必须打毛后才能覆漆，所以最好每天一道以保证工程质量。  \n\n聚氨酯沥青漆示例。  \n\n(1）制备预聚物先将麻油与甘油按 ${\\mathrm{~1~:~0.~48~}}$ 摩尔比进行醇解，以环烷酸钙为催化剂，每公斤油加钙(按金属计) $\\phantom{-}0.04\\phantom{0}\\phantom{.0}\\phantom{0}$ ，在240℃醇解2h后用 $84\\%Z$ 醇水溶液测容忍度，至大于25时为终点，冷却至 $60^{\\circ}\\mathrm{C}$ ，加入二甲苯共沸脱水并调整不挥发分至 $70\\%$ ，得溶液备用，其羟值为 $150\\sim165$  \n\n另将聚醚（羟值 $460\\sim470$ ）用甲苯共沸脱水，并调整不挥发分至 $80\\%$ ，得溶液备用，其羟值为 $360\\sim380$ 身  \n\n将甲苯二异氰酸酯 $24\\upkappa_{\\mathrm{{B}}}$ 投入反应签，开动搅拌并加热至 $50\\%$ ，加人上述醇解物溶液$32\\mathbf{k}_{\\mathbf{B}}$ ，升温至 $60\\sim65\\mathrm{{C}}$ ，加入上述聚醚溶液 $6.75\\mathrm{kg}$ ，再加人甲苯 $24\\mathbf{k}\\mathbf{g}$ ，升温至 $70\\Upsilon$ ，保温至NCO基含量为 $6.0\\%\\sim6.8\\%$ ，黏度达加氏管 $17\\mathrm{\\sim}22\\mathrm{s}$ 为终点，加人 $22g$ 稀磷酸溶液（磷酸 $2\\%$ 环己酮溶液）揽匀，降温至 $50\\mathrm{{^c}}$ 以下出料。加磷酸的效用可以提高贮存稳定性，抵消  \n\n在醇解时加入环烷酸钙的催化作用。  \n\n（2）制备沥青溶液将煤焦沥青（软化点 $45\\sim55\\mathrm{{C}}$ ） $400\\mathbf{kg}$ 投入釜内，加热使熔化，开动搅拌，升温至 $130{\\sim}150\\Upsilon$ 后保温。每小时取样测软化点，至达 $579\\mathbb{C}\\pm3\\mathbb{C}$ 范围内为终点，降温至110～120°℃，加人脱过水的混合溶剂266kg（环己酮：甲苯：二甲苯=40：35：25)，搅匀，降温至 $50\\mathrm{^c}$ 以下出釜，澄清或经离心机，不挥发分为 $60\\%\\pm2\\%$ α",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 393,
+        "chunk": "# (3）沥青底浆研磨  \n\n配方：  \n\n沥青溶液（60%） 31. 5kg 锌黄 33.2kg634环氧二甲苯溶液（80%） 4.5kg 云母粉 9. 4kg铁红 4.7kg 混合溶剂（见上） 16.7kg研磨至 $80\\mu\\mathrm{m}$ 以下，用混合溶剂调整不挥发分至 $75\\%$ 费  \n\n<html><body><table><tr><td colspan=\"2\">(4）配漆</td><td></td><td></td></tr><tr><td colspan=\"2\">清漆（面漆）</td><td>沥青溶液</td><td>50kg一</td><td></td></tr><tr><td colspan=\"2\">底漆</td><td>沥青颜料浆</td><td></td><td>一62kg</td></tr><tr><td>预聚物溶液</td><td colspan=\"2\">38kg 50kg</td><td></td><td></td></tr></table></body></html>  \n\n(5）施工可用刷涂或喷涂，适用于金属或混凝土。每道厚度约 $50\\mu\\mathrm{m}$ 。对于防腐蚀涂层应刷二道底漆、二道面漆共4道，要求较高时应涂 $5{\\sim}6$ 道。  \n\n下面介绍一种聚氨酯沥青漆，该漆是由TDI/TMP加成物为甲组分，由煤焦沥青及聚醚（含8.5%羟基）组成乙组分。涂膜厚度 $180\\mu\\mathrm{m}$ ，涂布后在21天内测其涂膜的摆杆硬度(Konig)。从图2-1-47可见在 $20\\%$ 硬度较高，在 $4\\mathbb{C}$ 时虽涂膜硬度稍低，但仍可超过30s，表示该漆在低温仍有良好的干燥性。在4C时与环氧沥青漆比较，样板涂布经24h后浸入鼓空气的海水中，结果聚氨酯沥青漆的防腐蚀性优良得多，表示该漆在低温时良好的干燥性。经试验：聚氨酯沥青漆可用作船舶的阴极保护漆，在超电压电位 $1250\\mathrm{mV(Cu/CuSO_{4})}$ 电极)的海水浸渍6个月后，涂膜保持良好，并与各种车间底漆的配套性良好。  \n\n制造聚氨酯沥青漆的要点是其施工时限较短促，因此宜选用聚醚，因聚醚含仲羟基较多，反应性较慢。挑选较强的溶剂也可延长施工时限。有些煤焦沥青的催化作用很强，缩短了施工时限，对此可事先对该沥青加入少量的单官能异氰酸酯处理之（如甲苯磺酰异氰酸酯，或少量MDI）则可延长施工时限（见图2-1-48）。  \n\n![](images/35f012457d9677168026d40c4da4468482451e06fd256a7f1661f7a450ee7f82.jpg)  \n图2-1-47聚醚沥青/TDI加成物涂料的固化硬度（膜厚 $180\\mu\\mathrm{m})$ 1—在20℃固化；2—在4℃固化  \n\n![](images/ab8406d63a8379ef43ab63a63011e9728aadc73164f17f8f3cff924293c4712a.jpg)  \n图2-1-48聚醚沥青/TDI加成物涂料的黏度行为1一未处理过的沥青；2一处理过的沥青  \n\n我国冯明霞试制了聚氨酯沥青涂料，应用于渔站压力输水管内壁、油田注水井下的钢管、水澄清槽内壁以及泵的叶轮防腐，性能较为理想。上海市涂料研究所顾根福、胡岳楠等试制了厚膜型聚氨酯沥青涂料，应用于重防腐系统，可在低温下固化，耐腐蚀性良好。聚氨酯沥青涂料不可用于船舶的压载水舱。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 394,
+        "chunk": "# 10.弹性聚氨酯漆  \n\n前述各种聚氨酯漆大多供涂覆刚性底材（钢铁、铝、木材等)，涂膜一般很坚硬，但弹性伸长率不大，涂膜处在玻璃态。对于挠性底材如纺织品、皮革、橡胶、软泡沫塑料等，则需要高弹性涂料，以适应变形扭曲。弹性聚氨酯漆的伸长率可达到 $300\\%\\sim600\\%$ 。涂膜的玻璃化温度低，涂膜在常温是处于高弹态。高弹态的特征表现在较小的外力作用下即发生很大的形变，并且当外力除去之后能够恢复原来的形状。要使聚氨酯漆具备高度弹性，则其结构必须是由线型长链大分子组成（分子量范围在几百至几千的各种类型树脂均不能显现出高弹性)，并具有适度的交联（或称硫化)。线型大分子间存有弱的分子间力，在常温是柔顺无规线团，能够移动或转动。在柔性链段之间需有短的刚性链段，示意式如下：  \n\n上式中，短节的二元醇（G）所生成的氨酯链段呈刚性，在分子间氢键吸力大，可起到弱的交联点的作用，而长链部分的链段柔软。刚性部分的数量决定涂膜的硬度和高温性质。柔软部分的数量决定涂膜的弹性、低温性质、耐水解性、耐溶剂性。  \n\n制造弹性聚氨酯漆的方法可分为以下几类。  \n\n(1）固化型  \n\n$\\Phi$ 长链低支化度聚酯与多异氰酸酯反应。  \n$\\textcircled{2}$ 长链预聚物与芳胺反应。  \n$\\textcircled{3}$ 长链聚酯-氨酯二醇与多异氰酸酯热固化。  \n\n(2）挥发型  \n\n$\\textcircled{1}$ 长链预聚物用二元醇扩链。  \n$\\textcircled{2}$ 长链预聚物用二元胺扩链。  \n\n上述第一种方法是早就采用的。首先制备长链低支化度的聚酯，例如：  \n\n己二酸 $3\\mathrm{mol}$ 一缩乙二醇 三羟甲基丙烷 0. 291mol  \n\n2. 91mol  \n\n可制得聚酯，是流动液体，羟基含量 $1.8\\%$ 左右。用此聚酯与TDI加成物配合，加环烷酸皂类催化剂，可获得柔韧的弹性涂层。用此聚酯与液化MDI或PAPI配合，可制无溶剂弹性涂料，适宜涂覆混凝土表面。混凝土收缩变形产生裂缝时，弹性涂层能延伸而不开裂，保持膜层的完整。  \n\n这类配套的双组分的反应，在NCO与OH结合形成聚氨酯的同时，NCO也会与周围的水分反应生成脲。因此受施工时的空气湿度、底材的含水量、混凝土的碱性催化作用等影响，在不利的施工条件下不能把羟基组分充分地连接起来形成大分子，对弹性不利。  \n\n为了改善上述情况，可利用氨基与NCO基反应活性极高（超过空气中潮气）的特点来制备聚氨酯弹性体，尽可能减少潮气等竞争反应，以获得高分子量的结构规整的线型分子。其方法是先制备线型的预聚物，再用芳香族二胺例如4，4'-二氨基-3，3'-二氯二苯甲烷（简称MOCA）或间苯二胺等来固化。脂肪族胺反应太快不宜用。  \n\n第一步：先制备聚酯。  \n\n葵二酸聚酯 己二酸聚酶 癸二酸聚酯 己二酸聚酯 葵二酸 59.4kg 一缩乙二醇 38.6kg 46.1kg 己二酸 53.9kg 三羟甲基丙烷 2.0kg  \n\n第二步：制备预聚物。  \n\n<html><body><table><tr><td>葵二酸聚酯 己二酸聚酯TiO（6/4）色浆</td><td>37.6kg 15.5kg</td><td>己二酸聚酯SiO：（9/1）色浆 二甲苯</td><td>6.3kg 28.0kg</td></tr><tr><td>TDI(2,4体)</td><td>12.6kg</td><td></td><td></td></tr><tr><td>配漆：</td><td></td><td></td><td></td></tr><tr><td>预聚物色浆（72%固体溶液）</td><td>75.5%</td><td>涂膜伸长率</td><td>450%~550%</td></tr><tr><td>MOCA(30%醋酸乙酯溶液）</td><td>24.5%</td><td>涂膜拉伸强度</td><td>15~20MPa</td></tr><tr><td></td><td>100.0%</td><td>NCO/NH</td><td>1/0.9</td></tr><tr><td>不挥发分</td><td>61.7%</td><td></td><td></td></tr></table></body></html>  \n\n上面介绍的是冷固化涂料，供各种现场施工。纺织品的弹性聚氨酯涂料则都是加热干燥，分为两种，固化型和挥发型。  \n\n固化型示例：用XDI（或其他二异氰酸酯）先制成长链的聚酯-氨酯-二元醇，再加入少量的交联剂，可获得似橡胶的弹性膜。首先制备羟基封端的长链聚酯-氨酯-二元醇：  \n\n聚酯（己二酸/1,4-丁二醇，分子量约 0. 68mol 一缩乙二醇 0. 35mol 1000，端羟基） NCO/OH=1. 0/1. 03   \nXDI 1. 00mol  \n\n以上反应时可酌加一部分醋酸乙酯，最后再加醋酸乙酯稀释成35%溶液，黏度（加氏管25℃）为 $10\\mathrm{\\sim}12\\mathrm{s}$ 。  \n\n配漆：  \n\n<html><body><table><tr><td>聚酯-氨酯-二元醇（35%溶液） TiO(金红石型)</td><td>100g 17.5g</td><td>丁醚化三聚氰胺树脂（50%溶液） XDI/TMP加成物（75%）</td><td>5.0g 10.0g</td></tr><tr><td>MPA溶剂</td><td>17.5g</td><td></td><td></td></tr><tr><td>在120℃烘10min左右，涂膜性能如下：</td><td></td><td></td><td></td></tr><tr><td>伸长率</td><td>340%</td><td>拉伸强度</td><td>33MPa</td></tr><tr><td>100%伸长时模量</td><td>6.5MPa</td><td>褪色仪照射100h后</td><td>不泛黄</td></tr><tr><td>表面状况</td><td>不发</td><td></td><td></td></tr></table></body></html>  \n\n加 XDI/TMP加成物及三聚氰胺树脂的量可酌量调节。在烘干过程中，NCO基不仅与羟基交联，也能与氨酯键的氢原子交联。  \n\n挥发型聚氨酯弹性涂料涂覆在纺织品上，使用颇广。它不需固化，漆料配合后不会变稠，没有施工时限问题。涂布产品的质量好，可用转印法施工，涂成光亮的，或消光的，或呈压印花纹的人造革，耐磨、耐晒、耐油、耐低温、手感滑爽柔软，比聚氯乙烯人造革优良，可供作优级防雨布、帐篷、袋包、汽车坐垫、充气船等。  \n\n漆在成膜过程中并无交联固化，仅是溶剂挥发，因此树脂本身必须事先具备良好的物理机械强度，要有足够大的分子量，而且柔性长链和刚性短节的交替结构要有适当的比例。长链分子段之间的氨酯键，彼此间有氢键相吸，类似于橡胶的硫化键的作用。所不同者，后者是化学键，而前者只是次价键。但是它也能使这种聚氨酯漆具有弹性。  \n\n制造这种热塑性树脂，以对称的二异氰酸酯（例如MDI）产物的性能较好。用二官能度的聚酯与MDI及TDI制造弹性涂料如下。  \n\n<html><body><table><tr><td></td><td>MDI型</td><td>TDI型</td><td></td><td>MDI型</td><td>TDI型</td></tr><tr><td>二官能度聚酯</td><td>1. 0mol</td><td>1. 0mol</td><td>溶剂（二甲基甲酰胺/丁酮）</td><td>111</td><td>112</td></tr><tr><td>1,4-丁二醇</td><td>1. 0mol</td><td>0. 95mol</td><td></td><td>75%</td><td>70%</td></tr><tr><td>三羟甲基丙烷</td><td>一</td><td>0. 05mol</td><td>涂膜伸长率/%</td><td>740</td><td>650</td></tr><tr><td>MDI</td><td>2. 0mol</td><td>一</td><td>拉伸强度/MPa</td><td>28</td><td>3.4</td></tr><tr><td>TDI</td><td></td><td>2. 0mol</td><td>300%伸长时模数/MPa</td><td>6.6</td><td>1.08</td></tr><tr><td>辛酸亚锡</td><td>0.01%</td><td>0.01%</td><td>耐磨性（Taber，磨耗量）/mg</td><td>1.1</td><td>5.5</td></tr><tr><td>不挥发分</td><td>25%</td><td>30%</td><td></td><td></td><td></td></tr></table></body></html>  \n\n可见，由于MDI的对称结构，使高分子键之间容易敛集，所以其强度、耐磨性、伸长率均远比TDI产品优越。对于要求装饰性的用途，MDI容易泛黄不宜用，以HMDI较好。一般的制漆法是，先用长链的聚酯与HMDI反应，制成端基为NCO的预聚物，再用二元醇或二元胺扩链。用二元醇扩链的产品溶液稳定性较好，但需用二甲基甲酰胺等高价溶剂，而且涂膜在 $100^{\\circ}\\mathrm{C}$ 以上会发黏。上面介绍的MDI型，就是用二元醇（丁二醇）扩链的例子。用二元胺扩链的涂料的溶液稳定性较差，黏度逐渐上升，约于25天之后胶凝，但胶凝并非由于化学键产生三维立体结构，只是来自分子间的氢键，只要再加热回温搅拌，即可恢复原状供使用。  \n\n二元胺扩链涂层的耐热性可达 $200\\mathrm{\\dag}$ 不发黏，这是因为二元胺生成脲键，比醇产生的氨酯键多一个氢原子，能生成更多的氢键，分子间吸力大。示例如下。  \n\n二羟基聚酯 1. 0mol羟基 二月桂酸二丁基锡 0  \nHMDI 1.9mol氨酯基 溶剂（甲苯：异丙醇：丁酮一  \n乙二胺(无水） 0.81mol氨基 35 + 30  35)  \n不挥发分 25%  \n\n操作：将HMDI及锡催化剂投入5L反应烧瓶，搅拌、升温至 $40\\Upsilon$ ，缓缓加入聚酯的甲苯溶液，渐渐升温至 $80^{\\circ}\\mathrm{C}$ 保持约4h，或保持到NCO含量降至理论值为止。加甲苯稀释至67%固体含量，冷却至室温，得预聚物液。用二丁胺分析法精确测定其NCO含量。将配方所需的乙二胺、丁酮、甲苯、异丙醇预先混合，在剧烈搅拌下迅速全部加入反应烧瓶，搅拌使充分反应即得弹性涂料溶液，在常温的贮藏稳定性约为25天。制造时，原料须充分共沸脱水，准确分析和称量。加入胺的量为预聚物NCO当量的 $90\\%\\sim95\\%$ ，太少则强度下降，太多则溶液的稳定性差。聚酯的分子量约2000左右。采用聚酯而不用聚醚，是因为聚酯涂膜的耐溶剂性较好。溶剂用异丙醇，是因为它是仲醇，漆的稳定性较好。若采用伯醇，则会在长期贮存中与氨酯键、脲键起酯交换反应，使高聚物降解。现今溶剂型弹性涂料很多被水性涂料所替代。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 395,
+        "chunk": "# 11.近年来的进展  \n\n聚氨酯涂料性能优良，但通常含有不少溶剂，污染大气，有损工人健康，有火灾爆炸危险，且溶剂挥发掉，也是资源浪费。全世界涂料发展方向是，降低这些有机挥发物VOC，  \n\n积极的努力方向是： $\\textcircled{1}$ 高固体或无溶剂涂料； $\\textcircled{2}$ 粉末涂料；  \n$\\textcircled{3}$ 水性涂料，包括光固化。  \n\n聚氨酯耐磨自愈弹性涂料的自愈合机理如图2-1-49所示。  \n\n(1）高固体涂料溶剂的作用是稀释成膜物质，以便于涂布施工。所以降低树脂的黏度即可减少溶剂需量（或完全不需溶剂)。降低聚氨酯系成膜物质黏度的措施，可分两方面探讨。  \n\n![](images/8a77400f67f3802fe1415f192a411cc9c6e0f3b0ebe11bc0288b96772975f8ab.jpg)  \n图2-1-49聚氨酯耐磨自愈弹性涂料的自愈合机理  \n\n$\\Phi$ 羟基组分降低黏度措施在双组分聚氨酯涂料配方中，羟基组分占重量最多，对涂料黏度的贡献最大，应尽力降低聚酯或丙烯酸树脂的黏度。 迎  \n\nPCI2001年5月报道，EdBarsa等采用VOC豁免的TBAc（醋酸叔丁酯）作溶剂，配合低黏度的丙烯酸多元醇可制备超低VOC的高固体分聚氨酯涂料。  \n\n制备低黏度和高官能度的丙烯酸多元醇或聚酯多元醇的技术途径较多。其中选择适当的引发剂和高温反应$c>160^{\\circ}$ ）比较常用。另据报道，采用 $\\mathrm{C}_{13}\\mathrm{\\sim}\\mathrm{C}_{16}$ 的叔碳酸缩水甘油酯与丙烯酸反应生成位阻型的一OH，极大减少了分子间生成氢键的能力，从而引起树脂黏度大大下降，由此可制备固含量 $590\\%$ 的丙烯酸多元醇。  \n\n![](images/c1e3ad16798f72fa3db4a004667a8ef234e70d622dfb4fba537d435d81afa891.jpg)  \n\n其工艺过程可用丙烯酸单体与叔碳酸缩水甘油醚先反应制备预聚物后参与聚合反应；也可以待丙烯酸单体聚合后，再与叔碳酸缩水甘油醚反应。通常采用后一种工艺。  \n\n酮亚胺或醛亚胺是二元伯胺与酮或醛的羰基缩合，产生水和亚胺，前在环氧涂料章中已介绍作为潜固化剂。该漆涂布后遇空气中潮气会释出胺与NCO反应，这也是一类降低黏度的活性稀释剂，商品醛亚胺黏度 $23^{\\circ}\\mathrm{C}$ ）约 $25\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$ ，酮亚胺约 $80\\mathrm{{mPa}\\cdot\\mathrm{{s}.}}$ ，此外尚有一种活性稀释剂，是双唔唑烷，IndustrialCopolymer公司的商品名IncozolLV。  \n\n![](images/1711989cbd03afb1d38e0583a83035140fc86afcb2532567552bf3660f139a54.jpg)  \n\n涂布后遇潮气析出氨基和羟基，会与NCO交联。配入涂料中可以提高固体含量（最多取代 $30\\%$ ）提高涂膜硬度和抗化学性，不产生 $\\mathrm{CO}_{2}$  \n\n$\\textcircled{2}$ 异氰酸酯组分的黏度降低将TDI、IPDI、HDI等二异氰酸酯原料，加工成为缩二脲、加成物、异氰脲酸酯等多异氰酸酯，以配制双组分涂料。不同的加工工艺可控制产物的性质和黏度。例如拜耳公司用HDI制造缩二脲有三种规格。  \n\n<html><body><table><tr><td></td><td>黏度（23C)/mPa•s</td><td>固体分</td></tr><tr><td>Desmodur N100（标准品）</td><td>10000</td><td>100%</td></tr><tr><td>Desmodur N3200（低黏度品）</td><td>2500</td><td>100%</td></tr><tr><td>Desmodur N75</td><td>255（含溶剂）</td><td>75%</td></tr></table></body></html>  \n\n拜耳公司用HDI制成异氰脲酸酯也有不同规格。  \n\n<html><body><table><tr><td></td><td>黏度（23C)/mPa * s 固体分</td></tr><tr><td>Desmodur N3300（标准品） 3000</td><td>100%</td></tr><tr><td>Desmodur N3600（低黏度品） 1200</td><td>100%</td></tr><tr><td>Desmodur NXP2410（非对称品） 700</td><td>100%</td></tr></table></body></html>  \n\n上述的3300和3600都是对称的三聚体，而XP2410则是新产品非对称体，黏度很低，化学名称是Iminooxadiazindione（亚胺氧杂二嗪二酮），其涂膜性质与对称体相似，但黏度低是其特点。  \n\n![](images/f13e8f7feac8ba3c55a807376115d91b14336ba64b82ceb0cb9da52622e8d261.jpg)  \n\n此不对称体的制备法是用苄基三甲基的氢氧化铵作催化剂，可参见拜耳公司Richter的美国专利US 5717091。还有用Phosphoniumpolyfluoside催化剂，此外，尚可将HDI制成脲基甲酸酯allophanate，黏度仅 $300\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$ ，若制成二聚体脲二酮Uretdione，黏度更低达$170\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$ ，后二者官能度低，只可作为活性稀释剂，掺入常规的三聚体中。商品Trimer，从上可见：商品虽简称三聚体，但其低黏度牌号所含三聚体也只有约 $70\\%$  \n\n简称三聚体，实际上是聚异氰尿酸酯的混合物：  \n黏度23℃，mPa·s干性  \n低聚体分布  \n\n\n<html><body><table><tr><td colspan=\"3\"></td><td>#=3</td><td>#=5</td><td>#>5</td></tr><tr><td>高黏度牌号</td><td>15000</td><td>快</td><td>约30%</td><td>约20%</td><td>约50%</td></tr><tr><td>标准品牌号</td><td>3500</td><td>中</td><td>约50%</td><td>约20%</td><td>约30%</td></tr><tr><td>低黏度牌号</td><td>1200</td><td>慢</td><td>约70%</td><td>约15%</td><td>约15%</td></tr></table></body></html>  \n\n因为异氰酸酯会与水反应产生 $\\mathrm{CO}_{2}$ ，所以制造水性聚氨酯涂料较为困难，必须采取特殊工艺。水性聚氨酯涂料可分为：  \n\n$\\textcircled{1}$ 单组分热塑性聚氨酯分散体PUD（polyurethane dispersion）；  \n$\\textcircled{2}$ 单组分自交联聚氨酯分散体；  \n$\\textcircled{3}$ 双组分水性聚氨酯涂料。  \n\n单组分热塑性PUD的制法：在制造热塑性PUD的方法中，以D.Diterich等在1970年开发的采用二羟甲基丙酸（DMPA）以合成聚氨酯离子体乳液（Ionomeremulsion）（80）的方法最普遍。DMPA的羧基受到两个羟甲基的位阻保护，基本上不会与NCO反应而保留在产物链中。  \n\n制造的步骤如下。  \n\na.选择分子量约1000～2000的二元醇，如：  \n\n聚醚（EO/PO) 价廉，硬度和强度低；或选聚四氢呋聚酯 价廉，硬度中，强度好聚碳酸酯 价高，硬度和强度高，抗化学品好。  \n\nb.选择异氰酸酯。  \n\nIPDI是采用最多的原料。  \n\nHMDI国外拜耳公司和EVONIK公司生产反式-反式4， $4^{\\prime}$ -HMDI，价较贵，生产的PUD有结晶性，故强度高性能好。  \n\nTMXDI是氰特Cytec公司产品，因其四甲基的特点，不必用NMP溶剂。  \n\nTDI是芳香族异氰酸酯，与水反应太快，且会泛黄，国外很少采用。而我国研究者很多采用，因为价廉。  \n\nc.二羟甲基丙酸必须先用NMP（N甲基吡咯烷酮）溶解或较多的丙酮溶解，然后投入到上述低聚物二元醇中，才可与IPDI等二异氰酸酯反应。因为DMPA的熔点高！ $:185\\sim$ $190^{\\circ}\\mathrm{C};$ ，必须溶解在NMP溶剂中，而NMP又有毒性。据报道二羟甲基丁酸（DMBA）可以代替DMPA。  \n\n它的熔点较低，易溶解于低聚物二元醇中，不需溶剂（或只需少量溶剂）。  \n\nd.将上述低聚物二元醇、DMPA、二异氰酸酯等反应。因异氰酸酯过量，生成端NCO的预聚体，其分子链中含有DMPA的羧基。  \n\ne.用三乙胺等叔胺，对上述的羧基中和成铵盐。  \n\nf.加水高速搅拌使相反转成水分散体。  \n\ng.水中含有乙二胺、肼等，与分散体中尚剩的NCO基反应扩链，提高性能。  \n\n我国研究此类PUD的报告很多，用环氧和三羟甲基丙烷等改性的PUD，性能优良，示例如下：  \n\n<html><body><table><tr><td>TDI</td><td>155g</td><td>丙酮</td><td>23g</td></tr><tr><td>聚醚二元醇（N210）</td><td>122g</td><td>三乙胺</td><td>17g</td></tr><tr><td>DMPA</td><td>25g</td><td>乙二胺</td><td>3g</td></tr><tr><td>1,4-丁二醇</td><td>10g</td><td>水</td><td>605g</td></tr><tr><td>NMP</td><td>26g</td><td>合计</td><td>1000g</td></tr><tr><td>环氧树脂E-20</td><td>15g</td><td></td><td></td></tr></table></body></html>  \n\n操作：先将聚醚二元醇在减压下脱除水分，将它和TDI置人 $\\scriptstyle2000{\\mathrm{mL}}$ 四口烧瓶，在$70\\sim80^{\\circ}C$ 反应 $1.5{\\sim}2\\mathrm{h}$ ，加人丁二醇在 $70\\sim80\\Upsilon$ 反应1.5h，加人DMPA的NMP溶液和环氧树脂溶液，在 $60\\sim65^{\\circ}\\mathrm{C}$ 反应达到NCO理论值，降温至 $40\\%$ 加入三乙胺中和，添加丙酮稀释，在常温水中乳化，用乙二胺扩链，减压脱去丙酮。此类配方中含有少量环氧或三羟甲基丙烷可提高抗水性及硬度。  \n\n上述的PUD在涂料应用中常配人丙烯酸乳液，可降低成本，并提高耐水性和机械强度，这种混合物常称为PUA，表示PU分散体之中含有不少聚丙烯酸酯（Acrylic)。虽可将PUD与丙烯酸乳液简单混合，但其微相结构不均匀，最好是采用原位聚合，产物称为Hy-brid杂交体。  \n\nTMXDI的PUD：TMXDI是氰特公司（Cytec）的产品，它有两个叔异氰酸酯，因其甲基的空间位阻，与水反应非常缓慢。文献介绍叔异氰酸酯在 $25\\mathrm{{^{q}C}}$ 时的相对反应速率（反应条件 ${\\mathrm{OH}}:{\\mathrm{NCO}}$ 为 $10:1)$ 如下：伯丙醇 $1,02\\mathrm{h}^{-1}$ ；仲丙醇 $0.173\\mathrm{h}^{-1}$ ；水 $0.042\\mathrm{h}^{-1}$ 。可见其与水反应缓慢。  \n\n![](images/a2f000393155962ccbde9a45244492fd4b6095a8486d1fcd2fbab605d3dcee1c.jpg)  \n\n通常制造PUD，其中用DMPA，必须先用NMP或许多丙酮溶解，使残留有毒的NMP，而TMXDI则不需溶剂，只要反应时升温至 $95\\mathrm{{^circ}C}$ 使DMPA熔化，此时DMPA的羧基不会与TMXDI的叔异氰酸酯反应，仍保留在链中，可与三乙胺等中和，制得不含溶剂的PUD。配方示例如下：  \n\n<html><body><table><tr><td colspan=\"3\">聚酯（新戊二醇/己二酸） TMXDI</td><td>38.9g 52.1g</td><td>TMP DMPA</td><td>0.5g 4.5g</td></tr><tr><td colspan=\"3\">新戊二醇</td><td>4.0g</td><td>扩链剂2-甲基戊二胺</td><td>10.4g</td></tr><tr><td rowspan=\"3\">涂膜性质</td><td>抗拉强度</td><td>41.8MPa</td><td></td><td></td><td></td></tr><tr><td>伸长率硬度</td><td>3%</td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n(2）单组分自交联聚氨酯分散体上述的热塑性PUD，虽经多年研究发展，在皮革涂料、塑料涂料等应用领域，已有良好成绩，而在木器、细木工等领域仍在不断改进中，与传统的溶剂型聚氨酯涂料相比，在硬度、耐水性、耐醇、丰满度等方面，仍有差距，因为其涂膜没有交联，故耐热水、耐粘连性等方面尚须改进。为此开发了自交联的分散体，以保持单罐装的方便，而具有一定的交联度。  \n\n此单组分自交联的水性PUD报道很多，举两个例子说明。其一是将豆油、三羟甲基丙烷、  \n\nLiOH、季戊四醇在240℃醇解，至甲醇容忍度>1：3透明，降温出料。在反应瓶中投入醇解物、共溶剂、端羟基环氧乙烷化合物及小分子二元醇，混匀后分批加入TDI，在70～80℃保温2h，加入由共溶剂溶解的DMPA反应2h，加入少量小分子醇醚以封闭残余NCO，用三乙胺中和，经过水分散得半透明的PUD。醇解时油与多元醇重量比为85：15，油度为50%，引人DMPA的酸值约20mgKOH/g，NCO/OH为0.88。此PUD配入水性的金属催干剂，涂膜性能良好，室温干7天后，硬度达2H，与溶剂型氨酯油相等。  \n\n另一种单组分自交联PUD是在其分子链中，含有一些可辐射固化的丙烯酸基团，在紫外光照射和光引发剂的作用下，能快速固化成膜。以往常规的光固化涂料黏度高，必须加人活性稀释剂（常对人体有刺激过敏)，涂膜刚脆，水性光固化PUD则不受高黏度之限，不需活性稀释剂，涂膜可调节柔韧性及厚度。国外拜耳公司的C.Irle和A.Wade介绍此类光固化水性PUD如BayhydrolUV2282。Cytec公司也有类似产品。我国也研究。  \n\n(3）双组分水性聚氨酯涂料双组分水性聚氨酯涂料的性能优良，比单组分的PUD好。但因其异氰酸酯组分会与水反应，所以有特殊的制造方法，不同于通常的溶剂型2K涂料，要制成水分散体。  \n\na.羟基组分大都是聚丙烯酸酯（因主链不会水解，贮藏稳定)。但它必须是由溶剂型树脂经过相反转工艺乳化而制成（称二级乳化)。  \n\nb.异氰酸酯组分需要改性成亲水性，以便在应用施工前，可用手工搅拌，与羟基组分拌匀。  \n\nc.异氰酸组分若未改成亲水性，则施工单位必须有强制的高压射流分散器才能将2K组分充分搅匀，否则不能施工。  \n\nd.溶剂型2KPU涂料，混合后的时限是视其黏度上升。水性PU涂料的介质是水，其施工时限并非按黏度反映。而是涂膜光泽降低等其他参数。  \n\na.羟基组分双组分水性聚氨酯涂料的羟基组分，不是普通的聚丙烯酸酯乳液，因为配漆后其外观欠佳，而且不易混合。工业上是先将含羟基单体、羧基单体等在溶剂中聚合（所以分子量较低)，完成后降温，减压蒸除溶剂，加入中和剂分散在水中。此种工艺称为二级乳化，产物称分散体。它能有助于将僧水的多异氰酸酯分散于水中，涂膜的外观良好。例如拜耳公司的BayhydrolAl45，固体分为 $45\\%$ ，OH含量 $3.3\\%$ ，酸值22，pH8.0，中和剂二甲基乙醇胺含助溶剂乙二醇丁醚 $4\\%$ ，芳烃 $4\\%$ 。除聚丙烯酸外，拜耳公司的BayhydrolVPLS2290是聚酯/丙烯酸，OH基含量 $3.8\\%$ ，酸值29，中和剂同上， $\\mathrm{pH}7.0$ ，接近中性，以防酯键的水解。  \n\nb.疏水多异氰酸酯通常的异氰酸酯都是疏水的，为了尝试将其分散在水相中，人们尽力降低其黏度，可见前节所述的DesmodurN3600、NXP2410、脲二酮等。近来又报导有低分子量的三异氰酸酯壬烷，习称TIN（Triisocyanatononane）。  \n\n$$\n\\begin{array}{c}{{\\mathrm{CH_{2}N C O}}}\\\\ {{\\downarrow}}\\\\ {{\\mathrm{OCNCH_{2}C H_{2}C H_{2}C H C H_{2}C H_{2}C H_{2}C H_{2}C H_{2}N C O}}}\\end{array}\n$$  \n\n它是高沸点无嗅液体，含NCO约 $48\\%\\sim51\\%$ 。各种疏水多异氰酸酯难以用手揽动分散于水中，必须有射流分散器，在 $100\\times10^{5}\\mathrm{Pa}$ 的高压力剪切下，将羟基分散体和疏水多氰酸酯共同分散至约 $500\\mathrm{nm}$ 的细度，才能充发反应交联成膜。  \n\nc.亲水多异氰酸酯这是将HDI三聚体与中等长度的聚环氧乙烷单醚亲水基连接，拜耳公司牌号为Bayhydur3100。  \n\n![](images/8773a290940ae9ff65012fa6534b3721328dab42ad1bd0a6cff6f3e2fd892a0d.jpg)  \n\n它的制法是，采用1000g的HDI三聚体（其NCO含量为21.6%，平均官能度3.3）加人80.8g，聚乙二醇单丁醚（分子量1145），在50℃反应，至110℃加热2h，冷却，所得产品含 $8018.4\\%$ ，黏度 $2500\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$ ，可在水中分散。  \n\n另一种产品叫Bayhydur 304，是将上述亲水性HDI三聚体的氨酯基的活泼氢原子与另一个 $\\mathrm{\\DeltaHDI}$ 三聚体结合成脲基甲酸酯。  \n\n![](images/1ecba6c21b7434929f26e53d27dbdd27ed5bba93d26659ec8a7b8141c730de14.jpg)  \n\n以上两种是聚醚改性、亲水的多异氰酸酯。含亲水基太多会影响涂膜抗水性。新开发的是离子型亲水多异氰酸酯：  \n\n![](images/ca5ee3103be10976bde7c49c26cbdfaca625c4da739609ca5091b468afaa290d.jpg)  \n\n这种磺酸盐比上述聚醚改性异氰酸酯有以下优点：前两种含亲水的醚氧分子较多，而磺酸盐分子量较低；  \n\nNCO含量更高；  \n提高涂膜硬度和干性；  \n改善耐化学品性。  \n\n拜耳公司共有两种磺酸盐商品：BayhydurXP2487/1；Bayhydur XP2570，更亲水，易手工搅匀。  \n\n拜耳公司的IPDI三聚体也有非离子型亲水异氰酸酯，牌号为BayhydurVPLS2150/1。  \n\n兹将前述亲水性多异氰酸酯列于表2-1-188，XP表示experimental实验产品，VP表示德文Versuch Product实验产品。LS是表示涂料和特种产品。  \n\n表2-1-188亲水性多异氰酸酯  \n\n\n<html><body><table><tr><td>项 目</td><td>Bayhydur 3100</td><td>Bayhydur 304</td><td>Bayhydur XP 2487/1</td><td>Bayhydur XP 2570</td><td>BayhydurVPLS2150/1</td></tr><tr><td>类别</td><td>HDI三聚体 亲水非离子</td><td>聚体 亲水非离子</td><td>HDI三聚体 亲水磺酸盐</td><td>HDI三聚体 亲水磺酸盐</td><td>IPDI三聚体 亲水非离子</td></tr><tr><td>固体分/%</td><td>100</td><td>100</td><td>100</td><td>100</td><td>70</td></tr><tr><td>黏度/mPa·s</td><td>2800</td><td>4000</td><td>6000</td><td>3500</td><td>600</td></tr><tr><td>NCO含量/%</td><td>17.4</td><td>18.2</td><td>20.5</td><td>20.5</td><td>13.4</td></tr><tr><td>官能度</td><td>3.2</td><td>3.8</td><td>3.4</td><td>30</td><td>3.0</td></tr></table></body></html>  \n\n法国Rhodia公司生产亲水性的脂肪族多异氰酸酯，最初牌号为RhodocoatWT2102，其后开发了HDI系的RhodocoatXEZM502，其后又开发了RhodocoatXEZD401和 $\\textbf{\\textrm{X E Z}}$ D803。EZ表示容易手工混合（EasyMix)，M502是HDI系，D401和D803是HDI和IPDI杂化系，因为IPDI的 $T_{*}$ 高，所以D系的涂料物理干燥快，涂饰后的家具等物件，可以较快干燥堆放。  \n\n双组分水性涂料示例（表2-1-189），选3种拜耳Bayhydrol示例。  \n\n表2-1-1893种双组分水性涂料示例  \n\n\n<html><body><table><tr><td>A145</td><td>聚丙烯酸酯分散体</td><td>固体分约45%</td><td>OH基含量约8.0%</td><td>高光，硬</td></tr><tr><td>VPLS 2058</td><td>聚酯/丙烯酸酯分散体</td><td>约42%</td><td>约2.0%</td><td>中</td></tr><tr><td>PT241</td><td>聚酯分散体</td><td>约41%</td><td>约2.5%</td><td>柔韧</td></tr></table></body></html>  \n\n它们用Bayhydur304固化，按NCO/OH为 $1.5/1.0$ ，施工时限为2h，涂膜性能见表2-1-190。  \n\n表2-1-1903种双组分水性涂料涂膜性能  \n\n\n<html><body><table><tr><td>项目</td><td>摆杆硬度/s</td><td>光泽20°</td><td>耐沥青沾污（24h)△E</td></tr><tr><td>A145</td><td>168</td><td>86.1</td><td>1.4</td></tr><tr><td>VPLS 2058</td><td>88</td><td>85.6</td><td>10.9</td></tr><tr><td>PT 241</td><td>18</td><td>90.2</td><td>41.4</td></tr></table></body></html>  \n\n配制水性涂料，需加人BYK，AirProduct公司等助剂，Rhodocoat推荐的经验是NCO/OH比例不必1.5/1.0，一般为 $(1,2{\\sim}1,4)/1.0$ 即可，太高会缩短施工时限。双组分之间必须混溶良好。用助溶剂稀释，会影响分散体的粒径，如用乙二醇丁醚醋酸酯稀释，粒径为 $100\\mathrm{nm}$ ，用一缩丙二醇二甲醚粒径为 $250\\mathrm{nm}$ ，用丙二醇甲醚醋酸酯粒径为 $280\\mathrm{nm}$ ，粒径越细涂膜的外观，光泽越好。  \n\n举例拜耳的BayhydrolVPLS2235是聚丙烯酸分散体，固体分 $45\\%$ ，固体含OH基$3.3\\%$ ，用二甲基乙醇胺中和，含助溶剂 $8\\%$ ，用它可配制水性涂料用于工具车，农机车。  \n\n投料 Bayhydrol VPLS 2235 (45%) 34.56g 助剂 Surfynol 104E 0.79g TiO 29.30g 去离子水 4.67g  \n\n珠磨 $15\\mathrm{min}$ ，调稀加入：  \n\nBayhydrol VPLS 2235 (45%) 13.88g增剂（10%水溶液） 1.55g有机硅助剂（1) 0.16g有机硅助剂（2) 0. 31g固化剂 Bayhydur304 14.80gNCO/OH=1. 5 100.00g施工时，加去离子水至30s黏度，喷涂。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 396,
+        "chunk": "# 四、安全、计算",
+        "category": " Introduction"
+    },
+    {
+        "id": 397,
+        "chunk": "# 1.异氰酸酯的劳动保护  \n\n异氰酸酯有毒，能与人体的蛋白质反应，必须注意劳动保护。异氰酸酯的口服毒性（动物试验）结果如下：  \n\n口服致死中量LDso g/kg(大鼠） XDI 0.84   \nTDI(80/20) 1. 95\\~5. 8 苯异氰酸酯 0.94  \n\n<html><body><table><tr><td>HDI</td><td>0. 35 ~1. 05</td><td>IPDI</td><td>1. 0</td></tr><tr><td>IPDI</td><td>2.25</td><td>HDI</td><td>1.25</td></tr><tr><td>TDI(2,4体)</td><td>4.9~6.7</td><td>苯异氰酸酶</td><td>3.5~4.4</td></tr><tr><td>HDI缩二脉（75%溶液）</td><td>19.8</td><td>MDI</td><td>10</td></tr><tr><td>MDI</td><td>31.6</td><td>HDI缩二脲（75%溶液）</td><td>15.8</td></tr><tr><td>经皮肤吸人致死中量LDso</td><td>g/kg（兔）</td><td>TDI(2,4体）</td><td>16</td></tr><tr><td>对眼损伤 (兔)： 严重：苯异氰酸酯、HDI、TDI 轻徽：MDI、IPDI</td><td></td><td>中等：HDI缩二脲（75%溶液）</td><td></td></tr></table></body></html>  \n\n异氰酸酯对人体的最大危害是它的蒸气。二异氰酸酯的蒸气刺激眼黏膜，具有强烈的催泪作用。吸入后刺激呼吸系统，引起干咳、喉痛。长期吸入二异氰酸酯将损伤肺部，引起头痛、支气管炎和哮喘。对个别人员（例如患哮喘的过敏体质者）可能引起呼吸困难，应特别注意。在常用的几种二异氰酸酯中，MDI的分子量较大，蒸气压低，对眼及呼吸系统的刺激就较小。表2-1-191列出几种二异氰酸酯的蒸气压(数据来自不同文献，略有参差)。  \n\n表2-1-191几种二异氰酸酯的蒸气压 单位：Pa  \n\n\n<html><body><table><tr><td>温度/C</td><td>TDI</td><td>MDI</td><td>HDI</td><td>IPDI</td><td>XDI</td><td>TMDI</td><td>HMDI</td></tr><tr><td>20 25 30</td><td>5.6 3.3</td><td>0.012</td><td>4.5 1.4</td><td>0.04</td><td>0.8</td><td>0.09</td><td>约0.1</td></tr><tr><td>92~96 129 130</td><td>10.7 2000</td><td></td><td>8.7 133 约1500</td><td></td><td>1.6</td><td></td><td></td></tr></table></body></html>  \n\n表2-1-192介绍几种二异氰酸酯在 $25\\mathrm{^c}$ （在空气中）的饱和浓度。  \n\n表2-1-192不同的异氰酸酶在25℃时的饱和浓度  \n\n\n<html><body><table><tr><td>品种</td><td>ppm</td><td>mg/ma</td><td>品种</td><td>ppm</td><td>mg/m</td></tr><tr><td>TDI</td><td>30</td><td>235</td><td>HMDI</td><td>0.9</td><td>10.6</td></tr><tr><td>HDI</td><td>13</td><td>96</td><td>MDI</td><td><0.01</td><td><0.1</td></tr><tr><td>IPDI</td><td>0.4</td><td>3.6</td><td></td><td></td><td></td></tr></table></body></html>  \n\n为了避免异氰酸酯蒸气对人体的危害，各国均规定了空气中二异氰酸酯的最高容许浓度。先前曾规定为 $0.01\\mathrm{mg}/\\mathrm{m}^{3}$ (0.1ppm）以下，1961年后改定为 $0.02\\mathrm{mg/m^{3}}$ $(0,02\\mathrm{ppm})$ 以下，最近又改为 $0.1\\mathrm{mg}/\\mathrm{m}^{3}$ (0.lppm）以下（按每日工作8h计)，美国的政府工业卫生师会议（ACGIH）公布的经时加权平均TWA的临界限值TLV为 $0.005\\mathrm{mg/m^{3}}$ (0.05ppm)。美国的职业安全卫生署OSHA补充规定：短时曝露限值空气中浓度0.02mg/m（0.02ppm）。MAC或TLV意义相同，取决于各不同国家所采用名称，指按工人每天工作7～8h，每周工作40h的工作场所大气中所容许最高的浓度。通常或用体积比表示或以每立方米空气中所含异氰酸酯质量表示之（mg/m，μg/m），例如德国有：  \n\n<html><body><table><tr><td>TLV</td><td>ppm</td><td>mg/ma</td><td>TLV</td><td>ppm</td><td>mg/ma</td></tr><tr><td>TDI</td><td>0.01</td><td>0.07</td><td>IPDI</td><td>0.01</td><td>0.09</td></tr><tr><td>MDI</td><td>0.01</td><td>0.10</td><td>HMDI</td><td>0.01</td><td>0.11</td></tr><tr><td>HDI</td><td>0.01</td><td>0.07</td><td></td><td></td><td></td></tr></table></body></html>  \n\n美国的NIOSH则更严格推荐工作场所的TWA（按每周40h工作）的浓度极限值为5μg/m（5ppb)，即每立方米大气中含TDI极限为35μg，MDI为50μg，HDI为35μg，IPDI为 $45\\mu_{B}$ ，HMDI为 $55\\mu g$ 通  \n\n因此，贮罐、输送管道、反应釜都必须密闭良好以免漏泄，工作场所必须充分通风。若在密闭工作场所（例如油罐、油舱的内部涂漆）通风困难，必须戴有送风的面具。空气中的TDI浓度达 $0.1{\\sim}1\\mathrm{mg}/\\mathrm{m}^{3}$ 时就能被闻到，因此当闻到TDI气味时即表示浓度已超过了容许极限，不宜在此场所持续工作，并采取通风、戴面具等保护措施。刷涂或滚涂施工，挥发的蒸气较少。喷涂施工则不仅挥发的异氰酸酯蒸气多，且雾化漆滴呈气溶胶状态浮在周围空气中，漆滴均小于 $7\\mu\\mathrm{m}$ ，能透人肺中，更应引起注意。优质的多异氰酸酯（即聚氨酯漆的固化剂)，在工厂制造过程中经减压薄膜蒸发，保持其中游离二异氰酸酯含量大多在 $0.5\\%$ 以下，则在刷涂、滚涂过程中，随着排除溶剂的通风，可使空气中的异氰酸酯浓度在容许限度以下，喷涂则须注意气溶胶。  \n\n在欧洲共同体内，规定含TDI、HDI、IPDI、HMDI产品的容器外壁必须标明以下内容。  \n\n$\\Phi$ 游离单体（二异氰酸酯）含量在 $0.5\\%$ 以下者，外壁标明“含异氰酸酯”。  \n\n$\\textcircled{2}$ 游离单体含量在 $0.5\\%\\sim2.0\\%$ 者，标明“有害”的警告标志及“含异氰酸酯”。  \n\n$\\textcircled{3}$ 游离单体含量在 $2\\%$ 以上者，标明“有毒”，并附有骷髅及白骨交叉标志，也标明“含异氰酸酯”。  \n\n操作异氰酸酯液体时要戴防护镜，如溅到眼睛或皮肤，有刺激作用，必须立即洗除。眼晴用水充分冲洗，若情况严重则立即送医院。皮肤用乙醇和肥皂液洗涤。若异氰酸酯液体溅泼于地，可用三乙醇胺液或氨水等处理，能在数分钟内使之破坏。洗涤液配方如下：  \n\n水  \n\n8g  \n\n洗涤剂  \n\n含异氰酸酯的涂料经充分固化（如经高温烘烤，或在常温经长时间充分干燥）成为聚氨酯或聚脲涂膜后，对人体并无毒害。但在涂膜初干几天之内，膜中仍含有未反应而残留的异氰酸酯基，可用偶合试剂检测出来。因此对于初干涂膜经打磨散出的尘末，不可吸入人体，要戴口罩、排风，或采用其他保护措施。  \n\n检验空气中异氰酸酯含量，一般的方法是将抽样中所含异氰酸酯转化为胺，再经重氮化、偶合，产生色素，予以光电比色。  \n\n国外有仪器可连续测定空气中异氰酸酯含量。例如德国的GMDAutostep920，PCM个人连续监察仪（DEHAHaan&Wittmer公司，D-7259，Friolzheim），英国MDA Scientific公司的7100 型检测仪（在 Ferndown Industrial Estate，Wimborne，Dorset BH 21 7RZ，UK)。  \n\n据介绍，快速的试纸法是将硝酸钠、醋酸铵、偶合试剂5-羟基 $3^{\\prime}$ $4^{\\prime}$ -苯并咔唑-4-羧基-对酰-N-茴香胺(5-hydroxy $3^{\\prime}$ $4^{\\prime}$ benzocarbazole-4-carboxy-p-anisilide）、邻苯二甲酸二乙酯、甲醇、水等配成溶液，将滤纸浸渍干燥，即成试纸。空气中含 $0.01{\\sim}0.1\\mathrm{mg/m}^{3}$ C $_{0,01\\sim}$ 0.1ppm）的TDI时试纸立即变色。  \n\n汽车修补喷漆工场空气中游离的脂肪族二异氰酸酯，可用分光比色法（ $353\\mathrm{nm}$ 处的吸光度）测出空气中 $2\\mu_{B}/\\mathrm{m}^{3}$ (2ppb)的浓度。 O  \n\n含异氰酸酯的罐听中若混人少量水，会产生 $\\mathrm{CO}_{2}$ 而使听内产生压力而鼓胀，此时必须覆以油帆布，将鼓气的听刺小孔使泄气（戴面罩及防护手套服装)，泄毕后用黑胶带将小孔密封。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 398,
+        "chunk": "# 2.聚氨酯漆的计算方法  \n\n（1）简单化合物当量数的计算简单化合物当量数的计算见表2-1-193。  \n\n表2-1-193简单化合物与当量数计算  \n\n\n<html><body><table><tr><td>品名</td><td>分子量</td><td>官能度</td><td>当量</td><td>品名</td><td>分子量</td><td>官能度</td><td>当量</td></tr><tr><td>二异氰酸酯</td><td></td><td></td><td></td><td>含羟基化合物</td><td></td><td></td><td></td></tr><tr><td>TDI</td><td>174.15</td><td>2</td><td>87.08</td><td>乙二醇</td><td>62.07</td><td>2</td><td>31.04</td></tr><tr><td>MDI</td><td>250.1</td><td>2</td><td>125.05</td><td>季戊四醇(纯)</td><td>136.15</td><td>4</td><td>34.04</td></tr><tr><td>HDI</td><td>168.1</td><td>2</td><td>84.05</td><td>麻油</td><td>一</td><td>一</td><td>约345</td></tr><tr><td>XDI</td><td>188.19</td><td>2</td><td>94.1</td><td>苯酚(封闭剂)</td><td>94.11</td><td>1</td><td>94.11</td></tr><tr><td>HMDI</td><td>262.3</td><td>2</td><td>131. 15</td><td>甲酚（封闭剂）</td><td>108.13</td><td>1</td><td>108.13</td></tr><tr><td>IPDI</td><td>222.36</td><td>2</td><td>111.18</td><td>其他化合物</td><td></td><td></td><td></td></tr><tr><td>TMXDI</td><td>201.26</td><td>2</td><td>100.63</td><td>乙二胺</td><td>60.10</td><td>2</td><td>30.05</td></tr><tr><td>含羟基化合物</td><td></td><td></td><td></td><td>MOCA</td><td>267.16</td><td>2</td><td>133.58</td></tr><tr><td>三羟甲基丙烷</td><td>134.17</td><td>3</td><td>44.9</td><td>己内酰胺（封闭剂）</td><td>113.16</td><td>1</td><td>113.16</td></tr><tr><td>甘油</td><td>92.1</td><td>3</td><td>30.7</td><td>丁酮肪（封闭剂）</td><td>87.124</td><td>1</td><td>87.124</td></tr><tr><td>丁二醇</td><td>90.12</td><td>2</td><td>45.06</td><td>丙二酸二乙酯（封闭</td><td>160.17</td><td>1</td><td>160.17</td></tr><tr><td>一缩乙二醇</td><td>106.12</td><td></td><td>53.06剂）</td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n对于聚酯、丙烯酸树脂、聚醚、环氧树脂、多异氰酸酯加成物、预聚物、缩二脲、三聚体等加工产品，它们都不是单纯的化合物，不能简单地通过计算其分子量及官能度求出其当量，必须通过分析测定其活泼基团含量再计算其当量数。一般表示多异氰酸酯产品的NCO含量的方式有两种：  \n\nA—NCO含量的质量百分率；  \n\nB—胺当量数，是指含有leqNCO基（或相当于leq的二丁胺）的多异氰酸酯的质量数。  \n\n以上两种表示方式的数值之间的关系如下：  \n\n$$\nA=\\frac{4200}{B}(\\%)\\xrightarrow[]{=}B=\\frac{4200}{A}\n$$  \n\n式中A—NCO百分含量，%；  \n\nB—胺当量。  \n\n以上公式是通过下列计算得出：按每 $B_{\\mathrm{{g}}}$ 产品中含有leqNCO，即含有NCO基42. $\\scriptstyle02g$  \n\n$$\nN C O/\\%=\\frac{42.02}{B}\\times100\\%=\\frac{4202}{B}\\%\\approx\\frac{4200}{B}\\%\n$$  \n\n对于加成物或预聚物类型的产品，胺当量数的理论值可按下式计算（不挥发分计算）：  \n\n$$\nB=\\frac{18}{[n-n^{\\prime}]}\\frac{17}{18}A=\\frac{[n-n^{\\prime}]\\times4200}{184444}(\\%)\n$$  \n\n式中π—投人的NCO的总当量数；  \n\n$n^{\\prime}$ —投人的OH的总当量数。  \n\n例如，TDI/TMP加成物  \n\n![](images/5108f5ee2d80b74a3e29dac455408622ec06343aede6c0bc3be32eb792f31de7.jpg)  \n\n由3molTDI（6eq）和1mol三羟甲基丙烷（3eq）组成。  \n\n$$\nB{=}\\frac{\\sharp\\notin\\#\\#\\#\\#}{[6-3]}{=}\\frac{3\\times174,15{+}134.17}{3}{=}219\n$$  \n\n$$\nA{=}\\frac{[6{-}3]}{3{\\times}174.15{+}134.17}{=}19.19\\%\n$$  \n\n若加入溶剂稀释成 $75\\%$ 溶液，则：  \n\n$$\nA=19,19\\times75\\%=14.39\\%\n$$  \n\n实际工业产品的 $N C O\\%$ 比计算值略低。  \n\n典型的多异氰酸酯工业产品的NCO含量如下，可供计算参考：  \n\nHDI三聚体（无溶剂） 21.8 TDI加成物（75%溶液） 13%左右 HDI三聚体（90%溶液） 19.4%左右 TDI加成物（67%溶液） 11.6%左右 IPDI三聚体（70%溶液） 11.5%\\~12.0% TDI加成物（50%溶液） 8.7%左右 TDI三聚体（51%溶液） 8%左右 XDI加成物（75%溶液） 11.4%左右 TDI/HDI三聚体（60%溶液） 10.5%左右 HDI缩二脲（75%溶液） 16.5%左右 苯酚封闭TDI加成物（固体） 12%\\~13% HDI缩二脲（100%固体分） 22%\\~23% 己内酰封闭IPDI加成物（固体） 15%左右  \n\n羟基含量的表示方式有3种：  \n\nC一羟基含量的质量百分率；D-羟基当量，即指含1mol（当量）的羟基的试样的质量数；E一羟值，即表示酰化每克样品中所含羟基所需的羧酸，以其相当量的KOH毫克数表示之。按以上定义，则每羟基当量（D）中含有1mol羟基，即含有 $17_{8}$ 羟基，则其质量百分率该为：  \n\n$$\nC(\\%)=\\frac{17}{D}\\times100(\\%)\n$$  \n\n$$\nC{=}\\frac{1700}{D}\\Re\\bar{\\Re}D{=}\\frac{1700}{C}\n$$  \n\n按定义，羟值以每克样品相当量之KOH毫克数表示，羟值为 $^1$ 即表示1mgKOH(E值)。  \n\n但按 $D$ （羟基当量）应该相当于1mol羟基的试样的质量，即相当于 $1\\mathrm{mol}$ 的KOH，即56100mgKOH。  \n\n即羟基当量≈56100mgKOH  \n\n$$\n\\frac{D}{1}=\\frac{56100}{E},\\textcircled{\\sharp}D=\\frac{56100}{E}\n$$  \n\n从而得到：  \n\n$$\n{\\frac{1700}{C}}={\\frac{56100}{E}}\n$$  \n\n则： $C{=}\\frac{E}{33}$ 或 $\\scriptstyle{E=C\\times33}$ 9  \n\n例如：已知某聚酯的羟基含量为 $5\\%$ ，则其羟基当量为 $D{=}\\frac{1700}{C}{=}\\frac{1700}{5}{=}340$ 或其羟值为 $E=C\\times33=5\\times33=165$ (mgKOH/g)。  \n例如：聚醚N-210的羟值为100，  \n则其羟基含量C= $C=\\frac{E}{33}{=}\\frac{100}{33}{=}3\\%$   \n其羟基当量D=56100_56100 2=561。  \n\n我国造漆工业生产的聚酯大多用羟基含量（%）表示，而有些聚醚则习惯用羟值表示。它们之间可用上式相互换算。尚须特别指出，我国以往的环氧树脂羟值指标沿用Shell公司习惯，有其独特的表示方式，与其他大多数的油脂或树脂不同。它的羟值是指每100g树脂今数其的摩尔数，例如： 0. 36mol/100g  \n\n0.16mol/100g E-06环氧树脂羟值为 0.40mol/100g E-42环氧树脂羟值为 0. 32mol/100g E-03环氧树脂羟值为 E-20环氧树脂羟值为 0. 34mol/100g l加．F-20环氧树脂，每100g树脂含  \n\n因此在聚氨酯漆中必须统-换算，以免错误。例如：E-20氧树肌，基0.32eq，即含羟基0.32×17g。则羟基百分含量为：  \n\n$$\n\\frac{0.32\\times178}{100}\\times100\\%=5.44\\%\n$$  \n\n同理： 2.72% E-06环氧树脂含OH基E-42环氧树脂含OH基 5,78% E-03环氧树脂含OH基19环氨射脂含OH基  \n\n耶酯（固体分）的羟基含量的理论值可按下式计算：  \n\n2. 82mol  \n\n例如，1600号聚酯是由下列原料组成：3mol 一编乙二醇  \n己二酸 0.6mol  \n三羟甲基丙烷  \n可以计算出产品的羟基含量，见表2-1-194。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 399,
+        "chunk": "# 2-1-1941600号聚酯产品羟基含量  \n\n<html><body><table><tr><td></td><td>摩尔数</td><td></td><td>质量/g</td><td>基摩尔数</td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>3 162</td><td></td><td></td><td></td><td>###</td></tr><tr><td>三羟甲基丙烷</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>合计</td><td>6</td><td>18</td><td>108.0</td><td></td><td>1.44</td></tr><tr><td>出水</td><td></td><td></td><td>709.</td><td></td><td></td></tr></table></body></html>  \n\n①产品净重.  \n②过量羟基。  \n\n理论 OH(%)=1.44×17g×100%=3.5%  \n\n又例如，147号醇酸树脂是由323g苯酐、166g甘油、511g麻油所组成。产品的羟基",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 400,
+        "chunk": "# 含量计算如下：",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 401,
+        "chunk": "# 骏基摩尔数  \n\n![](images/28dd3e5906ab2f6005d1da7ef0cf642b7ed5c0ae66d0457018dfd6c65d07943d.jpg)  \n\n以上从聚酯的配方计算产品的羟基含量只提供一个参考数据，实际上产品的羟基含量往往低于计算值，因为在酯化制造过程中，多元醇的羟基之间会缩合成醚，或多元醇随水及溶剂蒸出。所以聚酯产品的羟基含量必须经过分析才能确定。  \n\n(2）双组分配漆比例的计算通常聚氨酯漆产品中活泼基团含量大多是采用质量百分数表示的。例如：  \n\n甲组分TDI加成物（50%溶液） （含NCO)8.7% 乙组分聚酯（50%溶液） （含OH)2.0%甲、乙两个组分之间配漆的质量配比可计算如下：  \n\n若取NCO/ $\\mathrm{OH}{=}1\\mathrm{mol}/1\\mathrm{mol}$ .  \n则甲/乙质量比应为 $={\\frac{1\\ R{\\ddot{\\mathbf{x}}}\\equiv{\\mathfrak{u}}\\{\\mathbf{\\mathbf{x}}}\\mathbf{\\mathbf{\\mathbf{\\ell}}}(\\mathbf{\\mathbf{g}})}{1\\ {\\ddot{\\mathbf{g}}}\\mathbf{\\mathbf{k}}\\mathbf{\\mathbf{\\ell}}{\\overset{\\mathrm{\\tiny~{..}}}{\\equiv}}\\mathbf{\\ddot{\\mathbf{\\upmu}}}{\\mathrm{\\hat{\\mathbf{u}}}}\\mathbf{\\mathbf{\\ell}}(\\mathbf{\\mathbf{g}})}}={\\frac{B}{D}}$ 但 $B{=}\\frac{4200}{A}$ $D{=}\\frac{1700}{C}$   \n代人上式 ${\\frac{\\frac{4200}{A}}{\\frac{1700}{C}}}={\\frac{4200}{1700}}\\times{\\frac{C}{A}}=2.47\\times{\\frac{C}{A}},$  \n\n因此，上例若取 $\\mathrm{{NCO/OH}=1:1}$ 时  \n\n$$\n\\frac{\\mathrm{\\Delta}\\Psi}{\\mathrm{\\Delta}Z}{=}2.47\\times\\frac{2.0}{8.7}{=}\\frac{0.57}{1.00}\n$$  \n\n即每 $1\\mathbf{kg}$ 乙组分需配 $0.57\\mathrm{kg}$ 甲组分。  \n\n若通过试验，得知该涂料在潮湿环境下施工，NCO/OH比例（习称Isocyanate index异氰酸酯指数） $f$ 以 $1.2:1.0$ 较佳，则：  \n\n$$\n{\\frac{\\#}{\\mathsf{Z}}}{=}f{\\times}2.47{\\times}{\\frac{C}{A}}{=}1.2{\\times}2.47{\\times}{\\frac{2.0}{8.7}}{=}{\\frac{0.68}{1.00}}\n$$  \n\n即每 $1\\mathbf{k}_{\\mathbf{B}}$ 乙组分需配 $0.68\\mathbf{kg}$ 甲组分。  \n\n同理，用上述TDI加成物溶液，与E-12环氧树脂配合，按NCO/ $\\mathrm{OH}=1.2$ ：1.0，则：  \n\n$$\n{\\frac{\\boxplus}{\\b{\\bigstar}}}=f\\times2.47\\times{\\frac{C}{A}}=1.2\\times2.47\\times{\\frac{5.78}{8.7}}={\\frac{1.96}{1.00}}\n$$  \n\n即每1kgE-12环氧树脂需配以 $1.96\\mathbf{kg}\\mathrm{TDI}$ 加成物溶液。以上仅是示例，实际上NCO/$_\\mathrm{OH}$ 比例会影响涂膜性质，有时NCO/OH比例显著超过 $1:1$ ，有时不足 $1:1$ ，必须通过实验而确定，以满足对涂膜性能的要求。举例如下： 19.  \n\n某IPDI系粉末涂料，对其NCO/OH比作梯度试验（laddertest)，测其原始的性能，及经3000小时人工老化后的性能（氙光老化，相对湿度 $80\\%\\sim85\\%$ ，每 $17\\mathrm{{min}}$ 干照后，水淋 $3\\mathrm{min})$ ，其杯突试验（Erichsen-Tiefung）结果如下：  \n\n<html><body><table><tr><td>NCO/OH</td><td>原始值/mm</td><td>3000h老化后/mm</td><td>NCO/0H</td><td>原始值/mm</td><td>3000h老化后/mm</td><td></td></tr><tr><td>0.8 ± 1.0</td><td>>10</td><td>3.1</td><td>1.1  1.0</td><td>>10</td><td>9.6</td><td></td></tr><tr><td>0.9 ± 1. 0</td><td>>10</td><td>5.5</td><td>1. 2 + 1. 0</td><td>>10</td><td>9.8</td><td></td></tr><tr><td>1.0 ± 1.0</td><td>>10</td><td>>10</td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n又例如某快干（喷用）木器清漆配方（NCO/OH为 $0.5:1.0)$ 如下：甲组分",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 402,
+        "chunk": "# 乙组分  \n\n1300号聚酯（75%溶液） 28.3g 甲基异丁基酮 10.2gVAGH氯醋共聚体（20%溶液） 10.0g 甲苯 6.0g硅油（1%溶液） 0.6g MPA溶剂 3.4g醋酸乙酯 27.2g  \n\n对于在潮湿环境下施工的涂料，NCO/OH常超过1；对于需耐溶剂、耐化学品侵蚀的涂料，NCO/OH也常超过1。  \n\n为了简化配漆计算，可采用图算法（Nomogram）见图2-1-50。  \n\n![](images/e6656a9cb12621203e6afeb168d14922fb9706eaf01349c9b82813763d9efcb4.jpg)  \n图2-1-50配漆图算图  \n\nC一羟基树脂的羟基含量，%；A一多异氰酸酶树脂NCO含量，%； X-按NCO/OH=1/1，每100g羟基树脂所需多异氰酸酯树脂，g  \n\n图算方法：选一支透明无色塑料尺，于其背面用刀刻划一直线，刻痕处涂红色墨水或漆，措除多余部分，使成一条红色细线，即可应用。计算时，将尺下面的红线对准 $c$ 线的羟基含量读数，移动此尺使红线再交A线于NCO含量数，则尺下红线所交 $x$ 线的数目即是每 $100\\mathbf{g}$ 羟基树脂所需甲组分（多异氰酸酯树脂）的克数。  \n\n例如，甲组分的NCO含量为 $11.6\\%$ ，乙组分的OH含量为 $3\\%$ ，则首先将红线对准 $c$ 线的3.0点，再对准A线的11.6点，红线交中央 $x$ 线之处为64，即表示每 $^{100}\\mathbf{g}$ 羟基树脂（乙组分）需 $64\\mathbf{g}$ 甲组分。  \n\n对于制备预聚物的配方中所需二异氰酸酯的量可按下例初步估计，但是主要尚需通过试  \n\n验来确定最适当的 $\\operatorname{NCO}/\\operatorname{OH}$ 的比例。  \n\n例如聚酯溶液的羟基含量为 $3.0\\%$ ，用TDI制预聚物，取 $\\mathrm{NCO/OH{=}2}$ ，则：  \n\n$$\nD{=}\\frac{1700}{C}{=}\\frac{1700}{3.0}{=}567\n$$  \n\n即每 $567_{\\mathbf{B}}$ 聚酯溶液相当于1molOH，按 $\\mathbf{NCO}/\\mathrm{OH}=2$ ，需2mol的NCO基，即需1mol的TDI,  \n\n即每 $1\\mathbf{k}_{\\mathbf{{g}}}$ 聚酯溶液需投料TDI $307_{8}$  \n\n上例配比的产物是按 $\\mathrm{NCO}/\\mathrm{OH}{=}2$ 计算，即每1molTDI与羟基加成时，一个 NCO基化合，另一个NCO基残留。因此，制成的预聚物的 NCO含量为：  \n\n$$\nA{=}\\frac{307\\times\\frac{42}{174}}{1000+307}{\\times}100\\%{=}5.66\\%\n$$  \n\n关于封闭型聚氨酯漆的计算，它虽然是单罐包装，但是实质上含两种组分，可按上述双组分漆的同样方法计算。关于聚氨酯漆中的组分（聚酯、加成物、预聚物、弹性涂料的树脂等）的平均分子量可按Carothers 公式大略估计。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 403,
+        "chunk": "# 3.分析方法  \n\n见本书第四篇第三章。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 404,
+        "chunk": "# 第九节聚脲树脂",
+        "category": " Introduction"
+    },
+    {
+        "id": 405,
+        "chunk": "# 一、概述  \n\n聚脲树脂是含有异氰酸基—NCO的单体或预聚物与含有氨基一 $\\mathrm{NH}_{2}$ 、—NRH 的单体或预聚物经加成缩合反应得到的聚合物树脂。  \n\n$$\n\\bf\\Theta(\\widehat{P}-N C O_{3}+H_{1}N-\\widehat{\\mathbb{Q}})\\_{\\widehat{\\bf\\Gamma}\\mathrm{~-~}\\widehat{\\bf\\Theta}\\mathrm{~NH-}\\widehat{\\bf\\Theta}\\mathrm{~C-NH-}\\widehat{\\mathbb{Q}}\\mathrm{~}}\n$$  \n\n$\\textcircled{P}$ 代表单体或预聚物。  \n\n通常-- $\\mathrm{NH}_{2}$ 与—NCO的反应速率比一OH与—NCO的反应速率要快得多。例如，目前以氨基聚醚与MDI制备的喷涂聚脲体系，采用特种喷枪混合喷涂后，材料在几秒至十几秒之内即可胶化，几分钟完成交联反应。通过降低胺或一NCO的反应活性，可以得到从几分钟至几十分钟之内固化的聚脲材料。而且可以用含一OH的多元醇或环氧改性聚脲材料，制备具有不同技术性能和施工性能的聚脲聚氨酯、环氧改性聚脲等成膜物体系适应不同的性能要求。  \n\n聚脲树脂是一类具有高性能的材料，其力学性能可由弹性至刚性体在广泛的范围内变化，其耐磨性、防滑性和强度等综合性能是现有聚合物材料中最佳选择之一，因此在涂料领域具有广阔的应用前景。其中喷涂聚脲弹性体是20世纪90年代后期最早开发并开始应用推广的品种之一。随着天冬氨酸酯等受阻胺，低活性脂肪族和芳香族异氰酸酯预聚物的开发，慢固化、高装饰性及各种功能化的产品不断面世。  \n\n喷涂聚脲弹性体（spray polyurea elastomer，SPUA）技术是国外近二十年来，继高固体分涂料、水性涂料、辐射固化涂料、粉末涂料等低（无）污染涂装技术之后，为适应环保需求而研制、开发的一种新型无溶剂、无污染的绿色施工技术，与传统环保型涂装技术相比，SPUA技术具有以下优点。  \n\n$\\Phi$ 不含催化剂，快速固化，可在任意曲面、斜面及垂直面上喷涂成型，不产生流挂现象，5s凝胶，1min即可达到步行强度。  \n\n$\\textcircled{2}$ 对水分、湿气不敏感，施工时不受环境温度、湿度的影响。  \n\n$\\textcircled{3}$ 100%固含量，不含任何挥发性有机物（VOC)，对环境友好。  \n\n$\\textcircled{4}$ 可按 $1:1$ 体积比进行喷涂或浇注，一次施工的厚度范围可以从数百微米到数厘米克服了以往多次施工的病。  \n\n$\\textcircled{5}$ 优异的理化性能，如拉伸强度、伸长率、柔韧性、耐磨性、耐老化性、防腐蚀性等$\\textcircled{6}$ 具有良好的热稳定性，可在 $120^{\\circ}\\mathrm{C}$ 下长期使用，可承受 $150\\mathrm{^{\\circ}C}$ 的短时热冲击。  \n\n$\\textcircled{7}$ 可以像普通涂料一样，加入各种颜、染料，制成不同颜色的制品。  \n\n$\\textcircled{8}$ 配方体系任意可调，手感从软橡皮（邵尔A30）到硬弹性体（邵尔D65)  \n\n$\\textcircled{9}$ 原形再现性好，涂层连续、致密，无接缝、无针孔，美观实用。  \n\n$\\textcircled{10}$ 使用成套设备，施工方便，效率极高；一次施工即可达到设计厚度要求，克服了以往多层施工的病。  \n\n由此可见，SPUA技术是一种新型“万能”（国外称为versatile）涂装技术，它集塑料、橡胶、涂料、玻璃钢多种功能于一身，全面突破了传统环保型涂装技术的局限。因此，该技术一问世，便得到了迅猛的发展。  \n\nSPUA技术将聚脲的优异性能和快速喷涂、现场固化的施工技术有机地结合在一起，使其在工程应用中显示出无可比拟的优越性。目前在通用的高固体分涂料、水性涂料、光固化涂料、粉末涂料等环保型涂料中，有的施工一道后，至少需要 $12\\sim24\\mathrm{h}$ 的干燥时间，才能投入使用或进行下一道施工；有的一次施工的最大厚度小于 $800\\mu\\mathrm{m}$ ，且不允许连续加厚，施工效率极低。SPUA技术则不同。由于其快速的固化反应，层间施工间隔只需几分钟，即一道施工结束，就可立即进行下一道施工，对涂层最终的施工厚度没有限制，而且能够在垂直面连续施工不产生流淌现象。如施工 $1000\\mathbf{m}^{2}$ 的平面涂层，仅需6h即可完成施工， $2\\sim3\\mathrm{h}$ 即可投入使用，深受广大用户的欢迎。  \n\n该技术还有一个显著特点就是 $100\\%$ 固含量，只要正确使用该技术，无论是施工期间，还是材料投入使用后，涂层均不产生有害物质和刺激性气味，对环境保护极为有益，属新型环境友好型材料。  \n\n鉴于SPUA技术具有卓越的物理性能和施工性能，它可以完全或部分替代传统的聚氨酯、聚氨酯/聚脲、环氧树脂、玻璃钢、氯化橡胶、氯磺化聚乙烯以及聚烯烃类化合物，在化工防腐、管道、建筑、舰船、水利、交通、机械、矿山耐磨等行业具有广阔的应用前景。",
+        "category": " Introduction"
+    },
+    {
+        "id": 406,
+        "chunk": "# 二、聚脲树脂所用原料  \n\n喷涂聚脲弹性体用的原料主要有三大类，即端氨基聚醚、异氰酸酯和扩链剂。除此之外，有时为了改善黏度、阻燃、耐老化、抗静电、外观色彩、附着力等性能，还需加人稀释剂、阻燃剂、抗氧剂、抗静电剂、颜料、硅烷偶联剂等助剂。在SPUA技术中，将异氰酸酯与聚醚多元醇生成的半预聚体（quasi-prepolymer）组分定义为A料；将含有端氨基聚醚、液体胺类扩链剂和其他助剂的组分定义为B料或者R料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 407,
+        "chunk": "# 1.异氰酸酯  \n\n异氰酸酯是聚脲弹性体A料的主要原料之一，合成A料用的异氰酸酯包括二异氰酸酯、  \n\n三异氰酸酯以及它们的改良体。  \n\n在SPUA技术中，由于甲苯二异氰酸酯（TDI）的蒸气压低、气味大、毒性强，几乎无人使用，所以A料的合成中，通常选用MDI或MDI的改性物与聚合物二元或三元醇反应制得。  \n\n（1）芳香族异氰酸酯  \n\n$\\Phi$ 二苯基甲烷二异氰酸酯（MDI）二苯基甲烷-4，4'-二异氰酸酯简称MDI，纯MDI商品为白色或浅黄色固体。其主要化学结构为 $4,4^{\\prime}{\\cdot}\\ensuremath{\\mathrm{MDI}}$ ，此外它还有另外两种异构体： $^{2,4^{\\prime}\\mathrm{.}}$ MDI和 $_{2,2^{\\prime}}$ -MDI。  \n\n![](images/d8164ba2dcf3b71112ce0923399d3fcb10e188290726da997aa161830d532698.jpg)  \nMDI主要物理性能指标列于表2-1-195。  \n\n表2-1-195MDI主要物理性能指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>外观 分子量</td><td>白色或浅黄色固体结品 250.26 2</td><td>凝固点/C 纯度/% —NCO含量/%</td><td>>38 >99. 5 约33.4</td></tr></table></body></html>  \n\nMDI合成方法是由苯胺与甲醛缩合成二苯基甲烷二胺（MDA)，再光气化而得：  \n\n![](images/d411f2d44bff0e23aa7c4753991092308dc1b36cd2800e80ca51accefe28b26b.jpg)  \n\n根据原料配比、工艺合成路线的不同，蒸馏出来的MDI中3种异构体的含量也有差异，作为工业商品，通常蒸馏生产出的MDI产品中3种异构体的比例控制在如下比例：4，4'-MDI $60\\%\\sim99.5\\%$ $^{2,4^{\\prime}}$ -MDI0. $5\\%\\sim40\\%$ ；2,2'-MDI $0.0\\%\\sim2.0\\%$ 。烟台万华聚氨酯股份公司相应产品牌号为MDI-100和MDI-50。  \n\n在聚氨酯工业中所用的MDI主要是指 $4,4^{\\prime}–\\mathbf{MDI}$ ，在SPUA技术中所用的 $2,4^{\\prime}–\\mathbf{MDI}$ 与${4,4^{\\prime}–M D I}$ 相比，具有常温下呈液体状态，便于生产和运输；结构不对称，反应活性平缓；生成的SPUA材料强度高、伸长率大、对底材附着力强等优点，是SPUA技术中非常重要的原材料。  \n\nMDI在室温下长期贮存会产生自聚等反应，易生成不溶解的二聚体，使产品颜色黄变，溶解后液体将变得浑浊，出现不溶性细微颗粒，影响产品品质，并会对制品性能产生不利影响。故MDI不宜直接贮存于室温下，应在 $15\\%$ 以下，最好是在 $5\\mathrm{{^{\\circ}C}}$ 以下贮运，并尽早使用。此外，添加稳定剂可改善MDI的贮存稳定性。甲苯磺酰异氰酸酯、亚磷酸三甲苯酯与4,4'-二硫（6-叔丁基 $^{\\cdot3,3^{\\prime}}$ -甲酚）混合物等可作为MDI贮存稳定剂。  \n\n$\\textcircled{2}$ 多苯基甲烷多异氰酸酯（PAPI）多苯基甲烷多异氰酸酯实际上是MDI和聚合MDI等的混合物。国外习惯按最早UCC公司命名的商品名称，简称其为PAPI，也有人称其为聚合MDI或粗品MDI。其结构式如下：  \n\n![](images/50e1161fec2dc4ac558d3ffb8568f23dbccde5ec93ab62de6dad61fc24e6e385.jpg)  \n\n式中， $\\scriptstyle n=0$ ，1，2，3…  \n\nPAPI是一种含有不同官能度的多异氰酸酯混合物，其中 $\\scriptstyle n=0$ 的二异氰酸酯（MDI)占混合物总量的 $50\\%$ 左右，其余则是三官能度平均分子量为 $350{\\sim}420$ 的低聚合度异氰酸酯褐色透明液体。  \n\nPAPI的生产方法与MDI相同，都是由苯胺与甲醛缩合生成二苯基甲烷二胺（MDIA)，  \n然后进行光气化制得。这些二胺的生成数量取决于工艺条件与原料配比。工业上一般采用  \nMDI和PAPI联产的方式生产，不将缩合产物分离，而直接进行光气化反应合成出粗品  \nMDI，再经过脱气、高真空蒸馏、提纯、分离等后处理工作，从光气化液中分离出纯MDI  \n和不同官能度的PAPI。在实际生产中，根据产品使用目的、性能要求不同，控制反应工艺  \n条件，可生产出不同的PAPI产品。如含纯MDI约 $35\\%$ 的高聚合度产品，官能度为 $3\\sim$   \n3.2；含纯MDI约 $40\\%$ 的中等聚合度产品，官能度约2.7；含纯MDI约 $65\\%$ 的低聚合度产  \n品，官能度约2.3。烟台万华聚氨酯股份公司的PM-200、PM-300、PM-400即属该类产品。PAPI主要物理性能指标列于表2-1-196中。  \n\n表2-1-196PAPI主要物理性能指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指 标</td></tr><tr><td>外观</td><td>棕色透明液体</td><td>凝固点/℃</td><td><10</td></tr><tr><td>分子量</td><td>131.5~140（胺当量）</td><td>纯度/%</td><td>一</td></tr><tr><td>官能度</td><td>2.7~2.8</td><td>-NCO含量/%</td><td>30.0~32. 0</td></tr><tr><td>沸点/C</td><td>约260，自聚放出CO</td><td>水解氯含量/%</td><td><0.13</td></tr><tr><td>相对密度（d）</td><td>1. 23~1. 25(20℃)</td><td>酸度（以HCI计）/%</td><td>0.11</td></tr><tr><td>黏度/mPa•s</td><td>150~250(25C)</td><td>蒸气压/×10-Pa</td><td></td></tr><tr><td>闪点/C</td><td>>200</td><td></td><td>3.20</td></tr><tr><td>色度（APHA)</td><td>一</td><td>10°C 25℃</td><td>2.13</td></tr></table></body></html>  \n\n$\\textcircled{3}$ 液化型二苯基甲烷二异氰酸酯（LMDI）液化型二苯基甲烷二异氰酸酯简称液化MDI，是一种改性MDI。由于纯MDI的凝固点为 $39.5\\Upsilon$ ，常温下为固体，在使用前必须进行加热熔融，不仅操作复杂，还给使用者带来诸多不便，同时还存在室温下贮存稳定性差等缺点。液化改性后的MDI产品，可有效地避免在贮存、运输时的苛刻条件，同时对制品性能的提高和改善提供了在MDI原料上进行大范围改性的基础。MDI改性的方法较多，按制法划分有如下三种类型。 Y  \n\na.掺混MDI苯胺与甲醛缩合时，借助固体酸性硅、改性硅黏土、硅铝等催化剂，提高产物中 $^{2,4^{\\prime}}$ -MDI异构体的比例到 $94\\%$ ，然后经光气化得到液化MDI。通常，在MDI中，当 $_{2,4^{\\prime}-M D I}$ 异构体的含量达到 $25\\%$ 以上时在常温下就成为液体。  \n\nb.氨基甲酸酯改性MDI（U-MDI）该改性方法一般采用低分子量多元醇化合物、聚醚多元醇（如PPG-600）或聚酯多元醇与过量的 $4,4^{\\prime}–\\mathbf{MDI}$ 反应，生成带有端基为一NCO基团的氨基甲酸酯改性MDI。它实际上是一种半预聚物，常温下为液态，一般—NCO基团含量在 $20\\%$ 以上，常温下黏度在 $1000\\mathrm{{mPa}}$ ·s以下。  \n\nc.碳化二亚胺改性MDI（C-MDI）MDI在磷化物存在下，加热至 $200\\mathrm{\\textperthousand}$ ，部分缩合脱去 $\\mathrm{co}_{2}$ ，生成含有碳化二亚胺结构的MDI改性产物，同时在反应中易生成少量脲酮亚胺，使C-MDI的官能度略大于2。典型的C-MDI商品为浅黄色透明液体，—NCO 基含量为$28\\%\\sim30\\%$ ， $25\\mathrm{{^{\\circ}C}}$ 下的黏度在 $100\\mathrm{{mPa}}$ $\\cdot$ s以下。用C-MDI制得的喷涂聚脲弹性体，其耐热性、耐水性、阻燃性均得到改善。表2-1-197列出了四家公司的C-MDI产品规格供参考。  \n\n表2-1-197碳化二亚胺改性MDI产品规格  \n\n\n<html><body><table><tr><td>商品牌号</td><td>Isonate-143L</td><td>Millionate-MTL-S</td><td>Suprasec 2020</td><td>MDI-100LL</td></tr><tr><td>生产厂家</td><td>日本化成厄普姜</td><td>日本聚氨酯公司</td><td>美国亨斯迈</td><td>烟台万华</td></tr><tr><td>外观</td><td>淡黄色液体</td><td>淡黄色液体</td><td>淡黄色液体</td><td>淡黄色液体</td></tr><tr><td>相对密度（25C）</td><td>1.22</td><td>1. 22</td><td>1. 22</td><td>1.21~1.23</td></tr><tr><td>黏度（25C）/mPa• s</td><td>25~30</td><td>30~70</td><td>35</td><td>25~60</td></tr><tr><td>—NCO含量/%</td><td>28.1~29.6</td><td>28.5~29.5</td><td>29.3</td><td>28~30</td></tr><tr><td>酸度（以HCI计）/%</td><td>≤0.02</td><td>≤0.02</td><td>≤0.006</td><td>≤0.04</td></tr><tr><td>蒸气压（25℃）/Pa</td><td>3.8X10</td><td>一</td><td>1.0×10~</td><td>一</td></tr></table></body></html>  \n\n在芳香族SPUA中，几乎全部采用MDI和改性MDI，而不采用PAPI。MDI常被用来和聚醚多元醇合成预聚物。通过把MDI制成预聚物，可以改善原料体系的相容性，而且对于控制反应物的黏度、反应活性、反应放热和聚合物的结构也是有利的。目前一些公司销售预聚物，使用这些预聚体在某些生产上是有好处的。虽然购买预聚体要比自己合成贵一些，但是它可避免在操作过程中异氰酸酯的挥发，大规模工业化生产有利于产品质量的稳定，并且公司可提供对这些材料的服务。表2-1-198列出了美国Huntsman 公司的系列预聚物产品，其商品牌号为Rubinate°。国内烟台万华聚氨酯股份公司也开发了以WANNATE 8312（—NCO%=15.5）为代表的系列预聚体，详细情况可登陆该公司网站：www.ytpu.com。  \n\n表2-1-198Huntsman公司系列预聚物产品  \n\n\n<html><body><table><tr><td>牌号</td><td>组成</td><td>官能度</td><td>NCO含量/%</td><td>当量</td><td>25℃时的黏度/mPa·s</td></tr><tr><td>Rubinate*9009</td><td>普通MDI预聚物</td><td>2.1</td><td>16.0</td><td>262</td><td>1000</td></tr><tr><td>Rubinate9257</td><td>高官能度预聚物</td><td>2.9</td><td>30.2</td><td>139</td><td>900</td></tr><tr><td>Rubinate9258</td><td>高2.4体MDI预聚物</td><td>2.3</td><td>31. 8</td><td>132</td><td>40</td></tr><tr><td>Rubinate9433</td><td>纯2.4体MDI预聚物</td><td>2.0</td><td>31. 9</td><td>132</td><td>18</td></tr><tr><td>Rubinate®9480</td><td>普通MDI预聚物</td><td>2.0</td><td>15.5</td><td>271</td><td>600</td></tr><tr><td>Rubinate9483</td><td>普通MDI预聚物</td><td>2.0</td><td>15.0</td><td>280</td><td>300</td></tr><tr><td>Rubinate9484</td><td>普通MDI预聚物</td><td>2.0</td><td>16.0</td><td>262</td><td>300</td></tr><tr><td>Rubinate9485</td><td>高2.4体MDI预聚物</td><td>2.6</td><td>31.2</td><td>135</td><td>130</td></tr></table></body></html>  \n\n如果准备合成预聚物，那么了解下面典型的操作程序是有帮助的。  \n\na.加热690g（1.38当量）的分子量为1000的聚醚，在90℃下，真空揽拌1～2h，除去所存在的湿气。  \n\nb.氮气保护下冷却至 $70\\Upsilon$ 。  \n\nc.加人 $435g$ （3.5当量）的纯MDI。  \n\n反应热将使温度升高至 $(80\\pm4)^{\\circ}C$ ，保持这个温度 $_{1\\sim2\\mathrm{h}}$ ，确保反应完全。整个反应要求在氮气保护下进行，生成的预聚物也必须充入氮气进行保护，用这种技术生产的预聚物，在室温下可贮存数月，甚至一年。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 408,
+        "chunk": "# (2）脂肪族异氰酸酯  \n\n$\\textcircled{1}$ 六亚甲基二异氰酸酯（HDI）六亚甲基二异氰酸酯（HDI）是典型的脂肪族异氰酸酯。结构式为OCN—（ $\\mathrm{CH}_{2}$ )6—NCO，属于不黄变的异氰酸酯，反应活性比芳香族异氰酸酯低得多。以HDI为代表的脂肪族异氰酸酯制成的SPUA具有光稳定性好、不黄变的突出优点。  \n\nHDI是由己二胺与光气反应制得：  \n\nHDI主要物理性能指标见表2-1-199。  \n\n表2-1-199HDI主要物理性能指标  \n\n\n<html><body><table><tr><td>项目</td><td>指 标</td><td>项目</td><td>指 标</td></tr><tr><td>外观</td><td>无色或浅黄色透明液体</td><td>闪点/C</td><td>130</td></tr><tr><td>分子量</td><td>168.2</td><td>纯度/%</td><td>>99.5</td></tr><tr><td>沸点/C</td><td></td><td>折射率（）</td><td>1.4530</td></tr><tr><td>5X133. 32Pa</td><td>112</td><td>水解氯含量/%</td><td><0.03</td></tr><tr><td>14X133. 32Pa</td><td>130</td><td>蒸气压/Pa</td><td>1.5(20C)</td></tr><tr><td>相对密度（d）</td><td>1.05</td><td></td><td></td></tr></table></body></html>  \n\nHDI产品反应活性低，因其挥发性较高，毒性也强，所以常以HDI与水反应生成的缩二脲三异氰酸酯和HDI的三聚体作为商品销售。  \n\n1958年Bayer公司率先开发和生产的这种HDI缩二脲多异氰酸酯有溶剂型和非溶剂型两种，产品牌号为DesmdurN-75（固含量 $75\\%$ ）和DesmordurN-100（固含量 $100\\%$ 。HDI三聚体是后来开发的，它的黏度比HDI缩二脲低，含稳定的异氰酸酯环，不易变质，耐候性和保光保色性比HDI缩二脲更好，用量也与日俱增。HDI三聚体产品规格见表2-1-200。  \n\n表2-1-200HDI三聚体产品规格  \n\n\n<html><body><table><tr><td>项 目</td><td>指 标</td><td>项 目</td><td>指 标</td></tr><tr><td>固含量/%</td><td>90</td><td>色度（APHA，最大）</td><td>60</td></tr><tr><td>NCO含量/%</td><td>20±1</td><td>黏度（25℃）/mPa•s</td><td>550±150</td></tr><tr><td>游离HDI含量（最大）/%</td><td>0.2</td><td>密度（25℃）/(g/cm）</td><td>1. 12</td></tr><tr><td>NCO当量</td><td>210</td><td>闪点/C</td><td>41</td></tr></table></body></html>  \n\n近年来，HDI三聚体产量日益增加，很受用户的欢迎，它的主要优点如下。  \n\na.HDI的黏度比缩二脲低，有利于少用溶剂，可配制成高固含量产品，降低大气的污染，有利于环境的保护。  \n\nb.HDI三聚体比较稳定，不易变质，长久贮存后黏度变化不大。  \nc.HDI三聚体制品的耐光性较好，并且制品的硬度较高。  \n\nHDI三聚体在SPUA技术中，主要用于制备聚天冬氨酸酯SPUA材料。它成为继普通脂肪族SPUA材料之后的第三代喷涂聚脲。  \n\n$\\textcircled{2}$ 异佛尔酮二异氰酸酯（IPDI）异佛尔酮二异氰酸酯学名为3-异氰酸酯基亚甲基-3，5,5-三甲基环已基二异氰酸酯，简称IPDI。IPDI属于不黄变的脂环族异氰酸酯，耐光性同  \n\n六亚甲基二异氰酸酯（HDI）一样好。  \n\nIPDI是由丙酮三聚生成的异佛尔酮，与氢氰酸反应生成氰化异佛尔酮，然后经加氢还原和光气化反应制得。  \n\n![](images/1a489f0e82a9525e5b71ef7eddfed203a1cc7e3fd5f88c16c078ae450e9a13e1.jpg)  \n\n独特的化学结构使IPDI具有和其他异氰酸酯不同的特性，3个甲基的存在，使IPDI能与其他化学品极好地相溶，在SPUA原料制备中，不仅能与聚醚多元醇、端氨基聚醚有极好的相溶性，同时与各种配合助剂也能很好地相溶。IPDI的2个异氰酸酯基团活性差别极大，使得用IPDI制备SPUA预聚体A料的过程中能极好地选择所需产物的结构，同时也能大大降低单体IPDI的残留浓度，与聚醚多元醇或端氨基聚醚反应制成的半预聚物具有非常好的贮存稳定性。  \n\nIPDI的工业产品是含顺式异构体（占 $75\\%$ ）和反式异构体（占 $25\\%$ ）的混合物。其反应活性比芳香族异氰酸酯低，蒸气压比HDI低。IPDI主要物理性能指标见表2-1-201。  \n\n表2-1-201IPDI主要物理性能指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>外观</td><td>无色或浅黄色液体</td><td>自燃点/C</td><td>430</td></tr><tr><td>分子量</td><td>222.3</td><td>纯度/%</td><td>≥99.5</td></tr><tr><td>凝固点/C</td><td>60</td><td>NCO含量/%</td><td>37.8</td></tr><tr><td>沸点/C</td><td>158(10×133. 32Pa)</td><td>总氯含量/%</td><td>≤0.04</td></tr><tr><td>密度/（g/cm）</td><td>1. 058(20°C)</td><td>水解氯含量/%</td><td>≤0.02</td></tr><tr><td>黏度/mPa• s</td><td></td><td>蒸气压/Pa</td><td></td></tr><tr><td>0C</td><td>37</td><td>20°C</td><td>0.04</td></tr><tr><td>20°C</td><td>15</td><td>50°C</td><td>0.9</td></tr><tr><td>闪点/℃</td><td>163</td><td>折射率（）</td><td>1.4829</td></tr></table></body></html>  \n\n用IPDI制备的脂肪族SPUA具有极好的光泽度、良好的丰满度、卓越的光学稳定性和耐化学药品性，但因价格较高，多用于高档SPUA产品的制备。  \n\n$\\textcircled{3}$ 苯二亚甲基异氰酸酯（XDI）苯二亚甲基异氰酸酯（XDI）是由二甲苯（通常为 71%的间二甲苯和 $29\\%$ 的对二甲苯的混合物）与氨氧化制得苯二甲腈，经加氢还原成苯二 甲胺，再光气化而成。 福  \n\n![](images/3f53649640e36ce9b7cef852fb6fa3e3bbfdda762d6d4343f880a44e45bac65e.jpg)  \n\n从XDI结构上看，由于—NCO基团与苯环之间有一个亚甲基相隔，防止—NCO基团与苯环形成共振，所以不会产生SPUA产品黄变现象。XDI耐光性接近脂肪族异氰酸酯，不易黄变，而反应活性比HDI高，容易固化凝胶。  \n\nXDI在室温下为无色透明液体，蒸气压较低，毒性较小，易溶于芳香烃、酯、酮等有 机溶剂。XDI的物理性能及质量指标见表2-1-202。  \n\n表2-1-202XDI的物理性能及质量指标  \n\n\n<html><body><table><tr><td>项 目</td><td>间位XDI</td><td>对位XDI</td><td>工业产品</td></tr><tr><td>外观</td><td>一</td><td>一</td><td>无色透明液体</td></tr><tr><td>分子量</td><td>188.19</td><td>188.19</td><td>188.19</td></tr><tr><td>化学式及组成</td><td></td><td></td><td>间位XDI,70%~75%</td></tr><tr><td>纯度/%</td><td>一</td><td>一</td><td>对位XDI，30%~25% ≥99. 5</td></tr><tr><td>凝固点/℃C</td><td>7.2</td><td>45~46</td><td>5.6</td></tr><tr><td>沸点/C</td><td>159~162(1. 6kPa)</td><td>165(1. 6kPa)</td><td>140(0. 27 ~0. 4kPa)</td></tr><tr><td>闪点/℃</td><td>一</td><td>一</td><td>151(0. 8kPa) 185</td></tr><tr><td>密度/（g/cm）</td><td>一</td><td>一</td><td>1. 202(20°C)</td></tr><tr><td>黏度/mPa·s</td><td>一</td><td>一</td><td>3.6(25℃)</td></tr><tr><td>蒸气压/Pa</td><td></td><td>一</td><td>0.8(20°C)</td></tr><tr><td>表面张力/（×10-N/m）</td><td>一</td><td>一</td><td>37.4(30C)</td></tr><tr><td>折射率（n）</td><td>一</td><td>一</td><td>1.429</td></tr><tr><td>溶解性</td><td colspan=\"3\">易溶于甲苯、乙酸乙酯、丙酮、氯仿、乙醚等</td></tr></table></body></html>  \n\n$\\textcircled{4}$ 环己烷二亚甲基二异氰酸酯（ $\\mathbf{H}_{6}\\mathbf{XDI})$ 环已烷二亚甲基二异氰酸酯又称氢化苯二亚甲基二异氰酸酯，简称氢化XDI，写成 $\\bf{H}_{\\mathrm{6}}X D I$ 或 HXDI。它是为了进一步改善 XDI的耐黄变性而开发的。将生产XDI的中间体苯二甲胺氢化成环已烷二甲胺，再光气化就可制得氢化XDI。所以它也和 XDI一样，是约 $70\\%$ 的间位和约 $30\\%$ 的对位两种异构体的混合物。  \n\n![](images/b3de8e87a7d8cf1693feea2b5cede59717b14967a755fd6c264d3882b65ac941.jpg)  \n\n氢化XDI不仅光稳定性得到了改进，贮存稳定性也好，可用于脂肪族SPUA材料的制备。  \n\n日本武田药品公司生产氢化XDI，分子量194.2，相对密度（ $d_{4}^{25}$ ）1.1，凝固点约$-50\\Upsilon$ ，黏度 $5.8\\mathrm{{mPa}\\bullet\\textbf{s}(25^{\\circ}C)}$ ，蒸气压53Pa $(98\\bar{\\mathrm{{C}}})$ ，闪点 $150\\mathrm{{^{\\circ}C}}$ 。  \n\n$\\textcircled{5}$ 4 $\\cdot4^{\\prime}$ 二环己基甲烷二异氰酸酯 $\\langle\\mathrm{H}_{12}\\mathrm{MDI}\\rangle$ 。 $_{4,4^{'}}$ 二环己基甲烷二异氰酸酯简称氢化MDI，简写为 $\\mathtt{H}_{12}\\mathtt{X D I}$ 或 HDMI。结构式如下：  \n\n氢化MDI分子内有两个环已基，是对称性的二异氰酸酯。它在化学结构上与 $_{4,4^{'}}$ 二苯基甲烷二异氰酸酯 $(4,4^{\\prime}–\\mathbf{MDI})$ ）相似，但氢化MDI是以六元环的脂环取代苯环。由于芳环被氢化，它的活性比MDI低得多。氢化MDI属于不泛黄的脂环族二异氰酸酯，它的蒸气压较高，是最有害的异氰酸酯之一。  \n\nHMDI是以4， $4^{\\prime}$ -二氨基二苯基甲烷（MDA）为原料，在钉系催化剂存在下，经加氢和光气化制得。氢化MDI的物理性能及质量指标见表2-1-203。  \n\n表2-1-203氢化MDI的物理性能及质量指标  \n\n\n<html><body><table><tr><td>项目</td><td>指 标</td><td>项目</td><td>指 标</td></tr><tr><td>分子量</td><td>262</td><td>密度/（g/cma）</td><td>1. 07±0.02</td></tr><tr><td>胺当量</td><td>≤132</td><td>酸度（以HCI计）/%</td><td>≤0.005</td></tr><tr><td>凝固点/℃</td><td>10~15</td><td>水解氯含量/%</td><td>≤0.005</td></tr><tr><td>黏度/mPa•s</td><td></td><td>色度（APHA)</td><td>≤35</td></tr><tr><td>25°℃</td><td>30±10</td><td>闪点/℃</td><td>201</td></tr><tr><td>50℃</td><td>12±4</td><td>蒸气压/Pa</td><td>0.093(25C)</td></tr></table></body></html>  \n\n氢化MDI主要生产厂家有DuPont公司，牌号为Hylene-W，现归属 Bayer 公司，其商品牌号为Desmodur-W。  \n\n$\\textcircled{6}$ 四甲基苯二亚甲基二异氰酸酯（TMXDI）四甲基苯二亚甲基二异氰酸酯简称TMXDI，它是一种间位结构的二异氰酸酯，所以也有用 ${\\bf{m}}$ -TMXDI表示的。其分子结构是XDI的两个亚甲基上的氢原子被甲基取代，甲基取代了氢原子以后，提高了耐紫外线老化性和水解稳定性，减弱了氢键作用，使伸长率增加，而且由于甲基的屏蔽影响，使—NCO基团的反应活性减弱，同时具有低毒、常温下是液体等特点，是早期的脂肪族SPUA材料使用最多的一种二异氰酸酯。结构式如下：  \n\n![](images/392c2ecb08d5178722fa9edb32e1b7ccd4bf7190e974b0f8b5b5ae21f97ce99b.jpg)  \n\n美国氰特（Cytec）公司所生产的TMXDI的物理性能及质量指标见表2-1-204。  \n\n表2-1-204美国Cytec公司所生产的TMXDI的物理性能及质量指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>外观</td><td>无色液体</td><td>熔点/℃</td><td>10</td></tr><tr><td>分子量</td><td>244.3</td><td>蒸气压/Pa</td><td>0.39 (25℃)</td></tr><tr><td>—NCO含量/%</td><td>34.4</td><td>闪点/℃</td><td>93</td></tr><tr><td>当量</td><td>122.1</td><td>黏度/mPa• s</td><td></td></tr><tr><td>沸点/C</td><td>150(0.4kPa)</td><td>0°C</td><td>25</td></tr><tr><td>自燃温度/C</td><td>450</td><td>20°℃</td><td>9</td></tr><tr><td>密度/（g/cm）</td><td>1.05(20°C)</td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 409,
+        "chunk": "# 2.聚醚  \n\n在 SPUA技术中用到的聚醚有两类：一类是用于芳香族A料合成的端羟基聚醚；另一类是用于脂肪族A料合成以及B料制备的端氨基聚醚。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 410,
+        "chunk": "# (1）端羟基聚醚  \n\n$\\textcircled{1}$ 聚氧化丙烯醚多元醇聚氧化丙烯醚多元醇（包括环氧乙烷封端的活性聚醚）是聚脲芳香族A料合成中用量最多的端羟基聚醚，即人们常说的聚醚或PPG。这类聚醚是在起始剂和催化剂存在下，由环氧丙烷开环聚合制得的。SPUA用聚醚主要采用二元醇起始剂，如丙二醇等，有时也掺混部分三官能团多元醇。聚醚的官能度是由起始剂的官能度或活泼氢个数决定的。  \n\n式中—聚合度；x—官能度；YH—起始剂主链；R—烷基或氢。  \n\n聚氧化丙烯醚多元醇的品种很多，但能够用于SPUA材料中A料合成的品种规格不多，常用的几种见表2-1-205。  \n\n表2-1-205用于SPUA技术的聚氧化丙烯醚二元醇物理性能指标  \n\n\n<html><body><table><tr><td>规格</td><td>官能度</td><td>羟值 /(mgKOH/g）/(mgKOH/g)</td><td>酸值</td><td>平均 分子量</td><td>pH</td><td>水分/%</td><td>相对密度</td><td>色度 (APHA)</td><td>总不饱和度 /(mmol/g)</td></tr><tr><td>PPG-400</td><td>2</td><td>270~290</td><td>≤0.05</td><td>约400</td><td>6~8</td><td>≤0.05</td><td>1. 008</td><td>≤50</td><td></td></tr><tr><td>PPG-700</td><td>2</td><td>155~165</td><td>≤0.05</td><td>约700</td><td>6~7</td><td>≤0.05</td><td>1. 006</td><td>≤50</td><td>≤0. 01</td></tr><tr><td>PPG-1000</td><td>2</td><td>109~115</td><td>≤0.05</td><td>约1000</td><td>5~8</td><td>≤0.05</td><td>1.005</td><td>≤50</td><td>≤0.01</td></tr><tr><td>PPG-1500</td><td>2</td><td>72~78</td><td>≤0.05</td><td>约1500</td><td>5~8</td><td>≤0.05</td><td>1. 003</td><td>≤50</td><td>≤0.03</td></tr><tr><td>PPG-2000</td><td>2</td><td>54~58</td><td>≤0.05</td><td>约2000</td><td>5~8</td><td>≤0.05</td><td>1. 003</td><td>≤50</td><td>≤0.04</td></tr><tr><td>PPG-3000</td><td>2</td><td>36~40</td><td>≤0.05</td><td>约3000</td><td>5~8</td><td>≤0.05</td><td>1. 002</td><td>≤50</td><td>≤0.01</td></tr></table></body></html>  \n\n聚醚的分子量越大，单羟基聚醚的含量越高。这些单羟基聚醚分子的存在如同链终止剂，势必阻碍与二异氰酸酯的链增长反应，影响最终产品的性能。为了降低聚醚中一元醇（即单羟基聚醚）的含量，提高SPUA材料的性能，近年来美国的Arco和德国的Bayer等公司，进行了大量的研究开发工作，1995年Arco公司推出了商品牌号为Ac-claim，不饱和度仅为 $0.005\\mathrm{mmol/g}$ 的聚醚。Acclaim聚醚的特点是在具备高分子量$(2000{\\sim}8000$ ）的同时，具有极低一元醇含量，而且分子量分布很窄，分布系数 $M_{\\ast}/M_{n}$ 接近1，黏度低，贮存稳定性好，具有良好的工艺操作性能。将Acclaim聚醚用于SPUA材料，可赋予材料优良的力学强度和高回弹性。表2-1-206、表2-1-207列出了这些聚醚的性能指标。  \n\n表2-1-206普通聚醚（PPG-2000）和Acclaim聚醚不饱和度等质量指标的比较  \n\n\n<html><body><table><tr><td colspan=\"2\">规 格</td><td>不饱和度或一元醇含量 /(mmol/g)</td><td>一元醇含量计算 （摩尔分数）/%</td><td>实际官能度f （计算官能度）</td></tr><tr><td rowspan=\"2\">M,2000二元醇</td><td>普通PPG-2000</td><td>0.03</td><td>8</td><td>1.92</td></tr><tr><td>Acelaim 2200</td><td>0.005</td><td>1</td><td>1.99</td></tr><tr><td rowspan=\"2\">M4000二元醇</td><td>普通PPG-4000</td><td>0.09</td><td>30</td><td>1.70</td></tr><tr><td>Acclaim 4200</td><td>0.005</td><td>2</td><td>1.98</td></tr><tr><td>M8000二元醇</td><td>Acclaim 8200</td><td>0.005</td><td>4</td><td>1.96</td></tr></table></body></html>  \n\n表2-1-207普通聚醚（PPG-2000）和Acclaim聚醚性能指标的比较  \n\n\n<html><body><table><tr><td rowspan=\"2\">项目</td><td colspan=\"2\">普通聚醚</td><td colspan=\"5\">Acclaim聚醚</td></tr><tr><td>PPG-2025</td><td>PPG-4025</td><td>2200</td><td>4200</td><td>8200</td><td>6300</td><td>3201</td></tr><tr><td>分子量</td><td>2000</td><td>4000</td><td>2000</td><td>40000</td><td>8000</td><td>6000</td><td>3000</td></tr><tr><td>标称官能度</td><td>2</td><td>2</td><td>2</td><td>2</td><td>2</td><td>3</td><td>2</td></tr><tr><td>黏度/mPa•s</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>20C</td><td>520</td><td>1685</td><td>465</td><td>1225</td><td>4215</td><td>1900</td><td>775</td></tr><tr><td>40°C</td><td>56</td><td>28</td><td>56</td><td>28</td><td>14</td><td>28</td><td>37</td></tr><tr><td>羟值/（mgKOH/g)</td><td>56</td><td>28</td><td>56</td><td>28</td><td>14</td><td>28</td><td>37</td></tr><tr><td>不饱和度/（mmol/g)</td><td>0.025</td><td>0. 085</td><td>0.005</td><td>0.005</td><td>0.005</td><td>0.005</td><td>0.005</td></tr><tr><td>酸值/（mgKOH/g)</td><td>0.010</td><td>0. 017</td><td>0.02</td><td>0.018</td><td>0.02</td><td>0.02</td><td>0.018</td></tr><tr><td>含水量/%</td><td>0.035</td><td>0.035</td><td>0.025</td><td>0.025</td><td>0.025</td><td>0.025</td><td>0. 025</td></tr><tr><td>色度（Pt-Co,40℃）</td><td>30</td><td>50</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 聚四氢呋喃多元醇聚四氢呋哺多元醇简称聚四氢呋喃(PTHF)，又称聚四亚甲基醚二醇（PTMEG)、聚四亚甲基二醇（PTMG或PTG)、聚1,4-氧四亚甲基二醇（POT-MD)，聚丁二醇是由四氢呋喃开环聚合制得的较低分子量的聚醚二醇，其结构式如下：  \n\n醚键氧原子相邻的碳原子易被空气氧化，也易受紫外线攻击。所以PTMG产品中需添加抗氧剂（如抗氧剂264)，添加量约为 $200\\mathrm{mg/kg}$ ，此外，还需采取防潮措施，注意密封保存。  \n\n$\\textcircled{3}$ 聚e-己内酯多元醇聚e-己内酯多元醇简称聚己内酯（PCL)，是20世纪50年代中期由美国UCC公司开发的，60年代初用于聚氨酯合成。它是在起始剂和催化剂存在下由e-己内酯开环聚合制得的，常用的催化剂有四丁基钛酸酯、四异丙基钛酸酯、辛酸亚锡等。  \n\nUCC公司生产的聚己内酯多元醇商品牌号为NiaxPolyol，有4种规格的分子量，主要用于聚氨酯弹性体，包括 TPU、CPU和 MPU。主要物理性能指标见表2-1-208。  \n\n表2-1-208聚6-已内酯多元醇商品牌号及规格  \n\n\n<html><body><table><tr><td>项 目</td><td>Niax Polyol-D510</td><td>D520</td><td>D540</td><td>D560</td></tr><tr><td>平均分子量M。</td><td>530</td><td>830</td><td>1250</td><td>2000</td></tr><tr><td>羟值/(mgKOH/g)</td><td>210±10</td><td>135 ±7</td><td>90±5</td><td>56±3</td></tr><tr><td>酸值/(mgKOH/g)</td><td>0.3</td><td>0.3</td><td>0.3</td><td>0.3</td></tr><tr><td>凝固点/℃</td><td>30~40</td><td>35~45</td><td>40~50</td><td>45~55</td></tr><tr><td>密度（40℃）/（g/cm）</td><td>1.083</td><td>1.083</td><td>1.082</td><td>1.081</td></tr><tr><td>黏度（40℃)/mPa • s</td><td>70</td><td>130</td><td>230</td><td>500</td></tr><tr><td>水分/%</td><td><0.03</td><td><0.03</td><td><0.03</td><td><0.03</td></tr><tr><td>色度（APHA）</td><td><100</td><td><100</td><td><100</td><td><100</td></tr></table></body></html>  \n\n据介绍，近年来国外推出了分子量分布很窄的聚e-已内酯二醇，其商品牌号为PCL-210N和PCL-220N。前者分子量为1000，后者分子量为2000。与普通的PCL-210和 PCL-220 相比，其分子量分布 $(M_{\\mathrm{w}}/M_{\\mathrm{n}}$ )，前者由2.00降至1.24，后者由1.88降至1.34。用PCL-210N或PCL-220N和MDI制得预聚物与B料反应生成的SPUA材料，其力学强度、耐磨性和回弹性都比普通聚醚好，适用于制造衬里、停车场和矿山输送设备等。  \n\n(2）端氨基聚醚端氨基聚醚（amine terminated polyether，或者polyetheramine）是一类由伯氨基或仲氨基封端的聚氧化烯烃化合物，也是SPUA技术非常关键的原材料。由于大分子链的端氨基含有活泼氢，能与异氰酸酯基团和环氧基团反应，因此，近年来端氨基聚醚主要用于聚氨酯（聚脲）材料的合成原料和环氧树脂的交联剂。除此之外，端氨基聚醚还可在发动机燃油中用于抗浑浊、抗沉降添加剂。  \n\n根据端氨基相连烃基结构的不同，端氨基聚醚可分为芳香族和脂肪族两类；根据氨基基团中氢原子被取代的个数，又可分为端伯氨基和端仲氨基聚醚。以叔氨基为端基的聚醚没有反应活性，某些低分子量产物只能作为溶剂。另外，如果聚酯的分子链段末端被氨基封端，则称为端氨基聚酯。  \n\n端氨基聚醚应用于聚氨酯（聚脲）材料，基于两个主要优点： $\\textcircled{1}$ 氨基化合物与异氰酸酯反应速率比羟基快，可缩短反应的时间； $\\textcircled{2}$ 由氨基化合物与异氰酸酯反应生成的聚脲，在相邻的双氢键（bifurcated hydrogen bond）作用下，其极性要比羟基与异氰酸酯基反应所生成的氨基甲酸酯基强得多。因此，聚脲结构中分子间的作用力特别强，硬链段和软链段的相分离更加明显，聚合物中硬链段区域的熔融温度比起聚氨酯结构也更高，表现在弹性体制品的性能上，聚脲的物理性能和耐热性能远优于聚氨酯。  \n\n端氨基聚醚的合成方法，见诸报道的已有很多，用于工业生产的也有几种。下面分芳香族和脂肪族端氨基聚醚两类对几种具有代表性的端氨基聚醚的合成方法进行介绍。一般来说，芳香族的端氨基聚醚活性稍低，适用于RIM制品；脂肪族端氨基聚醚活性较芳香族的高，黏度较芳香族的低，更适合于SPUA工艺。这两类端氨基聚醚在合成方法上并没有严格的界限，有时是可以互换的。  \n\n$\\Phi$ 芳香族端氨基聚醚的合成方法  \n\na.Simons法早在1957年，杜邦公司的D.M.Simons就首次报道了芳香族端氨基聚醚的合成方法。在他的专利中，提出了芳香族端氨基聚醚的三种合成方法。第一种方法是，先用对硝基苯异氰酸酯对聚醚二元醇进行封端，然后通过加氢反应，使硝基转化为氨基。第二种方法是聚醚双氯甲酯与苯二胺反应，得到端氨基聚醚。反应式如下：  \n\n![](images/77a3d73041d948505c547676b402e4c368099fced7b0a0cab9dfc7b2d4606d41.jpg)  \n\nSimons在他的专利中还提出了第三种合成方法，即异氰酸酯预聚体经水解反应而得到端氨基聚醚的一些原则方法。这是Simons富有前瞻性的专利发现，因为后来工业化生产芳香族端氨基聚醚正是采用了这一思路。  \n\nb.水解法1982年Bayer公司的Rasschover等提出了将聚醚或聚酯多元醇的TDI预聚体通过与碱性水溶液反应，生成含有氨基甲酸酯的中间体，然后再得到化合物的方法。这一方法的关键在于第一步反应必须在低温. $(18\\sim20\\Upsilon$ ）下进行，以保证氨基甲酸酯的全部形成，第二步通过升高温度，使端氨基甲酸酯基团分解，形成氢键，并释放二氧化碳。  \n\n![](images/993ba6be69bcbb2d64436d38356bdf84bbb97f4513b9ac0083aee244e33c36e9.jpg)  \n\n该合成方法的优点是反应体系的黏度在反应过程中没有明显的增大。这是因为在第一步反应加碱水过程中，控制体系在低温下反应，抑制了聚脲的生成，因而没有明显的扩链反应。由于氨基甲酸酯键在此反应条件下较稳定，—NCO基团的水解反应有很高的选择性，只有极少数的氨基甲酸酯因断裂而形成微量的游离甲苯二胺TDA。因而可以说，最终产物的黏度和游离TDA 的含量取决于预聚物的起始黏度和游离TDA 的含量。  \n\nc.氨苯氧基法氯代硝基苯在强碱和极性溶剂（如二甲基亚矾）的作用下，与聚醚多元醇反应，得到聚醚被硝苯氧基封端的中间产物，然后再通过加氢反应，使硝苯氧基化合物还原为氨苯氧基化合物。  \n\n![](images/57f70606c22cbb037dc05514f6d48b1c8e74b7f9156064ad5dcae659c657cc35.jpg)  \n\n在第一步反应中，活泼氢的亲核取代需要在强碱和极性溶剂条件下进行，否则难以获得高产率的硝苯基氧化物；而第二步的加氢反应则比较容易。利用这种方法得到的氨苯氧基封端的端氨基聚醚具有相当低的黏度，并且从反应活性看，能很好地满足RIM工艺对原料的要求。  \n\n$\\textcircled{2}$ 脂肪族端氨基聚醚的合成方法  \n\na.氨解法将醇、氨和氢气的气态混合物在 $200\\mathrm{\\textperthousand}$ 左右和一定压力下，通过Cu-Ni催化作用而完成。整个反应过程包括醇的脱氢、醛的加成氨化、羟基胺的脱水和烯亚胺的加氢生成胺等步骤。  \n\nb.离去基团法氨解反应由于需要高温高压等条件，因此设备投资和操作成本都较高。Simons提出了将胺与含有离去基团（leaving groups）的聚醚反应，可得到端氨基聚醚，而且成本较低。其过程是首先将聚醚多元醇与光气反应，在聚醚两端引人氯甲酸酯基团：  \n\n然后用二元胺与聚醚氯甲酸酯进行反应。氨基与氯甲酸酯基团的摩尔比为 $3:1$ ，便可得黏度极低的由氨基甲酸酯键连接的端氨基聚醚。过量的二元胺可作为HCI的吸收剂。  \n\n$$\n\\mathrm{CloCO-OCOCl\\+H_{2}N-R-N H_{2}\\ -\\Sigma\\Sigma^{\\mathrm{-HCl}}\\Sigma\\Sigma\\Sigma^{}-R-N H C O O-O C O N H-R-N H_{2}}\n$$  \n\n值得指出的是，在第一步氯甲酸酯的形成过程中，有可能存在羟基与氯的亲核取代副反应，特别是当反应物中含有二甲基甲酰胺（DMF）时，副反应就会变成主要的反应而生成端氯代烷基聚醚。  \n\n$$\n\\mathrm{HO\\simOH+2COCl_{2}\\frac{D M F}{-C O_{2},\\Delta-H C l}^{+}\\ C l\\sim C l}\n$$  \n\n在HCI吸收剂存在下，端氯代烷基聚醚可与脂肪族的一元伯胺反应，得到由仲胺封端的聚醚：  \n\n$$\n\\mathrm{Cl\\simCl~+2RNH_{2}\\xrightarrow{~-H C l~}~H N\\sim N H}\n$$  \n\n这种含仲氨基的端氨基聚醚，其黏度甚至比它的起始聚醚还低。氯化聚醚如果与二元伯胺反应，则端氨基聚醚的末端含有伯氨基。  \n\n后来还有人发现，甲磺酰基团是比氯更有效的离去基团，利用甲磺酰氯可非常容易地将甲磺酰基引入聚醚的两端，并且甲磺酰基团与胺的亲核取代反应也能很好地进行：  \n\n$$\n\\mathrm{{HO-OH}+2C H_{3}S O_{3}C l\\xrightarrow{\\mathrm{{~-HCl}~}}C H_{3}S O_{3}O{\\sim}O S O_{3}C H_{3}~\\xrightarrow[\\mathrm{{~-CH_{3}S O_{3}H}}]{+R N H_{2}}~H N{\\sim}N H}\n$$  \n\nc.氨基丁烯酸酯法与前两种脂肪族端氨基聚醚合成方法不同，利用氨基丁烯酸酯(aminocrotonates）法制备端氨基聚醚，可非常灵活地选择聚醚两端的氨基种类。首先用二烯酮（diketen）或者通过乙酰乙烯乙酯与聚醚多元醇的酯交换反应，在聚醚的两端接上乙酰乙酸乙酯基团，然后将被乙酰乙酸酯键封端的聚醚与一元伯胺、氨基醇胺或二元伯胺进行胺化，得到端基为氨基丁烯酸酯、黏度很低的亚胺化合物。  \n\n$$\n\\begin{array}{r l}{\\mathbf{H}0\\longrightarrow\\mathrm{OH~}+2\\mathrm{CH}_{3}\\mathrm{COCH}_{4}\\mathrm{COOC}_{2}\\mathbb{H}_{5}\\xrightarrow[]{-\\mathbf{C}_{2}\\mathbb{H}_{5}\\mathrm{OH}_{+}}\\mathrm{OOCH}_{2}\\mathrm{COCH}_{1}\\mathrm{C}\\longrightarrow\\mathrm{OCOCH}_{1}\\xrightarrow[]{+2\\mathbb{R}\\mathrm{NH}_{2}}}&{\\frac{+2\\mathbb{R}\\mathrm{NH}_{2}}{-2\\mathbb{H}_{1}\\mathrm{O}}}\\\\ {\\mathrm{CH}_{1}\\underset{\\mathrm{NHR}}{\\longrightarrow}\\mathrm{OCOCH}-\\mathrm{H}_{2}\\mathrm{CC}}&{\\frac{1}{\\mathrm{NHR}}}\\\\ {\\mathrm{NHR}}&{\\frac{1}{-2\\mathbb{H}_{2}\\mathrm{O}}}\\end{array}\n$$  \n\n在第一步反应中，如果需要部分地将聚醚乙酰乙酸酯基化，则选用叔丁基乙酰乙酸（TBAA）作为封端基，能有效地进行定量反应。在这里，TBAA不是直接与多元醇进行亲核取代反应，而是先通过消去-加成反应生成一个乙酰乙基酮中间体，再由这个中间体与聚醚多元醇反应，得到封端产物：  \n\n$$\n\\begin{array}{r}{\\begin{array}{r l}&{\\mathrm{CH_{3}C O C H_{2}C O O C(C H_{3})_{3}}\\xrightarrow[-\\mathrm{C(CH_{3})_{3}O H}^{\\star}\\mathrm{CH_{3}C O C H}\\mathrm{-c}\\mathrm{-}0}\\\\ &{\\mathrm{~HO-oH}+\\mathrm{CH_{3}C O C H}\\mathrm{-c}\\mathrm{-}0\\mathrm{-}\\mathrel{\\longrightarrow}\\mathrm{OOCH_{2}C O C H_{3}C-}\\mathrm{OCOCH_{2}C O C H_{3}}}\\end{array}}\\end{array}\n$$  \n\n这个反应中的副反应特别少，生成的叔丁醇纯度很高，完全可以直接回收，用于TBAA的再生。  \n\n在第二步的胺化反应中，所采用的氨基化合物可以是一元伯胺，也可以是二元伯胺，还可以是链烷醇胺，甚至还可以是芳香族伯胺。对于一元胺，胺化反应需要有催化剂（如质子酸或路易斯酸）的作用，并且要利用甲苯回流的方法除去生成的水；而对于脂肪族的二元胺，胺化反应虽然不再需要催化剂，但是两个氨基易于同时参加反应，从而引起扩链，黏度会有一定程度的增加。不过由这类反应得到的端氨基聚醚黏度已足够低，因此，黏度的适当增加在实际使用中是可以接受的。  \n\n氨基丁烯酸酯的反应活性取决于所用氨基化合物的活性，因而这类端氨基聚醚的活性范围可以覆盖很广。如果选择如2-乙基戊二胺这样的无位阻作用的脂肪族二元胺作胺化剂，所得到的端氨基聚醚的活性可与活性非常高的JEFFAMINE°相当。另外，还应指出的是，虽然乙酰乙酸酯中酯键的稳定性不尽如人意，但是，由这类端氨基聚醚制得的聚氨酯弹性体具有非常稳定的物理特性，特别是它们的耐水解性尤为突出。这是因为氨基丁烯酸酯基团本身能够形成一个含有定位很好的氢键（well-positionedhydrogenbond）的环状结构，具有较高的稳定性。核磁共振谱图也已经证实了这种结构的存在。  \n\n![](images/01838023e1e5cfa12cb767b255ecd07b7276fff5869264bce29800cb2eea0cd7.jpg)  \n\n以上介绍了芳香族与脂肪族端氨基聚醚几种典型的合成方法。与芳香族端氨基聚醚相比，脂肪族端氨基聚醚以其更低的黏度和更高的活性，在SPUA工艺中起了决定性的作用。但不管是芳香族端氨基聚醚，还是脂肪族端氨基聚醚，它们与异氰酸酯反应所形成的聚脲结构的优越性，已日益被人们所重视，因而端氨基聚醚在聚氨酯领域里的地位和作用已越来越重要。下面着重介绍端氨基聚醚在聚脲工业的应用情况。  \n\n20世纪70年代，美国Texaco（今Huntsman）公司在世界上最先获得了端氨基聚氧化丙烯醚的专利生产权（商品牌号为JEFFAMINE°），当时生产的目的主要是用于环氧树脂的增韧固化剂。到20世纪80年代初期，随着RIM技术的崛起，人们发现了将JEFFAM-INE用于快速成型的聚氨酯（脲）体系中的明显优势。而真正将它用于SPUA技术的是Texaco 公司的化学家Dudley』．PrimeauxⅡI先生。他在当时Texaco 公司的Austin 实验室，发明了SPUA技术，并最早于1989 年发表研究文章。  \n\nHuntsman公司的JEFFAMINE产品有两个系列（表2-1-209），即三官能度的T系列（图2-1-51）和二官能度的D系列（图2-1-52)。  \n\n表2-1-209JEFFAMINE系列聚醚  \n\n\n<html><body><table><tr><td>牌 号</td><td>官能度</td><td>分子量</td><td>牌 号</td><td>官能度</td><td>分子量</td></tr><tr><td>T5000</td><td>3</td><td>5000</td><td>D4000</td><td>2</td><td>4000</td></tr><tr><td>T3000</td><td>3</td><td>3000</td><td>D2000</td><td>2</td><td>2000</td></tr><tr><td>T403</td><td>3</td><td>400</td><td>D230</td><td>2</td><td>230</td></tr></table></body></html>  \n\n![](images/53bc3e9fbd0d4b8e2db8a3011a1613fcc1060b1dee19a474aebc9fe9f1668525.jpg)  \n图2-1-51T系列聚醚分子结构  \n\n![](images/dc893e2e71c0a50c3619bd73ebbe3a9ebc91faedad60199c20833a4299082919.jpg)  \n图2-1-52D系列聚醚分子结构  \n\n由于Huntsman公司长期垄断JEFFAMINE产品的制造权，使得该产品的价格一直居高不下。从发明SPUA产品的意义上讲，Huntsman公司对世界聚脲工业的诞生和发展功不可没。但是，从发展的眼光来看，由于它的价格垄断策略，从某种意义上讲，也阻碍了SPUA技术的快速发展。2000年以来，随着端氨基聚醚专利保护期的解禁，德国BASF公司利用其生产化工中间体的技术优势，迅速将端氨基聚醚产业化（表2-1-210)，并以较低的价格占领市场。  \n\n表2-1-210BASF公司生产的端氨基聚醚  \n\n\n<html><body><table><tr><td>牌 号</td><td>黏度(25C)/mPa·s</td><td>色</td><td>相对糖度</td><td>当量</td><td>分子量</td></tr><tr><td>D230</td><td>9.4</td><td>≤30</td><td>0.95</td><td>60</td><td>230</td></tr><tr><td>D400</td><td>26.5</td><td>≤100</td><td>0.97</td><td>115</td><td>400</td></tr><tr><td>D2000</td><td>430.7</td><td>≤75</td><td>1.00</td><td>514</td><td>2000</td></tr><tr><td>T403</td><td>70</td><td>1</td><td>一</td><td>81</td><td>400</td></tr></table></body></html>  \n\n国内也在加紧研制端氨基聚醚，江苏化工研究所于2002年开发成功端氨基聚醚，并与扬州晨化科技集团公司合作生产出了系列产品（表2-1-211)。  \n\n表2-1-211 国产端氨基聚醚的性能指标  \n\n\n<html><body><table><tr><td>牌号</td><td>黏度（25C） /mPa•s</td><td>相对 密度</td><td>色泽 /Hazen</td><td>活性氢 当量</td><td>特性</td><td>用途</td></tr><tr><td>CGA-D230</td><td>5~50</td><td>0.95</td><td>≤30</td><td>60</td><td>色浅，黏度低，中温固化，柔软 性好</td><td>涂料、灌注、胶黏剂、复合 材料</td></tr><tr><td>CGA-D400</td><td>20~100</td><td>0.97</td><td>≤30</td><td>115</td><td>使涂料增加柔软性，耐磨性、冲 击性好</td><td>涂料、灌注、胶黏剂</td></tr><tr><td>CGA-T403</td><td>50~100</td><td>0.98</td><td>≤100</td><td>81</td><td>三官能团，硬度高，耐候性、耐热 性好</td><td>灌封、胶黏剂</td></tr><tr><td>CGA-D2000</td><td>200～500</td><td>0.99</td><td>≤100</td><td>514</td><td>与其他固化剂配合，赋予更好的 柔韧性</td><td>环氧树脂增韧剂、聚脲</td></tr><tr><td>CGA-T5000</td><td>600~800</td><td>1.0</td><td>≤100</td><td>850</td><td>是一种PU用活性扩链剂，由于 具有脂肪族长链结构、可降低硬 度，在环氧工业中可用于增韧剂</td><td>环氧树脂增韧剂、聚脲</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 411,
+        "chunk": "# 3.扩链剂  \n\n喷涂聚脲弹性体配方多种多样，产品应用十分广泛，但其合成工艺过程一般使用一步半法。一步半法也称半预聚物法或半预聚体法。它是将二异氰酸酯和低聚物多元醇或氨基聚醚反应先合成半预聚物。通常这种半预聚物分子的端基为异氰酸酯基（—NCO)，平均分子量较低，一般在5000以下。要将预聚物加工成制品，还需要加入胺类扩链剂和氨基聚醚的混合物与之反应。胺类扩链剂中的氨基与上述预聚物中的—NCO端基反应，生成氨基甲酸酯或脲，起扩链作用。活泼氢个数大于2的二胺化合物与上述半预聚物反应时，既可起扩链作用，又可起交联作用，可称为扩链交联剂。一般二胺类扩链剂有两个氨基，含4个活泼氢原子。它与半预聚物反应时，随着胺指数（一 ${\\cdot}\\mathrm{NH}_{2}$ ：—NCO）的变化，可产生不同的化学反应。当一 $\\mathbf{NH}_{2}$ ：—NCO≥1时，在适宜的条件下， $-\\mathrm{N}\\mathrm{H}_{2}$ 基只与--NCO基反应起扩链作用。但当一 $\\mathrm{\\cdotNH}_{2}:-\\mathrm{NCO}{<}1$ 时， $-\\mathrm{NH}_{2}$ 基上的一个氢原子与预聚物中的—NCO基反应生成脲结构，起扩链作用。多余的—NCO基在较高的温度下还能与上述生成的脲基上的活泼氢原子进一步反应，生成缩二脲支化或交联。生产喷涂聚脲弹性体时，通常将异氰酸酯指数（即—NCO： $-\\mathrm{NH}_{2}$ 的当量比）定在 $1.05{\\sim}1.1$ 之间，其目的就是要使加工的制品具有适当的交联密度，以改善压缩永久变形和耐溶胀等性能。所以一般的二胺类扩链剂在实际使用中，除了起扩链作用外，还可在过量一NCO基存在下，在大分子之间产生缩二脲交联。  \n\n二胺是浇注型聚氨酯（CPU）的重要扩链剂，主要用于TDI系列预聚物的硫化剂。脂肪族二胺碱性强，活性高，与异氰酸酯反应十分剧烈，成胶速率太快，难以控制，在CPU生产中无使用价值。但在SPUA生产中，可用于脂肪族SPUA扩链剂使用。芳香族二胺的活性比较适中，并能赋予弹性体良好的物理机械性能，是在SPUA中使用最为广泛的扩链剂。  \n\n（1）固体胺类扩链剂（MOCA）讲到芳香族二胺扩链剂，首先应介绍3， $3^{\\prime}$ 二氯-4，4'-二氨基二苯甲烷（MOCA)。MOCA是浇注型聚氨酯弹性体消耗量最大的一种扩链剂。它是聚氨酯弹性体中用量最多的品种，它的消耗量一直占绝对优势。虽然它在SPUA材料中很少采用，但它促进人们利用空间位阻效应开发了一系列的液体胺类扩链剂。  \n\nMOCA结构式如下：  \n\n![](images/08ae69b0b78dfa438455fe382ee64b42620abcebce92e25fc211e3e18d15c3f6.jpg)  \n\nMOCA是40多年前由DuPont公司开发的，它是由邻氯苯胺和甲醛缩合而成的。在缩合产物中除了上述反应生成的 $^{4,4^{\\prime},}$ 对位二胺外，还有少量的异构体和三元胺生成，其含量一般在 $10\\%$ 以下，实际上MOCA熔点范围的大小就反映了MOCA纯度的高低。  \n\nMOCA在高温或长时间加热时会氧化，使颜色变深，所以规定MOCA的加热温度不要超过 $135\\mathrm{{\\ttC}}$ 。20世纪60年代美国ACC公司对MOCA（牌号为Cyanaset-M）在不同温度下允许加热的时间做了如下规定：  \n\n<html><body><table><tr><td>加热温度/C</td><td>110</td><td>120</td><td>132</td></tr><tr><td>允许加热时间/天</td><td>4</td><td>2</td><td>1</td></tr></table></body></html>  \n\nMOCA的价格比其他的液体胺类扩链剂要低得多，因此在SPUA中使用MOCA，主要为降低成本，同时还可降低反应速率，提高表观性能。其使用方法是将一定量的MOCA与氨基聚醚混合后加热至 $105\\mathrm{{T}}$ 左右，熔化后即可使用。为了改善扩链剂与MDI预聚物的配伍性，苏州市湘园特种精细化工有限公司于近年来开发出液体胺类扩链剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 412,
+        "chunk": "# (2）液体胺类扩链剂  \n\n$\\Phi$ 二乙基甲苯二胺（DETDA）虽然MOCA在聚氨酯工业中的作用很大，但其熔化加工工艺给SPUA的生产带来麻烦。20世纪80年代初美国Ethyl公司开发生产的二乙基甲苯二胺（DETDA)，其商品牌号为ETHACURE°100，是目前颜色最浅的已商品化的液体芳香胺类扩链剂。它是由甲苯二胺和乙烯在三氯化铝催化下进行烷基化反应制得的。由3，5-二乙基-2，4-甲苯二胺和3，5-二乙基-2，6-甲苯二胺两种主要异构体组成。  \n\n![](images/70d035649f773f8fa2ae5b63acab87bcbbfe7f62155c762997b1ca25fb675af6.jpg)  \n\n它的标准组成如下：  \n\n3,5-二乙基-2，4-甲苯二胺 75.5%\\~81.0% 其他三羟基间苯二胺 0\\~0.4%3,5-二乙基-2，6-甲苯二胺 18.0%\\~20.0% 2,4,6-三乙基-1，3-二胺0\\~0.1%二羟基间苯二胺 0.3%\\~0.5%  \n\nDETDA的主要物理性能和质量指标见表2-1-212。  \n\n表2-1-212 DETDA的主要物理性能和质量指标  \n\n\n<html><body><table><tr><td>项 目</td><td>指 标</td><td>项 目</td><td>指 标</td></tr><tr><td>外观</td><td></td><td>澄清的琥珀色液体燃点（TCC在热导池中）/C</td><td>>135</td></tr><tr><td>分子量</td><td>178.28</td><td>黏度/mPa·s</td><td></td></tr><tr><td>相对密度（20°C）</td><td>1.022</td><td>20℃</td><td>280</td></tr><tr><td>凝固点/℃</td><td>15</td><td>25℃</td><td>155</td></tr></table></body></html>  \n\nDETDA常温下为液体，可在 $100^{\\circ}\\mathrm{C}$ 以下使用，是芳香族SPUA使用最广泛的扩链剂。它具有反应速率快、初始强度高、保色性好等特点，适用于生产浅色产品，同时还能提高产品拉伸强度、冲击强度和耐热性。  \n\n$\\textcircled{2}$ 二甲硫基甲苯二胺（DMTDA或DADMT）Ethyl公司后来开发的另一种类似结构的液体二胺扩链剂名为3，5-二甲硫基甲苯二胺（DMTDA或DADMT)，其商品牌号为ETHACURE300。现美国雅宝公司（Albemarle）生产这种扩链剂，它由3，5-二甲硫基-2,4-甲苯二胺和3,5-二甲硫基-2,6-甲苯二胺两种异构体组成，比例为 $80:20$ ，结构式如下：  \n\n![](images/001d96ceccec5e3a265763e3499650e1b76ac6e342894283b071916b3262e4ac.jpg)  \n\nDADMT的物理性能和质量指标见表2-1-213。  \n\n表2-1-213DADMT的物理性能和质量指标  \n\n\n<html><body><table><tr><td>项 目</td><td>指标</td><td>项 目</td><td>指标</td></tr><tr><td>外观</td><td>琥珀色液体</td><td>燃点（PMCC)/C 凝固点/C</td><td>176 4</td></tr><tr><td>分子量 相对密度</td><td>214</td><td>黏度/mPa·s</td><td></td></tr><tr><td>20°C</td><td>1. 208</td><td>20℃</td><td>690</td></tr><tr><td>60℃</td><td>1.18</td><td>60°C</td><td>22</td></tr><tr><td>100°C</td><td>1.15</td><td>100℃</td><td>5</td></tr><tr><td>蒸气压（2.23kPa）/C</td><td>200</td><td></td><td></td></tr></table></body></html>  \n\nDMTDA与预聚物反应的速率比DETDA低很多，与DETDA混合使用，能赋予弹性体良好的表面流平性能，同时对力学性能影响不大。由于它是液体，且黏度不大，便于使用，是新开发的二胺类扩链剂中较有推广价值的品种之一。不足之处是它不能用于浅色制品，同时由于其分子中含有甲硫基（一SCH3），有刺激性异味，所生产出的SPUA也有这种味道，不适合于室内使用；在室外使用容易变色、泛黄，不能用于对保色性要求较高的场合。  \n\n使用平均分子量为2000的聚己二酸乙二醇酯与TDI制备预聚物，再分别与TX-2、DADMT、MOCA扩链生成聚氨酯弹性体，其综合性能比较见表2-1-214。结果表明，TX-2扩链剂的性能与DADMT很接近。  \n\n表2-1-214几种扩链剂的综合性能比较  \n\n\n<html><body><table><tr><td>项 目</td><td>TX-2</td><td>DADMT</td><td>MOCA</td><td>项 目</td><td>TX-2</td><td>DADMT</td><td>MOCA</td></tr><tr><td>混合温度/C</td><td></td><td></td><td></td><td>断裂伸长率/%</td><td>600</td><td>560</td><td>490</td></tr><tr><td>预聚物</td><td>80</td><td>80</td><td>80</td><td>300%定伸强度/MPs</td><td>10.9</td><td>15.0</td><td>12.3</td></tr><tr><td>扩链剂</td><td>20</td><td>20</td><td>120</td><td>撕裂强度/（kN/m）</td><td>95</td><td>86</td><td>86</td></tr><tr><td>凝胶时间/min</td><td>8</td><td>5</td><td>9</td><td>硬度（邵尔A）</td><td>86</td><td>90</td><td>89</td></tr><tr><td>拉伸强度/MPa</td><td>55.5</td><td>55.5</td><td>56.8</td><td>冲击弹性/%</td><td>12</td><td>18</td><td>14</td></tr></table></body></html>  \n\n$\\textcircled{3}$ N, $N^{\\prime}$ -二烷基甲基二胺（UNILINK4200）N， $N^{\\prime}$ 二烷基甲基二胺（UNILINK?4200）是美国UOP（UniversalOilProducts，Co.）公司开发的一种位阻型仲胺类扩链剂。UNILINK°4200结构式如下：  \n\n![](images/2aa17e7cc1845fb0c324ba51986a43e3fb9351c479d35820d1622246989d3ff5.jpg)  \n\n其分子中含有一个不稳定的一H基和一个烷基，烷基在分子中相当于内增塑剂，由于这种内增塑剂是化学键结合在弹性体中，所以不会迁移和挥发，其物理性能见表2-1-215。与其他的芳香族液体胺类扩链剂相比，UNILINK°4200与异氰酸酯的反应速率要慢，可以获得较好的表面状态，同时可以降低硬度、提高抗冲击性和低温性能。单独使用UNILINK?4200作为扩链剂，喷涂体系的凝胶时间可以延长到40s以上，也可以与DETDA混合使用，延长凝胶时间，提高附着力和表面状态。  \n\n表2-1-215UNILINK4200的物理性能  \n\n\n<html><body><table><tr><td>项 目</td><td>指 标</td><td>项 目</td><td>指 标</td></tr><tr><td>外观</td><td>深瑰珀色液体</td><td>密度（20C）/(g/cm）</td><td>0.996</td></tr><tr><td>分子量</td><td>310</td><td>黏度（38℃）/mPa·s</td><td>115</td></tr><tr><td>当量</td><td>155</td><td>闪点/℃</td><td>149</td></tr></table></body></html>  \n\n$\\textcircled{4}\\ N,N^{\\prime}.$ 二烷基苯二胺（UNILINK $\\otimes$ 4100）美国UOP公司还推出另外一种用于SPUA技术的位阻型仲胺类扩链剂N， $N^{\\prime}$ 二烷基苯二胺（UNILINK $\\otimes$ 4100)，虽然其结构与UNILINK $\\otimes$ 4200有所不同，但也可用于B料的配方设计中，起到延长凝胶时间、降低反应速率的作用。UNILINK $\\mathfrak{s}$ 4100结构式如下：  \n\n![](images/e6014de6c3991d7dcfda81b5c0f62f9ac389a34fe88e4d6e9e0c938ea56d43df.jpg)  \n\nUNILINK4100的物理性能见表2-1-216。  \n\n表2-1-216UNILINK4100的物理性能  \n\n\n<html><body><table><tr><td>项 目</td><td>指 标</td><td>项 目</td><td>指 标</td></tr><tr><td>外观</td><td>深红色液体</td><td>密度（20℃）/（g/cm）</td><td>0.94</td></tr><tr><td>分子量</td><td>220</td><td>黏度（38℃）/mPa* s</td><td>8.5</td></tr><tr><td>当量</td><td>110</td><td>闪点/C</td><td>115</td></tr></table></body></html>  \n\n③UNILINK4102和UNILINK°4132UNILINK°4102是一种用于聚氨酯的液态芳香族二胺扩链剂。UNILINK?4102结构式如下：  \n\n![](images/9017c893fe18c910460016bd8e77ac640c46f62e11685a6256d439df76e50714.jpg)  \n\nUNILINK°4102具有独特的性能：有很长的施工寿命，制品的硬度很低；UNILINK?4132是 $70\\%$ 的UNILINK?4102和 $30\\%$ 的四羟基交联剂的混合体，两者的物理性能见表2-1-217。  \n\n表2-1-217UNILINK°4102和UNILINK\\*4132的物理性能  \n\n\n<html><body><table><tr><td>项 目</td><td>UNILINK*4102UNILINK4132</td><td></td><td>项 目</td><td></td><td>UNILINK4102UNILINK4132</td></tr><tr><td>形态</td><td>深色液体</td><td>深色液体</td><td>黏度（38C）/mPa·s</td><td>8</td><td>28</td></tr><tr><td>当量</td><td>110</td><td>99</td><td>闪点/C</td><td>130</td><td>118</td></tr><tr><td>相对密度（16℃）</td><td>0.94</td><td>0.96</td><td></td><td></td><td></td></tr></table></body></html>  \n\nUNILINK?4102可以单独用于低硬度弹性体的扩链剂，同时UNILINK $\\otimes$ 4102和UNILINK $\\otimes$ 4132一般都能在扩链剂组分中起到提高弹性体物理性能的作用。两者的主要优点有：a.与其他扩链剂组分相容性好；b.液态化合物，使用方便；c.性价比高，是MDI型弹性体理想的胺类扩链剂之一。和其他UNILINK扩链剂混合后，具有延长施工寿命、降低产品硬度、改善压缩变形等优点。  \n\n$\\textcircled{6}$ UNILINK4230UNILINK4230是一种易混合、易流动的液体扩链剂，能够使SPUA材料的扩链和交联达到很好的平衡。UNILINK4230是 $70\\%$ 的UNILINK?4200和 $30\\%$ 的四（2-羟丙基）乙二胺混合而成的，其中UNILINK4200给这个扩链剂以优异的扩链性能，而四官能度的多元醇赋予交联性能。  \n\nUNILINK°4230的主要优点有：a.预先进行了混合，容易使用；b.液态化合物，使用方便；c.延长施工寿命；d.不易吸潮；e.同许多扩链剂都有较好的相容性等，其物理性能见表2-1-218。  \n\n表2-1-218 UNILINK°4230的物理性能  \n\n\n<html><body><table><tr><td>项 目</td><td>指 标</td><td>项 目</td><td>指 标</td></tr><tr><td>物理形态</td><td>深珑珀色液体</td><td>当量</td><td>130</td></tr><tr><td rowspan=\"2\">组成</td><td>70%(eq)UNILINK4200</td><td>相对密度（16℃）</td><td>1.01</td></tr><tr><td>30%（eq）四官能度多元醇</td><td>黏度（38℃）/mPa·s</td><td>265</td></tr></table></body></html>  \n\n(3）脂肪族二胺扩链剂  \n\n$\\Phi$ 异佛尔酮二胺（IPDA）异佛尔酮二胺（IPDA）是一种通过异佛尔酮化学反应制成的脂环族二胺，是由3-氨甲基-3，5，5-三甲基环己基胺的两种异构体形成的混合物，IPDA(3-aminomethyl-3，5，5-trimethylcyclohexylamine）是一种无色有轻微氨味的低黏度液体，IPDA结构式如下：  \n\n![](images/dbc9a9ec992a98db5f6daf3ca1d62ff495191d1c3684dd1aab78cf23959a9eee.jpg)  \n\n异佛尔酮二胺（IPDA）的物理性能见表2-1-219。  \n\n表2-1-219IPDA的物理性能  \n\n\n<html><body><table><tr><td>项 目</td><td>指 标</td><td>项 目</td><td>指 标</td></tr><tr><td>分子量</td><td>170.3</td><td>蒸气压（25C）/Pa</td><td>1.467</td></tr><tr><td>异构体比例（邻位！对位）</td><td>3.2:1</td><td>熔点/C</td><td>10</td></tr><tr><td>色度（APHA)</td><td><15</td><td>沸点(101325Pa)/C</td><td>247</td></tr><tr><td>胺值/(mgKOH/g)</td><td>644</td><td>闪点/℃</td><td>112</td></tr><tr><td>胺当量</td><td>85.1</td><td>自燃温度/C</td><td>112</td></tr><tr><td>相对密度[25℃（77F）]</td><td>0.920~0.925反射系数（25C）</td><td></td><td>1.4877</td></tr><tr><td>黏度[20°℃（68°F）]/mPa·s</td><td>18</td><td>水溶性</td><td>可溶</td></tr><tr><td>蒸气相对密度（空气=1）</td><td>5.9</td><td></td><td></td></tr></table></body></html>  \n\nIPDA的反应速率比DETDA要快得多，因此不适合用于芳香族SPUA，主要用于脂肪族SPUA，所制得的产品收缩率小，色泽稳定性、耐化学品性和力学性能好。  \n\n$\\textcircled{2}$ CLEARLINKTM系列脂肪族胺类扩链剂CLEARLINKTM系列脂肪胺是美国UOP公司所开发的新型抗紫外线老化扩链剂，与异氰酸酯的反应速率比其他的脂肪胺类扩链剂要慢，可用于脂肪族SPUA材料的制备，产品的力学性能、耐热性能和抗紫外线老化性能均较好。  \n\nCLEARLINKTM系列脂肪胺类扩链剂有两个品种：CLEARLINKTM1000和CLEARLINKTM3000，CLEARLINKTM 3000 的反应速率要比CLEARLINKTM 1000 慢得多。  \n\nCLEARLINKTM1000结构式如下：  \n\n![](images/cbc86ccb32448bc22262daceac0db9dbcddb44d0b3b27c65cfb4d829636c2250.jpg)  \n\nCLEARLINKTM 3000结构式如下：  \n\n![](images/1c1b83c90d0d55a48eabfeb5a34da646dfd2ccd9d6d1ad43ee8beadcf29eb031.jpg)  \n\nCLEARLINKTM系列脂肪胺的物理性能见表2-1-220。  \n\n表2-1-220CLEARLINKTM系列脂肪胺的物理性能  \n\n\n<html><body><table><tr><td>项 目</td><td>1000</td><td>CLEARLINKTMCLEARLINKTX 3000</td><td>项 目</td><td>CLEARLINKTM 1000</td><td>CLEARLINKTM 3000</td></tr><tr><td>外观</td><td>无色透明液体</td><td>无色透明液体</td><td>含水量（质量分数）</td><td><600X10-§</td><td><300×10b</td></tr><tr><td>相对密度</td><td>0.90</td><td>0.90</td><td>毒性（LDso）/(mg/kg)</td><td>482</td><td>523</td></tr><tr><td>凝固点/℃</td><td>-42</td><td>30</td><td>分子量</td><td>322</td><td>350</td></tr><tr><td>闪点/C</td><td>141</td><td>93</td><td>当量</td><td>161</td><td>175</td></tr><tr><td>黏度（25C）/mPa·s</td><td>110</td><td>270</td><td>羟值/（mgKOH/g）</td><td>348</td><td>321</td></tr></table></body></html>  \n\n$\\textcircled{3}$ VERSALINKTM系列扩链剂VERSALINKTM系列扩链剂是由AirProducts公司所开发的脂肪胺类扩链剂，物理性能见表2-1-221。  \n\n表2-1-221 VERSALINKTM系列脂肪胺的物理性能  \n\n\n<html><body><table><tr><td>牌 号</td><td>官能度</td><td>分子量</td><td>含水量</td><td>熔点/C</td><td>黏度（40C)/mPa*s</td><td>密度 /（kg/m）</td></tr><tr><td>VERSALINKTM250</td><td>2</td><td>470</td><td>550X10-§</td><td>56</td><td><300(85°C)</td><td>1040~1100</td></tr><tr><td>VERSALINKTM 650</td><td>2</td><td>830</td><td>一</td><td>15</td><td>2500</td><td>1000~1050</td></tr><tr><td>VERSALINKTM 1000</td><td>22</td><td>1200</td><td>一</td><td>18~21</td><td>3000</td><td>1010~1060</td></tr><tr><td>VERSALINKTM 740M</td><td></td><td>314</td><td>一</td><td>125~128</td><td></td><td>1140（熔化）</td></tr></table></body></html>  \n\n其中VERSALINKTM74OM由于熔点太高，不适合于喷涂使用。而VERSALINKTM250、VERSALINKTM650、VERSALINKTM1000是由聚四氢呋喃改性而成的二胺，既可用于脂肪族SPUA材料，又可用于耐磨型芳香族SPUA材料的制备。  \n\n$\\textcircled{4}$ JEFFLINKTM系列胺类扩链剂美国Huntsman公司所生产的JEFFLINKTM系列脂肪胺类扩链剂有如下几个牌号：JEFFLINKTM555、JEFFLINKTM754、JEFFLINKTM7027，均可用于脂肪族SPUA材料的生产。  \n\nJEFFLINKTM754结构式如下：  \n\n![](images/abff294ac03c93c96f6b1e21fb97b246d9d2790d29055e6ebbcce906293ec857.jpg)  \n\n其中JEFFLINKTM 555由于含有羟基，因此反应速率相对较慢，适合于生产手工聚脲，与UNILINK420O相比，制品的伸长率提高明显，而硬度和拉伸强度有所下降。JEF-FLINKTM754是一种脂环族仲胺，反应速率较慢，用于脂肪族SPUA，可以提高表面状态和力学性能。JEFFLINKTM7027是一种位阻型胺类扩链剂的混合物，实际上是一种含有聚醚软段的反应型内增塑剂，具有反应速率较慢、弹性好、伸长率高等优点，主要用于手工灌注聚脲（例如黏合剂、密封剂、灌封料等）的生产。JEFFLINKTM系列脂肪胺类扩链剂的物理性能见表2-1-222。  \n\n表2-1-222JEFFLINKTM系列脂肪胺类扩链剂的物理性能  \n\n\n<html><body><table><tr><td>项目</td><td>JEFFLINKTM 555</td><td>JEFFLINKTM 754</td><td>JEFFLINKTM 7027</td></tr><tr><td>外观</td><td>无色到乳黄色微浑浊液体</td><td>无色透明液体</td><td>无色透明液体</td></tr><tr><td>色度(Pt-Co)</td><td>≤100</td><td><50</td><td>20</td></tr><tr><td>密度/(g/mL)</td><td>1. 09</td><td>0.858</td><td>0.917</td></tr><tr><td>黏度（25C)/mPa·s</td><td>一</td><td>13</td><td>66</td></tr><tr><td>闪点/C</td><td>170</td><td>104</td><td>116</td></tr><tr><td>总胺量/（mmol/g）</td><td>7.5~8. 2</td><td>7.8</td><td>4.43</td></tr><tr><td>伯胺量/(mmol/g)</td><td>一</td><td>≤0.3</td><td>0.54</td></tr><tr><td>权胺量/（mmol/g)</td><td>一</td><td>≤0.3</td><td>≤0.60</td></tr><tr><td>胺当量</td><td>一</td><td>127</td><td>226</td></tr><tr><td>含水量/%</td><td>≤0.25</td><td>一</td><td>≤0.15</td></tr></table></body></html>  \n\n$\\textcircled{5}$ 助剂在SPUA材料的生产和贮存过程中，由于其自身的涂料特征，往往需要添加多种助剂来改善其工艺和贮存稳定性，提高产品质量，以及扩大应用范围。用于SPUA材料的助剂有很多，如稀释剂、分散剂、防沉降剂、着色剂、阻燃剂、脱模剂、填充剂、防霉剂、抗静电剂、抗氧剂、光稳定剂和增塑剂等，详细情况可参考《喷涂聚脲弹性体技术》等专业书籍及资料。  \n\n此外，通过引人不同的助剂，还能进一步赋予材料不同的特性和优点，比如用于户外施工的 SPUA组合料，就可以在配方设计时加入一些紫外线稳定剂和抗氧剂；用于加油站地面等对防静电要求比较高的场合，就可以加入一些抗静电剂和阻燃剂。灵活地加人各种助剂，大大拓展了聚脲的使用范围，同时也较好地解决了聚脲施工与生产中的一些问题，并赋予聚脲更优异的性能。  \n\n在SPUA材料的助剂选用过程中，其基本思路与通常的涂料配方设计相同，但基于  \n\nSPUA技术自身的特点，还需要在把握涂料配方设计基本概念的前提下，加以活学活用。近年来，国内外在研制、开发涂料助剂方面日益专业化、系列化和全球化，很多常规涂料配方设计所涉及的助剂品种，在SPUA技术中也同样适用。国外的一些大公司，例如美国的气体化工产品公司（Air Products＆Chemicals）、康普顿公司（Crompton）、威科公司（Wit-co）和德国的毕克公司（BYK)、高施米特公司（Gold Schmidt）等，还生产聚氨酯专用助剂，目前，这些公司在国内都有经销商。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 413,
+        "chunk": "# 三、聚脲化学反应原理",
+        "category": " Introduction"
+    },
+    {
+        "id": 414,
+        "chunk": "# 1.半预聚物合成  \n\n在聚脲化学中，一般把A组分的—NCO含量作为区分预聚物和半预聚物的标准。预聚物的—NCO含量一般在 $12\\%$ 以下；而半预聚物的—NCO含量一般在 $12\\%\\sim25;$ %之间。在喷涂聚脲弹性体中，A组分一般采用的是半预聚物，主要原因有：黏度较低；固化产物的物理性能好；反应活性适中。  \n\n在合成半预聚物的过程中，有以下几种反应并存： $\\textcircled{1}$ 芳香族异氰酸酯同端羟基聚醚的反应； $\\textcircled{2}$ 脂肪族异氰酸酯与端氨基聚醚的反应； $\\textcircled{3}$ 异氰酸酯同端氨（或羟）基聚醚等原料中微量水分的反应； $\\textcircled{4}$ 异氰酸酯的自聚反应。  \n\n芳香族异氰酸酯同端羟基聚醚的反应是合成半预聚物最基本的化学反应，反应生成以氨基甲酸酯为特征结构的、--NCO封端的聚氨酯半预聚物。在半预聚物的合成中，常用的羟基化合物有聚氧化丙烯醚多元醇、聚四氢呋哺多元醇（PTMEG）、聚e-已内酯多元醇、端羟基聚丁二烯等。其中最常用的是聚氧化丙烯醚多元醇，它的原材料来源广泛，价格低廉，合成的半预聚物黏度低，是SPUA技术应用最广的一种原材料，可以满足一般防水、防腐蚀、耐磨等领域的要求；在对耐磨性、力学强度等要求较高的场合，一般选择聚四氢呋喃多元醇，但其价格昂贵，并且合成的半预聚物黏度较大，贮存稳定性较差。为了提高聚脲弹性体力学性能并且降低成本，有资料介绍用一部分低不饱和度聚醚多元醇（如Acclaim2200、Acclaim4200等）代替部分聚四氢呋喃二元醇合成半预聚物，固化后的产物力学强度无明显降低，但伸长率成倍地提高，同时半预聚物的黏度大大降低，更适合于喷涂施工。虽然由聚酯多元醇合成的半预聚物具有很高的拉伸强度、撕裂强度，但由于其黏度太高，在喷涂聚脲弹性体中很少采用。用端羟基聚丁二烯合成的半预聚物的最突出的性能是水解稳定性、电绝缘性及低温柔顺性，但由于端羟基聚丁二烯的极性较低，与二异氰酸酯的相容性较差，合成的半预聚物容易浑浊。  \n\n(1）脂肪族异氰酸酯与端氨基聚醚的反应由于芳香族异氰酸酯同端氨基聚醚的反应活性很高，半预聚物合成时只能在很低的温度下进行，并且对氨基聚醚的加入方式（滴加）和分散措施也要求很高，所得到的预聚物黏度大，贮存稳定性差，很少采用；而脂肪族异氰酸酯如IPDI、TMXDI等与端羟基化合物反应活性很低，固化产物力学性能差。为了提高生产效率及SPUA材料的力学性能，利用端氨基聚醚与脂肪族异氰酸酯反应合成半预聚物，并以此作为喷涂脂肪族聚脲弹性体的A组分，可以得到耐候性好、不粉化的高档装饰材料。其反应式如下：  \n\n(2）异氰酸酯与水分的反应聚醚、聚酯等多元醇以及其他原料中都难免有微量水分存在，所以异氰酸酯与水的反应是经常遇到的，而且该反应在异氰酸酯与多元醇的反应条件下会同时发生。  \n\n化学家伍尔兹（Wurtz）认为异氰酸酯与水的反应，先生成不稳定的氨基甲酸，然后很快分解生成胺和二氧化碳。1mol水能生成22.4L二氧化碳气体（标准状态下）。  \n\n由上述反应可以看出，水可以产生两种作用：生成脲基使预聚物黏度增大；以脲基为支化点还能进一步与异氰酸酯反应，形成缩二脲交联，而使预聚物的贮存稳定性降低甚至凝胶。由此可见，如果对聚醚、聚酯等多元醇以及其他原料中的微量水分不加以控制，势必会出现半预聚物黏度过大，造成供料困难，混合效果变差等不良后果。为了确保预聚物质量，必须严格控制低聚物聚醚多元醇或聚酯中的水分含量，必要时要进行脱水处理，保证所用聚合物多元醇或聚酯的水分含量低于 $0.05\\%$  \n\n(3）异氰酸酯的自聚反应二苯基甲烷二异氰酸酯（MDI）是SPUA技术中最常用的多异氰酸酯，但它具有很强的自聚倾向，易发生二聚体与三聚体的环化反应：  \n\n![](images/53b3b7ed2fccc62b492a41d893b10f4a1e4a7971fb696007649780790785887c.jpg)  \n三聚环化反应  \n\n二聚体受热时又能分解为初始单体。而三聚体含有异氰尿酸酯环，对热及许多化学药品稳定。因此，为了保证半预聚物的质量，MDI最好在冷冻条件下 $:-5\\sim5^{\\circ}C$ ）贮运，并且在保质期内使用。MDI精品保质期与贮存温度的关系见表2-1-223。  \n\n表2-1-223MDI精品保质期与处存温度的关系  \n\n\n<html><body><table><tr><td>贮存温度</td><td>保质期</td><td>贮存温度</td><td>保质期</td></tr><tr><td>0C</td><td>3个月左右</td><td>20℃</td><td>4天</td></tr><tr><td>5C</td><td>30天</td><td>70°C</td><td>1天</td></tr></table></body></html>  \n\n温度越高，MDI的自聚倾向越大，生成的半预聚物黏度越高，贮存稳定性越差，因此在合成半预聚物时，必须在较低的温度下进行。综合考虑生产效率及产品质量，合成温度一般控制在 $60{\\sim}80^{\\circ}\\mathrm{C}$ @",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 415,
+        "chunk": "# 2.SPUA材料的生成反应  \n\nSPUA材料的特征反应是半预聚物同氨基聚醚与液体胺类扩链剂之间进行的，在高温时，还有半预聚物同脲基的副反应。  \n\n（1）半预聚物同端氨基聚醚及伯胺扩链剂的反应聚脲反应的实质是半预聚物与氨基聚醚及胺类扩链剂的反应。由于氨基聚醚活性很高以及N原子的碱性，反应不需要催化剂就在极短的时间内固化成型。因此，喷涂聚脲弹性体可以在极为苛刻的条件下施工，即使底材完全被水浸湿或空气中湿度很大时，SPUA材料仍未有任何发泡的迹象。甚至在很低的温度下（如 $-20\\mathrm{\\bar{C}})$ ，SPUA材料仍会固化。而喷涂聚氨酯弹性体SPU或喷涂聚氨酯（脲）SPU（A）弹性体反应机理与SPUA材料截然不同，由于含有反应活性很低的端羟基化合物，要想达到较快的反应速率必须加入大量的催化剂，而催化剂的引入有如下缺点： $\\Phi$ 催化剂既可以加速端羟基聚醚与异氰酸酯的反应，同时也可以加速水与异氰酸酯的反应，因而容易发泡； $\\textcircled{2}$ 催化剂既可以加速弹性体的生成反应，同时也可以加速弹性体的降解，所得弹性体的耐老化性差； $\\textcircled{3}$ 在环境发生温度变化时，催化剂对反应的催化效果相差较大，体系不稳定；$\\textcircled{4}$ 在喷涂聚氨酯弹性体或喷涂聚氨酯（脲）弹性体时，一般采用有机金属类催化剂与叔胺类催化剂进行复配，但叔胺类催化剂在较高的温度下容易挥发，喷涂时气味大，损害人体健康。  \n\n![](images/2cb2564aee6c6c08924488be9b86ce86419c93900a698f2db8ab99927e6863fd.jpg)  \n\n从分子结构分析，SPUA材料中的脲基呈现以C一O基团为中心的几何对称结构，比聚氨酯材料的氨基甲酸酯基稳定，所以聚脲材料的耐老化、耐化学介质、耐磨、耐核辐射和耐高温等综合性能优于聚氨酯。  \n\n(2）半预聚物同仲氨基聚醚及仲胺扩链剂的反应芳香族异氰酸酯与常规的氨基聚醚（如JEFFAMINE系列）、液体胺类扩链剂（如ETHACURE100）反应速率极快，通常凝胶时间少于 $3\\sim5\\mathrm{s}$ ，因而存在对底材的润湿能力弱、附着力低、层间结合不理想、涂层表观状态差、涂层内应力大等一系列缺点。如果在SPUA配方中，加入一部分仲氨基（尤其是位阻型）扩链剂（如UNILINK4200）或仲氨基聚醚，可以把凝胶时间延长至 $30\\sim60s$ 西涂层具有更好的流平性及附着力，同时减少了涂层的内应力。  \n\n（3）半预聚物的交联反应SPUA材料要满足使用要求，常常需要在大分子之间形成适度的化学交联。它可以提高SPUA材料的撕裂强度、耐介质性及压缩强度，降低压缩变形率，改善施工性能等。化学交联一般可以采用如下方法获得： $\\textcircled{1}$ 官能度大于2的多异氰酸酯合成的半预聚物； $\\textcircled{2}$ 官能度大于2的氨基聚醚与半预聚物反应； $\\textcircled{3}$ 过量的异氰酸酯与脲基反应生成缩二脲交联。反应生成三维立体网状结构（图2-1-53)。  \n\n![](images/8ddad01f7522f0e5036ac940ae7d73caf14e92c11dc6e6037ab2a592b89003e2.jpg)  \n图2-1-53聚脲弹性体的立体网状结构  \n\n（4）半预聚物同脲的副反应半预聚物同氨基聚醚或胺类扩链剂反应生成脲基。在100℃以上，异氰酸酯与脲基就有适中的反应速率，生成缩二脲支链或交联。缩二脲基团的生成，对弹性体的耐热性、低温柔顺性以及力学强度等带来不利影响。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 416,
+        "chunk": "# 3.反应速率  \n\n(1）活泼氢化合物结构的影响活泼氢化合物与异氰酸酯的反应速率主要取决于活泼氢化合物分子中亲核中心的电子云密度和空间效应。如与—OH或—NHz相连接的R基系吸电子基，则降低O原子或N原子的电子云密度，从而降低一OH或一 $\\cdot\\Nu\\mathrm{H}_{2}$ 与—NCO的反应活性；反之，如果R基系推电子基，则促进一OH或一 $\\cdot\\mathrm{NH}_{2}$ 与—NCO的反应。表2-1-224是异氰酸酯同各种活泼氢化合物的相对反应速率。  \n\n表2-1-224异氰酸酯同各种活泼氢化合物的相对反应速率  \n\n\n<html><body><table><tr><td>活泼氢化合物</td><td>典型结构</td><td>相对反应速率</td><td>活泼氢化合物</td><td>典型结构</td><td>相对反应速率</td></tr><tr><td>脂肪族伯胺</td><td>R—NHz</td><td>100000</td><td>仲醇</td><td>RR’CHOH</td><td>30</td></tr><tr><td>脂肪族仲胺</td><td>RR'NH</td><td>20000~50000</td><td>脲</td><td>R—NHCO—NH—R</td><td>15</td></tr><tr><td>芳香族伯</td><td>Ar—NH</td><td>200~300</td><td>权醇</td><td>RR'RCOH</td><td>0.5</td></tr><tr><td>伯醇</td><td>RCHOH</td><td>100</td><td>氨基甲酸酯</td><td>R—NHCOO—R</td><td>0.3</td></tr><tr><td>水</td><td>HOH</td><td>100</td><td>酰胺</td><td>RCO—NH</td><td>0.1</td></tr><tr><td>羧酸</td><td>RCOOH</td><td>40</td><td></td><td></td><td></td></tr></table></body></html>\n\n$\\Phi$ 25℃，无催化剂。  \n\n由上表可知，醇、胺等活泼氢化合物与异氰酸酯的反应活性顺序可归纳如下：脂肪族$\\mathrm{NH}_{2}>$ 脂肪族 $\\ N\\mathrm{H>}$ 芳香族 $\\mathbf{NH}_{2}>$ 伯一 $\\mathrm{OH>}$ 水 $>$ RCOOH（羧酸） $>$ 仲一 $\\mathrm{\\DeltaOH>}$ 脲 $>$ 叔$-\\mathrm{OH>}$ 氨基甲酸酯 $>$ 酰胺。脂肪族伯胺或仲胺与异氰酸酯的反应速率远远大于其与水分的反应速率，因而喷涂聚脲弹性体材料受环境湿度的影响小，材料性能稳定，不会产生发泡倾向。而在喷涂聚氨酯弹性体或喷涂聚氨酯（脲）弹性体材料的过程中，聚环氧丙烯醚多元醇（伯醇或仲醇）的反应速率与空气中水的反应速率在同一层次上，当这两种体系在潮湿环境下施工时，就会产生水、聚环氧丙烯醚多元醇同异氰酸酯之间强烈的竞争反应，这就是在湿度较大的情况下，喷涂聚氨酯弹性体或喷涂聚氨酯（脲）弹性体材料很容易发泡的根本原因。  \n\n(2）喷涂聚脲弹性体常用氨基组分的反应活性SPUA常用的氨基组分有： $\\textcircled{1}$ 端氨基聚醚，如JEFFAMINE°D-2000、JEFFAMINE\\*T-5000、JEFFAMINE°D-230、JEFFAM-INET-403等，它们的反应活性一般遵循如下规律：即在相同分子量的前提下，官能度越高，反应速率越快；在官能度相同的条件下，分子量越低，反应速率越快。 $\\textcircled{2}$ 扩链剂，如ETHACURE100、ETHACURE300、UNILINK°4200等。根据表2-1-224的结论，由快到慢顺序为：JEFFAMINE?T-403>JEFFAMINED-230>JEFFAMINET-5000>JEFFAMINE°D-2000>ETHACURE? $100>$ ETHACURE? $300>$ UNILINK?4200。根据氨基组分反应活性的差异，可以针对不同的需要设计出不同的配方。如果外观要求平整、光亮，或者需要在SPUA材料表面铺撒防滑粒子（如金刚砂、橡胶粒、石英砂等)，该体系应选择化学活性较低的仲胺或位阻型伯胺（如UNILINK4200或E-300等）以降低反应速率，延长凝胶时间，保证有足够的时间使喷涂材料流平、铺撒防滑粒料。而对于在垂直壁、天花板上喷涂，须采用快速反应体系（伯氨基聚醚、E-100等)，防止流挂；还可以利用其凝胶速率快的优点，利用喷涂技巧，人为地制造防滑粒子。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 417,
+        "chunk": "# 4.异氰酸酯结构的影响  \n\n（1）电子效应的影响异氰酸酯基（—NCO）是以亲电子中心——正碳离子与活泼氢化合物的亲核中心配位产生极化导致反应进行的，所以与—NCO基连接的烃基（R）的电子效应对异氰酸酯活性的影响正好与R基对活泼氢化合物活性的影响相反，即R若系吸电子基（如芳环)，则降低—NCO基中C原子的电子云密度，从而提高—NCO基的反应活性；若R系供电子基（如烷基)，则降低—NCO基的反应活性。异氰酸酯基的反应活性按下列R基团的排列顺序递减：  \n\n$$\n0.1-(1-x-1)-3-(7-2)-1.5-(7)-3+1.0-(7)=4.5\n$$  \n\n因为苯环是吸电子基，烷基是供电子基，所以芳香族异氰酸酯的活性比脂肪族异氰酸酯大得多。就芳香族异氰酸酯而言，苯环上引入吸电子基（如一 $\\mathrm{NO}_{2}$ 基等)，会使—NCO基中的C原子的正电性更强，从而促进它与活泼氢化合物的反应。反之，苯环上引入供电子基（如烷基)，则增加—NCO基中C原子的电子云密度，使—NCO基的活性降低。  \n\n(2）位阻的影响除了上述苯环上的取代基的电子效应外，取代基的位阻效应同样会降低—NCO基的活性，特别是邻位取代基的位阻效应影响更大。因此同种二异氰酸酯的不同异构体的反应活性也是不同的，如二苯基甲烷二异氰酸酯（MDI）的两种异构体，4，4'-MDI和2,4'-MDI，其结构式如下：  \n\n![](images/b3dbf2f17d153b4c432763576bb8e52bc70e23558da848591baced2311c36778.jpg)  \n\n由于空间位阻影响，其2位的—NCO的反应活性约是4位的 $^{1/3}$ ，所以在喷涂聚脲弹性体A组分（半预聚物）的合成配方中，如果加人一定量的 $^{2,4^{\\prime}}$ -MDI，则能有效地降低反应速率，延长凝胶时间，提高混合效果及表面状态。  \n\n(3）喷涂聚脲弹性体常用芳香族多异氰酸酯反应性能SPUA常用的芳香族多异氰酸酯主要有 ${4,4^{\\prime}–M D I}$ 、高2,4'含量的MDI、液化MDI、PAPI等。其中PAPI的反应性能最为复杂，它是二苯基甲烷二异氰酸酯与多亚甲基多苯基异氰酸酯的混合物，其结构式如下：  \n\n![](images/6874718a52a68cae221cd40edef54303fdb48e0edc99807338da2dab6789c668.jpg)  \n\n就分子结构方面，主要有三个因素影响PAPI的反应性能：二苯环产物的含量、2，4'体含量和每种多苯环产物的含量。二苯环产物的空间位阻小，其第一个—NCO基团的反应活性不会受到附加苯环的供电效应的影响，故反应中表现出初期反应活性较高的特点。但当第一个—NCO基团反应生成氨酯基后，将对第二个—NCO基团产生一定的供电效应，使第二个—NCO基团的反应活性下降，故当PAPI中的二苯环产物含量较高时，表现出初期反应活性较高，但后固化较慢。2，4'体含量较高时，由于空间位阻的影响，反应活性将大大降低。在二苯环产物含量及 $_{2,4^{\\prime}}$ 体含量相同，多苯环产物中每种苯环产物的含量不同时，对反应活性也有一定的影响，这是因为： $\\textcircled{1}$ 苯环数越多，供电效应越大，导致第一个一NCO基团的反应活性降低。 $\\textcircled{2}$ 苯环数越多，因中间以一 $\\cdot\\mathrm{CH}_{2}$ 一为间隔，导致其链传递作用迅速减弱，致使已反应掉的第一个—NCO基团形成的氨酯基对另一端的第二个—NCO基团的影响越小。故苯环数越多，其第二个一NCO基团的反应活性越高。 $\\textcircled{3}$ 苯环数越多，最后一个—NCO基团的反应活性越低。最后参与反应的--NCO基团是夹在链中间的位阻最大且受供电效应最大的邻位—NCO基团，因此其反应活性是较低的。因此，使用PAPI时，一定要注意其成分中主要组成分布，并要进行严格的对比试验，确认其反应性能后方可使用。液化MDI主要有三种，即氨酯改性MDI、碳化二亚胺改性MDI以及脲酮亚胺改性MDI，其中最常用的是碳化二亚胺改性MDI。它们的反应速率由快到慢的顺序为：液化 $\\ensuremath{\\mathrm{\\Delta}}\\mathbf{M}\\ensuremath{\\mathrm{DI}}>4$ ,4'-MDI>PAPI>高 $2,4^{\\prime}–\\mathbf{MDI}$ 。  \n\n(4）脂肪族喷涂聚脲弹性体常用多异氰酸酯的反应性能脂肪族SPUA常用的多异氰酸酯有异佛尔酮二异氰酸酯（IPDI)、六亚甲基二异氰酸酯（HDI)、4， $4^{\\prime}$ 二环己基甲烷二异氰酸酯（ $\\mathbf{H}_{\\mathrm{12}}\\mathbf{MDI})$ 、TMXDI等，其中最常用的是IPDI、TMXDI。HDI的挥发性比TDI还要高，因此在SPUA中一般不采用HDI的单体合成半预聚物，而是使用其二聚体或三聚体，但合成的半预聚体黏度较大。IPDI的两个—NCO基团活性有一定差异，其连在六元环上一NCO基团的活性大约是连在亚甲基基团活性的 $1.3{\\sim}2.5$ 倍，因此与TDI一样，在合成半预聚物时，控制反应初期在较低的温度下进行，使活性较高的—NCO基团首先与氨基聚醚或聚合物多元醇反应，这样有利于生成分子结构规整、黏度较低的半预聚物。IPDI的反应性能较高，大约是 HDI的 $4\\mathord{\\sim}5$ 倍。TMXDI有两种异构体，包括 p-TMXDI和 ${\\mathbf m}$ -TMXDI。其中 $\\mathfrak{p}$ -TMXDI的反应活性和IPDI的反应活性相当， ${\\bf m}$ -TMXDI的反应活性与HMDI相当。TMXDI的挥发性介于MDI与TDI之间。上述脂肪族多异氰酸酯耐紫外线老化性、保色性都很出色，但挥发性较强，给生产施工时的劳动保护提出了严格的要求。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 418,
+        "chunk": "# 5.化学计算  \n\n在聚脲或聚氨酯配方计算中经常用当量这一化学量，因为一切化学反应都遵循等当量的反应原理。对于组成和结构单一的化合物，可由组成和官能度直接计算当量，如TDI、MDI、1,4-丁二醇等。但是，对于聚醚、聚酯、PAPI和预聚物，由于它们都是由多种分子量不同的化合物组成的，而且组成比例也不可能固定不变，所以，它们的当量只有通过官能团的分析才能计算出来，而且是一个数学平均值。  \n\n(1）端异氰酸酯组成物的当量属于这类组成物的主要有PAPI、液化MDI和端异氰酸酯预聚物等，其当量可通过一NCO基含量的分析，根据由部分求整体的数学原理进行计算。其计算公式为：  \n\n(2）端羟基组成物的当量各种聚醚、聚酯及各种多元醇的混合物都属于此类。根据羟值的定义（与每克试样中羟基含量相当的KOH的毫克数）和由部分求整体的数学原理，可按下列公式计算：  \n\n端羟基组成物的当量粒子=56.1×1000  \n\n(3）胺当量胺当量即前面所述的所有端异氰酸酯基化合物的实际当量。因为是采用二正丁胺法分析测定的，所以称为“胺当量”，即与1mol二正丁胺反应的端异氰酸酯基化合物的质量。  \n\n(4）胺值胺值定义是每克端氨基聚醚、胺类扩链剂等含氨基（一 $\\Nu\\mathrm{H}_{2}$ ）的物质的量，胺值分析值可反映该二胺的纯度或含量。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 419,
+        "chunk": "# 四、喷涂聚脲弹性体结构与性能的关系",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 420,
+        "chunk": "# 1.芳香族SPUA材料  \n\n芳香族SPUA材料是聚脲最早进行研究和投人商业应用的品种，对它的研究和开发经验比较丰富。本节重点介绍预聚物官能度、2，4'体MDI含量、减速剂对芳香族SPUA材料固化速率、固化效率和最终力学性能的影响等内容。  \n\n(1）预聚物官能度随着官能度的增加，预聚物的密度和黏度也随之增大。预聚物的黏度对SPUA材料的影响很大，因为A、B物料只有在很短的时间内进行混合、反应，如果它们的黏度差距很大，势必影响混合效果，导致材料的最终力学性能变差。  \n\n$\\Phi$ 预聚物官能度对黏度的影响A料黏度太高的体系难以喷出，即使加人了稀释剂，在75℃时，黏度仍很高。  \n\n因为A、B料的反应活性非常高，凝胶时间非常短，如果出现A料黏度过大，或者A、B料的黏度差值很大，势必难以在体积非常小的撞击混合室中实现充分混合，造成“五指状”、“麻绳状”液流喷出，固化的SPUA材料表面凹凸不平，力学性能较差。  \n\n$\\textcircled{2}$ 预聚物官能度对固化时间的影响评价SPUA材料固化时间的术语有两个：凝胶时间（geltime）和表干时间（tack-free time）。凝胶时间是指经喷枪喷射出的物料，在涂有脱模剂的PVC板表面产生不能流动或者拉丝现象时的时间；表干时间是指经喷枪喷射出的物料，在涂有脱模剂的PVC板表面产生不粘手或者有初始强度现象时的时间。  \n\nMDI预聚物官能度的增加会对体系的反应活性产生强烈影响，随着A料官能度的增加，凝胶时间和表干时间相应缩短；但是，在缩短速率方面，表干时间比凝胶时间降低得更快。在实际的配方设计和产品开发过程中，除了需要考虑A料的因素外，B料的化学组成对体系的整体固化时间具有更为重要的影响。  \n\n由于A、B料混合后的反应速率极快，加上商品化的测量仪器尚未开发出来，因此很难精确测定体系的凝胶时间和表干时间。所以，测量结果在很大程度上取决于操作者的经验，但是总的规律还是很容易发现的，即随着MDI预聚物官能度的提高，体系的反应速率加快；当官能度达到很高时，表干时间的缩短速率比凝胶时间的快。  \n\n有效地控制凝胶时间和表干时间，对研制、开发具有不同功能的SPUA材料具有重要意义，超重防腐材料（外壁）需要凝胶时间短，防止流挂；表干时间略长，增加对钢底材的附着力。屋面防水材料和工业地坪材料要求凝胶时间和表干时间中等，既要考虑到屋面和地坪大面积施工时的流平性和对底材的附着力，又要兼顾对女儿墙、屋檐等少数垂直部位施工时，不能产生流挂；当然两者在考虑其他性能的出发点上也略有差别，屋面防水材料重点强调耐日光老化、价廉物美；工业地坪材料侧重注意抗冲击、耐磨损。防滑铺地材料需要在喷涂SPUA材料之后，抛撒防滑粒料，因此对固化时间（尤其是凝胶时间）要求延长，配方设计时，A料要选择高 $2,4^{\\prime}\\d\\slash\\slash\\slash\\hat{\\ast}$ MDI含量、低官能度的预聚物，B料应筛选长链、位阻型胺类扩链剂；超重防腐材料内壁对固化时间的要求与超重防腐材料外壁相似，但更注重提高交联密度，增加体系抵抗长期腐蚀介质侵蚀的能力和耐温性。SPUA-402防腐保温材料用于大型贮罐、管道外壁聚氨酯泡沫保温层表面保护，配方设计比较简单，要求凝胶时间和表于时间都短，有利于提高施工速度。道具保护材料用于聚苯乙烯泡沫（EPS）雕塑物体表面保护，由于EPS耐热性不高，要求喷出的SPUA材料不能集中放热，否则会使EPS表面熔化，破坏原有的雕刻造型。因此它对固化时间的要求是，凝胶时间短，便于快速定型，防止流挂；表干时间长，有利于均匀释放热量，防止集中放热将EPS雕刻制品烫坏变形。用于钢质管道的内外壁防腐的防腐材料，由于钢质材料是热量传递的良导体，反应产生的热量极易散失，容易导致后期固化不彻底、时间长，影响管道的下线码垛，因此需要它的凝胶时间和表干时间都短。  \n\n$\\textcircled{3}$ 预聚物官能度对断裂伸长率的影响SPUA材料是一种集塑料、橡胶、玻璃钢和涂料多种功能于一身的高性能材料，因此衡量它的理化性能的指标和术语，往往需要涉及众多领域。例如，凝胶时间、表干时间、黏度、附着力、流平性、耐介质性等词汇是用来描述涂料特征的术语，而拉伸强度、断裂伸长率、模量、邵尔硬度、撕裂强度、耐磨性、抗冲击性等指标是用来表征塑料、橡胶、玻璃钢的专业词汇。所以，喷涂聚脲弹性体技术是一门综合技术，国外有人把它总结为“万能”（versatile）技术。  \n\n研究结果表明，随着预聚物官能度的提高，SPUA材料的断裂伸长率下降（图2-1-54)。在表2-1-54的三个B料中，虽然含有UNILINK $\\mathfrak{P}$ 4200的B-3慢固化样品的官能度只有2.09，但它在预聚物官能度较低时的断裂伸长率却达到了最高；但在预聚物官能度较低时的断裂伸长率却不及官能度只有2.0的B-1样品。  \n\n![](images/dbfcdc22d8502b78919fbdfbb72c40b0ec3031cc77c71aed11ac65690db632b1.jpg)  \n图2-1-54预聚物官能度对断裂伸长率的影响→-B-3，f=2. 09；B-1，f=2. 00；B-2，f=2.14  \n\n$\\textcircled{4}$ 预聚物官能度对邵尔硬度的影响表征SPUA材料邵尔硬度的方法有两个：邵尔A和邵尔D，两者的测试方法是一样的，但所使用的仪器略有差异。邵尔A硬度计的顶针比较圆钝，适合于测试与橡胶、软塑料类似的材料；邵尔D硬度计的顶针比较尖锐，适合于测试与玻璃钢、硬塑料类似的材料。  \n\n研究结果表明，随着预聚物官能度的提高，SPUA材料的硬度几乎没有明显变化（图2-1-55)  \n\n![](images/2572738358036d1a93f09010cb2b61c35fae7ee90e8d6076b7cf62589ba26254.jpg)  \n图2-1-55预聚物官能度对邵尔硬度的影响 邵尔A，B-2；邵尔A，B-1；=邵尔A，B3 邵尔D，B-2；邵尔D，B-1；邵尔D，B-3  \n\n$\\textcircled{5}$ 预聚物官能度对撕裂强度的影响研究结果表明，随着预聚物官能度的提高，  \n\nSPUA材料的撕裂强度都出现不同程度的下降，这是由于SPUA材料中存在两种交联，即物理交联和化学交联。物理交联是聚脲材料的硬段之间，通过氢键相互吸引所产生的交联，也就是通常所说的微相分离；化学交联是通过官能度大于2的物质，产生化学结合力所产生的交联。多官能度物质的存在，影响了聚脲材料软、硬段的微相分离，因而效率没有充分发挥。  \n\n$\\textcircled{6}$ 预聚物官能度对拉伸强度的影响研究结果表明，随着预聚物官能度的提高，SPUA材料的拉伸强度都出现不同程度的下降，规律与撕裂强度相似。  \n\n$\\textcircled{7}$ 预聚物官能度对耐磨性的影响预聚物官能度越低，体系的耐磨性越好（图2-1-56)。  \n\n![](images/a17796aadf9a0fd94dac3467a370de2812307ed76a89c265cb5808419cb5708c.jpg)  \n图2-1-56预聚物官能度对耐磨性的影响  \n\n$\\textcircled{8}$ 预聚物官能度对耐介质性的影响分别以甲醇、丙酮、二甲苯、环己烷、刹车油、柴油、汽油、乙二醇为介质，根据ASTMD1308方法，进行测试。测试结果表明，随着预聚物官能度的提高，材料的耐介质性下降。B-3慢反应体系的耐介质性最差，但它对相应A料官能度的变化不太敏感。  \n\n(2）2,4'体MDI含量2,4'体MDI对提高 SPUA材料的综合力学性能，降低A、B料的反应活性，延长凝胶时间，改善喷涂体系的流平性和表面状态，增加对底材的附着力等方面，都具有非常重要的作用。  \n\n(3）碳酸丙酯（PC）的影响将适量碳酸丙酯（PC）加人A料中，不仅降低了黏度，改善了混合和雾化效果，而且还能够部分提高材料的力学性能（表2-1-225)。  \n\n表2-1-225碳酸丙酯对SPUA材料性能的影响  \n\n\n<html><body><table><tr><td rowspan=\"2\">组成及性能</td><td colspan=\"2\">样 品号</td><td rowspan=\"2\">组成及性能</td><td colspan=\"3\">样 晶 号</td></tr><tr><td>1*</td><td>2 3#</td><td>1</td><td>2#</td><td>3</td></tr><tr><td>A组分</td><td colspan=\"3\"></td><td>1.15</td><td colspan=\"3\">1.15 1.16</td></tr><tr><td>MDI基预聚物</td><td>100</td><td>95 90</td><td>A、B质量比 物理性能</td><td></td><td colspan=\"3\"></td></tr><tr><td>JEFFSOLT*PC</td><td>0</td><td>5</td><td>10</td><td>凝胶时间/s</td><td>2.5</td><td>3.0</td><td>4.0</td></tr><tr><td>—NCO含量/%</td><td>15.815.1</td><td></td><td>14. 3</td><td>表干时间/8</td><td></td><td>约10约10</td><td>约10</td></tr><tr><td>B组分</td><td colspan=\"3\"></td><td></td><td></td><td>60</td><td>59</td></tr><tr><td>JEFFAMINE* D-2000</td><td>71.1</td><td>72. 9</td><td>74.5</td><td>硬度（邵尔D) 拉伸强度/MPa</td><td>60</td><td></td><td>13.1014.1315.86</td></tr><tr><td>ETHACURE100</td><td>28.9</td><td>27.1</td><td>25.5</td><td>伸长率/%</td><td>210</td><td>240</td><td>270</td></tr><tr><td>参数</td><td></td><td></td><td></td><td>100%模量/MPa</td><td>2.20</td><td>2.10</td><td>2.00</td></tr><tr><td>异氰酸酯指数</td><td>1.10</td><td>1.10</td><td>1. 10</td><td>素裂强度/（kN/m）</td><td>56.9</td><td>57.1</td><td>57.4</td></tr><tr><td>A、B体积比</td><td>1. 0</td><td>1.0</td><td>1.0</td><td></td><td></td><td></td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 421,
+        "chunk": "# 2.脂肪族SPUA材料  \n\n（1）JEFFAMINE氨基聚醚作为扩链剂A料由m-TMXDI与高分子量的JEFFAM-INE?氨基聚醚合成；B料由不同分子量的JEFFAMINE°氨基聚醚组合而成（表2-1-226)。这样，高分子量的JEFFAMINE°作为软段，低分子量的JEFFAMINE°作为硬段，由于软、硬段结构极其相似，造成了这类喷涂聚脲弹性体材料过于柔软（表2-1-227）。  \n\n<html><body><table><tr><td>牌 号</td><td>官能度</td><td>分子量</td><td>牌 号</td><td>官能度</td><td>分子量</td></tr><tr><td>JEFFAMINET-5000</td><td>3</td><td>5000</td><td>JEFFAMINE*D-2000</td><td>2</td><td>2000</td></tr><tr><td>JEFFAMINE* T-3000</td><td>3</td><td>3000</td><td>JEFFAMINE$ T-403</td><td>3</td><td>400</td></tr><tr><td>JEFFAMINE* D-4000</td><td>2</td><td>4000</td><td>JEFFAMINE*D-230</td><td>2</td><td>230</td></tr></table></body></html>  \n\n表2-1-227JEFFAMINE扩链剂体系脂肪族SPUA材料性能  \n\n\n<html><body><table><tr><td>指标</td><td>配方1</td><td>配方2</td><td>配方3</td><td>配方4</td></tr><tr><td>异氰酸酯指数</td><td>1.00</td><td>1.00</td><td>1.05</td><td>1.05</td></tr><tr><td>A、B体积比</td><td>1.00</td><td>1.00</td><td>1.00</td><td>1.00</td></tr><tr><td>A、B质量比</td><td>1.05</td><td>1.07</td><td>1.10</td><td>1.10</td></tr><tr><td>硬段含量/%</td><td>38.8</td><td>48.7</td><td>58.3</td><td>65.5</td></tr><tr><td>凝胶时间/s</td><td>5.0</td><td>3.0</td><td>2.0</td><td>1.5</td></tr><tr><td>拉伸强度/MPa</td><td>3.76</td><td>7.52</td><td>6.59</td><td>11.4</td></tr><tr><td>伸长率/%</td><td>319</td><td>319</td><td>327</td><td>111</td></tr><tr><td>撕裂强度/（kN/m)</td><td>19.4</td><td>45.5</td><td>46.7</td><td>58.5</td></tr><tr><td>硬度(邵尔D)</td><td>26</td><td>37</td><td>46</td><td>51</td></tr><tr><td>100%模量/MPa</td><td>1.65</td><td>3.61</td><td>4.78</td><td>9.47</td></tr></table></body></html>  \n\n由于不含催化剂，SPUA材料表现出优异的耐老化性。虽然在芳香族SPUA中，会出现泛黄和褪色，但绝无粉化和开裂现象出现。表2-1-228是芳香族SPUA材料经过 $50\\mathrm{^c}$ ，3871h人工紫外线加速老化试验前后的性能变化。脂肪族SPUA材料的耐老化性则更是无与伦比（表2-1-229)，在 $50^{\\circ}\\mathsf{C}$ 、5280h人工紫外线加速老化后，材料不变色，说明它更适合在户外使用。  \n\n表2-1226 JEFFAMINE氨基聚醚规格  \n表2-1-228芳香族SPUA材料的耐老化性  \n\n\n<html><body><table><tr><td>项 目</td><td>老化前</td><td>老化后</td><td>项目</td><td>老化前</td><td>老化后</td></tr><tr><td>拉伸强度/MPa</td><td>13.5</td><td>13.5</td><td>撕裂强度/(kN/m)</td><td>76.4</td><td>84.4</td></tr><tr><td>伸长率/%</td><td>137</td><td>110</td><td>硬度（邵尔D）</td><td>59</td><td>63</td></tr></table></body></html>  \n\n表2-1-229 脂肪族SPUA材料的耐老化性  \n\n\n<html><body><table><tr><td>性能</td><td>1*</td><td>2</td><td>性 能</td><td>1</td><td>2</td></tr><tr><td>TiO质量分数/%</td><td>10.0</td><td>20.0</td><td>硬度（邵尔D)</td><td>22</td><td>46</td></tr><tr><td>拉伸强度/MPa</td><td>4.5</td><td>8.9</td><td>100%模量/MPa</td><td>1.5</td><td>5.4</td></tr><tr><td>伸长率/%</td><td>398</td><td>338</td><td>300%模量/MPa</td><td>3.3</td><td>8.0</td></tr><tr><td>撕裂强度/（kN/m）</td><td>18. 9</td><td>52.9</td><td>颜色变化</td><td>几乎没有</td><td>无</td></tr></table></body></html>\n\n$\\Phi$ 被测材料含 $\\mathrm{TiO}_{2}$ ②紫外线老化试验，5280h材料颜色变化。  \n\n(2）环脂肪二胺作为扩链剂为了改善D-230、T-403这类低分子量JEFFAMINE°氨基聚醚作为扩链剂，造成喷涂聚脲弹性体材料过于柔软的缺点，DudleyPrimeauxⅡI又试验了另外两种低分子环脂肪二胺扩链剂：1,4-环己二胺、异佛尔酮二胺（IPDA）（表2-1-230)。  \n\n表2-1-230环脂肪二胺扩链剂体系脂肪族SPUA材料性能  \n\n\n<html><body><table><tr><td>指 标</td><td>JEFFAMINE氨基聚醚</td><td>1.4-环已二胺</td><td>异佛尔酮二胺</td></tr><tr><td>异氰酸酶指数</td><td>1.05</td><td>1.05</td><td>1.05</td></tr><tr><td>A、B体积比</td><td>1.00</td><td>1.00</td><td>1.00</td></tr><tr><td>A、B质量比</td><td>1.07</td><td>1. 06</td><td>1.06</td></tr><tr><td>硬段含量/%</td><td>48.7</td><td>33.7</td><td>37.9</td></tr><tr><td>凝胶时间/s</td><td>2.0</td><td>1.5</td><td>1.5</td></tr><tr><td>拉伸强度/MPa</td><td>6.56</td><td>6.90</td><td>6.45</td></tr><tr><td>伸长率/%</td><td>391</td><td>664</td><td>357</td></tr><tr><td>撕裂强度/（kN/m）</td><td>38.2</td><td>43.9</td><td>53.6</td></tr><tr><td>硬度（邵尔D)</td><td>40</td><td>31</td><td>44</td></tr><tr><td>100%模量/MPa</td><td>2.90</td><td>2.86</td><td>5.26</td></tr><tr><td>300%模量/MPa</td><td>4.91</td><td>4.12</td><td>6.14</td></tr></table></body></html>  \n\n在脂肪族SPUA材料中引人环脂肪二胺扩链剂代替JEFFAMINE氨基聚醚扩链剂后，能够改善材料的高温区力学性能。在低温区，用JEFFAMINE氨基聚醚作为扩链剂的脂肪族SPUA，在 $-50\\tau$ 左右出现损耗峰；使用1，4-环己二胺、异佛尔酮二胺作为扩链剂的样品，也在 $-50\\Upsilon$ 左右出现损耗峰。  \n\n(3）新型脂肪二胺作为扩链剂虽然1，4-环己二胺、异佛尔酮二胺作为扩链剂对提高脂肪族SPUA材料的强度和硬度有所帮助，但是它的高反应活性使得在喷涂的过程中很难得到光滑的涂层表面效果。为了解决脂肪族SPUA材料存在的上述问题，有关原材料厂家开展了大量的研究和开发工作，其中较为有代表性的脂肪族二元胺扩链剂是UOP公司开发的CLEARLINK $\\mathfrak{s}$ 1000和Huntsman 公司生产的JEFFLINKTM 754。  \n\nUOP公司生产出了CLEARLINK $\\otimes$ 1000二元胺，解决了很多影响脂肪族聚脲弹性体走向商业化应用的实际问题，它是一种环脂肪仲胺，有一个六元环取代基团连在N原子上，基于这种空间位阻效应，它的反应速率比伯胺慢得多，从而带来凝胶时间的延长，有助于形成光滑的涂层表面。Huntsman公司生产的JEFFLINKTM 754与CLEARLINK°1000有相似之处。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 422,
+        "chunk": "# 3.聚天冬氨酸酯SPUA材料  \n\n(1）物理化学特性聚天冬氨酸酯实际上是一种脂肪族仲胺，它最早于1990年由Zwiener等发现可以用于溶剂型聚氨酯涂料的反应型稀释剂，它能够与普通含有羟基的聚酯、聚丙烯酸酯共聚物混溶，从而降低涂料体系中的VOC含量。当它与同是脂肪族的HDI三聚体反应时，能够得到耐候性非常好的新型脂肪族SPUA材料，见表2-1-231。具体表现在：聚天冬氨酸酯黏度低；与HDI三聚体的反应速率可以因不同的取代基团而不同，凝胶时间从 $\\mathrm{5min}$ 延长至 $120\\mathrm{min}$ ；施工寿命可以从5min延长到2h以上；喷涂一道就可达到$0.6\\mathrm{mm}$ ；涂层表面无气孔产生；配方体系的可调节范围很宽；对紫外线有很好的耐受性，光泽持久，色彩稳定，不泛黄；喷涂时的材料损耗少；固含量可以从 $70\\%$ 调节到 $100\\%$ 。  \n\n表2-1-231聚天冬氨酸酯SPUA材料组成  \n\n\n<html><body><table><tr><td>项 目</td><td>A组分</td><td>B组分</td><td>项 目</td><td>A组分</td><td>B组分</td></tr><tr><td>名称</td><td>HDI三聚体</td><td>聚天冬氨酸酯</td><td>黏度/mPa· s</td><td>1000~3000(25℃)</td><td>240~1500(25℃)</td></tr><tr><td>组成</td><td>脂肪</td><td>位阻型脂肪族仲胶</td><td>当量</td><td>195~205</td><td>230~325</td></tr><tr><td>固含量/%</td><td>100</td><td>100</td><td></td><td></td><td></td></tr></table></body></html>  \n\n(2）反应活性表2-1-232的结果说明，聚天冬氨酸酯与HDI三聚体的反应活性远远低于以往的脂肪族、芳香族扩链剂。因此，人们就可以按照施工季节的户外环境温度，确定B料的组成，从而有效地掌握施工节奏和进度，大大提高施工效率，节约材料和费用。  \n\n表2-1-232 2几种聚天冬氨酸酶与HDI三聚体的反应活性  \n\n\n<html><body><table><tr><td>B组分</td><td>A组分</td><td>凝胶时间（22℃）</td><td>凝胶时间（0℃）</td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td>1111</td><td></td></tr><tr><td>Desmophen NH XP-7068 与 NH 1420按50 + 50混合</td><td>Desmodur XP-7100</td><td>27min</td><td>27min</td></tr><tr><td>Desmophen NH 1420 与 NH 1220按50 + 50混合</td><td></td><td></td><td></td></tr><tr><td>CLEARCUINK 100</td><td></td><td></td><td>6min</td></tr><tr><td></td><td></td><td></td><td></td></tr></table></body></html>\n\n① HDI三聚体，—NCO含量20.5%，黏度1000mPa·s（25℃）。  \n\n表2-1-233 3几种天冬氨酸酯与芳香族预聚物的反应活性  \n\n\n<html><body><table><tr><td>B组分</td><td>A组分</td><td>凝胶时间（22℃）</td><td>凝胶时间（0℃）</td></tr><tr><td>Desmophen NH 1420</td><td>NOI案16%</td><td>1min</td><td>4min</td></tr><tr><td>Desmophen NH 1220</td><td>MO答案8%</td><td>0.5min</td><td>0. 5min</td></tr><tr><td>Desmophen NH 1420</td><td>MDI量16%</td><td>5min</td><td>一</td></tr><tr><td>Desmophen NH 1420</td><td>TDO量3%</td><td>40~60min</td><td>90min</td></tr><tr><td>Desmophen NH 1220</td><td>TDI量物3%</td><td>5min</td><td>9min</td></tr></table></body></html>  \n\n从表2-1-232、表2-1-233中可以发现，空间位阻效应、异氰酸酯种类对聚天冬氨酸酯的反应活性影响很大，据此，可以按照配方设计的需要，人为地制备出凝胶时间在几分钟至几小时的喷涂体系，满足不同使用场合的需求。  \n\n(3）材料性能所有喷涂样品需要在室温22℃、相对湿度55%的环境下养护14天，才能进行性能测试。  \n\n选择不同的聚天冬氨酸酯与—NCO含量为20.5%的HDI三聚体反应，所生成的SPUA材料的拉伸强度和伸长率差别很大（表2-1-234)。它表明，含有环已烷结构的DesmophenNH XP-7068和Desmophen NH1420样品的拉伸强度都在45MPa以上，但断裂伸长率只有$4\\%$ 4%，基本上属于刚性材料。而含有直链烷烃结构的Desmophen NH1220和DesmophenNHXP-7161样品的拉伸强度都只有12～16MPa，但是，其断裂伸长率比环已烷结构有了显著的提高，特别是不含侧甲基的DesmophenNHXP-7161样品，其断裂伸长率达到了84%，从而成为一种很有韧性的材料，这一点与通常的MDI基SPUA材料差别很大，主要原因是两者的相分离特性不同。  \n\n表2-1-234 4聚天冬氨酸酯对20.5%的HDI三聚体力学性能的影响  \n\n\n<html><body><table><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td>DemoduxP-</td><td>15.0</td><td>238</td></tr></table></body></html>\n\n①HDI三聚体，—NCO含量20.5%，黏度1000mPa·s（25℃）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 423,
+        "chunk": "# 五、喷涂聚脲弹性体的性能",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 424,
+        "chunk": "# 1.力学性能  \n\n(1）附着力喷涂而成的 SPUA材料对钢、铝和混凝土等底材，均具有良好的附着力。通过配方调节，即使是凝胶时间在3s左右的快体系仍具有很好的附着力。甚至可以调节配方得到附着力强度超过SPUA 自身强度的体系。表2-1-235列出了芳香族SPUA 与几种材料的附着力数据(GB5210拉开法)。  \n\n表2-1-235SPUA材料在不同底材上的附着力  \n\n\n<html><body><table><tr><td>底 材</td><td>底材处理方法</td><td>附着力/MPa</td><td>破坏形式</td></tr><tr><td rowspan=\"3\">钢</td><td>表面清洁</td><td>2.4</td><td>从底材脱开</td></tr><tr><td>喷砂</td><td>9.8</td><td>涂层剩离、黏合剂破坏</td></tr><tr><td>涂底漆</td><td>13.6</td><td>涂层剥离、黏合剂破坏</td></tr><tr><td rowspan=\"3\">铝</td><td>表面清洁</td><td>1.4</td><td>从底材剥离</td></tr><tr><td>喷砂</td><td>4.5</td><td>局部从底材剥离</td></tr><tr><td>涂底漆</td><td>5.2</td><td>局部从底材剥离</td></tr><tr><td rowspan=\"3\">混凝土</td><td>表面干燥</td><td>2.2</td><td>混凝土破坏</td></tr><tr><td>表面潮湿</td><td>1.4</td><td>从底材剥离</td></tr><tr><td>涂底漆</td><td>2.6</td><td>混凝土破坏</td></tr><tr><td rowspan=\"2\">木材</td><td>表面清洁</td><td>1.7</td><td>木材破坏</td></tr><tr><td>涂底漆</td><td>3.5</td><td>木材破坏</td></tr></table></body></html>  \n\n(2）耐交变压力性采用SPUA技术，在密度只有0.28g/cm的聚异氰尿酸酯-唑烷酮轻质、高强度泡沫表面，喷涂“SPUA-401超重防腐材料”，制备水下300m机器人用的“SSB-300固体浮力材料”。技术指标要求耐4.5MPa水压，不吸水，不变形。  \n\n极限打压试验结果发现，当过载压力增加至12MPa时，尽管高强度泡沫芯材已经被打疱、变形严重，但表面的SPUA封闭涂层仍然完整，没有丝毫破损和进水（图2-1-57、图2-1-58)。再继续进行加压、卸压疲劳试验，表层的SPUA材料仍完好无损，吸水率为零。  \n\n![](images/6f51d4ed1cfcd9d31849182f0035147a63b50b4594cc79d376c6c0fadb707752.jpg)  \n图2-1-57打压12MPa前的“SSB-300固体浮力材料”  \n\n![](images/89303027ad65c05f8e8e5a9dc011ce5fa9952648aa0e9e2db1187413f110e9a3.jpg)  \n图2-1-58打压12MPa后的“SSB-300固体浮力材料”  \n\n这表明，采用SPUA技术，能够对形状复杂的泡沫芯材进行整体包覆，所形成的新型固体浮力材料，具有厚度均匀、外观光顺、强度高、韧性好、耐疲劳变形、封闭性突出等特点。  \n\n(3）耐磨性聚脲弹性体被称为“耐磨橡胶”，具有优异的耐磨性，其耐磨性是碳钢的10倍，是环氧树脂的 $3{\\sim}5$ 倍。因此，SPUA技术特别适合用于经常有人员或车辆活动的工业重载地坪，加之SPUA材料具有良好的伸长率，其使用寿命比环氧地坪更长。聚脲弹性体还可用于解决各种环境下的耐磨损、抗冲击、防腐蚀等问题。  \n\n(4）耐冲击性（11个月，上万次冲击、碾压）为了考核 SPUA材料的耐疲劳冲击性，用大锤将一块 $500\\mathrm{mm}\\times1000\\mathrm{mm}\\times50\\mathrm{mm}$ 的钢筋混凝土板敲裂，在其表面喷涂 $3\\sim$ $4\\mathrm{mm}$ 的“SPUA-102防水耐磨材料”，放置于车辆进出的必经之地。经过近一年、上万次的车辆冲击、碾压，除了表面有轻微划伤迹象外，涂层至今完好，没有出现断裂、开裂和破损现象（图2-1-59)。它表明，SPUA材料具有非常优异的抗冲击、抗疲劳破坏的能力。  \n\n![](images/0d5fdbe6b148ec07b6c777d82a4eec48352d37a0cea55f6afda897979bcfc69e.jpg)  \n图2-1-59 SPUA材料耐冲击性试验  \n\n(5）耐疲劳破坏性在EVA不吸水泡沫芯材的外壁，喷涂“SPUA-601柔性防撞材料”进行包覆，然后放入万能材料试验机中，进行疲劳压缩试验，每次的压缩量为圆柱体原直径的1/2。在测试进行的100次疲劳压缩试验中，聚脲涂层仍能恢复到原来的形状，表面无任何开裂和破坏现象。  \n\n(6）耐 $15\\mathrm{m/s}$ 水流冲刷（1000h）首先，将 $100\\mathrm{mm}\\times250\\mathrm{mm}\\times1.5\\mathrm{m}$ $\\mathsf{5m m}$ 钢板表面经过喷砂除锈至 $\\mathtt{S a2.5}$ 级后，临时用D-31底漆封闭；其次，再在其表面喷涂 $75\\mathrm{mm}\\times170\\mathrm{mm}\\times$ $2,5\\mathrm{mm}$ （编号：2、3、4、5）和 $75\\mathrm{mm}\\times170\\mathrm{mm}\\times5\\mathrm{mm}$ （编号：6、7、8、9）的“SPUA-102防水耐磨材料”；最后，分别在聚脲涂层表面涂刷防污漆和船壳漆，数量各为4块（图2-1-60)，按照GB7789—1987方法进行耐 $15\\mathrm{m/s}$ 水流冲刷试验。  \n\n![](images/853d0f4f7dae8868bb535dc2e1ebc1a4505554153a3bc01236de2d939ca2e825.jpg)  \n图2-1-60耐 $15\\mathrm{m/s}$ 水流冲刷试验前的样板  \n\n![](images/551b1d5f14757aa66f48defeabd967533b1faf54f777a0b0f1c6cd5a312d31c2.jpg)  \n图2-1-61耐 $\\scriptstyle15m/\\mathbf{s}$ 水流冲刷试验后的样板  \n\n该试验方法规定旋转200h为一个周期。上述所有样板全部通过了五个周期（累计1000h）的高速水流冲刷试验，两种不同厚度的“SPUA-102防水耐磨材料”均完好无损；与之配套的防污漆、船壳漆附着良好（图2-1-61)。但是，由于高速水流的冲击和空泡腐蚀，在“SPUA-102防水耐磨材料”下面的 $1.5\\mathrm{{mm}}$ 厚的钢板表面，出现了严重的锈蚀，钢板边缘固定区域还出现了断裂现象。说明SPUA材料具有优异的耐水性、耐疲劳冲击性、耐腐蚀性，并且能够在苛刻的海洋工作环境下，与钢板有良好的附着力。  \n\n(7）耐空泡腐蚀性诸如水力发电机的涡轮、舰船螺旋桨等高速旋转、推进装置，当其运转起来后，局部的气体会产生“空化”现象。那些被压缩出来的气泡，随着高速旋转的叶轮被甩出来，犹如坚硬的金属颗粒击打在叶轮上，形成比其他腐蚀情况更为严重的“空泡腐蚀”。传统的叶轮防护都采用环氧树脂等刚性材料作为保护层，大量的气泡长时间冲击刚性材料，会造成蜂窝状孔洞，并逐渐将保护层磨损掉（图2-1-62)，对叶轮的使用寿命造成极大危害。  \n\n![](images/f968d2cd8c9ab9356c2d98b037e600a75dc08b204e67a79453627a2baa8e9fe1.jpg)  \n图2-1-62空泡腐蚀形成的蜂窝状孔洞  \n\n因此，在选择涡轮、螺旋桨等高速旋转装置表面的防护材料时，应杜绝以往硬碰硬的做法，而改用“以柔克刚”的策略，选择柔性材料的黏弹性来耗散冲击能量，是防止空泡腐蚀的有效措施。根据美国ASTM标准G32—2003的规定，分别对不同材料进行耐空泡腐蚀试验，结果见表2-1-236。  \n\n表2-1-236耐空泡腐蚀测试数据  \n\n\n<html><body><table><tr><td>材 质</td><td>试验时间</td><td>质献损失</td><td>损失</td><td>材 质</td><td>试验时间</td><td>质量损失</td><td>损失</td></tr><tr><td>环氧树脂</td><td>45</td><td>91</td><td>2.02</td><td>SPUA(2. 5mm)</td><td>600</td><td>9.4</td><td>0.016</td></tr><tr><td>乙烯基树脂</td><td>140</td><td>132.4</td><td>0.95</td><td>SPUA(1. 25mm)</td><td>600</td><td>7.3</td><td>0.012</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 425,
+        "chunk": "# 2.耐受性能  \n\n(1）耐介质性SPUA材料致密、连续、无接缝，其干燥、固化过程中，完全依靠的是化学反应，而不会像以往涂料的干燥过程中，需要向空气中挥发有机溶剂或者水分。因此就不会有针孔、气泡、缩孔等缺陷产生，实际上也就杜绝了外界腐蚀介质入侵的途径，所以防腐蚀性十分突出。同时，由于其优异的柔韧性，完全能够抵御昼夜、四季环境温度变化带来的热胀冷缩，不会产生开裂和脱落现象，使得SPUA材料表现出十分优异的耐化学介质性（表2-1-237)，在材料保护领域具有广泛的应用前景。  \n\n表2-1-237SPUA材料的耐介质性  \n\n\n<html><body><table><tr><td colspan=\"2\">介质名称</td><td>浸泡结果</td><td>介质名称</td><td></td><td>浸泡结果</td></tr><tr><td rowspan=\"5\">盐蒂液</td><td>饱和盐水（130000μg/L）</td><td>良好</td><td rowspan=\"10\">有机溶剂</td><td>苯</td><td>变色，发泡</td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td>好</td><td></td><td>变，发微变色</td></tr><tr><td></td><td>皮好</td><td></td><td></td></tr><tr><td rowspan=\"2\">酸</td><td colspan=\"2\"></td><td>良好</td></tr><tr><td colspan=\"2\"></td><td>内酮</td><td></td></tr><tr><td rowspan=\"15\">碱溶液</td><td>乙酸（10%）</td><td>良好</td><td rowspan=\"5\">三氧乙烧</td><td>变色，发泡</td></tr><tr><td>醋（乙酸）</td><td>良好</td><td></td><td>变色，发泡</td></tr><tr><td></td><td>变包、发腹</td><td>甲醇</td><td>变色，发泡</td></tr><tr><td>盐酸(5% 10%)</td><td></td><td>丙烷</td><td>轻微起皱</td></tr><tr><td>硫酸（5%，10%，20%)</td><td>良好</td><td>二甲基甲酰胺</td><td>变色，发脆</td></tr><tr><td>酸溶液 硫酸(50%)</td><td></td><td colspan=\"3\">汽油</td></tr><tr><td></td><td></td><td></td><td>矿物油</td><td>良好 良好</td></tr><tr><td>磷酸（50%）</td><td>变色，发脆</td><td rowspan=\"9\">其他溶剂</td><td>柴油</td><td>良好</td></tr><tr><td>氢氟酸</td><td>变色，发脆</td><td>液压油</td><td></td></tr><tr><td>柠橡酸</td><td>良好</td><td></td><td>良好</td></tr><tr><td></td><td></td><td>防冻液（50%乙醇）</td><td>良好</td></tr><tr><td>氨(水中的浓度仅为200g/L).。数变色</td><td></td><td>电机化肥</td><td>良好，轻微变色</td></tr><tr><td colspan=\"2\" rowspan=\"3\">氢氧化钠（5%，10%，20%） 良好</td><td></td><td></td></tr><tr><td>化肥（28-0-0)</td><td>良好</td></tr><tr><td>良好，轻微变色 硬脂酸</td><td>良好</td></tr><tr><td>氢氧化钠（50%） 氢氧化钾（10%）</td><td>良好</td><td>水</td><td>良好</td></tr><tr><td>氢氧化钾（20%）</td><td>良好，轻微变色</td><td>铬酸砷（工作溶剂）</td><td>良好</td></tr><tr><td>氨水（20%）</td><td>良好</td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr></table></body></html>\n\n注：1.未注明浓度的介质均为饱和溶液。2.样片在各介质中的浸泡时间均为1星期（24h×7天)，室温为 $25t$ ，测试方法见GB1763—1979。3.在规定的浸泡时间内，若样片无起泡、起皱、变色（允许轻微变色）现象，结果定为良好。  \n\n(2）耐浸泡性合理的配方设计和喷涂工艺参数控制，能够获得耐水、耐油长期浸泡的高性能SPUA材料。  \n\n(3）户外耐老化性由于聚脲特定的分子结构以及体系中不含催化剂，SPUA材料表现出优异的耐老化性。虽然在芳香族SPUA中会出现泛黄现象，但经过专门的配方设计，并添加适当的抗氧剂和紫外线吸收剂的聚脲材料不会粉化和开裂，脂肪族SPUA材料的耐老化性则更是无与伦比。  \n\n(4）耐核辐照性SPUA材料具有很好的耐核辐照性，在 $10^{3}\\mathrm{Gy}$ 中等剂量下，可以长期使用；在 $10^{5}\\mathrm{Gy}$ 较高剂量下，也不失为一种中等弹性的高分子材料，可进行有限条件的使用(表2-1-238)。 1  \n\n(5）耐阴极剥离性将涂有普通防锈底漆和SPUA-406管道防腐材料的样板，浸渍于设定电压为1.5V的电解质溶液中，经过60天的耐阴极剥离试验后，涂有SPUA-406管道防腐材料的样板无起泡、脱落、锈蚀现象，涂膜无法剥离，附着力良好（图2-1-63)。这种优异的耐阴极剥离性，与SPUA材料自身的力学强度以及对底材良好的附着力有关，使得该材料能够长期应用于海洋、地下钢结构设施的腐蚀环境中，达到终身免维护的功能。  \n\n表2-1-238耐核辐照试验结果  \n\n\n<html><body><table><tr><td rowspan=\"2\">材 质</td><td colspan=\"3\">拉伸强度/MPa</td><td colspan=\"3\">伸长率/%</td><td colspan=\"3\">撕裂强度/（kN/m）</td></tr><tr><td>参比样</td><td>10°Gy</td><td>10°Gy</td><td>参比样</td><td>10°Gy</td><td>10°Gy</td><td>参比样</td><td>10°Gy</td><td>10°Gy</td></tr><tr><td>1橘红</td><td>13.4</td><td>13.7</td><td>8.65</td><td>368</td><td>383</td><td>271</td><td>44.9</td><td>41.5</td><td>30.7</td></tr><tr><td>2中灰</td><td>9.6</td><td>8.9</td><td>6.9</td><td>339</td><td>329</td><td>246</td><td>54.0</td><td>55.8</td><td>44. 9</td></tr><tr><td>3紫红</td><td>13.6</td><td>11.9</td><td>6.9</td><td>385</td><td>382</td><td>248</td><td>62.9</td><td>61.8</td><td>48.0</td></tr><tr><td>4蛋黄</td><td>9.6</td><td>10.2</td><td>5.5</td><td>324</td><td>349</td><td>181</td><td>60.9</td><td>66.5</td><td>42.6</td></tr></table></body></html>\n\n注：°CoY射线辐射源；检测环境条件：温度11℃，相对湿度75%。  \n\n![](images/18595aaf5228ce0237e2d5845a2e906e863c383bf49163016742bf552c619648.jpg)  \n图2-1-63 耐阴极剥离试验  \n\n而涂有普通防锈底漆的样板，经过 $_{3\\sim5}$ 天即出现严重的鼓泡、脱落和腐蚀现象，与SPUA材料形成了鲜明的对比。  \n\n(6）耐低温性SPUA材料具有很好的低温韧性。这方面完全不像玻璃钢材料，虽然力学强度很高，但在低温条件下很脆，应用受限。（7）耐热氧老化性SPUA材料经过热氧老化后的拉伸强度和撕裂强度都有较大提高，断裂伸长率略有下降。实际上，热氧老化过程相当于对SPUA材料进行后期加热熟化，更有利于材料强度的提高。这一点不同于通常的硫化橡胶，在热氧老化后会造成其力学性能的下降（表2-1-239)。  \n\n表2-1-239热氧老化试验前后的性能变化  \n\n\n<html><body><table><tr><td>测试项目</td><td>老化前</td><td>老化后</td><td>测试项目</td><td>老化前</td><td>老化后</td></tr><tr><td>拉伸强度/MPa 伸长率/%</td><td>12.8 412</td><td>16.0 395</td><td>撕裂强度/（kN/m）</td><td>66.8</td><td>80.2</td></tr></table></body></html>  \n\n(8）耐海洋环境性海洋环境中钢结构和混凝土结构腐蚀防护问题一直是人们关注的热点。试验证明，聚脲材料具有优异的耐盐雾和耐海水腐蚀的能力，这种新型材料将在海洋腐蚀防护领域大显身手。  \n\n普通的管道防腐材料如熔结环氧粉末的耐盐雾试验一般不超过500h，实际使用寿命在10年以下。聚脲涂层由于致密、连续、无接缝，所以其耐盐雾性十分优异。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 426,
+        "chunk": "# 六、底材处理与施工工艺",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 427,
+        "chunk": "# 1.混凝土底材表面处理  \n\n清除混凝土表面杂质和缺陷的方法很多，国内外目前采用的有化学清理、碳氢化合物溶剂清理、蒸汽清理、化学剥离、抛丸处理、喷砂清理、耙路机处理、真空吸尘/压气吹洗、酸蚀和高压水冲洗等。施工时应根据工程的具体情况，选择合适的处理方法，使混凝土露出清洁、坚固的表面，应尽量避免锤击和粗琢，以免在混凝土表面以下约 $9\\mathrm{mm}$ 范围内形成开裂区。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 428,
+        "chunk": "# 2.钢材表面处理  \n\n（1）除油去除钢质底材表面的油污，可增强聚脲涂层的附着力。  \n\n除油（脱脂）主要是利用各种化学物质的溶解、皂化、乳化、润湿、渗透和机械等作用去除物体表面的油污，常用的材料主要是碱液、有机溶剂、清洗剂（脱脂剂）等，常用的清洗工艺主要有擦拭、浸泡、喷射、火焰、蒸汽等方法，此外还有超声波、电化学、辊简和机械喷砂等方法。  \n\n(2）除锈细致地去除钢铁表面的锈垢，以提高聚脲涂层的附着力，可延长其使用寿命。这一做法通过不断实践，已经获得公众的承认。常用的除锈方法有手工、小型机械（风动、电动)、喷（抛）丸（砂)、酸洗以及电化学和火焰等方法。各种除锈方式特征比较见表2-1-240。  \n\n表2-1-240各种除锈方式特征比较  \n\n\n<html><body><table><tr><td>除锈方式</td><td>优点</td><td>缺点</td><td>注意事项</td><td>处理</td><td>表面</td></tr><tr><td>喷丸</td><td>①除锈彻底； ②处理效：</td><td>①对环境有污染； 一般在室内进行大</td><td>操作时，应逮蔽其他相邻 物体</td><td>优</td><td>优</td></tr><tr><td>喷砂</td><td>①除锈彻底； 效整养种形状的表面，</td><td>①对环境污染极大； ②料不可进收其他作业</td><td>①操作时，应遮蔽其他相邻 采取必要措施，减少粉尘</td><td>优</td><td>优</td></tr><tr><td>真空喷丸</td><td>①钙环境</td><td>①不能处理形状复杂的 表除绣效率低</td><td>与其他小型工具配合使用</td><td>优</td><td>优</td></tr><tr><td>小型机械</td><td>①除锈彻底； 机动性好：</td><td>①除锈效率低，尤其是去除 化度技大</td><td>①根据不同对象选择相应的 工用于对旧漆面打毛处理</td><td>一般</td><td>较差</td></tr><tr><td>纯手工</td><td>①工具简便； ②机动性好</td><td>整度小； ③劳动强度大</td><td>主要用于小面积除铸和其他 工具难以达到的边角除锈</td><td>差</td><td>差</td></tr><tr><td>酸洗</td><td>①客种零部件</td><td>①酸雾和废水排放造成环境 不能用于度据和大型部件工放好方破保护相三度比理 ③易返锈，尤其是酸残留时</td><td>①重视酸洗后冲洗和干燥 工作</td><td>较好</td><td>较差</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 429,
+        "chunk": "# 3.有色金属的表面处理  \n\n铜、锌、铝等有色金属及其合金器件表面在喷涂聚脲前同样需要表面处理。材质不同，  \n\n表面处理方法也不同。  \n\n有色金属物件表面去除油污的方法基本与钢铁表面去油方法相同，但由于有色金属耐碱性差，不宜使用强碱性清洗液清洗，一般推荐采用有机溶剂除油、表面活性剂除油，或用由磷酸钠、硅酸钠配制的弱碱性清洗液。  \n\n为得到附着良好的表面，可采用手工或机械打磨、喷砂或酸洗方式处理表面，使其具有一定的粗糙度。通常采用表面化学处理在表面形成一层转化膜，不但可提高涂膜结合力，而且可提高涂层防腐蚀性。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 430,
+        "chunk": "# 4.木材的表面处理  \n\n$\\Phi$ 木材的干燥在木质基材上对附着力影响最大的首推湿度。新木材含有很多水分，并从潮湿空气中继续吸收水分，所以在施工之前，必须对木材的含水率进行严格控制，在喷涂或封闭处理前应用湿度计测量木材的含水率，一般室外用木材的含水率要求小于 $9\\%sim$ $14\\%$ ；室内用木材的含水率要求小于 $5\\%\\sim10\\%$ ；地板用木材的含水率要求小于 $6\\%\\sim9\\%$ 。所以喷涂前木材在室外过夜或雨淋湿后，湿度会上升，不宜进行涂装。木材的干燥方法一般采用自然干燥（自然挥发、风吹、日晒）或低温烘干两种。  \n\n$\\textcircled{2}$ 污物的清除和封闭基材表面的胶痕、油迹等污物，必须在涂装前完全除尽，可以采用砂纸、精刨、汽油、火燎等工具和方法进行清洁。当污物渗入木材管孔后，无法去除，可以用生胶、铝粉漆等封闭底漆进行处理。  \n\n$\\textcircled{3}$ 去松脂和封闭大多数针叶类树木木材中都含有松脂，尤其是在有木节的地方，它会严重影响涂层的附着和均匀性，在高温时，有较强的溢出性，清除方法一是挖补，将松脂用刀挖去，再补以相同材质、相同纤维方向的木材。二是用汽油、松节油、甲苯、丙酮、酒精等有机溶剂或 $5\\%$ 的烧碱清洗干燥后，涂剧 $_{1\\sim2}$ 道虫胶漆（可加人少量铝粉增强虫胶漆的封闭效果）等封闭底漆，封闭的范围要大于松脂部位的 $2.5\\mathrm{cm}$ 以上，以涂刷2道以上为佳。  \n\n$\\textcircled{4}$ 去毛刺在木制品表面有很多细微的木质纤维，它们吸潮后，会因膨胀而竖起，如果此时喷涂，由于聚脲快干的特性，涂层会在木毛上堆积、固化，表面会出现很多小疙瘩，使表观变差，影响涂层的均匀和光滑性。一般采用下述方法去除。  \n\na.用湿布擦拭表面（可以加入一点骨胶)，使毛刺竖起后用砂纸或研磨膏打磨。  \nb.在表面上刷上稀虫胶清漆 $(15\\%Z$ 醇溶液），毛刺竖起并发脆后打磨。  \nc.刷上一层乙醇，用火燎一下，使毛刺发脆后打磨。  \n\n$\\textcircled{5}$ 表面刨平及打磨用机械或手工进行刨平，然后开始打磨。首先将两块新砂纸的表面相互摩擦，以去除偶然存在的粗砂粒，然后再进行打磨，打磨的工具可用一小块长软木板 $(200\\mathrm{cm}\\times5\\mathrm{cm}\\times20\\mathrm{cm})$ 制成，板面胶黏上软的法兰绒、羊毛毡、软橡胶、泡沫塑料之类均可，然后裹上砂纸，打磨时用力要均匀一致。打磨完毕后用抹布擦净木屑等杂质。  \n\n$\\textcircled{6}$ 木材管孔的封闭木材表面，尤其是横断面，存在很多吸收性极强的木质管孔、孔槽、钉眼等孔洞，对潮气有很大的吸收能力，必须进行封闭。封闭的方法是根据底材孔眼的大小用松节油调出不同稠度的腻子进行刷、刮等处理，用砂纸打磨平整后再涂刷封闭底漆。也可以在腻子前先刷一道封闭底漆，以增强封闭腻子的附着力。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 431,
+        "chunk": "# 5.塑料、橡胶、玻璃钢等低表面能材料的表面处理  \n\n塑料常用的表面处理方法及特点见表2-1-241。  \n\n表2-1-241塑料常用的表面处理方法及特点  \n\n\n<html><body><table><tr><td>处理方法</td><td>效 果</td><td>药剂、工具</td><td>工艺条件</td><td>优点</td><td>缺点</td></tr><tr><td>溶剂清洗（蒸汽法）</td><td>去除油脂和增塑剂等</td><td>三氯乙烷</td><td>2min</td><td>自动化</td><td>效果一般</td></tr><tr><td>化学药品处理</td><td>引人极性基团</td><td>HSO • KCO, · HO</td><td>2min(70C)</td><td>适用面广</td><td>需三废处理</td></tr><tr><td>火焰处理</td><td>引人极性基团</td><td>氧化焰</td><td><10s</td><td>处理简单</td><td>易过度变形</td></tr><tr><td>打磨</td><td>增加表面粗糙度</td><td>砂布、喷砂等</td><td>1 ~3min</td><td>处理简单</td><td>产生灰尘</td></tr><tr><td>等离子处理</td><td>引入极性基团</td><td>电</td><td>10~30s</td><td>时间矩、效果好</td><td>设备费用高</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 432,
+        "chunk": "# 6.泡沫的表面处理  \n\n(1）EPS泡沫的表面处理  \n\n$\\textcircled{1}$ 首先检查泡沫表面，看表面是否有缺陷和小孔，如果有，用刮刀将配套修补腻子刮涂到小孔及缺陷中，修理平整。  \n\n$\\textcircled{2}$ 将修补的地方打磨平整，这一点十分重要。由于喷涂聚脲快速固化的特性，因此其原形再现性良好，即下面的底材是什么形状，喷出来就是什么形状。如果不能打磨平整，将会影响外观。  \n\n$\\textcircled{3}$ 将表面不需要的凸起部分打磨平整。  \n\n(2）PU（聚氨酯）泡沫的表面处理  \n\n$\\Phi$ 首先将表面的脱模剂用溶剂擦掉，可用二甲苯、酒精等。作为道具的聚氨酯泡沫一般是在模具中成型，聚氨酯对大多数材料都有很强的黏合性，包括金属材料在内，因此必须使用脱模剂。常使用的是高熔点微晶蜡或水溶液以及聚乙烯分散液，也有采用长效模具处理剂，如各种硅、氟树脂等。由于脱模剂都是一些低表面能物质，如果不进行处理，会影响聚脲涂层与泡沫的附着力。  \n\n$\\textcircled{2}$ 打磨泡沫表面，使表面的泡孔暴露出来。泡沫表面不可避免地会有一些孔洞，这是由于发泡而引起的，有些孔洞直接暴露在外，另外有些孔洞紧贴着表面，只有一层薄薄的表皮，需要进行打磨才能发现。打磨时一般不使用电动工具，以免控制不当损伤表面。通常使用砂纸进行手工打磨，将表面的泡孔彻底暴露出来。如果不这样处理，喷涂聚脲弹性体后会出现鼓泡现象，影响表面美观度。  \n\n$\\textcircled{3}$ 使用配套腻子修补泡沫表面。在打磨完成后进行修补，修补的部位包括打磨出的孔洞以及脱模时产生的缺陷，应尽量修补平整。  \n\n$\\textcircled{4}$ 打磨修补过的表面。打磨时应尽量平整，以免喷涂后影响表面美观度。打磨后可能会有一些新的泡孔暴露出来，已修补过的部位也可能会损坏，因此需要再次修补和打磨。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 433,
+        "chunk": "# 7.施工工艺  \n\n(1）混凝土底材  \n\n$\\textcircled{1}$ 新水泥底材应完全水化，干燥28天后，待水分充分挥发后才能进行施工，否则，其内部所积蓄的水分在受热后会挥发，导致涂层鼓泡。  \n\n$\\textcircled{2}$ 如前面混凝土底材处理及检测方法所述，进行底材处理及含水率检测，使混凝土底材表面无油污、灰尘及碎裂的水泥块等杂质。  \n\n$\\textcircled{3}$ 混凝土底材表面应保持干燥和完整。  \n\n$\\textcircled{4}$ 收头部位按图纸要求进行处理。  \n\n(2）金属底材处理如前面金属底材处理所述，选择合适的处理方法进行底材处理，然后按图纸要求对收头部位进行处理。  \n\n（3）底漆、堵孔料、密封胶的施工  \n\n①施工配套底漆。不要让底漆弄脏或者堵死收头部位的槽式结构。金属底材一般不需要底漆，如果喷涂SPUA材料用来作衬里，则金属底材表面需要涂刷底漆。  \n\n$\\textcircled{2}$ 堵孔料填充底材上的孔洞，要堵实，否则，SPUA固化过程中所释放的热量会使孔洞中的空气膨胀，造成涂层鼓泡。  \n\n$\\textcircled{3}$ 密封胶的施工。按施工图纸的要求施工密封胶：在施工根、孔、座、角等部位时，密封胶的剖面应是一个直角边为 $5\\mathrm{mm}$ 的直角三角形；施工其他部位时，按图纸要求过渡下来就可以了。  \n\n(4）SPUA材料的施工  \n\n$\\boldsymbol{\\Phi}$ 施工时机和施工方法尽量在增强层施工12h内施工SPUA材料，如超过12h，应打磨增强层，刷涂或喷涂一道层间黏合剂， $20\\mathrm{{min}}$ 后再施工SPUA涂层。施工SPUA涂层时，下一道要覆盖上一道的 $50\\%$ ，俗称“压枪”，同时下一道和上一道的喷涂方向要垂直，只有这样才能保证涂层均匀。施工前，底材上的渣子和杂物要尽量清理干净，可使用吸尘器进行清理。  \n\n$\\textcircled{2}$ 特殊工艺处理对于防滑要求较高的地方，可以在未干的涂层上人为造粒或手工铺撒防滑粒子（如橡胶粒、金刚砂等）。  \n\n人为造粒的具体操作如下：利用SPUA技术快速固化的原理，通过施工者对喷射角度和流量的控制，在最后一道涂层还没有完全固化前，在距离施工部位一定距离的地方，打开喷枪，让已混合雾化的喷涂料自由地降落在施工部位上，从而形成一定大小的颗粒，得到具有粗糙的防滑颗粒表面，起到防滑和消光（主要用于影视、娱乐业及室内灯光球场等场合）作用。人为造粒时应注意风向和风力，施工者应处于上风口，风力以3级以下为宜，以减小雾化粒子向施工人员和设备的飘落。  \n\n手工铺撒防滑粒子的具体操作如下：在最后一道涂层还没有完全固化之前，手工将防滑粒子均匀地抛撒在施工部位上，待涂层固化后，清扫撒防滑粒子的部位，将未粘上的防滑粒子清扫干净。  \n\n$\\textcircled{3}$ 平面施工对于平面施工，除注意压枪和喷涂方向外，还要注意及时清理底材上未处理干净的渣子以及喷涂过程中落到底材上的杂物。在每一道喷涂完毕后，马上进行检查，找到缺陷并进行处理。对于针孔和大的缺陷，使用快速固化的堵孔料进行修补；对于表面因杂质而造成的凸起，可用裁纸刀割除。一般处理两次后，表面已基本无缺陷。  \n\n$\\textcircled{4}$ 垂直面和顶面施工垂直面和顶面施工除进行以上步骤外，还要注意每道喷涂不要太厚，这既可以通过喷枪、混合室、喷嘴的不同组合来控制，也可以通过控制枪的移动速度来进行。  \n\n$\\textcircled{5}$ 复杂面的施工像雕塑、道具、标本、护舷等复杂构件，需要有特殊的施工工艺。下面以小型护舷（直径小于 $800\\mathrm{mm}$ ）为例，阐明其加工方法。加工芯材时要在其中一端中心的部位留出一个圆柱孔，直径和深度为 $100\\mathrm{{mm}}$ ，以便用特制的叉子插入孔中，然后用专门的旋转装置将叉子连同护舷一起转动，同时进行喷涂。  \n\n（5）面漆施工芳香族SPUA材料经紫外线照射后会出现泛黄现象，这对有浅色要求的场合是不利的，因此，建议涂刷相应的耐黄变面漆。涂刷面漆应在SPUA涂层施工12h内进行。如果超过12h，应打磨SPUA涂层，刷涂或喷涂一道层间黏合剂，然后再施工面漆。  \n\n(6）修补SPUA材料本身的力学性能十分优良，正常使用时，一般不会损坏。一旦出现意外损坏（如重物砸落、撞击等)，可用SPUA-202S修补料进行局部修补。具体步骤如下。  \n\n$\\Phi$ 打磨待修补的表面，打磨的边缘要比待修补的表面向外扩展 $150\\mathrm{mm}$  \n\n$\\textcircled{2}$ 施工层间黏合剂。  \n\n$\\textcircled{3}$ 在已打磨的部位施工修补料。要注意使修补料的涂层平滑过渡到周围涂层。  \n\n$\\textcircled{4}$ 对于特殊应用，施工与之相匹配的面漆。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 434,
+        "chunk": "# 七、安全防护",
+        "category": " Introduction"
+    },
+    {
+        "id": 435,
+        "chunk": "# 1.施工防毒  \n\nSPUA技术采用的化学原料如异氰酸酯（及A组分）、端氨基聚醚（及B组分）都带有一定的毒性，在喷涂施工中如果不注意安全与防护，很可能会造成施工人员出现一些不良症状。  \n\nSPUA所用的A 组分通常是 MDI或LMDI或 PAPI的半预聚体（quasi-prepolymer)，含有大量的未反应异氰酸酯单体，对眼睛、呼吸系统和皮肤均有一定的损害。  \n\n$\\Phi$ 呼吸系统对呼吸道有刺激作用，是一种潜在的呼吸道过敏源。吸入一定量的气体或浮游物会引发呼吸道感染，并对肺造成损伤，并可能会伴有喉干、胸闷、呼吸困难和/或类似感冒的症状。  \n\n$\\textcircled{2}$ 皮肤接触可能会造成皮疹、红肿、刺疼、化学灼伤，反复或长时间接触会造成皮肤过敏。动物试验的研究结果可以在一定限度内证明皮肤接触可能会引起呼吸道过敏。  \n\n$\\textcircled{3}$ 眼睛接触浮游物、蒸气或液体会对人眼产生刺激，严重的可引起眼睛的化学灼伤。  \n\n(1）喷涂聚脲弹性体生产及施工时安全防护由于喷涂施工时物料温度较高（一般在$60\\ensuremath{\\mathbb{C}}$ 左右)，又存在飞溅，因此施工人员一定要做好个人安全保护。  \n\n$\\textcircled{1}$ 眼睛的保护喷涂过程中可能接触其气雾时，应该佩戴化学安全护目镜。  \n\n②呼吸系统的保护喷涂过程中会产生大量的气雾，将对呼吸道有一定刺激性，故施工时，施工人员应佩戴经认证的呼吸防护设备。  \n\n$\\textcircled{3}$ 皮肤的保护因喷涂时飞溅的气雾固化后形成的微小颗粒物易沾附到施工人员的皮肤、头发及衣物鞋袜上，虽不会造成伤害，但却不易清除，故仍须对身体采取必要的防护措施。对于手的防护可佩戴化学品手套，如氯丁橡胶、丁腈橡胶、丁基橡胶手套等。对于脚的防护则可以采取直接将塑料或布制鞋套套于所穿鞋外部的方法，此外也可以穿耐化学药品的长简靴。对于身体的防护则应外穿一般的连体式防护工作服。  \n\n(2）急救措施如果生产或施工人员感觉到任何不适，应立即查询药物建议（如果可能，展示材料安全数据)。  \n\n$\\Phi$ 吸入将病人从现场撤出，让其在温暖处休息。接受药物治疗。治疗主要针对严重发炎或呼吸困难。如果呼吸十分困难，应在专业人员的照料下吸氧。在呼吸停止或即将停止的情况下，要进行人工呼吸抢救。  \n\n$\\textcircled{2}$ 皮肤接触替换受污衣物，用水和肥皂彻底清洗受污的地方。如果有发炎、发红或灼烧感等情况发生并持续，应进行药物治疗。在受污的衣物再次使用前，应彻底清洗干净。  \n\n$\\textcircled{3}$ 眼睛接触立即用流动性水冲洗眼睛 $15\\mathrm{{min}}$ 以上，冲洗时撑开眼帘。如果发炎不消除，应反复冲洗，并立即接受药物治疗。  \n\n$\\textcircled{4}$ 摄入不要采用呕吐方法。保持病人一直处于清醒状态，先漱清口腔，然后再喝1～2 杯水。并向专业医务人员请求迅速的药物治疗。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 436,
+        "chunk": "# 2.施工防火防爆  \n\nSPUA技术采用的是低温（施工温度不超过 $70\\Upsilon$ ）施工喷涂技术，所用原材料 $100\\%$ 固含量，无挥发性成分。因此它不像其他涂料一样，施工过程中伴随着大量溶剂的挥发，在涂装场所的高温、明火、冲击火花、电火花、静电等都可能引起这些易燃物质燃烧。SPUA材料的出现大大减轻了这些危害，是涂料涂装技术的一项重大革新。但是为了安全施工，还是需要一些防范措施，防患于未然。  \n\n（1）杜绝火源在室内喷涂以及室外的工作区域内，必须做到严禁吸烟，禁止携带火种(如火柴、打火机)。严禁任意使用明火和易于燃烧的用具及装置。  \n\n（2）施工场所保证良好的通风在室内喷涂时，每次喷涂完毕都要采用特定的清洗剂对喷枪进行清洗，而喷枪清洗剂是一种易挥发溶剂，具有挥发、易燃、易爆特性。  \n\n溶剂在室内挥发与空气混合后，达到一定温度时，遇火种就会引起突然闪光（初次开始闪光时的温度，称为闪点)。如果温度比闪点高，溶剂蒸气遇火种就会引起燃烧。如果溶剂蒸气与空气混合达到一定浓度，遇火种就会爆炸。  \n\n在室内施工时，必须注意保证通风良好。控制施工现场溶剂蒸发浓度不得越过规定标准；严禁溶剂接触高温，以防止接触温度高于该种溶剂闪点时遇明火引起燃烧。  \n\n施工场所良好的通风条件还可以将有害挥发物质及时带走，有利于施工人员的身体健康。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 437,
+        "chunk": "# 第十节氯化聚烯烃树脂及应用  \n\n氯化聚烯烃树脂泛指主链为氯原子部分取代的脂肪烃树脂（chlorinatedpolyalefine res-in，CPR)。主要品种有：氯化橡胶（CR)、氯磺化聚乙烯（CSPE)、过氯乙烯（HPVC)、高氯化聚乙烯（HCPE)、氯化聚丙烯（CPP)、氯化乙烯-醋酸乙烯共聚物（CEVA）以及氯乙烯-乙烯基异丁基醚共聚物等。含氯聚合物大分子中引入了氯元素，构成了极性较大的C—CI键，具有优良的耐候性、耐臭氧、耐化学介质（酸、碱、盐）性及一定的耐脂肪烃溶剂和成品油、润滑油性等，可用于制备单组分涂料，施工方便，不受施工环境影响。因此它广泛地应用于防腐涂料；同时CPR对低表面能的塑料具有优良的附着力，也适用于一些装饰涂料领域。  \n\n经过半个世纪的发展，CR、CSPE、HPVC、HCPE、MP等含氯树脂已形成系列化的防腐涂料、装饰涂料产品，并有国家或行业的标准，在船舶、石油化工等重防腐领域形成了较为完整的产品配套体系。但随着人们环境保护意识的增强，卤代化合物对人体健康的“三致”效应以及卤代化合物对大气平流层中臭氧的破坏越来越引起人们的关注。如何减少使用或者替代卤代化合物的使用已经成为环保界、工商企业界以及政府等最为关心的课题之一。《蒙特利尔议定书》等ODS的相关法规中，明确了对卤代化合物的限制和淘汰计划；欧盟于2005年通过了关于限制使用含氯类溶剂使用的提案。诸多法律法规的设定对相关工业的发展提出了挑战。氯化聚烯烃树脂及涂料因为其具有独特的防腐性能而尚无法完全替代。  \n\n下面就氯化聚烯烃树脂的品种分别加以介绍。",
+        "category": " Introduction"
+    },
+    {
+        "id": 438,
+        "chunk": "# 一、氯化橡胶",
+        "category": " Introduction"
+    },
+    {
+        "id": 439,
+        "chunk": "# 1.氯化橡胶的制备及特点  \n\n(1）氯化橡胶的制备氯化橡胶由天然橡胶经过炼解或合成异戊二烯橡胶溶于四氯化碳中，通入氯气反应而成。在氯化反应过程中有加成、取代和环化反应。为了使橡胶中的双键饱和，以免老化降解，必须通入足够多的氯使其含氯量达65%左右。所以原先的橡胶是弹性体，而制成的氯化橡胶则是脆硬的白色多孔性固体物质。除溶剂法，还有水相法、固相法和乳液法，通常含氯量在 $60\\%\\sim67\\%$ 。其化学结构示意如下：  \n\n![](images/f8142865e08709c03194195d9a9b08057ccde2ef4226c3e060ddc4a2531bf677.jpg)  \n\n$\\textcircled{1}$ 溶剂法传统的溶剂法制备氯化橡胶是将橡胶切块，于 $50\\mathrm{{^{v}C}}$ 左右烘干排除水分和预热，经过双辊机和轧片塑炼切片后，按 $4.5\\%$ 浓度的比例投入装有四氯化碳溶剂的专用反应釜中，在 $20^{\\circ}\\mathrm{C}$ 以下的较低温度中碘催化剂存在下通入氯气进行氯化反应。同时经过反应釜的冷凝器、吸收塔不断吸收氯化氢得副产物盐酸。通氯气直到产物含氯量达到 $62\\%$ 以上，而且氯化氢停止产生为止。将反应产物溶液经过中间贮槽后再喷射（雾化）进入 $80\\sim90^{\\circ}\\mathrm{C}$ 的热水沉淀锅中，氯化橡胶则呈细粉末状沉于热水中，而四氯化碳（沸点 $75.50$ ）受热气化，由冷凝器回收循环利用。将沉淀物（氯化橡胶）送入离心机用清水洗涤数次，以除净其残剩的氯化氢至中性时再离心脱水，经过烘廊干燥，压缩、包装、人库。  \n\n$\\textcircled{2}$ 水相法20世纪80年代以来，四氯化碳对臭氧层的破坏及对人体有致癌作用引起全球的关注。1995年在联合国主持下通过了蒙特利尔公约，各国加紧了对氯化橡胶生产中四氯化碳释放量的控制，给含氯聚合物的生产企业和涂料行业带来巨大的冲击。目前世界各主要防腐涂料生产国都在花大力气进行含氯聚合物新技术、新工艺的研究。水相法氯化橡胶生产工艺就是在这种形势下发展起来的。  \n\n水相法氯化橡胶的制备就是采用天然橡胶乳液作为原料，加入适量助剂，排除蛋白质、脂肪酸和糖分等杂质，然后用浓盐酸水溶液进行酸化处理至一定 $\\mathbf{\\pH}$ 值， $20\\sim40^{\\circ}C$ 下通人氯气进行氯化反应一定时间，再在催化剂作用下， $40\\sim70^{\\circ}C$ 深度氯化，通氯气直到产物含氯量达到 $60\\%$ 以上。将反应产物溶液经过水洗脱酸。将沉淀物（氯化橡胶）送人离心机用清水洗涤数次，以除净其残剩的氯化氢至中性时再离心脱水，经过烘廊干燥，压缩、包装、入库。  \n\n$\\textcircled{3}$ 固相法将100份天然橡胶和400份硫酸钠磨碎混合，在耐压容器中， $20\\sim25\\Upsilon$ 下用液氯氯化8h后，将氯化产品水洗除盐，可得到成品，固相氯化反应控制困难，工业化意义不大。  \n\n$\\textcircled{4}$ 乳液法将天然橡胶与氯气加压分散于次氯酸钠溶液中，配成 $70\\%$ 的乳液，通氯气4h后冷却加人 $20\\%$ 氢氧化钠溶液（含氯 $6\\%$ ，得到悬浮液。此时固体物氯含量为 $54\\%\\sim$ $56\\%$ 。再通氯气 $2\\sim3\\mathrm{h}$ 后，洗涤、过滤、干燥，即得氯含量为 $62\\%\\sim65\\%$ 的氯化橡胶。此法反应体系稳定性差，且为非均相反应，存在胶粒内外氯化不均匀问题，产品稳定性差，因而工业生产也很少采用。  \n\n(2）氯化橡胶的特性氯化橡胶为无毒、无味、对人体皮肤无刺激性的白色粉末或细片状固体，溶液黏度因橡胶降解程度而异。  \n\n$\\textcircled{1}$ 吸水率低，约为 $0.1\\%\\sim0.3\\%$ （相对湿度 $80\\%$ ，24h)$\\textcircled{2}$ 易溶于芳烃、卤烃、酯类和酮类，脂肪烃是其稀释剂。$\\textcircled{3}$ 相对密度 $1.50{\\sim}1.65$ ，酸值 ${\\leqslant}0$ $2\\mathrm{mgKOH/g}$ 。  \n\n涂膜特性如下。  \n\n$\\textcircled{1}$ 由于分子结构规整、饱和、极性小，无活性化学基团，故涂膜化学稳定性高，耐酸、碱、盐、氯化氢、硫化氢、二氧化硫等化学品侵蚀，但不耐浓硝酸和氢氧化铵；长期与动物油、植物油和脂肪接触，涂膜软化和膨胀。  \n\n$\\textcircled{2}$ 对光、热不稳定， $130^{\\circ}\\mathrm{C}$ 以上时开始分解，在潮湿条件下 $60^{\\circ}\\mathrm{C}$ 就开始分解，所以使用温度低于 $60^{\\circ}\\mathrm{C}$ 。即使达 $200^{\\circ}\\mathrm{C}$ 以上也不熔、不软化、不燃烧，仅继续分解。  \n\n$\\textcircled{3}$ 与大部分合成树脂相比，水、水蒸气通过率低，抗渗透性好。  \n\n$\\textcircled{4}$ 无毒、快干、单组分、不受施工温度限制。  \n\n$\\textcircled{5}$ 附着力好，无层间附着问题。  \n\n$\\textcircled{6}$ 含氯量高，因此阻燃性好，且在潮湿条件下可防霉。  \n\n$\\textcircled{7}$ 氯化橡胶能和多种树脂混溶，如醇酸、环氧酯、环氧、煤焦沥青、热塑性丙烯酸以及乙烯-醋酸乙烯共聚树脂（EVA）等，以改进其柔韧性、耐候、耐腐蚀性等。  \n\n$\\textcircled{8}$ 单独用于涂料时，涂膜较脆，制漆时需加入增塑剂或其他塑性好的树脂，低分子量的增塑剂，如氯化石蜡、氯化联苯，或邻苯二甲酸酯类，常因其往表面迁移和亲水性而影响涂层性能。  \n\n$\\textcircled{9}$ 合成氯化橡胶时采用四氯化碳作溶剂，其成品也往往含有一定量的游离的四氯化碳，破坏大气中的臭氧层，目前从世界范围内正在禁止溶剂法的氯化橡胶的生产。正在大力发展水相法的氯化橡胶，但水相法氯化橡胶较溶剂法的氯化橡胶的性能尚有--定的差距。  \n\n氯化橡胶自问世以来，国外有较多品种，主要牌号如下。  \n\n英国：ALLOPRENE 日本：ADEKA德国：PERGUT 德国：CHLORFAN美国：PARLON 意大利：CLORTEX  \n\n规格也较多，原来如ICI公司（英国帝国化学公司）根据黏度分为6个规格。参见2-1-242。  \n\n表2-1-242ICI公司对氯化橡胶的分类  \n\n\n<html><body><table><tr><td>品种</td><td>黏度/mPa•s</td><td>主要用途</td><td>品种</td><td>黏度/mPa • s</td><td>主要用途</td></tr><tr><td>R-5</td><td>4~6</td><td>高固体分油漆油墨用</td><td>R-40</td><td>36~44</td><td>特种刷涂漆黏合剂用</td></tr><tr><td>R-10</td><td>9~12</td><td>喷涂漆和厚浆型漆用</td><td>R-90</td><td>85~119</td><td>特种刷涂漆黏合剂用</td></tr><tr><td>R-20</td><td>18~22</td><td>制刷涂漆用</td><td>R-125</td><td>120~180</td><td>特种黏合剂，耐水耐火用</td></tr></table></body></html>\n\n$\\Phi$ 系20%甲苯溶液，以毛细管黏度计于25℃测定。  \n\n随着蒙特利尔公约的实行，西欧原有的英国、意大利等国溶剂法氯化橡胶生产装置都已关闭，只有德国的Bayer公司还在采用溶剂法生产氯化橡胶，但Bayer公司的生产装置也进行了改进，与原方法不同点在于氯化结束后不是用传统的水洗分离或喷雾干燥，而是利用氯化橡胶在甲苯中的溶解度更大，将甲苯加入反应好的氯化液中，然后利用四氯化碳与甲苯的沸点不同把四氯化碳蒸馏出来，经处理后再回收利用，能满足蒙特利尔公约的要求。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 440,
+        "chunk": "# 2.氯化橡胶涂料的组成  \n\n由于氯化橡胶有许多特点，因此氯化橡胶涂料仍然是目前重防腐涂料的一个重要品种。  \n\n（1）成膜物氯化橡胶可以与多种树脂混溶，因此可以组成不同的复合体系，满足其不同需要。可以与氯化橡胶混溶的树脂有中长油度醇酸树脂、聚氨酯树脂、氧树脂、氯化联苯、松香、甘油松香酯、季戊四醇松香酯、顺丁烯二酸酐改性甘油松香酯、丙烯酸树脂、酚醛树脂、烯树脂、环氧树脂等。  \n\n(2）溶剂氯化橡胶能溶于芳香烃、氯化烃、酯类及酮类等溶剂，脂肪烃是其稀释剂。对溶剂的选择是很重要的，同一种聚合度（分子量）的氯化橡胶在不同溶剂中所形成溶液的黏度差别很大。2氯化橡胶在不同溶剂中的黏度见表2-1-243。  \n\n选择溶剂应从技术要求（生产、贮存性、施工和成膜性能)、环境因素及其他因素来考虑。氯化橡胶漆中常用的混合溶剂是二甲苯：200号煤焦溶剂：200号溶剂汽油 $=45:40:15$ 票其中200号溶剂汽油加入具有一定的降低新涂层对底层干膜的溶解作用，从而在一定程度上改进了漆的涂刷和重涂性，即可减轻咬底的病。  \n\n表2-1-2432氯化橡胶在不同溶剂中的黏度  \n\n\n<html><body><table><tr><td>溶剂品种</td><td>黏度/mPa•s</td><td>溶剂品种</td><td>黏度/mPa·s</td></tr><tr><td>甲乙酮</td><td>13</td><td>甲基异丁酮</td><td>20</td></tr><tr><td>甲苯</td><td>18</td><td>200号煤焦溶剂</td><td>30</td></tr><tr><td>二甲苯</td><td>19</td><td>200号溶剂汽油·煤焦溶剂=1:4</td><td>34</td></tr><tr><td>乙酸乙酯</td><td>19</td><td></td><td></td></tr></table></body></html>\n\n①20%浓度，25℃奥氏计测，  \n\n（3）颜、填料与一般涂料所用颜、填料用法相似，不详细介绍。  \n\n(4）助剂  \n\n$\\Phi$ 增塑剂氯化橡胶的涂膜呈脆性，要制备涂料，一般都要添加增塑剂。正确选择和添加增塑剂对于改变涂膜的性能有着非常重要的作用。由于氯化橡胶是情性树脂，因此对增塑剂的要求是增塑效果明显和能够基本上接近氯化橡胶的性能(呈情性)，以保证基料的稳定。因为许多增塑剂都能与氯化橡胶相容，所以选择的范围较广。例如：氯化石蜡、邻苯二甲酸二丁酯、邻苯二甲酸二辛酯、磷酸三甲酚酯、磷酸二苯基酯和干性油（亚麻仁油、桐油、豆油和环氧化豆油）等。其中以氯化石蜡应用最广泛，因为它除了具备上述要求外还具有极佳的颜料润湿性和分散性，与其他涂料用树脂的混溶性以及优良的耐化学品性能等。因此，氯化石蜡是氯化橡胶类漆中最广泛使用的增塑剂。另外需耐候性好的面漆中，也可选用邻苯二甲酸酯作为增塑剂。  \n\n氯化橡胶与氯化石蜡的比例对涂膜的拉伸强度、伸长率、柔韧度、水蒸气渗透性及附着力等性能均有很大的影响（见表2-1-244)。要得到能够使各项性能最好的平衡，最适宜的比例范围是很窄的。  \n\n表2-1-244增塑的氧化橡胶薄膜的水蒸气渗透性  \n\n\n<html><body><table><tr><td>配比</td><td rowspan=\"2\">90 · 10</td><td rowspan=\"2\">801 20</td><td rowspan=\"2\">70  30</td><td rowspan=\"2\">65 · 35</td><td rowspan=\"2\">60 · 40</td></tr><tr><td>增塑剂品种</td><td></td></tr><tr><td>氯化石蜡（CP-42）</td><td>3.0</td><td>2.98</td><td>4</td><td>6.1</td><td>5.6</td></tr><tr><td>氯化石蜡（CP-52)</td><td></td><td>3.4</td><td>3.3</td><td>3.5</td><td>3.8</td></tr><tr><td>邻苯二甲酸二辛酯</td><td>3.5</td><td>4.0</td><td>9.8</td><td>16.3</td><td></td></tr><tr><td>邻苯二甲酸二丁酯</td><td></td><td>21.5</td><td>21.5</td><td></td><td>24.9</td></tr></table></body></html>\n\n$\\Phi$ 单位为 $\\scriptstyle10^{-\\gamma}\\mathbf{k}_{\\mathbf{g}}/(\\mathbf{m}^{2}\\cdot\\mathbf{s})$ （干膜厚 $25\\mu\\mathrm{m})$  \n\n$\\textcircled{2}$ 稳定剂氯化橡胶是高度氯化的聚合物，若漆液中存在有铁离子或含有铝、铜及其他氯化物（除氯化铝、氯化铜以外）等物质，则在贮存过程中漆液因受较高温度、水分等的作用，往往会发生化学反应生成如氯化铝、氯化铁等产物，放出氯化氢气体，并在分子中形成双键而发生交联，放出热量促使漆液温度升高，黏度迅速增加直至凝胶。为了保证漆液的贮存稳定性，生产配方中必须加入稳定剂，如氧化锌、氧化镁、环烷酸锌溶液、低碳酸钡、低分子环氧树脂、环氧化豆油、环氧氯丙烷、二月桂酸二丁基锡、顺丁烯二酸二丁基锡等物质。其用量一般为颜料量的 $1\\%$ 查 Y  \n\n$\\textcircled{3}$ 防沉剂为了防止和改善氯化橡胶色漆内颜料的沉淀结块，漆液内应添加 $0.5\\%$ 以内的防沉剂，如有机膨润土、气相二氧化硅、氢化麻油等，其中氢化麻油有明显的增厚防沉效用。  \n\n为了改善氯化橡胶漆的施工、成膜性能和增加每道涂膜厚度，在配制厚膜型漆时常采用酰胺改性氢化麻油作为触变剂。而且使用了触变剂后则不必再使用其他的防沉剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 441,
+        "chunk": "# 二、氯磺化聚乙烯",
+        "category": " Introduction"
+    },
+    {
+        "id": 442,
+        "chunk": "# 1.氯磺化聚乙烯的制备及特点  \n\n氯磺化聚乙烯是由分子量20000左右的高压聚乙烯溶解于四氯化碳，在偶氮二异丁睛的作用下与氯、二氧化硫进行氯化和磺化制得，反应产物的结构式是：  \n\n氯磺化聚乙烯含硫量为 $1.2\\%\\sim1.5\\%$ ，含氯量为 $26\\%\\sim29\\%$ ，相对密度为1.12，杜邦公司商品名为海泊隆（HAPOLON)，聚乙烯的主链上每7个碳原子才有一个氯原子。大约每 $84\\sim90$ 个碳原子中有一个氯磺酰基。分子结构中有氯原子可增强涂膜的抗油性、耐燃、耐溶剂性及提高物理机械性能等。而氯磺酰基的存在可使聚合物在铅或其他金属氧化物作用下易于发生交联。由于氯磺化聚乙烯是聚乙烯的衍生物，是以聚乙烯作主链而不含双键结构的完全饱和型橡胶，因而与其他饱和型橡胶一样，耐气候性、抗老化性、耐臭氧性及耐化学品性，尤其是能耐氧化剂的性能远优于含有双键结构的不饱和型橡胶。氯磺化聚乙烯橡胶在低温下也能形成柔软的薄膜，此薄膜的透湿性和透气性明显地低于其他的大部分弹性体。因此可以配制成涂料，涂装于各种织物、纤维制品、泡沫制品等表面作为防护涂层。",
+        "category": " Introduction"
+    },
+    {
+        "id": 443,
+        "chunk": "# 2.氯磺化聚乙烯橡胶漆  \n\n氯磺化聚乙烯橡胶漆是由固化剂与氯磺酰基反应交联而固化的。固化剂一般为氧化铅、氧化锰、氧化镁、三碱式马来酸铅、二酚基丙烷等联苯酚与六亚甲基四胺的缩合物、胺环氧加成物、聚酰胺树脂、氢化松香、芳烃二胺、二氰乙基化六亚甲基二胺、聚甲基氮硅烷、含氮有机硅化合物等。  \n\n涂料的特性与固化剂的关系见表2-1-245。  \n\n表2-1-245涂料的特性与固化剂的关系  \n\n\n<html><body><table><tr><td>固化剂种类</td><td rowspan=\"3\">一氧化铅</td><td rowspan=\"3\">碱式马来酸铅</td><td rowspan=\"3\">氧化镁</td><td rowspan=\"3\">环氧树脂</td><td rowspan=\"3\">聚酰胺</td></tr><tr><td>特性</td></tr><tr><td></td></tr><tr><td>耐水性</td><td>10</td><td></td><td>1</td><td>8</td><td>5</td></tr><tr><td>耐热性</td><td>8</td><td>8</td><td>10</td><td></td><td>7</td></tr><tr><td>耐化学品性</td><td>10</td><td>8</td><td>5</td><td>10</td><td>7</td></tr><tr><td>贮存稳定性（单组分）</td><td>7</td><td>10</td><td>1</td><td>9</td><td>1</td></tr><tr><td>干燥速度</td><td>9</td><td></td><td>8</td><td>7</td><td>10</td></tr><tr><td>对白色保色性</td><td>6</td><td>9</td><td>10</td><td>9</td><td>9</td></tr><tr><td>保色性</td><td>4</td><td>9</td><td>10</td><td>7</td><td>8</td></tr><tr><td>耐硫化物腐蚀性</td><td>3</td><td>5</td><td>10</td><td>10</td><td>10</td></tr><tr><td>澄清度</td><td>2</td><td>2</td><td>3</td><td>10</td><td>10</td></tr><tr><td>分散性</td><td>5</td><td>6</td><td>7</td><td>9</td><td>10</td></tr></table></body></html>\n\n注：10-优秀；1=差。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 444,
+        "chunk": "# 3.氯磺化聚乙烯橡胶漆参考配方  \n\n（1）氯磺化聚乙烯灰色磁漆（双组分）  \n\n(2）氯磺化聚乙烯黑色防腐蚀漆   \n\n\n<html><body><table><tr><td>甲组分</td><td>含量/%</td><td>乙组分</td><td>含量/%</td></tr><tr><td>氯磺化聚乙烯H-20 二甲苯 石油溶剂 丁醇</td><td>44.5 38.0 14.3 3.2</td><td>氧化铅 金红石型钛白 炭黑 沉淀硫酸钡 硫基咪唑 双甲苯胍</td><td>15.5 13.0 0.2 16.3 1.0</td></tr><tr><td>合计</td><td>100</td><td>氢化松香 二甲苯 石油溶剂 合计</td><td>4.0 34.7 13.3 100</td></tr></table></body></html>  \n\n<html><body><table><tr><td>甲组分</td><td>含量/%</td><td>乙组分</td><td>含量/%</td></tr><tr><td>氯磺化聚乙烯H-20 邻苯二甲酸 酸性陶土</td><td>48.2 0.8 1.0</td><td>炭黑 氧化铅</td><td>16.8 18. 0</td></tr><tr><td>1%甲基硅油二甲苯液 二甲苯</td><td>1.6</td><td>酸性陶土 二硫化二苯井噻唑</td><td>1.5 0.5</td></tr><tr><td>石油溶剂 丁醇</td><td>40. 0 3.7 4.7</td><td>双甲苯胍 氢化松香 二甲苯</td><td>0.7 4.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 445,
+        "chunk": "# 三、过氯乙烯",
+        "category": " Introduction"
+    },
+    {
+        "id": 446,
+        "chunk": "# 1.过氯乙烯的制备及特点  \n\n过氯乙烯是将聚氯乙烯溶解于氯苯中再通入氯，使含氯量达 $64\\%$ 左右，即每3个氯乙烯分子中添1个氯原子。原先的聚氯乙烯不溶于酯类等溶剂，经再氯化后，降低了聚氯乙烯的规整性，使过氯乙烯能溶解于酯、酮及芳烃等溶剂中，便于制成涂料，过氯乙烯不含双键，而其侧基氯原子的体积小，高分子之间距离近，所以其膜致密，耐化学腐蚀优良，耐大气老化性也好。但因它的结构较氯化橡胶规整，所以涂膜的附着力差，必须有配套的底漆。过氯乙烯的溶解度低，所制涂膜薄，需涂多道才能达到所需厚度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 447,
+        "chunk": "# 2.过氯乙烯防腐蚀涂料的配方  \n\n过氯乙烯防腐蚀涂料配方见表2-1-246。  \n\n表2-1-246过氯乙烯防腐蚀涂料配方  \n\n\n<html><body><table><tr><td rowspan=\"2\">组分</td><td colspan=\"5\">质量分数/%</td></tr><tr><td>铁红底漆</td><td>锌黄底漆</td><td>清漆</td><td>白磁漆</td><td>红磁</td></tr><tr><td>过氯乙烯树脂</td><td>9.3</td><td>14.1</td><td>12.00</td><td>10.24</td><td>10.00</td></tr><tr><td>邻苯二甲酸二丁酯</td><td>2.9</td><td>4.7</td><td>1.25</td><td>2.49</td><td>2.68</td></tr><tr><td>五氯联苯</td><td></td><td></td><td>1.25</td><td></td><td></td></tr><tr><td>磷酸三甲酚酯</td><td></td><td></td><td>1.00</td><td></td><td></td></tr><tr><td>中油亚麻油醇酸</td><td>5.0</td><td>6.0</td><td></td><td>4.25</td><td>4.00</td></tr><tr><td>环氧氯丙烧</td><td></td><td></td><td>0.40</td><td></td><td></td></tr><tr><td>麻油酸钡</td><td></td><td></td><td></td><td>0.19</td><td>0.18</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td rowspan=\"2\">组分</td><td colspan=\"5\">质量分数/%</td></tr><tr><td>铁红底漆</td><td>锌黄底漆</td><td>清漆</td><td>白磁漆</td><td>红磁漆</td></tr><tr><td>低碳合成脂肪酸</td><td></td><td>0.5</td><td></td><td>10.93</td><td></td></tr><tr><td>钛白 铁红</td><td>23.0</td><td></td><td></td><td></td><td>10.50</td></tr><tr><td>沉淀硫酸钡</td><td>13.3</td><td></td><td></td><td></td><td></td></tr><tr><td>滑石粉</td><td>1.5</td><td>4.7</td><td></td><td></td><td></td></tr><tr><td>锌铬黄</td><td></td><td>15.5</td><td></td><td></td><td></td></tr><tr><td>氧化锌</td><td></td><td>7.5</td><td></td><td></td><td></td></tr><tr><td>乙酸丁酯</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td>10. 0</td><td></td><td></td><td></td></tr><tr><td>乙酸丁酯·丙酮：甲苯（10：15：75） 固体分/%</td><td>45.0 约55</td><td>37.0 63</td><td>84.10 16</td><td>71.30 29</td><td>72.64 27</td></tr></table></body></html>\n\n过氯乙烯树脂漆目前主要用于机床涂料，在相关章节中有更详尽的介绍。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 448,
+        "chunk": "# 四、高氯化聚乙烯树脂",
+        "category": " Introduction"
+    },
+    {
+        "id": 449,
+        "chunk": "# 1.高氯化聚乙烯树脂的制备和产品特点  \n\n高氯化聚乙烯HCPE是中国20世纪90 年代率先开发并产业化的CPR。HCPE的制备首先实现工业化试验——500t/年规模的固相法氯化工艺。将聚乙烯粉末在反应器中处于悬浮状态下，在自由基引发剂和紫外光照射下通氯气进行取代反应至含氯量 $>60\\%$ ，同时回收氯化氢制备盐酸。由于固相法产品分子量太大，反应不均一性，在溶剂中溶解性欠佳，黏度高，而且放置一段时间后发生“肝化”。至1997年后水相法HCPE产品问世后即退出市场。  \n\n水相法HCPE工艺过程为采用适当分子量和粒度的聚乙烯粉末，分散剂和水或稀盐酸-与PE比例为 $1:(8\\sim10)$ ，均匀分散在塘瓷反应罐中，加入引发剂并在UV光照射下，搅拌下通氯气反应，控制温度程序和时间、压力，计量通氯量至氯含量 $>60\\%$ 并停止反应。反应副产物氯化氢回收制备稀盐酸。HCPE沉降后用水和碳酸钠漂洗至中性，离心脱水至气流干燥工段，检验包装入库。产品主要指标：含氯量 $55\\%\\sim65\\%$ ， $M_{n}$ 分子量1万 $\\sim2.5$ 万，白色粉末，热分解温度 ${>}1100$ ，残留酸值< $\\mathsf{\\Omega}{=}0,2\\mathsf{m}\\mathsf{g}/100\\mathsf{g}$ 产品。  \n\n与氯化橡胶结构不同，HCPE主链是直链氯原子取代的线型大分子，不带侧链取代基，因此极性较低，与金属底材附着力较差，与其他改性树脂的混溶性不如CR。为此可选用改性的带极性基团的PE为原料制备高性能的HHCPE，如浙江奉化裕隆化工新材料公司产品（HHCPE)，以及日本制纸株式会社产品（HE-510)，指标如下：  \n\n<html><body><table><tr><td colspan=\"2\">HE-510</td><td>HHCPE 65</td></tr><tr><td colspan=\"2\">含氯量/% ></td><td>65</td></tr><tr><td colspan=\"2\">黏度（25℃，20%二甲苯溶液）/mPa·s 180 OK</td><td>200</td></tr><tr><td colspan=\"2\">溶解性</td><td>OK</td></tr><tr><td colspan=\"2\">色数</td><td>3</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 450,
+        "chunk": "# 2.HCPE涂料应用和配方特点  \n\nHCPE是国内最早替代溶剂法CR在涂料中应用的CPR。普通的HCPE性能/价格比优于CR。但在防腐底漆中必须使用酮醛树脂，环氧树脂，二甲苯树脂，芳烃石油树脂，古玛隆树脂等改性以增强其对底材的附着力。其他增塑剂、稳定剂、颜填料等要求与氯化橡胶涂  \n\n料基本相同。  \n\n近十年来HCPE广泛地应用于船舶涂料、防火涂料、防腐涂料、装饰涂料等领域取代CR，出现丙烯酸树脂、环氧丙烯酸树脂改性等众多新产品。  \n\n下面例举一个典型的高光耐候HCPE面漆配方。  \n\n\n<html><body><table><tr><td>原料名称</td><td>配比（质量比）</td><td>原料名称</td><td>配比(质量比)</td></tr><tr><td>HHCPE</td><td>13</td><td>BYK168分散剂</td><td>0.2</td></tr><tr><td>60%B特种丙烯酸树脂</td><td>18~26</td><td>金红石钛白粉</td><td>15</td></tr><tr><td>氯化石蜡CP-42</td><td>5~6</td><td>云母粉</td><td>5</td></tr><tr><td>环氧601</td><td>1~1.5</td><td>石英砂(600目)</td><td>5~10</td></tr><tr><td>亚磷酸三苯酯</td><td>0.6</td><td>其他调色颜料</td><td>0. 5~1.5</td></tr><tr><td>混合溶剂（二甲苯：S-100）</td><td>20：20(质量比）</td><td></td><td></td></tr><tr><td colspan=\"4\">另例举一个典型的防腐底漆配方如下。</td></tr><tr><td>原料名称</td><td>配比（质量比）</td><td>原料名称</td><td>配比（质量比）</td></tr><tr><td>HCPE(30%二甲苯液）</td><td>25~30</td><td>云母氧化铁（320目）</td><td>10~15</td></tr><tr><td>古玛隆树脂（50%二甲苯液）</td><td>10~15</td><td>有机陶土</td><td>0.5</td></tr><tr><td>氯化石蜡CP-50</td><td>5~8</td><td>混合溶剂</td><td>适量</td></tr><tr><td>复合磷酸锌（三聚磷酸铝）</td><td>6~8</td><td></td><td></td></tr></table></body></html>  \n\n上述底、面漆的性能指标可以达到或超过溶剂法氯化橡胶同类产品的水平。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 451,
+        "chunk": "# 五、氯醚树脂",
+        "category": " Introduction"
+    },
+    {
+        "id": 452,
+        "chunk": "# 1.氯醚树脂的制备和产品特征  \n\n氯醚树脂由德国BASF公司20世纪70年代开发并推向市场，其商品名为LAROFLEXMP树脂，简写为LMP树脂。它是 $75\\%$ 的氯乙烯和 $25\\%$ 的乙烯异丁基醚经悬浮乳液聚合而得的共聚物。其产品规格按黏度大小分5个规格：MP15为 $12\\sim18\\mathrm{{mPa}\\cdot{\\ s}}$ ：MP25为$(25\\pm4)\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$ ；MP35为 $(35\\pm5)\\mathrm{{mPa}\\cdot{\\mu}}$ ；MP45为 $(45\\pm8)\\mathrm{{mPa}\\cdot{\\ s}}$ ：MP60为 $(60\\pm$ $10)\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$ 费  \n\n一般性能：  \n\n<html><body><table><tr><td>K值(fikentscher) (DIN53726)</td><td>约35</td><td>软化点(DIN53460)</td><td>48~52</td></tr><tr><td>密度d/（g/cm）（DIN53217）</td><td>1.24</td><td>含氯量/%</td><td>44</td></tr></table></body></html>  \n\n溶解性易溶于芳烃，氯代烃、酯类、酮类溶剂。脂肪烃和醇作为稀释剂（非）真溶剂。  \n\n混溶性可与聚丙烯酸酯、不饱和聚酯、马来酸改性醇酸树脂、环己酮树脂、古玛隆树脂、石油树脂、氨基树脂、焦油沥青等混溶或部分混溶。  \n\n由于分子中引人 $25\\%$ 的乙烯异丁基醚结构，LMP树脂除具有氯化橡胶等CPR共有的耐臭氧、耐大气老化、耐化学介质和良好的施工性能外，具有内增塑性而不必使用迁移性增塑剂可达到足够的柔韧性。LMP树脂极性更高，与底材附着力更佳。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 453,
+        "chunk": "# 2.氯醚树脂的应用和配方原则  \n\n(1）溶剂体系的选择真溶剂和稀释剂的配比直接关系到溶液的黏度，成膜性能。下面列举一些参考数据(质量份)。 心  \n\n<html><body><table><tr><td></td><td>MP25</td><td>MP35</td><td>MP25</td><td>MP35</td><td>MP25</td><td>MP35</td><td>MP25</td><td>MP35</td></tr><tr><td>稀释剂</td><td colspan=\"4\">松香水沸点150~180℃松香水佛点65～95℃</td><td colspan=\"2\">异丁醇</td><td colspan=\"2\">乙醇</td></tr><tr><td>真溶剂</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>甲萃</td><td></td><td></td><td>80(L)</td><td>60</td><td>45(F)</td><td>23</td><td>45(L)</td><td>50</td></tr><tr><td>二甲苯</td><td>60(F)</td><td>22</td><td></td><td></td><td>60(L)</td><td>40</td><td></td><td></td></tr><tr><td>S-100</td><td>80(L)</td><td>50</td><td></td><td>O</td><td>60(L)</td><td>40</td><td>O</td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td></td><td>MP25</td><td>MP35</td><td>MP25</td><td>MP35</td><td>MP25</td><td>MP35</td><td>MP25</td><td>MP35</td></tr><tr><td>乙二醇乙醚乙酸酯</td><td>170(F)</td><td>140</td><td></td><td></td><td>110(F)</td><td>90</td><td>90(L)</td><td>70</td></tr><tr><td>乙酸乙酯</td><td></td><td></td><td>200(F)</td><td>120</td><td></td><td></td><td>40(F)</td><td>25</td></tr><tr><td>乙酸异丁酯</td><td>100(F)</td><td>40</td><td>220(F)</td><td>150</td><td>120(F)</td><td>35</td><td>100(L)</td><td>80</td></tr><tr><td>乙酸丁酯</td><td>90(F)</td><td>35</td><td>220(L)</td><td>170</td><td>110(F)</td><td>80</td><td>100(L)</td><td>80</td></tr><tr><td>甲乙酮</td><td></td><td></td><td>240(F)</td><td>150</td><td></td><td></td><td>40(F)</td><td>25</td></tr><tr><td>环己酮</td><td>220(F)</td><td>90</td><td></td><td>O</td><td>160(F)</td><td>140</td><td></td><td></td></tr></table></body></html>\n\n注：○一稀释剂挥发速率较慢，即使低比例可能引起涂料混浊。一不予测定，实际中无意义。(F)一稀释至一定程度后，浅色清漆可是乳光。(L)一稀释一定程度后，基料分离沉淀。  \n\n醇醚类与低挥发溶剂混用可显著降低黏度，但同时易产生溶剂滞留而影响耐水性，而且乙二醇醚类由于毒性较大已被禁用或限用，目前基本被丙二醇醚类取代。酮类溶剂尽量少用，它们易滞留在涂膜中影响力学性能。  \n\n(2）涂料的黏度和流变性涂料的黏度由LMP溶液黏度与溶剂体系、浓度及温度相关，颜料吸油度和颜基比，改性树脂的特性和配比，以及流变助剂的性能和用量等多种因素有关，配方时应综合平衡。以下例举几个参考配方。  \n\n$\\Phi$ 云母氧化铁防腐底漆（质量份）  \n\n\n<html><body><table><tr><td>原料名称</td><td>MP25/纯酚醛树脂</td><td>MP25</td></tr><tr><td>LMP25</td><td>15.77</td><td></td></tr><tr><td>LMP35</td><td></td><td>16.2</td></tr><tr><td>纯酚醛树脂PA101</td><td>3.15</td><td></td></tr><tr><td>触变剂</td><td>0.15</td><td>0.48</td></tr><tr><td>氯化石蜡，CP-50</td><td>3.94</td><td>1.62</td></tr><tr><td>CP-70</td><td></td><td>1.62</td></tr><tr><td>氧化铁红</td><td>9.46</td><td>8.60</td></tr><tr><td>Rs锌白</td><td>1.26</td><td>1.30</td></tr><tr><td>滑石粉</td><td>9.46</td><td></td></tr><tr><td>磷酸锌</td><td></td><td>8.33</td></tr><tr><td>云母氧化铁</td><td>11. 04</td><td>24.31</td></tr><tr><td>非浮型铝粉</td><td>7.88</td><td>3.24</td></tr><tr><td>二甲苯</td><td>31.57</td><td>200 26.24</td></tr><tr><td>S-100芳烃溶剂</td><td>6.32</td><td>40.0 7.00</td></tr><tr><td>颜料体积浓度/%</td><td>33.7</td><td>40.0</td></tr><tr><td>总不挥发分</td><td>59.3</td><td>65.6</td></tr><tr><td>产品密度/(kg/L)</td><td>1.32</td><td>1.52</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 面漆（质量份）  \n\n\n<html><body><table><tr><td>原料名称</td><td>白色厚涂面漆</td><td>耐化学品面漆</td></tr><tr><td>LMP35树脂</td><td>18.79</td><td>21.23</td></tr><tr><td>K80环已酮树脂</td><td></td><td>2.12</td></tr><tr><td>氯化石蜡CP-50</td><td>1.87</td><td>2.12</td></tr><tr><td>二甲苯</td><td>32.45</td><td>36.66</td></tr><tr><td>S-100</td><td>10.80</td><td>12. 20</td></tr><tr><td>触变剂</td><td>0.37</td><td>0.21</td></tr><tr><td>Bentone 34浆</td><td>3.76</td><td>4.24</td></tr><tr><td>金红石钛白粉</td><td>13.16</td><td>10.61</td></tr><tr><td>重金石粉</td><td>5.64</td><td>10.61</td></tr></table></body></html>  \n\n<html><body><table><tr><td>原料名称</td><td>白色厚涂面漆</td><td>耐化学品面漆</td></tr><tr><td>滑石粉</td><td>11. 28</td><td></td></tr><tr><td>锌白</td><td>1. 88</td><td></td></tr><tr><td>颜料体积浓度/%</td><td>34.50</td><td>19.7</td></tr><tr><td>总不挥发分/%</td><td>53.3</td><td>47.3</td></tr><tr><td>产品密度/(kg/L)</td><td>1.25</td><td>1.15</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 454,
+        "chunk": "# 六、其他的氯化聚烯烃树脂  \n\n氯化聚丙烯含氯 $20\\%\\sim25\\%$ ，目前仍采用四氯化碳法生产。其生产工艺禁用四氯化碳已列入国家环保总局履约办的第二期工作目标。它主要用于塑料油墨的基料。在涂料行业中仅限于聚乙烯或聚丙烯等低表面能难粘底材作为附着力促进剂，或底涂层，用量较少。由于在塑料涂料节中有详细叙述，在此不展开了。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 455,
+        "chunk": "# 第十一节硝酸纤维素",
+        "category": " Introduction"
+    },
+    {
+        "id": 456,
+        "chunk": "# 一、概述  \n\n纤维素硝酸酯，通常称为硝酸纤维素、硝化纤维素、硝基纤维素，比起其他的纤维素产品，是唯-得到商业上重要、大量应用的纤维素的无机酸酯。它也是纤维素衍生物中最古老的一种。人们对于硝酸纤维素的兴趣原先是在炸药领域，其先行者包括法国的Braconnet(1832年)，瑞士的Schoenbein（1845年)，英国的Parkes（1855年)。第一次世界大战之后，氮含量为 $10.5\\%\\sim12.2;$ 6的硝酸纤维素被迅速用于涂料工业，特别是用于汽车面漆；硝酸纤维素以其耐久性、坚固性、溶解性和在外界干燥条件下溶剂的快速释放性而成为传统和有效的涂料成膜物质。在我国，硝酸纤维素大多用短绒的棉花作为原料，产品称为硝化棉。2005年，我国硝化棉的产量为75500t。",
+        "category": " Introduction"
+    },
+    {
+        "id": 457,
+        "chunk": "# 二、硝酸纤维素的生产工艺",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 458,
+        "chunk": "# 1.硝酸纤维素的合成反应  \n\n纤维素的化学结构是大量的无水葡萄糖单位（anhydroglucoseunits）用醚键连接起来，化学上纯净的纤维素分子里有 $500\\sim2500$ 个葡萄糖单位，而每个葡萄糖单位可被视为三元醇。硝酸纤维素是纤维素与硝酸和硫酸的混合酸进行酯化反应的产物。反应式如下：  \n\n![](images/01103223ebc7f3007b4560524b117642aff09fbfda781a7a34e35843a4ccf652.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 459,
+        "chunk": "# 2.生产工艺  \n\n（1）纤维素的精制以优质短绒棉（cottonlinters）形式的纤维素在加入湿润剂（如松香皂）的苛性碱中隔离空气煮沸以除去脂肪、蜡、表皮质等脏物和不纯物，然后经漂洗、漂白处理、机械碾压和热空气烘干而成为精制脱脂棉，它含有 $98\\%$ 以上的α纤维素。由木材制造纯纤维素有类似的过程，其手续更为复杂。  \n\n(2）硝酸纤维素的生产工业上生产硝酸纤维素分间歇式和连续式两类。  \n\n$\\Phi$ 间歇式生产工艺在间歇式的硝酸纤维素生产中，以脱脂棉为原料，用硝酸、硫酸的混合酸进行酯化。硝酸、硫酸和纤维素的反应是经过仔细和精确地控制的，直到达到预想的硝化度。硫酸用来带走反应中形成的水。再经驱酸、安定处理和加压降黏处理，脱水，再加湿润剂（乙醇、异丙醇或丁醇）驱水及混合、离心，所得的产品，称为硝化棉。目前市场上销售的硝化棉一般是以含 $70\\%$ 的硝化棉、 $30\\%$ 的醇湿润剂的形式供应的。  \n\n![](images/288effef0d4d48983acc9a5b68fbcac03cf5705bc8ca3432cbaadfa70695a088.jpg)  \n图2-1-64连续法纤维索确化流程  \n\n$\\textcircled{2}$ 连续式生产工艺图2-1-64是美国HERCULES公司的连续式生产硝酸纤维素的简要流程。纤维素（主要是精制的木浆粗）与混合硝化酸被连续、同时地输送到一个容器中，并在其中发生纤维素的硝化，经过硝化以后和用过的酸被连续地输送进某一离心机中，该机被设计为分区进行，硝酸纤维素被断断续续地从一个区输送到下一区。在头一区，大多数硝化了的原酸被移走，在随后的各区，硝酸纤维素中的酸被更弱的酸所取代，在最后一区，则被水所取代。最后取代的酸和水洗的量正好足够前一个取代的有一点酸浓度的水的冲洗量，如此运行，最后离开系统的回收的酸的浓度与用过的酸的浓度相接近。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 460,
+        "chunk": "# 三、硝酸纤维素的分类及应用  \n\n硝酸纤维素一般按其氮含量和聚合度的不同而分类，置换度和聚合度是硝酸纤维素的两个特性，是将硝酸纤维素进行分类的重要依据。  \n\n在纤维素分子的结构中，每个葡萄糖单位有三个羟基存在，其反应活力有所不同，伯醇基活力最大，与其较近的仲醇基反应活力最差，活力较大的醇基在硝化反应中较先被硝基所置换。此外，混合酸浓度、硫酸和硝酸的比例不同，也影响硝酸纤维素氮含量的高低，一般而言，水分的增加会使氮含量提高，硫酸比例提高，可制得较高氮含量的硝酸纤维素。  \n\n$\\textcircled{1}$ 置换度（degree of substitution，DS）用硝基置换纤维素上的每一个无水葡萄糖单位（anhydroglucose unit）上的平均羟基数，1个羟基被硝基置换DS为1.0——-氮含量6. $77\\%$ ，两个羟基被硝基置换DS为2.0——氮含量11. $13\\%$ ，全部三个羟基被硝基置换DS为3.0——氮含量14. $14\\%$ ，实际上能达到的最大DS为2.9，即氮含量 $13.8\\%$ ；用于漆、薄膜和塑料的工业硝化纤维素DS为 $1.8{\\sim}2.5$ ，氮含量为 $8.5\\%\\sim12.2\\%$ (图2-1-65)。  \n\n![](images/46abc60b4f9bcedfa1618b5858118b27185db45b2e0f34d1081edea95a8e560e.jpg)  \n图2-1-65-硝化棉的氮含量与羟基置换度的关系  \n\n$\\textcircled{2}$ 聚合度（degree of polymerization，DP）在硝酸纤维素分子中葡萄糖单位的平均数称为聚合度。在硝酸纤维素的生产过程中，硝酸纤维素被加水煮沸，会逐渐发生分子裂解，其聚合度减小，尤其是悬浮在水中而在不同的时间周期用水蒸气加热和加压，可降低聚合度，得到不同链长的硝酸纤维素。硝酸纤维素的聚合度越小，以相同浓度溶解于给定的溶剂得到的溶液的黏度就越小。  \n\n(1）以ICI硝酸纤维素为代表的英制硝酸纤维素分类法ICI公司的工业硝酸纤维素，如果是用木浆制造的硝化纤维素，其型号加前缀A，而用棉绒制造的则没有这一前缀。  \n\nICI硝酸纤维素分为H和L两类，H表示高氮含量，氮含量为11 $3\\%\\sim12.2\\%$ ；L表示低氮含量，氮含量为 $10.7\\%\\sim11.2\\%.$ ，这两大类又可以分成四种黏度的等级：“H”为高黏，在 $100\\mathrm{mL}$ 溶剂中3g干硝酸纤维素的浓度；“M”为中黏，在 $100\\mathrm{mL}$ 溶剂中 $10\\mathbf{g}$ 干硝酸纤维素的浓度；“L”为低黏，在 $_{\\mathrm{100mL}}$ 溶剂中 $20\\mathbf{g}$ 干硝酸纤维素的浓度；“X”为超低黏，在 $100\\mathrm{mL}$ 溶剂中 $40\\mathrm{g}$ 干硝酸纤维素的浓度。  \n\n例如，AHX3/5表示从木浆粗中所制造的硝酸纤维素的等级，氮含量在11.3%～12. $2\\%$ 之间，在 $100\\mathrm{mL}$ 的试验溶剂中的 $40g$ 棉的黏度在 $0.3{\\sim}0.5\\ensuremath{\\mathbf{Pa}}\\cdot\\ensuremath{\\mathbf{s}}$ 之间。  \n\n下面是 $^{11}$ 种常用的硝酸纤维素的规格。  \n\n·AHX系列 AHX3/5、AHX8/13、AHX30/50、AHX120/170。  \n·ALX系列 ALX3/5、ALX8/13、ALX20/40。  \n·AHL系列 AHL30/40、AHL 120/170。  \n·AHM系列 AHM 15/30、AHM100/200。  \n\n(2）以HERCULES的规格为代表的美制硝酸纤维素分类法RS类型的平均氮含量为$12\\%$ (11. $8\\%\\sim12.2\\%)$ ，AS类型的平均氮含量为11. $5\\%$ (11.3%\\~11. $7\\%$ ，SS类型有$11\\%$ (10 $9\\%\\sim11.2\\%)$ 的平均氮含量。具体的牌号和黏度见表2-1-247。  \n\n(3）欧制的型号依黏度、浓度值而定，表示溶于 $25\\Upsilon$ ， $100\\mathrm{mL}$ 溶剂（丙酮：水 $\\c=$ $95:5)$ ，生成溶液黏度为 $0.4\\mathrm{Pa}\\cdot\\mathrm{s}$ 硝酸纤维素溶液中的干硝酸纤维素克数。较高氮含量型由1E至38E，较低氮含量型由7A至 $35\\mathrm{A}$  \n\n（4）我国工业用的硝化棉规范（WJ9028—2005）我国工业用硝化棉的分类方法类似美制的方法，都是通过测定落球时间来确定黏度的方法。我国涂料用的硝化棉分为低氮含量（10.7%～11.4%）的L型和高氮含量 $(11.5\\%\\sim12.2\\%)$ 的H型，其黏度的规格见表2-1-248。  \n\n表2-1-247 美制硝酸纤维素的分类  \n\n\n<html><body><table><tr><td rowspan=\"2\">牌号</td><td rowspan=\"2\">氮含量/%</td><td rowspan=\"2\">12.2%溶液的 黏度/mPa*s</td><td colspan=\"3\">时间/s</td></tr><tr><td>溶液浓度12.2%</td><td>溶液浓度20%</td><td>溶液浓度25%</td></tr><tr><td>RS18-25eps RS30-35cps</td><td rowspan=\"10\">11.8~12.2</td><td>18~25 30~35</td><td>一 _—</td><td>一 一</td><td>一</td></tr><tr><td>RS1/4-sec</td><td>一</td><td></td><td>一</td><td>~5</td></tr><tr><td></td><td></td><td>一</td><td>一</td><td>6~8</td></tr><tr><td>RS3/8-sec</td><td>一</td><td></td><td></td><td></td></tr><tr><td>RS1/2-sec</td><td>一</td><td>一</td><td>3~4 6~8</td><td>一</td></tr><tr><td>RS 3/4-sec</td><td>一</td><td></td><td></td><td></td></tr><tr><td>RS1-205e</td><td>——</td><td>5~-25</td><td>—一</td><td>——</td></tr><tr><td></td><td></td><td>30~40</td><td>一</td><td>-</td></tr><tr><td>RS30-40sec</td><td>一</td><td>60~80</td><td>一</td><td>一</td></tr><tr><td>RS60-80sec RS125-175see</td><td>一</td><td>125~175</td><td>一</td><td>一</td></tr><tr><td>RS600-1000sec</td><td>一 一</td><td>600~1000</td><td>--</td><td>一</td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td>RS1000-1500sec</td><td></td><td>1000~1500</td><td>一 二</td><td>一</td></tr><tr><td>RS1500-2000sec</td><td></td><td>一</td><td>1500~2000</td><td></td></tr><tr><td>AS 1/2-sec</td><td>11. 3~11.7</td><td>一 二</td><td></td><td>3~4</td><td>一 一</td></tr><tr><td>AS5-6-sec</td><td rowspan=\"5\">10.9~11. 2</td><td>30~35</td><td>5~6.5</td><td>一</td><td></td></tr><tr><td>SS30-35cps</td><td></td><td>一</td><td>一</td><td></td></tr><tr><td>SS 1/4-see</td><td>一</td><td>一 一</td><td>一</td><td>4~6</td></tr><tr><td>SS 1/2-sec</td><td>一</td><td></td><td>3.4</td><td>一</td></tr><tr><td>SS5-6-sec SS40-60-sec</td><td>一 二</td><td>5~6.5 40~60</td><td>一 二</td><td>一 二</td></tr></table></body></html>  \n\n表2-1-248我国硝酸纤维素的分类  \n\n\n<html><body><table><tr><td rowspan=\"2\">型号</td><td rowspan=\"2\">规格</td><td colspan=\"3\">溶液浓度（品质百分浓度）</td></tr><tr><td>12.2%</td><td>20.0%</td><td>25.0%</td></tr><tr><td rowspan=\"5\">L （低氮含量 10.7%~11.4%)</td><td>1/8</td><td></td><td></td><td>1. 7~3. 0</td></tr><tr><td>1/4a</td><td></td><td></td><td>3. 1~4. 9</td></tr><tr><td>1/4b</td><td></td><td></td><td>5.0~10.0</td></tr><tr><td>1/2a</td><td></td><td>3. 2~6. 0</td><td></td></tr><tr><td>1/2b</td><td></td><td>6.1~8,4</td><td></td></tr><tr><td rowspan=\"14\">H 11. 两~12.2%)</td><td>1/16</td><td></td><td></td><td>1. 0~1. 6</td></tr><tr><td>1/8</td><td></td><td></td><td>1. 7~3. 0</td></tr><tr><td>1/4a</td><td></td><td></td><td>3.1~4.9</td></tr><tr><td>1/4b</td><td></td><td></td><td>5.0~8.0</td></tr><tr><td>1/4c</td><td></td><td></td><td>8.1~10.0</td></tr><tr><td>1/2a</td><td></td><td>3.2~6.0</td><td></td></tr><tr><td>1/2b</td><td></td><td>6.1~8.4</td><td></td></tr><tr><td>1</td><td></td><td>8.5~16.0</td><td></td></tr><tr><td>3</td><td>2.0~4.0</td><td></td><td></td></tr><tr><td>10</td><td>5.0~12</td><td></td><td></td></tr><tr><td>15</td><td>13~20</td><td></td><td></td></tr><tr><td>30</td><td>21~40</td><td></td><td></td></tr><tr><td>60</td><td>41~80</td><td></td><td></td></tr><tr><td>120</td><td>81~160</td><td></td><td></td></tr></table></body></html>  \n\n工业上生产硝基木器漆常常使用1/4s和1/2s的硝酸纤维素。低于1/4s的硝酸纤维素，如1/8s和1/16s，虽然可以制出黏度较低，固体分高，在硬度和耐打磨性上较好的漆，但其抗拉性、耐寒性、耐久性较差，在低温及冷热交替时易产生裂痕，涂膜易流挂，易在紫外线的作用下变脆。使用5s、20s或更高黏度的硝酸纤维素制成的漆，流平性差，易引起橘皮、针孔和拉丝等漆病，而且漆的固体分偏低，并增加了VOC 的排放量。但是高黏度的硝酸纤维素制成的漆具有优良的柔韧性、拉伸强度及不易脆裂的特性，使其适于用在织物用漆、皮革漆、室外帆布用漆上（表2-1-249)。  \n\n表2-1-249不同氮含量和黏度的硝化棉在涂料和油墨中的应用  \n\n\n<html><body><table><tr><td>型号</td><td>主要应用</td></tr><tr><td>L1/8</td><td>柔版油墨、回版油墨、木器覆膜涂料、木器喷漆、皮革用水性乳液</td></tr><tr><td>L1/4、L1/2</td><td>柔版油墨、凹版油墨、木器抛光罩面漆、木器手扫漆、木器覆膜涂料、木器底漆、木器喷漆、日历、 挂历、卡板纸、纸张覆膜涂料、包装纸、金属箔、订书钉、皮革用水性乳液</td></tr><tr><td>H1/32、H1/16、H1/8</td><td>柔版油墨、回版油墨、木器覆膜涂料、木器喷漆、汽车漆、皮革用水性乳液</td></tr><tr><td>H1/4、H1/2、H1</td><td>柔版油墨、回版油墨、木器抛光罩面漆、木器手扫漆、木器覆膜涂料、木器底漆、木器喷漆、日历、 挂历、卡板纸、纸张覆膜涂料、包装纸、汽车漆、金属箔、订书钉、金属底漆、皮革用水性乳液、皮革 底涂、指甲油、木材填孔剂、生物膜</td></tr><tr><td>H5、H20、H30</td><td>卡板纸、包装纸、皮革用水性乳液、皮革底涂、皮革顶涂、木材填孔剂</td></tr><tr><td>H60、H80、H120、H800</td><td>皮革用水性乳液、皮革顶涂、木材填孔剂、白炽灯涂料</td></tr></table></body></html>  \n\n(5）硝酸纤维素的性质涂料用硝酸纤维素的理化指标见表2-1-250。  \n\n表2-1-250涂料用硝酸纤维素的理化指标（中国标准的规定）  \n\n\n<html><body><table><tr><td colspan=\"2\">指标名称</td><td colspan=\"2\">指标</td></tr><tr><td colspan=\"2\"></td><td>一级</td><td>二级</td></tr><tr><td colspan=\"2\">硝酸纤维索溶液透光率/%</td><td colspan=\"2\">≥90 ≥85</td></tr><tr><td rowspan=\"3\">酸度(以硫酸计)/%</td><td>1/16s,1/8s</td><td colspan=\"2\">≤0.08</td></tr><tr><td>1/4s</td><td colspan=\"2\">≤0.07</td></tr><tr><td>其他</td><td colspan=\"2\">≤0.06</td></tr><tr><td>80C耐热试验/min</td><td colspan=\"4\">≥10</td></tr><tr><td>爆发点/℃</td><td colspan=\"4\">≥180</td></tr><tr><td>灰分/%</td><td colspan=\"4\">≤0.2</td></tr><tr><td>水分试验</td><td colspan=\"4\">在混合溶剂中不显浑浊</td></tr><tr><td>湿润剂含量（醇或水）/%</td><td></td><td colspan=\"2\">30 ±2</td><td></td></tr></table></body></html>  \n\n$\\textcircled{1}$ 酸度关系到游离酸硝酸纤维素由脱脂棉与硝酸、硫酸之混合酸，进行酯化反应所得。有释放出 $\\mathbf{NO}_{2}$ 成为游离酸的存在可能，如酸度超过指标，则会加剧 $\\mathrm{NO}_{2}$ 的释放，而反应放出的热量如不能及时散发则会升温加速进一步的分解，甚至引发燃烧和爆炸，因此要控制游离酸值。 X  \n\n$\\textcircled{2}$ 爆发点是指硝酸纤维素自燃时的最低温度。这是硝酸纤维素产品质量必须检测的一个项目，但一般涂料生产厂家因多种原因而不予检测，这是存在的安全隐患之一。当然作为硝酸纤维素生产企业，“爆发点”是作为必须检测项目，爆发点低于 $180^{\\circ}\\mathrm{C}$ 的硝酸纤维素，不能作为成品流入市场或进入下一道工序。  \n\n$\\textcircled{3}$ 耐热度 $80^{\\circ}\\mathrm{C}$ 耐热试验）是指在 $80^{\\circ}\\mathrm{C}$ 时硝酸纤维素开始分解产生二氧化碳，使碘淀粉试纸变色所用的时间。同样也是硝酸纤维素产品质量的必须检测项目，它关系到硝酸纤维素的安全使用和安全贮存的问题。  \n\n硝酸纤维素的安定度，主要取决于以上耐热度、爆发点和酸度三项。  \n\n$\\textcircled{4}$ 灰分水质较硬时，对硝酸纤维素的多次洗涤可使灰分增高，而灰分增高时，会引起清漆浑浊、透明度及光泽度下降等质量问题。  \n\n$\\textcircled{5}$ 水分水分来自脱水时未能脱尽的残留部分，会随着硝酸纤维素进入涂料中。涂料中水分高时会使涂料浑浊，在干燥过程中水分还会引起涂膜发白，严重时导致部分硝酸纤维素或树脂沉淀以致涂膜破坏，从而影响涂膜性能。  \n\n$\\textcircled{6}$ 湿润剂湿润剂多采用乙醇（也有加异丙醇的)，是在脱水后加人的，按规定应加$30\\%$ 。因配方设计及投料时是按 $70\\%$ 硝酸纤维素含量计算的，所以如果湿润剂含量不准确，就会引起配方与投料之间的偏差。硝化棉若用水作为湿润剂，得到的产品俗称“水棉”，多用于轧制硝基色片。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 461,
+        "chunk": "# 四、硝酸纤维素的溶解",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 462,
+        "chunk": "# 1.溶解硝酸纤维素的溶剂  \n\n溶解硝酸纤维素的溶剂包括活性溶剂、非活性溶剂和助溶剂。  \n\n能溶解硝酸纤维素漆的活性溶剂（或称真溶剂）（true oractive solvents）有酯类、酮类、醚醇类、酮醇类等。考虑到溶解力和经济因素，酯类以乙酸乙酯、乙酸丁酯、乙酸异丁酯等应用得最多。近年来有些企业也较多地使用乙酸仲丁酯、碳酸二甲酯；酮类以丙酮、甲乙酮、甲基异丁酮应用得较多；常用的醚醇类和酮醇类有丙二醇乙醚、丙二醇丁醚和二丙酮醇等品种。  \n\n醇类常被用于溶解硝酸纤维素的助溶剂或潜溶剂（co-solvents)，醇类具有潜在的溶解能力，它们往往不能单独溶解涂料用的硝酸纤维素，但与真溶剂配合时，能有同样或更大的溶解力。应用最多的醇类有丁醇、异丁醇、异丙醇和乙醇等。甲醇是例外，它本身能够溶解氮含量为 $10.9\\%\\sim12.2\\%$ 6的硝酸纤维素，但它属于有害大气污染物，其毒性和过高的挥发速率限制了甲醇的使用。  \n\n烃类、脂肪族或芳香族醚被称为稀释剂（diluents）或非溶剂（non-solvents），即非活性稀释剂。它们不能溶解硝酸纤维素。然而，只要稀释剂的成分不是太高，不致阻止硝酸纤维素的完全溶解，溶剂和助溶剂的混合物可以通过加入稀释剂而不会引起有害的影响。为了获得良好的干膜，必须保持溶剂和稀释剂的挥发平衡。稀释剂通常是硝基漆中树脂的良好溶剂，且价格比真溶剂便宜。因此，只要是切实可行，在清漆中通常采用含量尽可能高的稀释剂。最常用的稀释剂是甲苯和二甲苯，但是，甲苯和二甲苯也属有害大气污染物（HAPS)，近年来，出于环保和健康的原因也用溶剂汽油等脂肪烃作为稀释剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 463,
+        "chunk": "# 2.硝酸纤维素的溶解  \n\n硝酸纤维素在溶液中作为一种胶体（colloidal)，不能形成真溶液而是形成亲油的溶胶。硝酸纤维素的溶解（国内称为“溶棉”)，需使用一套合适的混合设备，把硝酸纤维索与溶剂、助溶剂和稀释剂的混合物进行混合。混合器的类型一般选用配有旋转搅拌的垂直缸。有些混合器仅装备推进器型的叶片，有些是涡轮型或碟式搅拌，能使溶液上下旋转运动。对于最快和最有效的溶解，高速搅拌是最有意义的（为了溶解的安全必须采取一定的措施)。假若同时使用现代的、高剪切力的搅拌机并具有正确的溶解技术，所有规格的硝酸纤维素都可  \n\n以迅速地溶解。  \n\n正确溶解硝化纤维素的方法和要求如下。  \n\n$\\Phi$ 先用非活性溶剂进行搅拌，打碎厚实的结块以形成均匀的糊状浆。  \n$\\textcircled{2}$ 搅拌糊状浆并缓慢地加入活性溶剂，以便快速地溶解硝酸纤维素。  \n\n由于硝酸纤维素高度的活泼性，必须用这样的方法来溶解，否则可能会造成胶凝化或是延长溶解的时间，从而造成生产的损失、过滤的问题和硝酸纤维素的浪费。  \n\n为了得到有效的预湿润，1份（质量）的硝酸纤维素需要至少1.5～2份（质量）的非活性稀释剂。  \n\n注意：如果混合溶液中有高比例的稀释剂，则建议留下多余的稀释剂，先加入真溶剂和助溶剂，让硝酸纤维素完全溶解后，再慢慢加入剩余的稀释剂，并加以充分搅拌。  \n\n为了保证高剪切力下溶解的安全，正在溶解的硝酸纤维素必须完全浸泡在溶剂中。  \n\n对于溶解的速率来说，加入的顺序和所用液体成分的量有重要的关系。假如硝酸纤维素先与助溶剂或者稀释剂相混合，又或者是先与稀释剂和一部分的活性溶剂相混合，随后才加入剩余的活性溶剂，溶解时所需的时间会明显减少。当使用低速、简单推进器型搅拌时，这一程序特别有效。  \n\n硝酸纤维素通常在存放一段时间后黏度会略有下降，这种现象被称为延迟溶液效应(delayed solution effect)。  \n\n表2-1-251给出硝酸纤维素在含有乙醇-甲苯-乙酸乙酯的混合溶剂中发生这一效应的数据。在硝酸纤维素被分散在混合溶液中后，最先测量到的这一下降值为最大。  \n\n表2-1-251RS硝酸纤维素溶液的延迟溶液效应  \n\n\n<html><body><table><tr><td rowspan=\"2\">加人溶液后的时间 /h</td><td colspan=\"3\">标准黏度法的时间/s</td></tr><tr><td>1/2s(20%溶液）</td><td>5~6s(12.2%溶液）</td><td>15 ~20s(12.2%溶液)</td></tr><tr><td>1</td><td>3.8</td><td>5.3</td><td></td></tr><tr><td></td><td>3.7</td><td>5.2</td><td>19.4</td></tr><tr><td>4 8</td><td>3.6</td><td>5.0</td><td>19.0</td></tr><tr><td>24</td><td>3.5</td><td>4.8</td><td>18.8</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 464,
+        "chunk": "# 3.硝酸纤维素及其溶液的调黏  \n\n利用落球法公式 $\\scriptstyle\\eta=K(a-b)t$ ，把纵坐标设为的对数，可以作出适合我国硝酸纤维素用的调整黏度的混合图（图2-1-66)。  \n\n如果有两种不同黏度规格的硝酸纤维素，可以利用混合图来定量地调配出所需黏度的硝酸纤维素的用量。图2-1-66是国产硝酸纤维素的黏度混合图，在图中的举例是从1/4bs和10s硝酸纤维素混合得到 $1/2b s$ 的硝酸纤维素。代表前两种黏度等级的100%含量黏度的连线与代表 $1/2b\\mathbf{s}$ 硝酸纤维素黏度区相交点的垂直线显示，低黏度的1/4bs产品的用量是$60\\%$ ，高黏度的10s产品的用量是 $40\\%$ ，由此可算出这两种黏度等级产品所要求的投料量。  \n\n上述混合图的方法只是一个近似的计算方法，有一定的局限性，当高黏度和低黏度两个等级过于接近时，比值的误差较大，而当两个等级的黏度差过远时，有可能造成低黏度等级的硝酸纤维素快速溶解，消耗大量的活性溶剂，造成高黏度等级的硝酸纤维素不能完全地溶解，结果引起硝酸纤维素溶液的浑浊和“起胶粒”。 M  \n\n在硝基漆的生产中，为了稳定漆的质量，要求采用的硝化棉液的黏度被控制在尽可能小的范围内，有人利用落球法的公式和混合图的原理，推导出一个更为简单的公式，用于从黏度大小不一的两批硝酸纤维素中生产中间黏度的硝化棉液，也用于从两种黏度的硝化棉液调  \n\n![](images/d607571614f9df9b66d6518dfc0c39143651753243c67f200d51777e23a3946e.jpg)  \n图2-1-66硝化棉黏度混合图  \n\n整出某一中间黏度的硝化棉液：  \n\n$$\nX_{\\star}=\\frac{\\log t_{\\sf t}=-\\log t_{\\sf\\ A}}{\\log t_{\\star}-\\log t_{\\sf\\ A}}\n$$  \n\n$$\nX_{\\curlywedge}=1-X_{\\star}\n$$  \n\n式中， $x_{\\star}$ 是黏度大的硝化棉分数； $\\mathsf{l}_{\\mathsf{B}}t_{\\mp}$ ， $\\mathsf{I}_{\\mathsf{B}^{t}\\star}$ ， $\\mathsf{l g}t_{\\hbar}$ 是落球经过中间黏度、大小黏度的同溶剂配方的硝化棉液所用秒数的对数，由多功能计算器则很容易算出对数值（也可列表供查看）。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 465,
+        "chunk": "# 五、硝酸纤维素的运输、贮存和应用的安全问题  \n\n硝酸纤维素属危险化学品，其运输、贮存和使用必须引起特别注意（表2-1-252）。  \n\n表2-1-252硝酸纤维素的危险化学品分类及特性  \n\n\n<html><body><table><tr><td>危险货物类别</td><td>危险货物编号</td><td>名称</td><td>危险特性</td><td>UN号</td></tr><tr><td>GB1.1类 爆炸品</td><td>11032 （干的或含水或 乙醇<25%）</td><td rowspan=\"5\">硝 纤 维 素 速其分解，其至能自燃着火或爆炸</td><td rowspan=\"5\">能着火和爆炸，威力取决于氮含量的多少。干燥的硝酸 纤维素易被点燃，松散的硝酸纤维素在空气中燃烧不留残 渣，增大密度时，燃烧速率下降。大量硝酸纤维素在堆积或</td><td>0340</td></tr><tr><td>GB1.1类 11032 爆炸品 （含增塑剂<18%）</td><td>酸 密闭容器中燃烧能转为爆轰。干燥的硝酸纤维素在较低温</td><td>0341</td></tr><tr><td>GB1.3类 13014</td><td>度下能自行缓慢分解，放出大量的有毒易燃气体并伴随放 热，温度会迅速上升而自燃。自燃点170℃，闪点约13℃。 如含水量或含醇量在25%以上时较为安全。干燥的硝酸纤</td><td></td></tr><tr><td>爆炸品 （含乙醇≥25%） GB1.3类 爆炸品</td><td>维素因摩擦面产生静电，由于成品中含有少量残酸，会加</td><td>0342</td></tr><tr><td>13015 （含增塑剂≥18%）</td><td></td><td>0343</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>危险货物类别</td><td>危险货物编号</td><td>名称</td><td>危险特性</td><td>UN号</td></tr><tr><td>GB4.1类 易燃固体</td><td>41031 （含水≥25%）</td><td rowspan=\"3\">硝 酸纤 维素</td><td rowspan=\"3\">脱敏爆炸品。该品遇到火星、高温、氧化剂以及大多数有 机胺(对黎二甲等）发生炎，爆，如超度超过40</td><td>2555</td></tr><tr><td></td><td>（含氮≤12.6%）)</td><td>2557</td></tr><tr><td>燃1体</td><td></td><td>人或在醇作为密的为如器翻剂挥发后，易发生火灾。 2556</td></tr><tr><td>体</td><td>(含氮≤12.6%;含硝化硝 纤维索≤55%）</td><td>溶液</td><td>大 无 硝酸纤维素溶液卷入火内时会放出有毒烟雾</td></tr><tr><td></td><td>41546</td><td>硝酸 漆片</td><td>性明火极易燃。，燃出量。需，其火灾危险， 无 发霉时在积热不散的情况下，易引起自燃</td></tr></table></body></html>  \n\n根据《建筑设计防火规范》和《易燃易爆性商品贮藏养护技术条件》的规定：建硝酸纤维素贮存仓库必须是一级耐火等级，硝酸纤维素适宜的贮藏温度 $\\leqslant25\\mathtt{C}$ ，相对湿度 $380\\%$ 。有关硝酸纤维素贮存、运输的重点是防止硝酸纤维素久贮、过干、过热、震动和混放。消防措施、安全注意事项以及泄漏物、废弃物的处理等，都要遵照有关法规和规定。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 466,
+        "chunk": "# 第十二节有机硅树脂涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 467,
+        "chunk": "# 一、概述",
+        "category": " Introduction"
+    },
+    {
+        "id": 468,
+        "chunk": "# 1.定义  \n\n有机硅树脂（siliconeresin）是指分子中含Si—C键的有机聚合物，也称硅树脂、硅酮树脂。对硅氧烷（silicone）单体和它的预聚物及树脂，也可统称为有机硅，以它们为成膜物制备的涂料称为有机硅树脂涂料，也可简称为有机硅涂料（silicone paints)。",
+        "category": " Introduction"
+    },
+    {
+        "id": 469,
+        "chunk": "# 2.发展简况  \n\n20世纪30年代，直接合成有机硅树脂中间体—有机氯硅烷的方法获得成功，为有机硅树脂工业化开创了新路，1943年正式开始工业化生产。由于有机硅材料（silicone materi-als）应用广、性能优良，因此发展较快。2003年全球有机硅材料的品种已达上万种，总消耗量达74万吨，比10年前增加了 $50\\%$ 以上，整个消费构成为：橡胶、树脂、涂料、纤维、化妆品及相关行业占 $40\\%$ ，电子、电气占 $20\\%$ ，土木建筑占 $20\\%$ ，其他占 $20\\%$ ，总市场规模为80亿美元。  \n\n国内在20世纪50年代开始有机硅产品研发，20世纪90年代出现年产1万吨的企业，现已发展了年产数万吨至10万吨的企业。20世纪60年代开始有机硅树脂涂料研究，2007年全国溶剂型有机硅树脂涂料消耗量在1万吨以上，有机硅改性树脂涂料和水性硅丙涂料的用量较大，但未见统计数据。",
+        "category": " Introduction"
+    },
+    {
+        "id": 470,
+        "chunk": "# 3.有机硅树脂涂料的分类及其性能  \n\n(1）按涂料成膜物的类型分类按成膜物的类型可分为纯有机硅树脂涂料和有机硅改性树脂涂料。纯有机硅树脂涂料耐热性与绝缘性突出，在较高温度的环境下显示出优良的耐候性、耐腐蚀性，也是优良的高温绝缘涂料。  \n\n有机硅改性树脂涂料包括有机硅改性酚醛、醇酸、聚酯、丙烯酸、环氧、聚氨酯树脂，根据有机硅材料用量多少，可以不同程度地提高改性树脂的耐热性、耐候性、耐腐蚀性、柔韧性及其他性能，同时也可改善有机硅树脂的成膜性能。  \n\n有机硅改性醇酸树脂涂料，有机硅用量适当时，耐候性可提高4倍；耐热性、耐腐蚀性明显改善，整个涂料档次提高。有机硅改性醇酸树脂涂料大量用于高压输电线路铁塔、铁路公路桥梁、货车、动力站、开采石油设备、室外化工装置、农业机械的涂装。还常用于金属及塑料防腐保护涂料、耐候和耐化学介质及附着力好的涂料、印刷油墨以及船舶的水线上涂料及工厂用耐候性涂料。  \n\n有机硅改性聚酯-氨基涂料，其使用温度从 $120{\\sim}150\\ensuremath{\\mathrm{~c~}}$ 可以提高到 $180\\sim200^{\\circ}{\\mathrm{C}}$ ，其耐候性、耐腐蚀性也明显提高。有机硅改性聚酯-氨基涂料的一个主要用途是用于卷材涂料，提高其抗酸雨腐蚀性和耐候性，扩大彩板建筑物外用范围。  \n\n有机硅改性丙烯酸树脂涂料，改进其耐寒性、耐水性、耐碱性和耐候性，并改善其电性能。用3-甲基丙烯酰氧基丙基三甲氧基硅烷（MPTS）和丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸正丁酯共聚，MPTS用量占总单体量 $30\\%$ 时，耐候性优良，其物理性能与综合性能也较好。  \n\n上述有机硅改性树脂涂料，在国内外一些文献中都有详细报道，本章内不再赘述。  \n\n氟化改性有机硅涂料，可以进一步降低有机硅涂料的表面能，改进其防沾污性；可提高氟树脂耐热性，能够综合氟树脂与有机硅树脂二者的优点。在本章第三节专门阐述。  \n\n(2）按是否属环境友好型涂料分类按品种是否对环境友好来分类有溶剂型和环境友好型的有机硅树脂涂料，前述有机硅改性树脂均属于前一类。  \n\n环境友好型有机硅树脂涂料有高固体分的有机硅与有机硅改性树脂涂料、水性有机硅与有机硅改性树脂涂料、辐射固化有机硅涂料，在本章第四～六节分别介绍。  \n\n(3）有机硅助剂有机硅助剂在涂料中广泛应用，如对颜料的润湿分散；涂料的抑泡、消泡；湿膜的流平、消除涂膜端；涂膜的消光、增光。特别是硅烷偶联剂，可以作为多种用途的助剂，含官能基的硅氧烷偶联剂可以改性其他树脂，促进涂层对底材、层间的附着力，取代六价铬进行表面处理，对改进涂料与涂膜性能起着特殊作用。可参见本书助剂和表面处理部分。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 471,
+        "chunk": "# 二、有机硅功能与专用性树脂涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 472,
+        "chunk": "# 1.有机硅树脂合成与成膜原理  \n\n(1）合成与成膜原理用于制备涂料的有机硅材料， $90\\%$ 以上是以硅氧键（-Si-O-Si--)为骨架组成的（聚）硅氧烷（silicone)，由有机氯硅烷（如 $\\mathbf{MeSiCl_{3}}$ ， $\\mathbf{Me}_{2}\\mathbf{SiCl}_{2}$ 、MePhSiClz、PhSiCla、 $\\mathrm{Ph}_{2}\\mathrm{SiCl}_{2}$ ）出发，经水解缩合及重排，制成室温下稳定的硅氧烷预聚物。制成的涂料，在涂装施工后，在空气中湿气作用下或加热催化下交联固化成膜。合成反应及固化反应过程如图2-1-67所示（R代表Me或Ph）。  \n\n(2）结构与性能的关系从图2-1-67可以看出，有机硅树脂是由硅氧键（—Si—O—Si—）为骨架（主链）、烷基为侧基，属半无机与半有机结构的聚合物，兼有有机/无机聚合物的特性。在涂膜中是以Si-O键为主，Si和O原子形成d-pπ键，具有高于C—C键、C—O键的键能（Si—O键452kJ/mol；C—C键345.6kJ/mol；C—O键357.7kJ/mol)，对热和氧化稳定，并对Si原子所连接的烷基起屏蔽作用。在Si原子上连接的取代基有甲基、苯基、其他的烷基或芳基，还可以是不饱和的烷基。侧基赋予树脂反应性能与固化速率、线型结构程度、耐化学药品性及柔韧性等。但侧基含量高，相对降低—Si—O—Si一基含量，影响树脂的耐热性与抗氧化性。侧基（R）与Si有一定的比例（R/Si)，以满足不同性能要求。  \n\n![](images/feca971ca27ea4f22f5b654c0bb1efba27e7fb83a9c45b31c09ca4ba47947d91.jpg)  \n图2-1-67有机硅预聚物的制备及其固化成膜的反应过程  \n\n侧基中的苯基（Ph）和甲基（Me）相对含量不同（Ph/Me不同），树脂的性能也不同。Me含量高，树脂固化快，力学性能、耐水性较好，但耐热性与其他有机树脂的混溶性差。  \n\n根据对树脂结构与性能关系的研究进展，按照各种应用要求，设计相应的配方，优化R/Si与Ph/Me的比值。R/Si、 $\\mathbf{\\mathrm{Ph}}/\\mathbf{M}\\mathbf{\\mathrm{e}}$ 对有机硅成膜物性能的影响如图2-1-68、图2-1-69所示。  \n\n![](images/ef5e1edd4de9c8fa79e21a84de89ce8e0408e9814793363d3494d5a7031d3228.jpg)  \n图2-1-68R/Si对硅树脂性能的影响  \n\n![](images/bacff61bc11ce652554efa2e8cd717e4eb80754bf45c89570e9285e5caf0325c.jpg)  \n图2-1-69苯基含量对硅树脂性能的影响  \n\n(3）固化成膜的催化剂有机硅树脂借硅醇基、烷氧基等官能基之间缩合反应进行缩聚固化（图2-1-70)，反应速率较慢，需在200～250℃下烘烤1h，并且要用催化剂加速固化。胺、酸和碱也可以催化聚合，但这些催化剂对贮存稳定性和颜色有负面影响，一般不采用。  \n\n![](images/a4e5675579c24319453a169683c49ff97e9692f1c105d79d228032ec9f217e64.jpg)  \n图2-1-70有机硅树脂的基团间的反应  \n\n较好的固化催化剂是有机金属，其催化活性按以下顺序降低：Pb>Fe>Co>Mn>Zn。其中，月桂酸锌是较好的催化剂，它虽不是活性最高的，但在涂料制造过程中不至于产生凝胶化。环烷酸锌也可使用，但对涂膜颜色不利影响大于月桂酸锌。有机酸铝与铁盐催化活性太高，故有机硅树脂涂料要用塑料容器或塑料衬里的金属容器包装，避免因金属离子催化而使涂料过快地增稠甚至胶化。钻和锰加深涂膜颜色，一般只能在对涂膜颜色要求不严的场合使用。  \n\n人们对催化剂的活性和有机硅涂料贮存性、涂料施工前的使用寿命的平衡进行了许多研究，催化剂要在涂料制造中加入，保证良好的混溶性。为保证涂料贮存稳定，如果留出部分催化剂在施工前加入，会产生混溶性不良现象，尤其是有机硅树脂含量在 $75\\%$ 以上的情况更严重，使最后所得涂膜产生失光。可以在有机硅涂料中加入少量抗氧化剂或正丁醇和戊二酮，以延长贮存时间。有机酸金属盐催化剂一般配制成 $20\\%$ 的溶液加人。不同固化剂对有机硅性能的影响列于表2-1-253。  \n\n表2-1-253固化剂对有机硅树脂性能的影响  \n\n\n<html><body><table><tr><td>硅树脂类型</td><td>固化剂用量/%</td><td>固化时间（230C）/min</td><td>适用期</td><td>热稳定性/h</td></tr><tr><td>高交联度甲基环烷酸钻2.0 苯基硅树脂</td><td>无 环烷酸铅0.66 环烷酸锌2.0 环烷酸铅0.66，环烷酸钴2.66 环烷酸铅0.05，环烷酸锌2.0</td><td>约180 >5 约60 约60 <5 10</td><td>无限 1天 数月 数月 14天 >3个月</td><td>>2000 24 >2000 >2000 >2000 >2000</td></tr><tr><td>低交联度甲基环烷酸钻2.0 苯基硅树脂</td><td>无 环烷酸铅0.66 环烧酸锌2.0 环烷酸铅0.66，环烷酸钻2.66 环烷酸铅0.1，环烷酸锌2.0</td><td>约1800 10 600 600 10 45</td><td>无限 4天 数月 数月 18天 3个月</td><td>>2000 100 >2000 >2000 >2000 >2000</td></tr></table></body></html>  \n\n所有重金属固化剂对固化后涂膜的热稳定性有不利影响，而Co盐、 $Z_{\\Omega}$ 盐、Fe盐对涂膜热稳定性影响较小。使用 $\\mathrm{MeCOCH_{2}C O E t}$ ， $\\mathsf{M e C O C H_{2}C O M}.$ e、 $\\mathrm{HOOCC}_{3}\\mathrm{H}_{6}\\mathrm{COOH}$ 等作为整合剂，可大大提高铅盐催化剂的适用期。使用铝整合物作为固化剂时，还具有低温稳定、高温固化活性高等优点。采用 $\\mathtt{C u}$ 、Ni、Co、Cr等金属为中心原子的胺类络合物作为固化剂，可低温固化，并可改善有机硅清漆的贮存稳定性，固化后的树脂热力学性能、耐热性、电性能优异。这类固化剂不仅有单核的络合物，也有多核的。  \n\n近年来出现的含磷、钛、硼的硅氮树脂或硅氮化合物是较有效的固化剂，如含硼的聚甲基苯基硅氮、含硼的聚甲基硅氮、含磷钛的甲基硅氮等固化剂，可以作为有机硅涂料的常温固化剂，并能改善涂料的热稳定性和耐油性。原化工部涂料工业研究所采用含羟基的聚有机硅氧烷、耐热颜料、填料、N-5硅氮固化剂，研制出常温固化有机硅耐热防腐涂料，固化剂用量为 $3\\%\\sim5\\%$ 时，涂膜性能最好。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 473,
+        "chunk": "# 2.有机硅功能性涂料  \n\n(1）耐高温涂料有机硅树脂最突出的性能是优异的热氧化稳定性，主要是由于—Si—O—Si--为骨架，清漆可以在 $200{\\sim}250^{\\circ}\\mathrm{C}$ 下长期使用而不分解或变色。在更高的温度下（如 $400^{\\circ}\\mathrm{C}$ 以上)，Si原子上连接的烷基分解（或燃烧）掉，分子间形成新的—Si—O—Si—键和—Si—O—M—键，而不是树脂的分解（图2-1-71)。网络中的M（金属离子）是来自耐高温颜料和金属底材。  \n\n![](images/b29d78b12922301e18ccf0897dd873f75544ba49e37ca13b2ce1ec61ea90dcaa.jpg)  \n图2-1-71有机硅涂料在400℃以上进一步产生交联  \n\n由于有这一特点，用甲基硅氧烷树脂和高含量铝粉（用量在 $360_{\\mathrm{B}}/\\mathrm{L}$ 左右）的涂料，使用温度可以达到 $649^{\\circ}\\mathrm{C}$ 。与陶瓷釉料或磁性瓷料配合，使用温度可以达到 $816^{\\circ}C$ 。这些耐高温的有机硅涂料代表性应用有排烟管、烤炉、马弗炉、高炉（燃烧室）、热交换器、锅炉、烤肉架及器皿、喷气发动机零部件、排气管和其他发动机设备。美国Tempil公司生产一种能耐1370℃高温的有机硅消融隔热涂料，商品牌号为Pyromark2500，用于登月飞船的外表面保护。  \n\n适用于 $288\\sim316\\Upsilon$ 的白色和彩色的装饰性硅氧烷为基础的装饰性涂料，主要用于工业维护和用于高强度热轧钢设备、织物干燥器、烘炉以及用于需要耐高温和需要保光保色性好的场所。  \n\n耐高温的有机硅树脂涂料要求耐高温的颜料、填料与之匹配，并且对有机硅树脂无不良影响。白色颜料如使用 $\\mathrm{TiO}_{2}$ ，有机硅树脂涂料可在 $350\\sim400^{\\circ}\\mathrm{C}$ 下使用。其他彩色颜料一般采用无机颜料如铁系、镉系、铬系等，但也要考虑重金属对环境的污染。金属颜料可用铝、锌、不锈钢及钛镁粉，对提高耐热性和耐腐蚀性有利。体质颜料可用滑石粉、云母粉、碳酸钙、硫酸钡、石膏、硅藻土、二氧化硅等。  \n\n有机硅各色耐高温涂料、高温防腐涂料、有机硅陶瓷涂料的配方与工艺参见国内有关专著。  \n\n(2）绝缘涂料有机硅树脂的另一突出性能是其优良的电绝缘性，属H级绝缘材料，其介电损耗角正切、体积电阻率在 $0\\sim250\\ensuremath{\\mathrm{~\\circ~}}$ 之间变化不大（图2-1-72、图2-1-73)，是一种较好的耐高温电绝缘涂料，可长期在 $200^{\\circ}\\mathrm{C}$ 下使用。涂膜具有耐潮湿、耐酸碱、耐辐射、耐臭氧、耐电晕、耐燃、无毒等特性，广泛用于需要高温绝缘（H级）的各种电动机、电器的绝缘与保护要求。  \n\n![](images/10f26e6f7cbe2d75461a828184d75b509bb5994e4367dc993ffad506f3d4d403.jpg)  \n图2-1-72甲基苯基硅树脂及其他有机漆的介电损耗角正切与温度的关系  \n\n![](images/9a01354577f15e29f7a4ad75eab9560b820d168852b3e3f1c91f424379ce2148.jpg)  \n图2-1-73在1000V下甲基苯基硅树脂及某些有机漆的体积电阻率  \n\n(3）防粘脱模涂料除氟碳树脂外，有机硅树脂表面能低于其他各种有机树脂，制成防粘涂料，可长期在 $250^{\\circ}\\mathrm{C}$ 下使用。与聚四氟乙烯（特氟隆）或其他含氟树脂不粘涂料相比，虽然防粘性能稍逊，但是有机硅不粘涂料对铁、铝等基材具有较好的附着力，不产生有害的裂解产物，有机硅及其改性产品，也广泛用于炊具、食品加工机械的防粘涂料，成本也低于氟树脂不粘涂料。全国每年不粘涂料市场价值2亿多元，有机硅系列产品占有较大比例。  \n\n杜邦公司的特氟隆不粘涂料系列产品，由于在合成过程中使用了全氟辛酸铵，是否属于致癌物质尚无定论，但在国内外已被炒得沸沸扬扬，严重影响了其销路。使用有机硅系列防粘涂料，目前尚无此类问题产生。  \n\n用有机硅脱模涂料可通过喷涂、刷涂或者浸涂方法施涂于需要处理的表面上，烘烤固化，可获得一层坚韧、平滑、无色的半永久性涂膜。优点是省去脱模润滑剂和人工费，提高生产效率和产品质量，改善劳动条件，延长模具和型腔的使用寿命。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 474,
+        "chunk": "# 三、氟化基团改性有机硅涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 475,
+        "chunk": "# 1.氟化基团改性有机硅涂料进展概况  \n\n如前所述，有机硅涂料具有许多优点，广泛用于工业与国防军工领域，用途不断扩大，受到了国内外涂料科技界高度重视。近年来，氟化有机硅已成为该类涂料中一个十分活跃的研究领域。其原因是有机硅涂料虽具有杰出的耐高温性、电绝缘性和柔韧性，以及低于一般树脂的表面能，但其耐溶剂性、耐油脂性、耐燃料油性并不理想。和“异军突起”的氟树脂涂料相比较，树脂的表面能较高，化学稳定性差，耐候性也逊色。用氟化烷基改性，可使氟碳树脂涂料和有机硅涂料二者优势互补，开发出一类新型的氟硅复合树脂涂料，满足高科技产业与国防工业发展的需要。  \n\n氟化硅氧烷（fluorosiloxane或fluorosilicone）是个歧义性术语，并不能明示硅和氟原子在树脂中的分布及二者的连接方式。树脂中以Si—O、F—C键为主，也有Si—H、Si—C、C--H、C—O、O—H键，但没有Si—F键。因为和Si原子连接的F原子很活泼，极不稳定，离子化趋向 $70\\%$ 。由于这个原因，在Si原子和F—C键之间要引人亚乙基桥$-\\mathbf{C}\\mathbf{H}_{2}\\mathbf{C}\\mathbf{H}_{2}$ 一以助稳定。  \n\n在氟碳树脂工业中代表性的品种是聚四氟乙烯（PTFE)，而在有机硅工业中代表性的品种是聚二甲基硅氧烷（PDMS)。用氟化改性硅氧烷一般以PDMS作为对照物，进行性能对比，考察改性的效果。氟化硅氧烷的最早品种是聚二甲基三氟丙基硅氧烷（PMTFPS)，1950年以不同分子量的液体聚合物用于密封胶或弹性体，在有机溶剂、油脂和燃料油存在的环境使用，取代PDMS，减小树脂的溶胀率。PDMS、PMTFPS和PTFE的性能列于表2-1-254。  \n\n表2-1-254典型的硅氧烷工业产品与PTFE的性能  \n\n\n<html><body><table><tr><td>项 目</td><td>PDMS</td><td>PMTFPS</td><td>PTFE</td></tr><tr><td>分子式</td><td>[(CH)SiO}</td><td>(CH[CF(CH)2]SiO)</td><td>[CFCFz]</td></tr><tr><td>密度/（g/cm²）</td><td>1. 04~1, 51</td><td>1. 35~1. 65</td><td>2.13~2.19</td></tr><tr><td>硬度（邵尔A)</td><td>30~-80</td><td>20~80</td><td>邵尔D50~65</td></tr><tr><td>拉伸强度/MPa</td><td>1. 55 ~9. 0</td><td>5. 5~11. 7</td><td>27~41</td></tr><tr><td>伸长率/%</td><td>430~725</td><td>100~600</td><td>300~450</td></tr><tr><td>压缩永久变形(22h/177℃)/%</td><td>10</td><td>10~40</td><td></td></tr><tr><td>撕裂强度(die B)/(kN/m)</td><td>4.9 ~37.7</td><td>10.5~46.6</td><td>140~350</td></tr><tr><td>巴肖尔弹性/%</td><td>30~65</td><td>10~40</td><td></td></tr><tr><td>介电常数</td><td>2.8~3.7</td><td>7.0</td><td><2.1</td></tr><tr><td>临界表面张力/（mN/m）</td><td>20~23</td><td>21.4</td><td>18.5</td></tr><tr><td>密度参数/MPg1/2</td><td>15.1</td><td>17.9</td><td></td></tr><tr><td>O渗透系数</td><td>7.0</td><td>1. 6</td><td></td></tr></table></body></html>\n\n$\\Phi$ 渗透系数单位为（35℃，100psi）×10-1cm（STP） $\\mathrm{\\cm/(S\\cdot\\cm^{2}\\cdot\\ P a)}$ 。  \n\n虽然PMTFPS在使用中耐溶剂性、耐油性优于PDMS，但从表2-1-254中可以看出，氟碳树脂的优点并不突出，如临界表面张力改进不明显。显然，氟化改性硅氧烷不能满足于低氟化的PMTFPS品种，还应包括高氟化改性。长期的研究实践已形成共识，树脂的表面张力随其氟原子含量增加而降低，如聚甲基九氟己基硅氧烷（PMNFHS)，其临界表面张力降到 $16.3\\mathrm{mN/m}$ ，比PDMS的临界表面张力降低了 $5.1\\mathrm{mN/m}$  \n\n氟化改性的出发点主要是降低PDMS的表面张力、改进耐溶剂性，而不降低其稳定性和主链的柔韧性，这就是氟化改性硅氧烷的重点。当然，还要考虑其性价比。试验证实，不仅氟原子含量影响其表面张力，而且氟碳基结构及在树脂分子中所处位置对降低表面张力均有较大影响（表2-1-255)。从表2-1-255中可以看出，全氟甲基—CF3的临界表面张力最低$\\left(6\\mathrm{mN}/\\mathrm{m}\\right)$ ，通常处于端基，引入树脂中对降低表面张力效果明显。如果让H取代一个F原子，变成一 $\\mathrm{CF}_{2}\\mathrm{H}$ ，临界表面张力增加1.5倍（ $15\\mathrm{mN/m})$ 。如果全氟取代基在链中间$-\\mathrm{CF}_{2}$ 一，表面张力增加2倍。这为氟化改性硅氧烷提供了一个思路。  \n\n表2-1-255 氟取代基的结构与其临界表面张力  \n\n\n<html><body><table><tr><td>取代基</td><td>临界表面张力/（mN/m）</td><td>取代基</td><td>临界表面张力/（mN/m）</td></tr><tr><td>CF</td><td>6</td><td>CH</td><td>31</td></tr><tr><td>CFH</td><td>15</td><td>-CHCHCI-</td><td>39</td></tr><tr><td>CF-</td><td>18</td><td>聚酯</td><td>43</td></tr><tr><td>CH</td><td>22</td><td></td><td></td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 476,
+        "chunk": "# 2.氟化改性聚硅氧烷的途径  \n\n（1）主链、侧链同时氟化改性较早的氟化聚硅氧烷的合成方法，是在主链和侧基上同时引人氟取代基和氟碳键，合成了均聚物和共聚物。  \n\n![](images/9c96f8a3af05a83daca45ba58c2fd87d3e6828d0bafa52bea713e8a995634f9a.jpg)  \n均聚物  \n\n![](images/9782f4653ce1cb076c37ddc59d6e7a6312a6203c62a9f10dd1053094008517f6.jpg)  \n\n共聚物中，R代表一 $\\mathrm{CF}_{3}$ 封端的不同碳数的侧链， $\\mathbb{R}^{1}$ 、 $\\scriptstyle\\mathbf{R}^{2}$ 代表一 $\\mathbf{\\cdotCH_{3}}$ 或一 $\\cdot\\mathrm{CF}_{3}$ 封端的不同链长的侧基。均聚物的热稳定性略优于共聚物。这种高氟化、高一 ${\\cdot}{\\bf C}{\\bf F}_{3}$ 基的氟化改性硅氧烷虽然性能改进十分明显，但所用氟代硅氧烷单体昂贵，合成工艺复杂，所得产品成本较高，只是在基础研究上有意义，距离实际应用要求甚远。  \n\n（2）氟化硅氧烷和PMMA嵌段改性用氟化烷基硅氧烷如十三氟-1，1，2，2-四氢辛基硅氧烷（TFOS)、十七氟-1,1,2,2-四氢癸基硅氧烷（HFDS）和聚甲基丙烯酸甲酯（PMMA)合成嵌段共聚物；临界表面张力分别为 $11\\mathrm{mN/m}$ 和 $9\\mathrm{mN/m}$ ，表面能明显降低，氟化硅氧烷含量在 $18\\%$ 左右，还可和PMMA掺混，使氟化硅氧烷用量进一步降低，但从性价比考虑，仍难以实用化。  \n\n(3）用溶胶-凝胶法制备氟化硅氧烷  \n\n$\\Phi$ 溶胶-凝胶法的应用用溶胶-凝胶法制备新型有机-无机杂化涂料，由于工艺简便，获得具有纳米结构和纳米相的涂膜，赋予特殊性能，受到了国内外涂料界广泛重视。这里介绍用带支链的三乙氧基[4，4-（三氟甲基)-5，5,6,6,7,7,7-七氟庚烷］硅烷 $\\mathrm{CF}_{3}\\mathrm{CF}_{2}\\mathrm{CF}_{2}-$ $\\mathrm{C(CF_{3})_{2}C H_{2}C H_{2}C H_{2}S i(O C_{2}H_{5})_{3}(D3E t)}$ 和四乙氧基硅烷 $(\\mathbf{C}_{2}\\mathbf{H}_{5}\\mathbf{O})_{4}$ Si(TEOS)，进行溶胶-凝胶反应，其组成见表2-1-256。  \n\n表2-1-256涂料的组成  \n\n\n<html><body><table><tr><td rowspan=\"2\">组成</td><td colspan=\"3\">烷氧化物</td><td colspan=\"2\">溶剂</td><td colspan=\"3\">催化剂</td></tr><tr><td>D3Et</td><td>TEOS</td><td>MTM</td><td>乙醇</td><td>丁醇</td><td>HCI</td><td>HPO</td><td>HO</td></tr><tr><td>D3</td><td>0.1</td><td>1</td><td></td><td></td><td></td><td>0.07</td><td></td><td>11</td></tr><tr><td>MT</td><td></td><td></td><td>1</td><td>7</td><td>7</td><td></td><td>0.07</td><td>7</td></tr><tr><td>TS</td><td></td><td>1</td><td></td><td>7</td><td></td><td>0.07</td><td></td><td>11</td></tr></table></body></html>\n\n注；1.表中数据为摩尔比。2.MTM代表甲基三甲氧基硅烷。  \n\n以R-Si- $\\mathrm{OC}_{2}\\mathrm{H}_{5}$ 代表TEOS，以 $\\begin{array}{r l}{\\mathbf{R}_{i}{-}{\\mathbf{S}}\\mathbf{i}{-}\\mathbf{OC}_{2}\\mathbf{H}_{5}}\\end{array}$ 代表D3Et，在HCI催化下发生以下反应：  \n\n含氟碳的涂膜形成历程如图2-1-74所示。  \n\n![](images/ef3b5a8f1cba5fac3e7535b8ffee4df8c1e5c2a80d6093d2ba83fe7200ff50aa.jpg)  \n图2-1-74含氟碳的涂膜形成历程  \n\n![](images/4dc1a1e4197e5c30573021319d3ef0da26e543a43d05de1149f5368cb2ef2886.jpg)  \n图2-1-75 水的接触角 a—D3Et+ TEOS; b—TMT; c--TEOS  \n\n②对表面的改性图2-1-75中可以看出，二氧化硅-凝胶为网络基体，氟化硅烷Ri趋向富集于表面。对在不同的温度下烘烤的涂膜与水接触角测定结果示于图2-1-76，在烘烤温度 $400\\ensuremath{\\mathbb{C}}$ 以下的D3Et与TEOS涂膜对水接触角大于$100^{\\circ}$ ，显示降低表面自由能明显。  \n\n![](images/13b7f3f5b2c64aca0d4d3411572b28901c5722f8064ee16704cb02785f33d264.jpg)  \n图2-1-76水在涂膜表面接触角与D3Et $\\mathbf{\\sigma}:\\mathbf{\\sigma}$ TEOS（摩尔比）的关系  \n\n引人D3Et，在D3Et $\\because$ TEOS (摩尔比) ${>}0.02:1.0$ 水的接触角达到 $101^{\\circ}$ ，D3Et用量继续增加，水的接触 角平稳，说明少量D3Et就可以明显改进表面性能（图 2-1-76)。  \n\n这样的涂膜具有和PTEF同样的低表面能。经过XPS 对表面组成分析，氟化改性二氧化硅-凝胶涂膜的低表面能是由于氟碳分子富集于涂膜最上层的缘故。  \n\n(4）全氟代侧链改性利用聚合物的氟化侧链自组装作用形成均一的三氟甲基 $(\\mathrm{-CF_{3}}$ ）的有序排列特点，使表面能达到 $8\\mathrm{mN/m}$ 夏  \n\n用官能性全氟化醚（PFE）对硅氧烷弹性体改性，  \n\nPFE用量1.0%～1.5%，与水的接触角达到140°，表面自由能降到8mJ/m以下，而不影响弹性体的其他性能。全氟醚单体虽然价格不菲，但用量很少，有实用的前景。  \n\n含支链型聚氟化硅氧烷如三乙氧基［4,4-二(三氟甲基)-5,5,6,6,7,7,7-七氟庚基］硅氧烷（D3Et）和四乙氧基硅烷（TEOS）用溶胶-凝胶法实行氟化改性硅氧烷，D3Et：TEOS $\\c=$ 0.1：1.0（摩尔比)，表面能降低到10mJ/m²以下。改性剂用量少，性价比高，有工业化意义。  \n\n本节重点叙述官能性全氟化醚对硅氧烷的改性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 477,
+        "chunk": "# 3.官能性全氟醚改性硅氧烷树脂的制备与表征  \n\n(1）全氟醚改性硅氧烷树脂的制备以乙烯基聚二甲基硅氧烷（PDMS）为改性对象物，用杜邦公司生产的Krytox全氟醚烯丙基酰胺（PFE）为改性剂，在含SiH基的交联剂和铂催化剂存在下，SiH加成到乙烯基与丙烯基上，产生氢硅烷化反应［图2-1-77(a)]，  \n\n![](images/e630451fbe300601e8a1b4e186a5711c5a3e85b1bd8015b329bdea2d2e5894c9.jpg)  \n图2-1-77全氟醚烯丙基酰胺对PDMS的加成改性  \n\n生成弹性网络结构[图2-1-77（b）]。  \n\n加成反应步骤：先由乙烯基封端的PDMS和交联剂通过氢硅烷反应合成低聚物，该低聚物中仍含有部分SiH基，然后和少量Krytox全氟醚烯丙基酰胺（PFE）进行SiH基加成到烯丙基的双键上的反应（氢硅烷化反应），形成PFE改性的PDMS弹性网络[图2-1-77(b)]。在合成过程中会遇到PFE在PDMS溶液中低溶解性问题，PFE 在混合物中含量小于$0.5\\%$ （质量分数，以下同）时，混合物透明，对于PFE含量为 $0.5\\%\\sim1.5\\%$ ，混合物开始发雾(乳光)，如加热到固化温度 $70\\Upsilon$ 时，混合物变得很透明。在PFE含量大于 $1.5\\%$ 时，固化的涂膜也发雾，是不溶解的PFE所造成的。发雾的涂膜在分析测试之前，要将游离的涂膜用氯仿在索氏萃取器中萃取除去未反应的物料，然后将涂膜彻底干燥后再进行化学物理和抗粘性的测试分析。  \n\n(2）全氟醚（PFE）改性硅氧烷树脂的表面性能及其表征用PFE改性，是设想在铂催化剂存在下，甲苯作为反应介质，PFE和含SiH基的PDMS低聚物在 $75\\%$ 下进行氢硅烷化反应，生成PDMS弹性体。反应用HNMR监测，由 $-\\mathrm{siCH}_{2}\\mathrm{CH}_{2}\\mathrm{NH}{=}0$ 在0.488和$-\\mathrm{sicH_{2}C H_{2}C H_{2}N H{=}0}$ 在 $1.66\\delta$ 出现特征峰，以SiH在4.63o的特征峰的消失证实一SiH加到烯丙基酰胺的烯丙基双键上。  \n\n改性的和未改性的PDMS涂膜表面组成是用X射线光电光谱（XPS）分析测定的，所得到的谱线适用于涂膜表面下厚约30A。 $1\\dot{\\Lambda}=$ $0.1\\mathrm{nm};$ ）的膜层区。碳（1s）区的光谱示于图2-1-78。未改性的碳原子在形成的甲基中占统治地位，在PFE改性的PDMS涂膜的光谱中，结合能294eV、292eV是代表—CF和一 $\\cdot\\mathrm{CF}_{2}-$ 基团，在PFE含量为 $2\\%$ 时显示较大强度。改性的结果，氟碳基通过自组装富集在涂膜的表面上[图2-1-77（b)]，提供了明显表面改性的证明。  \n\n![](images/f658575302466b4e8b064c1be73d9d209b157e2f6003462d7aa117895388e6b8.jpg)  \n图2-1-78未改性和PFE改性的PDMS的XPS光谱  \n\n![](images/034ad86df0d11cdfa9ea20de7b7a0991863b4ce22cafa1a9b387463d655dbadb.jpg)  \n图2-1-79混合物中不同PFE含量（质量分数）对应于PDMS涂膜表面氟原子含量  \n\n![](images/a7f295eccbd89b732dc2ddc768e78dfa0b8532fabd397b215ba7f95f1b71e220.jpg)  \n图 2-1-80PFE改性的PDMS的表面能（通过十六烷静态接触角测定）  \n\n图2-1-79证实，PDMS涂膜表面氟原子含量随PFE在PDMS混合物中含量增加而增加，当PFE含量达到1.5%时，氟原子含量达到平衡值（ $30\\%)$ 。改性的PDMS表面自由能测定也证实PFE用量达 $1.5\\%$ 以上时，表面能从 ${20}\\mathrm{mJ}/\\mathrm{m}^{2}$ 降到最低点！ $\\scriptstyle<8\\mathrm{mJ}/\\mathrm{m}^{2}$ ，图2-1-80)。这些结果进一步证实PFE改性的结果。  \n\n在测定PDMS涂膜表面对水的接触角，随PFE含量从0增至1.25%时，前进接触角从120°增至 $\\boldsymbol{140^{\\circ}}$ ；在同样PFE浓度下，后退接触角从 $90^{\\circ}$ 降至 ${50}^{\\circ}$ （图2-1-81)，也说明表面张力明显降低。滞后作用（前进接触角与后退接触角之差）从 $30^{\\circ}$ 增至 $90^{\\circ}$ 。这表明在PDMS涂膜中存在高能酰氨基（极性基团)，它隐藏在PFE单分子层下面，在遇到极性大的水时，产生分子重组，显露出较大的滞后作用。与水接触角因引入PFE而增加 ${20}^{\\circ}$ ，改性效果明显。结合图2-1-79～图2-1-81，也证实PFE的用量在 $1.5\\%$ （质量分数）左右较合适，这不会增加过多成本。  \n\n(3）全氟醚对改性硅氧烷树脂（PDMS）其他性能的影响在改性的PDMS弹性体中引入酰氨基，对于含氟碳基（尤其是-CF基）的PFE趋向于表面富集和自组装排列，起推力作用，使PDMS的表面能有效地降低，而且PFE用量降低。但酰氨基是极性基团，尽管掩藏在低表面能的PFE分子层下面，但遇到含高能基（极性基）介质时就显露出作用力，增加改性的PDMS的黏结力，对于防粘作用可能带来影响。  \n\n采用丙烯酸做工业压敏胶（PSA）的胶带纸贴在PFE改性的PDMS涂膜上进行 $90^{\\circ}\\sharp$ 负荷剥离试验，测定剥离速率对每单位面积剥离断裂（开）能量的影响关系如图2-1-82所示。虽然PFE改性明显降低了PDMS的表面自由能，但剥离断裂（开）能量随PFE用量增加而明显增加。随着PFE用量从0增至 $1.5\\%$ ，对于剥离速率 $1000\\mu\\mathrm{m/s}$ ，剥离断裂（开）能量增加5倍（图2-1-82）。因为剥离断裂（开）能量与剥离速率遵循 $G=v^{n}$ 关系，为剥离速率，v增加对G影响较大。这说明PFE改性PDMS对PSA胶带纸黏结力大于未改性的PDMS。这可以通过调整PFE用量来有效调节PDMS的黏结力。对剥离的表面进行XPS分析证实，没有丙烯酸压敏胶从胶带纸面转黏附到PDMS表面上，也没有材料从PDMS表面转黏附到胶带纸面上，说明PFE改性的PDMS弹性体虽然略微增加了黏结性，但不影响它在防粘涂料中应用。  \n\n通过对未改性和改性的PDMS的动力机械分析证实，不论是聚合物的玻璃化温度还是动态剪切模量，都随PFE加人量变化而变化，但和未改性的PDMS相比较，模量（modulus）  \n\n![](images/029c6f2804e4b2a25502788f76426d926aeb81f5116cfd5b47b37edbee478552.jpg)  \n图2-1-81水的前进接触角和后退接触角  \n\n![](images/ac0795ea0e0a7e489de508cf487a68b871618dbe690c86c1bffedf166f45d6e7.jpg)  \n图2-1-82丙烯酸压敏胶在未改性和PFE改性的PDMS涂膜表面上的剥离试验  \n\n变化不大。聚合物模量反映它在外应力作用下抵抗形变能力的大小。模量越大越不易变形，  \n\n表明材料的刚度越大。贮存模量（storagemodulus）是模量的实数部分 $(E^{\\prime})$ ，表示黏弹性材料在形变过程中由于弹性形变而贮存的能量；损耗模量（lossmodulus）是模量的虚数部分 $(E^{\\prime\\prime})$ ，表示黏弹性材料在形变过程中能量的损耗。从图2-1-83中可以看出，PFE改性对PDMS的模量变化影响不大，说明改性对PDMS的弹性影响不明显。  \n\n(4）小结由烯丙基酰胺封端的全氟醚（PFE）和含SiH基的PDMS低聚物在铂催化剂存在下，通过氢硅烷化反应制得PFE改性PDMS，只需用少量PFE改性剂$(<1.5\\%)$ 可明显改进PDMS表面性能而不影响PDMS网络的弹性和刚度，有合理  \n\n![](images/f9602d9c8be8cbaf69dd00ede879bcbfeb69ab84d8230bd9c9078887befdf9a8.jpg)  \n图2-1-83未改性和PFE改性的（分别用实线和虚线代表）PDMS贮存模量E和损耗模量 $\\boldsymbol{E^{*}}$  \n\n的性价比。表面与水的接触角滞后作用是由于膜中酰氨基与水相互作用，虽然工业压敏胶带试验显示其断裂能量增加，但是结合剥离效果，通过调节PFE用量，不影响在不粘涂料中应用。酰氨基对于PFE基趋向表面富集与均匀排列起推斥作用，PFE形成均一的单分子层，对设计易控制的不粘涂料提供了有益的设计思路。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 478,
+        "chunk": "# 4.氟化聚硅氧烷在涂料中应用  \n\n氟化聚硅氧烷具有有机硅热稳定性、柔韧性，具有和聚四氟乙烯相同或更低的表面能，提高了有机硅的耐溶剂性和耐候性，使氟化聚硅氧烷在涂料中的应用范围日益扩大。氟化聚硅氧烷在涂料中应用领域列于表2-1-257。 C  \n\n(1）低表面能涂料氟化聚硅氧烷具有低于有机硅和氟碳树脂的表面能，在许多低表面能的涂料品种中得到应用。最大的应用是防粘涂料，这与用于厨具、食品加工机械等的不粘涂料不同，不粘涂料主要功能是防食物黏附、易于清洗，要求耐高温、耐刮擦、防腐、与食品接触无毒。防粘涂料（剥离涂料）主要是用在两种材料之间的界面，以便防止强黏结而不易剥离。已制造出了脱膜涂料、自粘贴衬里、橡皮糖包装纸衬里涂层。防粘（剥离）涂料最大的市场是保护用压敏胶涂覆的产品，特别是适用于以聚二甲基硅氧烷（PDMS）为基础的压敏胶的剥离涂料，低表面能的性能帮助润湿衬垫塑料纸表面，获得平滑、均匀的涂层，满足易剥离的需要。  \n\n表2-1-257氟化聚硅氧烷在涂料中应用领域  \n\n\n<html><body><table><tr><td>低表面能涂料</td><td>耐大气腐蚀涂料</td><td>特种功能型涂料</td><td>助 剂</td></tr><tr><td>不粘涂料、防沾污自洁涂 料、海洋舰船底防污涂料</td><td>耐候性涂料、沙漠地区太 阳能装置涂料、耐冰雪涂料</td><td>耐汽车、飞机用燃料油的 涂料、抗菌涂料、电子敏感元车专用防护脂、织物整理剂</td><td>消泡剂、抛光剂、偶联剂、轿</td></tr></table></body></html>  \n\n临界表面张力低于 $8\\mathrm{mN/m}$ 的氟化烷基侧链改性聚硅氧烷，是制备防沾污自洁建筑涂料的成膜材料。防沾污涂料可以用于精密仪器、器具、医疗设备的表面涂料，减少沾污沾尘，并易于清洁。在传感器和电子敏感元件上也得到了应用。  \n\n用支化和超支化的氟化烷氧基改性聚硅氧烷可以达到超低表面张力 $(6\\mathrm{mN/m})$ ，代替有机硅用于海洋舰船底部的自抛光无毒防污涂料，代替有机硅自抛光涂料，效果很好。和纳米结构材料配合，使防污涂料具有纳米尺寸的粗糙度，减少海洋微生物如藤壶、管状软体虫和其他海洋微生物的附着力，在舰船行驶时，借助海水的扰动与船底的摩擦，微生物被甩掉，起到防污作用。这为开发无毒的防污涂料提供了新途径。  \n\n利用全氟取代基侧链改性聚硅氧烷获得了成功，这是利用全氟侧链在涂膜中聚集于涂膜表面，自组装排列成氟碳基单分子层，降低表面能，提高整体涂膜的化学稳定性、耐候性，同时可使配方中氟含量降到最低，降低成本，吸引了国内外涂料工作者关注，发展了全氟侧链改性的低表面能的新树脂材料。如主链为聚酯、聚矾嵌段共聚，侧链为全氟烷基，可以得到临界表面张力小于 ${\\mathfrak{g}}_{\\mathrm{mN/m}},$ 。在舰船防污涂料、人体器官移植等特种涂料上得到应用。以聚苯乙烯为主链、全氟烷基为侧链的半氟化嵌段共聚物，得到临界表面张力接近 $8\\mathrm{mN/m}$ 的低表面能的新树脂材料。  \n\n(2）耐大气腐蚀涂料有机硅涂料耐候性处于合成树脂涂料的中高档次，但逊于氟碳树脂涂料。氟碳树脂涂料虽具有超常的耐候性，由于价格偏高，影响推广。利用氟碳基团在涂膜中趋向富集于表面的特点，采用少量支化氟碳烷基硅氧烷改性有机硅涂料，可使其耐候性接近氟碳涂料，又有较易接受的性价比，这是一类有开发前途的品种。  \n\n氟化聚硅氧烷涂料表面疏水，具有较好热稳定性和低温柔韧性，制备电热涂料，用于铁轨融雪、飞机机翼除冰、高压电缆除冰去霜。  \n\n(3）特种功能型涂料有机硅涂料虽能耐高温，但耐油性、耐燃料油性比较差，限制了在航空、汽车中使用。氟化改性聚硅氧烷制备涂料提高了耐油性、耐溶剂性、耐燃料油性，用于飞机等航空器、汽车等发动机内壁、管路连接等防腐蚀，处于不可替代的位置。  \n\n润滑、耐磨涂料广泛用于矿山、冶金、建材、能源、农机、交通运输各种机械的零部件上，特别适用于航空、航天、军工器械上。这些要求涂料热稳定性好，表面能低，耐化学腐蚀，自润滑性和耐磨性好。聚四氟乙烯（PTFE）在润滑、耐磨涂料领域占有重要位置。氟化聚硅氧烷的出现，可以得到低于PTFE 的表面能，具有更有效的润滑、耐磨作用，使润滑、耐磨涂料质量水平大为提高，更扩大了应用。  \n\n氟化聚硅氧烷涂料不支持霉菌生长，和纳米 $\\mathrm{TiO}_{2}$ 配合制成抗菌涂料，效果优于其他同类品种。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 479,
+        "chunk": "# 5.结论  \n\n氟化改性聚硅氧烷能保持有机硅热稳定性和主链柔韧性，能明显改进耐溶剂性，达到比聚四氟乙烯更低的临界表面张力，基本上综合了氟硅材料的优点。利用氟碳基尤其是全氟取代基具有趋向于表面、自组装排列成单分子层的特性，使改性聚合物临界表面张力可以降到$\\scriptstyle10\\mathrm{mN/m}$ ，甚至更低，少量的全氟改性剂就可以收到明显改性效果，而不影响改性的有机硅整体性能。这为尽量减少氟化改性剂用量、降低成本提供了十分有益的启示。  \n\n由于氟化聚硅氧烷综合了二者优点，在工业涂料、特种涂料、涂料助剂中得到了应用，并具有进一步扩大市场的巨大潜力。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 480,
+        "chunk": "# 四、有机硅高固体分涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 481,
+        "chunk": "# 1.纯有机硅高固体分涂料  \n\n(1）纯有机硅涂料高固体分化的趋势有机硅高固体分涂料包括纯有机硅型和有机硅改性树脂型两种类别。纯聚有机硅烷或硅氧烷树脂主要用于耐高温涂料，最早是1934年用于电动机绝缘玻璃纸的耐热涂层，第二次世界大战后，有机硅树脂开发了数以百计的耐高温涂料配方。  \n\n耐高温涂料的定义有不同说法，国内文献认为能长期经受 $200^{\\circ}\\mathrm{C}$ 以上温度，涂膜保光保色性较好，涂膜完整，没有碎裂现象，仍能保持适当的物理机械性能和起防护作用的涂料，称为耐高温涂料。有的认为，能满足123.6℃（250°F）～760℃（1400°F）的温度范围使用的涂料称为耐高温涂料。  \n\n国际上对涂料中VOC（volatileorganiccompouds，有机挥发物）的限值法规日趋严格，如美国1999年生效的《建筑涂料和工业维护涂料管制条例》规定工业涂料VOC为 $250\\sim$ $450\\mathrm{g/L}$ ，水性涂料为 $\\mathrm{voc}{\\leqslant}250\\mathbf{g}/\\mathrm{L}$ （扣水计算），随后进一步修订标准，工业涂料VOC向$200\\mathbf{g}/\\mathrm{L}$ 以下，水性涂料VOC向 $100\\mathrm{g/L}$ （扣水计算）以下的目标趋近。  \n\n有机硅耐高温涂料通常是固体分在 $50\\%$ 左右的二甲苯液，虽属于特种涂料，但同样受到降低VOC法规的压力。1994年美国要求耐高温（ $1000^{\\circ}\\mathrm{F}$ ，折合 $537.8\\Upsilon$ ）涂料的VOC要降至 $419.58/\\mathrm{L}$ ，比原来的VOC降低41. $66\\%$ 。但对于温度较低（204.4℃）的耐热涂料则要求降至 $299,6g/\\mathrm{L},$ 。可见，作为特种涂料的有机硅耐高温涂料也要降低VOC，这就是纯有机硅涂料高固体分化的必要性。国内对特种涂料降低VOC要求也会很快提到日程上。  \n\n(2）纯有机硅高固体分耐高温涂料  \n\n$\\Phi$ 有机硅树脂高固体分化途径传统的有机硅耐高温涂料的有机硅树脂分子量为40万～50万，配制成50%二甲苯液，施工时还要用芳香烃溶剂稀释至施工黏度，是低固体分高VOC涂料。要降低VOC，提高固体分，有效的途径是设计低分子量、高交联活性的有机硅树脂。一般有两种途径。 4  \n\n第一种途径是在有机溶剂中水解苯基甲基氯硅烷并部分缩合硅醇以形成部分水解物，是一种低分子量的高反应性的低聚物，可以大幅度提高固体分，如表2-1-258的A和C。树脂A中二官能度的硅氧烷多于树脂C，二者在同样固体分下，A的黏度低。涂料施涂后可借助锌、钻或铁的月桂酸盐进一步缩合固化成膜。  \n\n实行高固体分的第二种途径是由官能基烷氧基硅烷和聚有机硅烷，与硅醇官能基聚有机硅氧烷按一定比例混合，施涂后，通过钛酸酯催化固化或加热固化成膜，如树脂B。产品虽是无溶剂的，但加热固化时释放出部分甲醇属VOC，故固体分是 $90\\%$ (表2-1-258)。  \n\n表2-1-258 有机硅树脂特性  \n\n\n<html><body><table><tr><td>树 脂</td><td>非挥发分（质量分数）/%</td><td>黏度/mPa*s</td><td>官能度</td></tr><tr><td>低VOC</td><td></td><td></td><td></td></tr><tr><td>A(软）</td><td>80</td><td>2000</td><td>SiOH(3%)</td></tr><tr><td>B(硬)</td><td>90</td><td>550</td><td>SiOH(2%) SiOMe(15%)</td></tr><tr><td>C(硬）</td><td>80</td><td>7000</td><td>SiOH(3%)</td></tr><tr><td>高VOC</td><td></td><td></td><td></td></tr><tr><td>D（软）</td><td>50</td><td>1250</td><td>SiOH(1%)</td></tr><tr><td>E(硬）</td><td>50</td><td>1250</td><td>SiOH(1%)</td></tr></table></body></html>  \n\n这两种方法制备高固体分涂料及涂膜固化的有关化学反应见有关文献。  \n\n$\\textcircled{2}$ 高固体分有机硅耐热性白色涂料用表2-1-258中所列五种有机硅树脂分别制备白色涂料，金红石型 $\\mathrm{TiO}_{2}$ ：有机硅树脂 $=45:45$ （质量比)，另加云母粉10份，用 $3200~\\mathrm{r/min}$ 高速搅拌分散 $15\\mathrm{min}$ ，用二甲苯稀释到喷涂黏度（2号Zahn杯，30s），然后测试涂料特性与施工。将五种白色涂料喷涂在已喷砂处理的冷轧钢板上，在 $232.24\\times$ （450°F)/30min下固化，涂膜附着力采用划格法检测，试验样板暴露在 $250\\mathrm{\\textperthousand}$ 下，分别测定其光泽度、颜色和其他损坏情况。检测结果列于表2-1-259和表2-1-260。  \n\n表2-1-259有机硅白色涂料特性  \n\n\n<html><body><table><tr><td rowspan=\"2\">白涂料</td><td rowspan=\"2\">非发</td><td rowspan=\"2\">/L</td><td rowspan=\"2\">VOC)</td><td rowspan=\"2\">60°光泽度</td><td rowspan=\"2\">硬度</td><td rowspan=\"2\">附着力</td><td colspan=\"2\"></td></tr><tr><td></td><td></td></tr><tr><td>低VOC</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>A(软)</td><td>77</td><td>12.3</td><td>348</td><td>4</td><td>3B</td><td>100</td><td>100</td><td>100</td></tr><tr><td>B(硬)</td><td>83</td><td>12.3</td><td>252</td><td>25</td><td>H</td><td>100</td><td>18</td><td>27</td></tr><tr><td>C(硬)</td><td>74</td><td>12.3</td><td>383</td><td>23</td><td>F</td><td>100</td><td>8</td><td>9</td></tr><tr><td>高VOC</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>D(软)</td><td>54</td><td>10.3</td><td>575</td><td>54</td><td>2B</td><td>100</td><td>2</td><td>2</td></tr><tr><td>E(硬）</td><td>56</td><td>10.5</td><td>563</td><td>57</td><td>B</td><td>82</td><td>2</td><td>2</td></tr></table></body></html>  \n\n表2-1-260有机硅白色涂料耐热性比较   \n\n\n<html><body><table><tr><td rowspan=\"2\">白色涂料</td><td colspan=\"4\">60°光泽度/%</td><td colspan=\"3\">色差(△E)</td><td colspan=\"3\">其他性能</td></tr><tr><td>0</td><td>100h</td><td>300h</td><td>500h</td><td>100h</td><td>300h</td><td>500h</td><td>100h</td><td>300h</td><td>500h</td></tr><tr><td>低VOC A(软) B(硬) C(硬)</td><td>4 25 23</td><td>5 18</td><td>5 17</td><td>5 16</td><td>1.1 0.9</td><td>1.2 0.8</td><td>1.0 0.7</td><td>10 10</td><td>10 10</td><td>10 10 10</td></tr></table></body></html>\n\n$\\Phi$ 10=无损坏，  \n\n从表2-1-259看出，A（软）和D（软）相比，VOC的量减少 $227_{8}/\\mathrm{L}$ ，其固体分提高$20\\%$ 以上；B（硬）和E（硬）相比，固体分提高 $27\\%$ ，而B（硬）的VOC只有E（硬）的一半。A、B、C三种有机硅树脂的VOC量均比美国标准规定的 $419,58/\\mathrm{L}$ 要低得多。B（硬）是多官能度的硅氧烷低聚物，交联活性大，其VOC量达到耐热涂料的 $299,6g/\\mathrm{L}$ 的严格标准。  \n\n低VOC的A（软）的涂膜光泽度很低，硬度也低，但耐溶剂性好；B（硬）和E（硬)相比，涂膜硬度、附着力、耐溶剂性，前者优于后者。  \n\n表2-1-260的结果证实，样板在 $250\\Upsilon$ 下试验 $100\\mathrm{{h}}$ ， $_{300\\mathrm{h}}$ . $500\\mathrm{h}$ ，涂膜光泽度、色差和其他损坏情况对比，低VOC的A、B、C三种白色涂料不比高VOC的D、E差。  \n\n综合以上情况，证实有机硅耐高温的高固体分涂料（ $250\\sim537.8\\mathcal{C}$ ）在技术上是可行的。  \n\n$\\textcircled{3}$ 高固体分有机硅耐高温铝粉涂料铝粉和有机硅树脂配合可以提高涂料的耐热性，可使涂膜在 $500\\mathrm{^q}$ 以上高温下应用。将表2-1-258中的A、B、D、E四种有机硅树脂分别制成铝粉涂料，有机硅树脂（以固体树脂计）：飘浮型铝粉 $\\mathbf{\\tau}=1:1$ (质量比)，用二甲苯稀释至喷涂黏度30s(2号Zahn杯)。将制得的上述铝粉涂料分别喷涂在冷轧钢板（032）上，在 $232.37.$ $(450^{\\circ}\\mathrm{F})/30\\mathrm{min}$ 下固化，涂料B用 $6\\%$ （以固体树脂计）的四丙基钛酸酯作为催化剂。有机硅铝粉涂料的特性及其涂膜的物性和耐热性列于表2-1-261。涂膜耐热性试验是在喷砂的冷轧钢板上，在 $232.2^{\\circ}\\mathrm{C}$ （450F）/30min下固化，样板放在 $537.8\\mathrm{^qC}$ （1000°F）的马弗炉中进行耐热性试验，考察涂膜在100h、250h和500h时的耐热性，以涂膜损失（失重）、开裂或其他变化来评价耐热性，评定为10，是无损坏；9是痕量损坏；8是 $1\\%\\sim5\\%$ 损坏（表2-1-261)。  \n\n表2-1-261有机硅铝粉涂料特性及其涂膜性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">铝粉涂料</td><td rowspan=\"2\">非挥发分</td><td rowspan=\"2\">密度L</td><td rowspan=\"2\">VOL)</td><td rowspan=\"2\">铅笔硬度</td><td rowspan=\"2\">(</td><td colspan=\"2\">(米</td><td colspan=\"3\"></td></tr><tr><td></td><td></td><td>100h</td><td>耐热性</td><td>500h</td></tr><tr><td>低VOC A(软) B(硬) 高VOC</td><td>58 60</td><td>1.09 1.11</td><td>455 455</td><td>2H 5H</td><td>100 100</td><td>45 56</td><td>60 90</td><td>10 10</td><td>10 10</td><td>8 9</td></tr></table></body></html>  \n\n从表2-1-261中的低VOC的A（软）、B（硬）与高VOC的D（软)、E（硬）的铝粉涂料特性及其涂膜性能对比检验结果，高固体分有机硅铝涂料的固体分提高了 $19\\%$ ，而VOC相应降低了 $180\\mathbf{g}/\\mathrm{L}$ （软）和 $156\\mathrm{g/L}$ (硬)，而各种性能，尤其是耐热性不比传统的树脂D、E差，而耐溶剂性较优，证实可以开发出性能优良的较高固体分耐高温的有机硅耐热铝粉涂料。高固体分有机硅铝粉涂料的VOC虽然降到 $455\\mathrm{g/L}$ ，但离美国规定的 $419,58/\\mathrm{L}$ 仍有一定差距。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 482,
+        "chunk": "# 2.有机硅改性丙烯酸树脂高固体分涂料  \n\n(1）用硅氧烷封闭羟基的丙烯酸高固体分涂料  \n\n$\\textcircled{1}$ 封闭的羟基丙烯酸酯合成丙烯酸低聚物中羟基是交联用的官能基，极性大，使低聚物黏度提高。为降低树脂极性，采用硅氧烷预先封闭羟基（甲基）丙烯酸单体中的羟基：  \n\n![](images/649556547ad250ba198057d8c715c415e0acbe30434817456e3c2c5546ae4049.jpg)  \n\n将甲基丙烯酸 $\\scriptstyle{a}$ 羟基乙基酯作为“捕获”反应中产生的HCl的三乙基胺、正已烷（溶剂）加入反应瓶中，然后在冷却状态下滴加三甲基氯硅烷。过滤去除所得铵盐。减压蒸馏得到甲基丙烯酸三甲基硅氧乙基酯（TMSEMA)。这是含有封闭羟基的甲基丙烯酸酯单体，用B一OH代表，可以和其他丙烯酸酯、乙烯基单体共聚制成丙烯酸酯低聚物。被封闭的羟基可以在催化剂或水分作用下解封释放出羟甲基和硅烷基。由于羟基被极性很低的硅氧基封闭，含B—OH的丙烯酸低聚物极性降低，黏度比含有未封闭羟基的丙烯酸低聚物要小得多，固体分却提高了 $20\\%$ 身",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 483,
+        "chunk": "# $\\textcircled{2}$ 丙烯酸低聚物合成  \n\na.丙烯酸低聚物配方配方及有关技术参数见表2-1-262。  \n\n表2-1-262丙烯酸低聚物配方及有关技术参数  \n\n\n<html><body><table><tr><td>项目</td><td>单体</td><td>R-1</td><td>R-2</td><td>R-3</td><td>R-4</td><td>R-5</td><td>R-6</td></tr><tr><td>非官能性单体</td><td>St</td><td>20.4</td><td>20.4</td><td>2</td><td>0.4</td><td>26.2</td><td>29.6</td></tr><tr><td></td><td>α-EHA</td><td>36.7</td><td>36.7</td><td>24</td><td>20.7</td><td>45.5</td><td>45.9</td></tr><tr><td>B—OH</td><td>TMSEMA</td><td>66.7</td><td>一</td><td>40.5</td><td>58.6</td><td></td><td></td></tr><tr><td>含一OH基</td><td>HEMA</td><td>一</td><td>42.9</td><td>一</td><td>一</td><td>一</td><td>一</td></tr><tr><td>含环氧基</td><td>GMA</td><td>一</td><td>一</td><td>35.6</td><td>41.2</td><td>一</td><td>一</td></tr><tr><td>二元酸</td><td>ITAn</td><td>一</td><td>一</td><td>-</td><td>一</td><td>28.3</td><td>一</td></tr><tr><td></td><td>MAn</td><td>一</td><td>一</td><td>一</td><td>一</td><td>一</td><td>24.5</td></tr><tr><td>f/(1000g/mol)</td><td></td><td>3.3</td><td>3.3</td><td>2.5</td><td>2.9</td><td>2.5</td><td>2.5</td></tr><tr><td>M</td><td></td><td>1. 0×10</td><td>1.1×10a</td><td>0.86×10</td><td>0.76×10a</td><td>1.2×10</td><td>1.2×10</td></tr><tr><td>M</td><td></td><td>1.6X10</td><td>1.7×10a</td><td>1.5 ×10a</td><td>1. 4×10a</td><td>2. 0×10a</td><td>2. 0×10</td></tr><tr><td>M/M</td><td></td><td>1.6</td><td>1.6</td><td>1.7</td><td>1.3</td><td>1.7</td><td>1.7</td></tr><tr><td>T/C</td><td></td><td>0</td><td>0</td><td>10</td><td>15</td><td>0</td><td>0</td></tr></table></body></html>\n\n注：St为苯乙烯；a-EHA为丙烯酸-a-乙基已酯；TMSEMA为甲基丙烯酸三甲基硅氧乙基酯；B—OH为羟基被硅氧 基封闭；HEMA为甲基丙烯酸-a-羟乙基酯；GMA为甲基丙烯酸缩水甘油酯；ITAn为反丁烯二酸酐；MAn为顺丁烯二 酸酐。  \n\nb.合成工艺基本和一般丙烯酸树脂合成工艺相似。将单体混合物和α，α-偶氮二异丁睛（按需要量配制成溶液）分别置于两个滴加器中，在 $140^{\\circ}\\mathrm{C}/6\\mathrm{h}$ 搅拌下滴加到预先放置有二甲苯（总投料量 $75\\%$ ）的反应釜中，物料滴加完后在 $140^{\\circ}\\mathrm{C}$ 下保持 $5\\mathrm{h}$ ，然后减压蒸去二甲苯。分别制得含B—OH基和—OH基的R-1与R-2；含B—OH基和环氧基而原料配比与官能度不同的R-3和R-4；含不同酸酐的低聚物R-5和R-6。这些低聚物的数均分子量为$760\\sim1200$ ，多分散性均为1 $\\cdot6{\\sim}1.7$ (GPC 测定)。  \n\n$\\textcircled{3}$ 汽车清面漆（罩光漆）中应用  \n\na.B—OH/—NCO体系交联固化反应涂料是双包装体系，含封闭羟基（B-OH）的丙烯酸低聚物（R-1）为一包装，多异氰酸酯为另一包装，在 $140\\mathrm{^c/20min}$ 下固化，经历以下反应（图2-1-84)：  \n\n![](images/4de9879143f5d0d83afcd94fdf8a875fcd434a0844c324ff7fe4be5538bf4935.jpg)  \n图2-1-84含封闭OH基的丙烯酸低聚物/多异氰酸酯体系的反应机理  \n\n反应第一步是催化剂或水分存在下，封闭的羟基解封，释放出一OH基和生成三烷基（甲基）硅醇，三烷基硅醇可以自缩合成硅氧烷留在涂膜中，对涂膜外观起调整作用，同时生成封闭羟基解封所需要的水分。第二步是熟悉的一OH/—NCO反应，交联成涂膜。  \n\nb.B—OH/环氧/酸酐体系杂化交联固化含B--OH的丙烯酸低聚物（R-1)、含B—OH与环氧基丙烯酸低聚物（R-3、R-4）和含酸酐的丙烯酸低聚物（R-5、R-6）配成清漆，进行杂化交联，在 $140\\%/20\\mathrm{min}$ 下固化反应机理如下（图2-1-85）：  \n\n![](images/49362235aa6e3c8fd39effb107eea6b89a8ba4a6929e7c96500701defc553e66.jpg)  \n图2-1-85B—OH/酸酐/环氧体系反应机理  \n\n反应第一步和图2-1-84的第一步相同，反应第二步是新释放出的—OH基和酸酐开环反应，产生—COOH基，一COOH基再与环氧反应交联成涂膜。也是双包装体系，含B—OH的丙烯酸低聚物和含环氧基的丙烯酸低聚物为一包装，其他组分为另一包装。  \n\nc.汽车清面漆性能B—OH/—NCO体系与—OH/--NCO、氨基丙烯酸体系的配方与性能列于表2-1-263。  \n\n表2-1-263—OH/—NCO（HAS-1)、B—OH/—NCO（HAS-2）和氨基丙烯酸（HAS-3)三个体系的配方和140℃/20min下固化的涂膜性能  \n\n\n<html><body><table><tr><td>组分</td><td>HAS-1</td><td>HAS-2</td><td>HAS-3</td><td>组分</td><td>HAS-1</td><td>HAS-2</td><td>HAS-3</td></tr><tr><td>R-1</td><td>一</td><td>58.2</td><td>一</td><td>非挥发分/%</td><td>66</td><td>83</td><td>47</td></tr><tr><td>R-2</td><td>58.2</td><td></td><td></td><td>耐二甲苯摩擦</td><td>好</td><td>好</td><td>好</td></tr><tr><td>A-345</td><td>一</td><td></td><td>70</td><td>抗摩划性（保光率）/%</td><td>73</td><td>76</td><td>23</td></tr><tr><td>DN-990S</td><td>41.8</td><td>41.8</td><td></td><td>凝胶分数/%</td><td>98.2</td><td>98.8</td><td>95.4</td></tr><tr><td>L-117-60</td><td>一</td><td>一</td><td>30</td><td>固化涂膜T/C</td><td>85</td><td>85</td><td>110</td></tr><tr><td>烷基磷酸酯</td><td>2</td><td>2</td><td>一</td><td>Mc</td><td>740</td><td>770</td><td>549</td></tr></table></body></html>\n\n$\\Phi$ A-345：汽车涂料通用的丙烯酸树脂，DIC的产品，$\\oslash$ DN-990S：多异氰酸酯树脂，DIC的产品。$\\textcircled{3}$ L-117-60：三聚氰胺甲醛树脂，DIC的产品。$\\textcircled{4}$ 非挥发分（固体分）：在喷涂施工黏度（25℃，幅特杯20s）下的非挥发分（固体分）。$\\textcircled{5}$ 抗摩划性：用质量1. $6|\\mathbf{x}_{\\mathbf{B}}$ 的清洁器摩擦30min后，测20\\*的涂膜光泽度，对比计算保光率。$\\textcircled{6}$ 凝胶分数：制得的游离涂膜用丙酮萃取24h，然后在60°℃干燥1h，根据萃取前后的涂膜质量计算凝胶分数。$\\oslash M_{\\complement}$ ：涂膜交联点之间分子量， $1/M_{\\mathrm{C}}$ 表征交联密度，  \n\n从表2-1-263中的非挥发分、抗摩划性可以看出，HAS-2（含B—OH）大大优于HAS-  \n\n3传统的氨基丙烯酸涂料，也优于未封闭一OH基的HAS-2。  \n\nB--OH/环氧/酸酐体系杂化交联的清漆配方与在140℃/20min下固化涂膜性能列于表2-1-264。  \n\n表2-1-264B—OH/环氧/酸酐清漆配方和固化涂膜性能  \n\n\n<html><body><table><tr><td>组分</td><td>HAS-4</td><td>HAS-5</td><td>HAS-6</td><td>组分</td><td>HAS-4</td><td>HAS-5</td><td>HAS-6</td></tr><tr><td>R-3</td><td>50</td><td>一</td><td>一</td><td>1-甲基咪唑</td><td>1.0</td><td>1. 0</td><td>1.0</td></tr><tr><td>R-4</td><td>一</td><td>46.3</td><td>46.3</td><td>凝胶分数/%</td><td>93.8</td><td>93,4</td><td>93.4</td></tr><tr><td>R-5</td><td>50</td><td>53.7</td><td>一</td><td>抗摩划性（保光率）/%</td><td>32.8</td><td>62.9</td><td>65.3</td></tr><tr><td>R-6</td><td>一</td><td>一</td><td>53.7</td><td>固化涂膜T/C</td><td>78.8</td><td>93.8</td><td>95.5</td></tr><tr><td>烷基磷酸酯</td><td>2</td><td>2</td><td>2</td><td>Mc</td><td>599</td><td>489</td><td>470</td></tr></table></body></html>  \n\n烷基磷酸酯和1-甲基咪唑分别为B—OH解封和环氧/一COOH反应的催化剂。  \n\n从表2-1-264中的抗摩划性、 $\\boldsymbol{T_{s}}$ 与交联密度可以看出，以HAS-6为优，说明顺丁烯二骏酐（HAS-6）优于反丁烯二酸酐（HAS-5)，官能度高的低聚物R-4也起了作用。  \n\n从筛选的配方HAS-2（含B—OH丙烯酸低聚物/—NCO体系）、混合交联（B—OH/环氧/酸酐）的HAS-6和传统的氨基丙烯酸配方HAS-3，都配成汽车清面漆，用氨基丙烯酸色漆作为底色漆，喷涂后接着分别喷三种清面漆，两喷一烘，在 $140\\%/20\\mathrm{min}$ 下固化，涂膜性能检测结果列于表2-1-265。  \n\n表2-1-265汽车清面漆性能比较  \n\n\n<html><body><table><tr><td>检测项目</td><td>化</td><td></td><td></td><td>检测项目</td><td>化</td><td></td><td></td></tr><tr><td>铅笔硬度</td><td>HB</td><td>H</td><td>F</td><td>耐酸雨性</td><td>好</td><td>好</td><td>差</td></tr><tr><td>20°光泽度/%</td><td>86</td><td>87</td><td>88</td><td>凝胶分数/% 非挥发分/%</td><td>98.8 88</td><td>96.2 90</td><td>95.4</td></tr><tr><td>二甲苯摩擦</td><td>好</td><td>好</td><td>好</td><td></td><td></td><td></td><td>44</td></tr><tr><td>抗冲击性/cm</td><td>50</td><td><50</td><td>30</td><td>固化膜的T/C</td><td>110</td><td>110</td><td>110</td></tr><tr><td>耐水性</td><td>好</td><td>好</td><td>好</td><td>贮存稳定性（福特杯4）/s</td><td>胶凝</td><td>胶凝</td><td></td></tr><tr><td>抗摩划性（保光率）/%</td><td>74</td><td>94</td><td>25</td><td>Mc</td><td>596</td><td>240</td><td>549</td></tr></table></body></html>\n\n①23℃下贮存24h后测黏度变化。  \n\n检测结果证实，B—OH/—NCO交联、杂化交联体系的施工黏度下非挥发分比氨基丙烯酸要高44%以上，耐酸雨性优，抗摩划性也高于传统氨基丙烯酸清漆。  \n\n$\\textcircled{4}$ 小结用硅氧烷封闭羟基，使丙烯酸低聚物极性大大降低，使施工黏度下的涂料固体分大为提高（ $80\\%$ 以上)。取代传统氨基丙烯酸涂料，涂膜抗酸雨等性能好。封闭羟基的技术路线为开发耐酸雨侵蚀的高固体分硅-丙涂料提出了新的思路。B一OH/环氧/酸酐杂化交联的涂膜交联密度高（ $M_{\\mathrm{C}}=240)$ ，抵抗环境腐蚀性强，但户外耐久性尚未见数据，要达到工业化应用尚需进一步完善。  \n\n(2）有机硅改性丙烯酸高固体分涂料某些有机硅聚合物黏度很低，在喷涂施工黏度下，固含量可达 $100\\%$ ，并具有优良的耐久性和抗酸雨性。如何将有机硅聚合物通过化学反应引入丙烯酸树脂结构中是国内外涂料界思考的一个课题，用新的交联反应化学以取代传统的三聚氰胺甲醛树脂交联反应化学。  \n\n根据硅橡胶室温硫化在双键上产生氢化硅烷化反应的研究启示，可以设计含SiH基的有机硅聚合物和含双键的丙烯酸低聚物配合作为成膜物，用含双键的醚低聚物作为活性稀释剂的高固体分清漆配方。为使组分混溶性好，有机硅聚合物分子侧链要有苯基。丙烯酸和醚的低聚物分子中双键要在侧链，易于交联反应，涂膜性能好。  \n\n聚二苯基甲基氢硅烷（PMHS）是由0.84mol六甲基硅氧烷、0.16mol聚甲基氢硅烷和2.0mol二苯基二甲氧基硅烷在10℃反应24h，硫酸作为催化剂。合成的PMHS结构式如下：  \n\n![](images/b45d9ddc7123633f678e3200c9bce73c596e4bd0ed21afcbb7ac943a27b67d5c.jpg)  \n\n含双键的丙烯酸低聚物有以下单体：  \n\n2MBA（甲基丙烯酸-α-丁烯酯）  \n\n![](images/abd1c9e854ebf92ded3a55a14cf602964b27e75efd93bc0a2288f9cfbded6308.jpg)  \n\n3M3BA（甲基丙烯酸-3-甲基-3-丁烯酯）  \n\nAMA（甲基丙烯酸烯丙基酯）  \n\n利用2，2'-偶氮（2-甲基丁睛）作为引发剂，二甲苯作为溶剂， $120^{\\circ}\\mathrm{C}$ 下游离基聚合成含双键的丙烯酸低聚物。  \n\n固化交联反应式如下：  \n\n![](images/6db94340c83d6675b799318771e8e46183b89d691fa1d79fcd4c9928dd0f7557.jpg)  \n\n用含双键的醚低聚物HPE-1030作为活性稀释剂，配制清漆在施工黏度（福特 $^{4^{\\sharp}}$ 杯，$20{\\mathrm{s}}/25{\\mathrm{\\mathsf{C}}}$ ）下固体分 $70\\%\\sim90\\%$ ，在 $140^{\\circ}\\mathrm{C}/30\\mathrm{min}$ 下固化，涂膜具有优良的物理机械性能和优良的抗溶剂性、抗酸雨性。  \n\n含双键的醚聚合物HPE-1030结构式如下：  \n\n![](images/7c5472003fa2ea8b4db949635da0b5ca7384e12b7ec5cc2eda0b22ec75d64183.jpg)  \n\n利用SiH基和双键的氢化硅烷化反应引入有机硅聚合物提高固体分、改进抗酸雨性，是开发抗酸雨性优良的高固体分丙烯酸汽车涂料的一个新途径。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 484,
+        "chunk": "# 五、辐射固化有机硅涂料  \n\n紫外线固化涂料（ultraviolet-curingcoatings，简称UV固化涂料）和电子束固化涂料(electronbeamcuringcoatings，简称EB固化涂料）统称辐射固化涂料，由于UV固化涂料的涂装设备投资低，应用推广比EB固化涂料迅速得多。  \n\nUV固化涂料具有固化速率快（以秒计）、VOC低、符合环保要求、效率高和节能等优点，尤其固化时放热少，适合各种对热敏感的材料如纸张、塑料、木材、皮革等涂装，所以UV固化涂料发展很快，UV固化的有机硅涂料也成为新发展的辐射固化涂料的一大类。",
+        "category": " Introduction"
+    },
+    {
+        "id": 485,
+        "chunk": "# 1.UV固化有机硅涂料  \n\n光固化的有机硅-丙烯酸酯低聚物按引人丙烯酰氧基 $\\mathrm{CH_{2}}$ CHCOO—的方式不同有四种合成路线。  \n\n$\\textcircled{1}$ 用二氯二甲基硅烷单体和丙烯酸羟乙酯在碱催化下水解缩合，丙烯酰氧基作为端基引入聚硅氧烷链上。  \n\n$\\textcircled{2}$ 由二烷氧基硅烷和羟基丙烯酸酯经酯交换反应，也是以丙烯酰氧基为端基引入。  \n\n$\\textcircled{3}$ 利用含羟基的硅烷和丙烯酸酯化，引入丙烯酰氧基。这三种合成路线获得相同的分子结构。  \n\n$$\n\\begin{array}{c}{{\\mathrm{O}}}\\\\ {{\\downarrow}}\\\\ {{\\mathrm{CH}_{\\imath}{\\mathrm{-CHCOCH}}_{\\imath}\\mathrm{CH}_{\\imath}{\\mathrm{CH}}_{\\imath}{\\mathrm{O-}}(\\stackrel{\\downarrow}{\\mathrm{Si}}{\\mathrm{-O}})_{\\overline{{\\imath}}}\\mathrm{CH}_{\\imath}{\\mathrm{CH}}_{\\imath}{\\mathrm{OCCH}}{\\mathrm{-CH}}_{\\imath}}}\\end{array}\n$$  \n\n$\\textcircled{4}$ 用端羟基硅烷与二异氰酸酯反应，再利用—NCO基和羟基丙烯酸酯反应，或用端羟基硅烷与二异氰酸酯-丙烯酸酯半加成物反应，引入丙烯酰氧基，这是UV固化的有机硅-聚氨酯-丙烯酸酯低聚物，仍以丙烯酰氧基封端。  \n\n普通UV固化是自由基聚合反应，引入对光敏剂敏感的丙烯酰氧基是UV固化有机硅-丙烯酸酯低聚物的重要前提。这类低聚物具有较低的表面张力，作压敏胶的防粘纸中的离形剂。由于主链为硅氧键，有极好的柔韧性、耐高低温性、耐湿性、耐候性、电性能，常用于电器和电子线路的保护和密封，特别是用于光纤保护涂料。此外，也能用于玻璃和石英材质光学器件的胶黏剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 486,
+        "chunk": "# 2.有机硅-环氧低聚物UV固化涂料  \n\n(1）光可固化的环氧化有机硅低聚物  \n\n$\\Phi$ 环氧化有机硅低聚物品种比较了缩水甘油基环氧和环脂烷基环氧接枝的硅氧烷在UV下的反应活性，环己基环氧功能基的硅氧烷的UV聚合反应较有优势，它们有环氧基封端和环氧基在链段中的两种类型（图2-1-86)。  \n\n![](images/fcce91710da47e371404d39605f5ddc6458a3001a63273707bc23fe2733e4979.jpg)  \n图2-1-86环氧功能基封端的有机硅低聚物和环氧功能基在链段中的有机硅低聚物  \n\n对环氧化有机硅低聚物等及单体要求纯度较高，否则有氢硅烷存在易产生副反应发生胶凝，用新工艺技术已制备出纯度符合要求的有关产品和单体（表2-1-266)。  \n\n表2-1-266中所列的环氧化有机硅低聚物可以作UV固化的防粘涂料、剥离涂料的成膜物，可以作UV固化罩光清漆或油墨的稀释剂，可以在UV固化白色罐头涂料中作助剂。  \n\n表2-1-266环氧化硅氧烷低聚物的溶解性[M\\*=可混合的（100%）；N.M=不混溶的（<3%）]  \n\n\n<html><body><table><tr><td rowspan=\"2\">组分</td><td rowspan=\"2\">度</td><td rowspan=\"2\">数离心高对</td><td colspan=\"3\"></td><td colspan=\"2\"></td><td colspan=\"2\">/</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>光敏剂(CPI 1)</td><td>powder</td><td>0</td><td>17.1</td><td>14.3</td><td>9.7</td><td>1.5</td><td>1. 11</td><td><5</td><td><10</td></tr><tr><td>光敏剂(FRPI1)</td><td>5</td><td>0</td><td>17.7</td><td>6.1</td><td>12.0</td><td>1.1</td><td>0.46</td><td><5</td><td>M*</td></tr><tr><td>硅氧烷低聚物</td><td>30</td><td>520</td><td>17.5</td><td>11.4</td><td>6.7</td><td>1. 25</td><td>0.71</td><td><10</td><td>M*</td></tr><tr><td>硅氧烷低聚物☆</td><td>40</td><td>380</td><td>15.4</td><td>12.2</td><td>5.4</td><td>1.1</td><td>0.89</td><td><10</td><td>M'</td></tr><tr><td>环氧硅氧烷聚合物①</td><td>50</td><td>140</td><td>13.3</td><td>4.8</td><td>3.35</td><td>0.28</td><td>1</td><td>M*</td><td><10</td></tr><tr><td>环氧硅氧烷聚合物</td><td>150~300</td><td>95</td><td>13.4</td><td>3.6</td><td>6.2</td><td>0</td><td>1.1</td><td>一</td><td>N. M*</td></tr><tr><td>环氧硅氧烷聚合物</td><td>100~250</td><td>425</td><td>15.4</td><td>12.3</td><td>5.5</td><td>1.1</td><td>0.9</td><td>M*</td><td>M’</td></tr><tr><td>环氧硅氧烷聚合物④</td><td>100~500</td><td>300</td><td>15.9</td><td>9.2</td><td>6.3</td><td>0.83</td><td>0.45</td><td>M*</td><td>M*</td></tr><tr><td>环氧硅氧烷聚合物</td><td>100~700</td><td>20</td><td>12.7</td><td>0.2</td><td>2.1</td><td>0.56</td><td>1.8</td><td>M'</td><td>N. M*</td></tr><tr><td>环脂基(A)</td><td>350</td><td>790</td><td>20.6</td><td>13</td><td>10.3</td><td>1.8</td><td>1.3</td><td>N. M°</td><td>M·</td></tr><tr><td>双酚A环氧(B)</td><td>11000</td><td>550</td><td>17.4</td><td>11.3</td><td>11.3</td><td>1.3</td><td>0.6</td><td>N. M*</td><td>M</td></tr><tr><td>丙烯酸酯(C)</td><td>20000</td><td>0</td><td>16.3</td><td>10.4</td><td>11.4</td><td>1.1</td><td>0.4</td><td><5</td><td>M°</td></tr><tr><td>丙烯酸聚酯(D)</td><td>1000</td><td>0</td><td>16.5</td><td>8.1</td><td>10.5</td><td>0.91</td><td>0</td><td><5</td><td>一</td></tr><tr><td>丙烯酸环氧(E)</td><td>20000</td><td>0</td><td>16.5</td><td>6.9</td><td>11.8</td><td>0.89</td><td>0.25</td><td>N. M*</td><td>M'</td></tr></table></body></html>\n\n$\\Phi$ $\\textcircled{5}$ 是环氧功能基封端的有机硅低聚物。 $\\textcircled{2}$ 。 $\\otimes$ $\\textcircled{4}$ 是环氧功能基在链段中的有机硅低聚物。A为3,4-环氧环己甲基-3′，4'-环氧环已烷碳酸酯；B为双酚A环氧树脂AralditGy 240；C为二季戊四醇五丙烯酸酯SR399；D为聚酯四丙烯酸酯Ebecryl Resin 810；E为双酚A环氧二丙烯酸酯EbecrylResin 600，代表①、 $\\textcircled{5}$ ，☆代表②、 $\\textcircled{3}$ \\* $\\textcircled{4}$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 487,
+        "chunk": "# 这些应用均明显改进体系的固化性能和物理性能。这将在后面应用实例中简介。  \n\n$\\textcircled{2}$ 溶解性通常UV固化涂料为克服氧抑制作用，液体光引发体系用量要达到涂料体  \n\n系的 $8\\%\\sim12\\%$ ，这样的体系虽具有低黏度，但增加了VOC，并有刺激性气味，这种体系也不能考虑作为无溶剂体系。  \n\n采用环氧化有机硅低聚物作为稀释剂，可以减少光引发剂的用量。这些化合物是不燃性化合物，闪点高于 $150\\mathrm{^c}$ 。  \n\n表2-1-266中 $D$ 是按汉森（Hansen）溶解度参数计算方程计算出的溶剂的溶解球之间的距离，当 $D$ 值小于 $1.0$ 时，化合物有高亲和力，作为溶剂或稀释剂是良性的。根据表2-1-266中 $D$ 值和溶解度可以选择稀释剂及所列组分之间的匹配性。环氧化有机硅低聚物降低UV固化树脂黏度的作用如图2-1-87所示。  \n\n（2）阳离子型光引发聚合前面介绍了UV固化涂料诸多优点，所以发展较  \n\n![](images/13c85be6f4175652a5ee2eb621af77fe63283b8436e0780e78498877a56fdf7e.jpg)  \n图2-1-87环氧化有机硅低聚物降低UV固化树脂黏度的作用稀释剂！硅氧烷低聚物 $^{-1}$ 11季戊四醇丙烯酸酯：丙烯酸聚酯：双酚A环氧稀释剂：环氧硅氧烷聚合物=2:3。丙烯酸聚酯  \n\n快，但也存在氧抑制作用，使涂膜表面固化不完全，耐溶剂性、耐水性差。涂膜经受快速固化和突然终止固化，涂膜起皱。采用阳离子型光引发剂固化，可以克服这些不足。  \n\n阳离子型光引发剂吸收光能后到激发态，分子发生光解反应，产生超强质子酸或路易斯酸，从而引发阳离子低聚物和活性稀释剂进行阳离子聚合。阳离子光聚合的低聚物和活性稀释剂主要有环氧化合物和乙烯基醚。环氧化有机硅低聚物适合进行阳离子型光引发聚合。  \n\n![](images/ad0e54fb366297cb57ee979b0be3af69caa88ff7a7252ae213dab7a645ea7a22.jpg)  \n图2-1-88光引发剂CPI1基本结构  \n\n一种新开发应用的阳离子型光引发剂是甲苯基对异丙苯基(枯基)碘基(五氟苯基)硼酸酯，结构如图2-1-88所示。它和光敏剂FRPI1（2-羟基-2-甲基-1-苯基-丙烷-1-酮）受光作用下发生光解反应，产生超强质子酸，引发环氧化有机硅低聚物聚合（图2-1-89)。  \n\n![](images/a0df4022ed5d6a22c642a840290d5142034094dcbaaae29fe555b6bda5fab2cb.jpg)  \n图2-1-89rhodorsil阳离子光引发剂2074（CPI1）和光敏剂（FRI1）的反应  \n\n(3）应用实例  \n\n$\\textcircled{1}$ UV剥离涂料、防粘涂料选择表2-1-266中的环氧化有机硅低聚物 $\\textcircled{2}$ ， $\\textcircled{3}$ ， $\\textcircled{4}$ 或 $\\textcircled{5}$ 作为剥离涂料的成膜物，环氧化有机硅低聚物的剥离力，远低于溶剂型丙烯酸树脂、天然橡胶；也低于水性和热塑性丙烯酸树脂涂料。  \n\nCPI1阳离子引发剂在环氧化有机硅低聚物中溶解性较好，配制的UV固化涂料的性能见表2-1-267。  \n\n表2-1-267UV阳离子固化可剥涂料的基本性能  \n\n\n<html><body><table><tr><td>项 目</td><td>指 标</td><td>项目</td><td>指 标</td></tr><tr><td>涂料形成 黏度/mPa·s 挥发分(质量分数)/%</td><td>单组分 300~600 <1.5</td><td>固化速率/（m/min） 剥离力/(mN/cm) TESA 4651 TESA 4970</td><td>>200 393.7 590.6~787.4</td></tr></table></body></html>  \n\n对这种体系聚合（固化）速率不受限制，用三个 $240\\mathrm{{W/cm}}$ 灯可以达到 $750\\mathrm{m/min}$ 的高固化速率，获得几微米厚的干膜。环氧基部分对底材具有良好附着力，有机硅结构部分降低表面剥离力，可用于优良的剥离涂料、不粘涂料、脱模涂料。 M ?  \n\n$\\textcircled{2}$ UV罩光清漆已设计出一种罩光清漆，可高速固化，不受空气中氧阻聚，涂膜具有较好的耐溶剂性和耐水性。  \n\n自由基光固化体系用光敏剂FRPI1要达到 $5\\%$ ，而对于阳离子光固化体系，只需0.5%的阳离子型光引发剂CPI1，用量只相当于前者的1/10。  \n\n将试验的样品分别配成清漆，在同样尺寸的铝板上，选择光固化速率 $100\\mathrm{m/min}$ ，在24h后做MEK（甲乙酮）摩擦试验，结果列在表2-1-268中。  \n\n表2-1-268罩光清漆光固化（绕线棒刮涂器2个；160W/cm汞灯2个）  \n\n\n<html><body><table><tr><td>有机树脂</td><td>固化速率 /(m/min)</td><td>指压干</td><td>氧阻聚</td><td>24h后附着力/% （划格法）</td><td>抗溶剂性</td></tr><tr><td>环氧丙烯酸酯(C)</td><td>100</td><td>不干</td><td>是</td><td>0</td><td>指纹痕迹</td></tr><tr><td>环氧丙烯酸酯(D)</td><td>100</td><td>不干</td><td>是</td><td>0</td><td>指纹痕迹</td></tr><tr><td>环氧丙烯酸酶(E)</td><td>100</td><td>好</td><td>不</td><td>0</td><td>>100</td></tr><tr><td>环脂烷基环氧(A)</td><td>50</td><td>5s</td><td>不</td><td>100</td><td>>100</td></tr><tr><td>环脂烷基环氧(A)</td><td>100</td><td>好</td><td>不</td><td>一</td><td>一</td></tr><tr><td>（A)40%（质量）</td><td>100</td><td>好</td><td>不</td><td>100</td><td>100</td></tr></table></body></html>\n\n注：表2-1-268中树脂（A）、（C)、（D)、（E）同表2-1-266.  \n\n从表2-1-268中看到，（A）和（D）树脂混合综合性能比较好，由此设计环氧化硅氧烷低聚物作为稀释剂的光固化罩光清漆配方。  \n\n试验配方： 环氧丙烯酸酶（D）85% 环氧硅氧烷稀释剂10%  \n\n光敏剂FRPI14.5%光引发剂CPI10.5%  \n\n在 $160\\mathrm{W/cm}$ 汞灯固化速率 $100\\mathrm{{m/min}}$ ，MEK来回摩擦通过100次，划格法附着力达到$80\\%$ （如固化速率 $20\\mathrm{m/min}$ ，划格法附着力可达 $100\\%)$ 8  \n\n$\\textcircled{3}$ UV固化白色涂料由于色漆中颜料吸收UV，使UV辐射难以完全穿透涂层和活化光引发剂。如UV白油墨配方中含二氧化钛（ $\\mathrm{TiO}_{2}$ > $40\\%\\sim60\\%$ （质量分数)，吸收全部UV直到 $400\\mathrm{nm}$ 的辐射光。这给UV固化带来了较大困难。  \n\n为达到完全固化，采用阳离子型光引发剂CPI1 $(0.5\\%$ ）和阳离子型光引发剂三芳基硫化物（CPI2， $1.0\\%$ ）混合光引发剂，并加入少量光敏剂噻吨酮（trioxanthone），提高涂膜完全实干的性能和附着力。试验发现，用环氧化有机硅低聚物 $\\textcircled{4}$ 预先处理 $\\mathrm{TiO}_{2}$ ，可以获得最高的性能，用于白色罐头涂料，环氧化有机硅低聚物 $\\textcircled{4}$ 起助剂作用。  \n\n试验配方：  \n\n<html><body><table><tr><td>环脂烷基环氧（A）</td><td>36%</td><td>环氧化丙烯酸酯（C)</td><td>14%</td></tr><tr><td>TiO（金红石型，R960）</td><td>45%</td><td>阳离子型光引发剂（CPI1）（CPI2）</td><td>1.5%</td></tr><tr><td>环氧化有机硅低聚物④</td><td>1.5%</td><td>光敏剂（噻吨酮类）</td><td>0.5%</td></tr></table></body></html>  \n\n用2Ga（）/ $\\mathrm{{\\dot{H}g}}$ （汞） $200\\mathrm{W/cm}$ 灯，用 $3\\sim5\\mu\\mathrm{m}$ 手动辊涂器得到几微米的涂膜，固化速率最高达到 $60\\mathrm{{m/min}}$ ，性能完全达到要求，涂料在常温下贮存3个月后，涂膜固化速率和物理性能没有变化。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 488,
+        "chunk": "# 3.辐射固化有机-无机杂化涂料和固化方法  \n\n有机-无机杂化涂料可以综合有机树脂的优良成膜性、柔韧性、基材附着力及较低成本和无机树脂的高强度、对热和化学药品的高稳定性及超常耐久性，克服彼此不足，达到优势互补，这是涂料新材料重要发展方向之一。有机-无机杂化方法虽有物理掺混法，但该法对无机结构成分引入量受限制，改性不明显。采用的主要方法是化学键合法，有溶胶-凝胶法(sol-gel法）、表面接触法、黏土插层法、聚倍半硅氧烷复合法等，但使用较多的是以含功能性硅氧烷结构单元的前驱体的溶胶-凝胶法，使用较为成功。采用辐照固化更是新发展的  \n\n涂料品种。  \n\n(1）辐射固化有机-无机杂化涂料的成膜物结构溶胶-凝胶法的原理是利用Si、Ti、A1、 $z_{\\mathrm{r}}$ 等烷氧化物作为无机前驱体，经水解、缩合形成无机网络溶胶，和加入的有机单体或低聚物聚合，形成有机-无机杂化凝胶体。其反应过程及杂化体基本机构如图2-1-90所示。  \n\n![](images/baaec53be9cb237fac6d1a0fa00d24cef1d8b10aed601fc293bc7e8a73173323.jpg)  \n图2-1-90烷氧基单体的溶胶-凝胶反应  \n\n用于制备杂化涂料成膜物的普通单体有形成无机网络的化合物「图 $2\\mathrm{-}1\\mathrm{-}91\\left(1\\right)\\sim$ （4)]，形成有机网络的化合物［图2-1-91（9）～（11)］及改进网络的化合物［图2-1-91$(5)\\sim(8)]$ α  \n\n![](images/e78b68efb33b35b0aed22a13e27ede22534face601615e57da8b01d467fa2489.jpg)  \n图2-1-91通常用于制备杂化涂料的单体  \n\n(2）UV固化工艺根据有机-无机杂化体系中引入的基团性质，采用阴离子或阳离子UV固化工艺，如果是丙烯酰氧基为主，用阴离子的UV固化工艺；如果是环氧基封端为主，则采用阳离子的UV固化工艺。 i  \n\n一个新的技术是采用大气压力的气溶胶促进等离子体工艺（aerosod assisted atmos-pheric plasma process，AAAP)，固化有机-无机杂化涂料，具有不用光敏剂，不受氧阻聚，可以固化UV不能固化和热不能固化的涂料，所得涂膜致密性强，性能良好，工艺成本低。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 489,
+        "chunk": "# 六、有机硅乳胶树脂涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 490,
+        "chunk": "# 1.有机硅乳液涂料  \n\n有机硅水性涂料包括纯有机硅乳胶涂料和有机硅改性有机树脂水分散体涂料，后面将分别介绍。  \n\n(1）有机硅乳胶树脂的合成纯有机硅水分散体树脂的合成在国内报道较少，有的文献虽有涉及，但对具体合成的配方设计与工艺过程着墨不多。这有经济和技术上的原因。国内有机硅单体品种在逐步发展，新单体价格仍高昂；和一般水分散体树脂相比较，合成技术有较大难度。这些原因影响了纯有机硅水分散体树脂合成技术发展。国外早在20世纪50年代中期开始研究，并有专利申请，纯有机硅乳胶树脂在建筑外墙装饰、耐高温涂料、特种涂料中获得应用。由于特种功能性涂料的VOC限值的矛盾并不十分突出，从性价比考虑，纯有机硅水分散体涂料应用在国外也未得到大面积推广。  \n\n纯有机硅乳胶树脂早期采取后乳化技术，从二官能度氯硅烷（ $\\mathrm{CH}_{3})_{2}$ SiCl $\\mathrm{Ph}_{2}$ SiCl）（以D表示）和三官能度氯硅烷 $\\mathrm{CH_{3}S i C l_{3}}$ （PhSiCl）（以T表示）出发，根据涂料的性能要求，用不同比例的D与T的甲基或苯基氯硅烷，经常规有机硅树脂合成方法合成有机硅树脂。利用官能度D与T的比例调节树脂分子量，在溶剂与水乳化剂存在下，乳化分散成水分散体有机硅树脂。这种工艺的不足是体系需含足够的溶剂，才可获得较低黏度，选择合适的乳化剂，用机械剪切方法乳化，然后除去部分溶剂，这种工艺不符合国外水性涂料VOC限值的法规要求。采用新的“热工艺”，可以获得接近零VOC的水分散体有机硅树脂。  \n\n对甲基硅烷为基础、经乳液聚合得到羟基有机硅水分散体树脂，具有反应性组分 $40\\%$ ·乳液粒径从 $0.1\\mu\\mathrm{m}$ 到几微米。近年来，纯硅氧烷微乳液得到发展，采用水不溶的低分子量硅氧烷乳化剂，微胶固体分可达到 $100\\%$ ，当用水稀释时，树脂转成微细尺寸乳液，具有优良稳定性，可以和溶剂型硅氧烷同样方法使用。  \n\n(2）涂膜的固化羟基化有机硅乳胶由羟基之间醚化交联成膜的固化速率与 $\\mathfrak{p H}$ 有关，添加1%甲基硅酸钾51T可以作固化剂（同时提高 $\\mathsf{p H})$ ，可以加速固化反应，固化过程如图2-1-92所示。  \n\n![](images/71ff6894eb0404f0f2bf6fae7a64a6afedeb0e7e9d529ee2940250e7627856aa.jpg)  \n图2-1-92羟基有机硅乳液的固化过程  \n\n树脂羟基含量和固化剂对固化也有影响，对比检测结果列于表2-1-269。  \n\n表2-1-269有机硅乳胶树脂羟基与固化剂对固化的影响  \n\n\n<html><body><table><tr><td>交联条件</td><td>含2%—OH基树脂</td><td>含5%-OH基树脂</td></tr><tr><td>乳液pH<7</td><td colspan=\"2\">在干燥7天后，涂膜发黏</td></tr><tr><td>用NHOH中和乳液pH为9</td><td colspan=\"2\">在干燥7天后，涂膜发黏</td></tr><tr><td>用甲基硅酸钾51T中和乳液，pH为9</td><td>涂膜24h干燥，涂膜干燥8天后，缨 杆硬度100s</td><td>涂膜2h千燥，涂膜干燥24h后，摆杆硬 度100s</td></tr></table></body></html>  \n\n从表2-1-269中看出，羟基 $5\\%$ 的树脂比羟基 $2\\%$ 的树脂的固化速率要快得多。用$\\mathbf{NH}_{\\mathrm{4}}\\mathbf{OH}$ 中和乳液提高 $\\mathfrak{p H}$ 至9，但并不提高固化速率，只有用甲基硅酸钾51T中和乳液提高 $\\mathfrak{p H}$ 至9，才大大提高涂膜固化速率，证实甲基硅酸钾51T明显起固化剂作用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 491,
+        "chunk": "# 2.有机硅乳胶树脂涂料的性能与应用  \n\n(1）外墙保护Kunzel理论只有当透气性和吸水性达到某一合适值时，涂膜或其他材料才具有优越的保护功能。以吸水系数 $\\omega$ 表示吸水性，则有：  \n\n$$\n\\omega{=}\\frac{Q}{t^{0,5}}\n$$  \n\n式中α—吸水系数， $\\mathbf{kg}/(\\mathbf{m}^{2}\\cdot\\mathbf{h}^{0.5})$ \\*$\\scriptstyle Q$ —吸水量， $\\mathbf{k}\\mathbf{g}/\\mathbf{m}^{2}$ t——吸水时间，h。  \n\n透气性是用水汽在涂层或其他材料扩散阻力来描述的，即用等效的静止空气层厚度表示透气性：  \n\n$$\nS_{\\mathrm{d}}=\\mu S\n$$  \n\n式中 $S_{\\phi}$ ——等效静止空气层厚度，m;$\\mu$ —扩散阻力系数，空气 $\\scriptstyle\\mu=1$ S—涂膜厚度，m。  \n\n使涂膜或其他保护材料达到吸水性和透气性的合适值要满足以下条件：  \n\n$$\n\\begin{array}{c}{\\omega{\\leqslant}0,5\\mathbf{k}\\mathbf{g}/(\\mathbf{m}^{2}\\cdot\\mathbf{h}^{0.5})}\\\\ {S_{d}{\\leqslant}2\\mathbf{m}}\\end{array}\n$$  \n\n我国JG149-—2003标准规定24h吸水量 $500\\mathrm{g}/\\mathrm{m}^{2}$ ，相当于欧洲标准中的吸水系数 $\\omega=$ $0.1\\mathbf{k}\\mathbf{g}/(\\mathbf{m}^{2}\\cdot\\mathbf{h}^{0.5})$ ，属低吸水性的涂料标准。  \n\n有的涂料如溶剂型涂料，其涂膜致密性好，对水渗透的屏蔽性强，8小；但透气性差，$\\ensuremath{\\boldsymbol{s}}_{\\ensuremath{\\boldsymbol{\\phi}}}$ 大，因墙体水汽不能透过涂膜逸出，产生气泡、开裂，保护功能不理想；有的涂料如硅酸盐涂料，其涂膜孔隙率高， $\\boldsymbol{s}_{d}$ 小，透气性好，但 $\\omega$ 也大，保护性能也差；只有有机硅、丙烯酸酯等水分散体涂料，具有合适的 $\\boldsymbol{w}$ $\\boldsymbol{S}_{\\mathrm{d}}$ 值，对墙体保护功能好。  \n\n(2）有机硅乳胶树脂的透气斥水性能纯有机硅乳液树脂粒径在 $0.1\\mu\\mathrm{m}$ 以上，成膜后有一定孔隙率，这是乳胶涂膜的共性，透气性优于溶剂型涂膜。但对于有机硅乳胶树脂分子具有表面活性剂作用，有助于水汽在涂层中扩散。用丙烯酸-苯乙烯共聚乳液DS910与有机硅乳液865A的不同比例混合，测定蒸汽渗透性，随着有机硅乳液865A的比例增加，蒸汽渗透性增加（图2-1-93)，说明纯有机硅乳液的透气性优于丙烯酸-苯乙烯共聚乳液。  \n\n有机硅低聚物乳液分子中硅烷基指向涂膜与空气的界面，如果是甲基硅烷基，自由表面会被甲基以紧密堆积的方式遮盖住，即在涂膜表面形成斥水层（图2-1-94），故有机硅乳液涂膜的斥水性也较好。  \n\n试验选定丙烯酸-苯乙烯共聚乳液与有机硅乳液合适的质量比 $(40:60)$ ，合适的颜料与基料比（PV $1C=42\\%)$ ，这种复合乳胶涂料具有合适的 $w$ ， $S_{d}$ 值，在Kunzel理论图中处于最佳位置（图2-1-95），涂料的 $\\boldsymbol{w}$ ， $S_{\\mathrm{d}}$ 值越接近零越好。  \n\n（3）有机硅乳液的应用纯有机硅乳胶涂料完全可以达到溶剂型有机硅的优良的耐热性、绝缘性，良好的防粘性、耐候性。但是常温的固化性能仍需要改进，热固化可以改进涂膜性能，可以用于电镀钢板的预涂涂料、高档维护涂料及理想的黏结剂。但偏高的价格也限制了它的扩大应用。有机硅乳液的突出优点是透气性优良，同时有良好的斥水性，可以降低涂膜沾污性，为获得满意的性价比，一般是与丙烯酸酯类乳胶配合使用，这使有机硅改性丙烯酸酯乳胶涂料获得了迅速发展。  \n\n![](images/1a03d63c663d72f88ebfe4f4622033d88c72d1ee3dbce5f1518ba607f0d00514.jpg)  \n图2-1-93水汽对有机硅乳液涂膜的渗透性  \n\n![](images/73ae210c269a65681339996fc1ee20b5021251d3861a23b7f19da2cdff875f53.jpg)  \n图2-1-94聚二甲基硅烷低聚物乳液涂膜斥水层  \n\n![](images/a8ab01fc018ebf7286422f841c5d2b948b3b18968a56d837a32260a4a36fafb2.jpg)  \n图2-1-95有机硅乳液-丙烯酸苯乙烯 共聚乳液复合涂料的W、 $\\boldsymbol{s}_{d}$ 值范围",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 492,
+        "chunk": "# 3.有机硅改性丙烯酸树脂水分散体涂料  \n\n(1）硅-丙乳液及涂料  \n\n$\\textcircled{1}$ 基本配方参照常州涂料化工研究院发表的工作报告，基本配方见表2-1-270。  \n\n表2-1-270有机硅改性丙烯酸乳液配方  \n\n\n<html><body><table><tr><td>原材料</td><td>规格</td><td>质量分数/%</td><td>原材料</td><td>规格</td><td>质量分数/%</td></tr><tr><td>甲基丙烯酸甲酯（MMA）</td><td>工业品</td><td>82.0</td><td>过硫酸铵</td><td>试剂纯</td><td>1.5 ~2. 0</td></tr><tr><td>丙烯酸丁酯（BA)</td><td>工业品</td><td>120. 0</td><td>NaHCO</td><td>试剂纯</td><td>2.0</td></tr><tr><td>丙烯酸（AA)</td><td>工业品</td><td>2.7</td><td>抑制剂G</td><td>试剂纯</td><td>3.0~4.0</td></tr><tr><td>硅氧烷单体</td><td></td><td>68.0</td><td>去离子水</td><td></td><td>301.3</td></tr><tr><td>保护胶（25%）</td><td>自制品</td><td>9.0~10.0</td><td>合计</td><td></td><td>600</td></tr><tr><td>乳化剂FM（25%）</td><td>自制品</td><td>11.2~12. 0</td><td></td><td></td><td></td></tr></table></body></html>  \n\n配方中，有机硅单体约占单体总量 $24.94\\%$ ，硬、软单体之比是 $0,683:1$  \n\n$\\textcircled{2}$ 工艺在装有冷凝器、搅拌器的三口烧瓶中加入水和保护胶，升温，搅拌。待温度达到 $82\\ensuremath{\\mathbb{C}}$ 时，加人 $_{1/2}$ 的引发剂过硫酸铵，保温 $10\\mathrm{{min}}$ 后，加人1/10混合单体和1/10乳化剂， $10\\mathrm{{min}}$ 后开始滴加剩余混合单体和剩余引发剂、缓冲剂 $\\mathrm{\\DeltaNaHCO_{3}}$ 和抑制剂G的混合溶液，在 $82\\sim84\\Upsilon$ 用3h滴加完，保温1h，降温，过滤出料。  \n\n$\\textcircled{3}$ 乳液技术指标乳液技术指标见表2-1-271。  \n\n表2-1-271乳液技术指标  \n\n\n<html><body><table><tr><td>控制项目</td><td>指标</td><td>控制项目</td><td>指标</td></tr><tr><td>外观</td><td>乳白色，蓝光</td><td>残余单体含量/%</td><td><0.5</td></tr><tr><td>固体分/%</td><td>46</td><td>5%CaCl稳定性</td><td>通过</td></tr><tr><td>MFT/C</td><td>24~26</td><td>机械稳定性</td><td>通过</td></tr><tr><td>粒径/μm</td><td>0.1~0.2</td><td>热稳定性</td><td>通过</td></tr></table></body></html>\n\n$\\Phi$ MFT为最低成膜温度，该乳液树脂最低成膜温度为24～26℃，比较高。  \n\n$\\textcircled{4}$ 乳液涂料配制与性能按通常的丙烯酸乳液涂料配方，设计白色硅-丙乳液涂料配方。将水、分散剂、助溶剂、防霉剂和消泡剂等混合，在搅拌下加人颜、填料，混合均匀后，用砂磨分散至细度小于 $60\\mu\\mathrm{m}$ ，过滤出料。加人有机硅改性丙烯酸乳液、成膜助剂等，用流变控制剂调整至适当黏度。涂刷施工后，按相关标准检测，涂膜性能比较优良，结果列于表2-1-272。  \n\n表2-1-272硅-丙乳液涂料的性能与技术指标  \n\n\n<html><body><table><tr><td>检验项目</td><td>指标</td><td>检验项目</td><td>指标</td></tr><tr><td>容器中状态</td><td>搅拌后呈均匀状态</td><td>耐洗刷性/次</td><td>>10000</td></tr><tr><td>涂膜外观</td><td>平整</td><td>对比率</td><td>≥0.93</td></tr><tr><td>干燥时间/h</td><td>≤2</td><td>冻融稳定性</td><td>不变质</td></tr><tr><td>施工性</td><td>涂剧二道无障碍</td><td>耐温变性(10次循环)</td><td>无异常</td></tr><tr><td>耐水性(7天)</td><td>无异常</td><td>人工老化(1000h)</td><td></td></tr><tr><td>耐碱性(7天)</td><td>无异常</td><td>粉化/级</td><td>0</td></tr><tr><td>耐沾污性（15次循环白度下降）</td><td><10</td><td>变色/级</td><td>1~2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 493,
+        "chunk": "# (2）影响乳液聚合的因素  \n\n$\\Phi$ 有机硅单体对乳液聚合的影响聚合体系中，有丙烯酸单体间自聚、有机硅单体间自聚和二者之间的共聚反应的竞争，希望二者共聚反应达到要求的程度。特别是有机硅单体易水解、缩聚反应，产生凝胶性的不溶物质，影响乳液的稳定性。选用的有机硅单体在水中溶解度、空间位阻影响其水解、缩聚反应速率。含不同烷氧基的不饱和硅氧烷在pH为3.5时的水解速率和使用 $3\\%$ 硅烷改性丙烯酸乳液的稳定性见表2-1-273。乙烯基三异丙氧基硅烷水解最慢（约 $600\\mathrm{{min})}$ ， $z$ 烯基三甲氧基硅烷水解最快（约 $2\\mathrm{min})$ ，是空间位阻差异所致。  \n\n表2-1-273不同有机硅氧烷对乳液稳定性的影响  \n\n\n<html><body><table><tr><td>硅氧烷类型</td><td>水解时间/min</td><td>凝胶量/%</td><td>硅氧烷类型</td><td>水解时间/min</td><td>凝胶量/%</td></tr><tr><td>乙烯基三甲氧基硅烷</td><td>约2</td><td>2.15</td><td>乙烯基-三（2-甲基乙氧基）硅烷</td><td>约10</td><td>0.97</td></tr><tr><td>乙烯基三乙氧基硅烷</td><td>约30</td><td>1.75</td><td>乙烯基三异丙氧基硅烷</td><td>约600</td><td>0.015</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 494,
+        "chunk": "# $\\textcircled{2}$ 反应条件对乳液聚合的影响  \n\na.反应温度的影响反应温度对硅氧烷的水解、缩聚有明显影响，在固定硅氧烷单体品种与用量的条件下，反应温度对乳液聚合的影响见表2-1-274。  \n\n表2-1-274反应温度对乳液聚合的影响  \n\n\n<html><body><table><tr><td>反应温度/℃</td><td>54~56</td><td>62~64</td><td>70~74</td><td>80~84</td></tr><tr><td>乳液状态</td><td>白色，残余单体气味重</td><td>乳白色，蓝光，无凝聚物</td><td>乳白色，蓝光，无凝聚物</td><td>乳白色，蓝光，凝聚物较多</td></tr></table></body></html>  \n\nb.pH对乳液聚合的影响通常情况下，碱性条件对硅氧烷的水解、缩聚交联有促进作用；但酸性条件对硅氧烷的水解、缩聚同样有促进作用。试验结果证实，反应体系 $\\mathsf{p H}$ 为$6{\\sim}7$ ，乳液聚合稳定（表2-1-275）。  \n\n表2-1-275反应体系pH对乳液聚合的影响  \n\n\n<html><body><table><tr><td>pH</td><td>3.1</td><td>4.2</td><td>5.4</td><td>6.0</td><td>7.1</td><td>7.6</td><td>10.0</td></tr><tr><td>乳液状态</td><td></td><td></td><td>自自自自自自</td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\nc.水解抑制剂的影响采用二元醇如乙二醇、丙二醇、丙二醇丙醚等可有效抑制反应体系中硅氧烷的水解，使反应过程在较宽的 $\\mathsf{p H}$ 范围（5～8）及较高的温度 $80\\sim88\\Upsilon$ 反应，有利于工艺控制，因为硅氧烷基水解产生醇，添加二元醇使水解反应不易于向反应方程式的右边进行，因而能抑制水解反应。  \n\nd.引发剂用量的影响采用过硫酸钾（KPS）为引发剂，固定有机硅氧烷单体及配方中其他组分用量，不同KPS用量对乳液性能的影响见表2-1-276，KPS添加量以 $0.6\\%$ \\~$0.8\\%$ 为佳。  \n\n表2-1-276不同引发剂用量对乳液性能的影响  \n\n\n<html><body><table><tr><td>KPS用量（质量分数）/%</td><td>0.2</td><td>0.4</td><td>0.6</td><td>0.8</td></tr><tr><td>乳液粒径/nm</td><td>283.7</td><td>186.4</td><td>135.6</td><td>246.3</td></tr><tr><td>转化率/%</td><td>73</td><td>89</td><td>98</td><td>98</td></tr><tr><td>凝胶量/%</td><td>3.67</td><td>1.85</td><td>0.46</td><td>2.82</td></tr><tr><td>冻融稳定性</td><td>凝胶</td><td>凝胶</td><td>通过</td><td>通过</td></tr></table></body></html>  \n\n$\\textcircled{3}$ 有机硅氧烷含量的影响如果不添加水解抑制剂，采用空间位阻大的-甲基丙酰氧基三异丙氧基硅烷，其用量可占单体总量的 $10\\%$ （质量分数)，可得稳定的硅-丙乳液，其他位阻较小的硅氧烷，用量占单体总量的 $5\\%$ （质量分数）以上时，乳液有凝胶产生。  \n\n改性的硅-丙乳液性能是与硅氧烷在单体总量中所占比例有关。采用水解抑制方法可使硅氧烷单体占单体总量的 $30\\%$ （质量分数）以上。硅氧烷含量对涂料性能的影响见表2-1-277。  \n\n表2-1-277硅氧烷在单体总量中的比例对涂料性能的影响  \n\n\n<html><body><table><tr><td>涂料性能</td><td colspan=\"4\">硅氧烷含量（质量分数）/%</td></tr><tr><td>人工老化500h(1000h)</td><td></td><td></td><td>1(1~2)</td><td></td><td></td></tr><tr><td>变色/级 粉化/级</td><td>3() 0(0)</td><td>2(一) 0(0)</td><td>0(0)</td><td>1(1~2) 0（0)</td><td>1(1~2) 1（0）</td></tr><tr><td>耐洗刷性/次</td><td>>10000</td><td>>10000</td><td>>10000</td><td>>10000</td><td>>3000</td></tr><tr><td>耐沾污性（15次循环白度下降）/%</td><td>10~15</td><td>10~15</td><td>10~15</td><td><7</td><td><7</td></tr></table></body></html>  \n\n从表2-1-277中可以看出，当硅氧烷单体占单体总量的 $20\\%$ 时，涂料性能改进明显，体现了高性能，人工老化1000h，变色 $_{1\\sim2}$ 级，这是普通纯丙烯酸乳液涂料无法达到的。在天然曝晒一年后，各色硅-丙乳液涂膜的变色 $\\scriptstyle\\Delta E$ 为 $0.48\\sim0.85$ ；而纯丙烯酸乳液涂膜变色$\\Delta E$ 为 $0.95\\sim1.80$ ，硅-丙乳液涂膜抗变色性的改进明显。  \n\n虽然改性丙烯酸酯乳胶树脂性能是与树脂中硅氧烷含量成比例，但树脂的原料成本也随硅氧烷含量增加而明显上升，工艺控制难度也加大；添加二元醇抑制剂，可以解决工艺控制问题，但增加了涂料中的VOC。另外，硅氧烷用量增加过多，控制稍不恰当，涂膜易开裂。综合考虑，在改进性能达到要求的前提下，硅氧烷单体用量应尽量减少。  \n\n近来浙江大学的W.Zhang和M.J.Yang针对硅氧烷用量对涂料性能的影响进行了研究，用丙烯酸丁酯（BA）、甲基丙烯酸甲酯（MMA）、丙烯酸（AA）、甲基丙烯酰氧丙基三甲氧基硅烷（MPTS）和聚二甲基硅氧烷（HDMPS）等单体，分别采用间歇法和半连续法聚合工艺聚合：  \n\n![](images/d44134e68dbbc88eb34845c5d1d7652d257f5bd0daf5442c71ac62650949c74c.jpg)  \n\n样品经户外曝晒15个月后，保光率是随硅氧烷在单体总量中比例增加而增加，硅氧烷占 $20\\%$ 的配方的涂料保光率为 $89\\%$ ，硅氧烷占 $8\\%$ 的配方的保光率为 $82\\%$ ；UV辐照500h后，保光率和户外曝晒试验结果相似，硅氧烷占 $8\\%$ 和 $20\\%$ 的配方的保光率分别为 $83\\%$ 和$88\\%$ 。涂膜拉伸强度、耐沾污性均随硅氧烷用量增加而提高与改进。综合各方面考虑尤其是从涂料的性价比考虑，硅氧烷单体在单体总量中占 $8\\%$ 可以获得耐候性、耐沾污性优良的外墙装饰涂料，工艺上是半连续法优于间歇法。  \n\n单体组成中MPTS是含乙烯基的硅烷偶联剂，与丙烯酸酯单体中双键加成易于进行，IR光谱分析证实，在乳液聚合过程中双键完全转化，表征C一C键特征峰 $1634\\mathrm{cm}^{-1}$ 在聚合后完全消失，这样反应会阻滞烷氧基、羟基间的自缩合反应。HDMPS是半成品或预聚物，位阻较大，也有利于阻滞硅氧烷单体的自缩合反应。加上合理控制加料顺序，使乳化聚合能按设计方向进行，得到稳定的乳液。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 495,
+        "chunk": "# 第十三节氟碳树脂  \n\n氟烯烃聚合物或氟烯烃与其他单体的共聚物称为氟碳树脂。氟碳树脂可以加工成塑料制品（通用塑料和工程塑料)、增强塑料（玻璃钢等）、合成橡胶和涂料（粉末、乳液、溶液）等产品。以氟碳树脂为主要成膜物制成的涂料，称为“氟碳涂料”。习惯上称为“含氟涂料”或“氟涂料”。目前，常见的氟碳树脂及由其制成的氟碳涂料按成膜物的化学组成大致分四类： $\\textcircled{1}$ 聚四氟乙烯（PTFE）氟碳树脂与氟碳涂料； $\\textcircled{2}$ 聚偏二氟乙烯（PVPF）氟碳树脂及氟碳涂料； $\\textcircled{3}$ 聚氟乙烯（PVF）氟碳树脂与氟碳涂料； $\\textcircled{4}$ 三氟氯乙烯（四氟乙烯）-乙烯基醚共聚物（PEVE）氟碳树脂与氟碳涂料。按物质的性状可分为： $\\textcircled{1}$ 溶剂型氟碳树脂与氟碳涂料； $\\textcircled{2}$ 水性氟碳树脂与氟碳涂料； $\\textcircled{3}$ 粉末氟碳树脂与氟碳涂料。本书就物质性状分类对涂料常用氟碳树脂进行介绍。  \n\n自1934年德国赫斯特公司发现聚三氟氯乙烯，特别是1938年美国杜邦公司R.J.Plunkett博士发明了聚四氟乙烯以来，氟碳树脂以其优异的耐热性、耐化学药品性、不粘性、耐候性、低摩擦系数和优良的电气特性，博得了人们的青睐。1946年杜邦公司将聚四氟乙烯商业化，商品名为特氟隆（Teflon）。同时氟碳树脂的成型加工、各种含氟单体及其聚合物的研究和开发也十分活跃，加工方法的进步和应用领域的发展，又推动了氟碳树脂的研究开发。  \n\n在氟碳树脂中，聚四氟乙烯树脂虽然占据主导地位，但是聚四氟乙烯树脂本身也存在某些缺点，如不粘性和熔融流动性差，从而限制了某些场合的应用。为了拓宽聚四氟乙烯酯的应用领域，通过改性研究开发了多种新型氟碳树脂和改性产品。近年来，各种氟碳树脂在涂料及涂装领域获得了广泛的应用。  \n\n氟碳树脂的生产和消费主要集中在美国、欧洲和日本，具体情况见表 $2\\cdot1\\cdot278\\sim$ 表2-1-280。2001年，全世界的氟碳树脂消费量达到了 $112\\mathbf{kt}$ ，价值21亿美元，而且每年以$5\\%$ 左右的速度在增长。聚四氟乙烯继续统治着氟碳树脂市场，到2001年，在北美、西欧和日本的市场，聚四氟乙烯至少占所有氟碳树脂消费量的 $60\\%$ 。在发展中的市场，这个百分数甚至更高。  \n\n表2-1-2782001年氟碳树脂消费的种类和地区 单位：kt  \n\n\n<html><body><table><tr><td>国家或地区</td><td>PTFE</td><td>FEP</td><td>PVDF</td><td>PFA</td><td>ETFE</td><td>PVF</td><td>ECTFE</td><td>总计</td></tr><tr><td>美国</td><td>22</td><td>14</td><td>9</td><td>2</td><td>2</td><td>1</td><td>1</td><td>51</td></tr><tr><td>西欧</td><td>21</td><td>１</td><td>4</td><td>一</td><td>一</td><td></td><td></td><td>28</td></tr><tr><td>日本</td><td>8</td><td>1</td><td>2</td><td>2</td><td>1</td><td></td><td></td><td>14</td></tr><tr><td>其他</td><td>17</td><td>一</td><td></td><td>一</td><td></td><td></td><td></td><td>20</td></tr><tr><td>世界总量</td><td>68</td><td>17</td><td>16</td><td>6</td><td>4</td><td>1</td><td>1</td><td>113</td></tr><tr><td>世界需求量（百分数）</td><td>60%</td><td>15%</td><td>15%</td><td>4%</td><td>3%</td><td>2%</td><td>1%</td><td>100%</td></tr></table></body></html>\n\n注：PTFE为聚四氟乙烯；FEP为聚全氟乙烯；PVDF为聚偏氟二乙烯；PFA为四氟乙烯-全氟乙烯基醚共聚物； ETFE为乙烯-四氟乙烯共聚物；PVF为聚氟乙烯；ECTFE为聚三氟氯乙烯。  \n\n表2-1-279世界生产氟碳树脂的主要公司  \n\n\n<html><body><table><tr><td>氟碳树脂品种</td><td>生产公司</td><td>生产国家</td></tr><tr><td rowspan=\"9\">聚四氟乙烯（PTFE,F4）</td><td>Ausiment</td><td>美国</td></tr><tr><td>Asahi Glass/ICI</td><td>日本</td></tr><tr><td>Daikin</td><td>日本</td></tr><tr><td>Du Pont</td><td>美国、荷兰</td></tr><tr><td>Du Pont/Mitsui</td><td>日本</td></tr><tr><td>Hoechst</td><td>德国</td></tr><tr><td>ICI</td><td>英国、美国</td></tr><tr><td>Montefkuns</td><td>意大利</td></tr><tr><td>其他</td><td>中国、印度、俄罗斯</td></tr><tr><td rowspan=\"5\">可熔性聚四氟乙烯（PFA)</td><td>Asahi Glass</td><td>日本</td></tr><tr><td>Daikin</td><td>日本</td></tr><tr><td>Du Pont</td><td>美国、日本</td></tr><tr><td>Hoechst</td><td>德国</td></tr><tr><td>Montefkuns</td><td>意大利</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>氟碳树脂品种</td><td colspan=\"2\">生产公司</td><td colspan=\"2\">生产国家</td></tr><tr><td rowspan=\"6\">聚全氟乙丙烯（FEP，F46）</td><td colspan=\"2\">Ausiment</td><td colspan=\"2\">美国</td></tr><tr><td colspan=\"2\">Asahi Glass</td><td colspan=\"2\">日本</td></tr><tr><td colspan=\"2\">Daikin</td><td colspan=\"2\">日本</td></tr><tr><td colspan=\"2\">Du Pont</td><td colspan=\"2\">美国、荷兰</td></tr><tr><td colspan=\"2\">Hoechst</td><td colspan=\"2\">德国</td></tr><tr><td colspan=\"2\">Montefkuns</td><td colspan=\"2\">意大利</td></tr><tr><td rowspan=\"5\">乙烯-四氟乙烯共聚物（ETFE，F40)</td><td colspan=\"2\">Asahi Glass</td><td colspan=\"2\">日本</td></tr><tr><td colspan=\"2\">Daikin</td><td colspan=\"2\">日本</td></tr><tr><td colspan=\"2\">Du Pont</td><td colspan=\"2\">日本</td></tr><tr><td colspan=\"2\">Hoechst</td><td colspan=\"2\">德国</td></tr><tr><td colspan=\"2\">Montefkuns</td><td colspan=\"2\">意大利</td></tr><tr><td rowspan=\"6\">聚偏二氟乙烯（PVDF，F2）</td><td colspan=\"2\">Atochem</td><td colspan=\"2\">法国</td></tr><tr><td colspan=\"2\">Kurehs</td><td colspan=\"2\">日本</td></tr><tr><td colspan=\"2\">Daikin</td><td colspan=\"2\">日本</td></tr><tr><td colspan=\"2\">Montefkuns</td><td colspan=\"2\">美国</td></tr><tr><td colspan=\"2\">Pennwalt</td><td colspan=\"2\">美国</td></tr><tr><td colspan=\"2\">Salay</td><td colspan=\"2\">法国</td></tr><tr><td>聚三氟氯乙烯（ECTFE,F30）</td><td colspan=\"2\">Ausiment</td><td colspan=\"2\">美国</td></tr><tr><td>特氟隆（Teflon,AF)</td><td colspan=\"2\">Du Pont</td><td colspan=\"2\">美国</td></tr><tr><td colspan=\"5\">表2-1-280 美国、日本和欧洲氟碳树脂的消费结构</td></tr><tr><td colspan=\"2\"></td><td colspan=\"2\">欧洲</td><td>单位：% 日本</td></tr><tr><td>应用领域 化工</td><td colspan=\"2\">美国 24</td><td colspan=\"2\"></td><td></td></tr><tr><td></td><td colspan=\"2\"></td><td colspan=\"2\">34</td><td>30</td></tr><tr><td>汽车和机械</td><td colspan=\"2\">17</td><td colspan=\"2\">22</td><td>31</td></tr><tr><td>电子和电器</td><td colspan=\"2\">45</td><td colspan=\"2\">20</td><td>23</td></tr><tr><td>其他</td><td colspan=\"2\">14</td><td colspan=\"2\">24</td><td>16</td></tr><tr><td>合计</td><td colspan=\"2\">100</td><td colspan=\"2\">100</td><td>100</td></tr></table></body></html>  \n\n在国内，氟碳树脂研究比国外落后20年左右。PVDF树脂只有屈指可数的几家单位生产，而且生产量不大。近几年，我国在以三氟氯乙烯和四氟乙烯为原料合成常温固化涂料用树脂方面取得了一系列具有自主知识产权的科研成果，并研究成功一系列不同用途的氟碳涂料，已成功应用在体育场馆等大型标志性建筑工程的防腐涂装上。  \n\n氟碳树脂具有以下化学特性。  \n\n$\\textcircled{1}$ 碳-氟键的高键能是氟碳树脂用于高耐候性涂料的基础，C—F键能（451～485kJ/mol）$>$ Si-O键能 $(318\\mathbf{kJ}/\\mathbf{mol})$ 。阳光中的紫外线波长为 $220\\sim400\\mathrm{nm}$ ， $220\\mathrm{nm}$ 波长的光子的能量为 $544\\mathrm{kJ/mol}$ ，只有小于 $220\\mathrm{nm}$ 波长的光子才能使氟碳树脂的C--F键破坏。在阳光中，小于 $220\\mathrm{nm}$ 波长的光子比例很小，阳光几乎对氟碳树脂没有任何影响一——显示了氟碳树脂的高耐候性。  \n\n$\\textcircled{2}$ 氟碳树脂具有极高的化学稳定性，氟原子具有最高的电负性和较小的原子半径，碳-氟键的键能大，碳链上的氟原子排斥力大，碳链呈现螺旋状结构且被氟原子包围—屏蔽效  \n\n应，从而决定了氟碳树脂极高的化学稳定性。",
+        "category": " Introduction"
+    },
+    {
+        "id": 496,
+        "chunk": "# 一、常用氟化物单体",
+        "category": " Introduction"
+    },
+    {
+        "id": 497,
+        "chunk": "# 1.四氟乙烯  \n\n四氟乙烯（TFE）单体可以通过氟氯甲烷脱卤化氢（工业生产)、四氟二氯乙烷脱氯、三氟醋酸钠脱二氧化碳、各种元素的氟化物与碳反应和聚四氟乙烯的热分解五种方法合成。20世纪60年代，日本研究了二氟一氯甲烷和水蒸气共存下的热分解，用此法制备四氟乙烯，不仅转化率高，而且高沸点副产物少，易于提纯。纯四氟乙烯单体极易自动聚合，即使在黑暗的金属容器中也是如此，而且聚合是剧烈的放热（爆聚）反应。在室温下处理四氟乙烯很不安全，运输时更是如此。为了安全起见，通常在四氟乙烯单体中加人一定量的三乙胺以阻止发生自聚。四氟乙烯的主要物理常数见表2-1-281。  \n\n表2-1-281四氟乙烯的主要物理常数  \n\n\n<html><body><table><tr><td>项 目</td><td>指标</td><td>项 目</td><td>指标</td></tr><tr><td>沸点/C</td><td>-76.3</td><td>临界压力/MPa</td><td>3.94</td></tr><tr><td>熔点/</td><td>142. 5</td><td>临界密度/（g/cm²）</td><td>0.58</td></tr><tr><td>临界温度/℃</td><td>33.3</td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 498,
+        "chunk": "# 2.六氟丙烯  \n\n六氟丙烯（HFP）单体可以通过二氟一氯甲烷裂解、三氟甲烷裂解、四氟乙烯裂解、六氟一氯丙烷热分解、全氟丁酸的碱金属盐脱二氧化碳、八氟环丁烷热分解、四氟乙烯与八氟环丁烷共热分解和聚四氟乙烯热分解合成。实验室采取聚四氟乙烯热分解的方法制取六氟丙烯单体，而工业上则采取六氟一氯丙烷的热分解来制取。六氟丙烯的主要物理常数见表2-1-282。  \n\n表2-1-282六氟丙烯的主要物理常数  \n\n\n<html><body><table><tr><td>项 目</td><td>指标</td><td>项 目</td><td>指标</td></tr><tr><td>沸点/℃ 熔点/C</td><td>29.4 156.2</td><td>蒸气压p(T=232~293K)</td><td>Igp（mmHg)=7. 44806 1060. 757/(T10. 66)</td></tr><tr><td>临界鲨度/g/cm²）</td><td>105.8</td><td>液体密度d(40℃）/(g/cm)</td><td>1.583</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 499,
+        "chunk": "# 3.三氟氯乙烯  \n\n三氟氯乙烯（CTFE）单体可以通过三氟三氯乙烷脱氯、三氟二氯乙烷脱氯、氟氯代羧酸的碱金属盐脱二氧化碳、二氟一氯甲烷与一氟二氯甲烷的共热分解和聚三氟氯乙烯的热分解五种方法合成。虽然三氟氯乙烯单体可由多种方法合成，但是在工业上基本是采用三氟三氯乙烷脱氯来完成。三氟三氯乙烷可先由乙炔制取三氯乙烯，然后合成六氯乙烷，再在五氯化的存在下与无水氟化氢反应生成。三氟三氯乙烯具有醚类的气味，是无色气体，三氟氯乙烯的主要物理常数见表2-1-283。 g  \n\n表2-1-283三氟氯乙烯的主要物理常数  \n\n\n<html><body><table><tr><td>项 目</td><td>指 标</td></tr><tr><td>沸点/C</td><td>27.9</td></tr><tr><td>熔点/C</td><td>157.5</td></tr><tr><td>临界温度/C</td><td>105.8</td></tr></table></body></html>  \n\n续表  \n\n<html><body><table><tr><td>项 目</td><td>指标</td></tr><tr><td>临界压力/MPa</td><td>4.06</td></tr><tr><td>临界密度/(g/cm）</td><td>0.55</td></tr><tr><td>蒸气压p</td><td></td></tr><tr><td>T=-67~-11℃</td><td>Igp(mmHg) = 6. 90199850. 649/(T+239. 91)</td></tr><tr><td>T=25~105. 8°C</td><td>lgp(mmHg)= 7. 754121392. 82/(T+319. 70)</td></tr><tr><td>液体密度d(T=-41~-40C）/(g/cm）</td><td>d=1. 38—0. 0029T</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 500,
+        "chunk": "# 4.氟乙烯  \n\n氟乙烯（VF）单体可以通过乙炔与氟化氢加成、氟（氯）乙炔脱卤化氢、氯乙烯或氯乙烷与氟化氢反应和乙炔与氟乙烷共热分解合成。工业上制备氟乙烯单体最常用的方法是乙炔的气相氢氟化。氟乙烯的主要物理常数见表2-1-284。  \n\n表2-1-284 氟乙烯的主要物理常数  \n\n\n<html><body><table><tr><td>项 目</td><td>指标</td><td>项 目</td><td>指标</td></tr><tr><td>沸点/℃</td><td>72.0</td><td>蒸气压（21C）/MPa</td><td>2.55</td></tr><tr><td>熔点/</td><td>160.0</td><td>液体密度（21℃）/(g/cm）</td><td>0.636</td></tr><tr><td>临界温度/C</td><td>54.7</td><td>水溶性（27C,2.76MPa,100g水中）/g</td><td>1. 1</td></tr><tr><td>临界压力/MPa</td><td>5.24</td><td>爆炸范围（空气中)/%</td><td>2.6~21.7</td></tr><tr><td>临界密度/(g/cm）</td><td>0.32</td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 501,
+        "chunk": "# 二、溶剂型氟碳树脂  \n\n氟碳（涂料）树脂发展经过热熔型、溶剂可溶型、常温/室温固化型、水性/高固体分、粉末涂料（树脂）几个阶段。最早出现的溶剂型氟碳树脂为聚偏二氟乙烯（PVDF）分散液。1982年，日本旭硝子公司研究开发出溶剂可溶型三氟氯乙烯-乙烯基醚共聚物（FEVE)氟碳树脂，商品名为Lumiflon，使溶剂型氟碳树脂由热塑性进入热固性（反应交联型）时代，这类氟碳树脂可广泛溶于芳香烃、酯类或酮类溶剂，可在室温到高温范围固化，由其制备的氟碳树脂涂料也广泛应用于多种领域。  \n\n1982年后，ElfAltochem公司研究成功偏二氟乙烯-四氟乙烯-六氟丙烯共聚物（VDF-TFE-HEP）和含偏二氟乙烯的功能性聚合物，特点是可以常温固化，但耐溶剂性差。Ausi-montSPA公司，研究成功端羟基全氟聚醚树脂，可以配制常温固化的自清洁型涂料。20世纪90年代，美国华盛顿海军研究室的F.B.Robert研究成功聚四氟乙烯-含氟多元醇涂料，可以常温固化。  \n\n目前国内市场用量和影响最大的氟烯烃共聚物主要为溶剂可溶室温/中低温固化型氟烯烃-乙烯基醚/酯共聚物氟碳树脂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 502,
+        "chunk": "# 1.原料  \n\n制备溶剂型氟碳树脂的氟烯烃单体包括三氟氯乙烯（CTFE)、四氟乙烯（TFE)、六氟丙烯、偏氟乙烯、含氟丙烯酸酯等。溶剂型氟碳树脂包括氟烯烃单体的均聚物和共聚物。均聚物主要有聚偏二氟乙烯、聚氟乙烯等。烷基乙烯基醚类单体包括甲基乙烯基醚、乙基乙烯基醚、异丙基乙烯基醚、正丙基乙烯基醚、正丁基乙烯基醚、叔丁基乙烯基醚、异丁基乙烯基醚、环己基乙烯基醚等。烷基乙烯基酯类单体包括醋酸乙烯酯、丙酸乙烯酯、乳酸乙烯酯、新戊酸乙烯酯、己酸乙烯酯、辛酸乙烯酯、葵酸乙烯酯、月桂酸乙烯酯、豆蔻酸乙烯酯、棕榈酸乙烯酯、硬脂酸乙烯酯、叔碳酸乙烯酯Veova-9和Veova-10（壳牌公司产品商品名)。羟基单体包括羟乙基烯丙基醚、羟丙基烯丙基醚、羟基异丙基烯丙基醚、羟丁基烯丙基醚、羟乙基乙烯基醚、羟丙基乙烯基醚、羟丁基乙烯基醚。烯酸单体包括丙烯酸、甲基丙烯酸、丁烯酸、油酸、富马酸、马来酸、乙烯基乙酸和十一碳烯酸等。  \n\n溶剂型氟碳树脂包括氟烯烃单体的均聚物和共聚物。均聚物主要有聚偏二氟乙烯、聚氟乙烯等。溶剂型氟烯烃-乙烯基醚/酯共聚物氟碳树脂主要由三氟氯乙烯/四氟乙烯、烷基乙烯基醚/烷基乙烯基酯、羟烷基烯醚、烯酸等单体共聚而成。由于以氟烯烃-乙烯基醚/酯共聚物氟碳树脂为基料的涂料主要是外用，一般不采用芳香基醚，也不采用丙烯酸酯。在多元共聚氟烯烃-乙烯基醚/酯共聚物氟碳树脂中，氟烯烃单体能够提供树脂超长耐候性和耐化学药品性，烷基乙烯基醚能够提供树脂在有机溶剂中溶解性，使氟碳树脂常温下可溶解在普通的溶剂中，给后期涂料施工带来很大便利，同时使氟碳树脂透明度提高，涂膜光泽改善。烯酸单体能够提高树脂对颜料的润湿性和对底材的附着力。羟烷基乙烯基醚使涂料在常温或中低温下可和多异氰酸酯固化剂或氨基树脂交联固化成膜。  \n\n近年来，由于多种含氟丙烯酸酯单体相继产业化，如甲基丙烯酸六氟丁酯、甲基丙烯酸-2,2,2-三氟乙酯、甲基丙烯酸十二氟庚酯和丙烯酸六氟丁酯等，使溶剂型含氟丙烯酸树脂及涂料也有较快发展，通过含氟丙烯酸酯与其他丙烯酸类单体共聚，提高氟碳树脂涂料（涂层）的光泽度和柔韧性，也可以降低氟碳树脂成本。  \n\n基于安全环保因素，国家近年来对芳香烃、脂肪烃和酮类等高毒性溶剂使用与排放限制越来越严格，很多溶剂型氟碳树脂、涂料领域的科技工作者已经开展了对低毒性溶剂型氟碳树脂的研究，用低毒性的溶剂，如汽油、正丁醇、乙醇和丙酮混合溶剂代替溶剂型涂料中的三苯溶剂（苯、甲苯和二甲苯)。采用碳酸二甲酯（DMC）等低毒性高效溶剂开展对高固体分溶剂型氟碳树脂的研究工作。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 503,
+        "chunk": "# 2.制备方法简述  \n\n制备溶剂型氟碳树脂最常用、最成熟的聚合工艺就是溶液聚合。根据氟碳树脂性能和工艺需要，工业上也有采用悬浮聚合和乳液聚合工艺进行合成的。  \n\n聚偏二氟乙烯氟碳树脂主要可由两种聚合方法合成，即乳液聚合和悬浮聚合。界面聚合和辐射引发聚合也可用于聚偏二氟乙烯氟碳树脂的制备。在乳液聚合时，采用含氟表面活性剂、引发剂和链终止剂，反应终了后去除残余的引发剂和表面活性剂。然后乳胶干燥，研磨成平均粒径为 $2\\sim4\\mu\\mathrm{m}$ 的细粉末。悬浮聚合可以在水介质中进行，在引发剂、胶体分散剂（不一定都需要）和控制分子量的链转移剂存在下聚合，得到颗粒状聚合物。一般用于生产溶剂型氟碳涂料的聚偏二氟乙烯树脂采用乳液聚合工艺生产。  \n\n溶剂可溶常温固化氟烯烃-乙烯基醚/酯共聚物氟碳树脂工业化生产大都采用溶液聚合工艺。由于氟烯烃（三氟氯乙烯和四氟乙烯）单体在常温下呈气态，聚合反应为高压聚合反应。聚合反应用引发剂一般为偶氮二异丁睛、过氧化二苯甲酰和有机过氧化酯类。  \n\n溶剂型含氟丙烯酸酯类氟碳树脂都是采用常压溶液聚合工艺生产。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 504,
+        "chunk": "# 3.溶剂型氟碳树脂种类  \n\n溶剂型氟碳树脂包括溶剂分散型和溶剂可溶型两类。按成膜物的性质和成膜机理可分为单组分氟碳树脂与双组分氟碳树脂两类。溶剂型双组分氟碳树脂配制成涂料时，如果采用封闭异氰酸酯固化剂或三聚氰胺树脂固化，由于包装采用单包装桶，也被认为是溶剂型单组分氟碳涂料。常用溶剂型氟碳树脂有FEVE、PVDF、含氟丙烯酸酯树脂等。  \n\n(1）溶剂分散型氟碳树脂主要是指聚偏二氟乙烯分散液，以溶剂分散体用于涂料，熔点在160～170C之间。美国ElfAtochem公司是首先向涂料（涂装）工业提供聚偏二氟乙烯树脂的公司之一，品牌为 $\\mathrm{\\Kynar{500}}$ ，目前的产量最大，此外还有Ausimont公司的Hylar5000和日本吴羽化学工业的Kfpolymer。这类产品用以生产以聚偏二氟乙烯树脂为主要成分的外墙耐候性氟碳涂料。表2-1-285给出美国 $\\mathrm{\\Kynar{500}}$ 聚偏二氟乙烯树脂的部分性能。  \n\n表2-1-285美国Kynar500聚偏二氟乙烯树脂的部分性能  \n\n\n<html><body><table><tr><td>项 目</td><td>指 标</td><td>测定方法和标准</td></tr><tr><td>氟含量（质量分数）/%</td><td>59</td><td>理论计算</td></tr><tr><td>密度/（g/cm）</td><td>1.75 ~1.77</td><td>ASTM D 792</td></tr><tr><td>极限氧指数/%</td><td>43</td><td>ASTM D 2863</td></tr><tr><td>吸水率/%</td><td>≤0.04</td><td>ASTM D 570</td></tr><tr><td>折射率（25C)</td><td>1.42</td><td>ASTM D 542</td></tr><tr><td>熔点/C</td><td>160</td><td>ASTM D 3418</td></tr><tr><td>玻璃化温度（T）/C</td><td>-40</td><td>动态机械分析法</td></tr><tr><td>分解温度/C</td><td>382~393</td><td>热解重量分析法</td></tr><tr><td>拉伸强度/MPa</td><td>33~55</td><td>ASTM D 638</td></tr><tr><td>冲击强度/（J/m²）</td><td>800~4270</td><td>ASTM D 256</td></tr><tr><td>比热容/[J/(g·K)]</td><td>1.24</td><td>差示扫描量热法</td></tr></table></body></html>  \n\n(2）溶剂可溶型氟碳树脂包括单组分和双组分氟碳树脂两类，单组分氟碳树脂市场常见产品主要是溶剂型含氟丙烯酸酯树脂。溶剂型含氟丙烯酸酯树脂配制涂料主要应用于建筑外墙，含氟丙烯酸酯类氟碳树脂的含氟基团分布在聚合物侧链上，而氟烯烃-乙烯基醚/酯共聚物氟碳树脂含氟基团则存在于聚合物主链上，导致氟烯烃-乙烯基醚/酯共聚物氟碳树脂配制涂料的耐候性和耐化学药品性要优于含氟丙烯酸酯类氟碳树脂配制的涂料，因此也有人建议将含氟丙烯酸酯类氟碳树脂划归于氟改性丙烯酸酯树脂，不把它列入氟碳树脂范畴。但和普通聚酯、丙烯酸树脂配制涂料相比，溶剂型含氟丙烯酸酯涂料在自洁性、耐化学药品性等方面还是有很多优势。另外，由于含氟丙烯酸酯单体生产成本一直居高不下，也限制了单组分含氟丙烯酸酯树脂的应用。  \n\n溶剂可溶型双组分氟碳树脂主要是指溶剂型FEVE氟碳树脂。溶剂型氟碳树脂结构式（以氟烯烃-乙烯基酯共聚氟碳树脂为例）如下：  \n\n![](images/2210aabbf2a69e886a8f80c3428dcb117f84e11b050aa51c539c7d02910068b6.jpg)  \n\n按采用含氟单体不同（三氟氯乙烯和四氟乙烯)，分为“3F”型溶剂型氟碳树脂和“4F”型溶剂型氟碳树脂；按共聚单体类别不同，分为氟烯烃-乙烯基酯共聚氟碳树脂和氟烯烃-乙烯基醚共聚氟碳树脂；按应用领域不同，分为建筑用溶剂型氟碳树脂、钢结构用溶剂型氟碳树脂和卷材用溶剂型氟碳树脂等品种。从理论上分析，“3F”型氟碳树脂溶解性、相容性和硬度要比“4F”型氟碳树脂好一些；“4F”型氟碳树脂耐候性和耐化学药品性比“3F”型氟碳树脂好一些；氟烯烃-乙烯基醚共聚氟碳树脂是一个完全交替排列的共聚物，而氟烯烃-乙烯基酯共聚氟碳树脂是不完全交替排列的共聚物，氟烯烃-乙烯基醚共聚氟碳树脂耐候性和耐化学药品性比氟烯烃-乙烯基酯共聚氟碳树脂好一些。表2-1-286列出溶剂型双组分氟碳树脂技术指标，表2-1-287列出不同规格溶剂型双组分氟碳树脂技术指标。  \n\n表2-1-286溶剂型双组分氟碳树脂技术指标  \n\n\n<html><body><table><tr><td colspan=\"2\">项 目</td><td>技术指标</td><td>项 目</td><td>技术指标</td></tr><tr><td colspan=\"2\">氟含量/%</td><td>25~35@</td><td>分子量分布系数</td><td>1. 5 ~2. 5</td></tr><tr><td colspan=\"2\">密度/（g/cm²）</td><td>1.4~ 1. 5</td><td>玻璃化温度/℃</td><td>20~70</td></tr><tr><td colspan=\"2\">羟值/（mgKOH/g）</td><td>40~150</td><td>分解温度/°C</td><td>240~250</td></tr><tr><td colspan=\"2\">酸值/（mgKOH/g）</td><td>0~30</td><td>耐温性/℃</td><td>30~150</td></tr><tr><td rowspan=\"2\">分子量</td><td>M</td><td>0.8×10~6×10*</td><td>溶解度参数</td><td>8.8（计算）</td></tr><tr><td>M</td><td>1.0×10*~15×10</td><td></td><td></td></tr></table></body></html>\n\n$\\Phi$ 以三氟氯乙烯（CTFE）为基础的树脂氟含量为25%～29%（质量分数）；以四氟乙烯（TFE）为基础的树脂氟含量最高达35%。$\\oslash$ 旭硝子公司早期发表的Lumiflon的分子量 $M_{\\mathfrak{n}}$ 为0 $\\cdot2\\times10^{4}\\sim10\\times10^{4}$ ，M 为0. $4\\times10^{4}\\sim20\\times10^{4}$ 。表中采用的是1997年报道的数据.$\\textcircled{3}$ 溶剂型双组分氟碳树脂玻璃化温度T依照引入烷基醚的结构和数量而变化。  \n\n表2-1-287不同规格溶剂型双组分氟碳树脂技术指标  \n\n\n<html><body><table><tr><td rowspan=\"2\">项 目</td><td colspan=\"4\">技术指标</td></tr><tr><td>A</td><td>B</td><td>C</td><td>D</td></tr><tr><td>固含量/%</td><td>60</td><td>40</td><td>50</td><td>65</td></tr><tr><td>羟值/（mgKOH/g)</td><td>32</td><td>21</td><td>31</td><td>59</td></tr><tr><td>酸值/(mgKOH/g)</td><td>0~6.5</td><td>2.0</td><td>0</td><td>6.5</td></tr><tr><td>黏度（25℃）/Pa·s</td><td>4.0</td><td>0.40</td><td>0.65</td><td>3.00</td></tr><tr><td>数均分子量M。</td><td>20000</td><td>20000</td><td>200000</td><td>6000</td></tr><tr><td>玻璃化温度/C</td><td>45~50</td><td>20</td><td>3</td><td>40~45</td></tr></table></body></html>  \n\n表2-1-287中列出的是用于不同目的的几种溶剂型双组分氟碳树脂规格，B型和C型氟碳树脂是玻璃化温度较低的品种，它们能制成高韧性涂膜，适用于卷材涂料和塑料用涂料。分子量较低而羟值较高的D型树脂，活性较大，与固化剂交联反应快，交联密度大，涂膜具有高光泽度、高硬度及良好的耐溶剂性，适用于汽车及飞机涂料。A型树脂玻璃化温度较高，分子量也较高，羟值不低，可作为通用型溶剂型双组分氟碳树脂用于建筑外墙涂料与工业维修涂料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 505,
+        "chunk": "# 4.溶剂型氟碳树脂制备过程  \n\n溶剂型氟碳树脂种类较多，下面以最为常见的聚偏二氟乙烯（PVDF）和氟烯烃-乙烯基酯共聚物（FEVE）氟碳树脂为例（实验室配方）来说明溶剂型氟碳树脂的制备过程。  \n\n（1）聚偏二氟乙烯氟碳树脂的制备过程聚偏二氟乙烯树脂是一种高分子量的半晶体聚合物。由1，1-二氟乙烯 $_{\\mathrm{{\\cdotH}_{2}C-C F_{2}}}$ ）加聚而成。以下以乳液聚合为例说明聚偏二氟乙烯树脂的制备过程。  \n\n把 $50\\mathrm{g}$ 偏氟乙烯、 $15\\mathrm{mL}$ 去离子水、 $_{0.58}$ 二异丙基过氧化碳酸盐、0.05g甲基纤维素置于 ${300}\\mathrm{ml}.$ 的高压反应釜中，在 $20\\Upsilon$ 聚合 $20\\mathbf{h}$ ，聚偏氟乙烯的收率大于 $98\\%$ 。偏氟乙烯的乳液聚合一般采用氟系表面活性剂，如5～15个碳的全氟、w-氯全氟羧酸盐、氟磺酸盐、全氟苯甲酸类和全氟邻二苯甲酸类等。采用二异丙基过氧化物等为引发剂，以全氟辛酸盐为表面活性剂，在 $80\\sim110^{\\circ}C$ 和10.4～34.32MPa条件下进行乳液聚合。用1份无水全氯邻苯二甲酸、200份去离子水和0.2份过硫酸铵，在 $86^{\\circ}C$ 和 $2.76\\ensuremath{\\mathrm{MPa}}$ 的条件下，也可以得到聚偏二氟乙烯乳液。  \n\n(2）溶剂型氟烯烃-乙烯基酯共聚物氟碳树脂制备在2L带有电磁揽拌的高压釜中加入$200{\\bf g}$ 乙酸丁酯、 $2,5{\\mathrm{g}}$ 偶氮二异丁睛，将高压釜抽空，充氮，然后用计量泵加入126g环已基乙烯基醚（CHVE)、 $17.2g$ 醋酸乙烯酯（VAc)、 $147.2g$ 叔碳酸乙烯酯、 $116g$ 羟丁基乙烯基醚（HBVE)、 $300\\mathbf{g}$ 丙酮，然后通人四氟乙烯至反应釜压力为 $0.5\\ensuremath{\\mathrm{MPa}}$ ，将高压釜逐渐加温至 $70\\%$ ，通入四氟乙烯至反应釜压力为1.5MPa，维持压力，保持温度在 $70\\Upsilon$ 。反应时间为 $4.5\\mathrm{h}$ 。降温出料。得到清澈透明的无色或浅黄色黏稠液体。该黏稠液体的固含量为$55\\%$ （质量分数)。取部分该黏稠液体，用石油醚作为沉淀剂进行沉淀，然后将沉淀物在$60\\ensuremath{\\mathrm{\\overline{{C}}}}$ 下真空干燥24h得到样品。该样品氟含量为 $27.03\\%$ ，羟值为 $56,3\\mathrm{mgKOH/g}$ ，单体共聚比例为四氟乙烯：环己基乙烯基醚：羟丁基乙烯基醚：醋酸乙烯酯：叔碳酸乙烯酯 $^{=48}$ \\*$15.8:16.3:4.4:15.5.$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 506,
+        "chunk": "# 5.溶剂型氟碳涂料配方实例和性能  \n\n以聚偏二氟乙烯树脂为基础的有机溶剂分散体涂料的主要组成为：聚偏二氟乙烯树脂、丙烯酸树脂、颜料、有机溶剂和添加剂（助剂)。制成溶剂型氟碳树脂涂料，其方法是将聚偏二氟乙烯制成粉末，然后分散在热塑性的丙烯酸树脂溶液中，实际是有机溶胶，涂覆后，在 $230^{\\circ}\\mathrm{C}$ 以上加热，借助丙烯酸树脂和高沸点溶剂熔融聚偏二氟乙烯粉末，流平成涂膜。  \n\n丙烯酸树脂作为改性剂，其主要作用是改善树脂对颜料的分散性，提高对底材的附着力和改善涂膜的稳定性。比较常用的是以甲基丙烯酸甲酯为基础的热塑性丙烯酸树脂，也可采用热固性涂料用丙烯酸树脂。聚偏二氟乙烯系列树脂是热塑性树脂，和热塑性丙烯酸树脂配合使涂膜具有同一固化机理，树脂间相容性好，能形成高分子树脂合金，丙烯酸树脂也改进涂膜的硬度和光泽度。当丙烯酸树脂含量超过 $30\\%$ （质量分数）以上时，会导致涂膜的耐溶剂性及抗断裂拉伸性降低。  \n\n颜料筛选要和聚偏二氟乙烯树脂一样具有长期耐候性（20年以上）。通常可被选用的颜料包括耐候性金红石型二氧化钛、外用级的珠光云母颜料等。有机颜料、荧光颜料、锐钛型二氧化钛等耐候性差的颜料不推荐使用。  \n\n有机溶剂对固体组分（树脂、颜料和其他固体添加剂）起分散介质作用，改善涂料黏度以符合相应的施工要求，溶解聚偏二氟乙烯树脂和在涂膜烘烤过程中促进与丙烯酸树脂改性剂的熔融混合。用于以聚偏二氟乙烯树脂为基础溶剂型氟碳树脂涂料的有机溶剂分三类：活性溶剂、潜溶剂和非溶剂。溶剂分类见表2-1-288。  \n\n表2-1-288聚偏二氟乙烯氟碳树脂所使用的溶剂分类  \n\n\n<html><body><table><tr><td>活性溶剂</td><td>潜溶剂（溶解温度）</td><td>非溶剂</td></tr><tr><td>丙酮</td><td>丁内酯（65℃)</td><td>已烷</td></tr><tr><td>四氢呋哺</td><td>异佛尔酮（75℃）</td><td>戊烧</td></tr><tr><td>甲乙酮</td><td>甲基异戊酮(102℃)</td><td>苯</td></tr><tr><td>二甲基甲酰胺(DMF)</td><td>环已酮（70℃)</td><td>甲苯</td></tr></table></body></html>  \n\n<html><body><table><tr><td>活性溶剂</td><td>潜溶剂（溶解温度）</td><td>非溶剂</td></tr><tr><td>二甲基乙酰胺</td><td>邻苯二甲酸二甲酯（110℃）</td><td>甲醇</td></tr><tr><td>四甲脉</td><td>丙二醇甲醚（115℃)</td><td>乙醇</td></tr><tr><td>二甲基亚矾</td><td>碳酸丙烯酯（80℃）</td><td>四氧化碳</td></tr><tr><td>磷酸三甲酯</td><td>二丙酮醇（100°℃）</td><td>邻二氯苯</td></tr><tr><td>N-甲基吡咯酮</td><td>甘油三醋酸酯（100℃）</td><td>三氯乙烯</td></tr></table></body></html>  \n\n其中，在一定温度下， $5\\%\\sim10\\%$ （质量分数）的聚偏二氟乙烯树脂可溶解于活性溶剂中，由此可制成有机溶胶型涂料。潜溶剂是PVDF的最常用溶剂，由其制成的分散体涂料固体分可达 $40\\%\\sim50\\%$ （质量分数）。在分散体涂料体系中，PVDF树脂以粉末形态悬浮在其中，在室温下保持稳定的流体形态。在加热烘烤过程中，树脂被溶解，并随溶剂挥发而聚结成膜。非溶剂对PVDF树脂无溶解作用，主要作用为稀释涂料和改善涂料溶剂释放性能。在配制溶剂型聚偏二氟乙烯涂料时也要添加一些相应的助剂，来赋予涂料不同的性能。常用助剂包括防沉剂、消泡剂和抑泡剂、分散剂和乳化剂、防菌剂、流平剂、触变改性剂等。表2-1-289列出以聚偏二氟乙烯树脂为基础的氟碳涂料一般配方，表2-1-290列出具体实验室配方。  \n\n表2-1-289 以聚偏二氟乙烯树脂为基础的氟碳涂料一般配方  \n\n\n<html><body><table><tr><td>原 料</td><td>用量/%</td><td>备 注</td></tr><tr><td>聚偏二氟乙烯树脂</td><td>20~25</td><td>占树脂总量70%，总固体量中至少占40%</td></tr><tr><td>丙烯酸树脂</td><td>8~11</td><td>热塑性树脂</td></tr><tr><td>颜料</td><td>12~16</td><td></td></tr><tr><td>溶剂</td><td>50~60</td><td>Kynar 500的潜溶剂</td></tr></table></body></html>  \n\n续表  \n表2-1-290以聚偏二氟乙烯树脂为基础的氟碳涂料配方（实验室）  \n\n\n<html><body><table><tr><td colspan=\"2\">项 目</td><td>指标</td><td colspan=\"2\">项 目</td><td>指标</td></tr><tr><td rowspan=\"6\">用量/%</td><td>聚偏二氟乙烯树脂</td><td>23.8</td><td rowspan=\"5\">板面温度/℃C 时间/s 条件 底漆厚度/μm</td><td>240~255</td></tr><tr><td>Paraloib B44@</td><td>21.7</td><td></td></tr><tr><td>异佛尔酮</td><td>28.1 施工应</td><td>烘烤45~60</td></tr><tr><td>邻苯二甲酸二甲酯</td><td>4.8 用工艺</td><td>5~7</td></tr><tr><td>TiOz-Pipure R960@</td><td>21.6</td><td></td></tr><tr><td>合件分/%</td><td>105</td><td rowspan=\"2\">面漆厚度/μm</td><td rowspan=\"2\">20~25</td></tr><tr><td></td><td></td></tr></table></body></html>\n\n$\\Phi$ Rohm &.Hass 公司产品：40%的甲基丙烯酸甲酯树脂溶液。$\\textcircled{2}$ 杜邦公司钛白粉牌号，  \n\n聚偏二氟乙烯氟碳涂料具有超强的耐候性和优良的化学稳定性，具体表现为寿命长、不褪色、无污染和耐老化等。表2-1-291列出聚偏二氟乙烯树脂为基础的氟碳涂料的特殊性能总结。  \n\n表2-1-291以聚偏二氟乙烯树脂为基础的氟碳涂料的特殊性能总结   \n\n\n<html><body><table><tr><td>要求的涂料性能</td><td>聚偏二氟乙烯为基础的涂料的特殊性能</td></tr><tr><td>外用耐久性</td><td>抗UV降解，长期的保光保色性，高抗粉化性</td></tr><tr><td>能抗大气污染物、气体和液体腐蚀，低维护性</td><td>优良的抗化学药品酸和液碱性，不受臭氧攻击</td></tr><tr><td>污染物吸附性低</td><td>硫水表面，低表面能</td></tr><tr><td>表面无积存污点</td><td>低摩擦系数</td></tr><tr><td>低霉菌和细菌污染性</td><td>具有一定抗霉菌、细菌性</td></tr><tr><td>能抗机械损伤和磨损</td><td>抗摩擦性好，抗冲击性好</td></tr><tr><td>好的防腐蚀性</td><td>优良的抗化学药品性，对氟和湿气腐蚀离子低渗透性，高电阻，黏结性好</td></tr><tr><td>涂装后成膜性</td><td>在一定应力下力学性能、柔韧性、附着力好</td></tr></table></body></html>  \n\n溶剂型含氟丙烯酸酯树脂涂料配方及主要性能和普通丙烯酸树脂涂料类似，在此就不再做介绍。  \n\n下面以ZB-F400树脂为例，简单介绍溶剂型氟烯烃-乙烯基醚共聚氟碳树脂涂料配方实例与主要性能。表2-1-292列出ZB-F400溶剂型氟碳树脂白漆基本配方。表2-1-293列出ZB-F400溶剂型氟碳树脂涂料技术指标。  \n\n表2-1-292ZB-F400溶剂型氟碳树脂白漆基本配方（实验室）  \n\n\n<html><body><table><tr><td colspan=\"3\">配 比</td><td>白色高光氟碳面漆/%</td><td>白色亚光氟碳面漆/%</td></tr><tr><td rowspan=\"7\">主剂</td><td>氟碳树脂</td><td>F400</td><td>68.9</td><td>60.0</td></tr><tr><td>溶剂</td><td>乙酸丁酯</td><td>4.5</td><td>10.5</td></tr><tr><td rowspan=\"4\">助剂</td><td>消光剂</td><td>一</td><td>5.5</td></tr><tr><td>防浮色剂</td><td>一</td><td>0.3</td></tr><tr><td>润湿分散剂</td><td>1.1</td><td>1.2</td></tr><tr><td>流平剂</td><td>0.5</td><td>0.5</td></tr><tr><td>颜料</td><td>金红石型钛白粉</td><td>25.0</td><td>22.0</td></tr><tr><td colspan=\"2\">总计</td><td>100.0</td><td>100.0</td></tr><tr><td colspan=\"2\">主剂：3390@（质量比）</td><td>151</td><td>17:1</td></tr></table></body></html>\n\n$\\Phi$ 3390为拜耳公司多异氰酸酯固化剂商品牌号。  \n\n表2-1-293 ZB-F400溶剂型氟碳树脂技术指标  \n\n\n<html><body><table><tr><td>检验项目</td><td>技术指标</td><td>技术标准</td></tr><tr><td>附着力(划画法)/级</td><td>1</td><td>GB/T1720-1979(1989)</td></tr><tr><td>干燥时间(表干)/h</td><td>1</td><td>GB/T1728—1979(1989)乙法</td></tr><tr><td>干燥时间(实干)/h</td><td>24</td><td>GB/T1728—1979（1989）甲法</td></tr><tr><td>耐冲击性/cm</td><td>50</td><td>GB/T 1732—1993</td></tr><tr><td>铅笔硬度</td><td>3H</td><td>GB/T 6739—1996A法</td></tr><tr><td>柔韧性/mm</td><td>1</td><td>GB/T 1731—1993</td></tr><tr><td>光泽度(60°)/%</td><td>80</td><td>GB/T 9754—1988</td></tr><tr><td>耐酸性（侵人15%HNO：溶液中7天）</td><td>无变化</td><td>GB/T 92741988甲法</td></tr><tr><td>耐水性（浸7天)</td><td>无变化</td><td>GB/T 1733-1993甲法</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>检验项目</td><td>技术指标</td><td>技术标准</td></tr><tr><td>耐酸性(浸入15%HCl溶液中7天)</td><td>无变化</td><td>GB/T 9274—1988甲法</td></tr><tr><td>耐酸性(浸人15%HzSO溶液中7天)</td><td>无变化</td><td>GB/T 9274—1988甲法</td></tr><tr><td>耐碱性（浸人15%NaOH溶液中7天）</td><td>无变化</td><td>GB/T 9274—1988甲法</td></tr><tr><td>耐湿热性（1000h)</td><td>无变化</td><td>GB/T 17401979</td></tr><tr><td>耐盐雾性（2000h)</td><td>无变化</td><td>GB/T 1771-1991</td></tr><tr><td>耐人工老化试验（3000h）</td><td>失光1级，变色2级， 粉化0级，龟裂0级</td><td>GB/T 18641997</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 507,
+        "chunk": "# 6.主要用途及方向  \n\n近年来，以三氟氯乙烯和四氟乙烯为主要原料合成常温固化涂料用树脂方面取得了很多成果，已经研究成功一系列不同用途的氟碳树脂涂料。溶剂型氟碳树脂涂料的应用涉及现代工业各领域：高档建筑和重点市政工程；新兴的海洋工程——海上设施、海岸和海湾构造物及海上石油钻井平台等；现代化的交通运输—桥梁、船舶、集装箱、火车、汽车、高速公路和铁路护栏等；重要的能源工业—油管、油罐、输变电设备、核电设备和煤矿设备等；大型工矿企业——化工、石油化工、钢铁、化肥等工厂的管道、贮槽、设备以及大型矿山的冶炼设备等。在化工、大气和海洋环境里溶剂型氟碳涂料一般可使用15 年以上，在酸、碱、盐和有机溶剂介质里且有一定温度的腐蚀条件下，一般可使用5年以上。  \n\n随着环境保护意识的增强和各国对环境保护法规的健全，低毒性溶剂型、高固体分等环保型溶剂型氟碳树脂是今后溶剂型氟碳树脂重点研发的方向之一。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 508,
+        "chunk": "# 三、水性氟碳树脂  \n\n由于全世界对挥发性有机化合物（VOC）的排放做出了严格限制，涂料界面临严峻的挑战，大力推广环境友好型涂料已成为共识。因此，水性氟碳树脂的研究开发成为国内外关注和研究的重点课题。  \n\n水性氟碳树脂是以水为分散介质的一类氟碳树脂，呈乳白色或半透明状。水性氟碳树脂具有超耐久性、耐沾污性、耐化学介质性、热稳定性等，是继溶剂型氟碳树脂之后，因符合环境保护要求而重点开发研究的氟碳树脂品种。",
+        "category": " Introduction"
+    },
+    {
+        "id": 509,
+        "chunk": "# 1.原料  \n\n制备水性氟碳树脂常用的含氟单体有四氟乙烯（TFE)、三氟氯乙烯（CTFE)、偏二氟乙烯（VDF)、氟乙烯（VF)、六氟丙烯（HFP)、含氟烷基乙烯基（烯丙基）酯或醚等。从产业化角度，制备氟碳树脂仅使用其中一种，以三氟氯乙烯使用最为常见，在文献报道中也有将几种氟烯烃单体放在一起使用，如VDF、TFE 和CTFE三种氟烯烃的混合使用。它们的均聚或共聚的氟烯烃聚合物耐高温稳定、耐候、化学稳定、热稳定，但只能做成高温热塑性涂料。因此需引进非氟烯烃单体来降低结晶度，以获得在常温或中温条件下交联固化的氟碳树脂。  \n\n亲水性非氟烯烃单体包括乙烯基烷基醚（酯)、烯丙基烷基醚（酯)、不饱和羧酸等，如羟丁基乙烯基醚（HBVE)、乙基乙烯基醚（EVE)、环已基乙烯基醚、羟乙基烯丙基醚、醋酸乙烯酯、丁酸乙烯酯、叔碳酸乙烯酯（Veova-9和Veova-10)、丙烯酸乙酯、（甲基）丙烯酸丁酯等，不饱和烯酸包括巴豆酸、十一烯酸、（甲基）丙烯酸等。含羟基官能团单体可用来制备热固性氟碳树脂。根据性能要求，还可以引人其他不同的功能单体，如引进乙烯基烷氧基硅烷单体以提高对基材的附着力，若引进参与聚合的可适度交联单体，能够提高乳液薄膜的耐溶剂擦拭特性。  \n\n制备水乳型水性氟碳树脂需要使用乳化剂，在考虑聚合稳定性和后期使用性能方面，引人量要适当，种类以含氟乳化剂为最适宜，如全氟辛酸铵等；也可以采用常规乳化剂，一般采用阴离子乳化剂和非离子乳化剂混合使用，以保证乳液有良好的化学稳定性、机械稳定性以及冻融稳定性等，如十二烷基硫酸钠、烷基（苯）磺酸钠、脂肪醇聚氧乙烯醚、烷基酚聚氧乙烯醚等。  \n\n在进行溶液聚合-相反转法制备水性氟碳树脂时，引发剂通常选择偶氮类引发剂，如偶氮二异丁睛等，而乳液聚合过程通常选择水溶性过硫酸盐类引发剂，如过硫酸钾、过硫酸钠等；或者选择氧化还原引发体系，如过氧化氢-氯化亚铁、过硫酸钾-氯化亚铁等。为了稳定聚合体系 $\\mathsf{p H}$ ，保证引发过程正常进行，在聚合过程中要加入碳酸（氢）钠、磷酸氢钠等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 510,
+        "chunk": "# 2.制备方法简述  \n\n水性氟碳树脂制备方法一般包括溶液聚合-相反转法和乳液聚合法，其中乳液聚合法根据实施的特点可以分为常压聚合法、低压聚合法、核壳聚合法和无皂聚合法。  \n\n溶液聚合-相反转法是通过设计合适的羧基值、分子量以及调节聚合过程溶剂使用来制备有机溶剂可溶性氟碳树脂，在一定温度下蒸除大部分溶剂，同时通过氨化成盐法以及适量乳化剂存在下，使氟碳树脂稳定分散在水相中而获得水性氟碳树脂，也可称水可稀释性水性氟碳树脂。因溶液聚合法成熟，采用该方法相对简单，容易实施，树脂保留了溶剂型树脂性能特点，能够较好满足应用要求。不足之处在于溶剂气味重，生产过程中溶剂要进行回收利用，能源消耗较大。  \n\n乳液聚合法是将各种单体和乳化剂、调节剂等助剂混合在水相中，控制合理的工艺条件，即可制备贮存稳定、性能优异的氟碳树脂乳液。其中常压聚合法和低压聚合法是针对聚合过程所使用单体物理特性而定，如含氟烷基乙烯基（烯丙基）酯或醚等单体为液相，则采用常压乳液聚合法，相对容易实现，国内该方法的文献报道很多，而四氟乙烯（TFE)、三氟氯乙烯（CTFE)、偏二氟乙烯（VDF）等氟单体在常温常压下是气相，因此需要在压力状态下实施聚合，加之运输困难，在一定程度上限制了相关树脂产品的开发。核壳乳液聚合法也可称多段聚合法，在原料配方不变的情况下通过改变加料工艺方式，即先做核，再做壳，使乳液粒子结构改变，达到所要设计的性能，国外有很多专利报道。而无皂乳液聚合法则是避开常规乳液聚合过程中采用低分子乳化剂和保护胶体，而采用高分子乳化剂、聚合物分散液或可参与反应并对单体有乳化能力的乳化剂（包括具有内乳化作用的大分子单体)等，在含有引发剂的水相中进行乳液聚合制备水性氟碳树脂。该方法制备的水性氟碳树脂在耐水性、抗沾污性、光泽等性能上有很大改善，是当前重要发展方向。  \n\n此外，可通过分散（悬浮）聚合法制备水可分散型氟碳树脂，如聚三氟氯乙烯（PCT-FE）水分散液、聚四氟乙烯（PTFE）水分散液等。以PTFE为例，可以在不锈钢压力容器中，以过硫酸盐为引发剂，加入全氟羧酸盐等含氟类分散剂，通入四氟乙烯气体，加入一定量活化剂，在一定温度下引发聚合，制备聚四氟乙烯分散液，再通过浓缩过程使分散液浓度达 $60\\%$ ，并通过非离子表面活性剂稳定而获得乳白色水分散液。分散（悬浮）聚合法有合成条件苛刻、操作烦琐、要使用有机溶剂等缺陷，要制备稳定性好、颗粒细微的悬浮液比较困难，目前逐渐呈现出被乳液聚合法所替代的趋势。表2-1-294是国内相关厂家水性氟碳树脂指标。  \n\n表2-1-294国内相关厂家水性氟碳树脂指标  \n\n\n<html><body><table><tr><td rowspan=\"2\">项 目</td><td colspan=\"2\">指 标</td></tr><tr><td>上海市有机氟材料研究所氟树脂301</td><td>晨光化工研究院二分厂</td></tr><tr><td>外观</td><td>乳白色或微黄色液体</td><td>白色均匀乳液</td></tr><tr><td>密度（20℃）/(g/cm）</td><td>1.50</td><td>1. 50 ~1. 55</td></tr><tr><td>pH</td><td>9~10</td><td>≥8</td></tr><tr><td>黏度（25C）/(mm²/s)</td><td>10~12</td><td>6~15</td></tr><tr><td>表面张力/（×10-N/cm)</td><td>33~34</td><td>一</td></tr><tr><td>固含量/%</td><td>60±1</td><td>60±2</td></tr></table></body></html>  \n\n上述水性氟碳树脂制备方法各有其特点，应根据实际需要选择不同的合成方法、合适的氟烯烃单体及可聚合的不饱和烯烃单体，严格控制合成工艺，以制得结构可控、性能符合要求的水性氟碳树脂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 511,
+        "chunk": "# 3.水性氟碳树脂种类  \n\n水性氟碳树脂包括水乳型水性氟碳树脂、水溶性（或称水可稀释性）水性氟碳树脂和水分散型水性氟碳树脂三类。根据性能特点和涂料使用的要求，又可分为单组分热塑性乳液、双组分交联热固性乳液和单组分可交联型乳液，后两者乳液聚合物中要引进特殊的功能单体。而水乳化氟碳树脂按照氟单体种类，市场上出现两种：一种是以含氟丙烯酸单体（如丙烯酸六氟丁酯等）为氟化单体的氟碳树脂乳液，单体价格比较贵，引进的单体数量有限，氟含量低且氟原子存在于聚合物支链，通常将此类树脂称为氟改性丙烯酸乳液；另一种是以三氟氯乙烯为主要含氟单体的水性氟碳树脂，氟原子存在于聚合物主链，是目前国内市场上应用较多的水性氟碳树脂，比较有代表意义的是大连振邦生产的F500、F600两类产品。由于两种含氟单体物化性质不同，前者制备过程同普通丙烯酸乳液制备差异不大，很容易实施获得产品，本节不做详细介绍。而后者的制备过程则需要在压力状态下进行，生产工艺控制比较复杂。据报道，国内已合成出了以四氟乙烯单体为主要原料的聚四氟乙烯乳液，该乳液性能稳定，可用来制备性能优良且用途广泛的含氟涂料。下面以三氟氯乙烯为例介绍目前国内水性氟碳树脂的合成方法。",
+        "category": " Introduction"
+    },
+    {
+        "id": 512,
+        "chunk": "# 4.水性氟碳树脂制备过程  \n\n典型热塑性水性氟碳树脂组成见表2-1-295。  \n\n表2-1-295热塑性水性氟碳树脂配方（工业配方）  \n\n\n<html><body><table><tr><td>组 分</td><td>投料量（质量分数）/%</td><td>组 分</td><td>投料量（质量分数）/%</td></tr><tr><td>三氟氯乙烯</td><td>13.40</td><td>烷基酚聚氧乙烯醚</td><td>1. 60</td></tr><tr><td>酷酸乙烯酶</td><td>20.32</td><td>碳酸氢钠</td><td>0.13</td></tr><tr><td>丙烯酸丁酯</td><td>11.33</td><td>过硫酸铵</td><td>0.03</td></tr><tr><td>甲基丙烯酸</td><td>0.53</td><td>去离子水</td><td>52.64</td></tr><tr><td>十二烷基苯磺酸钠</td><td>0.02</td><td>合计</td><td>100.00</td></tr></table></body></html>  \n\n操作方法：在高压反应釜中加入定量去离子水、部分乳化剂及碳酸氢钠，搅拌溶解均匀后，加入按一定预乳化工艺进行乳化的单体预乳化液 $4\\%\\sim6\\%$ ，开动搅拌混合均匀后，开始升温，当温度达到 $(60\\pm2)^{\\circ}\\mathrm{C}$ ，加人 $20\\%$ 引发剂溶液，因反应放热温度自行升高，控制温度在75～85℃，当温度平稳时，滴加单体预乳化液和引发剂溶液，在2～4h内加完，当系统压力逐步下降直至平衡时，反应结束。冷却到40℃以下。加入中和剂，调节pH为7～8，过滤，包装。  \n\n若在聚合过程中引人双丙酮丙烯酰胺（DAAM）功能单体参与聚合，先制成含有活泼羰基的水性氟碳树脂，然后加入适量多元酰肼，由于活泼羰基能与酰肼基反应生成和水，是一个可逆反应，尤其是乳液中存在大量水时，该反应实际上是不能进行的，只有在干燥成膜过程中，随着水从涂膜中逸出，反应才可进行，因此用其可制成可交联的单组分氟碳树脂涂料，试验路线如图2-1-96所示。由于在成膜过程中聚合物发生交联固化反应，因而形成的膜具有更佳的力学性能、耐候性、耐溶剂性等。  \n\n![](images/162936dbf5de51c301b886c0043fbaa82391e402f1a453ea2732ec2e01be2f2d.jpg)  \n图2-1-96试验路线  \n\n含羟基水性氟碳树脂制备可以采用乳液聚合方式，但按乳液聚合机理可用于乳液聚合的含一OH基单体并和含氟单体共聚的工业产品比较少见，目前主要采用溶液聚合-相反转法。典型组成见表2-1-296。  \n\n表2-1-296含羟基水性氟碳树脂配方（工业配方）  \n\n\n<html><body><table><tr><td>组 分</td><td>投料量（质量分数）/%</td><td>组 分</td><td>投料量（质量分数）/%</td></tr><tr><td colspan=\"2\">基础氟碳树脂的制备</td><td colspan=\"2\">水可稀释性氟碳树脂的制备</td></tr><tr><td>三氟氯乙烯</td><td>39.11</td><td>基础氟碳树脂</td><td>35.39</td></tr><tr><td>醋酸乙烯酯</td><td>21.04</td><td>0S-15</td><td>1.97</td></tr><tr><td>羟乙基烯丙基醚</td><td>6.2</td><td>烷基酚聚氧乙烯醚</td><td>1.97</td></tr><tr><td>功能单体</td><td>适量</td><td>氨水（25%)</td><td>适量</td></tr><tr><td>乙酸丁酯</td><td>32.59</td><td>去离子水</td><td>60.67</td></tr><tr><td>引发剂</td><td>1.06</td><td>合计</td><td>100</td></tr><tr><td>合计</td><td>100</td><td colspan=\"2\"></td></tr></table></body></html>  \n\n操作方法：除三氟氯乙烯外，将上述原料单体加入高压反应釜中，减压抽出空气，加入三氟氯乙烯，在 $65\\sim75\\Upsilon$ 反应 $_{20\\mathrm{h}}$ ，得氟碳树脂产品，固含量 $56\\%\\sim58\\%$ ，涂-4杯黏度139s，羟值 $55{\\sim}75\\mathrm{mgKOH/g}$ （以固体树脂计)，羧值 $19\\mathrm{mgKOH/g}$ （以固体树脂计)。将基础氟碳树脂加入反应釜中，在搅拌状态下，加热升温，蒸除基础氟碳树脂中大部分溶剂，加入氨水调节 $\\mathsf{p H}$ 为8，同时加入两种乳化剂和水，搅拌至半透明乳白色液体，获得水性氟碳树脂，固含量 $40\\%$  \n\n上述两种不同方法制备的水性氟碳树脂指标见表2-1-297。  \n\n表2-1-297水性氟碳树脂指标  \n\n\n<html><body><table><tr><td rowspan=\"2\">项 目</td><td colspan=\"2\">指 标</td></tr><tr><td>ZB-F500-1~3</td><td>ZB-F600</td></tr><tr><td>类型</td><td>热塑性</td><td>热固性 ?</td></tr><tr><td>外观</td><td>乳白色液体</td><td>淡黄色半透明液体</td></tr><tr><td>不挥发分/%</td><td>42~47</td><td>40~42</td></tr><tr><td>氟含量/%</td><td>≥11</td><td>≥19</td></tr></table></body></html>  \n\n<html><body><table><tr><td rowspan=\"2\">项 目</td><td colspan=\"2\">指 标</td></tr><tr><td>ZB-F500-1~3</td><td>ZB-F600</td></tr><tr><td>pH</td><td>7~9</td><td>7~9</td></tr><tr><td>黏度/mPa·s</td><td>30~300</td><td>10~30</td></tr><tr><td>羟值/（mgKOH/g）</td><td>一</td><td>65 ±10</td></tr><tr><td>数均分子量</td><td>30000~50000</td><td>20000~30000</td></tr><tr><td>最低成膜温度/C</td><td>10~30</td><td>一</td></tr><tr><td>贮存稳定性</td><td colspan=\"2\">无硬块，无絮凝，无明显分层和结皮</td></tr><tr><td>机械稳定性</td><td colspan=\"2\">2500r/min.30min，不破乳，无明显絮凝物</td></tr><tr><td>钙离子稳定性</td><td colspan=\"2\">5mL乳液加1mL0.5%CaCl溶液，通过</td></tr></table></body></html>  \n\n在国内市场上出现的国外产品主要是日本旭硝子公司推出的FEVE乳液以及日本大金公司的ZEFFLE SE 系列水性含氟聚合物乳液。其中FEVE乳液包括热塑性和热固性两种。据报道，在制备过程中，为了获得稳定的FEVE共聚物乳液，在共聚物中引入了具有内乳化作用的聚氧乙烯基醚大分子单体 $\\mathbf{CH}_{2}{\\mathrm{-CHOR}}_{4}$ $(\\mathbf{C}_{2}\\mathbf{H}_{4})_{n}\\mathbf{H}$ (EOVE)；ZEFFLE SE系列水性含氟聚合物乳液是偏氟乙烯（VDF）共聚物与聚甲基丙烯酸甲酯（PMMA）的共聚物。由于PMMA的酯基与PVDF单元之间相互作用强烈，使酯基能受到PVDF 的保护，因此涂膜具有良好的耐水性及优异的耐候性，产品指标见表2-1-298。  \n\n表2-1-298 ZEFFLESE系列水性含氟树脂指标  \n\n\n<html><body><table><tr><td>项 目</td><td>FE-4100</td><td>FE-4200</td><td>ZEFFLE SE</td></tr><tr><td>类型</td><td>热塑性</td><td>热固性</td><td>热塑性</td></tr><tr><td>外观</td><td>乳白色液体</td><td>乳白色液体</td><td>乳白色液体</td></tr><tr><td>羟值/（mgKOH/g)</td><td>16</td><td>55</td><td>一</td></tr><tr><td>最低成膜温度/C</td><td>35~55</td><td>38</td><td>45~60</td></tr><tr><td>不挥发分/%</td><td>≥51</td><td>≥40</td><td>≥50</td></tr><tr><td>pH</td><td colspan=\"2\">8.0 ±1.5</td><td>一</td></tr><tr><td>粒径/nm</td><td colspan=\"2\">100~200</td><td>一</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 513,
+        "chunk": "# 5.水性氟碳涂料配方实例和性能  \n\n以ZB-F500为例介绍水性氟碳涂料性能。基本参数为：颜基比（P/B）1.97，颜料体积浓度（PVC) $35\\%\\sim38\\%$ ，体积固体分（NVV） $37\\%$ ，黏度 $85\\sim92\\mathrm{KU}$ ，细度 ${\\leqslant}40\\mu\\mathbf{m}$ 。水性氟碳涂料配方见表2-299。并依据国家标准（GB/T9755—2001）进行检测，主要性能指标见表2-1-300。  \n\n续表  \n表2-1-299水性氟碳涂料配方（工业配方）  \n\n\n<html><body><table><tr><td>组 分</td><td>投料量（质量分数）/% T</td><td>备 注</td></tr><tr><td>HO</td><td>14.0</td><td></td></tr><tr><td>SN-5040</td><td>0.44</td><td>汉高助剂</td></tr><tr><td>PE-100</td><td>0.1</td><td>汉高助剂</td></tr><tr><td>NXZ</td><td>0.14</td><td>汉高助剂</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>组 分</td><td>投料量（质量分数）/%</td><td>备 注</td></tr><tr><td>丙二醇</td><td>1.08</td><td></td></tr><tr><td>钛白粉2310</td><td>21.46</td><td></td></tr><tr><td>重质碳酸钙</td><td>13.87</td><td>1250目</td></tr><tr><td colspan=\"3\">高速分散、研磨，细度≤40m，过滤</td></tr><tr><td>水性氟碳树脂ZB-F500</td><td>41.95</td><td>自制</td></tr><tr><td>醇酯-12</td><td>1.79</td><td>伊斯曼</td></tr><tr><td>F-111</td><td>0.10</td><td>汉高助剂</td></tr><tr><td>DSX2000</td><td>2.10</td><td>汉高助剂</td></tr><tr><td>SN-636</td><td>2.97</td><td>汉高助剂</td></tr><tr><td colspan=\"3\">低速分散20~30min</td></tr></table></body></html>  \n\n表2-1-300水性氟碳涂料主要性能  \n\n\n<html><body><table><tr><td>项 目</td><td>GB/T 9755—2001优等品指标</td><td>水性氟碳涂料</td></tr><tr><td>对比率</td><td>0.93</td><td>0.95</td></tr><tr><td>耐洗刷性/次</td><td>≥2000</td><td>≥20000</td></tr><tr><td>耐沾污性/%</td><td>≤15</td><td>≤5.1</td></tr><tr><td>耐人工老化性</td><td>600h，粉化小于1级，变色小于2级</td><td>2000h，粉化小于0缓，变色小于2级</td></tr></table></body></html>  \n\n上述数据说明水性氟碳树脂具有优异的耐候性和耐污染性，利用其制备水性氟碳涂料，在建筑涂料方面具有很大应用优势。  \n\n若使用热固性水性氟碳树脂制备涂料时则需使用水性多异氰酸酯作为交联剂，如日本聚氨酯公司的AQ210以及Rhodia公司的WT2102等产品，形成的涂膜的机械强度、耐沾污性、耐溶剂性、耐热性、耐化学腐蚀性等方面都优于热塑性水性氟碳涂料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 514,
+        "chunk": "# 6.主要用途及发展方向  \n\n目前以水乳性或水可稀释性氟碳树脂为基料制备的水性氟碳涂料在建筑涂料等领域获得了极大应用。由于其特殊的表面性质，在医院、幼儿园、学校等公共场所内墙面以及生活用炊具上也获得成功应用。受合成技术、性能等因素影响，水性氟碳树脂在工业涂料领域的应用还十分有限，尤其是某些性能优于非交联型氟碳树脂的交联型水性氟碳树脂，应重点在工业和特殊领域进行开发应用，如卷材涂层、金属结构涂层、桥梁、镀锌铁板和钢铁表面等，以充分表现其防腐效果好、防护时间长等特性。单组分可交联型水性氟碳树脂属于适度交联，交联密度比双组分要小，但是施工简便，在木器等内用或外用涂料方面会得到很好的应用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 515,
+        "chunk": "# 四、粉末氟碳树脂  \n\n粉末氟碳树脂是近十几年发展起来的新型粉末涂料用树脂，是无液体的纯固体氟碳树脂。由于环保和经济原因，粉末氟碳树脂用量近年来逐年增加。广义来讲，粉末氟碳树脂基本上分两类：一类是热塑性粉末氟碳树脂；另一类是热固性粉末氟碳树脂。在粉末氟碳树脂中，热塑性氟碳树脂占绝大部分。粉末氟碳树脂各项理化性能可以和溶剂型氟碳树脂相媲美，某些性能甚至超过溶剂型氟碳树脂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 516,
+        "chunk": "# 1.原料的选择  \n\n制备粉末氟碳树脂可用氟烯烃单体包括三氟氯乙烯（CTFE)、二氯二氟乙烯、四氟乙烯（TFE)、六氟丙烯、偏氟乙烯、氟乙烯、六氟异丁烯、全氟乙烯基醚等。  \n\n热塑性粉末氟碳树脂主要为上述氟烯烃单体的均聚物和共聚物。均聚物用量最大的氟烯烃单体为四氟乙烯和偏氟乙烯。在热塑性粉末氟碳树脂共聚物中，有几种氟烯烃单体共同使用，如四氟乙烯和六氟丙烯，也有用其他第二和第三单体对含氟共聚物进行改性，以降低含氟均聚物的熔点、结晶度和加工温度，提高其加工和施工应用性能，如采用乙烯和四氟乙烯共聚合成乙烯-四氟乙烯共聚物粉末氟碳树脂，乙烯和三氟氯乙烯共聚合成乙烯-三氟氯乙烯共聚物粉末氟碳树脂。  \n\n热固性粉末氟碳树脂一般为氟烯烃、脂肪酸乙烯基酯/脂肪族乙烯基醚、羟烷基烯丙基醚和烯酸的共聚物。氟烯烃在共聚组分中主要起到提高耐候性和耐化学药品性作用，氟烯烃所占比例太小，涂膜耐候性和耐化学药品性差；氟烯烃所占比例太大，涂膜硬度高，耐冲击和弯曲性能差。热固性粉末氟碳树脂中常用含氟单体为三氟氯乙烯和四氟乙烯，由于三氟氯乙烯单体均聚物硬度和玻璃化温度要高于四氟乙烯单体均聚物，因此在热固性粉末氟碳树脂中三氟氯乙烯单体更为常见。脂肪酸乙烯酯/脂肪族乙烯基醚单体在粉末涂料烘烤时可改善其熔融流动性。常见脂肪酸乙烯酯类单体包括醋酸乙烯酯、丙酸乙烯酯、乳酸乙烯酯、新戊酸乙烯酯、己酸乙烯酯、辛酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯、豆蔻酸乙烯酯、棕榈酸乙烯酯、硬脂酸乙烯酯、叔碳酸乙烯酯Veova-9和Veova-10，脂肪酸乙烯酯结构式如下：  \n\n常见脂肪族乙烯基醚单体包括甲基乙烯基醚、乙基乙烯基醚、异丙基乙烯基醚、正丙基乙烯基醚、正丁基乙烯基醚、叔丁基乙烯基醚、异丁基乙烯基醚、环己基乙烯基醚等。  \n\n羟烷基烯丙基醚和烯酸决定共聚物羟值和酸值，因此它们所占比例对涂膜性能也有很大影响。常见羟烷基烯丙基醚单体包括羟乙基烯丙基醚、羟丙基烯丙基醚、羟基异丙基烯丙基醚、羟丁基烯丙基醚、羟烷基烯丙基醚结构式如下：  \n\n$$\n\\mathrm{H}{-}(\\mathrm{OC}_{n}\\mathrm{H}_{2n})_{\\overline{{x}}}\\mathrm{O}{-}\\mathrm{CH}_{2}{-}\\mathrm{CH}{-}\\mathrm{CH}_{2}\n$$  \n\n常见烯酸单体包括丙烯酸、甲基丙烯酸、丁烯酸、油酸、富马酸、马来酸乙烯基乙酸和十一碳烯酸，结构式如下：  \n\n其中，n为整数，在 $_{1\\sim10}$ 之间；R为H或 $\\mathrm{CH_{3}}$ 4  \n\n根据选择聚合工艺方法的不同，在制备粉末氟碳树脂过程中要选择相应的引发剂和引发体系。主要聚合引发剂为过硫酸盐和有机过氧化物。用有机过氧化物引发剂制得的粉末氟碳树脂热稳定性较高。在粉末氟碳树脂聚合反应过程中，尤其在热塑性粉末氟碳树脂合成过程中，为了控制树脂分子量和其他性能，在聚合反应期间还需要加入链转移剂或自由基终止剂。链转移剂一般为含氟化合物。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 517,
+        "chunk": "# 2.制备方法简述  \n\n一般来讲，粉末氟碳树脂可通过悬浮聚合、溶液聚合、溶液沉淀聚合和乳液聚合等工艺方法合成。  \n\n实际生产应用中，对于热塑性粉末氟碳树脂，如乙烯-三氟氯乙烯共聚物、乙烯-四氟乙烯共聚物，早期都是采用溶液聚合，以过氧化二氟丙酰之类的有机过氧化物为引发剂，以二氟二氯乙烷为溶剂，在温度 $60^{\\circ}\\mathrm{C}$ 下聚合。后来采用过氧化二（三)氯乙酰类有机过氧化物为引发剂，在二氟二氯乙烷溶剂和少量氯仿调节剂的存在下，在 $0\\sim5\\bar{\\mathrm{C}}$ 和 $0,49\\sim0.98\\mathrm{MPa}$ 下进行水相悬浮聚合。  \n\n近年来，也有专利文献报道采用溶液沉淀聚合方法来合成热塑性粉末氟碳树脂，如乙烯-三氟氯乙烯共聚物。聚合反应采用氟利昂溶液沉淀聚合体系，以三氟三氯乙烷和水作为反应介质，选用合适有机过氧化物为引发剂，加入适量的链转移剂，在一定温度和压力下自由基引发聚合，产物通过沉淀、分离、干燥、粉碎而成。  \n\n对于热固性粉末氟碳树脂，主要是指含羟基官能团的氟烯烃-乙烯基醚/酯共聚物，在自由基引发剂存在条件下， $30\\mathrm{\\sim}100\\mathrm{\\textperthousand}$ 之间，可通过溶液聚合、乳液聚合或悬浮聚合进行共聚反应。采用溶液聚合工艺时，制得共聚物树脂溶解在溶液中，通过沉淀剂进行沉淀，树脂从溶液中分离、干燥。采用乳液聚合或悬浮聚合时，制得共聚物氟碳树脂从乳液或悬浮液中分离、水洗、干燥。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 518,
+        "chunk": "# 3.粉末氟碳树脂种类  \n\n如前所述粉末氟碳树脂按照成膜机理和性能主要有两大类：一类是热塑性粉末氟碳树脂，包括PTFE（聚四氟乙烯）、PVDF（偏氟乙烯）、PCTFE（聚三氟氯乙烯）、PVF（聚氟乙烯)、FEP（全氟乙丙烯)、PFA（四氟乙烯-全氟烷基醚共聚物)、ETFE（乙烯-四氟乙烯共聚物)、ECTFE（乙烯-三氟氯乙烯共聚物）等；另一类是热固性粉末氟碳树脂，主要是指树脂主链中含羟基官能团的三氟氯乙烯/四氟乙烯和乙烯基醚或乙烯基酯类共聚物。  \n\n热塑性粉末氟碳树脂中，生产量最大的是乙烯-四氟乙烯共聚物。乙烯-四氟乙烯共聚物粉末氟碳树脂是继聚四氟乙烯和聚全氟乙丙烯后开发的第三大氟碳树脂品种，也是第二个含四氟乙烯的可熔融加工聚合物，它既具有聚四氟乙烯的耐温性、耐介质性和耐老化性，又具有聚乙烯可热塑性加工特性。美国和日本先后于1974年和1976 年投产，已经发展到上万吨的规模。20世纪末，美国和日本等国家大力开发应用领域，促使乙烯-四氟乙烯共聚物迅速发展。在国内，20世纪60年代，上海有机所开发了乙烯-四氟乙烯共聚物（FS-40)，用于原子能工业的耐辐射材料，之后开展了共聚物结构改性和聚合方法的研究，80年代研究成功了乙烯-四氟乙烯共聚物氟塑料，其性能接近国外同类材料水平。  \n\n热固性粉末氟碳树脂软化点在 $80^{\\circ}\\mathrm{C}$ 左右，100℃左右熔融，其颜料分散性优异，且可以用一般的粉末涂装工艺。四氟乙烯和乙烯基醚类单体共聚物玻璃化温度低（一般在 $0\\sim35\\Upsilon$ 之间)，采用这类单体合成热固性粉末氟碳树脂贮存稳定性差，树脂实用性差。三氟氯乙烯-乙烯基酯共聚物热固性粉末氟碳树脂具有较好的贮存稳定性，但其耐候性和耐化学药品性等主要性能与三氟氯乙烯-乙烯基醚共聚热固性粉末氟碳树脂相比要差一些。因此开发贮存稳定性好和耐候性、耐化学药品性优异的热固性粉末氟碳树脂，是今后粉末氟碳树脂开发工作者的研发重点之一。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 519,
+        "chunk": "# 4.粉末氟碳树脂制备过程  \n\n粉末氟碳树脂种类很多，下面以工业生产应用较为广泛的乙烯-三氟氯乙烯共聚物粉末氟碳树脂和三氟氯乙烯-乙烯基酯共聚物粉末氟碳树脂为例，简单介绍粉末氟碳树脂的制备过程，实例为实验室配方。 ?  \n\n(1）乙烯-三氟氯乙烯共聚物热塑性粉末氟碳树脂的制备过程采用2L带有电磁揽拌的高压反应釜，釜内设有夹套冷却，釜外壁附有电加热装置。试验前高压反应釜抽真空脱氧，氧气浓度为 $42\\mu\\mathrm{L}/\\mathrm{L}$ ，接着向高压反应釜中加入混合溶剂（ $1240_{B}$ 三氟三氯乙烷、20g脱氧去离子水)，开启搅拌，加热升温，初始进料槽混合三氟氯乙烯、乙烯反应单体进料（三氟氯乙烯：乙烯=52.1：47.9)，当温度升到50℃时用高压计量泵打入1.0g过氧化二碳酸环己酯，同时初始进料槽停止进料，此时初始混合反应单体共加入130g，补加进料槽中，将混合三氟氯乙烯、乙烯反应单体进料（三氟氯乙烯：乙烯 $=62.4:37.6)$ ，反应温度控制在$50\\sim60^{\\circ}\\mathrm{C}$ ，反应压力维持在 $1.55\\mathrm{{MPa}}$ ，恒压反应，聚合时间 $1.0\\mathrm{h}$ ，停止加料，补加混合反应单体共加入 $12.18$ 费  \n\n第二步反应，向高压反应釜中加入 $180{\\bf g}$ 脱氧去离子水调整反应体系中混合溶剂配比，反应温度控制在 $60{\\sim}85\\Upsilon$ ，补加进料槽中，将乙烯、三氟氯乙烯混合反应单体进料，继续反应，反应压力维持恒压1.55MPa，反应时间3.0h，补加入混合反应单体共加入 $31.2g$ 表结束反应。  \n\n将聚合产物溶液投入蒸馏釜，加人 $1000\\mathbf{g}$ 去离子水，开启搅拌，加热蒸馏回收有机溶剂，之后冷却，放料，干燥，得到粉状聚合物 $158g$  \n\n上述方法制备乙烯-三氟氯乙烯热塑性粉末氟碳树脂主要性能指标见表2-1-301。  \n\n表2-1-301乙烯-三氟氯乙烯热塑性粉末氟碳树脂主要性能指标  \n\n\n<html><body><table><tr><td>项 目</td><td>指 标</td><td>项 目</td><td>指标</td></tr><tr><td>熔点/C</td><td>223.87</td><td>抗拉强度/MPa</td><td>25.84</td></tr><tr><td>结晶熔/(J/g)</td><td>19.714</td><td>断裂伸长率/%</td><td>203</td></tr><tr><td>熔体指数（230C，5kg负荷）/(g/10min）</td><td>78.16</td><td></td><td></td></tr></table></body></html>  \n\n(2）三氟氯乙烯-乙烯基酯共聚物粉末氟碳树脂的制备过程在一个带电磁搅拌2L不锈钢高压反应釜中加人 $270_{8}$ 醋酸乙烯酯、 $82g$ 羟乙基烯丙基醚、8g乙烯基乙酸、 $4,6\\mathbf{g}\\ 2\\$ 正丙基过氧化二碳酸酯、 $506\\mathbf{g}$ 乙酸丁酯。高压反应釜中用氮气置换。加人 $576\\mathrm{g}$ 三氟氯乙烯(CTFE)。将反应釜内温度逐渐升至 $40^{\\circ}\\mathrm{C}$ ，在该温度下，聚合反应持续进行 $24\\mathrm{h}$ 。反应结束后，从高压釜中排出未反应三氟氯乙烯，取出反应溶液。反应溶液倒入正已烷中沉淀得到氟碳树脂共聚物。氟碳树脂共聚物研磨粉碎，反复水洗后过滤。在 $40^{\\circ}\\mathrm{C}$ 减压恒温真空干燥树脂。  \n\n最后得到氟碳树脂共聚物 $768\\mathbf{g}$  \n\n上述方法制备三氟氯乙烯-乙烯基酯共聚物热固性粉末氟碳树脂主要性能指标见表2-1-302。  \n\n表2-1-302三氟氯乙烯-乙烯基酯共聚物热固性粉末氟碳树脂主要性能指标  \n\n\n<html><body><table><tr><td>项 目</td><td>指 标</td><td>项 目</td><td>指标</td></tr><tr><td>数均分子量（凝胶渗透色谱法，GPC)</td><td>21500</td><td>酸值/（mgKOH/g)</td><td>6.0</td></tr><tr><td>氟含量（质量分数）/%</td><td>24</td><td>熔体黏度（100°℃，剪切速率10²s1）/mPa·s</td><td>3.5X10*</td></tr><tr><td>羟值/（mgKOH/g）</td><td>56</td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 520,
+        "chunk": "# 5.粉末氟碳涂料配方实例和性能  \n\n粉末氟碳树脂涂料配方和制造方法与一般热塑性和热固性粉末涂料类似，下面以乙烯三氟氯乙烯共聚物粉末氟碳树脂和三氟氯乙烯-乙烯基酯共聚物热固性粉末氟碳树脂为例，分别简单介绍热塑性和热固性粉末氟碳涂料配方和性能。 C  \n\n(1）乙烯-三氟氯乙烯共聚物粉末氟碳涂料配方实例和性能乙烯-三氟氯乙烯共聚物粉末氟碳树脂属于高分子量热塑性氟碳树脂，熔点高，很难熔融挤出，分子量大，硬度高，韧性强，普通粉碎设备很难将其进行超细粉碎（粉碎细度一般大于 $100\\mu\\mathrm{m})$ 。国外通常采用液氮粉碎设备在零下一百多摄氏度粉碎，粉碎设备昂贵，成本高。目前工业上一般采用树脂、颜料、填料、助剂干混法进行配漆。表2-1-303给出乙烯-三氟氯乙烯共聚物粉末氟碳涂料白色、黑色、绿色基本配方。表2-1-304给出乙烯-三氟氯乙烯共聚物粉末氟碳涂料主要性能指标。  \n\n表2-1-303乙烯-三氟氯乙烯共聚物粉末氟碳涂料白色、黑色、绿色基本配方  \n\n\n<html><body><table><tr><td>项 目</td><td>白色含量/%</td><td>黑色含量/%</td><td>绿色含量/%</td></tr><tr><td>二氧化钛</td><td>15.0</td><td></td><td></td></tr><tr><td>炭黑</td><td></td><td>0.4</td><td></td></tr><tr><td>氧化铬绿</td><td></td><td></td><td>15. 0</td></tr><tr><td>粉末氟碳树脂</td><td>83.7</td><td>89.3</td><td>83.7</td></tr><tr><td>填料</td><td></td><td>8.0</td><td></td></tr><tr><td>润湿剂</td><td>1. 0</td><td>2.0</td><td>1. 0</td></tr><tr><td>流平剂</td><td>0.2</td><td>0.2</td><td>0.2</td></tr><tr><td>消泡剂</td><td>0.1</td><td>0.1</td><td>0.1</td></tr></table></body></html>  \n\n表2-1-304乙烯-三氟氯乙烯共聚物粉末氟碳涂料主要性能指标  \n\n\n<html><body><table><tr><td colspan=\"2\">检验项目</td><td>技术指标</td><td>技术标准</td></tr><tr><td colspan=\"2\">筛余物（125μm）</td><td>全通过</td><td>HG/T 2597-1994</td></tr><tr><td colspan=\"2\">颜色及外观</td><td>颜色符合色差要求，涂膜平整，允许轻微橘皮</td><td>JG/T 3045. 2—1998</td></tr><tr><td colspan=\"2\">相对密度</td><td>1. 68 ~1.70</td><td>GB/T 17131989</td></tr><tr><td colspan=\"2\">吸水性（24h）/%</td><td><0.1</td><td>HG/T 3344—1985</td></tr><tr><td colspan=\"2\">固化温度/C</td><td>260±2</td><td>JG/T 3045. 2—1998</td></tr><tr><td colspan=\"2\">固化时间/min</td><td>20</td><td>JG/T3045.21998</td></tr><tr><td colspan=\"2\">干膜厚度/μm</td><td>100~150（二道，可多次喷涂）</td><td>GB/T 1764—1989</td></tr><tr><td colspan=\"2\">铅笔硬度（划破）</td><td>≥H</td><td>GB/T 6739-1996</td></tr><tr><td colspan=\"2\">光泽度（60°)/%</td><td>亚光，10~30</td><td>GB/T 9754-1988</td></tr><tr><td colspan=\"2\">附着力（划格法）/级</td><td>≤1</td><td>HG/T 92861998</td></tr><tr><td colspan=\"2\">耐冲击性/cm</td><td>≥40</td><td>HG/T 1732—1993</td></tr><tr><td colspan=\"2\">杯突试验/mm</td><td>≥7</td><td>HG/T 9753—1988</td></tr><tr><td rowspan=\"2\">弯曲试验/mm</td><td></td><td>≤2</td><td>HG/T 6742—1986</td></tr><tr><td>98%浓硫酸，7天</td><td>不起泡，不变色</td><td>GB1763-1979</td></tr><tr><td rowspan=\"2\">耐酸性 耐碱性</td><td>37%浓盐酸，7天</td><td>不起泡，不变色</td><td>GB1763-1979</td></tr><tr><td>45%氢氧化钠，7天</td><td>不起泡，不变色</td><td>GB1763-1979</td></tr><tr><td colspan=\"2\">30%氢氧化铵，7天</td><td>不起泡，不变色</td><td>GB1763-1979</td></tr><tr><td colspan=\"2\">三氯甲烷（7天）</td><td>不起泡，不变色</td><td>GB1763-1979</td></tr><tr><td colspan=\"2\">二甲苯（7天）</td><td>不起泡，不变色</td><td>GB1763-1979</td></tr><tr><td colspan=\"2\">丁酮（7天）</td><td>不起泡，不变色</td><td>GB1763-1979</td></tr><tr><td colspan=\"2\">耐湿热性（1000h)</td><td>≤1级</td><td>JG/T1740-1989</td></tr><tr><td colspan=\"2\">耐盐雾性（2000h）</td><td>不起泡，不脱落，允许轻微失光或变色</td><td>GB/T 1771-1991</td></tr><tr><td colspan=\"2\">耐人工老化试验（3000h） 耐温变性（10次）</td><td>失光1级，变色2级，粉化0级，龟裂0级 涂膜无变化</td><td>GB/T1864—1997 GB 9154-1988</td></tr></table></body></html>\n\n注：浸泡试验，喷涂试棒做试验。  \n\n(2）三氟氯乙烯-乙烯基酯热固性粉末氟碳涂料配方实例和性能热固性粉末氟碳涂料生产工艺和普通环氧、聚酯树脂类似。表2-1-305给出三氟氯乙烯-乙烯基酯热固性粉末氟碳涂料白高光漆配方。表2-1-306给出三氟氯乙烯-乙烯基酯热固性粉末氟碳涂料主要性能指标。  \n\n表2-1-305三氟氯乙烯-乙烯基酯热固性粉末氟碳涂料白高光漆配方  \n\n\n<html><body><table><tr><td>项 目</td><td>质量分数/%</td><td>项 目</td><td>质量分数/%</td></tr><tr><td>氟碳粉末树脂</td><td>50.3</td><td>流平剂</td><td>1.5</td></tr><tr><td>封闭异氰酸酯固化剂</td><td>8.4</td><td>抗冲改性剂</td><td>5.0</td></tr><tr><td>消泡剂</td><td>1.2</td><td>钛白粉</td><td>33.0</td></tr><tr><td>安息香</td><td>0.5</td><td>合计</td><td>100.0</td></tr><tr><td>DBTDL</td><td>0.1</td><td></td><td></td></tr></table></body></html>  \n\n表2-1-306热固性粉末氟碳涂料主要性能指标  \n\n\n<html><body><table><tr><td>项 目</td><td>技术指标</td><td>技术标准</td></tr><tr><td>膜厚/μm</td><td>50~70</td><td>GB/T 1764-1989</td></tr><tr><td>光泽度(60°)/%</td><td>10~80</td><td>GB/T 97541988</td></tr><tr><td>附着力（划格法）/级</td><td>1</td><td>GB/T 92861998</td></tr><tr><td>耐冲击性/cm</td><td>50</td><td>GB/T 1732—1993</td></tr><tr><td>杯突试验/mm</td><td></td><td>GB/T 9753—1988</td></tr><tr><td>铅笔硬度</td><td>≥2H</td><td>GB/T 67391996 A法</td></tr><tr><td>耐盐雾性</td><td>3000h，无变化</td><td>GB/T 17711991</td></tr><tr><td>耐人工老化试验(UVA)</td><td>3000h，无粉化，无龟裂，失光率≤20%</td><td>GB/T 18641997</td></tr><tr><td>耐酸性（10%硫酸，10天）</td><td>无变化</td><td>GB/T 17631979(1989)</td></tr><tr><td>耐碱性（10%氢氧化钠，10天）</td><td>无变化</td><td>GB/T 1763—1979(1989)</td></tr><tr><td>二甲苯（7天)</td><td>无变化</td><td>GB/T 1763—1979(1989)</td></tr><tr><td>耐湿热性</td><td>1000h无变化</td><td>JG/T 1740—1989</td></tr><tr><td>耐湿热试验后附着力（划格法）/级</td><td></td><td>GB/T 92861998</td></tr></table></body></html>  \n\n上述数据表明，热塑性粉末氟碳涂料和热固性粉末氟碳涂料都具有优异的物理机械性能和耐候性、耐化学药品性，热固性粉末氟碳涂料还具有高装饰性和优异的耐沾污性。表2-1-307和图2-1-97给出热固性粉末氟碳涂料和几种耐候性粉末涂料的综合性能比较。  \n\n表2-1-307几种耐候性粉末涂料的综合性能比较  \n\n\n<html><body><table><tr><td>类别</td><td>外观</td><td>力学性能</td><td>耐化学药品性</td><td>耐候性</td><td>综合成本</td><td>应用举例</td></tr><tr><td>聚酯树脂</td><td>8</td><td>8</td><td></td><td></td><td>6</td><td>空调、建材</td></tr><tr><td>聚氨酯树脂</td><td>10</td><td>7</td><td>9</td><td>8</td><td>5</td><td>建材、汽车部件</td></tr><tr><td>丙烯酸树脂</td><td>g</td><td>9</td><td>8</td><td></td><td>6</td><td>建材、汽车面漆</td></tr><tr><td>氟碳树脂</td><td></td><td>8</td><td>10</td><td>10</td><td>5</td><td>建筑材料</td></tr></table></body></html>\n\n注：1级最差，10级最好。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 521,
+        "chunk": "# 6.主要用途及方向  \n\n热塑性粉末氟碳涂料综合性能优异，现已被广泛应用于化工、石油的排水、洗涤、污水处理系统，以及装置的化学清洗系统，化学药品的分配系统等。例如，在氯气洗涤塔里使用乙烯基树脂涂层，由于介质能渗透过树脂层的玻璃钢层，导致了腐蚀损坏，最多只能有3年使用寿命。如果采用了乙烯-三氟氯乙烯共聚物涂层，使用8年以后，设备仍保持完好。乙烯-三氟氯乙烯共聚物粉末氟碳涂料也可用于氢氟酸输送管路等重防腐领域，还可重新涂装或修复旧设备。乙烯-四氟乙烯共聚物涂层还可用于涂装罐体及反应釜衬里等。聚偏氟乙烯和乙烯-四氟乙烯共聚物、乙烯-三氟氯乙烯共聚物等热塑性粉末氟碳涂料虽然各项性能优异，但因其施工困难，烘烤温度高（一般为250～300℃），静电喷涂较困难（一般需要热喷涂)，而且其树脂颜料分散性差，光泽度低，表面铅笔硬度低，遮盖力差，表面质感和光洁度与普通环氧、聚酯粉末涂料相比有较大差距，用途较窄。涂料装饰性能较差，只能用于某些特殊用途，成为涂料中的“贵族”，在粉末涂料中所占的比重非常小。同时热塑性粉末氟碳涂料推广应用困难的主要原因是价格高和涂层制备困难，涂层的使用性能与氟碳树脂本身的性质不匹配，以致涂层产品的使用性能与价格不匹配，在国内还没有形成热塑性粉末氟碳涂料的系列产品。  \n\n![](images/aaae78ec236c8bb9889719d02fd8610ba7f5cdf7cf239af998b1d5aabe77c02d.jpg)  \n图2-1-97热固性氟碳粉末涂料与其他类型涂料耐候性试验比较结果热固性氟碳粉末涂料：—溶剂型氟涂料：→丙烯酸粉末涂料：一\\*聚酯粉末涂料：—\\*环氧粉末涂料  \n\n热固性粉末氟碳涂料颜料分散性优异，烘烤温度和涂装工艺与普通粉末涂料相似，具有优异的耐化学药品性、耐候性及高装饰性，可满足更好保护工业装置和其他设施结构专用涂料日益增长的需要，广泛应用于桥梁、门窗、围墙、家用标色材料等建筑材料、汽车车体、家电产品等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 522,
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Paint and Surface Coatings. Theory and Practice,Woodhead Publishing Limited,1999； 674.  \n[202] 洪啸吟，冯汉保编著，涂料化学，北京：科学出版社，1997；131-134.  \n[203] Ichiro Azuma, et al.Acrylic oligomer for high solid automotive topcoating system having excellent acid resistance.Prog in Org Coat, 1997, 32; 1-7.  \n[204] Hisaki Tanabe, et al.A new resin system for super high solid coatings.Prog in Org Coat, 1997, 32: 197-203.  \n[205] 刘国杰主编. 现代涂料工艺新技术，北京：中国轻工业出版社，2000：378-379.  \n[206] 管从胜，王威强，氟树脂涂料及应用，北京：化学工业出版社，2004：17-24.  \n[207] 安静雯等. 可溶型含氟涂料树脂及其制备方法：ZL，200310109383.8.2003-12-15. 汽  \n[208] 刘国杰等．氟碳树脂涂料及施工应用．北京：中国石化出版社，2005：107-132.  \n[209] [211] 刘珠，达，金字飞料用氟碳乳的制备涂料工业，02，3（10）9-10 刘洪珠，高达， 水性氟（碳）树脂制备及应用研究，新型建筑材料，2005，（9). 众 鹭  \n[212] 国家发明专利：CN：122752.9. 20. AH  \n[214] EP 0556729A1. L y  \n[215] 刘国杰等. 氟碳树脂涂料及施工应用，北京：中国石化出版社，2005：107-132.  \n[216] 章云样等， 乙烯-三氟氯乙烯共聚物的制备方法：ZL，200410058026.8.2003-8-9.  \n217] 巩水忠，蔡玉波，孙艳，乙烯-三氟氟乙烯氟碳粉末涂料及耐化学腐蚀性研究，中国涂料，2004，（9）：20-22.",
+        "category": " References"
+    },
+    {
+        "id": 523,
+        "chunk": "# 颜料与填料",
+        "category": " Introduction"
+    },
+    {
+        "id": 524,
+        "chunk": "# 第一节颜料与填料的概述  \n\n颜料和填料是涂料的重要组成部分，根据涂料使用要求，颜料与填料的加入品种、数量有所不同，有用单一的，也有用两三种复合的，复杂时要用十多种搭配使用；添加数量从百分之几到百分之几十，甚至高达60%以上。这些颜料与填料不仅能保证涂料具有良好的遮盖力、丰富的色彩，还能赋予涂膜与施工各项其他特殊功效。作为涂料用的颜料与填料必须对分散性、白度、颜色、遮盖力、着色力、吸油量、粒度分布、耐酸碱性、耐光性、耐候性及耐温性等根据用途进行规定。",
+        "category": " Introduction"
+    },
+    {
+        "id": 525,
+        "chunk": "# 一、颜料与填料的定义  \n\n颜料是一类有色（含白色）的微细颗粒状物质，不溶于分散介质中，是以其“颗粒”展现其颜色（简称“颜料发色\"）为特征的一类无机或有机物质。颜料的粒度范围通常介于30nm～100um之间。颜料的颜色、遮盖性、着色性及其他特性与其在介质中的分散状态（颤料颗粒在介质中的存在状态）有极大的相关关系。  \n\n颜料中的有机颜料与染料有很多相似之处，其最根本的区别在于，“染料”是可溶解在分散介质中，以其“分子基团”展现其颜色（简称“分子发色\"）的。  \n\n填料是一类在介质中以“填充”为主要作用的微细颗粒状物质，不溶于分散介质中，也称体质颜料。填料干粉的外观大多为白色或浅灰色，一般其在介质中遮盖力、消色力均很低。通过在介质中加入填料，可有效改变介质中的非颜色性的物理和化学性质。",
+        "category": " Introduction"
+    },
+    {
+        "id": 526,
+        "chunk": "# 二、颜料与填料的作用",
+        "category": " Introduction"
+    },
+    {
+        "id": 527,
+        "chunk": "# 1.颜料的作用  \n\n颜料是涂料色漆生产中不可缺少的成分之一。其作用除了为涂膜提供色彩装饰外，还可以为涂料提供更多的物理和化学性能的改善，如遮盖性、耐光性、耐候性、耐温性、耐化学药品性、光泽及机械强度等。在涂料中使用功能性颜料可以赋予涂料特殊性能，如特种装饰效果（金属质感、珠光光泽、夜光、荧光等)、防腐、防火、导电、抗静电、示温等特种功能。",
+        "category": " Introduction"
+    },
+    {
+        "id": 528,
+        "chunk": "# 2.填料的作用  \n\n填料在涂料中主要有两方面作用：一是“填充”作用，降低成本；二是通过加入填料改变涂膜或漆料的物理和化学性质。现代涂料技术更加重视填料的第二方面的作用，如通过选  \n\n择不同种类和数量的填料，可有效改善涂料的贮存性能和施工性能，提高涂膜的机械强度、耐磨性、耐水性、抗紫外线性、隔热性和抗龟裂性等。  \n\n与颜料相比，大部分填料具有成本低、吸油量低和较易分散等优点。  \n颜料与填料在涂料中的作用见表2-2-1。  \n\n表2-2-1颜料与填料在涂料中的作用  \n\n\n<html><body><table><tr><td>颜料类别</td><td>作用与功能</td></tr><tr><td>着色颜料</td><td>1.赋予涂料与涂膜众多色彩，提高涂膜的装饰性与保护性（颜色的搭配性）； 2.涂料遮盖力与鲜艳度的保证； 3.颜色耐性（耐光、耐候、耐酸、耐碱、耐溶剂、耐温等)的保证； 4.颜料在涂料中的分散性、展色性的保证；</td></tr><tr><td>防锈颜料</td><td>5.提供安全色（安全标志） 活性防金表而发生学或电化受、有物理铸与化学防钢），如非活性的铝粉、石墨、氧化铁红；</td></tr><tr><td>特殊功能颜料</td><td>赋予涂层特殊功能效果，如珠光颜料使涂膜具有绚丽的珍珠光泽效果；金属颜料使涂膜具有金属闪光 效果；纳米颜料使涂膜具有抗紫外线、防霉、耐水及超耐候、耐温等效果；还有示温颜料、夜光颜料、荧光 颜料、变色颜料和耐高温颜料等均能使涂膜获得相应的效果</td></tr><tr><td>填料</td><td>1.提高涂料与涂膜的机械强度； 2.填充作用，提高固体含量，减少树脂与溶剂用量，降低成本； 3.梦与科好的流动性、开效果生、施工性能，作增用，途漆度使用寿命； 5.特殊功能性，如紫外线屏蔽、耐热、毒性极小： 6.还可改善其他添加剂性能，如增稠剂、流变剂、抗静电剂、紫外线稳定剂等</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 529,
+        "chunk": "# 三、颜料与填料的分类  \n\n颜料按化学组成分类，可分为有机颜料和无机颜料，无机颜料主要包括炭黑、铁、锌、铅、铬、镉和钛等金属的氧化物和盐；有机颜料可分为偶氮颜料类（单偶氮、双偶氮）、色淀类、铜菁类、稠环类及有机大分子颜料。根据来源可分为天然颜料与合成颜料，天然颜料主要来源于天然矿物，如朱砂、红土、黄土、赭石等；合成颜料如钛白粉、铁红、菁蓝及DPP红等。根据颜料功能分为发光颜料、防锈颜料、磁性颜料、珠光颜料、导电颜料、高温颜料及示温颜料等。按颜色分为白色颜料、黄色颜料、橙色颜料、红色颜料、蓝色颜料、绿色颜料、紫色颜料、棕色颜料、黑色颜料。按主化学元素分为铁系颜料、铬系颜料、钛系颜料、铅系颜料、锌系颜料等。按应用领域可分为涂料用颜料、油墨用颜料、塑料用颜料、橡胶用颜料、糖瓷用颜料。根据在涂料应用中所起的主要作用的应用，可分为着色颜料、体质颜料、防锈颜料及特殊功能颜料。颜料分类五花八门，不同领域均有其习惯的分类方式，很难统一。对于涂料领域，通常习惯按颜料的化学组成、颜色以及功能、性能进行分类。",
+        "category": " Introduction"
+    },
+    {
+        "id": 530,
+        "chunk": "# 第二节颜料的特性和指标  \n\n丰富的涂料品种对所选用的颜料有着众多的性能要求，如颜料的颜色、装饰性、润湿性、分散性、着色力、消色力、吸油量、吸水性、耐光性、耐候性、耐酸性、耐碱性、化学组成、晶型、耐热性、密度、粒径、粒径分布、比表面积、界面张力、亲水亲油平衡性及制漆性能等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 531,
+        "chunk": "# 一、颜料基本性能",
+        "category": " Introduction"
+    },
+    {
+        "id": 532,
+        "chunk": "# 1.颜色  \n\n颜色是颜料（尤其是着色颜料）最为重要的性能指标之一，已经形成一门学科，它涉及光学、生理学及心理学等。颜料的颜色主要取决于其化学组成和结构、粒子的大小与晶型，同时还与光源环境、观测者等因素有关。颜料的颜色是构成涂料色彩多样化的基础。  \n\n颜色的品种数以万计，大致可分为红、橙、黄、绿、青、蓝、紫、黑、灰与白等诸色。它们并非孤立存在，各种颜色之间存在一定的内在联系，每种颜色都可通过自身的三种基础特质（色调、明度、饱和度）来完整表现。在表征颜色的立体模型中的每一部位各代表一个特定的颜色，目前，国际上已广泛采用孟赛尔颜色系统（将在第四节做详细描述)，作为分类和标定表面色的方法，其表示方法符号为HV/C，H代表色调（hue)，V代表明度（val-ue)，C代表彩度（chroma)。通过三者来描述颜色，可以准确地鉴别一个颜色，并区别于其他颜色。两个颜色完全相同的充要条件是H、V、C三要素的值都相同。  \n\n(1）色调色调是彩色彼此相互区别的特性，可见光波段的不同波长刺激人眼产生不同的色彩感觉，色调体现了颜色在“质”方面的关系。色调也称色相，即表示红、黄、蓝、紫等颜色的特性，是一种视觉感知属性。物体的色调取决于光源的光谱组成和物体表面所反射（或透射）的各波长辐射的比例对人眼所产生的感觉。  \n\n(2）明度明度是人眼对光源或物体明亮程度的感觉，能够表征出颜色明暗深浅的差别，受视觉感受性和过去经验的影响。明度体现了颜色在“量”方面的不同。即表征的是一个物体反射光线多少的知觉属性。明度与反射率有关，物体表面反射率越高，其明度越高，白比灰高，黄比红高。光源的亮度越大，明度越高；黑白图像用灰度、灰阶描述。  \n\n(3）饱和度饱和度是颜色在色调“质”的基础上所表现的色彩纯洁程度，所以饱和度又称“彩度”。它是光谱中波长段是否窄、频率是否单一的表示。当物体反射出光线的单色性越强，则饱和度越大。黑白色只用明度描述，不用色调、饱和度描述。",
+        "category": " Introduction"
+    },
+    {
+        "id": 533,
+        "chunk": "# 2.润湿性与分散性  \n\n(1）润湿性润湿性是指颜料与树脂、溶剂或其他混合物的亲和性。颜料在使用时，原有的固/气界面（颜料颗粒/空气或潮气）消失，形成新的固/液界面（颜料颗粒/助剂或体系溶剂、水)，这一过程称为“润湿”。润湿与颜料的表面能有关，当颜料粒子加入树脂或溶剂中，如果界面张力过大，就不能被树脂、溶剂所润湿，颜料将不能均匀地分布到树脂与溶剂中去，其结果是，颜料粒子从树脂、溶剂中离析，形成涂膜后将产生诸如颗粒、凹坑、颜色不均匀等涂膜病态，即使通过添加大量润湿剂也很难达到理想效果。  \n\n颜料的润湿性主要取决于颜料的表面化学物理特性。通过对颜料表面进行合理处理可以有效降低颜料的表面能，提高其表面活性，使颜料粒子获得良好的润湿性，如包膜钝化处理、表面活性剂处理等。  \n\n颜料润湿性好将十分有利于颜料在涂料树脂中的分散，从而避免色漆涂膜的多种病产生，如颜色不够鲜艳（饱和度低)、光泽低、容易浮色发花、抗絮凝性差、涂料贮存稳定性不好及颗粒过大等。  \n\n(2）分散性分散性就是颜料团粒（附聚体）在树脂和溶剂中分离成理想的原生粒子分散体的能力，并将这种分散状态尽可能稳定地维持，但事实上不可能达到原生粒子状态，往往是通过合理添加分散助剂和采用好的研磨设备与分散工艺，使颜料团粒打开，并被助剂分子充分润湿，从而形成稳定的、颜料颗粒极小的颜料分散体。  \n\n颜料的分散性，不仅取决于颜料粒子的粒度分布、聚集状态的可分散性，也取决于粒子表面状态（亲水性或亲油性）和涂料介质的特性。  \n\n一般分散好的颜料随贮存时间增加，絮凝程度也相应略有增加。  \n\n分散不好的颜料随贮存时间增加，絮凝程度会明显增加，形成较粗颜料颗粒，从而会导致颜料自身着色强度与遮盖力下降、颜料颗粒过粗、涂膜光泽降低等多种涂膜端。  \n\n要形成稳定的颜料分散体，添加分散剂是必要的，分散剂在颜料的分散过程中起到促进分散、润湿及防止凝聚的作用，分散剂被吸附于颜料颗粒表面，通过静电斥力或空间位阻作用，防止它们再结合，降低了研磨能耗，缩短了研磨时间。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 534,
+        "chunk": "# 3.着色力与消色力  \n\n(1）着色力着色力又称着色强度（tintingstrength)，是表征某一种颜料与另一基准颜料混合后所显现颜色强弱的能力，通常以白色颜料为基准来衡量各种彩色或黑色颜料的着色能力。  \n\n着色力的量度是与标准样品做比较，以式（2-2-1）所得百分数表示：  \n\n式中B——标准颜料所需白色颜料数；A——待测颜料所需白色颜料数。  \n\n着色力是颜料对光线吸收和散射的结果，主要取决于吸收，吸收能力越大，其着色力越高。着色力是控制颜料质量的一个重要指标，当颜料用于着色时，着色力高的颜料在获得同样着色强度时，颜料用量就比着色力低的颜料少。  \n\n着色力的强弱不仅与颜料的化学组成有关，还与颜料粒子大小、形状、粒径分布、晶型结构和颜料粒子在涂膜中的分散度等因素有关。  \n\n着色力一般随着颜料的粒径减小而加强，当超过一定极限后，其着色力会因粒径减小而减弱，所以存在使着色力最强的最佳粒径。  \n\n由于着色力主要取决于吸收，因此吸收系数越大，则着色力越高。  \n\n彩色颜料的着色力随颗粒大小波动情况远不如折射率大的白色颜料表现明显，而且在颗粒增大到一定程度后，着色力变得很低，从着色力曲线所表现的“左偏斜”，说明选用细颗粒颜料有助于着色力的提高。  \n\n图2-2-1为彩色颜料粒径与着色力关系，n代表折射率，k代表吸收系数。图2-2-2为白色颜料（金红石型钛白和硫化锌）粒径与着色力关系。  \n\n![](images/c358a2e57c6b3aed8257c40cecf43085d2eaa3e021de8d792d45f8c5b4e18d71.jpg)  \n图2-2-1彩色颜料粒径与着色力关系1-低n高k；2-n、A都中等；3-高n低k  \n\n![](images/e0473cb2621b65287e353c6ab5963cc2b3aa6de18f2c64b72bfd64008af23a80.jpg)  \n图2-2-2白色颜料粒径与着色力关系1-金红石型TiO；2—ZnS  \n\n从图2-2-1和图2-2-2可以看出，前者是彩色颜料，由于着色力主要取决于吸收，即主要决定于其化学物质的本质，因此和粒径关系不十分突出，但吸收系数作用较大，同样粒径下吸收系数k值大的着色力要强。后者是白色颜料，它的吸收作用是很小的，此时着色力主要取决于散射，由于散射和颗粒大小关系紧密，因此白色颜料着色力随颗粒粒径变化较明显，而且折射率越高，颜料随粒径变化越显著。  \n\n着色力与颜料粒子在涂膜中的分散程度有关，分散得越好，着色力越强，为了提高颜料本身的着色力，对颜料的加工、后处理要给予足够的重视，如预分散、研磨、助剂的添加及分散工艺等。  \n\n另外，不同化学组成的颜料，由于颗粒形状、结晶类型不同也影响了着色力，所以着色力的影响因素很多，评价着色力的高低要从多方面进行分析。  \n\n(2）消色力消色力是指一种颜色的颜料抵消另一种颜料颜色的能力。一般颜料的着色力越强，其消色力也越强，通常用于评定白色颜料。一般来说，颜料有较大的折射率，就有较高的消色力。金红石型钛白粉在白色颜料中的折射率最大，它的消色力也最高。几种常用白色颜料的折射率见表2-2-2。  \n\n表2-2-2几种常用白色颜料的折射率  \n\n\n<html><body><table><tr><td>颜料名称</td><td>折射率</td><td>颜料名称</td><td>折射率</td><td>颜料名称</td><td>折射率</td></tr><tr><td>金红石型钛白粉</td><td>2.71</td><td>锑白</td><td>2.20</td><td>铅白</td><td>2.00</td></tr><tr><td>锐钛型做白粉</td><td>2.55</td><td>锌白</td><td>2.01</td><td>锌钡白</td><td>1.84</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 535,
+        "chunk": "# 4.遮盖力  \n\n颜料加在透明基料之中使之成为不透明，完全盖住测试基片的黑白格所需的最少颜料量称为遮盖力，通常以每平方米底材面积所需覆盖干颜料克数来表示，单位为 $\\mathbf{g}/\\mathbf{m}^{2}$  \n\n遮盖力（hidingpower）是由于颜料和存在其周围的介质的折射率之差造成的。当颜料的折射率和基料的折射率相等时就是透明的，当颜料的折射率大于基料的折射率时就出现盖，两者的差越大，则表现的遮盖力越强，几种常见物质的折射率见表2-2-3。  \n\n表2-2-3几种常见物质的折射率  \n\n\n<html><body><table><tr><td>颜料名称</td><td>折射率</td><td>颜料名称</td><td>折射率</td><td>颜料名称</td><td>折射率</td></tr><tr><td>空气</td><td>1.0</td><td>碳酸钙</td><td>1.58</td><td>硫化锌</td><td>2.37</td></tr><tr><td>水</td><td>1.33</td><td>二氧化硅</td><td>1.55</td><td>金红石型钛白粉</td><td>2.71</td></tr><tr><td>油</td><td>1.48</td><td>立德粉</td><td>1.84</td><td>锐钛型钛白粉</td><td>2.55</td></tr><tr><td>树脂</td><td>1.55</td><td>氧化锌</td><td>2.02</td><td></td><td></td></tr></table></body></html>  \n\n例如，碳酸钙在湿的状态下涂刷在墙上时，由于它和水的折射率相差不多，看起来遮盖力很差，但干了以后，由于空气取代了水，此时两者折射率之差变大了，所以干后看起来遮盖力大大增加（干遮盖）。  \n\n本来涂料中颜料粒子应被漆基所润湿，为了增加遮盖力，可以增添一部分低遮盖力的体质颜料，例如，在建筑涂料中掺加体质颜料作适当的填充，其用量超过临界颜料体积浓度（CPVC）时，形成有一些颜料粒子被空气包围，不被漆基润湿，反而提高了这部分颜料的遮盖能力。用低遮盖力的体质颜料代替部分高遮盖力、价格较高的钛白粉，既降低成本，又不影响遮盖力。  \n\n遮盖力是颜料对光线产生散射和吸收的结果，主要是靠散射。对于白色颜料更是主要靠散射，彩色颜料则吸收能力也要起一定作用，高吸收的黑色颜料也具有很强的遮盖能力。由于遮盖力的产生和光学过程密切相关，因此当颜料化学组成固定后，颗粒大小、分布、晶  \n\n型、晶型结构就都与遮盖力大小有关。  \n\n白色颜料主要是散射，由散射而产生的遮盖力主要与洛伦兹（Lorentz）因子、颜料粒子大小和颜料浓度三个因素有关。洛伦兹因子反映颜料与成膜物的折射率关系，如式(2-2-2）所示。  \n\n$$\n\\scriptstyle L={\\frac{n_{\\mathrm{p}}^{2}-n_{\\mathrm{b}}^{2}}{n_{\\mathrm{p}}^{2}+2n_{\\mathrm{b}}^{2}}}\n$$  \n\n式中L——洛伦兹因子；np——颜料折射率；—成膜物折射率。  \n\n经验表明，遮盖力与 $L$ 的平方成正比。这说明颜料与成膜物的折射率差越大，遮盖力就越高。  \n\n颜料的遮盖力与粒径大小有关，一般高折射率颜料与粒径关系较大，低折射率颜料与粒径关系较小，通过图2-2-3可以看出，高 $n$ 值的颜料要比低 $n$ 值的颜料遮盖力强，每条随粒度而变的遮盖力曲线都存在一个最高值。在最佳粒径产生最大遮盖力的原因是由于光的衍射作用，当颜料粒径相当于波长的1/2时，效果最佳，粒径再小时，光线会绕过颜料粒子，发生衍射，就不能发挥最大遮盖作用，同时随着粒径变小，透明度增强，遮盖力下降。超过粒径的最佳状态时，随着粒径的变大，光的散射作用越来越差，遮盖力同样会下降。  \n\n![](images/50fe62884b56805fff45cbc72d323d97284a51562ec0c338730713bee9c75084.jpg)  \n图2-2-3颜料粒径与着色力、遮盖力关系n—折射率；k—吸收系数  \n\n粒径对散射有较大影响。当粒径很小时，散射很小。随着粒径的增大，金红石型钛白粉、锐钛型钛白粉和硫化锌的散射迅速提高，达到最大值，而氧化锌和立德粉的散射相对较慢地提高至最大值。随着粒径的进一步增大，散射下降。不同颜料的最佳散射粒径是不同的。当入射光为可见光的平均波长 $:\\lambda=550\\mathrm{nm})$ ， $n_{\\mathrm{b}}=1.55$ 时，常用白色颜料的最佳散射粒径列于表2-2-4。  \n\n表2-2-4常用白色颜料的最佳散射粒径  \n\n\n<html><body><table><tr><td>麒料</td><td>最佳粒径/μm</td><td>颜料</td><td>最佳粒径/μm</td></tr><tr><td>金红石型钛白粉TiO:</td><td>0.27</td><td>立德粉BaSO·ZnS</td><td>1.20</td></tr><tr><td>锐钛型钛白粉TiOz</td><td>0.37</td><td>硫酸BaSO</td><td>4.0</td></tr><tr><td>硫化锌ZnS</td><td>0.40</td><td>气泡</td><td>0.70</td></tr><tr><td>氧化锌ZnO</td><td>0.74</td><td></td><td></td></tr></table></body></html>  \n\n由表2-2-4可以看出，金红石型钛白粉最佳粒径约为可见光平均波长的1/2。这也是市售金红石型钛白粉粒径一般都处于 $0.2\\sim0.4\\mu\\mathrm{m}$ 的原因所在。  \n\n颜料体积浓度对涂膜遮盖力有一定程度的影响。实验表明，当钛白粉含量低于 $10\\%$ PVC时，遮盖力随浓度提高而线性增加；当其浓度超过 $10\\%$ PVC时，遮盖力随浓度提高而增加，但非线性；当其浓度超过 $30\\%$ PVC后，由于钛白粉附聚，遮盖力不再随浓度提高而增加，甚至略有下降。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 536,
+        "chunk": "# 5.吸油量与比表面积  \n\n（1）吸油量颜料的吸油量是指每 $100\\mathbf{g}$ 干粉颜料所能吸收的精制亚麻仁油的最低值，单位为 $\\mathbf{g}/100\\mathbf{g}$ ，它反映颜料吸附油性介质的能力。  \n\n颜料的吸油量与颜料化学组成、粒径、形状、表面积、颗粒表面的微观结构、颗粒间的自由空隙大小等因素有关。颜料颗粒的平均粒径越小，比表面积越大，吸油量越大；反之亦然。  \n\n对于涂料制备来说，吸油量是重要指标。一般希望颜料有较低的吸油量，吸油量越小，所消耗的油性介质和树脂用量越少，可以适当节省成本；反之，当吸油量大时，油性介质和树脂用量也大，而且颜料浓度很难提高，性能也比较难以调整，成本还会提升。  \n\n(2）比表面积基于化学结构、生产工艺及后处理方法的不同，颜料产品具有不同的颗粒状态，并显示特定的比表面积。该数值越高，表明粒径越细，具有孔隙特征，表面积较大，使颜料的透明度较高。  \n\n不难想象颜料粒子的表面积与粒径成反比。这个最重要的理论关系，看似简单，却是理解颜料分散技术的关键。颜料粒子重量保持恒定时，粒径缩小一半，表面积则增大一倍。假定把颜料数学模型处理为球形时，则可以用式（2-2-3）表示这种关系：  \n\n$$\nS{=}\\frac{6}{{\\pi}d^{3}{\\rho}}{\\pi}d^{2}{=}\\frac{6}{d{\\rho}}\n$$  \n\n式中S—表面积；d-—粒径；p---密度。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 537,
+        "chunk": "# 6.耐光性与耐候性  \n\n颜料的耐光性和耐候性是衡量颜料应用性能的重要指标。耐光性主要是指耐日光照射（特指紫外线）的能力；耐候性则是指耐大气环境侵蚀（包括日光、雨水、湿气等)）的能力。  \n\n颜料长期受到日光的曝晒，雨水等的侵袭，其化学组成会发生某种程度的变化（光化学反应)，其结果是色彩发生迁移，一般有机着色颜料的色彩渐渐褪去，无机着色颜料的色彩会不断加深（偏暗)。决定颜料耐光性和耐候性的主要因素是颜料的化学组成和结构，还与周围介质、颜料粒径分布及表面处理等有一定关系。一般来说，无机颜料耐光性和耐候性比有机颜料好，但也不是绝对的。也有一些无机颜料受到光着色后其化学组成发生变化，颜色将会发生明显变化。例如，铬黄、钼镉红的耐光性仅为 $4{\\sim}5$ 级，耐候性为3级，经表面包膜处理的铬黄、钼镉红的耐光性可达8级，耐候性为 $4{\\sim}5$ 级。一些多环有机颜料具有优异的耐光性、耐候性，甚至要高于多数无机颜料，例如，喹吖啶酮红（P.R.122）、DPP红(P.R.254）、葱醒红（P.R.168）、异吲哚啉酮黄（P.Y.109）、喹酮黄（P.Y.138）等耐光性均可达 $\\scriptstyle7\\sim8$ 级，耐候性可达 $4{\\sim}5$ 级。同一结构的有机颜料因晶型、粒度分布、表面包覆及使用介质不同，耐光性、耐候性也略有所不同。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 538,
+        "chunk": "# 7.耐酸碱性与耐化学药品性  \n\n颜料的耐酸碱性是指颜料耐酸 $(\\mathrm{H^{+}})$ 、耐碱（ $\\mathrm{OH^{-}}$ ）的侵蚀能力。通常颜料耐酸性不好，就不能用于酸性介质中着色，耐碱性不好就不能在碱性环境下使用。  \n\n颜料耐酸碱性的测定是将颜料分别与酸溶液、碱溶液接触（浸泡）后，观察溶液的沾色与颜料本身的变色情况。  \n\n耐酸性较好的颜料有炭黑、钛白及多数多环类、缩偶氮类、酞菁类有机颜料。  \n\n耐碱性优良的颜料有炭黑、钛白、金属氧化物颜料及多数多环类、缩偶氮类、献菁类有机颜料。  \n\n耐化学药品性是指在化学药品中，除去酸、碱等腐蚀性物质之外，还有如耐盐类、耐强氧化剂、耐油、耐强溶剂类等的腐蚀。盛装和输送这些物质的设备管道防腐涂料，应当考虑所选用的颜料必须能长期耐受这些物质的侵蚀。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 539,
+        "chunk": "# 8.化学组成与晶型  \n\n颜料的化学组成是颜料间相互区分的主要标志，除了体现出颜料的一系列物理性能如颜色、遮盖力、着色力、表面电荷与极性等外，更为重要的是决定了化学结构的稳定性和各项牢度数据，如耐光性、耐候性、耐酸性、耐碱性、耐温性及耐化学药品性等。因此在选择颤颜料时，应根据应用要求，有针对性地对颜料的化学组成进行评估，选择符合要求的颜料。  \n\n晶体的几何形态特征称为晶型（crystalshape)，同一化学结构的颜料有多种晶型，其化学稳定性、色光及色饱和度等有所不同。很多有机颜料同其他结晶物质一样，存在“同质多晶现象”（polymorphism)。晶体的晶格中由于分子排列不同，可以组成多种晶型（crystalform)，各种晶型可以根据其X射线衍射图谱所具特征加以区别。例如，钛白有金红石和锐钛型两种不同的晶型，颜料蓝15（菁蓝B）已知的有α、β、、、ε、ⅡI、X、R、p九种晶型。商品有α型、β型、e型。α型呈红光，β型呈绿光，e型呈大红光。颜料紫19（喹吖啶酮红）有α、β、、θ、n五种晶型。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 540,
+        "chunk": "# 9.耐热性  \n\n根据颜料在涂料中着色要求不同，很多涂料体系对颜料耐热性有一定要求，如粉末涂料、卷材涂料、亲水铝箔涂料、塑胶漆等在制造或施工过程中要耐受一定的温度，如一般要求耐 $140{\\sim}250^{\\circ}\\mathrm{C}$ 的温度不变色，高的要求耐300℃以上的高温。耐热性差的颜料就会严重地变色，为此颜料的耐热性测定能帮助选用能耐受一定温度范围的颜料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 541,
+        "chunk": "# 10.粒径与粒度分布  \n\n颜料粒径是指颜料粒子的形状与大小。粒度是颗粒大小的量度，而颜料样品是由成万上亿个颗粒组成的，颗粒之间大小互不相同，其大小需要用粒度分布来描述。所谓粒度分布，通常是指粉体样品中各种大小的颗粒所占颗粒总数的比例（如干粉粒度分布图)。一般用激光粒度分布仪进行测定，有干法与湿法两种形式。  \n\n颜料粒子的大小、形状会影响其遮盖力、着色强度、色光、耐性及牢度等。颜料对光的反射作用与其自身同周围介质的折射率之差有关，折射率差别越大，反射作用越强，遮盖力越高。在一定范围内，随粒度的降低，颜料的遮盖力增加，同时粒子变小，比表面积增大，着色强度也随之提高。但粒子过于细小时会发生光的绕射现象，遮盖力反而降低，因此粒子的大小应控制在适当的范围内。颜料粒子的分布对颜料的色光也有影响。通常，粒子粗大，粒度分布较宽，色光发暗；反之则色光鲜艳。粒径分布还会影响颜料的耐光性、耐候性、牢  \n\n度等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 542,
+        "chunk": "# 11.临界表面张力  \n\n颜料临界表面张力 $(\\boldsymbol{\\gamma_{c}}$ ）是衡量颜料表面润湿难易程度的一个重要指标。  \n\n无机颜料临界表面张力较高，其表面属高能表面，所以较易分散在介质中。有机颜料临界表面张力较低，其表面属低能表面， $\\gamma_{\\mathrm{e}}<100\\mathrm{mN/m}$ ，所以较难湿润分散。例如，献菁蓝和甲苯胺红的临界表面张力分别为3 $1.3\\mathrm{mN/m}$ 和 $27.5\\mathrm{mN/m}$  \n\n颜料临界表面张力可以Zisman法测定，采用几种具有不同表面张力的液体，分别测定它们与被测颜料的接触角。以接触角的余弦对表面张力作图，得一直线，外推至 $\\scriptstyle\\cos\\theta=1$ ·即接触角为 $0^{\\circ}$ ，此交点相对应的表面张力称为被测颜料的临界表面张力。  \n\n表面活性剂具有降低表面张力、改变粒子表面极性的功能，作为润湿剂、乳化剂等广泛应用于颜料的生产中。基本原理是：分子中含有亲水性及亲油性基团的表面活性剂可以依据电荷的特性吸附于颜料粒子表面上。以阴离子表面活性剂为例，亲油性烷基碳链吸附于颜料的非极性区域，亲水性基团扩散到水介质中，在粒子周围产生同性电荷形成保护壁垒；在油性介质中亦然。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 543,
+        "chunk": "# 12.亲水亲油平衡性  \n\n亲水亲油平衡值（HLB）是在乳液聚合时为选择乳化剂而发展起来的。  \n使用HLB值的一般原则如下。  \n\n(1）表面活性剂混合物的HLB值可按混合物中各个表面活性剂的HLB值与其质量分数加权平均求得。(2）表面活性剂混合物的稳定性优于单个表面活性剂。(3）HLB值正好匹配并不能保证最好的稳定性，它只能提供该表面活性剂体系可能得到的最大稳定性。  \n\n一般来说，多数无机颜料具有较高的亲水亲油平衡值，即显示出较强的亲水性，属于亲水性颜料。而与无机颜料相比，多数有机颜料属于亲油性颜料。不同结构有机颜料的HLB计算值见表2-2-5。  \n\n表2-2-5不同结构有机颜料的HLB计算值  \n\n\n<html><body><table><tr><td colspan=\"2\">HLB值≤8</td><td colspan=\"4\">HLB值=8~12</td><td colspan=\"2\">HLB值≥12</td></tr><tr><td>颜料</td><td>HLB值</td><td>颜料</td><td>HLB值</td><td>颜料</td><td>HLB值</td><td>颜料</td><td>HLB值</td></tr><tr><td>P. Y. 81</td><td>7.6</td><td>P. Y. 14</td><td>8.4</td><td>P. R. 144</td><td>8.2</td><td>P. Y. 120</td><td>13.7</td></tr><tr><td>P. Y.16</td><td>7.8</td><td>P. Y.3</td><td>8.5</td><td>P. R. 166</td><td>8.3</td><td>P.Y.180</td><td>13.9</td></tr><tr><td>P. Y.13</td><td>8.0</td><td>P. Y. 12</td><td>8.8</td><td>P. R. 2</td><td>8.4</td><td>P. Y.139</td><td>18.9</td></tr><tr><td>P. O.5</td><td>7.5</td><td>P. Y.1</td><td>9.1</td><td>P. R. 180</td><td>8.6</td><td>P.R.175</td><td>12</td></tr><tr><td>P. R.40</td><td>6.3</td><td>P. Y. 83</td><td>10.5</td><td>P. R.8</td><td>8.7</td><td>P.R.176</td><td>12.1</td></tr><tr><td>P. R. 6</td><td>6.6</td><td>P. Y.97</td><td>11.2</td><td>P. R. 21</td><td>8.9</td><td>P.R. 112</td><td>12.6</td></tr><tr><td>P. R. 3</td><td>6.7</td><td>P. Y.154</td><td>11. 3</td><td>P. R. 23</td><td>9.3</td><td>P.R.122</td><td>12.6</td></tr><tr><td>P. R.1</td><td>7.1</td><td>P.Y.65</td><td>11.7</td><td>P. R. 37</td><td>9.6</td><td>P.V.19</td><td>13.4</td></tr><tr><td>P. R. 7</td><td>7.7</td><td>P. Y.74</td><td>11.7</td><td>P. R. 170</td><td>11.6</td><td>P.B.15  2</td><td>11~13</td></tr><tr><td>P. R. 52 + 1</td><td>6~8</td><td>P.O.43</td><td>8.4</td><td>P. R. 146</td><td>11.8</td><td>P. B.15 + 3</td><td>14~16</td></tr><tr><td>P. R. 424</td><td>7.4</td><td>P.0.13</td><td>8.7</td><td>P. R. 57 + 1</td><td>10~12</td><td>P.G.7</td><td>10~12</td></tr><tr><td>P. R. 214</td><td>7.5</td><td>P.O.36</td><td>10.9</td><td>P.V.23</td><td>9.4</td><td>P.G.36</td><td>12~14</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 544,
+        "chunk": "# 13.颜料的毒性  \n\n(1）含重金属的无机颜料大都是有毒的，如含铅Pb、镉Cd、锑Sb、锡Sn、硒Se及铬  \n\n酸盐 $\\mathrm{CrO}_{4}^{2-}$ 等的颜料。部分无机有毒颜料品种及毒性见表2-2-6。  \n\n表2-2-6部分无机有毒颜料品种及毒性  \n\n\n<html><body><table><tr><td>类 型</td><td>主要品种</td><td>毒性备注</td></tr><tr><td>含铅颜料</td><td>铅白、红丹、黄丹</td><td>较大</td></tr><tr><td>含铬酸盐CrO颜料</td><td>锌黄、锶黄、锌铬黄、铬黄</td><td>引起皮炎及致癌</td></tr><tr><td>含颜料</td><td>镉红、镉黄、钼镉红</td><td>较大，禁止用于食品、药物、化妆品</td></tr><tr><td>含硅酸盐颜料</td><td>石英（0.5~5μm）、石棉粉</td><td>较大</td></tr><tr><td>含可溶性、钡、砷等超标的无机颜料</td><td></td><td>均有较大毒性，随含量增加而增大</td></tr></table></body></html>  \n\n颜料作为着色剂，尤其是在民用装饰涂料中，其重金属含量等有害物质越来越引起人们的重视，在国内对涂料中一些有害物质都有相应的法律法规和标准要求。部分水性涂料中对有害物质限量要求见表2-2-7。  \n\n表2-2-7部分水性涂料有害物质限量标准  \n\n\n<html><body><table><tr><td>产 晶种类</td><td>内墙涂料</td><td>外墙涂料</td><td>墙体用 底漆</td><td>水性木器漆、水性防 腐涂料、水性防水涂料等</td><td>腻子</td></tr><tr><td>挥发性有机化合物（VOC)的含量限值</td><td>≤80g/L</td><td>≤150g/L</td><td>≤80g/L</td><td>≤250g/L</td><td>（粉状、音状） ≤10g/kg</td></tr><tr><td>卤代经（以二氟甲烷计）/（mg/kg）</td><td colspan=\"5\">≤500</td></tr><tr><td>苯、甲苯、二甲苯、乙苯的总量/（mg/kg）</td><td colspan=\"5\">≤500</td></tr><tr><td>甲醛/（mg/kg）</td><td colspan=\"5\">≤100</td></tr><tr><td>铅/(mg/kg)</td><td colspan=\"5\">≤90</td></tr><tr><td>镉/（mg/kg）</td><td colspan=\"5\">≤75</td></tr><tr><td>铬/（mg/kg）</td><td colspan=\"5\">≤60</td></tr><tr><td>汞/（mg/kg)</td><td colspan=\"5\">≤60</td></tr></table></body></html>  \n\n(2）有机颜料则因化学结构比较稳定，相对都比较安全，但仍有一些合成中间体与杂质的存在，具有一定的毒性。如多氯联苯（PCBs)、芳胺及一些重金属元素及其化合物等具有较大的毒性，甚至具有致癌作用。  \n\n(3）涂料生产过程中产生的粉尘也是颜料毒性或污染的主要因素之一，不论是有机颜料还是无机颜料，都会产生一定的毒性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 545,
+        "chunk": "# 二、颜料标准及检验方法  \n\n颜料标准及检验方法均在各颜料产品标准中直接引用。各通用的检验项目，只在颜料产品标准中记录下引用方法的标准号。进行检验时应完全按照标准中规定的方法、试剂、仪器进行检测。  \n\n标准及检验方法也是在不断改进的，随着科技的进步，会不断地引入新的测定方法和应用新的仪器，以改进原来的测定方法。 二  \n\n我国的国家标准GB与ISO、ASTM、DIN 的颜料标准检验方法已经接轨。相应的标准大全中有详细的叙述。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 546,
+        "chunk": "# 三、颜料的特性  \n\n无机颜料与有机颜料性能见表2-2-8。  \n\n表2-2-8无机颜料与有机颜料性能  \n\n\n<html><body><table><tr><td>性能</td><td>无机颜料</td><td>有机颜料</td></tr><tr><td>色诺</td><td>较窄，颜色品种少</td><td>较宽，品种较多</td></tr><tr><td>颜色特性</td><td>颜色暗淡、多数不够鲜艳</td><td>明亮、鲜艳</td></tr><tr><td>着色强度</td><td>绝大多数低</td><td>高</td></tr><tr><td>遮盖强度</td><td>着色颜料强，体质颜料弱</td><td>略弱</td></tr><tr><td>可用着色品种</td><td>较少</td><td>较多</td></tr><tr><td>耐久性（耐光、耐晒、耐候）</td><td>多数品种较好</td><td>酸菁与稠环等高档品种优异</td></tr><tr><td>毒性（重金属）</td><td>部分品种较高</td><td>多数较低</td></tr><tr><td>毒性（二氯联苯胺DCB)</td><td>无</td><td>酸菁与高档品种无，部分偶氮较低</td></tr><tr><td>耐酸碱性</td><td>部分变色、分解</td><td>多数品种优良</td></tr><tr><td>耐溶剂性</td><td>良好</td><td>多数品种优良</td></tr><tr><td>成本</td><td>较低</td><td>多数价格较高</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 547,
+        "chunk": "# 第三节颜料与填料各论",
+        "category": " Introduction"
+    },
+    {
+        "id": 548,
+        "chunk": "# 一、无机颜料",
+        "category": " Introduction"
+    },
+    {
+        "id": 549,
+        "chunk": "# 1.白色颜料  \n\n(1）钛白粉[C.I.PigmentWhite6（77891)][13463-67-7］钛白粉是最为重要的白色颜料，化学名称为二氧化钛颜料（titanium dioxidepigment)，分子式 $\\mathrm{\\TiO}_{2}$ ，分子量79.90，是一种情性极强的化合物。对大气中各种化学物质稳定，不溶于水和弱酸，微溶于碱。具有较高的消色力和遮盖力，白度好，耐光、耐晒、耐热等。  \n\n二氧化钛有三种结晶体：锐钛型、板钛型和金红石型。涂料产品中用得最多的是锐钛型(A型）和金红石型（R型)，同属四方晶系，但晶体结构的紧密程度不同，锐钛型晶体空间空隙大，在常温下稳定，高温下则转变为金红石型；金红石型是最稳定的结晶形态，结构致密，比锐钛型有更高的硬度、密度、介电常数和折射率，在耐候性和抗粉化方面比锐钛型优越，但锐钛型的白度比金红石型好。金红石型钛白粉对靠近蓝端的可见光谱吸收稍多于锐钛型，因而色调略带黄相。A型与R型性能比较见表2-2-9。  \n\n表2-2-9A型与R型性能比较  \n\n\n<html><body><table><tr><td>项目</td><td>R型</td><td>A型</td><td>项目</td><td>R型</td><td>A型</td></tr><tr><td>晶型</td><td>四方晶系</td><td>四方晶系</td><td>晶格常数a/nm</td><td>0.458</td><td>0.378</td></tr><tr><td>折射率</td><td>2.74</td><td>2.52</td><td>晶格常数c/nm</td><td>0.795</td><td>0.949</td></tr><tr><td>密度/（g/cm)</td><td>4.2</td><td>3.9</td><td>熔点/C</td><td>1858</td><td>高温向金红石型转化</td></tr><tr><td>莫氏硬度</td><td>6.0~7.0</td><td>5.5~6.0</td><td>吸油量/(g/100g）</td><td>20~22</td><td>23~25</td></tr><tr><td>介电常数</td><td>114</td><td>48</td><td>耐光牢度</td><td>很高</td><td>偏低</td></tr><tr><td>这盖力（PVC20%)</td><td>414</td><td>333</td><td>抗粉化性</td><td>优</td><td>差</td></tr><tr><td>消色力</td><td>1700</td><td>1300</td><td></td><td></td><td></td></tr></table></body></html>  \n\n钛白粉经表面包膜处理后，可提高其耐候性、分散性、光泽度及化学稳定性等。常用的无机表面处理剂为 $\\mathrm{SiO}_{2}$ ， $\\mathbf{Al}_{2}\\mathbf{O}_{3}$ ， $Z r\\mathrm{O}_{2}$ $\\mathsf{A l}_{2}\\mathsf{O}_{3}$ 包膜能产生光泽，有利于分散， $\\mathbf{SiO}_{2}$ 包膜能得到高耐候性， $Z r0_{2}$ 包膜能改善 $\\mathrm{TiO}_{2}$ 表面和包膜层之间的附着力，提高钛白粉抗粉化性和光泽度。应用有机表面处理主要是提高钛白粉在多种介质中的润湿分散性和流变性。  \n\n折射率是不透明度、遮盖力和着色力的物理基础，是取决于物质内部晶体结构的特性常数。折射率越大，遮盖力就越强，透明度越差。钛白粉是折射率最大，遮盖力最强，性能也最好的白色颜料。常用白色颜料的折射率和反射率见表2-2-10。  \n\n表2-2-10 常用白色颜料的折射率和反射率  \n\n\n<html><body><table><tr><td>颜料名称</td><td>折射率</td><td>反射率</td><td>不明度</td><td>颜料名称</td><td>折射率</td><td>反射率</td><td>不明度</td></tr><tr><td>钛白（R型）</td><td>2.71</td><td>8.26</td><td>100</td><td>锦白</td><td>2.01</td><td>2.11</td><td>26</td></tr><tr><td>钛白(A型)</td><td>2.55</td><td>6.70</td><td>81</td><td>铅白</td><td>2.00</td><td>2.04</td><td>25</td></tr><tr><td>锑白</td><td>2.20</td><td>3.58</td><td>43</td><td>锌银白</td><td>1.84</td><td>1.04</td><td>13</td></tr></table></body></html>  \n\n钛白粉在涂料中起到遮盖、消色及保护作用，是效果最好的白色颜料，约占其总量的$60\\%$ 是在涂料中使用。随着涂料产量越来越大，品种越来越多，钛白粉的需要量也就越来越大，品种也越来越齐全。硫酸法和氯化法生产的二氧化钛颜料在不同要求的涂料中得到了广泛的应用。  \n\n国外主要钛白粉生产厂家有：杜邦（DuPont）、美利联（Millennium）、克尔麦奇(Kerr-McGee）、亨茨曼（Huntsman）、克朗诺斯（Kronos）等。  \n\n普通二氧化钛的粒径为 $0.2\\sim0.3\\mu\\mathrm{m}$ ，对整个光谱都具有同等程度的强烈反射，外观呈白色，遮盖力很强，颗粒近似圆形。  \n\n纳米二氧化钛的粒径只有普通二氧化钛的1/10 $\\mathrm{:10\\sim15nm})$ ，颗粒呈棒状。纳米 $\\mathrm{\\TiO_{2}}$ 具有较强的紫外线吸收和散射性能，适量在涂料配方中添加纳米 $\\mathrm{TiO}_{2}$ ，可以有效提高涂料的抗紫外（耐老化）性。  \n\n超细二氧化钛和云母钛珠光颜料拼用时可以产生双色光效应，促进效应颜料的闪光效果。这种金属闪光涂层从不同方向观察，能看到不同随角异色的蓝光。如超细二氧化钛与银白色珠光颜料或铝粉颜料拼用，正视时涂膜呈金色金属外观，掠视或平视时则呈蓝色闪光，而金光和蓝光之间的连续变化会贯穿涂膜表面的所有弧面和棱角，能增加金属面漆颜色的丰满度和色彩美感。  \n\n(2）氧化锌[C.I.PigmentWhite 4（77947)][1314-13-2]氧化锌（zine oxide)，又称锌白（zincwhite)、锌白粉、锌氧粉，分子式 $z_{\\mathrm{nO}}$ ，分子量81.37，为白色六角晶系结晶或粉末，无毒、无味，不溶于水和乙醇，易溶于无机酸，也溶于氢氧化钠和氨水中。氧化锌具有良好的耐热性和耐光性，不粉化，可用于外用漆。在含硫化物环境中使用尤为适合，因为氧化锌能与硫结合成硫化锌，这也是一种白色颜料。氧化锌主要物化指标见表2-2-11。  \n\n表2-2-11氧化锌主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>外观</td><td>白色粉末</td><td>折射率</td><td>2.01</td><td>熔点/C</td><td>1975</td></tr><tr><td>密度/（g/cm）</td><td>5.6</td><td>莫氏硬度</td><td>4</td><td>吸油量/（g/100g）</td><td>10~25</td></tr></table></body></html>  \n\n氧化锌的遮盖力和消色力低于钛白和立德粉。氧化锌呈碱性，能与漆基中游离的脂肪酸作用生成锌皂，从而使漆料增稠，并能使涂膜柔韧、坚固而不透水、阻止金属的锈蚀。氧化锌与钛白粉、立德粉等配合使用能改善涂层的粉化。  \n\n氧化锌按制造方法不同，分为直接法氧化锌、间接法氧化锌和含铅氧化锌。它们的颗粒状态、化学组成都有一定的区别，因此选用时要加以注意。  \n\n纳米氧化锌（ $z_{\\mathrm{nO}};$ ）在阳光尤其在紫外线照射下，在水和空气中能分解出自由移动的电子（e）及带正电荷的空穴 $(\\mathrm{h^{+}})$ ，这种空穴可以激活空气中的氧变成活性氧，活性氧具有极强的化学活性，能与多种有机物发生氧化反应（包括细菌内的有机物)，从而把大量病菌和病毒消灭。将纳米 $z_{\\mathrm{nO}}$ 与其他纳米材料配合用于涂料中，可使涂层具有屏蔽紫外线、吸收红外线及抗菌防霉作用，既能净化空气，又能抗菌除臭。  \n\n由于纳米 $z_{\\mathrm{nO}}$ 吸收紫外线能力强，可作为涂料的抗老化添加剂。纳米氧化锌是采用湿法生产的粒径在 $0.1\\mu\\mathrm{m}$ 以下的活性氧化锌，具备常规块体材料所不具备的光、磁、电、敏感等性能，产品活性高，具有抗红外线、紫外线和杀菌的功能。  \n\n(3）立德粉[C.I.PigmentWhite5（77115)][1345-05-7］立德粉（lithoppne），又称锌钡白。标准立德粉是硫酸钡和硫化锌的等分子混合物，分子式 $\\mathrm{BaSO_{4}}\\cdot\\mathrm{ZnS}$ ，分子量330.8。  \n\n立德粉为白色的晶状物质，含有少量的氧化锌杂质，遮盖力为钛白粉的 $25\\%$ 左右，不溶于水，与硫化氢和碱溶液无作用，具有良好的化学情性和耐碱性，遇酸类则使它分解而放出硫化氢。其缺点是在光的照射下，当含有可溶性盐时，可促使硫化锌分解成硫，同时伴有金属锌的析出，颜色变暗，为了提高其耐光性可添加少量的钻盐。立德粉还兼具价廉、无毒等优点。立德粉主要物化指标见表2-2-12。  \n\n表2-2-12立德粉主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>外观</td><td>白色粉末</td><td>折射率</td><td>1.84~2. 0</td><td>比表面积/（m²/g）</td><td>4~5</td></tr><tr><td>密度/(g/cm）</td><td>4.3</td><td>莫氏硬度</td><td>4</td><td>安息角/(*)</td><td>40~50</td></tr><tr><td>平均粒径/μm</td><td>0.3~0.5</td><td>吸油量/(g/100g)</td><td>10~17</td><td></td><td></td></tr></table></body></html>  \n\n立德粉属三大白色颜料之一，与钛白、锌白比较，它具有良好的分散性、耐碱性、耐热性和贮存性。在发达国家立德粉基本被钛白粉所取代，在我国广泛应用在水性涂料中，占消费总量的 $50\\%$ 以上，主要用于生产中、低档涂料。  \n\n(4）锑白[C.I.PigmentWhite11（77052）][1309-64-4］锑白（antimonywhite），化学组成为三氧化二锑（antimonytrioxide），分子式 $\\mathrm{{\\bfSb}}_{2}\\mathrm{{O}}_{3}$ ，分子量291.50。  \n\n锑白是白色结晶粉末，是一种两性化合物，不溶于水、醇、稀硝酸、苛性钠、硫化钠、酒石酸、乙酸、浓硫酸、浓硝酸。锑白赤热时像黄色液体，冷却后呈白色结晶。耐候性优于锌钡白，具有粉化性小、耐光、耐热、阻燃、无毒等特性。与脂肪酸不起反应，用在高酸值漆料中不会皂化。必须与氧化锌配合使用，方可提早干结期及使油膜坚韧。佛白主要物化指标见表2-2-13。  \n\n表2-2-13白主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>外观</td><td>白色细微粉末</td><td>密度/(g/cm）</td><td>5.3~5.7</td><td>熔点/℃</td><td>656</td></tr><tr><td>折射率</td><td>2.0~2.09</td><td>吸油量/（g/100g）</td><td>11~14</td><td></td><td></td></tr></table></body></html>  \n\n纯三氧化二锑是一种优良的白色颜料，可用于涂料、防火漆。  \n\n(5）铅白[C.I.PigmentWhite1（77597）][1319-46-6]铅白（whitelead)，又称白铅粉，化学成分为碱性碳酸铅，分子式 $\\mathsf{2P b C O_{3}\\cdot P b(O H)_{2}}$ 。呈无定形粉末，相对密度 $6.4\\sim$ 6.8，折射率 $1.94{\\sim}2.09$ ，不溶于水及乙醇，溶于乙酸、硝酸等。能与酸值高的油生成铅皂，加强涂膜，防止粉化。遇硫会变成黑色的硫化铅，所以不能与银朱、镉黄、群青等含硫颜料配用。  \n\n由于在应用过程中可能会带来铅中毒，以及用铅白制备的涂料易增稠，有与硫化氢长期接触白度降低、热稳定性差等缺点，使用受到很大限制。但用铅白制备的涂料涂膜致密坚固，具有优良的耐光性、耐候性、防锈性与耐潮湿性，常作为生产厚浆漆、防锈漆和户外漆  \n\n使用。  \n\n2.炭黑颜料[C.I.PigmentBlack7（77266）][1333-86-4］炭黑（carbonblack），又称乌烟、烟黑，化学式C，分子量12.01。炭黑的主要组成物是碳元素，含有少量的氢、氧、硫、灰分、焦油和水分。炭黑具有较高的绝热能力，主要应用于橡胶工业，作为补强填充剂。炭黑具有较好的化学情性、耐光牢度、耐候牢度、耐热牢度及较强的着色力与遮盖力，也常作为着色剂使用，广泛应用于各类涂料、油墨、塑料和造纸的着色。  \n\n(1）炭黑的分类炭黑的分类，按照习惯，大体上可以按生产方式或用途来分。按生产方式，可把其分为灯黑、槽黑、炉黑和热裂黑等。按用途可把其分为色素用炭黑和橡胶用炭黑两大类。  \n\n四种主要类型炭黑的性能见表2-2-14。  \n\n表2-2-14四种主要类型炭黑的性能  \n\n\n<html><body><table><tr><td>性能</td><td>槽黑</td><td>炉黑</td><td>灯黑</td><td>热裂黑</td></tr><tr><td>平均粒径/nm</td><td>10~27</td><td>17~70</td><td>50~100</td><td>150~500</td></tr><tr><td>比表面积/（m²/g)</td><td>100~125</td><td>20~200</td><td>20~95</td><td>6~15</td></tr><tr><td>DBP值/(mL/100g)</td><td>60~100</td><td>67~195</td><td>105~115</td><td>30~46</td></tr><tr><td>pH</td><td>3~6</td><td>5~9.5</td><td>3~7</td><td>7~8</td></tr><tr><td>挥发分/%</td><td>3.5~16. 0</td><td>0.3~2.8</td><td>0.4~9.0</td><td>0.1~0.5</td></tr><tr><td>氢含量/%</td><td>0.3~0.8</td><td>0.70~0.45</td><td>一</td><td>0.3~0.5</td></tr><tr><td>氧含量/%</td><td>2.5~11.5</td><td>0.2~1.2</td><td>一</td><td>0~0.1</td></tr><tr><td>硫含量/%</td><td>0~0.10</td><td>0.05~1.50</td><td>一</td><td>0~0.25</td></tr><tr><td>苯抽出物/%</td><td>0</td><td>0.01~0.18</td><td>0~1.4</td><td>0.02~1.70</td></tr><tr><td>灰分/%</td><td>0~0.1</td><td>0. 1~1. 0</td><td>一</td><td>0.02~0.38</td></tr><tr><td>真实密度/（g/cm）</td><td>1.75</td><td>1.80</td><td>一</td><td></td></tr></table></body></html>  \n\n（2）色素炭黑国际上根据炭黑的着色力，通常把它分为三类，即高色素炭黑、中色素炭黑和低色素炭黑，这个分类系统常用三个英文字母表示。前两个字母表示炭黑的着色能力。最后一个字母表示生产方法。国际通用代码如下：  \n\n<html><body><table><tr><td>分类</td><td>国际通用代码</td><td>分类</td><td>国际通用代码</td></tr><tr><td>高色素槽黑</td><td>HCC(High Color Channel)</td><td>中色素炉黑</td><td>MCF(Medium Color Furnace)</td></tr><tr><td>高色素炉黑</td><td>HCF(High Color Furmace)</td><td>低色素炉黑</td><td>LCF(Low Color Furnace)</td></tr><tr><td>中色素槽黑</td><td>MCC(Medium Color Channel)</td><td></td><td></td></tr></table></body></html>  \n\n色素用炭黑分类见表2-2-15。  \n\n表2-2-15色素用炭黑分类  \n\n\n<html><body><table><tr><td>类型</td><td>粒径/nm</td><td>黑度指数</td><td>比表面</td><td>类型</td><td>粒径/nm</td><td>黑度指数</td><td>比表面积</td></tr><tr><td>HCC</td><td>10~14</td><td>260~188</td><td>1100~695</td><td>MCF</td><td>17~-27</td><td>173~150</td><td>235~100</td></tr><tr><td>MCC</td><td>15~27</td><td>175~150</td><td>275~115</td><td>LCF</td><td>28~70</td><td>130~60</td><td>65~20</td></tr></table></body></html>\n\n注：黑度指数为260则表明黑度最高，黑度指数为0则表明黑度最低。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 550,
+        "chunk": "# (3）色素炭黑的特性与应用关系  \n\n$\\Phi$ 炭黑的粒径与应用性能关系一般粒径越小，比表面积越大，炭黑的黑度越高。由于细粒子炭黑的吸光率比粗粒子炭黑的更高，所以着色力更强。细微原生粒子赋予炭黑更大的比表面积，同时增加分散难度和黏度，一般通过表面处理可调整润湿性和改善分散性。粒径减小时，由于蓝光被优先吸收，为此色调变成棕相。粒径减小，导电性提高。  \n\n$\\textcircled{2}$ 炭黑的结构与应用性能关系炭黑粒子不仅以原生粒子形式存在，而且在生产中熔结成凝聚体，这种凝聚体是由原生粒子经化学键结合而形成的。在凝聚过程中，由大量链枝的原生凝聚体构成的炭黑称为高结构炭黑。而原生凝聚体由较少链枝原生粒子组成的炭黑则称为低结构炭黑（图2-2-4)。炭黑结构与应用性能比较见表2-2-16。  \n\n![](images/564ad34beb7798135bcbfe29d34549ee73798181d99e3d790d00011993d13fb9.jpg)  \n图2-2-4炭黑的结构  \n\n表2-2-16炭黑结构与应用性能比较  \n\n\n<html><body><table><tr><td>性能</td><td>高结构</td><td>低结构</td><td>性能</td><td>高结构</td><td>低结构</td></tr><tr><td>分散性</td><td>更易</td><td>更难</td><td>导电性</td><td>更高</td><td>更低</td></tr><tr><td>润湿性</td><td>更慢</td><td>更快</td><td>粘度</td><td>更高</td><td>更低</td></tr><tr><td>主色黑度</td><td>更低</td><td>更高</td><td>填充量</td><td>更低</td><td>更高</td></tr><tr><td>光泽</td><td>更低</td><td>更高</td><td>着色力</td><td>更低</td><td>更高</td></tr></table></body></html>  \n\n(4）涂料用炭黑性质及对涂料性能的影响涂料用炭黑的典型性质见表2-2-17。炭黑性质与涂料性能变化对照见表2-2-18。  \n\n表2-2-17涂料用炭黑的典型性质  \n\n\n<html><body><table><tr><td>发黑类型</td><td>粒径/nm</td><td>比表面积/（m²/g）</td><td>黑度指数</td><td>pH</td><td>挥发分/%</td><td>DBP值/(mL/100g)</td></tr><tr><td>HCC-1</td><td>10</td><td>1125</td><td>275</td><td>3</td><td>16</td><td>470</td></tr><tr><td>HCC-2</td><td>11</td><td>1065</td><td>240</td><td>3</td><td>14</td><td>366</td></tr><tr><td>HCC-3</td><td>13</td><td>900</td><td>220</td><td>3</td><td>13</td><td>278</td></tr><tr><td>HCC-4</td><td>13</td><td>750</td><td>216</td><td>4</td><td>7</td><td>240</td></tr><tr><td>HCC-5</td><td>13</td><td>900</td><td>220</td><td>3</td><td>14</td><td>275</td></tr><tr><td>HCC-7</td><td>13</td><td>600</td><td>220</td><td>3</td><td>14</td><td>117</td></tr><tr><td>MCC-1</td><td>14</td><td>700</td><td>190</td><td>3</td><td>11</td><td>168</td></tr><tr><td>MCC-2</td><td>16</td><td>275</td><td>175</td><td>5</td><td>5</td><td>139</td></tr><tr><td>MCF-4</td><td>18</td><td>190</td><td>170</td><td>6</td><td>1.8</td><td>73</td></tr><tr><td>MCC-3</td><td>20</td><td>160</td><td>166</td><td>5</td><td>5</td><td>122</td></tr><tr><td>MCF-3</td><td>21</td><td>125</td><td>166</td><td>7</td><td>1.3</td><td>68</td></tr><tr><td>MCF-1</td><td>24</td><td>100</td><td>160</td><td>7</td><td>1.0</td><td>70</td></tr><tr><td>MCF-2</td><td>27</td><td>80</td><td>150</td><td>7</td><td>1.0</td><td>75</td></tr><tr><td>MCF-5</td><td>28</td><td>123</td><td>160</td><td>8</td><td>2.0</td><td>85</td></tr><tr><td>MCF-6</td><td>28</td><td>96</td><td>150</td><td>8.7</td><td>0.7</td><td>75</td></tr><tr><td>LCF-1</td><td>29</td><td>65</td><td>130</td><td>8</td><td>1.2</td><td>113</td></tr><tr><td>LCF-2</td><td>33</td><td>60</td><td>126</td><td>？</td><td>1.4</td><td>85</td></tr><tr><td>LCF-3</td><td>55</td><td>35</td><td>95</td><td>7</td><td>1.2</td><td>29</td></tr><tr><td>LCF-5</td><td>60</td><td>35</td><td>93</td><td>8</td><td>0.7</td><td>68</td></tr><tr><td>LCF-4</td><td>62</td><td>30</td><td>77</td><td>9</td><td>0.5</td><td>79</td></tr><tr><td>LCF-6</td><td>70</td><td>23</td><td>58</td><td>9</td><td>0.3</td><td>74</td></tr></table></body></html>  \n\n表2-2-18炭黑性质与涂料性能变化对照   \n\n\n<html><body><table><tr><td>炭黑性质变化</td><td colspan=\"2\">涂料性能变化情况</td></tr><tr><td>粒径减小或比表面积增大</td><td>黑度增加 黏度增加 分散性降低 光泽降低</td><td>光吸收更多，反射更少，使人觉得更黑； 基料需要量较多，自由流动的漆料量减少； 粒子间引力增大，需要更多的能量破坏附聚体； 较高的基料需要量，涂层中供光反射的基料量减少</td></tr><tr><td>结构增大</td><td>黑度降低 黏度增加 分散性增加 光泽降低</td><td>纤维状聚集体增多，相当于较粗粒子的效果； 基料需要量增加，自由流动的漆料量减少； 由于黏度增加，产生更大的剪切力破坏附聚体； 基料需要量增加，涂层表面上自由基料减少</td></tr><tr><td>表面酸度增加</td><td>黑度增加 度性加 光泽增加</td><td>料多数的料面，表面酸值增，相当基加人一种有效润湿分散剂，额</td></tr></table></body></html>  \n\n国外主要炭黑生产厂家有：卡博特（COBAT)、德固萨（DEGUSSA)、哥伦比亚（CO-LOMBIA)、印度伯拉（BIRLA)、日本东海（TOKAI）等，其中卡博特、德固萨和哥伦比亚三家顶级炭黑公司就占据了世界炭黑市场 $57\\%$ 的份额。  \n\n国内规模较大的生产厂家有：江西黑猫炭黑股份、中橡化学工业、上海卡博特、上海焦化、河南鹤壁炭黑、天津海豚炭黑等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 551,
+        "chunk": "# 3.铁系颜料  \n\n（1）氧化铁黄[C.I.PigmentYellow 42（77492）][51274-00-1]氧化铁黄（yellowi-ronoxide)，又称铁黄，是一种化学性质比较稳定的碱性化合物颜料，分子式 $\\mathrm{Fe}_{2}\\mathrm{O}_{3}\\cdot\\mathrm{H}_{2}\\mathrm{O}$ 或FeOOH，分子量177.71。色泽带有鲜明而纯洁的赭黄色，并有从柠檬色到橙色一系列色光的产品。合成氧化铁黄主要物化指标见表2-2-19。  \n\n表2-2-19合成氧化铁黄主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>外观</td><td>黄色粉末</td><td>密度/（g/cm）</td><td>4.10</td><td>折射率</td><td>2.30~2.40</td></tr><tr><td>纯度（FeO）/%</td><td>86~88</td><td>吸油量/(g/100g)</td><td>30~40</td><td>速盖力/(g/m²)</td><td>10~15</td></tr><tr><td>平均粒径/μm</td><td>0.10~0.80</td><td>pH</td><td>5~8</td><td>结晶形状</td><td>针状</td></tr></table></body></html>  \n\n具有典型无机颜料特性，优异的耐光、耐候、耐溶剂、耐碱、无毒等特性，价格较低；其缺点是不耐高温、不耐酸，易被热的浓强酸溶解；在 $135\\mathrm{{C/h}}$ 或 $177\\mathrm{\\vec{C}/5\\mathrm{min}}$ 因逐渐失去结晶水而向红转变，不能应用于烘干温度较高的涂料中。  \n\n合成氧化铁黄着色力高、色光较亮，可按需要制造出各种色相的铁黄，研磨分散性也比较好，在紫外线以及可见的蓝色光谱段都有强烈吸收，具有屏蔽紫外线辐射的作用，使聚合物延缓降解，延长涂层使用寿命。可与稳定型酥菁蓝、铁蓝等配成绿色，与铁红、铁黑等配成棕色。  \n\n(2）氧化铁红[C.I. Pigment Red101（77491)][1307-37-1]氧化铁红（red iron ox-ide)，简称铁红或铁红粉。化学名称为三氧化二铁，分子式 $\\mathrm{Fe}_{2}\\mathrm{O}_{3}$ ，分子量159.69。同样的化学成分，由于原料、生产工艺的不同，物理性能差异较大，用途也有所不同。  \n\n氧化铁红为红色粉末，其色光变化幅度较大，当颗粒度为 $0.2\\mu\\mathrm{m}$ 时，带黄相，比表面积、吸油量等也较大；颗粒度增大时，色相就从红向紫移动，比表面积、吸油量也随之变化。按粒子大小可分为普通氧化铁红、超细氧化铁红及纳米氧化铁红。合成氧化铁红主要物化指标见表2-2-20。  \n\n表2-2-20合成氧化铁红主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>外观</td><td>亮橙色至深红紫色</td><td>密度/（g/cm）</td><td>4.50~5.18</td><td>折射率</td><td>2.94~3.22</td></tr><tr><td>纯度（FeO）/%</td><td>>96</td><td>吸油量/(g/100g）</td><td>15~35</td><td>遮盖力/（g/m²）</td><td>5~10</td></tr><tr><td>平均粒径/μm</td><td>0.20~0.90</td><td>pH</td><td>4~7</td><td>结晶形状</td><td>菱形</td></tr></table></body></html>  \n\n氧化铁红是一种最经济，遮盖力仅次于炭黑的颜料，具有很高的耐热性，在 $500\\mathrm{{\\textperthousand}}$ 不变色，在 $1200\\mathrm{{\\tau}}$ 时也不改变化学结构，极为稳定；能吸收阳光中的紫外光谱，对涂层有保护作用；还具有极高的着色强度、耐光性、耐候性、耐碱性、耐水性、耐溶剂性及耐稀酸性，可广泛应用于各类涂料着色。缺点是不能耐强酸，颜色红中带黑，不够鲜艳。  \n\n铁红大量用于防锈涂料，具有物理防锈功能，使大气中的水分等不能渗透到金属中，增加涂层的致密性与机械强度。应用于防锈漆的铁红，水溶盐较低，有利于提高防锈效果；但经长期曝晒后，含有铁红的涂层容易产生粉化现象，特别是颗粒度较小的铁红，粉化速度更快。  \n\n(3）氧化铁黑[C.I.PigmentBlack11（77499）][12227-89-3］氧化铁黑（black ironoxide)，简称铁黑，分子式 $\\mathrm{Fe_{3}O_{4}}$ 或 $\\mathrm{Fe}_{2}\\mathrm{O}_{3}\\cdot\\mathrm{FeO}$ ，化学名称为四氧化三铁，属于尖晶石型。具有饱和的蓝墨光黑色，遮盖力、着色力均很高，对光和大气的作用稳定性较好，不溶于碱，微溶于稀酸，在浓酸中则完全溶解，耐热性差，在较高温度下易氧化，生成红色的氧化铁。氧化铁黑主要物化指标见表2-2-21。  \n\n表2-2-21氧化铁黑主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>外观</td><td>黑色粉末</td><td>密度/（g/cm）</td><td>4.95</td><td>遮盖力/（g/m²）</td><td>7~10</td></tr><tr><td>纯度（FeO）/% 平均粒径/μm</td><td>>95 0.20~0.60</td><td>吸油量/(g/100g) pH</td><td>15~25 5~8</td><td>结晶形状</td><td>立方形</td></tr></table></body></html>  \n\n氧化铁黑因遮盖力、着色力强，耐光性、耐候性及耐碱性好，广泛用于各种涂料及水泥制品着色。因具有很强的磁性，可用于生产金属底漆，其附着力和防锈性好。  \n\n（4）氧化铁棕[C.I.PigmentBrown6（77492）][52357-70-7]氧化铁棕，简称铁棕，是氧化铁红、氧化铁黄和氧化铁黑的混合物。色相随配料拼色比例的变化，可得到多种色光的氧化铁棕。其着色力和遮盖力很高，耐光性、耐碱性好，无水渗性和油渗性。氧化铁棕主要物化指标见表2-2-22。  \n\n表2-2-22氧化铁棕主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>外观 纯度（FeO）/%</td><td>棕色粉末 >80 0.20~0.40</td><td>密度/（g/cm） 吸油量/(g/100g) pH</td><td>4.4~5.0 25~35 5~7</td><td>这盖力/（g/m） 结晶形状</td><td>一 混合形</td></tr></table></body></html>  \n\n氧化铁棕主要用于水泥着色、配制木器漆、色漆以及皮革上色等。  \n\n(5）纳米氧化铁纳米级氧化铁颜料具有纳米粒子效应，当与光作用时产生小尺寸效应，表现在对可见光波的散射能力降低、遮盖力下降，呈现“透明”状态，对短波长的紫外线还具有较强的吸收能力。它保持了氧化铁颜料的化学组成和晶型，具有很好的化学稳定性，无毒、无味、价廉，以及很好的耐温性、耐候性、耐酸性、耐碱性及高彩度、高着色力、高透明度，同时克服了传统氧化铁颜料饱和度低，颜色不够鲜艳，在高档涂料中使用受到限制的缺点。  \n\n纳米粒径的透明氧化铁（transparentironoxide）具有较强的吸收紫外线的能力，不但自身光学稳定，而且可以提高各类高聚物的抗老化性，广泛应用于高档工业、建筑及装饰涂料。透明氧化铁颜料正逐步替代传统氧化铁颜料，越来越受到人们的青睐。  \n\n德国的巴斯夫公司和美国的希尔顿戴维斯公司是世界上最大的透明氧化铁生产商。巴斯夫公司生产著名的Sicotrans系列透明氧化铁，最近又推出了两个新的预分散透明氧化铁产品：XFastYellowED7800和XFastRedED7795，这两个产品能提高木材质感。近年来国内出现了几家规模生产透明氧化铁的高科技企业，如浙江省上虞市正奇化工有限公司、浙江神光材料科技有限公司等均有生产透明氧化铁的能力。透明氧化铁主要物化指标见表2-2-23。  \n\n表2-2-23透明氧化铁主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>透明氧化铁黄</td><td>透明氧化铁红</td><td>透明氧化铁棕</td><td>透明氧化铁黑</td></tr><tr><td>外观</td><td>黄色粉末</td><td>红色粉末</td><td>褐色粉末</td><td>黑色粉末</td></tr><tr><td>纯度（FeO)/%</td><td>≥82</td><td>≥90</td><td>≥90</td><td>≥93</td></tr><tr><td>平均粒径/μm</td><td>0. 01~0.10</td><td>0.01~0.10</td><td>0.01~0.10</td><td>0. 01~0.10</td></tr><tr><td>吸油量/(g/100g)</td><td>35~50</td><td>35~45</td><td>35~45</td><td>35~40</td></tr><tr><td>结晶形状</td><td>针状</td><td>菱形</td><td>混合形</td><td>混合形</td></tr><tr><td>水溶物/%</td><td>≤0.20</td><td>≤0.20</td><td>≤0.20</td><td>≤0.20</td></tr><tr><td>水悬浮液pH</td><td>3~5</td><td>6~8</td><td>5~7</td><td>6~8</td></tr><tr><td>遮盖力/（g/m）</td><td>透明</td><td>透明</td><td>透明</td><td>透明</td></tr><tr><td>耐酸性/级</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>耐碱性/级</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>油渗性/级</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>耐水性/级</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>耐热性/℃</td><td>160</td><td>≥300</td><td>160</td><td>160</td></tr><tr><td>紫外线吸收能力/%</td><td>≥95</td><td>≥95</td><td>≥85</td><td>≥85</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 552,
+        "chunk": "# (6）其他氧化铁  \n\n$\\Phi$ 耐热级氧化铁一般的氧化铁黄、氧化铁黑因含结晶水，在 $177^{\\circ}\\mathbb{C}$ 下开始脱水或氧化变色，因此不能用于需要较高温度下加工的塑料和烘烤型涂料中。经包核处理后的耐热级氧化铁，可提高耐热性，适用于聚丙烯、汽车维修漆、卷材涂料、各种色浆和高光泽乳胶漆等。  \n\n$\\textcircled{2}$ 低吸油量和高分散性氧化铁为了方便使用，现代无机颜料也开始考虑制造高浓度色浆颜料，这就要求颜料具有较低的吸油量和很好的分散性。通过添加表面处理剂和机械粉碎，可以改变粒子形状、降低吸油量和提高分散性。  \n\n$\\textcircled{3}$ 天然云母氧化铁（micaceousironoxide）是天然矿石精选后，经过粉碎、水漂、干燥、过筛分级而成。具有金属光泽，呈云母状片晶，带有红相的灰色粉末，其主要成分的化学式为 $\\scriptstyle\\alpha-\\mathrm{Fe}_{2}\\mathrm{O}_{3}$ ，其含量 $85\\%\\sim90\\%$ ，密度 $4.7\\sim4.9\\ensuremath{\\mathbf{g}}/\\ensuremath{\\mathrm{cm}^{3}}$ ，莫氏硬度6.0，水悬浮液 $\\mathsf{p H}$ $6.0{\\sim}8.0$ ，粒度 $5\\sim100\\mu\\mathrm{m}$ ，含有非片状粒子。由于具有良好的片状形态，化学稳定性好，用它制备的防锈涂料可起到屏蔽作用，防止腐蚀性介质渗入被保护底材，适用于各种钢结构的保护。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 553,
+        "chunk": "# 4.铬酸盐颜料  \n\n(1）铅铬黄［C.I.PigmentYellow34（77600)][1344-37-2]铅铬黄颜料的主要化学成分为 $\\mathrm{PbCrO_{4}}$ 、PbSO及 $\\mathrm{PbCrO_{4}\\cdot\\mathrm{PbO}}$ 。亮黄色单斜晶系结晶体，熔点844℃。不溶于水、油和乙酸，溶于强酸或强碱。遇硫化氢变为黑色，遇碱变为橙红色。随原料配比和制备条件，颜色由柠檬黄色至橘黄色，形成一段连续的黄色色谱。着色力与遮盖力较强，经日光曝晒，色泽变暗，有毒，不能与立德粉、群青同时使用，可用于涂料着色。铅铬黄是用量最大的黄色颜料，随着禁用含铅颜料法规日益从紧，其替代品的开发已列人议事日程。铅铬黄主要物化指标见表2-2-24。  \n\n(2）钼铬红[C.I.PigmentRed104（77605）][12656-85-8］钼铬红（molybdeniumchromiumred)，又称3710钼酸红、107钼铬红、3710钼铬红。钼铬红分子式为 $x{\\mathrm{PbCrO}}_{4}$ ·$_{y\\mathrm{PbSO_{4}}}\\cdot2\\mathrm{PbMoO_{4}}$ 。钼铬红主要物化指标见表2-2-25。  \n\n207钼铬红主要成分为铬酸铅、硫酸铅、钼酸铅；107钼铬红除与207钼铬红有相同的主要成分外，还有少量氢氧化铝、磷酸铝。  \n\n表2-2-24铅铬黄主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>柠檬铬黄</td><td>浅铬黄</td><td>中铬黄</td><td>深铬黄</td><td>橘铬黄</td></tr><tr><td>外观</td><td>柠檬黄色粉末</td><td>浅黄色粉末</td><td>中黄色粉末</td><td>深黄色粉末</td><td>橘黄色粉末</td></tr><tr><td>络酸铅（PbCrO）/%</td><td>≥50.0</td><td>≥60.0</td><td>≥90.0</td><td>≥85.0</td><td>≥55. 0</td></tr><tr><td>密度/(g/cm）</td><td>5.51~5.73</td><td>5. 44~6.09</td><td>5.58~6.04</td><td>5.58~6.04</td><td>6.62~7.07</td></tr><tr><td>吸油量/(g/100g)</td><td>20~30</td><td>20~30</td><td>16~22</td><td>16~22</td><td>9~15</td></tr><tr><td>遮盖力/（g/m²）</td><td>≤95</td><td>≤75</td><td>≤55</td><td>≤45</td><td>≤40</td></tr><tr><td>耐光性/级</td><td>4~5</td><td>5</td><td>4~5</td><td>5</td><td>5~6</td></tr><tr><td>耐候性/级</td><td>1~4</td><td>2~4</td><td>2~4</td><td>2~4</td><td>3~4</td></tr><tr><td>耐酸性/级</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td></tr><tr><td>耐碱性/级</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3</td></tr><tr><td>油渗性/级</td><td>1</td><td>1</td><td>1</td><td>1</td><td>1</td></tr><tr><td>耐热性/C</td><td>140</td><td>140</td><td>140</td><td>140</td><td>150</td></tr><tr><td>比表面积/(m²/g)</td><td>7.2</td><td>7.2</td><td>4.0</td><td>4.0</td><td>1.28</td></tr><tr><td>折射率</td><td>2.11~2.40</td><td>2.11~2.40</td><td>2.30~2.66</td><td>2.30~2.66</td><td>2.40~2.70</td></tr></table></body></html>  \n\n表2-2-25钼铬红主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td></td><td>红色粉木</td><td>密度[/cm)</td><td>15.41~46.4</td><td>遮董力/（g/m²）</td><td>≤40</td></tr><tr><td>外度（PbCrO)/%</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>0. 1~1.0</td><td>耐酸性/级</td><td></td><td>耐热性/级</td><td>140</td></tr><tr><td>平均粒极/m</td><td></td><td></td><td>~</td><td></td><td></td></tr><tr><td>耐水性/级</td><td>5</td><td>耐油性/级</td><td>5</td><td></td><td></td></tr></table></body></html>  \n\n钼铬红的颜色可以由橘红色至红色。具有较高的着色力及很好的耐光性和耐热性，能耐溶剂，无水渗性和油渗性，可与有机颜料混合应用；但耐酸性、耐碱性差，遇硫化氢气体变黑。  \n\n钼铬红用于涂料中，可与白色防锈颜料配合制成钼铬红防锈漆，与耐晒性好的有机颜料拼色，可得到耐溶剂、不泛金光、耐烘烤温度的大红色烘漆。其缺点在于晶型易变化、使色泽改变、耐光性和耐候性不很理想。现在使用锑或硅化合物对其进行表面处理，可以使钼铬红的耐光、耐候指标大大提高。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 554,
+        "chunk": "# 5.镉系颜料  \n\n(1）镉黄[C.I.PigmentYellow 37（77199)][68859-25-6]镉黄（cadmiun yellow）在化学组成上基本上为硫化镉（CdS)，或硫化镉与硫化锌（ZnS）的固溶体，或该两种镉黄与硫酸钡（ $\\mathrm{\\DeltaBaSO_{4}}$ ）组成的填充型颜料（CdS/BaSO或 $\\mathrm{CdS/ZnS/BaSO_{4}};$ 。镉黄主要物化指标见表2-2-26。 or Q  \n\n表2-2-26锡黄主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>外观 平均粒径/μm</td><td>黄色粉末 0.04~0.40</td><td>密度/（g/cm） pH</td><td>4.5~5.9 5~8</td><td>比表面积/（m²/g）</td><td>7~8</td></tr></table></body></html>  \n\n镉黄的颜色鲜艳而饱和，其色谱范围可以从淡黄、正黄直至红光黄。镉黄不溶于水、碱、有机溶剂和油类，微溶于5%稀盐酸，溶于浓硫酸、稀硝酸及沸腾稀硫酸 ${(1:5)}$ ，不受 $\\mathbf{H}_{2}\\mathbf{S}$ 的影响。镉黄的研磨性好，易与胶黏剂黏合，但耐磨性差，着色力和遮盖力不如铬黄。耐光性、耐候性优良，不迁移，不渗色。有毒，在潮湿空气中可氧化为硫酸镉。  \n\n可用于耐高温涂料的着色，不宜与含铜或铜盐的颜料拼用，以免生成黑色的硫化铜或绿  \n\n色的硫酸铜。  \n\n(2）镉红[C.I. Pigment Red108（77202）][12214-12-9]镉红（cadmiun red)，又称大红色素。硫硒化镉红是由硫化镉和硒化镉所组成的，其化学组成可用通式nCdS $\\cdot$ CdSe或${\\mathrm{Cd}}(\\mathsf{S}_{x}\\mathsf{S e}_{1-x})$ ）来表示。  \n\n镉红是最牢固的红颜料，颜色非常饱和而鲜明，色谱范围可从黄光红，经红色直至紫酱色。镉红中CdSe含量越高，红光越强，颜色越深。镉红颗粒形态基本上为球形，其晶体结构主要为六方晶型，也有立方晶型，其耐热性在 $600^{\\circ}\\mathrm{C}$ 左右。镉红在热分解时，固溶体变为CdS与CdSe的混合物，在高温下与氧作用，CdSe可氧化成CdO和 $\\mathbf{SeO}_{2}$ 。镉红的耐候性和耐腐蚀性优良，遮盖力强，不溶于水、有机溶剂、油类和碱性溶剂，微溶于弱酸，溶解于强酸并放出有毒气体 $\\mathrm{H}_{2}\\mathrm{Se}$ 和 $\\mathrm{H}_{2}\\mathrm{S}$ 西  \n\n镉红广泛用于糖瓷、陶瓷、玻璃、涂料、塑料、美术颜料、印刷油墨、造纸、皮革、彩色沙石建筑材料和电子材料等行业。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 555,
+        "chunk": "# 6.其他无机着色颜料  \n\n(1）钒酸［C.I.PigmentYellow184（771740)][14059-33-7］钒酸秘是复相氧化物颜料，一般认为其通式为 $\\mathbf{BiVO_{4}}$ 。在通常使用比例下，遮盖力比有机颜料高很多，着色力则不如有机颜料，耐久性不管是深色还是浅色都极好。主要用于外墙涂料，但由于其价格较贵而用量较少。  \n\n(2）钛镍黄[C.I.PigmentYellow 53（77788)][8007-18-9］钛镍黄是镍和锑在1000℃左右高温下，通过热扩散的方式进入 $\\mathrm{TiO}_{2}$ 的晶格中的。淡黄色粉末， $\\mathrm{TiO}_{2}$ 含量为 $78\\%\\sim$ $80\\%$ ，为金红石结构。其化学性质十分稳定，不仅对酸碱都有优良的稳定性，而且对氧化剂、还原剂及硫化物都非常稳定。其耐候性和耐久性甚至超过金红石型钛白，可用于卷钢、汽车和航空涂料；也可用于标牌、路标涂料等；利用其优异的耐热性，可用于耐高温涂料；利用其化学稳定性，可用于化工厂的设备和墙壁涂料、水泥涂料、乳胶涂料和酸固化氨基树脂涂料；由于其无毒，故可用于玩具涂料、食品罐的印刷油墨等。  \n\n其缺点在于着色力低、粒度粗、分散性差，不宜单独作为黄色颜料。一般和其他有机黄色颜料配合使用，用于浅色耐候性外用涂料。  \n\n(3）氧化铬绿[C.I.PigmentGreenl7（77288)][1308-38-9]氧化铬绿（chromic oxide)，又称塘瓷铬绿，其化学组成为三氧化二铬，分子式 $\\phantom{+}\\mathrm{Cr}_{2}\\mathbf{O}_{3}$ ，分子量151.99。  \n\n氧化铬绿为六方晶系或无定形深绿色粉末，氧化铬 $\\scriptstyle(\\mathbf{C}\\tau_{2}\\mathbf{O}_{3}$ ）含量大于 $95\\%$ ，具有金属光泽。熔点 $(2266\\pm25)\\mathrm{^{\\circ}C}$ ，沸点 $4000\\Upsilon$ 。不溶于水和酸，可溶于热的碱金属溴酸盐溶液中。其突出优点在于对光、大气及腐蚀性气体（ $\\mathrm{\\so}_{2}$ ， $\\mathbf{H}_{2}\\mathbf{S}$ 等）极稳定，耐酸、耐碱，耐高温达 $1000^{\\circ}\\mathrm{C}$ ，具有磁性，但色泽不光亮。  \n\n氧化铬绿具有极高的热稳定性和化学稳定性，可用于高温漆的制造，以及化学环境恶劣条件下使用的防护漆；还用于糖瓷和瓷器的彩绘，人造革、建筑材料等作为着色剂；用于制造耐晒涂料和研磨材料、绿色抛光膏及印刷钞票的专用油墨。  \n\n(4）钻蓝[C.I.Pigment Blue 28（77346)][1345-16-0]钻蓝（cobaltous blue）的主要成分为铝酸钴，分子式 $\\mathrm{Co}(\\mathrm{AlO}_{2})_{2}$ ，分子量176.89。  \n\n钻蓝的主要组成是 $\\mathbf{CoO}$ ， $\\mathbf{Al}_{2}\\mathbf{O}_{3}$ ，其实际组成 $\\mathbf{Al}_{2}\\mathbf{O}_{3}$ 为 $65\\%\\sim70\\%$ ，CoO为 $30\\%$ Q$35\\%$ 。钴蓝是带有尖晶石结晶的立方晶体，由于是高温烧，颜料颗粒度较高。钻蓝是一种带有绿光的蓝色颜料，有鲜明的色泽，有极优良的耐候性、耐酸碱性，能耐受各种溶剂，耐热可达 $\\mathtt{1200T}$ ，着色力较弱。属无毒颜料。  \n\n主要用于耐高温涂料，陶瓷、糖瓷、玻璃和塑料着色及耐高温的工程塑料着色，还可以作为美术颜料。  \n\n(5）群青[C.I.Pigment Blue 29（77007）][57455-37-5]群青（uitramarineblue），又称云青、石头青、洋蓝、佛青、群青蓝，分子式 $\\mathrm{Na}_{6}\\mathrm{Al}_{4}\\mathrm{Si}_{6}\\mathrm{S}_{4}\\mathrm{O}_{20}$ ，分子量862.558。  \n\n蓝色粉末，色调艳丽、清新。折射率 $1.50\\sim1.54\\$ ，密度 $2.35\\sim2.74g/\\mathrm{cm}^{3}$ 。不溶于水和有机溶剂。具有极好的耐光性、耐碱性、耐热性、耐候性。在 $200^{\\circ}\\mathrm{C}$ 条件下长期不变色；有较好的亲水性，但易被酸的水溶液所破坏。  \n\n群青除蓝色以外，还有粉红色和绿色的，但无论是哪种颜色其遮盖力都很弱。群青的色调与它的颗粒大小有关，深色品种的颗粒大小为 $3\\sim5\\mu\\mathrm{m}$ ，冲淡后呈红相；浅色品种的颗粒大小为 $0.5\\sim1.0\\mu\\mathrm{m}$ ，着色力稍强，冲淡后呈绿相。  \n\n群青用在涂料中，可以消除或降低白色涂料或其他白色材料中含有黄色色光的效能。在灰、黑等色中掺入群青，可使颜色具有柔和的光泽。也可以用群青单独着色，但其遮盖力和着色力稍弱。  \n\n(6）铁蓝[C.I.Pigment Blue 27（77510，77520)][12240-15-2］铁蓝（iron blue）的几个品种都是以氰基配合物为基础的蓝色颜料，由于性能上的细小差异，而具有不同的名称，如华蓝、普鲁士蓝、铁蔚蓝、密罗里蓝、腾堡蓝、铜光蓝、非铜光蓝等。铁蓝是$\\mathrm{Fe}_{4}\\mathrm{[Fe(CN)_{6}]_{3}}$ 与 ${\\bf K}_{4}\\mathrm{Fe}({\\bf C N})_{6}$ 或 $\\mathrm{(NH_{4})_{4}F e(C N)_{6}}$ 及水组成的复杂化合物。  \n\n深蓝色粉末，相对密度1.8。不溶于水、乙醇和醚，遇碱分解，遇弱酸不发生化学变化，遇浓硫酸煮沸则分解。耐晒、耐光，吸油量大，遮盖力略差。在空气中加热到 $140^{\\circ}\\mathrm{C}$ 以上，即发生燃烧。  \n\n铁蓝的色光根据其成分组成不同介于暗蓝到亮蓝之间，含碱金属越多，同时Fe(CN)s原子团越多，水分越少，则其颜色越亮。  \n\n铁蓝着色力高、耐光性好且价格低廉，故大量应用于新闻油墨、磁漆、硝基漆、号码漆、商标漆、文教用品着色等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 556,
+        "chunk": "# 二、有机颜料  \n\n有机颜料具有鲜艳的色泽，高的着色力，齐全的色谱，有些品种的性能十分优秀，但遮盖力相对较弱。主要用于油墨、涂料与塑料着色等。根据美国的统计，用于油墨、涂料、塑料和其他领域的有机颜料分别为 $45\\%$ 。 $26\\%$ ， $20\\%$ 和 $9\\%$ ，具有一定的代表性，同世界性的消费结构大致相似。  \n\n有机颜料的产量比无机颜料小得多。据统计，2003年世界颜料总产量为630万吨，其中 $62\\%$ 为钛白粉， $18\\%$ 为氧化铁， $12\\%$ 为颜料级炭黑，其他彩色无机颜料为 $4\\%$ ，有机颜料为25.1万吨，仅占 $4\\%$ 。无机颜料中的钛白在世界的颜料产值和产量中均占首要的地位，但有机颜料却在油墨、涂料与塑料等领域发挥重要作用。  \n\n近年来，我国有机颜料产量迅速增加。2006年我国有机颜料产量约为18万吨，大约占全球有机颜料总产量的 $60\\%$ 以上，而且品种增多，并开发出特殊偶氮、多环类颜料高档新品种与专业剂型。  \n\n世界有机颜料生产以欧洲、美国、日本为主，如德国巴斯夫（BASF)、德国科莱恩(Clariant）、瑞士汽巴（Ciba）、德国拜耳（Bayer）、大日本油墨（DinipponInk）及美国太阳化学（SunChem）等。  \n\n随着有机颜料的应用越来越广泛，高档涂料、油墨的需求量不断增大，有机颜料也朝着高性能、低污染等方向发展，偶氮缩合、HPP类产品增长迅猛，逐步取代有毒、性能较低的无机颜料与传统偶氮颜料。本节简单介绍以下涂料用有机颜料情况。按其分子化学结构中含有特定的发色团或官能团实施化学结构分类，可分为偶氮颜料（单偶氮、双偶氮)、菁颜料、多环颜料及其他颜料等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 557,
+        "chunk": "# 1.偶氮颜料  \n\n偶氮颜料是指化学结构中含有偶氮基 $(-\\mathbf{N}-\\mathbf{N}-\\mathbf{\\partial}^{\\cdot},$ ）的颜料，其分子中的偶氮基是通过重氮化与偶合反应而引入的。偶氮颜料色泽鲜艳，色谱分布广，着色力强，密度小，体质软，耐性较好，广泛用于油墨、涂料、橡胶、塑料等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 558,
+        "chunk": "# (1）单偶氮颜料  \n\na.耐晒黄10G耐晒黄10G（hansa yelow 10G，segnele light yellow l0G），又称1104耐晒黄10G、汉黄10G、颜料黄10G、1002汉沙黄10G。耐晒黄10G主要物化指标见表2-2-27。  \n\n表2-2-27耐晒黄10G主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>C. I Pigment</td><td>Yellow 3</td><td>色光</td><td>亮绿光黄</td><td>耐温性/C</td><td>160</td></tr><tr><td>C.L结构号</td><td>11710</td><td>密度/(g/cm²）</td><td>1.60</td><td>耐酸性/级</td><td>5</td></tr><tr><td>CAS No</td><td>[6486-23-3]</td><td>熔点/℃</td><td>258</td><td>耐碱性/级</td><td>5</td></tr><tr><td>EU No</td><td>[229-355-1]</td><td>平均粒径/μm</td><td>0.48~0.57</td><td>耐水性/级</td><td>4</td></tr><tr><td>分子式</td><td>CHClNO</td><td>吸油量/（g/100g)</td><td>22~60</td><td>耐油性/级</td><td>4</td></tr><tr><td>分子量</td><td>395.20</td><td>耐光性/级</td><td>6</td><td>pH（10%水浆）</td><td>6.0~7.5</td></tr></table></body></html>  \n\n耐晒黄10G为带绿光的淡黄色粉末。色泽鲜艳，着色力强，高遮盖力，耐晒性、耐热性好，微溶于乙醇、苯和丙酮等有机溶剂。主要用于涂料、涂料印花、油墨、彩色颜料、文教用品和塑料制品着色。  \n\nb.耐晒黄5GX耐晒黄5GX（pigmentyellow 5GX)，又称颜料黄5GX。是涂料与油墨的主要品种，国外各大公司都生产此品种，如德国巴斯夫（BASF)、德国科莱恩（Clari-ant)、瑞士汽巴（Ciba）等根据不同用途都有几个品种面向市场。属中等绿光黄，有逮盖型与透明型两种，着色力可与联苯胺黄相媲美，比一般单偶氮颜料要高。具有较好的耐光性、耐候性及耐溶剂性，是取代铬黄的重要品种之一。耐晒黄5GX主要物化指标见表2-2-28。  \n\n表2-2-28耐晒黄5GX主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>C. L Pigment</td><td>Yellow 74</td><td>色光</td><td>亮黄</td><td>耐温性/C</td><td>160</td></tr><tr><td>C.I结构号</td><td>11741</td><td>密度/（g/cm²）</td><td>1. 28~1.51</td><td>耐酸性/级</td><td>5</td></tr><tr><td>CAS No</td><td>[6358-31-2]</td><td>熔点/</td><td>275~293</td><td>耐碱性/级</td><td>5</td></tr><tr><td>EU No</td><td>[228-768-4]</td><td>平均粒径/μm</td><td>0.18</td><td>耐水性/级</td><td>4~5</td></tr><tr><td>分子式</td><td>CHNO</td><td>吸油量/(g/100g）</td><td>27~45</td><td>耐油性/级</td><td>5</td></tr><tr><td>分子量</td><td>386.36</td><td>耐光性/级</td><td>6</td><td>pH（10%水浆）</td><td>5.5~7.5</td></tr></table></body></html>  \n\nc.永固黄FGL永固黄FGL（permanertyellowFGL）是20世纪60年代开发的品种，各项牢度优异，耐热性、耐迁移性较好，除高档涂料外还用于各种油墨、塑料中。主要生产厂家有：德国巴斯夫（BASF）、德国科莱恩（Clariant）及杭州胜达、杭州新晨等。永固黄FGL主要物化指标见表2-2-29。  \n\n$\\Phi$ 芳基吡唑啉酮系颜料（表2-2-30）芳基吡唑啉酮系颜料耐光性良好，在醇类、芳香烃中有少量渗性。主要用于涂料、油墨中，目前市场品种较少。  \n\n表2-2-29永固黄FGL主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>C. L. Pigment</td><td>Yellow 97</td><td>色光</td><td>艳黄色</td><td>耐温性/C</td><td>200</td></tr><tr><td>C.I结构号</td><td>11767</td><td>密度/（g/ema）</td><td>1. 30~1.41</td><td>耐酸性/级</td><td>5</td></tr><tr><td>CAS No</td><td>[12225-18-2]</td><td>熔点/C</td><td>330</td><td>耐碱性/级</td><td>5</td></tr><tr><td>EU No</td><td>[235-427-3]</td><td>平均粒径/μm</td><td>0.16</td><td>耐水性/级</td><td>5</td></tr><tr><td>分子式</td><td>CH7CINOS</td><td>吸油量/(g/100g)</td><td>40~52</td><td>耐油性/级</td><td>5</td></tr><tr><td>分子量</td><td>591.08</td><td>耐光性/级</td><td>7~8</td><td>pH（10%水浆）</td><td>7.0~8.0</td></tr></table></body></html>  \n\n表2-2-30芳基吡唑啉酮系颜料结构式  \n\n\n<html><body><table><tr><td>结构式</td><td>主要品种</td><td>X</td><td>Y</td><td>Z</td></tr><tr><td>X NH N -CH N</td><td>颜料货1ellowR 颜料橙6 Pigment Fast Orange 4G</td><td>CI NO</td><td>H CH</td><td>Cl H</td></tr></table></body></html>  \n\n②乙萘酚系颜料（表2-2-31）甲苯胺红是此类的主要品种，商品有多种色光及牌号，大量用于油性漆和乳化漆中。由于耐溶剂性不佳，在醇酸树脂漆中使用受到限制。  \n\n表2-2-31乙蔡酚系颜料结构式  \n\n\n<html><body><table><tr><td>结构式</td><td>主要品种</td><td>X</td><td>Y</td></tr><tr><td>X</td><td>永固橙RN 甲苯胺红</td><td>NO NO</td><td>NO CH</td></tr></table></body></html>  \n\n银朱R是带黄相的大红，至今仍是重要的大红色品种，用于制漆及文教用品着色。  \n\n永固橙RN的牢度与颜料红3#相仿，是橙色中主要品种，用于制漆和油墨。其结构中含有两个硝基，在生产和使用时应当注意安全，不能和氧化铅并用，在干燥、粉碎和研磨过程中，要避免高温和冲击，以免发生危险。主要乙萘酚系颜料主要物化指标见表2-2-32。  \n\n表2-2-32主要乙蔡酚系颜料主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>甲苯胺红</td><td>银朱R</td><td>水固橙RN</td></tr><tr><td>C.L Pigment</td><td>Red 3</td><td>Red 4</td><td>Orange5</td></tr><tr><td>C.L结构号</td><td>12120</td><td>12085</td><td>12075</td></tr><tr><td>CAS No</td><td>[2425-85-6]</td><td>[2814-77-9]</td><td>[3468-63-1]</td></tr><tr><td>EU No</td><td>[219-372-2]</td><td>[220-562-2]</td><td>[222-429-4]</td></tr><tr><td>分子式</td><td>CH NO</td><td>C HoCINO</td><td>CsHoNOs</td></tr><tr><td>分子量</td><td>307.30</td><td>327.72</td><td>338.27</td></tr><tr><td>色光</td><td>黄光红</td><td>黄光红</td><td>亮红光橙</td></tr><tr><td>密度/（g/cma）</td><td>1.34~1.52</td><td>1. 45~1.60</td><td>1.48~2.00</td></tr><tr><td>吸油量/（g/100g）</td><td>33~80</td><td>34~70</td><td>35~50</td></tr><tr><td>耐光性/级</td><td>6</td><td>6</td><td>6~7</td></tr><tr><td>耐温性/C</td><td>120</td><td>100</td><td>130</td></tr><tr><td>耐酸性/级</td><td></td><td>5</td><td>5</td></tr><tr><td>耐碱性/级</td><td>4</td><td>5</td><td>4</td></tr><tr><td>耐水性/级</td><td>3</td><td>5</td><td>4~5</td></tr><tr><td>耐油性/级</td><td>3</td><td>4</td><td>4</td></tr><tr><td>pH(10%水浆）</td><td>6.0~7.0</td><td>5.5~7.5</td><td>6.5</td></tr></table></body></html>  \n\n$\\textcircled{3}$ 色酚AS系颜料（表2-2-33）主要为红色品种居多，一般具有较好的牢度性能，特别是耐碱性尤为优越。  \n\n表2-2-33色酚AS系颜料结构式  \n\n\n<html><body><table><tr><td></td><td>主要品种 X</td><td>Y</td><td>Z</td><td>U</td><td>V</td><td>W</td></tr><tr><td>大红粉 U</td><td>H</td><td>H</td><td>H</td><td>H</td><td>H</td><td>H</td></tr><tr><td>颜料亮红N</td><td>CH</td><td>H</td><td>NO</td><td>H</td><td>H</td><td>H</td></tr><tr><td>永固红FGR</td><td>C1</td><td>CI</td><td>CI</td><td>CH</td><td>H</td><td>H</td></tr><tr><td>永固桃红FBB</td><td>OCH3</td><td>H</td><td>NHCO</td><td>OCH</td><td>CI</td><td>OCH</td></tr><tr><td>水固桃红F3RK</td><td>H</td><td>CONH</td><td>H</td><td>OCHs</td><td>H</td><td>H</td></tr></table></body></html>  \n\n其中，国内使用最多的是大红粉，大红粉广泛用于制造涂料。颜料永固红FGR、永固红F3RK、颜料亮红N是色彩鲜艳的大红色，牢度优异，主要用于涂料、水性涂料、涂料印花浆和人造丝的着色。永固桃红FBB带蓝光的红色，各项牢度优异，适用于涂料、汽车漆、橡胶、涂料印花浆和塑料中。色酚AS系颜料主要物化指标见表2-2-34。  \n\n表2-2-34色酚AS系颜料主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>大红粉</td><td>颜料亮红N</td><td>永固红FGR</td><td>永固桃红FBB</td><td>水固红F3RK</td></tr><tr><td>C. L Pigment</td><td>Red 21</td><td>Red 22</td><td>Red 112</td><td>Red 146</td><td>Red170</td></tr><tr><td>C.L结构号</td><td>12300</td><td>12315</td><td>12370</td><td>12485</td><td>12475</td></tr><tr><td>CAS No</td><td>[6410-26-0]</td><td>[6448-95-9]</td><td>[6535-46-2]</td><td>[5280-68-2]</td><td>[2786-76-7]</td></tr><tr><td>EU No</td><td>[229-096-4]</td><td>[229-245-3]</td><td>[229-440-3]</td><td>[226-103-2]</td><td>[220-509-3]</td></tr><tr><td>分子式</td><td>CzsHCINO</td><td>CHNO</td><td>CHClNO</td><td>Cs Hz CINOs</td><td>Ca HNO</td></tr><tr><td>分子量</td><td>401.84</td><td>426.42</td><td>485.76</td><td>611. 04</td><td>454.48</td></tr><tr><td>色光</td><td>黄光红</td><td>黄光红</td><td>艳红</td><td>蓝光红</td><td>蓝光红</td></tr><tr><td>密度/(g/cm）</td><td>-</td><td>1. 30~1.47</td><td>1. 38~1.65</td><td>1. 35 ~1. 40</td><td>1.25~1.36</td></tr><tr><td>吸油量/（g/100g）</td><td>57</td><td>34~68</td><td>35~88</td><td>65~70</td><td>59~81</td></tr><tr><td>耐光性/级</td><td>3~4</td><td>5</td><td>7</td><td>5</td><td>7~8</td></tr><tr><td>耐温性/C</td><td>100</td><td>120</td><td>150</td><td>160</td><td>200</td></tr><tr><td>耐酸性/级</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>耐碱性/级</td><td>3</td><td>2</td><td>5</td><td>4~5</td><td>5</td></tr><tr><td>耐水性/级</td><td>3~4</td><td>4</td><td>5</td><td>#</td><td>4</td></tr><tr><td>耐油性/级</td><td>1</td><td>2</td><td>4~5</td><td>5</td><td>4</td></tr><tr><td>pH(10%水浆)</td><td>7</td><td>7</td><td>3.5~7.0</td><td>5.5~7.0</td><td>6.0~7.0</td></tr></table></body></html>  \n\n$\\textcircled{4}$ 苯并咪唑酮系颜料（表2-2-35）苯并咪唑酮系单偶氮颜料的结构中引入环状酰氨基团，提高分子的极性，使分子间形成较强的氢键，从而影响分子的聚集状态，降低了颜料在有机溶剂中的溶解度，增强了耐迁移性。氢键的存在，能提高颜料分子的稳定性，增强对光和热的抵抗能力，使耐光性、耐热性都有明显改善。苯并咪唑酮系颜料主要物化指标见表2-2-36。  \n\n(2）双偶氮颜料双偶氮颜料是指颜料的分子中含有两个偶氮基的颜料，这类颜料的母体大多数为联苯胺和对苯二胺。  \n\n$\\textcircled{1}$ 双芳胺类黄色双偶氮颜料结构式及主要品种（表2-2-37)  \n\n表2-2-35苯并咪唑酮系颜料结构式  \n\n\n<html><body><table><tr><td>黄橙色结构式</td><td>主要品种</td><td>X</td><td>Y</td><td>Z</td><td>W</td></tr><tr><td>X W- -NNHCONH NH COCH °0</td><td>水固黄H4G 永固黄H3G 永固橙HL</td><td>COOH CF NO</td><td>H H H</td><td>H H CI</td><td>H H H</td></tr><tr><td>红色结构式</td><td>主要品种</td><td>X</td><td>Y</td><td colspan=\"2\">Z</td></tr><tr><td>X HQ CONH- BH NN H *0</td><td>洋红HF3C 洋红HF4C</td><td>OCH CH</td><td>H CH HNSO;</td><td colspan=\"2\">-NHCO OCH3</td></tr></table></body></html>  \n\n表2-2-36苯井咪唑酮系颜料主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>永固黄H4G</td><td>永固黄H3G</td><td>永固橙HL</td><td>洋红HF3C</td><td>洋红HFC</td></tr><tr><td>C.I. Pigment</td><td>Yellow 151</td><td>Yellow 154</td><td>Orange 36</td><td>Red 176</td><td>Red 185</td></tr><tr><td>C.L结构号</td><td>13980</td><td>11781</td><td>11780</td><td>12515</td><td>12516</td></tr><tr><td>CAS No</td><td>[31837-42-0]</td><td>[68134-22-5]</td><td>[12236-62-3]</td><td>[12225-06-8]</td><td>[51920-12-8]</td></tr><tr><td>EU No</td><td>[250-830-4]</td><td>[268-734-6]</td><td>[235-462-4]</td><td>[235-425-2]</td><td>[257-515-0]</td></tr><tr><td>分子式</td><td>CHis NsOs</td><td>CHFNsOs</td><td>C HCINOs</td><td>CsHNsOs</td><td>Can HNOS</td></tr><tr><td>分子量</td><td>381.34</td><td>405.33</td><td>416.81</td><td>572.57</td><td>560.63</td></tr><tr><td>色光</td><td>绿光黄</td><td>绿光黄</td><td>红光橙</td><td>艳蓝光红</td><td>艳蓝光红</td></tr><tr><td>密度/（g/cm）</td><td>1.57</td><td>1.57</td><td>1.62</td><td>1.45</td><td>1.45</td></tr><tr><td>吸油量/(g/100g)</td><td>52</td><td>61</td><td>80</td><td>70~88</td><td>_97</td></tr><tr><td>耐光性/级</td><td>7~8</td><td>7~8</td><td>7~8</td><td>7~8</td><td>7~8</td></tr><tr><td>耐温性/C</td><td>250</td><td>250</td><td>240</td><td>250</td><td>250</td></tr><tr><td>耐酸性/级</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>耐碱性/级</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>耐水性/级</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>耐油性/级</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>pH(10%水浆）</td><td>7.3</td><td>6.5</td><td>7</td><td>7</td><td>7.5</td></tr></table></body></html>  \n\n表2-2-37双芳胺类黄色双偶氮颜料结构式  \n\n\n<html><body><table><tr><td>结构式</td><td colspan=\"4\">U X Y H V- -NHCO- C N—N- W COCH Y</td></tr><tr><td>主要品种</td><td>X</td><td>Y</td><td>u</td><td>V</td><td>W</td></tr><tr><td>联苯胺黄G 永固黄2GS 永固黄HR</td><td>CI Cl Cl</td><td>H H H</td><td>H CH OCH; H/H</td><td>H H Cl H/OCH</td><td>H H OCH</td></tr></table></body></html>\n\n$\\textcircled{2}$ 吡唑啉酮类双偶氮颜料结构式及主要品种（表2-2-38）几种双偶氮颜料主要物化指标见表2-2-39。  \n\n表2-2-38吡唑啉酮类双偶氮颜料结构式  \n\n\n<html><body><table><tr><td>结构式</td><td>主要品种</td><td>X</td><td>Y</td><td>U</td><td>V</td></tr><tr><td>X X U- U N OH HO V V</td><td>永固橘黄G 永固橙RL</td><td>Cl C1</td><td>H H</td><td>CH CH</td><td>H CH</td></tr></table></body></html>  \n\n表2-2-39几种双偶氨颠料主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>联苯胺黄G</td><td>水固黄2GS</td><td>水固黄HR</td><td>水固黄DGR</td><td>水固橘黄G</td><td>永固橙RL</td></tr><tr><td>C.IL. Pigment</td><td>Yellow 12</td><td>Yellow 14</td><td>Yellow 83</td><td>Yellow 126</td><td>Orange13</td><td>Orange 34</td></tr><tr><td>C.I.结构号</td><td>21090</td><td>21095</td><td>21108</td><td>21101</td><td>21110</td><td>21115</td></tr><tr><td>CAS No</td><td>[6358-85-6]</td><td>[5468-75-7]</td><td>[5567-15-7]</td><td>[61815-08-5]</td><td>[3520-72-7]</td><td>[15793-72-4]</td></tr><tr><td>EU No</td><td>[228-787-8]</td><td>[226-789-3]</td><td>[226-939-8]</td><td>[228-787-8]</td><td>[222-530-3]</td><td>[239898-6]</td></tr><tr><td>分子式</td><td>CaHClNO</td><td>CHClNOCaHClNO</td><td></td><td>一</td><td></td><td>CHClNOCHClNO</td></tr><tr><td>分子量</td><td>629.49</td><td>657.55</td><td>818.49</td><td>一</td><td>623.48</td><td>651.60</td></tr><tr><td>色光</td><td>黄色</td><td>红光黄</td><td>红光黄</td><td>绿光黄</td><td>红光橙</td><td>红光橙</td></tr><tr><td>密度/(g/cm）</td><td>1.40</td><td>1. 14~1.52</td><td>1. 27~1.50</td><td>1.38</td><td>1. 31~1.60</td><td>1. 30~1.40</td></tr><tr><td>吸油量/(g/100g)</td><td>25~80</td><td>29~75</td><td>39~98</td><td>77</td><td>28~85</td><td>43~79</td></tr><tr><td>耐光性/级</td><td>4</td><td>4</td><td>6</td><td>4~5</td><td>4~5</td><td>6</td></tr><tr><td>耐温性/C</td><td>180</td><td>180</td><td>200</td><td>200</td><td>140</td><td>180</td></tr><tr><td>耐酸性/级</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td><td>4</td></tr><tr><td>耐碱性/级</td><td>5</td><td>5</td><td>5</td><td>5</td><td>4</td><td>5</td></tr><tr><td>耐水性/级</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td><td>4</td></tr><tr><td>耐油性/级</td><td>4</td><td>4</td><td>5</td><td>4</td><td>4</td><td>5</td></tr><tr><td>pH(10%水浆）</td><td>6~8</td><td>6~8</td><td>6~7</td><td>6~8</td><td>6~7</td><td>6~7</td></tr></table></body></html>  \n\n(3）偶氮缩合颜料偶氮缩合颜料结构式如图2-2-5所示。几种偶氮缩合颜料主要物化指标见表2-2-40。  \n\n![](images/d3c3708d24e772f016d7b5bedc8baa878b706f119cc09a3b973769acad39fb9a.jpg)  \n图2-2-5偶氮缩合颜料结构式  \n\n表2-2-40几种偶氮缩合额料主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>黄8GN</td><td>红BRN</td><td>缩偶氨大红R</td><td>缩偶氮大红4RF</td></tr><tr><td>结构式中X</td><td>CH</td><td>C1</td><td>Cl</td><td>CF</td></tr><tr><td>结构式中Y</td><td>Cl</td><td></td><td>H</td><td>Cl</td></tr><tr><td>结构式中Z</td><td>FcYYa</td><td>H</td><td>H</td><td>Cl</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>项目</td><td>黄8GN</td><td>红BRN</td><td>缩偶氮大红R</td><td>缩偶氮大红4RF</td></tr><tr><td>C. L Pigment</td><td>Yellow 128</td><td>Red 144</td><td>Red 166</td><td>Red 242</td></tr><tr><td>C.L结构号</td><td>20037</td><td>20735</td><td>20730</td><td>20067</td></tr><tr><td>CAS No</td><td>79953-85-8</td><td>5280-78-4</td><td>3905-199</td><td>52238-92-3</td></tr><tr><td>EU No</td><td>279-356-6</td><td>226-106-9</td><td>223-460-6</td><td>257-776-0</td></tr><tr><td>分子式</td><td>CssHClFNO</td><td>CHCl NO</td><td>CoHClNO</td><td>CaHClFNO</td></tr><tr><td>分子量</td><td>1229. 25</td><td>828.94</td><td>794.50</td><td>930.46</td></tr><tr><td>色光</td><td>绿光黄</td><td>蓝光红</td><td>黄光红</td><td>黄光红</td></tr><tr><td>密度/(g/cm）</td><td>1.53</td><td>1. 45 ~1. 55</td><td>1.57</td><td>1.61</td></tr><tr><td>吸油量/（g/100g)</td><td>56~70</td><td>50~60</td><td>55</td><td>55</td></tr><tr><td>耐光性/级</td><td>7~8</td><td>7</td><td>7~8</td><td>7~8</td></tr><tr><td>耐温性/C</td><td>200</td><td>250</td><td>250</td><td>200</td></tr><tr><td>耐酸性/级</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>耐碱性/级</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>耐水性/级</td><td>5</td><td>4</td><td>5</td><td>5</td></tr><tr><td>耐油性/级</td><td>5</td><td>4</td><td>5</td><td>5</td></tr><tr><td>pH(10%水浆）</td><td>5~6</td><td>6.8</td><td>7</td><td>6~7.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 559,
+        "chunk": "# 2.酥菁颜料  \n\n(1）菁蓝酞菁蓝主要组成是细结晶的铜酞菁（图2-2-6)。具有鲜明的蓝色，耐光性、耐热性、耐酸性、耐碱性、耐化学药品性优良。着色力强，是当前性能最为优越的蓝色  \n\n颜料。酥菁蓝分子式 $\\mathrm{C_{32}H_{16}C u N_{8}}$  \n\n![](images/18a30212db7743e5817ca56ee52b591fe9cddb8eaa79f9e332ed6037672df045.jpg)  \n图2-2-6铜菁结构式  \n\nCuPc最先是在1935年由ICI公司制造出来的，当时是以苯酐与尿素为原料，应用钼酸铵为催化剂提高了收率；1936年IG.染料公司在德国Ludwishafen开始了CuPc 的生产；1937年美国杜邦公司生产菁颜料并投放市场；1949年稳定的β型铜菁问世。菁蓝15已知的有α、β、、、、Ⅱ、X、R、p九种晶型。晶型的不同可影响其应用性能，如着色强度、色光及耐热稳定性等。α型呈红光，β型呈绿光，e型呈大红光，其热力学稳定性： $\\alpha{\\approx}\\gamma{<}\\delta{<}\\epsilon{<}\\beta,$  \n\n$\\Phi$ 菁蓝15（蓝B）为亚稳α型酥菁蓝，带红光蓝色粉末，色泽鲜艳，着色力高，具有较高的性价比。此类颜料晶型稳定性较差，遇 $200^{\\circ}\\mathrm{C}$ 左右高温或芳香族溶剂会产生“结晶”现象，其颜料晶型发生转变，主要应用于油墨、涂料及涂料印花浆等。  \n\n$\\textcircled{2}$ 酥菁蓝 $15:1$ （蓝BS）为稳定α型菁蓝，带红光蓝色粉末，具有耐有机溶剂性和抗结晶性。与献菁蓝15比较，透明度和着色力都有所降低。但有好的耐光性、耐候性、耐迁移性及耐热稳定性等，不具有抗絮凝性，可应用于各种涂料中，但不能应用于一些特殊要求的涂料体系。  \n\n$\\textcircled{3}$ 酞菁蓝 $15:2$ （蓝BS）为抗结晶性、抗絮凝性的α型菁蓝，主要应用于涂料着色。  \n\n$\\textcircled{4}$ 酞菁蓝 $15:3$ （蓝BGS)，为β型酞菁蓝，这是一种稳定的晶型。色光明显偏绿，高着色力、易分散。具有较好的耐光性、耐候性和热稳定性，良好的耐溶剂性、耐皂化性及耐酸碱性，是涂料工业中最为重要的蓝色颜料品种。  \n\n$\\textcircled{5}$ 酞菁蓝 $15:4$ 为抗结晶性、抗絮凝性的 $\\upbeta$ 型酞菁蓝，主要应用于涂料着色。除分散性、抗絮凝性及流动性外，其他性能与酞菁蓝 $15:3$ 基本一致，应用于各类涂料，目前市场上量很少。  \n\n$\\textcircled{6}$ 酞菁蓝 $15:5$ 为型肽菁蓝，是一种不稳定酞菁蓝。酞菁蓝 $15:6$ 为型菁蓝，晶型比较稳定，红光为所有菁蓝最强，着色力比α型菁蓝要高20%以上，具有良好的流动性、耐光性、耐候性、耐溶剂性及耐热性等。有生产商，但产量均比较小。  \n\n(2）酞菁绿酥菁绿G，化学组成为多氯代铜酞菁。色光呈蓝光绿色，具有良好的应用性能，如耐光性、耐候性、耐热稳定性及耐溶剂性等，是涂料的重要绿色品种。颜料绿36是氯溴混合取代的铜菁颜料。属黄光菁绿，耐性较好，分子量是菁绿G的7倍，但着色力比菁绿G要低，档次价格要高，主要应用于高档涂料及油墨等。  \n\n重要的菁颜料品种主要物化指标见表2-2-41。  \n\n表2-2-41重要的献菁颜料品种主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>菁蓝15</td><td>献菁151</td><td>菁蓝1513</td><td>献菁绿G</td><td>颜料绿36</td></tr><tr><td>C. L. Pigment</td><td>Blue 15</td><td>Blue 15 • 1</td><td>Blue 15 • 3</td><td>Green 7</td><td>Green 36</td></tr><tr><td>C.I结构号</td><td>74160(a型)</td><td>74160(稳定α型）</td><td>74160(β型)</td><td>74260</td><td>74265</td></tr><tr><td>CAS No</td><td>[147-14-8]</td><td>[12239-89-1]</td><td>[147-14-8]</td><td>[1328-53-6]</td><td>[14302-13-7]</td></tr><tr><td>EU No</td><td>[205-685-1]</td><td>[205-685-1]</td><td>[205-685-1]</td><td>[215-524-7]</td><td>[238-238-4]</td></tr><tr><td>分子式</td><td>CHsCuN</td><td>Caz HCuNs</td><td>C HsCuNs</td><td>C HClsCuNs</td><td>C32BrCloCuNs</td></tr><tr><td></td><td></td><td>C HsCICuNs</td><td></td><td>CsHClCuNs</td><td></td></tr><tr><td>分子量</td><td>576.07</td><td>576~610</td><td>576.07</td><td>1029~1127</td><td>1293. 90</td></tr><tr><td>平均粒径/μm</td><td>0.08</td><td>0.05</td><td>0. 07~0.09</td><td>0. 03~0.07</td><td>0.03~0.06</td></tr><tr><td>色光</td><td>红光蓝</td><td>亮红光蓝</td><td>绿光蓝</td><td>蓝光绿</td><td>黄光绿</td></tr><tr><td>密度/(g/cm）</td><td>1. 50~1.70</td><td>1. 50~1. 70</td><td>1. 55~1. 65</td><td>1.80~2.40</td><td>2.31~3.19</td></tr><tr><td>比表面积/(m²/g)</td><td>30~90</td><td>53~92</td><td>38~90</td><td>41~62</td><td>30~54</td></tr><tr><td>吸油量/（g/100g）</td><td>32~70</td><td>30~80</td><td>45~60</td><td>22~50</td><td>20~46</td></tr><tr><td>耐光性/级</td><td>7~8</td><td>7~8</td><td>7~8</td><td>7~8</td><td>7~8</td></tr><tr><td>耐温性/C</td><td>200</td><td>200</td><td>220</td><td>220</td><td>300</td></tr><tr><td>耐酸性/级</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>耐碱性/级</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>耐水性/级</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>耐油性/级</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>pH(10%水浆）</td><td>6.5~8.0</td><td>5.0~8.0</td><td>5.0~8. 0</td><td>4.0~9. 0</td><td>4.5~7.5</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 560,
+        "chunk": "# 3.多环颜料  \n\n(1）喹吖啶酮类颜料（表2-2-42）喹吖啶酮颜料的化学结构是四氢喹啉二吖啶酮，习惯称喹吖啶酮。尽管其分子量比菁类颜料小得多，但它们像菁类颜料一样具有很好的耐晒牢度与耐候牢度等，主要色调为红紫色，通常也称为菁红或菁紫。主要应用于高档工业漆、水性装饰漆、建筑漆及户外广告漆等。几种喹吖啶酮类颜料主要物化指标见表2-2-43。  \n\n表2-2-42.多环颜料结构式  \n\n\n<html><body><table><tr><td>结构式</td><td>主要品种</td><td>X</td><td>Y</td><td>Z</td><td>U</td><td>V</td><td>W</td></tr><tr><td rowspan=\"5\"></td><td>瞳吖啶酮紫P.V.19</td><td>H</td><td>H</td><td>H</td><td>H</td><td>H</td><td>H</td></tr><tr><td>喹吖啶酮品红 P. R. 122</td><td>H</td><td>H</td><td>CH</td><td>H</td><td>H</td><td>H</td></tr><tr><td>喹吖啶酮品红 P. R. 202</td><td>H</td><td>H</td><td>Ci</td><td>CH</td><td>H</td><td>H</td></tr><tr><td>唑吖啶酮红 P. R. 206</td><td>H</td><td>H</td><td>H</td><td>Cl</td><td>H</td><td>H</td></tr><tr><td>唑吖啶酮红 P. R. 209</td><td>H</td><td>Cl</td><td>H</td><td>H</td><td>C</td><td>H</td></tr></table></body></html>\n\n(2）二嗪类颜料二嗪类颜料的母体是三苯二嗪，该系列颜料主要为紫色，主要品种为颜料紫23与颜料紫37。  \n\n表2-2-43几种瞳吖啶酮类颜料主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>瞳吖啶酮紫 P.V.19</td><td>唑吖啶酮红 P. R.122</td><td>喹吖啶酮红 P. R. 202</td><td>瞳吖啶酮红 P.R.206</td><td>唑吖啶酮红 P.R.209</td></tr><tr><td>C. 1. Pigment C.I结构号 CAS No</td><td>Violet 19 73900 [1047-16-1]</td><td>Red 122 73915 [980-26-7]</td><td>Red 202 73907 [3089-17-6]</td><td>Red 206 73900/73920 [1503-48-6] [71819-76-6]</td><td>Red 209 73905 [3573-01-1]</td></tr><tr><td>EU No 分子式</td><td>[213-879-2] Cao HNO</td><td>[16043-40-6] 213-561-3 CHs NO</td><td>[221-424-4] Cao HoClNO</td><td>[216-125-0] CHNO</td><td>一 Cao HoClNO</td></tr><tr><td>分子量</td><td>312.32</td><td>340.37</td><td>381.22</td><td>CHo NO 一</td><td>381.22</td></tr><tr><td>色光 密度/(g/cm)</td><td>紫、黄光红 1.50~1.80</td><td>蓝光红 1. 40~1.50</td><td>蓝光红 1.51~1.71</td><td>红褐色 1.45~1.52</td><td>晶红色 1.56</td></tr><tr><td>吸油量/(g/100g)</td><td>40~70</td><td>40~65</td><td>34~50</td><td>27~39</td><td>60</td></tr><tr><td></td><td></td><td></td><td>7~8</td><td>7~8</td><td>7~8</td></tr><tr><td>耐光性/级</td><td>7~8</td><td>7~8</td><td></td><td></td><td></td></tr><tr><td>耐温性/C</td><td>200</td><td>250</td><td>250</td><td>250</td><td>250</td></tr><tr><td>耐酸性/级</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>耐碱性/级</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>耐水性/级</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>耐油性/级</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>pH(10%水浆)</td><td>6~9</td><td>6.2~6.7</td><td>3~6</td><td>3.5~9. 0</td><td>5~7</td></tr></table></body></html>  \n\n①颜料紫23，又称6520永固紫RL，还称为咔唑紫，分子呈对称性与平面性，使其十分稳定。在冲淡色情况下仍具有优异的耐光牢度、耐候牢度，是一种通用型紫色颜料，色调有蓝光与红光两种，色泽鲜艳，着色强度高，耐晒牢度好，耐热性比其他类多环颜料要低些，通常在160℃左右就发生变化。它几乎耐所有有机溶剂，可在很多介质中使用。永固紫主要物化指标见表2-2-44。  \n\n表2-2-44永固紫主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>C. L Pigment</td><td>Violet 23</td><td>色光</td><td>蓝光紫</td><td>耐温性/℃</td><td>160</td></tr><tr><td>C.L结构号</td><td>51319</td><td>密度/（g/cm）</td><td>1.40~1.60</td><td>耐酸性/级</td><td>5</td></tr><tr><td>CAS No</td><td>[6358-30-1]</td><td>熔点/℃</td><td>430~455</td><td>耐碱性/级</td><td>5</td></tr><tr><td>EU No</td><td>[228-767-9]</td><td>平均粒径/μm</td><td>0. 04~0.07</td><td>耐水性/级</td><td>5</td></tr><tr><td>分子式</td><td>CHClNO</td><td>吸油量/(g/100g)</td><td>45</td><td>耐油性/级</td><td>5</td></tr><tr><td>分子量</td><td>589.50</td><td>耐光性/级</td><td>？</td><td>pH（10%水浆）</td><td>6.2</td></tr></table></body></html>  \n\n②颜料紫37比颜料紫23色光要红得多，遮盖力强，着色力弱，具有较好的流动性与光泽。其他各项性能基本与颜料紫23一样。主要应用于高档汽车漆、工业漆，目前仅瑞士Ciba 公司有生产，且产量较小。颜料紫37主要物化指标见表2-2-45。  \n\n表2-2-45颜料紫37主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>C. L Pigment</td><td>Violet 37</td><td>色光</td><td>蓝光紫</td><td>耐温性/C</td><td>160</td></tr><tr><td>C.L结构号</td><td>51345</td><td>密度/(g/cm）</td><td>一</td><td>耐酸性/级</td><td>5</td></tr><tr><td>CAS No</td><td>[57971-98-9]</td><td>熔点/C</td><td>一</td><td>耐碱性/级</td><td>5</td></tr><tr><td>EU No</td><td>一</td><td>平均粒径/μm</td><td></td><td>耐水性/级</td><td>5</td></tr><tr><td>分子式</td><td>CHNO</td><td>吸油量/（g/100g）</td><td>一</td><td>耐油性/级</td><td>5</td></tr><tr><td>分子量</td><td>726.90</td><td>耐光性/级</td><td>二</td><td>pH(10%水浆）</td><td>6.2</td></tr></table></body></html>  \n\n(3）异吲哚啉酮系颜料和异吲哚啉系颜料异吲哚啉酮系颜料和异吲哚啉系颜料是20世纪60年代中期，继喹吖啶酮和二嗪颜料之后发展起来的一类新型高档有机颜料。此类颜料具有很好的耐溶剂性、耐迁移性、耐酸碱性、耐氧化还原性，耐热性高达400℃，耐晒牢度、耐光牢度也非常好，主要应用于高档工业漆及油墨。  \n\n①颜料黄109呈亮绿光黄，着色力高，易分散，耐晒牢度随TiO的加人先升高再降低，如本色耐光性为6～7级，而深色（颜料：TiO=1：1）时，耐晒牢度可达7级，按(1：3)～（1：25）用TiO冲淡耐晒牢度可达7～8级。冲淡比例再升高，耐晒牢度会明显下降。主要应用于高档工业漆、建筑涂料及油墨。颜料黄109主要物化指标见表2-2-46。  \n\n表2-2-46颜料黄109主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>C. L Pigment</td><td>Yellow 109</td><td>色光</td><td>绿光黄</td><td>比表面积/(m²/g)</td><td>29</td></tr><tr><td>C.I结构号</td><td>56284</td><td>密度/（g/cm）</td><td>1. 84</td><td>耐酸性/级</td><td>5</td></tr><tr><td>CAS No</td><td>[5045-40-9]</td><td>熔点</td><td>301</td><td>耐碱性/级</td><td>5</td></tr><tr><td>EU No</td><td>一</td><td>吸油量/(g/100g)</td><td>40~55</td><td>耐水性/级</td><td>5</td></tr><tr><td>分子式</td><td>CHClgNO</td><td>耐温性/C</td><td>250</td><td>耐油性/级</td><td>5</td></tr><tr><td>分子量</td><td>655.96</td><td>耐光性/级</td><td>7~8</td><td>pH（10%水浆）</td><td>5.8</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 颜料黄110为红光较重的黄色，是异吲哚啉酮系颜料中重要品种，也被认为是所有有机颜料红光黄色中最为稳定的一种，广泛应用于高档汽车漆、工业漆、建筑漆。颜料黄110主要物化指标见表2-2-47。  \n\n表2-2-47 颜料黄110主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>C. L Pigment</td><td>Yellow 110</td><td>色光</td><td>红光黄</td><td>耐酸性/级</td><td>5</td></tr><tr><td>C.I.结构号</td><td>56280</td><td>密度/(g/cma)</td><td>1.82</td><td>耐碱性/级</td><td>5</td></tr><tr><td>CAS No</td><td>[5590-18-1]</td><td>吸油量/(g/100g）</td><td>36~77</td><td>耐水性/级</td><td>5</td></tr><tr><td>EU No</td><td>[226-999-5]</td><td>比表面积/（m²/g）</td><td>40~65</td><td>耐油性/级</td><td>5</td></tr><tr><td>分子式</td><td>CHClNO</td><td>耐温性/C</td><td>250</td><td>pH(10%水浆)</td><td>6.5~8.7</td></tr><tr><td>分子量</td><td>641.94</td><td>耐光性/级</td><td>7~8</td><td></td><td></td></tr></table></body></html>  \n\n$\\textcircled{3}$ 颜料黄139为异吲哚啉系颜料中重要品种，红光黄色，其各项性能良好，广泛应用于高档涂料、油墨及塑料。其在水性体系中耐碱性不是很理想，一般不推荐用于水性装饰漆。颜料黄139主要物化指标见表2-2-48。  \n\n表2-2-48颜料黄139主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>C. I. Pigment</td><td>Yellow 139</td><td>色光</td><td>红光黄</td><td>耐酸性/级</td><td>5</td></tr><tr><td>C.I.结构号</td><td>56298</td><td>密度/(g/cm)</td><td>1.74</td><td>耐碱性/级</td><td>5</td></tr><tr><td>CAS No</td><td>[36888-990]</td><td>平均粒径/μm</td><td>0.15~0.35</td><td>耐水性/级</td><td></td></tr><tr><td>EU No</td><td>[253-256-2]</td><td>吸油量/(g/100g)</td><td>45~69</td><td>耐油性/级</td><td></td></tr><tr><td>分子式</td><td>CHNO</td><td>耐温性/℃</td><td>200</td><td>pH(10%水浆)</td><td>5.5~7.0</td></tr><tr><td>分子量</td><td>367.30</td><td>耐光性/级</td><td>8</td><td></td><td></td></tr></table></body></html>  \n\n（4）吡咯并吡咯二酮系颜料（表2-2-49）吡咯并吡咯二酮系颜料（即DPP系颜料）是由瑞士Ciba公司在1983年研制的一类全新结构的高性能有机颜料。属氢键交叉共轭型发色体系，其分子结构具有很好的对称性，分子呈平面排列，显示强烈的 $\\pi-\\pi$ 共轭作用，同时分子间形成氢键与范德华力，形成更大的分子。主要色谱为红色和橙色，该系列颜料颜色鲜艳，着色力高，流动性好，同时具有良好的耐光性、耐候性和耐热性，但耐碱性不如其他类多环有机颜料。广泛应用于高档涂料中，尤其是汽车漆、工业漆及建筑漆等。  \n\nDPP红（P.R.254）是Ciba公司在1986年开发的第一个DPP系颜料商品，具有很好的着色性能和牢度性能，色泽鲜艳，着色强度高。广泛应用于工业漆、水性漆等；DPP 红(P.R.255）呈黄光红色，具有较高的遮盖力，优异的耐候牢度，被推荐用于汽车漆和高级工业漆；DPP红（P.R.264）呈蓝光红色，具有较高的透明度和着色强度，耐酸性、耐碱性均为5级，耐有机溶剂性为 $4\\sim5$ 级，主要推荐使用在汽车漆和高档工业漆中；DPP橙（P.O.73）呈艳丽的橙色，耐芳香烃类溶剂牢度为5级，但耐酮、醇、酯类溶剂的牢度为3级或 $3{\\sim}4$ 级。几种DPP颜料主要物化指标见表2-2-50。  \n\n表2-2-49吡咯井吡咯二酮系颜料结构式  \n\n\n<html><body><table><tr><td>DPP结构式</td><td>主要品种</td><td></td><td>Y</td></tr><tr><td rowspan=\"4\">X X X- 0</td><td>P.0.73</td><td>C(CH)</td><td>H</td></tr><tr><td>P. R. 254</td><td>Cl</td><td>H</td></tr><tr><td>P. R. 255</td><td>H</td><td>H</td></tr><tr><td>P. R. 264</td><td>Ph</td><td>H</td></tr></table></body></html>  \n\n表2-2-50几种DPP颜料主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>DPP. 3</td><td>PP 25</td><td></td><td>PP </td></tr><tr><td>C. L Pigment</td><td>Orange 73</td><td>Red 254</td><td>Red 255</td><td>Red 264</td></tr><tr><td>C.I结构号</td><td>56117</td><td>56110</td><td>561050</td><td>一</td></tr><tr><td>CAS No</td><td>[71832-85-4]</td><td>[84632-65-5]</td><td>[120500-90-5]</td><td>二</td></tr><tr><td>EU No</td><td>[276-057-2]</td><td>[402-400-4]</td><td></td><td>一</td></tr><tr><td>分子式</td><td>CaHNO</td><td>C HoClNO</td><td>CHzNzO</td><td>一</td></tr><tr><td>分子量</td><td>400.52</td><td>357.19</td><td>288.30</td><td></td></tr><tr><td>色光</td><td>艳橙色</td><td>亮红色</td><td>黄光红</td><td>蓝光红</td></tr><tr><td>密度/(g/cma）</td><td>1.3</td><td>1.60</td><td>1.41</td><td>1.35</td></tr><tr><td>吸油量/(g/100g）</td><td>53</td><td>60</td><td>40~59</td><td>57</td></tr><tr><td>耐光性/级</td><td>7~8</td><td>7~8</td><td>7~8</td><td>7~8</td></tr><tr><td>耐温性/C</td><td>200</td><td>200</td><td>200</td><td>200</td></tr><tr><td>耐酸性/级</td><td>5</td><td>4~5</td><td>5</td><td>5</td></tr><tr><td>耐碱性/级</td><td>5</td><td>4~5</td><td>5</td><td>5</td></tr><tr><td>耐水性/级</td><td>5</td><td>4~5</td><td>5</td><td></td></tr><tr><td>耐油性/级</td><td>4~5</td><td>4~5</td><td>4~5</td><td>4~5</td></tr></table></body></html>  \n\n(5）喹酞酮系颜料喹酮本身是一类古老的化合物，但作为颜料的使用历史不长。是  \n\n![](images/5b0b72fdad132cba72c6e0a309de2197eb1a9368bdaa6c8713c121646f171721.jpg)  \n图2-2-7 颜料黄138结构式  \n\n20世纪70年代由HF公司研制开发的新型高档有机颜料。该类颜料具有耐晒性、耐候性、耐热性、耐溶剂性及耐迁移性。色光主要为绿光黄色，颜色鲜艳，其中最为典型品种是BASF公司生产的P.Y.138，具有高着色强度，优异的牢度。最近几年国内也有个别厂家生产。主要用于汽车漆、高档工业漆及塑料中着色。颜料黄138结构式如图2-2-7所示。颜料黄138主要物化指标见表2-2-51。  \n\n表2-2-51颜料黄138主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>C. I. Pigment</td><td>Yellow 138</td><td>色光</td><td>红光黄</td><td>耐光性/级</td><td>7~8</td></tr><tr><td>C.L结构号</td><td>56300</td><td>密度/(g/cm²)</td><td>1.82</td><td>耐酸性/级</td><td>5</td></tr><tr><td>CAS No</td><td>[30125-47-4]</td><td>平均粒径/μm</td><td>0.22~0.39</td><td>耐碱性/级</td><td>5</td></tr><tr><td>EU No</td><td>[250-063-5]</td><td>吸油量/(g/100g)</td><td>30~40</td><td>耐水性/级</td><td>5</td></tr><tr><td>分子式</td><td>C26 HClNO</td><td>熔点/C</td><td>480</td><td>耐油性/级</td><td>5</td></tr><tr><td>分子量</td><td>693.94</td><td>耐温性/C</td><td>250</td><td>pH（10%水浆）</td><td>？</td></tr></table></body></html>  \n\n(6）葱系颜料葱醒系颜料是指分子中含有葱构造或以葱为起始原料的一类颜料，是一类还原颜料。色泽非常稳定，色谱范围较广，但生产特别复杂，生产成本过高。其颜料具有优良的耐光牢度，很好的耐溶剂性与耐迁移性。几种葱系颜料主要物化指标见表2-2-52。  \n\n表2-2-52几种葱醒系颜料主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>葱醒黄P.Y.24</td><td>葱红P.R.168</td><td>蕙醒红P.R.177</td><td>蕙醒蓝P.B.60</td></tr><tr><td>C. I. Pigment</td><td>Yellow 24</td><td>Red 168</td><td>Red 177</td><td>Blue 60</td></tr><tr><td>C.L结构号</td><td>70600</td><td>59300</td><td>65300</td><td>69800</td></tr><tr><td>CAS No</td><td>[475-71-8]</td><td>[4378-61-4]</td><td>[4051-63-2]</td><td>[81-77-6]</td></tr><tr><td>EU No</td><td>[207-498-0]</td><td>[224-481-3]</td><td>[223-754-4]</td><td>[201-375-5]</td></tr><tr><td>分子式</td><td>CasHNO</td><td>CaHaBrO</td><td>CHNO</td><td>CaHNO</td></tr><tr><td>分子量</td><td>408.42</td><td>464.11</td><td>444</td><td>442.42</td></tr><tr><td>色光</td><td>红光黄</td><td>黄光红</td><td>红光</td><td>红光蓝</td></tr><tr><td>密度/（g/cm²）</td><td>1.55~1.65</td><td>1,40~1.99</td><td>1.45~1. 53</td><td>1.45~1.54</td></tr><tr><td>吸油量/（g/100g）</td><td>39~49</td><td>40~58</td><td>55~62</td><td>27~80</td></tr><tr><td>耐光性/级</td><td>7</td><td>8</td><td>8</td><td>8</td></tr><tr><td>耐温性/℃</td><td>250</td><td>180</td><td>250</td><td>230</td></tr><tr><td>耐酸性/级</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>耐碱性/级</td><td>4</td><td>5</td><td>5</td><td>5</td></tr><tr><td>耐水性/级</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>耐油性/级</td><td>5</td><td>4~5</td><td>5</td><td>5</td></tr></table></body></html>  \n\n葱醒黄（P.Y.24）呈红光黄色，与铝粉浆复合使用，具有很好的耐候性与耐温性，非常适用于汽车面漆与其他多种涂料着色。  \n\n葱红（P.R.168）呈黄光大红色，颜色鲜艳，具有优异的各项应用牢度，其耐晒牢度与耐候牢度是已知有机颜料中最好的品种之一，几乎耐所有有机溶剂，主要应用于高档汽车漆与工业漆。但应用于烘烤温度过高的涂料中，耐重涂性不是非常理想，一般比较适合$120{\\sim}160\\ensuremath{\\uptau}$ 烘烤条件。  \n\n葱醒红（P.R.177）主要应用于高档工业漆、塑料等。具有很好的透明度和各项应用牢度，但用 $\\mathrm{TiO_{2}}$ 冲淡耐候牢度明显下降，同时会与铝或其他还原性物质起反应。 4  \n\n葱酿蓝（P.B.60）作为颜料使用前，一直当成还原染料使用。具有良好的透明性和耐候性，着色力强，但较菁蓝要低些。主要应用于轿车漆，特别是金属漆中着色。．  \n\n（7）系与茜酮颜料系与茜酮颜料均属还原颜料。花系颜料主要为红色品种，也称花红颜料，有大红与紫红等色谱；茜酮颜料品种较少，主要有颜料黄194与颜料橙43。其性能可与喹吖啶酮红相媲美，耐晒性、耐候性较好，耐热性高达 $350^{\\circ}\\mathrm{C}$ 以上。目前颜料品种较多，但商品化品种比较少，主要应用于高档工业漆、耐热要求较高的涂料产品。几种花系与茜酮颜料主要物化指标见表2-2-53。  \n\n苝红（P.R.179）是系颜料中最为重要的品种，尤其适用于高档汽车漆（OEM)及末道漆，呈正红色，具有极好的耐候牢度和耐溶剂性，对碱十分稳定，可应用于各类水性漆。  \n\n花红（P.R.123）呈中红色，具有好的耐候牢度和耐溶剂性，比较适合应用于一般涂料或建筑乳胶漆着色。  \n\n花红（P.R.224）品种较多，主要适用于工业漆，尤其是轿车面漆，高透明性品种主要用于金属漆。由于它是一个酸酐，对碱十分敏感，一般不能用于碱性体系。  \n\n茜酮橙（P.O.43）是反式异构体，呈红光橙色，比顺式异构体（颜料黄194）商业价值要大得多。是涂料工业的一种重要橙色品种，本色与深色在户外曝晒容易变暗，用 $\\mathrm{TiO}_{2}$ 冲淡具有较好的耐候牢度。  \n\n表2-2-53几种花系与茜酮颜料主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>红P. R. 123</td><td>苝红 P. R. 179</td><td>花红P.R.224</td><td>茜酮橙P.O.43</td></tr><tr><td>C. I. Pigment</td><td>Red 123</td><td>Red 179</td><td>Red 224</td><td>Orange43</td></tr><tr><td>C.L结构号</td><td>711450</td><td>71130</td><td>71127</td><td>71105</td></tr><tr><td>CAS No</td><td>[24108-89-2]</td><td>[5521-31-3]</td><td>[128-69-8]</td><td>[4424-06-07]</td></tr><tr><td>EU No</td><td>[246-018-4]</td><td>[226-886-1]</td><td>[204-905-3]</td><td>[224-597-4]</td></tr><tr><td>分子式</td><td>CHzsNO</td><td>CaHNO</td><td>CHOs</td><td>CasH2NO</td></tr><tr><td>分子量</td><td>630.64</td><td>418.40</td><td>392.32</td><td>412.40</td></tr><tr><td>色光</td><td>红色</td><td>暗红色</td><td>蓝光红</td><td>红光橙</td></tr><tr><td>密度/（g/cma）</td><td>1. 43 ~1. 52</td><td>1.41~1. 65</td><td>1. 58~1.75</td><td>1. 49~1.87</td></tr><tr><td>吸油量/(g/100g)</td><td>45~49</td><td>17~50</td><td>25~50</td><td>96</td></tr><tr><td>耐光性/级</td><td>7</td><td>8</td><td>7~8</td><td>6~7</td></tr><tr><td>耐温性/C</td><td>220</td><td>200</td><td>260</td><td>200</td></tr><tr><td>耐酸性/级</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>耐碱性/级</td><td>4</td><td>5</td><td>3</td><td>5</td></tr><tr><td>耐水性/级</td><td>5</td><td>5</td><td>5</td><td>5</td></tr><tr><td>耐油性/级</td><td>5</td><td>5</td><td>5</td><td>5</td></tr></table></body></html>  \n\n(8）硫靛类颜料靛类颜料也属于还原颜料。其色光鲜艳，着色力高，色谱主要为红色与紫色，常应用于汽车漆与高档塑料制品。由于对人体毒性较小，也可作为食用色素使用。  \n\n![](images/848f0a50cf39023f6570dfcf8b6ef36f4c8e5efd87c20af2cc3b1eb391ee57b5.jpg)  \n图2-2-8颜料红88结构式  \n\n硫靛红（P.R.88）是硫靛的四氯代衍生物，主要应用于涂料中，呈鲜艳紫红色，具有较好的遮盖力、耐晒牢度及耐候牢度。硫靛红（P.R.181）对人体几乎无毒，可作为食用色素使用。颜料红88结构式如图2-2-8所示。颜料红88主要物化指标见表2-2-54。  \n\n表2-2-54颜料红88主要物化指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td><td>项目</td><td>指 标</td></tr><tr><td>C. L Pigment</td><td>Red 88</td><td>色光</td><td>红光紫</td><td>耐光性/级</td><td>6~7</td></tr><tr><td>C.I结构号</td><td>73312</td><td>密度/(g/cm)</td><td>1. 47~1.90</td><td>耐酸性/级</td><td>5</td></tr><tr><td>CAS No</td><td>[14295-43-3]</td><td>早均粒径/μm</td><td>0.10</td><td>耐碱性/级</td><td>3~4</td></tr><tr><td>EU No</td><td>[238-222-7]</td><td>吸油量/（g/100g)</td><td>33~58</td><td>耐水性/级</td><td>5</td></tr><tr><td>分子式</td><td>CHClOS</td><td>熔点/C</td><td>460</td><td>耐油性/级</td><td>5</td></tr><tr><td>分子量</td><td>434.14</td><td>耐湿性/℃</td><td>180</td><td>pH（10%水浆）</td><td>7.0</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 561,
+        "chunk": "# 三、填料 (体质颜料)  \n\n在涂料中使用的体质颜料主要品种有天然的碳酸钙、重晶石粉、石英粉、滑石粉、高岭土、云母粉、硅灰石、白云石、凹凸棒土（含水硅酸镁铝）以及人工合成的轻质碳酸钙、沉淀硫酸钡、合成硅酸钙、硅铝酸钠等品种。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 562,
+        "chunk": "# 1.碳酸钙  \n\n碳酸钙是无臭、无味的白色粉末，是应用最广的填料之一，化学式 $\\mathbf{CaCO_{3}}$ ，分子量100.09。碳酸钙主要分为两大类（表2-2-55）。  \n\n![](images/34ec3c98661a83e3145de0172222b9462f75a3e059cec3a95dae2e2c8cb8c3fc.jpg)  \n\n沉淀碳酸钙（轻质）是指用化学方法合成的碳酸钙，其白度在 $90\\%$ 左右，密度 $2.6g/$ $\\mathrm{cm}^{3}$ 。重质碳酸钙是以天然方解石、石灰石、白垩、贝壳为原料，用机械的方法将其磨碎，并达到一定的细度。碳酸钙性能见表2-2-56。  \n\n表2-2-56碳酸钙性能  \n\n\n<html><body><table><tr><td>碳酸钙品种</td><td>沉降体积/（mL/g）</td><td>吸油值/（mL/100g)</td><td>比表面积/（m²/g）</td></tr><tr><td>沉淀碳酸钙（轻质）</td><td>2.4~3.3</td><td>60~90</td><td>5左右</td></tr><tr><td>普通重质碳酸钙</td><td>1.2~1.9</td><td>27左右</td><td>1左右</td></tr><tr><td>重质微细碳酸钙</td><td>2.2~2.6</td><td>48左右</td><td>1.45~2.1</td></tr><tr><td>微细、超细碳酸钙</td><td>2.6~8.0</td><td>150~300</td><td>27~87</td></tr></table></body></html>  \n\n在涂料工业中，因碳酸钙具有价廉、无毒、色白、资源丰富、易于在配方中混合及性质较为稳定等优点，被大量用于填充剂。具体来说，用于底漆中，可增强底漆对于基层表面的沉积性和渗透性；用于厚漆中，可以使涂料增稠、加厚，起填充和补平作用；在半光或无光漆中，则是理想的消光填料；在金属防锈涂料中，碳酸钙水解能生成氢氧化钙，可与铁表面形成氢键而增强涂膜的附着力，还可以吸收 $\\mathrm{H^{+}}$ ；重质碳酸钙用在建筑涂料中，吸油量较低，对乳液需要量低，既可以降低乳胶漆的成本，又起骨架作用，增加涂膜厚度，提高机械强度、耐磨性等，因而成为乳胶漆中最常用的体质颜料。  \n\n纳米碳酸钙具有细腻、均匀、白度高、光学性能好等优点，随着纳米碳酸钙的粒子微细化，填料粒子表面的原子数目占整个总原子数目的比例增大，使粒子表面的电子结构和晶体结构都发生变化，到了纳米级水平。纳米填料粒子会表现出常规粒子所没有的表面效应和小尺寸效应，具有一系列优良的理化性能。 9  \n\n将纳米碳酸钙添加到涂料中具有增强作用，并可提高涂料的透明性、触变性和流平性。同时，涂膜具有纳米粒子表面效应，形成屏蔽作用，从而达到抗紫外线老化的效果与提高涂料的机械强度等多种优点。",
+        "category": " Introduction"
+    },
+    {
+        "id": 563,
+        "chunk": "# 2.硫酸钡  \n\n硫酸钡的化学成分是 $\\mathrm{{BaSO_{4}}}$ ，天然产品称为重晶石粉，合成产品称为沉淀硫酸钡。它  \n\n对光的吸收能力高，可以吸收 $\\mathbf{x}$ 射线，外观是致密的白色粉末，密度较大，为 $4,3\\sim4,5\\mathbf{g}/$ $\\mathsf{c m}^{3}$ ，也有的资料认为在 $4,0\\sim4,9$ 之间。通常密度越大的体质颜料其折射率就越大，故硫酸钡的折射率也达到了 $1.63\\sim1.65$ ，表现出颜色较白，具有一定的遮盖力。  \n\n硫酸钡耐酸、耐碱、耐光、耐热，熔点高达 $1580^{\\circ}\\mathrm{C}$ ，不溶于水，吸油量低，天然产品 吸油量在 $9\\mathbf{g}/100\\mathbf{g}$ 左右，合成产品为 $10\\mathrm{\\sim}15\\mathrm{\\g}/100\\mathrm{g}$ 要  \n\n天然产品硫酸钡纯度为 $85\\%\\sim95\\%$ ，粒度较粗，粒度分布宽，一般为 $2.0\\sim30\\mu\\mathrm{m}$  \n\n合成产品硫酸钡纯度通常都大于 $97\\%$ ，粒度小，分布均匀，一般在 $0.3\\mu\\mathrm{m}$ 到几微米之间。  \n\n重晶石粉在涂料工业中主要用于底漆中，利用它的低吸油量，耗漆量少，可制成厚膜底漆，填充性好、流平性好、不渗透性好，增加涂膜硬度和耐磨性。  \n\n合成硫酸钡性能要优于天然产品，其白度高，质地细腻，抗起霜，抗铁锈污染，是建筑涂料常用填料之一。其缺点是密度大，漆料易沉淀。",
+        "category": " Introduction"
+    },
+    {
+        "id": 564,
+        "chunk": "# 3.二氧化硅  \n\n二氧化硅的分子式是SiO，有天然产品和人造产品两大类，主要成分都是二氧化硅，部分品种是含水二氧化硅。  \n\n由于天然产品的来源和合成路线的不同已形成系列产品，在外观和使用性能上有很多差异。在化学属性上都具有 $\\mathrm{SiO}_{2}$ 的特性，为白色粉末中性物质，化学稳定性较高，耐酸不耐碱，不溶于水，耐高温，但在物理状态上却有极大的差别。一般来讲，天然产品颗粒粗大，吸油量很低，颜色不够纯净，白色或近灰色，比较致密，质地硬，耐磨性强。  \n\n天然二氧化硅密度小，是体质颜料中折射率较低的品种，但比合成二氧化硅高，达$1.54\\mathrm{g}/\\mathrm{cm}^{3}$ 左右。合成产品颗粒一般较细，吸油量高，颜色白或略带蓝相，折射率较低，在1.45左右。  \n\n(1）天然无定形二氧化硅无定形是指非结晶形，颗粒大部分在 $40\\mu\\mathrm{m}$ 以下，为细白粉末，密度 $2.658/\\mathrm{cm}^{3}$ ，折射率 $1.54{\\sim}1.55\\$ ，吸油量 $29\\sim31\\mathbf{g}/100\\mathbf{g}$ ，熔点 $1704\\Upsilon$ $\\mathbf{pH}$ 为7。因其价廉和化学稳定性好，在涂料中广泛用于填料，如用于底漆、平光漆和地板漆等。  \n\n(2）天然结晶形二氧化硅天然结晶形二氧化硅即天然石英砂，经纯化、研磨和过筛制成。为白色粉末，吸油量 $24\\sim36\\mathbf{g}/100\\mathbf{g}$ ，密度 $2.65g/\\mathrm{cm}^{3}$ ，折射率1.55， $\\mathfrak{p H}$ 为7，粒径$1.5\\sim9.0\\mu\\mathrm{m}$ 。由于它色白、耐热、化学稳定性好，在涂料中不仅起到填充作用，而且涂料涂刷性及耐候性均好。粉状石英砂还大量用于真石漆和饰纹涂料中。  \n\n(3)天然硅藻土硅藻土为含水二氧化硅，水的数量不定，其分子式 $\\mathrm{SiO}_{2}\\cdot\\mathrm{\\Delta}n\\mathrm{H}_{2}\\mathrm{O}$ 它是海生生物的遗骸，资源非常丰富。由于来源和制造方法不同，质量波动比较大，可由灰色粉末至细白粉末。其密度很小，为 $\\scriptstyle2_{8}/\\cos^{3}$ ，质轻，颗粒蓬松，折射率相当低 $(1,42\\sim$ 1.48)，颗粒较粗，粒径为 $4\\sim12\\mu\\mathrm{m}$ ，具有多孔性，吸油量高达 $120{\\sim}180\\mathbf{g}/100\\mathbf{g}$ 。它的多孔性特点具有提高遮盖力的作用，主要用于平光涂料和厚质涂料中。  \n\n(4）沉淀法二氧化硅沉淀法二氧化硅的外观为白色无定形（非晶体）粉末，密度 $\\scriptstyle2_{\\mathbf{{g}}/}$ $\\mathsf{c m}^{3}$ ，吸油量 $110\\sim160\\mathbf{g}/100\\mathbf{g}$ ，折射率1.46，平均粒径 $0.02\\sim0.11\\mu\\mathrm{m}$ 。其化学成分为$\\mathrm{SiO_{2}}\\cdot\\ n\\mathrm{H}_{2}\\mathrm{O}$ ，其结合水含量通常为 $4.6\\%$ ，具有吸湿性。产品中还有一定量的游离水分，在较高温度下灼烧可失去部分水分。在涂料工业中用于体质颜料、中性颜料，其稳定性好，但难以分散。  \n\n(5）合成气相二氧化硅合成气相二氧化硅又称白炭黑，是一种极纯的无定形二氧化硅，在不吸附水的情况下，其纯度超过 $98.8\\%$ 。外观为带蓝相或白色松散粉末，密度 $2,2_{8}/$ $\\mathrm{cm}^{3}$ ，折射率-1.45。粒度极为微细，平均粒径为 $0.012\\mu\\mathrm{m}$ ，粒度范围 $0.004{\\sim}0.17\\mu\\mathrm{m}$ ，由于颗粒细，比表面积可达 $50\\mathrm{\\sim}350\\mathrm{m}^{2}/\\mathrm{g}$ ，吸油量高达 $280\\mathbf{g}/100\\mathbf{g}$ 。化学稳定性强，除了氢氟酸和强碱外，不溶于所有溶剂。  \n\n气相二氧化硅比一般的二氧化硅性能优良。经表面处理后，按照用途不同形成系列产品，主要有疏水和憎水两大类。它主要用于黏结剂、涂料、制药、塑料、硅橡胶等行业。  \n\n气相二氧化硅在液体介质中呈现增稠性和触变性，在静止情况下形成一定的结构，从而使体系黏度提高，当受外界机械力作用时，形成的结构被破坏，体系的黏度降低，利用这个性能可使涂料呈现适度的触变结构，从而使较厚的涂膜不致出现流挂现象，一般加人1%～4%就可获得适宜的触变性。  \n\n气相二氧化硅还可防止颜料在涂料中下沉，因为二氧化硅颗粒可形成三维链状结构，轻微的触变性可改善涂料的涂覆性，减轻流挂及发花现象。由于颗粒极小，在涂料中不能起平光作用。使用憎水型气相二氧化硅可作为防沉降剂，同时提高涂膜的耐水性。  \n\n(6）纳米二氧化硅纳米二氧化硅是无定形白色粉末，表面存在不饱和的残键及不同键合状态的羟基，其分子状态呈三维链状结构，这种结构可以赋予涂料优良的触变性和分散稳定性。同时，纳米 $\\mathbf{S}_{1}^{\\mathrm{{iO}_{2}}}$ 具有极强的紫外线反射能力，在涂料中能形成屏蔽作用，达到抗紫外线老化的目的，同时增加涂料的隔热性。  \n\n纳米 $\\mathrm{SiO}_{2}$ 是一种良好的涂料添加剂。在涂料中加入纳米二氧化硅可明显改善涂料的开罐效果，涂料不易分层，具有触变性，防流挂，施工性能良好，抗老化性、热稳定性、强度等都会有所提高。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 565,
+        "chunk": "# 4.硅酸盐类  \n\n(1）滑石粉滑石粉是将天然滑石矿粉碎而成，其主要成分为水合硅酸镁，分子式$3\\mathrm{M}_{8}\\mathrm{O}\\cdot\\mathrm{SiO}_{2}\\cdot\\mathrm{H}_{2}\\mathrm{O}$ ，为白色鳞片状结晶，并含有纤维状物，含有杂质者呈淡黄色、淡绿色、淡蓝色等。滑石粉晶体属单斜晶系，呈六方形或菱形。滑石粉中与氧结合的镁原子夹在两个片状二氧化硅之间，形成层状结构，相邻层之间依靠弱的范德华力结合在一起，当有剪切力作用时，层间容易分离。滑石粉是已知矿物中最软的，莫氏硬度1，密度 $2,7\\sim2.8\\&/$ $\\mathrm{cm}^{3}$ ，化学性质不活泼，在加热至 $900\\mathrm{^\\circC}$ 高温时仍稳定，非导电体，有滑腻感。  \n\n滑石粉其片状结构对其应用具有决定性的影响。其吸油量也比球状填料大，能影响涂料的黏度和流变性质，通常表现出结构黏度的性质。在临界PVC以下时，滑石粉几乎没有速盖力，一旦超过临界PVC时，其遮盖力变大。与云母相比，滑石粉的增强效果没有那么显著，但却可以降低裂纹敏感性。  \n\n在用于典型的内墙涂料时，可提高耐擦洗性；用于防腐涂料时，由于延长了腐蚀物质的扩散路径，可改善防护效果；与沉淀硅酸盐相似，滑石粉也可以充当颜料的隔离剂，提高颜料的着色效果。其缺点在于易于粉化，因此必须选择适当用量。  \n\n(2）高岭土高岭土通常也称瓷土、中国黏土，主要矿物成分为高岭石，它是各种结晶岩破坏后的产物，分子式 $\\mathrm{Al_{2}O_{3}}\\cdot\\mathrm{SiO_{2}}\\cdot n\\mathrm{H}_{2}\\mathrm{O}$ ，它也是片状结构。  \n\n由于其电荷分布的作用，高岭土在水介质中形成一种不很稳定的结构。电荷的分布是这样的，即在片状颗粒的边缘带正电，表面带负电。如果用量大，这种作用会形成凝胶，使涂料不能流动，且会受到浸润剂和分散剂的抑制。一般加人高岭土，可以改善触变性和抗沉淀性。烧黏土对流变性能没有影响，但却可以像没有经过处理的黏土一样，具有消光作用、增加遮盖性和增加白度，这些都类似于滑石粉。  \n\n高岭土一般吸水性较大，不适合提高涂料的触变性，不适合于制备僧水性涂膜。高岭土产品粒径在0.2～1μm之间。粒径大的高岭土吸水性小；消光效果好，粒径小的高岭土$(1\\mu\\mathbf{m}$ 以下)，可用于半光涂料和内用涂料。  \n\n高岭土可分为烧高岭土和水洗高岭土。一般来说，烧高岭土的吸油量、不透明性、孔隙率、硬度和白度都高于水洗高岭土。二者性能对比见表2-2-57。  \n\n表2-2-57烧高岭土和水洗高岭土比较  \n\n\n<html><body><table><tr><td>性能</td><td>烧高岭土</td><td>水洗高岭土</td><td>性能</td><td>烧高岭土</td><td>水洗高龄土</td></tr><tr><td>折射率</td><td>1.62</td><td>1.56</td><td>吸油量/（g/100g）</td><td>50~95</td><td>30~45</td></tr><tr><td>相对密度</td><td>2.50~2.63</td><td>2.58</td><td>比表面积/(m²/g)</td><td>8~16</td><td>6~20</td></tr><tr><td>莫氏硬度</td><td>3~4</td><td>2</td><td>赫格曼细度/pum</td><td>4~5.5</td><td>5~6</td></tr><tr><td>GE白度/%</td><td>84~97</td><td>80~92</td><td>10%悬浮液的pH</td><td>5.0~6.0</td><td>3.5~8.0</td></tr><tr><td>中位粒径/μm</td><td>0.8~2. 9</td><td>0.2~4.8</td><td>粒子形状</td><td>片状</td><td>卷曲状/片状</td></tr></table></body></html>  \n\n(3）硅灰石硅灰石的主要成分为偏硅酸钙，理论组成是 $\\mathrm{CaSiO_{3}}$ ，分子量116.4。硅灰石颜色为白色，莫氏硬度 $4,5\\sim5,0$ ，相对密度2.8，折射率1.62。它具有湿膨胀性低、吸油率低、电耗率低等特性。硅灰石属三斜晶系，经常呈针状或纤维状，在一定程度上硅灰石可以代替石棉使用。它具有增强作用、降低裂纹敏感性及一定的增稠和触变作用。  \n\n硅灰石在涂料工业中可以作为体质颜料兼增量剂使用，它能增加白色涂料明亮的色调，在不使涂料白度和遮盖力下降的条件下，能取代部分钛白粉，并能长时间保持这种色调。硅灰石吸油量低，具有很高的填充量，可以降低涂料成本；硅灰石的针状结晶使它可以作为涂料良好的平光剂，并可改善涂料的流平性；硅灰石的粒子形状，使它还可以作为涂料良好的悬浮剂，使色漆的沉淀柔软易于再分散；硅灰石碱性大，非常适用于聚醋酸乙烯涂料，能使着色颜料分散均匀；硅灰石还具有改进金属涂料的防腐蚀能力，在自清洁型涂料中作为增强剂；除用于水性涂料外，还可以用于底漆、中间涂层、油性涂料、路标涂料等；在沥青涂料中可用来取代石棉；硅灰石用于涂料中，能提高涂料的耐磨性和耐候性，其原因是由于它的片状和纤维状结构，在涂膜中薄片相叠，除能增加涂膜的屏蔽性外，还有较强的反射紫外线的能力，因而提高了涂膜的耐老化性；硅灰石和二氧化硅一样，可增加涂膜的遮盖力。据资料介绍，用它代替 $20\\%$ 的钛白也不会改变涂膜的不透明性和其他性质；硅酸盐和二氧化硅的不透明度大，原因是粒子表面富有亲水性。水向这些颜料粒子中扩散要比向乳胶粒子中扩散容易得多，干燥以后在融合的乳液涂膜内形成微细的空气/二氧化硅界面，提高了涂膜的不透明性。  \n\n人工合成产品为水合硅酸钙，其化学组成为 $\\mathrm{CaSiO_{3}}\\cdot n\\mathrm{H}_{2}\\mathrm{O}$ 。它是由硅藻土与石灰混合后，高温下在水浆中形成，这种合成产品又可分为常规型和处理型。它是白色蓬松粉末，比天然硅灰石质轻、蓬松，具有较高吸附能力，粒度较小（ $10\\sim12\\mu\\mathrm{m})$ ，高比表面积$(175m^{2}/\\mathbf{g})$ ，吸油量高达 $280\\mathbf{g}/100\\mathbf{g}$ ，密度 $2.26g/\\mathrm{cm}^{3}$ ，折射率1.55， $\\mathsf{p H}$ 为9.8。  \n\n(4）云母粉云母是复杂的硅酸盐类。从化学组成来看，云母就是滑石粉的晶格中的硅一部分被铝所取代，属单斜晶系，晶体常呈六方片状，属于片状填料，有玻璃光泽。云母的组成非常复杂，因为含有各种不同的金属盐，所以有不同的光泽。  \n\n云母粉是天然云母经过干式或湿式研磨后，除去杂质，经分级过滤、干燥而成。外观为银白色至灰色，密度在 $\\boldsymbol{2.82g/\\mathrm{cm}^{3}}$ 左右，折射率1.58，吸油量 $40\\sim70\\mathrm{g}/100\\mathrm{g}$ ，硬度2.5，粒径5～20μm。 1  \n\n云母粉在涂料中的水平排列可阻止紫外线的辐射而保护涂膜，可以改善整个系统的光稳定性，还可防止水分穿透。云母粉具有优良的耐热性、耐酸性、耐碱性和电气绝缘性，能起阻尼、绝缘、减震的作用，能提高涂膜的机械强度、抗粉化性、耐久性，可用于阻尼漆、防  \n\n火漆、乳胶漆等。  \n\n在含有滑石粉的配方中加入云母，涂料的抗腐蚀性提高，表面硬度增加，耐擦洗性提高，颜料的效率提高。  \n\n(5）绢云母绢云母是一种细粒的白云母，属层状结构的硅酸盐，结构是由两层硅氧四面体夹着一层铝氧八面体构成的复式硅氧层。分子式 $\\mathrm{K_{2}O_{3}A l_{2}O_{3}\\bullet\\mathrm{SiO_{2}\\bullet2H_{2}O}}$ ，晶体为鳞片状，富弹性，可弯曲。其粒度 $200\\sim3000$ 目，吸油量 $20\\mathrm{\\sim}50\\mathbf{g}/100\\mathbf{g}$ . $\\mathbf{\\pH}$ 为 $5\\sim8$ 。绢云母具有良好的耐酸性、耐碱性，化学稳定性好，有中等的干遮盖力和较好的悬浮性。用在涂料中可提高涂料的耐候性，阻止水汽穿透，防止龟裂，延迟粉化。  \n\n(6）合成硅酸铝合成硅酸铝实际上是硅酸铝钠，是一种无定形高分散的体质颜料，密度 $2.0{\\sim}2.1\\mathbf{g}/\\mathrm{cm}^{3}$ ， $\\mathsf{p H}$ 为 $9.5\\sim10.5\\$ ，它是一种优良的涂料原料。合成硅酸铝通常粒子粒径为 $1.5\\mu\\mathrm{m}$ ，粒径小，粒度分布窄，没有沉淀分层现象，使涂料的悬浮性大大提高，使涂料色相纯正，着色力强，遮盖力提高，可提高涂料的分散性及细度指标，对涂料的外观、光泽度、丰满度、硬度都有良好的效果。  \n\n合成硅酸铝不会与磷酸盐分散剂作用，可使乳胶漆具有良好的分散稳定性。合成硅酸铝的超细性能及高分散性，能使乳胶漆稍微增稠，以防止颜料沉淀及表面分层现象。另外乳胶漆的涂膜耐擦洗性及耐候性不会因超细硅酸铝的加入而下降。合成硅酸铝也可用于无光和半光溶剂型漆及白二道漆等颜料体积浓度较高的配方中，替代钛白粉用量的 $10\\%\\sim20\\%$ ，漆的遮盖力不会减弱。  \n\n合理采用硅酸铝替代部分钛白粉生产的乳胶漆具有以下特点。  \n\n$\\Phi$ 由于粒径小、粒径分布窄，没有沉淀分层现象，填料的悬浮性大大提高，开罐效果良好。$\\textcircled{2}$ 涂料色相纯正，着色力强，遮盖力提高。$\\textcircled{3}$ 由于改善了涂料的分散性及细度指标，对涂料的外观、光泽度、丰满度、硬度以及分散性都有良好效果。  \n\n$\\textcircled{4}$ 由于节省了 $10\\%\\sim20\\%$ 金红石型钛白粉，从而大幅度降低涂料生产成本。此外，合成硅酸铝呈碱性，在涂料中对酸碱性起到缓冲作用，特别是在醋酸乙烯乳胶漆体系中，能防止在贮存过程中因醋酸乙烯酯水解导致乳胶漆 $\\mathsf{p H}$ 下降。  \n\n由于其比表面积大，吸油量高达 ${75\\sim150\\mathbf g/10\\mathbf g}$ ，而且必须彻底分散才能发挥其增效作用，否则容易造成后增稠。此外，它具有消光作用，故不宜用在高光漆中。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 566,
+        "chunk": "# 四、特种功能颜料",
+        "category": " Introduction"
+    },
+    {
+        "id": 567,
+        "chunk": "# 1.珠光颜料  \n\n珠光颜料因其光泽强、装饰效果好、无毒、耐光性、耐候性、耐酸性、耐碱性、耐热性、分散性好、不导电、不导磁等优良特性，而使其广泛应用于汽车漆、摩托车漆、自行车漆及玩具、装饰品涂层等。珠光颜料是一种片状效应颜料，有高的折射率，由于光的干涉作用呈现珠光色泽。这种颜料呈现珠光色泽是依靠它的光学性能，所以常有化学组成不同的珠光颜料具有近似的珠光效果。  \n\n天然的珠光颜料来自珍珠、鱼鳞。人工合成的品种早期有含 $\\mathbf{H}_{\\mathbf{B}\\imath}\\mathbf{C}\\mathbf{l}_{2}$ 、PbHPO或PbHAsO的制品，后来出现了碱式碳酸铅型珠光颜料，均有一定毒性。在20世纪60年代初又出现毒性较低的氯氧化秘型（BiOCI）珠光颜料。  \n\n如今生产的珠光颜料以云母钛型为主，它是以云母、片状石英、片状氧化铝或片状玻璃粉末为基材，在其表面包覆一层高折射率的金属氧化物透明薄膜复合而成，当光照射到珠光颜料平整界面时，会产生反射光和折射-反射光，它们之间的相互干涉产生一种立体感强的珠光色彩。  \n\n云母钛型珠光颜料是以 $\\mathrm{TiO}_{2}$ 沉积在玻璃光泽的白云母或金云母片上，一般呈银白色的珠光色泽，如改变 $\\mathrm{TiO}_{2}$ 的厚度可以产生彩虹系列的珠光颜料。如在 $\\mathrm{TiO_{2}}$ 中加人 $\\mathrm{Fe}_{2}\\mathrm{O}_{3}$ 或少量的 $\\mathrm{Cr}_{2}\\mathrm{O}_{3}$ ，可以产生金色视觉的颜料，如全部以 $\\mathrm{Fe}_{2}\\mathrm{O}_{3}$ 沉积于云母片可以得到青铜色或紫铜色等金属光泽。目前还有在沉积 $\\mathrm{TiO_{2}}$ 后的珠光颜料配上各种颜料或色浆调色，可得到一系列的着色珠光颜料，如有红、蓝、绿、紫等深浅不同的品种。  \n\n金属氧化物包膜云母氧化铁珠光颜料是一种新型的合成珠光颜料，它以云母氧化铁粉末为基片，在其表面包上一层金属氧化物膜，利用二者对光的折射率的差异，干涉出五光十色，其作用的基本原理如下：当光线由低折射区域射向其表面时，部分光被反射而部分光被透射。透射光到达下一颜料片层时又被再次反射和透射，许多颜料层构成多层次的反射，而人的眼睛又不可能聚焦于任何一颜料层上，从而产生了多层光反射的交叉网络效果，这就是  \n\n![](images/f31444829e4001211732f43fc437fdf148b29cd4c144a097ee78bf29ce711e07.jpg)  \n图2-2-9云母氧化铁颜料薄膜反射示意图I一人射光；t一金属氧化物层的几何厚度； $R_{1}-\\widehat{\\ast}$ 属氧化物层的反射光；R一云母氧化铁的反射光；mo一介质的折射率； $n_{1}$ 一金属氧化物薄膜的折射率：  \n\nn—云母氧化铁的折射率；T—透射光所谓的薄膜反射干涉原理（图2-2-9）。  \n\n从图2-2-9可知，当入射光 $\\boldsymbol{\\mathit{I}}$ 照射到颜料表面时，一部分光被金属氧化物薄膜反射 $(R_{1})$ ，另一部分光透过金属氧化物层到达云母氧化铁层界面，这时再次发生反射 $(R_{2})$ ，反射光 $R_{1}$ 和 $R_{2}$ 之间的相互作用可产生光的干涉效应，这样就星现出颜料的珠光光泽。  \n\n反射光的强弱及反射光的颜色，会随着入射角和观察角的不同而变化。云母氧化铁珠光颜料的颜色由金属氧化物层的光学厚度、折射率、几何厚度来决定。随着厚度的增加，颜色按顺序变化，而且这种变化可以呈周期性的重复。同时，所处的介质不同，所显示的颜色也不一样。一般对于相同粒径的云母氧化铁，随着包覆剂的沉积量的增加而显示不同的颜色变化：金黄色→红色→紫色。  \n\n珠光颜料可分为银白色型、彩虹色型和有机/无机物着色型。  \n\n(1）银白色型当云母表面 $\\mathrm{TiO}_{2}$ 薄膜的光学厚度小于 $200\\mathrm{nm}$ 时，呈银白色，其珠光色泽随云母的粒径和 $\\mathbf{TiO_{2}}$ 包覆率（即比表面积上的 $\\mathrm{TiO}_{2}$ 含量）的不同而呈现银白色丝光变化。粒度较粗的颜料因折射率高，光泽较强，而呈现星光闪烁的金属视感；粒度较细的颜料虽然遮盖力较强，但光泽较弱，而呈现丝绸或软缎一般细腻而柔和的珍珠光泽，而且 $\\mathrm{TiO}_{2}$ 包覆率越高，颜料的珍珠光泽也越强烈。  \n\n(2）彩虹色型当云母表面所镀氧化物薄膜的厚度为 $200\\sim400\\mathrm{nm}$ 时，随着薄膜厚度的不同，产生的光学效应也不相同，从而引起不同的干涉色效应，使颜料呈现出绚丽多彩的色泽，从而拓宽了其色相范围，完善了色谱，提高了装饰性能，进而扩大了其应用领域。据报道，随着 $\\mathrm{Fe}_{2}\\mathrm{O}_{3}$ 含量由 $12.6\\%$ 增至59. $1\\%$ ，颜料的干涉色也发生了从银白色→绿色→金红色 $\\rightarrow$ 红色→紫色的一系列变化。  \n\n(3）着色型在已制得的云母基珠光颜料表面再包覆一层透明或半透明的有色无机物或有机物（如铁的氧化物、铁蓝、铬绿、炭黑、有机颜料及染料等)，利用这些着色物色谱广、色泽鲜艳、分散性好、色调饱和度高等优点，使颜料的珠光光泽和有色物质的光学性共同起作用，提高其着色性能。近年来还发展了以稀土氧化物包膜的新型珠光颜料，此方法可视作  \n\n颜料的后处理。",
+        "category": " Introduction"
+    },
+    {
+        "id": 568,
+        "chunk": "# 2.荧光颜料  \n\n有机荧光颜料也称为日光荧光颜料，是吸收可见光及紫外线后，能把原来人眼不能感觉到的紫外荧光转变成一定颜色的可见光，其总的反射强度高于一般普通有色颜料。荧光颜料分为荧光色素颜料和荧光树脂颜料两种类型。制成的荧光涂料可用于安全通道、安全门、消防器材、交通标志等，还有引人注目的广告、建筑物、装饰品等，起到警示，提高视觉效果等作用。  \n\n荧光的产生包括具有光学活性的原子或分子对光的吸收和再发射过程。普通材料在光照条件下，部分入射光被选择性地吸收变成热能而消耗掉，其余部分则散射回材料表面或透过材料，使其呈现出这部分散射或投射光的颜色。而荧光材料所吸收的辐射能中，除转变为热能而损耗的以外，其余部分激发产生新的辐射能。当激发产生的辐射波长在可见光范围时，便产生荧光现象。具有特定频率 $(\\gamma_{2}$ ）的入射光激发电子跃迁进入高能态，随后处于这种不稳定高能态的电子发射光子而重新回到低能态。发射能量与光子频率的关系为[式(2-2-4)]：  \n\n$$\n\\scriptstyle{E=h\\gamma_{2}}\n$$  \n\n式中E—光子能量；h—普朗克常数；$\\gamma_{2}$ 光子频率。  \n\n由于在发射前有少量能量耗散，使发射光的能量减少，从而使发射光的频率低于所吸收的入射光的频率（图2-2-10)。若要发射出可见光，即产生所谓日光荧光，则要求吸收较高频率的入射光，如紫外线辐射的长波段和可见光范围的蓝一紫色光谱段。从入射光的吸收到荧光发射，整个过程只需约 $8\\mathrm{\\sim}10\\mathrm{s}$ ，入射光一且消失，荧光现象也立即停止。  \n\n![](images/3d61ec091bb9b1eee86687a850d827c2ba79c6c30c8515111541a1ea6bc8cc16.jpg)  \n图2-2-10发射光与人射光关系  \n\n无机荧光颜料主要组成是 $z_{\\mathrm{nS}}$ 和CdS，并含有微量的 $\\mathtt{C u}$ ， $\\mathbf{A}_{\\mathbf{B}}$ 、Mn等金属化合物为激活剂，根据不同的激活剂可以呈现出绿、红、蓝、黄光。无机荧光颜料在日光下无色或呈微弱的颜色，也有只有在紫外线照射下才呈现颜色的品种。",
+        "category": " Introduction"
+    },
+    {
+        "id": 569,
+        "chunk": "# 3.示温颜料  \n\n示温颜料即随温度变化可产生颜色变化的颜料。使用变色颜料做成示温漆，涂刷在不易测量温度变化的地方，可以从涂膜颜色的变化观察到温度的变化，这种颜料称为热敏性颜料或示温颜料。 1  \n\n这类颜料分为两类：一类为可逆性示温颜料，当温度升高时颜色发生变化，冷却后又恢复到原来的颜色；另一类为不可逆示温颜料，它们在加热时发生不可逆的化学变化，因此在冷却后不能恢复到原来的颜色，可用颜色的变化记录下经历的最高温度或温度分布。  \n\n（1）常用的不可逆变色颜料有铅、镍、钴、铁、镉、锶、锌、锰、钼、钡、镁等的硫酸盐、硝酸盐、磷酸盐、铬酸盐、硫化物、氧化物以及偶氮颜料、献菁颜料、芳基甲烷染料等。其种类及变色温度列于表2-2-58。  \n\n表2-2-58常用不可逆变化颜料的变色温度及颜色变化  \n\n\n<html><body><table><tr><td>变色颜料</td><td>变色温度</td><td>颜色变化</td><td>变色颜料</td><td>变色温度</td><td>颜色变化</td></tr><tr><td>NiNHPO · 6HO</td><td>120</td><td>亮绿色→灰蓝色</td><td>PbCO</td><td>290</td><td>白色→黄色</td></tr><tr><td>C/CO(PO)· 8HO</td><td>140</td><td>粉红色→天蓝色</td><td>CoCO</td><td>300</td><td>粉色→黑色</td></tr><tr><td>NHVOs</td><td>150</td><td>白色→棕色</td><td>Ca HNgCu</td><td>460</td><td>绿色→无色</td></tr><tr><td>(NH)PO · 12MoOs</td><td>160</td><td>黄色→黑色</td><td>PbO</td><td>600</td><td>橙色→黄色</td></tr><tr><td>Cd(OH)2</td><td>200</td><td>白色→黄色</td><td>CdSO</td><td>700</td><td>白色→棕色</td></tr><tr><td>Fe[Fe(CN)]t</td><td>250</td><td>蓝色→棕色</td><td>PbCrO</td><td>800</td><td>黄色→绿色</td></tr><tr><td>FeO·OH</td><td>280</td><td>黄色→红棕色</td><td>CoO+AlOs</td><td>900</td><td>灰色→蓝色</td></tr></table></body></html>  \n\n值得注意的是所有活性颜料、偶氮染料、分散型染料在 $60\\sim300^{\\circ}\\mathrm{C}$ 变色并不明显或由于渐变原因而导致失去使用价值。而某些碱性染料、配合物及无机盐类在 $300^{\\circ}\\mathrm{C}$ 以下存在变色点，所以可做温致变色（示温）颜料。  \n\n不可逆示温颜料的变色都是因为示温颜料受热时发生了物理或化学变化，改变了原来的物理化学性质，从而产生颜色变化，一般变化类型可分为以下几种情况。  \n\n$\\Phi$ 升华具有升华性质的某些示温颜料与填料配合显示一种颜色，但当加热到一定温度时（在一定压力下)，它则由固态分子直接变为气态分子逸出连接料，此时只显示填料的颜色，可利用这种机理达到温致变色目的。  \n\n$\\textcircled{2}$ 熔融熔融型温致变色是根据纯结晶变色颜料具有固定熔点的原理设计的。结晶示温颜料在一定温度下由有色的固态物质经熔融变为透明的液态物质，外观颜色发生变化，起到温致变色的作用。例如，使用硬脂酸铅和乙基纤维素溶液研磨成白色色浆，喷涂或印刷在深色底材上形成白色涂层，当加热至100℃时，白色硬脂酸铅熔融而成透明的液体，立即显示出深色底材的颜色，由此可以确定加热所达到的温度。  \n\n$\\textcircled{3}$ 热分解无论是有机物热敏材料，还是无机物热敏材料，在一定压力和温度下，大部分能发生分解反应。这种分解反应破坏了原来的物理结构，分解产物与原来物质的化学性质截然不同，呈现新的颜色。同时，伴随分解有气体放出，如 $\\mathrm{CO}_{2}$ ， ${\\bf s o}_{3}$ ， $\\mathrm{H}_{2}\\mathrm{O}$ . $\\mathrm{NH}_{3}$ 等。因此可以利用这种特性达到温致变色的目的。  \n\n$\\textcircled{4}$ 氧化氧化反应是一种常见的化学变化。不少物质在氧化条件下加热可以发生氧化反应，生成一种与原组成不同的物质，同时产生一种新的颜色，达到温致变色的目的。  \n\n$\\textcircled{5}$ 固相反应固相反应也是变色的一种机理，利用两种或两种以上物质的混合物，在特定温度范围内发生固相间的化学反应，并生成一两种或更多种新物质，从而显示与原来截然不同的颜色。例如，钢灰色的氧化钻与白色的氧化铝配成灰色的混合物，当加热至$1000^{\\circ}\\mathrm{C}$ 左右，此混合物则生成蓝色的铝酸钻。由于固相反应速率远比溶液中的反应速率慢，同时随着反应温度的升高或反应时间的延长，新物质在逐渐增多。颜色变化是逐渐变深的。所以这种涂料变色温度区间较宽，精确度也低。 二  \n\n(2）常用的可逆示温颜料主要是Ag、 $\\scriptstyle{\\mathrm{~H}}_{\\mathbb{B}}$ 、Cu的碘化物、配合物或复盐的钻盐、镍盐与六亚甲基四胺所形成的化合物等。  \n\n可逆性变色颜料在受热时变色物质发生了一定程度的改变，如复盐的变体、结晶水的失去，冷却后，物质结构又可恢复到原来的状态，或由于吸收空气中的水分又形成结晶水，因此可逆性变色颜料只能用于 $100^{\\circ}\\mathrm{C}$ 以内温度变化的场合(表2-2-59)。  \n\n表2-2-59常用的可逆变化颜料的变色温度及颜色变化  \n\n\n<html><body><table><tr><td>变色颜料</td><td>变色温度/℃C</td><td>颜色变化</td></tr><tr><td>CoCl * 2CHN • 10HO</td><td>35</td><td>粉红色→天蓝色</td></tr><tr><td>CoBr • 2CHN • 10HO</td><td>40</td><td>粉红色→天蓝色</td></tr><tr><td>Hglz • AgI</td><td>45</td><td>暗黄色→暗褐色</td></tr><tr><td>Agz HgI</td><td>50</td><td>黄色→橙色</td></tr><tr><td>Col· 2CHzN •10HO</td><td>50</td><td>粉红色→绿色</td></tr><tr><td>CoSO • 2CHN ·10HO</td><td>60</td><td>粉红色→紫色</td></tr><tr><td>NiCl • 2CHN · 10HO</td><td>60</td><td>亮绿色→黄色</td></tr><tr><td>NiBrz • 2CHN • 10HO</td><td>60</td><td>亮绿色→天蓝色</td></tr><tr><td>Hglz • Cal</td><td>65</td><td>胭脂红色→咖啡色</td></tr><tr><td>CuHgI</td><td>70</td><td>洋红色→红棕色</td></tr><tr><td>Co(NO) • 2CHN • 10HO</td><td>75</td><td>粉红色→缝红色</td></tr><tr><td>Hgl</td><td>137</td><td>红色→蓝色</td></tr></table></body></html>  \n\n$\\Phi$ 失去结晶水含有结晶水的物质加热到一定温度后会失去结晶水，从而引起物质颜色变化；一经冷却，该物质又能吸收空气中的水汽，逐渐恢复原来的颜色。例如，粉红色的氯化钴、六亚甲基四胺，于 $35\\mathrm{^c}$ 失去结晶水而变为天蓝色。  \n\nCoCl·2CHN·10HO(粉红色)—→ $\\mathrm{CoCl_{12}}\\cdot2\\mathrm{C_{6}}\\mathrm{H_{12}}\\mathord{\\mathbb{N}}$ 4（天蓝色） $\\boldsymbol{\\cdot}+10\\mathsf{H}_{2}\\boldsymbol{\\mathrm{O}}$  \n\n$\\textcircled{2}$ 晶型转变有些变色颜料是一种结晶物质，在一定温度作用下其晶格发生位移，即由一种晶型转变为另外一种晶型，从而导致颜色的改变。当冷却至室温，晶型复原，颜色也随之复原。例如，正方体（红色）的碘化汞（ $\\mathrm{H}_{\\mathbb{E}}\\mathrm{I}_{2}$ ）当加热至 $137^{\\circ}\\mathsf{C}$ 时变为蓝色斜方晶体。冷却至室温后，又恢复到正方体晶型，颜色复原。  \n\n必须指出，变色颜料的晶体位移变化比温度变化得慢，因而晶型改变所出现的颜色变化滞后于温度变化。而晶型恢复过程要比改变过程中的颜色变化滞后现象更为明显。  \n\n$\\textcircled{3}$ pH变化某些物质与高级脂肪酸混合，当加热到一定温度时，酸中离解出的羧酸分子导致 $\\mathsf{p H}$ 提高，产生变化，温度降低，pH又下降，物质颜色亦随之复原，因此，可以利用 $\\mathsf{p H}$ 随温度变化而改变某种物质颜色的原理达到温致变色的目的。例如，硬脂酸与溴酚蓝在 $55\\mathrm{^{\\circ}C}$ 时颜色由黄色变为蓝色，发生变色，冷却至室温颜色又复原。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 570,
+        "chunk": "# 4.金属颜料  \n\n金属颜料是颜料中的一个特殊种类，其历史悠久。随着现代工业的发展，对金属粉的需求量越来越大，种类也随之增加。常见的金属粉有铝粉、锌粉、铅粉，合金形式的金属粉有铜锌粉（俗称金粉）、锌铝粉、不锈钢粉等。  \n\n与其他颜料相比较，金属颜料有它的特殊性。由于粉末状的金属颜料以金属或合金组成，有明亮的金属光泽和颜色，因此许多金属颜料用于装饰性颜料，如铜锌粉、铝粉等。  \n\n大多数金属颜料都是鳞片状粉末，它调入成膜物而且涂装成膜时，像落叶铺地一样与被涂物表面平行，互相搭接，互相遮掩，多层排列，形成屏障，金属鳞片阻断了成膜物的微细孔，产生“迷宫效应”阻止外界有害气体或液体在涂膜中的渗透，保护了涂膜及被涂装物品，提高了涂层物理屏蔽的防腐蚀能力；金属粉能反射日光中紫外线的 $60\\%$ 以上，故又能防止涂膜因紫外线照射老化，有利于延长涂膜的寿命；同时其反射光能起到闪光、装饰功能。 +  \n\n金属颜料是极微细的粉末，多属鳞片状，但也有球形、水滴形、树枝形的，都与其制造方法有关。金属粉末须经过表面处理才具有颜料特性，如分散性、遮盖力等，不同的表面处理可使金属颜料表面呈亲油性或亲水性，以适应不同涂料的要求。  \n\n大多数金属颜料通过物理加工方式进行生产，使纯金属或合金成为特定的粉末，如从固态、液态及气态金属转化为粉末。  \n\n$\\textcircled{1}$ 由金属的气相状态转化为粉末，如升华法制取锌粉、超细铝粉。  \n\n$\\textcircled{2}$ 由金属的液相状态转化为粉末，如气动雾化法制取铝粉、锌粉及铜锌粉。  \n\n$\\textcircled{3}$ 由金属的固相状态转化为粉末，如切削法、球磨法制造镁粉、铝粉、锌粉、不锈钢粉及钛粉。  \n\n选用不同的粉末制造方法要根据被加工的金属的物理特性，如熔点、气化温度、硬度和延展性，还要按照产品粉末的构造特征，如颗粒度、形状等，从经济合理的角度出发，选取加工成本和耗能最低的方法。加工方法的选择还要注重它的安全性，多数金属粉有良好的还原性，急剧氧化会放出大量的热并产生高温，容易发生爆炸危险。金属粉末，尤其是重金属粉末对人的健康有危害，所以在选择加工方式上保证安全是一条重要原则。  \n\n对于各种纯金属及合金金属选取不同的加工方式见表2-2-60。金属粉末颜料使用量最大的是铝粉（包括铝粉浆)、铜锌粉及锌粉，这几种金属粉末的生产工艺和步骤很近似，本节以铝粉浆生产工艺为典型介绍。  \n\n表2-2-60金属粉末的制取方法  \n\n\n<html><body><table><tr><td rowspan=\"2\">加工类型</td><td rowspan=\"2\">加工方法</td><td rowspan=\"2\">适用的原材料</td><td colspan=\"2\">粉末类型</td></tr><tr><td>金属粉末</td><td>合金粉末</td></tr><tr><td rowspan=\"3\">机械粉碎法</td><td>机械研磨</td><td>延展性金属</td><td>Al.Cu、Zn</td><td>钢合金</td></tr><tr><td>旋涡研磨</td><td>金属或合金</td><td>Fe、Al</td><td></td></tr><tr><td>气流粉碎</td><td>金属或合金</td><td>Fe</td><td>不锈钢</td></tr><tr><td rowspan=\"2\">雾化法</td><td>气流雾化</td><td>液态金属及合金</td><td>Al、Pb、Cu、Zn、Fe</td><td>黄钢、青钢、合金钢</td></tr><tr><td>水流雾化</td><td>液态金属及合金</td><td>Al.Cu、Fe</td><td>黄钢、青钢</td></tr><tr><td>气相沉积法</td><td>金属蒸气冷凝</td><td>气态金属</td><td>Zn、Mg</td><td></td></tr><tr><td>还原法</td><td>金属还原</td><td>金属化合物</td><td>Ti</td><td></td></tr></table></body></html>  \n\n（1）铝粉及铝粉浆  \n\n$\\Phi$ 铝粉又称铝银粉，化学式A1，分子量27，相对密度2.55，熔点 $685\\mathrm{^\\circ}$ 。铝粉由于用途广、需求量大、品种多，是金属颜料中的一大类。  \n\n颜料用的铝粉粒子是鳞片状的，也正是由于这种鳞片状的粒子状态，铝粉才具有金属色泽和屏蔽功能。铝粉的特性表现如下。  \n\na.鳞片遮盖铝粉粒子呈鳞片状，其片径与厚度的比例大约为 $(40:1)\\sim(100:1)$ .铝粉分散到载体后具有与底材平行的特点，众多铝粉互相连接，大小粒子相互填补形成连续的金属膜，遮盖了底材，又反射涂膜外的光线，这就是铝粉特有的遮盖力。其大小取决于表面积的大小，即径厚比。  \n\nb.屏蔽特性分散在载体内的铝粉发生漂浮运动，其运动的结果总是使自身与被载体涂装的底材表面平行，形成连续的铝粉层，且在载体膜内多层平行排列。各层铝粉之间互相错开，切断了载体膜的毛细微孔，外界的水分、气体无法透过毛细孔到达底材，这使铝粉具有良好的物理屏蔽性。  \n\nc.光学特性铝粉表面光洁，能反射可见光、紫外线和红外线的 $60\\%\\sim90\\%$ ，用含有铝粉的涂料涂装物体，其表面银白光亮。  \n\nd.双色效应铝粉由于具有金属光泽和平行于被涂物的特性，在含透明颜料的载体中，铝粉的光泽度和颜色深浅随入射光的入射角度和视角的变化而发生光和色的变化，产生随角异色效应。  \n\ne.漂浮特性铝鳞片表面的氧化膜是亲水性的，用脂肪酸包裹处理后是疏油性的，在油性涂料载体内不被浸润。当载体溶剂挥发时，带动铝粉浮向载体上表层。随着溶剂的蒸发和树脂的黏度上升，铝粉被固定在载体表面，形成一层金属膜，形成良好的屏蔽层。  \n\n铝粉遮盖力强，粒径越小遮盖力越强，耐候性良好，耐含硫气体。用于配制涂料，能起到屏蔽作用和反射一部分光波，可引起色调和金属光泽的变化，常用于配制锤纹漆、底面两用漆及美术漆等。  \n\n$\\textcircled{2}$ 铝粉浆由于铝粉质轻，易在空气中飞扬，遇火星易发生爆炸，为了消灭爆炸危险，常加人溶剂油，制成铝粉浆使用，又称铝银浆（一般铝银浆的固含量为 $65\\%$ 。其用途和特性与铝粉大致相同，使用起来更简便、更安全，其产量和用量更大。  \n\n根据使用目的的不同，常用的铝银浆溶剂有 $200^{\\#}$ 溶剂油(MS)、高沸点芳香烃溶剂（HA)、乙酸乙酯（EA）、乙酸丁酯（BA）等。除溶剂外，为了保证体系的稳定，通常还需加入各种表面活性剂和稳定剂。表2-2-61为各类铝粉浆的配料。  \n\n表2-2-61各类铝粉浆的配料  \n\n\n<html><body><table><tr><td>铝粉浆类型</td><td>溶剂</td><td>表面活性剂及其他助剂</td></tr><tr><td>漂浮型铝粉浆</td><td>脂肪烃溶剂、芳香烃溶剂</td><td>硬脂酸、软脂酸、二十二烷酸、钛酸酯、稳定剂、分散剂</td></tr><tr><td>非漂浮塑铝粉浆</td><td>脂肪烃溶剂、芳香烃溶剂</td><td>油酸、亚油酸、亚麻油酸、金属皂类、分散剂</td></tr><tr><td>水分散型铝粉浆</td><td>脂肪烃溶剂、醇、水、酶</td><td>金属皂类、表面活性剂</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 571,
+        "chunk": "# 常用铝粉浆规格见表2-2-62。  \n\n表2-2-62常用铝粉浆规格  \n\n\n<html><body><table><tr><td>类型</td><td>金属含量/%</td><td>水分/%</td><td>相对密度</td><td>平均粒度/μm</td></tr><tr><td>漯浮型铝粉浆</td><td>65</td><td>≤0.1</td><td>1.4</td><td>5~20</td></tr><tr><td>非漂浮型铝粉浆</td><td>65</td><td>≤0.1</td><td>1.5左右</td><td>10~30</td></tr></table></body></html>  \n\n(2）铜锌粉铜锌粉是铜锌合金制成的鳞片状细粉末，俗称金粉。这种金属粉有类似黄金的色光。  \n\n铜锌粉最早出现在德国，18世纪当地工匠制造出了像黄金一样的铜合金箔并粉碎成粉末，用于涂漆装饰，继而又用到印刷业上制造印金油墨。印金的印刷品华丽夺目，又显得贵重，所以发展非常迅速，印刷业的一些特殊要求又促进了铜锌粉的发展。目前，各种不同色光、细度和特性的铜锌粉种类繁多。  \n\n我国铜锌粉工业在20世纪60年代建立起来，生产数量、品种和生产厂家逐年增加，基本满足了需要。  \n\n铜锌粉是包覆着表面处理剂的铜合金鳞片粉末，有各种不同的色相，可分为青光、青红光和红光三种。  \n\n铜含量为 $75\\%\\sim80\\%$ 的称为青光铜锌粉，也称绿金色金粉。  \n\n铜含量为 $84\\%\\sim86\\%$ 的称为青红光铜锌粉，又称浅金色金粉，呈纯金色相，铜含量在 $88\\%$ 左右的称为红光铜锌粉，又称赤金色金粉，呈红金色相。  \n\n铜锌粉的一个特点是粒子为鳞片结构，铜锌合金有良好的延展性，在多次研磨之后形成平展、光洁的微细薄片。这种粒子结构决定了它有与被涂物平行排列的特性，当含铜锌粉的载体成膜后，铜锌粉鳞片径向互相连接，形成连续的金属膜，这层金属膜反射外来光线而呈现金色色光。  \n\n铜锌粉颜料粒子均包覆一层有机物膜，在铜锌粉鳞片形成过程中有机物如硬脂酸便吸附在粉的表面，硬脂酸包覆膜既减小粉的密度，又增加其表面张力，因此铜锌粉混入载体时具有漂浮性。  \n\n铜锌粉的粒子细度分布范围较窄，不同细度的粉末反光能力不同，色相不一致。在印刷中粗粒子不易从辊轴转移到纸张上去，造成漏印。所以，铜锌粉在生产过程中严格控制粒度分布。  \n\n铜锌粉主要用于装饰涂料的颜料，用于建筑物、装饰品的涂刷等。  \n\n(3）锌粉及其他金属颜料  \n\n$\\Phi$ 锌粉纯锌是灰色金属，有金属光，熔点 $419.5\\mathrm{^{\\circ}C}$ ，沸点 $918^{\\circ}\\mathrm{C}$ ，密度 $7.13g/\\mathrm{cm}^{3}$ 制造锌粉使用的原料是金属锌锭，其牌号为ZN-4。纯度 $99.5\\%$ (GB 470—1964)。锌在大气中具有相当高的耐腐蚀性，但在酸式盐、碱式盐中不耐腐蚀，当锌同正电性较强的金属接触时，锌首先被腐蚀，生成氧化物，所以锌可用于保护层，大量的锌粉在涂膜内互相连成导电层，当涂层遇到电化学腐蚀时，由于锌比铁具有负的电极电位差，首先被腐蚀，起到阴极保护作用，保护了钢铁底材；锌与酸性食物接触能生成锌盐有毒性，故不能用于食品设备的涂装。  \n\n锌粉在色漆中主要作为防锈颜料使用。一般用量较高，达到 $60\\%\\sim80\\%$ ，制成富锌（底）漆。锌粉密度大、易沉淀，制漆时除加少量防沉剂外，一般与漆基分装，现用现配。  \n\n$\\textcircled{2}$ 钛粉钛在常温下对各种酸、碱类物质都有很好的耐腐蚀性，钛对氧的亲和力很强，在其表面生成致密的氧化膜，具有良好的化学稳定性。  \n\n钛粉的防腐蚀、化学稳定性优良和无毒的特点使之在化学工业、食品工业方面的涂装有广泛的使用范围。  \n\n$\\textcircled{3}$ 不锈钢粉不锈钢粉具有良好的化学稳定性，能防止化学腐蚀。颜色浅、高光泽的金属粉还有保温能力，这类金属粉几乎不吸收光线，能反射可见光、紫外线，对于热辐射也是如此，因此可用于需要保温、防止光和热辐射的物品上，如贮存油品、气体的罐、塔上。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 572,
+        "chunk": "# 5.防锈颜料  \n\n防锈颜料不以着色为目的，而是用于配制防锈漆的一类颜料，有保护金属表面不被腐蚀的作用。早期的品种是红丹、铬酸盐颜料，其防腐蚀的效果早已有定论，因含有铅及六价铬，属有毒颜料，当前应积极发展一些高效、无毒的防锈颜料，以取代早期的有毒品种。  \n\n(1）红丹、黄丹及其他含铅防锈颜料红丹 $\\mathrm{(Pb_{3}O_{4}}$ ）是最重要的传统防锈颜料，它的防锈效果可靠。  \n\n黄丹（PbO）属生产红丹的中间产品，也是一种化工产品，统计产量时合在一起计算为红黄丹。  \n\n红丹因含铅而逐步退出防锈颜料的行列，但它本身是一种不能替代的化工原料，在蓄电池、玻璃、陶瓷、橡胶等行业广泛应用，总的产量不见减少。  \n\n为了节约用铅，现已有以部分钙取代铅的品种铅酸钙（ $\\mathrm{Ca_{2}P b O_{4}}$ ），防锈效果据试验已达到红丹的防锈能力，因含有铅而未能推广应用。  \n\n硅铬酸铅也属红丹的代用品，它是一种包核颜料，铅同硅酸盐紧密结合，毒性较低，在部分地区得到推广应用。此外尚有氰氨（基）化铅、碱式硅酸铅、二碱式亚磷酸铅等含铅品种。  \n\n但由于铅对人体的毒性越来越受到社会的关注，目前已在多国（包括中国）制定了各种法规和标准，对涂料中含铅颤料的使用进行了限制或禁用。  \n\n(2）铬酸盐类防锈颜料锌铬黄、四碱式锌黄、锶铬黄、钡铬黄、钙铬黄等铬酸盐类防锈颜料均含有六价铬，属有毒颜料。其防锈机理在于六价铬在金属表面可形成钝化层，防锈效力很可靠，因毒性问题，这类颜料也逐步由无毒防锈颜料所取代。  \n\n(3）磷酸盐类防锈颜料磷酸锌是20世纪60年代才开始应用的，它是最重要的无毒防锈颜料。磷酸锌的水解产物能同钢铁表面反应并形成铁锌磷酸复合盐的保护膜，被认为是较理想的红丹替代品，不过它同红丹的防锈机理不尽相同。随后又出现了一些磷酸锌的改性品种，以及多种复合的磷酸盐防锈颜料新品种，如聚磷酸铝、磷酸铬、磷钼酸锌、磷钼酸钙锌、羟基亚磷酸锌、磷硼酸锌、磷化铁等。  \n\n德国、美国、法国、西班牙、英国、日本均有开发产品，这方面的开发工作相当活跃。我国自20世纪70年代开始用磷酸锌及其他磷酸盐类防锈颜料替代含铅、铬的颜料，取得一定的效果。  \n\n（4）硼酸盐类防锈颜料偏硼酸钡 $\\mathrm{\\langleBaB}_{2}\\mathrm{O}_{4}\\cdot\\mathrm{H}_{2}\\mathrm{O})$ 是这类颜料的主要产品。美国开发这种产品，其目的是制备一种防霉、防锈的品种。  \n\n（5）离子交换防锈颜料这种颜料的主要组成是含钙离子的沸石或硅胶。它能以 ${\\mathbf{C}}{\\mathbf{a}}^{2+}$ 交换涂膜中的氢离子，从而使酸性物质得到中和，而 ${\\mathrm{Ca}}^{2+}$ 又能同金属氧化物膜相结合，维持较高的 $\\mathsf{p H}$ ，起到了防腐蚀的效果。这种颜料因不含重金属而无毒，受到一定的重视，英国于20世纪80年代起开发这类颜料。  \n\n（6）屏蔽型防锈颜料一般的防锈颜料的防锈作用均属化学性质，如与金属表面生成络合物、提高 $\\mathsf{p H}$ 、起钝化作用等。  \n\n通过大量观察和研究，人们注意到片状颜料能在涂料中排列成层、层层叠加，形成交叉而封闭性良好的屏蔽层，使外界的水分、气体、紫外线无法侵入金属表面，起到防腐蚀的效果，其作用的性质属于物理性的。  \n\n天然云母氧化铁 $({\\mathrm{Fe}}_{2}{\\mathrm{O}}_{3}$ )，具有云母状的片状结构，属屏蔽型防锈颜料，为防锈底漆、重防腐涂料所选用。  \n\n合成云母氧化铁于20世纪80年代在英国投产，改变工艺参数可控制产品的片径、厚度，质量较天然产品更加符合配漆的要求，但生产成本较天然产品高。  \n\n目前云母氧化铁颜料主要是使用在防腐涂料体系的中涂层中。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 573,
+        "chunk": "# 6.耐高温彩色复合颜料  \n\n耐高温彩色复合颜料为金属氧化物的混合相颜料，是在晶格中引入其他离子，这类颜料具有更高的耐热性 $(1000^{\\circ}\\mathrm{C})$ ，耐光性、耐候性也很好，可应用于各种高温涂料中。  \n\n德国Bayer公司Light-Fast颜料品种和结构见表2-2-63。  \n\n表2-2-63德国Bayer公司Light-Fast颜料品种和结构  \n\n\n<html><body><table><tr><td>产品名称</td><td>组分</td><td>结晶结构</td><td>产品名称</td><td>组分</td><td>结晶结构</td></tr><tr><td>Light黄8G</td><td>(Ti,Ni,Sb)O</td><td>金红石型</td><td>Light蓝100</td><td>Co(Al,Cr)O</td><td>尖晶石型</td></tr><tr><td>Light黄3G</td><td>(Ti,Cr,Sb)O</td><td>金红石型</td><td>Light 蓝2R</td><td>CoAlzO</td><td>尖晶石型</td></tr><tr><td>Light绿5G</td><td>（Co,Ni，Zn）（TiAI）O</td><td>尖晶石型</td><td>Fast黑100</td><td>Cu(Cr,Fe)O</td><td>尖晶石型</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 574,
+        "chunk": "# 7.含镍不锈钢片颜料  \n\n目前国外使用一种含镍不锈钢颜料，耐腐蚀性强，能通过500h的盐雾试验（ASTM法)，即使在水性漆中也很稳定。  \n\n有浆状和粉状两种商品，可用于家电、自行车、办公家具用漆，比铅粉效果好，不变  \n\n色，不与酸发生作用，也无释放出氢气的病。  \n\n另有 $\\mathrm{Brnnze~}925$ 片状颜料，为高纯合金粉末，耐腐蚀性好，可用于粉末涂料及户外高耐久性涂料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 575,
+        "chunk": "# 第四节着色与配色原理—色彩学",
+        "category": " Introduction"
+    },
+    {
+        "id": 576,
+        "chunk": "# 一、色彩学的意义  \n\n颜色除了有它的物理学意义、生理学意义外，还有心理学意义。彩色涂料涂覆在物体表面后，除了能改善被涂覆物的某些特定性能外，还有一个很重要的功能就是赋予物体各色的装饰效果，给观测者不同的视觉和心理感受。  \n\n没有光就不会有色彩的感觉，光是物理学上客观存在的一种物质，光是产生色彩感觉的刺激物，因此，颜色具有物理属性。牛顿的光学实验告诉人们，色的概念实际上是不同波长的光刺激人眼的视觉反映。  \n\n色彩是视觉器官感觉的结果。人的眼睛是最精密、灵敏的感受器，世界万物的明暗、色彩、形状、空间是靠眼睛来认识和辨别的。但视觉功能不是万能的，有时候因视觉生理功能的局限性而产生错觉与幻觉，因而会导致主观感觉和客观现实之间存在一定差异。  \n\n色彩心理是指客观色彩世界引起的主观心理反映。不同色彩必然会产生某种感情的心理活动。事实上色彩生理与色彩心理是同时交替进行的，相互联系，相互制约。当色彩刺激引起生理变化时，必定伴随心理的变化。不同色调给人不同感觉，伴随人们不同心情的描述，如白色象征纯洁、朴素，黄色使人兴奋，红色是热情、喜庆、正义的象征，绿色是温柔、富有朝气，青色体现宁静，蓝色反映稳重、平和，黑色显得庄严。同时，颜色的韵律具有一定规律性，如有暖色、冷色与中性色，即红、橙、黄为暖色，绿、青、蓝、紫为冷色，中驼、浅灰、淡紫为中性色。",
+        "category": " Introduction"
+    },
+    {
+        "id": 577,
+        "chunk": "# 二、颜色基本概念",
+        "category": " Introduction"
+    },
+    {
+        "id": 578,
+        "chunk": "# 1.光与色  \n\n光在物理学上是一种客观存在的物质（而不是物体)，它是一种电磁波。电磁波包括宇宙射线、X射线、紫外线、可见光、红外线和无线电波等。它们都各有不同的波长和振动频率，在整个电磁波范围内，并不是所有光的色彩肉眼都可以分辨，只有波长在380～780nm之间的电磁波才能引起人的色知觉，这段波长的电磁波称为可见光谱，在这段可见光谱内，不同波长的光会对人的眼睛产生不同的刺激，进而产生不同的颜色感觉。 福  \n\n光与色，光是人们感觉所有物体形态和颜色的唯一物质；色是由物体的化学结构和粒子形态决定的一种光学特征。",
+        "category": " Introduction"
+    },
+    {
+        "id": 579,
+        "chunk": "# 2.光源色、固有色、环境色  \n\n光源色是指照射物体光线的颜色。不同的光源会导致物体产生不同的色彩，相同的景物在不同光源下会出现不同的视觉色彩。光线强弱会引起物体色调、纯度和饱和度的变化。光线强时，物体的明度会提高；光线弱时，物体的纯度和饱和度会降低。  \n\n固有色并非一个非常准确的概念，因为物体本身并不存在恒定的色彩，是一种习以为常的称谓。便于人们对物体的色彩进行比较、观察、分析和研究。光线强时，物体的固有色体  \n\n现在接近受光部位和明暗转折之间的灰色中间区域；光线弱时，物体的固有色变得暗淡模糊。色彩学指出：物体在中等光线下(也可以说阳光间接反射或漫射光)，其他色光影响较小时，物体可呈现的固有色最明显。  \n\n环境色也称“条件色”。自然界中任何事物和现象都不是孤立存在的，--切物体色均受到周围环境不同程度的影响。环境色是一个物体受到周围物体反射的颜色影响所引起的物体固有色的变化。物体呈现何种色彩，是光源色、固有色、环境色三个因素综合作用的结果。",
+        "category": " Introduction"
+    },
+    {
+        "id": 580,
+        "chunk": "# 3.色彩的三要素  \n\n色调、明度与饱和度在色彩学上也称色彩的三要素、三属性或三特征。色调体现了颜色在“质”方面的关系；明度体现了颜色在“量”方面的不同；饱和度是表示颜色饱和和纯洁的一种特性（我们在第二节颜色中对颜色的三要素已有阐述)。",
+        "category": " Introduction"
+    },
+    {
+        "id": 581,
+        "chunk": "# 三、色彩基本理论",
+        "category": " References"
+    },
+    {
+        "id": 582,
+        "chunk": "# 1.色的混合——配色原理  \n\n(1）原色理论三原色也称三基色，就是指这三种色中的任意一色都不能由另外两种原色混合产生，而其他色可由这三色按照一定的比例混合出来，色彩学上将这三个独立的色称为三原色。国际照明委员会（CIE）将色彩标准化，正式确认色光的三原色（即RGB三原色）为红、绿、蓝（蓝紫色)，颜料的三原色为红（品红）、黄（柠橡黄)、青（湖蓝)。  \n\n(2）混色理论由两种以上不同的色相混合会产生新的颜色，这就是混色。包括两种形式，加色法混色和减色法混色。这种现象在实际配色工作中起着很重要的作用，可以运用混色理论对三原色进行解释。  \n\n$\\textcircled{1}$ 加色法混合理论加色法混色指的是各色光的混合，其光亮度是各色光亮度的总和，随各色光混合量的增加，色光明度逐步提高，最后会产生白光。根据物理光学实验中得出光的三原色的红 $700\\mathbf{nm})$ 、绿（ $546.1\\mathrm{nm})$ 、蓝 $(435,8\\mathsf{n m})$ ）是不能通过其他光混合出来的，是加色比较理想的三原色，通过三原色可以混合出几乎所有的颜色。  \n\n从加色法混色规律图2-2-11可以得出：  \n\n红光 $^+$ 绿光 $\\c=$ 黄光  \n红光 $^+$ 蓝光 $\\c=$ 品红光  \n蓝光十绿光 $\\c=$ 青光  \n红光 $^+$ 绿光 $^+$ 蓝光=白光  \n\n只要改变三原色光的混合比例就可得到不同色光。如红光与绿光通过不同比例可以得到橙、黄、黄绿等。  \n\n$\\textcircled{2}$ 减色法混色理论减色法混色指的是色料（着色剂）的混合，也就是颜料的混色。色料指的就是对不同波长的可见光进行了选择性吸收后，经反射呈现各种不同色彩的颜料或染料等有色物质。颜料的混色会变深变暗最后变为黑色，这称为减色法混色。理论上讲，颜料的三原色为品红、黄、青混合可以得出所有颜色，将两种不同原色混合称为间色，将间色与原色混合或间色与间色混合称为复色。  \n\n![](images/09136d34f4fae3d69ee7b8f3fc861abfa63244a0aa408f43f7f3aa6cdbe11fb3.jpg)  \n图2-2-11加色法混色规律  \n\n减色法混色的原理，只是为色料混合提供了一些规律，实际配色过程中，仅用三原色配色是非常困难的。这是因为目前生产的品红、青、黄等颜料的纯度、色调和饱和度远远达不到要求，从而大大缩小了三原色的混色范围。  \n\n从减色法混色规律图2-2-12可以得出：  \n\n![](images/e45dd7e5561a83fc082ed24cc5b59217ce3f905fc5275c7373b374cb78e5c643.jpg)  \n图2-2-12减色法混色规律  \n\n同时改变三原色色料的比例可得到各种不同的颜色。如品红色料与黄色色料通过不同比例混合可以得到红、橙等不同色相、不同饱和度的颜色。若两种颜色相混呈现灰色或黑色时，那么这两种颜色被称为互补色。如红与绿，黄与紫，青与橙。  \n\n关于涂料的着色与配色，一般所指的都是减色法混色原理。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 583,
+        "chunk": "# 2.牛顿色相环  \n\n三原色中任何一种原色都是其他两种原色之中间色的补色；也可以说，三间色中任何一种间色都是其他两种间色之原色的补色。在牛顿色相环上，表示色相的序列以及色相间的相互关系。将色圆环分为六等份，分别为红、橙、黄、绿、青、紫六个色相，通过图2-2-13可以很清晰表示三原色、三间色、邻近色、对比色及互补色的相互关系。  \n\n![](images/bc64297f9c96c1f11e28b9d9b00b5b121cb96a35aebfcddc22ef008425a37534.jpg)  \n图2-2-13三原色与三间色之间的关系  \n\n![](images/69aa67890101057b02a787ea684f235f5a6db039d30f272b083020f54ddbe6cb.jpg)  \n图2-2-14色球仪",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 584,
+        "chunk": "# 3.色立体  \n\n牛顿色相环建立了色相之间相互关系，而色彩的基本特性除了色相外，还有明度与纯度，显然用二维平面无法描述三个基本属性。而色立体是借助于三维空间来表示色相、纯度、明度的关系。色彩的关系可以用图2-2-14色球仪上的位置和结构来表示：赤道部分表示纯色相环；南北两极连成的中心轴为无彩色系的明度序列，B极为黑，W极为白，球心为正灰；南半球为深色系，北半球为明色系；球表面为清色系；球内为含灰色系（浊色系)；  \n\n球表面任何一个到球中心轴的垂直线上，表示着纯度序列；与中心轴相垂直的圆直径两端表示补色关系。这个色立体只是一个理想化的示意图，便于理解颜色三特性的相互关系。事实上纯度最大的黄色不在中等明度的赤道上，而是偏向白色一极；纯度最大的蓝紫色也不在赤道上，而是偏向黑色一极。孟赛尔颜色体系对此都做了相应的修正，使色彩关系的表达更加准确。在实际涂料配色中，色立体是一个非常实用的配色的工具。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 585,
+        "chunk": "# 4.孟赛尔颜色体系  \n\n1905 年美术家孟赛尔（A.H.Mun.Sell）发明了一种用心理学三维空间的类似球体的模型把各种表面色的三种颜色参数—色调、明度、饱和度全部表现出来，在立体模型中的每一部位各代表一个特定的颜色，目前国际上已广泛采用孟赛尔颜色系统作为分类和标定表面色的方法，其表示方法符号为HV/C，H代表色调(Hue)，V代表明度（Value)，C代表彩度（Chroma)。  \n\n对于无彩色的黑白系列中性色用N表示，在N后面给出明度值V，斜线后面不写彩度，以NV/表示。  \n\n关于颜色3个参数之间的关系可用图2-2-15枣核形颜色立体来加以描述，但它只是一个过于简单化的模型。枣核形最大截面圆周上各点为色调的变化，其颜色的饱和度最大。最大截面的半径方向为饱和度的变化，越靠近圆心饱和度就越小，通过圆心与水平截面垂直的立轴为明度的变化，越向上明度就越大，颜色越白。  \n\n![](images/dc674635c8a70d1b1811f71f3667853bdba72ca14b546f63d337ab4444b2db20.jpg)  \n图2-2-15枣核形颜色立体  \n\n图2-2-16是孟赛尔颜色立体，它与枣核形颜色立体基本是相同的，只是又进一步从心理学角度，根据颜色的视觉特点制定颜色分类和标定系统，具体分类方法是：把明度分为10个等级，彩度也按视觉分成相等的等级，对每种色调彩度不尽相同，个别色调的彩度可达20。通过图2-2-17孟赛尔颜色立体水平剖面可以看出，色调表示分成5个主色调，分别以红(R)、黄（Y)、绿（G)、蓝（B)、紫（P）表示，还有5个中间色调，分别以黄红(YR)、绿黄（GY)、蓝绿（BG)、紫蓝（PB)、红紫（RP）表示，为了更精细划分，每一色调又分成10个等级，每种颜色在孟赛尔系统中都可以用3个坐标值——色调、明度和彩度来表示。孟赛尔颜色立体比起理想的颜色立体更接近实际情况，虽然不是完善的，但对颜色性质的理解已更深入一步。  \n\n![](images/99dc60a0f79579cb377be6ea8e4e093c8edcb2621b09ddd6b391c3efee98fd88.jpg)  \n图2-2-16孟赛尔颜色立体  \n\n图2-2-17孟赛尔颜色立体水平剖面",
+        "category": " Introduction"
+    },
+    {
+        "id": 586,
+        "chunk": "# 5.奥斯特瓦尔德色相环  \n\n奥斯特瓦尔德（W.Ostwald，是曾获诺贝尔奖的德国化学家)，创立了奥斯特瓦尔德色彩体系。其色相环由24个色组成，他以赫林（E.Hering）的四色学说为理论基础，在黄、红、蓝、绿四色基础上分出橙、紫、蓝绿、黄绿组成8个基本色。然后再将每种颜色分为三种，形成24个基本色相，并分别以符号表示（表2-2-64)。  \n\n表2-2-64奥斯特瓦尔德色彩体系的色调、符号、编号与主波长  \n\n\n<html><body><table><tr><td>色调</td><td>符号</td><td>编号</td><td>主波长/nm</td><td>色调</td><td>符号</td><td>编号</td><td>主波长/nm</td></tr><tr><td rowspan=\"3\">黄色</td><td>1Y</td><td>1</td><td>573</td><td rowspan=\"3\">蓝色</td><td>1UB</td><td>13</td><td>464</td></tr><tr><td>2Y</td><td>2</td><td>579</td><td>2UB</td><td>14</td><td>473</td></tr><tr><td>3Y</td><td>3</td><td>582</td><td>3UB</td><td>15</td><td>479</td></tr><tr><td rowspan=\"3\">橙色</td><td>10</td><td>4</td><td>587</td><td rowspan=\"3\">蓝绿</td><td>1T</td><td>16</td><td>483</td></tr><tr><td>20</td><td>5</td><td>593</td><td>2T</td><td>17</td><td>485</td></tr><tr><td>30</td><td>6</td><td>602</td><td>3T</td><td>18</td><td>488</td></tr><tr><td rowspan=\"3\">红色</td><td>1R</td><td></td><td>617</td><td rowspan=\"3\">绿色</td><td>1SG</td><td>19</td><td>490</td></tr><tr><td>2R</td><td>8</td><td>494</td><td>2SG</td><td>20</td><td>494</td></tr><tr><td>3R</td><td>9</td><td>508</td><td>3SG</td><td>21</td><td>503</td></tr><tr><td rowspan=\"3\">紫色</td><td>1P</td><td>10</td><td>545</td><td rowspan=\"3\">黄绿</td><td>1LG</td><td>22</td><td>543</td></tr><tr><td>2P</td><td>11</td><td>557</td><td>2LG</td><td>23</td><td></td></tr><tr><td>3P</td><td>12</td><td>403</td><td>3LG</td><td>24</td><td>556 566</td></tr></table></body></html>  \n\n全部色块都是由纯色与适量的白与黑混合而成的，其关系为“白量 $\\boldsymbol{w}+$ 黑量 $^{B+}$ 纯色量 $c{=}100^{\\circ}$ (表2-2-65)。  \n\n表2-2-65奥斯特瓦尔德色彩体系记号的白黑含量  \n\n\n<html><body><table><tr><td>记号</td><td></td><td>C</td><td>e</td><td>g</td><td>i</td><td>1</td><td>n</td><td>P</td></tr><tr><td>白量W</td><td>89</td><td>56</td><td>35</td><td>22</td><td>14</td><td>8.9</td><td>5.6</td><td>3.5</td></tr><tr><td>黑量B</td><td>11</td><td>44</td><td>65</td><td>78</td><td>86</td><td>91.1</td><td>94.4</td><td>96.5</td></tr></table></body></html>  \n\n奥斯特瓦尔德颜色立体由复圆锥体构成，垂直中心轴南北两级分别为黑色（B）和白色(W)，轴上a、c、e、g、i、l、n、 $\\textsf{p8}$ 个符号分别为明度渐变的中性灰；纵断面为菱形，中心轴将菱形分割成两个对称的互为补色关系的色相三角形；色相三角形又分割成28个小菱形，分别由ca、ea、ga、ia、la、na、pa、ec、gc、ic、lc、nc、pc、ge、ie、le、ne、pe、ig、lg、ng、pg、li、ni、pi、nl、pl、 $\\mathtt{p n28}$ 个符号表示，第一个字母代表该色标中的含白量，第二个字母代表该色标中的含黑量，色相三角形的顶点为纯色，由符号 $c$ 表示。例如，某纯色色标为nc，n是含白量 $5.6\\%$ ，c是含黑量 $44\\%$ ，则其中所包含的纯色量为： $^{100-}$ 5 $\\cdot6+44)=50.4\\%$ 。再如，某纯色色标为pa，p是含白量 $3.5\\%$ ，a是含黑量 $11\\%$ ，所以含纯色量为： $100-(3.5+11)=85.5\\%.$ 西  \n\n在奥斯特瓦尔德色相三角形中，垂直于中心轴一边为明度系列，上边为明色系列，下边为暗色系列；被三边包围的内三角为含灰色的浊色系列；与中心轴线相平行的色组为等纯度系列，与上边线相平行的色组为等黑量系列，与下边线相平行的色组为等白量系列。每个色标的确定是根据该色中含有的纯色量、含白量、含黑量的比例在回旋板上通过快速旋转空间混合复制的（图2-2-18)。  \n\n![](images/4cdcc8cfcf76f445d12d99916ffbc6f43d222d43a8a24751657e14d453dc8046.jpg)  \n图2-2-18奥斯特瓦尔德色相三角形  \n\n奥斯特瓦尔德色彩体系中每一个色标都用色相号/含白量/含黑量表示，如 $8g\\mathrm{{a}}$ 表示：8号色为红色相，g为含白量 $22\\%$ ，a为含黑量 $11\\%$ ，那么此色为高明度的浅红色。  \n\n奥斯特瓦尔德色彩体系通俗易懂，它给调配使用色彩的人提供了有益的指示。在做色彩构成练习中的纯度推移时，其色相三角形不音可以视为一种配方的指导，此外，色相三角形的统一性也为色彩搭配特性显示了清晰的规律性变化。  \n\n该色系的缺陷在于等色相三角形的建立限制了颜色的数量，如果又发现了新的、更饱和的颜色，则在图上就难以表现出来。另外，等色相三角形上的颜色都是某一饱和色与黑和白的混合色，黑和白的色度坐标在理论上应该是不变的。则同一等色相三角形上的颜色都有相同的主波长，而只是饱和度不同而已，这与心理颜色是不符的。目前采用混色盘来配制同色相三角形，以弥补这一缺陷。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 587,
+        "chunk": "# 6.CIE标准色度体系  \n\nCIE（国际照明委员会，法文全称为“Commission Internationale de L'Eclairage\"）体系是1931年建立的一种色彩测量国际标准，当中规定 $700\\mathrm{nm}$ 的红、546.1nm的绿和435. ${8}\\mathrm{nm}$ 的蓝为色光的三原色。由此衍生出来1931CIE-XYZ系统。其中， $x$ 代表红原色，Y代表绿原色， $z$ 代表蓝原色。由$x$ 、Y、 $z$ 所形成的三角形包含了整个光谱轨迹，使得光谱轨迹上和轨迹之内的色度坐标都成为正值(图2-2-19)。  \n\n1964CIE补充了色度学系统。如果被观察或测定的颜色是大面积，视场角大于4°时，由于视网膜黄斑以外的杆形细胞参与了刺激作用，颜色视觉将会发生一定的变化，使得所观察的颜色饱和度降低，颜色视场出现不均匀的现象。故为适合10°大视场的色度测量系统。  \n\n![](images/c3394af642d35cf98d5a05e08742f2b25c902dda02cec4d17194db72873c4591.jpg)  \n\n1976年修正为 $\\mathrm{CIE}\\ L^{\\bullet}\\alpha^{\\bullet}b^{\\bullet}$ 。此体系用三个参数，一图2-2-191931CIE-XYZ色度图个是亮度L（luminance），另两个是颜色分量，一个为a，代表从绿（green）到红（red)，另一个是b，代表从蓝（blue）到黄（yellow）。",
+        "category": " Introduction"
+    },
+    {
+        "id": 588,
+        "chunk": "# 四、同色异谱颜色  \n\n当两个物体处于同一种照明条件（如日光）下颜色一致，但在另一种照明条件（如荧光）下颜色不相同时，这种现象人们把它称为同色异谱。这两个色样互称为同色异谱颜色，又称条件等色。虽然这两个色样在可见光范围内的光谱分布不同，但是对于特定的观察者和照明条件下具有相同的三刺激值的两个颜色。  \n\n评价颜色同色异谱程度有定性和定量两种表示方法，同色异谱图有相同的三刺激值，而光谱功率分布不同，从光谱分布的差异就可以定性描述出颜色同色异谱程度，如果颜色的光谱反射率曲线形状很不同，重合点又很少，那么同色异谱程度就高。相反，颜色之间的光谱反射率曲线很接近，重合点又很多，就表明同色异谱程度很低。用这种定性的方法虽然粗略，但有较实用的使用价值。  \n\n在大多数情况下，精确的同色异谱匹配。在特定的光源下观察原样与调配样，总会发现它们无论在明度、色相和饱和度上都可能有微小的差异。调配样与原样存在同色异谱差异。一般情况下，应允许有同色异谱差异存在，只是应尽量控制两个样品的色差，使之限制在足够小的范围内。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 589,
+        "chunk": "# 五、颜色的测量",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 590,
+        "chunk": "# 1.目测法  \n\n过去颜料色光的检测都采用目测法，规定在相同条件下将颜料分散至树脂或涂料中，然后涂布于铜版纸或玻璃片上，在日光下或标准光源下与标准样品进行平行比较，色光差异的评级分为：近似、微、稍、较四级。同时，颜料色光的测定对试验设备、光源条件、观测环境和观测者的比色条件都做了严格的规定。  \n\n在正常情况下凭肉眼观察虽然相当敏锐，而且分辨率高，但仍存在一定的局限性，对于不同色调饱和度的细微观察往往无能为力，而且目测法对色调或明度的比较结果只能做文字评述，很难做到准确。现在大多数国内外企业对颜料的测量都是通过目测法与仪器法测量相结合，来提高判断的准确性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 591,
+        "chunk": "# 2.仪器法测量  \n\n仪器法测量是运用现代先进的测色设备将制备颜料色样与标准色样用数字体现出来，通过数据与图表对待测颜料与标准颜料进行差异化描述。如通过色相、明度、饱和度及光谱反射率等对颜色进行描述，从而成为颜色沟通与传送的一种有效工具。 X  \n\n适用于染料和颜料以及应用染料和颜料加工的有色物测色仪器主要有分光光度计和光电测色仪两大类。分光光度计又随所测颜色是非透明物体的反射光，还是溶液透明色，分为反射分光光度计和透射分光光度计。也可分为单光束式分光光度计或双光束式分光光度计；还有单色扩散照明式分光光度计或多色扩散快速扫描式分光光度计；手动式分光光度计和自动式分光光度计，自动式分光光度计中又有光学平衡式分光光度计与电学平衡式分光光度计。  \n\n分光光度计生产厂家主要有DATACOLOR、MINOLTA、MACBEATH及X-rite等，其产品各有自己的特点，用户可以根据自身的需求进行选择。  \n\n仪器法测量的优点是：颜色描述数据化；颜色之间差异可以量化；配色过程具有指导性和配色成本分析功效，同时可提高配色人员的工作效率；提高配色准确性，利用仪器辅助人  \n\n工配色成了主流的配色方式。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 592,
+        "chunk": "# 3.色差的评定  \n\n在颜色测量过程中，人们一般把色差作为某物体色对比的数据表达。色差用 $\\scriptstyle\\Delta E$ 表示差异。现在大多数仪器的颜色分类系统皆以CIE中Lab色空间为基础，即将由 ${{\\mathbf{}}_{L}}\\cdot{\\mathbf{\\nabla}}$ 、a、b构成的三维空间中，以合乎标准样品的色度点为中心，以容差L'、a、b的大小为边长确定一个小型的空间区域。  \n\n色差的差异不单纯可以判断两个颜色的差距，更重要的还是对颜色混合后效果的评价，可通过已知的若干种颜色的基础数据存储在测色仪中的计算机内，然后把要求的混合色的颜色数据输入计算机，就可计算出所需要的颜色比例配方。  \n\n色差的计算有很多种计算方法，但现在普遍得到认可的就是CIE1976（L“a\"b\\*）计算方法，这是已知对用于表面颜色之间的色差定量最可靠的方法之一。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 593,
+        "chunk": "# 第五节色浆和电脑调色",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 594,
+        "chunk": "# 一、色浆（颜料制备物)  \n\n传统的颜料通常以微细粉末状态供应用户，其优点是通用性强、稳定性好及运输方便等；缺点是不能直接单独使用，往往需要添加分散剂、润湿剂等进行强力机械研磨，同时使用时粉尘较多，污染环境，配色不便。除了研制高性能颜料品种外，如何改进现有产品应用性能，提高使用价值，扩大应用范围也是非常必要的。  \n\n当前人类对环境日益关注，“三废”污染是各涂料生产企业所关注的。而使用水浆颜料（色浆）与其他非粉末颜料制备物（如各类颜料分散体、色母粒、色膏、可分散颜料等）可有效地解决粉尘与污水的污染。使用便捷，便于配色；省去了费能、费力、费时的分散研磨工序；改善颜料应用性能（如提高展色性、有效防止浮色与发花等)，提高工作效率。因此，颜料的新型制备物是颜料品种发展的主要方向之一。但通用性受到一定限制，专业性也越来越强，出现了多种剂型颜料制备物（如涂料色浆、皮革色膏、塑料色母粒、涂料印花浆、油星色浆及工业色浆等)。",
+        "category": " Introduction"
+    },
+    {
+        "id": 595,
+        "chunk": "# 1.涂料色浆的定义与分类  \n\n涂料色浆是指用于涂料调配色的一种着色剂，它是一种颜料制备物。是将粉末颜料、溶剂（水或有机溶剂）、树脂、颜料分散剂及多种功能稳定剂通过强力机械复合加工而成的，具有良好的分散性与稳定性，可流动，与涂料具有良好的相容性等。  \n\n涂料色浆按体系分为水性色浆、溶剂型色浆与水油两用色浆，还可分为含树脂色浆与无树脂色浆；按加工颜料特性分为无机颜料色浆与有机颜料色浆，耐晒型色浆与不耐晒型色浆，纳米色浆与普通色浆，透明色浆与遮盖型色浆；按用途分为工业漆色浆、建筑涂料（含乳胶漆色浆）色浆与装饰涂料色浆等；按颜色分为黄色色浆、蓝色色浆、红色色浆与黑色色浆等；按添加方式分为工厂调色（厂用）色浆与机械调色（机用）色浆；还可根据涂料用途、添加溶剂及树脂种类和环境要求（如重金属与VOC含量等）分类等。通常习惯按体系与添加方式进行分类。",
+        "category": " Introduction"
+    },
+    {
+        "id": 596,
+        "chunk": "# 2.水性色浆  \n\n水性色浆是以水为分散介质的颜料浓缩浆，它是通过分散剂、润湿剂、稳定剂及其他功能剂来使颜料充分润湿分散，达到优化颜料应用性能、稳定体系的效果。主要是利用静电屏蔽与空间位阻作用原理来分散稳定颜料颗粒。  \n\n(1）色浆加工的基本原理颜料分散润湿稳定机理是：正确使用分散润湿助剂，降低颜料与体系的界面张力，使颜料达到充分解絮凝，从而有效改善颜料的应用性能。  \n\n一般无机颜料分散是用离子型助剂，具有较高的表面极性，对助剂的吸附比较容易。有机颜料的分散则多用非离子高分子聚合物助剂。有机颜料有一个非极性的表面，对常规助剂的吸附比较困难，高分子聚合物助剂具有树脂那样的特性，有很多吸附基团，从而可使有机颜料颗粒表面形成吸附层，通过聚合物链的空间屏蔽作用产生了稳定化作用，具体体现如下。  \n\n①分散润湿助剂使颜料表面已吸附的空气和潮气排出，由原有的固/气界面（颜料颗粒/空气或潮气）转变为固/液界面（颜料颗粒/助剂或体系溶剂、水）。  \n\n②颤料研磨过程，通过机械能（剪切力和冲击力）使颜料颗粒分数，并使助剂分子充分润湿颜料颗粒，形成更为细小的颜料分散体（图2-2-20)。颜料分散体的粒径大小与粒度分布对水性色浆应用性能影响比较大，如色光、鲜艳度、分散性、耐光性及特殊薄漆膜要求等。  \n\n③利用特种阴离子分散助剂来增强颜料颗粒表面电荷，并通过同性电荷相斥的原理稳定颜料分散体（图2-2-21)。在静电屏蔽稳定作用下，每个颜料颗粒都包围着一个双层离子电荷。一个颜料粒子先吸附负离子[一]，随后会被一个正离子[十］层包围。当两个颜料颗粒彼此接近时，库仑排斥力占优势，从而改变它们的运行轨迹避免更接近。  \n\n![](images/fb2f84c8c055d5fe668cef9cbb5afcc724a553dbee1ee8383a60b39e2040fa3a.jpg)  \n图2-2-20颜料颗粒的分散与润湿过程  \n\n![](images/1361839a2d633c41329421594b277393357a7cbf52e8cd1e520459d9c7a58ebd.jpg)  \n图2-2-21电荷稳定作用  \n\n④利用含有多个“亲颜料”（如锚定基团等）基团的分散剂中亲颜料基团对颜料颗粒表面牢固、持久吸附，大量的碳氢链段（分散剂链）从颜料颗粒表面伸向周围，通过这种较厚的吸附层（一般要大于10nm），形成空间位阻作用，阻止颜料颗粒之间紧密接触，并形成一层保护膜“壳”，这种核-壳结构不仅能够改进颜料性能，还能有效降低颜料分散体之间吸附，提高色浆的稳定性（图2-2-22)。位阻作用机理可以在极性（如水）和非极性（如石油醚）溶剂中发挥作用。当电介质存在时，会使颜料分散体颗粒变大，粒径分布不均匀，分散  \n\n![](images/135e2d37450745795ed33cbd1efdea6515d5e4473d2ca477254754f452b87471.jpg)  \n图2-2-22空间位阻效应  \n\n性变差，其中价电子越大的离子影响越大，随着价电离子的价数减少，影响变小，这可能是  \n由于多价离子压缩了胶团表面的双电层厚度，使胶团带电量下降，减少颗粒之间排斥力，从  \n而使分散性下降。因此，色浆体系中有电介质存在，会对颜料分散体的粒径及分散性有较大  \n的影响。，  \n\n颜料与润湿分散助剂是否相匹配，不仅影响颜料分散体的抗絮凝程度、在其他介质中的分散性、贮存稳定性及颗粒大小与粒径分布，同时还会影响色浆的鲜艳度、着色强度、耐水性及耐晒性等应用性能。  \n\n(2）简单制备工艺水性色浆与涂料生产工艺基本相似，分为：水、溶剂与助剂的预分散工艺（预混合)→投人颜料后高速分散（强力机械剪切） $\\mathbf{\\rightarrow}$ 添加功能添加剂后进行研磨工艺(循环研磨，要求控制粒度大小与分布控制)→搅拌控制与熟化工艺（色相、着色力、黏度、密度等的测定与调整及体系熟化）。  \n\n(3）关键控制指标说明水性色浆的分散性、相容性、颜色、着色强度、耐性（耐光性、耐候性、耐酸性、耐碱性)、粒度分布与细度、贮存稳定性（常温、热贮与冷冻)、黏度、密度、外观、流动性及批次重现性是每个使用色浆人员所关注的，它涉及产品的品质与使用成本。与颜料相同，颜色、着色强度、耐性等主要取决于使用颜料的结构特性；粒径（细度）与粒度分布、黏度、密度、外观、流动性是反映色浆稳定性的重要指标，一般在色浆厂作为出厂检验指标提供给用户。控制好分散性、相容性（通用性)、pH、粒度分布与细度、长时间稳定性及批次颜色差异是制备好色浆的关键技术，也是用户考察是否选用色浆的前提条件。  \n\n着色强度也称色浓度，是水性色浆的一个重要指标，反映色浆的颜料含量、展色性及颜料分散体絮凝情况。一般数据是按颜色以达到国际标准深度（ISD）的1/25所需颜料浆的份数来衡量，数值越小，着色力越高。也可按照颜料着色力检测方法进行评定。  \n\n相容性与分散性是最能体现色浆品质的指标之一，也是色浆的一个重要应用指标。相容性是指色浆加人基础涂料中的展色情况描述，如立即出现增稠、返粗及起粒等现象，则属色浆与该涂料的相容性极差。一般检测方法是将色浆按照一定比例加入基础涂料中达到同等深度对涂膜进行指研，目测与仪器测量色差越小越好，并要求色浆在尽可能多的涂料体系中有好的相容性。分散性是指色浆中颜料分散体的大小、分布及在水、各类水性树脂、醇醚中稀释的状态情况。分散性也是描述色浆中颜料颗粒的解絮凝程度。一般来说，颜料颗粒在体系中不可能达到完全解絮凝（即颜料颗粒在体系中成为均一稳定原级粒子)，尽可能使颜料分散体小。这样还会直接影响色浆着色强度、展色性和贮存稳定性等。  \n\n粒度分布与细度是反映颜料、助剂的配伍及分散、研磨工艺合理性的一个综合性指标，也是用户选择色浆的重要依据之一。细度是从宏观角度描述颜料分散体大小，而粒度分布则是从微观角度反映了颜料分散程度的好坏。同时色浆在涂料中呈现出来的色光、鲜艳度、着色力及耐性与粒度分布有很大关系。  \n\n稳定性及批次颜色差异是用户比较关注的。如严重分层、沉降、絮凝、着色力下降等现象，导致用户很难稳定配色比例。一般对色浆稳定性测试是通过热贮、冷冻循环测试，比较着色力、细度、粒度分布差异及外观状态评估。批次颜色差异是指同一牌号色浆不同批次之间差异，一般用仪器法与目测法对待测样品与标准样品进行测量，比较差异。目测评级分为近似、微、稍、较四级；仪器测量用E、 $\\Delta H$ 、L、△a、b等进行描述。 K  \n\n涂料色浆在国内发展不到十年的时间，对色浆检测仪器设备及方法不多。选用色浆基本上还是以技术人员的经验判断、产品的品牌和进行简单的测试评估，导致一些用户在选用色浆时存在一定的盲目性。有的完全从众，有的也仅比较着色力，甚至对不同颜料索引号的颜料直接进行比较，还有的就是看看色浆厂家做的比较样板就选用。其实色浆在涂料中添加量与成本相对比较小，却起到关键作用（色彩效果、装饰效果、耐性效果)。因此，选择色浆必须慎重，多了解（多学习色浆颜料与助剂的知识)，多试验，多比较。其关键在于掌握色浆与涂料自身配伍性（分散性、相容性)、色浆本身的耐性（制备色浆颜料结构号）及应用特性。  \n\n(4）建筑涂料用水性色浆随着涂料工业的飞速发展和调色新技术的应用，尤其是建筑涂料，涂料行业专业化分工将是未来的发展趋势。专业的色浆企业和涂料厂家间的密切合作让涂料厂家得益匪浅。目前建筑涂料用水性色浆形成一种除粉末外颜料的最为主要的剂型，并已自成体系。国内外产品品种繁多，为规范色浆行业发展，促进涂料工业进步，我国已于2006年由中国化工建设总公司常州涂料化工研究院、昆山市世名科技开发有限公司等5个主要起草单位拟定了化工行业标准《建筑涂料用水性色浆》HG/T3951—2007，对色浆的着色力、颜色、黏度、有机挥发分（VOC）与重金属的限量及在容器中状态等16项进行了规定。  \n\n建筑涂料用水性色浆按使用方式分为厂用色浆与机用色浆。机用色浆在色浓度、色差、着色力、黏度、密度及装机稳定性等方面提出了更高的要求。厂用色浆不受品种数量限制，有的仅黄色品种就有十几支，用于不同要求。只要符合颜色、耐性等要求的品种就可以加工制备色浆出售；而机用色浆受调色设备的限制，一般为10支、12支、14支或16支组，每组还要求尽可能大地覆盖色空间，颜色还要均匀分布在整个色区中，便于调配更多颜色。  \n\n(5）市场主要产品目前，市场水性色浆国际色浆生产企业主要有芬兰迪古里拉(TIKURILA)、瑞士汽巴精化（Ciba）、德国科莱恩（Clariant)、德国德固萨（Degussa）及德国巴斯夫（BASF）公司等。国内色浆生产企业规模相对比较小，技术力量比较薄弱，不过近几年发展速度比较快，涌现了几家具有一定规模的生产企业。如上海德固萨、上海希必思、昆山世名科技、深圳海川色彩及广州科迪色彩等。主要生产厂家及产品性能可参考各个厂家的产品说明书。其主要产品系列如下。  \n\n$\\Phi$ 厂用色浆：汽巴色浆；科莱恩色浆；巴斯夫色浆；德固萨色浆；希必思色浆；昆山世名水性色浆；海川色浆。  \n\n$\\textcircled{2}$ 机用色浆：芬兰迪克里拉（TIKURILA）色浆；世名机用色浆；德固萨机用色浆。  \n\n$\\textcircled{3}$ 超低VOC环保水性色浆：世名NV系列色浆；德固萨COLORTRENDPLUS803系列色浆。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 597,
+        "chunk": "# 3.溶剂型色浆  \n\n溶剂型色浆是以有机溶剂和树脂为分散介质，着色强度和流变性经严格控制的颜料浆。由颜料、油性树脂（如多羟基不饱和聚酯、酚醛树脂、醛酮树脂及丙烯酸树脂等)、颜料分散助剂、稳定剂、助溶剂及功能助剂等组成。由于溶剂型涂料应用范围广，不同应用对象对涂料的性能要求不同，其取决于制备涂料所选用的树脂和配方设计。溶剂型涂料所用的树脂与溶剂种类繁多，不同极性溶剂和不同反应活性的树脂对色浆要求是不同的。这样很大程度上限制了溶剂型通用色浆的发展。选择溶剂型色浆的关键不只是色浆与涂料的相容性，更为重要的是考虑添加色浆后，色浆中的分散介质（树脂）对涂料性能负面影响程度，尤其是高档工业涂料。因此，大多数有规模的溶剂型涂料厂采用定制加工或自行研磨。如德固萨POLYTREND850系列主要用于不饱和聚酯中着色。人们还是希望能制备通用性更为广泛的溶剂型色浆，以满足一些常见溶剂型涂料的配色要求。因此选择研磨树脂至关重要，它不仅影响色浆与涂料的相容性、涂膜性，还影响色浆的色浓度、鲜艳度（光泽)、稳定性及流变性等。目前，通过涂料行业人士不断试验，认为醛酮树脂具有很好的通用性和颜料润湿性，比较适合制备溶剂型通用色浆。目前，也有无树脂溶剂型色浆，其通用性更强，但要开发高颜料含量无树脂溶剂型色浆，困难较大。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 598,
+        "chunk": "# 4.水油两用型色浆  \n\n水油两用型色浆是指既可以用于水性涂料着色，又可以用于溶剂型涂料着色的颜料浆。由于技术上不仅要解决色浆与水性涂料和溶剂型涂料相容性及分散性问题，还要解决色浆在水与其他多种有机溶剂中的稀释性（极性差异较大)，该类色浆开发难度较大。国外有一些色浆生产厂商也推出了此类色浆，多数为二元醇色浆，主要推荐应用于水性建筑、装饰涂料和一些中长油度的醇酸、丙烯酸涂料。因此，水油两用色浆原则上是指用于部分水性涂料中和一些弱极性油性涂料着色的颜料浆。主要是为了方便一些民用涂料零售店家装涂料配色。这类色浆市场上比较少，需求量也不是非常大。如德固萨COLORTREND888系列色浆、世名公司的U系列色浆。",
+        "category": " Introduction"
+    },
+    {
+        "id": 599,
+        "chunk": "# 二、配色  \n\n涂料配色是涂料制备的一个重要组成部分。主要分为人工配色和电脑配色。",
+        "category": " Introduction"
+    },
+    {
+        "id": 600,
+        "chunk": "# 1.人工配色  \n\n人工配色是指根据对色样（色卡、实物及颜色数据描述等）进行目测后，选用着色剂（色浆或色膏）搭配涂料进行调配的一种配色方法。也可以通过测色设备对原样颜色与所调配颜色进行色差评定。  \n\n涂料配色主要是根据减色法混色原理。减法混合的三原色就是颜料的三原色，即品红、黄、青（湖蓝)，它们的补色是绿、紫、橙。由于生产的三原色颜料色光、饱和度都偏暗，同时涂料对颜色性能（如耐晒牢度、耐碱性及耐溶剂性）与成本也有不同的要求，因此，在实际配色工作中直接采用三原色难度是非常大的。涂料着色颜料品种繁多，几乎覆盖色空间每个区域，大大增加了涂料配色的难度。人工配色对配色人员要求较高，既要了解涂料与着色剂性能，又要熟悉配色知识（主要配色原理在第四节色彩基本理论有详细介绍）。  \n\n人工配色步骤总体可分为：（1）接单（确定色样—色卡、实物及颜色数据描述)；(2）颜色分析（仪器或经验——类似留样比较分析，并确立着色剂品种)；（3）结合涂料要求，选用合适的着色剂做相容性实验（颜色选择—色相、饱和度、耐性)；（4）结合涂料配色小样（要求精确计量及记录配方，涂膜干燥条件，颜色比对时需考虑环境、涂料自身光泽等因素)；（5）批量调色（注意需预留基础涂料，出现其他非配色相关技术问题与涂料技术人员沟通，并给出解决办法)；（6）确认交单及存档管理（主管或用户确认、填写配色流程记录单并存档管理、留样保存)。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 601,
+        "chunk": "# 2.电脑配色  \n\n电脑配色是一种基于现代色彩学、光学、计算机科学和仿真学理论，用数字化的软件形式取代传统依赖人工经验的一种配色模式。近年来电脑配色技术发展非常快，已经在纺织、印染、油墨及涂料行业广泛应用。目前，已有一些成型产品，如美国的X-rite、Photo Research公司、瑞士的 $\\scriptstyle\\mathrm{Textest}$ 公司等，国内涂料用配色软件产品如昆山世名电脑配色系统。  \n\n(1）涂料电脑配色的基础理论电脑配色的理论基础是Kubelka-Munk理论，根据K  \n\nM理论，涂层内表面处颜料的光谱反射率 $R$ 为：  \n\n$$\n1+\\frac{k}{s}-\\frac{1}{21}\\left[2\\left(1+\\frac{k}{s}\\right)-1\\right]\n$$  \n\n式中k——颜料的吸收系数；s—颜料的散射系数。  \n\n涂料中的颜料含量越大，对光的吸收量越多，反射量越少，即涂料的颜色浓度与光谱反射率有一定的关系。因此，可以用分光光度计测量不同试样的光谱反射率，进而计算出 $k/s$ 总值，再存储于计算机中。  \n\n同时，在不发生干扰的情况下，涂膜颜色 $k/s$ 值是各颜料组分的 $k/s$ 值之和，即：  \n\n$$\n(\\frac{k}{s})m\\lambda=[(\\frac{k}{s})a+(\\frac{k}{s})b+(\\frac{k}{s})c+(\\frac{k}{s})R]\\lambda\n$$  \n\n式中 $(k/s)m$ 涂料涂膜的 $k/s$ $(k/s)_{\\alpha}$ ， $(k/s)b$ ， $(k/s)c$ —各颜料的 $k/s$ (k/s)R—基料的k/s;-—人射光波的波长。  \n\n配色时，先测出标样的三刺激值 $x_{*}$ ， $\\scriptstyle\\mathbf{Y}_{3}$ ， $z_{*}$ ，再由计算机估算出配色仿样的三刺激值$X_{\\mathrm{m}}$ ， $Y_{\\mathrm{ra}}$ ， $Z_{\\mathrm{m}}$ ，继而将两组三刺激值进行比较，使 $\\boldsymbol{X}_{s}=\\boldsymbol{X}_{\\mathrm{m}}$ ， $Y_{\\mathrm{s}}=Y_{\\mathrm{m}}$ ， $Z_{\\mathrm{*}}=Z_{\\mathrm{*}}$ (s表示标样，m表示仿样)。若两者的三刺激值不一致，可再进行校正计算，直至一致为止，同时可得到各着色剂（色浆）的添加量，即调色配方。  \n\n(2）电脑配色系统的组成  \n\n$\\Phi$ 电脑配色结构流程配色结构流程如图2-2-23所示。  \n\n![](images/e73111d2f3205534a4f557c495e7673addda2e5579ec49bcfab23d7692ff3954.jpg)  \n图2-2-23配色结构流程  \n\n$\\textcircled{2}$ 配色软件主要构架给出颜色准确与否主要取决于所选用的配色软件的配色算法，这也是整个电脑配色的核心部分。配色算法主要由以下三块组成。  \n\na.着色剂（色浆）库建库算法实际上就是将着色剂的颜色属性用数学参数进行描述的过程，即数学建模过程。每种配色软件都有自己独特的建库过程与方法，目的就是尽量精确地描述着色剂的颜色属性（算法不做详细介绍）。  \n\nb.配色算法电脑配色软件，通常建立基于浓度的相对 $\\kappa$ ， $s$ 参数模型，然后通过测量相关色料的 $\\kappa$ ， $s$ 值来求解配方，其核心算法为：  \n\n$$\n\\frac{C_{\\circ}\\left(\\frac{K}{S}\\right)_{\\dot{\\Theta}}+C_{1}\\left(\\frac{K_{1}}{S_{\\dot{\\Theta}}}\\right)+\\dots+C_{n}\\left(\\frac{K_{n}}{S_{n}}\\right)}{C_{\\circ}+C_{1}\\left(\\frac{S_{1}}{S_{\\dot{\\Theta}}}\\right)+\\dots+C_{n}\\left(\\frac{S_{n}}{S_{n}}\\right)}=\\left(\\frac{K}{S}\\right)_{\\mathfrak{m e}}\n$$  \n\n其中，涂料的 $\\kappa$ ， $s$ 值与白涂料的 $s$ 值都是波长的函数，在可见光范围 $400\\sim700\\mathrm{nm}$ 每隔 $10\\mathrm{nm}$ 列一个方程，共31个方程。  \n\n$$\nC_{1}+C_{2}+\\cdots+C_{n}=100.0\n$$  \n\n再加上以上方程[式（2-2-8）］共有32个方程。配色算法的基本思想是使 $\\scriptstyle\\Delta E$ 最小，而$\\Delta E$ 与 $\\Delta x\\Delta y\\Delta z$ 直接相关。故根据式（2-2-9）进行首次配色计算：  \n\n$$\n\\begin{array}{c}{{\\displaystyle\\Delta X=\\sum_{0}^{30}E\\bar{x}\\frac{\\mathrm{d}R}{\\mathrm{d}\\left(\\frac{K}{S}\\right)}\\biggl[\\frac{K}{S_{\\Theta\\Psi}}-1\\left(\\frac{K}{S}\\right)_{\\mathrm{\\tiny{\\oplus}}}-\\frac{C_{1}}{C_{0}}\\Bigl(\\frac{K_{1}}{S_{\\Theta}}\\Bigr)-\\cdots-\\frac{C_{n}}{C_{0}}\\Bigl(\\frac{K_{n}}{S_{n}}\\Bigr)\\biggr]\\Delta S}}\\\\ {{\\displaystyle\\Delta Y=\\sum_{0}^{30}E y\\frac{\\mathrm{d}R}{\\mathrm{d}\\left(\\frac{K}{S}\\right)}\\biggl[\\frac{K}{S_{\\Theta\\Psi}}-1\\left(\\frac{K}{S}\\right)_{\\mathrm{\\tiny{\\oplus}}}-\\frac{C_{1}}{C_{0}}\\Bigl(\\frac{K_{1}}{S_{\\Theta}}\\Bigr)-\\cdots-\\frac{C_{n}}{C_{0}}\\Bigl(\\frac{K_{n}}{S_{n}}\\Bigr)\\biggr]\\Delta S}}\\\\ {{\\displaystyle\\Delta Z=\\sum_{0}^{30}E z\\frac{\\mathrm{d}R}{\\mathrm{d}\\left(\\frac{K}{S}\\right)}\\biggl[\\frac{K}{S_{\\Theta\\Psi}}-1\\left(\\frac{K}{S}\\right)_{\\mathrm{\\tiny{\\oplus}}}-\\frac{C_{1}}{C_{0}}\\Bigl(\\frac{K_{1}}{S_{\\Theta}}\\Bigr)-\\cdots-\\frac{C_{n}}{C_{0}}\\Bigl(\\frac{K_{n}}{S_{n}}\\Bigr)\\biggr]\\Delta S}}\\\\ {{\\displaystyle C_{0}+C_{1}+\\cdots+C_{n}=100}.}\\end{array}\n$$  \n\n因为 $\\Big(\\frac{S_{v\\ast}}{S_{\\mathsf{H}}}\\Big)\\div\\frac{}{\\mathsf{I}}\\Big(\\frac{K_{v\\ast}}{S_{\\mathsf{H}}}\\Big);$ 都是浓度的函数，故式（2-2-9）得到的初始解需要代入式（2-2-10)选代计算几次以便求出精确解。  \n\n$$\n\\begin{array}{r}{\\Delta X=\\underset{0}{\\overset{.}{\\sum}}E\\bar{x}\\frac{\\mathrm{~d}R}{\\mathrm{~d}\\left(\\frac{K}{S}\\right)}\\left[\\frac{K}{\\bar{S}\\otimes\\Psi}-\\frac{C_{0}\\left(\\frac{K}{S}\\right)_{\\oplus}}{C_{0}+C_{1}\\left(\\frac{S_{1}}{S_{0}}\\right)+\\dots+C_{n}\\left(\\frac{K_{n}}{S_{n}}\\right)}{\\bar{S}\\otimes\\Psi}\\right]\\Delta S\\right]}\\\\ {\\Delta Y=\\underset{0}{\\overset{.}{\\sum}}E\\bar{y}\\frac{\\mathrm{~d}R}{\\mathrm{~d}\\left(\\frac{K}{S}\\right)}\\left[\\frac{K}{\\bar{S}\\otimes\\Psi}-\\frac{C_{0}\\left(\\frac{K}{S}\\right)_{\\oplus}+C_{1}\\left(\\frac{K_{1}}{S_{0}}\\right)+\\dots+C_{n}\\left(\\frac{K_{n}}{S_{n}}\\right)}{C_{0}+C_{1}\\left(\\frac{S_{1}}{S_{0}}\\right)+\\dots+C_{n}\\left(\\frac{S_{n}}{S_{n}}\\right)}\\right]\\Delta S\\right\\}}\\\\ {\\Delta Z=\\underset{0}{\\overset{.}{\\sum}}E\\bar{z}\\frac{\\mathrm{~d}R}{\\mathrm{~d}\\left(\\frac{K}{S}\\right)}\\left[\\frac{K}{\\bar{S}\\otimes\\Psi}-\\frac{C_{0}\\left(\\frac{K}{S}\\right)_{\\oplus}+C_{1}\\left(\\frac{K_{1}}{S_{0}}\\right)+\\dots+C_{n}\\left(\\frac{K_{n}}{S_{n}}\\right)}{C_{0}+C_{1}\\left(\\frac{S_{1}}{S_{0}}\\right)+\\dots+C_{n}\\left(\\frac{S_{n}}{S_{n}}\\right)}\\right]\\Delta S\\right]}\\end{array}\n$$  \n\nc.配方修正算法当按照配方配出的颜色与样卡相差较大时，可以使用配方修正算法，计算出着色剂的调整量，减少手工调整的工作量。配方修正的计算，首先假设色浆的参数不变，然后以仿样色卡与样卡的xy为已知量，配方的修正量为方程的另一边（算法不做详细介绍）。  \n\n·配色软件的功能电脑调色软件功能大致分为系统设置、着色剂库管理、样卡管理、配方管理、配色计算、误差评定、配方修正等。其中核心是具有配色能力的配色计算功能。  \n\n·配色辅助设备主要包括计算机和分光光度计等。  \n\n(3）电脑调色一体化电脑调色一体化是以电脑配色软件为核心，借助调色设备（如调色机、混合机）等，能够快速有效解决涂料颜色问题的一种配色系统，同时还可以进行颜色性能评估与成本分析。该系统主要包括色样［PANTONE色卡、国标色卡、建筑涂料色卡(GSB16-1629-2003）、各类涂料厂家色卡、颜色实物及标准数据描述]，可调色基础漆（不同消色力的涂料用来调配不同深度颜色漆)，机用色浆（要求装机稳定性、性能保证、批次一致性)，配色软硬件（分光光度计、软件、电脑等），调色设备（各类调色机12/16、混合机等）等几个组成部分。它能一体化地满足用户从选色、测色、配色到颜色实现的各个环节，是一种全面的调色解决方案。其工作模式如图2-2-24所示。  \n\n![](images/6a9dc7a96995446f6d05002a1b7a0e2d93c0c1edf8ea9f8ff36c450b73074d6e.jpg)  \n图2-2-24 电脑调色工作模式",
+        "category": " Introduction"
+    },
+    {
+        "id": 602,
+        "chunk": "# 第六节颜料和填料的发展趋势",
+        "category": " Introduction"
+    },
+    {
+        "id": 603,
+        "chunk": "# 一、开发高性能颜料品种  \n\n开发新型化学结构颜料品种的目的是提高颜料的耐久性、耐热性、耐溶剂性与耐迁移性等。主要途径是合成新型的多环结构颜料及稳定晶型结构，使其具有良好的分子平面性、对称性，含有特定取代基，改变分子极性，形成分子间氢键。  \n\n随着涂料工业的发展，高性能有机颜料（HPOP）应用越来越广泛。开发高性能有机颜料主要包括喹吖啶酮类颜料、特殊偶氮颜料〔缩合偶氮颜料（大分子有机颜料)]、吡咯并吡咯二酮（DPP）类颜料、葱类颜料、靛族与硫靛类颜料、系与花系颜料、异吲哚啉酮及异吲哚啉类颜料和喹酞酮类颜料等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 604,
+        "chunk": "# 二、颜料表面处理  \n\n为改进现有品种的性能，提高其使用价值，对现有颜料的颗粒表面进行表面处理，可以改变颜料的表面特性，使其满足更广泛的应用要求。经过表面处理后的颜料，用于涂料中可以改善颜料的分散性与着色性，提高颜料的耐候性、耐光性及耐化学药品性等。目前，颜料表面处理在我国仅处在初级阶段，颜料的应用性能与国外同结构产品差异较大。因此，如何提高颜料表面处理效果对提升我国颜料品质是至关重要的。主要表面处理技术简单介绍如下。  \n\n①高分子聚合物包膜处理方法，可以改善颜料的分散性、鲜艳度、耐久性与耐溶剂性等。  \n\n②有机硅、有机铝化合物对无机颜料进行表面改性处理技术，可以降低颜料的吸油量，提高其抗紫外线能力与耐溶剂性等。 二  \n\n③颜料衍生物（有色或无色）表面改性方法，可以提高颜料分散稳定性，提高抗絮凝性。  \n\n④无机氧化物与有机络合物沉淀改性技术，可以增强颜料的润湿性。  \n\n③合成复合性有机颜料技术，可以改善一些反应性颜料的性能。如化学型“混晶”DPP颜料的制备。  \n\n③其他表面处理技术（超临界流体中颜料化技术、激光辐射颜料分散技术与等离子体  \n\n溅射颜料改性技术等）。",
+        "category": " Introduction"
+    },
+    {
+        "id": 605,
+        "chunk": "# 三、颜料与填料的超微粉碎或纳米化  \n\n通过超微粉碎技术使一些常用无机颜填料纳米化，使颜填料颗粒达到纳米范围$_{<100\\mathrm{nm}}$ ）的尺寸。纳米是一个长度计量单位， $\\scriptstyle1\\mathrm{nm}$ 等于 $10^{-9}\\mathrm{m}$ 。纳米技术是以 $\\ 0.1\\sim$ $100\\mathrm{nm}$ 尺寸的物质为研究对象，研究纳米材料的制备及其应用的高新科技。纳米材料（具有纳米尺寸的材料因表面富集原子及分子结构活性中心骤增）具有量子尺寸效应、小尺寸效应、表面效应、宏观量子隧道效应和介电限域效应等特殊效应。如果将纳米化后的颜料和填料，稳定分散（以纳米尺寸分散）在涂料基料中后，可赋予涂料许多新的特殊功能。  \n\n常见的在涂料工业中应用的纳米颜填料有纳米二氧化钛、纳米氧化锌、纳米二氧化硅、纳米碳酸钙、纳米氧化铁、纳米氧化锡、纳米氧化锆、纳米金属粉等。涂料中加入上述纳米材料后，可制成高级闪光汽车漆，防红外线、防声呐、防雷达和多种电磁波的伪装涂料，自抛光船舶防污涂料，自洁装饰涂料，杀菌涂料，静电屏蔽涂料，防紫外线涂料等，提高涂料的力学性能、耐候性和其他功能。  \n\n因此颜料和填料的纳米化（特别是无机颜填料）是近年来的发展趋势之一。但是实现颜填料纳米化后带来的问题是如何使这些颗粒极细，比表面积极高的材料能稳定地以纳米尺寸分散在色料中，这是纳米材料在涂料中应用的一个“瓶颈”。纳米化后的颜填料必须经表面修饰，再配合使用合适的分散剂助剂，才能保持分散体具有良好的稳定性，才能充分发挥上述的纳米颜填料的几大效应，使涂料的性能有“质”的飞跃，或具有特殊的功能。使其具有量子尺寸效应、小尺寸效应、表面效应、宏观量子隧道效应、介电限域效应等纳米粒子的特殊效应。颜料粒径变小、粒度分布变窄，可改善颜料的着色强度、色光、抗紫外线性（耐候性)、杀菌防霉性与透明性等。不同纳米材料在对涂料改性方面可起到不同的作用。因此，部分无机颜料纳米化是近年来发展的一大趋势。",
+        "category": " Introduction"
+    },
+    {
+        "id": 606,
+        "chunk": "# 四、颜料与填料的剂型化  \n\n传统的颜料通常以粉末状态供应给用户直接使用，其缺点是使用过程中容易产生粉尘飞扬，对整个生产车间环境污染比较大。用于涂料着色时还需要数道研磨分散工序，且不利于调色。而将粉末颜料加工成各种新剂型或专用剂型（即各类颜料制备物)，如色浆，膏状、流体颜料分散体及色母粒等。不仅可以避免粉尘飞扬，简化费时费力的研磨工序，同时还有利于配色，提高颜料的着色性（如着色力、鲜艳度及抗絮凝性等)。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 607,
+        "chunk": "# 五、颜料与填料的环保化  \n\n$\\Phi$ 开发生产防尘颜料及颜料品种剂型化，可以减少粉尘飞扬，是颜料加工的一个重要发展方向。  \n\n$\\textcircled{2}$ 开发生产无毒、无害的高性能有机颜料来取代含铅、铬、镉、汞等金属化合物及一些使用多氯联苯（PCBs）与多氯二苯等致癌物质为中间体的偶氮类有毒颜料。 YO  \n\n$\\textcircled{3}$ 降低颜料中对人类有害的重金属含量。  \n\n$\\textcircled{4}$ 在生产过程中控制“三废”的产生，减少环境污染。",
+        "category": " Introduction"
+    },
+    {
+        "id": 608,
+        "chunk": "# 参考文献  \n\n[1］涂料工艺编委会，涂料工艺，第3版，北京：化学工业出版社，2001.  \n[2]朱骐良，吴申年，颜料工业学，第2版，北京：化学工业出版社，2002.  \n[3] 周春隆，穆振义，有机颜料，北京：化学工业出版社，2002.  \n[4] 沈永嘉，有机颜料- 一品种与应用．第2版，北京：化学工业出版社，2002.  \n[5] 杜克生，李光源，颜料染料涂料检验技术，北京：化学工业出版社，2005.  \n[6] 徐扬群，珠光颜料的制造加工与应用，北京；化学工业出版社，2005.  \n[7] 周春隆，穆振义. 有机颜料索引卡，北京：中国石化出版社，2004.  \n[8] [加]GeorgeWypych编，填料手册，程斌，于运花译，北京：中国石化出版社，2002.  \n[9] 周学良. 颜料，北京：化学工业出版社，2002.  \n[10] 韩长日，宋小平，颜料制造与色料应用技术，北京：科学技术文献出版社，2001.  \n[11] 沈浩．制漆配色调制工，北京：化学工业出版社，2006.  \n[12] 黄国松. 色彩设计学，北京：中国纺织出版社，2001.  \n[13] 全国涂料和颜料标准化技术委员会，化学工业标准汇编-涂料与颜料（上、下）.  \n[14] 林宜益. 乳胶漆. 北京：化学工业出版社，2004.  \n[15] 张红鸣， 徐捷. 实用着色与配色技术，北京：化学工业出版社，2001.  \n[16] 周震，武兵. 印刷油墨的配方设计与生产工艺，北京：化学工业出版社，2004.  \n[17] 石玉梅. 建筑涂料与涂装技术400间，第2版，北京：化学工业出版社，2002.  \n[18] 陈泽森，刘俊才，水性建筑涂料生产技术，北京：中国纺织出版社，2001.  \n[19] 吴立峰，塑料着色和色母粒，北京：化学工业出版社，1998.  \n[20]Hager Gregory Todd, Ashley Michael L, Pillars Darci.Method for making high tint strength pigment composi-tions; US， 2007137526.2007-06-21.  \n[21] Oyanagi, TakashiNakano,Pigment dispersedliquid,production method for the same,andlight curable ink com-position using the pigment dispersed liquid; EP, 1798265. 2007-06-20,  \n[22] Cepria G, Roque J,Molera J.Electroanalytical studyof the composition of the raw pigmentmixtures that yield themetalic lustre onceramies.A link between composition and final result,Electroanalysis, 2007, 19（11)1167-1176.  \n[23]Criado Maria N,Romero Maria P,Motilva Maria J.Efectof the technological and agronomical factors on pigmenttransfer during olive oil extraction.Journal of Agricultural and Food Chemistry, 207, 55 (14): 56815688.  \n[24]Halova Jaroslava,Suloova Petra,Kupka Karel.Computerized pigment design based on property hypersurfaces,Journal of Physies and Chemistry of Solids, 2007, 68 (5-6) 744-746.  \n[25]Doering Georg Josef,Reisacher Hansulrich,Mauthe Uwe,Method for the dispersion of solid pigment preparationsin liquid medis； WO, 2007065839,2007-06-14.  \n[26]Jing Chen,Hanbing,Shi XiaoboThe preparationand characteristicsof cobalt blue colored mica titania pearlescentpigment by microemulsions, Dyes and Pigments, 2007, 75 (3); 766-769.  \n[27]Karlis james, Zickell Thomas,Weatherproof underlayment withhigh filer content polymer asphalt layer; CA,2550172. 2007-06-01.",
+        "category": " References"
+    },
+    {
+        "id": 609,
+        "chunk": "# 分散介质和溶剂",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 610,
+        "chunk": "# 第一节概述  \n\n涂料工业中，常用的分散介质有两种，即水和有机溶剂（以下简称溶剂）。其主要作用有以下几点： $\\textcircled{1}$ 溶解或分散成膜物成均一分散体系； $\\textcircled{2}$ 与颜料相互作用，与助剂和成膜物形成稳定的分散体系； $\\textcircled{3}$ 成膜过程中逐步挥发，调节最低成膜温度帮助成膜物流平成膜。涂料按分散介质可分为如下三类： $\\textcircled{1}$ 水性涂料（水溶型、水分散型、水乳化型）； $\\textcircled{2}$ 溶剂型涂料；$\\textcircled{3}$ 无溶剂涂料。其中水性涂料和无溶剂涂料的VOC挥发分较少或不含VOC，已成为今后涂料行业的发展趋势。  \n\n涂料中几乎所有的有机溶剂，对于人体来说都是毒性物质。有机溶剂接触人的皮肤会脱去表面的油脂，使皮肤失去保护层，导致皮肤在接触空气中毒性物质、细菌、真菌后会产生发红、皮疹，甚至皮炎等现象。有些有机溶剂，当人吸人后，还会对人体的循环系统、中枢神经系统、肺、肝等产生影响。总之，人类和各种动物对同样的有机溶剂会产生不同的反应和不同程度的伤害。从卫生学的观点上看，降低涂料中的有机溶剂的用量以及尽可能取代它们，肯定是有利的。从生态学的角度，烟雾的形成和森林的死亡都与有机溶剂有关。许多有机溶剂已被不同国家或组织，如美国、欧盟等的机构和条例认定为有害空气污染物HAPs，以限制这些有机溶剂在空气中的含量。",
+        "category": " Introduction"
+    },
+    {
+        "id": 611,
+        "chunk": "# 第二节水的主要特性  \n\n水性涂料是以水作为溶剂或分散介质形成的涂料。进入20世纪90年代，水性涂料发展速度非常快，已形成多品种、多功能、多用途的产品体系。水性涂料具有无毒、无味、无污染等优点，这些特性已逐渐被人们所认识，在很多应用领域，已作为含溶剂涂料系统（简称溶剂涂料）的替代品。水与普通的溶剂相比，水有明显不同的性质（见表2-3-1)。  \n\n水性涂料按其树脂与水相溶的关系，可分为水溶型涂料、水分散型涂料和水乳化型涂料三种。最早的商品化水性涂料是在20世纪30年代出现的，当时在加拿大出现了以聚醋酸乙烯胶乳为粘接剂的商品涂料。随着合成树脂技术的不断发展和各种单体不断商品化，出现了多种树脂胶乳，包括聚丙烯酸酯胶乳、苯乙烯-丁二烯共聚胶乳、苯乙烯-丙烯酸酯共聚胶乳、醋酸乙烯-丙烯酸酯共聚胶乳和醋酸乙烯-乙烯共聚胶乳等。在水性涂料中，水作为溶剂和分散介质，与普通的溶剂和分散介质相比，水有以下明显的特点。  \n\n表2-3-1水与溶剂的性能比较  \n\n\n<html><body><table><tr><td>性 能</td><td>水</td><td>有机溶剂（二甲苯)</td><td>性’ 能</td><td>水</td><td>有机溶剂（二甲苯）</td></tr><tr><td>沸点/C</td><td>100.0</td><td>144.0</td><td>相对挥发性（二乙醚=1）</td><td>80.0</td><td>14.0</td></tr><tr><td>凝固点/℃</td><td>0.0</td><td>25.0</td><td>25℃时的蒸气压/hPa</td><td>23.8</td><td></td></tr><tr><td>溶解度参数/（J/cm）1/2</td><td rowspan=\"4\">12.6 32.1</td><td rowspan=\"4\">17.8 3. 18.0</td><td>比热容/[J/(g·C）]</td><td>4.2</td><td>1.7</td></tr><tr><td>品</td><td>挥发热/（J/g）</td><td>2300</td><td>390.0</td></tr><tr><td></td><td>介电常数</td><td>78.0</td><td>2.4</td></tr><tr><td>49.3</td><td>热导率/[kW/（m²·C）]</td><td>5.8</td><td>1. 6</td></tr><tr><td>综合 氢键指数</td><td>39.0</td><td>4.5</td><td>相对密度d20</td><td>1. 0</td><td>0.9</td></tr><tr><td>偶极矩/D</td><td>1.8</td><td>0.4</td><td>折射率n2</td><td>1.3</td><td>1.5</td></tr><tr><td>表面张力a/（mN/m）</td><td>73.0</td><td>30.0</td><td>闪点/℃</td><td>一</td><td>23</td></tr><tr><td>黏度/mPa•s</td><td>1.0</td><td>0.8</td><td></td><td></td><td></td></tr></table></body></html>\n\nE $\\Phi$ 1D=3. 33564×10\\~°C ·m.$\\textcircled{2}$ 以二乙醚的挥发性为比较值，  \n\n$\\textcircled{1}$ 水在 $0\\%$ 结冰，根据这一规律，水性涂料应保存在凝固点以上，应随时检查涂料的技术性能（稳定性、使用性、表面特性）是否因温度变化而变化。  \n\n$\\textcircled{2}$ 水在 $100^{\\circ}\\mathrm{C}$ 沸腾，单一的水挥发时其挥发性比溶剂低得多。对于含有机溶剂的涂料溶剂会随时间均匀挥发而形成光滑的涂料表面，而对于水性涂料要形成平整光滑的表面就很困难。  \n\n$\\textcircled{3}$ 水的表面张力明显比有机溶剂高。这就导致水性涂料对被涂基层的浸润较差。所以在使用水性涂料时必须提供清洁的基层，必要时需加入助剂来降低水的表面张力。  \n\n$\\textcircled{4}$ 与溶剂相比，水的汽化热很高。因此水性涂料的干燥需要更多的能量，也需更长的时间。对于没有吸收能力的基层比具有吸收能力的基层（与含溶剂涂料相比）干燥时需更多的能量。使用溶剂型涂料时，因为存在爆炸危险，总要保持通风，以保证有机溶剂与空气的比例不超过爆炸极限。使用水性涂料时，也需保证一定的通风量，以带走不燃的水蒸气和可能存在的辅助溶剂及凝聚物。  \n\n$\\textcircled{5}$ 水具有不燃性，这一优点可以降低保险费用，同时也有利于安全贮存和运输，使用时接触也安全得多。使用水性涂料最大好处之一就是使用过程中没有燃爆的危险。  \n\n$\\textcircled{6}$ 水具有有机溶剂完全不同的溶解度参数。它比有机溶剂具有明显的极性，能形成更多的氢键。树脂与水之间的相互作用在性质和强度方面都与溶剂型涂料不同。  \n\n$\\textcircled{7}$ 水的偶极矩和介电常数与有机溶剂有不同的值。  \n$\\textcircled{8}$ 水的电导率和热导率与有机溶剂有明显区别。",
+        "category": " Introduction"
+    },
+    {
+        "id": 612,
+        "chunk": "# 第三节有机溶剂的主要特性指标及应用  \n\n溶剂包括能溶解树脂的溶剂（亦称为真溶剂），能增进溶剂溶解能力的助溶剂，能稀释树脂溶液的稀释剂和能分散树脂的分散剂4种。现代涂料产品又开发应用了一种既能溶解或分散树脂，又能在涂料成膜过程中和树脂发生化学反应，形成不挥发组分而留在涂膜中的化合物，它也属于溶剂的一种，称为反应性溶剂或活性稀释剂。至于在纤维素等涂料产品中所使用的旨在赋予涂膜以柔韧性和增加附着力的不挥发性液体，即我们通常所讲的增塑剂，不  \n\n属于溶剂的范畴。  \n\n涂料中的有机溶剂兼有促进涂料的成膜和控制、改善涂料性能等多重作用，归纳起来溶剂在涂料中的具体作用有如下几点：  \n\n$\\Phi$ 溶解树脂；$\\textcircled{2}$ 使组成成膜物的组分均一化；$\\textcircled{3}$ 改善颜料和填料的湿润性，减少颜料的漂浮；$\\textcircled{4}$ 延长涂料的存放时间；$\\textcircled{5}$ 在生产中，调整操作黏度，用溶剂来优化涂料，减少问题的发生；$\\textcircled{6}$ 改善涂料的流动性和增加涂料的光泽，对有特殊要求的表面，可调整其表面状态；$\\textcircled{7}$ 在涂刷时，可以帮助被涂表面与涂料之间的浸润，特别是对未进行脱油及清洁处理的被涂表面，可增加与被涂表面的粘接；$\\textcircled{8}$ 当涂刷垂直物体表面时，可校正涂料的流挂性及物理干燥性；$\\textcircled{9}$ 减少刷痕、气孔、接缝及涂料的混浊；$\\textcircled{10}$ 选择合适的活性溶剂，可以有效降低涂料在干燥过程中产生的VOC。溶剂的选择需要考虑的因素很多，主要有溶剂与树脂和涂料中其他成分间的物理化学作用；溶剂的黏度；溶剂的挥发理论；溶剂的电阻率；溶剂的表面张力及溶剂的毒性与安全性方面。",
+        "category": " Introduction"
+    },
+    {
+        "id": 613,
+        "chunk": "# 一、溶解力  \n\n在涂料工业中，溶剂的溶解力是指溶剂溶解树脂而形成均匀的高分子聚合物溶液的能力。溶剂将高聚物分散成小颗粒，形成均匀溶液的能力；一定浓度的树脂溶液形成的速度；一定浓度溶液的黏度以及溶剂之间的互溶性是我们设计色漆配方时选择溶剂首先要考虑的问题。  \n\n通过对物质溶解过程的研究表明，低分子化合物在液体物质中的溶解和高分子化合物溶解在有机溶剂中的机理是完全不同的。当把低分子的固体溶质加到溶剂中去，溶质表面上的分子或离子由于本身的热运动和受到溶剂分子更大的作用力的影响，克服了溶质内部分子或离子间的引力，逐渐离开溶质表面，并通过扩散作用均匀地分散到溶剂中去，成为均匀的溶液。例如将低分子量的葡萄糖溶于水中，很容易溶解，溶解过程能迅速完成。由于高分子聚合物内聚集的高分子链比低分子大得多，而且分子又存在多分散性，其溶解过程比低分子化合物要复杂得多。将高分子化合物溶解于溶剂中，首先是接触溶剂的表面上的分子链段最先被溶剂化，溶剂分子在高分子聚合物表面起溶剂化作用的同时，溶剂分子也由于高分子链段的运动，而能扩散到高分子溶质的内部去，使内部的链段（它是由若干个链节连接起来，具有独立活动功能的小区段，包括几个到几百个链节不等）逐步溶剂化，因此高分子聚合物在溶解前总会出现大量吸收溶剂、体积膨胀的阶段，这个阶段就是我们通常所讲的高聚物“溶胀”阶段。随着溶剂分子不断向内扩散，必然使更多的链段松动，外面的高分子链首先达到全部被溶剂化而溶解，里面又出现新表面进行溶剂化而使其溶解，最终形成均匀的高分子化合物溶液。这就是高分子聚合物溶解过程的特点。因此我们不难看出，溶剂对高分子聚合物溶解力的大小、溶解速度的快慢，主要取决于溶剂分子和高分子聚合物分子间亲和力的大小，溶剂向高分子聚合物分子间隙中扩散的难易，也即溶剂对于高聚物的溶解力不是溶剂单方面的性质。判断溶剂对高分子聚合物溶解能力大小的理论，也是由此基础逐步发展起来的。",
+        "category": " Introduction"
+    },
+    {
+        "id": 614,
+        "chunk": "# （一）极性相似的原则  \n\n极性相似的原则是最早出现的判断溶剂对物质溶解能力大小的经典理论。依据该原则，图2-3-1(a）中的四氯化碳的分子是个对称的四面体，任何沿着C—CI键中之一的应力都被其他的C--CI键所抵消。整个分子没有电性的不对称，因此测得这个溶剂的偶极矩等于零，称作非极性物质。而与四氯化碳形成对比的甲醇分子见图2-3-1(b)。它的一端是羟基基团显电负性，另一端的甲基显电正性，由于分子中电性的不对称分布，应力不再平衡，分子两端各带有不同的电荷，因此这种物质可以测得其偶极矩的数值，我们称其为极性物质。偶极矩数值由零到越来越大，则构成非极性物质-弱极性物质-极性物质系列。  \n\n![](images/c93ddbd7b47014c465252a45fdd715a9148343d4c2366fe66615eea287d48741.jpg)  \n图2-3-1分子结构与极性  \n\n这里所讲的偶极矩是指两个电荷中，-个电荷的电量与这两个电荷距离的乘积。即一个分子中的正电荷（十e）与负电荷（一）的中心分别为 $d_{1}$ 和 $d_{2}$ 时，则偶极矩 $\\scriptstyle\\mu=\\varepsilon d_{1}d_{2}$ ，用以表示一个分子中的极性大小。如果一个分子中的正电荷和负电荷排列不对称，则引起电性的不对称，分子中的一部分具有较显著的电正性而另一部分具有显著的电负性，这些分子彼此之间能够互相吸引，因此偶极矩的大小表示了分子极化程度的大小，是分子极性理论中判断物质是极性物质、弱极性物质还是非极性物质的依据。如图2-3-1中四氯化碳偶极矩是零，为非极性物质；甲醇的偶极矩为1.7，是极性物质；而色漆中经常使用的二甲苯偶极矩为0.4，是弱极性物质，表2-3-2中列出了一些溶剂的偶极矩数据。  \n\n表2-3-2溶剂的偶极矩  \n\n\n<html><body><table><tr><td>名称</td><td>偶极矩/10-°C·m</td><td>名称</td><td>偶极矩/10-C·m</td><td>名称</td><td>偶极矩/10-℃C·m</td></tr><tr><td></td><td>0.0</td><td>丙酮</td><td>8.97</td><td>乙二醇乙醚</td><td>7.50(25C)</td></tr><tr><td>甲苯</td><td>1.23</td><td>环已酮</td><td>10.0</td><td>醋酸酯</td><td></td></tr><tr><td>对二甲苯</td><td>0.0</td><td>二丙酮醇</td><td>10.8</td><td>二氯甲烷</td><td>3.80</td></tr><tr><td>间二甲苯</td><td>1.134</td><td>异佛尔酮</td><td>13.2(25°C)</td><td>1,1,1-三氯</td><td>5.24</td></tr><tr><td>邻二甲苯</td><td>1,47</td><td>醋酸乙酶</td><td>6.27</td><td>乙烷</td><td></td></tr><tr><td>甲醇</td><td>5.55</td><td>醋酸戊酯</td><td>6.37</td><td>三氯甲烧</td><td>1.2</td></tr><tr><td>乙醇</td><td>5.6</td><td>醋酸正丁酯</td><td>6.14</td><td>氯苯</td><td>1.6</td></tr><tr><td>正丙醇</td><td>5.53</td><td>醋酸异丁酯</td><td>6.24</td><td>环已烷</td><td>0.0</td></tr><tr><td>异丙醇</td><td>5.60</td><td>醋酸异戊酯</td><td>6.07</td><td>石脐油</td><td>0.0</td></tr><tr><td>正丁醇</td><td>5.60</td><td>乳酸丁酯</td><td>1.9</td><td>苯乙烯</td><td>0.0</td></tr><tr><td>异丁醇</td><td>5.97</td><td>乙二醇乙醚</td><td>2.08(25°C)</td><td></td><td></td></tr></table></body></html>  \n\n如图 2-3-1(c）所示，在极性溶剂中，一个分子负极的一端很明显地倾向于被相邻的分子正极一端所吸引，形成“分子缔合”。当物质A加人物质B时，只有当A能够分散或至少能削弱分子B之间的吸引力，并让自己本身为B所吸引的时候，A才会被溶解。如果A是非极性的，而B是极性的，A在B中是不能溶解的。若A、B系液体时，则形成互不混溶的分层状态；相反，如果A的极性和B的极性相接近时，A分子将被B分子吸引，A就会溶解于B中。因此产生这样一条规律：非极性溶质溶于非极性或弱极性溶剂中，极性溶质溶于极性溶剂中，简单地讲就是：“同类溶解同类”—这就是极性相似原则的核心。  \n\n依此原则，由于乙醇是极性的，因此能够和极性的水完全混溶；而苯是非极性的，所以和水不能混溶。硝基纤维素是极性的，能够溶解于极性的酯和酮类化合物中，而不能溶于烃类化合物中，因为它们是非极性或弱极性的。再来看一下脂肪酸在水中的溶解情况，甲酸（HCOOH）和醋酸 $\\langle\\mathbf{CH_{3}C O O H}\\rangle$ ）是极性物质，极易溶于水中，不溶于烃类溶剂中。但是随着分子中烃链的增长，分子中非极性部分越来越大，而极性的羧基（一COOH）对维持分子的极性的作用越来越小，因此高级脂肪酸（如亚麻酸、亚油酸等）只有微弱的极性，因而不再溶于水中，反而溶于烃中。反之，当涂料厂为生产电泳漆而制备水溶性油时，将顺丁烯二酸酐通过1，4-加成反应，连接到亚麻酸和亚油酸的双键处，使得脂肪酸在其非极性烃链不变的情况下，增加了分子中的极性基团羧基的比例，从而增强了分子的极性，使原本不溶于水的脂肪酸又变成可以水溶。  \n\n尽管“同类溶解同类”的极性相似的原则至今仍被涂料工作者在阐述溶解问题时引以为据。但是，实践证明，这个规律仅仅是定性的，说法比较笼统，有时甚至是错误的。例如；硝基甲烷就不能溶解硝化纤维素，而混合溶剂对聚合物的溶解能力更不能以这种“同类溶解同类”的规律进行判断，比较科学的方法是用“溶解度参数相近的原则”进行判断。",
+        "category": " Introduction"
+    },
+    {
+        "id": 615,
+        "chunk": "# （二）溶解度参数相近的原则",
+        "category": " Introduction"
+    },
+    {
+        "id": 616,
+        "chunk": "# 1.溶解度参数的定义及其物理意义  \n\n根据赫尔德布兰德（Hildebrand）的定义，溶解度参数是内聚能密度（CED）的平方根，它是分子间力的一种量度，其数学表达式为  \n\n$$\n\\delta=(\\Delta E/V)^{1/2}\n$$  \n\n式中8—溶解度参数， $(\\mathsf{c a l}/\\mathsf{c m}^{3})^{1/2}$ 和 $\\mathrm{(J/m^{3})^{1/2}}$ \\* $1({\\mathrm{cal/cm}}^{3})^{1/2}=2.046\\times10^{3}({\\mathrm{J/m}}^{3})^{1/2}$ △E——每摩尔物质的内聚能；$\\boldsymbol{v}$ 摩尔体积。  \n\n我们知道，溶质在溶剂中的溶解与溶质和溶剂分子自身的内聚力以及溶质和溶剂分子间的作用力大小有关，如果以A表示溶剂，B表示溶质。以 $F_{\\mathrm{AA}}$ 表示溶剂分子间的自聚力， $F_{\\mathrm{BB}}$ 表示溶质分子间的自聚力， $F_{\\mathsf{A B}}$ 表示溶剂和溶质分子间的相互作用力。若同种分子间的自聚力大于不同分子间的作用力，即 $F_{\\mathsf{A A}}{>}F_{\\mathsf{A B}}$ 或 $F_{\\mathrm{BB}}{>}F_{\\mathsf{A B}}$ ，则两种分子趋于自聚，不相混溶。反之，如果 $F_{\\mathsf{A B}}{\\geqslant}F_{\\mathsf{A A}}$ 且 $F_{\\mathrm{AB}}{\\geqslant}F_{\\mathrm{BB}}$ 时，则溶质便可以溶解在溶剂中。物理化学领域的研究表明，作用于分子间的作用力通常包括范德华力和氢键力，范德华力又包括取向力、诱导力和色散力。在一种物质和另一种物质混合之前，必须克服这些吸引力，即作用于溶剂和溶质分子间的作用力相同时，最容易实现自由混合。而我们前面讲到的溶解度参数（8）的定义，它是单位体积内全部分子的吸引力，既然如此，不难看出当溶剂和溶质的溶解度参数（8）相同时，就表示其单位体积内全部分子的作用力相同，这时溶质在溶剂中便可以溶解，因此溶解参数作为物质分子间的吸引力的一种量度，可以作为表征物质溶解性的一个物理量。  \n\n从热力学的观点来看，溶质溶于溶剂中的溶解过程可以由体系的变和自由能的改变予以描绘。根据热力学方程式：  \n\n$$\n\\Delta F_{\\mathrm{m}}{=}\\Delta H_{\\mathrm{m}}{-}T\\Delta S_{\\mathrm{m}}\n$$  \n\n式中 $\\Delta F_{\\m\\m_{\\m\\m}}$ —混合自由能的变化；$\\Delta H_{\\mathrm{m}}$ ——混合热的变化；T—热力学温度，K；  \n\n$\\triangle S_{\\mathrm{ra}}$ —混合变。  \n\n对于完全自发的互溶体系，混合自由能的变化应当为负值，即 $\\Delta F_{\\mathrm{m}}<0$ ，由于互溶体系的无规度增加，在溶解过程中，混合变总是增大的，即 $\\Delta S_{\\mathrm{m}}$ 一定为正值。所以 $T\\Delta S_{\\mathrm{m}}$ 一项恒小于零，为负值。因此，欲 $\\Delta F_{\\mathrm{m}}$ 减小，则要求 $\\Delta H_{\\mathrm{m}}$ 尽可能地小，也就是说混合热 $\\Delta H_{\\mathrm{m}}$ 起着决定性的作用， $\\Delta H_{\\mathrm{m}}$ 的变化在很大程度上控制着混合自由能变化的大小，决定着体系能否自溶。  \n\n通过溶解过程能量变化的研究和对非极性分子体系的能量变化公式的推导，可得溶解过程混合热变化的公式为  \n\n式中 $\\Delta H_{m}$ —混合热的变化；  \n\n$N_{\\mathsf{A}}$ ， $N_{B}$ —A，B两种物质的摩尔分数；  \n$\\boldsymbol{V_{\\mathrm{A}}}$ . $V_{\\ B}$ —A，B两种物质的摩尔体积；  \n$E_{\\wedge}$ $E_{\\mathrm{B}}$ —A，B两种物质的摩尔蒸发能，即内聚能。  \n\n将式（2-3-1）代人式（2-3-3）中可得  \n\n$$\n\\Delta H_{\\mathrm{m}}=\\left[(N_{\\mathrm{A}}V_{\\mathrm{A}})(N_{\\mathrm{B}}V_{\\mathrm{B}})/(\\ N_{\\mathrm{A}}V_{\\mathrm{A}}+N_{\\mathrm{B}}V_{\\mathrm{B}})\\right](\\hat{\\sigma}_{\\mathrm{A}}-\\hat{\\sigma}_{\\mathrm{B}})^{2}\n$$  \n\n由上论述可知，欲 $\\Delta H_{\\mathrm{m}}$ 尽可能地小，最好是 $\\Delta H_{\\mathrm{m}}=0$ 。从而保证式（2-3-2）中的混合自由能变化量 $\\Delta F_{\\mparallel}$ 为负值，使体系中两组分充分互溶，那么就必须使式（2-3-4）中的 $\\delta_{\\mathsf{A}}=$ $\\delta_{\\mathrm{B}}$ 。这就是说，两种物质的溶解度参数相近，最好是相同时才可以互溶。这就是溶解度参数的物理意义以及我们依靠溶解度参数相近的原则预测体系能否互溶的理论依据。  \n\n把这个规律推广到高聚物的溶剂体系中时，上述式(2-3-4）的混合热熔变化的表达式要进行修正。因为高分子化合物的体积要比小分子溶剂的体积大得多，在溶剂和高聚物混合时，溶剂是对以链段为体积对等单位的高聚物进行“单方面混合”渗人的。设高分子化合物体积比溶剂分子的体积大 $\\boldsymbol{r}$ 倍，那么以 $\\boldsymbol{V_{\\mathrm{B}}}=\\boldsymbol{r}\\boldsymbol{V_{\\mathrm{A}}}$ 代入式（2-3-4）中可得  \n\n$$\n{\\Delta H_{\\mathrm{m}}}^{\\prime}{=}\\lbrack N_{\\mathrm{A}}N_{\\mathrm{B}}r V_{\\mathrm{A}}/\\ (N_{\\mathrm{A}}{+}N_{\\mathrm{B}})\\rbrack\\ (\\hat{\\vartheta}_{\\mathrm{A}}{-}\\hat{\\vartheta}_{\\mathrm{B}})^{2}\n$$  \n\n该式表明，对于高分子聚合物和有机溶剂的非极性分子体系，当高聚物的溶解度参数和溶剂的溶解度参数相同或接近时，高聚物就能溶解于该溶剂中，通常当 $(\\delta_{\\mathsf{A}}-\\delta_{\\mathsf{B}}){<}1.3\\sim$ 1.8时，就可以估计为能够溶解，当然，两者之差值越小越好。",
+        "category": " Introduction"
+    },
+    {
+        "id": 617,
+        "chunk": "# 2.溶解度参数的测定  \n\n溶剂和高分子聚合物的溶解度参数 $\\delta$ 的值，基本上可以通过4种方法进行测定，即；  \n\n$\\textcircled{1}$ 从已知或可测得的物理常数进行计算求得；  \n$\\textcircled{2}$ 从物质的化学结构计算求得；  \n$\\textcircled{3}$ 从物质对另一个已知8值的物质溶解度参数相同或相近而求得；  \n$\\textcircled{4}$ 从反相色谱求得。  \n\n现简要叙述如下。  \n\n（1）溶剂和混合溶剂的溶解度参数溶剂的溶解度参数，通常可以通过汽化热、蒸气压及表面张力这些已知或可测得的物理常数进行计算求得。  \n\n由前所述，内聚能等于蒸发能，类似有机溶剂这样的可挥发物质，其蒸发能可以由汽化热而测得。  \n\n$$\n\\Delta E{=}\\Delta H_{\\mathbf{V}}{-}R T\n$$  \n\n式中E——内聚能；  \n\n$\\Delta H_{\\mathrm{V}}$ —摩尔蒸发汽化热（蒸发热)；R——气体常数，8.29J/（K·mol);  \n\nT—热力学温度，K。  \n\n在 $25\\Upsilon$ 时，  \n\n$$\n\\Delta E_{25\\uptau}\\approx\\Delta H_{\\mathrm{V},25\\uptau}-600\n$$  \n\nHv.2s℃可以从文献中查得，对于大多数溶剂如果不能直接测得其摩尔蒸发热，或者在文献中无法找到，那么最方便的办法，是采用Hildebrand的经验方程式：  \n\n$$\n\\Delta H_{\\mathrm{V,257}}=23.7T_{\\mathrm{b}}+0.020T_{\\mathrm{b}}{}^{2}-2950\n$$  \n\n式中 $T_{\\flat}$ —沸点，K。  \n\n但是式（2-3-8）仅适用于无氢键存在的有机溶剂，对于醇、酯、酮类形成氢键能力强的溶剂，如果其沸点在 $100\\Upsilon$ 以下时，可以依下式进行校正：  \n\n醇 $1.4\\dot{+}\\delta$ 计算值酯 $0.6\\dot{+}\\delta$ 计算值酮 $0.5\\dot{+}\\delta$ 计算值  \n\n$\\Delta{H_{\\mathrm{V}}}$ 的值也可以通过克劳修斯-克拉伯龙（Clausius-Clapeyron）方程式，根据表征蒸气压随温度的改变计算求得，即由下式：  \n\n$$\n\\Delta H_{\\mathrm{V}}/R T^{2}=\\mathrm{{\\dln}\\it{p}/\\mathrm{{d}\\it{T}}}\n$$  \n\n当 $\\scriptstyle{\\pmb{\\mathscr{p}}}$ 值低于 $5332,88\\mathrm{{Pa}}$ 时， $\\Delta H_{\\mathrm{V}}$ 随 $\\scriptstyle{\\boldsymbol{\\phi}}$ 值从 $133.322\\sim5332.88\\mathrm{Pa}$ 范围内与温度是线性关系，采用外推法或内插法而求得。  \n\n由于溶解度参数 $\\delta$ 的值与表面张力 $\\gamma$ 的值有关，通常具有高的溶解度参数的液体，必定产生高的表面张力 $\\gamma$ 值。因此，赫尔德布兰德和司考特（Hildebrandand Scott）首先提出了下述关系式：  \n\n$$\n\\scriptstyle{\\delta=K\\gamma/(V^{1/3})^{a}}\n$$  \n\n式中V——摩尔体积；  \n\nK，a—常数，列于表2-3-3中。  \n\n表2-3-3液体溶剂的K，α值   \n\n\n<html><body><table><tr><td>液体类型</td><td>K值</td><td>a值</td><td>液体类型</td><td>K值</td><td>值</td></tr><tr><td>不含氧的碳氢化合物</td><td></td><td></td><td>所有不含氧的</td><td>4.21</td><td>0.43</td></tr><tr><td>脂肪族和饱和的</td><td>4.31</td><td>0.40</td><td>含氧化合物</td><td></td><td></td></tr><tr><td>芳香族</td><td>4.56</td><td>0.37</td><td>酯、醚和酰胺</td><td>3.58</td><td>0.56</td></tr><tr><td>含卤素化合物</td><td>4.29</td><td>0.41</td><td></td><td>5.96</td><td>0.25</td></tr><tr><td>胺类</td><td></td><td></td><td>醇</td><td>5.86</td><td>0.39</td></tr><tr><td>伯胺（除乙基胺）</td><td>3.93</td><td>0.47</td><td>羧酸</td><td>4.12</td><td>0.58</td></tr><tr><td>仲胺和叔胺</td><td>4.10</td><td>0.44</td><td></td><td></td><td></td></tr></table></body></html>  \n\n通常，涂料工业常用的有机溶剂的溶解度参数的数据可以直接从有关文献资料中查得。现将涂料工业中常用有机溶剂的溶解度参数 $\\delta$ 的数值列于表2-3-4中。  \n\n以上介绍了单一溶剂的溶解度参数，而在涂料工业中为了获得比较理想的溶解和挥发成膜的效果，往往使用混合溶剂，混合溶剂的溶解度参数可近似地用各组分的溶解度参数及其体积之和来表示，即：  \n\n$$\n\\hat{\\delta}_{\\mathrm{mix}}=\\phi_{1}\\hat{\\delta}_{1}+\\phi_{2}\\hat{\\delta}_{2}+\\phi_{3}\\hat{\\delta}_{3}+\\dots+\\phi_{n}\\hat{\\delta}_{n}=\\sum_{1}^{n}\\phi_{i}\\delta_{i}\n$$  \n\n式中—各组分的体积分数；——各组分的溶解度参数。  \n\n表2-3-4涂料工业常用有机溶剂的溶解度参数及氢键值  \n\n\n<html><body><table><tr><td rowspan=\"2\">名称</td><td colspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\">名称</td><td colspan=\"2\"></td><td rowspan=\"2\"></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td>9.2</td><td>18.82</td><td>0.0</td><td>苯甲醇</td><td>12.1</td><td>24.76</td><td>18.7</td></tr><tr><td>甲苯</td><td>8.9</td><td>18.21</td><td>4.5</td><td>二丙酮醇</td><td>9.2</td><td>18.82</td><td>13.0</td></tr><tr><td>二甲苯</td><td>8.8</td><td>18.00</td><td>4.5</td><td>丙酶</td><td>9.9</td><td>20.25</td><td>9.7</td></tr><tr><td>乙苯</td><td>8.8</td><td>18.00</td><td>1. 5</td><td>环己酮</td><td>9.9</td><td>20.25</td><td>一</td></tr><tr><td>Solvesso 100</td><td>8.6</td><td>17.60</td><td>一</td><td>异佛尔酮</td><td>9.1</td><td>18.62</td><td>一</td></tr><tr><td>Solvesso 150</td><td>8.5</td><td>17.39</td><td></td><td>甲乙酮（丁酮）</td><td>9.3</td><td>19.03</td><td>7.7</td></tr><tr><td>Solvesso 200</td><td>8.7</td><td>17.80</td><td></td><td>苯乙酮</td><td>10.6</td><td>21.69</td><td>一</td></tr><tr><td>石脑油</td><td>7.6</td><td>15.55</td><td>0.0</td><td>甲基正丁基酮</td><td>8.5</td><td>17.39</td><td>8.4</td></tr><tr><td>苯乙烯</td><td>9.3</td><td>19. 03</td><td>1.5</td><td>甲基异丁基酮</td><td>8.4</td><td>17.19</td><td>7.7</td></tr><tr><td>正已烷</td><td>7.3</td><td>14.94</td><td>0.0</td><td>甲基正戊基酮</td><td>8.0</td><td>16.37</td><td>7.7</td></tr><tr><td>正庚烷</td><td>7.4</td><td>15.14</td><td>0.0</td><td>甲基异戊基酮</td><td>8.3</td><td>16.98</td><td>7.4</td></tr><tr><td>环已烧</td><td>8.2</td><td>16.78</td><td>0.0</td><td>二乙基酮</td><td>8.8</td><td>18.00</td><td>7.7</td></tr><tr><td>松节油</td><td>8.1</td><td>16.50</td><td>一</td><td>甲基丙基酮</td><td>8.9</td><td>18.21</td><td>8.0</td></tr><tr><td>双戊烯</td><td>8.5</td><td>17.39</td><td></td><td>甲基苯基酮</td><td>10.6</td><td>21.69</td><td>一</td></tr><tr><td>三氯甲烧</td><td>9.7</td><td>19.85</td><td></td><td>二异丁基甲酮</td><td>7.8</td><td>15.96</td><td>8.4</td></tr><tr><td>二氯乙烧</td><td>9.8</td><td>20.05</td><td></td><td>酯酸甲酯</td><td>9.6</td><td>19.64</td><td>8.4</td></tr><tr><td>1,1,1-三氯乙烷</td><td>9.6</td><td>19. 64</td><td></td><td>醋酸乙酯</td><td>9.1</td><td>一</td><td>8.4</td></tr><tr><td>氯苯</td><td>9.6</td><td>19.64</td><td>1.5</td><td>酯酸正丁酯</td><td>8.5</td><td>17. 39</td><td>8.8</td></tr><tr><td>硝基乙烧</td><td>11. 1</td><td>22.71</td><td>2.5</td><td>醋酸异丁酯</td><td>8.3</td><td>一</td><td>8.8</td></tr><tr><td>2-硝基丙烷</td><td>10.7</td><td>21.89</td><td>2.5</td><td>醋酸戊酯</td><td>8.5</td><td>17.39</td><td>9.0</td></tr><tr><td>硝基苯</td><td>10.0</td><td>20.46</td><td>一</td><td>醋酸异戊酯</td><td>7.8</td><td>15.96</td><td>一</td></tr><tr><td>甲醇</td><td>14.6</td><td>29.67</td><td>18.7</td><td>乳酸丁酯</td><td>9. 4</td><td>19.23</td><td>7.0</td></tr><tr><td>乙醇</td><td>12.9</td><td>26.39</td><td>18.7</td><td>-丁内酯</td><td>15.5</td><td>31.71</td><td>9.7</td></tr><tr><td>正丙醇</td><td>11. 9</td><td>24.35</td><td>18.7</td><td>乙二醇乙醚</td><td>9.9</td><td>20.25</td><td>13.0</td></tr><tr><td>异丙醇</td><td>11.5</td><td>23.53</td><td>一</td><td>乙二醇乙酸醋酸酶</td><td>8.7</td><td>17.80</td><td>9.4</td></tr><tr><td>正丁醇</td><td>11. 4</td><td>23.32</td><td>18.7</td><td>二甘醇乙醚</td><td>9.6</td><td>19.64</td><td>13.0</td></tr><tr><td>异丁醇</td><td>10.8</td><td>22.10</td><td>一</td><td>二甘醇丁醚</td><td>8.9</td><td>18.21</td><td>13.0</td></tr><tr><td>仲丁醇</td><td>11. 1</td><td>22.71</td><td>-</td><td>二甘醇乙醚醋酸酯</td><td>8.5</td><td>17.39</td><td>9.1</td></tr></table></body></html>  \n\n【例题2-3-1】已知二甲苯的溶解度 $\\delta=8,8$ ， $\\gamma$ 丁内酯（y-Butyrolaetone）的溶解度$\\delta{=}12,6$ ，试问若以体积分数计，配制成 $33\\%$ 二甲苯和 $67\\%$ 的丁内酯的混合溶剂，该混合溶剂的溶解度参数 $\\delta_{\\mathrm{mix}}$ 是多少？  \n\n解依据式(2-3-11)  \n\n$$\n\\hat{\\delta}_{\\mathrm{mix}}=\\phi_{1}\\hat{\\delta}_{1}+\\phi_{2}\\hat{\\delta}_{2}=0.33\\times8.8~+0.67\\times12.6=11.3\n$$  \n\n(2）高分子聚合物的溶解度参数由于高分子聚合物是不挥发性物质，不能应用汽化热等参数通过计算而求得其溶解度参数，所以通常是通过物质的化学结构计算求得，从对已知溶解度参数的溶剂而求得及反相色谱法测定等途径而得到其溶解度参数。  \n\n关于物质结构的计算方法是基于1928年由Dunkel提出的物质内聚能具有基团加和性的理论，以及所推导出的在室温下化合物基团对液体内聚能贡献的数据。随后发展了Small方法（1961年）、VanKrevelen方法（1965年）和Hoy方法（1970年）等，由于有关文献有专门学术性的讨论，本节不再详述。  \n\n$\\Phi$ 反相色谱法将待测的聚合物在载体上制样，用低分子化合物作为探针分子，进行反相色谱法测定并进行一系列计算而求得溶解度参数的方法。  \n\n另一种以高分子聚合物和已知溶解度参数的溶剂相溶而求得其溶解度参数范围的方法，是目前用于确定高分子化合物溶解度参数比较简便直观的方法，通常分为“特性黏度法”和“平衡溶胀法”两种方法。  \n\n$\\textcircled{2}$ “特性黏度法”称取一定量的聚合物溶解于具有不同的溶解度参数的溶剂中，在一定温度下测定其特性黏度，所得最大的特性黏度的体系即认为聚合物的溶解度参数等于该体系的溶解度参数数值。如图2-3-2所示，聚醋酸乙烯酯的溶解度参数 $\\delta{=}9.43$  \n\n![](images/d7d36b2196f3754fcfd32d1cd8118db0471c3b4bc3a75dde096d6acdf6f18b13.jpg)  \n图2-3-2聚醋酸乙烯酯溶液的特性黏度 a-丁酮；b—甲基异丁基酮；c—甲苯；d-苯； e-氯仿；f-甲酸乙酯；g—氯苯；h—丙酮  \n\n![](images/1def337e780c576c7ec02c17358c5558fc94033fc85d6f548dbeaac487e8ab29.jpg)  \n图2-3-3线型和交联聚合物和溶剂溶解度参数的函数关系  \n\n$\\textcircled{3}$ “平衡溶胀法”在一定温度下将交联的高分子聚合物放到具有不同溶解度参数的溶剂中进行溶胀，当达到平衡后，测定其溶胀度。最大溶胀度的体系，所对应的溶剂体系的溶解度参数即为该高聚物的溶解度参数，如图2-3-3所示。  \n\n以上介绍了测定高聚物溶解度参数的常用方法，涂料工业常见树脂的溶解度参数可以从文献中查得。现将涂料工业中常用树脂的溶解度参数 $\\delta$ 值列于表2-3-5中。  \n\n如果说每一种溶剂的溶解度参数都具有其特定的数值的话，那么高分子聚合物的溶解度参数值则是一个范围，对于不同的树脂这一范围的宽度往往有很大差异。 0",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 618,
+        "chunk": "# 3.溶解度参数的应用  \n\n溶解度参数在涂料工业科研和生产实践中的应用，大致可以归纳为以下几个方面。  \n\n$\\textcircled{1}$ 依据溶解度参数相同或相近互溶的原则，可以判断树脂在溶剂（或混合溶剂）中是否可以溶解。  \n\n【例题2-3-2】已知聚苯乙烯树脂的溶解度参数 $\\delta\\mathrm{=}~8.5\\sim9.3\\$ ，聚醋酸乙烯酯树脂的溶解度参数 $\\delta$ 的平均值为9.4，试问前者在丁酮中，后者在苯、甲苯及氯仿中可否溶解？  \n\n解查表2-3-4知丁酮的溶解度参数 $\\delta_{1}=9,3$ ，和聚苯乙烯树脂的溶解度参数 $\\delta_{2}$ 的差$|\\delta_{1}-\\delta_{2}|=0\\sim0.6$ ，差值范围小于 $1.3{\\sim}1.8$ 所以聚苯乙烯树脂在丁酮中可以溶解。  \n\n由表2-3-4中同时可查得苯、甲苯及氯仿的溶解度参数 $\\delta_{1}$ 分别为9.2、8.9和9.7。和聚醋酸乙烯酯溶解度参数8的差值的绝对值分别为0.2，0.5和0.3，差值范围小于1.3～1.8，所以聚醋酸乙烯酯可以在这3种溶剂中溶解。  \n\n表2-3-5涂料中常用树脂的溶解度参数  \n\n\n<html><body><table><tr><td rowspan=\"2\">树脂名称</td><td colspan=\"2\"></td><td colspan=\"2\">8</td><td colspan=\"2\"></td></tr><tr><td>(cal/cm)1/2</td><td>10a(J/m)1/2</td><td>(cal/en)1/2</td><td>10a(J/ma)1/2</td><td>(eal/em3)1/#</td><td>10a(J/m²)1/2</td></tr><tr><td>虫胶</td><td>0</td><td>0</td><td>10. 0~11. 0</td><td>20.46~22.50</td><td>9.5~14. 0</td><td>19.44~28.64</td></tr><tr><td>天然橡胶</td><td>8.1~8.5</td><td>16. 5~17. 39</td><td>。</td><td></td><td>0</td><td>0</td></tr><tr><td>氯化橡胶</td><td>8.5~10.6</td><td>17. 39~21. 69</td><td>7. 8~10. 8</td><td>15.96~22.10</td><td></td><td>0</td></tr><tr><td>硝基纤维</td><td>11. 1~12.7</td><td>22. 71~25.98</td><td>7.8~14.7</td><td>15.96~30.08</td><td>12.7~14.5</td><td>25.98~29.67</td></tr><tr><td>醋酸纤维</td><td>11. 1 ~12. 5</td><td>22. 71~25.58</td><td></td><td>10. 0~14.520.46~29.67</td><td>0</td><td>0</td></tr><tr><td>醋酸丁酸纤维素(CAB1/2s)</td><td>11.1~12.7</td><td>22. 71~25.98</td><td>8.5~14.7</td><td>17.39~30.08</td><td>12.7~14.5</td><td>25.98~29.67</td></tr><tr><td>聚乙烯醇缩丁醛</td><td>0</td><td>0</td><td>9.0~11. 0</td><td>18.41~22. 50</td><td>9.0~15.0</td><td>18.41~30.69</td></tr><tr><td>聚氯乙烯</td><td>8.5~11. 0</td><td>17. 39~22.5</td><td>7.8~10.5</td><td>15.96~21.48</td><td></td><td>0</td></tr><tr><td>乙烯树脂VYHH</td><td>9. 3~11. 1</td><td>19. 03~22.71</td><td>7.8~13. 0</td><td>15.96~26.60</td><td>。</td><td>0</td></tr><tr><td>氯乙烯-醋酸乙烯树脂 VAGH</td><td>9. 0~11.1</td><td>18. 41~22. 71</td><td>7. 0~14. 0</td><td>14. 32~28. 64</td><td>0</td><td>0</td></tr><tr><td>松香甘油酯树脂</td><td>7.0~10. 6</td><td>14. 32~21. 69</td><td>7.4~10. 8</td><td>15.14~22.10</td><td>9. 5~10. 9</td><td>19. 44 ~22.30</td></tr><tr><td>酚醛树脂</td><td>8.5~11.5</td><td>17.39~23.53</td><td>7.8~13.2</td><td>15.96~27.01</td><td>9.3~13. 6</td><td>19. 03~27.83</td></tr><tr><td>短油度醇酸树脂</td><td>8.0~11.0</td><td>16. 37~22. 5</td><td>7.0~12.0</td><td>14.32~24.55</td><td>9.0~11. 0</td><td>18.41~22.5</td></tr><tr><td>中油度醇酸树脂</td><td>7.0~11. 0</td><td>14.32~22. 5</td><td>7. 0~12. 0</td><td>14.32~24.55</td><td>9.0~11. 0</td><td>18.41~22.5</td></tr><tr><td>长油度醇酸树脂</td><td>7.0~11.0</td><td>14.32~22.5</td><td>7.0~10. 0</td><td>14.32~20.46</td><td>9.0~11. 0</td><td>18.41~22.5</td></tr><tr><td>聚酯树脂</td><td>8.0~11. 0</td><td>16.37~22.5</td><td>7.0~12.0</td><td>14.32~24.55</td><td>9.0~11. 0</td><td>18.41~22.5</td></tr><tr><td>三氯氰胺甲醛树脂</td><td>8. 5~11.1</td><td>17.39~22. 71</td><td>7. 4~11.1</td><td>15. 14~22.71</td><td>9. 5~11. 9</td><td>19. 44~24.35</td></tr><tr><td>脲醛树脂[Beetle227-8（干）]</td><td>0</td><td>0</td><td>0</td><td></td><td>9.5~11. 4</td><td>19. 44~23. 32</td></tr><tr><td>环氧树脂（环氧当量为400～ 500)</td><td>10. 0~11. 0</td><td>20.46~22.5</td><td>8. 0~13. 0</td><td>16.37~26.60</td><td>0</td><td>0</td></tr><tr><td>环氧树脂(环氧当量为800～ 900)</td><td>0</td><td>0</td><td>8. 0~13. 0</td><td>16.37~26.60</td><td>0</td><td>0</td></tr><tr><td>环氧树脂（环氧当量为1700～ 2000)</td><td>0</td><td></td><td>8.0~13.0</td><td>16.37~26.60</td><td>0</td><td>0</td></tr><tr><td>环氧树脂(环氧当量为2000～ 4000)</td><td>0</td><td>0</td><td>8. 0~10. 0</td><td>16.37~20.46</td><td>0</td><td>0</td></tr><tr><td>干性油脂肪酸环氧酯</td><td>8. 0 ~11. 0</td><td>16.37~22.5</td><td>7.0~10.0</td><td>14.32~20.46</td><td></td><td>。</td></tr><tr><td>聚氨基甲酸酯</td><td>8.0~11. 0</td><td>16.37~22.5</td><td>8. 0~12.0</td><td>16.37~24.55</td><td></td><td>。</td></tr><tr><td>不饱和聚酯</td><td>9. 2~12.7</td><td>18.82~25.98</td><td>8. 0~14.7</td><td>16.37~30.08</td><td></td><td>0</td></tr><tr><td>聚甲基丙烯酸甲酯</td><td>8.0~13.0</td><td>16.37~25.6</td><td>8.0~13. 0</td><td>16.37~26.60</td><td>。</td><td>。</td></tr><tr><td>丙烯酸酯共豪物(AcylodD-</td><td>10. 6 ~12.7</td><td>21.69~25.98</td><td>8.9~13.3</td><td>18. 21~27.21</td><td>0</td><td>0</td></tr><tr><td>有机硅树脂</td><td>7.0~9.5</td><td>14.32~19.44</td><td>9. 3~10.8</td><td>19. 03~22.10</td><td>9.5~11.5</td><td>19.44~23.53</td></tr><tr><td>聚苯乙烯</td><td>8.5~11.1</td><td>17. 39~22.71</td><td>9. 3~9.9</td><td>19. 03~20.25</td><td></td><td></td></tr><tr><td>聚四氯乙烯</td><td>5.8~6.4</td><td>11. 87~13. 09</td><td></td><td></td><td></td><td></td></tr><tr><td>聚碳酸酯</td><td>9.5~10.6</td><td>19.44~21. 69</td><td>9.5~10.0</td><td>19.44~20.46</td><td></td><td></td></tr></table></body></html>\n\n注：8表示弱氢键溶解度参数；表示中等氢键溶解度参数；表示强氢键溶解度参数。  \n\n【例题2-3-3】今有环己酮、甲基苯基酮和甲基正丁基酮3种溶剂，试确定哪种可以溶解氯乙烯-醋酸乙烯酯共聚树脂？  \n\n解查表2-3-4知环己酮、甲基苯基酮和甲基正丁基酮的溶解度参数 $\\delta$ 值为9.9、10.6和8.5。查表2-3-5知，氯乙烯-醋酸乙烯树脂的溶解度参数 $\\delta$ 平均值为10.5。由于3种溶剂和其溶解度参数差值的绝对值分别是 $0.6,\\ 0.1$ 和2.0。所以环已酮和甲基苯基酮的溶解度参数与氯乙烯共聚树脂的溶解度参数差值小于 $1.3{\\sim}1.8$ ，可以溶解该树脂，而甲基正丁基酮和该树脂溶解度参数差值的绝对值大于1.8，故不能溶解该树脂。  \n\n【例题2-3-4】已知天然橡胶的溶解度参数平均值为8.2，正己烷的溶解度参数 $\\delta$ 值为7.3与8.2相差很少（为0.9），可以很好地溶解天然橡胶，但若加人适量的甲醇可以使其溶解增强，试求甲醇的最佳加入量是多少？  \n\n解设加入甲醇后，在甲醇-正丁烷的混合溶剂中。甲醇所占的体积分数为 $\\varphi$ ，正丁烷的体积分数为 $_{1-\\varphi}$ 。查表2-3-4知，甲醇的溶解度参数值为14.6。根据式(2-3-11)，混合溶剂的溶解度参数为  \n\n$$\n\\delta_{\\operatorname*{mix}}=14.6\\varphi+7.3(1-\\varphi)\n$$  \n\n欲使此混合溶剂对天然橡胶有最大的溶解能力，混合溶剂和天然橡胶的溶解度参数值最好是相同，即 $\\delta_{\\mathrm{mix}}=8.2$ ，代人上式得  \n\n$$\n8,2{=}14,6\\varphi{+}7,3(1{-}\\varphi)\n$$  \n\n解此方程得 $\\scriptstyle{\\varphi=0,125}$ ，即在正已烷中加人12.5%的甲醇（以体积计)，所得的混合溶剂对天然橡胶的溶解力最强。  \n\n$\\textcircled{2}$ 依据溶解度参数值相同或相近可以互溶的原则，预测两种溶剂的互溶性。  \n\n$\\textcircled{3}$ 依据溶解度参数可以估计两种或两种以上树脂的互溶性。如果这几种树脂的溶解度参数（或溶解度参数数值范围的平均值）彼此相同或相差不大于1，这几种树脂就可以互溶。这将对预测混合树脂溶液的贮存稳定性及固体涂膜的物化性能（如透明度、光泽等）具有理论及实用价值。  \n\n$\\textcircled{4}$ 利用涂料用树脂在一系列已知溶解度参数的溶剂中的溶解情况，可以通过实验确定该树脂的溶解度参数的范围。  \n\n设有一组溶剂，其溶解度参数 $\\delta$ 值分别为7.0、7.5、8.0、8.5、9.0、9.5、10.0、10.5。将某树脂分别溶于这些溶剂中，假如在 $\\hat{\\sigma}$ 值为7.0和7.5的溶剂中不溶，在8值为9.5以上的溶剂中也不溶，而在8.0，8.5和9.0的溶剂中可以溶解，那么，我们就可以断定，该树脂的溶解度参数值为 $8.0\\sim9.0$ 身  \n\n$\\textcircled{5}$ 利用溶解度参数我们可以判断涂膜的耐溶剂性。如果涂料中所用的成膜物，其溶解度参数和某一溶剂（或混合溶剂）的溶解度参数数值相差较大，该涂膜对该溶剂而言，就有较好的耐溶剂性能。  \n\n$\\textcircled{6}$ 在涂料产品中，为了提高漆膜的柔韧性、附着力，克服硬脆易裂的缺点。常在树脂中加入增塑剂。增塑剂应具有与树脂混溶的性能，能溶于涂料用溶剂的性能。实践证明，增塑剂的选用，也可以用溶解度参数相同或相近时可以相溶的原则，若两种增塑剂混合使用时，混合物的溶解度参数 $\\delta_{\\widehat{\\mathfrak{M}}\\widehat{\\mathfrak{G}}}$ 的计算方法和混合溶剂的计算方法相同。表2-3-6列出了一些常用增塑剂的溶解度参数。  \n\n表2-3-6一些常用增塑剂的溶解度参数值  \n\n\n<html><body><table><tr><td rowspan=\"3\">增塑剂</td><td colspan=\"2\">8值</td><td rowspan=\"3\">增塑剂</td><td colspan=\"2\">值</td></tr><tr><td>(eal/em)1/</td><td>10°(J/m)1/2</td><td>(eal/cm)1/2</td><td>10*(J/ma)1/2</td></tr><tr><td>石蜡油</td><td>7.5</td><td>15.35</td><td>邻苯二甲酸二(2-丁氧乙酯）</td><td>9.3</td><td>19.03</td></tr><tr><td>芳香油</td><td>8.0</td><td>16.37</td><td>邻苯二甲酸二丁酯</td><td>9.4</td><td>19.23</td></tr><tr><td>樟脑</td><td>7.5</td><td>15.35</td><td>磷酸三苯酯</td><td>9.4</td><td>19.23</td></tr><tr><td>己二酸二异辛酯</td><td>8.7</td><td>17.8</td><td>磷酸三甲苯酯</td><td>9.8</td><td>20.05</td></tr><tr><td>邻苯二甲酸二异葵酶</td><td>8.8</td><td>18.00</td><td>二苯甲醚</td><td>10.0</td><td>20.46</td></tr><tr><td>葵二酸二丁酯</td><td>8.9</td><td>18.21</td><td>甘油三醋酸酯</td><td>10.0</td><td>20.46</td></tr><tr><td>邻苯二甲酸二异辛酯</td><td>8.9</td><td>18.21</td><td>邻苯二甲酸二甲酯</td><td>10.5</td><td>21.48</td></tr></table></body></html>  \n\n$\\textcircled{7}$ 利用溶解度参数可以在研制塑料涂料过程中选用适当的树脂和溶剂。通常将塑料涂料涂装于塑料产品表面时，既要求涂料对塑料底材有较好的附着力，又不能出现涂料中所用的溶剂将被涂装的塑料咬起现象。这就要求塑料涂料中使用的树脂的溶解度参数要尽量接近塑料的溶解度参数值，以使涂膜有较好的附着力。但是涂料用溶剂的溶解度参数与塑料的溶解度参数相差得越大越好，以确保塑料表面不被溶解或咬起。同时也要求塑料涂料中树脂的溶解度参数与塑料底材中所使用的增塑剂的溶解度参数值相差得越大越好，以保证增塑剂不渗析。表2-3-7列出了一些常用塑料材料的溶解度参数的数据。  \n\n表2-3-7一些常用塑料材料的溶解度参数6值  \n\n\n<html><body><table><tr><td rowspan=\"2\">塑料材料</td><td colspan=\"2\">值</td><td rowspan=\"2\">塑料材料</td><td colspan=\"2\">&值</td></tr><tr><td>(cal/ma)1/2</td><td>10a(J/m)1/z</td><td>(cal/cm)1/</td><td>10a(J/m)1/2</td></tr><tr><td>高压法聚乙烯 聚丙烯 聚苯乙烯 丙烯酸树脂</td><td>7.9 7.8~8.0 8.6~9.7 9.0~9.5</td><td>16.16 15.96~16.37 17. 60~19.85</td><td>酯酸纤维素树脂 聚碳酸酯 聚酰胺</td><td>10.9 9.8 12.7~13.6</td><td>22.30 20.05 25.98~27.83</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 619,
+        "chunk": "# 4.溶解度参数和氢键力  \n\n如上所述，借助于溶解度参数相同或相近的原则，似乎就可以比较有把握地预测高分子聚合物在溶剂（或混合溶剂）中的溶解性了。但是实践证明，其预测的准确性仅为 $50\\%$ 要这是因为赫尔德布兰德（Hildebrand）的推导是限于非极性分子混合时无放热或吸热的体系，对于强极性分子构成的体系，因为有氢键形成，混合时放热，则该推导结果不适合。因此，在表2-3-4中所列出的溶解度参数仅适用于非极性混合体系，而对于强极性分子体系，便会产生误差。  \n\n美国涂料化学家伯里尔（Burrell）在1955年提出的方法，将上述原则予以完善，使涂料工作者能对不同类型的体系较合理地判断某一聚合物的溶解能力。他提出对每一种液体有两个因素（或称参数）与液体的溶解能力有关。第一个因素是液体的氢键力。根据氢键力的强弱，伯里尔将溶剂分成3组： MP  \n\n第一组，弱氢键（烃类、氯化烷烃、硝基化烷烃)；  \n第二组，中氢键（酮类、酯类、醚类和醇醚类）；  \n第三组，强氢键 (醇类和水)。  \n\n表2-3-8是伯里尔从各种溶剂中选出了30种溶剂，按其氢键力强弱和 $\\delta$ 值递增顺序排列出的表格。  \n\n表2-3-8溶剂依氢键力强弱的分组表  \n\n\n<html><body><table><tr><td colspan=\"3\">第一组</td><td colspan=\"3\">第二组</td><td colspan=\"3\">第三组</td></tr><tr><td rowspan=\"3\">溶剂名称</td><td colspan=\"2\"></td><td rowspan=\"3\">溶剂名称</td><td colspan=\"2\"></td><td rowspan=\"3\">溶剂名称</td><td colspan=\"2\"></td></tr><tr><td>(cal/cm²)/(J/m3）1/2</td><td>10</td><td></td><td>10 (cal/ cm²)/(/m²)1/2</td><td></td><td>10 (cal/emn)/(J/m²)1/2</td></tr><tr><td>正戊烷</td><td>7.0</td><td>14.32</td><td>乙醚</td><td>7.4</td><td>15.14</td><td>2-乙基已醇</td><td>·9. 5</td><td>19.44</td></tr><tr><td>正已烧</td><td>7.3</td><td>14.94</td><td>醋酸甲基戊酯</td><td>8.0</td><td>16.39</td><td>正辛醇</td><td>10.3</td><td>21.07</td></tr><tr><td>环已烷</td><td>8.2</td><td>16.78</td><td>醋酸丁酯</td><td>8.5</td><td>17.39</td><td>正皮醇</td><td>10.9</td><td>22.3</td></tr><tr><td>正戊烯</td><td>8.5</td><td>17.39</td><td>丁基卡必醇</td><td>8.9</td><td>18.21</td><td>正丁醇</td><td>11. 4</td><td>23.32</td></tr><tr><td>甲苯</td><td>8.9</td><td>18.21</td><td>邻苯二甲酸二丁酯</td><td>9.3</td><td>19.03</td><td>正丙醇</td><td>11. 9</td><td>24.35</td></tr><tr><td>萃</td><td>9.2</td><td>18.82</td><td>溶纤剂</td><td>9.9</td><td>20.26</td><td>乙醇</td><td>12.7</td><td>25.98</td></tr><tr><td>四氯苯</td><td>9.5</td><td>19.44</td><td>环戊酮</td><td>10.4</td><td>21.28</td><td>甲醇</td><td>14.5</td><td>29.67</td></tr><tr><td>硝基苯</td><td>10.0</td><td>20.46</td><td>甲基溶纤剂</td><td>10. 8</td><td>22.10</td><td></td><td></td><td></td></tr><tr><td>1-硝基丙烷</td><td>10.7</td><td>21.89</td><td>碳酸丁烯酯</td><td>12.1</td><td>24.76</td><td></td><td></td><td></td></tr><tr><td>硝基乙烷</td><td>11. 1</td><td>22.71</td><td>碳酸丙烯酯</td><td>13. 3</td><td>27.21</td><td></td><td></td><td></td></tr><tr><td>乙晴</td><td>11. 9</td><td>24.35</td><td>碳酸乙烯酯</td><td>14.7</td><td>30.08</td><td></td><td></td><td></td></tr><tr><td>硝基甲烷</td><td>12.9</td><td>26.39</td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>\n\n$\\Phi$ 8为溶解度参数。②二乙二醇单丁醚，  \n\n雷伯曼（Lieberman）设想以氢键程度的表征平均值（相对值）来定量氢键力，依其设定，弱氢键力平均值为0.3，中氢键力平均值为1.0，强氢键力平均值为1.7。且混合溶剂的氢键力的表征平均值，可以用下式计算：  \n\n混合溶剂氢键力表征平均值 $=\\varphi_{1}A+\\varphi_{2}B+\\cdots$ 式中1，— -溶剂A，B在混合溶剂中的体积分数；  \n\nA、B—溶剂A，B的氢键力表征平均值。  \n\n第二个因素是溶解度参数。溶剂的溶解度参数 $\\delta$ 可按溶剂的氢键力大小分成3个等级，即强氢键溶解度参数 $(\\delta_{\\mathfrak{s}})$ 、中氢键溶解度参数 $(\\delta_{\\mathfrak{m}}$ )、弱氢键溶解度参数 $(\\delta_{\\mathfrak{p}}$ )。醇类溶剂属于强氢键等级；酮类、醚类和酯类溶剂属于中氢键等级；烃类溶剂则属于弱氢键等级。表2-3-9是各类溶剂的溶解度参数的大致范围。 Q  \n\n表2-3-9各类溶剂的溶解度参数的范围  \n\n\n<html><body><table><tr><td rowspan=\"3\">溶剂的</td><td colspan=\"6\">3种氢键等级的溶解度参数</td></tr><tr><td colspan=\"2\">强氢键&</td><td colspan=\"2\">中等氢键</td><td colspan=\"2\">弱氢键8</td></tr><tr><td>(cal/em)1/2</td><td>10*(J/m)1/</td><td>(cal/em)1/2</td><td>10(J/m)1/</td><td>(cal/cm)1/2</td><td>10°(J/m）1/z</td></tr><tr><td>醇类</td><td>11~13</td><td>22.50~26.60</td><td>8~10</td><td></td><td></td><td></td></tr><tr><td>酮类</td><td></td><td></td><td></td><td>16. 37~20.46</td><td></td><td></td></tr><tr><td>醚类</td><td></td><td></td><td>9~10 8~9</td><td>18.41~20.46</td><td></td><td></td></tr><tr><td>酯类</td><td></td><td></td><td></td><td>16.37~18.41</td><td></td><td></td></tr><tr><td>脂肪烃类</td><td></td><td></td><td></td><td></td><td>7~8</td><td>14.32~16.37</td></tr><tr><td>芳香经类</td><td></td><td></td><td></td><td></td><td>8~9</td><td>16.37~18.41</td></tr></table></body></html>  \n\n依据伯里尔提出的方法，当判断一种树脂在一种溶剂（或混合溶剂）中是否溶解时，首先要确认该树脂和溶剂的氢键力大小的等级，然后依据树脂和溶剂在相同氢键等级内的溶解度参数大小是否相同或相近的原则，来判断该树脂在该溶剂中是否溶解。这样就将分子极性及氢键力对溶解性的影响考虑在内了，因此和单纯依据溶解度参数一个因素进行判断的方法相比，预测的准确程度可以提高到 $95\\%$ 。将氢键力和溶解度参数结合起来考虑的方法就是通常讲的“两维方法”。  \n\n例如：E-20环氧树脂的中等氢键溶解度参数 $\\delta_{m}$ 为 $8\\sim13$ ，因此可以溶解于具中等氢键溶解度参数的溶剂中，即第二组其溶解度参数相近的溶剂，如醋酸正丁酯 $(\\delta_{\\mathrm{m}}=8,5)$ ，丙酮 $(\\delta_{\\mathrm{m}}=9,9)$ ，乙二醇单丁醚 $(\\delta_{\\mathrm{m}}=9,5)$ 等。但是它不能溶于强氢键等级（即第三组）的醇类溶剂内，如正丁醇 $\\delta_{\\mathfrak{m}}=11,4$ ）和弱氢键等级（即第一组）的烃类溶剂内，如二甲苯$(\\delta_{p}=8.8)$ ，因为E-20环氧树脂的 $\\delta_{*}$ 和 $\\delta_{\\mathfrak{p}}$ 的数值都是0。但是如果将 $70\\%$ （以体积计）的二甲苯和 $30\\%$ 的正丁醇配成混合溶剂，该混合溶剂的氢键力 $=0.7\\times0.3+0.3\\times1.7{\\approx}0.8$ 属于中等氢键力范围。该混合溶剂的溶解度参数 $\\delta_{\\#}=0,7\\times8.8+0.3\\times11.4\\approx9.6$ 量  \n\n由计算结果可以看出，E-20环氧树脂和该混合溶剂属同一氢键等级，而溶解度参数又相近，故E-20环氧树脂可以溶于该混合溶剂中。  \n\n问题讨论到这里，我们便清楚地知道，高分子聚合物相对于表2-3-8中每一组溶剂都有一个溶解度参数范围，即 $\\delta_{\\mathfrak{p}}$ ， $\\delta_{\\mathfrak{m}}$ 和 $\\delta_{*}$ 。这些数值可以通过计算而求得，但通常采用试验的方法来测得。根据伯里尔的方法，我们在 $^{*}3$ ：溶解度参数的应用”项下 $\\textcircled{4}$ 部分讨论过的。通过高聚物在已知溶解度参数的溶剂中的溶解情况，确定高聚物溶解度参数范围的方法，可以进一步完善。即对某一种要测定其溶解度参数的树脂，按照其实际使用的浓度（如对硝基纤维素其浓度为 $20\\%$ ，对醇酸树脂则为 $50\\%$ ）选择表2-3-8某一组内的溶剂进行试验，如果该树脂在表中同一组中两种溶剂都溶解，那么这一组内位于这两种溶剂之间的溶剂都能溶解该树脂，这就找出了该树脂在这种氢键力等级内的溶解度参数范围。  \n\n雷伯曼（Lieberman）在精辟地闸述了氢键概念的基础上，提出了一种用图示法来绘制各种树脂“溶解度的等高线”的方法，这一两维曲线的方法，在选择树脂良溶剂时，至今仍然常用。 ”  \n\n![](images/584888c00128a186b5b32e9e6c6be348592ab4ad1e569eee6e1173e19d304dd2.jpg)  \n图2-3-4各类溶剂在溶解度参数图中的近似位置  \n\n![](images/a0721e2a4ee2f44921e7940ab3863bb58d6e111d7259129d0cdf5051cbfe4ca4.jpg)  \n图2-3-5乙烯树脂的等高线图  \n\n在一个两维溶解度参数氢键图上，各种类型溶剂的近似位置如图2-3-4所示，每一种溶剂分别有一个特定的溶解度参数和一个氢键值。这些数据已在表2-3-4中列出，将表中数据  \n\n标在图上，则如图2-3-4所示。  \n\n图2-3-5是乙烯树脂的等高线图，这种方法的第一个步骤在ASTMD3132中有介绍，这是将树脂加入各种溶剂中，在适当混合及熟化后，就可以用完全溶解、边界溶液或不溶性溶液来对这些溶液进行评价。绘制出的树脂溶解度的等高线则将溶液划分为溶解和不溶解两种类型。我们可以从表2-3-4中所给出的溶解度参数和氢键数据，选择出在图中溶解度区内的溶剂，这些溶剂必定是该树脂的良溶剂。  \n\n图2-3-6和图2-3-7给出了利用“树脂溶解度等高线”选择混合溶剂的过程。图中丁醇、二甲苯和2-硝基丙烷的溶解度参数和氢键值可以从表2-3-4中查得，并在图中标出3个点，连接这3个点形成一个三角形覆盖在乙烯树脂的等高线上，而混合溶剂的溶解度区如图2-3-6中的阴影部分所示。假设图2-3-7中的 $\\boldsymbol{E}$ 点是溶解度图中选出的一个理想点，为了计算混合溶剂的组成，首先要从三角形的一个顶点通过 $\\boldsymbol{E}$ 点向对面画直线，该线与对边的交点为D。两相混合物的组成可以通过测量 $B D$ 和 $c D$ 的相对长度来确定。这样，所有3种成分的含量就全部确定了。用数学方式表示该过程如下：  \n\n![](images/106d16ccfdb3403961e805ecaf8e3f6a94a31f6532fe347476ccb6a1886cdc34.jpg)  \n图2-3-6可能形成树脂良溶剂混合物的区域图  \n\n![](images/581235ead7c2837314ac1db0898d206a3e1bec3a07943c93c5adb42a0c2d67e3.jpg)  \n图2-3-7利用线性混合规则计算理想溶剂混合物组成  \n\n丁醇的体积分数( $\\varphi_{\\mathrm{B}})=100-(\\varphi_{\\mathrm{X}})\\times D C/B C=50\\%\\times2/4=25\\%$  \n\n在多数情况下，利用溶解度参数和氢键值绘制的两维曲线所确定的树脂溶解度范围，或依已知的树脂溶解度等高线选择溶剂或混合溶剂的结果是令人满意的。  \n\n汉森（Hunsen）和嘉顿（Gardon）又进一步把分子间的相互作用力分为3种类型，即色散力 $\\Delta E_{\\mathrm{d}}$ 、诱导力 $\\Delta E_{\\scriptscriptstyle\\mathsf{P}}$ 和氢键力 $\\Delta E_{\\mathrm{h}}$ 。并且指出上述3种作用力对溶剂总的溶解度参数$\\delta_{\\perp}$ 的贡献值为 $\\delta_{\\phi}$ ， $\\delta_{\\mathfrak{p}}$ 和 $\\hat{\\sigma}_{\\mathrm{h}}$ ，且推导出：  \n\n$$\n\\delta_{B}=(\\delta_{d}{}^{2}+\\delta_{p}{}^{2}+\\delta_{\\mathrm{h}}{}^{2})^{1/2}\n$$  \n\n希望通过三维溶解度参数的方法使溶解度参数在应用方面更为精确。遗憾的是，这些新的修正几乎都使溶解度参数在实际应用上更为困难。而伯里尔最初提出的方法至今仍为涂料工作者所乐于采用。  \n\n现在，高聚物是否溶于混合溶剂的配方设计可采用计算机进行，即先制成一个可溶解的体系，设计一定的程序将所得的数据贮存在计算机中，即可进行计算，尤其当混合溶剂体系，要以某组分取代另一组分时，计算更为快捷准确。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 620,
+        "chunk": "# （三）溶剂化原则  \n\n聚合物的溶胀和溶解与溶剂化作用有关，溶剂化作用是高分子聚合物和溶剂接触时，溶剂分子对高聚物分子相互产生的作用力，此作用力大于高聚物分子间的内聚力，故可以使高聚物分子彼此分离而溶解于溶剂中。极性溶剂分子和高聚物的极性基团相互吸引能产生溶剂化作用，使聚合物溶解。这种溶剂化作用主要是高分子上的酸性基团（或碱性基团）能与溶剂中的碱性基团（或酸性基团）起溶剂化作用而溶解。这里所指的酸、碱是广义的，酸就是指电子接受体（即亲电子体)，碱就是电子给予体（即亲核体)。所以，把二者放到一起就会相互作用，发生溶剂化使高聚物溶解。不同的酸和碱其强弱有所不同，常见亲电、亲核基团的强弱次序列举如下：  \n\n亲电子基团亲核基团  \n\n-CHNH>—CHNH>—CON(CH)2>—CONH—>=PO>—CHCOH->—CHOCOCH—>—CH--O-CH-  \n\n如聚合物分子中含有大量亲电子基团，则能溶于含有给电子基团的溶剂中，如硝基纤维素含有亲电子基团 $\\mathrm{ONO_{2}}$ ，可溶于有给电子基团的溶剂，如丙酮、丁酮中，也可溶于醇醚混合物，即含有一OH与—O—的混合溶剂中。  \n\n如高聚物分子中含有上述序列中的后几个基团时，由于这些基团的亲电子性或给电子性比较弱，要溶解这类聚合物，应该选择含有相反系列中最前几个基团的溶剂。  \n\n以上所述的判断溶剂溶解能力的三原则，即极性相似原则、溶解度参数相近原则和溶剂化原则，应用时应合在一起考虑，才能得到准确的结果。例如聚碳酸酯（ $\\delta{=}9.5)$ 、聚氯乙烯 $(\\delta\\mathbf{=}9,7)$ ，它们的溶解度参数极为相近，如按“同类溶解同类”和“溶解度参数相近”的原则，应能溶于极性溶剂氯仿 $\\langle\\delta=9.3\\rangle$ 、二氯甲烷（ $\\delta{=}9,7$ ）和环已酮（ $\\delta=9,9)$ 。实际上聚碳酸酯不溶于环己酮，只溶于氯仿和二氯甲烷。而聚氯乙烯，只溶于环己酮，不溶于氯仿和二氯甲烷中。这种现象可用溶剂化原则来解释：由于聚碳酸酯是给电子性聚合物，而聚氯乙烯是一个弱亲电子性聚合物，它们与其相应的良溶剂进行溶剂化作用，并与两种给电子性溶剂相吸，有利于溶解。它们之间的作用可以表示如下：  \n\n![](images/9c64240979de1a8ff0a57175cd8703e2c75cfd0ca1a16d4ba77447cd2b17559c.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 621,
+        "chunk": "# （四）其他测定溶剂溶解能力的方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 622,
+        "chunk": "# 1.贝壳松脂 $\\cdot$ 丁醇值（KB值）试验  \n\nKB值是测定烃类溶剂溶解能力最常用的方法，即在一定量的贝壳松脂·丁醇溶液中滴加烃类溶剂至出现沉淀或浑浊时所需的毫升数。具体试验方法是将 $100\\mathbf{g}$ 贝壳松脂溶于 $500g$ 丁醇中配制成标准溶液，温度在 $25^{\\circ}\\mathbb{C}\\pm2\\mathbb{C}$ ，取 $20\\mathbf{g}$ 贝壳松脂·丁醇溶液滴加烃类溶剂至出现浑浊时，求所需烃类溶剂的毫升数，试验平均误差为 $\\pm0.1\\mathrm{mL}$ ，所需烃类溶剂的毫升数愈高，表示溶解能力越强。表2-3-10为烃类溶剂的平均贝壳松脂 $\\cdot\\cdot$ 丁醇试验值（KB值)。从表中可知，芳香烃溶剂的数值高，脂肪烃溶剂的数值低。  \n\n表2-3-10烃类溶剂的平均贝壳松脂·丁醇试验值  \n\n\n<html><body><table><tr><td colspan=\"2\">溶 剂</td><td>KB值</td><td colspan=\"2\">剂</td><td>KB值</td></tr><tr><td rowspan=\"5\">脂肪烃</td><td rowspan=\"5\">石油醚 戊烷</td><td rowspan=\"2\">25 25</td><td rowspan=\"2\">脂肪烃</td><td>辛烷</td><td>32</td></tr><tr><td>200号涂料溶剂油</td><td>37</td></tr><tr><td rowspan=\"3\">2.3035</td><td rowspan=\"3\">芳香烃</td><td></td><td>107</td></tr><tr><td></td><td></td></tr><tr><td>二甲苯</td><td>103</td></tr></table></body></html>  \n\n对于涂料用烃类溶剂来说，可根据其KB值来估算溶解度参数。  \n\n脂肪烃 $\\delta{=}6.3\\mathrm{+}0.03\\mathrm{\\times}\\mathrm{KB}$ 值 芳香烃 $\\delta\\mathrm{=}6.9\\mathrm{+}0.02\\times\\mathrm{KB}$ 值",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 623,
+        "chunk": "# 2.苯胺点法  \n\n苯胺点法是用于测定脂肪烃溶剂的溶解能力的。它是相同体积的苯胺和溶剂相混得到清澈溶液的最低温度。该温度就是人们熟悉的“临界溶液温度”。此值越低说明溶解能力越高，反之则溶解能力越低。测试时将 $10\\mathrm{ml},$ 溶剂与 $10\\mathrm{mL}$ 苯胺在一个带有套管的测试管中混合起来，在测试中要连续不断地摇动溶液，如果混合物开始是清澈的，那么将其冷却到浑浊，这一由清澈变浑浊的转变点就是苯胺点。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 624,
+        "chunk": "# 3.混合苯胺点法  \n\n混合苯胺点法是用来测定芳香烃溶剂的溶解能力的。除了将样品先与等体积的正庚烷混合，然后再将此混合物与等体积的苯胺混合测试外，其他方法与苯胺点法相似。这样最后被测试的混合物含有 ${\\mathrm{5mL}}$ 的样品、5mL的正庚烷和 $10\\mathrm{mL}$ 的苯胺。因为芳香烃溶剂与苯胺的混合物在和苯胺冰点一样的低温下能形成透明的均相混合物，所以在测试过程中需要进行调节。正庚烷能提高混合物的浊点，将比例调节以后对测试高溶解力的芳香烃溶剂更为方便。混合苯胺点值越低，表明溶剂的溶解能力越强，否则相反。表2-3-11是部分溶剂苯胺点（或混合苯胺点）的数据。  \n\n表2-3-11部分溶剂苯胺点（或混合苯胺点）数据  \n\n\n<html><body><table><tr><td>溶剂</td><td>苯点混合</td><td>溶剂</td><td>点、混合</td><td>溶剂</td><td>苯点合</td><td>溶剂</td><td>苯胶点混合</td></tr><tr><td>苯</td><td>30</td><td>邻二甲萃</td><td>20</td><td>丁烧</td><td>107.6</td><td>庚烷</td><td>70.0</td></tr><tr><td>甲苯</td><td>30</td><td>异丙苯</td><td>-5</td><td>异戊烷</td><td>77.8</td><td>异丁烷</td><td>14.9</td></tr><tr><td>乙蓉</td><td>-30</td><td>丙苯</td><td>-30</td><td>已烷</td><td>68.6</td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 625,
+        "chunk": "# 4.稀释比法  \n\n在涂料产品中，为了提高性能或降低成本，在配方中除了加人能溶解成膜物（树脂）的溶剂以外，还要加入一部分不能溶解成膜物质，只能稀释树脂溶液的稀释剂。稀释比即是用来测定溶解硝化纤维素的溶剂中，可以加人稀释剂的最大数量，以稀释剂和溶剂的比值表示，即：  \n\n溶剂稀释比=稀释剂的加人量（呈浑浊点）/溶剂量  \n\n测定时先配制成含量一定的硝化纤维素溶液，再用稀释剂滴定至开始出现浑浊为止，然后求出稀释比值。比值越大，即稀释剂允许加入的量越多，说明溶剂的溶解能力越强。  \n\n依据上面所讨论的溶剂对树脂溶解力的理论预测方法及试验测定方法，最终目的是选择合适的溶剂，纳入色漆配方，使其能溶解色漆中的树脂，形成均匀且稳定的溶液，这是保证漆液性能的基本前提。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 626,
+        "chunk": "# 二、黏度  \n\n在涂料工业中，我们不仅关心树脂能否溶解在溶剂中，形成均匀的溶液。同时也关心所形成的树脂溶液黏度，即希望相同浓度（或固体含量）的树脂溶液黏度越低越好。这样，当达到相同的施工黏度时，漆液的固体含量较高，从而使施工效率提高，而挥发到大气中的溶剂量较少，对环境的污染较轻。  \n\n![](images/871bc2294c800d998a04f288d82e70fd13db5a799a819415b020e63cb444245b.jpg)  \n图2-3-8溶剂的溶解力对树脂溶液黏度的影响  \n\n溶剂通常是以如下两种方式影响着树脂溶液的黏度： $\\textcircled{1}$ 溶剂对高聚物的溶解力；$\\textcircled{2}$ 溶剂自身的黏度。  \n\n前者的作用为人们所普遍认识，而后者的作用往往为人们所忽视。  \n\n对于高聚物的浓溶液（涂料工业所用的树脂溶液均为此类型)，溶剂的溶解力越强，所形成的树脂溶液黏度越低。如图2-3-8所  \n\n示，由于甲苯对中油度醇酸树脂及亚麻油的溶解力比正庚烷强，故而所得树脂溶液在相同浓度时黏度较低。  \n\n惊人的事实是：往往被人们所忽视的溶剂自身的黏度，对树脂溶液黏度的影响十分显著，溶剂自身黏度相差不大于 $1\\mathrm{{mPa}\\cdot\\mathrm{{~s~}}}$ 时，会使树脂溶液的黏度相差几百甚至上千$\\mathbf{\\sigma}_{\\mathrm{m}}\\mathrm{Pa}\\cdot\\mathbf{s}$ 。表2-3-12所示3种相同相对分子质量范围的烃类溶剂的性质。  \n\n分析表2-3-12中的数据可见，甲苯（KB值105，混合苯胺点 $11\\mathrm{\\bar{C}}$ ）的溶解力优于甲基环己烷，甲基环已烷又优于正庚烷。但是从最低的溶液黏度的角度来看，正庚烷则是优选的溶剂，因为它的黏度最低。确实，上述3种溶剂的黏度相差不大（最大相差 $0.3\\ \\mathrm{mPa\\cdots)}$ ·而溶液的黏度却相差甚大。图2-3-9是这3种溶剂的黏度和它们的石灰松香溶液（固体含量为 $50\\%$ ）黏度的关系图。由图中可以看出，溶剂自身黏度对溶液黏度的影响是明显的，溶液黏度n/溶剂黏度 $\\eta_{0}=75$ 。而溶剂溶解力的影响仅为次要作用，如甲苯虽然溶解力大大优于正庚烷，但是，由于其自身黏度较高，致使树脂溶液的黏度仍然比以正庚烷作溶剂的树脂溶液高。  \n\n若溶剂类型保持恒定的话，溶剂和溶液黏度间的关系则更为密切。例如，图2-3-10为3种异链烷烃溶剂（其中KB值基本相同）的黏度和 $40\\%$ （质量分数）长油度醇酸树脂溶液黏度的关系。由图中可知，溶液黏度 $\\eta$ 和溶剂黏度 $\\eta_{0}$ 之比为220。因此溶液黏度降低$0.5\\mathrm{{mPa}\\cdot{s}}$ 时，足可以使 $40\\%$ （质量分数）浓度的树脂溶液的黏度下降 $110\\mathrm{{mPa}\\cdot\\mathrm{{s}\\ (220\\times0.5)}}$ 费  \n\n表2-3-12具有相同相对分子质量范围的3种经类溶剂的性质  \n\n\n<html><body><table><tr><td>项目</td><td colspan=\"3\">溶剂范围</td></tr><tr><td>溶剂</td><td>（烷烃） 正庚烷</td><td>(芳香烃) 甲苯</td><td>（环己烷）</td></tr><tr><td>结构式</td><td>CHCHCHCHCHCHCH</td><td>CH</td><td>甲基环已烷 -CH</td></tr><tr><td>相对分子质量</td><td>100</td><td>92</td><td>98</td></tr><tr><td>25℃下的黏度/mPa • s</td><td>0.39</td><td>0.56</td><td>0. 69</td></tr><tr><td>黏度比</td><td>1. 00</td><td>1.44</td><td>1.77</td></tr><tr><td>沸点/C</td><td>98</td><td>110</td><td>101</td></tr><tr><td>KB值（贝壳松脂·丁醇值）</td><td>25</td><td>105</td><td>50</td></tr><tr><td>混合苯胺点/C</td><td>70</td><td>11</td><td>54</td></tr></table></body></html>  \n\n![](images/aa566fb93c736873a8efd67b769f46685ca52ec70e2ae77428a000fa52c7f951.jpg)  \n图2-3-9 $50\\%$ （质量分数）石灰松香在3种烃类溶剂中的溶液黏度和溶剂黏度的关系  \n\n![](images/0c5d465ac4ce77d9d76cafeb46203c874dedd4fbccd65ab972eabdfdc2209fb9.jpg)  \n图2-3-103种异链烷烃溶剂的黏度和 $40\\%$ （质量分数）长油度醇酸树脂溶液黏度的关系  \n\n因此，我们在配制任何一种涂料用树脂溶液（漆料）或涂料产品时，为使其黏度能满足预定的要求指标，在选择溶剂时，必须考虑溶剂的溶解力和溶剂的自身黏度这两个重要因素。  \n\n单一溶剂的黏度，可以由有关资料查得。表2-3-13列出了涂料常用溶剂的黏度。  \n\n但是涂料产品往往使用的是混合溶剂。理想的（即不相互作用的）混合溶剂的黏度可由式(2-3-17）精确求得。即  \n\n$$\n\\scriptstyle1_{B}\\eta=\\sum(\\ w\\ \\log)_{i}\n$$  \n\n式中 $\\eta$ —混合溶剂的黏度，mPa·s；$\\boldsymbol{w}_{i}$ —第i组分的质量分数， $\\%$ $\\eta_{i}$ —第i组分的自身黏度， $\\mathbf{\\sigma}_{\\mathrm{m}}\\mathbf{P}\\mathbf{a}\\cdot\\mathbf{\\sigma}_{\\mathrm{s}}$ 。  \n\n【例题2-3-5】试计算由 $48\\%$ 丁酮（质量分数） $(\\eta{=}0,41\\ \\mathrm{{mPa}\\ {\\bullet}\\ \\mathrm{{s})}}$ ， $32\\%$ （质量分数）醋酸正丁酯 $\\mathrm{:\\eta=0.68~mPa\\cdot\\s)}$ 和 $20\\%$ （质量分数）甲苯（ $\\eta{=}0,55\\ \\mathrm{mPa}\\ {\\bullet}\\ s)$ 组成的混合溶剂的黏度。  \n\n解由于酮类、酯类和烃类溶剂混合时不会发生相互作用，将已知数据代入式(2-3-17)，即可求得混合溶剂的黏度为  \n\n$$\n\\mathbf{lg}\\eta=0.48\\times1\\mathbf{g}\\ 0.\\ 41+0.32\\times1\\mathbf{g}\\ 0.\\ 68+0.20\\times1\\mathbf{g}\\ 0.\\ 55\n$$  \n\n表2-3-13常用溶剂的黏度（20℃）  \n\n\n<html><body><table><tr><td>名称</td><td>黏度 /mPa • s</td><td>名称</td><td>黏度 /mPa• s</td><td>名称</td><td>黏度 /mPa• s</td><td>名称</td><td>黏度 /mPa • s</td></tr><tr><td>苯</td><td>0.60</td><td>异丙醇</td><td>2.431</td><td>醋酸乙酯</td><td>0.449</td><td>乙二醇丁醚醋酸酯</td><td>1. 80</td></tr><tr><td>甲苯</td><td>0.5866</td><td>正丁醇</td><td>2.95</td><td>醋酸正丁酯</td><td>0.734</td><td>正已烷</td><td>0.32</td></tr><tr><td>间二甲苯</td><td>0.579Φ</td><td>异丁醇</td><td>3.95</td><td>醋酸异丁酯</td><td>0.697</td><td>正庚烷</td><td>0.409</td></tr><tr><td>Solvesso 100</td><td>0.80</td><td>仲丁醇</td><td>4. 210</td><td>醋酸正戊酯</td><td>0. 924</td><td>二氯甲烷</td><td>0.425</td></tr><tr><td>Solvesso 150</td><td>0.10</td><td>丙酮</td><td>0.316</td><td>醋酸异戊酯</td><td>0.872</td><td>1,1,1-三氯乙烷</td><td>0.903</td></tr><tr><td>Solvesso 200</td><td>2.80</td><td>甲基丙酮</td><td>0.423</td><td>乳酸丁酯</td><td>3.58</td><td>硝基乙烷</td><td>0.661</td></tr><tr><td>苯乙烯</td><td>0.696</td><td>异佛尔酮</td><td>2.62</td><td>乙二醇乙醚</td><td>2.05</td><td>硝基丙烷</td><td>0.798</td></tr><tr><td>甲醇</td><td>0.5945</td><td>环己酮</td><td>2.20</td><td>二甘醇乙醚</td><td>3.85</td><td></td><td></td></tr><tr><td>乙醇</td><td>1.09</td><td>丁酮</td><td>0.423</td><td>二甘醇丁醚</td><td>6.49</td><td></td><td></td></tr><tr><td>丙醇</td><td>2.26</td><td>二丙酮醇</td><td>2.9</td><td>乙二醇乙醚酯酸酯</td><td>1.025</td><td></td><td></td></tr></table></body></html>\n\n$\\Phi$ 为25℃时的黏度数值。  \n\n上述混合溶剂实际测定出的黏度为 $0.49\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$ ，和计算值误差不大。  \n\n但是，很多混合溶剂，特别是含有羟基的溶剂（如醇类)，由于分子间彼此有相互作用，故为非理想的混合溶剂，不能直接用式(2-3-17）来计算其黏度。所以有必要对式（2-3-17)进行修正，以使其适合于非理想的混合溶剂。因此，对含有两种相互作用溶剂的混合体系，有人提出把其中一种溶剂规定其所谓的有效黏度值，以便更精确地反映这两种溶剂在发生相互作用时的混合特性，有效黏度由实验数据确定。这种已规定有效黏度值的溶剂在有机溶剂中的质量分数规定不超过20%～40%。表2-3-14和表2-3-15分别为醇类溶剂和烃类溶剂混合时的有效黏度及含氧溶剂和水混合时的有效黏度数据。研究结果表明，当已规定有效黏度的溶剂在混合溶剂中的质量分数不超过 $20\\%\\sim40\\%$ 时，可以将式（2-3-17）修正为式(2-3-18)。在式(2-3-18）中将其中可以发生相互作用的溶剂以其有效黏度代替真实黏度。即  \n\n$$\n\\begin{array}{r}{\\log\\eta{=}\\sum(w\\log\\mathsf{l g}\\eta_{\\mathsf{a}})_{i}+\\sum(w\\log\\mathsf{l g}\\eta_{\\mathsf{e}})_{j}}\\end{array}\n$$  \n\n上式同样适用于含氧有机溶剂与水的混合液。由于水的黏度值为 $0,92\\mathrm{{mPa}\\cdot{s_{e}}}$ 将其直接代人式(2-3-18）后，可简化为式(2-3-19)。  \n\n$$\n\\begin{array}{r l}&{\\mathsf{l g}\\eta=\\sum(w\\mathrm{\\mathsf{lg}}\\mathrm{\\mathsf{\\Omega}}_{0},92)_{\\mathrm{H_{2}O}}+\\sum(w\\mathrm{\\mathsf{lg}}\\eta_{\\mathrm{e}})_{j}}\\\\ &{\\qquad=(-0,0362w)+\\sum(w\\mathrm{\\mathsf{lg}}\\eta_{\\mathrm{e}})_{j}}\\end{array}\n$$  \n\n表2-3-14各种醇类溶剂在25℃的真实黏度和有效黏度（与烃类溶剂混合，醇类溶剂的含量在 $30\\%\\sim40\\%$ 以下)  \n\n\n<html><body><table><tr><td rowspan=\"2\">醇类溶剂</td><td colspan=\"2\">黏度/mPa•s</td><td rowspan=\"2\">黏度比n/</td><td rowspan=\"2\">醇类溶剂</td><td colspan=\"2\">黏度/mPa*s</td><td rowspan=\"2\">黏度比n/n</td></tr><tr><td>真实黏 度</td><td>有效黏 度</td><td>真实黏</td><td>有效黏 度张</td></tr><tr><td>乙醇</td><td>1.30</td><td>1.05</td><td>0.81</td><td>二丙酮醇</td><td>度 2.90</td><td>2.00</td><td>0.69</td></tr><tr><td>乙二醇单甲醚</td><td>1.60</td><td>1.20</td><td>0.75</td><td>异丁醇</td><td>3.40</td><td>1.80</td><td>0.53</td></tr><tr><td>乙二醇单乙醚</td><td>1.90</td><td>1.20</td><td>0.63</td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>2. 00</td><td></td><td>0. 70</td><td>甲基异丁基甲醇</td><td>3.80</td><td>1.80</td><td>0.47</td></tr><tr><td>丙醇</td><td></td><td>1. 40</td><td></td><td>一缩二乙二醇单丁醚</td><td>5.30</td><td>2.15</td><td>0.41</td></tr><tr><td>丁醇</td><td>2.60</td><td>1.60</td><td>0.62</td><td>2-乙基己醇</td><td>7.78</td><td>3.30</td><td>0.42</td></tr><tr><td>仲丁醇</td><td>2.90</td><td>1.40</td><td>0.48</td><td>平均</td><td></td><td></td><td>0.59</td></tr></table></body></html>  \n\n【例题2-3-6】试计算甲苯 $\\left(\\eta=0,55\\mathrm{mPa}\\cdot\\mathbf{s}\\right)$ 和异丙醇 $70:30$ （质量比）混合溶剂的黏度。  \n\n解由于异丙醇在和烃类溶剂的混合溶剂中的含量没超过 $40\\%$ ，该混合溶剂的黏度可由式（2-3-18）求得。异丙醇的有效黏度系采用表2-3-14中的数据。  \n\n表2-3-15含氧有机溶剂在25℃的真实黏度和有效黏度  \n（与水混合，含氧有机溶剂含量在20%～30%以下）  \n\n\n<html><body><table><tr><td rowspan=\"2\">含氧溶剂</td><td colspan=\"2\">黏度/mPa·s</td><td rowspan=\"2\">黏度比/</td><td rowspan=\"2\">含氧溶剂</td><td colspan=\"2\">黏度/mPa·s</td><td rowspan=\"2\">黏度比μ/%</td></tr><tr><td>真实黏 度</td><td>有效黏 度</td><td>真实黏 度</td><td>有效黏 度</td></tr><tr><td>丙酮</td><td>0.31</td><td>6.06</td><td>19.5</td><td>一端二乙二醇单乙醚</td><td>4.00</td><td>26.1</td><td>6.5</td></tr><tr><td>丁酮</td><td>0.41</td><td>9.8</td><td>23. 9</td><td>叔丁醇</td><td>4.50</td><td>116.4</td><td>25.9</td></tr><tr><td>乙二醇单甲醚</td><td>1.60</td><td>14.0</td><td>13. 0</td><td>一缩二乙二醇单丁醚</td><td>5.30</td><td>35.0</td><td>6.6</td></tr><tr><td>乙二醇单乙醚</td><td>1.90</td><td>24.4</td><td>8.8</td><td>乙二醇</td><td>17.4</td><td>10.0</td><td>0.57</td></tr><tr><td>异丙醇</td><td>2.10</td><td>59.3</td><td>28. 2</td><td>二甘醇</td><td>28.9</td><td>15.6</td><td>0.54</td></tr><tr><td>二丙酮醇</td><td>2.90</td><td>22.2</td><td>7.7</td><td>已二醇</td><td>29.8</td><td>65.0</td><td>2.2</td></tr><tr><td>缩二乙二醇单甲醚</td><td>3.08</td><td>17.3</td><td>4.6</td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n值得注意，醇类溶剂体系的有效黏度与真实黏度的比值（ $\\eta_{n}/\\eta_{e}$ ）变化不大，平均为0.59，而含氧溶剂和水混合的体系中这个比值的变化却相当大，由于水性体系在涂料工业中日益发展，能以适当的精度预测出水性混合溶剂的各种不同的黏度特性将日趋重要，故本节也将这方面的问题一并讨论之。  \n\n【例题2-3-7】试计算 $10\\%$ （质量分数）的异丙醇、 $10\\%$ 甲氧基乙醇（质量分数）和$80\\%$ 水（质量分数）的混合溶剂的黏度。  \n\n解将由表2-3-14中查得的有效黏度的数值代人式（2-3-19）中得  \n\n$$\n\\mathbf{lg}\\pmb{\\eta}=(-0.0362\\times0.80)+0.10\\times\\mathbf{lg}59.3+0.10\\times\\mathbf{lg}14\n$$  \n\n$$\n=-0.0290+0.1773+0.1146=0.263\n$$  \n\n上述混合溶剂实测出的黏度为 $1.81\\mathrm{{mPa}\\cdot\\varepsilon}$ 和计算值 $1.83\\mathrm{mPa}\\cdot\\mathrm{s}$ 极为接近。  \n\n式(2-3-18）和式（2-3-19）仅适用于已规定了有效黏度值的那类溶剂，而且在混合溶剂中其含量为 $30\\%\\sim40\\%$ 的体系。但是，可借助于另一公式来消除这种局限性。例如对水-醇二元混合体系而言，有人推荐采用式（2-3-20），该式在任意混合范围内计算值均近似于实测值（式中 $\\boldsymbol{w}$ 为溶剂的质量分数）。  \n\n$$\n\\begin{array}{r}{\\log{\\eta_{2}}=(1-w)\\log{\\eta_{1}}_{\\tau}0+w_{2}\\log{\\eta_{2}}+(w-w_{2})\\log{\\eta_{\\Sigma}}}\\end{array}\n$$  \n\n这种类型的公式也可推广到多元醇类组分的混合溶剂，得式(2-3-21)，式中 ${\\boldsymbol{w}}_{j}$ 是j个醇类组分的质量分数。  \n\n【例题2-3-8】试计算 $35\\%$ （质量分数）异丙醇、 $25\\%$ （质量分数）乙二醇和 $40\\%$ （质量分数）水的混合溶剂的黏度。  \n\n解把已知数据代入式(2-3-21)，（注意 $\\pmb{w=}0,35+0,25=0,60)$ $1_{\\mathbf{g}}\\eta=0.\\ 40\\times1_{\\mathbf{g}}0.\\ 92+0.\\ 35\\times0.\\ 60\\times1_{\\mathbf{g}}2.\\ 10+0.\\ 25\\times0.\\ 60\\times1_{\\mathbf{g}}17.\\ 4+$ $0.35\\times0.40\\times1\\mathbf{g}59.3+0.25\\times0.40\\times1\\mathbf{g}10=0.588$ n=3.87mPa·s",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 627,
+        "chunk": "# 三、挥发速率  \n\n干燥的涂膜是在溶剂挥发过程中形成的。在这个过程中，溶剂的作用是控制涂膜形成时的流动特性，如果溶剂挥发太快，那么涂膜既不会流平，也不会对基材有足够的湿润，因而不能产生很好的附着力。挥发过于迅速的溶剂，还会导致由于迅速冷却而使湿膜表面的水蒸气冷凝而形成的涂膜发白。如果溶剂挥发太慢，不仅会延缓干燥时间，同时涂膜会流挂而变得很薄。如果溶剂组成在挥发过程中发生不理想的变化，就会产生树脂的沉淀和涂膜的缺陷。因此溶剂的挥发速率是影响涂料及涂膜质量的一个重要因素。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 628,
+        "chunk": "# （一）溶剂从涂膜中的挥发速率",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 629,
+        "chunk": "# 1.纯溶剂的挥发速率  \n\n尽管曾有人提出可将溶剂的沸点作为预测其挥发性的依据，可是只有同系物之间或石油溶剂之间符合这一规律，作为一种通用的方法并不科学，结果也不准确。例如，丁醇的沸点$(118^{\\circ}\\mathrm{C}$ ）比醋酸正丁酯（127℃）低 $^{\\mathfrak{g}\\mathfrak{C}}$ ，而丁醇的挥发速率（0.4）比醋酸丁酯（1.0）却慢 $60\\%$ ，因此，以溶剂沸点的低、中、高来预测挥发速率的快、中、慢是不准确的。  \n\n毫无疑问，预测纯溶剂挥发性最好的依据是其蒸气压。对于理想系统，其蒸气压和挥发速率的关系由拉乌尔定律来确定，其数学表达式如下所示：  \n\n$$\n\\phi_{1}=\\phi_{1}^{0}x_{1}\n$$  \n\n式中 $\\pmb{\\mathscr{p}}_{1}$ —混合物中组分的分压， $\\mathbf{P_{\\lambda}}_{\\mathbf{a}}$ $p_{1}^{0}$ —纯组分的蒸气压，Pa；$_{x_{1}}$ —液体组分的摩尔分数。  \n\n拉乌尔定律的这种最简单的形式说明了混合物中某一组分的分压等于其摩尔分数与其纯组分蒸气压的乘积。对于非理想系统，有必要在公式中加入活性系数这一概念。即  \n\n$$\n\\scriptstyle\\pmb{\\mathscr{p}}_{1}=\\pmb{\\mathscr{r}}_{1}\\pmb{\\mathscr{p}}_{1}^{0}\\pmb{\\mathscr{x}}_{1}\n$$  \n\n通过测量系统的总蒸气压和挥发相的组成，就可以直接得到挥发系统的活性系数。  \n\n涂料工业中，对纯溶剂挥发率的表示使用的是相对挥发速率的概念。依据ASTMD3539—76（81）规定方法，用Shell薄膜挥发仪测定。将一定体积的溶剂分布在标准面积的滤板上，在一定的温度和湿度下，气流以一定的流量通过，记录一定时间间隔的挥发量，并将挥发量为 $90\\%$ 的挥发时间 $(t_{90}$ ）与醋酸丁酯挥发量为 $90\\%$ 的时间 $\\dot{\\iota}_{90}=456\\mathrm{s})$ 的比值，称为该溶剂的相对挥发速率，即  \n\n$$\nR^{\\circ}=456/t_{90}\n$$  \n\n式中 $R^{\\circ}$ ——单一纯溶剂相对醋酸正丁酯的挥发速率；  \n\n$t_{90}$ 1 溶剂试样依ASTMD3539--76（81）规定的方法挥发 $90\\%$ 体积所需的时间，s；  \n\n456——醋酸正丁酯的 $\\scriptstyle t_{90}$ 时间，s。  \n\n因而，醋酸正丁酯的 $R^{\\circ}=1$ 9 $R^{\\circ}$ 的数值越大，表示该溶剂挥发得越快。表2-3-16列出了涂料常用溶剂的沸点及挥发速率的数据。  \n\n表2-3-16涂料常用溶剂的沸点及挥发速率（醋酸正丁酯挥发速率 $\\mathbf{\\Omega}=1,0\\dot{}$   \n\n\n<html><body><table><tr><td>名称</td><td>分子式</td><td>相对分子质量</td><td>沸点/C</td><td>挥发速率</td></tr><tr><td colspan=\"2\">石油醚</td><td>低级烷烃混合物</td><td></td><td>30~120</td><td>一</td></tr><tr><td colspan=\"2\">200号涂料溶剂油</td><td>主要成分为戊烷、已烷、庚烷、辛烷</td><td>一</td><td>145~200</td><td>约0.18</td></tr><tr><td colspan=\"2\">正庚烷</td><td>CH16</td><td>100.21</td><td>98.4</td><td>约0.2</td></tr><tr><td colspan=\"2\">正辛烷</td><td>CgH18</td><td>114. 23</td><td>125.6</td><td>约0.2</td></tr><tr><td colspan=\"2\">萃</td><td>CH6</td><td>78.11</td><td>79.6</td><td>5.0</td></tr><tr><td colspan=\"2\">甲苯</td><td>CHCH</td><td>92.13</td><td>111.0</td><td>1.95</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>名称</td><td>分子式</td><td>相对分子质量</td><td>沸点/C</td><td>挥发速率</td></tr><tr><td>二甲苯</td><td>CH(CH)</td><td>106.13</td><td>135.0</td><td>0.68</td></tr><tr><td>Solvesso 100</td><td>CH(CH)s</td><td>一</td><td>157~174. 0</td><td>0.19</td></tr><tr><td>Solvesso 150</td><td>CH(CH)</td><td>一</td><td>188. 0~210. 0</td><td>0.04</td></tr><tr><td>Solvesso 200</td><td>CH(CH）2</td><td>一</td><td>226.0~279. 0</td><td>0.04</td></tr><tr><td>溶剂石脑油</td><td>主要成分为甲苯、二甲苯、乙苯及 异丙苯</td><td>一</td><td>120~200</td><td>一</td></tr><tr><td>松节油</td><td>由a蒙烯及β薇烯组成</td><td>一</td><td>150~170</td><td>0.45</td></tr><tr><td>双戊烯</td><td>Ce H16</td><td>一</td><td>160~190</td><td></td></tr><tr><td>甲醇</td><td>CHOH</td><td>32. 04</td><td>64.65</td><td>6.0</td></tr><tr><td>乙醇</td><td>CHsOH</td><td>46.07</td><td>78.3</td><td>2.6</td></tr><tr><td>正丙醇</td><td>CH(CH)OH</td><td>60.10</td><td>97.2</td><td>1. 0</td></tr><tr><td>异丙醇</td><td>(CH)CHOH</td><td>60.09</td><td>82.5</td><td>2.05</td></tr><tr><td>正丁醇</td><td>CHCHCHOH</td><td>74.12</td><td>117.1</td><td>0.45</td></tr><tr><td>异丁醇</td><td>(CH)CHCHOH</td><td>74.12</td><td>107.0</td><td>0.83</td></tr><tr><td>仲丁醇</td><td>CHCHOHCHs</td><td>74.12</td><td>99.5</td><td>1.15</td></tr><tr><td>醋酸甲酯</td><td>CHCOOCH</td><td>74.08</td><td>59~60</td><td>10.4</td></tr><tr><td>醋酸乙酯</td><td>CHCOOCHs</td><td>88.10</td><td>77.0</td><td>5.25</td></tr><tr><td>醋酸正丙酯</td><td>CHCOOCH</td><td>102.14</td><td>101. 6</td><td>2.3</td></tr><tr><td>醋酸异丙酯</td><td>CHCOOCH(CH)</td><td>102.13</td><td>89.0</td><td>4.35</td></tr><tr><td>醋酸正丁酯</td><td>CHCOOCH</td><td>116.15</td><td>126.5</td><td>1. 0</td></tr><tr><td>醋酸异丁酯</td><td>CHCOOCHCH(CH)</td><td>116.15</td><td>118. 3</td><td>1.52</td></tr><tr><td>醋酸戊酯</td><td>CHCOOCH</td><td>130. 18</td><td>130.0</td><td>0.87</td></tr><tr><td>醋酸异戊酯</td><td>CHCOOCHCHCH(CH)</td><td>130.18</td><td>142. 0</td><td></td></tr><tr><td>乳酸丁酯</td><td>CHCHOHCOOCH</td><td>146.18</td><td>188.0</td><td>0.06</td></tr><tr><td>乙二醇乙醚</td><td>CHOCHOH</td><td>90.12</td><td>135.0</td><td>0.4</td></tr><tr><td>乙二醇乙醚醋酸酯</td><td>CHCOOCHCHOCHs</td><td>132.16</td><td>156.3</td><td>0.2</td></tr><tr><td>二甘醇乙醚</td><td>CHO(CH)OCHOH</td><td>134.17</td><td>201.9</td><td><0.01</td></tr><tr><td>二甘醇丁醚</td><td>CH,OCHOCHOH</td><td>162.2</td><td>230.4</td><td><0. 01</td></tr><tr><td>二甘醇乙醚醋酸酯</td><td>CHCOOCHOCHOCHs</td><td>176. 51</td><td>217.4</td><td><0.01</td></tr><tr><td>二甘醇丁醚醋酸酯</td><td>CHCOOCHOCHOCH</td><td>204.26</td><td>246.8</td><td><0.01</td></tr><tr><td>丙二醇甲醚</td><td>CHoO</td><td>90.12</td><td>118~119</td><td>0.7</td></tr><tr><td>丙二醇乙醚</td><td>CHO</td><td>104.15</td><td>132.2</td><td>0.5</td></tr><tr><td>丙二醇丁醚</td><td>HOCHOCH</td><td>154</td><td>170.1</td><td>0.08</td></tr><tr><td>丙二醇甲醚醋酸酯</td><td>CHO</td><td>132.16</td><td>146</td><td>0.14</td></tr><tr><td>丙酮</td><td>CHCOCH</td><td>58.08</td><td>56.1</td><td>7.2</td></tr><tr><td>环己酮</td><td>CH(CH）CO</td><td>98.14</td><td>155. 0</td><td>0.25</td></tr><tr><td>二丙酮醇</td><td>(CH)COHCHCOCH</td><td>116.15</td><td>166.0</td><td>0.15</td></tr><tr><td>丁酮</td><td>CHCOCHs</td><td>72.10</td><td>79.6</td><td>4.65</td></tr><tr><td>甲基异丁基酮</td><td>CHCOC H</td><td>100. 15</td><td>118.0</td><td>1.45</td></tr><tr><td>异佛尔酮</td><td>CHO</td><td>138. 21</td><td>215.2</td><td>0.03</td></tr><tr><td>二乙基酮</td><td>CHsCOCHs</td><td>86.10</td><td>102.0</td><td>2.8</td></tr><tr><td>甲基丙基酮</td><td>CHCOCH</td><td>96.08</td><td>103.0</td><td>2.5</td></tr><tr><td>二氯甲烷</td><td>HCCl</td><td>84. 94</td><td>39.8</td><td>29.0</td></tr><tr><td>1,1,1-三氯乙烷</td><td>CHCCl</td><td>133.41</td><td>74.0</td><td>1.5</td></tr><tr><td>2-硝基丙烷</td><td>CHCHNOCH</td><td>89.10</td><td>120.3</td><td>1.2</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 630,
+        "chunk": "# 2.影响溶剂挥发速率的因素  \n\n(1）氢键的影响溶剂分子间的相互作用，影响混合物中组分的挥发，特别是氢键的存在，将明显地限制溶剂的挥发速率。如表2-3-16 所示，乙醇和苯的沸点接近，而苯的挥发  \n\n速率为乙醇的2倍，正丁醇的沸点比醋酸正丁酯低，而挥发速率也低，由此可以看出氢键对限制溶剂的挥发起着重要作用。  \n\n(2）温度的影响溶剂的相对挥发速率与其蒸气压紧密相关。而蒸气压又随着温度的变化而变化，温度越高，蒸气压也越高，溶剂的挥发速率也越快，以质量为基础的溶剂挥发速率 $\\scriptstyle{E_{\\mathrm{{w}}}}$ 和温度的关联式可以表示如下：  \n\n$$\n\\lvert\\mathbf{g}(E_{\\mathbb{w}1}/E_{\\mathbb{w}2})=0.825\\Delta H(1/T_{2}-1/T_{1})\n$$  \n\n式中 $E_{\\mathrm{w1}}$ 一 温度为 $T_{1}$ 时溶剂的挥发速率（以质量为基础)； $E_{\\mathrm{W}2}$ 一 温度为 $T_{2}$ 时溶剂的挥发速率（以质量为基础)； $\\triangle H$ 3 摩尔蒸发潜热， $\\scriptstyle{\\mathrm{J/mol}}$ $T_{1}$ ， ${{T}_{2}}$ 温度，K。  \n\n【例题2-3-9】 $25\\mathrm{{^{q}C}}$ 醋酸正丁酯的蒸发潜热为 $2.53~\\mathrm{{kJ/mol}}$ ，假定此值在有关的温度变化内基本上是一个常数，试计算 $15^{\\circ}\\mathrm{C}$ 及 $35\\mathrm{^{*}C}$ 时醋酸正丁酯的相对挥发速率。  \n\n解根据定义 $t=25\\%$ （298K）时，醋酸正丁酯的相对挥发速率是1.00。依次将这些数值代人式（2-3-25）中，按所要求的温度 $15\\mathrm{{C}}$ （288K）及 $35\\mathrm{^\\circC}$ （308K）计算。  \n\n$$\n\\bf\\ddot{\\sigma}:\\ l g({1/\\sigma}E_{w2})=0.825\\times2.53\\times10^{3}\\times(\\frac{1}{288}-\\frac{1}{298})\n$$  \n\n$$\n\\mathfrak{X}^{\\bullet}:\\mathsf{l}_{\\mathtt{g}}(1/\\mathrm{\\partial}E_{\\mathtt{W}_{2}})=0.825\\times2.53\\times10^{3}\\times(\\frac{1}{308}-\\frac{1}{298})\n$$  \n\n$$\n\\therefore E_{{\\mathrm{w}}2}=1.70(35^{\\circ}\\mathrm{C})\n$$  \n\n从计算结果可以看出，相对小的温度变化，会导致溶剂挥发速率极为显著地变化，醋酸正丁酯在 $25\\sim35\\Upsilon$ 温度范围内，温度每变化 $1\\%$ ，相对挥发速率则平均增长 $6\\%$ 。因此，涂料产品中使用的混合溶剂在不同的季节，要调整其组成，以调节其挥发速率，如夏季需用部分挥发速率慢的溶剂，取代部分挥发速率快的溶剂，而冬季则反之。  \n\n(3）表面气流的影响由于多数溶剂蒸气比空气重，除非用空气气流将其带离溶剂层表面，它们趋于留在溶剂层表面，如果溶剂蒸气积聚使涂膜表面空间趋于饱和，则严重阻碍溶剂挥发，所以涂膜表面气流速率越大，溶剂挥发速率就越快。因此，保持空气流通对于涂膜的挥发过程起主要影响。  \n\n(4）比表面积大小的影响单位体积的表面积——比表面积越大，挥发速率越快，这是因为溶剂只在表面挥发的缘故。在涂料施工中，用喷枪喷涂，对溶剂挥发速率的要求就和用刷涂或浸涂方法施工要求不同，由于喷涂时漆液被雾化成小的液滴，比表面积很大，气流也较大，溶剂挥发速率就快。如果溶剂选择不当，臂如混合溶剂的挥发速率如果较快，则会导致喷涂时的“拉丝”、“干喷”现象，这时就需要增加挥发速率慢、而溶解能力强的溶剂组分，以调整溶剂的挥发速率。  \n\n(5）高分子聚合物的影响在涂料产品中，混合溶剂的挥发速率是不能从各个溶剂各自的挥发速率来准确预测的。这是因为，除了溶剂分子间的相互作用会延缓溶剂的挥发以外，高分子聚合物和溶剂分子之间的吸引力也会延缓溶剂的挥发，所以在高分子溶液中，溶剂的挥发将比预料的慢。但是稀释剂的挥发速率则不受高分子聚合物的影响，由此可见，各种溶剂的挥发速率数据至多只能作为涂料溶剂选择的粗略指导而已。因此有必要对某一涂料中选用的混合溶剂进行实际试验，以验证其挥发速率是否符合要求。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 631,
+        "chunk": "# 3.混合溶剂的挥发速率  \n\n混合溶剂的挥发速率等于各溶剂组分的挥发速率之总和。大多数混合溶剂，由于其分子  \n\n结构的不同，不能看作是理想溶液，因而溶剂在其混合物中的挥发速率不等于其纯组分时的挥发速率，两者的关系如下：  \n\n$$\nR_{i}/R_{i}^{0}=\\alpha_{i}\n$$  \n\n式中 $R_{i}$ —溶剂i在混合溶剂中的挥发速率；$R_{i}^{0}$ —溶剂 $i$ 在纯组分时的挥发速率；$\\alpha_{i}$ —溶剂i在混合溶剂中的活度。  \n\n混合溶剂的总挥发速率 $R_{\\checkmark}{}_{\\check{\\rho}\\check{\\rho}}$ 表示为  \n\n$$\nR_{B,\\mu}=a_{1}\\ R_{1}^{0}+a_{2}\\ R_{2}^{0}+\\cdots=\\sum_{i=1}^{n}a_{i}R_{i}^{0}\n$$  \n\n在非理想溶剂中引人以体积为依据的活性系数（又称释放系数） $r$  \n\n$$\n\\scriptstyle{r=a_{i}/c_{i}}\n$$  \n\n式中C—组分i在混合溶剂中的浓度。  \n\n联系式（2-3-27）和式（2-3-28）得：  \n\n$$\nR_{\\bar{\\imath}\\bar{\\imath}}={c_{1}r_{1}R_{1}^{0}}+{c_{2}R_{2}R_{2}^{0}}+\\cdots=\\sum_{i=1}^{n}c_{i}r_{i}R_{i}^{0}\n$$  \n\n严格地讲 $R_{\\vec{E}^{*_{0}}}$ 只表示混合溶剂瞬间的挥发速率，但是实际混合溶剂（非理想系统）中，不同溶剂由于挥发到大气中的相对损失并不与原始溶剂组成相同。因此，当挥发过程进行时，留下来的溶剂组成在变化。剩余液体溶剂变化的方向可以定量测定。用其初期组成分数对比其在溶剂蒸气中的组成分数，就可以鉴别出随时间变化，滞留于涂膜中的溶剂分数是减少还是富集了。并且从此趋势可以定性地确定溶剂混合物中变化的方向。此方向可能是十分重要的，因为一旦有了这种趋势，此趋势就会加强，挥发溶剂蒸气的组成可以由式(2-3-29)左右两边皆除以 $R_{\\sun*}$ ，即  \n\n$$\n1.\\ 00{=}c_{1}r_{1}R_{1}^{0}/\\ R_{B,\\#}+\\ c_{2}R_{2}R_{2}^{0}/\\ R_{B,\\#}+\\ c_{n}r_{n}R_{n}^{0}/\\ R_{B,\\#}\n$$  \n\n依次将其中某一溶剂在混合溶剂中的起始分数和其在溶剂蒸气中的分数进行比较，用以定性地描述挥发过程进行时溶剂组成的变化。  \n\n活性系数是混合溶剂中不同组分间相互作用（或相互亲和力）的量度，其值随混合溶剂中各溶剂组分的类型及浓度而变化。  \n\n图2-3-11提出了一种简洁的活性系数推算方法。这种方法是基于溶剂的活性系数主要取决于该溶剂官能团的性质，并且分子的官能团相似，则其活性系数也相似，与分子的大小和分子中碳氢结构无关。因而把溶剂分为3种类型—烃类、酯类/酮类和醇类/醚-醇类。  \n\n利用图2-3-11可以很容易地求得多组分混合溶剂的活性系数。但在使用时应注意以下几点。  \n\n$\\textcircled{1}$ 图中所示的浓度（体积分数）代表给定的同一类型的溶剂的浓度之和［如混合溶剂中二甲苯占 $20\\%$ ，200号涂料溶剂油占 $30\\%$ ，则在图2-3-11(a)中按烃类体积分数 $50\\%$ 查找r值]。  \n\n$\\textcircled{2}$ 对于一种类型的所有组分，假设有相同的值。  \n\n$\\textcircled{3}$ 图中所示曲线代表两种类型的混合溶剂，当用于3种类型混合溶剂时，则用二元曲线的质量平均值。  \n\n【例题2-3-10】某硝化纤维素溶液的溶剂配方的体积分数为醋酸正丁酯（ $R_{\\mathrm{V}}^{0}=1.0$ 一$35\\%$ ；甲苯 $(R_{\\mathbf{V}}^{0}=2.0$ ) $50\\%$ ；乙醇 $(R_{\\mathrm{V}}^{0}=1.7$ 。 $10\\%$ 及正丁醇 $(R_{\\mathbf{V}}^{0}=0.4$ 。 $5\\%$ 。试计算该混合溶剂的相对挥发速率，并评述挥发进行时，滞留在涂膜中的溶剂组成的变化。  \n\n![](images/0750bf9c0a836775df01ad8224335434ebd00abe95f0ab59c5b85efe94737b61.jpg)  \n图2-3-11按溶剂类型分类的溶液浓度与溶剂的活性系数关系  \n\n解从图2-3-11(a)～（c）中分别读出甲苯、醋酸正丁酯、乙醇和正丁醇的活性系数。为了便于确定数值，图中有圈的地方即为读数的位置，将此数据代入式（2-3-29）中，$R_{\\perp}{\\bf{s}}=(0.35\\times1.6\\times1.0)+(0.50\\times1.4\\times2.0)+(0.10\\times3.9\\times1.7)+(0.05\\times3.9\\times1.0)+(0.05\\times3.9\\times1.0)^{2}$ （0.4)${\\bf\\Pi}=0.$ 56（醋酸正丁酯）十1.4（甲苯） $+0.$ 66（乙醇） $+0.08$ （正丁醇） $^{,}=2.7$  \n\n依据式（2-3-30）得  \n\n$1.\\ 00=0.\\ 56/2.\\ 73+1.\\ 4/2.\\ 73+0.\\ 66/2.\\ 73+0.\\ 08/2.\\ 73$ $\\scriptstyle=0.$ 21(醋酸正丁酯)十0.51(甲苯)+0.24(乙醇)+0.03(正丁醇)  \n\n从上述计算结果可知，醋酸正丁酯在蒸气相中的浓度低于原始溶剂混合物（0.21对0.35)，结果是挥发进行时，体系中此高溶解能力的组分富集起来。此富集作用部分地来自多挥发掉的甲苯稀释剂（甲苯在蒸气相中的浓度为 $52\\%$ ，其在混合溶剂中的起始浓度为$50\\%)$ ，同时，计算结果表明，混合溶剂的挥发速率较任何单一溶剂组分为快。故此硝化纤维素溶液的溶剂平衡良好。随着时间的推移可得到更高的溶解能力，因而可防止不良的效应，如针孔/缩孔及发白等。  \n\n由于混合溶剂的组成常常已知，初期相对挥发速率和初期起始组成随时间的变化趋势二者均可测定。一般可概括如下：  \n\n$\\textcircled{1}$ 后期挥发速率低于初期挥发速率，但是等于或高于挥发速率最慢的溶剂；  \n\n$\\textcircled{2}$ 初期溶剂体系组成的变化趋势并不会向相反方向变化，事实上应该加速。这些重要的观察对涂料科技工作者可以提供合理的基础进行判断，然而研究人员有必要更深人地研究变化中溶剂体系。目前，气相色谱分析是测定溶剂组成最简便的方法。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 632,
+        "chunk": "# 4.混合溶剂从涂膜中的挥发  \n\n(1）“两阶段挥发”理论溶剂从施工后的涂膜中挥发是一个相当复杂的过程，不少学者对此作过描述。但是最有实用价值的当属汉森（Hansen）提出的“两阶段挥发”理论，即溶剂从涂膜中挥发分为两个连贯而又重叠的阶段。在第一阶段即“湿”阶段，溶剂分子的挥发是受溶剂分子穿过涂膜液-气边界层的表面扩散阻力所制约，溶剂挥发的模式多少类似上述单纯的混合溶剂的挥发行为。在涂膜开始凝定后，即进入第二个阶段，即“干”阶段，在“干”阶段，溶剂挥发损失决定于溶剂从相对于的聚合物扩散到涂膜表面的能力，因此在“干”阶段溶剂的挥发速率明显降低。  \n\n图2-3-12所给出的干燥曲线是某假想的施工后涂料的挥发模式，分成初期湿阶段，挥发相对快，由表面来控制（溶剂由液态表面逃逸）；以及最后干燥阶段，溶剂损失很慢，完全由扩散所控制（溶剂首先扩散到涂膜表面，再从实际上干的涂膜表面逃逸)。应该看出，为了引人注意，溶剂初期及最后挥发中相对挥发时间完全不同，采用了对数时间坐标。  \n\n（2）“湿”阶段的挥发速率影响“湿”阶段的因素如前面在“影响溶剂挥发速率的因素”所讨论的那样。其中高分子聚合物对溶剂挥发速率的影响，一般来说倾向于阻滞与其有相似官能团的溶剂。例如醇酸树脂涂膜中，保留溶剂的数量按下列顺序增加：  \n\n![](images/7c6659ff2e23f66a618cecbc7d73ea3d5a80adb666cd85a46c64c1f2833e096f.jpg)  \n图2-3-12某假定的涂膜连续干燥模式湿、干特性图  \n\n饱和烃<芳香烃<醇和醇醚类<酮和酯类  \n\n并且高分子聚合物对于溶剂挥发的影响主要发生在后期，随树脂溶液浓度的增加而提高。  \n\n据Sletmoe的实验表明，在“湿”阶段，混合溶剂从湿膜中的挥发速率近似值可以由式（2-3-29）计算求得，所谓“近似”是依此式计算时作了如下假定：  \n\na.假定在湿阶段的挥发速率较大，且该阶段为恒速率挥发阶段，即 $R_{\\#\\#}=R_{\\#\\#}$ (初始阶段），事实是该阶段的溶剂挥发速率是个逐渐降低的过程；b.树脂对溶剂挥发的影响，主要考虑与官能团的相互作用；c.颜料对溶剂的挥发是情性的。  \n\n(3)“干”阶段的挥发速率“干”阶段的挥发是“降低速率”阶段。影响“干”阶段溶剂挥发速率的因素可以定性地归纳如下。  \n\n$\\Phi$ 溶剂分子大小和形状的影响如前所述，在“干”阶段，溶剂挥发损失决定于溶剂从相对于聚合物扩散到涂膜表面的能力。而底部溶剂的扩散是采取由一个孔隙跳到另一个孔隙，即从高分子聚合物产生的自由体系中扩散至表面而逸出。因此溶剂的分子越小、形状越规整、扩散就越容易。例如甲基丁基酮与甲基异丁基酮从表面挥发速率考虑，甲基异丁基酮比甲基丁基酮挥发速率快，而到干燥过程，从底部的扩散，甲基异丁基酮的分子支链多，其截面积比甲基丁基酮大，所以扩散速率慢。 D  \n\n$\\textcircled{2}$ 溶剂在聚合物中保留能力的影响溶剂释放并不表现出与溶剂挥发性和溶解能力相平行。这是出乎预料的。表2-3-17按在聚合物中保留能力增强的顺序所列出22种常见溶剂。  \n\n$\\textcircled{3}$ 聚合物和溶剂相互作用的影响聚合物分子链上有极性基团如羟基、羧基，产生氢键时，会降低溶剂的扩散速率。聚合物的性质也对溶剂保留有肯定的作用，但是这仅是一般的影响。  \n\n表2-3-17聚合物中保留能力增强顺序列出的22种溶剂  \n\n\n<html><body><table><tr><td>溶剂</td><td>R</td><td>溶剂</td><td>R</td></tr><tr><td>甲醇（最不易保留）</td><td>4.1</td><td>甲苯</td><td>2.3</td></tr><tr><td>丙酮</td><td>10.2</td><td>2-硝基丙烷</td><td>1.5</td></tr><tr><td>乙二醇甲醚</td><td>0.5</td><td>二甲萃</td><td>0.8</td></tr><tr><td>甲乙翻</td><td>4.5</td><td>甲基异丁基酮</td><td>1.4</td></tr><tr><td>醋酸乙酯</td><td>4.8</td><td>醋酸异丁酯</td><td>1.7</td></tr><tr><td>乙二醇丁醚</td><td>0.4</td><td>2,4-二甲基戊烷</td><td>5.6</td></tr><tr><td>正庚烷</td><td>3.3</td><td>环已烷</td><td>5.9</td></tr><tr><td>醋酸正丁酯</td><td>1.0</td><td>二丙酮</td><td>0.1</td></tr><tr><td>苯</td><td>5.4</td><td>甲基环已烧</td><td>0.3</td></tr><tr><td>醋酸-2-甲氧基乙酯</td><td>0.4</td><td>甲基环已酮(最易保留)</td><td>0.2</td></tr><tr><td>醋酸-2-乙氧基乙酯</td><td>0.2</td><td></td><td></td></tr></table></body></html>  \n\n$\\textcircled{4}$ 聚合物玻璃化温度的影响如聚合物玻璃化温度的关系示意图（图2-3-13）所示。假如有两个高分子聚合物体系，一个体系的 $T_{\\mathrm{s}}$ 低于室温[图2-3-13（a)]，另一个体系的 $\\boldsymbol{\\tau_{s}}$ 高于室温[图2-3-13(b)]。对于 $T_{*}$ 小于室温的高聚物，由于体系中存在溶剂，使 $T_{\\mathrm{s}}$ 降低，即使在涂膜干燥的最后阶段，因为原来 $\\boldsymbol{T}_{\\kappa}$ 就小于室温，所以还有一部分自由体积，使底部的溶剂可以扩散出来。而对于 $T_{\\mathrm{~g~}}$ 高于室温的体系，随着溶剂的不断挥发， $T_{\\mathrm{s}}$ 也不断增加，到达室温，由于 $T_{\\mathrm{g}}>T_{\\mathrm{\\bar{w}\\bar{s}}}$ ，体系的自由体积仍很少，底部溶剂的扩散就困难，从而导致溶剂容易残留下来。这些溶剂可以起到增塑作用，对涂膜性能产生一定影响。随着时间的延长，溶剂会慢慢挥发，涂膜性能也会慢慢变化，因此测定涂膜性能的时间很重要。  \n\n![](images/6e34186303f6cd4570c1b720b97f5d7c9237d2503277f909d592add58e7fa4ef.jpg)  \n图2-3-13聚合物玻璃化温度的关系示意图  \n\n当然，这部分滞留下来的溶剂，也可以采取烘烤的办法，令 $T_{\\mathfrak{R}\\mathfrak{Q}}>T_{\\varepsilon}$ ，使溶剂扩散并逸出，从而改善涂膜性能。这就是为什么室温干燥的涂膜经低温烘烤后性能有所改善的原因之一。同理，在涂料中使用增塑剂也有利于溶剂扩散逸出。 欢  \n\n$\\textcircled{5}$ 水的影响涂料产品中有高聚物，整个体系的黏度与混合溶剂的比例有关系。在低湿度时，水的挥发速率比等量溶剂挥发得快。而在高湿度时，水会残留下来，对整个体系的黏度有很大影响。 大  \n\n因此，在低湿度喷漆膜流平性很好，而防流挂性不好。在高湿度下施工时，流平性不好，而无流挂现象。对作业环境讲，湿度往往很难变动。因此，可酌情调整溶剂以求适应。即在高湿度施工时要用挥发速率慢的溶剂，而在低湿度施工时，为跟上水的挥发速率，可采用挥发速率快的溶剂。  \n\n$\\textcircled{6}$ 涂膜厚度的影响残留溶剂多少和涂膜厚度的关系可以由式（2-3-31）表示：  \n\n$$\n\\scriptstyle\\operatorname{l}_{\\mathbf{B}}c=A\\operatorname{l}_{\\mathbf{B}}(X^{2}/t)+B\n$$  \n\n式中 $\\textit{\\textbf{c}}$ —溶剂浓度（按溶剂质量与单位聚合物质量之比表示）；$x$ —膜厚， $\\mu\\mathrm{m}$ tt—时间，h;A，B常数。  \n\n对于“干”阶段挥发速率而言，除了最后的溶剂痕迹损失之外，公式（2-3-31）是有效的，厚度的关键作用表现在式中，它以平方项出现。因此，对指定聚合物/溶剂体系而言，达到任何特定干燥阶段浓度 $\\textit{\\textbf{c}}$ 时， $X^{2}/t$ 比率为常数，所以一般可以认为：保留时间与施工的涂膜厚度平方成反比。例如，假定涂膜厚度增加1倍，则保留时间增加4倍。  \n\n【例题2-3-11】热塑性氯乙烯/醋酸乙烯共聚树脂溶于甲基异丁基酮（MIBK）施工于底材上形成 $7.0\\mu\\mathrm{m}$ 干膜。1h后，以聚合物计，保留溶剂为 $12.2\\%$ （0.122)，一天后为$8.6\\%$ (0.086)。试问两周后保留浓度 $\\textit{\\textbf{c}}$ 为多少？再者，假定涂膜厚度只有 $3,0\\mu\\mathrm{m}$ ，则保留量为多少？  \n\n解首先将已知数据依次代人式（2-3-31），求得常数 $A$ 和 $B$  \n\n$$\n\\scriptstyle1_{8^{0.}}122=A1_{\\mathbf{g}}(49/1)+B\n$$  \n\n$$\n1\\mathbf{g}0.086=A l\\mathbf{g}(49/24)+B\n$$  \n\n将上式减下式，消去 $B$ ，求解 $A$ 。然后将 $A$ 代入任一方程，求解B。将式（2-3-31）换写成已计算出的常数式：  \n\n$$\n\\mathsf{l g}c=0,11\\mathsf{l g}(X^{2}/t)-1,10\n$$  \n\n将 $\\scriptstyle t=336$ 之值代人式（2-3-32），求得两周后溶剂保留量。  \n\n$$\n\\begin{array}{c}{{\\lfloor\\mathbf{g}c=0.11\\lfloor\\mathbf{g}(49/336)-1.10}}\\\\ {{c=0.064(6.4\\%)}}\\end{array}\n$$  \n\n3. $0\\mu\\mathrm{m}$ 厚涂膜的保留量用相同方法计算：  \n\n$$\n\\mathsf{l g}c=0.11\\mathsf{l g}(9/336)-1.10\n$$  \n\n由上述计算结果可知，极薄的涂膜（如3. $0\\mu\\mathrm{m}$ ）在相当长的时间内（如 $_2$ 周）仍有持久的溶剂保留。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 633,
+        "chunk": "# （二）溶剂平衡  \n\n溶剂平衡是指涂料在成膜过程中，混合溶剂的各组分相对挥发速率要与溶剂组成保持对应。换言之，从涂膜中逸出的混合溶剂蒸气的组成与混合溶剂的组成要大体保持一致。如果溶解能力强的溶剂组分比其他组分挥发得快，则在干燥后期树脂可能析出，涂膜表面产生颗粒，相反溶解能力强的组分挥发得太慢，又因树脂有阻滞与其结构相似的溶剂挥发特性，会增加该溶剂在涂膜中的残留量。  \n\n溶剂在初始挥发阶段的蒸气组成 $\\boldsymbol{V}_{i}$ 可用下式表示：  \n\n$$\nV_{i}{=}R_{i}/R_{i3,\\ast\\mathrm{{u}}}{=}c_{i}r_{i}r_{i}^{0}/\\sum_{i=1}^{n}c_{i}r_{i}R_{i}^{\\circ}\n$$  \n\n显然， $\\boldsymbol{V}_{i}=\\boldsymbol{c}_{i}$ 时，可以认为溶剂在初始阶段是处于相对平衡的挥发状态。如果 $V_{i}>_{\\epsilon_{i}}$ （特别是溶解能力强的组分），则意味着可能有树脂颗粒析出。若 $\\smash{V_{i}<}c_{i}$ 则该溶剂在涂膜中的残留量将增加。  \n\n由于“湿”阶段为恒速挥发阶段，以及“湿”阶段的挥发决定“干”阶段开始时溶剂混合物的组成，因此，必须使混合溶剂在初始挥发阶段就处于平衡挥发状态。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 634,
+        "chunk": "# 四、表面张力  \n\n所谓“表面张力”应用于液体时指的是在液相和气相之间形成一个单位面积表面所需要的功。或者定义为，在液体表面上垂直作用于单位长度线段上的表面紧缩力。所以，表面张力的单位是以 $\\mathbf{J}/\\mathbf{m}^{2}$ 或 $\\mathbf{N}/\\mathbf{m}$ 来表示的。  \n\n在涂料中“表面张力”是个重要的指标，低的树脂溶液的表面张力和低的液体涂料的表面张力，无疑是有益的，表现在以下几方面：  \n\n$\\Phi$ 低表面张力的树脂溶液（漆料)，有利于对颜料的湿润，便于颜料在漆料中的分散，提高色漆制造研磨分散效率，并有利于漆浆的稳定；  \n\n$\\textcircled{2}$ 低表面张力的液体涂料有利于涂膜对底材的湿润，因此便于涂膜的流平和提高涂膜对底材的附着力；  \n\n$\\textcircled{3}$ 高固体分涂料的表面张力对其喷涂时的雾化性能的影响比涂料黏度的影响更为重要，由于低表面张力的液体涂料喷涂时容易断裂和雾化，所以低表面张力的高固体分涂料容易获得满意的喷涂效果；  \n\n$\\textcircled{4}$ 某些漆膜病态也与表面张力有关，例如陷穴缩孔和镜框效应（Picture framins)。当涂料喷涂于表面玷污的底材上时会产生陷穴。这是由于类似灰尘和油污这样的污染物，通常都比周围表面的表面张力低些，因此，当涂料涂于该表面上时，玷污物就会溶于涂料中，使这部分涂料的表面张力降低，而表面张力低的地方的涂料会向附近表面张力高的地方流动，周围涂料增加，中间形成陷穴。镜框效应也是由类似的原因造成的。这是由于溶剂自底的四周边缘或弧形表面上的挥发速率比底材平面上的涂膜中的溶剂挥发速率快，随着固体分的提高，表面张力增加得也快。那么，底材平面上表面张力低的涂料就会移向边缘，使那里的涂膜增厚，而形成“镜框效应”。通常，最大限度地降低高固体分涂料的表面张力，可以使上述漆膜病态得到缓解。  \n\n既然漆料及涂料的表面张力对色漆制造、涂料喷涂施工及涂膜质量有如此密切的关系，那么降低漆料及涂料的表面张力就是十分重要的课题了，而认真选择溶剂是降低漆料及涂料表面张力的途径之一。  \n\n涂料配方中的成膜物—高分子聚合物的表面张力比较高，一般在 $32\\sim61\\mathrm{mN/m}$ （表2-3-18聚合物的临界表面张力)，而各类溶剂的表面张力相对比较低，约在 $18\\mathrm{\\sim}35\\mathrm{mN/m}$ 范围内(表2-3-19各类溶剂的表面张力)。  \n\n表2-3-18聚合物的临界表面张力  \n\n\n<html><body><table><tr><td>聚合物</td><td>表面张力/（mN/m)</td><td>聚合物</td><td>表面张力/（mN/m)</td></tr><tr><td>聚甲基丙烯酸正丁酯</td><td>32</td><td>聚甲基丙烯酸甲酯</td><td>41</td></tr><tr><td>聚醋酸乙烯酯</td><td>36</td><td>环氧树脂</td><td>47</td></tr><tr><td>聚氯乙烯 三聚氰胺树脂</td><td>39 39</td><td>尿素-甲醛树脂</td><td>61</td></tr></table></body></html>  \n\n表2-3-19各类溶剂的表面张力范围  \n\n\n<html><body><table><tr><td>溶剂类型</td><td>表面张力/（mN/m）</td><td>溶剂类型</td><td>表面张力/（mN/m）</td></tr><tr><td>醇类</td><td>21.4~35.1</td><td>乙二醇醚酯类</td><td>28.2~31.7</td></tr><tr><td>酯类</td><td>21.2~28.5</td><td>脂肪烃</td><td>18.0~28.0</td></tr><tr><td>酮类</td><td>22.5~26.6</td><td>芳香烃</td><td>28.0~30.0</td></tr><tr><td>乙二醇醚类</td><td>26.6~34.8</td><td>水</td><td>72.7</td></tr></table></body></html>\n\n含有大量溶剂的传统涂料表面张力值都比较低。例如，典型的汽车涂料，其表面张力约  \n\n为26mN/m。传统的聚酯磁漆表面张力为31.5mN/m，所以传统涂料很少遇到上述由于表面张力高所造成的各种问题。只有对于表面张力相当低的底材——聚乙烯或聚丙烯塑料等，才会遇到对底材湿润的问题。但是，由于涂料表面张力是随着其固体分的增加而增高的。因此，对于合成树脂涂料，特别是高固体分涂料而言，由于成膜材料成了主要成分，其表面张力又比较高，而溶剂比例又大幅度降低，以有限的溶剂，又要将树脂溶液的表面张力降低到尽量低的限度。这就要十分严格地选择溶剂的表面张力，如表2-3-20所示，以低表面张力的溶剂配制成涂料就可以获得比较低的表面张力。  \n\n表2-3-20含颜料丙烯酸/三聚氰胺涂料的表面张力（0.34kg溶剂/L涂料）  \n\n\n<html><body><table><tr><td>溶 剂</td><td>溶剂的表而张力</td><td>涂料的表面张力</td><td>溶 剂</td><td>溶剂的表面张力</td><td>涂料的表面张力</td></tr><tr><td>异丁酸异丁酶(IBIB) 甲基戊基酮</td><td>23.2 26.1</td><td>26.5 29.5</td><td>Ektasoive EE醋酸酯 二甲苯</td><td>28.2 28.0</td><td>32.0 31.5</td></tr></table></body></html>  \n\n所以，在选择溶剂组成色漆配方时，除考虑前面所论述的溶解力、黏度、挥发速率等因素外，溶剂的表面张力也是一个重要的因素。在平衡各项因素的前提下，应当尽量选用低表面张力值的溶剂。表2-3-21介绍了一些溶剂的表面张力。  \n\n表2-3-21溶剂的表面张力①  \n\n\n<html><body><table><tr><td>名称</td><td>表面张力 /(mN/m)</td><td>名称</td><td>表面张力 /(mN/m)</td><td>名称</td><td>表面张力 /(mN/m)</td></tr><tr><td>甲醇</td><td>22.55</td><td>二丙二醇甲醚</td><td>28</td><td>硝基萃</td><td>43.35</td></tr><tr><td>乙醇</td><td>22.27</td><td>二氯甲烷</td><td>28.12</td><td>醋酸正丙酯</td><td>24.2</td></tr><tr><td>丙醇</td><td>23.8</td><td>甲基丙基甲酮</td><td>24.1</td><td>醋酸异丙酯</td><td>21.2</td></tr><tr><td>异丙醇</td><td>21.7</td><td>二异丁基酮</td><td>22.5</td><td>醋酸丁酯</td><td>25.09</td></tr><tr><td>正丁醇</td><td>24.6</td><td>甲基异戊酮</td><td>25.8</td><td>醋酸异丁酯</td><td>23.7</td></tr><tr><td>异丁醇</td><td>23.0</td><td>甲基戊基甲酮</td><td>26.1</td><td>醋酸戊酯</td><td>25.68</td></tr><tr><td>仲丁醇</td><td>23.5</td><td>二异戊基酮</td><td>24.9</td><td>醋酸异戊酯</td><td>24.62</td></tr><tr><td>丙酮</td><td>23.7</td><td>环己酮</td><td>34.5</td><td>乳酸丁酯</td><td>30.6</td></tr><tr><td>甲基丙酮</td><td>23.97</td><td>二丙酮醇</td><td>31.0</td><td>Ektasolve EE醋酸酯</td><td>28.2</td></tr><tr><td>丁酮</td><td>24.6</td><td>萃</td><td>28.18</td><td>EktasolveDB醋酸酯</td><td>30.0</td></tr><tr><td>甲基异丁基酮</td><td>23.9</td><td>甲苯</td><td>28.53</td><td>乙二醇乙醚</td><td>28.2</td></tr><tr><td>二甘醇乙醚</td><td>31.8</td><td>间二甲苯</td><td>28.08</td><td>Solvesso 100</td><td>27.4</td></tr><tr><td>二甘醇丁醚</td><td>33.6</td><td>醋酸乙酯</td><td>23.75</td><td>Solvesso 150</td><td>34.0</td></tr><tr><td>乙二醇乙醚乙酸酯</td><td>31.8</td><td>1,1,1-三氯甲烷</td><td>25.56</td><td>Solvesso 200</td><td>36.0</td></tr><tr><td>丙二醇甲醚酯酸酯</td><td>27</td><td>硝基乙烷</td><td>31. 0</td><td></td><td></td></tr></table></body></html>\n\n$\\Phi$ 表中表面张力除标注的外皆为20℃时数据。$\\textcircled{2}$ 为24.8℃时的表面张力值。$\\circledcirc$ 为25℃时的表面张力值。  \n\n由表中的数据不难看出：通常挥发速率快的溶剂表面张力值相对低。在大多数情况，随着挥发速率的减慢，溶剂的表面张力也增加（只有乙二醇醚类溶剂例外)。同时带有支链的溶剂比与其相对应的直链溶剂的表面张力低。例如， $20\\Upsilon$ 醋酸异丁酯的表面张力为23 $\\mathrm{\\nabla.7mN/m}$ ，而醋酸丁酯的表面张力为 $25.09\\mathrm{mN/m}$ ，异丁醇的表面张力为 $23.0\\mathrm{mN/m}$ ，而正丁醇的表面张力为 $24.6\\mathrm{mN/m}$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 635,
+        "chunk": "# 五、电阻率  \n\n由于静电喷涂施工具有：所获涂膜均匀、装饰性好、生产率高、适合批量生产、涂料利用率高、能减少溶剂扩散污染的优点，因此许多用户采用静电喷涂的方式进行涂料产品的涂装，在配制静电喷涂涂料时，电阻率则成为一个重要的指标，最佳的涂料电阻率是静电喷涂施工的必要的参数之一。  \n\n组成涂料的各个组分，包括树脂、颜料、添加剂和溶剂都会影响涂料的电阻率。但是选择树脂和颜料往往是出于对涂膜所需要的装饰性能、力学性能、耐老化性能等多方面考虑而确定的，而以变更这些组分来调节涂料的电阻率，在大多数情况下是不现实的，添加剂的用量一般较少，为达到特定的目的而选择特定的添加剂往往比较严格，因此，通过溶剂的选择来调整涂料的电阻率就显得十分必要了。  \n\n不同种类的溶剂，依据其极性程度不同，具有不同的电阻率。醇类溶剂、酮类溶剂和醇醚类溶剂极性较强，具有低的电阻率；烃类和酯类溶剂的极性较弱，具有较高的电阻率。当一种高电阻率溶剂和一种低电阻率溶剂混合时，产生中等的电阻率。混合溶剂的电阻率取决于溶剂的组成，如图2-3-14所示，将正丁醇（极性）加入二甲苯和IBIB（非极性）溶剂内，电阻率迅速下降，而用甲基戊基酮与二甲苯及IBIB混合时，电阻率则呈较平稳的改变。  \n\n![](images/a9236c76fdbdbcc57da005af10eb8a8f1ec3d12eb0bb203089fba1315057f7f0.jpg)  \n图2-3-14混合溶剂的电阻率1一二甲苯/甲基戊基酮；2-IBIB/甲基戊基酮；3—二甲苯/正丁醇；4—IBIB/正丁醇  \n\n![](images/4a77c48b4bebc2b3a6600096f710e87b949eddd92ad57b7b0be673c8e3fbe960.jpg)  \n图2-3-15溶剂电阻率和介电常数之间的关系  \n\n如本节前面所述，溶剂分子极化程度大小（也即溶剂极性强弱）是由其偶极矩决定的，而偶极矩又与其介电常数有关。所谓介电常数是指在同一电容器内，用某一物质作为电介质时的电容（C）和为真空时的电容（ $\\scriptstyle\\mathbf{C}_{0}$ ）的比值，即 $\\scriptstyle{\\varepsilon=C/C_{\\circ}}$ ，表示电介质在电场中贮存静电能的相对能力，介电常数愈小，绝缘性能愈好（即电阻率愈高)。溶剂电阻率和介电常数的关系，如图2-3-15所示。  \n\n表2-3-22列出了不同极性的常用溶剂；表2-3-23列出了常用溶剂的电阻值（涂料的电阻值可以用电导率仪或旋转兆欧表测定)。  \n\n表2-3-22依挥发速率由高到低排列的常用溶剂的极性  \n\n\n<html><body><table><tr><td>高极性</td><td>中极性</td><td>低极性</td><td>非极性</td></tr><tr><td>丙酶</td><td>醋酸戊酯</td><td>甲基戊醇</td><td>苯</td></tr><tr><td>醋酸乙酯</td><td>丁醇</td><td>乳酸丁酯</td><td>甲苯</td></tr><tr><td>甲醇 甲基乙基酮</td><td>乙二醇乙醚</td><td>200号涂料溶剂油</td><td>二甲苯 Solvesso 100</td></tr></table></body></html>  \n\n表2-3-23常用溶剂的电阻值  \n\n\n<html><body><table><tr><td>溶剂名称</td><td>电阻值/Mn</td><td>溶剂名称</td><td>电阻值/MΩ</td><td>溶剂名称</td><td>电阻值/Mn</td></tr><tr><td>甲苯</td><td>400</td><td>酯酸丁酯</td><td>70</td><td>二甲苯</td><td>400</td></tr><tr><td>乙醇</td><td>12</td><td>二丙酮醇（92%以上）</td><td>0.12</td><td>乙二醇乙醚</td><td>0.15</td></tr><tr><td>酷酸乙酯</td><td>12</td><td>二丙酮醇（92%以下）</td><td>0.4</td><td>醛酯</td><td></td></tr><tr><td>仲丁醇</td><td>50</td><td>醋酸仲丁酯</td><td>300</td><td>醋酸甲酯</td><td>500 13</td></tr><tr><td>改性乙醇</td><td>60</td><td>环已酮</td><td>1.5</td><td>200号涂料溶剂油</td><td>500</td></tr><tr><td>无水乙醇</td><td>100</td><td>一氯甲苯</td><td>100</td><td></td><td></td></tr></table></body></html>  \n\n在涂料用静电喷涂方式施工时，首选的自然是容易带电的涂料，但是在实际工作过程中，往往遇到某些不易带电的涂料，这些难以带电的涂料分为两类：第一类是不易接受静电荷的涂料；第二类是具有特别高或特别低电阻值的涂料。对于第一类涂料，常采用的方法是控制性地加入极性溶剂，从而改变其带电性能，顺利地进行静电喷涂；对于第二类涂料则分别添加极性和非极性溶剂，将其电阻值调整到适当的范围。通常，使用非极性溶剂为主要溶剂，加人少量极性溶剂是一般的规律。例如，喷涂A04-9 氨基烘漆时，其电阻值为100MΩ左右，加入少量极性溶剂二丙酮醇，使其电阻值下降到5～15MΩ，然后用二甲苯调整到喷涂黏度，即可进行静电喷涂施工。  \n\n对于高固体分的涂料，由于溶剂加入量较少，调整其电阻值相对困难一些。但是通过正确的选择溶剂，将涂料调整到大多数静电喷涂设备所要求的电阻值范围内，是可以做到的。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 636,
+        "chunk": "# 六、毒性和安全性  \n\n在选择溶剂、设计色漆配方时，应十分重视溶剂的气味、对人体的毒性、空气污染限制和安全性。对于具有令人不愉快气味的溶剂、对人体毒性大的溶剂、易燃易爆的溶剂和不符合空气污染法限制的溶剂应尽量不选用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 637,
+        "chunk": "# 1.气味  \n\n溶剂的气味与对人体的毒性没有任何关系。例如氰乙酸乙酯是一种十分有毒的气体，它虽具有芳香气味，但却能导致死亡。环己酮尽管有难闻的臭味，但是却比具有芳香气味的苯的毒性低得多。涂料产品中所用的溶剂如果具有令人不悦的难闻气味，也是使用者所不愿接受的，特别是在这种气味短时间内难以扩散掉的情况下，将直接影响涂料产品的应用范围。",
+        "category": " Introduction"
+    },
+    {
+        "id": 638,
+        "chunk": "# 2.毒性  \n\n毒性是一种物质对机体造成损害的能力。物质的毒性跟此种物质与机体接触的量、本身的理化性质及其与机体接触的途径有关。  \n\n溶剂可以通过皮肤、消化道和呼吸道被人体吸收而引起毒害。大多数有机溶剂对人体的共同毒性是在高浓度蒸气接触时表现的麻醉作用。一切有挥发性的物质其蒸气长时间、高浓度与人体接触总是有害的。随着中毒程度的加深和持续性的影响，会导致急性中毒和慢性中毒。常温下挥发速率高的溶剂在空气中的浓度比挥发速率低的溶剂高得多。因此，对人体毒性比较大、低挥发速率的溶剂相对比较安全，但是不慎内服或经皮肤吸收同样会引起中毒。  \n\n根据我国国家标准GB5044—85《职业性接触毒性危险程度分级》将毒性分为I级（极度危害)、Ⅱ级（高度危害)、Ⅲ级（中度危害)、IV级（轻度危害）四个类型。联合国世界卫生组织推荐了一个五级急性毒性分级标准（表2-3-24)，用于对外来化合物的急性毒性进行评价。目前各种急性毒性分级标准还未完全统一，均存在不少缺点，因为它们主要是通过经验确定，客观性还不足。  \n\n表2-3-24外来化合物急性毒性分级（WHO）  \n\n\n<html><body><table><tr><td>毒性分级</td><td>大鼠一次经口 LDso/(mg/kg)</td><td>6只大人 2~4只的浓度/10-</td><td>LDse /(mg/kg)</td><td>兔经皮 /(g/kg)</td><td>对人可能致死亡的 /(g/60kg)</td></tr><tr><td>剧毒</td><td><1</td><td><10</td><td><5</td><td><0.05</td><td>0.1</td></tr><tr><td>高毒</td><td>l~</td><td>10~</td><td>5~</td><td>0.05~</td><td>3</td></tr><tr><td>中等毒</td><td>50～</td><td>100～</td><td>44~</td><td>0.5~</td><td>3</td></tr><tr><td>低毒</td><td>500~</td><td>1000~</td><td>350~</td><td>5~</td><td>250</td></tr><tr><td>微毒</td><td>5000～</td><td>10000~</td><td>2180～</td><td>>15</td><td>>1000</td></tr></table></body></html>  \n\n毒性是溶剂的危险性之一，了解溶剂的毒性，是涂料安全生产和使用的基础。溶剂的毒性通常可以进行如下分类。  \n\n(1）根据溶剂对生理作用产生的毒性分类  \n\n$\\Phi$ 损害神经的溶剂如伯醇类（甲醇除外)、醚类、醛类、酮类、部分酯类、苄醇类等；  \n$\\textcircled{2}$ 肺中毒溶剂如羧基甲酯类、甲酸酯类等；  \n$\\textcircled{3}$ 血液中毒溶剂如苯及其衍生物、乙二醇类等；  \n$\\textcircled{4}$ 肝脏及新陈代谢中毒的溶剂如卤代烃类；  \n$\\textcircled{5}$ 肾脏中毒的溶剂如四氯乙烷及乙二醇类。  \n\n(2）根据溶剂对健康的损害分类$\\Phi$ 第一类无害溶剂。  \n\na.基本上无害，长时间使用对健康没有什么影响，如戊烷、石油醚、轻质汽油、己烷、庚烷、200号涂料溶剂油、乙醇、氯乙烷、醋酸乙酯等；  \n\nb.稍有毒性，但挥发性低，在通常情况下使用基本无危险，如乙二醇、丁二醇等。  \n\n$\\textcircled{2}$ 第二类在一定程度上有害或稍有毒害的溶剂，但在短时间最大容许浓度下没有重大的危害，如甲苯、二甲苯、环己烷、异丙苯、环庚烷、醋酸丙酯、戊醇、醋酸戊酯、丁醇、三氯乙烯、四氯乙烯、氢化芳烃、石脑油、硝基乙烷等。  \n\n$\\textcircled{3}$ 第三类有害溶剂，除在极低浓度下无危害外，即使是短时间接触也是有害的，如苯、二硫化碳、甲醇、四氯乙烷、苯酚、硝基苯、硫酸二甲酯、五氯乙烷等。  \n\n(3）根据溶剂在工厂使用条件下的危险性进行分类  \n\n$\\Phi$ 第一类弱毒性溶剂，如200号溶剂油、四氢化萘、松节油、乙醇、丙醇、丁醇、戊醇、溶纤剂、甲基环己醇、丙酮、醋酸乙酯、醋酸丙酯、醋酸丁酯、醋酸戊酯等；  \n\n$\\textcircled{2}$ 第二类中毒性溶剂，如甲苯、环己烷、甲醇、二氯甲烷；  \n$\\textcircled{3}$ 第三类 强毒性溶剂，如苯、二硫化碳、氯仿、四氯化碳、氯苯、2-氯乙醇等。  \n\n为了避免溶剂通过呼吸道被人体吸收，而对健康造成危害，必须严格保证生产作业场所的溶剂蒸气浓度应在安全限度以下。表2-3-25所列出的数据，系我国2007年颁布的GBZ2.1—2007《工业场所有害因素职业接触限值》所公布的一部分内容，职业接触限值（Oc-cupationalexposurelimit，OEL）是职业性有害因素的接触限制量值，指劳动者在职业活动过程中长期反复接触对肌体不引起急性或慢性有害健康的容许接触水平。化学因素的职业接触限值分为时间加权平均容许浓度、最高容许浓度和短时间接触容许浓度三类。时间加权平均容许浓度（Permissible concentration-timeweighted average，PC-TWA）指以时间为权数规定的8h工作日的平均容许接触水平；最高容许浓度（Maximum allowable concentration，MAC）指工作地点、在一个工作日内、任何时间均不应超过的有毒化学物质的浓度；短时间接触容许浓度（Pemissble concentration-short term exposure limit，PC-STEL)，在遵守  \n\n表2-3-25工作场所空气中有害物质的容许浓度  \n\n\n<html><body><table><tr><td rowspan=\"2\">序号</td><td rowspan=\"2\">中文名</td><td rowspan=\"2\">英文名</td><td rowspan=\"2\">化学文</td><td colspan=\"3\">MAC FC/WA PCSTEL</td><td rowspan=\"2\">备注</td></tr><tr><td></td><td></td><td></td></tr><tr><td>1</td><td>氨</td><td>ammonia</td><td>7664-41-7</td><td>一</td><td>20</td><td>30</td><td></td></tr><tr><td>2</td><td>苯</td><td>benzene</td><td>71-43-2</td><td>一</td><td>6</td><td>10</td><td>皮，G1</td></tr><tr><td>3</td><td>苯胺</td><td>aniline</td><td>62-53-3</td><td>一</td><td>3</td><td>一</td><td>皮</td></tr><tr><td>4</td><td>苯基醚（二苯醚）</td><td>phenyl ether</td><td>101-84-8</td><td>一</td><td>7</td><td>14</td><td></td></tr><tr><td>5</td><td>苯乙烯</td><td>styrene</td><td>100-42-5</td><td>一</td><td>50</td><td>100</td><td>皮，G2B</td></tr><tr><td>6</td><td>吡啶</td><td>pyridine</td><td>110-86-1</td><td>一</td><td>4</td><td>一</td><td>一</td></tr><tr><td>7</td><td>苄基氯</td><td>benzyl chloride</td><td>100-44-7</td><td>5</td><td></td><td>一</td><td>G2A</td></tr><tr><td>8</td><td>丙醇</td><td>propyl alcohol</td><td>71-23-8</td><td>一</td><td>200</td><td>300</td><td>一</td></tr><tr><td>9</td><td>丙酸</td><td>propionic acid</td><td>79-09-4</td><td></td><td>30</td><td></td><td>一</td></tr><tr><td>10</td><td>丙酮</td><td>acetone</td><td>67-64-1</td><td>一</td><td>300</td><td>450</td><td>一</td></tr><tr><td>11</td><td>丙酮氰醇（按CN</td><td>Cactone cyanohydrin as</td><td>75865</td><td>3</td><td>一</td><td>一</td><td>皮</td></tr><tr><td>12</td><td>丙烯醇</td><td>allyl alcohol</td><td>107-18-6</td><td>一</td><td>2</td><td>3</td><td>皮</td></tr><tr><td>13</td><td>丙烯晴</td><td>acrylonitrile</td><td>107-13-1</td><td>一</td><td>1</td><td>2</td><td>皮，G2B</td></tr><tr><td>14</td><td>丙烯醛</td><td>acrolein</td><td>107-02-8</td><td>0.3</td><td>一</td><td>一</td><td>皮</td></tr><tr><td>15</td><td>丙烯酸</td><td>acrylic acid</td><td>79-10-7</td><td>一</td><td>6</td><td>一</td><td>皮</td></tr><tr><td>16</td><td>丙烯酸甲酯</td><td>methyl acrylate</td><td>96-33-3</td><td>一</td><td>20</td><td>二</td><td>皮敏</td></tr><tr><td>17</td><td>丙烯酸正丁酯</td><td>n-butyl acrylate</td><td>141-32-2</td><td></td><td>25</td><td>一</td><td>敏</td></tr><tr><td>18</td><td>丙烯酰胺</td><td>acrylamide</td><td>79-06-1</td><td>-一</td><td>0.3</td><td>一</td><td>皮，G2A</td></tr><tr><td>19</td><td>草酸</td><td>oxalie acid</td><td>144-62-7</td><td>一</td><td>1</td><td>2</td><td>一</td></tr><tr><td>20</td><td>抽余油(60~220°C)</td><td>raffinate(60~220°C)</td><td></td><td>一</td><td>300</td><td>一</td><td>一</td></tr><tr><td>21</td><td>碘仿</td><td>iodoform</td><td>75-47-8</td><td>一</td><td>10</td><td>一</td><td>一</td></tr><tr><td>22</td><td>碘甲烷</td><td>methyl iodide</td><td>74-88-4</td><td></td><td>10</td><td>一</td><td>皮</td></tr><tr><td>23</td><td>丁醇</td><td>butyl aicohol</td><td>71-36-3</td><td></td><td>100</td><td>一</td><td>一</td></tr><tr><td>24</td><td>1,3-丁二烯</td><td>1,3-butadiene</td><td>106-99-0</td><td>一</td><td></td><td>一</td><td>G2A</td></tr><tr><td>25</td><td>丁醛</td><td>butylaldehyde</td><td>123-72-8</td><td></td><td>5</td><td>10</td><td>一</td></tr><tr><td>26</td><td>丁酮</td><td>methyl ethyl ketone</td><td>78-93-3</td><td></td><td>300</td><td>600</td><td></td></tr><tr><td>27</td><td>丁烯</td><td>butylene</td><td>25167-67-3</td><td>一</td><td>100</td><td>一</td><td>一</td></tr><tr><td>28</td><td>对苯二甲酸</td><td>terephthalic acid</td><td>100-21-0</td><td></td><td>8</td><td>15</td><td>一</td></tr><tr><td>29</td><td>对二氯苯</td><td>p-dichlorobenzene</td><td>106-46-7</td><td>**</td><td>30</td><td>60</td><td>G2B</td></tr><tr><td>30</td><td>对菌香胺</td><td>p-anisidine</td><td>104-94-9</td><td>*</td><td>0.5</td><td>一</td><td>皮</td></tr><tr><td>31</td><td>对叔丁基甲苯</td><td>p-tert-butyltoluene</td><td>98-51-1</td><td></td><td>6</td><td>一</td><td></td></tr><tr><td>32</td><td>对硝基苯胺</td><td>p -nitroaniline</td><td>100-01-6</td><td>一</td><td>3</td><td>一</td><td>皮</td></tr><tr><td>33</td><td>对硝基氯苯</td><td>p-nitrochlorobenzene</td><td>100-00-5</td><td>一</td><td>0.6</td><td>一</td><td>皮</td></tr><tr><td>34</td><td>异氨亚甲基多苯基多</td><td>ypolymetyhlene Pphe-</td><td>57029-46-6</td><td>一</td><td>0.3</td><td>0.5</td><td>一</td></tr><tr><td>35</td><td>二苯胺</td><td>diphenylamine</td><td>122-39-4</td><td>一</td><td>10</td><td>一</td><td></td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td rowspan=\"2\">序号</td><td rowspan=\"2\">中文名</td><td rowspan=\"2\">英文名</td><td rowspan=\"2\">化学文摘</td><td colspan=\"3\">MACPCWAPC-STEL</td><td rowspan=\"2\">备注</td></tr><tr><td></td><td></td><td></td></tr><tr><td>36</td><td>酸二*基甲烷二异氨</td><td>dipherlnethanedi</td><td>101-68-8</td><td>一</td><td>0.05</td><td>0.1</td><td>一</td></tr><tr><td>37</td><td>二丙二醇甲醚</td><td>dipropylene glycol meth- yl ether</td><td>34590-94-8</td><td>一</td><td>600</td><td>900</td><td>皮</td></tr><tr><td>38</td><td>2-N-二丁氨基乙醇</td><td>2-N-dibutylamino etha- nol</td><td>102-81-8</td><td></td><td>4</td><td>一</td><td>皮</td></tr><tr><td>39</td><td>二氟氯甲烷</td><td>chlorodifluoromethane</td><td>75-45-6</td><td></td><td>3500</td><td>一</td><td>一</td></tr><tr><td>40</td><td>二甲胺</td><td>dimethylamine</td><td>124-40-3</td><td>一</td><td>5</td><td>10</td><td>一</td></tr><tr><td>41</td><td>体二甲苯（全部异构</td><td>xylene(all isomers)</td><td>1330-20-7； 158-3</td><td></td><td>50</td><td>100</td><td></td></tr><tr><td>42</td><td>二甲基苯胺</td><td>dimethylanilne</td><td>121-69-7</td><td></td><td></td><td>10</td><td>皮</td></tr><tr><td>43</td><td>酸陷3二甲基丁基酯</td><td></td><td>108-84-9</td><td>***</td><td>300</td><td>一</td><td>一</td></tr><tr><td>44</td><td>二甲基二氯硅烷</td><td>dimethyl dichlorosilane</td><td>75-78-5</td><td>2</td><td>二</td><td></td><td>一</td></tr><tr><td>45</td><td>二甲基甲酰胺</td><td>dimethylformamide(DMF)</td><td>68-12-2</td><td>一</td><td>20</td><td>一</td><td>皮</td></tr><tr><td>46</td><td>3,3-二甲基联苯胺</td><td>3,3-dimethylbenzidine</td><td>119-93-7</td><td>0.02</td><td>一</td><td>一</td><td>皮,G2B</td></tr><tr><td>47</td><td>N,N二甲基乙 酰胺</td><td>dimethyl acetamide</td><td>127-19-5</td><td>一</td><td>20</td><td>一</td><td>皮</td></tr><tr><td>48</td><td>二聚环戊二烯</td><td>dicyelopentadiene</td><td>77-73-6</td><td></td><td>25</td><td>一</td><td>一</td></tr><tr><td>49</td><td>1,1-二氯-1-硝基 乙烧</td><td>1,1-dichloro-1-nitroethane</td><td>594-72-9</td><td>一</td><td>12</td><td>一</td><td>一</td></tr><tr><td>50</td><td>1.3-二氯丙醇</td><td>1,3-dichloropropanol</td><td>96-23-1</td><td>一</td><td>5</td><td>一</td><td>皮</td></tr><tr><td>51</td><td>1.2-二氯丙烷</td><td>1,2-dichloropropane</td><td>78-87-5</td><td></td><td>350</td><td>500</td><td>一</td></tr><tr><td>52</td><td>1,3-二氯丙烯</td><td>1,3-dichloropropene</td><td>542-75-6</td><td></td><td>4</td><td>一</td><td>皮，G2B</td></tr><tr><td>53</td><td>二氯二氟甲烷</td><td>dichlorodifluoromethane</td><td>75-71-8</td><td></td><td>5000</td><td>--</td><td>一</td></tr><tr><td>54</td><td>二氯甲烷</td><td>dichloromethane</td><td>75-09-2</td><td>一</td><td>200</td><td>一</td><td>G2B</td></tr><tr><td>55</td><td>二氯乙炔</td><td>dichloroacetylene</td><td>7572-29-4</td><td>0.4</td><td>一</td><td></td><td>一</td></tr><tr><td>56</td><td>1,2-二氯乙烷</td><td>1,2-dichloroethane</td><td>107-06-2</td><td>一</td><td>7</td><td>15</td><td>G2B</td></tr><tr><td>57</td><td>1,2-二氯乙烯</td><td>1,2-dichloroethylene</td><td>540-59-0</td><td></td><td>800</td><td>一</td><td>一</td></tr><tr><td>58</td><td>二缩水甘油醚</td><td>diglycidyl ether</td><td>2238-07-5</td><td>一</td><td>0.5</td><td>一</td><td>一</td></tr><tr><td>59</td><td>二硝基苯（全部异 构体)</td><td>dinitrobenzene ( all iso- mers)</td><td>528-2-0 100-25-4</td><td>一</td><td>1</td><td>一</td><td>皮</td></tr><tr><td>60</td><td>二硝基甲苯</td><td>dinitrotoluene</td><td>25321-14-6</td><td></td><td>0.2</td><td></td><td>皮，G2B(2， 二</td></tr><tr><td>61</td><td>4,6-二硝基邻苯 甲酚</td><td>4,6-dinitro-o-cresol</td><td>534-52-1</td><td>一</td><td>0.2</td><td></td><td>硝基甲苯） 皮</td></tr><tr><td>62</td><td>二硝基氯苯</td><td>dinitrochlorobenzene</td><td>25567-67-3</td><td>=</td><td>0.6</td><td>一</td><td>皮</td></tr><tr><td>63</td><td>2-二乙氨基乙醇</td><td>2-diethylaminoethanol</td><td>100-37-8</td><td>一</td><td>50</td><td></td><td>皮</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td rowspan=\"2\">序号</td><td rowspan=\"2\">中文名</td><td rowspan=\"2\">英文名</td><td rowspan=\"2\">化学文</td><td colspan=\"3\">MAC PCT(WAC- STEL</td><td rowspan=\"2\">备注</td></tr><tr><td></td><td></td><td></td></tr><tr><td>64</td><td>二亚乙基三胺</td><td>diethylene triamine</td><td>11-40-0</td><td>一</td><td>4</td><td>一</td><td>皮</td></tr><tr><td>65</td><td>二乙基甲酮</td><td>diethyl ketone</td><td>96-22-0</td><td></td><td>700</td><td>900</td><td>一</td></tr><tr><td>66</td><td>二乙烯基苯</td><td>divinyl benzene</td><td>1321-74-0</td><td>一</td><td>50</td><td>一</td><td>一</td></tr><tr><td>67</td><td>二异丁基甲酮</td><td>disobutyl ketone</td><td>108-83-8</td><td>一</td><td>145</td><td>一</td><td>一</td></tr><tr><td>68</td><td>（二异氨酸甲苯酯</td><td>( tolue2,4 disorae</td><td>584-84-9</td><td>一</td><td>0.1</td><td>0.2</td><td>敏，G2B</td></tr><tr><td>69</td><td>酚</td><td>phenol</td><td>108-95-2</td><td>一</td><td>10</td><td>一</td><td>皮</td></tr><tr><td>70</td><td>呋哺</td><td>furan</td><td>110-00-9</td><td>一</td><td>0.5</td><td></td><td>G2B</td></tr><tr><td>71</td><td>氟化氢（按F计）</td><td>hydrogen fluoride, as F</td><td>7664-39-3</td><td>2</td><td>一</td><td>一</td><td>一</td></tr><tr><td>72</td><td>氟物（不含氨化</td><td>afloride (except HF),</td><td></td><td>一</td><td>2</td><td>一</td><td>一</td></tr><tr><td>73</td><td>过氧化苯甲酰</td><td>benzoyl peroxide</td><td>94-36-0</td><td>一</td><td>5</td><td>一</td><td>一</td></tr><tr><td>74</td><td>过氧化氢</td><td>hydrogen peroxide</td><td>7722-84-1</td><td></td><td>1.5</td><td>一</td><td>一</td></tr><tr><td>75</td><td>环已胺</td><td>cyclohexylamine</td><td>108-91-8</td><td>一</td><td>10</td><td>20</td><td>一</td></tr><tr><td>76</td><td>环己醇</td><td>cyciohexanol</td><td>108-93-0</td><td>一</td><td>100</td><td>一</td><td>皮</td></tr><tr><td>77</td><td>环已酮</td><td>cyelohexanone</td><td>108-94-1</td><td></td><td>50</td><td>一</td><td>皮</td></tr><tr><td>78</td><td>环己烧</td><td>cyclohexane</td><td>110-82-7</td><td>一</td><td>250</td><td>一</td><td>一</td></tr><tr><td>79</td><td>环氧丙烧</td><td>propylene oxide</td><td>75-56-9</td><td>一</td><td>5</td><td>一</td><td>敏，G2B</td></tr><tr><td>80</td><td>环氧氯丙烷</td><td>epichlorohydrin</td><td>106-89-8</td><td>一</td><td>1</td><td>2</td><td>皮，G2A</td></tr><tr><td>81</td><td>环氧乙烷</td><td>ethylene oxide</td><td>75-21-8</td><td>一</td><td>2</td><td>一</td><td>G1</td></tr><tr><td>82</td><td>己二醇</td><td>hexylene glycol</td><td>107-41-5</td><td>100</td><td>一</td><td>一</td><td>一</td></tr><tr><td>83</td><td>1.6-己二异氰酸酶</td><td> hexametylen lisoeya-</td><td>822-06-0</td><td>一</td><td>0.03</td><td>一</td><td>一</td></tr><tr><td>84</td><td>已内酰胺</td><td>caprolactam</td><td>105-60-2</td><td>一</td><td>5</td><td>一</td><td>一</td></tr><tr><td>85</td><td>2-已酮</td><td>2-hexanone</td><td>591-786</td><td>一</td><td>20</td><td>40</td><td>皮</td></tr><tr><td>86</td><td>甲苯</td><td>toluene</td><td>108-88-3</td><td>一</td><td>50</td><td>100</td><td>皮</td></tr><tr><td>87</td><td>N-甲苯胺</td><td>N-methyl aniline</td><td>100-61-8</td><td>一</td><td>2</td><td>一</td><td>皮</td></tr><tr><td>88</td><td>甲醇</td><td>methanol</td><td>67-56-1</td><td>一</td><td>25</td><td>50</td><td>皮</td></tr><tr><td>89</td><td>甲基丙烯腩</td><td>methylacrylonitrile</td><td>126-98-7</td><td></td><td>3</td><td></td><td>皮</td></tr><tr><td>90</td><td>甲基丙烯酸</td><td>methacrylic acid</td><td>79-41-4</td><td>一</td><td>70</td><td>一</td><td></td></tr><tr><td>91</td><td>甲基丙烯酸甲酯</td><td>methyl methacrylate</td><td>80-62-6</td><td>一</td><td>100</td><td>一</td><td>敏</td></tr><tr><td>92</td><td>油甲基丙烯酸缩水甘</td><td>glycidyl methacrylate</td><td>106-91-2</td><td>5</td><td>一</td><td>一</td><td></td></tr><tr><td>93</td><td>甲基肼</td><td>methyl hydrazine</td><td>60-34-4</td><td>0.08</td><td>一</td><td></td><td>皮</td></tr><tr><td>94</td><td>甲硫醇</td><td>methyl mercaptan</td><td>74-93-1</td><td>一</td><td></td><td>一</td><td></td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td rowspan=\"2\">序号</td><td rowspan=\"2\">中文名</td><td rowspan=\"2\">英文名</td><td rowspan=\"2\">化学文摘</td><td colspan=\"3\">MAC PCWA P STEL</td><td rowspan=\"2\">备注</td></tr><tr><td></td><td></td><td></td></tr><tr><td>95</td><td>甲醛</td><td>formaldehyde</td><td>50-000</td><td>0.5</td><td>一</td><td>一</td><td>敏，G1</td></tr><tr><td>96</td><td>甲酸</td><td>formie acid</td><td>64-18-6</td><td>一</td><td>10</td><td>20</td><td>一</td></tr><tr><td>97</td><td>甲氧基乙醇</td><td>2-methoxyethanol</td><td>109-86-4</td><td>一</td><td>15</td><td>一</td><td>皮</td></tr><tr><td>98</td><td></td><td>hydrazine</td><td>302-01-2</td><td>一</td><td>0.06</td><td>0.13</td><td>皮，G2B</td></tr><tr><td>99</td><td>糠醇</td><td>furfuryl aleohol</td><td>98-00-0</td><td>一</td><td>40</td><td>60</td><td>皮</td></tr><tr><td>100</td><td>橡醛</td><td>furfural</td><td>98-01-1</td><td>一</td><td>5</td><td>一</td><td>皮</td></tr><tr><td>101</td><td>联苯</td><td>biphenyl</td><td>92-52-4</td><td>一</td><td>1.5</td><td>一</td><td></td></tr><tr><td>102</td><td>邻苯二甲酸二丁酯</td><td>dibutyl phthalate</td><td>84-74-2</td><td>一</td><td>2.5</td><td>一</td><td>一</td></tr><tr><td>103</td><td>邻苯二甲酸酐</td><td>phthalie anhydride</td><td>85-44-9</td><td>1</td><td>一</td><td>一</td><td>敏</td></tr><tr><td>104</td><td>邻二氯苯</td><td>o-dichlorobenzene</td><td>95-50-1</td><td>一</td><td>50</td><td>100</td><td></td></tr><tr><td>105</td><td>邻菌香胺</td><td>o-anisidine</td><td>90-04-0</td><td></td><td>0.5</td><td>一</td><td>皮，G2B</td></tr><tr><td>106</td><td>邻氯苯乙烯</td><td>o-chlorostyrene</td><td>2038-87-47</td><td>一</td><td>250</td><td>400</td><td>一</td></tr><tr><td>107</td><td>磷酸</td><td>phosphoric acid</td><td>766438-2</td><td>一</td><td>1</td><td>3</td><td>一</td></tr><tr><td>108</td><td>磷酸二丁基苯酯</td><td>dibutyl phenyl phosphate</td><td>2528-36-1</td><td>一</td><td>3.5</td><td>一</td><td>皮</td></tr><tr><td>109</td><td>硫酸二甲酯</td><td>dimethyl sulfate</td><td>77-78-1</td><td>一</td><td>0.5</td><td>一</td><td>皮，G2A</td></tr><tr><td>110</td><td>硫酸及三氧化硫</td><td>sulfuric acid and sulfur trioxide</td><td>7664-93-9</td><td>一</td><td>1</td><td>2</td><td>G1</td></tr><tr><td>111</td><td>硫酰氟</td><td>sulfuryl fluoride</td><td>2699-79-8</td><td>一</td><td>20</td><td>40</td><td>一</td></tr><tr><td>112</td><td>六氟丙酮</td><td>hexafluoroacetone</td><td>684-16-2</td><td>*</td><td>0.5</td><td>一</td><td>皮</td></tr><tr><td>113</td><td>六氟丙烯</td><td>hexafluoropropylene</td><td>116-15-4</td><td>一</td><td>4</td><td>一</td><td>一</td></tr><tr><td>114</td><td>六氟化硫</td><td>sulfur hexafluoride</td><td>2551-62-4</td><td>一</td><td>6000</td><td></td><td>一</td></tr><tr><td>115</td><td>六氯丁二烯</td><td>hexachlorobutadine</td><td>87-68-3</td><td></td><td>0.2</td><td>一</td><td>皮</td></tr><tr><td>116</td><td>六氯环戊二烯</td><td>dithexachoneylie n</td><td>77-47-4</td><td>一</td><td>0.1</td><td>一</td><td>一</td></tr><tr><td>117</td><td>六氰蔡</td><td>hexachloronaphthalene</td><td>1335-87-1</td><td>一</td><td>0.2</td><td>一</td><td>皮</td></tr><tr><td>118</td><td>六氯乙烷</td><td>hexachloroethane</td><td>67-72-1</td><td></td><td>10</td><td></td><td>皮，G2B</td></tr><tr><td>119</td><td>氧苯</td><td>chlorobenzene</td><td>108-90-7</td><td>/</td><td>50</td><td>-</td><td>一</td></tr><tr><td>120</td><td>氯丙酮</td><td>chloroacetone</td><td>78-95-5</td><td>4</td><td></td><td>=</td><td>皮</td></tr><tr><td>121</td><td>氯丙烯</td><td>allyl chloride</td><td>107-05-1</td><td>一</td><td>2</td><td>4</td><td>一</td></tr><tr><td>122</td><td>β氯丁二烯</td><td>chloroprene</td><td>126-99-8</td><td>一</td><td>4</td><td>一</td><td>皮，G2B</td></tr><tr><td>123</td><td>氯化氢及盐酸</td><td>hydrogen chloride and chlorhydric acid</td><td>7647-01-0</td><td>7.5</td><td>一</td><td></td><td></td></tr><tr><td>124</td><td>氯甲基甲醚</td><td>chloromethyl methyl e- ther</td><td>107-30-2</td><td>0.005</td><td>一</td><td>一</td><td>G1</td></tr><tr><td>125</td><td>氯甲烷</td><td>methyl chloride</td><td>74-873</td><td>一</td><td>60</td><td>120</td><td>皮</td></tr><tr><td>126</td><td>氯联苯（54%氯）</td><td>chlorodiphenyl (54%CI)</td><td>11097-69-1</td><td>一</td><td>0.5</td><td>一</td><td>皮，G2A</td></tr><tr><td>127</td><td>氯萘</td><td>chloronaphthalene</td><td>90-13-1</td><td>一</td><td>0.5</td><td>一</td><td>皮</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td rowspan=\"2\">序号</td><td rowspan=\"2\">中文名</td><td rowspan=\"2\">英文名</td><td rowspan=\"2\">化学文摘号 (CAS No. )</td><td colspan=\"3\">OELs/(mg/m²)</td><td rowspan=\"2\">备注</td></tr><tr><td>MAC</td><td>PC-TWA</td><td>PC-STEL</td></tr><tr><td>128</td><td>氯乙醇</td><td>ethylene chlorohydrin</td><td>107-07-3</td><td>2</td><td>一</td><td>一</td><td>皮</td></tr><tr><td>129</td><td>氯乙醛</td><td>chloroacetaldehyde</td><td>107-20-0</td><td>3</td><td>一</td><td>一</td><td>一</td></tr><tr><td>130</td><td>氯乙酸</td><td>chloroacetic acid</td><td>79-11-8</td><td>2</td><td>一</td><td>一</td><td>皮</td></tr><tr><td>131</td><td>氯乙烯</td><td>vinyl chloride</td><td>75-01-4</td><td>一</td><td>10</td><td>一</td><td>G1</td></tr><tr><td>132</td><td>（煤集油沥青挥发物</td><td>as bel tar pitdblelae</td><td>65996-93-2</td><td>一</td><td>0.2</td><td>一</td><td>G1</td></tr><tr><td>133</td><td>蔡</td><td>naphthalene</td><td>91-20-3</td><td>一</td><td>50</td><td>75</td><td>皮，G2B</td></tr><tr><td>134</td><td>蔡烷</td><td>decalin</td><td>91-17-8</td><td>一</td><td>60</td><td>一</td><td></td></tr><tr><td>135</td><td>偏二甲基肼</td><td>hydrasmmetic dimehgl</td><td>57-14-7</td><td>一</td><td>0.5</td><td>一</td><td>皮，G2B</td></tr><tr><td>136</td><td>氢醒</td><td>hydroquinone</td><td>123-31-9</td><td>一</td><td>1</td><td>2</td><td>一</td></tr><tr><td>137</td><td>氢氧化钾</td><td>potassium hydroxide</td><td>1310-58-3</td><td>2</td><td>一</td><td>一</td><td>一</td></tr><tr><td>138</td><td>氢氧化钠</td><td>sodium hydroxide</td><td>1310-73-2</td><td>2</td><td>一</td><td>一</td><td>一</td></tr><tr><td>139</td><td>氰化物（按CN计）</td><td>cyanides, as CN</td><td>460-19-5 (CN)</td><td>1</td><td>一</td><td>一</td><td>皮</td></tr><tr><td>140</td><td>氰戊菊酯</td><td>fenvalerate</td><td>51630-58-1</td><td>一</td><td>0.05</td><td>一</td><td>皮</td></tr><tr><td>141</td><td>全氟异丁烯</td><td>perfluoroisobutylene</td><td>382-21-8</td><td>0.08</td><td>一</td><td></td><td>一</td></tr><tr><td>142</td><td>壬烧</td><td>nonane</td><td>111-842</td><td>一</td><td>500</td><td>一</td><td>一</td></tr><tr><td>143</td><td>溶剂汽油</td><td>solvent gasolines</td><td></td><td>一</td><td>300</td><td>一</td><td>一</td></tr><tr><td>144</td><td>乳酸正丁酶</td><td>n-butyl lactate</td><td>138-22-7</td><td>一</td><td>25</td><td>一</td><td>一</td></tr><tr><td>145</td><td>（黑三亚甲基三硝基酸</td><td>cyelonite (RDX)</td><td>121-82-4</td><td>一</td><td>1.5</td><td>一</td><td>皮</td></tr><tr><td>146</td><td>三氟化氯</td><td>chlorine trifluoride</td><td>7790-91-2</td><td>0.4</td><td></td><td>一</td><td>一</td></tr><tr><td>147</td><td>三氟化硼</td><td>boron trifluoride</td><td>7637-07-2</td><td>3</td><td>一</td><td>一</td><td>一</td></tr><tr><td>148</td><td>三氟甲基次氟酸酯</td><td>trifluoromethyl hypoflu- orite</td><td></td><td>0.2</td><td>一</td><td>一</td><td>一</td></tr><tr><td>149</td><td>三甲苯磷酸酯</td><td>tricresyl phosphate</td><td>1330-78-5</td><td></td><td>0.3</td><td>--</td><td>皮</td></tr><tr><td>150</td><td>1.2.3-三氯丙烷</td><td>1,2,3-trichloropropane</td><td>96-18-4</td><td></td><td>60</td><td>一</td><td>皮，G2A</td></tr><tr><td>151</td><td>三氯甲烷</td><td>trichloromethane</td><td>67-66-3</td><td>一</td><td>20</td><td>=</td><td>G2B</td></tr><tr><td>152</td><td>三氯乙醛</td><td>trichloroacetaldehyde</td><td>75-87-6</td><td>3</td><td>一</td><td>一</td><td>一</td></tr><tr><td>153</td><td>1,1,1-三氯乙烧</td><td>1,1;1-trichloroethane</td><td>71-55-6</td><td></td><td>900</td><td>一</td><td>一</td></tr><tr><td>154</td><td>三氯乙烯</td><td>trichloroethylene</td><td>79-01-6</td><td></td><td>30</td><td>厂</td><td>G2A</td></tr><tr><td>155</td><td>三硝基甲苯</td><td>trinitrotoluene</td><td>118-96-7</td><td>一</td><td>0.2</td><td>0.5</td><td>皮</td></tr><tr><td>156</td><td>双丙酮醇</td><td>diacetone alcohol</td><td>123-42-2</td><td>一</td><td>240</td><td>一</td><td></td></tr><tr><td>157</td><td>双氟甲醚</td><td>bis(chloromethyl) ether</td><td>542-88-1</td><td>0.005</td><td>一</td><td>一</td><td>G1</td></tr><tr><td>158</td><td>四氯化碳</td><td>carbon tetrachloride</td><td>56-23-5</td><td>一</td><td>15</td><td>25</td><td>皮，G2B</td></tr><tr><td>159</td><td>四氯乙烯</td><td>tetrachloroethylene</td><td>127-18-4</td><td></td><td>200</td><td>一</td><td>G2A</td></tr><tr><td>160</td><td>四氢呋哺</td><td>tetrahydrofuran</td><td>109-99-9</td><td>一</td><td>300</td><td>一</td><td>一</td></tr><tr><td>161</td><td>四澳化碳</td><td>carbon tetrabromide</td><td>558-13-4</td><td>一</td><td>1.5</td><td>4</td><td>一</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td rowspan=\"2\">序号</td><td rowspan=\"2\">中文名</td><td rowspan=\"2\">英文名</td><td rowspan=\"2\">化学文摘号</td><td colspan=\"3\">MACPC-WACSTEL</td><td rowspan=\"2\">备注</td></tr><tr><td></td><td></td><td></td></tr><tr><td>162</td><td>松节油</td><td>turpentine</td><td>8006-64-2</td><td>一</td><td>300</td><td>一</td><td>一</td></tr><tr><td>163</td><td>基氟</td><td>carbonyl fluoride</td><td>353-50-4</td><td></td><td>5</td><td>10</td><td></td></tr><tr><td>164</td><td>五氟氯乙烷</td><td>chloropentafluoroe thane</td><td>76-15-3</td><td>一</td><td>5000</td><td>一</td><td>一</td></tr><tr><td>165</td><td>戊醇</td><td>amyl alcohol</td><td>71-41-0</td><td>一</td><td>100</td><td>一</td><td>一</td></tr><tr><td>166</td><td>戊烷(全部异构体)</td><td>pentane (all isomers)</td><td>78-78-4； 109-66-0</td><td></td><td>500</td><td>1000</td><td>一</td></tr><tr><td>167</td><td>硝基苯</td><td>nitrobenzene</td><td>463-82-1 98-95-3</td><td></td><td>2</td><td>一</td><td>皮，G2B</td></tr><tr><td>168</td><td>1-硝基丙烷</td><td>1-nitropropane</td><td>108-03-2</td><td></td><td>90</td><td>一</td><td>一</td></tr><tr><td>169</td><td>2-硝基丙烷</td><td>2-nitropropane</td><td>79-46-9</td><td>一</td><td>30</td><td>一</td><td>G2B</td></tr><tr><td>170</td><td>硝基甲苯（全部异 构体)</td><td>nitrotoluene (all isomers)</td><td>88-72-2 99-08-1；</td><td>一</td><td>10</td><td>一</td><td>皮</td></tr><tr><td>171</td><td>硝基甲烷</td><td>nitromethane</td><td>99-99-0 75-52-5</td><td></td><td>50</td><td>一</td><td>G2B</td></tr><tr><td>172</td><td>硝基乙烷</td><td>nitroethane</td><td>79-24-3</td><td>一</td><td>300</td><td></td><td></td></tr><tr><td>173</td><td>辛烷</td><td>octane</td><td>111-65-9</td><td>一</td><td>500</td><td></td><td>一</td></tr><tr><td>174</td><td>澳甲烷</td><td>methyl bromide</td><td>74-83-9</td><td>一</td><td>2</td><td>一</td><td>皮</td></tr><tr><td>175</td><td>一甲胺</td><td>monomethylamine</td><td>74-89-5</td><td>一</td><td></td><td>10</td><td>一</td></tr><tr><td>176</td><td>乙肢</td><td>ethylamine</td><td>75-04-7</td><td>=</td><td></td><td>18</td><td>皮</td></tr><tr><td>177</td><td>乙苯</td><td>ethyl benzene</td><td>100-41-4</td><td></td><td>100</td><td>150</td><td>G2B</td></tr><tr><td>178</td><td>乙醇胺</td><td>ethanolamine</td><td>141-43-5</td><td>一</td><td>8</td><td>15</td><td>一</td></tr><tr><td>179</td><td>乙二胺</td><td>ethylenediamine</td><td>107-15-3</td><td>一</td><td>4</td><td>10</td><td>皮</td></tr><tr><td>180</td><td>乙二醇</td><td>ethylene glycol</td><td>107-21-1</td><td></td><td>20</td><td>40</td><td>一</td></tr><tr><td>181</td><td>乙二醇二硝酸酯</td><td>ethylene glycol dinitrate</td><td>628-96-6</td><td></td><td>0.3</td><td>一</td><td>皮</td></tr><tr><td>182</td><td>乙酐</td><td> acetic anhydride</td><td>108-24-7</td><td></td><td>16</td><td>一</td><td>一</td></tr><tr><td>183</td><td>乙基戊基甲酮</td><td>ethyl amyl ketone</td><td>541-85-5</td><td>=</td><td>130</td><td>一</td><td>一</td></tr><tr><td>184</td><td>乙腊</td><td>acetonitrile</td><td>75-05-8</td><td></td><td>30</td><td>一</td><td>皮</td></tr><tr><td>185</td><td>乙硫醇</td><td>ethyl mercaptan</td><td>75-08-1</td><td>一</td><td>1</td><td></td><td>一</td></tr><tr><td>186</td><td>乙醚</td><td>ethyl ether</td><td>60-29-7</td><td></td><td>300</td><td>500</td><td>一</td></tr><tr><td>187</td><td>乙硼烷</td><td>diborane</td><td>19287-45-7</td><td>一</td><td>0.1</td><td>一</td><td>一</td></tr><tr><td>188</td><td>乙醛</td><td>acetaldehyde</td><td>75-07-0</td><td>45</td><td>=</td><td>一</td><td>G2B</td></tr><tr><td>189</td><td>乙酸</td><td>acetic acid</td><td>64-19-7</td><td>一</td><td>10</td><td>20</td><td>5</td></tr><tr><td>190</td><td>2-甲基乙基乙</td><td>2-methoxyethyl acetate</td><td>110-49-6</td><td>一</td><td>20</td><td>一</td><td>皮</td></tr><tr><td>191</td><td>酸酯 乙酸丙酯</td><td>propyl acetate</td><td>109-60-4</td><td>一</td><td>200</td><td>300</td><td>一</td></tr><tr><td>192</td><td>乙酸丁酯</td><td>butyl acetate</td><td>123-86-4</td><td></td><td>200</td><td>300</td><td></td></tr><tr><td>193</td><td>乙酸甲酯</td><td>methyl acetate</td><td>79-20-9</td><td></td><td>200</td><td>500</td><td></td></tr><tr><td>194</td><td>梅乙酸戊酯（全部异</td><td>meamyl acete (allio</td><td>628-63-7</td><td>一</td><td>100</td><td>200</td><td></td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td rowspan=\"3\">序号</td><td rowspan=\"2\">中文名</td><td rowspan=\"2\">英文名</td><td rowspan=\"2\">化学文摘号</td><td colspan=\"3\">MAC PC-WAPC STEL</td><td rowspan=\"2\">备注</td></tr><tr><td></td><td></td><td></td></tr><tr><td>195</td><td>乙酸乙烯酯</td><td>vinyl acetate</td><td>108-05-4</td><td>一</td><td>10</td><td>15</td><td>G2B</td></tr><tr><td>196</td><td>乙酸乙酯</td><td>ethyl acetate</td><td>141-78-6</td><td>一</td><td>200</td><td>300</td><td>一</td></tr><tr><td>197</td><td>乙烯酮</td><td>ketene</td><td>463-51-4</td><td>一</td><td>0.8</td><td>2.5</td><td>一</td></tr><tr><td>198</td><td>2-乙氧基乙醇</td><td>2-ethoxyethanol</td><td>110-80-5</td><td>一</td><td>18</td><td>36</td><td>皮</td></tr><tr><td>199</td><td>2 酸酯</td><td>2-ethoxyethyl acetate</td><td>111-15-9</td><td></td><td>30</td><td>一</td><td>皮</td></tr><tr><td>200</td><td>异丙胺</td><td>isopropylamine</td><td>75-31-0</td><td>一</td><td>12</td><td>24</td><td>一</td></tr><tr><td>201</td><td>异丙醇</td><td>isopropyl alcohol(IPA)</td><td>67-63-0</td><td></td><td>350</td><td>700</td><td>一</td></tr><tr><td>202</td><td>N-异丙基苯胺</td><td>N-isopropylaniline</td><td>768-52-5</td><td>一</td><td>10</td><td>-</td><td>皮</td></tr><tr><td>203</td><td>异佛尔酮</td><td>isophorone</td><td>78-59-1</td><td>30</td><td>一</td><td>一</td><td>一</td></tr><tr><td>204</td><td>异佛尔酮二异氰 酸酯</td><td>isophorone diisocyanate (IPDD)</td><td>4098-71-9</td><td>一</td><td>0.05</td><td>0.1</td><td>一</td></tr><tr><td>205</td><td>异氰酸甲酯</td><td>methyl isocyanate</td><td>624-83-9</td><td>一</td><td>0.05</td><td>0.08</td><td>皮</td></tr><tr><td>206</td><td>异亚丙基丙酮</td><td>mesityl oxide</td><td>141-79-7</td><td></td><td>60</td><td>100</td><td>一</td></tr><tr><td>207</td><td></td><td>indene</td><td>95-13-6</td><td></td><td>50</td><td>一</td><td>一</td></tr><tr><td>208</td><td>正丁胺</td><td>n-butylamine</td><td>109-73-9</td><td>15</td><td>一</td><td>一</td><td>皮</td></tr><tr><td>209</td><td>正丁基硫醇</td><td>n-butyl mercaptan</td><td>109-79-5</td><td>-一</td><td>2</td><td>一</td><td>一</td></tr><tr><td>210</td><td>正丁基缩水甘油醚</td><td>n-butyl glycidyl ether</td><td>2426-08-6</td><td>一</td><td>60</td><td></td><td>一</td></tr><tr><td>211</td><td>·正庚烧</td><td>#-heptane</td><td>142-82-5</td><td></td><td>500</td><td>1000</td><td>一</td></tr><tr><td>212</td><td>正已烷</td><td>n-hexane</td><td>110-54-3</td><td>一</td><td>100</td><td>180</td><td>皮</td></tr></table></body></html>\n\n注：1.有（皮）标记者为除呼吸道吸收外，尚易于皮肤吸收的有毒物质；有（敏）标记者是指已被人或动物资料证实该物质可能有致敏作用。  \n\n2. G1：确认人类致癌物（carcinogenic to humans）； G2A；可能人类致癌物(probably carcinogenic to humans)；G2B：可疑人类致癌物（possibly carcinogenic to humans)）；G3；对人及动物致癌性证据不足（not calssifiable as to carci-nogenicity to humans)； G4:未列为人类致癌物(probably not carcinogenic to humans)  \n\n3.本表摘自GBZ2.1—2007《工业场所有害因素职业接触限值》  \n\nPC-TWA前提下容许短时间 $\\mathrm{:}15\\mathrm{min}^{\\cdot}$ ）接触的浓度。为达到此标准则要求使用溶剂的设备尽量采取密闭操作，保持车间自然通风及安装强制换气设备。  \n\n另外，也应注意不用皮肤和溶剂直接接触，特别是不与高浓度的溶剂接触，以避免通过皮肤吸收中毒。  \n\n国际劳工组织于1990年6月讨论通过了《工作场所安全使用化学品》170号公约，我国1994年10月27日第八届全国人大常委会第十二次会议讨论批准了170号公约。为贯彻170号公约，国家相关部委颁布了《工作场所安全使用化学品规定》，规定要求所有生产和经营化学品的企业，必须进行危险化学品登记，在包装上加贴安全标签和编印安全技术说明书。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 639,
+        "chunk": "# 3.空气污染限制  \n\n空气污染限制是出于对生态环境保护的目的而提出的。第一个最著名的溶剂空气污染管理法是洛杉矶国家空气污染控制第66号区域管理法规（简称66法规)，于1967年7月1日生效的。它的目的是在周围空气环境中减少臭氧量（烃类在太阳光下把氧催化而形成臭氧)。  \n\n66法规是基于光学反应，并根据烃类促使臭氧形成的速率是根据分子类型而变化的概念而制定的，因此原始法规包括以下内容：光化学反应溶剂是指按下列分类的化合物总体积超过 $20\\%$ ，或各自组成超出下列极限的溶剂。  \n\n$\\textcircled{1}$ 具有不饱和键的烃、醇、醛、酯、醚或酮混合的溶剂、烯烃或环烯烃： $5\\%$ $\\textcircled{2}$ 除乙苯外具有8个或8个以上碳原子的芳烃分子的混合溶剂： $20\\%$  \n\n无论什么时候，任一有机溶剂或任何有机溶剂的组成，可根据其化学结构分成比上述有机化合物更多的类别，也应看成是最活性化合物分类的一种，它在溶剂总体积中也应占最小的百分数。  \n\n虽然洛杉矶的空气污染管理法吸收了南海岸空气质量管理法，而且在那个机构中66法规被102法规和422法规所替代，但66法规还是立刻被那些关心溶剂污染空气的人所确认。它被作为全国甚至世界某些地区许多法规的典范。  \n\n1976年，美国环境保护局（EPA）确定光化学反应不是控制污染物的有效基础。因为所有溶剂都是反应的，它们的区别仅在于反应速率。新法规规定对于高固体分涂料，每立方米涂料中挥发性有机化学物含量不超过 $0.34\\mathsf{k g}$ 的规定。因此，选用较低密度，而有较高的溶解力的溶剂是获得指定黏度下，每立方米涂料含有较少挥发性溶剂的有效途径，这也是涂料工作者为符合空气污染管理法，在选用溶剂时需要考虑的一个重要因素。",
+        "category": " Introduction"
+    },
+    {
+        "id": 640,
+        "chunk": "# 4.安全性  \n\n众所周知，溶剂型涂料是易燃易爆的化学品，而决定其燃烧和爆炸危险程度的主要因素，是涂料产品中使用的溶剂，因此，溶剂的安全性直接影响着涂料产品在生产、贮存、运输及涂装过程中的起火及爆炸的危险程度。我们设计色漆配方时，在满足产品对溶剂的上述诸项要求的同时，充分考虑溶剂的安全性指标也是涂料工作者应当高度重视的一个问题。  \n\n(1）燃烧及自燃溶剂在安全性方面的主要危险是燃烧和爆炸。燃烧是一种放热发光的化学反应，物质燃烧必须同时具备3个条件：有可燃性的物质存在；有氧的存在及有火源存在。溶剂的燃烧不是液体溶剂本身的燃烧，而是溶剂液体的蒸气被氧化分解而形成燃烧。  \n\n闪点是用以评价溶剂燃烧危险程度的一个重要指标。闪点是可燃性液体受热时，其液体表面上的蒸气和空气的混合物接触火源发生闪燃时的最低温度。所谓“闪燃”是因为温度尚低，可燃性液体产生蒸气的速率尚慢，其上部蒸气一经燃烧，新的蒸气补充不上来，则造成燃烧现象一闪即逝，故称闪燃。可燃性液体能发生闪燃时的温度称作它的闪点。从发生着火的危险角度而言，达到闪点已经达到了可能燃烧的信息点，因此，将闪点作为评价溶剂燃烧温度的指标。  \n\n如果将达到闪点温度的可燃性液体继续加热，当温度上升到某一点，在该温度下，可燃性液体的蒸气和空气的混合物接触火源发生燃烧，而移去火源后仍能继续燃烧，那么这一温度就是该可燃性液体的燃点，或称作着火点。因为达到燃点时可燃性液体就可以形成连续燃烧了，所以作为火灾的危险的信息就为时太晚了，故规定以闪点作为物质火灾危险程度的评价指标。依据闪点可以将可燃性液体分为两类四级，闪点越低、危险性越大，而溶剂的密度越小、挥发速率越快、闪点就越低（见表2-3-26）  \n\n自燃是有机溶剂发生火灾的另一种表现形式。这是由于其受热后发生氧化反应而产生的热量不能释放，导致温度继续升高及氧化反应加剧，最后自燃起火的现象。溶剂不需火源即可自行起火并继续燃烧的最低温度称作自燃点（或自行着火点）。在产生及使用溶剂的过程中，必须保持温度低于其自燃温度。浸有溶剂的物质不可随处丢放，以免导致自燃。  \n\n表2-3-26 易燃和可燃液体的易燃性分级标准  \n\n\n<html><body><table><tr><td colspan=\"2\">类别</td><td>闪点/C</td><td>举例</td></tr><tr><td rowspan=\"2\">易燃液体</td><td>一级</td><td><28</td><td>汽油、乙醇、苯</td></tr><tr><td>二级</td><td>28~45</td><td>煤油、松节油</td></tr><tr><td rowspan=\"2\">可燃液体</td><td>三级</td><td>45~120</td><td>柴油</td></tr><tr><td>四级</td><td>>120</td><td>甘油</td></tr></table></body></html>  \n\n(2）爆炸爆炸和燃烧没有本质区别，可燃性液体的蒸气剧烈燃烧，产生的能量以冲击波的形式释放出来就叫爆炸。  \n\n可燃性液体的蒸气和空气的混合物不是在任何状况下都可以爆炸的，其蒸气浓度和空气的混合物必须达到一定范围，在这个范围内遇到火源才发生爆炸。这个浓度范围叫作爆炸浓度极限，简称爆炸极限。能发生爆炸的最低浓度称作爆炸下限，能发生爆炸的最高浓度称作爆炸上限。可燃性液体蒸气浓度在爆炸下限以下或在爆炸上限以上，由于热量不足或氧气量不够，不能发生燃烧和爆炸。只有在爆炸下限和爆炸上限这个浓度范围内方可以发生爆炸，这个区间称为爆炸极限范围。爆炸极限范围常以可燃性液体蒸气的体积分数表示。  \n\n可燃性液体蒸气的爆炸危险可以用爆炸危险度表示，即爆炸危险度 $\\c=$ （爆炸上限浓度一爆炸下限浓度）/爆炸下限浓度  \n\n上式说明，爆炸下限浓度越低，而爆炸上限越高，即爆炸极限范围越宽时，出现爆炸的机会就越多，爆炸危险性就越大。火灾爆炸的危险程度越高，工厂设计及建筑要求也越苛刻，项目投资也越大。因此，在设计溶剂型涂料选择溶剂时要在满足产品需要的情况下，尽量选取用火灾及爆炸危险性小的溶剂。以降低产品工业化的难度和提高规模化生产的安全性，表2-3-27列出了溶剂的闪点、爆炸极限及自燃点数据。  \n\n表2-3-27溶剂的闪点、自燃点及爆炸极限（体积分数）  \n\n\n<html><body><table><tr><td rowspan=\"2\">名称</td><td rowspan=\"2\">点</td><td colspan=\"2\"></td><td rowspan=\"2\">自燃</td><td rowspan=\"2\">名称</td><td rowspan=\"2\">点</td><td colspan=\"2\"></td><td rowspan=\"2\"></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td>石油醚</td><td><0</td><td>1.4</td><td>5.9</td><td></td><td>甲基异丁基酮</td><td>23</td><td>1.4</td><td>7.5</td><td>459</td></tr><tr><td>200号溶剂油</td><td>33</td><td>1.0</td><td>6.2</td><td></td><td>二丙酮醇</td><td>64</td><td>1.8</td><td>6.9</td><td></td></tr><tr><td>苯</td><td>11.1</td><td>1.4</td><td>21</td><td>562.1</td><td>丙二醇甲醚醋酸酯</td><td>48</td><td>1.5</td><td>7</td><td>333</td></tr><tr><td>甲苯</td><td>4.4</td><td>1.27</td><td>7.0</td><td>552</td><td>丙二醇甲醚</td><td>32</td><td>3.0</td><td>12.0</td><td>532</td></tr><tr><td>二甲萃</td><td>25.29</td><td>1.0</td><td>5.3</td><td>530</td><td>醋酸乙酯</td><td>4.0</td><td>2.18</td><td>11.4</td><td>425.5</td></tr><tr><td>Solvesso 100</td><td>44</td><td>1.0</td><td>6.0</td><td>530</td><td>醋酸丁酯</td><td>27</td><td>1.4</td><td>8.0</td><td>421</td></tr><tr><td>Solvesso 150</td><td>63</td><td>1.0</td><td>6.0</td><td>463</td><td>醋酸异丁酯</td><td>17.8</td><td>2.4</td><td>10.5</td><td>422.8</td></tr><tr><td>松节油</td><td>35</td><td>0.8</td><td></td><td>253.3</td><td>醋酸戊酯</td><td>25</td><td>1.1</td><td>7.5</td><td>378.9</td></tr><tr><td>甲醇</td><td>12</td><td>6.0</td><td>36.5</td><td>470</td><td>醋酸异戊酯</td><td>25</td><td>1. 0</td><td>7.5</td><td>379.4</td></tr><tr><td>乙醇</td><td>14</td><td>4.3</td><td>19.0</td><td>390~430</td><td>乳酸丁酯</td><td>71</td><td></td><td></td><td>382.2</td></tr><tr><td>丙醇</td><td>27(开)</td><td>2.6</td><td>13.5</td><td>440</td><td>乙二醇乙醚</td><td>45</td><td>1.8</td><td>14.0</td><td>238</td></tr><tr><td>异丙醇</td><td>11.7</td><td>2.02</td><td>7.99</td><td>460</td><td>二甘醇乙醚</td><td>94</td><td></td><td></td><td></td></tr><tr><td>正丁醇</td><td>35.0</td><td>1.45</td><td>11.25</td><td>340~420</td><td>二甘醇丁醚</td><td>110</td><td></td><td></td><td></td></tr><tr><td>异丁醇</td><td>27.5(开）</td><td>1.65</td><td></td><td></td><td>乙二醇乙醚醋酸酯</td><td>51</td><td>1.7</td><td></td><td></td></tr><tr><td>仲丁醇</td><td>31(开)</td><td>1.7</td><td>9.8</td><td>406</td><td>乙二醇丁醚醋酸酯</td><td>88（开）</td><td></td><td></td><td></td></tr><tr><td>丙酮</td><td>17.8</td><td>2.55</td><td>12.80</td><td>561</td><td>硝基乙烷</td><td>41（开）</td><td>4.0</td><td></td><td>414</td></tr><tr><td>甲基丙酮</td><td>-7.2</td><td>1. 81</td><td>11.5</td><td>5.6</td><td>硝基丙烷</td><td>37.8</td><td>2.6</td><td></td><td>421</td></tr><tr><td>异佛尔酮</td><td>96(开)</td><td></td><td></td><td>462</td><td>二氯甲烷</td><td>34(开)</td><td></td><td></td><td>622</td></tr><tr><td>环已酮</td><td>44</td><td>1.1</td><td>8.1</td><td>420</td><td>1,1,1-三氯乙烷</td><td>无</td><td>10.0</td><td></td><td></td></tr></table></body></html>  \n\n由以上论述不难看出，目前大量应用的传统溶剂型涂料中，不可避免地要使用大量的有机溶剂，而在这些涂料产品形成涂膜的过程中，又要挥发到大气中去，这不仅造成对人体的毒害、对生态环境的污染、增加了生产及施工场所的火灾及爆炸危险，并且也是能源及资源的巨大浪费。因此，国内外涂料工业正在下大力气致力于研究及使用不含或少含有机溶剂的低污染涂料，如高固体分涂料、无溶剂涂料、水性涂料及粉末涂料。这些涂料产品的应用和发展，无疑会给人类社会带来福音。  \n\n以上我们阐述了溶剂的6个特性。其中溶解力和挥发速率是最主要的特性，表面张力和黏度对漆料及涂料性能的影响日趋重要，生态环境和人体健康的保护将对溶剂选用的限定更加严格。除此之外溶剂作为涂料生产的原料，其价格及资源也是不容忽视的因素。因此依据本节所论述的溶剂的溶解力、黏度、挥发速率、表面张力、电阻率、毒性和安全性，以及价格和资源诸项因素，科学地选择溶剂，组成涂料产品配方，是一个全面衡量及扶择的过程。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 641,
+        "chunk": "# 第四节活性分散介质  \n\n现代意义上的无溶剂涂料系指采用活性溶剂作为溶解介质的涂料。在其成膜过程中，活性溶剂与树脂交联反应，成为涂膜的组成部分，而不像一般溶剂那样挥发逸出。与溶剂型涂料比较，特点是：一次涂装可得较厚涂膜，提高工效；无溶剂挥发到大气中，减少污染，避免溶剂中毒和火灾。常用的品种有： $\\textcircled{1}$ 无溶剂聚酯涂料，即不饱和聚酯涂料； $\\textcircled{2}$ 无溶剂环氧涂料 (小分子缩水甘油醚类)； $\\textcircled{3}$ 光固化丙烯酸涂料 (如季戊四醇三丙烯酸酯等)； $\\textcircled{4}$ 无溶剂聚氨酯涂料； $\\textcircled{5}$ 无溶剂有机硅涂料等。目前有关活性稀释剂的应用主要集中在无溶剂环氧涂料和光固化丙烯酸涂料，技术比较成熟。",
+        "category": " Introduction"
+    },
+    {
+        "id": 642,
+        "chunk": "# 一、无溶剂环氧涂料用活性稀释剂  \n\n环氧活性稀稀剂主要为小分子缩水甘油醚类，分为单环氧化物和多环氧化物，按其类型又分为脂肪族型和芳香族型。从理论上讲，单环氧活性稀释剂会使热变形温度降低，而多环氧活性稀释剂影响较小。脂肪族型比芳香族型稀释效果好，而芳香族型有更好的耐酸碱性。因此，应根据环氧涂料固化的性能（黏度、力学性能、耐酸碱性、耐热变形温度等）进行选择。单环氧活性稀释剂稀释能力大于多环氧活性稀释剂，而多环氧活性稀释剂对维持环氧涂料性能较好。而从热力学性能分析，热变形温度——物体受热开始发生变形的临界温度是衡量环氧固化物的一个重要指标，由于多环氧活性稀释剂交联密度高，因此热力学性能较单环氧活性稀释剂损失小，而芳香族活性稀释剂由于具有较好的刚性结构因此较脂肪族活性稀释剂热力学性能损失小。环氧活性稀释剂对力学性能和热力学性能的影响：多环氧活性稀释剂交联密度高，因此较单环氧活性稀释剂力学性能好，芳香族活性稀释剂由于具有较好的刚性结构因此较脂肪族活性稀释剂力学性能好，长分子链的活性稀释剂有很好的增韧能力，这对改进环氧产物刚性大、韧性低有很好的作用。以下介绍几种国内外主要环氧活性稀释剂品种。",
+        "category": " Introduction"
+    },
+    {
+        "id": 643,
+        "chunk": "# 1.三羟甲基丙烷三缩水甘油醚  \n\n分子式： $\\mathrm{C_{15}H_{26}O_{6}}$ ，相对分子质量：398，密度为 $1.16\\mathrm{g}/\\mathrm{cm}^{3}$ ，环氧当量为 $135\\sim160$ 具有三个羟基的环氧稀释剂，因为三个羟基及三个环氧基的存在使其在作为环氧树脂的稀释剂使用时，在降低环氧体系产品的耐温性方面有较强的优越性。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 644,
+        "chunk": "# 2.新戊二醇二缩水甘油醚  \n\n分子式：CH2oO，相对分子质量：216，密度为1.04g/cm，环氧当量为143～166，由新戊二醇与环氧氯丙烷脱水反应而成，无刺激性气味，沸点大于150℃，分子内含有两个环氧基团，固化时参与反应，形成链状及网状。稀释效果与单缩水甘油醚相当。但固化后树脂的拉伸强度，弯曲强度，抗压强度，冲击强度等力学性能以及适应期均优于单缩水甘油醚固化的树脂。作为环氧树脂的活性稀释剂可以在同样温度条件下降低环氧树脂与固化剂的反应活性，广泛用于地坪、无溶剂涂料、层压、胶黏剂和透明环氧体系及电工浇注成形的环氧体系。作为纤维素整理剂可增加纤维素的柔韧性、牢度、耐碱性、染色性等，可用于棉、麻，毛丝等织物整理。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 645,
+        "chunk": "# 3.1,4-丁二醇二缩水甘油醚  \n\n分子式： $\\mathrm{C_{10}H_{18}O_{4}}$ ，相对分子质量：202，密度为 $1.10\\mathbf{g}/\\mathrm{cm}^{3}$ ，环氧当量为 $130\\sim175$ .由正丁醇与环氧氯丙烷脱水反应而成，无刺激性气味，沸点大于 $150^{\\circ}\\mathrm{C}$ ，分子内含有两个环氧基团，固化时参与反应，形成链状及网状。固化后树脂的拉伸强度，抗弯曲强度，抗压强度，抗冲击强度等力学性能以及适应期均优于单缩水甘油醚固化的树脂。由于是长链型环氧活性稀释剂通常作为环氧树脂的柔性增韧剂，广泛用于无溶剂涂料、层压、胶黏剂等环氧体系。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 646,
+        "chunk": "# 4.聚丙二醇二缩水甘油醚  \n\n环氧当量为 $278\\sim360$ ，由聚丙二醇与环氧氯丙烷脱水反应而成，淡黄色液体，由于其独特的长链型分子结构因此完全可以取代通用的环氧柔性增韧剂，被广泛用于无溶剂涂料、层压、胶黏剂等环氧体系。作为纤维素整理剂可增加纤维素的柔韧性、牢度、耐碱性、染色性等，可用于棉、麻、毛丝等织物整理。可使纤维的拉伸强度提高。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 647,
+        "chunk": "# 5、乙二醇二缩水甘油醚  \n\n分子式： $\\mathbf{C}_{10}\\mathbf{H}_{14}\\mathbf{O}_{4}$ ，相对分子质量：198，密度为 $1.08\\mathbf{g}/\\mathbf{cm}^{3}$ ，环氧当量为 $133\\sim155$ 由乙二醇与环氧氯丙烷脱水反应而成，浅黄色透明液体，被广泛用于无溶剂涂料、层压、胶黏剂等环氧体系。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 648,
+        "chunk": "# 6.苄基缩水甘油醚  \n\n密度为 $0.98g/\\mathrm{cm}^{3}$ ，环氧当量为 $_{130\\sim175}$ ，由苯甲醇与环氧氯丙烷脱水反应而成，无色透明液体，黏度低、气味小、沸点高、固化物耐热性较好、韧性优良等诸多优越性，可广泛用于高要求环氧树脂灌封料、透明灌封树脂、无气味环氧地坪涂料等要求较高的环氧树脂，无溶剂稀释。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 649,
+        "chunk": "# 7.丁基缩水甘油醚  \n\n分子式： $\\mathbf{C}_{7}\\mathbf{H}_{15}\\mathbf{O}_{2}$ ，相对分子质量：131，密度为 $0.878/{\\mathrm{cm}}^{3}$ ，无色透明液体，低毒。其化学名称为环氧丙烷丁基醚，系丁醇与环氧氯丙烷经开环醚化再经环氧化而制得的缩水甘油型活性环氧稀释剂，分子内含醚键和环氧基，稀释环氧树脂效果好，固化时参与固化，形成均一体系，是常用的环氧树脂活性稀释剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 650,
+        "chunk": "# 8.脂肪缩水甘油醚  \n\n密度为 $0.89\\mathrm{g}/\\mathrm{cm}^{3}$ ，环氧当量为 $285\\sim330$ ，无色透明液体，它是一种单官能基稀释剂，用于降低树脂体系的黏度，要达到理想的降黏效果，必须添加到最适比例。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 651,
+        "chunk": "# 9.烯丙基缩水甘油醚  \n\n分子式： $\\mathbf{C}_{6}\\mathrm{H}_{10}\\mathbf{O}_{2}$ ，相对分子质量：114，密度为 $0.97\\mathrm{g}/\\mathrm{cm}^{3}$ ，环氧当量为 $98\\sim102\\$ ，是一种单官能基稀释剂，用于降低树脂体系的黏度，与环氧树脂搭配使用，可以加入较高比例填料，具有较高的渗透性。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 652,
+        "chunk": "# 10.苯基缩水甘油醚  \n\n由苯酚与环氧氯丙烷经开环醚化，再经环氧化而制得的缩水甘油醚型活性稀释剂，黏度较低 $(0,007\\mathrm{{Pa}\\cdot\\circ}\\$ 左右），能与环氧树脂以任意比例混溶。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 653,
+        "chunk": "# 11.脂环族环氧树脂化合物  \n\n无色或淡黄色透明油状液体，对皮肤无刺激，无异味，能与苯、甲苯、丙酮等有机溶剂互溶，是环氧树脂很好的稀释剂。随着用量的增加，显著降低环氧体系黏度，热变形温度几乎不变，这是一般环氧稀释剂不能与之相比的。固化后交联度高，并保持原有环状结构，所以耐热温度高、力学性能好。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 654,
+        "chunk": "# 二、聚氨酯涂料用活性稀释剂",
+        "category": " Introduction"
+    },
+    {
+        "id": 655,
+        "chunk": "# 1.-丁内酯  \n\n无色油状液体，有类似丙酮气味，沸点范围 $201\\sim206^{\\circ}\\mathrm{C}$ ，凝固点约 $-43\\mathrm{{\\bar{C}}}$ ，密度$(20^{\\circ}\\mathsf{C})1.13\\mathsf{g}/\\mathsf{c m}^{3}$ ，闪点 $104\\Upsilon$ ，能与水、醇、酯及芳烃混溶，有限溶解于脂肪烃和环脂烃。可用作聚氨酯的强度改性剂（活性稀释剂）以及聚氨酯和氨基涂料体系的固化剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 656,
+        "chunk": "# 2.亚丙基碳酸酯  \n\n亚丙基碳酸酯是一种低黏度、高沸点化合物，具有生物降解性能，广泛应用于溶剂。可作为聚氨酯预聚体的降黏剂、活性稀释剂和增塑剂，用于喷涂聚氨酯弹性体体系等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 657,
+        "chunk": "# 3.唑烷  \n\n唑烷活性稀释剂的水解活性比醛（酮）亚胺低，稳定性较好，在固化环境下遇湿离解后产生羟基或仲氨基，参加固化反应，而生成的少量副产物酮（或醛）与树脂具有良好的相容性，慢慢挥发，不影响固化后树脂的外观。它不但不会像增塑剂那样降低硬度，而且可得到良好耐化学品性能、柔韧性、抗冲击性、耐磨性和附着力好的涂膜。唑烷与水反应快，因而体系中无 $\\mathrm{CO}_{2}$ 气体生成，防止涂层发泡和针孔现象的发生。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 658,
+        "chunk": "# 三、光固化涂料用活性稀释剂  \n\n光固化涂料中的活性稀释剂通常称为单体（monomer）或功能性单体（functionalmon-omer)，它是一种含有可聚合官能团的有机小分子，在光固化涂料的各种组分中活性稀释剂都是一个重要的组成。它不仅溶解和稀释低聚物，调节体系的黏度，而且参与光固化过程，影响涂料的光固化速率和固化膜的各种性能，因此选择合适的活性稀释剂是光固化涂料配方设计的重要环节。  \n\n光固化涂料用活性稀释剂从结构上看，自由基光固化用的活性稀释剂都是具有C—C不饱和双键的单体，如丙烯酰氧基、甲基丙烯酰氧基、乙烯基、烯丙基，光固化活性依次为丙烯酰氧基>甲基丙烯酰氧基 $>$ 乙烯基>烯丙基。因此，自由基光固化活性稀释剂主要为丙烯酸酸类单体。阳离子光固化用的活性稀释剂为具有乙烯基醚 $\\mathrm{CH}_{2}\\mathrm{\\mathrm{~-CH}\\mathrm{-}O}$ 一或环氧基的单体。乙烯基醚类单体可参与自由基光固化，因此可用作两种光固化体系的活性稀释剂。  \n\n活性稀释剂按其每个分子所含反应性基团的多少，可以分为单官能团活性稀释剂、双官能团活性稀释剂和多官能团活性稀释剂。每个分子中含有官能团的数目为官能度，所以单官能团的活性稀释剂的官能度为1，双官能团活性稀释剂的官能度为2，多官能团的活性稀释剂的官能度可以是3、4或更多。活性稀释剂中含有可参与光固化反应的官能团越多，官能度越大，则光固化反应活性越高，光固化的速率越快。从光固化活性看：多官能团活性稀释剂 $>$ 双官能团活性稀释剂 $>$ 单官能团活性稀释剂。  \n\n随着光固化涂料用活性稀释剂官能度的增加，除了增加光固化反应活性外，同时增加固化膜的交联密度。单纯的单官能团的单体聚合后，只能得到线型聚合物，不发生交联。当官能度 ${\\geqslant}2$ 的活性稀释剂存在时，光固化后得到交联聚合物网络，官能度高的活性稀释剂可得到高交联度的网状结构。交联度的高低对固化膜的物理力学性能和化学性能产生极大的影响。表2-3-28列出了活性稀释剂官能度和分子量对固化膜性能的影响规律。  \n\n表2-3-28活性稀释剂官能度和分子量对固化膜性能的影响规律  \n\n\n<html><body><table><tr><td>固化膜性能</td><td>团化速率</td><td>交联度</td><td>伸长率</td><td>硬度</td><td>柔韧性</td><td>耐磨性</td><td></td><td>抗冲击性 热稳定性 耐化学性</td><td></td><td>收缩率</td></tr><tr><td>官能度提高</td><td>馒一快</td><td>低→高</td><td>高→ 低</td><td>软硬</td><td></td><td>差好</td><td>好一差</td><td>一好</td><td>差→好</td><td>低→商</td></tr><tr><td>分子量增加</td><td>慢→快</td><td>高一→低</td><td>低→高</td><td>硬1→ 软</td><td></td><td>好→差</td><td>差→好</td><td>好→差</td><td>好→差</td><td>商→低</td></tr></table></body></html>  \n\n活性稀释剂自身的化学结构对固化膜的性能有很大影响，因此在制备光固化涂料时，要根据涂料性能要求，选择合适的活性稀释剂结构。表2-3-29列出活性稀释剂化学结构对固化膜性能的影响。  \n\n表2-3-29活性稀释剂化学结构对固化膜性能的影响  \n\n\n<html><body><table><tr><td>活性稀释剂结构</td><td>固化膜性能特点</td></tr><tr><td>链烷结构</td><td>耐高湿，疏水性，耐候性，抗黄变，耐化学药品，促进附着力</td></tr><tr><td>酶结构</td><td>耐候性（耐高温、耐黄变、抗紫外线），耐溶剂，但遇碱易水解，良好的附着力</td></tr><tr><td>芳香环结构</td><td>耐高温，耐化学药品，提供硬度、附着力、疏水性，易黄变</td></tr><tr><td>酯环结构</td><td>耐高温，耐候性，不黄变，耐化学药品，提供附着力、疏水性</td></tr><tr><td>醚结构</td><td>固化快，耐碱和链烷类溶剂，对环氟和聚氨酯溶解力良好，一旦氧化易黄变</td></tr></table></body></html>  \n\n活性稀释剂中随着官能团的增多，其分子量也相应增加，分了间相互作用力增大，因而黏度也增大，这样稀释剂作用就减少。从活性稀释剂的黏度看：多官能团活性稀释剂 $>$ 双官能团活性稀释剂 $>$ 单官能团活性稀释剂。从活性稀释剂的稀释作用看：单官能团活性稀释剂 $>$ 双官能团活性稀释剂 $>$ 多官能团活性稀释剂。在制备光固化涂料选择活性稀释剂时，应考虑以下因素： $\\textcircled{1}$ 低黏度，稀释能力强； $\\textcircled{2}$ 低毒性，低气味，低挥发，低刺激； $\\textcircled{3}$ 低色相，特别在无色体系、白色体系中必须加以考虑； $\\textcircled{4}$ 低体积收缩，增加对基材的附着力； $\\textcircled{5}$ 高反应性，提高光固化速率； $\\textcircled{6}$ 高溶解性，与树脂相溶性好，对光引发剂溶解性好； $\\textcircled{7}$ 高纯度，水分、溶剂、酸含量、聚合物含量低； $\\textcircled{8}$ 玻璃化温度适合涂层性能的要求； $\\textcircled{9}$ 热稳定性好，利于生产加工、运输和贮存； $\\mathfrak{Q}$ 价格便宜，降低生产成本。要根据光固化涂料涂装需要的黏度、固化速率、基层的附着性能、涂层所要求的物理力学性能综合考虑进行选择。单一的活性稀释剂不能满足上述要求，大多要选择两种或多种不同官能度的活性稀释剂搭配，以获得  \n\n综合性能最佳的涂料配方。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 659,
+        "chunk": "# （一）单官能团活性稀释剂  \n\n单官能团活性稀释剂每个分子仅含一个可参与光固化反应的活性基材，分子量较低，因此具有如下的特点： $\\textcircled{1}$ 黏度低，稀释能力强； $\\textcircled{2}$ 光固化速率低，这是因为单官能团活性稀释剂的反应基团含量低，导致光固化速率低； $\\textcircled{3}$ 交联密度低，只含一个光活性基团，因此在光固化反应中不会产生交联点，使反应体系交联密度下降； $\\textcircled{4}$ 转化率高，由于单官能团活性稀释剂的碳碳双键的含量低，黏度小，容易参与聚合，故转化率高； $\\textcircled{5}$ 体积收缩率低，在自由基加成聚合时，碳碳双键转化成单键，由原来分子间距离变成碳-碳单键，距离变小、密度增大，造成体积收缩。但单官能团活性稀释剂因碳-碳双键含量低，所以体积收缩较少；$\\textcircled{6}$ 挥发性较大，气味大、易燃，毒性也相对较大。单官能团活性稀释剂从结构上的不同可分为丙烯酸烷基酯、（甲基）丙烯酸羟基酯、带有环状结构或苯环的（甲基）丙烯酸酯和乙烯基活性稀释剂。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 660,
+        "chunk": "# 1.丙烯酸烷基酯  \n\n(1）丙烯酸丁酯（BA）低黏度，稀释效果好，早期作为活性稀释剂使用，但气味大、挥发性大、易燃，故现在已基本上不再使用。(2）丙烯酸异辛酯（2-EHA）相对分子质量为184，沸点为 $213^{\\circ}\\mathrm{C}$ ，密度为 $0.881_{\\mathbf{B}}/$ $\\mathsf{c m}^{3}$ ，低黏度，稀释效果好，低玻璃化温度，有较好的增塑效果，早期作为活性稀释剂使用，有气味大、挥发性稍大等缺点。(3）丙烯酸异癸酯（IDA）相对分子质量为212，沸点为 $158^{\\circ}\\mathrm{C}$ ，密度为0. $885\\mathrm{g}/\\mathrm{cm}^{3}$ 低黏度，稀释效果好，低玻璃化温度，有较好的增塑效果，挥发性较小。（4）丙烯酸月桂酯（LA）相对分子质量为240，密度为 $0.888/{\\mathrm{cm}}^{3}$ ，低黏度，低挥发，有疏水性脂肪族长主链，低玻璃化温度，有较好的增塑效果。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 661,
+        "chunk": "# 2.（甲基）丙烯酸羟基酯  \n\n（1）丙烯酸羟乙酯（HEA）和丙烯酸羟丙酯（HPA）这两种活性稀释剂具有高沸点、低黏度、低玻璃化温度、反应活性适中，带有羟基，有利于提高对极性基材的附着力，是早期最常用的活性稀释剂，但皮肤刺激性和毒性较大，目前也较少使用。由于HEA和HPA分子带有丙烯酰氧基，又含有羟基，可与异氰酸基反应，现主要用于制备PUA的原料。  \n\n(2）甲基丙烯酸羟乙酯（HEMA）和甲基丙烯酸羟丙酯（HPMA）这两种活性稀释剂具有高沸点、低黏度，因是甲基丙烯酸酯，所以固化速率比HEA和HPA慢，但皮肤刺激性和毒性低于HEA和HPA，带有羟基，有利于提高对极性基材的附着力。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 662,
+        "chunk": "# 3.带有环状结构或苯环的（甲基）丙烯酸酯  \n\n（1）甲基丙烯酸缩水甘油酯（GMA）相对分子质量为142，沸点为 $176^{\\circ}\\mathrm{C}$ ，密度为$1.07318/\\mathrm{cm}^{3}$ ，黏度较低，带有环氧基，有利于提高附着力，但价格较贵，因是甲基丙烯酸酯，所以固化速度较慢。  \n\n(2）甲基丙烯酸异冰片酯（IBOA）相对分子质量为208，沸点为 $275^{\\circ}C$ ，密度为$0.990\\mathrm{g}/\\mathrm{cm}^{3}$ ，具有黏度较低、高折射率和高玻璃化温度、固化收缩率低 $(8,2\\%)$ ，有利于提高附着力，低皮肤刺激性，但价格高，又有气味，影响其使用。  \n\n(3）甲基丙烯酸四氢呋喃甲酯（THFFA）具有高沸点、黏度较低、玻璃化温度较低含有极性的四氢呋喃环，有利于附着力的提高。  \n\n（4）丙烯酸苯氧基乙酯（POEA）相对分子质量为192，沸点为 $134^{\\circ}\\mathrm{C}$ ，密度为 $1.10\\mathbf{g}/\\mathrm{cm}^{3}$ 具有高沸点、黏度低、玻璃化温度较低，反应活性较高，低皮肤刺激性，但有酚的气味。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 663,
+        "chunk": "# 4.乙烯基活性稀释剂  \n\n（1）苯乙烯（ST）最早与不饱和聚酯配合作为第一代光固化涂料应用于木器涂料，虽然价格较低、黏度低、稀释能力强，但因其高挥发性、高易燃性、气味大、毒性大以及固化速率较慢等缺点，目前在光固化涂料中很少使用ST作活性稀释剂。  \n\n(2）醋酸乙烯酯（VA）价格便宜，低黏度，稀释能力强，反应活性较高，但低沸点、高挥发性、易燃易爆，实际上光固化涂料中不采用VA作为活性稀释剂。  \n\n(3）N-乙烯基吡咯烷酮（NVP）低黏度，稀释能力强，反应活性高，低皮肤刺激性，曾是最受欢迎的活性稀释剂。但因价格较贵、气味大，特别是发现有致癌毒性，限制了它的使用。一般用量不能超过 $10\\%\\sim20\\%$ ，因NVP及其聚合物都是水溶性的，加人量大会影响涂料的耐水性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 664,
+        "chunk": "# （二）双官能团活性稀释剂  \n\n双官能团活性稀释剂每个分子中含有两个可参与光固化反应的活性基团，因此光固化速率比单官能团活性稀释剂要快，成膜时发生交联，有利于提高固化膜的力学性能和耐抗性。由于分子量增大，黏度也相应增加，但仍保持良好的稀释性，挥发性较小，气味较低，因此双官能团活性稀释剂大量应用于光固化涂料中。双官能团活性稀释剂从二元醇结构上可分为乙二醇类二丙烯酸酯、丙二醇类二丙烯酸酯和其他二醇类二丙烯酸酯。",
+        "category": " Introduction"
+    },
+    {
+        "id": 665,
+        "chunk": "# 1.乙二醇类二丙烯酸酯  \n\n(1）二乙二醇类二丙烯酸酯（DEGDA）相对分子质量为214，沸点为 $\\mathrm{\\dot{~}}100\\dot{0}$ ，密度为$1.006\\mathrm{g/cm^{3}}$ ，具有低黏度、光固化速率快的特点，但皮肤刺激性严重，故现在很少使用。  \n\n(2）三乙二醇类二丙烯酸酯（TEGDA）相对分子质量为258，沸点为 $162^{\\circ}\\mathrm{C}$ ，密度为$1.109\\mathrm{g}/\\mathrm{cm}^{3}$ ，具有低黏度、光固化速率快等特点，因皮肤刺激性大，现在很少使用。  \n\n(3）聚乙二醇二丙烯酸酯系列包括聚乙二醇（200）二丙烯酸酯［PEG（200）DA]、聚乙二醇（400）二丙烯酸酯［PEG（400）DA]、聚乙二醇（600）二丙烯酸酯[PEG（600）DA］三种，随着分子量的增加，黏度变大，玻璃化温度下降，毒性和皮肤的刺激性降低，因此，漆膜的柔韧性增加，疏水性也相应增加。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 666,
+        "chunk": "# 2.丙二醇类二丙烯酸酯  \n\n(1）二丙二醇类二丙烯酸酯（DPGDA）具有低黏度、稀释能力强、光固化速率快的特点，但皮肤刺激性稍大，是光固化涂料常用的稀释剂之一。  \n\n(2）三丙二醇类二丙烯酸酯（TPGDA）黏度较低，稀释能力强，光固化速率快，体积收缩较小，皮肤刺激性也较小，价格较低，是目前光固化涂料最常用的双官能团活性稀释剂。 K 形",
+        "category": " Introduction"
+    },
+    {
+        "id": 667,
+        "chunk": "# 3.其他二醇类二丙烯酸酯  \n\n(1）1，4-丁二醇二丙烯酸酯（BDDA）相对分子质量为198，沸点为 $275^{\\circ}C$ ，密度为$1.0578/{\\mathrm{cm}}^{3}$ ，低黏度，对低聚物溶解性好、稀释能力强，但对皮肤刺激性较大。  \n\n(2）1，6-己二醇二丙烯酸酯（HDDA）相对分子质量为226，沸点为 $295\\mathrm{^{\\circ}C}$ ，密度为$1.038/\\mathrm{cm}^{3}$ ，具有低黏度、稀释能力强、对塑料附着力好的特点，可改善固化膜的柔韧性，但对皮肤刺激性较大，价格较高，是光固化涂料常用的活性稀释剂之一。  \n\n（3）新戊二醇二丙烯酸酯（NPGDA）相对分子质量为212，密度为1.03g/cm，具有低黏度、稀释能力强、高活性、光固化速率快的特点，对塑料附着力好，玻璃化温度较高，但对皮肤刺激性较大，是光固化涂料常用的活性稀释剂之一。  \n\n（4）邻苯二甲酸乙二醇二丙烯酸酯（PDDA）价格便宜，光固化速率快，是我国自行开发的活性稀释剂，效果稍差。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 668,
+        "chunk": "# （三）多官能团活性稀释剂  \n\n多官能团活性稀释剂每个分子中含有三个或三个以上可参与光固化反应的活性基团，因此不仅光固化速率快，而且交联密度大，相应地固化膜硬度高，脆性大，耐抗性优异。分子量大，黏度高，稀释能力较差；高沸点，低挥发性，收缩率大。常用的多官能团活性稀释剂有以下几种。  \n\n（1）三羟甲基丙烷三丙烯酸酯（TMPTA）相对分子质量为296，密度为 $1.11_{8}/{\\mathrm{cm}}^{3}$ ·黏度较大，但在多官能团活性稀释剂中是最低的一种，光固化速率快，交联密度大，固化膜坚硬而发脆，耐抗性好。价格较便宜，虽然皮肤刺激性较大，但仍是光固化涂料中最常用的多官能团活性稀释剂。  \n\n(2）季戊四醇三丙烯酸酯（PETA）和季戊四醇四丙烯酸酯（PETTA）这两种活性稀释剂黏度大，稀释能力差；光固化速率快，交联密度大；固化膜硬而脆，耐抗性好。PETA有羟基，有利于提高附着力，但PETA毒性大，怀疑有致癌性，因而限制其使用。  \n\n(3）二缩三羟甲基丙烷四丙烯酸酯（DTMPTTA）相对分子质量为482，密度为$1.11\\mathrm{g/cm^{3}}$ ，具有高黏度，反应活性较高，高交联密度，极低的皮肤刺激性，固化膜较硬，富有弹性而不脆，耐拉伸性优良。在光固化涂料中不作活性稀释剂，而作为提高光固化速率和交联密度使用。  \n\n(4）二季戊四醇五丙烯酸酯（DPPA）和二季戊四醇六丙烯酸酯（DPHA）这两种活性稀释剂黏度高，极高的反应活性和交联密度，极低的皮肤刺激性；固化膜有极高的硬度、耐刮性和耐抗性。在光固化涂料中作为提高光固化速率和交联密度使用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 669,
+        "chunk": "# （四）新型的活性稀释剂  \n\n乙烯基醚类活性稀释剂是20世纪90年代开发的一类新型活性稀释剂，它是含有乙烯基醚或丙烯基醚结构的活性稀释剂。氧原子上的孤电子对与碳-碳双键发生共轭，使双键的电子云密度增大，所以乙烯基醚的碳-碳双键是富电子双键，反应活性高，能进行自由基聚合、阳离子聚合和电荷转移复合物交替共聚。因此，乙烯基醚可在多种辐射固化体系中应用，例如，在自由基固化体系、阳离子固化体系以及混杂体系（自由基光固化与阳离子光固化同时存在）中作为活性稀释剂使用。另外，如与马来酰亚胺类缺电子双键配合，则乙烯基醚与马来酰亚胺形成强烈的电荷转移复合物，经光照后，可在没有光引发剂存在下发生聚合，这也是正在研究开发中的无光引发剂的光固化体系。  \n\n乙烯基醚与丙烯酸酯类活性稀释剂相比，具有低黏度、稀释能力强、高沸点、气味小、毒性小、皮肤的刺激性低、优良的反应活性等优点，但价格较高，影响了它在光固化涂料中的应用。目前商品化的乙烯基醚类活性稀释剂有：三甘醇二乙烯基醚（DVE-3）、1，4-环已基二甲醇二乙烯基醚（CHVE）、4-羟丁基乙烯基醚（HBVE）、甘油碳酸酯丙烯基醚(PEPC)、十二烷基乙烯基醚（DDVE)。  \n\n最新开发的第三代（甲基）丙烯酸酯类活性稀释剂为含甲氧端基的（甲基）丙烯酸酯活性稀释剂，它们除了具有单官能团活性稀释剂的低收缩性和高转化率外，还具有高反应活性。表2-3-30是沙多玛公司和科宁公司的几种甲氧基化丙烯酸酯活性稀释剂的物理性能。  \n\n表2-3-30甲氧基化丙烯酸醋活性稀释剂的物理性能  \n\n\n<html><body><table><tr><td>公司</td><td>活性稀释剂</td><td></td><td>黏度（25C）/mPa·s密度（25C）/（g/cm）表面张力/（mN/m）</td><td></td><td>玻璃化温度/C</td></tr><tr><td rowspan=\"4\">沙多玛</td><td>CD550</td><td>19</td><td></td><td></td><td>62</td></tr><tr><td>CD552</td><td>239</td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td>65</td></tr><tr><td>CD553</td><td>50</td><td></td><td></td><td></td></tr><tr><td rowspan=\"3\">科宁</td><td>8016</td><td>8</td><td>0.99</td><td>30.1</td><td></td></tr><tr><td>8127</td><td>8</td><td>0.96</td><td>25.7</td><td></td></tr><tr><td>8148</td><td>28</td><td>1.08</td><td>35.2</td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 670,
+        "chunk": "# 四、活性稀释剂的毒性  \n\n目前光固化涂料中常用的活性稀释剂大多数沸点很高，蒸气压很小，不易挥发，在光固化过程中又都参与固化反应，所以在生产和涂装中极少挥发到大气中，也就是说具有很低的挥发性有机物（VOC）含量，这就使光固化涂料成为低污染的环保型涂料。  \n\n从化学品的毒性看，光固化涂料所用的丙烯酸酯类活性稀释剂具有较低的毒性，但在生产和使用时，长时间暴露在丙烯酸酯的气氛下，则会引起皮肤、黏膜和眼睛的刺激，直接接触会产生刺激性疼痛，甚至出现过敏、灼伤；由于沸点高，室温下蒸气压很低，对呼吸系统没有明显伤害。  \n\n化学毒性通常用半致死计量 $\\mathrm{LD}_{50}$ （lethaldose-50）来表示毒性程度，通过实验动物（鼠、兔）的经口吸收、皮肤吸收和吸人吸收造成死亡的 $50\\%$ 来确定毒性大小，单位$\\mathbf{m}_{B}/\\mathbf{k}_{B}$ ，见表2-3-31。  \n\n<html><body><table><tr><td>LDs /(mg/kg)</td><td><</td><td>1~50</td><td>50~500</td><td>500~5000</td><td>5000~15000</td><td>>15000</td></tr><tr><td>毒性程度</td><td>剧毒</td><td>高毒</td><td>中毒</td><td>低毒</td><td>实际上无毒</td><td>相当非毒品</td></tr></table></body></html>  \n\n皮肤刺激性可用初期皮肤刺激指数PII（primary skininitiationindex）来表示，见表2-3-32。  \n\n表2-3-32初期皮肤刺激指数PII的皮肤刺激性程度表示  \n\n\n<html><body><table><tr><td>PII</td><td>0.00~0.03</td><td>0.04~0.99</td><td>1. 00 ~1.99</td><td>2.00~2.99</td><td>3.00~-5.99</td><td>6.00~8.00</td></tr><tr><td>皮肤刺激性程度</td><td>无刺激</td><td>略感刺激</td><td>蒋刺激</td><td>中刺激</td><td>刺激性较强</td><td>强刺激</td></tr></table></body></html>  \n\n表2-3-33和表2-3-34分别列出了部分活性稀释剂的半致死计量 $\\scriptstyle\\mathrm{LD}_{50}$ 和初期皮肤刺激指数PII。  \n\n表2-3-31半致死计量LDs的毒性表示  \n表2-3-33部分活性稀释剂的半致死计量 $\\mathbf{LD_{50}}$   \n\n\n<html><body><table><tr><td colspan=\"2\">活性稀释剂</td><td>BA</td><td>2-EHA</td><td>IDA</td><td>HEA</td><td>HPA</td><td>IBOA</td><td>DEGDA</td><td>TMPTA</td><td>PETA</td><td>NGA(PO)DA</td></tr><tr><td>LDso/</td><td>经口</td><td>3730</td><td>5600</td><td>10885</td><td>600</td><td>1120</td><td>2300</td><td>1568</td><td>>5000</td><td>1350</td><td>15000</td></tr><tr><td>(mg/kg）皮肤</td><td></td><td>3000</td><td>7488</td><td>3133</td><td></td><td></td><td></td><td></td><td>5170</td><td>>2000</td><td>5000</td></tr></table></body></html>  \n\n在生产和使用过程中，应避免直接接触活性稀释剂，一旦接触应立即用清水冲洗有关部位。若发现出现红斑甚至水疱，应立即去医院进行治疗。  \n\n表2-3-34部分活性稀释剂的初期皮肤刺激指数PII  \n\n\n<html><body><table><tr><td>活性稀释剂</td><td>NVP</td><td>IDA</td><td>POEA</td><td>IBOA</td><td>DEGDA</td><td>TEGDA</td><td>PEG(200)DAPEG(400)DA NPGDA</td><td></td><td></td></tr><tr><td>PII</td><td>0.4</td><td>2.2</td><td>1.5</td><td>1.8</td><td>6.8</td><td>6.0</td><td>3.0</td><td>0.9</td><td>4.96</td></tr><tr><td>活性稀释剂</td><td>DPGDA</td><td>TPGDA</td><td>BDDA</td><td>HDDA</td><td>TMPTA</td><td>PETA</td><td>PETTA</td><td>DTMPTTA</td><td>DPPA</td></tr><tr><td>PII</td><td>5.0</td><td>3.0</td><td>5.5</td><td>5.0</td><td>4.8</td><td>4.3</td><td>0.4</td><td>0.5</td><td>0.54</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 671,
+        "chunk": "# 五、活性稀释剂的贮存和运输",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 672,
+        "chunk": "# 1.贮存容器  \n\n活性稀释剂要存放在不透明、深色、干燥的内衬酚醛树脂或聚乙烯的铁桶或深色的聚乙烯桶内。铁或铜类容器会引发聚合，因此应避免接触这类材料。注意容器中要留有一定空间，以满足阻聚剂对氧气的需要。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 673,
+        "chunk": "# 2.贮存温度  \n\n贮存温度低于 $30\\Upsilon$ ，最好 $10\\mathrm{{^circC}}$ 左右。大批贮存推荐温度为 $16\\sim27^{\\circ}C$ 。如果发生冻结，请将材料加热至 $30\\mathsf{C}$ ，并低温搅拌混合，使阻聚剂均匀混在材料中。这些预防措施对于保持产品的性能指标是必要的，否则容易发生聚合反应，而使产品固化报废。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 674,
+        "chunk": "# 3.贮存条件  \n\n贮存时除注意温度条件外，应避免阳光直射，避免与氧化剂、引发剂和能产生自由基的物质接触。贮存时需加入足量的阻聚剂对甲氧基苯酚或对苯二酚，以增强在贮存时的稳定性。注意定期检查阻聚剂含量及材料黏度的变化以防止聚合。产品在收到6个月内使用可得到最好的效果。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 675,
+        "chunk": "# 4.运输  \n\n运输时，注意避免阳光直射，温度不要超过 $30\\mathrm{{^c}}$ ，要防止局部高温，以免发生聚合，同时不能与氧化剂、引发剂等物质放在一起。在生产过程中输送活性稀释剂时，必须要用不锈钢、聚乙烯管或其他塑料管道。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 676,
+        "chunk": "# 第五节涂料常用有机溶剂  \n\n涂料用溶剂，除水以外，一般都是挥发性的有机溶剂。由于分类方法不同可以划分为不同的系列。如按沸点高低可以分为低沸点溶剂、中沸点溶剂和高沸点溶剂；按来源划分，可以分为石油溶剂、煤焦溶剂等；按化合物类型划分，可分为脂肪烃经溶剂、芳香烃溶剂、烯类溶剂、醇类溶剂、酮类溶剂、酯类溶剂、醇醚及醚酯类溶剂和取代烃类溶剂8个系列。下面以化合物类型分类方法为序，对涂料常用的有机溶剂特性及其应用进行概述。 4",
+        "category": " Introduction"
+    },
+    {
+        "id": 677,
+        "chunk": "# 一、脂肪烃类溶剂  \n\n脂肪烃类溶剂的化学组成主要是链状烃类化合物，系石油分馏的产物。",
+        "category": " Introduction"
+    },
+    {
+        "id": 678,
+        "chunk": "# 1.石油醚  \n\n石油醚是石油的低沸点馏分，为低级烷烃的混合物。我国按沸点不同分为30～60℃、$60\\sim90\\ensuremath{\\uptau}$ 和 $90\\mathrm{\\sim}120\\mathrm{\\textperthousand}$ 三类。外观为无色透明的液体，有类似乙醚的气味。工业石油醚中含有不饱和烃、芳香烃、硫化物、酸性物质和不挥发物等杂质。可以用浓硫酸、碱、水依次洗涤，经脱水剂干燥后，再经过精馏而得到精制品。  \n\n石油醚不溶于水，能与丙酮、醋酸已酯、苯、氯仿以及甲醇以上的高级醇类混溶。能溶解甘油松香脂，部分溶解松香、沥青和芳香烃树脂。不溶解虫胶、氯化橡胶、硝化纤维素、醋酸纤维素和苄基纤维素。所以石油醚在涂料中作为成膜物溶剂的用途不大，却往往被采用为萃取剂和精制溶剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 679,
+        "chunk": "# 2.200号涂料溶剂油  \n\n溶剂汽油是由含 $\\mathbf{C}_{6}{\\sim}\\mathbf{C}_{11}$ 的烷烃、烯烃、环烷烃和少量芳香烃组成的混合物，主要成分是戊烷、已烷、庚烷和辛烷等。由原油直接蒸馏制得的直蒸汽油基本不含烯烃，通过裂化而得的汽油则含有相当量的烯烃，作溶剂使用的汽油要求不含裂化馏分和四乙基铅。200号油漆溶剂油是溶剂汽油中的一种，其沸程范围为 $145\\mathrm{\\sim}200^{\\circ}\\mathrm{C}$ ，但很少一部分可达 $210^{\\circ}\\mathrm{C}$  \n\n由于石油产地不同，其中烷烃、环烷烃和芳香烃含量不同，故来源不同的200号溶剂油的组成，特别是芳香烃含量也不同，所以其溶解力也不同。  \n\n200号涂料溶剂油开始是代替松节油在涂料工业中广泛使用的，故历史上也称作“松香水”，在国外也称作矿油精。它的溶解力属中等范围（苯胺点为 $65.6\\Upsilon$ ，贝壳松脂·丁醇值为36），可与很多有机溶剂互溶。可溶解生油、精制油，也可溶解低黏度的聚合油。但对高黏度的聚合油溶解能力差。酚醛树脂漆料、酯胶漆料、醇酸调合树脂及长油度醇酸树脂可以全部用200号涂料溶剂油溶解。中油度醇酸树脂需要和少量芳香烃一起使用。短油度醇酸树脂及其他合成树脂不能用200号涂料溶剂油溶解。除此之外，甘油松香脂、改性酚醛树脂、玛树脂、天然沥青和石油沥青都可以溶于200号涂料溶剂油，所以它在涂料工业中用途很大。",
+        "category": " Introduction"
+    },
+    {
+        "id": 680,
+        "chunk": "# 3.抽余油  \n\n抽余油系石油裂解的烷烃经铂重整后，抽提芳香烃和萘烃后余下的组分，故称作抽余油。其成分是 $C_{6}{\\sim}C_{9}$ 的脂肪烃。主要是庚烷和辛烷，芳烃占 $2.07\\%\\sim10\\%$ 。在涂料工业中主要是代替苯和甲苯，在硝基漆中做稀释剂使用，以便降低溶剂的毒性。  \n\n工业品为无色透明液体，密度为 $0.725\\mathrm{g/cm^{3}}$ ? $20\\%$ )，馏程为初馏点 $355\\mathrm{^c}$ ，50%体积馏分 $75\\mathsf{C}\\pm5\\mathsf{C}$ ， $90\\%$ 体积馏分 $100\\mathtt{C}\\mathtt{\\pm}10\\mathtt{C}$ ，终馏点 $150^{\\circ}\\mathrm{C}$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 681,
+        "chunk": "# 二、芳香烃类溶剂  \n\n芳香烃溶剂是目前涂料工业用溶剂中使用品种最多、用量最大的一类。由于其来源和分类比较复杂，加之历史上沿袭的名称及近年来规范化以后的名称混杂在一起使用，因此，从某种程度上造成了混乱。 R  \n\n根据来源不同，可将芳香烃分为焦化芳烃和石油芳烃两大类。焦化芳烃系由煤焦油分馏而得，石油芳烃系由石油产品经铂重整油、催化裂化油及甲苯歧化油精馏而得。，  \n\n焦化芳烃和石油芳烃又根据其碳原子的多少，进一步分为轻芳烃和重芳烃，一般 $\\mathbf{C}_{8}$ （包括 ${\\bf C}_{8}$ ）以下的称作轻芳烃， ${\\bf C}_{8}$ 以上的，主要是 $\\mathbf{C}_{9}\\sim\\mathbf{C}_{10}$ 的组分称作重芳烃。焦化芳烃的轻芳烃溶剂，包括焦化苯、焦化甲苯、焦化二甲苯和溶剂石脑油。石油芳烃的轻芳烃包括石油苯、石油甲苯和石油二甲苯。 ?  \n\n焦化芳烃的重芳烃在涂料中常用的有精重苯、重溶剂油和200号焦油溶剂。石油芳烃的重芳烃主要是抽提 ${\\bf C}_{8}$ 馏分以后余下的 $\\mathbf{C}_{9}$ 芳烃、 $\\mathbf{C}_{10}$ 芳烃和少量 $\\mathbf{C}_{11}$ 组分。在我国开始是以未经分馏的混合物在涂料中使用，作二甲苯和200号涂料溶剂油的替代产品。主要是为利用资源和降低成本，通用名称叫做“重芳烃”。而以后又依其馏程不同将“重芳烃”进一步分成不同的窄馏程组分，得到不同牌号的产品，在涂料中使用不仅可以代替部分二甲苯以开发资源、降低成本，同时在烘漆及卷材涂料等产品中使用，还具有其独有的特点，是二甲苯不可比拟的。这些由混合重芳烃经精馏后而得到的石油芳烃的窄馏程产品，一般称作高沸点芳烃溶剂，如以美国Exxon公司的Solvesso 100，Solvesso 150，Solvesso 200为代表的一类产品。我国天津、北京、江都等地也相应开发了类似的产品，并且已在涂料中得到广泛的应用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 682,
+        "chunk": "# 1.苯  \n\n工业苯为无色透明液体，有芳香经特有的气味，所含的杂质主要有芳香族同系物、噻吩及饱和烃等，必要时需精制除掉。苯难溶于水（偶极矩为零)，除甘油、乙二醇、二甘醇、1,4-丁二醇等多元醇外，能与乙醇、氯仿、四氯化碳、二硫化碳、冰醋酸、丙酮、甲苯、二甲苯以及脂肪烃等大多数有机溶剂相混溶。苯能溶解松香、甘油松香脂、甘油醇酸树脂、乙烯基树脂、苯乙烯树脂、丙烯酸树脂等合成树脂。聚醋酸乙烯酯树脂部分溶于苯；乙基纤维素、苄基纤维素可溶于苯；醋酸纤维素和硝基纤维素难溶于苯。  \n\n苯在涂料中的主要用途是和醋酸丁酯（或醋酸乙酯)、丙酮和丁醇配合使用，作为硝基漆的稀释剂，由于苯蒸气对人体有剧毒，故现在多被其他溶剂代替，趋于淘汰。",
+        "category": " Introduction"
+    },
+    {
+        "id": 683,
+        "chunk": "# 2.甲苯  \n\n工业甲苯为无色透明液体，有类似苯的气味，有时可能含有很少比例的相同沸程的脂肪烃。与苯相似，甲苯不溶于水，能和甲醇、乙醇、氯仿、丙酮、冰醋酸和苯多种有机溶剂混溶。甲苯能溶解干性油和除氯乙烯外的其他乙烯树脂、醇酸树脂。在甲苯中加入甲醇和乙醇可增加对醋酸纤维素的溶解能力。  \n\n由于甲苯挥发速度较快（约为二甲苯的3倍)，故很少作为溶剂使用，目前主要用作乙烯类涂料和氯化橡胶涂料混合溶剂中的组分之一。在硝基纤维素涂料中则用作稀释剂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 684,
+        "chunk": "# 3.二甲苯  \n\n涂料用二甲苯系邻、间、对位二甲苯3种同分异构体的混合物，3种异构体的任何一种都不适于单独作为溶剂在涂料中使用。  \n\n工业混合二甲苯系无色透明液体，具有芳香烃特有的气味，有时会发出微弱的荧光。由于来源不同，又分为石油混合二甲苯和焦化二甲苯。前者按馏程不同又分为 $3^{\\circ}$ 混合二甲苯和5°混合二甲苯；后者可分为 $3^{\\circ}$ $5^{\\circ}$ 和 ${{10}^{\\circ}}$ 二甲苯，其他参数基本相同。  \n\n依来源及加工路线不同，混合二甲苯中3种异构体的含量也不同，表2-3-35列出了3种路线制得的石油混合二甲苯的组成。同时混合二甲苯中往往含有乙苯、少量的甲苯、三甲苯、脂肪烃和硫化物。  \n\n单位：%  \n\n表2-3-35混合二甲苯的组成  \n\n\n<html><body><table><tr><td>异构体 类别</td><td>铂重整油</td><td>催化裂化油</td><td>甲苯歧化油</td></tr><tr><td>邻二甲苯</td><td>16~23</td><td>10~19</td><td rowspan=\"3\">23 52</td></tr><tr><td>间二甲苯</td><td>43~44</td><td>27~34</td></tr><tr><td>对二甲苯</td><td>18</td><td>12~16</td></tr><tr><td>乙苯</td><td>13~18</td><td>39~41</td><td rowspan=\"2\">22 3</td></tr><tr><td></td><td></td><td></td></tr></table></body></html>  \n\n涂料产品往往要求使用无水二甲苯。除去混合二甲苯中的少量水分，可以使用氯化钙、无水硫酸钠、五氧化二磷或分子筛作脱水剂。  \n\n二甲苯不溶于水，能与乙醇、乙醚、芳香烃和脂肪烃溶剂混溶。由于其溶解力强、挥发速率适中，是短油度醇酸树脂、乙烯树脂、氯化橡胶和聚氨酯树脂的主要溶剂，也是沥青和石油沥青的溶剂，在硝基纤维素涂料中可用作稀释剂。在二甲苯中加入 $20\\%\\sim30\\%$ 的正丁醇，可提高二甲苯对氨基树脂漆料和环氧树脂等的溶解力。由于二甲苯既可以用于常温干燥涂料，也可用于烘漆，因此是目前涂料工业中应用面最广、使用量最大的一种溶剂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 685,
+        "chunk": "# 4.溶剂石脑油  \n\n溶剂石脑油为无色或浅黄色液体，系煤焦轻油分馏所得的焦化芳香烃类混合物。沸程为$120\\sim200\\Upsilon$ ，主要由甲苯、二甲苯异构体、乙苯、异丙苯等组成。密度为（20℃/4℃）$0.85\\sim0.95\\mathrm{g/cm^{3}}$ ，闪点为 $35\\sim38\\Upsilon$ ，化学性质和甲苯、二甲苯相似。能与乙醇/丙酮等混溶，能溶解甘油松香酯、沥青等，主要用作煤焦沥青和石油沥青的溶剂，在石脑油中加人脂肪烃溶剂可提高其溶解能力，其中高沸点馏分也可用作合成树脂及纤维树脂的稀释剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 686,
+        "chunk": "# 5.高沸点芳经溶剂  \n\n如前所述，石油芳烃的重芳烃是提取 $\\mathbf{C}_{8}$ 馏分以后，余下的 $C_{9}$ ， $\\mathbf{C}_{10}$ 等高沸点馏分的混合物。开始是以“重芳烃”的名称在涂料中应用，主要目的是开发二甲苯的代用资源及降低成本。但是，在实践过程中逐渐认识到，这种开发利用资源的方法实际上是一种浪费。因为将“重芳烃”通过进一步精细加工，不仅可以分离出偏三甲苯、均三甲苯、乙基甲苯和均四甲苯这些有着非常重要用途，而又难以合成的产品，同时将余下的混合物分馏成不同沸程的窄馏分的芳烃溶剂，在涂料中使用，可使涂料用芳烃溶剂的沸程范围延伸 $50\\Upsilon$ 以上，它在溶解能力及挥发速率方面的特点都是二甲苯所不能比拟的，因此有其独特的用途。这类由石油“重芳烃”通过精馏后而制得的窄馏程产品，就是本文所述的“高沸点芳烃溶剂”，借此和粗品“重芳烃”予以区分。但是目前也有将“高沸点芳烃溶剂”称作 ${}^{\\ast}\\mathrm{c}_{\\vartheta}$ 芳烃”、“C1o芳烃”或仍然沿袭“重芳烃”名称的。  \n\n美国埃克森美孚公司生产的Solvesso系列高沸点芳烃溶剂是目前我国涂料工业使用较多的进口产品。该产品属窄馏程产品，依沸点不同分为Solvesso100、Solvesso150和Solvesso 200三种规格产品。Solvesso系列高沸点芳烃溶剂是由带有烷基支链的苯环化合物组成。Solvesso 100中 $80\\%$ 组分为 $\\mathbf{C}_{9}$ 系列芳香烃，包括甲基乙基苯及三甲基苯、满；Solvesso150主要为 $\\mathbf{C}_{10}{\\sim}\\mathbf{C}_{11}$ 系列芳香烃，包括甲基满、萘；Solvesso200则主要含有二甲基萘。它们的主要物化性能见表2-3-36。  \n\n表2-3-36Solvesso100、150、200的物化性能  \n\n\n<html><body><table><tr><td>项目</td><td>Solvesso 100</td><td>Solvesso 150</td><td>Solvesso 200</td></tr><tr><td>平均C原子数 馏程/℃</td><td>9 157~174</td><td>10 188~210</td><td>11. 3 226~279</td></tr><tr><td>混合苯胺点/C</td><td>14</td><td>16</td><td>13</td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td>贝壳松脂·丁醇值</td><td>91</td><td>90</td><td>一</td></tr><tr><td>溶解度参数</td><td>8.6</td><td>8.5</td><td>8.7</td></tr><tr><td>芳香烃含量（质量分数）/%</td><td>99</td><td>98</td><td>99</td></tr><tr><td>密度（15C/4C)/(g/cm）</td><td>0.872</td><td>0. 895</td><td>0.985</td></tr><tr><td>折射率(20°C）</td><td>1. 4993</td><td>1.5083</td><td>1.5920</td></tr><tr><td>颜色（赛波特色）</td><td>+30</td><td>+30</td><td>+10</td></tr><tr><td>闪点/°C</td><td>42</td><td>66</td><td>103</td></tr><tr><td>自燃温度/℃C</td><td>471</td><td>443</td><td>484</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>项 目</td><td>Solvesso 100</td><td>Solvesso 150</td><td>Solveso 200</td></tr><tr><td>相对挥发速率</td><td>19</td><td>4</td><td>1</td></tr><tr><td>蒸发潜热/（kJ/kg）</td><td>322</td><td>312</td><td>310</td></tr><tr><td>黏度(25℃)/mPa·s</td><td>0.8</td><td>1.1</td><td>2.8</td></tr><tr><td>表面张力（25℃）/(mN/m)</td><td>34.0</td><td>34.0</td><td>36.0</td></tr><tr><td>铜片腐蚀</td><td>1</td><td>1</td><td>1</td></tr></table></body></html>\n\n$\\Phi$ 以醋酸丁酯为100，  \n\n我国各地利用自己的石油产品资源生产的高沸点芳烃溶剂，由于粗重芳烃组成不同和加工的精细程度不同，致使产品的规格不尽统一，质量差异较大。通常对于 $\\mathbf{C}_{9}$ 重芳烃采用连续分馏的方法，截获 $145{\\sim}200^{\\circ}\\mathrm{C}$ 馏程范围内的较宽馏程的产品。而 $\\mathbf{C}_{10}$ 重芳烃采用分馏段截取馏分的方法获得的是窄馏程产品。  \n\n表2-3-37为国产 $\\mathrm{c}_{\\vartheta}$ 重芳烃的代表性产品；表2-3-38为国产 $\\mathbf{C}_{10}$ 高沸点芳烃溶剂。  \n\n表2-3-37国产C重芳烃的代表性产品  \n\n\n<html><body><table><tr><td>产地</td><td rowspan=\"2\">天津石化公司</td><td rowspan=\"2\">鞍山化工三厂</td><td rowspan=\"2\">北京前进化工厂</td></tr><tr><td>项目</td></tr><tr><td>外观</td><td>无色透明液体</td><td>无色透明液体</td><td>无色透明液体</td></tr><tr><td>馏程/C</td><td>145~185</td><td>145~200</td><td>157~200</td></tr><tr><td>密度（20C)/(g/cm）</td><td>0.85~0.87</td><td>0.86~0.875</td><td>0.878</td></tr><tr><td>闪点/C</td><td></td><td>40</td><td></td></tr></table></body></html>  \n\n表2-3-38 国产Co高沸点芳经溶剂  \n\n\n<html><body><table><tr><td></td><td colspan=\"3\">天津石化公司</td><td colspan=\"2\">江都县化工厂</td></tr><tr><td>项目</td><td>I *</td><td>I</td><td>Ⅲ</td><td>S-1500</td><td>S-2000</td></tr><tr><td>外观</td><td colspan=\"5\">水白色透明液体</td></tr><tr><td>馏程/℃</td><td>180~195</td><td>190~205</td><td>208~236</td><td>170~205</td><td>180~215</td></tr><tr><td>芳烃含量（质量分数)/%</td><td>99.9</td><td>99.9</td><td>99.8</td><td>98</td><td>98</td></tr><tr><td>闪点/℃</td><td></td><td></td><td></td><td>43</td><td>58</td></tr><tr><td>混合苯胺点/C</td><td>15.4</td><td>14.5</td><td>14.3</td><td></td><td></td></tr><tr><td>密度（20℃）/(g/cm²）</td><td>0.869</td><td>0.889</td><td>0.925</td><td>0.875</td><td>0.889</td></tr><tr><td>色相</td><td>+30</td><td>+30</td><td>+27</td><td>+30</td><td>+27</td></tr></table></body></html>  \n\n高沸点芳烃溶剂具有以下的特点：  \n\n$\\textcircled{1}$ 主要含量为芳香烃，在涂膜干燥、溶剂挥发的全部过程中都能保持高度溶解力；$\\textcircled{2}$ 在溶剂挥发的最后阶段，仍保持高度溶解力，故使涂膜无橘皮形成，并具有光泽；$\\textcircled{3}$ 可与二甲苯混合，在保持溶解能力的前提下，调整挥发速率，也可与200号溶剂油混合，在保持挥发速率的情况下提高溶解性；  \n\n$\\textcircled{4}$ 闪点较高，较安全。  \n\n高沸点芳烃溶剂对醇酸树脂的溶解力比二甲苯低，故代替二甲苯用于醇酸树脂漆中仅具有经济价值。但对于丙烯酸树脂、氨基醇酸树脂、丙烯酸醇酸树脂等有较强的溶解能力。对于汽车涂料、自行车涂料、家用电器涂料、卷材涂料、罐头涂料等烘烤型漆，则有突出的溶解能力、适宜的挥发速率和后期涂膜的流平性能。因此，易得到平整高光泽的涂膜，使用时需认真考虑混合溶剂的组成和各组分的相对比例。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 687,
+        "chunk": "# 三、烯类溶剂  \n\n烯来源于松树，它是涂料中使用最早的溶剂。在涂料中有使用价值的有松节油和双戊烯。",
+        "category": " Introduction"
+    },
+    {
+        "id": 688,
+        "chunk": "# 1.松节油  \n\n根据生产方法不同，可将松节油分为4类：松树脂松节油、木材松节油、分解蒸馏木材松节油和硫酸木材松节油。涂料生产中使用的为前两类。  \n\n采集松树脂得到的树汁，然后再经过水蒸气蒸馏得到的松节油，是由 $60\\%\\sim65\\%$ 的 $\\alpha-$ 烯和 $3\\%\\sim38\\%$ 的 $\\beta$ 烯组成。木材松节油是将树干经过破碎、溶剂萃取和蒸汽蒸馏提取的方法生产的，产品包含 $80\\%$ 的 $\\alpha$ 烯和很少的其他烯。  \n\n松节油曾是传统涂料产品中广为应用的溶剂，但是由于它比来源于石油的脂肪烃溶剂价格高，资源也相对少，加之气味较大、溶解力范围窄，故近年逐渐为200号油漆溶剂油所取代。但严格地讲，两者作为溶剂使用还是有所区别的，松节油的溶解力比200号溶剂油稍强，且200号溶剂油的作用是纯物理性的，当完成其作用后，几乎完全从涂膜中挥发除去，而松节油则有促进涂料干燥的作用，因为松节油所含的店烯能和氧结合成过氧化物而促进干燥。目前松节油尚少量用于油基涂料和醇酸树脂涂料中，以提高涂料的贮存稳定性。",
+        "category": " Introduction"
+    },
+    {
+        "id": 689,
+        "chunk": "# 2.双戊烯  \n\n双戊烯是由木材松节油分馏而得，分子式和烯相同（Co $\\mathbf{H}_{16})$ ，但没有旋光性。工业品中还含几种其他烃类，所以蒸馏范围比较宽 $(160\\sim190\\Upsilon)$ ，对大多数天然树脂和合成树脂的溶解力都很强。由于其挥发速率比较低，故可以延长涂膜干燥时间，可用以改变装饰性面及底漆的湿边时间，也可用于氧化干燥性涂料中起抗结皮作用。但是随着烃类溶剂的发展和防止结皮剂的应用，双戊烯在涂料中已很少应用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 690,
+        "chunk": "# 3.松油  \n\n松油是通过松树干、松树籽和松针的蒸汽蒸馏和分解蒸馏而得，其成分比较复杂，主要成分是二醇。松油的沸点比双戊烯高（约 $204\\sim218^{\\circ}\\mathrm{C}$ )，因而具有相对低的挥发速率及较高的溶解力，在涂料中的应用主要是提高涂膜的流平性，然而，往往要和挥发速率快的溶剂混合使用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 691,
+        "chunk": "# 四、醇类溶剂  \n\n醇、酮、酯和醇醚这4类溶剂常常被统称为含氧溶剂。所谓含氧溶剂就是分子中含有氧原子的溶剂。它们是涂料用溶剂中极其重要的一部分，因为它们能提供范围很宽的溶解力和挥发性。很多树脂不能溶于烃类溶剂中，但能溶于含氧溶剂，这些溶剂具有更大的极性，通过混合可以得到理想的溶解度参数和氢键值的混合溶剂。  \n\n含氧溶剂除个别情况外，很少单独使用，它们常和其他化合物混合而得到适宜的溶解力、挥发速率及较廉价的成本。 1OA",
+        "category": " Introduction"
+    },
+    {
+        "id": 692,
+        "chunk": "# 1.甲醇  \n\n甲醇为无色透明有特殊气味的液体。有吸水性，与水和许多有机溶剂可以任意比相混溶，几乎不溶于脂肪和油，与脂肪烃溶剂仅部分相溶。大量的无机物（许多盐）溶于甲醇。甲醇对于极性树脂、硝基纤维素和乙基纤维素有良好的溶解力，也能溶解油改性醇酸树脂、聚醋酸乙烯酯、聚乙烯基醚、聚乙烯吡咯酮，但不能溶解其他聚合物。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 693,
+        "chunk": "# 2.乙醇  \n\n乙醇俗称酒精，为无色透明，具有特殊芳香气味的液体。工业品是体积含量为 $95\\%$ 的乙醇。能与水、乙醚、氯仿、酯和烃类衍生物等混溶，能溶解虫胶、聚乙烯醇缩丁醛树脂、苯酚甲醛树脂而制成相应的涂料。因其极性较弱，还可以溶解聚酯和聚醋酸乙烯树脂等。但乙醇一般很少单独使用，大多和其他溶剂配合，得到较好的综合性能。如乙醇和醚类溶剂混合可以提高对硝基纤维素的溶解能力，在硝基纤维素涂料中用作稀释剂可以降低溶液黏度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 694,
+        "chunk": "# 3.异丙醇  \n\n异丙醇和水能以任何比例混合，溶解力、挥发速率和乙醇相似。但它的臭味更强烈，现主要用作硝基纤维素和醋酯纤维素涂料的助溶剂。异丙醇与芳烃的混合物能溶解乙基纤维素。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 695,
+        "chunk": "# 4.正丁醇  \n\n正丁醇为无色透明液体，有特异的芳香气味，它能和醇、醚、苯等多种有机溶剂混溶，能溶解尿素甲醛树脂、三聚氰胺甲醛树脂、聚醋酸乙烯树脂、短油度醇酸树脂等。正丁醇和二甲苯的混合溶剂广泛用于氨基烘漆及环氧树脂漆中。正丁醇是硝基纤维素树脂的助溶剂，由于其沸点较高、挥发较慢，故有“防白作用”。用在水性涂料中，可以降低水的表面张力，促进涂膜干燥，增加涂膜的流平性。正丁醇的一个端是具有较高的黏度，这对溶液的黏度影响较大。  \n\n正丁醇尚有另外3种异构体，即异丁醇、仲丁醇和叔丁醇。随着支链的增加，其沸点降低，挥发速率提高，溶解力下降。异丁醇往往可以应用于使用正丁醇的场合。仲丁醇是一种中沸点的助溶剂。叔丁醇则很少作溶剂使用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 696,
+        "chunk": "# 5.己醇  \n\n已醇较重要的异构体是正已醇、2-乙基-1-丁醇和甲基异丁基卡必醇（4-甲基-2-戊醇)。已醇是高沸点溶剂，故可用于提高涂料的流动性和表面性质。它也可用作脂肪、蜡和染料的溶剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 697,
+        "chunk": "# 6.2-乙基己醇  \n\n无色液体，有特殊气味。实际上不溶于水，可与常用的有机溶剂混溶。是许多植物油和脂肪、染料、合成和天然树脂原材料的良溶剂。它也作为颜料的研磨助剂、表面浸溃剂使用，有利于颜料在非水溶剂中的分散。作为高沸点溶剂少量加入涂料配方中，可以提高烤漆的流平性和光泽度。 Y",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 698,
+        "chunk": "# 7.苄醇  \n\n能与除脂肪烃外的有机溶剂混溶。它可以溶解纤维素酯和醚、脂肪、油、醇酸树脂和着色剂等。对聚合物都不溶解（低分子量聚乙烯基醇醚和聚醋酸乙烯酯除外)。少量的苄醇可以提高涂料的流动性和光泽，延长其他组分溶剂的挥发时间，并且在涂料的物理干燥过程中有增塑效应。它可用于圆珠笔油墨，可以降低双组分环氧体系的黏度。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 699,
+        "chunk": "# 8.甲基苄醇(1-苯基乙醇)  \n\n甲基苄醇几乎无色，中性液体，与水混溶度有限，略带苦杏仁味。对醇溶性硝酸纤维素、醋酸纤维素酯、醋酸丁基纤维素酯、许多天然和合成树脂、脂肪以及油有很高的溶解力。与苄醇相比，它可与200号溶剂油混溶。  \n\n甲基苄醇可像苄醇一样使用，在烤漆中具有使用优势。在硝酸纤维素和醋酸纤维素清漆中，甲基苄醇可以帮助提高涂膜生成的流动性，阻止在相对高的空气湿度环境下涂膜发白。鉴于其溶解特性和较长的挥发时间，它也是非常有效的脱漆剂中的添加剂。甲基苄醇对着色剂的溶解力与苄醇类似。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 700,
+        "chunk": "# 9.环己酮  \n\n像樟脑一样的味道，在水中溶解度为 $2\\%$ ，可与其他溶剂混溶，可溶解脂肪、油、蜡和沥青，但不溶解纤维素衍生物。环己酮用于硝酸纤维素漆以及油基涂料中，可延长干燥时间，阻止发白，提高流平性和光泽。在面漆和清漆中，环己醇可能防止对底漆的溶解。环己醇也用于从矿物油中除去链烷烃，可作为蜡、清洁剂以及上光剂中的溶剂和喷雾液的润湿剂使用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 701,
+        "chunk": "# 10.甲基环己醇  \n\n市场上销售的是各种甲基环已醇异构体的混合物。樟脑味，不溶于水，但与所有有机溶剂混溶，溶解性质与环已醇类似。鉴于其对脂肪的溶解性，甲基环己醇可以提高涂料对涂装前不能完全脱脂的底材的黏结。",
+        "category": " Introduction"
+    },
+    {
+        "id": 702,
+        "chunk": "# 11.四氢糠醇  \n\n无色液体，能与水和除脂肪烃以外的有机溶剂混溶。溶解硝酸和醋酸纤维素、氯乙橡胶、虫胶和许多树脂基料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 703,
+        "chunk": "# 12.二丙酮醇  \n\n二丙酮醇是一种无色无嗅的透明液体，其分子中含有一个酮基和一个羟基，分子式为$(\\mathrm{CH}_{3})_{2}\\mathrm{COHCH}_{2}\\mathrm{COCH}_{3}$ 。因此是许多树脂，如醇酸树脂、环氧树脂、酚醛树脂、聚醋酸乙烯树脂、硝基纤维素等的良好溶剂，涂料中常用以配制静电稀释剂调节静电喷涂时的涂料导电性。",
+        "category": " Introduction"
+    },
+    {
+        "id": 704,
+        "chunk": "# 五、酮类溶剂  \n\n酮类溶剂是另一类含氧溶剂。涂料用重要的酮类溶剂有丙酮、甲乙酮、甲基异丁基酮环己酮、异佛尔酮和二丙酮醇等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 705,
+        "chunk": "# 1.丙酮  \n\n丙酮是一种沸点低，挥发速率快的强溶剂。是挥发性涂料，如硝基纤维素涂料、过氯乙烯涂料、热塑性丙烯酸树脂涂料的良好溶剂。但是由于其快速挥发的冷却作用，能引起空气中水蒸气在涂膜表面的冷凝，而导致涂膜表面结霜发白，故常和能起防白作用的低挥发醇类和醇醚类溶剂共同使用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 706,
+        "chunk": "# 2.甲乙酮  \n\n甲乙酮（MEK）是广泛应用于涂料中的一种酮类溶剂。它的溶解能力和丙酮相同，但其挥发速率较慢，是硝基纤维素、丙烯酸树脂、乙烯树脂、环氧树脂和聚氨酯树脂常用的溶剂之一。",
+        "category": " Introduction"
+    },
+    {
+        "id": 707,
+        "chunk": "# 3.甲基丁基酮  \n\n甲基丁基酮微溶于水，与有机溶剂混溶。作为中沸点溶剂可溶解硝酯纤维素、乙烯基树脂和其他天然和合成树脂等。它能增加非溶剂与稀释剂的稀释作用。作为涂料溶剂，甲基丁  \n\n基酮仅在热喷涂和卷材涂料中使用较多。因为它为光化学情性，故作溶剂使用时，不会有“光雾”生成。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 708,
+        "chunk": "# 4.甲基异丁基酮  \n\n甲基异丁基酮（MIBK）是一种中沸点的酮类溶剂，用途和甲乙酮相似，但挥发速率稍慢一些，是一种溶解力强、性能良好的溶剂。甲基异丁基酮是一种无色有甜味的液体，与水部分相溶，但与有机溶剂完全混溶。它是许多天然与合成树脂，如硝酸纤维素、聚醋酸乙烯酯、氯乙烯共聚物、环氧树脂、大多数丙烯酸树脂、醇酸树脂、古马隆和树脂、氨基树脂、酚醛树脂、橡胶和氯化橡胶、松香、松香脂、天然树脂、玛树脂、松树胶和古巴酯、脂肪和油等的溶剂。甲基异丁基酮作为中沸点溶剂广泛用于涂料工业，它可赋予硝基纤维索清漆良好的流动性和光泽度，提高抗泛白能力，允许含有高比例廉价稀释剂的高浓缩溶液的生产。甲基异丁基酮与醇和芳香烃溶剂配合，是所有环氧树脂配方中的一个重要组分，是低分子量PVC和氯乙烯共聚物的良溶剂，可用来制备具有较高的芳烃可稀释度的低黏度溶液。甲基异丁基酮也作为中沸点溶剂组分用于钢、马口铁板或铝材的压花漆。可降低醇酸树脂漆的黏度，并用于丙烯酸漆中，是聚氨酯涂料中非常重要的无水和不含羟基的溶剂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 709,
+        "chunk": "# 5.甲基戊基酮和甲基异戊基酮  \n\n它们是高沸点溶剂，溶解力良好，与甲基异丁基酮有相似的溶解特性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 710,
+        "chunk": "# 6.乙基戊基酮  \n\n乙基戊基酮不溶于水，与有机溶剂混溶，属于高沸点溶剂，有良好的溶解力，可提高涂料的流动性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 711,
+        "chunk": "# 7.二异丙基酮  \n\n二异丙基酮是高沸点溶剂，用于涂装皮革的硝基纤维素乳液的生产和氯化橡胶涂料中，是聚氯乙烯有机溶胶的稀释剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 712,
+        "chunk": "# 8.二异丁基酮  \n\n二异丁基酮为无色低黏度液体，由2，6-二甲基-4-庚酮和2，4-二甲基-6-庚酮这两个异构体的混合物组成。与水不相溶，但与所有常用有机溶剂可以任意比例相溶，为高沸点溶剂，对硝基纤维素、乙烯基树脂、蜡和许多天然合成树脂有良好的溶解力。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 713,
+        "chunk": "# 9.环己酮  \n\n环己酮也是一种强溶剂，挥发速率较慢，对多种树脂有良好的溶解能力。主要用于聚氨酯涂料、环氧树脂涂料和乙烯树脂涂料。可提高涂膜的附着力，并使涂膜平整美观。当用作硝基喷漆的溶剂时，能提高涂料的防潮性及降低溶液的黏度。 Wr Q",
+        "category": " Introduction"
+    },
+    {
+        "id": 714,
+        "chunk": "# 10.甲基环己酮  \n\n甲基环已酮是一种工业异构体的混合物，与环已酮的溶解力和混溶性相似，但不溶解醋酸纤维素酯。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 715,
+        "chunk": "# 11.二甲基环己酮  \n\n二甲基环己酮为工业品，为顺、反异构体混合物，与甲基环已酮有相似的溶解力和混溶性。",
+        "category": " Introduction"
+    },
+    {
+        "id": 716,
+        "chunk": "# 12.三甲基环己酮  \n\n三甲基环已酮为无色高沸点溶剂，具有薄荷醇的芳香余味，与水部分相溶，与所有有机溶剂可以任意比相混溶。三甲基环己酮可溶解硝酸纤维素酯、低分子量级PVC、聚醋酸乙烯酯、氯乙烯-醋酸乙烯酯共聚物、氯化橡胶、醇酸树脂、不饱和聚酯树脂、环氧树脂、丙烯酸树脂等。  \n\n在涂料工业中，它用作气干和烘干体系的流平剂，以减少气泡和缩孔的生成，提高流动性和光泽。它的添加，使得有高含水量稀释剂存在的低分子量聚氯乙烯或氯乙烯共聚物的乙烯基涂料表现出良好的贮存稳定性。三甲基环己酮配合适宜的稀释剂也作为聚氯乙烯加工过程中的暂时增塑剂。在由聚氯乙烯和增塑剂组成的厚膜型涂料中，它作为具有低凝胶倾向的稀释剂使用。三甲基环己酮也用作涂装皮革的硝酸纤维素酯乳液中的溶剂，杀虫剂配方中的共溶剂。三甲基环己酮在气干型涂料中有防结皮作用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 717,
+        "chunk": "# 13.异佛尔酮  \n\n异佛尔酮（Isophorone）简称IP，化学名称为3,5,5-三甲基-2-环已烯-1-酮。为一种淡黄色的液体，有类似樟脑的气味，具有较高的沸点，很低的吸湿性，较慢的挥发速率和突出的溶解能力，能与大部分有机溶剂和多种硝基纤维素涂料混溶。特别是对硝化纤维素、乙烯树脂、三聚氰胺树脂、聚酯树脂、醇酸树脂、环氧树脂溶解力强，能赋予涂膜很好的流平性。因此，作为酮类溶剂应用范围很广。",
+        "category": " Introduction"
+    },
+    {
+        "id": 718,
+        "chunk": "# 六、酯类溶剂  \n\n酯类溶剂也是含氧溶剂的一种。涂料中常用的酯类溶剂大多数都是醋酸酯，也有少量其他有机酸的酯类。  \n\n酯是由醇和酸通过酯化反应而生成的，因此低碳醇的酯易水解。醋酸酯内常含有的醋酸、相应的醇及水等杂质可以通过洗涤-干燥剂干馏-蒸馏的方法进行精制。  \n\n作为溶剂常用的醋酸酯类化合物，其溶解力随分子量增大及分子中支链的增加而降低。而挥发速率则随分子量的增加而降低，但随着分子中支链的增加而增加。",
+        "category": " Introduction"
+    },
+    {
+        "id": 719,
+        "chunk": "# 1.甲酸异丁酯  \n\n微溶于水，溶解脂肪、油、许多聚合物和氯化橡胶，但不溶解醋酸纤维素酯。商业上它作为涂料的混合溶剂中的组分。",
+        "category": " Introduction"
+    },
+    {
+        "id": 720,
+        "chunk": "# 2.醋酸甲酯  \n\n与水部分混溶，易与大多数有机溶剂混溶，对纤维素酯和醚、松香、脲醛、三聚氰胺甲醛、酚醛树脂、聚醋酸乙烯酯、醇酸树脂以及其他树脂有良好的溶解力。但不溶解虫胶、玛树脂、古巴树脂或聚氯乙烯。醋酸甲酯单独作为高挥发性溶剂与醇、其他酯混合可降低涂料的黏度。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 721,
+        "chunk": "# 3.醋酸乙酯  \n\n醋酸乙酯系一种无色透明液体，有水果香味。能与醇、醚、氯仿、丙酮、苯等大多数有机溶剂混溶，能溶解植物油、甘油松香酯、硝化纤维素、氯乙烯树脂及聚苯乙烯树脂等。在涂料中可以用作硝化纤维素、乙基纤维素、聚丙烯树脂及聚氨酯树脂的溶剂。  \n\n醋酸乙酯是快干涂料（硝酸纤维素木材漆）中最重要的溶剂之一。它也常用于聚氨酯涂料，能增加非溶剂与稀释剂的可稀释度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 722,
+        "chunk": "# 4.醋酸正丁酯  \n\n醋酸正丁酯系无色液体，有水果香味，与其低级同系物相比，醋酸正丁酯难溶于水，也  \n\n较难水解。能与醇、醚等一般有机溶剂混溶，对植物油、甘油松香酯、聚醋酸乙烯树脂、聚丙烯醋酸酯、氯化橡胶等有良好的溶解能力，系硝基纤维素涂料、聚丙烯酸酯涂料、氯化橡胶涂料及聚氨酯涂料中常用的溶剂。系醋酸酯类溶剂中应用比较广泛的一种。",
+        "category": " Introduction"
+    },
+    {
+        "id": 723,
+        "chunk": "# 5.醋酸异丁酯  \n\n醋酸异丁酯的性质和涂料中的用途与醋酸正丁酯类似，仅是闪点比较低 $(17.8\\mathsf{^{c}}$ ，而醋酸正丁酯为 $27\\Upsilon)$ ，因此火灾危险性比前者大。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 724,
+        "chunk": "# 6.高碳醇醋酸酯  \n\n醋酸己酯（Exxate600）、醋酸庚酯（Exxate700）和醋酸癸酯（Exxate1000）是3种碳醇的醋酸酯，作为高沸点的酯类溶剂，它既有含氧溶剂的较高的溶解力，又保持有机烃类溶剂的性质。  \n\n用醋酸已酯和醋酸庚酯合成高固体分丙烯酸树脂时，不仅可以改进对树脂分子量大小及分子量分布的控制，以获得低分子量和较窄的分子量分布，从而得到交联能力高、涂膜光泽好和耐久能力强的高固体分涂料。另外，含有这类溶剂的配方也可以获得较高的电阻率，由于电阻率影响涂料的雾化特性和静电喷涂时的转移效率，一般将静电喷涂时的涂料电阻率调整到 $0.6{\\sim}1.$ 0MΩ，但是这对于金属闪光涂料等却是一个难题，而使用具有接近烃类溶剂电阻率的高碳醇的醋酸酯溶剂不仅可获得高的电阻率，同时又可获得烃类溶剂难以提供的溶解能力，这无疑是解决此类难题的一个诱人途径。表2-3-39为以醋酸庚酯（Exxate700）代替甲基戊基甲酮（MAK）用于金属闪光涂料时对涂料电阻率的提高和喷涂转移效率的影响的实例。  \n\n表2-3-39溶剂对转移效率的影响  \n\n\n<html><body><table><tr><td>最后挥发的溶剂</td><td>甲基戊基甲酮</td><td>醋酸庚酯</td></tr><tr><td>电阻率/MΩ 转移效率/%</td><td>0.07 73</td><td>0.31 83</td></tr></table></body></html>  \n\n与醇醚醋酸酯和高沸点酮类溶剂相比，将醋酸己酯用于对潮气敏感的各种气干型涂料中，不仅由于其较慢的挥发速率而有效地减少涂膜的“发白”倾向，而且由于其从涂膜中扩散逸出的速率比前者快，故可同时得到较快的干燥速率，实验证明在正常的温度条件下醋酸已酯比乙二醇乙醚醋酸酯的干燥速率要快 $15\\%\\sim30\\%$ ，这一特性使其在硝基纤维素涂料、双组分聚氨酯涂料及挥发型丙烯酸树脂漆中应用时显示出独特的优势。表2-3-40列出高碳醇醋酸酯溶剂的特性指标。  \n\n表2-3-40高碳醇醋酸酯溶剂特性表  \n\n\n<html><body><table><tr><td>项目</td><td>醋酸己酯</td><td>醋酸庚酯</td><td>醋酸癸酯</td></tr><tr><td>沸程/C</td><td>164~176</td><td>176~200</td><td>230~248</td></tr><tr><td>密度（20C）/(g/cm)</td><td>0.874</td><td>0.874</td><td>0.873</td></tr><tr><td>相对挥发速率（醋酸乙酯=1)</td><td>0.17</td><td>0.08</td><td><0.01</td></tr><tr><td>颜色(赛波特色）</td><td>10</td><td>10</td><td>10</td></tr><tr><td>表面张力/(mN/m)</td><td>25.7</td><td>26.0</td><td>27.0</td></tr><tr><td>黏度(20℃)/mPs·s 溶解度（25℃）</td><td>1.05</td><td>1.24</td><td>2.27</td></tr><tr><td>水在溶剂中（质量分数）/%</td><td></td><td></td><td></td></tr><tr><td>溶剂在水中（质量分数）/%</td><td>0.66 0.02</td><td>0.58 0.01</td><td>0.25 不溶</td></tr><tr><td>用 途</td><td>纤维素涂料、聚氨酯涂料、环氧聚酰胺涂 料、卷材料涂料、罐头涂料、烘漆、高固体分 丙烯酸酯涂料</td><td></td><td>卷材涂料、罐头涂料、烘漆</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 725,
+        "chunk": "# 7.乳酸丁酯  \n\n乳酸丁酯又称2-羟基丙酸正丁酯，分子式为 $\\mathrm{CH_{3}C H(O H)C O O C_{4}H_{9}}$ 。系由乳酸和正丁醇在硫酸催化下酯化的产物，乳酸丁酯是一种有轻微气味的无色液体，沸程 $155\\sim200^{\\circ}\\mathrm{C}$ ·密度 $(20\\mathfrak{C})0.974\\sim0.984\\mathrm{g}/\\mathrm{cm}^{3}$ ，闪点71℃。溶解能力好，挥发速率慢，对多种溶剂及稀释剂的互溶性好。在涂料中使用可以提高涂膜的流平性，有利于得到高光泽、柔韧性好、附着力好的涂膜，对于清漆还可以提高涂膜的透明度，可以应用于氨基醇酸烘漆、氨基固化丙烯酸树脂漆和硝基纤维素漆中。",
+        "category": " Introduction"
+    },
+    {
+        "id": 726,
+        "chunk": "# 七、醇醚及醚酯类溶剂  \n\n将乙二醇和乙醇醚化反应，可制得乙二醇乙醚，如将乙二醇乙醚上的羟基（一OH）再与醋酸进行酯化反应，则会制得乙二醇乙醚醋酸酯。这是目前我国涂料工业常用的一类醇醚和醚酯类溶剂。  \n\n另一类则是以二乙二醇代替乙二醇而发展起来的，比如二乙二醇乙醚、二乙二醇丁醚、二乙二醇乙醚醋酸酯及二乙二醇丁醚醋酸酯等。如果以丙二醇代替乙二醇，则会发展出丙二醇乙醚、丙二醇丁醚、丙二醇乙醚醋酸酯及丙二醇丁醚醋酸酯等一类醇醚和醚酯类溶剂。其他，如3-乙氧基丙酸乙酯和4-丁氧基丙酸丁酯（BPB）等也属于醚酯类溶剂。  \n\n尽管乙二醇醚及醚酯类溶剂目前尚在我国的涂料产品中应用，但是自20世纪80年代以来，工业卫生专家郑重指出乙二醇醚及其酯类溶剂的毒性是十分严重的，它对血液循环系统、淋巴系统及动物的生殖系统均有极大危害，会导致雌性不育、胎儿中毒、畸形胎、胚胎消融、幼子成活率低及先天低智能等病状。美国政府已于1982年6月将乙二醇甲醚及乙醚的最低工作环境允许浓度限制在 ${<}5\\mathrm{mg/m^{3}}$ ，相当于我国毒性等级中“高毒”级，德国也已宣布禁止使用乙二醇醚类溶剂。实践证明丙二醇醚及其醚酯类溶剂在涂料中应用性能与乙二醇醚极为相似，而其毒性要比乙二醇乙醚小得多。因此本节虽然向读者也介绍了乙二醇醚及醚酯类溶剂，但提倡以丙二醇醚及其醚酯取代之。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 727,
+        "chunk": "# 1.乙二醇乙醚  \n\n乙二醇乙醚又称甘醇乙醚或乙基溶纤剂。为无色液体，有温和的香味。能与水、醇、醚、丙酮等多种溶剂混溶。能溶解硝化纤维素、醇酸树脂、聚醋酸乙烯酯树脂，但不溶解醋酸纤维素及聚甲基丙烯酸甲酯。对松香、虫胶、甘油松香酯等也有一定的溶解能力。  \n\n乙二醇乙醚用作涂料溶剂，由于对水溶解能力大，单独使用容易发生乳化现象，因此在溶剂型涂料中往往和其他溶剂混合使用，它的作用是可以容忍较大量的稀释剂，并可在大多数溶剂挥发以后，来保持湿涂膜的流动性，而在水性涂料中则是很好的助溶剂。主要用作硝基纤维素涂料、电绝缘用硅氧烷改性聚酯涂料的溶剂及作为助溶剂用于水性涂料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 728,
+        "chunk": "# 2.乙二醇丙醚和乙二醇异丙基醚  \n\n与乙二醇乙醚有相当的溶解性和混溶性，但挥发更慢，并且对低极性树脂有较好的溶解力。比乙二醇乙醚毒性小，故正逐步替代乙二醇乙醚。",
+        "category": " Introduction"
+    },
+    {
+        "id": 729,
+        "chunk": "# 3.乙二醇乙醚醋酸酯  \n\n乙二醇乙醚醋酸酯又称甘醇乙醚醋酸酯、乙基溶纤剂醋酸酯或醋酸-2-乙氧基乙酯。为 无色液体，微有芳香味。  \n\n由于乙二醇乙醚醋酸酯的分子结构中存在醚和酯的结构，具有脂肪醚和脂肪酯的特性，它能与多种溶剂相混溶。能溶解油脂、松香、氯化橡胶、硝基纤维素、醇酸树脂、酚醛树脂、三聚氰胺甲醛树脂、聚醋酸乙烯酯、聚甲基丙烯酸甲酯及聚苯乙烯等多种涂料产品。由于其高溶解力及与其他溶剂的高比例混溶性，以及挥发速率较慢，因而便于涂膜的流平，使涂膜均匀、光泽及附着力提高。  \n\n由于乙二醇乙醚醋酸酯在水中溶解性能较好（ $20\\%$ 时在水中溶解度为 $22.9\\%$ ，质量分数)，对水相和油相都具有突出的亲和性，因而具有表面活性剂的作用，而成为水性涂料良好的助溶剂。乙二醇乙醚醋酸酯还是一种非光化学反应性的溶剂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 730,
+        "chunk": "# 4.乙二醇丁醚醋酸酯  \n\n乙二醇丁醚醋酸酯又称甘醇丁醚醋酸酯、丁基溶纤剂醋酸酯或醋酸-2-丁氧基乙酯。为无色液体，在水中溶解度比乙二醇乙醚醋酸酯低， $20\\Upsilon$ 在水中溶解 $1.1\\%$ ，水在其中溶解$1.6\\%$ ，能溶解乙基纤维素、聚醋酸乙烯酯、聚苯乙烯等，但不能溶解醋酸纤维素、聚甲基丙烯酸甲酯、聚乙烯醇缩丁醛等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 731,
+        "chunk": "# 5.丙二醇醚类溶剂  \n\n丙二醇醚类溶剂主要包括丙二醇甲醚、丙二醇乙醚、丙二醇丁醚及其酯类。  \n\n丙二醇醚具有两个强溶解功能的基团—醚键和羟基，前者具有亲油性，可溶解憎水性化合物，后者具有亲水性，可溶解水溶性化合物。丙二醇醚与相应的乙二醇醚类溶剂化学性质相似，但是毒性却低得多。由于丙二醇醚也具有醇醚类溶剂共同的特点—溶解能力强及挥发慢，因此作为溶剂可以提高涂膜的流平性、光泽和丰满度，克服某些涂膜常见的病态。可用作硝化纤维素涂料、氨基醇酸涂料、丙烯酸树脂涂料、环氧树脂涂料的良好溶剂。  \n\n丙二醇醚可以与水以任何比例互溶，因此又是水性涂料最佳的助溶剂及成膜助剂。在水溶性电泳漆中以丙二醇醚作为助溶剂，可以开发出高性能的电泳涂料。作为乳胶漆的成膜助剂可以显著地降低乳液的最低成膜温度。丙二醇醚类溶剂在涂料中的应用可以见表2-3-41。  \n\n表2-3-41丙二醇醚类溶剂在涂料工业中的应用  \n\n\n<html><body><table><tr><td>用 途</td><td>应用的产品</td><td>作用与效果</td></tr><tr><td>溶剂型清漆和色漆的溶剂和 助溶剂，如基料为聚丙烯酸、环 氮、氨基、醇腋及硝化纤维素等</td><td>丙二醇甲醚 丙二醇乙醚 二丙二醇甲醚 丙丙二醇乙酯酸酶 丙二醇乙醚酸酸酯</td><td>1.增加树脂的溶解均匀性 2.促进涂料各组分间的偶联 3.调节涂料溶剂的挥发速率 4.改进涂膜的涂刷性 5.改进涂膜的平整度和光泽、克服橘皮等涂膜病</td></tr><tr><td>水溶性树脂的助溶剂</td><td>丙二醇甲醚 丙二醇乙醚 二丙二醇甲醚 二丙二醇乙醚 丙二醇甲醚醋酸酯 丙二醇乙醚醋酸酯</td><td>1.使树脂和水偶联 2.调节涂料黏度 3.改进涂料的流平性 4.改进涂膜的流平性、光泽等</td></tr><tr><td>乳胶漆的成膜助剂</td><td>丙二醇丁醚 二丙二醇甲醚 二丙二醇乙醚</td><td>1.使高分子链互相溶化凝结 2.增加涂膜光泽</td></tr><tr><td>木材染色涂料（水基、油基助 溶剂)</td><td>丙二醇甲酰 丙二醇甲醚醋酸酯 丙二醇乙醚醋酸酯</td><td>1.完全溶解着色染料，使着色均匀 2. 控制对发速率渗保证些,使均匀无搭接痕迹</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>用 途</td><td>应用的产品</td><td>作用与效果</td></tr><tr><td>脱漆剂的组成溶剂</td><td>丙二醇甲醚醋酸酯 丙二醇乙醚醋酸酯</td><td>1.溶解脱漆剂组分中的纤维素类增酮剂 2.增加脱漆剂在旧漆中的渗透性使旧漆树脂溶胀</td></tr><tr><td>色浆用溶剂</td><td>二丙二醇乙酸醚</td><td>增加水和有机物的偶联作用</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 732,
+        "chunk": "# 6.三乙二醇醚类溶剂  \n\n三乙二醇乙醚：几乎无色、中性、气味温和的液体，低吸水性，溶于水和大多数有机溶剂，但与芳香烃及脂肪烃仅部分相溶。三乙二醇乙醚可溶解硝酸纤维素、虫胶、松香、酮树脂、马来酸树脂、氯化橡胶、醇酸树脂以及许多其他涂料用树脂。但不溶解醋酸纤维素酯、聚氯乙烯、氯乙烯共聚物、脂肪、油和橡胶。  \n\n三乙二醇乙醚的用途与二乙二醇乙醚相似。它还可以作为不相溶液体的增溶剂，也可用于杀虫剂、手洗洗涤剂的制造。它也用于印刷油墨。木材漆中加人少量三乙二醇乙醚可以阻止涂刷过程中表面的木材纤维倒立。  \n\n三乙二醇丁醚：几乎无色、中性、气味轻微的液体，溶于水和大多数有机溶剂，但仅与芳香烃和脂肪烃溶剂部分相溶。其溶解性可与二乙二醇丁醚相比。三乙二醇丁醚可作为互不相溶液体的增溶剂，用于家具漆的生产、金属清洁剂以及木材防腐。它适宜作为高沸点溶剂用于烘漆，作为流平剂、木材漆中的助溶剂来阻止木材纤维从表面倒立。",
+        "category": " Introduction"
+    },
+    {
+        "id": 733,
+        "chunk": "# 7.3-乙氧基丙酸乙酯  \n\n3-乙氧基丙酸乙酯是一种高性能的醚酯类溶剂，分子式为 $\\mathrm{C}_{2}\\mathrm{H}_{3}\\mathrm{OC}_{3}\\mathrm{H}_{4}\\mathrm{OOC}_{2}\\mathrm{H}_{5}$ 。相对分子质量146.29，密度 $0.95g/\\mathrm{cm}^{3}$ ，相对挥发速率0.12（醋酸正丁酯 $=1$ )，表面张力$23\\Upsilon$ ）27. $0\\mathrm{mN/m}$ ，电阻20MΩ，溶解度参数为8.8，黏度 $(20\\%$ )1 $\\mathbf{\\nabla}_{\\cdot}0\\mathbf{m}\\mathbf{Pa}\\cdot\\mathbf{s}$ ，沸程为 $165\\sim$ $172^{\\circ}\\mathrm{C}$ 。3-乙氧基丙酸乙酯是配制优质烘漆及空气干燥涂料的有效溶剂，具有下述优良性能。  \n\n$\\textcircled{1}$ 挥发速率慢可防止纤维素涂料发白，提高涂膜流平性及投影光泽，以便获得高质量的涂膜。  \n\n$\\textcircled{2}$ 溶解能力强溶解范围广，作为线型醚酯类溶剂对硝化纤维素、醋酸纤维素、环氧树脂、丙烯酸树脂、三聚氰胺甲醛树脂、无油聚酯树脂、聚氨酯树脂都有很好的溶解性。加之，其溶解能力强及自身黏度低的原因，所得的树脂溶液黏度也较低。  \n\n$\\textcircled{3}$ 表面张力低及溶剂释放快可以提高涂膜的防缩孔性、流平性、重涂性及对底材的湿润性，提高附着力，由于溶剂释放快，可提高涂膜“干”阶段的干燥性能，减少溶剂残留。  \n\n$\\textcircled{4}$ 电阻高可以弥补高固体分涂料在静电喷涂时，由于配方中极性溶剂电阻低，而使涂料电阻达不到喷涂所要求的最佳电阻范围缺陷，方便地调整电阻值。因此，是一种值得推广应用及开发的溶剂品种。 Ar",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 734,
+        "chunk": "# 8.β丁氧基丙酸丁酯  \n\n$\\beta$ 丁氧基丙酸丁酯（BPB)，是一种具有线型结构的醚酯类溶剂。分子式为$\\mathrm{C}_{4}\\mathrm{H}_{9}\\mathrm{OC}_{2}\\mathrm{H}_{3}\\mathrm{COOC}_{4}\\mathrm{H}_{9}$ 。密度为 $0.98/\\mathrm{cm}^{3}$ ，沸程为 $170{\\sim}230\\Upsilon$ （纯品为 $220{\\sim}230\\%$ 的无色液体，对丙烯酸树脂、氨基树脂、醇酸树脂、环氧树脂、聚氨酯树脂、硝基纤维素及CAB等都具有良好的溶解性能。由于挥发速率慢，一般仅适用于烘烤，对改善涂膜流平性、提高光泽有明显的效果。 C",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 735,
+        "chunk": "# 八、取代烃类溶剂  \n\n取代烃类溶剂通常仅在特殊场合下才能独立使用，其中有价值的为氯化烃及硝基烃。  \n\n1,1，1-三氯乙烷是涂料中经常会遇到的氯化烃类溶剂。这种化合物会进行无光化学反应。氯化烃溶剂的一个优点是不易燃烧。它是比脂肪烃溶剂溶解力较强（溶解度参数为9.6)，而又具有较低氢键值（为1.5）的溶剂，缺点是挥发较快。  \n\n硝基烃中属2-硝基丙烷应用量较大。它具有较高的溶解度参数（10.7）和较低的氢键值（为2.5），其挥发速率（为1.2）和醋酸正丁酯基本相当。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 736,
+        "chunk": "# 九、其他溶剂",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 737,
+        "chunk": "# 1.1,1-二甲基乙烷  \n\n中性液体，与水和有机溶剂混溶。它能溶解硝酸纤维素、纤维素醚、一些氯乙烯共聚物、合成和天然树脂。但不溶解聚氯乙烯、聚苯乙烯、氯化橡胶和醋酸纤维素酯。可用于涂料、黏合剂的生产。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 738,
+        "chunk": "# 2.N,N-二甲基甲酰胺（DMF）  \n\n与水和除脂肪烃外的所有有机溶剂混溶，是纤维素酯和醚、聚氯乙烯、氯乙烯共聚物、聚醋酸乙烯酯、聚丙烯腈、聚苯乙烯、氯化橡胶、聚丙烯酸酯和酚醛树脂等的良好的高沸点溶剂。但不溶解聚乙烯、聚丙烯、脲醛树脂、橡胶和聚酰胺。常作为溶剂用于印刷油墨、聚丙烯睛纺织溶液和乙炔的合成中。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 739,
+        "chunk": "# 3.N,N-二甲基乙酰胺（DMA）  \n\n与水和有机溶剂混溶，对许多树脂和聚合物有非常好的溶解力。用于丙烯酸纤维、薄膜、板材和涂料的生产，并且作为有机合成中的反应介质和中间体。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 740,
+        "chunk": "# 4.二甲亚矾（DMSO）  \n\n为无色透明液体，有吸湿性。能与水、乙醇、乙醚、丙酮、乙醛、吡啶、乙酸乙酯、苯二甲酸二丁酯、二暖烷和芳烃化合物等任意互溶，不溶于乙炔以外的脂肪烃类化合物。是纤维素酯和醚、聚醋酸乙烯酯、聚丙烯酸酯、氯乙烯共聚物、聚丙烯腈、氯化橡胶和许多树脂的良好高沸点溶剂。也可用于聚丙烯睛纺丝溶液和脱漆剂，用作分散液的成膜助剂以及提取剂和有机合成中的反应介质。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 741,
+        "chunk": "# 5.1-硝基丙烷  \n\n无色、非吸水性液体，气味温和。能溶解硝酸纤维素、纤维素醚、醇酸树脂、氯化橡胶、聚醋酸乙烯酯、氯乙烯共聚物等。但不溶解聚氯乙烯、松香、聚丙烯腈、蜡、橡胶和虫胶。作为共溶剂用于涂料中用来提高颜料的润湿、流动性和改善静电工艺，可减少涂料的干燥时间。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 742,
+        "chunk": "# 6.N-甲基吡咯烷酮  \n\n相当温和，氨味，能与水和大多数有机溶剂混溶。对纤维素醚、乙二醇-丙烯睛共聚物、聚酰胺、聚丙烯睛、蜡、聚丙烯酸酯、氯乙烯共聚物和环氧树脂有良好的溶解力。用于脱漆剂以及涂料可以降低涂料的黏度，提高涂料体系的润湿力。 我",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 743,
+        "chunk": "# 7.1,3-二甲基-2-咪唑烷酮  \n\n无色、高沸点、高极性、情性质子溶剂。低毒，具有良好的化学和热稳定性。与水和大多数有机溶剂混溶。是制造甲油、圆珠笔油和涂料的原料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 744,
+        "chunk": "# 8.六甲基磷酸三胺  \n\n碱性、高极性、非可燃溶剂，有非常好的溶解能力。其溶解性可与DMSO和DMA相  \n\n比。也可作为抗冻剂和抗静电剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 745,
+        "chunk": "# 第六节有关环保法规  \n\n涂料中的溶剂对环境产生多方面影响，包括涂料生产中溶剂的释放；涂料施工中溶剂及有毒物质的释放；在涂层的使用期间、脱漆过程中溶剂的释放等，对环境造成了不同程度的污染。大多数国家和组织对挥发性有机物质（VOC）的定义是指沸点低于或等于 $250\\Upsilon$ 的任何有机化合物，多达900多种。其部分已被列入致癌物，如氯乙烯、苯、多环芳烃等。涂料中的VOC是指在涂料的使用过程中，挥发到大气中的溶剂和一些化学物质，这些物质会危害环境。",
+        "category": " Introduction"
+    },
+    {
+        "id": 746,
+        "chunk": "# 一、国外涂料工业环保发展历程  \n\n1966年7月，美国针对出现的环境污染问题，制定了限制光化学性挥发有机溶剂的66法规，开始对涂料中挥发性有机溶剂量进行限定。1970年设立环境保护局（EPA)，1977年环境保护局对涂料生产和施工提出了管理要求（简称CTG)，对全美国各州规定了臭氧浓度限定值。更加严格的是，规定了VOC的上限。美国所有州均采用表2-3-42的规定。欧美和其他国家都采用相同措施来限制涂料中VOC的排放浓度。EPA对溶剂型常温干燥涂料的规定VOC值为 $420\\mathrm{g/L}$ 。其中热塑性乙烯类、氯化橡胶类涂料中VOC均超标，因此欧洲一些国家已基本用其他品种来取代。相适应于VOC值为340g/L要求的品种有：无机富锌底漆、环氧、改性环氧、聚氨酯、醇酸树脂类涂料。相适应于VOC值为 $210_{8}/\\mathrm{L}$ 以下要求的品种有：改性环氧、焦油环氧树脂涂料。  \n\n表2-3-42美国环保局（EPA）规定涂料中的VOC值  \n\n\n<html><body><table><tr><td rowspan=\"2\">CTG对象分类</td><td rowspan=\"2\">涂料品种</td><td colspan=\"2\">涂料中的VOC值</td></tr><tr><td>1b/gal</td><td>g/L</td></tr><tr><td>I类范围 轿车及轻型车用涂料</td><td>底涂漆 面涂漆</td><td>1.9</td><td>228</td></tr><tr><td>罐头用涂料</td><td>修补漆 底漆、面涂漆 罐头内壁 罐头接缝涂料</td><td>2.8 4.8 2.8 4.8</td><td>336 575 336 564</td></tr><tr><td>卷材涂料 金属家具</td><td>终端密封涂料 底漆、面漆、底面合一漆 底漆、面漆、底面合一漆</td><td>5.5 3.7 2.6</td><td>660 444 312</td></tr><tr><td>大型机电产品涂料 纤维用涂料</td><td>底漆、面漆、底面合一漆 流水线涂装</td><td>3.0 2.8 2.9</td><td>360 336 348</td></tr><tr><td>纸张涂料 磁导线涂料</td><td>乙烯型涂装流水线 流水线涂装线</td><td>3.8</td><td>456</td></tr><tr><td>I类范围 各种金属构件及其制品涂料</td><td>流水线涂装线</td><td>2.9 1.7</td><td>348 204</td></tr></table></body></html>  \n\n1990年美国环保署颁布了CAAA90（空气净化法修正案）和HAPs（有害空气污染物）法规，对89种溶剂增加了排放标准，其中包括甲醇、甲乙酮、甲基异丁基酮、甲苯、二甲苯等涂料常用的溶剂。1996年5月美国环境保护署又在CAAA90中增加了危险品管理条例(RMP)。该条例对77种有毒物质和63种易燃易爆物质的管理作出了规定，即在任何贮存、使用、生产、运输以及废弃物质的处理过程中，条例规定的77种有毒物质的操作量不得超过 $500{\\sim}200001\\mathrm{k}$ . $\\mathbf{:11b=}0.454\\mathbf{kg})$ ，而易燃物质的操作量不得超过100001b，并对各单元操作之间及工厂设备与周围环境之间应当保持安全距离，以及在发生意外事故、出现有毒有害和易燃易爆物质泄漏时的应急措施等都做了详细的规定。涂料生产设备在贮存和使用这些物质时必须严格遵守该条例中的规定，大型浸涂槽等设备也不例外。1996年美国环境保护署起草了AIM条例——-建筑涂料和工业维护涂料管理条例，其重点在于管制涂料中的VOC，该条例于1999 年生效。条例规定了70余种除工业涂料以外的几乎所有建筑和工业维护涂料品种的VOC上限值，对内外墙乳胶漆做出 $250_{8}/\\mathrm{L}$ 的限制规定。美国环境保护署于2002年设立了有关涂料行业有毒有害空气污染物的排放标准，并于2005年12月颁布最新版的《混合涂料生产的有毒有害气体排放标准》（40 CFR Part 63National Emission Standards for Haz-ardous Air Pollutants: Miscellaneous Coating Manufacturing； Final Rule)。  \n\n美国大气污染物排放法规体系中包括了对贮罐、工艺设备、废水收集和输送系统，输送系统及辅助设备等排放的HAPs 的限值，规定了溶剂可使用品种。主要的HAPs为甲苯、甲醇、二甲苯、氯化氢、二氯甲烷等。HAPs 法规豁免的只剩下乙醇、异丙醇、丙二醇醚、一缩乙二醇醚、醋酸丁酯、叔丁酯、丙酮、甲戊酮和脂肪烃等十余种溶剂。因此，未来涂料行业中可使用的溶剂种类十分有限。近年来HAPs法规也得到日本和欧盟等发达国家的认可。  \n\n欧洲装饰性涂料工业年销售量约330万吨，占其总的涂料市场份额的 $60\\%$ 。过去几十年，在装饰性涂料市场中，水性产品的使用越来越广，到目前大约已增至为装饰性涂料总量的 $70\\%$ ，这主要归因于水性涂料的特殊性能。与此同时，欧洲各国已对环境保护达成共识，并出台了涂料工业在其全世界范围的涂料管理方案（World-wide Coatings Care Pro-gramme)。  \n\n大多数溶剂型装饰性涂料在使用前不要求加入溶剂或稀释剂，溶剂经常用于清洗施工设备。这些产品中所用的溶剂和清洗设备用溶剂均为VOC。尽管水性涂料主要以水作为载体，但也常含少量的添加剂，如成膜助剂等。尽管这些添加剂常为VOC，但它们是达到所要求的性能和施工性所必不可少的。  \n\n装饰性涂料中所含的大多数VOC是在施工和干燥过程中排放出来的。由于装饰性涂料的使用，对VOC排放量有一定的影响，在欧洲人为总VOC排放量中，这部分占了不到 $3\\%$ 。  \n\n在欧洲，民众对提高空气质量非常关注，对减少硫与氮的氧化物，氨和挥发性有机化合物的排放尤为关心，降低VOC的排放对涂料工业来说非常重要。1999年3月11日，欧盟委员会颁布了1999年第13号委员会命令（CouncilDirective1999/13/EC)，即所谓的溶剂释放标准。随着溶剂排放令（The Solvents Emission Directive）的实施，VOC 排放会显著减少。欧洲CEPE（欧洲涂料、印刷油墨、颜料工业协会）下发了关于装饰性涂料中挥发性有机化合物指导书。  \n\n欧盟在1993年通过了《ExistingSubstances》法规，其目的在于对危险品进行评价和管理，从10万多种受法规限制的化学品中选出了100多种危险品，将其分配给各成员国，分别进行化学品的危险性评价。芬兰和丹麦等国提出，没有经过危险性评价的化学物质不能进  \n\n人市场。  \n\nREACH是欧盟规章《化学品注册、评估、许可和限制》（RegulationconcerningtheRegistration，Evaluation，Authorization and Restriction of Chemicals）的简称，是欧盟建立的，并于2007年6月1日起实施的化学品监管体系。REACH法规将欧盟自产或出口到欧盟市场上约3万种化工产品，以及涉及所有使用化工产品的下游产品，如纺织、轻工、玩具、机电等产品分别纳入注册、评估、许可等几个管理监控系统，以规范欧盟市场上化学品的制造、使用和流通。REACH法规的实施将有助于改善人类的健康，避免环境的损害，优化产业结构、提高产品质量，促进我国涂料行业可持续发展。  \n\n另外，墨西哥政府规定所有涂料产品中的VOC含量不得超过 $490_{8}/\\mathrm{L}$ ，并即将颁布对甲醇使用的限制法规。表2-3-43～表2-3-45列出了有关VOC及限制重金属使用与排放的一些法规。  \n\n表2-3-43欧盟指令关于清漆和色漆VOC含量限量的要求  \n\n\n<html><body><table><tr><td rowspan=\"2\">种类</td><td rowspan=\"2\">类型/光泽范围</td><td colspan=\"2\">VOC含量最大限值/（g/L)</td></tr><tr><td>第一阶段（2007年）</td><td>第二阶段（2010年)</td></tr><tr><td rowspan=\"4\">内墙及天花板用涂料</td><td>水性涂料 光泽（60°)<25</td><td>75</td><td>30</td></tr><tr><td>溶剂型涂料光泽（60°)<25</td><td>400</td><td>30</td></tr><tr><td>水性涂料 光泽(60°)>25</td><td>150</td><td>100</td></tr><tr><td>溶剂型涂料 光泽(60°)>25</td><td>400</td><td>100</td></tr><tr><td rowspan=\"2\">无机底材外墙涂料</td><td>水性涂料</td><td>75</td><td>40</td></tr><tr><td>溶剂型涂料</td><td>450</td><td>450</td></tr><tr><td rowspan=\"2\">室内外木器或金属装饰装修 用涂料</td><td>水性涂料</td><td>150</td><td>130</td></tr><tr><td>溶剂型涂料</td><td>500</td><td>400</td></tr><tr><td rowspan=\"2\">漆室内外透和清漆透明 (Lasure）以及不透明末器着</td><td>水性涂料</td><td>150</td><td>130</td></tr><tr><td>溶剂型涂料</td><td>500</td><td>400</td></tr><tr><td rowspan=\"2\">室内外薄涂涂料</td><td>水性涂料</td><td>150</td><td>130</td></tr><tr><td>溶剂型涂料</td><td>700</td><td>700</td></tr><tr><td rowspan=\"2\">木器或墙面及天花板用封闭 底漆</td><td>水性涂料</td><td>50</td><td>50</td></tr><tr><td>溶剂型涂料</td><td>450</td><td>350</td></tr><tr><td rowspan=\"2\">稳定底材或有疏水性的黏合 底漆</td><td>水性涂料</td><td>50</td><td>50</td></tr><tr><td>溶剂型涂料</td><td>750</td><td>750</td></tr><tr><td rowspan=\"2\">单组分特性涂料</td><td>水性涂料</td><td>140</td><td>140</td></tr><tr><td>溶剂型涂料</td><td>600</td><td>600</td></tr><tr><td rowspan=\"2\">双组分反应性特性涂料</td><td>水性涂料</td><td>140</td><td>140</td></tr><tr><td>溶剂型涂料</td><td>550</td><td>500</td></tr><tr><td rowspan=\"2\">多彩涂料</td><td>水性涂料</td><td>150</td><td>100</td></tr><tr><td>溶剂型涂料</td><td>400</td><td>100</td></tr><tr><td rowspan=\"2\">美饰涂料</td><td>水性涂料</td><td>300</td><td>200</td></tr><tr><td>溶剂型涂料</td><td>500</td><td>200</td></tr></table></body></html>  \n\n表2-3-44德国的TA-Luft法规  \n\n\n<html><body><table><tr><td>级别</td><td>挥发性溶剂排放量/（kg/h)</td><td>最大容许浓度/（mg/m）</td></tr><tr><td>I</td><td>0.1~3</td><td>20</td></tr><tr><td></td><td></td><td>150</td></tr><tr><td>目</td><td>~</td><td></td></tr><tr><td>级别</td><td>致癌性挥发溶剂排放量/（kg/h）</td><td>最大容许浓度/（mg/m）</td></tr><tr><td></td><td>0.3~5</td><td>0.1</td></tr><tr><td>I Ⅱ</td><td>5~25</td><td>1</td></tr><tr><td>Ⅲ</td><td>25</td><td>5</td></tr></table></body></html>  \n\n表2-3-45日本限制铅使用和排放的有关法规  \n\n\n<html><body><table><tr><td>法 规</td><td>目 标</td></tr><tr><td>有毒有害物质控制法规</td><td>限制特种铅化合物的使用及处理</td></tr><tr><td>铅化合物的使用法规</td><td>限制含铅涂料的生产、含铅涂膜的处理、防止危害工人卫生</td></tr><tr><td>防止大气污染法规</td><td><0.1mg/m（以铅计）（废物燃烧排放的废气）</td></tr><tr><td>防止水体污染法规</td><td><0.1mg/m（以铅计）（废水）</td></tr><tr><td>与废物处理有关法规</td><td>埋于土壤中的可溶性铅3mg/L,今后将降低至<0.3mg/L</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 747,
+        "chunk": "# 二、我国涂料工业环境保护现状  \n\n我国涂料工业的环境保护起步较晚，长期以来由于缺少相应的环保法律法规，涂料行业有毒有害物质的排放和管理以及危险化学品的管理处于无政府状态。1999 年国家环境保护局颁布了适合涂料行业的第一项标准，绿色标志涂料—水性涂料标准。2002年1月1日国家质量监督检验检疫总局颁布实施《室内装饰装修材料有害物质限量》等10项强制性国家标准。这一标准从材料上规定了污染物限量，其中与涂料有关的标准有GB18582—2001《室内装饰装修材料溶剂型木器涂料中有害物质限量》、GB18581—2001《室内装饰装修材料溶剂型木器涂料中有害物质限量》，这两个标准对涂料中的有害物都作了明确规定。按照标准要求，生产企业必须按强制性标准生产，有害物质含量超标的涂料则将一律禁止销售。对于水性涂料国家环保总局环保认证中心在原有水性涂料标准的基础上做了进一步规范，颁布了《环境标志产品技术要求水性涂料》（标准号HJ/T201—2005)，标志为圆形、绿色，并标有“中国环境标志”。其中，对水性木器涂料、水性防腐涂料、水性防水涂料等产品，要求VOC含量应小于 $250_{8}/\\mathrm{L}$ ，内墙涂料要求VOC含量应小于 $80\\mathrm{g/L}$ ，外墙涂料要求VOC含量应小于 $150\\mathbf{g}/\\mathrm{L}$ ，墙体用底漆要求VOC含量应小于 $80\\mathbf{g}/\\mathrm{L}$ ；产品生产过程中不得人为添加含有重金属的化合物，不得人为添加含有甲醛的化合物，对重金属和甲醛含量都作了严格的规定。近几年通过国家强制性标准的实施，加强对市场的监控力度，我国在环境保护方面取得了一定的成效。但是传统的高VOC的涂料仍占据着主要市场，其总量不少于100万吨，其VOC一般高于 $550_{B}/\\mathrm{L}$ ，与发达国家现在要求的 $420\\sim450\\mathrm{g/L}$ 的差距还很大。  \n\nGB18581一2001《室内装饰装修材料溶剂型木器涂料中有害物质限量》规定的溶剂型木器涂料中有害物质限量值见表2-3-46。水性木器涂料中对人体有害物质的含量比溶剂型涂料要少得多，是木器涂料的发展方向。 八  \n\nGB18582—2001《室内装饰装修材料内墙涂料中有害物质限量》的技术要求为：VOC含量 ${\\leqslant}200\\mathbf{g}/\\mathrm{L}$ ；游离甲醛 $\\leqslant0.1\\mathbf{g}/\\mathbf{kg}$ ；重金属含量：可溶性铅 ${\\leqslant}90\\mathrm{mg/kg}$ ，可溶性银 $\\leq75\\mathrm{mg/kg}$ ，可溶性铬不大于 $60\\mathrm{{mg/kg}}$ ，可溶性汞 ${\\leqslant}60\\mathrm{mg/kg}$ 0  \n\n表2-3-46溶剂型木器涂料中有害物质限量  \n\n\n<html><body><table><tr><td colspan=\"2\">项目</td><td>硝基漆类</td><td>聚氨酯漆类</td><td>醇酸漆类</td></tr><tr><td colspan=\"2\">挥发性有机化合物（VOC）/（g/L）</td><td>≤750</td><td>光泽（60）≥80%≤600</td><td>≤550</td></tr><tr><td colspan=\"2\">苯/%</td><td>≤0.5</td><td>≤0.5</td><td>≤0.5</td></tr><tr><td colspan=\"2\">甲苯和二甲苯总和/%</td><td>≤45</td><td>≤40</td><td>≤10</td></tr><tr><td colspan=\"2\">游离甲苯二异氰酸酯（TDI)/%</td><td>一</td><td>≤0.7</td><td>一</td></tr><tr><td rowspan=\"4\">重金属（限色漆）/(mg/kg）</td><td>可溶性铅</td><td rowspan=\"4\"></td><td colspan=\"2\">≤90</td></tr><tr><td>可溶性</td><td colspan=\"2\">≤75</td></tr><tr><td>可溶性络</td><td colspan=\"2\">≤60</td></tr><tr><td>可溶性汞</td><td colspan=\"2\">≤60</td></tr></table></body></html>  \n\n随着改革开放的不断深入发展，我国政府和人民越来越重视对环境的保护，逐步建立起一系列与国际接轨的环保法规。环保法规的规定是涂料市场发生变革的主要原因。法规总是能催生变革，但现今的环保标准波动所造成的变革比以往都要大。环保法规变革的前沿就是要限制VOC排放到大气中去。基于上述原因，我们应该将研究力度集中在低溶剂和无溶剂的涂料产品的发展上。",
+        "category": " Introduction"
+    },
+    {
+        "id": 748,
+        "chunk": "# 第七节发展趋势  \n\n由于传统涂料对环境与人体健康有影响，所以现在人们都在想办法开发环境友好型涂料。第一，人们努力降低涂料总有机挥发量（VOC)，有机挥发物对我们的环境和人类自身构成直接的危害。除交通运输业带来的污染外（比如汽车尾气、油品渗透等)，涂料是现代社会中的第二大污染源。因此，涂料对环境的污染问题越来越受到重视。美国洛杉矶地区在1967年实施了限制涂料中挥发性有机溶剂量的66法规。自此以后，国外对涂料中溶剂的用量的限定也愈来愈严格。开始只对一些可发生光化学反应的溶剂实施限制，但后来发现几乎所有的溶剂都能发生光化学反应（除了水、丙酮等以外)。我们应该尽量减少这些溶剂的用量。第二，大家更加关注溶剂的毒性，那些和人体接触或吸入后可导致疾病的溶剂，如大家熟知的苯、甲醇便是有毒的溶剂。乙二醇的醚类曾是一类水性涂料常用的溶剂，在20世纪70年代，它作为溶剂而被大量使用；但在20世纪80年代初发现乙二醇醚是一类剧毒的溶剂，目前，在涂料工业中正逐步被淘汰。有毒的溶剂对生产和施工人员都会造成直接危害。第三，使用安全问题也引起人们的极大注意，一般说来涂料干燥以后，它的溶剂基本上可以挥发掉，但这要有一个过程，特别是室温固化的涂料，有的溶剂挥发得很慢，这些溶剂的量虽然不大，但由于用户长时间的接触，也会造成对人体健康的伤害，因此在制备时一定要限制有毒溶剂的使用。20世纪70年代以前，几乎所有涂料都是溶剂型的。70年代以来，由于溶剂的昂贵价格和降低VOC排放量的要求日益严格，越来越多的低有机溶剂含量和不含有机溶剂的涂料得到了快速发展。尽管为满足日益苛刻的环保要求，低VOC的乳胶漆、水性涂料、UV光固化涂料及粉体涂料得到了迅速地发展，但溶剂型涂料以其性能和施工优势仍在涂料领域中占有相当重要的地位。在中国涂料工业，溶剂正朝着以下方向发展。",
+        "category": " Introduction"
+    },
+    {
+        "id": 749,
+        "chunk": "# 1.低毒甚至无毒化  \n\n美国国会在1990年列出了将要减少使用危害空气污染物（HAP）清单，其中包括MI-BK、BCs、芳烃、甲醇、乙二醇及乙二醇醚等。  \n\n苯属中毒性溶剂，会导致造血系统的病害，不能用于涂料中，中国及国际上多数国家对溶剂苯含量都有严格的限制；乙二醇醚及其酯类溶剂（尤其是CAC）属高毒溶剂，应禁止使用；某些溶剂对于涂料来说仍必不可少，如甲苯、二甲苯、混合芳烃S-100、MIBK及乙二醇丁醚等。目前人们正积极寻找新的不在HAP清单上的溶剂。欧盟已立法在与人接触的产品中对某些物质设限，其中包含PAHs多环芳香烃。",
+        "category": " Introduction"
+    },
+    {
+        "id": 750,
+        "chunk": "# 2.使用高效溶剂  \n\n除使用较多的正丁醇、异丁醇、异丙醇、丁酮、丙酮、醋酸丁酯、醋酸乙酯以外，其实有不少性能优良的溶剂可以采用。如甲戊酮（2-庚酮）用于硝基漆中可有效地改善漆膜延展性、防潮性和光泽性；三甲基环已酮在涂料中可用作气干和烘干体系的流平剂，可以减少气泡和缩孔的生成，提高流动性和光泽；将二异丁基酮（DIBK）用于以聚酯树脂为基材的卷材涂料和罐装涂料中可有效改进涂料的涂膜性能等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 751,
+        "chunk": "# 3.无苯化  \n\n人们正在努力减少芳烃溶剂的用量。减少甲苯、二甲苯及混合芳烃用量，一直是各油漆厂家努力的方向。  \n\n脱芳烃溶剂油有望用于替代甲苯、二甲苯及混合芳烃。目前国内市场的脱芳烃溶剂油主要以烷烃、环烷烃为主。烷烃分为正构和异构两类，在常温下其化学稳定性比较好，密度小。环烷烃的化学稳定性良好，与烷烃近似，凝点低、润滑性好并且无毒。混合烷烃又称D系列脱芳烃溶剂油，它们不含多环芳香烃，芳烃含量被控制在 $100{\\sim}150\\mathrm{ppm}^{\\bullet}$ 范围。对人基本无毒，性能稳定。但基本上由环烷烃和烷烃组成，无极性，与众多带极性基团的树脂混溶性差，对众多带极性基团的树脂基本无溶解力。直接在配方中用D系列脱芳烃溶剂油替代甲苯、二甲苯和三甲苯被证明难度大，开发与之配套的助溶剂有望提高其混溶性。随着混溶性改进、烷烃溶剂以其低毒性及相对稳定的成本会被更广泛使用。  \n\n碳酸二甲酯（Dimethylcarbonate，DMC）常温时是一种无色透明、略有气味、微甜的液体，熔点4℃，沸点 $90.1\\mathrm{{^{\\circ}C}}$ ，密度1 $\\mathrm{.069g/cm^{3}}$ ，难溶于水，但可以与醇、醚、酮等几乎所有的有机溶剂混溶。DMC毒性很低，在1992年就被欧洲列为无毒产品，是一种符合现代“清洁工艺”要求的环保型溶剂，近年来引起了广泛的重视。由于其分子结构中含有羰基、甲基、甲氧基和羰基甲氧基，作为溶剂，DMC可望部分替代甲苯、二甲苯等用于涂料中。目前DMC市场售价与甲苯、二甲苯处于相当范围。在涂料中的应用有望快速增长。  \n\n当然，由于高活性，碳酸二甲酯的贮存稳定性一直困扰着经销商。  \n总之，高效、低毒性及高性价比将是涂料溶剂发展的方向。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 752,
+        "chunk": "# 参考文献  \n\n[4] Hildebrand J, Scot R.The solubility of Non-electrolytes,Third Edition,New York; Reinhold publishing Cx[5] Burrell H. offiecial DIGEST, 1995, 27； 369.  \n[6] Lieberman E P. official DIGEST, 1962, 34: 444.  \n[7] 孙信德．涂料工艺，1983，2.  \n[8] ［美］T.C.巴顿著，涂料流动和颜料分散，郭隽奎，王长卓译，北京：化学工业出版社，1988.  \n[9] 赵敏主编，涂料毒性与安全实用手册，北京：化学工业出版社，2004.  \n[10] 李华昌，符斌主编，简明溶剂手册，北京：化学工业出版社，2009.  \n[11] 魏杰，金养智编著，光固化涂料，北京：化学工业出版社，2005.  \n[12] 刘振宇主编，涂料涂装技术强制性标准认证全书：第1，2册，吉林：吉林摄影出版社，2002.  \n[13] 刘泽眼， 涂料工业与环境保护，精细与专用化学品，2002，（17）：3-6.  \n[14] 刘秀娟，陈千贵，谢慧玲，溶剂型涂料环境保护问题的变革，中国涂料，2006，（8）；35-47.  \n[15] 寇辉，唐军，水性涂料中VOC的危害与控制，中国涂料，2005，（9)：39-40.  \n[16] 杨向宏，中国涂料业溶剂使用及发展趋势，hc360慧聪网，2009-6-9.",
+        "category": " References"
+    },
+    {
+        "id": 753,
+        "chunk": "# 助剂",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 754,
+        "chunk": "# 第一节助剂的分类、作用及整体匹配性  \n\n涂料生产工艺的强化、涂料贮运中的稳定性、涂层的配套性及涂膜缺陷的克服、涂装施工性能的改善和提高，都与涂料助剂的应用分不开。  \n\n为了更专业化和高效地从事涂料技术的研发，涂料工作者都必须掌握涂料助剂的化学、物理性质，功能特性及应用方法。  \n\n要涂料生产工艺和涂料性能达到某种特定要求而少量添加的一些辅助的特殊材料，称为涂料助剂。  \n\n涂料助剂在涂料中可发挥出30种以上的功能。任何一个优秀的涂料配方中都会包含几种助剂，至少也要有两种，多者达到5种以上。一般常规的溶剂型涂料助剂的应用总量是涂料质量的1%～3%，特殊高档涂料有的甚至达到10%。水性乳胶漆助剂的通常用量是涂料总量的5%～8%。在国外高档漆中，助剂的价格成本可占到30%左右。",
+        "category": " Introduction"
+    },
+    {
+        "id": 755,
+        "chunk": "# 一、涂料助剂的作用及分类  \n\n涂料助剂作用广泛，品种繁多，其分类方法很多，通常是按其用途及作用位置和方式来分类。",
+        "category": " Introduction"
+    },
+    {
+        "id": 756,
+        "chunk": "# 1.按用途分类  \n\n这种分类法是按涂料助剂在涂料生产、涂装等不同阶段的应用情况进行归纳分类。  \n\n(1）在涂料制造时发挥作用的助剂在这个阶段主要应用的助剂有润湿分散剂、消泡剂、脱泡剂、乳化剂、引发剂、催化剂、链终止剂等。其中乳化剂、引发剂、催化剂等是用于树脂合成及乳液制备过程，应属于涂料半成品的生产。颜料的润湿分散是涂料生产的技术关键，对涂料的性能有极大的影响。为了提高颜料与基料的亲和性及其在分散体中的稳定性，有时单独依靠树脂是不够的，必须使用润湿分散剂。它可以降低颜料与树脂之间的界面张力，提高润湿效率，减少研磨时间，降低能耗，还可以提高涂料贮存稳定性，防止涂膜浮色发花，增强颜料的着色力、展色力、遮盖力，降低成本。还可以赋予涂膜良好的耐候性及光泽。  \n\n消泡剂是水性涂料生产时必不可少的一种助剂，水性涂料特别容易起泡，若不及时消除，生产及包装就无法进行。  \n\n(2）在贮运中发挥作用的助剂在这个阶段产生作用的助剂有增稠剂、防沉剂、防结皮剂、杀菌防腐剂、防锈剂等。涂料在生产阶段属于高剪切速率的运动状态，在贮存中几乎没有剪切力，颜料容易产生絮凝、返粗、沉淀、结皮、增稠等不良现象。增稠剂、防沉剂、分散剂可防止颜料产生沉淀，使涂料分散体处于稳定状态。防结皮剂可以防止氧化干燥聚合的油性涂料产生结皮，减少浪费。分散剂还可以防止因颜料絮凝而产生增稠现象，影响涂料的颜色及光泽。  \n\n(3）在涂料和涂膜干燥时发挥作用的助剂在这个阶段发挥作用的助剂有流动和流平促进剂、表面状态控制剂、防浮色发花剂、防流挂剂、消泡剂、基材润湿剂、防闪锈剂、催干剂、固化促进剂等。  \n\n涂料在这个阶段理化性质会产生较大的变化。成膜前涂料是液态，成膜后变成固态。涂装后的表面积与涂装前罐中液态时的表面积相比，增加是巨大的，所以在涂装过程中涂料的流动性质是非常重要的。除此之外还有许多新问题，被涂物表面与涂料之间的界面张力会影响涂料的流平性，涂膜的附着力。涂膜干燥过程中，溶剂挥发，体积收缩率可达 $30\\%\\sim70\\%$ ，造成表面张力失衡，会产生强大的涡流作用，造成橘皮、缩孔、浮色发花等不良现象。  \n\n针对这些问题要选择不同的助剂帮助解决。用流平剂可解决涂料的流动和流平的问题；用基材润湿剂可解决基材与涂膜之间的界面张力；用表面状态控制剂可解决表面失衡、涡流问题。  \n\n为了提高涂膜的干燥速率，缩短干燥时间，氧化聚合干燥的涂料必须使用催干剂。交联固化型涂料，多用固化促进剂。对甲苯磺酸或其盐可降低氨基烘漆的固化温度，缩短干燥时间。又如聚氨酯涂料，特别是无溶剂的不饱和聚酯涂料、环氧涂料，除交联固化剂外，还经常使用固化促进剂提高干燥速率。乳胶漆要使用成膜助剂，光敏涂料要使用光引发剂。  \n\n帮助涂料固化成膜的助剂虽然称呼不同，但是作用目的却是相同的，全是为了加快涂膜的固化速率，缩短干燥时间。  \n\n在涂料进行立面涂装时，经常会发生不同程度的流挂现象，严重地影响了涂膜的装饰性。为了克服这种不良现象，人们常用的添加剂是触变剂，即在高剪切速率下，涂料的结构黏性被破坏，黏度下降，涂料具有流动和流平性，在低剪切速率下结构黏性恢复，起到防沉、防流挂的作用。  \n\n触变剂是乳胶漆必用的添加剂，主要是控制高中低剪切速率下的黏度，来达到防沉、防分水及涂膜流平的目的。现在甚至有人将缔合型的中剪切速率下的PU增稠剂称为“流平剂”。  \n\n涂料的涂装方法很多，有刷涂、喷涂、浸涂、辊涂、静电喷涂、电泳涂装等。无论采用哪种方法，涂膜难免产生缺陷，出现问题时一定要根据涂料的类型，并结合涂装方法来选择合适的助剂，在助剂应用时还要注意它们之间的整体匹配性。  \n\n(4）在涂膜中发挥作用的助剂在这个阶段体现出作用的助剂有紫外线吸收剂、光稳定剂、划痕防止剂、防粘连剂、防霉剂、导电剂、防污剂、阻燃剂等。这些助剂都在涂膜形成后在涂膜中发挥作用。  \n\n当涂膜在氧存在的条件下，树脂基料受紫外线的照射会发生光化学降解反应，涂膜遭受破坏。为了保护涂膜，人们采用紫外线吸收剂吸收紫外线，再将热能释放出来，抑制或减缓了化学反应的发生，保护了涂膜，延长了涂膜的使用寿命。防霉剂是一种能杀死霉菌和藻类的助剂，可以防止霉菌和藻类在涂膜表面上的生长，提高了涂膜的使用寿命和装饰性。防污剂也是一种助剂，含有防污剂的防污涂料涂在船舶水线和水线以下的船底部位，防止海生物的附着。涂料中添加阻燃剂可以防止或减缓火焰的蔓延，保护建筑物和人身的安全。导电涂料是一种功能型涂料，由于涂料中添加了导电剂，涂料具有导电性、抗静电性、屏蔽电磁波的功能。抗划伤、抗粘连剂，实际上是降低了涂膜的表面粗糙度，在涂层表面起到了润滑剂的作用，减少了摩擦阻力，产生滑爽感，起到抗划伤、抗粘连的作用。有机硅类和氟类的流平剂及蜡类助剂都具有这些作用。  \n\n有些助剂能够赋予涂料某些新的功能，涂料也常以其赋予的功能命名。例如，使用了阻燃剂的涂料常称为阻燃涂料，还有防污涂料、导电涂料、防霉涂料等都因助剂而得名。  \n\n有些助剂只能在某-方面发挥一种作用。例如阻燃剂、导电剂、防锈剂等。有些助剂在上述所有阶段都能发挥作用，有的助剂只能在一个或两个以上阶段发挥作用。有的只有一种作用，有的具有多种作用。例如，消泡剂可以在生产、贮运、施工中只发挥消泡作用。而流平剂和润湿分散剂能在每个阶段发挥出多种作用。对这些具有多功能的助剂在应用时要进行全面分析、实验、权衡利再作取舍。尤其是有负面作用的助剂，绝对不应因其在某些方面有缺欠而全面否定，要扬长避短，对各种助剂之间的作用功能要进行整体平衡。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 757,
+        "chunk": "# 2.按作用位置和方式分类  \n\n还可按照助剂在涂料中起作用的位置和方式对它们进行分类。  \n\n(1）具有界面活性的助剂这类助剂是界面活性剂。它们拥有吸附基，吸附在相的界面处。它们的功能作用是在界面或接近界面的地方发挥的。比如润湿分散剂，依靠吸附基吸附在颜料的表面，降低颜料/基料的界面张力，从而起到润湿、分散、稳定的作用。流平剂会在涂膜表面定向排布，降低涂膜的表面张力，使表面张力趋于平衡，达到控制表面状态的目的。消泡剂在涂料中会在空气/基料的界面处排布，起到脱泡和消泡的作用。  \n\n具有界面活性的助剂有润湿剂、分散剂、防浮色发花剂、流动和流平剂、表面状态控制剂、基材润湿剂、附着力促进剂、表面调理剂、消泡剂、防结皮剂、乳化剂、防沉剂、抗静电剂等。  \n\n涂料生产和施工过程中使用的这类助剂很多，这些助剂还可以按结构划分成阴离子型、阳离子型、非离子型、两性、电中性和高分子聚合物型等。  \n\n具有界面活性的高分子润湿分散剂，它的研制开发受颜料浆稳定的空间位阻理论的影响是极大的。这种分散剂的结构完全不同于传统型的表面活性剂。分子中具有与颜料表面亲和的锚定基团，为提高与颜料表面吸附的牢度，亲和基团多到数十个甚至几百个。还有与分散介质相容的伸展链段。锚定基团牢牢地吸附在颜料的表面上，伸展基伸展在基料中，构成空间位阻，达到了颜料分散的稳定性。高分子活性分散剂有溶剂型的、水性的，还有水油两性的。这类分散剂近年来发展特别快，如受控游离基聚合制备的分散剂。这是在界面处发挥作用的一个典型代表。  \n\n(2）非界面活性的助剂非界面活性的助剂绝大部分是在涂料和涂膜中发挥作用的。多数是为了增强涂料和涂膜某些性能或强化某个工艺过程。这些助剂主要有催干剂、消光剂、增塑剂、防腐剂、防霉剂、防污剂、导电剂、阻燃剂、紫外线吸收剂、固化促进剂、增稠剂、触变剂、防流挂剂、防沉剂等。一般来讲，具有界面活性的助剂多在液态中发挥作用，用量相对比较低，占整体配方的 $0.05\\%\\sim1.0$ %时就能产生很明显的效果。而非界面活性的助剂一般用量比较高，大约要占配方总量的 $1.0\\%\\sim3.0\\%$ 6时才能获得较佳的效果。  \n\n涂料助剂的分类方法还有一些，在此只列举大家所熟悉的这两种。  \n\n现将涂料助剂在涂料的各个阶段所发挥的作用及作用的位置归纳于表2-4-1。  \n\n表2-4-1涂料助剂发挥作用的阶段及位置  \n\n\n<html><body><table><tr><td>涂料助剂名称</td><td>发挥作用阶段</td><td>发挥作用位置</td></tr><tr><td>乳化剂</td><td>树脂，乳液聚合</td><td>单体/介质，界面</td></tr><tr><td>引发剂、催化剂、链终止剂</td><td>树脂合成</td><td>单体聚合反应相中</td></tr><tr><td>润湿剂、分散剂、消泡剂、脱泡剂</td><td>涂料生产、颜料分散 涂料生产、研磨、包装</td><td>颜料/基料，界面 涂料/空气，界面</td></tr><tr><td>触变剂、防沉剂、罐内防腐剂（杀菌剂）、缓冲剂、防结皮剂、pH调节剂</td><td>贮存、运输</td><td>介质中（漆料）</td></tr><tr><td>防锈剂</td><td>贮存、运输</td><td>漆料/铁罐壁，界面</td></tr><tr><td>动滑泡剂、脱泡剂、表面状态控制剂（防缩孔剂、防橘皮剂、防发花剂）、流</td><td rowspan=\"4\">涂装成膜过程</td><td>涂膜/空气，界面</td></tr><tr><td>颜料稳定剂（分散剂）</td><td>颜料/基料，界面</td></tr><tr><td>基材润湿剂、闪蚀抑制剂、附着力促进剂</td><td>基材/漆料，界面</td></tr><tr><td>催干剂、催化剂、固化剂、固化促进剂、成膜剂、消光剂</td><td>漆料中（涂膜中）</td></tr><tr><td></td><td rowspan=\"2\">在干燥的涂膜中</td><td>涂膜/空气，界面</td></tr><tr><td>表面调整剂、增光剂、增滑剂、抗静电剂 消光剂、紫外线吸收剂、导电剂、防霉剂、热稳定剂</td><td>涂膜中</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 758,
+        "chunk": "# 二、涂料助剂应用的整体匹配性  \n\n涂料是多种材料的组合体，助剂是涂料生产必不可少的材料。为了更好地发挥助剂的作用，一定要注意助剂的整体匹配性。主要注意的问题应有以下三方面：首先是助剂与基料之间的相容性；其次是助剂与助剂之间的协同性；最后是用助剂协调涂料性能要求之间矛盾的平衡性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 759,
+        "chunk": "# 1.涂料助剂与基料之间的相容性  \n\n涂料各组分之间的相容性是涂料配方设计中的首要问题，相容性不好会给涂料性能造成极大影响，轻者会影响涂料的透明性，重者会使涂料许多性能受到破坏。涂料助剂的应用也不例外，首先要与基料有良好的相容性。尤其是具有界面活性的助剂。  \n\n润湿分散剂、消泡剂、流平剂都要求与基料有良好的或一定限度的相容性。否则助剂不但不会发挥良好的功能作用，反而会造成负面影响，甚至起破坏作用。  \n\n关于消泡剂的相容问题，大家知道消泡剂若相容性太好，消泡能力会相对下降，消泡剂相容性不好往往消泡能力很强，但会造成许多病，如光泽不好，影响层间附着力等。所以消泡剂应用时一定要注意消泡能力与产生泡沫的活性物的匹配性，也就是说消泡剂的表面张力一定要比产生泡的活性物的表面张力低。另外要注意消泡剂在基料中应具有兼容性，既不能不容，又不能完全相容，应达到有限相容。  \n\n润湿分散剂特别是高分子型分散剂，若相容性不好，还不如不添加的好。高分子型分散剂如果与树脂基料相容不好，它的长链伸展基在分散剂中卷缩成线团状，伸展不开，即使吸附基吸附在颜料的表面上也构不成空间位阻效应，对颜料分散没有任何好处。会导致色浆的黏度高，展色力差，返粗增稠，涂膜光泽下降，所以应用时一定要首先检查助剂与树脂的相容性。另外当购买色浆配复色漆时，一定要注意色浆之间的相容性，如果相容性不好会导致浮色发花，多数原因是分散剂之间不相容，产生颜色的分离现象。也可能是其中某种分散剂与树脂基料不相容。可通过架桥的分散剂来连接不相容的双方进行解决，最好的办法是更换分散剂和色浆。当然更换树脂也是可行的，不过这种做法更复杂。  \n\n除上述的分散剂要与基料有良好的相容性外，还要注意分散剂之间的相容性。若要复配用两种以上分散剂制备的色浆时，选用的分散剂最好具有良好的相容性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 760,
+        "chunk": "# 2.尽量发挥正面作用，减少互相“拆台”的负面影响  \n\n所用助剂并不是只有发挥功能作用的正面影响，也时也有相互“拆台”的负面影响，在应用之中一定要注意助剂之间的协同性，减少和消除相互抵消的“拆台”作用。  \n\n聚醚改性的聚二甲基硅氧烷，有控制涂膜表面状态，降低界面张力，提高基材的润湿性，增强附着力和展布性的能力。但它还有稳泡，不利于涂料流动，影响层间附着力，过温烘烤容易分解变成长链硅氧烷等造成表面缺陷等负面影响。  \n\n分散剂，特别是传统型的，对颜料润湿分散有帮助，但却有起泡的负面作用。特别是在水性涂料中。还要注意分散剂所含成分与树脂的相互作用关系，比如含氨基的高分子分散剂对环氧涂料的贮存稳定性会产生影响。  \n\n水性涂料用的缔合型增稠剂，特别是PU类的增稠剂对分散剂、消泡剂、共存溶剂都有敏感性。其疏水基会与分散剂的疏水基、树脂的亲油基缔合，导致颜料分散性变差、增稠效果不佳，严重者会使涂料变稀。  \n\n助剂造成的负面影响是很多的，涂料工作者应平衡助剂对涂料的利害关系，使负面作用减到最低程度。有机硅类流平剂容易稳泡，可以改用丙烯酸类流平剂，既不稳泡还有助消泡作用。另外，即使同属硅类流平剂，其稳泡程度也不一致，可选择不稳泡和稳泡程度低的流平剂，还可选择硅类和丙烯酸类流平剂搭配使用。传统型分散剂易起泡，可选择高分子型分散剂。PU类增稠剂敏感，可以选用HASE（疏水改性的碱溶胀乳液）和HMPE（疏水改性聚醚）等。  \n\n如不能更换，可采用折中方法。根据要求增减助剂添加量，削弱一方，增强另一方。比如乳化剂、分散剂易起泡，可以增加消泡剂的用量或更换消泡能力更强的消泡剂。在这种情况下，选择消泡剂时，一定要在添加了分散剂、流平剂、基材润湿剂等之后，再通过实验来确定消泡剂的种类和用量。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 761,
+        "chunk": "# 3.协调涂料性能要求之间矛盾的平衡性  \n\n涂料中有些性能要求是相互矛盾的。涂料的流平性与防流挂是相互矛盾的。低黏度的牛顿流体对流平是非常有利的。但这种涂料在立面涂装时是极易产生流挂的。为了防止流挂，要添加触变剂，使涂料变成触变流体。黏度变大有助于防流挂，但对流动和流平会产生影响。黏度太低又达不到防流挂的目的。为此一定要合理选择触变剂的种类和添加量，调整屈服值，控制结构黏度的恢复时间。也就是说黏度恢复到能够阻止流挂产生的程度时，恰好也是涂料完成了流平的时间。  \n\n触变剂是协调涂料流平与流挂关系的平衡助剂，可使矛盾双方达到统一，既可流平又不流挂。  \n\n氧化聚合干燥型涂料的干燥和防结皮，是干燥过程中的矛盾双方。加催干剂的目的是为了加速干燥成膜。但这类涂料在贮存中由于表面与空气接触，在短时间内就可以氧化聚合，形成干燥结皮，皮层会越结越厚，涂装施工时必须清除掉，一桶漆多次使用多次清除，造成极大浪费，因此人们提出了防结皮的要求。  \n\n不加催于剂，涂膜不干，行不通。最初采用高沸点溶剂盖面，后来又采用酚类化合物，这种化合物虽可达到防结皮的目的，但影响干率。最后人们开发了类化合物，特别是甲乙酮，在贮存中可以阻止氧化聚合反应达到不结皮的目的。但在成膜时它会很快离开涂膜挥发掉，所以对涂膜干燥构不成影响。  \n\n防结皮与干燥是将涂料的一个主要性能分解成矛盾的两方面，快干和不允许干。不需要干的时候就别干，需要干的时候再干。用两种助剂来分解这个主体性能，催干剂和防结皮剂，达到整体性能要求的匹配性。  \n\n另外，基材润湿与涂膜的流平也是矛盾的，这在溶剂型涂料中表现得不明显。但在水性涂料、高固体分涂料和无溶剂型涂料中就显得特别重要。这些涂料中几乎都没有溶剂，表面张力都比较高，都存在对基材润湿性差的问题。添加基材润湿剂可以提高涂料对基材的润湿性，但却会给流平带来负面影响。所以在选择基材润湿剂时要注意挑选对涂层表面影响不大的，能够多数趋向于液/固界面定向排布的基材润湿剂，如TegoWetKL245。能够降低涂料的界面张力，具有很好的展布性，还能增加附着力。  \n\n对于这类矛盾的平衡，最好选择适宜的基材润湿剂配合不降低表面张力的丙烯酸类流平剂来促进表面的流动性。增强基材润湿性，平衡表面的流动性不伤害任何一方的性能来达到整体的匹配性。  \n\n前面讲过，涂料是多种材料的组合体，将许多材料组合到一起产生一些矛盾是很正常的。涂料工作者只有做好各种材料之间的匹配，做好各种性能之间的匹配，协调各种矛盾，才能做出好的涂料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 762,
+        "chunk": "# 第二节助剂各论",
+        "category": " Introduction"
+    },
+    {
+        "id": 763,
+        "chunk": "# 一、润湿分散剂",
+        "category": " Introduction"
+    },
+    {
+        "id": 764,
+        "chunk": "# 1.引言  \n\n涂料与油墨制造过程中的颜料分散剂是指在机械力的作用下，颜料的二次团粒经过润湿、分散在展色剂中，得到一个稳定的颜料分散悬浮体。悬浮体的稳定性与颜料、树脂、溶剂三者的性质及其相互作用有关。要想制得一个良好的颜料分散体，有时必须要借助于润湿分散剂的帮助。  \n\n颜料的润湿、分散和稳定这三个过程是紧密相连、不可分离的。润湿是一个颜料表面置换的过程；分散是颜料的聚集体在外力作用下分离的过程；稳定是颜料经分散后不再发生絮凝（返粗）的过程。  \n\n润湿剂和分散剂都是界面活性剂，润湿剂能降低液/固之间的界面张力，增强颜料表面的亲液性，提高机械研磨效率，分散剂吸附在颜料的表面上构成电荷作用或空间位阻效应，使分散体处于稳定状态：  \n\n润湿和分散，尽管这两个词就词义而言是不完全相同的，但其作用达到的结果却是极其相似的，往往很难区分，尤其是高分子分散剂，同时兼具润湿和分散作用，因此，人们常称其为润湿分散剂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 765,
+        "chunk": "# 2.颜料的润湿性  \n\n颜料润湿是一个表面置换过程，将固/气界面变成固/液界面。只有在颜料与树脂溶液的亲和力大于基料中树脂之间的亲和力时才会实现。  \n\n(1）接触角与润湿当液体与固体接触时会形成一个夹角，这个角被称为接触角，它是液体对固体润湿程度的一个衡量标志。杨氏方程表示了接触角与界面张力的关系。  \n\n$$\n\\gamma_{\\mathrm{so}}=\\gamma_{\\mathrm{sl.}}+\\gamma_{\\mathrm{l.G}}\\cos\\theta\n$$  \n\n式中  \n\n$\\gamma_{\\mathrm{{sG}}}$ —固/气界面张力；  \n$\\gamma_{\\mathrm{s{L}}}$ 固/液界面张力；  \n$\\gamma_{\\mathrm{{LG}}}$ 液/气界面张力；0—液体与固体的接触角。  \n\n由式（2-4-1）可导出式(2-4-2)：  \n\n$$\n\\mathrm{cos}\\theta{=}\\frac{\\gamma_{\\mathrm{sc}}-\\gamma_{\\mathrm{sL}}}{\\gamma_{\\mathrm{l,c}}}\n$$  \n\n当 $\\gamma_{\\mathrm{sc}}{<}\\gamma_{\\mathrm{st,}}$ ，那么 $\\cos\\theta<0$ . $\\theta>90^{\\circ}$ 。不润湿。当 $\\theta=180^{\\circ}$ 时，完全不润湿，液体会形成水珠滚动现象。  \n\n当 $\\gamma_{\\mathrm{LG}}{>}\\gamma_{\\mathrm{SG}}{-}\\gamma_{\\mathrm{SL}},$ ，则 $1{>}\\cos\\theta{>}0$ . $\\theta{<}90^{\\circ}$ 。液体可以润湿固体，但不会完全润湿，银展不好。  \n\n当 $\\gamma_{_{\\mathrm{LG}}}=\\gamma_{_{\\mathrm{SG}}}-\\gamma_{_{\\mathrm{SL}}}$ ，则 $\\scriptstyle\\cos\\theta=1$ ， $\\scriptstyle\\theta=0^{\\circ}$ 。液体会完全润湿固体，形成良好的铺展现象。  \n\n既然润湿是颜料由固/气界面转换成固/液界面，润湿效率BS就应为：  \n\n$$\nB S{=}\\gamma_{\\mathrm{sG}}{-}\\gamma_{\\mathrm{sL}}\n$$  \n\n若将式（2-4-3）代入式（2-4-1)，润湿效果则为：  \n\n$$\nB S{=}\\gamma_{\\mathrm{{l,G}}}{\\cos\\theta}\n$$  \n\n因为 $\\gamma_{\\mathrm{{LG}}}$ 和 $\\theta$ 角都可以测定出来，所以润湿效率是可以计算的。但计算时要注意修正。  \n\n(2）影响润湿效率的其他因素影响润湿效率的因素除界面张力和接触角外，还有颜料集合体中空隙度的孔径和深浅，树脂基料的黏度。  \n\nWashborre用公式表示了颜料粒子润湿的初始阶段，各种因素与润湿效果的关系。  \n\n式中K-—常数；$\\boldsymbol{\\gamma}_{\\mathrm{{F1}}}$ —基料的表面张力；$R$ 颜料颗粒中的空隙半径；$\\scriptstyle{L}$ —颜料颗粒中的空隙长度；$\\eta$ 一基料黏度。  \n\n式(2-4-5）中的 $\\gamma_{\\mathrm{{F1}}}\\cos\\theta$ 就是式（2-4-4）所述的润湿效率。除此之外，Washborre把颜料粒子的状态、空隙度的大小及深浅，还有树脂基料的黏度等与润湿效率结合起来了。  \n\n综上分析，颜料润湿缓慢的原因如下。  \n\n（1）扩散压力非常小（界面张力高，如疏水性颜料在水中分散）。  \n\n（2）颜料颗粒中空隙度的孔径小而深（如絮凝体颜料粒子）。  \n\n（3）基料黏度高（与研磨相反，在高黏度下可获得强的剪切力，能提高研磨效率，但对制造高浓度颜料色浆却不利)。  \n\n（4）要提高润湿效率，采用润湿分散剂降低界面张力，减小接触角是一个非常有效的方法。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 766,
+        "chunk": "# 3.颜料分散体的稳定性  \n\n分散体稳定性差主要表现在颜料分散粒子产生絮凝和沉降。这对涂料和油墨的光泽、着色力、遮盖力、耐候性会产生极大的影响。同时还会导致涂料浮色发花、开罐质量不佳，出现浮油、分层、沉淀等不良现象。 76  \n\n(1）比表面积与稳定性的关系颜料的聚集体被研磨分散成小粒子时，比表面积增加了。设颗粒的边长为 $\\textbf{\\em L}$ ，粉碎后小粒子的边长为 $x.$  \n\n那么小粒子的个数为 $L^{3}/X^{3}$ (个)。  \n\n分散后小粒子的总面积为： $6X^{2}(L^{3}/X^{3})=6(L^{3}/X)$  \n\n假设把一个边长 $5\\mu\\mathrm{m}$ 的大颗粒粉碎成边长 $0.5\\mu\\mathrm{m}$ 的小粒子。粒子的个数、比表面积、边、角的变化情况见表2-4-2。  \n\n表2-4-2边长由5μm变成 $0.5\\upmu\\mathrm{m}$ 个数、总面积、边、角的变化情况  \n\n\n<html><body><table><tr><td>边长/μm</td><td>粒子个数/个</td><td>总边长/μm</td><td>总面积/μm</td><td>总角数/个</td></tr><tr><td>5</td><td>1</td><td>5X12=60</td><td>5X5X6=15</td><td>- 8</td></tr><tr><td>0.5</td><td>10×10×10=1000</td><td>0.5×12×1000=6000</td><td>0. 5×0. 5×6× 1000=1500</td><td>8X1000=8000</td></tr></table></body></html>  \n\n由上表可知，由一个边长 $5\\mu\\mathrm{m}$ 的大粒子变成边长 $0.5\\mu\\mathrm{m}$ 的小粒子时，角增加了1000倍，边长增加了100倍，面积增加了10倍。  \n\n颜料粒子表面原子的价力饱和程度是有差异的。在棱、角、边及凹凸部位剩余价力较多，吸附力较强，具有很强的凝聚力。  \n\n另外，就热力学而言，粒子变得越小，比表面积（S）变得越大，表面自由能就越大，假设分散体内部的自由能没有变化，分散体系的自由能就受 $G_{s}=\\gamma_{s}$ 支配。表面张力不会变，比表面积增大，表面自由能肯定增大，所以稳定性就变差了。  \n\n机械分散后微粒新增加面积、边、角都是疏液的，若得不到润湿及很好的能障保护，这些新分散的细小微粒更容易产生絮凝。  \n\n(2）颜料沉淀颜料分散体中的颜料粒子处于不停的运动状态，运动的速度是受粒径、形状、密度、絮凝度等诸多因素影响的。  \n\n在无限扩展的牛顿流体分散体系中，单一球形粒子的沉降速率可用Stokes公式求出：  \n\n$$\nv_{\\flat}=\\frac{2a^{2}(\\rho-\\rho^{\\circ})_{\\mathscr{E}}}{9\\eta}\n$$  \n\n式中 $v_{\\ast}$ —等速运动的终点速度；α-粒子半径；$\\rho$ —分散相的密度；$\\rho^{\\circ}$ —分散介质的密度；， 一重力加速度。  \n\nKersse将Stokes公式简化成式（2-4-7）：  \n\n可用该式探讨设计涂料配方中的颜料是否有浮色的倾向，以便制定相应处理措施。如用醇酸树脂、 $\\mathrm{TiO}_{2}$ 和 $\\mathrm{Fe}_{2}\\mathrm{O}_{3}$ 制造浅红色漆。  \n\n醇酸树脂密度， $0.98g/\\mathrm{cm}^{3}$ ； $\\mathrm{TiO}_{2}$ ，密度 $4.20\\mathrm{g/cm^{3}}$ ，细度 $0.25\\mu\\mathrm{m}$ . $\\mathrm{Fe}_{2}\\mathrm{O}_{3}$ ，密度$5.00\\mathbf{g}/\\mathrm{cm}^{3}$ ，细度0. $25\\mu\\mathrm{m}$ 中 $\\mathrm{TiO}_{2}$ 的沉降速率， $(4.2-0.98)\\times0.25^{2}=0.2005$ $\\mathrm{Fe}_{2}\\mathrm{O}_{3}$ 的沉降速率， $(5-0.98)\\times0.05^{2}=0.0100$ 5。  \n\n钛白的沉降速率大约是铁红的20倍，如果处理不当会浮红，表面颜色变深。如果色浆配方设计合理，选用恰当的醇酸树脂浓度或者使用适宜的润湿分散剂，该颜料分散体系还是比较稳定的。  \n\n制造天蓝色涂料时，经常采用钛白与菁蓝组合，该分散体的稳定性非常差，经常出现浮色发花现象，其原因是钛白密度高，粒径比较大，运动速度缓慢。菁蓝密度低，粒径小，运动速度快。当 $\\mathrm{TiO}_{2}$ 沉降，献菁蓝处于分散状态时，会浮蓝。因菁蓝运动速度快，碰撞概率大，若没有能有效保护，易于产生絮凝，颗粒变大，发生沉降，出现浮色现象。所以在这个体系中浮蓝、浮白或者发花是不固定的。比较有效的控制办法是选择适宜的钛白粉，配合恰当的润湿分散剂。如以R-820钛白配合国产的菁蓝，使用流平润湿剂和分散剂，混合后共同上磨研磨，可大大改善浮色发花问题。  \n\n在分散体系中沉降和布朗运动并不是等量运动。沉降会产生浓度差，布朗运动会使其均一化。若沉降速率过大，就会出现沉降体积，出现浮色发花等不良现象。要减小沉降速率，只有减小粒径，粒径变小又会出现热力学的不稳定现象。为克服这些病只有借助于润湿分散剂的帮助。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 767,
+        "chunk": "# 4.分散体系的稳定机理  \n\n分散体系的稳定机理主要有电荷斥力学说和空间位阻学说。  \n\n(1）DLVO理论颜料粒子在水性分散体中，甚至在油性分散体中会因不同原因而带电。由于粒子带电，在粒子界面的周围必然会吸附等量的反电荷，形成双电层结构。DLV()理论是在扩散双电层基础上建立起来的理论，它是电荷斥力学说的中心。解释分散体稳定的原因主要有以下两点。  \n\n$\\Phi$ 胶粒间引力是范德华力，因胶粒是由许多分子集聚而成的，胶粒间的引力是所有分子引力的总和，这种粒子间的引力是远程作用的范德华力，用 $\\mathbf{{V}_{A}}$ 表示。它与距离的3次方成反比。与一般分子间的引力与距离的6次方成反比不同。  \n\n$\\textcircled{2}$ 粒子间相互排斥的力是由带电粒子产生的，用 $\\boldsymbol{V_{\\mathrm{R}}}$ 表示。  \n\n可以把一个带电粒子形成的双电层看成四周为离子氛包围的带电粒子（图2-4-1)。  \n\n![](images/1c0a97cd18eb14120e6e8bc413048493bbcafa9ae7b8cb84402bc580a845abdf.jpg)  \n图2-4-1离子氛重叠  \n\n图中粒子带正电荷，虚线表示正电荷作用的范围，由于离子氛中反离子的屏障效应，虚  \n线以外就不受电荷影响，当两个粒子接近时，如果离子氛尚未接触，粒子间并无排斥作用。  \n当粒子相互接近到离子氛产生重叠时，重叠区域离子浓度变大，破坏了原先电荷分布的对称  \n性，导致离子氛中电荷重新分布。即离子从浓度较大的重叠区域向外扩散，其结果正电荷离  \n子产生斥力，使相近的粒子脱离。理论证明这种斥力为粒子间距离指数函数。其斥力用 $V_{\\mathrm{~R~}}$ 表示。  \n\n当分散体系中带相同电荷的粒子相互接近时体系的总能量 $\\boldsymbol{v}$ 为 ${\\boldsymbol{V}}_{\\mathbb{A}}+{\\boldsymbol{V}}_{\\mathbb{R}}$  \n\n![](images/82de380a4bf7171a791b110ff3e4c23fff53a553b12a4259bb20409e90430871.jpg)  \n图2-4-2粒子间相互作用的电势能曲线  \n\n随着距离的缩短， $V_{\\mathrm{{A}}}$ 增加， $\\boldsymbol{V}_{\\mathrm{R}}$ 亦增加，但两个能量的方向是相反的（图2-4-2）。  \n\n由图2-4-2可知，单个粒子相距较远时，离子氛重叠，只有引力起作用。就是图中的第二极小区域，总势能为负值。  \n\n粒子间相吸产生的絮凝物是松软的、可逆的。随着距离缩短，离子氛重叠，如图2-4-1（b）所示，斥力开始出现，总势能逐渐上升为正值。但此时引力也随距离变小而增大。在一定距离出现最大相斥势能 $\\scriptstyle{V_{\\mathrm{resx}}}$ 。距离在缩小，引力又占据优势，势能开始下降，进入图2-4-2中的第一极小区域，粒子会形成坚硬的凝聚物。  \n\n如果小于动能（KT）的 $2{\\sim}3$ 倍，由于引力 $\\boldsymbol{v_{\\mathrm{A}}}$ 的作用，粒子间将产生凝聚。若离子周围有高分子分散剂吸附层存在则情况就不相同了。如果Vmax在（20～25）KT以上时，粒子间由于斥力作用，凝聚不会发生。  \n\n$$\nK T=m V\n$$  \n\n式中m—粒子质量；$\\boldsymbol{v}$ —粒子运动速度；$\\kappa$ —波耳兹曼常数；KT—微粒热运动平均能量。$\\boldsymbol{V_{\\mathbb{R}}}$ 是斥力，其大小与扩散双电层的电势一样，随着距离增加成指数函数减少，其减少  \n程度是由德拜长度决定的。  \n\n(2）空间位阻稳定机理由于空间位阻作用，吸附在胶体粒子表面上的高分子聚合物能有效地阻止胶体粒子的凝聚，使分散体处于稳定状态。这种稳定作用被称为空间位阻效应。  \n\nMackor首先指出位阻稳定，但他认为是由斥力决定的。 $\\Delta G=-T\\Delta S$ ，这就是说永远是斥力，不可能产生絮凝。但实际并非如此。  \n\nNapper认为位阻稳定的分散体系，色散力并不是其不稳定的主要原因。产生絮凝的原因是溶剂的溶解力，当溶剂的溶解力降至 $\\theta$ 点以下时，分散介质中的高分子会相互吸引。这种引力作用会导致 $\\theta$ 点附近的分散胶粒产生絮凝。  \n\n通过实践证实，具有最好空间位阻作用的分散剂应具有颜料锚定基团，通过化学或物理吸附牢固地锚定吸附在颜料粒子的表面上，以确保粒子运动时分散剂聚合物不会脱吸。还应具有与分散介质树脂溶液相容的自由伸展链部分。构成一定厚度的吸附层，可使粒子间保持一定距离。一旦吸附层重叠，可以靠重叠区域内产生的自由能将粒子斥开，达到远程排斥作用。  \n\n当两个带吸附层的粒子相互接近，还没有重叠时，相互之间不发生作用。吸附层重叠时会出现以下两种现象(图2-4-3)：  \n\n![](images/4c116150be517e5da26074d20436d09319c83d9b37dac495f79248138e4eeefd.jpg)  \n图2-4-3厚度为S的两个粒子 接近时吸附层重叠情况  \n\n$\\Phi$ 渗透压效果或反溶剂化效果 $:\\Delta G_{\\mathbb{M}}$ ；  \n\n$\\textcircled{2}$ 妨碍吸附层中高分子链运动的斥力（ $:\\Delta G_{\\mathrm{V}}$ 。  \n\n根据赫西克（Hesselink）等的计算，Ottewill、Walker得出了 $\\Delta G_{\\mathrm{M}}$ 的计算公式：  \n\n$$\n\\Delta G_{\\mathrm{M}}=\\frac{4\\pi K T c_{\\mathrm{s}}^{2}}{3V_{1}\\rho_{2}^{2}}-(\\Psi_{1}-K_{1})\\left(\\bar{\\delta}-\\frac{h}{2}\\right)\\left(3a+\\delta+\\frac{h}{2}\\right)\n$$  \n\n式中 $c_{*}$ —吸附层中聚合物的浓度；$\\boldsymbol{V}_{1}$ —溶剂分子的体积；$\\rho_{2}$ —聚合物自身的密度；  \n$\\varPsi_{1}-K_{1}$ —聚合物稀释之时热力学参数（ $\\psi_{1}$ 为煸项， $\\scriptstyle K_{1}$ 为熔项)；a常数；—吸附层厚度。  \n\n$\\varPsi_{1}-K_{1}$ 是从测定聚合物黏度求出来的数值。在良溶剂中为正值，在贫溶剂中为负值。因此，在良溶剂中 $\\Delta G_{\\mathrm{M}}>0$ 是正值。吸附层显示出排斥作用。而且这个作用是随着 $c_{*}$ 增大而增大。如若 $\\delta$ 变大就构成了远距离排斥作用。  \n\n关于 $\\Delta G_{\\mathrm{V}}$ 还提不出像式(2-4-9）那样的解析公式。其主要作用原理是斥力。当两个带着吸附层的粒子重叠时，在重叠区域内聚合物伸展在液相中的链节，运动的自由度就因位阻而消减，重叠区域内斥力减少，因为一个体系总是朝煸增加的方向自发变化，在煸斥力的作用下，颗粒有再次分开的倾向，根据计算，其数值与 $\\Delta G_{\\mathrm{M}}$ 大体相同。  \n\n由位阻稳定的胶体分散体系对温度变化很敏感，尤其是在临界絮凝点附近。但对许多体系而言，可能在很大的浓度范围内都很敏感。絮凝通常是可逆的，在加热和冷却时都可以发生。絮凝能否发生取决于吉布斯自由能的正负。  \n\n$$\n\\Delta G_{\\mathrm{f}}{=}\\Delta H_{\\mathrm{f}}{-}T\\Delta S_{\\mathrm{f}}\n$$  \n\nNapper等使用吉布斯自由能分析了导致絮凝的热力学因素，当 $\\Delta G_{t}>0$ 时分散体系是稳定的，当 $\\Delta G_{t}$ 是负值时会产生絮凝。为了保证分散体系的稳定性，可通过以下3种方法调整 $\\Delta G_{t}$ 为正值。  \n\n（1）当 $\\Delta H_{\\mathrm{f}}>0$ · $\\Delta S_{\\mathrm{f}}>0$ 时，很明显增加有利于稳定，增加会对絮凝有利。是稳定。  \n(2）当 $\\Delta H_{\\uparrow}<0$ ， $\\Delta S_{i}<0$ 时，熔增加不利，煸增加有利于稳定。是稳定。  \n（3）当 $\\Delta H_{\\mathrm{f}}>0$ . $\\Delta S_{i}<0$ 时，肯定 $\\Delta G>0$ 是不会产生絮凝的，称为-熔共同稳定体系。  \n\n实验证明，水性分散体系中稳定更为普遍。而在非水分散体系中煸稳定则是常见的。  \n\n综上所述，两个具有吸附层的粒子间的力有以下几种，首先是范德华引力 $\\boldsymbol{V_{\\mathrm{A}}}$ ；容积限制的斥力 $G_{\\mathbf{V}}>0$ ；渗透区或反溶剂化效果 $G_{\\mathrm{M}}>0$ 或 $G_{\\mathrm{M}}<0$ ：吸附链的吸附交联能 $G_{{\\mathrm a d}}<0$ 前面讲的电荷斥力 $G_{e}>0$ 。 $G_{\\mathrm{V}}$ 斥力是正值，在良溶剂中 $G_{\\mathbb{M}}$ 也是正值，只有 $G_{\\**}$ 是负值。只要使粒子表面达到饱和吸附，有足够厚的吸附层，基本可以保证分散体系的稳定性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 768,
+        "chunk": "# 5.润湿分散剂类别  \n\n润湿分散剂按分子量的差异可分成低分子量的传统型的表面活性剂和高分子量的新型的具有表面活性的聚合物。  \n\n低分子量的润湿分散剂是指分子量为数百 $(800\\sim1000)$ ）的低分子化合物。  \n\n高分子量的润湿分散剂是指分子量在数千至几万的具有表面活性的高分子化合物。  \n\n按其应用领域，又被划分为水性润湿分散剂和油性润湿分散剂。还有既可在水性领域也 可在油性领域中应用的水油两性润湿分散剂。  \n\n(1）低分子量润湿分散剂这类润湿分散剂属于传统型的表面活性剂，分子具有两亲结构，其活性是由非对称的分子结构决定的。  \n\n$\\textcircled{1}$ 阴离子型，其亲水基是阴离子，带负电。例如油酸钠。主要亲水基有羧酸基、磺酸基、硫酸基、磷酸基等。  \n\n$\\textcircled{2}$ 阳离子型，其亲水基是阳离子，带正电。例如油酸铵。主要是铵盐、季铵盐。  \n\n$\\textcircled{3}$ 非离子型，不电离、不带电。主要有聚乙二醇型和多元醇型两大类。例如脂肪族聚酯。 $\\mathrm{C_{17}H_{33}C O(O C H_{2}C H_{2})_{n}O H}$ 多用于水性体系。  \n\n$\\textcircled{4}$ 两性润湿分散剂，分散剂同时具有两种离子性质。例如卵磷脂。  \n\n$\\textcircled{5}$ 电中性是指化合物中阴离子和阳离子都有大小相同的有机基团，整个分子呈电中性，但却有极性。这种助剂在涂料中应用相当广泛，几乎每个涂料助剂生产厂家都有几个电中性的产品。例如 $[\\mathrm{CH}_{3}-(\\mathrm{CH}_{2})_{x}-\\mathrm{CH}_{2}-\\mathrm{NH}_{3}][\\mathrm{OOC}-\\mathrm{CH}_{2}-(\\mathrm{CH}_{2})_{x}-\\mathrm{CH}_{3}],$  \n\n按应用效果，可将这类分散剂划分成解絮凝型和控制累凝型两大类。  \n\n解絮凝的润湿分散剂多数只有一个极性吸附基，能够牢固地吸附在颜料表面上。另一端伸展在分散介质中起稳定作用。这类分散剂多推荐用在面漆中，可降低涂料的黏度，改善涂料的流动性，提高涂膜光泽。  \n\n控制絮凝的润湿分散剂，是通过分散剂的架桥作用，把数个分散的颜料粒子连接在一  \n\n起。一般是通过以下几种方式连接的。  \n\na.以游离的分散剂为桥，通过极性分散剂与吸附在颜料粒子上的分散剂的极性基相连接构成单元絮凝体。b.分散剂形成双重层，第二层分散剂通过极性基相连接构成单元絮凝体。c.通过吸附在颜料粒子上的分散剂的极性基直接连接在一起构成絮凝体。连接形成如图2-4-4所示。  \n\n![](images/edebc7eb35e1d602e54a3413e191b6239e02129619bd285cf74522e48e7a5d5d.jpg)  \n图2-4-4控制絮凝型分散剂的连接形式  \n\n这种絮凝是分散剂通过氢键力或范德华力把颜料粒子连接起来的，结合力比较弱，在高剪切速率下会受到破坏，结构黏性降低。当剪切停止时，黏性会恢复。正是这种微弱的触变性赋予了涂料许多良好的性能。能起到防沉、防浮色发花和防流挂的作用，弥补了因分子量低、空间位阻效应不足的缺陷。  \n\n低分子量润湿分散剂对无机颜料有很强的亲和力。因为无机颜料通常是金属氧化物或含有金属阳离子及氧阴离子的化合物，表面具有酸性、碱性或两性兼具的活性中心，它们与阴离子、阳离子表面活性具有很强的化学吸附作用，能够形成表面盐，牢固地锚定在无机颜料的表面上。  \n\n这种酸、碱基的相互作用对于有机颜料是不可能的。因为有机颜料的分子是由C、H、O、N等元素组成的。这些原子不能被电荷化，所以有机颜料表面没有像无机颜料那样的活性中心。因此，传统型的润湿分散剂不能稳定有机颜料分散体，而多数被推荐用于无机颜料的分散。对于有机颜料需要使用高分子量润湿分散剂。  \n\n(2）高分子量润湿分散剂传统型的低分子量的润湿分散剂有确定的分子结构和分子量。但高分子量分散剂却与其不同，分子结构和分子量都不固定。它是不同分子结构和不同分子量的分子集合。分子量大的在 $5000{\\sim}30000$ 之间，有的可能比这还高些。多数是嵌段共聚的聚氨酯和长链线型的聚丙烯酸酯化合物。它具有与颜料表面亲和的锚定基和构成空间位阻的伸展链。锚定基必须能够牢固地吸附在颜料表面上，伸展链又必须能与树脂溶液相容。很显然均聚物满足不了这两个常常是相互矛盾的要求，所以必须是某种形式的官能化聚合物或共聚物。  \n\n高分子量分散剂的伸展链多数是聚酯构成的，它能在多种溶剂中有效。较高分子量的聚酯在芳香烃类溶剂中可溶。而较低分子量的聚酯在酮、酯类溶剂及二甲苯/丁醇混合之类溶剂中有很好的溶解性。所以聚酯化合物会在诸多溶剂中提供良好的空间位阻效应。  \n\n制成一种与某种溶剂相容的聚合物稳定化链，并不是设计高分子量分散剂的最终结果。而是要设计出既能与溶剂相容又能与溶剂挥发后的树脂相容，而又不影响涂料各项性能指标的稳定化伸展链才是最重要的。所以在选择使用高分子量润湿分散剂时除要注意其与树脂溶液的相容性，同时还要测试加人分散剂后干涂膜的光泽与基材的附着力、耐久性等各项指标。  \n\n高分子量分散剂的锚定基是吸附在颜料粒子表面上的基团。是根据颜料表面的特殊性和吸附机理而设计的。对于具有酸、碱性吸附中心的颜料可以采用胺类、铵、季铵基团；羧基、磺酸基、磷酸基及其他盐类，酸式磷酸盐、磷酸酯等均可为锚定基。通过酸/碱或离子对吸附在颜料粒子表面上。对于具有氢键给予体和接受体的颜料表面可采用多胺和多醇为锚定基。对于依靠极性吸附和范德华力吸附的颜料可采用聚氨酯类化合物为锚定基。对于像献菁蓝、二嗪紫类有机颜料可采用它们自身的衍生物为锚定基。  \n\n了解高分子量分散剂的结构对选择使用是至关重要的。要获得良好的涂料、油墨分散体，一定要选择适宜的润湿分散剂。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 769,
+        "chunk": "# 6.润湿分散剂的应用  \n\n如何润湿颜料粒子？又如何使颜料分散体处于稳定状态？这是涂料工作者必须思考的问题。在涂料、油墨中颜料表面会产生竞争吸附。怎样调整树脂聚合物和分散剂在颜料表面上的吸附作用，保证颜料的润湿和分散的稳定性，是控制涂料性能指标的重要因素。  \n\n(1）润湿分散剂在极性活性基料中的应用当无机颜料和具有活性吸附团的树脂聚合物配合使用时，特别是像甘油和季戊四醇油改性的醇酸树脂，分子中含有大量活性官能团。分子量不算大，但具有很强的极性。应该说它们是一种具有润湿分散功能的基料。从测定炭黑及钛白在季戊四醇醇酸树脂中分散情况得知，分散体系的稳定性存在一个最佳树脂浓度值。  \n\n所谓最佳树脂浓度值，是指研磨色浆时所用树脂的固含量。含有活性基，而且分子量分布宽的树脂，如上所述的醇酸树脂。当其与无机颜料配合时，树脂浓度高，小分子量的极性强的醇酸树脂会优先吸附在颜料粒子表面上，形成的树脂吸附层薄，位阻效应差，不可能获得稳定的颜料分散体。如果降低树脂浓度，如选择 $20\\%$ 或 $30\\%$ 的树脂溶液为研磨基料，配合高颜基比。这样做有两个好处： $\\textcircled{1}$ 树脂浓度低会使色浆的黏度下降，有助于生产高浓度色浆，提高生产率； $\\textcircled{2}$ 树脂浓度低可限制极性强的、小分子量树脂的吸附，强制大分子量树脂的吸附，有利于空间位阻效应。  \n\n还应指出，颜料在具有少量活性官能团树脂溶液中的分散与具有大量活性官能团的树脂溶液中的分散是有区别的。前者必须借助于分散剂的帮助，提高润湿效率，增强分散的稳定性。后者因活性官能团多，只要选择适宜的树脂浓度、恰当的颜基比，可以不使用润湿分散剂。若使用润湿分散剂也可以缩短研磨时间、提高分散效率。  \n\n为了获得更好的涂料性能，在含活性基的树脂溶液中使用分散剂，最好要让润湿分散剂先吸附在颜料粒子的表面上，为此要注意以下几点。  \n\n$\\textcircled{1}$ 色浆研磨料的添加顺序，最好是先加溶剂，而后加润湿分散剂，再加颜料，最后加树脂溶液。  \n\n$\\textcircled{2}$ 颜料表面特性，无机颜料要知道其表面的酸、碱性。  \n\n$\\textcircled{3}$ 树脂的活性基是什么，是酸性的还是碱性的。  \n\n$\\textcircled{4}$ 再根据颜料表面的特性和树脂活性基及酸、碱强度来选择润湿分散剂。一定要注意两者之间的酸、碱性关系。  \n\n(2）润湿分散剂在非活性基料中的应用每种颜料的分散效率都是颜料、树脂溶液和助剂三者作用的结果。溶剂作用也很大，它主要是作为分散介质，对颜料的润湿和分散是间接起作用的。无机颜料在含活性基的极性树脂基料中分散时可以不用分散剂，而在不含活性基的非极性树脂基料中则不同，不加润湿分散剂是无法制成颜料分散体系的。  \n\n前苏联学者在过氯乙烯树脂中分散华蓝，经过120h的研磨，颜料细度还高于 $130\\mu\\mathrm{m}$ 9若在该分散体系中添加占华蓝量 $3\\%\\sim4$ %的十八烷胺，24h研磨分散，细度不超过 $10\\mu\\mathrm{m}$ .约有 $85\\%$ 的粒径是 $5\\mu\\mathrm{m}$ 。如果助剂用量增加2倍，分散效果不再继续提高，如果超出华蓝的化学吸附量，分散效果会变坏。  \n\n华蓝颜料表面具有两种活性中心。但胺的吸附量高于酸的吸附量，因为华蓝表面存在大量能与胺发生吸附反应的[Fe(CN)6]-中心。十八烷胺和硬脂酸在华蓝表面都没有物理吸附，而十八烷醇只有物理吸附没有化学吸附。  \n\n这个实例说明，在非极性的无活性官能团的基料中分散颤料没有润湿分散剂是办不到的，不但要用润湿分散剂，还要根据颜料表面的特性来选择润湿分散剂的种类，种类选定了还要注意添加量。  \n\n涂料中使用的无活性官能团的非活性树脂是很多的，例如乙烯类树脂、热塑性丙烯酸树脂、过氯乙烯、高氯聚乙烯、橡胶树脂等。因为树脂聚合物缺乏活性官能团，很难在颜料表面产生牢固的吸附层，没有吸附层就无法产生空间位阻效应，所以分散体的稳定性不良。  \n\n在这种非极性树脂基料中，无机颜料可以采用低分子量的控制絮凝型润湿分散剂，色浆制造时也一定要注意树脂浓度和颜基比，这类助剂通过架桥达到控制絮凝，弥补了树脂和其自身分子量小的缺陷，能起到防沉、防浮色发花的作用。  \n\n有机颜料在这种基料中分散时最好选择高分子量分散剂，关键是要注意分散剂与树脂的相容性、添加量和添加顺序。  \n\n（3）润湿分散剂的添加量及添加顺序润湿分散剂的添加量应根据添加剂的种类、颜料的种类、颜料的特性而定。  \n\n无机颜料一般用低分子量的润湿分散剂就可以，用量可控制在颜料的 $1\\%\\sim5\\%$  \n\n有机颜料多使用高分子量分散剂。使用时首先要注意树脂与分散剂的相容性，相容性不好，高分子量分散剂的伸展链是卷缩的，造成吸附层薄，空间位阻效应差。  \n\n每种颜料在一个特定的分散体系中都存在一个最佳的浓度值。这个最佳值跟颜料的比表面积、吸油量、最终要求的细度，研磨时间和色浆中所有树脂聚合物的特性有关，要根据这些条件试验而定。在试验时一定要把设备因素考虑进去。  \n\nCiba公司关于高分子量分散剂添加量的确定推荐了许多方法。  \n\n$\\Phi$ 无机颜料高分子量分散剂固体分添加量，可按颜料吸油值的10%计算。  \n\n$\\textcircled{2}$ 炭黑高分子量分散剂有效分的添加量，可按DBP吸附值的 $20\\%$ 计算。  \n\n$\\textcircled{3}$ 有机颜料高分子量分散剂有效分的添加量，应是颜料BET的 $20\\%\\sim50\\%$ 。BET大的用量就要大些。  \n\n$\\textcircled{4}$ 分散剂添加顺序无机颜料，极性含活性官能团的树脂，可在加树脂前后添加，影响不大，因为起作用的主要是树脂。  \n\n若无活性树脂，使用高分子量分散剂或低分子量分散剂，最好是先加颜料，再加分散剂，最后加树脂。  \n\n要使分散剂更好地发挥作用，应当让分散剂与颜料表面有最多的接触机会。所以使用树脂含量不宜多，一般控制在 $10\\%$ 左右，以免让树脂占据颜料更多的表面，树脂用量大了对色浆的黏度不利。  \n\n添加顺序是先将分散剂加到溶剂中，在搅拌的情况下添加颜料，加完后搅拌 $5\\sim10\\mathrm{min}$ 最后添加树脂溶液，揽拌均匀后上磨粉碎至 $5\\mu\\mathrm{{m}}$ 以下。  \n\n以上对润湿分散剂的种类、结构组成、应用机理等做了简要介绍，仅供读者参考。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 770,
+        "chunk": "# 二、流平和防流挂剂",
+        "category": " Introduction"
+    },
+    {
+        "id": 771,
+        "chunk": "# 1.引言  \n\n涂膜的主要作用之一是保护性和装饰性。而涂膜的表面状态，会对这两项功能产生极大的影响。尤其是装饰性，如果涂膜表面状态不佳，这项功能就有可能完全丧失。所以涂膜的表面状态被视为涂料的主要考核指标之一。涂膜表面会经常发生的缺陷有橘皮、缩孔、波纹、浮色发花、气泡、针孔、刷痕、辊痕、流挂等病。其产生的原因与涂料配方组成和涂装工艺有关，特别是与涂料黏度、表面张力、溶剂、颜料的润湿分散、涂料对基材的润湿能力，涂装时动态表面张力是否平衡，涂装方法及环境等诸多因素有关。  \n\n黏度，通常的概念是黏度低流平性好，黏度高流平性差，调整黏度要用溶剂。但并不尽然，黏度是由涂料流变性决定的，要改善涂料的流动和流平性，就要改变涂料的流变性，通常使用黏度调整剂，构成结构黏性，来平衡流平与流挂的关系。调整触变指数改善刷痕和辊痕。  \n\n(1）表面张力表面张力是涂膜流动和流平的主要动力，如果出现表面张力差，不但对流平无益，还会产生许多病，如缩孔、波纹、贝纳尔涡流，涡流运动又会导致橘皮、发花等表面缺陷。  \n\n(2）溶剂溶剂是涂膜流平的主要支柱，是调节涂料黏度的主要材料。溶剂使用不当，对涂料的黏度、流动与流平、干燥及其他性能都会有极大影响，随之而来的会产生许多表面病，如橘皮、暗泡、波纹、刷痕等。所以配漆时一定要注意溶剂的三要素：溶解力、挥发速率和挥发平衡。  \n\n(3）颜料分散颜料润湿分散得好，涂料黏度低，结构黏性也小，流动与流平性就好，如果颜料润湿分散不好，就会产生颜料絮凝、分离，在涂膜表面形成浮色发花现象，所以良好的解絮凝型润湿分散剂，不仅可以使颜料处于稳定的分散状态，还可以提高和改善涂料的流动与流平性。  \n\n（4）基材润湿若涂料的表面张力高于被涂物的表面张力，涂料对基材润湿不良，会产生缩孔，严重者会出现不浸湿、不展布，大面积卷缩现象。遇到这种现象最好使用基材润湿剂，降低涂料与基材的界面张力，能够提高涂料的展布性，防止缩孔，增强附着力。  \n\n(5）动态表面张力失衡多发生在高表面张力的水性涂料中，当高剪切速率涂装时，在新的表面，表面活性剂来不及重新排布，造成动态下表面张力失衡，会产生大片缩孔，展布性不好的表面缺陷。可以采用在新表面能够快速定向排布并能迅速降低表面张力的表面活性剂。  \n\n(6）气泡涂料中进入空气，极性物或表面活性剂就会在气/液界面定向排布产生气泡，涂料若脱气不良，就会在涂膜表面产生针孔、鱼眼、暗泡等不良表面现象。最好的消除办法是使用消泡剂或脱泡剂。  \n\n（7）涂装方法及涂装工艺控制涂料对涂装方法的适应性，涂装工艺的控制，如涂装黏度、涂膜厚度、干燥条件等。如果这些条件控制不当都会产生涂膜缺陷。如辊痕、刷痕、流挂、爆泡等。  \n\n这样叙述并不是说一种病态只有一种原因，恰恰相反，一种病态往往会由多种原因所造成。所以要消除涂膜表面的弊病一定要找出其真正原因，再对症下药，选择适宜的助剂或方法进行克服。 D  \n\n以上仅对涂膜表面缺陷及产生的原因和解决的方法做了极其简要的介绍，关于涂料的黏度调整剂、消泡剂和脱泡剂、颜料的润湿分散剂都有专门章节进行详细论述，本书只论述与表面张力有关的表面状态控制剂——流平剂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 772,
+        "chunk": "# 2.流动与流平  \n\n黏度是液体流动特性的标识，当剪切力作用于液体时，该液体会在力的作用下产生流动，流动速度受液体内部阻力控制，不同液体的流变性是不同的，主要有以下几种类型。流动曲线如图2-4-5所示。  \n\n![](images/759fc17294c8e528845513515bb4d684a6d680a46df2754e5392dd6cec3bd135.jpg)  \n图2-4-5流动曲线  \n\n1—牛顿流体；2—假塑性流体；3—膨胀流体；4—塑性流体  \n\n(1）牛顿流体剪切力与剪切速率的比值是一个常数，黏度不受剪切速率变化影响。如水、矿物油、沥青等都是牛顿流体。这种流体有助于流平和流动，这并不等于所有牛顿流体在任何情况下都能得到一个光滑平整的表面状态。  \n\n(2）塑性流体这种流体具有结构黏性，剪切力必须达到破坏结构黏性的程度（“屈服值\")，液体才开始流动。以后随剪切速率的提高，黏度开始下降，当剪切停止时，黏度会按先前路线返回原点。这类流体有润滑油、腻子、唇膏等。  \n\n(3）假塑性流体这种流体没有“屈服值”，剪切速率低时就开始流动，此时呈现牛顿流体特性。随着剪切速率进一步提高，黏度会急剧下降，当降到一定程度时，剪切速率再提高，黏度也不再变化，又呈现牛顿流体特性。低剪切速率段的牛顿流体和高剪切速率段的牛顿流体，分别称为第一牛顿段和第二牛顿段。许多涂料有这种流动特性。  \n\n(4）膨胀流体随剪切速率的增大，黏度也随之增加，如分散炭黑浆和搅拌水泥浆，初始剪切阶段黏度是很大的，尤其是研磨没有润湿分散剂的炭黑浆时，这种现象非常明显。  \n\n(5）触变流体该流体有“屈服值”，随剪切速率和剪切时间的增加，黏度不断下降。黏度下降路线和返回路线不相同，当剪切速率相同时，返回的黏度比下降时的黏度低。下降和返回之间有一个滞后区，滞后区内有无数黏度值。 25 D  \n\n这种流动特性给人们提供了一个非常好的控制涂膜表面状态的途径。如调整立面喷涂时的流平与流挂的关系，控制贝纳尔涡流产生，防止颜料沉降絮凝等。这是涂料中用途最大、最广泛的一种流体。  \n\n涂料在力的作用下，按其流动的特性流成涂膜，但液态涂膜在无外力作用下会自动流平，这种促使涂膜流平的力就是表面张力，所以涂料在成膜和成膜后流平时的力是不相同的。剪切的外加力使涂料通过流动变成涂膜，表面张力使涂膜通过流平由不规整的表面变成光滑平整的涂膜。不管是流动，还是流平，都是涂料的运动形式，都要受到涂料流动特性——黏度的影响。  \n\n黏度不仅决定了液体的流动特性，而且对涂膜的流平也有相当重要的作用。表面张力不仅是流平的动力，而且对流动也同样会产生影响。  \n\n由此可以得出这样的结论：流动与流平两个定义之间没有什么太大的区别，涂料要求达到光滑平整的表面，需要涂料具有良好的流动与流平性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 773,
+        "chunk": "# 3.表面张力与涂膜表面缺陷  \n\n涂膜流平的主要动力是表面张力，所以要想控制涂膜的表面状态，必须控制和调整涂膜的表面张力。  \n\n(1）表面张力与缩孔的关系产生缩孔的主要原因是涂膜表面出现了表面张力差。将产生缩孔的物质称为缩孔施体，将涂膜称为缩孔受体。也就是说缩孔施体的表面张力和缩孔受体的表面张力不平衡，当其远远低于缩孔受体的表面张力时，便会在缩孔受体上（涂膜表面）形成凹陷的孔穴，这就是缩孔。  \n\n可以用杨氏公式解释，产生缩孔的展布力与缩孔施体的表面张力和缩孔受体的表面张力之间的关系如下：  \n\n$$\nS{=}(r_{w}{-}r_{1}){-}r_{\\mathrm{L}}\n$$  \n\n式中S—展布系数；rw—缩孔受体的表面张力；——缩孔施体的表面张力；$r_{1}$ ——缩孔受体与缩孔施体之间的界面张力。  \n\n$s$ 是正值时，才能自发展布，只有 $r_{\\mathrm{L}}{<}r_{\\mathrm{w}}$ 时 $s$ 才是正值。也就是说只有缩孔施体的表面比缩孔受体小时才能产生缩孔。 $r_{\\mathrm{t}}$ 越小 $s$ 值越大，缩孔越严重。涂膜产生缩孔的原因归纳为以下几种。  \n\n$\\Phi$ 涂料组成物含有缩孔因素，缩孔的产生是来自涂料的组成物内部。主要原因有三个。a.树脂中少量大分子聚合物聚集，产生溶剂所不溶的胶粒析出，其表面张力低于树脂溶液。涂料成膜后，会马上出现缩孔。b.溶剂挥发不平衡。在溶剂的挥发过程中，某些溶剂挥发过快、过多，破坏了溶剂与混合树脂的溶解平衡，使部分溶解性差的树脂析出，这种缩孔多在涂膜干燥过程中出现。c.涂料中含有表面张力低的活性物，如添加了相容性过差或过量的消泡剂及其他硅、氟类的助剂等，这种原因造成的缩孔，涂装后会马上出现。  \n\n$\\textcircled{2}$ 外部污染，是指涂料涂装成膜后，由外部污染所致。如空气中飘浮的低表面张力的污染物，像硅粒子、油脂微粒等落到刚涂装完的涂膜上，使涂膜产生缩孔。另外涂装设施，像喷漆房、烘道、涂装物贮存室等地方的空气不干净，漆雾微粒或其他空气浮沉物等落到未干的湿膜表面上也会造成缩孔。  \n\n$\\textcircled{3}$ 基材表面张力低，涂料的表面张力高于被涂物的表面张力。其原因有三个。a.材质本身的表面张力就比较低，如PE和PP塑料。b.基材表面有涂覆物，如挤压成型的材质，表面有脱模剂没处理干净。或者表面涂覆了低表面张力的物质，如镀锌、镀镍铁板，涂覆了含硅或含氟的涂料等。c.基材处理不合格，污染没有完全清除干净。这类情况，涂覆后马上就会出现缩孔。严重者无法成膜，即使勉强成膜，附着力也不好。  \n\n$\\textcircled{4}$ 动态表面张力失衡，采用高剪切速率涂装时，由于涂料的比表面积在瞬间大幅度增加，涂料中的表面活性剂来不及在新增的表面上重新排布，导致涂料表面张力不平衡，这种表面张力不平衡的涂料落到基材上便会出现满板的缩孔。如用刷子刷涂水性PU涂料，可能板面效果很好，光滑平整。若改用空气喷涂，可能满板都是缩孔，无法成膜。此时若添加TegoWet500，它能迅速地降低涂料的动态表面张力。喷涂施工时，涂膜是光滑平整的，不再出现缩孔。若刷涂更不会出现问题，事实告诉人们，能够刷涂的水性涂料不一定适宜喷涂，但适宜喷涂的涂料，一定适宜刷涂。要保证水性涂料在不同的剪切速率下都可以涂装，必须添加降低动态表面张力的表面活性剂。如TegoWet500、505、510等。  \n\n（2）表面张力与波纹的关系无论是平面涂装，还是立面涂装，在涂膜干燥过程中，表面时有波纹产生。这种波纹的产生与表面张力有着密切的关系。  \n\n$\\Phi$ 平面涂装时的波纹，平面涂装后，涂膜的表面张力是，涂膜的平均厚度是h(图2-4-6)。在干燥过程中由于受热不均匀，表层溶剂挥发不平衡，右侧挥发速率大于左侧。因此，右侧的表面张力比左侧高，涂料就会自左向右流动，这是产生波纹的主要原因。其移动的力 $F$ ，可用式(2-4-11）计算出来。  \n\n图2-4-6中表面张力差促使涂膜中涂料的流动：  \n\n![](images/da41a73f52565b870346e5feaf8495a6c2809265eeeba04876a4779ac3f93b03.jpg)  \n图2-4-6平面涂装的涂膜  \n\n$$\nF{=}\\frac{\\mathrm{d}r}{\\mathrm{d}x}\n$$  \n\n式中F—推动涂料移动的力；dr——涂膜受热后左、右侧的表面张力差；$\\operatorname{d}x$ —涂膜中涂料向右移动的距离；r 涂装后涂膜的表面张力。  \n\n涂料的移动速度用 $q$ 表示，可用式（2-4-12）求出：  \n\n$$\nq{=}\\frac{1}{2}{\\times}\\frac{F}{\\eta}h^{2}\n$$  \n\n将式（2-4-11）带人式（2-4-12）得出式（2-4-13）。  \n\n$$\nq{=}\\frac{1}{2}{\\times}\\frac{h^{2}}{\\eta}{\\times}\\frac{\\mathrm{d}r}{\\mathrm{d}x}\n$$  \n\n从式（2-4-13）中可以得出这样的结论：涂膜中涂料的移动速度与涂膜厚度和涂膜的表面张力差成正比，跟黏度和移动距离成反比。为控制波纹的产生提供了技术方向。增加黏度和减少表面张力差都是可行的。平面涂装时最好不要改变黏度，只用表面状态控制剂，减少表面张力差即可。  \n\n$\\textcircled{2}$ 立面涂装时的波纹，含有降低表面张力的流平剂的涂料，在立面喷涂时，经常出现上下波纹。如图2-4-7所示，这种波纹的产生与重力、表面张力差、涂膜的厚度、黏度有关。如果单纯是重力下垂，应该只有向下的帘幕式的流挂波纹，不会有向上的波纹，肯定还有一种向上的力，推动涂料向上移动。这种力应该是涂膜上下的表面张力差。  \n\n![](images/8fd2d3f5846f134b01f0cf3218f54d2079e355094ec0ababe3714003e14e13a3.jpg)  \n图2-4-7立面涂装的波纹  \n\n表面张力差产生的原因是，流平剂迁移至涂膜表面后，受重力作用，随涂料下坠，下面的流平剂会比上面多，那么下面的表面张力会比上面低，由于Marangoni作用表面活性剂会带动涂料由下向上移动。也就是说，下垂在先，上移在后，这样就会产生上下波纹。  \n\n牛顿流体涂料，涂装时涂膜流挂速度可用式（2-4-14）表示。  \n\n$$\n\\scriptstyle V={\\frac{\\rho g h^{2}}{2\\eta}}\n$$  \n\n如果下垂和上移是同时发生的，就要视下垂的重力（pg）和表面张力差产生的动力（F）之间的关系。如果两力大小相等就不会有波纹产生。两力相减，若重力大就只有下垂；若动力大就只有向上的波纹。但多半是先产生流挂，而后才有的表面张力差所产生的动力，所以经常看到的是上下波纹。  \n\n可以选用能微弱控制絮凝的分散剂，制成具有弱结构黏性的涂料，改用不降低或少降低表面张力的流平剂。这个问题就可以解决了。  \n\n如果涂料有特殊要求，必须选择有强降低表面张力的高滑爽度的流平剂，那就只好来调整涂料的屈服值了。  \n\n在立面上涂膜产生流挂时，涂膜厚度和屈服值的关系可用式（2-4-15）表示。  \n\n$$\nh_{0}=\\frac{S_{0}}{\\rho g}\n$$  \n\n式中 $h_{0}$ —流挂极限膜厚；  \n\n$S_{0}$ 一屈服值。  \n\n由上式可知，流挂的极限膜厚与屈服值成正比，屈服值越大，抗流挂性越好。但流平性未必好。若要使选择的流变助剂，既能达到防止波纹产生的目的，又要有良好的流平性，就必须要调整涂料的流变性。  \n\n室井、森野氏等概括了涂料的流变性与涂料涂装和涂膜形成时的流动和流平关系。列于表2-4-3，即流变指数（低剪切速率时的黏度/高剪切速率时的黏度比）小或接近1的涂料，无论在涂装过程中，还是在成膜后，其流平性均极其优良。  \n\n表2-4-3流变特性与流动和流平的关系  \n\n\n<html><body><table><tr><td rowspan=\"2\">涂料</td><td colspan=\"3\">流变特性</td><td colspan=\"2\">涂装过程</td><td colspan=\"2\">涂膜的流动和流平</td></tr><tr><td>低剪切速率时的黏度</td><td>高剪切速率时的黏度</td><td>触变指数</td><td>流动性</td><td>流平性</td><td>薄涂膜</td><td>厚涂膜</td></tr><tr><td>1</td><td>高</td><td>低</td><td>很大</td><td>不良</td><td>不良</td><td>极差</td><td>极差</td></tr><tr><td>2</td><td>低</td><td>低</td><td>中</td><td>不良</td><td>良</td><td>极差</td><td>良</td></tr><tr><td>3</td><td>高</td><td>高</td><td>中</td><td>良</td><td>不良</td><td>良</td><td>良</td></tr><tr><td>4</td><td>低</td><td>高</td><td>小</td><td>良</td><td>良</td><td>非常好</td><td>非常好</td></tr><tr><td>5</td><td>低</td><td>很高</td><td>很小（约1.0）</td><td>非常好</td><td>良</td><td>非常好</td><td>非常好</td></tr></table></body></html>  \n\n以上论述说明，表面张力、重力都是促使涂膜流动和流平的力，借助黏度调整剂可以控制它们的平衡。  \n\n(3）表面张力与刷痕的关系将刷痕和辊痕的流平作为量纲解释时可借助于式(2-4-16)进行分析：  \n\n式中 $\\Delta t$ —涂膜流平到一定状态时所需的时间；  \n\n—刷痕的波长。  \n\n这个公式说明只有表面张力高才能缩短流平时间，而且表面张力越大，流平时间越短。  \n\n是否能提出消除刷痕、辊痕的最好方法？提出单一的方法，恐怕还是解决不了。因为涂料许多性能之间都是相互矛盾的。必须采取“综合治理”的方法。可以改善涂膜的厚度；调整溶剂的挥发速率；使用高、低剪切的黏度调整剂，减小触变指数，改变流变性；最重要的是不要使用强降低表面张力的流平剂，最好使用不降低表面张力的流平剂，如Tego  \n\nFlow 300。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 774,
+        "chunk": "# 4.流平剂的种类及作用机理  \n\n表面状态控制剂是能定向排列到液/气界面的表面活性物质。它们在表面积聚的原理与传统的、亲水、亲油性的两亲结构表面活性剂不同。它们可能是树脂状的产品，是靠它们与树脂基料的有限相容性，迁移至界面与空气生成一层新的低表面能的界面，控制表面的状态。这种物质也称为表面活性剂。  \n\n属于这类表面状态控制剂的有树脂类型、有机改性聚硅氧烷类型和氟碳化合物类型的三大类。  \n\n(1）丙烯酸聚合物流平剂树脂型的表面流动控制剂，多数是线型树脂聚合物，主要有丙烯酸树脂、脲醛树脂及三聚氰胺甲醛树脂。在通用体系中这些树脂的相容性是受限的，它们会积聚至表面形成一层新的树脂膜层，使涂膜的表面张力趋于平衡，但它们不会降低表面张力，所以不影响涂料的流动，多被称为流动促进剂。这类流平剂中丙烯酸树脂是主体。  \n\n丙烯酸酯类流平剂不仅可以促进涂膜的流动和流平，还不会影响涂膜的层间附着力，并且还有消泡的作用。  \n\n丙烯酸酯类流平剂的相容性是其控制涂膜表面状态能力的一项重要指标。相容性太好，溶在涂膜中，不会在涂膜表面形成新的界面，提供不了流平作用；相容性太差，不可能均匀地分布在涂膜表面，会相互集聚在一起，容易产生类似缩孔状的缺陷。会使涂膜光泽下降，产生雾影等不良的副作用。只有理想的受控相容性，才会在涂膜表面形成新的界面层，起到流平的作用。  \n\n丙烯酸酯类流平剂的受控性是通过改变分子量和极性来实现的。均聚物的相容性就不如共聚物的好，如均聚的丙烯酸通常与环氧、聚酯、聚氨酯等涂料所用的树脂相容性较差，若将其以物理方法混合则将形成表面状态不良的无光涂膜，所以丙烯酸均聚物不太适宜作流平剂。理想的流平剂多采用共聚物，可以是三元共聚物，也可以是改性共聚物，只有共聚物才能通过不同的单体改变聚合物的极性和玻璃化温度。  \n\n通常丙烯酸酯类流平剂的数均分子量被控制在 $6000{\\sim}20000$ 之间，分子量分布比较窄，玻璃化温度控制在 $-20^{\\circ}\\Upsilon$ 以下，表面张力在 $25{\\sim}26\\mathrm{mN/m}$ 以下。这种相容性受限的丙烯酸共聚物被认为是良好的流平剂。  \n\n丙烯酸酯类流平剂可以是均聚物，也可以是共聚物；可以是线型结构的，也可以是带支链的；可以是无规共聚的，也可以是嵌段共聚的。  \n\n$\\Phi$ 氟改性的丙烯酸酯类流平剂这类流平剂目前应用得比较广泛，用氟改性丙烯酸使氟和丙烯酸的优缺点互补，使这类流平剂更趋于完美。丙烯酸和氟类流平剂的优缺点见表2-4-4。  \n\n表2-4-4丙烯酸和氟类流平剂的优缺点  \n\n\n<html><body><table><tr><td>流平剂</td><td>优 点</td><td>缺点</td></tr><tr><td>丙烯酸类流平剂</td><td>强的流平性，具有消泡能力，不影响层间附着力</td><td>基材润湿性差，不能消除缩孔</td></tr><tr><td>氟类流平剂</td><td>基材润湿性良好，防缩孔能力强</td><td>稳泡，层间附着力差，无法重涂，价格贵</td></tr></table></body></html>  \n\n通过改性的流平剂，具有较好的表面状态控制能力，不稳泡，可以重涂，具有良好的抗缩孔和基材润湿的能力。  \n\nCiba公司提供的结构式如下：  \n\n![](images/36382bec1d521ba7fa73e7bcddded1156f76c5deeaeb6f87735caff200c37d6b.jpg)  \n\n结构式中的丙烯酸丁酯和丙酯是起流动和流平、消泡及改善层间附着力作用的。氟碳链是起控制表面状态、基材润湿及防缩孔作用的。该公司提供的产品有EFKA3777、3772、3600、3500。  \n\n$\\textcircled{2}$ 丙烯酸酯类流平剂的应用纯丙烯酸酯类流平剂因其对表面张力影响不大，所以多将其用于流动和流平助剂，特别是印铁涂料、卷材涂料，对消除辊痕是有益的。还有刷涂的木器漆对消除刷痕也是有帮助的。  \n\n应用时要特别注意与涂料的相容性，一般情况是分子量大的相容性差，但流动与流平性好；分子量小的相容性好，但流动与流平性要差些。  \n\n丙烯酸烷基酯类流平剂是粉末涂料常用的流平剂，这类流平剂多以粉体形式供货。可以将丙烯酸酯类流平剂分散在二氧化硅的粒子表面上，也可以用固体壳包裹丙烯酸酯类流平剂制成粉体形式的。在粉末涂料制造时混炼到粉体材料之中，在粉末涂料熔融固化成膜时起到流动和流平作用。  \n\n氟改性的丙烯酸烷基酯类流平剂，设计理念是兼具氟和丙烯酸两类流平剂的优点，几乎涵盖了流平剂的所有功能。尽管如此，在实际应用中，还要从实践出发，经过实践确定其应用和添加量。  \n\n丙烯酸酯类流平剂要在调漆时加入，因其有效分、结构不同，无法建议添加量，只能建议确定添加量实验时最好从漆量的 $0.03\\%\\sim0.05\\%$ 开始。  \n\n（2）有机硅类流平剂表面张力是涂膜流平的主要动力，但表面张力差，却是产生涂膜表面缺陷的主要根源。提高涂膜的表面张力，达到表面张力平衡，这对涂膜的流动和流平是非常有益的，但却办不到。所以人们只好采用降低涂膜的表面张力来消除表面张力差，控制涂膜的表面状态，消除表面缺陷。如消除贝纳尔涡流，防止发花和橘皮的产生。消除涂膜表面的表面张力梯度差，防止缩孔和波纹的产生。降低涂料与基材的界面张力，增强涂料的展布性，改善附着力，减少或消除因基材而造成的缩孔。硅油和有机改性聚硅氧烷是涂料行业使用较早、应用较为广泛的一种表面状态控制剂，基本可以消除因表面张力差而产生的表面缺陷。  \n\n$\\Phi$ 硅油·通常使用的硅油有聚二甲基硅氧烷和聚甲基苯基硅氧烷。涂料、油墨中应用的是聚二甲基硅氧烷。聚甲基苯基硅氧烷虽然相容性好，但不具备表面状态控制能力，所以在流平剂中基本不使用，多用于耐高温方面。  \n\n聚二甲基硅氧烷虽然具备良好的表面状态控制能力，但有许多缺点，相容性不好，会影响涂膜的光泽，还会经常出现缩孔、层间附着力问题等。  \n\n聚二甲基硅氧烷分子量不同，其相容性和用途也不相同。  \n\n![](images/d08871fe665e3cc9f39fd9a86a5d4ce92d9324697fff43356805cb6e3ba703ae.jpg)  \n\n![](images/604676962a703f3f63ee530792de1338ee541f63431e306c0e1ed6f56403d84a.jpg)  \n\n有机改性聚二甲基硅氧烷与硅油相比有明显的优越性，既保留了硅氧烷的优点，又用改性物克服了它的缺点，发挥出了许多特殊功能效应。  \n\n改性硅氧烷的性能及用途，关键是硅氧烷的分子量、类型、改性化合物的类别及在分子中的位置，改性的途径是很多的，本书根据涂料中常用的几种做简要的介绍。  \n\n$\\textcircled{2}$ 聚醚聚酯改性的有机硅氧烷结构式如下：  \n\n![](images/ce7cabfbc651ee2c60a7c2b251b9df75fcddeae8903b27a2bc88264fe86c8b77.jpg)  \n\n由结构式可以看出这一系列产品是属于梳状结构的有机聚硅氧烷。  \n\n$n+m$ 约为 $50\\sim250$ ，分子量控制在 $1000{\\sim}150000$ 之间。其相容性是依靠聚醚和聚酯来调整的。链越长相容性越好。这类产品中聚醚改性的最多，通常使用环氧乙烷和环氧丙烷。随乙氧基 $\\scriptstyle+\\mathbf{C}\\mathbf{H}_{2}-\\mathbf{C}\\mathbf{H}_{2}-\\mathbf{O}\\neq_{n}$ 含量的增加，其与水的相容性也随之提高，因此也完全可以合成水溶性的硅氧烷类的流平剂。环氧乙烷和环氧丙烷可以单独使用，也可以混合使用，用其来控制亲水、亲油性。如果同时含有乙氧基和丙氧基，就制成了水油两用的硅氧烷类的流平剂。  \n\n一般R为聚醚时称为聚醚改性的聚硅氧烷，R为聚酯时称为聚酯改性的聚硅氧烷。无论是聚醚还是聚酯，其链段越长与树脂的相容性就越好，也就是说，“ $\\scriptstyle{\\dot{n}}^{\\prime\\prime}$ 越大与树脂的亲和性越好。“m”越大表示其硅氧烷含量越多，其表面状态控制能力就越强，增滑性、抗粘连性就越好，与树脂的相容性就越差。  \n\n改性用的聚酯或聚醚与硅氧烷联结有两种方法：一种是硅氧键（—Si—O—)；另一种是硅碳链（-—Si—C—)。一般来讲，前者的热稳定性和耐水性不如后者好。  \n\n用聚醚、聚酯改性硅氧烷与树脂的相容性得到了很大的改善，降低表面张力，控制表面流动的能力、增滑性、抗缩孔、抗粘连的效果也都很好，个别产品还有层间附着力问题。尤其是聚醚改性的聚硅氧烷，热稳定性不好，容易稳泡。在应用时一定要注意这些产品的负面影响。  \n\n$\\textcircled{3}$ 烷基改性的有机硅氧烷前面提到了聚醚改性的聚硅氧烷有些不足之处；烷基改性的聚硅氧烷恰恰具备了这些方面的优点。  \n\n![](images/b169ba37b5895a6bbef2537dd3aa9bf8a71257a1416900e4226cbc107995634a.jpg)  \n\n式中，R为烷基。  \n\n这一系列聚硅氧烷产品也属于梳状结构。这类产品的分子量比较小，在10000左右， $^{n+}$ m约为 $30{\\sim}50\\$ 。用烷基改性的目的主要是为了提高热稳定性、相容性和不稳泡性，甚至有消泡功能。但随改性烷基链的增长，其降低表面张力的能力也随之下降。烷基链长度与表面张力的关系见表2-4-5。  \n\n表2-4-5烷基链长度与表面张力的关系  \n\n\n<html><body><table><tr><td>改性的烷基链</td><td>CH</td><td>CHCH</td><td>(CH）CH</td></tr><tr><td>表面张力/（mN/m）</td><td>20.6</td><td>26.2</td><td>31.4</td></tr></table></body></html>  \n\n一般碳链控制在 $\\mathbf{C}_{1}\\sim\\mathbf{C}_{14}$ 之间，所以分子量不太大。  \n\n上面介绍了聚二甲基硅氧烷的三种改性方法，改性方法不同，改性剂的用量和结构不同，其产品的性能也不同，三种不同改性方法生产的流平剂，其耐热性也截然不同(表2-4-6)。  \n\n![](images/a5df132f9d30c01f87b1e902087fabfc7d4ef2e1cb6a08cc379d837b50c7357c.jpg)  \n表2-4-6不同基团改性的有机硅的热稳定性烷基改性：■聚酯改性：A聚醚改性  \n\n从表中可以看出，热稳定性最好的是烷基改性的聚硅氧烷，最差的是聚醚改性的聚硅氧烷，在 $170\\%$ 时已损失了 $25\\%$ ，烷基改性的聚硅氧烷在 $300^{\\circ}\\mathrm{C}$ 时才损失了 $7\\%\\sim8\\%$ 曲  \n\nTego Glide 420、BYK-310、EFKA3236、EFKA3522等有机改性聚硅氧烷都具有很好的耐热性，这些流平剂都可在 $200{\\sim}220^{\\circ}\\mathrm{C}$ 的温度范围内使用。  \n\n$\\textcircled{4}$ 赋予优异滑爽性的端基改性有机硅为了赋予涂膜良好的滑爽性，EFKA公司推出了终端改性的有机硅。其结构式如下：  \n\n![](images/d0bfcb48556d3361346ace8acf2efb6b9331f34328735731453dab52eaa59365.jpg)  \n\n式中， $n{=}10{\\sim}40$ $m{=}10{\\sim}20$ ；分子量约为 $2000{\\sim}8000$ 。产品有EFKA3232、EFKA3033、EFKA3288等。  \n\n$\\textcircled{5}$ 反应性的流平剂在辐射固化的涂料、油墨体系中，存在基材润湿不良、不够滑爽、易刮伤、流平性差的缺陷。针对这些问题，Degssa公司提供了一系列的反应性的有机改性聚硅氧烷丙烯酸型流平剂，有TegoRad2100、2200、2250、2600、2700等产品，号码越小相容性越好，滑爽性越差；号码越大相容性越差，滑爽性越好。其结构式如下：  \n\n![](images/3085f58f868436dd422d59047cd6efa7a5eeb28ec494fa6a0e908cb8761667a2.jpg)  \n\n由结构式中可见改性的有机物是丙烯酸酯，用其调整它的流动性和相容性，它的滑爽性是由硅氧烷来决定的。丙烯酸基团的双键可以参加游离基的聚合反应，与树脂一起形成涂膜牢固地锚定在涂膜的表面上。  \n\nCiba 公司EFKA也提出了系列反应性的永久增滑、抗划伤的流平剂。其结构式如下：  \n\n![](images/8ad1a77f651affd0b8e372e9beec42314be65820da12e1c6d1a1201e913251a7.jpg)  \n\n从结构式中可以看出这个产品是两个端基改性的，具有两个反应活性基团：一端是丙烯酸酯基，可以参加游离基聚合反应；另一端是异氰酸酯基，可以与树脂中的羟基反应，在常温下即可进行，Ciba公司这类产品有EFKA3883、EFKA3886、EFKA3888、EFKA3835。  \n\n另外还有许多终端基改性的活性有机硅单体。这些单体的两端分别含有氨基、羧基、羟基、环氧基、丙烯酸酯基等反应活性基团。可与其单体进行聚合反应。生成含硅的树脂聚合物，这种树脂也具有增滑、抗粘连、防水、流动和流平作用。上述讲的活性单体，Degssa公司全部都有产品供市。例如，其中的TegomerH-Si2311是端羟基改性的。  \n\n式中， $\\scriptstyle n=30$ 。分子量为2500。  \n\n该单体可以与聚酯多元醇或/和聚醚多元醇一起与异氰酸酯单体反应制成水性的或溶剂型的PUD和PU树脂，用于皮革涂饰剂、制造合成革、制造木器漆等，具有良好的滑爽性、抗粘连性、防水性，手感也非常好。该单体还可用于制造醇酸树脂，改善醇酸树脂的耐候性、耐水性、抗粘连性等性能指标。  \n\n(3）有机硅流平剂的应用由上述可知，有机硅类流平剂的改性方法不同，改性材料不同，结构不同，分子量不同，用途也各异。因此在应用时要注意以下几点。  \n\n$\\Phi$ 依据问题选择流平剂硅类流平剂没有什么问题都能解决的“万能型”。如果选择不当会带来负面影响。如要消除表面张力差，最好选择降低表面张力强的、聚醚改性的聚硅氧烷，不要选择烷基改性的聚硅氧烷。要求耐高温烘烤的，就不能选择聚醚改性的，要选择烷基改性的或聚酯改性的。要求长期具有滑爽性，不能选择添加型的，要选择反应型的。要求改善界面关系，降低界面张力，最好选用小分子量的聚醚改性的基材润湿剂。  \n\n$\\textcircled{2}$ 层间附着力问题这类流平剂虽然经过改性，相容性和附着力问题都得到了改善，但有的还存在问题。迁移性差的流平剂，待涂膜完全干硬后再涂第二层就容易出问题。此外过热烘烤，破坏了流平剂的结构，极易出现附着力问题。要选择改性剂终端不含活性基的、迁移性好的有机硅流平剂。最著名的TegoGlide450流平剂具有良好的迁移性，涂完第二层，它会很快由第一层的表面迁移至第二层的表面，两层之间没有流平剂薄膜存在，所以它不影响层间附着力。TegoGlide450控制表面状态能力强，滑爽性高，通用性好（水油两用)，性价比好。  \n\n另外改善附着力还可选择小分子量的流平剂，因为，短链的硅氧烷，不易在气/液界面形成连续不断的膜，所以，增加了面漆和底漆的接触面积，改善了层间附着力。  \n\n$\\textcircled{3}$ 稳泡性几乎是降低表面张力越强的流平剂稳泡性越强，特别是聚醚改性的聚硅氧烷，极易在气/液界面处定向排布，在涂料中的空气，被流平剂给“包裹”着就形成了气泡。在应用时要特别注意，可以选择不稳泡的，或者配合消泡剂一起使用。  \n\n$\\textcircled{4}$ 热稳定性在加热固化型涂料中使用时，一定要注意流平剂的耐热范围，烘烤温度要在流平剂的耐热范围内，否则流平剂在过热烘烤时会产生分解，导致涂膜产生缩孔、重涂困难、光泽下降等负面影响。底漆或二道底浆，最好使用不降低表面张力的烷基改性的聚硅氧烷，面漆可采用能够重涂的聚酯改性的聚硅氧烷，例如TegoGlide420、BYK-310、EFKA3239等。  \n\n③用量及添加方法用量要视需要而定，总的建议添加量为漆量的0.01%～1.0%，究竟多少为宜，这要视配方组成、溶剂的溶解力、树脂的相容性、助剂之间的相互作用关系等因素而定。添加量不足效果不明显，添加量过大会产生细皱纹，甚至缩孔。所以用量一定要适中。  \n\n面漆和罩光清漆最好选用有机硅类流平剂配合丙烯酸类流平剂一起使用，例如TegoGlide $^{450+}$ TegoFlow300。TegoGlide450兑稀成 $12.5\\%$ 加 $0.3\\%\\sim0.5\\%$ ；TegoFlow 300加0. $2\\%\\sim0.3\\%$ ，效果极佳。  \n\n刷涂和辊涂为消除刷痕和辊痕，最好不要使用降低表面张力的流平剂，可用丙烯酸类流平剂或烷基改性的流平剂，尽量保持涂料的表面张力对流平是有帮助的，添加量为 $0.3\\%$ \\~$0.5\\%$ ，也可配合溶剂型流平剂一起使用。  \n\n作为流平剂最好在调漆时添加，若作为颜料润湿剂使用可在磨色浆时加人。  \n\n(4）其他类流平剂流平剂还有氟碳类和高沸点溶剂类。氟碳流平剂具有最高表面活性，可将涂料的表面张力降至 $16\\sim18\\mathrm{mN/m}$ ，因此具有最强的表面状态控制能力。概括来讲，有机硅流平剂所具备的功能，氟碳类流平剂全都具备，比有机硅类流平剂更好的是降低表面张力的能力更强，表面状态控制的效果就更好。但也有其负面作用，像层间附着力，稳泡就更难以克服。其价格也特别昂贵，影响了它的应用。最近杜邦公司推出了Zonyl系列氟碳类表面活性剂，据介绍可以和碳氢表面活性剂配合使用，大大降低了使用成本。  \n\n溶剂类流平剂多是高沸点溶剂的混合物，其主要作用机理是减缓溶剂挥发速率、降低涂料黏度、改善流平性。但其与环保、流挂控制、快干要求是相的，所以人们使用也不多。  \n\n关于这两类流平剂本书就不再多做介绍了。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 775,
+        "chunk": "# 三、防沉剂  \n\n涂料既是一个多相体系，又是一个粗分散体系。在热力学上是不稳定体系，颜料和填料在重力作用下会沉淀。如何延缓其沉淀，或即使产生沉淀，该沉淀也是疏松易重新分散的，这是涂料生产者必须面对的问题。加防沉剂就是解决此问题的方法之一。",
+        "category": " Introduction"
+    },
+    {
+        "id": 776,
+        "chunk": "# 1.防沉机理  \n\n涂料中颜料、填料粒子的沉淀是一个复杂的问题。为讨论方便起见，从简化入手。对于单一球形粒子在牛顿液体中的沉降速率可用斯托克斯（Stokes）公式表示：  \n\n$$\nv{=}\\frac{2r^{2}(\\rho{-}\\rho_{1})}{9\\eta}\n$$  \n\n式中v—粒子沉降速率；球形粒子半径；$\\rho$ 一粒子密度；P—液相密度；液体黏度。  \n\n由上式可知，粒子在液体中沉降速率与粒子半径的平方成正比，与粒子和液体的密度差成正比，与液体黏度成反比。据此，提高体系黏度，使分散体系稳定，降低密度差，也能使分散体系稳定。当然，减小颜料、填料粒径，更能达到稳定的目的。  \n\n上式还没有考虑界面层和粒子间的相互作用，二者都能大大降低沉降速率。  \n\n从流变学的角度看，结合涂料使用性能要求，防沉最理想的流变性就是触变性。提高涂料黏度，并使其具有一定的触变性。从而使颜料、填料粒子质量所产生的剪切力低于屈服应力，触变体不会流动，颜料和填料不会沉淀。这就是产生触变性的防沉剂防沉机理。  \n\n有的防沉剂是通过在颜料、填料表面的吸附，形成一定结构的界面层，降低颜料、填料粒子和液相的密度差，或产生相互作用等，达到防沉目的。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 777,
+        "chunk": "# 2.分类  \n\n如上所述，按防沉机理分，防沉剂可分为触变型防沉剂和其他型防沉剂。触变型防沉剂有有机改性膨润土、气相二氧化硅、氢化麻油蜡及其衍生物、部分金属皂类（二型稠厚剂）等。另一部分金属皂类，如一型稠厚剂，也有人称为絮凝型防沉剂。如按涂料分，可分为溶剂型涂料防沉剂和水性涂料防沉剂。但通常所说的防沉剂大都是指溶剂型涂料防沉剂。其实，未经有机改性的膨润土是亲水的，就是触变型水性涂料防沉剂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 778,
+        "chunk": "# 3.常用防沉剂和选用  \n\n（1）有机改性膨润土膨润土是亲水的，与溶剂型涂料不相容。因此，必须用季铵盐对膨润土进行改性，在其分子中引入憎水性的烷基，才可用于溶剂型涂料中。有机改性膨润土经过活化处理后，在溶剂中溶胀，通过边缘的一OH形成氢键，产生触变性，达到防沉作用。  \n\n不同改性的膨润土，具有不同的极性。不同极性的涂料体系，应选用与之相应极性的有机膨润土。如海名斯特殊化工公司的Bentone34适用于中至低极性溶剂型内外墙建筑涂料、船舶涂料和木器涂料等，而Bentone57适用于高极性溶剂型工业涂料和维护涂料等。  \n\n李正莉等在铜系环氧导电涂料中使用有机改性膨润土防沉剂，结果很好地解决了铜粉沉降问题，从而极大地提高了涂层表面导电性，涂层表面电阻率最小可达到6 $0\\times10^{-3}\\Omega/\\mathrm{cm}^{2}$  \n\n这种防沉剂通常用于颜料分较低的体系，高颜料分体系不宜使用，因为会造成过度增稠。  \n\n有机改性膨润土防沉剂也存在色泽深、透明度差、对光泽有影响、易产生刷痕、增加溶剂用量、漆液固含量难以保证等缺点。  \n\n(2）气相二氧化硅它是由四氯化硅在氧-氢焰中水解而成的，为无定形物质，粒径小，比表面积大。气相二氧化硅的颗粒为球形，表面有硅醇基，颗粒之间通过氢键互相结合，形成三维网络结构，赋予涂料触变性，产生防沉效果。  \n\n气相二氧化硅的防沉作用，在非极性涂料体系，如脂肪烃和芳香烃等，比较有效；而在极性体系，如醇类和水，则效果较差。  \n\n(3）氢化麻油蜡及其衍生物麻油是一种半干性油，是麻油酸的甘油酯，分子中含有双键和羟基。麻油氢化后，双键消失，状态由液态变成固态，外观为蜡状。成分为12-羟基硬脂酸三甘油酯。该分子是三维结构，含有可能形成氢键的羟基。  \n\n在非极性和低极性涂料中，如以烃类为溶剂的中油、长油醇酸树脂涂料中，氢化麻油分散后就溶胀，形成凝胶结构而具有触变性，因此有防沉作用。在极性涂料中，氢化麻油可能发生溶解，防沉效果较差。 人  \n\n(4）金属皂主要是锌皂和铝皂，特别是硬脂酸铝在溶剂型涂料中被用于防沉剂。它们被溶剂溶解成胶束并形成凝胶结构。防沉效果在很大程度上取决于铝和硬脂酸的比例。要想取得较强的防沉作用，就要将硬脂酸铝中所含铝的比例提高。在气干型醇酸漆中，催干剂会与硬脂酸铝产生强烈的相互作用，以致防沉作用消失。  \n\n(5）触变树脂聚酰胺或聚氨酯改性的醇酸树脂也可用于防沉剂。既可用于色漆，也可用于清漆。限制使用在短油醇酸体系和含极性溶剂体系中。触变树脂广泛使用于中、低  \n\nPVC溶剂型建筑涂料中。过量也许会导致光泽下降和黄变。  \n\n![](images/fc67323fdf36e3019250815bd7a485d38e3e22d1d6ba96ebb059b928dc36c74c.jpg)  \n图2-4-8改性聚脲增稠剂结构式$\\scriptstyle{\\mathsf{R}}=$ 低、中、高极性编基；R=中间链（二元胺骨架）  \n\n(6）改性聚脲增稠剂改性聚脲增稠剂的结构如图2-4-8所示。它的增稠防沉机理是：既有氢键的作用，也有端基的缔合作用。与一般增稠剂比较，它的防沉降和抗流挂性能好。根据端基的不同极性，改性聚脲增稠剂可分为三种：低极性聚脲增稠剂、中极性聚脲增稠剂和高极性聚脲增稠剂。前两种用于溶剂型涂料增稠防沉，而高极性聚脲增稠剂既可用于高极性溶剂型涂料中，也可用于水性涂料增稠。低极性、中极性和高极性聚脲增稠剂的商品分别有BYK-411、BYK-410和BYK-420。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 779,
+        "chunk": "# 四、消泡剂",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 780,
+        "chunk": "# 1.概述  \n\n消泡剂是一种表面活性剂，在气/液界面处发挥作用。能消除涂料生产和施工时所产生的泡沫。  \n\n以往，溶剂型涂料的消泡问题并未引起人们太多的重视，其原因是传统型涂料起泡的概率并不高，再者消泡也比较容易。现在不同了，由于我国涂料工业的快速发展，涂料品种不断增加，档次不断升级，高档的汽车涂料、木器涂料、修补涂料、卷材涂料等层出不穷，人们对涂料的装饰性、保护性要求更高，所以消泡已成为高档产品必须考虑的技术措施。  \n\n再者，由于环保意识的强化，节约资源环保型涂料、绿色健康型涂料得以快速发展。这些涂料包括水性涂料、无溶剂型涂料、高固体分涂料、UV涂料等。特别是水性涂料，还有水性油墨等。这些新产品不断出现，与传统溶剂型涂料相比更易起泡，而且难以消除，涂料工业的发展对消泡提出了更高层次的要求。  \n\n还有涂装技术的发展，当今的涂装技术是以高速、省力、自动化为主流。  \n\n这些技术的应用使涂料体系内发生紊流、飞溅和冲击、产生气涡的概率增大，容易产生传统工艺中不易出现的病，消泡也是其中一个急需解决的问题。  \n\n因此，不仅传统溶剂型涂料需要消泡剂，而且新型的涂料及新型的涂装工艺更为需要。消泡剂已成为当前涂料工艺必不可少的一种助剂，在涂料助剂的市场中占有相当大的比重。",
+        "category": " Introduction"
+    },
+    {
+        "id": 781,
+        "chunk": "# 2.泡沫的形成及其稳定  \n\n(1）泡沫及泡沫的产生泡沫可以定义为空气泡在液体中的一种稳定分散形式。  \n\n用热力学解释，泡沫是一种热力学不稳定的两相体系，泡沫的表面积越大，体系的能量增加越多，当泡沫破灭后，体系的总面积大大减小，于是能量也相应降低，所以称为热力学不稳定体系。  \n\n当空气在含有表面活性剂的液体中填充时，表面活性剂就会在气/液界面处定向排布。疏水基朝向空气，亲水基朝向基料。包裹着空气，产生大量气泡，由于气体的密度远远小于液体的密度，所以气泡会很快地向液面迁移。被表面活性剂包裹着的气泡升至表面时，在液面定向排布的表面活性剂单分子层，就会再将其包裹形成中间夹着液体的泡沫双层膜。泡沫的形成如图2-4-9所示。  \n\n被较多液体包裹着的球形泡称为微泡，被薄层包裹着的大的球形或多角形的泡被称为宏泡。  \n\n多数泡沫是3个气泡相交，壁面棱边组合在一起，其组合角总是 $120^{\\circ}$ ，这就是所谓的  \n\n![](images/0cf436c890271bccd10ba7f155593af6f6bfab98dadca21dd82caad2f336fd0a.jpg)  \n图2-4-9泡沫的形成  \n\nPlateau交界（图2-4-10)  \n\n根据Laplace公式可知，液膜 $P$ 处压力小于A处，于是液体会自动由 $A$ 处流到 $P$ 处，结果使液膜变薄，这就是液膜的排液过程。重力也会导致液膜排液，但这只能发生在厚液膜的条件下。无论哪种排液，液膜薄到一定程度都会导致泡沫自行破灭，但这时会受到Marangoni效应的影响，使泡沫趋向稳定。  \n\n在涂料及油墨中产生泡沫的原因如下。  \n\n$\\Phi$ 涂料和油墨生产时由于机械搅拌会把空气夹带到涂料和油墨中。  \n\n![](images/005064196b720716d124f9248938c76dc193384e70bd68ca5fcaa6558ad52ffd.jpg)  \n图2-4-10 Plateau交界  \n\n$\\textcircled{2}$ 涂料涂装过程中带人的空气，如刷涂、辊涂、高压无气喷涂，油墨的丝网印刷过程中等。  \n\n$\\textcircled{3}$ 双组分涂料，施工前混合时，搅拌混入的空气。  \n\n$\\textcircled{4}$ 被涂物的孔隙较多，由于涂料的渗入空气被赶出形成空气泡，如在多孔的木材和水泥墙上涂漆施工时。  \n\n$\\textcircled{5}$ 化学反应产生的气泡，如双组分PU涂料中的多异氰酸酯与微量水反应会产生 $\\mathrm{co}_{2}$  \n\n在涂料中泡沫的存在会导致针孔、缩孔、鱼眼、橘皮等不良现象，影响涂料的涂饰性和保护性。  \n\n特别是针孔，它是小气泡在涂膜干燥时逸出而产生的微细气孔。在干燥过程中，由于黏度增大，气孔微细管道不易闭合，而最终保留在干燥的涂膜中。这些针孔不但会影响装饰性，还会导致湿气和盐类物质的渗人引起腐蚀，使涂膜失去保护功能。  \n\n如果涂膜表层干得过快，气泡被截留在涂膜内表面，这就是平时经常提及的暗泡，类似“鱼眼”，导致该处涂膜厚度变薄，保护性变弱，还严重影响装饰性。  \n\n(2）泡沫的稳定泡沫的产生和稳定是两个概念，前者是指泡沫产生的过程及其量的多少，后者是指泡沫形成后的稳定程度。在涂料及油墨体系中影响泡沫稳定性的主要因素有以下几方面。 贝  \n\n$\\Phi$ 表面张力泡沫的生成伴随着气/液界面的扩大，其所做的功可用“表面张力×表面积”表示，当起泡扩张的表面积相同时，表面张力小，形成泡沫所需要的功也小，也就是说，表面张力小的液体容易起泡。表面张力对泡沫的形成有影响，但并不一定是其稳定的因素。丁醇等醇类溶液的表面张力（约 $25\\times10^{-5}\\mathbf{N}/\\mathbf{m})$ ，比一般表面活性剂的水溶液还低（十二烷基硫酸钠水溶液的表面张力约 $38\\times10^{-5}\\mathrm{{N/m})}$ 。但后者的起泡性、稳泡性都胜于前者。  \n\n又如蛋白质的水溶液表面张力比表面活性剂的水溶液高，但其却有较强的稳泡性。表面张力的稳泡性表现在：当表面膜有一定强度，能形成多面体的泡沫时，低表面张力才有助于泡沫的稳定。  \n\n$\\textcircled{2}$ 表面黏度液膜强度是稳定泡沫的主要因素之一，强度的大小又取决于表面吸附膜的坚固性，其坚固性的量度为表面黏度。通过实验证明，表面黏度较大的溶液所产生的泡沫寿命也较长（表2-4-7）。  \n\n表2-4-7表面活性剂溶液、表面张力与泡沫稳定性的关系  \n\n\n<html><body><table><tr><td>表面活性剂</td><td>表面张力/（N/m）</td><td>表面黏度/mPa·s</td><td>泡沫寿命/min</td></tr><tr><td>Triton X-100</td><td>30.5×10~5</td><td>一</td><td>60</td></tr><tr><td>Santomerse 3</td><td>32.5×10§</td><td>3</td><td>440</td></tr><tr><td>E607L</td><td>25.6X105</td><td>4</td><td>1650</td></tr><tr><td>月桂酸钾</td><td>35.0×10-5</td><td>39</td><td>2200</td></tr><tr><td>十二烷基硫酸钠</td><td>23.5X105</td><td>55</td><td>6100</td></tr></table></body></html>  \n\n可见表面黏度越高，泡沫的寿命越长，但表面张力与泡沫的寿命并无明确的数学对应关系。  \n\n![](images/095bcc9adadc44fcca4892782e02e41d70924110a5fc0a6b2c09c1200022641b.jpg)  \n图2-4-11重力排液及Marangoni运动  \n\n吸附在液膜上的活性物，若其分子间作用力较强，排列得比较密，尤其是疏水基之间能形成氢键键合结构的表面活性化合物，其表面黏度较大，寿命长。也就是说，表面膜的强度与表面吸附分子之间的相互作用有关，相互间引力大者，膜的强度也大；反之则强度小。强度大者泡沫稳定性好，小者稳定性差。  \n\n$\\textcircled{3}$ 表面张力的“修复”作用所谓表面张力的“修复”作用，实际上是Marangoni效应在起作用。也就是液体从低表面张力处向高表面张力处的流动现象。由图2-4-11中可知，排液是由A处向 $P$ 处流动，由于表面活性物质在 $P$ 处的积存，使 $P$ 处的表面张力低于A处的表面张力，表面活性剂就会带着基部的液体由 $P$ 处逆向返回到A处，使因排液变薄的液膜恢复到原来的厚度，这就是Marangoni效应。  \n\n重力排液，参见图2-4-11，箭头表示在重力作用下液体向下流动。液体的流动也带动了吸附在液膜表面上的表面活性物质向下移动。于是膜底部表面活性物质的浓度增加，大于膜上部的浓度，也就是说，下部的表面张力低于上部，根据Marangoni理论，下部低表面张力处的表面活性物质会向上部高表面张力处迁移，并带动底部的液体同时向上部移动。这种活性物质沿膜壁向上移动的作用也是Marangoni运动。使因重力作用变薄的泡沫又恢复了厚度，从而使泡沫稳定下来，延长了泡沫的寿命。  \n\n当一破坏性的外力（该外力可以是机械力或热冲击力）作用于泡沫膜时，表面活性物质便会迅速改变泡沫膜的表面张力，以抵消该外力的作用，使泡沫膜恢复到稳定状态。当泡沫局部受到拉伸时，该处液膜变薄，表面积增大，吸附的表面活性物质浓度降低，表面张力增加 $(r_{1}$ 变成 $r_{2}$ $r_{2}>r_{1})$ ，如图2-4-12所示。  \n\n那么 $r_{1}$ 处的表面活性物质就会向 $r_{2}$ 处迁移。随着活性物质的迁移，液体也返回到 $r_{2}$ 处使泡沫膜恢复到原来状态，这还是Marangoni效应。  \n\n![](images/4346475d647c176e26a50ba9606b87570371e540986dc8aa7f416bbf23d7f717.jpg)  \n图2-4-12泡沫膜局部变薄引起表面张力的变化  \n\n用能量观点分析，吸附着表面活性剂的液膜，若表面扩大，其所吸附的分子浓度便会降低，表面张力也将随之增大，这需要做很大的功。若表面收缩，表面吸附的分子浓度会增大，同时表面张力下降，于是不利于进一步收缩。所以这种吸附着表面活性剂的液膜有反抗液膜表面扩张或收缩的能力。这就是表面弹性的基本原理，也是表面活性剂具有吸附“修复”作用的原因。  \n\n$\\textcircled{4}$ 溶液的黏度它虽然不是稳泡的决定因素，但它对消泡的影响却很大。当涂料黏度高时，小气泡分布在其内部，浮力很难将其推向表面，它会长期悬浮在涂料内而不破灭，若留在涂膜中，将产生针孔、缩孔、鱼眼等病。另外，当外部溶液黏度高时，泡沫膜内的液体不易排出，泡沫膜厚度的减小很缓慢，所以泡沫的寿命较长。尤其是在高黏度的无溶剂型涂料中常会遇到这种现象。其次，在有孔隙的底材上涂装时，随着涂料向孔隙内渗入，孔隙内空气被挤出，若涂层较厚，表层溶剂挥发过快，黏度快速升高，气泡浮力无法克服黏度的阻滞作用，被截留在涂膜中形成鱼眼、缩孔、针眼等。在有孔的木材上涂装，这种现象很常见。  \n\n$\\textcircled{5}$ 表面活性剂的电荷排斥作用泡沫双层液膜的表面活性剂是带有相同电荷的，在泡沫壁较厚时，静电不显示作用；当排液泡沫壁变薄时，双层表面活性剂的间距缩短，静电排斥产生作用，阻止了泡沫膜进一步变薄，限制了排液，延长了泡沫的寿命。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 782,
+        "chunk": "# 3.消泡剂和脱泡剂的组成  \n\n具有消泡作用的助剂可分成消泡剂和脱泡剂。在水性涂料中主要使用消泡剂，在溶剂型和无溶剂型涂料中使用的多是脱泡剂。  \n\n(1）消泡剂的组成一般来说，消泡剂是由三种基本成分组成的，即载体、活性剂、扩散剂(主要是润湿剂和乳化剂，也可以不用)。  \n\n在水性乳胶漆和水性油墨中，使用矿物油系消泡剂是很多的。这类消泡剂的活性剂主要有脂肪酸金属皂、有机磷酸酯、脂肪酸酰胺、脂肪酸酰胺酯、脂肪酸酯、多亚烷基二醇、疏水二氧化硅等。活性化合物可以是固体的，也可以是液体的，固体的必须是微细的颗粒，液体的必须是乳液液滴。有时是单一的一种，也有时是复合的，还有的加入少量的有机硅。  \n\n扩散剂大部分是乳化剂和润湿剂，用以保证活性物质的渗透性及扩散性，典型的扩散剂有脂肪酸酯、脂肪醇、辛基酚聚氧乙烯醚、脂肪酸金属皂、磺化脂肪酸、脂肪酸硫代琥珀酸酯等。  \n\n载体也可称为溶剂组分，通常是脂肪烃。但以往多用芳香烃，因其对人体健康和环保有危害，限制了它们的应用。脂肪烃毒害性小，但在水相中溶解性较低，对光泽有不利的影响。载体可将消泡剂所有成分组合到一起，便于添加，同时还可以降低成本。另外，载体的自身表面张力也很低，体现出了消泡的特性。但对泡沫体系来说，对载体是有选择性的。  \n\n有机硅系列是现代水性涂料和水性油墨所用消泡剂的主流产品。  \n\n其活性部分是聚硅氧烷链段，依靠改性的聚醚链段来控制其相容性。多数是采用疏水和/或部分亲水聚醚来改性聚硅氧烷。聚醚与有机硅是依靠--Si—O—C—键和—Si-C—键相连1接。后者耐温性和耐水解性更好些。其结构形式大致有嵌段共聚、枝状接枝共聚、梳状接枝共聚等。  \n\n产品有浓缩型的、 $100\\%$ 活性物质和乳化型的。乳化型的必定含有乳化剂，载体多数是水。这些产品中有的含有疏水 $\\mathrm{SiO_{2}}$ 粒子，有的不含。由于某些聚醚改性硅氧烷具有高的展布力，它不添加疏水性的固体粒子，也同样具有出色的消泡能力。例如TegoFoamex 805和7447就属这类不含固体疏水粒子的产品。  \n\n(2）脱泡剂的组成脱泡剂必须与涂料体系有一定的不相容性，相容性太好，会导致脱泡失效；相容性过差，会导致产生缩孔之类的负面作用。因为涂料体系是千差万别的，一种脱泡剂不可能与所有涂料体系都相匹配，所以脱泡剂不可能是通用的。  \n\n脱泡剂的活性物质有有机硅类、聚合物类、氟硅类、有机硅/聚合物混合类几大类。  \n\n有机硅类脱泡剂又可分为聚二甲基硅氧烷（硅油)、聚醚改性聚硅氧烷、烷基、芳基改性聚硅氧烷等。  \n\n有机硅类脱泡剂表面张力比较低，非常容易进入泡沫体系，添加量比较少，不易引起浑浊，脱泡能力好，可快速将微泡带至表面。这类脱泡剂的缺点是，当泡沫形成后，不易消除，抑泡能力比较低。  \n\n聚合物非硅类的脱泡剂主要有聚醚、聚丙烯酸酯、氟碳共聚物、氯醋共聚物、丙烯酸共聚物等。  \n\n这类脱泡剂一般对表面张力影响不大，向涂料中调入时不如硅类脱泡剂，需要时间较长。当泡沫形成后，非常容易消除，具有很强的抑泡性能。这类脱泡剂的缺点是，相容性差，容易引起浑浊，脱泡能力差。  \n\n通常是采用改变聚合物的化学结构，对脱泡剂进行平衡调整。  \n\n通过对聚合物极性的改变，可以使消泡剂拥有不同的相容性，具有不同的扩散能力；通过对聚合物分子量的改变，可以使消泡剂拥有不同的相容性，具有不同的消泡能力。  \n\n因脱泡剂多用于溶剂型涂料，其载体绝大部分是各类不同类型的有机溶剂，有酮类、酯类及芳香烃类化合物，还有些载体是由两种或两种以上的混合溶剂组成的。  \n\n扩散剂不常用，但用于水性涂料的脱泡剂也有乳化型的，乳化剂是少不了的。  \n\n对于消泡剂和脱泡剂来说，欲使其具有良好的效果，活性剂的表面张力必须比成泡介质低，并能进入和迅速扩散于成泡介质中，通常用渗透系数（E）和扩散系数（S）来表示。  \n\n$$\n\\begin{array}{c}{E=r_{\\mathrm{F}}+r_{\\mathrm{DF}}-r_{\\mathrm{D}}}\\\\ {S=r_{\\mathrm{F}}-r_{\\mathrm{DF}}-r_{\\mathrm{D}}}\\end{array}\n$$  \n\n式中 $r_{\\mathrm{F}}$ ——泡沫的表面张力；$r_{\\tt D F}$ —消泡剂与泡沫膜的界面张力；D——消泡剂的表面张力。  \n\n当 $E{>}0$ 时，说明消泡剂或脱泡剂进人成泡介质中；当 $s{>}0$ 时，说明消泡剂或脱泡剂具有扩散性。也就是说，只有当 $\\scriptstyle{E}$ 和 $s$ 都是正值时，才能呈现消泡或脱泡效果，这也就说明了表面活性剂的表面张力越低，消泡和脱泡效果越好。  \n\n消泡剂和脱泡剂经常含有疏水的固体粒子，例如 $\\mathrm{\\SiO_{2}}$ 粒子。其消泡原理是反润湿效果，  \n\n稳定泡沫的表面活性剂的双分子膜层无法润湿疏水的固体粒子，造成局部区域表面张力失衡，形成膜层不稳定，导致泡沫破裂，提高了消泡效果。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 783,
+        "chunk": "# 4.消泡和脱泡机理  \n\n无论是脱泡还是消泡都是由活性物质来完成的。在涂料中表面活性剂都应与体系具有一定的不相容性，选用哪种消泡剂和脱泡剂，在很大程度上是取决于涂料体系也就是成泡介质的性质。  \n\n(1）消泡剂的消泡机理消泡剂是指对已形成的泡沫的消除作用（图2-4-13）。  \n\n![](images/aec73c7598dbf430d819d662d9eb31ece48dfa2bb61d09b4c31639e57da6adc2.jpg)  \n图2-4-13消泡剂的消泡过程  \n\n消泡剂的微小液滴迁移至液面，当被表面活性剂包裹着的气泡上升到表面时，消泡剂的活性物质便与稳定泡沫的表面活性剂层相结合，进入泡沫双层液膜内，消泡剂活性物质迅速扩散斥开稳定的表面活性剂，抵消了Marangoni效应，使失衡的泡沫的表面张力再也无法进行“修复”作用，消泡剂会穿过裂开的表面活性剂层，使泡沫的弹性大幅度降低。最后是稳定泡沫的双分子膜层完全破裂，达到消泡目的。泡沫破灭后，消泡剂再进人另一个泡沫液膜内重复上述过程。这个过程将循环往复地进行下去。  \n\n(2）脱泡剂的脱泡机理脱泡剂是分散在液态涂料中的非极性物质，与基料有一定的不相容性，促使其聚集在气/液界面处。减弱了包裹气泡的表面活性剂与基料之间的作用力。因此，加快了微泡向上迁移的速度。另外，当两个被脱泡剂包裹着的微泡相互靠近时，由于脱泡剂与基料之间的亲和力小于脱泡剂与脱泡剂之间的亲和力，受极性影响就必然会合并到一起。使小泡变成大泡。Stokes定律指出，当黏度恒定时，气泡上升速度（v）与气泡半径(r）的平方成正比。  \n\n$$\nv{\\sim}\\frac{r^{2}}{\\eta}\n$$  \n\n式中气泡上升速度；—气泡半径；$\\eta$ —体系黏度。  \n\n气泡上升到表面，由于没有表面活性剂稳定就必然会破灭。  \n\n通过上述可以看出，消泡剂是在涂膜的表面发挥作用，破坏已生成的泡沫，避免空气截留于涂膜表面。脱泡剂是防止泡沫形成，使涂膜中的微泡变大泡，提高泡沫上升的速度，脱泡剂是在涂料内部发挥作用的，两者之间的差别，在一定程度上讲只是理论上的。在实际应用中，一种好的消泡剂也可以像脱泡剂那样阻止泡沫的生成。另外，脱泡剂和消泡剂的作用结果是一样的，都是消除涂料中的泡沫。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 784,
+        "chunk": "# 5.选择及应用消泡剂和脱泡剂时应注意的因素  \n\n选用涂料的消泡剂和/或脱泡剂时，一定要注意涂料的种类、体系构成成分、起泡的原因、运输贮存条件、涂装方法等诸多因素与消泡剂和脱泡剂性能的关系。  \n\n要有良好的消泡效果，选用的消泡剂和脱泡剂的表面张力一定要比涂料的表面张力低。与涂料体系要有一定的不相容性，但不能产生负面作用。在涂料体系内还要有良好的分散性，也就是说，消泡剂和脱泡剂一定要有较高的渗透系数和扩散系数。消泡剂和脱泡剂不应与涂料组分发生反应。  \n\n在应用时还要注意消泡剂和脱泡剂的添加方法和添加时间。  \n\n(1）破泡效果与涂料体系的关系通过对多种消泡剂和脱泡剂的筛选评价实验，得出以下结论。  \n\n$\\boldsymbol{\\Phi}$ 同一种消泡剂或脱泡剂在不同的涂料体系中消泡效果不同。  \n\n$\\textcircled{2}$ 在同一种涂料体系中，不同的消泡剂或脱泡剂会表现出不同的消泡效果。  \n\n$\\textcircled{3}$ 涂料类别相同，但所用树脂结构不同（如聚酯氨基烘漆，所用部分聚酯树脂不同），消泡或脱泡效果也不一样。  \n\n$\\textcircled{4}$ 涂料所用树脂类型相同，若组成树脂的原料有所不同，对消泡或脱泡效果也会构成影响。例如，都是二元醇、甲苯二异氰酸酯组成的水性聚氨酯分散体，若改变其中二元醇的类型，消泡效果会产生明显的变化。  \n\n$\\textcircled{5}$ 同一种涂料体系，同一种消泡剂或脱泡剂在清漆和色漆中效果不一样。  \n\n这些结论说明，消泡剂或脱泡剂的应用效果与涂料体系及树脂的组成物有密切关系。因为不同树脂与溶剂组成的涂料的表面张力与消泡剂或脱泡剂的差别是不可能一样的，它们之间的相容性也不可能相同。另外，涂料构成不同，形成泡沫和稳泡的因素肯定不同，所以消泡剂和脱泡剂的破泡效果不相同那是必然的。  \n\n(2）破泡效果与涂料起泡因素的关系涂料体系不同，起泡程度不同。涂料体系相同，配方不同，起泡程度也不同。这就是说，在涂料配方中有许多因素对起泡和稳泡有影响，通过实验和生产实践可归纳出以下几方面。  \n\n$\\Phi$ pHpH会影响消泡剂的效果。例如，消泡剂是在某种 $\\mathbf{pH}$ 范围内选定的，此时涂料可能偏碱性，经贮存或涂膜干燥过程，涂料变成偏酸性，这样消泡效果会有所下降。  \n\n$\\textcircled{2}$ 表面张力涂料表面张力的高低对消泡剂有较大的影响，消泡剂的表面张力必须比涂料的表面张力低，否则就无法起到消泡和抑泡作用。涂料的表面张力是一个可变因素，所以选用消泡剂时要恒定表面张力，再将表面张力变化因素考虑在内。  \n\n$\\textcircled{3}$ 其他助剂的影响在涂料中使用的表面活性剂多数是与消泡剂趋向于功能不相容的关系。特别是乳化剂、润湿分散剂、基材润湿剂、流平剂等会对消泡剂的效果产生影响。因为这些助剂都有稳泡作用（在气/液界面定向排布)，使消泡剂用量加大或性能下降。溶解性强的表面活性剂还有可能溶解消泡剂，使消泡剂经时失效。所以在各种助剂配合使用时一定要注意不同助剂之间的关系，选择最佳平衡点。  \n\n例如，在使用聚醚改性聚硅氧烷流平剂或基材润湿剂时，会导致稳泡性的提高，最好配合消泡剂使用。例如，使用TegoGlide450流平剂，最好配合脱泡剂Airex931，也可以配合具有消泡作用的流平剂TegoFlow300。使用基材润湿剂WetKL-245，在水性涂料中最好配合消泡剂 $\\mathrm{Foamex}\\ 825$ 、815N及822等。因此，选择消泡剂时最好在配方各项材料都确定以后再进行筛选。  \n\n$\\textcircled{4}$ 烘烤温度涂料在常温下进入高温烘烤，开始瞬间黏度会下降，气泡可移至表面，然而由于溶剂的挥发、涂料的固化、表面黏度的增加，会使泡沫更趋于稳定，截留在表面，产生缩孔和针孔，所以烘烤温度、固化速率、溶剂挥发速率对消泡剂的效果也有  \n\n影响。  \n\n$\\textcircled{5}$ 涂料的固含量、黏度、弹性高固体分厚涂膜、高黏度、高弹性涂料都是非常难以消泡的，在这些涂料中消泡剂扩散困难，微泡变大泡速率缓慢，泡沫向表面迁移能力下降，泡沫膜黏弹性大等不利消泡因素很多。这些涂料中的泡沫是相当难以消除的。最好选用消泡剂和脱泡剂配合使用。以低表面张力的硅类消泡剂为好，脱泡剂对涂料的亲和性要好些，使其容易在涂料内扩散，抑泡性要强。  \n\n$\\textcircled{6}$ 涂装方法和施工温度涂料施工涂装方法很多，包括刷涂、辊涂、淋涂、刮涂、高压无气喷涂、丝网印涂等。采用的涂装方法不同，涂料的起泡程度也不同。刷涂、辊涂泡沫多于喷涂和刮涂，泡沫最多的是油墨的丝网印刷，而且不好消除。温度高比温度低时泡沫多，但温度高时泡沫比温度低时好消除。  \n\n上述这些因素对涂料的起泡性、稳泡性都有某种不同程度的影响，在选择消泡剂、脱泡剂时一定要特别注意。  \n\n(3）消泡剂和脱泡剂的添加方法消泡剂多用于水性涂料，一般有三种类型：100%有效分的浓缩型；乳化型，消泡剂已被乳化或粒径理想的乳液液滴；还有一种就是在上述两种类型中分别含有疏水固体粒子，如气相 $\\mathrm{\\SiO_{2}}$  \n\n供货形式不同，添加方法也有所区别。浓缩型的一定要经过充分分散，最好在研磨前添加，经过分散，使其具有良好的消泡粒径。消泡剂分散过细、过粗对消泡效果都不好。要控制在适宜的粒径，过细，消泡效果会降低；过粗，初期效果好，经时会下降，甚至会出现缩孔。也可以后添加，但要兑稀后加人，最好是用两性溶剂稀释到方便添加的浓度来添加。一定要现用现兑稀，以免失效。  \n\n经过乳化的消泡剂可以在生产的任何阶段添加，可在研磨前加人，也可在调稀时加入，很容易分散在水性涂料和水性油墨中。  \n\n脱泡剂多用于溶剂型涂料，绝大多数在调漆时加入，但对无溶剂、高固体分厚浆型涂料最好研磨前添加，也可分两次添加，研磨前加一部分，调漆时再加一部分。这种类型涂料可选择两种或三种脱泡剂和消泡剂配合使用。有的脱泡剂抑泡效果好，但消泡效果不强，为了避免泡沫遗留在表面，最好配上消泡剂，这种搭配使用效果更佳。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 785,
+        "chunk": "# 6.消泡剂和脱泡剂应用效果的检测方法  \n\n选择消泡剂和脱泡剂时经常采用一些方法测定它们消除泡沫的效果，以便确定涂料配方。  \n\n(1）水性涂料用消泡剂的检测方法  \n\n$\\Phi$ 泡沫高度测试法通常有两种做法：第一种方法是，取一定数量的涂料，倒入带有标线刻度的量杯里，用微型空气压缩机将空气导入涂料体系内，观察杯内含有不同类型消泡剂的涂料高度，涂料液面越高，消泡效果越差；第二种方法是，取一定数量的涂料，在一定条件下，用高速搅拌涂料数分钟，然后马上倒入带有标线刻度的量筒内，测量涂料的高度，同时称重，密度小、液面高的消泡效果不佳。  \n\n$\\textcircled{2}$ 淋涂试验法除可以评价消泡效果外，还可以评价消泡剂与涂料的相容性。将经高速搅拌的含有消泡剂的涂料，立刻倾倒在与框架成25°角摆放的聚酯膜上，观察干膜的表面状态，检查消泡及脱泡效果。观察相容性时一定要用清漆。  \n\n$\\textcircled{3}$ 密度测定法测长效性将经高速搅拌后的涂料倒进密度杯内，测定涂料密度，然后将涂料密封贮存，经过一定时间再测定密度，检查密度值是否有变化。若密度小，说明消泡剂有部分失效或全部失效。一定要在标准条件下进行。  \n\n$\\textcircled{4}$ 辊涂试验法取一定数量的涂料，在一个不渗漆、无孔的底材上（玻璃或聚酯片)，用海绵辊子，辊涂同样面积的涂膜，观察干燥后的涂膜表面状态。这种方法非常接近实际应用。  \n\n(2）溶剂型涂料用脱泡剂效果检测方法溶剂型涂料用脱泡剂效果检测方法与水性涂料的消泡剂有所不同，因为溶剂型涂料多数是微泡，所以密度测定法不太适宜。  \n\n$\\Phi$ 涂膜观测法用 $3000\\mathrm{r/min}$ 以上的转速搅拌涂料一定时间，然后淋涂在与框架成 $25^{\\circ}$ 角摆放在玻璃板上的聚酯上，待其干燥后观察涂膜的表面状态。  \n\n$\\textcircled{2}$ 模拟施工法对于高黏度、厚浆型涂料采用上述方法不行。可事先模拟现场施工方法进行检测。例如，双组分的地坪环氧自流平涂料可按涂装厚度，将其浇注到一个可以脱出来的小型模具内，待其干燥后，取其观测是否有针孔等病。  \n\n$\\textcircled{3}$ Tego 的硫酸铜试验法这种方法特别适用于防腐涂料，有些微小气泡用肉眼看不到，只好采用化学方法。将待测涂料以一定膜厚涂于磨砂钢盘上。待涂料固化后，把约$\\scriptstyle4\\mathrm{mL}$ 的 $10\\%$ 硫酸铜溶液倒人透明玻璃皿，将涂膜表面朝下盖在玻璃皿上，然后把盘和皿-一起倒转 ${180}^{\\circ}$ 。24h后，用清水冲洗涂膜表面。出现红点表明涂膜有微孔存在，这些红点是与铁起氧化还原反应还原出来的铜。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 786,
+        "chunk": "# 五、消光剂  \n\n消光剂就是能使涂膜表面光泽明显降低的物质。  \n\n光泽是涂膜的重要物理性能，光泽用光泽度来定量表征。其定义如下：从规定入射角照射涂膜表面的光束，其正反射光量与在相同条件下从标准板面上正反射光量之比，以百分数表示，称为涂膜的光泽度。  \n\n有时人们需要涂膜有光泽，而很多应用场合又不需要有光涂膜。因此，需要添加消光剂使涂膜表面光泽下降。",
+        "category": " Introduction"
+    },
+    {
+        "id": 787,
+        "chunk": "# 1.涂膜表面的消光原理  \n\n涂膜表面光泽度下降是由于干燥的涂膜表面形成微小的凹凸不平，该表面对人射光线形成漫反射造成的。  \n\n涂装过程中，刚涂上的涂膜表面并不很平整，由于表面张力的作用，力图保持最小的表面积，从而就变成光滑的湿膜，流平剂的使用加速这一进程。在涂膜表干之前，由于溶剂的作用，光泽度往往很高。干燥时涂膜表面形成微小的凹凸不平，变成粗糙的固体表面，光泽度就下降了。  \n\n涂层表面要形成微小凹凸不平一般要有两个条件：--是湿膜中存在足够量的粒径适宜的消光剂粒子；二是涂膜干燥或固化过程中产生体积收缩。如果有一个条件不能充分满足，消光效果是不理想的。体积收缩主要由溶剂挥发造成，但涂料组分的化学反应对此也有影响。传统的溶剂型涂料，挥发物含量在 $30\\%\\sim80!$ %之间，因而在干燥或固化过程中，随着挥发分的挥发，涂膜收缩明显，消光较容易。水性涂料用水作为稀释剂，在干燥或固化过程中，由于水分的蒸发，涂膜收缩也是明显的，因此消光并不难。随着环保要求的严格，涂料技术向逐渐减少挥发性有机物（VOC）含量方向发展，如高固体分涂料，固含量 $70\\%\\sim90\\%$ ，消光难度不断增大；UV光固化涂料，固含量 $100\\%$ ，固化收缩小于 $10\\%$ ，难以消光；而粉末涂料没有有机挥发分，固含量 $100\\%$ ，最难消光。对于这些涂料，在干燥或固化过程中，涂膜收缩很小甚至不收缩，消光要采用特殊消光剂，仍然要在涂层表面形成微小凹凸。  \n\n使用消光剂使涂层表面形成微小的凹凸，这只是光学上的不平整而已，肉眼是看不见的。  \n\n因此，当光线以一定角度照射到涂层表面上，如果其表面接近于光学平面，则会造成全反射，其反射角等于人射角，光泽度高。当人射光到达微小凹凸的表面时，随着涂层表面平均粗糙度的增大，散射光逐步代替反射光，使其光泽度不断下降，最终将形成无光涂层。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 788,
+        "chunk": "# 2.消光剂特点  \n\n涂料用消光剂应具备以下特点。  \n\n(1）化学情性高，不与涂膜中任何组分发生反应。  \n（2）对涂膜的透明性干扰小。  \n(3）易于分散。  \n(4）消光性能好，低加入量即可产生强消光性能。  \n(5）在液体涂料中，悬浮性好，长时间贮存，不会产生硬沉淀。  \n（6）不污染环境，不会对人体造成危害。",
+        "category": " Introduction"
+    },
+    {
+        "id": 789,
+        "chunk": "# 3.涂料消光剂的主要品种  \n\n1947年，美国Grace公司开发了第一个消光剂品种。半个多世纪以来，品种规格越来越多，用量越来越大。据德国Degussa公司统计，2000年亚洲地区微米合成二氧化硅消光剂的用量超过 $10\\mathbf{k}\\mathfrak{t}/\\mathbf{a}$ ，其中一半以上用于木器涂料。  \n\n(1）微米级合成二氧化硅目前微米级合成二氧化硅主要有以下三类。  \n\n$\\Phi$ 微米级合成二氧化硅气凝胶它是高孔隙率的二氧化硅凝胶（简称硅胶）经过严格控制的研磨工艺制成的微米级粒子。硅胶具有一次粒子形成的三维空间网状结构，骨架稳固，强度好。在涂料分散过程中，耐过度研磨。  \n\n硅胶类消光剂的另一特点是孔容积大。通常把孔容积大于 $\\boldsymbol{1.5\\mathrm{mL}/g}$ 的硅胶，称为气凝胶。孔容积越大，消光效果越高。  \n\n此外，消光涂膜的透明度较高，对涂层干燥特性无影响，该类消光剂对涂膜力学性能、耐候性影响小也是其优点。  \n\nGrace公司生产的Syloid系列二氧化硅气凝胶消光剂是这类消光剂的代表。SyloidED系列是1981年推向市场的，20世纪90年代进入我国涂料市场，在高档亚光涂料中占有大部分市场。该公司1997年推出的C系列，性能更优异，消光效果更高。据称，可比ED系列节省用量1/3。目前ED系列逐渐被C系列所代替。  \n\n英国INEOS（Crosfield）公司也是微米级二氧化硅气凝胶消光剂的主要生产厂家，其产品牌号为Gasil和HP系列。日本FujiSylysia公司的Sy系列，韩国OCI公司的ML系列等也在国内有一定市场。  \n\n国内一些硅胶生产厂家也在研制该产品，但还只处于中试或试生产阶段，试制产品与Grace公司的ED系列还有差距，市场上还未见到与SyloidC系列相当的国产消光剂。  \n\n$\\textcircled{2}$ 微米级沉淀二氧化硅沉淀二氧化硅是由多个一次粒子絮凝而形成的，没有规则的三维空间网状结构。可以想象为葡萄申状物质。沉淀二氧化硅消光剂是由干燥后的产品经过研磨而成的。  \n\n此类典型的产品有Degussa公司的HK和OK系列。此外，还有美国PPG公司，代表的牌号为Lover系列，日本NipponSilica公司的Niposil系列，法国Rodia公司也有生产。  \n\n国内这种类型消光剂产量最大，价格竞争激烈，质量更难以提高，只用于低档涂料。个别厂家选用固定来源的原料，粒度控制较好的可用于中档涂料。天津化工研究设计院开发的沉淀二氧化硅，平均粒径 $5\\mu\\mathrm{m}$ (激光衍射法)，孔容积 $\\boldsymbol{1.8\\mathrm{mL}}/\\boldsymbol{\\mathrm{g}}$ 曲  \n\n$\\textcircled{3}$ 气相合成二氧化硅目前只有Degussa公司的TS100和TT600消光剂是气相合成的。气相合成二氧化硅是由四氯化硅在氢氧焰 $1400\\mathrm{\\textperthousand}$ ）中水解生成的。目前最常用的是TS100，用于高档家具漆和皮革的消光，消光性好，涂膜透明性高，消除蓝相。缺点是价格昂贵，为OK系列的2倍以上。且需与疏水气相二氧化硅R972合用，以防止生成硬沉淀。国内曾有厂家研制气相二氧化硅消光剂，但产品还未出现在市场上。  \n\n(2）微粉蜡微粉蜡主要有合成蜡和半合成蜡。合成蜡包括微粉聚乙烯蜡、微粉聚丙烯蜡、微粉聚乙烯/聚丙烯蜡、微粉聚四氟乙烯蜡等。半合成蜡由天然蜡人工改性而成，如微粉脂肪酸酰胺蜡、微粉聚乙烯棕榈蜡、微粉聚丙烯棕榈蜡等。  \n\n产品有德国BYK公司的Ceraflour系列微粉蜡，Shamrock公司的Uniflat等系列，MicronPowder公司的Micropro 系列，Langer 公司的Lanco-Wax系列，Allied Signal（Honiver）公司的Acumist系列等。  \n\n国内微粉蜡刚刚起步，尚未达到与国外产品匹敌的水平。  \n\n（3）硬脂酸盐铝、钙、镁、锌的硬脂酸盐，应用开发较早，曾经是涂料的主要消光剂，在微米级合成二氧化硅进入市场后，其重要性大大降低。在底漆中应用较多，可以提高打磨性。  \n\n(4）Steamat（滑石粉/绿泥石粉）RIOTINTOMinerals公司开发了装饰漆的消光剂，主要成分是滑石粉/绿泥石粉，称为Steamat。当Steamat的用量在 $10\\%$ 以上时，亚光漆 $85^{\\circ}$ 的光泽度可降至1%以下。",
+        "category": " Introduction"
+    },
+    {
+        "id": 790,
+        "chunk": "# 4.消光剂的选用  \n\n除消光剂本身的物理化学性能外，用量、粒径、粒径分布、二氧化硅消光剂的孔容积等都是决定消光剂选用的重要因素。用量越多，光泽下降越多。粒径越大，消光越有效，当然，粒径要与涂膜厚度相适应。水性涂料、高固体分涂料、辐射固化涂料、粉末涂料等用消光剂与传统溶剂型涂料差别很大。  \n\n(1）传统溶剂型涂料由于含有有机溶剂，成膜收缩大，消光容易。虽然由于这类涂料树脂体系和涂膜厚度的不同，使用消光剂也有差别。但通用性大，主要是用于调整消光剂的用量和粒度上。高孔容积的合成二氧化硅凝胶最有效。为了防止消光剂在清漆中沉淀，优先选用蜡处理的二氧化硅消光剂。  \n\n如SyloidC803粒径最小，涂膜手感细腻平滑，透明度高，适用于高质量的薄层涂料和木器涂料。  \n\n(2）水性涂料水性涂料很少用挥发性有机溶剂。干燥的水合二氧化硅消光剂不很合适，因为微米级合成二氧化硅消光剂是多孔性物质，吸水能力强。在水性涂料中会吸附作为稀释剂的水分，使涂料组分的比例发生变化，基料颗粒的稳定性变差，造成基料颗粒絮凝，从而影响涂膜连续性，使涂膜质量变差。  \n\nGrace公司的SyloidW300、W500、W900型消光剂是水凝胶型二氧化硅消光剂，含水量达到 $55\\%$ ，干燥后孔容积 $\\boldsymbol{1.2\\mathrm{mL}/\\mathrm{g}}$ 。外观仍然是流动性白色粉末。易于添加，润湿性强，分散容易，不吸水，无气泡产生，干燥后粒度分布不变。虽然W型消光剂孔容积较小，由于水性涂料在干燥时水的挥发使涂膜表面收缩，消光相对比较容易，所以对水性涂料是个较理想的消光剂。  \n\nDegussa公司的ACEMATTTS100也能用于水性涂料的消光。  \n\n(3）卷材涂料卷材涂料为烘干型涂料。为了降低烘干温度和缩短烘干时间，加人不同结构的磺酸（如对甲苯磺酸）作催化剂。一般合成二氧化硅消光剂的 $5\\%$ 悬浊液 $\\mathtt{p H}$ 为 $6\\sim$ 8，对磺酸催化剂有吸附作用。Grace公司的SyloidC807、C809就克服了这一缺点，其水悬浊液 $\\mathsf{p H}$ 在3.5左右，对酸催化剂不吸附，不会影响卷材涂膜的干燥时间。除 $\\mathtt{p H}$ 不同外，C807、C809的孔容积也由 $\\boldsymbol{1.8}\\mathrm{mL}/\\mathrm{g}$ 上升至 $\\scriptstyle2,0\\mathrm{mL}/\\mathbf{g}$ ，而且粒度分布窄，分散非常容易，消光效率高，加入量减少，对涂膜理化性能的负面影响小。  \n\n(4）高固体分涂料涂料固含量超过 $70\\%$ 时，消光困难。对于高固体分醇酸涂料和聚氨酯涂料消光，粗二氧化硅消光剂最有效，且要较高用量。对于高固体分涂料消光，平均粒径达 $11\\mu\\mathrm m$ ，高孔容积（） $\\mathrm{1.8{\\sim}2.0m L/g)}$ ，微米级合成二氧化硅气凝胶已商品化。  \n\n(5）UV光固化涂料UV光固化涂料因不含挥发性有机溶剂，湿膜干燥后收缩很小，且干燥时间短。总体来说，消光困难。但反应活性低的涂料消光相对容易些，而反应活性高的涂料很难消光。  \n\n用原有的消光剂很难使其消光，经表面处理的消光剂有可能引起“稳泡”作用，影响涂膜透明度，甚至外观。Grace公司最近开发的SyloidRAD2005和2105很好地解决了这方面的问题。这两个品种消光剂的平均粒度小（Malvern法测定为 $4.5\\sim6\\mu\\mathrm{m})$ ，孔容积小，实际测定值只有 $\\boldsymbol{0.9\\mathrm{mL/g}}$ ，表面处理剂（蜡）高达 $15\\%\\sim20\\%$ ，但不会引起“稳泡”，消光效率高。INEOS公司的GasilUV55C和UV70C也是专门用于UV光固化涂料。Degussa公司的 $\\tt{O K}500$ 和 $\\mathrm{OK}~520~\\$ 也适合于UV光固化涂料。  \n\n(6）粉末涂料常用的消光剂有蜡型消光剂、非蜡型消光剂和消光固化剂。  \n\n蜡型消光剂是非反应性的，主要是通过与成膜物之间的混溶性等物理作用而产生消光。蜡型消光剂有聚乙烯蜡、聚丙烯蜡、聚乙烯共聚物蜡、聚丙烯共聚物蜡、改性聚氟乙烯蜡和脂肪族酰胺改性蜡等。  \n\n非蜡型消光剂如捷通达化工有限责任公司的SA2065和SA2066。  \n\n消光固化剂的消光原理是利用粉末涂料配方中两种不同反应活性固化剂，一种反应活性大，反应速率快，而另一种反应活性低，反应速率慢，由于反应速率差和反应产物间相容性的差别，产生微观上的粗糙表面，对光漫反射而达到消光。通过调节树脂和消光固化剂的用量，就能控制涂膜光泽，使用较方便。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 791,
+        "chunk": "# 六、防浮色发花剂",
+        "category": " Introduction"
+    },
+    {
+        "id": 792,
+        "chunk": "# 1.引言  \n\n涂料的颜色多数是几种颜料拼配起来的复合色。涂料涂装后，涂膜在干燥过程中有时颜色会发生变化，造成涂膜表面颜色的缺陷，经常遇到的有以下几种：浮色（flooding)、发花(floating）、丝纹（silking）、花斑（motting）、条痕（striation）。  \n\n虽然称谓不同，但其根本原因是涂料中颜料组分的一种或几种产生沉降、絮凝，造成颜料分离，导致涂膜表面颜色发生变化。将其归纳，可分为“浮色”和“发花”。  \n\n发花，是指涂膜中颜料组分分布不均匀，呈现出条斑或蜂窝状的花纹，可以理解为颜料垂直方向的分离。  \n\n浮色，是指涂装后，涂膜中的颜料组分呈现出均匀层状分离现象，其中的一种或几种颜料以较高浓度均匀地分布在表层，上下层的颜色差距较大。可以理解为颜料水平方向的分离。  \n\n丝纹，是指浸涂或流涂后在涂膜表面呈现的条纹状的花纹。实际上也是发花的一种表现形式。",
+        "category": " Introduction"
+    },
+    {
+        "id": 793,
+        "chunk": "# 2.浮色发花形成的原因  \n\n产生浮色发花的原因是很多的。一般认为，贝纳尔涡流、颜料粒子运动速度的差别、颜料粒子絮凝等是主要原因。但颜料组合匹配不当、添加剂运用不宜、容积不匹配、树脂拼合不合理等也会造成浮色发花。  \n\n（1）贝纳尔涡流涂料涂装后，涂膜表层溶剂挥发，表面温度下降，表层密度和表面张力增加，上层密度大，受重力作用向下沉。下层富含溶剂，表面张力低，受表面张力梯度作用，又推动涂料由下（表面张力低）向上（表面张力高）运动，新上来的富含溶剂的涂料表面张力比周边低，因此涂料又由中心被推向“边缘“，并在此堆积，向下沉降，形成了规整的六边形，这就是贝纳尔涡流（图2-4-14）。  \n\n![](images/97fb54dd3db326ed127299e01163fa7055a3bce2a049159e6e5750e6a3d96247.jpg)  \n图2-4-14贝纳尔涡流作用原理  \n\n溶剂与其缔合的基料，携带颜料粒子一同由涡流的中心上升到涂膜的表面。但其所携带的各种颜料粒子的比率却不相同，比表面积大的，粒径小，比表面积小的，粒径大得多，这是因为小粒子运动速度快，其结果导致颜料的分级或重新分布，使一种颜料在表面呈现出较高的浓度。  \n\n由涡流中心携带颜料上升到表层的富含溶剂的涂料，因其表面张力比周边低，因此，它会向表面张力高的六边形的边缘处运动，并在此堆积，所以人们看到边缘处颜色深，并有“小丘”，这就是发花及橘皮的简单成因。  \n\n(2）颜料粒子运动速度的差别各种颜料粒子在分散体系中，布朗运动速度是不相同的。颜料粒子运动速度受粒径、形状、密度、絮凝度、电荷等各种因素影响。在显微镜下不同粒子的运动会看得很清楚。  \n\nStokes定律指出，球形颜料粒子下沉的速率主要与粒径有关：  \n\n$$\nv{=}\\frac{2r^{2}(\\rho_{1}-\\rho_{2})_{\\it g}}{q\\eta}\n$$  \n\n式中，v为沉降速率； $\\rho_{1}$ 为颜料的密度； $\\rho_{2}$ 为树脂基料的密度；为颜料粒子半径；$\\eta$ 为树脂基料黏度； $_{g}$ 为重力加速度。  \n\n该式说明粒径越大，沉降速率越快。为了计算方便，可将该式简化。Kresse将其简化成下式：  \n\n$$\nv=(\\rho_{1}-\\rho_{2})r^{2}\n$$  \n\n该式更便于讨论粒度对浮色发花的影响，可初步判断出某种颜料分散体系是否有浮色发花的倾向。  \n\n如醇酸树脂密度 $0.92\\mathrm{g}/\\mathrm{{{cm}^{3}}}$ . $\\mathrm{TiO}_{2}$ 密度 $4.28/\\mathrm{cm}^{3}$ ，粒径 $r=0,25\\mu\\mathrm{m}$ ；菁蓝密度  \n\n1.73g/cm，粒径r=0.05μm。通过上式可以算出钛白的沉降速率大约是酸菁蓝的100倍以上，如果处理不当有浮蓝的倾向，表面颜色变深。  \n\n在制漆时钛白经常与彩色颜料组合，钛白与菁蓝组合经常会出现浮色发花，这是因为这两种颤料粒子的密度、粒径、运动速度都相差很大。在分散体系中，如果这两种颤料粒子都经过了良好的润湿分散，就不会出现浮色发花问题，但若对运动速度没有进行控制，有可能还会出现浮色发花现象，浮蓝的可能性大。钛白会因重力下沉。两种颜料粒子都没有经过良好的润湿分散，有可能浮蓝，也有可能浮白。若是浮白，因为菁蓝过度絮凝，受粒径影响，菁蓝下沉，钛白上浮。如两种颜料中有一种具有良好的分散润湿效果，而另外一种没有，那么浮在上边的多半是具有良好润湿分散效果的颜料粒子。  \n\nStokes公式只说明沉降速率，但各种颜料粒子还有各自的运动特性，一般是密度低，比表面积大，粒径小的粒子运动速度快，例如，炭黑的运动速度是钛白的10000倍。一定会产生浓度差，造成浮色。而布朗运动会使分散体系均一化，但条件是颜料粒子表面必须要具备足够的能障保护，防止范德华引力而造成的絮凝。  \n\n(3）颜料粒子絮凝颜料混合物中若某种颜料产生过度絮凝会造成浮色发花。  \n\n实践经验证实，比表面积大、粒径小的有机颜料，比比表面积小、粒径大的无机颜料更容易产生絮凝，例如，菁蓝、有机红、炭黑等在与无机颜料组合的分散体系中更容易产生絮凝。絮凝的原因有很多，以下就几种主要原因做简要叙述。  \n\n$\\Phi$ 颜料粒子的自体絮凝颜料团粒经研磨分散后，比表面积、棱角个数及边线长度均大幅度增加。表面能也随之加大，在分散体系中的不稳定因素大大增加。没有能障保护的裸露粒子，在范德华引力作用下会很快地絮凝在一起。有机颜料的表面性质不同于无机颜料表面的特性。有机颜料表面的活性吸附基团少，树脂聚合物对其的润湿性差，加之其粒径小，运动速度快，碰撞的频率高，更容易产生絮凝。而无机颜料表面一般具有反应活性中心，容易与树脂和助溶剂的活性基团产生反应，使其锚定在颜料表面上，起到良好的润湿分散的作用。因此，在钛白复配彩色颜料的体系中，浮白或白中漂浮蓝、红、黄、黑等花斑的发花现象是常见的。  \n\n$\\textcircled{2}$ 架桥絮凝主要是依靠架桥剂将颜料粒子连接在一起，颜料粒子表面没有达到饱和吸附时，有剩余的活性中心，吸附在其他颜料上的聚合物分子的另一端，会通过颜料粒子上剩余中心将两个或多个颜料粒子连接起来，构成杂絮凝，如果这种絮凝是微量的，是有益的，若是严重的，则是有害的，会产生沉降、返粗、失光甚至报废等不良影响。  \n\n分散剂应用不当或者用量不足也会产生架桥絮凝。但有一种控制絮凝的分散剂，这种助剂是通过吸附在颜料粒子表面上的饱和吸附层，将一定量的颜料粒子连接起来，这种控制絮凝是有益的。还有电荷作用产生的絮凝，如果两种颜料粒子的表面所带的电荷不相同，会通过静电作用吸附到一起产生絮凝。产生电荷的原因是很多的，例如，氧化物颜料粒子在酸性或碱性介质中会带电，吸附离子型表面活性剂电离后会带电，带电的渠道是很多的。这种絮凝也可以认为是架桥絮凝。  \n\n$\\textcircled{3}$ 颜料和基料之间的絮凝涂料的展色剂绝大多数是数种聚合物的混合体。一旦树脂之间极性不同，分子量不同，那么与颜料粒子的亲和性也就不同。极性大、分子量小的树脂会被颜料优先吸附（特别是无机颜料），如果颜料粒子吸附的聚合物分子量过低，能障小于范德华引力就会产生絮凝，过度絮凝就会造成浮色发花。  \n\n即使展色剂是单一的聚合物，假若分子量分布过宽，小分子量、极性大的聚合物也会优先吸附到颜料粒子的表面上，导致粒子的吸附层比较薄，没有足够厚的空间位阻作用，所以颜料粒子就会产生絮凝，在相同界面处浓集或沉淀、产生浮色发花。  \n\n$\\textcircled{4}$ 水性涂料中共溶剂的影响在水性涂料中使用的有机溶剂对颜料分散的稳定性构成影响，这种影响主要取决于颜料与所用分散树脂的疏水部分相互作用的程度，这种相互作用的程度与“水/有机溶剂”之间的界面张力有关，界面张力越小，颜料吸附树脂的量就越少，这是因为树脂与有机溶剂的相互作用程度增大所致。所以当水性分散体系主要依靠树脂为颜料分散材质时，要注意选择水和所用有机溶剂之间的界面张力。以免颜料产生絮凝、分离等不良现象，造成浮色发花。  \n\n还有许多其他原因也能造成颜料絮凝，产生浮色发花现象。比如分散剂用量不够；与树脂聚合物不相容；分散剂带电与树脂电荷不相符；分散剂与分散剂之间不匹配，分散剂与其他助剂不匹配等都能造成颜料絮凝、产生浮色发花。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 794,
+        "chunk": "# 3.防止浮色发花的对策  \n\n防止颜料絮凝，控制贝纳尔涡流，调整颜料粒子运动速度，注意粒子带电的一致性，就可以最大限度地防止浮色发花的产生。  \n\n(1）防止贝纳尔涡流的产生前面讲述贝纳尔涡流是产生浮色发花的主要原因之一，如能阻止贝纳尔涡流的形成就可以防止浮色发花的产生。  \n\n若能达到以下诸多条件，就可以防止贝纳尔涡流的产生。  \n\n溶剂溶解树脂的能力要强，溶剂的溶解度参数和氢键参数要与树脂的溶解度参数和氢键参数相同或相近。也就是说溶剂必须是树脂的真溶剂。  \n\n另外，溶剂与树脂的密度、溶剂与树脂的表面张力也要相接近。  \n\n在涂料配方中这些条件若能满足，贝纳尔涡流就不会产生。但这种匹配条件是困难的，很难得以实现，即使可以实现，成本往往也是人们所不能接受的。而加人流平剂工艺简单，成本低，是人们经常采用的控制贝纳尔涡流的有效方法。  \n\n控制贝纳尔涡流的流平剂必须具备降低涂料表面张力的能力。有机硅流平剂是人们经常使用的一种表面状态控制剂，具有较好的防止发花效果。这类流平剂通常有三种结构不同的产品，其降低表面张力的效果也各不相同。有些聚醚改性的聚硅氧烷，可以把水的表面张力降至 $25\\mathrm{mN/m}$ 以下。  \n\n这种改性的聚硅氧烷与树脂聚合物的相容性是受限的，再加之有机硅的蠕变特性，涂装后有机硅流平剂会很快地由涂料内部迁移至涂膜表面，形成单分子膜层，降低涂膜的表面张力，使涂膜的表面张力趋于平衡，贝纳尔涡流无法把内部富含溶剂的涂料推到表面张力比较低的涂膜表面上来。贝纳尔涡流又无法把下面的颜料推上来。因此，达到了防止发花的效果。浮色与贝纳尔涡流无关，是颜料贮存稳定性的问题。所以流平剂只能防止发花，而不能防止浮色。防止浮色要靠分散剂或增稠剂等添加剂解决。 Y  \n\n这类助剂很多，例如Degussa公司的TegoGlide-410、450、TegoFlowATF-2等产品都有很好的防发花、增滑、防缩孔等表面控制效果。  \n\n(2）使用润湿分散剂使用润湿分散剂控制颜料浮色发花是一种非常有效的方法。无论是控制絮凝型的分散剂，还是解絮凝型的分散剂，应用得当，它们都会使分散体中的颜料处于稳定状态。 工  \n\n$\\Phi$ 控制絮凝型分散剂这类分散剂一般都是传统型的低分子量化合物。依靠自身把一定量的颜料粒子连接在一起，控制颜料粒子的运动性，防止颜料粒子过度絮凝，起到了防止浮色发花的目的。  \n\n特别是聚羧酸化合物类分散剂，其分子结构中含有较多羧基，通常会与含羧基的树脂聚合物有好的相容性。特别是与醇酸树脂、聚酯树脂等合成树脂涂料的相容性很好。在应用时如果配上有机硅流平剂，可以有效地控制以钛白为主，配合其他有机颜料制成的彩色涂料的浮色发花问题。  \n\n这是因为这种分散剂可以使钛白与有机颜料形成共絮凝。锚定吸附在钛白上的分散剂与吸附在有机颜料表面上的分散剂通过极性或氢键连接起来。颜料粒子以分散剂为桥形成一个网状的絮凝结构。粒子间，隔有分散剂，基本上还是处于分散状态。这种分散体系在静止状态下通常黏度有所增加，当高速剪切时分散剂之间的结合键遭到破坏，黏度下降，提高了涂料的流动性，当剪切停止时，结构重新恢复，黏度上升，起到了防止颜料沉降，控制粒子运动速度的作用。因此，对防止颜料浮色发花是相当有益的。颜料分散时添加的有机硅流平剂是颜料的润湿剂，能够降低颜料和基料之间的界面张力，有助于颜料粒子对分散剂及树脂聚合物的吸附作用。没有被颜料吸附的多余部分，还可以迁移至表面，发挥涂膜表面状态控制作用。也有防止发花的效果。  \n\n这类控制絮凝的分散剂很多，还有聚羧酸的长链胺的高分子化合物。属于电中性的。胺对有机颜料的吸附是有效的，与有机颜料表面通过氢键结合。羧基与钛白表面的碱性中心，进行酸碱吸附，形成表面盐化合物，牢牢地锚定在钛白的表面。吸附在有机颜料表面的分散剂与吸附在钛白表面的分散剂通过质子的授受形成氢键结构连接在一起。构成颜料粒子的控制絮凝，起到防止浮色发花的效果。  \n\n根据作者的经验，使用R-820钛白粉配上菁蓝，用聚羧酸化合物为分散剂，加上流平剂TegoGlide450，上磨混研，基本上可以控制浮色发花的现象；同样使用上面介绍的钛白配上有机黄颜料，加上聚羧酸长链胺盐类分散剂，例如Tego、Dispers 630，再配上流平剂Tego Glide 450，上磨混研，基本上也可以控制浅黄色或浅绿色涂料的浮色发花的现象。  \n\n$\\textcircled{2}$ 解絮凝型分散剂这类分散剂绝大多数是高分子聚合物型分散剂。其主要特点是分子量比较大，多数在1万 ${\\sim}2.5$ 万之间。有铺定吸附链段，有与树脂相容的伸展链段，构成空间位阻稳定作用。目前市场上供应的产品主要有聚氨酯型和丙烯酸共聚物型两大类产品。多数是用于有机颜料的分散。锚定段通过许多锚定基牢固地吸附在有机颜料粒子的表面上。伸展基依靠伸展链段在颜料粒子的周围构成空间位阻，可使颜料粒子间的距离在 $20\\mathrm{nm}$ 以上，处于稳定的分散状态。同时高分子聚合物分散剂能够控制颜料粒子的运动速度，使各种颜料粒子的运动速度达到平衡状态。还有学者指出，调整高分子聚合物分散剂的添加顺序，可让颜料粒子带有相同电荷，控制因电荷引起的絮凝，造成浮色发花的不良现象。  \n\n使用高分子聚合物分散剂要注意以下几点。  \n\na.要注意分散剂与树脂的相容性，若相容性不好，不但达不到防止浮色发花的效果，而且还会使分散体系处于不稳定状态，产生增稠、返粗、沉降等病。b.还要注意添加量，一定要使颜料表面达到饱和吸附。有机颜料按比表面积添加，比表面积越大，添加量越多，如添加量不足，还不如不加，既浪费成本，又达不到分散效果。c.还有一点就是要注意添加顺序，一般是先加溶剂（包括水)→分散剂→颜料（揽拌）→适量的树脂溶液（注意树脂浓度）。  \n\n高分子聚合物分散剂目前是最好的分散剂。它能够分散稳定各类颜料，彻底解决浮色发花问题。尤其对小粒径的颜料，特别是炭黑和有机颜料效果更显著；能够提高颜料的着色力、鲜艳度；不影响涂膜的光泽和透明性；在水性体系中具有优异的耐水性和耐皂化性。  \n\n(3）采用增稠剂使用增稠剂防止颜料浮色发花，也是常见的一种方法。在许多增稠的涂料体系中，由于黏度调整剂的应用，往往赋予涂料一种结构黏性，这种结构黏性可以控制颜料粒子的运动，能够防止沉降，减弱或消除贝纳尔涡流。所以利用增稠剂防止浮色发花也是一种有效的方法。但是要注意其对光泽和流动性等方面的影响。涂料增稠的方法还是很多的，可以使用高吸油量的颜填料，也可以利用碱性颜填料与树脂中残留的酸进行化学反应增稠。但这些方法会对涂料性能构成影响，所以在高档涂料中基本不采用，多数使用黏度调整剂来增稠。  \n\n$\\Phi$ 在基料中膨润分散的增稠剂这类增稠剂在树脂溶液中膨润分散，形成网状结构，赋予涂料结构黏性，使涂料变成触变流体。  \n\n主要产品有氢化麻油，麻油加氢成为12-羟基饱和脂肪酸的甘油三酸酯。依靠羟基在非极性溶剂中形成网状结构，起到增稠触变作用。在使用时要注意应用温度范围，以免温度过高熔融，冷却后产生结晶析出，丧失增稠效果，而且影响涂料的表观性能。  \n\n有机改性膨润土也是目前应用范围最广泛的一种产品。它是 $_2:1$ 层状结构黏土，上下两层为硅氧结构四面体，中间一层是八面体，由铝或镁与6个氧原子或氢氧原子团配位。八面体中的高价带正电荷原子，被低价带正电荷原子取代。造成正电荷缺陷，负电荷过剩，提供了用有机阳离子表面活性剂改性的条件，生产出有机改性膨润土。  \n\n膨润土利用边缘的羟基或氧形成氢键结构形成网状体，赋予涂料良好的触变性。使用时注意溶剂的极性要与有机改性膨润土的极性相一致。例如，Benton34是用于极低极性溶剂中的，Benton38是用于中极性到极低极性溶剂中的。应用时最好先制成膨润土膏。活化时可以使用含微量水的乙醇。最好是用电中性的分散剂。  \n\n属于这类增稠剂的还有金属皂类化合物，但这类产品目前在涂料中使用很少。  \n\n$\\textcircled{2}$ 分散性胶体构成的增稠剂在涂料中以胶体状态分散，依靠分散胶体形成网状结构，使涂料黏度增加。当遇到高剪切速率时涂料的结构黏性破坏，黏度随之下降。  \n\n聚乙烯蜡是一种胶体分散体，是乙烯和其他单体在高压下经自由基聚合反应制得的。也可采用高分子量聚乙烯降解法生产。制造时可通过氧化处理方法引入羧基、羟基、醛基、酮基及过氧化基等极性基团。一般分子量控制在 $1500\\sim3000$ 。分子上含的极性基可以定向吸附在颜料粒子表面上，碳链伸展在漆料中。由于溶剂化作用，聚乙烯蜡与颜料粒子一起形成触变凝胶结构。起到了防沉、防浮色发花的效果。但分子结构极性和支化度不同，凝胶效果也有所差异。  \n\n聚乙烯蜡是一种非溶解性的，胶体溶胀分散体，对涂料黏度影响甚微，与其他增稠防沉剂有本质上区别，它不易受颜料和漆料的性能影响。  \n\n使用时可将其与溶剂一起加热制成糊状物添加到涂料中，也可将其直接加到色浆中与颜料一起研磨分散。  \n\n超细二氧化硅也是胶体分散体增稠防沉剂。其比表面积为 $150\\mathrm{\\sim}380\\mathrm{m}^{2}/\\mathbf{g}.$ 。由于制造方法不同，表面所含硅醇基数量不同。硅醇基数量少的适宜作增稠剂，多的不适宜作增稠剂。原因是硅醇基多，羟基之间的距离太小，粒子上的羟基自己形成氢键结构，不能将粒子连接起来，形不成网状结构，没有增稠效果。硅醇基数量少的二氧化硅粒子之间通过羟基形成氢键结构，将粒子连接起来，形成网状结构，起到增稠防沉的作用。粒子之间的氢键结构越多，涂料的结构黏性就越大，防止浮色发花效果就越强。但会影响涂料的流动和光泽。所以对黏度要注意控制，以免影响涂料的其他性能。  \n\n二氧化硅在不同极性介质中，其触变结构效果不同。在烃、卤代烃类极低极性溶剂中，结构黏性破坏后，恢复极快，有的只要几分之一秒。在具有氢键键合倾向的极性液体中，黏度有时达数月之久才能恢复。当然这也与气相二氧化硅的浓度和分散程度有关。 ?  \n\n使用时最好先制成母料，再将其分散到涂料中去。分散不好容易产生沉淀，在溶剂型涂料中最好使用经过表面处理的气相二氧化硅。  \n\n属于这类增稠防沉剂的产品还有焙烧型的超细的沉降碳酸钙。但应用并不广泛。综上所  \n\n述，可以得出以下结论。  \n\n制造复色漆选择颜料时，要注意颜料的密度、粒子的比表面积。在条件许可的情况下最好是选用密度、粒径比较相近的颜料进行复配。如果条件不许可就要事先计算出是否会有絮凝浮色发花产生。若有这种危险性就要采取一定措施进行预防。  \n\n首先要选用恰当的分散剂，有机颜料最好选用高分子聚合物解絮凝型的分散剂。有机无机混合颜料，可选用控制絮凝的传统型分散剂，成本允许，当然最好选用高分子型分散剂。  \n\n增稠防沉剂也是人们常用的添加剂，除可以控制密度大的颜料沉降外，还可以控制贝纳尔涡流的产生及粒子的运动速度，对防止絮凝是有益的。  \n\n最后还要注意流平剂的应用。流平剂不但可以控制涂膜的表面状态，还可以防止贝纳尔涡流在涂料表面发生。是防止发花非常好的助剂。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 795,
+        "chunk": "# 4.浮色发花的检测方法  \n\n浮色发花严重时用肉眼就可以看到，有时观察不到，特别是浮色，需要采用一些方法进行检测。  \n\n(1）指擦法制板后，待涂膜溶剂挥发至半干时，用食指在该涂膜上作划圈式研磨直至全干。如果指研区域颜色与未擦地方深浅不一，说明有浮色发花现象产生。单色漆也可以用该法检验，若指研地方颜色深，光泽高或更透明，也说明颜料产生了絮凝。若没有差别，说明颜料分散稳定性非常好。  \n\n除用肉眼观察外，还可以采用色差仪进行指擦色差试验， $\\scriptstyle\\Delta E$ 值越小，表明色差越小，说明颜料分散稳定性越好。  \n\n(2）揉摩法实际与指擦法相似，将待查漆滴到玻璃板上，稍稍晾干后，用手指使劲揉摩湿态漆，直到粘手指状态，目的是为了破坏漆中的颜料絮凝物，待其干燥后将其与未揉摩的地方相比较，观察表面色相的差别，判断是否有浮色发花产生。  \n\n(3）滴查法将漆滴到玻璃板上，待其干燥后观察其表面是否有六角涡流现象。还可以查看漆滴上部和下部之间色相上的差别。  \n\n（4）采用不同涂装方法，观察涂膜表面色相变化喷涂、刷涂、辊涂、浸涂、淋涂各种施涂方法，涂装时的剪切应力不同，剪切速率也不同，对涂料结构黏性破坏程度不一。如制出的样板有色相差别，则可判定涂料有浮色发花现象。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 796,
+        "chunk": "# 七、增稠剂  \n\n水性涂料是以水为分散介质的涂料。而水的黏度很低，不能满足涂料涂装的要求。因此，生产时一般通过加增稠剂调节流变性，以满足各种要求。乳胶漆是使用面最广、使用量最多的水性涂料，下面以乳胶漆为主，介绍增稠剂。其他水性涂料可参照使用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 797,
+        "chunk": "# 1.乳胶漆对流变性的要求  \n\n乳胶漆在生产、贮存、施工和成膜过程中，都分别要求有与其相适应的流变性。  \n\n巴顿介绍，制造过程中，在高速分散机的分散盘附近，其剪切速率范围约为 $1000\\sim$ $10000{\\bf s}^{-1}$ ，而在容器顶部，剪切速率仅为 $\\scriptstyle1\\sim108^{-1}$ ，接近容器壁的涂料实际是静止的。乳胶漆泵送进贮槽或装灌至桶里后，剪切速率下降至 $0.001{\\sim}0.58^{-1}$ 。在施工时，蘸漆时的剪切速率估计为 $15\\sim30{\\mathrm{s}}^{-1}$ ，而涂刷时的剪切速率与高速分散时差不多，约为 $1000{\\sim}10000\\mathbf{s}^{-1}$ 。在施工后，乳胶漆会产生流平、流挂和渗透，这时典型的剪切速率在 $100{\\bf s}^{-1}$ 以下。  \n\nJain列出了涂料生产、贮存和施工等不同阶段的剪切速率，见表2-4-8。对于同一阶段，不同的人介绍的剪切速率会有差别。  \n\n表2-4-8涂料生产、贮存和施工等不同阶段的剪切速率  \n\n\n<html><body><table><tr><td>工 序</td><td>剪切速率/s-1</td><td>工 序</td><td>剪切速率/s-1</td></tr><tr><td>贮存</td><td>0.001~0.01</td><td>流平和沉淀</td><td>0. 01~1. 0</td></tr><tr><td>运输</td><td>0.01~1.0</td><td>流挂</td><td>0. 05~0.5</td></tr><tr><td>混合和搅拌</td><td>1.0~100</td><td>剧涂</td><td>10~100</td></tr><tr><td>泵送</td><td>1000~1500</td><td>辊涂</td><td>100~1000</td></tr><tr><td>分散</td><td>10000~100000</td><td>喷涂</td><td>10000~100000</td></tr></table></body></html>  \n\n为了提高生产率，得到优良的产品，人们提出了不同的流变性要求，见表2-4-9。  \n\n表2-4-9乳胶漆对流变性的要求  \n\n\n<html><body><table><tr><td>过 程</td><td>剪切速率/s-1</td><td>黏度/Pa·s</td><td>屈服值/Pa</td></tr><tr><td>贮存</td><td>0.1</td><td>>50</td><td>>1.0</td></tr><tr><td>漆刷蘸漆而不滴落</td><td>20</td><td>>2.5</td><td>>1. 0</td></tr><tr><td>好的丰满度</td><td>10000</td><td>0.1~0.3</td><td><0.25</td></tr><tr><td>流平和防止流挂</td><td>1.0</td><td>5~10</td><td><0.25</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 798,
+        "chunk": "# 2.增稠剂种类及增稠特点  \n\n乳胶漆对流变性的要求，主要是通过增稠剂的使用而得到满足的。增稠剂多种多样，并具有各自的增稠特点。",
+        "category": " Introduction"
+    },
+    {
+        "id": 799,
+        "chunk": "# (1）纤维素醚及其衍生物  \n\n$\\Phi$ 纤维素醚及其衍生物目前，纤维素醚及其衍生物类增稠剂主要有羟乙基纤维素(HEC)、甲基羟乙基纤维素（MHEC)、乙基羟乙基纤维素（EHEC)、甲基羟丙基纤维素(MHPC)、甲基纤维素（MC）和黄原胶等，这些都是非离子增稠剂，同时属于非缔合型水相增稠剂。其中在乳胶漆中最常用的是HEC。MHEC、EHEC、MHPC具有一定的疏水性，在ICI黏度、抗飞溅和流平等方面，比HEC稍好。另外，聚阴离子纤维素（PAC）也开始在涂料中使用。  \n\n这类增稠剂的增稠机理是由于氢键使其有很高的水合作用及其大分子之间的缠绕。当其加入乳胶漆后，能立即吸收大量的水分，使其本身体积大幅度膨胀，同时高分子量的该类增稠剂互相缠绕，从而使乳胶漆黏度显著增大，产生增稠效果。  \n\n这类增稠剂的特点是：水相增稠，与乳胶漆中各组分相容性好，低剪切速率增稠效果好，对 $\\mathbf{pH}$ 变化容忍度大，保水性好，触变性高。由于低剪切速率黏度高，触变性高，所以抗流挂性好，但流平性差，并且对涂膜光泽有影响。因为分子量较大，分子链较柔韧，高剪切速率时黏度又低，所以涂料辊涂抗飞溅性差。高剪切速率时黏度低，导致涂膜丰满度差。易受细菌侵蚀降解而使涂料黏度下降，甚至变质，因此，使用时体系中必须添加一定的防腐剂。  \n\n$\\textcircled{2}$ 疏水改性纤维素（HMHEC）疏水改性纤维素（HMHEC）是在纤维素亲水骨架上引人少量长链疏水烷基，从而成为缔合型增稠剂。由于进行了疏水改性，在原水相增稠的基础上又具有缔合增稠作用，能与乳液粒子、表面活性剂以及颜料等疏水组分缔合作用而增加黏度，其增稠效果可与分子量大得多的纤维素醚增稠剂品种相当。它提高了ICI黏度和流平性，降低了表面张力。HMHEC使HEC的不足之处得到改善，可用于丝光乳胶漆中。  \n\n(2）碱溶胀型增稠剂碱溶胀增稠剂分为两类：非缔合型碱溶胀增稠剂（ASE）和缔合型碱溶胀增稠剂（HASE），它们都是阴离子增稠剂。  \n\n$\\Phi$ 非缔合型碱溶胀增稠剂非缔合型的ASE是聚丙烯酸盐碱溶胀型乳液，它是由不饱和共聚单体和羧酸等共聚而成的。  \n\nASE增稠机理是在碱性体系中发生酸碱中和反应，树脂被溶解，羧基在静电排斥的作用下使聚合物的链伸展开，从而使体系黏度提高，达到增稠结果的。  \n\n其增稠效果受pH影响很大， $\\mathsf{p H}$ 变化时，增稠效果随之变化。  \n\n$\\textcircled{2}$ 缔合型碱溶胀增稠剂缔合型HASE是疏水改性的聚丙烯酸盐碱溶胀型乳液。其骨架是由约 $49\\%$ （摩尔分数）甲基丙烯酸、约 $50\\%$ （摩尔分数）丙烯酸乙酯和约 $1\\%$ （摩尔分数）疏水改性的大分子构成的。同时还有少量交联剂，在中和膨胀时，使聚合物保持在一起。选用甲基丙烯酸是因为其在低 $\\mathsf{p H}$ 时能进入胶束，而丙烯酸乙酯是由于其低玻璃化温度和高亲水性而被采用。其中疏水基R对增稠效果等影响很大，R可以是壬基苯等。  \n\n其增稠机理是在ASE的增稠基础上，加上缔合作用，即增稠剂聚合物疏水链和乳胶粒子、表面活性剂、颜料粒子等疏水部位缔合成三维网络结构，此外还有胶束作用，从而使乳胶漆体系的黏度升高。  \n\n其特点是增稠效率较高，因为本身的黏度较低，在涂料中极易分散。大多数品种有一定的触变性，也有高触变性的产品可供选择，同时也有适度的流平性，涂料辊涂抗飞溅性较好，抗菌性好，对涂膜的光泽无不良影响，价格便宜。但对pH敏感，即黏度随 $\\mathrm{\\tt{pH}}$ 变化而变化。  \n\n由于含有大量甲基丙烯酸，所以HASE是电解质。这种增稠剂也有含聚氨酯和不含聚氨酯两类。  \n\n(3）聚氨酯增稠剂和疏水改性非聚氨酯增稠剂  \n\n$\\Phi$ 聚氨酯增稠剂聚氨酯增稠剂简称HEUR，是一种疏水基改性的乙氧基聚氨酯水溶性聚合物，属于非离子型缔合增稠剂。  \n\nHEUR由疏水基、亲水链和聚氨酯基三部分组成。疏水基起缔合作用，是增稠的决定因素，通常是油基、十八烷基、十二烷苯基、壬酚基等。亲水链能提供化学稳定性和黏度稳定性，常用的是聚醚，如聚氧乙烯及其衍生物。HEUR分子链是通过聚氨酯基来扩展的，所用聚氨酯基有IPDI、TDI和HMDI等。  \n\n缔合型增稠剂的结构特点是疏水基封端。  \n\n增稠机理是HEUR在乳胶漆水相中：一是分子疏水端与乳胶粒子、表面活性剂、颜料等疏水结构缔合，形成立体网状结构，这也是高剪黏度的来源；二是犹如表面活性剂，当其浓度高于临界胶束浓度时，形成胶束，中剪黏度 $(1\\sim100\\mathrm{s}^{-1}$ ）主要由其主导；三是分子亲水链与水分子以氢键起作用，从而达到增稠结果。  \n\n其特点是：由于低剪切速率黏度低，所以流平性较好，对涂料的光泽无影响。而高剪切速率黏度高，故涂膜丰满度高。分子量较低，并且高剪切速率黏度高，因此涂料辊涂施工抗飞溅性好。在这些方面一般优于碱溶胀型增稠剂。另外，抗菌性好，屈服值低。但是，配方中表面活性剂、乳液、溶剂等对其增稠效果都有很大影响。如乳液含量提高、表面张力降低和粒径减小，都会使增稠效果提高。因为疏水结构互相吸附缔合，所以体系中任一组分HLB值改变，增稠效果也随之改变。即对配方变动非常敏感。但配方中的水、湿润剂、钛白粉、填料和水溶性溶剂等，与缔合型增稠剂相互作用较弱，所以对黏度影响较小。  \n\n环境友好的缔合型聚氨酯增稠剂开发受到普遍重视，如不含VOC和APEO的缔合型聚氨酯增稠剂。  \n\n除了上面介绍的线型缔合型聚氨酯增稠剂外，还有梳状缔合型聚氨酯增稠剂。所谓梳状缔合型聚氨酯增稠剂是指每个增稠剂分子中间还有垂挂的疏水基。这类增稠剂有SCT-200  \n\n和 SCT-275等。  \n\n②疏水改性非聚氨酯增稠剂这类疏水基改性的乙氧基非聚氨酯水溶性聚合物，也属于非离子型缔合增稠剂，性能与HEUR相似。如疏水改性氨基增稠剂（hydrophobicallymodified ethoxylated aminoplastthickener，HEAT）、疏水改性聚醚增稠剂（HMPE）和改性聚脲增稠剂等。  \n\n(4）无机增稠剂目前用于乳胶漆的无机类增稠剂主要有膨润土、凹凸棒土和气相二氧化硅。这三种无机增稠剂的共同特点是抗生物降解性好，低剪切速率增稠效果好，但辊涂抗飞溅性差。(5）络合型有机金属化合物类增稠剂它的显著特点是抗流挂性、辊涂抗飞溅性、流平性等都优于纤维素醚类增稠剂。其增稠机理也是通过氢键作用。这种增稠剂对采用HEC保护胶体的乳液是有效的。",
+        "category": " Introduction"
+    },
+    {
+        "id": 800,
+        "chunk": "# 3.增稠剂的选择  \n\n这里分如下几方面介绍增稠剂的选择。  \n\n(1）增稠剂性能和比较各种缔合型增稠剂的性能比较见表2-4-10。  \n\n表2-4-10缔合型增调剂的性能比较  \n\n\n<html><body><table><tr><td>性 质</td><td>HEUR</td><td>HASE</td><td>HMHEC</td></tr><tr><td>成本</td><td>最高</td><td>视品种而定</td><td>稍高于HEC</td></tr><tr><td>抗飞燕性</td><td>优</td><td>很好</td><td>很好</td></tr><tr><td>流平性</td><td>优</td><td>尚好到优</td><td>好</td></tr><tr><td>高剪切速率黏度</td><td>很好</td><td>尚好到很好</td><td>尚好</td></tr><tr><td>高光泽潜力</td><td>很好</td><td>尚好到很好</td><td>尚好</td></tr><tr><td>抗压黏性</td><td>尚好</td><td>好到很好</td><td>好</td></tr><tr><td>对配方中表面活性剂和共溶剂的敏感性</td><td>很敏感</td><td>中度到很敏感</td><td>中度敏感</td></tr><tr><td>对pH的敏感性</td><td>不敏感</td><td>中度敏感</td><td>不敏感</td></tr><tr><td>耐水性</td><td>稍低于HEC</td><td>低于HEC</td><td>稍低于HEC</td></tr><tr><td>耐擦洗性</td><td>很好</td><td>稍好到好</td><td>好</td></tr><tr><td>耐碱性</td><td>很好</td><td>不好到好</td><td>很好</td></tr><tr><td>抗腐蚀性</td><td>很好</td><td>不好</td><td>不详</td></tr><tr><td>对电解质的敏感性</td><td>不敏感</td><td>中度到很敏感</td><td>不敏感</td></tr><tr><td>微生物降解</td><td>无影响</td><td>无影响</td><td>可能发生</td></tr></table></body></html>  \n\n另外，Shay等试验得出，对水分亲和性的一般次序是：酸形式的碱溶胀增稠剂<非离子合成增稠剂（如HEUR） $<$ 纤维素增稠剂 $\\approx$ 盐形式的碱溶胀增稠剂。  \n\n(2）增稠剂和涂料其他组分的相互作用增稠剂的选择不能仅考虑增稠剂，还要结合乳胶漆体系来选择增稠剂。尤其是采用缔合型增稠剂时，要考虑乳液、表面活性剂、成膜助剂和颜料等综合影响，因为它们之间具有交互作用。  \n\n林涛等在研究分散剂和缔合型增稠剂配合时得出，HASE类增稠剂可将多元酸共聚物分散剂从颜料和填料表面置换出来，从而引起桥式絮凝，而HEUR类增稠剂在多元酸均聚物分散剂存在时会发生盐析。如Tamol1254和Tamol850是多元酸均聚物分散剂，Tamol  \n\n850是甲基丙烯酸均聚物；而Orotan731A是多元酸共聚物分散剂，二异丁烯和马来酸的共聚物。为了避免此类问题发生，建议将多元酸均聚物分散剂与HASE类增稠剂配合使用，而多元酸共聚物分散剂和HEUR类增稠剂配合使用。  \n\n张朝平试验得出如表2-4-11和表2-4-12的结果。HASE类增稠剂与多元酸均聚物类分散剂配合使用最好，与亲水性（高酸含量）多元酸共聚物类分散剂搭配使用尚可，而不能与疏水性（低酸含量）多元酸共聚物类分散剂一起使用。HEUR类增稠剂却宜与硫水性多元酸共聚物类分散剂配合使用。  \n\n表2-4-11HASE类增稠剂与不同分散剂配合使用测试结果  \n\n\n<html><body><table><tr><td>增稠剂</td><td>分散剂类型</td><td>光泽度/%</td><td>贮存稳定性</td><td>对比率</td></tr><tr><td rowspan=\"3\">三个不同公司的三个 HASE类增稠剂</td><td>多元酸均聚物</td><td>20~30</td><td>无分层，无沉淀，黏度变化小</td><td>0.94</td></tr><tr><td>亲水性多元酸共聚物</td><td>16~18</td><td>无明显分层，无沉淀</td><td>0.92</td></tr><tr><td>蔬水性多元酸共聚物</td><td>5~8</td><td>胶结干化</td><td>0.87</td></tr></table></body></html>  \n\n表2-4-12HEUR类增稠剂与不同分散剂配合使用测试结果  \n\n\n<html><body><table><tr><td>增稠剂</td><td>分散剂类型</td><td>光泽度/%</td><td>贮存稳定性</td><td>对比率</td></tr><tr><td rowspan=\"4\">三个不同公司的三个HEUR类增稠剂</td><td>小分子磷酸盐类</td><td>10~14</td><td>分层</td><td>0.78~0.85</td></tr><tr><td>多元酸均聚物</td><td>19~22</td><td>分层</td><td>0.75~0.88</td></tr><tr><td>亲水性多元酸共聚物</td><td>19~23</td><td>略有分层</td><td>0.88~0.90</td></tr><tr><td>疏水性多元酸共聚物</td><td>21~25</td><td>无分层</td><td>0.92~0.95</td></tr></table></body></html>  \n\nShaw 等研究了疏水改性纤维素（HMHEC）与乳胶漆组分的相互作用得出，对于颜料和填料，HMHEC类增稠剂NatrosolPlus Grade 330与烧高岭土的缔合比钛白粉和碳酸钙都强。  \n\n对于乳液得出，在醋丙内墙平光乳胶漆中，NatrosolPlusGrade 330 的增稠效率与HEC-250HBR相同，而在丙烯酸内墙平光乳胶漆和外墙平光乳胶漆（不管乳液类型）中，Natrosol Plus Grade 330 的增稠效率比 HEC-250HBR 高 $10\\%\\sim20\\%$ 。Natrosol Plus Grade330还提供比HEC更高的ICI黏度和较好的流平性。  \n\n对于不同HLB值的表面活性剂得出，表面活性剂的HLB值对HEC的增稠效率没有影响，而达95KU 的NatrosolPlus Grade 330 用量却随表面活性剂的HLB值升高而增加，ICI黏度也有提高，见表2-4-13。试验时表面活性剂用量为配方总量的 $0.3\\%$ 。  \n\n表2-4-13表面活性剂的HLB值对涂料流变性的影响  \n\n\n<html><body><table><tr><td rowspan=\"2\">表面活性剂</td><td rowspan=\"2\">HLB</td><td colspan=\"3\">HEC-250HBR</td><td colspan=\"3\">Natrosol Plus Grade 330</td></tr><tr><td>流平性</td><td>ICI</td><td>达95KU增稠剂用量/%</td><td>流平性</td><td>ICI</td><td>达95KU增翻剂用量/%</td></tr><tr><td>Igepal CO-430</td><td>8.8</td><td>5</td><td>0.6</td><td>0.74</td><td>7</td><td>1.0</td><td>0.80</td></tr><tr><td>Igepal CO-610</td><td>12.2</td><td>6</td><td>0.6</td><td>0.76</td><td>6</td><td>1.2</td><td>0.92</td></tr><tr><td>Igepal CO-730</td><td>15.0</td><td>6</td><td>0.7</td><td>0.77</td><td>5</td><td>1.2</td><td>0.99</td></tr><tr><td>Igepal CO-897</td><td>17.8</td><td></td><td>0.6</td><td>0.74</td><td>5</td><td>1.2</td><td>0.99</td></tr></table></body></html>  \n\nMing-RenTarng等研究了非离子表面活性剂和HEUR类增稠剂在无机物和有机物包膜的钛白粉上竞争吸附，得出钛白粉包膜影响分散剂的吸附量。  \n\nMahli等研究了表面活性剂对缔合型增稠剂溶液、增稠乳液分散体和乳胶漆的黏度影响。  \n\nCackovich等认为，在空间位阻稳定时，乳液吸附了乳化剂，指向水中的是亲水层，因此降低了缔合型增稠剂的增稠作用。  \n\nKostansek等用相图表示缔合型增稠剂、乳液和表面活性剂之间的相互作用。相图上分为桥式絮凝区（bridging flocculation region）、好分散区（good dispersion region）和空位絮凝区（depletion flocculation region）。把HEUR类增稠剂加人乳液中，它们就被吸附在乳胶粒上，并把乳胶粒连接起来，而产生桥式絮凝。在粒子之间，由于渗透压，未被吸附的增稠剂分子被排出，形成空位，由此而产生的絮凝称为空位絮凝。他们得出，对好分散区和絮凝区大小影响最大的是乳胶粒大小、电解质浓度以及成膜助剂的类型和浓度。在试验浓度范围内，采用聚氧乙烯类非离子表面活性剂时，如TritonX-100，相图只有桥式絮凝区和好分散区，而没有空位絮凝区。  \n\n成膜助剂、助溶剂和缔合型增稠剂相互作用与其氢键作用参数有关。氢键作用参数大、水混溶性好的溶剂，与缔合型增稠剂的相互作用一般导致黏度下降，如丙二醇和乙二醇。氢键作用参数小、不溶于水的溶剂，一般使黏度上升，如Texanol。  \n\n(3）增稠剂的选择从以上各类增稠剂的增稠机理及特性分析中，可以得到这样一个结论：任何一类增稠剂都有其特点，在涂料的增稠体系中，如果只用一种增稠剂，很难达到长久的贮存稳定性、良好的施工效果和理想的涂膜外观等的统一。通常，在涂料增稠体系中，大多数都是采用两种增稠剂搭配使用来达到较理想的效果。  \n\n纤维素增稠剂的选用原则见表2-4-14。  \n\n表2-4-14纤维素增稠剂的选用原则  \n\n\n<html><body><table><tr><td>No.</td><td>要求性能</td><td>推荐纤维素增稠剂</td><td>No.</td><td>要求性能</td><td>推荐纤维素增柯剂</td></tr><tr><td>1</td><td>增稠效率</td><td>高分子量</td><td>6</td><td>流平性</td><td>低分子量</td></tr><tr><td>2</td><td>贮存稳定性</td><td>高分子量</td><td>7</td><td>抗流挂性</td><td>高分子量</td></tr><tr><td>3</td><td>防酶降解性</td><td>低分子量</td><td>90</td><td>涂刷性</td><td>高分子量</td></tr><tr><td>4</td><td>抗飞溅性</td><td>低分子量</td><td>9</td><td>开放时间</td><td>低分子量</td></tr><tr><td>5</td><td>耐洗刷性</td><td>高分子量</td><td></td><td></td><td></td></tr></table></body></html>  \n\n结合乳胶漆的PVC，可按如下原则选择增稠剂。  \n\n对于高PVC乳胶漆，由于乳液含量低，而颜料和填料用量高，为了保证贮存中不分层，其低剪切速率黏度和触变性应就高控制，因此可采用HEC和碱溶胀增稠剂配合，来调整黏度。PVC越高，选用的HEC分子量也越大，这样配方中增稠剂的成本就可越低。  \n\n中等PVC和低PVC乳胶漆，由于乳液含量较高，可将黏度曲线不同的缔合型增稠剂配合使用，以达到贮存、施工、流平等方面较好的平衡。  \n\n也有人建议，在大多数情况下，以HASE、HEUR一起搭配HEC，或者以HASE搭配HEUR来使用，均能取得满意的结果。仅以HEC和HEUR搭配使用，因为亲水亲油性差距太大，往往导致分水。  \n\n对于厚质和拉毛的涂料，可采用高触变性的纤维素增稠剂或碱溶胀增稠剂。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 801,
+        "chunk": "# 八、催干剂和防结皮剂  \n\n能加速涂膜氧化、聚合、干燥的有机酸金属皂称为催干剂。它主要是由具有变价功能的  \n\n一些金属和其他金属与含 $_{7\\sim22}$ 碳的一元羧酸反应而得的产物。  \n\n传统催干剂的使用形式一般是制成环烷酸、辛酸等有机酸的金属皂。其催干活性高，使用方便。在涂料生产中，将金属皂溶于有机溶剂中，配制成不同浓度的催干剂溶液使用，通称燥液。在油墨中，则将金属皂溶于油中，或与填充料轧制成膏状物使用，称为燥油。",
+        "category": " Introduction"
+    },
+    {
+        "id": 802,
+        "chunk": "# 1.催干剂的作用机理  \n\n油基漆的成膜过程较复杂，一般认为有四个阶段： $\\Phi$ 诱导期； $\\textcircled{2}$ 过氧化物的形成； $\\textcircled{3}$ 过氧化物的分解； $\\textcircled{4}$ 聚合。这一过程虽能自发进行，但速度很慢，需几天时间。其中最慢的一步反应是过氧化物的分解。  \n\n催干剂对油基漆的氧化成膜有加速作用，但其加速机理尚不十分清楚。一般认为它有四个作用： $\\textcircled{1}$ 缩短诱导期； $\\textcircled{2}$ 加快吸氧和过氧化物的形成； $\\textcircled{3}$ 催化过氧化物分解成自由基；$\\textcircled{4}$ 促进聚合。也有人认为，钴和锰类催干剂的作用是： $\\textcircled{1}$ 加速氧的吸收； $\\textcircled{2}$ 催化过氧化物分解成自由基。而铅、锆、钙和铈类催干剂可能是通过催干剂的金属与成膜物中羧基和羟基互相作用而促进干燥。  \n\n对于催干剂加速氧化干燥的机理研究最多的是钻皂。Muller提出的机理是钻的价数的重复转换 $\\mathbf{C}o^{2+}{\\rightarrow}\\mathbf{C}o^{3+}{\\rightarrow}\\mathbf{C}o^{2+}$ 。Girard 等用光谱方法证实了这一点。由数据得出，钴催干剂与酯键中的不饱和部分形成弱配位化合物，伴随着的是共轭化合键的增加。已经确认，这是决定酯吸收氧气快慢的关键。人们发现，在辛酸钻的存在下，吸收氧所需的活化能是$5.44\\mathrm{kJ/mol}$ ，而缺钻的情况下为 $43.10\\mathrm{kJ/mol}$ 。这些研究进一步表明，钻对氧吸收和干燥过程有催化作用。钻皂是通过金属离子的变价而起催干作用，它通过本身的变价而催化氧的获取、质子的释放、双键的活化、酸的分解及过氧化物的分解。  \n\n一般把具有多种化合价的金属皂催干剂称为活性催干剂，它们都容易进行氧化还原反应。如钴皂以催化氧化聚合为主，铅皂以催化加聚为主。锆皂不但有一般的催干特性，而且具有配位能力，与醇酸树脂链上的极性基团如羟基形成配位键，生成更大分子的配位络合物。不但能加速干性，而且能改善涂膜性能。把一些不易变价的金属皂催干剂划分为辅助催干剂，如钙、锌等金属，它们单独使用不具有催干特性，但当与活性催干剂配合使用时，也能改进干性，其机理尚不清楚。有人提出，辅助催干剂能增强活性催干剂的溶解性。也有人认为，辅助催干剂能使活性催干剂保持在更有利的化合价，或者能降低变换化合价所需的能量。也有人提出，辅助催干剂有利于活性催干剂与漆料整合，从而帮助干燥。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 803,
+        "chunk": "# 2.催干剂的类型及其特性  \n\n催干剂有金属氧化物、金属盐、金属皂三类使用形式。金属氧化物和金属盐都是在熬漆过程中加人，形成油酸皂后才呈现催干作用。目前使用最多的还是金属皂这种形式，金属皂是有机酸与某些金属反应而成的。它的通式为RCOOMe，Me表示金属部分，RCOO表示有机酸部分。催干剂的特性决定于金属部分，而有机酸部分使金属成盐后溶解于醇酸树脂介质中，并对催干效果也有一定影响。实际使用最多的为钴、锰、锌、钙、铁；锆、铈/稀土是新型催干剂。  \n\n(1）催干剂的阴离子部分—有机酸有机酸的种类很多，有环烷酸、脂肪酸、2-乙基己酸（异辛酸）等，又发展了新癸酸和异壬酸。催干剂的有机酸决定金属皂在涂料中的溶解性和相容性。催干剂中有机酸虽不相同，但其呈现的催干特性基本相同，如环烷酸铅和亚油酸铅都以催底干为主，但亚麻酸皂因其溶解性差而降低其催干活性。  \n\n近年来，由于环烷酸的资源日益减少，而合成脂肪酸的化学纯度要比天然脂肪酸好得多，因而以合成羧酸皂混合物为基础的催干剂在市场上普遍供应，生产厂家常以其羧酸来命名其催干剂牌号，合成羧酸的高酸值使其金属皂具有较高的含量，黏度也低。由于其耗酸量低，成本与环烷酸皂相近。  \n\n石蜡氧化制取的合成脂肪酸，都为直链酸。其色泽较浅，价格低，但其金属皂的溶解性差。可将其 $C_{6}{\\sim}C_{9}$ 合成脂肪酸与环烷酸或支链脂肪酸拼用，以降低成本。  \n\n(2）催干剂的阳离子部分—一金属离子催干剂可分为活性催干剂 (或称为主催干剂)和辅助催干剂，其中活性催干剂又可分为氧化型和聚合型，见表2-4-15。  \n\n表2-4-15催干剂的分类  \n\n\n<html><body><table><tr><td rowspan=\"4\">活性催干剂</td><td rowspan=\"2\">氧化型(表干型)： Co,Mn,V,Ce,Fe</td><td>锰钻是最活泼的氧化型，剂，促进氧的吸收，过氧化物的形感和分剂。</td></tr><tr><td>锰为氧化型及聚合型双功能催干剂</td></tr><tr><td>聚合型（底干型）：</td><td>铅是最早用的聚合型催干剂，锆是用在不能用铅催干剂的配方中，稀土催</td></tr><tr><td></td><td>Pb,Zr,La,Nd,Al,Bi,Ba,Sr</td><td>干剂用于低湿及高湿环境</td></tr><tr><td>辅助催干剂</td><td>轴助裂（助催干型）：</td><td>钙能提高表干和底干催干剂的效果。锌能改善钴催干剂干性，防止皱皮</td></tr></table></body></html>  \n\n催干剂作用决定于其中的金属离子部分。因此涂料催干剂的用量都是以其所含的金属量来计算，各种催干剂都规定其金属离子浓度。在实际应用时，对于油基清漆是以植物油中的金属百分含量来表示，各种合成树脂涂料，则以树脂固体分中的金属百分含量来表示。  \n\n$\\Phi$ 钴催干剂它是催干活性最强的氧化型催干剂，因氧化作用是从涂膜表面开始，因而它使涂膜表面干燥加速，常作面催干剂。  \n\n钴催干剂一般与铅、锰、钙等催干剂配合使用，使涂层表里平衡干燥。如单独使用或用量过多，会使涂膜表面很快干结而收缩，产生皱皮和因底干不透而发软等各种涂膜缺陷。特别是其强烈的催化氧化性，促使涂膜过早老化并发脆。以钙、锌等助催干剂配合使用，可有效地调节其表面干燥速率。用量超过 $0.08\\%$ 则须注意，必须仔细进行试验评价。  \n\n钻催干剂也可用于热固性涂料如氨基烘漆中以提高其硬度，用量为 $0.005\\%\\sim0.02\\%$ 与铁、锰催干剂相比，不易变色，但硬度和坚韧性不及后者。在油墨中因涂膜极薄，故可单用钻催干剂。  \n\n钻皂与类抗结皮剂混用会形成金属-络合物而呈现红色至紫红色，各种产生不同的颜色，但涂膜干燥后其颜色即消失。  \n\n$\\textcircled{2}$ 锰催干剂锰催于性较钴催干剂弱，具有良好的底催干性能。一般与钴、铅皂配合使用。  \n\n锰催干剂在热固性涂料中使用可提高涂膜的坚韧性与硬度，其效果要比钻皂好，但色深并易泛黄，不宜用于白色漆中。其用量为 $0.005\\%\\sim0.02\\%$ 。  \n\n锰催干剂在使用时，常会使涂膜出现一些反常现象，如皱皮、发霜等，须特别注意；特别是在铅存在下，锰催干剂的缺陷更为显著，配合钙催干剂可改善清漆发浑、色漆皱皮。  \n\n在低温时影响干性较小，在表干要求不高时，可用锰催干剂取代钴催干剂。但锰催干剂易变色，特别是在烘烤时更为严重。  \n\n锰催干剂虽能有效地催底干，但仍须与助催干剂拼用。  \n\n$\\textcircled{3}$ 钙催干剂钙催干剂没有显著的催干作用，但与钴催干剂、锆催干剂配合使用，可以提高其催干效果，还可以使表干与底干平衡，消除起皱。钙催干剂对颜料有润湿和分散作用。它属于助催干剂。  \n\n$\\textcircled{4}$ 锌催干剂锌催干剂为助催干剂，因它能保持涂膜有较长的开放时间，使涂膜能较彻底干燥，故在某些涂料中使涂膜具有较好的硬度。锌催干剂在很多涂料中使用，能延迟其表干。它与环烷酸铅及钙一样，是优良的颜料润湿剂，因而在研磨阶段加入，能改进颜料的分散性，并能降低其失干性。也有报道锌催干剂能消除活性金属复合物的形成而产生的变色现象，因为先形成的锌复合物是无色的。  \n\n$\\textcircled{5}$ 铁催于剂铁催干剂在室温时无明显的催干作用， $130^{\\circ}\\mathrm{C}$ 以上则具有强烈的聚合催干作用，使涂膜具有更大的硬度和坚韧性，主要用于热固性涂料。但铁催干剂颜色很深。  \n\n$\\textcircled{6}$ 钒催干剂钒催干剂的活性很高，但由于其高价的化合态，贮存性极不稳定。并且由于其颜色深并有失干的倾向，故其应用受到了很大的限制。  \n\n$\\textcircled{7}$ 铈/稀土催干剂稀土混合催干剂是铈、镧、铕、钇羧酸皂的混合物，其主要组分为铈羧酸皂，其催干特性与铈催干剂一致。而镧、铕、钇的羧酸皂没有明显的催干作用。因而稀土混合催干剂中的组分及含量的控制极为重要。  \n\n铈/稀土催干剂兼具表干及底干的催干性能，而且具有配位性，能促进醇酸树脂等涂料的实干。铈/稀土催干剂可取代铅、锰、锌、钙等催干剂，并且其活性比铅、锰等要高，其用量只相当于铅、锰、锌、钙等催干剂总量的 $40\\%\\sim80\\%$ ，可以降低涂料成本。  \n\n$\\textcircled{8}$ 锆催干剂锆催干剂实际是聚合的锆氧基与合成有机酸的配位化合物，属于配位型聚合催干剂，能与连接料中的羟基或其他极性基团络合，生成更大分子量的配位络合物，锆催干剂本身成为涂膜的组成，因而具有独特的催干性。  \n\n锆催干剂对其他催干剂有较强的促催干作用，能有效地提高钴、锰皂的催干性，对铅、钙皂也有辅助作用，本身又具有类似铅皂的催底干性。由于锆催干剂的多功能性，在气干型涂料及烘干型涂料中采用锆催干剂能提高涂膜的全面性能，如硬度、光泽等。  \n\n$\\textcircled{9}$ 铅催干剂铅催干剂为聚合型催干剂，在大多数醇酸涂料中能促进涂膜底层干燥而得到坚韧而硬的涂膜，并能提高涂膜的附着力及耐候性。但其氧化催干性低，必须与钴、锰催干剂配合使用。一般用量为钻用量的10倍，正常用量为 $0.5\\%\\sim1\\%$  \n\n铅皂对颜料有润滑分散作用，颜料分较多的漆浆，在轧制前加入以降低其黏稠度，并能改善其失干倾向。铅皂具有抗腐蚀作用，在润滑油或润滑脂中使用有防老化性及抗腐蚀性。  \n\n铅皂的色泽较淡，一般为淡黄色液体，还可制得近于无色的精制品而用于白色漆中。  \n\n铅皂与醇酸树脂中游离的苯二甲酸酐形成溶解度较小的铅盐而析出，使清漆发浑。铅皂与空气中的硫化物作用而变色，因而使涂膜沾污而变暗。铝粉漆中若使用铅皂，铝粉表面的硬脂酸膜为铅皂取代而失去漂浮性，因而使铝粉漆涂膜亮度差而发灰。  \n\n铅皂有毒性，使用受到严格限制，尤其在玩具及儿童用品的涂料中严禁用铅皂作催干剂。常以铈或锆催干剂代之。  \n\n此外，还有其他催干剂，如铝催干剂、钡催干剂、催干剂、锂催干剂等。  \n\n催干剂是自动氧化的催化剂，它使涂料快干，但它残留在涂膜中，也可使涂膜老化降解和黄变。有人建议用 $^{58}{\\bf C}_{0}$ 同位素代替普通Co，由于其半衰期短，易退化掉。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 804,
+        "chunk": "# 3.催干剂的选用  \n\n由于涂料体系的组分不同，对应的干燥速率要求也不同，因此，应选择不同的催干体系。  \n\n常用的催干剂是钻、锰、锌、钙等，近年来又逐步使用铈/稀土、锆催干剂。将几种催干剂配合使用，不但能使催干效力显著提高，而且使涂膜的表干及底干一致。如在醇酸滋漆中以钻、锆、钙3种催干剂配合使用，其催干性好，并能提高涂膜的性能。  \n\n影响干性的因素有温度、湿度、光线、树脂类型、溶剂、涂膜厚度、颜料等。因此，催干剂的选用应根据这些实际情况加以调整。  \n\n(1）催干剂的推荐用量范围催干剂的配比是以树脂固体分所需催干剂金属百分数表示。一些资料的推荐用量范围见表2-4-16。不同树脂推荐催干剂组合见表2-4-17。  \n\n表2-4-16催干剂的推荐用量范围  \n\n\n<html><body><table><tr><td rowspan=\"2\">序号</td><td rowspan=\"2\">催干剂</td><td colspan=\"4\">推荐用量（配比）/%</td><td colspan=\"2\">金属浓度/%</td></tr><tr><td>文献[1]</td><td>文献[2]</td><td>文献[2]最大用量</td><td>文献[3]</td><td>文献[1]</td><td>文献[3]</td></tr><tr><td>1</td><td>钙</td><td>0.05~0.2</td><td>0.2</td><td>0.4</td><td>0.05~0.1</td><td>4/6/10</td><td>3/6</td></tr><tr><td>2</td><td>钻</td><td>0.02~0.06</td><td>0.06</td><td>0.2</td><td>0. 03~0. 1</td><td>4~12</td><td>6/11</td></tr><tr><td>3</td><td>铅</td><td>0.5~1</td><td>0.5</td><td>1.0</td><td>0.5~2</td><td>12~36</td><td>12/18/24/32</td></tr><tr><td>4</td><td>锰</td><td>0. 02~0.08</td><td>0.02</td><td>0.1</td><td>0.02~0.1</td><td></td><td>6/8</td></tr><tr><td>5</td><td>锌</td><td>0.03~0.2</td><td>0.2</td><td>0.4</td><td>0.05~0.1</td><td>6/8/16/18</td><td>6/12</td></tr><tr><td>6</td><td>锆</td><td>0.03~0.2</td><td>0.3</td><td>0.4</td><td>0.1~0.3</td><td>6/12/18/24</td><td>6/12</td></tr><tr><td>7</td><td></td><td></td><td>0.2</td><td>0.4</td><td></td><td></td><td></td></tr><tr><td>8</td><td></td><td></td><td>0.03</td><td>0.05</td><td></td><td></td><td></td></tr><tr><td>9</td><td></td><td></td><td>0.3</td><td>0.5</td><td></td><td></td><td></td></tr><tr><td>10</td><td></td><td></td><td>0.4</td><td>0.6</td><td></td><td></td><td></td></tr><tr><td>11</td><td>钾</td><td></td><td>0.03</td><td>0.08</td><td></td><td></td><td></td></tr><tr><td>12</td><td>锂</td><td></td><td>0.03</td><td>0.05</td><td></td><td></td><td></td></tr><tr><td>13</td><td>铈/稀土</td><td>0.2~0.5</td><td>0.2</td><td>0.6</td><td></td><td>6/8/12</td><td></td></tr></table></body></html>  \n\n表2-4-17不同树脂推荐催干剂组合  \n\n\n<html><body><table><tr><td>序号</td><td>树 脂</td><td>主催干剂</td><td>辅催干剂</td></tr><tr><td>1</td><td>干性油</td><td>0.03Co或Mn</td><td>0. 2Zr,0.1 Ca</td></tr><tr><td>2</td><td>中油醇酸树脂</td><td>0.04Co</td><td>0. 2Zr,0.1Ca</td></tr><tr><td>3</td><td>长油醇酸树脂</td><td>0.05Co</td><td>0. 3Zr,0.2Ca</td></tr><tr><td>4</td><td>环氧酯</td><td>0.03Co</td><td>0. 1Ce</td></tr><tr><td>5</td><td>聚氨酯</td><td>0.02Co或Mn</td><td>0.1Zr,0. 05Ca</td></tr><tr><td>6</td><td>含油系</td><td>0.03Co或Mn</td><td>0. 2Zr,0.1Ca</td></tr><tr><td>7</td><td>聚酯</td><td>0.01Co</td><td></td></tr></table></body></html>  \n\n(2）铅催干剂的取代由于铅催干剂有毒，其使用受到限制。一般用 $\\scriptstyle\\mathbf{Co-Zr-Ca}$ 组合取代 $\\scriptstyle\\mathbf{Co-Pb-Ca}$ 组合。取代采用如下步骤进行。  \n\n首先，用 $60\\%$ 的锆催干剂代替铅催干剂，如 $0.3\\%$ 的锆催干剂代替 $0.5\\%$ 的铅催干剂；其次，将钴催干剂增加 $20\\%$ ；接着，将钙催干剂增加 $50\\%\\sim100\\%$ ；最后，还要考虑防失干问题。当然，计算的取代还要经实践检验。  \n\n(3）催干剂配比筛选一般筛选方法常以原来的配比作为对比依据，通过配漆、刷板、贮存及曝晒等方面的试验，以确定每种涂料的催干剂配比及用量。 Y气干型涂料的干燥速率是考核催干剂催干性能的主要指标。  \n\n对于涂料用户来说，涂膜的干燥时间短些，可使涂膜免遭尘埃沾污，井能缩短施工时间。但涂料生产厂家因使用材料的限制及施工时的温度及湿度变化，并要兼顾涂膜的其他性能，对各种类型涂料确定并考核不同的干燥时间。  \n\n一些用于筛选的试验做法如下。  \n\n$\\Phi$ 干性在马口铁皮上涂一道漆，测定其表干及硬干时间。  \n\n$\\textcircled{2}$ 涂膜外观在马口铁皮或打过底的木片上涂漆，以观察涂膜的保色性、保光性和起霜性。观察发雾和起霜，至少要继续一个月。  \n\n抗厚膜皱皮试验：在样板上称出漆的质量或是用注射器挤出一定体积的漆在小玻璃片或在马口铁样板 $(5\\mathrm{cm}\\times15\\mathrm{cm})$ ）上涂漆样。将约 $_{2g}$ 漆在样板上四面倾斜使均匀散布，不使漆流出边缘。样板放在一个水平桌面上，干燥3天，若只在厚边缘上起皱，则可确定具有优良的抗厚膜起皱性。  \n\n$\\textcircled{3}$ 贮存性能贮存一个月后重复检定一次干性及黏度。  \n\n$\\textcircled{4}$ 曝晒试验在正常催干剂用量范围内，其耐候性相差不大。若钻、锰催干剂用量过多，则须进行天然曝晒试验。  \n\n综合考虑各种影响，通过各催干剂的复配和用量的筛选，得到了优化催干剂体系。  \n\n(4）催干剂投量计算催干剂投量 $\\L=$ [树脂投量 $\\times$ 树脂固含量 $(\\%)x$ 催干剂配比 $(\\%)]\\div$ 催干剂金属浓度 $(\\%)$ 。如某一醇酸清漆，亚油醇酸树脂投量 $96\\mathbf{kg}$ ，固含量 $50\\%$ ，钻催干剂配比 $0.033\\%$ ，锰催干剂配比 $0.05\\%$ 。使用的钻、锰催干剂浓度都为 $2\\%$ ，分别求催干剂的投量。  \n\n(5）水性气干型涂料中的应用传统催干剂不易分散于水性醇酸涂料的共溶剂中，可以在催干剂中加人适当的乳化剂和醇醚溶剂，如乙二醇或丙二醇醚等，制成水混溶性催干剂，然后再用于水性醇酸涂料中。阴离子（酸性部分）对催干剂的水解是否有影响尚有争议，但是现有数据显示，催干剂的水解是极轻微的，对催干剂性能的影响很小。水性气干型涂料以水为溶剂或分散介质，氧在水中的溶解度比在有机溶剂中的溶解度要小得多，水会减慢吸氧速率，延长诱导期，从而使干燥变慢。因此，催干剂用量大。传统的实干催干剂在水性气干型涂料中作用较小，可不用。  \n\n主催干剂的预配位能优化其在水性涂料中的催干性能。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 805,
+        "chunk": "# 4.催干剂对生态影响和毒性  \n\n根据欧盟导则，催于剂的风险和安全分类见表2-4-18。  \n\n表2-4-18催干剂的风险和安全分类  \n\n\n<html><body><table><tr><td>催干剂</td><td colspan=\"2\">明 示</td><td>化学文摘登录号CASNo</td></tr><tr><td>银12.5</td><td>Xn-有害</td><td>R20/22（吸人和吞下有害） R36/38时眼睛和，有刺激于净） S36/37（穿工作服和戴手套保护）</td><td>68876-86-8</td></tr><tr><td>钙10</td><td>Xi-刺激</td><td>R38（对皮肤有激）</td><td>681-1-7-性）)</td></tr><tr><td>铈10</td><td>Xi-刺微</td><td>R38（对皮肤有刺激） S37（戴手套保护）</td><td>24593-34-8</td></tr><tr><td>钻10</td><td>Xi-刺激</td><td>R43（皮肤接触可能过敏） R38（对皮皮触） S36/37（穿工作服和戴手套保护）</td><td>68409-81-4</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>催干剂</td><td>明</td><td>示</td><td>化学文摘登录号CASNo</td></tr><tr><td>锰10</td><td>Xi-刺激</td><td>R38（对皮肤有刺激） S37（戴手套保护）</td><td>6855142-8</td></tr><tr><td>德10</td><td>Xi-刺激</td><td>R38（对皮）</td><td>2457-02-5</td></tr><tr><td>锌12</td><td>Xi-刺激</td><td>38（對皮有）</td><td>68551-44-0</td></tr><tr><td>锆6</td><td>Xn-有害</td><td>R38（对皮肤有刺激） R35（下对肺有害） S62（吞下不会呕吐，立即看医生并按标签明示处置）</td><td>22464-99-9</td></tr><tr><td>锆12</td><td>Xn-有害</td><td>R38（对皮肤有刺激） 35（委下可保对肺有害）</td><td>22464-99-9</td></tr><tr><td>错18</td><td>Xi-刺激</td><td>S62（吞下不会呕吐，立即看医生并按标签明示处置） R38（對皮）</td><td>22464-99-9</td></tr><tr><td>铅36</td><td>T-有毒</td><td>R20/22（吸入和吞下有害） R33（有积聚危险） R61（卷许对会出生孩子有着医生并按标签明示处置） S36/37/39（穿工作服、戴手套和眼镜保护） S45（不舒服或紧急情况，立即看医生）</td><td>15696-43-2(中性） 68603-83-8（碱性）</td></tr><tr><td>锂2</td><td>Xi-刺激</td><td>S53（使用前获取专门指导） R38（对皮肤有激）</td><td>27253-30-1</td></tr><tr><td>钾10</td><td>Xi-刺激</td><td>R38（支肤有数）</td><td>68604-78-4</td></tr><tr><td>铁6</td><td>Xi-刺激</td><td>R38（對皮）</td><td>68308-20-3</td></tr><tr><td>辛酸铬</td><td>Xn-有害</td><td>R22（吞下有害） R43（皮肤接触可能过敏） S24（避免与皮肤接触） S28（接触皮肤后，立即冲洗干净） S36/37（穿工作服和戴手套保护）</td><td>20195-23-7</td></tr><tr><td>铜</td><td>Xn-有害</td><td>R22（吞下有害）（R10易燃） S24/25(免作皮肤、眼肿）） S46(吞下，立即看医生并按标签明示处置）</td><td>6833-192-</td></tr><tr><td>钒</td><td>Xi-刺激</td><td>R38（对皮有激）</td><td>68815-09-5</td></tr><tr><td>辛酸</td><td>Xi-刺激</td><td>R38（对皮数） R36/38（对眼睛和皮肤有刺激）</td><td>67874-71-9</td></tr><tr><td>辛酸锡</td><td>Xi-刺激+N-环境风险</td><td>R52/53(水生物，，也许对环境造成长期负面影响） S28(接触皮肤后，立即冲洗干净）</td><td>301-10-0</td></tr><tr><td>异辛酸镍</td><td>Xi-刺激</td><td>R38（对皮肤有刺激） R43（皮肤接触可能过敏） S24（避免与皮肤接触） S28（接触皮肤后，立即冲洗干净） S36/37（穿工作服和戴手套保护）</td><td>7580-31-6</td></tr></table></body></html>  \n\n根据欧盟导则67/548的第21次修订，铅催干剂是有毒的，并要在标签上标明R61（也许对未出生孩子有害）和Xi-刺激的。这适用于所有浓度等于和大于0.5%的铅催干剂。  \n\n由于催干剂的金属离子不能生物降解，尤其是重金属，所以催干剂不能流入公共水域。而其合成酸组分一般是容易生物降解的。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 806,
+        "chunk": "# 5.抗结皮剂  \n\n气干型涂料在使用及贮存过程中会结皮。抗结皮剂能有效地防止结皮。理想的抗结皮剂不但具有高效的抗结皮效果，而且无损害涂料性能的负面作用，如延迟干性、影响色泽及气味等。抗结皮剂有酚类及类两种。有些溶剂如双戊烯等具有一定的抗结皮作用，可配合酚类或类抗结皮剂使用。也可将几种抗结皮剂混合使用。  \n\n(1）酚类抗结皮剂酚类化合物都为抗氧化剂，本身易氧化而使油基漆的氧化结膜受阻以延迟其表面结膜。一般的酚类如对苯二酚与连接料的混溶性较差，而其氧化活性极强，使用时不易控制，常选择邻位、对位有取代基的酚类化合物作抗结皮剂，其氧化性较适宜，并与油基漆、醇酸漆有良好的混溶性。  \n\n酚类抗结皮剂价格较低，但对涂料的干性影响较大，用量稍不适宜，会使涂料涂刷后几天不结膜。酚类化合物易泛黄，与铁反应呈棕色，还具有一些刺激性气味，故一般的涂料不宜采用酚类抗结皮剂。酚类抗结皮剂能延迟油基漆的表干，因而使底干较彻底，适用于底漆及浸涂施工的烘干涂料，因这类涂料的干性较快，在施工过程中长期与空气接触而结皮。酚类抗结皮剂常用于油墨，因油墨的涂膜极薄，并能向纸张中渗透，因而对油墨施工后的干性影响较小。  \n\n最常用的是2，6-二叔丁基苯酚，还有邻甲氧基苯酚和邻异丙基苯酚等。  \n\n拜耳公司生产的AscininP抗结皮剂为酚类抗结皮剂，是取代酚类在二甲苯及丁醇混合液（95：5）中的 $40\\%$ 溶液。  \n\n(2）类抗结皮剂具有—C—NOH官能团的化合物称为类。常用的类抗结皮剂有甲乙酮、丁醛、环己酮和丙酮，其理化特性见表2-4-19。  \n\n表2-4-19常用类抗结皮剂  \n\n\n<html><body><table><tr><td>类抗结皮剂</td><td>甲乙酮</td><td>丁醛</td><td>环已酮肪</td></tr><tr><td>分子结构</td><td>HHH H-C—C—C—C—H HHH OH</td><td>CH—CH—NOH</td><td>-NOH</td></tr><tr><td>外观 沸点/C 闪点/℃</td><td>清激无色液体 151~155 52</td><td>清激无色液体 151. 5~154 69 0.916</td><td>浅灰红色粉末 204 112 0.981</td></tr></table></body></html>  \n\n类抗结皮剂的抗结皮机理如下。  \n\n$\\Phi$ 抗氧化作用类化合物易氧化，能阻止漆的氧化聚合而成膜。  \n\n$\\textcircled{2}$ 溶解作用液态的类化合物为强溶剂，能延迟胶凝体的形成而抗结皮。  \n\n$\\textcircled{3}$ 络合作用能与催干剂的金属部分形成络合物，使催干剂失去催干性而延迟其结皮。在涂装后，类快速挥发而使络合物分解，催干剂恢复其催干性。  \n\n类抗结皮剂与催干剂形成络合物的情况较复杂。在某些连接料中与钻催干剂能呈现较深的色泽，但在涂膜干结后则恢复原来色泽。抗结皮剂加人次序与呈色反应有关，在加催干剂以前加入则色深，因而抗结皮剂都在加催干剂后才加人。  \n\n在类抗结皮剂中，最常用的是甲乙酮。它抗结皮性好，用量低，无负面作用。甲乙酮蒸气压高，涂料涂装后，它能快速挥发，因此几乎不影响涂料的干燥。在传统醇酸漆中，其用量一般为0.1%～0.5%。另外，钴催干剂用量大，甲乙酮抗结皮剂用量也大。在高反应性的氧化干燥高固体分涂料中，其用量可达 $0.7\\%$ 。  \n\n环己酮在使用时需先溶解于适当溶剂中，在室温较低时，易结晶析出。丁醛则适用于油基漆及酚醛漆中，甲乙酮则适用于醇酸漆及环氧酯涂料中。丙酮挥发比环己酮快，无气味，故可用于无气味涂料中。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 807,
+        "chunk": "# 九、防腐剂、防霉剂和防藻剂  \n\n涂料在生产和贮存中可能发生的微生物污染问题是罐中防腐问题，是细菌带来的问题，要通过加防腐剂（in can preservative)、环境净化和严格的生产管理来解决。  \n\n涂膜有亲水成分，有一定吸水性，同时含有微生物的养分，在湿热环境中，容易长霉，在有阳光的地方，还会生长藻类。因此，对涂膜来说，存在干膜防霉防藻问题，主要是通过加防霉防藻剂（dry film fungicide/algicide）来解决。",
+        "category": " Introduction"
+    },
+    {
+        "id": 808,
+        "chunk": "# 1.防腐剂、防霉剂和防藻剂作用机理  \n\n对防腐剂、防霉剂和防藻剂作用机理的研究是揭示药剂通过何种方式和途径来影响病原菌状态和生理生化过程，这对于防腐剂、防霉剂和防藻剂的选用和合成都具有实际指导意义。  \n\n防腐剂、防霉剂和防藻剂对菌类、藻类的抑制和毒杀性能，不仅取决于其组成、结构、浓度和作用时间，还与菌类和藻类本身有关。  \n\n通常，根据作用方式和机理，防腐剂和防霉剂可分为三类。  \n\n(1）膜活性防腐剂和防霉剂它们能与菌类膜起作用，造成细胞内物质泄漏，导致细胞  \n死亡。(2）亲电子防腐剂和防霉剂它们与亲核细胞物（如氨基酸、蛋白质和酶）起反应，不  \n可逆地阻止活细胞功能。(3）整合型防腐剂和防霉剂它们通过与新陈代谢起关键作用的金属离子整合而发挥防  \n腐和防霉作用。防藻剂是通过阻断光合作用而达到防藻效果的。",
+        "category": " Introduction"
+    },
+    {
+        "id": 809,
+        "chunk": "# 2.腐败和霉变的主要菌属及其最低抑制浓度MIC  \n\n据报道，导致涂料腐败的主要微生物是革兰阴性菌，尤其是大肠产氧菌属和假单胞菌属。表2-4-20是引起乳液和涂料腐败的主要菌属。表2-4-21是引起干膜霉变的主要菌属。不同地区造成腐败和霉变的主要菌属会有差异，内墙涂料霉变菌属与外墙也不一样。  \n\n表2-4-20引起乳液和涂料腐败的主要菌属  \n\n\n<html><body><table><tr><td colspan=\"2\">国际生物腐败小组（涂料）</td><td colspan=\"2\">参考文献</td></tr><tr><td>英文名称</td><td>菌株号NCIMB</td><td>中文名称</td><td>英文名称</td></tr><tr><td>Providentin rettgeri</td><td>10842</td><td>铜绿色假单胞菌</td><td>Pseudomonasaeruginosa</td></tr><tr><td>Flavobacterium odoratum</td><td>13294</td><td>大肠杆菌</td><td>Escherichia coli</td></tr><tr><td>Enterobacter aerogenes</td><td>19192</td><td>阴沟肠杆菌</td><td>Enterobacter cloacae</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td colspan=\"2\">国际生物腐败小组（涂料）</td><td colspan=\"2\">参考文献</td></tr><tr><td>英文名称</td><td>菌株号NCIMB</td><td>中文名称</td><td>英文名称</td></tr><tr><td>Pseudomonas versicularis</td><td>13293</td><td>英膜红假单胞菌</td><td>Rhodopseudomonascapsulata</td></tr><tr><td>Escherichia coli</td><td>12793</td><td>枯草杆菌</td><td>Bacillus subtilis</td></tr><tr><td>Alaligenes faecalis</td><td>13147</td><td>金黄色葡萄球菌</td><td>Sta phylococcus aureus</td></tr><tr><td colspan=\"2\"></td><td>乳酸链球菌</td><td>Sterephylococcus lactis</td></tr><tr><td colspan=\"2\">NCIMB--NationalColectionof Idustrial and MarineBacteria海生黄杆菌</td><td>普通变形杆菌</td><td>Proteus vulgaris</td></tr><tr><td colspan=\"2\">Aberdeen, UK.</td><td></td><td>Flavobacteriummarinum</td></tr><tr><td colspan=\"2\">即英国阿伯丁国家工业和海洋细菌收集中心</td><td>黄色八叠球菌</td><td>Sarcina flava</td></tr><tr><td colspan=\"2\"></td><td>草状芽孢杆菌 念珠小球菌</td><td>B.mycoiacs M. canaiaus</td></tr></table></body></html>  \n\n表2-4-21引起千膜霉变的主要菌属  \n\n\n<html><body><table><tr><td colspan=\"2\">英 国</td><td colspan=\"2\">乳胶漆霉变的常见菌属</td></tr><tr><td>中文名称</td><td>英文名称</td><td>英文名称</td><td>中译</td></tr><tr><td>链格孢霉</td><td>Alternaria alternata</td><td>Altermaria alterata(Alternaria tenuis)</td><td>链格孢霉</td></tr><tr><td>杂色曲莓</td><td>Aspergillus versicolor</td><td>Aspergillus flavus</td><td>黄曲霉</td></tr><tr><td>芽枝状枝孢菌</td><td>Cladosporium cladosporioides</td><td>Aspergillus niger</td><td>黑曲霉</td></tr><tr><td>球孢枝孢菌</td><td>Cladosporium sphaerospermum</td><td>Aspergillus ustus</td><td></td></tr><tr><td>出芽短梗霉</td><td>Aureobasidium pullulans</td><td>Aureobasidium pululans</td><td>出芽短梗霉</td></tr><tr><td>枝孢霉</td><td>Cladosporium herbarum</td><td>Cladosporium herbarum</td><td>枝孢霉</td></tr><tr><td>宛氏拟青霉</td><td>Paecilomyces variot</td><td>Paecukimyces cariotl</td><td></td></tr><tr><td>产紫青霉</td><td>Penicillium purpurogenum</td><td>Penicillium citrinum</td><td></td></tr><tr><td>整点每</td><td>Phoma violacea</td><td>Stach ybotrys chartarun</td><td></td></tr></table></body></html>  \n\n只有当防魔剂和防霉剂用量中其活性组分高于最低抑制浓度MIC时，才能达到有效的保护作用。搭配得好的活性组分具有协同作用。  \n\n一般认为，当MIC大于 $500\\mathrm{mg/kg}$ 时，该防腐防霉剂对该微生物无效。  \n\n然而，不同来源的MIC测定数据常常存在差异，有的差异还相当大。原因是影响测试结果的因素比较多，如测试菌株、接种量、培养基、培养温度、培养时间、pH等，而且这些因素很难恒定所致。当差异较大时，应从各方面比较判别其可靠性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 810,
+        "chunk": "# 3.常用防腐剂  \n\n现在市面上的防腐剂品种繁多，厂家牌号多得令人眼花缭乱。就其活性组分进行分析，较常用的如下。  \n\n(1）1,2-苯并异噻唑琳-3-酮1,2-苯并异噻唑琳-3-酮（1,2-benzisothiazolin-3-one），简称BIT，化学文摘登录号CASNo2634-22-5，其结构式如下：  \n\n![](images/6b023d9ee56b41b0a06fd88482e9a00d5b737c135e9629d80c872ad85a6ed3e9.jpg)  \n\nBIT的优点是不释放甲醛，不含卤素，不挥发。具有热稳定性，180℃才开始轻微失重；对酸碱稳定，可在广泛的pH范围使用；化学稳定性好，与胺类相容。BIT及其制剂对金属无腐蚀作用。  \n\n其缺点是，杀菌性较慢。抗菌谱中有空隙。遇强氧化还原剂时，防腐性降低。对皮肤有刺激。防霉性较差。  \n\n在使用时，由于BIT稳定性较好，应尽可能在打浆开始时就加入，这有利于防腐。  \n\n(2）5-氯-2-甲基-4-异噻唑啉-3-酮/2-甲基-4异噻唑啉-3-酮5-氯-2-甲基-4-异噻唑啉-3-酮（化学文摘登录号CASNo26172-55-4)/2-甲基-4-异噻唑琳-3-酮（化学文摘登录号CASNo 2682-20-4)，英文名 5-chloro-2-methyl-4-isothiazolin-3-one/2-methyl-4-isothiazolin-3-one，简称CMIT/MIT，其 $3:1$ 混合物化学文摘登录号CASNo55965-84-9，是-种性价比较高的常用罐内防腐剂，其结构式如下：  \n\n![](images/96e72f068ecb00169b0ef07bc29e09a208fedbad40bfe9c1de587d50fb912f74.jpg)  \n\n通常，CMIT $\\because$ MIT=3：1。这是因为在合成过程中，分离这两种化合物的工艺非常复杂而不经济，所以该产品以混合物的形式生产和使用。  \n\n另外，防腐剂中一般还含硝酸盐和亚硝酸盐，以稳定活性组分。也有报道以铜盐或1，6-二羟基-2，5-氧杂已烷等稳定的。  \n\nCMIT/MIT抗菌谱广，其中CMIT是速效杀菌剂，其杀菌效力是MIT的 $50\\sim200$ 倍。  \n\nCMIT/MIT的优点是，广谱杀菌，高效。不释放甲醛，不挥发，相容性好。  \n\n其缺点是， $\\mathsf{p H}$ 大于9.5时，不稳定。热稳定性差，温度不宜长期高于 $40\\%$ 。遇还原剂时，防腐性降低。与胺不相容，会降解。含氯，对皮肤有很强刺激。  \n\n为了避免打浆时温度高而分解，一般应在调漆后阶段加入这类防腐剂。  \n\n(3）释放甲醛型防腐剂众所周知，福尔马林是一种防腐剂。其实，福尔马林就是$35\\%\\sim40\\%$ 的甲醛水溶液。  \n\n甲醛，化学文摘登录号CASNo55-00-0，对各种微生物都具有高效杀灭作用，包括细菌繁殖体、芽孢、分枝杆菌、真菌和病毒，是一种常用的杀菌防腐剂。它对细菌的抑杀性能比霉菌强。  \n\n其优点是，快速广谱杀菌，高效，尤其是具有气相杀菌能力，使容器上部空间得到保护，这对于贮罐贮存和管道输送的大生产是需要的。价格适中。  \n\n其缺点是，甲醛被怀疑是第三类致癌物。热稳定性差。 $\\mathrm{\\pH}{<}6$ 时，效率会降低。挥发并有强烈味道。  \n\n现在趋向采用释放甲醛型防腐剂（formaldehydereleaser，FR），它有甲醛的优点，而可减少甚至消除甲醛的缺点。释放甲醛型防腐剂是一种经过缩聚的羟甲基有机物，能够在一定时间内缓慢地解聚，释放出微量的甲醛，从而达到一定的杀菌和抑菌效果。  \n\n属于释放甲醛型防腐剂有N-缩甲醛（N-formal）、O-缩甲醛（O-formal)。N-缩甲醛，如羟甲基脲、二羟甲基二甲基海因、三羟甲基-1-脲基间二氮杂环戊烷-2，4-二酮。O-缩甲醛，如苯基甲氧基甲醇、1,6-羟基-2,5-氧杂已烷。 $o$ 缩甲醛释放甲醛的速度高于N-缩甲醛。  \n\n由于我国内墙涂料对游离甲醛含量要求比较严，释放甲醛型防腐剂在内墙中使用时应控制游离甲醛不能超标。  \n\n(4)5-氯-2-甲基-4-异噻唑啉-3-酮/2-甲基-4-异噻唑啉-3-酮 $^+$ 释放甲醛型防腐剂在涂料工业中，不同的防腐组分可以不同的比例进行组合复配，以便优势互补，达到扩大抗菌谱、减少用量、降低成本和提高环境友好性等理想的结果，称为协同作用。5-氯-2-甲基-4-异噻唑啉-3-酮/2-甲基-4-异噻唑啉-3-酮+释放甲醛型防腐剂，简称CMIT/MIT+FR，是一种很常用的组合复配方式，有协同作用。既具有容器上部空间保护，又具有高效广谱杀菌作用。而且释放甲醛型防腐剂会提高CMIT的稳定性。当然，涂料中甲醛含量不能超标。但并不是所有的复配都有协同作用。  \n\n（5）1,2-苯并异噻唑琳-3-酮/2-甲基-4-异噻唑琳-3-酮1,2-苯并异噻唑琳-3-酮/2-甲基-4-异噻唑啉-3-酮，英文名1，2-benzisothiazolin-3-one/2-methyl-4-isothiazolin-3-one，简称BIT/MIT，是在1,2-苯并异噻唑啉-3-酮/2-甲基-4-异噻唑啉-3-酮（CMIT/MIT）罐内防腐剂受到环境限制后，开发出来的一种老活性组分、新复配组合的罐内防腐剂，具有协同作用。其结构式如下：  \n\n![](images/e65c5c38081d059565978123162dd728e76a7bee5d7dd894cca1fc40c90a8ce9.jpg)  \n\nBIT/MIT的优点是，抑菌谱比BIT广，也不释放甲醛，不含卤素，不挥发。稳定性较好，还原剂稳定， $\\mathfrak{p H}$ 不大于9.5时稳定。  \n\n其缺点是，杀菌性不如CMIT/MIT，杀菌速率也不如CMIT/MIT快。  \n\n在使用时，由于 $\\mathbf{BIT/MIT}$ 稳定性较好，热稳定性约为 $80^{\\circ}\\mathrm{C}$ ，可以在打浆开始时就加入，以利于防腐。用量一般为 $0.2\\%\\sim0.4\\%$ 9  \n\n(6）1,3,5-三(2-羟乙基)均三嗪1,3,5-三（2-羟乙基)均三嗪[1，3,5-tris(2-hydroxy-ethyl)-triazine]的化学文摘登录号CASNo 4719-04-4，其结构式如下：  \n\n![](images/7afccaf2dce60c3eee9dedb0593303b84e62de23478800af1ea7f94bdf8bf7d4.jpg)  \n\n1,3,5-三(2-羟乙基)均三嗪是释放甲醛型防腐剂，对各种革兰阳性菌或阴性菌、霉菌和酵母菌都有较强的抑杀力。  \n\n（7）其他防腐剂防腐剂还有许多。如六氢-1，3，5-三乙基-三嗪（hexahydro-1，3，5-triethyl-triazine)，化学文摘登录号CASNo 7779-27-3。1-(3-氯烯丙基)-3,5,7-三氮杂-1-氮镰金刚烷氯化物（chloroallyl-3,5,7-triaza-azonia-adamantane chloride），简称 CTAC，化学文摘登录号CASNo 51229-78-8（>97%）/4080-31-3(67%)。2,2-二澳基-3-(三价)氮基丙酰胺（2,2-dibromo-3-nitrilopropionamide），简称DBNPA，化学文摘登录号CAS No 10222-01-2，是一个快速杀菌剂，如可用于涂料厂的循环使用废水杀菌，设备清洗等。它是DBNPA在水和聚乙二醇中的 $20\\%$ 溶液。Proxel TN是 $_{\\mathrm{BIT+FR}}$ 的复配防腐剂。 $\\mathbf{BIT+CMT/MIT}$ 复配的防腐剂能优势互补，性能和环境友好折中平衡。MyacideAS（Tektamer）的活性组分是2-澳基-2-硝基-1,3-丙烷二醇（2-bromo-2-nitropropane-1,3-diol)，简称 Bronopol，化学文摘登录号CASNo52-51-7，也会释放甲醛，这是一个既高效又安全的防腐剂，但价格较高。将其与CMIT/MIT，或者与1,2-二澳-2,4-二氰基丁烷组合复配，都取得了较好的结果。 19八",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 811,
+        "chunk": "# 4.常用防霉防藻剂  \n\n防霉防藻剂的品种也很多，按活性组分，常用的如下。  \n\n干膜防霉防藻剂的关键是水溶性要低，否则会被水冲淋掉，影响防霉防藻时效性。当然，还有稳定性要好，包括紫外线稳定性、热稳定性和酸碱稳定性等。这样才能持久起作用。  \n\n另外，涂膜的致密性对防霉防藻时效性也有影响。亚光高PVC涂膜，因为孔隙大，防霉防藻剂易流失，防霉防藻时效性较短。半光中PVC涂膜其次。有光低PVC涂膜，致密性高，防霉防藻剂不易流失，防霉防藻时效性长。  \n\n(1）苯并咪唑氨基甲酸甲酯苯并咪唑氨基甲酸甲酯是常用的防霉剂，其英文名carbendazim，学名methyl-N-benzimidazol-2-yl-carbamate，别名多菌灵，简称BCM，化学文摘登录号CASNo10605-21-7，其结构式如下：  \n\n![](images/54917e6d6df5838f56475b7e64ed382336ed87a262cf4a4707e4c9aedd36e76e.jpg)  \n\nBCM能杀死或抑制大部分霉菌生长，是一个很好的防霉剂。但在相对湿度大的情况下，对毛霉、交链孢霉和根霉等无效。对细菌和酵母菌也无效。  \n\nBCM的优点是，水溶性低，在水中溶解度 $8\\mathrm{{mg/kg}}$ ，光稳定性好，热稳定性好，毒性低。  \n\n其缺点是，杀菌谱有缺陷。 $\\ell$ 欧洲危险物质导则》第29次技术修订将含量等于或大于0.1%的苯并咪唑氨基甲酸甲酯防霉剂列为2类致变物（mutagencategory2）和2类重现毒性物（reprotoxic category 2)。在高 $\\mathsf{p H}$ 时，即在养护期不够的新抹灰层上，有可能使白涂料变色。  \n\n在水性漆中，一般用量为 $0.5\\%\\sim1.0\\%$ 。与其他防霉组分复配使用，效果更好。  \n\n(2）2-正辛基-4-异噻唑啉-3-酮2-正辛基-4-异噻唑琳-3-酮（2-octyl-4-isothiazolin-3-one）简称OIT，也是一种常用的防霉剂，化学文摘登录号CASNo26530-20-1，其结构式如下：  \n\n![](images/cf42041103c01e3a73ea01e4c077bde294f33262e9301f9ea99fe3c52db6e90b.jpg)  \n\nOIT的优点是，广谱杀菌，既防霉又抗藻。稳定性好。  \n\n其缺点是，水溶性较大，在水中溶解度 $480\\mathrm{{mg/kg}}$ ，在涂膜中的防霉剂较易被雨水冲刷掉。对皮肤刺激性大。  \n\n(3）3-碘-2-炔丙基丁基氨基甲酸酯3-碘-2-炔丙基丁基氨基甲酸酯（3-iodopropargyl-N-butylcarbamate）简称IPBC，是环境友好型防霉剂，化学文摘登录号CASNo 55406-53-6，其结构式如下：  \n\n这是用于涂料工业的唯一线型防霉剂。  \n\nIPBC的优点是，具有均衡而高效的防霉能力，pH稳定性好。  \n\n其缺点是，水溶性较大，在水中溶解度 $190\\mathrm{mg/kg}$ 。价格很贵，可能会造成变色。  \n\n（4）四氯间苯二甲晴四氯间苯二甲腈（tetrachloroisophthalonitrile）简称TPN或CLT，俗名百菌清，化学文摘登录号CAS No 1897-45-6，其结构式如下：  \n\n![](images/90e4ae22106d50243280d8ce580a4dfbfd8e85b88bba9f4623d76d9c45429693.jpg)  \n\n纯TPN是无色无味结晶体，在水中溶解度极低，约 $0.5\\mathrm{mg/kg}$ 。工业品（纯度约为  \n\n98%）为淡黄色结晶体，稍有刺激性气味。在通常情况下，对酸碱和紫外线都是稳定的，也不腐蚀容器。  \n\nTPN的优点是，水溶性低，防霉性较好。而缺点是，抗菌谱有缺陷。它是一个含氯产品。(5）4,5-二氯-2-正辛基-4-异噻唑琳-3-酮4，5-二氯-2-正辛基-4-异噻唑啉-3-酮的英文名4,5-dichloro-2-octyl-4-isothiazolin-3-one，简称DCOIT，化学文摘登录号 CAS No 64359-81-5，其结构式如下：  \n\n![](images/2dc74ab3ccbeb65b744f7d93eed6f1f48dac77a1441261880e5043b3b2c39b81.jpg)  \n\n4，5-二氯-2-正辛基-4-异噻唑琳-3-酮抗菌谱广。  \n\nDCOIT的优点是，既能用于干膜防霉，又可用于罐内防腐，所试微生物的MIC 都在$20\\mathrm{mg/kg}$ 以下，是广谱高效防腐防霉防藻剂。水溶性低，在水中溶解度 $\\scriptstyle14\\mathrm{mg}/\\mathbf{kg}$ 9  \n\nDCOIT的缺点是，渗析较严重，对皮肤刺激性较大。  \n\n(6）吡啶硫酮锌吡啶硫酮锌是防霉防藻剂，英文名zinc pyrithione，是锌的整合物，简称ZPT，化学文摘登录号CASNo13463-41-7，其结构式如下：  \n\n![](images/10fda2ce2fc1622e159804adf57844b93800b1c2718b66ac3a1ee0a488a0b04a.jpg)  \n\n吡啶硫酮锌的优点是，抗菌谱广，毒性低，它不仅作为防霉防藻剂，而且还用在洗发剂和化妆品中，在洗发剂中用于去头皮屑。  \n\n吡啶硫酮锌既能用于干膜防霉，又可用于干膜防藻。在水中溶解度低，约 $8\\mathrm{m}g/\\mathrm{kg}$ ，在丙二醇中溶解度 $200\\mathrm{{mg/kg}}$ 。热稳定性好，在 $100^{\\circ}\\mathrm{c}$ 至少能稳定 $120\\mathrm{{h}}$ 。可在 $\\mathrm{pH}~4.5\\sim9.5$ 之间使用。  \n\n吡啶硫酮锌的缺点是，在紫外线下会逐步降解。贮存温度应在 $10\\Upsilon$ 以上。当低于$1.5t$ ，吡啶硫酮锌会沉淀结块。  \n\n除上述防霉剂外，还有许多，如四甲基二硫化秋兰姆（thiram），俗名福美双，商品名TMTD，化学文摘登录号CASNo137-26-8等。  \n\n（7）常用防藻剂 $N^{\\prime}$ -(3,4-二氯苯基)-N，N-二甲基脲（diuron）是一种常用的防藻剂，国内又称其为敌草隆，化学文摘登录号CASNo330-54-1，其结构式如下：  \n\n![](images/ea3a13d8088bed4b5dc5fc5651df841c587af5a7236af82e4a2998368af3e627.jpg)  \n\n它防藻性能好，价格适中，如有防藻要求，往往需要加该组分。但它对其他作物也有同样的杀害作用，好在其水溶性低，约 $32\\mathrm{mg/kg}$ 。单组分的 $N^{\\prime}$ （3,4-二氯苯基）-N，N-二甲基脲产品有Algicide $\\mathrm{~D~}500$ 和Durashield F-500等。  \n\n2-甲硫基-4-叔丁基氨基-6-环丙基氨基-三嗪（2-methylthio-4-tert-butylamino-6-cyclo-propylamino-s-triazine)，或称N-环丙基 $N^{\\prime}$ -（1,1-二甲基乙基）-6-甲硫基-1，3，5-三嗪-2,4-二胺[N-cyclopropyl ${\\bf\\nabla}\\cdot{\\bf N^{\\prime}}$ -（1,1-dimethylethylene）-6-methylthio-1，3，5-triazine-2，4-diamine]，化学文摘登录号CAS No 28159-98-0，简称Irgarol或Cybutryne，及其变体Terbutryne，都是新开发的防藻剂，安全性好。Irgarol或Cybutryne的结构式如下：  \n\n![](images/f576a3a08aa563f8eda257cb11038a85952822053a3cffa86a0cabc47b645c7f.jpg)  \n\n吡啶硫酮锌，除防霉外，还是很好的防藻剂。  \n\n（8）复配防霉防藻剂许多防霉防藻剂是复配的，以便能起互补和协同作用。例如，Rocima 350是DCOIT和IPBC的复配。Rocima361是BCM与 $N^{\\prime}$ (3,4-二氯苯基)-N,N-二甲基脲的复配，具有防霉防藻的作用。MycavoidDFP和MycavoidDFS是 $\\mathrm{OIT+IPBC}$ 与$N^{\\prime}$ (3,4-二氯苯基)-N， $N$ 二甲基脲的三组分复配。MycavoidDFW是 $\\mathbf{OIT}+\\mathbf{BCM}$ 和 $N^{\\prime}$ (3,4-二氯苯基)-N,N-二甲基脲的三组分复配。Mergal $\\mathrm{~s~}90$ Paste是 $\\mathbf{BCM+OIT}$ 和2-甲硫基-4-叔丁基氨基-6-环丙基氨基-S-三嗪复配而成。而MycavoidDF3是 $\\mathbf{OIT+CMT/MIT}$ 的三组分复配，具有防腐防霉的功能等。  \n\n应注意的是，不是所有的复配都能起互补和协同作用。复配能否起互补和协同作用，关键看试验和实际使用结果。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 812,
+        "chunk": "# 5.防腐剂、防霉防藻剂的选用  \n\n选择防腐剂、防霉剂和防藻剂的原则是高效、低毒、广谱、相容、稳定、持久和高性价比。首先要看防腐剂、防霉剂和防藻剂的组成，其次看其有效组分浓度，然后考虑价格。一般选择两个活性组分及其以上的复配防腐剂和防霉防藻剂。  \n\n防腐剂、防霉剂和防藻剂在涂料中的用量，应使其有效成分浓度至少等于或大于最低抑制浓度（MIC)。复配并具有协同作用的，根据复配后的MIC确定。  \n\n一般来说，按全配方质量计，防腐剂 $0.1\\%\\sim0.3\\%$ ，防霉防藻剂 $0.3\\%\\sim1.2\\%$ 、具体根据原料含菌情况，防腐剂和防霉剂中有效组分浓度，涂料所经受的温度，产品的pH和所含氧化还原剂情况，以及产品要求等，通过试验确定。同时还要注意所选的防腐剂和防霉剂在涂料体系中是稳定的，以保证防腐剂和防霉剂（防藻剂）持久地起作用。  \n\n据介绍，欧美21家公司对防腐剂试验表明，掺加 $0.1\\%\\sim0.2\\%$ 的含CMIT/MIT释放甲醛型防腐剂都能达到防腐目的。  \n\n在生产中，防腐剂和防霉防藻剂通常在颜料和填料研磨分散阶段开始时就加入，以抑制或杀死水和原材料中的细菌。对于热稳定性差的防腐剂和防霉防藻剂，应在调漆后阶段加人，以防颜料和填料研磨分散时温度过高使其分解而失效。  \n\n筛选防腐防霉防藻剂时，或测定涂料防腐防霉防藻性时，往往都需进行防腐防霉防藻性试验。防霉防藻的时效性也可通过淋水和人工老化后测定防霉防藻性而得到，还可通过自然曝晒测定。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 813,
+        "chunk": "# 6.防腐剂和防霉剂的发展  \n\n(1）有机防腐剂和防霉剂的发展有机防腐剂和防霉剂主要向不含氯、低毒高效、广谱、长效和降低挥发性有机物（VOC）方向发展。  \n\n防腐剂和防霉剂的发展受环保法规影响较大。一是对甲醛的限制；二是对含氯防腐剂和防霉剂的限制，例如，《欧洲危险物质导则》（EuropeanDangerous Substances Directive）规定，当5-氯-2-甲基-4-异噻唑啉-3-酮/2-甲基-4-异噻唑啉-3-酮（简称CMIT/MIT）超过$\\mathbf{15mg/kg}$ 时，应贴危险品标签，因此，就有以CMIT/MIT和1,2-苯并异噻唑琳-3-酮（简称  \n\nBIT）复合或1，2-苯并异噻唑琳-3-酮/2-甲基-4-异噻唑啉-3-酮（简称BIT/MIT）取代CMIT/MIT的发展趋势；三是对VOC的限制，促进低VOC（甚至是零VOC)、无气味防腐防藻剂发展。  \n\n《欧洲危险物质导则》第29次技术修订将含量等于或大于 $0.1\\%$ 的苯并咪唑氨基甲酸甲酯(carbendazim）防霉剂列为2类致变物（mutagencategory2）和2类重现毒性物（reprotoxiccategory2)，根据其在涂料中的含量，应明示。  \n\n(2）无机抗菌剂的发展除上面介绍的有机抗菌剂外，还有一类无机抗菌剂，目前也开始在涂料中应用。它抗菌谱广，抗菌期长，毒性低，不产生耐药性，耐热性好。  \n\n其中，一类是利用银、铜、锌、钛等金属及其离子的杀菌或抑菌能力制得的抗菌剂。引人注目的是无机金属离子型抗菌防霉剂。人们先后选择沸石、硅灰石、陶瓷、不溶性磷酸盐等与金属离子化学结合力较强的物质作载体，如负载银离子制备抗菌剂。  \n\n在涂料工业中，常见的无机金属氧化物抗菌剂是纳米 $z_{\\mathrm{nO}}$ 和纳米 $\\mathrm{TiO}_{2}$ 。纳米 $z_{\\mathrm{nO}}$ 和纳米 $\\mathrm{TiO}_{2}$ 是一类光催化性无机抗菌剂。  \n\n纳米 $\\mathrm{TiO}_{2}$ 光催化性无机抗菌剂一般采用锐钛型 $\\mathrm{\\DeltaTiO_{2}}$ 。它具有良好的抗菌、净化空气和降解有机物的作用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 814,
+        "chunk": "# 十、光稳定剂  \n\n固化涂层，特别是处于户外的涂层经常遭受阳光（主要是紫外线和短波可见光）、热、潮湿、氧气、臭氧、油污、酸雾、废气中的芳香烃化合物及其他污染物的作用，可能发生涂层内部聚合物链化学转变，表现为涂层光泽度下降、褪色、发黄、粉化、变脆等。最终使涂层剥落，失去保护、装饰作用。化学键和聚合物链断裂反应是老化过程中最为常见的结构变化。老化过程还常表现为聚合物的复杂氧化反应，产生烷基过氧化氢、羟基、羰基等结构，伴随聚合物链断裂，羰基指数常作为衡量老化的指标。此外，以涂层的吸收光谱、光泽度、雾度、附着力、力学性能、热动态力学行为等指标变化来表征其抗老化性能。  \n\n有机涂层的老化过程非常复杂，可大致分为纯粹热老化、光老化及生物降解。此三种老化行为常常交织在一起，并可相互促进。一般常温环境下使用的有机涂料，光老化是主要老化形式，主要表现为聚合物的光氧化和光降解。在阳光中紫外线作用下，有机涂层中的结构基团，或吸光性添加剂和杂质，吸收光能，可能直接发生化学键断裂，也可能在氧的作用下，发生光氧化反应，最终导致聚合物链断裂，并在聚合物链上产生大量氧化基团和小分子氧化产物。常见聚合物中，只有聚四氟乙烯的光稳定性较高，绝大多数聚合物由于本身弱键、敏感基团的存在，以及催化性、光敏性杂质的存在，都存在不同程度的光老化倾向。因此，涂层的光稳定化是一项不可或缺的保护工程。 ?",
+        "category": " Introduction"
+    },
+    {
+        "id": 815,
+        "chunk": "# 1.光稳定剂和涂层的光稳定化  \n\n涂层光老化过程存在几个关键步骤：涂层中存在能够有效吸收阳光中紫外线的组分或结构，吸收光能后发生化学键断裂，产生自由基；光老化过程常伴随着光氧化反应，其中的单线态氧、臭氧以及基态氧的存在是该过程发生的关键；烷基过氧化氢、自由基（包括过氧自由基）是光氧化、光降解得以持续进行的重要环节。针对这些关键，通过添加不同功能助剂抑制或阻断这些步骤，将可大大缓解聚合物涂层的光老化，这种有助于提高涂层抗光老化性能的助剂称为光稳定剂。合适的光稳定剂应当满足良好相容性、低挥发性、长效性、低毒等基本特征。常见光稳定剂包括紫外线吸收剂（UVA）、自由基捕获剂（受阻胺HALS)、激发态猝灭剂及过氧化氢分解剂，这四大类光稳定剂通过各自不同的功能在聚合物光老化的不同阶段发挥作用（图2-4-15)，抑制聚合物光老化过程，在高分子材料抗光老化领域有着举足轻重的作用。  \n\n![](images/a37d00229b1a5a906b5cdbf24370bbdaca25cf1e07d4616abdc832c2056b2b03.jpg)  \n图2-4-15各类光稳定剂对聚合物作用示意图  \n\n（1）紫外线吸收剂紫外线吸收剂UVA的防护机理是基于吸收有害紫外线辐射，并将能量以热的形式耗散，而不致引起光敏化作用。UVA除了本身应具有足够的吸光能力外，还应具有较高的光稳定性。否则，它将很快在非稳定性次级反应中消耗掉。常见UVA包括2-羟基二苯甲酮类、苯并三唑类、羟基三芳基三嗪类等，母体分子上通常引入烷基或烷氧基以改善相容性，降低挥发和迁移。  \n\n2-羟基二苯甲酮类UVA的光稳定作用主要依靠2-羟基与羰基氧原子之间的氢键，分子吸光达到激发态，基氧原子碱性增强，夺取羟基质子，形成不稳定的烯醇-鼠式结构，再以热的形式将能量释放，烯醇-醒式结构重排回到原来的结构。作用过程如下：  \n\n![](images/641a6fd96646b263cbe080245b707a3051d553d101a235015f1e35af0ed79e76.jpg)  \n\n苯并三唑（BTZ）类UVA应用范围更加广泛，母体化合物为2-羟苯基苯并三唑，苯环上5位氯取代，以及 $3^{\\prime}$ 和5'位烷基取代都将使吸收光谱最大波长吸收峰红移。基态BTZ电子结构较为复杂，可看成几种共振结构的混杂结果，存在分子内氢键，与2-羟基二苯甲酮UVA的情形很相似，大致按如下方式发生光致异构化，起到吸光屏蔽保护作用。  \n\n![](images/f42a134912e41a0c3df33bdddba2f74737cce36c0470b0368e195f7428f6eece.jpg)  \n\n基于羟基三苯基三嗪（HPT）的UVA在 $280\\sim380\\mathrm{nm}$ 之间有较宽紫外线吸收，作用机理也是通过三嗪环所连苯环邻位羟基与氮原子的氢键作用，经吸光、重排，化解有害紫外线。三嗪类UVA耐光性好，碱性弱，耐酸能力强，是涂料光稳定化理想的紫外线屏蔽助剂之一，具有比BTZ类UVA略低的吸光强度，作用期限更长，而且与HALS组合所获得的光稳定化效果通常高得多。在传统溶剂型涂料、粉末涂料及光固化涂料中都有广泛应用。  \n\n![](images/73480d66b346fbbf68f277ef9c8f489411077d1acc31c1bde55f06dc9f0cfe30.jpg)  \n\n其他非主流UVA光稳定剂还有很多。涂料中添加炭黑、菁蓝等有色颜料也曾是较为常用的光稳定化方法，由于颜料本身强烈的吸光作用，可有效屏蔽紫外线，其光老化作用原理不仅仅是光屏蔽，还有更复杂的作用过程。  \n\n(2）受阻胺光稳定剂自由基捕获剂功能主要是捕捉涂层光老化时产生的自由基，包括烷基自由基、烷氧自由基、过氧自由基等，阻断这些活性种对聚合物网络的进一步氧化破坏作用。受阻胺光稳定剂（hindered amine light stabilizer，HALS）是目前聚合物材料防光老化工艺中应用最为广泛的光稳定剂。受阻胺包括哌啶系、咪唑烷酮系、氮杂环烷酮系等衍生物，其中以2，2，6，6-四甲基哌啶及其取代衍生物系列为主。  \n\n![](images/abe70d4a16a345b586280c03c3d2ad86d3d003fc24d22b29b2262d7d75b96733.jpg)  \n\nN-H结构和 $N\\cdot$ 甲基取代HALS较为常见。四甲基哌啶结构中不存在共轭结构和生色基团， $250\\mathrm{nm}$ 以上无吸收，其光稳定机理相当复杂。一般认为，真正对聚合物光稳定起直接作用的是受阻胺氮氧自由基，HALS只是活性光稳定物种的前体，在光氧化条件下，N-H和 $N\\cdot$ 甲基结构氧化为氮氧自由基，发挥自由基捕捉功能。在过氧自由基进一步作用下，氮氧自由基可自动再生，循环执行自由基捕捉功能，光稳定化功效大幅度增加。HALS具有胺的特性，显示一定碱性，遇酸质子化，活性下降，碱性偏高的HALS不宜用在酸性或酸催化涂料配方中，对含卤素阻燃涂料亦然。碱性过强的HALS在聚酯类涂料体系中，还可能促使酯键缓慢水解，加剧涂层老化。  \n\n(3）激发态猝灭剂由于光老化过程必须经历光敏基团、光敏杂质的激发态，将其能量转移给猝灭剂分子，而聚合物体系中的受激基团（通常为辨基）和分子无损伤回到基态，猝灭剂分子接受能量后，再以热或冷光等形式释放能量。激发态猝灭剂主要包括镍的某些有机整合物，通常要求使用浓度较高，因涉及能量匹配问题，适用对象具有明显选择性。  \n\n(4）过氧化氢分解剂烷基过氧化氢是聚合物光氧化过程中产生的一种关键中间体，如果任由其发展，将使聚合物链很快氧化分解，采用过氧化氢分解剂就可快速、有效清除该过氧化物，保护聚合物链免受进一步氧化攻击。主要包括二烷基二硫代氨基甲酸盐、二烷基二硫代磷酸盐和硫连双酚盐等含硫金属络合物等。  \n\n![](images/99f5397035b62b98c2aae273f7bd92db00f03f50f34e514c270a49f41df886ea.jpg)  \n\n激发态猝灭剂与过氧化氢分解剂在涂层光稳定化工艺中应用相对较少。其他改进类型的光稳定剂还有很多，如反应型光稳定剂，UVA或HALS中引入可聚合基团，参与涂层固化，使光稳定剂固着于涂层交联网络中，抑制迁移、挥发，提高光稳定化时效。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 816,
+        "chunk": "# 2.常用光稳定剂  \n\n涂料常用紫外线吸收剂UVA与受阻胺光稳定剂HALS品种见表2-4-22。  \n\n表2-4-22涂料常用紫外线吸收剂UVA与受阻胺光稳定剂HALS品种  \n\n\n<html><body><table><tr><td>名称</td><td>结构式</td></tr><tr><td>Tinuvin 384-2/ Tinuvin 99-2</td><td>CHCHCOCH</td></tr><tr><td>Tinuvin 1130</td><td>HO OH OH</td></tr></table></body></html>  \n\n续表  \n\n<html><body><table><tr><td>名称</td><td>结构式 CHCHCHOC2H/C3I↓?</td></tr><tr><td>Tinuvin 400</td><td>OH</td></tr><tr><td>Tinuvin 292</td><td></td></tr><tr><td>Tinuvin 123</td><td>CH</td></tr><tr><td>Tinuvin 928</td><td></td></tr><tr><td>Tinuvin 144</td><td>HO</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 817,
+        "chunk": "# 3.光稳定剂的选用  \n\n各类光稳定剂作用原理不同，所针对的光老化阶段也不相同，单纯采用一类光稳定剂往往达不到理想的光稳定化效果，常需组合使用，经典工艺为UVA与HALS的组合，发挥各自特点，功能互补，相互保护，提高并延长光稳定化效能，如苯并三唑UVA（Tinuvin234）与HALS（Tinuvin292）组合可大幅度提高对脂肪族聚氨酯涂层的光稳定化效果。对清漆而言，UVA用量一般在 $1\\%\\sim3\\%$ 之间调整，对于较低干膜厚的涂层（小于 $20\\mu\\mathrm{m})$ ，可适当提高UVA用量，例如提高到 $6\\%$ 。HALS用量通常为 $0.5\\%\\sim2\\%$ （质量分数)。对于着色涂料，HALS用量一般为 $1\\%\\sim3\\%$ ，因涂料本身使用颜料，具有一定光屏蔽效应，可根据需要减免UVA。UVA与HALS在涂料中的溶解分散性非常重要，特别是在固化后涂膜内的良好分散抗聚结性能对保证其抗光老化、保护涂层具有直接意义。  \n\n常见类型涂料的光稳定化设计可参考表2-4-23的基本方案。  \n\n表2-4-23常见涂料光稳定化设计方案  \n\n\n<html><body><table><tr><td rowspan=\"2\">涂料类型</td><td colspan=\"4\">UVA</td><td colspan=\"2\">HALS</td></tr><tr><td></td><td>Tinuvin 99-2Tinuvin 384Tinuvin 1130Tinuvin 400</td><td></td><td></td><td>Tinuvin 123</td><td>Tinuvin 292</td></tr><tr><td>环氧/骏基丙烯酸树脂（胺催化、金 属催化）</td><td>一</td><td>一</td><td>一</td><td>推荐</td><td>推荐</td><td>一</td></tr><tr><td>酸树规热固性涂料(丙酸树脂、醇</td><td>推荐</td><td>可用</td><td>可用</td><td>可用</td><td>可用</td><td>推荐</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td rowspan=\"2\">涂料类型</td><td colspan=\"4\">UVA</td><td colspan=\"2\">HALS</td></tr><tr><td></td><td></td><td>Tinuvin 99-2Tinuvin 384Tinuvin 1130 Tinuvin 400</td><td></td><td>Tinuvin 123</td><td>Tinuvin 292</td></tr><tr><td>酸催化热固性涂料（丙烯酸酶、醇 酸/蜜胺）</td><td>推荐</td><td>可用</td><td>一</td><td>可用</td><td>推荐</td><td>一</td></tr><tr><td>低温化双组分PU涂科(丙烯酸</td><td>可用</td><td>可用</td><td>推荐</td><td>可用</td><td>可用</td><td>推荐</td></tr><tr><td>水性涂料（丙烯酸分散系、双组分 PU系）</td><td>可用</td><td>一</td><td>推荐</td><td>可用</td><td>可用</td><td>推荐</td></tr><tr><td>水性涂料(丙烯酸酯乳液）</td><td>推荐</td><td>可用</td><td>可用</td><td>一</td><td>推荐</td><td>可用</td></tr><tr><td>酯热塑性涂料(素、酸乙系、丙酸）</td><td>推荐</td><td>可用</td><td></td><td>一</td><td>推荐</td><td>一</td></tr><tr><td>氧化固化涂料（长油基醇酸、酚醛等）</td><td>推荐</td><td>可用</td><td>一</td><td></td><td>推荐</td><td>可用</td></tr><tr><td>光固化与电子束固化涂料（丙烯酸 系、不饱和聚酯系）</td><td>一</td><td>可用</td><td>可用</td><td>推荐</td><td>可用</td><td>推荐</td></tr></table></body></html>  \n\n涂料涉及化学材料不同、加工工艺与固化方式不同，所选用的光稳定剂可能不一样，一般需要在推荐方案或文献基础上多次试验，确定光稳定剂品种、用量及添加方式等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 818,
+        "chunk": "# 十一、成膜助剂  \n\n乳胶漆的涂膜通常是热塑性的，为了保证其性能，所以不能太软。实际上，希望乳液聚合物的玻璃化温度尽可能高，这样涂膜的性能，尤其是硬度和耐沾污性，就比较好。但事情总是两方面的，高性能的同时是乳胶漆的最低成膜温度（MFT）也比较高，就会给较低温度下施工和成膜带来问题。因此，往往要加成膜助剂，降低MFT，达到高性能与低施工温度之间的平衡。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 819,
+        "chunk": "# 1.成膜助剂助成膜机理  \n\n成膜助剂的助成膜机理与自由体积紧密相关，因此，首先对自由体积做简单介绍。  \n\n(1）自由体积无定形材料的体积由两部分组成：一部分是被分子占据的体积，称为已占体积；另一部分是未被分子占据的体积，称为自由体积。以比容（单位质量的体积）对温度作图，结果如图2-4-16所示。阴影部分即为自由体积。  \n\n当高聚物冷却时，开始自由体积逐渐减小，到玻璃化温度 $T_{\\mathrm{s}}$ 时，自由体积达到最小值，即为 $2.5\\%$ ，这时高聚物进人玻璃态。但是快速冷却所得 $T_{\\kappa}$ 值低于慢速冷却所得 $T_{\\mathrm{~g~}}$ 值。在玻璃态下，自由体积被冻结，并保持恒值，分子链段运动亦被冻结。这时，没有足够的空间进行分子链扩散和构象调整。因此高聚物的玻璃态可视为等自由体积状态。  \n\n在玻璃态下，加热高聚物时，随着温度升高，分子已占体积膨胀，但自由体积没有膨胀。温度达到 $T_{\\mathrm{s}}$ 后，两部分体积同时膨胀。高分子聚合物链段获得足够的动能和必要的自由空间，进行扩散和构象调整。因此玻璃化温度也可定义为高聚物温度膨胀（或收缩）系数改变点。  \n\n![](images/dfd01131148bf395606ba70749ef24bed45f74d4b3164acd4b814913c5df7d8c.jpg)  \n图2-4-16 自由体积  \n\n只有当温度高于 $T_{\\mathrm{s}}$ 时，自由体积才超过 $2.5\\%$ ，其大小取决于 ${\\boldsymbol{T}}-{\\boldsymbol{T}}_{8}$ 温差和体积膨胀  \n\n系数。  \n\n(2）助成膜机理乳胶漆的成膜是由水分挥发，乳胶粒变形和乳胶分子链段扩散缠绕而融合成连续膜。乳胶粒变形和分子链段扩散都要求乳胶聚合物体系中有大于 $2.5\\%$ 的自由体积。这里所谓的乳胶聚合物体系，是指乳胶漆中除颜料和填料外的所有组分混合体。否则乳胶粒处于玻璃态而无法变形，乳胶分子链段和自由体积处于冻结状态而不能扩散。换言之，乳胶漆的成膜温度必须高于乳胶聚合物体系的 $T_{\\mathrm{s}}$ 。这里还要注意两个问题。一是在成膜过程中，乳胶聚合物体系的 $T_{\\mathrm{s}}$ 是变化的，随着成膜助剂和水的挥发，乳胶聚合物体系的 ${{T}_{\\mathrm{{g}}}}$ 会升高。二是实际上，由于颜料和填料的影响，乳胶漆的最低成膜温度还会高于乳胶聚合物体系的 ${T_{\\mathrm{*}}}$ 。也就是说，随着颜料和填料的加人，成膜难度会提高。乳胶漆的最低成膜温度是指乳胶漆形成不开裂的连续涂膜的最低温度。它不同于乳胶漆用乳液的最低成膜温度，在有颜料和填料的乳胶漆中，它高于乳胶漆用乳液的最低成膜温度。  \n\n可见，成膜助剂的助成膜机理就是在成膜过程中提供足够的自由体积，以使乳胶粒变形和乳胶分子链段扩散、缠绕而融合成连续膜。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 820,
+        "chunk": "# 2.成膜助剂的要求  \n\n实际上，成膜助剂是高沸点、低 $\\scriptstyle{T_{\\mathrm{g}}}$ 值、特慢挥发的极性溶剂。  \n\n（1）高助成膜性成膜助剂要求具有高助成膜性。一个聚合物，因其组成和结构不同而有其特征的 $T_{\\mathrm{s}}$ 值。这个聚合物乳液还有一个相应于其 $T_{\\mathrm{s}}$ 值的MFT值。如果在这个乳液中添加了成膜助剂，有效的成膜助剂一定是乳液聚合物的良好溶剂。因此，溶解度参数对理解、判别和选择成膜助剂具有指导意义。乳液聚合物的溶解度参数与成膜助剂的溶解度参数相同或相近时，成膜助剂才能具有较好的助成膜性。在乳胶漆中，处于聚合物粒子和水界面上的成膜助剂，因溶解作用而使乳胶粒子表面有所软化，从而使粒子变形容易，并在较小作用力下就能紧密靠拢。又因成膜助剂是低 $T_{*}$ 的，在施工温度下，能提供较多的自由体积，使聚合物分子链互相扩散，融合而成膜。这就是说，一个 $T_{\\mathrm{s}}$ 值较高的聚合物在使用了成膜助剂的情况下，就可以在较低的温度下成膜。从而使较高的涂膜性能和较低的施工温度得到统一。同时，人们要求成膜助剂能有效地降低体系的MFT，即用量尽量低。  \n\n(2）低挥发速率成膜助剂要特慢挥发。在成膜前，成膜助剂不能挥发掉，所以要求其比水挥发慢得多。一旦成膜后，成膜助剂完成了它们的使命，就要挥发掉。有人认为，成膜助剂存留100h左右是比较合适的。实际上，成膜是一个较长的过程，成膜助剂存留可能要长得多，如4周左右。此外，实际成膜时间长短与 ${\\mathcal{T}}{-}T_{*}$ 温差及相对湿度等有关。  \n\n(3）低分配系数成膜助剂在水中的溶解度要很低，也就是说，要亲树脂乳液，这决定了成膜助剂在乳胶漆体系中处在乳胶粒表面，能发挥最大助成膜的作用。成膜助剂在水相中的浓度 $c_{*}$ 和其在乳胶粒中的浓度 $C_{p}$ 之比称为分配系数 $D$ ，即 $D{=}C_{*}/C_{p}$ 。  \n\n成膜助剂的分配系数要小，才有明显的助成膜效果。乙二醇、丙二醇等分配系数大，不能作成膜助剂，而只是助溶剂。烃类溶剂分配系数太小，成膜助剂不是处在乳胶粒表面，而是进入乳胶粒中，助成膜效果也不好。  \n\n氢键作用参数是表示溶剂通过氢键和水相作用的能力。它强烈地影响分配系数。氢键作用参数高的溶剂主要在水相中，即分配系数大，而氢键作用参数低的溶剂主要在乳液聚合物和水界面上，即分配系数小。因此，低氢键作用参数的成膜助剂助成膜效果好。 Y同一种成膜助剂，由于乳液的组成和结构不同，其分配系数也不同。  \n\n(4）其他成膜助剂还应有好的水解稳定性，和乳液相容性好，尽量无其他负面作用，低冰点，环保和低气味，最好是无气味。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 821,
+        "chunk": "# 3.成膜助剂的组成和结构  \n\n因为材料的性能是由其组成和结构决定的，成膜助剂也一样。  \n\n常用的成膜助剂有 Texanol、Lusolvan FBH、Coasol、DBE-IB、DPnB、Dowanol PPh、醇酯12等，而Texanol是最常用的，也常被作为比较基准。  \n\nAlahapperuma和Glass认为，已知某些成膜助剂是混合物，很可能所有商品成膜助剂都不是单组分的，而是混合物。  \n\nTexanol化学名为2,2,4-三甲基-1,3-戊二醇单异丁酸酯，是Eastman公司的产品，其结构式如下：  \n\nLusolvanFBH、Coasol和DBE-IB都是丁二酸二异丁酯、戊二酸二异丁酯和己二酸二异丁酯的混合物，其结构式如下：  \n\n![](images/ba190cb95130caf26dc15f7f201771714e577b7836baaed6f895ec0aa11a0a9d.jpg)  \n\nLusolvanFBH是BASF公司的产品。Coasol是英国Chemoxy公司的产品，丁二酸二异丁酯 $15\\%\\sim25\\%$ 、戊二酸二异丁酯 $55\\%\\sim65\\%$ 、己二酸二异丁酯 $12\\%\\sim23\\%$ 的混合物。DBE-IB是美国DuPont公司的产品，丁二酸二异丁酯 $15\\%$ 、戊二酸二异丁酯 $58\\%$ 、已二酸二异丁酯 $27\\%$ 的混合物。  \n\nDPnB是二丙二醇丁醚，是DowChemical公司的产品，其结构式如下：  \n\nDowanolPPh是丙二醇苯醚，也是DowChemical公司的产品，其结构式如下：  \n\n成膜助剂的结构特点见表2-4-24。  \n\n表2-4-24成膜助剂的结构特点  \n\n\n<html><body><table><tr><td>成膜助剂</td><td>Texanol</td><td>Lusolvan FBH、Cossol 和 DBE-IB</td><td>DPnB</td><td>Dowanol PPh</td></tr><tr><td>结构特点</td><td>1个羟基、1个酶键</td><td>2个酯键</td><td>1个羟基、2个醚键</td><td>1个羟基、1个醚键</td></tr><tr><td>碳原子数/个</td><td>12</td><td>12,13,14</td><td>10</td><td>9</td></tr><tr><td>分子量</td><td>216</td><td>230,244,258</td><td>190</td><td>152</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 822,
+        "chunk": "# 4.成膜助剂的分类  \n\n成膜助剂可按其在体系中所处的位置进行分类，见表2-4-25。  \n经验表明，AB型成膜助剂是目前使用中较有效的成膜助剂。  \n\n其实，乳胶粒表面吸附着乳化剂，AB型成膜助剂是处在乳液聚合物和乳化剂之间，过是和乳化剂交错吸附在乳液聚合物上，或是其他方式，未见报道。  \n\n甲基吡咯烷酮（NMP）可作为聚氨酯涂料的成膜助剂。可再分散乳胶粉涂料的成膜助剂一般是固体，或将其吸附在填料上。  \n\n表2-4-25成膜助剂分类  \n\n\n<html><body><table><tr><td>类型</td><td>在体系中所处位置</td><td>物质类别</td><td>实例</td><td>说 明</td></tr><tr><td>A型</td><td>在乳液聚合物中</td><td>经类</td><td>石油醚</td><td></td></tr><tr><td rowspan=\"2\">AB型</td><td rowspan=\"2\">在乳液聚合物和水的界</td><td>双酯类</td><td>DBE二甲基酯 DBE二异丁基酶 二异下基已二酸酯</td><td>Estasol、Du Pont DBE类 Coasol,Lusolvan、DBE-IB Chemoxy新产品</td></tr><tr><td>醇酯类</td><td>二丁基邻二甲酸酯 双醇单酯</td><td>Texanol</td></tr><tr><td></td><td>ABC型和在聚合物颗粒间、边界上</td><td>乙二醇酯与乙二醇酯醚</td><td>文有与其公</td><td></td></tr><tr><td>C型</td><td>在水中</td><td>乙二醇</td><td>二乙二醇 二丙二醇 三乙二醇</td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 823,
+        "chunk": "# 5.成膜助剂的性能比较  \n\n对成膜助剂的各种性能进行比较，如性能参数、降低乳液MFT和相容性等。  \n（1）成膜助剂性能参数成膜助剂的性能参数见表2-4-26。  \n\n表2-4-26成膜助剂的性能参数  \n\n\n<html><body><table><tr><td colspan=\"2\">性能参数</td><td>Texanol</td><td>DBE-IB</td><td>Coasol</td><td>Lusolvan FBH</td><td>DPnB</td><td>Dowanol PPh</td></tr><tr><td colspan=\"2\">闪点/℃</td><td>120</td><td>131</td><td>131</td><td>131</td><td>100</td><td>120</td></tr><tr><td colspan=\"2\">沸点/℃</td><td>255</td><td>271</td><td>274</td><td>>260</td><td>230</td><td>243</td></tr><tr><td colspan=\"2\">20C蒸气压/Pa</td><td>1</td><td>0.1</td><td>0.4</td><td>1</td><td>0.04</td><td>0.01</td></tr><tr><td colspan=\"2\">水中溶解度/%</td><td><1</td><td><1</td><td>0.1</td><td>不溶</td><td>4.5</td><td>1.0</td></tr><tr><td colspan=\"2\">20℃密度/（g/cm）</td><td>0.95</td><td>0.96</td><td>0.96</td><td>0.96</td><td>0.91</td><td>1.06</td></tr><tr><td colspan=\"2\">20℃黏度/mPa·s</td><td>13.5</td><td>21</td><td>5.3(25°C)</td><td>7(23C)</td><td>4.9</td><td>24.5</td></tr><tr><td colspan=\"2\">比挥发速率（乙酸正丁酯</td><td>0.2</td><td>0.12</td><td><1</td><td></td><td>0.6</td><td>0.2</td></tr><tr><td rowspan=\"3\">数汉森溶娜度参</td><td>品</td><td>9.8</td><td>7.4</td><td></td><td></td><td>8.7</td><td>11.3</td></tr><tr><td></td><td>6.1</td><td>2.0</td><td></td><td></td><td>2.5</td><td>5.7</td></tr><tr><td></td><td>15.8</td><td>16.2</td><td></td><td></td><td>14.8</td><td>18.7</td></tr></table></body></html>  \n\n由表2-4-26可以看出， $\\mathrm{DPnB}$ 、DowanolPPh在水中的溶解度较大。  \n\n(2）成膜助剂降低MFT成膜助剂的用量主要取决于乳液聚合物的最低成膜温度和成膜助剂的效能。降低乳液聚合物最低成膜温度是成膜助剂的重要指标。  \n\n表2-4-27是不同的乳液、采用不同量的Texanol所能达到的最低成膜温度。  \n\n表2-4-27不同用量的Texanol所能达到的最低成膜温度  \n\n\n<html><body><table><tr><td>以乳液固体量为基准 的Texanol用量/%</td><td>纯丙Rhoplex HG-74 /℃</td><td>苯丙 Acronal 296 D /C</td><td>纯丙Rhoplex AC-2507 /</td><td>醋丙Flexbond 325</td></tr><tr><td>0</td><td>16</td><td>12</td><td>14</td><td>12</td></tr><tr><td>2</td><td>14</td><td>9</td><td>6</td><td>7</td></tr><tr><td>4</td><td>11</td><td>4</td><td>2</td><td>4</td></tr><tr><td>6</td><td>？</td><td>。</td><td><0</td><td>1</td></tr><tr><td>8</td><td>4</td><td><0</td><td><0</td><td><0</td></tr></table></body></html>  \n\nTexanol和DBE-IB对不同乳液MFT的下降能力比较见表2-4-28。  \n\n表2-4-28Texanol和DBE-IB对不同乳液MFT的下降能力比较  \n\n\n<html><body><table><tr><td>乳液</td><td colspan=\"2\">内墙纯丙半光</td><td colspan=\"2\">外墙醋丙半光</td><td colspan=\"2\">外境纯丙</td></tr><tr><td>成膜助剂</td><td>DBE-IB</td><td>Texanol</td><td>DBE-IB</td><td>Texanol</td><td>DBE-IB</td><td>Texanol</td></tr><tr><td>成膜助剂用量/%</td><td>2.2</td><td>2.2</td><td>3.5</td><td>3.5</td><td>1.7</td><td>1.7</td></tr><tr><td>MFT/C</td><td>9.1</td><td>6.2</td><td>15.1</td><td>13.3</td><td>16.2</td><td>-16.2</td></tr></table></body></html>  \n\n由表2-4-28可以看出，与Texanol相比，DBE-IB降低MFT的能力较强。  \n\n伊斯曼欧洲技术中心—Kirkby实验室为了降低Texanol的气味，试验采用TXIB（2，2，4三甲基-1，3-戊二醇单异丁酸二酯）和TXIB：Texano $\\mathbf{\\tau}=1:1$ 的混合成膜助剂。该试验以LusolvanFBH和Texanol为比较基准，共采用九种不同乳液，分别从降低MFT、光泽、低温颜色变化和耐洗刷性四个方面进行评价，降低乳液MFT的结果见表2-4-29。  \n\n表2-4-29降低乳液MFT的比较  \n\n\n<html><body><table><tr><td>乳液</td><td>类 型</td><td>生产企业</td><td></td><td></td><td>Lusolvan FBHTexanolTXIB:Texanol=1  1TXIB</td><td></td></tr><tr><td>Primal AC265</td><td>纯丙</td><td>Rohm &. Haas</td><td>2</td><td>1</td><td>4</td><td>3</td></tr><tr><td>Acronal 296D</td><td>苯丙</td><td>BASF</td><td>1</td><td>4</td><td>3</td><td>2</td></tr><tr><td>Viking 5455</td><td>苯丙</td><td>Viking</td><td>1</td><td>2</td><td>3</td><td>3</td></tr><tr><td>EmultexVV563</td><td></td><td>Harlow</td><td>3</td><td>3</td><td>3</td><td>4</td></tr><tr><td>EmultexVV573</td><td></td><td>Harlow</td><td>1</td><td>2</td><td>3</td><td>4</td></tr><tr><td>EmultexVV574</td><td></td><td>Harlow</td><td>1</td><td>2</td><td>3</td><td>4</td></tr><tr><td>Vinamul 3650</td><td>醋酸乙烯-氯乙烯-乙烯-丙烯酸</td><td>Vinamul</td><td>1</td><td>2</td><td>3</td><td>4</td></tr><tr><td>Vinamul 3469</td><td>醋酸乙烯-氯乙烯-乙烯</td><td>Vinamul</td><td>2</td><td>1</td><td>3</td><td>4</td></tr><tr><td>Vinamul 7172</td><td></td><td>Vinamul</td><td>1</td><td>3</td><td>2</td><td>2</td></tr></table></body></html>\n\n注：1表示最好；2表示好；3表示中；4表示差，  \n\n由表2-4-29可以看出，总体来说，这四种成膜助剂降低乳液聚合物MFT由强至弱的次序是Lusolvan FBH、Texanol、TXIB 和 Texanol混合物、TXIB。  \n\n对光泽、低温颜色变化和耐洗刷性主要与成膜性有关，四种成膜助剂相差不大。  \n表2-4-30是对于不同乳液聚合物，达到最低成膜温度为 $0\\mathrm{{^{*}C}}$ 时，不同成膜助剂的用量。  \n\n表2-4-30达到最低成膜温度为0℃时的成膜助剂用量 单位：%  \n\n\n<html><body><table><tr><td>乳液</td><td>固含量</td><td>Texanol</td><td>苯甲醇BA</td><td>乙二醇丁醚EB</td><td>丙二醇苯醚PPh</td></tr><tr><td>6512苯丙</td><td>49~51</td><td>6</td><td>4</td><td>11</td><td></td></tr><tr><td>B-96苯丙</td><td>47~49</td><td></td><td>6</td><td>N</td><td>6</td></tr><tr><td>3518醋丙</td><td>57~59</td><td>5</td><td>N</td><td>N</td><td>4</td></tr><tr><td>3501权醋</td><td>55~57</td><td></td><td>N</td><td>N</td><td>6</td></tr></table></body></html>\n\n注：N表示相容性不好，未测。  \n\n对于苯丙乳液，苯甲醇的用量比Texanol低，可能是因为相似相溶原理，苯甲醇能在最大限度上软化苯丙乳液粒子，使之以较少的用量将乳液的最低成膜温度降至 $0\\%$ 。但苯甲醇毒性较大，与其他类型乳液相容性较差。乙二醇丁醚溶于水，且挥发速率高，所以用量大，助成膜效果差。丙二醇苯醚试验结果还是不错的。  \n\n表2-4-31是Texanol、二丙二醇醚和二乙二醇二乙醚降低有机硅-苯丙乳液MFT的情况。  \n\n单位：℃  \n\n表2-4-31不同成膜助剂降低有机硅-苯丙乳液MFT  \n\n\n<html><body><table><tr><td>成膜助剂用量/%</td><td>。</td><td>2</td><td></td><td>6</td><td>8</td><td>10</td></tr><tr><td>Texanol</td><td>20.4</td><td>13.2</td><td>8.5</td><td>7.6</td><td>3.5</td><td>1. 2</td></tr><tr><td>二丙二醇醚</td><td>20.4</td><td>13.1</td><td>7.3</td><td>4.2</td><td>0.3</td><td>1. 6</td></tr><tr><td>二乙二醇二乙醚</td><td>20.4</td><td>11. 9</td><td>7.6</td><td>3.7</td><td>。</td><td>3.5</td></tr></table></body></html>  \n\n对该试验中有机硅-苯丙乳液，三者中，二乙二醇二乙醚降低MFT最有效。  \n\n(3）成膜助剂和乳液的相容性成膜助剂和乳液的相容性是配方中必须考虑的问题之一，表2-4-32是几种成膜助剂对一些乳液的试验结果，此结果仅供选用时参考。  \n\n表2-4-32成膜助剂和乳液的相容性  \n\n\n<html><body><table><tr><td>乳液</td><td>Texanol</td><td>苯甲醇BA</td><td>乙二醇丁醚EB</td><td>丙二醇苯醚PPh</td></tr><tr><td>AC-261纯丙</td><td>正常</td><td>絮凝</td><td>絮凝</td><td>絮凝</td></tr><tr><td>1118纯丙</td><td>正常</td><td>絮凝</td><td>絮凝</td><td>絮凝</td></tr><tr><td>6512苯丙</td><td>正常</td><td>正常</td><td>正常</td><td>正常</td></tr><tr><td>B-96苯丙</td><td>正常</td><td>正常</td><td>絮凝</td><td>正常</td></tr><tr><td>3518醋丙</td><td>正常</td><td>絮凝</td><td>絮凝</td><td>正常</td></tr><tr><td>3501叔醋</td><td>正常</td><td>絮凝</td><td>絮凝</td><td>正常</td></tr></table></body></html>  \n\n从表2-4-32可以看出，Texanol与不同类型乳液的相容性都很好，且添加方便。丙二醇苯醚和纯丙乳液会产生絮凝。苯甲醇只与苯丙乳液相容。而乙二醇丁醚仅与长兴6512苯丙乳液相容。  \n\n(4）成膜助剂的负面作用Schwartz等认为，成膜助剂能降低MFT和提高耐洗刷性，但也会影响涂膜硬度的发展和整个使用期的表面黏性，亦即影响涂膜的耐沾污性。  \n\n通常，随着成膜助剂的加人，会降低乳液和乳胶漆的稳定性，这一点在成膜助剂和乳液的相容性介绍中已看得很清楚，尤其快速加入时，有的甚至会造成乳液破乳。  \n\n通常成膜助剂是VOC，对环境友好不利，选用时要注意所在国家或地区对VOC的有关规定。  \n\n成膜助剂对缔合型增稠剂的增稠作用会有影响。因此使增稠系统调整较复杂。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 824,
+        "chunk": "# 6.成膜助剂的使用  \n\n(1）成膜助剂的用量成膜助剂的用量主要应根据乳液的MFT、乳胶漆的MFT和成膜助剂的助成膜效能，通过试验确定。  \n\n一般都认为，成膜助剂的用量按配方中乳液量考虑。其实不完全如此。低PVC时，应少于按配方中乳液量得到的结果。高PVC时，应多于按配方中乳液量而求到的数值。实际使用经验表明，确定成膜助剂用量的较方便方法是，根据乳液和乳胶漆的MFT高低，以及成膜助剂的助成膜效能，按配方总量来计算。因为随着PVC的提高，尽管乳液量减少，但体系颜料和填料增加，一方面成膜困难加大，另一方面颜料和填料黏附成膜助剂量也会增大，成膜助剂效能降低，所以需要更多的成膜助剂。 话  \n\n确定成膜助剂用量时，不仅要考虑乳液的低温成膜性，更应注意乳胶漆的低温成膜性，如在 $5\\mathrm{{c}}$ 或较低温度下的成膜性，因为部分乳胶漆会在这种条件下施工。  \n\n(2）成膜助剂的加料次序通常，成膜助剂在调漆阶段加入，并在乳液加入后，应一边慢速加人一边不停地混合。  \n\n也有将成膜助剂在颜料和填料研磨分散前加入的，这对乳液比较安全。但憎水的成膜助剂会被润湿分散剂乳化，也有可能被颜料和填料黏着吸人了一部分。  \n\n(3）成膜助剂的搭配使用成膜助剂一般是单独使用的，但也可搭配使用，以便取得更好结果。如LusolvanFBH、Coasol和DBE-IB本身就是混合成膜助剂，Texanol和TXIB搭配在基本保证效能的前提下以降低气味，用较有效降低Tg的成膜助剂EastmanEEH和Texanol搭配使用（当然，EastmanEEH也可单独使用）能降低VOC等。  \n\n（4）成膜助剂的验收由于我国市场还不成熟，通过试验确定所用成膜助剂后，对于每个批号的进货，通常还要进行验收检验。测试内容如折射率、馏程、密度、外观和气味等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 825,
+        "chunk": "# 7.成膜助剂的发展趋势  \n\n尽管成膜助剂对乳胶漆的成膜有很大作用，但成膜助剂是有机溶剂，对环境是有影响的，所以发展的方向是环境友好型的有效成膜助剂。  \n\n一是降低气味。Coasol、DBE-IB、Optifilm Enhancer 300（2,2,4-trimethyl-1,3-pen-tanedioldiisobutyrate，即2,2,4-三甲基-1,3-戊二醇二异丁酸酯）、TXIB以及TXIB和 Tex-anol的混合物都能降低气味。尽管TXIB在降低MFT和早期耐洗刷性稍差，但通过和Tex-anol的混用，能在这些方面得到改善。  \n\n二是降低挥发性有机物（VOC)。双子表面活性剂（geminisurfactants），如烷基酯、链烷二醇等，能降低乳液聚合物的MFT，从而也降低了VOC。低HLB值的双子表面活性剂更有效些。在欧洲，VOC是指那些沸点等于或低于 $250\\%$ 的化学物质。沸点超过 $250^{\\circ}\\mathrm{C}$ 的那些物质不归人VOC的范畴，所以使成膜助剂向高沸点发展。如Coasol、LusolvanFBH、DBE-IB、OptifilmEnhancer 300、EdenolEFC-100（丙二醇单油酸酯，科宁公司产品）、二异丙醇己二酸酯。  \n\n三是低毒、安全、可接受的生物降解性。  \n\n四是活性成膜助剂。丙烯酸双环戊烯基氧乙基酯（DPOA）是不饱和的可聚合有机物，均聚物 $T_{\\mathrm{s}}=33^{\\circ}\\mathrm{C}$ ，无气味。其结构式如下：  \n\n![](images/f5e60eb01d816cfb4d623c4d45e65dcfedf5dd9105638bd4a7b796f2fb4cfff5.jpg)  \n\n在较高 $T_{\\mathrm{~g~}}$ 值的乳胶漆配方中，不需成膜助剂，而加DPOA，并加人少量催干剂，如钴盐。DPOA就可降低成膜温度，使乳胶漆在室温成膜。但DPOA不挥发，不仅环境友好，而且在催干剂作用下进行氧化自由基聚合，增加了涂膜的硬度、抗粘连性和亮度。因此，DPOA被称为活性成膜助剂。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 826,
+        "chunk": "# 十二、乳化剂  \n\n乳化剂是表面活性剂中一员。表面活性剂分子结构中含亲水和亲油两部分，因此，加入少量就可显著改变气-液、液-液、液-固界面性质，起降低界面张力、渗透、润湿、乳化、增溶、分散、清洗、发泡等作用。在许多领域，它们被广泛应用。根据使用场合不同，分别称为乳化剂、去污剂、湿润剂、分散剂、发泡剂等。 5  \n\n2000年北美通过乳液聚合的方式消耗掉93000t表面活性剂，市值约为1.87亿欧元。大约 $52\\%$ 是阴离子型表面活性剂， $47\\%$ 是非离子型表面活性剂。非离子表面活性剂现在主要还是烷基酚聚氧乙烯醚（alkyl phenolethoxylates，APEOs），少量是脂肪醇聚氧乙烯醚。脂肪醇聚氧乙烯醚具有良好的生态毒性指标，又称绿色表面活性剂。  \n\n到目前为止，在APEOs中，壬基酚聚氧乙烯醚（NPEOs）是最重要的产品。1995年欧洲消耗掉约75000t。据估计整个乳液聚合工业消耗掉约11000tAPEOs。由于该类产品的乳化效率高，经济，容易使用，并有40年以上的使用经验，因此被广泛应用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 827,
+        "chunk": "# 1.乳化剂的分类  \n\n乳化剂分子同时含有亲水基团和亲油基团，按其亲水基团性质的不同可将乳化剂分成四类，即阴离子型乳化剂、阳离子型乳化剂、非离子型乳化剂及两性乳化剂。  \n\n阴离子型乳化剂，亲水基团为阴离子，所接头部基团可为羧酸盐、磺酸盐、硫酸盐、醚硫酸盐、（醚）磷酸盐、琥珀磺酸盐等。  \n\n阳离子型乳化剂，亲水基团为阳离子，如各种结构类型的季铵盐和胺盐。  \n\n非离子型乳化剂，该类表面活性剂在水溶液中不会离解成离子，它的效能与 $\\mathsf{p H}$ 无关，分子结构有烷基芳基或者脂肪醇的聚氧乙烯醚、烷基糖苷、山梨醇酯等。  \n\n两性乳化剂，分子结构中同时包含阴离子和阳离子基团，通常它们在亲水基团部分含有氨基和羧基。  \n\n阴离子型乳化剂是乳液聚合工业中应用最广泛的乳化剂，通常是在 $\\mathbf{p}\\mathbf{H}{>}7$ 的条件下使用。用它生产的乳胶粒子外层具有静电荷，能够防止离子聚集，因此乳液的机械稳定性好，但化学稳定性差，对电解质（包括水的硬度）非常敏感。与非离子型乳化剂相比，其产品乳胶粒子粒径较小，涂膜光泽好。  \n\n阳离子型乳化剂一般是在 $\\mathrm{pH}<7$ 的条件下使用，最好低于5.5。由于胺类化合物具有阻聚作用，且易被过氧化物引发剂氧化而发生副反应，因此阳离子型乳化剂的应用较少。但由于阳离子型乳化剂不怕硬水及可在酸性条件下应用等特点，其用途正日趋扩大。  \n\n非离子型乳化剂可适用于很宽的 $\\mathbf{pH}$ 条件，且不怕硬水，化学稳定性好。该类乳化剂可以很方便地调节分子中亲水基团和亲油基团的比例，以满足不同的需要。一般而言，单纯用非离子型乳化剂进行乳液聚合反应，反应速率低于阴离子型乳化剂参加的反应，且生产出的胶乳粒子粒径较大，涂膜光泽差。几十年来，在乳液聚合中，烷基酚聚氧乙烯醚具有很好的乳化性。但近几年，由于其生态毒性不断招致批评，因此逐步被较环保的产品取代。  \n\n两性乳化剂分子中同时含有碱性基团和酸性基团，在酸性介质中可离解成阳离子，而在碱性介质中又可离解成阴离子，故该种乳化剂在任何 $\\mathsf{p H}$ 下都有效。由于该类乳化剂的低毒性、低生物刺激性和杀菌抑霉性，目前在消毒剂、化妆品、香波、洗涤剂行业正得到极大的重视。但因其价格昂贵，尚未能在乳液聚合工业上体现其独特的性能优势，如良好的乳化分散性，与几乎所有类型乳化剂的配伍性，极好的耐硬水性，耐高浓度电解质性，良好的生物降解性等。但有理由相信，随着人们对高性能产品需求的提高和对生态环境污染问题的更加关注，两性乳化剂在高分子工业中必将发挥更大的作用。  \n\n此外，还有高分子乳化剂、聚合型乳化剂和分解型乳化剂等。高分子乳化剂是相对于常规乳化剂而言，常规乳化剂为低分子量化合物，其分子量一般在300左右，人们把分子量在3000以上的乳化剂称为高分子乳化剂。 9  \n\n聚合型乳化剂又称反应型乳化剂，分子结构中含有可聚合基团，如可参与自由基聚合的双键。在乳液聚合中，这种乳化剂不仅具有良好的乳化性能，而且作为共聚单体直接参与聚合反应，使乳化剂分子以共价键结合到乳液聚合物分子上，有效地提高成膜聚合物的耐水性、黏结性和涂膜性。 二",
+        "category": " Introduction"
+    },
+    {
+        "id": 828,
+        "chunk": "# 2.乳化剂的主要特征参数  \n\n乳化剂的主要特征参数有临界胶束浓度、HLB值、浊点、三相点、转相点等。这里仅介绍临界胶束浓度和HLB值。  \n\n(1）临界胶束浓度当浓度很低时，乳化剂以分子分散状态溶解在水中。当浓度达到某一值后，乳化剂分子就会形成一个球状、棒状或层状的聚集体，它们的亲油基团彼此靠在一起，而亲水基团则向外伸向水相，这样的聚集体称为胶束。能够形成胶束的最低乳化剂浓度称为临界胶束浓度（criticalmicelleconcentration），简称CMC值。  \n\n(2）HLB值乳化剂亲水性和疏水性的相对大小将直接影响其使用效能，尤其是乳化效果的好坏。Griffin提出的乳化剂亲水亲油平衡值HLB（hydrophilelipophilebalance）就是用来衡量乳化剂分子中亲水部分和亲油部分对其性质所做贡献大小的物理量。每一种乳化剂都具有某一特定的HLB值，对于大多数乳化剂来说，其HLB值落在 $1\\sim40$ 之间。油酸$\\mathrm{HLB}{=}1$ ，油酸钾 $\\mathrm{HLB}{=}20$ ，十二烷基硫酸钠 $\\mathrm{HLB}{=}40$ 。非离子型乳化剂HLB处在 $_{1\\sim20}$ 之间，离子型乳化剂HLB处在 $1\\sim40$ 之间。HLB越低，表明其亲油性越大；HLB越高，表明亲水性越大。一般而言 $\\mathbf{H}\\mathbf{L}\\mathbf{B}{=}4{\\sim}6$ ，大都是W/O型乳液乳化剂。 $\\mathrm{HLB}{=}8{\\sim}18$ ，则为O/W型乳液乳化剂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 829,
+        "chunk": "# 3.乳化剂的作用  \n\n并非所有的表面活性剂都可以用在乳液聚合中。只有那些对聚合物乳液体系有着有效的稳定作用，同时又不影响聚合反应的表面活性剂，才适合作乳液聚合的乳化剂。乳化剂在乳液聚合中的作用是多样的，例如，对水不溶单体的增溶作用，降低表面张力和界面张力，乳化、分散和稳定等作用，并对乳胶粒直径、数目、聚合物分子量、聚合反应速率和乳液的性能等均有明显的影响。  \n\n(1）对聚合的作用一般来说，阴离子型乳化剂负责胶粒的形成。在没有应用要求的情况下，阴离子型乳化剂的选择将依赖于所要求的粒径。高CMC的乳化剂，例如琥珀磺酸盐，比较容易形成较大的粒子，但是琥珀磺酸盐也能得到较窄的粒径分布。  \n\n非离子型乳化剂尽管有较低的CMC，但是对胶束的形成没有显著的效果。这被归结于该类乳化剂优先进入单体相。  \n\n阴离子型乳化剂在水中的浓度大于CMC时会形成碗状的胶束，非离子型乳化剂在高于CMC时通常形成栅状结构胶束。乳液聚合中，常常把阴离子型乳化剂和非离子型乳化剂配合使用，这时会形成各种形状的胶束。  \n\n(2）对稳定的作用不同类型的乳化剂防止被乳化液滴或固体颗粒相互聚结而达到稳定的机理是不同的。  \n\n$\\Phi$ 双电层静电排斥作用吸附在乳胶粒表面的离子型乳化剂，在一定pH下是以离子的形式存在的，这就给乳胶粒表面带上一层电荷。根据乳化剂离子性质的不同，电荷可能为正，也可能为负。这一层电荷是不动的，称为固定层。在固定层周围，由于静电引力会吸附一层异性离子，称为吸附层。吸附层中的一部分带电离子将扩散到周围介质中。使乳胶粒表面（包括固定层和吸附层）带上与固定层离子符号相同的电荷，而在乳胶粒周围的介质中则带上异号电荷。这样的结构称为双电层。双电层重叠时的静电斥力和粒子间的长程范德华吸引力之间建立平衡，从而使聚合物乳液具有稳定性。  \n\n$\\textcircled{2}$ 空间位阻保护作用对于非离子型乳化剂和水溶性聚合物稳定的乳液而言，乳胶粒表面上吸附或接枝的大分子链的几何构型使得乳胶粒周围形成了有一定厚度和强度的吸附层，这种空间位阻保护作用阻碍了乳胶粒之间产生聚结而使乳液稳定。 学  \n\n一般而言，乳胶粒周围的双电层静电排斥作用使乳液具有较强的机械稳定性，但抗电解质性很差；而空间位阻保护作用则使乳液体系具有较强的电解质稳定性，而机械稳定性差。在实际应用中，往往是将两者结合起来。  \n\n(3）负面作用首先，由于乳化剂的存在，乳液在调漆时容易起泡，因此在调漆阶段一般要加消泡剂。处理不好，影响调制、输送和涂布施工，其结果甚至影响涂膜质量。  \n\n其次，乳化剂是亲水物质，乳胶漆成膜后，它们仍残留在涂膜中，对涂膜的耐水性和吸水性带来不良影响。而被雨水冲淋后，会在涂膜表面造成凹凸不平，影响光泽保持。采用聚合型乳化剂能降低此影响。  \n\n再者，乳化剂多半是低分子物质，对温度敏感，成膜后留在涂膜中，会影响涂膜耐沾污性。而且，乳化剂对工厂废水处理也是一个不易解决的问题。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 830,
+        "chunk": "# 4.常用乳化剂  \n\n(1）阴离子型乳化剂  \n\n$\\Phi$ 烷基硫酸盐烷基硫酸钠是乳液聚合反应中最广泛使用的乳化剂。原因主要是该类产品可以得到相对纯度高的成品，以及碳链分布方面的高度灵活性。该类产品的CMC取决于它们分子结构上的疏水部分，碳链数越高CMC就越低。  \n\n脂肪醇硫酸盐在乳液聚合的最初阶段就被用于乳化剂，而且以其较好的乳化性能和制得超细粒径乳液而闻名。部分不饱和的十八烷基/十六烷基硫酸盐可作为乳化剂用于低泡聚合物乳液的生产。  \n\n从工业化生产的角度来看，烷基硫酸盐有其不足之处，那就是它们的溶液在低温下很难保持液状，而且在酸性条件下会水解。  \n\n$\\textcircled{2}$ 烷基芳基磺酸盐这些是经济实惠的化学产品，因此广泛适用于乳液聚合。  \n\n烷基苯磺酸盐是表面活性剂和洗涤剂中最重要的一类。直链十二烷基苯磺酸盐，作为阴离子型乳化剂，常应用于聚氯乙烯的生产以及其他聚合物乳液，而支链的四丙基苯磺酸盐（TPS)，则仅限于少量用途。原因之一就是该化学结构生物降解能力差，曾导致许多环境问题。  \n\n在乳液聚合中，烷基二苯醚二磺酸盐作为乳化剂稳定性较好。但比起简单的磺酸盐，该乳化剂的原料明显昂贵得多。  \n\n$\\textcircled{3}$ 琥珀磺酸盐该类产品，由于链长度的不同而造成CMC 的不同。短链的CMC 高，己基二酯和环己基二酯是乳液聚合常用的乳化剂，尤其是要求大粒径的时候。  \n\n琥珀磺酸二酯在美国的乳液聚合配方中的地位是最重要的。它们很少作为主要乳化剂使用，只是用于辅助剂，例如，用于高固含量、低黏度的丙烯酸乳液的生产。支链的二-2-乙基己基琥珀磺酸钠被广泛使用，原因就是除了良好的乳化性能外，还有优良的润湿性能。  \n\n④醚硫酸盐烷基酚醚硫酸盐、磷酸盐和琥珀磺酸盐主要作为基础阴离子型乳化剂，广泛用于丙烯酸酯、苯乙烯-丙烯酸酯和醋酸乙烯酯共聚物的生产。  \n\n(2）非离子型乳化剂正如前面提到的，烷基酚聚氧乙烯醚在乳液聚合中作为非离子型乳化剂使用已经有很多年了。由于丙烯和丁烯的价格优势，壬基（三聚丙烯）酚聚氧乙烯醚和辛基（二聚丁烯）酚聚氧乙烯醚已被广泛使用。一般来说，低乙氧基化程度的该类乳化剂，只能与阴离子型乳化剂配合使用；中乙氧基化程度的该类乳化剂，能较好地提高乳液机械稳定性；高乙氧基化程度的该类乳化剂，则能提高抗金属离子的能力。  \n\n脂肪醇聚氧乙烯醚和一些特别开发的产品，作为APEOs的替代型非离子型乳化剂已被使用。  \n\n聚烷基糖苷是绿色环保型表面活性剂，它完全起源于可再生资源淀粉和蔬菜油，而且也可以作为非离子型乳化剂，用于乳液聚合。 ！  \n\n(3）反应型乳化剂在大多数场合，乳化剂是吸附于乳胶粒表面，与水处于动态平衡。在某些不利情况下，如聚合反应中的某些突变，冻融循环时温度变化，水相离子强度的变化，乳化剂可能解吸，随之乳液失去稳定。  \n\n为了避免这些情况的发生，目前有用聚合型乳化剂永久性地锚固在乳胶表面。这能提高乳液稳定性和降低涂膜对水的敏感性。业已商业化的有烷基烯丙基琥珀磺酸钠等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 831,
+        "chunk": "# 5.乳化剂的选择  \n\n合理选择乳化剂，优化其用量，并确定适宜加人方式，是获得优质乳液的前提条件之一。  \n\n(1）所选乳化剂的HLB值应和乳液聚合体系相匹配表2-4-33给出不同乳液聚合体系与乳化剂HLB的相关值。这些HLB值是在一定条件下得出的结果，可作为乳化剂粗选参考。  \n\n表2-4-33不同乳液聚合体系所要求乳化剂HLB值  \n\n\n<html><body><table><tr><td>乳液聚合体系</td><td>温度/C</td><td>HLB值</td><td>乳液聚合体系</td><td>温度/C</td><td>HLB值</td></tr><tr><td>聚苯乙烯</td><td></td><td>13. 0~16.0</td><td>聚丙烯睛</td><td></td><td>13.3~13.7</td></tr><tr><td></td><td></td><td></td><td>1.5~17.5甲基丙烯酸甲酶/丙烯酸乙酯</td><td></td><td></td></tr><tr><td>聚酯酸乙始</td><td>70</td><td></td><td></td><td></td><td>12. 0~13.1</td></tr><tr><td>聚甲基丙烯酸甲酯</td><td></td><td>12.1~13.7</td><td>聚丙烯酸丁酯</td><td>40</td><td>14.5</td></tr><tr><td>聚丙烯酸乙酯</td><td></td><td>11.8~12.4</td><td>聚丙烯酸丁酯</td><td>60</td><td>15.5</td></tr><tr><td>聚丙烯酸乙酯</td><td>40</td><td>13.7</td><td>聚丙烯酸-2-乙基已酯</td><td>30</td><td>12.2~13.7</td></tr><tr><td>聚丙烯酸乙酯</td><td>60</td><td>15.5</td><td></td><td></td><td></td></tr></table></body></html>  \n\n对于乳液共聚体系，所要求的HLB值可将各组分的HLB值按质量分数进行加权平均求取：  \n\n式中 $\\mathrm{HLB_{1}}$ · $\\mathrm{HLB}_{2}$ ———共聚组分1、2的均聚物所要求的HLB值；  \n\n$W_{1}$ . $\\boldsymbol{w}_{z}$ —共聚组分1、2的质量分数。  \n\n(2）用于乳液聚合的乳化剂通常为阴离子型乳化剂和非离子型乳化剂的复配物，两者并用，能取得相得益彰的效果。  \n\n（3）所选用的离子型乳化剂的三相点应低于反应温度。  \n\n（4）所选用的非离子型乳化剂的浊点应高于反应温度。  \n\n(5）对离子型乳化剂来说，一个乳化剂分子的覆盖面积 $\\scriptstyle\\alpha_{*}$ 越大，乳胶粒表面电荷密度越小，乳液越不稳定，故应选用 $\\alpha_{\\mathrm{{s}}}$ 尽量小的乳化剂；对非离子型乳化剂来说，a越大时，其水化作用越强，对乳液稳定作用增强，所以应选用 $\\scriptstyle a_{\\mathbf{s}}$ 大的乳化剂。  \n\n(6）应选用临界胶束浓度尽量小的乳化剂。  \n\n(7）应选用增溶度大的乳化剂。  \n\n(8）所选用的乳化剂不应干扰聚合反应。  \n\n(9）选择乳化剂时应考虑其后的生产工艺和聚合物乳液的应用，例如，某些乳化剂尽管乳化效果好，但是在生产条件下起泡沫严重，不宜选用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 832,
+        "chunk": "# 6.乳化剂的发展趋势  \n\n乳化剂的发展趋势之一是逐步取代聚氧乙烯烷基苯酚醚（APEO或APE）类湿润剂，原因是其生化毒性，如科宁公司产品按欧盟生化毒性分类（2002年）见表2-4-34。可见，随着APE的取代不断进展，毒性逐步降低。  \n\n表2-4-34科宁公司产品按欧盟生化毒性分类  \n\n\n<html><body><table><tr><td>科宁公司产品</td><td>是否含APE</td><td>生化毒性</td></tr><tr><td>Dispolin NP 10</td><td>含APE</td><td>Xn—有害； N—环境风险； R22——吞下有害； R41—对眼睛严重有害； R51—对水生物有毒； R53—-可能给水环境造成长期负面影响</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>科宁公司产品</td><td>是否含APE</td><td>生化毒性</td></tr><tr><td>Dispolin A 1080</td><td>第一代取代品DispolinA系列</td><td>Xn- 一有害； R22- -吞下有害； R41- 对眼睛严重有害； R51—对水生物有毒； -可能给水环境造成长期负面影响</td></tr><tr><td>Dispolin AFX 1080</td><td>第二代取代品Dispolin AFX系列</td><td>R53- 刺对性睛严重有害</td></tr></table></body></html>  \n\n双子表面活性剂也是发展新热点。它是由间隔基连接的两个双亲分子。双子表面活性剂最显著的特点是临界胶束浓度（CMC）比其“单胞”表面活性剂低一个多数量级，其次是高效。TEGOTwin 4000，它就是双子硅氧烷表面活性剂，并具有不稳泡和消泡性。AirProducts开发了双子表面活性剂。传统的表面活性剂具有一个疏水基的尾和一个亲水基的头，而这种新表面活性剂却具有两个亲水基和两个或三个疏水基，是一种多功能表面活性剂，称为乙炔二醇类，产品如EnviroGemAD01。  \n\n还有就是开发了可降解的表面活性剂。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 833,
+        "chunk": "# 十三、特种功能添加剂  \n\n特种功能添加剂比较多，此处仅介绍纳米助剂和负离子添加剂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 834,
+        "chunk": "# 1.纳米助剂  \n\n所谓纳米助剂，是指大小在 $1\\sim100\\mathrm{nm}$ 之间，当其添加人涂料中后，能明显提高涂料性能或赋予涂料新功能的材料。  \n\n纳米材料具有小尺寸效应、表面效应、量子尺寸效应和宏观量子隧道效应等基本特性。因此，人们将其作为涂料助剂对涂料进行改性。如纳米二氧化硅和纳米三氧化二铝能提高涂膜硬度和抗刮伤性，纳米锐钛型二氧化钛可作光催化剂和自清洁剂，纳米金红石型二氧化钛、纳米二氧化硅、纳米云母和纳米氧化锌可赋予涂膜抗紫外线性，纳米锐钛型二氧化钛和纳米氧化锌具有抗菌防霉性，纳米磁性材料、纳米硼化物和纳米碳化物可用于隐身涂料，纳米三氧化二铁、纳米二氧化钛、纳米三氧化二铬和纳米氧化锌使涂膜具有抗静电性，无机纳米材料与聚合物杂化使黏结剂兼具有机和无机优点等。  \n\n在涂料中加入纳米助剂是一件不难的事，但要使其保持纳米状态，并起改性作用，从而大大改进和提高涂料性能，或产生新的应用性能，这才是纳米助剂的关键所在，难点所在。  \n\n王雪松等采用纳米级氧化锡锑粉，经选用合适的分散剂种类和用量以及分散工艺等，得到约 $28\\mathrm{nm}$ 的分散体。再和聚丙烯酸乳液、其他颜料和填料等制成导电乳胶漆。当纳米分散体达到一定量时，涂膜达到导静电的要求，表面电阻率不大于 $10^{9}\\Omega$ ，体积电阻率不大于$10^{8}\\Omega\\cdot\\mathrm{cm}$ 。与微米级导静电粉相比，纳米级导静电粉在加量少时即可获得导静电效果。  \n\n自从1972年本田和藤岛昭发现二氧化钛的光催化性以来，光催化材料的制备和应用研究不断取得进展。人们以纳米锐钛型二氧化钛为光催化剂生产能净化空气的涂料。  \n\n混晶催化剂、掺杂不同价态金属离子、与其他半导体化合物或微结构矿物复合等能提高纳米锐钛型二氧化钛光催化活性。 P据报道，用氮和碳等掺杂能使纳米锐钛型二氧化钛光催化活性移至可见光区。  \n\n纳米助剂的商品，如BYK公司的纳米氧化铝系列助剂Nanobyk-3600、Nanobyk-3601、Nanobyk-3602，纳米二氧化硅助剂Nanobyk-3650，纳米氧化锌紫外线吸收剂Nanobyk-  \n\n3820、Nanobyk-3840、Nanobyk-3860。其中Nanobyk-3820用于水性木器涂料，Nanobyk  \n3860用于建筑涂料。另外，还有我国浙江舟山明日纳米助剂公司的相关产品等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 835,
+        "chunk": "# 2.负离子添加剂  \n\n现代环境卫生学的调查研究表明，空气中负离子对人体健康有利。在内墙涂料中，加人负离子添加剂，从而使涂膜不断放出负离子，改善室内空气质量。  \n\n负离子添加剂是经过处理的天然矿物粉体，如奇冰石、电气石、神州奇石、麦饭石、桂阳石等。  \n\n在涂料成膜后，空气中的水分子可以通过涂膜与负离子添加剂接触，在负离子粉体颗粒电极附近的强电场作用下，电离成氢氧根离子和氢离子。氢氧根离子进入空气，吸收空气中水分子，形成水合羟基离子 $\\mathbf{H}_{3}\\mathbf{O}_{2}^{-}$ ，即为负离子。从而增加空气中负离子浓度，达到提高空气质量的目的。  \n\n另外，负离子添加剂还有去除空气中甲醛、氨等有害物质和抗菌抑菌作用。  \n\n该类负离子添加剂，如北京朗诺环保科技有限公司的负离子涂料添加剂。  \n\n尽管负离子添加剂已在涂料中应用，但在负离子释放性能上还有待进一步提高。目前所采用的手段是用稀土元素对负离子添加剂进行活化。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 836,
+        "chunk": "# 参考文献  \n\n[1] 胡英，陈学识，吴树森，表面化学：物理化学，北京：人民教育出版社，1979：64.  \n[2] Capelle Dr A, Bieleman J H. Polymer Paint and Colour Journal, 1979, 169 (407): 854.  \n[3] Peter Quednau. 非水系塗料湿润、 分散。装七料，1982，（347)：46-48.  \n[4] 大数權昭 期料分散 色材会話，1986，59（2）：23-24.  \n[5] 沈- 表面活性剂的基本性质： 高分子表面活性剂. 北京；化学工业出版社，2002；11-12.  \n[6] 顾国芳 用助剂 理和应用 北京：化学工业出版社，2003.  \n[7] 赵国 表面 北京大学出版社，1984.  \n[8] 林宜益 北京 工业出版社，2006.  \n[9] 部隽奎等译. 北京：化学工业出版社，1988.  \n[10] 朱传榮等译. 上海：上海科技文献出版社，2000.  \n[11] 周大纲， 北京： 中国轻工业出版社，1998.  \n[12] L央 包 华等译 北京： 中国石化出版社，2003.  \n[13] [瑞典 性剂和聚合物. 韩丙勇，张学军译，北京：化学工业出版社，2005.  \n[14] Bieleman einhein Wiley-VCH Verlag GmbH, 2000.  \n[15] Gerry Additiv Coatings, UK, The Royal Society of Chemistry, 2003.  \n[16] Kent D J ntin May 63-70.  \n[17] Bentley J, croduction to Paint Chemistry and Principles of Paint Technology. fourth edition. London: Published by &. Hall, 1998; 173-174.  \n[18] Gite Kulkarni R D t al. Paintindia，2005, Nov; 63-70.  \n[19] Paulus W Directory of Mirobicides for the Protection of Materials A Handbook, The Netherlands;  \nSpringer, 2005.  \n[20] 陈仪本等编著. 工业杀菌剂. 北京： 化学工业出版社，2001：232-237.  \n[21] Valet A. Polym Paint Coat J, 1995, (185)； 31.  \n[22] 潘江庆. 高分子通报， 1992, (3)；138.  \n[23] Decker C, Biry S, Zahouilly K, Polym Degrad Stab, 1995, (49): 111.  \n[24] Fernandez A M, et al, New Generation of Alkyl Phenol-free Nonionic Surfactants for Emulsion Polymerization2005,(7).  \n[25] Bieieman J. Surface Coatings International Part A, 2004, (4): 173-178.  \n[26] 廖有为，熊平凡，赵舒超等，现代涂料与涂装，2007，（7)：1-4，7.",
+        "category": " References"
+    },
+    {
+        "id": 837,
+        "chunk": "# 第三篇 涂料各论",
+        "category": " Introduction"
+    },
+    {
+        "id": 838,
+        "chunk": "# 第一节乳胶漆",
+        "category": " Introduction"
+    },
+    {
+        "id": 839,
+        "chunk": "# 一、乳胶漆概述",
+        "category": " Introduction"
+    },
+    {
+        "id": 840,
+        "chunk": "# 1.乳胶漆定义  \n\n在我国，人们习惯上把以合成树脂乳液为基料，以水为分散介质，加入颜料、填料和助剂，经一定工艺过程制成的涂料，叫做乳胶涂料，简称乳胶漆。  \n\n乳胶漆的关键特征是以合成树脂乳液为基料，以水为分散介质。乳胶漆是合成树脂固体微粒在水中分散体和颜料、填料颗粒在水（各种助剂的水溶液）中分散体的混合物。前一分散体属于胶体分散，而后一分散体属于悬浮分散或叫做粗分散。就乳胶漆而言，属于粗分散体系。乳胶漆一般都含有颜料和填料，但乳胶清漆不含颜料和填料，有光乳胶漆往往仅含颜料而不含填料。  \n\n乳液（emulsion）、乳胶（latex）和分散体（dispersion），都是指一种物质（分散相）在另一种物质（分散介质）中的分散体系。其中乳液是一种液体以极小的液滴形式分散在另一种互不相溶的液体中所构成的分散体，乳胶是由乳液聚合制得、不溶于水的合成树脂以微粒形式分散在水中而形成的分散体，而两者都可称为分散体。但在涂料界，往往不加以区别，读者自己心中要清楚，当然也有人是严格加以区别的。",
+        "category": " Introduction"
+    },
+    {
+        "id": 841,
+        "chunk": "# 2.乳胶漆的特点  \n\n(1）优点乳胶漆具有一系列优点。  \n\n①以水为分散介质，是一种既省资源又安全的环境友好型涂料。②施工方便，可刷涂、滚涂和喷涂。可用水稀释，涂刷工具可以很方便地用水立即清洗。③涂膜干燥快，在合适的气候条件下，一般4h左右可重涂，1天可施涂二三道。④透气性好，对基层含水率的要求不如溶剂型涂料那么严，能避免因不透气而造成的涂膜起泡和脱落问题，还能大大缓解结露，或不结露。  \n\n③耐水性好，乳胶漆是单组分水性涂料，但其干燥成膜后，涂膜不溶于水，具有很好的耐水性。  \n\n$\\textcircled{6}$ 性能能满足保护和装饰等要求，所以使用范围不断扩大。  \n\n(2）缺点乳胶漆也存在一些不尽如人意的地方。  \n\n$\\Phi$ 最低成膜温度高，一般为5℃以上，所以在较冷的地方冬季不能施工。  \n\n$\\textcircled{2}$ 干燥成膜受环境温度、湿度和风速等影响较大。  \n\n$\\textcircled{3}$ 干燥过程长。前面已提到涂膜干燥快，这里又说干燥过程长，看似矛盾。其实涂膜干燥快是指表干，不到2h，当然是千燥快。干燥过程长是指实干，完全成膜，需几周。  \n\n$\\textcircled{4}$ 贮存运输温度要在 $0\\%$ 以上。  \n\n$\\textcircled{5}$ 光泽也比较低。",
+        "category": " Introduction"
+    },
+    {
+        "id": 842,
+        "chunk": "# 3.乳胶漆的发展  \n\n乳胶漆的发展在涂料的发展长河中还只是短暂的一段。涂料的发展已有以千年计的历史，而乳胶漆的发展只有约60年的历史。  \n\n聚合物是涂料的最重要的组分，在某种意义上说，聚合物的发展水平就代表了涂料的发展水平。同样，乳液是乳胶漆的关键组分，所以也可以说乳液发展情况就是乳胶漆发展情况的缩影。  \n\n表3-1-1是罗姆哈斯公司的乳液开发史。罗姆哈斯公司是一家世界著名乳液生产和供应企业。因此，对于乳胶漆的发展，从中人们可以略见一斑。  \n\n表3-1-1罗姆哈斯公司的乳液开发史  \n\n\n<html><body><table><tr><td>年份/年</td><td>开发的乳液</td><td>特 点</td></tr><tr><td>1948</td><td>丁二烯-苯乙烯乳液</td><td>该乳液不是罗姆哈斯公司开发的，以下都是该公司开发的</td></tr><tr><td>1953</td><td>RhoplexAC-33纯丙乳液</td><td>全世界第一个乳胶漆用纯丙乳液</td></tr><tr><td>1961</td><td>RhoplexAC-34丙烯酸乳液</td><td>聚合时，加人功能单体，提高了附着力</td></tr><tr><td>1965</td><td>RhoplexAC-35丙烯酸乳液</td><td>好的附着力、抗粉化和保色性</td></tr><tr><td>1967</td><td>RhoplexAC-388丙烯酸乳液</td><td>好的丰满度和耐久性</td></tr><tr><td>1967~1970</td><td>RhoplexAC-22丙烯酸乳液 RhoplexAC-490丙烯酸乳液</td><td>较低成本的内墙平光乳胶漆用乳液 内墙半光乳胶漆用乳液</td></tr><tr><td>1970</td><td>RhoplexAC-507丙烯酸乳液</td><td>外墙半光乳胶漆用乳液</td></tr><tr><td>1974</td><td>Rhoplex AC-64丙烯酸乳液</td><td>在粉化基面上具有好的附着力</td></tr><tr><td>1974~1978</td><td>Rhoplex AC-417丙烯酸乳液</td><td>成本可接受的内墙半光乳胶漆用乳液</td></tr><tr><td>1979</td><td>RhoplexMV-23丙烯酸乳液</td><td>底涂用乳液</td></tr><tr><td>1980</td><td>RopaqueOP-42不透明聚合物</td><td>引人气孔，产生速盖力</td></tr><tr><td>1981~1983</td><td>AcrysolRM-4和RM-5乳液 QR-708和Acrysol MR-825乳液</td><td>疏水改性碱溶胀增稠剂（HASE) 疏水改性豪氨酯增稠剂（HEUR）</td></tr><tr><td>1983</td><td>Acrysol RM-1020 RhoplexAC-829丙烯酸乳液 RhoplexHG-74纯丙乳液</td><td>高剪切黏度疏水改性聚氨酯增稠剂（HEUR） 与HEC、HASE和HEUR兼容 外墙高光乳胶漆用乳液</td></tr><tr><td></td><td>RhoplexHG-44纯丙乳液</td><td>较硬的外墙高光乳胶漆用乳液</td></tr><tr><td>1984</td><td>Roplex HG-54丙酸乳液</td><td>金腐用用乳液 sem</td></tr><tr><td>1987</td><td>Rhoplex ML-100丙烯酸乳液</td><td>非球形粒子乳液</td></tr><tr><td>1989</td><td>Rhoplex ML-200丙烯酸乳液</td><td>配色性更好</td></tr><tr><td>1990</td><td>Rhoplex SG-10M丙烯酸乳液 Rhoplex2020NPR乳液</td><td>内外墙半光乳胶漆用乳液 水性疏水改性聚氨酯增稠剂（HEUR）</td></tr></table></body></html>  \n\n<html><body><table><tr><td>年份/年</td><td>开发的乳液</td><td>特 点</td></tr><tr><td>1993</td><td>RhoplexHG-95P纯丙乳液</td><td>具有氧化交联的外墙高光乳胶漆用乳液</td></tr><tr><td>1995</td><td>Rhoplex SF-3122丙烯酸乳液</td><td>在正常情况下，不用成膜助剂的乳液</td></tr><tr><td>1996</td><td>Acrysol RM-12W乳液</td><td>低剪切黏度水性硫水改性聚氨酯增稠剂（HEUR）</td></tr><tr><td>1998</td><td>RopaqueUltra不透明聚合物</td><td>改变粒径和粒子形态，使之更有效</td></tr><tr><td>2001</td><td>Rhoplex SG-30丙烯酸乳液</td><td>低VOC半光乳胶漆用乳液</td></tr><tr><td>2002</td><td>RhoplexHG-700丙烯酸乳液</td><td>低VOC高光乳胶漆用乳液</td></tr></table></body></html>  \n\n另据报道，在 $1930{\\sim}1935$ 年，开发了漆用油性乳液。 $1946\\sim1950$ 年，用乳液聚合法合成了丁二烯-苯乙烯乳液（简称丁苯乳液）和醋酸乙烯乳液。  \n\n1951年，用乳液聚合法合成了丙烯酸乳液。丙烯酸聚合物性能优良。  \n\n以聚醋酸乙烯乳液作为基料时，必须进行增塑，但由于增塑剂的蒸发、迁移等缺点，所以在 $1953\\sim1954$ 年前后，开发了醋酸乙烯共聚乳液。起初与顺丁烯二酸二丁酯或反丁烯二酸二丁酯的共聚为主。  \n\n1957年，瓦克化学品公司开发了醋酸乙烯均聚物可再分散乳胶粉。由于不耐碱，会皂化，不能用于对水泥改性。1959 年推出醋酸乙烯-乙烯共聚物可再分散乳胶粉。从此，开创了合成聚合物应用新天地，如对水泥改性和生产乳胶粉末涂料等。  \n\n进入20世纪60年代，突出的是醋酸乙烯-乙烯、醋酸乙烯-叔碳酸乙烯酯共聚物有所发展，产量也有所增加。20世纪60年代末，开发了硅树脂复合乳胶漆。  \n\n20世纪70年代以来，由于环境保护法强化，限制有机溶剂及有害物质的排放，而使溶剂型涂料使用受到种种限制。其中以美国加州著名的“66-法规”和美国环保局1977年提出的“四E”原则（经济、效率、环保和节能四原则）为转折点，涂料的发展朝着省资源、省能源、无污染方向发展。借此东风，乳胶漆的发展驶上了快车道。  \n\n20世纪80年代，合成了不透明聚合物、疏水改性碱溶胀增稠剂HASE、疏水改性聚氨酯增稠剂HEUR、金属防腐乳液和弹性乳液等功能性乳液。  \n\n20世纪90年代以来，乳胶漆沿着低VOC、零VOC、低气味和环境友好型进一步发展。并开发了光催化涂料。20世纪90年代末，又开发了含氟聚合物乳液，并制成了氟树脂乳胶漆。  \n\n21世纪，乳胶漆将继续沿着提高性能、增加功能、降低成本、低VOC、零VOC、低气味和环境友好型方向发展。  \n\n随着新单体的开发，乳液聚合技术的进步，各种助剂的发展，乳胶漆配方技术的改进，乳胶漆逐渐地改进和发展。它不断地蚕食着溶剂型涂料的固有领地，在建筑涂装领域，乳胶漆已成为龙头老大。在防水涂料、工业涂料和维护涂料等范围内，也有非凡表现。  \n\n随着改革开放的春风，20世纪80年代末，世界乳液生产企业罗姆哈斯（Rohm&Haas)、巴斯夫（BASF）和联碳（UnionCarbide）来我国设厂生产乳液。世界著名的助剂供应商，如汉高（Henkel)、毕克化学公司（BYK)、联合胶体（AlliedColloids）等纷纷来我国设立代表处，销售助剂，并进而在国内生产助剂。同时，卜内门（ICI)、立邦（Nip-pon）、迪诺瓦（Dinova，现为Sto申得欧）和阿克苏·诺贝尔（AkzoNobel）等“多国部队”，浩浩荡荡进人我国建厂生产乳胶漆。他们带来了新技术、新设备、新产品、新观念。他们投入大量的人力、物力资源，宣传推销自己的产品。与此同时，也就宣传推广了乳胶漆。我国乳胶漆的发展情况喜人，与发达国家的水平也基本接近。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 843,
+        "chunk": "# 二、乳胶漆的组成  \n\n通常，乳胶漆由合成树脂乳液、颜料与填料、助剂和水组成。",
+        "category": " Introduction"
+    },
+    {
+        "id": 844,
+        "chunk": "# 1.合成树脂乳液  \n\n合成树脂乳液是由乳液聚合法制取的合成树脂在水中的稳定分散体。  \n\n(1）特性和作用乳液是乳胶漆的核心。涂料用的乳液聚合物具有很好的成膜性和黏结性。干燥成膜后，它把涂料的各组分黏结在一起，形成一层薄膜，并牢牢地附着在基层上。  \n\n乳液聚合物分子量高，大约在 $10^{5}\\sim10^{7}$ ，同时乳液固含量处在比较高的水平，一般为$50\\%$ 左右，而黏度又比较低。高分子量赋予涂膜优良性能，低黏度给乳胶漆的生产、施工应用带来便利。  \n\n尽管乳液以水为分散介质，但乳液聚合物本身不溶于水，它仅以固体微粒形式分散在水中，并借助乳化剂而处于稳定状态。当水分蒸发，干燥融合成膜后，涂膜不溶于水，随着表面活性剂等亲水物质被水冲洗去以后，涂膜憎水性还会有所提高。  \n\n用于乳胶漆的乳胶粒径一般为 $0.05\\sim0.5\\mu\\mathrm{m}$ 。当处于偏细端时，乳液呈半透明。更细时，甚至可能是透明的。但通常是零点几微米，呈乳白色，其中较细时带蓝光，较粗时带红光。  \n\n目前绝大多数乳液聚合物都是线型热塑型聚合物。就是说，其干燥成膜后，涂膜会受热变软，遇冷变硬。因此，耐沾污性、抗粘连性和最低成膜温度之间存在难以调和的矛盾。目前的趋势是乳液聚合物玻璃化温度向较高方向发展。当然，开发常温交联型乳液也是解决此问题的方法之一。  \n\n(2）分类乳胶漆用热塑性聚合物乳液，通常是按其单体分类。  \n\n$\\Phi$ 醋酸乙烯系聚合物乳液该类乳液有醋酸乙烯酯均聚物乳液(简称醋均乳液)；醋酸乙烯-丙烯酸酯共聚物乳液(简称醋丙乳液，或乙丙乳液)；醋酸乙烯-叔碳酸乙烯共聚物乳液（简称醋叔乳液)；醋酸乙烯-乙烯共聚物乳液（简称EVA乳液）等。这类乳液基本上用于生产室内乳胶漆。叔碳酸乙烯含量等于或大于醋叔乳液总量的 $25\\%$ 时，醋叔乳液可用于外用乳胶漆生产。EVA乳液常用于生产可再分散乳胶粉。  \n\n$\\textcircled{2}$ 丙烯酸系共聚物乳液这类乳液有苯乙烯-丙烯酸酯共聚物乳液，简称苯丙乳液；纯（甲基）丙烯酸酯共聚物乳液，简称纯丙乳液；有机硅改性丙烯酸乳液，简称硅丙乳液等。该类乳液都可用于外用乳胶漆的生产，但苯丙乳液也大量用于内用乳胶漆生产。  \n\n$\\textcircled{3}$ 其他乳液比如聚氨酯乳液、含氟聚合物乳液等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 845,
+        "chunk": "# 2.颜料和填料  \n\n颜料和填料是乳胶漆的四大组分之一。在亚光漆中，就数量而言，是用量最大的组分。  \n\n(1）水浆化生产的发展导致了工艺的变革，颜料和填料不再以粉态出现在制漆工艺中。钛白、碳酸钙等颜料或填料品种实现水浆化，它们以 $70\\%$ 左右的固含量进入乳胶漆生产流程。  \n\n乳胶漆的生产流程演变为钛白和填料水浆散装罐车运人厂内，送入带有定时揽拌装置的贮罐，颜料浆、填料浆、乳液和助剂从各自的罐里直接按指令依顺序进入高速分散机，完成制漆后，过滤并进入成品贮罐，接到订单后，仅需配色就能交给客户。  \n\n(2）表面处理和超细化颜料有没有表面处理，这不仅关系到颜料的性能，也关系到颜料分散的难易和分散体系稳定性。涂料用颜料、填料需要有针对性的表面处理。  \n\n超细化是如今许多颜料、填料制造工艺的组成部分。超细化使乳胶漆制造企业放弃了高能耗的研磨机。但是，一般的乳胶漆不会像工业用漆那样要求极高的细度，因为细度越细，吸油量越高，乳液需用量越大，所以应综合考虑。  \n\n(3）色浆色浆的专业生产使乳胶漆制造简化，环境卫生改善，而产品质量得到提高，色浆行业在国外已经存在半个世纪，而在我国还是近几年的事。  \n\n为了适应自动调色的需要，发展了通用色浆。所谓通用色浆，是指颜色、着色力、流变性等都经过严格控制的色浆，具有较高的稳定性和批次之间的一致性。当然，这里所指的严格控制都是有具体容许误差要求的。比如，科莱恩（Colanyl）色浆，着色力要求与标准色浆比较，误差控制在 $\\pm3\\%$ 以内，即相对着色力为 $97\\%\\sim103\\%$ 。色调差 $\\triangle H$ 控制在 $\\pm0.5$ 以内，彩度差 $\\bigtriangleup C$ 控制在 $\\pm0.8$ 以内。希必思色浆的着色力控制在士1. $5\\%$ 以内，色差 $\\Delta E<$ 0.3。当然希必思色浆的颜料含量低于科莱恩色浆，也就是说，其着色力低于科莱恩色浆，所以误差可以降低。  \n\n通用色浆的生产导致建筑涂料零售业发生革命性变革。由于有了通用色浆，零售商仅需库存 $_{12\\sim16}$ 种色浆和 $2{\\sim}3$ 种待着色的基础漆，就能为客户提供上千种颜色。  \n\n此外，随着人们环保意识的提高和科学技术的发展，不含乙二醇，甚至无溶剂、低重金属含量、低甲醛释放的环境友好型色浆也已进人市场。  \n\n(4）快速分散颜料颜料一般是通过研磨分散和揽拌混合后，而加入涂料配色的。最近，开发了仅通过搅拌混合即可配色的快速分散颜料粉。这种颜料粉颗粒外有包裹层，极易分散。如巴斯夫的快速分散颜料粉（Xfast stir-in pigments）就是其中之一。  \n\n(5）不透明聚合物不透明聚合物是有机体质颜料，也称有机颜料。通常，它是苯丙共聚乳液，粒子呈中空球状，其中充满水。这是一种不成膜的乳液聚合物。当涂料成膜时，随着粒子中的水不可逆地挥发，中空部分被空气填充。不透明聚合物和空气的折射率分别为1.55和1.0，因而产生光的散射，使聚合物具有一定的遮盖力，故称不透明聚合物。  \n\n不透明聚合物除了具有一定的遮盖力外，还具有如下特点。  \n\n$\\Phi$ 粒径较细，对其他颜料，尤其是钛白粉，具有很好的空间位隔作用，能提高这些颜料的效率。  \n\n$\\textcircled{2}$ 粒子呈球形，相同体积的情况下表面积最小，因此乳液需要量最少，故能提高乳胶漆的临界颜料体积浓度CPVC。在相同乳液用量的情况下，能提高乳胶漆的性能。在相同性能的情况下，可减少乳液用量。  \n\n$\\textcircled{3}$ 粒子细而均匀，使乳胶漆膜表面平整，减少积灰，提高了耐沾污性。  \n\n$\\textcircled{4}$ 不需分散，只需搅拌混合均匀。  \n\n$\\textcircled{5}$ 密度低，自重轻。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 846,
+        "chunk": "# 3.水和助溶剂  \n\n在乳胶漆中水起分散介质的作用。助溶剂具有四个功能：一是调节水挥发速率，防止接痕出现；二是协同成膜助剂促进乳胶漆成膜；三是降低乳胶漆的冰点，起防冻作用；四是降低水的表面张力，提高对颜料和基层的湿润能力。  \n\n（1）水水不仅是乳胶粒的分散介质，约占乳液总重量的 $50\\%$ ，而且作为颜料和填料的分散介质，约占乳胶漆总重量的 $35\\%\\sim50\\%$ 。乳胶漆生产用水不像乳液聚合用水那样严格，自来水和饮用水都可以用，但应尽量注意多价离子含量。因为多价离子不仅压缩双电层有效厚度而影响乳胶漆稳定性，而且水的硬度还影响分散剂的用量。与普通溶剂相比，水具有明显不同的性质，详见表3-1-2。  \n\n$\\Phi$ 水无毒无味，完全满足环境友好要求。  \n\n表3-1-2水和有机溶剂性能比较  \n\n\n<html><body><table><tr><td>性能</td><td>水</td><td>有机溶剂（二甲苯)</td></tr><tr><td>环境友好型</td><td>无毒无味</td><td>有毒有芳香气味</td></tr><tr><td>安全性</td><td>不爆炸、不燃烧</td><td>一级易燃、爆炸极限低</td></tr><tr><td>闪点（闭口）/℃</td><td>一</td><td>25.3</td></tr><tr><td>沸点/C</td><td>100</td><td>135~143</td></tr><tr><td>凝固点/℃</td><td>0</td><td>25</td></tr><tr><td>溶解度参数/（×103J1/2/m/2） 8d 8</td><td>12.6 32.1</td><td>17.8 1.0</td></tr><tr><td>品</td><td>35.1</td><td>3.1</td></tr><tr><td>氢键参数</td><td>49.3 39. 0</td><td>18.0 4.5</td></tr><tr><td>偶极距/D</td><td>1.8</td><td>0.4</td></tr><tr><td>表面张力（20℃）/(mN/m)</td><td>72.8</td><td>30.0</td></tr><tr><td>黏度（20℃）/mPa·s</td><td>1.0</td><td>0.8</td></tr><tr><td>相对蒸发速率（醋酸丁酯E-1）</td><td>0.31(25C,RH=0.5%)</td><td>0.68</td></tr><tr><td>蒸气压（25C）/X10²Ps</td><td>0(25°C,RH=100%) 23.8</td><td></td></tr><tr><td>比热容/J/(g·C)</td><td>4.2</td><td>1.7</td></tr><tr><td>蒸发潜热（101.3kPa)/(kJ/mol)</td><td>44</td><td>36</td></tr><tr><td>介电常数（20℃）</td><td>80.1</td><td>2.4</td></tr><tr><td>热导率/[kW/（m²·C）]</td><td>5.8</td><td>1.6</td></tr><tr><td>相对密度</td><td>1.0</td><td>0.9</td></tr><tr><td></td><td></td><td></td></tr><tr><td>折射率</td><td>1.3</td><td>1.5</td></tr></table></body></html>\n\n$\\textcircled{1}10=3,34\\times10^{-20}\\mathrm{C}\\cdot\\mathrm{m},$  \n\n$\\textcircled{2}$ 水不爆炸，不燃烧，安全无害。  \n\n$\\textcircled{3}$ 尽管淡水仅占地球上总水量的 $0.73\\%$ ，但相对于溶剂来说，水还是属于便宜易得。  \n\n$\\textcircled{4}$ 借助于助剂，以水为分散介质的乳胶漆性能可满足需要。  \n\n这四点就是选用水作为乳胶漆分散介质的原因，但以水为分散介质确实也有许多不利因素。  \n\n$\\Phi$ 水的表面张力比有机溶机高得多，这就导致对颜料、填料和被涂基层湿润较差的问题。为此，需加入表面活性剂来降低表面张力。而表面活性剂的加入也会造成气泡的问题，所以又需加消泡剂，从而使配方复杂化。另外，乳胶漆成膜后，表面活性剂留在涂膜中，影响涂膜耐水性，并且可能成为渗透剂。 2  \n\n$\\textcircled{2}$ 水具有与有机溶剂完全不同的溶解度参数。它与有机溶剂相比，具有明显的极性，形成很强的氢键。在乳胶漆中，水不是溶剂，它不能溶解乳液聚合物，在使用环境中也不允许它溶解乳液聚合物，它只是分散介质而已。而在溶剂型涂料中，溶剂是要溶解成膜物的。  \n\n$\\textcircled{3}$ 与有机溶剂相比，水的蒸发热高。因此乳胶漆干燥成膜时需要更多的热量，也需要更长的时间。  \n\n$\\textcircled{4}$ 水的挥发速率与环境的相对湿度和温度以及基层的温度关系甚大。 $25\\mathrm{{C}}$ ， $\\mathbf{RH}=0\\sim$ 5%时，水在滤纸上的相对蒸发速率是0.31，当 $R H=100\\%$ ，水的相对蒸发速率成为0。温度愈高，水的挥发速率愈快。此外，还与风速有关。  \n\n$\\textcircled{5}$ 水在0℃结冰。尽管加入防冻剂、成膜助剂和溶质后，冰点会下降，以至乳胶漆能通过 $-5t$ 的低温贮存稳定性的检验。但为了保险起见，乳胶漆还是应贮存在水的凝固点 $0^{\\circ}\\mathrm{C}$ 以上。  \n\n$\\textcircled{6}$ 水的介电常数高。可以通过静电斥力使体系稳定。而有机溶剂介电常数低，一般通过空间位阻稳定。当然，水性体系也有空间位阻稳定。  \n\n$\\textcircled{7}$ 水的电导率高，易使金属腐蚀，所以乳胶漆最好采用塑料桶包装。电导率高还使乳胶漆静电喷涂困难。  \n\n$\\textcircled{8}$ 与溶剂型涂料的基料相比，水的黏度低，所以乳胶漆需要增稠剂增稠，才能保持较好的贮存稳定性和施工性。  \n\n$\\textcircled{9}$ 水是微生物生存的温床，因此乳胶漆生产用水应注意杀菌、防腐、保洁。自动化程度越高，越要重视此问题。  \n\n(2）助溶剂这里所说的助溶剂是指丙二醇、乙二醇、 $200^{\\#}$ 溶剂油和埃克森化工公司(Exxon）D60等一些溶剂，有些书也把它们归入成膜助剂，但它们要么水溶性太大，要么一点也不溶于水，单独使用时，降低乳胶成膜温度的能力很有限，往往是与成膜助剂配合使用，所以称它们为助溶剂。  \n\n这些助溶剂能软化或溶解乳胶微粒，协同成膜助剂促进乳胶漆成膜。这些助溶剂挥发速度比水慢，所以有利于延长乳胶漆的开放时间和搭接时间，从而有利于乳胶漆在基面上的铺展，并且避免出现接痕。有些助溶剂如丙二醇、乙二醇等冰点较低，还能降低乳胶漆的冰点，提高乳胶漆的低温稳定性和防冻能力。有些助溶剂如乙二醇表面张力比水低，所以当其加入水中时，能降低水的表面张力，从而提高对颜料和基层的湿润能力。助溶剂还对乳胶漆的黏度有调节作用，如二醇类助溶剂的存在，会降低协和型增稠剂的增稠效果。一些助溶剂的性能列于表3-1-3。  \n\n表3-1-3助溶剂的性能  \n\n\n<html><body><table><tr><td>性能</td><td>乙二醇</td><td>1.2-丙二醇</td><td>200*溶剂油</td><td>Exxsol D60</td></tr><tr><td>沸程（101.3kPa)/C</td><td>198</td><td>187</td><td>145~200</td><td>181~216</td></tr><tr><td>熔点/C</td><td>12.6</td><td>59.5</td><td></td><td></td></tr><tr><td>相对密度（20°℃）</td><td>1.1155</td><td>1. 0381</td><td>0.780</td><td>0.787</td></tr><tr><td>折射率(20℃）</td><td>1.4318</td><td>1.4329</td><td></td><td></td></tr><tr><td>介电常数（20℃）</td><td>38.66</td><td>32.0</td><td></td><td></td></tr><tr><td>偶极矩（30℃）/×10-C·m</td><td>7.34</td><td>7.51</td><td></td><td></td></tr><tr><td>黏度/mPa * s</td><td>25. 66(16°C)</td><td>56.0(20°C)</td><td></td><td>1.28</td></tr><tr><td>表面张力/（mN/m）</td><td>46.49(20°C)</td><td>72.0(25°C)</td><td></td><td>24.9</td></tr><tr><td>闪点/C</td><td>111.1</td><td>98.9（闭口）</td><td>≥33（闭口）</td><td>64</td></tr><tr><td>燃点/℃</td><td>118</td><td>421</td><td></td><td></td></tr><tr><td>溶解性</td><td>能与水混溶</td><td>能与水混溶</td><td>不溶于水</td><td>不溶于水</td></tr><tr><td>蒸发热/(kJ/mol)</td><td>57.11</td><td>538. 1kJ/kg</td><td></td><td></td></tr><tr><td>爆炸极限（下限，体积分数）/%</td><td>3.2</td><td>2.6</td><td></td><td></td></tr><tr><td>挥发速率</td><td></td><td></td><td>3~4.5</td><td>5</td></tr><tr><td>芳香烃含量/%</td><td></td><td></td><td>≤15</td><td>0.7</td></tr></table></body></html>  \n\n助溶剂的功能与许多因素有关，如极性、HLB值和挥发速率等，但有一点是很明显的，与其在乳胶漆中所处的位置紧密相关。如果较取向于在水中的话，则较多地表现为流变助剂、防冻剂、干燥调节剂和湿润剂的作用。如果较取向于在聚合物粒子中的话，则较多地表现为成膜助剂的作用。如 $200^{\\circ}$ 溶剂油、D60和成膜助剂复配，对苯丙乳液的成膜很有帮助。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 847,
+        "chunk": "# 4.助剂  \n\n乳胶漆以水为分散介质，具有环境友好和安全特点，但水也给其生产和应用带来一些问题。这些问题都是通过助剂来解决的。尽管助剂用量只有千分之几至百分之几，但它对乳胶漆的生产工艺、产品质量、稳定贮存、方便施工和涂膜性能等都有很大作用。乳胶漆所用助剂比较多，有湿润分散剂、消泡剂、增稠剂、成膜助剂、防腐防霉剂和 $\\mathfrak{p H}$ 调节剂等，从而致使乳胶漆的配方比较复杂，这也是乳胶漆的一个缺点。助剂详见第二篇第四章内容。",
+        "category": " Introduction"
+    },
+    {
+        "id": 848,
+        "chunk": "# 三、乳胶漆的配方设计  \n\n乳胶漆的配方设计是一项综合性的工作，目前还处于技艺至科学的转变过程中。配方设计首先要目标明确，其次是对原材料的了解，包括其价格，以及对各组分相互作用的知识。另外，还要有比较丰富的经验等，才能完成一个比较合理的乳胶漆配方设计。",
+        "category": " Introduction"
+    },
+    {
+        "id": 849,
+        "chunk": "# 1.性能目标确定  \n\n当接受一项乳胶漆的配方设计任务时，首先要明确的是所设计乳胶漆品种的应用目标和性能要求，当然也包括环保方面的要求。无论所设计的是通用或专用品种，都要既定性又定量地列出要求达到的技术指标，并明确考核各项指标的检测方法。如果研制的是一个通用型品种，则很可能这些指标就是既有的国内外某个标准或层次的技术指标。如果研制的是一个特殊品种，则所罗列的技术指标将来会构成一个新的产品标准。  \n\n这里要注意的是：首先，不要盲目地把指标定得过高，因为高指标是要高成本支撑的，以够需要为度；其次，要兼顾性能的平衡，不要顾此失彼；最后，乳胶漆性能测试结果往往波动比较大，所以确定指标时，既要心中有数，又要留有余地。",
+        "category": " Introduction"
+    },
+    {
+        "id": 850,
+        "chunk": "# 2.原料选择  \n\n目标确定后，接着就是选择原材料。有一点是共同的，就是不管什么原料，都要求其稳定，稳定对生产是十分重要的。原料选择关系到供应商的选择。一定要选择那些不仅能提供合格原料，而且能提供稳定合格原料与优质服务的供应商和生产厂家。  \n\n(1）乳液选择对于内墙乳胶漆，一般可选用苯丙乳液、醋丙乳液、醋叔乳液和醋酸乙烯-乙烯共聚乳液。国内用得较多的是苯丙乳液和醋丙乳液。醋丙乳液价格适中，苯丙乳液黏结颜料能力高。  \n\n对于外墙乳胶漆，硅丙乳液、纯丙乳液、苯丙乳液、醋叔乳液均可选择。国内目前用得最多的也是苯丙乳液，因为其性能价格比易于被人们接受。  \n\n玻璃化温度、最低成膜温度、平均粒径和粒径分布等是影响聚合物乳液选择的定量指标，如有光乳胶漆一般选用 $T_{*}$ 较高的乳液，平均粒径较细的乳液对颜料、填料的黏结能力往往比较强。但真正决定乳液选择的往往是一些说明书上没有直接表达的定性和定量指标或因素。例如，聚合物的构成、残余单体含量、乳液对漆膜光泽、附着力、物理机械性能和室内外耐用性能的影响等。这些指标或因素，有的是厂家保密而难以提供，有的是配方影响因素太多，无法简单的定量。但是对产品说明书的全面消化，尤其是它们的配方举例，包括与乳液供应厂家技术人员的交流，加上自身对聚合物乳液的知识积累，能较准确地选出有资格进入筛选过程的备选品，然后通过试验比较确定。例如如下做法。  \n\n将乳液涂布在玻璃板上，如在 $(50\\pm2)\\tau$ 放置4h，观察乳液膜的透明度，越透明越好。  \n\n将上述玻璃板浸泡在蒸馏水中，观察其出现泛白所需的时间，时间越长说明耐水性越子。这可用于选择真石漆用乳液参考。当然，影响因素很多，应具体问题具体分析。  \n\n对外墙乳胶漆用乳液的选择，也可通过白石试验（Whitestone test)。所谓白石试验，就是以白色大理石屑片为填料配制乳胶漆，白色大理石屑片是易显色粒子，经人工加速老化或自然曝晒后，很易鉴别，从而确定乳液性能的一种试验方法。  \n\n白石试验乳胶漆的配方见表3-1-4。  \n\n表3-1-4白石试验乳胶漆的配方  \n\n\n<html><body><table><tr><td>No</td><td>原 料</td><td>配 比</td></tr><tr><td>1</td><td>乳液（50%)</td><td>195</td></tr><tr><td>2</td><td>羟乙基纤维素（4%)</td><td>36</td></tr><tr><td>3</td><td>乙氧基醋酸丁酯(butyloxyethyl acetate）</td><td>15</td></tr><tr><td>4</td><td>防腐剂</td><td>2</td></tr><tr><td>5</td><td>白色大理石屑片（2mm）</td><td>750</td></tr><tr><td>6</td><td>消泡剂</td><td>2 1000</td></tr><tr><td colspan=\"3\">合计</td></tr></table></body></html>  \n\n将该白石试验乳胶漆用 $0.03\\%$ 菁蓝着色。试验表明， $0.03\\%$ 酞菁蓝对乳液试验影响可以忽略。  \n\n选用白色大理石屑片，一是因为当蓝色乳液膜粉化脱落后，白色大理石就显示出来，很容易识别；二是减少填料吸收紫外线而对试验结果的影响。  \n\n加入乙氧基醋酸丁酯，是为了避免干燥时间的差异。  \n\n可在纤维水泥板上涂布白石试验乳胶漆进行试验。  \n\n据介绍，用白石试验法评估聚合物乳液光化学稳定性，可以比自然曝晒缩短 $4{\\sim}5$ 倍的试验时间。白石试验表明，如果一种聚合物乳液仅6个月就有可以看得出的降解，该乳液不应用于富含乳液的配方中，如有光漆和清漆。  \n\n(2）颜料填料选择一般乳胶漆所用的颜料，其所起作用不外是提供遮盖力和装饰性。对颜料的首要要求是具有尽可能高的遮盖力和明亮、美丽的颜色。但是，为了使颜料得以长远地履行其遮盖和装饰的作用，还必须十分地注意颜料的稳定性和易分散性。对光稳定可以保色性好，耐久性佳；对热稳定可以耐烘烤；物理化学性质的稳定可保乳胶漆黏度的稳定，耐候性好；分散状态稳定包括不沉淀、不絮凝、不浮色、不发花等。易分散性的重要性是不言自明的，它有助于控制工厂的投资，有助于降低生产的成本，并提高产品质量。  \n\n常规颜色包括红、黄、蓝、绿、白、黑、金属色等，对乳胶漆来说，一般白色用得较多。钛白粉，尤其是金红石钛白粉是最好的白色颜料。国外发达国家不仅外墙乳胶漆，而且内墙乳胶漆也用金红石型钛白粉。对水性漆和有光漆，厂商均有专品供应，配方师们也很熟悉，针对性地选用，必能受惠。在工业发达国家，生产乳胶漆时，不用立德粉。但是，国内在生产内墙乳胶漆时，也有使用立德粉的。立德粉配方平衡费力，遮盖力低，耐光耐候性差。氧化锌在乳胶漆中可部分地用于防腐蚀颜料或防霉，也有遮盖作用，对含游离羧基的聚合物不宜选用。彩色和黑色颜料其作用不过是配色而已。因此，着色力是否够强，着色牢度是否够高，色相是否纯正鲜明，就很重要。此外，墙漆的基材通常为水泥砂浆和混合砂浆，碱性较强，因而颜料的耐碱性也是重要的。这就是为什么建筑乳胶漆不使用铁蓝的原因。在我国，外用漆常采用深色调，红色、绿色也很普遍。这时，对颜料的耐晒牢度就有较高的要求。红色以氧化铁红为主。在当前的国内市场上，色相较鲜而耐晒优良的氧化铁红已不难得，它们也具有极佳的抗酸碱性。如果要求极鲜艳的红色，那就只能求诸价格昂贵的高级有机红了。如颜料红254和颜料红168等。黄色以氧化铁黄为主，如要比较鲜艳的黄色，有高价格的钒酸（颜料黄184)，或有机黄，如颜料黄109和颜料黄110等。绿色有酞菁绿，蓝色有酞菁蓝和钴蓝，黑色有氧化铁黑和炭黑。有机颜料和炭黑都是难分  \n\n散的亲油性颜料。  \n\n乳胶漆对颜料的另一个要求就是遮盖力。金红石型钛白粉的遮盖力是最好的，其他颜料也有一定遮盖力，具体视其对光的散射和吸收能力而异。鲜艳的黄色和红色乳胶漆应特别注意其遮盖力是否达到要求。  \n\n在乳胶漆中使用填料亦称体质颜料，有如下结果：降低成本；增加乳胶漆的稠度，防止颜料填料的沉降；影响乳胶漆的流动性、流平性；影响漆膜的光泽；有助于漆膜染污的清除；增加漆膜的抗抛光性；影响漆膜的耐久性、粉化性和耐擦洗性；增加漆膜的整体性和屏蔽性等。填料的品种又非常多，选择起来确实比较复杂。但是，既然叫做填料，便宜当然是第一要义，光图便宜自然不行，还要根据主次，兼顾其他目的。作为填料，在乳胶漆中加得越多，成本降低越甚。但是，其添加量需视乳胶漆的性能要求、填料的细度、吸油量等而定，还要考虑黏结剂对颜料的黏结力。  \n\n填料的吸油量在许多手册中或产品说明书中可以查到。细度在产品说明书上会有记载。现在，许多填料也有超细分散的品种。它们白度好、沉降性低，在使用上有其有利之处。但价格较贵，吸油量高，用量上有时会受到限制。在给定的条件下，吸油量高，细度细，往往用量低；反之则高。定配方时，必须根据具体情况加以权衡。常用填料及其特性见表3-1-5。  \n\n表3-1-5常用填料及其特性  \n\n\n<html><body><table><tr><td>填料</td><td>特 性</td></tr><tr><td>烧高岭土</td><td>干这盖力好，悬浮性好，降低流挂，吸油量较高</td></tr><tr><td>石英粉</td><td>消光，抗抛光，耐磨，耐擦洗</td></tr><tr><td>滑石粉</td><td>易粉化，防沉降，提高漆膜屏蔽性和整体性，施工性好</td></tr><tr><td>重质碳酸钙</td><td>可改善保色性和抗粉化性，超细粒子能提供位隔作用，增加钛白粉遮盖效能</td></tr><tr><td>轻质碳酸钙</td><td>悬浮性较好，能提供位隔作用，吸油量高，室外耐久性稍差</td></tr><tr><td>沉淀硫酸</td><td>不易起白霜和染污，吸油量低，易沉降</td></tr><tr><td>硅灰石粉</td><td>耐候性好，耐洗刷，易沉降</td></tr><tr><td>云母粉</td><td>增强漆膜坚韧性，减少漆膜透水性，抗紫外线，防开裂</td></tr></table></body></html>  \n\n不同填料的粒子形状是不相同的，具有片状粒子的滑石粉能提高涂膜的整体性，从而也对耐水性、耐碱性等有利。具有圆形粒子的碳酸钙，则当粗细搭配使用时，容易发挥其填充效应。填料粒径较粗，具有对漆膜消光作用。  \n\n金红石型钛白粉虽有最高的散射能力，但价格也很高，如果其颗粒产生附聚，就会影响其遮盖能力的发挥。体质颜料，如碳酸钙、滑石粉和高岭土等，其折射率基本与乳液聚合物相同，因此没有遮盖力。但较细的体质颜料，通过调节钛白粉在涂膜中空间位置，使钛白粉不团聚，达到最大的光散射能力，从而得到最高的遮盖力。而粗的体质颜料，由于造成钛白粉在其粒隙中聚集，从而降低了钛白粉的遮盖效率。对遮盖力问题颇有研究的Steig认为，体质颜料粒径为钛白粉粒径的四倍（约 $0.8\\mu\\mathrm{m}$ ）时，空间位隔作用十分有效，钛白粉能得到最有效的光散射。  \n\n在可取代钛白粉的填料中，应提及有机体质颜料或称为不透明聚合物，将其用于乳胶漆配方中，除达到取代部分钛白粉的作用外，对提高漆膜硬度、平滑度、内用漆的耐擦洗性、外用漆的抗积尘性均有明显效果。  \n\n填料选择时还应注意搭配使用。不同填料搭配得好，不仅能提高涂膜的密实度，还可降低乳液用量。从而达到降低成本、提高性能的目的。  \n\n（3）助剂选择乳胶漆配方中必须使用众多品种的助剂，这里仅提三点。  \n\n$\\Phi$ 任何助剂，当使用得当时，就会发挥事半功倍的正面作用，但它门也必然会有副作用。如湿润分散剂，能降低水的表面张力，促进颜料、填料的湿润分散，提高其分散稳定性，同时有利于涂料对基面的湿润。但湿润分散剂在生产和施工中会产生气泡；乳胶漆成膜后，湿润分散剂留在涂膜中，就成为渗透剂，从而提高涂膜的吸水性，降低耐水性和耐洗刷性。  \n\n$\\textcircled{2}$ 任何助剂，其用量均以能解决问题为度，超量使用是花钱买副作用。  \n\n$\\textcircled{3}$ 要十分注意助剂之间的相互作用，竞争吸附。要把助剂放在乳胶漆体系中考虑，如乳液的乳化剂，色浆的湿润分散剂和增稠剂等，都要统一考虑，不能就助剂论助剂。要使其相互增益，防止相互抵消，甚至出现麻烦。  \n\n因此，要从助剂的组成、结构和作用机理出发，通过试验和不断实践，积累经验，逐步进人“自由王国”。  \n\n(4）水和助溶剂的选择也许人们要问，水还要选择？水是乳胶漆的一个组分，应该注意其质量。尤其是多价离子和细菌，长期在水箱中静置的水要杀菌处理后才能用，尤其是在天热时。还有铁锈和杂质，应过滤掉。助溶剂的选择应注意性能与环保的统一，如目前的趋势是用丙二醇，尽管乙二醇性能不错，也不用乙二醇。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 851,
+        "chunk": "# 3.颜料体积浓度（PVC）和颜基比（P/B)  \n\n(1）PVC 和CPVC颜料体积浓度是指涂膜中颜料和填料的体积占涂膜总体积的百分数，以PVC表示，如下式所示。  \n\n$$\n\\mathrm{PVC}={\\frac{V_{\\mathrm{p}}+V_{\\mathrm{e}}}{V_{\\mathrm{p}}+V_{\\mathrm{e}}+V_{\\mathrm{b}}}}={\\frac{{\\frac{W_{\\mathrm{p}}}{d_{\\mathrm{p}}}}+{\\frac{W_{\\mathrm{e}}}{d_{\\mathrm{e}}}}}{{\\frac{W_{\\mathrm{p}}}{d_{\\mathrm{p}}}}+{\\frac{W_{\\mathrm{e}}}{d_{\\mathrm{e}}}}+{\\frac{W_{\\mathrm{b}}}{d_{\\mathrm{b}}}}}}\n$$  \n\n式中， $\\boldsymbol{V}_{\\flat}$ 为颜料体积； $\\boldsymbol{v}_{\\ast}$ 为填料体积； $\\boldsymbol{V_{\\mathrm{b}}}$ 为干乳液聚合物体积； $\\boldsymbol{W}_{p}$ 为颜料质量；$\\boldsymbol{w}_{\\mathrm{~e~}}$ 为填料质量； $\\boldsymbol{W_{\\flat}}$ 为干乳液聚合物质量； $d_{p}$ 为颜料密度；d为填料密度； $d_{\\mathrm{b}}$ 为干乳液聚合物密度。  \n\n涂料中最主要的固体组分是颜料、填料和基料聚合物。它们也是构成干膜的关键组分。从某种意义上说，颜料和填料在涂膜中起骨架作用，而乳液聚合物起黏结作用。PVC就是反映这三者在涂膜中的体积关系。PVC高，说明黏结剂少，颜料填料多；反之，说明黏结剂多，颜料填料少。  \n\nPVC可根据涂料性能要求来确定，也能按配方进行计算。  \n\n临界颜料体积浓度是指基料聚合物恰好覆盖颜料和填料粒子表面，并充满颜料和填料粒子堆积所形成空间时的颜料体积浓度，以CPVC表示。乳胶漆的临界颜料体积浓度一般以LCPVC 表示。CPVC的计算公式如下。 Ar  \n\n$$\n\\mathrm{CPVC}{=}\\frac{1}{1{+}\\frac{\\mathrm{OA}\\rho}{93.5}}\n$$  \n\n式中OA—吸油量， $\\mathbf{g}/100\\mathbf{g}$ $\\rho$ 一颜料密度， $\\mathbf{g}/\\mathbf{cm}^{3}$ 93.5—亚麻仁油密度， $\\times100$  \n\n由式（3-1-2）可以看出，颜料吸油量低些能提高涂料的CPVC，从而在相同的原材料成本下，得到较好性能的涂料。或者在相同涂料性能时，降低成本，但有时也并非绝对如此。  \n\n最初选定亚麻仁油作为吸油量介质是很自然的，因为20世纪20年代，亚麻仁油是主要的涂料基料。现在涂料工业仍继续采用亚麻仁油来评价涂料颜料，但也出现了一些替代  \n\n液体。  \n\n由于乳胶漆是以水为分散介质，所以也有以吸水量来评价乳胶漆用颜料。  \n\n乳胶漆一般由多种颜料和填料配制而成，CPVC也可通过式（3-1-3）计算。  \n\n$$\n\\mathrm{CPVC}=\\frac{\\displaystyle\\sum_{i=1}^{n}\\frac{W_{i}}{\\rho_{i}}}{\\displaystyle\\sum_{i=1}^{n}\\frac{W_{i}}{\\rho_{i}}+\\sum_{i=1}^{n}\\frac{\\mathrm{OA}_{i}W_{i}}{93.5}}\n$$  \n\n式中 $\\boldsymbol{W}_{i}$ -颜料i的质量，g;  \n\n$\\rho_{i}$ —颜料i的密度， $\\mathsf{g}/\\mathsf{c m}^{3}$ $\\mathrm{OA}_{i}$ -颜料i的吸油量， $\\scriptstyle{\\mathbf{g}/100_{\\mathbf{E}}}$ 计算CPVC可供参考。计算例子见配方举例一节。  \n\n(2）LCPVC 的测定LCPVC可以通过涂膜性能在LCPVC 附近小范围内突变来测定，例如，干膜应力、孔隙率、遮盖力和透水汽性等。  \n\n$\\textcircled{1}$ 沥青LCPVC测定法（Gilsonite test）该方法原理是利用涂膜对沥青溶液的不可逆吸收，同时孔隙率越大，吸收沥青溶液越多，变色越明显。因为在LCPVC处，涂膜孔隙率突然增大，所以测定一系列不同PVC涂膜试板在浸沥青溶液前后颜色变化，就能确定LCPVC。  \n\n$\\textcircled{2}$ 应力LCPVC测定法该测定方法的原理是在LCPVC处涂膜中应力最大，因此卷曲也最厉害，从而就能确定LCPVC。  \n\n测定LCPVC还有遮盖力法、透水汽法和消色力法等。  \n\n(3）影响LCPVC的因素乳胶漆的临界颜料体积浓度不同于溶剂涂料CPVC，一般认为，在相同的颜料和填料时，LCPVC小于溶剂涂料CPVC。它不仅与颜料和填料包覆性有关，而且还和乳液、成膜助剂和成膜时的温度等有关。  \n\n$\\Phi$ 乳液的影响乳液对LCPVC的影响见表3-1-6。这六种商品乳液的组成和结构互不相同。  \n\n表3-1-6乳液对LCPVC的影响  \n\n\n<html><body><table><tr><td rowspan=\"2\">No.</td><td rowspan=\"2\">乳液类型</td><td rowspan=\"2\">图含量</td><td rowspan=\"2\">平均粒径</td><td rowspan=\"2\">MFT</td><td rowspan=\"2\">稳定系统</td><td colspan=\"4\">对比CP/造水汽法</td></tr><tr><td>沥青法</td><td></td><td></td><td>平均</td></tr><tr><td>1</td><td>苯丙</td><td>50</td><td>0.15</td><td>22</td><td>乳化剂</td><td>58</td><td>59</td><td>61</td><td>59</td></tr><tr><td>2</td><td>苯丙</td><td>50</td><td>0.1</td><td>20</td><td>乳化剂</td><td>59</td><td>60</td><td>61</td><td>60</td></tr><tr><td>3</td><td>苯丙</td><td>50</td><td>0.1</td><td>7</td><td>乳化剂</td><td>59</td><td>58</td><td>61</td><td>59</td></tr><tr><td>4</td><td>苯丙</td><td>50</td><td>0.15</td><td>8</td><td>乳化剂</td><td>56</td><td>55</td><td>56</td><td>56</td></tr><tr><td>5</td><td>纯丙</td><td>50</td><td>0.1</td><td>13</td><td>乳化剂</td><td>59</td><td>61</td><td>62</td><td>61</td></tr><tr><td>6</td><td>乙烯氯乙</td><td>50</td><td>0.7</td><td>4</td><td>保维体</td><td>53</td><td>55</td><td>53</td><td>54</td></tr></table></body></html>  \n\n结合其他试验得出，相同组成和结构的乳液聚合物粒子变细，LCPVC升高。不同组成和结构的聚合物乳液，既使聚合物粒径相同，LCPVC也不同。乳液聚合物 $T_{\\mathrm{*}}$ 下降，LCPVC提高。从表3-1-6还可以看出，同类乳液，如 $\\mathrm{v}_{0}.1{\\sim}\\mathrm{No}.\\mathrm{\\dot{4}}$ 苯丙乳液，LCPVC有变化，但不大。  \n\n$\\textcircled{2}$ 钛白粉的影响钛白粉对LCPVC 的影响如图 3-1-1所示。LCPVC 以沥青法测定，试验所用的金红石型钛白粉列于表3-1-7。填料分别采用沉淀碳酸钙SocalP2和方镁石粉  \n\nMicrodol1。SocalP2平均粒径0.3μm，吸油量26g/100g。Microdol1平均粒径7μm，吸油量 $11\\mathbf{g}/100\\mathbf{g}$ 。钛白粉：填料 $=40:60$ 9  \n\n表3-1-7试验所用的钛白粉  \n\n\n<html><body><table><tr><td>No.</td><td>钛白粉</td><td></td><td>TiO/%吸油量/（g/100g）No.</td><td></td><td>饮白粉</td><td>TiOz/%</td><td>吸油量/（g/100g）</td></tr><tr><td></td><td>Kronos 2044</td><td>82</td><td>35</td><td>4</td><td>Kronos 2190</td><td>94</td><td>18</td></tr><tr><td>2</td><td>Kronos 2043</td><td>85</td><td>34</td><td>5</td><td>Kronos 2300</td><td>94</td><td>16</td></tr><tr><td>3</td><td>Kronos 2065</td><td>93</td><td>21</td><td>6</td><td>Kronos 2310</td><td>93</td><td>18</td></tr></table></body></html>  \n\n![](images/1807a8f7819269a10fdcc371766df9baa22fccce159ac13d3625e541a9f74ff8.jpg)  \n图3-1-1钛白粉No $\\begin{array}{r}{1\\sim\\mathbf{N}\\circ.}\\end{array}$ 4、No.6 对LCPVC的影响△LR为反射系数差  \n\n表3-1-8试验所用填料  \n\n\n<html><body><table><tr><td rowspan=\"2\">No.</td><td rowspan=\"2\">填 料</td><td rowspan=\"2\">平均粒径</td><td rowspan=\"2\">吸油</td><td rowspan=\"2\">No.</td><td rowspan=\"2\">填 料</td><td rowspan=\"2\">平均粒径</td><td rowspan=\"2\"></td></tr><tr><td></td></tr><tr><td>1</td><td>重质碳酸钙，Durcal 2</td><td>3</td><td>18</td><td>4</td><td rowspan=\"2\">滑石粉，Talcum N 铝硅酸盐，P820</td><td rowspan=\"2\">S</td><td rowspan=\"2\">32</td></tr><tr><td>2</td><td>沉淀碳酸钙，Socal P2</td><td>0.3</td><td>26</td><td>5</td></tr><tr><td>3</td><td>方镁石粉，Microdol1</td><td>7</td><td>11</td><td></td><td></td><td>0.035</td><td>120</td></tr></table></body></html>  \n\n由图3-1-1可以看出，钛白粉的吸油量越低，LCPVC就越高。  \n\n![](images/fc3a7f478f1a8e8f1c6a057389e7bdc2dbcc3b46059f9ac16042a544b055e272.jpg)  \n图3-1-2填料No. $1\\sim\\N_{0\\cdot}$ 5对LCPVC的影响LR为反射系数差  \n\n$\\textcircled{3}$ 填料的影响填料对LCPVC的影响如图3-1-2所示。LCPVC以沥青法测定，试验所用的钛白粉同样见表3-1-7，填料见表3-1-8。钛白粉：填料 $=10:90$ 。  \n\n一般来说，填料的粒径越细，吸油量越大，LCPVC就越低。如铝硅酸盐P820，LCPVC低至 $40\\%$ 。这是一种很容易使涂膜产生干燥裂缝的填料。  \n\n另外，片状滑石粉TalcumN的吸油量是 $32g/100g$ ，以沥青法测得的LCPVC却高达 $74\\%$ ，当然，这是一个偏高的数据。实际上，以应力法测得的LCPVC是  \n\n$64\\%$ 。这说明，一是高吸油量有时也不一定就得低LCPVC；二是沥青LCPVC测定法存在一定的局限性。  \n\n表3-1-9是不同金红石型钛白粉和不同填料混合物的LCPVC。  \n\n表3-1-9不同金红石型钛白粉和不同填料混合物的LCPVC 单位：%  \n\n\n<html><body><table><tr><td rowspan=\"2\">钛白粉</td><td rowspan=\"2\">吸油量 /(g/100g)</td><td rowspan=\"2\">钛白粉 /填料</td><td colspan=\"2\">沉淀碳酸钙，Socal P2</td><td colspan=\"2\">重质碳酸钙，Durcal2</td><td colspan=\"2\">方镁石粉，Microdol 1</td></tr><tr><td>沥青法</td><td>应力法</td><td>沥青法</td><td>应力法</td><td>沥青法</td><td>应力法</td></tr><tr><td>Kronos 2043</td><td>34</td><td>10/90</td><td>50</td><td>50</td><td>61</td><td>62</td><td>64</td><td>66</td></tr><tr><td>Kronos 2065</td><td>21</td><td>10/90</td><td>50</td><td>50</td><td>61</td><td>62</td><td>64</td><td>66</td></tr><tr><td>Kronos 2190</td><td>18</td><td>10/90</td><td>51</td><td>52</td><td>62</td><td>64</td><td>65</td><td>66</td></tr><tr><td>Kronos 2300</td><td>16</td><td>10/90</td><td>52</td><td>52</td><td>62</td><td>62</td><td>64</td><td>64</td></tr><tr><td>Kronos 2044</td><td>35</td><td>40/60</td><td>50</td><td>48</td><td>57</td><td>56</td><td>62</td><td>60</td></tr><tr><td>Kronos 2043</td><td>34</td><td>40/60</td><td>52</td><td>50</td><td>59</td><td>58</td><td>64</td><td>62</td></tr><tr><td>Kronos 2065</td><td>21</td><td>40/60</td><td>56</td><td>54</td><td>63</td><td>60</td><td>66</td><td>65</td></tr><tr><td>Kronos 2190</td><td>18</td><td>40/60</td><td>57</td><td>54</td><td>65</td><td>62</td><td>70(偏高）</td><td>64</td></tr><tr><td>Kronos 2310</td><td>18</td><td>40/60</td><td>57</td><td>55</td><td>65</td><td>62</td><td>70（偏高）</td><td>66</td></tr></table></body></html>  \n\n从表3-1-9可见，当钛白粉：填料 $=10:90$ 时，沥青法和应力法测得的LCPVC非常一致，而且影响LCPVC的主要是填料，因为其量大，不同钛白粉几乎没影响。当钛白粉：填191198 $14=40:60$ 时，钛白粉和填料对其混合物LCPVC都有影响，而沥青法对低吸油量钛白粉和粗填料混合物LCPVC测定结果偏高。  \n\n$\\textcircled{4}$ 成膜助剂等的影响合适的成膜助剂，当其用量达到最佳用量时，LCPVC最大。成膜时的温度升高，LCPVC也升高。  \n\n(4）PVC、LCPVC 和乳胶漆的性能关系Asbeck 和 $\\mathbf{V}\\mathrm{an~}\\mathrm{L.oo}$ 说明了各种涂料性能与颜料体积浓度的关系（图3-1-3)。尽管该图有些过分简化，但还是显示了CPVC的基本特性。乳胶漆性能与PVC的关系如图3-1-4所示。Floyd认为，和Asbeck关系图相似，其大多数性能在一个小的PVC范围内明显变化，该一小范围称为LCPVC。有意义的是，少数几个性能，如光泽和耐腐蚀性，对PVC变化反应比其他性能敏感。CPVC，至少是LCPVC，不简单是开始产生气孔，而是共连续相结构的相转变点，即由聚合物为主连续相转变为空气为主连续相。  \n\n![](images/ff29a72d17ceba0c970c145700d8b392fd1b79cd6515e83b247312958c6e08df.jpg)  \n图3-1-3CPVC对涂料性能的影响A一光泽；B起泡；C—生锈；D-渗透  \n\n![](images/3788989ab5d3a62ff22b5bf0a16bae1db3960c70e61b2c395aab0be366bbe425.jpg)  \n图3-1-4乳胶漆性能与PVC的关系Glo代表光泽；EH代表瓷漆不渗性（enamelholdout)；SR代表耐洗剧性；TS代表拉伸强度；CR代表对比率；Cor代表耐腐蚀性  \n\n配制低PVC乳胶漆时，在干膜中，颜料和填料粒子分散在乳液聚合物的连续相里。随着颜料和填料的增加，PVC提高，当其超过某一极限，即超过LCPVC时，乳液聚合物就不能将颜料和填料粒子间的空隙完全充满，这些未被填充的空隙就留在涂膜中，由空气来填充，涂膜的性能就急剧下降。乳胶漆的PVC也并非越低越好，要综合考虑性能、价格等因素确定。不同光泽乳胶漆的大致PVC列于表3-1-10。  \n\n把PVC/CPVC的比值定义为对比PVC。在进行涂料的配方时，对比PVC或PVC与CPVC的距离比PVC更能反映本质。它们不仅反映了乳胶漆中两个成膜物质—乳液和颜料填料体积关系，而且反映了与LCPVC的距离，从而与乳胶漆的性能挂上了钩。有人建议建筑乳胶漆的PVC/LCPVC值见表3-1-11。实际上，内用平光乳胶漆对比PVC有达1.35的，外用平光乳胶漆对比PVC也有超过1的。  \n\n<html><body><table><tr><td>乳胶漆</td><td>有光</td><td>半光</td><td>蛋壳光</td><td>平光</td></tr><tr><td>PVC/%</td><td>10~18</td><td>18~30</td><td>30~40</td><td>40~80</td></tr></table></body></html>  \n\n表3-1-11建筑乳胶漆的PVC/LCPVC  \n\n\n<html><body><table><tr><td>建筑乳胶漆</td><td>外用平光</td><td>内用平光</td><td>半光</td></tr><tr><td>PVC/CPVC</td><td>0.95~0.98</td><td>0.98~1.1</td><td>0.6~0.85</td></tr></table></body></html>  \n\n也有人认为配方设计时最好避开 $\\mathrm{PVC/CPVC}{=}1.0$ ，因为该点附近性能波动很大。  \n\n总之，乳胶漆最佳配方中的关键因素是PVC/LCPVC。LCPVC的大小与所用原料的种类及配比有关。最佳配方首先是通过调整LCPVC使之尽可能地高，并根据乳胶漆的性能要求，将PVC设定在离LCPVC有一定距离的安全范围内。其次是协调地用好助剂。  \n\n(5）颜基比所谓颜基比是指颜料和填料的质量分数对固体树脂（在乳胶漆中，指固体乳液聚合物）质量分数之比，以 $\\mathbf{P}/\\mathbf{B}$ 表示。颜基比简单，还有不少人使用它。不同乳胶漆的 $\\mathbf{P}/\\mathbf{B}$ 见表3-1-12。 茶 o  \n\n表3-1-10不同光泽乳胶漆的PVC  \n表3-1-12不同乳胶漆的P/B  \n\n\n<html><body><table><tr><td>乳胶漆</td><td>有光乳胶漆</td><td>半光乳胶漆</td><td>外墙乳胶漆</td><td>内墙乳胶漆</td></tr><tr><td>P/B</td><td>0.4~0.6</td><td>0.6~2.0</td><td>0.4~5.0</td><td>0.6~7.0</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 852,
+        "chunk": "# 4.半个世纪前的乳胶漆配方  \n\n1953年，第一个涂料用纯丙乳液诞生了。那时，乳液制造商推荐了一个配方，见表3-1-13。这是一个半个世纪前的乳胶漆配方。  \n\n可以看出，那时乳胶漆的配方在助剂使用方面是十分简单的，只有分散剂和二乙二醇。虽然不完善，但它是环境友好型涂料，代表了涂料的发展方向。因此，很有生命力，终于经  \n\n过半个世纪的演变和发展，成为现代的乳胶漆配方和今天人们所使用的乳胶漆。  \n\n表3-1-13世界上第一个纯丙乳胶漆配方  \n\n\n<html><body><table><tr><td>No.</td><td>原料</td><td>用量/质量份</td><td>制造商</td></tr><tr><td>1</td><td>钛白粉</td><td>267.0</td><td></td></tr><tr><td>2</td><td>立德粉</td><td>76.3</td><td></td></tr><tr><td>3</td><td>云母粉</td><td>51.7</td><td></td></tr><tr><td>4</td><td>石英粉</td><td>81.0</td><td></td></tr><tr><td>5</td><td>分散剂(Tamol N)</td><td>6.8</td><td>罗姆哈斯</td></tr><tr><td>6</td><td>二乙二醇</td><td>7.2</td><td></td></tr><tr><td>7</td><td>水</td><td>190.0</td><td></td></tr><tr><td>8</td><td>乳液[Phoplex AC-33,（46%)]</td><td>516.0</td><td>罗姆哈斯</td></tr><tr><td></td><td>合计</td><td>1196.0</td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 853,
+        "chunk": "# 5.现代乳胶漆配方中各组分的作用及相互关系  \n\n表3-1-14是乳液制造商推荐的白色外墙乳胶漆的推荐配方。仅以此为例，说明各组分的作用及相互关系。因为该配方来自美国，所以一般有两种配比，质量和体积，体积总量为100。这样做的原因是生产数量通常是100单位体积的倍数，另外，也便于人们比较配方组成的体积分数。另一方面，许多组分是以质量为基准加入的，所以也有质量配比。我国一般是采用质量配比。  \n\n表3-1-14白色外墙乳胶漆的推荐配方  \n\n\n<html><body><table><tr><td rowspan=\"2\">序 号</td><td rowspan=\"2\">原料</td><td colspan=\"2\">配比/%</td><td rowspan=\"2\">原料供应商</td></tr><tr><td>质量</td><td>体 积</td></tr><tr><td>1</td><td>Natrosol 250 MHR(2. 5%)</td><td>120.0</td><td>14.40</td><td>Aqualon</td></tr><tr><td>2</td><td>乙二醇</td><td>25.0</td><td>2.68</td><td></td></tr><tr><td>3</td><td>丙二醇</td><td>35.0</td><td>4.04</td><td></td></tr><tr><td>4</td><td>Tamol 1124(50%)</td><td>4.6</td><td>0.47</td><td>Rohm &Haas</td></tr><tr><td>5</td><td>Triton CF-10</td><td>1.0</td><td>0.11</td><td>Union Carbide</td></tr><tr><td>6</td><td>Colloid 643</td><td>2.0</td><td>0.26</td><td>Rhodia</td></tr><tr><td>7</td><td>Ti-Pure R-902</td><td>150.0</td><td>4.50</td><td>Du Pont</td></tr><tr><td>8</td><td>Minex 4</td><td>50.0</td><td>2.30</td><td>Indusmin, Inc</td></tr><tr><td>9</td><td>Icecap K</td><td>15.9</td><td>0.68</td><td>Unimin Specialty Minerals, Inc</td></tr><tr><td>10</td><td>Celite 281</td><td>45.0</td><td>2.34</td><td>Johns Manville</td></tr></table></body></html>  \n\n高速分散机分散 $20\\mathrm{{min}}$ 然后较低速度下加人以下组分  \n\n\n<html><body><table><tr><td>11</td><td>Ropaque OP-62LO(36. 5%)</td><td>120. 0</td><td>13.96</td><td>Rohm &.Haas</td></tr><tr><td>12</td><td>Rhoplex Multilobe 200(53. 5%)</td><td>336.8</td><td>37.96</td><td>Rohm & Haas</td></tr><tr><td>13</td><td>Texanol</td><td>11.2</td><td>1.41</td><td>Eastman Chemical</td></tr><tr><td>14</td><td>Colloid 643</td><td>2.0</td><td>0.26</td><td>Rhodia</td></tr><tr><td>15</td><td>NHOH (28%)</td><td>0.6</td><td>0.08</td><td></td></tr><tr><td>16</td><td>Natrosol MHR (2.5%)</td><td>49.0</td><td>5.88</td><td>Aqualon</td></tr><tr><td>17</td><td>水</td><td>72.3</td><td>8.67</td><td></td></tr><tr><td></td><td>合计 ，</td><td>1039.5</td><td>100.00</td><td></td></tr></table></body></html>  \n\n特性  \n\n\n<html><body><table><tr><td>PVC/% 体积固含量/% 质量固含量/% pH 斯托默黏度（平衡值）/KU ICI黏度（平衡值）/Pa·s VOC(扣水）/(g/L)</td><td>47.0 36.4 46.7 8.8~9.0 88 0.095 196</td><td></td></tr></table></body></html>  \n\nNatrosol $250~\\mathrm{MHR}$ 是羟乙基纤维素（HEC）增稠剂，在配方中的作用是增稠，提高乳胶漆在制造和施工过程中的外相黏度，并控制乳胶漆的最终黏度。黏度会影响乳胶漆的涂刷性、涂膜厚度、流平性、流挂性和贮存稳定性等。外相黏度还控制漆液渗透入多孔基层的速率。如果迅速渗透，多孔基面上乳胶漆的黏度和PVC就会上升，导致流平性变差，留在多孔基面上的涂膜质量下降。由于羟乙基纤维素保水性好，所以能延长开放时间。在序号1加入HEC，一是可以有足够的水来配制HEC水溶液，并使其有足够的时间溶胀和均匀分散；二是提高颜料、填料分散体的黏度，有利于分散。  \n\n乙二醇和丙二醇的主要作用有两个：一是防冻作用，提高乳胶漆的低温稳定性；二是调节乳胶漆干燥速率，延长湿边时间，防止产生接痕。从环保角度看，丙二醇比较环保，所以发展趋势是使用丙二醇，而不是乙二醇。  \n\nTamol1124是阴离子分散剂，促进颜料、填料分散稳定。TritonCF-10是一种非离子表面活性剂，能有效地降低表面张力，使颜料、填料较好地湿润，提高其分散稳定性。同时，由于乳胶漆表面张力降低，从而提高对基面的湿润能力，有利于获得较高的附着力，或湿润表面张力较低的基材。非离子表面活性剂和阴离子分散剂的搭配使用有利于提高系统稳定性。  \n\nColloid 643是消泡剂，一般在打浆和制漆阶段分别加1/2。必须用尽可能少的消泡剂量来控制泡沫，过量的消泡剂会导致施工时缩孔。  \n\nTi-Pure R-902是金红石型钛白粉，其作用是提供涂膜遮盖力。金红石型钛白粉价格高，在达到要求的情况下，能少用尽量少用。这里以不透明聚合物RopaqueOP-62LO为补充，以满足遮盖力的要求。  \n\nMinex4是一种钠钾铝的硅酸盐填料，吸油量 $26,6\\mathbf{g}/100\\mathbf{g}$ 。Icecap K是铝硅酸盐填料。Celite 281是硅藻土吸油量很大， $139\\mathbf{g}/100\\mathbf{g}$ 。它们的主要作用是降低成本，增加涂膜的体积，改善乳胶漆及其涂膜的性能。这些填料的折射率与涂料基料的折射率差不多，它们本身几乎没有遮盖力。但它们很细，具有位隔作用，能提高钛白粉的遮盖效率。  \n\n颜料、填料经高速分散，分散细度检验合格后，在低速揽拌的情况下，加人不透明聚合物 RopaqueOP-62LO和乳液。RopaqueOP-62LO除了能提供遮盖力外，因其粒子细而均匀，能提高涂膜表面平整度，从而改善涂膜的耐沾污性。  \n\n乳液把乳胶漆各组分黏结在一起，形成涂膜，同时又使涂膜附着在基面上。它是乳胶漆的最主要组分。在低速搅拌下加入乳液是防止其破乳而影响乳胶漆的性能。  \n\nTexanol是成膜助剂，其化学名为2,2,4-三甲基-1,3-戊二醇单异丁酸酯。顾名思义，其作用是帮助乳液成膜，即降低乳胶漆的最低成膜温度，使乳液在施工的温度、湿度等条件下，尤其是冬天，形成连续膜。随着成膜过程的进行，成膜助剂会逐渐挥发，乳胶漆的最低成膜温度逐步升高，涂膜不断变硬，直至成膜过程结束。高浓度的成膜助剂易使乳液絮凝，因此，在此阶段加入时，应在低速搅拌的条件下，慢慢地加人，并搅拌均匀。也有将成膜助剂在打浆阶段加入的。其好处是可以避免乳液絮凝危险，但也有一些成膜助剂可能被颜料填料吸入颗粒中。至于成膜助剂的用量，绝大多数人认为，根据配方中乳液量来确定，因为其是帮助乳液成膜的。但事实是，随着颜料、填料的加人，乳液在乳胶漆中的最低成膜温度是不同于纯乳液的最低成膜温度的，它会升高。因此，根据配方中乳液量来确定成膜助剂用量时，如果采用同一比例的话，对于高PVC的乳胶漆，成膜助剂用量不够；而对于低PVC的乳胶漆，成膜助剂用量太多。综上所述，成膜助剂用量可根据其降低聚合物最低成膜温度的能力和对乳胶漆最低成膜温度的要求来确定，一般为乳胶漆总量的 $1.5\\%\\sim3\\%$  \n\nNHOH，即氨水，是pH调节剂，当然是起调节pH值的作用。乳胶漆一般是偏碱性的。这使碱增稠剂充分发挥增稠作用，也有利于乳胶漆的防腐。当乳胶漆装在有涂层的马口铁桶中时，涂层难免有些损坏，在这种情况下，高pH还能使桶的腐蚀最小化。  \n\n最后两项是水和羟乙基纤维素（HEC）增稠剂，主要是用于调节乳胶漆的最终黏度。当然也可以用其他类型的增稠剂调节乳胶漆的最终黏度。不同类型的增稠剂搭配使用，可使乳胶漆的黏度曲线较符合实际要求。  \n\n配方中防腐剂是一定要加的，否则乳胶漆在贮存期内要变质，尤其是以纤维素为增稠剂的乳胶漆。一般可加0.15%左右的防腐剂。热稳定性好的防腐剂可在打浆前加入，热稳定性差的防腐剂应在调漆后阶段加人，以防打浆时温度较高而使防腐剂分解失效。防霉剂可根据防霉要求，加或不加，或加多少。  \n\n该乳胶漆的PVC是 $47\\%$ ，比LCPVC低得多，所以是一种高性能的外墙乳胶漆。但就光泽来说，仍属于亚光乳胶漆。  \n\n乳胶漆的体积固含量是36. $4\\%$ ，质量固含量是46.7%。在计算乳胶漆干膜厚度时，可将单位面积的乳胶漆用量 $\\scriptstyle({\\mathrm{mL}}/{\\mathrm{m}}^{2}$ ）乘以其体积固含量而求得，而不是乘以其质量固含量。  \n\nICI黏度是高剪切速率黏度，基本反映刷涂、滚涂和喷涂时的黏度。乳胶漆的ICI黏度一般为 $0.10{\\sim}0.12\\mathrm{Pa}\\cdot\\mathbf{s}$ ，该配方为 $0.095\\mathrm{Pa}^{\\cdot\\cdot\\mathrm{\\Omegas}}$ ，处于下限。这是因为配方中仅采用羟乙基纤维素（HEC）增稠剂所致，因为羟乙基纤维素增稠剂的高剪切速率黏度较低。合适的ICI黏度是控制乳胶漆施工厚度的主要因素。  \n\n斯托默黏度是中低剪切速率黏度，也是建筑涂料工业常用的黏度。一般认为在 $75\\sim$ 95KU。该配方实测结果是88KU。  \n\n挥发性有机物（VOC）含量是环境友好型涂料的一个重要指标。该外墙乳胶漆扣水后VOC为 $196g/\\mathrm{L}$ ，未达到HJ/T201—2005《环境标志产品技术要求水性涂料》的要求。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 854,
+        "chunk": "# 6.提高遮盖力的措施  \n\n乳胶漆的遮盖力是乳胶漆装饰功能的基础。没有足够的遮盖力，就谈不上装饰作用。首先，遮盖力产生于颜料与介质的折射率差，差值越大，遮盖力越高。金红石型钛白粉折射率最高，所以遮盖力也最好。其次，遮盖力还与颜料的浓度有关。因此，要提高遮盖力，一般是多加钛白粉。金红石型钛白粉很贵，尤其是单位体积的价格，详见表3-1-15。因此，在保证遮盖力的前提下，能节省就尽量节省。从而就产生了提高遮盖力的各种措施。 2  \n\n表3-1-15乳胶漆主要原料成本  \n\n\n<html><body><table><tr><td>原料</td><td>价格/（元/吨）</td><td>密度（固体）/(g/cm²）</td><td>单价/（元/kg固体）</td><td>单价/（元/L固体）</td></tr><tr><td>金红石型钛白粉</td><td>20000</td><td>4.0</td><td>20</td><td>80</td></tr><tr><td>纯丙乳液(50%)</td><td>11000</td><td>1.12</td><td>22</td><td>24.6</td></tr><tr><td>苯丙乳液（50%）</td><td>7500</td><td>1.12</td><td>15</td><td>16.8</td></tr><tr><td>填料</td><td>900</td><td>2.7</td><td>0.9</td><td>2.43</td></tr></table></body></html>  \n\n(1）引进气孔提高遮盖力如上所述，乳胶漆的遮盖力不仅取决于颜料的浓度，而且同颜料与介质的折射率差有关，差值愈大，遮盖力愈高。如果保持颜料的折射率不变，降低介质的折射率，差值增大，乳胶漆的遮盖力就可以提高。  \n\n在涂膜中，引进气孔，就能降低介质的折射率。空气和干乳胶的折射率分别为1.0和  \n\n1.5，假设介质的空隙率为PI，则含气孔介质的折射率 $n_{\\mathrm{b}}$ 见式（3-1-4)  \n\n$$\nn_{\\mathrm{b}}=1.\\ 0\\mathrm{PI}+1.\\ 5\\left(1-\\mathrm{PI}\\right)=1.\\ 5-0.\\ 5\\mathrm{PI}\n$$  \n\n由式（3-1-4）可知，引进气孔越多，含气孔介质的折射率越低，颜料与该介质的折射率差越大，乳胶漆的遮盖力越好。  \n\n$\\textcircled{1}$ PVC大于LCPVC在配方时，通过将PVC提高至LCPVC以上，在涂膜中引进气孔，从而达到提高遮盖力的结果。价廉物美地高PVC乳胶漆，大多是内墙乳胶漆，也有外墙乳胶漆，就是以此来达到较好的遮盖力的。  \n\n表3-1-16是一个通过加人超细填料，降低LCPVC，保持PVC不变，从而增大PVC与LCPVC的距离，在涂膜中引进气孔，达到降低钛白粉而保持遮盖力不变的例子。钛白粉用量从 $16\\%$ 降至 $10\\%$ ，遮盖力基本保持不变。烧高岭土PoleStar400A是ECC公司的产品。平均粒径为 $0.5\\mu\\mathrm{m}$ ，小于 $2\\mu\\mathrm{m}$ 的粒径占 $92\\%$ ，吸油量是 $95\\ \\mathbf{g}/100\\mathbf{g}$  \n\n表3-1-16引进气孔提高遮盖力 单位：质量份  \n\n\n<html><body><table><tr><td>No.</td><td>原料</td><td>配方1</td><td>配方2</td><td>配方3</td><td>配方4</td></tr><tr><td>1</td><td>厚包膜钛白粉</td><td>16.0</td><td>14. 0</td><td>12.0</td><td>10.0</td></tr><tr><td>2</td><td>般烧高岭土PoleStar 400A</td><td>0</td><td>2.0</td><td>4.0</td><td>6.0</td></tr><tr><td>3</td><td>不透明聚合物RopaqueOP62</td><td>8.2</td><td>8.2</td><td>8.2</td><td>8.2</td></tr><tr><td>4</td><td>碳酸钙Micocal Spa C120</td><td>24.5</td><td>24.5</td><td>24.5</td><td>24.5</td></tr><tr><td>5</td><td>湿润分散剂Dispex N40</td><td>0.3</td><td>0.3</td><td>0.3</td><td>0.3</td></tr><tr><td>6</td><td>湿润分散剂Caigon S</td><td>0.1</td><td>0.1</td><td>0.1</td><td>0.1</td></tr><tr><td>7</td><td>氨水</td><td>0.2</td><td>0.2</td><td>0.2</td><td>0.2</td></tr><tr><td>8</td><td>防腐剂Acticide BX</td><td>0.2</td><td>0.2</td><td>0.2</td><td>0.2</td></tr><tr><td>9</td><td>丙二醇</td><td>0.8</td><td>0.8</td><td>0.8</td><td>0.8</td></tr><tr><td>10</td><td>消泡剂Nopco NXZ</td><td>0.3</td><td>0.3</td><td>0.3</td><td>0.3</td></tr><tr><td>11</td><td>增稠剂Natrosol 250MR(3%）</td><td>18.3</td><td>18.3</td><td>18.3</td><td>18.3</td></tr><tr><td>12</td><td>成膜助剂Texanol</td><td>1.8</td><td>1. 8</td><td>1.8</td><td>1.8</td></tr><tr><td>13</td><td>乳液Vinamul 3469(55%)</td><td>16.6</td><td>16.6</td><td>16.6</td><td>16.6</td></tr><tr><td>14</td><td>水</td><td>12.7</td><td>12.7</td><td>12.7</td><td>12.7</td></tr><tr><td></td><td>合计</td><td>100.0</td><td>100.0</td><td>100.0</td><td>100.0</td></tr></table></body></html>  \n\n涂料和涂膜  \n\n\n<html><body><table><tr><td>1</td><td>PVC/%</td><td>70</td><td>70</td><td>70</td><td>.70</td></tr><tr><td>2</td><td>质量固含量/%</td><td>53.5</td><td>53.5</td><td>53.5</td><td>53.5</td></tr><tr><td>3</td><td>体积固含量/%</td><td>35.4</td><td>35.6</td><td>35.8</td><td>36.0</td></tr><tr><td>4</td><td>密度/(g/cma）</td><td>1.4</td><td>1.39</td><td>1.38</td><td>1.37</td></tr><tr><td>5</td><td>涂布率为20m²/L的对比率</td><td>94.0</td><td></td><td></td><td></td></tr><tr><td>6</td><td>颜色</td><td></td><td>93.9</td><td>93.9</td><td>93.8</td></tr><tr><td></td><td>L</td><td>97.7</td><td>97.6</td><td>97.6</td><td>97.5</td></tr><tr><td></td><td></td><td>+0.09</td><td>+0.01</td><td>+0.01</td><td></td></tr><tr><td></td><td>b</td><td>+0.65</td><td>+0. 72</td><td></td><td>-0.02</td></tr><tr><td>7</td><td></td><td>7</td><td></td><td>+0.80</td><td>+0.85</td></tr><tr><td>8</td><td>85°光泽/%</td><td></td><td>7</td><td>7</td><td>8</td></tr><tr><td>9</td><td>ASTM耐洗刷性/次 抗裂性/μm</td><td>270 850</td><td>260 850</td><td>250 850</td><td>230 825</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 不透明聚合物不透明聚合物也是通过在涂膜中引进气孔，产生遮盖作用的，同时它粒径比较细，还有位隔作用，提高颜料的遮盖力。同样由于粒径比较细，用于外墙涂料，还能增加涂膜的表面平整度，而改善耐沾污性。  \n\n有关不透明聚合物在乳胶漆中的应用结果列于表3-1-17。  \n\n表3-1-17不透明聚合物在乳胶漆中的应用结果 单位：质量份  \n\n\n<html><body><table><tr><td>序号</td><td>原料</td><td>对照配方</td><td>配方1</td><td>配方2</td><td>配方3</td><td>配方4</td></tr><tr><td>1</td><td>水</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td></tr><tr><td>2</td><td>X-405湿润剂</td><td>1. 5</td><td>1.5</td><td>1</td><td>1</td><td>1</td></tr><tr><td>3</td><td>丙二醇</td><td>25</td><td>25</td><td>25</td><td>25</td><td>25</td></tr><tr><td>4</td><td>5040分散剂</td><td>6</td><td>6</td><td>5</td><td>5</td><td>4</td></tr><tr><td>5</td><td>681F消泡剂</td><td>2</td><td>2</td><td>2</td><td>2</td><td>2</td></tr><tr><td>6</td><td>LXE防腐剂</td><td>1.5</td><td>1. 5</td><td>1.5</td><td>1.5</td><td>1.5</td></tr><tr><td>7</td><td>R-706钛白粉</td><td>245</td><td>225</td><td>205</td><td>185</td><td>165</td></tr><tr><td>8</td><td>烧高岭土</td><td>70</td><td>70</td><td>70</td><td>70</td><td>70</td></tr><tr><td>9</td><td>1500目重钙</td><td>60</td><td>60</td><td>60</td><td>60</td><td>60</td></tr><tr><td>10</td><td>AC-261纯丙乳液</td><td>350</td><td>350</td><td>350</td><td>350</td><td>350</td></tr><tr><td>11</td><td>醇酯-12成膜助剂</td><td>14</td><td>14</td><td>14</td><td>14</td><td>14</td></tr><tr><td>12</td><td>8034L消泡剂</td><td>1</td><td>1</td><td>1</td><td>1</td><td>1</td></tr><tr><td>13</td><td>250HBR羟乙基纤维素增稠剂（2.5%）</td><td>60</td><td>60</td><td>60</td><td>60</td><td>60</td></tr><tr><td>14</td><td>水</td><td>59.5</td><td>59.5</td><td>61</td><td>61</td><td>41.5</td></tr><tr><td>15</td><td>不透明聚合物</td><td>0</td><td>20</td><td>40</td><td>60</td><td>100</td></tr><tr><td>16</td><td>TT-935疏水改性碱增稠剂</td><td>1.5</td><td>1.5</td><td>1.5</td><td>1.5</td><td>1.5</td></tr><tr><td>17</td><td>SN-Thickener612聚氨酯增剂</td><td>3</td><td>3</td><td>3</td><td>3</td><td>3.5</td></tr><tr><td>合计</td><td></td><td>1000.0</td><td>1000. 0</td><td>1000.0</td><td>1000. 0</td><td>1000. 0</td></tr><tr><td colspan=\"2\">性能</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td colspan=\"2\">对比率</td><td>0.945</td><td>0.956</td><td>0.970</td><td>0.985</td><td>0.968</td></tr><tr><td colspan=\"2\">60°光泽/%</td><td>76.2</td><td>76.0</td><td></td><td>75.8</td><td></td></tr><tr><td colspan=\"2\">耐人工老化性/h</td><td>600</td><td>600</td><td>76.0</td><td></td><td>73.6</td></tr><tr><td colspan=\"2\"></td><td>30</td><td></td><td>600</td><td>600</td><td>500</td></tr><tr><td colspan=\"2\">耐沾污性/%</td><td></td><td>26</td><td>18</td><td>10</td><td>8</td></tr><tr><td colspan=\"2\">耐洗刷性(2000次)</td><td>般</td><td>一般</td><td>较好</td><td>好</td><td>好</td></tr><tr><td colspan=\"2\">原料成本/（元/kg）</td><td>10.5</td><td>10.0</td><td>9.8</td><td>9.4</td><td>9.2</td></tr></table></body></html>  \n\n由表3-1-17可以看出，随着不透明聚合物取代钛白粉的增加，直至 $8\\%$ （质量分数），对比率、耐沾污性和耐洗刷性提高，原料成本略有降低。  \n\n亚洲热带地区的曝晒结果表明，在乳胶漆配方中，如含有 $30\\%$ PVC 左右的 RopaqueOP-62，不管该配方的PVC是高于CPVC，还是低于CPVC，外墙乳胶漆的耐沾污性都能得到相当大的改善。  \n\n据报道，不透明聚合物取代钛白粉的最高量与钛白粉、不透明聚合物和乳液的价格有关。在大多数配方中， $4\\%$ PVC 的Rhopaque OP-62约等于 $1\\%$ PVC钛白粉。如下一些使用不透明聚合物的经验可供参考。  \n\n钛白粉的PVC大于22%时，可减少其中25%的钛白粉。钛白粉的PVC小于22%时，可减少其中 $20\\%$ 的钛白粉。  \n\n乳胶漆的PVC大于 $55\\%$ 时，以5倍量的OP62取代钛白粉，OP-62的最大PVC为$15\\%$ ，最小PVC为 $8\\%$ 。乳胶漆的PVC小于 $55\\%$ 时，以4倍量的 ${\\phantom{-}0962}$ 取代钛白粉，OP-62的最大PVC为 $20\\%$ 9  \n\n不透明聚合物也可取代超细填料。如果超细填料的PVC大于 $10\\%$ 时，可减少其中的1/3。如果超细填料的PVC小于 $10\\%$ 时，可减少其中的1/2。  \n\n如果原配方采用厚包膜R3钛白粉，且用量较低 $(3\\%\\sim7\\%)$ ，而现在要在配方中加不透明聚合物，那么用通用型R2钛白粉等量取代R3钛白粉是有利的。  \n\n(2）通过位隔作用提高遮盖力粗的填料会使钛白粉在乳胶漆干膜中堆积在一起，从而使其遮盖力降低，而细的填料能把钛白粉分隔开，从而提高其遮盖力。人们把细填料的这种作用叫做位隔作用（spacing），把这种细填料叫做位隔填料（spacing extender 或 spacer），或钛白粉位隔剂，或钛白粉稀释剂。位隔作用可以用对钛白粉稀释效率（Ea）来表示。稀释效率定义为作为钛白粉位隔剂的那部分填料体积与该填料总体积之比，详见表3-1-18。  \n\n表3-1-18不同粒径填料的稀释效率  \n\n\n<html><body><table><tr><td>填 料</td><td>稀释效率（E)</td><td>填料</td><td>稀释效率（E)</td></tr><tr><td>12.5μmCaCO</td><td>0</td><td>2. 0μm SiOz</td><td>0.40</td></tr><tr><td>7.5μm滑石粉</td><td>0.07</td><td>1.8μm烧高岭土</td><td>0.74</td></tr><tr><td>5. 5μm CaCO</td><td>0.15</td><td>1.0jum锻烧高岭土</td><td>0.85</td></tr><tr><td>3. 0μm CaCO</td><td>0.30</td><td>0. 8μm CaCO</td><td>0.99</td></tr></table></body></html>  \n\n位隔作用提高遮盖力可通过式（3-1-5）计算。  \n\n式中HP——对比率等于0.98时的遮盖力， $\\mathbf{m}^{2}/\\mathrm{L}$  \n\nW-—钛白粉浓度，kg/L涂料；PVCe——有效钛白粉体积浓度，小数表示。  \n\n$$\n\\mathrm{PVC}_{\\mathrm{e}}=\\frac{V_{\\mathrm{t}}}{V_{\\mathrm{t}}+V_{\\mathrm{e}}E_{\\mathrm{d}}+V_{\\mathrm{b}}}\n$$  \n\n式中，V：为钛白粉体积； $\\boldsymbol{v}_{\\star}$ 为填料体积； $\\boldsymbol{V_{\\mathrm{b}}}$ 为干乳胶体积。  \n可以看出，填料变细， $E_{\\mathrm{d}}$ 增大， $\\mathrm{PVC_{\\mathrm{e}}}$ 降低，遮盖力提高。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 855,
+        "chunk": "# 7.开放时间  \n\n在乳胶漆的涂刷过程中，前一道刚涂刷的湿涂膜，在一定的时间间隔内，将被后一道湿涂膜所搭接，干燥成膜后，看不出接痕的最长时间间隔就叫做该乳胶漆的开放时间。  \n\n乳胶漆的干燥成膜不仅与乳胶漆的组成有关，而且受周围环境的温度、湿度和基层的温度、吸水性强烈影响。为了便于比较，可把在 $(23\\pm2)\\tau$ ， $\\mathrm{RH}=(50\\pm5).$ %和规定基层的标准条件下的开放时间称为标态开放时间。而将实际施工条件下的开放时间称为实际开放时间。实际开放时间随施工条件改变而变化。尤其是在夏天施工时，气温高，干燥快，实际开放时间短，很容易出现接痕。  \n\n为了避免出现接痕，乳胶漆实际开放时间应大于互相搭接的二道涂膜涂刷的时间间隔。但乳胶漆开放时间也不能过长，否则，既影响涂膜干燥时间，又容易造成涂膜被污染。对于外墙乳胶漆，还会推迟其涂膜耐雨淋的时间。据介绍，在涂刷底涂后的低吸水性基层上，最佳的开放时间是 $10\\mathrm{\\sim}12\\mathrm{min}$ or  \n\n乳胶漆的开放时间，可以通过加减二醇类溶剂、高沸点溶剂、成膜助剂和延长开放时间助剂等来调节。对于不含溶剂的零VOC乳胶漆，当然不能加入溶剂来调节其开放时间，因此，只能通过固含量和纤维素增稠剂等来调节。 双",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 856,
+        "chunk": "# 8.抗干燥收缩裂缝  \n\n抗干燥收缩裂缝（mudcracks）是指涂膜抵抗因干燥收缩而产生裂缝的能力。它是指在湿涂膜干燥成膜过程中出现的裂缝，而不是干燥成膜后，在使用过程中出现的裂缝。  \n\n(1）测试方法抗干燥收缩裂缝通常以带楔子缝隙涂布器涂布湿膜，如樱子缝隙涂布器的缝隙为 ${50\\sim2000\\mu\\mathrm{m}}$ ，宽度为 $156\\mathrm{mm}$ ，涂布后的湿膜在（ $23\\pm2)\\uptau$ ， $\\boldsymbol{\\mathrm{RH}}=$ C $50\\pm5)$ %的标准条件下养护 $48\\mathrm{h}$ ，然后观测干膜在何一厚度开始开裂。这个开始开裂的干膜厚度就是该乳胶漆的抗干燥收缩裂缝的极限，叫做抗干燥收缩裂缝，以 $\\scriptstyle\\mu\\ m$ 来表示，如图3-1-5所示。  \n\n![](images/6ee6207fe6c548b4ac873cc9bbf1ea1a4b1a33c19b3c7c363e2ecf7e457bf63c.jpg)  \n图3-1-5抗干燥收缩裂缝测定结果  \n\n(2）抗干燥收缩裂缝的要求对于内墙乳胶漆，抗干燥收缩裂缝的要求是400um。对于外墙乳胶漆，由于基层平整度较差，所以抗干燥收缩裂缝的要求提高至900μm。这是德国对乳胶漆抗干燥收缩裂缝的要求。  \n\n由于我国施涂的涂膜一般比德国薄，质感又不强，抗干燥收缩裂缝的要求可以适当放宽一些。但对于浮雕漆上施涂的乳胶漆，抗干燥收缩裂缝的要求是绝对不能放宽的，而且还要提高。  \n\n(3）干燥收缩裂缝产生原因干燥收缩裂缝是由于涂膜干燥收缩应力大于其抗拉强度而产生。随着颜料和填料混合物的比表面积增加，涂膜干燥收缩应力提高，产生干燥收缩裂缝的可能性增大。成膜助剂用量不足、涂膜过厚、基层凹凸不平、干燥太快等都可能导致出现干燥收缩裂缝。  \n\n(4）如何提高抗干燥收缩裂缝能力由于涂膜干燥收缩应力过大而导致干燥收缩裂缝，因此，一切能降低涂膜干燥收缩应力的措施，都能提高乳胶漆抗干燥收缩裂缝能力。如适当提高填料的粒径，降低其吸油量，或增加成膜助剂用量，采用一些纤维状或片状填料等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 857,
+        "chunk": "# 9.配方设计举例  \n\n以下是一个美国东南部的内墙乳胶漆配方。主要通过触变型填料（structuredextend-ers）和非触变型填料（non-structuredextenders）组合来达到所要求的性能。触变型填料为烧高岭土和硅藻土。非触变型填料为碳酸钙和石英粉。因为涂料组分是以体积组成干膜的，所以配方都是以体积计算的，这一点与我国是不一样的。另外性能指标也与我国不同，对内墙乳胶漆，我国偏重耐洗刷性和对比率。  \n\n（1）初始配方根据经验和调查了解，选定原材料，见表3-1-19。并确定配方参数，不包括助剂，乳胶漆的体积固含量为 $33\\%$ ，颜料体积浓度PVC为 $63\\%$  \n\n在100L乳胶漆中，固体为33L，颜料和填料总体积为33×63%=20.79（L)，乳液固体体积33-20.79=12.21（L)。配方中乳液用量12.21÷53.09%×1.08=24.84（kg）。  \n\n表3-1-19原材料  \n\n\n<html><body><table><tr><td>序号</td><td>原料</td><td>密度 /(kg/L)</td><td>质量固含量 /%</td><td>体积固含量 /%</td><td>吸油量 /（g/100g)</td><td>威本 /（美元/USgal）</td></tr><tr><td>1</td><td>水</td><td>1.00</td><td>0</td><td>。</td><td></td><td></td></tr><tr><td>2</td><td>羟甲基纤维素Celflow S-100</td><td>1.39</td><td>100</td><td>100</td><td></td><td>3.75</td></tr><tr><td>3</td><td>pH调节剂AMP-95</td><td>0.95</td><td>95</td><td>95</td><td></td><td>1.50</td></tr><tr><td>4</td><td>丙二醇</td><td>1. 04</td><td>0</td><td>0</td><td></td><td>0.77</td></tr><tr><td>5</td><td>成膜助剂Texanol</td><td>0.95</td><td>0</td><td>0</td><td></td><td>0.70</td></tr><tr><td>6</td><td>防腐剂AMA480</td><td>1. 00</td><td>1.5</td><td>1. 5</td><td></td><td>5.28</td></tr><tr><td>7</td><td>消泡剂Colloid 643</td><td>0.84</td><td>100</td><td>100</td><td></td><td>0.55</td></tr><tr><td>8</td><td>湿润剂Triton N 101</td><td>1.04</td><td>100</td><td>100</td><td></td><td>0.96</td></tr><tr><td>9</td><td>分散剂Colloid 226(35%)</td><td>1.27</td><td>35</td><td>33.27</td><td></td><td>0.50</td></tr><tr><td>10</td><td>钛白粉</td><td>4.10</td><td>100</td><td>100</td><td>17</td><td>1.10</td></tr><tr><td>11</td><td>13μm粗碳酸钙</td><td>2.71</td><td>100</td><td>100</td><td>12</td><td>0.06</td></tr><tr><td>12</td><td>3μm细碳酸钙</td><td>2.71</td><td>100</td><td>100</td><td>16</td><td>0.09</td></tr><tr><td>13</td><td>1.5μm烧高岭土</td><td>2.63</td><td>100</td><td>100</td><td>55</td><td>0.20</td></tr><tr><td>14</td><td>硅藻土</td><td>2.05</td><td>100</td><td>100</td><td>110</td><td>0.13</td></tr><tr><td>15</td><td>12.5μm粗石英粉</td><td>2.66</td><td>100</td><td>100</td><td>28</td><td>0.10</td></tr><tr><td>16</td><td>3μm细石英粉</td><td>2.66</td><td>100</td><td>100</td><td>30</td><td>0.15</td></tr><tr><td>17</td><td>醋丙乳液（55%）</td><td>1.08</td><td>55</td><td>53.09</td><td></td><td>0.40</td></tr></table></body></html>\n\n注：1US gal= 3. 78dm。  \n\n根据经验，一般平光内墙乳胶漆中钛白粉为 $18.09\\mathrm{kg/100L}$ （150lb/100gal)。则100L乳胶漆中钛白粉的体积为 $18.09\\div4.1=4.41$ (L)。填料的体积为 $20.79-4.41=16.38$ (L)，假定烧高岭土用量为 $18\\mathbf{kg}$ ，即体积为 $18\\div2.63=6.84$ (L)，则碳酸钙体积为16.38—6. $84=9.54$ (L)，用量为 $9.54\\times2.71=25.85(\\mathbf{kg})$ 。  \n\n确定初始配方ILF-01，见表3-1-20。  \n\n表3-1-20初始配方ILF-01  \n\n\n<html><body><table><tr><td>序号</td><td>原 料</td><td>配比/kg</td><td>配比/L</td></tr><tr><td colspan=\"4\">打浆</td></tr><tr><td>1</td><td>水</td><td>34.23</td><td>34.23</td></tr><tr><td>2</td><td>羟甲基纤维索CelflowS-100</td><td>0.54</td><td>0.39</td></tr><tr><td>3</td><td>pH调节剂AMP-95</td><td>0.18</td><td>0.19</td></tr><tr><td>4</td><td>丙二醇</td><td>3.13</td><td>3.00</td></tr><tr><td>5</td><td>成膜助剂Texanol</td><td>0.95</td><td>1.00</td></tr><tr><td>6</td><td>防腐剂AMA480</td><td>0.24</td><td>0.21</td></tr><tr><td>7</td><td>消泡剂Colloid 643</td><td>0.36</td><td>0.39</td></tr><tr><td>8</td><td>湿润剂Triton N 101</td><td>0.26</td><td>0.25</td></tr><tr><td>9</td><td>分散剂Colloid 226(35%)</td><td>0.72</td><td>0.57</td></tr><tr><td>10</td><td>钛白粉</td><td>18.09</td><td>4.41</td></tr><tr><td>11</td><td>13μm粗碳酸钙</td><td>25.85</td><td>9.56</td></tr><tr><td>12</td><td>1.5μm烧高岭土</td><td>18.00</td><td>6.82</td></tr></table></body></html>  \n\n调漆   \n\n\n<html><body><table><tr><td>13</td><td>水</td><td>14.61</td></tr><tr><td>14</td><td>羟甲基纤维索Celflow S-100</td><td>0.27</td></tr><tr><td>15</td><td>消泡剂Colloid 643</td><td>0.20 0.23 0.25</td></tr><tr><td>16</td><td>醋丙乳液（55%) 合计</td><td>24.84 24.00 142.50 100.00</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 858,
+        "chunk": "# (2）重要配方参数计算  \n\n$\\textcircled{1}$ LCPVCLCPVC按式（3-1-3）计算。配方ILF-01计算情况列表3-1-21。  \n\n表3-1-21LCPVC计算  \n\n\n<html><body><table><tr><td>原 料</td><td>密度p/（kg/L)</td><td>吸油量OA/(g/100g）</td><td>质量W;</td><td>W/p</td><td>OA·W</td></tr><tr><td>钛白粉</td><td>4.10</td><td>17</td><td>18.09</td><td>4.41</td><td>307.53</td></tr><tr><td>13μm粗碳酸钙</td><td>2.71</td><td>12</td><td>25.85</td><td>9.54</td><td>310.20</td></tr><tr><td>1.5μm烧高岭土</td><td>2.63</td><td>55</td><td>18.00</td><td>6.84</td><td>990.00</td></tr><tr><td>合计</td><td></td><td></td><td>61.94</td><td>20.79</td><td>1607.73</td></tr></table></body></html>  \n\n$$\n\\mathrm{LCPVC}=\\frac{20.79}{20.79+\\frac{1607.73}{93.5}}=0.5474=54.74\\%\n$$  \n\n$\\textcircled{2}$ 对比PVC对比PVC以 $\\lambda$ 表示， $\\lambda{=}\\operatorname{PVC/LCPVC}{=}63/54.74{=}1.15$ 。说明干膜中孔隙还是比较低的。  \n\n$\\textcircled{3}$ 体积固含量将初始配方ILF-01中的体积配比乘以原料的体积固含量就得乳胶漆的体积固含量 $35,37\\%$ 。乳胶漆的体积固含量也是一个重要的参数。单位面积的涂料体积用量乘以体积固含量就等于干膜厚度。  \n\n(3）试验配方在保持成本、钛白粉用量、对比PVC、 $85^{\\circ}$ 掠角光泽和 ${{60}^{\\circ}}$ 光泽、颜色、黏度基本不变的情况下，采用触变填料和非触变填料，设计如表3-1-22 的试验配方。  \n\nILF-01就是初始配方。  \n\nILF-16仅用非触变碳酸钙，粗细碳酸钙搭配可达到预期的85°掠角光泽和 ${60}^{\\circ}$ 光泽。碳酸钙吸油量低，LCPVC高。为了保持对比PVC不变，所以PVC也高，固含量也高，乳液用量少。  \n\nILF-13用了两种触变填料。由于吸油量高，LCPVC 低。为了保持对比PVC 不变，所以PVC也低，固含量很低，乳液用量多。  \n\nILF-04用单-非触变粗石英粉配制。  \n\nILF-14用两种粗细石英粉搭配。  \n\n表3-1-22试验配方  \n\n\n<html><body><table><tr><td>序号</td><td>原</td><td>料</td><td>ILF-01</td><td>ILF-16</td><td>ILF-13</td><td>ILF-04</td><td>ILF-14</td></tr><tr><td colspan=\"8\">打浆</td></tr><tr><td>1</td><td>水</td><td></td><td>34.23</td><td>34.23</td><td>34.23</td><td>34.23</td><td>34.23</td></tr><tr><td>2</td><td>羟甲基纤维素Celflow S-100</td><td></td><td>0.54</td><td>0.54</td><td>0.54</td><td>0.54</td><td>0.54</td></tr><tr><td>3</td><td>pH调节剂AMP-95</td><td></td><td>0.18</td><td>0.18</td><td>0.18</td><td>0.18</td><td>0.18</td></tr><tr><td>4</td><td>丙二醇</td><td></td><td>3.13</td><td>3.13</td><td>3.13</td><td>3.13</td><td>3.13</td></tr><tr><td>5</td><td>成膜助剂Texanol</td><td></td><td>0.95</td><td>0.95</td><td>0.95</td><td>0.95</td><td>0.95</td></tr><tr><td>6</td><td>防腐剂AMA480</td><td></td><td>0.24</td><td>0.24</td><td>0.24</td><td>0.24</td><td>0.24</td></tr><tr><td>7</td><td>消泡剂Colloid 643</td><td></td><td>0.36</td><td>0.36</td><td>0.36</td><td>0.36</td><td>0.36</td></tr><tr><td>8</td><td>湿润剂Triton N 101</td><td></td><td>0.26</td><td>0.26</td><td>0.26</td><td>0.26</td><td>0.26</td></tr><tr><td>9</td><td>分散剂Colloid226(35%）</td><td></td><td>0.72</td><td>0.72</td><td>0.72</td><td>0.72</td><td>0.72</td></tr><tr><td>10</td><td>钛白粉</td><td></td><td>18.09</td><td>18.09</td><td>18.09</td><td>18.09</td><td>18.09</td></tr><tr><td>11</td><td>13μm粗碳酸钙</td><td>25.85</td><td></td><td>58.88</td><td>0</td><td>0</td><td>0</td></tr><tr><td>12</td><td>1.5μm烧高岭土</td><td></td><td>18.00</td><td>。</td><td>14.18</td><td>0</td><td>0</td></tr><tr><td>13</td><td>3μm细碳酸钙</td><td></td><td>0</td><td>35.01</td><td>0</td><td></td><td></td></tr><tr><td>14</td><td>硅藻土</td><td></td><td></td><td>。</td><td>4.79</td><td>。</td><td>5。</td></tr><tr><td>15 16</td><td>12.5μm粗石英粉</td><td></td><td></td><td></td><td>0</td><td>53.34</td><td>26.96</td></tr><tr><td></td><td>3μm细石英粉</td><td>。</td><td></td><td></td><td>。</td><td></td><td>44.45</td></tr><tr><td colspan=\"8\">调漆</td></tr><tr><td>17</td><td>水</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>18</td><td>羟甲基纤维索Celflow S-100</td><td>14.61 0.27</td><td></td><td></td><td>20.26 0.42</td><td>9.22 0.24</td><td>7.53</td></tr><tr><td>19</td><td>消泡剂Colloid 643</td><td>0.23</td><td>0 0.23</td><td></td><td>0.23</td><td></td><td>0</td></tr><tr><td>20</td><td>醋丙乳液（55%）</td><td>24.84</td><td>21. 14</td><td></td><td></td><td>0.23</td><td>0.23</td></tr><tr><td></td><td>合计</td><td>142.50</td><td>173.96</td><td></td><td>27.68 126.26</td><td>27.51 149.24</td><td>21.29 159.16</td></tr></table></body></html>  \n\n(4）性能测试试验配方的性能测试结果见表3-1-23。  \n\n表3-1-23试验配方的性能测试结果  \n\n\n<html><body><table><tr><td>性能及参数</td><td>ILF-01</td><td>ILF-16</td><td>ILF-13</td><td>ILF-04</td><td>ILF-14</td></tr><tr><td>对比PVC</td><td>1.15</td><td>1.14</td><td>1.19</td><td>1.17</td><td>1.38</td></tr><tr><td>赫格曼细度（ASTMD1210)</td><td>4</td><td>4</td><td>4</td><td>3</td><td>4 #</td></tr><tr><td>密度（ASTM D1475)</td><td>1.44</td><td>1.78</td><td>1.28</td><td>1.49</td><td>1.61</td></tr><tr><td>黏度/KU(ASTMD 562)</td><td>92</td><td>97</td><td>93</td><td>92</td><td>99</td></tr><tr><td>每升涂料60g氧化铁红着色后黏度/KU</td><td>93</td><td>99</td><td>95</td><td>93</td><td>100</td></tr><tr><td>pH</td><td>8.9</td><td>9.3</td><td>8.7</td><td>9.4</td><td>8.8</td></tr><tr><td>75μm涂布器涂布的涂膜反射率，Y值/%</td><td>91.10</td><td>90.68</td><td>90.49</td><td>85.62</td><td>88.02</td></tr><tr><td>75μm涂布器涂布的涂膜对比率/%</td><td>95.75</td><td>95.82</td><td>94.94</td><td>93.76</td><td>97.34</td></tr><tr><td>150μm涂布器涂布的涂膜反射率，Y值/%</td><td>92.63</td><td>91.94</td><td>91.64</td><td>86.40</td><td>88.38</td></tr><tr><td>150μm涂布器涂布的涂膜对比率/%</td><td>98.56</td><td>98.77</td><td>98.36</td><td>98.51</td><td>99.59</td></tr><tr><td>每升涂料60g氧化铁红着色后75m涂布器涂布的涂膜反</td><td>26.78</td><td>26.12</td><td>26.53</td><td>23.14</td><td>27.29</td></tr><tr><td>射率(Y值)/%</td><td>0.00</td><td>4.20</td><td></td><td>21. 23</td><td></td></tr><tr><td>相对着色强度/% 75μm涂布器涂布的涂膜散射系数</td><td>2.813</td><td>2.763</td><td>1.61 2.469</td><td>1.724</td><td>3.34</td></tr><tr><td>150μm涂布器涂布的涂膜散射系数</td><td>2.582</td><td>2.573</td><td>2.253</td><td>1.633</td><td>2.897</td></tr><tr><td>平均散射系数</td><td>2.698</td><td>2.668</td><td>2.361</td><td></td><td>2.691</td></tr><tr><td>85°掠角光泽（ASTMD523)</td><td></td><td></td><td></td><td>1.679</td><td>2.794</td></tr><tr><td></td><td>1.9</td><td>2.1</td><td>1.9</td><td>0.5</td><td>1.8</td></tr><tr><td>60*光泽（ASTMD 523) 150μm涂布器涂布的涂膜孔除率（Y值保持率，ASTMD</td><td>2.6 87.57</td><td>2.6 85.36</td><td>2.6 88.53</td><td>2.0 95.38</td><td>2.5</td></tr><tr><td>3258)/%</td><td></td><td></td><td></td><td></td><td>80.55</td></tr><tr><td>耐洗刷性（ASTMD2486)/次</td><td>1043</td><td>439</td><td>1402</td><td>2000+</td><td>843</td></tr><tr><td>流平性（ASTMD 4062)</td><td>5</td><td>3</td><td>4</td><td>5</td><td>4</td></tr><tr><td>抗流挂性（ASTMD 4400)/mil</td><td>10</td><td>14</td><td>12</td><td>14</td><td>14</td></tr><tr><td>辊涂抗飞溅性（ASTMD4707）</td><td>8</td><td>8</td><td>8</td><td>7</td><td>7</td></tr><tr><td>均匀性（framing)</td><td>8.0</td><td>6.0</td><td>8.5</td><td>7.0</td><td>7.0</td></tr><tr><td>修补性（touch-up)</td><td>8.0</td><td>5.0</td><td>8.5</td><td>6.0</td><td>7.0</td></tr><tr><td>抗水迹性（water spotting）</td><td>10.0</td><td>10.0</td><td>10.0</td><td>10.0</td><td>10.0</td></tr></table></body></html>\n\n注：1mil=2.54×10\\~§m,  \n\n其中国内较少见的试验项目简述如下。  \n\n①白漆的着色强度和相对着色强度该试验是测定白漆或基础漆达到给定深度颜色所需色浆量。正负百分数是相对于标准漆而言的。着色强度越高，所需色浆越多。着色采用工业标准含二醇类色浆，用量为每升涂料60g氧化铁红。在不透明干膜上测定反射率，相对着色强度按纽约钛白粉颜料公司1955年修订版手册第92页计算。  \n\n②亚光内墙涂料的均匀性（framing）这一试验是测试当采用辊涂法涂装墙面，用刷涂修边时，所得涂膜的均匀性。选用0.14m²或大于0.14m的试板，先用被试涂料涂一遍，干燥24h。涂料和试板都放置在约25℃的环境中。然后用刷子在试板四周涂刷约8cm宽的涂膜，表干后即滚涂一遍试板，同时覆盖刷涂部分。干燥24h后，观测涂膜的均匀性，以0～10打分，0表示刷涂和辊涂之间无差别，即均匀性好，10表示差别严重。 X  \n\n$\\textcircled{3}$ 亚光内墙涂料的修补性（touch-up）这一试验是评估涂膜损坏后经修补和原涂膜的一致性。在均匀性（framing）测验后的试板上，立即用2in（lin=2.54cm）的刷子涂刷一个大“×”。干燥24h后，以 $\\times$ 的明显度打分。0表示看不出 $\\times$ ，10表示×十分明显。  \n\n$\\textcircled{4}$ 亚光内墙涂料的抗水迹性（water spottingresistance）将修补性（touch-up）测验后的试板直立，立即用 $0.5\\mathrm{mL}$ 的水流过试板。24h后观测水迹，以 $0\\sim10$ 打分，0表示未见水迹，抗水迹性好，10表示水迹十分严重，抗水迹性差。  \n\n综合试验结果虽然在表中没有列出，但由于相同的钛白粉使用量，湿遮盖力是一样的。因为石英粉的颜色较深，所以 $\\tt I L F-O4$ 和ILF-14两配方的反射率 $\\boldsymbol{Y}$ 值较低。综合各项结果，ILF-01配方把触变填料和非触变填料搭配使用的涂料性能比较好。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 859,
+        "chunk": "# 10.配方的优化  \n\n配方优化的目的是达到乳胶漆的性能要求，寻求乳胶漆性能与其配方成本之间的最佳平衡点，举例说明如下。  \n\n(1）内墙乳胶漆配方调整高遮盖力平光内墙乳胶漆的配方调整优化见表3-1-24。  \n\n表3-1-24高遮盖力平光内墙乳胶漆配方调整优化 单位：质量份  \n\n\n<html><body><table><tr><td>原 料</td><td></td><td>A1初始配方</td><td>A2</td><td>A3</td><td>A4</td></tr><tr><td>水</td><td></td><td>382.7</td><td>382.7</td><td>318</td><td>318</td></tr><tr><td>无机增稠剂Bentone EW</td><td></td><td>3.3</td><td>3.3</td><td>一</td><td>一</td></tr><tr><td>无机增稠剂Bentone LT</td><td></td><td>一</td><td>一</td><td>5</td><td>5</td></tr><tr><td>防腐剂 Parmentol A 23</td><td></td><td>2</td><td>2</td><td>1. 5</td><td>1.5</td></tr><tr><td>湿润分散剂Calgon N</td><td></td><td>0.5</td><td>0.5</td><td>0.5</td><td>0.5</td></tr><tr><td>湿润分散剂Coatex P90</td><td></td><td>2.5</td><td>2.5</td><td>一</td><td>一</td></tr><tr><td>湿润分散剂Orotan 731</td><td></td><td>一</td><td>一</td><td>4</td><td>4</td></tr><tr><td>增稠剂MC(30000mPa·s)</td><td></td><td>3</td><td>3</td><td>一</td><td>一</td></tr><tr><td>增稠剂MC(2000mPa·s)</td><td></td><td>3</td><td>3</td><td>一</td><td>一</td></tr><tr><td>消泡剂Agitan280</td><td></td><td>2</td><td>2</td><td>1</td><td>1</td></tr><tr><td>钛白粉Kronos2190</td><td></td><td>180</td><td>180</td><td>170</td><td>一</td></tr><tr><td>钛白粉Kronos 2043</td><td></td><td>一</td><td>一</td><td>一</td><td>180</td></tr><tr><td>硅铝酸盐P820</td><td></td><td>55</td><td>55</td><td>40</td><td>一</td></tr><tr><td>重质碳酸钙Durcal 5</td><td></td><td>235</td><td>一</td><td>一</td><td>一</td></tr><tr><td>重质碳酸钙Industrie Spez</td><td></td><td>一</td><td>60</td><td>80</td><td>60</td></tr><tr><td>滑石粉TalkumV70</td><td></td><td>一</td><td>75</td><td>一</td><td>一</td></tr><tr><td>滑石粉Talkum N</td><td></td><td>一</td><td>一</td><td>100</td><td>150</td></tr><tr><td>微细滑石粉Microtalc(3μm）</td><td></td><td>一</td><td>50</td><td>50</td><td>50</td></tr><tr><td>云母粉MicaW160</td><td></td><td></td><td>50</td><td>一</td><td>一</td></tr><tr><td>湿磨云母粉Glimmer 2038</td><td>一</td><td></td><td>一</td><td>25</td><td>25</td></tr><tr><td>氨水（25%）</td><td>1</td><td></td><td>1</td><td>1</td><td>1</td></tr><tr><td>水</td><td></td><td>一</td><td>一</td><td>100</td><td>100</td></tr><tr><td>增稠剂MC(6000mPa·s)</td><td></td><td>一</td><td>一</td><td>3</td><td>3</td></tr><tr><td>成膜助剂Texanol</td><td>10</td><td>10</td><td></td><td>20</td><td>20</td></tr><tr><td>丙二醇</td><td>20</td><td></td><td></td><td></td><td>一</td></tr><tr><td>消泡剂Agitan 280</td><td>一</td><td>20 一</td><td></td><td>1</td><td>1</td></tr><tr><td>乳液Acronal 290 D</td><td>100</td><td>100</td><td></td><td>80</td><td>80</td></tr><tr><td>合计</td><td></td><td>1000</td><td>1000</td><td>1000</td><td>1000</td></tr><tr><td>PVC/%</td><td>78</td><td></td><td></td><td>81</td><td></td></tr><tr><td>LCPVC/%</td><td>58</td><td>78</td><td></td><td></td><td>81 61</td></tr><tr><td>PVC与LCPVC的差值</td><td>+20</td><td>58</td><td>61</td><td></td><td></td></tr><tr><td></td><td>0.960</td><td>+20 0.983</td><td></td><td>+20</td><td>+20</td></tr><tr><td>对比率（100μm） 孔除率</td><td>34.6</td><td></td><td>29.2</td><td>0.983 21. 6</td><td>0.985 24.7</td></tr><tr><td></td><td>400</td><td></td><td></td><td>>900</td><td>>800</td></tr><tr><td>抗干燥收缩裂缝/μm 耐洗刷性（DIN53778)/次</td><td>3600</td><td>>900 10000</td><td></td><td>9000</td><td>8000</td></tr><tr><td>原料成本（马克/kg）</td><td>1.43</td><td>1.57</td><td></td><td>1.39</td><td>1.39</td></tr></table></body></html>  \n\n调整说明如下。  \n\nA2配方与A1配方相比，是以层状填料和3um重质碳酸钙搭配组合代替5μm重质碳酸钙。结果是在保持PVC和LCPVC不变的情况下，对比率、抗干燥收缩裂缝、耐洗剧性都得到较大提高，而孔隙率下降。当然原料成本约提高了 $10\\%$  \n\nA3配方在A2配方基础上，进一步进行优化，降低原料成本主要是通过减少钛白粉含量，同时提高PVC和LCPVC，但保持PVC和LCPVC的距离不变。从而既保持A2配方的优良性能，又降低了原料成本，并使其比A1配方成本还低。说明成本低，并不一定代表质量差。  \n\nA4配方和A3配方相比，首先是将A3配方中的钛白粉Kron0s2190（吸油量为 $18\\mathrm{g}/\\$ 100g）用钛白粉Kronos2043（吸油量35g/100g）取代，同时为了保持LCPVC和PVC不变，在A4配方中去掉了硅铝酸盐P820，并稍微调整了钛白粉、滑石粉和 $3\\mu\\mathrm{m}$ 重质碳酸钙的含量。这说明，高遮盖力平光内墙乳胶漆既可以用正常表面包膜钛白粉生产，也可以用高表面包膜钛白粉生产，原料成本不变，性能相似。据钛白粉生产商介绍，高表面包膜钛白粉是专为生产高PVC涂料而设计的。在高PVC 涂料生产中，采用高表面包膜钛白粉应有其优点，说明A4配方还可进一步优化。  \n\n又如一个低成本高PVC的内墙乳胶漆配方（表3-1-25)，在保持其他组分不变的情况下，提高乳液用量，能提高耐洗刷性，但会使对比率下降。配方调整应综合考虑各方面因素。  \n\n表3-1-25高PVC的内墙乳胶漆配方调整 单位：质量份  \n\n\n<html><body><table><tr><td>序号</td><td>原料</td><td>配方1</td><td>配方2</td><td>配方3</td></tr><tr><td>1 2 3</td><td>水 乙二醇 分散剂 湿润剂</td><td>20.0 1.5 0.5 0.1 0.15</td><td></td><td></td></tr><tr><td>4 5 消泡剂 6 7 8</td><td>立德粉B301 重钙(1250目) 轻钙（400目)</td><td>20.0 5.0 12.0</td><td>同配方1</td><td>同配方1</td></tr><tr><td>9 10</td><td>滑石粉（325目） 高岭土(TSP-88) Texanol成膜助剂</td><td>8.0 10.0 0.7</td><td></td><td></td></tr><tr><td>11 12</td><td>消泡剂</td><td>0.15</td><td></td><td></td></tr><tr><td>13</td><td>乳液</td><td>11</td><td>13</td><td>15</td></tr><tr><td>415</td><td>测剂</td><td>0.0</td><td>同配方1</td><td>同配方1</td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td>16</td><td>水</td><td>10.2</td><td>8.2</td><td>6.2</td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>合计</td><td>100.00</td><td>100.00</td><td></td></tr><tr><td></td><td></td><td></td><td></td><td>100.00</td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>PVC/% 对比率</td><td>75 0.94</td><td>71 0.91</td><td>70 0.89</td></tr></table></body></html>\n\n注：随着乳液用量增加，水减少，为了保持黏度不变，增稠剂用量要稍微降低。  \n\n(2）外墙乳胶漆配方调整平光外墙乳胶漆的配方调整优化见表3-1-26。  \n\n表3-1-26平光外墙乳胶漆配方调整优化 单位：质量份  \n\n\n<html><body><table><tr><td>配方</td><td>B1初始配方</td><td>B2</td><td>B3</td><td>配方</td><td>B1初始配方</td><td>B2</td><td>B3</td></tr><tr><td>水</td><td>174</td><td>207</td><td>201</td><td>成膜助剂Texamol</td><td>20</td><td>20</td><td>20</td></tr><tr><td>无机增稠剂 Bentone LT</td><td>6</td><td>6</td><td>2</td><td>丙二醇</td><td>20</td><td>20</td><td>20</td></tr><tr><td>防腐剂Parmentol A23</td><td>1.5</td><td>1.5</td><td>1. 5</td><td>乳液 Acronal 290 D</td><td>320</td><td>267</td><td>267</td></tr><tr><td>湿润分散剂Calgon N</td><td>1</td><td>1</td><td>1</td><td>增稠剂Rheolate 278</td><td>一</td><td></td><td>10</td></tr><tr><td>湿润分散剂Coatex 90</td><td>2.5</td><td>2.5</td><td>2.5</td><td>合计</td><td>1000</td><td>1000</td><td>1000</td></tr><tr><td>湿润剂Genapol PN30</td><td>2</td><td>2</td><td>2</td><td>PVC/%</td><td>50</td><td>55</td><td>55</td></tr><tr><td>消泡剂Agitan 280</td><td>2</td><td>2</td><td>2</td><td>LCPVC/%</td><td>58</td><td>66</td><td>66</td></tr><tr><td>钛白粉Kronos 2310</td><td></td><td>205</td><td>205</td><td>PVC 与LCPVC的差值</td><td>-8</td><td>- 11</td><td>11</td></tr><tr><td>钛白粉Kronos 2043</td><td>205</td><td>一</td><td></td><td>孔雕率</td><td>1. 9</td><td>2.1</td><td>2.0</td></tr><tr><td>0.7μm重质碳酸钙</td><td>100</td><td>120</td><td>120</td><td>对比率（150μm)</td><td>0.978</td><td>0.978</td><td>0.978</td></tr><tr><td>10μm滑石粉</td><td>75</td><td>75</td><td>75</td><td>抗干燥收缩裂缝/μm</td><td>>900</td><td>>900</td><td>>900</td></tr><tr><td>3μm滑石粉</td><td>50</td><td>50</td><td>50</td><td>耐洗刷性（DIN53778）/次</td><td>>10000</td><td>>10000</td><td>>10000</td></tr><tr><td>8μm云母粉</td><td>20</td><td>20</td><td>20</td><td>原料成本/（马克/kg）</td><td>2.03</td><td>1.93</td><td>1.93</td></tr><tr><td>氨水（25%）</td><td>1</td><td>1</td><td>1</td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n调整优化说明如下。  \n\n对于B1初始配方，钛白粉选择有些欠妥，因为高表面包膜、高吸油量的钛白粉Kronos2043一般用于高PVC乳胶漆，现平光外墙乳胶漆PVC不高，所以一般不应选该钛白粉。  \n\nB2配方在B1配方基础上，将钛白粉Kronos2043换成钛白粉Kronos2310，另外降低了乳液的用量，增加了 $0.7\\mu\\mathrm{m}$ 重质碳酸钙用量。从而LCPVC从 $58\\%$ 提高至 $66\\%$ ，PVC与LCPVC的距离从 $8\\%$ 增至 $11\\%$ 。结果是原料成本下降，而乳胶漆性能提高。  \n\nB3配方在B2配方基础上，调整了增稠系统，采用无机增稠剂与缔合型聚氨酯增稠剂结合，提高了高剪切力时的黏度、改善了流变性。使乳胶漆性能进一步提高。  \n\n(3）利用数理统计和计算机技术进行配方设计和优化在乳胶漆的配方设计和优化中，采用数理统计知识，如正交试验设计、回归分析等，结合计算机技术，进行试验设计和优化处理，往往能少做试验、较快较好地取得结果，即达到事半功倍的效果。目前，市场上已有该类计算机软件出售，且包括原材料管理等多项内容，使用十分方便。  \n\n(4）通过生产调整配方通过试验室试验确定的配方，在实际生产时，有时还难以保证试验结果重现，因为生产设备与实验设备不同，计量也不一样等，还应根据实际生产产品的检验结果进行调整，以达到预期结果。  \n\n谁都希望有一个最佳配方，但最佳配方不是从资料上找来的，不是由原材料供应商送的，也不是花钱买的。最佳配方应当是根据原材料的情况、设备的特点、管理水平、市场定位、有关标准和法规等因素，逐步调整完善而达到的一个适合本公司实际情况的动态折中和平衡，因为一是涂料的某些性能犹如跷晓板；二是情况总是变化发展的。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 860,
+        "chunk": "# 四、乳胶漆的生产  \n\n乳胶漆的生产过程包括颜料和填料分散、乳液漆的调制、配色、过滤、灌装和质量控制等工序。如果自己不合成乳液，乳胶漆的生产没有化学反应，只是物理的分散混合过程。在配方确定以后，剩下的问题就是准确地计量、有效地分散、均匀地混合、稳定地贮存和严格地控制等。在各组分的混合过程中，由于乳液和颜料填料的数量最大，所以，主要指这两种组分的混合方法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 861,
+        "chunk": "# 1.原料检验和控制  \n\n原料检验和控制是质量管理的重要环节，是乳胶漆生产第一关，一定要把好这一关。设置性能指标和允许波动范围，确定试验方法，建立验收程序。根据原材料在乳胶漆生产中的重要等级、检测难易程度和测试设备情况等，分别采取实际检测和验证供方提供的检验报告等方法。  \n\n（1）乳液配方确定后，乳液就是影响乳胶漆质量的最关键因素，因此要高度重视其质量。乳液的检验可参照GB/T20623—2006《建筑涂料用乳液》，要求见表3-1-27，可选取其中某些项目检验控制。  \n\n表3-1-27 建筑涂料用乳液性能要求  \n\n\n<html><body><table><tr><td>序号</td><td>性 能</td><td>要 求</td></tr><tr><td>1</td><td>容器中状态</td><td>乳白色均匀流体或膏状物，无杂质，无沉淀，不分层</td></tr><tr><td>2</td><td>不挥发物[（150±2)C，15min]/%</td><td>45或商定</td></tr><tr><td>3</td><td>pH值</td><td>商定</td></tr><tr><td>4</td><td>黏度</td><td>商定</td></tr><tr><td>5</td><td>最低成膜温度/℃C</td><td>商定</td></tr><tr><td>6</td><td>玻璃化温度/C</td><td>商定</td></tr><tr><td></td><td>冻融稳定性[（-5±2）℃]/次</td><td>3</td></tr><tr><td></td><td>贮存稳定性[（50±2)℃，20h]</td><td>无硬块，无絮凝，允许有分层但易于搅匀</td></tr><tr><td>g</td><td>稀释稳定性[（3±0.5）%，72h]/% 上层清液体积</td><td>≤5</td></tr><tr><td>10</td><td>下层沉淀体积 ≤5 机械稳定性(440mm,2500rpm,0.5h)/%</td><td>≤不破乳，无明显絮凝物</td></tr><tr><td>11</td><td>钙离子稳定性（0.5%CaCl）</td><td>48h无分层、无沉淀、无絮凝</td></tr><tr><td>12</td><td>残余单体总和/%</td><td>≤0.10</td></tr><tr><td>13</td><td>甲醛含量/（g/kg）</td><td>≤0.08</td></tr><tr><td>14</td><td>挥发性有机物/（g/L)</td><td>≤30</td></tr></table></body></html>\n\n注：标准规定第13和第14项是仅对内墙乳胶漆用乳液的要求，但外墙涂料有害物质限量即将实施，因此，外墙乳胶漆用乳液也按此要求。  \n\n(2）颜料填料钛白粉在原料成本中所占比例大，我国市场目前有些不够规范，一定要有控制手段。一般可对遮盖力、吸油量或吸水量、细度、颜色等设置控制指标。  \n\n填料检验和控制在国内没有引起足够的重视。有些生产企业不检验，不控制；有些生产企业基本不检验，不控制；有些生产企业想检验，要控制，但又找不到合适的标准和测试方法。其实，ISO3262系列填料标准就是现成的标准，列于下面，可以参考选用。  \n\nISO 3262-1:1997 色漆用体质颜料 规格和试验方法 -1：总则和通用试验方法，ISO 3262-2； 1998 色漆用体质颜料 规格和试验方法一 -2：重晶石粉（天然硫酸钡）。ISO 3262-3: 1998 色漆用体质颜料 规格和试验方法- -3：沉淀硫酸钡，ISO 3262-4; 1998 色漆用体质颜料 规格和试验方法 4；大白粉，ISO 3262-5； 1998 色漆用体质颜料 规格和试验方法一 -5；重质碳酸钙，ISO 3262-6； 1998 色漆用体质颜料 规格和试验方法- -6：沉淀碳酸钙，ISO 3262-7: 1998 色漆用体质颜料- 规格和试验方法 -7：白云石。ISO 3262-8； 1999 色漆用体质颜料 规格和试验方法 -8：天然瓷土。ISO 3262-9； 1997 色漆用体质颜料 规格和试验方法 -9：烧瓷土。ISO 3262-10； 2000 色漆用体质颜料 规格和试验方法 10：天然薄片状滑石/绿泥石，ISO 3262-11: 2000 色漆用体质颜料- 规格和试验方法一 -11：含碳酸盐的薄片状滑石。ISO 3262-12； 2001 色漆用体质颜料 规格和试验方法 -12：白云母。ISO 3262-13； 1997 色漆用体质颜料 规格和试验方法--13；研磨过的天然石英。  \n\nISO 3262-14; 2000 色漆用体质颜料 规格和试验方法 14：方晶石。  \nISO 3262-15； 2000 色漆用体质颜料- -规格和试验方法一 -15；透明二氧化硅，ISO 3262-16； 2000 色漆用体质颜料 规格和试验方法 16： 氢氧化铝.  \nISO 3262-17； 2000 色漆用体质颜料 规格和试验方法一 -17：沉淀硅酸钙。  \nISO 3262-18:2000 色漆用体质颜料 规格和试验方法一 -18：沉淀硅酸铝钠。  \nISO 3262-19； 2000 色漆用体质颜料- 规格和试验方法一 -19：沉淀二氧化硅。  \nISO 3262-20: 2000 色漆用体质颜料 规格和试验方法一 -20：气相二氧化硅。  \nISO 3262-21: 2000 色漆用体质颜料 规格和试验方法一 -21：硅砂(未经粉碎的天然石英)。  \n\n现以ISO3262-5重质碳酸钙为例来说明。其中化学分析（基本要求）见表3-1-28，物理性能（条件要求）见表3-1-29。  \n\n表3-1-28化学分析（基本要求）  \n\n\n<html><body><table><tr><td>特 性</td><td>单位</td><td>一级</td><td>二级</td><td>三级</td><td>四级</td><td>试验方法</td></tr><tr><td>CaCO含量</td><td>%</td><td>99</td><td>98</td><td>95</td><td>90</td><td>ISO 3262-1</td></tr><tr><td>105℃挥发物 ≤#</td><td>%</td><td colspan=\"4\">0.4</td><td>ISO 787-2</td></tr><tr><td>烧失量 ≤</td><td>%</td><td colspan=\"4\">46</td><td>ISO 3262-1</td></tr><tr><td>水溶物 ≤</td><td>%</td><td colspan=\"4\">0.5</td><td>ISO 787-3或ISO 787-8</td></tr><tr><td>pH</td><td></td><td colspan=\"4\">8~10</td><td>ISO 787-9</td></tr><tr><td>HCI不溶物 ≤</td><td>%</td><td>1</td><td>2</td><td>2</td><td>8</td><td>ISO 3262-5</td></tr></table></body></html>  \n\n表3-1-29物理性能（条件要求）  \n\n\n<html><body><table><tr><td>特 性</td><td>单 位</td><td>指 标</td><td>试验方法</td></tr><tr><td>45μm筛余</td><td>%</td><td>双方商定</td><td>ISO 787-7</td></tr><tr><td>粒径分布（仪器法）</td><td>%</td><td colspan=\"2\">双方商定</td></tr><tr><td>颜色</td><td></td><td>双方商定</td><td>ISO 3262-1</td></tr><tr><td>明度</td><td></td><td colspan=\"2\">双方商定</td></tr><tr><td>水萃取物电阻率</td><td>·m</td><td>双方商定</td><td>ISO 787-14</td></tr></table></body></html>  \n\n可以根据企业实际情况，选择其中一些项目进行检验控制，尤其是表3-1-29的内容。  \n\n(3）溶剂（成膜助剂和助溶剂）可测试外观、颜色、折射率和馏程等，加以控制。这些项目测试简便，十分有效。  \n\n(4）助剂助剂可以功能为主，兼顾其他指标进行检验。功能检验是指在特定条件下，测试其功能，以便比较。如增稠剂，可测试某一浓度下的黏度。(5）水对水可设置硬度或电导值进行控制。若有条件，细菌也可作为监测指标。(6）色浆一般对色浆的着色力、相容性和色相等进行检验和控制。  \n\n为了对两种色浆的着色力进行比较，首先应选择一个适当的白色乳胶漆，称取同样重量分别置于两个容器中。在一个容器中加入一定量的色浆标准样，在另一个容器中加入同样量的色浆待测样。把容器固定在装有计时器的振动混合器上混合一定时间。混合后，平行地刮涂试板。分为马上和/或干燥后两次进行，目测着色力、色相和遮盖力。如有条件，可用测色仪测定。相容性可用指研法测定。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 862,
+        "chunk": "# 2.颜料填料分散方法  \n\n无论是颜料还是填料，在买来的时候，都是由数百个到数千个一次粒子（primary par-ticle）凝聚起来的二次粒子（secondary particle）组成的。在和乳液混合的时候，分为是将颜料和填料的二次粒子还原成一次粒子后再混合，还是将二次粒子直接加到乳液中后分散混合。据此，配制方法有明显的不同。前一种混合方法叫做研磨着色法（grindingpigmenta-tion)；后一种方法叫做干着色（dry pigmentation）法。当配方中总用水量不足以采用研磨着色法时，可以在水中先加入部分乳液，然后将颜料和填料的二次粒子加入其中分散，分散达到要求后，将剩下的乳液加入混合均匀，此法称为半干着色法。  \n\n研磨着色法是对颜料和填料二次粒子施加大量的机械能，使其先在水中解聚、分散形成料浆，再与基料混合。与此相反，干着色法是将颜料和填料二次粒子直接加入到基料中进行分散搅拌，因此，两种配制方法所制造的乳胶漆，其固体分和颜料、填料的解聚、分散状态有所不同。  \n\n在不同PVC下计算得到的研磨着色法和干着色法的固含量见表3-1-30。在计算时假定乳液固含量为 $50\\%$ 、聚合物密度为 $1.0\\mathbf{g}/\\mathrm{cm}^{3}$ 、颜料和填料的平均密度为 $2.8g/\\mathrm{cm}^{3}$  \n\n单位：%  \n\n表3-1-30乳胶漆的配制方法和固含量  \n\n\n<html><body><table><tr><td rowspan=\"2\">PVC</td><td colspan=\"2\">研磨着色法</td><td rowspan=\"2\">干著色法</td><td rowspan=\"2\">PVC</td><td colspan=\"2\">研磨着色法</td><td rowspan=\"2\">干着色法</td></tr><tr><td></td><td>磨料固含量65%磨料固含量55%</td><td>磨料固含量65%磨料固含量55%</td><td></td></tr><tr><td>20</td><td>55.2</td><td>51.9</td><td>63.0</td><td>50</td><td>60.2</td><td>53.6</td><td>79.2</td></tr><tr><td>30</td><td>57.2</td><td>52.6</td><td>68.8</td><td>60</td><td>61.5</td><td>54.0</td><td>83.9</td></tr><tr><td>40</td><td>58.8</td><td>53.2</td><td>74.1</td><td>70</td><td>62.5</td><td>54.3</td><td>88.3</td></tr></table></body></html>  \n\n因为在研磨着色法中磨料的调制受黏度的制约，所以打浆时磨料的固含量一般在 $70\\%$ 以下。在磨料固含量为 $65\\%$ 的情况下，用该法制造的涂料在表3-1-30所列的实用PVC范围内，其固含量最高可达 $62\\%$ 左右。而用干着色法制造的涂料，其固含量可高达 $88\\%$ 。不管是研磨着色法，还是干着色法，乳胶漆的固含量都随PVC的增大而提高。  \n\n就颜料的分散状态来说，干着色法对于二次粒子的解聚不像研磨着色法那样充分，而且这种倾向在颜料粒子越小时越明显。因此，对于有光乳胶漆，一般均采用研磨着色法生产。  \n\n干着色法和半干着色法都要求乳液机械稳定性好，高速分散时不破乳。现在许多乳液能达此要求。  \n\n对于弹性乳胶漆、立体花纹饰面涂料和砂壁状饰面涂料等厚质涂料，因为其涂膜厚度厚，在干燥成膜时，容易产生收缩裂缝，为了避免此倾向，往往需要降低涂料含水量，并且尽量不使用太细颜料和填料。另外，作为厚质涂料，要求一次施涂厚度也比较厚，因此也需要提高其含固量。这就造成厚质涂料含水量低，无法采用研磨着色法生产，只能采取半干着色法和干着色法生产。  \n\n对于薄层涂料和配方中含水量足够采用研磨着色法生产的涂料，应采用研磨着色法生产。  \n\n在采用研磨着色法或半干着色法生产时，颜料和填料分散完成后，一般应将乳液慢速加入颜料和填料浆中调制成漆，而不是反之。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 863,
+        "chunk": "# 3.乳胶漆的调制  \n\n乳胶漆的调制与传统的涂料生产工艺大体相同，一般分为预分散、分散、调和、过滤、包装等。但是就传统涂料来说，漆料作为分散媒在预分散阶段就与颜料、填料相遇，颜料、填料直接分散到漆料中，而对乳胶漆而言，由于乳液对剪应力通常较为敏感，在低剪力混合阶段，使之与颜料、填料分散浆相遇才比较安全。因而颜料、填料在分散阶段仅分散在水中，水的黏度低，表面张力高，因而分散困难，所以在分散作业中需加入润湿剂、分散剂、增稠剂。由于分散体系中，有大量的表面活性剂，容易产生气泡而妨碍生产进行。因而分散作业中，还必须加消泡剂。显然乳胶漆的调制较复杂。  \n\n乳胶漆生产线上直接生产的主要是白漆和基础漆，色浆一般是另行制备的。生产作业线主要考虑钛白粉等白色颜料和填料的分散。现代钛白粉中有专供乳胶漆使用的属于极易分散的品种，常用的填料一般也都是经过超细处理的。加之建筑乳胶漆对细度要求不高，所以乳胶漆生产线上通常只需装置高速分散机。高速分散机最好带有调速装置，这样分散和调漆就可以在一台高速分散机中完成。  \n\n当然，在特定条件下，为了适应对细度的较高要求，或适应可能遇到的较粗颜料和填料，除高速分散机以外，有些乳胶漆车间也装备有砂磨机和球磨机等设备。  \n\n乳胶漆生产中加料顺序是相当重要的，一般如下。  \n\n首先在搅拌缸中加入水、防腐剂、防霉剂、湿润分散剂、约 $_{1/2}$ 的消泡剂、增稠剂、助溶剂，充分混合均匀。如必需时，也可加入部分乳液。对于热稳定性差的防腐剂和防霉剂，应在调漆后阶段加入，以防制浆时温度过高使其分解而失效。  \n\n然后，将分散盘中心靠近搅拌缸底部，低速旋转，将颜料、填料逐渐加入纵深的漩涡中，先加细的颜料、填料，后加更粗的颜料、填料。这样加既有利于分散，又有利于消泡。随着颜料和填料的加人，磨料变稠，应提高分散盘的位置，使漩涡变浅，并相应提高转速。当所有的颜料和填料加完以后，将转速提高，使分散盘周边线速度为 $20{\\sim}25\\mathrm{m}/\\mathrm{s}$ ●  \n\n一般认为，在该转速下颜料和填料分散最好。研磨分散时间一般为 $15\\mathrm{min}$ 左右，具体应以达到分散细度要求为度，对于丝光、半光和有光乳胶漆磨料，细度一般应少于 $20\\mu\\mathrm{m}$ .对于平光内墙乳胶漆磨料，细度一般可控制在 $40\\mu\\mathrm{m}$ 以下；对于平光外墙乳胶漆磨料，细度甚至可放至 $100\\mu\\mathrm{m}$ 以下。应注意分散时磨料的温度，温度太高，如超过 $45\\%$ 时，黏度下降，分散将无法进行，可暂停下来，待冷却后，再分散。  \n\n分散细度合格后，在低速搅拌情况下，加入乳液、成膜助剂、部分增稠剂和另外约1/2消泡剂。  \n\n至于 $\\mathsf{p H}$ 调节剂，如是AMP-95，在颜料和填料分散前加入；如是氨水，可在乳液加入后加入；如为 $\\mathrm{\\DeltaNaOH}$ 、KOH，可在颜料和填料分散后，乳液加人前加入。  \n\n也有将成膜助剂在颜料和填料分散前加入的，这对乳液比较安全，但有可能被颜料和填料黏着吸人一部分。  \n\n这是一般的加料次序，具体可根据原料性能、分散设备、实际操作情况和对分散的要求等而定。  \n\n千万别将制备好的而未加乳液的颜料和填料浆放置超过24h，尤其是有光乳胶漆的颜料和填料浆，以防止絮凝、结块和不稳定等。当制浆时还未加防腐剂、防霉剂时，由于温度较高，甚至有可能被细菌污染而报废的危险。  \n\n由于乳胶漆发展非常快，产量剧增，成为重要的涂料品种。钛白粉工业也相应发展了钛白水浆，碳酸钙工业也有碳酸钙浆。以水浆生产乳胶漆，不但使钛白粉工业和碳酸钙工业节省了干燥、气流粉碎和分级作业能耗，而且也使涂料工业缩短工时，提高工效，节省分散作业能耗。  \n\n现代乳胶漆专业生产厂的流程模式大致是这样的：用汽车槽车将乳液、钛白浆、散装填料送入厂内，用泵将其送到贮罐和粉料仓中。配料时，加水和助剂，并用泵等输送设备将钛白浆、填料通过计量器送至高速分散机，用高速挡进行分散作业。分散作业完成后，降低转速，将乳液通过流量计用泵送到高速分散机中，并加入其他助剂，搅拌均匀。这样制备完成的往往是白色乳胶漆和基础漆。  \n\n经检验合格后，白色乳胶漆和基础漆被送至贮罐。在接到订单后，即可灌装或配色，从  \n\n而在最短时间内就能交货。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 864,
+        "chunk": "# 4.生产过程控制  \n\n在生产过程中，对乳胶漆的半成品进行检验。经检验合格后，才能转序。这里所说的半成品，包括浆料（未加乳液）、基础漆和白乳胶漆。  \n\n(1）分散细度在打浆阶段完成后，乳液加入之前，要对分散细度进行检验，以确定是否达到分散要求。  \n\n(2)pH $\\mathsf{p H}$ 虽然不反映乳胶漆质量，但它与乳胶漆的稳定性，包括冻融稳定性、纤维索增稠剂和碱溶胀型增稠剂的增稠效果以及防腐等都存在一定关系，所以乳胶漆生产企业一般都将 $\\mathsf{p H}$ 控制在一定的范围内。  \n\n(3）固含量在相同湿膜条件下，固含量较高的涂料能得到较厚的干膜厚度。在相同涂膜质量时，较厚的涂膜使用寿命一般较长。  \n\n另外，固含量的测试结果还能反映乳胶漆的批和批之间的稳定性及一致性。因此有些企业将固含量作为内控指标进行控制。  \n\n（4）黏度在特定的生产工艺中，黏度可以反映乳胶漆的贮存稳定性和施工性，还能检查计量情况和原材料的波动，生产企业通常检验并控制该指标。  \n\n（5）密度密度不是乳胶漆的质量指标，测试它也能反映批和批之间的稳定性。  \n\n(6）细度细度检验对于乳胶漆来说，是需要的，尤其是丝光乳胶漆、半光乳胶漆和有光乳胶漆。该项细度与分散细度有联系，但也有区别。它是加入乳液后制得的白乳胶漆和基础漆的细度。  \n\n可选择部分项目检验或对上述项目都进行检验。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 865,
+        "chunk": "# 5.配色  \n\n色彩丰富是乳胶漆的一大特点。目前白色乳胶漆约仅占 $20\\%$ 以下，有色乳胶漆却占80%以上。因此配色就成为乳胶漆生产中的重要环节。  \n\n(1）色浆配色首先就要选择色浆。  \n\n内用乳胶漆颜色可自由选择，因为室内紫外线很弱，又没有雨水等降解作用，所以保色性不成问题。  \n\n外用乳胶漆应尽量选择耐光和耐候好的色浆，最好是耐光性达8级，耐候性达5级；而且冲淡后还要保持较高的耐光性和耐候性，因为乳胶漆配色时，颜料浓度往往是比较低的。同时建筑乳胶漆涂剧的基面绝大多数是碱性较强的水泥砂浆和混合砂浆抹灰层，色浆的耐碱性也是必须考虑的。如无机类色浆和酞菁系列色浆，能达此要求。另外，对于相同的颜色，深色比浅色保色性好。也就是说，对有些保色性不是很好的色浆，配深色乳胶漆能用，但生产浅色乳胶漆就不能用。  \n\n色浆应稳定，包括贮存稳定、颜色稳定色强度稳定和批次之间稳定等。对于自动配色体系，颜色稳定色强度稳定和批次之间稳定尤其重要。  \n\n色浆应和被配色的乳胶漆具有良好的相容性，不絮凝、不浮色等。这主要是指色浆助剂和被配色的乳胶漆助剂之间没有负面作用。当出现相容性不好时，可通过选择相容性好的色浆或改变乳胶漆助剂的方法解决。  \n\n色浆应尽量与环境友好。挥发性有机物（VOC）低，重金属含量低，甲醛含量符合要求，不含烷基酚乙氧基酯（APEO)，该类表面活性剂对人体的内分泌有干扰作用，用丙二醇而不用乙二醇等。  \n\n色浆还应有合理的性能价格比。  \n\n(2）配色方法目前乳胶漆生产企业大多采用全白色乳胶漆配色法和基础漆配色法两种。所谓基础漆配色法，指乳胶漆生产企业生产白色乳胶漆和透明乳胶漆（亦称基础漆），透明乳胶漆是指不含钛白粉等具有遮盖力颜料的乳胶漆，用白色乳胶漆和色浆配浅色漆，用透明乳胶漆和色浆配深色漆，用不同比例搭配的白色乳胶漆和透明乳胶漆同色浆配中色漆。  \n\n用透明乳胶漆和色浆配深色漆时，除了注意配色准确外，还要注意深色漆的遮盖力是否达到要求，尤其是配鲜艳的深黄色漆和深红色漆时。对于深色漆，尽管国家标准GB/T9755和GB/T9756都没有规定其对比率的指标要求，但实际使用时是需要达到一定遮盖力要求的。当遮盖力达不到要求时，可以钛白浆和含钛白粉的白色乳胶漆进行调整。  \n\n有些中小乳胶漆厂习惯采用全白色乳胶漆配色法。用白色乳胶漆来配深色甚至中色乳胶漆，必须加入大量的色浆才能达到一定的饱和度，其结果：大量色浆加入使配色成本大幅度提高，使乳胶漆性能下降，而产生不必要的遮盖力过剩。这是高成本而低质量的做法。  \n\n基础漆配色法，加上调色设备、混匀设备、通用色浆和计算机管理硬软件等，就构成现代调色系统。它可以把配色从涂料生产企业移至各零售店进行，达到就地配色，满足远程用户要求，并降低小批量配色成本。  \n\n(3）库贝尔卡-芒克配色理论传统上，加色法和减色法配色的称呼是用于区分色光的混合和着色剂的混合。加色法的原色是红、绿、蓝，而减色法的原色是绿、黄、蓝，或者是蓝绿、紫和黄。涂料配色是颜料混合，总是采用减色法。减色法配色是指除去物体上来自某个光源的部分光线。除去光线的方法包括吸收和散射。把仅使用吸收而不使用散射的方法称为简单减色法，而把同时使用吸收和散射的方法称为复杂减色法。颜料对光线一般既吸收又散射，所以涂料配色一般采用复杂减色法。库贝尔卡-芒克（Kubelka-Munk）方程就是广泛使用的描述复杂减色法配色的近似方程。  \n\n$\\Phi$ 库贝尔卡-芒克方程考虑一个薄膜，它既散射光，也吸收光，同时还有部分光透过。设膜厚为 $\\boldsymbol{x}$ ，背景反射率为 $R_{8}$ 。厚度变量在背景界面处的厚度为零，光入射界面处的厚度为 $x$ ，反射率为 $R$ ，则：  \n\n$$\n\\begin{array}{c}{{R=\\displaystyle\\frac{1-R_{\\mathrm{g}}(a-b\\coth b S X)}{a-R_{\\mathrm{g}}+b\\coth b S X}}}\\\\ {{a=1+\\displaystyle\\frac{K}{S}\\qquadb=(a^{2}-1)^{\\frac{1}{2}}}}\\end{array}\n$$  \n\n式中 $\\kappa$ —吸收系数；S—散射系数；coth—双曲余切函数。$\\coth b S X=[\\exp(b S X)+\\exp(-b S X)]/[\\exp(b S X)-\\exp(-b S X)]$ 式（3-1-7）就是库贝尔卡-芒克方程（简称K-M方程）的基本形式。  \n\na.简化K-M方程对于不透明薄膜，即在式（3-1-7）中，使散射系数 $s$ 或薄膜厚度 $x$ 逐渐增加，则很快就可以发现 $\\exp(-b S X)$ 对于 $\\exp({6S X})$ ）可以忽略，方程简化为：  \n\n$$\nR_{\\infty}=1+{\\frac{K}{S}}-\\Bigl[\\Bigl({\\frac{K}{S}}\\Bigr)^{2}+2\\Bigl({\\frac{K}{S}}\\Bigr)\\Bigr]^{\\frac{1}{2}}\n$$  \n\n式中 $R_{\\infty}$ ———无限厚度的反射率。  \n\n所谓无限厚度，对涂料来说，是指涂膜具有的遮盖力足以使基层对其视在颜色产生的影响可忽略不计。涂料配色当然要达到该要求。  \n\n式（3-1-9）表明此时厚度进一步增厚将不再影响薄膜的反射率。由式（3-1-9）导出：  \n\n$$\n\\frac{K}{S}{=}\\frac{(1{-}R_{\\infty})^{2}}{2R_{\\infty}}\n$$  \n\n式（3-1-9）和式（3-1-10）是对不透明样品普遍适用的，这里膜厚 $x$ 和背景反射率 $R_{\\mathrm{~s~}}$ 都没有在式中出现。式（3-1-10）也称为简化库贝尔卡-芒克方程。  \n\nb.双常数K-M理论由于吸收系数和散射系数具有加和性。在基体中，当存在n种着色剂，并考虑基体的颜色时，则混合体系的吸收系数：  \n\n$$\nK=k_{1}+c_{1}k_{1}+c_{2}k_{2}+\\cdots+c_{n}k_{n}\n$$  \n\n式中 k：—没有着色剂的基体吸收系数；$c_{1}$ ,C2，…,C——各种着色剂的浓度；$k_{1}$ + $k_{2}$ .,k-各种着色剂的吸收系数，它们是光波长的函数。  \n\n同理，混合体系的散射系数：  \n\n$$\nS=s_{0}+c_{1}s_{1}+c_{2}s_{2}+\\cdots+c_{n}s_{n}\n$$  \n\n式中st—没有着色剂的基体散射系数；  \n$s_{1}$ ,S2，\\*\\*\\*,Sn 一各种着色剂的散射系数，它们也是光波长的函数。  \n\n由式(3-1-11）和式(3-1-12）就可得出，对于混合体系：  \n\n$$\n\\frac{K}{S}=\\frac{k_{1}+c_{1}k_{1}+c_{2}k_{2}+\\cdots+c_{n}k_{n}}{s_{1}+c_{1}s_{1}+c_{2}s_{2}+\\cdots+c_{n}s_{n}}\n$$  \n\n这就是双常数K-M理论。双常数K-M理论常用于涂料的配色和塑料的染色  \n\nc.单常数K-M理论当着色剂的散射性质与其介质相比可以忽略时，对于这样的材料，如织物、纸张和高钛白粉含量的涂料，可只用 $k/s$ 一个参数来表征着色剂。当然， $k/s$ 也是光波长的函数。  \n\n$$\n\\frac{K}{S}{=}\\left(\\frac{k}{s}\\right)_{\\mathrm{t}}{+}c_{1}\\left(\\frac{k}{s}\\right)_{\\mathrm{1}}{+}c_{2}\\left(\\frac{k}{s}\\right)_{\\mathrm{2}}{+}\\cdots{+}c_{n}\\left(\\frac{k}{s}\\right)_{n}\n$$  \n\n这就是单常数K-M理论。单常数K-M理论常用于织物和纸张的染色。对于钛白粉含量高的涂料，尽管其他颜料对光线也有散射，但当加入少量时，也可近似地以单常数K-M理论处理。  \n\nd.对折射率不连续性的桑德森（Saunderson）修正因为K-M理论假设折射率不发生变化，而实际上，折射率是不连续的。对此，采用桑德森修正。  \n\n$$\nR_{\\mathrm{m}}={\\frac{K_{1}+\\left[(1-K_{1})(1-K_{2})~R_{\\infty}\\right]}{1-K_{2}R_{\\infty}}}\n$$  \n\n$$\nK_{1}=\\frac{(n-1)^{2}}{(n+1)^{2}}\n$$  \n\n![](images/045dc3ba4e99ba062cf99630da73c16db2583fc6e7a3ca01ce17e43e36c75a44.jpg)  \n图3-1-6涂料反射率与波长的关系曲线  \n\n式中 $R_{\\mathrm{ro}}$ ——光谱光度计测得的反射率；$K_{1}$ 平行光的菲涅尔（Fresnel）反射系数；——介质的折射率，对于大多数涂料聚合物， $n=$ 1.5，计算得 $K_{1}=0.\\ 04$ .$K_{2}$ ——从内部射向表面的漫射光的菲涅尔（Fresnel）反射系数，对于完全漫射光， $K_{2}$ 的理论值为0.6, $\\boldsymbol{K}_{2}$ 通常在 $0.4\\sim0.6$ 之间变化。  \n\n式(3-1-15）就是桑德森修正。  \n\n$\\textcircled{2}$ 计算举例利用K-M理论确定不透明涂料的颜料配方。该涂料B呈棕色，其反射率与波长的关系曲线如图3-1-6所示，由黄、红和白色颜料配成。试确定其颜料配比。  \n\n先配制白色涂料W，仅含白色颜料；配制黄色涂料Y，包含黄色颜料和白色颜料，黄色颜料占颜料总量的 $18.5\\%$ \\*配制红色涂料R，包含深红色颜料和白色颜料，深红色颜料占颜料总量的13. $6\\%$ 。这三种涂料反射率与波长的关系曲线如图3-1-6所示。  \n\n通常，双常数K-M理论应用于涂料配色。在本例中，做一个简化假定：与白色颜料相比，彩色颜料的散射量相对较小。因此，可以采用单常数K-M理论进行计算。  \n\n因为要确定两个未知含量，所以需要选择两个合适波长，如 $420\\mathrm{nm}$ 和 $560\\mathrm{nm}$ 。根据光谱测试结果，由图3-1-6得波长为 $420\\mathrm{nm}$ 和 $560\\mathrm{nm}$ 的反射率，以分数表示，见表3-1-31。  \n\n表3-1-31波长为420nm和560nm的反射率  \n\n\n<html><body><table><tr><td>涂料试样</td><td>w</td><td>Y</td><td>R</td><td>B</td></tr><tr><td>波长420nm的反射率</td><td>0.768</td><td>0.216</td><td>0.384</td><td>0.167</td></tr><tr><td>波长560nm的反射率</td><td>0.882</td><td>0.872</td><td>0.146</td><td>0.163</td></tr></table></body></html>  \n\n将表3-1-31的数据代人式（3-1-10），得 $\\kappa/s$ 值，列于表3-1-32。  \n\n表3-1-32各涂料试样的K/S值  \n\n\n<html><body><table><tr><td>涂料试样</td><td>w</td><td>Y</td><td>R</td><td>B</td></tr><tr><td>波长420nm的K/S</td><td>0.035</td><td>1. 423</td><td>0.494</td><td>2.078</td></tr><tr><td>波长560nm的K/S</td><td>0.007</td><td>0.009</td><td>2.498</td><td>2.149</td></tr></table></body></html>  \n\n在忽略没有颜料的基体 $(k/s)_{\\mathrm{t}}$ 值的条件下，将R和丫涂料试样中颜料的配比及表3-1-32中 $\\kappa/s$ 值代入式(3-1-14)，得各颜料的 $k/s$ ，见表3-1-33。  \n\n表3-1-33各颜料的k/s值   \n\n\n<html><body><table><tr><td>颜料</td><td>白色</td><td>黄色</td><td>深红色</td></tr><tr><td>波长420nm的k/s</td><td>0.035</td><td>7.538</td><td>3.410</td></tr><tr><td>波长560nm的k/s</td><td>0.007</td><td>0.018</td><td>18.323</td></tr></table></body></html>  \n\n在B涂料试样中，有白色、黄色和深红色三种颜料。看起来有三个未知量，而相对于 $420\\mathrm{nm}$ 和 $560\\mathrm{nm}$ 两个波长，只能写出两个方程。但三种颜料的总和等于 $100\\%$ .这里只有两个自由度。解决这类问题的常用方法是假定白色颜料的含量为1。同样在忽略没有颜料的基体 $(k/s)_{\\ell}$ 值的条件下，将各颜料的 $k/s$ 值和B涂料试样 $\\kappa/s$ 值代人式(3-1-14)，得二元一次联立方程组，解得黄色颜料含量为0.218，深红色颜料含量为0.117。化为百分比，白色、黄色和深红色三种颜料含量分别为：74.9%、16. $3\\%$ 和 $8.8\\%$ 。  \n\n（4）计算机配色简介计算机自动配色设备由分光光度计、带配色软件的计算机和输出装置组成。其中大多数配色软件是基于库贝尔卡-芒克方程，涉及颜色试样的光谱反射率 $R$ （）与吸收系数K、散射系数S之间的关系，以及 $\\kappa$ 值、 $s$ 值和色浆浓度 $\\textit{\\textbf{c}}$ 之间的加和特性。  \n\n$\\textcircled{1}$ 数据库配色软件最主要的组成要素是色浆的数据库。该数据库包括各种色浆的吸收和散射性能，以及理论浓度和有效浓度之间的关系，是对每个波长采用多项式或其他曲线拟合技术，作成 $\\kappa/s$ 对浓度的曲线。数据库就等于配色师的经验。  \n\n$\\textcircled{2}$ 光谱光度法色浆鉴别所谓光谱光度法色浆鉴别，就是根据可见光光谱曲线，鉴别出所要配颜色样品中包含哪几种色浆。色浆本身的光谱反射比曲线对于鉴别色浆是很有用的，但是浓度变化会引起曲线形状发生较大变化。替代方法是把光谱反射比转化为$\\kappa/s$ 的对数。 $\\kappa/s$ 对数光谱曲线的形状几乎与浓度无关，因此可以鉴别所要配颜色样品中的色浆。  \n\n③光谱匹配法光谱匹配法包括色浆选择、初始配方预测和整批校正。首先从数据库中选择能产生最近似光谱匹配的色浆。再进行最小二乘法计算，得到各色浆的有效浓度。使用数据库将有效浓度转变为理论浓度。  \n\n④色度匹配法配色时，首先应考虑用多少种色浆，这就是自由度问题。对于乳胶漆，需要四种色浆，即三个自由度才能实现三刺激值的匹配，因为四种色浆总和等于1。  \n\n测定标样的三刺激值。假定浓度与色度坐标之间存在线性关系，则可以通过解三个联立方程求得四色浆的浓度。实际上，浓度与刺激值之间是高度非线性的。因此，要通过连续逼近的方法，求得真实浓度。色度匹配中最常用的连续逼近法是牛顿-拉夫逊（Newton-Raph-son）法。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 866,
+        "chunk": "# 6.填料对配色的影响  \n\n填料对配色的影响包括填料对LCPVC的影响、填料对遮盖力的影响、填料对消色力的影响和填料对保色性影响等。前两者前文已谈及，此处仅涉及后两者。  \n\n(1）填料对消色力的影响在配色过程中，要达到乳胶漆颜色的准确性和重复性，必须做到三准确和两稳定，即色漆配方、注浆和基础漆计量的准确，色浆和基础漆的稳定。以下就基础漆的稳定中，常被人们忽略的填料对消色力影响做一介绍。  \n\n消色力（lighteningpower或reducingpower）是指在规定的条件下，白色颜料使有色颜料颜色变浅的能力。  \n\n一般来说，基础漆的消色力越高，遮盖力越好，但配制同一颜色所用色浆量越大。在乳胶漆中，对消色力影响最大的是钛白粉。填料几乎没有遮盖力，但对钛白粉的遮盖效率有影响，对消色力也有影响。  \n\n采用灰浆消色力的方法，即在白色乳胶漆中加人炭黑。本试验中，炭黑用科莱恩的炭黑浆ColanylBlackPR，乳液为巴斯夫的Acronal290D（这是在德国生产的，相当于在我国生产的Acronal296D)，在白色乳胶漆中使用通用钛白粉Kronos2300，试验所用填料见表3-1-34，钛白粉：填料 $=40:60$ ，乳胶漆的PVC为 $50\\%$ ，低于LCPVC，这样就排除了填料的干遮盖力影响。因为是灰浆，填料的白度影响就可以忽略不计。  \n\n表3-1-34试验所用填料  \n\n\n<html><body><table><tr><td>序号</td><td>填料</td><td>商品名称</td><td>平均粒径/μm</td><td>吸油量/（g/100g）</td></tr><tr><td>1</td><td>重质碳酸钙</td><td>Durcal10</td><td>10</td><td>13</td></tr><tr><td>2</td><td>重质碳酸钙</td><td>Calcider BL</td><td>？</td><td>14</td></tr><tr><td>3</td><td>重质碳酸钙</td><td>Durcal 2</td><td>3</td><td>18</td></tr><tr><td>4</td><td>重质碳酸钙</td><td>Calcider 2</td><td>2.7</td><td>18</td></tr><tr><td>5</td><td>重质碳酸钙</td><td>Hydrocarb</td><td>1.5</td><td>18</td></tr><tr><td>6</td><td>湿磨重质碳酸钙</td><td>Setacarb OG</td><td>0.7</td><td>21</td></tr><tr><td>7</td><td>沉淀碳酸钙</td><td>Socal P2</td><td>0.3</td><td>26</td></tr><tr><td>0</td><td>滑石粉</td><td>Luzenac OXO</td><td>10</td><td>33</td></tr><tr><td>9</td><td>细高岭土</td><td>Chinafill F86</td><td>1.7</td><td>43</td></tr></table></body></html>  \n\n填料对消色力的影响如图3-1-7和图3-1-8所示。在图3-1-7中，以钛白粉Kronos2300：填料2（重质碳酸钙Calcider $\\mathbf{BL})=40~:~60$ 为基准，然后，重质碳酸钙CalciderBL与图示各种填料分别以75/25、50/50、25/75和 $0/100$ 共混成填料混合物，并保持钛白粉：填料混合物 $=40:60$ 。如图3-1-8所示是以钛白粉Kronos2300：填料8（滑石粉LuzenacOXO) $=40:60$ 为基准对消色力的影响，填料混合物的配制方法与图3-1-7相同。  \n\n![](images/a2adf4aa1742bc419d0fe590e9dcf855f1635d1a0713df29b8b4b3ad8265da6d.jpg)  \n图3-1-7以填料2为基准，不同填料对消色力影响  \n\n![](images/d403c65e6ddc56cce1bd18a1d8daacb6fa0efc83c9c2b5dadb82f6ff8c0a098f.jpg)  \n图3-1-8以填料8为基准，不同填料对消色力影响  \n\n由图3-1-7可以看出，钛白粉Kronos2300和填料2以40/60比共混时，其消色力只有22.5。当用更粗的球状重质碳酸钙Durcal10取代填料2时，消色力进一步下降。用更细的填料取代填料2时，消色力提高。但填料6湿磨重质碳酸钙是一个例外，其平均粒径0.7μm，却比平均粒径1.5μm的填料5重质碳酸钙消色力低。这说明，除了粒子的细度外，填料的粉磨工艺对消色力也有影响。填料粒子的形状不同，消色力也不相同，片状填料比球状填料更有效，以填料9细高岭土的消色力最高，达25.7，填料8滑石粉的消色力其次，尽管填料8是很粗的。图3-1-8和图3-1-7是一致的。  \n\n这些试验结果可作为调整基础漆消色力和提高基础漆稳定性的参考。  \n\n(2）填料对保色性的影响在乳胶漆配色中，首先，填料吸油量越高，基础漆的消色力越高，配制相同颜色所用色浆量越大，有时甚至差二三倍。其次，填料吸油量越高，一般所配制的乳胶漆LCPVC 就越低，尤其是配制高PVC乳胶漆时，即使在相同PVC下，PVC与LCPVC距离也拉大，从而使乳胶漆对颜料的保护作用减少，乳胶漆的褪色加快，保色性明显降低。若该两项叠加，影响更大，如图3-1-9所示。图3-1-9中，左边的乳胶漆加 $5\\%$ 色浆，而右边乳胶漆的基础漆中加了烧高岭土，应加 $15\\%$ 色浆才配成同样深的颜色。两年自然曝晒后，两者褪色差十分明显。  \n\n![](images/608d02da416c2826c9c61132416e65fd323e23cabbbc52969db38dc6f41ebe91.jpg)  \n图3-1-9两年自然曝晒后  \n\n另外，填料吸油量越高，在高PVC乳胶漆中引进气孔提高遮盖力的效能越好。粒径细的填料，通过位隔作用提高遮盖力效果也较好。  \n\n应结合乳胶漆的要求特点，综合考虑各方面的影响，做出选择。  \n\n对于内墙乳胶漆，保色性要求不高，对装饰性要求较高，深色漆也用得不多，因此，可较多考虑采用细填料，保持遮盖力不变时，减少钛白粉用量。  \n\n对于外墙乳胶漆，保色性往往是其最薄弱环节，且深色漆也用得较多。因此，可考虑采用较粗填料，一方面，降低基础漆的消色力，从而降低配色成本，提高保色性；另一方面，较粗填料还能提高乳胶漆的耐久性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 867,
+        "chunk": "# 7.色差  \n\n颜色在建筑涂料的装饰效果中起着极其重要的作用，因此它特别引人注意是理所当然之事。如果出现色差，装饰效果将打折扣，所以应千方百计避免色差。  \n\n(1）色差产生建筑涂料经过涂布、干燥后形成涂膜。其颜色取决于涂膜本身的性质、基层、光源和观察者，因为颜色是一种视觉，所谓视觉就是不同波长的光刺激人的眼睛之后，在大脑中所引起的反映。  \n\n当这些因素变化时，都会产生视觉上的差异，如：  \n\n$\\textcircled{1}$ 同一品种、同一颜色，不同批号的涂料往往会产生色差；  \n\n$\\textcircled{2}$ 基层的材料、结构、吸水性等差异，会造成色差；  \n\n$\\textcircled{3}$ 光泽不同也会产生色差；  \n\n$\\textcircled{4}$ 先后涂刷时间间隔较长，先涂涂膜的褪色和沾污，也可能导致色差；  \n\n$\\textcircled{5}$ 当配色的色浆批号变化时，也有可能出现色差；  \n\n$\\textcircled{6}$ 当原材料变化时，也有可能导致色差；  \n\n$\\textcircled{7}$ 白色乳胶漆、基础漆和色浆计量不准，会导致色差；  \n\n$\\textcircled{8}$ 由于色卡属于印刷品，与实际墙面上涂膜的颜色在视觉上也不同；  \n\n$\\textcircled{9}$ 环境条件不同，同一颜色在视觉上也不一样等。  \n\n(2）色差度量大多数涂料生产企业是根据用户所选定的色卡上某一颜色或所给定的颜色样板进行生产的。生产后按国家标准GB/T9761—2008《色漆和清漆色漆的目视比色》(eqvISO3668—1998）进行两者间的目测对比，如果色差在允许范围内，则认为合格。否则继续调配至合格。  \n\n虽然一般用肉眼可以区分涂膜颜色的差别，而且实际涂刷后，有关色差以及色差大小都是以人眼观察的。但目测法标准难以统一，各人有各人掌握的尺度，人为影响因素比较大，基本上是属于定性的方法。所以一些大企业或质量控制比较严的企业采用测色仪，根据GB/T11186.1～3-89《涂膜颜色的测量方法》，在CIELAB色空间中，对颜色进行定量测试，并设置定量的色差指标，对色差进行控制。这样控制标准就可以统一，结果比较客观。．  \n\n两颜色间的总色差 $\\scriptstyle\\Delta E$ 是它们在CIELAB色空间中两位置间的几何距离，以式计算：  \n\n$$\n\\Delta E=\\sqrt{(\\Delta L)^{2}+(\\Delta a)^{2}+(\\Delta b)^{2}}\n$$  \n\n式中L——明度差， $\\Delta L>0$ ，表示比标准色浅， $\\Delta L<0$ ，表示比标准色深；$\\scriptstyle\\Delta a$ —红度-绿度差， $\\Delta a>0$ ，与标准色比偏红， $\\Delta a<0$ ，与标准色比偏绿；$\\Delta b$ 一黄度-蓝度差， $\\Delta b>0$ ，与标准色比偏黄， $\\Delta b<0$ ，与标准色比偏蓝。  \n\n色差的单位为NBS（nationalbureau of standardsunit），原为美国国家标准局所制订，一个NBS单位表示一般目光能辨别的极微小颜色间的差别。该单位数值与人的感觉关系见表3-1-35。 OV  \n\n但测色仪测色也存在问题，因为肉眼对不同波长颜色具有不同敏感度。有些颜色，测色仪测出的E已很小，但肉眼却感觉色差很大，不能接受。反之也一样。把肉眼与客观快速的仪器测试相结合，是度量色差最有效的方法。  \n\n表3-1-35色差数值与人的感觉之间关系及其评定级别  \n\n\n<html><body><table><tr><td>NBS单位</td><td>相应于人的色差感觉</td><td>灰长</td><td>NBS单位</td><td>相应于人的色差感觉</td><td>评卡色</td></tr><tr><td>0~0.5</td><td>极轻微（trace）</td><td>5</td><td>3.0~6.0</td><td>严重（appreciable)</td><td>2</td></tr><tr><td>0.5~1.5</td><td>轻微(slight）</td><td></td><td>6.0~12.0</td><td>强烈（much)</td><td>１</td></tr><tr><td>1. 5 ~3. 0</td><td>明显（noticable）</td><td>43</td><td>>12. 0</td><td>极强烈（verymuch)</td><td>二</td></tr></table></body></html>  \n\n(3）色差控制范围《建筑用氟涂料与喷涂技术》一文中谈及，对于铝幕墙板色差，美国建材协会标准（AAMA2605—1998）控制 $\\Delta E{\\leqslant}2,0$ ，日本最高标准 $\\Delta E{\\leqslant}1,0$ ，国内先进标准 $\\Delta E{\\leqslant}1.2$ 费  \n\n《电脑配色仪、（ACS系统）在汽车涂料中的应用》一文中写道，汽车行业已将颜色色差这一技术指标，由原来的定性要求变为定量指标，颜色色差 $\\Delta E{\\leqslant}1{\\sim}1.3$ 票  \n\n结合建筑涂料的实际和可能，对于用户的第一批订单，除特殊要求外，控制实际生产涂料的颜色和标准色板颜色之间的色差 $\\Delta E{\\leqslant}2\\sim3$ ，是既较经济又较合理的。对于补色，色差$\\Delta E$ 控制要严格得多。比如说，同一小区，不同幢建筑物，色差 $\\Delta E{\\leqslant}1$ ；同一幢建筑物，不同墙面， $\\Delta E\\leqslant0.6$ ；如果是同一墙面，一般不能用两批涂料，万不得已采用两批涂料时，$\\Delta E\\leqslant0.4$ 。因为人眼对不同颜色的敏感程度是不一样的，另外， $\\scriptstyle\\Delta E$ 中还包含三个分量，所以还要具体颜色具体对待。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 868,
+        "chunk": "# 8.成品最终检验  \n\n成品最终检验一般包括出厂检验、形式检验和其他检验。  \n\n(1）出厂检验出厂检验项目包括容器中状态、施工性、干燥时间、涂膜外观和对比率等，按相关标准进行。但对比率的测试，试板需在标准条件下养护24h，有时企业为了满足用户急需，不允许养护如此长的时间。可以在 $40\\%$ ，烘干一定时间，其测试结果与标准条件下养护24h基本一致。这样做也是标准GB/T9755—2001和GB/T9756—2009。许可的。  \n\n(2）型式检验可按有关标准进行，测试频率按规定和需要确定。所谓规定，是指标准的规定，如有的标准规定，在正常情况下，形式检验项目每年测定一次。因此就得每年有一次的型式检验。所谓需要，是指生产的要求，即不需要对全部项目进行检验，而要对薄弱环节加强控制。如某一高PVC的内墙合格品乳胶漆，若耐洗刷性富余不多，就要定期对它进行测试，以防不合格品出厂。  \n\n(3）其他检验这里所谓其他检验项目，是指型式检验项目外的检验项目。如自然曝晒、低温成膜性、保色性、涂刷性、辊涂性和溅落等。尽管国家标准或行业标准没有规定，但实际是需要了解和控制的。  \n\n总之，有选择地对产品性能进行检验控制，尤其是产品性能中的薄弱环节，要多检，确保出厂乳胶漆性能符合规定要求和使用要求，使施工人员容易施工，使用户满意。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 869,
+        "chunk": "# 五、乳胶漆的品种  \n\n乳胶漆的品种多种多样，并且还在不断发展，下面择其常用的做一介绍。这里主要介绍建筑乳胶漆。",
+        "category": " Introduction"
+    },
+    {
+        "id": 870,
+        "chunk": "# 1.底涂  \n\n过去，人们主要使用溶剂型底涂。由于环境的原因和水性底涂性能的改进，水性底涂使用越来越多。据报道，1996年，估计欧洲使用底涂13万吨，其中，2/3是溶剂型底涂，1/3是水性底涂。1998年，仅德国就生产了8.6万吨水性底涂。足见底涂从溶剂型转为水性之快。下面就底涂的作用、分类和标准做一介绍。  \n\n(1）作用底涂是涂膜系统的重要组成部分。其作用如下。  \n\n$\\textcircled{1}$ 加固基层对于比较疏松的基层，必须先用底涂处理，将其加固，然后才能施涂中涂料。这类似于对混凝土进行浸溃处理以提高混凝土的性能。  \n\n$\\textcircled{2}$ 降低并均匀基层吸水性建筑涂料的基层大多是水泥砂浆和混合砂浆抹灰层，吸水性较大。如果不涂底涂，就直接涂乳胶漆时，乳胶漆中的乳液粒子较细，流动性较好，就会被吸入基层中，留在表面的将是较高颜料填料、较高PVC的乳胶漆膜，影响其质量。其次，水分吸收过快，也不利于成膜。另外，吸水性不均匀，会造成涂膜厚度不均匀，并有可能导致色差。因此，应涂底涂以降低并均匀基层吸水性。 ·  \n\n$\\textcircled{3}$ 提高中涂层在基层上的附着力涂膜与基层的接触区是整个涂膜系统最薄弱的一环，因此，附着力就成为涂膜保护作用和装饰功能等的基础。乳胶漆涂膜主要通过机械咬合力和范德华力与基面结合的。底涂一般黏度低，表面张力适中，粒子细，流动性好，渗透性好。它能在较细的毛细孔中扎根，并且能渗入一定深度，从而产生较强的机械咬合力。当打磨基面时，难免在基面上还附有粉尘。直接涂刷涂料，就犹如在桌上打面时先撒一点面粉，尽管湿面粉很黏，是无论如何粘不到桌面上的。打面是不希望粘桌面而散一点面粉，而施涂涂料是希望粘得越牢越好，所以不能有粉尘。哪怕是一点粉尘，也会严重影响附着力，从而影响使用寿命。用底涂可以加固打磨而浮在基面上的粉尘。另据虞兆年介绍，他们曾在上海江宁路采用相同路标漆施工了四条路标线，其中三条都涂了底涂，只有一条未涂底涂。结果该未涂底涂的路标线投入使用两周后全面剥落，其余三条路标线用了两年。涂底涂的路标线使用寿命是未涂底涂的52倍。可见底涂对附着力的重要意义。  \n\n$\\textcircled{4}$ 封闭作用底涂一方面填充了部分毛细孔；另一方面聚合物的表面张力低，僧水性比抹灰层高，所以降低了吸水性，并防止盐、碱随水分迁移，具有一定的封闭作用。当然，填充得越致密，聚合物的表面张力越低，憎水性越强，封闭作用越好。但还要兼顾中涂在其上的复涂性和一定的透气性。  \n\n(2）分类按有无颜料填料分，乳液型底涂一般可以分为两类，清漆型底涂和有色底涂。清漆型底涂是不含颜料和填料的，能较好地发挥上述底涂作用，尤其是微乳液或阳离子乳液制成的清漆型底涂。有色底涂是含有颜料和填料的，因此具有一定的遮盖力，但会牺牲上述底涂的部分功能。  \n\n按乳液离子性分，可将乳液型底涂分为阴离子底涂和阳离子底涂。  \n\n用阳离子乳液制成的底涂叫阳离子底涂。阳离子底涂可以是清漆型底涂，也可以是有色底涂。粒径小、表面张力低的阳离子乳液渗透性好。另外，阳离子表面活性剂对固体表面，尤其是硅酸盐类的固体表面，具有很强的附着力。因此，阳离子底涂附着力高，封闭性好。  \n\n(3）标准底涂性能一般要符合JG/T210—2007《建筑内外墙用底漆》的规定。",
+        "category": " Introduction"
+    },
+    {
+        "id": 871,
+        "chunk": "# 2.内墙乳胶漆  \n\n内墙乳胶漆是目前用得最多的建筑涂料之一。  \n\n(1）内墙乳胶漆简介内墙乳胶漆已成为室内墙面和顶棚装饰的首选材料。其主要产品有苯丙乳胶漆、醋丙乳胶漆和乙烯-醋酸乙烯乳胶漆。  \n\n醋丙内墙乳胶漆（亦称乙丙内墙乳胶漆）和苯丙内墙乳胶漆，由于性能好，价格适中，是目前最广泛使用的两种内墙乳胶漆。  \n\n乙烯-醋酸乙烯内墙乳胶漆，由于其所用的乳液聚合物经乙烯改性后，成膜性能好，高温下不回黏，因此提高了涂膜的耐水性、耐碱性和耐污性。乙烯-醋酸乙烯共聚乳液还能较方便地制成低VOC（挥发性有机物）或零VOC内墙乳胶漆。  \n\n纯丙内墙乳胶漆，质量好，但比较起来价格较高，目前使用很少。  \n\n根据光泽不同，内墙乳胶漆还可分为平光内墙乳胶漆，丝光内墙乳胶漆，半光内墙乳胶漆和有光内墙乳胶漆等。我国没有具体划分标准，德国和欧盟有此类标准，如EN13300：2001。  \n\n光泽是涂膜表面对光的反射能力，以涂膜表面反射光和黑平玻璃表面（ $_{;n_{\\mathrm{D}}}{=}1.567;$ 反射光之比乘以100表示。光泽与观察角、涂膜表面平整度和涂膜材料的折射系数等有关。通常，观察角为 $20^{\\circ}$ ， ${60}^{\\circ}$ 和 $85^{\\circ}$ ，特殊情况为 $45^{\\circ}$ 曲  \n\n(2）性能和环保要求我国内墙乳胶漆的性能要求见GB/T9756—2009合成树脂乳液内墙涂料。  \n\n我国内墙乳胶漆在环境友好方面尚需满足GB18582-2008（表3-1-36）的要求，才能允许进入市场销售。挥发性有机化合物主要来自成膜助剂、助溶剂、乳液、色浆和其他助剂，苯、甲苯、乙苯、二甲苯主要来自溶剂油。游离甲醛超标时，首先检查防腐防霉剂，其次是乳液，这是容易出现问题的地方，不管生产和使用都应注意。重金属来自于颜料和填料，一般也不会超标。  \n\n表3-1-36GB18582—2008室内装饰装修材料内墙涂料中有害物质限量  \n\n\n<html><body><table><tr><td>项 目</td><td>限量值</td><td></td><td>项目</td><td>限量值</td></tr><tr><td>挥发性有机化合物（VOC)/(g/L)</td><td>≤ 120</td><td></td><td>可溶性铅</td><td>90</td></tr><tr><td>苯、甲苯、乙苯、二甲苯总和/（mg/kg）</td><td>≤ 300</td><td>重金属/（mg/kg）</td><td>可溶性</td><td>VV 56</td></tr><tr><td>游离甲醛/(mg/kg）</td><td>≤ 100</td><td></td><td>可溶性汞</td><td>≤ 60</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 872,
+        "chunk": "# 3.外墙乳胶漆  \n\n外墙乳胶漆全名为合成树脂乳液外墙涂料，它是目前最普遍使用的一种外墙涂料。  \n\n外墙乳胶漆的主要问题是最低成膜温度高，通常必须在 $5\\mathrm{{c}}$ 以上施工才能保证质量，有的还要在 $10\\Upsilon$ 以上。对于我国的北方，造成一年内可施工时期较短。  \n\n(1）分类外墙乳胶漆的分类有多种分法。  \n\n根据所使用乳液的不同，外墙乳胶漆又可分为硅丙乳胶漆、聚氨酯丙烯酸乳胶漆、纯丙乳胶漆、苯丙乳胶漆和醋叔乳胶漆等。其中苯丙乳胶漆和纯丙乳胶漆，因为性能能满足要求，价格适中，是目前广泛使用的两种乳胶漆。硅丙乳胶漆由于其拒水性、透气性好，耐沾污性和耐久性也好，当然价格也较高，在一些要求较高的工程中被使用。水性聚氨酯丙烯酸乳胶漆是由聚氨酯分散体、丙烯酸乳液、颜料、填料和助剂组成。脂肪族聚氨酯分散体耐光性和耐候性好，与水反应活性低，适用于水性外墙乳胶漆。聚氨酯分散体涂料流平性突出。脂肪族聚氨酯涂膜耐低温性、耐沾污性和耐酸性也很好。但聚氨酯分散体价格较高，配色性差。因此，将其和丙烯酸乳液一起使用，使水性聚氨酯丙烯酸乳胶漆优势互补，具有很好的保护作用和装饰功能。  \n\n另外，还有含氟树脂乳液涂料，简称含氟乳胶漆。  \n\n根据光泽不同，外墙乳胶漆可分为平光外墙乳胶漆、丝光外墙乳胶漆、半光外墙乳胶漆、有光外墙乳胶漆和高光外墙乳胶漆。我国没有具体划分标准，欧盟有此类标准，如：EN1062-1:2002。  \n\n根据质感不同，外墙乳胶漆可分为薄质外墙乳胶漆、厚质外墙乳胶漆、饰纹外墙乳胶漆  \n\n和砂壁状外墙乳胶漆等。  \n\n根据黏结剂种类多少，外墙乳胶漆可分为普通单一黏结剂外墙乳胶漆和复合外墙乳胶漆。复合外墙乳胶漆，如硅溶胶丙烯酸复合外墙乳胶漆、硅酸盐丙烯酸复合外墙乳胶漆和硅丙复合外墙乳胶漆等。  \n\n(2）性能要求我国外墙乳胶漆性能要求如GB/T9755—2001合成树脂乳液外墙涂料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 873,
+        "chunk": "# 4.弹性乳胶漆  \n\n弹性乳胶漆既可以用于外墙，也可以用于内墙。它是属于功能性建筑涂料。由于它能遮盖墙体的毛细裂缝和防止混凝土碳化，因此越来越受到用户的青睐，市场占有率不断扩大。弹性建筑乳胶漆的弱点是耐沾污性不够理想。  \n\n（1）发展Hill等观察得出，一年后，用普通外墙涂料涂装的外墙面，基本上都出现裂缝。Schwartz等认为， $2\\mathrm{mm}$ 以内的裂缝虽对结构完整性无大影响，但会使水进人。因此，人们开发弹性建筑乳胶漆以解决此问题。起初，人们开发了以醋酸乙烯酯共聚物为黏结剂的弹性乳胶漆，由于其透气性不太好，涂膜容易起泡，所以逐步失去了市场。紫外线交联丙烯酸弹性乳胶漆由于其低温弹性好、透气性好、耐沾污性尚可等原因，从而取代了醋酸乙烯弹性乳胶漆，成为目前主要使用的弹性建筑乳胶漆。但是，在紫外线不足的地方，紫外交联丙烯酸弹性乳胶漆干燥较慢。硅丙弹性乳胶漆拒水性好，耐沾污性不错，且具有优异的耐候性。然而，硅丙弹性乳胶漆遮盖裂缝的能力不如紫外交联丙烯酸弹性乳胶漆。  \n\n有人预言，耐沾污性好的弹性乳胶漆是亚洲涂料的未来。  \n\n(2）特点弹性乳胶漆的生产与一般乳胶漆基本相似，但也有其自身的特点。  \n\n第一，是所用的乳液不同，弹性乳胶漆选用低玻璃化温度（ $T_{\\mathrm{{g}}}$ ）弹性乳液，即在使用温度范围内，具有弹性的乳液。也就是说，即使在冬天，也应有弹性。而一般乳胶漆采用较高 $T_{\\mathrm{s}}$ 乳液。  \n\n第二，是颜料和填料分散方法不同，弹性乳胶漆由于用水量较小，往往采取半干着色法，而一般乳胶漆则采用研磨着色法。  \n\n第三，弹性乳胶漆在配方设计上，也有一些特殊的考虑。例如，为了达到弹性要求，弹性乳胶漆是富乳液含量的，即具有较低PVC。而一般亚光乳胶漆，PVC 较高。弹性乳胶漆通常黏度比较高，消泡比一般乳胶漆困难，要采用在高黏度下具有较好消泡能力的消泡剂。弹性乳胶漆一般也不用成膜助剂。  \n\n另外，为了达到较理想的遮盖裂缝能力，弹性乳胶漆的涂膜厚度往往比较厚。  \n\n(3）弹性机理高聚物由于温度不同而呈现三种力学状态——玻璃态、橡胶态和黏流态。玻璃化温度 $T_{\\mathrm{s}}$ 是高聚物的特征指标。当高聚物在其玻璃化温度以下时，处于玻璃态，变成坚硬的固体，没有弹性，一般的涂膜基本就是这种情况。当高聚物在其玻璃化温度以上时，处于橡胶态，此时所呈现的力学性能是高弹性。弹性乳胶漆就是基于高聚物的这一力学性能而制成的。也可以说，弹性乳胶漆就是将使用温度置于成膜物质的橡胶态平台上的涂料。  \n\n由于涂膜使用温度是客观存在的，是人们无法改变的，所以要使涂膜的使用温度高于高聚物的玻璃化温度，唯一的方法就是降低成膜物质高聚物的玻璃化温度。所以说，生产弹性乳胶漆的乳液是玻璃化温度很低的弹性高聚物。比如说，有的甚至低至一45℃。不仅涂膜的最低使用温度要高于 $T_{\\ast}$ ，而且最高使用温度也必须在橡胶态平台上，而一年内最高温度和最低温度差约 $40\\mathrm{\\sim}50^{\\circ}C$ ，这就要求高聚物有一个足够宽的橡胶态平台。  \n\n此外，选择作为弹性乳胶漆的成膜物质，应既软又韧，弹性模量低，极限强度适中，延伸率高。  \n\nWicks认为，把玻璃化温度作为柔性和脆性的分界点是错误的。柔性和脆性的分界点是脆化温度 $T_{\\mathrm{b}}$ ，而不是玻璃化温度 $T_{\\ast}$ 。在 $T_{\\mathfrak{b}}$ 以下，聚合物是脆的；在 $T_{\\flat}$ 和 $T_{\\mathrm{{s}}}$ 之间，聚合物是硬而可延展的；在 ${T_{\\mathrm{s}}}$ 以上，聚合物是软的。  \n\n脆化温度（brittlenesstemperature）是塑料、橡胶在规定的冲击条件下出现脆性破坏的温度，是表征耐寒性的一个重要指标。  \n\n不同热塑性聚合物的 $T_{\\mathrm{s}}$ 和 $T_{\\mathrm{b}}$ 差别很大。聚苯乙烯的 $T_{\\mathrm{b}}$ 比 $T_{\\mathrm{{g}}}$ 约低 $10\\%$ ，而双酚A聚碳酸酯的 $T_{\\mathrm{b}}$ 比 $T_{\\ast}$ 低 $350\\mathrm{^q}$ 。聚丙烯酸酯和聚甲基丙烯酸酯的 $T_{\\flat}$ 和 ${T_{s}}$ ，有的是很接近的，而有的差别较大。  \n\n据此估计，弹性乳液聚合物的 $T_{\\mathrm{b}}$ 约比 $T_{\\mathrm{s}}$ 低 $10\\Upsilon$ ，具体视其组成和结构而定。这也就  \n\n是说，当使用温度在 $T_{\\mathrm{*}}$ 以下约 $10\\%$ 内时，弹性乳胶漆涂膜不是脆的，而是硬而有延展的。  \n\n(4）遮盖裂缝的能力弹性建筑乳胶漆的遮盖裂缝能力和乳液性能、颜料体积浓度PVC、涂膜厚度、延伸率保持率、使用温度等因素有关。  \n\n$\\textcircled{1}$ 乳液性能乳液性能是弹性建筑乳胶漆遮盖裂缝能力的基础。乳液聚合物的组成和结构在很大程度上决定了橡胶态的平台和遮盖裂缝的能力。聚合物分子间相互作用较弱，分子链柔顺性较好，易于变形，富有较高弹性。增塑类型对延伸率有明显影响，外增塑聚合物表现出很高的延伸率，但温度范围较窄，当增塑剂用量提高时，延伸率曲线形状基本不变，但曲线向低温侧移动。外增塑聚合物随着增塑剂的挥发，弹性降低。内增塑聚合物刚好相反，其最大延伸率比外增塑体系低，但温度范围较宽，没有增塑剂挥发问题。两者的比较如图3-1-10所示。一个适合一年四季变化的弹性温度范围对于使用来说，是十分重要的。因此弹性建筑乳胶漆一般采用内增塑。  \n\n![](images/036c4de0a2a07cca6c24cc380ccf8217ef95ff161e068b8d40140e9c842bb220.jpg)  \n图3-1-10内外增塑聚合物的延伸率实线表示内增塑；点划线表示较低增塑剂外增塑；虚线表示较高增塑剂外增塑  \n\n有时，生产弹性建筑乳胶漆时，为了降低成本或改善耐沾污性，也可以把弹性乳液和普通乳液混用，但要注意其相容性。随着普通乳液的加人，乳胶漆遮盖裂缝能力降低，拉伸强度提高，尤其是在使用温度更低时。见表3-1-37。  \n\n表3-1-37全弹性乳液和掺普通乳液的弹性乳胶漆延伸率和抗拉强度比较  \n\n\n<html><body><table><tr><td colspan=\"2\">PVC/%</td><td colspan=\"2\">30</td><td colspan=\"2\">40</td></tr><tr><td colspan=\"2\">Primal 2438/AC-261</td><td>100/0</td><td>70/30</td><td>100/0</td><td>70/30</td></tr><tr><td>廷伸率/%</td><td>-10℃ 2℃ 40°C</td><td>510 321 408</td><td>87 105</td><td>262 11 241</td><td>29 52.6</td></tr><tr><td>拉伸强度/MPa</td><td>-10℃ 40C</td><td>5.5 2. 8 2.4</td><td>256 8.1 5. 6 2.0</td><td>5.6 2.9 2.0</td><td>282 12.2 9. 4 </td></tr></table></body></html>  \n\n弹性乳胶漆的PVC一般在 $25\\%\\sim45\\%$ ，具体视所要求的弹性而定。弹性要求高，PVC偏低控制，弹性要求低，PVC偏高控制。  \n\n$\\textcircled{2}$ 涂膜厚度为了达到遮盖裂缝的效果，弹性乳胶漆干膜必须有一定厚度。裂缝扩展涂膜受拉伸时，是要缩颈的。  \n\n不同干膜厚度的延伸率、拉伸强度和遮盖裂缝宽度见表3-1-38。试验采用RhoplexEC-2848弹性乳液， $P V C=37\\%$  \n\n表3-1-38不同干膜厚度的延伸率、拉伸强度和遮盖裂缝宽度  \n\n\n<html><body><table><tr><td colspan=\"2\">干膜厚度/μm(mil）</td><td>127(5)</td><td>254(10)</td><td>508(20)</td></tr><tr><td rowspan=\"2\">24°C</td><td>延伸率/%</td><td>432</td><td>490</td><td>510</td></tr><tr><td>拉伸强度/MPa 遗盖裂缝宽度/μm</td><td>1.16 889</td><td>1.21</td><td>1.08</td></tr><tr><td rowspan=\"2\"></td><td>延伸率/%</td><td>208</td><td>1651 204</td><td>3429 262</td></tr><tr><td>拉伸强度/MPa</td><td>5.24</td><td>5.91</td><td></td></tr><tr><td>-18C</td><td>遮盖裂缝宽度/μm</td><td>330</td><td>711</td><td>5.13 1397</td></tr></table></body></html>  \n\n从表3-1-38可以看出，干膜厚度对拉伸强度没有影响，对延伸率有影响，但不大。随着干膜厚度增加，延伸率略有增加。干膜厚度对遮盖裂缝宽度作用重大，大致与其成正比例关系。  \n\n温度影响较大。温度降低，抗拉强度提高，延伸率和遮盖裂缝宽度下降。  \n\n综上所述，兼顾经济，弹性建筑乳胶漆干膜厚度：平涂 $150\\sim250\\mu\\mathrm{m}$ ，拉毛 $250\\sim$ $350\\mu\\mathrm{m}$ 是比较合适的。  \n\n$\\textcircled{3}$ 延伸率保持率涂膜在环境的作用下是要老化的，老化后弹性建筑乳胶漆的弹性又如何变化呢？这对实际应用是需要知道的。将六组不同PVC的试样，人工QUV老化1000h前后，分别测定其延伸率。 $23\\Upsilon$ 时，六组试样延伸率平均保持率为 $44\\%$ 。 $-15\\Upsilon$ 时，六组试样延伸率平均保持率为 $47\\%$ 。当然，不同弹性涂料的延伸率保持率是不一样的。  \n\n$\\textcircled{4}$ 使用温度如前所述，弹性建筑乳胶漆的使用温度应该在弹性乳液聚合物的橡胶态平台上。各种乳胶漆都有一个最大延伸率，但是不同乳胶漆达到最大延伸率的温度是不同的。在最高延伸率的两侧，不管是随着温度降低，还是随着温度升高，延伸率都将下降，低温侧下降更快。  \n\n(5）耐沾污性由于弹性乳胶漆必须使用很低 $T_{*}$ 的弹性乳液，所以先天性的耐沾污性就比较差。比如说，采用 $T_{\\mathrm{{s}}}=-15\\mathrm{{\\sfC}}$ 的乳液，在冬天使用温度为 $T_{*}$ 时，耐沾污性系数为1，而到夏天，使用温度升为 $40\\%$ 时，涂膜就很软，耐沾污性系数就下降为0.25，耐沾污性自然很差。  \n\n(6）附着力弹性乳胶漆的涂膜有时能被成条成片地撕下来，而亚光乳胶漆的涂膜却没有这种问题。于是有人以为弹性乳胶漆涂膜的附着力不如普通亚光乳胶漆。其实不然，它们的附着力是基本相同的。我国不同标准对粘接强度有不同规定，便于比较，将一些非涂料产品也列于表3-1-39。  \n\n表3-1-39我国不同标准对粘接强度的规定  \n\n\n<html><body><table><tr><td rowspan=\"2\" colspan=\"3\">标准</td><td colspan=\"2\">粘接强度/MPa</td></tr><tr><td>标准状态</td><td>浸水后</td></tr><tr><td colspan=\"2\">JG/T24--2000《合成树脂乳液砂壁状建筑涂料）</td><td>≥0.70</td><td></td><td>≥0.50</td></tr><tr><td colspan=\"3\">JG/T157—2004（建筑外境用腻子）</td><td>≥0.6</td><td>冻融循环≥0.4</td></tr><tr><td colspan=\"2\">JGJ/T110——2008（建筑工程饰面砖粘接强度检验标准）</td><td>≥0.4</td><td></td><td></td></tr><tr><td rowspan=\"2\">JG149—2003(膨胀聚苯板薄抹灰外墙 外保温系统）</td><td>胶黏剂</td><td>苯≥0.10披坏界面在膨胀察</td><td>聚耐水≥0.10-破坏界面在膨胀</td><td></td></tr><tr><td>抹面胶浆</td><td></td><td>苯≥0.10,破坏界面在膨胀素面水冻酸≥0.10,破坏界</td><td></td></tr></table></body></html>  \n\n在外墙外保温体系中，最薄弱环节是胶黏剂和聚苯板的粘接面上，因为粘贴面积一般为40%，因此，粘接强度约只有0.1×40%=0.04MPa。即使在这种情况下，体系安全系数也是足够的。面砖粘接强度也只有0.4MPa。  \n\n弹性乳胶漆涂膜的附着力一般在 $0.7\\ensuremath{\\mathrm{MPa}}$ 以上，是足够安全的。但其涂膜的拉伸强度比较高，往往大于 $1\\mathrm{MPa}$ ，高于弹性乳胶漆的附着力，所以就能成片撕下。有光乳胶漆涂膜也有类似情况。亚光乳胶漆涂膜就不一样，其拉伸强度与其粘接强度基本相同，因此一撕就碎，不会出现被成条成片撕下现象。  \n\n这并不是说弹性乳胶漆的涂膜一定会被成片撕下来。通过合适的底涂和基层处理，也可通过弹性乳胶漆本身的改进，提高涂膜附着力，使其与拉伸强度相当，就不会被成条成片撕下来。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 874,
+        "chunk": "# 5.真石漆  \n\n真石漆属于合成树脂乳液砂壁状建筑涂料。它通常以合成树脂乳液为基料，以不同粒径的彩色砂、花岗岩和填料等为骨料，加助剂和水配制而成。通过喷涂和抹涂，在建筑物表面形成酷似大理石、花岗岩等天然石材质感的涂层，给人以返归自然的感觉。因此，亦称石头漆、仿石漆。  \n\n(1）涂层组成和作用真石漆涂层系统一般由封闭底漆、真石漆和罩面清漆组成。  \n\n封闭底漆的作用是加固基层，增强真石漆与基层的附着力，降低并均匀基层吸水性，对碱和盐的渗透迁移起封闭作用。  \n\n真石漆是形成图案和立体质感，达到足够高的硬度，并赋予涂层天然石材颜色的关键组分。  \n\n罩面清漆层处于涂层系统的最外面，它要拒水透气，抗污染，耐紫外线辐射，防霉防藻。  \n\n(2）原料和生产真石漆所用的乳液必须具有很好的耐水性、粘接强度和耐老化性。苯丙乳液、纯丙乳液和硅丙乳液都可选用。无皂乳液耐水性更好。据介绍，乳液的最低成膜温度不应低于 $20\\Upsilon$ ，其与施工温度之间的矛盾可通过成膜助剂来解决。  \n\n真石漆以彩色砂、普通石英砂、花岗岩、石粉等为骨料。真石漆的质感和颜色取决于这些骨料的大小、级配和颜色。彩砂可分为天然石英砂和人工着色石英砂。天然彩色砂资源丰富，价格便宜，但颜色一致性较差，色感灰暗，较鲜艳的颜色品种少。人工着色石英砂是采用陶瓷颜料和釉料，经烧而使石英砂着色的。色彩丰富，颜色一致性好，粒度均匀。天然花岗岩坚硬，不易粉化，颜色自然，保色性好。选择不同颜色和不同尺寸的骨料，能配制出丰富多彩的真石漆。大小骨料要搭配使用，形成合适的配比。当粗骨料太多时，会产生大量孔隙，容易积灰。细骨料太多时，会影响真石漆的质感。也有人在填料中选用一些玻璃微珠、云母粉和切片等。玻璃微珠可以提供真石漆透视性和反光效果，给涂膜增添意想不到的效果。云母粉可增加迷彩效果，还有防开裂作用。切片使色彩更多样化。  \n\n由于彩砂的可变性，控制真石漆色彩和质感的均匀一致性就是生产的重要一环。  \n\n真石漆的助剂选择与一般乳胶漆相似，但要特别注意协助达到施工时少掉砂，干燥时不开裂，遇水时不泛白。  \n\n真石漆的生产主要是混合均匀，而不是高速分散。因此，生产的设备是混合机，不是高速分散机。  \n\n(3）性能要求真石漆的性能一般要求按JG/T24—2000《合成树脂乳液砂壁状建筑涂料》标准执行。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 875,
+        "chunk": "# 6.硅酸盐乳胶涂料  \n\n硅酸盐乳胶涂料是以水玻璃或硅溶胶和乳液为基料，并同颜料、填料、助剂和水配制而成的涂料。它具有透气性好、耐热性佳、环境友好等特点。在我国、德国、奥地利和瑞士等有一定应用。  \n\n在生产硅酸盐乳胶涂料时，乳液的耐碱性、耐水解性以及和水玻璃的相容性是十分重要的，因为水玻璃的 $\\mathfrak{p H}$ 在11以上。相容性可通过试验确定，即将乳液和等量的水玻璃用调墨刀搅拌混合，当乳液和水玻璃都没有凝聚和结块时，认为相容性合格。凝聚和结块是乳液聚合物中羧酸功能单体和强碱作用的结果。  \n\n乳液的一般用量，以固体分计，约为总配方固含量的 $4.5\\%$  \n\n生产硅酸盐乳胶涂料的加料次序也有自己的特点。水玻璃必须在最后加入，以防强碱使乳液凝聚和结块。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 876,
+        "chunk": "# 六、乳胶漆的成膜机理和涂膜结构  \n\n了解乳胶漆的成膜机理对于乳胶漆的研究开发、配方设计、生产和施工应用等都是十分重要的。  \n\n另外，涂膜的性能是由涂膜的组成和结构决定的。仅了解涂膜的组成是不够的，必须进一步了解涂膜的结构。尽管有关涂膜的结构的资料很少，但还是将其进行简单介绍，以利发展。",
+        "category": " Introduction"
+    },
+    {
+        "id": 877,
+        "chunk": "# 1.乳胶漆的成膜机理  \n\n对于乳胶漆的成膜机理，有多种说法，还没有取得一致的结论，尚在形成发展之中。择其主要的作介绍。  \n\n(1）乳胶漆的成膜过程乳胶漆的成膜是一个从分散着聚合物颗粒和颜料填料颗粒相互聚结成为整体涂膜的过程。该过程大致分为三个阶段：初期、中期和后期。  \n\n$\\Phi$ 初期乳胶漆施工后，随着水分逐渐挥发，原先以静电斥力和空间位阻稳定作用而保持分散状态的聚合物颗粒和颜料、填料颗粒逐渐靠拢，但仍可自由运动。在该阶段，水分的挥发与单纯水的挥发相似，为恒速挥发。  \n\n$\\textcircled{2}$ 中期随着水分进一步挥发，聚合物颗粒和颜料、填料颗粒表面的吸附层被破坏，成为不可逆的相互接触，达到紧密堆积，一般认为此时理论体积固含量为 $74\\%$ ，即堆积常数是0.74。该阶段水分挥发速率约为初期 $5\\%\\sim10\\%$ 。  \n\nHoy等用悬臂梁重量法堆积测定仪［cantilevered gravimetric beam（CGB）packome-ter］测试后得出，均匀球形粒子优先堆积排列是随机的密堆积（Bernal堆积），其堆积常数不是0.74，而是0.635；其最接近的平均粒子数不是12，而是8.5。  \n\n大致可以把涂膜表干定义为中期的结束。这时涂膜水分含量约为 $2.7\\%$ ，黏度为 $10^{3}\\mathrm{\\Pa\\bullet\\bullet_{\\circ}}$  \n\n$\\textcircled{3}$ 后期在缩水表面产生力的作用下，也有认为在毛细管力或表面张力等的作用下，如果温度高于MFT，乳液聚合物颗粒变形，聚结成膜，同时聚合物界面分子链相互扩散、渗透、缠绕，使涂膜性能进一步提高，形成具有一定性能的连续膜。此阶段水分主要是通过内部扩散至表面而挥发的，所以挥发速率很慢。另外，还有成膜助剂的挥发。在此阶段初，成膜助剂的挥发，是由挥发控制的；随后，成膜助剂的挥发，是由扩散控制的，如图3-1-11所示。 Q  \n\n(2）乳胶漆的成膜条件乳胶漆成膜条件之一是水分挥发。水分不挥发，乳胶漆就不会成膜。而水分挥发的速率，就乳胶漆来说，与其所含的成膜助剂和助溶剂等有关；就其施工应用来说，不仅与周围环境的温度、相对湿度和风速等有关，而且与基层的温度、含水率、  \n\n![](images/4dee5c6c0ca52e2457f6cc2bed2b8fcd219512c28149ace84762d26c5fa53423.jpg)  \n图3-1-11含成膜助剂的苯丙乳液膜在成膜过程中 $T_{\\ast}$ 值的变化试验条件：23C，25%RH，膜厚38. $1\\mu\\mathrm m$ ，风速402. $s_{\\mathrm{m/h}}$ 成膜助剂：DPM、DPnP、苯甲醇、KP-140  \n\n吸水性有关。因此综合平衡诸因素，使其有一个合适的水分挥发速率，以获得优良的涂膜。  \n不能太快，也不能太慢。  \n\n乳胶漆成膜条件之二是施工时的环境温度和基层温度必须高于乳胶漆的最低成膜温度。否则，尽管水分挥发，但乳胶漆还是不能成膜的。  \n\n因为成膜需要乳胶粒子变形，分子链相互扩散和渗透，以致相互缠绕，达到聚结的。而这些都要求乳胶漆体系中有大于 $2.5\\%$ 的自由体积。这里所谓的乳胶漆体系，是指乳胶漆中所有组分混合体。否则乳胶粒处于玻璃态而无法变形，乳胶分子链段和自由体积处于冻结状态而不能扩散。  \n\nHill等用正电子理灭寿命光谱仪［positron annihilation lifetime spectroscopy（PALS)]和原子力显微镜，研究了乳胶膜结硬和成膜过程中自由体积的分布。从而得出，当温度低于$T_{\\mathrm{{g}}}$ 时，由于没有明显的相互扩散，结硬的乳胶膜是脆的。  \n\n另外，乳胶漆的最低成膜温度是指乳胶漆形成不开裂的连续涂膜的最低温度。它不同于乳胶漆用乳液（包含成膜助剂）的最低成膜温度。一般来说，由于颜料填料等影响，尽管表面活性剂也有一定的降低乳液最低成膜温度的作用，乳胶漆的最低成膜温度也高于其所用乳液的最低成膜温度。  \n\n2000年11月初，上海市房地产科学研究院对“迎APEC（亚太经济合作组织）会议”用外墙涂料质量进行了控制检验，结果见表3-1-40。  \n\n表3-1-40迎APEC会议外墙涂料检验情况  \n\n\n<html><body><table><tr><td>项目</td><td>总样品</td><td>5C涂膜开裂</td><td>5℃涂膜达不到标准要求</td><td>不合格总计</td><td>合格</td></tr><tr><td>样品/个</td><td>42</td><td>13</td><td>12</td><td>25</td><td>17</td></tr><tr><td>比例/%</td><td>100</td><td>31</td><td>29</td><td>60</td><td>40</td></tr></table></body></html>  \n\n从表3-1-40可以看出，这次检验的外墙涂料中，有 $31\\%$ 的涂料最低成膜温度高于 $5\\mathrm{{c}}$ 所以在 $5\\mathrm{{v}}$ 时，尽管水分挥发，但不能形成连续膜。有 $29\\%$ 的涂料，虽然在 $5\\mathrm{{c}}$ 时能成膜，但 ${\\boldsymbol{T}}{\\mathrm{-}}\\mathbf{M}\\mathbf{F}\\mathbf{T}$ 值太小，所成涂膜质量达不到GB/T9755的要求。这是因为随着乳胶漆成膜过程的进行，成膜助剂和二醇类溶剂的挥发，乳胶漆系统的 $T_{*}$ 或最低成膜温度会逐步升高。如图3-1-11所示是含成膜助剂的苯丙乳液膜在成膜过程中 $T_{\\mathrm{*}}$ 值的变化。当乳胶漆的最低成膜温度升高至环境温度时，成膜过程就无法进行。当然，GB/T9755要求养护条件是 $23^{\\circ}\\mathrm{C}$ ，  \n\n$R H50\\%$ 。但有时实际施工温度是远远低于 $23\\%$ ，这对乳胶漆的成膜是有影响的。可见，所成涂膜质量与施工时的环境温度、基层温度与最低成膜温度差 $T{\\mathrm{-}}\\mathbf{M}\\mathbf{F}\\mathbf{T}$ 有关。 $T{\\mathrm{-}}\\mathbf{M}\\mathbf{F}\\mathbf{T}$ 值大些有利于成膜。  \n\n乳胶漆表干在2h以内，是比较快的。然而，完全成膜的时间是比较长的，大约需要四周以上的时间。在相同条件下，软的聚合物粒子成膜比硬的聚合物粒子慢。在整个成膜过程中，尽管随着溶剂的挥发，乳胶漆的最低成膜温度会逐步升高，但在整个成膜过程中，都应保持T一MFT值大于零，这样，才能形成好涂膜。  \n\n(3）乳胶漆的成膜驱动力关于乳胶漆的成膜驱动力，目前还没有统一的看法。  \n\nDillion等认为，是聚合物的表面张力驱动乳液聚合物粒子变形而成膜。  \n\n巴顿和Brown认为，固体颗粒间的水溶液产生毛细管力，尽管该毛细管力绝对值不大，但其相对于乳胶漆粒子的重量来说，是很大的。正是该毛细管力，促使乳胶漆粒子聚结成膜。  \n\nEckersley等认为，仅毛细管力不足以驱使成膜，是界面张力和毛细管力一起促使乳胶粒子成膜。  \n\nVisschers认为，缩水表面产生的力（the force by the receding water surface）是驱动乳胶漆成膜的主要动力。他根据乳胶漆粒子半径 $r_{\\mathsf{p}}=250\\mathrm{nm}$ ，哈梅克（Hamaker）常数 $A=$ $1.05\\times10^{-20}.$ ，表面电位 $\\mathrm{U}=-20\\mathrm{m}\\mathrm{V}$ ，盐值（salt level） $S{=}1\\mathrm{mmol/L}$ ，水表面张力 $\\scriptstyle\\gamma=$ ${70}\\mathrm{mN/m}$ ，接触角 $\\scriptstyle\\theta=0^{\\circ}$ ，聚合物模量 $E{=}10^{7}\\mathrm{Pa}$ ，计算得乳胶膜干燥时，各作用力的典型值，如表3-1-41所示。  \n\n表3-1-41乳胶膜干燥时各作用力的大小  \n\n\n<html><body><table><tr><td>类 型</td><td>作用力</td><td>大小/N</td><td>类 型</td><td>作用力</td><td>大小/N</td></tr><tr><td rowspan=\"3\">促使聚结</td><td>缩水表面产生的力</td><td>2.6X10</td><td rowspan=\"3\">阻碍聚结</td><td>弹性变形抗力</td><td>1. 0×10-</td></tr><tr><td>巴水的毛细管力</td><td></td><td>静电斥力</td><td>1.8×1010</td></tr><tr><td>重力</td><td>1.1×10- 6.4×10~17</td><td></td><td></td></tr></table></body></html>  \n\n由表3-1-41可以看出，缩水表面产生的力、凹月面水的毛细管力和弹性变形抗力在同一数量级，而主要是缩水表面产生的力和毛细管力克服弹性变形抗力而聚结成膜。另外这里把乳胶粒子的变形看成弹性变形，其实乳胶粒子是黏弹体，还要考虑与时间相关的流变性，但这样处理相当复杂，故简化处理。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 878,
+        "chunk": "# 2.乳胶漆的涂膜结构  \n\n乳胶漆是由乳液、颜料、填料、助剂和水组成。当环境温度和基层温度高于乳胶漆的最低成膜温度时，由于水分挥发而干燥聚结成膜。涂膜是由固体聚合物、颜料、填料、部分残留助剂和气孔组成的一个多相体系。  \n\n固体聚合物是乳液水分挥发后留下的部分。在合适的成膜条件下，乳液聚合物颗粒变形，聚结成连续涂膜，同时聚合物界面分子链相互扩散、渗透、缠绕，使乳胶粒子消失，成为整体。固体聚合物的数量按配方的不同约占涂膜总重量的 $10\\%\\sim50\\%$ 业 ?  \n\n颜料填料大小范围比较宽，颜料约为 $0.1\\sim10\\mu\\mathrm{m}$ ，填料是涂膜体系中最粗的组分，大多为 $0.5\\sim50\\mu\\mathrm{m}$ ，甚至达 $100\\mu\\mathrm{m}$ ，质感涂料中填料也有达几毫米的。对于亚光乳胶漆膜，颜料和填料也是数量最多的组分，这一组分起骨架的作用。  \n\n助剂原来在乳胶漆中用量就比较少，成膜后留在涂膜中就更少了。水溶性的那一部分残留助剂对涂膜的耐水性、耐洗刷性和表面张力等有一定影响。对于外墙涂膜，随着雨水的冲洗，该部分残留助剂将逐渐被冲洗去，而逐步留下孔隙。  \n\n一般认为，当PVC>CPVC时，会产生气孔，其总孔隙率 $^{-1-}$ CPVC/PVC。气孔随着PVC的增大而增大。也有研究者发现，不管PVC>CPVC，还是PVC $\\asymp$ CPVC，都存在气孔。CPVC，至少是LCPVC，不简单是开始产生气孔，而是共连续相结构的相转变点，即由聚合物为主连续相转变为空气为主连续相。  \n\n作为一个整体，多相组成的涂膜性能主要取决于界面结构，例如，颜料和填料/乳液聚合物、基层/乳液聚合物的界面。这是二个最主要的界面。  \n\n颜料颗粒填充在填料颗粒之间，小颗粒填充在大颗粒之间。固体聚合物主要是通过界面机械咬合力和范德华力把颜料填料黏结在一起，而形成涂膜。助剂的作用是双面刃。如湿润分散剂，一方面，它能降低表面张力，有利于乳液聚合物渗入颜料和填料表层，而产生较大的机械咬合力和范德华力；另一方面，成膜后，这些湿润分散剂会残留在颜料和填料/乳液聚合物界面，成为透湿剂，影响涂膜性能。因此，关键在于用量。用量适中，正面作用为主，负面作用为辅。涂膜中还有孔隙，这是一个非均相体系，是一个有机和无机的复合材料体系。薄层内墙涂膜厚度一般为 $50\\sim150\\mu\\mathrm{m}$ ，而薄层外墙涂膜厚度一般为 $80\\sim200\\mu\\mathrm{m}$  \n\n涂膜通过固体聚合物附着在基层上。作为建筑乳胶漆，基层一般是水泥砂浆抹灰层、水泥石灰砂浆抹灰层和水泥粉煤灰砂浆抹灰层等，这些基层是多孔的。具有较低黏度、较细粒径和合适表面张力的底涂或乳胶漆，深深地渗入基层中，很细的毛细孔里也能渗透进去，当然主要是乳液渗入基层中，成膜后而产生附着力，其中主要是机械咬合力和范德华力，也可能存在少量化学键力、静电引力和扩散力等。由此可以看出，聚合物在涂膜中起着多么重要的作用。  \n\n底涂层、中涂层和面涂层共同构成涂膜整体。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 879,
+        "chunk": "# 七、外墙保护理论  \n\n外墙涂料是建筑物的外衣，穿上它，既能实现有效的保护，又能达到理想的装饰。装饰效果人人皆知，保护作用往往不太被人们重视。  \n\n建筑物损坏的大敌之一就是水。水能产生溶蚀破坏。渗人的水冬天结冰，体积膨胀$9\\%$ ，从而产生膨胀应力，造成建筑物破坏。侵蚀性的气体如 $\\mathrm{CO}_{2}$ ， $\\mathrm{SO_{2}}$ ， ${\\mathsf{s o}}_{3}$ 等，也是通过水变为酸而导致建筑物损坏的。如果建筑外墙涂料不透气，水汽扩散受阻，一是阻碍墙体向外排湿；二是产生应力，使涂膜起泡，脱皮；三是导致墙身含湿量逐步增加，产生冷凝水富集，从而给墙体热工、结构等性能带来不利影响。所以要讨论保护问题，就必须涉及水，要达到保护的目的，就必须拒水和透气。透气才能居住舒适；不透气，犹如晴天穿雨衣一样，使人不舒服。",
+        "category": " Introduction"
+    },
+    {
+        "id": 880,
+        "chunk": "# 1.Kuenzel外墙保护理论  \n\n根据德国Kuenzel教授的外墙护理论，只有当透气性和吸水性达到某一合适值时，涂膜或其他材料才具有优越的保护功能。  \n\n通常，以吸水系数来表达吸水性，即：  \n\n$$\n\\scriptstyle{W={\\frac{Q}{t^{0,5}}}}\n$$  \n\n式中W——吸水系数， $\\bf k g/(m^{2}\\cdot\\bf h^{0.5})$ \\*Q——吸水量， $\\mathbf{kg}/\\mathbf{m}^{2}$ t—吸水时间，h。  \n\n这里采用时间的开方，是因为在一定时间内，材料的吸水量与时间的平方根成正比。吸水性一般按EN1062-3：1998《色漆和清漆抹灰层和混凝土基面上的外用涂料和涂料系统分类—一3.吸水性的测定和分类》测定。  \n\n用等效静止空气层厚度来描述水汽扩散阻力，即透气性。  \n\n$$\n\\boldsymbol{S_{d}}=\\mu s\n$$  \n\n式中 $\\boldsymbol{S}_{\\mathrm{d}}$ -—等效静止空气层厚度，m；μ扩散阻力系数，空气μ=1;s——涂膜厚度，m。  \n\n从保护的角度来说，吸水性越小越好，透气性越大越好。透气性一般按ENISO7783-2：1999《色漆和清漆抹灰层和混凝土基面上的外用涂料和涂料系统分类——2.透水汽性的测定和分类》测定。  \n\n理想的外墙系统应既没有吸水性，又没有水汽扩散阻力，但事实上这是不可能的，只能两者兼顾和统一，即：  \n\n$$\n\\mathbf{W}{\\leqslant}0,\\ 5\\mathbf{kg}/(\\mathbf{m}^{2}\\ {\\bullet}\\ \\mathbf{h}^{0.5})\n$$  \n\n$$\nW S_{d}{\\leqslant}0,1\\mathbf{k}\\mathbf{g}/(\\mathbf{m}\\bullet\\mathbf{h}^{0.5})\n$$  \n\n式(3-1-20）是选材时对材料吸水性的要求，也就是说，必须选用拒水材料才能达到保护的目的。各种不同基层的吸水性见表3-1-42。  \n\n表3-1-42基层材料吸水性 单位： $\\mathbf{kg}/(\\mathbf{m}^{2}\\cdot\\mathbf{h}^{0.5})$   \n\n\n<html><body><table><tr><td>材 料</td><td>吸水系数</td><td>材 料</td><td></td><td>吸水系数</td></tr><tr><td>纯石灰砂浆</td><td>7.0</td><td>混凝土</td><td></td><td>1. 1~1. 8</td></tr><tr><td>石灰水泥砂浆</td><td>2.0~4.0</td><td>灰砂砖</td><td></td><td>3.0~7.7</td></tr><tr><td>水泥砂浆</td><td>2.0~3.0</td><td>多孔砖</td><td></td><td>8.3~8.9</td></tr><tr><td>加气混凝土</td><td>4.4~7.7</td><td>实心砖</td><td></td><td>2.9 ~25.1</td></tr><tr><td>浮石混凝土</td><td>1.9~2.9</td><td></td><td></td><td></td></tr></table></body></html>  \n\n正如表3-1-42所示，砖、砂浆、混凝土材料的吸水系数大，达不到该要求，因此难以起保护作用。没有保护层的房屋的东墙遇风雨时变湿就是一个例证。  \n\n式(3-1-21）是选材时对透气性的要求，必须选用透气性好的材料，气密性太高也是达不到保护目的的。  \n\n式(3-1-22）说明两者之间的平衡关系，即拒水性和透气性的统一，从而得到有效的保护功能。  \n\n![](images/a56dff2b185a94c0369935f5bb462beda58be85a933bf594269aa40be9a668e7.jpg)  \n图3-1-12Kuenzel外墙保护理论  \n\n式（3-1-20）～式（3-1-22）的综合结果如图3-1-12所示，涂料的拒水和透气性必须落在阴影的面积中，才能有较好的保护功能。越接近原点，拒水透气性性能越好，保护功能越强。有机硅树脂涂料的拒水透气性就比较接近原点。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 881,
+        "chunk": "# 2.外墙保护理论应用  \n\n涂料固然有好坏，但涂料的选择，涂料和基底的匹配也是非常重要的。好的涂料，匹配不好，用得不当，也得不",
+        "category": " Introduction"
+    },
+    {
+        "id": 882,
+        "chunk": "# 到好效果。  \n\n选择涂料和施工时，要满足外墙保护理论提出的要求。两种涂料的性能参数见表3-1-43。  \n\n表3-1-43两种涂料的性能参数  \n\n\n<html><body><table><tr><td>性 能</td><td>涂料1</td><td colspan=\"2\">涂料2</td></tr><tr><td>涂层厚度S/m</td><td>200X10-§</td><td>200×10§</td><td>150×10</td></tr><tr><td>吸水系数W/[kg/(m²·h5）]</td><td>0.1</td><td>0.3</td><td>0.3</td></tr><tr><td>扩散阻力系数μ 等效静止空气层厚度/m WS/[kg/(m • h5)]</td><td>400 0.08 0.008</td><td>2000 0.4 0.120 不满足</td><td>2000 0.3 0.09 满足</td></tr></table></body></html>  \n\n由表3-1-43可以看出，涂料1符合保护理论要求，而涂料2的气密性很好，如果施工时涂层厚度为 $200\\mu\\mathrm{m}$ ，虽然透气性单项能满足 $S_{d}=0,4\\mathrm{{m}}{\\leqslant}2\\mathrm{{m}}$ 要求，但综合起来 $\\boldsymbol{w s_{\\mathrm{d}}}=$ $0.12\\mathrm{kg/(m\\cdoth^{0.5})}$ ，不能满足 $W S_{d}{\\leqslant}0.1\\mathbf{k}\\mathbf{g}/(\\mathbf{m}\\bullet\\mathbf{h}^{0.5},$ ）的要求。只有当涂层厚度为 $150\\mu\\mathrm{m}$ 时，才能满足要求。这表明，即使从保护角度来看，涂层厚度也不是越厚越好。  \n\n此外，墙体吸水性要由内向外逐层减少（这里所指的是相同材料层)，以防水渗入墙内。墙体的扩散阻力也要求由内向外逐层递减，以便水汽顺利地由内向外扩散。这是因为我国所处的气候带，在寒冷的季节，水汽扩散始终是由内向外。扩散的推动力是由于屋内和屋外空气温度与湿度不同，扩散流试图要达到平衡。而在温暖季节，这一扩散就近乎停止，这是由于墙内外两侧情况近乎相等。当然，这是指没有空调的情况。  \n\n涂料生产时，也要考虑拒水和透气两个方面，做到拒水和透气的统一，虽然国标中对涂料拒水和透气没有规定，但这是两个重要指标。设计涂料配方时，应予以考虑。  \n\n欧洲标准EN1062-1：2002待批稿按吸水性将涂料分为三类，高吸水性 $\\begin{array}{r}{W>0.}\\end{array}$ $5\\mathrm{kg/(m^{2}}$ ·$\\ensuremath{\\mathrm{h}}^{0.5})$ ，中等吸水性 $0.5\\mathrm{kg/(m^{2}\\cdot h^{0.5})}\\geqslant\\mathrm{W}>0.1\\mathrm{kg/(m^{2}\\cdot h^{0.5})}$ ，低吸水性 $\\begin{array}{r}{W\\leqslant0.}\\end{array}$ $\\scriptstyle1\\log(m^{2}$ ·$\\mathbf{h}^{0.5})$ 。按透气性亦将涂料分为三类，高透气性 $\\ensuremath{S_{\\mathrm{d}}}<0.14\\ensuremath{\\mathrm{m}}$ ，中等透气性 $1.4\\mathrm{m}>S_{\\mathrm{d}}\\geqslant0.14\\mathrm{m}$ 低透气性 $S_{d}{\\geqslant}1,4\\mathbf{m}$ 。  \n\n当然，Kuenzel外墙保护理论也是一个涂膜使用寿命的预测理论。  \n\n在Kuenzel理论中，透气性条件对于夏热地区开空调房间的墙体，还未考虑。  \n\n另外，因为这是一个外墙保护理论，如果同时考虑装饰作用，即考虑耐沾污性，有些提法可能要加限制，即边界条件。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 883,
+        "chunk": "# 八、乳胶漆性能评价  \n\n乳胶漆产品质量的优劣，往往是在长期的使用过程中才能反映出来的。但是为了使用的科学性、合理性、经济性和可靠性，必须事先了解或知道乳胶漆质量，也就是乳胶漆性能评价。 V",
+        "category": " Introduction"
+    },
+    {
+        "id": 884,
+        "chunk": "# 1.组成和结构  \n\n目前虽然还不能通过乳胶漆的组成和结构的设计而得到所要求性能的乳胶漆，但可以通过各组分的组成和结构以及它们之间关系的分析，来评价乳胶漆的性能。这种评价还是比较准确的。  \n\n乳胶漆的性能是由乳胶漆的组成及结构决定的。而对乳胶漆的组成及结构的影响最大的三个因素是乳液的组成和结构、颜料的组成和结构以及对比PVC。  \n\n乳液和颜料是乳胶漆的主要成膜物。其组成和结构对乳胶漆的组成及结构的影响是不言而喻的。而对比PVC是乳液和颜料之间关系调节杠杆。  \n\n乳液聚合物的耐久性是乳胶漆耐久性的基础。其 $T_{\\mathrm{{g}}}$ 反映涂膜的硬度、耐磨性和耐沾污性、其极性基与附着力紧密相关等。  \n\n颜料的组成和结构是乳胶漆保色性的基础。氧化铁类无机颜料和金属氧化物混相颜料保色性较好。菁类有机颜料保色性也不错。  \n\n通常，对比PVC低些，涂料性能会好些。  \n\n人们开发涂料产品时一般就是这样考虑的。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 885,
+        "chunk": "# 2.产品标准  \n\n乳胶漆性能好坏可通过比较而评定，在开发、生产和销售过程中也往往就是这样。通常比较的基准是某一标准，或另一乳胶漆。在我国，和国家标准、行业标准比较，或与国外先进国家标准比较是确定乳胶漆性能好坏常用的方法。这些标准如GB/T9756—2009《合成树脂乳液内墙涂料》、GB/T9755—2001《合成树脂乳液外墙涂料》、JG/T24—2000《合成树脂乳液砂壁状建筑涂料》、JC/T172—2005《弹性建筑涂料》和日本JISK5663--2002《合成树脂乳液涂料》等。  \n\n产品的实际使用质量特性有时很难确定。因此在制定乳胶漆标准时，往往采用易于测定并能反映产品实际质量特性的代用质量特性指标，用于评价和控制产品质量。但是代用质量特性指标并不等同于实际使用质量特性。  \n\n另外，产品标准只代表某一阶段人们对该产品质量的认识，认为这些项目对该产品质量是重要的，必须的，而且是可测的。产品标准也只反映某阶段人们生产该产品质量的水平。随着人们对该产品认识的深化，测试技术的发展，以及该产品质量水平的提高，产品标准将不断被修订，被完善提高。因此，产品标准的修订也往往滞后于科技进步和生产发展。  \n\n标准中的性能指标和实际使用结果的相关性对使用来说是重要的。参照GB/T9755-2001《合成树脂乳液外墙涂料》，介绍一些标准中性能指标和实际使用结果的相关性。  \n\n首先，必须明确，测试的性能指标不等于实际使用结果，但标准中规定的测试性能指标能否反映实际使用结果是很重要的。就最低要求来说，两者趋向要一致，最好是两者之间相关性要好。  \n\n(1）耐沾污性一方面，我国环境污染比较严重，空气中可吸人颗粒物（ $\\mathrm{PM}_{10}$ ）比较高；另一方面，我国没有屋檐的建筑物又比较多，以致墙面就成导流雨水的渠道。造成部分涂装并非因涂膜降解破坏而失去使用价值，而是因为严重污染而失去使用价值。因此在发达国家不是问题的外墙面污染在我国就是一个突出的问题。外墙建筑涂料的耐沾污性就成为我国的基本要求。  \n\n以粉煤灰为污染源，在实验室测定的耐沾污性，与自然曝晒以及实际使用结果之间的相关性鲜见有文章报道。上海申得欧有限公司的厂内 $90^{\\circ}$ 朝南几年自然曝晒结果和实际经验表明，在玻璃化温度对耐沾污性影响方面，以粉煤灰测定的耐沾污性与自然曝晒、实际使用结果之间有一定的相关性。在PVC对耐沾污性影响方面，以粉煤灰测定的耐沾污性和自然曝晒、实际使用结果之间恰好相反。如对于低PVC建筑外墙乳胶漆，以粉煤灰测定的耐沾污性是差的，甚至是不合格的，但自然曝晒及实际使用结果却是好的。所以以粉煤灰测定的耐沾污性有时会把人引向错误的方向。  \n\n耐沾污性测试结果能否反映建筑涂料涂膜实际耐沾污性是最关键的。只有在能反映实际使用耐沾污性的前提下，再求试验方法的简便性和重现性才有意义。一个测试结果与建筑涂料涂膜实际耐沾污性相关性好的测试方法，才能促进我国建筑涂料的生产、科学研究和开发向着确确实实提高建筑涂膜耐沾污性的正确方向前进。  \n\n现在耐沾污性测试的污染源已由粉煤灰改为配制灰，标准更新为GB/T9780—2005《建筑涂料涂层耐沾污性试验方法》。测试耐沾污性与实际使用耐沾污性的相关性还有待试验总结。  \n\n(2）耐人工气候老化性资料和经验都表明，GB/T9755—2001中的耐人工气候老化性与实际使用耐久性之间相关性也不好。更何况我国各质检站的人工老化仪器、操作条件等相差甚大。因人工老化仪器和操作条件等波动而造成测试结果的变化远远大于因产品质量波动而造成测试结果的变化屡见不鲜。因此，仅以人工老化判定外墙涂料耐久性不够科学。  \n\n这往往是因为人工老化箱中不存在大气环境中没有的紫外线、喷淋水没有达到实验室二级水的要求等。另外，自然条件很难模拟，而要加速则更加困难。  \n\n应把人工老化和自然曝晒以及实际使用结果结合起来，并以自然曝晒和实际使用结果为主。这做起来有点难度，但一定要逐步向此方向努力，别无捷径。一些涂料强国都已这样做了。  \n\n(3）耐水性和耐碱性根据GB/T9755—2001国家标准，耐水性和耐碱性按GB/T1733和GB/T9265进行测试。对丝光、半光和有光外墙乳胶漆，甚至弹性建筑乳胶漆，也就是低PVC的乳胶漆，往往会出现测试结果不合格的现象。而实际使用中，在完全成膜后，不存在该类问题。分析出现此矛盾结果的原因如下。  \n\n其一，就是GB/T9755—2001规定试板的养护期是7天，其实乳胶漆完全成膜需四周甚至更长的时间。7天时，丝光、半光、有光乳胶漆和弹性乳胶漆只是部分成膜，成膜乳液较多，其性能还不足以抵抗乳化剂等亲水组分因吸水而产生的应力，因此在测试中常出现耐水性问题。  \n\n其二，测试条件与实际情况不符。测试时，试板是浸在蒸馏水或 $\\mathrm{Ca(OH)_{2}}$ 饱和溶液中。实际使用时，涂膜不是浸泡在水中，而只是受到雨淋。  \n\n其三，因为丝光、半光和有光乳胶漆以及弹性乳胶漆，PVC较低，乳液含量较高，因此乳化剂含量也较高所致。在乳胶漆中，乳化剂作为稳定剂而吸附在乳胶粒表面。在乳胶漆成膜过程中或成膜后，乳化剂作为中间相而处在乳胶粒的界面上，或迁移至基层界面处，或由于乳液聚合物分子的互相扩散而夹杂在乳胶膜中。这些亲水性的乳化剂就是造成涂膜对水敏感和影响附着力的主要原因。  \n\n其四，由于丝光、半光和有光乳胶漆以及弹性乳胶漆，PVC较低，因此涂膜较致密，孔隙率较低。水一旦进入涂膜，蒸发时不易找到足够多的通路离开，所以易产生鼓泡。  \n\n另外，对于丝光、半光和有光乳胶漆以及弹性乳胶漆，耐碱性测定结果不合格，往往实质也是水的问题。因为耐碱性试验时，是将试板浸泡在 $\\mathrm{Ca(OH)}_{2}$ 的饱和溶液中。往往不是碱使其鼓泡，而是水使其鼓泡。 S  \n\n为了解决丝光、半光和有光乳胶漆以及弹性乳胶漆实际使用时耐水性和耐碱性是好的，但检测时耐水性和耐碱性不合格这一矛盾，建议将丝光、半光和有光乳胶漆以及弹性乳胶漆的试板养护期至少延长至14天，最好是28天。这样做虽不能完全解决上述矛盾，但至少能缓解矛盾。日本JISK5660—2002《合成树脂乳液有光涂料》规定对耐水性和耐碱性的试板养护期就是14天，而JISK5663—2002《合成树脂乳液涂料》规定对耐水性和耐碱性的试板养护期仅5天。美国和欧盟对乳胶漆没有耐水性和耐碱性检测项目。 C  \n\n(4）保色性水桶理论告诉人们，一个水桶盛水量的多少只与最短的那块板有关，而不管其他板的长短。建筑涂料的质量也一样，其使用寿命同样取决最薄弱的组分。  \n\n例如彩色外墙乳胶漆，从分子量的角度看，乳液聚合物分子量高，为 $10^{5}\\sim10^{7}$ ，而有机颜料分子量低，为 $10^{2}{\\sim}10^{3}$ 。有机颜料分子量比乳液聚合物分子量低得多，低 $2{\\sim}5$ 个数量级，当然，它们的组成和结构也是不同的。因此，用有机颜料配制彩色外墙乳胶漆时，往往首先是有机颜料降解褪色而失去装饰效果。当然，这是一个重要指标，但GB/T9755—2001对彩色乳胶漆的保色性还没有规定。确实，颜色有各种各样，规定也难。  \n\n色彩丰富是乳胶漆的最大优点之一。乳胶漆的装饰性能主要通过色彩、质感和光泽来体现。因此，保色性是外墙乳胶漆的重要性能。生产企业应选择保色性好的色浆，严格控制色浆用量和基础漆的质量，保证外墙乳胶漆的保色性。保色性可以通过自然曝晒等确定。  \n\n也有用户要看实际工程，如涂装后若干年的工程。这也是既简便又有效的方法。  \n\n总之，GB/T9755—2001虽然有些指标测试结果和实际使用性能之间的相关性不那么好，但它对于规范我国外墙乳胶漆的质量还是起了重要作用，并将继续起作用。  \n\n国内其他标准也有相似情况。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 886,
+        "chunk": "# 3.功能性  \n\n乳胶漆除了保护和装饰作用外，功能化成为其明显的发展趋势。如遮盖裂缝的弹性涂料、防止混凝土碳化的防碳化涂料、防霉涂料、隔热保温涂料、抗氯离子渗透涂料等。  \n\nJG/T172—2005《弹性建筑涂料》以涂膜在标准状态下、 $-10\\%$ 和 $80^{\\circ}\\mathrm{C}$ 热处理后的断裂伸长率来评价弹性。EN1062-7：2001《色漆和清漆抹灰层和混凝土基面上的外用涂料和涂料系统分类—7.遮盖裂缝能力的测定》也与其相似。  \n\n欧洲标准EN1062-1：2002《色漆和清漆抹灰层和混凝土基面上的外用涂料和涂料系统分类》（待批稿）以透二氧化碳量 $\\mathbb{L}\\mathbb{g}/(\\mathbf{m}^{2}\\cdot\\mathbf{d})$ 』或透二氧化碳阻力来划分抗碳化性，测试按EN1062-6：1999《色漆和清漆抹灰层和混凝土基面上的外用涂料和涂料系统分类——6.透二氧化碳性的测定》进行。  \n\n防霉性按GB/T1741—2007《漆膜耐霉菌性测定法》进行，也可按ASTMD5590—2000《4周琼脂板加速测定涂膜和相关涂层防霉性》，或英国标准BS3900PartG6—1989及相关涂层防霉测定法进行。防藻性的检验可按GB/T21353—2008《漆膜抗藻性测定法》或ASTMD5589—1997《涂膜和相关涂层防藻测定法》进行。  \n\n涂料的隔热保温性可通过反射率、发射率和热导率测定评价。这方面的测试标准有ASTMC1549——2004《用便携式太阳反射计确定常温下太阳光反射比的标准试验法》，ASTMC1371—2004《用便携式发射仪确定材料常温下发射率的标准试验法》，ASTME903—1996《用积分球法确定材料太阳光吸收率、反射率和透过率的试验法》，ASTMC177—2004《用护热板法测定稳态热通量和传导性的标准试验方法》，中华人民共和国国家军用标准GJB2502—1995《卫星热控涂层测试方法》，GJB5023.1—2003《材料和涂层反射率和发射率测定方法第1部分：反射率》，GJB5023.2—2003《材料和涂层反射率和发射率测定方法第2部分：发射率》，GB/T10294—1988《绝热材料稳态热阻及有关特性的测定防护热板法》（等效采用ISO8302—1991）等。  \n\n未见有涂膜抗氯离子渗透性的专用测试方法，一般参照混凝土抗氯离子渗透性测定方法，如ASTMC1202—97《混凝土抗氯离子渗透性电化学测定法》，北欧标准NTBuild492《氯离子扩散系数快速实验方法》，中国土木工程协会标准CCES01—2004《混凝土结构耐久性设计与施工指南》等。  \n\n对于这些功能的测试指标与实际使用结果之间的相关性未见有报道。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 887,
+        "chunk": "# 4.环保性  \n\n内墙乳胶漆的环保性应符合国家强制性标准GB18582—2008 $\\ell$ 室内装饰装修材料内墙涂料中有害物质限量》的要求。只有符合该强制性标准要求的内墙建筑涂料，才能进入市场销售。也就是说，该强制性标准是内墙建筑涂料环保方面的起码要求，也是最低要求。因为不符合该强制性标准要求的内墙建筑涂料就不能销售了。  \n\n国家强制性标准GB18582—2008有四方面要求：一是内墙建筑涂料挥发性有机化合物（VOC）不得大于 $120\\mathbf{g}/\\mathrm{L}$ 涂料 (扣除涂料中的水)；二是游离甲醛含量不得大于$100\\mathrm{{mg/kg}}$ 涂料；三是苯、甲苯、乙苯、二甲苯总和不得大于 $300\\mathrm{mg/kg}$ 涂料；四是重金属含量，包括可溶性的铅、镉、铬和汞，分别不得大于 $90\\mathrm{mg/kg}$ 涂料、 $75\\mathrm{mg/kg}$ 涂料、$60\\mathrm{mg/kg}$ 涂料和 $60\\mathrm{{mg/kg}}$ 涂料。  \n\n环境标志建筑涂料一般是指通过有关认证、符合国家环保总局HJ/T201—2005《环境标志产品技术要求水性涂料》标准要求。HJ/T201—2005 的要求见表3-1-44。在挥发性有机化合物方面，HJ/T201—2005要求内墙建筑涂料不得大于 $80\\mathbf{g}/\\mathrm{L}$ 涂料（扣除涂料中的水)。对游离甲醛的要求，国家环保总局的HJ/T201—2005《环境标志产品技术要求水性涂料》标准要求游离甲醛含量不得大于 $100\\mathrm{mg/kg}$ 涂料，与GB18582—2008一样。对苯、甲苯、乙苯、二甲苯总和的要求，国家环保总局的HJ/T201—2005规定不得大于 ${500}\\mathrm{mg/}$ $\\mathbf{k}_{\\mathbf{E}}$ 涂料，GB18582—2008规定不得大于 $300\\mathrm{mg/kg}$ 涂料，GB18582—2008反比HJ/T201—2005要求严格。在重金属含量要求方面两个标准是一样的。  \n\n表3-1-44水性涂料中有密物限量要求  \n\n\n<html><body><table><tr><td>产晶种类</td><td>内墙涂料</td><td>外墙涂料</td><td>墙体用底漆</td><td>水性木器漆、水性防腐涂料、 水性防水涂料等产品</td><td>腻子(粉状、膏状)</td></tr><tr><td>（挥发性有机化合物的含量</td><td>≤80g/L</td><td>≤150g/L</td><td>≤80g/L</td><td>≤250g/L</td><td>≤10g/kg</td></tr><tr><td>卤代烃（以二氯甲烷计）/ (mg/kg)</td><td colspan=\"5\">≤500</td></tr><tr><td>量、甲苯、二甲苯、乙苯的总</td><td colspan=\"5\">≤500</td></tr><tr><td>甲醛/(mg/kg）</td><td colspan=\"5\">≤100</td></tr><tr><td>铅/(mg/kg)</td><td colspan=\"5\">≤90 *</td></tr><tr><td>幅/（mg/kg）</td><td colspan=\"5\">≤75</td></tr><tr><td>铬/(mg/kg）</td><td colspan=\"5\">≤60</td></tr><tr><td>汞/(mg/kg)</td><td colspan=\"5\">≤60</td></tr></table></body></html>  \n\n德国蓝天使环境标志RAL-UZ102—2000对内墙建筑涂料的环保要求是最严格的要求之一。如其对挥发性有机化合物的要求是不得大于 $700\\mathrm{mg/kg}$ ，即仅 $1,05g/\\mathrm{L}$ 涂料。  \n\n有的发达国家还把气味作为环保要求。  \n\n另外，欧盟规定，防腐剂、防霉剂和防藻剂中某些活性组分在涂料中达到某一数量时要明示。例如，《欧洲危险物质导则》（European Dangerous Substances Directive）规定，当5-氯-2-甲基-4异噻唑琳-3-酮/2-甲基-4异噻唑啉-3-酮（简称CMIT/MIT）超过15mg/kg时，应标R43-皮肤接触时可能造成敏感反应。《欧洲危险物质导则》第29次技术修订将含量等于或大于 $0.1\\%$ 的苯并咪唑氨基甲酸甲酯（carbendazim）防霉剂列为2类致变物（mutagencategory 2）和2类重现毒性物（reprotoxiccategory 2），根据其含量，见表3-1-45。  \n\n假定防霉剂中苯并咪唑氨基甲酸甲酯含量为 $10\\%$ ，防霉剂在涂料配方中加量为 $1\\%$ ，则 涂料中苯并咪唑氨基甲酸甲酯含量刚好为 $0.1\\%$ 。也就是说，涂料配方中加量等于或大于  \n\n1%时，要明示；少于1%时，无需标识。我国在该方面工作还没有起步。  \n\n表3-1-45苯并咪唑氨基甲酸甲酯（carbendazim）的分类和明示  \n\n\n<html><body><table><tr><td>BCM含量/%</td><td>标志</td><td>危害标识</td><td>R-风险和S-安全</td><td>限定使用者</td><td>MSDS材料安全表</td></tr><tr><td><0.1</td><td>无</td><td>无</td><td>无</td><td>无</td><td>无</td></tr><tr><td>0.1~0.25</td><td>T</td><td>有毒</td><td>R43.S45</td><td>限定专业使用者</td><td>2类致变物</td></tr><tr><td>0.25~0.5</td><td>T</td><td>有毒</td><td>R46、R52/53 S53、S45</td><td>限定专业使用者</td><td>2类致变物</td></tr><tr><td>0.5~2.5</td><td>T</td><td>有毒</td><td>R46、R60.R61.R52/53</td><td>限定专业使用者</td><td>2类数性物</td></tr><tr><td>2.5~25</td><td></td><td>T、N有毒、对环境有危害</td><td>R46,R60、R61、R51/53 S53、S45,S60、S61</td><td>限定专业使用者</td><td>2类致变物 2类重现毒性物</td></tr><tr><td>≥25</td><td></td><td>T、N 有毒、对环境有危害</td><td>R46、R60、R61,R50/53</td><td>限定专业使用者</td><td>2类致变毒性物</td></tr></table></body></html>\n\n注：1.T代表白骨和酷，N代表死鱼和死树。  \n\n2.R46代表也许损害遗传；R60代表也许损害生殖；R61代表也许对未出生孩子有害；R52/53代表对水生物有害，也许对水环境造成长期负面影响；R51/53代表对水生物有毒，也许对水环境造成长期负面影响；R50/53代表对水生物很毒，也许对水环境造成长期负面影响，  \n\n3.S53代表用前有专门指导，避免接触；S45代表接触到或不适，即请医生咨询；S60代表该物品及其包装须按危险品处理；S61代表避免排人环境，参见材料安全数据表。  \n\n4.耿盟成员国在2005年10月31日前将《歌洲危险物质导则）第29次技术修订内容变成本国立法。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 888,
+        "chunk": "# 5.其他评价方法  \n\n外墙乳胶漆所使用的环境条件比较严酷，有强烈的太阳光照射，其中包括紫外线，有风、霜、雨、雪、凝露和冰冻的影响，有气温变化的作用，有霉菌和藻类等微生物的破坏，有的还有酸雨和化学物质的腐蚀等，因此，对外墙乳胶漆的性能要求也比较高。  \n\n(1）自然曝晒和加速曝晒评估涂膜质量较可靠的方法是，在强太阳光辐照地区自然曝晒中，监测其失光、保色性、开裂和粉化等。这些强太阳光辐照地区，如美国的佛罗里达和亚利桑那，我国的广州和海南岛等。对较耐久的涂料体系，这类方法可能要花5年以上时间，才能获得显著结果。而反射镜加速曝晒法和带喷水循环的反射镜加速曝晒法，由于有一组反射镜增强照于样板上的太阳光，使所需曝晒时间缩短为 $12{\\sim}18$ 个月。虽然佛罗利达等曝晒和反射镜加速曝晒法评价较可靠，但这两种方法本身是较费时和费钱的。  \n\n(2）扫描电镜和X射线光电子能谱在老化实验期间，可用扫描电镜（SEM）摄取表面形态的照片，以观察其变化。SEM的放大倍率可高达 $10^{5}$ 倍，分辨率达 $8\\mathrm{nm}$ 。X射线光电子能谱（XPS）被公认为研究固态聚合物表面结构和性能的最好技术之一，其典型取样深度小于 $10\\mathrm{{nm}}$  \n\n(3）动态力学分析动态力学分析法（DMA）是对涂膜破坏趋势相当灵敏的技术。涂膜老化使其力学性能失去平衡，这是由于在老化过程中，涂膜聚合物的降解和交联的结果。在动态力学谱中，降解表现为贮存模量和 $T_{\\mathrm{s}}$ 的下降，而交联却表现为贮存模量和 $T_{\\mathrm{s}}$ 的升高。老化时，降解和交联虽同时发生，但由于涂膜的组成和结构不同，使用环境条件的差异，一般只有一个是主导的。因此，可用动态力学分析法对涂膜使用寿命作预测。  \n\n(4）傅里叶变换红外光声光谱傅里叶变换红外光声光谱（FTIR-PAS）技术在高聚物表面研究中得到广泛应用。它不仅用于高聚物的鉴别，而且用于研究高聚物的老化和测定老化深度。制样也很方便，无需将涂膜从基层上剥离下来就可对其进行分析。  \n\n(5）电子自旋共振谱法在涂膜老化研究中，可用电子自旋共振谱法（ESR）来监测其自由基浓度的变化和过氧化氢生成速度等，从而对涂膜耐久性进行预测。  \n\n(6）原子力显微镜原子力显微镜（AFM）是由Binning等在1986年开发出来的一种新型显微镜。它使用一个尖端的探针扫描试样表面，通过控制及检出探针与试样表面间的相互作用力来形成试样表面形态图像。其分辨率可达原子水平 $(10^{-10}\\mathbf{m})$ 。对于非导电、非导热性的试样也能观测，如聚合物和生物分子等，且无真空要求，在常温常压下就能观测。因此，发展很快，已有多种类型AFM。这些原子力显微镜可分别用于研究材料表面形貌、力学特性、电磁特性、表面热特性和光特性等。  \n\n（7）计算机模拟计算根据现有知识和试验结果，编成程序，用计算机模拟计算，得出评价结果。  \n\n随着科学技术的发展，检测仪器设备的开发完善，对涂膜降解机理研究的深入，试验数据和使用结果资料的积累，计算机科学的前进等，人们对涂料性能评价将越来越接近实际。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 889,
+        "chunk": "# 九、乳胶漆的进展  \n\n这几年，由于乳液聚合、颜料和填料加工制造、助剂生产和配方技术的进展，乳胶漆的产品质量有了较大的提高，乳胶漆的品种有了长足的发展。高性能和多功能的环境友好型乳胶漆成为发展趋势。",
+        "category": " Introduction"
+    },
+    {
+        "id": 890,
+        "chunk": "# 1.低VOC和零VOC乳胶漆  \n\n目前，还没有统一的低VOC和零VOC乳胶漆的确切定义。暂且将VOC低于 $30\\mathbf{g}/\\mathrm{L}$ 定义为低VOC乳胶漆，将VOC低于 $1\\mathrm{g/L}$ 定义为零VOC乳胶漆。  \n\n(1）普通乳胶漆的分析生产乳胶漆最关键的组分是乳液。乳液聚合物的玻璃化温度C $T_{\\mathrm{s}}$ ）和最低成膜温度（MFT）是乳液的两个重要参数。乳液生产者和乳胶漆制造者都对它们予以极大的关注，因为 $T_{\\mathrm{s}}$ 决定乳胶漆的硬度、耐磨性和耐沾污性等，MFT与乳胶漆的最低施工温度和成膜助剂用量等密不可分。市场上有代表性乳液的 $T_{\\mathrm{s}}$ 和MFT见表3-1-46。  \n\n表3-1-46普通乳液的 $\\pmb{T_{8}}$ 和MFT  \n\n\n<html><body><table><tr><td>乳 液</td><td>类 型</td><td>T/C</td><td>MFT/C</td><td>供应商</td></tr><tr><td>Primal AC-261</td><td>纯丙</td><td>27</td><td>20</td><td>罗门哈斯</td></tr><tr><td>Acronal 296 DS</td><td>苯丙</td><td>22</td><td>20</td><td>巴斯夫</td></tr><tr><td>UCAR R-350A</td><td>醋丙</td><td>28</td><td>16</td><td>联合碳化</td></tr><tr><td>UCARR323</td><td>叔醋</td><td>21</td><td>20</td><td>联合碳化</td></tr></table></body></html>  \n\n由表3-1-46可以看出，通常， $\\textstyle{\\mathcal{T}}_{\\mathfrak{s}}$ 在 $20\\mathrm{{^{c}}}$ 以上，MFT比 $T_{\\mathrm{s}}$ 低几摄氏度，但仍比要求的最低施工温度 $5\\Upsilon$ 高许多。  \n\n为了满足最低施工温度的要求，乳胶漆生产企业的常规做法是加成膜助剂来降低MFT。只有当乳液聚合物的MFT降至 $5\\mathrm{{c}}$ 以下时，才能使乳胶漆的MFT达到 $^{5\\Upsilon}$ ，因为乳胶漆中还有颜料和填料，它们对乳胶漆的MFT也有影响。目前成膜助剂的加量为 $1\\%$ 左右，具体视成膜助剂性能、乳液和乳胶漆的MFT而定。一般还加 $2\\%$ 左右二醇类溶剂。对于乳液，希望 $T_{\\mathrm{*}}$ 尽量高些，在没有成膜助剂的条件下，希望MFT尽量低些，两者之间的距离尽量大些。理想的 $T_{\\mathrm{s}}$ 在 $29\\Upsilon$ 以上（对内墙乳胶漆，可低些，比如19℃以上)，理想的MFT在$3\\%$ 以下。这样成膜助剂和二醇类溶剂就不再需要了。这就是生产低VOC和零VOC乳胶漆的思路。  \n\n(2）生产低VOC和零VOC乳胶漆用乳液生产低VOC和零VOC乳胶漆的关键就是合成基本不需要或不需要成膜助剂和溶剂就能低温成膜的乳液。  \n\n①选择合适单体由于醋酸乙烯酯具有水增塑性，即水能犹如成膜助剂一样降低醋酸乙烯酯乳液的MFT，使其在低温下能形成完整的涂膜。乙烯的Tg为一68℃，具有独特的内增塑作用，其共聚乳液不仅在低温下成膜性能好，而且在高温下不回黏。再通过新的聚合技术，调整聚合物组分，引入某些功能单体，控制聚合物的分子量，就能合成不需成膜助剂而其性能完全满足要求的乳液。这种乳液的 $T_{8}$ 在 $15t$ 左右，而其MFT为 $0\\%$ 左右。由该类乳液生产的低气味无溶剂乳胶漆已成为广为销售的商品。  \n\n为了改善乳液的抗水解性，也有再引入部分丙烯酸酯单体，合成三元共聚乳液。这类乳液生产的低气味无溶剂乳胶漆具有与加成膜助剂和少量溶剂的乳胶漆一样的性能。  \n\nResolution（原壳牌）公司将醋酸乙烯和C11叔碳酸乙烯（VeoVa11）以50/50配比，将醋酸乙烯、VeoVa10和丙烯酸2-乙基已酯以55/20/25配比，将醋酸乙烯、VeoVal0和丙烯酸丁酯以60/20/20配比，分别制成不需成膜剂的乳液。这三种乳液的计算 ${{T}_{\\mathrm{{s}}}}$ 和MFT列于表3-1-47。  \n\n表3-1-47无溶剂VeoVa乳液的T和MFT  \n\n\n<html><body><table><tr><td>乳 液</td><td>T（计算）/C</td><td>MFT/C</td></tr><tr><td>VA/VeoVa 11(50/50)</td><td>-9</td><td>≤</td></tr><tr><td>VA/VeoVa 10/2-EHA(55/20/25)</td><td></td><td></td></tr><tr><td>VA/VeoVa 10/BA(60/20/20)</td><td>5</td><td>5</td></tr></table></body></html>  \n\n据介绍，以这三种乳液配制的低气味无溶剂亚光乳胶漆，性能达到要求。未见 $\\boldsymbol{T}_{\\mathrm{s}}$ 测试值和抗回黏性报道。  \n\n$\\textcircled{2}$ 引进功能单体以具有空间位阻作用的二甲基一间异丙烯基苄基异氰酸酯单体（TMI）为交联剂，通过氧化-还原引发体系，合成醋丙、苯丙和纯丙乳液，以这些乳液配制的乳胶漆，在相同的颜料体积浓度（PVC）下，性能与需成膜助剂乳液制成的乳胶漆相当，而VOC可降至 $0.58/\\mathrm{L}$ 以下。  \n\n$\\textcircled{3}$ 硬乳液和软乳液共混硬乳液和软乳液共混以获得零VOC乳胶漆，软乳液的 $\\textstyle T_{\\mathrm{*}}$ 在室温以下，即使与相当量的硬乳液相混，不加成膜剂，也能在室温干燥成膜。在此试验结果的基础上，调整软硬乳液的 $T_{\\mathrm{{s}}}$ 值、粒径和用量等参数，就能生产低VOC和零VOC乳胶漆。  \n\n$\\textcircled{4}$ 核壳乳液聚合乳胶粒子的结构形态对乳液的MFT有很大影响。以甲基丙烯酸甲酯（MMA）单体和丙烯酸乙酯（EA）单体进行核壳乳液聚合为例。MMA和EA各 $50\\%$ ，按Fox方程计算，其 $T_{\\mathrm{s}}{=}28.7\\Upsilon$ 。共聚乳液的MFT为 $30\\Upsilon$ ，而以PMMA为核，PEA为壳的乳液的MFT为 $0^{\\circ}\\mathrm{C}$ 。可见核-壳乳液聚合显著改变了乳液的成膜性。  \n\n(3）生产低VOC和零VOC乳胶漆尽管不需要成膜助剂和溶剂就能成膜的乳液对于生产低VOC和零VOC乳胶漆是至关重要的，但仅此是不够的，还要求这类乳液具有很低的残余单体含量，比如说 $100\\mathrm{mg/kg}$ 以下，因为残余单体不仅提高VOC含量，而且还产生难闻气味。同时要有不含溶剂、环境友好型的助剂和色浆与之配套。还要求乳液和色浆中不含烷基酚聚氧乙烯醚（APE)，APE降解性差，对人体内分泌有干扰作用。此外，防腐剂和$\\mathsf{p H}$ 调节剂的释放物问题亦需考虑，防腐剂中防腐组分，即有毒有害物质，也应有控制。  \n\n在德国斯堪的纳维亚等地区，这类低气味无溶剂的亚光、有光内墙乳胶漆已是成熟的产品，销售多年。  \n\n在我国，也有一些公司生产低VOC和零VOC的内墙乳胶漆。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 891,
+        "chunk": "# 2.乳胶粉涂料  \n\n乳胶粉是将乳液通过喷雾干燥而制取的。目前，大部分乳胶粉是醋酸乙烯类共聚物，也  \n\n有苯丙和纯丙类的。自20世纪50年代以来，乳胶粉逐步应用于水泥材料的改性、瓷砖黏结剂、墙纸糊裱和黏结胶浆等。  \n\n用乳胶粉来生产乳胶粉涂料，具有如下优点。  \n\n(1）运输和贮存方便普通涂料中约含 $20\\%\\sim50\\%$ 的水，而在乳胶粉末涂料中，这部分水要到使用时才加人。也就是说，这部分水既不需运输，也不需要贮存。另外，含水的涂料，当运输和贮存的温度低于 $\\mathsf{o r}$ 时，往往会冻坏，而乳胶粉末涂料不存在此问题。  \n\n(2）无需防腐剂乳胶漆中既有水，又有细菌的食粮，容易被细菌污染。因此，为了防止变质，要加防腐剂。乳胶粉末涂料中，没有水，被细菌污染的可能性就少得多，所以一般不需防腐剂。  \n\n生产乳胶粉末涂料，像生产一般乳胶漆一样，也需要高速分散机。同时乳胶粉的价格也高于同类乳液，而有的乳胶粉重新分散成乳液后的质量与原乳液还有差距。故乳胶粉涂料还处于试验阶段。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 892,
+        "chunk": "# 3.荷花效应乳胶漆  \n\n房屋所有者和房屋建造者都希望外墙面保持干燥清洁。但由于我国环境条件还不尽人意，外墙面往往会受到污染，有的甚至受到严重污染。因此，人们一直在探求能保持外墙面干燥清洁的建筑涂料。  \n\n荷叶效应乳胶漆就是能保持外墙面干燥清洁的一种建筑涂料，它是仿生学在建筑涂料中应用的一个例子。  \n\n(1）荷叶效应乳胶漆的开发很久以来，优化的自洁功能已在自然界存在，荷叶就是其中的代表。荷叶表面具有很好的僧水性，实际上是不能湿润的，它还出污泥而不染，这是为了适应环境而长期演变的结果。  \n\n德国玻恩大学植物学教授W.Bartblott研究了荷叶的结构和荷叶效应机理。经研究发现，荷叶之所以具有以上性能，是因为叶子表面既憎水，又有一个显微结构。  \n\n德国Sto上市公司下属ISPO公司，根据荷叶效应机理和硅树脂外墙涂料的实际应用结果，经过三年的研究工作，成功地把荷叶效应移植到外墙乳胶漆中，开发了微结构有机硅乳胶漆，即荷叶效应乳胶漆。  \n\n这种荷叶效应乳胶漆采用具有持久憎水性的少乳化剂有机硅乳液等一些专门物质，并形成一个纳米级显微结构，从而使其涂膜具有类似荷叶的表面结构，达到拒水保洁功能。荷叶和荷叶效应乳胶漆的结构比较如图3-1-13所示。可以看出，二者的结构非常相似。  \n\n![](images/718fa4604298cf0204a400754c0060bdf94599c9dc05da23ddcd70c2ef99c06f.jpg)  \n图3-1-13荷叶和荷叶效应乳胶漆结构  \n\n(2）荷叶效应机理市场上的荷叶效应涂料或乳液，绝大多数是通过降低表面张力来实现的。这种通过降低表面张力，其提高与水的接触角有限，约能提高至 $120^{\\circ}$ 左右，如市场上的硅树脂涂料与水的初始接触角为 $93^{\\circ}\\sim115^{\\circ}$ ；它们与灰尘的接触面积基本不变，因此，荷叶效应的结果是有限的，很难达到既保持涂膜干燥，又具有自洁功能。  \n\n与水的接触角至少要达到 $130^{\\circ}$ ，这时表面具有显著的惜水性，成珠滚落的雨水才具有自洁功能。  \n\n把降低表面张力和形成显微结构结合起来，才能取得很好的荷叶效应结果。根据表面物理化学中表面平整度对接触角的影响规律可知，当接触角小于 $90^{\\circ}$ 时，表面粗糙度大些能使接触角进一步减小；而当接触角大于 $90^{\\circ}$ 时，粗糙表面能使接触角进一步提高。荷叶效应乳胶漆涂膜与水的接触角大于 $90^{\\circ}$ ，所以粗糙的显微结构可提高接触角，约能提高至 ${{140}^{\\circ}}$ 另一方面，一个显微粗糙表面，还可以使灰尘与涂膜的接触面积降至原来的 $1\\%$ 以下，从而使灰尘与水的黏附力大于灰尘与涂膜的附着力。因此，下雨时，雨水在墙面上成珠滚落，同时把灰尘带走，使墙面保持干燥和清洁，如图3-1-14所示。这就是乳胶漆的荷叶效应机理。  \n\n![](images/76bc0d894451b370ece3eae59ed0d41e9ebe5a915aabd9248f946330828f8ac6.jpg)  \n图3-1-14雨水成珠滚落，灰尘随之带走  \n\n(3）移动水的自洁作用德国玻恩大学开发出一个快速测定移动水清洁作用的试验方法，称为集灰试验。即在涂膜试板上，撒一些炭黑或粉煤灰，接着滴几滴水，使试板稍微倾斜晃动，从而水就在试板上来回移动。对于普通的涂膜，包括硅树脂涂膜，随着水的移动，在涂膜上留下含灰的水迹。对于荷叶效应乳胶漆涂膜，水成为一个大珠点，炭黑或粉煤灰集聚在大水珠的外围，而涂膜仍保持干净清洁。  \n\n表3-1-48是水、炭黑、荷叶和一些涂膜的表面张力以及部分材料与水的接触角。  \n\n表3-1-48材料的表面张力及其与水的接触角  \n\n\n<html><body><table><tr><td>材料</td><td>表面张力/（mN/m）</td><td>色散分量/（mN/m）</td><td>极性分量/（mN/m）</td><td>与水的接触角/（*）</td></tr><tr><td>水</td><td>73</td><td>19</td><td>54</td><td></td></tr><tr><td>炭黑</td><td>30</td><td>30</td><td></td><td></td></tr><tr><td>硅树脂涂料C</td><td>20</td><td>15</td><td>5</td><td>93</td></tr><tr><td>特氟隆</td><td>18</td><td>18</td><td>。</td><td>111</td></tr><tr><td>硅树脂涂料A</td><td>17.4</td><td>17.2</td><td>0.2</td><td>115</td></tr><tr><td>荷叶效应乳胶漆</td><td>8</td><td>8</td><td>。</td><td>142</td></tr><tr><td>荷叶</td><td>7.5</td><td>7.5</td><td>0</td><td>145</td></tr></table></body></html>  \n\n只有当涂膜材料的表面张力色散分量明显少于水的表面张力色散分量，另外，其表面张力的极性分量为零时，移动的水珠才能收集灰尘。在已检测的硅树脂涂膜中，其表面张力中相对高的色散分量和存在极性分量都会降低其憎水性，从而影响其自洁性。  \n\n特氟隆，这种经典的不粘涂料，当其结构为显微平表面时，一点也没有自洁功能，而只  \n\n是容易擦干净而已。  \n\n（4）荷叶效应乳胶漆的耐沾污性测试涂料耐沾污性较可靠的方法是将试板90°放置的自然曝晒法。如图3-1-15所示是按DIN53166标准自然曝晒两年后，各种涂料明度值 $\\scriptstyle L$ 的降低情况。在这里，耐沾污性以明度值 $L$ 的降低来表示。可见，荷叶效应乳胶漆具有很好的耐沾污性。  \n\n![](images/40d4e9f95ebbeb0f75069c8b14d0040b6b413622a6a40ad381abd9ac57e8b1c8.jpg)  \n图中数字所表示的涂料  \n图3-1-15耐沾污性（明度降低）  \n\n<html><body><table><tr><td></td><td>憎水的乳胶硅酸盐复合涂料A</td><td>6</td><td>高PVC乳胶漆A</td></tr><tr><td>2</td><td>荷叶效应乳胶漆</td><td></td><td>低PVC乳胶漆B</td></tr><tr><td>3</td><td>增水的乳胶硅酸盐复合涂料B</td><td>0</td><td>高PVC乳胶漆B</td></tr><tr><td>4</td><td>硅树脂涂料B</td><td></td><td>低PVC乳胶漆A</td></tr><tr><td>5</td><td>硅树脂涂料A</td><td></td><td></td></tr></table></body></html>  \n\n由图3-1-15还可以看出，除了荷叶效应乳胶漆外，乳胶硅酸盐复合涂料具有很好的耐沾污性。经观察，其耐沾污性好是通过较大的表面粉化而达到的。而荷叶效应乳胶漆是由于自洁功能使其具有很好的耐沾污性。实际工程的效果也证明了这一点。  \n\n此外，荷叶效应乳胶漆具有很好的拒水透气性和耐久性等。但在某些地区，还要注意所谓的雨筋问题。  \n\n总之，这是人们首次把自然界的荷叶效应应用于涂料产品。荷叶效应乳胶漆把硅树脂涂料的优点和上万年来自然界演变结果结合起来，进一步发展了现有的外墙涂料，尤其是硅树脂涂料，从而使外墙保持干燥、清洁、耐久成为可能。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 893,
+        "chunk": "# 4.保洁弹性外墙乳胶漆  \n\n为了遮盖基层裂缝，人们开发了弹性乳胶漆。弹性乳胶漆所用乳液的玻璃化温度（ $T_{\\mathrm{*}}$ >往往比较低，通常在 $-45\\mathrm{\\sim}-10\\mathrm{\\bar{C}}$ ，因此，使用温度一般高于 $T_{\\mathrm{s}}$ ，其涂膜比较软，耐沾污性成为弹性建筑乳胶漆这个水桶的最短的一块板。只有提高最短一块板的高度，才能提高弹性建筑乳胶漆这个水桶的盛水量。 9  \n\n弹性乳液是生产弹性乳胶漆的核心原料。要提高弹性乳胶漆的耐沾污性，首先从弹性乳液开始。  \n\n(1）选用合适的单体为了提高弹性建筑乳胶漆的耐沾污性，Roy等将一些特殊单体引人乳液聚合物骨架中，这些特殊单体如异甲基丙烯酸冰片酯、异丙烯酸癸酯、Veova11和甲基丙烯酸乙酯（EMA）等。结果发现，在相似玻璃化温度下，MMA/BA/EMA/MAA配方的耐沾污性和弹性都比MMA/BA/MAA配方稍好。当然，甲基丙烯酸乙酯较贯。  \n\n(2）表面自交联在弹性乳液中引入交联剂。当弹性乳胶漆干燥成膜时，通过交联反应，如紫外线自交联反应，形成一定交联密度的表面，提高表面Tg值，基本不影响涂膜的弹性，提高其硬度，从而提高了弹性建筑乳胶漆的耐沾污性。  \n\nRoy等在前面提及的引入特殊单体基础上，再加入交联剂，如二丙烯酸己二醇酯、甲基丙烯酸缩水甘油酯和甲基丙烯酸乙酰乙酸乙酯，发现二丙烯酸己二醇酯可明显改善耐沾污性。继续加2,2-二甲氧基-2-苯基苯乙酮和二苯甲酮衍生物光引发剂试验，得出两者都能提高耐沾污性，但2，2-二甲氧基-2-苯基苯乙酮更好些。  \n\n紫外线和太阳光交联目前广泛地被用来提高弹性外墙乳胶漆涂膜硬度、抗粘连性和耐沾污性。  \n\n(3）核-壳乳液聚合与普通核-壳乳液刚好相反，弹性乳液在采用核-壳乳液聚合时，核为软单体聚合物，壳为相对较硬单体聚合物。软核主要提供弹性，相对较硬壳主要是提高表面 $T_{\\ast}$ 值，改善耐沾污性。相辅相成，达到较好的综合效果。  \n\n(4）有机硅改性弹性乳液王国建以八甲基环四硅氧烷（D）、乙烯基环四硅氧烷$(\\mathrm{D}_{4})$ 、丙烯酸丁酯（BA)、甲基丙烯酸甲酯（MMA）和丙烯酸（AA）单体，分别通过预乳化连续滴加法和种子聚合法合成有机硅改性弹性乳液。种子聚合法合成时，以聚丙烯酸酯为种子乳液，以有机硅聚合物为壳。结果发现，预乳化连续滴加法的改性效果优于种子聚合法。因此，他采用预乳化连续滴加法。  \n\n在采用预乳化连续滴加法时，他得出：随着有机硅单体含量提高，乳液膜拉伸强度和耐沾污性提高，延伸率先提高后降低。有机硅单体含量占单体总量的 $13\\%$ ，乙烯基环四硅氧烷的含量占有机硅单体总量的 $4\\%\\sim6\\%$ ，相容剂的含量占单体总量的 $2\\%$ ，能取得较好结果。  \n\n谢家仓等用相似的单体，采用核-壳聚合技术，但以聚硅氧烷为核，以聚丙烯酸酯为壳，合成弹性乳液。他们认为，乙烯基环四硅氧烷的用量一般为 $0.3\\%\\sim5\\%$ ，八甲基环四硅氧烷的用量占单体总量的 $5\\%\\sim20\\%$ ，聚丙烯酸酯中，硬软单体比例为 $2{\\sim}3$ ，得到弹性乳液性能较好。  \n\n其实，在有机硅改性时，是提高涂膜的憎水性。其提高耐沾污性的机理是降低了涂膜的吸水性，从而减少了溶解或分散在雨水中灰尘被吸入涂膜而造成的沾污。  \n\n(5）水性聚氨酯弹性乳液张宪康等采用异佛尔酮二异氰酸酯（IPDI)、分子量为2000的聚丙二醇（PPG)、二羟甲基丙酸（DMPA）和二乙烯三胺（DETA）等为原料，用预聚体直接分散法合成水性聚氨酯弹性乳液。用该乳液生产水性聚氨酯弹性涂料，测试耐沾污性很好。  \n\n(6）乳液表面亲水亲油性卢荣明等提出，使涂膜表面适度带亲水基有利于生产保洁弹性乳胶漆。由于亲水基团的憎油性，油污或带油污的灰尘即使附着到涂膜表面，也难以向涂膜内部迁移渗透，只能形成暂时的污染。在雨水的冲刷下，污物会随雨水冲走。据此，他们在合成弹性乳液时，采用核-壳乳液聚合，并在乳液表面引进一定亲水基团。以这种弹性乳液生产的弹性外墙乳胶漆耐沾污性得到较大提高。  \n\n（7）聚合型乳化剂普通乳化剂会迁移到涂膜表面，这些小分子的乳化剂既影响涂膜耐水性，又影响耐沾污性。采用聚合型乳化剂就不会出现此情况，从而对提高耐沾污性有帮助。  \n\n(8）调整配方除了核心组分弹性乳液外，通过调整配方改善耐沾污性也有一定余地。如不用成膜助剂，虽会降低初期延伸率，但能提高耐沾污性。此外，加特殊助剂也能改善耐  \n\n沾污性等。  \n\n(9）涂装设计和涂装作业由于弹性建筑乳胶漆的耐沾污性是其弱项，所以正确的涂装设计和涂装作业对涂膜保洁尤显重要。如做好滴水线和泛水坡度等。  \n\n在采取一些耐沾污性改进措施后，弹性建筑乳胶漆的实际使用耐沾污性是能满足涂装要求的。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 894,
+        "chunk": "# 5.单组分常温自交联乳胶漆  \n\n目前，绝大部分的乳液聚合物都是热塑性的，因此其抗粘连性、耐沾污性、耐溶剂性、耐热性等尚存在一定问题。在乳液聚合时，引入可实现交联的官能团，使其在成膜时，产生交联，形成三维网状结构，克服以上不足之处，更好地满足使用要求，是建筑涂料发展方向之一，也是目前研究的热点之一。  \n\n作为建筑乳胶漆，这种交联必须是常温交联，而且为了使用的方便，最好是单组分的。  \n目前有如下一些方法制备单组分常温交联建筑乳胶漆。  \n\n(1）失逸性交联双丙酮丙烯酰胺，英文名diacetoneacrylamide，缩写为DAAM，学名N-(1,1-二甲基-3-氧丁基）丙烯酰胺，是丙烯睛和丙酮在磺酸催化下缩合而成。这是一个特殊的反应型多功能单体，其结构式如下。  \n\n$$\n\\begin{array}{c}{{0\\quad\\mathrm{{CH_{1}}\\quad0}}}\\\\ {{\\big\\downarrow\\quad}}\\\\ {{\\mathrm{CH_{2}{\\longrightarrow}C H C N H C{\\longrightarrow}C H_{2}C{\\longrightarrow}C H_{3}}}}\\\\ {{\\big\\downarrow\\quad}}\\\\ {{\\mathrm{CH_{3}}}}\\end{array}\n$$  \n\n因为DAAM是不饱和的单体，可聚合，均聚物 $T_{\\mathrm{{s}}}=65^{\\circ}\\mathrm{{C}}$ ，可见是一个硬单体。它也可与许多烯类单体共聚，其竞聚率见表3-1-49。由表3-1-49可以看出，DAAM与苯乙烯和甲基丙烯酸甲酯共聚是方便的。从而可在交联单体DAAM参与下进行乳液聚合，使乳液聚合物中引进酮羰基。这种乳液，可以是丙烯酸乳液、苯丙乳液、硅丙乳液和氟碳乳液等。  \n\n表3-1-49DAAM在乳液聚合时的竞聚率  \n\n\n<html><body><table><tr><td>单体1</td><td>单体2</td><td></td><td>Y</td></tr><tr><td>苯乙烯</td><td>DAAM</td><td>1.77</td><td>0.49</td></tr><tr><td>甲基丙烯酸甲酯</td><td>DAAM</td><td>1.68</td><td>0.57</td></tr></table></body></html>  \n\n在聚合结束后将交联剂己二酸二酰肼计量加人到乳液中。己二酸二酰肼，英文名adipicdihydrazine，缩写为ADH，其结构式如下。  \n\n乳液中虽然同时存在酮基和ADH，而且酮基能与酰肼基进行加成反应生成踪和水，反应式如下所示，但该反应是一个可逆反应。尤其是乳液中存在大量水时，该加成脱水反应实际上是不能进行的。因此，制成的乳液和乳胶漆在贮存期都是稳定的。  \n\n乳液或乳胶漆在干燥成膜过程中，由于水不断从涂膜中逸出，酮基与酰肼基进行加成反应生成踪和水的反应不断进行，涂膜逐步干燥成膜。这就称之为失逸性交联。  \n\n一般来说，乳液聚合物中的酮羰基与ADH交联比较慢，因为乳液聚合物是不溶于水的，而ADH是溶于水的，尤其当酮羰基被埋在乳液聚合物中时。若通过核-壳乳液聚合，使酮羰基处于壳层，并在聚合物酮羰基周围带上一些亲水基团，如羧酸盐和羟基等，有利于  \n\n交联进行。  \n\n此外，使用3-甲基丙烯酰氧基丙基三异丁氧基硅烷为共聚单体，通过乳液聚合，也能制得具有失逸交联性的三烷氧基甲硅氧化丙烯酸乳液和醋酸乙烯乳液。  \n\n(2）紫外和太阳光交联丙烯酸双环戊烯基酯，英文名dicyclopentenylacrylate，缩写为DCPA，是可聚合的单体，均聚物 $T_{\\mathrm{{g}}}=98^{\\circ}\\mathrm{{C}}$ ，但有臭味。其结构式如下。  \n\n在乳液聚合时，加入各种组分，如丙烯酸丁酯、甲基丙烯酸甲酯等，和紫外交联剂DC-PA进行聚合，所合成乳液聚合物中含有环戊烯基和丙烯位氢，可供交联。聚合完成后，加人少量的二苯酮光引发剂。当乳液和乳胶漆贮存时，因为没有紫外光，不发生交联，乳液和乳胶漆是稳定的。当其施工后成膜时，在太阳光的照射下，产生紫外交联，从而使涂膜性能提高。  \n\n另据介绍，以二酮类物质「如樟脑醒 $(\\mathbf{C}_{10}\\mathbf{H}_{14}\\mathbf{O}_{2})$ 为光引发剂，用量以质量计约 $1\\%$ ·以三丙烯酸三羟甲基丙烷酯（TMPTA)、二丙烯酸二聚氧乙烯酯（PEGDA2）等为交联剂，如TMPTA的最佳用量为 $7\\%\\sim10\\%$ ，生产可见光和太阳光交联乳液及乳胶漆。其性能优于未交联的乳胶漆，还可以生产低VOC和零VOC乳胶漆。也有人以氧化麟（ $\\mathrm{{\\bf{H}}}_{3}\\mathrm{{\\bf{P}}}0$ ， $\\mathbb{R}_{3}\\mathbb{P}\\mathrm{O}_{\\mathrm{\\ell}}^{\\mathrm{\\cdot}}$ 。为光引发剂，制成可见光交联乳液。  \n\n（3）氧化交联丙烯酸双环戊烯基氧乙基酯（DPOA）也是可聚合的单体，均聚物 $T_{\\mathrm{{g}}}=$ $337$ ，无气味。其结构式如下。  \n\n![](images/b4aaaffba796bb58834ade79b01a3176092e374b7f60b86aec94ed36264ed9f4.jpg)  \n\n在较高 $T_{\\mathrm{s}}$ 值的乳胶漆配方中，不需成膜助剂，而加DPOA，并加入少量催干剂，如钴盐。DPOA就可降低成膜温度，使乳胶漆在室温成膜。但DPOA不挥发，不仅环境友好，而且在催干剂作用下进行氧化自由基聚合，增加了涂膜的硬度、抗黏性和亮度。因此，DPOA被称为活性成膜助剂。  \n\n另外，也有人开发了烯丙基取代的乳液，贮存时是稳定的，只有在施工后，与空气中的氧气反应才交联。  \n\n(4）TMI交联众所周知，在合适的条件下，异氰酸酯能制得优质涂料，但它极易与水反应。甲基苯乙烯异氰酸酯单体（TMI）具有空间位阻作用，是一种既可与其他乙烯基单体共聚，又留有一NCO基供进一步交联的特殊交联剂，其结构如下。  \n\n![](images/c82543170a500c6c7cf9db2ae6328b1629f66a43e205b305553c63f79733f9a8.jpg)  \n\n通过氧化-还原引发体系，合成醋丙、苯丙和纯丙乳液。以这些乳液配制的低气味无溶剂乳胶漆，在相同的颜料体积浓度（PVC）下，耐洗刷性比需成膜助剂乳液制成的乳胶漆有较大提高，其他性能与其相当，而挥发性有机物（VOC）降至 $0,5g/\\mathrm{L}$ 以下。这种乳液可用于生产内墙乳胶漆。  \n\n(5）整合交联在乳液合成时，引入少量羧基功能单体，如甲基丙烯酸（MAA）、丙烯酸（AA）等，并加入金属盐，如醋酸锌。在成膜时，乳胶粒子界面间金属离子与羧酸根发生整合交联，使涂膜的耐水性、抗粘连性、耐沾污性等明显提高。金属离子的加入一般会降低乳液的稳定性。只有合理地选择含羧基功能单体的种类、用量、加料方式，以及金属盐交联剂的种类和用量等，才能取得预期的室温交联结果。  \n\n许振阳等采用醋酸锌为交联剂，得出：当丙烯酸含量为单体总量的 $4\\%\\sim8\\%$ ，醋酸锌 与丙烯酸摩尔比为 $0.3\\sim0.4$ 时，锌离子交联苯丙乳胶漆具有较好性能。  \n\n通过交联，乳液聚合物的分子量进一步提高，形成网状结构，并使涂膜逐步致密，热塑性降低，从而提高了涂膜性能。单组分常温交联是生产高性能低VOC建筑乳胶漆的一种有效途径。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 895,
+        "chunk": "# 6.氟碳乳胶漆  \n\n氟碳涂料的发展，经历了单一氟单体自聚（如聚四氟乙烯)，多种氟单体共聚，单一/多种氟单体聚合物和不含氟聚合物共混，单一/多种氟单体和不含氟单体共聚。制备方法也由早期的溶液聚合发展至乳液聚合。引入不含氟组分，目的是在保持氟碳涂料优异性能的前提下，改善其附着力，调节 $\\boldsymbol{T_{\\mathrm{s}}}$ 值，降低成本等。所研究的不含氟单体有：丙烯酸酯、环氧、聚氨酯、聚酯和醇酸等。其中，丙烯酸酯和氟碳互补性强，价格适中。  \n\n氟碳乳胶漆是以氟碳聚合物乳液为成膜物质，配以颜料、填料、助剂等而制成的氟乳液涂料。  \n\n尽管国内市场上也有不少氟碳乳胶漆。除了有些卖点外，未见有高性能的氟碳乳胶漆。也许是因为氟含量不足所致。",
+        "category": " Introduction"
+    },
+    {
+        "id": 896,
+        "chunk": "# 7.负离子乳胶漆  \n\n空气中负离子对人体健康有利，被称为空气中的维生素。在内墙乳胶漆中，加人负离子添加剂，从而使涂膜不断放出负离子，称为负离子乳胶漆。  \n\n成膜后，空气中的水分子可以通过涂膜与负离子添加剂接触，在负离子粉体颗粒电极附近的强电场作用下，电离成氢氧根离子和氢离子。氢氧根离子进入空气，吸收空气中水分子，形成水合羟基离子 $\\mathbf{H}_{3}\\mathbf{O}_{2}^{-}$ ，即为负离子。从而增加空气中负离子浓度，达到提高空气质量的目的。  \n\n另外，负离子涂料还有去除空气中甲醛、氨等有害物和抗菌抑菌作用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 897,
+        "chunk": "# 8.光催化乳胶漆  \n\n目前人们所说的环境友好型涂料，一般是指基本不影响或不影响环境的涂料。但这还不够，人们还在努力开发能净化空气涂料。  \n\n光催化涂料是指通过一定波长光的照射而具有催化反应功能的涂料。这种涂料具有抗菌、降解有机物和净化空气的作用。  \n\n（1）纳米 $\\mathbf{TiO}_{2}$ 光催化机理由纳米二氧化钛光催化剂配成涂料，当受紫外光照射时，这种半导体的光催化剂受激发产生电子-空穴对，如图3-1-16所示。电子和空穴使周围的氧气和水分子成为活性自由基，而活性自由基能将空气中有机或无机污染物，如氮氧化合物（ $\\mathrm{NO}_{x}$ 、甲醛、苯、二氧化硫等，直接分解成无害的物质，从而达到消除污染、净化空气的目的。  \n\n![](images/ae9f57ac1a800648cd05f9d8081d2f3772fec698390ec3bc1f02db25a7b07a75.jpg)  \n图3-1-16光催化剂受激发产生电子-空穴对示意图  \n\n其催化反应机理如下。  \n\n光（波长 ${\\leqslant}388\\mathrm{nm}$ 紫外光） $^+$ 纳米锐钛型 $\\mathrm{TiO}_{2}$ （禁带宽度3.2eV)—→价带（带正电的空穴 $\\mathbf{h}^{+}$ )十导带（带负电的高活性电子 $e^{-}$ >  \n\n这些自由基的氧化能都在 $500\\mathrm{kJ/mol}$ 以上。  \n\n有害物质大都含有如表3-1-50的化学键，所以自由基的氧化能足以使其降解。通常即：有机化合物（有害物质、异味等）—→二氧化碳（ $\\scriptstyle\\mathrm{:co_{2}}$ )+水（ $\\mathbf{H}_{2}(\\mathbf{\\mathrm{~O~}})$ 等。  \n\n表3-1-50部分化学键的键能  \n\n\n<html><body><table><tr><td>化学键</td><td>C-C</td><td>C-H</td><td>C-N</td><td>C-0</td><td>0-H</td><td>N-H</td></tr><tr><td>键能/（kJ/mol）</td><td>347</td><td>414</td><td>305</td><td>351</td><td>464</td><td>389</td></tr></table></body></html>  \n\n(2）光催化乳胶漆光催化涂料能降解有害物质，同样也会降解涂料中的有机物，如梨结剂、有机颜料等。通过原料选择和配方，达到两者之间平衡。  \n\n纳米锐钛型 $\\mathrm{TiO}_{2}$ 在涂料中应充分分散，并稳定地保持下来，以达到一定的催化活性。  \n\n据介绍，某一稀土掺杂的纳米锐钛型 $\\mathrm{TiO}_{2}$ 光催化剂的杀菌率，对金黄色葡萄球菌6h为 $100\\%$ ，对大肠杆菌6h为 $100\\%$ 。  \n\n光催化乳胶漆降解有毒有害物质、消除异味和抗菌的作用不仅与光催化剂的粒径、浓度和性能有关，而且与照射光的波长分布和照度、环境的湿度等相关。这一般是外墙光催化乳胶漆。  \n\n室内几乎没有紫外光，只有可见光，一般的紫外光催化涂料没有催化作用。因此，生产光催化内墙乳胶漆，关键是研制可见光催化的锐钛型 $\\mathrm{TiO}_{2}$  \n\n(3）光催化乳胶漆的特点光催化乳胶漆在光照射下能净化空气，其净化作用具有无可比拟的优点。  \n\n$\\Phi$ 把光能转化为化学能加以利用，无需另加能量。  \n\n$\\textcircled{2}$ 净化在常温常压下进行。  \n\n$\\textcircled{3}$ 能在较短时间内降解有毒有害物。当然，其前提条件是有毒有害物与涂层接触。  \n\n$\\textcircled{4}$ 锐钛型 $\\mathrm{TiO}_{2}$ 光催化剂稳定性好，无毒，不会产生二次污染。  \n\n$\\textcircled{5}$ 锐钛型 $\\mathrm{TiO}_{2}$ 光催化剂可持久长效作用。  \n\n因此，可见光催化内墙乳胶漆是一个无需耗能的环境友好型持续净化技术。涂刷一次，持久有效。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 898,
+        "chunk": "# 9.纳米乳胶漆  \n\n所谓的纳米乳胶漆，是指在其组成中，至少有一相尺寸在 $1{\\sim}100\\mathrm{nm}$ 之间，且与普通乳胶漆相比，其性能得到明显提高的乳胶漆。  \n\n在乳胶漆中加入纳米组分是一件不难的事，但要使该组分保持纳米状态，并起改性作用，从而大大改进和提高乳胶漆的性能，或产生新的应用性能，这才是纳米乳胶漆的关键所在，也即难点所在。",
+        "category": " Introduction"
+    },
+    {
+        "id": 899,
+        "chunk": "# 10.反射隔热乳胶漆  \n\n具有隔热保温性能的涂料叫隔热保温涂料。隔热是通过对太阳能的反射、对温度波动的 衰减、延迟等而达到，保温由高热阻来实现。按照隔热保温机理，可将隔热保温涂料分为阻 隔性隔热保温涂料、反射隔热涂料及辐射隔热保温涂料三类。 ?  \n\n反射隔热乳胶漆是由合成树脂乳液、热反射颜料、填料和助剂等组成。  \n\n这种薄层隔热反射涂料的热反射率高，一般在 $80\\%$ 以上，隔热作用明显。但如上所述颜色对热反射率有很大影响。另外，尽管薄层隔热反射涂料热导率不高，自身热阻较大，但  \n\n因涂膜厚度比较薄，总热阻有限，保温效果不大。可与其他保温材料配合使用。  \n\n通过传热系数 $\\kappa$ 值的计算能清楚地说明这一点。已知：外墙为双排孔混凝土小砌块190mm×190mm，内侧20mm石灰水泥砂浆找平层，如要求墙体K=1时，问需多厚隔热保温涂料？  \n\n$$\nK={\\frac{1}{R_{\\mathrm{i}}+{\\frac{\\delta_{1}}{\\lambda_{1}}}+{\\frac{\\delta_{2}}{\\lambda_{2}}}+\\cdots+{\\frac{\\delta_{n}}{\\lambda_{n}}}+R_{\\mathrm{e}}}}={\\frac{1}{0.11+{\\frac{0.02}{0.87}}+{\\frac{0.19}{0.69}}+{\\frac{\\delta_{3}}{0.05}}+0.04}}=1\n$$  \n\n式中 $8.$ -一每层材料的厚度，m；  \n\n——每层材料的热导率， $\\mathbf{W}/(\\mathbf{m}\\cdot\\mathbf{K})$ .$R_{\\mathrm{i}}$ · $R_{e}$ —外墙内、外表面换热传热阻，取 $0.11\\mathrm{m}^{2}\\cdot\\mathrm{K}/\\mathrm{W}$ 和 $0.04\\mathrm{m}^{2}\\cdot\\mathrm{K}/\\mathrm{w}.$  \n\n代人得 $\\delta_{3}=0,0276\\mathrm{m}=27.6\\mathrm{mm}$ ，也就是说涂膜厚度要达 $27.6\\mathrm{mm}$ ，这是既不经济，不可能的。  \n\n其实，要保温，就要求有一定的热阻。即要求材料不仅有低的热导率，而且还要有一定的厚度，两者缺一不可。  \n\n薄层隔热反射涂料的隔热原理主要是因热反射率高，有效地降低辐射传热和对流传热。  \n\n要达到高的热反射率，必须选用高折率的颜料，涂膜颜色选用白色或浅色比较容易达到，或采用光谱选择性材料配成一定颜色，配制有色隔热反射涂料的关键之一是选择较低吸收率的黑色颜料。美国军标规定深色漆反射率在 $50\\%$ 以上。  \n\n美国ASTMC1483—2004《建筑外用太阳能辐射控制涂料标准规程》规定，太阳能辐射控制涂料的反射率应等于或大于 $80\\%$ ＆  \n\n建设部JG/T235—2008《建筑反射隔热涂料》对建筑反射隔热涂料的隔热性能要求见表3-1-51。  \n\n表3-1-51建筑反射隔热涂料的隔热性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">序号</td><td rowspan=\"2\">项 目</td><td colspan=\"2\">指 标</td></tr><tr><td>屋面反射隔热涂料</td><td>外墙反射隔热涂料</td></tr><tr><td>1</td><td>太阳反射比(白色）</td><td colspan=\"2\">≥0.80</td></tr><tr><td></td><td>半球发射率</td><td colspan=\"2\">≥ 0.80</td></tr><tr><td>23</td><td>隔热温差/C</td><td colspan=\"2\">≥10</td></tr><tr><td>4</td><td>隔热温差衰减（白色）/℃</td><td>①</td><td>≤12</td></tr></table></body></html>\n\n$\\Phi$ 根据不同工程的需要，由设计确定，  \n\n这种产品现已用于海上钻井平台、油罐、石油管道、建筑业的钢结构屋顶和玻璃幕墙等，降低暴露在太阳热辐射下装备的表面温度和内部温度，改善工作环境，提高安全性等。  \n\n反射隔热乳胶漆可单独使用，也可与其他多孔保温材料配合使用，如作为外墙外保温的配套材料，尤其是用于夏热冬冷和夏热冬暖地区，构成高反射和低传热结构，达到既隔热又保温的效果。该涂料可刷涂和喷涂施工。 光",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 900,
+        "chunk": "# 十、乳胶漆的涂装  \n\n从生产的角度来说，乳胶漆是成品。但从使用的角度来看，乳胶漆只是半成品，而通过涂装、干燥成膜，并附着在基面上的涂膜才是成品。优质的乳胶漆，只有通过专业的基层处理和涂装，在合适的干燥成膜条件下，才能形成牢牢地附着在基面上的涂膜。这种涂膜才能起到长久的保护、理想的装饰以及其他的作用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 901,
+        "chunk": "# 1.涂装设计  \n\n有涂装设计和没有涂装设计，往往涂装结果会有很大区别。所谓涂装设计，就是根据用户要求，针对建筑物和周围环境等特点，选用合适的乳胶漆，采用不同的色彩、质感、光泽、线条和分格等，进行合理的基层处理，采用合适的施工步骤，达到对建筑物的持久保护、理想装饰和其他一些特殊作用。  \n\n(1）装饰效果乳胶漆的装饰效果主要是通过颜色、质感、光泽和线条来体现的。线条是纯属设计范围。  \n\n一般来说，乳胶漆的色彩是相当丰富的。但在一般色彩的基础上，又加上金属色或切片，颜色就更丰富多彩了，可选范围很大。  \n\n通过不同材料的搭配使用，如纤维壁布和丝光乳胶漆、厚质饰纹涂料和普通乳胶漆，能得到不同质感和花纹的涂装效果。  \n\n采用不同的涂料、不同的工具或施工方法，能涂饰出各种各样的造型，如仿面砖、拉毛、地中海风情和橘皮状等。建筑涂料，绝不仅仅只有平涂。  \n\n乳胶漆的光泽，除亚光、丝光和有光外，也可引进金属光泽。  \n\n对于涂装面积较大的墙面，可作墙面装饰性分格设计。  \n\n窗边和层间等还可设计线条。  \n\n(2）涂层配套性涂装设计包括选择底涂层（含腻子）、面涂层等整体配套体系。从性能优化、实用性、经济性、环保安全等方面设计出满足客户需求的最佳方案。  \n\n(3）防污染一般来说，外墙涂装最易因污染而失去装饰效果。因此，外墙面绝对不能作为流水的渠道，这对涂装设计来说是十分重要的。外窗盘粉刷层两端应粉刷出挡水坡端，檐口、窗盘底部必须按技术标准完成滴水线构造措施。对女儿墙和阳台的压顶，其粉刷面应有指向内侧的泛水坡度。分格线做成半圆柱面形，而不是燕尾形，以防横向分格线积灰，下雨时产生流挂。坡屋面建筑物的檐口，应超出墙面，以防雨水污染墙面。  \n\n对出墙的管道和在外墙面上的设备，如空调室外机组和滴水管，应作合理的建筑处理，以防安装底座的锈迹和滴水污染外墙。  \n\n屋顶最好有檐口，这样有利于降低外墙饰面污染。有檐口的外墙涂装工程，往往是比较干净和清洁的。",
+        "category": " Introduction"
+    },
+    {
+        "id": 902,
+        "chunk": "# 2.基层  \n\n基层是涂装工作的基础，其质量好坏直接关系到整个涂装的结果。因此，对基层提出要求，进行处理，并经验收合格后，才能开始涂装。  \n\n（1）基层材料基层材料通常是水泥抹灰砂浆、混合抹灰砂浆、混凝土、石膏板、装饰砂浆、黏土砖和旧涂层等。  \n\n绝大部分基层材料中关键的组分是水泥。如，水泥抹灰砂浆一般是水泥：砂子 $\\O=$ $1:(2\\sim3)$ ，混合抹灰砂浆一般是水泥：石灰：砂子 $=1:1:4$ 。水泥的主要矿物组成是硅酸三钙 $(\\mathbf{C}_{3}$ S—3CaO·SiO）、硅酸二钙 $(\\mathrm{C}_{2}\\mathrm{S}-2\\mathrm{CaO}\\cdot\\mathrm{SiO}_{2})$ 、铝酸三钙 $(\\mathbf{C}_{3}$ A-3CaO·$\\mathbf{Al}_{2}\\mathbf{O}_{3}$ ）和铁铝酸四钙 $(\\mathrm{C_{4}A F}\\mathrm{-4CaO\\cdotAl_{2}O_{3}\\cdot F e_{2}O_{3}})$ ）等。这些组分加水时，会发生水化反应，形成水化硅酸钙、水化铝酸钙、水化铁铝酸钙和氢氧化钙等，从而使砂浆硬化并产生强度。其化学反应式大致如下。  \n\n4CaO ·AlO • FezO+2Ca(OH)+10HO—→(3CaO·AlO · 6HO-3CaO · Fe O · 6HO)固溶体  \n\n由于生成氢氧化钙，初始 $\\mathsf{p H}$ 值高达12以上，碱度很高。基层如养护期不够，或处理不当，泛碱等涂膜缺陷就可能由此而发生。  \n\n(2）基层要求通常认为，基层应符合下列要求。  \n\n$\\textcircled{1}$ 基层应牢固即不开裂、不掉粉、不起砂、不空鼓、无剥离、无石灰爆裂点和无附着力不良的旧涂层等。因为基层是涂膜附着的基础，如果基层不牢固，涂膜就无法扎下牢固的根，从而不会有好的附着力。基层是否牢固，可以通过敲打和刻划检查。  \n\n$\\textcircled{2}$ 基层应平整即表面平整，立面垂直，阴阳角垂直、方正和无缺棱掉角，分格缝深浅一致且横平竖直。它们的允许偏差应符合表3-1-52的要求。对于外墙面，表面应做到平而不光，因为平整的基面是涂膜装饰作用的前提。但压得太光，既影响涂膜的附着力，又使水泥净浆被压至表面，比较容易开裂。对于内墙面，应抹平收光，因为内墙面温变范围较小，一般不会开裂。  \n\n单位：mm  \n\n表3-1-52抹灰质量的允许偏差  \n\n\n<html><body><table><tr><td>平整内容</td><td>普通抹灰</td><td>中级抹灰</td><td>高级抹灰</td></tr><tr><td>表面平整</td><td>≤5</td><td>≤</td><td>≤2</td></tr><tr><td>阴阳角垂直</td><td>一</td><td>≤4</td><td>≤2</td></tr><tr><td>阴阳角方正</td><td>一</td><td>≤4</td><td>≤2</td></tr><tr><td>立面垂直</td><td>一</td><td>≤5</td><td>≤3</td></tr><tr><td>分格继深浅一致和横平竖直</td><td>一</td><td>≤3</td><td>≤1</td></tr></table></body></html>  \n\n基层表面是否平整，可用 $2\\mathrm{m}$ 直尺和楔形尺检查。阴阳角是否垂直，可用 $2\\mathbf{m}$ 托线板和尺检查。阴阳角是否方正，可用 $\\scriptstyle200{\\mathrm{mm}}$ 方尺检查。立面是否垂直，可用质量检查尺检查。分格缝深浅是否一致和横平竖直，可用拉线和量尺检查。  \n\n$\\textcircled{3}$ 基层应清洁即表面无灰尘、无浮浆、无油迹、无锈斑、无霉点、无盐类析出物和无青苔等杂物。基层是否清洁，可目测检查。  \n\n当基层有脱模剂等油污时，可用 $5\\%\\sim10,$ %的氢氧化钠水溶液洗刷，然后用清水冲洗干净。  \n\n$\\textcircled{4}$ 基层应干燥即涂刷溶剂型涂料时，基层含水率应不大于 $8\\%$ ；而乳胶漆涂膜的透气性比较好，所以一般认为基层含水率可以放宽至不大于 $10\\%$ 。其实对基层的干燥要求也不是绝对的，如防水涂料施工对基层的要求是可以潮湿而没有明水。根据经验，抹灰基层养护$_{14\\sim21}$ 天，混凝土基层养护 $_{21\\sim28}$ 天，一般能满足涂装要求。含水率太高时，涂膜可能会起泡，尤其是像弹性乳胶漆和有光乳胶漆的涂膜，因其透气性较低。含水率可用砂浆表面水分测定仪测定，也可用塑料薄膜覆盖法粗略判断。  \n\n$\\textcircled{5}\\mathtt{p H}$ 值从涂装的角度看，一般认为基层的 $\\mathsf{p H}$ 应不大于10。pH太高，涂膜容易出现泛碱等缺陷。但从砂浆和混凝土对钢筋的保护角度来说， $\\mathsf{p H}$ 不能低于9.5。否则，砂浆和混凝土会碳化，碳化后中性的砂浆和混凝土会失去对钢筋的保护。可以看出，涂料涂装和钢筋保护对基层pH要求是矛盾的，只能折中处理，甚至偏向于砂浆和混凝土对钢筋的保护。因此，基层的 $\\mathsf{p H}$ 不大于10是仅指表层而言的，而且还可以稍高些。酸碱度可用pH试纸或 $\\mathbf{pH}$ 试笔通过湿棉测定。 Y  \n\n$\\textcircled{6}$ 体积稳定性对于外墙，基层还要耐水，而且体积应稳定。否则，一下雨，基层松软，甚至体积膨胀。雨停后，基层干燥，体积收缩，涂膜就会成片脱落。  \n\n涂装前，应对基层进行验收。合格后，再进行涂装施工。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 903,
+        "chunk": "# 3.乳胶漆的选择  \n\n由于乳胶漆涂膜性能能满足建筑物和构筑物的保护及装饰等要求，同时又以水为分散介质，比较安全卫生，所以不管在欧美还是在我国，也不管是内墙还是外墙，乳胶漆都已成为最主要的建筑装饰材料。  \n\n目前国内市场上供应和使用较广泛的乳胶漆有：内墙乳胶漆、外墙乳胶漆、弹性建筑乳胶漆、合成树脂乳液砂壁状建筑涂料、复层建筑涂料等。在选择乳胶漆时，既要注意产品的性能要求，又要关注安全、健康和环保的要求。  \n\n(1）内墙乳胶漆选择内墙乳胶漆选择原则是好的装饰性和环保性，适宜的保护作用，合理的耐久性和经济性。  \n\n$\\Phi$ 装饰性装饰性包括颜色、质感、光泽、擦净性和对比率等内容。内墙乳胶漆涂膜不像外墙乳胶漆涂膜那样，需经受日晒雨淋，霜雪冰冻，对颜色的耐光性、耐候性要求比较低，颜色可选范围大。大多数内墙乳胶漆是薄层内墙涂料，质感不明显，也可与玻璃纤维墙纸配合使用，花纹、质感跃于墙面。对于光泽，大多数人喜欢亚光，也有喜欢丝光、半光和金属光泽的。丝光和半光内墙乳胶漆耐洗刷性特别好，其缺点是对基面的不平整度反应十分敏感，基面稍有一点不平，就会看得很清楚。对于擦净性，国家标准中虽没有规定，但对内墙的装饰性是绝对需要的，因为难免会弄脏。这里姑且用耐洗刷性代之，可选择耐洗刷性比较好的涂料。对比率是反映涂料消除底材颜色的能力。一般说来，高比低好。  \n\n$\\textcircled{2}$ 环保性环保性对于内墙乳胶漆来说，是十分重要的。根据目前的认识，内墙乳胶漆的环保性包括挥发性有机物、重金属、甲醛含量、气味等指标。国家标准GB18582—2008《室内装饰装修材料内墙涂料中有害物质限量》和国家环境保护总局标准HJ/T201--2005《环境标志产品技术要求水性涂料》是判别内墙乳胶漆环保性能好坏的主要依据。目前，只有符合国家标准GB18582—2008《室内装饰装修材料内墙涂料中有害物质限量》的内墙乳胶漆，才允许进人市场销售。也就是说，国家标准GB18582—2008是一个准入标准。在准入的产品中，只有提出申请，并按国家环境保护总局标准HJ/T201—2005《环境标志产品技术要求水性涂料》的要求，所用原料、生产过程、“三废”排放等经检查合格，产品抽检也合格的，才能获得中国环境标志产品认证证书。HJ/T201—2005是环境标志标准，要求高于GB18582—2008准入标准。在我国，只有符合国家环境保护总局标准HJ/T201—2005的涂料，才能称环保涂料、绿色涂料。  \n\n我国的经济正在与国际接轨，我国的市场也是国际市场的一部分。据报道，在全世界涂料界，RAL-UZ—2000德国蓝天使环境标志是环保方面要求较高的品种之一。它远远高于我国环境保护总局HJ/T201—2005 标准。达到德国蓝天使环境标志的产品会更安全、更卫生。  \n\n内墙乳胶漆的气味问题也是用户、施工者和生产企业关注的问题。用户和施工者当然要求低气味或无气味的乳胶漆。科研单位和生产企业也在努力开发、生产低气味或无气味的乳胶漆。这也是环境友好型乳胶漆所要求的。当然，含有香味的乳胶漆也是用户和施工者青睐的。  \n\n$\\textcircled{3}$ 保护作用可由耐洗刷性和耐碱性等来体现，但目前耐碱性测试结果不能反映实际结果。在我国，判别内墙乳胶漆性能好坏的依据是国家标准GB/T9756—2009《合成树脂乳液内墙涂料》。该标准对内墙乳胶漆提出了八项性能指标要求，并根据对比率（逮盖力）和耐洗刷性高低将其分为三等：合格品、一等品和优等品。用户在购买内墙乳胶漆时，要求高的可选优等品，要求一般的可选一等品，要求低的可选合格品。  \n\n$\\textcircled{4}$ 名牌或有品牌的产品尽量选用名牌或有品牌的产品，这些产品的生产企业规模较大，产量较高，管理较严格，有较好的质量保证体系，产品质量一般有保障。  \n\n③标识齐全选用包装标识齐全的产品。在包装桶上应有商标、生产厂家名称、地址和电话以及生产日期、重量（或容量)、执行标准、质保期、合格证等较为重要的标识。  \n\n$\\textcircled{6}$ 正轨购货渠道购货数量大时，应实地考察，货比三家，直接从厂家购货，或从厂家的代理商购货比较可靠。用量少时，最好在建材商城或专卖店购买，这些商店较注重进货渠道和商品信誉，产品质量较有保证。千万不要贪图便宜，购买“三无”产品。  \n\n(2）外墙乳胶漆选择这里所说的外墙乳胶漆是指薄质外墙乳胶漆、弹性建筑乳胶漆、合成树脂乳液砂壁状建筑涂料和合成树脂乳液复层建筑涂料。  \n\n薄质外墙乳胶漆主要品种有苯丙乳胶漆、纯丙乳胶漆、硅丙乳胶漆和氟碳乳胶漆等。其性能指标应符合GB/T9755—2001《合成树脂乳液外墙涂料》的要求。该标准对外墙乳胶漆提出了十二项性能指标要求，并根据对比率（遮盖力）、耐洗刷性、耐沾污性和耐人工老化的不同将其分为三等：合格品、一等品和优等品。  \n\n弹性建筑乳胶漆的主要技术指标应符合JG/T172—2005《弹性建筑涂料》的规定。开发弹性建筑乳胶漆的目的是为了遮盖墙面的裂缝，因此，弹性是其最主要的技术指标。不仅常温有弹性，而且低温也应有弹性。  \n\n合成树脂乳液砂壁状建筑涂料的主要技术指标应符合JG/T24—2000《合成树脂乳液砂壁状建筑涂料》的规定。  \n\n合成树脂乳液复层建筑涂料的主要技术指标应符合GB/T9779—2005《复层建筑涂料》的规定。  \n\n外墙乳胶漆选择的原则是好的保护作用和装饰效果，适宜的施工条件，合理的耐久性和经济性，兼顾环保要求。  \n\n$\\Phi$ 保护作用保护作用对外墙乳胶漆来说是十分重要的。它包括耐紫外线、耐候、耐碱、拒水、透气等性能指标。丙烯酸乳胶漆、硅丙乳胶漆、氟碳乳胶漆，保护作用是比较突出的。当然，当基层开裂时，这些涂膜也随着开裂。弹性乳胶漆具有遮盖裂缝的功能。  \n\n$\\textcircled{2}$ 装饰效果装饰效果由耐沾污性、颜色、质感和光泽等来体现。就耐沾污性而言，乳液聚合物玻璃化温度高的外墙乳胶漆、硅丙乳胶漆、氟碳乳胶漆耐沾污性较好，弹性乳胶漆和合成树脂乳液砂壁状涂料沾污性差些。  \n\n颜色对装饰效果来说是很重要。要尽量选择保色性好的颜料，如无机颜料，虽然颜色鲜艳性差些，但耐光、耐候性好。也就是说，不易褪色。  \n\n合成树脂乳液砂壁状建筑涂料和复层涂料属厚质涂料，一般来说，对基面的平整度要求不高，且质感强些。这些建筑涂料在建筑物上能形成具有仿石或仿砖等质感。  \n\n光泽：外墙乳胶漆除了亚光外，还可有丝光、半光、有光和金属光泽。绝大多数用的是亚光外墙乳胶漆。  \n\n$\\textcircled{3}$ 施工条件乳胶漆施工时，环境温度和基层温度必须高于乳胶漆的最低成膜温度。否则，乳胶漆干燥后仍不能成膜。不同乳胶漆的最低成膜温度是不同的，一般乳胶漆的最低成膜温度在 $5\\Upsilon$ 左右，但有些乳胶漆的最低成膜温度在 $10\\Upsilon$ 左右。当在冬季、初春或深秋施工时，应根据施工时的气温，选择最低成膜温度合适的乳胶漆。一般来说，施工时的气温比乳胶漆的最低成膜温度高些较有利于成膜。  \n\n$\\textcircled{4}$ 环保性乳胶漆以水为分散介质，无毒无害，使用安全。同等条件下，可优先选用符合国家环境保护总局标准HJ/T201—2005《环境标志产品技术要求水性涂料》的产品，或符合更高环保要求的产品。  \n\n$\\textcircled{5}$ 涂层体系涂层体系包括腻子、底涂、中涂和面涂，要配套选用。相同的涂料，采用不同的底涂，所得结果是不同的。采用封闭底涂是解决泛碱的措施之一。与其说选择涂料，不如说选择涂层系统更合适，可根据生产厂家的建议选用。  \n\n$\\textcircled{6}$ 性价比要根据所要求的涂膜性能和经济效益的关系来选用涂料。对于外墙涂料，采用性价比较好的涂料，也就是说，采用性价比合理的涂料是有利的，由于其涂膜使用期的延长，最终还是合算的。当选用质量较差的外墙涂料，虽然眼前价格比较便宜，但可能引起涂膜的早期损坏，达不到应有的保护作用和装饰效果。搭脚手架、返修、甚至重涂，将给用户造成更大的费用。  \n\n$\\textcircled{7}$ 标识齐全所选用的涂料应有产品名称、执行标准、种类、颜色、生产日期、保质期、生产企业地址、使用说明和产品合格证等，并具有生产企业的质量保证书。  \n\n总之，外墙乳胶漆的选用恰当与否，直接影响涂装效果，作为涂装设计人员应像大夫熟悉药品和病人一样，熟悉乳胶漆性能，熟悉被涂对象，综合分析，平衡各种因素，才能正确、合理地选用好涂料。  \n\n(3）外墙外保温饰面的涂料选择因为外墙外保温基面与普通外墙面是不同的，所以外墙外保温饰面的涂料选择与普通外墙涂料选择也不一样。根据JG149—2003《膨胀聚苯板薄抹灰外墙外保温系统》规定，作为外墙外保温饰面的建筑涂料，必须与薄抹灰外保温系统相容，其性能指标应符合外墙建筑涂料的相关标准。除上述外墙乳胶漆选择要求外，外墙外保温饰面用涂料选择还有其他一些需关注的。  \n\n$\\Phi$ 组分之间的匹配性溶剂型涂料不能用于外墙外保温体系。因为外墙外保温体系一般采用聚苯乙烯（EPS、XPS）或聚氨酯（PU）等为保温层，根据相似相溶原则，溶剂能溶解聚苯乙烯和聚氨酯。即使是水性涂料中常用的 $200^{\\sharp}$ 溶剂油，其中芳香烃也能溶解聚苯乙烯保温层，因此，其含量也需根据实际使用情况予以控制。  \n\n另外，玻纤外的涂塑也可能被溶剂溶解，使其耐碱性受影响，从而使防护层降低或失去抗裂和耐冲击等性能。  \n\n$\\textcircled{2}$ 涂料的拒水透气性JG149—2003《膨胀聚苯板薄抹灰外墙外保温系统》规定，外 保温系统的 $\\mathsf{5m m}$ 厚防护层，浸水24h，吸水量要 $\\leqslant500\\mathbf{g}/\\mathrm{m}^{2}$ ；外保温系统防护层和饰面涂 层一起水蒸气湿流密度要≥0. $85\\mathbf{g}/(\\mathbf{m}^{2}\\cdot\\mathbf{h})$ @  \n\n对于外墙面，就吸水性来说，一般外层要求比内层低，也就是说外饰涂层要低于防护层，即涂层吸水量要少于 $500\\mathrm{g}/\\mathrm{m}^{2}$ ，这样才能使比较少的水进入墙体。就水蒸气湿流密度来说，一般外层要求比内层高，也就是说外饰涂层要高于防护层，即涂层水蒸气湿流密度要远远大于 $0.85\\mathbf{g}/(\\mathbf{m}^{2}\\cdot\\mathbf{h})$ ，这样水蒸气才能畅通无阻地排出。  \n\n欧洲标准EN1062-1：2002《色漆和清漆抹灰层和混凝土基面上的外用涂料和涂料系统分类—1.分类》，根据涂料的透水汽性、吸水性等将外用涂料和涂料系统分类分级，以便于用户选用。吸水性按EN1062-3：1998《色漆和清漆抹灰层和混凝土基面上的外用涂料和涂料系统分类—3.吸水性的测定和分类》测定。透水汽性按ENISO7783-2：1999《色漆和清漆抹灰层和混凝土基面上的外用涂料和涂料系统分类-——-2.透水汽性的测定和分类》测定。  \n\n尽管JG149—2003和EN1062-3对吸水量的测试方法略有差别，主要是基层不同，将它们粗略做一比较，24h吸水量 $500\\mathrm{g/m^{2}}$ 相当于吸水性 $\\mathbf{W}=0.1\\mathbf{kg}/(\\mathbf{m}^{2}\\cdot\\mathbf{\\lambda}\\mathbf{h}^{0.5})$ ，是欧洲标准EN1062-1中最低一档吸水量。也就是说，是最严格的要求。Kuenzel理论仅要求 $W\\leqslant$ $),5\\mathbf{kg}/(\\mathbf{m}^{2}\\cdot\\mathbf{h}^{0.5})$ 9  \n\n对于吸水量来说，弹性涂料、有光涂料、水性金属漆和荷花王涂料，一般均能满足要求。而相当一部分的涂料达不到该要求。有些涂料要与某些底涂配合使用，才能达到要求。  \n\nJG149—2003标准中的水蒸气湿流密度是按GB/T17146—1997《建筑材料水蒸气透过性能试验方法》中的水法测定，是通过水的相对湿度100%与实验室相对湿度差产生水蒸气流。而ENISO7783-2的测试方法与GB/T17146—1997不同。它是由 $23\\Upsilon$ 磷酸二氢铵相对湿度 $93\\%$ 与实验室相对湿度 $50\\%$ 差产生水蒸气流。严格地说，不同测试方法所得结果不能比较。大致说，水蒸气湿流密度 $0.85\\mathbf{g}/(\\mathbf{m}^{2}\\mathbf{\\Sigma}^{}\\cdot\\mathbf{h})$ 相当于 $V=20,4\\beta/(\\mathrm{m}^{2}\\cdot\\mathrm{d})$ ，即相当于$\\mathbf{S}_{\\mathrm{d}}=1$ .2m静止空气层阻力，属于欧洲标准EN1062-1中的中等透水汽性。Kuenzel理论要求 $\\scriptstyle s_{\\mathrm{d}}\\leqslant2\\bmod$  \n\n涂层水蒸气湿流密度太低，轻者造成表面色差，重者导致发霉和热工性能变差，甚至不同程度的破坏。对于水蒸气湿流密度来说，弹性涂料可能达不到要求。硅树脂涂料等能符合水蒸气湿流密度的要求。  \n\n另外，水蒸气湿流密度大小不仅与涂料有关，还与涂膜的厚度成反比。  \n\n对于外墙外保温体系，吸水量（拒水性）和水蒸气湿流密度（透气性）是要同时满足的，所以要综合平衡。从拒水透气的角度看，JG149—2003标准对外墙外保温饰面用涂料的要求比普通外墙涂料高得多，有些符合产品标准要求的外墙涂料却达不到此要求。有些可以通过与底涂等搭配的涂层系统予以解决。  \n\n$\\textcircled{3}$ 涂料的耐久性JGJ144--2004《外墙外保温工程技术规程》规定，外墙外保温工程的使用年限不应少于25年。外墙涂料使用年限不仅与外墙涂料的质量有关，而且与基层、施工、使用环境条件和维护保养等因素有关，一般为 $5\\mathord{\\sim}15$ 年，使用年限达30年的也有报道。因此应尽量选用耐久性好的外墙涂料，尤其是使用彩色涂料时，优先选择保色性好的无机色浆，另外，还要做好及时维护翻新。  \n\n$\\textcircled{4}$ 涂料的颜色涂料的颜色主要牵涉太阳能的吸收和反射问题。当太阳辐射能人射到不透明的涂层表面时，一部分能量被吸收，另一部分能量被反射，而透过的能量可忽略不计。  \n\n对于外墙外保温饰面来说，夏天希望更多地反射太阳能，而冬天希望更多地吸收太阳能。热传递有三种：传导、对流和辐射。太阳辐射热是影响建筑热过程的主要热源。而辐射与温度的四次方成正比。夏天温度高，辐射热大，日照时间长，另外保温层密度低，隔热性差，涂层颜色影响大。冬天温度低，辐射热少，日照时间短，保温层热导率低，涂层颜色影响小。因此，外墙外保温饰面涂料颜色的选择应以夏天隔热为主。也就是说，不能选择太深的颜色，如最低明度值应大于 $20\\%$ 要  \n\n(4）底涂和腻子底涂和腻子对于涂装质量是重要的。建筑涂装中配套使用的腻子和底涂必须与所选用饰面乳胶漆性能相适应，内墙腻子的技术指标要符合JG/T3049—1998《建筑室内用腻子》的规定，外墙面如平整的话，可不使用腻子，如使用时，其性能要符合JG157—2004《建筑外墙用腻子》行业标准的规定。外墙腻子不能用106、803等胶水配制，因为其主要组分是聚乙烯醇和聚乙烯醇缩甲醛。它们是水溶性的，不耐水，遇水膨胀，甚至被水冲掉，从而造成涂膜起壳脱落。  \n\n对于涂装工程中所用的底涂，要符合JG/T210—2007《建筑内外墙用底漆》。阳离子乳液底涂和硅树脂乳液底涂封碱性能较好。同时必须使用与基层、腻子和面涂材料相匹配的底涂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 904,
+        "chunk": "# 4.施工  \n\n乳胶漆的施工和验收可参见JGJ/T29—2003《建筑涂饰工程施工及验收规程》、GB50210—2001《建筑装饰装修工程质量验收规范》或DG/TJ08-504—2000《上海市工程建设规范外墙涂料工程应用技术规程》等进行。  \n\n涂装施工可分为施工准备和施工两个阶段。  \n\n（1）施工准备首先，施工单位应根据建筑工程情况、设计选定式样、涂饰要求、涂料种类、基层条件、施工平台及涂装工具设备等编制涂饰工程施工方案。  \n\n涂饰作业平台应符合JGJ80《建筑施工高处作业安全技术规范》的规定。施工面与施工平台间的距离，要考虑涂料的种类和涂装式样，便于操作。  \n\n施工单位应根据选定的品种和要求，实际涂装面积和材料单耗以及损耗，确定备料量。  \n\n根据设计选定的颜色，以色卡或颜色样板订货。  \n\n乳胶漆应存放在指定的专用库房内，应按品种、批号、颜色分别堆放。贮存温度应在0℃以上，40℃以下，并避免日晒。  \n\n大面积施工前应由施工人员按工序要求先做好样板或样板间，并保存到峻工。  \n\n涂装机具对涂装质量和装饰效果有很大影响，因此施工前应准备好合适的涂装机具对空气压缩机、毛辊、漆刷等，应按涂装材料种类、式样、涂装部位等选择适用的型号。  \n\n(2）施工涂装一般应按底涂层、中间涂层、面涂层的要求进行施工。后一遍涂料的施工，必须在前一遍涂料表面干燥后进行。每一遍涂料都应涂均匀，各层之间必须结合牢固。对有特殊要求的工程可增加面涂层次数。  \n\n在施工过程中，涂料的兑水应严格按说明书进行，根据施工方法、施工季节、涂装要求、温度、湿度、基层等情况控制，兑水后应搅拌均匀，不得随意多加水。  \n\n对于外墙涂料的涂装，同一墙面同一颜色应用同一批号的涂料。当颜色相同而批号不同时，应预先混匀，以保证同一面墙不产生色差。  \n\n常采用的涂装方法如下。  \n\n$\\Phi$ 刷涂一般使用排笔进行涂刷。横、纵向交叉施工。如施工常用的“横三竖四手法”。通常刷两道，刷涂时，第一道涂料刷完后，待干燥后（至少2h)，再刷第二道涂料。由于乳胶漆干燥较快，尤其是夏天，每个刷涂面应尽量一次完成，否则易产生接痕。  \n\n$\\textcircled{2}$ 辊涂可用羊毛辊。这是较大面积施工中常用的施工方法。毛辊辊涂时，不可蘸料过多，最好配有蘸料槽，以免产生流淌。在辊涂过程中，要向上用力、向下时轻轻回带，否则也易造成流滴病。辊涂时，为避免辊子痕迹，搭接宽度为毛辊长度的1/4。一般辊涂两遍，其间隔应2h以上。  \n\n$\\textcircled{3}$ 喷涂首先将门窗及不喷涂部位进行遮挡，调整好喷枪的喷嘴，应控制涂料黏度，将压力控制在所需要压力。喷涂时手握喷斗要平稳，走速均匀，喷嘴距墙面距离$30\\sim50\\mathrm{cm}$ ，不宜过近或过远。喷枪有规律地移动，横、纵向呈S形喷涂墙面。要注意接茬部位颜色一致、厚薄均匀，且要防止漏喷、流淌。一般两道成活，其间隔时间应在2h以上。  \n\n采用传统的辊简和毛刷进行涂装时，每次蘸料后在匀料板上来回滚一遍，或在桶边舔料，涂装时涂膜不能过厚或过薄。 Y  \n\n大面积涂饰时，当干燥较快时，应多人配合操作，流水作业，沿同一方向涂装，以避免接痕。  \n\n外墙涂装应自上而下，施工分段应以墙面分格线、阴阳角或落水管为分界线。  \n\n下面以弹性涂料施工为例加以说明。表3-1-53～表3-1-55分别是弹性内墙涂料、平涂弹性外墙涂料、厚浆型弹性涂料的施工工序。  \n\n表3-1-53弹性内墙涂料的施工工序  \n\n\n<html><body><table><tr><td>次序</td><td>工序名称</td><td>次序</td><td>工序名称</td></tr><tr><td>1</td><td>清理基层</td><td>8</td><td>涂底涂</td></tr><tr><td>2</td><td>填补缝隙、局部刮腻子</td><td>9</td><td>复补腻子</td></tr><tr><td>3</td><td>磨平</td><td>10</td><td>磨平</td></tr><tr><td>4</td><td>第一遍满刮腻子</td><td>11</td><td>局部涂底涂</td></tr><tr><td>5</td><td>磨平</td><td>12</td><td>第一遍面层涂料</td></tr><tr><td>6</td><td>第二遍满刮腻子</td><td>13</td><td>第二遍面层涂料</td></tr><tr><td>7</td><td>磨平</td><td></td><td></td></tr></table></body></html>\n\n注：1.对于石膏板内墙、顶棚表面，应进行板缝处理。2.步骤9～11是否需要，视具体情况而定。  \n\n表3-1-54平涂弹性外墙涂料的施工工序  \n\n\n<html><body><table><tr><td>次序</td><td>工序名称</td><td>次序</td><td>工序名称</td></tr><tr><td>1</td><td>清理基层</td><td>4</td><td>涂底涂</td></tr><tr><td>2</td><td>填补缝隙，满批腻子或局部刮腻子</td><td>5</td><td>第一遍面层涂料</td></tr><tr><td>3</td><td>磨平</td><td>6</td><td>第二遍面层涂料</td></tr></table></body></html>\n\n注：施工时，要保证弹性乳胶漆涂膜厚度，因为遮盖裂缝的能力与涂膜厚度成正比。  \n\n表3-1-55厚浆型弹性涂料的施工工序  \n\n\n<html><body><table><tr><td>次序</td><td>工序名称</td><td>次序</td><td>工序名称</td></tr><tr><td>1</td><td>清理基层</td><td>5</td><td>涂饰中间层涂料（一道或两道）</td></tr><tr><td>2</td><td>填补缝隙、局部刮腻子</td><td>6</td><td>拉毛</td></tr><tr><td>3</td><td>磨平</td><td>7</td><td>面层涂料</td></tr><tr><td>4</td><td>涂底涂</td><td></td><td></td></tr></table></body></html>\n\n注：1.涂中间层涂料时，应根据不同花纹要求，控制涂料的黏度，用长毛辊简或海绵机理筒将涂料均匀地涂在基层上。2.然后立即用海绵机理辑简来回滚动，理出大小均匀、方向一致的拉毛涂层。3.面层涂料根据需要而定。  \n\n旧墙面翻新施涂乳胶漆时，视不同基层情况进行不同处理。如旧涂层墙面，应清除粉化的和疏松起壳的旧涂层，并将墙面清洗干净，再作修补。待干燥后，按选定的乳胶漆施工工序施工。  \n\n涂装完毕后，施工工具应及时用水清洗干净或浸泡在水中。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 905,
+        "chunk": "# 5.涂装中易出现的问题和解决方法  \n\n乳胶漆涂装中，由于种种原因，有时会出现一些问题。对于那些较易出现的问题，应分析产生原因及提出解决方法。  \n\n（1）露底露底是涂膜未能达到完全遮盖底材颜色的缺陷。就总体而论，其成因可能如下。  \n\n$\\Phi$ 乳胶漆的遮盖力不够，如钛白粉的用量太少，着色颜料遮盖力差，尤其如黄色有机颜料等。  \n\n$\\textcircled{2}$ 涂膜厚度不足，如兑水太多。  \n\n$\\textcircled{3}$ 涂膜厚度不均匀。  \n\n$\\textcircled{4}$ 基面压得太光而吸水性太低，或底涂增水性太强，所以用量上不去。其实也是涂膜厚度不足。  \n\n$\\textcircled{5}$ 局部地方漏涂。  \n\n$\\textcircled{6}$ PVC太高的乳胶漆，干膜遮盖力是可以的，有的下雨淋湿后，微孔中的空气被水取代时，也可能出现露底现象。  \n\n针对上述问题，可采取如下解决方法。  \n\n①提高乳胶漆的遮盖力，如提高钛白粉的用量。对于着色颜料遮盖力差的乳胶漆，可先涂刷一道白色乳胶漆，然后再涂彩色乳胶漆，也能避免露底。  \n\n②施涂适当厚度的涂膜。如兑水太多的，不仅使乳胶漆固含量降低，而且黏度也降低，两者都导致涂膜厚度减小。因此，应严格按要求兑水。  \n\n$\\textcircled{3}$ 首先分析造成涂膜厚度不均匀的原因，然后加以解决。如是施工问题，则改进施工，如是乳胶漆的流平性问题，则改进乳胶漆的流平性。  \n\n$\\textcircled{4}$ 基面当然要做平，但不要压得太光。底涂憎水性要适中。  \n\n$\\textcircled{5}$ 顺次涂刷，避免漏涂。  \n\n$\\textcircled{6}$ 适当降低乳胶漆的PVC。  \n\n(2）流挂乳胶漆施涂到垂直墙面后，受到重力的作用而向下流动，称为流挂。流挂 $\\mathbf{\\chi}_{t}$ 时间后湿膜的体积为：  \n\n$$\nV_{t}=\\frac{x^{3}\\rho g t}{3\\eta}\n$$  \n\n式中， $\\rho$ 为乳胶漆的密度； $g$ 为重力加速度； $_x$ 为湿膜厚度； $\\eta$ 为乳胶漆接近零剪切速率的黏度。  \n\n由式（3-1-23）可以看出，造成流挂的原因如下。  \n\n$\\boldsymbol{\\Phi}$ 乳胶漆接近零剪切速率的黏度过低或兑水太多。  \n\n$\\textcircled{2}$ 施涂厚度过厚，流挂体积与湿膜厚度的立方成正比。  \n\n$\\textcircled{3}$ 在乳胶漆中，可能有较多高密度的颜料和填料，导致乳胶漆的密度较高。  \n\n$\\textcircled{4}$ 基层压得太光，吸水性太低或底涂的憎水性太强。  \n\n$\\textcircled{5}$ 施工环境的湿度过大，温度过低，或基层太湿。  \n\n就以上分析的原因，解决方法可以如下。  \n\n$\\textcircled{1}$ 控制流挂的首要任务是调整黏度，使乳胶漆在低剪切速率下具有较高的黏度。同时，在施工时，严格按说明书要求兑水。  \n\n$\\textcircled{2}$ 辊筒蘸料后，最好通过均料板使其均匀，以控制好湿膜厚度。  \n\n$\\textcircled{3}$ 设计乳胶漆配方时，高密度颜料和填料使用要适当。  \n\n$\\textcircled{4}$ 基面应做到平而不光。底涂憎水性要适中。对于僧水性强的底涂，可缩短中涂和底涂之间的涂剧间隔。  \n\n$\\textcircled{5}$ 基层太湿不能施工，要晾干。施工环境相对湿度应小于 $85\\%$ (3）接痕接痕是指涂膜在涂装搭接处出现颜色和/或光泽等的差异。可能的原因如下。  \n\n$\\Phi$ 乳胶漆的开放时间较短。  \n\n$\\textcircled{2}$ 涂装时的温度太高，相对湿度较低，干燥速率太快。  \n\n$\\textcircled{3}$ 基层吸水太大。  \n\n$\\textcircled{4}$ 涂装时未能保持“湿边”状态。  \n\n解决方法是延长乳胶漆的开放时间，尽量不要在烈日直射下施工。基层吸水太大时，用底涂对基层进行处理。  \n\n此外，涂装时，向前涂完一块待涂区域后，再反向涂装刚涂过涂料的区域，以保持湿边，这样施工有利于克服接痕。  \n\n(4）开裂开裂是指乳胶漆涂刷后干燥过程中出现的裂纹。产生裂纹的可能原因如下。  \n\n$\\Phi$ 乳胶漆的抗干燥收缩裂缝性能较低。  \n\n$\\textcircled{2}$ 湿膜厚度过厚，或中涂未干就涂面涂时。  \n\n$\\textcircled{3}$ 在弹涂压花基面上施涂时。  \n\n④环境和/或基层的温度低于乳胶漆的最低成膜温度。如相当多乳胶漆的最低成膜温度高于 $5\\mathrm{{c}}$ ，所以在 $5\\mathrm{v}$ 或以下施工时，涂膜在干燥过程中开裂，不能形成连续膜。  \n\n$\\textcircled{5}$ 环境温度太高，风较大，干燥太快。  \n\n针对上述问题，通常可采取如下解决方法。  \n\n$\\textcircled{1}$ 提高乳胶漆的抗干燥收缩裂缝性能，如在配方中提高较粗填料用量，增加乳液用量，加延长开放时间的助剂等。  \n\n$\\textcircled{2}$ 一次不要涂刷太厚。掌握好面涂与中涂之间的时间间隔。  \n\n$\\textcircled{3}$ 在弹涂压花基面上施涂时，对乳胶漆的抗裂性要求特别高。要专门设计抗裂性好的乳胶漆。  \n\n$\\textcircled{4}$ 环境和/或基层的温度一定要高于乳胶漆的最低成膜温度，这是乳胶漆成膜的两个条件之一。  \n$\\textcircled{5}$ 避免在高温烈日直射下施工。  \n\n(5）兑水后乳胶漆发臭乳胶漆在施工时，往往要兑水。但兑水后乳胶漆应尽快用掉，否则容易发臭。因为乳胶漆是以水为分散介质，水是生命之源，同样也是细菌生长和繁殖之源。生产企业在生产乳胶漆时，为了防止乳胶漆在贮存期变质，加入了防腐剂。施工时兑水后，一是将防腐剂的浓度稀释了，有时不足以抑制细菌繁殖；二是可能又带人部分细菌，所以乳胶漆就容易发臭，尤其是在炎热的夏天。  \n\n(6）兑水过多为了降低单位面积的乳胶漆用量，有时有的施工单位往往兑水太多。兑水太多会带来一系列的问题。  \n\n$\\Phi$ 导致乳胶漆的黏度大幅度下降，施工时容易产生流挂。  \n\n$\\textcircled{2}$ 导致乳胶漆的固含量下降，施工时涂膜厚度变薄。  \n\n$\\textcircled{3}$ 导致乳胶漆的表面张力提高，对基层和颜料、填料的湿润、渗透能力降低，从而影响涂膜的附着力和对颜料填料的黏结力，因此易粉化。  \n\n(7）针孔和爆孔乳胶漆涂刷施工时，或在干燥成膜过程中，部分气泡在高黏度的湿膜表面破裂，而邻近的乳胶漆黏度太高已不能流平，从而留下针孔和爆孔，严重影响涂膜外观和性能。如高黏度的弹性乳胶漆常会出现此类问题。  \n\n解决问题的方法：一是做好乳胶漆的消泡工作，从源头控制针孔和爆孔发生；二是选用合理的辊筒，避免在施工过程中带人气泡。  \n\n(8）内墙乳胶漆泛黄在内装修时，相当多的施工人员按如下次序进行施工：先用乳胶漆涂刷墙面，接着用聚氨酯涂料漆地板、踢脚线、墙裙和门等。这种施工工序对保持清洁是有利的。但有的聚氨酯涂料含有较多的游离甲苯二异氰酸酯（TDI)，在涂刷和干燥过程中，这些游离TDI挥发，不仅对环境造成污染，对人体造成毒害，而且会导致乳胶漆涂膜泛黄。  \n\n为了避免此问题的发生，施工工序应倒过来。先用聚氨酯涂料漆地板、踢脚线、墙裙和门等，待其干燥后，再用乳胶漆涂刷墙面。  \n\n(9）鼓泡乳胶漆涂刷施工后，有的会出现鼓泡的缺陷。其原因是基层内有水分。温度和湿度要平衡，即水汽要排出。当涂膜透气性又比较差时，阻碍水汽排出，于是就产生应力。新涂涂膜的附着力还比较低，当产生的应力大于这时涂膜的附着力时，就出现鼓泡。大致有如下一些情况会出现鼓泡。  \n\n$\\Phi$ 基层有水或基层太潮湿，而乳胶漆涂膜透气性又比较差，如弹性乳胶漆和有光乳胶漆。  \n\n$\\textcircled{2}$ 基层温度太高，而湿膜厚度比较厚、涂膜透气性又比较差。  \n\n$\\textcircled{3}$ 涂刷后没多久，就下雨，雨过天晴，而乳胶漆涂膜透气性又比较差。  \n\n$\\textcircled{4}$ 涂料本身消泡性能不好。  \n\n解决的方法如下。  \n\n$\\Phi$ 使基层进一步干燥。  \n\n$\\textcircled{2}$ 涂刷底涂，湿膜厚度不要太厚。  \n\n③通过原料选择、配方调整、涂刷底涂、增加基面的粗糙度等来提高涂膜的附着力。  \n\n$\\textcircled{4}$ 提高消泡剂用量或更换消泡剂。  \n\n（10）色差色差是涂膜出现颜色不一致的缺陷。  \n\n出现色差的原因，如采用同色不同批的涂料、不同部位之间涂装间隔过长、基层材质不同等。  \n为了达到理想的装饰效果，必须避免色差。一般可采取如下措施。  \n\n$\\Phi$ 一幢建筑同一墙面，应采用同一批号的乳胶漆。对于大型的高层建筑，争取在尽可能快的时间内涂装完毕。  \n\n$\\textcircled{2}$ 工程所用涂料应按品种、批号、颜色分别堆放。当同一品种同--颜色，批号不同时，应一并倒入大型容器中搅拌均匀，确保一幢建筑同一墙面所用涂料不产生色差的条件下才能使用。  \n\n$\\textcircled{3}$ 当同一墙面有贯穿到两边的不同颜色涂料涂刷的分格线时，至少在同一分格区内采用同一批号乳胶漆。  \n\n$\\textcircled{4}$ 当采用多层的涂层结构时，至少同一墙面整个面涂层使用同一批号涂料。  \n\n$\\textcircled{5}$ 尽量采用双排脚脚手架或吊篮施工，以彻底避免脚手架孔洞修补造成色差。  \n\n$\\textcircled{6}$ 如确需对脚手架孔洞等进行修补时，基层所用的材料要和原来材料相同，基层平整度等也与周围一致，并在尽可能短的时间内，应采用与原来相同批号的涂料修补。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 906,
+        "chunk": "# 6.验收  \n\n涂装工程应待涂膜养护期满后进行质量验收，步骤如下。  \n\n(1）查资料  \n\n$\\Phi$ 涂装工程的施工图、设计说明及其他设计文件。  \n\n$\\textcircled{2}$ 涂装工程所用材料的产品合格证书、性能检测报告及进场验收记录。  \n\n$\\textcircled{3}$ 基层检验记录。  \n\n$\\textcircled{4}$ 施工自检记录及施工过程记录。  \n\n(2）看工程涂装工程的检验按批进行。室外涂装工程每一栋楼的同类涂料涂装墙面每$1000\\mathrm{{m}^{2}}$ 划分为一个检验批，不足 $1000\\mathrm{m}^{2}$ 作为一个检验批。室内涂装工程每50间同类涂料涂装的墙面划分为一个检验批，不足50间作为一个检验批。  \n\n涂装工程每个检验批的检查数量为：室外每 $100\\mathrm{m}^{2}$ 检查一处，每处 $10\\mathrm{m}^{2}$ ；室内按有代表性的自然间，而大面积房间和走廊按10延长米为一间，抽查 $10\\%$ ，但不少于5间。  \n\n下面也以弹性涂料为例说明。弹性内墙涂料和弹性外墙涂料的涂装工程质量，分别要符合表3-1-56和表3-1-57的规定。  \n\n表3-1-56弹性内墙涂料涂装工程的质量要求  \n\n\n<html><body><table><tr><td>项次</td><td>项 目</td><td>普通级涂饰工程</td><td>中级涂饰工程</td><td>高级涂饰工程</td></tr><tr><td>1</td><td>掉粉、起皮</td><td>不允许</td><td>不允许</td><td>不允许</td></tr><tr><td>2</td><td>漏刷、透底</td><td>不允许</td><td>不允许</td><td>不允许</td></tr><tr><td>3</td><td>泛碱、咬色</td><td>不允许</td><td>不允许</td><td>不允许</td></tr><tr><td>4</td><td>流坠、疙瘩</td><td>允许少量</td><td>允许少量</td><td>不允许</td></tr><tr><td>5</td><td>光泽和质感</td><td>光泽较均匀</td><td>手感较细腻，光泽较均匀</td><td>手感细腻，光泽均匀</td></tr><tr><td>6</td><td>颜色、刷纹</td><td>颜色一致</td><td>颜色一致</td><td>颜色一致，无刷纹</td></tr><tr><td>7</td><td>分色线平直（拉5m线检查，不偏差不大于3mm 足5m拉通线检查）</td><td></td><td>偏差不大于2mm</td><td>偏差不大于1mm</td></tr><tr><td></td><td>门窗、灯具等</td><td>洁净</td><td>洁净</td><td>洁净</td></tr></table></body></html>  \n\n表3-1-57弹性外墙涂料的涂装工程质量要求  \n\n\n<html><body><table><tr><td>项次</td><td>项 目</td><td>普通级涂饰工程</td><td>中级涂饰工程</td><td>高级涂饰工程</td></tr><tr><td>1</td><td>反锈、掉粉、起皮</td><td>不允许</td><td>不允许</td><td>不允许</td></tr><tr><td>2</td><td>漏剧、透底</td><td>不允许</td><td>不允许</td><td>不允许</td></tr><tr><td>3</td><td>泛碱、咬色</td><td>不允许</td><td>不允许</td><td>不允许</td></tr><tr><td>4</td><td>涂膜厚度</td><td>符合要求</td><td>符合要求</td><td>均匀，符合要求</td></tr><tr><td>5</td><td>颜色、刷纹</td><td>颜色一致</td><td>颜色一致</td><td>颜色一致，无刷纹</td></tr><tr><td>6</td><td>造型</td><td>可以</td><td>较一致</td><td>均匀一致</td></tr><tr><td>7</td><td>开裂</td><td>不允许</td><td>不允许</td><td>不允许</td></tr><tr><td>8</td><td>针孔、砂眼</td><td>一</td><td>允许少量</td><td>不允许</td></tr><tr><td>9</td><td>分色线平直（拉5m线检查、不足5m拉通线检查）</td><td>偏差不大于5mm偏差不大于3mm偏差不大于1mm</td><td></td><td></td></tr><tr><td>10</td><td>五金、玻璃等</td><td>洁净</td><td>洁净</td><td>洁净</td></tr></table></body></html>\n\n注：开裂是指涂料本身开裂，不包括基层开裂所引起的涂料开裂。由以上可以看出，这种验收只是资料、涂膜外观、颜色、光泽等的验收。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 907,
+        "chunk": "# 7.维护和翻新  \n\n通过验收后的涂装，往往是一次性使用到损坏。其实这种使用是不经济的，应视具体情况定期维护，以保持较好的保护和装饰等效果，延长使用寿命，这样能降低使用成本。  \n\n$\\Phi$ 对于仅被污染而影响装饰效果的涂装，可采用自来水清洗除去污染。  \n\n$\\textcircled{2}$ 若泛水、滴水线和屋檐等损坏时，应马上修复，以免造成涂膜污染。  \n\n$\\textcircled{3}$ 如罩光涂层粉化或面涂层粉化、褪色时，可仅重涂罩光层或面涂层。  \n\n$\\textcircled{4}$ 当涂层出现明显粉化、褪色或较严重污染，甚至有极少量剥落等缺陷时，要进行清洗和局部修补后，重涂翻新。  \n\n总之，要在不需要铲除旧涂层的情况下，及时进行这种维修翻新，这才是最方便和最经济的。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 908,
+        "chunk": "# 第二节溶剂型建筑涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 909,
+        "chunk": "# 一、定义、种类与性能特征",
+        "category": " Introduction"
+    },
+    {
+        "id": 910,
+        "chunk": "# 1.定义与性能特征  \n\n（1）定义以溶剂型树脂为成膜物质，以有机溶剂为分散介质制备的建筑涂料称为溶剂型建筑涂料。  \n\n(2）性能特征溶剂型建筑涂料的基本特征是流平性好，施工的温度范围宽，涂膜装饰效果好，物理力学性能优异，例如涂膜致密，耐水、耐腐蚀和耐老化性能好等。此外，在建筑涂料中，溶剂型涂料还有以下特征。  \n\n$\\Phi$ 溶剂型建筑涂料集中了各种高性能的建筑涂料，这类涂料的耐久性、耐沾污性均好，耐水、耐酸雨和耐大气中其他化学物质的腐蚀性好。例如氟树脂涂料、聚氨酯丙烯酸酯复合涂料、有机硅丙烯酸酯复合涂料和丙烯酸酯涂料等，均比相应水性涂料的物理性能优异。  \n\n②溶剂型建筑涂料的物理性能优于同类水性类建筑涂料的性能。涂料实现了水性化后，虽然从环保性能上来说，具有极大优势，并已经成为不可逆转的发展趋势，但就目前的技术水平来说，由于水性化使-些易溶于水的表面活性剂、增稠剂和保护胶体等留在涂料中，使得涂料的某些性能降低，这也是某些必须要求高性能涂料的应用场合（例如汽车涂料）目前尚难以完全实现水性化或者水性化程度很低的原因。  \n\n③溶剂型建筑涂料具有水性涂料所无法比拟的施工性能。溶剂型涂料可以通过调整树脂分子量的高低而在一定程度上调整涂料的黏度，使涂料获得较好的流平性，而水性涂料很难做到这一点，水性涂料只有通过使用增稠剂才能使涂料达到满意的黏度要求，这往往同时带来涂料流平性的不良。  \n\n此外，控制涂料中溶剂的挥发速率，是获得优质涂膜的重要途径，溶剂型涂料很容易做到这一点，只要调整混合溶剂的比例即可，而这对于水性涂料则是不可能的。正因为如此，溶剂型涂料可以通过使用稀释剂或调整溶剂比例的方法来满足涂料在不同气候（例如低温甚至负温，高温、高湿度等）条件下的要求。但水性涂料则不能在负温或低温下施工，高湿度下施工也会给涂料性能带来一定影响。  \n\n$\\textcircled{4}$ 溶剂型涂料具有更稳定的涂料性能。由于溶剂型树脂本身是稳定的，所以溶剂型涂料在低温、高温下都很稳定，而水性涂料由于水在零摄氏度要结冰，其低温稳定性较差，由于水性树脂的性能原因，在常温下涂料的贮存稳定性也不如溶剂型涂料。  \n\n$\\textcircled{5}$ 由于涂料组成中大量溶剂的使用，溶剂型涂料的主要问题是环保、成本、生产、贮运和使用过程中的安全问题（易燃、易爆和毒性等）。",
+        "category": " Introduction"
+    },
+    {
+        "id": 911,
+        "chunk": "# 2.溶剂型建筑涂料的种类  \n\n根据不同的分类方法可以得到不同种类的溶剂型建筑涂料。除了常用的根据涂料成膜物质种类进行的分类方法以外，还可以根据涂膜的装饰特征、涂料在涂层结构中的部位和涂料固化机理等进行分类，见表3-1-58。  \n\n表3-1-58溶剂型建筑涂料的种类  \n\n\n<html><body><table><tr><td>分类方法</td><td>涂料种类</td><td>组成及性能特征</td></tr><tr><td rowspan=\"4\">按照成膜物质 的种类进行分类</td><td>氟树脂外墙涂料</td><td>这类涂料也称氟碳涂料，选用能够常温干燥成膜的有机氟树脂，主要使用聚偏 二氟乙烯树脂（PVDF）共聚物和氟乙烯烷基乙烯基醚共聚物（FEVE）两种，可拼 用其他树脂如丙烯酸树脂、聚氨酯等。涂料具有极为优异的耐久性、耐腐蚀性和 光泽保留性，涂膜硬度高，被称为超耐久性涂料</td></tr><tr><td>聚氨酯丙烯酸酯 复合建筑涂料</td><td>这类涂料通常为双组分NCO/OH型涂料。由含异氰酸酯的甲组分与含羟基 树脂色浆的乙组分组成 外用涂料的甲组分使用脂肪族异氰酸酶，常用HDI缩二脲，也可用HDI三聚 体或IPDI三聚体，涂膜硬度和耐候、保光性优于缩二脲。乙组分含羟基树脂与 颜料制成涂料组分，树脂常用含羟基丙烯酸树脂，因此具有优良的保光、保色性 内用型涂料的甲组分可使用脂肪族异氰酸酯如HDI缩二脲，或与芳香族异氰 酸酯如TDI加成物混合使用。乙组分使用E-12，E-20型环氧树脂，加入部分聚 酯可提高柔韧性，加入氨基树脂、醋丁纤维素可以改近流平性能</td></tr><tr><td>有机硅丙烯酸酯 复合外墙涂料</td><td>采用有机硅-丙烯酸酯复合树脂为基料，涂料为单组分。这类涂料结合了有机硅 涂料耐沾污性好，耐高温和耐老化等以及丙烯酸酯涂料附着力强、对颜料和基层的 铺展性好以及耐水、耐光等特点，因而涂料具有很好的耐久性、耐腐蚀性和光泽保留 性等。涂料性能仅次于氟树脂涂料，但成本要低得多，因而具有很好的性价比</td></tr><tr><td>丙烯酸酯外 墙涂料</td><td>主要成膜物质为热塑性丙烯酸酯树脂，其中，丙烯酸酯及甲基丙烯酸酯共聚 树脂（纯丙树脂）耐光、耐老化性能优于苯乙烯-丙烯酸酯共聚树脂（苯丙树脂）和 乙酸乙的酸与（乙近，证明用部分乙三 料，但成本也相对低，是性能优异的通用型外墙涂料</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>分类方法</td><td>涂料种类</td><td>组成及性能特征</td></tr><tr><td rowspan=\"2\">按照涂膜的装 饰特征进行分类</td><td>普通平面涂料</td><td>氟树脂类、聚氨酯丙烯酸酶类、有机硅丙烯酸酯复合类和丙烯酸酯类涂料都可 以配制成普通平面涂料，这也是最常用的涂膜装饰种类，有平光(无光)、半光（蛋 壳光）和有光型平面涂料，这类饰面涂料保持各类涂料的性能，同时施工简单、施 工方法灵活（例如刷涂、滚涂和喷涂等）</td></tr><tr><td>金属质感外墙涂料</td><td>颜料以金属颜料（例如铝颜料）为主，使涂膜有金属质感和光泽。以氟树脂为 成膜物质配制金属质感外墙涂料，采用特殊工艺涂装面得到的仿金属铝板涂膜 （也称仿幕墙涂装）</td></tr><tr><td rowspan=\"3\">按照涂料在涂 层结构中的部位 进行分类</td><td>面涂料</td><td>也称罩面涂料，涂料组成中不含或仅含有少量颤料，具有光泽度较高（但也有 根据装饰效果要求而加入消光剂而制成无光涂料的）和很好的涂膜性能，通常为 了提高涂料性能和降低涂层综合成本而将面涂料和中层涂料分开制备。有些罩 面龄料需要保持涂膜透明,不能含有颜料，例如用于复层涂料、砂壁状涂料等罩</td></tr><tr><td>中层涂料</td><td>建筑涂料的中层涂料是为了降低涂层成本与面涂分开制备。中层涂料的 PVC往往较高，基料用量少，涂料成本低，涂膜的光泽和综合性能比面涂料的差</td></tr><tr><td>封闭底漆</td><td>通常不含或仅含少量颜料、填料，具有很高的渗透性能和耐碱性、层间黏结力 及易施工性等，能够对基层起到加固、封闭、稳定、黏结和过渡等作用，并对防止 涂膜泛碱产生重要作用</td></tr><tr><td rowspan=\"2\">按照涂料的固 化机理进行分类</td><td>溶剂挥发固化型</td><td>经涂装成膜后，涂料中的溶剂挥发面从涂膜中散逸出去，涂料中的树脂分子和 颜料颗粒在此过程中发生位移，互相黏结在一起而成膜。该类涂料包装与施工 简便，但涂膜耐溶剂性相对较差</td></tr><tr><td>反庭固化型</td><td>建筑涂料中反应固化型涂料通常只有聚氨酯类和氟树脂类涂料，其固化机理 都是通过涂料中的—NCO基和固化剂中的一OH基的反应组成大分子物质而 固化成膜，由于在反应过程中没有小分子生成，因而涂膜具有很好的综合性能， 特别是耐溶剂性突出</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 912,
+        "chunk": "# 二、丙烯酸酯类和丙烯酸酯-聚酯类外墙涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 913,
+        "chunk": "# 1.配方  \n\n(1）配方举例表3-1-59中列出丙烯酸类和丙烯酸酯-聚酯类外墙建筑涂料的配方。  \n\n表3-1-59丙烯酸酯类外墙涂料配方举例  \n\n\n<html><body><table><tr><td rowspan=\"2\">材料名称</td><td rowspan=\"2\">涂料组分或功能</td><td colspan=\"2\">用量（质量分数）/%</td></tr><tr><td>丙烯酸树脂类</td><td>丙烯酸酯-聚酯类</td></tr><tr><td>热塑性丙烯酸树脂溶液 丙烯酸酯-聚酯树脂溶液</td><td>成膜物质 成膜物质</td><td>48.5</td><td>一 45.0</td></tr><tr><td>邻苯二甲酸二丁酯</td><td>增塑剂</td><td>一 1.0</td><td>0.8</td></tr><tr><td>金红石型钛白粉</td><td></td><td>22.0</td><td>15.0</td></tr><tr><td></td><td>颜料</td><td></td><td></td></tr><tr><td>滑石粉</td><td>填料</td><td>5.0</td><td>6.0</td></tr><tr><td>硫酸钡</td><td>填料</td><td>3.0</td><td>5.0</td></tr><tr><td>有机黏土流变增稠剂</td><td>流变增稠剂</td><td>1. 0</td><td></td></tr><tr><td>5%硅油二甲苯溶液</td><td>消泡剂</td><td><1.0</td><td><1. 0</td></tr><tr><td>润湿分散剂</td><td>润湿分散</td><td>适量</td><td>适量</td></tr><tr><td>乙酸丁酯</td><td>溶剂</td><td>5.9</td><td>6.0</td></tr><tr><td>乙醇</td><td>溶剂</td><td>3.0</td><td></td></tr><tr><td>丁醇</td><td>溶剂</td><td>5.9</td><td>3.0</td></tr><tr><td>甲苯</td><td>溶剂</td><td>5.0</td><td>8.0</td></tr><tr><td>二甲苯</td><td>溶剂</td><td>一</td><td>10.0</td></tr><tr><td>合计</td><td>一</td><td>100</td><td>100</td></tr></table></body></html>  \n\n(2)配方分析表3-1-59所列两种涂料的配方都是使用的混合溶剂，适当地调整不同溶剂的用量能够调整涂料的干燥时间并在一定程度上控制流动性；两种涂料都使用约占树脂量2%的增塑剂，这个用量很高，也可以通过选择玻璃化温度低的树脂而减少用量，但高温回黏问题会变得突出；由于溶剂型涂料中表面活性剂用量少，消泡问题并不突出，因而使用有机硅油作为消泡剂即可；使用有机黏土作为流变增稠剂，增稠和防沉淀效果都好，但对涂料流平不利；在涂料的流平性不能满足要求时，可改用商品流变增稠剂。  \n\n溶剂型丙烯酸酯类建筑涂料近年来得到很多研究，在应用技术方面取得一些进展，下面介绍一些改性研究。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 914,
+        "chunk": "# 2.使用含氟丙烯酸酯改性丙烯酸酯涂料  \n\n含氟丙烯酸酯单体具有优良的均聚性和与其他单体的共聚性。含氟丙烯酸酯聚合物比通常的氟树脂的溶解性好，透明性高。由于含氟丙烯酸酯类聚合物的长氟烷基侧链所赋予聚合物的低表面能，这类聚合物可以用于配制抗沾污性涂料、流平剂和抗粘连剂等。  \n\n使用含氟丙烯酸酯单体、甲基丙烯酸酯类单体、丙烯酸酯类单体等，在引发剂存在的条件下进行引发聚合，能够得到具有较强憎水性能的含氟丙烯酸酯改性的丙烯酸酯树脂。  \n\n使用含氟丙烯酸酯改性丙烯酸酯的原理如下。  \n\nCH—CRCOOR’ + CHCRCOORf + CH—C(CH)COO(CH)Si(OCH)  \n\n(KH570)  \n\n![](images/abc7500a6d8bb836a25363b1abb07cc9539c0b79f86b5bfad2672307f91d6ab7.jpg)  \n\nKH570是 $\\gamma-$ （甲基丙烯酰氧）丙基三甲氧基硅烷的商品名称。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 915,
+        "chunk": "# 3.使用有机硅改性丙烯酸酯涂料  \n\n有机硅单体和丙烯酸单体通过自由基引发聚合能够形成有机硅改性的丙烯酸酯树脂。在有机硅-丙烯酸酯树脂中，有机硅主要改善涂膜硬度、降低涂膜的表面能和提高涂膜的耐沾污性。有机硅-丙烯酸酯树脂中有机硅的含量对这些性能中某些性能的影响见表3-1-60。  \n\n表3-1-60聚丙烯酸酯与有机硅的比例对共聚物性能的影响  \n\n\n<html><body><table><tr><td>有机硅/聚丙烯酸酯</td><td>共聚物的T/℃</td><td>涂膜摆杆硬度</td><td>涂膜外观状态</td><td>附着力（划格法）</td></tr><tr><td>30/70</td><td>35</td><td>0.32</td><td>良好，很柔软</td><td>75</td></tr><tr><td>40/60</td><td>43</td><td>0.46</td><td>良好，柔软</td><td>82</td></tr><tr><td>50/50</td><td>52</td><td>0.54</td><td>良好，柔软</td><td>85</td></tr><tr><td>60/40</td><td>62</td><td>0.66</td><td>良好，较硬，合适</td><td>100</td></tr><tr><td>70/30</td><td>68</td><td>0.71</td><td>良好，较硬，合适</td><td>100</td></tr><tr><td>80/20</td><td>73</td><td>0.74</td><td>良好，较脆，易开裂</td><td>100</td></tr></table></body></html>\n\n①丙烯酸酯混合单体配比（质量比）为：丙烯酸丁酯：甲基丙烯酸甲酯丙烯酸 $\\scriptstyle=$ 30702$\\textcircled{2}$ 质量比、",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 916,
+        "chunk": "# 4.使用苯乙烯改性丙烯酸酯涂料  \n\n将苯乙烯引入丙烯酸酯共聚物中，可以提高涂膜的耐水性、硬度、抗沾污性和抗粉化性以及降低成本等。在这几种功能中，尤以降低成本的目的最直接，最为常用。丙烯酸酯中引  \n\n入苯乙烯所产生的不利作用是，与苯环相连的叔碳原子容易被氧化生成发色基团，使涂膜在紫外线下更易于泛黄和保色性变差。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 917,
+        "chunk": "# 三、有机硅建筑涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 918,
+        "chunk": "# 1.有机硅建筑涂料的耐候性和耐沾污性  \n\n(1）耐候性有机硅建筑涂料也称有机硅-丙烯酸酯复合建筑涂料，简称硅丙涂料。有机硅树脂的耐热性好，涂膜硬度高、耐沾污性好。在氟树脂涂料、聚氨酯丙烯酸酯复合涂料和有机硅丙烯酸酯复合涂料三种高性能外墙涂料中，以有机硅丙烯酸酯涂料的成本最低，其性能仅次于价格昂贵的氟树脂涂料，如图3-1-17所示。  \n\n一般认为，溶剂型有机硅-丙烯酸酯类外墙涂料的使用寿命在10年以上，能够达到15年，甚至达到20年（如日本的“泽姆拉库”涂料）。德国的硅丙涂料已在美国白宫应用，显示非常优异的耐久性能。  \n\n（2）耐沾污性有机硅外墙涂料的耐沾污性非常好，仅次于氟树脂涂料，表3-1-61中展示出几种溶剂型外墙涂料的耐沾污性，从中可以看出有机硅-丙烯酸酯复合外墙涂料的耐沾污性最好。  \n\n![](images/19bc2fb7bd0b79592fc56de0d8925e200c255a0ddab348d30736d19658fb67e0.jpg)  \n图3-1-17氟树脂、聚氨酯-丙烯酸酯和有机硅-丙烯酸酯等涂料耐候性的比较1-氟树脂涂料；2一有机硅丙烯酸酯树脂涂料；3—聚氨酯丙烯酸酯树脂涂料；4一丙烯酸酯树脂涂料  \n\n表3-1-61几种溶剂型外墙涂料的耐沾污性  \n\n\n<html><body><table><tr><td>涂料品种</td><td>耐沾污性（5次循环 白度下降率）/%</td><td>涂料品种</td><td>耐沾污性（5次循环 白度下降率）/%</td></tr><tr><td>氯化橡胶涂料</td><td>22.1~27. 2</td><td>聚氨酯-丙烯酸酯复合外墙涂料</td><td>3~5</td></tr><tr><td>丙烯酸酯外墙涂料（A）</td><td>7.7~7.9</td><td>有机硅-丙烯酸酯复合外墙涂料</td><td>3</td></tr><tr><td>丙烯酸酶外墙涂料（B)</td><td>9.6~9.8</td><td></td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 919,
+        "chunk": "# 2.有机硅外墙涂料配方举例  \n\n有机硅外墙建筑涂料配方举例见表3-1-62。  \n\n表3-1-62有机硅涂料配方举例  \n\n\n<html><body><table><tr><td>原材料</td><td>用量（质量分数）/%</td><td>原材料</td><td>用量（质量分数)/%</td></tr><tr><td>有机硅-丙烯酸酯复合树脂</td><td>48.0</td><td>润湿分散剂</td><td>适量</td></tr><tr><td>邻苯二甲酸二丁酯</td><td>1.0</td><td>有机黏土流变剂</td><td>1.0</td></tr><tr><td>金红石型钛白粉</td><td>17.0</td><td>乙酸丁酯</td><td>6.0</td></tr><tr><td>滑石粉</td><td>6.0</td><td>二甲苯</td><td>11. 0</td></tr><tr><td>硫酸钡</td><td>7.0</td><td>丁醇</td><td>3.0</td></tr><tr><td>5%硅油二甲苯溶液</td><td><1. 0</td><td></td><td></td></tr><tr><td>合计</td><td>100.0</td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 920,
+        "chunk": "# 3.有机硅-丙烯酸酯树脂用量对涂料性能的影响  \n\n表3-1-63中列出关于有机硅-丙烯酸酯树脂用量对涂膜的光泽和耐紫外线影响的试验结果。从表中的结果可以大致地确定外墙用亚光涂料的树脂用量为 $30\\%\\sim40\\%$ 或 $40\\%\\sim50\\%$ 有光涂料的树脂用量为 $50\\%\\sim60\\%$ ；高光泽涂料的树脂用量为 $60\\%\\sim70\\%$ ，可用于复层涂料的罩光。当然，树脂的用量还与涂料中颜料、填料的使用有关。  \n\n表3-1-63有机硅-丙烯酸酯树脂用量对涂料性能的影响  \n\n\n<html><body><table><tr><td rowspan=\"2\">涂料性能</td><td colspan=\"5\">有机硅-丙烯酸酯树脂用量/%</td></tr><tr><td>20~30</td><td>30~40</td><td>40~50</td><td>50~60</td><td>60~70</td></tr><tr><td>光泽/%</td><td>35~40</td><td>50~55</td><td>65~70</td><td>75~80</td><td>85~90</td></tr><tr><td>紫外线照射（500W，250h）</td><td>颜色变深</td><td>无变色、无脱粉</td><td>无变色、无脱粉</td><td>无变色、无脱粉</td><td>无变色、无脱粉</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 921,
+        "chunk": "# 4.有机硅树脂在建筑涂料中的应用方式  \n\n建筑涂料中使用有机硅树脂目前主要是用于对丙烯酸酯树脂建筑涂料的改性，有三种形式可以实现这一目的。第一种方法是将可共混用的有机硅树脂预聚体直接与丙烯酸酯树脂拼混使用进行改性。这是最简单的方法，但改性效果较差。第二种方法是用有机硅树脂的中间体例如正硅酸乙酯（或由其合成的聚硅氧烷）和羟基丙烯酸酯聚合，合成出有机硅-丙烯酸酯复合树脂。这种方法从合成树脂人手改性，所得到的产品贮存稳定，能够有效地将两种树脂的优点，即丙烯酸酯树脂的黏结性、底材湿润性、经济性和有机硅树脂的耐水性、耐热性和耐沾污性结合于一体。第三种方法是根据涂料自分层原理，用有机硅和丙烯酸酯两种树脂制成自分层涂料，其涂膜具有很低的表面能和优异的耐沾污性能。这种方法的优点在于其一次涂装即可形成满足实际使用所希望具有的两层涂膜，且两层涂膜之间具有良好的附着力，克服了由于涂膜层间附着力不良造成的缺陷以及经济性能好等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 922,
+        "chunk": "# 四、聚氨酯类外墙涂料和氟树脂建筑涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 923,
+        "chunk": "# 1.聚氨酯类外墙涂料配方  \n\n表3-1-64中列出内、外用聚氨酯类涂料的配方。  \n\n表3-1-64内、外用聚氨酯涂料的配方  \n\n\n<html><body><table><tr><td rowspan=\"2\">原材料名称</td><td rowspan=\"2\">涂料组分或功能</td><td colspan=\"2\">用量（质量分数）/%</td></tr><tr><td>外用聚氨酯涂料</td><td>内用聚氨酯仿瓷涂料</td></tr><tr><td>羟基树脂色浆组分（乙组分） 羟基丙烯酸酯树脂溶液 E-20环氧树脂</td><td>成膜物质</td><td>64.0</td><td>一</td></tr><tr><td>E-12环氧树脂 聚酯树脂（7110J)</td><td>成膜物质 成膜物质 增塑</td><td>一 一 一</td><td>4.2 9.6 5.7</td></tr><tr><td>氨基树脂（590-3)</td><td>流平 流变增稠</td><td>一</td><td>1.8 0.3</td></tr><tr><td>醋酸丁酸纤维索 金红石型钛白粉</td><td>颜料</td><td>一 17.5</td><td>30.0</td></tr><tr><td>201甲基硅油 润湿分散剂</td><td>消泡</td><td>适量</td><td>5.7 适量</td></tr><tr><td>醋酸丁酯</td><td>润湿分散 溶剂</td><td>适量 4.0</td><td></td></tr><tr><td>环已酮</td><td>溶剂</td><td>4.0</td><td>7.2</td></tr><tr><td>二甲苯 小计</td><td>溶剂</td><td>10. 0</td><td>11.7</td></tr><tr><td>固化剂组分（甲组分）</td><td></td><td>100</td><td>70.0</td></tr><tr><td>HDI缩二脲（75%)</td><td>成膜、固化</td><td>15~20</td><td>9.9</td></tr><tr><td>聚氨酯预聚体</td><td>成膜、固化</td><td>一</td><td>20.1</td></tr><tr><td>小 混合比例（甲乙）</td><td></td><td>（15~20)100</td><td>30.0 37</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 924,
+        "chunk": "# 2.氟树脂建筑涂料  \n\n(1）单组分氟树脂建筑涂料文献中介绍的单组分氟树脂建筑涂料基本配方见表3-1-65。  \n\n表3-1-65单组分氟树脂外墙涂料参考配方  \n\n\n<html><body><table><tr><td>原材料名称</td><td>商品型号</td><td>用量（质量分数）/%</td></tr><tr><td>F-300氟树脂</td><td>固体含量46%</td><td>64.0</td></tr><tr><td>金红石型钛白粉</td><td>2310</td><td>21.0</td></tr><tr><td>云母粉</td><td>800目</td><td>2.0</td></tr><tr><td>润湿分散剂</td><td></td><td>1.0</td></tr><tr><td>消光剂</td><td>ED-30</td><td>2.4</td></tr><tr><td>流平剂</td><td></td><td>0.3</td></tr><tr><td>稀释剂</td><td></td><td>9.3</td></tr></table></body></html>\n\n(2）日本的FEVE氟树脂涂料日本的FEVE氟树脂涂料的典型配方组成见表3-1-66。  \n\n表3-1-66日本的FEVE氟树脂涂料的典型组成  \n\n\n<html><body><table><tr><td rowspan=\"2\">材料组分</td><td colspan=\"3\">用量（质量分数）/%</td></tr><tr><td>配方1</td><td>配方2</td><td>配方3</td></tr><tr><td>Lumiflon清漆（LF100氟树脂）</td><td>100</td><td>100</td><td>100</td></tr><tr><td>溶剂</td><td></td><td></td><td></td></tr><tr><td>二甲苯</td><td>25</td><td>25</td><td>25</td></tr><tr><td>正丁醇</td><td>一</td><td>75</td><td>二</td></tr><tr><td>甲基异丁基甲酮</td><td>75</td><td></td><td>75</td></tr><tr><td>催化剂</td><td></td><td></td><td></td></tr><tr><td>对甲苯磺酸</td><td>一</td><td>0.1</td><td>一</td></tr><tr><td>二丁基二月桂酸锡</td><td>0. 00035</td><td></td><td>0.00035</td></tr><tr><td>颜料（TiOz）</td><td>21</td><td>21</td><td>21</td></tr><tr><td>固化剂</td><td></td><td></td><td></td></tr><tr><td>封闭型异氰酸酯</td><td>16.8</td><td>一</td><td>一</td></tr><tr><td>氨基树脂</td><td>一</td><td>3</td><td>一</td></tr><tr><td>异氰酸酯</td><td>一</td><td>一</td><td>9.3</td></tr></table></body></html>  \n\n(3）氟树脂建筑涂料氟树脂涂料的许多性能直接取决于氟树脂的性能，而由于氟原子的极性低，表面性质光滑，具有不粘性和平滑性，因而保持氟树脂中一定的氟含量，能够使氟树脂涂料具有突出的抗污染特性和自洁性；由于氟原子的特殊物性和氟原子三维排列的螺旋结构，氟树脂的耐热性、耐化学腐蚀性、抗光化学降解性等也很突出。但是，过高的氟含量对于涂料的附着力、光泽、溶解性和颜料相容性等性能会产生不利影响。表3-1-67中是使用国产溶剂型氟树脂，制备不同氟含量的白色、银色等涂料，在标准条件下用石棉水泥板制成涂膜样板，从耐久性等方面进行测试所得到的结果。  \n\n表3-1-67不同氟含量的涂料及其涂膜性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">氟含量/%</td><td rowspan=\"2\">涂膜颜色</td><td rowspan=\"2\">老化试验 后的保光率/%</td><td rowspan=\"2\">E</td><td colspan=\"2\">耐化学腐蚀性（常温7天）</td><td rowspan=\"2\">耐溶剂性（MEK擦拭）</td></tr><tr><td>5%HSO</td><td>5%NaOH</td></tr><tr><td>23</td><td>白色</td><td>64</td><td>1.1</td><td>无异常</td><td>无异常</td><td>光泽轻微降低</td></tr><tr><td>23</td><td>白色</td><td>55</td><td>1.4</td><td>无异常</td><td>无异常</td><td>涂膜溶解，光泽降低</td></tr><tr><td>23</td><td>白色</td><td>63</td><td>1,1</td><td>无异营</td><td>无异常</td><td>光泽轻微降低</td></tr><tr><td>19</td><td>白色</td><td>69</td><td>1.0</td><td>无异常</td><td>有变化</td><td>光泽降低</td></tr><tr><td>27</td><td>银色</td><td>74</td><td>0.5</td><td>无异常</td><td>有变化</td><td>光泽降低</td></tr><tr><td>23</td><td>银色</td><td>57</td><td>7.0</td><td>无异常</td><td>无异常</td><td>无异常</td></tr><tr><td>22</td><td>银色</td><td>37</td><td>4.4</td><td>无异常</td><td>无异常</td><td>只有擦拭痕迹</td></tr><tr><td>19</td><td>钣色</td><td>32</td><td>4.0</td><td>无异</td><td>有变化</td><td>光泽降低</td></tr><tr><td>19</td><td>茶色</td><td>29</td><td>6.7</td><td>无异常</td><td>无异常</td><td>涂膜稍有溶解</td></tr><tr><td>27</td><td>绿色</td><td>14</td><td>5.8</td><td>无异常</td><td>有变化</td><td>只有擦拭痕迹</td></tr><tr><td>20</td><td>洗灰色</td><td>15</td><td>1.8</td><td>无异常</td><td>有变化</td><td>涂膜溶解，光泽降低</td></tr><tr><td></td><td>灰色</td><td>66</td><td>0.4</td><td>无异常</td><td>无异常</td><td>光泽降低</td></tr></table></body></html>\n\n$\\Phi$ 指经过1000h的人工加速老化试验（QUV).$\\textcircled{\\oslash}$ 甲乙酮，即甲基乙基甲酮。$\\textcircled{3}$ 有变化指涂膜的表面发生变化，即涂膜的光泽降低、变色或起泡等。  \n\n从表3-1-67可以看出，所有涂料耐 $5\\%$ $\\mathrm{H}_{2}\\mathrm{SO}_{4}$ 的性能都非常良好；多数涂料耐 $5\\%$ $\\mathbf{NaOH}$ 的性能也很好，而少数涂料耐 $5\\%\\ \\mathrm{NaOH}$ 的性能较差；在MEK（甲乙酮）擦拭试验中，多数涂膜的光泽都降低；在经过1000h的人工加速老化试验后，涂膜保光率的差别很大。同时，从表3-1-67还可以看出，涂料的性能并不完全取决于氟含量。总之，氟含量是氟树脂性能的重要指标，但还与氟树脂的分子结构有关；同时，氟树脂涂料的性能还与涂料配方等因素有关。因而，对于不同类型的氟树脂，有不同的可比性，其含量的高低对涂料性能的影响也不一致，应根据涂料使用环境和性能的要求，做到氟含量与涂料性能之间的平衡。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 925,
+        "chunk": "# 五、金属光泽外墙涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 926,
+        "chunk": "# 1.基本配方  \n\n作为外墙面使用的金属光泽涂料，与汽车涂装使用的金属光泽涂料有以下明显差别：一是涂装时基层的不同（金属和混凝土的差别)；二是涂膜表面的装饰效果要求的不同。因而，配制外墙金属光泽涂料时，应考虑到这些具体情况的不同。表3-1-68展示出以丙烯酸树脂为基料的金属光泽外墙涂料的参考配方；表3-1-69为双组分氟树脂金属光泽建筑涂料的基本配方。  \n\n表3-1-68金属光泽外墙涂料配方举例  \n\n\n<html><body><table><tr><td>原材料</td><td>功 用</td><td>用量（质量分数）/%</td></tr><tr><td>B66丙烯酸树脂</td><td>基料</td><td>30.0~40.0</td></tr><tr><td>金属铝粉浆</td><td>金属额料，产生金属效果</td><td>3.0~6.0</td></tr><tr><td>防沉剂</td><td>防止沉淀，促进铝鳞片定位</td><td>2.5~5.5</td></tr><tr><td>流平剂</td><td>促进涂料流平和铝鳞片定位，有利于溶剂挥发</td><td>0. 3~0. 8</td></tr><tr><td>溶剂</td><td>分散介质</td><td>补足100%配方量</td></tr></table></body></html>  \n\n表3-1-69具有金属质感的双组分氟树脂外墙涂料参考配方   \n\n\n<html><body><table><tr><td>原材料名称</td><td>商品型号</td><td>生产厂商</td><td>用量（质量分数）/%</td></tr><tr><td>涂料组分</td><td></td><td></td><td></td></tr><tr><td>氟树脂</td><td>XF-ZB200</td><td>大连明辰振邦公司</td><td>35~50</td></tr><tr><td>有机硅-丙烯酸酯树脂</td><td>坚固王</td><td>上海市建筑科学研究院</td><td>0~15</td></tr><tr><td>CAB凝胶</td><td></td><td>美国伊士曼（Eastman）公司</td><td>25~30</td></tr><tr><td>铝粉浆（50%）</td><td>②</td><td>进口</td><td>8~10</td></tr><tr><td>分散剂</td><td>TEXAPHOR3073</td><td>德国汉高公司（Henkel）</td><td>0.5</td></tr><tr><td>消泡剂</td><td>PERENOL E9</td><td>德国汉高公司（Henkel）</td><td>0.5</td></tr><tr><td>固化剂组分</td><td></td><td></td><td></td></tr><tr><td>固化剂</td><td>与XF-ZB200树脂配套产品</td><td>大连明辰振邦公司</td><td>5~10</td></tr></table></body></html>\n\n$\\Phi$ CAB凝胶的配方（质量分数，%）为：二甲苯25；醋酸丁酯4；甲基异丁基甲酮17；CAB381-0.510；CAB381-206（CAB381-0.5和CAB381-20）均为美国伊士曼（Eastman）公司的商品；制备时将CAB加人溶剂中，中速搅拌至CAB完全溶解，体系呈透明凝胶态。$\\textcircled{2}$ 铝粉浆是提前24h将铝粉和二甲苯以1：1的比例混合，低速到中速搅拌 $30\\mathrm{\\sim}40\\mathrm{min}$ ，直至体系完全混合均匀。  \n\n在金属光泽外墙涂料中，除铝粉颜料外，有的情况下需要配制具有一定色彩的涂料，这时还需要使用着色颜料。由于颜料的使用总是会对涂膜的金属光泽产生不良影响，因而应考虑两个问题：一是颜料的耐候性必须很好；二是对涂料的光泽不能影响太大。因而，应选择诸如透明氧化铁系颜料、透明菁蓝、菁绿等颜料，并且在满足颜色要求的情况下应尽量减少其用量，以免对涂料的金属光泽产生太大的影响。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 927,
+        "chunk": "# 2.生产和使用技术要点  \n\n（1）金属光泽外墙涂料在生产过程中只能采取适当的速率（中速到高速）搅拌，不能研磨。需要使用的着色颜料在应制备成色浆加人。  \n\n(2）使用不同的成膜物质，可以得到不同性能和不同装饰效果的涂料。例如，在相同的配方组成情况下，使用聚氨酯-丙烯酸复合基料，得到的涂料无论是涂膜的金属光泽效果，还是涂膜的各种物理力学性能，都优于丙烯酸系涂料。  \n\n(3）为了提高涂膜的金属闪光效果，在涂装时可以采取涂饰罩面涂料的施工措施。应注意所使用的罩面涂料要有良好的耐黄变性。  \n\n（4）为了保证金属闪光效应，金属光泽涂料中的金属铝粉粒度一般较粗，因而在贮存过程中较易沉淀，为此除了使用一些助剂以外，涂料的黏度一般保持得较高。因此涂料在施工时需要加人稀释剂。  \n\n(5）金属光泽外墙涂料的涂膜一般较薄，宜采取喷涂施工。喷涂前，应先用稀释剂稀释。稀释后的涂料黏度低，便于涂料在成膜过程中溶剂挥发时铝鳞片平行于基层的定向排列，以得到金属光泽效果充分的涂膜。若采用刷涂施工，则涂膜的金属光泽效果变差。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 928,
+        "chunk": "# 六、溶剂型耐酸雨涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 929,
+        "chunk": "# 1.酸雨对外墙涂料的影响  \n\n酸雨是一种pH值小于5.6的酸性降水，含有许多无机酸和有机酸，其中绝大部分是硫酸和硝酸。多数情况下，酸雨成分以硫酸为主，从污染源排出的 $\\mathrm{so}_{2}$ 和 $\\mathsf{N O}_{x}$ 是形成酸雨的主要起始物。此外，酸雨还含有NO和CI、F、N等离子。  \n\n如果涂膜控制水分的能力差，大气中的湿气就很容易透过涂膜进入墙体，在露点以下容易在墙面与涂膜之间凝露，形成液态水，然后与基底发生化学反应，生成水化产物氧化钙，其反应式如下。  \n\n$$\n\\begin{array}{r}{2(3\\mathrm{CaO}\\cdot\\mathrm{SiO}_{2})+6\\mathrm{H}_{2}\\mathrm{O}\\longrightarrow3\\mathrm{CaO}\\cdot\\mathrm{SiO}_{2}\\cdot3\\mathrm{H}_{2}\\mathrm{O}+3\\mathrm{Ca}(\\mathrm{OH})_{2}}\\\\ {2(3\\mathrm{CaO}\\cdot\\mathrm{SiO}_{2})+4\\mathrm{H}_{2}\\mathrm{O}\\longrightarrow3\\mathrm{CaO}\\cdot\\mathrm{SiO}_{2}\\cdot3\\mathrm{H}_{2}\\mathrm{O}+3\\mathrm{Ca}(\\mathrm{OH})_{2}}\\end{array}\n$$  \n\n水化产物易吸收空气中的二氧化碳，发生碳酸化反应，生成碳酸钙结晶。由于氢离子的存在，使碳酸钙溶解度增加， $\\mathrm{Ca^{2+}}$ 浓度增大，溶液中的 $\\mathbf{Ca^{2+}}$ 易与酸雨中的 $\\mathrm{so}_{\\ell}^{2-}$ 作用生成疏松的石膏或氧氧化钙，直接与硫酸作用生成硫酸钙结晶，发生膨胀，使涂膜与基底之间附着力降低，随着时间延长还会造成涂膜疏松，出现粉化、鼓泡或剥落等现象，从而影响涂膜的耐久性。其相应的反应式如下。  \n\n$$\n\\begin{array}{c}{{\\mathrm{CaCO_{3}+H^{-}-\\ddots\\ C a^{2+}+\\ H C O_{3}^{-}}}}\\\\ {{\\mathrm{CaCO_{3}+S O_{4}^{2-}+H^{-}+H_{2}O-\\ddots\\ C a S O_{4}\\cdot2H_{2}O+C O_{2}}}}\\\\ {{\\mathrm{Ca(OH)_{2}+H_{2}S O_{4}\\longrightarrow C a S O_{4}+2H_{2}O}}}\\end{array}\n$$  \n\n总体来说，酸雨中的硫酸根离子会以各种形式沉积到涂膜表面，经催化氧化成硫酸，使涂膜局部表面酸性较强，且硫酸根离子浓度高。酸雨对涂膜的腐蚀是酸雨中 $\\mathbf{H}^{+}$ 、 $\\mathrm{so}_{4}^{2-}$ 协同侵蚀作用的结果，主要是 $\\mathbf{H}^{+}$ 的溶解腐蚀和 $\\mathrm{{so}_{4}^{2-}}$ 的膨胀腐蚀，导致涂膜体积膨胀，发生粉化、脱落、起泡等现象。  \n\n我国大、中城市降水中硫酸根离子和钙离子含量分别为美国的3倍和10倍，在某些城市（例如重庆）或地区，酸雨已经对建筑物产生严重的污染或破坏。对于大气污染严重的城市，特别是酸雨污染严重的城市，适宜选择溶剂型耐酸雨外墙涂料。而为了减少涂料中溶剂对大气的污染，应注意增大耐酸雨涂料的固体含量，降低溶剂用量。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 930,
+        "chunk": "# 2.耐酸雨外墙涂料的技术要点  \n\n（1）基料的选用目前，用于耐酸雨涂料的基料主要有硅丙树脂、含氟树脂和丙烯酸树脂三类。为了适应城市高层建筑外墙装饰与保护的需要，应使用溶剂型的高性能硅丙外墙涂料和氟树脂涂料等，而尤以硅丙树脂外墙涂料具有较好的综合效益。用人工配制的 $\\mathrm{H}_{2}\\mathrm{SO}_{4}$ ，$\\mathrm{\\DeltaHNO_{3}}$ 和HCI稀溶液（pH值 $\\scriptstyle=3,2;$ ）进行涂料破坏点蚀试验证明，硅丙涂料在 $71\\mathrm{\\bar{C}}$ 的高温下仍具有抗酸蚀能力，并优于聚氨酯、环氧树脂等涂料。  \n\n(2）颜填料的选用耐酸雨外墙涂料必须既有良好的装饰性，又有优异的耐候性、耐沾污性和耐酸雨性。耐酸雨外墙涂料用的颜料，应首选金红石型钛白粉。填料方面，重晶石粉常用于耐酸涂料中；绢云母粉粒子呈微细鳞片状，透明、高亮度、难溶于酸、碱溶液，在涂膜中由细到粗级配，在涂膜中能够平行于基层重叠，相互填充，增大涂膜的致密性和屏蔽紫外线的功能，从而增大涂膜的抗老化性、耐候性、耐水性和耐洗刷性，是耐酸雨涂料的优质功能型填料。  \n\n(3）采用新技术例如在涂料中使用纳米材料以改善涂料的性能，提高涂膜的耐沾污性、耐候性和保光、保色性等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 931,
+        "chunk": "# 七、溶剂型涂料生产技术  \n\n建筑涂料的生产程序因为涂料的品种不同而略有差异，一般来说溶剂型涂料属于薄质涂料，其生产大体上可以分成料浆制备、料浆研磨、涂料调制和过滤、罐装等程序过程，所使用的设备有配套涂料罐的调速揽拌机、研磨料浆的研磨设备（一般使用砂磨机或者胶体磨）、涂料调制设备（即配套有涂料罐的调速揽拌机）和过滤设备（袋式过滤机、振动筛或过滤罗筛等）以及罐装设备等。其中，如果因为受到生产工艺设置或者设备的限制，涂料调制程序可以使用和料浆制备的同一设备。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 932,
+        "chunk": "# 1.料浆的制备  \n\n料浆的制备也称颜料、填料的预分散。制备时，先将分散介质投入涂料罐中，按照设计的配方投入各种助剂，搅拌均匀后再投入颜料和填料，充分搅拌并使之均匀，得到预分散料浆。其中，作为分散介质的溶剂一般不止一种，大多是使用混合溶剂。根据情况可以将各种溶剂全部投入，也可以预留一部分溶剂留待涂料调制程序中加入。在助剂的投料过程中一般是先投入消泡剂、润湿剂、分散剂等，搅拌均匀后再投入流变增稠剂。  \n\n为了使料浆具有一定黏度以利于研磨操作，并方便其后的涂料调配操作，在料浆制备时常常加入一定量的树脂溶液。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 933,
+        "chunk": "# 2.料浆的研磨  \n\n将经过预分散的料浆通过液体输送设备（如配套有输送管道的齿轮泵、螺杆泵等）输送到砂磨机或者胶体磨中，按照设备操作程序进行磨细操作。研磨时如果一遍不能达到细度要求，可以反复多道研磨，直至达到要求的细度为止。 型",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 934,
+        "chunk": "# 3.料浆与基料（树脂溶液）的混合  \n\n将磨细的料浆转移至混料罐中，在混料罐中的磨细料浆处于搅拌的状态下，将基料缓慢地投入混料罐中，搅拌均匀，制成涂料混合料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 935,
+        "chunk": "# 4.涂料调制  \n\n按照涂料性能要求的黏度，使用增稠剂、溶剂等材料将涂料的黏度调整至规定值。溶剂  \n\n型建筑涂料的黏度一般应调整在涂-4杯黏度 $60\\sim120\\mathrm{s}$ 的范围内。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 936,
+        "chunk": "# 5.过滤与罐装  \n\n将磨细后的料浆通过振动筛或其他过滤设备过滤，以去除生产操作过程中混入的机械杂质。然后，取样检查，合格后包装入库，得到成品涂料。  \n\n上述工艺程序以简要的工艺流程图描述，则如图3-1-18所示。  \n\n![](images/f88f322b65fd0bfbc0520572953e0a78a5d69f3757b109a9c44e4abb662cbd51.jpg)  \n图3-1-18液体薄质建筑涂料的工艺程序示意图",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 937,
+        "chunk": "# 6.涂料调配时可能出现的问题及避免措施  \n\n在涂料调配时，可能出现以下几个问题。  \n\n(1）两种组成相差较大的基料突然接触而出现“胶体冲突”现象。除基料的组成外，基料的温度、黏度、表面张力等方面的不同也能造成“冲突”现象，从而引起树脂析出、剥离、聚集以及溶剂扩散等，进而造成涂料的稳定性不良。  \n\n(2）由于合成树脂对溶剂有一定的容忍度，树脂溶液的固体含量在其允许的范围以内，树脂可以溶解，低于其允许范围，树脂就会析出而形成沉淀。在涂料调配过程中如果操作不当而使树脂溶液低于其允许范围，就会导致树脂的暂时性析出，使原来包覆有树脂膜的颜料粒子间的空间位阻降低，颜料粒子就有可能产生絮凝，使分散体系的稳定性不良。  \n\n(3）溶剂迁移现象的发生，这是在把一种浓度较高的树脂溶液加入到溶剂含量较高的研磨料浆（如砂磨机研磨料浆）时的一种导致颜料絮凝返粗的情况。溶剂迁移引起颜料絮凝或返粗的原因在于，把高浓度的树脂溶液加入到树脂浓度低的研磨料浆中，研磨料浆中低黏度的溶剂向浓度高的树脂溶液中扩散，颜料则会集留在原来的研磨料浆中。在溶剂向树脂溶液中迁移扩散的同时，研磨料浆的体积不断缩小。结果，集留的颜料粒子在研磨料浆收缩过程中被挤压得越来越密集，直至相互接触并絮凝。  \n\n综上所述，在涂料调配操作中应注意以下几个问题。  \n\n(1）对于所使用的溶剂体系，应将溶剂适当地分配于研磨料浆中。溶剂分配的原则是能延缓溶剂从一种树脂溶液向另一种溶液中迁移，使其变得可以控制并防止局部地区出现过高的迁移速率。  \n\n(2）涂料调配时，涂料调配罐中的物料处于充分搅拌状态，可以避免混合不均匀及物料中因局部增量太大而造成的稳定性不良现象。调深色涂料时，由于所需向研磨料中加入的溶剂还很多，尤需特别注意。这种情况下也可以将树脂溶液用剩余的溶剂稀释，再将树脂稀释液和磨细料浆混合，整个操作过程尤应注意充分搅拌，缓慢加料。  \n\n(3）配制研磨料浆时，应首先使用高沸点、低挥发速率的溶剂，既可缓解涂料调配时的溶剂迁移现象，在料浆磨细期间溶剂的挥发损失也会降低且减少环境污染。  \n\n（4）对于较长期贮存的色浆，可能其黏度偏高，应先以强力搅拌破坏其触变性，也可视情况先用树脂溶液将其调稀，然后再用于涂料调配。  \n\n(5）由于将温度低而黏度又较高的树脂溶液与树脂含量很低的研磨料浆混合时，易出现树脂聚集或溶剂迁移现象，造成胶态分散不良或颜料分散不良等问题。因而在树脂溶液加入磨细料浆中之前，应先做黏度及温度的调整，尽量避免将黏度和温度相差很大的组分互相混合。  \n\n涂料的生产工艺随着加工设备技术的进步及涂料原材料的变化也在发生变化。例如，近年来出现并得到应用的、称为高效涂料岛的全自动化涂料生产线，将涂料的分散、研磨、过滤和罐装等程序集中于一体，并处于同一底座上，因而称为“加工岛”。此外，涂料原材料的进步，也使得涂料的生产工艺得以简化。例如，现代超细粉体加工技术使得细度能够达到1000目以上的涂料用颜料、填料十分常见。对于这类超细颜料、填料，再加上涂料润湿剂的应用，可以使涂料生产过程中的研磨工序得以简化。而颜料、填料表面处理技术的进步，使得经过处理的颜料、填料，也能够在简化掉研磨工序的情况下，使颜料、填料能够得到更可靠的分散。在这些情况下，既可以简化建筑涂料的生产过程，又能够降低生产过程中的能耗，提高生产能力等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 938,
+        "chunk": "# 八、技术性能指标",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 939,
+        "chunk": "# 1.国家标准规定的技术性能指标  \n\n溶剂型建筑涂料的技术性能应能够满足国家标准GB/T9757—2001《溶剂型外墙涂料》的技术要求，见表3-1-70。  \n\n表3-1-70溶剂型外墙涂料的技术性能指标  \n\n\n<html><body><table><tr><td rowspan=\"2\">性能指标项目</td><td colspan=\"3\">性能指标</td></tr><tr><td>优等品</td><td>一等品</td><td>合格品</td></tr><tr><td>容器中状态 施工性</td><td>无硬块，搅拌后呈均匀状态 剧涂两道无障碍</td><td>无硬块，搅拌后呈均匀状态 剧涂两道无障碍</td><td>无硬块，搅拌后呈均匀状态 剧涂两道无障碍</td></tr><tr><td>干燥时间(表干)/h ≤</td><td>2</td><td>2</td><td>2</td></tr><tr><td>涂膜外观</td><td>正常</td><td>正常</td><td>正常</td></tr><tr><td>对比率（白色和浅色） ≥</td><td>0. 93</td><td>0.90</td><td>0.87</td></tr><tr><td>耐水性</td><td>168h无异常</td><td>168h无异常</td><td>168h无异常</td></tr><tr><td>耐碱性</td><td>48h无异常</td><td>48h无异常</td><td>48h无异常</td></tr><tr><td>耐洗刷性/次</td><td>5000</td><td>3000</td><td>2000</td></tr><tr><td>≥ 耐人工气候老化性</td><td></td><td></td><td></td></tr><tr><td>白色和浅色</td><td></td><td>1000h不起泡、不剥落、无裂纹500h不起泡、不剥落、无裂纹</td><td>300h不起泡、不剥落、无裂纹</td></tr><tr><td>粉化/级 VW</td><td>1</td><td>1</td><td>1</td></tr><tr><td>变色/级</td><td>2</td><td>2</td><td>2</td></tr><tr><td>其他色</td><td>商定</td><td>商定</td><td></td></tr><tr><td>耐沾污性（白色和浅色）≤</td><td>10</td><td>10</td><td>商定</td></tr><tr><td></td><td></td><td></td><td>15</td></tr><tr><td>涂层耐温变性（5次循环）</td><td>无异常</td><td>无异常</td><td>无异常</td></tr></table></body></html>\n\n$\\Phi$ 浅色是指以白色涂料为主要成分，添加适量色浆后配制成的浅色涂料形成的涂膜所呈现的浅颜色，按GB/T15608—1995中4.3.2规定明度值为 $\\scriptstyle6\\sim9$ （三刺激值中的 $Y_{\\mathrm{DSS}}{\\geqslant}31.26)$ 重",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 940,
+        "chunk": "# 2.化工行业标准规定的氟树脂涂料的技术性能指标  \n\n化工行业标准HG/T3792—2005《交联型氟树脂涂料》根据交联型氟树脂涂料的两个主要应用领域，分为两种类型，I型为建筑外墙用氟树脂涂料，Ⅱ型为金属表面用氟树脂涂料，该标准规定的技术性能指标见表3-1-71。  \n\n表3-1-71交联型氟树脂涂料的技术性能指标  \n\n\n<html><body><table><tr><td rowspan=\"2\">项</td><td rowspan=\"2\">目</td><td colspan=\"3\">指 标</td></tr><tr><td>I型</td><td></td><td>型</td></tr><tr><td colspan=\"2\">容器中状态</td><td colspan=\"3\">搅拌后均匀无硬块</td></tr><tr><td colspan=\"2\">细度（含铝粉、珠光颜料的涂料组分除外）/μm</td><td colspan=\"3\">商定</td></tr><tr><td rowspan=\"2\">不挥发物/% ≥</td><td>白色和浅色（含铝粉、 珠光颜料的涂料除外）</td><td rowspan=\"2\">一</td><td>50</td></tr><tr><td>其他色</td><td>40</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td colspan=\"2\">项</td><td colspan=\"2\">指 标</td></tr><tr><td rowspan=\"2\">溶剂可溶物氟含量/% ></td><td>目</td><td>I型</td><td>Ⅱ型</td></tr><tr><td>双组分(漆组分)</td><td>18</td><td></td></tr><tr><td rowspan=\"3\">干燥时间/h ≤</td><td>单组分</td><td></td><td>10</td></tr><tr><td>表干（自干漆）</td><td>2</td><td></td></tr><tr><td>实干</td><td>24</td><td></td></tr><tr><td rowspan=\"3\">遮盖率</td><td>烘干（烘烤型漆）[（140±2)℃] 白色和浅色（含铝粉、</td><td></td><td>0.5或商定</td></tr><tr><td>珠光颜料的涂料除外）</td><td>0.90</td><td></td></tr><tr><td>其他色</td><td>商定</td><td></td></tr><tr><td colspan=\"2\">涂膜外观</td><td>正常</td><td></td></tr><tr><td colspan=\"2\">适用期（5h)（烘烤型除外）</td><td>通过</td><td></td></tr><tr><td colspan=\"2\">重涂性</td><td colspan=\"2\">重涂无障碍</td></tr><tr><td colspan=\"2\">光泽（60°）（含铝粉、珠光颜料的涂料除外）</td><td>商定</td><td></td></tr><tr><td colspan=\"2\">铅笔硬度(擦伤)</td><td></td><td>F</td></tr><tr><td colspan=\"2\">耐冲击性</td><td></td><td>40</td></tr><tr><td colspan=\"2\">附着力/级</td><td>1</td><td></td></tr><tr><td colspan=\"2\">≤ 耐弯曲性/mm ≤</td><td></td><td>3</td></tr><tr><td colspan=\"2\">耐酸性（168h)</td><td colspan=\"2\">无异常</td></tr><tr><td colspan=\"2\">耐砂浆性(24h)</td><td>无变化</td><td></td></tr><tr><td colspan=\"2\">耐碱性(168h)</td><td>一</td><td>无异常</td></tr><tr><td colspan=\"2\">耐水性(168h)</td><td>无异常</td><td></td></tr><tr><td colspan=\"2\">耐湿冷热循环性(10次)</td><td colspan=\"2\">无异常</td></tr><tr><td colspan=\"2\">耐洗刷性/次</td><td>10000</td><td></td></tr><tr><td colspan=\"2\">耐污染性</td><td colspan=\"2\">通过</td></tr><tr><td colspan=\"2\">外耐沾污性(白色和浅色少）含铝粉、珠光颜料的涂料除</td><td>10</td><td></td></tr><tr><td colspan=\"2\">耐溶剂擦拭性（I型为二甲苯；Ⅱ型为丁酮）/次</td><td>100</td><td></td></tr><tr><td colspan=\"2\">耐湿热性</td><td>一</td><td>1000h不起泡、不生锈、不脱落</td></tr><tr><td colspan=\"2\">耐盐雾性</td><td>一</td><td>1000h不起泡、不生锈、不脱落</td></tr><tr><td rowspan=\"5\">耐人工气候老化性</td><td>白色和浅色</td><td>2500h不起泡、</td><td>2500h不起泡、不开裂、 不生锈、不脱落</td></tr><tr><td>粉化/级 VWW</td><td>不脱落、不开裂 商定</td><td>商定</td></tr><tr><td>变色/级</td><td>商定</td><td>商定</td></tr><tr><td></td><td></td><td></td></tr><tr><td>失光/级</td><td>商定</td><td>商定</td></tr></table></body></html>\n\n$\\Phi$ 浅色是指以白色涂料为主要成分，添加适量色浆后配制成的浅色涂料形成的涂膜所呈现的浅颜色，按GB/T15608—1995中4.3.2规定明度值为 ${\\mathfrak{s}}{\\sim}9$ （三刺激值中的 $Y_{53}331.26)$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 941,
+        "chunk": "# 3.建工行业标准规定的合成树脂幕墙的技术性能指标  \n\n按照建工行业标准JG/T205—2007《合成树脂幕墙》的要求，合成树脂幕墙包括氟树脂、聚酯树脂和硅树脂幕墙三类，该标准规定的这三类幕墙的技术性能指标见表3-1-72～表3-1-74。  \n\n表3-1-72氟树脂幕墙技术要求  \n\n\n<html><body><table><tr><td>项 目</td><td>指 标</td></tr><tr><td>外观</td><td>正常</td></tr><tr><td>硬度</td><td>H</td></tr><tr><td>耐冲击性/cm</td><td>50</td></tr><tr><td>耐水性</td><td>168h无异常</td></tr><tr><td>耐碱性</td><td>168h无异常</td></tr><tr><td>耐酸性</td><td>168h无异常</td></tr><tr><td>耐洗刷性/次</td><td>≥10000</td></tr><tr><td>耐人工老化性</td><td></td></tr><tr><td>白色及浅色</td><td>3000h不起泡、剥落，无裂纹</td></tr><tr><td>粉化/级</td><td>VWW 1</td></tr><tr><td>变色/级</td><td>2</td></tr><tr><td>失光/级</td><td>2</td></tr><tr><td>耐沾污性（白色及浅色）/% ≤</td><td></td></tr><tr><td>涂层耐温变形（20次循环）</td><td>无异常</td></tr><tr><td>粘接强度/MPa 》</td><td>1. 0</td></tr><tr><td>拉伸强度/MPa</td><td>≥ 3.5</td></tr></table></body></html>\n\n$\\Phi$ 浅色是指以白色涂料为主要成分，添加适量色浆后配制成的浅色涂料形成的涂膜所呈现的浅颜色，按GB/T15608—1995中4.3.2规定明度值为 $6\\sim9$ （三刺激值 $Y_{\\mathrm{DAB}}{\\geqslant}31.26)$  \n\n表3-1-73聚酯树脂幕墙技术要求  \n\n\n<html><body><table><tr><td>项 目</td><td>指 标</td></tr><tr><td>外观</td><td>正常</td></tr><tr><td>硬度</td><td>HB</td></tr><tr><td>耐冲击性/cm</td><td>50</td></tr><tr><td>耐水性</td><td>168h无异常</td></tr><tr><td>耐碱性</td><td></td></tr><tr><td>耐酸性</td><td>48h无异常</td></tr><tr><td>耐洗刷性/次</td><td>48h无异常 8000</td></tr><tr><td>耐人工老化性</td><td></td></tr><tr><td>白色及浅色</td><td>2000h不起泡、剥落，无裂纹</td></tr><tr><td>色/级</td><td>VVV 122</td></tr><tr><td>失光/级 耐沾污性（白色及浅色）/%</td><td>≤ 10</td></tr><tr><td>涂层耐温变形（20次循环）</td><td>无异常</td></tr><tr><td>粘接强度/MPa</td><td>≥ 1.0</td></tr><tr><td>拉伸强度/MPa</td><td>3.0</td></tr></table></body></html>\n\n$\\Phi$ 浅色是指以白色涂料为主要成分，添加适量色浆后配制成的浅色涂料形成的涂膜所呈现的浅颜色，按GB/T15608—1995中4.3.2规定明度值为6\\~9（三刺激值 $\\begin{array}{r}{Y_{\\tt D S}\\geqslant31.}\\end{array}$ 26)。  \n\n表3-1-74硅树脂幕墙技术要求  \n\n\n<html><body><table><tr><td>项 目</td><td>指 标</td></tr><tr><td>外观</td><td>正常</td></tr><tr><td>硬度</td><td>B</td></tr><tr><td>耐冲击性/cm</td><td>50</td></tr><tr><td>耐水性</td><td>168h无异常</td></tr><tr><td></td><td>48h无异常</td></tr><tr><td>耐碱性</td><td>48h无异常</td></tr><tr><td>耐酸性</td><td>6000</td></tr><tr><td>耐洗刷性/次 耐人工老化性</td><td></td></tr><tr><td>白色及浅色</td><td>1500h不起泡、剥落，无裂纹</td></tr><tr><td>粉化/级</td><td>1</td></tr><tr><td>变色/级</td><td>2</td></tr><tr><td>失光/级</td><td>2</td></tr><tr><td>耐沾污性（白色及浅色）/%</td><td>≤ 12</td></tr><tr><td>涂层耐温变形（20次循环）</td><td>无异常</td></tr><tr><td>粘接强度/MPa 拉伸强度/MPa</td><td>≥ 1. 0 ≥ 2.5</td></tr></table></body></html>\n\n$\\Phi$ 浅色是指以白色涂料为主要成分，添加适量色浆后配制成的浅色涂料形成的涂膜所呈现的浅颜色，按GB/T15608—1995中4.3.2规定明度值为 $_{6\\sim9}$ （三刺激值 $Y_{\\mathrm{DBS}}{\\geqslant}31,26)$ \\*",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 942,
+        "chunk": "# 九、普通涂装的溶剂型建筑涂料施工技术",
+        "category": " Introduction"
+    },
+    {
+        "id": 943,
+        "chunk": "# 1.涂装工序及其施工技术要点  \n\n(1）施工准备包括材料准备、材料检查、工具准备、涂料处理（调整黏度、搅拌均匀等)、人员准备等。  \n\n(2）基层处理  \n\n$\\textcircled{1}$ 基层条件砂浆、混凝土及砖砌体基层表面应达到坚硬、平整、粗糙、干净、湿润基层应有满足施工要求的强度（一般需2周以上的养护期)。  \n\n$\\textcircled{2}$ 基层处理先全面检查清理墙面，除去基层表面的浮灰、脏物等，然后用砂纸打磨，清扫干净。基层如有较大、较深的凹坑、裂缝等，应预先用聚合物乳液水泥砂浆填平、嵌实腻子，干燥后用铲刀刮一遍。对于外墙面，刷 $1{\\sim}2$ 道耐碱封闭底漆。  \n\n$\\textcircled{3}$ 基层要求由于溶剂型涂料的涂膜透气性低，不透水且具有疏水性，因此要求基层干燥，其含水率低于 $8\\%$ ，并以偏低为好。  \n\n(3）施工程序  \n\n$\\Phi$ 腻子采用聚合物水泥腻子或者苯丙乳胶腻子满刮 $_{1\\sim2}$ 道。  \n\n$\\textcircled{2}$ 涂料采用羊毛辊筒或漆刷进行辊涂或刷涂施工。也可以采取喷涂方法施工，喷涂时每道不宜喷涂得太厚，以防流挂。通常涂装两遍，两道之间的间隔时间在2h左右。溶剂型涂料与水性涂料不同，可在较低温度下施工。但是，在炎热的夏季，气温太高时溶剂挥发较快，涂料黏度升高，涂层表面可能留有刷痕，也有可能将第一道涂装的涂膜溶解而造成涂膜弊病，影响涂膜质量。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 944,
+        "chunk": "# 2.施工质量缺陷及其防治措施  \n\n(1）流挂（流坠、流等）问题出现的可能原因： $\\textcircled{1}$ 涂料黏度低； $\\textcircled{2}$ 涂层过厚； $\\textcircled{3}$ 涂料本身具有流挂的质量问题；④喷涂施工时，喷枪与墙面距离太近，或涂料未搅匀，上层涂料过稀。  \n\n防治措施： $\\textcircled{1}$ 要求涂料的黏度合格，颜料、填料的配比适当，并在施涂前一定要搅拌均匀； $\\textcircled{2}$ 涂料每道不可涂装太厚，施工工具（刷子或辊筒）每次蘸涂料量不可太多； $\\textcircled{3}$ 与生产厂商协商解决流挂问题； $\\textcircled{4}$ 按正确的喷涂施工方法进行。  \n\n(2）涂膜遮盖力不良问题出现的可能原因： $\\textcircled{1}$ 涂料本身的遮盖力不良； $\\textcircled{2}$ 涂料黏度低； $\\textcircled{3}$ 对于有沉淀分层的涂料涂装前没有充分搅拌均匀； $\\textcircled{4}$ 底漆或腻子层与面涂料的颜色差别较大。  \n\n防治措施： $\\Phi$ 选用遮盖力（对比率）符合质量标准要求的涂料； $\\textcircled{2}$ 提高涂料施工黏度；$\\textcircled{3}$ 对于有沉淀或分层的涂料在涂装前要充分搅拌均匀； $\\textcircled{4}$ 调整底涂料或腻子的颜色尽量一致，或者多涂装一道面涂料。  \n\n(3）涂料光泽不均匀问题出现的可能原因： $\\textcircled{1}$ 稀释涂料时稀释剂选用不当； $\\textcircled{2}$ 施工时涂膜厚薄不均匀； $\\textcircled{3}$ 涂装道数不够。  \n\n防治措施： $\\Phi$ 按规定选用稀释剂； $\\textcircled{2}$ 施工时注意涂膜厚薄均匀； $\\textcircled{3}$ 涂装至足够的道数，必要时增加涂装道数。  \n\n(4）涂装后短期内即有变色或褪色现象问题出现的可能原因： $\\textcircled{1}$ 涂料中所用颜料耐光性、耐碱性差，或易粉化； $\\textcircled{2}$ 基料耐候性差； $\\textcircled{3}$ 涂料耐老化性能差。  \n\n防治措施： $\\Phi$ 涂料生产时要选用耐光性、耐碱性好的颜料； $\\textcircled{2}$ 选用耐候性好的基料；$\\textcircled{3}$ 选用耐老化性能合格的涂料。  \n\n(5）涂膜发花问题出现的可能原因： $\\textcircled{1}$ 涂料本身有浮色； $\\textcircled{2}$ 涂料中颜料分散不好；$\\textcircled{3}$ 涂膜厚薄不均； $\\textcircled{4}$ 基层表面粗糙程度不同，或基层碱性过大； $\\textcircled{5}$ 涂料在不同的颜色搭界处，颜色相互渗透。  \n\n防治措施： $\\Phi$ 在涂料中适当地加入防浮色、防发花助剂，并充分揽拌均匀； $\\textcircled{2}$ 生产涂料时要选用质量好的颜料，并使其在涂料中分散好，提高涂料的黏度； $\\textcircled{3}$ 施涂时应均匀，使涂膜厚薄一致； $\\textcircled{4}$ 可进行底涂封闭处理； $\\textcircled{5}$ 重复涂施涂料时，先涂不易渗色的涂料，后涂容易渗色的涂料，并在涂料彻底干燥后再涂装。  \n\n（6）涂膜起皮、脱落等问题出现的可能原因： $\\Phi$ 腻子粘接强度低； $\\textcircled{2}$ 基层含水率过高； $\\textcircled{3}$ 腻子未彻底干燥就施涂涂料。  \n\n可以采取的防治措施： $\\textcircled{1}$ 选用粘接强度高、耐水性好、符合外墙腻子标准要求的腻子；$\\textcircled{2}$ 使基层符合涂装条件要求； $\\textcircled{3}$ 待腻子层干透后再施工涂料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 945,
+        "chunk": "# 十、氟树脂涂料仿铝板涂层施工技术",
+        "category": " Introduction"
+    },
+    {
+        "id": 946,
+        "chunk": "# 1.概述  \n\n用涂料通过一定的施工方法涂装出类似于铝塑板装饰效果的涂膜饰面，提高了涂膜的装饰效果，是近几年发展起来的新的施工工艺，在高档建筑工程中已有应用。仿铝板装饰涂层也称仿金属漆、合成树脂幕墙系统，指的都是在外墙抹灰面上做出分隔缝，用配套腻子批刮、打磨、抛光，然后喷涂溶剂型碱金属质感的氟树脂涂料（也可以是金属质感的聚氨酯涂料、有机硅-丙烯酸涂料）而达到的类似于铝板装饰效果的涂层饰面。涂层可制成有金属光泽的饰面，也可以是无光泽的饰面，均具有特殊的装饰效果，属于高装饰性墙面涂料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 947,
+        "chunk": "# 2.仿铝板氟树脂涂料施工的材料配套  \n\n仿铝板氟树脂涂料配套材料不仅产品功能各有不同，而且品种多样，目前市场上不同品  \n\n种的材料搭配形式多样。仿铝板氟树脂涂料的材料体系见表3-1-75。  \n\n表3-1-75仿铝板氟树脂涂料常用材料  \n\n\n<html><body><table><tr><td>体系</td><td>材料名称</td><td>用途</td><td>简要说明</td></tr><tr><td rowspan=\"5\">基层处理、 找平和修 补等材料</td><td>抗裂复合体系腻子、耐碱网格布、分格缝专 用弹性腻子、旧墙面翻新专用弹性腻子</td><td>新墙抗裂处理 与旧墙界面处 理、抗裂处理</td><td>途径，伸缩缝的处理可以减缓裂 缝的产生；旧墙翻新专用腻子是 刚性和柔性复合的抗裂方法是 目前解决墙面裂缝的方向和最佳</td></tr><tr><td>补洞腻子（也称聚合物水泥砂浆）</td><td>修补润口</td><td>旧墙翻新的强力界面材料 防止产生洞、疤或色差、凹陷等</td></tr><tr><td>点补腻子、氟树脂涂料喷涂专用找平腻子</td><td>基层表面找平</td><td>处理 主要用于基层表面的平整度</td></tr><tr><td>氟树脂涂料专用滑爽腻子（双组分）、氟树 脂涂料专用滑爽腻子（单组分）、氟碳喷涂专 用抛光腻子、滑爽抛光二合一腻子</td><td>基层表面抛光</td><td>配套性进行选用 这些不同的腻子主要用于增加 基层表面的平滑度，可以根据不 同的体系要求和材料的易得性、</td></tr><tr><td>瓷砖翻新专用腻子、溶剂型填补腻子</td><td>旧墙处理</td><td>瓷砖凿掉，既省工，又不会给施工 具有和瓷砖表面的高强黏结性 能，可以直接批涂于旧瓷砖表面 而不必像传统翻新方法那样将旧</td></tr><tr><td rowspan=\"3\">涂料体系</td><td>涂塑耐碱玻璃纤维网格布</td><td>基层处理</td><td>带来环境影响 与面层砂浆的黏结性能良好， 能够抵抗砂浆中出现的微细裂缝</td></tr><tr><td>烯酸底涂、水性封闭底涂） 氟碳喷涂专用封闭底漆（环氧封闭底涂、丙</td><td>封闭体系</td><td>封闭基层微量水分，抵抗碱性 侵蚀</td></tr><tr><td>氟碳喷涂专用中涂（白色或彩色）</td><td>中涂</td><td>提高遮盖力、丰满度等，为高质 量的面漆提供一个好的基础</td></tr><tr><td>助剂体系</td><td>氟碳面涂（色漆、银色漆、金属漆其他金属 色面漆）、氟碳喷涂专用罩光清漆 慢干性涂料助剂、快干性涂料助剂</td><td>面涂 干燥速度调节材料</td><td>得到耐候性、耐沾污性和装饰 效果等性能均优良的氟碳涂膜 调整涂料干燥时间，提高涂料 在不同温度下的干燥性能的适</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 948,
+        "chunk": "# 3.仿铝板涂膜施工技术  \n\n(1）基本施工程序仿铝板涂膜施工的基本程序如图3-1-19所示。  \n\n![](images/083d6408069c27f152a69f934571d1a24caaf621806f3fcf9a9dd52eb87d8465.jpg)  \n图3-1-19仿铝板涂膜施工的基本程序(2）仿铝板氟碳涂膜的施工工艺表3-1-76中概述了仿铝板氟碳涂膜的施工工艺。  \n\n表3-1-76仿铝板氟树脂涂料施工工艺概述  \n\n\n<html><body><table><tr><td>工序</td><td>材料名称</td><td>功能特点</td><td>施工工具与施工方法</td><td>施工道数与定额</td></tr><tr><td>基层表面检查</td><td>仅人工与器具，无</td><td>整度检查空、开裂、平</td><td>橡皮锤、靠尺、红笔</td><td>要处理的部位 1道：用红笔记录需</td></tr><tr><td>基层表面处理</td><td>点补腻子</td><td>模充力强、附着力好、干</td><td>批刀、切割机</td><td>而~2 道：定额依现场</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>工序</td><td>材料名称</td><td>功能特点</td><td>施工工具与施工方法</td><td>施工道数与定额</td></tr><tr><td>分格缝施工</td><td>弹性巴氏胶</td><td>填充分格缝、补裂缝，弹 性好、抗开裂</td><td>复合管、切割机、 批刀</td><td>巴氏胶1道：定额依 现场面定</td></tr><tr><td>界面处理</td><td>头道找平腻子</td><td>填充性好，附着力强，干 燥快</td><td>批刀，批涂</td><td>1~2道：定额依现场 而定</td></tr><tr><td>防覆复合体系专用腻动裂复合体系专用</td><td></td><td>强度高，防止开裂，保证 原有防水效果，耐碱，寿</td><td>辊筒、批刀</td><td>1道：定额2.5kg/m²</td></tr><tr><td>头道腻子施工</td><td>找平腻子</td><td>基层表面找平，附着力 好，防水，施工性能好，抗</td><td></td><td>2～3道：定额约 纸打、排机、移35km,具体依现场</td></tr><tr><td>保护</td><td></td><td>成保护包括其他相关的半</td><td>批刀、美纹纸</td><td>具体依据现场面定</td></tr><tr><td>打磨养护</td><td></td><td>强工作窗更平常，保证</td><td>打磨板</td><td>具体依据现场而定</td></tr><tr><td>二道腻子施工</td><td>滑爽腻子</td><td></td><td>纸、打刀、被搅排机、砂</td><td>0. 1k 2 道:定额约</td></tr><tr><td>三道腻子施工</td><td>抛光腻子</td><td></td><td>板，批刀、砂纸、打磨</td><td>0. 2 2 道:定额约</td></tr><tr><td>喷涂封闭底漆</td><td>氟碳专用封闭底漆</td><td>封闭底层水分，抵抗碱 性侵蚀，附着力好，封闭性 好，防水性好，耐候性好</td><td>喷枪、空气压缩机、 油水分离器、打磨板， 喷涂</td><td>1道：定额0.1kg/m²</td></tr><tr><td>喷涂氟碳中涂</td><td>中建筑装饰专用氟碳</td><td></td><td>水分、打糖</td><td>1道：定额0.1kg/m</td></tr><tr><td>喷涂氟树脂涂料面涂</td><td>氟树脂涂料面涂 （色漆、金属漆、银色、 金色系列)</td><td>20年以上超长寿命最佳 装效果起泡洁，防水，耐 复杂气候</td><td>喷枪、空气压缩机、 油水分离器、打磨板， 喷涂</td><td>2道：定额0.2kg/m²</td></tr><tr><td>分格缝上色</td><td>建筑装饰分格缝专 用漆</td><td>20年以上超长寿命最佳 装饰效果，自洁，防水，不 开裂，不起泡，耐温差，耐</td><td>喷枪、空气压缩机、 油水分离器、打磨板， 喷涂</td><td>2道：定额0.2kg/m²</td></tr><tr><td>修整、清理、验收</td><td>对应材料</td><td>对应材料的功能和特点</td><td>对应施工工具</td><td>具体依现场而定</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 949,
+        "chunk": "# 十一、应用与发展展望  \n\n我国建筑涂料以水性产品为主，是所有涂料中水性化程度最高的涂料品种。由于涂料水性化会带来涂层某些性能的损失，因而溶剂型涂料中集中了几种高性能的建筑涂料。这类涂料的主要特征体现于耐日光和大气老化及耐污染几个方面，因而在建筑涂饰市场的高端得到一定的应用。例如，近年来发展的仿幕墙涂料和应用于复层涂料罩面的金属光泽涂料等。  \n\n但是，溶剂型涂料用于外墙面也有其弱点，使其应用和发展受到某种程度的制约。第一，外墙面是水泥基材料，在户外各种因素的作用下，开裂、渗水是常见的问题，而且这种问题处于动态变化中，很难根治。而目前的溶剂型建筑涂料对此是无能为力的，与能够遮蔽墙面微细裂缝的水性弹性涂料相比其缺陷显而易见，这在很大程度上限制了其应用。  \n\n第二，近年来随着国家建筑节能政策的强制实施，我国建筑业发生了重大变化，建筑物的围护结构都需要来取保温隔热措施。建设部提倡采用外墙外保温技术，目前，我国南北不同的气候区域广泛使用胶粉聚苯颗粒外墙外保温系统、膨胀聚苯板薄抹灰外墙外保温系统和挤塑聚苯板薄抹灰外墙外保温系统作为保温隔热措施。这三个系统的主体保温材料都是聚苯乙烯基的，将对溶剂型外墙涂料的应用与发展产生重要的影响。因为涂料中的很多溶剂会对聚苯乙烯产生溶解作用，即和系统是不相容的，不能与外墙外保温工程配套使用。  \n\n第三，由于我国多年来的改革开放和发展经济政策，在经济得到快速发展的同时，所面临的环境压力也越来越大，国家对环境保护空前重视。溶剂型涂料中含有大量溶剂会污染环境，其环保性能无法与水性涂料相比。  \n\n综上所述，溶剂型建筑涂料的使用将会受到越来越多的限制，在普通的工业与民用建筑上的应用会越来越少，其主要应用将向一些特殊工程转移，如近海构筑物，某些可能会受到高腐蚀性的建筑物等。  \n\n由于溶剂型建筑涂料的应用受到限制，其发展也将会受到影响。一些高性能的溶剂型涂料品种，例如氟树脂涂料、有机硅-丙烯酸酯共聚涂料、丙烯酸酯-聚氨酯复合涂料等应朝着水性化发展。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 950,
+        "chunk": "# 第三节无机建筑涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 951,
+        "chunk": "# 一、定义、种类与性能特征",
+        "category": " Introduction"
+    },
+    {
+        "id": 952,
+        "chunk": "# 1.定义与性能特征  \n\n（1）定义使用无机成膜物质（通常为硅酸盐类和二氧化硅的水分散体）和以水为分散介质制备的建筑涂料称为无机建筑涂料。  \n\n(2）性能特征无机涂料主要应用于外墙，在内墙的应用很少。本节讨论以应用于外墙的无机涂料为主。  \n\n外墙无机建筑涂料无毒、无环境和健康危害、节省能源、价格低廉，易于涂装，能常温干燥成膜。所形成的涂膜耐光、耐碱性优良，且耐候性好，耐热、防火性好，与基层的附着力高，特别是由于硅酸盐溶液中硅酸盐的大小为分子级，而硅溶胶的粒径处于纳米级，粒径都极其细微，析胶时的 $\\mathrm{SiO}_{2}$ 具有很高的活性，除了能够对颤料、填料颗粒产生很高的黏结力之外，细微的颗粒能够通过毛细管作用渗入到基层内部，并与水泥类无机基材中的Ca(OH)2发生化学反应，生成具有黏结性能的CaSiO凝胶，使涂料对基层产生很强的黏结力和封闭作用，增强涂膜与基层的附着力以及对基层的封闭性，消除或减缓可能出现的盐析或泛碱现象。无机涂膜的硬度较高，耐污染性好。此外，无机涂料有很好的防霉性。无机涂料涂料中不含或仅含少量的有机营养物质，微生物没有生存条件，不会滋生菌类、藻类；碱金属硅酸盐还可以杀死所涂基层中的菌类孢子，涂料中无需使用防霉杀菌剂，从另一个角度起到环保作用。  \n\n外墙无机建筑涂料的流平性不好，涂膜质脆，对基层体积变化的适应性差。此外，某些硅酸盐类外墙无机建筑涂料的耐水性不良以及涂料中因使用了密度大的颜料、填料而导致贮存过程中易产生沉淀结块等，这是该类涂料需要解决的性能不足之处。",
+        "category": " Introduction"
+    },
+    {
+        "id": 953,
+        "chunk": "# 2.分类与种类  \n\n在现行的建筑工业行业标准JG/T26—2002《外墙无机建筑涂料》中，无机外墙涂料被分成 $\\mathrm{~I~}$ 类和Ⅱ类两大类。其中，I类指的是以碱金属硅酸盐（硅酸钾、硅酸钠、硅酸锂或它们的混合物）加人相应的固化剂或合成树脂乳液为基料制成的涂料；Ⅱ类是指硅溶胶加入合成树脂乳液或辅助成膜物质为基料制成的涂料。国内目前应用的无机建筑涂料基本上属于这两类。",
+        "category": " Introduction"
+    },
+    {
+        "id": 954,
+        "chunk": "# 二、无机建筑涂料的应用及发展  \n\n我国古代将石灰加黏土，再和水一起混合成膏状，抹涂于墙面，这可能是最早的无机建筑涂料。欧洲从19世纪开始将水溶性的碱金属硅酸盐用于涂料。那时，人们把水玻璃与天然无机颜料及填料混合在一起，制成了原始的无机涂料应用于建筑装饰。那个时期的许多建筑及精工细琢的壁画在经历了漫长恶劣气候的考验后，至今依然展现出当年绚丽的风采，说明这类无机涂料具有很好的耐久性。  \n\n在近代，无机建筑涂料的开发应用始于20世纪70年代初期石油危机出现后，市场上需求经济耐用的建筑涂料。当时，日本首先研究开发成功了以硅酸盐无机高分子为成膜物质的涂料；德国的BASF、WACKER、BAYER和KEIMFARBEN等公司，也先后研制出了以特制液态硅酸钾为主要成膜物质的新型无机建筑涂料。此后，美国在无机涂料、无机-有机复合建筑涂料方面也有了较快发展。到20世纪80年代初，我国也有这类涂料研究成功的报道。20世纪80年代后期，国内研制了数种硅酸钠、硅酸钾等为成膜物的无机涂料。但是，真正在工程上得到大量应用的主要是以硅溶胶为主要成膜物质、以合成树脂乳液为辅助成膜物质的无机外墙涂料和以硅酸钾为主要成膜物质的双组分外墙涂料。近二十年来，这些建筑涂料已在全国范围内生产应用。有些无机外墙涂料的使用寿命超过十年，仍然不粉化、无脱落、开裂等现象，涂膜基本完好，尚具有一定的装饰效果。  \n\n除了普通装饰功能为主的外墙涂料以外，无机功能性墙面涂料也得到了很好的应用与发展，其主要品种有无机防霉涂料、无机绝热涂料、无机防结露涂料和无机防火涂料等，见表3-1-77。其中，无机防火涂料主要应用于钢结构的构件中，而在墙面上的应用较少。  \n\n表3-1-77无机功能性建筑涂料的种类和特性  \n\n\n<html><body><table><tr><td>涂料种类</td><td>主要组成材料</td><td>优 点</td><td>缺 点</td></tr><tr><td>无机防霉涂料</td><td></td><td></td><td>性装饰效果差,涂膜</td></tr><tr><td>无机绝热涂料</td><td>（复、钠水玻璃（配森》化剂）或溶胶 剂等</td><td>合耐热性好（可用4℃，右场 长霉</td><td>易吸湿，吸湿后绝 热效果降低</td></tr><tr><td>无机防结露涂料</td><td>等无机摄料（水泥料硅溶胶或硅酸盐溶液</td><td>耐防好效果最为显著，成本低，</td><td>涂对于有机学料 能差</td></tr><tr><td>有机-无机复合型防 水涂料</td><td>硅酸盐或普通硅酸盐水泥、情性填充 材料和弹性合成树脂乳液以及助剂等</td><td>生产技术简单，防水效果可靠， 施工简单,成本低,耐久性和环保</td><td>双组分，施工质量 易受影响，成本高</td></tr><tr><td>无机防火涂料</td><td>合酸盐(）或殖(质形燃生成 助剂）</td><td>能好</td><td>装饰效果差，涂膜 性脆</td></tr></table></body></html>  \n\n无机涂料的发展已经受到普遍重视，日本和欧洲一些国家提出“涂料无机化”的观点，我国台湾和东南亚地区对此也很重视。无机涂料的应用与发展在范围方面基本上是集中在建筑涂料和功能型涂料领域（包括建筑涂料和工业涂料)；在技术方面则是利用无机成膜物或/和有机成膜物一起拼混制成涂料（单组分和双组分)。近年来，欧美和日本等国家利用溶胶-凝胶法制备水性无机涂料，从技术上上了一个台阶。该类技术能够克服水性无机涂料所存在的许多性能缺陷。我国台湾的一些学者已经利用溶胶-凝胶技术发展了系列水性无机涂料。此外，利用溶胶-凝胶技术已经进行的无机涂料的改进工作有： $\\Phi$ 改善单包装硅酸盐类涂料的贮存稳定性、成膜性能和装饰性能，扩大其功能应用范围，如用硅酸盐为主成膜材料，配合少量偶联剂制成水性无机建筑涂料，具有抗菌、除臭、难燃和自洁作用，这类涂料已经在建筑装修中大量使用，并在工业防腐涂装中推广； $\\textcircled{2}$ 在硅溶胶类涂料中不用或少用合成树脂乳液，由于溶胶-凝胶技术使涂料性能的提高，所得到的涂料不仅用于建筑装修，而且开始用于不同领域的工业涂装。  \n\n在国内，由于无机涂料的许多优点已得到广泛认同，近年来建筑涂料行业虽然是以合成树脂乳液涂料为主导产品，但对无机建筑涂料的研究与开发并没有停止过，并出现了新的现象。国内已经有多家专门生产无机建筑涂料的企业。实践证明，无机建筑涂料要发展，必须提高无机建筑涂料的产品质量，生产高性能以及能够满足涂料施工、涂膜装饰和各种物理化学性能的产品满足市场。",
+        "category": " Introduction"
+    },
+    {
+        "id": 955,
+        "chunk": "# 三、无机建筑涂料的基料",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 956,
+        "chunk": "# 1.水玻璃  \n\n（1）种类及组成水玻璃分子式的通式为 $\\mathrm{Me}_{2}\\mathrm{O}\\cdot n\\mathrm{SiO}_{2}\\cdot m\\mathrm{H}_{2}\\mathrm{O}$ ，Me可以是钠、钾、锂和铵四种离子，n为模数。水玻璃根据Me离子的不同分别称为钾水玻璃、锂水玻璃、钠水玻璃、铵水玻璃等。锂水玻璃和铵水玻璃价格高，在外墙涂料中的实用价值不大。钾水玻璃价格中等，且成膜后涂膜的耐水性好；钠水玻璃虽价格低廉，但因为制成的涂料性能差，因而在建筑涂料中的应用有限。  \n\n(2）水玻璃的物理化学特性及作为涂料基料的性能  \n\n$\\Phi$ 物理化学特性水玻璃的外观是呈无色、青绿色或棕色的固体或黏稠类液体。水玻璃的质量以无色透明者为好。液体水玻璃可以与水以任何比例混合而成为浓度不同的溶液。水玻璃的组成中包含有多种成分，包括无定形的二氧化硅、水合物、氢氧化物、正硅酸以及多种聚硅酸盐阴离子。阴离子的种类及其含量与水玻璃的模数及 $\\mathsf{p H}$ 有关。  \n\n$\\textcircled{2}$ 水玻璃作为涂料基料使用时的性能水玻璃的主要特性有：良好的黏结性能；硬化时析出的硅酸凝胶有堵塞毛细孔隙而防止水渗透的作用；不燃烧，耐热，在高温下硅酸凝胶干燥得更加强烈而强度并不降低，甚至有所增强以及具有高度的耐酸性能等。  \n\n水玻璃作为涂料基料使用时具有的优点有：a.具有不燃性、无烟性，在发生火灾时完全不产生烟和有毒有害性气体；b.具有优异的耐热性和耐候性，紫外线和臭氧等引起的副作用小，耐热度一般为 $500\\sim600^{\\circ}\\mathrm{C}$ ，使用耐热性填料的涂料可在 $1000^{\\circ}\\mathrm{C}$ 的场合下使用；c.与无机类基材有牢固的黏结力；d.具有调湿、防结露性、防霉性，霉菌不容易生长，并有一定的防虫效果；e.膜层的硬度很高，不容易受到机械损伤；f.有一定的导电性，因静电而吸附的尘埃较少（与有机涂料相比)；g·溶于水，易处理，资源丰富，无环境危害之虞。  \n\n水玻璃作为涂料基料使用时具有的缺点有：a.耐水性差，必须掺用固化剂，且由于硬化收缩可能会导致涂膜开裂或黏结性不良；b.涂层脆而无弹性，没有适应基材胀缩变化和裂缝张闭的能力，耐冲击性也较差；且与有机材料的黏结不良；c.涂层无光泽，不透明；d.透水性、透气性大，故防渗透性差。  \n\n(3）水玻璃的固化技术液体水玻璃在空气中吸收二氧化碳，形成无定形硅酸并逐渐干  \n\n燥而固化。其固化成膜机理的反应式如下。  \n\n![](images/0844cac8a52bee9b3d31a8c384d5aa33d1d39047808dfb89589b3edc3a8a40fe.jpg)  \n网状结构的涂膜  \n\n式中，Me为碱金属离子，如Na、K等；n为水玻璃的模数； $_x$ 为大于或等于1的自然数。  \n\n由于水玻璃在空气中固化过程很缓慢，且所得到的涂膜耐水性不良，为了加速固化和提高涂膜的耐水性，常常向水玻璃涂料中加人固化剂，固化剂既可以与碱金属离子反应生成水不溶物，又可以促进二氧化硅胶体进一步缩合成耐水涂膜。该法称为水玻璃的固化技术，也称为水玻璃的碱金属离子固定化技术。  \n\n过去，建筑上常使用氟硅酸钠 $(\\mathrm{Na}_{2}\\mathrm{SiF}_{6}$ ）作为固化剂加入到钠水玻璃中。钠水玻璃在加入氟硅酸钠以后会发生化学反应，促进硅酸凝胶加速析出。氟硅酸钠的用量为水玻璃重量的 $12\\%\\sim15\\%$ 时较为适宜。用量少不但硬化速率慢，达不到所希望的促进硬化效果，强度降低，同时未经反应的水玻璃易溶于水，因而耐水性也差；用量大则会导致凝结硬化速度过快，不但使用困难，而且渗透性增大，强度也会降低。氟硅酸钠既影响水玻璃的固化速率，对涂料的干燥速率必然产生一定影响。  \n\n在硅酸钾建筑涂料中，典型的是使用缩合磷酸盐（AI、 $\\mathbf{M}_{\\mathbf{\\overline{{B}}}}$ 、Ca盐等）或 $\\beta$ 硅酸二钙作为固化剂；或者除使用缩合磷酸盐类材料作为主固化剂以外，还采用一种或几种辅助固化剂（主要为 $z_{\\mathrm{nO}}$ 。 $\\mathrm{Al}_{2}\\mathrm{O}_{3}$ 、硼酸盐等)，以取得较好的固化效果。  \n\n当使用缩合磷酸盐作为固化剂时，缩合磷酸盐在涂料中缓慢水解，释放出 $\\mathrm{H^{+}}$ ·$\\mathbf{H}^{+}$ 与水玻璃反应，使其析出胶体二氧化硅，胶体二氧化硅自行缩合形成以—Si—O—Si一为主链的无机网状薄膜，磷酸根则与金属离子 $\\mathrm{Al^{3+}}$ 、 $\\mathrm{\\DeltaNa^{+}}$ 、 $\\mathrm{K^{+}}$ 等反应形成不溶于水的复盐。  \n\n目前在市场上并没有作为硅酸钾建筑涂料固化剂使用的缩合磷酸盐商品，一般是生产涂料时合成。  \n\n(4）水玻璃的改性水玻璃用作涂料基料时其耐水性不良是其性能上的不足。可以通过一些改性措施来提高其耐水性能以及其他性能。如酸改性水玻璃、与合成树脂乳液复合使用、钠水玻璃的偶联剂改性、用锂水玻璃改性钠水玻璃、钾水玻璃等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 957,
+        "chunk": "# 2.硅溶胶  \n\n(1）定义与特性硅溶胶亦称硅酸溶胶，文献资料上也有将其称为纳米二氧化硅或者硅酸溶胶的，是一种含有一定浓度的、颗粒粒径为纳米级的无定形二氧化硅的水溶胶分散体，一般成透明、半透明或乳白色液体，浓度高时呈胶状。硅溶胶的分子式可表示为 $m\\mathrm{{SiO_{2}}}$ ·$n\\mathrm{H}_{2}\\mathrm{O}$ 。由于纳米胶体硅是无机二氧化硅的水溶胶，因而是一种无毒、无环境危害的产品。硅溶胶种类很多，根据化学成分可以分为改性钠型、铵型和超纯型等；根据 $\\mathsf{p H}$ 的不同可以分为酸性、中性和碱性等；根据所带电荷的不同可以分为阴离子型、阳离子型和去离子  \n\n型等。  \n\n硅溶胶中的二氧化硅颗粒粒径一般为 $5\\sim150\\mathrm{nm}$ ，比表面积为 $20\\sim800\\mathrm{m}^{2}/\\mathrm{g}$ ：pH值可以为 $2\\sim4$ 或 $_{9\\sim11}$ 。另外，硅溶胶的黏度较小，一般小于 $\\mathrm{5mPa\\cdot}$ 3。特殊情况下，黏度可为 $1{\\sim}155\\mathrm{mPa}\\cdot\\mathrm{s}$ 。  \n\n(2）硅溶胶的涂料特性硅溶胶用于涂料的一个最突出的优点就是具有一旦成膜就不会再溶解的特性，因而使用硅溶胶作基料生产的涂料通常具有很好的耐水性。此外硅溶胶作为涂料基料使用时还具有如下特点。  \n\n$\\Phi$ 因颗粒细微(接近分子状态)，析胶时的 $\\mathrm{SiO}_{2}$ 具有较高的活性，黏结包裹涂料中的粉状颗粒，与某些无机盐类、金属氧化物生成新的硅酸盐无机高分子化合物，硬化成膜。细微的颗粒对基层渗透力强，可通过毛细管作用渗入到基材的内部，并与混凝土基层中的$\\mathrm{Ca(OH)}_{2}$ 生成硅酸钙 $\\mathrm{CaSiO_{3}}$ )，使涂料具有较强的黏结力。  \n\n$\\textcircled{2}$ 硅溶胶中 $_{\\textrm{N a2}}\\textrm{N a}$ 含量低，因而涂膜具有较好的耐水性；由于与基层反应缓慢，涂料具有较好的涂刷性，无盐析现象，颜色均匀，装饰效果好。  \n\n$\\textcircled{3}$ 硅溶胶和某些有机高分子聚合物混溶能硬化成膜。这种涂膜保持了无机涂料具有的硬度；又具有一定的柔性，保持了有机涂料快干、易刷性，兼具无机涂料和有机涂料的优点。  \n\n(3）硅溶胶使用注意事项  \n\n$\\Phi$ 硅溶胶的添加量硅溶胶的添加量一般为乳液固体成分的 $30\\%\\sim60\\%$ ，与合成树脂乳液的性能，例如玻璃化温度、成膜助剂等的使用有关。当合成树脂乳液的玻璃化温度较低时，硅溶胶的用量可以大些。但是，如果硅溶胶的添加量过高，会导致涂膜的耐化学腐蚀性和耐冲击性降低。  \n\n$\\textcircled{2}$ 注意材料之间的相容性使用硅溶胶时，应首先注意检查其和分散剂、合成树脂乳液的相容性，根据相容性确定各种材料的选用。  \n\n$\\textcircled{3}$ 注意涂料助剂的选用配制硅溶胶涂料时除应按水性涂料的要求使用各种助剂外，还可以根据硅溶胶涂料的特点，有目的地选择能够改善性能的功能性添加剂。例如，使用商品名称为 $\\mathsf{K H-}560$ 的硅烷偶联剂能够实现硅溶胶和合成树脂乳液之间的偶合，很多硅溶胶有机-无机复合涂料的研究中都有这类助剂的应用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 958,
+        "chunk": "# 四、外墙无机建筑涂料的配制要点及生产技术分析",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 959,
+        "chunk": "# 1.硅溶胶外墙涂料  \n\n因为硅溶胶的固体含量低、干燥收缩大，所以仅使用硅溶胶不能够制成具有实用意义上的建筑涂料，而是需要复合一定数量的合成树脂乳液。因而，这类涂料也称为有机-无机复合外墙涂料，是得到广泛应用的无机外墙涂料，具有如下特点：  \n\n$\\textcircled{1}$ 硅溶胶中Si一O键的键能大，具有较好的键合稳定性，再加上丙烯酸酯的涂膜性能也非常优异，所以复合涂料的耐候性比未复合的涂料品种有提高；  \n\n$\\textcircled{2}$ 微细的 $\\mathrm{\\SiO}_{2}$ 颗粒具有很大的比表面积，容易形成牢固的硅氧键网状结构，使涂料具有很好的耐水性、耐洗刷性和耐碱性；  \n\n$\\textcircled{3}$ 从微观结构的研究分析可知，涂膜中复合基料粒子呈球形或接近球形排列，表面平整致密，间隙很小，使得细微的尘埃不易侵入其间隙中；同时，Si一O键的结构属于离子型，具有较好的导电性，不会产生电荷积累，即不产生静电，尘埃难以黏附，加之涂膜中无机基团的引入，改善了丙烯酸酯的回黏性，因而涂膜具有很好的耐沾污性能。  \n\n但这类涂料在配制技术上有一定难度，主要是涂料的贮存稳定性问题。处理得不好会导  \n\n致涂料的贮存性能不良。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 960,
+        "chunk": "# (1）配方举例和配制  \n\n$\\Phi$ 配方表3-1-78中列示出无机-有机复合外墙涂料的配方。该配方中的硅溶胶的用量和丙烯酸酯乳液的用量基本上相当。表3-1-79为另一个硅溶胶建筑涂料配方实例，其硅溶胶的用量远高于丙烯酸酯乳液的用量。像这类以硅溶胶为主而只复合少量丙烯酸酯乳液的涂料，一般称为无机建筑涂料比较合适。  \n\n表3-1-78无机-有机复合外墙涂料配方举例  \n\n\n<html><body><table><tr><td>涂料组分</td><td>原材料名称</td><td>用量（质量分数）/%</td></tr><tr><td>基料</td><td>复合基料</td><td>46.0</td></tr><tr><td rowspan=\"3\">颜料、填料</td><td>钛白粉</td><td>18.0</td></tr><tr><td>硅灰石粉</td><td>10.0</td></tr><tr><td>滑石粉</td><td>6.0</td></tr><tr><td rowspan=\"6\">助剂</td><td>F-974成膜助剂</td><td>2.8</td></tr><tr><td>Tamol 731湿润分散剂</td><td>0.5</td></tr><tr><td>DX消泡剂</td><td>适量</td></tr><tr><td>羟乙基纤维素</td><td>0.5</td></tr><tr><td>有机增稠剂</td><td>0.9</td></tr><tr><td>氨水（pH调节剂）</td><td>适量</td></tr><tr><td>分散介质</td><td>水</td><td>补足100%用量</td></tr></table></body></html>  \n\n表3-1-79无机外墙建筑涂料的配方举例  \n\n\n<html><body><table><tr><td>原材料名称</td><td>用量（质量分数)/%</td><td>原材料名称</td><td>用量（质量分数）/%</td></tr><tr><td>硅溶胶（20%）</td><td>35.88</td><td>增稠剂-B</td><td>1.55</td></tr><tr><td>丙烯酸酯乳液（40%）</td><td>13.04</td><td>分散剂-6</td><td>0.05</td></tr><tr><td>金红石型钛白粉</td><td>9.67</td><td>分散剂-N</td><td>0.18</td></tr><tr><td>轻质碳酸钙</td><td>7.25</td><td>消泡剂</td><td>0.02</td></tr><tr><td>滑石粉</td><td>8.70</td><td>成膜助剂</td><td>3.14</td></tr><tr><td>瓷土</td><td>2.90</td><td>防腐剂</td><td>0.36</td></tr><tr><td>云母粉</td><td>2.42</td><td>水</td><td>7.25</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 根据当丙烯酸酯乳液和硅溶胶所含固体摩尔比为 $1.4{\\sim}1.5$ 时，体系最为稳定”的研究结果来分析计算，并考虑常用涂料原材料情况，即当丙烯酸酯乳液和硅溶胶的固体含量分别为 $49\\%$ 和 $25\\%$ 时，复合基料的丙烯酸酯乳液和硅溶胶的用量分别为 $19.17\\%\\sim19.$ 94%和$26.06\\%\\sim26.83\\%$ 西  \n\n(2）配制程序表3-1-79中配方的生产工艺如下：按配方，把水和硅溶胶投人反应釜中混合均匀，再投入分散剂搅拌均匀后，投入颜料和填料，充分搅拌均匀。然后，将混合料浆通过砂磨机或胶体磨进行磨细/研磨后进行调漆操作，即投入乳液和助剂，充分搅拌混合均匀，过滤包装，得到成品无机外墙建筑涂料。  \n\n(3）硅溶胶复合建筑涂料的稳定性问题硅溶胶复合建筑涂料在我国使用已有20多年历史，这类涂料的优异性能已经得到比较一致的认同。但是，这类涂料的贮存稳定性问题也一直受到重视，原因是稳定性问题影响这类涂料的使用。根据作者以及其他人对这类涂料的研究，认为影响其贮存稳定性问题的有复合涂料体系的 $\\mathsf{p H}$ 、硅溶胶粒子的粒径以及颜料、填料、拼混使用的乳液性能和助剂的使用等因素。  \n\n$\\textcircled{1}$ 复合涂料体系的pH $\\mathsf{p H}$ 对硅溶胶的稳定性会产生重要影响，进而影响涂料的稳定性。有研究表明，硅溶胶类复合涂料的pH对其贮存稳定性的影响如图3-1-20所示。  \n\n处于 $\\mathsf{p H}$ 为7的中性状态的硅溶胶会迅速凝胶，这是因为当 $\\mathbf{pH}$ 等于7时，硅溶胶颗粒表面双电层消失；而当 $\\mathfrak{p H}$ 大于12时，硅溶胶转变为模数等于或大于5的水不溶性硅酸钠而发生凝胶，导致体现不稳定。  \n\npH对硅溶胶稳定性的影响可以从硅溶胶自身的结构中得到解释。硅溶胶是聚偏硅酸的胶体溶液，胶体粒子表面一般都带电荷，并分散于介质中， $\\mathrm{SiO}_{2}$ 和水作用发生水化，产生羟基，羟基解离使粒子的表面带电。粒子表面的电位随介质的pH发生变化。  \n\n![](images/f4e3a5c4bddc60d014058aa33d3a531862a9e38b1e99df52ed73434fd48ca3fb.jpg)  \n图3-1-20硅溶胶类复合涂料的pH对其贮存稳定性的影响  \n\n在低 $\\mathsf{p H}$ 条件下，因质子的加入， $\\mathrm{\\SiO}_{2}$ 粒子表面带正电。当提高体系的pH值时，因 $\\mathrm{OH^{-}}$ 的作用 $\\mathrm{\\SiO_{2}}$ 粒子表面带负电。粒子表面电荷为零时介质的 $\\mathsf{p H}$ 即是该氧化物的等电点。 $\\mathrm{SiO}_{2}$ 的等电点，即 $\\mathbf{\\Pi}_{\\mathbf{pH}}$ 值为 $1.~5\\sim3.~7$ 。因而，通常商品硅溶胶有两类：一类是碱性氧化钠稳定型， $\\mathfrak{p H}$ 值为 $8.5\\sim10.5$ ；另一类是酸性无稳定型， $\\mathsf{p H}$ 值为 $2\\sim4$ α  \n\n实际上，当 $\\mathbf{p}\\mathbf{H}{>}7$ 时， $\\mathrm{SiO}_{2}$ 胶体粒子表面全部带负电，胶体因静电排斥而稳定；而当$\\mathrm{\\pH}<3$ 时， $\\mathrm{SiO}_{2}$ 胶体粒子表面全部带正电荷，胶体亦会因静电排斥而稳定。在 $3<p\\mathrm{H}<7$ 的情况下，胶体易凝聚而破坏。当氧化钠含量过多， $\\mathsf{p H}=11$ 时，胶体也易凝聚而破坏。因此，当硅溶胶和合成树脂乳液复合时需要保证体系的 $\\mathsf{p H}$ 呈弱碱性，即使体系的 $\\mathsf{p H}$ 值为$8.5\\sim10.0$ 费  \n\n因此，在生产硅溶胶类复合涂料时，应当设法将涂料体系的 $\\mathsf{p H}$ 控制在 $8.5\\sim10.0$ 的范围内以保持涂料的稳定性。至于调整涂料体系的 $\\mathsf{p H}$ 的方法，可以用最常见的氨水进行调整；也可以用其他更为优异的涂料助剂（例如AMP-95多功能涂料助剂）或材料调整。  \n\n$\\textcircled{2}$ 硅溶胶粒子的粒径硅溶胶粒子的粒径分布为 $5\\sim80\\mathrm{nm}$ ，在此范围内，硅溶胶外观基本成透明状态。在粒径小于 $5n\\mathbf{m}$ 时，胶体微粒的比表面积巨大，水的隔离作用减弱，粒子发生凝聚的概率增大。在粒径大于 $30\\mathrm{nm}$ 时，硅溶胶外观出现浑浊，对颜料的包裹能力差，涂料沉降快，不稳定。表3-1-80表明，小粒径硅溶胶的添加量低 $(<12\\%)$ ，涂料的稳定性好；用量大时涂料的稳定性下降，涂膜的耐水性也下降，浸水易起泡。大粒径的硅溶胶的添加量大，体系的稳定性好。对于使用纯硅溶胶配制的无机涂料体系，硅溶胶有凝聚的可能性。  \n\n表3-1-80硅溶胶粒径和涂料稳定性及涂膜耐水性的关系  \n\n\n<html><body><table><tr><td rowspan=\"2\">性能</td><td colspan=\"4\">粒径SiO</td></tr><tr><td>5~8nm</td><td>8~15nm</td><td>20nm</td><td>25nm</td></tr><tr><td>涂料贮存稳定性 涂膜耐水性</td><td>无异常 起泡</td><td>无异常 无变化</td><td>结块 无变化</td><td>结块 无变化</td></tr></table></body></html>\n\n$\\Phi$ “涂料贮存稳定性”试验的贮存时间为6个月。$\\textcircled{2}$ “涂膜耐水性”试验的浸水时间为20天。  \n\n$\\textcircled{3}$ 颜料、填料当复合涂料体系的颜料、填料选用得不当时也有导致涂料体系不稳定的可能。例如，涂料体系中使用了氧化锌、游离氧化钙含量较高的轻质碳酸钙等，就有可能造成这类涂料的贮存稳定性不良。  \n\n复合涂料中不宜使用氧化锌颜料的原因在于，氧化锌作为颜料使用时其活性较大，且 $Z n^{2+}$ 具有导致某些使用阴离子乳化剂的乳液破乳的可能性，而复合涂料的成膜物质中的有机组分即为合成树脂乳液（例如丙烯酸酯类乳液、聚醋酸乙烯酯类乳液和有机硅-丙烯酸酯共聚乳液等)，因而，白色颜料仍以使用金红石型钛白粉为宜。轻质碳酸钙是由氧化钙和二氧化碳反应而得到的。当因种种原因的影响而使碳化进行得不完全时，产品中就会残留有含量较高的游离氧化钙。这部分氧化钙会改变涂料体系的 $\\mathsf{p H}$ 。此外，其中的游离氧化钙还会影响乳液的钙离子稳定性，又有可能和硅溶胶产生下述化学反应。  \n\n$$\n\\mathrm{Ca(OH)}_{2}+\\mathrm{H}_{2}\\mathrm{SiO}_{3}\\longrightarrow\\mathrm{CaSiO}_{3}\\cdot2\\mathrm{H}_{2}\\mathrm{O}\n$$  \n\n所生成的 $\\mathrm{CaSiO_{3}}\\cdot2\\mathrm{H}_{2}\\mathrm{O}$ 是凝胶，是可能具有一定强度的固体，从而导致涂料体系不稳定。  \n\n可见，为了使硅溶胶复合涂料具有好的贮存稳定性，应尽可能使涂料体系的pH控制在$8.5\\sim10.0$ 的范围内。显然，复合涂料中还不应使用 $\\mathfrak{p H}$ 在 $8.5\\sim10.0$ 范围内不稳定的材料，而游离氧化钙较高的轻质碳酸钙就是如此。  \n\n$\\textcircled{4}$ 拼混使用的乳液性能的影响不同性能的硅溶胶与同一种合成树脂乳液（主要指丙烯酸酯乳液或苯丙乳液）拼混使用时，或者两者拼混的比例不同时，所得到的复合体系会表现出不同的稳定性。同样，同一种合成树脂乳液与不同性能的硅溶胶拼混使用，或者两者拼混的比例不同时，也可能得到稳定性不同的复合体系，即硅溶胶和合成树脂乳液复合时有一个品种适应性和最佳比例的问题。因而，在制备复合涂料时，应对所选用的原材料进行试验。  \n\n$\\textcircled{5}$ 助剂助剂不但会影响复合涂料的稳定性，用得不当也会造成其他类涂料的不稳定，因而必须注意正确选用。一般来说，分散剂应当选用分散效果稳定的阴离子分散剂；增稠剂宜选用黏度型号适当的羟乙基纤维素或者羟丙基甲基纤维素。此外，选用适当的分散剂对复合体系中的硅溶胶进行保护，也是得到稳定性良好的复合涂料的一种方法。 $\\mathrm{SiO}_{2}$ 粒子属于无机氧化物，具有极性，需要选择具有特殊结构的湿润分散剂才能吸附于 $\\mathrm{SiO}_{2}$ 粒子表面而使之得到保护。因而，湿润分散剂的选择非常重要。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 961,
+        "chunk": "# 2.硅酸钾（钾水玻璃）外墙涂料  \n\n硅酸钾外墙涂料有两类：一类是复合少量合成树脂乳液的单组分涂料；另一类是施工时外加固化剂的双组分涂料。在硅酸钾涂料中加入超微细滑石粉，当滑石粉的细度达到3000目，而特别是达到5000目时，涂料的附着力能够得到十分明显的改善。  \n\n(1）配方表3-1-81中给出了单组分和双组分的两种硅酸钾无机外墙涂料的配方。在单组分硅酸钾类配方中，使用了较高比例的SBR乳液，这是一种物理拼混法的有机-无机复合型涂料。双组分硅酸钾涂料能够体现出无机外墙涂料所具有的各种特征，例如硬度、性脆、耐老化性能好和成本低等一些特性。  \n\n(2）涂料生产工艺表3-1-81中单组分硅酸钾外墙涂料的生产程序类似于硅溶胶类复合外墙涂料，简述如下。  \n\n表3-1-81无机硅酸钾外墙涂料配方  \n\n\n<html><body><table><tr><td rowspan=\"2\">原材料</td><td colspan=\"2\">用量（质量分数)/%</td></tr><tr><td>单组分硅酸钾类</td><td>双组分硅酸钾类</td></tr><tr><td>钾水玻璃</td><td>100.0</td><td>40.0</td></tr><tr><td>苯丙(苯乙烯-丙烯酸酯）乳液</td><td>20. 0~25.0</td><td></td></tr><tr><td>颜料和填料</td><td>35. 0~48. 0</td><td>100. 0~160. 0</td></tr><tr><td>分散剂（阴离子型）</td><td>0.3~0.6</td><td>0. 3~1.35</td></tr><tr><td>消泡剂</td><td>0.2 ~0.4</td><td>消泡量</td></tr><tr><td>增稠剂</td><td>适量</td><td>3.0~5.0</td></tr><tr><td>成膜助剂</td><td>1.0~3.0</td><td>一</td></tr><tr><td>其他助剂</td><td>一</td><td>常用量</td></tr><tr><td>固化剂(缩合磷酸铝)</td><td>一</td><td>6.0~8.0</td></tr><tr><td>水</td><td>10.0~20.0</td><td>15. 0~25.0</td></tr></table></body></html>\n\n$\\Phi$ 为江阴国联化工公司生产的钾水玻璃。$\\textcircled{2}$ 颜料、填料的种类和用量（%）如下：金红石型钛白粉22；超细懒烧高岭土16；重质碳酸钙37；滑石粉10；氧化锌15。  \n\n$\\textcircled{1}$ 把硅酸钾溶液投入搅拌罐中，加水搅拌均匀。  \n\n$\\textcircled{2}$ 向搅拌罐中投入分散剂，然后投入各种颜料、填料，搅拌均匀后，再投入成膜助剂和部分消泡剂，高速 $(800{\\sim}1000\\mathrm{r/min})$ 搅拌0.5h得到料浆。将该料浆经砂磨机研磨至细度小于 $60\\mu\\mathrm{m}$ ，再将磨细的混合料浆转移至搅拌罐中。  \n\n$\\textcircled{3}$ 在低速 $(300{\\sim}500\\mathbf{r}/\\operatorname*{min})$ 搅拌状态下，将SBR乳液缓慢地加人揽拌罐中，加完后再搅拌约 $20\\mathrm{min}$ 使之均匀。视泡沫的多少再酌加适量消泡剂，搅拌消泡。  \n\n$\\textcircled{4}$ 如果需要配制彩色涂料，可以根据色卡经试验确定加入色浆的种类和数量，然后搅拌均匀调配成所需要的颜色。  \n\n双组分硅酸钾外墙涂料的生产工艺和上述单组分涂料的大同小异。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 962,
+        "chunk": "# 3.新型水玻璃基涂料——地聚物涂料  \n\n在20世纪70年代末，美国的J.Davidovits对水玻璃激发偏高岭土进行了详细研究，所得的黏结剂称为地聚物水泥（geopolymericcement），该水泥在 $20\\%$ 硬化4h后的抗压强度能够达到 $20\\mathrm{MPa}$ ，28天后的抗压强度达 ${70}\\mathrm{{\\sim}100}\\mathrm{{MPa},}$ ，自1976年申请一项美国专利以来，在英国、法国、欧洲等国已获专利30余项，内容涉及混凝土、耐火材料、涂料以及其他建筑材料等。  \n\n(1）地聚物水泥的基本特性地聚物水泥的最终产物类似天然沸石矿物，其结构是三维铝硅酸盐结构， $\\mathrm{{Na^{+}}}$ ， $\\mathbb{K}^{+}$ 等阳离子存在于三维结构的空腔中，以平衡V配位 $\\mathsf{A l^{3+}}$ 的负电荷。其经验化学式如下：  \n\n$$\n[(\\mathbf{M}\\mathbf{n})(\\mathbf{S}\\mathbf{i}\\mathbf{O}_{2})_{\\pmb{\\imath}}-\\mathbf{A}\\mathbf{l}_{2}\\mathbf{O}_{3}]_{\\pmb{\\imath}}\\cdot\\boldsymbol{w}\\mathbf{H}_{2}\\mathbf{O}\n$$  \n\n式中，Mn是 $\\mathrm{{Na^{+}}}$ ， $\\mathbf{K}^{+}$ 等阳离子； $n$ 是聚合度； $_z$ 的值1，2，3；w是结合水量，  \n\n天然沸石类矿物是自然界的造岩矿物，其溶解度非常低，这从根本上解决了水玻璃基涂料的耐水性问题。  \n\n地聚物水泥与传统水泥的主要区别在于地聚物不存在硅酸钙的水化反应，其最终产物以离子键以及共价键为主，以范德瓦尔斯键为辅，其性能类似天然沸石矿物，而传统水泥则以范德瓦尔斯键以及氢键为主。因此其主要性能优于传统水泥。地聚物在工艺上采用了诸如陶瓷生产的方法，又被称为低温非烧陶瓷或化学键合陶瓷。地聚物是由无机的硅-氧四面体与铝-氧四面体聚合而成，所以地聚物又具有有机高聚物的键接结构。总之，地聚物兼有有机高聚物、陶瓷、水泥的特点，又不同于上述材料，具有许多独特的材料性能。我国对水玻璃激发偏高岭土的研究与利用尚没有引起足够的重视，特别是用作涂料的研究还是空白。  \n\n(2）涂料的耐腐蚀性及分析将上述制得的地聚物涂料和水玻璃涂料的涂膜试板分别置于去离子水、海水、4.4%硫酸钠溶液和0.001mol/L硫酸溶液中分别浸泡1天、30天和180天。结果表明，地聚物涂料在这四种介质中浸泡至180天，其涂膜仍保持完整；而水玻璃基涂料浸泡1天其涂膜就软化并脱落。说明这两种涂料的耐化学侵蚀性有本质差别。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 963,
+        "chunk": "# 五、外墙无机建筑涂料的技术性能要求  \n\nJG/T26—2002规定的外墙无机建筑涂料的技术性能指标见表3-1-82。从表中可见，无机外墙建筑涂料的耐人工老化性较合成树脂乳液类外墙涂料要求的时间长，也说明这类外墙涂料具有更好的耐久性。  \n\n表3-1-82外墙无机建筑涂料技术性能指标  \n\n\n<html><body><table><tr><td>技术性能项目</td><td>指标要求</td></tr><tr><td>容器中状态</td><td>搅拌后无结块、呈均匀状态</td></tr><tr><td>施工性</td><td>刷涂两道无障碍</td></tr><tr><td>涂膜外观</td><td>涂膜外观正常</td></tr><tr><td>对比率（白色和浅色）</td><td>≥0.95</td></tr><tr><td>热贮存稳定性（30天）</td><td>无结块、凝聚、霉变现象</td></tr><tr><td>低温贮存稳定性(3次)</td><td>无结块、凝聚现象</td></tr><tr><td>表干时间/h</td><td>≤</td></tr><tr><td>耐洗刷性/次</td><td>≥1000</td></tr><tr><td>耐水性(168h)</td><td>无起泡、裂纹、剥落，允许轻微掉粉</td></tr><tr><td>耐碱性(168h)</td><td>无起泡、裂纹、剥落，允许轻微掉粉</td></tr><tr><td>耐温变性(10次)</td><td>无起泡、裂纹、剥落，允许轻微掉粉</td></tr><tr><td>耐沾污性/%</td><td></td></tr><tr><td>I类</td><td>≤20</td></tr><tr><td>Ⅱ类</td><td>≤15</td></tr><tr><td>耐人工老化性（白色和浅色）</td><td></td></tr><tr><td>I类800h</td><td>无起泡、裂纹、剥落，粉化≤1级；变色≤2级</td></tr><tr><td>Ⅱ类500h</td><td>无起泡、裂纹、剥落，粉化≤1级；变色≤2级</td></tr></table></body></html>\n\n$\\Phi$ 浅色是指以白色涂料为主要成分，添加适量色浆后配制成的浅色涂料形成的涂膜所呈现的灰色、粉红色、奶黄色、浅绿色等浅颜色，按GB/T15608--1995中4.3.2规定的明度值为6～9.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 964,
+        "chunk": "# 六、无机外墙建筑涂料施工技术",
+        "category": " Introduction"
+    },
+    {
+        "id": 965,
+        "chunk": "# 1.外墙基层的类型及其缺陷处理  \n\n(1）基层类型及其特征外墙建筑涂料施工中常见的基层材料有混凝土、水泥砂浆、混合砂浆等，其共同特点是吸水率高、碱性大。表3-1-83中列出这些基层的基本特征。  \n\n表3-1-83外墙基层及其特征  \n\n\n<html><body><table><tr><td>基层种类</td><td>特 征</td></tr><tr><td>混凝土（包括轻混 凝土、加气混凝土、预 制混凝土等）</td><td>表面多孔、粗糙、吸水率大，碱性较大，经长时间才能中和，内部渗出的水分也呈碱性；干燥较慢， 并受厚度影响；强度高、坚固</td></tr><tr><td>水泥砂浆</td><td>层厚在10～25mm范围不等；表面状态有粗糙的、有平整光滑的以及不规则的表面；碱性比混凝</td></tr><tr><td>混合砂浆</td><td>土更强，内部渗出的水分也呈现碱性；表面干燥快，内部的含水率受主体结构的影响：强度高，坚固 碱性比水泥砂浆更强，强度不如水泥砂浆高，其他同水泥砂浆</td></tr></table></body></html>  \n\n(2）基层处理基层处理分基层检查、基层清理和基层修补等工序，见表3-1-84。  \n\n表3-1-84基层处理的基本工序  \n\n\n<html><body><table><tr><td>工序名称</td><td>主要内容</td></tr><tr><td>检查基层</td><td>进行基层状况的检查时，应注意：①检查基层的表面有无裂缝、麻面、气孔、脱壳、分离等缺陷；② 检查基层表面有无粉化、硬化不良、浮浆以及有无隔离剂、油类物质等；③检查基层的含水率及碱性</td></tr><tr><td>基层清理</td><td>状况 对基层表面进行清理主要是清理去除表面附着物和不符合要求的疏松部分、粉化层、旧涂层、油 迹、隔离剂、密封材料沾染物、锈迹、霉斑等缺陷</td></tr><tr><td>基层缺陷修补</td><td>对基层进行检查、清理后，对所发现的各种缺陷应根据具体的基层情况和缺陷种类，采取相应的 措施进行修补。</td></tr></table></body></html>  \n\n(3）基层条件建筑工业行业标准JGJ/T29-2003《建筑涂饰工程施工及验收规程》中对基层质量的要求如下：  \n\n$\\textcircled{1}$ 基层应牢固，不开裂、不掉粉、不起砂、不空鼓、无剥离、无石灰爆裂点和无附着力不良的旧涂层等；  \n\n$\\textcircled{2}$ 基层应表面平整，立面垂直、阴阳角垂直、方正和无缺棱掉角，分割缝深浅一致且横平竖直，允许偏差应符合表3-1-85的要求且平而不光；  \n\n表3-1-85涂饰涂料的基层抹灰质量的允许偏差 单位：mm  \n\n\n<html><body><table><tr><td>平整内容</td><td>普通级</td><td>中级</td><td>高级</td></tr><tr><td>表面平整</td><td>5</td><td>4</td><td>2</td></tr><tr><td>阴阳角垂直</td><td>一</td><td>4</td><td>2</td></tr><tr><td>阴阳角方正</td><td>一</td><td>4</td><td>2</td></tr><tr><td>立面垂直</td><td>一</td><td>5</td><td>3</td></tr><tr><td>分割缝深浅一致和横平竖直</td><td>一</td><td>3</td><td>1</td></tr></table></body></html>  \n\n$\\textcircled{3}$ 基层应清洁，表面无灰尘、无浮浆、无油迹、无锈斑、无霉点、无盐类析出物和无青苔等杂物；  \n\n$\\textcircled{4}$ 基层应干燥，涂刷溶剂型涂料时，基层含水率不得大于 $8\\%$ ；涂刷乳液型涂料时，基层含水率不得大于 $10\\%$  \n\n$\\textcircled{5}$ 基层的 $\\mathsf{p H}$ 不得大于10。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 966,
+        "chunk": "# 2.外墙无机建筑涂料的基本施工工序  \n\n(1）混凝土及抹灰外墙面薄质涂料按JGJ/T29—2003《建筑涂饰工程施工及验收规程》的要求，混凝土及抹灰外墙面施工无机薄质涂料的主要施工工序见表3-1-86。  \n\n表3-1-86混凝土及抹灰外墙表面施工无机涂料工程的主要工序  \n\n\n<html><body><table><tr><td>次 序</td><td>工序名称</td><td>次 序</td><td>工序名称</td></tr><tr><td>1</td><td>清理基层</td><td></td><td>第一遍面层涂料</td></tr><tr><td>2</td><td>填补缝隙、局部刮腻子、磨平</td><td>45</td><td>第二遍面层涂料</td></tr><tr><td>3</td><td>涂饰底涂料</td><td></td><td></td></tr></table></body></html>  \n\n(2）厚质建筑涂料厚质建筑涂料主要指砂壁状建筑涂料和复层建筑涂料。可参照JGJ/T29—2003《建筑涂饰工程施工及验收规程》中合成树脂乳液类砂壁状建筑涂料的主要施工工序。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 967,
+        "chunk": "# 3.薄质无机墙面涂料的施工  \n\n(1）施工程序和操作技术要点无机外墙涂料的施工基本上是采用辊涂-刷涂结合的方  \n\n法涂装，近年来由于施工技术逐渐受到重视，喷涂和无气喷涂施工技术也应用于无机外墙涂料的施工。  \n\n(2）施工质量问题及其防免无机外墙涂料在施工时由于涂料质量、基层处理不当、施工质量等原因均会出现施工质量问题，与其他建筑涂料相同，这些问题在施工前采取适当的措施是完全可以避免的。  \n\n(3）施工质量要求无机外墙涂料涂饰工程质量的技术要求见表3-1-87。  \n\n表3-1-87无机外墙涂料涂饰工程质量的技术要求  \n\n\n<html><body><table><tr><td>项次</td><td>项 目</td><td>普通级涂饰工程</td><td>中级涂饰工程</td><td>高级涂饰过程</td></tr><tr><td>1</td><td>反锈、掉粉、起皮</td><td>不允许</td><td>不允许</td><td>不允许</td></tr><tr><td>2</td><td>漏刷、透底</td><td>不允许</td><td>不允许</td><td>不允许</td></tr><tr><td>3</td><td>泛碱、咬色</td><td>不允许</td><td>不允许</td><td>不允许</td></tr><tr><td>4</td><td>流坠、疙瘩</td><td></td><td>允许少量</td><td>不允许</td></tr><tr><td></td><td>颜色、刷纹</td><td>颜色一致</td><td>颜色一致</td><td>颜色一致，无剧痕</td></tr><tr><td>6</td><td>光泽</td><td></td><td></td><td>均匀一致</td></tr><tr><td>7</td><td>开裂</td><td>不允许</td><td>不允许</td><td>不允许</td></tr><tr><td>8</td><td>针孔、砂眼</td><td></td><td>允许少量</td><td>不允许</td></tr><tr><td>9</td><td>分色线平直（拉5m线检查，不足5m拉通线检查）</td><td>偏差不大于5mm</td><td>偏差不大于3mm</td><td>偏差不大于1mm</td></tr><tr><td>10</td><td>五金、玻璃等</td><td>洁净</td><td>洁净</td><td>洁净</td></tr></table></body></html>\n\n注：开裂是指涂料开裂，不包括因结构开裂引起的涂料开裂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 968,
+        "chunk": "# 第四节建筑防水涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 969,
+        "chunk": "# 一、概述",
+        "category": " Introduction"
+    },
+    {
+        "id": 970,
+        "chunk": "# 1.定义与作用  \n\n建筑防水涂料简称防水涂料，是指能够形成防止水通过或渗透的涂膜防水材料，是以防水为主要目的的功能性建筑涂料。防水涂料主要用于建筑物某些可能受到水侵蚀的结构部位或结构构件，例如屋面、地下室、厕浴间、水塔、水池、贮水罐等结构的防水、防潮和防渗等。同一般功能性建筑涂料所不同的是，在很多种情况下，防水几乎成为其主要功能和目的，其装饰功能甚至可以忽略不计。例如，大部分屋面用的防水涂料对于装饰功能是没有要求的（有小部分要求其具有装饰性，而配制成彩色涂料)；再例如，地下室外墙面使用的防水涂料，由于结构很快被回填而处于地下土壤中，装饰功能根本就没有意义；用于厕浴间地面防水等许多情况都是如此，这是防水涂料区别于其他功能性建筑涂料的最大的特征。当然，一般建筑涂料也要求具有防水性能，但这种要求与相对于以防水为主要目的的防水涂料来说在应用场合、环境和对涂膜耐水性的要求来说是完全不同的。  \n\n建筑防水涂料的主要应用场合是建筑物的屋面、卫生间和地下室等，这些结构部位可能是长期处于水中或受到水的作用的环境之下，其对涂膜的耐水和防水性能的要求必然要十分苛刻。此外，这些结构部位温度变化较大，且其基层一般是水泥类材料，因各种原因造成的裂缝更是十分常见，因而对防水涂膜的耐高、低温性能，对结构变化的适应性也和防水性能一样重要。所以防水涂膜一般要求具有很好的低温柔性、延伸率、拉伸强度和对基层具有一定的附着力。  \n\n从防水涂料的组成来说，防水涂料中使用的颜料（包括填料）的量很小，有些根本不含颤料（例如有些聚氨酯防水涂料)，以保证涂膜致密而不透水。  \n\n防水涂料的用量很大，对建筑物使用功能的影响也很大，同其他功能性建筑涂料相比，与建筑物的功能关系更为密切，因而受到高度重视，这也是防水涂料有别于其他功能性建筑涂料的重要方面。",
+        "category": " Introduction"
+    },
+    {
+        "id": 971,
+        "chunk": "# 2.建筑防水涂料的分类与种类  \n\n防水涂料品种较多，是应用较广泛的建筑涂料类别。根据材料组成，防水涂料的主要类别见表3-1-88。  \n\n表3-1-88防水涂料的分类与主要类别  \n\n\n<html><body><table><tr><td>主要类别</td><td>涂料类型</td><td>产品举例</td></tr><tr><td rowspan=\"3\">合成树脂类</td><td>单组分</td><td>①溶剂型：聚氯乙烯 ②水性：丙烯酸酯；苯乙烯-丙烯酸酯；丙烯酸-丙烯腈-苯乙烯共聚型涂</td></tr><tr><td>双组分</td><td>料等 聚硫环氧树脂（溶剂型);氯丁橡胶沥青</td></tr><tr><td>单组分</td><td>①溶剂型：氯磺化聚乙烯橡胶、乙丙橡胶；聚氨酯 ②水性：硅橡胶、丁苯（丁二烯-苯乙烯)橡胶、基丁苯橡胶、氯丁（氯乙 烯-丁二烯）橡胶</td></tr><tr><td></td><td>双组分</td><td>溶剂型：焦油聚氨酯、沥青聚氨酯、聚硫橡胶</td></tr><tr><td>沥青类</td><td>单组分</td><td>性型土水青防水涂料</td></tr><tr><td>橡胶及改性沥青类</td><td>单组分</td><td>①溶剂型：氯丁橡胶沥青、再生橡胶沥青类、SBS改性沥青、丁基橡胶沥青 ②水性：氯丁橡胶沥青、基氯丁橡胶沥青、再生橡胶沥青</td></tr><tr><td rowspan=\"3\">无机类</td><td>涂层覆盖型</td><td>确保时（COPROX)、防水宝、M1500、HM1500和TM1500 稳挡水（VANDEX，德国）、赛柏斯（XYPEX，加拿大）、KRYSTOL（加拿</td></tr><tr><td>结晶渗透型</td><td>大)、房挡水（FORMDEX，新加坡）、彭内传（PENETRON，美国），DIPSEC</td></tr><tr><td></td><td>（法国）、CRYSTAL（澳大利亚）、PANDEX(日本)以及国产的各种类型的水 混基渗透结品型防水涂料等</td></tr><tr><td>有机-无机复合类</td><td>双组分</td><td>聚合物水泥复合型防水涂料：丙烯酸酯乳液-硅溶胶复合防水涂料等</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 972,
+        "chunk": "# 二、聚氨酯防水涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 973,
+        "chunk": "# 1.特征与种类  \n\n(1）性能特征聚氨酯防水涂料通常为液态双组分反应固化型或单组分潮气固化型。具有如下特性；  \n\n$\\Phi$ 防水效果好聚氨酯防水涂料固化后能够形成无接缝、完整的涂膜防水层，提高了工程的防水抗渗能力，其效果是其他许多防水材料所无法达到的。  \n\n$\\textcircled{2}$ 适用范围广聚氨酯涂膜的耐水性非常好，聚醚型双组分聚氨酯涂膜在常温 $25\\mathrm{{C}}$ 。下浸泡自来水，经过6年之久，强度虽然下降 $20\\%\\sim30\\%$ ，但涂膜还不起泡，涂膜外观也无变化。因而，聚氨酯防水涂料可应用于长期浸水部位，以及在许多结构场合使用。例如，用于屋面、地下室、厕浴间、水池等许多需要防水的结构部位的防水施工，尤其适合于接头复杂、管道纵横部位的防水施工。例如，阴阳角、管道根部和端部收头等。  \n\n$\\textcircled{3}$ 施工简便聚氨酯防水涂料采用冷施工法，双组分型施工时仅需要将甲、乙料按比例混合均匀，采取一定的施工方法（例如刷涂）施工在基面上即可。施工无特殊技术要求，易于掌握。单组分型的聚氨酯防水涂料施工更为方便。  \n\n$\\textcircled{4}$ 物理力学性能好聚氨酯防水涂膜具有很高的弹性和很大的延伸率，对基层开裂或伸缩等变形的适应性强。  \n\n③容易维修当聚氨酯防水涂膜在使用过程中出现损坏时，只需要对损坏的部位进行局部修补，就可以达到原来的防水效果，省时、简单、费用低。  \n\n$\\textcircled{6}$ 使用寿命长聚氨酯防水涂膜富有弹性，耐冻、耐热、耐腐蚀，有保护层的聚氨酯防水涂膜的使用寿命可长达35年以上。  \n\n缺点是溶剂型聚氨酯防水涂料中的溶剂和施工过程中使用的稀释剂都会对环境和人体健康产生不良影响。尤其是涂料中所含有的游离TDI（异氰酸酯）毒性很大，当其含量高时会严重影响施工人员的健康，并在施工后的短时间内对周边环境产生不利影响。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 974,
+        "chunk": "# (2）聚氨酯防水涂料的种类  \n\n聚氨酯防水涂料的种类和性能特征见表3-1-89。  \n\n表3-1-89聚氨酯防水涂料的种类与性能特征  \n\n\n<html><body><table><tr><td>分类依据</td><td>涂料种类</td><td>基本组分</td><td>性能特征</td></tr><tr><td rowspan=\"2\">根据应用 场合不同 分类</td><td>外露型聚氨 酶防水涂料</td><td>甲组分是以脂肪族甲苯二异氰酸酯（HDI） 或二苯基甲烷二异氰酸酯（MDI)与混合聚醚 合成的预聚体；乙组分采用混合聚醚，并添加 各种颜料、填料和助剂后制成的双组分防水 涂料</td><td>在使用前混合，并需要在一定的时间内用完；涂 膜具有优良的耐热性、抗碱性、光稳定性和耐老化 性：涂料可以根据需要制成各种颜色，满足装饰性 要求；涂料的制造成本高</td></tr><tr><td>非外露型聚 氨酯防 水涂料</td><td>甲组分是以芳香族甲苯二异氰酸酯（TDI) 与混合聚醚合成的预聚体；乙组分采用含有 大量芳香族材料（如煤焦油或石油沥青），并 添加各种颜料、填料和助剂后制成的双组分</td><td>在使用前混合，并需要在一定的时间内用完；涂 膜结构中含有芳香族氨酯键，裂解温度低，耐碱性 差，与胺反应转化为脲而性脆；退醇而醇解后耐紫 外线照射或耐热性能差；涂料的制造成本比外露</td></tr><tr><td rowspan=\"2\">根据涂料 组分不同 分类</td><td>单组分聚 氨酯防 水涂料</td><td>防水涂料 以含有—NCO端基的预聚物为成膜物质， 防水涂料</td><td>型产品显著降低 涂料为单组分，可直接使用，不要求在严格规定 的时间内用完；涂膜性能与相应的双组分型产品 添加各种颜料、填料和助剂后制成的单罐装的相似或稍差；涂料对于包装要求严格，制造成本 更高；涂料可以根据需要制成各种颜色，满足装饰 性要求</td></tr><tr><td>双组分聚 氨酯防 水涂料</td><td>涂料的甲组分是以甲苯二异氰酸酶（TDI) 或二苯基甲烷二异氰酸酯（MDI)与混合聚醚 合成的预聚体；乙组分系采用混合聚醚制成 的含—OH基团树脂或其他含-OH、—NHz 活泼基团的材料（如石油沥青），添加各种颜 料、填料和助剂后制成的双组分防水涂料</td><td>在使用前混合，并需要在一定的时间内用完；涂 料的制造成本相对低；涂膜性能视制造涂料时使 用的原材料品种而异，例如使用脂肪族多异氰酸 酯制得的产品具有良好的耐碱性、耐紫外光性和 耐老化性，可以应用于外露场合；而使用芳香族多 异氰酸酯制得的产品，因涂膜结构中含有芳香族 氨酯键，耐热、耐碱性差、性脆以及耐紫外线照射 或耐热性能差等而不能应用于外露场合</td></tr><tr><td rowspan=\"2\">根据分散 介质不 同分类</td><td>溶剂型 聚氨酯 防水涂料</td><td>盖范围较广，包括单组分与双组分产品、 外露型与非外露型产品等多种，其涂料的构料可以使用溶剂型稀释剂进行稀释，涂料能够低 成组分因涂料品种不同而异，但其共同特点 是含有少量有机挥发分和游离异氰酸酯。这有机挥发分和游离异氰酸酯，因而对人体健康和 类涂料是我国聚氨酯防水涂料的主要品种 有单组分和双组分两种：单组分涂料由单</td><td>涂料性能因品种不同面异，但其共同特点是涂 温施工以及淹平性优良等。由于涂料中含有少量 环境有不良影响</td></tr><tr><td></td><td>组分聚氨酯水分散体、颜料、填料和助剂等构保性，例如基本上无有机挥发物污染，无游离异氰 类涂料目前尚处于实验室的研制阶段，在实 际中使用的极少</td><td>水性聚氨酯防水涂料的主要性能优势在于其环 涂膜性能相对变差；此外，单组分涂料的耐水性、 耐溶剂性和硬度较差</td></tr></table></body></html>  \n\n国家标准GB/T19250—2003《聚氨酯防水涂料》根据我国聚氨酯防水涂料的应用状况，将聚氨酯防水涂料按产品组分分为单组分（S）和多组分（M）两种，每种产品中又按拉伸性能分为I、Ⅱ两类产品。除此之外，还有根据材料化学组成的不同将聚氨酯防水涂料分为芳香族聚氨酯防水涂料、脂肪族聚氨酯防水涂料和聚醚型以及羟丁型聚氨酯防水涂料等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 975,
+        "chunk": "# 2.弹性聚氨酯树脂  \n\n弹性聚氨酯树脂是构成聚氨酯防水涂料的基本材料。其主要特性是涂膜的断裂伸长率较高，在常温下能够达到 $300\\%\\sim600\\%$ 甚至更高；涂膜的玻璃化温度很低，在常温下处于高弹态。即在较小的外力作用下能够发生很大的形变，而且当外力除去后又能够恢复原来的形状。要使聚氨酯树脂具备高度弹性，则其结构必须是由线型长链大分子组成（分子量范围在几百至几千的各种类型的树脂均不能够显现出弹性)，并且具有适度的交联（或称硫化)。线型大分子间存在弱的分子间力，常温下是柔顺的无规线团，能够移动或者转动。在柔性链段之间需要有短的刚性链段，如下式所示。  \n\n![](images/c93e9f0c2c6da3a3aeba85a0dfdfae5b87a6352d899266932b7d3e49d89e08e6.jpg)  \n\n上式中，短节的二元醇（G）所生成的氨酯链段呈现刚性；在分子间氢键吸力大，能够起到弱交联点的作用，而使长链部分的链段柔顺。刚性部分的数量决定涂膜的硬度和耐高温性；柔顺部分的数量决定涂膜的弹性、低温柔性、耐水性和耐溶剂性等。  \n\n柔性链段可以通过改变端羟基化合物的种类和分子量的大小来实现，使得大分子链易卷曲和自由运转，涂膜弹性增大，软化点、硬度和机械强度降低；刚性链段则可以由二异氰酸酯的品种和扩链剂的类型变化而改变。因为刚性链段能够束缚大分子的自由旋转，空间位阻大，其结果会使涂膜的机械强度和硬度增大，软化点升高。通过控制反应条件，使这两种性质互相矛盾的链段形成嵌段结构，而达到相对的平衡，从而得到符合性能要求的弹性聚氨酯树脂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 976,
+        "chunk": "# 3.双组分聚氨酯防水涂料  \n\n（1）组成材料、作用和固化成膜原理  \n\n$\\textcircled{1}$ 组成材料及其作用双组分聚氨酯防水涂料由预聚体组分（甲组分）和固化填充剂（乙组分）组成。预聚体组分是以甲苯二异氰酸酯（TDI）与聚醚多元醇（简称聚醚）的多种型号混合物逐步加成聚合而成。为获得合理的拉伸强度和延伸率，一般要求预聚体的—NCO质量分数控制在 $4\\%\\sim5\\%$ \\*  \n\n乙组分的主要成分是能够与—NCO反应的聚醚、带有结晶水的无机化合物；助剂有固化剂摩卡（MOCA)，它具有对称的芳环结构及邻位氯原子，前者的刚性以及与其他基团反应生成的脲键的极性吸引力，使聚氨酯具有很高的机械强度，后者的空间位阻和吸电子效应降低了氨基的反应速率，使双组分涂料有足够的施工时间；增塑剂邻苯二甲酸二丁酯、葱油等可调整产品的拉伸强度及延伸率；催化剂（或扩链剂）能够缩短反应的时间；紫外线吸收剂能够提高涂膜的耐老化性能；消泡剂能够消除涂料的气泡；填料不仅可以降低成本，而且可以改善产品的耐高低温性能、施工性及贮存稳定性；有的产品还加人催化剂以提高冬季成膜性以及使用一定量的溶剂以调整涂料的黏度等。  \n\n$\\textcircled{2}$ 增混剂增混剂也称增溶剂、助溶剂等，不是通用的商品涂料助剂，是为了解决石油沥青和聚氨酯树脂相容性而使用的一类材料，在沥青聚氨酯防水涂料中是十分重要的助剂。石油沥青聚氨酯防水涂料生产中的一个重要问题是石油沥青和聚氨酯树脂相容性的问题。  \n\n通常，人们把石油沥青和聚氨酯的相容性分为初始相容性和增塑相容性两个阶段。初始相容性是指甲、乙组分经充分搅拌，混合后形成均一体系。增塑相容性是指完全固化后的聚氨酯防水涂料具有均匀的结构。  \n\n$\\textcircled{3}$ 固化成膜原理双组分聚氨酯防水涂料施工固化成膜后，预聚体组分中的异氰酸基（—NCO）与固化剂、填充剂组分中的含活泼氢（一OH、 $-\\mathrm{NH}_{2}$ 、一COOH）的多元醇、多元酚、多元胺和水等进行加成反应而固化成膜。化学反应过程如下所示。  \n\n![](images/b5446ad250dd1b4097b09e4c310b8dd4669c687060fa638a235e81b0d5170535.jpg)  \n\n(2）预聚体的合成  \n\n$\\Phi$ 配方目前国内双组分聚氨酯防水涂料的预聚体组分的组成相差不大，基本上都以甲苯二异氰酸酯（TDI）与聚醚多元醇（简称聚醚）的多种型号混合物加成聚合而成。合成这类双组分聚氨酯防水涂料预聚体使用的某些配方见表3-1-90。  \n\n表3-1-90合成预聚体使用的配方举例  \n\n\n<html><body><table><tr><td>原材料名称</td><td>用量/质量份</td></tr><tr><td>聚醚二元醇（商品牌号如204、210、220等）</td><td>200~380</td></tr><tr><td>聚醚三元醇（商品牌号如303、330等）</td><td>50~180</td></tr><tr><td>TDI甲苯二异氰酸酯（规格80/20）</td><td>50~88</td></tr><tr><td>PAPI多亚甲基多苯基二异氰酸酶</td><td>10~20</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 预聚体的合成工艺按配方称取聚醚多元醇（N220、N330），置于反应釜中加热脱水。当温度升至 $80^{\\circ}\\mathrm{C}$ 左右时，开动真空泵进行抽真空脱水，抽真空的压力保持为 $66.66\\sim$ 93.33kPa且始终搅拌。再加热至 $110^{\\circ}\\mathrm{C}$ ，继续脱水2h。然后关闭蒸汽阀和真空泵，同时开启冷却水，使反应釜内的物料冷却，降温至 $50\\mathrm{^c}$ 以下。按配方称取TDI和PAPI，在该过程中勿使温度超过 $85^{\\circ}C$ 。当TDI和PAPI加完后，关闭冷却水。继续用蒸汽加热升温。升至85℃后，保温2h。反应完毕，可再适当真空脱水，以防止成品内含有水分影响涂料的贮存稳定性。  \n\n将制作好的预聚体密闭装存于包装容器中，避免与空气接触。  \n\n（3）石油沥青聚氨酯乙组分的合成工艺由于含有大量煤焦油的焦油型聚氨酯防水涂料已经禁止使用，因而常常使用石油沥青代替煤焦油，即沥青型聚氨酯防水涂料。石油沥青聚氨酯防水涂料中乙组分的制备程序一般为：将石油沥青、填充料加热至 $130\\sim140{\\uptau}$ 熔化、脱水1.5～2h；加人增容剂、增塑剂、MOCA，115～120℃下搅拌20～30min；降温至$80\\sim85\\mathrm{\\top}$ ，并加人复合溶剂，揽拌均匀制得乙组分。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 977,
+        "chunk": "# 4.几种新型双组分聚氨酯防水涂料  \n\n(1）使用石油树脂代替石油沥青的聚氨酯防水涂料使用石油树脂可以代替石油沥青生产双组分聚氨酯防水涂料，其生产工艺与使用沥青相比没有明显改变，而且石油树脂比石油沥青容易混溶，石油树脂的颜色浅，能够制成彩色聚氨酯涂料。同时，所得到的涂料性能也更为优异，并且也为石油树脂开拓了新的应用领域。但是，涂料的生产成本比使用沥青的高。  \n\n(2）使用水为固化剂的聚氨酯防水涂料由于是通过加水使其固化，该涂料固化迅速，同样形成性能优异的取代脲（传统的胺类固化剂摩卡与异氰酸酯反应生成取代脲)，其性能可完全达到GB/T15923—2003《聚氨酯防水涂料》标准。因而，水固化聚氨酯的原理可概括为：游离状态的水和以—NCO基为端基的多异氰酸酯预聚体发生反应，生成脲键而固化，水起了扩链即固化剂作用；生成的 $\\mathrm{CO}_{2}$ 气体可通过气体吸收剂吸收，形成致密的聚氨酯弹性体涂膜。  \n\n(3）丁晴羟/聚醚并用型沥青聚氨酯防水涂料沥青聚氨酯防水涂料虽然具有较好的性能，但沥青的极性小，聚醚型聚氨酯预聚体的极性强，因而两者相容性差，影响了涂料的性能。使用端羟基聚丁二烯丙烯睛制备的预聚体（丁睛羟预聚体）极性弱，和沥青的相容性好，但制造成本较高。而将不同比例的丁睛羟预聚体相混，能够改善甲、乙双组分的相容性，提高涂膜的力学性能。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 978,
+        "chunk": "# 5.单组分聚氨酯防水涂料  \n\n单组分聚氨酯防水涂料有两种制备方法：一种制备方法与双组分的预聚体相似，只是为了施工后便于固化，降低了—NCO含量，即是将乙组分中的部分聚醚先加入甲组分中参与反应，这种预聚体需要更高密闭性能的容器，以免吸收潮气，贮存期也较短；另一种方法是将二异氰酸酯与分子量较低的二元醇或三元醇的聚醚反应， $-\\mathrm{NCO}/\\mathrm{-OH}$ 低于2，一般在$1.2{\\sim}1.8$ 。由于一NCO/一OH低于2，在以异氰酸酯封端的同时，使预聚物的分子量提高，聚醚链段中嵌人氨酯键，提高机械强度，并保证迅速干燥。聚醚的羟基大多数是仲羟基，在单组分潮气固化型聚氨酯防水涂料生产过程中，可在反应釜中加热，使仲羟基充分反应，留出端基—NCO以潮气固化。这类涂料通常的制备工艺流程如下。  \n\n![](images/74dddd1149a30edbc73cfca2c76d8a2cd853990bd93c59ad5dda57a25e682995.jpg)  \n\n可以根据不同的原料和配比以及生产涂料性能的要求对生产工艺进行适当的调节例如：  \n\n![](images/c8c852ee99875f1ecc7b3d5c50937118f8cf8bad02db2ec37cb07cbb9f697e7c.jpg)  \n\n上述投料比例（摩尔比）为：聚醚N303/聚醚 $\\mathrm{N}204/\\mathrm{TDI}=2/1/6$ 。操作程序为：将聚醚N303投入反应釜中，加入 $5\\%$ 苯脱水，冷却至 $35\\mathrm{{^circ}C}$ ，加人TDI，通氮气，搅拌，升温至$60\\sim70^{\\circ}C$ 反应，加人 $10\\%$ 甲苯以调节黏度，然后加人二元聚醚N204（预先用苯脱水），升温至 $80\\sim90^{\\circ}C$ ，保温 $2\\sim3\\mathrm{h}$ ，取样以二丁胺测—NCO含量决定终点。该例的—NCO/—OH  \n\n比为1.5。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 979,
+        "chunk": "# 6.改善聚氨酯防水涂料性能的途径  \n\n（1）使用纳米材料和晶须类材料改善聚氨酯防水涂料的性能  \n\n①纳米材料对聚氨酯防水涂料性能的改善所得到的综合效果是在涂料成本稍有降低的情况下使涂料的各项性能有所提高。  \n\n$\\textcircled{2}$ 晶须类材料对聚氨酯防水涂料性能的改善使涂膜的各种物理性能得到综合性改善。  \n\n(2）使用蒙脱土改善双组分聚氨酯防水涂料的性能使用蒙脱土能够改善双组分聚氨酯防水涂料的性能。由此而制得的双组分聚氨酯防水涂料，力学性能明显得到改善，涂膜的断裂延伸率和拉伸强度均有较大提高，而吸水率显著降低。  \n\n(3）使用蒙脱土改善单组分聚氨酯防水涂料的性能，力学性能有很好的改善作用。  \n\n(4）粉煤灰在双组分聚氨酯防水涂料中的应用粉煤灰的物理性能和外观形态使之能够良好地应用于双组分聚氨酯防水涂料中，起到改善涂料性能和降低成本的作用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 980,
+        "chunk": "# 7.聚氨酯防水涂料的施工与应用  \n\n聚氨酯防水涂料是高性能、多用途的新型防水材料，根据品种、型号的不同可以分别用于各种建筑物的屋面、卫生间的地面、地下室的底板、外墙等场合或其他能够满足要求的特殊场合的防水施工。  \n\n以聚氨酯防水涂料在屋面防水工程中应用的施工技术为例。  \n\n（1）基层处理和基层条件对于潮湿不宜直接施工聚氨酯防水涂料的基层，因工期或其他原因而需要施工的情况，可以先施涂潮湿基层隔离剂。潮湿基层隔离剂可在新浇注1～2天的混凝土基层上或在未干的水泥砂浆基层表面进行施工。施工前，先把基层表面处理干净，擦去明水。其后配制潮湿基层隔离剂。当隔离剂表面出现光泽而不粘手时，即可进行防水涂料的施工。  \n\n(2）防水层施工  \n\n$\\Phi$ 清扫将基层表面的砂浆疙瘩、尘土、杂物等彻底清扫干净。  \n\n②涂布底涂料将已搅拌均匀的底涂料用辊刷涂布在基层表面上。待底涂料涂布后干燥 $8\\sim24\\mathrm{h}$ 再进行下一工序的施工。  \n\n$\\textcircled{3}$ 防水涂膜的施工防水层涂料按配料比例，用电动搅拌器混合均匀，施工屋面时，将已搅拌均匀的聚氨酯防水涂料用橡胶刮板先均匀涂刮天沟、泛水、穿通管、阴阳角等特殊部位，然后再做大面积施工。 茶  \n\n④撒布细石当需要在防水涂膜表面做保护层且如果保护层是水泥砂浆，或者需要用水泥砂浆粘贴贴面材料（如瓷砖）时，应在刮涂最后一道涂料时，在其表面撒布少量干净的、粒径 $2\\sim3\\mathrm{mm}$ 的细石粒，以增加防水层和水泥砂浆的黏结力。  \n\n$\\textcircled{5}$ 防水保护层的施工根据需求采用不同保护层。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 981,
+        "chunk": "# 8.聚氨酯防水涂料的技术标准  \n\nGB/T19250—2003将聚氨酯防水涂料产品按其组分分为单组分（S）和多组分（M)两种；按拉伸性能分为I、Ⅱ两类。  \n\n按照GB/T19250—2003标准的要求，聚氨酯防水涂料的技术指标见表3-1-91和表3-1-92。  \n\n表3-1-91GB/T19250—2003单组分聚氨酯防水涂料技术指标   \n\n\n<html><body><table><tr><td>序号</td><td colspan=\"2\">项 目</td><td></td><td>I类产品</td><td>Ⅱ类产品</td></tr><tr><td>1</td><td colspan=\"2\">拉伸强度/MPa</td><td>1. 9</td><td colspan=\"2\">2.45</td></tr><tr><td>2</td><td colspan=\"2\">断裂伸长率/%</td><td></td><td>550</td><td>450</td></tr><tr><td>3</td><td colspan=\"2\">撕裂强度/（N/mm）</td><td></td><td>12</td><td>14</td></tr><tr><td>4</td><td colspan=\"2\">低温弯折性/C</td><td>≤</td><td colspan=\"2\">-40</td></tr><tr><td>5</td><td colspan=\"2\">不透水性（0.3MPa,30min）</td><td></td><td colspan=\"2\">不透水</td></tr><tr><td></td><td colspan=\"2\">固体含量/%</td><td>AWW</td><td colspan=\"2\">80</td></tr><tr><td>６7</td><td colspan=\"2\">表干时间/h</td><td></td><td colspan=\"2\">12</td></tr><tr><td>8</td><td colspan=\"2\">实干时间/h</td><td></td><td colspan=\"2\">24</td></tr><tr><td>9</td><td>加热伸缩率/%</td><td></td><td>V</td><td colspan=\"2\">1.0</td></tr><tr><td>10</td><td colspan=\"2\">潮湿基面粘接强度/MPa</td><td></td><td colspan=\"2\">4.0 0.50</td></tr><tr><td>11</td><td>加热老化 定伸时老化</td><td></td><td></td><td colspan=\"2\">无裂纹及变形</td></tr><tr><td rowspan=\"3\">12</td><td rowspan=\"3\">热处理</td><td>人工气候老化 拉伸强度保持率/%</td><td></td><td colspan=\"2\">无裂纹及变形 80~150</td></tr><tr><td>断裂伸长率/%</td><td>500</td><td colspan=\"2\">400</td></tr><tr><td>低温弯折性/C ≤</td><td></td><td colspan=\"2\">35</td></tr><tr><td rowspan=\"3\">13</td><td rowspan=\"3\">碱处理</td><td>拉伸强度保持率/%</td><td></td><td colspan=\"2\">60~150</td></tr><tr><td>断裂伸长率/% #</td><td>500</td><td colspan=\"2\">400</td></tr><tr><td>低温弯折性/C ##</td><td></td><td colspan=\"2\">-35</td></tr><tr><td rowspan=\"3\">14</td><td rowspan=\"3\">酸处理</td><td>拉伸强度保持率/%</td><td></td><td colspan=\"2\">80~150</td></tr><tr><td>断裂伸长率/% ≥</td><td></td><td></td><td>400</td></tr><tr><td>低温弯折性/℃ #</td><td>500</td><td colspan=\"2\">35</td></tr><tr><td rowspan=\"3\">15</td><td rowspan=\"3\">人工</td><td>拉伸强度保持率/%</td><td colspan=\"2\">80~150</td><td></td></tr><tr><td>断裂伸长率/%</td><td colspan=\"2\">500</td><td>400</td></tr><tr><td>低温弯折性/C ≤</td><td>-35</td><td colspan=\"2\"></td></tr></table></body></html>\n\n$\\Phi$ 仅用于地下工程潮湿基面时要求。$\\textcircled{1}$ 仅用于外露使用的产品。  \n\n表3-1-92多组分聚氨酯防水涂料技术指标  \n\n\n<html><body><table><tr><td>序号</td><td>项 目</td><td>I类产品</td><td></td><td>Ⅱ类产品</td></tr><tr><td>1</td><td>拉伸强度/MPa</td><td>≥</td><td>1.9</td><td>2.45</td></tr><tr><td>2</td><td>断裂伸长率/%</td><td>≥</td><td>450</td><td>450</td></tr><tr><td>3</td><td>撕裂强度/（N/mm）</td><td></td><td>12</td><td>14</td></tr><tr><td>4</td><td>低温弯折性/C</td><td>≤</td><td>35</td><td></td></tr><tr><td>5</td><td>不透水性（0.3MPa,30min）</td><td></td><td>不透水</td><td></td></tr><tr><td>6</td><td>固体含量/%</td><td></td><td>92</td><td></td></tr><tr><td>7</td><td>表干时间/h</td><td></td><td>8</td><td></td></tr><tr><td>8</td><td>实干时间/h</td><td>≤</td><td>24</td><td></td></tr><tr><td>9</td><td>加热伸缩率/%</td><td>≥</td><td>1.0 4. 0</td><td></td></tr><tr><td>10</td><td colspan=\"2\">潮湿基面粘接强度/MPa</td><td colspan=\"2\">0.50</td></tr></table></body></html>  \n\n<html><body><table><tr><td>序号</td><td colspan=\"2\">项目</td><td>I类产品</td><td>Ⅱ类产品</td></tr><tr><td>11</td><td>定伸时老化</td><td>加盖老老化</td><td colspan=\"2\">无裂纹及变形</td></tr><tr><td>12</td><td>热处理</td><td>拉伸强度保持率/% 断裂伸长率/% V 低温弯折性/℃</td><td>80~150</td><td>400</td></tr><tr><td>13</td><td>碱处理</td><td>拉伸强度保持率/% 断裂伸长率/% V 低温弯折性/C</td><td></td><td>30 60~150 400</td></tr><tr><td>14</td><td>酸处理</td><td>拉伸强度保持率/% 断裂伸长率/% 低温弯折性/C</td><td></td><td>~30 80~150 400 30</td></tr><tr><td>15</td><td></td><td>拉伸强度保持率/% 断裂伸长率/% # 低温弯折性/C</td><td colspan=\"2\">80~150 400 30</td></tr></table></body></html>\n\n$\\Phi$ 仅用于地下工程潮湿基面时要求。$\\oslash$ 仅用于外露使用的产品。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 982,
+        "chunk": "# 三、聚合物水泥防水涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 983,
+        "chunk": "# 1.性能特征及应用  \n\n聚合物水泥防水涂料，通常称之为JS防水涂料，是以丙烯酸酯等聚合物乳液和水泥为主要原料，加入其他外加剂制得的单组分或双组分水性建筑防水涂料。这种涂料由于综合了聚合物和水泥的优势，而被认为具有“刚柔相济”的特性，即既有聚合物涂膜的延伸性、防水性，也有水硬性胶凝材料强度高、与潮湿基层粘接能力强的优点。该种涂料以水作为分散剂，解决了因采用焦油、沥青等溶剂型防水涂料所造成的环境污染以及对人体健康的危害。  \n\n我国20世纪90年代初开始研制聚合物水泥防水涂料，目前在全国范围内得以应用，其良好的防水效果得到普遍的接受与认可。该类涂料可用于屋面防水、厕浴间和地下室防水、混凝土保护、缝隙遮蔽、装饰瓷砖外墙面渗漏的修补等。  \n\n在聚合物水泥类防水涂料中，得到广泛应用的是丙烯酸酯和乙烯-醋酸乙烯（VAE）两类，分单组分和双组分两种，见表3-1-93。  \n\n表3-1-93丙烯酸酯树脂类和VAE类聚合物水泥防水涂料的类型  \n\n\n<html><body><table><tr><td rowspan=\"2\">组分</td><td colspan=\"2\">防水涂料种类</td></tr><tr><td>单组分粉状涂料</td><td>双组分防水涂料</td></tr><tr><td>胶结材料</td><td>可再分散丙烯酸酯树脂粉末或可再分散乙烯- 醋酸乙烯树脂粉末、硅酸盐水泥或普通硅酸盐 水泥或其他水泥</td><td>弹性丙烯酸酯乳液或乙烯-醋酸乙烯乳液、硅酸盐水 泥或普通硅酸盐水泥或其他水泥</td></tr><tr><td>填料、颜料</td><td>不同粒径、配比的石英砂和着色颜料等</td><td>不同粒径、配比的石英砂和着色颜料等</td></tr><tr><td>助剂</td><td>粉状消泡剂、粉状增塑剂等</td><td>消泡剂、增塑剂等 分别将各类粉料和各类液体材料按一定配方混合均</td></tr><tr><td>产品制备和特性</td><td>将各类材料按一定配方混合均匀得到粉状产 品，使用前加人适量水搅拌均匀即可使用</td><td>匀形成粉料组分和液料组分并分开包装，使用前将两 个组分按设定比例搅摔混合均匀即可使用</td></tr><tr><td>应用特点</td><td>现场加水揽拌后必须在规定时间内用完，产 品具有优异的防水性、抗老化性、低温柔性等特 点，环保型产品，不含有机溶剂，可再分散丙 烯酸酯树脂粉末的成本相对高于乳液的成本</td><td>现场搅拌，双组分混合后必须在规定时间内用完，产 品具有优异的防水性、抗老化性、低温柔性等特点，环 保型产品，不含有机溶剂。产品成本相对较低，但双组 分产品在包装、运输和贮存等方面不如单组分方便</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 984,
+        "chunk": "# 2.水泥改性机理  \n\n(1）水泥的聚合物改性通过使用聚合物改性，能够降低和补偿水泥材料的干缩和结构收缩，减少或消除微细裂缝，适当增加水泥材料的柔韧性，并提高致密性。聚合物水泥防水涂料就是利用这一原理，使用聚合物对水泥进行改性的，它把聚合物的柔性、弹性及对基层的黏结力与水泥的低成本、耐水性、防水性及耐老化性结合起来，使得防水涂料具有优异的性能，且成本适中。  \n\n(2）聚合物改性水泥材料中聚合物与水泥的结合聚合物改性水泥材料中聚合物与水泥的结合有两种方式：一种是物理结合，即聚合物成膜后覆盖于水泥凝胶体表面（聚合物多于水泥组分的情况）或水泥水化物填充于聚合物网络之间（聚合物少于水泥组分的情况)，有机物和无机物仅为情性地、机械式地相互填充；另一种是反应性的聚合物与水泥之间的化学结合，这两种结合同时存在。聚合物与水泥之间的化学结合通过化学反应而产生。化学反应有两种反应形式：一种是聚合物之间（或聚合物与固化剂之间）的交联固化反应，形成大分子；另一种是聚合物活性基团与水泥水化产物之间发生化学反应，形成以化学键结合的界面结构，通过界面增强导致材料性能的提高。通过适当的改性工艺，可以大大加强聚合物与水泥水化产物的化学结合。  \n\n含有—COOH等官能团的聚合物，能够与水泥水化产物中的 $\\mathrm{Ca^{2+}}$ 发生作用，从而显著地提高材料的强度和耐水性，所以在国外这类材料被称为反应型聚合物水泥基材料(RPMC)。RPMC是用活性聚合物、水泥、引发体系和集料制成的。与通常使用的聚合物改性水泥材料的差别在于，复合材料在结构的形成过程中聚合物和水泥都起到了活性（反应）作用，由于聚合物与水泥界面具有化学结合，使界面的承载能力提高，从而提高了截面韧性和断裂能，产生出良好的物理力学性能。  \n\n（3）聚合物改性水泥涂料的成膜聚合物改性水泥涂料在混合后变成由水泥、聚合物乳液和填料等组成的复合体系。在该体系的成膜过程中，对于普通的聚合物乳液来说，水泥因聚合物中的水分而发生水化反应，形成一定量的水泥凝胶体；乳液中的聚合物颗粒向料浆中分散，吸附在水泥和水泥的水化产物以及填料、颜料的表面。随着水分的消耗和散失，聚合物颗粒之间逐渐的靠拢，最终相互的凝聚在一起，并粘接水化和未水化的水泥颗粒、填料、颜料以及基层等而形成涂膜。由于涂膜中聚合物形成的网络是连续网络，而水泥的硅酸盐网络结构已经不连续，因此涂膜呈现聚合物膜的性能而具有较高的拉伸强度和柔韧性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 985,
+        "chunk": "# 3.聚合物水泥防水涂料生产技术  \n\n聚合物水泥防水涂料一般采用液体组分和粉料组分分开包装的双组分型，因为在相同技术性能的情况下，双组分涂料的成本要比单组分的粉状涂料的低得多。  \n\n(1）乙烯-醋酸乙烯（VAE）乳液水泥防水涂料$\\Phi$ 配方乙烯-醋酸乙烯（VAE）乳液水泥防水涂料参考配方见表3-1-94。  \n\n表3-1-94乙烯-醋酸乙烯（VAE）乳液水泥防水涂料配方举例  \n\n\n<html><body><table><tr><td>原材料名称</td><td>用量/质量份</td><td>原材料名称</td><td>用量/质量份</td></tr><tr><td>粉料组分 普通硅酸盐水泥（标号≥52.5号）</td><td>100</td><td>粉料组分 细砂（160目）</td><td>200</td></tr><tr><td>粉状消泡剂</td><td>适量</td><td>液料组分</td><td></td></tr><tr><td>粉状湿润、分散剂 粉状分散剂</td><td>适量 适量</td><td>乙烯-醋酸乙烯共聚乳液（固体含量≥48%）</td><td>100</td></tr></table></body></html>  \n\n②配制说明将粉料各个组分投入混料机中混合均匀，作为粉料组分包装；液料组分分开包装，使用时混合均匀。  \n\n$\\textcircled{3}$ 粉料和液料的配合比粉料：液料 $\\c=$ $(1,5\\sim3,0):1,$ 西",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 986,
+        "chunk": "# （2）丙烯酸酯乳液水泥防水涂料配方举例  \n\n$\\Phi$ 配方丙烯酸酯乳液水泥防水涂料的参考配方见表3-1-95。  \n\n表3-1-95丙烯酸酯乳液水泥防水涂料配方举例  \n\n\n<html><body><table><tr><td>原材料名称</td><td>用量/质量份</td><td>原材料名称</td><td>用量/质量份</td></tr><tr><td>粉料组分</td><td></td><td>液料组分</td><td></td></tr><tr><td>普通硅酸盐水泥（标号≥52.5号）</td><td>182</td><td>丙烯酸酯乳液（AcronalS-400)</td><td>191</td></tr><tr><td>粉状消泡剂</td><td>14</td><td>消泡剂</td><td>2</td></tr><tr><td>粉状湿润、分散剂</td><td>2~4</td><td>防霉剂</td><td>适量</td></tr><tr><td>石英砂（不同粒径进行合理级配）</td><td>531</td><td>水</td><td>273</td></tr></table></body></html>\n\n配方参数和主要技术性能：聚灰比0.6；拉伸强度（23C）1.6MPa；断裂伸长率（23℃）62%；48h吸水率约9%  \n\n$\\Phi$ 通过适当增大聚灰比（聚合物的固体量与水泥的质量比），可以适当提高涂膜的断裂伸长率，使之符合JC/T894—2001《聚合物水泥防水涂料》规定的要求。  \n\n$\\textcircled{2}$ 配制说明将粉料各个组分投入混料机中混合均匀，作为粉料组分包装；液料组分分开包装，使用时混合均匀。  \n\n(3）单组分聚合物水泥防水涂料  \n\n$\\textcircled{1}$ 配方表3-1-96中给出以可再分散丙烯酸酯树脂粉末或可再分散乙烯-醋酸乙烯树脂粉末为有机组分的防水涂料配方，以供参考。该类涂料目前应用不多。  \n\n表3-1-96单组分聚合物水泥防水涂料配方  \n\n\n<html><body><table><tr><td>原材料名称</td><td>功能作用</td><td>用量/质量份</td></tr><tr><td>普通硅酸盐水泥（标号≥42.5级） 粉状消泡剂 粉状湿润、分散剂</td><td>赋予涂膜粘接力、防水性和耐久性 消泡 湿润、分散</td><td>48.0 0.1 0.2~0.4</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 配制说明将涂料各个组分材料投入圆锥形螺旋混料机中混合均匀。为了保证各组分能够充分混合均匀，可将用量小的消泡剂、分散剂和甲基纤维素先和少量的石英粉混合均匀，然后再和涂料其他组分混合，作为粉料组分包装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 987,
+        "chunk": "# 4.聚合物水泥防水涂料的技术性能  \n\nJC/T894—-2001《聚合物水泥防水涂料》的技术要求，见表3-1-97。在该标准中，把产品分为I型和Ⅱ型两种。I型是以聚合物为主的防水涂料；Ⅱ型是以水泥为主的防水涂料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 988,
+        "chunk": "# 5.聚合物水泥防水涂料的应用和施工技术  \n\n(1）聚合物水泥防水涂料的施工工艺聚合物水泥防水涂料施工操作简便，施工人员容  \n\n表3-1-97聚合物水泥防水涂料的技术要求  \n\n\n<html><body><table><tr><td rowspan=\"2\" colspan=\"2\">技术指标项目</td><td colspan=\"2\">指标要求</td></tr><tr><td>I型</td><td>Ⅱ型</td></tr><tr><td>固体含量/%</td><td>≥</td><td>65</td><td>65</td></tr><tr><td>干燥时间/h</td><td></td><td></td><td></td></tr><tr><td>表干</td><td>≤#</td><td>4</td><td>4</td></tr><tr><td>实干</td><td>#</td><td></td><td>8</td></tr><tr><td>拉伸强度</td><td></td><td></td><td></td></tr><tr><td>无处理/MPa</td><td>》</td><td>1.2</td><td>1.8</td></tr><tr><td>加热处理后保持率/%</td><td></td><td>80</td><td>80</td></tr><tr><td>碱处理后保持率/%</td><td></td><td>70</td><td>80</td></tr><tr><td>紫外线处理后保持率/%</td><td></td><td>80</td><td>80</td></tr><tr><td>断裂伸长率</td><td></td><td></td><td></td></tr><tr><td>无处理/%</td><td></td><td>200</td><td>80</td></tr><tr><td>加热处理/%</td><td></td><td>50</td><td>65</td></tr><tr><td>碱处理/%</td><td></td><td>140</td><td>65</td></tr><tr><td>紫外线处理/%</td><td></td><td>150</td><td>65</td></tr><tr><td>低温柔性（P10mm棒）</td><td></td><td>10C无裂纹</td><td>一</td></tr><tr><td>不透水性(0.3MPa,30min)</td><td></td><td>不透水</td><td>不透水</td></tr><tr><td>潮湿基面粘接强度/MPa</td><td></td><td>0.5</td><td>1.0</td></tr><tr><td>抗渗性（背水面）/MPa</td><td></td><td></td><td>0.6</td></tr></table></body></html>\n\n$\\Phi$ 如产品用于地下工程，该项目可以不测试。$\\textcircled{2}$ 如产品用于地下防水工程，该项目必须测试。  \n\n易掌握。可直接在潮湿或干燥的砖石、砂浆、混凝土和各种防水层（例如沥青、橡胶、SBS防水卷材、APP防水卷材和聚氨酯防水涂膜）等基层表面施工。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 989,
+        "chunk": "# $\\Phi$ 工法选择  \n\n对于不同的防水工程，选用聚合物水泥防水涂料施工时，可以选择F4、F5、S5三种工法中的一种或两种进行。  \n\na.F4（四涂）工法施工顺序：打底层→下层→中层→面层。  \n\n该法适用于等级较低以及旧的建筑物维修的防水施工。  \n\nb.F5（五涂）工法施工顺序：打底层→下层→中层→中上层→面层。  \n\n该法适用于等级较高以及重要建筑物的防水施工。  \n\nc.S5（四涂一布）工法施工顺序：打底层 $\\mathbf{\\Psi}_{\\rightarrow}$ 下层→布层→中层→面层。  \n\n该法适用于建筑物的异型部位（如管根、墙根、落水口和阴阳角等）的防水和等级较高的防水施工。  \n\n$\\textcircled{2}$ 配料聚合物水泥防水涂料的基色为白色或灰白色，川以根据需要加入不同的颜料制成不同颜色的涂膜。颜料应选用耐碱、耐候性好的无机颜料，例如氧化铁黄、氧化铁红、氧化铬绿和稳定型菁蓝等。  \n\n配料时若需要加水，应把水加在液料中，搅拌均匀后再在搅拌的状况下将粉料加入液料中，然后充分搅拌均匀，至涂料中不含有没有搅拌不开的料团、颗粒等。最好采用手提式搅拌器搅拌。为了保证粉料均匀地混入液料中，在搅拌后最好使涂料过60目的筛网。  \n\n(2）涂料施工对于大面积的平面基层的施工，可以使用长毛辊简进行辊涂施工；对于小面积的局部施工，可以采用刮板刮涂施工或用刷子刷涂施工。施工时应按选定的工法，按顺序逐层完成。各层之间的时间间隔以前一道涂膜干燥为准。  \n\n这类防水涂料施工方便，对旧屋面的维修更具有优势。特别是丙烯酸酯类乳液和水泥的优良的耐久性，使得防水涂膜具有可靠的防水效果和优良的耐老化性能。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 990,
+        "chunk": "# 四、聚合物乳液防水涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 991,
+        "chunk": "# 1.基本组成和性能特征  \n\n(1）基本组成聚合物乳液防水涂料一般是指以丙烯酸酯乳液或者以乙烯-醋酸乙烯（VAE）乳液为基料，并以水为分散介质配制成的厚质防水涂料。这类涂料可应用于各种屋面、墙面和室内等非长期浸水环境下的建筑防水工程的防水和装饰的施工，其技术、生产、应用和性能等特征与本章前面介绍的合成树脂乳液类弹性外墙涂料相似，但对于屋面工程用涂料的耐沾污性能和装饰性能的要求都很低。  \n\n(2）性能特征水性丙烯酸酯防水涂料的最大特征在于其环境安全性，该涂料无毒、无环境不利影响、施工安全、操作方便、对施工人员的健康无不良影响，对基层含湿量要求不严。这类防水涂料属于新型的装饰性防水涂料，具有如下特性。  \n\n$\\Phi$ 耐老化性优良，在紫外线、光、热和氧的作用下性能稳定，可直接用于屋面等暴露于自然环境的结构场合，材料使用寿命可在10年以上。  \n\n$\\textcircled{2}$ 粘接力强、渗透性好。刷涂底涂料时可以渗透到水泥基材料的孔隙中，堵塞了渗水通道，防水效果可靠。  \n\n$\\textcircled{3}$ 延伸率好，断裂伸长率大于 $300\\%$ ，一般在 $300\\%\\sim500\\%$ ，因此其抗裂性优良，对基层的裂缝有很高的遮蔽作用，即使基层因外界因素产生微小裂缝，也不会产生渗漏作用。  \n\n$\\textcircled{4}$ 耐高低温性好，产品在高温（ $80^{\\circ}\\mathrm{C}$ ）不流淌，低温 $(-20\\mathbb{C}$ ）不脆裂，最低可达-30℃不脆裂。  \n\n$\\textcircled{5}$ 产品具有鲜艳的色彩，可根据设计要求和用户的需要调配至所需要的色彩，白色屋面在夏季具有反射太阳光、降低顶层房间温度的功能；彩色屋面具有装饰和美化环境的功能。因而，这类涂料属于新型的装饰性防水涂料。  \n\n该类产品由于以合成树脂乳液为基料，其不足之处为耐水性不良，不宜用于长期受水侵蚀的场合，例如地下防水和厨、卫间地面防水等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 992,
+        "chunk": "# 2.聚合物乳液防水涂料生产技术  \n\n进行聚合物乳液防水涂料的配方设计时，考虑到涂料的PVC对涂膜的延伸率和拉伸强度影响显著，因而应按照涂料的PVC小于其CPVC的原则设计配方。表3-1-98给出聚合物乳液防水涂料的参考配方。  \n\n表3-1-98生产聚合物乳液防水涂料的参考配方  \n\n\n<html><body><table><tr><td>原材料</td><td>用量/质量份</td><td>原材料</td><td>用量/质量份</td></tr><tr><td></td><td> #</td><td></td><td>2010130</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 993,
+        "chunk": "# 3.聚合物乳液防水涂料技术性能要求  \n\n聚合物乳液防水涂料的技术性能指标应符合建材行业JC/T864—2000《聚合物乳液建筑防水涂料》规定的技术要求，见表3-1-99。在JC/T864--2000标准中，按物理力学性能把产品分为I型和Ⅱ型两种。  \n\n表3-1-99聚合物乳液建筑防水涂料的技术要求  \n\n\n<html><body><table><tr><td rowspan=\"2\" colspan=\"2\">技术 指 标 项 目</td><td colspan=\"3\">指标要求</td></tr><tr><td>I型</td><td></td><td>Ⅱ型</td></tr><tr><td colspan=\"2\">外观</td><td colspan=\"3\">产品经搅拌后无结块，呈均匀状态</td></tr><tr><td>干燥时间/h</td><td></td><td></td><td></td><td></td></tr><tr><td>表干</td><td></td><td></td><td>4</td><td>4</td></tr><tr><td>实干</td><td></td><td>VV</td><td>8</td><td>8</td></tr><tr><td>拉伸强度/MPa 断裂延伸率/%</td><td></td><td></td><td>1. 0 300</td><td>1.5</td></tr><tr><td>低温柔性（绕10mm棒）</td><td></td><td></td><td>-10℃无裂纹</td><td>300 -20C无裂纹</td></tr><tr><td>不透水性（0.3MPa,30min）</td><td></td><td></td><td>不透水</td><td>不透水</td></tr><tr><td colspan=\"2\">老化处理后的拉伸强度保持率/%</td><td></td><td colspan=\"2\"></td></tr><tr><td>加热处理</td><td></td><td>八</td><td colspan=\"2\">80</td></tr><tr><td>紫外线处理</td><td></td><td></td><td colspan=\"2\">80</td></tr><tr><td>碱处理</td><td></td><td></td><td colspan=\"2\">60</td></tr><tr><td>酸处理</td><td></td><td>≥</td><td colspan=\"2\">40</td></tr><tr><td>加热伸缩率/%</td><td></td><td></td><td colspan=\"2\"></td></tr><tr><td>伸长</td><td></td><td></td><td colspan=\"2\">1.0</td></tr><tr><td>缩短</td><td></td><td>≤</td><td colspan=\"2\">1.0</td></tr><tr><td colspan=\"2\">老化处理后的断裂延伸率/%</td><td></td><td colspan=\"2\"></td></tr><tr><td>加热处理</td><td></td><td></td><td colspan=\"2\">200</td></tr><tr><td>紫外线处理</td><td></td><td></td><td colspan=\"2\">200</td></tr><tr><td>碱处理</td><td></td><td></td><td colspan=\"2\">200</td></tr><tr><td>酸处理</td><td></td><td></td><td colspan=\"2\">200</td></tr></table></body></html>  \n\n聚合物乳液防水涂料主要应用于非长期浸水结构部位的防水工程，建筑物的这类结构部位主要有屋面和内、外墙面。在屋面防水工程中应用的施工技术与上述聚合物水泥防水涂料相似，这里不赘述。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 994,
+        "chunk": "# 五、渗透结晶型防水涂料  \n\n水泥基渗透结晶型防水涂料是一种粉状材料，经过加水拌和可调制成膏状，通过刷涂或喷涂在水泥混凝土表面，亦可将其干粉撒覆并压人未完全凝固的水泥混凝土表面（有的产品也可以在配制混凝土时掺加在混凝土中）达到防水目的。我国于20世纪80年代开始引进渗透结晶型防水涂料，初期应用于上海地铁工程。90年代中期开始从国外引进应用于涂料中的活性化学物质（渗透结晶母料)，并在国内生产。该类产品已经大量应用于地下工程、地铁工程、饮用水厂、污水处理设施、桥面、隧道、水利工程和核电站等工程领域，由于具有独特的防水功能，受到工程界的重视。目前已经有较多种类不同的产品，各种产品的性能差异较大。",
+        "category": " Introduction"
+    },
+    {
+        "id": 995,
+        "chunk": "# 1.渗透结晶型防水涂料的机理及主要特性  \n\n(1）防水机理当混凝土结构在使用的过程中因各种原因而在内部产生微细裂缝而发生渗漏时，渗透结晶型防水涂料中的活性物质在遇到水后能够在基层的裂缝缺陷处产生二次结  \n\n晶，堵塞裂缝而起到防水作用。即渗透结晶型防水涂料具有自动修复微裂缝等缺陷的功能。  \n\n(2）主要特性自动修复性、整体防水性、同步（“永久\"）防水性、能够耐化学腐蚀，对钢筋起到防锈作用，无毒、无公害（国外的有些产品已经在饮用水工程中得到安全应用）等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 996,
+        "chunk": "# 2.配方与生产技术  \n\n当以采购渗透结晶型防水涂料的母料生产防水涂料时，该类涂料的生产技术较为简单，和一般粉状建筑涂料的生产过程极为相似，是一般的粉状物料的物理混合过程。以某母料生产商提供生产涂料的参考配方为例，这类涂料的参考配方见表3-1-100。  \n\n表3-1-100使用渗透结晶母料生产防水涂料的参考配方  \n\n\n<html><body><table><tr><td>原材料名称</td><td>技术要求</td><td>功能与作用</td><td>用量（质量分数）/%</td></tr><tr><td>水泥</td><td></td><td>的强酸等级为52.5 级或更高强度等缓作为除料的成膜物质和结品活性母</td><td>87</td></tr><tr><td>渗透结晶母料</td><td></td><td>技符会企业标准Q/SKRX4-2005的提供向混凝土中渗透结晶的活性</td><td>4</td></tr><tr><td>粉状硅酸钠</td><td>模数>2.0</td><td>助凝作用</td><td>3</td></tr><tr><td>石英砂</td><td>80目的过筛石英砂，不能使用磨细砂</td><td>填料</td><td>5</td></tr><tr><td>糖</td><td>优等品粉状蔗糖或葡萄糖</td><td>防止涂膜脱粉，改善施工性能</td><td>1</td></tr></table></body></html>\n\n$\\Phi$ 不应使用普通硅酸盐水泥。$\\textcircled{2}$ 该企业标准的技术要求为：细度（0.135mm筛筛余）≤3.0%；pH=12.0±1.0；不溶物含量≤0.5%；总碱量$(\\mathrm{Na}_{2}\\mathrm{O}-0.$ 658 $K_{2}(0)=35,0\\pm2,0,$ 氯离子含量≤1.0%。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 997,
+        "chunk": "# 3.渗透结晶型防水涂料的质量要求  \n\nGB18445—2001《水泥基渗透结晶型防水材料》分别规定了渗透结晶型防水涂料和渗透结晶型防水剂的质量要求。其中，渗透结晶型防水涂料的物理力学性能指标见表3-1-101（该标准正在修订中）。  \n\n表3-1-101渗透结晶型防水涂料的物理力学性能质量要求  \n\n\n<html><body><table><tr><td rowspan=\"2\">试验项目</td><td>性能指标</td></tr><tr><td>I型 I型</td></tr><tr><td>安定性</td><td>合格</td></tr><tr><td>凝结时间 初凝/min</td><td>20</td></tr><tr><td>终凝/h 抗折强度/MPs 7天</td><td>24 2.80</td></tr><tr><td>28天 抗压强度/MPa 7天</td><td>3.50 M 12.0</td></tr><tr><td>28天 湿基面粘接强度/MPa</td><td>18.0</td></tr><tr><td>抗渗压力(28天)/MPa 第二次抗渗压力（56天）/MPa ≥</td><td>1. 0 0.8 1.2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 998,
+        "chunk": "# 第五节其他功能型建筑涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 999,
+        "chunk": "# 一、概述  \n\n根据国家标准GB/T2705—2003《涂料产品分类和命名》对涂料的分类，建筑涂料分为墙面涂料、防水涂料、地坪涂料和功能性建筑涂料四类，见表3-1-102。前三类涂料，即墙面涂料、防水涂料和地坪涂料已经分别在之前的内容介绍过，本节介绍功能性建筑涂料中的部分涂料种类。  \n\n表3-1-102 建筑涂料的分类与种类  \n\n\n<html><body><table><tr><td colspan=\"2\">主要产品类型</td><td>主要成膜物质类型</td></tr><tr><td>墙面涂料</td><td>合成树脂乳液内墙涂料 合成树脂乳液外墙涂料 溶剂型外墙涂料 其他墙面涂料</td><td>丙烯酸酯类及其改性共聚乳液：醋酸乙烯及其改性共聚乳液；聚 氨酯、氟碳等树脂；无机黏合剂等</td></tr><tr><td>防水涂料</td><td>溶剂型树脂防水涂料 聚合物乳液防水涂料 其他防水涂料</td><td>EVA、丙烯酸酯类乳液；聚氨酯、沥青、PVC胶泥或油膏、聚丁二 烯等树脂</td></tr><tr><td>地坪涂料</td><td>水泥基等非木质地面用涂料 防火涂料</td><td>聚氨酯、环氧树脂等树脂</td></tr><tr><td>功能性建筑涂料</td><td>防霉涂料 保温隔热涂料 其他功能性建筑涂料</td><td>聚氨酯、环氧树脂、丙烯酸酯类、乙烯类、氟碳等树脂</td></tr></table></body></html>\n\n注：主要成膜物质类型中树脂类型包括水性、溶剂型、无溶剂型等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1000,
+        "chunk": "# 二、抗菌、防霉涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 1001,
+        "chunk": "# 1.防霉涂料的主要应用场所  \n\n微生物在自然界中可谓无处不在，居室内不通风的墙角和厨、卫间的瓷砖缝内所能够见到的霉斑、霉迹即是微生物繁殖生长的表现。霉菌的繁殖生长（长霉）并不仅仅是影响美观，还会对环境造成污染，使材料的质量发生劣变，并影响人们的身体健康，有的还会引发疾病。建筑防霉涂料是应用广泛的建筑功能性涂料品种之一。通常，建筑防霉涂料主要应用于以下三种场所。  \n\n$\\textcircled{1}$ 住宅建筑物墙壁用防霉涂料。  \n\n$\\textcircled{2}$ 特殊生产车间（如制药、啤酒、豆制品、乳制品、酿造、皮革、化妆品等）的防霉$\\textcircled{3}$ 地下工程用防霉涂料。 冷盛",
+        "category": " Introduction"
+    },
+    {
+        "id": 1002,
+        "chunk": "# 2.新型防霉技术的应用  \n\n过去使用具有防霉杀菌性能的助剂（即防霉剂）是防霉涂料最主要的防霉杀菌方式，但传统防霉剂的应用有很大局限性。传统的防霉杀菌剂大多数属于有机产品，在起到防霉杀菌的同时也为环境带来不良影响，人及动物接触到后或吸入体内也会受到影响甚至毒害。  \n\n采用有机防霉、杀菌剂所带来的不利因素已经引起重视，进而提倡使用无机防霉杀菌技术。  \n\n这类防霉杀菌材料绝大多数是由纳米材料制成的，因而也称纳米型防霉杀菌（抗菌）材料。  \n\n纳米型防霉杀菌（抗菌）材料主要是银系抗菌剂和具有光催化作用的物质。银系抗菌剂具有很好的抗菌效果和耐久性。金属离子如银、铜、锌等的无机盐对微生物具有抗菌作用。金属离子在使用过程中缓慢溶出，对微生物的细胞膜产生损伤，同时通过电化学反应破坏微生物体内的电子传导系统来杀死细菌。利用无机载体承载具有抗菌作用的金属离子，可以提高其抵抗光、热及共存物质影响的能力，使其在使用过程中缓慢溶出，具有缓释性。因此无机纳米抗菌剂是具有抗菌性的金属离子或其无机化合物与无机载体的复合体（物)，它有别于传统的有机抗菌剂和抗菌性金属及其化合物。  \n\n具有光催化作用的物质主要是指纳米 $\\mathrm{TiO}_{2}$ 和纳米 $z_{\\mathrm{nO}}$ ，利用光催化作用产生的强氧化性使微生物或微生物细胞组织失去活性。由于在作用过程中，纳米粒子本身没有参与反应，没有任何损失，因此具有长效的抗菌作用。在抗菌持效性、化学稳定性、耐热性、使用安全性、防抗药性以及抗菌、杀菌的广谱性等众多方面有了极大的改善。  \n\n采用无机纳米材料作为杀菌剂，制得的防霉杀菌涂料属于绿色环保型纳米复合杀菌乳胶漆，它无毒无味、安全环保，具有较好的杀菌效果。防霉涂料的发展正是顺应着这种市场导向，即安全性高、防霉功能强而持久、对环境友好等方面发展。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1003,
+        "chunk": "# 3.无机纳米防霉抗菌剂的种类和特征  \n\n(1）种类无机纳米防霉抗菌剂主要有金属离子型和氧化物光催化型两大类。  \n\n$\\Phi$ 金属离子型无机纳米抗菌剂金属离子型无机纳米抗菌剂是将具有抗菌功能的金属离子加载在各种无机天然或者人工合成的矿物载体上。使用时，载体缓释抗菌离子或活性氧化组分，使制品具有抗菌和杀菌的效果。在金属离子型无机抗菌剂中使用效果较好的金属离子有 $\\Lambda_{8}^{\\mathrm{~+~}}$ ， ${\\mathrm{Cu}}^{2+}$ ， $Z n^{2+}$ 等。可以使用的矿物载体很多，总的要求载体具有多孔、比表面积大、吸附性能好、无毒、化学性质稳定、不破坏抗菌成分和具有持久的缓释性能等。常用的载体有硅酸盐型、磷酸盐型和层状黏土矿物等。  \n\n$\\textcircled{2}$ 氧化物光催化型抗菌剂氧化物光催化型抗菌剂是利用N型半导体材料，如 $\\mathrm{TiO}_{2}$ ZnO、 $\\mathrm{Fe}_{2}\\mathrm{O}_{3}$ ， $\\mathbf{wo}_{3}$ 、CdS等金属氧化物在光催化作用下，将吸附在表面上的 $\\mathrm{OH^{-}}$ 和 $\\mathrm{H}_{2}\\mathrm{O}$ 分子氧化成具有强氧化能力的OH $\\cdot$ 自由基，OH·自由基具有抑制和杀灭环境中的微生物的功能。  \n\n(2）无机纳米防霉抗菌剂的特征无机纳米防霉抗菌剂在安全性、广谱性、抗药性和耐热加工性等方面具有优于有机防霉、杀菌剂的明显优势。采用无机纳米抗菌剂制备杀菌涂料具有抗菌防霉、无毒、安全、防霉时效性长等特点。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1004,
+        "chunk": "# 4.使用纳米抗菌剂制备防霉抗菌涂料技术  \n\n（1）涂料配方设计基本思路聚丙烯酸酯乳液，包括纯丙、苯丙共聚乳液，具有优良的成膜性、粘接强度、耐化学性和抗老化性，是防霉涂料的优选基料，能够制得低VOC或环境友好型产品。这类乳液作防霉涂料的基料时，应选择聚合物玻璃化温度偏高的型号，这样可以使所获得的涂膜具有适当的硬度，不易黏附环境中飞扬的营养物质和微生物孢子，即使被沾污也容易清洗。因此无机纳米防霉抗菌涂料应选择聚丙烯酸酯乳液、硅溶胶等为基料。  \n\n从有关文献资料中可以看出，由于无机纳米抗菌剂的广谱高效性和使用上的方便性，即使在普通涂料中将这类抗菌剂充分分散于涂料中，也能够得到良好的抗菌效果。但总体来说，应注意到这类涂料属于高性能功能型涂料，在配方设计时应将其PVC设置小于其CPVC，以保证涂料在发挥防霉杀菌功能的前提下具有良好的物理力学性能和耐久性能。  \n\n(2）低VOC纳米改性抗菌内墙乳胶漆使用低温成膜性好的核-壳结构乳液和功能性复合纳米材料，制备VOC含量低，防腐、防霉、抗菌效果好，且能分解周围环境中有害有机化合物的内墙乳胶漆，用于室内墙面装饰，具有环保性。  \n\n$\\Phi$ 聚丙烯酸酯乳液品种的选择从环保性能和对涂料性能的影响等因素考虑，应选择玻璃化温度低、固体含量高、乳胶颗粒的粒径细及粒径分布范围窄的乳液。这里所述的纳米抗菌乳胶漆选用低温成膜性好的核-壳结构乳液，以降低涂料中成膜助剂的用量。  \n\n$\\textcircled{2}$ 基本配方基本配方为：水 $18\\sim24$ 份；润湿分散剂 $0.4\\sim1.0$ 份；复合纳米材料$).1{\\sim}0.3$ 份；纳米硅基氧化物 $1,0\\sim3.0$ 份；二氧化钛 $10\\sim20$ 份；填料 $25\\sim35$ 份；消泡剂o $1\\sim0.2$ 份；丙烯酸醋乳液 $25\\sim35$ 份；增稠剂 $0.3{\\sim}0.4$ 份；流平剂 $0.2{\\sim}0.3$ 份。  \n\n(3）纳米改性内墙涂料与普通内墙乳胶漆的性能比较与普通内墙乳胶漆相比，纳米改性内墙乳胶漆具有更好的开罐效果，优异的耐沾污性、耐洗刷性和抗菌性，能有效催化分解周围空气中的有害有机化合物。由于制备纳米改性乳胶漆时基料选用核-壳异相构型丙烯酸酯液，具有较低的成膜温度 $(0\\sim5\\Upsilon$ ）和较高的玻璃化温度 $(5\\mathord{\\sim}14\\mathfrak{C})$ ，此涂料具有良好的成膜性能，降低成膜助剂用量，使涂料VOC含量降低。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1005,
+        "chunk": "# 5.防霉涂料的涂装  \n\n防霉涂料涂装和一般涂料涂装有所不同，主要表现在对基层的要求和处理上。防霉涂料涂装对基层有一定要求，基层最好是密实、平整、干燥、无疏松、起壳、脱落等现象的水泥砂浆墙面，混合砂浆墙面次之。在涂料涂装前，要先除去墙面上的污物、浮灰，并用热水、碱水或清水擦冲，如旧墙面上曾刷过涂料等，还需彻底清除表面涂层，露出基底，然后再作净化处理。  \n\n防霉涂料涂装的关键步骤是对墙面进行杀菌净化处理。在经过清洁处理的墙面上，用防霉洗液溶液，涂刷 $2{\\sim}3$ 道即可达到一定的杀菌效果。用于批刮的腻子最好采用有防霉性能的建筑胶或防霉型合成树脂乳液加水泥调和腻子，避免基层发生霉变。等腻子干燥后，用砂纸打磨平整。最后一道工序就是涂装防霉涂料，和一般涂料涂装要求一样。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1006,
+        "chunk": "# 6.防霉抗菌涂料的性能要求  \n\n按照HG/T3950—2007《抗菌涂料》的规定，抗菌涂料的性能要求分常规涂料性能、有害物质限量和抗菌性能三个方面。常规涂料性能应符合相关涂料产品标准规定的技术要求；抗菌涂料的有害物质限量，对于合成树脂乳液水性内用抗菌涂料，应符合GB18582中技术要求的规定；抗菌涂料的抗菌性能应符合表3-1-103和表3-1-104的规定。  \n\n表3-1-103抗细菌性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">项目名称</td><td colspan=\"2\">抗细菌率/%</td></tr><tr><td>I</td><td>Ⅱ</td></tr><tr><td>抗细菌性能</td><td>99</td><td>90</td></tr><tr><td>抗细菌耐久性能</td><td>95</td><td>85</td></tr></table></body></html>  \n\n表3-1-104抗霉菌性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">项目名称</td><td colspan=\"2\">长霉等级/级</td></tr><tr><td></td><td></td></tr><tr><td>抗霉菌性能</td><td></td><td>1</td></tr><tr><td>抗霉菌耐久性能</td><td>0</td><td>1</td></tr></table></body></html>  \n\n抗菌涂料按抗菌效果的程度，分为I级和 $\\mathbb{I}$ 级两个等级。I级适用于抗菌性能要求高的场所， $\\mathbb{I}$ 级适用于有抗菌性能要求的场所。 A",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1007,
+        "chunk": "# 三、可改善空气质量的内墙涂料  \n\n能够改善空气质量的内墙涂料主要有两类：一类是具有杀菌、防霉功能（纳米光催化）  \n\n的涂料；另一类是能够向空气中释放负离子（加入负离子添加剂）而改善室内空气质量的涂料。这两类涂料的性能特征的比较见表3-1-105。  \n\n表3-1-105纳米光催化涂料和可释放负离子涂料的特征比较  \n\n\n<html><body><table><tr><td>性能特征</td><td>纳米光催化涂料</td><td>可释放负离子涂料</td></tr><tr><td>产生功能的作用条件</td><td>需要外部紫外光源的照射</td><td>不需要任何外界能源的激发</td></tr><tr><td>净化空气的作用原理</td><td>电子-孔穴对，产生OH·自由基和O活性 氧以及氧化-还原作用等</td><td>静电场电离空气产生羟基负离子（HO或 HzO·OH）进而具有物理吸附、电性中和化学反 应等综合作用</td></tr><tr><td>材料特性</td><td>具有纳米材料的优点，同时具有化学性质 稳定、无毒和难溶等特点</td><td>水久释放负离子，产生波长范围较大的远红外线， 抗菌杀菌、消臭去味</td></tr><tr><td>功能作用</td><td>抗菌、消臭，抗紫外线、消除NO和 VOC等</td><td>去除室内空气中的甲醛、氨和苯等有害气体，抗 菌、杀菌</td></tr><tr><td>使用效果</td><td>具有明显的抗菌作用，对NO有明显的净 化效果，对其他有害气体也有一定的净化 作用</td><td>96h内对甲醛、氨、苯等的净化可达90%，有明显 的抑菌杀菌作用</td></tr><tr><td>产品优点</td><td>二低耗、操作髓便，无毒，反应条件温和，无</td><td>安全、高效、持久、广谱、便捷等</td></tr></table></body></html>  \n\n![](images/8764c3d8a63a6083eaf8d52c2ccfdd50da165a4b69176a660812e0d25143a8c3.jpg)  \n图3-1-21纳米 $\\mathrm{TiO}_{2}$ 涂料的光催化净化大气和抗菌杀菌机理示意  \n\n纳米 $\\mathrm{TiO}_{2}$ 涂料的光催化净化大气和抗菌杀菌机理如图3-1-21所示。  \n\n配制光催化杀菌型净化空气涂料的方法很重要。其中包括纳米 $\\mathrm{TiO}_{2}$ 的添加方法和与涂料中其他组分的比例，总的原则是既要保证涂料有一定的涂装黏度和涂膜物理力学性能，又不能因为其他物料比例太大，将纳米$\\mathrm{TiO}_{2}$ 包覆住，而导致光催化作用显著降低。  \n\n可释放负离子涂料是通过加入负离子添加剂形成羟基负离子而达到释放负离子作用的，羟基负离子形成过程如图3-1-22所示，化学反应如下所示。  \n\n![](images/1065c751611f5831881d04803610bd9819bf723039a36d54e3797aaefda8f9fd.jpg)  \n图3-1-22羟基负离子的形成过程示意",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1008,
+        "chunk": "# 四、保温隔热涂料",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1009,
+        "chunk": "# 1.我国建筑保温隔热涂料发展简历  \n\n我国的保温隔热涂料是在20世纪80年代末开始研制并投入应用的，并以高温场合使用  \n\n的保温隔热涂料为起点。  \n\n到90年代初，人们在硅酸盐复合保温隔热涂料的基础上开发了用于内墙墙面用的保温隔热涂料，并根据内墙墙面的环境情况，改变了基料以无机类材料为主的情况，而是采用聚乙烯醇缩醛胶、合成树脂乳液等有机基料为主要胶黏材料，将无机粗质轻填料（或者称保温隔热骨料）改变为有机材料，例如聚苯乙烯泡沫颗粒，并适量地应用了废弃材料，使涂料成本降低，绝热性能提高。  \n\n随着建筑节能工作的要求不断提高，近年来，由于墙体内保温存在很多病，外墙外保温受到重视并得以推广。建筑保温隔热涂料也开始从内墙向外墙转变。特别是隔热性能显著的反射型隔热涂料备受瞩目，且有产品问世。由于该类涂料对太阳热反射作用的特殊性能，并能够解决外墙外保温系统的开裂、渗透等问题，其应用将会受到重视并得到更多的应用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1010,
+        "chunk": "# 2.日光热反射型涂料的应用原理  \n\n日光热反射涂料的基本原理是通过涂膜的反射作用将日光中的红外辐射反射到外部空间，从而避免物体自身因吸收辐射导致的温度升高。反射型隔热涂料中通过选择透明性好的树脂和反射率高的填料，可以制得高反射率的涂膜，以达到反射热的目的。此外，反射型隔热涂料本身也具有很低的热导率，涂膜对热的传导性阻力很大，因而，即使涂膜吸收少量的太阳能，也不会通过涂膜传导。这种性能与过去的铝粉涂料具有很高的热导率的性能是完全不同的。  \n\n(1）太阳光的热辐射能任何物质都具有反射或吸收一定波长的太阳光的性能。由太阳光谱能量分布曲线可知，太阳能绝大部分处于可见光和近红外区，按波长可分为三部分，各部分在总能量中的分布见表3-1-106。  \n\n表3-1-106不同波长太阳光的热辐射能量比例  \n\n\n<html><body><table><tr><td>太阳光区</td><td>波长范围/nm</td><td>热辐射能量比例/%</td></tr><tr><td>紫外线区</td><td>200~300</td><td>5</td></tr><tr><td>可见光区</td><td>400~720</td><td>45</td></tr><tr><td>近红外区（NIR)</td><td>720~2500</td><td>50</td></tr></table></body></html>  \n\n实际上，太阳辐射热绝大部分处于 $400\\sim1800\\mathrm{nm}$ 的范围内。在该波长范围内，反射率越高，隔热效果就越好。日光热反射涂料就是通过适当选择树脂和反射填料，而制得高反射率的涂膜，以达到反射热的目的。  \n\n(2）反射机理入射在涂层上的太阳辐射能被吸收、透射或反射，其吸收率。、透射率$\\rho$ 和反射率之间有如下的关系。  \n\n$$\n\\sigma+\\rho+\\tau=1\n$$  \n\n由于涂料中存在颜料、填料，故日光热反射型涂料一般不透明。其透射率 $\\rho$ 近似为0。因此，只有提高涂层的反射率 $\\tau$ ，才可以使涂层表面吸收较少的能量，涂层温度上升的幅度不至于太高。  \n\n反射太阳光的强弱主要用物质的折射率表征，折射率越大，对太阳光的反射能力越强。常用涂料成膜物质的有机树脂的折射率为 $1.45\\sim1.50$ ，如醇酸树脂和环氧树脂的折射率接近1.48；含氟聚合物的折射率为 $1,34{\\sim}1,42$ 。从这一点来说，选择不同的有机树脂，涂层的太阳热反射效果不会发生显著的改变。  \n\n日光热反射型涂料的反射率取决于涂料中颜料、填料的光学属性（全反射和散射)，涂料中的颜料、填料主要以散射为主。颜料的折射率 ${\\mathfrak{n}}_{\\mathfrak{p}}$ 除以树脂的折射率 $n_{\\tau}$ 可计算出颜料对白光的散射能力 $m$ ，即  \n\n$$\nm{=}\\frac{n_{\\mathrm{p}}}{n_{\\mathrm{r}}}\n$$  \n\n由式(3-1-25）可见，颜料、填料的折射率与树脂的折射率相差越大，对太阳光的反射就越强。颜料、填料与树脂的这种折射率的关系，与颜料、填料的遮盖力有一定的关联。  \n\n除颜料品种外，颜料、填料的粒径对涂层的热反射性也起很大作用。散射能力m固定的颜料、填料，不同的粒径 $^d$ 有着不同的最佳反射波长 $r$ ，如式（3-1-26）所示  \n\n$$\n\\scriptstyle{r={\\frac{d}{k}}}\n$$  \n\n$$\nk={\\frac{0,90(m^{2}+2)}{n\\pi(m^{2}-1)}}\n$$  \n\n式中——涂料中树脂的反射指数；$m$ —颜料、填料的散射能力。  \n\n当 $n$ 、m为定值时，反射波长 $\\boldsymbol{r}$ 仅与颜料、填料粒径d有关。由式（3-1-26）和式(3-1-27)可见，反射较长波长的红外辐射将需要较大粒径的颜料、填料。通常二氧化钛颜料的粒径一般为 $0,2\\mu\\mathrm{m}$ ，其最佳反射波长为 $0.5\\mu\\mathrm{m}$ 。通过式（3-1-26）和式（3-1-27），根据需要反射的波长来选用合适粒径的颜料、填料，可以取得最佳的反射效果。  \n\n(3）辐射制冷机理热反射涂料在反射外部能量的同时，还会吸收部分能量。同时，涂层本身也以一定的红外波长向外辐射内部能量。物体辐射的能量可由Stenfan-Bohzman公式计算。  \n\n式中a—-Stenfan-Boltzmann 常数（斯蒂芬-玻耳兹曼），为 $5.67\\times10^{-8}\\mathrm{W}/(\\mathrm{m}^{2}\\cdot\\mathrm{K}^{4})$ ·e—物体表面发射比。  \n\n式（3-1-28）表明，物体辐射的总能量W与表面发射比和绝对温度 $T$ 的四次方成正比。随着物体表面温度的增加，发射的能量显著增加，且最大发射波长由热红外光区向近红外光区迁移。  \n\n一般来说，好的吸收体也是好的发射体，而差的吸收体必然是差的发射体。表面发射比是指物体的发射比与同样温度下的理想黑体的发射比的比率，绝大部分有机树脂有着高的发射比 $(0.85{\\sim}0.95)$ 。当辐射体的散热大于吸收，就会出现降温现象。若涂料对 $8\\sim13.5\\mu\\mathrm{m}$ 波段的吸收率很高，但对其他波段有着很高的反射比，由于黑体辐射效应的存在，可以不断地向外界辐射内部能量，从而产生散热效果。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1011,
+        "chunk": "# 3.反射型隔热涂料配制技术  \n\n(1）原材料的选用一般来说，使用不同的乳液只会影响涂料的物理力学性能，而不会对涂膜的反射性能产生显著影响。例如，有机硅-丙烯酸复合乳液能有效抵御紫外线对涂膜的光氧化降解，并因涂膜的硬度高、表面能低而提高涂膜的耐沾污性，尤其适合于制备反射型绝热涂料。颜料和填料的选用主要是着眼于反射性能。 A  \n\n近年来，使用玻璃空心微珠为功能性填料，制备的日光反射型绝热涂料具有很好的反射性能，使得这类涂料成为崭新的涂料品种，并提高了应用性能，扩大了应用领域。  \n\n(2）涂料配方设计日光热反射型隔热涂料是一种用于室外的高性能功能性涂料，对涂料的其他物理性能要求也高，例如耐候性、耐大气腐蚀性、耐酸雨等。因而，其配方的特征：一是在满足涂膜反射性能的要求下涂料的PVC浓度不能太高，否则对涂料的性能不利；二是配方的空心玻璃微珠的含量不能太低，应能够形成连续的反射面，从各种文献中的参考值来看，其用量以质量计应高于 $20\\%$ ；三是如果基料使用热塑性树脂，应注意树脂的玻璃化温度不能太低，一般应高于 $25\\Upsilon$ ；四是不能选用会显著吸收光和热的材料，特别是填料、颜料的选用。表3-1-107中给出了日光热反射型绝热涂料的参考配方。  \n\n表3-1-107生产日光热反射型绝热涂料的基本配方  \n\n\n<html><body><table><tr><td rowspan=\"2\">原材料</td><td colspan=\"2\">用量（质量分数）/%</td><td rowspan=\"2\">原材料</td><td colspan=\"2\">用量（质量分数）/%</td></tr><tr><td>配方1</td><td>配方2</td><td>配方1</td><td>配方2</td></tr><tr><td>水</td><td>12. 0</td><td>90.0</td><td>钛白粉（金红石型）</td><td>20.0</td><td>一</td></tr><tr><td>防霉剂</td><td>0.1</td><td>2.0</td><td>功能性填料</td><td>一</td><td>150.0</td></tr><tr><td>乙二醇(或丙二醇)</td><td></td><td>10.0</td><td>空心玻璃微珠</td><td>25.0</td><td>200.0</td></tr><tr><td>酯醇-12（或丙二醇丁醚）</td><td>2.0~2.5</td><td></td><td>着色颜料或色浆</td><td>一</td><td>适量</td></tr><tr><td>阴离子型分散剂</td><td>0.6~0.8</td><td>2.0</td><td>弹性聚丙烯酸酯乳液</td><td>40.0</td><td>500.0</td></tr><tr><td>润湿剂</td><td>一</td><td>1.0</td><td>消泡剂</td><td>0.4</td><td>适量</td></tr><tr><td>氨水（pH缓冲剂）</td><td>一</td><td>0.4</td><td></td><td></td><td></td></tr></table></body></html>  \n\n日光热反射绝热涂料的制备同普通涂料相似，都是物理混合过程，但在生产程序的设计上应注意空心玻璃微珠不能够受到研磨，否则会使其破碎而失去反射性能。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1012,
+        "chunk": "# 4.日光热反射型绝热涂料的性能影响因素  \n\n(1）涂料的PVC对涂膜反射性能的影响涂料的PVC影响涂膜的许多性能，研究中发现，PVC对反射型绝热涂料的涂膜反射热的性能的影响见表3-1-108和图3-1-23所示。  \n\n表3-1-108PVC对涂膜热反射率的影响  \n\n\n<html><body><table><tr><td>涂料PVC值/%</td><td>18</td><td>26</td><td>32</td><td>42</td></tr><tr><td>涂膜实测温度/℃</td><td>67.0</td><td>64.7</td><td>64.5</td><td>64.3</td></tr></table></body></html>  \n\n从图3-1-23中可以看出，随着涂料PVC值的增加，白色涂膜的反射率上升，上升到 $15\\%$ 时达到最大值，其后随着PVC值的增加反射率又下降，而在PVC值达到 $45\\%$ 以后，反射率又随着PVC值的增加而增加，并趋于平缓。其原因如下：当PVC值 $K15\\%$ 时，随着PVC值的增加，涂膜内颜料的相对密度增大，起反射作用的颜料粒子数增多，因而反射率呈上升趋势。但是，当PVC值达到 $15\\%$ 以后，随着涂料PVC值的增加，由于颜料粒子产生聚集效应，使散射的比表面积减小，散射率又降低，故反射率下降。到了 $45\\%$ 左右的PVC值时，可能已经达到了该类涂料的临界PVC值，因而PVC值再增大时，基料已不足以润湿全部颜料粒子，涂膜内有孔隙。由于孔隙中空气与颜料粒子界面之间的散射，使反射率逐渐升高。  \n\n![](images/e462ed9e50e4980a163ee4999bea37a042c8dcd2c3aa9e31968bd7b22e68c911.jpg)  \n图3-1-23太阳热反射涂料的PVC对涂膜反射率的影响  \n\n![](images/8989e3fe495ff8da4d75b1a72816ade1cc29e8fc9fd15741a61dbf379a47721c.jpg)  \n图3-1-24空心玻璃微珠对涂膜热导率的影响  \n\n(2）空心玻璃微珠对涂膜性能的影响空心玻璃微珠是反射型绝热涂料的主要功能型填料，除了影响涂膜的反射率外，也影响涂膜的热导率。涂料中添加不同体积分数的空心玻璃微珠，对涂膜热导率的影响如图3-1-24所示。  \n\n(3）不同厚度涂膜的光、热反射性能经对某进口日光热反射涂料进行的热工性能测定，这种日光热反射涂料对太阳光和辐射热的反射率可以达到 $80\\%$ 以上，其实测结果见表  \n\n3-1-109。实测结果表明日光热反射涂料对光和热辐射的反射率与其涂膜厚度的关系不大。  \n\n表3-1-109不同厚度的日光热反射涂膜对光和热的反射率  \n\n\n<html><body><table><tr><td>涂层喷涂道数</td><td>1</td><td>2</td><td>4</td><td>8</td><td>16</td></tr><tr><td>对太阳光的反射率</td><td>0.783</td><td>0.783</td><td>0.832</td><td>0.832</td><td>0.833</td></tr><tr><td>对热辐射的反射率</td><td>0.843</td><td>0.843</td><td>0.849</td><td>0.845</td><td>0.841</td></tr></table></body></html>  \n\n我国研究者配制的太阳热反射涂料也有类似的结果，即在一定的厚度范围内，涂膜反射率随着涂膜厚度的增加而提高，但达到一定值后，由于光线并不能够透过涂膜照射到基层，因而涂膜厚度再增加，对反射率的影响不大。具体地说，在涂膜厚度达到 $60\\mu\\mathrm{m}$ 后，涂膜的反射率基本不随着涂膜厚度的增加而变化，见表3-1-110。  \n\n表3-1-110涂膜摩度与反射率的关系  \n\n\n<html><body><table><tr><td>涂膜厚度/μm</td><td>20</td><td>40</td><td>60</td><td>80</td><td>100</td><td>120</td></tr><tr><td>反射率</td><td>0.769</td><td>0.805</td><td>0.813</td><td>0.814</td><td>0.816</td><td>0.815</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1013,
+        "chunk": "# 5.反射隔热涂料的性能要求  \n\n根据行业标准JC/T1040—2007《建筑外表面用热反射隔热涂料》，按产品分散介质的不同分为水性和溶剂型两类。建筑反射隔热涂料的技术要求应符合表3-1-111的规定。  \n\n表3-1-111建材行业标准JC/T1040—2007对建筑反射隔热涂料的质量要求  \n\n\n<html><body><table><tr><td rowspan=\"2\">性能指标项目</td><td colspan=\"2\">性能指标</td></tr><tr><td>W</td><td>S</td></tr><tr><td>容器中状态 施工涂</td><td>搅拌后无硬块、凝聚，呈均匀状态 刷涂两道无障碍</td><td>搅拌后无硬块、凝聚，是均匀状态 剧涂两道无障碍</td></tr><tr><td>膜外观性 低温稳定性</td><td>无针孔、流挂，涂膜均匀 无硬块、凝聚及分离</td><td>无针孔、流挂，涂膜均匀</td></tr><tr><td>干燥时间(表干)/h</td><td>2</td><td>2</td></tr><tr><td>耐碱性</td><td>48h无异常</td><td>48h无异常</td></tr><tr><td></td><td></td><td></td></tr><tr><td>耐水性</td><td>96h无异常</td><td>168h无异常</td></tr><tr><td>耐洗刷性/次</td><td>2000</td><td>5000</td></tr><tr><td></td><td></td><td></td></tr><tr><td>耐沾污性（白色和浅色）</td><td>20</td><td>10</td></tr><tr><td>涂层耐温变性(5次循环)</td><td>无异常</td><td>无异常</td></tr><tr><td>太阳反射比(白色)</td><td>0.83</td><td>0.83</td></tr><tr><td>半球发射率</td><td>0.85</td><td>0.85</td></tr><tr><td>耐弯曲性/mm</td><td></td><td>2</td></tr><tr><td>拉伸性能</td><td></td><td></td></tr><tr><td>拉伸强度/MPa</td><td>1.0</td><td></td></tr><tr><td>断裂伸长率/%</td><td>100</td><td></td></tr><tr><td>耐人工气候老化性</td><td></td><td></td></tr><tr><td>外观</td><td>400h不起泡、不剥落、无裂纹</td><td>500h不起泡、不刺落、无裂纹</td></tr><tr><td>粉化，级</td><td>1</td><td>1</td></tr><tr><td>变色（白色和浅色）/级</td><td>2</td><td>2</td></tr><tr><td>太阳反射比（白色）</td><td>0. 81</td><td>0.81</td></tr><tr><td>半球发射率</td><td>0.83</td><td>0.83</td></tr><tr><td>不透水性</td><td>0.3MPa、30min不透水</td><td></td></tr><tr><td>水蒸气渗透率/[g/（m²·s▪Pa)]≥</td><td>8.0×10*</td><td></td></tr></table></body></html>\n\n$\\Phi$ 浅色是指以白色涂料为主要成分，添加适量色浆后配制成的浅色涂料形成的涂膜所呈现的浅颜色，按GB/T15608—1995中4.3.2规定明度值为 $\\scriptstyle6\\sim9$ （三刺激值中的 $Y_{\\mathrm{res}}{\\geqslant}31.26)$ .",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1014,
+        "chunk": "# 参考文献  \n\n[1] 管从胜，王威强编著，氟树脂涂料及其应用，北京：化学工业出版社，2004：201-202.  \n[2] 刘洪珠，氟含量与氟碳涂料性能关系浅析，现代涂料与涂装，2005，8（3）：4-6.  \n[3] 张良均等，硅酸锂的合成与应用研究，现代涂料与涂装，2002，（4)：4-5.  \n[4] 陈素平等，第二届中国建筑涂料发展战略与技术研讨会论：硅溶胶在建筑涂料中应用研究，上海：上海建筑科学研究院，2002.  \n[5] 张季冰，徐忠珊，石油沥青聚氨酯防水涂料甲乙组分相容性研究，新型建筑材料，2002（5)：20.  \n[6] 王庆安，高果桃，水固化聚氨酶——一种新型防水涂料，中国建筑防水，2005，（10）：8-9.  \n[7］余剑英，颜永斌，缪沾等，单组分聚氨酶/蒙脱土纳米复合防水涂料的研究，新型建筑材料，2004，（7）：55-57.  \n[8] 沈培康等，纳米材料在建筑涂料中的应用研究，建筑涂料，2004，（1)：12-13.  \n[9] 马宏，刘文兴，孟军锋等，高性能太阳热反射隔热涂层的研制，现代涂料与涂装，2006，9（7）：55-56.  \n[10] 林宣益，乳胶漆，北京：化学工业出版社，2004.  \n[11]PraneJ R.Journal of Coatings Technology，1996, 68 (860) 74-79.  \n[12] Hill WH StauffrJ G.Brush Strokes (A Rohm and Haas Company Publication)，,2003, (1) 4-21.  \n[13] 云华，中国涂料，1998；（4)；5-8.  \n[14]Juan Antonio,Gonzalez omez,Asia PacificCoatingsJournal,2005,(4)12-16.  \n[15] 朱传榮．中国涂料，1997，（5)：24-26.  \n[16] Schwartz M, Baumstark R.Waterbased Acrylates for Decorative Coatings, Hannover : Vincentz Verlag, 2001[17] Doer H,Holzinger F.Kronos Titandioxid in Dipersionsfarben,Dortmund Fritz BuscheDuckereigeselschaft mbH1990[18] OliverW.Polymerdispersions asbinders in silicone resin system，BASFTechnicalData,1997;16-20[19] Asbeck W K, Van Loo M. Ind. Eng. Chem, • 1949. (41); 1470.  \n[20] Floyd FL,Holsworth RM,Journalof Costings Technology,1992,64（806)65-69.  \n[21]Schallr E J. Journal of PaintTechnology,1968, 40(525) 433.  \n[22]［美]T.C.巴顿著，涂料流动与颜料分散，郭隽奎等译，北京：化学工业出版社，1988.  \n[23]ZenoWicksW等著，有机涂料科学和技术．经良等译，北京：化学工业出版社，2002.  \n[24] Woodbridge R,Principles of Paint Formulation.New York: Chapman and Hall, 1991.  \n[25]Stieg F B.Journal of Costings Technology, 1981 •53(680)；680.  \n[26]BroomeTT.Approaches to Formulating Interior LatexPaints for the Southeastern U.S.Paintand Coatings indus-try,2007, 23(4): 66-83.  \n[27] Berns RC编著．颜色技术原理. 李小梅等译，北京：化学工业出版社，2002：216-288.  \n[28] 李亨著，颜色技术原理及其应用北京：科学出版社，1994：233-242.  \n[29] 涂料工艺编委员编，涂料工艺. 第三版（下册）．北京：化学工业出版社，1997.  \n[30] 周春隆，穆振义，编著，有机颜料化学及工艺学（修订版）．北京：中国石化出版社，2002.  \n[31] Lin XuanyiEuropeanCoatingsJournal，002，(12）32-34.  \n[32] 歇耀宗，曹同玉主编 合成聚合物乳液制造与应用技术，北京：中国轻工业出版社，1999.  \n[33] Born A,Ermuth J.Farbe&Lack,1999, (3)96-104.  \n[34] Born A, Ermuth J.Neinbuis C, Phanomen Farbe, 200, (2)； 34-36.  \n[35] Born A, Ermuth J.Farbe & Lack, 2001, (7): 87-93,[36] 张宪康. 水性聚氨酯外墙涂料研究，2005中国建筑涂料制造技术研讨会，2005，上海.  \n[37] Taylor J W, Minnik M A.Journal of Coatings Technology Research,2004， (3)；163-190,[38] Yasuharu Nakayama. Prog. Org. Coat， 2004， (51)； 280-299.  \n[39] 蒋硕健，张斌，李明谦， 中国涂料工业咨讯报告会论文集：（甲基）丙烯酸的双环戊烯基酯与双环戊烯基氧乙基酯的性能特点与应用，北京：中国涂料协会，2004.9：70-82.  \n[40] Zakir H. Ansari paintindia，2003, (6)：39-46.  \n[41] 冀志江，王晓燕，王静，金宗哲，中国建材科技，2004，（3）；1-4.  \n[42] 季君晖，史维明编著，抗菌材料，北京：化学工业出版社，2003.",
+        "category": " References"
+    },
+    {
+        "id": 1015,
+        "chunk": "# 汽车涂料  \n\n汽车工业是国民经济的重要支柱产业。自改革开放以来，汽车工业获得了飞速的发展，汽车总产量由1980年的22万辆增加到2008年的1000万辆以上，轿车产量也由1985年的8825辆增加到600万辆左右。其增长速度不仅惊人，而且大大超过不少发达国家。汽车工业的迅速发展，为汽车涂料提供了广阔的发展空间，近年来我国不少大中型涂料骨干企业通过引进技术、合资合作，已经形成年产汽车涂料20余万吨的生产能力，这和当前汽车工业对其涂料的需求大体相当。目前我国汽车业每年约需汽车涂料20余万吨，其中汽车原厂漆（OEM）16万～17万吨（电泳底漆5万 ${\\sim}7$ 万吨，中涂7万 ${\\sim}8$ 万吨，各类面漆4万 ${\\sim}5$ 万吨)，PVC抗石击涂料2万 ${\\sim}3$ 万吨，其他类型涂料2万吨左右，汽车修补漆大约10万吨左右。  \n\n众所周知：汽车涂料和建筑涂料一直以来都是涂料工业的两大支柱产业，建筑涂料的支柱作用体现在“量”上，而汽车涂料的支柱作用则体现在“质”上（2004年的统计数据表明；即使在西方发达国家，汽车涂料也不过才占到涂料总产量的 $7\\%$ 左右)。  \n\n就其涂装工艺而言；汽车涂装领域囊括了涂料行业中诸如阴、阳极电泳、空气雾化喷涂、高压无气喷涂、静电旋杯等几乎所有的施工手段。因此不少人士都认为；汽车涂料，尤其是轿车涂料领域，可以代表一个国家涂料工业的最高技术水平和发展方向。因此，熟悉了解，进而掌握汽车涂料的基本技术对于一个涂料工作者而言就显得格外重要了。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1016,
+        "chunk": "# 第一节底漆及电泳底漆  \n\n按照传统概念，底漆的作用主要在于金属基材的防锈及增强面漆对基材的附着力。其实，底漆对整个涂装系统的质量及装饰性也有着非常重要的影响。汽车业和涂料行业从来都没有忽视过底漆的功能。自汽车问世以来，底漆大体经历了如下演变过程(表3-2-1)。  \n\n油性底漆—→硝基底漆—→醇酸（或酚醛）底漆—→环氧酯底漆-→阳极电泳底漆—→阴极电泳底漆  \n\n可以从这几代底漆的耐盐水（或盐雾）性能的演变看出汽车行业对涂料的要求不断升级的趋势。在汽车刚刚问世的那几年间，底漆采用的是醇酸或环氧酯底漆。其中醇酸或环氧酯铁红底漆应用最为广泛。这两类底漆因综合力学性能优良，一直占据着工业底漆的绝大部分市场。从表3-2-2中数据可知；传统的醇酸铁红底漆的物理力学性能都非常优良，但其耐盐雾性、与面漆的配套性（底漆自身的铁红色与汽车常用色之间往往存在巨大反差，不能形成最佳覆盖）等均无法满足汽车工业对涂料行业越来越苛刻的需求。此后，虽然也有水性喷涂底漆、溶剂型及水性浸涂漆投人到汽车底漆市场，但使用面并不太广，真正主导汽车底漆市场的仍然是晚些时候出现的电泳底漆。  \n\n表3-2-1历代汽车用底漆膜厚及耐介质性能  \n\n\n<html><body><table><tr><td></td><td>底漆类型</td><td></td><td>耐盐水性能/h</td><td>耐盐雾性能/h</td></tr><tr><td>酚醛底漆</td><td></td><td></td><td></td><td></td></tr><tr><td>铁红</td><td></td><td></td><td>24</td><td></td></tr><tr><td>锌黄</td><td></td><td></td><td>36</td><td></td></tr><tr><td>醇酸底漆</td><td>铁红</td><td></td><td>24</td><td></td></tr><tr><td>酚醛阳极电泳底漆</td><td></td><td>铁红（膜厚25μm）</td><td>24~48</td><td></td></tr><tr><td>环氧阳极电泳底漆</td><td>铁红（膜厚25μm）</td><td></td><td>24~48</td><td></td></tr><tr><td>聚丁二烯阳极电泳底漆（膜厚25μm）</td><td></td><td></td><td></td><td>192~480（磷化钢板）</td></tr><tr><td>第一代阴极电泳底漆（膜厚18pm）</td><td></td><td>中灰</td><td></td><td>720</td></tr><tr><td>第二代阴极电冰底漆（膜厚30～35μm）</td><td></td><td>中灰</td><td></td><td>1000</td></tr><tr><td>第三代阴极电泳底漆（膜厚23～25μm）</td><td></td><td>中灰</td><td></td><td>1000</td></tr></table></body></html>  \n\n表3-2-2醇酸铁红底漆性能  \n\n\n<html><body><table><tr><td>项 目</td><td>性能指标</td><td>检测标准</td></tr><tr><td>漆膜颜色及外观</td><td>平整、光滑，铁红色</td><td>GB 17291979</td></tr><tr><td>原漆黏度(涂-4杯)/s</td><td>≥80</td><td>GB 1723—1993</td></tr><tr><td>原漆细度/μm</td><td>≤50</td><td>GB 1724—1989</td></tr><tr><td>原漆不挥发分/%</td><td>≥50</td><td>GB 1725—1989</td></tr><tr><td>烘烤时间（105℃±2℃）/min</td><td>30</td><td></td></tr><tr><td>硬度</td><td>≥0.3</td><td>GB 1730—1993</td></tr><tr><td>柔韧性/mm</td><td>≤1</td><td>GB 17311993</td></tr><tr><td>冲击性/cm</td><td>≥50</td><td>GB 17321993</td></tr><tr><td>附着力（划圈法）/级</td><td>≤1</td><td>GB 1720—1989</td></tr><tr><td>耐盐雾性/h</td><td>72</td><td>EQ Y-2381994</td></tr><tr><td>与面漆的配套性</td><td>尚可</td><td></td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 1017,
+        "chunk": "# 一、浸涂及自泳底漆  \n\n浸涂工艺相比喷涂而言具有漆料利用率高、VOC极低、设备比较简单以及特别适合涂装形状复杂的工件的几大特点，一直以来被广泛用于工业底漆的涂装中。在汽车行业，浸涂工艺多被用于汽车底盘以及大型巴士的底漆涂装。与涂料行业其他领域的发展趋势一样，浸涂工艺的水性化比喷涂工艺的发展要快得多，溶剂型浸涂漆已差不多完全为水性浸涂漆所替代。今天真正用于汽车总装厂浸涂工艺的浸涂漆有水性丙烯酸和水性环氧酯等几类。在浸涂工艺领域又发展了一种将表面处理技术与之良好结合的所谓自泳涂装技术被有效用于大型车辆车身的涂装中，现分述如下。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1018,
+        "chunk": "# 1.浸涂底漆  \n\n因安全方面原因，溶剂型浸涂漆已经基本退出汽车涂装市场，尚存浸涂漆几乎都是水性丙烯酸或环氧酯类。  \n\n水性丙烯酸类浸涂漆借鉴溶剂型烤漆的交联系统，除引入适量羧基以保证其水稀释性外，还需引入适量的羟基。与溶剂型丙烯酸树脂合成工艺不同的是，这里必须采用亲水性溶剂，如醇类、醇醚类等。现举一实用范例供参考。  \n\n（1）配方（质量份）  \n\n<html><body><table><tr><td>异丁醇</td><td>39.2</td><td>丙烯酸</td><td>20.4</td></tr><tr><td>丙烯酸丁酯</td><td>10.7</td><td>BPO</td><td>2. 0</td></tr><tr><td>苯乙烯</td><td>19.3</td><td>乙醇胺</td><td>1.8</td></tr><tr><td>丙烯酸羟丙酯</td><td>7.6</td><td></td><td></td></tr></table></body></html>  \n\n(2）工艺  \n\n$\\Phi$ 将异丁醇加人到反应釜中，升温至回流，保持稳定 $10\\mathrm{min}$  \n\n$\\textcircled{2}$ 将丙烯酸丁酯、苯乙烯、丙烯酸羟丙酯、丙烯酸、BPO混合，搅拌至完全混溶，在搅拌下滴加到大约4/5的混合物（耗时约2h）后暂停，保温2h，然后继续滴加，耗时约$30\\mathrm{{min}}$ ，继续保温 $^{3\\mathrm{h}}$ 。  \n\n$\\textcircled{3}$ 降温至 $110^{\\circ}\\mathrm{C}$ ，加入乙醇胺，搅拌约 $30\\mathrm{min}$  \n\n$\\textcircled{4}$ 降温至 $60^{\\circ}\\mathsf{C}$ ，过滤、出料。  \n\n在水性浸涂漆系统中采用的氨基树脂也必须能够与水以任何比例混容。甲醚化三聚氰胺甲醛树脂是最为适用的氨基树脂，这种氨基树脂与羟基丙烯酸树脂交联成膜后具有硬度高、柔韧性好以及耐各类介质性能突出等特点，为大多水性丙烯酸浸涂漆所采用。  \n\n在浸涂漆中可采用的颜料有；氧化铁系、偏硼酸钡、三聚磷酸铝、锶黄以及铬黄等，上述颜料大都能够提升水性浸涂漆的耐盐雾性能。  \n\n现举一例铁红水性丙烯酸浸涂漆配方（质量份）：  \n\n\n<html><body><table><tr><td>水性羟基丙烯酸树脂</td><td>30.10</td><td>锌铬黄</td><td>0.35</td></tr><tr><td>六甲氧基三聚氰胺甲醛树脂</td><td>8.25</td><td>超细沉淀硫酸侧</td><td>13.10</td></tr><tr><td>氧化铁红</td><td>9.00</td><td>滑石粉</td><td>10.20</td></tr><tr><td>云母粉</td><td>0.50</td><td>去离子水</td><td>28.50</td></tr></table></body></html>  \n\n采用上述配方制得的浸涂漆经烘烤成膜后，耐盐雾性能可达360h左右。与喷涂、电泳涂装工艺相比，它可使工件内外表面，包括焊缝、棱角等部位均能涂覆一层均匀、完整的漆膜，使工件整体防腐蚀能力大大提高。  \n\n值得注意的是；浸涂涂装工艺与电泳类似，日常管理及控制非常重要，对槽液黏度、温度、不挥发分等均需经常检测，以进行适当调节。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1019,
+        "chunk": "# 2.自泳底漆  \n\n自泳涂装与电泳涂装工艺类似，也是以浸涂方式完成涂装的一种比较新的涂装技术。自泳涂装技术虽然几乎与电泳涂装技术同时为人们所了解，但迄今所占市场份额却相对较小。目前汽车行业内只有那些生产如豪华巴士一类的大型车辆的总装厂选用这种比较特殊的工艺。与电泳涂装工艺相比，自泳涂装工艺具有以下特点。  \n\n$\\textcircled{1}$ 基本建设投资较少自泳涂装不需要磷化处理之类电泳涂装系统中必不可少的前处理工艺，缩短了流程、减少了占地面积；  \n\n$\\textcircled{2}$ 节约能源自泳涂装与电泳涂装不同，它是一种纯化学作用过程，因此可大大节约涂装用电能。  \n\n$\\textcircled{3}$ 涂装效率高自泳涂装中当工件离开槽液时，湿漆膜仍然可以继续进行化学反应而成膜，显然通过水洗而去掉的多余漆料远远少于电泳涂装。  \n\n$\\textcircled{4}$ 泳透率高自泳底漆的泳透率极高，换言之，在自泳涂装系统中根本就不存在泳透率的问题，它对于任何复杂表面的覆盖都十分均匀，有关数据显示，性能良好的自泳底漆的厚度差不会超出 $2\\mu\\mathrm{m}$  \n\n$\\textcircled{5}$ 维护简便自泳涂装系统的日常维护大大低于电泳涂装系统，如挂具的清理、超滤系统、泵循环系统等。  \n\n$\\textcircled{6}$ 耐各种介质性能耐盐雾性能优于普通AED但低于CED，大约与聚丁二烯类AED相当。  \n\n$\\textcircled{7}$ 前处理尽管自泳涂装系统不需要磷化之类表面处理，但它对表面状态的要求一点也不低于CED，如油污、润滑脂、焊渣等异物的清洗要求非常高，甚至对其粗糙度都有非常苛刻的需求。  \n\n自泳涂装用底漆由含颜料的乳液、氢氟酸以及氧化剂（双氧水或重铬酸盐）所组成。在金属工件浸人到槽液中时，工件表面立即被酸侵蚀，产生多价金属离子，这些金属离子与聚合物乳胶发生反应，使之失去亲水性而沉积在工件表面，大体基本原理如下。  \n\n伴随着聚合物乳胶粒子与基材表面的二价铁离子的结合，基材表面逐步被完全涂装，反应也随之终止。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1020,
+        "chunk": "# $\\Phi$ 自泳底漆涂装槽液的配方（mL/L)  \n\n自泳底漆漆料（NVM $\\c=$ 40%) 125.0\\~150.0 HF(40%) 1.0\\~2.5  \nFeF溶液（Fe含量2%） 25.0\\~50.0 HO(35%) 2.0\\~5.0  \n\n$\\textcircled{2}$ 自泳底漆涂装工艺管理自泳底漆涂装与电泳底漆类似，其涂装质量的保证除底漆自身质量外，还需要对槽液参数进行严格的管理。主要控制参数有：槽液不挥发分、总铁及亚铁含量、 $\\mathsf{p H}$ 值、槽液温度以及所谓凝聚值等。这些对于保证涂装质量、延长槽液的寿命、提高槽液的稳定性均起到重要作用。上述参数的监控除不挥发分和凝聚值可每周监测一次外，其他参数均需每天进行一次。  \n\n以德国汉高公司用于自泳涂装的Autophoretic866产品为例，其槽液的不挥发分一般控制在 $5\\%\\sim7\\%$ ，涂装时间一般为 $1.5{\\sim}2.5\\mathrm{min}$ ，烘烤条件为 $115\\mathrm{^c\\times45min}$ ，据称其耐盐雾时间可达600h左右（划叉），超过一般阳极电泳底漆，而与聚丁二烯类阳极电泳底漆大体相当。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1021,
+        "chunk": "# 3.水性浸涂漆的技术标准  \n\n1999年发布了“涂装作业安全规程-—浸涂工艺安全”国家标准（GB17750—1999），对于规范浸涂漆的工艺，保障操作人员和财产的安全发挥了重要作用。现将水性浸涂漆常见标准列于表3-2-3。  \n\n表3-2-3水性漫涂漆的技术标准  \n\n\n<html><body><table><tr><td>项目</td><td>技术指标</td><td>检测标准</td><td>项目</td><td>技术指标</td><td>检测标准</td></tr><tr><td>不挥发分/%</td><td>≥50</td><td>GB 17251979</td><td>柔韧性/mm</td><td>≤3</td><td>GB 1731—1979</td></tr><tr><td>细度/μm</td><td>≤30</td><td>GB 1724—1979</td><td>冲击性/cm</td><td>50</td><td>GB1732—1979</td></tr><tr><td>附着力/级</td><td>≤2</td><td>GB 1720-1979</td><td>铅笔硬度/H</td><td>2</td><td>GB1739-1979</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1022,
+        "chunk": "# 二、电泳底漆  \n\n汽车等交通运输车辆涂装用底漆自20世纪60年代美国福特公司第一个阳极电泳槽、70年代第一个阴极电泳槽开始运行以来，这种涂装工艺在过去的40多年中已经成为汽车底漆涂装的最为主要的施工手段。电泳底漆之所以能够取代其他喷涂、浸涂类底漆，究其主要原因可以归纳为以下几点。  \n\n涂装效率高高达 $90\\%\\sim95$ %的涂料利用率，远非其他施工手段所能比拟。  \n\n你农从平间 阿②防腐蚀性能优良由表3-2-1中可以看到，各类电泳底漆均具有出色的防腐蚀性能。③极低的VOC值各类电泳底漆均以水为主要溶剂，而在新一代的阴极电泳底漆中作  \n为助溶剂的醇醚类或醚酯类溶剂的量也由以往的2%～3%降低到0.4%～0.8%这样非常低  \n的水平。④ 经济效益高适应于大规模的工业涂装线生产，可非常方便地实现机械化、自动化。$\\textcircled{5}$ 具有良好的漆膜外观漆膜平整光滑、致密，对面漆的烘托性能良好。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1023,
+        "chunk": "# 1.电泳的基本原理  \n\n众所周知，所谓“电泳”不过是电泳涂装过程中的一个环节，它至少包含电泳、电解、电沉积以及电渗四大阶段。因此，把这种施工工艺称之为“电沉积”似乎更为科学一些。举阳极电泳过程为例，其原理是；阴离子型水性树脂微粒在电场作用下，向作为阳极的待涂装工件运动，放电后形成非水溶粒子在工件表面沉积，沉积的漆膜经过电渗析过程完成最后的涂装。在阳极电泳涂装的过程中，阳极和阴极也将可能发生其他电极反应，如：  \n\n$$\n2{\\bf O}{\\bf H}^{-}-2{\\bf e}^{-}\\longrightarrow{\\bf H}_{2}{\\bf O}+\\frac{1}{2}{\\bf O}_{2}\\uparrow\n$$  \n\n反应中产生的气体容易使所沉积的涂层表面出现针孔、气泡，同时由于基材金属以离子形式溶出，必将破坏被涂工件的表面处理膜（磷化膜、钝化膜）使表面变得粗糙，降低表面的致密性，影响漆膜的防锈性能。而且，已溶出的 $\\mathrm{Fe}^{2+}$ ，不仅仅污染了槽液，还将影响槽液的工作参数。更为严重的是，它还可能与树脂微粒发生反应，生成不溶于水的沉淀，影响槽液的稳定性，严重时将对槽液带来灾难性的破坏。  \n\n阴极电泳底漆的涂装过程正好相反，作为成膜物质的带正电荷的阳离子树脂在电场作用下，向作为被涂工件的阴极运动，并在其上沉积。总之电泳涂装过程是一系列电化学反应的结果，现将电解、电泳、电沉积、电渗等几个过程分别表述如下。  \n\n（1）电解电解是电介质（如盐类溶液）在电流的作用下分解，从而导致在电极附近产生离子。以水分子为例，产生 $\\mathrm{OH^{-}}$ 和 $\\mathbf{H}^{+}$  \n\n(2）电泳分散在极性介质中的带电粒子在电场的作用下向相对应的电极移动。由此，在阳极电泳中，带负电荷的粒子移向阳极，而阴极电泳时，则是带正电荷的粒子则移向阴极。  \n\n(3）电沉积漆料粒子由于电化学反应而沉积在作为极板的金属工件上，生成具有紧密附着的涂层。电荷中和后，粒子析出和附着是由沉积粒子的结构来决定的。在电沉积的过程中，电场力是影响涂层致密、均一性的重要因素。随着电沉积过程的进行，漆膜厚度逐渐增加，其电阻也随之而提高，直至工件变得完全绝缘，电沉积停止。涂层厚度与电流的关系如图3-2-1所示。  \n\n![](images/0b7d523333489c88d6abebfe4a6a534981846fc504ac848fb077c019ef95fdf5.jpg)  \n图3-2-1膜厚与电流随时间的变化曲线  \n\n（4）电渗析电渗析过程是上述电泳的逆过程。在电场的作用下，如果析出的粒子黏附于工件表面而不再运动，而分散介质则从不致密的松散粒子反向移动而出，这一电化学过程使得溶剂和低分子化合物渗析出来，漆膜则变得更为致密、坚韧。  \n\n总之，电泳涂装过程可以归结如下：  \n\n$\\Phi$ 通电、加电压，产生电流； $U=I R$   \n$\\textcircled{2}$ 电极附近水分子分解——电解；  \n$\\textcircled{3}$ 漆料粒子向与其电荷极性相反的电极移动——电泳；  \n$\\textcircled{4}$ 漆料粒子析出——电沉积；  \n$\\textcircled{5}$ 随着溶剂等低分子物质的渗出，漆料粒子更为紧密地黏附于工件表面—电渗析；  \n$\\textcircled{6}$ 随着涂层厚度的增加，工件变成绝缘体；  \n$\\textcircled{7}$ 电沉积自动终止。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1024,
+        "chunk": "# 2.阳极电泳底漆（以下略为AED）  \n\n虽然AED先于CED问世，但当今汽车总装厂大都采用各类阴极电泳底漆。不过到20世纪80年代为止，在西欧和日本仍有 $20\\%\\sim25\\%$ 的汽车上采用阳极电泳底漆。相继问世的AED主要有环氧酯类、酚醛类、聚丁二烯、丙烯酸等几大类。  \n\n(1）环氧酯类环氧类阳极电泳底漆是由环氧树脂（多为E-20、E-51等）用干性油（如亚麻仁油、桐油等）脂肪酸酯化，再与不饱和羧酸（如：顺丁烯二酸酐、反丁烯二酸酐等）加成后用某些水溶性胺类（如一乙醇胺、二乙醇胺等）中和制得可用作阳极电泳底漆的水分散性树脂。  \n\n脂肪酸的羧基与环氧树脂的环氧基、羟基发生酯化反应生成环氧酯。通常这类反应是在无机或有机碱存在进行的。由于环氧基比羟基活泼，故首先羧基与环氧基反应生成半酯。其反应式如下：  \n\n$$\n\\sum\\limits_{\\mathrm{o}}[I_{\\frac{\\cdot}{\\cdot}\\frac{\\cdot}{\\mathrm{o}}}+\\substack{\\mathrm{RCOOH}\\longrightarrow\\mathrm{RCO0}}[]_{\\frac{\\cdot}{\\cdot}\\frac{\\cdot}{\\mathrm{o}\\mathrm{H}}}]_{\\bullet\\mathrm{OH}}\n$$  \n\n式中，RCOOH为不饱和脂肪酸，如亚油、桐油以及脱水麻油脂肪酸等；七为组成环氧树脂的基干基团，如双酚A、双酚F等。  \n\n除上述半酯化反应外，尚有环氧基与羟基的酯化反应生成全酯、环氧基与羟基的醚化反应以及脂肪酸碳链上的双键的聚合反应等。这些反应中，半酯化与全酯化反应是生成环氧酯必要的反应，而醚化和聚合反应则是应该尽可能避免的副反应。  \n\n制得环氧酯后再使其与不饱和羧酸（如顺丁烯二酸酐、反丁烯二酸酐等）进行加成反应，在其大分子主链上引入羧基，其反应式如下。  \n\n![](images/3a80bd7193377b4346dcf629a7bdebc83dd4a5c48bb713308277e16fa86bedc5.jpg)  \n\n在环氧酯的主链上引人羧基后，再用有机胺类中和即得可分散于水中的聚合物。  \n\n$\\textcircled{1}$ 主树脂原料  \n\na.环氧树脂阳极电泳底漆用环氧树脂的虽然分子量越高，力学性能和耐介质性能等均可得到提高，但水分散性能却同步变差。故一般采用较低分子量的环氧树脂，如E-20、E-51等。  \n\nb.脂肪酸为了在主链上引人一定数量的羧基，要求脂肪酸含有一定量的不饱和双键，此外，这类阳极电泳底漆固化的基础是“氧化交联”成膜，同样需要不饱和双键。为了保证足够的不饱和度，选择单一亚油已远远无法满足上述要求，一般采用与桐油拼用的办法，或者选用脱水麻油酸，可以获得较好的综合力学性能及耐腐蚀性能。  \n\n$\\textcircled{2}$ 颜料、填料由于阳极电泳底漆的颜色一般比较单一，多为铁红色、黑色、灰色等，故所采用的颜料不外乎钛白、铁红、炭黑以及某些起防腐蚀作用的颜料及一般填料。  \n\na.钛白粉涂料行业中各类底、中以及面漆中应用最为广泛的主要的白色颜料。由于二氧化钛虽然对大气中各类化合物质稳定，不溶于水和弱酸，但微溶于碱，故阳极电泳底漆中采用的钛白粉必须是氧化铝和二氧化硅包覆的产品，如杜邦公司的R900等标明可用于水性涂料中的牌号。  \n\nb.炭黑因生产工艺不同，炭黑有槽黑、灯黑、炉黑、乙炔黑等多个品类，前三类应用较为普遍。由于槽黑偏酸性，它的 $\\mathsf{p H}$ 较低，与较高 $\\mathtt{p H}$ 的AED无法匹配，故不适合用于AED之中，只可采用 $\\mathfrak{p H}$ 相对较高的炉黑或灯黑。如德固萨的LampBlack101和卡伯特的Monarch 880等。  \n\nc.铁红铁红是氧化铁系颜料中用于涂料行业量最大的一个品种，其化学组成为三氧化二铁。在阳极电泳底漆中被广泛用作着色及主要防锈颜料。这类颜料具有下述特点：  \n\n·极高的化学稳定性、耐碱性、耐稀酸性；·对热、光均稳定，耐热性高达1200℃以上；·遮盖力高，是除炭黑外遮盖力最好的品类之一；·着色力较好，可用作着色颜料，但因生产工艺及生产厂家的不同，色相稳定性一般不太好；·同样因生产厂家的不同，导致吸油量也有差异；·密度较大，在各类电泳底漆中使用时容易发生沉降现象。  \n\nd.铁黑铁黑是氧化铁系列中黑色类颜料，它具有氧化铁红几乎所有特点，一般在AED中用作炭黑颜料的补充。  \n\ne.硫酸锁应用最为普遍的填料之一，其化学成分为 $\\mathrm{BaSO_{4}}$ ，有天然和合成两大类天然矿物产品俗称重晶石粉，合成的产品则被称为沉淀硫酸钡。两者的特点如下：  \n\n·折射率较高（填料类中)，故表观颜色较白，遮盖力较高；  \n·中性填料，耐酸、耐碱，对热、光稳定；  \n·吸油量较低，特别适用于厚浆底漆；  \n·密度较高，是填料中最高的品种，尤其是天然产品。  \n\n由于这类填料中，天然产品—重晶石粉的密度较高，故对于要求抗沉降性突出的电泳底漆系统中，普遍采取将重晶石粉与沉淀硫酸钡搭配使用的方案以弥补彼此的不足。  \n\nf.碳酸钙碳酸钙的化学成分为 $\\mathrm{CaCO_{3}}$ ，亦有天然和合成之分。天然品称为重质碳酸钙，合成品成为轻质碳酸钙。碳酸钙可溶于酸，属碱性填料，其 $\\mathbf{\\pH}$ 高达9左右，可用于乳胶漆和AED中。  \n\ng.滑石粉滑石粉为天然矿物产品，其主要成分为 $3\\mathbf{M}\\mathbf{g}0\\cdot4\\mathbf{S}\\mathrm{iO}_{2}\\cdot\\mathrm{H}_{2}\\mathbf{O}$ ，粒子形态有片状和纤维状两大类。特点如下：  \n\n·形态呈纤维状的滑石粉在涂层中还可起补强作用；  \n·用于底漆中不易沉降，而且还可防止其他颜料沉降。  \n因此滑石粉广泛被用来与其他防锈颜料配合，用于各类防锈底漆中。  \n\n(2）酚醛类酚醛类阳极电泳底漆是采用“油溶性”酚醛树脂（如叔丁酚甲醛树脂、苯基苯酚甲醛树脂）与干性油（如亚麻油、桐油、脱水麻油等）共聚生成酚醛改性油。然后采用与环氧酯类相类似的方式进行水性化。即先与不饱和羧酸加成，引入羧基，然后再胺化成盐。油溶性酚醛树脂与干性油的反应原理如下：  \n\n![](images/9eb6e32b6ef550df55c33c723475243dd32fce1a84758ee7322ed3eb5df7f735.jpg)  \n\n![](images/e23269eed6741a8eeb5e8c6ad8cad4d6704cb8c604383c4fae90179aeb7dd560.jpg)  \n\n然后，再采取与环氧酯类似的方式引人羧基，最后胺化，获得水稀释性。酚醛类AED与环氧酯类AED的性能大体处于同一水平，它们几乎同时上市，随着性能更为优越的聚丁二烯类、丙烯酸类AED以及后来CED的问世，它们也几乎同时衰落，到目前为止，无论汽车行业还是其他工业领域都已经比较少见了。  \n\n(3）聚丁二烯类聚丁二烯类阳极电泳底漆在电泳涂料的发展史上具有特殊的地位。这类AED因其突出的耐极性介质性能在CED尚未问世的那一段时期内曾超过环氧酯类、酚醛类AED，在20世纪的70年代一度成为涂料业界的热门话题。今天虽然随着CED的问世和不断完善，聚丁二烯类AED已逐步淡出汽车底漆市场，但在一些特殊领域，如以轻质合金为车身材料的跑车类底漆的应用上，仍然占有一席之地。因此以下较为详尽地介绍这类AED的特性及其应用。  \n\n聚丁二烯类AED是以低分子量聚丁二烯替代传统植物油作为基干树脂，再通过与不饱和脂肪酸的加成反应引入羧基，最后以水溶性胺中和得可水稀释性的树脂。  \n\n$\\textcircled{1}$ 低分子量聚丁二烯树脂（LPB）AED用低分子量聚丁二烯树脂多采用阴离子聚合或活性（living）聚合法制造而得。分子量为 $1000{\\sim}4000$ ，实际市场上所谓1,2-PB、1,4-PB也不过就是以某类构型为主的树脂。如采用活性聚合法生产LPB的日本曹达公司的1,2-PB树脂，其中含1，2-构型的约占 $80\\%$ 。其他采用阴离子聚合法生产的LPB则以1，4-构型为主，其中1,4-构型约占 $65\\%$ ，采用活性聚合的LPB树脂具有极为狭窄的分子量分布，而且能够在PB大分子端基上引入活性基团，为进一步改性提供可能性，是理想的AED原料树脂，但工艺要求颇高，价格也较贵。  \n\n$\\textcircled{2}$ 引人羧基在LPB大分子中引人羧基最为常见的方法就是LPB与顺酐或反丁烯二酸酐进行加成反应。  \n\n![](images/a6ce9b3ec63179b1ee6df068bcc4d603628850767a27be7df1b25be85fd32e02.jpg)  \n\n从上述两类反应可以看出；产物的不饱和度均未发生改变，加成反应一个通过与双键相邻的叔碳上的氢，一个是双键发生转移。  \n\n为获得理想的可用于AED的水稀释性聚合物，顺酐的用量大约应控制在 $10\\%\\sim30\\%$ 顺酐用量过高虽然可获得较好的水稀释性，但将导致漆膜的耐介质性能下降，而用量较低，则将使聚合物的水稀释性下降。较合理的用量应控制在 $15\\%\\sim25\\%$ α  \n\nLPB长期受热时易于发生聚合反应，因此在顺酐化的加成反应中应添加一定量的阻聚剂。常用的阻聚剂有取代酚类（如2，6-二叔丁基对甲酚、对甲氧基苯酚）、有机胺类（如三乙胺、三丁胺)、咪唑类（如甲基咪唑）等。阻聚剂的合理使用可有效控制反应产物的黏度，提高工艺的稳定性，防止凝胶事故的发生。  \n\n顺酐化引入羧基的加成反应的条件一般为 $190\\sim200\\mathrm{\\textperthousand}$ ， $6\\sim10\\mathrm{h}$ ，一般如控制得当，其顺酐的加成率可达 $98\\%$ 以上。  \n\n$\\textcircled{3}$ 聚丁二烯树脂的改性LPB与常用植物油相比，不饱和双键的含量相当高，除1，2-构型的PB具有一定厌氧性外，两类具有1，4-构型的PB均可在空气中的氧的参与下发生氧化交联反应。因此，以未经改性的LPB制得的AED（无论是以1,2-构型为主，还是1,4-构型为主的树脂)，漆膜的力学性能会随着时间的推移而逐渐变得硬、脆，乃至失去原有的机械强度。毫无疑问，这就是氧化交联反应所带来的恶果。为了克服上述不足，人们进行了种种尝试，如采用不饱和双键含量相对较低的氢化LPB、部分氧化LPB，与某些植物油共顺酐化以及在LPB刚性较高的C—C链段中嵌人柔性链段等。  \n\n几种改性途径中比较具工业化价值的当属链扩展，即在LPB刚性较高的C—C链段中嵌入柔性链段以改善LPB的物理力学性能。比较典型的范例是采用具有端羟基的LPB与含NCO基团的异氰酸酯进行链扩展反应，从而使得大分子链段具有刚柔相济的特性。其典型改性路径如下。  \n\n![](images/4cc910a1c7c837e705e8adfebddff25000a3ea152ca2b9bbfdf7d71e6112868a.jpg)  \n\n含羟基的LPB经TDI之类二异氰酸酯链扩展后，再按照常规步骤进行顺酐化，可得综合力学性能较为理想的AED涂料。此法最大的缺憾就是工业上制造LPB普遍采用的阴离子聚合法，不能得到含端羟基的LPB，必须采用所谓活性聚合工艺方能实现。  \n\nLPB型AED涂料的耐盐雾性能可达200h左右，为AED中耐介质性能最好的品种。  \n\n(4）丙烯酸类环氧酯、酚醛类AED电泳涂料不易制浅色和彩色涂料的根本原因是原料本身颜色较深。如酚醛树脂呈棕红色；环氧树脂呈黄-褐黄色；亚麻仁油呈黄色；亚麻酸呈棕褐色等。丙烯酸类阳极电泳涂料不再采用常用的亚麻仁油等干性植物油为主要原料，而是采用丙烯酸及其衍生物共聚反应而成。由此克服了由于植物油引起的高温潮湿时长霉变质的可能性，同时也克服了烘烤过程中油脂挥发对烘箱、烘道的污染。也不再采用顺丁烯二酸酐加成在高分子链上引入羧基，而采用共聚单体（如丙烯酸、甲基丙烯酸等）直接引入羧基，此法可制得无色透明的、可水稀释的丙烯酸树脂（丙烯酸酯单体本身无色透明），且在交联固化时不变色。用其电泳可以保持金属本色，起到罩光的作用，为制成白漆、浅色漆和其他各种鲜艳色彩的电泳涂料创造了条件。丙烯酸阳极电泳涂料基本无板结现象的发生，提高了树脂的可溶性和槽液的稳定性。  \n\n前面讨论过的几类AED（环氧酯类、酚醛类以及聚丁二烯类）的烘烤干燥原理均为氧化交联反应，丙烯酸类阳极电泳底漆的又一大特点就是可以采用添加交联剂的方式以进一步提高漆膜的综合力学性能及耐介质性能（表3-2-4)。添加的方式可以是外加，亦可采用“内加”方式。所谓“内加”就是在丙烯酸树脂的主链上引人可交联的活性基团，从而使其在烘烤温度下发生自交联反应。显然，“内加”法更适合用于AED涂装系统。可用作自交联反应的单体很多，如羟甲基、羟基、羧基、环氧基、酰氨基等。实际上，较适合用于丙烯酸类AED的可交联单体如羟甲基丙烯酰胺等，其典型的配方及工艺如下。  \n\n表3-2-4丙烯酸类与环氧酯类、酚醛类阳极电泳底漆基本性能比较  \n\n\n<html><body><table><tr><td>参比项目</td><td>A</td><td>B</td><td>C</td></tr><tr><td>原料</td><td>丙烯酸类单体</td><td>干性油、环氧树脂、顺酐</td><td>干性油、酚醛树脂、顺酐</td></tr><tr><td>槽液抗霉性</td><td>不长霉</td><td>易长霉</td><td>易长霉</td></tr><tr><td>漆膜颜色</td><td>可调制成各种颜色</td><td>色深</td><td>色深</td></tr><tr><td>击穿电压/V</td><td>≥200</td><td>≤150~170</td><td>≤150~170</td></tr><tr><td>施工电压/V</td><td>40~200</td><td>50~100</td><td>50~100</td></tr><tr><td>膜厚/μm</td><td>10~40</td><td>15~20</td><td>15~20</td></tr><tr><td>原漆细度/μm</td><td>≤20</td><td>20</td><td>20</td></tr><tr><td>槽液稳定性</td><td>不易沉淀、抗杂离子干扰能力强</td><td>易沉淀</td><td>易沉淀</td></tr><tr><td>附着力/级</td><td>1</td><td>1</td><td>1</td></tr><tr><td>柔韧性/mm</td><td>1</td><td>1</td><td>1</td></tr><tr><td>冲击性/cm</td><td>50</td><td>50</td><td>50</td></tr><tr><td>耐盐水性（25℃，3%NaCl）/h</td><td>24</td><td>24</td><td>24</td></tr></table></body></html>  \n\n$\\textcircled{1}$ 配方（质量份）  \n\n\n<html><body><table><tr><td>乙二醇单甲醚</td><td>28.1</td><td>丙烯酸</td><td>5.6</td></tr><tr><td>甲基丙烯酸甲酯</td><td>21.1</td><td>羟甲基丙烯酰胺</td><td>3.5</td></tr><tr><td>丙烯酸乙酯</td><td>15.4</td><td>偶氮二异丁晴（一）</td><td>1.4</td></tr><tr><td>丙烯酸丁酯</td><td>13.1</td><td>乙二醇单甲醚</td><td>1.0</td></tr><tr><td>丙烯酸羟丙酯</td><td>4.9</td><td>偶氮二异丁晴(二)</td><td>0.3</td></tr><tr><td>苯乙烯</td><td>5.6</td><td>二乙醇胺</td><td>适量</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 工艺  \n\na.将甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸羟丙酯、苯乙烯、丙烯酸、羟甲基丙烯酰胺、偶氮二异丁腈（一）混合均匀，然后加人到高位槽中备用。  \n\nb.将乙二醇单甲醚加入到反应釜中， ${\\bf N}_{2}$ 保护下升温至 $90^{\\circ}\\mathrm{C}$ ，稳定 $10\\mathrm{{min}}$ 鼎c.滴加高位槽中的混合物，耗时约3h；继续保温 $^{3\\mathrm{h}}$ 。d.通过高位槽加人乙二醇单甲醚和偶氮二异丁睛（二）的混合物，耗时约 $10\\mathrm{{min}}$ ；继续保温2h；e.加人适量二乙醇胺调整 $\\mathsf{p H}$ 至8左右。  \n\nf.降温、出料。  \n\n$\\textcircled{3}$ 树脂半成品指标  \n\n外观 透明、黏稠液体 不挥发分/% 70±1  \n黏度（25℃，格氏管）/s 180\\~200  \n\n将上述聚合物用去离子水稀释，可配制成10%的槽液。在下列电泳条件下进行涂装：  \n\n电泳电压/V 60 烘烤条件/CXmin 120×30  \n电泳时间/min 2  \n\n所得漆膜性能优良，添加颜料、填料后可得各种色彩鲜艳的涂层。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1025,
+        "chunk": "# 3.阴极电泳底漆（以下略为CED）  \n\n(1）CED的发展阶段阴极电泳底漆之所以受到汽车行业的青，究其主要原因则在于它的防腐蚀性能、物理力学性能以及对面漆的烘托性能等方面都较阳极电泳底漆优越得多。可以用作阴极电泳底漆的主成膜物质很多，大体包括丙烯酸树脂、环氧树脂、聚氨酯树脂以及聚丁二烯树脂等几大类，但真正用于汽车工业生产中的则主要有两大体系，即以美国PPG公司为主导的环氧/聚氨酯系以及德国赫斯特集团的环氧/聚酰胺/聚酯系等阳离子型合成树脂。无论是哪一类系统，总体来说，CED经历了以下几个发展阶段。  \n\n$\\textcircled{1}$ 第一代CED首次实现工业化的第一代CED是所谓薄涂层的通用型电泳底漆。其干膜厚度为 $18\\mu\\mathrm{m}$ 左右，防腐蚀性能的关键指标——盐雾时间为 $400\\sim500\\mathrm{h}$ 。目前国外大多数车厂、国内多数大型车厂已逐渐将其淘汰。北京红狮涂料公司20世纪80年代引进奥地利Stollack公司（德国Herberts下属子公司）的G1083就属于这一品种。  \n\n$\\textcircled{2}$ 第二代CED随着汽车行业的发展，给汽车底盘的防腐蚀也提出了更为苛刻的要求，另一方面也考虑是否能够用厚的CED底漆来代替一部分中间涂层，这样就发展了所谓厚涂层的CED。即干膜厚为 $30\\sim35\\mu\\mathrm{m}$ 、盐雾时间达1000h以上的CED。  \n\n$\\textcircled{3}$ 第三代CED汽车行业在使用厚涂层CED中发现用价格不菲的CED来代替中间涂层不一定合算，另外从节约能源的角度，需要减轻汽车车身的总重。于是向涂料行业提出了能否在保持防腐蚀性能的前提下，减少CED涂层的厚度。于是中厚膜CED应运而生，即干膜厚度为 $25\\mu\\mathrm{m}$ 左右，盐雾时间 $800{\\sim}1000\\mathrm{h}$ 。目前世界上大多数汽车厂都采用了这一品种。  \n\n$\\textcircled{4}$ 第四代CED关于第四代CED，涂料行业有很多不同的概念，各大涂料公司也有自己的一套说法。总体来讲可以归纳为以下几点。  \n\na.保持第三代CED的基本特性。  \n\nb.涂料公司各赋予其产品各自相应特点，如填平性优良，良好的尖劈效应（有人称其为边角覆盖性)，装饰性好，无铅，对面漆的烘托性优良等。目前国内外各大车厂已相继采用这类品种。第四代CED其主要特点为：  \n\n·良好的尖劈效应，装饰性好，对面漆的烘托性优良；  \n·更新期长，非常适合我国一些生产量一时上不去的中小型车厂使用；  \n·超滤水几乎不需要排放而形成封闭式的循环体系。  \n\n$\\textcircled{5}$ 第 $N$ 代CED再往后有关第几代CED的提法就无从统一了，在有关科技文献资料中第五代、第六代甚至第七代的都可以看到。但大体来说，新一代的CED应具备以下特点。  \n\na.环保无毒无铅、无锡、无秘、无重金属，可满足欧盟、北美等最新环保法规的要求。  \n\nb.高泳透率、低使用量降低外板膜厚在 $20\\sim22\\mu\\mathrm{m}$ ，提高内板膜厚在 $13\\sim16\\mu\\mathrm{m}$ 。可在降低单台涂料使用量的情况下，提高车体整体耐盐雾水平，保证在1000h以上。可采用四枚盒法测试泳透力，用锐角刀片腐蚀点法测试边角耐腐蚀性能。  \n\nc.低烘干温度可选择 $150^{\\circ}\\mathrm{C}\\times20\\mathrm{min}$ 或 $160^{\\circ}\\mathrm{C}\\times10\\mathrm{min}$ 进行烘干，大量节约能源消耗。d.低加热减量加热减量控制在 $4\\%$ 以内，一般在 $2\\%$ 左右，减少挥发物排放，降低环境污染。  \n\ne.在低T.O.值下的槽液稳定性即使在生产量较小、槽体较大的情况下，或者在零部件生产的涂装线上，当出现涂料更新周期较长的情况下，也能保证非常好的槽液稳定性能。  \n\nf.低溶剂含量采用不同的技术，控制槽液中的有机溶剂的含量在 $1\\%$ 以内，降低阴极电泳漆的VOC排放量。  \n\ng.高平滑性采用独特表面控制技术，降低电泳涂膜的表面粗糙度 $R_{\\circ}{\\leqslant}0.2\\mu\\mathrm{m}$ ，提高电泳涂膜的表面平滑性，增加中、面漆的外观装饰性。  \n\n(2）阴极电泳底漆（CED）用原料CED是由阳离子树脂、交联剂、颜料、填料、助剂、助溶剂、去离子水等所组成。可用来合成CED阳离子树脂的高分子聚合物有环氧树脂、丙烯酸树脂、聚丁二烯树脂等，目前应用最为普遍的则是环氧树脂。制取阳离子树脂的途径是；首先在环氧树脂上引入含N、P、S等元素的可成盐基团（一般采用有机胺类)，再用有机酸中和成盐使之分散在去离子水中。这种阳离子树脂分散液加入其他成分后配制成槽液。电泳涂装时在电场的作用下，发生电解作用，带正电荷的树脂离子挟带着颜、填料等成分向阴极运动进行电泳、电沉积以及电渗等电化学过程，完成电泳涂装。  \n\n$\\textcircled{1}$ 主成膜物质现今世界上主要汽车总装厂均采用环氧树脂作为主体成膜物质。环氧树脂阳离子化最简捷的办法就是直接胺化，从而达到使其水性化用于阴极电泳底漆的目的。如采用仲胺或亚胺酮胺化：  \n\n![](images/17c07e71bf26b4442aa9209d17598294334ace6b732396d3a04e1728dd2c89d9.jpg)  \n\n然后，再用酸中和成铵盐赋予树脂以阳离子特性：  \n\n![](images/a11caf8d76933080346bb645db613aa54e910faf97c32280f20afdfb7b88a179.jpg)  \n\n除以双酚A型环氧树脂为基干大分子外，采用含环氧基的丙烯酸单体与其他丙烯酸单体共聚生成含环氧基的丙烯酸聚合物，胺化后，再酸化成盐制得阳离子型丙烯酸树脂。这类树脂的重要特点是树脂颜色较浅，可制备浅色CED。  \n\n也有人尝试用带亚氨基的化合物与环氧树脂反应生成端基为季氨基的中间体，然后再用半封闭的异氰酸酯进行链扩展，可得环氧-聚氨酯型阳离子树脂，此类树脂用作CED的主成膜物质时不必另外添加交联剂，烘烤条件下解封释放出—NCO基团与树脂中的 NH和一OH进行交联反应。  \n\nCED中所用的环氧树脂以下述原料制备的环氧树脂为主：  \n\n![](images/f4857ffae722d2ca5474a4eb788f689a1a4586ceaf4a0a3185ecd187bd9e839e.jpg)  \n\n由上述环氧树脂制备的不同分子量的环氧树脂结构如下：  \n\n![](images/c83bfd9e47d671fad941e71ce673c25fb7f33ae793ef1f746125ed2f13e9b62a.jpg)  \n\n除双酚系列环氧树脂外，也有采用脂肪族环氧树脂的范例，如采取以下结构的脂肪族线性环氧树脂：  \n\n![](images/73a1e82ed257c184df09ef8027db6605eebfd3d72088cb94b7ff9c8be529e0bb.jpg)  \n脂肪族线型环氧树脂  \n\n式中，R为长链烷烃。  \n\n采用线型脂肪族环氧树脂可以制得力学性能突出的CED涂料，就像溶剂型防腐蚀涂料中不同类型的环氧树脂表现出来的性能差别一样；双酚型环氧在防腐蚀性能方面更为优异。故现今汽车行业采用的CED多采用双酚系列的环氧树脂。虽然如此，直接取商品环氧树脂做原料并不适用，因为它们的分子大小、主链的刚柔性并不符合CED的诸多要求。所以现今汽车工业常见的CED都需要采取某些改性措施，如采用低分子量环氧树脂与各类链扩展剂进行反应，这样就可以在保持原有防腐蚀性能的前提下，改善交联漆膜的黏附性、柔韧性。可用来进行链扩展的化合物有联苯二酚、双酚A、长链的烷基酚、长链的一元羧酸或多元酸、聚醚多元醇等。采用上述化合物进行链扩展反应，可以得到适当分子量的环氧树脂。然后再利用接枝或嵌段反应接入柔性链段，以调节整个大分子链的刚柔性。如采用低分子量环氧树脂、双酚以及长链的烷基酚类制备环氧中间体。  \n\n第一步：  \n\n第二步：  \n\n![](images/d481550ec6056c6409d507171fe133ad77161acee5f40cdff1346aa3b4adb19e.jpg)  \n\n式中，R为长链烷基； $m,n$ 为自然数， $n>m$ 链扩展与嵌段（或接枝）反应既可同时进行，亦可分两步进行。现举一一步法的实例：a.配方 （质量份）  \n\nE-51环氧树脂  \n\n壬基酚 二甲苯 b.工艺  \n\n·将E-51环氧树脂、壬基酚、二甲苯、双酚A按计量依次投入到反应釜中，然后开揽拌，升温至 $125^{\\circ}\\mathrm{C}$  \n\n·停止加热，加入亚磷酸三苯酯（用足够的二甲苯将亚磷酸三苯酯调成糊状）耗时约1h，降温，使反应温度保持在 $130\\Upsilon$  \n\n取样测EEW值，当 $\\mathbf{EEW}{=}710\\sim740$ （理论值为730）时停止反应，降温，得扩链后的高分子量环氧树脂中间体。  \n\n然后该中间体中的环氧基再与胺（如N-甲基乙醇胺、二乙醇胺、二丙醇胺、二甲氨基丙胺、二甲氨基丁胺等）反应，得到胺封闭的主树脂。最后该树脂以酸中和后再与交联剂和助剂一道分散在水-酸溶液中。 9八  \n\n上述制备阳离子化树脂的前期，反应大都在有机溶剂参与下进行，故反应后期还有一个重要的抽提有机溶剂工序。这一步非常重要，如果有机溶剂抽提不完全，则极有可能使CED漆膜对缩孔非常敏感。一般工厂都采用气相色谱来进行监控，但最直接的、也是最有效的办法就是取样配槽，观察所制得的样板上有无缩孔来做最终判断。  \n\n总之，制备环氧系CED用树脂的各个阶段都非常重要，忽视任何步骤都可能带来灾难  \n\n性的后果。  \n\n$\\textcircled{2}$ 交联剂CED中采用的交联剂多为封闭型异氰酸酯类化合物。在这里既可采用芳香族异氰酸酯类，亦可采用脂肪族或脂环族异氰酸酯类。有时为了平衡交联漆膜的物理力学性能，采用芳香族与脂肪族异氰酸酯搭配使用，如采用TDI与HDI搭配可得刚柔并济的良好效果。所采用的封闭剂对于水稀释性涂料系统而言，大多为亲水性醇醚类、胺类等，这里需要考虑的是其解封条件应能适应CED绝大多数涂装线的工艺要求。以二乙二醇乙醚封闭TDI单体为例，其反应式如下。  \n\n![](images/cd1fd22b084ae4c909d40dce0f7fc9c63fc3a5ca88585a07350d4f302c7b4646.jpg)  \n\n封闭反应最好在有催化剂（如月桂酸二丁基锡、二丁基氧化锡等）存在的条件下进行，反应温度为 $60\\mathrm{\\sim}80\\mathrm{\\top}$ ，反应时间为 $2\\mathord{\\sim}3\\mathrm{h}$ 。有关封闭型异氰酸酯类方面的知识详见本章面漆有关部分。  \n\n在CED的实际应用中，更多采用的则是以TDI的三聚体或与二乙二醇、三羟甲基丙烷、季戊四醇等的加成物为原料，再进行封闭反应而得。以醇醚封闭TDI与三羟甲基丙烷加成物的合成工艺及配方如下。  \n\na.配方（质量份）  \n\n甲基异丁基酮（一) 6.75 甲基异丁基酮（二） 9.50  \nTDI 38.16 丙二醇乙醚 23.11  \n月桂酸二丁锡 0.02 甲基异丁基酮（三) 12.96  \n三羟甲基丙烷 9.50  \n\nb.工艺  \n\n·将甲基异丁基酮（一）、TDI、月桂酸二丁锡加到反应釜中，加热到 $40^{\\circ}\\mathrm{C}$ 要  \n\n·将三羟甲基丙烷和甲基异丁基酮（二）在配料罐中混合，混合物的温度应为 $55\\sim70\\ensuremath{\\mathrm{\\:c}}$ （如果温度太低，TMP可能结晶析出）。  \n\n·将混合好的三羟甲基丙烷和甲基异丁基酮（二）溶液以稳定的速度慢慢加到反应釜中，此时釜温应低于 $60^{*}\\mathrm{C}$ $(45\\sim55\\Upsilon)$ ，加完后，在 $60^{\\circ}\\mathrm{C}$ 下保温，取样检验黏度和NCO值。  \n\n·如果NCO当量合格，在 $30\\sim60\\mathrm{min}$ 内加入丙二醇乙醚，并且升温至 $115\\%$ ，保温，大约2h可封闭完成。  \n\n·最后加人甲基异丁基酮（三)，冷却至 $60^{\\circ}\\mathrm{C}$ ，过滤，包装。  \n\n注；1.三羟甲基丙烷或丙二醇乙醚中不能含水，否则将导致制成品黏度偏高，甚至成为非均相。  \n\n2.三羟甲基丙烷/MIBK溶液的温度不可高于75°℃，  \n\n$\\textcircled{3}$ 研磨树脂如前所述，主树脂经链扩展、接枝（或嵌段）共聚改性后引入氨基，最后与固化剂半成品一起酸化成可水稀释性树脂。为了避免研磨加工时封闭异氰酸酯解封，不少厂家还专门设计了专用于研磨加工的研磨树脂。该研磨树脂的基本结构与主树脂大体相同，但其结构和分子量因考虑到对颜料的润湿性和研磨性能而有所不同。相比呈乳液形态的主树脂而言，它应更具亲水性，而以可水稀释形态存在。这样在研磨加工时，就可承受高剪切速率而不会“破乳”。还有一点不同的就是研磨树脂中不含任何交联剂。  \n\n$\\textcircled{4}$ 颜料、填料由于汽车行业用CED的颜色较为单一，一般包括黑色、中灰色、浅灰色等有限的几种，故所涉及的颜料、填料品种不多。  \n\n阴极电泳涂料的颜基比是一个较为重要的工艺参数。一般颜料与成膜物质的沉积比会有所不同，这样在日常运作的过程中就会导致颜基比的变化。太高的颜基比将使漆膜的光泽下降，漆膜琉松，性能下降，槽液的沉淀增多，从而使泵、管路的负荷加大。太低的颜基比又会引起槽液的泳透率下降，膜厚降低。低颜基比是一个CED水平的衡量参数之一，一般可控制在 $0.12{\\sim}0.18$ 费  \n\na.白色颜料仍然以钛白为主，可用于CED系统中的几种品牌，如杜邦的900，Tiox-ide公司的R-TC90、R-HD6、R-HD2，NL化学品公司的RN45、RN56、RN59、RN61，帝国化工公司的JR-600E、JR-602等均可。  \n\nb.黑色颜料炭黑系颜料是CED系统中的主要黑色颜料，其中多采用炉黑，而较少用其他几类炭黑，如哥伦比亚公司的Raven410、卡波特公司的Elftex125等均为炉黑。  \n\nc.硅酸铝合成硅酸铝主要用于水性系统中作为功能性填料。  \n\nd.沉淀硫酸钡CED中主要采用“超细”沉淀硫酸钡，为使其产品真正符合“超细”的称号，不少生产厂家都将粒径控制在0.7～4μm的范围内，不仅如此，还规定45pm的筛余物应低于0.01%～0.001%。有关资料显示：在CED中，超细硫酸钡除起重要的防沉降作用外，还可用它来取代近20%左右的钛白粉。  \n\ne.碱式硅酸铅铅作为重要的固化交联催化剂及防腐防锈颜料一直到现在仍然是所谓前四代阴极电泳漆体系的主要成分，其中较典型的就是碱式硅酸铅。在早期的CED系统中它被广泛用作防锈颜料，就像其他铅系颜料一样，近年来由于环保方面的原因碱式硅酸铅已经逐渐淡出涂料行业而为其他性能优越而又不含重金属离子的防锈颜料所替代。  \n\nf.秘盐无铅、锡等重金属防锈颜料的开发中比较成功的就是盐的应用，如乳酸、二羟甲基丙酸、氨基磺酸秘、羟基磺酸和烷基磺酸等。金属离子可以替代铅离子作为阴极电沉积涂料催化固化剂，且在不降低漆膜性能的前提下，可以降低烘烤温度，减少了能耗。含有离子的阴极电沉积涂料相对铅而言，具有更为优良的硬度和耐盐雾性能。  \n\n③溶剂乳液中的溶剂是树脂和交联剂生产中所不可少的溶剂混合物，它们的存在对于保证漆膜的厚度是必要的。丙二醇醚或乙二醇醚类都可以添加到槽液中以改善流平或调整漆膜的厚度。新一代的CED中助溶剂的含量可低于1%。  \n\n③助剂CED系统中用得最多的助剂有消泡剂、稳定剂以及膜厚调整剂等。在溶剂型色漆系统中经常用到的润湿分散剂在CED中却不太常见，主要是因为CED用研磨树脂本身就具有良好的润湿、分散功能。  \n\na.膜厚调整剂烷基酚的醚类具有较好的膜厚调整功能，如乙二醇苯基醚、聚乙二醇苯基醚、丙二醇苯基醚、聚丙二醇苯醚等。  \n\nb.消泡剂在CED系统中多用到消泡剂，如槽液泵循环过程中泡沫的消除等。所用消泡剂最好为非硅氧烷系列产品，炔醇类、改性脂肪酸类以及矿物油类等。  \n\n(3）色浆的制造CED用色浆的制造与溶剂型色浆大体相同，但这里对研磨过程中漆料的温度控制较为严格，因此建议采用砂磨机上配备有温度显示可以监控酮体内温度的机型。另外，由于CED对于油污特别敏感，故砂磨机的轴封方式及材料也应重点考虑。现国内外普遍采用的双筒式砂磨机基本符合上述要求。由于CED的颜色比较单一，故研磨时不如面漆部分那么复杂，有的就将全部颜料、填料一起研磨，有的则单独研磨黑色浆，一方面可以提供黑色CED，另外，也可为客户供应不同灰度的CED。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1026,
+        "chunk": "# 第二节中间涂料  \n\n中间涂料是介于底漆和面漆之间的一种涂料。涂料工通常习惯把传统底漆叫做“头道浆”；那么中间涂料就顺理成章地被使用者称为“二道浆”、“二道底漆”了。汽车行业对中间涂料的需求量相当大，有关统计资料显示；全世界每年的产量达13万吨之多。汽车行业用中间涂料按照其用途来分类有；通用型中间涂料、抗石击型中间涂料以及线上修补型中间涂料等。按其形态来分则有溶剂型中间涂料、水性中间涂料、粉末中间涂料三大类。大约20年前，在汽车行业中溶剂型中间涂料还占据着统治地位，但近年来以欧洲、北美为先导，粉末及水性中间涂料逐渐显露出一定的势头。表3-2-5中列出了2003年世界各地三类中间涂料所占的市场份额。  \n\n表3-2-52003年世界各地三类中间涂料所占的市场份额 单位：%  \n\n\n<html><body><table><tr><td>类型</td><td>欧洲</td><td>北美</td><td>南美</td><td>亚洲</td><td>非洲</td></tr><tr><td>溶剂型</td><td>46</td><td>65</td><td>83</td><td>95</td><td>71</td></tr><tr><td>水性</td><td>52</td><td>5</td><td>17</td><td>5</td><td>20</td></tr><tr><td>粉末</td><td>2</td><td>30</td><td>0</td><td>0</td><td>9</td></tr></table></body></html>  \n\n从表3-2-5中数据可知，欧洲的水性中间涂料发展迅速，南美稍次。而北美在粉末中间涂料的应用方面处于领先地位。亚洲则在上述两类先进技术上远远落后于其他地区。  \n\n汽车行业使用的三类中间涂料的基本技术参数见表3-2-6。  \n\n表3-2-6三类中间涂料的技术参数  \n\n\n<html><body><table><tr><td>项目</td><td>溶剂型中间涂料</td><td>水性中间涂料</td><td>粉末型中间涂料</td></tr><tr><td>不挥发分/%</td><td>50~65</td><td>35~45</td><td>100</td></tr><tr><td>VOC/(g/L)</td><td>390~420</td><td>170~230</td><td>0</td></tr><tr><td>相对密度/（g/cm）</td><td>1. 1~1. 3</td><td>1. 1~1. 3</td><td>0.5~0.7</td></tr><tr><td>烘烤条件/min×℃</td><td>20×(130~165)</td><td>20×(130~165)</td><td>20 × (160~190)</td></tr><tr><td>膜厚/pm</td><td>35~50</td><td>25~35</td><td>55~100</td></tr><tr><td>黏度（20℃）/mPa·s</td><td>60000~100000</td><td>60000~100000</td><td>固体</td></tr><tr><td>贮存温度/C</td><td>5~35</td><td>5~35</td><td>5~30</td></tr><tr><td>涂料使用效率/%</td><td>75</td><td>70~80</td><td>98</td></tr><tr><td>保质期/月</td><td>6</td><td>6</td><td>12</td></tr></table></body></html>  \n\n中间涂料的主要功能是进一步改善工件已涂装底漆的表面，作进一步的填补、修正，提高其平整度，以使面漆的鲜映性、丰满度、光泽等均有较大程度提高。另外，良好的中间涂料还可以吸收一定的冲击能量，对于提高涂层系统的整体抗石击性能也大有神益。  \n\n为了满足汽车行业对中间涂料的上述要求，在设计中间涂料的配方时需要考虑以下因素。  \n\n·主成膜物质应选择刚柔相济的树脂，如异氰酸酯改性聚酯树脂、聚酯树脂、合成脂肪酸醇酸树脂等。  \n\n·交联剂采用三聚氰胺甲醛树脂与封闭异氰酸酯搭配作交联剂。  \n\n·颜料、填料的选用重点考虑填平性、打磨性、对面漆的烘托性，在颜色方面则需要考虑与面漆颜色相近的原则，以达到最佳覆盖。  \n\n·溶剂适用于各种喷涂手段，如空气雾化喷枪、静电高速旋杯等。  \n\n·助剂原则上禁止在中间涂料配方中采用各种硅系列流平剂，包括聚醚改性硅氧聚酯改性硅氧烷等，如BYK300、BYK331、BYK310、BYK320等。应选用对层间附着力影响不大的某些氟、硅系列的产品，如BYK306、BYK307，EFKA的3777等。  \n\n近代汽车行业对中间涂料的要求也越来越苛刻，各国汽车涂料生产厂家也投入不少力量从事研发工作，中间涂料的主要发展趋势大体如下：  \n\n·进一步改善中间涂料的外观，提高其对面漆的“烘托”性能；  \n·厚膜化，重点在于提高一次成膜厚度；  \n·进一步提高其施工性能，使之具有良好的抗起泡性、流平流挂性能；  \n·抗石击性，能有效吸收汽车表面受到冲击时的能量；  \n·良好的层间附着力；  \n·高不挥发分、低VOC，符合越来越苛刻的环保标准要求等。  \n\n目前我国汽车行业仅在轿车、中巴、皮卡等中、高档汽车上使用中间涂料，而在一些轻卡、重型卡车、农用车等较低档车型上因成本方面原因，往往省去了此道工序。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1027,
+        "chunk": "# 一、原料  \n\n中间涂料所采用的原材料与面漆基本一样，也是由主成膜物质、颜填料、溶剂以及助剂等组成，现分述如下。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1028,
+        "chunk": "# 1.主成膜物质  \n\n现今世界上无论是溶剂型，还是水性、粉末等几乎所有汽车用中间涂料的主成膜物质都采用聚酯树脂或异氰酸酯改性聚酯树脂。合成中间涂料用聚酯树脂时所采用的多元醇或多元酸与面漆略有不同。其主要区别是这里所需要考虑的重点在于它更加偏重于前面所提到的中间涂料所需要的一些性能，如层间附着力、平整度、对面漆的烘托性以及抗石击性能等。因此在多元酸或多元醇的使用上与面漆树脂将有所不同。现举两例较为典型的中间涂料用聚酯树脂的合成范例，读者可以从中领悟它们与面漆用聚酯树脂的异同点。  \n\n(1）配方（质量份）  \n\n<html><body><table><tr><td></td><td>DC8879A</td><td>DC8879B</td><td></td><td>DC8879A</td><td>DC8879B</td></tr><tr><td>三羟甲基丙烷</td><td>6.50</td><td>12.10</td><td>豆油脂肪酸</td><td></td><td>11. 08</td></tr><tr><td>新戊二醇</td><td>22.02</td><td>11. 64</td><td>二甲苯(回流)</td><td>3.00</td><td>3.00</td></tr><tr><td>四氢苯酐</td><td>17.22</td><td></td><td>二甲苯(兑稀）</td><td>33.92</td><td>22.93</td></tr><tr><td>苯二甲酸酐</td><td>8.82</td><td>22.90</td><td>100*芳烃溶剂</td><td></td><td>12.00</td></tr><tr><td>己二酸</td><td>8.51</td><td>4.34</td><td></td><td></td><td></td></tr></table></body></html>  \n\n(2）工艺$\\textcircled{1}$ 工艺一  \n\na.将新戊二醇、三羟甲基丙烷、四氢苯酐、苯二甲酸酐、己二酸以及回流二甲苯等原料投入反应釜中，分水器中加好二甲苯。  \n\nb.升温到固体物料全部熔融后再开启搅拌。在 $175\\mathrm{^{\\circ}C}$ 反应1.5h，保持正常回流。升温到 $190^{\\circ}\\mathrm{C}$ ，反应2h，然后继续升温至 $200^{\\circ}\\mathrm{C}$ ，保温回流。  \n\nc.在 $200\\Upsilon$ 下，保温回流至酸值为 $_{9\\sim13}$ ，测黏度。  \n\nd.如果酸值合格，而黏度偏低，则可升温至 $210^{\\circ}\\mathrm{C}$ ，保温回流直至黏度合格。  \n\ne.待黏度合格后将物料抽至兑稀罐中。降温至 $130^{\\circ}\\mathrm{C}$ 以下，加入兑稀的二甲苯，搅拌均匀，然后降温至 $70\\%$ 以下，过滤、包装。  \n\n$\\textcircled{2}$ 工艺二  \n\na.将新戊二醇、三羟甲基丙烷、苯二甲酸酐、己二酸、豆油脂肪酸以及回流二甲苯等一起投入到反应釜中。  \n\nb.开始升温，待固体物料全部熔融后再开动搅拌。在 $175\\mathrm{^q}$ 的温度下保持1.5h，使其回流充分。再升温至 $190^{\\circ}\\mathrm{C}$ ，保持回流1.5h。升温至 $200\\%$ ，在此温度下保持到酸值为 $4\\sim$ $7~\\mathrm{{\\tmg\\KOH/g}}$ 漆基）为止。  \n\nc.如果此时黏度还达不到指标，可将温度升至 $210^{\\circ}\\mathrm{C}$ ，保温回流至黏度合格为止。  \n\nd.降温至 $180^{\\circ}\\mathrm{C}$ ，加人 $100^{\\sharp}$ 芳烃兑稀，待温度降至 $130\\mathrm{^{\\circ}C}$ 时加入二甲苯兑稀。温度降至 $70\\%$ 时过滤，包装。  \n\n(3）技术指标两种树脂的技术指标见表3-2-7。  \n\n表3-2-7两种树脂的技术指标  \n\n\n<html><body><table><tr><td>项目</td><td>DC8879A</td><td>DC8879B</td><td>项目</td><td>DC8879A</td><td>DC8879B</td></tr><tr><td>外观</td><td>透明黏稠黄色液体</td><td>透明黏稠黄色液体细度/μm</td><td></td><td>15</td><td>≤15</td></tr><tr><td>黏度（涂-4)/s</td><td>140~180</td><td>120 ~160</td><td>酸值/（mgKOH/g)</td><td>9~13</td><td>4~7</td></tr><tr><td>颜色（Fe-Co）</td><td>≤8</td><td>≤8</td><td>不挥发分/%</td><td>62±1</td><td>60±2</td></tr></table></body></html>  \n\n上述两种树脂均可用来配制性能优良的汽车用中间涂料（详见本节涉及制漆配方方面的内容)。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1029,
+        "chunk": "# 2.交联剂  \n\n中间涂料用主成膜物质聚酯树脂等与之配套的交联剂多为三聚氰胺甲醛树脂、苯代三聚氰胺甲醛树脂以及封闭型异氰酸酯类等。其中甲醇醚化三聚氰胺甲醛树脂，尤其是具有单三嗪环的六甲氧基三聚氰胺甲醛树脂最为普遍。如果醚化度不高，则游离的羟甲基可发生自缩聚反应，对溶剂型系统而言，以此可以得到较高的硬度，但对水性系统而言，却可能导致系统不稳定。  \n\n在溶剂型系统中，苯代三聚氰胺甲醛树脂可改善漆膜的外观、光泽以及附着力，但其耐候性能稍差。对此，不建议采用这类交联剂的中间涂料与遮盖力较差的底色漆（如以珠光颜料为主的底色漆）配套。  \n\n封闭型异氰酸酯类用作中间涂料的交联剂可赋予漆膜优异的综合物理力学性能及耐化学腐蚀性能。几乎所有的异氰酸酯类均可用于中间涂料系统，即脂肪族、脂环族以及芳香族等均可，如六亚甲基二异氰酸酯（HDI)、异佛尔酮二异氰酸酯（IPDI）以及甲苯二异氰酸酯（TDI）等。芳香族异氰酸酯类表现出较高的反应活性，且给出刚性较高的漆膜，而脂肪族异氰酸酯类则表现出较好的柔性和突出的耐候性。与HDI相比，IPDI具有较好的成膜性能，尤其是采用湿碰湿施工工艺时，它的物理干燥性能特别良好。  \n\n在水性中间涂料系统中，异氰酸酯基的存在有助于树脂的水分散稳定性，而不需要另外的羧基，这是因为NH 基与水分子间存在相互作用的缘故。  \n\n封闭剂的选用原则与面漆部分大体相同，有关知识将留待面漆系统中再详细讨论。  \n\n尽管中间涂料系统的主成膜物质以聚酯树脂为主，但也有采用环氧树脂的范例。环氧系中间涂料具有优良的力学性能、施工工艺性能、优异的防腐蚀性能以及对金属基材优良的附着力等。溶剂型环氧系中间涂料中所采用的环氧树脂多为的低分子量双酚A型环氧树脂，而具有两个以上双酚A单元的固体环氧树脂则多用于粉末中间涂料中。双酚A型环氧树脂的耐紫外光性能较差，因此在有些情况下采用脂环族环氧树脂或丙烯酸缩水甘油酯等。耐候性较好的环氧系的例子是基于异氰酸酯的环氧类交联剂，如三缩水甘油基异氰酸酯（TGIC)。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1030,
+        "chunk": "# 3.颜料、填料  \n\n中间涂料中采用的颜料、填料与面漆、底色漆不同，它不仅仅需要提供一定的色泽，而且还需要赋予漆膜一定的补强性能。采用的颜料多为钛白、炭黑，填料则多为沉淀硫酸钡、碳酸钙、滑石粉、硫酸锌以及白土等。  \n\n(1）钛白粉钛白粉由于自身具有接近石英的硬度，故能赋予漆膜以良好的抗石击性能。颜料钛白有两类晶型，即金红石型和锐钛型。金红石型具有较高的折射率、较好的耐化学腐蚀性能及耐紫外光性能，是使用最为普遍的颜料之一。  \n\n（2）硫酸钡硫酸钡的密度为 $4.1g/\\mathrm{cm}^{3}$ 左右，有天然硫酸钡（俗称重晶石粉）和沉淀硫酸钡两种。沉淀硫酸钡在制造时，沉淀工艺可以将填料粒子的粒径控制在一个较为狭窄的范围内，而且纯度很高。相反，天然硫酸钡的纯度不高，其中大约含有 $10\\%$ 的不纯物（锶和钙的硫酸盐)，这两种硫酸钡均可用于中间涂料中。由于硫酸钡的折射率只有1.64，故它不能赋予漆膜颜色，只是一种填充料。它们对酸、碱均呈现情性，且具有良好的耐候性能。最为重要的是它的价格低廉，非常适合与钛白粉拼用。  \n\n(3）滑石粉滑石粉最显著的特征就是片状或纤维状结构、憎水性能和相对低的硬度。其中的憎水性能可赋予滑石粉以良好的分散性。在中间涂料系统中滑石粉专用于调节漆膜的被破坏性能。在某些情况下，滑石粉的应用可以使漆膜的内聚强度降低，则在漆膜承受强烈的石击作用时，就可以避免成片脱落。滑石粉产自天然矿物，它具有较好的化学稳定性，其天然矿物有白云石和绿泥石两大类。  \n\n（4）二氧化硅二氧化硅的密度为 $2.28/\\mathrm{cm}^{3}$ 左右，1942年具有狭窄粒径范围的裂解法二氧化硅正式投入市场。它的粒径范围仅为 $0.007{\\sim}0.020\\mu\\mathrm{m}$ 。由于它们有着较高的比表面积 $(200\\mathbf{m}^{2}/\\mathbf{g})$ ，一般将其加工成聚集态的商品出售。  \n\n作为填料，由于它具有与其他物质相互作用的强烈倾向，故它可赋予涂料以触变性能。另外，它还可用作消光剂，用于亚光涂料特别是粉末涂料中。  \n\n(5）中国白土中国白土的化学名称为硅酸铝，它们常常以矿物形态存在于大自然中。涂料用白土常常加工成粒径小于 $10\\mu\\mathrm{m}$ 的填料，其密度一般为 $2.6~\\mathrm{g/cm^{3}}$ 左右。白土在中间涂料配方中常用来提高漆膜的硬度，有时还用来调整漆膜的打磨性。  \n\n(6）炭黑中间涂料的颜色以中灰、浅灰等淡色调为主，很少见到纯黑色的中间涂料，故炭黑仅作为调色颜料使用。炉黑、槽黑及灯黑几类炭黑均可用于溶剂型中间涂料中，但对于水性中间涂料系统而言，则建议采用炉黑或灯黑。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1031,
+        "chunk": "# 4.添加剂  \n\n在水性中间涂料中，助剂的应用远较溶剂型中间涂料复杂，因为在这里需要同时考虑树脂、颜料以及作为溶剂水的相互间的作用。此时添加的助剂有；颜料的润湿分散剂、消泡剂、脱泡剂、对基材表面的润湿剂以及流变剂等。需要补充一点的是；在中间涂料系统中，有时还需要添加催化剂及导电剂等。采用硅氧烷系助剂时，要特别留意！因为硅系助剂对层间附着力的影响非常大，应特别关注它对罩面面漆的影响。  \n\n中间涂料系统中采用的润湿分散剂与面漆部分基本一致，无特殊需求。与溶剂型中间涂料系统不同，在水性和粉末中间涂料系统中需要采用消泡剂或脱泡剂。 O  \n\n在添加剂的使用中，最为重要的是流变助剂。这种助剂的使用可以在一定程度上赋予涂料在高剪切应力的作用下，表观黏度较低，而在低剪切应力的作用下，表观黏度较高的特性。无疑，那些选用了合适流变助剂的涂料必然有着良好的施工工艺性能。在保证有足够一次成膜厚度的前提下，所得涂层的外观肯定会平整光滑。适用的流变助剂有高聚物类，如聚氨酯、脲醛树脂以及丙烯酸树脂等；无机添加剂，如气相白炭黑、有机膨润土等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1032,
+        "chunk": "# 5.溶剂  \n\n在溶剂型中间涂料系统中采用的有机溶剂有芳烃类、醇醚类以及酯类等。一般将这三类溶剂搭配使用，搭配时主要应该考虑以下因素：溶解性、黏度、沸点及其沸程、相对挥发速率、闪点、化学性能、毒性以及价格等。当今汽车行业尤其注重气味、毒性、价格等。通常，在稀释剂的配制中应考虑慢干、流展快的溶剂与沸点较低的溶剂之间的平衡。慢干溶剂可以减少缩孔产生的概率，而快干溶剂则对防止流挂有好处。  \n\n在水性中间涂料系统中应采用亲水性有机溶剂，最好是水溶性的溶剂，但有时也加入一些不溶于水的有机溶剂。  \n\n在聚酯树脂类中间涂料系统中，芳烃溶剂添加到配方中起“冲淡”作用，以协助喷涂施工时漆料更好地雾化。当然，这类溶剂并非“良”溶剂，故用量应严格控制，以免造成树脂系统不稳定。在水性中间涂料系统中，也有用到少量芳烃类溶剂，在这里主要起“破泡”的作用。  \n\n醇、溶纤剂以及酯类溶剂等所有含氧溶剂对聚酯树脂系统而言均为“真”溶剂。三类溶剂选择的原则是施工和稳定两个方面的因素。众所周知，在采用三聚氰胺甲醛树脂为交联剂的烤漆系统中，丁醇起着重要的稳定作用。在水性涂料系统中，乙二醇丁醚是最为普遍的助溶剂，它可以起稳定和改善树脂与水相间的相互作用，且赋予体系以流变性能。具有较高沸点的二乙二醇醚酯类溶剂可改善喷涂施工时基材以及漆膜表面漆雾的溶结。  \n\n四氢化蔡或松根油沸点较高，多数典型的中间涂料配方中均含有少量的这类“稀释剂”，它们对保持漆膜适当的湿度、防止缩孔形成非常有益。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1033,
+        "chunk": "# 二、几类中间涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 1034,
+        "chunk": "# 1.通用型中间涂料  \n\n中间涂料中使用最为普遍的是通用型的品种。此类中间涂料具有中间涂料的基本特点，用于一般中、高档汽车涂装中。现举一例浅驼灰中间涂料。  \n\n$\\Phi$ 配方(质量份）  \n\n\n<html><body><table><tr><td>DC8879A</td><td>28.53</td><td>氧化铁红</td><td>0.15</td></tr><tr><td>DC8879B</td><td>18.21</td><td>甲醇</td><td>1.00</td></tr><tr><td>混合醚化三聚氰胺甲醛树脂</td><td>16.00</td><td>丁醇</td><td>1.60</td></tr><tr><td>R900钛白粉</td><td>20.21</td><td>乙二醇丁醚</td><td>1.50</td></tr><tr><td>沉淀硫酸</td><td>8.36</td><td>CAC</td><td>4.00</td></tr><tr><td>炭黑</td><td>0.14</td><td>润湿分散剂</td><td>0.30</td></tr><tr><td>②技术指标</td><td></td><td></td><td></td></tr><tr><td>外观</td><td>浅灰色均匀黏稠液体</td><td>细度/μm</td><td>≤15</td></tr><tr><td>黏度（涂-4杯，23℃）/s</td><td>40~70</td><td>烘烤条件/CXmin</td><td>(150±2)×20</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1035,
+        "chunk": "# 2.抗石击中间涂料  \n\n目前，我国的汽车涂装线几乎均采用聚酯/醇酸/丙烯酸/氨基体系的溶剂型漆种进行汽车中间涂层的涂装。随着用户要求的质量越来越高，对汽车的耐石击性能的要求也逐渐苛刻，汽车的发动机罩盖、侧下围等易受路面小石子攻击的部位漆膜崩裂破损，严重影响车体外观和耐腐蚀性能。为此，新一代抗石击中间涂料应运而生。近年来，各大汽车公司已经逐渐采用新一代抗石击性中间涂料进行车体的涂装来克服小石子的冲击。改善中间涂层耐石击性的方法有很多种，欧美体系采用封闭的异氰酸酯交联剂来改善中间涂层的耐石击性能；日本则采用改良树脂的结构和弹性加上配合防石击颜料来实现。两者各有千秋，均能达到不同厂家、不同车型、不同部位、不同成本的多样化需求。新一代耐石击性中间涂料的主要特点如下：  \n\n$\\Phi$ 采用具有一定线型结构的聚酯树脂，活性适中、柔韧性好；  \n\n$\\textcircled{2}$ 固化剂采用三聚氰胺甲醛树脂与封闭型异氰酸酯结合，赋予交联漆膜良好的物理力学性能；  \n\n$\\textcircled{3}$ 添加改善流挂性能的树脂，如SCA改性聚酯树脂，使漆料具有良好的施工性能；  \n$\\textcircled{4}$ 非硅系列流平剂的采用，可赋予漆料良好的流平性，且不影响层间附着力。  \n\n现举一例抗石击中间涂料用树脂合成的范例供参考（质量份）。  \n\n<html><body><table><tr><td>线型聚酯树脂</td><td>38.0</td><td>超细滑石粉</td></tr><tr><td>SCA改性聚酯树脂</td><td>8.0 炭黑</td><td>5.0 0.2</td></tr><tr><td>封闭型异氰酸酯</td><td>8.0</td><td>膨润土胶（10%） 6.0</td></tr><tr><td>异丁醇醚化三聚氰胺甲醛树脂</td><td>13.0</td><td>BYK -358 0.2</td></tr><tr><td>钛白粉</td><td>11. 0</td><td>100*溶剂 2.6</td></tr><tr><td>超细硫酸</td><td>8.0</td><td></td></tr></table></body></html>  \n\n采用上述配方配制的中间涂料具有良好的综合物性及对面漆的烘托性能。特别突出的是，该中间涂料的抗石击性能优异，配方中，封闭型异氰酸酯的用量对抗石击性能影响明显，当其用量达 $10\\%$ 时，其抗石击性能可小于1级，杯突性能可达 $8\\mathrm{mm}$ 以上。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1036,
+        "chunk": "# 3.线上修补用中间涂料  \n\n汽车原厂漆中也有用到“修补涂料”的情况。主要是因为涂装过程中控制再严密，也难免有点、流挂、橘纹等漆膜病存在。这就需要及时进行线上“修补”，因此原厂漆的中间涂料就有“修补用中间涂料”这类品种。修补用中间涂料与汽车修补漆中所采用的中间涂料大同小异，基本属于硝基类涂料。要求快干、易打磨、附着力良好。现举一例典型范例供参考(质量份)。  \n\n<html><body><table><tr><td>麻油短油醇酸树脂</td><td>23. 0</td><td>超细碳酸钙</td></tr><tr><td>苯二甲酸二丁酯</td><td>1. 2 钛白</td><td>2.0</td></tr><tr><td>NC溶液（1/2s，35%)</td><td>36.0 滑石粉</td><td>3.0 6.5</td></tr><tr><td>膨润土胶液（10%）</td><td>1. 5</td><td>硬脂酸锌</td></tr><tr><td>炭黑</td><td>0.1</td><td>0.3 二甲苯</td></tr><tr><td>立德粉</td><td>10.2</td><td>10.0</td></tr><tr><td>超细硫酸</td><td>3.0 TT-88</td><td>醋酸丁酯 3.0 0.2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1037,
+        "chunk": "# 三、中间涂料的技术标准  \n\n中间涂料的技术标准多属于各汽车总装厂自定或与供漆厂协议标准，但大多如表3-2-8所列。  \n\n表3-2-8中间涂料的技术标准  \n\n\n<html><body><table><tr><td>项 目</td><td>指标</td><td>测定方法</td></tr><tr><td>漆膜外观及颜色 黏度（涂-4杯，25℃）/s</td><td>符合标准板，平整光滑 40~70</td><td></td></tr><tr><td>细度/μm</td><td>≤20</td><td>GB/T1723—1993 GB/T1724—1979</td></tr><tr><td>烘烤条件/CXmin</td><td>(150±2)×20</td><td></td></tr><tr><td>光泽/%</td><td>70</td><td>GB/T 9754-1988</td></tr><tr><td>硬度</td><td>≥0.6</td><td>GB/T1730—1979</td></tr><tr><td>柔韧性/mm</td><td>≤</td><td>GB/T1731—1993</td></tr><tr><td>冲击性/cm</td><td>≥50</td><td>GB/T1732-1993</td></tr><tr><td>附着力/级</td><td>≤</td><td>GB/T92861988</td></tr><tr><td>杯突性能/mm</td><td>≥4</td><td>GB/T9753-1988</td></tr><tr><td>耐水性（40CX240h）</td><td>不起泡，允许轻微失光</td><td></td></tr><tr><td>耐候性（广州曝晒1年）</td><td>龟裂0级，失光1级</td><td>GB/T1733-1993</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1038,
+        "chunk": "# 第三节面漆  \n\n汽车面漆具有赋予汽车色彩以及对整个涂装系统保护的功能。在汽车刚刚问世的那段时间，汽车的颜色仅有一种黑色。然而在21世纪的今天，有关统计数据披露，每年约有近1000种新的颜色被用于汽车上，而近30年来在汽车颜色库里大约保存了25000～40000种颜色。因此有人说，汽车漆应归于颜色科学的范畴倒也颇有几分道理。  \n\n汽车面漆与其他领域的面漆一样，主要有清漆和色漆，而色漆中又可细分为含一般赋色颜料的本色漆、本色底色漆和含效应颜料的金属闪光漆等。  \n\n人们知道，色漆主要由成膜物质、颜料、溶剂以及助剂所构成。色漆的生产按其加工工艺分类有传统的主色浆法和新近发展起来的单色浆法。所谓单色浆法就是预先将各种颜料分别分散在成膜物质中制成色浆，然后再按照配方，将主成膜物质、各种色浆、助剂以及溶剂等混合均匀，调配成各色漆。姑且将传统的色漆生产工艺称为主色浆法。这种工艺乃是将配方中的所有颜料全数加入到研磨漆料中，再分散、研磨，待细度合格后再补加树脂、助剂、溶剂等调配成漆。最后再根据肉眼或测色仪器的判断，添加某些单色浆以对其颜色进行微调，配制成漆。两种工艺各有优劣，现将其特点比较如下。  \n\n·生产周期两种工艺生产色漆的总生产周期虽然差别不大，但因为单色浆工艺中，各种色浆均已贮存在库，故无需临时对颜料进行研磨、分散，只要按配方加入各种成分再混合均匀即可。从接到订单到交货，及时、快捷，显然供货周期比主色浆法要短得多。  \n\n·对助剂的要求单色浆工艺对分散助剂的要求较高，相对于同一品种的颜料而言，助剂的用量一般要比主色浆法高。涂料厂研磨和配漆工段有经验的师傅们都知道；几种颜料在一起混合研磨制得的色漆，比起分开研磨后再混合的工艺来，不容易浮色、发花、絮凝。显而易见，单色浆工艺为了避免色漆成品的上述病，在制备单色浆时，必须加强对助剂的评估，必要时还得相应增加助剂的用量或添加助分散剂。  \n\n·对研磨树脂的要求主色浆法对研磨树脂几乎无要求，只要采用色漆中的主成膜物质即可。单色浆法则不然，必须认真考虑研磨树脂与本公司各类漆种中主成膜物质的相容性。·对生产设备的要求两种工艺对生产设备本身并无特殊要求，但以单色浆工艺法生产的工厂至少应配备 $5{\\sim}6$ 台砂磨机，分别研磨黑、白、红紫、蓝绿、褐黄五大类颜色的色浆，而且还要求尽可能彻底地清洗设备，否则必将给单色浆带来污染，为下一步调色、配漆带来麻烦。  \n\n·经济性研磨树脂不是万能的成膜物质，它不可能照顾到方方面面的漆膜性能，为了降低研磨树脂对色漆成品物性的影响，应尽可能减少色浆中研磨树脂的用量。这样势必需要增加润湿分散助剂的用量。采用价格相对昂贵的润湿分散剂来替代研磨树脂，从经济的角度来看，显然不划算。  \n\n有人曾就这两类工艺技术经济性方面的优劣作过详细比较，他们认为：如果仅仅从技术和生产的角度来看，单色浆工艺显然优于主色浆法，但单色浆工艺比较适合批量小于500kg产品的生产。生产批量较大的色漆时，如果采取单色浆工艺，则工厂成本将可能要高出$20\\%\\sim25\\%$ 9  \n\n综上所述，两类工艺各有优劣，制漆时可根据自身的条件和需要进行选择。汽车原厂漆的生产因车型不同而采用不同的工艺。如卡车、轻型车等用漆，因批量大、花色变化相对较少，故而普遍采用主色浆法。轿车、微型车等小型车用漆则因其批量小、花色多而主要采用单色浆法。而对于多层金属闪光漆的生产，因其中含有效应颜料，如铝粉、珠光粉以及石墨粉等，具有独特的片状结构，为使其不被破坏，不能采用传统的研磨分散设备进行分散加工，甚至连高速搅拌都不允许，因此无法采用传统的主色浆工艺生产，而必须采用单色浆工艺。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1039,
+        "chunk": "# 一、色浆  \n\n如上所述，采用单色浆生产工艺时都要用到“单色浆”。在汽车原厂漆中采用的单色浆应具备以下性能：  \n\n$\\textcircled{1}$ 要求与系统中主成膜物质的混容性良好；$\\textcircled{2}$ 贮存和运输过程中，无分层、絮凝、返粗现象；$\\textcircled{3}$ 色调、色强度、色纯度稳定，无任何色污染；$\\textcircled{4}$ 具有一定的热稳定性，能耐高温下烘烤（甚至是“过”烘）无明显色差；$\\textcircled{5}$ 黏度适当，易于操作；$\\textcircled{6}$ 对成品漆各项性能的影响不明显；$\\textcircled{7}$ 混入基料及其他组分的工艺简洁，只需低剪切力下搅拌、加人即可，不要求刀力分散的条件下，尽可能慢慢地加人”，届时不会产生絮凝、返粗甚至结块等猜$\\textcircled{8}$ 研磨树脂及分散助剂的用量相对较低，以尽量减少它们对最终产品性能的影响。  \n\n汽车原厂漆中用到的色浆系统主要包含两大类，即含普通彩色颜料（包括钛白、炭黑）的色浆和含铝粉、珠光粉、纳米级钛白之类效应颜料的色浆。一般稍具规模的汽车原厂漆生产厂家的色浆系统由数十个甚至上百个色浆组成，以对现有汽车面漆的颜色形成较为完整的色空间覆盖，现分述如下。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1040,
+        "chunk": "# 1.研磨树脂  \n\n如前所述，在单色浆工艺中研磨树脂的选择至关重要，在汽车原厂漆系统中，适用的研磨树脂应具备如下条件。  \n\n（1）混容性研磨树脂至少应与漆料中各类树脂的混容性良好。如主成膜物质（醇酸树脂、丙烯酸树脂、聚酯树脂等）、交联剂（氨基树脂、封闭型异氰酸酯等）以及其他辅料（能赋予体系流变性能的某些树脂或助剂等）。  \n\n(2）分散性对各类颜料（包括有机、无机颜料）的润湿性、分散性均优。（3）对成品性能影响各种色浆配漆后，对成品漆的物理力学性能、耐极性、非极性介质性能、耐老化性能等均无不良影响。  \n\n在汽车原厂漆单色浆系统中选择研蘑树脂时，偏重于性能方面的考量，而较少考虑它们的通用性。也就是说；重点在于看其是否影响到最终漆膜的性能，而不太注重它们与其他不常用到树脂的混容性。因此，在汽车原厂漆单色浆系统中很少像汽车修补漆那样采用所谓“通用色浆树脂”，而较为简捷地采取就地取材的方式。由于当今汽车原厂漆仍然以醇酸-氨基或丙烯酸-氨基类烤漆系统居多，故不少厂家都选择了对各类颜料润湿分散性均较好的氨基树脂与主成膜物质搭配以构成复合的研磨树脂。一般来说，在本色漆系统中的主成膜物质多为醇酸树脂或丙烯酸树脂，在金属闪光底色漆系统中则多为聚酯树脂以及聚酯树脂与丙烯酸树脂搭配等。另外，在金属闪光漆系统中采用CAB与氨基树脂的搭配也是一个不错的选择。总之，相对汽车修补涂料系统而言，汽车原厂漆系统的研磨树脂的选择比较简单，上述组合举例很容易满足单色浆系统对研磨树脂的基本要求。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1041,
+        "chunk": "# 2.彩色颜料  \n\n汽车漆（无论是原厂漆还是修补漆）是各类涂料中采用颜料品种最为广泛、要求也较为苛刻的领域。在汽车漆领域中，颜料的选择非常重要。应该根据颜料的种种特性慎重进行挑选，一般情况下，以下几项基本性能需特别留意。  \n\n(1）着色力着色力有时也被称为色强度，是某一颜料与另外一种颜料混合后影响最终颜色的能力。它是某种颜料对光线吸收和散射的结果。除了与自身化学性质有关外，还和颜料粒子的形状、大小、分布以及在展色剂中的分散有关。在汽车原厂漆以及汽车修补漆的色浆系统中，它是一项非常关键的性能指标。  \n\n(2）耐候性有些颜料在户外阳光的作用下，自身的颜色会产生不同程度的变化，变化程度越大，则说明颜料的光稳定性越差。这种现象多半是颜料自身发生化学反应所造成的。汽车漆对颜料的耐候性有着非常背刻的要求。选用任何品种的颜料前，必须通过严格的人工加速老化和户外曝晒实验。  \n\n（3）耐热性某些颜料，特别是某些有机颜料，如苯胺系、偶氮系等化合物受热易分解从而造成颜料的颜色变暗、褪色。汽车原厂漆多为高温 $(120\\sim160\\Upsilon$ ）烘烤固化，有时候还必须考虑“过烘”问题。因此，它们对颜料的耐热性要求颇高。而汽车修补漆的固化通常是室温，充其量也就低温 $(60\\sim70^{\\circ})$ ）短时间烘烤。对此项性能则要低得多。  \n\n（4）耐溶剂性某些颜料在与某些溶剂接触时会出现渗色现象，即表示该颜料的耐溶剂性差。汽车漆的涂装中，不少品种要求采用“湿碰湿”工艺，如双层金属闪光漆和本色底色漆系统就是如此。这两种系统的底色漆中采用的颜料如果耐溶剂性能差，将出现严重的渗色、色迁移现象，这是绝对不能允许的。  \n\n(5）水分含量颜料是一种微细粉末状物质，表面积较大，常常吸附空气中的一些水分。当颜料粒子中水分含量过高时，往往会带来一系列弊病，如絮凝、返粗、增稠等。在汽车修补涂料中，2K系统的色浆由于多为双组分聚氨酯类，所用颜料的含水量应尽可能少，否则颜料中所含的水分将会与异氰酸酯类固化剂的—NCO基团反应，释放出气体，可能给漆膜带来“痱子”，甚至起泡的危险。在汽车原厂漆中，则有可能带来“闷光”、“雾影”等光泽下降的漆膜病。  \n\n在高档汽车漆中，所采用的颜料大部分来自汽巴（Ciba-Geigy）、科莱恩（Clariant）、巴斯夫（BASF）等几家国际知名的高档颜料生产厂家。高档颜料中虽已有部分国产化。但不得不承认大多数国产颜料的分散性能仍然低于进口的同类产品。表现在分散时间较长、所得产品黏度偏高以及流动性较差等。更为关键的是几乎所有国产颜料都无法克服不同生产批次之间的色差，难以满足汽车漆调色系统对单色浆质量的要求。  \n\n我国的中、低档汽车原厂漆中大量采用了国产颜料，除红色系列外，其他颜色系列如蓝色系列（菁蓝、菁绿)、黄色系列（铬黄、镉黄等)、白色系列（金红石型钛白）、黑色系列（炭黑、铁黑等）等均已替代价格较高的同类进口产品。  \n\n现就可用于汽车漆系统中的颜料按颜色分类评述如下。  \n\n(1）红紫色系列红紫系列颜料大部分为有机颜料，计有花系列（PR179为红色、PV29为紫色）、双（对氯苯基)-1，4-二酮-吡咯并吡咯（PR254）、喹丫啶酮（PV19、PR122、PR202，其中晶型为红色， $\\beta$ 晶型为紫色）、二嗪（PV23）、吡葱酮、葱醒、 $\\beta$ 羟基萘酸酰胺、 $\\beta$ 羟基萘酸锰盐以及偶氮类等。暗红色色调采用无机颜料，如铁红、镉红等。应根据色鲜艳度、透明、半透明以及不透明等分别选择适用于金属闪光漆和本色漆色浆中的品种。汽巴公司的二酮-吡咯-吡咯、喹丫啶酮类，巴斯夫公司的花系列红色颜料等色泽鲜艳，各项性能均较突出，是汽车漆的首选品种。汽巴公司的IrgazinDPPBO，巴斯夫公司Paliogen red L3530，克莱恩公司 Novoperm rot BL、Novoperm pink E、Novoperm ER02 等产品耐热性达 $200\\ensuremath{\\mathbb{C}}$ 以上，特别适合用于原厂漆中。  \n\n(2）黄色系列黄色系列颜料与红色稍有不同，有机和无机颜料均可采用。黄色有机颜料有四氯异吲哚啉酮（PY110）、异吲哚啉（PY139）、苯并咪唑酮（PY154）、镍络偶氮黄(PY150)、偶氮类（PY213）以及芳酰胺类等。黄色无机颜料有钒酸（PY184）、钼铬酸铅、铁黄等。黄色有机颜料色泽鲜艳，耐候性也不错，但价格昂贵。黄色无机颜料中，铬黄系列因其价格低廉，性能尚可，用于涂料中由来已久。但因含有铬、铅之类重金属不符合环保方面要求，且耐候性能稍嫌不足，不建议选用。  \n\nBASF公司最先开发出一种新型黄色无机颜料作为铬黄的代用品—钒酸秘类，商品牌号为SicopalYellowL1100。这是一类新型黄色无机颜料，简称黄。它的颜色鲜艳，性能优异，已被不少汽车漆厂商所选用。其后汽巴、拜耳、Cappelle等公司均有同类产品进入市场。  \n\n金属氧化物混相颜料是几种金属氧化物通过高温固相反应使金属离子经热扩散进入到基本晶格结构中，部分取代晶格中的阳离子，形成具有全新晶格结构的化合物。这类颜料因其耐候性、耐热性均特别突出，再加上安全、无毒，一上市就受到涂料业界的特别青。金属氧化物混相颜料品种较多，有钛镍、钛铬、钛锯铬等。BASF公司的SicotanYellowL1010和L1012属钛镍锑黄，SicotanYellowL1910、L2010、L2011、L2110等属钛铬锑黄。拜耳、Shephered、Sandoz以及日本的石原产业也都有金属氧化物混相颜料面世。IrgazinYellow2093带绿光的钒酸秘鲜黄是汽巴的新产品，具有高的色饱和度、遮盖力、耐候性、耐热性等。被推荐用于汽车原厂漆和修补漆中。  \n\n(3）蓝色及绿色系列蓝色及绿色系列颜料以酸菁系列有机颜料为主（PB15、PG7、PG36)。另外还有少量阴丹士林蓝（PB60）。无机颜料中铬绿、铁蓝等因颜色深暗，不够鲜艳，在高档轿车漆中用得不多，但中、低档汽车漆（如一般卡车、农用车等）中仍然可以采用。  \n\n通常人们所采用的菁蓝颤料，更确切地说应该叫菁铜。由于其晶相的不同使它的色调有所差别。晶相为α型的菁蓝显红光， $\\beta$ 型显绿光，而e型显更为鲜艳的红光。菁蓝颜料色相鲜艳、着色力强，而且耐酸、耐碱、耐候性均佳，其中 $\\beta$ 型菁蓝最为稳定，如为α型，则一定要标明是稳定型的品种。一般涂料工业中都采用稳态献菁蓝。BASF公司的献菁颜料系列比较齐全，在该公司的HeliogenBlue系列产品中，L6875、L6900、L6901、L6920、L6930、L6975属于α型，L7020、L7080、L7081、L7101F属于 $\\beta$ 型，L6700属于型。另外该公司还推出一种α型无金属菁蓝颜料，HeliogenL7560。该产品因其低的随角异色效应被推介用于金属闪光底色漆中。汽巴公司的IrgaliteGLNF、PG、GLVO等属 $\\beta$ 型，BSNF属α型。国产的菁系列颜料性能也不错，在一般汽车漆中多有采用，如北京、天津产的酞菁蓝被业内简称为京酞蓝、津蓝等。  \n\n群青是一种无机蓝色颜料，用于涂料工业中已有多年的历史。这是一种复杂的铝、钠硫硅酸盐类，它的颜色鲜艳，耐候、耐碱、耐热，着色力特别强，多用于辅助调色，特别是白色涂料的所谓“提蓝”增白中。  \n\n菁铜的氯或溴代产品就是菁绿。它与菁蓝的特点类似，颜色鲜艳、着色力强，而且耐酸、耐碱、耐候性均佳，所以在涂料业被作为绿色系列颜料普遍采用。  \n\n蓝紫系列颜料多为有机芳杂环化合物，如咔唑二唔嗪，它的着色力强，耐热性、耐候性优良，但价格稍高，多与菁蓝系颜料拼用以调整色漆的红相。  \n\n(4）白色颜料钛白粉是涂料工业中用量最大的颜料，它的用量要占到涂料用颜料总量的90%以上，占涂料用白色颜料的95%以上。按晶型分，钛白有金红石型和锐钛型两种。汽车漆中多采用金红石型钛白，而且最好采用耐候性特别优良的品牌，如杜邦的R-960，拜耳的R-KB-5，SCM的RCL-666等。至少也要采用通用型的产品，如R-902，R-KB-6，RCL-535，RCL-575等。  \n\n(5）黑色颜料黑色颜料中主要有炭黑和铁黑两种。我国涂料原料市场的炭黑供应商主要有德固萨（Degussa）和卡伯特（Cabot）等外国公司，其中德固萨占据绝大部分。国产炭黑颜料大都只能用于低档汽车以及一般工业、家私等对耐候性要求不高的场合，高档汽车漆领域用得较少。主要存在问题是黑度不够、分散性能差，特别容易絮凝、返粗。  \n\nFW 200、1300均为黑度值最好、泛蓝光的炭黑，用于制造纯黑色色漆中，如奥迪黑、奔驰黑等高级轿车色。101灯黑遮盖力较低，多用于金属闪光底色漆中作调色用。  \n\n（6）氧化铁系颜料氧化铁系颜料是一大类历史非常久远的老品种。据考证几万年前就有人把天然铁红用作绘画颜料。这类颜料因具有不渗色、耐各种介质、吸收紫外线以及价格低廉等特点，而成为涂料工业中使用量仅次于钛白粉的第二大无机颜料。  \n\n氧化铁系颜料包含铁红、铁黄、铁黑、铁棕等。早期的氧化铁系颜料多为天然矿物制品，现已有 $80\\%$ 以上改用合成产品。合成氧化铁系颜料的色泽比天然制品鲜艳，色调也要稳定一些，另外其他方面性能也有所改善。过去氧化铁系颜料，特别是氧化铁红多作为防锈颜料用于底漆中，极少用作面漆中的赋色颜料。主要是因为它们的色相偏暗，远不如红色有机颜料鲜艳，在很大程度上限制了它们的使用范围。  \n\n拜耳公司是国外知名氧化铁系颜料商，该公司的这类产品色泽相对鲜艳，且色相稳定，已被国内外不少汽车漆制造厂选用，如Bayferrox110M、120M、120FS、130FS、140M、160FS、180M、915、943等，型号中数字后面M代表超细，FS代表抗絮凝性能好的新产品。  \n\n氧化铁系颜料粒子的粒径一般在 $0.1\\sim0.5\\mu\\mathrm{m}$ 、粒径小于 $0.1\\mu\\mathrm{m}$ 的氧化铁系颜料呈透明或半透明状，属纳米级产品。有透明铁红、透明铁黄、透明铁黑以及透明铁棕四大类。因其价廉物美已有不少厂家将其制成1K色浆用于金属闪光底色漆中。世界上主要生产透明氧化铁颜料的厂商有德国的BASF、美国的Hilton-Davis、比利时的Cappelle等。  \n\n(7）钻盐BASF公司的透明蓝和透明绿是一种尖晶石钴盐，亦属透明颜料，SicotransBlue L6315为氧化铝-钻盐，Sicotrans GreenL9715为氧化锌-钻盐。该公司的 Sicotrans 系列颜料均被推荐用于汽车漆，特别是金属闪光漆中。其中除L2715和L2915D为半透明外，其余均为透明颜料。L2915D冲淡后可显示出特别的黄白色调。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1042,
+        "chunk": "# 3.效应颜料  \n\n汽车漆中采用的效应颜料主要有铝粉、珠光粉、纳米钛白粉以及石墨粉等。  \n\n（1）铝粉涂料用铝粉颜料是以高纯度金属铝为原料，按照湿法球磨工艺生产而得的片状颜料。早期铝粉粒子鳞片状结构的形状并不规范，类似玉米片，后来在粒子形状方面发展了银圆型，在表面状态方面发展了抛光型，在表面处理方面发展了耐酸型，使铝粉颜料的遮盖力、光亮度、随角异色效果、鲜映性更佳，耐介质性能特别是汽车涂料中所要求的耐酸雨性能有了相当大程度的提高。铝粉颜料的粒径和粒径分布对铝粉的各项性能影响极大，是反映铝粉质量的关键控制指标。铝粉平均粒径对光学性能的影响见表3-2-9。  \n\n表3-2-9铝粉平均粒径对其光学性能的影响  \n\n\n<html><body><table><tr><td>平均粒径</td><td>一</td></tr><tr><td></td><td></td></tr><tr><td>光亮度</td><td></td></tr><tr><td>闪烁度</td><td></td></tr><tr><td>色饱和度</td><td></td></tr><tr><td></td><td></td></tr><tr><td>随角异色效果</td><td></td></tr><tr><td>遮盖力 鲜映性</td><td>←</td></tr></table></body></html>  \n\n汽车漆中采用的铝粉颜料主要依靠进口，生产厂家主要有德国爱卡（Eckart-Werke）、美国希伯来（Silberline ManufacturingCo.inc）以及日本东洋（TOYOAluminium K.K.）等。近年来已有不少国产铝粉投入市场，但大都用于低档汽车漆以及一般工业和民用涂料中，能用于汽车漆中的品种并不多。主要差距如下。  \n\n$\\Phi$ 表面处理与进口产品相比尚存一定差距，表现在贮存稳定性差。铝粉漆贮存一段时期后，允许铝粉颜料沉底，但应该很容易揽拌分散。有些国产铝粉则很难搅开。此外还表现在光亮度（白度）逐渐下降，漆膜表面容易产生颗粒等。  \n\n$\\textcircled{2}$ 粒径特别是粒径分布不稳表现在不同生产批号间普遍存在色差、闪烁效果不一，有时甚至肉眼都能看出前后两批铝粉原料粒子间的明显差异。  \n\n爱卡公司产品中Metallux2000系列属银圆型。8000系列铝粉表面经抛光处理，粒度一般较小，粒径分布窄，高白度、清晰明亮，属光亮型。9000系列粒径由中细到很细，粒径分布窄，具有高亮度和丝光效果。Tufflake型系列铝粉抗降解性能特别好。  \n\n铝粉中可用于汽车漆中的应首选银圆型系列、铝粉表面经抛光处理、耐酸型等品种。平均粒径从 $10\\sim40\\mu\\mathrm{m}$ 的细银（南方称之为幼银）到粗银的普通型铝粉及闪烁型铝粉，通常采用 $\\scriptstyle7\\sim9$ 种铝粉。  \n\n(2）珠光颜料珠光类颜料能反射出柔和的珍珠光泽，是效应颜料中除铝粉外又一大类产品。珠光颜料是在云母片表面包覆金属氧化物所构成。用于包覆的金属氧化物有 $\\mathrm{TiO}_{2}$ ，$\\mathrm{Fe}_{2}\\mathrm{O}_{3}$ ， ${\\mathrm{TiO}}_{2}+{\\mathrm{Fe}}_{2}{\\mathrm{O}}_{3}$ ， $\\mathrm{TiO}_{2}+\\mathrm{C}\\tau_{2}\\mathrm{O}_{3}$ 等。正是云母表面的这些品种各异的包覆膜使珠光颜料显现出不同的颜色特征。  \n\n除表面包覆膜外，云母的粒径对珠光颜料的性能也有很大影响，如遮盖力、闪烁效果（表3-2-10)。  \n\n表3-2-10云母粒径对遮盖力、闪烁效果的影响  \n\n\n<html><body><table><tr><td>粒径/μm</td><td>遮盖力</td><td>闪烁效果</td></tr><tr><td></td><td></td><td></td></tr><tr><td>20~500</td><td>大中</td><td>差中 ↑</td></tr><tr><td></td><td>小数小</td><td>好好</td></tr><tr><td>5~25</td><td></td><td></td></tr></table></body></html>  \n\n同样作为金属闪光底色漆效应颜料的珠光粉与铝粉相比有所不同：铝粉完全不透明，而珠光粉则为透明到半透明。珠光粉的这一特点使它在受到可见光照射时产生多重反射、折射、透射等光学现象。这给珠光颜料带来柔和如珍珠般的光泽、诱人的干涉色、优异的随角异色效应等。这些都是采用铝粉所无法得到的效果。涂料用珠光颜料又细分为银白色、彩色、彩虹色等系列。  \n\n$\\textcircled{1}$ 银白色系列为云母的二氧化钛包覆物。因包覆膜的厚度、云母粒子的大小不同可得十几种银白色珍珠光泽颜料。粒子越大，显现金属色调闪烁光泽越强；粒子越小，则展现出如丝绸般柔和的光泽。包覆的二氧化钛采用锐钛型或金红石型均可。前者用于一般涂料产品，而后者用于对户外性能要求较高的场合，如汽车涂料等。  \n\n$\\textcircled{2}$ 彩虹色系列此系列珠光颜料能显现出如彩虹般幻彩效果。当可见光照射到这类颜料表面时，入射光将被分解为反射光（此时假设为红色）和透射光（作为前者补色则为绿色)。如果包覆膜厚度改变，将形成不同的反射色光和透射色光。采用彩虹色系列颜料时，涂层的底色的选择很重要。当底色为白色时，透射色光被再度反射而与原来的反射色光混合还原为入射光，这将降低反射光的效果。当底色为黑色时，透射色光被底层吸收，反射色光将被进一步反衬出来。  \n\n$\\textcircled{3}$ 彩色系列颜料既具有珍珠特色，亦能表现铝粉、金粉、合金粉等金属颜料所特有的金属光泽。彩色系列颜料因包覆膜不同而分为两大类。  \n\na.氧化铁光泽、着色力强，具有金属色调。  \n\nb.二氧化钛 $^+$ 氧化铁不但具有珍珠光泽，而且还带有各种氧化铁的色彩，结合成彩色珍珠色调。  \n\n上述几大类珠光颜料中均有耐候级产品和一般工业用产品。默克公司将耐候级产品标以WR字样。该公司对世界各国汽车漆生产厂选用他们的珠光颜料做过一番统计，资料显示，有关厂家选用的全都是WR系列产品。在各类名车中采用最多的是Iriodin9225WR、9235WR、9504WR以及9121WR。  \n\n汽车漆中采用的珠光颜料其粒径多为 $10\\sim40\\mu\\mathrm{m}$ 范围的产品。其他粒径范围的产品采用不多。近年来默克公司又开发了第二代外用珠光粉颜料，代号为WRⅡ，如Iriodin9514WR丝光红，这是一种 $\\mathrm{Fe}_{2}\\mathrm{O}_{3}+2\\mathrm{rO}_{2}$ 包覆云母珠光颜料。在QUV人工加速老化1000h后其光泽保留率在 $92\\%$ 以上，灰度等级为4，足见其卓越的耐候性能。  \n\n(3）纳米级钛白粉纳米级钛白粉粒径大约在 $10\\sim50\\mathrm{nm}$ ，它对可见光没有散射，透射能力非常强，故而几乎没有遮盖力。这种超细钛白只能反射可见光中短波波段的光波，所以看起来是一种带少许蓝色调的乳白色。基于这样的光学特性，决定了纳米级钛白不能像铝粉或珠光粉那样单独作为效应颜料使用，只有与铝粉或珠光粉一起拼用时才能发挥它独有的特点。当它与珠光粉一起使用时可进一步加强珠光颜料的干涉色。在与铝粉拼用时，它可散射较短波段的光线，而形成蓝色的侧视色调，与此同时将波段较长的红、绿光透射到铝粉层再次被反射出来，形成正视的金黄色。这样所产生的随角异色效应所带来的柔和、乳白色调的视觉效果给人以豪华、亮丽的艺术感染力。  \n\n纳米级钛白粉的生产厂家有德国的德固萨、日本帝国化工、石原产业等。这些厂家为方便客户使用，其商品一般都不是粉状，而是预制成在溶剂中的分散液，以色浆形式提供给客户。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1043,
+        "chunk": "# 4.助剂  \n\n在本色漆用色浆的制造中，可根据需要添加某些润湿分散剂，而在金属闪光底色漆中采用的助剂则主要针对效应颜料的定向，防止这类密度较大的颜料粒子沉降、结块等。分散剂的合理选用对于提高效应颜料（铝粉、珠光粉等）的定向、改善施工性、减少在罐内沉降倾向、改善清漆层的映象清晰度都能够发挥非常关键的作用。可采用的助剂主要有润湿分散剂、分散蜡和醋酸丁酸纤维素等。  \n\n(1）润湿分散剂如前所述，在现有的氨基烤漆系统中由于采用了对各类颜料润湿分散性能均较好的氨基树脂作为研磨树脂，一般情况下，在研磨色浆时都可以不加或仅需添加少量的润湿分散剂。但润湿分散剂的添加有助于效应颜料更好地分散和提高贮存稳定性却是不争的事实。有关润湿分散剂的特性及选用原则可参见下一节本色漆部分。  \n\n(2）分散蜡在各类溶剂型金属闪光底色漆中，为了帮助效应颜料在漆膜中更好地定向、分散和防沉，往往还要添加一种“分散蜡”。适用于金属闪光漆中的分散蜡主要有两大类，即乙烯类共聚物（包括乙烯-醋酸乙烯共聚物、乙烯-丙烯酸共聚物等）和聚酰胺蜡。  \n\nCerafak100、Cerafak103、Cerafak106是毕克公司用于溶剂型金属闪光漆中的蜡分散体。Cerafak100、Cerafak106均为乙烯-醋酸乙烯共聚物分散体（EVA)，而Cerafak103为乙烯-丙烯酸共聚物。  \n\nDisperKC568为澳大利亚KemperialCo.产分散蜡系防沉剂，属一种改性乙烯-醋酸乙",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1044,
+        "chunk": "# 烯类共聚物。  \n\nDisparlon6900-20X为日本楠本化成株式会社产品，它是聚酰胺在二甲苯溶液中通过溶胀而形成的蜡质糊状物。  \n\n这两类分散蜡助剂用于各类溶剂型金属闪光底色漆中，都能起分散、防沉和定向等方面的作用。它们不仅大大改善了该类产品中的效应颜料（铝粉、珠光粉以及超细钛白等）在漆浆和成品底色漆中的分散性、沉降性能，而且还有效地改善了效应颜料的定向作用，使之具有更好的白度和随角异色性、较少的云斑色差及雾影等。  \n\n比较这两类助剂总效果大体相差不多，但Disparlon 6900-20X和DisperKC568的增稠效果明显，而BYK的Cerafak106则表现稍差（表3-2-11)。  \n\n表3-2-11金属闪光底色漆用分散蜡助剂品牌及规格  \n\n\n<html><body><table><tr><td>商品牌号</td><td>产地</td><td>类型</td><td>NVM/%</td><td>黏度/mPa* s</td><td>溶剂</td></tr><tr><td>Disparlon 6900-20X</td><td>A</td><td>聚酰胺</td><td>20</td><td></td><td>X/EtOH</td></tr><tr><td>Cerafak 106</td><td>B</td><td>乙烯-醋酸乙烯共聚物</td><td>6</td><td>10</td><td>X/BuAc/BuOH</td></tr><tr><td>Disper KC 568</td><td>C</td><td>改性乙烯-醋酸乙烯共聚物</td><td>10</td><td></td><td>X/BuOH</td></tr></table></body></html>\n\n注：A为日本楠本化成株式会社，B为毕克化学，C为澳大利亚Keperial；X为二甲苯，BuAc为醋酸丁酯，BuOH为丁醇，EtOH为乙醇。  \n\n(3）醋酸丁酸纤维素（CAB）CAB在金属闪光底色漆中和分散蜡助剂一样，对效应颜料起定向、防沉等方面的作用，另外它还是辅助成膜物质，对于湿涂层的溶剂释放性（即漆膜的物理干燥性能)，湿喷湿施工性以及漆膜硬度的改善都有非常重要的作用。在采用湿喷湿施工工艺的金属闪光底色漆系统中，CAB的使用比分散蜡更为普遍。CAB目前仍然依赖进口，其主要供应商为依士曼公司，它的商品牌号及规格将在以后汽车修补漆的有关章节中再详细介绍，使用时可参考有关数据。在实际使用的配方中，大都选择至少两种CAB搭配，搭配的目的多为调整漆料的黏度、物理干燥性能、不挥发分以及漆膜的硬度等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1045,
+        "chunk": "# 5.单色浆的制造  \n\n(1）彩色颜料单色浆制造选择适当的研磨树脂、颜料、润湿分散剂以及溶剂，再通过实验验证以确定色浆配方。实验中除了首先应该考核研磨时间、色浆的流动性等性能外，还必须采用以下两项试验方法来检验色浆配方的可行性。  \n\n$\\textcircled{1}$ 浓色浆的冲淡性能用面漆中的主成膜物质配制成的调合漆料分别将该浓色浆按照一定的比例冲淡，以下方法可供选作参考：裁取 $10\\mathrm{mm}\\times100\\mathrm{mm}$ 的透明聚酯膜片，以浸涂方式薄薄地涂上一层已冲淡的色浆漆料；待风干后观察涂层是否出现浑浊、颗粒、网纹等现象，如均匀、透明则表示合格。  \n\n$\\textcircled{2}$ 与系统内其他色浆的配合性能考核该色浆与系统内其他品种的色浆配合时是否会出现浮色、发花等问题。将该色浆与白色色浆按 $1:1$ 的比例混合均匀，然后用指研法看其是否出现分色现象。必要时还要与一些拼合时有可能出问题的色浆进行补充实验，如前面提到的菁系列色浆就需要多做几次混合实验。  \n\n在选定了研磨树脂、颜料、润湿分散剂后就可以制造色浆了。色浆制造分为两步：第一步是制造浓色浆；第二步将浓色浆冲淡成便于调色的色浆。  \n\n$\\Phi$ 浓色浆的制造工艺  \n\na.在配料缸中加入配方中所列溶剂及主成膜物质（如醇酸树脂、聚酯树脂等)，搅拌均匀。  \nb.在搅拌下慢慢加人颜料，加完后再搅拌一定时间。  \nc.在揽拌下慢慢加人氨基树脂，加完后再高速分散一定时间使之完成预分散。  \n\nd.在砂磨机上研磨至细度小于 $10\\mu\\mathrm{m}$ 费e.过滤、出料。$\\textcircled{2}$ 冲淡工艺a.在调漆缸中先加人上述制备的浓色浆。b.根据不同品种浓浆黏度的具体情况，在搅拌下分批逐步加入冲淡用调和漆料。c.第一批投入后，慢搅 $10\\mathrm{{min}}$ 直至浓浆变成均匀、流动性较好的糊状物（批量的大小应根据浓浆的黏度及生产总批量的大小而定）。  \n\nd.然后再继续加入后几批冲淡用调和漆料，最后加溶剂。再继续搅拌至少 $10\\mathrm{min}$  \n\n典型的浓色浆配方列于表3-2-12～表3-2-14中。其中表3-2-12为典型醇酸-氨基本色漆用色浆，表3-2-13为以CAB溶液和氨基树脂搭配作研磨树脂体系的色浆，而表3-2-14则为以聚酯树脂为研磨树脂的色浆。制得浓色浆后，再用面漆中的主成膜物质配制的调和漆料将其冲淡成调色色浆。  \n\n表3-2-12典型醇酸氨基烤漆用色浆配方例 单位：质量份  \n\n\n<html><body><table><tr><td>组成</td><td>白色</td><td>特黑</td><td>皇室蓝</td><td>鲜紫</td><td>鲜红</td><td>铁红</td><td>鲜黄</td></tr><tr><td>DC8868</td><td>20.0</td><td>40. 0</td><td>64.0</td><td>50.0</td><td>55. 0</td><td>50. 0</td><td>40.0</td></tr><tr><td>DC8868A Bentone 34（10%胶液）</td><td>10.0 1. 0</td><td>16.0 1.0</td><td></td><td></td><td>10.0</td><td>2.5</td><td></td></tr><tr><td>醋酸丁酯（98%）</td><td>55.0</td><td></td><td>3.0</td><td></td><td></td><td></td><td></td></tr><tr><td>Maprenal MF650</td><td>6.0</td><td>8.0</td><td></td><td>10.0</td><td>10.0</td><td>13.0</td><td>5.0</td></tr><tr><td>异丁醇</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td>3.0</td><td>3.0</td><td></td><td></td></tr><tr><td>二甲苯</td><td></td><td></td><td>24.8</td><td>17.0</td><td>14.0</td><td>14.5</td><td>5.0</td></tr><tr><td>DC8868</td><td></td><td>27.0</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>BYK130</td><td></td><td></td><td>0.2</td><td></td><td></td><td></td><td></td></tr><tr><td>2059 Kronos TiOz</td><td>8.0</td><td>16.0</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>FW200</td><td></td><td>8.0</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>7101(酸菁蓝）</td><td></td><td></td><td>8.0</td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>RV6911</td><td></td><td></td><td></td><td>10.0</td><td></td><td></td><td></td></tr><tr><td>A2B(鲜红）</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td>8.0</td><td></td><td></td></tr><tr><td>140M(铁红）</td><td></td><td></td><td></td><td></td><td></td><td>20.0</td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>L 2135S</td><td></td><td></td><td></td><td></td><td></td><td></td><td>45.0</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>BYK110</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>5.0</td></tr></table></body></html>  \n\n表3-2-13典型金属闪光底色漆用色浆配方例 单位：质量份  \n\n\n<html><body><table><tr><td>组成</td><td>透明红</td><td>翠绿</td><td>鲜黄</td><td>深暴</td><td>艳紫</td><td>艳蓝</td></tr><tr><td>CAB381-2溶液 Maprenal MF650 醋酸丁酯 醋酸甲氧基丙酯 二甲苯 DC8868 BYK130 L2817(红) Lag-C(翠绿） L6482(菁蓝） RL sp A2B(鲜红）</td><td>42.0 10.0 38.0 10.0</td><td>42.0 10.0 36.0 12. 0</td><td>39.0 9.3 42.4</td><td>42.0 7.5 33.0</td><td>50.0 10.0 27.5 5.0 7.5</td><td>50.0 10.0 29.0 5.0 6.0</td></tr></table></body></html>  \n\n表3-2-14典型金属闪光底色漆用色浆配方例 单位：质量份  \n\n\n<html><body><table><tr><td>组成</td><td>鲜红</td><td>暗绿</td><td>橘黄</td><td>透明黑</td><td>紫色</td><td>深蓝</td></tr><tr><td>DC8868</td><td>72.0</td><td>65.0</td><td>40.0</td><td>65.0</td><td>60.0</td><td>73.0</td></tr><tr><td>醋酸丁酯 醋酸甲氧基丙酯</td><td>20.0</td><td>20.0</td><td>5.0</td><td>10.0</td><td>33.0</td><td>20.0</td></tr><tr><td>二甲苯 DC8868</td><td></td><td></td><td></td><td>12.8</td><td></td><td></td></tr><tr><td>BYK130</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>GBL 7975Z(橘黄)</td><td></td><td></td><td>50.0</td><td></td><td></td><td></td></tr><tr><td>Lag-C(翠绿）</td><td></td><td>15.0</td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>L6480(酸菁蓝）</td><td></td><td></td><td></td><td></td><td></td><td>7.0</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td>6.0</td><td></td></tr><tr><td>RL sp</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>RV6832(红)</td><td>8.0</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>FW101</td><td></td><td></td><td></td><td>12.0</td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>流变助剂液</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td>5.0</td><td></td><td></td><td></td></tr></table></body></html>\n\n注：表3-2-12～表3-2-14中颜料产地如下：汽巴（Ciba-Geigy），A2B；巴斯夫（BASF），L2817、L6480、L6482、Lag-C、L1916、L7101、L2135S;克莱恩（Clariant），RL sp；卡珀（Cappelle），GBL 7975Z；德固萨（Degussa），FW200、FW101；拜耳（Bayer)，140M、RV6832、RV6911；Hoechst，Maprenal MF650（异丁醇醚化三聚氰胺甲醛树脱）。  \n\n表3-2-15中标出了色差和色强度的指标范围，色差 $\\Delta E{\\leqslant}1$ ，色强度波动范围则在5%以内。由于单色浆不允许调色，如果出现色差，不能通过加入某种色浆来调整色调，所以这两项指标的控制在实际生产中难度极大，要求极严格的质量控制措施和企业管理才能有效实施。  \n\n表3-2-15彩色颜料色浆技术标准  \n\n\n<html><body><table><tr><td>色差（△E)</td><td>≤1</td><td>电脑配色仪或色差仪</td></tr><tr><td>色强度/%</td><td>100±5</td><td>电脑配色仪或色差仪</td></tr><tr><td>漆膜外观</td><td>平整光亮</td><td>目测</td></tr><tr><td>细度/μm</td><td>≤10</td><td>GB 1724-1979</td></tr><tr><td>黏度（涂-4杯，23℃）/s</td><td>70~120</td><td>GB 1723—1993</td></tr><tr><td>不挥发分/%</td><td></td><td>GB 1725—1979</td></tr></table></body></html>\n\n注：标准中黏度指标控制范围较大是因为不同品种色浆之间的差异，具体到某个品种时，则范围还是较窄，  \n\n(2）效应颜料浆的制造金属闪光涂料独特的光学效果不单单来自效应颜料本身，而且和成膜物质、助剂、溶剂、生产工艺，甚至施工工艺都息息相关。在选定了各种组分、确定了配方之后，下一个重要环节就是生产加工。铝粉、珠光粉之类的效应颜料的分散与彩色颜料不同，它们独特的鳞片状的结构不允许承受高剪切速率下的切变作用，即分散时不能采用高速揽拌，就更不用说砂磨机了。为避免铝粉或珠光粉颜料粒子的鳞片在分散过程中被破坏，除尽可能采用低速搅拌外，建议采用叶片式桨叶而不采用通常高速搅拌机上的圆盘式桨叶。生产实践告诉人们：低转速时，叶片式桨叶的搅拌效果比盘式桨叶要好。  \n\n$\\boldsymbol{\\Phi}$ 生产工艺及流程示意a.效应颜料浆典型的生产工艺·将效应颜料先加入到配料罐中。  \n\n·然后分批加入溶剂，此时慢慢开动搅拌，将效应颜料搅成稀糊状。继续揽拌10～$20\\mathrm{{min}}$ 身  \n\n·溶剂：效应颜料 $=(1{\\sim}2):1$  \n\n·熟化 $10\\sim24\\mathrm{h}$ 录  \n·揽拌下慢慢加入调和漆料、助剂（注意切不可反过来添加，否则容易形成颗粒)。·加入适量溶剂调整黏度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1046,
+        "chunk": "# b.基本流程示意  \n\n![](images/286382b1d0c9f1bacf9c8211454688ebf9a7ffc66a472c1c68a4737b7f368b58.jpg)  \n\n总结效应颜料色浆生产工艺，有三点要素必须注意：低速、慢加和熟化。熟化阶段非常重要，它可使效应颜料与展色剂间的润湿、渗透更为完全，对减少漆膜表面因铝粉或珠光粉分散不佳而形成的颗粒，防止色浆沉降、抗絮凝等都大有禅益。  \n\n$\\textcircled{2}$ 效应颜料色浆配方举例效应颜料色浆中效应颜料的用量因品种不同而有所差异。大体的用量范围为：铝粉 $5\\%\\sim8\\%$ ：珠光粉 $8\\%\\sim12\\%$  \n\n现举一例典型轿车金属闪光底色漆用效应颜料浆的配方和工艺供参考。  \n\na.配方（质量份）  \n\n<html><body><table><tr><td>分散蜡液（6%）</td><td>23.0</td><td>MF 650氨基树脂</td><td>15. 0</td></tr><tr><td>热固性丙烯酸树脂</td><td>13.9</td><td>BYK 300</td><td>1. 0</td></tr><tr><td>聚酯膨润土胶液（10%）</td><td>8.3</td><td>松节油</td><td>1.00</td></tr><tr><td>聚酯树脂</td><td>5.0</td><td>PMA</td><td>10. 0</td></tr><tr><td>Setal 90173 SS 50</td><td>1.7</td><td>Alpate 8160 AR(铝粉浆）</td><td>2.3</td></tr><tr><td>CAB 381-0.5溶液(20%)</td><td>10. 0</td><td>Aipate8820（铝粉浆）</td><td>1.2</td></tr><tr><td>CAB381-2溶液（20%）</td><td>2.0</td><td>二甲苯</td><td>6.1</td></tr></table></body></html>\n\n注：Setal 90173SS50，AKZO产；Alpate8160AR、8820，日本东洋株式会社产。  \n\nb.工艺  \n\n·将分散蜡液 $(6\\%$ ）添加到配漆缸中，搅拌 $10\\mathrm{{min}}$ 左右，检查细度（如 ${\\leqslant}20\\mu\\mathrm{m})$ 。然后在搅拌下慢慢加人热固性丙烯酸树脂，再继续搅拌至少 $30\\mathrm{{min}}$ ，检查细度应合格（如${\\leqslant}20\\mu\\mathbf{m})$ 。  \n\n·依次加入聚酯膨润土胶液 $(10\\%)$ 、聚酯树脂、Setal90173SS50、CAB381-0.5溶液$(20\\%)$ 、CAB381-2溶液 $(20\\%)$ 、MF650氨基树脂、BYK300、松节油，然后在揽拌下慢慢加入PMA、Alpate816AR（铝粉浆）、Alpate8820（铝粉浆）、二甲苯，继续搅拌 $30\\mathrm{{min}}$ 费  \n\n·至少熟化10h以上，方可用于配制底色漆。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1047,
+        "chunk": "# 二、本色漆  \n\n早期的汽车面漆主要采用醇酸树脂类以及硝基纤维素类，由于其在耐候性方面的不足，后改为热塑性丙烯酸类。直到20世纪的70年代，汽车涂装系统仍然有不少厂家采用一涂一烘（1C1C）的工艺。单层本色漆仍然为汽车总装厂的首选。直到最近，欧洲以及世界上其他地区仍有不少汽车总装厂将醇酸-氨基烤漆用于轿车、轻卡、卡车等车辆上。而在北美等地则习惯采用丙烯酸-氨基烤漆。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1048,
+        "chunk": "# 1.主成膜物质  \n\n如前所述，可用于汽车本色漆的树脂因地域及习惯的不同，既可为醇酸树脂亦可为热固性丙烯酸树脂，对这两类树脂的具体要求分述如下。  \n\n(1）热固性丙烯酸树脂含羟基丙烯酸类树脂中加入氨基树脂即为丙烯酸-氨基烤漆，主要用于汽车原厂漆、摩托车、家电以及其他对装饰性要求较高的工业领域。  \n\n①官能基团对树脂性能的影响影响羟基丙烯酸类涂料最终性能的各项因子中以羟基值对漆膜性能的影响最大。表3-2-16中列举了羟基值对羟基丙烯酸类涂料漆膜的力学及化学性能的影响。  \n\n表3-2-16羟基值对羟基丙烯酸类涂料漆膜性能的影响  \n\n\n<html><body><table><tr><td>项目</td><td>羟基值- →</td><td>项目</td><td>羟基值- →</td></tr><tr><td>相容性 铅笔硬度 附着力</td><td></td><td>柔韧性 耐磨耗性 耐水性</td><td>← →</td></tr></table></body></html>\n\n注：一→表示向好、高、大发展的趋向，  \n\n表3-2-16中数据表明；除对漆膜柔韧性有负面影响外，其他方面均有向好的趋势。尽管如此，也并不是说羟基含量越高越好，羟基含量与聚合物分子量之间存在一定的相关关系，分子量较高，则羟基含量可以稍低一些，反之则应稍高一些，应以确保每个大分子上的官能度不少于2～5的水平为宜。一般羟基含量的大致范围为1%～6%（基于树脂不挥发分)。用于丙烯酸-聚氨酯类树脂的分子量及玻璃化温度的设计一般比高温烤漆高，故羟基含量可取下限值。过高的羟基含量不仅需要增加固化剂的用量，而且会在一定程度上影响到漆膜的其他方面的性能，如表干及实干时间、耐极性介质性能等。而丙烯酸-氨基烤漆系统则根据产品性能的特殊需要可取上限值。还需要特别强调的是，罩光清漆用树脂的羟基含量较高，而一般本色漆（即普通瓷漆）树脂的羟基含量中等，最低的则是底色漆与本色底色漆用树脂。一般而言，用于丙烯酸-氨基烤漆的丙烯酸树脂中的羟基单体多为含仲羟基的丙烯酸羟丙酯（HPA)、甲基丙烯酸羟丙酯（HPMA）等，否则将无法保证所配制漆料的贮存稳定性。  \n\n②含羟丁基的丙烯酸树脂如前所述，常见热固性丙烯酸树脂合成中均采用丙烯酸羟丙酯(或甲基丙烯酸羟丙酯)。采用这类丙烯酸单体时，人们发现：随着羟基含量的增加，漆膜的一般物性均可得到改善，但柔韧性却会变差。漆膜柔韧性之所以逐渐变差的关键在于树脂大分子侧链上的羟基仅仅通过两个碳原子与主链相连（丙烯酸羟丙酯)，这样形成的交联键刚性有余而柔韧性欠缺。为提高羟基与大分子主链相连接的碳链的柔顺性，曾有人尝试过采用丙烯酸（或甲基丙烯酸）羟丁酯来替代羟丙酯的方案，即将酯基碳链的碳原子数由2个增至4个。将羟基单元由原来的含羟乙基、羟丙基改为羟丁基，可在一定程度上缓解硬度与柔韧性之间的矛盾。在丙烯酸聚合物的主链上引人羟丁基的方法比较简单，只需将原来采用的丙烯酸羟丙酯（或羟乙酯）在不变动羟基含量的基础上改为羟丁酯即可。具体参考配方及工艺如下。  \n\nSolvesso 150\\* (—) 36.68 甲基丙烯酸羟丁酯 8.85   \n乙丙烯酸丁酯 35. 67 过繁化 2-乙基已酸叔丁脂 1. 00   \n甲基丙烯酸羟丙酯 5.67 Solvesso 150\\* (二) 3.40  \n\n$\\textcircled{2}$ 工艺  \n\na.将Solvesso150#（--）加入反应釜中，通Nz升温至140℃。b.将苯乙烯、甲基丙烯酸丁酯、甲基苯烯酸羟丙酯、甲基丙烯酸羟丁酯、丙烯酸以及过氧化2-乙基已酸叔丁酯、Solvesso150\\*分别混合均匀然后分别加入到两个高位槽中。  \n\nc.同时滴加两种混合物，滴加时间分别为4h和5h。  \n\nd.滴加完成后，继续保温 $^{2\\mathrm{h}}$ e.降温、出料。  \n\n$\\textcircled{3}$ 指标  \n\n不挥发分/%  \n酸值/（mg KOH/g)  \n黏度/mPa• s  \n\n羟基单元采用（甲基）丙烯酸羟丁酯合成的热固性丙烯酸树脂制得的漆膜虽然柔韧性得到一些改善，但其改善程度仍然有限。比较有效的技术路线是在丙烯酸类聚合物大分子主链上引人e-己内酯或叔碳酸缩水甘油酯。  \n\ne-己内酯的引人可使原来仅通过两个碳原子连接到聚合物主链上的羟基变为通过己内酯与之连接，实验数据表明，漆膜的柔韧性可得到大幅提升。将e-已内酯引入丙烯酸类树脂可使其具有非常良好的柔韧性和较高的交联反应活性。因为己内酯与其他羟基进行酯交换反应，开环后生成的羟基为具有较高活性的伯羟基，另外己内酯的引人使得丙烯酸类聚合物主链上含羟基的侧链加长，增加了交联键的柔顺性。因此含己内酯的丙烯酸类树脂不仅可以做到高不挥发分、低黏度，而且还成功解决了漆膜刚性和柔韧性的矛盾。  \n\ne-己内酯引入丙烯酸类树脂的技术路线有如下两条。  \n\n$\\Phi$ e-己内酯与含羟基丙烯酸类单体开环反应e-己内酯与甲基丙烯酸羟乙酯或丙酯进行酯交换开环反应得到一种新的含羟基丙烯酸类单体。因己内酯相互间可以发生酯化反应，故其酯交换物可以含一个亦可含几个己酰氧基单元，加成反应式如下。  \n\n式中，R为乙基或丙基；n为1、2、3  \n\n目前这类新型单体已经有商品出售，如道化学公司的TONETMM-10O与TONETMM-201，它们分别是甲基丙烯酸羟乙酯与e-已内酯 $1:2$ 和 $1:1$ 的加成物。这两种新型单体与其他丙烯酸类单体共聚制得的丙烯酸树脂不仅可使成膜后的漆膜兼顾刚性和柔韧性，而且树脂的黏度也较低，现举一个实例供参考。  \n\na.配方（质量份）  \n\n甲基丙烯酸羟乙酯  \n\nc-己内酯  \n\n注：Cat2005为一种主要成分二丁基氧化锡的催化剂。  \n\nb.工艺将配方量的物料全部投入到三口瓶中，在 $\\Nu_{2}$ 保护下升温至 $140^{\\circ}\\mathrm{C}$ ，保温3h即得相当于TONETMM-201的产品。把这种新型含羟基丙烯酸酯类单体作为羟基单元，按常法与其他丙烯酸类单体共聚即可得相应的已内酯改性丙烯酸类树脂。  \n\n$\\textcircled{2}$ 利用丙烯酸类聚合物上的羟基与e-己内酯进行酯交换开环反应其基本反应式如下。  \n\n利用丙烯酸类聚合物上的羟基与e-己内酯进行酯交换开环反应的技术路线又可细分为先聚合后开环以及聚合反应与开环反应同时进行的两种方法。其中聚合反应与开环反应同时进行的技术路线已经实现工业化生产，现举一个合成范例以供参考。  \n\na.配方（质量份）  \n\n<html><body><table><tr><td>己内醋</td><td>29.16</td><td>丙烯酸</td><td>0.22</td></tr><tr><td>100*溶剂(一)</td><td>10.00</td><td>过氧化苯甲酸叔戊酯（一)</td><td>3.23</td></tr><tr><td>酸酸甲氧基丙酯（--)</td><td>8.00</td><td>醋酸甲氧基丙酯（二）</td><td>2.92</td></tr><tr><td>Cat 2005</td><td>0.03</td><td>100*溶剂（二)</td><td>0.80</td></tr><tr><td>甲基丙烯酸-2-乙基已酯</td><td>17.12</td><td>过氧化苯甲酸叔戊酯（二）</td><td>0.10</td></tr><tr><td>甲基丙烯酸甲酯</td><td>12. 11</td><td>100°溶剂（三）</td><td>0.58</td></tr><tr><td>丙烯酸-2-乙基已酯</td><td>2.46</td><td>100*溶剂(四)</td><td>0.50</td></tr><tr><td>丙烯酸羟乙酯</td><td>10.93</td><td>醋酸甲氧基丙酯（三）</td><td>1.00</td></tr></table></body></html>  \n\nb.工艺  \n\n·反应釜充分清洁、干燥，然后通 ${\\bf N}_{2}$ @  \n\n·将己内酯、 $100^{*}$ 溶剂（一）、醋酸甲氧基丙酯（一）、Cat2005加人到反应釜中，揽半下在2h内升温至 $160^{\\circ}\\mathrm{C}$ @  \n\n·将甲基丙烯酸-2-乙基己酯、甲基丙烯酸甲酯、丙烯酸-2-乙基己酯、丙烯酸羟乙酯、丙烯酸加入到单体高位槽中，混合均匀。  \n\n·将过氧化苯甲酸叔戊酯（一）和醋酸甲氧基丙酯（二）加人到催化剂高位槽中，混合均匀。  \n\n·同时滴加单体混合物和催化剂，分别耗时4h和4.5h。  \n\n·所有材料加完后，升温至回流。  \n\n·用 $100^{\\sharp}$ 溶剂（二）清洗单体高位槽和管道。  \n\n·加入过氧化苯甲酸叔戊酯（二）和 $100^{\\sharp}$ 溶剂（三）混合溶液，耗时 $10\\mathrm{min}$ 费·然后用 $100^{*}$ 溶剂（四）清洗催化剂高位槽和管道。  \n\n· $155^{\\circ}\\mathrm{C}$ 下保温5h，然后加人醋酸甲氧基丙酯（三）。  \n\n·抽样检验，用甲基戊基酮调整不挥发分。  \n\n·降温至 $80\\sim90^{\\circ}C$ ，过滤、包装。  \n\nc.技术指标  \n\n<html><body><table><tr><td>黏度（25℃，加氏管）</td><td>U~W</td><td>羟值mgKOH/g</td><td>75~80</td></tr><tr><td>酸值/(mg KOH/g)</td><td>5~7</td><td>不挥发分/%</td><td>73~75</td></tr><tr><td>颜色（Fe-Co）/</td><td>1*</td><td></td><td></td></tr></table></body></html>  \n\n从上述指标中可看到：采用了己内酯的丙烯酸类树脂不仅不挥发分高，而且其加氏黏度仅为 $\\mathbf{U}{\\sim}\\mathbf{w}$ ，为一种典型的高不挥发分、低黏度丙烯酸类树脂。采用该树脂配制的清漆不仅平整光滑，光泽、鲜映性优异，而且具有良好的物理力学性能。 2  \n\n将叔碳酸缩水甘油酯（E-10）引入丙烯酸类树脂以形成新的、通过长的侧链连接到主链上的羟基也是一条比较成功的技术路线，该单体具体的化学名为1，1-二甲基-1-已基乙酸缩水甘油酯，俗称叔碳酸缩水甘油酯，其化学结构式如下。 1  \n\n![](images/30e1dcf1b27a7a7e74349eab64d0a7bf529ad6dee18d532260aef05013bb1c20.jpg)  \n\nCarduraE-10引入的方式是利用丙烯酸共聚物分子上的羧基与E-10分子上的环氧基发生开环反应，在与丙烯酸共聚物大分子连接的同时释放出新的羟基。CarduraE-10的引人，增加了树脂在有机溶剂中的溶解性，降低了体系的黏度，同时对最终漆膜的物性也有一定程度的改善。总体来说，E-10的引人可为丙烯酸类树脂带来如下特点。  \n\na.由于E-10带有一个支链烷基基团，因其空间位阻效应，使该丙烯酸类树脂的耐极性介质性能得到相当大的改善。  \n\nb.E-10的引入使丙烯酸树脂具有双极性机构单元。其中支链烷基部分带来与其他烷烃良好的相容性，而甘油酯和羟基部分则为树脂带来较高的极性，使之比较容易与其他极性分子形成氢键，这就使树脂同时具备了与涂料系统中极性和非极性组分相容的能力。这样就不难理解E-10给树脂带来的一系列特点，如黏度的降低、对颜料以及基材润湿性的提高、漆膜良好的光泽等。  \n\n以叔碳酸缩水甘油酯改性丙烯酸类树脂的技术路线与上述己内酯的大体相似，也有以下两种途径。  \n\na.先与丙烯酸（或甲基丙烯酸）进行开环反应得到一种新型单体，再与其他丙烯酸类单体共聚。  \n\n叔碳酸缩水甘油酯分子中的环氧基反应性与其他环氧化合物类似，在有机麟、锡等催化剂和阻聚剂存在下与丙烯酸（或甲基丙烯酸）进行开环加成反应，其基本反应方程式如下。  \n\n![](images/87138134c548cb6de909e4aaee3d92fff2b6070f2c2cd4b92831d60f101ad1ef.jpg)  \n\n从上述反应方程式中可以看到：E-10与丙烯酸（或甲基丙烯酸）的开环加成反应生成了含伯羟基和含仲羟基的两种化合物。显而易见，这两种单体与其他丙烯酸类单体共聚生成的树脂既可用于低温固化的丙烯酸-聚氨酯，亦可用于丙烯酸-氨基高温烘烤型涂料系统中。唯一的担心是它的伯羟基是否会导致这种丙烯酸-氨基涂料的贮存稳定性。然而有关实验数据表明：只要氨基树脂选配得当，一般没有上述所担心的问题发生。这主要是因为环氧化合物与羧酸的酯化反应主要生成含仲羟基的化合物，而伯羟基的含量相对较少。另外，也是由于空间位阻效应的作用，这里的伯羟基比常用的丙烯酸（或甲基丙烯酸）羟乙酯羟基的活性低。  \n\n在确定E-10与丙烯酸的酯化加成反应条件时应该留意到一些可能发生的副反应，如羧基与生成的羟基发生酯化反应以及环氧基与羟基间的醚化反应等。为了尽可能降低副反应发生的概率，以较低的酯化温度为宜。  \n\nb.先合成一种高酸价的丙烯酸类聚合物，然后再与E-10进行开环反应。  \n\n此种工艺又可分为“先聚合后酯化”和“聚合与酯化同时进行”两种。两种工艺各有优劣，先聚合后酯化法可使两步反应本身相对简单，副反应较少，但中间控制繁杂，反应周期较长。聚合与酯化同时进行的方法可大大缩短反应周期，但两类反应同时进行，必然导致复杂的副反应增多，造成树脂质量的波动。但如果能够认真权衡影响树脂的配方的各种因素，严格工艺纪律，是可以获得理想的结果的。采用聚合与酯化同时进行的工艺需要注意如下几方面问题。  \n\n·选择合适的引发剂，最好采用叔戊基、叔丁基过氧化物。  \n\n·高不挥发分、低黏度丙烯酸树脂中惯用的良溶剂酮类，因可能和E-10之间发生副反应，故在反应前期不得加入到聚合反应系统中，建议作为兑稀溶剂使用。  \n\n·添加合适的酯化催化剂，如有机麟、亚锡等化合物。  \n\n这里附带要提请注意的是，在合成高不挥发分丙烯酸类树脂时，有时要用到一些带活性基团的链转移剂，使分子量分布趋窄，如硫基乙醇、硫基丙酸、硫基月桂酸等硫基类化合物。这些硫基类化合物虽然可使聚合物的分子量分布趋窄、黏度下降，但遗憾的是这类化合物有一种令人不愉快的气味，即使用量非常少也在所难免。如果在引入E-10 的聚合反应中，采用硫基羧酸为链转移剂则可避免上述不足。因为E-10可以和硫基羧酸中的羧基反应，使不愉快的气味从产品中消失。上述实例中就采用了硫基丙酸作为链转移剂，其结果不仅黏度较低，而且闻不到通常的硫基化合物的气味。  \n\n(2）醇酸树脂可用于汽车原厂本色漆的醇酸树脂多为短油醇酸树脂。制造这类树脂时采用的一元酸、多元酸、多元醇等考虑的原则如下。  \n\n$\\Phi$ -元酸因考虑耐候方面的因素，所采用的脂肪酸一般为碘值较低的植物油脂肪酸（如豆油酸、棕榈油酸、椰子油酸、月桂酸等）或合成脂肪酸（如 $C_{9}$ 酸、 $\\mathbf{C}_{10}$ 酸、 $\\mathbf{C}_{12}$ 酸等)。卡车、轻卡、农用车等大众车辆多采用短油醇酸树脂，而高档轿车用漆，则多采用合成脂肪酸改性醇酸树脂或聚酯树脂。  \n\n$\\textcircled{2}$ 多元酸仍然以苯二甲酸酐为主，极少采用理论上耐老化性能较好的四氢苯酐、间苯二甲酸等。另外，顺丁烯二酸酐可以有效降低树脂颜色、提高产品黏度，但因其耐老化性能较差，故不建议采用这类含不饱和双键的多元酸。  \n\n$\\textcircled{3}$ 多元醇由于至今汽车面漆都采用三聚氰胺甲醛树脂为交联剂，故不建议采用含伯羟基的多元醇，如三羟甲基丙烷、季戊四醇等，最好采用甘油之类。当然，如果与汽车总装厂互有约定，如涂料到厂后，贮存期不得超过3个月等。乙二醇、二乙二醇、丙二醇等也常被用于醇酸树脂合成中，这类二元醇均可为树脂带来较好的柔韧性，但采用乙二醇类作为多元醇单元的树脂的耐水性稍差。  \n\n现分别列举用于卡车漆及高级轿车漆用醇酸树脂合成的范例供参考。  \n\n$\\Phi$ 卡车漆用棕榈油醇酸树脂",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1049,
+        "chunk": "# a.配方（质量份）  \n\n棕榈油 22.70 回流二甲苯 6.00   \n甘油（含量≥96%) 14.25 苯二甲酸酐 25.00   \nLiOH 0. 04 兑稀二甲苯 32.41  \n\nb.工艺  \n\n·将棕榈油和甘油投入到反应釜中，在 ${\\bf N}_{2}$ 保护下升温至 $150^{\\circ}\\mathrm{C}$  \n\n·将LiOH（预先将其与部分棕榈油混合成浆状物）加人到反应釜中，升温至 $230^{\\circ}\\mathrm{C}$ 呆温至 $1:5$ 清 (甲醇)。  \n\n·降温至 $150\\Upsilon$ ，加入回流二甲苯和苯二甲酸酐，升温至 $180^{\\circ}\\mathrm{C}$ ，回流至AV约为30。  \n\n·继续升温至 $200^{\\circ}\\mathrm{C}$ ，保温至 $\\mathbf{A}\\mathbf{V}{\\leqslant}15$ ，黏度为 $15\\sim20{\\mathrm{s}}$ 。  \n\n·降温，加入兑稀二甲苯，过滤、出料。  \n\nc.技术指标  \n\n颜色（Fe-Co) ≤10\\* 不挥发分/%黏度（25℃，格氏管）/s 15\\~20  \n\n55±2",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1050,
+        "chunk": "# $\\textcircled{2}\\mathsf{C}_{9}$ 脂肪酸醇酸树脂  \n\na.配方 (质量份）  \n\n<html><body><table><tr><td>异壬酸</td><td>24.08</td><td>二甲苯（-)</td><td>14.32</td></tr><tr><td>三羟甲基丙烷</td><td>18.11</td><td>二甲苯(二)</td><td>0.80</td></tr><tr><td>季戊四醇</td><td>6.60</td><td>丙二醇丁醚</td><td>5.67</td></tr><tr><td>苯酐</td><td>22.69</td><td>二甲苯(三)</td><td>10.85</td></tr><tr><td>亚麟酸三苯酯</td><td>0. 11</td><td>二甲苯(四)</td><td>6.62</td></tr><tr><td>二丁基氧化锡</td><td>0.41</td><td>二甲苯（五）</td><td>3.00</td></tr></table></body></html>  \n\nb.工艺  \n\n·反应釜应清洁、干燥，在分水器中加满回流溶剂，通 ${\\bf N}_{2}$ @  \n\n·按顺序加人异壬酸、三羟甲基丙烷、季戊四醇、苯酐、亚麟酸三苯酯、二丁基氧化锡（注：亚麟酸三苯酯和二丁基氧化锡需称量精确)，关闭反应釜，最后加人二甲苯（一）。  \n\n·在 ${\\bf N}_{2}$ 保护下升温至 $200\\Upsilon$ ，当釜内温度达到 $100^{\\circ}\\mathrm{C}$ 时，停通 ${\\bf N}_{2}$ ，关闭部分热媒油管，此时有放热反应发生，故釜内温度上升到 $135\\mathrm{^{\\circ}C}$ 垂  \n\n·再次开启热媒油管，继续升温至回流、脱水。  \n\n·待出水量达到总投料量的 $5.5\\%$ 时，加入二甲苯(二)，继续回流至黏度 $\\mathbf{\\Delta}=\\mathbf{V}\\sim\\mathbf{W}$ $\\scriptstyle\\mathbf{A}\\mathbf{V}=5\\sim7$ 。  \n\n取样配比如下。  \n\n样品 50.0 二甲苯 丙二醇丁醚 15.0  \n\n·当抽样合格后，停加热，加人丙二醇丁醚，搅拌均匀后，将物料转移至加有二甲苯（四）的兑稀釜中。  \n\n·反应釜用二甲苯（五）清洗，放人兑稀釜。  \n\n·降温至 $80^{\\circ}\\mathrm{C}$ 左右，过滤、包装。  \n\nc.技术指标  \n\n外观 黄色黏稠液体 AV/(mgKOH/g) 4\\~8  \n不挥发分/% 70±1 颜色（Fe-Co) ≤3  \n黏度（加氏管，23℃） V\\~X 羟值/(mgKOH/g) 140\\~170",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1051,
+        "chunk": "# 2.交联剂  \n\n(1）氨基树脂汽车行业的丙烯酸-氨基烘烤型涂料中使用的氨基树脂主要有丁醇醚化三聚氰胺甲醛树脂、异丁醇醚化三聚氰胺甲醛树脂、甲醇醚化三聚氰胺甲醛树脂以及丁醇和甲醇混合醚化三聚氰胺甲醛树脂等几种类型。至于烃基三聚氰胺甲醛树脂、脲醛树脂等在汽车涂料中不太常用。主要因为前者的性能虽好，但价格昂贵；后者的耐候性较差，仅仅在一些较低档的普通工业涂料中采用。  \n\n丁醇醚化三聚氰胺甲醛树脂因原料配比、制造工艺等方面的差别，氨基树脂分子中的羟甲基数、丁氧基数和亚甲基数不同，性能也各不相同。丁氧基数量越多，则醚化度越高，与其他树脂的混容性也越好，反之则越不好。所以氨基树脂又可分为高醚化度和低醚化度两大类。高醚化度氨基树脂的容忍度大于 $1:10$ （样品： $200^{\\#}$ 溶剂油），低醚化度氨基树脂的容忍度范围为 $1:(3\\sim5)$ 。在合成氨基树脂时，因三聚氰胺、甲醛、脂肪醇等物料不同的配比、催化剂的类型及用量以及其他工艺参数等决定了自缩聚反应以及醚化的程度，也决定了产品的分子量及其分布。氨基树脂的关键参数为；不挥发分含量、黏度、容忍度、颜色等。  \n\n甲醇醚化三聚氰胺甲醛树脂具有低黏度、高交联反应活性、优良的混容性、漆膜丰满光亮、柔韧性好等特点，广泛用于水溶性涂料以及高不挥发分、低黏度的涂料中。这类氨基树脂以六甲氧基三聚氰胺甲醛树脂为典型代表，它们与丁醇改性的氨基树脂比较，主要异同点见表3-2-17。  \n\n表3-2-17甲醇醚化与丁醇醚化的三聚氰胺甲醛树脂性能比较  \n\n\n<html><body><table><tr><td>性能</td><td>甲醇醚化</td><td>丁醇醚化</td></tr><tr><td>结构</td><td>基本上是一个三嗪环</td><td>可能有自缩聚物，即多个三嗪环</td></tr><tr><td>交联反应速率</td><td>慢、需添加催化剂</td><td>较快</td></tr><tr><td>漆膜力学性能</td><td>柔韧性与硬度可以兼得</td><td>难以解决柔韧性与硬度的矛盾</td></tr><tr><td>使用量</td><td>相对较低</td><td>相对较高</td></tr></table></body></html>  \n\n如表3-2-17所述，甲醇醚化与丁醇醚化的三聚氰胺甲醛树脂各有所长，于是人们开始构思如何把这两类氨基树脂的特长集合在一起的技术路线，那就是丁醇和甲醇混合醚化的三聚氰胺甲醛树脂。这类氨基树脂综合了这两种脂肪醇单独醚化的特点，而又有所折中。国内各树脂生产厂家大都没有该类型的产品，而主要见诸于进口品牌系列中。因混合醚化势必增加生产工艺的难度，故此类树脂的使用范围并不太广，而仅限于汽车原厂漆之类高档烤漆的领域。有人认为混合醚化的三聚氰胺甲醛树脂作交联剂时，对复合涂层的层间附着力有好处，对此似乎从理论上很难进行解释。估计可能是底涂层“欠熟”，或者说“固化不充分”造成的误解。混合醚化三聚氰胺甲醛树脂衍生物：分子量及羟甲基含量较高，可提供较好的固化性能，特别是抗污染物的迁移性(有人将其称为“打电报\")。  \n\n![](images/3aa5cb3618096930786478c4ce08989215b1f51b2278126d9eaffd0a059ff0de.jpg)  \n\n鉴于混合醚化三聚氰胺甲醛树脂有如此多的优越，有人提出了一个简化的建议，即在配方中同时选用两种醇醚化的三聚氰胺甲醛树脂可大体获得采用混合醚化物类似的效果，这样就可以回避混合醚化时制造工艺复杂的问题。事实上已有一些制漆厂在其高档氨基烤漆配方中采用了类似配合。  \n\n(2）封闭型异氰酸酯由于环境污染现象的日益严重，酸雨对汽车表面涂层的影响也越来越受到有关方面的高度重视。这主要是因为酸性介质对面漆的侵蚀直接导致了涂层失光、变色，使汽车，特别是高级轿车失去原有华丽的外观，这是大多数车主所极不愿意见到的现象。因此，各种耐酸性介质性能突出的汽车面漆应运而生。如前所述；汽车面漆常用的氨基烤漆最大的病就在于采用三聚氰胺甲醛树脂作交联剂。因为这类交联剂在与主成膜物质（丙烯酸树脂或醇酸树脂）的羟基发生交联反应时常常产生对酸性水解非常敏感的“醚键”。这就是各类氨基烤漆不耐酸雨的祸根。封闭型异氰酸酯类固化剂替代氨基树脂用于丙烯酸类或醇酸树脂类烤漆中是近年来涂料行业的较新成果。在烤漆中采用这类固化剂除可以得到综合性能非常突出的性能外，最重要的是突出的耐水性可以获得较大程度的改善。  \n\n用于制备封闭型异氰酸酯类固化剂只能采用脂肪族、脂环族等户外性能优异的异氰酸酯类，如六亚甲基二异氰酸酯（HDI)、异佛尔酮二异氰酸酯（IPDI）等。IPDI是一种脂环族多异氰酸酯类化合物，其—NCO基团的反应活性比芳香族异氰酸酯的低，蒸气压也低。IP-DI分子中2个—NCO基团的反应活性不同，因为IPDI分子中伯—NCO受到环已烷环和α-取代甲基的位阻作用，使得连在环已烷上的仲—NCO基团的反应活性比伯—NCO的高$1.3{\\sim}2.5$ 倍；IPDI与羟基的反应速率比HDI与羟基的反应速率快 $4{\\sim}5$ 倍。  \n\n可用作封闭剂的化合物则较多，见表3-2-18。  \n\n上述各种化合物均可用作异氰酸酯类—NCO基团的封闭剂，其中适合用作汽车原厂烤漆的封闭剂却不太多。从表3-2-19中列出的各种封闭剂解封的温度就可以看出：只有那些解封温度在 $120{\\sim}160^{\\circ}\\mathrm{C}$ 的封闭剂才可能用于汽车原厂漆中。  \n\n表3-2-18常见封闭剂及其特点  \n\n\n<html><body><table><tr><td>封闭剂类别</td><td>典型化合物</td><td>特 点</td></tr><tr><td>酚类</td><td>酸苯酚、甲酚、二甲酚、硝基苯酯、叔丁</td><td>常见，解封温度较醇类低</td></tr><tr><td>醇类</td><td>丁醇、乙基己醇、乙二醇单丁醚、丙 二醇单乙醚等</td><td>解封温度较高，热稳定性好</td></tr><tr><td>类</td><td>甲乙酮、环己酮肪、丙酮厉等</td><td>特别适合脂肪族或脂环族异氰酸酯类的封闭，解封温 度低</td></tr><tr><td>酰胺、酰亚胺类</td><td>乙酰苯胺、N-甲基乙酰胺、己内酰 胺、环丁基酰亚胺等</td><td>可形成六元环的中间体，解封温度较低</td></tr><tr><td>咪唑类</td><td>2-甲基咪唑、2-甲基4-乙基咪唑等</td><td>可形成五元环的中间体，解封温度较低</td></tr><tr><td>吡唑和三唑类</td><td>3.5-二甲基吡唑、1,2,4-三唑等</td><td>可形成五元环的中间体，解封温度较低</td></tr><tr><td>仲胺类</td><td>2,2,6,6-四甲基院、4-（二甲氨 基）-2,2,6,6-四甲基啶等</td><td>可形成二聚体</td></tr><tr><td>活性亚甲基化合物</td><td>环二脲等</td><td>可形成二聚体</td></tr></table></body></html>  \n\n表3-2-19常见封闭剂的解封温度  \n\n\n<html><body><table><tr><td rowspan=\"2\">封闭剂</td><td colspan=\"2\">解封温度/C</td><td rowspan=\"2\">封闭剂</td><td colspan=\"2\">解封温度/℃C</td></tr><tr><td>无催化剂</td><td>有催化剂存在</td><td>无催化剂</td><td>有催化剂存在</td></tr><tr><td>乙醇</td><td>180~185</td><td>150~155</td><td>丙酮</td><td>130~150</td><td></td></tr><tr><td>苯酚</td><td>140~145</td><td>105~110</td><td>甲乙酮肪</td><td>130~135</td><td>125~130</td></tr><tr><td>己内酰胺</td><td>160</td><td></td><td>乙酰丙酮</td><td>140~150</td><td></td></tr><tr><td>丙二酸二乙酯</td><td>130~140</td><td></td><td>咪唑</td><td>130~140</td><td></td></tr><tr><td>乙酰乙酸乙酯</td><td>125~150</td><td>125~130</td><td></td><td></td><td></td></tr></table></body></html>  \n\n相对三聚氰胺甲醛树脂类交联剂而言，封闭型异氰酸酯类交联剂的成熟商品所见不多，这主要是因为各类封闭型异氰酸酯类的解封温度不同，适用范围受限的缘故。拜耳公司的Desmodur AP 为一种解封温度在 $160^{\\circ}\\mathrm{C}$ 以上的酚封闭芳香族异氰酸酯，DesmodurBL1100、1190、1265亦为封闭芳香族异氰酸酯，其解封温度为 $140^{\\circ}\\mathrm{C}$ 以上。Desmodur BL 3175、4165则属于封闭型脂肪族异氰酸酯类。众所周知，脂肪族异氰酸酯类具有良好的耐黄变性能，这样它就可作为交联剂用于汽车面漆之中。虽然3175的解封温度高达 $160^{\\circ}\\mathrm{C}$ 以上，但在促进剂（如月桂酸二丁基锡）存在的前提下，可使烘烤温度低至 $130\\sim140^{\\circ}\\mathrm{C}$ ，完全适应多数汽车总装厂面漆、中间涂料涂装线的工艺参数。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1052,
+        "chunk": "# 3.助剂  \n\n(1）流变助剂液体的流变性与流动性是不一样的。所谓流变性主要反映液体经受高剪切速率和低剪切速率时不同的流动性能。流变助剂是一类能够改变涂料流变性能的新型涂料添加剂。在国外，一些高档汽车原厂漆，特别是轿车用漆大都广泛使用了某种类型的流变助剂。这类助剂的使用可以在一定程度上赋予涂料在高剪切应力的作用下，表观黏度较低，而在低剪切应力的作用下，表观黏度较高的特性。这样，涂料在贮存、运输的过程中就不会产生因涂料系统黏度偏低而产生的诸如沉降、分层、乃至结块之类的病，大大提高了涂料的贮存稳定性。在施工时，由于涂料在喷枪口附近经受到的是高剪切应力，故其表观黏度非常低，涂料特别容易被雾化。而漆雾一旦凝聚在基材表面成膜时，所受到的压缩空气的外力消失，此时工件表面即使是处于垂直状态，涂料自身所受到的外力至多也只是因自身重力而带来的低剪切应力，其表观黏度会变得很高，故不易发生流挂等现象。加有合适流变助剂的涂料必然有着良好的施工工艺性能，一次成膜厚度较大，所得漆膜的外观也必然平整光滑。  \n\n我国台湾德隆公司的275就是属于一种防沉降、防流挂助剂。该助剂的添加量为0.2%～1.0%（总投料量)，无论在颜料研磨前后添加均可。赫斯公司的Ser-ADBEZ75，毕克化学公司的Anti-Terra-203、Anti-Terra-204也都是一类专用于防沉和抗流挂的助剂。  \n\n从某种意义上来说，增稠剂也可纳入流变助剂的范畴。因为不少增稠剂在一定程度上不仅可起防沉作用，而且也能抗流挂。涂料行业中一直都在采用的有机膨润土就是其中一例。美国NL公司、Grace公司等均有不同型号的有机膨润土打入我国涂料助剂市场，其中Ben-tone 27、Bentone SD-2、Bentone SD-3等均可用于丙烯酸-氨基或醇酸-氨基烤漆中。  \n\nSCA改性树脂则是另一类能够改变涂料流变性能的树脂，此方面最为突出的生产厂家为AKZONobel公司。该公司向市场推出他们将其称之为SCA改性树脂。SCA为流挂控制剂（sagcontrolcoagent）的英语缩写。这类树脂进入市场后，首先在汽车原厂漆领域内获得成功。不少汽车原厂漆生产厂家，包括BASF、PPG、HERBERTS等均采用了该公司的这类产品。AKZO的这类SCA改性树脂多用于厚膜清漆和要求一次成膜厚度较大的瓷漆中(表3-2-20)。  \n\n表3-2-20 AKZONobel SCA改性树脂  \n\n\n<html><body><table><tr><td>牌号</td><td>树脂类型</td><td>不挥发分/%</td><td>黏度（23℃）/Pa·s</td></tr><tr><td>Setal 90173 SS-50</td><td>饱和聚酯</td><td>49~52</td><td>8.0~28</td></tr><tr><td>Setal 90176 SS-60</td><td>饱和聚酯</td><td>59~62</td><td>3.0~7.5</td></tr><tr><td>Setal 91703 SS-53</td><td>饱和聚酯</td><td>50~53</td><td>1. 5~5. 0</td></tr><tr><td>Setalux C91756 SS-60</td><td>热固性丙烯酸</td><td>58~61</td><td>7.0~12</td></tr><tr><td>Setalux C91757 VX-60</td><td>热固性丙烯酸</td><td>58~61</td><td>5.0~12</td></tr><tr><td>Setalux C91795 VX-60</td><td>热固性丙烯酸</td><td>59~62</td><td>1. 5~ 3. 5</td></tr><tr><td>Setalux XL 1029</td><td>热固性丙烯酸</td><td>58~62</td><td>1. 0~5.0</td></tr></table></body></html>  \n\n树脂的选择原则是以漆料系统中主成膜物质的类型而异，如在丙烯酸涂料系统中最好选择Setalux系列丙烯酸类SCA改性树脂，而在聚酯树脂系统中则最好选择Setal系列的聚酯树脂。  \n\n如其他类型助剂使用时采用复配的手法一样，为进一步提高其对涂料流变性能影响的力度，流挂助剂也讲究搭配使用。如有的资料介绍，上述助剂如和有机膨润土拼用，可起到增效作用，而对漆膜的其他物性则几乎没有影响。  \n\n(2）紫外光吸收剂所谓紫外光吸收剂是指那些能够吸收紫外光，并将其所吸收的能量转化为无害能量的一类化合物。具有这种特性的化合物很多，如二苯甲酮类、水杨酸酯类、某些杂环类、取代丙烯睛类以及某些金属络合物等。能够提高聚合物材料光稳定性能的助剂有光屏蔽剂、抗氧剂、紫外光吸收剂、自由基捕获剂以及能分解过氧化氢的化合物等。因此将其简化统括为“光稳定剂”更能反映这类助剂的本质。一般情况下，以采用紫外光吸收剂为主，然后辅以其他类型的光稳定剂。  \n\n在各种汽车漆，特别是罩光清漆中加入紫外光吸收剂旨在进一步提高其耐候性，特别是保光、保色性能。太阳光中，波长为 $200\\sim411~\\mathrm{nm}$ 的光波辐射能最强，破坏力也最大。它能够促进聚合物大分子链节自动氧化过程的进行，从宏观的角度来看，也就是加速漆膜的降解。某些紫外光吸收剂能够有效地吸收这一波长范围内的光辐射能，然后将其转化为其他无害能量，从而有效地延缓了上述降解过程，实际上起到了抗老化作用。如二苯甲酮类化合物能够通过整合氢键的形成，使一定波长的紫外光能转化为热能，从而消除或减弱了紫外光辐射能对漆膜的破坏作用。不少二苯甲酮类的衍生物已经形成商品在市面上流通。除此而外，苯并三唑类杂环化合物也有不少用作紫外光吸收剂，如羟基苯并三唑类等。作为一种理想的  \n\n涂料用紫外光吸收剂必须具备以下特性：  \n\n①对于涂料的其他物理力学性能无任何不良影响；  \n$\\textcircled{2}$ 与主成膜物质的混容性良好；  \n$\\textcircled{3}$ 挥发性小，不容易被水、溶剂萃取，同时也无迁移特性；  \n$\\textcircled{4}$ 对光、热稳定性良好，无色、无味、低毒；  \n$\\textcircled{5}$ 价格适当。  \n\n紫外光吸收剂的品种很多，不同的紫外光吸收剂对紫外光敏感的波长范围不都一样，例如：二苯甲酮类在波长230～390nm范围内有较强的吸收；苯并三唑类则在300～385nm范围内有较强吸收；丙烯睛衍生物在 $310\\sim320\\mathrm{nm}$ 范围内有较强吸收；而芳香族酯类化合物则对 $340\\mathrm{nm}$ 以下的短波紫外光比较敏感。而作为涂料成膜物质的聚合物，它的品种不同，其大分子链节对于不同波段的紫外光的敏感程度也不一样。因此，必须根据涂料中所采用的聚合物的类型，选择几种紫外光吸收剂搭配使用，才有可能获得满意的效果。  \n\n为了延缓丙烯酸-氨基类涂料漆膜的老化过程，在生产实际中往往采用抗氧剂、紫外光吸收剂等拼用的办法。一个比较典型的例子就是采用紫外光吸收剂与自由基捕获剂拼用。受阻胺光稳定剂（HALS）是自由基捕获剂中的一种，它与等量的紫外光吸收剂混用可以获得比较明显的增效作用 (或者叫协和作用)。  \n\n（3）流平剂显而易见，汽车行业对于汽车涂层外观的要求是非常苛刻的。因此大多数汽车涂料制造厂商在产品定型时，都对其流变性能作过认真、仔细的考虑。已经比较圆满地解决了成膜厚度、流挂与流平之间的综合平衡。因此国外一些名牌汽车涂料制造厂家的产品，大都具有良好的施工性能。具体反映在一次成膜厚度能够达到汽车总装厂的要求，且不流挂，橘纹轻微，光泽和鲜映性也都很理想等。虽然这些厂家制漆的技术要领各不相同，但有一点则肯定一致，那就是选配适当的流平剂。  \n\n所谓流平剂是指那些能够改善涂料成膜时流动特性的物质。它的主要作用是降低涂料系统的表面张力，增加其在低剪切力下的流动性能，使漆膜达到平整光滑，无缩孔、凹陷、刷痕以及橘纹等表面缺陷的目的。可用作涂料流平剂的种类很多，如高沸点混合溶剂、有机硅化合物、有机氟化合物、某些丙烯酸系聚合物、丁醇改性三聚氰胺树脂、聚乙烯醇缩丁醛、醋酸丁酸纤维素等。  \n\n聚氨酯类涂料，特别是聚酯-聚氨酯类涂料，由于其体系自身的表面张力一般较高，尤其需要使用一些能够大大降低表面张力的流平剂，以消除橘纹、针孔、凹陷、缩边等表面缺陷。如聚醚-聚硅氧烷类、聚酯-聚硅氧烷类、含氟聚合物类等。国外流平剂的品牌很多，如德国毕克公司的BYK300、BYK301、BYK302、BYK306、BYK310、BYK323、BYK331、BYK333、BYK354、BYK358、BYK359、BYK390、TSB等；EFKA公司的EFKA3030、EFKA3031、EFKA3032、EFKA3033、EFKA3034、EFKA3035、EFKA3232、EF-KA3236、EFKA3239、EFKA3777、EFKA3778等。国内台湾德隆公司的411、433、435、455、466、HS-321等产品。其中毕克公司的BYK306、BYK307，EFKA公司的EF-KA3777、EFKA3778以及德隆公司的466等虽同属氟硅类型助剂，但它们对复合涂层的层间附着力无不良影响。  \n\n醋酸丁酸纤维素（CAB）是另外一大类聚氨酯涂料系统中用得较为普遍的流平剂。目前市场上进口产品较多，如伊士曼公司（EastmanCo.）的CAB381-0.1、CAB551-0.2、CAB551-0.01、CAB381-2；拜耳公司的CellitBP300等。  \n\n由于所有牌号的CAB产品均为固态粉末状物质，故一般应将其配制成 $10\\%\\sim20\\%$ 的溶液以方便使用。所采用的溶剂多为醋酸溶纤剂与二甲苯的混合溶液。这类流平剂的用量比上述流平剂的用量都要大一些，否则其流平效果不明显。通常其用量为 $1\\%\\sim5\\%$  \n\n汽车总装厂涂装车间空气质量再好也难免点等漆膜病的存在。因此，线上修补是涂装中无法避免的再加工过程。于是重涂时的层间附着力就成为面漆指标中非常重要的一项。众所周知，影响层间附着力的主要因素在多数情况下与漆料配方中流平剂的使用有关。一般来说硅系列流平剂对层间附着力的不良影响，但仍然有一些品种不会影响到重涂时的层间附着力。如BYK公司的BYK306、BYK307，EFKA公司的EFKA3777、EFKA3778，澳大利亚Kemperial公司的KC510、KC515以及台湾德隆公司的466等虽同属氟、硅类型助剂，但它们对复合涂层的层间附着力无不良影响。合理地选用流平剂是汽车面漆配方设计中非常重要的一环。  \n\n(4）润湿分散剂颜料在展色剂中的润湿、分散是色浆、色漆制造中异常关键的两个步骤。颜料分散的第一步就是以有机相替代吸附在颜料粒子表面的空气和水分，这一步谓之润湿。然后在高剪切力的作用下颜料的二次团粒结构解体，形成稳定的分散悬浮体，这一步谓之分散。为使这两个过程更加迅捷、有效，实际生产中都要添加一些助剂。传统观念中将适合这两个阶段使用的助剂分别称之为润湿剂和分散剂。同时具有润湿和分散作用的助剂则被称为润湿分散剂。  \n\n一般低分子量润湿分散剂更有利于润湿，而高分子量润湿分散剂则更有利于分散、稳定等。现代色漆制造中，有关润湿、分散的理论研究与实践告诉人们，润湿分散剂的高分子化将更为有利。高分子润湿分散剂具有如下特性：  \n\n$\\Phi$ 非常有效地抗絮凝；  \n\n$\\textcircled{2}$ 对有机和无机颜料均能适用；  \n\n$\\textcircled{3}$ 高分子量润湿分散剂与传统型助剂不同，不少是能够成膜的聚合物，润湿分散剂参与成膜后能赋予涂层耐水性和抗皂化性能，由此不仅不会给漆膜性能带来负面影响，而且往往还能提升原有漆膜的性能。  \n\n目前市面上采用较多的高分子量润湿分散剂主要有两大类；即含叔胺类颜料亲和基团的聚氨酯与丙烯酸聚合物。其中丙烯酸聚合物分子量可做得更大些。而聚氨酯型的降黏效果更好。市面上流行的一些润湿分散剂以高分子量聚合物居多。这不仅因为新的高分子量润湿分散剂能极好地发挥润湿、分散、稳定功能，而且有的高分子量润湿分散剂还能参与成膜。这就将人们平常担心的助剂对成品性能的影响降低到几乎可以忽略不计的地步。  \n\n在汽车原车漆中选择润湿分散剂时，除了涂料系统对这类助剂的一般要求外，还应留意它们对其耐候性、耐介质性能的影响。另外在高温烘烤条件下，有无失光、变色的倾向等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1053,
+        "chunk": "# 4.各类本色漆  \n\n本色漆所采用的树脂、交联剂以及助剂等配方成分因车型不同而有不同的要求。以我国为例；卡车、轻卡等采用一般短油醇酸-氨基；轿车面漆则多采用耐候性更为优越的聚酯-氨基或合成脂肪酸醇酸-氨基；豪华巴士等大型高级车辆则采用丙烯酸-聚氨酯、聚酯-聚氨酯双组分本色漆，现分述如下。  \n\n(1）卡车、轻卡车面漆我国卡车及轻卡用面漆多采用低不饱和度或合成脂肪酸改性短油醇酸树脂配制的氨基烤漆，这类醇酸树脂所采用的脂肪酸以豆油、棕榈油以及椰子油脂肪酸为主，油度大约为 $30\\%\\sim35\\%$ 。豆油醇酸-氨基烤漆的施工性能较好，但耐过烘性能较差。一旦涂装线日常运行时某些工艺参数发生改变（如线速减慢、炉温过高等)，则汽车面漆间将出现明显色差。棕榈油及椰子油醇酸-氨基烤漆的光泽、硬度较高，耐过烘性能突出，但其施工性能略逊于豆油醇酸。采用棕榈油醇酸树脂与普通三聚氰胺甲醛树脂搭配用于卡车  \n\n面漆效果非常不错，配方如下（质量份）。  \n\n\n<html><body><table><tr><td>棕榈油醇酸树脂（油度34%）</td><td>60.00</td><td>汉高Texaphor 963分散剂 0.10</td></tr><tr><td>丁醇醚化三聚氰胺甲醛树脂</td><td>20.00 BYK 306</td><td>0. 10</td></tr><tr><td>中铬黄</td><td>0.85 BYK 331</td><td>0.05</td></tr><tr><td>深色素炭黑</td><td>0.31 150*芳烃</td><td>3.92</td></tr><tr><td>津酸藏</td><td>0.67 二丙酮醇</td><td>2.00</td></tr><tr><td>杜邦902钛白</td><td>12.00</td><td></td></tr></table></body></html>  \n\n虽然所采用的棕榈油醇酸树脂的颜色较深（Fe-Co $10^{\\sharp}$ )，但采用上述配方制成的色漆却具有非常良好的耐过烘烤性能。  \n\n(2）轿车面漆轿车本色漆除应具有一般汽车面漆所应有的性能外，最为重要的是必须具有良好的外观和对各类涂装线的适应性能。一般所采用的主成膜物质多为的合成脂肪酸改性醇酸树脂或聚酯树脂，其特点是：不饱和度极低，故耐候性突出。除交联剂外，在本色漆配方中搭配适当的具有抗流挂功能的树脂也是不可或缺的要素之一，如AKZO生产的SCA类改性树脂。高添加量的SCA改性聚酯树脂可以赋予漆料以优异的流平、流挂性之间的平衡。换言之；就是在获得较理想的一次成膜厚度的同时，还可使漆料具有良好的流平性能。据了解，某些汽车原厂本色漆的配方中流变性能改善树脂的用量超过主成膜物质。如以下配比 (质量份)。  \n\n<html><body><table><tr><td>主成膜物质</td><td>31 三聚氰胺甲醛树脂</td></tr><tr><td>SCA改性聚酯树脂 37</td><td></td></tr></table></body></html>  \n\n颜料则应选择那些耐候性优良的品种，此外对本色漆而言，良好的遮盖性能也非常重要，它是漆膜光泽、流平性以及流挂性能平衡的重要保证。一般设计本色漆配方时，将 $\\mathbf{P}/\\mathbf{B}$ 设定为 $0.65{\\sim}0.7$ 。过高的颜基比会带来光泽下降，保光性也不足，漆膜外观也欠佳。过低的颜基比则会导致遮盖力下降。  \n\n在本色漆的配方设计中，助剂的选用也是不可忽视的重要因素，尤其是有关流平剂系统的选择，这不仅仅关系到漆膜的流平性能，而且还应考虑重涂时对层间附着力的影响。最好选用那些已经证实对层间附着力没有影响的流平剂。一般多采用氟碳系以及某些硅系列流平剂，如BYK307、BYK307、BYK306 等。以下举一例采用聚酯树脂、短油醇酸树脂以及SCA改性聚酯树脂的典型本色漆配方供参考(质量份)。  \n\n<html><body><table><tr><td>聚酯树脂</td><td>30.00</td><td>丁醇</td><td>2.00</td></tr><tr><td>TiO</td><td>27.20</td><td>紫外光吸收剂Tinuvin 123</td><td>0.30</td></tr><tr><td>SCA改性聚酯树脂</td><td>1.20</td><td>BYK 331</td><td>0.05</td></tr><tr><td>短油醇酸树脂</td><td>18.90</td><td>BYK 306</td><td>0.40</td></tr><tr><td>丁醇改性三聚氰胺甲醛树脂</td><td>17.30</td><td>100°芳烃溶剂</td><td>6.65</td></tr><tr><td>乙二醇单丁醚</td><td>2.00</td><td></td><td></td></tr></table></body></html>  \n\n(3）大型巴士面漆基于大型巴士体积庞大，建设烘房投资巨大等方面原因，这里所采用的面漆多为丙烯酸-聚氨酯或聚酯-聚氨酯类双组分面漆。有关方面介绍详见汽车修补漆部分内容。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1054,
+        "chunk": "# 三、金属闪光底色漆  \n\n汽车行业自20世纪80年代伊始出现一种具有金属闪光效果的面漆，即金属闪光漆。最先问世的是单层金属闪光漆，后来又发展了所谓双层（或多层）金属闪光漆，即金属闪光底色漆-罩光清漆(或金属闪光底漆-底色漆-罩光清漆)。由于这类面漆能够给人以优异、独特的视觉感受，故发展迅速，至今各类金属闪光漆已占到汽车面漆的70%以上，成为汽车面漆的主要品种。这其中的银灰色被涂料界称为汽车永恒的流行色。  \n\n多层金属闪光漆中的底色漆是指含有某些效应颜料及着色颜料的一类涂料，它是涂于中间涂料之上，罩光清漆之下的涂层。因具有赋予车辆以特殊效果色以及打底色的功能，故被命名为“底色漆”（basecoat）。早期面市的底色漆固含较低，仅为 $10\\%\\sim15\\%$ ，稍后一些时候发展了中固体分底色漆，固含为 $15\\%\\sim20\\%$ ，这种中固体分底色漆施工黏度仅为 $100\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$ $(1000\\mathbf{r}/\\operatorname*{min})$ 。高固体分底色漆是在中固体分底色漆基础上发展起来的，为了保持良好的喷涂施工性能，需要极大地降低树脂的分子量，以获得较低的黏度。这样技术处理的副作用是涂层的物理干燥性能下降，抗流挂性能降低。为了克服高固体分底色漆施工时的流挂现象，要么使漆料具有假塑性，即在高剪切速率下表现出切变稀化，要么使漆料在某一低剪切速率下表现出高黏性行为。比较通常的做法是添加利用非水乳液聚合生成的聚合物微胶以获得切变稀化的效果。在高固体分底色漆中，添加聚合物微胶和有机膨润土等流变控制剂可有效地降低在高剪切速率下的黏度，以利于喷涂时漆料的雾化。  \n\n现今汽车行业中多采用以下三类底色漆（表3-2-21）：  \n\n表3-2-21几类底色漆系统的工艺数据  \n\n\n<html><body><table><tr><td>性能</td><td>中固体分</td><td>高固体分</td><td>水 性</td></tr><tr><td>固体分/%</td><td></td><td></td><td></td></tr><tr><td>本色底色漆 金属闪光底色漆</td><td>25~40 15~25</td><td>45~60 40~50</td><td>20~45 15~25</td></tr><tr><td>VOC/(g/L)</td><td>450~600</td><td>250~400</td><td>100~150</td></tr><tr><td>施工黏度</td><td></td><td></td><td></td></tr><tr><td>/S(DIN 4,23°C)</td><td>20~30</td><td>15~20</td><td>35~60</td></tr><tr><td>/mPa • s(1000r/min)</td><td>40~50</td><td>30~40</td><td>60~120</td></tr><tr><td>腹厚/μm</td><td></td><td></td><td></td></tr><tr><td>本色底色漆</td><td>15~25</td><td></td><td></td></tr><tr><td>金属闪光底色漆</td><td>10~15</td><td>20~30 15~20</td><td>15~25</td></tr><tr><td></td><td></td><td></td><td>10~15</td></tr><tr><td>罩光前闪蒸/C×min</td><td>23X(2~3)</td><td>23X (3~5)</td><td>(50~80)×(3~8)</td></tr></table></body></html>\n\n$\\textcircled{1}$ 中固体分底色漆；$\\textcircled{2}$ 高固体分底色漆；$\\textcircled{3}$ 水性底色漆。  \n\n北美多采用高固体分底色漆，而欧洲则倾向于使用水性底色漆，其他地区主要采用中固体分底色漆。仅就施工性能而言。固体分越低，也越容易获得良好的施工效果，如效应颜料的排布、雾影、色斑以及色差等方面的差异等。因此固体分的高低显示在底色漆方面的技术进步。  \n\n在汽车涂装的整个工艺流程中，金属闪光底色漆是溶剂排放量最高的涂装工段。有人曾对世界上几个主要大型汽车总装厂的涂装线做过仔细的考察统计，各工序的溶剂释放量大体见表3-2-22。  \n\n表3-2-22涂装施工中各工序的溶剂排放量  \n\n\n<html><body><table><tr><td>工 序</td><td>排放量/%</td><td>工 序</td><td>排放量/%</td></tr><tr><td>阴极电泳底漆</td><td>1~5</td><td>罩光清漆</td><td>8~13</td></tr><tr><td>中间涂料</td><td>14~16</td><td>防护蜡</td><td>13~14</td></tr><tr><td>抗石击涂料</td><td>0.5~1</td><td>洗涤溶剂</td><td>4~5</td></tr><tr><td>金属闪光底色漆</td><td>38~52</td><td>其他</td><td>2~3</td></tr><tr><td>本色漆</td><td>7~10</td><td></td><td></td></tr></table></body></html>  \n\n由表3-2-22所列数据可知：在涂装线各工序中，金属闪光底色漆是溶剂挥发比率最高的环节。由此大幅降低金属闪光底色漆中的VOC对降低整个涂装系统的溶剂释放具有举足轻重的作用。  \n\n除了提高施工固含量采用高不挥发分的品种外，降低涂料中VOC的含量的另外一个有效途径就是水性化。水性金属闪光底色漆降低VOC的效果非常显著，其有关数据见表3-2-23。  \n\n表3-2-23水性金属闪光底色漆对涂料系统中VOC的影响  \n\n\n<html><body><table><tr><td>类 别</td><td>涂料VOC/(g/L)</td><td>类别</td><td>涂料VOC/(g/L)</td></tr><tr><td>传统底色漆</td><td>600~700</td><td rowspan=\"2\">水性底色漆</td><td rowspan=\"2\">100~400</td></tr><tr><td>高不挥发分底色漆</td><td>250~610</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1055,
+        "chunk": "# 1.水性金属闪光底色漆  \n\n对于对装饰性要求较高的汽车特别是高级轿车用涂料而言，水性化的难度无疑远远大于其他涂料领域。主要体现在水性化后对漆膜耐水性、附着性特别是耐候性能的影响。另外由于水性涂料系统的稀释剂是挥发速率较慢的水，故使得涂装系统对施工条件特别是施工环境的要求更为苛刻，如相对湿度对施工环境的影响。另外基于水性底色漆特殊的流变特性，也使得铝粉、珍珠粉等效应颜料在涂层内相对而言更易移动，同时比较容易出现流挂等漆膜病。因此水性金属闪光底色漆开发的首要课题就是应尽可能扩大其对施工环境的适应性。  \n\n$\\textcircled{1}$ 颜料分散性不好。水性漆属于聚合物分散体系，颜料分散性不是很好，因此须采取措施加以改善。  \n\n$\\textcircled{2}$ 分散粒子的稳定性差。  \n\n$\\textcircled{3}$ 溶解的分子对剪切力、热、 $\\mathfrak{p H}$ 等都很稳定，而分散的粒子不稳定，因此要对分散体系采取稳定措施。分散粒子受剪切力后会被破坏，因而须考虑在制造、输送水性漆过程中避免剪切力的作用。分散粒子对 $\\mathbf{pH}$ 很敏感，漆中混人酸性物质会形成酸性粒子，从而产生胶化破坏水性漆。另外水性漆在运输过程中受寒冻结后分散粒子也会被破坏。  \n\n$\\textcircled{4}$ 表面张力大。水的表面张力大，故水性漆的表面张力也较大，在施工过程中要加强管理，否则涂装时易产生下列缺陷和漆膜病。  \n\na.易流挂。  \nb.展平性不好。  \nc.易产生缩孔、针孔。  \nd.不易渗入被涂物表面细小的缝隙中。  \n\n$\\textcircled{5}$ 蒸发热和热容值高，受温度、湿度的影响大。水的高蒸发热和热容值使水性漆中的水蒸发慢。溶剂型漆中溶剂总量的 $50\\%$ 在喷涂雾化过程中挥发掉，而对于水性漆仅为$25\\%$ 。水蒸发慢在涂装时易产生流挂，且使涂装效率变差。因此，需设置中间加热区将水从水性底漆涂层中强制挥发出去。在喷涂清漆前必须把 $90\\%$ 的水从水性底漆涂层中除掉（防止在最终烘烤时沸腾的水穿过清漆而挥发出来）以获得最佳的漆膜外观，从而避免水性底漆被清漆返溶。水的蒸发速率与相对湿度密切相关，相对湿度高时，水的蒸发速率很低。因此，喷漆室的相对湿度和温度必须控制在一定范围内，以确保喷漆雾化过程中适量的水挥发掉，并且使水和有机溶剂在涂膜中保持适当平衡。这个适当的平衡是很重要的，其可使涂料有合适的表面张力以润湿喷涂表面。  \n\n$\\textcircled{6}$ 导电性好。水的介电常数大，因此水性漆的导电性好，一般水性漆的电阻小于0.1MΩ，而溶剂型漆有一定的电阻 $(0.5\\sim20\\ensuremath{\\mathrm{M}}\\Omega^{\\cdot}$ 。水性漆的导电性好，当采用静电喷涂  \n\n时有特殊要求。  \n\n②腐蚀性大。水性漆含有大量水，因而对容器、输送管路、喷漆室体等易受潮部位有腐蚀性，需用不锈钢或塑料材料制作。  \n\n③流变行为。流体黏度随剪切率的增加而减少时称为假塑性流体。假塑性流体的流变行为与其流变所走路径有关，也就是对时间有依赖，故称之为触变性流体。有的公司的水性金属漆和水性色漆本质上属假塑性流体；有的公司的水性漆具有触变性，其黏度取决于所用的剪切速率及其剪切历程。基于水性漆的特性，用流出杯测量黏度值不具有重现性，只有用旋转黏度计测出包括低剪切速率下和高剪切速率下的数据点完整流变曲线才能给出水性漆流变行为的完整特性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1056,
+        "chunk": "# 2.底色漆的基本特性  \n\n金属闪光底色漆自身性能中最为重要的就是效应颜料的排列、定向以及系统的流变行为。底色漆的漆膜厚度取决于自身的遮盖力，这与效应颜料品种的关系极大。如银白色相具有最好的黑-白遮盖力，漆膜厚度仅需 $10\\mu\\mathrm m$ 左右；而白色，则需要 $20\\mu\\mathrm{m}$ ；黄、红相则需要$30\\mu\\mathrm{m}$ 。含效应颜料漆膜的色相取决于这些效应颜料在漆膜中的排列、定向。为了表述这一性质，人们引入了“随角异色效应”指数的概念。所谓“随角异色效应”是指漆膜因观察角度的不同而呈现出不同的色相。对于本色漆而言，其随角异色效应指数为0，而对于性能良好的金属闪光漆，其随角异色效应指数可达 $15{\\sim}17$ 。其计算公式如下。  \n\n随角异色效应指数=2.69(L1s-Lu）11式中L15\\*-—15°角反射光强度；$L_{45^{*}}$ 45°角反射光强度；$L_{110^{*}}$ ——110°角反射光强度。  \n\n有两种机理可以用来解释效应颜料在金属闪光漆漆膜中的排列、定向问题。  \n\n第一种是有关漆雾粒子在被涂物表面流展的过程，如图3-2-2所示，漆雾凝聚成的小珠垂直于涂装面有一个向侧面方向的动力。在这个侧向力的驱使下，小珠沿侧向力的方向流展，于是效应颜料也随之定向。  \n\n![](images/322986520c6343ed81c85e53126f1eedbe6648d52111a716be37b1222322401d.jpg)  \n图3-2-2成膜过程中效应颤料定向的机理  \n\n第二种是用漆膜收缩的机理来解释效应颜料的排列、定向问题，即随着溶剂的挥发，凝结在涂装表面的漆液收缩成膜的过程中，效应颜料随之定向（图3-2-3)。效应颜料（如铝粉、珠光粉等）的定向也受施工方式的影响。采用高速静电旋杯制备的底色漆漆膜与空气雾化喷枪的效果就不一样。这可能与静电旋杯制得的漆膜较“干”，漆雾到达涂装表面后侧向力不足以使其很快变形、流展，不利于效应颜料的排布和定向的缘故。  \n\n效应颜料在漆膜中的排列、定向受漆料的流变行为影响极大。由可溶性树脂配制的溶剂型底色漆呈现出牛顿型流动特征，如果不添加流变助剂，则底色漆中效应颜料的定向极差，且在垂直涂装面上几乎无法实现不流挂成膜。微胶蜡分散液、脲基SCA（sagcontrolagent）流挂控制剂等添加到配方中，可有效改变系统的流变性能。常见SCA改性树脂均是六亚甲基二异氰酸酯与苄基胺的脲系加成物。  \n\n施工时，这类漆料在不同的剪切速率下表现出不同的流变性能。漆料贮存在涂料罐中且未揽拌时，其剪切速率为0，此时漆料黏度非常高，有效地防止密度相对较高的效应颜料沉降。而稍加搅拌或将其泵入输送管路，则其黏度迅速下降，表现出良好的泵送性能。施工时，在喷嘴及旋杯杯沿附近，剪切速率最高，漆料的黏度也极低，对漆料的雾化非常有利。此种黏度较低的状态一直延续到雾化的粒子在车身表面变形、流展、凝聚成膜以及效应颜料的定向。一旦流平过程结束，剪切应力消失，黏度变得很高，此时有利于防止流挂的发生。  \n\n![](images/b54ac10612737b96ef825ff250bcc05485610c02e50fe0f420c96d6b24d7646f.jpg)  \n图3-2-3漆膜收缩助效应颜料定向  \n\n不仅仅溶剂型底色漆如此，水性底色漆也表现出类似的流变行为，但有些许滞后。从图3-2-4中可看到：在贮存和施工条件下，高固含量底色漆和水性底色漆不同的剪切速率及黏度之间的关系。  \n\n![](images/a780f16a7512d4873c31f01e449fd6cf13273ab3efeeaec3d9f1f0d474c91804.jpg)  \n图3-2-4水性底色漆和高固含底色漆的流变行为",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1057,
+        "chunk": "# 3.主成膜物质  \n\n溶剂型底色漆中采用的成膜物质一般为热固性丙烯酸树脂与聚酯树脂组合，再配以SCA改性聚酯树脂、氨基树脂以及CAB等。在树脂组分中，聚酯树脂占 $16\\%\\sim26\\%$ ，丙烯酸树脂占 $27\\%\\sim32\\%$ ，SCA改性聚酯树脂占 $3\\%\\sim15\\%$ ，而CAB则大约为10。一般将聚酯与丙烯酸两类树脂的配比控制在 $1:1$ 左右，可获得各方面良好的平衡。CAB约占总树脂量的 $10\\%$ ，一般建议采用几种CAB搭配使用，这样可以调节施工固含量、防止罩光时的重溶、合适的物理干燥时间等。SCA改性聚酯树脂是一种起流挂控制作用的树脂，它可防止漆膜流挂，赋予湿漆膜以触变性能。这一点对于浅色金属闪光漆尤为重要，它可有效防止色斑和局部色差。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1058,
+        "chunk": "# 4.分散蜡及助剂  \n\n金属闪光底色漆中采用分散蜡以帮助效应颜料排列、定向是人们熟知的手段。在本章第五节汽车修补涂料中将详细讨论分散蜡的类型、性能等。这里需要特别强调的是，在以室温或低温干燥（或称固化）的汽车修补涂料系统中，以采用聚酰胺蜡较多，如日本楠本化成株式会社的Disparlon 6900-20X等。但在以高温烘烤固化为主的汽车原厂漆系统中，则多采用乙烯类共聚物（包括乙烯-醋酸乙烯共聚物、乙烯-丙烯酸共聚物等），如毕克公司的Cerafak100、Cerafak 103、Cerafak 106，Morton S.A.的 Polyslip VM 56，Kemperial Co.的 Dis-per KC 568等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1059,
+        "chunk": "# 5.典型底色漆  \n\n<html><body><table><tr><td>（1）配方（质量份）</td><td></td><td></td><td></td></tr><tr><td>分散蜡液（10%）（一）</td><td>19.4</td><td>丁基溶纤剂（一)</td><td>7.5</td></tr><tr><td>热固性丙烯酸树脂</td><td>11. 70</td><td>101灯黑</td><td>0.5</td></tr><tr><td>聚酯树脂</td><td>11. 2</td><td>Alpate 8160 AR</td><td>1. 9</td></tr><tr><td>Setal 90173 SS 50</td><td>1.40</td><td>Alpate 8820 AR</td><td>1. 0</td></tr><tr><td>CAB 381-0. 5(20%)()</td><td>8.5</td><td>分散蜡液（10%）（二）</td><td>4.0</td></tr><tr><td>CAB 381-2(20%)</td><td>1. 7</td><td>CAB 381-0. 5(20%)(二)</td><td>2.0</td></tr><tr><td>甲醚化三聚氰胺甲醛树脂</td><td>13.2</td><td>丁基溶纤剂(二)</td><td>11.5</td></tr><tr><td>BYK 306</td><td>0.4</td><td>醋酸丁酯</td><td>3.1</td></tr><tr><td>100*芳烃</td><td>1. 0</td><td></td><td></td></tr></table></body></html>  \n\n(2）工艺  \n\n$\\Phi$ 将分散蜡液（ $10\\%$ ）（一）加到配料罐中，搅拌并检查细度，此时应 ${\\leqslant}20\\mu\\mathrm{m}$ 。然后在搅拌下加入热固性丙烯酸树脂、聚酯树脂，搅拌 $30\\mathrm{{min}}$ ，检查细度应 ${\\leqslant}20\\mu\\mathrm{m}$  \n\n$\\textcircled{2}$ 依次将Setal90173SS50、CAB381-0.5（ $20\\%$ ）（一）、CAB381-2（ $20\\%)$ 、甲醚化三聚氰胺甲醛树脂、BYK306、 $100^{\\sharp}$ 芳烃、丁基溶纤剂（一）加到罐中，然后再慢慢将101灯黑在搅拌下加入，高速分散1h。混合物用装有双层过滤袋的袋式过滤机过滤。  \n\n$\\textcircled{3}$ 将Alpate8160AR和Alpate8820AR加到另外-个罐中，然后加人分散蜡液$10\\%$ ）(二)，高速分散 $\\mathrm{1h}$ 。在搅拌下加人CAB381-0.5（ $20\\%$ ）（二）继续搅拌 $30\\mathrm{min}$ 。检查细度，应 ${\\leqslant}20\\mu\\mathrm{m}$ 要  \n\n$\\textcircled{4}$ 铝粉浆制备完成后，应熟化 $^{10\\mathbf{h}}$ ，使用前再搅拌 $30\\mathrm{min}$ a  \n\n$\\textcircled{5}$ 将调制好的清漆溶液在搅拌下慢慢加到铝粉浆中，分散 $30\\mathrm{{min}}$ 。采用滤网过滤，然后再搅拌2h。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1060,
+        "chunk": "# $\\textcircled{6}$ 丁基溶纤剂（二）和醋酸丁酯用于调整色相和黏度。  \n\n(3）产品标准  \n\n<html><body><table><tr><td>黏度</td><td>施工</td><td>17~21</td></tr><tr><td>原漆（涂-4杯）/s</td><td>50</td><td>稀释率（醋酸丁酯：二甲苯=60：40）/% 35~45</td></tr><tr><td>施工</td><td>12</td><td>阻抗/MΩ 0.4~0.7</td></tr><tr><td>固体分/为</td><td>遮盖力/μm</td><td>8~10</td></tr><tr><td>原漆</td><td>26~28</td><td>固化条件/C×min 140×30</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1061,
+        "chunk": "# 四、罩光清漆  \n\n在汽车涂料的涂装系统中，无疑罩光清漆是起保护和装饰作用最为关键的一道涂层。汽车工业不仅仅要求罩光清漆具有良好的物理力学性能、优异的耐候性、耐各种介质性能等，还要求它具有非常好的施工适应性能。此外，现代汽车工业出于环境方面因素的考虑，对罩光清漆系统中溶剂的含量也提出了日益苛刻的要求。如欧盟早在1993年就在“溶剂控制指令——汽车涂装过程排放限制”中严格规定了轿车涂装线有机溶剂的释放量（包括底漆、中间涂料、面漆等）不得高于 $45\\mathrm{g}/\\mathrm{m}^{2}$ 。因此现代不少汽车总装厂所采用的罩光清漆多为高不挥发分溶剂型丙烯酸（或丙烯酸改性聚酯）清漆、粉末罩光清漆以及水性罩光清漆等。这几类罩光清漆的技术经济方面各有优劣，见表3-2-24。  \n\n表3-2-24几类罩光清漆技术经济性能比较  \n\n\n<html><body><table><tr><td>项目</td><td>溶剂型</td><td>水 性</td><td>粉末</td></tr><tr><td>有机溶剂含量/%</td><td>>30</td><td>2~10</td><td>无</td></tr><tr><td>施工工艺</td><td>施工工艺成熟，成 本较低</td><td>需新建涂装线，包括烘道，对施工环 境要求苛刻，需增加基本建设投资</td><td>需新建涂装线，生产效率高，几 乎无污染物排放</td></tr><tr><td>烘烤条件</td><td>成熟</td><td>雷增加预烘烤烘道</td><td>较为成熟</td></tr><tr><td>漆膜性能</td><td>综合性能好，成熟</td><td>硬度高</td><td></td></tr><tr><td>发展方向</td><td>高不挥发分</td><td>降低施工条件限制</td><td>提高耐候性、漆膜外观等</td></tr></table></body></html>  \n\n总之，作为一个理想的罩光清漆必须具备以下特点：  \n\n$\\Phi$ 良好的外观特别是应具有较高的光泽；  \n$\\textcircled{2}$ 施工性能优良，能适应汽车厂绝大多数涂装线；  \n$\\textcircled{3}$ 较低的烘烤温度；  \n$\\textcircled{4}$ 较好的耐划伤性能；  \n$\\textcircled{5}$ 良好的耐酸雨性能；  \n$\\textcircled{6}$ 高不挥发分，较低的VOC；  \n$\\textcircled{7}$ 优良的耐候性，保光、保色性等。  \n当今汽车行业所用的罩光清漆可归结为以下四大类：$\\textcircled{1}$ 单组分溶剂型罩光清漆；  \n$\\textcircled{2}$ 双组分溶剂型罩光清漆；  \n$\\textcircled{3}$ 单组分水性罩光清漆；  \n$\\textcircled{4}$ 粉末罩光清漆。  \n\n上述四类罩光清漆的市场占有率见表3-2-25，从表中的数据可知：传统单组分溶剂型罩光清漆，即丙烯酸-氨基类烤漆仍然拥有汽车罩光清漆市场的最大份额，但其占有率有所下降，这在欧洲特别明显。而在新技术的使用上（水性和粉末罩光清漆）欧洲要领先于世界上其他地区，现分述如下。  \n\n<html><body><table><tr><td>单位：%</td></tr><tr><td></td></tr><tr><td></td></tr></table></body></html>  \n\n表3-2-25几类罩光清漆的市场占有率  \n\n\n<html><body><table><tr><td>类别</td><td>欧洲</td><td>世界</td><td>类别</td><td>欧洲</td><td>世界</td></tr><tr><td>单组分溶剂型罩光清漆</td><td>64</td><td>81</td><td>单组分水性罩光清漆</td><td>1</td><td>0</td></tr><tr><td>双组分溶剂型罩光清漆</td><td>33</td><td>18</td><td>粉末罩光清漆</td><td>2</td><td>1</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1062,
+        "chunk": "# 1.单组分溶剂型罩光清漆  \n\n单组分溶剂型罩光清漆中以丙烯酸-氨基烤漆为主，但细分起来却有 $5\\mathord{\\sim}6$ 种之多。现分述如下。  \n\n(1）单组分丙烯酸-氨基清漆丙烯酸-氨基类罩光清漆是应用最为广泛的品种之一，这类清漆之所以获得如此广泛的应用其主要原因如下。  \n\n$\\Phi$ 丙烯酸类聚合物C一C主链结构赋予其良好的耐老化及耐各种介质，特别是非极性介质性能。丙烯酸类单体分子上的不饱和双键经聚合反应，形成具有C一C主链的高分子化合物。高聚物结构理论告诉人们：由C一C主链构成的高分子化合物一般都具有良好的抗氧化性及耐介质性能。这一抗氧化性能不仅仅可为丙烯酸类涂料带来突出的保光、保色性，而且也为通过聚合反应制造丙烯酸树脂时带来方便。也就是说，相对其他涂料用合成树脂而言（如醇酸树脂、聚酯树脂、酚醛树脂、环氧树脂等)，即使在聚合反应的相对高温下，空气中的氧也很难使丙烯酸类聚合物的大分子链氧化降解。这样就不难理解为什么只要原料及配方选配得当、聚合工艺合理，一般都可获得几乎无色透明的丙烯酸树脂了。  \n\n$\\textcircled{2}$ 丙烯酸类单体的性能各有不同，通过不同单体的组合，可较为简便地调整成品聚合物的物理力学性能，以满足用户的多方需求。  \n\n$\\textcircled{3}$ 相对于其他涂料用成膜物质而言，可通过共聚反应，比较方便地将某些特种活性官能团引入丙烯酸类聚合物主链，从而大大增加了丙烯酸类涂料的品种、拓宽其应用领域。  \n\n$\\textcircled{4}$ 施工性能优良：丙烯酸类涂料的施工性能良好，它们能够适应几乎所有的涂装工艺，而且还能满足施工方面的某些特殊要求。  \n\n$\\textcircled{5}$ 优良的装饰性能。正是由于丙烯酸类涂料良好的施工性能，使得这类涂料很容易获得非常理想的装饰效果。尽管在丙烯酸类涂料发展的初期，还有人对这类涂料涂层的“丰满度”存在疑虑，但近年来高不挥发分、低黏度丙烯酸树脂的出现已经成功地弥补了这一缺憾。丙烯酸类涂料的高光泽、高鲜艳性已经得到市场普遍赞许。因此在汽车类对涂层的装饰性要求比较苛刻的领域，大量采用了丙烯酸类罩光清漆。  \n\n然而这类罩光清漆也存在儿乎无法克服的缺欠，那就是在羟基丙烯酸树脂与烷基醚化三聚氰胺甲醛树脂烘烤固化的交联反应中会形成一定数量的醚键。这类交联键在偏酸性（如$\\mathrm{pH}\\leqslant6$ ）的条件下对水解敏感，致使成膜物质降解，而使涂层明显失光、变色等。  \n\n典型溶剂型丙烯酸-氨基罩光清漆由主成膜物质（热固性丙烯酸树脂)、交联剂（各种三聚氰胺甲醛树脂)、各种助剂（流变剂、流平剂以及紫外光吸收剂等）以及溶剂所组成（图3-2-5)。热固性丙烯酸类树脂和三聚氰胺甲醛树脂两者的比例大约为 $(65\\sim75):(25\\sim35)$ 助剂中的流平剂以有机硅系流平剂为主，比较常见的采用BYK331与306配伍。BYK331可赋予涂层平滑光洁的表面，而306的引入可避免清漆因某种原因需要再涂时对层间附着力的影响。高级轿车用罩光清漆还需要添加光稳定剂，比较常见的组合是汽巴公司推荐的Tini-vinl130和Tinuvin292。溶剂中一般以极性溶剂为主，再辅以Solvesso $100^{\\sharp}$ 和 $150^{\\sharp}$ 等芳烃溶剂。作为丙烯酸-氨基涂料系统中的极性溶剂有醋酸丁酯等酯类、甲基戊基酮类、丁基溶纤剂、丙二醇丁醚等醇醚类溶剂以及醋酸丁氧基乙酯等高沸点醚酯类溶剂。高沸点极性溶剂对于采用高速旋杯、Ω静电喷涂等手段施工时尤其重要，在拟定配方时需认真考虑这些溶剂的用量。  \n\n![](images/fe064c849ce785cfaf68d537d60dd2e3e3808e2fcbc3dd49a016b600943a4c85.jpg)  \n图3-2-5丙烯酸-氨基烤漆交联过程中醚键形成示意  \n\n近几年国内不少涂料厂家学习了国外同行的先进经验，在实用中普遍采用了硬树脂和软树脂搭配的做法。也就是说他们为同一类型的涂料准备了硬、软两种树脂。在生产中可以根据客户的具体要求，选用不同比例的软、硬树脂搭配，以对其力学性能进行适当调节，满足客户的需求。这种构思比起过去国内比较流行的在一个配方中仅仅采用一个主成膜物质（树脂）的做法要科学、实用得多。从引进的国外相关技术的清漆配方中可以发现；清漆的成膜物质，丙烯酸类树脂和氨基树脂的搭配可以多到四个树脂以上，即两个热固性丙烯酸树脂、两个氨基树脂以及改善系统流变性能的抗流挂树脂等。两个热固性丙烯酸树脂中一个赋予涂层较高的硬度，而另一个则偏软些，可赋予涂层良好的柔韧性。三聚氰胺甲醛树脂则多按照固化速率的快慢来搭配，往往挑选一快一慢的氨基树脂组合。丙烯酸树脂与氨基树脂的配比大约为 $70:30$ 左右。现举一个采用几种丙烯酸及氨基树脂的清漆配方为供读者设计配方时参考。  \n\n$\\textcircled{1}$ 配方 (质量份）  \n\n\n<html><body><table><tr><td>DC2868</td><td>30.00</td><td>Tinuvin 292</td><td>0.60</td></tr><tr><td>DC2868B</td><td>22.00</td><td>10%BYK306溶液</td><td>1.10</td></tr><tr><td>Setalux C91795 VX-60</td><td>10.00</td><td>10%KT516溶液</td><td>0.70</td></tr><tr><td>异丁醇醚化三聚氰胺甲醛树脂</td><td>17.00</td><td>100#芳烃溶剂</td><td>7.20</td></tr><tr><td>正丁醇醚化三聚氰胺甲醛树脂</td><td>7.00</td><td>甲基戊基酮</td><td>3.50</td></tr><tr><td>Tinuvin 1130@</td><td>0.90</td><td></td><td></td></tr><tr><td colspan=\"4\">①大昌树脂；②AKZO；③汽巴；④Kenperial Co..</td></tr><tr><td colspan=\"4\">②典型罩光清漆的施工参数</td></tr><tr><td>施工黏度/s</td><td>12~15</td><td>第二道膜厚/μm</td><td>20~25</td></tr><tr><td>施工固含/%</td><td>40~50</td><td>闪蒸时间/min</td><td>10</td></tr><tr><td>施工设备</td><td>空气雾化喷枪或静电杯</td><td>烘烤条件/CXmin</td><td>(130~150) × (20~30)</td></tr><tr><td>第一道膜厚/μm</td><td>15~20</td><td>漆膜厚度/μm</td><td>35~45</td></tr><tr><td>闪蒸时间/min</td><td>2</td><td></td><td></td></tr><tr><td colspan=\"4\">③典型罩光清漆的物性</td></tr><tr><td>光泽(20°)/%</td><td>87</td><td>杯突/mm</td><td>≥3</td></tr><tr><td>附着力</td><td>A或B</td><td>锥弯/mm</td><td>≤14</td></tr><tr><td>单层</td><td>100/100</td><td>抗石击/级</td><td>≤3</td></tr><tr><td>复合涂层</td><td>100/100</td><td>硬度（柏萨兹）/s</td><td>≥150</td></tr></table></body></html>  \n\n(2）硅烷改性丙烯酸-氨基罩光清漆20世纪的90年代中叶，一种耐酸雨的单组分丙烯酸-氨基罩光清漆迅速进入汽车涂料市场，那就是硅烷改性丙烯酸-氨基罩光清漆。连接于聚合物主链上的这些硅烷基团在烘烤过程中会发生“水解反应”，形成硅羟基。这些硅羟基非常容易发生缩合反应形成含硅氧烷结构的交联键。这些硅氧烷交联键结构的存在不仅仅提高了交联密度，而且由于Si—O—Si网状结构的化学稳定性最终导致漆膜的抗酸性介质性能得到大幅度的改善。有人曾对硅氧烷的引人量对热固性丙烯酸树脂憎水性能的改善做过较为系统的研究，他们发现：未改性的高固体分羟基丙烯酸-聚氨酯漆膜的表面能较大，与水的接触角较小，大约为 $77^{\\circ}$ ，有一定的亲水性。随着硅氧烷引入量的增加，水接触角也逐渐增加。硅氧烷的引入量达到 $30\\%$ 时，漆膜的水接触角提高到 $88^{\\circ}$ 左右。从水接触角的变化来看，在聚合物链中引入硅烷可使漆膜表面的疏水性增加，这是因为硅烷偶联剂中所含的甲基丙烯酰氧基与甲基丙烯酸酯活性相近，极其容易与其他单体共聚形成无规共聚物。在聚合物链中引入含有丙烯酰氧基的硅单体后，树脂的疏水性增加，水接触角随硅单体用量的增加而增大，铅笔硬度从2H提高到4H。因此，硅烷改性丙烯酸-氨基烤漆漆膜的耐酸性介质性能得到大幅改善也就不足为奇了。  \n\n硅改性丙烯酸树脂中的丙烯酸单元与普通丙烯酸类树脂类似，也是由丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、苯乙烯等单体构成。在这类聚合物主链上引入烷氧基硅烷单元，利用硅烷上的烷氧基在酸、碱以及有机金属化合物催化剂存在的条件下水解、缩合，从而交联成膜。这类涂料具有超耐候性、耐沸水性、耐溶剂性、耐极性介质性、抗污染性等特点，漆膜的物理力学性能也较良好。这里举一例典型配方及工艺供参考。  \n\n$\\Phi$ 配方 (质量份）  \n\n甲 9.35 y-甲基丙烯酰氧丙基三甲氧基硅烷 4.93   \n丁醇 19.70 顺丁烯二酸单丁酯 1.18   \n苯乙烯 13.70 过氧化2-乙基己酸叔丁酯 0. 50   \n甲基丙烯酸甲酯 10.95 偶氮二异丁腊 1.00   \n甲基丙烯酸丁酯 12.30 甲 20.18   \n丙烯酸丁酯 6.21  \n\n$\\textcircled{2}$ 工艺  \n\na.将甲苯和丁醇加人到反应釜中，在 ${\\bf N}_{2}$ 保护下升温到 $80^{*}\\mathrm{C}$ 。  \n\nb.将苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸丁酯、-甲基丙烯酸氧丙基三甲氧基硅烷、顺丁烯二酸单丁酯、过氧化2-乙基己酸叔丁酯、偶氮二异丁晴、甲苯混合均匀，然后抽入高位槽中。  \n\nc.滴加混合物，耗时3h左右。  \n\nd.继续保温 $^{15\\mathrm{h}}$ 后，降温、出料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1063,
+        "chunk": "# $\\textcircled{3}$ 技术指标  \n\n不挥发分/%黏度（加氏黏度，25℃）  \n\n(3）含氨基甲酸酯基聚合物-氨基罩光清漆改善漆膜耐酸性介质的另一种途径就是在主成膜物质的大分子主链上引入氨基甲酸酯基（图3-2-6)。这样在烘烤成膜时，这些氨基甲酸酯基与氨基树脂之间发生交联反应，形成氨基甲酸酯的交联键。采用这类交联系统的罩光清漆已在美国成功用于汽车行业。  \n\n![](images/29c5f6d40f428b3ff04720f03613c7dd29e068bce5b9068f751d4043b45a7270.jpg)  \n图3-2-6含氨基甲酸酯交联键的罩光清漆  \n\n(4）单组分聚氨酯罩光清漆众所周知，在耐酸性介质侵蚀方面，双组分聚氨酯罩光清漆比丙烯酸-氨基或醇酸-氨基烤漆要优越得多。然而这类双组分产品因有一个所谓“适用期”的问题而并不适合大批量生产的汽车总装厂。采用封闭异氰酸酯交联体系的单组分罩光清漆恰恰弥补了上述双组分的缺点，很快就得到了汽车行业的认可。目前使用最为广泛的封闭异氰酸酯为六亚甲基二异氰酸酯（HDI)、异佛尔酮二异氰酸酯（IPDI）等脂肪族、脂环族异氰酸酯类。封闭剂多采用丙二酸酯类、二甲基吡唑类等。不少汽车漆生产厂家将封闭异氰酸酯交联剂与三聚氰胺甲醛树脂拼合使用。烘烤温度范围在 $130\\sim150^{\\circ}\\mathrm{C}$ 。欧洲的汽车总  \n\n装厂已开始采用这类交联系统的罩光清漆。  \n\n(5）单组分酸固化环氧基的罩光清漆含缩水甘油基的丙烯酸聚合物可与脂肪族多元羧酸发生交联反应固化成膜（图3-2-7）。在抵御酸性介质侵蚀方面这是最具商业价值的罩光清漆系统。增加聚合物主链上交联基团的数量可提高交联密度，进而提高耐酸性介质侵蚀和耐磨耗性能。为了避免羧基、羟基与环氧基团在涂料贮存过程中就发生反应，有时也将其配置为双组分。本系统已在日本一些汽车总装厂投入使用。  \n\n上述五类罩光清漆都是现代汽车行业常用的品种。其中除第一类外，其他几类都是针对汽车表面涂层的耐酸性介质而发展起来的。  \n\n以丙烯酸-氨基树脂为基础的上述几类罩光清  \n\n![](images/2a42307f1615fb45b3629f1231493cd204baeaaee7302c28d98ea206bf573538.jpg)  \n图3-2-7含缩水甘油基丙烯酸聚合物与羧基的交联反应代表丙烯酸聚合物主链  \n\n漆系统都是围绕耐酸性介质侵蚀而发展起来的品种。美国一家汽车涂料公司曾就此对它们的耐酸性介质性能做过系统比较，实验结果见表3-2-26。  \n\n表3-2-26几类罩光清漆的耐酸性介质性能  \n\n\n<html><body><table><tr><td>品 种</td><td>酸蚀速度</td><td>品种</td><td>酸蚀速度</td></tr><tr><td>丙烯酸-氨基</td><td>8.0~10.0</td><td>含缩水甘油基丙烯酸-羧酸酯</td><td>4.5~6. 0</td></tr><tr><td>硅烷改性丙烯酸-氨基</td><td>5. 0~7.0</td><td>丙烯酸-氨基甲酸酯</td><td>4. 5~6. 0</td></tr><tr><td>含氨基甲酸酯丙烯酸-氨基</td><td>5.0~7.0</td><td></td><td></td></tr></table></body></html>  \n\n注：美国佛罗里达州，表中数据为酸蚀分级评估（0～10）；0级为最好，无酸蚀；10级最差，完全锈蚀，一般汽车行业将其又分为三类。  \n一类：0～3，无明显酸蚀现象，最理想。  \n二类： $4\\sim6$ ，存在可见锈蚀，但经简单抛光，可修复。  \n三类： $7\\sim10$ ，锈蚀见底，需经正常修补作业方可修复。  \n\n从表3-2-27中所列数据可知：几种改性丙烯酸-氨基的耐酸性介质性能都有不同程度的改善。总体来说，漆膜的耐酸性介质性能与以下因素有关。  \n\n$\\textcircled{1}$ 交联漆膜的玻璃化温度玻璃化温度越高，其耐酸性介质性能越好。  \n\n$\\textcircled{2}$ 漆膜的亲水性漆膜的亲水性低，可使其水渗透性降低，从而使得耐酸性介质得到改善。$\\textcircled{3}$ 漆膜的交联密度交联密度越高，耐酸性介质性能越好。$\\textcircled{4}$ 紫外光稳定性漆膜的耐紫外光性能越好，其耐酸性介质性能也越好。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1064,
+        "chunk": "# 2.水性罩光清漆  \n\n20世纪90年代初水性罩光清漆就已进入汽车行业。最早采用的欧洲厂家应属德国的欧宝（Opel）汽车公司。今天，基于采用封闭异氰酸酯和三聚氰胺甲醛树脂交联剂的水性聚酯-丙烯酸树脂罩光清漆已经较为成熟，成为一些大型汽车总装厂罩光清漆的首选开发品种。典型水性罩光清漆的参数见表3-2-27。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1065,
+        "chunk": "# 3.粉末罩光清漆  \n\n自20世纪60年代粉末涂料问世以来，因其在高效、节能以及环境保护方面突出特点，粉末涂料获得了快速发展，成为仅仅次于水性涂料成长最快的新品种。预计到2010年，粉末涂料将要占到工业涂料消耗量的 $20\\%$ 。1993年美国福特、通用以及克莱斯勒三大汽车公司联手成立了“低VOC涂料联合研究会”共同开发汽车用低VOC排放量的涂料系统。最新的研究成果表明，VOC排放量最少的轿车车身涂装系统为：  \n\n表3-2-27两类水性罩光清漆特性比较   \n\n\n<html><body><table><tr><td>特性</td><td>单组分（低VOC)</td><td>单组分（零VOC)</td></tr><tr><td>不挥发分/%</td><td>40~41</td><td>36~37</td></tr><tr><td>VOC/(g/L)</td><td>130~140</td><td>接近零</td></tr><tr><td>施工黏度（DIN4-杯,23C）/s</td><td>30~32</td><td>60</td></tr><tr><td>膜厚/μm</td><td>35~45</td><td>35~45</td></tr><tr><td>闪蒸条件/C×min</td><td>23X5</td><td>22X2</td></tr><tr><td>预烘条件/C×min</td><td>50×2+80×7</td><td>50×5+80X7</td></tr><tr><td>烘烤条件/CXmin</td><td>150X24</td><td>155×24</td></tr></table></body></html>  \n\n阴极电泳底漆→粉末中间涂料→水性底色漆→粉末罩光清漆  \n\n在新的涂装系统中，粉末涂料占据其中的两个品种，由此可见粉末涂料在汽车行业中的前景。汽车行业用粉末罩光清漆具有如下优点：  \n\n$\\textcircled{1}$ 涂装效率高，由于粉末涂料特殊的涂装工艺，使得过喷的粉末可以直接回收而重复使用；  \n\n$\\textcircled{2}$ 无废水、废料排放；  \n\n$\\textcircled{3}$ 不必采用有机溶剂清洗喷漆设备和喷漆间，只需定时进行真空吸尘即可；  \n\n$\\textcircled{4}$ 节能、低毒，几无VOC排放；  \n\n$\\textcircled{5}$ 漆膜厚度均一，水平面或垂直面外观几无差别等。  \n\n可用于汽车工业的粉末涂料有聚酯、聚氨酯、丙烯酸以及环氧-聚氨酯等几大类。20世纪的90年代初，粉末涂料应用于汽车零部件上获得成功，此后相关技术人员在改善粉末涂料的装饰性、耐化学性、耐紫外光、抗划伤性等方面做了大量研究工作，现已能基本满足汽车工业的需要。到20世纪的末期，已有不少汽车总装厂的涂装线采用粉末涂料，如欧洲的“宝马”公司采用了高耐候性丙烯酸粉末涂料用作罩光清漆，其综合性能堪比溶剂型同类品种。  \n\n在粉末涂料系列中，聚酯、聚酯-聚氨酯一直是外用的主要品种，并且也被尝试用于汽车涂料上。然而随着汽车工业的不断发展，对所采用的涂料的性能要求愈来愈苛刻，如更高的耐候性、更高的硬度以及更为优越的附着力等。大大促进了丙烯酸粉末涂料技术的发展。现今丙烯酸粉末涂料不仅仅已经用于汽车各种零部件（铝合金车轮毂，车门手柄、雨刮等)，而且还用于汽车车身的表面涂装中。  \n\n粉末涂料用丙烯酸树脂为丙烯酸酯类、甲基丙烯酸酯类以及其他乙烯类单体共聚而其中，为给交联固化提供可反应基团，参与共聚反应的单体中必须包含：  \n\n$\\textcircled{1}$ 含羟基或缩水甘油基的单体；  \n$\\textcircled{2}$ 含羧基或酸酐基的单体；  \n$\\textcircled{3}$ 含氨基单体等。  \n\n其中以引入含羟基或含缩水甘油基单体最为常见。可用于制备丙烯酸树脂的单体种类较多，其大分子设计自由度较大，因此可以满足广大客户不同的需求。丙烯酸粉末涂料用常见的丙烯酸树脂的不挥发分几乎为 $100\\%$ ，分子量在 $3000{\\sim}5000$ ，玻璃化温度应不小于 $60^{\\circ}\\mathrm{C}$ .熔融温度应在 $75\\mathrm{\\sim}105\\mathrm{\\texttau}$  \n\n粉末涂料在汽车工业中的应用受到自身制造工艺的制约，目前还仅限于用作中间涂料和清漆。这主要是因为粉末涂料不像液体涂料那样容易换色。今后汽车用粉末涂料的发展方向仍然是继续提高其耐候性、装饰性、降低烘烤温度以及薄膜化等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1066,
+        "chunk": "# 五、汽车面漆标准  \n\n我国虽然制定有国家标准（GB/T13492—1992)，但汽车总装厂还是各自都制定特有的厂标，国外如此，我国各大汽车总装厂也都如此。南方某大型汽车总装厂的标准比较典型，既有采用国家标准的检测方法，也有参考国外著名车厂的拟定的标准（表3-2-28)。国外一些大型车厂往往还制定了独特的检测标准，如德国汽车业用来考核耐湿热性的VDA循环、抗石击性能检测、耐刷洗性能等这里就不一一列举了。  \n\n表3-2-28汽车面漆技术指标  \n\n\n<html><body><table><tr><td>类别</td><td>颜色与外观</td><td>技 术 标 指</td><td>标准</td></tr><tr><td rowspan=\"8\">原漆</td><td>黏度/s</td><td>40~70</td><td>GB 1723—1979</td></tr><tr><td>细度/μm</td><td>≤ 10</td><td>GB 17241979</td></tr><tr><td>不挥发分/%</td><td>55</td><td>GB 1725-1979</td></tr><tr><td>速盖力/μm 浅色漆</td><td>≤ 30</td><td>汽车总装厂自定标准</td></tr><tr><td>深色漆 流挂性/μm</td><td>25 25</td><td>汽车总装厂自定标准</td></tr><tr><td>杂质/点 ≤</td><td>40</td><td>汽车总装厂自定标准</td></tr><tr><td>干燥时间/min ≤ 140°C</td><td>30</td><td>GB 1728—1979</td></tr><tr><td>110°C</td><td>30</td><td></td></tr><tr><td rowspan=\"14\">漆膜</td><td>贮存稳定性（12个月）/级</td><td>沉降不大于0，各项性能不下降</td><td>GB 6753.31986</td></tr><tr><td>漆膜光泽（45*)/% 》</td><td>95</td><td>GB 17431979</td></tr><tr><td>镜面成像清晰度/PGD 硬度（双接仪）/</td><td>0.30（垂直面）</td><td></td></tr><tr><td>标准烘干 低温烘干</td><td>0.60 0.40</td><td>GB 1730—1988</td></tr><tr><td>抗拉伸性/mm ≤</td><td>10</td><td>ASTM MD522—1960</td></tr><tr><td>冲击性/cm ≥</td><td>30</td><td>GB 1732—1979 GB9753-1988</td></tr><tr><td>杯突性能/mm ≤</td><td>5</td><td></td></tr><tr><td>切割附着力（1mm）/级 耐水性（40C×240h）/级</td><td>1</td><td>GB 92861988</td></tr><tr><td>耐汽油性（120*汽油，24h）/级</td><td>起泡0级.1h恢复，允许轻微变色</td><td>GB 1733-1979</td></tr><tr><td></td><td>不起随 0级,1h恢复,不变色,不失光,硬度</td><td>GB 1734—1979</td></tr><tr><td>耐润滑油性（QC-30”油，24h）/级</td><td>不起牌0级，1b恢复,不变色，不失光，硬度</td><td>GB 9274-1988</td></tr><tr><td>抗二甲苯性（5min，恢复5min） 耐酸性(0.05mol/L HzSO ,24h)/级</td><td>无斑点，不变色 光率泡0级，刺落0级，不起皱，轻微变色,失</td><td>GB 9274-1988 GB 17631979</td></tr><tr><td></td><td></td><td></td></tr><tr><td>耐碱性（0. 1mol/L NaOH,24h)/级 耐湿热性[（47±1)C，RH（95 ±</td><td>光率不大级，刺落0级，不起皱，轻微变色，失 1</td><td>GB 1763-1979 GB 1740-1979</td></tr><tr><td rowspan=\"2\">2）%]/级</td><td>起泡、生锈、开裂、剥落为0级，失光不大于</td><td></td><td></td></tr><tr><td>耐老化性（人工加速老化，700h）/级</td><td>1级，允许轻徽变色（E≤2)</td><td>GB 1865-1980</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>类别</td><td>颜色与外观</td><td>技术指标</td><td>标准</td></tr><tr><td rowspan=\"5\">漆膜</td><td>耐候性（海南曝晒场，12个月）/级</td><td>综合等级：优</td><td>GB 1766,71979</td></tr><tr><td>耐低温性（10周期）/级</td><td>失光率：0级，裂纹：10</td><td>GB 92771988 Ford B 17-2</td></tr><tr><td>漆膜修补性（面30~40um，标准 条件下烘干，喷面漆 20~40pm,标准</td><td>层补部分与锋补部分颜色符合标准板，</td><td>汽车总装厂自定标准</td></tr><tr><td>过烘干性能（160C×30min）</td><td>颜色符合标准板</td><td></td></tr><tr><td>过喷施工性能（50~60μm）</td><td>无针孔、气泡</td><td></td></tr><tr><td>静电施工性能</td><td>适用于静电喷涂</td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1067,
+        "chunk": "# 第四节底盘抗石击涂料  \n\n汽车在高速运行中，快速滚动的车轮极易带起砂石、泥沙等，使车身受到强烈的冲击。这些砂石表面如果沾染有化学药品、防冻剂以及冬季用于融化道路表面冰层的食盐等，对汽车就会造成更为严重的损害。显然这种砂石冲击对汽车前盖和底盘的危害性较大，而首当其冲的无疑是汽车底盘。砂石冲击在破坏涂层的同时，也在破损部位带来了腐蚀的隐患。汽车制造者们为了尽可能减少此类现象的发生，采取了车身密封和底盘防护的措施，西方汽车业同行大都认为：密封胶和底盘防石击涂料不仅仅起密封和底盘抗石击作用，更为重要的是对车身焊缝和切口等部位起防腐蚀作用。  \n\n早先的密封胶和底盘防石击涂料大多采用同一品种，即PVC密封胶和PVC塑溶胶。后来则发展了线型聚酯-氨基、环氧-聚酯-封闭异氰酸酯等抗石击涂料，现分述如下。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1068,
+        "chunk": "# 一、PVC塑溶胶  \n\n塑溶胶类涂料乃是将某些热塑性塑料、橡胶等以溶胶形式分散在有机介质中。适用的热塑性塑料有聚氯乙烯、氯乙烯共聚物；橡胶有丁二烯-苯乙烯共聚物、乙烯-丙烯-丁二烯三元共聚物等。普遍用作汽车底盘塑溶胶的则是聚氯乙烯（PVC)。PVC与某些颜、填料一起制得的塑溶胶烘烤干燥后具有一定弹性和柔韧性，因此抗石击性能良好。但这类塑溶胶在经磷化处理过的钢板或涂装过CED的表面附着性能极坏，所以必须添加一种增黏剂，以提高其附着性能。适用的增黏剂一般采用以聚酰胺、多元醇、硫醇等为封闭剂的封闭型异氰酸酯。  \n\n典型配方及工艺如下。  \n\n(1）配方（质量份）  \n\n<html><body><table><tr><td>聚氯乙烯树脂</td><td>20.0 硅灰石</td><td></td><td>10.5</td></tr><tr><td>氯乙烯共聚物</td><td>10.0</td><td>重质硫酸</td><td>20.0</td></tr><tr><td>邻苯二甲酸酐二癸酶</td><td>30.0 碳酸钙</td><td></td><td>4.5</td></tr><tr><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n(2）工艺将上述组分投人到混炼机中混炼均匀，即可得塑溶胶。  \n\n塑溶胶产品的细度大都不作为关键指标控制，一般为90～200um，均采用高压无气喷涂的方式涂装，烘烤条件一般为（120～160℃）×（20～60min）。其主要技术指标有：剪切强度（≥0.5MPa）、吸水率（≤10%～15%）、尺寸稳定性（≤10%～20%）、热稳定性（180℃过烘烤时间≥45～60min）、柔韧性（锥弯曲试验≤10mm）等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1069,
+        "chunk": "# 二、聚酯型  \n\n由于PVC型塑溶胶性防石击涂料一般都需要涂装到 $500{\\sim}1000{\\mu}\\mathrm{m}$ 以上，大大增加了汽车车身的自重，故近年来已逐渐淡出汽车底盘涂料市场。取代它的有线型聚酯树脂-氨基-封闭型异氰酸酯、聚醚-聚酯-氨基等新型防石击涂料。值得注意的是：上述几乎所有聚酯树脂的合成中大都采用长链脂肪族羧酸、长链多元醇等以使聚合物的大分子主链具有相当的柔性。现举一例可用于底盘防石击涂料的聚酯树脂供参考。  \n\n（1）配方（质量份）  \n\n邻苯二甲酸酐 36.28 新戊二醇 30.17   \n己二酸 12.12 聚乙二醇（4000） 13.88   \n三羟甲基丙烧 7.50 二丁基氧化锡 0.05  \n\n(2）工艺  \n\n$\\Phi$ 将上述物料全数投入到反应釜中， ${\\bf N}_{2}$ 保护下升温至 $180\\sim240^{\\circ}\\mathrm{C}$  \n\n$\\textcircled{2}$ 待 $\\mathbf{AV}{\\leqslant}10$ 时，降温至 $120\\Upsilon$  \n\n③将物料放至加有100#芳烃、醋酸甲氧基丁酯（3：1）的兑稀釜中，使之兑稀成固含量大约为 $61\\%$ 的制品。  \n\n$\\textcircled{4}$ 过滤、包装。  \n\n上述树脂配制的涂料采用高压无气喷涂于CED上，晾置15min后，再在140℃烘烤20min，干膜厚为200μm，漆膜具有良好的耐腐蚀性及抗石击性能。该类型的底盘防石击涂料，膜厚仅仅200μm，这将大大减轻车身的质量，而丝毫不会影响到它的防护功能。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1070,
+        "chunk": "# 第五节汽车修补涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 1071,
+        "chunk": "# 一、汽车修补涂料面漆系统的基本构成  \n\n汽车修补涂装时原则上应该参照该车原有的涂装系统，但在实际应用中，汽车修配厂均采用底漆十中间涂料十腻子十面漆这种组合以满足绝大多数客户的需要。汽车修补涂料系统大体包括色母、清漆、调和清漆、中间涂料（二道浆）、腻子（填眼灰、原子灰）、底漆、固化剂、稀释剂、各类辅料以及与之配套的调色软件或菲林（汽车涂料色母配方单）等。  \n\n近年来ICI、DuPont、BASF、Herberts等外国著名汽车涂料公司产品相继进入国内汽车修补涂料市场，国内一些新建的修补涂料厂家也纷纷参照这些公司的配置模式设计自身的系统。即在面漆方面本色漆采用双组分丙烯酸-聚氨酯类，俗称2K系统；而金属闪光漆采用单组分热塑性丙烯酸底色漆（也有个别厂家采用聚酯树脂底色漆）十双组分丙烯酸-聚氨酯罩光清漆组合，俗称1K系统。中间涂料（或称为二道浆、苏灰士等）方面则以硝基纤维素类为主，也有部分采用双组分丙烯酸-聚氨酯类或聚酯-聚氨酯类。俗称填眼灰的腻子则多采用硝基纤维素类，另外有的则采用原子灰作较大缺陷的修补。底漆则多采用双组分环氧树脂类，而双组分聚氨酯类较为少见。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1072,
+        "chunk": "# 1.面漆的品种  \n\n汽车修补漆的面漆早期几乎清一色都是硝基纤维素系。到了20世纪60年代中期，热塑性丙烯酸树脂类在国外开始大量进入市场，并取代硝基纤维素类涂料而成为汽车修补主导产品。20世纪60年代国外研发的品种还有硝基改性丙烯酸树脂涂料、醋酸丁酸纤维素（CAB）改性丙烯酸树脂涂料等。20世纪70年代中期一系列双组分涂料开始进入市场，如硝基纤维素/丙烯酸/异氰酸酯、丙烯酸/异氰酸酯等。这些产品综合了挥发型涂料的快干性以及由于异氰酸酯参与交联反应使得漆膜性能获得较大程度的提高等两方面的特点，受到广大用户的欢迎。这些产品发展迅速，很快就成为汽车修补涂料中本色漆（即2K系列）特别是清漆市场的主导产品。  \n\n目前国外几种主要汽车修补涂料的市场占有率因来自不同的文献资料而有所不同，有的数据显示硝基纤维素系涂料已经完全退出汽车修补涂料市场。  \n\n<html><body><table><tr><td>聚酶-聚氨酯树脂涂料/%</td><td>60~65</td><td>CAB改性丙烯酸树脂涂料/%</td></tr><tr><td>丙烯酸-聚氨酯树脂涂料/%</td><td>20~25</td><td>1</td></tr><tr><td>热</td><td>其他/% 5~10</td><td></td></tr></table></body></html>  \n\n然而也有资料显示，硝基纤维素系涂料仍然占有一定的市场份额，西欧占到 $5\\%$ ，其他地区则超过 $10\\%$ 要  \n\n值得注意的是，近年来汽车行业以轻量化、防腐蚀为基点，汽车用材料已经有了较大的改变，非铁金属以及塑料等所占的比例越来越高。随着合成树脂材料、镀锌板以及铝合金材料的大量使用，势必影响到涂料品种尤其是配套底漆品种的改变。在对采用轻合金和塑料较多的车辆进行修补加工时就应充分注意到上述情况。2002年汽车上各种材料所占份额如图  \n\n在我国仍然有少数厂家采用较低档的其他品种，如硝基纤维素涂料、醇酸树脂系涂料等。采用这类涂料的主要原因有两个：一是喷漆工对于硝基纤维素涂料等传统涂料比较习惯；二是因为这类产品价格低廉。另外尚有部分国外名牌产品也向国内市场推出硝基纤维素涂料系统，如ICI的贝高（BELCO）系列，各项性能也都不错。因此在我国这类品种仍然占有一定的市场份额也就不足为奇了。  \n\n![](images/bcff112a1497964aa30a7a9a3192b51d85909ad764a1d798311ea0eb702ae492.jpg)  \n图3-2-82002年汽车上各种材料所占份额",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1073,
+        "chunk": "# 2.色浆 (色母)  \n\n在汽车修补涂料行业大都把作为商品之一的色浆称之为“色母”，另外也有人将冲淡前的浓色浆称为色母，而将冲淡后的产品才叫做色浆，应该说这是比较合理的称谓。汽车修补涂料行业则因其自身特点以及市场供货方面的需要，普遍采用单色浆法，并且以这些色浆构成一整套自有的调色系统，同时这些色浆（色母）还作为商品直接进入市场。  \n\n建立色浆系统首先考虑的就应该是颜色。一般人们习惯用三元刺激值来描述颜色，即色调、明度及色饱和度。三元刺激值构成一个颜色的立体坐标。立体坐标的球面可看作完整颜色空间的反映。专业的汽车修补涂料生产厂家大都备有一套色浆系统，以便借助这些色浆调配出各色汽车面漆。色浆系统的构成是一个厂的技术关键。衡量它是否实用或完善的判定标准就是考量该系统对整个颜色空间的覆盖程度。常听调色工反映：在调配一些比较特殊颜色的汽车漆时，采用国内某些品牌的色母很难调到位，而采用进口色母系统时，却比较容易完成就是这个道理。国外名牌汽车修补涂料生产厂家都有一套相对完整的色浆系统，这些系统包含的色浆一般都有上百种之多，且有专用电脑调色软件支持，以方便客户选择使用。一般进口名牌色浆系统的配备相当完全，如仅仅是蓝色色浆就按照不同色调、不同透明度最多设置达六七个之多。除此而外，他们甚至对同一颜料还配置了几种不同的含量，以此构成色浆色强度的梯度差，为客户调色尤其是金属闪光底色漆的调色提供方便。各涂料公司每年都会发布、推出一些新的色浆，淘汰一些用处不大的旧色浆，以不断完善自己的色浆系统，足见国外汽车修补涂料同行对色浆及其系统的高度重视。  \n\n大多数汽车修补涂料公司提供的单色浆可细分为金属闪光底色漆用色浆、银浆（包括珠光粉浆）（1K）和本色漆（汽车修补行业多称为实色漆、纯色漆）用双组分色浆（2K)。但也有少数几家公司向市场推出1K和2K系统中均可采用的通用色浆，如DoPont、广州浩宇等。应该说这类更加通用的色浆系列虽然可为客户提供不少方便，但在技术上给涂料生产厂也将带来一定难度，如在性能方面不打折扣，将是非常理想的。  \n\n作为一个合格的单色浆需具备以下条件：  \n\n$\\textcircled{1}$ 不仅仅要求与本公司1K和2K系统主成膜物质的混容性良好，最好和市面上常见的汽车修补涂料系统的混容性也好；  \n\n$\\textcircled{2}$ 贮存和运输过程中，无分层、絮凝、返粗现象；  \n\n$\\textcircled{3}$ 色调、色强度、色纯度稳定，无任何色污染；  \n\n$\\textcircled{4}$ 黏度适当，可适当流动，易于操作；  \n\n$\\textcircled{5}$ 对成品漆各项性能几乎无影响；  \n\n$\\textcircled{6}$ 混入基料及其他组分的工艺简洁，只需低剪切速率下揽拌、加入即可，不要求“在高剪切速率分散的条件下，尽可能慢慢地加入”。届时不会产生絮凝、返粗甚至结块等病；$\\textcircled{7}$ 研磨树脂及分散助剂的用量相对较低，以尽量减少它们对最终产品性能的影响。  \n\n汽车修补涂料中用到的色浆系统主要包含两大类，即含普通彩色颜料（包括钛白、炭黑）的色浆和含铝粉、珠光粉、纳米级钛白之类效应颜料的色浆，现分述如下。  \n\n（1）彩色颜料色浆彩色颜料色浆主要由研磨树脂、颜料、助剂、基料树脂以及溶剂所构成。制造步骤是先将颜料在润湿分散助剂的协助下分散在研磨树脂中，然后再用基料树脂将其冲淡成一定浓度，制得色浆。鉴于市场上均习惯将它们称之为色母，姑且把冲淡前的浓色浆称为色浆，把冲淡后的可以作为商品上市的色浆称为色母。  \n\n$\\textcircled{1}$ 研磨树脂如前所述，研磨树脂的选择至关重要，作为一个合格的通用色浆的研磨树脂应具备如下条件。  \n\na.混容性研磨树脂至少应与本系统内（1K和2K）各类树脂的混容性良好，最好和市面上各种品牌漆料的混容性也都好，这样可以进一步拓宽本系统在市场上的竞争性。目前世界上大多数汽车修补涂料系统中所采用金属闪光底色漆均为单组分，即通常所说的1K，而本色漆则均为双组分，即2K。它们的主成膜物质分别采用热塑性丙烯酸树脂和热固性丙烯酸树脂。熟悉丙烯酸酯聚合物化学的人都知道，这两类树脂一般互不相容。因此要求研磨树脂和这两类树脂都能混容，这就在相当大的程度上缩小了可能选择的范围。  \n\nb.分散性对各类颜料（包括有机、无机颜料）的润湿性、分散性均优。  \n\nc.对成品性能影响各种色浆配漆后，对成品漆的物理力学性能、耐极性、非极性介质性能、耐老化性能等均无不良影响。  \n\n可用作单色浆的研磨树脂主要有醛酮树脂、含特殊活性单体的丙烯酸树脂、改性聚酯树脂等。目前可见到的实用商品均依赖进口，如BASF公司的LaropalA81、K80，德固萨的KunstharzTC属醛酮树脂类。我国大昌树脂（惠州）的DC288R、台湾加合的D-11、D-12，罗门哈斯的 Acryloid B66、Acryloid B99、DM55，Kemperial公司的 KCR-2014以及EFKA公司的EFKA-1101、EFKA1120、EFKA1125、EFKA1500等属于丙烯酸树脂类或改性聚酯树脂类。D-11和KCR-2014 的规格见表3-2-29。EFKA公司产品见表3-2-30。  \n\n表3-2-29通用色浆树脂牌号规格  \n\n\n<html><body><table><tr><td>规格</td><td>D-11</td><td>D-12</td><td>KCR-2014</td><td>DC288R</td></tr><tr><td>外观</td><td>稍带浅黄色黏稠液体</td><td>浅色黏稠液体</td><td>白色黏液体</td><td>白色黏稠液体</td></tr><tr><td>颜色(Fe-Co比色号）≤</td><td>2</td><td>1</td><td>1</td><td>1</td></tr><tr><td>不挥发分/%</td><td>57.0 ±1.5</td><td>57.0±1.5</td><td>55. 0 ±1. 0</td><td>55.0±1.0</td></tr><tr><td>黏度（加氏管）</td><td>U~X</td><td>X~Z</td><td>U~Z</td><td>U~Z</td></tr><tr><td>羟值</td><td>20</td><td>20</td><td></td><td>25</td></tr><tr><td>溶剂</td><td>二甲苯、酰酸甲氧基丙酯</td><td>醋酸甲氧基丙酯</td><td>二甲苯、酯酸甲氧基丙酯</td><td>醋酸甲氧基丙酯</td></tr></table></body></html>  \n\n表3-2-30EFKA公司通用色浆树脂  \n\n\n<html><body><table><tr><td>规格</td><td>EFKA-1101</td><td>EFKA-1120</td><td>EFKA-1125</td><td>EFKA-1500</td></tr><tr><td>改性丙烯酸聚合物</td><td>改性丙烯酸聚合物</td><td>丙烯酸-醇酸</td><td>改性醇酸树脂</td><td>脂肪酸改性聚合物</td></tr><tr><td>颜色（Fe-Co比色号）≤</td><td>3</td><td>5</td><td>5</td><td>5</td></tr><tr><td>不挥发分/%</td><td>56~61</td><td>64~66</td><td>69~71</td><td>89~91</td></tr><tr><td>相对密度</td><td>1. 01~1.04</td><td>1.00~1.02</td><td>1.03</td><td>1.04~1.06</td></tr><tr><td>闪点/℃</td><td>24</td><td>30</td><td>41</td><td>36</td></tr><tr><td>溶剂</td><td>酸酸丁酯、酯酸甲氧基丙酯</td><td>醋酸丁酯、烷基苯</td><td>烷基苯</td><td>丙二醇甲醚</td></tr></table></body></html>  \n\nA81树脂为醛酮类固体树脂，使用前需先溶解在适当混合溶剂内。它与大多数涂料用合成树脂的混容性都好，但因为A81树脂性脆，用量稍高时，漆膜硬度高，但柔韧性也会急剧下降。使用时应尽可能控制它的用量。KCR-2014、D-11、D-12的混容性、颜料分散性、成膜后的物性都不错，但加量过多时对本色漆的光泽有一定影响。  \n\n$\\textcircled{2}$ 基料树脂颜料分散于研磨树脂中制成浓浆后还要分别用1K和2K树脂冲淡成一定浓度，得成品色母。2K树脂是高羟基含量的丙烯酸树脂。1K树脂是含少量羟基或其他活性基团的热塑性丙烯酸树脂。  \n\n实际生产中厂家大都将所用树脂配制成溶液，即所谓1K和2K调合漆料。调合漆料中均加有成品漆中应有的各种成分，如流平剂、催干剂、防沉剂以及各种溶剂等，以免冲淡调配加工时，配方中各种成分的配比发生改变。调合漆料的典型配方见表3-2-31。  \n\n表3-2-311K和2K调合漆料配方  \n\n\n<html><body><table><tr><td>组成</td><td>1K调合漆料2K调合漆料</td><td></td><td>组成</td><td></td><td>1K调合漆料2K调合漆料</td></tr><tr><td>醋酸乙酯</td><td></td><td>0.50</td><td>BYK 358</td><td></td><td>0.40</td></tr><tr><td>醋酸丁酯</td><td>29.52</td><td>14.00</td><td>BYK 325</td><td>0.37</td><td></td></tr><tr><td>二甲苯</td><td>6.15</td><td></td><td>月桂酸二丁基锡（1%）</td><td></td><td>0.10</td></tr><tr><td>100°芳经溶剂</td><td>7.38</td><td>7.20</td><td>CAB 381-2(10%)</td><td>8.61</td><td></td></tr><tr><td>DBE</td><td></td><td>3.50</td><td>Disper KC568溶液(6%)</td><td>12.30</td><td></td></tr><tr><td>异丁醇</td><td>3.69</td><td></td><td>KCR-2015丙烯酸树脂</td><td>29.52</td><td></td></tr><tr><td>松节油</td><td>2.46</td><td></td><td>高羟基含量丙烯酸树脂（70%）</td><td></td><td>74.30</td></tr></table></body></html>\n\n$\\Phi$ Disper KC 568溶液，NVM为6%。  \n\n有的汽车修补涂料厂为了客户调色、配漆的方便，也以商品形式向客户提供1K和2K的调合漆料。不过此时名称就改为调合清漆了，如ICI公司的P190-376、P017-404等。值得注意的是，调合清漆一般不能充当罩光清漆使用，也不能因成本方面的考虑添加到罩光清漆中。  \n\n$\\textcircled{3}$ 助剂彩色颜料浆的制备中，除了研磨树脂和基料树脂外，润湿分散剂的合理选用也是非常重要的环节。有关在色浆制造中润湿分散剂的作用，在本章第三节有关单色浆内容部分已有评述，这里需要特别强调的是，针对不同的颜料需要采用不同的润湿分散剂，对于那些容易发生絮凝、浮色、发花等病的颜料尤其要注意，如菁系列颜料、紫红系列、各类炭黑等。必要时应采用复合润湿分散剂以增加色浆的稳定性。  \n\n$\\textcircled{4}$ 彩色颜料单色浆制造  \n\na.常规生产法选择适当的研磨树脂、颜料、润湿分散剂以及溶剂，再通过实验验证以确定色浆配方。实验中除了首先应该考核研磨时间、色浆的流动性等性能外，还必须采用两项特殊的试验方法来检验色浆配方的可行性（详见本章第三节面漆部分)。  \n\n在选定了研磨树脂、颜料、润湿分散剂后即可制造色浆，色浆制造分为两步，首先制造浓色浆，然后将浓色浆冲淡成成品色母。  \n\n·浓色浆的制造工艺  \n■在流动缸中加入配方中所列溶剂及润湿分散剂，搅拌均匀。  \n■在搅拌下加入研磨树脂，加完后再搅拌 $30\\mathrm{min}$   \n■在搅拌下慢慢加入颜料，加完后再高速分散 $30\\mathrm{min}$ 。  \n■在砂磨机上研磨至细度小于 $10\\mu\\mathrm{m}$ \\*  \n·冲淡工艺  \n■在流动缸中先加入上述制备的浓色浆。  \n■根据不同品种浓浆黏度的具体情况，在搅拌下分批逐步加入冲淡用调合漆料。  \n\n■第一批投入后，慢搅10min直至浓浆变成均匀、流动性较好的糊状物（批量的大小应根据浓浆的黏度及生产总批量的大小而定)。  \n\n■然后再继续加人后几批冲淡用调合漆料，最后加溶剂，再继续搅拌 $10\\mathrm{{min}}$ 费·典型的浓色浆配方典型的浓浆配方列于表3-2-32中。  \n\n表3-2-32典型色浆配方  \n\n\n<html><body><table><tr><td>配方</td><td>嫣红</td><td>特黑</td><td>皇室蓝</td><td>艳绿</td><td>鲜黄</td><td>橘红</td><td>鲜紫</td></tr><tr><td>RKC 2014 醋酸丁酯 100# Disper KC 563</td><td>52.4 12.2 12.2 8.7</td><td>62.5 7.5 7.5</td><td>46.0 16.0 15.0</td><td>58.0 9.0 9.0</td><td>55.0 10.5 10.5 9.0</td><td>57.4 9.5 9.5 8.5</td><td>56.0 12.0 12.0 7.9</td></tr><tr><td>KC 3010 EFKA 4401 EFKA 6745</td><td></td><td>0.1 10.4 12.0</td><td>7.3 0.7</td><td>8.5 0.5</td><td></td><td>0.1</td><td>0.1</td></tr><tr><td>Poliogen Red 3885 FW 200 HoliogenBlue 6900 Irgalite green 6G</td><td>14.5</td><td></td><td>15.0</td><td>15.0</td><td>15.0</td><td></td><td></td></tr></table></body></html>  \n\n制得浓色浆后，再用1K或2K调合漆料和溶剂将其冲淡成成品色母。  \n\nb.直接溶解工艺彩色颜料色浆的制造除上述工艺外，另外还有一种溶解、冲淡法。20世纪60年代，硝基纤维素涂料比较流行时，涂料行业风行起硝基漆片生产工艺，即将硝基纤维素与颜料预先经研磨分散并压成漆片，生产时只需溶解、调和既可。按照这种工艺生产的硝基纤维素涂料不仅提高了配方的灵活性、简化了生产工艺，而且色相稳定、漆膜光泽也要好于按常规工艺生产的同类产品，可惜国内目前已不多见。但国外在单色浆原料领域还可发现采用类似工艺的漆片产品供应市场。比较典型的是比利时阳光化学公司（Sunchemi-cal KVK）的系列产品。该公司Predisol系列产品中有PredisolC、Predisol N、Predisol V、PredisolCAB等。其中C系列为硝基纤维素漆片，N系列为聚乙烯缩丁醛漆片，V系列为乙烯共聚物漆片。适用于汽车修补涂料中的当然是CAB系列的漆片。该公司在其产品说明书中特别声明：CAB漆片中所采用的高档无机或有机颜料均已通过佛罗里达州的户外曝晒实验。不少汽车修补涂料调色系统的色母制造中都采用了这类漆片，如PredisolBlackFW-CAB 62、Predisol Green 6YH-CAB 678、Predisol Pink E-CAB 663、Predisol Maroon 3BS-CAB 2647等。  \n\n$\\textcircled{5}$ 彩色颜料色浆标准彩色颜料色浆标准中除常见色漆中应有的诸如细度、黏度、不挥发分等指标外，作为调色系统中的一员，最为关键的是色强度和色差两项指标。现举一例汽车修补涂料厂调色系统色浆标准如下。  \n\n表3-2-15中标出了色差和色强度的指标范围，色差 $\\Delta E{\\leqslant}1$ ，色强度波动范围则在 $5\\%$ 以内。由于单色浆不允许调色，如果出现色差，不能通过加人某种色浆来调整色调，所以这两项指标的控制在实际生产中难度极大，要求极严格的质量控制措施和企业管理才能有效实施。  \n\n(2）效应颜料色浆（1K）效应颜料色浆主要由树脂、效应颜料、助剂以及溶剂所构成。  \n\n$\\Phi$ 树脂单组分效应颜料色浆中可采用的树脂绝大部分为含某些极性基团的热塑性丙烯酸树脂。当然也有部分涂料厂选用聚酯树脂或丙烯酸改性醇酸树脂。如果错误地选择了一般热塑性丙烯酸树脂，则市面上作为汽车修补用罩光清漆的丙烯酸-聚氨酯或聚酯-聚氨酯等将无法在底色漆表面形成有效附着，严重时可能会造成整片清漆脱落。  \n\n$\\textcircled{2}$ 效应颜料汽车修补涂料中采用的效应颜料主要有铝粉、珠光粉、纳米钛白粉以及石墨粉等。有关方面知识在汽车原厂漆面漆部分已有介绍，这里就不再赘述。  \n\n$\\textcircled{3}$ 助剂在金属闪光底色漆中采用的助剂主要针对效应颜料的定向、防止这类密度较大的颜料粒子沉降、结块等。分散剂的合理选用对于提高效应颜料（铝粉、珠光粉等）的定向、改善施工性、增强闪烁效应、减少在罐内沉降倾向、改善清漆层的映象清晰度都能够发挥非常关键的作用。可采用的助剂主要有以下几类：分散蜡、醋酸丁酸纤维素和润湿分散剂。  \n\na.分散蜡适用于金属闪光漆中的分散蜡主要有两大类，即乙烯类共聚物（包括乙烯-醋酸乙烯共聚物、乙烯-丙烯酸共聚物等）和聚酰胺蜡。Cerafak100、Cerafak103、Cerafak106是毕克公司用于溶剂型金属闪光漆中的蜡分散体。Cerafak100、Cerafak106均为乙烯-醋酸乙烯共聚物分散体（EVA)。而Cerafak103为乙烯-丙烯酸共聚物。DisperKC568为KemperialCo.产分散蜡系防沉剂，属于-种改性乙烯-醋酸乙烯类共聚物。Disparlon6900-20X为日本楠本化成株式会社产品，它是聚酰胺在二甲苯溶液中通过溶胀而形成的蜡质糊状物。  \n\n这两类分散蜡助剂用于各类溶剂型金属闪光底色漆中，都能起分散、防沉和定向等方面的作用。它们不仅大大改善了该类产品中的效应颜料（铝粉、珠光粉以及超细钛白等）在漆浆和成品底色漆中的分散性、沉降性能，而且还有效地改善了效应颜料的定向作用，使之具有更好的白度和随角异色性、较少的云斑色差和雾影等。  \n\n比较这两类助剂总效果大体相差不多，但Disparlon 6900-20X和Disper KC568的增稠效果明显，而BYK的Cerafak106在这方面表现稍差。  \n\nb.醋酸丁酸纤维素（CAB）CAB在金属闪光底色漆中和分散蜡助剂一样，对效应颜料起定向、防沉等方面的作用，另外它还是辅成膜物质，对于湿涂层的溶剂释放性、湿喷湿施工性以及漆膜硬度的改善都有非常重要的作用。依士曼公司商品牌号及规格见表3-2-33。  \n\n表3-2-33伊士曼公司CAB商品牌号及规格  \n\n\n<html><body><table><tr><td>商品牌号</td><td>乙酰基/%</td><td>丁酰基/%</td><td>羟基/%</td><td>黏度/s</td><td>T/C</td></tr><tr><td>CAB 551-0. 01</td><td>2.0</td><td>53. 0</td><td>1.5</td><td>0.01</td><td>85</td></tr><tr><td>CAB 551-0. 2</td><td>2.0</td><td>52. 0</td><td>1. 8</td><td>1.20</td><td>101</td></tr><tr><td>CAB 381-0.1</td><td>13.5</td><td>38.0</td><td>1.3</td><td>0.10</td><td>123</td></tr><tr><td>CAB 381-0. 5</td><td>13.5</td><td>38.0</td><td>1.3</td><td>0.50</td><td>130</td></tr><tr><td>CAB 381-2</td><td>13.5</td><td>38.0</td><td>1.3</td><td>2.00</td><td>133</td></tr><tr><td>CAB 381-2BP</td><td>14.5</td><td>35.5</td><td>1.8</td><td>2.20</td><td>130</td></tr></table></body></html>\n\n$\\Phi$ 黏度测定按ASTMD817标准。  \n\n从表3-2-34中不难看出：伊士曼商品牌号中几行数字的含义，即CAB381-0.5表示其丁酰基含量为 $38\\%$ ，黏度为0.5等，以此类推。  \n\n国内生产CAB的厂家不多，最早是杭州化工设计研究院研发了此类产品（表3-2-34），效果不错，但在价格上与国外同类产品比较并不占多大优势。  \n\n表3-2-34国产醋酸丁酸纤维素型号及规格  \n\n\n<html><body><table><tr><td>型号</td><td>丁酰基/%</td><td>乙酰基/%</td><td>黏度/Pa·s</td><td>游离酸/% ≤</td><td>水分/%</td></tr><tr><td>CAB-15-1</td><td>13~18</td><td>29~34</td><td>0.9~1.3</td><td>0.06</td><td>3</td></tr><tr><td>CAB-15-2</td><td>13~18</td><td>29~34</td><td>1.3~1.7</td><td>0.06</td><td>3</td></tr><tr><td>CAB-35-1</td><td>34~38</td><td>13~18</td><td>0.4~0.8</td><td>0.06</td><td>3</td></tr><tr><td>CAB-55-1</td><td>50~55</td><td>2~5</td><td>0.5</td><td>0.06</td><td>3</td></tr></table></body></html>  \n\n选用时可参考有关数据，实际使用的配方中，大都选择至少两种CAB搭配，如CAB551系列与CAB381系列搭配使用，或选择CAB381系列不同黏度的产品搭配等。  \n\nc.润湿分散剂多数情况下，添加润湿分散剂有助于效应颜料分散和提高贮存稳定性。适用的润湿分散剂有BYK P 104S、Disperbyk 161、Disper KC 763A、EFKA 5054等。  \n\n$\\textcircled{4}$ 效应颜料色浆的制造金属闪光涂料独特的光学效果不单单来自效应颜料本身，而且和成膜物质、助剂、溶剂、生产工艺，甚至施工工艺都息息相关。在选定了各种组分、确定了配方之后，下一个重要环节就是生产加工。在本章第三节中已经讲述过铝粉、珠光粉之类效应颜料的分散与彩色颜料不同，它们独特的鳞片状的结构不允许承受高剪切力作用。即分散时不能采用高速搅拌的道理，汽车修补漆系统中效应颜料色浆的制造常识与原厂漆基本雷同，生产工艺及流程、注意事项等均可参考有关内容。  \n\n效应颜料色浆配方举例：效应颜料色浆中效应颜料的用量因品种不同而有所差异，大体的用量范围为：铝粉 $5\\%\\sim8\\%$ ，珠光粉 $8\\%\\sim12\\%$  \n\n有些公司某些品种银浆的铝粉用量较大，如ICI公司的98系列银浆。不过这类银浆使用前需添加一定量的控银剂，到施工时，铝粉的含量和上述正常值接近。  \n\n·铝粉颜料浆（质量份）  \n\n\n<html><body><table><tr><td>醋酸丁酯</td><td>21.2</td><td>CAB 551-0. 01(10%)</td></tr><tr><td>二甲苯</td><td>15.7</td><td>KCR2015丙烯酸树脂</td></tr><tr><td>100*芳烃溶剂</td><td>6.4</td><td>分散蜡液（6%）</td></tr><tr><td>丁醇</td><td>5.2</td><td>Disper KC 563B</td></tr><tr><td>DBE</td><td>2.5</td><td>Sparkle Silver 3000-AR</td></tr><tr><td>CAB 381- 2(10%)</td><td>3.3</td><td>Sparkle Silver 5000-AR</td></tr></table></body></html>\n\n①分散蜡液：Disperlon6900-20X或DisperKC568因稠度较大，使用前均需预制成分散蜡液，制备方法是在揽拌下将二甲苯慢慢加入到分散蜡中，使之形成稀状可流动液体。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1074,
+        "chunk": "# ·珠光粉颜料色浆配方（质量份）  \n\n<html><body><table><tr><td>醋酸丁酯</td><td>21. 0</td><td>CAB 551-0. 01(10%)</td><td>3.1</td></tr><tr><td>二甲苯</td><td>12.2</td><td>KCR-2015丙烯酸树脂</td><td>25.0</td></tr><tr><td>100*芳烃溶剂</td><td>8.2</td><td>分散蜡液（6%）</td><td>10.3</td></tr><tr><td>丁醇</td><td>3.1</td><td>Disper KC 563B</td><td>0.3</td></tr><tr><td>DBE</td><td>2.1</td><td>Iriodin 9514 WRII</td><td>10.0</td></tr><tr><td>CAB 381-0.1(10%)</td><td>4.2</td><td></td><td></td></tr></table></body></html>  \n\n上述两个配方中列出了铝粉、珠光粉配制色浆的基本组成和配比。因铝粉、珠光粉品种不同，配方中采用的溶剂和主成膜物质的用量会有所变动，但大体应在上述配方规定的范围内，使用时可灵活掌握。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1075,
+        "chunk": "# 3.交联剂及其他助剂  \n\n(1）交联剂双组分丙烯酸-聚氨酯的固化交联剂部分是异氰酸酯类化合物。由于汽车修补涂料的外用、高耐候、高装饰性等特定要求，因此这里所能够采用的也只能是脂肪族或者是脂环族类不泛黄、耐候性特别突出的异氰酸酯类化合物。六亚甲基二异氰酸酯（HDI）的部分水解物——缩二脲是出现最早、应用得也最为普遍的外用双组分聚氨酯用固化剂。随着汽车工业以及涂料工业的发展，涂料品种档次的不断提高，性能更为突出的新型固化交联剂也相继问世，使得以往HDI缩二脲一花独放的不可替代的主导地位受到有力的挑战。新问世的产品主要有HDI三聚体、异佛二酮二异氰酸酯（IPDI）三聚体以及IPDI-TMP加成物等。现分述如下。  \n\n$\\textcircled{1}$ HDI缩二脲六次甲基二异氰酸酯（HDI）是最为典型的脂肪族异氰酸酯类。但是由于这种单体型化合物的分子量不大，有一定的挥发性和毒性，故工业上很少不经改性而直接使用。早期涂料行业大都采用被称之为缩二脲的化合物。缩二脲可用酯类或芳烃溶剂稀释，但不溶于脂肪族烃类溶剂。另外，溶剂分子中也不允许含有活性氢一类可与异氰酸酯基反应的基团，如醇类、胺类等。缩二脲对潮湿极为敏感，因此必须使用所谓“聚氨酯级”的溶剂（水分含量低于 $0.05\\%)$ 。尽管如此，它被稀释后的不挥发分仍然不得低于 $35\\%\\sim$ $40\\%$ ，否则即使采用的是“聚氨酯级”的溶剂，经过一段时间存放后，仍然会出现浑浊或沉淀等水解迹象。因此在一般情况下，最好不要将缩二脲稀释后保存。  \n\n$\\textcircled{2}$ HDI三聚体HDI三聚体与HDI缩二脲相比较具有干燥速率快、漆膜硬度高以及耐候性可得到进一步改善等方面的特点。这主要是因为该三聚体具有因自聚而形成的六元环结构，这种结构表现出较高的光、热稳定性。HDI三聚体的主要特点如下。  \n\na.快干，大大减少了涂装后漆膜沾灰的可能性，提高了涂装效率。  \nb.相对缩二脲而言，漆膜的硬度较高。  \nc.耐候性优良。  \nd.具有一定的耐温性能。  \n\n一般HDI三聚体与常用有机溶剂均有着良好的混容性，如酯类、醚酯类以及芳烃溶剂；脂肪烃类溶剂不适合含HDI三聚体的系统。  \n\nHDI三聚体与含羟基的丙烯酸系聚合物、含羟基聚酯树脂均有良好的混容性，亦可与缩二脲、异佛尔酮二异氰酸酯的衍生物混容（表3-2-35）。 1o)  \n\n表3-2-35HDI三聚体与缩二脲对漆膜干性、硬度影响比较  \n\n\n<html><body><table><tr><td>项 目</td><td>缩二脲</td><td>三聚体</td><td>项目</td><td>缩二豚</td><td>三聚体</td></tr><tr><td>干燥速度</td><td></td><td></td><td>60CX30min</td><td>5B</td><td>3B</td></tr><tr><td>表干/min</td><td>。6。</td><td></td><td>70C×30min</td><td></td><td>3B</td></tr><tr><td>实干/h</td><td>3.8</td><td></td><td>80°℃X30min</td><td></td><td>H</td></tr><tr><td>烘千硬度</td><td></td><td></td><td>100°C× 30min</td><td>BF阳 2H</td><td>2H</td></tr></table></body></html>  \n\nHDI三聚体作为双组分汽车修补涂料的固化剂尽管有着许多明显的优越之处，但与缩二脲相比仍然有一些不足之处，如柔韧性欠佳，价格也稍高等。因此在实用中大多推荐与缩二脲混拼的办法。  \n\n$\\textcircled{3}$ 异佛尔酮二异氰酸酯（IPDI）三聚体从1960年开始赫斯公司就开始了丙酮、异佛尔酮有关化学的研究，经过多年的努力，该公司的技术人员研发出一种新型脂环族异氰酸酯类，即异佛尔酮二异氰酸酯(IPDI)。他们认为这种新型异氰酸酯的衍生物极有可能成为新一代汽车修补涂料用固化交联剂。大约又经过了近20年的不懈努力，终于研发出一种IPDI系新型衍生物—IPDI三聚体。他们将这种IPDI三聚体用来取代HDI缩二脲或HDI三聚体取得成功，使得外用双组分聚氨酯涂料的广大用户在固化交联剂方面又有了一个不错的选择余地。IPDI三聚体商品牌号见表3-2-36。  \n\n表3-2-36IPDI三聚体商品牌号  \n\n\n<html><body><table><tr><td>项目</td><td>T1890E</td><td>T1890L</td><td>T1890M</td><td>T1890/100</td><td>Z4370</td></tr><tr><td>产地 不挥发分/% NCO/% 黏度(23℃)/mPa· s 残留IPDI单体含量/% <</td><td>赫斯公司 69~71 12.0±0.3 650~1150 0.5 醋酸丁酯</td><td>赫斯公司 69~71 12.0±0.3 1300~2100 0.5 醋酸丁酯 /100芳经溶剂</td><td>赫斯公司 69~71 12.0±0.3 3400~4600 0.5 Kristallo L30</td><td>赫斯公司 100 17.0±0.3 0.5</td><td>拜耳公司 70 11.5 1300~2700 0.5 PMA/二甲苯</td></tr></table></body></html>\n\n注：Kristallo L30为芳烃含量19%的石油溶剂，沸程范围130～175C；Shellsol A为混合芳烃，沸程范围165～179C；PMA为醋酸甲氧基丙酯。  \n\nIPDI与其他脂肪族或脂环族异氰酸酯相比，具有下述特点。  \n\na.与各类树脂、溶剂的混容性都非常好，它们可用芳烃或酯类溶剂稀释到 $10\\%$ 而不会出现浑浊或沉淀现象，为使用者设计配方带来极大的方便。  \n\nb.对空气中潮湿的敏感性相对偏低，这样在设计甲、乙两组分配比时可以不考虑NCO损失。OH与NCO之比可以由常用的 ${\\bf\\Phi}_{1}:{\\bf\\Phi}_{1,\\ 1}$ 降低为 $1:1$ 。同时还可以减少或避免因湿度较低而引起的一些漆膜病。  \n\nc.IPDI单体或三聚体的毒性较低。  \n\n<html><body><table><tr><td>口服 LDso/(mL/g)</td></tr><tr><td>IPDI</td></tr><tr><td>2.5 0.123</td></tr></table></body></html>  \n\n从上述数据可知，IPDI的毒性相当较低，与TDI相比几乎可以说不是一个数量级的化学物质。IPDI三聚体与目前市面上所普遍采用的HDI缩二脲和HDI三聚体的某些性能比较具有如表3-2-37所示的特点。 X5 O  \n\n表3-2-37IPDI三聚体与HDI缩二脲和HDI三聚体的某些性能比较  \n\n\n<html><body><table><tr><td>项目</td><td>HDI三聚体</td><td>HDI缩二脲</td><td>IPDI三聚体</td></tr><tr><td>活性</td><td>高</td><td>稍低</td><td>低</td></tr><tr><td>对潮湿的敏感性</td><td>高</td><td>高</td><td>较低</td></tr><tr><td>配漆时配比NCO/OH</td><td>(1. 1~1.5)  1</td><td>(1.1~1.5) + 1</td><td>1:1</td></tr><tr><td>混容性</td><td>有限</td><td>有限</td><td>好</td></tr><tr><td>不沾灰干燥</td><td>有限</td><td>较差</td><td>良好</td></tr><tr><td>毒性</td><td>较高</td><td>较高</td><td>较低</td></tr><tr><td>价格（相对）</td><td>1</td><td>1</td><td>1.25</td></tr></table></body></html>  \n\n从表3-2-37中数据可知，IPDI三聚体除价格稍高外，其他性能均比HDI的衍生物要好  \n\n一些。  \n\nIPDI三聚体在国外早已用于汽车修补涂料中。众所周知，作为汽车修补涂料的原料，除了要求一定的性能外，还要具有尽可能好的与其他原料的混容性。由于IPDI三聚体系列与各种树脂的混容性都好，它们几乎可以和所有的含羟基树脂、各类溶剂以及其他脂肪族异氰酸酯混容，这样就可给相关技术人员在设计配方时带来较大的自由度。  \n\n采用IPDI三聚体为固化剂的聚氨酯涂料的不沾灰时间较短，这是作为汽车修补涂料的一个非常关键的长处。但是IPDI三聚体的价格偏高，使得那些对HDI缩二脲的价格都觉得贵了的客户更加望而却步。为此有人建议将IPDI三聚体与HDI缩二脲混拼使用，以减少价格因素的消极影响。比较成熟的做法是将HDI缩二脲与IPDI三聚体按 $_3:1$ 混合使用。据称可以明显地缩短原单纯采用缩二脲时的不沾灰时间，同时漆膜的硬度、耐候性也有一定程度的改善。另外由于大大减少了IPDI三聚体的用量，使得总材料成本不致提升太高。  \n\n(2）面漆中助剂的应用现代涂料的生产和施工应用离不开助剂。如果选配得当，在提高或改善涂料的各项性能方面可收到事半功倍的突出效果。双组分聚氨酯涂料，特别是用于汽车修补的聚氨酯涂料，助剂的应用就更为重要。一般在这类涂料中添加助剂，主要围绕以下问题：  \n\na.改善涂料的施工性能；  \nb.改善漆膜的外观、装饰性；  \nc.提高涂料的贮存稳定性；  \nd.提高涂料的生产效率。  \n\n$\\Phi$ 催化剂在聚氨酯涂料的制造、加工以及施工后固化成膜的过程中都要使用催化剂。不过这里所采用的催化剂有时是用来加速异氰酸酯基与含活性氢化合物的反应，有时又是用来减缓这一反应过程，因此催化剂的正确选择非常重要。  \n\n用于加速异氰酸酯基与含活性氢化合物反应的催化剂主要有以下两类。  \n\na.有机胺类二乙烯三胺、三乙烯四胺、四乙烯五胺、多乙烯多胺、己二胺、二乙醇胺、三乙胺、4，4-二氨基-3，3-二氨基二苯基甲烷、二氮二杂环辛烷等。  \n\nb.金属盐类最常用的有锌盐和锡盐两大类，如环烷酸锌、异辛酸锌、月桂酸二丁基锡等。  \n\n用于延缓异氰酸酯基与含活性氢化合物反应的催化剂主要是各种酸类化合物。最常用的有磷酸、酸式磷酸酯类等。毕克公司的Bykanol-N就是属于有机酸式磷酸酯类化合物。据称，它可以在一定程度上解决丙烯酸-聚氨酯系涂料在环境温度较高的条件下施工时漆膜容易起痱子的病。同时它还可以延长配漆后，混合物料的“适用期”。  \n\n上述催化剂的用量取决于很多因素，如甲、乙两组分的品种、环境温度、反应条件以及催化剂的种类等。一般其用量在 $0.03\\%\\sim0.1\\%$ 。值得注意的是，那些能够加速异氰酸酯基与含活性氢化合物反应的催化剂，尽管能够有效地缩短漆膜的实干时间，但不可忽略它们对这些双组分品种配漆后的“适用期”的影响。两者之间应很好地权衡，然后再确定催化剂的正确用量。  \n\n$\\textcircled{2}$ 流平剂在本章第三节中已经提到流平剂在面漆中的作用和选定原则等。可用作汽车修补漆流平剂的种类也很多，如高沸点混合溶剂、有机硅化合物、有机氟化合物、某些丙烯酸系聚合物、醋酸丁酸纤维素等。特别应该留意的是在2KPU系统中很难添加对漆膜外观改善特别有效的硅系列流平剂。这主要是因为硅系列流平剂非常容易起“痱子”（也有称为暗泡）的缘故。通常解决的办法就是改用非硅系列流平剂，如聚丙烯酸酯类、含氟表面活性剂类等，可以避免上述病的发生。一般在中、低档修补漆中采用聚丙烯酸酯类流平剂，如BYK358、BYK358N等。因为采用丙烯酸酯类流平剂所制备漆膜的外观远不如硅系列流平剂的滑爽、丰满，手感也差。在高档产品中则建议添加含氟助剂，如EFKA的3777、3778等。  \n\n③消泡剂消泡剂对其他溶剂型涂料而言，其必要性似乎并不大。在很多情况下，即使不用消泡剂，对漆膜的外观也看不出什么影响。但是在聚氨酯涂料系统中，消泡剂却是不可小视的重要成分之一。  \n\n众所周知，各类聚氨酯系涂料的贮存稳定性或多或少都会存在一些问题。单组分涂料本身和双组分系统中的固化剂组分，在贮存过程中的黏度都有可能上升。而双组分系统则还会出现配漆后的适用期缩短等。另外在湿热的条件下施工时，漆膜特别容易起泡。这些现象大都是由于空气中所含的水分或者说潮气所带来的后果。单组分聚氨酯或双组分中的固化剂组分的大分子中，均含有一定量的NCO基团，它可与水分子发生反应，释放出二氧化碳和胺，而这些胺还将进一步和NCO基团反应形成脲。如果此时涂层已经表干，轻者则在漆膜表面形成所谓“痱子”，重者极可能大面积起泡。  \n\n漆膜中被带入水分的途径主要有如下两种。  \n\na.喷涂施工时混入压缩空气中，尤其是在湿热的环境下施工时这种可能性非常大。  \n\nb.溶剂，特别是极性溶剂中均含有一定量的水分。在环境温度偏高时，即使是非极性溶剂，其中的饱和水含量也不低。例如；常用的二甲苯，在室温 $25\\Upsilon$ 下，其饱和水含量大约为 $400~\\mathrm{{mg/L}}$ ；当环境温度升至 $35\\mathrm{^{\\circ}C}$ 时，其饱和水含量就提高到 $900~\\mathrm{{mg/L}}$ 。这样的水平已经足以在涂层中与NCO基团反应形成一定数量的“痱子”甚至气泡了。  \n\n可用于聚氨酯涂料中消泡剂的商品很多，如毕克公司的BYKETOLSperical、BYK104、BYK065、BYK066、BYK051、BYK052、BYK053、BYK057、BYK141等；德隆公司的5500、3200、6500等；EFKA公司的EFKA20、EFKA22、EFKA272、EFKA720等；汉高公司的Perenol S4、Perenol S43、Perenol El等。其中汉高公司的Perenol E1 为非有机硅系列消泡剂，据称这种消泡剂不仅仅消泡效果明显，而且可以避免采用有机硅系消泡剂对漆膜层间附着力的不良影响。  \n\n另外，过去在涂料制造中用作润湿剂的201甲基硅油也可用于聚氨酯系涂料的消泡。当然比起上述专用消泡剂来，效果肯定差一些，但价格低廉，也不失为一种选择。  \n\n$\\textcircled{4}$ 潮气消除剂针对潮气给聚氨酯涂料系统所带来的不良影响，国外研发了一种专用于聚氨酯涂料系统的所谓“潮气消除剂”，如异丁醛氧氮杂环戊烷、乙基氧氮杂环戊烷、酮基氧氮杂环戊烷等。据研发这类助剂的公司称：它们可以成功地消除聚氨酯系涂料在炎热的夏季施工时，因潮气所引起的痱子、气泡等漆膜病，延长双组分聚氨酯系涂料的适用期，避免单组分聚氨酯系涂料在贮存中发生“胀听”的问题，具有一定的实用价值。  \n\n拜耳公司的AdditiveT1和AdditiveOF也是一种潮气消除剂，值得注意的是这两种助剂需配合起来使用。在防止单组分聚氨酯涂料“胀听”，延长双组分聚氨酯涂料系统固化剂的贮存期以及配漆后的适用期方面效果都不错。  \n\nT1的化学名称为甲苯磺酰异氰酸酯，其分子式为：  \n\n![](images/38be9129fa6d7ca1dc9502ed5cb3cff73cd855449fdd6b0f1925756248905292.jpg)  \n\n由于分子中磺酰基的吸电子性，使得甲苯磺酰异氰酸酯分子中NCO基团的反应活性远远高于二异氰酸酯类化合物分子上的NCO基团，从而能够优先与系统中可能存在的水分反应生成对甲苯磺酸，所生成的对甲苯磺酸可起延缓NCO与OH反应的作用，另外还由于它是单官能化合物，故参与反应后不会造成系统黏度上升，更不可能导致胶化。  \n\nT1分子中的NCO活性较高，故对眼睛、皮肤都有强烈的刺激作用，使用时务必小心。原包装桶开封取料后应注意盖好桶盖，最好将包装桶倒置一下，利用桶内的物料将桶盖密封好。另外由于T1的价格较高，使用时最好与OF拼用。  \n\nOF的化学名为三乙氧基甲烷，俗称原甲酸乙酯，其分子式为：  \n\n三乙氧基甲烷可与系统中可能存在的水分反应生成乙醇，显然所生成的乙醇可能会与NCO反应，从而消耗一部分NCO，但可以成功地避免漆膜起泡。三乙氧基甲烷与水反应的反应式如下。  \n\n$$\n\\begin{array}{r}{\\underbrace{\\phantom{\\left(\\sum_{\\ell}\\mathbf{H_{\\ell}}\\right)_{\\ell}}\\mathrm{OC}_{2}\\mathrm{H}_{5}}_{\\mathrm{OC}_{\\ell}\\mathrm{H}_{5}}\\ +\\mathrm{H}_{2}\\mathrm{O}\\mathrm{~\\longrightarrow~\\Phi~}\\mathrm{H}\\underset{\\mathrm{OC}_{\\ell}\\mathrm{H}_{5}}{\\overset{\\mathrm{OH}}{\\longrightarrow}}\\ +\\mathrm{C}_{\\ell}\\mathrm{H}_{5}\\mathrm{OH}}\\\\ {\\underbrace{\\phantom{\\left(\\sum_{\\ell}\\mathbf{H}_{\\ell}\\right)_{\\ell}}}_{\\mathrm{OC}_{\\ell}\\mathrm{H}_{5}}\\ +\\mathrm{H}_{2}\\mathrm{O}\\mathrm{~\\longrightarrow~\\Phi~}\\ \\mathrm{H}_{\\ell}^{\\prime}\\ +\\mathrm{H}_{5}\\mathrm{OH}}\\end{array}\n$$  \n\n从上述反应式可以看出：1mol三乙氧基甲烷可与2mol水发生反应，吸水效果非常高。OF的价格远较T1便宜，与水反应的活性也不低，但由于OF与水反应后的副产物乙醇将可能消耗一部分系统中某一组分的NCO基团，为避免OF的这一不足，实用中常常采用 ${\\mathrm{~T1~}}$ 与OF拼用的方案，这样安排一方面由于T1可吸收OF与水反应释放出来的乙醇，另外也可降低吸水助剂系统总的价格。  \n\n$\\textcircled{5}$ 光稳定剂与紫外光吸收剂在各种聚氨酯系涂料中加入紫外光吸收剂旨在进一步提高其耐候性，特别是保光、保色性能。太阳光中，波长为 $200{\\sim}411\\ \\mathrm{nm}$ 的光波辐射能最强，破坏力也最大。它能够促进聚合物大分子链节自动氧化过程的进行，从宏观的角度来看，也就是加速漆膜的降解。某些紫外光吸收剂能够有效地吸收这一波长范围内的光辐射能，然后将其转化为其他无害能量，从而有效地延缓了上述降解过程，实际上起到了抗老化作用。如二苯甲酮类化合物，它能够通过整合氢键的形成，使一定波长的紫外光能转化为热能，从而消除或减弱了紫外光辐射能对漆膜的破坏作用。不少二苯甲酮类的衍生物已经形成商品在市面上流通。除此而外，苯并三唑之类的杂环化合物也有不少用作紫外光吸收剂，如羟基苯并三唑类等。  \n\n为了延缓这一过程的运行，在生产实际中往往采用抗氧剂、紫外光吸收剂等拼用的办法。一个比较明显的范例就是采用紫外光吸收剂与自由基捕获剂拼用。受阻胺光稳定剂（HALS）是自由基捕获剂中的一种，它与等量的紫外光吸收剂混用可以获得比较明显的增效作用（或者叫协和作用）。  \n\n$\\textcircled{6}$ 流变助剂流变助剂是一类新型涂料用添加剂，它可以有效改变漆料的流变性能。在汽车修补漆领域内广泛用于厚膜清漆之中，可保证良好的一次成膜厚度，而且所得涂层的外观平整光滑。  \n\n由于汽车修补漆的2K系统中，多采用羟基丙烯酸树脂，故选用的SCA改性树脂也多为SCA改性丙烯酸树脂。 Y  \n\n有机膨润土也常常用于汽车修补漆2K实色漆中，如Bentone27、Bentone34、BentoneSD-2、BentoneSD-3等均可。值得注意的是，在双组分聚氨酯系涂料中采用的有机膨润土助剂，预分散打浆时，最好不要采用以往常用的含羟基溶剂（如丁醇)，而建议采用如汉高的 Texaphor 963、Kimperial的Disper KC 761或其他分散助剂。  \n\n正如其他类型助剂使用时采用复配的手法一样，为进一步提高其对涂料流变性能影响的力度，流挂助剂也讲究搭配使用。如有的资料介绍，上述助剂如和有机膨润土拼用，可起到增效作用，而对漆膜的其他物性则几乎没有影响。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1076,
+        "chunk": "# 二、辅料  \n\n汽车修补配套材料主要是指进行汽车修补涂装系统所用的原材料。严格地说，这个完整的涂装系统所用的原材料主要包括底漆、腻子、中间涂料以及面漆等。国外大部分汽车涂料公司在其汽车修补涂料的说明书中都要严格地规定与面漆配套的底漆、中间涂料、封闭剂以及腻子等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1077,
+        "chunk": "# 1.底漆  \n\n母庸置疑，汽车修补用底漆远远比不上汽车总装厂用的阴极电泳底漆，但也有其自身的特殊要求和特点。目前国外多采用双组分聚氨酯、双组分环氧富锌底漆或锌黄底漆。  \n\n国产汽车修补用底漆过去多采用硝基类、环氧酯类、醇酸类等单组分制品，双组分环氧或双组分聚氨酯制品等。国内各大涂料厂都有可用于汽车修补的底漆供应市场（表3-2-38和表3-2-39)，但就性能和适用性而言已经落后于某些汽车修补涂料专业生产厂家。  \n\n(1）硝基纤维素底漆硝基纤维素底漆具有施工性能良好、易打磨、快干等优点，但作为头道底漆使用时，附着力方面的性能是它的致命伤。配方设计、原料选用、基材的表面处理等只要有一个环节稍有不慎即可造成附着不好的恶果。使用时务必小心在意。ICI公司贝高系列中P082-28防浮红底漆、P084-700风干中涂底漆均属此类产品。这两种产品使用时均采用贝高系列P851稀释剂。  \n\n表3-2-38国产汽车修补用硝基底漆  \n\n\n<html><body><table><tr><td>项 目</td><td>Q06-1</td><td>Q06-4</td></tr><tr><td>名称</td><td>黄硝基底漆</td><td>各色硝基底漆</td></tr><tr><td>组成</td><td>硝基纤维索、醇酸树脂</td><td>松香甘油酯、颜料、填料、增韧剂等</td></tr><tr><td>颜色及外观</td><td>黄色、平整光滑</td><td>各色、平整光滑</td></tr><tr><td>黏度（涂-1)/s</td><td>120~200</td><td>120~200</td></tr><tr><td>不挥发分/%</td><td>≥40</td><td>40</td></tr><tr><td>干燥时间/min</td><td></td><td></td></tr><tr><td>表干</td><td>10</td><td>10</td></tr><tr><td>实干</td><td>50</td><td>50 2</td></tr><tr><td>附着力/级</td><td>≤2</td><td></td></tr><tr><td>打磨性</td><td>打磨性好</td><td>200*砂纸打磨，不粘砂纸</td></tr><tr><td>用途</td><td>各种金属表面、车辆</td><td>各种金属表面、车辆</td></tr><tr><td>施工及配套</td><td>硝基瓷漆</td><td>硝基瓷漆</td></tr></table></body></html>  \n\n(2）环氧底漆用于汽车修补的环氧底漆有双组分环氧树脂底漆和单组分环氧酯底漆两种。  \n\n双组分环氧树脂底漆主成膜物质为中～低分子量环氧树脂，如E-12、E-14、E-20等。固化剂则采用脂肪族多元胺、改性多元胺类或聚酰胺等。其中聚酰胺的固化速率较慢，使用时需拼用一定量的催干剂，如三（二甲氨基甲基）苯酚（DMP-30)。双组分环氧树脂底漆的各项物性，包括干燥速率、打磨性、力学性能、耐介质性能等均与所用的固化剂关系密切。其综合性能除存在与聚氨酯类一样的“适用期”让操作者略感不便外，其他方面均优于单组分环氧酯底漆。德国BASF公司的汽车修补专用底漆EUROXY就是一种双组分环氧树  \n\n脂底漆。  \n\n单组分环氧酯底漆是涂料行业中底漆类的主导产品。其主成膜物质为环氧树脂的脂肪酸酯。在汽车修补业内，考虑到所采用的面漆多为双组分丙烯酸-聚氨酯类，其中所含溶剂大都为强极性溶剂。故多采用带有共轭双键的高不饱和度脂肪酸的环氧酯，以提高底漆的耐溶剂性。在性能检测中该项目被列为必测指标，称为底漆的耐硝基性。实际应用上多采用脱水麻油酸、亚油酸与桐油酸拼合使用等。  \n\n双组分和单组分环氧底漆中所含防锈颜料大多为锌黄或铁红。过去涂料行业在防锈底漆中普遍采用的防锈性能更好的红丹，因环保方面原因，现已很少采用。国产汽车修补用环氧底漆性能指标见表3-2-40。  \n\n表3-2-39国产环氧酯锌黄和铁红底漆 单位：质量份  \n\n\n<html><body><table><tr><td>组成</td><td>环氧雕锌货</td><td>铁环红漆</td><td>组成</td><td>环氧酸锦费</td><td></td></tr><tr><td>脱水麗麻油酸环氧酯</td><td>38.0</td><td>38.0</td><td>硫酸钡</td><td></td><td>8.0</td></tr><tr><td>丁醇改性三聚氰胺甲醛树脂</td><td>1.0</td><td></td><td>有机膨润土胶（10%）</td><td></td><td>0~5</td></tr><tr><td>109锌黄</td><td>15.0</td><td></td><td>防结皮剂</td><td>0.2</td><td>0.2</td></tr><tr><td>氧化铁红</td><td></td><td>14.0</td><td>双戊烯</td><td>2.0</td><td>2.5</td></tr><tr><td>CT钙铁粉</td><td>5.0</td><td>8.0</td><td>稀土干料</td><td>3.5</td><td>3.2</td></tr><tr><td>锌粉</td><td>8.5</td><td>5.0</td><td>二甲苯</td><td>12.8</td><td>12.1</td></tr><tr><td>滑石粉</td><td>14.0</td><td>6.5</td><td>丁醇</td><td></td><td>2.0</td></tr></table></body></html>  \n\n表3-2-40国产汽车修补用环氧底漆性能指标  \n\n\n<html><body><table><tr><td>性 能</td><td>H06-2</td><td>H06-10</td><td>H06-14</td></tr><tr><td>名称</td><td>铁红、锌黄环氧酶底漆</td><td>环氧酯富锌底漆</td><td>各色环氧底漆</td></tr><tr><td>组成</td><td>环氧酯、铁红或锌黄颜料、填料、催干剂、氨基树脂</td><td></td><td>环氧酯、锌粉、催干剂环氧树脂、多元胺、颜料、填料</td></tr><tr><td>颜色及外观</td><td>铁红色或黄色、平整</td><td>灰色、平整</td><td>各色、平整</td></tr><tr><td>黏度（涂-4杯）/s50~80</td><td></td><td>60~80</td><td></td></tr><tr><td>不挥发分/%</td><td>≥40</td><td></td><td></td></tr><tr><td>干燥时间/h</td><td></td><td></td><td></td></tr><tr><td>表干</td><td>2</td><td>18min</td><td>4</td></tr><tr><td>实干</td><td>24</td><td>12</td><td>24</td></tr><tr><td>附着力/级</td><td>≤1</td><td></td><td></td></tr><tr><td>打磨性</td><td>打磨性好，200*砂纸，不起卷，不粘漆</td><td></td><td>强度高，打磨性差</td></tr><tr><td>用途</td><td>各种金属表面，车辆</td><td>各种金属表面，汽车</td><td></td></tr><tr><td>施工及配套</td><td>各类瓷漆</td><td></td><td></td></tr></table></body></html>  \n\n杜邦公司的830R是一种环氧型无铬重防腐蚀底漆，它的不挥发分高、附着力好、耐各种介质均佳，且适用于铝材等轻质合金表面。  \n\nPPG公司的D834亦属双组分环氧类底漆，它既可作为封闭底漆亦可作二道浆使用。专用固化剂D835，配比高达 $1:1$ 。D835固化剂属于聚酰胺或其他改性胺类。  \n\n(3）聚氨酯底漆聚氨酯底漆是底漆类中的一大系列，它具有力学性能、耐各类介质性能、配套性能以及施工性能良好等方面的特点。在汽车修补涂料系列中，不少厂家都有这类产品。近年来高填充性、免打磨（或少打磨）需求越来越强烈，故底漆有厚膜化的发展趋势，不少厂家都推出了聚氨酯厚膜底漆。如ICI公司的P565-510、DuPont公司的1020R、广东东莞博德的AB888等，这些产品的一次成膜厚度可高达 $150\\mu\\mathrm{m}$ 左右。  \n\n双组分聚氨酯底漆技术关键首先在于主成膜物质的选择。如果树脂选择不当，即使罩面（喷中间涂料或面漆）的时间间隔足够，也非常容易出现咬底、渗色等病。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1078,
+        "chunk": "# $\\Phi$ 典型双组分聚氨酯底漆配方（质量份）  \n\nRKC-2015 41. 5 超细碳酸钙 23.3   \n锌黄 9.5 BYK-110 0.1   \n滑石粉 11.6 有机膨润土胶 0.4   \n钛白粉 2.0 醋酸丁酯 3.0   \n硬脂酸锌 3.7 二甲苯 5.0",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1079,
+        "chunk": "# $\\textcircled{2}$ 性能指标及施工参数实测南方某厂聚氨酯厚膜底漆数据如下。  \n\na.施工参数  \n\n<html><body><table><tr><td>配比</td><td>漆料·固化剂/稀释剂=4：1/</td><td>压缩空气压力/×10Pa</td><td>3.5</td></tr><tr><td></td><td>(100%~120%)</td><td>喷涂道数/道</td><td>3</td></tr><tr><td>施工黏度（涂-4\"杯）/s</td><td>20</td><td>干燥条件/C×min</td><td>60X30</td></tr><tr><td>b.性能指标</td><td></td><td></td><td></td></tr><tr><td>细度/μm</td><td>30</td><td>柔韧性/mm</td><td>2</td></tr><tr><td>黏度（涂-4杯，23℃）/s</td><td>195</td><td>冲击性/cm</td><td>50</td></tr><tr><td>漆膜厚度/μm</td><td>95</td><td>铅笔硬度</td><td>HB</td></tr><tr><td>附着力/级</td><td>2</td><td>打磨性（P600砂纸，2h后）</td><td>不粘砂纸，易打磨</td></tr><tr><td>速盖力/（g/m²）</td><td>90</td><td>耐硝基性能</td><td>不渗色、不咬底</td></tr></table></body></html>  \n\n(4）磷化底漆磷化底漆又名洗涤底漆。不仅仅在汽车修补行业，就是在一般工业涂料领域也不把它作为唯一的底漆使用。只是涂底漆之前预涂一薄层磷化底漆，起增强底漆的附着力和防锈能力的作用。它具有磷化和钝化双重功效。  \n\n磷化底漆一般有单组分和双组分两种，早期的磷化底漆大体由聚乙烯醇缩丁醛树脂、碱式铬酸锌、磷酸以及溶剂所组成。单组分磷化底漆因防锈效果不太理想已不常见，现多采用双组分。  \n\n磷化底漆中所采用的聚乙烯醇缩丁醛树脂丁酰基含量为 $44\\%\\sim48\\%$ 费碱式铬酸锌俗称锌黄，它的分子式为 $\\mathrm{2nCrO_{4}\\cdot4Z n(O H)_{2}}$  \n\n碱式铬酸锌对轻金属如铝、铜、铝镁合金以及钢铁等均具有良好的防锈能力，其防锈机理为。  \n\n$\\Phi$ 具有碱性；  \n\n$\\textcircled{2}$ 在水中能够慢慢溶解，离解出 $\\mathbf{CrO^{-}}$ 。这种离子可由漆膜中渗出达到金属基材表面，生成铬酸铁，使金属表面钝化。  \n\n这就是洗涤底漆防锈的基本原理所在。早期双组分磷化底漆大体组成如下。  \n\n甲组分（质量份）：  \n\n<html><body><table><tr><td>聚乙烯醇缩丁醛</td><td>7.2</td><td>异丙醇</td><td>48.7</td></tr><tr><td>碱式铬酸锌</td><td>6.9</td><td>丁醇</td><td>16.1</td></tr><tr><td>滑石粉</td><td>1.1</td><td></td><td></td></tr><tr><td>乙组分（质量份)：</td><td></td><td></td><td></td></tr><tr><td>磷酸</td><td>3.6</td><td>异丙醇</td><td>13.2</td></tr><tr><td>水</td><td>3.2</td><td></td><td></td></tr></table></body></html>  \n\n配方中甲组分需经研磨、分散后方可使用。使用时将两个组分混合均匀后，至少放置10s后，再薄薄地喷涂一层。涂层厚度最好控制在 $10\\mu\\mathrm{m}$ 左右。 三  \n\n当今环保部门有关条例限制了涂料原材料中铅、铬、镉等重金属的含量，故新一代的磷化底漆中已不再采用碱式铬酸锌类铬系颜料。新的磷化底漆在保持其防锈性能的基础上改用了其他磷酸盐类。这类磷酸盐防锈机理与上述铬酸盐有所不同。它是通过多聚磷酸根离子与金属离子生成整合物，在金属基材表面形成致密的 $\\begin{array}{r}{\\mathbb{M}_{z}\\mathrm{Fe}_{y}(\\mathrm{PO}_{4})_{z}}\\end{array}$ 钝化膜，这类钝化膜难溶于水、硬度高、附着力极强，对钢铁等金属的腐蚀具有极强的抑制作用。配方举例如下。  \n\n甲组分（质量份）  \n\n\n<html><body><table><tr><td>聚乙烯醇缩丁醛树脂</td><td>9.0</td><td>滑石粉</td><td>3.9</td></tr><tr><td>醇溶性酚醛树脂</td><td>11. 0</td><td>丁醇</td><td>11. 0</td></tr><tr><td>氧化铁黄</td><td>3.6</td><td>异丙醇</td><td>25.0</td></tr><tr><td>钼酸锌</td><td>2.5</td><td>甲苯</td><td>30.5</td></tr><tr><td>聚磷酸铝</td><td>2.5</td><td></td><td></td></tr><tr><td>乙组分(质量份)：</td><td></td><td></td><td></td></tr><tr><td>磷酸（85%)</td><td>9.0</td><td>异丙醇</td><td>86.0</td></tr><tr><td>水</td><td>5.0</td><td></td><td></td></tr></table></body></html>  \n\n配方中甲组分需经研磨、分散，然后按甲： ${Z=80:20}$ 的配比混合均匀即可。进口汽车修补涂料系统中不少配置有洗涤底漆。如日本立邦（Nippon）的V-110、PPG的D831、ICI的P565-597等均属于汽车修补专用磷化底漆。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1080,
+        "chunk": "# 2.腻子  \n\n腻子在汽车修补业内又被细分为“填眼灰”、“原子灰”等。它是为了填平由于各种原因造成的汽车待修补表面的机械凹陷，提高其平整度而必不可少的一类辅料。一般在底漆涂装并干透后都要刮涂腻子。适用于汽车修补的腻子很多，有醇酸树脂、硝基纤维素、环氧树脂以及不饱和聚酯树脂类等。  \n\n(1）硝基纤维素腻子很早以前硝基纤维素腻子就用于汽车修补中。直到今天各专业厂家，包括外国名牌汽车修补涂料公司仍然有硝基腻子产品。硝基腻子具有价廉、快干、与各类中间涂料配套性良好等特点，如果配方设计合理，还能赋予它优良的打磨性，与上、下层涂料之间不错的附着力等。基于诸多方面因素使其仍然受到众多客户的青睐。  \n\n硝基纤维素类腻子的组成与硝基纤维素面漆类似，它大体由硝基纤维素、醇酸树脂、增韧剂、颜料、填料以及助剂所组成。醇酸树脂和增韧剂用以调整腻子的刚柔性，起平衡力学性能的作用。腻子中填料的应用尤为重要，它应该在保证腻子打磨性优良的同时，给予腻子补强，使它具有一定的内聚强度。这样在整个涂层受到外界剥离应力时，既不允许在腻子处发生层间剥离，更不允许出现腻子内聚破坏。填料中具有针状结构的滑石粉可有效增加腻子的内聚强度，硬脂酸锌则具有优良的打磨性能。其典型配方举例如下。  \n\n$\\textcircled{1}$ 配方 （质量份）  \n\n<html><body><table><tr><td>醇酸树脂（70%)</td><td>9.5</td><td>超细轻质碳酸钙</td><td>3.7</td></tr><tr><td>醋酸丁酯</td><td>2.7</td><td>锐太型钛白粉</td><td>2.5</td></tr><tr><td>丁醇</td><td>0.5</td><td>氧化铁黄</td><td>0.5</td></tr><tr><td>环己酮</td><td>0.5</td><td>炭黑</td><td>少量</td></tr><tr><td>二甲萃</td><td>3.0</td><td>有机膨润土胶（8%）</td><td>8.0</td></tr><tr><td>硅油(1%)</td><td>0.2</td><td>硝基纤维素溶液（35%)</td><td>19.3</td></tr><tr><td>滑石粉</td><td>25.5</td><td>二甲苯</td><td>2.5</td></tr><tr><td>重晶石粉</td><td>16.6</td><td>醋酸丁酯</td><td>3.0</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 工艺  \n\na.将醇酸树脂（ $70\\%)$ 、醋酸丁酯、丁醇、环已酮、二甲苯、硅油投入到调漆缸中，搅  \n拌均匀。b.在搅拌下慢慢投人滑石粉、重晶石粉、超细轻质碳酸钙、锐太型钛白粉、氧化铁黄、  \n炭黑，再高速分散至少30s。c.在三辊机上研磨至细度 $<30\\mu\\mathrm{m}$ 鼎d.在搅拌下慢慢加人有机膨润土胶（ $8\\%$ ）和硝基纤维素溶液（ $35\\%$ ，搅拌均匀。e.用二甲苯和醋酸丁酯调黏。  \n\n表3-2-41中所列是较早时期的硝基腻子标准。现市面上流行的修补用填眼灰的标准则要简单和实用些。如南方某修补涂料厂所生产的填眼灰标准如下。  \n\n<html><body><table><tr><td>外观</td><td>均匀、无颗粒</td><td>细度/μm</td></tr><tr><td>刮涂性</td><td>滑爽、不起皮、不卷边</td><td>≤</td></tr><tr><td rowspan=\"2\">黏度（涂-4*杯，23℃）/min</td><td>31(产品用醋酸</td><td></td></tr><tr><td>丁酯1：1兑稀）</td><td></td></tr></table></body></html>  \n\n表3-2-41国产硝基纤维素腻子牌号及性能  \n\n\n<html><body><table><tr><td>性 能</td><td>Q07-5</td><td>Q07-6</td><td></td><td>Q07-7</td></tr><tr><td>名称</td><td rowspan=\"3\"></td><td>各色硝基腻子</td><td>灰硝基腻子</td><td>黄硝基腻子</td></tr><tr><td>颜色和外观</td><td colspan=\"3\">无粗粒、均匀</td></tr><tr><td>不挥发分/% 干燥时间/h</td><td>65</td><td>65</td><td>65</td></tr><tr><td rowspan=\"2\">柔韧性/mm</td><td rowspan=\"2\">≥ ≥</td><td>3</td><td>3</td><td>3</td></tr><tr><td>100</td><td>100</td><td>100</td></tr><tr><td colspan=\"2\">耐热性 打磨性</td><td colspan=\"4\">无可见裂纹 采用200°水砂纸打磨，不粘漆、平整 刮涂性好，不起卷、不卷边 干燥速率快，易打磨，供填平孔用</td></tr></table></body></html>\n\n①65\\~70°℃，6h,  \n\n(2）环氧腻子用于汽车修补的环氧型腻子既有双组分环氧树脂型，也有单组分环氧酯型，双组分环氧树脂采用的固化剂为多元胺类。H07-6环氧腻子，又名669环氧腻子。其基本性能如下。  \n\n<html><body><table><tr><td>外观</td><td>均匀膏状物、无颗粒</td><td>柔韧性/mm</td><td>50</td></tr><tr><td>干燥时间/h</td><td></td><td>打磨型</td><td>易打磨，不卷边</td></tr><tr><td>表干</td><td>≤4</td><td>耐硝基性</td><td>不咬底，不渗色</td></tr><tr><td>实干</td><td colspan=\"3\">≤18</td></tr></table></body></html>  \n\n单组分环氧酯腻子用得不多，主要是这类腻子的干燥速率，尤其是实干速率太慢，几乎达不到汽车修配厂生产周期的要求。它的刮涂性能特好，易于施工，但打磨性稍差，易粘砂纸。这也与它的干燥性能欠佳有关。单组分环氧酯腻子的牌号常见的有H07-5，所用主树脂仍然是脱水麻油酸环氧酯。典型配方如下（质量份）。  \n\n<html><body><table><tr><td>脱水麻油酸环氧酯</td><td>15.0</td><td>滑石粉</td><td>5.0</td></tr><tr><td>锌粉</td><td>12. 0</td><td>硬脂酸锌</td><td>4.0</td></tr><tr><td>重晶石粉</td><td>29.0</td><td>双戊烯</td><td>3.0</td></tr><tr><td>沉淀硫酸</td><td>6.0</td><td>铅干料</td><td>1.0</td></tr><tr><td>碳酸钙</td><td>23.0</td><td>锰干料</td><td>1.0</td></tr></table></body></html>  \n\n(3）醇酸腻子早期汽车修补除硝基腻子外，用得最多的就数醇酸腻子了。国内目前仍然有不少汽车修配厂还在使用。其特点是施工性能特别好，受到油漆工的普遍欢迎。醇酸腻子中主成膜物质为短油度醇酸树脂、改性醇酸树脂、酚醛树脂等。国产醇酸腻子的牌号及性能见表3-2-42。  \n\n(4）原子灰原子灰为填补基材上较大凹陷、焊缝、裂缝等缺陷所采用的--种腻子。实际上这是一类不饱和聚酯树脂型腻子的统称。目前已广泛用于汽车、火车等各种交通工具行业中。一般原子灰由主树脂浆和引发剂溶液（蓝、白水）所组成。两者的配比一般为： $100:(2{\\sim}4)$ 阜  \n\n主树脂浆由不饱和聚酯树脂、颜料、填料、乙烯基单体、阻聚剂、促进剂等组成。常见的腻子的形态及颜色多为灰色或灰白色膏状物。引发剂为过氧化环己酮、过氧化甲乙酮。催",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1081,
+        "chunk": "# 干剂为环烷酸钻或异辛酸钴。  \n\n表3-2-42可用于汽车修补的国产醇酸腻子牌号及性能  \n\n\n<html><body><table><tr><td>项 目</td><td>C07-5</td><td>C07-6</td><td>C07-4</td></tr><tr><td>名称 组成 颜色及外观 稠度/cm 干燥时间/h≤</td><td>各色醇酸腻子 醇酸树脂、颜料、填料、催干剂、助剂 无结皮、硬块 8~11</td><td>灰醇酸腻子 酚醛改性醇酸树脂、颜料、填料、助剂 无结皮、硬块 8~11</td><td>棕色醇酸腻子 醇酸树脂、酚醛树 脂、颜料、填料、助剂</td></tr><tr><td>刮涂性能 柔韧性/mm</td><td>18 良好、不卷边</td><td>18 不卷边</td><td></td></tr><tr><td>打磨性</td><td>≤100 200水砂纸打磨，均匀、平滑、无明显</td><td>不粘砂纸</td><td></td></tr><tr><td>性能及用途 施工和配套</td><td>白点 涂层坚硬、附着力强。用于一般交通工具</td><td>快干，适合各种交通工具</td><td>涂层坚硬</td></tr></table></body></html>  \n\n$\\Phi$ 不饱和聚酯树脂汽车修补原子灰的不饱和聚酯树脂是由多元醇、多元酸、不饱和多元酸等经酯化、缩聚反应而得。原子灰中所用的不饱和聚酯树脂与一般不饱和聚酯树脂有所不同。绝大多数的不饱和聚酯树脂中都加有特种改性剂，如环戊二烯、双环戊二烯或烯丙基醚类化合物等，主要用来克服不饱和聚酯树脂类型材料惯有的“厌氧性”，另外也能提高腻子的施工性能、耐介质性能等。原子灰用不饱和聚酯树脂应具有以下特性：  \n\na.常温干燥，且干燥速率快；  \nb.附着力好；  \nc.不影响面漆与中间涂料的层间附着力；  \nd.硬度高，易打磨，刮涂施工方便。  \n\n$\\textcircled{2}$ 引发剂和促进剂汽车修补的不饱和聚酯树脂腻子均采用低温引发剂，如过氧化环己酮、过氧化甲乙酮等。过氧化甲乙酮为液态，而过氧化环己酮为固态。目前市面上多采用过氧化环己酮。酮类过氧化物引发温度虽然较低，但要想在室温下引发不饱和聚酯树脂固化，则尚需添加金属皂类促进剂。常用的促进剂有环烷酸钴、合成脂肪酸钴等。这里需要特别提示的是，酮类过氧化物与金属皂促进剂切不可直接混合，使用前才能分别混入树脂浆料中，否则会发生危险。引发剂用量一般为树脂量的 $2\\%\\sim4\\%$ ，促进剂的用量为树脂量的 $1\\%\\sim2\\%$ 查  \n\n$\\textcircled{3}$ 活性稀释剂在不饱和聚酯树脂型原子灰中一般还要采用活性稀释剂。活性稀释剂的作用有两个：一是调整系统黏度；二是充当树脂的交联剂。常用活性稀释剂有苯乙烯、环戊二烯以及（甲基）丙烯酸酯类等。苯乙烯价格低廉、活性高，与大多数不饱和聚酯树脂的混容性良好，成品的性能也不错。但其挥发性较高，有一定刺激性气味。环戊二烯气味不大，成品的性能也不错，可惜价格稍高。  \n\n$\\textcircled{4}$ 触变剂为了防止不饱和聚酯树脂原子灰在垂直表面上施工时可能出现的流挂现象，常常要在其配方中添加触变剂。加有触变剂的原子灰显得更加细腻、滑爽，刮涂性能好，不流挂。常用的触变剂有气相白炭黑、聚氯乙烯粉等。气相白炭黑用得较多。 八  \n\n$\\textcircled{5}$ 颜料、填料不饱和聚酯树脂原子灰中采用的颜料、填料有钛白粉、炭黑、氧化铁红、氧化铁黄、碳酸钙、滑石粉、硫酸钡、硬脂酸锌等。如前所述，针状结构的滑石粉具有一定的补强作用，应将其与其他填料配合使用。硬脂酸锌具有改善腻子打磨性能的作用。  \n\n$\\textcircled{6}$ 阻聚剂为了延长不饱和聚酯树脂的贮存期，调整原子灰的固化速率，一般在配方中都加有一定量的阻聚剂。这里所采用的阻聚剂多为取代酚类，如氢醒、氢醒单甲醚、氢醒二甲醚、氢二乙醚、246等。阻聚剂一般加到主树脂浆中。  \n\n②封闭剂如前所述，不饱和聚酯树脂采用苯乙烯作稀释剂十交联剂时，一般都有“厌氧性”。改用其他丙烯酸酯类化合物稍好一些，但无法根本解决厌氧的问题。简单而价廉的办法是在其配方中加人某种封闭剂，以隔断空气中的氧进入腻子材料。最常用的封闭剂如石蜡。将石蜡与苯乙烯预先调成糊状物，再加到主树脂糊中。石蜡用量为 $0.01\\%\\sim0.03\\%$ 时即可将腻子的表干时间由原来的2h左右减少到只要 $30\\mathrm{min}$ 。此时腻子的打磨性尚可。  \n\n现举一例典型不饱和聚酯树脂型原子灰的基本配方及工艺。  \n\n$\\Phi$ 不饱和聚酯树脂的合成",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1082,
+        "chunk": "# a.配方 (摩尔比）  \n\n顺丁烯二酸酐 0.60 双环戊二烯 0.30   \n苯二甲酸酐 0.40 季戊二醇三烯丙基醚 0.10   \n二乙二醇 0.30 氢醒（占总量）/% 0.02   \n三乙二醇 0.55 二甲苯（占总量）/% 3.00  \n\nb.工艺  \n\n·将所有反应物全部投入到反应釜中，升温至 $160{\\sim}190^{\\circ}\\mathrm{C}$ 进行酯化反应3h。  \n\n·再在195℃下反应3h。  \n\n·打开回流冷凝器开关，蒸出二甲苯，大约需1h。  \n\n·加入苯乙烯兑稀成 $65\\%$ 的树脂溶液，此时的黏度大约为1.0～1.2Pa $\\cdot$ s(20℃)。  \n·降温、过滤、出料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1083,
+        "chunk": "# $\\textcircled{2}$ 汽车修补用腻子的制备  \n\n·配方（质量份）  \n\n<html><body><table><tr><td>不饱和聚酯树脂液</td><td>320</td><td>钛白粉</td><td>60</td></tr><tr><td>苯乙烯</td><td>20</td><td>异辛酸钻(8%)</td><td>6</td></tr><tr><td>滑石粉</td><td>300</td><td>过氧化环己酮（2%)</td><td>适量</td></tr><tr><td>·性能</td><td></td><td></td><td></td></tr><tr><td>划格法附着力</td><td>100/100</td><td>杯突性能/mm</td><td>≥3</td></tr><tr><td>光泽/%</td><td>98</td><td>干燥性</td><td>2h后可打磨</td></tr></table></body></html>  \n\n为进一步加快不饱和聚酯树脂原子灰的固化速率，缩短施工周期，可采取复合促进剂的办法。芳香族胺类可进一步加速金属皂类对酮类过氧化物的促进作用，可在产品配方中采用金属皂 $^+$ 芳香族胺复合促进系统。有一家公司原子灰的配方就是如此，其原料组成大体如下。  \n\n甲组分：不饱和聚酯树脂、苯乙烯、甲基丙烯酸羟乙酯、二甲基苯胺、氢、苯甲酸、环烷酸钴、滑石粉、钛白等。  \n\n乙组分：过氧化环已酮、永固黄等。  \n\n这里就采用了金属皂（环烷酸钴） $^+$ 芳香族胺类（二甲基苯胺）的复合促进剂系统，故它的固化速率比一般不饱和聚酯树脂型原子灰都快，而且它的附着力强、易打磨、光洁平整、耐油、耐硝基以及冲击强度高等，综合性能比较突出。  \n\n国产腻子与日本产腻子的性能比较见表3-2-43，应该说国产不饱和聚酯树脂原子灰大体上已经达到或接近国外先进水平。  \n\n为了尽可能减少涂料制造和涂装时对环境的污染所带来的公害，腻子也早已开始了水性化，国产水性腻子已进入修补涂料市场。无疑水性腻子气味小、无刺激性，施工性能良好。但也应该注意到采用水性腻子时一定要干透后才能罩二道浆或面漆，如果上层配套涂料采用的是聚氨酯类，则尤其应该小心，以免腻子中未能完全逸散出去的水分会与NCO发生反应，轻者形成痱子，严重时造成漆膜起泡。  \n\n表3-2-43国产原子灰与日本同类产品性能比较  \n\n\n<html><body><table><tr><td>性能</td><td>日本JISK5655</td><td>国产原子灰</td><td>日本产腻子</td></tr><tr><td>外观</td><td>搅拌时无硬块</td><td>无机械杂质和揽不开的硬块</td><td>无机械杂质和揽不开的硬块</td></tr><tr><td>混合性</td><td>易混合均匀</td><td></td><td></td></tr><tr><td>适用期</td><td><5h(20°C±1℃)</td><td>20min</td><td>8min</td></tr><tr><td>刮涂性</td><td>易刮涂</td><td>易刮涂</td><td>易刮涂</td></tr><tr><td>干燥时间/h</td><td><5(20°±1℃)</td><td>2</td><td>1.5</td></tr><tr><td>涂层外观</td><td>与标准板比较，颜色色差小，无 裂纹、气泡</td><td>刮涂后表面平整，干后无裂纹、 气泡</td><td>刮涂后表面平整，干后无裂 纹、气泡</td></tr><tr><td>打磨性(400*砂纸)</td><td>易打磨</td><td>易打磨成无光泽、平滑的表面， 不沾水砂纸</td><td>易打磨成无光泽、平滑的表 面，不沾水砂纸</td></tr><tr><td>冲击性/cm</td><td>50</td><td>10</td><td>15</td></tr><tr><td>柔韧性/mm</td><td></td><td>50</td><td>50</td></tr><tr><td>稠度/cm</td><td></td><td>10.5</td><td>11</td></tr><tr><td>耐油性</td><td></td><td>不透油</td><td>不透油</td></tr><tr><td>耐热性</td><td></td><td>明显变色</td><td>明显变色</td></tr></table></body></html>\n\n$\\Phi$ 30°机油，浸泡24h. $\\textcircled{2}$ 120°℃ ±2℃, 4h,",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1084,
+        "chunk": "# 3.中间涂料  \n\n目前市场上见得较多的中间涂料主要有硝基纤维素类、环氧树脂类以及醇酸树脂类等。至于双组分聚氨酯类中间涂料虽然也有少数几家修补涂料厂生产这一品种，但因为不容易解决它的固化速度较慢和耐硝基性欠缺等方面的问题，使用面不太广。  \n\n(1）硝基纤维素中间涂料早期汽车的面漆采用的都是硝基纤维素类涂料。显然与之配套的中间涂料必然也是硝基类。这类涂料的干燥速率快，打磨性、配套性、施工性、外观均可，而且价格低廉，长期以来深受汽车行业的欢迎。至今一些名牌汽车修补涂料公司如德国BASF、Herberts、美国PPG、DuPont等的中间涂料均有这-类品种。但是硝基纤维素类中间涂料的柔韧性欠佳，耐老化性能也不好，更为严重的是配方设计如稍有不当，即会带来附着性能差的病。使用一段时间后，漆膜经常容易发生龟裂、脱落的现象。因此认真选择与均衡配方中的各个成分，至关重要。硝基纤维素类中间涂料的构成与这一类型的面漆大同小异。现举一个典型范例予以说明。  \n\n$\\Phi$ 配方（质量份）  \n\n<html><body><table><tr><td>醇酸树脂</td><td>12.88</td><td>CM763</td></tr><tr><td>国产钛白粉</td><td>4.98</td><td>苯二甲酸丁苄酯</td></tr><tr><td>立德粉</td><td>8.06</td><td>膨润土胶（10%）</td></tr><tr><td>沉淀硫酸银</td><td>2.20</td><td>硝基纤维素溶液（35%）</td></tr><tr><td>滑石粉</td><td>16.57 醋酸丁酯</td><td></td></tr><tr><td>碳酸钙</td><td>0.35 二甲苯</td><td></td></tr><tr><td>硬脂酸锌</td><td>0.33 醋酸乙酯</td><td></td></tr><tr><td>炭黑</td><td>0.10</td><td>8.00</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 工艺  \n\na.将醇酸树脂、CM763、苯二甲酸丁苄酯以及部分醋酸丁酯、二甲苯投人到调漆缸中，搅拌均匀。  \n\nb.在搅拌下慢慢加人国产钛白粉、立德粉、沉淀硫酸钡、滑石粉、碳酸钙、硬脂酸锌、 炭黑，加完后再高速分散至少 $30\\mathrm{{min}}$  \n\nc.在砂磨机上研磨至细度合格 $(15\\mu\\mathrm{m}$ 以下)。d.在搅拌下慢慢加入膨润土胶（ $10\\%)$ 、硝基纤维素溶液（ $35\\%$ ）和剩余的醋酸丁酯、二甲苯。e.最后加入醋酸乙酯调黏。  \n\n制漆工艺中，添加硝基纤维素溶液和膨润土胶时，应特别留意搅拌的转速和物料的加入速率。如果太随意，则很容易发生“返粗”。其实这里的所谓“返粗”现象并不是颜料或填料出现絮凝，而是硝基纤维素或膨润土胶粒未能及时分散、溶解到漆料中的缘故。  \n\n几种国产硝基纤维素类中间涂料的性能比较见表3-2-44；可以发现；市面上各厂自行拟定的新标准更加简洁、实用。  \n\n表3-2-44国产硝基纤维素中间涂料性能比较  \n\n\n<html><body><table><tr><td>性能</td><td>Q06-5</td><td>Q700</td><td>YT-222</td></tr><tr><td>名称 组成 漆膜颜色及外观 黏度（涂-4杯）/s</td><td>灰硝基二道底漆 硝基纤维素、醇酸树脂、顺丁烯二 酸酐树脂、颜料、填料、溶剂等 灰白色，平整光滑，无明显粗粒 15~30 ≥50</td><td>二道底漆 硝基纤维素、醇酸树脂、改性醇 酸树脂、颜料、填料、助剂、溶剂等 灰白色，平整光滑 22±2 50±2</td><td>苏灰土 硝基纤维素、醇酸树脂、颜 料、填料、助剂、溶剂等 灰白色，平整光滑</td></tr><tr><td>附着力/级 打磨性 性能与用途</td><td>3 采用200*砂纸打磨，不粘漆，易 打磨，平滑 干燥速率快，填平性好，专用于填 平腻子孔腺及砂纸打磨痕迹</td><td>2 采用400砂纸打磨，易打磨， 不粘砂纸 干燥速率快，填平性好，专用于 填平腻子孔隙及砂纸打磨痕迹层</td><td>采用400～600\"砂纸干 打磨，800*～1000*砂纸湿 打磨，易打磨 层间附着力好，填充性、遮 盖力优异，易填补漆膜表面</td></tr><tr><td>施工及配套</td><td>可采用X-1硝基稀释剂稀释，湿 度太高时可加20%～30%F-1硝 基防潮剂，忌与其他不同品种的涂</td><td>间附着力好 采用X-1硝基稀释剂稀释， 可与各类腻子和面漆配套使用</td><td>细微缺陷 采用X-1稀释剂，可与各 类面漆配套使用</td></tr></table></body></html>\n\n$\\Phi$ Q700和YT-222均是南方一些汽车修补涂料专业厂产品。  \n\n(2）环氧树脂类中间涂料汽车修补行业中，环氧树脂类中间涂料现多采用双组分多元胺固化系统。单组分环氧酯不太常用，主要原因是它的耐硝基性能极容易出问题。而双组分环氧的配套性能良好，主要反映在它的耐硝基性能上，绝不会出问题。但固化时间长是它的致命伤。较典型的牌号及性能如下。  \n\n<html><body><table><tr><td>名称</td><td>各色环氧二道底漆 环氧树脂、颜料、填</td><td>干燥时间 表干</td><td>≤2</td></tr><tr><td>组成</td><td>料、多元胺、助剂等</td><td>实干</td><td>≤24</td></tr><tr><td>黏度（涂-4\"杯）/s</td><td>90~130</td><td>打磨性</td><td>易打磨</td></tr><tr><td>细度/μm</td><td>≤50</td><td>耐硝基性</td><td>不咬底、不渗色</td></tr><tr><td>不挥发分/%</td><td>75±5</td><td>性能及用途</td><td>附着力、机械强度、耐溶剂性均优，</td></tr><tr><td>柔韧性/mm</td><td>≤3</td><td></td><td>可用于汽车、火车等运输车辆</td></tr><tr><td>冲击性/cm</td><td>40</td><td></td><td></td></tr></table></body></html>  \n\n（3）醇酸树脂类中间涂料目前无论国内外，单纯采用醇酸树脂作为中间涂料的已不多见，而多采用一些改性的品种。正如前面提到的那样，硝基纤维素类中间涂料具有干燥速率快、硬度高、打磨性能好等方面的特点，但是它的柔韧性差，冲击强度较低，经长时间日晒夜露很可能发生整个涂层龟裂。而醇酸树脂类中间涂料，尽管柔韧性优良，但干燥速率较慢，打磨性差。采用硝基纤维素改性醇酸树脂能集中两者的优点，避免不足。国内一家大型企业曾引进国外某公司的修补涂料系统中的二道底漆就是一例。硝基纤维素拼合醇酸树脂中间涂料的配方及工艺大体如下。  \n\n$\\textcircled{1}$ 配方（质量份）  \n\n\n<html><body><table><tr><td>特殊改性醇酸树脂</td><td>23.0</td><td>钛白粉</td><td>4.0</td></tr><tr><td>二甲苯</td><td>6.0</td><td>硬脂酸锌</td><td>2.8</td></tr><tr><td>BYK110</td><td>0.3</td><td>磷酸三丁酯</td><td>1.2</td></tr><tr><td>立德粉</td><td>11. 0</td><td>TT-88A</td><td>0.1</td></tr><tr><td>硫酸钡</td><td>5.0</td><td>膨润土胶（10%）</td><td>1. 5</td></tr><tr><td>炭黑</td><td>0.1</td><td>硝基纤维素溶液（30%）</td><td>36.0</td></tr><tr><td>滑石粉</td><td>6.0</td><td>醋酸丁酯</td><td>4.0</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 工艺  \n\na.将特殊改性醇酸树脂、二甲苯、BYK110加人到调漆缸中，混合均匀。b.在搅拌下慢慢加入立德粉、硫酸钡、炭黑、滑石粉、钛白粉、硬脂酸锌、磷酸三丁酯、TT-88A，然后高速分散至少 $30\\mathrm{min}$ 。c.在砂磨机上研磨至细度合格。d.再在搅拌下慢慢加入膨润土胶 $(10\\%$ ）和硝基纤维素溶液 $(30\\%)$ 。e.用醋酸丁酯调黏。  \n\n这类以醇酸树脂、硝基纤维素为主成膜物质的中间涂料表面上看与前述硝基纤维素类中间涂料并无多大差别，无论是基本成分还是其配比也都差不多。但需指出的是，这里所采用的不是一般短油度醇酸树脂，乃是经特殊改性的品种。该中间涂料具有干燥速率快，硬度高，易打磨，特别突出的是它对面漆的烘托性特别好。罩面漆后，其光泽和鲜映性明显优于采用其他中间涂料的结果。现将国内外这几种类型的中间涂料性能对比罗列于表3-2-45中。  \n\n表3-2-45国内外几种中间涂料性能比较  \n\n\n<html><body><table><tr><td>项目</td><td>灰二道浆</td><td>灰硝基二道浆</td><td>浅灰硝基二道浆</td><td>灰二道浆</td></tr><tr><td>产地</td><td>国内某公司</td><td>国内某公司</td><td>美国某公司</td><td>美国某公司</td></tr><tr><td>颜色及外观</td><td>灰色，平整</td><td>灰色，平整</td><td>浅灰，平整</td><td>灰色，平整</td></tr><tr><td>黏度（6*流出杯）/s</td><td>34.7</td><td>28</td><td>40.6</td><td>25</td></tr><tr><td>细度/μm</td><td>35</td><td>50</td><td>30</td><td>40</td></tr><tr><td>速盖力/（g/m²）</td><td>80</td><td>110</td><td>110</td><td>80</td></tr><tr><td>干燥时间/min</td><td></td><td>10</td><td></td><td></td></tr><tr><td>表干</td><td>10</td><td></td><td></td><td>10</td></tr><tr><td>实干</td><td>60</td><td>60</td><td>10 60</td><td>50</td></tr><tr><td>柔韧性/mm</td><td>2</td><td>5.有银纹</td><td>5.有银纹</td><td>5.有银纹</td></tr><tr><td>冲击性/cm</td><td>40</td><td>20</td><td>10</td><td>10</td></tr><tr><td>硬度</td><td>0.68</td><td>0.60</td><td>3H</td><td>3H</td></tr><tr><td>耐介质性</td><td></td><td></td><td></td><td></td></tr><tr><td>0. 05mol/L HSO</td><td></td><td></td><td></td><td></td></tr><tr><td>24h</td><td>。</td><td>。</td><td>。</td><td></td></tr><tr><td>48h</td><td>△</td><td>△</td><td>△</td><td>△</td></tr><tr><td>0. 1mol/L NaOH</td><td></td><td></td><td></td><td></td></tr><tr><td>24h</td><td>。</td><td>。</td><td></td><td></td></tr><tr><td>48h</td><td>△</td><td>△</td><td>△</td><td>△</td></tr><tr><td>对面漆的烘托性（光泽）/%</td><td></td><td></td><td></td><td></td></tr><tr><td>A</td><td>92</td><td>85</td><td>90</td><td>92</td></tr><tr><td>B</td><td>95</td><td>90</td><td>90</td><td>95</td></tr></table></body></html>\n\n注：A代表热塑性丙烯酸瓷漆；B代表丙烯酸-聚氨酯瓷漆；代表无变化：代表稍有变化。  \n\n(4）可调灰度底漆二道浆现在市面上流行的底漆、中间涂料的颜色一般只有灰色和泥黄色两种，这不符合在颜色方面底漆和面漆之间配合的基本准则。面漆对底漆的遮盖不完全取决于面漆本身遮盖力的好坏，它与配套底漆的颜色也有很大关系。经验告诉人们，涂装面漆时，在颜色相近的底漆上达到完全遮盖的耗漆量远远低于两者颜色差别大的结果。基于这一现象，2000年杜邦公司就向国内市场推出了所谓“可调灰度底漆”的概念。它们打破以往底漆、中间涂料的颜色只有灰色和黄色两种系列的局限，将灰色底漆分为浅灰、中灰以及深灰三种颜色制成底漆二道浆商品供客户选择。商品牌号为1141S、1144S、1147S，客户可以利用这三种不同的颜色调配出各种不同色调的底漆使之与面漆形成最佳覆盖的配伍。近来ICI公司亦发展了可调灰度底漆，据称可提高色母的遮盖力，有效减少喷涂次数，省时省工。足见可调灰度底漆确有价值。至于有些公司在底漆或中间涂料中加入色母调色的可调色产品，因色母的价格与底漆不在一个档次上，从经济的角度看是否合适很值得商榨，故不属此列。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1085,
+        "chunk": "# 4.汽车塑料零部件用涂料  \n\n能源危机导致客户对汽车轻量化的要求愈加迫切，与此同时对汽车车身抗冲击的能力也提出了更高的要求。为此各国汽车行业加快了从保险杠、车轮罩等的轻质合金化、塑料化的步伐，其中塑料化的步伐尤其迅速。从图3-2-8中可以看到，塑料件在汽车中的比例已达$8\\%$ 以上。由于现在我国汽车总装厂大都与国外汽车公司合资，故我国现在每辆汽车消耗塑料件的品种和数量可以说已与国外基本想当。  \n\n汽车特别是轿车上所采用的塑料品种较多，分内用和外用两大部分。  \n\n(1）汽车外用塑料件汽车外部的塑料零部件如保险杠、挡泥板以及车门镶边等所选择的涂料品种，除必要的装饰性外，显然首先考虑的应该是耐候性。另外还要求具有较好的耐介质性和耐磨耗性能。这类涂料多为丙烯酸-聚氨酯、聚酯-聚氨酯、热塑性丙烯酸类涂料。热塑性丙烯酸类涂料由于其抗划伤性能相对较差，已比较少用。现在多选用前两者，尤其是丙烯酸-聚氨酯类涂料。  \n\n(2）汽车内部塑料件汽车内部用塑料件，如仪表盘、控制手柄、各种把手、贮物箱、坐椅等。常用涂料为热塑性丙烯酸、改性环氧、聚氨酯以及有机硅系涂料等。目前采用热塑性丙烯酸类涂料的较多。  \n\n在汽车塑料零部件用底漆和面漆中，配套面漆的选择相对简单--些，只要考虑内用和外用两方面因素即可。底漆的选择则相对复杂，应重点关注。  \n\n总体来说，汽车塑料零部件所采用的面漆无论从配色还是性能等角度出发，大都就便选择汽车其他部位采用的漆种。其实汽车塑料零部件用漆关键是底漆，底漆的选择要复杂得多。这主要是由于塑料自身特性所决定的，因各类塑料的极性、结晶度、溶解度参数、杨氏模量、表面硬度等性能方面的差异，配套底漆肯定不能选择同一漆种。尽管上面提到的汽车用塑料件的种类较多，但常用的却不外乎ABS工程塑料、聚烯烃（聚乙烯、聚丙烯）以及玻璃纤维增强塑料三大类，这里仅就这三类塑料件底漆的品种分类介绍如下。  \n\n（1）ABS工程塑料ABS工程塑料涂装时无需专用底漆，常用热塑性丙烯酸类涂料与它的附着力都不错。ABS工程塑料因其自身的结构特性，使得它的耐有机溶剂性能较差，因此所采用的涂料和稀释剂中应严格控制芳烃类、酯类以及酮类溶剂的含量，以免造成“咬底”（涂料用户多将其称为“烧胶\"）等现象。  \n\n适用于ABS工程塑料的漆种有热塑性丙烯酸、丙烯酸-聚氨酯、醇酸树脂等。现多采用热塑性丙烯酸类涂料。  \n\n(2）聚烯烃聚烯烃是聚乙烯、聚丙烯、乙烯-丙烯共聚物的统称。在汽车行业中用得最多的是聚丙烯（PP)。聚烯烃类塑料的主要特点是它们的极性低、结晶度高、溶解度参数与一般有机溶剂相去甚远，因此它们几乎不溶于任何有机溶剂。另外聚烯烃材料表面还存在所谓“弱界面层”，因此一般涂料在其表面涂装时，在很多情况下甚至连润湿、流展都无法实现，那就更加谈不上能否获得有效的附着了。毫无疑问，聚烯烃类材料是除含氟聚合物、有机硅聚合物外另一大类难粘、难涂材料。  \n\n在汽车行业，解决聚烯烃类塑料的涂装问题时均采用专用底漆，其基本原理都是在非极性的聚烯烃表面与相对高极性的面漆之间构筑一道低极性的过渡层，以解决极性材料在非极性材料表面的润湿、流展、附着等一系列与涂装有关的问题。  \n\n聚烯烃专用底漆中主成膜物质的选择，主要考虑的是附着力好坏。选择的原则一般是利用相近、相似的原理，如采用氯化聚乙烯、氯化聚丙烯、过氯乙烯之类含氯烯烃聚合物；低分子量液态聚丁二烯树脂类低极性聚合物及其改性制品等。单纯采用氯化烯烃聚合物作为主成膜物质的底漆可在聚烯烃上获得良好的附着，但由于其极性仍然偏低，在它上面直接喷涂常用面漆（如丙烯酸-聚氨酯、聚酯-聚氨酯等)，不能获得满意的附着，必须适当提高氯化烯烃聚合物的极性。目前比较通行的做法是在氯化烯烃的大分子主链上引入一定量的极性基团，如羧基、羰基、羟基、酰氧基等。常见的如顺丁烯二酸酐接枝共聚氯化聚丙烯、丙烯酸（酯）接枝共聚氯化烯烃、丙烯酸（酯）接枝共聚低分子量聚丁二烯等。现举一例较成熟的接枝共聚改性的配方及工艺如下。  \n\n$\\textcircled{1}$ 接枝共聚树脂的合成a.配方（质量份）  \n\n氯化聚丙烯（不挥发分28%±2%） 335 丙烯酸丁酯 20-甲苯 70 苯乙烯 25-甲基丙烯酸二甲氨基乙酯 10\\~15 偶氮二异丁腊 1\\~甲基丙烯酸甲酯 35\\~40  \n\nb.工艺  \n\n·将配方量的溶剂、树脂溶液、单体及 $2/3$ 的引发剂一起投人到反应釜中。  \n·升温至 $80^{*}\\mathrm{C}$ ，保温 $^{2\\mathrm{h}}$ 9·然后在2h内补加其余引发剂。  \n·继续保温15h。  \n·降温、过滤、出料。  \n\n$\\textcircled{2}$ 涂料制造配方（质量份）如下。  \n\n接枝共聚物 多元醇缩水甘油醚  \n\n适量  \n\n国外不少公司所谓聚烯烃材料附着促进剂其实就是氯化烯烃改性聚合物，这些氯化烯烃改性聚合物既可单独使用，亦可作为附着力增强剂混拼在其他涂料体系中使用。单独作为底漆使用时，只需喷涂 $2.5\\sim5.0\\mu\\mathrm{m}$ 厚，室温下干燥 $2\\sim3\\mathrm{{min}}$ 即可获得满意的效果。它也可作为附着力增强剂添加到常用涂料中，其用量大约是 $5\\%$  \n\n进口汽车修补涂料系统中大都配备有专用塑料底漆。如PPG公司的D815、ICI公司的P572-167等均属于聚丙烯、乙烯-丙烯共聚物以及乙丙三元共聚物等聚烯烃类难粘材料的专用底漆。  \n\n丙烯酸接枝共聚改性氯化聚烯烃的技术路线不乏成功的范例，据介绍，采用这类树脂配制的专用底漆对未经处理的聚烯烃塑料具有良好的附着力，而且与其他通用面漆的配套性能  \n\n良好。  \n\n值得注意的是，大部分的这类底漆因主成膜物质—改性氯化聚烯烃聚合物的内聚强度都不高，故底漆漆膜的厚度需严格控制，一般如前所述，大约在5～10μm。如厚度偏低，则底漆易被面漆溶解，无法起到应有的桥梁作用；如厚度偏高，虽底漆对聚烯烃基材表面的附着尚可，但由于底漆成膜物质的内聚强度偏低，故很容易出现内聚破坏，同样反映出“附着力差”。举保险杠为例，其涂装工艺如下。  \n\n$\\Phi$ 打磨清除保险杠毛坯表面存在的缺陷。  \n$\\textcircled{2}$ 清洗采用专用清洗剂，清除表面的油脂、脱模剂等污物。$\\textcircled{3}$ 静电除尘清除表面可能吸附的灰尘等杂质。  \n$\\textcircled{4}$ 喷涂底漆采用上述提到的专用底漆，漆膜厚度一般为 $5\\sim8\\mu\\mathrm{m}$ $\\textcircled{5}$ 喷涂底色漆漆膜厚度约为 $15\\sim20\\mu\\mathrm{m}$ 曲  \n$\\textcircled{6}$ 喷涂罩光漆漆漆膜厚度约为 $25\\sim35\\mu\\mathrm{m}$ 营  \n$\\textcircled{7}$ 烘烤成膜一般烘烤条件为 $(70{\\sim}75)\\%\\times(20{\\sim}30)\\mathrm{min}.$  \n\n(3）玻璃纤维增强塑料在汽车行业用到的玻璃纤维增强塑料主要有SMC和RIM两种。在塑料工业中，所谓SMC是指片状模压成型料，RIM为反应型注射模内成型料。  \n\n玻璃纤维增强塑料所采用的树脂多为不饱和聚酯树脂或环氧树脂。因此这类塑料件的涂装无需专用底漆，但是也有一些值得注意的所在。无论采用何种方式成型的塑料件，由于模具精度、模具使用时间等方面的原因，塑料表面总要遗留不同程度的表面缺陷，如针孔、裂纹、流痕、划痕等；另外这些塑料的表面硬度都不高，在运输过程中难免擦伤、碰伤，因此这类塑料涂装前必须进行仔细的表面处理。  \n\nRIM是一种新型的成型加工法，国外于20世纪80年代开始引入汽车行业。由于这种类型的材料经玻璃纤维增强后，其热膨胀系数与普通钢材接近，故它们与钢材很容易匹配。近年来RIM塑料在汽车行业的用量与日俱增。过去这类塑料在涂装前的表面处理相对复杂，一般要采用专用溶剂脱脂清洗，如采用三氯乙烯蒸汽处理 $2\\mathrm{{min}}$ ，再在 $80^{\\circ}\\mathrm{C}$ 下至少放置$10\\mathrm{{min}}$ 以待处理溶剂完全挥发，然后才能进行下一步的涂装施工。  \n\n国外汽车修补涂料系统中亦有配套底漆供应市场，如PPG公司的D816就是一种RIM塑料专用底漆。D816对罩面有比较特殊的要求，它规定在 $40\\mathrm{\\sim}120\\mathrm{min}$ 内完成罩面漆或其他底漆。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1086,
+        "chunk": "# 5.防锈蜡、稀释剂、驳口水等  \n\n防锈蜡以及稀释剂、驳口水、防白水等，溶剂类辅料尽管组分简单、配方也不复杂，但对修补涂装质量的好坏却影响甚大。  \n\n（1）防锈蜡汽车车身某些部位无法单单依靠涂层就可以达到防锈的作用的，如车身上通过点焊形成的缝隙，因磁屏蔽作用而造成的阴极电泳底漆达不到的一些空腔、夹层等，那里几乎没有电泳上涂层或很薄。有也只是 $2\\sim4\\mu\\mathrm{m}$ 厚的磷化膜。另外，由于“尖劈效应”的存在，大部分阴极电泳底漆在装配孔附近所形成的涂层都较薄，这些部位肯定都达不到有关防腐蚀规定的年限标准，如：  \n\n$\\textcircled{1}$ 前翼子板支撑板、后轮罩内壁、后翼子板内壁、焊缝、螺钉装配孔；  \n$\\textcircled{2}$ 前、后梁空腔、底板空腔、车门下部空腔等；  \n$\\textcircled{3}$ 后厢盖内筋板空腔等。  \n\n为此，国外汽车行业从20世纪40年代开始就发展了内腔喷蜡（或注蜡）防锈技术。至目前为止，随着该项技术的不断完善，已经成功地解决了汽车某些部位防锈的问题。  \n\n显而易见，正像涂料涂层久而久之会逐渐破坏-样，防锈蜡更不会例外。蜡层也绝不可能比涂层的寿命还长。一段时间以后，肯定需要重新喷蜡保护。因此汽车修补涂料系列产品中也少不了防锈蜡。修补用防锈蜡的技术指标与新车的要求差不多。  \n\n<html><body><table><tr><td>滴点/℃</td><td>100</td><td>雾化性能</td><td>雾化性能好，均匀，无滴落</td></tr><tr><td>闪点/℃</td><td>27</td><td>盐雾试验（脱脂钢板，240h）</td><td>0~1级</td></tr><tr><td>干燥残留物/%</td><td>35</td><td>湿热试验（脱脂钢板，30天）</td><td>0～1级</td></tr></table></body></html>  \n\n喷蜡工艺与新车的工艺完全一样，即应该在涂料修补施工完成后再进行喷蜡。国外一些汽车修补涂料生产厂家往往有配套的防锈蜡出售，如AKZO公司就有好几个品种的防锈蜡供应市场，其中既有溶剂型的，也有水性的。  \n\n(2）稀释剂各类涂料中稀释剂的应用都很重要，在汽车修补涂料中尤其如此。国内外汽车修补涂料生产厂家均有一系列稀释剂供应市场，以满足不同季节、施工环境的需要。有关稀释剂配制方面的知识有关章节已经讨论很多，这里不再重复。  \n\n(3）驳口水在汽车修补喷涂施工完成后，特别是在进行局部修补的情况下，新-旧漆膜表面间难免存在一定视觉差。这其中有调色准确与否造成色相方面的问题，也有属于涂料雾化程度好坏方面的问题。为使修补效果更为完美，这个差别必须加以解决。通常的做法是喷一道溶解性较强的混合溶剂以溶解新旧漆膜接口处的较粗糙的漆粒，令新-旧漆膜融为一体，使之“驳口”，“驳口水”因而得名。  \n\n汽车修补涂料公司都有配套的驳口水商品供应市场。驳口水一般由强溶剂混拼而成。有公司建议在适当的驳口水中添加 $20\\%\\sim50\\%$ 的所使用的罩光清漆会使得驳口效果更佳。有的公司甚至直接使用罩光清漆，采用特殊施工手法来完成驳口。  \n\n驳口工艺最普通的做法是在完成补漆后，立即在接口处轻喷驳口水一遍，大约20s后再喷一道即可。总体来说，常用的驳口工艺有以下三类。  \n\n$\\Phi$ 纯驳口水工艺  \n\na.适用范围除三层珍珠漆外的小修补驳口。适用于门框，不显眼区域及双层金属闪光漆。  \n\nb.表面处理确保将驳口区域被严格清洁及除油。  \n\n·用不粗于P800砂纸（或P400湿打磨）打磨修补区域；  \n\n·在周边区域用3M灰色丝瓜布或水性研磨膏打磨；  \n\n·喷涂前用一块布除油、一块布清洁。  \n\nc.喷涂方式  \n\n·用低压（0.196MPa）喷涂覆盖底漆，采用弧形手法将喷涂控制在打磨区域内； $\\textcircled{2}$ 将1份驳口水兑 $_{1\\sim2}$ 份上述涂料于喷枪中，用低压（ $\\mathrm{0.196MPa)}$ ，弧形手法覆盖上一层，仍将喷涂控制在打磨区域于内； ar 9  \n\n·按要求干燥涂料；  \n\n·抛光或重涂，对于底色漆，用普通方式喷涂2K清漆于打磨区域内或用上述方法驳口。对于双组分面漆或清漆，进行机械或手工打蜡、抛光。  \n\n$\\textcircled{2}$ 添加清漆驳口工艺  \n\na.适用范围适用于本色漆及单层金属闪光漆。  \n\nb.表面处理同纯驳口水工艺。  \n\nc.喷涂方式  \n\n·用正常调配的涂料喷涂覆盖底漆，用低压（0.196MPa)，弧形手法；·用1份正常调配的清漆兑2份涂料于喷枪中，用低压（0.196MPa)，弧形手法喷涂覆  \n\n盖上一层，结束后立即清洗喷枪；  \n\n·喷涂2层正常调配的清漆于整个区域，喷枪上的气压为0.294～0.363MPa；  \n·按要求干燥涂料。  \n\n$\\textcircled{3}$ 三层珍珠漆的驳口a.适用范围三层珍珠漆修补及驳口。  \n\nb.表面处理同纯驳口水工艺。  \n\nc.喷涂方式  \n\n·将调配好的底色漆用0.196MPa的压力喷涂覆盖底漆，注意不要超过打磨区；  \n\n·用 $^1$ 份驳口水与2份上述底色漆在喷枪内混合，用低压（0.196MPa)，弧形手法喷涂覆盖上一层漆膜；  \n\n·将1份调配好的珍珠漆与2份上述混合漆在喷枪内混合，喷涂 $1{\\sim}2$ 薄层于上述漆膜的漆面边缘内，喷涂时使用低压（0.196MPa)，完成后将使用过的漆倒掉并清洗喷枪；  \n\n·喷涂正常调配好的珍珠底色漆，用 $0.167\\sim0.196\\mathrm{MPa}$ 的压力，喷涂数层以达到颜色要求，尽量不要超出底色漆层；  \n\n·将1份驳口水及2份上述珍珠漆在喷枪内混合，用 $0.167\\sim0.196\\mathbf{MPa}$ 的压力喷涂，覆盖上一层喷涂的漆膜；  \n\n·将1份调配好的2K清漆及2份上一步使用的混合漆在喷枪内混合，用0.196～).225MPa的压力喷涂，将上一步喷涂的漆膜完全覆盖，完成后倒掉混合漆并清洗喷枪；  \n\n·用普通方式，0.294～0.362MPa的压力喷涂调配好的2K清漆整块板块或驳口边缘区域；·按要求干燥涂料。  \n\n(4）防白水高温、潮湿天气或大面积喷涂时，漆膜表面容易出现发白的现象，有时即使使用慢干稀释剂也无济于事。在稀释剂中添加高沸点极性溶剂可在一定程度上避免或缓解漆膜发白的问题。这类高沸点极性溶剂在这里被称为“防白水”，它可进一步延长挥发时间，使漆料更加易于喷涂，流平效果更佳，避免漆膜表面出现水汽乃至发白。一般室温到 $30\\sim40^{\\circ}C$ 时，可加人 $10\\%\\sim30\\%$ 的防白水于慢速稀释剂中，高于 $40^{\\circ}\\mathrm{C}$ 时也可直接用它代替稀释剂。  \n\n(5）防走珠水在汽车修补涂装施工中，因油污或其他污垢造成的污染，有时会使漆膜出现缩孔、针孔、凹陷一类表面缺陷。为了对此进行补救，可在已配好各种辅料的漆料中加人 $0.5\\%\\sim2\\%$ 的表面活性剂。然后将已加入表面活性剂的漆料湿喷一遍于已出现问题的漆膜上（注意：该漆膜应刚刚过正常的挥发时间)，往往能够消除上述缺陷。南方汽车修补业内称之为“走珠”，所添加的表面活性剂则被称为“走珠水”。走珠水多为降表面张力能力强的含聚硅氧烷或含氟表面活性剂。  \n\n(6）控银剂控银剂用于1K系统中，它的加入大大改善了该类产品中效应颜料（铝粉、珠光粉以及超细钛白等）在色浆和成品底色漆中的分散、沉降性能，而且还有效地增加了其效应颜料的定向作用，使之具有更好的随角异色性、较少的云斑色差和雾影等。部分汽车修补涂料公司有此类辅料出售，如ICI公司的P030-9938、P017-2040等。  \n\n控银剂的配方比起防白水、驳口水之类辅料来相对复杂些，它的基本构成大体与1K调和清漆相似。所不同的是CAB和分散蜡的用量相对偏高一些。典型配方如下（质量份）。  \n\n醋酸丁酯 30.6 CAB 381-2 4. 5   \n二甲 29.0 CAB 551-0. 1 3.5   \n100芳烃溶剂 3.0 KCR-2015 12.0   \n异丁醇 3. 0 Disper KC 568 12.0   \nDBE 3.0 BYK 161 0.4  \n\n配方中KCR-2015为Kemperial公司产特种丙烯酸树脂。按照上述配方配制的控银剂用于高浓银浆（如ICI公司的P425-984之类产品）中效果不错。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1087,
+        "chunk": "# 三、汽车修补涂料系统及计算机配色  \n\n色漆配色过去都是由具有丰富配色经验的调漆师傅或技术人员进行。显然这样既费时，又费工。而且在多数情况下，很难在短时间内将新配制的色漆与标准色板之间的色差准确地调整到客户所允许的范围内。这是因为不同人对颜色的三元刺激值的敏感程度并不一样。光源以及环境的改变也会对人的视觉感受产生不同影响。另外如果一个人长时间连续调色，还会出现所谓“视觉疲劳”，这就进一步增加了人工调色、配色的局限性。国外从事调色、测色的工作人员大都为女性，女性对颜色的辨认比男性敏感。然而这并不能从根本上解决问题。要想彻底避免人为因素带来的误差，不得不求助于仪器。  \n\n20世纪80年代中期，国外从事测色、配色仪器制造的厂家将原用于纺织和染料行业的计算机配色系统软件经修改、增补后用于涂料工业，为涂料工业带来真正意义上的计算机配色。  \n\n计算机配色系统主要由分光光度计和配套的配色软件所组成，其基本配色程序如下。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1088,
+        "chunk": "# 1.建立颜料数据库  \n\n$\\Phi$ 按照软件的要求，将常用颜料分别分散在指定树脂，最好是水白色热塑性丙烯酸树脂中（选择热塑性丙烯酸树脂作为展色剂的原因是它不需要烘干，这就避免了烘烤时的温度可能给颜料或基材带来的负面影响)。研磨至细度达到 $10\\mu\\mathrm{m}$ 以下，制成色浆。  \n\n$\\textcircled{2}$ 用标准白色浆（指定品牌的钛白粉分散在上述树脂中）将颜料浆冲淡，制成颜料含量呈不同梯度的色浆。冲淡过程应在搅拌下慢慢进行，以避免任何絮凝发生。至少应制备$8\\mathord{\\sim}9$ 个色浆。配比范围为钛白浆：颜料浆 $\\fint(0\\sim9)\\colon1$ 西  \n\n$\\textcircled{3}$ 将冲淡混合色浆用标准刮涂器刮涂于指定的白纸上，得到具有一定厚度的涂层，然后风干。  \n\n$\\textcircled{4}$ 分别在分光光度计下读数，经配色软件读人、计算，最后完成将该颜料的数据存入计算机。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1089,
+        "chunk": "# 2.测色、调色  \n\n$\\Phi$ 将待调色标准色板通过分光光度计读取数据。$\\textcircled{2}$ 计算机配色仪软件计算所读入的数据，经计算给出配方。$\\textcircled{3}$ 按照计算机给出的配方生产。$\\textcircled{4}$ 将生产所得色漆制板，并再次给分光光度计读数。↑ $\\textcircled{5}$ 在输入生产批量的前提下，计算机根据所测数据与标准色板比较，输出应补加的色浆品种和数量，补加色浆。  \n\n$\\textcircled{6}$ 重复 $\\textcircled{4}$ 、 $\\textcircled{5}$ 操作直至产品与标准色板之间的色差缩小到标准所要求的范围内。  \n\n汽车修补涂料利用计算机的测色、调色除了在用色母调配成品漆生产时，符合上述程序外，还要依靠计算机配色仪，控制浓色浆和成品色母的质量。  \n\n值得注意的是大部分计算机配色仪厂商原来的主要客户对象都是纺织或染料行业。不少计算机配色仪移植到涂料行业后，并未结合涂料产品的特殊性对软件进行适当修改，这样配套软件往往容易忽视涂料行业中特有的一些参数，如遮盖力、吸油量等。如不加以留意，计算机软件可能给出无法用于实际生产的配方。  \n\n应该说无论计算机测色、配色还是肉眼判断，两者都应相辅相成。计算机配色仪可以帮助调色工调色时少走弯路。而最终成品漆的颜色是否合格，不仅仅要看 $\\Delta E$ 是否在指标容许范围内，同时还应该辅以肉眼判断。  \n\n采用计算机配色仪最重要的操作在于第一步建立所用颜料的基本数据库。这一步操作应该非常严密，甚至苛刻地予以控制，稍有大意将为以后的测色、调色工作带来极大误差。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1090,
+        "chunk": "# 3.配色实践  \n\n修补施工开始前，首先应该查看汽车总装厂留在车身上色卡号，查阅涂料生产厂家提供的计算机查询系统或菲林以获取配漆配方，然后再用色母配漆。汽车总装厂留在车身上的有关色卡号的标牌并无统一规范。有的简单，有的则非常详细。如美国通用汽车公司的标牌上面列出了包括车身各个部位所用的材料、颜色以及车身各部位涂料材料的类型及颜色等。在涂料类型栏就可查看到该车所采用涂料的类别，不同的代码分别代表涂料类型是溶剂型自干涂料、非水分散涂料、高固体分涂料、水性涂料还是底色漆 $^+$ 罩光清漆等。大多数总装厂将标牌粘贴在车前盖底下的发动机仓内，打开前盖就可找到。有的厂则放在前车门缝部位。  \n\n由标记牌上的色卡号通过计算机查询系统查询配方、配漆的基本程序如下。  \n\n汽车总装厂名 → 色卡号 查询配方 → 配漆如：丰田 如：307/1744 得：2K530 364.62K544 493.62K010 69.52K611 140.2  \n\n注：2K530、2K544、2K010、2K611为德国Herberts公司施得乐（Standox）系统色母，配方亦为该公司的计算机查询系统提供，  \n\n按照查询到的配方配漆，如果采用的色母来自信誉较好的修补涂料厂的产品，应该不会有太大的色差，稍加微调即可。不过即使是进口产品，成品漆的颜色有时也需要微调。色差产生的原因是多方面的。既可能是操作不当，如生产厂控制不严，使用者搅拌不均匀（包括前一次使用该色母时没有搅匀）等，也可能是待修补的汽车已使用多年，车身上的涂层已有部分老化现象，按照原厂漆颜色配制出来的产品与旧涂层间存在一定色差。因此国外名牌汽车修补涂料厂除根据色卡号提供固定配方外，还向客户提供调色参考指导，如颜色太亮、颜色太暗、颜色太黄、颜色太红时应补加哪几种色母，为使用者提供不少方便。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1091,
+        "chunk": "# 4.调漆  \n\n在完成配漆、调色工作后还要加入稀释剂（如果是双组分还要加固化剂）将漆料兑稀成施工状态。这里首先需要注意的是稀释剂的类型，不要将1K和2K用的相混。因为1K稀释剂中多加有丁醇一类含羟基溶剂，如果错用于2K色母的兑稀，将对漆膜外观带来不利影响。其次是要注意环境温度的高低，以选择不同挥发速率的稀释剂。最后是施工黏度，一定要按照施工工艺参数调漆，过低或过高的施工黏度都会对漆膜外观带来不良影响。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1092,
+        "chunk": "# 第六节汽车涂料的涂装工艺  \n\n随着我国汽车行业的飞速发展、汽车制造工艺水平的不断提高和市场需求量的变化，越来越多的汽车制造厂家也不惜投入重金建设产能更大和制造水平更高的生产线，其中的重点就是占到汽车生产线总投资30%左右的汽车涂料涂装线。汽车行业如此重视汽车涂料的涂装是有充分道理的。众所周知，汽车涂料实质上包含涂料制造和涂装施工两个部分，两者之间相辅相成、息息相关，忽视任何一个方面都是错误的。涂料与多数其他领域的产品有所不同，其品质的充分发挥不仅与其自身的性能有关，而且和它们的施工性能好坏有着极为密切的关系，而汽车涂料和涂装技术之间的关系更可算涂料业中之最。因此，国外不少汽车涂料生产厂家都把汽车涂料研究开发中不少于1/3的人力、物力用于涂装技术研究上。有的超级大公司还为此设立专用于汽车涂装技术研究的研究所。由此可见国外同行对汽车涂料施工应用技术的重视。  \n\n汽车涂装系统近年来发展迅速，已经由原来的2C2B发展到3C2B、3C1B、4C3B、4C2B，即两涂两烘、三涂两烘、三涂一烘、四涂三烘、四涂两烘等。今天的高级轿车的涂装系统甚至发展到多达7C5B的程度。涂层总厚度也由原来的 $30\\sim45\\mu\\mathrm{m}$ 增加到 $130\\sim$ $150\\mu\\mathrm{m}$ ，逐步实现了由低级到高级的过渡。涂料行业已经基本做到了满足汽车行业对不同档次车辆涂装的要求。一般汽车总装厂主要根据所生产的汽车的档次来决定所应该采取的涂装系统及涂层厚度。汽车总装厂采用的涂装系统可以归纳为以下几类。  \n\n$\\textcircled{1}$ 底漆-腻子（密封胶)-本色漆。   \n$\\textcircled{2}$ 底漆-腻子（密封胶)-中间涂料-本色漆。   \n$\\textcircled{3}$ 底漆-腻子（密封胶)-中间涂料-单层金属闪光漆。   \n$\\textcircled{4}$ 底漆-腻子（密封胶)-中间涂料-金属闪光底色漆-罩光清漆。   \n$\\textcircled{5}$ 底漆-腻子（密封胶)-中间涂料-本色底色漆-罩光清漆。   \n$\\textcircled{6}$ 底漆-腻子 (密封胶)-防石击中间涂料-中间涂料-金属闪光底色漆-罩光清漆。   \n$\\textcircled{7}$ 底漆-腻子（密封胶)-中间涂料-金属闪光底漆-底色漆-罩光清漆。   \n$\\textcircled{8}$ 底漆-腻子（密封胶)-防石击中间涂料-中间涂料-金属闪光底漆-底色漆-罩光清漆。  \n\n上述涂装系统中，第 $\\Phi$ 类是汽车工业发展初期所采用的涂装系统。目前国外基本已不再采用。我国一些低档车辆，如载货汽车、农用车辆、公共汽车等的涂装系统仍然采用第 $\\Phi$ 类。第 $\\textcircled{2}$ ， $\\textcircled{3}$ 类涂装系统在国外被用于大型车辆如巴士、集装箱货车等中档车辆上，国内则用于小型面包车、各种微型车以及经济型轿车等中档车辆上。第 $\\textcircled{4}\\sim\\textcircled{6}$ 类系统则用于轿车涂装中。第 $\\textcircled{7}$ ， $\\textcircled{8}$ 类是近几年发展起来的一种新型涂装系统。它与以往的涂装系统的不同之处在于使用了金属闪光底漆 $^+$ 底色漆，而不是通常的金属闪光底色漆。在金属闪光底漆中不含着色的透明颜料，只有铝粉、珠光粉之类效应颜料。在底色漆中则不含效应颜料，只有着色颜料。金属闪光底漆和底色漆的涂装顺序有时也可能互换，即在采用只含珠光粉的底漆时，先喷底色漆。采用这类涂装系统，使涂层整体的装饰性更为华丽、美观、别致；铝粉、珠光粉之类效应颜料的排列更为规整，闪烁均匀，立体感更强。观察这类涂层时，明显感受到它不同寻常的丰满度、深度，其艺术感染力更为强烈。显然这类系统的涂装成本肯定不菲，在国外也仅仅用于一些豪华型高档车辆上。  \n\n值得注意的是现今汽车涂装业新发展起来的所谓3C1B，即在电泳底漆涂装后以湿碰湿的方式喷涂中涂、底色漆和罩光清漆，再一起烘烤的工艺。该工艺取消了中间涂料的烘烤设备，减少了占地面积，另外，还无需打磨中间涂料等，提高了生产效率，降低了能耗等，该工艺已在不少汽车总装厂投人使用。  \n\n本节中将分别就汽车原厂漆和汽车修补漆的施工作较为详细的介绍。至于涉及涂装线的布局、设计等方面的内容因限于篇幅，这里不加讨论。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1093,
+        "chunk": "# 一、汽车原厂漆",
+        "category": " Introduction"
+    },
+    {
+        "id": 1094,
+        "chunk": "# 1.阴极电泳底漆的投槽及日常维护  \n\n在电泳涂装中，涂装质量不仅仅与CED自身的质量有关，更为重要的是它和涂装线的整体设计、安装以及工艺设备是否合理、完善，生产的管理水平和管理质量有着更为密切的关系。从电泳涂装的一般工艺流程中可以看出，影响涂装质量主要是以下几道工序：  \n\n表面预处理（清除焊渣、毛刺）—→除油除锈—→表调、磷化、钝化—→水洗—→电沉积—→电沉积后水洗—→烘烤成膜  \n\n（1）表面预处理在对工件表面进行预处理之前要清除工件表面的焊渣、毛刺等附看物。一般进行本工序时，工件尚未上线。本工序处理质量是否达到要求，不仅关系着工件有关部位涂层的附着力，而且对涂装产品的外观质量影响极大。这是因为焊渣、毛刺等附着物凸出于工件表面，会影响到涂层的平整度。另外，焊渣中还含有碳、碳铁化合物等不纯物质，这些杂质如不清除，不仅会影响到工件表面的粗糙度，而且还将对该部位的工件的导电性能带来改变。  \n\n(2）除油除锈该工序是表面处理中最为重要的工序之一。本工序品质的好坏直接影响到最终涂装质量。以往较为常见的是酸洗法（或“二合一”法)，后来则发展起来了较为先进、有效的“超声波”法以及采用可生物降解的表面活性剂取代传统的烷基酚-聚乙二醇，以提高脱脂能力，改善水洗效果，减少COD排放等。影响除油、除锈处理质量的因素虽略有不同，但也有其共同之处，如工件的材质及其表面状态，除油、除锈液的种类和品质，以及运作过程中 $\\mathsf{p H}$ 的监控，工作液的温度和使用周期、 $\\mathrm{Fe}^{2-}$ 含量等。本道工序的质量控制关键在于工作液的 $\\mathbf{\\Pi}_{\\mathrm{pH}}$ 、温度以及工作周期。当发现处理效果明显下降时，就应采取一定措施，如提高pH或温度。一般采取上述措施后效果不明显时，则可以判断为工作液使用周期过长，应及时更换。  \n\n(3）表调、磷化、钝化有的车厂为了进一步提高磷化质量，在工件磷化前，表面还需要经过所谓“表调”。表调处理有液体和固体之分，液体表调剂主成分为磷酸锌铁，固体表调剂主要有磷酸钛等。液体表调剂具有使用方便、槽温稍高亦可保持稳定、施工工艺参数范围相对较宽、槽液使用寿命长等特点，故将逐步取代固体表调剂。  \n\n磷化处理：为了得到较高的磷化处理效果，如磷化膜要均匀、致密等，必须对磷化液进行不亚于选择CED涂料的精心挑选。影响磷化质量的因素除与磷化产品质量密切相关外，最主要的是工作液的温度、游离酸度、总酸度、促进剂浓度等。应定期进行监控，切实保证磷化膜均匀、致密，一般磷化膜膜厚约为 $1\\sim3\\mu\\mathrm{m}$ 费  \n\n传统的钝化剂为一种六价的铬盐，这是一类剧毒化合物，且有一定致癌作用。现在不少汽车预处理剂专业生产厂家致力于无铬钝化剂的研发，如采用六氟化铬钝化剂，具有钝化效果好、废水处理较为方便等优点。  \n\n(4）水洗磷化后水洗的目的不仅是清除工件表面残留的磷化液，避免对漆膜的性能带来影响，另外，这些残留在工件表面的磷化液如果被带入下道电泳槽的槽液中，则势必引起更为严重的后果。被磷化液污染的槽液其稳定性和电泳特性都会发生改变，从而降低电泳涂装的质量。另外，由于槽液被污染，其稳定性必将大大下降，严重时还会出现絮凝、沉降、结块，乃至变质报废。这不仅直接地影响涂装生产的正常进行，而且将严重地降低涂料利用率，从而导致涂装成本大幅度增加。此道工序的监控关键在于应随时观察工件表面是否有返锈现象，较为普遍和简单的做法是检测冲洗水由工件上滴落的液体的电导率和pH。如果超标，则必须加强水洗以及冲洗水本身质量的控制。  \n\n(5）电沉积该工序是整个电泳涂装的中心环节，因此，除了前处理质量应获得足够的保证外，要获得较好的涂装效果，必须严格控制有关参数，使各项工艺参数均处于正常的范围内，如槽液的固含量、颜基比、电导率、 $\\mathsf{p H}$ 、溶剂含量、槽液温度以及施工电压等。  \n\n(6）电沉积后水洗此道工序的目的是：冲洗干净工件表面电沉积后还残留的多余漆料，回收重复利用，以提高涂料利用率。一般电沉积后的水洗分两步：首先采用超滤液在工件升离槽液后，就在电泳槽中进行冲洗；然后待工件进入冲洗槽后再采用循环水冲洗。这样就可以获得外观良好的CED漆膜。  \n\n(7）烘烤成膜烘烤成膜是电泳涂装的最后一道工序，其关键是烘烤时间和烘道温度。烘烤时间可由传动链的链速来控制，而烘道温度（更为重要的是烘道中的温度梯度）则可通过对各加热单元的调控来实现。此道工序的要点是要避免“过烘”或“欠熟”的现象发生。为此建议有条件的涂装厂可配置烘道温度测定仪，以定时对烘道温度及其分布进行监控。  \n\n除上述各要点外，保持整个施工环境的整洁、有序，防止污染物或悬链轨道上的锈渣、尘埃、油污等掉落人工作液（特别电泳漆液）和涂件上，造成“二次污染”，也是非常重要的。  \n\n（1）投槽前系统的清洗及其他准备工作  \n\n$\\textcircled{1}$ 清洗清洗工作最好安排在整个涂装车间完工后，这样可以避免设备清洗后被二次污染。  \n\n$\\textcircled{2}$ 清洗前要做好下述准备工作。  \n\na.足够的去离子水（DI水)，其电导 ${\\leqslant}10\\mu\\mathbf{S}/\\operatorname{cm}$ （国内大部分要求≤20）。  \n\nb.清洗工具，如硬毛刷、长柄刷等。  \n\nc.可靠的水源，特别是高压水源（一般可利用消防水源）。  \n\nd.高压水系统。  \n\ne.指定的化学清洗材料。  \n\nf.列出具体的人员安排及时间进程表。  \n\n$\\textcircled{3}$ 清洗项目。  \n\na.电泳槽及相关的设备（如转移槽、管道、阀门、循环泵、过滤器及换热器等)。  \n\nb.电泳漆的加料装置及相关设备（加料泵、预混槽、管道等）。  \n\nc.阳极液循环系统（阳极液贮槽、流量计及管道系统）。  \n\nd.超滤系统（未安装超滤膜的超滤管、超滤液贮槽、流量计、管道系统及反冲洗系统等)。  \n\ne.电泳后面冲洗区的壁、槽体及有关系统（管道、过滤器、喷淋管及喷嘴）。  \n\nf.烘道及有关系统。  \n\ng.最后的验收以主槽为基准。  \n\n$\\textcircled{4}$ 清洗过程  \n\na.碱洗在电泳槽等设备中加满自来水，然后加 $0.5\\%$ 的氨水（浓度为 $25\\%$ ）和 $1\\%$ 的溶剂（根据CED的具体材料确定溶剂的品种）循环清洗 $12\\mathord{\\sim}24\\mathrm{h}$ Y  \n\nb.水洗排放所有的碱液至废水处理站，然后用高压水冲洗内壁。再用清洗工具手工清除残留的污垢、杂质等。注意不要破坏电泳槽内壁的绝缘衬里。  \n\nc.酸洗排空所有的清洗物料，再在电泳槽等设备中加满自来水，然后加入0.1%的有机酸（根据CED材料决定品种）进行中和及清洗，循环时间为 $12\\sim24\\mathrm{h}$ 。酸洗后水溶液的$\\mathfrak{p H}$ 应为 $5{\\sim}6$ 要 足d.二次水洗排放酸洗液后，再用高压水冲洗设备，同时辅以手工清洗。  \n\ne.DI水洗先用DI水（电导率 ${\\leqslant}10\\mu\\mathbf{S}/\\operatorname{cm};$ ）冲洗各部位并排空。在各过滤器中装入过滤袋（规格为 $50\\mu\\mathrm{m}$ 或 $25\\mu\\mathrm{m})$ ，然后在电泳槽中加满DI水，循环清洗至少12h。  \n\nf.检查清洗效果主要以电泳槽中水溶液的质量为基准，重点控制以下两项。  \n\n·水洗液的电导率应低于 $50\\mu\\mathrm{S}/\\mathrm{cm}$ ，否则应重新更换DI水再循环水洗。  \n\n·样板试验：在实验室配制的电泳小槽中，加人5%的DI水洗液，检测该槽液的各项参数并进行泳板实验，结果应与加水样前一样，否则应判为清洗不合格。  \n\n$\\textcircled{5}$ 其他准备工作  \n\na.阳极系统主要是阳极盒的安装，安装时间最好是在DI水循环清洗的时候。务必注意：阳极液循环一旦开始，在整个投槽的过程中都不能停止。  \n\nb.UF系统在DI水清洗后可安装UF膜，制备好的膜应浸泡在DI水中。  \n\nc.烘道的清理首先用机械方法全面清理烘道内部，然后安装过滤网。启动空气循环系统进行循环清洁。  \n\n(2）投槽在进行初次投槽之前，除完成设备清洗外，还必须完成电泳涂装线各工位的功能检查（包括传动系统、电泳涂装设备、能源、供电、DI水以及废水处理装置等)。  \n\n$\\boldsymbol{\\Phi}$ 投槽前的准备  \na.DI水的质量， $\\leqslant10\\mu\\mathrm{S}/\\mathrm{cm}$ . $\\mathrm{pH}6{\\sim}7.$ 西  \nb.DI水的产量应能保证供应。  \nc.CED及其辅料（中和剂、添加剂等）。  \nd.投槽时间表及应急方案。  \ne.现场服务技术人员的具体安排及检测手段。  \n\n$\\textcircled{2}$ 一般原则CED材料不同，投槽方式也不同。既可在预混槽中稀释后投，也可直接投入到主槽中。主槽中要加入一定量的DI水，并在加漆前开循环系统进行搅拌。此时应该注意的是，在投槽过程中槽液的固含量从0开始逐渐升高。这是一个渐变分散过程，要注意， $6\\%$ 的分散过程越短越好。因此，投槽前加入的DI水量应尽量控制在刚刚可以循环的水平，使得投槽开始时的固含很快就能 $55\\%$ ，然后随着漆液的加入逐渐补加DI水。在投槽过程中，槽液的固含不得超过标准过多，一般初次投槽的固含量要控制在略高于标准值，如标准为 $15\\%$ ，则控制在 $16\\%\\sim17\\%$ 。槽液的液面要低于正常的水平，为调整槽液留有余地。  \n\n$\\textcircled{3}$ 投槽工艺举例—-采用线内混合器在现代化大型车身涂装线上，广泛采用循环系统的线内混合器作为初次投槽和补漆的手段，即原漆与槽液按一定的比例［通常为（ $50\\sim$ 100）：1]经过线内混合器混合后直接进入溢流槽。这种工艺简便、高效，既适合连续均匀地补漆，从而保证在涂装过程中槽液的成分始终稳定，也可用于初次投槽，对槽液组成的变化进行适时而有效的控制。以一种进口线内混合器为例说明如下。  \n\na.排空系统内所有的DI水，装好各过滤器的滤袋。b.加DI水到主槽中，加量应足以启动循环系统，尤其是线内混合器所在的管道更应仔细清洗，充分循环。c.按0.0005%槽液（包括循环系统总体积）的比例加入乳酸，也有用甲酸或乙酸。d.用高黏度泵将乳液泵入槽内（也有将原漆泵入线内混合器）。  \n\n注意：每加入一定量的原漆后或每隔一定时间（如1h）从循环系统取样点取样，测$\\mathsf{p H}$ ，用玻璃片观察槽液的分散状态。必要时调整某些参数，如加料速率、槽液的流动等。一旦槽内体积容许，应尽快开动所有的循环泵并调整槽液的流动状态。加入预计量的原漆后，用DI水调整液位（应该比正常液位要略低)，调整槽液的流速。通常液面的流速${>}100\\mathrm{mm/s}$ ，入口处 ${>}200\\mathrm{mm/s}$ 西  \n\ne.检查槽液的各项指标。 $\\mathrm{\\dot{\\cdot}{\\mathbf{p}}H}$ 、电导率、NVM，灰分、MEQ以及溶解度等）。  \n\nf.调整所有的相关设备并投入运行，密切注视过滤器进出口的压差变化，了解槽液的分散情况以便及时采取措施。  \n\n$\\textcircled{4}$ 槽液的配制CED供给客户的形式有单组分亦有双组分，现今绝大多数阴极电泳漆都是以双组分供应给客户，即乳液树脂和颜料浆。树脂组分占所供体积的 $75\\%\\sim85\\%$ ，它是一种乳白色的液体，黏度和密度与水相似。颜料浆组分占所供体积的 $15\\%\\sim30\\%$ 。这两种组分按照上述工艺混合后，再加入去离子水就完成了槽液的配制。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1095,
+        "chunk": "# $\\textcircled{5}$ 投槽注意事项  \n\na.工件上线前必需要求跑空，最好用黏性车身走一遍。烘干室最好用黏性抹布擦拭干净。  \n\nb.过滤系统：过滤器的进出口管路上必需装置压力表，当压差达到 $0.078\\sim0.$ 112MPa时，必须更换滤袋，对前处理液和清洗水都要过滤 $(25\\sim30\\mu\\mathrm{m}$ 袋式过滤)，否则有可能使磷化不匀影响漆膜外观。  \n\n·槽液过滤细度 $50\\sim80\\mu\\mathrm{m}$ （有的汽车总装厂建议 $25\\sim50\\mu\\mathrm{m})$   \n·UF液过滤细度 $80\\sim150\\mu\\mathrm{m}$ 费  \n·前处理液及清洗水过滤细度 $25\\sim30\\mu\\mathrm{m}$ 克  \n\nc.阳极系统应有电导率测量和浊度控制，以便决定DI水、酸的补充以及阳极液的排放。阳极液要求控制：  \n\npH  \n\n300\\~1200  \n\nd.阳极液中的CI离子、Fe离子浓度应严格控制。一旦发现超标，应对阳极进行钝化处理。其方法是在阳极液中加人 $0.015\\%$ 的浓 $\\mathrm{HNO}_{3}$ ，至少循环3h，然后排放，再加人新鲜的阳极液。  \n\ne.循环泵应采用双机械密封，密封液为UF水，应定期检察浊度。循环次数一般为56次/h，不能间断。一般来说，2h不循环，漆液开始沉淀， $5\\sim6\\ensuremath{\\mathrm{h}}$ 不循环，将会结块。泵的转速一般不得超过 $1500\\mathrm{r/min}$ （曾有过国内某厂采用 $3000\\tau/\\mathrm{{min}}$ 的泵使CED槽液报废的案例)，这主要是因为漆液与泵叶片之间强大的剪切力使乳液破乳，另外，摩擦所产生的局部过热，也会使漆液结块。换用备用泵时，主泵要立即用DI水清洗。多数汽车总装厂负责维护CED槽的技术人员认为：不设置备用泵而采用坏了及时抢修的方法更好些，因为备用泵及其旁路系统长期不用会导致槽液沉降，严重时还会堵塞管道。  \n\nf.检查和调整电泳槽内喷射器的安装角度，一般为水平向下 $10^{\\circ}\\sim15^{\\circ}$ ，槽液流速底部为$\\geq0.4\\ensuremath{\\mathrm{m/s}}$ ，上层为≥0. $2\\mathrm{m/s}$  \n\ng.检查和调整溢流板的位置，溢流板的位置应使溢流槽的容积为电泳槽的1/10。对100t的电泳槽而言槽液至溢流槽的落差应为 $50\\mathrm{mm}$ ，如果大于 $150\\mathrm{mm}$ ，则在开启循环泵时将极有可能产生大量的泡沫。  \n\nh.槽液面应低于槽体表面 $300\\mathrm{{mm}}$ ，工件应低于槽液面 $200\\mathrm{{mm}}$  \n\ni.超滤系统的清洗必须完全。第一次UF水必需配槽以检验是否能并入系统。超滤系统一旦投入使用就不能停止，如果停止，势必产生漆浆沉降，给清洗带来困难。UF水应定期排放，否则槽液中的阳离子浓度超标 $(25\\mathrm{mg}/\\upk g)$ 导致漆料的水溶性变差，严重时会使涂装面上出现颗粒。 5  \n\nj.更新期上限为15周，如果大于此数，则槽中将有大量陈漆未被置换，势必导致槽液的电泳性质变坏以及漆膜性能变差。更新期的计算公式如下：  \n\n$$\n\\scriptstyle\\mathrm{TO=}V N K\\times{\\frac{10}{S H D}}\n$$  \n\n式中TO——更新期，月；V——槽容积， ${\\mathfrak{m}}^{3}$ N-—-NVM，%；  \n\n$\\kappa$ 电泳漆利用率， ${>}95\\%$ \\*$s$ —每月涂装总面积， $\\mathbf{m}^{2}$ /月；$H$ —干膜厚， $\\mu\\mathrm{m}$ $D$ -—干膜密度， $1.3{\\sim}1.4\\mathbf{g}/\\mathrm{cm}^{3}$  \n\nk.磷化膜厚：一般对磷酸锌磷化而言在 $2\\sim3\\mu\\mathrm{m}$ 。太厚，降低电沉积效率；太薄，则防腐蚀性差。磷化前工件应呈弱酸性，这样可以保证磷化膜结晶不致变粗。磷化后的清洗应看作磷化的基本组成部分，最后清洗水的电导率必须低于 $50\\mu\\mathrm{S}/\\mathrm{cm}$ ，循环DI水洗液的电导率为 $100\\mu\\mathrm{S/cm}$ 以下，新鲜DI水洗液的电导率为 $25\\mu\\mathrm{S}/\\mathrm{cm}$ ，这对防止漆膜出现针孔是有好处的。另外，这些污染物带人槽中会污染槽液，影响槽液的稳定性。磷化残渣应及时除去，要求在 $300\\mathrm{mg/kg}$ 以下。某些厂家甚至要求在 $40\\mathrm{\\sim}120\\mathrm{mg/kg}$ 。当磷化渣达到 $6000\\mathrm{mg/kg}$ 时，形成所谓渣爆炸，车身上将可能带有大量的白色磷化渣。添加结渣剂，加强结渣系统的运转。在前处理工序，应尽量避免槽与槽之间窜水，交叉污染。工位与工位之间过渡区的距离最少保持1.5个工件长度。  \n\n1.检查电源技术指标  \n\n·实验室用   \n电压调整范围 25\\~300V 纹波系数 ≤4% 电流 10mA\\~20A 交流电源 220V,10A 稳态电流 ≤10A  \n\n·工厂用以二段加压方式为例说明。  \n\n第一段：  \n电压调整范围 0\\~250V 电流 140A,4. 375A/m²工件第二段：  \n电压调整范围 300\\~450V 电流 250A,7. 8A/m² 工件  \n\n(3）CED槽运行过程中的注意事项  \n\n$\\textcircled{1}$ 槽液的 $\\mathsf{p H}$ 必须保持恒定，如果控制低限，对槽液稳定有利，但过低则将对设备腐蚀加剧（有资料报道 $\\mathrm{pH}{<}5.\\ 9$ ，槽液对泵和管道的腐蚀都加剧，使Fe离子进入电泳槽中），还有可能引起破乳。如果pH超出指标范围，会造成槽液不稳定，产生大量不溶性颗粒，沉积在工件表面，使表面粗化，产生所谓“痱子”。某大型汽车总装厂CED槽pH一直在指标范围内 $(6.5\\sim6.7)$ ，但运行3年后，槽液面变色，泡沫增多，涂装表面满布颗粒，只能清槽过滤，加酸以降低 $\\mathbf{pH}$ ，以及严格控制新漆的质量。经验表明，长期连续使用，槽液的老化和污染是不可避免的。采取下列措施可防止槽液的老化和污染。  \n\na.pH控制在 $6.1\\pm0.1$  \n\nb.定期排放UF水（有时电导率并未超标)，用DI水替换。  \n\n$\\textcircled{2}$ 一般情况下，电导率在小范围内波动 $(\\pm100\\mu\\mathrm{S/cm})$ ，虽然对漆膜性能的影响不大，但过大则会使漆膜变粗。一个300t的槽用20tDI水代替UF水可使电导率下降 $100\\mu\\mathrm{S}/\\mathrm{cm}$ 如果槽液的电导率升高，泳透力也随之升高，膜厚也会增加。另外，杂质含量偏高也会产生“盐析”作用，影响到乳液型槽液的稳定性。所以在控制电导率的同时还要定期监测杂离子含量。控制杂离子含量可采取下列措施。  \n\na.定期排放UF水（有时电导率并未超标)，用DI水替换。  \n\nb.严格控制杂离子的浓度，特别是Na、Ca等阳离子。  \n\n$\\textcircled{3}$ 槽液的NVM。补充新乳液或色浆应按比例进行，切不可一下加得太多或几天不加，应将指标控制在 $\\pm0.5\\%$ 的范围内。  \n\n$\\textcircled{4}$ 槽液温度一般应控制在标准所规定的范围内，如 $28\\mathsf{C}\\pm1\\mathsf{C}$ ，超过 $30\\Upsilon$ 槽液易变质。  \n\n有机物的水溶液在高温下易变质（如酸败、发臭等)，使糟液的稳定性变差。在节假日期间，槽液的温度可以在低于25℃下循环，PPG要求控制在0.5℃范围内，每平方米工件在电泳过程中放出的热量一般为 $668.8{\\sim}710.6\\mathbf{k}\\mathbf{J}/\\mathbf{h}$ ，CED比AED的发热要高。据了解，南方某大型汽车总装厂的CED槽，即使在冬季也从未使用过加热装置，反而要频繁开启冷却系统(CED电能转化为热能以及UF循环摩擦热都比AED高）。  \n\n$\\textcircled{5}$ 槽液在长期使用过程中与空气接触等方面原因产生老化，造成漆基的水溶性变差，电导率下降（有时 ${<}1000\\mu\\mathrm{S/cm})$ 。此时应加强UF水的排放以及适当将pH降低一些。  \n\n$\\textcircled{6}$ 电泳槽所在车间的空气中尘埃颗粒大小 $<5\\mu\\mathrm{m}$ ，尘埃个数 ${<}300$ 个 $\\mathbf{m}^{3}$ ，尘埃含量$<4.5\\mathrm{mg}/\\mathrm{m}^{3}$ 。对于 $35\\mu\\mathrm{m}$ 的漆膜，若空气中 $5\\mu\\mathrm{m}$ 的尘埃进入到漆膜中则影响不大，若停留在漆膜表面，则将形成一个点。  \n\n$\\textcircled{7}$ 槽液中杂离子含量容许浓度如下（mg/kg）。  \n\n$\\mathbf{Na}^{*}$ ,Ca+ $\\mathrm{PO}_{4}^{3-}$  \n\n$\\textcircled{8}$ 阳极。  \n\na.一般三年更换一次，好的情况下 $6{\\sim}7$ 年更换一次。  \n\nb.金属阳极腐蚀带来的铁离子堵塞隔膜，加快隔膜的老化变脆。  \n\nc.膜电阻一般为 $10\\Omega\\cdot\\mathrm{cm}^{2}$ ，工作一年后为 $3\\sim5\\mathrm{k}\\Omega\\cdot\\mathrm{cm}^{2}$ ，被污染的膜高达 $10\\sim$ $20\\mathrm{k}\\Omega\\cdot\\mathrm{cm^{2}}$ 。由于膜电阻的增大，在电泳过程中会产生所谓双性电泳现象，造成工件表面不平整。  \n\nd.阳极的腐蚀：阳极面积太小、温度太高、电流密度太高、阳极液电导率太高、循环不够、 $\\mathsf{p H}$ 过低、隔膜的性质不一样等均可能带来较快的阳极腐蚀（某大型车厂有一次只更换了部分阳极膜，结果不到四个月新装阳极盒内的阳极全部腐蚀）。  \n\n$\\textcircled{9}$ 溶剂含量：如含量过高（19%）会导致泳透力下降，击穿电压降低，漆膜易产生缩孔。溶剂含量与UF液关系密切，只要UF系统封闭循环，即可以维持溶剂含量在一定的水平。  \n\n$\\textcircled{10}$ 设备的清洗：设备清洗周期见表3-2-46。  \n\n表3-2-46设备清洗周期  \n\n\n<html><body><table><tr><td>名称</td><td>频率</td><td>备注</td><td>名称</td><td>频率</td><td>备注</td></tr><tr><td>电泳槽</td><td>1次/年</td><td>包括阳极罩</td><td>超滤器</td><td>1次/季</td><td></td></tr><tr><td>水洗槽</td><td>1次/季</td><td></td><td>喷嘴</td><td>1次/周</td><td></td></tr><tr><td>过滤器</td><td>1次/半月</td><td>根据进出口压差</td><td>更换隔膜</td><td>3~4年一次</td><td></td></tr><tr><td>阳极液探头</td><td>1次/周</td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n$\\textcircled{1}$ 现场检查。  \n\na.检查湿漆膜状况，看是否粘手（即电渗性的好坏）。  \n\nb.经常检查工作电流是否正常以及槽温、阳极液的流量（最好在 $10\\mathrm{L/min}$ 以上）。  \n\nc.定期挂板检查性能（车厢内外都应考察）。  \n\nd.节假日应适当补充一些酸和溶剂、助剂等。  \n\n$\\textcircled{12}$ 工件人槽前必需烘干或者是确保工件表面无水珠，有的工艺被设计成人槽前用DI水喷洒以使表面在全湿的状态下人槽。  \n\n$\\textcircled{13}$ DI水的电导率必须低于 $10\\mu\\mathrm{S/cm}$ ，如果高于 $25\\mu\\mathrm{S}/\\mathrm{cm}$ 则可能造成对槽液的污染。  \n\n$\\textcircled{14}$ 晾干室的温度近年来提高到 $30\\sim40^{\\circ}C$ ，并且设置预烘炉 $(60\\sim100)\\mathfrak{C}\\times40\\mathrm{min}$ ，再进人烘道。CED在烘烤过程中要产生较多的挥发物，其量为漆膜重量的1/10。油烟在烘道出入口处冷凝，因此挂具设计应该合理，能防止污染物滴落在工件上。  \n\n(4）日常槽液管理的控制项目  \n\n$\\Phi$ 固含量  \n\na.过高电沉积加快，漆膜平滑性下降。这是由于沉积太快，漆膜疏松多孔，冲洗后还会产生水痕。b.过低槽液的电导率偏低，涂层较薄。如果槽液长期在低浓度下则其稳定性会越来越差。这主要是因为槽液的黏度偏低，悬浮力低导致颜料沉降快的缘故。同时这将加速槽液的水解及电解反应，漆模外观及性能都会受到影响。严重时甚至会造成整槽槽液变质报废。对那些更新期较长的槽，更应该将NVM控制在上限。  \n\n$\\textcircled{2}$ 灰分灰分对漆膜的外观影响明显。  \n\na.过低在沉积的过程中击穿电压下降，漆膜出现明显的缩孔和堆积，电渗性变差，泳透力下降。b.过高光泽下降，颜料沉淀快造成管道以及超滤膜堵塞，UF水减少。在生产过程中，一般情况下是灰分下降。  \n\n$\\textcircled{3}$ pHpH是决定树脂水溶性以及槽液稳定性的重要控制参数。  \n\na.过低槽液中形成的胺盐较多，带正电荷的胶体粒子少，这样沉积到工件上的沉积物也少，漆膜变薄，甚至露底。pH低将会导致电导率增高，泳透力下降。  \n\nb.过高其危害性比过低要严重得多。除外观变差外，还会使槽液凝聚，沉降堵塞管道，严重时整槽的槽液都会报废。此外， $\\mathsf{p H}$ 高还会导致工件上的浮漆难以冲洗干净进而影响漆膜的外观。  \n\n为防止pH的波动，首先应该控制UF水的排放。通常UF水是不应该随便排放的，其次是槽液的温度不能偏高，以免中和剂大量挥发损失。平常最好控制 $\\mathbf{pH}$ 在指标的下限，这样有利于槽液的稳定。  \n\n$\\textcircled{4}$ 电导率槽液电导率的过高或者过低虽然对漆膜的质量或槽液的稳定性有所影响，但是CED的这项指标还是比较容易管理的。多年的实践证明，即使长期不排放UF水，槽液的电导率也不会有太大的变动，这应该是CED的优点之一，因此不少总装厂总是将CED槽的电导率控制在下限。  \n\na.过高槽液的温度过高，NVM高或中和剂浓度增高引起。  \n\nb.过低排放UF水过量。  \n\n$\\textcircled{5}$ 溶剂含量溶剂含量对槽液的稳定性、漆膜的平滑性以及厚度均有较大的影响。溶剂含量波动的原因与UF水排放有关，也和补漆的速率以及槽液的温度有关。  \n\na.过低漆膜薄，平滑性差。尤其是附着在工件上的浮漆干燥也快，如果不及时冲洗易造成麻点。  \n\nb.过高漆膜厚，易出现水痕且击穿电压降低，泳透力差。  \n\n(5）相关设备的管理首先，投槽前就要开始严格的工艺管理，除严格清洗设备外所有的管道，阀门都要清洗干净。防止阀门上的润滑剂、脱模剂（含Si）混人槽液内，因为CED对缩孔特别敏感。 9  \n\n$\\Phi$ 电泳槽  \n\na.防止槽内有死角，主槽纵断面的形状应与槽液的流向-致，尽量减少槽内不必要的金属构件。同时要防止构件的横断面与槽液的流向相对，建议主槽进口端的底部设置循环泵，泵的吸人口应设计成喇叭形。  \n\nb.主槽衬里表面必须要平整光滑，防止颜料在不平处沉积。  \n\nc.循环系统不采用备用泵，减少旁路。  \n\nd.主槽上的抽风机应设置在槽的两侧，不能在中心，以免启动时将异物或灰尘带进电泳槽内。  \n\n②循环搅拌系统循环搅拌是为了保证槽内各组分浓度均匀，改善槽液的分散，防止颜料下沉。消除在电沉积过程中所产生的气泡。CED产生的氢气量是AED产生的氧气量的2倍，如果搅拌不好所析出的气体会使漆膜产生针孔或缩孔，对泳透力也有影响。还应该注意，流速不均会造成轻质颤料上浮，一般每小时循环 $6{\\sim}8$ 次（也有提 ${>}5$ 次)。  \n\n③直流电源通常要求两段供电或电压斜升方式，主要原因是CED产生的气体量较大。为了避免大量气体的逸出，入槽初期电压低一点要好些。一般一段电压为两段电压的1/3左右，时间约 $10\\sim30{\\mathrm{s}}$ 费  \n\n④热交换装置一般情况下CED涂装线上不必考虑加热系统，只要设置冷却系统即可。建议日常槽温控制在工艺要求的下限。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1096,
+        "chunk": "# 2.面漆及中间涂料  \n\n汽车面漆、中间涂料的涂装普遍采用喷涂的方式。几年前我国还是以手工喷涂为主，近年来汽车行业引进建成一批现代化轿车车身涂装线，采用了较为先进的静电高速旋杯涂装设备，结合侧喷机、顶喷机等自动化设施，使我国汽车涂装的总体水平获得了质的飞跃。目前我国低档汽车涂装，如卡车、农夫车等还以手工喷涂为主，其他中、高档车型已经逐步过渡到机械手、顶喷机、侧喷机等自动化喷涂运作方式。  \n\n从漆料雾化的方式来分类，喷涂手段可分为以下三类：  \n\n$\\Phi$ 压缩空气雾化喷涂；  \n$\\textcircled{2}$ 高压无气喷涂；  \n$\\textcircled{3}$ 高速旋转雾化喷涂。  \n\n（1）压缩空气雾化喷涂压缩空气雾化喷涂所采用的各类喷枪的品种、调整、喷涂施工、维护等方面内容将会在本节有关汽车修补漆内容中详细讨论。值得注意的是，原厂漆采用的喷枪与汽车修补漆采用的喷枪有所不同。其主要差别在于喷枪型号、规格等有较大差别。汽车原厂漆施工中采用的典型喷枪结构如图3-2-9所示。  \n\n![](images/f75d2c114a8be7c739412f0d5e33350550b778cbca6852f9ed8a783be46fc170.jpg)  \n图3-2-9压缩空气雾化喷枪结构1一漆料；2-雾化空气调节；3-整形空气调节  \n\n(2）高压无气喷涂高压无气喷涂法是一种较为独特的涂装方法。它是利用压缩空气作为动力驱动高压泵，使漆料增压至10～25MPa，通过高压输送管道，从细小的孔隙中喷射而出，并雾化成漆雾，喷射到涂装表面，形成均匀的漆膜。高压无气喷涂与其他几种涂装手  \n\n段相比，具有以下特点：  \n\n$\\Phi$ 涂装效率较高，漆雾飞散、损失较少；  \n\n$\\textcircled{2}$ 对环境的污染较低；  \n\n$\\textcircled{3}$ 对漆料施工黏度的限制不高，适应范围广；  \n\n$\\textcircled{4}$ 特别适合涂装一次成膜厚度较高的场合；  \n\n$\\textcircled{5}$ 由于压缩空气只作为驱动动力，喷涂时不与漆料混合，进而雾化，故不存在其中含有的水分、油污、灰尘等给漆膜带来的各种病。  \n\n尽管高压无气喷涂有着上述诸多特长，但它对汽车行业来说却有着不可克服的缺憾，即它所涂装的漆膜的装饰性能远远比不上其他几种涂装工艺，因此，在汽车工业中这种涂装工艺只用于对装饰性要求不高的部位，如车底盘、发动机以及某些低档卡车的车厢等。  \n\n高压无气喷涂设备最为重要的关键元器件就是喷嘴，按照使用的功能和结构来划分有以下几类。  \n\n$\\textcircled{1}$ 标准型喷嘴使用最为普遍的一类喷嘴，如图3-2-10所示，喷嘴的开口类似橄榄形，喷出的漆雾为椭圆形。这类喷嘴的型号很多，有不少选择的余地。输漆量可在 $\\phantom{-}0.2\\sim$ 5.0L/min范围内选择，甚至可达10L/min以上，扇幅变动范围也较大，为150～600mm。  \n\n![](images/94be7cd8384a28c86cabbd4c030c4979cf542ca996a5ccc86828714dee7a8db9.jpg)  \n图3-2-10标准型喷嘴  \n\n![](images/125d8c7a517418011b0cc99d6b93cbd070616f67a75ed6a27849f8971a0ec0cd.jpg)  \n图3-2-11自清洗型喷嘴  \n\n②圆形喷嘴顾名思义，圆形喷嘴的开口呈圆形，喷出的漆雾也呈圆形，主要用于喷涂管型器件及较为狭窄的部位。  \n\n$\\textcircled{3}$ 自清洗型喷嘴自清洗喷嘴与众不同的是它装置有一个换向机构，一旦喷嘴堵塞时，将其旋转 ${180}^{\\circ}$ ，可进行清洗，故称自清洗喷嘴。这类喷嘴有球形和圆柱形两种，以圆柱形较为常用（图3-2-11)。  \n\n$\\textcircled{4}$ 可调喷嘴等可调喷嘴上装有一个调节塞，可在喷涂期间随时变换漆料的输出量及扇幅。  \n\n手工操作时，高压无气喷涂与压缩空气雾化喷涂的操作要领大同小异，关键是控制输漆量、漆料施工黏度、移动喷枪的速率、喷枪与工件的距离等（详见汽车修补漆施工部分）。  \n\n(3）高速旋转雾化喷涂在涂料喷涂施工中采用高速旋转雾化有两种模式：高速旋盘和高速旋杯。  \n\n$\\Phi$ 静电高速旋杯是一种利用旋杯高速旋转时产生的离心力，沿切线将漆料甩出，在极大的剪切力的作用下液滴破裂，进而雾化的喷涂形式。高速旋杯的典型结构如图  \n\n![](images/b880498822856f70bb26756f08e3c044a264e1ab59a91d89e615779cf88374c0.jpg)  \n图3-2-12高速旋杯结构示意图1-物料阀；2-供漆；3-回流；4一整形空气；5—驱动空气；6一回流气  \n\n![](images/98f66c4fdf36ac2552b1ce46a593b11d3b4f28543b79ab5f5ae99520c187459b.jpg)  \n图3-2-13装置在机械手上的换色系统  \n\n3-2-12所示。静电高速旋杯系统由旋杯、转速控制器、电压控制器三部分组成。它们可以结合机械手，采用单个旋杯用于较小面积部位的涂装，有人将其称之为“机械手旋杯”（robobell)，亦可设计成数个旋杯排列成一行，与顶喷机配合用于喷涂汽车车身表面。现代高速旋杯往往与加入静电、智能化等配置，成为现代轿车车身涂装的主要施工手段。智能化、静电高速旋杯涂装线具有以下特点：  \n\na.自动化程度可以设计得很高，可以自动识别车型、颜色，实现自动换色。图3-2-13显示的是装置在机械手上的换色软管的连接情况；b.在计算机的配合下，可自动调节工艺参数，如供漆量、供气量、旋杯转速、行程、旋杯矩阵与车身表面距离沿车型自动调节跟踪、换色间隙的清洗及自动报警等；c.与机械手配合可用于涂装各种形状复杂、工件产量较大的场合；d.雾化效果远远好于压缩空气雾化，可得更佳的外观等。  \n\n涂装设备公司发展了一种专用于底色漆的旋杯，名为“金属旋杯”（metallicbell)。金属旋杯与普通旋杯的异同点见表3-2-47，从表中数据可以看出，金属旋杯的转速、整形空气流量、旋杯直径等均比普通旋杯大得多，而且旋杯的边沿较为锐利，边角角度也更小，故采用这样的涂装设备，雾化漆料粒子的直径将更小，含溶剂量也更少，因此可以获得类似手工喷枪喷涂所得到的表面效果。  \n\n表3-2-47高速静电旋杯与金属旋杯的工艺参数比较  \n\n\n<html><body><table><tr><td>工艺参数</td><td>金属旋杯</td><td>普通旋杯</td></tr><tr><td>旋杯转速/（r/min）</td><td>75000</td><td>20000~50000</td></tr><tr><td>整形空气量/（L/min）</td><td>800</td><td>100~150</td></tr><tr><td>旋杯直径</td><td>大</td><td>小</td></tr><tr><td>雾化漆料的粒径/μm</td><td>10~40</td><td>10~80</td></tr></table></body></html>  \n\n为充分发挥静电高速旋杯的效能应掌握和调整好一些主要参数，包括旋杯转速、静电电压、输漆量、整形空气压、跟踪程序的设定等。现以与单个机械手配伍的旋杯的参数选择为例予以说明。 O  \n\na.旋杯转速旋杯转速范围应根据其杯体直径而定。如杯体直径为 $50\\mathrm{mm}$ ，则工作范围可在 $20000{\\sim}40000\\mathrm{r/min}$ 中选择，喷涂本色漆时使用 $20000\\mathrm{{0r/min}}$ ，而喷涂清漆时可高达$30000\\tau/\\mathrm{{min}}$ 。旋杯转速越高，其雾化效果越好。  \n\nb.静电电压一般静电发生器的电压范围可由 $_{0\\sim60\\mathbf{kV}}$ 可调，大部分采取分级调压。喷涂色漆时采用 $30{\\sim}45\\mathbf{kV}$ ，喷涂金属闪光漆时应采用低电压，以防止电流过大，而喷涂清  \n\n漆时可采用较高的电压。  \n\nc.输漆量输漆量的大小取决于被涂工件表面积的大小、膜厚、涂料的利用率以及机械手移动的速率等。此外，还应该考虑输漆计量泵的输送能力和旋杯的最大出漆量。确切地说，根本限制在于旋杯的最大出漆量。过大的出漆量将无法获得良好的涂装效果，以单个机械手配-个旋杯为例，一般选择 $200{\\sim}400\\mathrm{mL/min}$ 的出漆量。  \n\nd.整形空气压力的选择整形压力的调节是一个技术性极强的参数，正确的调节可使漆雾被约束在指定的范围内。压力过低，会使漆雾散开，不仅造成涂料利用率下降，而且无法获得理想的涂装效果。压力过高，也会使涂料利用率下降、扇幅不稳、污染旋杯等。总之，整形压力可以非常方便地调节扇幅（图3-2-14)。  \n\n![](images/a8f33b4dd278702fdadd27bc8a5585cdb7667739f58deef6a761ab1088e08f1e.jpg)  \n图3-2-14整形压力对扇幅的调节  \n\ne.开关喷枪点的选择在手工喷枪涂装过程中，一般是接近涂装表面时，提前开启喷枪，而离开涂装表面时，则延后关闭喷枪。在静电高速旋杯涂装中，因旋杯的旋转一直是稳定不变的，故不存在提前或延后，只需要准时开、关即可。  \n\n总之，静电高速旋杯是一种自动化程度较高的涂装系统，只要上述参数调节得当，即可获得满意的涂装效果。它不仅可替代技术熟练的喷漆工，而且涂料的利用率高，所得漆膜的装饰性好，质量稳定，生产效率高，节能等，无疑这是一种先进的涂装系统。  \n\n$\\textcircled{2}$ 静电高速旋盘静电高速旋盘涂装系统由液压驱动装置、静电旋盘喷枪、气动控制装置、高压静电发生器以及Ω形悬挂链所组成。与高速旋杯不同的是，这里用来雾化漆料的工具是一个圆盘，而不是旋杯。由于高速旋盘涂装线的传动链在经过旋盘附近时，多设计成类似希腊字母Ω形（俯视图），故而又被称为“Ω”涂装（或“DISC\"）。高速旋盘一般只与升降机配合使用，而不与顶喷机或侧喷机配套。由于它自身的特点所限，此类涂装手段不适合用于车身涂装，而只能用于汽车零部件的涂装施工中，如保险杠、倒视镜、手把等。  \n\n此类涂装设备中采用旋转圆盘的直径一般为 $200\\sim650\\mathrm{mm}$ ，转速为 $13000{\\sim}35000\\mathrm{r/min}$ 可调，静电高压可达 $_{120\\mathbf{k}\\mathbf{V}}$ 以上。  \n\n工作时，气动涡轮驱动旋盘而旋转，把通过输漆管路输送到圆盘上的漆料甩出。涂料粒子在被甩离圆盘边沿时，因锐利的边沿的电晕发电而带上负电，并且在飞往带正电的工件的过程中进一步分裂成更加微小的粒子，形成漆雾，最后被吸附于工件上溶结成膜。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1097,
+        "chunk": "# 二、汽车修补涂料  \n\n汽车修补涂装的施工方式与原厂漆不同，它只采用压缩空气雾化喷涂。因此以下重点讲述压缩空气雾化喷枪的类型、调试、使用等与施工有关的内容。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1098,
+        "chunk": "# 1.汽车修补喷枪的调试与维护",
+        "category": " Introduction"
+    },
+    {
+        "id": 1099,
+        "chunk": "# (1）喷枪的种类  \n\n喷枪的种类和型号很多，各家涂装设备制造公司的命名方法和分类虽然有所不同，但是大体上有以下几种分类方法。  \n\n$\\Phi$ 按供漆方式吸上式、压送式、重力式。  \n$\\textcircled{2}$ 按喷嘴类型对嘴式、单嘴式、扁嘴式。  \n$\\textcircled{3}$ 按雾化方式枪内混合式、枪外混合式。  \n\n如图3-2-15所示为实际喷涂施工中采用最多的吸上式喷枪，这种类型的喷枪由喷杯、喷嘴（扁形，可调节供漆量的大小)、空气帽、顶针、出漆量控制阀、控气阀杆、扳机、空气管接口以及枪体等组成。该喷枪的液体喷头高出空气帽约 $0.015\\sim0.020\\mathrm{mm}$ 。这样在液体喷头前，由于周边的压缩空气流形成局部真空，这一局部真空将液体涂料从喷杯中吸人至喷头，继而雾化喷出。图3-2-15为对嘴式喷枪，喷出的漆雾呈圆形，而扁嘴式喷枪（图3-2-16）则呈扇形，覆盖面积较上述对嘴式喷枪大，比较适合喷涂汽车损坏面积较大甚至需要进行整车修补的场合。这里以扁嘴式喷枪为例来简要地说明喷涂施工前喷枪的调试方法。  \n\n![](images/f6d407a39bd966acf3efd67848f20a6fdabf6ca1a88e25e8bccd688339be22af.jpg)  \n图3-2-15 吸上式喷枪示意",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1100,
+        "chunk": "# (2）喷枪的调试  \n\n$\\Phi$ 空气帽的调整在喷枪的调整中，空气帽的调整最为简单，只有垂直、水平两种状态。调整它可使喷枪喷出两种方向不同的雾束。  \n\na.垂直雾束旋转空气帽，使它的两个耳与地面平行，则喷出的雾束呈扁平扇面，且垂直于地面，这种方式是用得最多的一种形式。  \n\nb.水平雾束旋转空气帽使它的两个耳与地面垂直，则喷出的雾束呈扁平扇面，且平行于地面。这种状态多用来在喷完一道以后，需要喷第二道而进行的垂直扫枪，或进行交叉喷涂时所取的状态。实际上，这种情况在修补涂装施工中比较少见，除非是涂装大面积表面时才可能需要用到它。  \n\n$\\textcircled{2}$ 喷枪全开状态的调整对整车、车辆的一侧或较大面积进行修补时，应将喷枪调整至雾束全开状态。调整步骤如下。  \n\na.调整前的准备工作  \n\n·将喷杯加满涂料，并将喷杯接到喷枪上。·将压缩空气管接到喷枪上。·调整压缩空气压力。  \n\n这里特别值得一提的是对不同兑稀状态的涂料喷枪上压力应设置不同数值，例如，黏度较低的清漆可定为 $2.5\\times10^{5}\\mathrm{Pa}$ 黏度较大的瓷漆可定为 $4.2\\times10^{5}\\mathrm{Pa}$  \n\nb.将空气帽的位置调整到可喷水平雾  \n\n![](images/97dc8545c985cdb81db93642e26c7a76699401bc939e49f039c75d1ef7f7db58.jpg)  \n图3-2-16喷枪与表面的距离  \n\n束的状态，固定。  \n\nc.打开雾束控制阀，逆时针旋转至全开的位置。d.打开液体涂料控制阀，逆时针旋转至全开的位置，此时应该可以看到调节螺栓上的螺纹。e.拿起喷枪，对着垂直墙面上的某一点做雾束形状试验。试验时喷嘴与墙面相距约手掌打开时--手宽（图3-2-16），喷 $3{\\sim}4\\mathbf{s}$ 身  \n\nf.检查喷涂到墙面上所形成的涂层图形的均匀性。  \n\n$\\textcircled{8}$ 雾束分裂如图3-2-17和图3-2-18所示，在所得涂层上，两端的流淌长度大于中心点的长度。  \n\n![](images/e942ff01a68c54ee88816bc44ee62ad6bd8713746d3907c49cd426845d40f3b3.jpg)  \n图3-2-17流滴试验——雾束分裂（水平喷涂）  \n\n![](images/eee3b54a517dbdaddb78995b21a5b12557545fa9475020711ad1e05a71c55997.jpg)  \n图3-2-18流试验——雾束分裂（垂直喷涂）  \n\n解决办法如下。  \n\n·顺时针旋转雾束控制阀一圈，以缩小扇幅。重新进行上述试验，并检查结果。  \n·提高喷枪上的压缩空气压力大约 $0.35\\times10^{5}\\mathrm{Pa}$ ，重复上述试验，并检查结果。  \n\n必要时重复以上两项操作，直到所得涂层两端的流淌长度相等，如图3-2-19所示。  \n\n注意：这一试验的目的是希望所喷出的涂料的量在整个打开的雾束上几乎相等，从而使经过调整后的喷枪喷出的雾束比较均匀。  \n\n![](images/f9519951bde6a56aa0da94d60804621c6e79574800a24efb87d06e85cb04248d.jpg)  \n图3-2-19流滴试验-——雾束均匀  \n\n![](images/c1512279c608db638a459301cb649efad271c31c7f253589361aca7b5ecde4ae.jpg)  \n\n$\\textcircled{6}$ 雾束集中如图3-2-20和图3-2-21所示，在所得涂层上，两端的流淌长度小于中心点的长度。  \n\n解决办法如下。  \n\n·顺时针旋转液体物料控制阀半圈或再少一点。重复上述试验，并检查结果，直到涂层两端的流淌长度相等，如图3-2-19所示。  \n\n·开雾束控制阀，每次逆时针旋转半圈或再少一点。重复上述试验，并检查结果，直到涂层两端的流淌长度相等，如图3-2-19所示。  \n\n![](images/1bde03ca7fede3b695e8d8ce2e86f448ace64cbcd79cbb7118d32de93d1d81dd.jpg)  \n图3-2-20流淌试验—雾束集中（垂直喷涂）  \n图3-2-21流滴试验—雾束集中（水平喷涂）  \n\n$\\textcircled{3}$ 修补斑点时喷枪的调整斑点修补喷枪调整的关键通常是使一些调节阀处于半开状态。雾束的大小取决于待修补部位的尺寸。从刚好打开调整到全开的3/4。较小的雾束可以最大限度地节约原材料和人工。具体调整方法如下。  \n\na.雾束控制阀记录雾束控制阀全开到全闭之间处于半开状态的数据，以确定控制阀在半开时的位置。  \n\nb.液体物料控制阀记录液体物料控制阀全开到全闭之间处于半开状态的数据，以确定控制阀在半开时的位置。  \n\nc.做雾束调整试验具体试验方法与全开喷枪的调节部分相同。  \n\nd.检查所得涂层分析喷涂时涂料运行时的情况。  \n\n$\\textcircled{a}$ 雾束集中如图3-2-20和图3-2-21所示，在所得涂层上，两端的流淌长度小于中心点的长度。  \n\n解决办法如下。  \n\n·顺时针旋转液体物料控制阀大约 $1/4$ 圈，以减少供漆量。  \n\n·重复上述控制雾束实验，并且检查漆料的流淌情况。  \n\n·重复以上两步直到所得涂层的图形正常，如图3-2-19所示。  \n\n$\\textcircled{6}$ 雾束分裂如图3-2-17和图3-2-18所示，在所得涂层上，两端的流淌长度大于中心点的长度。  \n\n解决办法如下。  \n\n·逆时针旋转液体物料控制阀大约 $1/4$ 圈，以增加供漆量。  \n\n·重复上述雾束控制试验，并且检查漆料的流消情况。  \n\n·重复以上两步直到所得涂层的图形正常，如图3-2-19所示。  \n\n$\\textcircled{4}$ 干喷的调节所谓干喷的意思是涂装后，涂层非常干。喷漆工甚至刚刚喷涂完毕就可以马上用抹布擦拭新喷的表面涂层，以清除上面的尘埃或过喷涂所遗留下来的残留物。在以下的章节里将会介绍具体实施的工艺，这里仅仅介绍干喷时喷枪的调节方法。  \n\na.完全关闭液体物料控制阀和雾束控制阀。  \n\nb.打开雾束控制阀 $1/8\\mathrm{\\sim}1/4$ 圈。  \n\nc.打开液体物料控制阀 $1/4{\\sim}1/2$ 圈。  \n\nd.对准某一点做于喷试验，这个点的直径为 $5.0{\\sim}7.5\\mathrm{cm}$ ，其具体试喷方法如下。  \n\n·扣死板机，喷枪围绕上述圆圈做连续的圆周运动进行喷涂。  \n\n·保持喷枪离表面 $10{\\sim}15\\mathrm{cm}$ 要·压缩空气的压力与传统工艺相同。  \n\n·每 $5\\sim10s$ 停一次，观察表面状态平整与否，再用特殊的抹布擦拭，使其平整。  \n\n·重复上述过程，直到获得所要求的遮盖。  \n注意以下几点。  \n\n$\\textcircled{8}$ 如果材料太干，逆时针旋转液体物料控制阀1/8圈，以增加液体物料供给量。检查调整结果。  \n\n$\\textcircled{6}$ 如果材料太湿，即材料发黏。  \n\n·增加喷枪到表面的距离，离开 $2.5\\sim5\\mathrm{cm}$ ·关闭液体物料控制阀1/8圈，以减少供漆量。重复上述试验，检查结果。  \n\n·喷漆工应该能够在喷涂施工的任何时候擦干净表面的灰尘或打磨平整。  \n\n$\\textcircled{5}$ 空气雾化压力的调整压缩空气使涂料雾化的原理是在高速运动的空气流的作用下，喷出的液体涂料流束破裂，从而形成微小、均一的微粒子，飞向基材表面。在吸上式喷枪中，空气帽耳上雾束控制孔所喷出气流的压力大于空气帽上气孔的压力，使所喷出液体物料的方向改变，从而控制扇幅的大小。不仅如此，它还有助于液体物料中的稀释剂到达不了基材表面。比如：清漆中稀释剂的大约 $30\\%$ 就会在此阶段汽化。在喷涂瓷漆的时候，稀释剂蒸发相对较少一些。一个优秀的喷漆工就是要在喷涂时，应尽量使液体物料雾化，同时又要求液体物料中所含溶剂尽可能少地蒸发。一般情况下 $(20\\sim25\\Upsilon)$ ，在喷涂丙烯酸清漆时，将喷枪上的压力调整到 $(2.5\\sim2.8)\\times10^{5}\\mathrm{Pa}$ 。丙烯酸清漆在稀释 $150\\%$ 时，喷枪上压力调整为 $\\mathbf{2.5}\\times\\mathbf{10^{5}P a}$ 。这是比较好的雾化压力。丙烯酸清漆稀释 $125\\%$ 时，喷枪上压力调整为$2.8\\times10^{5}\\mathrm{Pa}$ 是最好的雾化压力。丙烯酸瓷漆或其他瓷漆则调整到 $(3.8\\sim4.2)\\times10^{5}\\mathrm{Pa}$ 左右。一般喷涂瓷漆时，喷枪上的压力调整到 $4\\times10^{5}\\mathrm{Pa}$ 左右。应养成严格遵守涂料产品说明书所提供的施工参数的良好习惯，因为只有这样做才能够获得理想的效果。比如，采用低于产品说明书的压力，极有可能雾化不好，涂料会像淋洒一样喷涂到基材表面，其效果可想而知。反过来，如果采用是的比说明书高的压力，则极有可能过蒸发，严重时形成所谓干喷现象，起码也会带来其他一些涂料病，如橘纹、光泽、鲜映性等参数都变差。  \n\n空气雾化压力调整时，下面一些简单的规律可以供调整时参考。  \n\na.喷涂清漆时，压力调整在 $2.8\\times10^{5}\\mathrm{Pa}$ ，喷涂瓷漆时，压力调整在 $3.5\\times10^{5}\\mathrm{Pa}$ ，按照前文中雾束实验部分的方法观察所得到的涂层是否均衡。b.设置空气压力比规定低一些，如 $1.4\\times10^{5}\\mathrm{Pa}$ ，用以喷涂黑漆。c.一手握喷枪并扣住扳机，喷出漆雾；另一只手拿一张 $22\\mathrm{cm}\\times28\\mathrm{cm}$ 或更大一点的白纸卷迅速横穿漆雾，保持纸卷长度的方向与雾束的方向一致。在这种情况下，如果留在纸卷上的涂料粒子的大小明显不一样，就可以认为雾化压力低了。d.不断提高压力，每次大约 $0.35\\times10^{5}\\mathrm{Pa}$ ，每提高一次压力，就用新的纸卷通过一次。及时检查纸卷上涂料粒子的大小，如有必要，用放大镜观察。一直把压力提高到涂料粒子非常均一细腻为止，此时的压力为最佳雾化压力。e.在获得最佳雾化压力之后，继续增加压力，如果发现涂料粒子的粒径不再降低，则表明在目前的条件下，已经没有必要采用更高的压力了。  \n\nf.喷枪未调整好时容易出现的故障及对策。  \n\n调整好喷枪以后，在正式涂装之前，为了保证施工质量，应认真按照产品说明书中所列的关键参数再仔细检查一遍。有时在施工开始阶段喷枪的性能良好，一段时间以后逐渐变差。还有的时候，比如重新往喷枪的喷杯中加注涂料后重新开始喷涂时，往往发现雾束发生了改变。有时这些改变已经完全不能适应原来的施工要求。因此每当喷涂施工因某种原因间断时，或者在工作一段时间以后都要对喷枪的雾束重新进行调整。其调整方法同前，也就是将喷枪对着合适的墙壁（可在墙面上挂一张白纸），距离大约在 $15\\sim20\\mathrm{cm}$ ，喷涂 $1\\sim2\\mathrm{s}_{\\circ}$ 检查墙面上所形成图形的形状、大小，看其是否适合当前施工的要求。一般喷枪容易出现的故障及对策归纳如下。  \n\n·液体顶针压紧螺帽引起液体泄漏   \n\n\n<html><body><table><tr><td>原因 压紧螺幅松动</td><td>对策 拧紧螺帽</td><td>原因 顶针填料甘油</td><td>对策 注油，然后拧紧螺帽</td></tr><tr><td>填料函损坏</td><td>更换新件</td><td></td><td></td></tr><tr><td>·压缩空气泄漏</td><td></td><td></td><td></td></tr><tr><td>原因</td><td>对策</td><td>原因</td><td>对策</td></tr><tr><td>空气阀或阀座被脏物污染清洗</td><td></td><td>顶针弯曲</td><td>更换</td></tr><tr><td>空气阀或阀座损坏</td><td>修理或更换</td><td>压盖螺帽太紧</td><td>松开一点，在填料函上加点油</td></tr><tr><td>空气阀弹簧断裂</td><td>更换</td><td>密封圈子损坏或未装</td><td>加装或更换</td></tr><tr><td>顶针缺润滑油</td><td>加轻质润滑油</td><td></td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td colspan=\"2\">·液体物料泄漏 原因</td><td>原因</td><td colspan=\"2\">对策</td></tr><tr><td></td><td>对策 修理或更换</td><td>顶针弹簧断裂</td><td>更换</td><td></td></tr><tr><td>由于顶针或喷嘴被污染</td><td></td><td>顶针尺寸不对</td><td></td><td>更换</td></tr><tr><td>使顶针无法到位</td><td>取下并清洗干净</td><td></td><td></td><td></td></tr><tr><td>液体喷嘴被污染 螺帽太紧</td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>松开一点</td><td></td><td></td><td></td></tr><tr><td colspan=\"5\">·雾束不稳，时大时小</td></tr><tr><td colspan=\"2\">原因</td><td colspan=\"3\">对策</td></tr><tr><td colspan=\"2\">喷杯中涂料不够</td><td colspan=\"3\">加足</td></tr><tr><td colspan=\"2\">喷枪倾斜的角度太大</td><td colspan=\"3\">增加喷杯中的涂料</td></tr><tr><td colspan=\"2\">液体管道堵塞</td><td colspan=\"3\">折下并清洗干净</td></tr><tr><td colspan=\"2\">连接喷杯或压料罐的管道破裂或者安装不紧</td><td colspan=\"3\">拆下所有的接头，更换损坏了的管道</td></tr><tr><td colspan=\"2\">喷松动或喷嘴座损坏</td><td colspan=\"3\">拧紧喷嘴或更换喷曬座</td></tr><tr><td colspan=\"2\">涂料黏度太大</td><td colspan=\"3\">进一步兑稀，如无可能则更换喷枪，如将喷枪由吸上</td></tr><tr><td colspan=\"2\"></td><td colspan=\"3\">式改为压送式</td></tr><tr><td colspan=\"2\">喷杯上空气出口被堵塞</td><td colspan=\"3\">清理</td></tr><tr><td colspan=\"2\">喷杯与枪体之间的连接螺帽松动，污染，损坏</td><td colspan=\"3\">紧固，清洗或更换</td></tr><tr><td colspan=\"2\">填料函缺油或顶针螺帽松动</td><td colspan=\"3\">加润滑油，紧固</td></tr><tr><td colspan=\"5\">·雾束集中</td></tr><tr><td colspan=\"2\">原因</td><td colspan=\"3\">对策</td></tr><tr><td colspan=\"2\">相对扇幅而言，供漆量太大</td><td colspan=\"3\">减少供漆量，将雾束控制阀开大一点</td></tr><tr><td colspan=\"2\">对于压送式喷枪，空气帽选小了</td><td colspan=\"3\">换大一点的</td></tr><tr><td colspan=\"2\">对于压送式喷枪，空气压力太小</td><td colspan=\"3\">增加空气帽中雾化空气压力</td></tr><tr><td colspan=\"2\">喷嘴尺寸太大</td><td colspan=\"3\">更换</td></tr><tr><td colspan=\"5\">·雾束分散</td></tr><tr><td colspan=\"2\">原因</td><td colspan=\"3\">对策</td></tr><tr><td colspan=\"2\">相对扇幅而言，供漆量太小</td><td colspan=\"3\">增加供漆量或减少一点扇幅</td></tr><tr><td colspan=\"2\">对于压送式喷枪，雾化压力太高，供漆量不足</td><td colspan=\"3\">稍稍增加一点的压力，同时降低雾化压力</td></tr><tr><td colspan=\"2\">喷嘴尺寸太小</td><td colspan=\"3\">更换尺寸大一点的喷嘴</td></tr><tr><td colspan=\"5\">·雾束顶部太大</td></tr><tr><td>原因</td><td>对策</td><td>原因</td><td></td><td>对策</td></tr><tr><td>雾束控制孔部分堵塞</td><td>清洗 清洗</td><td>空气帽或液体物料喷嘴被污染</td><td></td><td>清洗</td></tr><tr><td colspan=\"2\">液体物料喷嘴顶部堵塞</td><td colspan=\"3\"></td></tr><tr><td colspan=\"5\">·雾束底部太大</td></tr><tr><td>原因</td><td>对策</td><td>原因</td><td></td><td>对策</td></tr><tr><td>雾束控制孔部分堵塞</td><td>清洗 清洗</td><td>空气帽或液体物料喷嘴被污染</td><td></td><td>清洗</td></tr><tr><td colspan=\"2\">液体物料喷嘴底部堵塞</td><td colspan=\"3\"></td></tr><tr><td colspan=\"2\">·雾束偏右</td><td colspan=\"3\"></td></tr><tr><td>原因</td><td>对策 清洗</td><td>原因</td><td></td><td>对策 清洗</td></tr><tr><td colspan=\"2\">空气帽右耳雾束控制孔部分堵塞</td><td colspan=\"3\">液体物料喷嘴右边被污染</td></tr><tr><td colspan=\"2\">·雾束偏左</td><td></td><td colspan=\"2\">原因</td></tr><tr><td colspan=\"2\">原因</td><td></td><td colspan=\"2\"></td></tr><tr><td colspan=\"2\">空气幅左耳雾束控制孔堵塞</td><td></td><td colspan=\"2\">液体物料喷嘴左边被污染</td></tr></table></body></html>  \n\n上述雾束不正常的故障大部分都是由于有关零件被污染所致，解决办法无非是加强喷枪的清洗和维护。有经验的涂料工通常还利用一些简单的试验来判断堵塞发生地什么部位，发现雾束不正常后，将空气帽转半圈，再喷。如果所见到的雾束也反了过来，则可以判断是空气帽被污染了，否则就是液体物料喷嘴被堵塞。另外还应该经常检查液体物料喷嘴口上是否产生了毛边，这是高速通过的液体物料长期摩擦造成的，单靠清洗无法去掉它，可采用 $\\mathbf{No}.$ 600细砂纸细心地打磨平整，再用溶剂清洗干净。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1101,
+        "chunk": "# 2.喷涂施工技术  \n\n(1）一般要领  \n\n$\\Phi$ 握枪绝大多数喷漆工都像图3-2-22的标准方式握枪。按这种握法，喷枪乃是靠手掌、拇指、小指以及无名指握住的；中指和食指用以扣动扳机。有些喷漆工在较长时间工作时，时不时改换握枪的方式，有时仅仅用拇指、手掌配合小指，有时又是配合无名指握枪，中指和食指用来扣扳机。这样可以缓解疲劳，提高劳动效率。当然握枪方式的选择全凭喷漆工的自我感受，在这方面倒是没有一成不变的原则，可以根据各人的习惯和嗜好决定。  \n\n$\\textcircled{2}$ 喷枪对基材表面的方位喷枪对基材表面应该保持垂直，或者尽量保持垂直。如果喷枪有一些歪斜，其结果必然会造成喷幅带偏向一边流淌，而另一边则显得干瘦、缺漆，极有可能造成条纹状涂层。显而易见，只有压送式喷枪最适合喷涂车顶、前盖及后盖之类较大平面部位的涂装（因为这种类型的喷枪上不带喷杯，在喷涂施工时喷枪运动的方位就不会受到喷杯内所盛液体物料的限制)。  \n\n![](images/299b4cb9dba9f46a4afcaf7468c45085df294d9d4eff3d43f63a5a96306a4ca1.jpg)  \n图3-2-22正确的握枪方式  \n\n③喷枪至基材表面的距离对吸上式喷枪而言，最佳工作距离为15～20cm。如果距离太近，则可能产生流；在喷涂金属闪光漆时，极有可能造成颜色与预期的不一致。如果距离太远，比如超过20cm时，则可能导致干喷、过喷，使涂料的流平性变差；如果喷涂的是金属闪光漆，也可能带来颜色改变的可能性。压送式喷枪可以离工件表面远一点，一般最佳距离为 $20\\sim30\\mathrm{cm}$ 鼎  \n\n④喷枪的移动速度在喷涂时，喷枪的移动速度对涂装效果的影响非常之大，如果喷枪移动速度太快，涂层表面显得干瘦、粗糙、流平性差；如果喷枪移动速度太慢，则所形成的涂层太厚，极有可能产生流挂。实际上喷枪移动的速度也不能一概而论，对于不同的雾束、不同的供漆量，要求不同的移动速度。总之，喷枪的移动速度应针对不同的涂料品种、施工条件、施工工具，适当进行调整，以便喷涂时能够采用大体相同的移动速度。一般说来，如果仅仅作相对比较，那么压送式喷枪的移动速率要比另外两种类型喷枪的速度快一些。  \n\n③扳机的控制喷枪的工作是靠扳机来控制的。扳机扣得越深，液体流量越大。在传统走枪的过程中，扳机总是扣死，而不是半扣。为了避免每次走枪行将结束时所喷出的漆料堆积，有经验的喷漆工都要略微放松一点扳机，以减少供漆量。正确的扳机操作要领如下。 9  \n\na.手握喷枪向待喷涂表面移动，当喷枪移动到接近表面边缘地方，扣动扳机。说得更为具体一些，就是使喷枪口始终保持与待喷涂表面的垂直距离约15～20cm，慢慢地平行移动喷枪向待喷涂表面靠近，到距离待喷涂表面边缘大约5cm处，扣动扳机。  \n\nb.当喷枪扫完所有喷涂的表面后，松开扳机。也就是说在喷枪扫过已喷涂表面的边缘  \n\n大约5cm以外的地方松开扳机。  \n\n(2）收边喷漆工在进行斑点修补或局部板面修补（把新喷涂层与旧涂层之间的边缘进行润色加工）时，都要进行所谓“收边”或者叫“驳口”操作。“收边”的具体操作是在走枪开始时不扣死扳机，也就是说；此时供漆量较小；随着喷枪的移动，逐渐加大供漆量，直到走枪行将结束时再将扳机松开，使供漆量大大减少，从而获得一种特殊的过渡效果的操作。其具体操作方法如下。  \n\n$\\Phi$ 平稳地移动喷枪，到接近待喷涂基材表面时，逐渐扣紧扳机进行喷涂。然后在喷枪的继续移动中，平稳地松开扳机。这是从外向内喷。  \n\n$\\textcircled{2}$ 手持喷枪，位置处于待喷涂基材表面的上方，扣死扳机进行喷涂。然后平稳地由内向外移动喷枪，一旦喷枪接近收边区域时，慢慢且平稳地松开扳机，直到移动出收边区域。操作要平稳，这是从内向外喷。  \n\n(3）走枪喷漆时传统的走枪方式是保持喷枪离基材表面一定的距离，并且垂直于表面作水平方向的匀速运动（图3-2-23)。要求在每次喷漆走枪的过程中始终保持喷枪垂直于基材表面，且平行于表面移动。  \n\n![](images/4ed9b4ca122dfe352132a8249e831e8310609b0d34f0795a619cb23d64c9cbda.jpg)  \n图3-2-23喷枪对基材表面平行、等距离走枪  \n\n![](images/f0a6c2d99ce78910092f2cca3d855b1b664eed72e77bf291e08e2e07aa283502.jpg)  \n图3-2-24喷枪对基材表面弧形走枪  \n\n喷漆工（特别是学徒工）最容易犯的一个错误就是在喷漆走枪的过程中，不能始终保持喷枪与基材表面的距离相等。也就是说，喷枪移动的轨迹不是平行于基材表面的直线，而是一个大体上以手臂为半径的弧线，这样就极有可能造成走枪开始和结束部位涂层的厚度与中间不一样，如图3-2-24所示，这是应该尽量避免的。要尽快养成手握持喷枪喷涂时走直线，而不是弧线的良好习惯。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1102,
+        "chunk": "# 3.汽车修补涂装的一般施工工艺  \n\n(1）基本喷涂法汽车修补涂装中，按照喷涂手法来分类就有很多喷涂方式，如一道喷涂、带状喷涂、二道喷涂等。  \n\n$\\textcircled{1}$ 一道喷涂喷漆过程中，走枪最流行的手法是使喷枪从左到右，然后再从右到左（图3-2-25）移动。每扫一枪在开始和结束的时候分别扣动和松开扳机。扫下一枪时，再重复上述操作过程。整个过程应平稳而协调。值得注意的是： ?  \n\na.扫第一枪时，应该将雾束的中心对准待喷涂基材表面的边缘；  \nb.继续走枪时，应该将雾束中心对准上一枪雾束覆盖层的底部；  \nc.为了覆盖完好，喷涂区域顶部和底部的边缘应扫两次；  \n\nd.为了保证完全且均一的涂装，实际上应在距离每块待修补表面边缘 $2.5\\sim5.0\\mathrm{{cm}}$ 外的地方扣动或松开扳机。按照这类涂装方式，每道雾束之间大约应重叠 $50\\%$ 左右。  \n\n![](images/343e7adabf4f9cefbf2e7bd045a47bfcdcd6246b8adb0367d87ee000d0e80252.jpg)  \n\n$\\textcircled{2}$ 带状喷涂喷漆工在喷涂某些基材表面的边缘时，采用所谓“带状喷涂”法。此时喷漆工将扇幅调得相对窄一些，一般可将扇幅调整到大约 $10\\mathrm{cm}$ 宽。此时喷出的雾束比较集中，呈带状覆盖。这种手法对于某些特定基材表面而言可以达到减少过喷、节约原材料的目的。  \n\n$\\textcircled{3}$ 二道喷涂所谓二道喷涂指的是在一道喷涂完成后，马上进行第二道喷涂。二道喷涂通常应用于快干型涂料系统。有时涂料供应商在施工说明中建议二道涂装的方向与前一道涂装的方向不同。比如，第一道水平喷涂，第二道则要求采取垂直喷涂。这样更有利于覆盖和保持整个涂装表面涂层厚度均一。  \n\n$\\textcircled{4}$ 长板的喷涂对于汽车车身上较长板面的修补涂装一般可以采取垂直走枪的方法。但是多数喷漆工往往喜欢传统的水平走枪方式。喷漆工在喷涂长板时，为了方便将长板以$45\\sim90\\mathsf{c m}$ 的宽度将其分为几段，喷涂时就像喷涂短板那样进行施工。就像每道枪之间一样，各段之间交界处也需要重叠，一般在这里需要重叠覆盖大约 $10\\mathrm{{cm}}$ 左右的宽度。喷涂长板与喷涂边角不一样，没有必要采取带状喷涂法。另外当喷涂第二道时，最好改变雾束所重叠覆盖的部位，以免造成某一段的涂层过厚（图3-2-26）。  \n\n![](images/5f88d8cda66acc126e2b091937a3845065ca55e169270382a4ed6b789667801a.jpg)  \n图3-2-25板面喷涂重叠覆盖示意1in= 2. 54cm  \n图3-2-26长板喷涂法  \n\n$\\textcircled{5}$ 边角的喷涂喷涂边角时，应使雾束的中心对准边角，使边角的两边各覆盖 $50\\%$ 此时应使喷枪离基材表面的距离比正常距离近 $2.5\\sim5.0\\mathrm{cm}$ （图3-2-27)。  \n\n$\\textcircled{6}$ 棒状工件的喷涂喷涂汽车上一些细长、直径不大的棒状零部件时，最好将扇幅调窄一些与之配合。然而很多喷漆工为了省事，不愿意经常调整喷枪，而是将喷枪扇幅的方位及大小调到与棒状工件相当，这样既可以达到完全覆盖、又不过喷的目的（图3-2-28)。  \n\n![](images/78c126660b565dbb28d9c396407a6fce43bda8bdd4b46ddd8755427380b94918.jpg)  \n图3-2-27边角的喷涂法  \n\n![](images/0086dbc8fd2d040ef4cfa8f7edb2b350c3d8c64e11794f6ea3515288cc059d30.jpg)  \n图3-2-28棒状工件的喷涂法  \n\n大型水平表面的喷涂喷涂大型表面如发动机盖、车顶、后盖等，可以采用一道涂装法。即从左至右移动喷枪至接近基材表面时扣扳机，继续移动喷枪至已离开基材表面后放开扳机，这样可以获得充分润湿的涂层，而过喷或干喷最少。  \n\n如果所采用的是吸上式喷枪，当需要倾斜喷枪时，千万小心，不要让涂料滴落到基材表面上去。为了防止涂料泄漏、滴落，务请注意：  \n\na.在喷杯中不要把涂料装得太满；  \nb.在喷涂过程中不要作过于突然的运动，整个操作过程要平衡、协调；  \nc.确认喷杯上的通气孔向后，即靠近喷漆工身体的方位；  \nd.确认喷杯中的液体输送管靠喷杯前面；  \ne.确认喷杯的密封良好；  \nf.随时用抹布或纸巾擦干净泄漏出来的涂料。  \n8圆柱体的喷涂在喷涂直径较大的表面时，沿着圆柱的弧形表面走枪，使喷枪对基  \n\n![](images/8c190192a269b55de63bab5c3af86f59795b01ece1f8d4af25a2f6cecf2c80b7.jpg)  \n图3-2-29圆柱形工件的喷涂法  \n\nb.认真考虑一下喷涂色漆的方法；  \nc.稀释剂的选择。  \n进行斑点修补时主要应该注意：a.供漆量应该适应扇幅的大小；  \nb.空气压力应该适应正在进行的修补工艺；  \n\n材的距离始终保持一致，如图3-2-29所示。在喷涂直径较小的圆柱表面时，可使喷枪沿着工件长度的方向走枪。  \n\n(2）不同对象的喷涂施工  \n\n①斑点修补斑点修补包括喷涂色漆（如有必要也喷涂底漆）。其修补涂装工作有时面积较小，有时较大。喷漆工为了适应多种需要，往往采用很多不同的施工方法。一般说来喷漆工在进行斑点修补之前都必须认真考虑以下几个问题：  \n\na.认真挑选色漆系统和其他材料；  \n\nc.按照产品说明书的要求将涂料进行稀释；  \n\nd.准备好配套的驳口漆料；  \n\ne.配色；  \n\nf.如果需要的话，进行驳口或罩光；  \n\ng.如果需要的话，进行抛光。  \n\n$\\textcircled{2}$ 虚枪喷涂修补在喷涂色漆之后，将大量溶剂或固体分调整得极低的涂料喷涂在面漆上的操作称为虚枪喷涂。一般来说，在汽车修补中有两种类型虚枪喷涂法。  \n\na.在热塑性丙烯酸面漆上喷虚枪，用来使新喷的修补漆与原来的老漆之间润色，使汽车表面经过修补之后看不出修补的痕迹。  \n\nb.在新喷涂的丙烯酸或醇酸瓷漆上喷虚枪，用来提高其光泽，有时也用来在斑点修补时润色。  \n\n虚枪修补的具体施工方法如下。  \n\na.罩光清漆上的斑点修补$\\textcircled{8}$ 心喷枪调整  \n\n·调整扇幅，使其适应待修补区域的尺寸；  \n\n·调整供漆量，使其适应扇幅大小；  \n\n·确定空气压力 $(1\\sim2)\\times10^{5}\\mathrm{Pa}$ 势 ·喷枪与基材的距离为 $10\\sim15\\mathrm{cm}$  \n\n$\\textcircled{6}$ 施工工艺  \n\n·喷完色漆后立刻进行虚枪喷涂；  \n·在边角和润色区采用收边和弧线枪法；  \n·在润色区多次进行虚枪喷涂以获得湿润的涂层，不能只喷一次。  \n\n注意：在金属闪光漆新喷的清漆上不要进行虚枪喷涂。  \n\nb.在本色漆表面可以采用两种方法进行虚枪喷涂$\\textcircled{8}$ 采用原来本色漆的颜色进行斑点修补：  \n\n·将扇幅调整至中等水平；  \n\n·喷枪与基材的距离为 $10{\\sim}15\\mathrm{cm}$ ·如果需要的话，可对色漆和润色区进行虚枪喷涂。  \n\n$\\textcircled{6}$ 喷虚枪以提高色漆的光泽：  \n\n·调整扇幅至全开；·确定空气压力为 $(1.4{\\sim}2.1)\\times10^{5}\\mathrm{Pa}$ ·在整个表面上进行全湿虚枪喷涂。  \n\n$\\textcircled{3}$ 高雾化喷涂工艺在喷涂金属闪光漆或者碰到条纹、斑纹等病态时可以采用所谓高雾化喷涂法。在喷涂清漆或者瓷漆时均可采用，但是用得最多的还是在瓷漆上。首先按照说明书的要求兑稀，然后按下述方法施工。  \n\na.调整喷枪，全开。  \n\nb.距离是非常重要的，保持喷枪距表面 $30{\\sim}45\\mathrm{cm},$  \n\nc.走枪：  \n\n·扣紧扳机 $75\\%$ 至全开，而且始终保持不变；  \n\n·连续围绕待喷涂区进行喷涂，直到获得均一的金属闪光色和外观；  \n\n·继续移动喷枪至相邻区域，使这一区域的外观与上项一致$\\textcircled{4}$ 干喷色漆工艺干喷工艺是一种特殊的施工方法，采用这种方法可以用最小的过喷将面漆或底漆喷涂于待修补的部位。这种方法大大加速了修补过程，其具体施工方法如下。  \n\na.打开雾束控制阀 $1/8{\\sim}1/4$ 圈。  \nb.打开液体物料控制阀 $1/4{\\sim}1/2$ 圈。  \nc.采用下述干喷工艺对直径为 $5.0{\\sim}7.5\\mathrm{cm}$ 的斑点进行干喷。  \n$\\textcircled{8}$ 扣死扳机，使喷枪连续做圆周运动进行喷涂。  \n$\\textcircled{6}$ 保持喷枪与表面的距离为 $10\\sim15\\mathrm{cm}$ 。  \n$\\circledcirc$ 空气压力与传统喷涂方法相同。  \n$\\textcircled{2}$ 每 $5\\sim108$ 后停止喷涂，按下述方法检查喷涂情况。  \n·仔细观察表面的平整度。  \n·用黏性抹布擦拭表面以确定其平整度。  \n\n$\\circlede$ 继续喷涂直到达到所希望的遮盖。  \n\n注意：如果涂层太干，可增加供漆量，将液体物料控制阀打开1/8圈。如果涂层太湿，可增加喷枪至表面的距离，拿开 $2,5\\sim5,0\\mathrm{{cm}}$ ；关闭液体物料控制阀1/8圈，再次检查喷涂情况。涂料工必须习惯于在喷漆施工的任何时候用黏性抹布擦拭表面，以除去灰尘和粗糙的表层。  \n\n$\\textcircled{5}$ 整车喷涂如何对整车进行喷涂是对油漆工技术的一个真正的考验。这里包括确定喷涂程序，认真调整各项参数等。一般喷涂整车时多采用两种方法，如图3-2-30所示。这两种方法是由德国巴斯夫等公司推荐的，目前已为国内外汽车修配厂普遍采用。然而也有很多修配厂的喷漆工人先喷前盖，再喷车顶，然后是后盖、侧面、前面以及后面等。总之，在进行整车修补之前，一件非常重要的事情就是必须事先做好详细、周密的安排。  \n\n![](images/10514775632d1152a6a259439417f3635581050bfb35e613b1b95dbb8d79ff87.jpg)  \n图3-2-30整车修补涂装施工方案1\\~9—顺序  \n\n汽车上最为挑剔的部位正好也是最容易察觉的部位，像车顶、前盖及后盖等。因为这些地方便于在阳光下观察，从而检查起来也容易得多。在整车修补时，喷漆工碰到的最为头痛的问题就是在喷涂过程中如何控制和减少空气中有可能飘落到涂层上的尘埃粒子（小面积或斑点修补时，因为面积较小，灰尘问题还不很突出)。要想完完全全地解决这个问题要涉及很多方面，如喷漆间空气的过滤精度、压缩空气与涂料的清洁度、涂料的不粘灰时间以及汽车表面的清洁程度等。整车修补时经常还会碰到的另外一个问题是新喷涂料与原装涂料之间的色差问题，这首先要求人们在进行修补喷涂前认真调色，另外施工工艺的差异对色差也有一定程度的影响。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1103,
+        "chunk": "# 4.汽车修补涂装的一般施工工艺  \n\n(1）底漆的施工表面处理完成后，下一道工序就是喷涂底漆。在施工之前必须检查：  \n\n$\\Phi$ 是否清洗干净；  \n$\\textcircled{2}$ 车身上的旧漆是否已完全除掉；  \n$\\textcircled{3}$ 表面是否打磨平整；  \n$\\textcircled{4}$ 表面有无明显打磨痕迹、划痕等；  \n$\\textcircled{5}$ 表面是否符合涂料厂要求。  \n\n虽然金属的表面处理在本书的有关章节中已有比较详细的叙述，但是在这里还是要特别强调一下，表面的加工、维护万万不可粗心大意。值得注意的是，有些底漆不需要进行表面调整工序。这就需要在喷涂底漆之前认真阅读底漆的产品说明书。  \n\n底漆施工的具体工艺过程如下。  \n\n$\\textcircled{1}$ 按照底漆的产品说明书的要求调整黏度，如果天气较冷，还要来用黏度杯校正一下黏度。$\\textcircled{2}$ 薄薄地涂一层湿的底漆到裸露的金属上。所谓“薄”是几乎遮不住底层，所谓“湿”是覆盖住了基材。湿而不薄的底漆不符合施工要求。几乎可以肯定，过厚的底漆涂层必然会给整个涂装系统的力学性能带来极为不利的影响。  \n\na.对于较大面积，采用喷涂施工方法。  \n\nb.对于仅仅是小如斑点之类面积不大的修补区域，则可以采用刷涂的方法。  \n\n$\\textcircled{3}$ 根据说明书的要求，自然干后再喷涂中间涂层。但是有的涂料制造厂商则在施工说明中规定，在喷涂底漆后，按湿碰湿的工艺接着喷涂中间涂层，然后再一起干燥。  \n\n注意以下两点。  \n\na.有些底漆按照技术要求只能喷涂得很薄，在这种情况下底漆表面是不能打磨的，否则一不小心就有可能将底漆砂穿见底。国外涂料行业把这一类底漆称为“非砂型底漆”(nonsanding type primers），ICI公司的P565-597、立邦的V-110、PPG 的D831、启迪的合金底漆等即属此类产品。注意：切勿与另外一类厚度一般，但同样不需打磨的所谓“免磨底漆”相混淆，如ICI公司的P565-777即为此类产品。如果在新喷的底漆上存在一些疵点需要处理的话，则可以用No.400或更细的砂纸轻轻地砂光。  \n\nb.喷涂结束后，不要用手、抹布之类物品接触新喷的底漆表面。  \n\n(2）中间涂料的喷涂在喷涂中间涂料之前首先必须检查：  \n\n$\\textcircled{1}$ 底漆是否按产品说明书所规定的干燥时间已经干透；$\\textcircled{2}$ 中间涂料是否调整合适，符合施工要求，注意必须采用指定的稀释剂；$\\textcircled{3}$ 检查和调整喷枪，用雾束流淌试验法对喷枪作最后调整；$\\textcircled{4}$ 随便找一块平板，对着试喷一下，观察雾束的形状、大小；$\\textcircled{5}$ 调整喷枪上压缩空气的压力，对斑点作修补时压力为 $(2,0\\sim2.5)\\times10^{5}\\mathrm{Pa}$ ，喷涂较大面积时压力为 $(2.5\\sim3.0)\\times10^{5}\\mathrm{Pa},$  \n\n在上述准备工作完成后，即可开始喷中间涂料。  \n\n$\\Phi$ 像喷涂底漆一样，薄薄地喷一层，使其自然干燥。  \n\n$\\textcircled{2}$ 接着再喷 $3{\\sim}4$ 道，每一道之间留出一定的闪干时间。千万记住，绝不可以采用诸如向新喷表面吹风或者其他类似办法来加速溶剂挥发，以达到尽快表干的目的。一般每道中间涂层的厚度为 $15\\mu\\mathrm{m}$ 左右。总厚度打磨前为 $80\\mu\\mathrm{m}$ ，打磨后为 $25\\sim50\\mu\\mathrm{m}$  \n\n$\\textcircled{3}$ 放置，使其自然干燥，一般大约 $30\\mathrm{{min}}$ ，这要取决于涂料、稀释剂的品种以及喷漆间的温度等诸多条件。  \n\n④不要用增加漆料施工不挥发分的办法来试图减少喷涂的道数。只喷1～2次就达到多次喷涂所获得的厚度的做法是欲速则不达的，因为这将使中间涂层长时间都无法实干，造成表面硬而内不干。这对中间涂层的打磨性、面漆的烘托性能等均有不良影响，而且极有可能带来针孔、龟裂等涂料病。  \n\n$\\textcircled{5}$ 手工打磨时采用No.400水砂纸，手工机械打磨时采用No.320、No.360砂纸。一般来说，水砂纸打磨比干砂纸打磨好，但是干砂纸打磨快、省时。在打磨边角、脊背、折边等突出部位时务必小心，打磨时用力要适度，不要将已喷的底漆、中间涂层都打磨掉。  \n\n$\\textcircled{6}$ 用橡皮刮刀检查涂装质量。喷涂面漆前还要再次清洗一遍。  \n\n注意以下几点。  \n\n$\\Phi$ 如果打磨时不小心将部分中间涂层甚至连底漆都打磨掉，则必须把上述工艺过程重复一遍，再重新涂装底漆和中间涂层。  \n\n$\\textcircled{2}$ 有的油漆料在打磨中间涂层时喜欢加少量抛光膏，以使表面更加平整。当然这也可算是一个不错的主意，但是在打磨结束后，必须记住，要更加彻底地清洗表面，以避免微量蜡的残存于涂层表面。  \n\n(3）“标志涂料”的施工所谓“标志涂料”起“填充和打磨”的作用，它可以使表面更加平整。此外它还具备类似胶片“显影”的功能。喷涂一般中间涂料时，经打磨、砂光后，表面平整光滑，而它上面究竟有无砂痕、凹陷等细微的缺陷存在，此时肉眼是看不到的。只有在喷涂面漆之后，才可能发现表面到底有无这些缺陷。采用“标志涂料”则无此弊端，在未喷涂面漆之前，就可发现表面有无上述缺陷存在。比较典型的产品如：巴斯夫公司的281-4。标志涂料特别适合于收边操作，它可以将表面填得更平。喷涂标志涂料之后要进行适度的打磨，以除去在旧面漆和新喷中间涂层之间多余的标志涂料。在打磨标志涂料时务必小心谨慎，不要把不应该打磨掉的部分打磨掉，从而无法获得预期的效果。  \n\n$\\textcircled{1}$ 调制一种比中间涂料颜色深一点或浅一点的涂料作为“标志涂料”。  \n\na.首先在收边区域内喷涂两次，厚度中等。在两道之间要留出一定的闪干时间。  \n\nb.然后在比前两次喷涂区域大一点的范围内再喷涂两次。在两道之间要留出一定的闪干时间。  \n\n$\\textcircled{2}$ 取深色（或浅色）中间涂料，稀释一倍。  \n\na.在经打磨加工过的区域喷涂一道。  \n\nb.然后超出前次喷涂的范围再喷一次，在两道之间要留出一定的闪干时间。  \n\n$\\textcircled{3}$ 在室温下自然干燥大约 $30\\mathrm{{min}}$ 0  \n\n$\\textcircled{4}$ 用No.400水砂纸打磨（用或者不用打磨模块取决于待修补处的表面积）。  \n\na.如果原车面漆是热塑性丙烯酸清漆，则在打磨时要注意尽量不要打磨到丙烯酸面漆上。  \n\nb.从周边开始打磨，加足量的水。随着上次喷涂的“标志涂料”被打磨掉，继续打磨并逐渐向中心移。  \n\nc.最后打磨待修补的中心，不时用橡皮刮刀检查打磨效果，以决定打磨操作是否已完成。  \n\nd.清洗，下一步工艺操作之前，表面必须充分干燥。  \n\n注意：在待修补的中心不要打磨过分，一旦微小的划痕被打平，即刻停止打磨。  \n\n（4）封闭底漆的施工  \n\n$\\Phi$ 在已涂中间涂层的区域内，用清洗溶剂彻底清洗表面，进行表面处理。  \n\na.当面漆为在汽车总装厂涂装的已固化的本色漆时，用No.400、No.600或更细的砂  \n\n纸加清洗溶剂进行湿打磨。  \n\nb.当面漆为丙烯酸清漆时，只进行抛光及溶剂清洗。  \n\n②按照产品说明书的要求将封闭底漆兑稀（有些涂料厂供应的封闭底漆不需要兑稀)。  \n\n$\\textcircled{3}$ 按照产品说明书的要求，在适当的压力下喷 $_{1\\sim2}$ 道封闭底漆。  \n\n$\\textcircled{4}$ 在喷涂面漆之前应使封闭底漆自干 $30\\mathrm{{min}}$ 注意：不要让封闭底漆涂层的厚度超过产品说明书的指标。  \n\n（5）腻子的施工首先应该确定：  \n\n$\\textcircled{1}$ 车身表面的缺陷较严重，凹陷深度在 $100\\mu\\mathrm{m}$ 以上；  \n$\\textcircled{2}$ 所选用的腻子与当前所采用的中间涂料是否相适应；  \n$\\textcircled{3}$ 中间涂层至少已经干燥了 $10\\mathrm{{min}}$ 以上，并且已被彻底地清洗过。  \n\n刮涂腻子的具体操作方法如下。  \n\n$\\Phi$ 用橡皮刮刀刮腻子  \n\na.从装腻子的软管内挤出少量腻子在橡皮刮刀的边角上，或者用橡皮刮刀从包装罐中 蘸一点腻子。  \n\nb.尽快将腻子压入待修补斑点的缺陷中，并迅速刮平。再加一点压力，把腻子进一步压实，不要把任何微小的空气泡遗留在基材缺陷的缝隙中。第二次刮腻子一定要尽快进行，否则腻子的干燥速率很快，用不了太长的时间就不便于继续加工了。此时所表现出来的现象是再刮时很容易刮起“卷”来。  \n\nc.刮 $2{\\sim}3$ 次腻子，每次之间气干 $15\\mathrm{\\sim}20\\mathrm{min}$ 。这样做比厚厚地刮涂一层就达到同样的 厚度更能发挥腻子的效果，填充得要好。  \n\n$\\textcircled{2}$ 如有必要，再喷涂一次中间涂料。  \n\n$\\textcircled{3}$ 打磨掉多余的腻子：在打磨之前，应使其自然干燥，一直干燥到便于打磨。腻子的干燥时间因腻子的品种、厚度和天气条件而有所不同。如果所采用的属挥发型腻子、厚度中等，则大约需要干燥1h。一般采用No.360砂纸打磨。  \n\n$\\textcircled{4}$ 在喷涂面漆之前，用中间涂料或封闭底漆封闭可见的腻子。  \n\n注意以下两点。  \n\na.腻子最好采用自然干燥的方式，建议不要用加热的方式来加速干燥。  \n\nb.如果溶剂挥发干燥型腻子在已经开启过的或者是漏气的包装罐中因溶剂挥发而变硬了，可以补加一些高沸点的溶剂，调匀后使用。  \n\n(6）面漆的施工面漆的施工是汽车修补操作的关键。本道工序的加工质量是对前面所有工序工作水平的总评，因此万万不可粗心大意。在正式开始涂装之前，建议再一次检查喷枪并作最后的调整。 Y  \n\n$\\Phi$ 喷枪的检查（以吸上式喷枪为例）  \n\na.将喷杯接到枪体上，拧紧螺帽。  \n\nb.检查喷杯上的气孔，确认无污垢堵塞，且处于靠近喷枪手柄的方位。  \n\nc.拿起喷枪，将喷嘴对准下方，就像在喷涂汽车顶盖一样，检查喷杯上密封圈处是否会泄漏漆料。  \n\nd.把雾束控制阀全开，对准垂直的墙面做雾束分布试验，如有异常，应按照喷枪调整部分所介绍的办法重新进行调整。 A C  \n\ne.检查和调整空气压力。对于丙烯酸清漆，喷枪上的压力为 $(2.0{\\sim}2.8)\\times10^{5}\\mathrm{Pa}$ ，允许在大约 $0.35\\times10^{5}\\mathrm{Pa}$ 巴的范围内波动。对于一般本色漆，喷枪上的压力为（1 $.75\\sim3.2)\\times$ $10^{5}\\mathrm{Pa}$ ，除非所采用的产品另外指定范围，不过最大也不应超过 $(3.5\\sim5.0)\\times10^{5}\\mathrm{Pa}$ 对于任何涂料系统而言，最适当的空气压力只有一个，那就是能够使涂料获得最好雾化效果的最低空气压力。过高的压力会使漆雾粒子喷射到达基材表面后反弹回来，造成漆料损失（图3-2-31)。喷枪调整好后，应该能够获得分布均匀的雾束。  \n\n![](images/3c6d3246ee49d9eb5a6aca33d665eece3bb798a670a46ddc09872e959a11e283.jpg)  \n图3-2-31压缩空气压力过高造成漆雾粒子反弹  \n\n$\\textcircled{2}$ 喷漆前其他准备情况的检查  \n\na.喷漆设备是否完好，如压缩机、缓冲罐、软管等。  \nb.涂料及其配套稀释剂是否按照产品说明书的要求调整好。  \nc.所有容器是否干净，有无破损。压缩机、缓冲罐中是否残存有水或油。  \nd.其他配件，如涂料刷、车间抹布、黏性抹布、不干胶带等。  \ne.车身上靠近修补点附近的表面是否已用不干胶带粘贴覆盖好。  \n\n检查上述各项时，有些要非常仔细地进行。如对压缩机的检查就是如此，要接上电源，检查运行情况，观察压力是否达到额定的标准，是否稳定等。缓冲罐是否残留有水、油之类对涂层质量有影响的杂质。软管是否干净、通畅，有无泄漏、损坏等。  \n\n喷漆前最后一道工序是用气枪吹干净表面的灰尘，再仔细地用黏性抹布擦拭汽车待修补处的表面。其具体操作方法如下：  \n\n·用压缩空气吹汽车的各个部位，先吹后部，再吹前部；  \n\n·吹完后，用黏性抹布仔细地擦拭车身，就像喷漆施工一样，用黏性抹布擦拭表面也要求重叠，也就是说，前一次擦拭的区域和下一次擦拭的区域之间要有重叠。最后一次擦拭要采用新的黏性抹布。  \n\n至此喷涂面漆前所有的准备工作已经全部完成，接下来就可以进行喷涂施工了。由于面漆的喷涂工艺比较复杂，而且选用不同的品种其施工工艺也有所不同，因篇幅所限，这里无法一一加以阐述，有兴趣的读者可参考有关专著。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1104,
+        "chunk": "# 第七节汽车涂料性能检验与漆膜缺陷",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1105,
+        "chunk": "# 一、原漆性能检验",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1106,
+        "chunk": "# 1.溶剂型涂料性能检验  \n\n大型汽车总装厂往往都制定有一整套涂料检验方法和标准。各国涂料行业也制定有相应的标准和检验方法，如美国的ASTM、日本的JIS、德国的DIN、我国的GB等。正如其他领域的情况一样，一般是企业标准高于国家标准。另外，世界各国对于汽车本身各方面的要求也不一样，如外观、光泽、硬度、鲜映性及耐候性、防腐蚀性等。尤其是防腐蚀性这项性能指标与汽车的寿命关系密切，各国对汽车防腐蚀方面的要求有所不同，因此相应的标准也必然会不一样（表3-2-48）。  \n\n表3-2-48各国对汽车防腐蚀性的要求  \n\n\n<html><body><table><tr><td rowspan=\"2\">地 区</td><td rowspan=\"2\">项 目</td><td rowspan=\"2\">年限/年</td><td colspan=\"3\">防锈层保证年限/年</td></tr><tr><td>日本车</td><td>美国车</td><td>欧洲车</td></tr><tr><td rowspan=\"2\">北美</td><td></td><td>1.</td><td>~</td><td>。~</td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td rowspan=\"2\">欧洲</td><td>穿孔蚀</td><td></td><td>1~3</td><td></td><td>1~</td></tr><tr><td></td><td>86</td><td></td><td>16</td><td></td></tr></table></body></html>  \n\n近年来，为了更加有效、更加完善地控制产品的质量，各涂料生产厂家也相应地增加了一些特殊的检验项目，其中大部分均未列入该国的国家标准，如VDA循环、QUV加速人工老化、抗划伤性、抗石击性、耐洗刷性、长波及短波橘纹、粗糙度、雾光以及鲜映性等。这些标准的针对性都很强，可看作是涂料厂与汽车总装厂之间的协议标准。  \n\n国外有些大型汽车总装厂还要求涂料厂提供产品的红外光谱图，借以防止这些生产厂家未经客户容许就擅自更改原材料，最终达到控制该产品的基本成分的目的。总之，涂料质量的检验对供需双方而言都是至关重要的大事。我国适用于汽车涂料的检验方法分类及标准见表3-2-49。  \n\n表3-2-49汽车涂层评价试验方法  \n\n\n<html><body><table><tr><td rowspan=\"2\">分类</td><td rowspan=\"2\">项 目</td><td colspan=\"3\">适合部位</td><td rowspan=\"2\">采用标准</td></tr><tr><td>车外</td><td>车内</td><td>车下围</td></tr><tr><td>涂层外观</td><td>光泽，色差，鲜映性，粗糙度， 色调</td><td>O</td><td></td><td>O</td><td>GB 1729、GB 9724、GB 11186</td></tr><tr><td>遮盖性</td><td>这盖性，紫外光透过性</td><td></td><td></td><td>O</td><td>GB 1726</td></tr><tr><td>涂层力学性能</td><td>毒硬度,耐冲击性，柔性，耐石</td><td>O</td><td></td><td>O</td><td>52C0G732.GB3G 0 GB 1770</td></tr><tr><td>耐介质性</td><td>耐水性，耐酸性，耐碱性，耐油 性，盐雾</td><td></td><td>O</td><td></td><td>GB 1733、GB 1734、GB 1740、GB 1763、GB 5209、GB 1771</td></tr><tr><td>耐热性</td><td>耐热性，温循试验</td><td>。</td><td></td><td></td><td>GB 1735、GB 1762</td></tr><tr><td>耐候性</td><td>户外曝晒性，加速老化性</td><td>O</td><td></td><td></td><td>GB1766、GB1767.GB1856、GB11189</td></tr></table></body></html>\n\n注：○表示适合。  \n\n涂料产品的常规检验一般可以分为原漆性能检验和涂层性能检验两个方面，原漆性能检验包括外观（颜色、透明性)、黏度、不挥发分、密度、细度、遮盖力、贮存稳定性及干性等，涂层性能检验包括外观、厚度、光泽、色差、鲜映性、硬度、冲击性、弯曲、附着力、杯突以及耐各类介质性、耐候性等。 M  \n\n外观、透明度、颜色、密度、黏度、不挥发分、遮盖力等常规标准，读者可查阅相应国家标准，这里就不再赘述，只讨论一些较为特殊的检测方法或标准。  \n\n(1）细度和清洁度细度也是控制涂料质量的重要指标之一，主要用于检查色漆或色浆内颜料粒子的大小及分布均匀程度。过去对于清漆一般不做检验，但是现在国内外不少厂家为了更好地监控罩光清漆的质量，也在清漆的技术标准中增加了细度这一指标。  \n\n国外的高档涂料产品中引入了所谓“清洁度”的概念。如果用细度计检测时，某个部位哪怕只有 $2{\\sim}3$ 个颗粒，那么该部位的读数就被定义为“清洁度”。也就是说，对于高档汽车涂料而言，就存在两个指标——细度和清洁度。确切地说，细度反映了颜料粒子在成膜物质中的分散情况，而清洁度则反映了成品中是否混入某些尘埃之类的杂质。检测清洁度时，应采用细度范围较宽的细度板，至少是 $0\\sim150\\mu\\mathrm{m}$ 的板。采用范围较窄的细度板无法检测出较大颗粒的杂质。  \n\n(2）贮存稳定性贮存稳定性是考核涂料在密闭的容器中，贮存一段时间后，其自身质量是否发生了本质性改变的检验项目。涂料由生产厂出厂到客户开始使用之间往往要经过一定的商业环节，而且即使是涂料厂直接对用户也不一定是随到随用，都很可能要在仓库贮存几个月，乃至一年的时间，因此再好的涂料也不可避免或多或少会出现一些增稠、返粗、沉降以及结块等常见的涂料病。一般来说，涂料厂对于每一种产品都规定有一定的贮存期，国内各厂大都为一年，国外则大都为半年。产品在规定的贮存期内，涂料厂对产品的质量负完全责任。目前对于贮存稳定性大都按照GB/T6753.3-1986标准执行，一般是测定产品黏度、沉降性等。  \n\n$\\Phi$ 黏度产品经贮存一定时间后，测定其黏度的改变。按照GB/T6753.3—1986标准进行检验。取三份试样，将其装入规定的容器中，装样量应以离容器顶部尚差 $15m m$ 为宜。再在自然环境条件下贮存 $6\\sim12$ 个月或者在 $50\\Upsilon\\pm2\\Upsilon$ 的条件下贮存30天。一般在 $50\\%\\pm$ 2℃的条件下贮存30天，大致相当于自然环境下贮存半年至一年。根据贮存后黏度与原始黏度比值的百分数划为以下几个等级进行评定：  \n\n10—黏度改变值不大于 $5\\%$   \n8—黏度改变值不大于 $15\\%$   \n6——黏度改变值不大于 $25\\%$ ..  \n4——黏度改变值不大于 $35\\%$ \\*  \n2-—黏度改变值不大于 $45\\%$   \n0-—黏度改变值大于 $45\\%$ 。  \n\n最终评定时以“通过”或者“不通过”为结论性评定用语。例如，某大型汽车公司在卡车用面漆的标准中关于贮存稳定性限定为6级。也就是说，经过一定的贮存期后其黏度的改变不大于 $25\\%$  \n\n实际上，任何一家客户在对进厂产品进行验收时，根本不允许把该产品放置十天甚至半月以后再做出结论，而是及时检验，合格可以入库，不合格作退货处理。一般情况下，比较正规的大型涂料厂或者汽车总装厂都制定了相应的加速贮存试验方法。例如，北京某汽车厂关于贮存稳定性试验规定了下述条件。  \n\n$60^{*}\\mathrm{C}$ ，15h后，黏度增加不得超过20s，或者在室温下放置三个月后，黏度增加不得超过15s。换句话说，按照该厂规定的加速贮存条件，一天以内即可做出判断。据了解其他各大厂也有类似的自定标准。只要供需双方经过友好协商，共同确定试验条件和标准，不难找出有关涂料贮存稳定性的快速检验方法来。这里要特别强调指出的是，每种产品，特别是那些交联型涂料产品都有自己特有的活化温度。切记所确定的加速贮存温度不得高于该产品的活化温度，否则所得出结论的可靠性就很值得商權。  \n\n$\\textcircled{2}$ 沉降性对于沉降性的评定，GB/T6753.3—1986也规定了六级评定标准。  \n\n10——完全悬浮，于原漆状态比较几无差别。  \n\n8——有明显的沉降触感，并且调刀上留有少量的沉积物。用调刀的刀面在容器的底部推移，感觉不到明显的阻力。  \n\n6-—有明显沉积的颜料块，但是调刀的自重使其能够穿过沉积物落到容器的底部。用调刀的刀面推移，感觉到一定的阻力。凝聚部分的块状物可转移到调刀上。  \n\n4-—调刀的自重不能使调刀穿过沉积物落到容器的底部。用力使调刀穿过沉积物，再用调刀的刀面推移沉积物，感觉到阻力很大，而且沿着容器的器壁推移调刀都感觉到有的阻力，但是很容易将涂料重新揽拌成均匀状态。  \n\n2——用力使调刀穿过沉积物到容器底部，推移感到很困难。沿着容器的器壁推移，感觉到明显的阻力，但是可以将涂料重新搅拌均匀。  \n\n0--—涂料底部结成很坚硬的块状物，通过手工搅拌，在3～5min内无法将这些硬块与液体重新混合均匀。  \n\n沉降性试验的贮存周期与黏度测定是完全相同。沉降性试验不像黏度试验那样数据化，便于判断。  \n\n(3）干性［按GB/T1782—1979（1989）规定进行测定］涂料由液态转化为固体涂层的物理化学过程称为干燥。其实“干燥”只是一个古老或者传统的叫法。对于交联型涂料而言，严格说来叫“固化”更为合适。  \n\n涂料的干燥过程可分为不粘灰干燥、表干、实干及硬干等几个阶段。一般情况下只测定表干和实干时间，至于不粘灰时间和硬干时间则往往由客户和生产厂家之间协商确定。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1107,
+        "chunk": "# 2.电泳底漆原漆的性能检验  \n\n有关电泳底漆原漆的性能检验名目繁多，这里只讨论一些比较特殊、不太常见而又重要的项目。  \n\n（1）CED超滤（以下简称UF）能力  \n\n$\\Phi$ 概念超滤是近年来发展起来的一门较新的技术，它属于膜分离技术的范畴。应用超滤技术可以过滤出液体中混杂的诸如细菌、蛋白质以及胶体等采用普通过滤手段无法清除的细小粒子，因此将其称之为“超滤”。超滤效果的好坏对槽液的稳定性、电泳涂装的质量、CED的使用效率、回收利用都会起到极为关键的作用。总之，在整个CED涂装系统中必需设有UF工序。借助于UF，该系统就可以设计成封闭式循环系统。  \n\n$\\textcircled{2}$ 目的通过对UF液流速的测定来判定待测CED的UF能力。它的流速构成了CEL性能的重要参数。本方法即对此进行测定。  \n\n$\\textcircled{3}$ 实验用材料5LCED（已熟化24h）；实验室UF装置；泵—实验室用隔膜泵；膜—超滤膜； $250\\mathrm{mL}$ 量筒；秒表；带恒温、搅拌的槽；5L清洗溶液。  \n\n$\\textcircled{4}$ 实验方法实验前用去离子水（以下简称DI水）仔细清洗UF装置，然后在 $4\\times$ $10^{5}\\mathrm{{Pa}}$ 的压力下按循环模式用DI水循环 $10\\mathrm{{min}}$ （保持 $27\\mathrm{^c}$ )，测定产生 $250\\mathrm{mL}$ 水的时间（用量简测量）。水的流速采用式（3-2-3）计算  \n\n式中V-—测量容积读数，L；t—时间，s；A-—膜的表面积， $0.07\\ensuremath{\\mathrm{m}}^{2}$  \n\n如测出的流速低于 $\\scriptstyle250\\mathbf{L}/\\mathbf{m}^{2}$ ，则需再次清洗UF装置。拆除配件，安装新的UF膜。在将CED槽液投进装置之前，应测量其筛余物。槽液过筛并加热到 $27\\thinspace\\uptau$ 然后接入UF装置。为了避免CED槽液样品被稀释，应先用CED槽液洗一下UF装置使其基本无水。工作压力设成 $4\\times10^{5}\\mathrm{Pa}$ CED槽液通过温度设定为 $27\\mathbb{C}$ 的恒温槽循环。  \n\n循环 $10\\mathrm{{min}}$ ，6h，24h后，分别测量为获得 $100\\mathrm{mL}$ UF液所需时间，按式（3-2-3）计算流速，每种情况下测2次。根据不排放UF液的原则，测量中收集到的UF液应倒回到CED槽液中。  \n\nUF实验不用任何预过滤器。UF装置在做过实验后应采用DI水进行清洗，直到装置内所有的CED都被清除干净。然后再次测定CED槽液的筛余物。  \n\n按循环模式，用清洗溶液清洗UF装置 $30\\mathrm{s}$ 。可能的话稍稍提高一点温度！ $30\\sim35\\mathrm{^{\\circ}C}$ 。以尽可能干净地清除CED槽液。  \n\n$\\textcircled{5}$ 评价除了 $\\mathsf{p H}$ 、电导率、筛余物、固含量、灰分以及颜料含量外分析报告也应和相应图表一起列出流速值。CED流速（相对于起始值）的下降代表CED涂料的UF能力。  \n\n(2）CED涂料的抗剪切稳定性  \n\n$\\textcircled{1}$ 概念CED涂料是一种水性悬浮液，某些外界的物理应力可能会的影响到它的稳定性，如泵输送过程中产生的剪切应力。  \n\n$\\textcircled{2}$ 目的利用泵所产生的剪切应力来测量CED涂料的相对稳定性。  \n\n$\\textcircled{3}$ 实验材料4LCED槽液；5L玻璃烧杯； $350\\mathrm{mL}$ （底部直径为7cm）的塑料烧杯；No.8尼龙滤布 $(10\\mathrm{{cm}\\times10\\mathrm{{cm}}}$ ，80目)；直径为 $10\\mathrm{{cm}}$ 的罐；纸夹；精确度为 $0.01{\\tt g}$ 的天平；实验室用隔膜泵；实验架；恒温器；DI水洗瓶；实验室用鼓风烘箱。  \n\n$\\textcircled{4}$ 实验目的  \n\na.将尼龙滤布、罐、纸夹一起称重。取两个 $350\\mathrm{mL}$ 塑料烧杯，切去底部，两个烧杯之间用尼龙滤布隔开，再将一个烧杯的一端插人另外一个烧杯，以撑紧尼龙滤布。倒入4L槽液过滤，如不太好过滤则可用搅拌器或类似的装置协助。用装有DI水的洗瓶清洗滤布和筛余物，直到出来的是清洁的水。从塑料烧杯上取下滤布，折叠两道，用纸夹夹住，将其放入已称好重量的罐中。放人烘箱中， $60^{\\circ}\\mathrm{C}$ $90\\mathrm{min}$ 干燥，称重。  \n\nb.槽液经上述处理后，用泵循环 $16\\mathrm{h}$ 。为此倒 $350\\mathrm{mL}$ DI水到泵的吸入软管内以赶走里面的空气。为防止泵循环过程中产生的热量造成槽液温度的提高，应将泵和软管浸入到温度控制在 $27\\mathrm{\\ttT}$ 的恒温槽中。16h后，再将槽液泵回桶内。  \n\nc.按上述过滤工序过滤这些槽液。桶内的残留物用DI水洗到滤布上，然后清洗。  \n\nd.筛余物在 $60\\ensuremath{\\uptau}$ 干燥 $90\\mathrm{{min}}$ ，然后称重。  \n\ne.用清洗溶液进行大致清洗后，再将泵拆下进行进一步清洗。  \n\n$\\textcircled{5}$ 评价根据槽液经受剪切力前后筛余物的量，按下述标准评级。  \n\n0级： $<0.1g$ 筛余物/4L槽液。  \n\n1级：0. $1\\sim1.0\\mathbf{g}$ 筛余物/4L槽液。  \n\n3级：1 $\\phantom{0}.0\\sim2.0\\phantom{0}g$ 筛余物/4L槽液。  \n\n5级： $>2.08$ 筛余物/4L槽液。  \n\n实验过程中发生的任何事件，如停泵之类的故障都应写入报告。  \n\n(3）CED泳透力的测定泳透力就是电沉积涂料在电场的作用下，对待涂装表面背部（包括内面、凹面、缝隙等处）的涂覆能力。它主要用来判断CED材料对所采用的待涂工件的适应性，是观察工件内部能否泳涂上足够漆膜厚度的关键指标。泳透力的好坏直接影响到电泳涂装工艺的效率和最终漆膜的防腐蚀性能。泳透力的测量方法有被列为国家标准的钢管法和几大汽车公司普遍采用的福特盒法。  \n\n测定电泳漆泳透力的国家标准钢管法比较适合测定泳透力较低的品种，比较适合泳透力较低的阳极电泳漆，而不太适合泳透力较高的阴极电泳漆。在测量阴极电泳漆的泳透力时，测量结果多接近100%，不少实验人员采取降低钢管直径或减少阳极板面积的办法来应对方法本身存在的不足。  \n\n福特盒法比较适合阴极电泳漆，但因变动参数较多，如阴阳极比、电泳电压及时间、槽液温度、溶剂含量、电导率等均应调整到标准化的水平，现分别介绍如下。  \n\n$\\textcircled{1}$ 钢管法  \n\na.实验材料：5L已熟化好的槽液；塑料容器 $(\\$230\\times250\\mathrm{mm})$ ；钢管 $(\\phi20\\times300)$ ；实验室用电泳仪；实验室用搅拌；实验室用鼓风烘箱。  \n\nb.实验方法  \n\n·将熟化好的槽液装人到塑料容器中，插入揽拌，使揽拌器靠壁；  \n\n·将钢管插人到装有槽液的塑料容器中，深度为 $150\\mathrm{mm}$ 捷  \n\n·开动搅拌；  \n\n·按照标准条件进行电沉积涂装；  \n\n·取出钢管，水洗、烘干；  \n\n·锯开钢管，测量管内壁电沉积涂层情况，测得三个分区，A、B和C，A——完全涂有沉积漆膜部分；B———未完全涂覆沉积漆膜部分；C——完全未涂覆沉积漆膜部分。  \n\nc.计算方法$\\textcircled{2}$ 福特盒法  \n\na.实验材料：5L已熟化好的槽液；电泳槽（6L）；聚氯乙烯塑料块（ $\\mathfrak{g}_{\\mathrm{mm}}\\times\\mathfrak{g}_{\\mathrm{mm}}\\times$ $450\\mathrm{mm};$ ；样板 $(100\\mathrm{mm}\\times450\\mathrm{mm}\\times0.8\\mathrm{mm})$ ；电泳槽；实验室用鼓风烘箱；实验室用搅拌。  \n\nb.实验方法  \n\n·将熟化好的槽液装人到塑料容器中，插人搅拌，使搅拌器靠壁；  \n·将两块样板夹好聚氯乙烯塑料块，并用绝缘胶带封好；  \n·置入电泳槽中；  \n·按照标准电沉积条件涂装；  \n·取出样板，拆开、水洗、烘干；  \n·测量样板上已涂覆漆膜的高度。  \n\nc.计算方法  \n\n(4）CED槽液抗污性的测定  \n\n$\\Phi$ 概念在电泳涂装的过程中，被涂物或传动链系统中常有污物可能滴落到CED槽液中，如油脂、润滑油、焊料以及密封胶等。  \n\n$\\textcircled{2}$ 目的在标准条件下，用标准磷化样板在被指定物质污染的CED槽液或未被污染的槽液中进行涂装，以获得该CED材料的抗污染性能。  \n\n$\\textcircled{3}$ 实验材料5L槽液；1g试验物质；标准磷化样板；电泳槽；实验室用鼓风烘箱；揽拌器。 C  \n\n$\\textcircled{4}$ 试验方法·污染涂料；  \n\n·污染CED槽液。  \n\n在 $5\\mathbf{kg}$ 槽液中取 $200\\mathrm{mL}$ 与 $_{18}$ 待试验物质（ $10\\%$ 乙二醇丁醚溶液或在特殊情况下亦可将其配成二甲苯溶液）混合，并用高速搅拌混合 $1\\mathrm{min}$ ，然后将其倒人槽液内。  \n\n被污染的槽液在室温下熟化3h和96h后，取3块样板在特殊规定的条件下进行涂装。特别值得注意的是，必须保证涂层的厚度和烘烤温度恒定。  \n\n$\\textcircled{5}$ 样板的评价  \n\na.缩孔对样板的正面进行评价。数缩孔数，单位为个 $\\mathrm{i}\\mathrm{m}^{2}$ 。被污染槽液所得的缩孔数与未被污染的所得缩孔数进行比较。按照以下方式评价。  \n\n0:0个缩孔。 3:<20个缩孔.$_{1},<5$ 个缩孔， 4:<50个缩孔，$2_{1}<_{10}$ 个缩孔。 5:>50个缩孔b.其他表面缺陷如疤痕、裸露等。  \n\n（5）CED涂装过程中锌敏感性测定  \n\n$\\textcircled{1}$ 概念当镀锌板用于电泳涂装时，如施工电压过高常常会出现针孔，这是由于CED材料和被涂物间发生电化学作用的缘故。  \n\n$\\textcircled{2}$ 目的本方法乃是通过有限的实验确定一种CED涂料用于镀锌板涂装时，在某种条件下是否可能产生针孔。  \n\n$\\textcircled{3}$ 实验方法按照标准方法在两个电泳槽中泳涂样板。采用不同的涂装电压，但不加附加电阻。槽液温度控制在 $29\\mathrm{C}$ 。第1块样板的涂装电压比获得正常厚度的电压低 $30\\%$ ”然后按30V为一挡逐步升高，每挡涂装1块样板，直到达到所测试CED材料的标准膜厚为止。在标准条件下烘烤样板。  \n\n$\\textcircled{4}$ 评价测量膜厚，按式（3-2-6）计算起始电流密度 $J_{\\ast\\ast}$  \n\n$$\n\\scriptstyle J_{*}=\\mu\\frac{U}{10}\n$$  \n\n式中 $J_{\\ast}$ —起始电流密度， $\\mathrm{\\mA}/\\mathrm{cm}^{2}$ $\\mu$ —29℃下槽液电导率， $\\mathrm{mS/cm}$ $\\boldsymbol{{U}}$ —涂装电压，V。  \n\n测量每平方分米针孔数。如样板上布满了针孔，在样板每边随机各选择两个区域并划出边长为1cm的正方形，记录正方形内针孔数。计算四个正方形所得针孔数的平均值，再乘以100，得每平方分米的针孔数。如样板的每边没有那么多针孔，则可划边长为$10\\mathrm{cm}$ 的正方形，同样可得每平方分米针孔数。涂装电压与计孔数量之间的关系见表3-2-50。  \n\n表3-2-50涂装电压与针孔数量之间的关系  \n\n\n<html><body><table><tr><td>μ/(mS/cm)</td><td>U/V</td><td>J/(mA/em)</td><td>针孔数/（个/dm²）</td><td>膜厚/μm</td></tr><tr><td>1.33</td><td>250</td><td>33.2</td><td>0</td><td>14.3</td></tr><tr><td>1. 33</td><td>280</td><td>37.2</td><td>200</td><td>15.7</td></tr><tr><td>1.33</td><td>310</td><td>41.2</td><td>1000</td><td>19.0</td></tr><tr><td>1.33</td><td>340</td><td>45.2</td><td>4000</td><td>21.4</td></tr></table></body></html>  \n\n(6）CED槽液和UF液的起泡性  \n\n$\\textcircled{1}$ 概念在CED槽中可能产生泡沫，特别是在车身人槽和出槽时以及在淋洗区都有可能发生。起泡的程度可能与涂装线的布局以及材料本身有关。  \n\n$\\textcircled{2}$ 目的本法可用于测量材料的起泡性以及泡沫的稳定性。  \n\n$\\textcircled{3}$ 应用 CED材料及UF液。  \n\n④实验材料250mL量筒（刻度为2mL)；量筒用塑料塞；秒表；50mLCED槽液或UF液； $200\\mathrm{mL}$ CED材料用溶剂。  \n\n$\\textcircled{5}$ 实验方法用DI水彻底清洗量简，然后倒入 ${\\mathrm{50mL}}$ 槽液或UF液于量筒中。塞上塑料塞子，激烈摇动 $10\\mathrm{s}$ 。停止摇动后马上读取泡沫的高度（mL)，扣除原来的液体高度$50\\mathrm{mL}$ 。然后读取 $2.5\\mathrm{{min}}$ 、7.5min以及 $10\\mathrm{{min}}$ 后泡沫高度（mL）的数据。实验后量简要仔细清洗，先用乙二醇丁醚清洗，再用DI水清洗。  \n\n重点：必须采用本法中的清洗方法清洗量筒，采用其他清洗法无法获得可重复的数据。另外为比较起见，应总是让同一个实验人员进行。  \n\n注：由于槽液和UF液中的溶剂含量对起泡性有相当大的影响，故一般要对CED和UF中的溶剂含量进行分析。  \n\n$\\textcircled{6}$ 评价实验报告中将列出摇动后以及放置 $2,5\\mathrm{min}$ 、7.5min以及 $10\\mathrm{{min}}$ 后的泡沫高度$\\mathrm{{(mL)}}$ 。用起始值和 $10\\mathrm{{min}}$ 后的泡沫高度来计算泡沫消退的速度 $(\\%$ )，这是衡量泡沫稳定性的重要数据。  \n\n例：时间/ $\\mathrm{min}$ 02.557.510泡沫高度 ${\\mathrm{~}}_{\\mathrm{mL}}$ 6058503020泡沫消退速度为 $(0\\sim10\\mathrm{min}^{\\cdot}$ ）67%一种性能良好的CED，其泡沫消退速度应>75%。  \n\n(7）入槽痕迹(带电入槽)  \n\n$\\textcircled{1}$ 概念在很多CED涂装厂中，往往采用带电入槽的方式进行涂装，这样全部电压就加载到工件浸入槽液的部分面积上，这将很容易引起人们常说的“入槽痕迹”病态。  \n\n$\\textcircled{2}$ 举例  \n\na.部分击穿电流过高可能引起条状漆膜过厚（多为塑性堆积）。  \n\nb.条痕类似一串珠子，由平行于槽液表面的气泡包容在内引起。  \n\nc.湿/干痕疤痕。  \n\n$\\textcircled{3}$ 目的本法用于检验CED材料带电入槽时对漆膜缺陷的敏感性。事实上人槽痕迹可通过改变一些参数（施工条件，设备或涂料的配方）来模拟、减少或避免。  \n\n$\\textcircled{4}$ 实验材料CED槽液；带可带电人槽设施的电泳槽；烘箱；标准磷化样板；尺寸为$20\\mathrm{cm}\\times10\\mathrm{cm}$ 的板；防水钢笔；测厚仪。  \n\n$\\textcircled{5}$ 实验方法  \n\na.样板的准备用钢笔在样板上划一道 $1\\mathrm{mm}$ 宽的线，以将其划分为左右两个部分。右边用DI水润湿。  \n\nb.样板的涂装施工参数应维持不变，因为它们都可能对入槽痕迹有影响。然后变动其中的一个（如涂装电压、人槽角度、人槽速度)。样板上作了标记的一边是实验考察区，它必须正对电极。  \n\n<html><body><table><tr><td>槽液温度</td><td>标准</td><td>阳极/阴极距离/cm 10</td></tr><tr><td>涂装电压/V</td><td>40</td><td>涂装前样板底部距槽液表面的距离/cm 1</td></tr><tr><td>附加电阻/Q</td><td>0</td><td>带电人槽深度/cm 15</td></tr><tr><td>涂装时间/min</td><td>2</td><td>人槽角度/(*)</td></tr><tr><td>搅拌速度/（r/min）</td><td>500</td><td>90 人槽速度/(cm/s)</td></tr><tr><td>阳极/阴极比</td><td>1/4</td><td>1</td></tr></table></body></html>  \n\n$\\textcircled{6}$ 评价除了施工条件外，槽液的状态（固含，灰分，溶剂含量，pH值以及电导率）也对其有很大影响。样板上干湿两个区的状态分别用 $0\\sim5$ 级的评级标准来予以评价。  \n\n0级：无可见痕迹. 3级；平坦的塑性痕迹。  \n\n1级：仅仅轻微变化（光泽，色相）。 4级：严重的塑性痕迹（条痕），  \n\n2级：明显的可见痕迹。 5级：严重的塑性痕迹（击穿），  \n\n因CED材料的敏感性不同（对电压和预处理的敏感性)，在带电入槽时其漆膜厚度可能有改变。  \n\na.干、湿两区的漆膜厚度不同  \nb.样板底部和上部厚度不同。  \n如果存在这些现象，则可从表3-2-51中看到。  \n\n表3-2-51某厂实用中的CED带电入槽时膜厚差异 单位：μm  \n\n\n<html><body><table><tr><td>干边</td><td>DI水润湿边</td><td>干边</td><td>DI水润湿边</td></tr><tr><td>26</td><td>20</td><td>23</td><td>18</td></tr><tr><td>25</td><td>19</td><td>22</td><td>18</td></tr><tr><td>24</td><td>19</td><td></td><td></td></tr></table></body></html>  \n\n(8）CED涂料MEQ值的测定MEQ值是对于涂料固含量为 $100\\mathbf{g}$ 所需中和剂的量(mmol)，单位为 $\\mathrm{mmol}/100g$ 。换言之，为使成膜物质具有水稀释性所需要的中和剂的量。显然，它与直接反映游离氢离子浓度的 $\\mathsf{p H}$ 有所不同，但又存在一定关联。它是电泳槽日常运行中重要的控制参数。然而人们在使用CED的实践中发现；CED材料中酸和碱都是存在的。为了更好地监控树脂生产以及槽液日常运作时有关参数的改变，简单地以MEQ来度量所需中和剂的量并不全面。于是有人提出了MEQA和MEQB的概念，以此分别表述材料中酸和碱的存在，并且提出了总中和度（TN）的定义。  \n\n$$\n\\mathrm{TN}(\\%){=}\\frac{\\mathrm{ME}\\mathbf{Q}_{\\mathrm{A}}}{\\mathrm{MEQ}_{\\mathrm{B}}}\\times100\\%\n$$  \n\n(9)MEQA的测定  \n\n$\\Phi$ 概念此法用来测定CED材料中的总酸含量。  \n\n$\\textcircled{2}$ 方法综述精称样品于一个干净的小烧杯中，加入四氢呋喃、丙二醇（容积比$80:20:$ ）的混合溶液溶解，然后进行电位滴定。终点用于计算样品的总酸含量。  \n\n$\\textcircled{3}$ 仪器电位滴定仪；分析天平（精确到小数点后四位)； $150\\mathrm{mL}$ 烧杯；电磁搅拌器；0.1mol/LKOH-甲醇溶液；四氢呋喃；丙二醇；一次性塑料注射器（5mL)。  \n\n$\\textcircled{4}$ 操作过程  \n\na.将样品吸入5mL的塑料指示器中，擦拭干净、称重、记录；  \n\nb.注射 $_{2\\tt g}$ 样品于 $150\\mathrm{mL}$ 烧杯中；  \n\nc.注射器称重、记录（注意：称重前不得擦拭注射器，以免影响计量）；  \n\nd.加人 $70\\mathrm{mL}$ 混合溶液（四氢呋哺、丙二醇）于装有样品的烧杯中；  \n\ne.放入磁力搅拌棒，并将烧杯置于磁力搅拌器托盘上，揽拌至样品溶解；  \n\nf.提高搅拌器转速，直至产生漩涡；  \n\ng.靠烧杯壁插入电极（注意：不得贴靠烧杯）；  \n\nh.将滴定管置于烧杯的漩涡上方，用0.1mol/L的KOH-甲醇溶液滴定至终点（电位滴定曲线出现峰值）；  \n\ni.采用 $70\\mathrm{mL}$ 混合溶液（四氢呋喃、丙二醇）进行空白实验；  \n\nj.注意空白实验溶液样品应及时更新；  \n\nk.记录两次滴定容积；  \n\n1.取重复实验数据的平均值。  \n\n③计算按式（3-2-8）计算每克不挥发实验样品酸量。  \n\n$$\n\\mathbf{MEQ}_{\\Lambda}={\\frac{(V_{1}-V_{2})N_{1}}{(W_{1}-W_{2})N V}}\n$$  \n\n式中 $\\boldsymbol{V}_{1}$ —样品滴定至终点的体积，mL；$\\boldsymbol{V_{2}}$ ———空白样品滴定至终点的体积，mL；$N_{1}$ —滴定液的物质的量的浓度；$\\pmb{W}_{1}$ —注入样品前注射器的质量；$\\boldsymbol{W}_{2}$ —注入样品后注射器的质量；NV—实验样品的不挥发分，精确至小数点后2位数。注意事项：为尽可能减少因溶剂挥发而带来的误差，整个操作应尽快进行。  \n\n(10）MEQB的测定  \n\n$\\Phi$ 概念此法用来测定CED材料中的总碱的含量。  \n\n$\\textcircled{2}$ 方法综述精称样品于一干净的小烧杯中，加人四氢呋哺、丙二醇（容积比 $80:20.$ 的混合溶液溶解，然后进行电位滴定。终点用于计算样品的总碱含量。  \n\n$\\textcircled{3}$ 仪器电位滴定仪；分析天平（精确到小数点后四位）； $150\\mathrm{mL}$ 烧杯；电磁搅拌器；1mol/LHC1液；四氢呋喃；丙二醇；一次性塑料注射器（5mL）。  \n\n$\\textcircled{4}$ 操作过程  \n\na.将样品吸人 $\\scriptstyle5\\mathrm{mL}$ 的塑料指示器中，擦拭干净、称重、记录；  \n\nb.注射 $_{2g}$ 样品于 $150\\mathrm{mL}$ 烧杯中；  \n\nc.注射器称重、记录（注意：称重前不得擦拭注射器，以免影响计量）；  \n\nd.加人 $70\\mathrm{mL}$ 混合溶液（四氢呋喃、丙二醇）于装有样品的烧杯中；  \n\ne.放入磁力搅拌棒，并将烧杯置于磁力搅拌器托盘上，搅拌至样品溶解；  \n\nf.提高揽拌器转速，直至产生激涡；  \n\ng.靠烧杯壁插人电极（注意：不得贴靠烧杯)；  \n\nh.将滴定管置于烧杯的漩涡上方，用0.1mol/L的盐酸溶液滴定至终点（电位滴定曲线出现“S”形)；  \n\ni.采用 $70\\mathrm{mL}$ 混合溶液（四氢呋哺、丙二醇）进行空白实验（注意：空白实验溶液样品应及时更新)；  \n\nj.记录两次滴定容积；  \n\nk.取重复实验数据的平均值。  \n\n$\\textcircled{5}$ 计算按式（3-2-9）计算每克不挥发实验样品碱量。  \n\n$$\n\\mathbf{MEQ}_{\\mathrm{B}}={\\frac{(V_{1}-V_{2})N_{1}}{(W_{1}-W_{2})N V}}\n$$  \n\n式中 $\\boldsymbol{V}_{1}$ —样品滴定至终点的体积，mL；$\\boldsymbol{V}_{2}$ ——空白样品滴定至终点的体积，mL；$N_{1}$ —滴定液的物质的量的浓度；$\\boldsymbol{w}_{1}$ —注入样品前注射器的质量；$\\boldsymbol{W}_{2}$ ——注入样品后注射器的质量；NV-一实验样品的不挥发分，精确至小数点后2位数。  \n\n注意事项：为尽可能减少因溶剂挥发而带来的误差，整个操作应尽快进行，",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1108,
+        "chunk": "# 二、涂层性能检验  \n\n涂料经成膜后，其涂层的性能比该产品的原漆性能更加直观、更加实际地反映涂料的内  \n\n在质量，所以一直受到涂料生产厂家和客户（这里就是汽车厂）的一贯重视。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1109,
+        "chunk": "# 1.硬度  \n\n涂层的硬度是表征涂层机械强度的重要性能之一。其物理意义可以理解为漆膜表面对于作用其上的另外一个硬度较大的物体所表现出来的阻力。这个阻力可以通过一定重量的负荷，作用在比较小的接触面积上，测定漆膜抵抗变形的能力而表现出来。涂层硬度测定的方法很多，有摆杆式硬度、铅笔硬度、斯瓦特硬度（Sward）及压痕硬度等，其中以摆杆式硬度和铅笔硬度用得最多。  \n\n(1）摆杆式硬度测定法摆杆式硬度又可分为单摆式和双摆式两种，前者的测量值以时间（s）表示，后者则以相对于玻璃硬度的百分数表示。  \n\n单摆式又称为科尼格（Konig）和柏萨兹（Persoz）摆杆硬度。国外一些大型汽车涂料制造厂大都采用这两种硬度测试仪，其汽车涂料特别是面漆的硬度指标多以这两种硬度表示，如巴斯夫公司、斯托拉克公司、阿克苏公司等。几种摆杆阻尼试验的工作原理基本相同，即接触涂层表面的摆杆以一定的周期摆动时，摆杆摆幅衰的快慢来衡量硬度的高低。由于各种摆杆的结构、重量、尺寸、摆的周期及摆幅都不一样，另外摆杆与涂层之间的相互作用还取决于涂层自身的弹性和黏弹性，由此各种摆的测定结果无法建立相互之间的换算关系，因而在产品标准中列出涂层的摆杆硬度值时，必须同时指明所采用的摆杆仪的类型，如科尼格硬度一般情况下为柏萨兹硬度值的一半。  \n\n(2）Sward硬度计Sward硬度计由两个直径为 $100\\mathrm{mm}$ 的金属圆环组成，两环的间距为 $25\\mathrm{mm}$ 。在圆环的下半部有两个玻璃指示泡，用以表示试验开始或终了。测量时，让它在待测漆膜表面来回摆动，记录摆动的次数，且与玻璃值比较。计算比值即为Sward硬度值。本法现在无论国内外均已不太常用，很少见到某个产品的硬度值是以Sward硬度来表示的。  \n\n(3）铅笔硬度用一套铅笔来进行漆膜硬度的测定，其判定方法是以铅笔能够穿透漆膜而深达基材的铅笔的号数来表示。国内所用铅笔一般为中华牌高级绘图铅笔。为了避免人为因素的影响，国外推出了专用于铅笔硬度测定的铅笔硬度试验机。Erichsen公司型号为Model291。测定时只要用手把仪器轻轻向前推动即可。显然它可以在相当大的程度上减少人为因素的影响，所得检测数据的重复稳定性相对稳定。  \n\n铅笔硬度在汽车涂料领域内颇为流行，尤其是汽车用阴极电泳底漆及中间涂层等不少产品都是以铅笔硬度表示。这里需要特别指出的是，国产铅笔所测定的硬度值比国外铅笔所测定的硬度值要低 $_{1\\sim2}$ 级。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1110,
+        "chunk": "# 2.柔韧性  \n\n漆膜的柔韧性指标过去大都是将涂有漆膜的马口铁板在不同直径的轴棒上弯曲，以其弯曲后漆膜不被破坏的最小轴棒直径来表示。这种柔韧性试验器由精细度不同的6个钢制的棒轴组成，其尺寸分别是截面 $\\mathrm{1mm}\\times10\\mathrm{mm}$ ， $2\\mathrm{mm}\\times10\\mathrm{mm}$ ， $\\mathrm{3mm\\times10mm}$ $4\\mathrm{mm}\\times10\\mathrm{mm}$ $5\\mathrm{mm}\\times10\\mathrm{mm}$ 及直径 $10\\mathrm{mm}$ 、外径 $15\\mathrm{mm}$ 的套管。  \n\n圆柱形轴弯曲试验仪主要用于测定金属表面漆膜的抗开裂和抗剥离性能。一般厂家提供12个不同直径的圆柱形轴，其尺寸为 $2\\mathrm{mm}$ ， $3\\mathrm{mm}$ 、4mm、 $\\mathsf{5m m}$ ， $6\\mathrm{{mm}}$ ， $8\\mathrm{mm}$ ， $10\\mathrm{mm}$ .$12\\mathrm{mm}$ 。 $16\\mathrm{mm}$ $20\\mathrm{mm}$ 。 $25\\mathrm{mm}$ ， $32\\mathrm{mm}$ 。试验时将已涂漆的样板绕在圆柱形轴上，依次换成直径较小的圆柱形轴，直到漆膜发生开裂时为止。  \n\n锥形轴弯曲试验仪用于测定金属表面漆膜的拉伸性能。测定时将已涂漆的样板夹在仪器的适当位置，通过轧辊的旋转作用使样板绕在锥形轴上。锥形轴的长度为 $200\\mathrm{mm}$ ，大端直径为 $37\\mathrm{mm}$ ，小端直径为 $3\\mathrm{mm}$ 。弯曲后检查样板，找出因拉伸而造成漆膜损坏的最小直径的部位，该部位距小端的长度定义为锥形弯曲值，单位为mm。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1111,
+        "chunk": "# 3.冲击性  \n\n冲击性能反映涂层抗高速度负荷作用下变形的能力。表现了试验漆膜的弹性和附着力。所用仪器为冲击试验器。  \n\n以往国家标准的冲击试验器的重锤为 $1\\mathbf{k}\\mathbf{g}$ 。当时试验用基材均为马口铁板。但使用马口铁板不适用于汽车以及其他工业，故很多工业用漆的标准中都规定采用厚度为 $0.45\\sim1\\mathrm{mm}$ 的薄钢板。因此对冲击试验的重锤的重量又有了新的规定，如国外的落体冲击试验仪的重锤为 $2.7\\mathrm{kg}$ ，管式冲击试验仪的重锤的标准重量虽然还是 $1\\mathbf{k}\\mathbf{g}$ ，但是厂家备有加重重锤，重量也是 $1\\mathbf{k}_{B}$ ，这样两个重锤加起来就变成了 $2\\mathbf{k}\\mathbf{g}$ ，而落锤高度也由原来的 $50\\mathrm{cm}$ 增加到 $100\\mathrm{cm}$ 费",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1112,
+        "chunk": "# 4.附着力  \n\n漆膜与基材表面之间通过物理或化学力的作用结合在一起的能力称为附着力。要想真正测定漆膜与基材之间的附着力是比较困难的，目前只能采用一些间接的方法来测量。但是应该明白，这些数值并不单单是附着力的体现，也是某些其他综合性能的集中反映，如冲击性、柔韧性及压痕硬度等。测定附着力的方法有以下几种：划圈法、划格法以及拉开法等。  \n\n划格法评价的标准国内外大同小异，都将其分为6级。我国标准将其定为 $0{\\sim}5$ 级，国外则将其定为Gt0/5b、Gtl4b、Gt2/3b、Gt3/2b、Gt4/1b及Gt5/0b级。  \n\n值得注意的是，国外汽车行业早已不再采用划圈法测定附着力，从目前所见到的原厂漆的标准来看，大多数为划格法附着力的数据。  \n\n上述两种附着力的测定方法都存在一定的缺陷，影响因素很多，实际上它们并不能真正反映出涂层与基材之间黏合力的大小。于是，近年来某些工业领域仿照胶黏剂行业测定黏结强度的方法，发展了一种拉开法来测定涂层的附着力。所谓拉开法是指在规定的速度下，在试样的黏结面上施加垂直、均匀的拉力，以测定涂层之间或者是涂层与基材之间附着被破坏时所需要的外力，单位为千克力/厘米 $\\mathrm{(kgf/cm^{2}}$ ， $1\\mathrm{kg}\\mathrm{f}{=}9.8\\mathrm{N})$ 。这种测试方法在汽车行业倒是很少采用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1113,
+        "chunk": "# 5.光泽  \n\n所谓光泽，就是涂层表面把投射到它上面的光线朝同一方向反向出去的能力。也就是说，反射的光量越大，光泽就越高。很明显，漆膜表面的光泽对于汽车涂料之类对装饰性要求较高的涂层来讲，无疑是一项非常重要的指标。  \n\n测定光泽的基本原理是以一块高光泽的标准板为基准，并把它定为 $100\\%$ 。早期光泽测定试验方法采用单一的、固定的入射角。实际应用中发现这远远不能满足各种不同装饰效果、不同光泽范围测定的要求，为此国外早就采用了多变角光泽计来进行测定，并且为之制定了相应的标准。我国也于1988年制定了 $20^{\\circ}$ ， ${60}^{\\circ}$ 。 $85^{\\circ}$ 镜面光泽测定的标准。一般 $20^{\\circ}$ 对于高光泽色漆涂层具有很高的分辨率，它适合于 ${60}^{\\circ}$ 光泽测定时高于70单位的涂层。而 $85^{\\circ}$ 则对于低光泽涂层具有很高的分辨率，它适合于 ${60}^{\\circ}$ 光泽测定时低于30单位的涂层。测定时务必根据所测对象的具体情况确定适当的入射角。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1114,
+        "chunk": "# 6.杯突试验  \n\n冲击性试验数据显示的是涂层在经受高速度负荷作用下抵抗破坏的能力，而杯突试验则反映的是涂层经受低速度负荷作用下抵抗破坏的能力。该项试验指标在近年来工业涂料的标准中常常可以找到。可以说它是涂层的柔韧性、拉伸强度以及附着力等项性能指标的综合体现。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1115,
+        "chunk": "# 7.抗石击试验  \n\n抗石击性能是汽车漆关键指标之一，此项性能指标与漆膜其他项目有所不同，它往往按照各汽车总装厂自定标准进行检验。著名涂料仪器生产厂家Erichsen就分别为不同汽车总装厂生产其专用抗石击性能检测仪，如 Erichsen ATO/11-1/S、Erichsen Steinschlayprufgerat 508 为奔驰汽车公司专用，ErichsenD5870则为通用汽车公司专用。BASF自制抗石击试验仪则为大众专门设计等。不仅仅检测仪器，连试验用来冲击漆膜表面的介质也各有不同。上述各类抗石击检测仪器的检测数据间尚无准确的互换性，有待今后业内同人去规范这些标准，以求统一。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1116,
+        "chunk": "# 8.耐介质性  \n\n耐介质性包括耐水性、耐酸性、耐碱性、耐各种有机溶剂性以及盐雾、湿热等。对于汽车漆而言，这些项目的试验方法非常复杂。各汽车生产厂家往往都制定有自己专用的试验标准，比如有关盐雾、湿热交互实施的所谓VDA循环就可算一例。德国大众、奔驰、法国PSA集团、美国通用、福特等公司都有各自的试验标准。我国各大汽车公司由于均已选择了国外的合作伙伴，因此其检测标准往往也是参照某家外国公司。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1117,
+        "chunk": "# 9.耐候性  \n\n在影响汽车使用寿命的各项指标、性能中，最为重要的莫过于耐候性了。评价耐候性的试验方法主要有以下三种。  \n\n$\\Phi$ 在太阳光较强的地区建立曝晒站，进行直接曝晒试验。  \n$\\textcircled{2}$ 太阳跟踪聚焦曝晒试验。  \n$\\textcircled{3}$ 人工加速老化试验。  \n\n第一种试验方法是将试样直接放置在一年之中气象环境变化较小的乡间大气中，试验条件简单，试验结果的再现性良好。世界上比较有名的曝晒站有美国南佛罗里达州、日本广岛、我国的海南岛等。由于世界各地地理环境、气候条件的差别，各个曝晒站的试验结果不存在较为科学的相关性能，彼此之间也无线性关系，但是这些并不妨碍大多数专家都承认的多年来通过大量数据所总结出来的一些模糊结论。在这些曝晒站曝晒一年，如果是本色漆，则相当于实际使用三年；如果是金属闪光漆，则相当于一年半等。  \n\n为了加快试验速度，也可以采用太阳跟踪聚焦曝晒试验法。其试验速度比户外简单地曝晒试验要快6倍左右，但是其试验设备显然要复杂得多。  \n\n人工加速老化试验是通过采用不同的光源、不同的照射时间、不同的温度、不同的喷淋时间确定一个循环周期条件，以此使样板在较短的时间内达到天然条件下较长的时间才能达到的老化的结果。目前世界上流行的人工加速老化仪主要采用下述光源：阳光碳弧灯、氙光灯和紫外荧光灯。这三种光源中，目前以紫外荧光灯型在汽车行业中用得较多。最为流行的这种类型的仪器国外叫做QUV加速人工老化仪。  \n\n多年来，涂料工作者总是企图寻找加速人工老化和天然曝晒数据之间的线性关系，但是由于影响试验结果的因素太多，两者之间的线性关系的再现性均不理想。于是人们只好暂借用类似模糊数学的概念，就像上面提到的那样，用所谓某种类型的仪器中多少时间大致相当于某地多少年来描述。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1118,
+        "chunk": "# 三、漆膜缺陷、起因及解决措施  \n\n汽车原厂漆和修补漆的施工方式原则上可以说都是喷涂，不是采用压缩空气雾化就是高速旋杯雾化喷涂，或者高压无气喷涂等。这几种喷涂施工方式的整个过程中，必须考虑很多因素，比如稀释剂的沸程范围，稀释剂中所含高沸点溶剂与树脂的混容性，树脂溶液在凝聚、流展、溶剂挥发过程中表面张力的变化以及它们对涂层的流挂性、流平性、脱泡性的影响等。如有任何一个环节配置不当，就将无法得到理想的涂装效果。  \n\n以下所涉及的内容仅仅包括汽车漆经过涂装成膜以后所产生的缺陷，不包括原漆的质量问题。有关原漆的质量问题请参阅本节一和二部分。为了直观、明了地将各种漆膜缺陷进行分类，现按主要原因、预防措施及解决办法三个方面分别予以解释。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1119,
+        "chunk": "# 1.面漆  \n\n（1）浮色、发花这里所说的浮色、发花是指面漆表面的颜色不均匀，并不是指原漆的浮色、发花。当然原漆如果存在浮色、发花的质量问题，那么肯定会对漆膜表面颜色不均匀带来严重影响。除了原漆方面的原因外，以下问题处理不当也有可能造成面漆的浮色、发花现象。  \n\n$\\textcircled{1}$ 主要原因a.面漆涂层太厚；  \n\nb.原漆存在浮色、发花的病；  \n\nc.喷涂压力太高或太低；  \n\nd.稀释剂使用不当。  \n\n$\\textcircled{2}$ 预防措施为了避免上述缺陷，最好的办法是严格按照涂料制造厂的使用说明书的要求施工。采用高速旋杯进行喷涂施工时，严格保持工艺参数稳定。  \n\n$\\textcircled{3}$ 解决办法如果已经出现了上述缺陷，则只好用细砂纸打磨后再重新进行一次面漆的喷涂施工，或进行线上修补。  \n\n(2）轻微收缩、起皱面漆表面不均匀，呈现出轻微的纹理。即使纹理不明显，光泽也差。  \n\n$\\textcircled{1}$ 主要原因  \n\na.喷涂面漆前，底漆或者是中间涂层未干透，干燥时间太短，或漆膜太厚；  \n\nb.底漆或腻子中固化剂选用不当，底漆或腻子固化不完全；  \n\nc.面漆喷得太薄，对底层未能很好地覆盖；  \n\nd.喷涂面漆时（尤其是喷涂挥发型面漆时)，一道喷得太厚，当面漆实于后，涂层的内部还封闭了许多未能挥发的溶剂，随着时间的推移，内层溶剂还会继续挥发，并向面漆涂层迁移渗透。这样一来轻者导致面漆失光，重者引起面漆涂层收缩，进而产生纹理。  \n\n$\\textcircled{2}$ 预防措施为了避免上述现象的发生，必须按照涂料制造厂推荐的每道扫枪涂层的厚度来进行喷涂。每道涂层之间都要严格按照产品说明书的要求给予足够的闪蒸时间。  \n\n定期校正喷涂设备的工艺参数。  \n\n$\\textcircled{3}$ 解决办法了解待修补车辆车身上的涂层喷涂施工的时间。如果时间不长，则可以放置一段时间，使所有的涂层完全干燥。如果时间不允许而修配厂又具备条件的话，可以采取进烘房或者用红外灯进行低温烘烤的办法来解决。然后再用一定规格的砂纸打磨平整，重新喷涂面漆。  \n\n进行线上修补。  \n\n(3）起泡起泡的原因是多方面的。起泡往往以不同的形状、不同的区域、不同的大小及密度等形式出现，既可以在涂层与涂层之间，也可以在整个涂层内。一般来说，在喷漆间空气的相对湿度较低或气候较为干燥的条件下，涂层起泡的病相对较少一些。换句话说，施工环境相对湿度的大小是引起涂层起泡的主要原因之一。如果采用的是双组分聚氨酯系涂料的话，湿度的影响还可能要更大一些。  \n\n$\\textcircled{1}$ 主要原因  \n\na.采用交联型面漆时，烘烤温度偏高。  \n\nb.如果所采用的是水性底色漆或腻子，其中所含的水分未挥发完全，而面漆又采用的是双组分聚氨酯型涂料。  \n\nc.待涂装的表面未经认真地清洗。湿打磨时采用了不干净的水，或者是手上的汗导致水溶性盐的污染。工件长时间工作在潮湿的环境下，就有可能发生起泡现象。  \n\nd.由于外部原因造成部分损坏，其保护作用被破坏，这样空气中的潮气很容易通过受损坏部位渗透进人涂层，从而使受损涂层的周边区域特别容易发生起泡现象。  \n\n$\\textcircled{2}$ 预防措施  \n\na.待喷涂表面在进行最后的清洗时，应该采用干净的水或者喷热水进行清洗，或者使用除硅油清洗溶剂进行清洗。  \n\nb.要给底漆、中间涂层、腻子特别是水性材料留有足够的干燥时间，喷涂面漆要保证足够的厚度。  \n\nc.对于原子灰及聚氨酯系中间涂层等要采用干打磨的办法。  \n\n$\\textcircled{3}$ 解决办法如果发生了上述现象，只能按照修补的整套工艺过程重新进行修补，即除去受损坏部位所有的涂层，包括底漆在内。然后再按照下述程序进行：  \n\na.清洗；  \nb.表面处理；  \nc.底漆、中间涂料涂装；  \nd.面漆涂装等。  \n\n(4）遮盖力差透过面漆可以看到旧的涂层或者经过表面处理的基材表面、底漆、底色等，或者颜色不均匀。  \n\n$\\Phi$ 主要原因  \n\na.在修补范围内面漆的颜色不均匀；  \n\nb.面漆在使用前未经充分混合；  \n\nc.稀释剂使用不当；  \n\nd.面漆太薄。  \n\n$\\textcircled{2}$ 预防措施  \n\na.经过表面处理、喷涂底漆、中间涂层后，应使其表面呈现同一颜色。  \n\nb.在喷涂面漆前，必须经过充分地揽拌、混合。  \n\nc.应该严格按照产品说明书的要求选择稀释剂。  \n\nd.应该保证一定厚度的面漆。一般对于本色漆应该达到 $50\\sim70\\mu\\mathrm{m}$ ，双层金属闪光漆的底色漆应该达到 $12\\sim15\\mu\\mathrm{m}$ 。对于某些遮盖力差的面漆，建议在喷涂面漆之前先喷涂所谓“标志涂料”，或者采用颜色相近的中间涂料。  \n\n$\\textcircled{3}$ 解决办法在面漆充分干燥后，先用No.800砂纸进行湿打磨，再重新喷涂面漆。  \n\n(5）渗色渗色现象多以黄色或红色色相的形式出现在涂层中。多发生在汽车修补施工 时，原厂漆则较少见到。  \n\n$\\Phi$ 主要原因  \n\na.旧涂层中使用的某些颜料耐溶剂性能欠佳，被修补涂料中的溶剂所溶解，致使面漆褪色。  \n\nb.腻子中含有某些过量的有机过氧化物被修补材料中的溶剂所溶解、渗透，然后与涂层中的某些颜料反应。在这些刮涂腻子的部位发生向黄褐色转变的现象。在蓝色或绿色色调的面漆上特别容易发生。  \n\nc.中间涂层或腻子上残留有沥青或焦油等残留物。  \n\n$\\textcircled{2}$ 预防措施  \n\na.如果在长期的修补施工中发现某些车辆的涂层特别容易出现渗色现象，则应该在喷涂面漆之前，预先喷涂一层隔离层——中间涂层。  \n\nb.调制腻子时，务必注意按照说明书的配方比例加人有机过氧化物。切不可错误地以为有机过氧化物加得越多越好，实际上恰恰是适得其反。  \n\n$\\textcircled{3}$ 解决办法如果渗色严重，应该将全部涂层打磨掉，然后重新进行修补施工。  \n\n(6）工业污染面漆受到工业废气、汽油、某些化学品等有害物质的污染，会使面漆表面失光、变色，严重时甚至出现黑褐色斑点。汽车特别是高级轿车表面发生这种现象，问题就很严重了。  \n\n$\\Phi$ 主要原因  \n\na.面漆如果受到焦油的污染，涂层中部分成膜物质向表面迁移，形成黑褐色斑点。  \n\nb.工业废气、化学品或焦油渗透入面漆，使面漆褪色，这是由于涂层中颜料发生化学反应造成的。  \n\nc.有些有害物质，如鸟粪、汽油、某些树脂等，长期覆盖在面漆表面，严重侵蚀表面，并导致面漆表面进一步分解。  \n\n$\\textcircled{2}$ 预防措施为了避免工业污染，车辆应该经常清洗。最好在每次清洗后采用抛光蜡进行小心地抛光。实际上抛光蜡更为重要的是对于涂层的防护作用。  \n\n$\\textcircled{3}$ 解决方法轻微的褐色可以通过抛光来消除。如果无法清除，就需要进行彻底地打磨、砂光，再重新喷涂面漆。  \n\n（7）附着力不良附着力不良存在着两种情况：一是底漆对基材的附着问题；二是涂层与涂层之间的附着问题，涂料业界将后者称之为层间附着力。  \n\n$\\Phi$ 主要原因  \n\na.表面未清理干净，尚存在一些有碍附着的物质，如硅油、油脂、脂肪、蜡、铁锈以及抛光膏的残留物等。  \n\nb.底漆不合适。  \n\nc.基材打磨不充分或者根本未进行打磨。  \n\nd.喷涂底漆或面漆时采用了干喷的喷涂手法，或者是喷得太薄。  \n\ne.在喷涂金属闪光色漆时，层与层之间闪蒸时间太短，或者底色漆稀释不够。  \n\nf.底色漆或中间涂料中不恰当地使用了一些硅系列流平剂。  \n\n$\\textcircled{2}$ 预防措施a.认真清理表面。  \n\nb.正确选用底漆，尤其是在一些难粘表面上，如铝材之类轻合金、聚烯烃之类的工程塑料等。  \n\nc.严格按照涂料制造厂的要求进行施工，在喷涂时形成干喷。喷涂厚涂层时，一定要留出足够的闪蒸时间。  \n\nd.提请制漆厂注意流平剂的选用。  \n\n$\\textcircled{3}$ 解决办法打磨附着力不良的部位，重新进行修补施工。  \n\n(8）气泡面漆上的气泡形如麻点，中间有小孔，凸出于涂层的表面。  \n\n$\\Phi$ 主要原因  \n\na.面漆喷得太厚或者施工黏度偏高。  \n\nb.稀释剂使用不当，挥发速率太快。  \n\nc.层间的闪蒸时间太短。  \n\nd.工件温度太高，造成溶剂挥发速率太快。  \n\ne.双组分面漆烘烤前，闪蒸时间太长。  \n\nf.有时采用红外灯烘烤干燥时，红外灯距离基材太近，致使基材温度过高。  \n\n$\\textcircled{2}$ 预防措施  \n\na.采用与环境温度相适应的稀释剂。  \n\nb.严格控制面漆的膜厚，尤其是一次成膜厚度。  \n\nc.严格控制基材与红外灯的距离，保持正确的挥发时间与干燥温度。  \n\n$\\textcircled{3}$ 解决办法如果气泡面积不太，可以采用 $200^{\\sharp}$ 水砂纸打磨，然后再用抛光膏进行抛光。如果发生气泡的表面积较大，必须将其整个打磨平整，直到基材，再重新进行修补施工。  \n\n（9）鱼眼鱼眼又名凹陷，它一般呈现出圆形的凹痕，且其边缘凸起。底漆、中间涂层以及面漆表面都有可能发生。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1120,
+        "chunk": "# $\\textcircled{1}$ 主要原因  \n\na.基材表面未能彻底清理干净，尚留存有微量杂质，如硅油、油脂、蜡以及抛光膏等。  \n\nb.喷漆间空气过滤不良，由于不可预计的因素带来污染，例如混人了其他类型的漆雾或其他挥发性物质。  \n\nc.压缩空气的清洁器失效，未及时放水或混入了油污、水等污染物。  \n\nd.附近工厂的污染源。  \n\n$\\textcircled{2}$ 预防措施  \n\na.对表面进行彻底清洗，必要时采用除硅油专用清洗剂，如巴斯夫公司鹦鹉牌541-5硅油清洗剂。  \n\nb.如果在表面处理的过程中必须采用一些含硅油的产品（抛光膏），则更需要采用上述硅油清洗剂进行清洗。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1121,
+        "chunk": "# $\\textcircled{3}$ 解决办法  \n\na.如果一且发生鱼眼，而且十分严重，可采用No.1200或No.1500砂纸进行湿打磨，再采用抛光膏抛光。  \n\nb.如果经过抛光仍然无法除去鱼眼，则采用No.800砂纸彻底砂平，再重新进行修补施工。  \n\n(10）流挂流挂现象是小的液滴、小的连珠甚至是一些较大团的涂料沿着垂直的喷漆表面流淌而下形成的漆膜病。  \n\n$\\Phi$ 主要原因  \n\na.喷枪的喷嘴选择不当，太大了；  \n\nb.喷枪离工件太近或喷枪移动的速度太慢；  \n\nc.涂层喷得太厚或太湿；  \n\nd.每道枪之间的闪蒸时间太短；  \n\nc.稀释剂选配不当，挥发速率太慢。  \n\n$\\textcircled{2}$ 预防措施  \n\na.应该严格遵守涂料制造厂的建议；  \n\nb.选用合适喷枪的喷嘴；  \n\nc.选用与环境温度相适应的稀释剂；  \n\nd.调整走枪速度、喷枪与工件的距离等；  \n\ne.在进行斑点之类的局部修补时，应该采用快速稀释剂、较小的喷嘴。  \n\n$\\textcircled{3}$ 解决办法如果出现流挂的面积较小，可待涂层完全固化后，用 $\\mathrm{P1000}{\\sim}1200$ 号水砂纸将缺陷部位轻轻打磨掉，然后再用高光泽抛光蜡进行抛光。如果流挂的面积较大，则必须将其全部打磨平整，然后重新喷涂面漆。  \n\n(11）橘纹涂层表面不均匀，存在程度不一的纹理，看起来很像橘子皮。  \n\n$\\Phi$ 主要原因  \n\na.喷涂时喷枪与工件的距离太远；  \n\nb.压缩空气压力太低，涂料雾化不好；  \n\nc.喷涂的涂层太薄；  \n\nd.不恰当地采用了干喷技术或供漆量太少；  \n\ne.施工黏度太高；  \n\nf.稀释剂选用不当，挥发速率太快。  \n\n$\\textcircled{2}$ 预防措施  \n\na.应该严格按照产品说明书的要求；  \n\nb.调整施工参数；  \n\nc.选择合适的稀释剂。  \n\n$\\textcircled{3}$ 解决办法如果橘纹轻微，则可以采用P1200号水砂纸打磨，然后用高光泽抛光蜡抛光。如果橘纹严重，则应该采用P800号水砂纸打磨，然后再重新喷涂面漆。  \n\n(12）咬底咬底一般发生在新喷面漆涂层与旧涂层之间的驳口处或填补过原子灰的中间涂层上面。  \n\n$\\textcircled{1}$ 主要原因  \n\na.对旧涂层打磨不充分就喷涂新面漆；  \n\nb.底漆或腻子太厚或未干透；  \n\nc.底漆、中间涂料、面漆之间不配套。  \n\n$\\textcircled{2}$ 预防措施  \n\na.底漆和腻子的施工应该严格按照厂商的要求进行，确保底层干透；  \n\nb.必要时在面漆与底漆、腻子或中间涂层之间薄薄地喷涂一道封闭底漆。  \n\n$\\textcircled{3}$ 解决办法打磨平整，然后重新喷涂面漆。  \n\n(13）龟裂涂层表面存在的起皱向不同方向延展的不同长度、不同宽度的裂纹。  \n\n$\\textcircled{1}$ 主要原因a.涂层太厚；  \n\nb.在旧涂层上喷涂面漆时，旧涂层上已有裂纹，没有很好地进行打磨、填平等前处理；c.底漆、中间涂层或面漆之间刚柔性不相匹配，在冷热交变的条件下，因收缩、膨胀而导致开裂。  \n\n$\\textcircled{2}$ 预防措施a.认真挑选涂装体系；  \n\nb.严格按照产品制造商的要求进行施工。  \n\n$\\textcircled{3}$ 解决办法将裂纹彻底打磨平整，然后重新喷涂底漆和面漆。  \n\n(14）起皱如果第二道面漆比第一道面漆干燥得快些，则极有可能在表面形成无规则的凹痕和凸起。这种类型的漆膜病特别容易发生在热塑性合成树脂涂料的施工中。  \n\n$\\Phi$ 主要原因  \n\na.喷涂热塑性涂料时涂层太厚；  \n\nb.施工环境欠佳，如室温太高，湿度太大。  \n\n$\\textcircled{2}$ 预防措施  \n\na.严格遵照产品制造厂商的技术要求进行施工；  \n\nb.最好配置能够控制温度、湿度的喷漆间。  \n\n$\\textcircled{3}$ 解决办法  \n\na.如果起皱不太明显，则待面漆干燥彻底后再打磨平整、抛光；  \n\nb.如果起皱太明显，则必须采用脱漆剂或刮刀将涂层全部清理干净，再重新进行修补施工。  \n\n（15）砂痕喷涂面漆之前打磨过程中造成的痕迹。  \n\n$\\Phi$ 主要原因a.打磨底漆或腻子时所采用的砂纸太粗糙；b.底漆未干透，当喷涂面漆时，面漆中的溶剂通过打磨的涂层表面渗透进人下层，当  \n面漆硬干时，打磨的痕迹就显示出来了；c.采用机械打磨时砂轮太粗糙。$\\textcircled{2}$ 预防措施a.严格遵守操作规程，按照要求选定砂纸的规格；b.在打磨腻子或底漆前最好先喷涂一道标志涂料，待涂层干燥后，采用P800号砂纸进  \n行彻底打磨。$\\textcircled{3}$ 解决办法a.如果砂痕不明显，可采用P1200～1500号水砂纸打磨，然后采用高光泽抛光蜡进行抛光；b.如果砂痕非常明显，则需要彻底打磨再重新喷涂面漆。(16）点形状、大小不同的尘埃混入涂层，形成凸起的疵点。$\\Phi$ 主要原因a.打磨后工件未彻底清洗干净；b.车间抹布质量太差，擦拭时棉纤维黏附到工件上；c.压缩空气系统的空气清洁器出现故障，空气过滤不干净；d.喷漆间内形成负压，导致外面的空气进入喷漆间；e.工件未清理干净；f.涂料清洁度不合格。$\\textcircled{2}$ 预防措施a.加强压缩空气的清洁工作；b.选用合格的车间抹布认真进行工件的清理；c.保持喷漆间正压；d.加强对涂料产品质量的控制。$\\textcircled{3}$ 解决办法a.小的灰尘点可用P1200～1500号水砂纸打磨平整，然后再采用高光泽抛光蜡进行抛光；b.如果疵点颗粒较大且数量较多，则必须打磨平整后，再重新喷涂面漆。（17）光泽不良高光泽面漆、特别是清漆干燥后达不到应有的光泽指标，显现出雾光  \n或闷光现象。$\\textcircled{1}$ 主要原因a.稀释剂选用不当（型号错误、误选用了1K系列稀释剂或与环境温度不协调）；b.压缩空气压力过高或过低；c.中间涂料或其他底层未干透；d.稀释剂或压缩空气中水分含量超标；e.喷漆间湿度太高；f.喷漆间风向调整不当，有漆雾落到涂层表面。$\\textcircled{2}$  \n\n预防措施  \n\na.正确选用品种优良的稀释剂；  \n\nb.调整压缩空气压力；  \n\nc.调整喷漆间送风系统；  \n\nd.待底层干透后再喷涂清漆。  \n\n$\\textcircled{3}$ 解决办法  \n\na.待清漆干透后，使用抛光膏进行抛光；  \n\nb.用 $\\mathrm{P1200}{\\sim}1500$ 号水砂纸适度打磨，然后用高光泽抛光蜡进行抛光；  \n\nc.仍然解决不了，则将清漆全部打磨掉，再重新喷涂清漆。  \n\n(18）水痕水痕以环形斑纹出现，大部分是白色斑点或痕迹  \n\n$\\Phi$ 主要原因  \n\na.如果水滴和其他污染物在涂层表面而没有及时清洁，一起干燥，就会产生水痕。一般情况下这些水痕并没有造成涂层破坏，而只是在其边缘形成轻微的凸起。在没有彻底干燥的新喷涂层上最容易产生这一现象。  \n\nb.工件挂具设计不合理，有污染物滴落到工件上。  \n\n$\\textcircled{2}$ 预防措施  \n\na.当重新修补时，要对施工前后的温度及湿度条件控制妥当，避免潮湿空气的影响；  \n\nb.改进工件挂具结构；  \n\nc.一旦在工件上发现水滴，立即采用柔软的黏性抹布将其擦拭干净。  \n\n$\\textcircled{3}$ 解决办法  \n\na.采用 $\\mathrm{P1200}{\\sim}1500$ 号水砂纸打磨，然后用高光泽抛光蜡进行抛光；  \n\nb.如果无法消除水痕，则只能彻底打磨平整，重新喷涂面漆。  \n\n（19）云斑进行大面积金属闪光漆修补施工时出现的漆膜病  \n\n$\\Phi$ 主要原因  \n\na.喷涂金属闪光漆修补时涂层不均匀，喷涂时涂料未揽拌均匀，或者涂层内有些铝粉产生漂移、凝聚、位移等；  \n\nb.罩光清漆与金属闪光底色漆之间的闪干时间不足，导致部分底色漆被清漆溶解，结果铝粉或颜料的位置发生改变；  \n\nc.第一道罩光清漆喷得太湿，导致底色漆部分溶解。  \n\n$\\textcircled{2}$ 预防措施  \n\na.喷涂金属闪光底色漆时不能喷得太湿；  \n\nb.应严格按照厂商的规定进行调漆、喷漆；  \n\nc.而且确保一定的闪干时间。  \n\n$\\textcircled{3}$ 解决办法  \n\na.如果云斑出现在喷涂清漆之前，可重新调配底色漆，再进行喷涂施工，此时应将空气压调至最低；  \n\nb.如果云斑出现在喷涂清漆之后，则需待涂层彻底干透后，再采用 $\\mathtt{P800}\\sim1000$ 号水砂纸打磨平整，然后重新进行施工。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1122,
+        "chunk": "# 2.中间涂层  \n\n(1）开裂  \n\n$\\textcircled{1}$ 主要原因在外观良好的汽车表面喷涂过多的中间涂层。漆膜过厚，容易开裂。  \n\n$\\textcircled{2}$ 预防措施  \n\na.严格按照施工参数执行；b.在修补喷涂施工时，注意只喷到待修补的区域；c.有时将高度稀释了的中间涂料作为封闭底漆喷涂到热塑性丙烯酸面漆上，以减少原耗。(2）附着力差$\\textcircled{1}$ 主要原因a.表面未清洗干净，造成附着力差；b.选用了硅系列流平剂；c.干不透及其他问题。$\\textcircled{2}$ 预防措施a.在喷涂前采用清洗溶剂或金属调整剂清除掉所有表面的杂质（包括看得见和看不见的)；b.提请制漆厂注意选择合适的流平剂。  \n\n(3）表面粗糙  \n\n$\\Phi$ 主要原因有时涂料工在调漆时，经常把中间涂料的黏度调得高一点，以为这就可以一枪喷得厚一点来覆盖表面比较严重的划痕，结果造成表面粗糙、严重的橘纹。而且在清漆之后，还可能发现比较明显的打磨痕迹。这主要是因为在喷涂高黏度涂料时，涂料喷涂到表面之后，空气或溶剂蒸气无法像正常状态那样逸出而被包覆在有缺陷的基材上，一且中间涂层的溶剂挥发，或者喷涂面漆时，面漆中所含溶剂势必将渗透到中间涂层使其软化，涂层肯定会回落下陷按打磨轨迹形成划痕。另外还有可能的是表面打磨痕迹太明显，就像锉刀一样，此时即使黏度调整适当，也遮盖不了这些痕迹。  \n\n$\\textcircled{2}$ 预防措施  \n\na.按照产品说明书的要求进行稀释，每一道都要喷薄一点，形成薄的湿涂层；  \nb.每一道之间留下足够的闪蒸时间；  \nc.表面要打磨平整，既要求有一些粗糙，但打磨痕迹又不能太深。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1123,
+        "chunk": "# 3.腻子  \n\n如前所述，刮腻子的目的是填平斑点等小面积的缺陷，不是用来修补大面积的破损的。不少从事修补工作的工人把腻子当作可用来修复金属基材严重的万能胶。永远都要记住：首先应采用机械修复的办法使车身受损表面尽可能平整，然后再刮涂腻子。腻子不能用来填平深度大于 $100\\mu\\mathrm{m}$ 的凸凹不平的锤痕、深坑以及压延加工痕迹等，因为这将使干燥后的腻子容易因收缩而开裂。  \n\n4.阴极电泳底漆  \n\n\n<html><body><table><tr><td>主要原因</td><td>采取措施及解决办法</td></tr><tr><td>（1)漆膜太薄</td><td></td></tr><tr><td>a.pH过低、MEQ值偏高；</td><td>a.适当调整；</td></tr><tr><td>b.槽液温度较低；</td><td>b.检查热交换器，定期检查温控元件及加热系统；</td></tr><tr><td>c.槽液中有机溶剂含量下降；</td><td>c.适当调整；</td></tr><tr><td>d固体分下降； e.电沉积时间过短；</td><td>d.提高固体分，最好使其波动范围在标准的0.5%以内； e.延长时间；</td></tr><tr><td>f.电泳涂装后，UF水冲洗时间太长，产生再溶解；</td><td>f.缩短UF水冲洗时间，防止再溶解；</td></tr><tr><td>g.阴、阳极板比例失调； h.阳极液电导率太低；</td><td>g.检查极板是否有较大腐蚀现象发生或极板表面严重结垢； h.加速槽液更新，添加调整剂，提高槽液电导率，降低湿漆膜</td></tr><tr><td></td><td>电阻：</td></tr><tr><td></td><td></td></tr><tr><td>i.电冰电压偏低； j.电源接触不良</td><td>i适当提高电泳电压； j.检查电源系统，挂具是否被污染影响导电性</td></tr></table></body></html>  \n\n<html><body><table><tr><td></td><td></td></tr><tr><td>主要原因</td><td>采取措施及解决办法</td></tr><tr><td>（2）漆膜太厚</td><td>a.适当排放UF水，补加去离子水，降低槽液中杂离子</td></tr><tr><td>a.pH过高；</td><td>含量；</td></tr><tr><td>b.槽液温度偏高；</td><td>b.检查热交换器，定期检查温控元件及加热系统检查， 严格将槽温控制在工艺规定的范围内；</td></tr><tr><td>c.槽液中有机溶剂加量太多；</td><td>c.排放UF水，补加去离子水，延长新配槽液的熟化 时间；</td></tr><tr><td>d.固体分太高；</td><td>d.适当调整，最好使其波动范围在标准的0.5%以内；</td></tr><tr><td>e.电泳时间过长；</td><td>e.缩短电沉积时间，适当加快传动链链速；</td></tr><tr><td>f.阳极池电导率太高；</td><td>f.适当调整；</td></tr><tr><td>g电沫电压太高；</td><td>g.适当调整；</td></tr><tr><td>h.工件面积太小；</td><td>h.适当调整极比和阳极板的布局；</td></tr><tr><td>i工件周围槽液循环不良</td><td>i.大都因部分喷嘴堵塞所致，清理、维修</td></tr><tr><td>(3）漆膜粗糙</td><td></td></tr><tr><td>a.槽液温度太高；</td><td>a.检查槽液冷却系统；</td></tr><tr><td>b.电沫电压太高；</td><td>b.适当调整；</td></tr><tr><td>c.电沉积速率太快；</td><td>c.适当调整；</td></tr><tr><td>d.工件下槽前温度太高；</td><td>d.适当调整；</td></tr><tr><td>c.工件被导电性物质污染；</td><td>e.加强前处理及清洗工序检查；</td></tr><tr><td>f.槽液被油脂污染；</td><td>f.槽液循环系统中添加吸油过滤袋；</td></tr><tr><td>g.直流电纹波系数太高；</td><td>g.检查整流系统，特别是滤波系统电路；</td></tr><tr><td>h.有机溶剂含量超标；</td><td>h.适当排放UF液；</td></tr><tr><td>i.磷化膜粗糙</td><td>i检查磷化系统，改善工艺条件直至更换磷化处理剂</td></tr><tr><td>（4）漆膜针孔</td><td></td></tr><tr><td>a.电泳后冲洗不及时，造成再溶解针孔；</td><td>a.工件离开槽液后及时用UF水冲洗；</td></tr><tr><td>b.电沉积速度过快； c.槽液循环起泡严重；</td><td>b.调整工艺参数；</td></tr><tr><td>d.带电人槽模式下的针孔；</td><td>c.调整助剂，以利消泡，调整溶剂含量； d.控制杂离子浓度，调整磷化阶段工艺参数，使磷化膜</td></tr><tr><td></td><td>更加均匀、致密；</td></tr><tr><td>e.槽液温度偏低</td><td>e.调整槽液温度</td></tr><tr><td>(5）缩孔</td><td></td></tr><tr><td>a.溶剂含量不足；</td><td>a.适当添加溶剂；</td></tr><tr><td>b.前处理脱脂不良，磷化膜上有油污；</td><td>b.加强脱脂、除锈工序的控制，或更换处理液；</td></tr><tr><td>c.电沉积速率过快；</td><td>c.适当调整；</td></tr><tr><td>d.电流密度太高；</td><td>d.适当调整电压、降低槽液温度、适当延长电泳时间；</td></tr><tr><td>e.颜基比失调：</td><td>e.一般颜料分偏低，补加颜料浆；</td></tr><tr><td>f.槽液被污染；</td><td>f.在循环系统中加吸油过滤袋；</td></tr><tr><td>gpH太低；</td><td>g.适当调整；</td></tr><tr><td>h.槽液泡沫太多；</td><td>h.添加消泡剂、减缓槽液循环速率；</td></tr><tr><td>i.补充颜料浆或乳液混容性不良</td><td>i.补充颜料浆或乳液前加强质量监控</td></tr><tr><td>（6）漆膜光泽偏高</td><td></td></tr><tr><td>a.颜基比失调；</td><td>a.适当调整，补加颜料浆；</td></tr><tr><td>b.烘道温度异常；</td><td>b.一般偏低，适当调整；</td></tr><tr><td>c.烘烤时间太短</td><td>c.适当延长，减缓传动链运行速率</td></tr><tr><td>（7）漆膜光泽偏低</td><td></td></tr><tr><td>a.颜基比失调；</td><td>a.一般颜料分含量偏高，补加乳液；</td></tr><tr><td>b.冲洗水不纯；</td><td>b.加强冲洗水净化；</td></tr><tr><td>c.槽液被污染</td><td>c.在槽液循环系统中，加吸油滤袋</td></tr></table></body></html>  \n\n<html><body><table><tr><td>主要原因</td><td>采取措施及解决办法</td></tr><tr><td>（8）水痕</td><td></td></tr><tr><td>a.冲洗不良或冲洗水不纯；</td><td>a.加强水洗管理；</td></tr><tr><td>b.烘道温度异常，梯度设计不当，升温过快；</td><td>b.调整加热单元的工艺参数；</td></tr><tr><td>c.工件悬挂方位不当，致使某处有水残留；</td><td>c.调整工件悬挂方位；</td></tr><tr><td>d.进烘道前，挂具上滴落水到工件上</td><td>d.改进挂具结构，防止水等杂质滴落</td></tr><tr><td>（9）漆膜表面印痕（此项缺欠与水痕的不同就是带有水</td><td></td></tr><tr><td>痕的漆膜表面不平整，而印痕则仍然平整）</td><td></td></tr><tr><td>a.磷化后水洗不充分或冲洗水质不良；</td><td>a.加强磷化后的水洗，检查喷嘴是否堵塞，控制冲洗后</td></tr><tr><td>b.工件经预处理后，再次被污染</td><td>水滴的电导率，不应高出50S/cm； b.保持涂装场所的清洁卫生，改进挂具结构，防止挂具</td></tr><tr><td></td><td>上有水滴等杂物滴落</td></tr><tr><td>（10）漆膜厚度不均（类箱体结构的工件内、外不一） a.CED材料自身的泳透力较低；</td><td>a.选用泳透力较好的CED材料，CED材料的泳透力至</td></tr><tr><td></td><td>少要达到75%以上（一汽钢管法）；</td></tr><tr><td>b.电泳电压较低； c.槽液固体分偏低；</td><td>b.提高电泳电压：</td></tr><tr><td></td><td>c.及时监控槽液组成，及时补加漆料，使固体分始终保 持在工艺规定的范围内；</td></tr><tr><td>d.槽液搅拌效果不佳</td><td>d.加强槽液的循环、搅拌</td></tr><tr><td>（11）漆膜表面有脏物沉积</td><td></td></tr><tr><td>a.槽液过滤不良；</td><td>a.检查过滤系统；</td></tr><tr><td>b.磷化液带入槽内；</td><td>b.增加UF液排放；</td></tr><tr><td>c.槽液被电解质污染；</td><td>c.检查循环系统，排放UF液；</td></tr><tr><td>d.输送系统带人；</td><td>d.检查输送系统以及滴漏盘的设置是否合理；</td></tr><tr><td>e.pH太高； f.溶剂含量失调；</td><td>e.适当调整；</td></tr><tr><td>g.槽液循环系统异常</td><td>f.适当调整；</td></tr><tr><td>(12）流挂</td><td>g.检查槽液循环系统并作适当调整</td></tr><tr><td>a.电泳后水洗不良；</td><td>a.加强水洗，最好在电泳槽后增加一个浸入式清洗槽，</td></tr><tr><td>b.槽液固体分偏高，槽内冲洗水含漆量偏高；</td><td>适当提高循环去离子水的水温；</td></tr><tr><td>c.工件结构导致夹缝流挂；</td><td>b.增加UF液，补充去离子水；</td></tr><tr><td>d.烘道温度梯度设计不当</td><td>c.在工件上适当增开可供排水泄流孔；</td></tr><tr><td>（13）漆膜表面有疣点、颗粒</td><td>d.延长预热段的长度，使工件升温缓和</td></tr><tr><td>a.涂装环境太差；</td><td></td></tr><tr><td>b.槽液温度太高，致使槽液不稳定；</td><td>a.清理施工环境；</td></tr><tr><td></td><td>b.加强冷却系统运行；</td></tr><tr><td>c.烘道被污染；</td><td>c.定时清理烘道；</td></tr><tr><td>d.槽液被污染，有沉积物；</td><td>d.更换过滤袋为吸油型，加强槽液过滤；</td></tr><tr><td>e.槽液更新率太低；</td><td>e.加强日常槽液循环；</td></tr><tr><td>f.槽液过滤系统中过滤袋选择不当；</td><td>f.更换合适的过滤袋；</td></tr><tr><td>g.工件未处理干净，磷化后冲洗不够；</td><td></td></tr><tr><td></td><td>g.提高冲洗水的清洁度，加强水洗；</td></tr><tr><td>h.电泳后冲洗液脏</td><td>h.加强过滤，更换细度较小的过滤袋</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1124,
+        "chunk": "# 第八节发展和展望  \n\n随着汽车工业的稳步发展，汽车漆市场也获得了持续增长的商机。为适应汽车行业对市场提出的日渐苛刻的需求，各汽车漆生产厂家也不得不采用新技术、新工艺、新材料来应对汽车总装厂的对质量、性能、价格等方面的要求。汽车车身对涂层的基本要求大致可分为装  \n\n饰性、防护性两个方面：  \n\n$\\Phi$ 装饰性光泽、鲜映性、平整光滑以及滑爽的手感等。  \n\n②防护性耐候性、耐酸雨性能、抗洗刷性能、抗石击性能以及抗污性等。  \n\n显而易见，汽车漆的未来也是围绕上述两个方面而进行的。  \n\n除上述两方面的基本需求外，汽车业及其涂料行业也应适应和遵守当今社会愈来愈苛刻的环保法规。无疑，具有低VOC的环保型汽车漆也是今后汽车漆的重要发展方向之一。近年来汽车涂装工艺已经逐渐由以往常见的传统工艺过渡到新的涂装工艺。  \n\n$\\Phi$ 传统工艺 CED $^+$ 高固含中间涂料 $^+$ 高固含底色漆 $^+$ 高固含罩光清漆。  \n$\\textcircled{2}$ 新的理想工艺CED $^+$ 粉末中间涂料 $^+$ 水性底色漆 $^+$ 粉末罩光清漆。  \n\n这种过渡充分反映了汽车业及涂料业界在提高汽车漆性能的同时对环保法规的重视。有关资料显示，如果新的涂装工艺完全实施，则VOC排放量可由传统的 $60\\sim100\\mathrm{g/m^{2}}$ 可降低到 $12\\mathrm{g}/\\mathrm{m}^{2}$ ，这样既从根本上满足了环保法规对VOC排放的限制，也进一步提升了汽车漆自身的综合性能。现就阴极电泳底漆（CED)、中间涂料以及面漆几个方面的最新进展情况分别予以介绍。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1125,
+        "chunk": "# 一、阴极电泳底漆  \n\n现代的汽车生产线几乎都采用了高环保、高涂装效率的CED来进行车身的腐蚀底漆涂装。我国自20世纪80年代一汽、二汽开始在其涂装线上采用引进技术的CED，十余年来，所采用的CED从第1代产品陆续更新发展到第 $4{\\sim}5$ 代产品。目前，代表性的产品为日本关西的HB-2000系列、美国PPG的ED-5系列等。这类产品的主要特征为均采用重金属铅作为防腐蚀颜料和交联催化剂。铅一直以来均作为CED系统的重要固化交联催化剂及防腐、防锈颜料。它的最大隐患就是重金属污染所带来的环保问题。虽然有人尝试用毒性稍低的锡、秘等金属来取代铅，也能取得一定效果，但仍然不能从根本上解决重金属对环境污染的问题。于是新一代环保型CED应运而生，其中较有代表性的产品为美国PPG公司的EC6350产品系列、日本关西的GT-10LF产品系列等。  \n\n新一代CED的主要特征如下。  \n\n$\\textcircled{1}$ 环保无毒无铅、无锡、无秘、无重金属，可满足欧盟、北美等最新环保法规的要求。  \n\n$\\textcircled{2}$ 高泳透力高泳透力可使复杂工件的内、外表面的膜厚差低至 $6\\sim7\\mu\\mathrm{m}$ 的水平。这样，就可以提高和保证整个汽车车身的耐盐雾水平。  \n\n$\\textcircled{3}$ 低烘干温度将烘烤条件降低至 $150\\mathrm{^c}\\times20\\mathrm{min}$ 或 $160\\mathrm{{^c}\\times10\\mathrm{{min}}}$ ，极大地节约了能源消耗。  \n\n$\\textcircled{4}$ 低加热减量加热减量控制在 $4\\%$ 以内，一般在 $2\\%$ 左右，减少挥发物排放，降低环境污染。  \n\n$\\textcircled{5}$ 更新期当出现CED涂料更新周期较长的情况下，也能保证非常好的槽液稳定性能。  \n\n$\\textcircled{6}$ 低溶剂含量采用不同的技术，控制槽液中的有机溶剂的含量在 $1\\%$ 以内，降低阴极电泳漆的VOC排放量。  \n\n$\\textcircled{7}$ 高平滑性采用独特表面控制技术，使漆膜的表面粗糙度 $(R_{*}$ ）控制在0. $2\\mu\\mathrm{m}$ 以内，这就极大地改善了CED漆膜的表面平滑性，对面漆的烘托性能也将得到提高。  \n\n未来一代CED除具备上述特征外，新型超厚膜化（其漆膜厚度可调，且具有良好的抗石击性能，有别于早期的厚膜CED)、边角覆盖型、耐候型、低温固化型、紫外光固化型、高装饰型等也是各个汽车总装厂所追求的理想目标。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1126,
+        "chunk": "# 二、中间涂料  \n\n目前，我国的汽车业几乎均采用聚酯或醇酸-氨基体系的溶剂型中间涂料。施工固含大体为 $50\\%\\sim60\\%$ ，此时VOC为 $35\\%\\sim40\\%$ 。如果采用高固含的氨基树脂，可将固含提高到$65\\%\\sim70\\%$ 。然而，这并不能从根本上解决有关法规对溶剂排放的限制。欧洲早已开始使用水性中间涂料，北美则主张使用粉末型中间涂料，这样可以将VOC降低至 $0\\sim8\\%$ 0  \n\n现代汽车对耐石击性能的要求也逐渐苛刻，汽车的发动机罩盖、侧下围等易受路面小石子的冲击，漆膜容易崩裂破损，这将严重影响汽车外观和耐腐蚀性能。为此，采用封闭的异氰酸酯交联剂新一代耐石击中涂层漆应运而生。近年来，各大汽车公司已经逐渐采用新一代耐石击性中涂层漆来替代以往传统中间涂料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1127,
+        "chunk": "# 三、底色漆  \n\n如前所述，底色漆是整个涂装系统中溶剂释放量最高的工艺环节，因此，采用低VOC底色漆就成为从事汽车漆研发的技术人员的首要任务。一般底色漆的固含量为 $20\\%\\sim30\\%$ .前几年北美和欧洲改用高固含量的底色漆，固含提高到 $45\\%\\sim50\\%$ ，VOC仍然处于较高水平。水性底色漆的发展和完善，无疑是底色漆技术发展的目标和方向。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1128,
+        "chunk": "# 四、罩光清漆  \n\n罩光清漆的发展方向也包含两方面内容，即低VOC化和性能改善。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1129,
+        "chunk": "# 1.水性罩光清漆  \n\n在汽车行业中最先获得实施的水性罩光清漆由水性氨基树脂和水性丙烯酸树脂所组成，其中加有少量醇醚类助溶剂。其溶剂排放量仅为 $5\\sim10\\mathrm{g}/\\mathrm{m}^{2}$ ，远低于溶剂型罩光清漆的 $30\\sim$ $35g/\\mathrm{m}^{2}$ 。以封闭型异氰酸酯类化合物替代氨基树脂是改善漆膜耐酸雨性能的有效途径。近年来这类水性罩光清漆已成功用作汽车罩光清漆。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1130,
+        "chunk": "# 2.粉末罩光清漆  \n\n粉末罩光清漆因几无VOC排放、节约能源以及生产效率高等特点越来越受到汽车业界的关注。自1994年世界上第一辆以粉末涂料罩光的汽车下线以及1996年德国宝马汽车公司成功采用粉末型丙烯酸罩光清漆以来，粉末型罩光清漆获得了较快发展。现今已经工业化的粉末罩光清漆包括环氧-聚酯混合类、聚酯类、聚氨酯类以及丙烯酸类等。汽车罩光清漆未来的发展方向主要集中在如何进一步提高其表面装饰性能、耐酸雨性、耐洗刷性以及耐候性等。另外，还需要兼顾在涂装过程中低的VOC排放、低能耗以及较高的生产效率等。具体体现在采用新型固化剂（如：封闭型异氰酸酯类、改性异氰脲酸缩水甘油酯类等）、薄膜化（早期丙烯酸类粉末罩光清漆的漆膜厚度达 $100\\mu\\mathrm{m}$ 以上）以及降低固化温度等。在降低固化温度中采用紫外光固化技术是比较理想的技术路线。  \n\n紫外光固化粉末罩光清漆是欧洲近年来市场开发的最新成果，它是一项将传统粉末涂料与新固化技术相结合的产物。具有节约能源（耗能仅为热固型粉末涂料的 $1/5\\sim1/10)$ 、无排放、生产效率极高（固化速率极快，仅需 $0.1\\sim10\\mathrm{s}\\$ ）等特点，特别适合大型汽车总装厂涂装线的工艺。尽管该项技术具有巨大的商业发展潜力，但即使在汽车业较为发达的欧洲，也仍然还处在市场开发的前期阶段。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1131,
+        "chunk": "# 五、汽车修补漆  \n\n汽车修补漆与原厂漆发展趋势类似，也是低VOC排放和性能更加优化。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1132,
+        "chunk": "# 1.水性化  \n\n在欧洲，水性化的市场开发已基本完成，其中一些大型汽车修补漆制造厂家已向市场推出了较为成熟的水性汽车修补漆系统。如德国赫伯兹公司推介到我国汽车修补漆市场的“施必快”和“施得乐”两个系统就是其中比较典型的范例。这两个系统都比较完善、齐全，它们不仅拥有市场上所习惯采用的标准型、厚膜型修补漆系统，而且还包含有目前市面上尚不多见的水性汽车修补漆系统，如水性金属闪光底色漆、水性本色底色漆以及水性本色漆等。通过该公司提供给客户的计算机查询系统，可以从同一种车色的色卡号中发现；查询系统在显示溶剂型修补漆配方的同时，亦列出了水性漆的配方，如水性金属闪光底色漆 StandohydBase等。可惜目前在国内在汽车修补涂料面漆领域，水性汽车修补漆的市场还不多见，业内对于汽车修补涂料的水性化还没有引起足够关注。另外，上述系统中，不包含水性罩光清漆，采用水性罩光清漆也是今后业内共同努力的目标。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1133,
+        "chunk": "# 2.高功能化  \n\n在基本物性上，全面达到原厂漆的水平是汽车修补漆行业一直追求的理想目标。除此而外，汽车修补漆还必须满足某些特殊需求，如为了尽可能减少不粘灰时间以获得理想的外观所要求的“超快干”性能。杜邦公司前不久向市场推出了一种超快干罩光清漆，据称，该产品在喷涂成膜并经大约45min的低温烘烤后即可进行抛光作业，受到市场的普遍关注。  \n\n从理论上分析，欲达到如此快的干燥速率，采用传统羟基丙烯酸树脂 $^+$ 异氰酸酯类固化剂的系统，单纯依赖—OH与—NCO之间的交联反应，即使添加各种高效促进剂也无法达到上述要求。必须另辟新路，采用新的交联体系。  \n\n在尝试采用新型交联体系中，国内外均进行了一些探索试验，并取得进展，这其中最具实用价值的就是采用亚氨基替代传统的羟基。亚氨基（—NH）与—NCO反应速率大大快于一OH，较有可能大幅提升交联反应的速率，但也应留意随之而来“适用期”（漆料中加入固化剂后的可使用时间）过短的病。据有关资料披露，在羟基丙烯酸树脂中引入含某些取代基的亚氨基，既可使干燥速率加快，达到超快干，同时也可获得具有实用价值的“适用期”。这是因为该取代基对亚氨基产生一定空间位阻作用，可适当减缓亚氨基与—NCO的反应速率的缘故。这种同时含亚氨基和羟基的丙烯酸树脂，与适当的异氰酸酯类固化剂搭配是达成超快干目的的较为理想的技术路线。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1134,
+        "chunk": "# 缩略语  \n\nAED：阳极电泳底漆  \nBPO：过氧化苯甲酰  \nCAB：醋酸丁酸纤维素  \nCAC：醇酸乙氧基乙酯，俗称醋酸溶纤剂  \nCED：阴极电泳底漆  \nCOD：化学需氧量  \nDBE：混合羧酸二甲酯  \nEEW值：环氧当量  \nHDI：六次甲基二异氰酸酯  \n\nIPDI：异佛尔酮二异氰酸酯$\\mathrm{LD}_{50}$ ：半致死剂量LPB：液态聚丁二烯MIBK，甲基异丁基酮NC：硝化棉·NCO：异氰酸酯基NVM：不挥发分，以往俗称固含量PVC：在涂料领域，塑溶胶部分代表；聚氯乙烯树脂，色漆部分代表；颜料体积浓度QUV：紫外光人工加速老化仪SCA：流挂控制剂TDI：甲苯二异氰酸酯TMP：三羟甲基丙烷TO值：电泳涂装施工中的所谓“更新期”（turnover time)，即补漆固体分的累计量达到电泳槽内槽液固体分含量的时间，一般单位为“月”UF：超滤VDA循环：德国汽车总装厂通常采用的湿热与盐雾交替试验标准VOC：挥发性有机化合物含量△E：色差",
+        "category": " Introduction"
+    },
+    {
+        "id": 1135,
+        "chunk": "# 参考文献  \n\n[1] Hans-Joachim Streitberger.Automotive Paints and Coatings.KGaA: Wiley-Vch Verlag GmbH &. Co, 2007.   \n[2] Arthur A. Tracton Coatings Tech. Handbook. third edition, CRC, 2006.   \n[3] Rose A. Ryntz, Coatings Polym,&. Plastics,Marcel Dekker, Inc.2005, [4] Harry T. Chudy Automotive Refinish Second Edition Prentice Hall, Englewood Cliffs, 1988.   \n[5] Zeno W, Wicks, Jr.Organic Coatings Sei.&. Tech third edition.Wiley-Interscience 2007.   \n[6] Electrocoat Manual, Automotive OEM coatings BASF Corporation.   \n[7] Autophoretic 866 Manual Henkel Co.   \n[8] 小西彻， 自动车用耐酸雨涂料，工业涂装，1994（130)：17-23.   \n[9] Chatfield H W The Sei. of Surface Coatings Ernest Benn Limited, 1962.   \n[10] 汪盛藻. 汽车修补涂料与涂装技术，北京：中国石化出版社，2006.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,8647 @@
+[
+    {
+        "id": 1,
+        "chunk": "# COATINGS TECHNOLOGY",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# 涂料工艺  \n\n![](images/5e20664385dca52cee308e9b9e0c350fefe9881a9e0465959d0c0974f43c94a9.jpg)  \n\n《涂料工艺》第四版在保持第三版基本结构的基础上，从市场经济条件下对涂料技术发展和管理的要求出发进行修订。全书共分五篇：导论、涂料原材料、涂料各论、涂料的制造过程控制、涂装过程控制。涂料原材料篇尽量引人新观念、新材料、新原理和新标准，力求在与国际接轨的同时而又兼顾我国是发展中国家的现实，坚持先进性、实用性和经济性的统一。涂料各论篇按用途进行编写，涵盖涂料的基本品种，力求反映其现代技术水平，除提供实用的基础配方外重点讲述配方原理。涂料的制造过程控制篇介绍了涂料生产设备、涂料工厂设计、原料与产品的标准和检验，更加强调法规要求。涂装过程控制篇增加了涂料涂装工艺一体化的理念，强调了涂装现场管理和技术服务的重要性。  \n\n全书从涂料的基础知识、基本理论、原材料和产品性能要求和检测标准、配方原理、涂料生产过程控制、涂装工艺要求、涂装技术服务和涂装缺陷控制等方面对涂料工艺进行系统和全面的论述，帮助涂料行业从业人员树立涂料工艺的整体观，为涂料技术创新拓展思路。同时新版力求保持第三版实用性特点，所列配方翔实可靠，并标明原材料规格和供应商。本书可供涂料和涂装行业的工程技术人员、管理人员和技师阅读，也可作为大专院校相关专业师生的参考书。",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 图书在版编目（CIP）数据  \n\n涂料工艺/刘登良主编.一4版.一北京：化学工业出版社，2009.12ISBN 978-7-122-06676-3  \n\nI.涂·· Ⅱ．刘…． Ⅲ．涂料-工艺学 IV.TQ630.1中国版本图书馆CIP数据核字（2009）第165727号责任编辑：顾南君 文字编辑：冯国庆、王琪、向东、智景岩、林丹、李玥责任校对：宋夏 装帧设计：张辉  \n\n出版发行：化学工业出版社（北京市东城区青年湖南街13号邮政编码100011)  \n印刷：北京永鑫印刷有限责任公司  \n装订：三河市万龙印装有限公司  \n$787\\mathrm{mm}\\times1092\\mathrm{mm}$ 1/16印张129字数3428千字2010年1月北京第4版第1次印  \n\n购书咨询：010-64518888（传真：010-64519686） 售后服务：010-64518899网址：http://www.cip.com.cn凡购买本书，如有缺损质量问题，本社销售中心负责调换。  \n\n《涂料工艺》自1970年问世，历经 $1992{\\sim}1996$ 年改版为6个分册，1997年再改为第三版的合订两册。《涂料工艺》第二版于1997年获第八届全国优秀科技图书二等奖；于1998年获国家石油和化学工业局科技进步二等奖。作为涂料行业集体智慧的结晶和权威的专著哺育了两代涂料专业技术和管理人员，功不可没。但是，对涂料工艺的认识基本上还处在计划经济的思维体系和框架中。最近十几年来，在改革开放和国民经济快速稳定增长，以及中国成为“世界制造基地”，在经济全球化和市场国际化的推动下，中国涂料行业的发展进入了快车道。从20世纪90年代的100万吨/年猛增至2008年的600多万吨/年，中国已成为世界第一大涂料生产和消费国。世界排名前二十位的跨国公司都已进入中国市场并完成了本地化生产的战略布局，成为中国涂料行业重要组成部分。再加上大批原材料、涂料设备和检测仪器供应商的进驻，中国涂料行业的技术发展水平、产品结构和管理水平迅速与国际接轨，融入国际化竞争的大环境。与此同时，在涂料研发和生产工艺控制中，ISO9001质量管理体系、ISO14001环境管理体系、ISO-18000安全和职业健康管理体系等先进的管理理念在行业中实践了十多年。而可持续发展的科学发展观对行业的技术发展方向提出更高的要求：节能、减排、省资源、安全和环保，以及日益从紧的法律法规。涂料行业与涂装行业紧密结合，为用户提供满意的服务和最终效果，实现由涂料制造业向“加工服务业”转变的理念将推动涂料行业技术迈向新的台阶。此外，新版中还引入技术经济的观念。作为工艺学，处理好技术发展的先进性、实用性、可行性、经济性和可靠性-风险分析等之间的关系，并适当地介绍现代技术研发R&D的项目管理的基础要求，以提高研发的效率和效益。以上所述正是《涂料工艺》第四版编写的宗旨。  \n\n在整体结构保持第三版基本框架的基础上，按新的涂料分类标准GB/T2705-2003向国际标准靠拢，全书分为五篇：导论一—涂料基础知识和原理、涂料工艺范畴：原材料篇—介绍了成膜物、颜料、分散介质和助剂：涂料各论篇一—按用途叙述，充实内容、拓展领域：涂料制造过程控制篇一—涂料原材料、中间体和成品检测与质量控制，突出法律和法规的要求，补充现代质量管理体系：涂装过程控制篇一一突出涂料涂装一体化的理念、涂装现场管理和技术服务。帮助工程技术人员建立系统的涂料工艺观一——从原材料控制、涂料配方设计理论、涂料生产工艺、涂料性能检测至涂装工艺研发和涂装技术服务体系等。 020  \n\n本次改版工作得到中国涂料工业协会全力支持。以中涂协专家委员会为基础，动员了七十多位专家参与写作，力求从国际化视野反映我国目前涂料行业的技术水平，并对未来国际化竞争环境下涂料工艺的发展趋势加以阐述。同时聘请涂料行业的资深专家担任编委对各篇进行把关，其具体分工如下：虞兆年和洪啸吟负责原材料树脂、分散介质的审定，钱伯容负责颜填料、助剂、卷材涂料的审定，石玉梅负责建筑涂料的审定，叶汉慈负责不饱和树脂、木器涂料和塑料涂料的审定，沈浩负责涂料原材料和产品检验、涂料生产设备、工厂设计的审定，刘国杰负责有机硅树脂、航空航天涂料的审定，刘会成负责集装箱涂料、涂装过程控制篇的审定，王健和李荣俊负责海洋涂料和重防腐涂料的审定，刘登良负责导论编写及其余部分的审定并通审全稿。希望广大读者一如既往地支持《涂料工艺》新版发行，多提宝贵意见，以利于不断改进，办成精品，保持其在涂料行业的权威地位，为推动中国涂料行业的发展继续做贡献。  \n\n海洋化工研究院、中海油常州涂料化工研究院、江苏兰陵化工集团有限公司等对编委会的工作提供大力支持，在此表示衷心感谢！  \n\n《涂料工艺》编委会2009年9月",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# 第三章 重防腐涂料…. 991",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# 第一节 金属腐蚀与防护  \n\n简论 李荣俊 李兴仁991  \n一、金属腐蚀的定义 991  \n二、金属腐蚀的危害性 991  \n三、金属腐蚀的分类 992  \n四、金属在自然环境中的腐蚀 995",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 第二节 重防腐涂料简述··李荣俊 孙凌云1011  \n\n一、重防腐涂料的特点 1011  \n二、常用重防腐涂料简述 1014",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 第三节 重防腐涂料涂装  \n\n李荣俊 黄安李华刚1037  \n一、重防腐涂装设计原则 1037  \n二、“全寿命经济分析法”设计思想简介：1037  \n三、防腐涂层配套体系的设计 1037  \n四、重防腐涂装施工工艺要点 1046",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 第四节 混凝土结构的腐蚀  \n\n与防护 林绍基 李荣俊 1049  \n\n一、混凝土结构腐蚀的严重性 1049  \n二、钢筋混凝土结构的腐蚀机理 1051  \n三、钢筋混凝土腐蚀环境分析 1055  \n四、混凝土结构腐蚀防护措施 1056  \n五、混凝土防护涂层配套体系 1058  \n六、混凝土结构防护涂装的特殊性和施工  \n工艺要点 1059  \n[五节典型重防腐涂料与涂装 1 1062",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 一、桥梁防腐涂料与  \n\n涂装 孙凌云 李兴仁1062  \n二、石油化工防腐蚀涂料 +\\*\\*: 刘新1075  \n三、建筑钢结构防腐蚀涂料 ...++.. 刘新1088  \n四、港口机械与设备钢结构防护涂装．·…· 马赫 李荣俊 刘 新1096  \n五、电力系统用防腐涂料 ... 黄安李桂宁宋志荣 史春晖1101  \n\n六、地坪涂料 周子1122  \n七、耐温防腐涂料 000... 唐峰 王健1135  \n八、机车涂料 孟庆昂1142  \n九、工程机械涂料·…·．刘新 易海瑞1146  \n参考文献 1151",
+        "category": " References"
+    },
+    {
+        "id": 10,
+        "chunk": "# 第四章 海洋涂料 1153",
+        "category": " Introduction"
+    },
+    {
+        "id": 11,
+        "chunk": "# 第一节 船舶涂料 1153  \n\n一、船舶涂料概况 王健1153  \n二、车间底漆 王健 袁林森1155  \n三、船底防锈漆 金晓鸿1161  \n四、船底防污漆 任卫东 王健1166  \n五、船壳/甲板漆· 唐海英1186  \n六、各种舱室漆 金晓鸿 朱红1194  \n七、船舶漆的  \n\n涂装 ..0 龚骏朱洪王健1204",
+        "category": " Introduction"
+    },
+    {
+        "id": 12,
+        "chunk": "# 第二节 集装箱涂料 刘会成1220  \n\n一、集装箱涂料简介 1220  \n\n二、集装箱涂料的配套方案和集装箱涂料 1224",
+        "category": " Introduction"
+    },
+    {
+        "id": 13,
+        "chunk": "# 三、集装箱生产线及对涂料性能的要求和  \n\n影响 1230  \n四、常见的涂膜病及解决方法 1236  \n五、集装箱涂料、涂装的发展趋势 1239",
+        "category": " Table of Contents"
+    },
+    {
+        "id": 14,
+        "chunk": "# 第三节 海洋工程重防腐  \n\n涂料 刘新杜 阳1241  \n\n一、海洋油气资源开发及海洋工程简史·… 1241  \n二、海洋工程结构物分类 1242  \n三、海洋的腐蚀环境 1243  \n四、海洋工程防腐蚀涂料的发展 1245  \n五、海洋工程防腐涂料 1247  \n六、海洋工程防腐蚀涂料性能要求 1251  \n七、海洋工程防腐涂料系统 1257  \n八、海洋工程涂装质量要求 1263  \n：考文献 中 1266",
+        "category": " Introduction"
+    },
+    {
+        "id": 15,
+        "chunk": "# 第五章 预涂卷材涂料. 王利群1267  \n\n第一节 预涂卷材概述 1267  \n第二节 预涂卷材生产工艺 1270  \n第三节底材的预处理 -1272  \n一、脱脂 . ·1272  \n二、表面调整处理 1273  \n三、化学转化处理 ：1273  \n四、环保型处理液 ·1274  \n第四节预涂卷材涂料概述 1275  \n一、预涂卷材涂料的特点和性能  \n要求 ：1275  \n二、预涂卷材涂料的组成 ：1275  \n三、预涂卷材涂料性能的影响因素 1 ..1280  \n四、预涂卷材涂料的性能检验标准 ：1281  \n五、预涂卷材涂料的性能检验方法 ·1284  \n第五节预涂卷材用底漆 ：1284  \n一、预涂卷材底漆概述 助 1284  \n二、预涂卷材底漆的组成 ：1285  \n三、环氧类底漆 1288  \n四、聚酯类底漆 1289  \n五、高性能卷材底漆 1290  \n六、水性底漆 1290  \n第六节预涂卷材用面漆 1291  \n一、预涂卷材用面漆概述 1291  \n二、聚酯类面漆 ：1291  \n三、聚乙烯类面漆 1293  \n四、丙烯酸类面漆 1293  \n五、耐久型面漆 ：1294  \n第七节预涂卷材用背面漆 1296  \n一、背漆概述 1296  \n二、环氧背漆 1297  \n三、聚酯背漆 ·1297  \n第八节卷铝涂料 1299  \n一、卷铝及铝塑复合板生产工艺 1299  \n二、卷铝涂料 1301  \n第九节卷材涂料新进展 ：1304  \n一、家电用卷材涂料 ·1305  \n二、汽车用卷材涂料 ：1307  \n三、食品罐用卷材涂料 ：1308  \n四、隔热卷材涂料 ·1309  \n五、纳米材料的应用 1310  \n六、特殊功能性彩板用卷材涂料 1311  \n七、环保卷材涂料 ：1312  \n八、结论 ：1314  \n参考文献 1314",
+        "category": " Introduction"
+    },
+    {
+        "id": 16,
+        "chunk": "# 第六章 塑料涂料 李少香1316",
+        "category": " References"
+    },
+    {
+        "id": 17,
+        "chunk": "# 第一节 塑料底材的特征 1317  \n\n一、塑料的组成与分类 1317  \n二、塑料的特性 1318  \n三、常用塑料性能简介 1320  \n第二节 塑料涂料的附着力 1325  \n\n一、塑料制品的表面张力及液体在聚合物 表面润湿和铺展的基本条件 1325 二、溶解度参数 1327 三、提高漆膜附着的途径 1327",
+        "category": " Introduction"
+    },
+    {
+        "id": 18,
+        "chunk": "# 第三节 塑料底材的表面处理 1329  \n\n一、塑料的常规处理方法 1329  \n二、表面应力的消除 1344  \n三、表面处理的评价方法 1344",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 19,
+        "chunk": "# 第四节 塑料用涂料的分类 1345  \n\n一、塑料用涂料选择基本原则 1345  \n二、主要塑料底材用涂料 1347",
+        "category": " Introduction"
+    },
+    {
+        "id": 20,
+        "chunk": "# 第五节 塑料涂料的涂装 1359  \n\n一、塑料涂料涂装施工方法 1360  \n塑料制品表面处理 1361  \n三、涂膜干燥类型 1362  \n四、塑胶漆涂膜的性能测试 1362  \n五、最新塑胶涂装方法 1364  \n六、塑胶漆膜缺陷及分析 1365  \n参考文献 1366",
+        "category": " References"
+    },
+    {
+        "id": 21,
+        "chunk": "#",
+        "category": "ovide the text segment you'd like me to analyze, and I will classify it accordingly."
+    },
+    {
+        "id": 22,
+        "chunk": "# 第七章 木用涂料 1367  \n\n第一节 木用涂料沿革 叶汉慈1367  \n第二节 木材与木质材料的特性及涂装前的基  \n本要求 吴智慧 叶汉慈1367  \n一、木材的特性 1367  \n二、木质材料的特性 1371  \n三、木制品应为涂装提供的条件 1376",
+        "category": " Introduction"
+    },
+    {
+        "id": 23,
+        "chunk": "# 第三节 木用涂料的品种及  \n\n分类 叶汉慈 张纯名1376   \n一、木用涂料的品种 1376   \n二、木用涂料产品分类 1379   \n四节 木用涂料产品基础配方及原理   \n王庆生 谢晓芳 曾光明 赖华1382   \n一、腻子 1382   \n二、封闭底漆 1386   \n三、底漆 1388   \n四、面漆 1396   \n五、固化剂 1416   \n六、稀释剂 1441   \n七、蓝、白水 1443   \n八、着色材料 1445   \n第五节 木用涂料产品的   \n涂装应用 叶汉慈 张纯名1450   \n一、现场调配 1450   \n、涂料产品底面漆配套原理 1451   \n三、木用涂装常用涂装工艺 1452  \n\n第六节 木用涂装常见问题的现象、原因及处理 叶汉慈 张纯名1473",
+        "category": " Introduction"
+    },
+    {
+        "id": 24,
+        "chunk": "# 一、涂料涂装前常见漆病的预防及处理 1473  \n\n二、涂料涂装过程中常见漆病的预防及处理 1474",
+        "category": " Introduction"
+    },
+    {
+        "id": 25,
+        "chunk": "# 三、涂料涂装之后常见漆病的预防及  \n\n处理 1478",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 26,
+        "chunk": "# 四、木用涂料涂装管理与涂装难题 中 00000 1479  \n\n第七节 木用涂料主要性能指标及检验 刘红1481一、木用涂料需要控制的指标 :1481二、有关木用涂料性能的国家标准和行业标准 1482三、木质家具标准中对涂膜性能的要求：1486四、通用检验方法 1488五、特殊指标和特殊检测方法 1491",
+        "category": " Introduction"
+    },
+    {
+        "id": 27,
+        "chunk": "# 六、木用涂料生产、施工、成膜后的有害",
+        "category": " Introduction"
+    },
+    {
+        "id": 28,
+        "chunk": "# 物质标准及测试方法 1494",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 29,
+        "chunk": "# 第八节 木用涂料与涂装的发展 ·.叶汉慈1499  \n\n一、家具的发展 1499  \n二、底材应用 1499  \n三、木用涂料的发展 1499  \n四、木用涂装的发展 1501  \n五、综述 1501  \n：考文献 1501",
+        "category": " References"
+    },
+    {
+        "id": 30,
+        "chunk": "# 第八章 粉末涂料 史英骥1504",
+        "category": " References"
+    },
+    {
+        "id": 31,
+        "chunk": "# 第一节 热塑性粉末涂料 1505  \n\n一、乙烯基类粉末涂料 1506  \n二、聚烯烃粉末涂料 1509  \n三、尼龙粉末涂料 1513  \n四、热塑性聚酯粉末涂料 1515",
+        "category": " Introduction"
+    },
+    {
+        "id": 32,
+        "chunk": "# 第二节 热固性粉末涂料 1516  \n\n一、纯环氧型粉末涂料 1516  \n二、环氧/聚酯混合型粉末涂料 1519  \n三、纯聚酯型粉末涂料 1522  \n四、丙烯酸型粉末涂料 1525  \n五、其他类型粉末涂料及辐射固化的",
+        "category": " Introduction"
+    },
+    {
+        "id": 33,
+        "chunk": "#  \n\n粉末涂料 1526  \n第三节 热固性粉末涂料的生产技术 .... 1529  \n一、粉末涂料的配方及原材料 1529  \n二、粉末涂料的生产工艺 1544  \n三、粉末涂料生产及产品质量控制 1552  \n第四节热固性粉末涂料的涂装工艺 1557  \n一、表面处理 1557  \n二、粉末涂料的涂装 1560  \n三、展望 1573  \n参考文献 1574",
+        "category": " References"
+    },
+    {
+        "id": 34,
+        "chunk": "# 第九章 航空航天  \n\n涂料…孟军锋 马宏冯俊忠1575",
+        "category": " References"
+    },
+    {
+        "id": 35,
+        "chunk": "# 第一节 飞机蒙皮涂料 1576  \n\n一、飞机蒙皮涂料的现状及趋势 1576  \n二、飞机蒙皮涂料的作用 1579  \n三、飞机蒙皮涂料的组成 1582  \n四、飞机蒙皮涂料施工 1587  \n五、飞机蒙皮涂料展望 1588",
+        "category": " Introduction"
+    },
+    {
+        "id": 36,
+        "chunk": "# 第二节 消融隔热涂料 1589  \n\n一、概述 1589  \n二、消融材料 1591  \n三、消融隔热涂层的作用机理 1593  \n四、消融隔热涂料的配方设计原则 1598  \n五、消融隔热涂层的组成 1599",
+        "category": " Introduction"
+    },
+    {
+        "id": 37,
+        "chunk": "# 第三节 隔热保温涂料 1608  \n\n一、概述 1608   \n二、热控涂料 1609   \n三、耐高温隔热保温涂料 1617   \n四、小结 1621   \n参考文献 1621",
+        "category": " Introduction"
+    },
+    {
+        "id": 38,
+        "chunk": "# 第十章 机床涂料与涂装······….谢劲1623",
+        "category": " References"
+    },
+    {
+        "id": 39,
+        "chunk": "# 第一节 概述 1623  \n\n一、涂装的作用 1623  \n二、机床涂装作业特点 1623",
+        "category": " Introduction"
+    },
+    {
+        "id": 40,
+        "chunk": "# 第二节 机床涂装用涂料 1624  \n\n一、机床涂装用涂料选用原则 1624  \n二、机床涂装常用涂料 重 1625",
+        "category": " Introduction"
+    },
+    {
+        "id": 41,
+        "chunk": "# 第三节 机床涂装工艺 1638  \n\n一、机床零、部件涂装工艺 1638  \n二、机床钣金件涂装工艺 1641  \n三、成品机床涂装工艺 1642  \n四、机床一次涂装工艺 1644  \n五、美术漆及其涂装工艺 1645",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 42,
+        "chunk": "# 六、机床涂装中常见的漆膜病及防止  \n\n方法 1650  \n第四节机床色彩格调 中 1653  \n一、机床色彩格调选择原则 1653  \n二、机床色彩配置原则 1653  \n三、世界各地对色彩的爱好与禁忌 1654  \n第五节机床涂层质量的检验 1655  \n一、涂层外观质量检验 1655  \n二、涂层耐温热试验 1656  \n三、涂层耐工作介质试验 1657  \n参考文献 1657",
+        "category": " References"
+    },
+    {
+        "id": 43,
+        "chunk": "# 第十一章防火涂料 王华进1658  \n\n第一节 防火涂料概述 1658  \n第二节 防火涂料的分类 1659  \n第三节防火涂料的防火机理 1659  \n第四节防火涂料的组成 1673  \n一、基体树脂 1673  \n二、阻燃剂 1676  \n第五节防火涂料的配方设计 1680  \n一、钢结构防火涂料的配方设计 1681  \n二、环氧防火涂料的基本配方及检测方法 福 1690  \n第六节防火涂料的发展 1691  \n参考文献 1694",
+        "category": " Introduction"
+    },
+    {
+        "id": 44,
+        "chunk": "# 第十二章 道路交通标线涂料..··.杜玲玲1695  \n\n第一节 标线涂料的特殊性能要求 1695  \n第二节 我国现有标线涂料的主要品种 ...... 1696  \n第三节 标线涂料的组分、配方和生产·..1696  \n一、热熔标线涂料 1696  \n二、溶剂标线涂料 1699  \n三、水性标线涂料 1701  \n四、双组分标线涂料 1702",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 45,
+        "chunk": "# 五、路面防滑涂料 1703",
+        "category": " Introduction"
+    },
+    {
+        "id": 46,
+        "chunk": "# 第四节 标线涂料的标准和检测 1703  \n\n一、标线涂料的标准 1703  \n二、标线涂料特定的检测项目 1707  \n三、按普通涂料常规检测的检测项目 1709  \n四、标线涂料的实用性能考核 1709",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 47,
+        "chunk": "# 第五节 标线施工材料的合理选用 1710  \n\n一、各种标线涂料的性能和优缺点对比 . 1710  \n二、标线使用性能室内模拟试验结果 1710  \n三、标线涂料的合理选用 中 1711  \n四、标线用玻璃珠的正确选择和使用 .... 1712",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 48,
+        "chunk": "# 第六节 标线涂料的施工 1715  \n\n一、标线施工的特点 1715  \n二、市售标线涂料的选择依据 1716  \n三、标线的分类 1716  \n四、标线质量的基本要求 1716  \n五、标线划设的工序 1717  \n六、各种标线涂料的施工设备、施工参数  \n和注意事项 1717",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 49,
+        "chunk": "# 第七节 标线施工质量的控制 1720",
+        "category": " References"
+    },
+    {
+        "id": 50,
+        "chunk": "# 、标线施工质量的要求 1720  \n\n二、热熔标线涂层缺陷形态、产生原因和防止措施 1722  \n三、溶剂、水性和双组分标线涂层缺陷形态、产生原因和防止措施 1723",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 51,
+        "chunk": "# 第八节 标线涂料的技术进展 1725  \n\n一、新开发的标线涂料 1725  \n二、国外有关标线涂料的技术标准 1725",
+        "category": " Introduction"
+    },
+    {
+        "id": 52,
+        "chunk": "# 三、中国、日本、英国、美国热熔反光标  \n\n线涂料标准的对比 1727  \n\n四、欧洲标准ZTVM02手册对反光标线材料的最低要求 1728五、标线涂料的发展趋势 1729参考文献 1730",
+        "category": " References"
+    },
+    {
+        "id": 53,
+        "chunk": "# 第四篇涂料制造过程控制",
+        "category": " Introduction"
+    },
+    {
+        "id": 54,
+        "chunk": "# 第一章 涂料生产设备 1731  \n\n第一节树脂、漆料和清漆生产  \n设备 潘元奇1731  \n一、概述 1731  \n二、反应装置 1733  \n三、加热设备 1756  \n四、净化设备 1765  \n\n第二节色漆生产设备 潘元奇1775  \n\n一、概述 1775  \n二、预分散设备 1776  \n三、研磨分散设备 1788  \n四、调漆设备 1817  \n五、过滤设备 1819",
+        "category": " Introduction"
+    },
+    {
+        "id": 55,
+        "chunk": "# 第三节过程管理 陈苹1822  \n\n一、ISO9000标准 1822  \n二、过程管理的理解和应用 1824  \n三、涂料生产和服务提供的过程管理 .1826  \n四、ISO14000简介 1828  \n参考文献 1832",
+        "category": " References"
+    },
+    {
+        "id": 56,
+        "chunk": "# 第二章 涂料．设计……· 戴蓉晖1834  \n\n第一节 绪论 1834  \n第二节 商务计划、项目建议和工厂选址 1834  \n第三节 可行性研究 1836  \n第四节 工厂基础设计和配套设施设计 .....1839",
+        "category": " Introduction"
+    },
+    {
+        "id": 57,
+        "chunk": "#  \n\n一、总图总平面布置 1839  \n二、公用及辅助工程 1839  \n三、建筑结构形式 1841  \n四、消防 1845  \n五、环境保护 1849  \n六、职业安全卫生 1851  \n工厂生产装置",
+        "category": " Introduction"
+    },
+    {
+        "id": 58,
+        "chunk": "# 第五节 1855",
+        "category": " References"
+    },
+    {
+        "id": 59,
+        "chunk": "# 一、设备设计应遵循的主要法规和标准、  \n\n规范 1855  \n二、树脂合成工艺 1855  \n三、涂料生产工艺 1856  \n四、涂料生产主要设备 1857  \n参考文献 1858",
+        "category": " References"
+    },
+    {
+        "id": 60,
+        "chunk": "# 第三章 涂料性能测试. 钱叶苗1860",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 61,
+        "chunk": "# 第一节 概论 1860  \n\n一、涂料性能 1860  \n二、涂料产品的技术指标与标准 1861  \n三、涂料检测的目的与特点 1863  \n四、涂料检测的发展与标准化 1864",
+        "category": " Introduction"
+    },
+    {
+        "id": 62,
+        "chunk": "# 第二节 涂料产品检测 1865  \n\n一、涂料产品的取样 1865  \n二、涂料原始状态的检测 1867  \n三、涂料施工性能的检测 1879",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 63,
+        "chunk": "# 第三节 涂膜性能检测 1885  \n\n一、均匀涂膜的制备 1886  \n二、涂膜的表观及光学性能的检测 1887  \n三、涂膜力学性能的检测 1891  \n四、涂膜耐物理变化性能的检测 1901  \n五、涂膜耐化学及耐腐蚀性能的  \n检测 1902  \n六、涂膜耐久性能的检测 1909",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 64,
+        "chunk": "# 第四节 涂料和涂膜的组成分析 ..1914  \n\n一、涂料和涂膜的组分分离 1914  \n二、涂料组分的单项分析 1915  \n三、涂料和涂膜的全面分析 1916  \n四、涂膜结构电子显微镜检查 1919  \n考文献 1920",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 65,
+        "chunk": "# 第五篇涂装过程控制",
+        "category": " Introduction"
+    },
+    {
+        "id": 66,
+        "chunk": "# 第一章 涂料涂装一体化的概念···.….…1922",
+        "category": " Introduction"
+    },
+    {
+        "id": 67,
+        "chunk": "# 第一节 涂装配套设计 刘会成1922  \n\n一、涂膜使用环境分析 1923  \n二、经济性分析 1923  \n三、表面处理的类型和方法的选择 1924  \n四、涂料的选择 1924  \n五、涂膜期待使用寿命分析 1926  \n六、涂装配套的选定 1926",
+        "category": " Introduction"
+    },
+    {
+        "id": 68,
+        "chunk": "# 二、产品说明书的具体内容 ·1932",
+        "category": " References"
+    },
+    {
+        "id": 69,
+        "chunk": "# 第四节 化学品安全技术说明书的  \n\n编写 赵琪慧1933  \n-、MSDS的意义 1934  \n二、对于MSDS 的编制要求 1934  \n三、MSDS的使用 1936  \n参考文献 1937",
+        "category": " References"
+    },
+    {
+        "id": 70,
+        "chunk": "# 第二章 底材表面处理标准和检测方法·.1938",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 71,
+        "chunk": "# 第二节 涂装工艺的制定 刘会成1928 第一节 钢材表面的物理处理  \n\n一、表面处理要求及注意事项 1928  \n二、涂装方法的选择 1928  \n三、涂料的准备 1929  \n四、涂装过程的要求 1929  \n五、涂膜检验 1929  \n六、安全注意事项 1930  \n七、涂装工艺指导书举例 1930",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 72,
+        "chunk": "# 第三节产品说明书的编制 008 000 000 006 赵琪慧1931",
+        "category": " Introduction"
+    },
+    {
+        "id": 73,
+        "chunk": "# 一、产品说明书的基本要求 1931  \n\n方法 刘会成1938  \n一、手工工具清理 1938  \n二、动力工具清理 1939  \n三、喷射处理 1940  \n四、钢铁表面处理的相关标准 1943",
+        "category": " References"
+    },
+    {
+        "id": 74,
+        "chunk": "# 第二节 钢材表面的化学  \n\n处理 林安方达经1950  \n一、除油脂 1951  \n二、酸洗 1952",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 75,
+        "chunk": "# 三、磷化处理 1953  \n\n四、铬酸盐处理 1954  \n五、金属表面化学处理的检测标准 1956",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 76,
+        "chunk": "# 第三节 其他金属的表面处理 1957  \n\n一、锌及锌合金的表面预处理 1957  \n二、铝及铝合金的表面预处理 1958",
+        "category": " References"
+    },
+    {
+        "id": 77,
+        "chunk": "# 第四节 混凝土的表面处理 林安1960",
+        "category": " References"
+    },
+    {
+        "id": 78,
+        "chunk": "# 一、清除表面油污和其他脏物 1960  \n\n二、清除水泥浮浆、泛碱物及其他松散物质 1960三、清除表面光滑的方法 1960四、混凝土表面气孔及缝隙的处理 是量0d重 1960第五节 塑料及橡胶表面处理标准和检测方法 +++ 林安1960一、塑料及橡胶表面处理的方法 1961二、塑料及橡胶表面处理的检测方法·.1962  \n\n刘林生 罗先平 刘志刚周琼辉1962  \n一、本材的种类及特征 1962  \n二、木材涂装前处理的意义 1962  \n三、木材涂装前处理的方法 1963  \n参考文献 1965",
+        "category": " References"
+    },
+    {
+        "id": 79,
+        "chunk": "# 第三章 涂料施．方法…· 李继华1967",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 80,
+        "chunk": "# 第一节刷涂法 .0 ·\\*967  \n\n一、刷涂的特点 1967  \n二、漆刷的类型 1968  \n三、刷涂基本操作方法 1968",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 81,
+        "chunk": "# 第二节 刮涂法 1969  \n\n一、刮涂用具 1970  \n二、刮涂的基本技法 1970",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 82,
+        "chunk": "# 第三节 辊刷涂法 1971  \n\n一、辊刷涂法的特点 1971  \n二、辊刷的构造 1971  \n三、辊刷的种类 1971  \n四、辊刷涂操作要领 1972  \n第四节 丝网法 1973  \n第五节 喷涂法 1973  \n一、空气喷涂法 1973  \n二、无空气喷涂法 1977  \n三、高压辅气喷涂法 1983  \n四、静电喷涂法 1984  \n五、气雾罐喷涂法 1988  \n六、喷涂方法性能比较 1989",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 83,
+        "chunk": "# 第六节 浸涂法 1990",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 84,
+        "chunk": "# 一、原理 1990  \n\n二、特点 1990  \n三、浸涂设备 1990  \n四、浸涂工艺 1991",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 85,
+        "chunk": "# 第七节 帘幕淋涂法 1991  \n\n一、原理 1991  \n二、幕涂法的特点 1991  \n三、幕涂设备组成 1992  \n四、幕涂工艺 1993",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 86,
+        "chunk": "# 第八节 抽涂法 1993  \n\n一、原理 1993  \n二、特点 1994",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 87,
+        "chunk": "# 第九节 辊涂法 1994  \n\n一、原理 1994  \n二、辊涂机的构造 1994  \n三、辊涂机的种类 1995  \n四、辊涂工艺 1995",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 88,
+        "chunk": "# 第六节 木材的表面处理 第十节 电泳涂装法 1996  \n\n、原理 1996  \n、特点 1997  \n三、工艺过程 1997  \n四、主要工艺参数 1997  \n五、电泳涂装设备 1998",
+        "category": " References"
+    },
+    {
+        "id": 89,
+        "chunk": "# 第十一节 自沉积涂漆法 1999  \n\n一、原理 1999   \n二、特点 1999   \n三、自泳涂装工艺 1999   \n四、影响因素 2000",
+        "category": " Introduction"
+    },
+    {
+        "id": 90,
+        "chunk": "# 第十二节 粉末涂装方法 2000  \n\n一、静电涂装法 2000  \n二、流化床涂装法 2001  \n三、静电流化床涂装法 2002  \n四、火焰喷涂法 2003",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 91,
+        "chunk": "# 第十三节 自动涂装系统 2004  \n\n一、概述 2004  \n二、往复涂装机 2004  \n三、涂装机器人 2006  \n参考文献 2007",
+        "category": " References"
+    },
+    {
+        "id": 92,
+        "chunk": "# 第四章 涂装现场管理和技术",
+        "category": " Introduction"
+    },
+    {
+        "id": 93,
+        "chunk": "# 第一节 涂料的贮存和现场物料管理·.·..….2008  \n\n一、涂料的贮存 2008  \n二、涂料的现场管理 2009  \n第二节涂装环境管理 2010  \n一、照明的管理 2010  \n二、通风的管理 2010  \n三、温度的管理 2011  \n四、相对湿度的管理 2012  \n五、空气污染影响的控制 2013  \n第三节 涂装缺陷及现场处置 2014  \n第四节涂装验收 2014  \n一、涂膜表面状态的验收 2014  \n二、涂膜厚度的验收 2015  \n三、涂膜物理性能的验收 2016  \n第五节涂料施工的技术服务 2017  \n一、涂料施工技术服务的目的 2017  \n二、技术服务人员的主要工作内容 2017  \n三、技术服务人员的工作方法 2017  \n四、施工前的准备工作 2018  \n五、现场技术服务工作的展开 2019  \n六、技术服务的记录与报告 2020  \n参考文献 2022",
+        "category": " References"
+    },
+    {
+        "id": 94,
+        "chunk": "# 第五章 涂装施工安全、卫生和污染治理  \n\n祝家洵 钱捷 任卫东王健2024  \n\n第一节 概述 2024",
+        "category": " Introduction"
+    },
+    {
+        "id": 95,
+        "chunk": "# 第二节 涂装施工的危险因素及防护措施···2024  \n\n一、涂装施工的危险因素 2024  \n二、防护措施 2027  \n三、安全技术教育培训 2029  \n第三节一般安全措施 一般安全措施—个人劳动保护  \n用品 2030  \n一、个人劳动保护用品 2030  \n二、个人劳动保护用品须具备的特征 2030  \n三、个人劳动保护用品的维护和报废规定2032",
+        "category": " Introduction"
+    },
+    {
+        "id": 96,
+        "chunk": "# 第四节 涂料的安全施工指导 2033  \n\n一、健康危害 2033  \n二、有工作危险的人员 2033  \n三、防护措施 2033  \n四、工作服与装备 2034  \n五、急救措施 2035  \n六、泄漏应急处理 2036",
+        "category": " Introduction"
+    },
+    {
+        "id": 97,
+        "chunk": "# 第五节 健康和环保措施 2036  \n\n一、健康安全 2036参考文献 2041  \n\n水膜而到达金属表面甚为容易，氧的阴极去极化作用不受阻碍，因而腐蚀速率很快。水膜过薄，电解质溶液不充分，影响金属的溶解；水膜过厚，氧分子通过水膜而达到金属表面的过程变得缓慢，使阴极去极化作用减缓，腐蚀速率变慢。  \n\n通过以上分析可知，空气相对湿度对于金属大气腐蚀的影响是何等的重要。然而，在某些情况下，水分对金属实际腐蚀行为的影响要比预料的轻微得多，而较有决定性的影响因素，是有关金属的特性和大气中某些污染性杂质的影响。出现这种情况的原因，是由于上述腐蚀总反应[式(3-3-3)］对金属腐蚀行为的作用，反而不及一系列副反应的作用大。  \n\nb.温度的影响环境温度及其变化是影响大气腐蚀的又一个重要因素。因为它影响着金属表面水蒸气的凝聚、各种腐蚀性气体和盐类的溶解度、水膜的电阻以及腐蚀电池中阴、阳极过程的速率。温度的影响还要和湿度条件综合起来考虑。一般认为，当相对湿度低于金属临界相对湿度时 $(<65\\%$ )，温度对于腐蚀的影响很小，此时无论气温多高，金属不易生锈；而当相对湿度达到金属腐蚀的临界相对湿度时，温度的影响会很大，此时温度每升高$10^{\\circ}C$ ，腐蚀速率提高约2倍。所以，在湿热带或雨季，温度越高生锈越严重。我国的大多数地区夏季气温高雨水多，是金属最易生锈的季节，更要采取各种加强措施做好防锈工作。温度的变化对金属腐蚀的影响，主要表现在凝露现象上。当含有一定量水蒸气的空气，冷却到露点温度以下时，水分就要凝集出来，这就是常说的凝露现象，而金属表面一旦凝露必然加重腐蚀。所以，在金属制品生产中，应尽量避免温度的剧烈变化。在北方高寒地区和昼夜温差较大的地区，应设法控制室内温度在一定的范围之内。  \n\nc.空气中污染物质的影响  \n\n· $\\mathrm{SO_{2}}$ ； $\\mathrm{CO_{2}}$ 等污染性物质 这些污染性物质，在工业城市大气中是大量存在的。一个  \n\n$10^{5}\\mathrm{kW}$ 的火力发电站，每昼夜从烟肉中排放出的$\\mathrm{SO_{2}}$ 就有100t之多。这些污染物大都是酸性气体，在潮湿的条件下，与水化合生成相应的无机酸，并与金属表面直接接触而严重地影响着金属大气腐蚀过程。如图3-3-12所示为在洁净的空气和含有 $0.01\\%~\\mathrm{SO_{2}}$ 空气中，钢铁腐蚀增重随时间的变化。在洁净的空气中(相当于乡村大气)，当相对湿度由0逐渐增大时，腐蚀缓慢。但是，当溶人 $0.01\\%$ $\\mathrm{\\SO}_{2}$ 之后 (相当于工业城市大气)，相对湿度由0增到 $75\\%$ 左右时，腐蚀虽与在洁净空气中的情况差不多，但当相对湿度达到 $75\\%$ 以上时，腐蚀增重突然上升，腐蚀速率急剧加快  \n\n根据腐蚀总反应[式（3-3-3)]，水分的出现概率是钢铁大气腐蚀的控制因素，然而当大气受到 $S0_{2}$ 等杂质污染之后， $\\mathrm{\\bfSO_{2}}$ 却似一种催化剂，使另一类型的腐蚀反应成为腐蚀过程的主反应。可用下列简化的化学方程式表示。  \n\n![](images/cfe73eaf65256b333c5f48b89775a78e787f5587f22022756aa93b9c1e4c97d8.jpg)  \n图3-3-12 相对湿度和 $50_{2}$ 对钢铁大气腐蚀的影响  \n\n$$\n2S{\\dot{\\mathrm{O}}}_{2}+{\\mathrm{O}}_{2}+2{\\mathrm{H}}_{2}{\\mathrm{O}}\\longrightarrow2{\\mathrm{H}}_{2}S{\\mathrm{O}}_{4}\n$$  \n\n$$\n2\\mathrm{Fe}+2\\mathrm{H}_{2}\\mathrm{SO}_{4}+\\mathrm{O}_{2}\\longrightarrow2\\mathrm{Fe}\\mathrm{SO}_{4}+2\\mathrm{H}_{2}\\mathrm{O}\n$$  \n\n$$\n2\\mathrm{FeSO_{4}}+\\frac{1}{2}\\mathrm{O}_{2}+5\\mathrm{H}_{2}\\mathrm{O}\\longrightarrow2\\mathrm{Fe}(\\mathrm{OH})_{3}+2\\mathrm{H}_{2}\\mathrm{SO_{4}}\n$$  \n\n结果由于 $\\mathrm{{sO}_{2}}$ 的作用催化了腐蚀进程。此时，大气中降水甚至会减慢腐蚀，因为空降水可洗涤水溶性硫酸铁和硫，并对连锁反应有阻碍作用。  \n\n$\\cdot$ 氯离子的作用氯离子的作用也有类似的催化金属腐蚀的效果，这种情况在海洋大气  \n\n区特别明显。在这种情况下，氯离子的催化作用使另一类型腐蚀反应成为腐蚀过程的主反应而非上述反应[式（3-3-6)」。  \n\n$$\n\\mathrm{Fe}^{2+}+2\\mathrm{Cl}^{-}+2\\mathrm{H}_{2}\\mathrm{O}\\longrightarrow\\mathrm{Fe}(\\mathrm{OH})_{2}+2\\mathrm{HCl}\n$$  \n\n$$\n4\\mathrm{Fe(OH)}_{2}+\\mathrm{O}_{2}+2\\mathrm{H}_{2}\\mathrm{O}\\longrightarrow4\\mathrm{Fe(OH)}_{3}\n$$  \n\n海洋占地球表面积的 $70\\%$ 以上，大多数的金属和合金均经受不住海水和多雾的海洋大气腐蚀。这里影响腐蚀的主要因素是积聚在金属表面的盐粒和盐雾，特别是氯离子。而盐的沉积量是与海洋气候环境、距离海面的高度、远近及金属暴露时间的长短有关。  \n\n表3-3-5表明了离海岸不同距离空气中 $C1^{-}$ 和 $\\mathbf{Na}^{+}$ 的含量。在海盐中，特别是氯化钙和氯化镁吸湿性最强，极易在金属表面形成液膜，每当昼夜或季节气候变化达到露点时尤其明显。但是，随着离海距离的增加含盐量迅速下降，一般在无强烈风暴时，深入内陆 $\\mathbf{l},\\hat{\\mathbf{6}}\\mathbf{km}$ 大气中含盐量即趋于零。  \n\n表3-3-5 不同海岸距离空气中 $c1^{-}$ 和 $\\mathbf{Na}^{+}$ 的含量变化  \n\n\n<html><body><table><tr><td rowspan=\"2\">海岸距离/km</td><td colspan=\"2\">离子含量/(mg/L)</td><td rowspan=\"2\">海岸距离/km</td><td colspan=\"2\">离子含量/（mg/L)</td></tr><tr><td>C1</td><td>Na</td><td>Cl</td><td>Na</td></tr><tr><td>0.4</td><td>16</td><td>8</td><td>48.0</td><td>4</td><td>2</td></tr><tr><td>2.3</td><td>g</td><td>4</td><td>86.0</td><td>3</td><td>一</td></tr><tr><td>5.6</td><td></td><td>3</td><td></td><td></td><td></td></tr></table></body></html>  \n\nd.酸碱盐的影响水膜中电解质溶液酸碱性： $\\mathsf{p H}$ 对金属腐蚀有两方面的影响，一方面随着溶液酸性提高， $\\mathrm{H^{+}}$ 浓度增加 $\\tt p H$ 减小，使其更易于在阴极区吸收电子而强化去极化作用，促进了阴极析氢反应，从而加速腐蚀；另一方面，由于 $\\mathfrak{p H}$ 的改变，影响着金属本身在水膜电解质溶液中的溶解度和保护膜的生成，进而影响金属腐蚀的进程。  \n\n不同的金属在不同的介质中腐蚀过程各不相同。例如 $Z n$ 、A1、Pb、 $\\mathtt{C u}$ 在酸和碱溶液中均不稳定。这是因为它们都具有一定的两性，即其氧化物在酸或碱中均能溶解。Fe和 $\\mathbf{Mg}$ 由于它们的氢氧化物在碱中实际上不溶解，能在金属表面生成相对稳定的保护膜，结果它们在碱性溶液中的腐蚀速率比在中性和酸性溶液中要小得多。所以，一般钢铁零件的防锈水或冷却液呈弱碱性 $(\\mathrm{p}\\bar{\\mathrm{H}}=8\\sim9)$ 。但是这种碱性液体用于有色金属就不行了。Ni和Cd在碱性溶液中较稳定，而在酸液中易腐蚀，这一点与铁相似。  \n\n中性盐类的影响有许多因素，其中它们与金属反应所生成的腐蚀产物在水膜溶液中的溶解度是重要的因素，如金属钠和钾的碳酸盐、磷酸盐，能在钢铁表面的阳极区生成不溶性碳酸铁、磷酸铁薄膜，从而使阳极过程显著减缓。硫酸锌能在钢铁表面阳极区形成不溶性氢氧化物$(Z_{n}S O_{4})$ )。因此，钢铁和这些盐溶液接触都会大大减缓腐蚀速率。另一些盐类，如铬酸盐、重铬酸盐等，能在金属表面形成保护膜而使金属钝化。实际上，不少金属的盐类是金属缓蚀剂。此外，金属在盐溶液中的腐蚀速率还与其阴离子特性有关。例如氯离子，它对金属腐蚀的影响很大。因为氯离子半径很小，极易穿透水膜而与金属作用，既破坏了金属表面的钝化膜，生成的氯化铁又溶于水，对金属毫无保护作用。同时，氯化物的存在增加了水膜的导电性，而水膜的导电性越强，金属越易锈蚀。氯化钠很强的吸湿性也会降低临界相对湿变，促进腐蚀发生。  \n\ne.其他因素的影响影响金属腐蚀的外界因素是十分繁多的，除了以上所述的一些主要因素外，还有一些因时因地的因素。例如，在热带地区，蚊、蝇及各类小昆虫甚多，它们在车间飞行，在金属表面爬动，会将脏物及户体黏附于零件表面，而引起生锈；金属制品在生产、运输过程中可能带来诸多腐蚀性因素，如人汗、热处理残盐洗涤不净、零件叠放、保管不善、积满灰尘等不文明生产行为，都可能诱发腐蚀；不同地区水质差异也会对金属腐蚀  \n\n产生不同的影响。  \n\n以上分别讨论了影响金属大气腐蚀的各种因素。在评定各种大气的腐蚀性时，应当以相同的金属做成试件，进行长期的大气腐蚀试验，才能较为准确地鉴定特定区域的大气对某种金属材料的腐蚀性。  \n\n(5）大气腐蚀环境分类材料在不同大气环境中的腐蚀破坏程度差异很大，例如，距海$24.3\\mathrm{m}$ 处的钢腐蚀速率为距海 $243.8\\mathrm{m}$ 处的大约12倍。试验表明，若以 $\\mathbf{Q235}$ 钢板在我国拉萨市大气腐蚀速率为1，则青海察尔汉盐湖大气腐蚀速率为4.3，广州城市为23.9，湛江海边为29.4，相差近30倍。因此，在防腐蚀工程设计和制定产品环境适应性指标时，均需按大气腐蚀环境分类进行。  \n\n大气环境分类一般有两种方法：一种是按气候特征划分，即自然环境分类；另一种是按环境腐蚀严酷性划分。后者更接近于应用实际而被普遍采用。国际标准ISO $9223\\sim9226$ 便是根据金属标准试片在环境中自然暴露试验获得的腐蚀速率及综合环境中大气污染物浓度和金属表面润湿时间进行分类。将大气按腐蚀性高低分为5类，即：C1（很低)；C2（低)；C3（中）；C4（高）；C5（很高）。  \n\n在涂料界，国际标准化组织又颁布了更有针对性的标准：ISO12944-1～8：1998《色漆和清漆—保护漆体系对钢结构的防腐保护》（Paints and varnishes—Corrosion protectionof steel structures by protective paint systems)。这是一部在国际防腐界通行的、权威的防护涂料与涂装技术指导性国际标准。目前，在国内涂料、涂装行业、腐蚀与防护行业及相关设计研究院所、高等学校，以及在重大防腐工程设计、招投标及施工过程中都使用到这一综合性标准。标准共分八个部分。  \n\n其中第2部分系统地介绍了大气腐蚀环境分类。而导致腐蚀产生的环境因素主要有大气、各类水质和土壤三方面，所以标准规定了大气腐蚀环境级别和钢结构在水下和土壤中的腐蚀环境分类（表3-3-6和表3-3-7)。参照ISO12944-5，就可以针对某种腐蚀环境设计涂装系统（详见本章第三节重防腐涂装设计)。其中，该标准根据不同大气环境的腐蚀性及其特征污染物质的污染程度，将涂料产品面对的大气环境大致分为乡村大气、城市大气、工业大气和海洋大气四种类型。  \n\n表3-3-6ISO12944-2对大气腐蚀环境的分类以及典型环境的举例  \n\n\n<html><body><table><tr><td rowspan=\"3\">腐蚀 级别</td><td colspan=\"4\">单位面积的质量/厚度损失(暴露1年后)</td><td colspan=\"2\">温和的气候中，典型的环境举例（仅供参考）</td></tr><tr><td colspan=\"2\">低碳钢</td><td colspan=\"2\">锌</td><td rowspan=\"2\">外部的</td><td rowspan=\"2\">内部的</td></tr><tr><td>质量损失 /（g/m²)</td><td>厚度损失 /μm</td><td>质量损失 /(g/m²)</td><td>厚度损失 /μm</td></tr><tr><td>C1 很低</td><td>≤10</td><td>≤1.3</td><td>≤0.7</td><td>≤0.1</td><td></td><td>具有干净空气的建筑，如办 公室，商店，学校</td></tr><tr><td>C2 低</td><td>10～200</td><td>1.3~25</td><td>0.7~5</td><td>0.1～0.7</td><td>空气低污染，主要在乡村 地区</td><td>会发生露水的建筑，如体育 馆，航空站</td></tr><tr><td>C3 中等</td><td>200~400</td><td>25～50</td><td>5~15</td><td></td><td>在城市中，有工业气体，受 0.7～2.1SO2污染程度中等，或有低 盐分的海滨地区</td><td>湿度高和有一些空气污染的 生产车间，如食品加工厂、洗衣 店、酿酒厂、奶厂等</td></tr><tr><td>C4 高</td><td>400~650</td><td>50~80</td><td>15~30</td><td>2.1~4.2</td><td>工业区和具有中等盐分的 沿海地区</td><td>化工厂、游泳池、海船、码 头等</td></tr><tr><td>C5-1 很高(工业）</td><td>650~1500</td><td>80~200</td><td>30~60</td><td>4.2~8.4</td><td>高湿度的工业区，同时空 气污染严重</td><td>温度通常在露点以下，高污 染地区</td></tr><tr><td>C5-M 很高(海上)</td><td>650～1500</td><td>80~200</td><td>30~60</td><td>4.2~8.4</td><td>高盐分沿海或海上</td><td>温度通常在露点以下，高污 染地区</td></tr></table></body></html>\n\n注：1.该表中所用的腐蚀级别换算值同ISO9223一样。2.在沿海、湿热地区，如果质量和厚度损失超过 $C5-M$ 所列出的，那么在选择结构防腐涂料时需特别注意。  \n\n表3-3-7ISO12944-2对于钢结构所处水和土壤环境的分类  \n\n\n<html><body><table><tr><td>分类</td><td>环境</td><td>环境和建筑举例</td></tr><tr><td>Iml</td><td>新鲜水</td><td>河流装置水电厂</td></tr><tr><td>Im2</td><td>海水或盐水</td><td>港口区域的建筑结构，如：水闸门、锁等，海上结构</td></tr><tr><td>Im3</td><td>土壤</td><td>储油罐、钢桩、钢管</td></tr></table></body></html>  \n\n在我国，20世纪90年代也制定并颁布了类似标准，即GB/T15957—1995《大气环境腐蚀性分类》。该标准系以裸露的碳钢（以A3钢为基准）在不同大气环境下腐蚀等级划分和防护涂料及其类似防护材料品种选择为重要依据。该标准主要根据碳钢在不同大气环境下暴露第一年的腐蚀速率（ $\\bf(m m/a)$ ，将腐蚀环境类型分为：无腐蚀、弱腐蚀、轻腐蚀、中腐蚀、较强腐蚀、强腐蚀六大类，并给出不同腐蚀环境下的腐蚀速率等（表3-3-8)。该标准还按照影响钢铁腐蚀的气体成分与含量，将腐蚀性气体分为A、B、C、D四类，详见表3-3-9。  \n\n表3-3-8GB/T15957—1995大气腐蚀环境类型的技术指标  \n\n\n<html><body><table><tr><td colspan=\"2\" rowspan=\"2\">腐蚀类型</td><td rowspan=\"2\">腐蚀速率 /(mm/a)</td><td colspan=\"3\">腐蚀环境</td></tr><tr><td>环境气体类型</td><td>相对湿度(年平均)/%</td><td>大气环境</td></tr><tr><td>等级 I</td><td>名称 无腐蚀</td><td><0.001</td><td>A</td><td><60</td><td>乡村大气</td></tr><tr><td>Ⅱ</td><td>弱腐蚀</td><td>0.001~0.025</td><td>A</td><td>60~75</td><td>乡村大气</td></tr><tr><td>Ⅲ</td><td>轻腐蚀</td><td>0.025~0.050</td><td>B A B</td><td><60 >75 60~75</td><td>城市大气 乡村大气 城市大气和工业大气</td></tr><tr><td>IV</td><td>中腐蚀</td><td>0. 050~0.20</td><td>C B C</td><td><60 >75 60~75</td><td>乡村大气 工业大气和海洋大气</td></tr><tr><td></td><td>较强腐蚀</td><td>0.20~1.00</td><td>D C</td><td><60 >75</td><td>工业大气</td></tr><tr><td>VI</td><td>强腐蚀</td><td>1~5</td><td>D D</td><td>60~75 >75</td><td>工业大气</td></tr></table></body></html>\n\n注：在特殊场合与额外腐蚀负荷作用下，应将腐蚀类型提高等级。1.机械负荷： $\\textcircled{1}$ 风沙大的地区，因风携带颗粒（沙子等）使钢结构发生磨蚀的情况； $\\textcircled{2}$ 钢结构上用于（人或车辆）通行或有机械重负载并定期移动的表面。2.经常有吸潮性物质沉积于钢结构表面的情况。  \n\n表3-3-9 环境气体分类GB/T15957—1995  \n\n\n<html><body><table><tr><td>气体类别</td><td>腐蚀性物质名称</td><td>腐蚀性物质含量/（g/m）</td><td>气体类别</td><td>腐蚀性物质名称</td><td>腐蚀性物质含量/（g/m）</td></tr><tr><td rowspan=\"5\">A</td><td>二氧化硫</td><td><0.5</td><td rowspan=\"5\">C</td><td>氯化氢</td><td>0.05~5</td></tr><tr><td>氟化氢</td><td><0.05</td><td>二氧化硫</td><td>10~-200</td></tr><tr><td>硫化氢</td><td>≤0.01</td><td>氟化氢</td><td>5~10</td></tr><tr><td>氮的氧化物</td><td><0.01</td><td>硫化氢</td><td>5~100</td></tr><tr><td>氯</td><td><0.01</td><td>氮的氧化物</td><td>5~25</td></tr><tr><td rowspan=\"6\">B</td><td>氯化氢 二氧化碳</td><td><0.05 >2000</td><td></td><td>氯</td><td>1~5</td></tr><tr><td>二氧化硫</td><td>0. 5~10</td><td></td><td>二氧化硫</td><td>200～1000</td></tr><tr><td>氟化氢</td><td>0.05~5</td><td></td><td>氟化氢</td><td>10~100</td></tr><tr><td>硫化氢</td><td></td><td>D</td><td>硫化氢</td><td>>100</td></tr><tr><td>氮的氧化物</td><td>0.01～5</td><td></td><td>氮的氧化物</td><td>25~100</td></tr><tr><td>氯</td><td>0. 1~5 0.1~1</td><td></td><td>氯</td><td>5~10</td></tr></table></body></html>\n\n注：当大气中同时含有多种腐蚀性气体，则腐蚀级别应取最高的一种或几种为基准。  \n\n（6）防止钢铁大气腐蚀的主要措施  \n\n① 金属材料自身的抗蚀性：如在钢中加人Cu、P、Cr、Ni等，例如美国的COr-Ten钢，其耐大气腐蚀性能为碳钢的4～8倍。此外，通过均匀化热处理、表面渗氮、渗铬、渗铝等工艺方法，也可以提高金属材料的抗蚀性。  \n\n$\\textcircled{2}$ 有机、无机涂层和金属镀层。$\\textcircled{3}$ 缓蚀剂和暂时性防护涂层。$\\textcircled{4}$ 处理法防蚀：最常见的有氧化膜和磷化膜两种。$\\textcircled{5}$ 环境法防蚀。a.干燥空气封存法，也称控制相对湿度法。一般使空气相对湿度控制在 $\\leq35\\%$ ，金属则不易生锈，非金属也不易长霉。b.充氮封存法。c.隔离污染源法。$\\textcircled{6}$ 化学阴极保护法。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 98,
+        "chunk": "# 2.金属在其他环境中的腐蚀  \n\n在自然环境中大气腐蚀是金属腐蚀的最常见的主要形式。而在其他自然环境中，金属腐蚀也各有其特点。如海水腐蚀、土壤腐蚀、微生物腐蚀等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 99,
+        "chunk": "# (1）海水腐蚀  \n\n$\\textcircled{1}$ 海水的特性海洋约占地球表面积的7/10，海水中溶有大量的以 $\\mathbf{NaCl}$ 为主的盐类，是自然界量最大的天然电解质液体，具有极强的腐蚀性。一般以盐度（或氯度）来表示海水中含盐量。盐度 $5(\\%)$ 或氯度CI $(\\frac{\\pi}{2})$ ，分别指在 $\\mathbf{1000g}$ 海水中溶解的固体盐类（或氯离子）的总质量（g)，两者互算经验公式为：  \n\n$$\nS(\\%)=1.80655\\mathrm{Cl}(\\%)\n$$  \n\n正常海水的盐度一般在 $32\\%0.737.5\\%$ 之间变化。通常取盐度 $35\\text{\\textperthousand}$ （相应的氯度为 $19\\%$ ）作为海洋性海水的盐度平均值。海水的总盐度随地区而变化，在某些海区和隔离性的内海中，盐度有较大的变化，如在江河的入海口，海水被稀释，盐度变小。在地中海、红海这些封闭性海中，由于水分急速蒸发，盐度可高达 $40\\text{\\textperthousand}$ 。表3-3-10列出了海水中盐类的主要组成和各种的含量。  \n\n表3-3-10 海水主要成分及各种离子含量  \n\n\n<html><body><table><tr><td>组分</td><td>含量/（g/kg)</td><td>组分</td><td>含量/（g/kg)</td></tr><tr><td>氯化物 钠 硫酸盐 镁 钙 钾</td><td>19.353 10.76 2.712 1.294 0.413</td><td>重碳酸盐 澳化物 锶 硼 氟</td><td>0.142 0.067 0.008 0.004 0.001</td></tr><tr><td>阳离子 Na+</td><td>0.378 w/% 1.8556</td><td>阴离子 CI-</td><td>w/% 1.8980</td></tr><tr><td>Mg²+ Ca2+ K+ Sr²+</td><td>0.1273 0.400 0.0380 0.0013</td><td>SO²- HCO Br- HBO F-</td><td>0.2649 0.0140 0.0065 0.0026 0.0001</td></tr></table></body></html>  \n\n海水有很高的电导率，海水平均电导率约为 $4\\times10^{-2}{\\mathrm{S/cm}}$ ，远远超过河水 $(2\\times10^{-4}\\mathrm{S}/$ $\\mathrm{cm}$ ）和雨水 $(1\\times10^{-5}{\\bf S/c m})$ ）的电导率。海水 $\\mathbf{\\pH}$ 通常为 $8.1\\sim8.2\\$ ，且随海水深度变化而  \n\n![](images/ad7cc00a01dcb2cf22dc6621edcb3b72cf99ea2836cb21d321628a43deb6f3e3.jpg)  \n图3-3-13 钢桩在不同海水深度中腐蚀速率的变化  \n\n变化。  \n\n海水含氧量是海水腐蚀的主要因素。在海面正常情况下，海水表面层被空气饱和，标准大气压空气饱和下的溶氧量（氧的浓度）随水体在 $(5\\sim10)\\times10^{-6}$ 范围内变化。  \n\n海水是一种含有多种盐类近中性的电解质溶液，并溶有一定的氧，这决定了金属海水腐蚀的电化学特征。  \n\n$\\textcircled{2}$ 海水腐蚀机理与特征按照海洋工程钢结构工况条件，即金属与海水接触的情况，可将海洋腐蚀环境分为海洋大气区、飞溅区、潮汐区、全浸区和海泥区（图3-3-13)。表3-3-11列出普通碳钢在不同海水环境中的腐蚀速率。不难看出，飞溅区腐蚀速率最大，海泥区腐蚀速率最小，飞溅区金属表面潮湿，供氧充足，更因为干湿交替，盐分浓缩，腐蚀条件最充分，所以腐蚀速率最快。而海泥区充氧不足，腐蚀反应较慢，但可能存在泥浆-海水界面腐蚀或者微生物的腐蚀。  \n\n表3-3-11不同海洋环境中普通碳钢平均腐蚀速率  \n\n\n<html><body><table><tr><td>海洋环境</td><td>平均腐蚀速率/(mm/a)</td><td>海洋环境</td><td>平均腐蚀速率/(mm/a)</td></tr><tr><td>海洋大气区</td><td>0.128</td><td>全浸区</td><td>0.090</td></tr><tr><td>飞溅区</td><td>0.372</td><td>海泥区</td><td>0.075</td></tr><tr><td>潮汐区</td><td>0.083</td><td></td><td></td></tr></table></body></html>  \n\n由于影响因素的多元性、复杂性、多变性，使金属的海水腐蚀行为极为复杂，至今尚有许多问题和现象不能解释，一些腐蚀机理未能弄清楚。下面仅介绍学术界公认的内容，供参考。  \n\n![](images/fadffd14a72187e56f599ff956292d9827c30523439c4a76699ee90135ffee9e.jpg)  \n\na.除了镁及其合金既有吸氧腐蚀又有析氢腐蚀外，其他金属的腐蚀都属于氧去极化  \n过程。b.钢铁、锌、铜等常用金属的海水腐蚀阳极极化阻滞作用很小。极少数像钛、锆、锯、  \n钼等稀有金属才能在海水中保持钝态。c.海水是一种强电解质液体，所以电阻性阻滞作用很小。d.海水腐蚀形态主要是点腐蚀和缝隙腐蚀，高流速易产生冲击腐蚀和空蚀。$\\textcircled{3}$ 海水腐蚀影响因素  \n\na.盐度如图3-3-14所示，当盐浓度超过一定值时，由于氧的溶解度降低，使金属的腐蚀速率下降。  \n\n![](images/296f602e47c3cb5f45b3961209a64eb1ef0ce8757c31cc99a602a9fb88c0e067.jpg)  \n图3-3-14 钢的腐蚀速率与 $\\mathrm{\\DeltaNaCl}$ 浓度的关系  \n\nb.氧含量这是影响海水腐蚀的一个重要因素。海水中充氧量增加，强化了氧去极化阴极过程，金属的腐蚀速率增加。  \n\nc.温度一般认为，海水中温度每升高$10^{\\circ}C$ ，海水中金属腐蚀速率提高约1倍（图3-3-15)，但随着温度上升，氧的溶解度随之下降，又削弱了温度效应。一般来说，铁、铜和它们的合金在炎热的环境或季节里，海水腐蚀速率要快些  \n\nd.海水流速许多金属的腐蚀与海水流速有较大的关系。尤其是钢铁、铜等常用金属存在一个临界流速，超过此流速，金属腐蚀明显加快。碳钢的腐蚀速率随流速的变化如图3-3-16所示。但对某些金属则不然，有一定流速能促进钛、镍合金、高铬不锈钢的钝化和耐蚀性。  \n\ne.海洋生物的影响 海洋生物因素对腐蚀的影响很复杂。在本书船舶涂料等有关章节将有较详细的讨论。这里指出的是微生物的生理作用会产生氨、 $\\mathrm{CO}_{2}$ 及 $\\mathbf{H}_{2}\\mathbf{S}$ 等腐蚀性气体，尤其是硫酸还原菌的活动，会加速金属的腐蚀。  \n\n![](images/af62efe5cebd981b4c4b8807cc7c9127bbcf3a973ccde6728b087cc5235475e4.jpg)  \n图3-3-15 海水深度与温度、盐的 浓度及溶解氧的关系 1—溶氧量；2—总盐量；3—水温  \n\n$$\n2S+S O_{2}+2H_{2}O\\longrightarrow2H_{2}S O_{4}\n$$  \n\n![](images/469f449086a82ed9c3dd6bf816b8eb523a48c6526977d193a32d56671e6e4051.jpg)  \n图3-3-16 海水流动速度对低碳钢腐蚀的影响  \n\n$\\textcircled{4}$ 海水腐蚀的防护  \n\na.合理选择耐蚀性金属新材质钛、镍、铜合金在海水中较耐蚀，但价格高，只能用于关键部件，而量大面广的钢铁材料，一般在海洋环境下易腐蚀，需要外加防蚀措施。  \n\nb.使用涂层的方法 这是使用最普遍而实用的方法，如船舶涂料、重防腐涂料等。  \n\nc.阴极保护 这也是防止海水腐蚀的常用方法之一，一般只在全浸区才有效。  \n\n(2）土壤腐蚀土壤腐蚀顾名思义是指不同区域的土壤不同组分和性质对材料的腐蚀。而金属在土壤中的腐蚀属于最常见的实际腐蚀问题。如埋地长输管线、地下通讯设备、各类地下金属构件等，均不断地遭受土壤腐蚀，而且地下设施维修困难，结果造成很大的危害。因此，研究土壤腐蚀的规律和防护措施具有重要意义。  \n\n$\\textcircled{1}$ 土壤性质与特点土壤是一个集气、液、固三态物质为一体的复杂系统。其组成是由各种颗粒状的矿物质、有机物质及水分、空气和微生物等组成的多相的并且具有生物学活性及离子导电性的多孔毛细管胶体体系。  \n\n在20世纪初，所有的地下腐蚀都归结于来自有轨电车和地铁的杂散电流。然而研究发现，在没有杂散电流的土壤里，也有腐蚀现象发生，这表明土壤本身有腐蚀性。经大量研究发现土壤的腐蚀性和土壤的电阻率、孔隙度（氧含量）、含水量、可溶性盐类、pH、微生物以及它们之间的相互作用有关，而且这些因素还常常随时间、空间而发生变化，十分复杂。  \n\n$\\textcircled{2}$ 土壤腐蚀的电极过程土壤中最常用的金属结构是钢铁，以钢铁为例，土壤腐蚀的电极过程如下。  \n\na.阴极过程 主要是氧的还原  \n\n$$\n\\mathrm{O}_{2}+2\\mathrm{H}_{2}\\mathrm{O}+4\\mathrm{e}^{-}\\longrightarrow4\\mathrm{OH}^{-}\n$$  \n\n而在酸性土壤里会发生析氢反应。  \n\n$$\n\\mathrm{2H^{+}+2e^{-}\\longrightarrow H_{2}~4}\n$$  \n\n在硫酸还原菌参与下， $\\mathrm{SO_{4}^{2-}}$ 的还原是土壤腐蚀的阴极过程  \n\n$$\n\\mathrm{SO_{4}^{2-}+4H_{2}O+8e^{-}}\\longrightarrow\\mathrm{S^{2-}+8O H^{-}}\n$$  \n\n某些电极电位比铁更正的金属离子也可能被还原，也是一种阴极过程。  \n\n$$\n\\mathrm{M^{3+}+e^{-}\\Gamma\\xrightarrow{}M^{2+}}\n$$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 100,
+        "chunk": "# b．阳极过程  \n\n$$\n\\mathrm{Fe}+n\\mathrm{H}_{2}\\mathrm{O}\\longrightarrow\\mathrm{Fe}^{2+}\\cdot n\\mathrm{H}_{2}\\mathrm{O}+2\\mathrm{e}^{-}\n$$  \n\n只有在酸性较强的土壤中，才有相当数量的铁氧化成为二价或三价的离子，以离子状态存在于土壤之中。在稳定的中性或碱性土壤中：  \n\n在阳极区有氧存在时， $\\mathrm{Fe(OH)_{2}}$ 能氧化成为溶解度很小的 $\\mathrm{Fe(OH)_{3}}$ 。  \n\n$$\n2\\mathrm{Fe(OH)}_{2}+\\frac{1}{2}\\mathrm{O}_{2}+\\mathrm{H}_{2}\\mathrm{O}\\longrightarrow2\\mathrm{Fe(OH)}_{3}\n$$  \n\n$\\mathrm{Fe(OH)_{3}}$ 产物很不稳定，它会变成更稳定的产物。  \n\n当土壤中存在 $\\mathrm{\\DeltaHNCO_{3}^{-}}$ ， $\\mathrm{CO_{3}^{2-}}$ ， $S^{2-}$ 时：  \n\n$$\n\\mathrm{Fe^{2+}+C O_{3}^{2-}\\longrightarrow F e C O_{3}}\n$$  \n\n$$\n\\mathrm{Fe}^{2+}+\\mathrm{S}^{z-}\\xrightarrow{}\\mathrm{FeS}\n$$  \n\n$\\textcircled{3}$ 土壤腐蚀的影响因素如前所述，土壤的腐蚀性和土壤的电阻率、孔隙度（氧含量)、含水量、可溶性盐类、 $\\mathbf{pH}$ 、微生物以及它们之间的相互作用有关，简述如下。  \n\na.孔隙度（氧含量）孔隙度较大有利于氧气渗透。一般来说，孔隙度大，氧含量增大，是腐蚀初始发生的促进因素而加剧腐蚀。但也须考虑到在透气性良好的土壤中更易生成具有保护能力的腐蚀产物保护膜层，阻碍金属的阳极溶解，使腐蚀速率减慢下来。有许多相互矛盾的实例，如在考古发掘时发现埋在透气不良的土壤中的铁器历久无损，但另一些例子说明在密不透气的黏土中金属常发生更严重的腐蚀。造成情况复杂的因素在于有氧浓差电池、微生物腐蚀等因素的综合影响。需具体情况具体分析，不能一概而论。  \n\nb.含水量土壤中含水量对腐蚀的影响很大。当土壤含水量很高时，氧的扩散渗透受阻而腐蚀减缓，随着含水量的减少，氧的去极化变易，腐蚀速率增加，当含水量降落到约$10\\%$ 以下，由于水分的短缺、阳极极化和土壤比电阻加大，腐蚀速率又急速降低。另外，从长距离氧浓差宏电池的作用看，随着含水量增加，土壤比电阻减少，氧浓差电池的作用也增加。在含水量为 $70\\%\\sim90\\%$ 时出现最大值。当土壤含水量再增加接近饱和时，氧浓差腐蚀的作用减少了。在实际情况下，埋得较浅、含水量少的部位的管道是阴极，埋得较深、接近地下水位的管道，因为土壤湿度较大，成为氧浓差电池的阳极而被腐蚀。  \n\nc.电阻率土壤电阻率与土壤孔隙度、含水量及含盐量等因素有关。一般来说，土壤电阻率越小，土壤腐蚀越严重。但电阻率的大小与腐蚀速率之间并不存在明显的关系，当电阻率在 $5\\sim30\\Omega\\cdot\\mathrm{m}$ 左右时，随着电阻率的升高，腐蚀速率随之下降，而且趋势明显，当电阻率在 $30\\sim100\\Omega\\cdot\\mathrm{m}$ 左右时，腐蚀速率随电阻率升高而降低的趋势变得较为平缓。  \n\nd.酸度土壤酸度的来源很复杂，有的来自土壤中的酸性矿物质，有的来自生物和微生物的生命活动所形成的有机酸和无机酸，也有的来自于工业污水等人类活动造成的土壤污染。大部分土壤属中性范围， $\\mathsf{p H}$ 处于 ${\\mathfrak{G}}{\\sim}{\\mathfrak{g}}$ 。也有 $\\bar{\\mathbf{p}}\\bar{\\mathbf{H}}$ 为 $8\\sim10$ 的碱性土壤（如盐碱土）及$\\bar{\\mathsf{p H}}$ 为 $3\\sim6$ 的酸性土壤（如沼泽土、腐殖土)。随着土壤酸度增高，土壤腐蚀性增加，因为在酸性条件下，氢的阴极去极化过程已能顺利进行，强化了整个腐蚀过程，当土壤中含有大量有机酸时，其 $\\mathbf{p}\\mathbf{H}$ 虽然近于中性，但其腐蚀性仍然很强。  \n\ne.含盐量通常土壤中含盐量约为 $(80\\sim1500)\\times10^{-6}$ ，在土壤电解质中的阳离子一般是钾、钠、镁、钙等离子，阴离子是碳酸根、氯离子和硫酸根离子。土壤中含盐量大，土壤的电导率也增加，因而增加了土壤的腐蚀性。氯离子对土壤腐蚀有促进作用，所以在海边潮汐区或接近盐场的土壤，腐蚀性更强。但碱土金属钙、镁的离子在非酸性土壤中能形成难溶的氧化物和碳酸盐，在金属表面形成保护层而减少腐蚀。富钙、镁离子的石灰质土壤就是一个典型的例子，同样硫酸根离子也能和铅作用生成硫酸铅的保护层。硫酸盐和土壤腐蚀另一个重要关系是和微生物腐蚀有关。  \n\n$\\textcircled{4}$ 土壤腐蚀的主要形式如上所述，土壤腐蚀基本上属于电化学腐蚀，通常分为微观腐蚀电池（简称微腐蚀）和宏观腐蚀电池（简称宏腐蚀）两种形式。  \n\na.微观腐蚀电池钢铁材料，例如埋地钢管，主要由于本身成分、杂质及金相组织的  \n\n不均匀性等，造成钢管表面各部位常具有不同的电极电位而形成的腐蚀电池，属于微观腐蚀电池。如制管上的缺陷，管道表面可能夹杂有不同杂质、熔渣、焊缝、氧化皮等，与其基体金属在成分与性质上差异较大，当这种钢管表面差异性很大的管道埋地后，不同部位之间便产生了电极电位差，如钢管的焊缝熔渣与本体金属间的电位差可能高达 $0.275\\mathrm{V}$ 。例如，如图  \n\n![](images/ef2383911d89960e1dfcaf116004f11df32cf28737f545a1d36e160c19fd36b4.jpg)  \n图3-3-17 埋地钢管表面杂质（阴极）与钢管（阳极）形成的腐蚀微电池示意  \n\n3-3-17所示的是理地钢管表面杂质与钢管所生成的腐蚀微电池。  \n\nb.宏观腐蚀电池当埋地管线从土壤（A）进人另一种土壤（B）时，便形成了宏观腐蚀电池，它对埋地管线造成的腐蚀危害尤为严重。  \n\n钢管/土壤（A）//土壤（B)/钢管  \n\n主要因为土壤腐蚀介质差异引起的，例如，当长输埋地钢管通过土壤结构不同和潮湿程度不等的土壤时（如砂土和黏土)，由于充气不均匀而形成氧差电池的腐蚀，如图3-3-18所示。处在砂土中的管段，由于氧容易渗人，电位较高而成为阴极，而处于黏土中的管段，由于缺氧，电位低而成为阳极，这样钢管便在砂土段与黏土段之间形成了氧浓差腐蚀电池，属于宏观腐蚀电池。  \n\n![](images/9f27ca7ed23bd157e9cdbbf683c50e95199a09f065b0a3257f2b91849233abd4.jpg)  \n图3-3-18 管道在结构不同的土壤中所形成的氧浓差宏观电池  \n\nc.杂散电流腐蚀 杂散电流是在土壤介质中的导体因绝缘不良而漏失出来的电流，  \n\n或者说是正常电路以外流人的大小、方向都不固定的电流。地下埋设的金属构件物在杂散电流影响下所发生的腐蚀成为杂散电流腐蚀。正由于土壤中有杂散电流，对绝缘不良的管道，它可从绝缘损坏的某一点上流入管道，沿管道而在绝缘损坏的另一点上流出，流回杂散电流源头。在这种情况下，杂散电流从土壤进入金属管道的地方是腐蚀电池的阴极区，而电流经管道流出处则为阳极区，埋在阴极区土壤金属不会受到什么影响，而在阳极区则集中发生腐蚀。特别指出的是，在实际工程中杂散电流源的形成很普遍，如高压输配电系统的接地体、电气化铁路沿线、电解工厂、城市有轨电车、外接电流阴极保护装置等。如图3-3-19所示为电气化火车附近的埋地管道受杂散电流影响而引起的腐蚀破坏。  \n\n![](images/b60051fbf10860b972f1ffb1f4dcf1c6c2235010b0bc9d81c4035de406cb9b2f.jpg)  \n图3-3-19 土壤中的杂散电流影响而引起的埋地管道腐蚀示意  \n\n$\\textcircled{5}$ 土壤腐蚀的防治措施  \n\na.涂层保护。涂层保护一般采用熔结环氧（粉末涂料）、无溶剂液体环氧及沥青涂层作为管道外防腐涂层。为增强涂层的力学性能，一般外缠三层聚乙烯（PE）薄膜。防护总厚度为 $2,2{\\sim}2,9\\mathrm{mm}$  \n\n另外，对于气体长输管线的管道内壁喷涂减阻型环氧涂料，一方面为了降低气体与管道内壁的流动阻力，提高输气效率，同时为了防止管道内壁腐蚀，内涂层的厚度一般在$65\\sim75\\mu\\mathrm{m}$ 0  \n\nb.提高地下钢结构的绝缘性或使漏出电流沿适当回路流人供电网。  \n\nc.阴极保护。  \n\n(3）钢铁的微生物腐蚀凡是同水、土壤或湿润空气相接触的金属设施，都可能遭到微生物腐蚀。微生物包括真菌和细菌。与腐蚀有关的微生物主要有硫酸盐还原菌、硫氧化菌和铁细菌。近十年来，由于细菌腐蚀给冶金、航海、石油、石化、化工、煤炭、市政等行业带来了损失，因此，控制细菌腐蚀已成为一些企业正常生产的关键环节之一。  \n\n自然环境中的细菌成千上万，但参与金属腐蚀过程的菌种不多，根据生物新陈代谢模式，一般把腐蚀性细菌分为喜氧性菌和厌氧性菌两大类。  \n\n$\\textcircled{1}$ 喜氧性菌腐蚀喜氧性菌（或称嗜氧性菌）是指环境中有游离氧的条件下才能生存的一类细菌，主要有铁细菌和硫氧化菌。  \n\n②厌氧性菌腐蚀厌氧性菌是指在缺乏游离氧或几乎无游离氧的条件下才能生存，有氧反而不能生存的一类细菌，主要有硫酸盐还原菌。硫酸盐还原菌所造成的腐蚀一般呈局部腐蚀。  \n\n③细菌联合作用下的腐蚀喜氧性细菌和厌氧性细菌各自所需的生存条件截然不同，但在实际环境中，往往由喜氧性细菌的腐蚀造成了厌氧的局部环境，从而使厌氧性菌亦得到繁殖。这样，两类细菌相辅相成便加速了金属的腐蚀。细菌腐蚀的控制：  \n\na.外加电流阴极保护或牺牲阳极保护可以抑制细菌腐蚀；b.采用非金属覆盖层或金属镀层的方法；c.使用有机涂层在必要时加入适量灭菌剂、防霉剂等，如使用抗菌涂料和防霉涂料；d.在介质中投放高效、低毒的杀菌剂和除垢剂才能收到更好的效果。此外，施行清洁生产和文明生产，使设备维持清洁状态，亦是减少细菌腐蚀的一项不能忽视的措施。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 101,
+        "chunk": "# 第二节 重防腐涂料简述  \n\n所谓重防腐涂料，目前并无确切的定义。由日文转译的英文为Heavy-duty paint，其核心含义为涂层体系经适当涂装后在严酷的腐蚀环境下为底材提供较长期的防腐蚀保护。  \n\n一般来说，重防腐涂料在海洋环境和化工大气中通常可使用10年以上；而在酸、碱、盐及溶剂介质中，并有一定温度的条件下，一般可使用5年以上。目前，重防腐涂料的应用范围极为广泛，涉及现代化产业的各个领域：如桥梁工程、电力工程、海洋工程、石油化工、汽车和机车、大型贮罐、长输管道、地下工程、冶金、船舶、集装箱、港口设施、工程机械以及各类户外建筑钢结构等。重防腐涂料与涂装技术的发展是与现代工业技术的发展密切相关的，涉及多种学科的发展，如材料学、腐蚀理论、表面处理、新型合成材料、颜料与填料、特种助剂、环境科学、现代测试技术以及现代涂装技术等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 102,
+        "chunk": "# 一、重防腐涂料的特点  \n\n重防腐涂料除了具有在严酷腐蚀环境下应用和长效寿命特点外，还有以下几个特点而区别于一般防腐涂料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 103,
+        "chunk": "# 1．厚膜化  \n\n这是重防腐涂料重要标志之一。为此，现代重防腐涂料向高固体分、少溶剂、无溶剂化方向发展。涂层设计的目标是使用寿命，而使用寿命取决于腐蚀环境。这里使用寿命有两层含义：其一是指涂层运行使用至下一次维修时的间隔期限；其二是指一次性使用至涂层失去保护功能的期限。涂层的使用寿命是根据被保护对象本身的寿命、价值及维修的难易来确定的，ISO12944-5对于涂层的使用寿命分为三个等级。  \n\n<html><body><table><tr><td>低（low）</td><td>2～5年</td></tr><tr><td>中（medium)</td><td>5～15年</td></tr><tr><td></td><td></td></tr><tr><td>高（high）</td><td>15年以上</td></tr></table></body></html>  \n\n当然ISO12944-5所说的使用寿命绝不是商业“承诺防腐寿命”，而仅是涂装设计一个技术参数，它的作用主要是为设计者制定一个比较合理的维修涂装时间表以做参考。  \n\n涂层的厚度对使用寿命非常重要，实验已经证明，在一定的腐蚀环境下，涂层配套确定之后，涂层厚度与保护寿命呈直线关系，如图3-3-20所示。  \n\n![](images/1e886f7b2e027bfe51d0e9963be81f422fc9b0bcaa764442c5984f3a1a884a1b.jpg)  \n图3-3-20涂层的平均寿命和厚度的关系（油基漆和醇酸漆，每道漆膜厚度是 $25\\mu\\mathrm{m})$ A一一道底漆加一道面漆；B一两道底漆加两道面漆；C一一道底漆加三道面漆；D一两道底漆加四道面漆；E-一道底漆加五道面漆  \n\nFick定律：腐蚀介质渗透达到涂层-金属界面的时间与涂层的厚度平方成正比，与扩散系数成反比，其数学表示式为：  \n\n$$\nT{=}\\frac{L}{6\\bar{D}}\n$$  \n\n式中 $T-$ —液体腐蚀介质渗透至涂层-金属界面时间（ $T$ 值越大间接表明防腐寿命越长)；  \n\n$L$ ——涂层干膜厚度；  \n\n$D/$ -—介质扩散系数（取决于涂层与介质结构、渗透压力、温度等参数）。  \n\n由此可见，重防腐涂装应尽量厚膜化（干膜 $200\\mathrm{\\sim}1000\\mu\\mathrm{m})$ ，以提高涂层的使用寿命。  \n\n涂层厚度是根据腐蚀环境及使用寿命来确定的，三者的关系在ISO12944-5中有推荐要求，见表3-3-12。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 104,
+        "chunk": "# 2.高性能原材料的研发是重防腐涂料发展的关键  \n\n在防腐涂料的研究中，对于高性能的耐蚀合成树脂和新型的颜料、填料的研究与开发，国内外一直十分活跃。一个重要的研究方向是在保持原有性能的基础上，克服其缺点并开发多方面功能。  \n\n表3-3-12 腐蚀环境、使用寿命和涂层厚度的关系  \n\n\n<html><body><table><tr><td>腐蚀环境</td><td>使用寿命</td><td>干膜厚度/μm</td><td>腐蚀环境</td><td>使用寿命</td><td>干膜厚度/μm</td></tr><tr><td rowspan=\"2\">C2</td><td>低</td><td>80</td><td rowspan=\"2\">C4</td><td>低</td><td>160</td></tr><tr><td>中高</td><td>15020</td><td>中高</td><td>240(20锌粉)</td></tr><tr><td rowspan=\"2\">C3</td><td>低</td><td>120</td><td rowspan=\"2\">C5-I,C5-M</td><td rowspan=\"2\">低 中</td><td>280（不含锌粉） 200</td></tr><tr><td>中 高</td><td>160 200</td><td>280</td></tr></table></body></html>  \n\n(1）聚合硅氧烷树脂的研发为克服丙烯酸树脂耐溶剂性差、不耐高温的缺点，采用有机硅氧烷原位、接枝聚合改性丙烯酸树脂的方法，大大提高了丙烯酸树脂的耐热性和耐溶剂性，即丙烯酸聚硅氧烷涂料。美国AMERON公司生产的PSX70O环氧硅氧烷涂料，将无机硅氧烷主干与有机树脂结合，不仅克服了环氧树脂户外易粉化的缺点，而且实现了在一种涂料上同时具有高性能环氧漆和聚氨酯漆的性质，其耐腐蚀性、耐候性、耐热性及外观装饰性等均有突破性的提高。又如Hempel公司的老人牌聚硅氧烷面漆55000，是由聚硅氧烷树脂与脂肪族环氧树脂聚合而成的环氧-聚硅氧烷涂料。由于在聚合树脂结构中含有高键能$(446\\mathrm{kJ/mol})$ ）的Si一O键，因此其耐阳光、紫外线能力大大增强，而具有极强的抗老化、耐候性、耐腐蚀性能。  \n\n(2）氟碳树脂的研发与应用已从高温干燥型发展到常温自然干燥型；设法降低VOC含量和改善重涂性是氟碳涂料的研究方向。  \n\n(3）导电聚苯胺防腐涂料的研发树脂本身导电而且防腐性能优秀，属于本征型导电涂 料。它克服了导电性与防腐性的矛盾，技术上比常规导静电涂料高出一个档次。  \n\n(4）聚脲防腐弹性体涂料——聚天门冬氨酸酯聚脲性能与应用前景远优于聚氨酯。(5）新型鳞片状金属锌粉替代目前广泛使用的球状锌粉，防腐性提高（阴极保护十屏蔽效应)，锌粉用量可降1/3，制漆成本明显下降。(6）云母氧化铁和玻璃鳞片在环氧中层漆中推广应用。(7）水相法制备氯化橡胶中国政府已在禁止和限制使用四氯化碳和氟里昂等物质保护大气臭氧层的蒙特利尔国际公约上签字，承诺停止使用用四氯化碳法生产氯化橡胶。而氯化橡胶涂料在中国仍有很大市场，专业生产厂有数十家，年产能力5000t以上。禁用令使这些中、小企业面临生死出路，水相法制备的氯化橡胶因对环境友好而不在限制范围，这些企业又看到了希望。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 105,
+        "chunk": "# 3.重防腐涂装的表面处理  \n\n对于防腐工程表面处理的重要性怎么估计也不为过，如同一座高楼大厦不能建筑在沙滩上的道理一样。涂装前表面处理方法很多，如酸洗磷化、机械打磨、喷砂抛丸等。不同行业、不同的涂装对象可能采用不同的处理方法，但在重防腐领域，喷射除锈（俗称喷砂）迄今仍是最佳的工艺选择。其一，钢材表面清洁度达标有保证（ $(S_{\\mathrm{a}}\\geq2,5)$ ；其二，表面粗糙度均匀 $(R_{z}=40{\\sim}75\\mu\\mathrm{m})$ 。而涂装前钢材表面粗糙度不仅增加了钢材表面积，还为漆膜附着提供了合适的表面几何形状，有利于漆膜与底材之间的粘接和漆膜厚度分布的均匀一致；刚喷砂后的钢材，表面能增大，处于活化态，3h之内喷涂防锈底漆，是涂料分子与金属表面极性基团之间相互吸引与粘接的最佳时期。  \n\n喷砂工艺应尽量标准化、规范化。如应尽量采用金属磨料，执行GB/T18838.1《涂覆涂料前钢材表面处理喷射清理用金属磨料的技术要求》（等同ISO11124-1：1993)，并可参考美国钢结构涂装协会（SSPC-SPCOM）所列出的喷射不同磨料所测得的粗糙度；喷砂后表面清洁度应执行GB8923《涂装前钢材表面锈蚀等级和除锈等级》（等效采用ISO8501-1)；而表面粗糙度的检查应执行GB/T13288《涂装前钢材表面粗糙度等级的评定》（参照采用ISO8503）和GB6060.5《表面粗糙度比较样板抛（喷）丸、喷砂加工表面》等标准。  \n\n喷砂作业应尽量在喷砂房内进行，户外喷砂应采用带有布袋吸尘器的喷砂设备，以利环境保护和劳动保护。  \n\n涂装前表面处理除了喷砂除锈外，还包括喷砂前除油和除去可溶性盐等污染物，同样是十分重要的前处理工序。而一般施工者认为喷砂可以把它们清除，但是实际上只是把这些污染物的大部分深深的分散凿在钢材表面，形成更加隐蔽、危险性更大的污染。除油、除盐可采用高压喷射淡水（除油需加清洗剂）的工艺方法，可参照NACENo.5《高压淡水冲洗的清洁标准》（相对美国钢结构涂装标准SSPC-SP12）和GB/T13312《钢铁件涂装前除油程度检验方法》。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 106,
+        "chunk": "# 4.涂层配套的正确性  \n\n钢结构工程重防腐涂装，一般分为底漆、中间漆和面漆。底漆的主要功能是防锈，增强与金属表面附着力；中间漆的主要功能是增加漆膜厚度，以增强漆层体质；而面漆除了装饰性功能之外，还有更多方面的功能要求。在选择涂料时，力求“底-中-面”三涂层配套正确，即要讲究其配套性。一般没有固定规律可循，大都是长期施工经验的总结。例如：  \n\n$\\textcircled{1}$ 固化类型一致，例如不宜将烘干型涂料喷在溶剂挥发型（自然干燥）涂料上面；  \n$\\textcircled{2}$ 不宜将强溶剂的面漆喷涂在弱溶剂的底漆上面等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 107,
+        "chunk": "# 5．推荐采用“底-面合一”施涂工艺  \n\n近年来，为适应重防腐涂装的需要，已有“底-面合一”的厚涂涂料出现，采用高压无气喷涂技术，一次可以喷涂几百微米，甚至几毫米，在大型钢结构工程中得到迅速广泛的应用。最常用的是无溶剂、高黏度环氧、聚氨酯涂料等。这类漆固体含量一般在 $70\\%$ （体积分数）以上，甚至 $100\\%$ ，施工时一般不加稀释剂，因此宜采用高压无空气喷涂机进行喷涂，也可刷涂。由于环氧树脂极强的粘接性能，使涂层牢固地附着在钢材表面，形成一道厚厚的防护涂层，有效地阻缓外界腐蚀性介质的浸入。防护期可达10年以上。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 108,
+        "chunk": "# 6.现代涂装现场管理是实现重防腐涂装设计目标的重要环节  \n\n涂装的目的在于涂层质量，并通过科学而严格的质量管理而实现的。涂装工程质量管理是一项全员参与、贯穿全过程的系统工程。",
+        "category": " Introduction"
+    },
+    {
+        "id": 109,
+        "chunk": "# 二、常用重防腐涂料简述  \n\n重防腐工程一般采用复合涂层，分为底漆、中间漆和面漆。底漆主要有车间底漆、磷化底漆、磷酸锌环氧底漆以及富锌底漆；中间漆主要有环氧封闭漆和厚浆型环氧中层漆等；面漆主要有中、低档的有醇酸漆、丙烯酸漆、氯化橡胶漆；高档品种有聚氨酯面漆、氟碳面漆及聚硅氧烷面漆等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 110,
+        "chunk": "# 1.常用底漆  \n\n底漆的主要作用是：防腐蚀、确保涂层与底材的附着力并为后继涂层一一中间漆或面漆提供良好的附着基础。  \n\n(1）车间底漆车间底漆（shopprimer)，又称钢材预处理底漆或保养底漆（prefabri-cation primer)，这是一种工序间临时防护漆。主要应用于钢材喷砂后的一次表面处理阶段，对钢材在焊接与切割、弯曲与成型阶段起临时保护作用，其户外保护期为 $3\\sim9$ 个月。该底漆一般为可焊接底漆，在结构组装完成后，通常需要重新喷砂，去除车间底漆，并及时喷涂配套底漆。正由于车间底漆的临时保护作用，大大减少了在组装后二次除锈的工作量，有利于后续配套涂层的涂装。因此，车间底漆必须具备以下性能：  \n\n$\\textcircled{1}$ 在钢材组装前至少有3个月的防锈能力，一般为 $3\\sim9$ 个月户外防护期；$\\textcircled{2}$ 不影响焊接、切割速率和质量以及焊接强度；$\\textcircled{3}$ 焊接切割时不产生超过劳动保护允许范围的有害气体；$\\textcircled{4}$ 适应自动化流水线的施工要求；$\\textcircled{5}$ 漆膜快干（ $(3\\cdots5\\mathrm{min}).$ ）且力学性能好，耐磨性、耐弯曲性好，便于钢板在工序间便捷吊装与转运；$\\textcircled{6}$ 配套性好，能适应大部分涂料的覆涂。目前车间底漆主要有四种类型：聚乙烯醇缩丁醛车间底漆（PVB)、环氧含锌车间底漆、环氧铁红车间底漆及无机硅酸锌车间底漆。  \n\n无机硅酸锌车间底漆是目前主要应用的车间底漆类型。它以正硅酸乙酯为基料，配以锌粉以及其他颜填料、溶剂、添加剂等。其固化成膜依靠正硅酸乙酯吸收空气中的水分水解后缩聚，然后与锌粉及钢材表面活性铁反应生成锌-硅酸复合盐而牢固地附着于钢铁表面。具有良好的防锈性、力学性优良、耐热性好、热加工时损伤面少等突出性能。  \n\n最新发展的超高温耐热无机锌车间底漆，采用超耐热树脂对正硅酸乙酯进行改性，采用部分耐热防锈颜料与锌粉共用，在火工校正和电焊时，对涂层的烧损面积大大减少。  \n\n由于锌粉在焊接时会产生锌烟，对人体的健康不利，目前使用较多是中、低含锌型车间底漆。适当减少锌粉含量可以提高焊接质量与速率。详细的车间底漆介绍可参考船舶涂料部分。  \n\n(2）磷化底漆磷化底漆又称洗涤底漆（wash primer）或蚀刻底漆（etchingprimer）。磷化底漆通常由磷酸、聚乙烯缩丁醇、四碱式锌黄以及填料和醇类溶剂组成。通过磷酸的蚀刻作用，磷化底漆可与许多不易进行彻底表面处理的底材结合，形成附着优良的涂层；同时四碱式锌黄［ZnCrO·4Zn(OH)z］可以结合生成铬酸铁覆盖在钢铁表面，使金属表面钝化。一方面保证了磷化底漆与底材的结合力；另一方面起到较好的防锈蚀性能。  \n\n磷化底漆主要可以用于镀锌件、铝合金、不锈钢、喷锌喷铝等金属表面。为了确保磷酸的蚀刻作用，通常磷化底漆的漆膜厚度为 $10\\mu\\mathrm{m}$ 左右，太厚的涂层会影响附着力，而且不能用于自身覆涂。另外，虽然磷化底漆本身因含有优良的防锈颜料，具有一定的防锈效果，但由于漆膜很薄，通常它不能作为防锈底漆来使用。它的主要作用还是为底材与其后道涂层之间提供良好的附着性能。  \n\n磷化底漆中使用的四碱式锌黄虽然具有良好的防锈效果，但因为它是一种六价铬${\\mathrm{(}}{\\vec{\\mathrm{r}}}^{5+}$ ）化合物，有致癌作用，因此，近年来新型的磷化底漆逐渐使用磷酸锌、三聚磷酸铝、硼酸锌等防锈颜料来替代。但由于所有的这些防锈颜料都具有一定的水溶性，因此磷化底漆不推荐用于水下环境，  \n\n虽然磷化底漆在镀锌件等底材表面有非常良好的附着性能，但由于上述自身的这些缺陷，因此近年来它也逐渐被镀锌件等底材专用的环氧磷酸锌底漆所取代。表3-3-13列出以聚乙烯醇缩丁醛树脂为成膜剂的乙烯磷化底漆化工行业标准。  \n\n表3-3-13 HG/T3347—1987X06-1乙烯磷化底漆（分装）  \n\n\n<html><body><table><tr><td colspan=\"2\">项 目</td><td>指标</td><td>试验方法</td></tr><tr><td>颜色及外观</td><td>原漆 磷化液 漆膜</td><td>黄色半透明黏稠液体 无色至微黄色透明液体 黄绿色半透明，漆膜平整</td><td>GB/T 1721—1979 目测 GB/T 1729—1979</td></tr><tr><td colspan=\"2\">黏度(涂-4杯）/s 磷化液中磷酸含量/%</td><td>≥30 15~16 ≤30 I</td><td>GB/T1723—1979 乙法 HG/T3347第3.5条 GB/T 1728—1979</td></tr></table></body></html>  \n\n(3）磷酸锌底漆磷酸锌底漆，顾名思义是以磷酸锌为主要防锈颜料的底漆。磷酸锌$\\left[\\mathrm{Zn}_{3}\\left(\\mathrm{PO}_{4}\\right)_{2}\\cdot(2{\\sim}4)\\mathrm{H}_{2}\\mathrm{O}_{2}^{}\\right]$ 也是一种优良的缓蚀颜料。磷酸锌通过其本身包含的结晶水以及环境或底材表面的微量水逐渐水解，生成氢氧化锌和二代磷酸盐离子。这些水解产物形成附着和阻蚀络合物，可使金属表面磷化，形成在阳极范围内特别有效的保护层，白色凝胶状氢氧化锌和底材具有良好的附着力。  \n\n磷酸锌可与各种漆基相容，生产各种防腐涂料。如醇酸磷酸锌底漆、氯化橡胶磷酸锌底漆以及环氧磷酸锌底漆。由于环氧树脂出众的防腐效果以及优异的附着性能，因此磷酸锌防锈颜料与环氧树脂配合使用，在重防腐涂装领域有着广泛的应用。  \n\n（4）富锌底漆富锌底漆（zipcimer）是一种高效的防腐涂料，其防腐机理是基于金属锌粉对钢材表面的阴极保护作用。金属锌的电化学活性比铁更活泼（其标准电极电位为一0.763V，而铁为一0.409V)，因此，当锌粉足量时，即在钢铁表面形成一层锌粉膜，并与钢铁表面紧密接触，在腐蚀介质的作用下（主要是氧气、水分等)，便组成锌-铁腐蚀电池，锌为阳极“自我牺牲”被腐蚀，而钢铁作为阴极则受到保护，如图3-3-21所示。以常见的大气腐蚀中的吸氧腐蚀为例，其腐蚀电池电极反应方程式如下。  \n\n在阳极：锌原子失去电子在阴极：铁表面的氧分子获得电子  \n\n总反应：  \n\n$$\n\\mathrm{2Zn{-}4e^{-}}\\longrightarrow\\mathrm{2Zn^{2+}}\n$$  \n\n$$\n\\mathrm{O}_{2}+2\\mathrm{H}_{2}\\mathrm{O}+4\\mathrm{e}^{-}\\longrightarrow4\\mathrm{OH}^{-}\n$$  \n\n$$\n2\\mathrm{Zn}+\\mathrm{O}_{2}+2\\mathrm{H}_{2}\\mathrm{O}\\longrightarrow2\\mathrm{Zn}(\\mathrm{OH})_{2}\n$$  \n\n$$\nZ n(O H)_{2}\\longrightarrow Z n O+H_{2}O\n$$  \n\n![](images/7ec7c544ccb844a82aaa1b28fe3dd1f5965132b56b32a17ca49227e86d68e181.jpg)  \n图3-3-21 当有机面漆受损时富锌底漆起反应来保护钢材表面  \n\n金属锌的腐蚀产物-氧化锌（ZnO）呈白色粉末状，它同时也对漆膜形成封闭保护作用，  \n\n目前国内外防腐界广泛使用的富锌底漆有环氧富锌底漆和无机富锌两种。  \n\n![](images/a6cceb45acc315943a8966944f7751d57a2ebc4cfaa00931aa617a27a9e23970.jpg)  \n图3-3-22 氧化锌的封闭保护作用  \n\n如图3-3-22所示。  \n\n环氧富锌底漆利用环氧树脂优良的防腐与附着性能，兼有一定的韧性和耐冲击等漆膜物理性能，给予金属锌的电化学阴极保护作用提供了重要的补充。  \n\n无机富锌底漆则可以运用超CPVC（临界颜料体积浓度）配方设计技术，与环氧富锌底漆相比，漆膜拥有更高的锌含量，  \n\n从而达到更优越的阴极保护性能。同时，无机硅酸盐与锌粉反应生成硅酸锌，并与基体金属铁反应形成锌-硅酸-铁络合物，这些生成物薄膜致密、难溶、坚硬，有效阻止氧气、水分及盐类的侵蚀，起到辅助的防锈作用。  \n\n而水基富锌底漆以其优异的防锈性能也有大量的应用。但当前水基富锌底漆还存在一些缺陷：一是不适宜低温下施工（<5℃)；二是对表面处理要求十分严格，施工性欠佳。同时，如果配套涂层从底到面都采用水性漆，的确有利于环境保护；如果仅仅是底漆采用水基富锌，而中间漆/面漆仍沿用溶剂型涂料，那对环保的贡献有限，综合考虑不如选用无机富锌或环氧富锌底漆。三种富锌底漆各方面性能对比见表3-3-14。  \n\n表3-3-14 三种富锌底漆性能对比  \n\n\n<html><body><table><tr><td>项目</td><td>水基富锌底漆</td><td>溶剂基无机富锌底漆</td><td>环氧富锌底漆</td></tr><tr><td>表面处理</td><td>Sa3级</td><td>S.2.5或S3级</td><td>S2.5</td></tr><tr><td>最大干膜厚度/μm</td><td>200</td><td>175</td><td>80</td></tr><tr><td>防腐性</td><td>++++</td><td>++++</td><td>+++</td></tr><tr><td>耐热性</td><td>++++</td><td>++++</td><td>++</td></tr><tr><td>导电性</td><td>++++</td><td>++++</td><td>++</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>项目</td><td>水基富锌底漆</td><td>溶剂基无机富锌底漆</td><td>环氧富锌底漆</td></tr><tr><td>耐溶剂性</td><td>++++</td><td>++++</td><td>++</td></tr><tr><td>附着力</td><td>+++</td><td>++++</td><td>+++</td></tr><tr><td>配套性</td><td>十十</td><td>+++</td><td>+++→</td></tr><tr><td>对施工环境的要求</td><td>+++</td><td>十十</td><td>、十</td></tr><tr><td>施工性</td><td>十十</td><td>+++</td><td>++++</td></tr><tr><td>固化条件/℃</td><td>≥10</td><td>-10~40</td><td>≥一10（冬用型）</td></tr><tr><td>维修困难度</td><td>+++</td><td>++.</td><td></td></tr><tr><td>经济性</td><td></td><td>+++</td><td>++++</td></tr><tr><td>其他</td><td>需加喷封闭漆</td><td>需加喷封闭漆</td><td>不需加喷封闭漆</td></tr></table></body></html>\n\n注： $^{*}+{}^{*}$ 多，表明性能更好。  \n\n富锌底漆是通过牺牲阳极金属锌而起到对钢材阴极保护作用的。因此金属锌含量至关重要，它直接影响富锌底漆的防锈性能。通常，采用指标“漆膜干膜（或不挥发分）中的金属锌（质量）含量”来评估产品是“含锌底漆”还是“富锌底漆”。目前国内外都有相关的标准来定义富锌底漆，见表3-3-15。  \n\n表3-3-15 国内外相关标准对富锌底漆锌含量的规定  \n\n\n<html><body><table><tr><td>不挥发分中金属 锌含量/%</td><td>无机富锌底漆</td><td>环氧富锌底漆</td></tr><tr><td>标准名 HG/T3668—2000《富锌底漆》 （等效采用JISK5552—1991）</td><td>≥80</td><td>≥70</td></tr><tr><td rowspan=\"2\">美国钢结构涂装协会标准 SSPC PAINT 20 Zinc-Rich Coating，Type</td><td>1级 ≥85</td><td>1级 ≥85</td></tr><tr><td>2级 77~85</td><td>2级 77~85</td></tr><tr><td rowspan=\"2\">I -Inorganic and Type II -Organic ISO 12944-5:1998 Protective Paint Systems</td><td>3级 65~77</td><td>3级 65~77</td></tr><tr><td></td><td>≥80</td></tr></table></body></html>\n\n$\\textcircled{1}$ 该标准是美国涂料协会标准。  \n\nGB/T 6890、ISO3549及ASTMD520—2000、ASTMD6580—2000等国内外标准，均对富锌底漆所用金属锌粉分级及其检验方法作了具体规定，而目前市场上某些号称“富锌”的产品，售价很低，而锌含量不足 $50\\%$ ，充其量只能叫做“含锌”，不宜用作长效防腐底漆。此外，不同涂装用途对富锌底漆涂覆厚度要求不同，随之对锌粉粒度及粒度分布的要求也不同，对锌粉中水分、Pb、Ca等杂质含量也有严格的要求。这些因素便是当前市场上促使富锌底漆价格悬殊的原因之一。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 111,
+        "chunk": "# 2.中间漆  \n\n中间漆的主要功能是增加漆膜厚度，以增强漆层体质。作为底/面之间的过渡层，在涂层配套正确的前提下，具有提高层间附着力的作用。国内最常用的是环氧厚浆漆，而在桥梁、电站、港口和海上钢结构等重防腐工程中，却偏重于采用云母氧化铁环氧漆和玻璃鳞片涂料。两者均以耐蚀树脂为主要成膜物质（主要是环氧树脂)，分别以云母氧化铁和玻璃鳞片为防锈颜料，再加人其他助剂而组成的厚浆型涂料。  \n\n(1）云母氧化铁环氧漆云母氧化铁环氧漆的主要成分是 $a$ -三氧化二铁，其结晶体呈片状或平板状六角形，有较大的径厚比，径长从几十微米到 $100\\mu\\mathrm{m}$ ，厚度仅数微米到数十微米；这些片状粒子在涂膜中交叉排列，层层叠叠（图3-3-23)，切断了外界腐蚀性介质向涂层的通道一一毛细孔，从而形成了独特的屏蔽结构，具有极优良的抗介质渗透性，耐酸、耐碱、耐热、耐磨。广泛应用于钢结构桥梁、大型油罐、电站钢结构等户外防护涂层中间漆。  \n\n![](images/6e7a47833713ee36cde216f9b558d7674ecfe638673d96380e4280bfb1c8340a.jpg)  \n图3-3-23 云母氧化铁（MIO）在涂层中的分布示意  \n\n我国至今尚未制定云母氧化铁环氧漆的行业标准，但制定了云母氧化铁防锈颜料标准(GB/T6755—1988)，规定了以天然云母氧化铁为原料，经破碎、选矿、粉碎等工序而制得的云母氧化铁防锈颜料规格和相应的试验方法（表3-3-16)。日本工业生产标准JISK5555—1991《云母氧化铁环氧树脂漆》见表3-3-17。  \n\n表3-3-16 云母氧化铁技术要求（GB/T6755—1988）  \n\n\n<html><body><table><tr><td rowspan=\"2\">项目</td><td colspan=\"2\">技术指标</td><td rowspan=\"2\">试验方法</td></tr><tr><td>带有金属光泽的灰色</td><td>不带有金属光泽的红褐色</td></tr><tr><td colspan=\"2\">铁含量（以三氧化二铁表 示，颜料经105℃烘干后测</td><td>93.0</td><td>90.0</td><td>GB/T 6755中2.1</td></tr><tr><td colspan=\"2\">定)/% 105C挥发物/% ≤</td><td>0.5</td><td>0.5</td><td>GB 5211.3—1985</td></tr><tr><td colspan=\"2\">水溶物/%</td><td>0.1</td><td>0.3</td><td>GB 5211. 2-—1985</td></tr><tr><td rowspan=\"2\">筛余 物/%</td><td>≤ 筛孔45μm ≤</td><td>一</td><td>1.0</td><td>GB/T 1715—1979</td></tr><tr><td>筛孔63μm ≤</td><td>1.0</td><td></td><td></td></tr><tr><td colspan=\"2\">水悬浮液pH</td><td></td><td>一 5.5~7.5</td><td>甲法</td></tr><tr><td colspan=\"2\">吸油量/%</td><td>6.0~8.0 9~12</td><td>9~14</td><td>GB/T 1717—1986</td></tr><tr><td colspan=\"2\">二氧化硅含量/%</td><td>3.0</td><td>3.2</td><td>GB/T 1712—1979 GB/T 6755中2.2</td></tr></table></body></html>  \n\n表3-3-17 日本工业生产标准《云母氧化铁环氧树脂漆》 JISK5555—1991  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>容器中状态</td><td>双组分混合搅拌后无硬块，均匀一致</td><td>柔韧性</td><td>耐10mm弯曲</td></tr><tr><td>混合性</td><td>按比例混合搅拌均匀一致</td><td>面漆与中层间附着性</td><td>无异常</td></tr><tr><td>分散度/μm</td><td>80</td><td>耐盐水性</td><td>浸人NaCl溶液中后无异常</td></tr><tr><td>施工性</td><td>涂装无障碍</td><td>总固含量/%</td><td>73</td></tr><tr><td>流挂性</td><td>不流挂</td><td>溶剂不溶物/%</td><td>50~67</td></tr><tr><td>干燥时间/h ≤</td><td>16</td><td>酚醛类定性分析</td><td>含酚醛类</td></tr><tr><td>漆膜外观</td><td>正常</td><td>云母氧化铁定性分析</td><td>含有云母氧化铁</td></tr><tr><td>活化期/h 》</td><td>5</td><td>暴露后的层间附着性</td><td></td></tr><tr><td>面漆后的层间附着性</td><td>涂面漆无障碍</td><td></td><td>曝晒1年后，涂层无异常</td></tr></table></body></html>  \n\n(2）玻璃鳞片涂料美国欧文斯-康宁（Owens-Corning）玻璃纤维公司于1953～1955年间首先成功开发并制造出玻璃鳞片，接着将玻璃鳞片和环氧树脂等混合制成涂料，最初应用于混凝土基材和钢管内衬，并于1957年发表了玻璃鳞片涂料制造的第一个专利。从此被广泛推广应用。20世纪60年代初美国Ceilcote公司推出了环氧-沥青玻璃鳞片涂料，其他一批公司陆续开发出一系列玻璃鳞片涂料，并推广至欧洲。日本、中国多家公司也先后于20世纪60～70年代引进这项技术，并取得成功应用，在重防腐界引起广泛注意。  \n\n玻璃鳞片涂料是以耐蚀树脂为主要成膜物质，以薄片状的玻璃鳞片（glassflake）为骨料，再加上各种添加剂组成的厚浆型涂料。常用耐蚀树脂主要是热固性树脂，如乙烯基酯树脂（VE)、不饱和聚酯树脂（UP）、环氧树脂（EP）及聚氨酯树脂（PU）等。目前，在重防腐涂装中应用较多的是玻璃鳞片环氧树脂漆，其典型配方参见表3-3-18。  \n\n表3-3-18玻璃鳞片涂料基本配方  \n\n\n<html><body><table><tr><td>组分</td><td>耐蚀树脂</td><td>玻璃鳞片</td><td>触变剂</td><td>溶剂</td><td>颜料</td><td>其他助剂</td></tr><tr><td>质量分数/%</td><td>60~77</td><td>20~35</td><td>1~5</td><td>10~15</td><td>2~7</td><td>1~3</td></tr></table></body></html>  \n\n玻璃鳞片通常为钠碱玻璃类，组成复杂，主要成分为SiO、Na2O、CaO等。玻璃鳞片的厚度一般为2～5um、片径长度为100～3000um，由于涂层中的玻璃鳞片上下交错排列，使涂层形成了独特的“迷宫”式屏蔽结构（图3-3-24和图3-3-25）。在1mm干膜中玻璃鳞片可交错排列100层，使外界腐蚀性介质渗透至金属基体表面的路径变得曲曲折折，有效延长了渗透时间，大大提高了涂层的抗渗透性与防护寿命。  \n\n![](images/57ab789d93838fcdc012de6dbda1e3c49807f1f8a6cd31be09a5bcb09863e578.jpg)  \n图3-3-24 玻璃鳞片涂层结构示意  \n\n![](images/909b79bde357e668fa1a671a3986d9f77143c4194c45a4871ca7b378505ba598.jpg)  \n图3-3-25 电子显微镜下放大的玻璃鳞片涂层结构  \n\n显然，从图片直观上看来，玻璃鳞片涂层的屏蔽性更好些，漆膜机械强度更强，但质脆、抗变形性能差，柔韧性不如云母氧化铁环氧漆。如耐冲击强度按GB/T1732检测一般小于30kgf·cm。比较适合用于浪溅区、水下、桥墩、海洋工程设备防腐、化学品贮槽、排烟脱硫装置内衬等严重腐蚀环境下。但是，玻璃鳞片涂料价格通常较高，所以在一般大气下的钢结构防腐，选用云母氧化铁环氧漆作为中间涂层的较多，性价比较优。  \n\n玻璃鳞片涂料性能具有下列特点：  \n\n$\\textcircled{1}$ 极优良的抗介质渗透性，耐腐蚀性优异；  \n$\\textcircled{2}$ 优良的耐磨损性；  \n③硬化时体积收缩率小，热膨胀系数小；  \n$\\textcircled{4}$ 与基体的粘接性好，耐温度骤变性好；  \n③良好的施工工艺性，可采用喷、辊、刷和抹等工艺，而且易于修补。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 112,
+        "chunk": "# 3.普通面漆  \n\n（1）醇酸树脂涂料醇酸树脂是用油料、多元醇（如甘油和季戊四醇等）、多元酸（如苯二甲酸酐等）制备而成的一种聚酯。醇酸树脂漆的性能与脂肪酸含量（油度）有很大的关系，按油度可以分成短油度、中油度和长油度三类。制成的涂料各有特性，见表3-3-19。  \n\n表3-3-19不同油度的醇酸树脂涂料的性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">油度 短</td><td>脂肪酸含量/%</td><td>溶剂</td><td>硬度</td><td>刷涂性</td><td>保光性</td><td>泛黄性</td></tr><tr><td><40</td><td>芳烃</td><td>高</td><td>差，要喷涂</td><td>优</td><td>优</td></tr><tr><td>中</td><td>40~60</td><td>混合烃</td><td>中</td><td>中</td><td>好</td><td>好</td></tr><tr><td>长</td><td>>60</td><td>脂肪烃</td><td>低</td><td>良</td><td>中</td><td>中</td></tr></table></body></html>  \n\n用于防腐蚀涂料的面漆，通常采用长油度的醇酸树脂  \n\n与传统的油性涂料相比，醇酸树脂涂料的干性、保色性、耐候性、附着力等均有了很大程度的提高。因此在很长的一段时间内，它在重防腐涂装领域占有重要的地位。  \n\n但是醇酸树脂涂料有许多不足之处：干燥缓慢、硬度低、耐水性差、户外耐候性不良，日光照射易泛黄；而且基于醇酸树脂涂料的氧化干燥机理，其不能一次涂装太厚。已经不能满足现代涂装所要求的高效率和长效防护的要求了。  \n\n(2）氯化橡胶涂料氯化橡胶（chlorinatedrubber）是天然橡胶或合成的聚异戊二烯橡胶在氯仿或四氯化碳中于 $80{\\sim}100^{\\circ}C$ 氯化而成。由于氯化橡胶的分子结构致密，因此氯化橡胶涂料漆膜致密，水蒸气和氧气透过率极低，具有良好的耐水性和防锈性能；氯化橡胶在化学上呈惰性，因此具有良好的耐酸性和耐碱性。同时，氯化橡胶涂料属物理干燥型，因此重涂性能良好，干燥快，不受环境温度的限制。  \n\n正是由于诸多的优点，氯化橡胶涂料曾被广泛应用在现代重工业防腐蚀涂料中。氯化橡胶面漆在应用量最大的集装箱制造业和船舶制造业中，一度占据了主要地位，成为规定的标准配套方案。  \n\n氯化橡胶涂料由于是热塑型涂料，在干燥环境中温度高于 $130^{\\circ}C$ 即开始分解；潮湿环境下， $60^{\\circ}C$ 就开始分解，所以使用温度不能高于 $60\\sim70^{\\circ}C$ ；对溶剂的耐性也较差。因结构含氯，长期户外曝晒后，漆膜泛黄较严重，对面漆的装饰性影响较大。  \n\n而且更为重要的是，氯化橡胶生产过程残留的四氯化碳会对大气产生一定的污染，因此其应用受到各国环保的限制。  \n\n(3）丙烯酸涂料丙烯酸树脂通常以丙烯酸酯或/和甲基丙烯酸酯，以及苯乙烯为主的乙烯系单体共聚而成。丙烯酸树脂的主链是碳-碳键，对光、热、酸和碱十分稳定，用它制成的漆膜具有优异的户外耐候性能，保光、保色性好。它的侧链可以是各种基团，通过侧链基团的选择，可以调节丙烯酸树脂的混容性及可交联性能。  \n\n丙烯酸涂料有热塑型和热固型两类。热塑型丙烯酸树脂透明度高，在紫外线照射下不易褪光及变色，具有优良的保光保色性能。其漆膜光亮丰满，耐酸、耐碱和耐腐蚀性均较好。近年来，随着氯化橡胶的生产受到一定的限制后，丙烯酸树脂涂料因具备同氯化橡胶相类似的施工性能，如快干、无重涂间隔，已逐步取代了氯化橡胶涂料，成为防腐蚀涂料的常用面漆品种之一。在集装箱制造业中，现在所使用的面漆品种大多是丙烯酸树脂漆。但是热塑性丙烯酸对温度敏感，漆膜遇高温会软化发黏，打磨时会粘砂纸。在一些腐蚀环境严重的区域，它的总体效果还是不能令人满意。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 113,
+        "chunk": "# 4.高性能面漆  \n\n(1）聚氨酯涂料聚氨酯涂料可以分成单组分和双组分两大类。单组分聚氨酯涂料包括氨酯油、氨基醇酸树脂、湿固化聚氨酯和封闭型聚氨酯等。氨酯油和氨基醇酸树脂具有较好耐碱性、耐水性等化学耐性以及较好的透干性，因此通  \n\n常它们作为助树脂用于其他涂料品种中。  \n\n湿固化聚氨酯涂料则利用—NCO基团，在环境湿度下与空气中的水分反应生成脲键固化成膜。它既有聚氨酯涂料的优良性能，也具有较好的机械耐磨性，同时又有单组分涂料施工方便的特点。但其干燥速率受空气中湿度影响较大。在冬季低温和低湿环境下，反应缓慢；另外成膜固化时会产生许多 $\\mathrm{CO_{2}}$ ，不宜高厚膜化。  \n\n封闭型涂料是预先使用苯酚或其他单官能团的含活泼氢原子的物质将异氰酸酯封闭，在使用时通过高温使前两者分离，封闭剂挥发，异氰酸酯则继续与多羟基树脂聚合成膜。  \n\n综上几种单组分聚氨酯涂料，均不适宜以常温施工为主的重防腐涂装领域。  \n\n双组分聚氨酯涂料是以多异氰酸酯与多羟基树脂按比例混合聚合反应成膜的。根据多异氰酸酯的不同类型，通常将聚氨酯涂料分成芳香族聚氨酯涂料和脂肪族聚氨酯涂料；根据多羟基树脂的不同类型，又可以将聚氨酯涂料分为聚酯、丙烯酸树脂、聚醚、环氧聚氨酯涂料等。  \n\n芳香族聚氨酯涂料一般是以甲苯二异氰酸酯（TDI）为原料，价格较低，漆膜坚硬、耐磨，综合耐性好，干燥速率快。但由于苯环的存在，氨酯键受紫外线的照射后分解成胺，胺再被氧化产生深色产物，导致漆膜泛黄严重。聚醚和聚酯的耐化学性及柔韧性等性能优良，但由于醚键存在导致漆膜易失光、粉化；聚酯的硬度稍低。故而，上述几种产品通常用于室内底漆、中间漆或深色面漆等。  \n\n脂肪族丙烯酸聚氨酯涂料是以脂肪族多异氰酸酯，如六亚甲基二异氰酸酯（HDI）和多羟基丙烯酸树脂为原料聚合而成。由于不含苯环，与芳香族聚氨酯涂料相比，它的氨酯键分解产生的脂肪胺不易分解而变色；而丙烯酸树脂同样具有良好的耐候性，同时兼具硬度和柔韧性。因此脂肪族丙烯酸聚氨酯涂料具有很好的硬度，又有极好的柔韧性；耐化学腐蚀，突出的耐候性，光亮丰满，干性好，表干快而不粘灰等特性，是一种高性能的长效重防腐蚀涂料，是目前在重防腐涂装体系中的首选面漆，在大部分严重腐蚀环境中得到广泛的应用。目前在重防腐涂装领域，最经典、最有效的涂料配套是：富锌（有机或无机）底漆1道/环氧云铁中间漆 $1{\\sim}2$ 道/聚氨酯面漆2道，总干膜厚度 $200\\sim350\\mu\\mathrm{m}$ 。这--配套十多年来已被广泛应用于桥梁、石油化工、电站、船舶和海上设施等面对严重腐蚀的各个领域，并被证明是行之有效的。其涂层防护期，一般在沿海地区为10年左右，在内陆地区可达15年以上。  \n\n(2）氟碳涂料20世纪90年代，日本较多使用氟碳涂料作为钢结构桥梁防护涂层的面漆并取得成功。例如1999年建成的明石海峡大桥（跨度 $1990\\mathrm{m}$ 悬索桥)、多多罗大桥（跨度 $890\\mathrm{m}$ 的斜拉桥)，其钢梁、钢塔均采用氟碳面漆。  \n\n在化学元素中，氟原子具有最高的电负性和除氢原子以外的最小的原子半径，因此氟碳聚合物具有极高的稳定性。在氟碳聚合物中，氟原子取代了氢原子，包围在碳链外形成紧密的保护层，使其不易受到外界的侵袭；又因为氟碳聚合物中大量的F—C键，是一种高键能化学键 $(460,2\\mathrm{kJ/mol})$ ，因此具有优异的保光、保色性、耐候性以及耐热、耐腐蚀、耐化学品、耐沾污、耐摩擦等性能，在低温下也可以固化。  \n\n目前，用于制漆的氟碳树脂品种有十几种。但应用在重防腐涂装的，大多是采用氟乙烯烃基乙烯基醚共聚物（FEVE）为主要成膜物质的新型氟碳树脂涂料。FEVE是一种由氟烯烃结构单元与不同的烃基乙烯基醚结构单元交替排列而成的非晶态聚合物，其分子结构和性能如图3-3-26所示。  \n\n2005年我国在参考日本工业标准JISK5658—2002《建筑用氟树脂涂料》起草并颁布了HG/T3792—2005《交联型氟树脂涂料》国家化工行业标准，该标准根据交联型氟树脂涂料的主要应用领域，分为两种类型，I型为建筑外墙用氟树脂涂料，ⅡI型为金属表面用氟树  \n\n![](images/70abc4f465b3ea003121c87644c26f4c885dab1c3116c0d680a782caa858e3f9.jpg)  \n图3-3-26 氟碳树脂分子结构以及官能团与性能的关系  \n\n脂涂料。  \n\n由于氟碳树脂只有在含氟的溶剂中才能较好地溶解，要生产低VOC含量的产品有一定难度，同时它的反应物会仍然含有异氰酸酯，所以在环境友好和健康以及施工性能方面等还需要进一步改进。  \n\n（3）聚硅氧烷涂料 一般来说，无机物具有较好的耐化学性；有机物则具有较好的物理性能。将有机物引入无机物以达到最佳的产品特性是长久以来涂料工作者的重要研究课题。最初，是将两种树脂直接混合的方式，但由于混容性等诸多的问题，无法达到令人满意的效果。有机-无机混接技术，即利用无机树脂改性的有机树脂交联聚合，从而使两种材料形成共享一个化学键的聚合体网络。混接技术主要包括以下四个方面的内容：有机基体、无机基体、互穿网络和真接枝。  \n\n聚硅氧烷涂料的杰出耐性就来源于无机物-聚硅氧烷树脂的硅氧键Si一O，它有以下特点。  \n\n$\\textcircled{1}$ Si—O键的键能高。Si—O的键能为$446\\mathrm{kJ/mol}$ ，而且Si、O原子形成d-pπ键，增加了高聚物及键能稳定性，需要很高的能量才能把它打开；  \n\n②在Si—O键中，Si和O原子的相对电负性的差数大，因此Si—O键的极性大，有51%离子化的倾向，对Si上连接的烃基有偶极感应影响，提高了所连烃基对氧化作用的稳定性，即Si一O一Si键对烃基基团的氧化能起到屏蔽作用。  \n\n因此聚硅氧烷涂料具有优异的耐热、耐紫外线性能以及抗氧化和耐化学品性能。而通过改性引人的有机物链，则大大提高了漆膜性能，包括弯曲性能、柔韧性、光泽、附着力，同时产品的成本也得到有效的控制。通过无机-有机的混接技术，聚硅氧烷涂料实现了将有机物的最佳特性（如施工性好、绕性、韧性、光泽和气温固化）和无机物的最佳特性（惰性、硬度、附着力和抗化学性，耐高温、耐候、耐紫外线和耐磨）有机地结合在一起。  \n\n聚硅氧烷树脂涂料是以通过某些功能性有机物改性的苯基甲基聚硅氧烷树脂为主要成膜物的。常用于改性的功能性有机物有：氢化环氧树脂、脲烷丙烯酸酯树脂、改性丙烯酸树脂（如羟基丙烯酸树脂、烷氧基硅烷基丙烯酸树脂、含酸官能团丙烯酸树脂或含不饱和键丙烯酸树脂)、氟化醇类等。目前来看，技术较为成熟，并已在市场上有一定成功应用的是氢化环氧树脂和丙烯酸树脂改性的苯基甲基聚硅氧烷树脂，即常说的脂肪族环氧聚硅氧烷涂料和丙烯酸聚硅氧烷涂料。  \n\n聚硅氧烷涂料的聚合反应，无论是丙烯酸聚硅氧烷，还是环氧聚硅氧烷，都是由含氨基官能团的硅氧烷树脂在环境中微量水分存在下的自聚反应而开始。随后其自聚产物——聚硅氧烷中的活性官能团氨基，再与氢化环氧树脂、脲烷丙烯酸酯树脂或含酸官能团的丙烯酸树脂中相应的活性基团互相交联聚合，从而形成结构复杂、互穿网络的多交联聚合物。其反应机理如图3-3-27所示。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 114,
+        "chunk": "# 第一步：自聚反应  \n\n![](images/939bc5bdf961f1865cb544b0293e19f862cc99c21b5f48b581ad55aef255f2a2.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 115,
+        "chunk": "# 第二步：交联聚合",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 116,
+        "chunk": "# 1.与氢化环氧树脂聚合  \n\n![](images/8534fb8403768a2a9e0e9a3fed9bbaaa67ebda45d056e5670d00b373ae64abad.jpg)  \n图3-3-27 聚硅氧烷反应机理  \n\n第一步的自聚反应很迅速，通常该组分是要隔绝空气包装，比如采取充氮保护等措施；施工时必须在使用前才开桶，并确保在规定的使用期内使用。  \n\n与经典的传统重防腐高档面漆聚氨酯面漆相比，聚硅氧烷有许多更为突出的优点。  \n\n$\\textcircled{1}$ 更好的保光保色性聚硅氧烷的杰出保光保色性来源于硅氧键的强度（Si—O—Si的键能为 $446\\mathrm{kJ/mol})$ 比碳碳键（C—C的键能为 $\\mathbf{358kJ}/\\mathbf{mol};$ ）的强度更高，因此需要更高的能量才能把它打开。在实验室按照ASTMG53—1993的方法，对聚硅氧烷涂料和聚氨酯涂料进行人工加速老化对比试验（QUV)。结果显示，聚氨酯涂料在 $2000\\mathrm{h}$ 时尚能保持原始光泽的75%，到4500h光泽只剩下原来的10%左右。而聚硅氧烷涂料在4500h时光泽可保持到原始光泽的 $75\\%$ ， $8000\\mathrm{h}$ 时光泽仍可达原来的 $45\\%$ 左右。如图3-3-28所示为聚氨酯面漆和聚硅氧烷面漆保光性比较。  \n\n$\\textcircled{2}$ 更优越的防腐性能由于聚硅氧烷树脂中硅氧键高键能的保证，以及有机-无机聚合物形成的互穿交联网络所给予的更为致密的漆膜，使得其拥有较聚氨酯面漆更为出色的防腐性能，而且涂装后维修的费用大大降低。  \n\n③更快的干燥特性聚氨酯涂料是通过多异氰酸酯与多元醇交联聚合而成膜的。虽然芳香族聚氨酯涂料反应迅速，但通常重防腐涂装中常用脂肪族多异氰酸酯为原料，以确保漆  \n\n![](images/8bed8bf5aa8e56f825dae6194180d48aaef55db1dfdae7a0d61eb4720a714d67.jpg)  \n图3-3-29不同涂料品牌的改性聚硅氧烷产品渗水性对比曲线1—环氧硅氧烷A；2—环氧硅氧烷B；3—丙烯酸硅氧烷C；4—丙烯酸硅氧烷D；5—环氧树脂试验方法：ASTMD1653-03方法B试验条件： $23^{\\circ}C$ ，RH $50\\%$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 117,
+        "chunk": "# 5.功能性防腐蚀涂料  \n\n(1）环氧沥青涂料用于制造沥青涂料的沥青树脂主要有三种来源：天然沥青、石油沥青及煤焦油沥青。比较三者的耐水性和防腐性，煤焦油沥青更为突出，在防腐涂料中应用最多。并且多以环氧树脂改性成一种双组分聚酰胺固化的环氧煤焦油沥青涂料，可自作底漆，实施“底-面合一”涂装工艺。其性能兼顾环氧树脂和煤焦油沥青树脂两者的优点：  \n\n$\\textcircled{1}$ 突出的耐水性和防腐性；  \n$\\textcircled{2}$ 良好的耐酸、耐碱和耐油性；  \n$\\textcircled{3}$ 附着力强、韧性好；  \n$\\textcircled{4}$ 价格较低，性价比优。  \n\n环氧煤焦油沥青漆作为潮湿、涉水环境下的长效防腐涂料，常用于淡水、海水浸泡部位和潮汐区、飞溅区及其他潮湿阴暗处钢结构防腐。  \n\n虽然沥青漆是一种使用历史悠久的涂料品种，但沥青中含有葱、菲、吖啶，吡啶、咔啶、吲哚等光感物质(其中有的含致癌性)，因而接触沥青的身体部位在阳光照射下就会发生光敏感性皮炎；接触到沥青烟雾时（特别是在阳光照射下）会引起鼻炎、喉炎和支气管炎等。临床表现为：面部、颈部、四肢等暴露部位会发生大片红斑，并有瘙痒感和烧灼感，重者局部有水肿、水疱及渗液。全身症状可有头痛、眩晕、疲倦、关节酸痛、恶心、呕吐、腹痛、腹泻等，伴有发热及白细胞增高症，对人体健康有较大的危害性。考虑到沥青含有致癌性物质，欧美已经限制在涂料中使用，环氧沥青漆曾经是船舶压载水舱的主要应用区域，但是现在IMO已经制定新的标准（PSPC 将在船舶涂料部分详细介绍)，其压载舱面漆为浅色，故而深色的环氧沥青漆将被浅色环氧系列涂料替代。  \n\n(2）防静电涂料液体石油产品在流动、过滤、混合、搅拌、加注、抽提等状况下，会因摩擦而产生静电荷，特别是轻质油类。当产生静电荷速率大于其导出速率时，就会形成静电荷的积聚，电压不断高升，并在尖端放电。当积聚的静电荷放电能量处于可燃油品蒸气与空气的混合物爆炸极限范围内时，随时可能发生静电起火、爆炸危害。据资料介绍，石油化工行业的静电事故，国内外曾多次发生。近年来，我国石油化工发展迅猛，伴随而来的静电事故也屡有发生。仅在近年内，就有10多起。如空罐高位混装油品时引起静电着火、风吹计量塑料管触发静电荷放电引爆汽油罐、煤油进罐；操作刚停止，采样时引起静电起火等，均造成了巨大的人身与财产损失。因此，切实做好防静电工作是确保石油化工产品贮运生产安全的重要内容之一。  \n\n防静电涂料是近20年来才迅速发展起来的一种新型涂料。早在20世纪40年代就开始研究与应用。日本于1957年开发并生产了各种类型的导电涂料。美国出于航空航天和军事工业发展的需要，从20世纪50年代以来就研制了一系列飞机雷达罩用抗静电涂料，其表面电阻率为 $(5\\mathord{\\sim}15)\\times10^{6}\\Omega$ ，以确保泄放积聚的静电荷，防止静电事故，使无线电导航、通讯设备性能充分发挥。之后发展迅速，品种齐全，应用领域不断扩大，制定并颁布了相关导静电的美军标准和专业标准。  \n\n我国防静电涂料的研发也起步于20世纪50年代，但大部分是碳系（石墨）型、碳纤维复合材料等导电漆或导电胶。近年来，以金属及金属氧化物为导电填料的新型导静电涂料迅速发展，以适应国防、军工、石油化工等各行各业的需要。  \n\n$\\textcircled{1}$ 防静电涂料种类防静电涂料通常由基料、颜（填）料、溶剂及其他助剂组成。其中至少有一种组分具有导电性能，以保证形成的涂层为导体或半导体，即涂料涂层的体积电阻率小于 $\\underline{{10^{10}\\Omega\\cdot\\mathbf{m}}},$ 、面电阻率在 $10^{5}\\sim10^{9}\\Omega$ 范围内的一种涂料，用以消除静电灾害及由此导致的各类关联性生产障碍。  \n\n目前市场上防静电涂料基本上是添加型导电涂料，按其导电填料类型分类，有以下三大类。  \n\na.金属系 银、铜、镍、锌等。  \n\nb.碳系 导电性石墨或炭黑。  \n\nc.金属氧化物系氧化锡、氧化锌、氧化锑处理的二氧化钛、添加锑的氧化锡等。  \n\n![](images/7113e229b729caca2e3a75d3e6ad099f557d6e00af52aeef861918b16bee8dba.jpg)  \n图3-3-30 导静电网络模型  \n\n防静电涂料导电机理 当涂料中导静电填料的体积浓度低于涂料导电的临界体积浓度时，填料之间被分隔开不能形成网络，则漆膜表现为不导静电。而当涂料中导静电填料的体积浓度达到涂料导电的临界体积浓度时，填料之间连接接触形成网络，则漆膜表现为导静电。导静电网络模型如图3-3-30所示。  \n\n无机系防静电涂料是由于导电填料之间彼此接触而产生导电能力的。但在涂料干燥固化之前，基料与导电填料是彼此分开，互不连续，而处于绝缘状态；  \n\n当涂料固化成膜之后，随着溶剂的挥发彼此混合紧密连接为一体，从而产生了导电性，即自由电子沿外加电场方向传递而形成电流。  \n\n有机系防静电涂料的作用机理有多种解释。其中之一为润滑作用说，认为涂膜的润滑作用减轻了表面摩擦，减少甚至消除了静电荷的产生。但有人认为润滑作用虽有，但不是主要的，主要因素是导电填料分子连续地排列于表面并达到一定的数量，吸收空气中的水分子后，形成了肉眼看不见的“水膜”，形成了导电通路，增加了静电荷通向空气、地下的电传导作用，从而消除了静电积聚。这就是常说的“导电通道”学说。此外，还有“隧道效应”学说，除了上述导电粒子间的接触外，由于电子在分散于聚合物母体中的导电粒子间隙里迁移时所产生的导电网络，从导电机理来看，导电填料分布越均匀，导电网络链越完整，涂料的导电性越高，漆膜屏蔽效能越好。  \n\n分析导电涂料的导电机理，有助于了解影响防静电涂料导电性的各种因素：如导电填料种类、形状、尺寸、填充量（浓度)、分散状态、基料种类以及固化条件等，并进而加以调整与控制，是涂料配方设计与施工的重要依据。  \n\n②我国有关防静电主要标准GB13348—1992《液体石油产品静电安全规程》；GB15599—1995《石油和石油设施雷电安全规程》；GB6950—2001《轻质油品安全静电导电率》；GB16906—1977《石油罐导静电涂料电阻率测定法》；SY/T0319—1998《钢制贮罐液体环氧涂料内防腐层技术标准》；MHJ5008—1994《民用机场供油工程建设技术规范》。  \n\n$\\textcircled{3}$ 防静电涂料的主要技术要求  \n\na.防静电涂料的涂层体积电阻率应低于 $10^{8}\\Omega\\cdot\\mathrm{m}$ ，表面电阻率应低于 $10^{9}\\Omega$ 8b.具有优良的漆膜附着力和防锈性，新造贮罐大多要求涂层防护期7年以上。c、必须耐石油产品长年浸泡，且不污染油品或诱发产品变质。  \n\n国家经贸委、国家质检总局、中石油、中石化等主管部门明确规定：“油罐进行内壁防腐时，应采用防静电涂料，涂料面电阻率应小于 $10^{9}\\Omega$ 。同时要经过认真试验，确定涂料对所贮油品性质无害，方可应用”。此外，中国民用航空总局（行业）标准MH」5008—1994《民用机场供油工程建设技术规范》第10.0.2条规定：“航空煤油油罐、管道和配件内壁禁止镀锌、镀镉或涂以富锌的材料”。而对防静电涂料最详细的技术要求，出现在国家标准GB6950—2001《轻质油品安全静电导电率》附录D“石油导静电涂料技术指标”和GB16906—1977《石油罐导静电涂料电阻率测定法》附录A“石油罐导静电涂料施工及验收规程”等标准中。防静电涂料技术指标见表3-3-21。  \n\n表3-3-21GB6950中附录 $\\mathbf{D}$ 规定的《石油导静电涂料技术指标》  \n\n\n<html><body><table><tr><td>检验项目</td><td>环氧/聚氨酯型</td><td>无机富锌型</td><td>漆酚型</td><td>检验方法</td></tr><tr><td>电阻率/Ω</td><td>105~10°</td><td>10°~10°</td><td>105~109</td><td>ASTM D 257</td></tr><tr><td>容器内状态</td><td>未变稠，易搅匀</td><td>未变稠，易搅匀</td><td>未变稠，易揽匀</td><td>一</td></tr><tr><td>贮藏稳定性</td><td>易重新搅匀</td><td>易重新揽匀</td><td>易重新搅匀</td><td>一</td></tr><tr><td>喷涂特性</td><td>能喷得光滑漆面</td><td>能喷得光滑漆面</td><td>能喷得光滑漆面</td><td>一</td></tr><tr><td>混合特性</td><td>易混合无粗粒</td><td>易混合无粗粒</td><td>易混合无粗粒</td><td></td></tr><tr><td>干燥时间/h 表干 ≤ 实干 ≤</td><td>4</td><td>0.5</td><td>0.5</td><td>GB/T 1728</td></tr><tr><td>耐冲击性/kgf·cm≥</td><td>24 50</td><td>5 50</td><td>24 30</td><td>GB/T1732</td></tr><tr><td>耐热性(24h)</td><td>120℃漆膜完好</td><td>400℃漆膜完好</td><td>150℃漆膜完好</td><td>GB/T1735</td></tr><tr><td>溶剂</td><td>不含氯化合物、乙烯 基乙二醇醚及其醋酸酯</td><td>不含苯、氯化合物、乙 烯基乙二醇醚及其醋 酸酯</td><td>不含苯、氯化合物、乙 烯基乙二醇醚及其醋</td><td></td></tr><tr><td>对1：1(体积比）航 空煤油/水的耐受性 (52℃±1℃,21d)</td><td>漆膜完好</td><td>漆膜完好</td><td>酸酯 漆膜完好</td><td>ASTMD3359</td></tr></table></body></html>  \n\n(3）耐高温涂料一般金属在高温下表面都会被氧化，造成金属的损耗；还会造成金属中合金的贫化，影响金属质量和力学性能。耐高温涂料是防止高温设备表面产生高温氧化的最为有效的防护措施之一。耐高温涂料一般要满足下列基本要求： $\\textcircled{1}$ 漆膜结构致密，完整无孔，腐蚀介质不易透过； $\\textcircled{2}$ 与底层金属有很强的结合力； $\\textcircled{3}$ 高强度，耐磨、耐腐蚀以及耐高  \n\n温； $\\textcircled{4}$ 均匀分布，和基体热容性好。  \n\n目前常用的耐高温涂料主要分为无机涂料和有机涂料两种。  \n\n无机耐高温涂料中应用最为广泛的是无机硅酸锌涂料。金属锌粉的熔点约420℃，900℃以上会汽化，以锌为原料的涂料可以抵抗400℃的高温；同时无机硅酸锌涂料具有优异的阴极保护功能，因此它是 $\\rightharpoonup$ 种防腐性能优异的耐高温涂料。  \n\n有机耐高温涂料中最为普遍的是有机硅耐高温涂料，也称聚硅氧烷耐高温涂料。有机硅耐高温涂料的优越性能来源于有机硅树脂中的无机结构Si—O—Si键，它具有良好的热稳定性和耐高温氧化性。而有机硅树脂中的有机基团—硅烷醇基团为疏水基团，赋予了涂料良好的耐水性；同时有机基团的引入，也使有机硅树脂可以溶于甲苯、二甲苯等芳香族溶剂及酮类溶剂，为制备涂料提供了可能性。因此有机硅耐高温涂料具有无机和有机聚合物的双重性能，具有优良的介电性和耐高温性，耐水、耐潮、耐候性能良好。  \n\n有机硅耐高温涂料在常温下，随溶剂挥发成膜。但此时仅为有机硅树脂的物理干燥，没有交联固化的漆膜既软又不致密，无论是在力学性能，还是耐化学性能方面均较差。当温度升高至 $200^{\\circ}C$ 时，有机硅树脂开始聚合；在 $300^{\\circ}C$ 左右，有机硅树脂上有机基团如甲基、苯基大部分没分解，耐高温涂层具有有机涂层的某些性能，如柔软性、光泽性等；继续升温，有机基团则继续分解，在 $350^{\\circ}C$ 以上有机硅树脂就分解成无机硅氧交联结构。示意如图3-3-31所示。  \n\n![](images/edf677569f2fd743b90bdd737fe9ed2ce5e42017d8cb4ec65141ed7ab00123f9.jpg)  \n图3-3-31 有机硅树脂自交联机理$\\mathbb{R}_{1}\\dot{\\mathrm{\\Omega}}\\mathbb{R}_{4}=\\mathbb{C}\\mathrm{H}_{3}$ 或 $C_{E}\\cdot H_{E}$  \n\n这就是有机硅耐高温涂料的“二次成膜”机理。涂料成膜过程中，涂层中玻璃料熔化成膜，使耐高温涂层更加致密。  \n\n耐高温涂料的耐热性能还与所使用的颜料紧密关联。常用颜料的耐热性如下：  \n\n$\\textcircled{1}$ 钛白粉稳定性能优良，适用于 $200^{\\circ}C$ 长期耐热，短期极端最高耐温可达 $350{\\sim}400^{\\circ}\\mathrm{C}$ 不变色。$\\textcircled{2}$ 炭黑同样适用于 $200^{\\circ}C$ 长期耐热，短期极端最高耐温可达 $250^{\\circ}C$ ? $300^{\\circ}C$ 以上颜色会褪去。$\\textcircled{3}$ 酞菁蓝只能用于 $200^{\\circ}C$ 以下的环境。$\\textcircled{4}$ 酞菁绿也只能用于 $200\\%$ 以下的环境， $200^{\\circ}C$ 时 $0.5\\mathrm{h}$ 就会产生变化。$\\textcircled{5}$ 铬黄和钼红均在 $140^{\\circ}C$ 以上发生变化。$\\textcircled{6}$ 氧化铁黄在 $160^{\\circ}C$ 以上会脱去水分，颜色变红。$\\textcircled{7}$ 氧化铁红可以抵抗 $200\\%$ 高温环境。$\\textcircled{8}$ 金属颜料中铝粉的熔点高达 $600^{\\circ}C$ ，可以用来制备耐 $500\\sim600^{\\circ}C$ 的高温涂料；而锌粉则常用于制备耐 $400^{\\circ}C$ 的高温涂料。  \n\n因此，对于耐高温涂料的颜色选择应非常慎重，否则会导致涂层的耐热性能受到影响。通常耐高温涂料的颜色仅限于白色、黑色或金属色。常见的几种耐高温涂料的耐热性能见表3-3-22，供读者参考。耐高温涂料将在本章第五节详细介绍。  \n\n表3-3-22几种耐高温涂料的耐热性能  \n\n\n<html><body><table><tr><td>耐高温涂料品种</td><td>最高耐热温度/℃</td><td>耐高温涂料品种</td><td>最高耐热温度/℃</td></tr><tr><td>无机硅酸锌涂料</td><td>400</td><td>黑色有机硅涂料（含炭黑颜料）</td><td>200</td></tr><tr><td>白色有机硅涂料（含钛白粉颜料）</td><td>200</td><td>银色有机硅涂料（含金属铝粉）</td><td>600</td></tr></table></body></html>  \n\n(4）减阻型气体管道内涂漆气体管道特别是长输管线，内涂装的主要目的在于减低气体输送阻力，提高输气效率。据资料介绍，在相同条件下，未作内涂的管道气体输送效率只有 $81\\%\\sim85\\%$ ，而内壁喷涂了减阻型内涂层的管道气体输送效率增至 $95\\%$ 以上，与未作内涂的管道相比，输气率提高 $6\\%\\sim12\\%$ 。1958年，在田纳西气体管理公司的一条已使用10年、长 $19.\\ 14\\mathrm{km}$ 、管径 $60.96\\mathrm{cm}$ 、管壁厚 $0.635c m$ 的管道所进行内涂试验，证实了内涂层对气体输送的价值。当气体输送率在 $150{\\sim}450\\ensuremath{\\mathrm{MMsdf}}$ $\\mathrm{10^{6}f t^{3}/d}$ + $\\mathrm{1ft{=}0.305m)}$ ，测量得出的输气率增加为 $5\\%\\sim10\\%$ 。而实际的增量取决于管道长度和气体流动特性。而且，随着内涂技术的发展，效果愈明显。1998年，挪威科技大学进行的流动性测试确定内涂管道可提高气体输送量 $21\\%$ 0  \n\n据西气东输内涂装课题组2001年报告，天然气管道的减阻内涂技术是一项经济效益显著的高新技术。初期投入成本的增加将会有几倍的收益，管径越大、线路越长、输气量越大，收益就越高，主要体现在以下几方面。  \n\n$\\textcircled{1}$ 在管径不变的前提下，可提高输量 $(3\\%\\sim30\\%)$ 。  \n$\\textcircled{2}$ 在输量一定的前提下，可缩小管径节约钢材（约 $2\\%$ 。  \n$\\textcircled{3}$ 在压力不变的前提下，可减少压缩机站的数量(据测算西气东输减了3个加压站)。  \n$\\textcircled{4}$ 由于摩擦阻力减小，压缩机动力消耗减小（约 $20\\%$ 。  \n$\\textcircled{5}$ 延长清管周期，减少清管次数。  \n$\\textcircled{6}$ 减轻管内壁腐蚀，保证气体纯度。  \n\n技术要求如下。  \n\n输气管道内涂，应执行国内外相关标准：SY/T6530—2002《非腐蚀性气体输送用管线 内涂层》；APIRP5L2《非腐蚀性气体输送管道内覆盖层的推荐准则》；SY/T0457—2000 《钢质管道液体环氧涂料内防腐层》等。  \n\n对所选择的涂料，必须具有以下几方面的基本性能。  \n\n$\\textcircled{1}$ 第一是减阻，即通过内壁涂层减低输送气体与管道内壁表面之间的运动摩擦阻力。在相同的动力消耗下，可提高长输管线的输气效率，以体现其经济性。  \n\n$\\textcircled{2}$ 内涂层与管道内壁表面粘接力强，即漆膜附着力好，以确保涂层最大使用寿命。  \n\n$\\textcircled{3}$ 干膜厚不小于 $70\\mu\\mathrm{m}$ 睿$\\textcircled{4}$ 优异的防腐性能。  \n\n$\\textcircled{5}$ 符合“底-面合一”的工艺要求，既当底漆又当面漆，以适应管道内涂机械化涂装工艺条件。  \n\n根据SY/T6530—2002《非腐蚀性气体输送用管线内涂层》标准，减阻型气体管道内涂漆钢板样实验室性能试验技术条件见表3-3-23。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 118,
+        "chunk": "# 6.防腐蚀涂料的新发展  \n\n(1）鳞片状金属颜料的应用由于鳞片状颜（填）料在漆膜中互相平行交错叠加，切断漆膜中的毛细孔，起到迷宫效应，能有效屏蔽和极大阻缓了外界水、氧、氯离子等腐蚀性介质的渗透，提高涂层的抗腐蚀能力。目前，涂料工业中常用的鳞片状防锈颜料主要有云母氧化铁、玻璃鳞片等，属于非金属原料。考虑到片状金属具有良好的延展性、导热性、可加工性以及装饰效果独特，市场发展前景看好，除铝粉外，一些新型片状金属填料陆续投放市场，如鳞片状锌粉、鳞片状不锈钢粉等。  \n\n表3-3-23SY/T6530—2002钢板样实验室性能试验验收准则   \n\n\n<html><body><table><tr><td>序号</td><td>试验项目</td><td>验收准则</td><td>测试方法</td></tr><tr><td>1</td><td>耐盐雾（划×法）500h</td><td>涂层无鼓泡，用干净塑胶带拉拔，无任何方向 不大于3.2mm的撕裂涂层（包括划线在内）</td><td>ASTMB 117</td></tr><tr><td>2 水浸泡</td><td></td><td>距边缘6.3mm以内无鼓泡</td><td>饱和碳酸钙溶液、100%浸 泡，室温，21天</td></tr><tr><td>3</td><td>甲醇与水等体积混合、浸泡</td><td>距边缘6.3mm以内无鼓泡</td><td>100%浸泡、室温，5天</td></tr><tr><td>4</td><td>剥离</td><td>通过</td><td>SY/T 6530附录C</td></tr><tr><td>5</td><td>弯曲</td><td>或奔曲成≥13mm时目测无剩落、附着力下降</td><td>ASTM D 522</td></tr><tr><td>6</td><td>黏附力</td><td>除切口处外其他位置无任何剥离</td><td>SY/T6530附录D</td></tr><tr><td>7</td><td>硬度</td><td>25℃±1C时，Buchholz最小94</td><td>ISO 2815</td></tr><tr><td>8</td><td>气鼓泡</td><td>无鼓泡</td><td>SY/T 6530附录E</td></tr><tr><td>9</td><td>耐磨性</td><td>最小磨损系数23</td><td>ASTM D968方法A</td></tr><tr><td>10</td><td>水压鼓泡</td><td>无鼓泡</td><td>SY/T 6530附录F</td></tr></table></body></html>  \n\n① 鳞片状锌粉据资料介绍，全世界每年用于生产富锌涂料的锌粉量高达2万～4万吨，而金属锌资源有限，国际锌价不断攀升。因此，如何在不降低富锌涂料性能的前提下，节省锌粉用量，为业界关注焦点，而鳞片状锌粉的开发成功提供了一条出路。  \n\n德国Eckart-Werke、澳大利亚Benda、比利时锌加公司、美国的Dacro 公司等，生产了鳞片状锌粉并研发了多种鳞片型富锌涂料，所采用的基料包括：环氧树脂、氯化橡胶、硅酸乙酯等。由于鳞片型锌粉优良的屏蔽性能、平行搭接性能、电接触性能、易悬浮的特性使这一系列的鳞片型富锌涂料的防腐性以及施工性明显优于传统的球状锌粉富锌涂料。  \n\n从图3-3-32(a）中可以明显观察到，在球状锌粉富锌涂层中有大量的孔隙（图中黑色背景）存在，并且锌球与锌球之间是点接触的形式，只有少量树脂基料包裹在锌球上，涂层结构相对疏松；而图3-3-32（b）中的片状锌粉富锌涂层，片锌与片锌之间面面接触，交替垒叠，孔隙几乎都被树脂基料填满，涂层极为致密。  \n\n![](images/3f5fea4ca346bd5c57c5aa47f87af8c67d3e5559831ce5c7654f02f26bde2a33.jpg)  \n图3-3-32 两种结构锌粉的富锌漆涂层结构电子显微镜扫描照片  \n\n以鳞片状锌粉为防锈颜料，选用不同的基料（如硅酸乙酯、环氧树脂、氯化橡胶等）可以研制出种类繁多的水性、溶剂型、无机或有机片锌富锌涂料。这些涂料不仅抗腐蚀性能优于普通球锌富锌涂料，并且由于锌粉添加量的大幅度减低（例如：环氧富锌底漆，“球锌”不挥发分中锌含量在 $70\\%$ 左右，换成“片锌”锌含量可减至 $50\\%$ 左右，节省金属锌粉用量约1/3)，而且成本不高于甚至低于球锌涂料。更由于其单位面积的涂覆量更大，施工涂层更薄，已经被国外公司大量用于集装箱用车间底漆。所以，鳞片状锌基涂料将是未来富锌涂料的发展方向之一。  \n\n$\\textcircled{2}$ 鳞片状不锈钢粉不锈钢鳞片涂料最早被应用于石油管道的厚浆型重防腐涂料中，由于其本身的耐酸、耐碱、耐磨、耐高温等特性，增强了涂层的耐化学品性、耐老化性以及耐磨、耐温度变化的性能。不锈钢鳞片在涂层中与基体相互平行叠加排列，形成了致密的防渗透层。据测算，在涂层中不锈钢鳞片层的分布可达到上百层，延长了介质渗透扩散的路程，产生显著的迷宫效应。但是，传统的不锈钢鳞片的厚度太厚，其松装密度都在 $2.0{\\cdot}/\\cdot$ $\\mathrm{cm^{3}}$ 以上，这就造成了不锈钢鳞片在基料中的悬浮性不好，易沉淀。致使不锈钢鳞片通常只能应用在喷涂厚度达到数百微米乃至数千微米的场合，使其应用受到了限制。  \n\n近几年来，国外不锈钢鳞片涂料有了突破性的进展，其突破点在于采用新的工艺，开发出了超薄型的不锈钢鳞片。例如：美国No-vamet公司生产的超薄型不锈钢鳞片的松装密度在 $0.8\\mathrm{g}/\\mathrm{cm}^{3}$ 左右，片径在 $10\\sim30\\mu\\mathrm{m}$ ，厚度在 $0.6\\mu\\mathrm{m}$ 以下。采用这种薄型的不锈钢鳞片，选择适合的基料树脂，开发出超薄型不锈钢鳞片涂料，喷涂厚度仅为数十微米，而防腐性能却能达到喷涂厚度为数百微米的防腐效果。电子显微镜下放大的不锈钢鳞片结构如图3-3-33所示。  \n\n国外把超薄不锈钢鳞片用在粉末涂料、集装箱涂料、汽车涂料、建筑涂料、医疗器具、烹调器具（如不粘锅）上。一种由日本公司开发的通过采用两种高性能树脂作基料，超薄不锈钢鳞片作填料的“不锈钢耐蚀涂料”，经日本原子力研究所放射线照射检验卫生合格，并通过了日本食品卫生协会检验，其成膜有类似不锈钢的外观，当作面漆使用在包括化学、食品、环保、核能、临海、酸洗、电镀、染整、制药、钢铁、桥梁、电子等多种场合下防腐涂装。  \n\n![](images/60c4a01eb550944817b57f4ffb5bdceb5d89d638dfdb064480f91d6a331bd4d5.jpg)  \n图3-3-33不锈钢鳞片的电子显微镜扫描照片  \n\n美国TOD制造公司在电镀设备表面采用含有不锈钢颜料的各种涂料涂装，解决了电镀厂严重的腐蚀问题。多年来不再需要维护和重新涂装。美国Armour化学工业公司在过滤氯化铵醇溶液除去结晶的氯化钠工序中存在严重的腐蚀问题，通过在热交换器上喷涂含有不锈钢鳞片的涂料，解决了这个问题。此外，美国电力公司俄亥俄州Canton工业基地中，不锈钢鳞片涂料取得很好的防腐蚀效果。  \n\n总之，鳞片状金属颜料在涂层中形成了平行搭接，相互交错的层叠结构和“迷宫效应”提高了涂层的屏蔽性，延缓了腐蚀性介质到达金属基体的时间，从而延长了涂层的防腐寿命。  \n\n鳞片状锌基涂层，片锌间以面接触代替球锌间的点接触，大大提高了涂层的屏蔽性和导电性，从而提高了涂层的电化学保护性能。  \n\n鳞片状不锈钢粉的耐酸碱、耐高温、高耐磨、不失色以及具有不锈钢光泽装饰性的特征使其在防腐、装饰面漆领域具有广泛的应用前景。  \n\n(2）聚脲弹性体涂料 斗喷涂聚氨酯/聚脲弹性体技术是在反应注射成型（reactioninjec-tion molding，RIM）技术的基础上，于20世纪70 年代中、后期发展起来的。近十年来，国内的科研院所（如青岛海洋化工研究院）致力于此方面的研究，并在市场上取得了一些成功的应用。  \n\n喷涂聚氨酯/聚脲弹性体技术的基础是利用多异氰酸酯中—NCO键的活性，与多元醇或多元胺相反应而成。多异氰酸酯与多元醇反应，生成物成为聚氨酯；与多元胺反应，生成物成为聚脲。其主要反应简式如图3-3-34所示。  \n\n聚氨酯反应：  \n\n$$\n\\begin{array}{r l}{{\\mathrm{}}}&{{}\\mathrm{~\\boldmath~\\gamma~}_{\\mathrm{R}\\mathrm{-}\\mathrm{N}\\mathrm{-}\\mathrm{C}\\mathrm{-}\\mathrm{O}\\mathrm{~+~}\\mathrm{R}^{\\prime}\\mathrm{-}\\mathrm{OH}\\mathrm{~\\frac{\\partial~\\hat{\\mathcal{H}}(\\hat{\\mathcal{H}})}{\\partial\\mathrm{R}\\mathrm{-}\\mathrm{RH}\\mathrm{-}\\mathrm{C}\\mathrm{-}\\mathrm{OR}^{\\prime}}}}}\\end{array}\n$$  \n\n多异氰酸酯与水反应：  \n\n$$\n\\mathrm{R}{\\mathrm{-}}\\mathrm{N}{\\mathrm{-}}\\mathrm{C}{\\mathrm{-}}\\mathrm{O}\\ +\\mathrm{H}_{2}\\mathrm{O}\\ {\\longrightarrow}\\ \\mathrm{RNH}_{2}+\\mathrm{CO}_{2}\\ \\uparrow\n$$  \n\n聚脲反应：  \n\n$$\n\\begin{array}{r}{\\begin{array}{c c}{0}&{\\mathrm{~}}\\\\ {\\parallel}&{\\mathrm{~}}\\\\ {\\mathrm{R}\\mathrm{~}\\mathrm{~}\\mathrm{~N}=\\mathrm{C}\\mathrm{-}\\mathrm{0}\\ +\\textrm{\\texttt{R}}^{\\prime}\\mathrm{-}\\mathrm{NH}_{2}\\longrightarrow\\mathrm{~}\\mathrm{R}\\mathrm{-}\\mathrm{NH}\\mathrm{-}\\mathrm{C}\\mathrm{-}\\mathrm{NH}\\mathrm{-}\\mathrm{R}^{\\prime}}\\end{array}}\\end{array}\n$$  \n\n喷涂弹性涂料的发展经历了三个阶段。最早开发的是喷涂聚氨酯弹性涂料（简称SPU)，但由于在施工时，体系容易与周围环境中的水分、湿气反应，产生二氧化碳，生成泡沫状弹性体。为了克服SPU的这一弊端，人们在树脂成分中引人了端氨基化合物，即第二阶段的产品喷涂聚氨酯/聚脲弹性涂料（简称SPU/SPUA)。这样，可有效地阻止异氰酸酯与水分、湿气的反应，材料力学性能得到很大的改善，工程应用明显增加。  \n\n但是SPU/SPUA仍然没有从根本解决体系发泡的问题，在工程实践中，还是经常出现一些缺陷。从20世纪80年代中期开始，喷涂聚脲弹性体（SPUA）研制成功，并取代SPU和 SPU/SPUA成为喷涂弹性涂料市场的主体。从反应活性来说，SPU或SPU/SPUA必须使用催化剂，而SPUA端氨基聚醚和胺扩链剂作为活泼氢组分（以下简称R组分)，它与多异氰酸酯（以下简称A组分）的反应活性极高，无需任何催化剂，即可在室温（甚至 $0^{\\circ}C$ 以下）瞬间完成，从而有效地克服了SPU和SPU/SPUA在施工过程中，因环境温度和湿度的影响而发泡，造成材料性能急剧下降的致命缺点。表3-3-24通过三代喷涂弹性体的组成成分和主要的优缺点来简单地描述其发展历程，供读者参考。  \n\n表3-3-24 喷涂聚氨酯/聚脲弹性体的技术发展  \n\n\n<html><body><table><tr><td>阶段</td><td>体系</td><td>A组分</td><td>R组分</td><td>主要优、缺点</td></tr><tr><td>第一阶段</td><td>SPU（喷涂聚氨酯）</td><td>MDI基</td><td>EO封端多元醇、二醇扩链 剂、催化剂</td><td>优点：价廉 缺点：对水敏感，极易发泡； 力学性能差等</td></tr><tr><td>第二阶段</td><td>SPU/SPUA（喷涂聚氨 酯/聚脲）</td><td>MDI基</td><td>EO封端多元醇、芳香二胺 扩链剂、催化剂</td><td>优点：价格适中 缺点：发泡、力学性能一般</td></tr><tr><td>第三阶段</td><td>SPUA（喷涂聚脲）</td><td>MDI基 m-TMXDI基</td><td>端氨基聚醚、芳香二胺扩 链剂、端氨基聚醚、脂肪二胺学性能好，耐老化性能突出 扩链剂</td><td>优点：对温、湿度不敏感，力 缺点：价高</td></tr></table></body></html>\n\n注：MDI为二苯甲烷二异氰酸酯。TMXDI为四甲基苯二亚甲基二异氰酸酯。  \n\n喷涂聚脲弹性体（SPUA）有众多优越的性能，是保护钢铁构件和混凝土防湿、耐磨及防腐蚀的理想材料，其性能简述如下。  \n\n$\\textcircled{1}$ 固化速率极快。SPUA可在任意曲面、斜面及垂直面上喷涂成型，不产生流挂现象，不含催化剂、快速固化，5s胶凝、lmin可达步行强度、30min即可投人使用。  \n\n②对环境温度、湿度不敏感。可在高湿和低温环境下施工，  \n\n③100%固含量，零VOC含量，属环境友好型涂料；一次喷涂可达2000um，提高施工效率。$\\textcircled{4}$ 涂层的物理性能优异。高强度、耐冲击、耐磨，同时漆膜又兼有出色的弹性和柔韧性。$\\textcircled{5}$ 耐化学性能优良。可以抵抗多种化学介质的腐蚀。$\\textcircled{6}$ 具有良好的热稳定性。可以在 $150^{\\circ}C$ 下长期使用。$\\textcircled{7}$ 与颜料的相容性好。可以制成多色彩的产品。$\\textcircled{8}$ 配方可以调整。通过组分的改变，可以制成手感从软橡皮（邵氏A30，相当于乳胶手套）到硬弹性体（邵氏D65，相当于玻璃钢）的各种涂层。  \n\n由于SPUA的固化速率极快，因此它与一般的涂料在施工方式上有着很大的不同，需要使用专用的施工设备。包括物料输送系统、计量系统、混合系统、雾化系统和清洗系统。这在很大程度上限制了SPUA的推广使用。  \n\n近年来，国内外的研究机构在提高SPUA涂层的耐候性能和降低体系的反应速率方面做了大量的工作。青岛海洋化工研究院研制出聚天门冬氨酸酯为基材、一种新型脂肪族、慢反应型SPUA，具有高耐候性，并保留传统的SPUA品种漆膜优越的理化性能，但是它仍需要使用专门的SPUA设备施工。因此展望未来，设计出反应速率比较慢的体系，使得SPUA采用普通的喷涂设备就可以施工，仍是它的发展方向。  \n\n(3）高固体分涂料和无溶剂涂料通常防腐涂料每道涂覆干膜厚 $25\\sim50\\mu\\mathrm{m}$ ，要达到较厚的膜厚，必然增加涂覆次数，这不但费工费时，更带来大量的有机溶剂挥发而污染环境，不符合各国政府对涂料中挥发性有机化合物（volatileorganiccompounds，VOC）含量愈来愈严格的限制。而高固体分涂料和无溶剂涂料正由于其高固分、低VOC，不含或少含溶剂，符合涂料工业环保、经济、节能、高效这一大方向而日益受到重视。  \n\n在高固体分涂料中，环氧树脂涂料应用最为广泛。传统的环氧树脂涂料，体积固体分为$50\\%$ 左右，而高固体分涂料的体积固体分至少达到 $68\\%$ 以上。很多高固体分环氧涂料的体积固体分达到 $80\\%\\sim90\\%$ ，溶剂用量则大幅度地下降。  \n\n无溶剂涂料则是高固体分涂料发展的必然结果。由于彻底解决了有机溶剂挥发排放问题，对环境保护和劳动保护以及防火安全等均有积极意义。  \n\n无溶剂涂料广义地讲是指不含有机溶剂或水的涂料，狭义地说是指不含有机溶剂挥发到大气中的液体涂料。传统的清油、熟桐油是属于广义的无溶剂涂料。现代无溶剂涂料是指采用活性溶剂作为溶解介质的液体涂料。在其成膜过程中，活性溶剂与树脂反应交联而成为涂膜的组成部分，不像一般溶剂那样绝大部分挥发逸出。  \n\n当然，提高涂料固体分并不是单纯地靠减少或不用有机溶剂来达到，它涉及成膜树脂的低黏度化、活性稀释剂的应用以及新型助剂的应用等一系列新原料和新技术。黏度的高低主要在于树脂分子量大小及固体分的高低，Mercurio及Lewis所绘制的分子量、固体分的等黏度曲线（图3-3-35）说明了三者之间的关系。  \n\n![](images/1a7a785a927fbe30bf8c6a48c13f2d7f87846f6a407c87afda7836719ec109ba.jpg)  \n图3-3-35 分子量与固体分的等黏度曲线  \n\n假定施工应用的合适黏度为0.1Pa·s左右，则只有分子量为2000～3000时才能使固体分接近70%，还需通过选择适合的活性溶剂及助剂等技术措施。  \n\n无溶剂涂料的特点如下。  \n\n①厚膜化，一次可喷涂100～1000μm，大大提高工效。  \n\n②边缘覆盖性好，甚至对没有处理过的钢板边缘也有很强的覆盖能力，比溶剂型涂料效果更好。  \n\n③涂层不收缩，内应力较小，无伸长力。  \n\n$\\textcircled{4}$ ④突出的物理机械性能、耐磨性与耐化学品性。  \n\n③无溶剂挥发到大气中，对环境保护和劳动保护以及防火安全等均有积极意义。  \n\n(4）水性防腐涂料常用的重防腐涂料都是采用有机溶剂作为涂料体系的稀释物。现在，人们开始意识到有机溶剂的危害性，主要存在以下两方面。一方面是考虑人类自身的健康。多年来，世界卫生组织（WHO）一直关注着这方面的研究。多项研究表明，如果没有有效的防护措施，长期吸入有机溶剂，会导致所谓的“涂料综合征”（painter's syndrome），主要表现在容易疲劳、记忆力下降以及神经系统方面的疾病。另一方面是有机溶剂对于环境造成的危害。有机溶剂挥发后，在紫外线的作用下容易分解，产生具有高活性的产物。这些高活性的产物会与大气中的工业污染物以及汽车尾气，如氮氧化物和硫氧化物反应，生成一些对环境有害的物质，如臭氧等。这些有害物会导致烟雾、酸雨，影响生物的新陈代谢，导致全球气温变暖。  \n\n正因为有机溶剂的这些危害性，从20世纪70年代开始，欧美等国相继出台了相应的强制性法规，限制涂料中挥发性有机化合物（VOC）的含量，降低对环境的危害。近年来，国内也越来越关注此类问题，低VOC含量的产品成为今后涂料发展的趋势。  \n\n水性涂料，顾名思义，是以水为主要溶剂，同时以水来稀释和清洗的涂料。因此水性涂料的VOC含量较低，通常在 50g/L以下。水性涂料因为主要溶剂是水，因此具有以下优点。  \n\n$\\textcircled{1}$ 水的来源广泛，净化容易。  \n$\\textcircled{2}$ 在施工过程中无火灾危险。  \n$\\textcircled{3}$ 基本不含苯类等挥发性有机溶剂。  \n$\\textcircled{4}$ 水代溶剂，可节省大量资源。  \n$\\textcircled{5}$ 涂装时使用过的工具直接用水进行清洗。  \n$\\textcircled{6}$ 工件经除油、除锈等处理后，不待完全干燥即可施工。  \n在工业重防腐涂料体系中，主要应用的水性涂料有以下儿种类型。  \n$\\textcircled{1}$ 水性无机富锌底漆。  \n$\\textcircled{2}$ 水性环氧涂料（包括水性环氧富锌底漆）。  \n$\\textcircled{3}$ 水性丙烯酸涂料。  \n\n(1）水性无机富锌底漆目前最常见的是水性自固化无机富锌底漆，一般以碱金属硅酸盐为主要的成膜物，如硅酸钠（俗称水玻璃）、硅酸钾或硅酸锂。水性自固化无机富锌底漆由两部分组成，基料为碱金属硅酸盐水溶液，固化剂为金属锌粉和其他的填料。其固化过程可以分成三个步骤：首先，随着水分的挥发，碱金属硅酸盐水溶液浓缩并通过水解生产一定数量的聚硅酸；随后，在环境中水和二氧化碳的存在下，硅酸盐混合物（碱金属盐和聚硅酸）与金属锌以及钢材表面产生反应，生成硅酸锌以及锌-铁-硅酸盐的混合物。需要指出的是，体系中的碱金属盐可以加速反应的进行，从而确保其自固化反应的进行。水性无机富锌底漆的漆膜形成后，漆膜中的金属锌会继续和环境中的空气和水分反应，产生碳酸锌和氢氧化锌。经过一段时间后（几个月甚至一年的时间)，这些反应产物会完全填没漆膜的孔隙，最终形成连续、致密、附着力良好的坚固漆膜。  \n\n水性自固化型无机富锌底漆固化反应式如下。  \n\n反应一：随水分的挥发，碱金属硅酸盐的脱水、浓缩。  \n\n![](images/1d22d31d60f3c2778eb46f10f2a2d5104ab39ad82ce382c9765bf347e9935c15.jpg)  \n\n反应二：空气和环境中的水与锌、聚硅酸反应，漆膜开始固化；底材中的铁离子也同时与硅酸盐进行着反应。  \n\n![](images/870719e0f39904c543830111fba5bb97867b82d90d05316325c1f15b8d3984be.jpg)  \n\n反应三：经过一段时间的反应，空气、水、锌形成了连续坚固的漆膜。  \n\n![](images/182222e8f90359a4703cf760cf9373e7a4ed9e3747b54f7d92eed73541c9518d.jpg)  \n\n(2）水性环氧涂料主要是水分散型环氧涂料。环氧树脂虽不是水溶性的，但可以在水中乳化，通常由两组分组成：基料为憎水性的环氧树脂，固化剂为亲水性的胺类固化剂。水性环氧涂料的固化过程可以分为两个步骤；一是水分的挥发；二是环氧树脂与固化剂的交联反应。  \n\n水分散型环氧涂料固化原理如图3-3-36所示。  \n\n水性环氧富锌的固化原理与水性环氧涂料相似，只是在水性环氧基料中增加了一组分，即作为起到电化学阴极保护作用的防锈颜（填）料：金属锌。  \n\n![](images/934c7fc372a82052fb95d7b9c616806e990b6b965bcf5c2a118a84f7e075dc9a.jpg)  \n图3-3-36 水分散型环氧涂料固化原理示意  \n\n从水性环氧涂料的固化机理可以看出，成膜过程中水分的挥发速率非常关键，如果水分挥发过慢、低于环氧树脂与固化剂的交联速率，漆膜中就会含有水分，性能也会有所降低。因此其成膜固化过程对环境的温度、湿度和通风条件要求较高；同时，由于环氧树脂低温固化性能差这一固有的缺点，环境温度通常要求在 $10C$ 以上，相对湿度不能超过 $85\\%$ ，最好低于 $65\\%$ 。  \n\n同时，需要注意的是，水性环氧涂料的适用期（potlife）要比一般的溶剂型环氧漆要短，通常在 $2h$ 左右。与溶剂型环氧涂料不同，水性环氧涂料的适用期并不是由黏度增加来表现的。在20℃时，3h后的混合物看上去仍然可用，但这时涂料的保护性能已大受影响，所以不可再用。另外，温度降低也会缩短水性环氧涂料的适用期，这点也与溶剂型环氧涂料有很大的不同。另外，水性环氧涂料由于存在大量的亲水基团和较低的分子量，与溶剂型环氧涂料相比，耐化学品性能较差。  \n\n(3）水性丙烯酸涂料水性丙烯酸涂料是以水性丙烯酸树脂分散体为成膜物质的。一般水性丙烯酸分散体分子量较溶剂型丙烯酸树脂大。这些具有长链和三维立体结构的丙烯酸分散体被封闭成颗粒（直径通常小于 $0.5\\mu\\mathrm{m},$ ，分散在水和成膜溶剂中。在施工成湿膜后，水分逐渐挥发，分散着的聚合物颗粒逐渐靠近；而成膜溶剂挥发很慢，当水挥发到一定的程度，聚合物颗粒就紧紧地挤在一起了。这时成膜溶剂将聚合物颗粒的外壁溶解，释放出丙烯酸分散体，从而形成连续、内聚的漆膜。水性丙烯酸涂料的固化机理示意图如图3-3-37所示。  \n\n![](images/d4070e5105ccdbda730b127efbd5b38cb24904302855e1499d77d91f824753aa.jpg)  \n图3-3-37 水性丙烯酸涂料的固化示意  \n\n通过向共聚物分子链中引入带各种官能团的单体，水性丙烯酸涂料可以制成不仅耐候性能优良，而且致密、柔韧、耐腐蚀的漆膜。  \n\n水性丙烯酸涂料能制成有光和半光型，可作为底漆、面漆和用于混凝土表面的封闭漆。能在大多数的底材表面施工，如钢材、镀锌件、铝材、混凝土、砖石和木材等。  \n\n水性涂料是用水来做溶剂和稀释剂的，因此它的缺点也与水的自身特点有关。在低温和相对湿度高时水分挥发慢，而且在0℃时水会结冰，因此通常水性涂料要求在5℃以上才可施工，漆膜固化时的环境湿度最好在40%～60%。另外，由于水的表面张力高，因此配方中也必须引人一些助剂来改善漆对颜料和基材的润湿性，这些助剂会对漆膜的耐水性和渗透性有负面影响。还有一些助剂，如成膜溶剂也会产生少量的VOC量，即水性涂料中含有少量的挥发性有机化合物，通常在50g/L以下。  \n\n水性涂料在重防腐领域中的应用虽然仅有二三十年的时间，但大量的试验以及实际应用表明它有优良的表现。重防腐配套既可以单独用水性涂料体系，也可以将水性和溶剂型涂料体系混合搭配使用，都可以起到较好的防护效果。虽然，现在很多的条件/因素制约了水性涂料的应用，但它仍是今后涂料发展、应用的方向之一。另外，特别指出的是，水也是目前地球上一种重要的有限资源，因此，在生产水性涂料时，必须注意解决废水处理及其循环使用问题，以防止污染环境。  \n\n防腐涂装设计工作主要包括：根据工程或设备所处环境特点，进行腐蚀环境分析，判断腐蚀环境类别；分析工程或设备各部位结构特点和运行时的工况条件；评估业主对防护年限期望值的可行性；进而选择涂料种类及其配套，确定每层涂膜厚度及总膜厚等工艺参数、编制表面处理与涂装施工工艺规程、确定涂料技术性能指标和质量验收条件以及涂层外观色彩设计等。随着科学技术的发展，大型工程防护涂装设计已经成为整个工程设计中的一个重要的组成部分而日益受到重视。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 119,
+        "chunk": "# 一、重防腐涂装设计原则  \n\n①防腐年限是制定涂层配套方案的主要依据。②涂装体系与周围自然环境/工况条件的适应性。③执行相关国家（行业）标准，并参考相应的国外标准，例如ISO和SSPC标准。④编制正确、可行的涂层配套体系和涂装施工工艺，确保涂层施工质量与效率。③经济性与技术上先进性相结合，追求最佳的性能/价格比。遵循“全寿命经济分析”（LCCA）设计思想。涂层外观设计：工艺美学、环境和谐、漆膜性能三者协调。",
+        "category": " Introduction"
+    },
+    {
+        "id": 120,
+        "chunk": "# 二、“全寿命经济分析法”设计思想简介  \n\n这里着重介绍一下“全寿命经济分析”（LCCA）设计思想：在工程设计中，为了在众多满足安全性和耐久性的方案中找出经济性最优的方案，需要应用“全寿命经济分析法”(lifecyclecostanalysis)，或译为“寿命周期成本分析法”。其基本思想是：在设计施工阶段，不论是选择事先就采取防护措施，还是选择以后“坏了再修”，都要做出经济预算和比较。承建者要对工程的“全寿命”负责到底，以避免“短期行为”给后人带来的麻烦和巨大的经济损失。  \n\n在美国，近年来已在基建工程管理中强制实施“全寿命经济分析法（LCCA)”。举例说明：某混凝土桥梁工程处于氯盐腐蚀环境中，钢筋混凝土结构设计寿命为40年，前期实施了防护措施，主要是采用钢筋阻锈剂和涂料外防护，附加费用仅为0.85美元/m（混凝土桥面)；若前期不采取防护措施，那么15～20年开始修复，40年内累积维修费用为4.8美元/m²，是前者附加费的5.65倍。由此可见，推行“全寿命经济分析法（LCCA）”和倡导工程前期（设计、施工阶段）采取科学可行的腐蚀防护措施，已经不是单纯的技术问题，其重大意义和长远经济效益是不可低估的。  \n\n改革开放以来中国的基本建设规模宏大。例如新建、待建的桥梁数量已居世界第一，但其中为数不少的桥梁已暴露出缺陷，更有一些在远没有达到设计预期寿命时就出现了耐久性严重退化现象，甚至出现倒塌等毁灭性事故，造成非常严重的人员伤亡和经济损失。桥梁的耐久性已引起社会各界高度关注，有专家预言，耐久性的提高将是21世纪桥梁技术进步的重要标志之一。",
+        "category": " Introduction"
+    },
+    {
+        "id": 121,
+        "chunk": "# 三、防腐涂层配套体系的设计  \n\n防腐涂层配套体系的设计是涂装设计的核心内容，国内外防腐涂料与涂装界积累了丰富的经验。这里着重介绍ISO12944-5《色漆和清漆———保护漆体系对钢结构的防护》第5部分《保护漆体系》（Paints and varnishes-—---Corrosion protection of steel structures by pro-tective paintsystems)。主要内容包括各类涂层配套体系以及这些配套体系所能应用于何种腐蚀环境条件，预期的涂层防护寿命等；同时介绍了相关涂料主要成膜物质的基本化学成分和成膜过程以及每种涂料对底材表面处理的要求等。这些对于确立涂装体系、确保涂装质量以及核算涂装工程造价是非常重要的。",
+        "category": " Introduction"
+    },
+    {
+        "id": 122,
+        "chunk": "# 1.涂层配套体系耐久性影响因素  \n\n影响涂层配套体系耐久性的主要因素有以下几方面： $\\textcircled{1}$ 涂装对象物体的特点； $\\textcircled{2}$ 设计的配套体系类型及其总干膜厚度； $\\textcircled{3}$ 底材预处理前状态和表面处理等级； $\\textcircled{4}$ 涂装工艺标准；$\\textcircled{5}$ 施工条件； $\\textcircled{6}$ 施工后涂层暴露环境等。  \n\n必须指出的是：ISO12944-5中各类涂层配套体系所预期的涂层防护寿命而不是“承诺防护寿命”，而只是关于防护寿命的一个技术参数，主要用于协助选择配套体系和制定维修涂装计划表。",
+        "category": " Introduction"
+    },
+    {
+        "id": 123,
+        "chunk": "# 2.防护寿命与腐蚀环境及涂膜厚度的关系  \n\n这三者密切关联，见表3-3-25，  \n\n表3-3-25 腐蚀环境、防护寿命与涂膜厚度的关系  \n\n\n<html><body><table><tr><td>腐蚀环境</td><td>防护寿命</td><td>干膜厚度/μm</td><td>腐蚀环境</td><td>防护寿命</td><td>干膜厚度/μm</td></tr><tr><td>C2</td><td>√ 低 中高</td><td>80 120</td><td>C4</td><td>低 中高</td><td>160 2#</td></tr><tr><td>C3</td><td>低 中 高</td><td>120 160 200</td><td>C5-I,C5-M</td><td>低 中 高</td><td>200 280 320</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 124,
+        "chunk": "# 3.对应各腐蚀环境的涂层配套体系  \n\nISO12944-5描述了不同类型涂料的化学成分和成膜方式，针对ISO12944-2中描述的各种腐蚀环境，提供相应的防腐配套案例，反映了全世界范围内的最新发展方向。  \n\n表 $3-3-25\\cdots$ 表3-3-33是ISO12944-5：2007中所列举的涂装配套，遵循两个不同的原则。  \n\n$\\textcircled{1}$ 表3-3-26、表3-3-31～表3-3-33中列举的配套对应多种腐蚀环境（简称“综合表\"），涂装配套是按照面漆中的成膜物质种类来划分的。这种划分方式有利于业主以面漆的性能作为基础选择配套。在这种情况下，腐蚀等级不是很明确，而且每个涂装配套对应不止一种腐蚀等级。  \n\n$\\textcircled{2}$ 表 $3-3=27\\sim$ 表3-3-30中列举的配套是在单一的腐蚀环境等级下的涂装配套（简称“个别表\")，是按照底漆的主要成膜物质种类划分的。这种划分方式有利于对腐蚀环境等级很了解的业主选择涂装配套。  \n\n如果准备采用下表中的涂装配套体系，首先要判断是否从“综合表”中选择，还是在“个别表”中选择，因为两个列表中的涂装配套编号是不同的。  \n\n表中的涂装配套只是举例，其他类别的涂装配套也可能有同样的防腐作用。但是如果选用表中的涂装配套，那么在涂料施工进行前，就应确保所选的涂装体系满足指定的防腐耐久性。表中提到的漆膜厚度是一个配套指定的干膜厚度，厚度的单位为微米。  \n\n如果在配套中使用新产品，而又缺乏足够的工程业绩支持，则这个配套涂层至少要经过ISO12944-6标准中规定的各项实验验证合格后方能实际应用。  \n\n2-   \n\n\n<html><body><table><tr><td colspan=\"13\">基材：低合金碳钢 表面预处理：Sa2（锈蚀等级为A、B、C的基材，参见ISO 8501-1)</td></tr><tr><td rowspan=\"2\">配套号</td><td colspan=\"4\">底涂层 涂层体系</td><td colspan=\"3\">后道涂层</td><td colspan=\"8\">期望耐久性</td><td rowspan=\"2\"></td><td colspan=\"4\">i h.j 1'</td></tr><tr><td rowspan=\"2\">基料</td><td rowspan=\"2\">类型</td><td rowspan=\"2\">途数</td><td rowspan=\"2\">NDETO</td><td rowspan=\"2\">基料</td><td rowspan=\"2\"></td><td rowspan=\"2\">NDFT</td><td rowspan=\"2\"></td><td colspan=\"2\"></td><td colspan=\"2\">（参见ISO 12944-1和ISO12944-5)</td><td colspan=\"2\"></td><td></td><td rowspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\"></td></tr><tr><td>数</td><td>CH</td><td></td><td>LMH</td><td></td><td>CH</td><td></td><td>C</td></tr><tr><td>A1.01</td><td>AK.AY</td><td>Misc</td><td>1~2</td><td>100</td><td></td><td>1~2</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A.2</td><td></td><td></td><td></td><td></td></tr><tr><td>A1.02</td><td>EP,PUR, ESI</td><td>Zn(R)</td><td>1</td><td>60.</td><td>一</td><td></td><td>100</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A2.04</td><td></td><td></td><td></td><td></td></tr><tr><td>A1.03</td><td>AK</td><td>Misc</td><td>1~2</td><td>80</td><td>AK</td><td>1 2~3</td><td>60</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A2.08</td><td>A3.10</td><td></td><td></td><td></td></tr><tr><td>AI.Q4</td><td>AK</td><td>Misc</td><td>1~2</td><td>80</td><td>AK</td><td></td><td>120</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A2.02</td><td>A3.01</td><td></td><td></td><td></td></tr><tr><td>A1.05</td><td>AK</td><td>Misc</td><td>1~2</td><td>80</td><td>AK</td><td>24</td><td>160</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A2.03A3.02</td><td></td><td></td><td></td></tr><tr><td>A1.06</td><td>EP</td><td>Misc</td><td>I°</td><td>160</td><td>AY</td><td>3~5 2</td><td>200 200</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A3.03A4.01</td><td></td><td></td><td></td></tr><tr><td>A1.07</td><td>AK,AY,</td><td>Misc</td><td>1~2</td><td>80</td><td>AY.CR,PVC</td><td>2~4</td><td>160</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A4.06</td><td></td><td></td></tr><tr><td>A1.08</td><td>CR,PVC EP,PUR,ESI</td><td>Zn(R)</td><td>1</td><td>60</td><td>AY,CR,PVC</td><td>2~3</td><td>160</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A2.05</td><td>A2.03A3.05</td><td></td><td></td><td></td></tr><tr><td>A1.09</td><td>AK,AY,CR,</td><td>Misc</td><td>1~2</td><td>80</td><td>AY.CR,PVC</td><td>3~5</td><td>200</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A3.12A4.10 A3.04A4.02</td><td></td><td></td></tr><tr><td>A1.10</td><td>PVC EP,PUR</td><td>Misc</td><td>I~2</td><td>120</td><td>AY,CR,PVC</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A3.0.0451.01</td><td></td><td></td></tr><tr><td>A1.11</td><td>EP,PUR,ESI</td><td>Zn(R)</td><td>1</td><td>60</td><td>AY,CR,PVC</td><td>3~4 2~4</td><td>200 200</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>A1.12</td><td>AK,AY,CR</td><td>Misc</td><td>N12</td><td>80</td><td>AY,CR,PVC</td><td>3~5</td><td>240</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A4.03 A3.13A4.11</td><td></td><td></td></tr><tr><td>A1.13</td><td>EP,PUR,ESI</td><td>Zn(R)</td><td></td><td>60</td><td>AY,CR,PVC</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A4.05</td><td></td><td></td></tr><tr><td>A1.14</td><td>EP.PUR.ESI</td><td>Zn(R)</td><td></td><td>60</td><td>AY,CR,PVC</td><td>3~4 4~5</td><td>240 320</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A4.12</td><td></td><td></td></tr><tr><td>A1.15</td><td>EP</td><td colspan=\"2\">Misc 1~2</td><td>80</td><td>EP,PUR</td><td>2~3</td><td>120</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A5I. 06</td><td></td></tr><tr><td>A1.16</td><td>EP</td><td colspan=\"2\">Misc</td><td>1~2 80</td><td>EP,PUR</td><td>2~4</td><td>160</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A2.06</td><td>A3.07</td><td></td><td></td><td></td></tr><tr><td>A1.17</td><td>EP,PUR.ESI</td></table></body></html>  \n\n<html><body><table><tr><td rowspan=\"2\">底涂层基料</td><td colspan=\"3\">涂料(液体）</td><td rowspan=\"2\">面涂层基料</td><td colspan=\"3\">涂料（液体）</td><td rowspan=\"2\">①Zn（R）=富锌底漆； Misc=含防锈颜料的底漆； ②NDFT=设计干膜厚度； ③建议涂料供应商检测相 ③富锌底漆的NDFT在40～</td></tr><tr><td>组分</td><td></td><td>可水性化</td><td>组分</td><td></td></tr><tr><td></td><td>单组分双组分</td><td></td><td></td><td></td><td>单组分双组分</td><td></td><td>可水性化</td></tr><tr><td>AK=醇酸</td><td>X</td><td></td><td>X</td><td>AK=醇酸</td><td>X</td><td></td><td>X</td></tr><tr><td>CR=氯化橡胶</td><td>X</td><td></td><td></td><td>CR=氯化橡胶</td><td>X</td><td></td><td>容性； ④建议在硅酸类底漆上加涂</td></tr><tr><td>AY=丙烯酸</td><td>X</td><td></td><td>X</td><td>AY-丙烯酸</td><td>X</td><td></td><td>X</td></tr><tr><td>PVC=聚氯乙烯</td><td>X</td><td></td><td></td><td>PVC-聚氯乙烯</td><td>X</td><td></td><td>一道衔接涂层；</td></tr><tr><td>EP=环氧</td><td></td><td>X</td><td>X</td><td>EP=环氧</td><td></td><td>X</td><td>X 80μm为宜。</td></tr><tr><td>ESI=硅酸乙酯</td><td></td><td>X</td><td>X</td><td>PUR=聚氨酯（脂肪族）</td><td>X</td><td>X</td><td></td></tr><tr><td>PUR=聚氨酯（脂肪族或芳香族）</td><td>X</td><td>X</td><td>X</td><td>EPC=改性环氧</td><td>X</td><td>X</td><td></td></tr></table></body></html>  \n\n：：0  \n\n\n<html><body><table><tr><td rowspan=\"3\">配套 编号</td><td colspan=\"4\">底涂层</td><td>后道涂层</td><td colspan=\"2\">涂层体系</td><td colspan=\"8\"></td><td rowspan=\"2\"></td><td colspan=\"5\" rowspan=\"2\">分类表中对应的配套编号</td></tr><tr><td rowspan=\"2\">基料</td><td rowspan=\"2\">类型</td><td rowspan=\"2\">涂装 道数</td><td rowspan=\"2\">NDFT /um</td><td rowspan=\"2\">基料 道数</td><td rowspan=\"2\">涂装 NDFT</td><td rowspan=\"2\">C2</td><td rowspan=\"2\"></td><td rowspan=\"2\">C3</td><td rowspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\">（参见ISO12944-1和ISO12944-5） C5-I</td><td rowspan=\"2\">C5-M</td><td rowspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\"></td></tr><tr><td></td><td>C4 M</td></tr><tr><td></td><td>EP,PUR,ESI</td><td>Zn(R)</td><td>1</td><td>60</td><td>EP,PUR</td><td>3~4</td><td>/μm 200</td><td>LMH</td><td></td><td>LMH</td><td>L</td><td>H</td><td>M L</td><td>H L</td><td>MH</td><td>A.2</td><td>A.3</td><td>A.4 A4.14</td><td>A.5(I）</td><td>A.5(M</td></tr><tr><td>A1.19 A1.20</td><td>EP,PUR,ESI</td><td>Zn(R)</td><td>1</td><td>60</td><td>EP,PUR</td><td>3~4</td><td>240</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A4.15A5I.04A5M.0</td><td></td></tr><tr><td>A1.21</td><td>EP</td><td>Misc</td><td>1~2</td><td>80</td><td>EP,PUR</td><td>3~5</td><td>280</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A4.09</td><td></td><td></td></tr><tr><td>A1.22</td><td>EP,PUR</td><td>Misc</td><td>1</td><td>150</td><td>EP,PUR</td><td>2</td><td>300</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A5I.03</td><td>A5M.0</td></tr><tr><td>A1.23</td><td>EP,PUR,ESI</td><td>Zn(R）</td><td>1</td><td>60</td><td>EP,PUR</td><td>3~4</td><td>320</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A5I.05</td><td>A5M.</td></tr><tr><td>A1.24</td><td>EP,PUR</td><td>Misc</td><td>1</td><td>80</td><td>EP,PUR</td><td>3~4</td><td>320</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A51.02A5M.</td><td></td></tr><tr><td>A1.25</td><td>EP,PUR</td><td>Misc</td><td>1</td><td>250</td><td>EP,PUR</td><td>2</td><td>500</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A5M.</td></tr><tr><td>A1.26</td><td>EP,PUR</td><td>Misc</td><td>1</td><td>400</td><td></td><td>1</td><td>400</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A5M.</td></tr><tr><td>A1.27</td><td>EP</td><td>Misc</td><td>1</td><td>100</td><td>EPC</td><td>3</td><td>300</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A5M.</td></tr><tr><td>A1.28</td><td>EP,PUR</td><td>Zn(R)</td><td>1</td><td>60</td><td>EPC</td><td>3~4</td><td>400</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A5M.</td></tr></table></body></html>  \n\n基材：低合金碳钢  \n\n表面预处理： $\\mathrm{Sa2{\\frac{1}{2}}}$ （锈蚀等级为A、B、C的基材，参见ISO 8501-1)  \n\n表3-3-27在C2腐蚀环境下低合金碳钢的配套涂层  \n\n\n<html><body><table><tr><td rowspan=\"2\">配套 编号</td><td colspan=\"4\">'t -i. 底涂层</td><td>后道涂层</td><td colspan=\"2\">涂层体系</td><td colspan=\"3\">期望耐久性</td></tr><tr><td rowspan=\"2\">基料</td><td rowspan=\"2\">类型</td><td rowspan=\"2\">涂装道数</td><td rowspan=\"2\">NDFT /μm</td><td rowspan=\"2\">基料 .</td><td rowspan=\"2\">涂装道数</td><td rowspan=\"2\">NDFT /μm</td><td rowspan=\"2\">低</td><td rowspan=\"2\">中</td><td rowspan=\"2\">嵩</td></tr><tr><td>甲</td></tr><tr><td>A2.01</td><td>AK</td><td>Misc</td><td>1</td><td>40</td><td>AK</td><td>2</td><td>80</td><td></td><td></td><td></td></tr><tr><td>A2.02</td><td>AK</td><td>Misc</td><td>1~2</td><td>80</td><td>AK</td><td>2~3</td><td>120</td><td></td><td></td><td></td></tr><tr><td>A2.03</td><td>AK</td><td>Misc</td><td>1~2</td><td>80</td><td>AK.AY,PVC.CR</td><td>2-4</td><td>160</td><td></td><td></td><td></td></tr><tr><td>A2.04</td><td>AK</td><td>Misc</td><td>1~2</td><td>100</td><td></td><td>1~2</td><td>100</td><td></td><td></td><td></td></tr><tr><td>A2.05</td><td>AY.PVC,CR</td><td>Misc</td><td>1~2</td><td>80</td><td>AY,PVC,CR</td><td>2~4</td><td>160</td><td></td><td></td><td></td></tr><tr><td>A2.06</td><td>EP</td><td>Misc</td><td>1~2</td><td>80</td><td>EP,PUR</td><td>2~3</td><td>120</td><td></td><td></td><td></td></tr><tr><td>A2.07</td><td>EP</td><td>Misc</td><td>1~2</td><td>80</td><td>EP,PUR</td><td>2~4</td><td>160</td><td></td><td></td><td></td></tr><tr><td>A2.08</td><td>EP,PUR,ESI④</td><td>Zn(R)</td><td>1</td><td>60</td><td></td><td>1</td><td>80</td><td></td><td></td><td></td></tr></table></body></html>  \n\n表3-3-28 在C3腐蚀环境下低合金碳钢的配套涂层  \n\n\n<html><body><table><tr><td>底涂层基料</td><td>类型</td><td>可水性化</td><td>面涂层基料</td><td>类型</td><td>可水性化</td></tr><tr><td>AK=醇酸</td><td>单组分</td><td>X</td><td>AK=醇酸</td><td>单组分</td><td>X</td></tr><tr><td>CR=氯化橡胶</td><td>单组分</td><td></td><td>CR=氯化橡胶</td><td>单组分</td><td></td></tr><tr><td>AY=丙烯酸</td><td>单组分</td><td>X</td><td>AY=丙烯酸</td><td>单组分</td><td>X</td></tr><tr><td>PVC=聚氯乙烯</td><td>单组分</td><td></td><td>PVC=聚氯乙烯</td><td>单组分</td><td></td></tr><tr><td>EP-环氧</td><td>双组分</td><td>X</td><td>EP=环氧</td><td>双组分</td><td>X</td></tr><tr><td>ESI=硅酸乙酯</td><td>单或双组分</td><td>X</td><td>PUR=聚氨酯(脂肪族)</td><td>单或双组分</td><td></td></tr><tr><td>PUR=聚氨酯(脂肪族或芳香族)</td><td>单或双组分</td><td>X</td><td></td><td></td><td></td></tr></table></body></html>\n\n①Zn（R）=富锌底漆，Misc=含防锈颜料的底漆；②NDFT=设计干膜厚度；$\\textcircled{3}$ 建议涂料供应商检测相容性；④建议在硅酸类底漆（ESI）上加涂一道衔接涂层；③富锌底漆的NDFT在40～80μm为宜。  \n\n表面预处理：Sa2（锈蚀等级为A、B、C的基材，参见ISO8501-1）  \n\n<html><body><table><tr><td rowspan=\"2\">配套 编号</td><td colspan=\"4\">底涂层</td><td>后道涂层</td><td colspan=\"2\">涂层体系</td><td colspan=\"3\">期望耐久性</td></tr><tr><td>基料</td><td>类型</td><td>涂装道数</td><td>NDFT</td><td>基料</td><td>涂装道数</td><td>NDETO</td><td></td><td>中</td><td>高</td></tr><tr><td>A3.01</td><td>AK</td><td>Misc</td><td>1~2</td><td>80</td><td>AK</td><td>2~3</td><td>120</td><td></td><td></td><td></td></tr><tr><td>A3.02</td><td>AK</td><td>Misc</td><td>1~2</td><td>80</td><td>AK</td><td>2~4</td><td>160</td><td></td><td></td><td></td></tr><tr><td>A3.03</td><td>AK</td><td>Misc</td><td>1~2</td><td>80</td><td>AK</td><td>3~5</td><td>200</td><td></td><td></td><td></td></tr><tr><td>A3.04</td><td>AK</td><td>Misc</td><td>1~2</td><td>80</td><td>AY,PVC,CR</td><td>3~5</td><td>200</td><td></td><td></td><td></td></tr><tr><td>A3.05</td><td>AY,PVC,CR</td><td>Misc</td><td>1~2</td><td>80</td><td>AY,PVC,CR</td><td>2~4</td><td>160</td><td></td><td></td><td></td></tr><tr><td>A3.06</td><td>AY,PVC,CR</td><td>Misc</td><td>1~2</td><td>80</td><td>AY,PVC,CR?</td><td>3~5</td><td>200</td><td></td><td></td><td></td></tr><tr><td>A3.07</td><td>EP</td><td>Misc</td><td>1</td><td>80</td><td>EP,PUR</td><td>2~3</td><td>120</td><td></td><td></td><td></td></tr><tr><td>A3.08</td><td>EP</td><td>Misc</td><td>1</td><td>80</td><td>EP,PUR</td><td>2~4</td><td>160</td><td></td><td></td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>基材：低合金碳钢</td></tr><tr><td>表面预处理：Sa2（锈蚀等级为A、B、C的基材，参见ISO8501-1)</td></tr></table></body></html>  \n\n<html><body><table><tr><td rowspan=\"2\">配套 编号</td><td colspan=\"4\">底涂层</td><td rowspan=\"2\">后道涂层</td><td colspan=\"2\">涂层体系</td><td colspan=\"3\">期望耐久性</td></tr><tr><td>基料 =7</td><td>类型</td><td>涂装道数</td><td>NDFT /μm</td><td>基料</td><td>涂装道数</td><td>NDFT /μm</td><td>低中高</td><td></td></tr><tr><td>A3.09</td><td>EP</td><td>Misc</td><td>1</td><td>80</td><td>EP,PUR</td><td>3~5</td><td>200</td><td></td><td></td><td></td></tr><tr><td>A3.10</td><td>EP,PUR,ESI④</td><td>Zn(R)</td><td>1</td><td>60</td><td></td><td>1</td><td>60</td><td></td><td></td><td></td></tr><tr><td>A3.11</td><td>EP,PUR,ESI④</td><td>Zn(R)</td><td>1</td><td>60</td><td>EP,PUR</td><td>2</td><td>160</td><td></td><td></td><td></td></tr><tr><td>A3.12</td><td>EP,PUR,ESI</td><td>Zn(R)</td><td>-1</td><td>60</td><td>AY,PVC,CR</td><td>2~3</td><td>-160</td><td></td><td></td><td></td></tr><tr><td>A3.13</td><td>EP,PUR</td><td>Zn(R）</td><td></td><td>60</td><td>AY.PVC,CR</td><td>3</td><td>200</td><td></td><td></td><td></td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td rowspan=\"2\">配套 编号</td><td colspan=\"4\">底涂层</td><td>后道涂层</td><td colspan=\"2\">涂层体系</td><td colspan=\"3\">期望耐久性</td></tr><tr><td>基料</td><td>类型</td><td>涂装道数</td><td>NDFT /um</td><td>基料</td><td>涂装道数</td><td>NDFT /pm</td><td>低</td><td>中</td><td>高</td></tr><tr><td>A4.01</td><td>AK</td><td>Misc</td><td>1~2</td><td>80</td><td>AK</td><td>3~5</td><td>200</td><td></td><td></td><td></td></tr><tr><td>A4.02</td><td>AK</td><td>Misc</td><td>1~2</td><td>80</td><td>AY,CR,PVC③</td><td>3~5</td><td>200</td><td></td><td></td><td></td></tr><tr><td>A4.03</td><td>AK</td><td>Misc</td><td>1~2</td><td>80</td><td>AY,CR,PVC</td><td>3~5</td><td>240</td><td></td><td></td><td></td></tr><tr><td>A4.04</td><td>AY,CR,PVC</td><td>Misc</td><td>1~2</td><td>80</td><td>AY,CR,PVC③</td><td>3~5</td><td>200</td><td></td><td></td><td></td></tr><tr><td>A4.05</td><td>AY,CR,PVC</td><td>Misc</td><td>1~2</td><td>80</td><td>AY,CR,PVC④</td><td>3~5</td><td>240</td><td></td><td></td><td></td></tr><tr><td>A4.06</td><td>EP</td><td>Misc</td><td>1~2</td><td>160</td><td>AY,CR,PVC③</td><td>2~3</td><td>200</td><td></td><td></td><td></td></tr><tr><td>A4.07</td><td>EP</td><td>Misc</td><td>1~2</td><td>160</td><td>AY.CR,PVC</td><td>2~3</td><td>280</td><td></td><td></td><td></td></tr><tr><td>A4.08</td><td>EP</td><td>Misc</td><td>1</td><td>80</td><td>EP,PUR</td><td>2~3</td><td>240:</td><td></td><td></td><td></td></tr><tr><td>A4.09</td><td>EP</td><td>Misc</td><td>1</td><td>80</td><td>EP,PUR</td><td>2~3</td><td>280</td><td></td><td></td><td></td></tr><tr><td>A4.10</td><td>EP,PUR,ESI④</td><td>Zn(R)</td><td>1</td><td>60</td><td>AY,CR,PVC③</td><td>2~3</td><td>160</td><td></td><td></td><td></td></tr></table></body></html>  \n\n表3-3-29 在C4腐蚀环境下低合金碳钢的配套涂层  \n\n\n<html><body><table><tr><td>底涂层基料</td><td>类型</td><td>可水性化</td><td>面涂层基料</td><td>类型</td><td>可水性化</td></tr><tr><td>AK=醇酸</td><td>单组分</td><td>X</td><td>AK=醇酸</td><td>单组分</td><td>X</td></tr><tr><td>CR=氯化橡胶</td><td>单组分</td><td></td><td>CR=氯化橡胶</td><td>单组分</td><td></td></tr><tr><td>AY=丙烯酸</td><td>单组分</td><td>X</td><td>AY=丙烯酸</td><td>单组分</td><td></td></tr><tr><td>PVC=聚氯乙烯</td><td>单组分</td><td></td><td>PVC=聚氯乙烯</td><td>单组分</td><td></td></tr><tr><td>EP=环氧</td><td>双组分</td><td>X</td><td>EP=环氧</td><td>双组分</td><td>X</td></tr><tr><td>ESI=硅酸乙酯</td><td>单或双组分</td><td>X</td><td>PUR=聚氨酯(脂肪族)</td><td>单或双组分</td><td>X</td></tr><tr><td>PUR=聚氨酯(脂肪族或芳香族)</td><td>单或双组分</td><td>X</td><td></td><td></td><td></td></tr></table></body></html>\n\n$\\mathbb{D}\\ Z\\mathrm{n}(\\mathbb{R})=$ 富锌底漆，Misc $\\L=$ 含防锈颜料的底漆；$\\textcircled{2}$ $\\mathfrak{D F T}=$ 设计干膜厚度；$\\textcircled{3}$ 建议涂料供应商检测相容性；$\\textcircled{4}$ 建议在硅酸类底漆（ESI）上加涂一道衔接涂层；$\\textcircled{5}$ 富锌底漆的NDFT在 $40\\sim80\\mu\\mathrm{m}$ 为宜。  \n\n基材：低合金碳钢  \n\n表面预处理： $\\mathbb{S}\\mathbb{a}\\mathbb{Z}\\frac{1}{2}$ （锈蚀等级为A、BC的基材，参见ISO8501-1）  \n\n续表",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 125,
+        "chunk": "# 基材：低合金碳钢  \n\n表面预处理： $\\sin2\\frac{1}{2}$ （锈蚀等级为A、B、C的基材，参见ISO8501-1)  \n\n<html><body><table><tr><td rowspan=\"2\">配套 编号</td><td colspan=\"4\">底涂层</td><td>后道涂层</td><td colspan=\"2\">涂层体系</td><td colspan=\"3\">期望耐久性</td></tr><tr><td>基料</td><td>类型</td><td>涂装道数</td><td>NDFT@ :/pim</td><td>基料</td><td>涂装道数</td><td>NDFT /μm</td><td></td><td>低中高</td><td></td></tr><tr><td>A4.11</td><td>EP,PUR,ESI</td><td>Zn(R)</td><td>1</td><td>60</td><td>AY,CR,PVC④</td><td>2~4</td><td>200</td><td></td><td></td><td></td></tr><tr><td>A4.12</td><td>EP,PUR,ESI</td><td>Zn(R)</td><td>-1</td><td>60</td><td>AY,CR,PVC③</td><td>3~4</td><td>240</td><td></td><td></td><td></td></tr><tr><td>A4.13</td><td>EP,PUR,ESI④</td><td>Zn(R)</td><td>1.</td><td>60</td><td>EP,PUR</td><td>2~3</td><td>160</td><td></td><td></td><td></td></tr><tr><td>A4.14</td><td>EP,PUR,ESI</td><td>Zn(R)</td><td>1</td><td>60</td><td>EP,PUR</td><td>2~3</td><td>200</td><td></td><td></td><td></td></tr><tr><td>A4.15</td><td>EP,PUR,ESI</td><td>Zn(R）</td><td>1</td><td>60</td><td>EP,PUR</td><td>3~4</td><td>240</td><td></td><td></td><td></td></tr><tr><td>A4.16</td><td>ESI</td><td>Zn(R)</td><td>1</td><td>60</td><td></td><td>1</td><td>60</td><td></td><td></td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>底涂层基料</td><td>类型</td><td>可水性化</td><td>面涂层基料</td><td>类型</td><td>可水性化</td></tr><tr><td>AK=醇酸</td><td>单组分</td><td>X</td><td>AK=醇酸</td><td>单组分</td><td>X</td></tr><tr><td>CR=氯化橡胶</td><td>单组分</td><td></td><td>CR=氯化橡胶</td><td>单组分</td><td></td></tr><tr><td>AY=丙烯酸</td><td>单组分</td><td>X</td><td>AY=丙烯酸</td><td>单组分</td><td></td></tr><tr><td>PVC=聚氯乙烯</td><td>单组分</td><td></td><td>PVC=聚氯乙烯</td><td>单组分</td><td></td></tr><tr><td>EP=环氧</td><td>双组分</td><td>X</td><td>EP=环氧</td><td>双组分</td><td>X</td></tr><tr><td>ESI=硅酸乙酯</td><td>单或双组分</td><td>X</td><td>PUR=聚氨酯(脂肪族)</td><td>单或双组分</td><td>X</td></tr><tr><td>PUR=聚氨酯(脂肪族或芳香族)</td><td>单或双组分</td><td>X</td><td></td><td></td><td></td></tr></table></body></html>\n\n$\\mathbb{D}\\ Z\\mathrm{n}(\\mathbb{R})=\\sharp$ 锌底漆，Misc $\\circeq$ 含防锈颜料的底漆；$\\textcircled{2}$ NDFT $\\circeq$ 设计干膜厚度；$\\textcircled{3}$ 建议涂料供应商检测相容性；$\\textcircled{4}$ 建议在硅酸类底漆（ESI）上加涂一道衔接涂层；$\\textcircled{5}$ 富锌底漆的NDFT在 $40\\cdots80\\mu\\mathrm{m}$ 为宜。  \n\n表3-3-30在C5-I和C5-M腐蚀环境下低合金碳钢的配套涂层  \n\n\n<html><body><table><tr><td>基材：低合金碳钢 ： ”'..1 表面预处理：Sa2（锈蚀等级为A、B、C的基材，参见ISO8501-1)</td></tr></table></body></html>  \n\n<html><body><table><tr><td rowspan=\"2\">表面预处理：Sa2（锈蚀等级为A、B、C的基材，参见ISO8501-1) 配套编号</td><td colspan=\"4\">底涂层</td><td>后道涂层</td><td colspan=\"2\">涂层体系</td><td colspan=\"2\">期望耐久性</td></tr><tr><td>基料</td><td>类型</td><td>涂装道数</td><td>NDFT</td><td>基料</td><td>涂装道数</td><td>NDRT</td><td>低 中</td><td>高</td></tr><tr><td colspan=\"10\">C5-I</td></tr><tr><td>A5L.01</td><td>EP,PUR</td><td>Misc</td><td>1~2</td><td>120</td><td>AY,CR.PVC</td><td>3~4</td><td>200</td><td></td><td></td></tr><tr><td>A5L. 02</td><td>EP,PUR</td><td>Misc</td><td>1</td><td>80</td><td>EP,PUR</td><td>3~4</td><td>320</td><td></td><td></td></tr><tr><td>A51.03</td><td>EP,PUR</td><td>Misc</td><td>1</td><td>150</td><td>EP,PUR</td><td>2</td><td>300</td><td></td><td></td></tr><tr><td>A5I.04</td><td>EP,PUR,ESI④</td><td>Zn(R)</td><td>1.</td><td>60</td><td>EP,PUR</td><td>3~4</td><td>240</td><td></td><td></td></tr><tr><td>A51.05</td><td>EP,PUR,ESI④</td><td>Zn(R)</td><td>1</td><td>60</td><td>EP,PUR</td><td>3~5</td><td>320</td><td></td><td></td></tr><tr><td>A5L 06</td><td>EP,PUR,ESI④</td><td>Zn(R)</td><td>1</td><td>60</td><td>AY,CR,PVC</td><td>4~5.</td><td>320</td><td></td><td></td></tr></table></body></html>  \n\n续表  \n\n基材：低合金碳钢  \n\n表面预处理： $\\mathrm{|}\\tilde{\\mathrm{Sa2\\frac{~1~}{~2~}~}}$ （锈蚀等级为A、B、C的基材，参见ISO8501-1）  \n\n<html><body><table><tr><td rowspan=\"2\">配套编号</td><td colspan=\"4\">底涂层</td><td>后道涂层</td><td colspan=\"2\">涂层体系</td><td colspan=\"3\">期望耐久性</td></tr><tr><td>基料</td><td>类型</td><td>涂装道数</td><td>NDFT2 /μm</td><td>基料</td><td>涂装道数</td><td>NDFT /μm</td><td>低中</td><td></td><td>高</td></tr><tr><td colspan=\"9\">C5-M</td></tr><tr><td>A5M.01</td><td>EP.PUR</td><td>Misc</td><td></td><td>150</td><td>EP.PUR</td><td>2</td><td>300</td><td></td><td></td><td></td></tr><tr><td>A5M. 02</td><td>EP,PUR</td><td>Misc</td><td>1</td><td>80</td><td>EP,PUR</td><td>3~4</td><td>320</td><td></td><td></td><td></td></tr><tr><td>A5M.03</td><td>EP,PUR</td><td>Misc</td><td>1</td><td>400</td><td></td><td></td><td>400</td><td></td><td></td><td></td></tr><tr><td>A5M.04</td><td>EP,PUR</td><td>Misc</td><td>1</td><td>250</td><td>EP,PUR</td><td>2</td><td>500</td><td></td><td></td><td></td></tr><tr><td>A5M.05</td><td>EP,PUR,ESI④</td><td>Zn(R)</td><td>1</td><td>60</td><td>EP,PUR</td><td>4</td><td>240</td><td></td><td></td><td></td></tr><tr><td>A5M.06</td><td>EP,PUR,ESI④</td><td>Zn(R)</td><td>1.</td><td>60</td><td>EP,PUR</td><td>4~5</td><td>320</td><td></td><td></td><td></td></tr><tr><td>A5M.07</td><td>EP,PUR,ESI</td><td>Zn(R)</td><td></td><td>60</td><td>EPC</td><td>3-4</td><td>400</td><td></td><td></td><td></td></tr><tr><td>A5M.08</td><td>EPC</td><td>Misc</td><td>1</td><td>100</td><td>EPC</td><td>3</td><td>300</td><td></td><td></td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>底涂层基料</td><td>类型</td><td>可水性化</td><td>面涂层基料</td><td>类型</td><td>可水性化</td></tr><tr><td>EP=环氧</td><td>双组分</td><td>X</td><td>EP=环氧</td><td>双组分</td><td>X</td></tr><tr><td>EPC=改性环氧</td><td>双组分</td><td></td><td>EPC=改性环氧</td><td>双组分</td><td></td></tr><tr><td>ESI=硅酸乙酯</td><td>单或双组分</td><td>X</td><td>PUR=聚氨酯（脂肪族）</td><td>单或双组分</td><td>X</td></tr><tr><td>PUR=聚氨酯（脂肪族或芳香族）</td><td>单或双组分</td><td>X</td><td>CR=氯化橡胶</td><td>单组分</td><td></td></tr><tr><td></td><td></td><td></td><td>AY=丙烯酸</td><td>单组分</td><td>X</td></tr><tr><td></td><td></td><td></td><td>PVC=聚氯乙烯</td><td>单组分</td><td></td></tr></table></body></html>\n\n$\\textcircled{1}$ $)\\ Z\\mathtt{m}(\\mathbb{R})=$ 富锌底漆，Misc $\\equiv$ 含防锈颜料的底漆；$\\textcircled{2}$ NDFT $\\mathbf{\\equiv}=$ 设计干膜厚度；$\\textcircled{3}$ 建议涂料供应商检测相容性；$\\textcircled{4}$ 建议在硅酸类底漆（ESI）上加涂一道衔接涂层；$\\textcircled{5}$ 富锌底漆的NDFT在 $40\\sim80\\mu\\mathrm{m}$ 为宜。  \n\n表3-3-31在Iml、 $\\mathbf{Im}2$ 、Im3腐蚀环境下低合金碳钢的配套涂层  \n\n\n<html><body><table><tr><td colspan=\"8\">基材：低合金碳钢 1 y: 表面预处理：Sa2（锈蚀等级为A、B、C的基材，参见ISO8501-1) 本表不推荐低耐久性配套</td></tr><tr><td rowspan=\"2\">配套编号</td><td colspan=\"4\">底涂层</td><td colspan=\"2\">后道涂层</td><td colspan=\"4\">涂层体系 期望耐久性</td></tr><tr><td>基料</td><td>类型</td><td>涂装道数</td><td>NDFT -/μm 基料</td><td>涂装道数</td><td></td><td>NDFT</td><td>低</td><td></td><td>高</td></tr><tr><td>A6.01</td><td>EP</td><td>Zn(R）</td><td>1</td><td>60</td><td>EP,PUR</td><td>3~5</td><td>360</td><td></td><td></td><td></td></tr><tr><td>A6.02</td><td>EP</td><td>Zn(R)</td><td>1</td><td>60④</td><td>EP,PURC</td><td>3~5</td><td>1540</td><td></td><td></td><td></td></tr><tr><td>A6.03</td><td>EP</td><td>Misc</td><td>1</td><td>80</td><td>EP,PUR</td><td>2~4</td><td>380</td><td></td><td></td><td></td></tr><tr><td>A6.04</td><td>EP</td><td>Misc</td><td>1</td><td>80</td><td>EPGF,EP,PUR</td><td>3</td><td>500</td><td></td><td></td><td></td></tr><tr><td>A6.05</td><td>EP</td><td>Misc</td><td>1</td><td>80</td><td>EP</td><td>2</td><td>330</td><td></td><td></td><td></td></tr><tr><td>A6.06</td><td>EP</td><td>Misc</td><td>1</td><td>800</td><td></td><td></td><td>800</td><td></td><td></td><td></td></tr></table></body></html>  \n\n续表  \n\n基材：低合金碳钢  \n\n表面预处理：Sa2(锈蚀等级为A、B、C的基材，参见ISO8501-1)本表不推荐低耐久性配套  \n\n<html><body><table><tr><td rowspan=\"2\">配套 编号</td><td colspan=\"4\">底涂层</td><td>后道涂层</td><td colspan=\"2\">涂层体系</td><td colspan=\"3\">期望耐久性</td></tr><tr><td>基料</td><td>类型</td><td>涂装道数</td><td>NDFT</td><td>基料</td><td>涂装道数</td><td>NDET</td><td>低</td><td>中</td><td>高</td></tr><tr><td>A6.07</td><td>ESIO</td><td>Zn(R)</td><td>1</td><td>60④</td><td>EP,EPGF</td><td></td><td>450</td><td></td><td></td><td></td></tr><tr><td>A6.08</td><td>EP</td><td>Misc</td><td>1</td><td>.80</td><td>EPGF</td><td>3</td><td>800</td><td></td><td></td><td></td></tr><tr><td>A6.09</td><td>EP.PUR</td><td>Misc</td><td></td><td></td><td></td><td>1-3</td><td>400</td><td></td><td></td><td></td></tr><tr><td>A6.10</td><td>EP,PUR</td><td>Misc</td><td></td><td></td><td></td><td>1~3</td><td>600</td><td></td><td></td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>底涂层基料</td><td>类型</td><td>可水性化</td><td>面涂层基料</td><td>类型</td><td>可水性化</td></tr><tr><td>EP=环氧</td><td>双组分</td><td>X</td><td>EP=环氧</td><td>双组分</td><td>X</td></tr><tr><td>ESI=硅酸乙酯</td><td>单或双组分</td><td>X</td><td>EPGF=环氧玻璃鳞片</td><td>双组分</td><td></td></tr><tr><td>PURC=改性聚氨酯</td><td>双组分</td><td></td><td>PURC=改性聚氨酯</td><td>双组分</td><td></td></tr><tr><td>PUR=聚氨酯(脂肪族或芳香族)</td><td>单或双组分</td><td>X</td><td>PUR=聚氨酯(脂肪族或芳香族)</td><td>单或双组分</td><td>X</td></tr></table></body></html>\n\n①Zn（R）=富锌底漆，Misc=含防锈颜料的底漆；②NDFT=设计干膜厚度；$\\textcircled{3}$ ③建议在硅酸类底漆（ESI）上加涂一道衔接涂层；④富锌底漆的NDFT在40～80μm为宜；注：通常水性产品不适合用于浸没环境。  \n\n基材：热浸锌钢材  \n\nISO12944-4举了一些表面预处理的例子，应采用涂料供应商推荐的表面预处理方式和配套的涂层  \n\n表3-3-32在C2至C5-I和C5-M腐蚀环境下热浸锌钢材的配套涂层  \n\n\n<html><body><table><tr><td rowspan=\"2\">配套编号</td><td colspan=\"3\">底涂层</td><td>后道涂层</td><td colspan=\"2\">涂层体系</td><td colspan=\"10\">际店 期望耐久性 (参见ISO 12944-1和ISO12944-5)</td></tr><tr><td>基料</td><td>数</td><td>NDETO</td><td>基料</td><td rowspan=\"2\">数</td><td rowspan=\"2\">NDFTO</td><td colspan=\"2\">CH</td><td colspan=\"2\">3M</td><td colspan=\"2\"></td><td colspan=\"2\"></td><td colspan=\"2\"></td><td>CMH</td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>L</td><td></td><td>L</td><td>H</td><td>L</td><td>M</td><td>H</td><td></td><td></td><td>L</td><td></td><td></td></tr><tr><td>A7.01</td><td></td><td></td><td></td><td>PVC</td><td></td><td>80</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>A7.02</td><td>PVC</td><td>1</td><td>40</td><td>PVC</td><td>2</td><td>120</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>A7.03</td><td>PVC</td><td>1</td><td>80</td><td>PVC</td><td>2</td><td>160</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>A7.04</td><td>PVC</td><td>1.</td><td>80</td><td>PVC</td><td>3</td><td>240</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>A7.05</td><td></td><td></td><td></td><td>AY</td><td>H</td><td>80</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>A7.06</td><td>AY</td><td>1</td><td>40</td><td>AY</td><td>2</td><td>120</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>A7.07</td><td>AY</td><td>1</td><td>80</td><td>AY</td><td>N</td><td>160</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>A7.08</td><td>AY</td><td>1</td><td>80</td><td>AY</td><td>3</td><td>240</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>A7.09</td><td></td><td>一</td><td></td><td>EP.PUR</td><td>1</td><td>80</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>A7.10</td><td>EP,PUR</td><td>1</td><td>60</td><td>EP,PUR</td><td>2</td><td>120</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n续表  \n\n基材：热浸锌钢材  \n\nISO12944-4举了一些表面预处理的例子，应采用涂料供应商推荐的表面预处理方式和配套的涂层  \n\n<html><body><table><tr><td rowspan=\"2\">配套编号</td><td colspan=\"3\">底涂层</td><td>后道涂层</td><td colspan=\"2\">涂层体系</td><td colspan=\"10\">期望耐久性 （参见ISO12944-1 和ISO 12944-5)</td></tr><tr><td>基料</td><td>涂装 道数</td><td>NDFT /μm</td><td>基料</td><td>涂装 道数</td><td>NDFT /μm</td><td></td><td>C2</td><td></td><td>C3</td><td></td><td></td><td>C4</td><td></td><td>C5-I</td><td></td><td>C5-M</td><td></td></tr><tr><td>A7.11</td><td>EP,PUR</td><td></td><td>80</td><td>EP,PUR</td><td>2</td><td>160</td><td>L</td><td>M H</td><td>L</td><td>M</td><td>H L</td><td>M</td><td>H</td><td>L M</td><td>H</td><td>L</td><td>M</td><td>H</td></tr><tr><td>A7.12</td><td>EP,PUR</td><td>1</td><td>80</td><td>EP,PUR</td><td>3'</td><td>240</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>A7.13</td><td>EP,PUR</td><td>1</td><td>80</td><td>EP.PUR</td><td>3</td><td>320</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>底涂层基料</td><td>类型</td><td>可水性化</td><td>面涂层基料</td><td>类型</td><td>可水性化</td></tr><tr><td>AY=丙烯酸</td><td>单组分</td><td>X</td><td>AY=丙烯酸</td><td>单组分</td><td>X</td></tr><tr><td>PVC=聚氯乙烯</td><td>单组分</td><td></td><td>PVC=聚氯乙烯</td><td>单组分</td><td></td></tr><tr><td>EP=环氧</td><td>双组分</td><td>X</td><td>EP=环氧</td><td>双组分</td><td>X</td></tr><tr><td>PUR=聚氨酯(脂肪族或芳香族）</td><td>单或双组分</td><td>X</td><td>PUR=聚氨酯(脂肪族或芳香族)</td><td>单或双组分</td><td>X</td></tr></table></body></html>\n\n$\\textcircled{1}$ NDFT $\\mathbf{\\equiv}=$ 设计干膜厚度；$\\textcircled{2}$ 在这种情况下，配套涂层的耐久性和涂层与热浸锌表面的附着力有关。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 126,
+        "chunk": "# 表3-3-33在C4，C5-I，C5-M和 $\\mathbf{Im1{\\sim}I m3}$ 腐蚀环境下金属热喷涂表面的配套涂层  \n\n基材：金属热喷涂(锌，锌铝合金，铝)  \n表面预处理：参见ISO12944-4：1988第12章  \n金属热喷涂完毕后，建议在4h内涂装封闭层或配套体系中的第一道涂层；选用的封闭涂层时，应与后道涂层相配套  \n\n<html><body><table><tr><td rowspan=\"2\">配套 编号</td><td colspan=\"3\" rowspan=\"2\">底涂层</td><td rowspan=\"2\">后道涂层</td><td rowspan=\"2\">涂层体系</td><td rowspan=\"2\"></td><td colspan=\"15\">期望耐久性 （参见ISO12944-1 和ISO12944-5)</td><td rowspan=\"2\"></td></tr><tr><td>涂装 NDFT</td><td></td><td>C4</td><td></td><td></td><td></td><td>C5-I</td><td></td><td></td><td>C5-M</td><td></td><td></td><td>Im1~Im3</td></tr><tr><td></td><td>基料</td><td>涂装 道数</td><td>NDFT /μm</td><td>基料：</td><td>道数</td><td>7pim</td><td>L</td><td>M</td><td>H</td><td>L</td><td>M</td><td>H</td><td></td><td>L</td><td>M</td><td>H</td><td>L</td><td>M</td><td></td><td>H</td></tr><tr><td>A8.01</td><td>EP,PUR</td><td>1</td><td>NA</td><td>EP,PUR</td><td>2</td><td>160</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>A8.02</td><td>EP,PUR</td><td>1</td><td>NA</td><td>EP,PUR</td><td>3</td><td>240</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>A8.03</td><td>EP</td><td>1</td><td>NA</td><td>EP,PUR</td><td>3</td><td>450</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>A8. 04</td><td>EP,PUR</td><td>1</td><td>NA</td><td>EP,PUR</td><td>3</td><td>320</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>底涂层基料</td><td>类型</td><td>可水性化</td><td>面涂层基料</td><td>类型</td><td>可水性化</td></tr><tr><td>EP=环氧</td><td>双组分</td><td>X</td><td>EP=环氧</td><td>双组分</td><td>X</td></tr><tr><td>EPC=改性环氧</td><td>双组分</td><td></td><td>EPC=改性环氧</td><td>双组分</td><td></td></tr><tr><td>PUR=聚氨酯(芳香族)</td><td>单或双组分</td><td>X</td><td>PUR=聚氨酯(脂肪族)</td><td>单或双组分</td><td>X</td></tr></table></body></html>\n\n$\\textcircled{1}$ $)\\mathrm{\\DeltaNDFT=}$ 设计干膜厚度；$\\textcircled{2}$ 在这种情况下，配套涂层的耐久性和涂层与热喷涂表面的附着力有关；$\\textcircled{3}$ $\\mathbf{NA}=$ 不适合，封闭层的干膜厚度对总干膜厚度没有明显影响。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 127,
+        "chunk": "# 四、重防腐涂装施工工艺要点",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 128,
+        "chunk": "# 1.涂装前的表面处理  \n\n严格的表面处理是决定钢结构涂层寿命诸多因素中的首要因素。表面处理不但要形成一个清洁的表面，以消除金属腐蚀的隐患，而且要使该表面的粗糙度适当，以增加涂层与基体金属间的附着力。而喷砂迄今仍是涂装前表面处理的最佳工艺选择。  \n\n（1）相关标准  \n\nGB/T 8923—1998 涂装钢材表面锈蚀等级和除锈等级（等效采用国际标准ISO8501—1：1988）  \nGB/T 13288—1991 涂装前钢材表面粗糙度的评定（比较样块法）（参照采用国际标准ISO8503：1985）  \nGB/T 6807—2001 钢铁工件涂装前磷化处理技术条件  \nGB/T18838.1—2002涂覆涂料前钢材表面处理喷射清理用金属磨料的技术要求导则和分类（修改采用国际标准ISO11126-1：1993）  \nGB/T17850.1—2002涂覆涂料前钢材表面处理喷射清理用非金属磨料的技术要求导则和分类（修改采用国际标准ISO11124-1：1993）  \nGB/T18839.1—2002涂覆涂料前钢材表面处理表面处理方法总则（等效采用国际标准ISO8504-1：1988）  \nGB/T18839.2—2002涂覆涂料前钢材表面处理表面处理方法 磨料喷射清理（等效采用国际标准ISO8504-2：2000）  \nGB/T18839.3—2002涂覆涂料前钢材表面处理表面处理方法手工和动力工具清理（等效采用国际标准ISO8504-3：1988）  \nSY/T 0407—1997 涂装前钢材表面预处理规范  \nGB/T13312—1991 钢铁件涂装前除油程度检验方法（验油试纸法）（JB/Z236—  \n\n(2）喷砂前准备  \n\n$\\textcircled{1}$ 应在钢材切割、矫正、组装完成后进行。$\\textcircled{2}$ 应除去焊渣、起鳞、割孔、焊孔等表面缺陷，打磨圆顺所有锐边、尖角、毛刺，经检验合格后方可进行喷砂作业。$\\textcircled{3}$ 去除表面油污，用清洁剂进行低压喷洗或软刷刷洗，并用高压淡水冲洗掉所有残余物，干燥后经检验合格，再进行喷砂。$\\textcircled{4}$ 喷砂作业的环境条件：钢板表面温度高于露点 $3^{\\circ}C$ 以上，露天作业相对湿度低于 $85\\%$ 中$\\textcircled{5}$ 磨料：喷砂所用的磨料应符合GB6484、GB6485标准所规定的钢砂、钢丸或使用无盐分、无污染的石英砂、铜矿砂。磨料粒度和表面粗糙度的关系，参考TB/T1527附录A。  \n\n(3）喷砂工艺要求  \n\n$\\textcircled{1}$ 喷砂除锈等级应达到GB/T8923（等效采用ISO8501-1：1988）的 $s a2.5$ 级；对于分段对接处和喷砂达不到的部位，采用动力工具机械打磨除锈，达到上述标准中的St3级。  \n\n$\\textcircled{2}$ 涂装前钢材表面的粗糙度要求：按GB/T13288（或参照采用ISO8503-1：1988）标准规定，达到 $R_{z}40{\\sim}80\\mu\\mathrm{m}$ 粗糙度要求。符合粗糙度样板RugotestNo.3的 $R_{\\mathrm{a}}6.3{\\sim}12.5{\\mu}{\\mathrm{m}}$ 粗糙度要求。  \n\n$\\textcircled{3}$ 在喷砂施工期间，要确保磨料没有受到灰尘和有害物质的污染。  \n\n④ 检验：喷砂完工后，除去喷砂残渣，使用真空吸尘器或无油无水分压缩空气，吹去表面灰尘，经质量自检，并取得监理工程师认可，合格后必须在4h内喷漆。  \n\n③收砂：喷砂完成后应及时收砂，并经尘砂分离器分离。清洁的好砂可以回收，废砂及尘埃应及时清除出系统。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 129,
+        "chunk": "# 2.涂漆工艺要点  \n\n除了严格的表面处理和合理的涂装设计外，必须在整个涂装施工中确保每一个环节的质量。任何一个环节的疏忽都有可能对涂层的整体质量带来严重的影响。因此所有参与施工的人员，都必须严格地执行涂装工艺文件。  \n\n（1）施工人员在涂装前，应认真阅读每个系统的涂装工艺文件。了解各部位的涂料配套。阅读相关涂料产品说明书及其施工指导。  \n\n(2）质量不合格的涂料不能投人使用，所有涂料须报验合格后方可使用。禁止将不同品种、不同牌号和不同厂家的涂料混掺调用。  \n\n(3）对于将要喷涂的钢材表面需报验并确认其清洁度、粗糙度合格后方可涂装。  \n\n（4）确认施工现场环境和相对湿度符合所用相关涂料产品说明书所规定的范围，井做好涂装环境条件的记录、备查。  \n\n（5）检查每度涂料的准备和使用，包括涂料的型号、批号、色号、数量等；分清所用涂料的干燥类型，特别要注意双组分涂料的施工，包括固化剂和基料的混合比例、混合使用时间及固化剂的品牌随季节变化而变化的规定；正确使用稀释剂，注意随施工环境温度、湿度的变化而随时调整涂料的施工黏度，防止干喷和流挂。  \n\n(6）上度和下度涂料工序的间隔时间，要求严格遵守相关涂料产品说明书上所规定的重涂间隔时间。  \n\n(7）双组分涂料每次调配的数量要同工作量、涂料的混合使用时间和施工人力、作业班次相适应，太多或太少均不利于施工。混合比例要准确。根据涂料供应商产品说明书中规定的体积比（或质量比）混合加人。  \n\n(8）检查调整每度涂料施工设备、工具。做到配备齐全，并保证其处在最佳使用条件。喷漆前做好预涂。双组分涂料所用的喷枪，在每次喷涂完工后，要及时用配套稀释剂清洗喷枪和管路，以免涂料胶化而堵塞。采用高压无气喷涂工艺推荐执行JB/Z350—1989《高压无气喷涂典型工艺》标准。  \n\n（9）要注意涂料的存放、开启和使用前的混合、搅拌等具体要求。  \n\n（10）加强施工现场检测，特别是在涂装过程中要不断检测调节每度涂料的湿膜厚度，以控制干膜厚度，控制涂层系统的总干膜厚度。此外，随时目测每度涂料在成膜过程中的外观变化，注意有无漏喷、流挂、针孔、气泡、色泽不均、厚度不匀等异常情况，并在涂料供应商技术服务人员的指导下，随时调节、及时修补，并做好记录。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 130,
+        "chunk": "# 3.关于涂装现场管理和安全文明生产  \n\n大型钢结构涂装工程需要严格的现场管理。主要内容包括人员培训、工艺与工艺纪律、消防安全、质量控制、材料定额管理、吊装与运输、工具与装备、涂装环境控制等。此外，应按照GB7691—1987《涂装作业安全规程劳动安全和劳动卫生管理》、GB7692—1999《涂装作业安全规程涂漆前处理工艺安全及其通风净化》、GB6514—1984《涂装作业安全规程涂漆工艺安全》、GB12367—1990《涂装作业安全规程静电喷漆工艺安全》、GB12942—1991《涂装作业安全规程有限空间作业安全技术要求》等国家强制标准的要求，严格涂装现场文明生产、消防、卫生、安全等管理工作。  \n\n涂装工程质量管理系统图如图3-3-38所示。  \n\n![](images/8282c47e3275340bdc3016ee123c99f23112c523226a432a0d6f79c77c664a36.jpg)  \n图3-3-38 涂装工程质量管理系统图  \n\n笔者并非专门的质量管理人员，知之不多，提出这个问题，是因为在多年来从事涂料与涂装的实践中，体会到涂装工程的质量管理非常重要。例如，同样的配套，在不同环境下或施工方法稍有不同，所得到涂层质量常常差别很大。所以，质量管理事关工程的质量效果，提醒同行们重视。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 131,
+        "chunk": "# 第四节 混凝土结构的腐蚀与防护",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 132,
+        "chunk": "# 一、混凝土结构腐蚀的严重性  \n\n从1824年波特兰水泥的发明算起，混凝土材料至今已有150多年的历史。目前，全世界混凝土的年产量已达30亿立方米，并被广泛应用于土木建筑、水利水电、海洋及港口建设工程、交通运输、公路与铁路工程，甚至航空与航天工程等。可以说，混凝土材料为人类的文明与发展做出了巨大的贡献。  \n\n我国目前水泥年产量达6亿多吨，是水泥产量最多的国家；混凝土年产量也高达12亿～13亿立方米/年，约占世界总产量的40%，是世界上混凝土生产和应用最多的国家。  \n\n混凝土是一种人造石，应具有类似于天然石材的耐久性。坚硬的混凝土本身也是一种耐腐蚀的材料，所以在很多年以来，人们常常认为混凝土不需要保护，并且经常将混凝土用于钢结构的保护。但试验和应用证明，混凝土和钢筋混凝土在使用过程中，受到土壤、水及空气中有害介质的侵蚀，或混凝土本身组成材料有害成分的化学及物理作用，会产生劣化，宏观上会出现开裂、溶蚀、剥落、膨胀、松软及强度下降等，严重者会使结构破坏而倒塌，人们逐渐认识到混凝土也必须加以保护以延长其使用寿命，而最常用的方法是用涂料、涂装进行防护。  \n\n混凝土是由硅酸盐水泥、填充沙砾、水和助剂等混合后经水合浇筑而成，其中水泥、填充沙砾等作为“主剂”；而水作为“溶剂和固化剂”。水泥的基本化学组成为3CaO·SiOz和$\\beta{\\cdot}2\\mathrm{CaO}\\cdot\\mathrm{SiO}_{2}$ 以及少量的 $\\mathrm{3CaO\\cdotAl_{2}O_{3}}$ ? $4\\mathrm{CaO}\\cdot\\mathrm{Al_{2}O_{3}}\\cdot\\mathrm{Fe_{2}O_{3}}$ 或者是一些铁相的固体溶液 $\\bf{M g O}$ 、 $\\mathtt{C a O}$ 以及其痕量化合物。混凝土强度与硬化条件关系如图3-3-39所示。  \n\n混凝土的典型特性是易生产和浇筑；抗冲击、抗压、耐磨性较好；但是由于伸长强度差，需使用钢筋骨架来改善，而成为钢筋混凝土。混凝土通常需经过28天固化后方可达到应具备的物理力学性能（图3-3-40）。  \n\n![](images/2624b5fb93e5cd17e7d1a3fa3d903a1859a9f5395bef96ed6d11342206e69134.jpg)  \n图3-3-39 混凝土强度与硬化条件关系图  \n\n![](images/df5daa80420a89c3733e78191beb317666d137e6843d3ae04257b04d34176ee9.jpg)  \n图3-3-40 混凝土强度与水配比及硬化时间关系  \n\n钢筋混凝土结构结合了钢筋与混凝土的优点，已成为最常用的结构形式之一。但是钢筋腐蚀破坏造成的直接、间接损失之大远远超出人们的意料，在欧美发达国家已构成严重的财政负担。  \n\n钢筋混凝土结构在生产环境中往往存在多种酸、碱、盐等腐蚀性介质，形成了严重腐蚀的隐患。例如，海洋工程中广泛使用的钢筋混凝土结构因腐蚀引起破坏的情况尤其严重。除海洋环境本身属于强腐蚀环境因素外，从设计到施工的监管等诸多环节都有很大的防腐改善空间。尽管国内现行的《工业建筑防腐蚀设计规范》中规定了一系列钢筋混凝土结构设计防护方法及措施，但由于市场经济中投资与回报等因素，往往影响设计与施工单位的意向，防腐蚀形势仍不容乐观，需要投资方、设计、监理、涂料供应商及施工单位通力合作，把防腐蚀工作做好。  \n\n楼、地面及基础主要受到不同的腐蚀介质作用，在潮湿环境条件下，混凝土保护层易被介质侵蚀而脱落或损坏；柱、梁、顶棚及屋盖主要受气相腐蚀介质作用，在外界温度及湿度等因素影响下，介质附着物通过孔隙和裂缝侵入表皮锈蚀钢筋，降低了构件承载能力。用适当增加混凝土保护层厚度、提高其抗渗抗裂性能等办法便能阻止或减轻腐蚀介质的侵人。造成腐蚀的重要因素之一是施工质量问题。事实证明由于施工质量不能保证等因素，往往能够从报纸上看到我国混凝土结构大部分在使用10年左右即出现较严重的腐蚀破坏的报告。虽然国内现在的新科技有很多突破，但混凝土材料和结构的设计方法正处在由强度设计向耐久性设计过渡的阶段。影响混凝土耐久性的各种破坏过程几乎都与其孔隙组成有密切关系，混凝土的渗透性是一个关键的课题，因此提高混凝土耐久性与长寿命的手段是提高抗渗性。同样，混凝土的抗腐蚀性能取决于本身微观结构，现今的混凝土浆体的孔隙率较普通混凝土有明显改善，结果是浆体中水或侵蚀性介质侵入过程有关的物理和化学侵蚀作用就相对应的削弱。所以高性能混凝土比普通混凝土更耐久，更能抵抗环境腐蚀介质的破坏。但高性能混凝土作为结构材料本身内部也存在许多微裂缝，这些裂缝提供了环境中的侵蚀性组分进人基体的通道。加之混凝土承受外界荷载的作用，使其内部孔结构发生变化产生疲劳损伤，导致外界腐蚀介质容易进人内部，使其抗腐蚀性能有所降低。这种现象如果通过其他途径例如涂装封闭等手段是可以降低的，从而延长其使用寿命。",
+        "category": " Introduction"
+    },
+    {
+        "id": 133,
+        "chunk": "# 二、钢筋混凝土结构的腐蚀机理  \n\n影响混凝土结构耐久性的因素可分为内因和外因两个方面。内因即混凝土自身抵抗侵蚀和风化的能力。主要包括：混凝土的水灰化、钢筋保护层厚度、最大裂缝宽度、混凝土的搅拌与浇筑工艺及养护质量等；外因即外部环境条件，如空气中各种有害气体含量、湿度及温度等。如图3-3-41所示是混凝土腐蚀劣化常见因素分解图。  \n\n![](images/211744beb56235e7bce8843dba3d4cdefce302930475f1e7aa892ed34fef48a1.jpg)  \n图3-3-41钢筋混凝土结构腐蚀劣化因素分解图",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 134,
+        "chunk": "# 1.物理作用  \n\n物理作用主要是指在没有化学反应发生时，混凝土内的某些成分在环境因素的影响下，进行溶解或膨胀引起混凝土强度降低，导致结构破坏。  \n\n(1）外力作用超负荷承载和物体撞击对混凝土构筑物的损害最大，例如在码头、桥墩，由于长期处于超重工作状态，或受到撞击，出现长度几厘米至十几厘米、宽度不等的斜状裂缝或裂纹，致使保护层损坏，钢筋裸露，锈迹斑斑；又如工业厂房、车库的进出口等，也常常有这种破坏。  \n\n(2）浸析作用即环境介质将混凝土中易溶成分如Ca(OH)2溶解出来，引起pH降低，孔隙率增大、强度减小，使腐蚀介质更易进人混凝土内部。这种浸析作用循环反复，导致混凝土结构的很快破坏。  \n\n(3）结晶作用混凝土内的某些盐类（包括外来的和自身的）在湿度较大时溶于水中，而在湿度较低时结晶析出，并在结晶时按其特有的结晶学特征生长，对混凝土孔壁造成极大的结晶压力，从而引起混凝土的膨胀开裂。寒冷地区的冻融循环破坏也属此类反应，冻融循环越频繁，对混凝土的破坏就越大。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 135,
+        "chunk": "# 2.化学腐蚀  \n\n环境中的各种腐蚀介质如COz、CI-、SO—、Mg+等进人混凝土内，与之发生化学反应，造成化学腐蚀。  \n\n(1）碳化作用空气中或溶于水中的二氧化碳（CO）与水泥石中的氢氧化钙[Ca(OH)z]、水化硅酸钙（3CaO·2SiOz·3HzO）等起反应，导致混凝土碱度降低  \n\n![](images/6ec308ab01e655e4dd4f1648c4c1bd420bd9524fc7b961252dab503ce73e8701.jpg)  \n（@）：混凝出pH=123 （b）混凝土pH=9  \n\n图3-342钢筋混凝土碳化作用示意（中性化）和混凝土粉化，称为碳化作用（图3-3-42）。  \n\n混凝土中的氢氧化钙是一种高碱性物质，$\\mathbf{pH}$ 在12以上，混凝土中钢筋与 $\\mathrm{Ca(OH)_{2}}$ 溶液接触，表面会形成氧化亚铁钝化膜，对钢筋起到保护作用。这种钝化作用在碱性环境中是很稳定的。但是一旦有二氧化碳（或者二氧化硫）等酸性气体渗入，与氢氧化钙发生化学反应变成碳酸钙，发生了混凝土内部体系中性化过程，称为碳化作用。反应式如下。  \n\n$\\mathrm{CO_{2}+C a(O H)_{2}\\longrightarrow C a C O_{3}+H_{2}O}$ $\\mathrm{CO}_{2}+\\mathrm{H}_{2}\\mathrm{O}\\longrightarrow\\mathrm{H}_{2}\\mathrm{CO}_{3}$ $\\mathrm{Ca(OH)}_{2}+\\mathrm{H}_{2}\\mathrm{CO}_{3}\\longrightarrow\\mathrm{CaCO}_{3}+2\\mathrm{H}_{2}\\mathrm{O}$ 总反应： $2C O_{2}+2C a(O H)_{2}\\longrightarrow2C a C O_{3}+2H_{2}O$ 实际上，大气中另一种污染性气体二氧化硫也有类似的作用，亦可称作硫化作用。  \n\n$$\n2S O_{2}+2C a(O H)_{2}\\rightarrow2C a S O_{3}+2H_{2}O\n$$  \n\n当大量的碳酸钙或者亚硫酸钙形成时，混凝土内部趋于中性化，碱性环境受到破坏，达到一定程度时，如 $\\mathrm{\\bf{p}H}$ 在9以下时，钝态铁的保护层就失去作用，混凝土内的钢筋因为没有受到碱性环境的保护而产生锈蚀。  \n\n混凝土的碳化（硫化）程度取决于混凝土的多孔性，影响因素很多，例如，水泥本身的质量，施工时水分及水泥比例，固化时间及环境等。据以往的经验估计混凝土的表面碳化速度每年达0.5～1mm。由于一般混凝土表面离钢筋的距离为20～50mm，有些地方可能不足$10\\mathrm{mm}$ ，在这种情况下， $10{\\sim}15$ 年后可能就会看到混凝土表面的损坏了。  \n\n碳化（硫化）作用的结果不仅破坏了水泥的成分，而且由于碳酸钙或硫酸钙生成物体积增大，对混凝土产生膨胀侵蚀作用，并进一步与水泥化合物中铝酸三钙起反应，生成体积更大的碳酸钙铝或硫铝酸钙，可使砂石的结合聚集力大大降低，造成了混凝土的粉化。  \n\n(2）氯离子的侵蚀氯盐腐蚀是沿海混凝土建筑物和公路腐蚀破坏最重要的原因之一，氯盐既有可能来自于外部的海水、海风、海雾、化冰盐，也有可能来自于建筑过程中使用的海砂、早强剂、防冻剂等。它可以和混凝土中的 $\\mathrm{Ca(OH)}_{2}$ ， $3\\mathrm{CaO}\\cdot2\\mathrm{Al_{2}O_{3}}\\cdot3\\mathrm{H_{2}O}$ 等起反应，生成易溶的 $C a C l_{2}$ 和带有大量结晶水、比反应物体积大几倍的固相化合物，引起混凝土的膨胀破坏，反应式如下。  \n\n$2C I^{-}+C a(O H)_{2}=C a C l_{2}+2H_{2}O$ $2\\mathrm{Ca(OH)_{2}+2C l^{-}+(\\it n-1)H_{2}O}\\mathrm{-\\itCaO\\cdotCaCl_{2}\\cdot\\it n H_{2}O}$ $3\\mathrm{CaCl}_{2}+(3\\mathrm{CaO})\\cdot\\mathrm{Al}_{2}\\mathrm{O}_{3}\\bullet6\\mathrm{H}_{2}\\mathrm{O}+25\\mathrm{H}_{2}\\mathrm{O}\\longrightarrow3\\mathrm{CaO}\\cdot\\mathrm{Al}_{2}\\mathrm{O}_{3}\\bullet3\\mathrm{CaCl}_{2}\\bullet3\\mathrm{H}_{2}\\mathrm{O}$  \n\n更为严重的是氯离子一旦渗人混凝土内部并吸附于钢筋钝化膜处，达到一定浓度（即临界值）时，pH迅速降低，局部钝化膜开始受到破坏。由于氯离子破坏钝化膜使钢筋局部表面露出了铁基体，与尚完好的钝化膜区域之间构成电位差，铁基体作为阳极，钝化膜区域作为阴极，混凝土中的水或潮气作为电解质构成了一个腐蚀电池，钢筋开始发生点蚀，由于小阳极对应于大阴极，点蚀会迅速发展，降低结构物的强度和耐久性。研究表明，氯离子浓度为10-²g/mL时，电位下降时间为50s左右，而氯离子浓度为10-5g/mL时，电位下降时间为1500s左右，在没有氯离子存在的情况下，其电位保持稳定不变。这表明随着氯离子浓度增加，其阳极电位下降时间不断缩短，并迅速达到活化态电位，对钢筋表面钝化膜破坏作用的腐蚀性增强。总之，只要有氯离子存在，对混凝土中钢筋钝化膜的破坏就不可避免，而且这种破坏作用是钢筋腐蚀的首要因素。此外，氯离子还具有阳极去极化作用和导电性，提高了腐蚀电池工作效率，加速电化学腐蚀过程。因此，国外很多文献与规范中都提出在使用的混凝土添加剂与施工过程中要尽量避免把含氯离子的物质带进混凝土内部。  \n\n(3）硫酸盐的侵蚀由于在海水、湖水、盐沼水、地下水、某些工业污水及流经高炉矿渣或煤渣的水中常含有钠、钾、铵和镁等硫酸盐，其也是破坏混凝土结构耐久性的一个重要因素。硫酸及硫酸盐溶液进入混凝土的毛细孔中，硬化时水分蒸发，浓度提高，直接结晶，或直接与水泥石成分发生化学反应生成结晶，均导致混凝土结构体积膨胀，进而胀裂破坏。由于生成物的体积比反应物大15倍以上，呈针状结晶，引起很大的内应力，其破坏特征是在表面出现较粗大的裂缝，反应式如下。  \n\n$$\n4\\mathrm{CaO\\cdotAl_{2}O_{3}\\bullet12H_{2}O+3N a_{2}S O_{4}+2C a(O H)_{2}+20H_{2}O-\\dots+3C a O\\cdot A l_{2}O_{3}\\cdot C a S O_{4}\\cdot3H_{2}O+6H_{2}O}\n$$  \n\n$$\n\\mathrm{Ca(OH)_{2}+S O_{4}^{2-}+2H_{2}O\\longrightarrow C a S O_{4}\\uparrow2H_{2}O+2O H^{-}}\n$$  \n\n(4）镁盐的腐蚀由于海水中含有大量的镁盐（ $\\mathbf{MgSO_{4}}$ 和 $\\mathbf{MgCl}_{2}$ )，渗入混凝土中将和水泥石中的 $\\mathrm{Ca(OH)}_{2}$ 发生下列反应  \n\n$$\n\\begin{array}{r}{\\mathbf{Ca(OH)_{2}}+\\mathbf{MgSO_{4}}+2\\mathbf{H_{2}O}\\longrightarrow\\mathbf{CaSO_{4}}\\bullet2\\mathbf{H_{2}O}+\\mathbf{Mg(OH)_{2}}\\~\\downarrow}\\\\ {\\mathbf{Ca(OH)_{2}}+\\mathbf{MgCl_{2}}\\longrightarrow\\mathbf{CaCl_{2}}+\\mathbf{Mg(OH)_{2}}\\~\\downarrow}\\end{array}\n$$  \n\n生成的固相物积聚在孔隙内，在一定程度上能够阻挡侵蚀介质的侵入，但是大量的$\\mathrm{Ca(OH)_{2}}$ 与镁盐反应后，碱度降低，水泥石中的水化硅酸钙和水化铝酸钙便易与呈酸性的镁盐起反应，反应式如下（以 $\\bf{M g S O_{4}}$ 为例)。  \n\n$$\n\\mathrm{3CaO\\bulletAl_{2}O_{3}\\bullet6H_{2}O+3M_{g}S O_{4}+6H_{2}O\\longrightarrow(C a S O_{4}\\bullet2H_{2}O)+A l(O H)_{3}+3M_{g}(O H)_{2}\\bullet(O H)_{2}\\bullet(O H)_{4}\\bullet(O H)_{2}O\\ ,}\n$$  \n\n— $\\mathrm{3CaO\\bullet2SiO_{2}\\bullet\\mathrm{3H_{2}O+3M g S O_{4}+9H_{2}O\\longrightarrow\\mathrm{3(C}}}$ aSO·2HO)+2SiO·2HO↓+3Mg(OH)2↓所生成的 $\\mathbf{Mg(OH)_{2}}$ 还能与铝胶、硅胶缓慢反应。  \n\n$$\n\\mathrm{\\bfAl(OH)_{3}}]+\\mathrm{Mg(OH)_{2}}\\longrightarrow\\mathrm{\\bfMg(AlO_{3})_{2}}+4\\mathrm{H_{2}O}\n$$  \n\n$$\n2\\mathrm{SiO}_{2}\\cdot3\\mathrm{H}_{2}\\mathrm{O}+\\mathrm{Mg}(\\mathrm{OH})_{2}\\longrightarrow2\\mathrm{Mg}\\mathrm{SiO}_{3}+5\\mathrm{H}_{2}\\mathrm{O}\n$$  \n\n反应结果使水泥石粘接力减弱，而导致混凝土强变降低。  \n\n(5）酸腐蚀在化工生产车间和受酸雨危害的地区，混凝土构筑物受到强烈的腐蚀作用。酸对混凝土的腐蚀主要是酸能与水泥石中的 $\\mathrm{Ca(OH)_{2}}$ 发生中和反应生成可溶性的钙盐，破坏了水泥石中的碱度，使水化硅酸钙等其他水化产物自行分解，而且盐酸还能直接与这些水化产物反应生成可溶性钙盐，使单位体积内 $\\mathrm{Ca(OH)}_{2}$ 和 $\\mathrm{CSH(B)^{\\bullet}}$ 含量减少。混凝土孔隙率增大，力学性能劣化。酸还可以与混凝土中的某些成分发生反应生成非凝胶性物质或易溶于水的物质，使混凝土产生由外及内的逐层破坏。另外酸还可以促使水化硅酸钙和水化铝酸钙的水解，从而破坏了孔隙结构的胶凝体，使混凝土的力学性能劣化。  \n\n(6）碱腐蚀碱对混凝土的腐蚀首先表现在空气中的 $\\mathrm{CO_{2}}$ 在混凝土表面或孔隙中产生强烈的碳化作用，其反应式如下。  \n\n$$\n\\begin{array}{r}{\\mathrm{CO_{2}}+2\\mathrm{NaOH}\\longrightarrow\\mathrm{Na_{2}C O_{3}}+\\mathrm{H_{2}O}}\\\\ {\\mathrm{CO_{2}}+2\\mathrm{KOH}\\longrightarrow\\mathrm{K_{2}C O_{3}}+\\mathrm{H_{2}O}}\\end{array}\n$$  \n\n水分蒸发后碳酸盐结晶：  \n\n$$\n\\mathrm{Na_{2}C O_{3}+10H_{2}O-\\Sigma\\Sigma\\Sigma^{}N a_{2}C O_{3}\\ \\cdot\\ 10H_{2}O}\n$$  \n\n$$\n\\mathrm{K_{2}C O_{3}+15H_{2}O\\mathrm{-}\\mathrm{K_{2}C O_{3}\\ \\bullet\\ 15H_{2}O}}\n$$  \n\n碱腐蚀的另一个重要表现是混凝土碱-骨料反应，是指混凝土中某些活性矿物料与混凝土孔隙中的碱性溶液之间发生的反应，其生成物重新排列和吸水膨胀所产生的应力诱发产生裂缝，最后导致混凝土结构的破坏。根据反应机理，碱-骨料反应又可分为三种类型。  \n\n$\\textcircled{1}$ 碱硅酸反应碱与骨料中的活性 $\\mathrm{SiO_{2}}$ 反应，生成碱硅凝胶，碱硅凝胶吸水膨胀后产生内应力，导致混凝土开裂，碱硅酸反应发生最为普遍，危害也最为严重。  \n\n$\\textcircled{2}$ 碱碳酸盐反应碱与骨料中的碳酸钙镁反应，将白云石转化为水镁石和黏土，水镁石结晶重排和黏土吸水膨胀产生应力导致破坏。  \n\n$\\textcircled{3}$ 碱硅酸盐反应从机理上说仍属于碱硅酸反应，但膨胀进程缓慢。碱-骨料反应发生需要两个条件：第一是混凝土原材料中含碱量高，现在大多数国家规定骨料中的碱不超过 $0.6\\%$ 或混凝土含碱量不超过 $30k g/\\mathrm{m^{3}}$ ；第二是有水分和空气的供应，越是潮湿的环境碱-骨料反应越容易发生。硅灰、粉煤灰和高炉矿渣均可缓解、抑制碱-骨料反应的发生。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 136,
+        "chunk": "# 3.钢筋的电化学腐蚀  \n\n混凝土内埋置钢筋的锈蚀，导致混凝土开裂，构件承载力不足引起的结构耐久年限降低，是影响混凝土结构耐久性的最主要因素之一。在工业厂房中，除化工车间、酸洗车间等有侵蚀性化学物质扩散的车间外，因钢筋锈蚀引起的结构耐久性破坏比较多见。在水工、海工及道桥结构中，钢筋锈蚀开裂破损的现象也很普遍。  \n\n在混凝土结构中钢筋锈蚀大多数情况下为电化学腐蚀，此外，在特定条件下，也可发生杂散电流腐蚀、应力腐蚀及氢脆腐蚀。  \n\n（1）常见电化学腐蚀当钢筋在强碱性环境中（ $\\mathbf{pH}$ 为 $12.5\\sim13.2)$ ，表面会生成一层致密的薄膜皇钝化状态保护钢筋免受腐蚀。其周围混凝土对钢筋的这种碱性保护作用在很长时间内都是有效的。然而一旦钝化膜遭到破坏，钢筋就处于活化状态，就有受到腐蚀的可能性。使钢筋的钝化膜破坏的因素，如前所述主要有以下几点。  \n\n$\\textcircled{1}$ 碳化作用破坏钢筋钝化膜，$\\textcircled{2}$ 由氯离子作用破坏钢筋钝化膜  \n\n$\\textcircled{3}$ 由于 $50_{4}^{2-}$ 或其他酸性介质侵蚀而使混凝土碱度降低钝化膜破坏。  \n\n$\\textcircled{4}$ 混凝土中掺加大量活性混合材料或采用低碱度水泥，导致钝化膜破坏或根本不生成钝化膜。  \n\n(2）杂散电流腐蚀杂散电流腐蚀是由于漏电引起的，一般发生于电解车间，在其他厂房中由于在结构上违章接电或天车系统绝缘不良等，也会出现漏电现象。直流电解系统漏泄到地下的电流，对钢筋混凝土结构所造成的腐蚀破坏，其实质是一种电解作用。根据杂散电流流动方向和路径的不同，可以分为阳极腐蚀和阴极腐蚀。当混凝土中的钢筋处于阳极时，就发生氧化而出现阳极腐蚀，钢筋锈蚀膨胀，混凝土开裂；当钢筋处于阴极时，根据阴极保护理论，带阴极电流较小，一般不会发生腐蚀，若阴极电流较大，钢筋表面阴极反应速率加快，氧的去极化反应产生大量 $\\mathrm{\\Omega_{OH}-}$ ，使钢筋表面的混凝土过度碱化，并导致大量氢气析出，破坏钢筋与混凝土的粘接力，使混凝土开裂。钢筋表面尽管轻度锈蚀，但会增加氢脆的危险。  \n\n在杂散电流作用下，混凝土中电位发生大幅度变化。阳极部位电位正向变化且腐蚀速度较大，在短期内就可能造成危险性破坏；阴极部位的电位负向变化，遭受杂散电流作用的钢筋在锈蚀处呈针尖状的锈蚀状态。  \n\n此外，应力腐蚀和氢脆一般出现在预应力混凝土结构中。而一般混凝土结构中产生的钢筋腐蚀通常为电化学腐蚀。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 137,
+        "chunk": "# 4.生物腐蚀  \n\n生物对混凝土的腐蚀问题尚未引起国内重视，但在国际上20世纪70年代初已经提出混凝土结构抗生物腐蚀的问题，开始使用防霉剂、杀虫剂进行预防。生物腐蚀主要有以下儿种形式：一是生物物理作用，草、树根等在生长过程中，钻入混凝土的缺陷，破坏其密实度，将混凝土劈裂；二是类似于混凝土化学腐蚀的微生物腐蚀，如硫化菌利用下列反应：  \n\n$$\n\\mathrm{S}+\\mathrm{SO}_{2}+2\\mathrm{H}_{2}\\mathrm{O}\\longrightarrow2\\mathrm{H}_{2}\\mathrm{SO}_{4}\n$$  \n\n将S转变成 $\\mathrm{H_{2}S O_{4}}$ ，从而引起混凝土的硫酸和硫酸盐腐蚀。加入矿物粉细填料改善混凝土的孔结构，加人对人畜无害、具有长效性能的杀生物剂等，均可有效增强混凝土的抗生物侵蚀性能。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 138,
+        "chunk": "# 三、钢筋混凝土腐蚀环境分析  \n\n钢筋混凝土在不同的环境下会遭受不同的腐蚀条件，大气环境是其中首要因素，这包括施工时的环境因素与使用时的环境因素，如气候的变化、空气的质量、污染物出现的周期、温湿度的变化等。其次是钢筋混凝土结构所处的工况条件，即使在同一个大气环境的海域地区，结构的不同位置也会出现有不同的工况条件。以海洋环境为例具体说明如下。",
+        "category": " Introduction"
+    },
+    {
+        "id": 139,
+        "chunk": "# 1.大气区  \n\n在水面以上的区域称为大气区，由于长期处于海水、海风等环境中，钢筋混凝土通常会遭到腐蚀并破坏，维修很困难甚至无法维修。因此，混凝土结构的长期防腐是迫切需要解决的问题。这对海洋资源的开发、海工构筑物的建设、海军现代化等都有重要意义。",
+        "category": " Introduction"
+    },
+    {
+        "id": 140,
+        "chunk": "# 2.浪溅区——千湿交替  \n\n在水面以上， $1\\sim2\\ m$ 的区域称为浪溅区（处于干湿交替状态)。由于长期处于海浪的冲撞、拍打、阳光曝晒、海水蒸发交替作用下，同时氧气供应比较充裕，钢筋混凝土通常会遭到腐蚀并破坏。由于潮水高低交替，潮汐周期短，维修很困难甚至无法维修。此外，有些地方由于气候环境因素，使海生物附着在混凝土上生长，硫杆菌能将硫、硫化硫酸盐、亚硫酸盐等氧化成硫酸盐，最终转化成对混凝土有强腐蚀性的硫酸；硫酸盐还原菌还能将硫酸盐还原为强腐蚀性硫化氢，最终导致另外的一种破坏—微生物腐蚀。处于干湿交替状态下构件所选用的防腐涂料，既要耐阳光紫外线，又要有优良的耐海水性，加之由于潮汐周期短给涂料施工带来困难，所以浪溅区结构防腐是一个涂装难点而引起防腐界的关注。",
+        "category": " Introduction"
+    },
+    {
+        "id": 141,
+        "chunk": "# 3.水下区  \n\n在水面以下的区域称为水下区，由于长期处于海水流动，并受到海水中沙石杂物等的冲刷、撞击，同时海水含有很多对混凝土有害的物质，使钢筋混凝土受到的破坏特别严重，通常先是使混凝土层的分解，海水的渗透使钢肋腐蚀、膨胀等现象。维修很困难甚至无法维修。因此，防腐蚀是混凝土结构设计与施工的重要环节。",
+        "category": " Introduction"
+    },
+    {
+        "id": 142,
+        "chunk": "# 4.泥下区  \n\n在水下面的泥土层区域称为泥下区，混凝土结构的桩、支撑物等由于长期处在泥土中，而因为海水中溶解的化学物质比较多，通过渗透、吸收等，使泥土中含有多种电解质，导致泥下区混凝土受到比较复杂的电化学腐蚀破坏。即使在防腐设计时已充分考虑到各种腐蚀因素，但是由于防腐施工质量引致的问题，不是简单可以解释清楚，发生问题后，又由于种种原因，解决方案并不一定能够实施。因此精心设计、精心施工是长期防腐工程的唯一选择。  \n\n当然钢筋混凝土不完全处于海洋环境，对各种不同的环境和工况条件，要做具体分析与研究，制定科学而切实可行的防护措施。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 143,
+        "chunk": "# 四、混凝土结构腐蚀防护措施  \n\n提高钢筋混凝土结构的抗腐蚀性能与耐久性，可以从多方面进行：改变混凝土的质量，可以从选用高质量的材料，加入先进的外加剂与改变水灰、灰沙等材料的比例入手；同时要关注钢筋的选用，即选用已经经过处理的高防腐钢材；以高质量的施工来保证高质量的涂层质量等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 144,
+        "chunk": "# 1.选用耐蚀水泥  \n\n(1）针对不同环境选用不同品质的水泥如在酸性环境中选用耐酸水泥，在海水中选用耐硫酸盐水泥和普通硅酸盐水泥等。  \n\n(2）改善调配比例可使混凝土内部结构密实，强度高，抗渗性好。如果控制不好，会使混凝土收缩大，抗渗性低，混凝土不密实等。  \n\n(3）引入外加剂掺人引气剂、膨胀剂、减水剂、防水剂、粉煤灰和矿渣等新型外加剂可以显著改善混凝土的质量。如引气剂是一种具有憎水作用的表面活性剂，能显著降低混凝土拌和水的表面张力；加人聚合水化硅氧烷，加强混凝土的抗冻性，在低温条件下发挥比较理想的效果；新型的膨胀剂，可使混凝土抗渗能力提高。其他具有抗裂、抗冻融、提高强度功效的粉煤灰、火山灰等的使用可以提高混凝土的抗渗、抗碳化、抗浸析能力并有效地抑制碱-骨料反应。  \n\n(4）精心施工是确保混凝土质量的前提进行合理的搅拌、振捣和充分的湿养护，一般养护时间为28天。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 145,
+        "chunk": "# 2.增加混凝土密实度和钢筋保护层厚度  \n\n(1）提高钢筋保护层厚度所谓保护层是指钢筋四周混凝土的厚度。钢筋保护层是防止钢筋锈蚀的第一道屏障，必须有足够的厚度，由于海上混凝土结构，所处的环境比较严酷，应该适当加大其保护层厚度。一般来说在 $50\\mathrm{mm}$ 以上比较合适。  \n\n(2）加入钢筋阻锈剂在拌制混凝土时加人钢筋阻锈剂可提高混凝土钢筋的抗蚀能力。迁移型阻锈剂是近年来提出的全新概念。它可外涂，虽然不如内掺效果好，但它迁移到钢筋表面的这种性能是有重要意义的。迁移型阻锈剂的使用并不会降低混凝土的力学性能；吸水性等物理性能没有任何改变，相反可以提高混凝土的高温下（ $60^{\\circ}C$ ）的拉伸强度、弯曲强度。电化学研究表明，迁移型阻锈剂可显著降低腐蚀速率，且这种作用对低强度混凝土比对高强度混凝土更明显。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 146,
+        "chunk": "# 3.严格控制裂缝宽度  \n\n钢筋腐蚀产物—铁锈的体积为原先铁体积的 $2.5\\sim7$ 倍，所产生的膨胀压力会造成混  \n\n凝土的开裂、剥落。许多情况下先是由于结构上各种裂缝引起钢筋腐蚀，腐蚀的结果使得裂缝扩大、混凝土剥落。因此在结构设计和施工管理上，应尽量避免裂缝出现，或严格控制裂缝宽度。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 147,
+        "chunk": "# 4.钢筋表面防腐处理  \n\n钢筋表面防腐处理可分为金属的表面防护和非金属的表面防护。镀锌是常用的金属表面防护措施。它既可以使钢筋和外界环境隔离，又可起到牺牲阳极保护阴极（钢筋）的作用；非金属表面防护主要有环氧树脂（如液态环氧，粉末环氧）和其他聚合体树脂等。当然也可采用成本比较贵的不锈钢钢筋，国外有研究表明，它的寿命比普通钢筋耐用几倍，不需任何维护，在极其恶劣的海洋腐蚀环境中，可达到60年不损坏。  \n\n特别指出的是防止氯化物接触钢筋表面。控制混凝土材料中氯化物含量，一般要求，钢筋混凝土从各种组成材料引入的氯离子含量（折算成氯盐含量）为：不宜超过水泥用量的$0.2\\%$ （当结构处于干湿交替状态下或常年湿度大于 $80\\%$ 时）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 148,
+        "chunk": "# 5.涂装防护  \n\n在采取以上各项保护措施之后，尚须对混凝土结构外表面作全面涂料保护。目的在于阻  \n\n缓或屏蔽外界名种腐蚀性介质的入侵，如图3-3-43所示。  \n\n目前常用的混凝土防腐涂料有溶剂型与水性涂料两大类。环氧树脂、氯化橡胶、聚氨酯、丙烯酸树脂等是用得最多的成膜树脂。它们都有各自优良的防腐性能。然而，溶剂型涂料大部分使用有机溶剂，污染环境，危害人体健康，氯化橡胶甚至已被国际组织禁止或限制生产；而水溶性涂料在施工表现方面也有一定局限性。  \n\n![](images/dcb4d38268945a51d1d7dd7bf348f0874d00c7e6532eb1a702fa88e034194ce7.jpg)  \n图3-3-43 混凝土表面涂层保护示意  \n\n混凝土防腐涂料发展趋势随着世界各国环保法规的确立和环保意识的强化，出现了许多有发展前景的高性能、环保型涂料新技术。  \n\n(1）纤维增强材料将纤维材料与粘接性树脂（环氧树脂或乙烯醇树脂）混合，粘贴于结构表面，不仅增强对外界腐蚀介质的封闭作用，而且利用纤维材料良好的拉伸强度增强构件承载能力与刚度，以达到对结构及构件加固、补强的目的。目前流行碳纤维加固修补混凝土技术，但施工复杂，修复措施成本高。  \n\n(2）渗透型保护材料有机硅等渗透型保护材料喷涂在混凝土表面后能渗入混凝土毛细孔中，形成一定厚度的填充封闭层。可提高混凝土的密实度，防止内部钢筋锈蚀。但这种材料无弹性和韧性，使用前必须严格进行表面处理。  \n\n(3）无溶剂聚脲涂料（简称SPUA）SPUA是国内外近十年来刚刚兴起的一种新型，比较环保的涂料。SPUA具有优异的综合力学性能，耐候性好、耐冷、热冲击、对湿度和温度不敏感。它还可以加入各种颜料制成不同颜色产品，并可掺人其他填料如短玻璃丝纤维等对其进行增强。快速喷涂、现场固化。但由于目前该材料在国内价格较贵等因素，推广工作尚处于起步阶段。对于大型维修工程而言，SPUA 材料优异的性能和施工高效，从长远效益分析，很容易弥补材料的高成本。  \n\n综上所述，海洋等严酷的环境对混凝土构筑物有非常强的腐蚀破坏作用、混凝土的防腐问题有时甚至比混凝土的强度要求更为重要。为了提高混凝土的防腐性能，可以从以下两个  \n\n方面考虑综合防护措施。  \n\n①尽量避免或减轻形成混凝土劣化的任何条件。采用的措施有：选择合适的水泥品种、涂层、阴极保护等。  \n\n$\\textcircled{2}$ 优化钢筋混凝土结构的材料组分和细部构造以抵御严酷环境的作用，采用的措施有：适宜的结构形式、外加剂保护层、钢筋涂层、检测和保养等。  \n\n近十几年来，混凝土防护和修复方面出现了许多具有优异性能和发展潜力的新材料及新技术，如渗透型阻锈剂、不锈钢钢筋、渗透型保护材料、纤维增强材料以及SPUA材料的应用等，都将是这一领域今后的发展方向。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 149,
+        "chunk": "# 五、混凝土防护涂层配套体系  \n\n表3-3-34～表3-3-39列举了常见混凝土防护涂层配套体系，供参考。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 150,
+        "chunk": "# 1.水上区混凝土结构表面  \n\n表3-3-34 普通配套  \n\n\n<html><body><table><tr><td>涂层</td><td>涂料体系</td><td>干膜厚度/μm</td></tr><tr><td>封闭层</td><td>环氧封闭漆</td><td>按混凝土表面灵活掌握</td></tr><tr><td>腻子层</td><td>环氧腻子</td><td>用于填坑找平</td></tr><tr><td>中间层</td><td>环氧厚浆漆</td><td>100</td></tr><tr><td>面层</td><td>聚氨酯面漆</td><td>40</td></tr><tr><td>面层</td><td>聚氨酯面漆</td><td>40</td></tr><tr><td colspan=\"3\">总计 180</td></tr></table></body></html>  \n\n表3-3-35 防碳化配套涂料  \n\n\n<html><body><table><tr><td>涂层</td><td>涂料体系</td><td>干膜厚度/μm</td></tr><tr><td>封闭层</td><td>环氧封闭漆（只用于大面积有孔洞范围）</td><td>按混凝土表面灵活掌握</td></tr><tr><td>腻子层</td><td>环氧腻子</td><td>用于填坑、找平</td></tr><tr><td>封闭层</td><td>丙烯酸封闭漆（防碳化品种）</td><td>按混凝土表面灵活掌握</td></tr><tr><td>面层</td><td>丙烯酸面漆（防碳化品种）</td><td>50X2</td></tr><tr><td></td><td>总计</td><td>100</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 151,
+        "chunk": "# 2.浪溅区混凝土结构防护涂层配套  \n\n表3-3-36 超强环氧漆配套  \n\n\n<html><body><table><tr><td>涂层</td><td>涂料名称</td><td>干膜厚度/um</td></tr><tr><td>封闭层 腻子层</td><td>环氧封闭漆 环氧腻子</td><td>按混凝土表面灵活掌握 用于填坑、找平</td></tr><tr><td>底-面合一</td><td>超强环氧漆或环氧玻璃鳞片漆 总计</td><td>350～500 350～500</td></tr></table></body></html>  \n\n表3-3-37 湿固化聚氨酯漆配套  \n\n\n<html><body><table><tr><td>涂层</td><td></td><td>涂料名称</td><td>干膜厚度/μm</td></tr><tr><td>封闭层</td><td></td><td>环氧封闭漆</td><td>按混凝土表面灵活掌握</td></tr><tr><td>腻子层 中间漆</td><td></td><td>环氧腻子 湿固化环氧漆</td><td>用于填坑、找平 350~500</td></tr><tr><td>面漆</td><td></td><td>湿固化聚氨酯面漆</td><td>2X50</td></tr><tr><td></td><td>“</td><td>总计</td><td>450~600</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 152,
+        "chunk": "# 3.水下混凝土防护涂层配套  \n\n表3-3-38 环氧沥青漆涂层配套  \n\n\n<html><body><table><tr><td>涂层</td><td>涂料名称</td></tr><tr><td>环氧封闭漆</td><td>干膜厚度/μm 按混凝土表面灵活掌握</td></tr><tr><td>封闭层 环氧沥青漆</td><td>150</td></tr><tr><td>底-面合一</td><td>150</td></tr><tr><td>底-面合一 环氧沥青漆</td><td></td></tr><tr><td>底-面合一 环氧沥青漆 总计</td><td>150 450</td></tr></table></body></html>  \n\n表3-3-39 环氧玻璃鳞片漆涂层配套  \n\n\n<html><body><table><tr><td>涂层</td><td>涂料名称</td><td>干膜厚度/μm</td></tr><tr><td rowspan=\"3\">封闭层 底-面合一</td><td>环氧封闭漆</td><td>按混凝土表面灵活掌握</td></tr><tr><td>环氧玻璃鳞片漆</td><td>250</td></tr><tr><td>环氧玻璃鳞片漆 总计</td><td>250 500</td></tr></table></body></html>  \n\n混凝土表面涂层防护近年来受到各国的普遍使用，特别在桥梁、水工、港工结构表面上的应用，它能有效延长混凝土的使用寿命，大大减少了混凝土结构的维护费用；同时极大改善了混凝土结构外观装饰性和标志作用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 153,
+        "chunk": "# 六、混凝土结构防护涂装的特殊性和施工工艺要点",
+        "category": " Introduction"
+    },
+    {
+        "id": 154,
+        "chunk": "# 1.混凝土涂装的特殊性  \n\n混凝土表面的多孔性决定了混凝土防护涂装的特殊性，必须采用渗透性好、耐碱性优异的封闭漆进行封闭，甚至以腻子找平。而且孔洞的大小、形状、分布等也影响结构的强度，因此在封闭过程需要特别注意：一般规定， $0.3\\mathrm{mm}$ 以下的孔洞、裂缝等缺陷在表面处理后涂封闭漆，刮涂腻子即可； $0.3\\mathrm{mm}$ 以上较大的孔洞、裂缝、蜂窝及横板错位等，宜用聚合物水泥砂浆或无溶剂液态环氧腻子修补；对于较大的结构裂缝则应作除涂装范畴之外的综合处理。  \n\n涂装前混凝土表面处理方法与在什么时候开始处理比较适当也是值得思考的问题。不仅要清除表面的苔藓浮尘、浮浆、夹渣以及疏松组织外，对于海洋环境下钢筋混凝土结构表面要特别强调以高压淡水清除黏附的氯盐等腐蚀性介质。  \n\n涂漆程序的安排也关系涂装成败。一般混凝土刚刚完工时呈现高碱性，十分有利于对钢筋的保护，但是这时涂装，对于某些耐碱性差的涂料是不宜直接施涂的。要把这种碱性环境降低才能施工涂装。如果过了这段时间，在很多场合上需要增加工作台的成本与环境控制等成本，这是问题所在，因此何时施工涂装是与经济、现场环境因素、整体维修周期、使用寿命等有直接关系的。",
+        "category": " Introduction"
+    },
+    {
+        "id": 155,
+        "chunk": "# 2.主要引用标准  \n\nJTJ 275--2000   \nJT/T 695—2007   \nENV1504—2   \nENV1504—9   \nENV1504—10  \n\n海港工程混凝土结构防腐技术规范  \n混凝土桥梁表面涂层防腐技术条件  \n欧洲标准（混凝土表面保护涂层系统）  \n欧洲标准（混凝土保护涂层系统的选配与使用指引)  \n欧洲标准（混凝土保护涂层系统的施工与监管）  \nSSPC 美国标准混凝土表面涂装前的清理与涂装基本要求  \nNACENO5 高压淡水冲洗的清洁标准[相对于美国钢结构涂装标准（SPC-SP12）」  \nJB/Z350 高压无气喷涂典型工艺  \nGB1764 漆膜厚度测定法  \nGB/T5210 涂层附着力的测定法，拉开法  \nGB/T1771 色漆和清漆耐中性盐雾性能的测定（等效采用国际标准ISO7253：1984)  \nGB/T 1865 色漆和清漆人工气候老化和人工辐射暴露（等效采用国际标准ISO 11341:1994)  \nGB/T1740 漆膜耐湿热测定法  \nGB 7692 涂装作业安全规程 涂漆前处理工艺安全  \nGB6514 涂装作业安全规程涂漆工艺安全  \nGB/T15957—1995大气环境腐蚀性分类（漆膜其他物理力学性能测定执行对应的GB/T标准)",
+        "category": " References"
+    },
+    {
+        "id": 156,
+        "chunk": "# 3.施工工艺要点  \n\n(1）材料检测要求对于供应进场的涂料、喷砂使用的磨料、高压水的水质等均应按批量抽验，并按标书确定的合格指标判断可否投人使用，这是控制涂装质量的第一道把关口。  \n\n(2）涂层施工前技术准备影响混凝土结构涂装质量的几个因素如下。  \n\n$\\textcircled{1}$ 混凝土的结构及完整性；  \n\n$\\textcircled{2}$ 确保28天的混凝土养护期（硬化期)，使混凝土有足够的强度（压缩强度24000kPa以上)；$\\textcircled{3}$ 混凝土结构的渗透性；$\\textcircled{4}$ 混凝土结构的表面水分及水分含量；$\\textcircled{5}$ 混凝土结构的表面（特别裂缝处）盐分；$\\textcircled{6}$ 涂料体系的设计；$\\textcircled{7}$ 施工装备、现场检测仪表及施工队伍技术管理水平等。这些混凝土结构涂装前的主要技术准备内容详见表3-3-40。  \n\n表3-3-40 混凝土结构涂装施工前技术准备  \n\n\n<html><body><table><tr><td>要求</td><td>处理方法</td><td>检查方法</td></tr><tr><td>在20℃、相对湿度65%的条件下， 混凝土需要至少28天的硬化期</td><td>等过了规定的硬化期之后，才开始申请 进行涂装工程</td><td>请业主或混凝土承包商提供相关文 件或资料</td></tr><tr><td>混凝土表面无水浆、风化物、油污和 劣化的混凝土等</td><td>用磨料或高压水喷射的方法，除去混凝 土表面的水泥浮浆、风化物、油污和劣化的 混凝土等，然后用水淋洗，除去沉积物</td><td>通过观察和使用锋利小刀检查。对 有怀疑的区域，建议先进行小面积 试验</td></tr><tr><td>混凝土表面无风化物（白色沉积物）</td><td>出现白色沉积物的小区域，应用机械清 除或用10%盐酸溶液按以下步骤处理： ①用清洁水浸透表面； ②用10%盐酸溶液处理； ③用高压水大面积冲洗（最小150× 105Pa)</td><td>通过观察来检查。风化物是在混凝 土硬化过程中形成的水溶性盐，通过 水由混凝土内部带出表面</td></tr><tr><td>混凝土内的水含量小于4%</td><td>如果水含量大于4%，不进行涂装工程</td><td>需要专用的检测仪器</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>要求</td><td>处理方法</td><td>检查方法</td></tr><tr><td>混凝土的抗张强度最小要有： 1.2MPa=114psi（墙体和天花板）； 1.8MPa=26lpsi（地板和箱等受压 构件）</td><td>涂料说明书都会把混凝土适宜的抗张强 度要求列作必要条件</td><td>请业主或混凝土承包商提供相关文 件或资料</td></tr><tr><td>钢筋保护层厚度规定如下： 户内构件，最小10mm; 短期户外构件，最小20mm； 长期户外构件，最小30mm 如在恶劣环境下，例如，40℃、相对 湿度约60%，则钢筋保护层厚度至少 要加厚5倍</td><td>如混凝土钢筋保护层太薄，任何涂料配 套都难以起到好的保护效果。对于又陈旧 又薄的混凝土钢筋保护层，容易引起涂料覆盖层的厚度 的分层剥落</td><td>使用一种叫\"Covermeter\"或“Profo- meter”等类似的磁力仪器测量混凝土</td></tr></table></body></html>  \n\n(3）涂装施工工艺严格的表面处理是决定混凝土结构涂层寿命诸多因素中的首要因素。表面处理不但要形成一个清洁的表面，以消除混凝土施工后表面粉尘、临时砂浆、残余的脱模剂等容易使漆膜附着力降低的隐患，而且要使该表面的粗糙度适当，以增加涂层与基体间的附着力。喷砂、高压水冲刷、砂轮打磨等，仍是混凝土涂装前表面处理的最常用的工艺选择。  \n\n$\\textcircled{1}$ 表面处理  \n\na.高压淡水冲刷表面处理（检查程序）  \n\n$\\cdot$ 应清除所有杂物并安排良好的工作台、灯光照明、辅助工具等。  \n\n$\\cdot$ 去除表面油污，用乳化清洁剂进行低压淡水喷洗或软刷刷洗（具体清洗方法参见产品说明书)，并用高压淡水冲洗掉所有残余物，干燥后经检验合格方可进行下道工序作业。  \n\nb.冲砂作业的环境条件通过上述施工工艺，检查混凝土表面留下的水泥砂浆、填充腻子、风化物等附着物是否发生变化。使用冲砂方法除去所有不牢固的风化物、水泥砂浆、填充腻子等附着物，按照SSPC混凝土冲砂处理的规范，检查所有的混凝土表面达到良好牢固的混凝土表面。  \n\nc.二次高压淡水冲洗  \n\n$\\cdot$ 高压淡水冲洗，经过检查后达到要求。$\\cdot$ 涂装前混凝土表面应该有一定的粗糙度同时混凝土表面是清洁、无尘、无油等污物。$\\cdot$ 在高压淡水施工期间，要确保污水排放良好，已经清洁的表面没有受到灰尘和有害物质的污染。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 157,
+        "chunk": "# d.验收  \n\n高压淡水冲洗完工后，除去所有残渣，使用真空吸尘器或无油无水分压缩空气，吹去表面灰尘，经质量自检，并取得监理工程师认可，合格后必须在 $\\mathtt{4h}$ 内喷漆（由于混凝土可能会吸收水分，因此在涂料施工前需要检查混凝土含水量，确保含水量少于 $4\\%$ ）。  \n\n$\\textcircled{2}$ 涂层施工工艺要点除了严格的表面处理和合理的涂装设计外，必须在整个涂装施工中确保每一个环节的质量。任何一个环节的疏忽都有可能对涂层的整体质量带来严重的影响。因此所有参与施工的人员，都必须严格地执行协定的涂装工艺程序。  \n\na.通用工艺要点  \n\n$\\cdot$ 施工人员在涂装前，应认真阅读项目规范的每个系统的涂装工艺文件。了解结构构件各部位的涂料配套。学习指定的涂料产品说明书及其施工指导。  \n\n$\\cdot$ 质量不合格的涂料不能投入使用，所有涂料须报验合格后方可使用。禁止将不同品种、不同牌号和不同厂家的涂料混掺调用。  \n\n$\\cdot$ 对于将要喷涂的混凝土表面需报验并确认其清洁度、合格后方可涂装。  \n\n$\\cdot$ 确认施工现场环境和相对湿度符合所用的涂料产品说明书所规定的范围，并做好涂装环境条件的记录备查。  \n\n$\\cdot$ 检查每度涂装的准备和使用，包括涂料的型号、批号、色号、数量等；分清所用涂料的干燥类型，特别要注意双组分涂料的施工，包括固化剂和基料的混合比例、混合使用时间及固化剂的品牌随季节变化而变化的规定；正确使用稀释剂，注意随施工环境温度、湿度的变化而随时调整涂料的施工黏度，防止干喷和流挂。  \n\n·上、下度涂装工序的间隔时间，要求严格遵守涂料产品说明书上所规定的重涂间隔时间。  \n\n$\\cdot$ 双组分涂料每次调配的数量要同工作量、涂料的混合使用时间和施工人力、作业班次相适应，太多或太少均不利于施工。混合比例要准确，按涂料供应商产品说明书中规体积比（或质量比）混合加人。  \n\n$\\cdot$ 检查调整每度涂装施工设备、工具。做到配备齐全，并保证其在最简便、最佳施工条件。喷漆前做好预涂。双组分涂料所用的喷枪，在每次喷涂完工后，要及时用配套稀释剂清洗喷枪和管路，以免涂料胶化而堵塞。使用高压无气喷涂工艺参照JB/Z350执行。  \n\n·要注意涂料的存放、开启和使用前的混合、搅拌等具体要求。  \n\n·加强施工现场检测，特别是在涂装过程中要不断检测调节每度涂装的湿膜厚度，以控制干膜厚度，控制涂层系统的总干膜厚度。此外，随时目测每度涂料在成膜过程中的外观变化，注意有无漏喷、流挂、针孔、气泡、色泽不均、厚度不匀等异常情况，并在涂料供应商的技术服务人员的指导下，随时调节、及时修补，并做好记录。  \n\nb.封闭漆的重要性由于混凝土是一种多孔的表面，因此需要先施涂一度封闭层才可以施工后续保护漆，由于封闭漆需要有较好的渗透能力，所以一定要注意涂料黏度的控制。同时由于封闭漆会渗人基层有孔的地方，因此施工后有可能出现“发哑”现象，这是由于涂料渗透后出现的局部漆膜厚度不均的正常现象。注意施工后的表面不要出现发亮的表面。  \n\nc.刮涂腻子由于混凝土施工后会在表面接口位置出现凹凸不平、孔洞及其他美观上的问题，刮涂腻子是为了填平补齐。腻子需要施工在封闭漆的表面上，保证其粘接性。  \n\n③涂层施工现场管理重要性大型工程项目涂装现场需要严格的现场管理。主要内容包括人员培训、工艺与工艺纪律、质量控制、材料定额管理、吊装与运输、工具与装备、涂装环境控制等。此外，应按照GB7692、GB6514的要求，加强涂装现场文明生产、消防、卫生、安全等管理工作。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 158,
+        "chunk": "# 第五节 典型重防腐涂料与涂装",
+        "category": " Introduction"
+    },
+    {
+        "id": 159,
+        "chunk": "# 一、桥梁防腐涂料与涂装",
+        "category": " Introduction"
+    },
+    {
+        "id": 160,
+        "chunk": "# 1.中国桥梁防腐涂装的发展概况  \n\n桥梁是人类最杰出的建筑之一。从某种意义上说，桥梁已不仅仅是人类生活、交流的辅助设施，它更是人类的智慧与力量的结晶，是一件件人类创造的艺术瑰宝。  \n\n中国地域辽阔，境内河系众多，地形复杂。中国的桥梁历史甚至可以追溯到6000多年前。到了1000多年前的隋、唐、宋三代，古代桥梁发展到了巅峰时期。祖先不畏困难，依靠他们的勤劳智慧，建造了众多的古代桥梁。闻名遐迩的赵州桥、霁虹桥、洛阳桥等，都堪称现代桥梁的鼻祖。  \n\n到了近代，中国的桥梁技术却开始全面落后于世界的脚步。中国第一座现代化桥梁的出现距今仅100多年历史，而且是由外国人建造的。从钱塘江大桥算起，中国人自己设计现代桥梁的历史还不足70年；从南京长江大桥算起，中国人自行设计建造大型桥梁的历史仅30多年。但改革开放的这二十几年中，尤其是20世纪90年代以来，中国桥梁的建设又重新站到了世界前列。一座座大跨度的斜拉桥、悬索桥、钢拱桥的相继建成，使中国的桥梁建造技术取得了举世瞩目的成就。新建的江苏省苏通长江大桥和香港昂船洲大桥将以千米以上的跨径改写斜拉桥的世界纪录。中国已从桥梁大国成长为名副其实的桥梁强国。  \n\n中国桥梁的涂装发展历程，事实上也正反映了中国涂料工业的演变经历。  \n\n20世纪50年代，桥梁防护主要采用以天然原料为主的低档涂料，防护性能差，部分桥梁一年后就出现严重腐蚀。针对这一情况，铁科院先后同全国各大涂料生产厂家进行合作，开发了305锌钡白面漆、红丹防锈漆以及由金红石型钛白粉与长油度季戊四醇醇酸树脂制成的316面漆，并进行了实地涂桥试验，取得了良好的效果。  \n\n20世纪60年代，铁科院金化所与天津涂料厂再度合作，在原316面漆基础上，针对其采用钛白粉作颜料，颗粒状耐紫外线较差的特点，又开发了由片状锌铝粉作颜料并与长油度季戊四醇醇酸树脂制成的66面漆（即66灰色户外面漆或灰铝锌醇酸磁漆）。因片状锌铝粉能反射紫外线，抗褪色性及抗粉化性比以往任何灰色面漆都大有改善；同时由于片状层层相叠，水汽就不易通过，增强了防腐蚀性能。  \n\n20世纪70年代，进一步开发出当时具有国际先进水平的灰云铁醇酸磁漆，并在其原料筛选、配方调试以及漆膜耐候性等方面做了大量工作，解决了灰铝锌醇酸磁漆不能耐二氧化硫、不适于行驶蒸汽机车的桥梁上涂装使用的问题。最后于1976年5月、6月、10月以云铁醇酸面漆、调合云铁聚氨酯底漆和红丹防锈底漆，分别正式涂装于南京和武汉长江大桥。保护寿命长达5年以上，该漆成为我国后来近20年钢桥的主要涂装涂料。  \n\n20世纪80年代以来，随着交通事业的迅猛发展，各种形式大跨度桥梁制造技术被大量采用，对桥梁保护涂装也提出了新的要求。现在，环氧富锌、无机富锌、环氧云铁以及丙烯酸聚氨酯等一系列重防腐涂料已广泛在桥梁上采用。  \n\n进入21世纪以来，随着国民经济的迅猛发展和人民生活水平的不断提高，人们对于桥梁的涂装提出了更高的要求。既要求有更长的保护周期（20年、30年甚至更长)，又要求安全、健康和环保，符合最新的环境保护要求；既要美化环境，又要讲究成本和经济效益。因此，随着新原料的研究和开发，各种新型防腐涂料，如硅氧烷涂料和氟碳涂料，也开始在一些大型桥梁上逐步应用。  \n\n展望未来，随着中国经济的发展，一批更大的越江跨海工程的建设，中国桥梁将会创造更辉煌的成就，桥梁防腐涂装技术将随之发展，中华民族的伟大复兴，必将造就一代人去引领世界桥梁的未来。",
+        "category": " Introduction"
+    },
+    {
+        "id": 161,
+        "chunk": "# 2.桥梁的基本结构形式  \n\n通常，桥梁按照其用途或结构等可以有以下几种分类方式。  \n\n(1）按用途分类公路桥、铁路桥、公路铁路两用桥、人行桥以及各种用途的栈桥。(2）按结构形式分类梁桥（板梁桥、箱梁桥、桁梁桥、钢构桥)、拱桥、斜拉桥、悬  \n\n索桥等，如图3-3-44所示。  \n\n![](images/1304f8a52912f945fc678c2f262b5874692ff0c2fa8d301f8f505857f1109210.jpg)  \n图3-3-44常见桥梁结构形式示意图  \n\n(3）按支承条件分类简支梁桥、连续梁桥、悬臂锚跨梁桥、无支座桥梁等。  \n\n本节主要论述的是桥梁的防腐涂装。由于建造桥梁所使用材料的差异、防腐的材料选择及其涂装的工艺都会有很大的不同。因此本节主要按桥梁使用材料的不同进行分类，即：混凝土桥、钢桥、钢-混凝土复合桥梁（组合结构、混合结构)。",
+        "category": " Introduction"
+    },
+    {
+        "id": 162,
+        "chunk": "# 3.桥梁腐蚀的危害性  \n\n桥梁的建造，给人类的生活、交通带来了巨大的便利的同时，其本身也会受到损伤，需要进行维修，甚至报废重建。因此，对桥梁损伤的原因进行必要的研究，有利于桥梁的保养、维护，有利于延长桥梁的使用寿命。纵观桥梁失效的原因，主要是由于材料和制作不良、自然灾害、各类交通事故以及腐蚀等造成的。而各国桥梁专家统一的观念，桥梁腐蚀是桥梁损伤甚至失效的主要原因之一。  \n\n历史上，由于桥梁的腐蚀造成桥梁被迫关闭维修、甚至弃用重修新桥的事例有很多。曾是欧洲最大的混凝土悬索桥——唐卡维尔桥，由于两根主缆锈蚀严重，于1990年进行了更换，并为预防锈蚀作用带来的危害，又新增加了两根主缆。美国路易斯安那州新奥尔良的鲁林桥、阿根廷的扎拉特布拉什拉桥、委内瑞拉的马拉开波桥和中国的济南黄河大桥均进行过换索工程。英国的伦敦桥因主塔底钢梁锈蚀无法支撑大桥自重，被迫关闭重建新桥。中国的武汉长江大桥曾因铁路桥面系纵梁锈蚀而更换。2001年，中国的宜宾大桥因吊索钢丝锈蚀折断，造成桥梁断成三节。日本曾对104座悬索桥断桥事故进行了统计分析，其中19例与腐蚀有关。  \n\n桥梁因腐蚀需要进行涂装维修的事例更是不胜枚举。20世纪90年代以前，我国武汉长江大桥和南京长江大桥因涂装体系老化而产生局部腐蚀，每年都需对桥梁进行维护涂装。在美国，据美国高速公路管理局（FHWA）1998年的统计数据，美国境内洲际和国家级桥梁279543座，其中因腐蚀不合格需要维修的桥梁68466座，腐蚀率占 $24.5\\%$ ；城镇间桥梁309792座，腐蚀率达 $35.4\\%$ 。目前美国每个州每年都要拿出数千万美元用于桥梁防腐蚀涂装维修。",
+        "category": " Introduction"
+    },
+    {
+        "id": 163,
+        "chunk": "# 4.桥梁防腐涂装  \n\n（1）桥梁腐蚀环境分析  \n\n$\\textcircled{1}$ 大气腐蚀桥梁一般横跨江河或海湾，腐蚀环境非常复杂。我国地域辽阔，各桥梁所在的地理位置也千差万别。而桥梁的腐蚀速率和状况又与其所处的环境息息相关。因此，在设计桥梁防腐涂装前，首先对腐蚀环境进行分析是非常必要，也是至关重要的。",
+        "category": " Introduction"
+    },
+    {
+        "id": 164,
+        "chunk": "# a.中国的气候环境特点  \n\n·雨量分布中国气候受到洲际气象和特殊地理环境的影响很大，如图3-3-45所示，处于北上的太平洋和印度洋暖流及南下的西北冷空气交互作用之间，加之，西北角的天山山脉和紧连的祁连山山脉，西南边缘的喜马拉雅山山脉及青藏高原，均在海拔 $3000\\mathrm{m}$ 左右或以上，秋、冬、春季，印度洋暖流北上遇到喜马拉雅山和青藏高原的阻挡，顺着长江向东，遇到南下的冷空气，往往在长江流域及南方形成雨雪天气。北上的太平洋暖流，夏季被阻于东北、华北，一年中多半的雨水降在夏季；冬季被阻于江南和华南，导致一年四季都有雨水。然而在南疆、西北、直至内蒙，比较干燥少雨。表3-3-41为全国雨量及气温分布。  \n\n![](images/de9da53fca8e6f154dbf05120164a066b78bb00e72ddb27b47322911fe11104a.jpg)  \n图3-3-45中国气候说明简图  \n\n表3-3-41 雨量分布及其他  \n\n\n<html><body><table><tr><td>地区</td><td>年均降雨量/mm</td><td>年均湿度/%</td><td>露霜</td><td>气温范围/℃</td></tr><tr><td>西北、南疆、青藏、内蒙等地区</td><td>100~300</td><td><60</td><td></td><td>35~-30</td></tr><tr><td>华北、东北、西安至山东</td><td>500~800</td><td>60~80</td><td>一</td><td>35~-40</td></tr><tr><td>四川、重庆至上海长江流域、云南、贵州</td><td>1000~1200</td><td>>75</td><td>易结露、结霜</td><td>36～ -20</td></tr><tr><td>广东、广西珠江流域</td><td>1500~1700</td><td>>75</td><td>易结露</td><td>36～-5</td></tr><tr><td>海南、香港地区</td><td>2000</td><td>>750</td><td>易结露</td><td>35~0</td></tr></table></body></html>  \n\n根据各地的气温和湿度情况，通常将我国的气候环境分为以下五类。  \n\n热带湿热区：雷州半岛、海南岛和台湾南部。  \n\n亚热带湿热区：秦岭以南、长江流域、四川、珠江流域、台湾北部和福建。  \n\n亚热带干燥区：新疆天山以南、戈壁沙漠。  \n\n温带温和区：秦岭以北、内蒙南部、华北、东北南部。  \n\n寒带干燥区：内蒙北部、黑龙江省。  \n\n$\\cdot$ 酸雨分布根据中国环境监测报告，酸雨最严重地区是重庆！ $(\\mathrm{pH}\\approx4.4)$ ，其次是贵州、云南东部、广西、直至海南岛，再次为长江中下游。究其原因，是由于当地的燃料产生$\\mathrm{CO}_{2}$ ， ${\\bf S}{\\bar{\\bf O}}_{\\bar{z}}$ 较多，加之西北及北方产生的酸性气体随气流南下，遇到潮湿空气而变成酸雨。  \n\n$\\cdot$ 盐分分布空气中盐分最严重地区是近海岸 $100\\mathbf{m}$ 的地带，向内陆逐步减弱。  \n\nb.大气腐蚀环境的分类桥梁的腐蚀不仅仅受到温度和湿度的影响，更多的与大气环境中腐蚀物质、如氯离子、含硫化合物、氮氧化合物等有关。这些腐蚀物质是由于城市排放污染物，如汽车尾气或锅炉排放，工业排放物以及海洋大气直接或间接产生的。因此对钢结构桥梁所处的大气腐蚀环境进行综合分析，更接近于应用实际。有关大气腐蚀环境的分类、描述以及相关的国家和国际标准可以参考本章第一节中的“大气腐蚀环境分类”相关内容，这里不再赘述。  \n\n$\\textcircled{2}$ 水介质腐蚀大桥是横跨江河湖海的，桥梁的墩梁等不可避免地会处于水的腐蚀环境中。根据水的成分不同，水介质腐蚀通常分为淡水腐蚀和海水腐蚀。  \n\na.淡水腐蚀淡水的含盐量少，一般呈中性，如江河湖泊的水。一般情况下，淡水的腐蚀性较弱。淡水中的腐蚀主要是吸氧腐蚀。但是随着现代工业排放物对淡水的污染，会加速腐蚀的进行。这些外界因素对淡水腐蚀的影响是不可忽视的。  \n\nb.海水腐蚀海水是一种含多种盐类的电解质溶液，以 $3.2\\%\\sim3.75\\%$ 的 $\\mathrm{{NaCl}}$ 为主，$\\mathfrak{p H}$ 在 $7.5\\sim8.6$ ，溶解氧在 $\\mathrm{5\\sim10mg/kg}$ 范围内。海水腐蚀通常按物体与海水接触情况不同分为飞溅区、潮差区、全浸区和海泥区。其中飞溅区由于受风浪影响，海浪飞溅对物体表面频繁冲击、干湿交替，是防腐要求最高的区域。  \n\n有关海水腐蚀的详细内容，请参考本章第一节中的“海水腐蚀”相关内容。  \n\n$\\textcircled{3}$ 土壤腐蚀桥梁的支撑梁柱必然要立足于土壤之中，土壤对钢铁或混凝土的腐蚀直接影响着大桥的安全。土壤是由气相、液相和固相所构成的一个复杂系统，其中还生存着很多土壤微生物。影响土壤腐蚀的因素主要有：电阻率、含氧量、盐分、含水量、pH、温度和微生物等。  \n\n有关土壤腐蚀的详细内容，请参考本章第一节中的“土壤腐蚀”相关内容。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 165,
+        "chunk": "# （2）桥梁防腐涂装设计  \n\n$\\textcircled{1}$ 基本原则前面提到了桥梁所处的环境不同，其所受到的腐蚀因素也不尽相同。因此，桥梁涂装的防腐涂层配套必须遵循“量身定做”的设计理念。考虑到桥梁涂装中的各种因素，通常总结为以下四项涂装设计的基本原则。  \n\na.充分考虑桥梁所处的腐蚀环境如前节中所述，根据桥梁所处的大气、化学腐蚀环境的差异性，可以参照ISO12944-2：1999《钢结构保护涂层-环境的分类》腐蚀性环境分类标准和GB/T15957—1995《大气环境腐蚀性分类》，对桥梁所处的大气腐蚀环境进行分级。  \n\nb.充分考虑桥梁的结构与工况条件桥梁结构、形状与工况条件的不同，对表面处理和涂装作业的要求有很大的不同，是涂装设计量身定做的重要依据。这些因素主要有：  \n\n$\\cdot$ 钢结构还是混凝土结构；  \n$\\cdot$ 桥梁结构类型一一钢箱梁、钢板梁、钢桁梁、钢管拱；  \n$\\cdot$ 悬索桥、斜拉桥、拱桥中的缆索、风嘴的特殊性；  \n$\\cdot$ 桥梁结构中各部位工况及其小环境特点；  \n$\\cdot$ 桥梁外观与色彩设计要求；  \n$\\cdot$ 桥梁制造流程与涂装作业的衔接。  \n\nc.充分考虑施工工艺水平的高低涂料的防护功能有阴极保护、缓蚀作用、屏蔽作用三种作用。施工工艺直接影响底材的表面处理、涂料的成膜质量，进而影响涂料防护功能的发挥。例如，富锌漆涂在表面处理达不到 $\\mathsf{S a2.5}$ 等级的钢表面，无法达到满意的阴极保护效果。因此，现代桥梁涂装特别强调：底材的表面处理、选用优质的重防腐涂料、正确设计涂装的涂料配套、严格控制现场的施工质量、加强运营过程中的维护与保养，从而确保及延长桥梁的使用寿命。  \n\nd.充分考虑投资限制性因素涂装设计与任何设计一样，必须贯彻“全寿命经济分析法”（LCCA）设计思想（详见本章第三节叙述)；控制投资在允许的范围内，才是可行的。  \n\n②防腐涂层的使用寿命根据桥梁防腐预期寿命，选用优质的重防腐涂料体系。一般来说，新建大型桥梁在涂装施工质量达标、建成通车后对涂料涂层进行正常的维护及保养的前提下，目前国际上一般认为大型新建钢结构桥梁防护涂层的有效使用寿命可达到 $15\\sim20$ 年，国内有一部分大型新建桥梁防护涂层的设计有效使用寿命要求达到 $25\\sim30$ 年。  \n\n$\\textcircled{3}$ 防腐涂装设计的内容防腐涂装设计书主要应包含以下内容：a，涂层设计寿命；b.腐蚀环境分析；c.引用标准；d.配套体系；e.产品技术指标；f．涂装工艺方案；g．质量检验与验收。  \n\n$\\textcircled{4}$ 桥梁涂层色彩设计桥梁发展到今天，已经不再仅仅是传统意义上作为便利交通的一种工具了。很多的时候，桥梁代表了一个城市的象征、反映了一个城市的特色。润扬长江公路大桥的钢箱梁采用了金属铝色，横跨于万里长江之上，宛若银河落人间；汕头磐石大桥的斜拉索巧妙地选用了橙黄色，远远望去，好似万道霞光倾洒在绿波之上。云南小湾大桥采用冰灰色与周围绿水青山大自然色彩协调和谐，增添了旅游观赏性。所以桥梁成了城市或地区的一道道靓丽的风景线。因此，业主们在要求桥梁防腐蚀性能的同时，也越来越关注桥梁的外观、尤其是防腐涂层的颜色选择。  \n\n但是，色彩的设计也并非易事。首先，人类对于颜色的感觉非常复杂。某些颜色会使人宁静、舒畅；相反，有些颜色则使人烦躁、紧张。对于行车在桥梁上的人来说，颜色也关系到安全。其次，颜色对于产品的成本和耐性也影响巨大。某些颜色，如鲜红或鲜黄，若选用单偶氮类颜料，成本不高但耐候性差，不能达到长效防护的目标；而选用其他颜料，则成本可能会上升很多。因此，色彩的设计已经成为桥梁防护涂装设计中必不可少的一项内容。设计者们不但要考虑业主的要求，更应考虑安全、成本和耐候性方面的问题。  \n\n总之，在色彩设计上应遵循工艺美学、涂膜性能、技术经济及周围环境等多方面相协调与和谐的原则。",
+        "category": " Introduction"
+    },
+    {
+        "id": 166,
+        "chunk": "# 5.桥梁涂装标准  \n\n(1）基础性标准前面提到，桥梁的涂装设计要充分考虑到大气腐蚀环境的影响。ISO12944-2：1999《钢结构保护涂层-环境的分类》和GB/T15957—1995《大气环境腐蚀性分类》是目前涂装设计中采用最多，也是最实用的。具体分类方法可以参考本章第一节中的“大气腐蚀环境分类”相关内容。  \n\n(2）防腐涂料检测方法标准防腐涂料的检测可以分为两类：涂料物化性能指标的检测和涂料的漆膜耐性的检测。前者主要用于现场对涂料质量稳定性的评估，而后者则用来评估涂料是否符合涂装设计的要求。常用的检测方法标准如下：  \n\nGB/T 1727 漆膜一般制备方法  \nGB/T 1728 漆膜、腻子膜干燥时间测定法  \nGB/T 1729 漆膜颜色及外观测定法  \nGB/T 1731 漆膜柔韧性测定法  \nGB/T 1732 漆膜耐冲击测定法  \nGB/T6750 色漆和清漆密度的测定  \nGB/T 6751 色漆和清漆挥发物和不挥发物的测定  \nGB/T 6753.1 涂料研磨细度的测定  \nGB/T 9269 建筑涂料黏度的测定斯托默黏度测定法  \nGB/T 6742 漆膜弯曲试验（圆柱轴）  \nGB/T 5210 涂层附着力的测定法拉开法  \nGB/T9286 色漆和清漆漆膜的划格试验  \nGB/T1733 漆膜耐水性测定法  \nGB/T 1763 漆膜耐化学试剂性测定法  \nGB/T 1771 色漆和清漆耐中性盐雾性能的测定（等效采用ISO7253：1984）  \nGB/T1865 色漆和清漆人工气候老化和人工辐射曝露（等效采用ISO11341：1994）  \nGB/T 1740 漆膜耐湿热测定法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 167,
+        "chunk": "# （3）桥梁防腐涂装行业标准  \n\n$\\textcircled{1}$ 铁道行业标准目前我国铁道行业就钢桥防腐保护制定了4个行业标准。其中标准TB/T2486—1994《铁路钢梁涂膜劣化评定》规定了铁路钢梁涂膜劣化类型、劣化等级和评定方法，适用于评定钢梁涂膜的状态、质量以及铁路钢梁劣化涂膜涂装分类、桥梁其他钢铁结构；标准TB/T1527—2004《铁路钢梁保护涂装》规定了铁路钢桥保护涂装技术要求、试验方法和检验规则，适用于钢桥的初始涂装、钢桥涂膜劣化后的重新涂装和维护性涂装；标准TB/T2772—1997《铁路钢桥用防锈底漆供货技术条件》和TB/T2723—1997《铁路钢桥用面漆、中间漆供货技术条件》分别规定了铁路钢桥各涂装体系防锈底漆、中间层用漆、面漆的分类、技术要求、试验方法、检验规则及包装、标志、运输和贮存，适用于新建钢梁涂装、运营中钢梁重新涂装及维护涂装和其他钢结构涂装使用的防锈底漆、中间漆、面漆。  \n\n②化工行业标准标准HG/T3656—1999《钢结构桥梁漆》按使用年限，将钢桥涂装产品分为普通型和长效型两类。分别对这两类产品的防锈底漆、中间层用漆、面漆的技术要求、试验方法、检验规则及包装、标志、运输和贮存作了规定。同时在附录中列举了两类产品的常用品种，并介绍了几个实际应用配套体系。  \n\n标准HG/T3668—2000《富锌底漆》对近年来在桥梁重防腐涂装中广泛应用的富锌底漆进行了分类：1型无机富锌底漆（不挥发分中锌含量 $\\geq80\\%$ ）和2型有机富锌底漆（不挥发分中锌含量 $\\geq70\\%)\\bullet$ 。对此两类产品分别规定了技术要求、试验方法、检验规则及包装、标志、运输和贮存。标准中还详细介绍了富锌底漆一项重要指标：不挥发分中的金属锌含量的检测方法。目前，国内一般都依据此标准来检测锌含量，实践表明，由于金属锌在取样、调配测试过程中可能因部分被氧化成氧化锌及其他原因，锌含量检测结果往往偏低。  \n\n$\\textcircled{3}$ 交通行业标准  \n\nJT/T 722—2008 公路桥梁钢结构涂装技术条件JT/T 694—2007 混凝土桥梁表面涂层防腐技术条件JT/T695一2007悬索桥主缆防腐涂装技术条件  \n\n这是三份新标准。其中JT/T722—2008在总结了我国近十年来大型钢桥防腐涂装经验的基础上，按照ISO12944标准，对钢桥腐蚀环境、防腐寿命做出分级规定，并以此推荐了相应的涂层配套系统及其涂料、涂层的技术要求、试验方法、验收条件及涂装施工工艺要求等；JT/T694—2007标准，在对混凝土桥梁做出腐蚀环境与腐蚀因素分析的基础上，设计规定了混凝土桥梁在各种腐蚀环境条件下表面涂层配套体系及其性能指标，并对涂装施工、验收、安全、卫生及环境保护等做出具体的规定；JT/T695—2007标准适用于悬索桥主缆系统的防腐涂装。除规定了有关术语和定义外，着重设计规定了主缆系统涂装材料配套体系、施工工艺、相关材料的性能指标以及验收、安全、卫生、环保等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 168,
+        "chunk": "# 6.桥梁防腐涂装配套体系  \n\n（1）配套原则在设计桥梁防腐涂装配套时，首先应充分考虑配套的可行性。换而言之，也就是配套涂料之间的相容性。作为通用原则，涂层之间的配套应遵循以下条件。  \n\n$\\textcircled{1}$ 后继涂层应具有更好的柔韧性或较小的收缩率因为内应力的影响，如果不能满足条件，通常漆膜会发生开裂等缺陷。化学固化的产品通常较物理固化的产品柔韧性差，收缩率也大。因此，一般不会将化学固化的产品作为物理固化的产品后道涂层。  \n\n$\\textcircled{2}$ 后继涂层应含有较弱的溶剂如果后道涂层的溶剂较强，漆膜可能会产生咬底、渗色等病，这种现象在醇酸产品中尤为明显。  \n\n（2）钢结构桥梁的配套体系$\\textcircled{1}$ 钢结构（钢箱梁）外表面  \n\na．配套一红丹防锈底漆（2道 $80\\mu\\mathrm{m}$ 产 $+$ 灰云铁醇酸面漆（3道 $120\\mu\\mathrm{m},$ 。  \n\n1976年，红丹防锈底漆和醇酸云铁面漆开始在南京和武汉长江大桥上得到应用。但是，一方面由于油性醇酸是通过与氧气反应固化成膜，如果膜厚过高，不利于氧气的渗透与固化，因此，醇酸涂料必须多道喷涂以达到重防腐的厚膜设计要求；其次，从环保和职业安全的要求考虑，红丹底漆因含铅，毒性大，已渐渐地不再为世界各国所采用。另一方面，上述涂装系统的耐久性和维护涂装的经济性则显得不尽如人意。因此，目前该配套已基本不再为桥梁防腐配套设计者所考虑。  \n\nb.配套二环氧富锌底漆（1道 $80\\mu\\mathrm{m}$ $+$ 环氧云铁中间漆（1道 $100\\mu\\mathrm{m}$ )十氯化橡胶面漆（2道 $80\\mu\\mathrm{m},$  \n\n自20世纪90年代初开始，该配套开始应用于大型钢桥上，如上海的南浦和徐浦两座大桥均选用了该配套。  \n\n但是，氯化橡胶面漆的耐候性还是不强，二三年后漆膜开始出现粉化，而且因为含氯，保色性也不是最好，有黄变的趋势。对于大型桥梁，已逐步放弃了该配套。  \n\nc.配套三环氧富锌底漆（1道 $80\\upmu\\mathrm{m})+$ 环氧云铁中间漆（1道 $150\\mu\\mathrm{m}$ )+脂肪族聚氨酯面漆（2道 $80\\upmu\\mathrm{m}$ 。  \n\n该配套适用于处于一般至较严重的腐蚀环境下的桥梁，较为经济、实用。世界各国都有很多著名的桥梁采用上述配套，包括我国在建的黄埔珠江大桥和香港昂船洲大桥就采用此配套。一般防护寿命可达 $10\\sim15$ 年。  \n\nd.配套四无机富锌底漆（1道 $75\\mu\\mathrm{m}\\dot{}$ )十环氧封闭漆（1道 $25\\mu\\mathrm{{m}}$ )十环氧云铁中间漆(1道 $150\\mu\\mathrm{m})+$ 脂肪族聚氨酯面漆（2道 $80\\mu\\mathrm{m}\\mathrm{.}$ 。  \n\n无机富锌底漆配方设计可以超过CPVC（临界颜料体积浓度)，因此与环氧富锌底漆相比，拥有更高的锌含量，从而确保更优越的阴极保护性能。同时，其成分更可与钢材表面发生反应，从而保证优异的附着能力。  \n\n但是，无机富锌漆膜有多孔的特性，尤其是刚施工的漆膜。这会带来一系列的不利。虽然经过几个月的室外固化，其孔隙会逐渐被由于受大气中二氧化碳和湿气作用形成的锌盐填充而变得致密，但是桥梁的建造是不允许在涂下道漆前进行 $1\\sim2$ 个月的固化的，这就会造成后续涂层的起泡。为此，专门设计了用于无机富锌表面的环氧封闭漆则有助于减少其后续涂层起泡的风险。通常，环氧封闭漆选用较小分子的树脂，使其本身具有良好的渗透性。同时通过与一定比例的稀释剂混合使用，达到最佳的流动性和渗透性，填没无机富锌表面的孔隙，从而避免后续涂层的起泡。  \n\n此配套自20世纪90年代中期开始，广泛应用于我国大型桥梁的建设中。实践也证明了它确实拥有优异的防腐性能，堪称迄今为止桥梁最为经典的防腐配套。新建的世界第一的斜拉桥——苏通长江公路大桥就采用此配套。防护寿命可达15年以上。  \n\ne.配套五无机富锌底漆（1道 $75\\mu\\mathrm{m}$ )十环氧封闭漆（1道 $25\\mu\\mathrm{m})+$ 环氧云铁中间漆(1道 $150\\upmu\\mathrm{m}.$ $+$ 氟碳面漆或聚硅氧烷面漆（2道 $80\\mu\\mathrm{m}$ 。  \n\n为满足人们对大型桥梁的涂装有更长的防护周期的要求，近年来各国的涂料供应商都在抓紧研制、开发聚氨酯面漆的更新替代产品。氟碳面漆和聚硅氧烷面漆的出现，使桥梁涂装的防护周期延长，大大增加面漆得耐候性。桥梁防腐涂装达到了前所未有的快速发展。  \n\n氟碳面漆和聚硅氧烷面漆都是应用成膜树脂的分子键能高、不易断裂的设计原理，从而保证了漆膜具有更好的耐候性。在本章第一节中已有较详细的介绍。目前，这两种配套均已  \n\n开始在国内新建桥梁上得到应用。  \n\n$\\textcircled{2}$ 钢箱梁内表面  \n\na.配套一（配备抽湿设备）厚浆型环氧（云铁）漆（1道 $150\\mu\\mathrm{m})$ 。  \n\nb.配套二（不配备抽湿设备）环氧富锌底漆（1道 $80\\mu\\mathrm{m}$ )十厚浆型环氧（云铁）漆(1道 $150\\mu\\mathrm{m})$  \n\nc.配套三（不配备抽湿设备）环氧富锌底漆（1道 $80\\mu\\mathrm{m}$ )十环氧煤焦油沥青漆（1道$125\\mu\\mathrm{m})$  \n\nd.配套四 无机富锌底漆（1道 $80\\mu\\mathrm{m}\\mathrm{i}$ 。  \n\n考虑到箱梁内部相对比较密封的环境，采用低VOC（挥发性有机物含量）的高固体分（厚浆型）环氧漆更有利于健康和安全。  \n\n虽然云铁漆具有更好的屏蔽性，但由于云铁原料本身颜色较深，因此漆膜的颜色较暗。应用于箱梁内部，不利于检查、维护。因此现在有些桥梁设计者更倾向于选用浅色的环氧厚浆漆。  \n\n桥梁架设、拼接完成后，桥面需要铺设沥青。也就是说箱内顶桥面一侧对于瞬间高温（通常在 $130^{\\circ}C$ ）需要有足够的抵抗力。厚浆型环氧漆的最高瞬间耐温可以达到 $140{\\sim}150^{\\circ}C$ 。  \n\n煤焦油沥青成本低，且具有优良的耐水性。但因沥青的存在，漆膜颜色深，不利于检查、维修；而且煤焦油沥青含有致癌物质，在欧美国家已禁止使用，因此一般较少采用。  \n\n至于无机富锌底漆，因其对于钢材的表面处理要求高，而这在箱梁内比较难以操作；同时漆膜颜色偏暗，不利于检查、维修，因此一般较少采用。  \n\n$\\textcircled{3}$ 桥面  \n\na．配套一 环氧富锌底漆（1道 $80\\mu\\mathrm{m}\\mathrm{,}$ 。  \n\nb.配套二 无机富锌底漆（1道 $75\\mu\\mathrm{m}$ 。  \n\n环氧富锌底漆和无机富锌底漆均具有优良的防腐性能，并其漆膜硬度、耐磨性能非常优异。同时，经实践证明，两者与桥面的铺装材料之间的结合也非常良好。  \n\n尚须指出的是，电弧喷镀锌（铝）及其合金新工艺在桥梁防腐涂装工程也有应用，取代富锌底漆。从理论上讲其电化学阴极保护性能更佳，但施工工艺要求更加严格，特别是表面处理（喷砂至 $\\mathrm{Sa3}$ 级）和锌（铝）材质控制。参照执行国家标准GB/T9793—1997《金属和其他无机覆盖层热喷涂锌、铝及其合金》（相当于ISO2063：1991)，并合理选择封闭漆及其配套中间漆、面漆。显然，金属热喷涂也是一种高耗能工艺，对于大型钢结构件应谨慎选用。  \n\n（3）混凝土桥梁的配套体系  \n\n$\\textcircled{1}$ 配套一环氧封闭漆 (按混凝土表面状况灵活掌握) $+$ 环氧腻子 (用于填坑找平) $+$ 环氧厚浆漆（1道 $100\\mu\\mathrm{m})+$ 脂肪族聚氨酯面漆（2道 $80\\mu\\mathrm{m}.$ 。  \n\n由于混凝土是一种多孔的表面，因此需要施工一度封闭层才可以涂装保护漆，在涂装涂料前用来渗透、封闭、清洁固化后的混凝土结构表面，靠毛细孔的表面张力吸人深约数毫米的混凝土表层中，可显著降低混凝土的吸水性和氯化物的渗人。环氧封闭漆采用一种低黏度的双组分环氧清漆，有着极好的渗透性。  \n\n由于混凝土施工后会出现表面接口位置出现不平、砂孔等现象或者其他美观上的问题，就需要通过施工腻子来解决。考虑腻子的高PVC（颜料体积浓度）的特性，一方面通过环氧树脂增加其内聚力；另一方面，可根据施工中各种不同的需要，添加一定大小和数量的砂粒。同时，为了保证腻子和混凝土的粘接性，腻子必须是施工在封闭漆的表面上。  \n\n$\\textcircled{2}$ 配套二 (防碳化配套）环氧封闭漆 (按混凝土表面状况灵活掌握) $+$ 环氧腻子（用于填坑找平) $+$ 丙烯酸封闭漆（1道 $50\\mu\\mathrm{m}^{\\prime}$ )十丙烯酸面漆（2道 $\\times50\\mu\\mathrm{m}.$ 。  \n\n丙烯酸封闭漆是一种改良的丙烯酸涂料，具有良好的渗透性能及优异的耐粘污能力，能使混凝土表面具有抗碳化作用。  \n\n丙烯酸面漆具备极佳的保色性能，而且兼备防水及防碳化作用。  \n\n防碳化保护涂料能有效发挥保护作用，阻止混凝土的碳化。此配套体系具有“呼吸作用”，可以让混凝土内部的水以分子的形态透过漆膜，减少了涂料系统的内部渗透压，又防止了水以液体的形态进人混凝土内部加速碳化作用。  \n\n$\\textcircled{3}$ 配套三（浪溅区的配套）环氧封闭漆（按混凝土表面状况灵活掌握) $+$ 环氧腻子(用于填坑找平) $+$ 环氧厚膜漆（1道 $350\\mu\\mathrm{m}\\dot{}$ 。  \n\n浪溅区（干湿交替）受潮水涨退的时间影响，工作时间短，操作过程环境恶劣，因此需要采用比较特殊的配套产品。目前国内外较多采用的是特制的超强度环氧厚膜漆。这种采用特种胺加成物固化技术的环氧涂料，可形成坚韧的漆膜，具有突出的耐磨耐碰撞性能。同时其兼具快干性和耐水性。在常温的环境下，施工几小时后浸泡在水中，漆膜具有较强的抗压能力；而且漆膜可在水中继续固化。  \n\n(4）国内主要大型桥梁涂装配套体系简介表3-3-42是一些国内主要大型桥梁涂装配套体系，可作为读者阅读本节内容时的参考。  \n\n表3-3-42国内桥梁防腐涂装配套体系  \n\n\n<html><body><table><tr><td>桥梁名称</td><td>部位</td><td>品种</td><td>油漆名称</td><td>涂装道数</td><td>漆膜厚度/μm</td></tr><tr><td rowspan=\"2\">南京长江大桥 (1968年)</td><td>钢桁梁</td><td>底漆</td><td>醇酸红丹防锈漆</td><td></td><td></td></tr><tr><td></td><td>面漆</td><td>66灰色铝锌户外面漆</td><td></td><td></td></tr><tr><td>南京长江大桥 武汉长江大桥 (1976年)</td><td>钢桁梁</td><td>底漆 面漆</td><td>云铁酚醛底漆 云铁醇酸钢桥面漆</td><td>2 2</td><td>总膜厚200～300</td></tr><tr><td rowspan=\"4\">上海南浦大桥 (1991年) 上海杨浦大桥 (1993年)</td><td rowspan=\"2\">钢箱梁外表面</td><td>底漆</td><td>环氧富锌底漆</td><td>1</td><td>80</td></tr><tr><td>中涂漆</td><td>环氧云铁中间漆</td><td>2</td><td>100</td></tr><tr><td rowspan=\"2\"></td><td>面漆</td><td>氯化橡胶厚膜型面漆</td><td>2</td><td>45</td></tr><tr><td>底漆</td><td>环氧富锌底漆</td><td></td><td></td></tr><tr><td rowspan=\"4\">广东虎门大桥 （1997年）</td><td rowspan=\"2\">钢箱梁内表面</td><td>中涂漆</td><td>环氧云铁中间漆</td><td></td><td></td></tr><tr><td>面漆</td><td>环氧煤沥青涂料</td><td></td><td></td></tr><tr><td rowspan=\"2\">钢箱梁外表面</td><td>底漆</td><td>无机硅酸富锌底漆</td><td>1</td><td>75</td></tr><tr><td>封闭漆</td><td>环氧铁红封闭漆</td><td>1 2</td><td>25</td></tr><tr><td rowspan=\"4\">厦门海沧大桥 （1999年）</td><td rowspan=\"2\"></td><td>中间漆 面漆</td><td>环氧云铁中间漆 丙烯酸聚氨酯面漆</td><td>2</td><td>80 80</td></tr><tr><td>底漆</td><td>无机硅酸富锌底漆</td><td>1</td><td>80</td></tr><tr><td rowspan=\"3\">钢箱梁外表面</td><td>封闭漆</td><td>环氧封闭漆</td><td>1</td><td>25</td></tr><tr><td>中间漆</td><td>环氧云铁中间漆</td><td>2</td><td>80</td></tr><tr><td>面漆</td><td>脂肪族聚氨酯面漆</td><td>2</td><td>80</td></tr><tr><td rowspan=\"2\">芜湖长江大桥 (2000年)</td><td rowspan=\"2\">钢桁梁</td><td>底漆</td><td>环氧富锌底漆</td><td>2</td><td>80</td></tr><tr><td>中间漆</td><td>环氧云铁中间漆</td><td>1</td><td>50</td></tr><tr><td rowspan=\"5\">武汉军山长江大桥 (2000年）</td><td rowspan=\"2\"></td><td>面漆</td><td>灰铝粉醇酸面漆</td><td>2</td><td>80</td></tr><tr><td>喷铝</td><td>电弧喷铝</td><td>1</td><td>≥180</td></tr><tr><td rowspan=\"3\">钢箱梁外表面</td><td>封闭漆</td><td>环氧云铁封闭漆</td><td>1</td><td>20</td></tr><tr><td>中间漆</td><td>环氧云铁中涂漆</td><td>1</td><td>60</td></tr><tr><td>面漆</td><td>脂肪族聚氨酯面漆</td><td>2</td><td>60</td></tr><tr><td>钢箱梁内表面</td><td>防锈漆 底漆</td><td>厚浆型环氧耐磨漆</td><td></td><td>1</td><td>125</td></tr><tr><td rowspan=\"2\">风嘴内表面</td><td></td><td></td><td>无机硅酸富锌底漆</td><td>1</td><td>80</td></tr><tr><td>面漆</td><td>封闭漆</td><td>环氧封闭漆 环氧面漆</td><td>1 1</td><td>25 125</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>桥梁名称</td><td>部位</td><td>品种</td><td>油漆名称</td><td>涂装道数</td><td>漆膜厚度/μm</td></tr><tr><td rowspan=\"3\">重庆鹅公岩大桥 (2000年）</td><td></td><td>底漆</td><td>无机硅酸富锌底漆</td><td>1</td><td>70</td></tr><tr><td>钢箱梁外表面</td><td>封闭漆</td><td>环氧云铁封闭漆</td><td>1</td><td>25</td></tr><tr><td></td><td>中间漆</td><td>环氧云铁中间漆</td><td>1</td><td>80</td></tr><tr><td rowspan=\"6\">南京长江二桥 (2001年）</td><td></td><td>面漆</td><td>脂肪族聚氨酯面漆</td><td>2</td><td>80</td></tr><tr><td></td><td>底漆</td><td>无机硅酸富锌底漆</td><td>1</td><td>80</td></tr><tr><td>钢箱梁外表面</td><td>封闭漆</td><td>环氧封闭漆</td><td>1</td><td>30</td></tr><tr><td></td><td>中间漆</td><td>环氧云铁中间漆</td><td>2</td><td>80</td></tr><tr><td></td><td>面漆</td><td>脂肪族聚氨酯面漆</td><td>2</td><td>80</td></tr><tr><td>钢箱梁内表面</td><td>底漆 面漆</td><td>环氧云铁防锈漆</td><td>1</td><td>50</td></tr><tr><td rowspan=\"4\">宜昌长江大桥 (2001年)</td><td></td><td>底漆</td><td>环氧玻璃鳞片涂料 无机硅酸富锌底漆</td><td>1 1</td><td>50</td></tr><tr><td>钢箱梁</td><td>封闭漆</td><td>环氧封闭漆</td><td>1</td><td>80</td></tr><tr><td></td><td>中间漆</td><td>环氧云铁中间漆</td><td></td><td>25</td></tr><tr><td></td><td>面漆</td><td></td><td>2</td><td>80</td></tr><tr><td rowspan=\"6\">舟山桃天门大桥 (2004年）</td><td></td><td>喷铝层</td><td>脂肪族聚氨酯面漆 电弧喷铝</td><td>2 1</td><td>80 200</td></tr><tr><td>钢箱梁外表面</td><td>封闭漆</td><td>环氧云铁封闭漆</td><td></td><td></td></tr><tr><td></td><td>中间漆</td><td></td><td>1</td><td></td></tr><tr><td></td><td>面漆</td><td>环氧云铁中间漆</td><td>1</td><td>60</td></tr><tr><td></td><td>封闭漆</td><td>脂肪族聚氨酯面漆</td><td>2</td><td>80</td></tr><tr><td>混凝土主塔</td><td>中间漆</td><td>环氧封闭漆 环氧云铁中间漆</td><td></td><td></td></tr><tr><td rowspan=\"6\">润扬长江公路大桥 (2004年）</td><td></td><td>面漆</td><td>脂肪族聚氨酯面漆</td><td></td><td></td></tr><tr><td></td><td>底漆</td><td>无机硅酸富锌底漆</td><td>1</td><td>75</td></tr><tr><td>钢箱梁外表面</td><td>封闭漆</td><td>环氧云铁封闭漆</td><td>1</td><td>25</td></tr><tr><td></td><td>中间漆</td><td>环氧云铁中间漆</td><td>1</td><td>150</td></tr><tr><td></td><td>面漆</td><td>脂肪族聚氨酯面漆</td><td>2</td><td>80</td></tr><tr><td>钢箱梁内表面</td><td>底漆</td><td>磷酸锌环氧底漆</td><td>1</td><td>50</td></tr><tr><td></td><td></td><td>面漆</td><td>厚浆型环氧面漆</td><td>1</td><td>70</td></tr><tr><td rowspan=\"6\"></td><td>桥面</td><td>底漆</td><td>环氧富锌底漆</td><td>1</td><td>80</td></tr><tr><td></td><td>底漆</td><td>无机硅酸富锌底漆</td><td>1</td><td>75</td></tr><tr><td>钢箱梁外表面</td><td>封闭漆</td><td>环氧云铁封闭漆</td><td>1</td><td>25</td></tr><tr><td></td><td>中间漆</td><td>环氧云铁中间漆</td><td>1</td><td>150</td></tr><tr><td></td><td>面漆</td><td>脂肪族聚氨酯面漆</td><td>2</td><td>80</td></tr><tr><td>钢箱梁内表面</td><td>底漆</td><td>厚浆型环氧漆</td><td>1</td><td>70</td></tr><tr><td rowspan=\"2\">香港昂船洲大桥</td><td></td><td>面漆</td><td>厚浆型环氧漆</td><td>1</td><td>70</td></tr><tr><td>底漆</td><td>环氧富锌底漆</td><td>1</td><td></td><td>50</td></tr><tr><td rowspan=\"3\">(在建） 广州珠江黄埔大桥</td><td>钢箱梁外表面</td><td>中间漆</td><td>环氧云铁中间漆</td><td>2</td><td>300</td></tr><tr><td></td><td>面漆</td><td>脂肪族聚氨酯面漆</td><td>2</td><td>80</td></tr><tr><td></td><td>底漆</td><td>环氧富锌底漆</td><td>1</td><td>80</td></tr><tr><td rowspan=\"2\">（在建）</td><td>钢箱梁外表面</td><td>中间漆</td><td>环氧云铁中间漆</td><td>1</td><td>150</td></tr><tr><td>面漆</td><td>脂肪族聚氨酯面漆</td><td></td><td>2</td><td>80</td></tr></table></body></html>\n\n注：打“”为数据不详。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 169,
+        "chunk": "# 7.桥梁涂装工艺流程简介  \n\n（1）钢箱梁涂装工艺流程钢箱梁涂装流程如图3-3-46所示。(2）混凝土主塔的涂装工艺流程混凝土涂装流程如图3-3-47所示。(3）浪溅区的涂装工艺流程浪溅区（干湿交替）受潮水涨退的时间影响，工作时间短，操作过程环境恶劣，相对于正常区域的混凝土结构，表面处理的时间要求大大缩短，以便有足够的时间使涂料表干。高压淡水喷射时间快，而且有较好的效果；同时，高压淡水冲洗后采用热风吹干的方法，也可以大大缩短表面处理。因此，对于浪溅区的涂装，如有条件，最好在表面处理中增加此两道工序。浪溅区涂装流程图如图3-3-48所示。  \n\n![](images/bc86a49e7d9afc9fb2a9cd95d32f9ae61e87c8c9d5f13adce6c829d26218cd53.jpg)  \n图3-3-46 钢箱梁涂装流程图  \n\n![](images/392f9352b38ad6245ef0bf624f4d29ad7493f3030810bbe1316be24104d68f4e.jpg)  \n图3-3-47 混凝土涂装流程图  \n\n![](images/393d25938abb3bc4eb326ac0f21bf55b81137acb9920dd43c125faff0e16a656.jpg)  \n图3-3-48 浪溅区涂装流程图",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 170,
+        "chunk": "# 8.桥梁的维修涂装  \n\n(1）防腐涂层的失效分析防腐涂层失效是指涂层长期暴露在腐蚀环境下，而引起各种物理和化学性能的衰变，使其失去原有的性能，部分或全部失去对桥梁基体的保护作用。  \n\n桥梁的防腐涂层失效主要分为有机涂层失效和金属涂层失效两大类。  \n\n$\\textcircled{1}$ 有机涂层的失效分析主要是涂层受到化学物质的侵蚀，或受到外界环境如紫外线、冷热雨水等的长期作用，以及腐蚀介质对涂层的溶胀扩散等导致其受到破坏等。  \n\n$\\textcircled{2}$ 金属涂层的失效分析对于金属涂层，主要有热喷锌、热喷铝、热浸镀锌和富锌涂层几种。它们都是利用锌或铝在使用过程中起到的阴极保护作用、牺牲自己来保护钢铁底材的。金属涂层的失效形式为均匀的化学或电化学腐蚀，它的腐蚀寿命可以根据试验获得涂层的腐蚀速率，在已知金属涂层厚度的情况下，计算金属涂层的耐蚀寿命。富锌涂层的腐蚀失效则兼具有机涂层和金属涂层的特点，一方面富锌涂层对钢铁有阴极保护作用；另一方面有机涂层的失效会使金属锌粉附着不牢或脱落失去作用。因此，对于富锌涂层应视上述两种因素谁更占主导，则涂层的使用寿命就取决于那种因素。  \n\n$\\textcircled{3}$ 复合涂层的失效现代桥梁的重防腐体系，是以金属涂层和有机涂层相结合的保护涂层。外层的有机涂层可以有效地阻挡腐蚀因子对金属涂层和钢铁的侵蚀。复合涂层的失效首先就是外层有机涂层的失效，大多数情况为粉化、剥落等。由于有机涂层的损坏，腐蚀因子有机会渗人底面，再引起金属涂层的腐蚀失效，而腐蚀产物的生成和积累又会引起有机涂层的附着力下降等。  \n\n(2）维修涂装的依据由于防腐涂层的腐蚀失效，为了保护桥梁的安全性和耐久性，就有必要在一定时间内对原有的防腐涂层进行更新和维护。但是更新维护的依据是什么？简单地说，如何判断桥梁原有涂层的失效程度——是局部还是全部？在确保更经济、更合理的前提下，什么时候才必须对桥梁进行更新维护？  \n\nGB/T1766—1995《色漆和清漆涂层老化的评级方法》（参照采用ISO $4628/1{\\sim}5-\\$ 1982）提供了较为详尽的评估方法，通过对有机涂层的起泡、锈蚀、开裂、剥落等几个方面对其腐蚀失效的程度进行分级，为相关的管理维护部门制订维护方案提供了简单明了的依据。  \n\n按上述标准评级，通常认为有机涂层失效的综合等级达到3（S3）或4（S4）时，应尽早安排涂层的更新维修涂装。  \n\n需要说明上述标准中列举的锈蚀一项。锈蚀的产生是由于底材的表面处理不当、涂层的厚度过低或者涂层涂装不当，有贯穿孔隙存在等原因所造成的。出现锈蚀，说明涂层局部已完全失去作用，对于整个有机涂层的防腐性能也产生影响。同时锈蚀斑点处腐蚀产物的集聚，也会加速周边的涂层产生起泡、剥落、老化等失效作用。防腐技术认为，涂层的锈蚀面积等级达到了3级（相当于ISO4628/3中的Ri3或欧洲标准的Re3）就应对涂层进行维修涂装。  \n\n(3）维修涂装设计与施工制订桥梁的维修涂装方案要比制订一个新建桥梁的涂装规程复杂得多。必须要有一套系统的方法、进行一些特定的测试，来确定原有涂层的状态以及整体结构的完整性；同时还要仔细研究考虑施工地点的条件和相关的环境、安全方面的法律法规等一系列的工作，才能有针对性地制订出维修方案来。  \n\n(4）维修涂装用涂料的选择在选择维修用涂料前，首先要对原涂层进行全面的分析。这些工作包括原涂层的附着状况、原涂装配套系统的分析等。通过一些简单的现场测试，可以大致了解原涂层状况。比如划格法测试（GB/T9286—1988）可以简便、快速地了解涂层的附着（涂层之间、涂层内部或涂层与底材之间）状况；溶剂MEK（甲乙酮）擦拭法，根据涂层被擦拭后状况（溶解、咬起或起皱、影响不大)，可以大致分析出涂装的种类是物理干燥型、氧化固化型或是化学固化型。当然，这些测试的结果是粗略的，只能作为参考依据。要得到精确的结果，还需要另外的方法或是实验室的测试。  \n\n其次，还需要考虑选用的涂料对表面处理的要求、维修现场的工作条件以及相应的涂装设备和涂装技术。  \n\n通过上述的测试和分析，并参照涂层间相容性的因素，以及设计涂层的使用寿命，才能选择合适的维修涂装用涂料。  \n\n（5）维修涂装的施工根据原始涂层的老化程度，维修涂装可以选择局部维修或整体翻新。局部维修可以使用一些简单的手动动力工具对需维修的部位进行表面处理，采用辊涂、刷涂或喷涂等方式进行修补。而整体翻新则需要将原有涂层全部清除干净，并采用合适的表面处理方式（一般采用喷砂除锈)，按照新建桥梁结构的涂装施工要求，重新涂装新的防腐涂层。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 171,
+        "chunk": "# 二、石油化工防腐蚀涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 172,
+        "chunk": "# 1.石油化工防腐蚀涂料概述  \n\n石油化工是石油工业的下游工业，是一个复杂而庞大的工业体系，主要包括炼油和生产乙烯、丙烯、苯乙烯、聚酯、合成橡胶等，以及处于更为下游的各类化工品等。石油化工的腐蚀包括电化学腐蚀、化学腐蚀及由其造成的局部腐蚀、大气腐蚀、土壤腐蚀、海水腐蚀和高温腐蚀等。因此石油化工对于防腐蚀涂料的要求也是多样的，需要具有优良的耐化工大气、耐盐雾侵蚀、耐土壤腐蚀、耐高温腐蚀和耐酸耐碱性能。  \n\n石油化工传统上使用的涂料多为醇酸树脂涂料、氯磺化聚乙烯涂料、高氯化聚乙烯涂料、环氧煤沥青涂料等。传统的防腐蚀涂料产品在以往的使用中尽管有着令人满意的防腐蚀性能，但是挥发性有机物含量（VOC）太高，含有毒重金属的红丹漆、含致癌物的沥青漆仍有广泛应用。  \n\n现在石化行业提出了重防腐新概念：省时、环保和安全。在此新概念之下，与传统防腐迥然不同的一系列新型重腐蚀涂料产品，如环氧富锌、无机硅酸锌、环氧云铁、脂肪族聚氨酯涂料、玻璃鳞片涂料等开始大量应用。新型重防腐涂料具有不含重金属、不含沥青、低VOC、干燥迅速、低表面处理、厚膜型施工等特点。  \n\n无溶剂、高固体分和水性重防腐等低VOC涂料的应用，可以在保证防腐蚀性能的同时，有效地解决目前石化行业涂装过程中由于传统溶剂型涂料带来的安全隐患。在新建钢结构的工场涂装时，快速干燥的涂料体系以及厚膜型施工涂料能大大缩短涂装工时，加快钢结构的涂装、场地的周转以及钢结构的运输和安装。石化工厂在检修防腐涂装时，快速的涂装意味着较短的停车检修时间和更少的涂装工时，被涂装的设施可以在最短时间内恢复使用。  \n\n耐高温和低温是石油炼化厂的通常要求。在设备表面的温度有可能是环境温度，也可能是设备本身的操作温度。大气温度有可能从北方的零下几十摄氏度到南方的 $40^{\\circ}C$ 以上。操作温度可能会从一 $20^{\\circ}C$ 到 $538^{\\circ}C$ 的高温，比如冷藏系统的低温，或者锅炉上的高温等。在这一区间内的涂料选择，包括环氧、改性环氧、酚醛、丙烯酸有机硅、聚氨酯、无机锌、有机硅、热感应、玻璃填充无机物等。对于受到快速变化的表面，涂料还要耐受热冲击。如果涂料不能耐受温度，则会发生明显的损坏。  \n\n涂漆表面会受到空气中浮游物质如砂粒、炭灰或其他含颗粒物质的介质的冲刷磨蚀。在日常的维修过程中，会受到新装的管线或阀门的挤压，或者扳手等其他工具的跌落也会破坏涂层。安装涂漆部件时，吊索也会对涂层造成损坏。无机硅酸锌涂料的涂层比较坚硬，在pH=6～9的环境中，可以单独使用不需要面漆；如果需要涂面漆，环氧、丙烯酸、聚氨酯等是常用涂料品种。  \n\n大风、温差或者加工过程中的压力，会使构件变形弯曲。例如大型浮顶罐的浮顶在高速的大风下会变形达 $25.4\\mathrm{cm}$ 。加工操作中，加热和制冷时容器薄壁会膨胀和收缩。因此热膨胀系数在选择不同涂料时也要有所考虑。  \n\n不同的涂料耐紫外线和温度极限有很大区别。靠近赤道区域的涂料要能耐强辐射，靠近北极圈的地方，涂层要能耐严寒。环氧涂料不耐紫外线，很容易粉化，因此不易作为户外面漆使用，丙烯酸面漆、脂肪族聚氨酯面漆是较好的选择。  \n\n不同的涂膜耐水和耐溶剂的渗透性有很大区别，这对在潮湿环境下的涂层使用寿命有很大影响。在高湿环境下，水的渗透力会变大。碳氢树脂改性环氧涂料，无机硅酸锌底漆加涂聚酰胺环氧涂料和脂肪族聚氨酯面漆是常用的涂料配套体系，干膜厚度在$150{\\sim}200\\mu\\mathrm{m}$ 0  \n\n由于能量保存需要的增长，热辐射变得非常重要。涂料能用于降低或增加热传输以节省能源。黑色的热反射率接近于0，铝色和中灰在 $40\\%\\sim50\\%$ ，白色大于 $80\\%$ 睿",
+        "category": " Introduction"
+    },
+    {
+        "id": 173,
+        "chunk": "# 2.钢结构设备装置防腐蚀涂料  \n\n(1）钢结构设备装置的腐蚀石油化工中的钢结构主要分为装置钢结构、管廊钢结构和没有特殊防护要求设备装置的外露表面。装置钢结构位于各装置（如常减压、催化裂化、催化重整等）内，用于支撑各种设备和塔器等；管廊属公用工程，位于界区外公用工程中。其中最大量的钢结构应该是管廊架，它架设着各类工艺管线，同时还包括相配套的爬梯、栏杆和扶手等。大型的石化企业，管廊架有数十千米长。管廊架钢结构多以H型钢，用高强度螺栓构建而成。  \n\n石化生产企业的钢结构处于腐蚀性介质或气体包围中，腐蚀介质或气体的成分复杂、渗透力强，极易对钢结构产生破坏性腐蚀，钢结构的腐蚀破坏，会导致化工设备运转的不安全或遭到破坏，甚至钢结构的倒塌会导致装置停产、化工物料泄漏、爆炸、着火等事故；因此，为了安全，必须针对石油化工钢结构的腐蚀特点，采取适当的防腐措施。石油化工中的钢结构腐蚀主要为大气腐蚀。化工厂的大气中 ${\\bf S}{\\bf O}_{\\perp}$ ， $\\mathrm{H}_{2}\\mathbf{S}$ 、 $\\operatorname{Cl}_{2}$ 、HCl、 $N a C l$ 、灰尘等污染物质对钢结构的腐蚀影响较大，这些物质被钢铁表面的水膜溶解后，即成为导电性良好的电解质溶液，从而加速了腐蚀的进行。大气中相对湿度大于 $70\\%$ 时，只需含 $0.01\\%$ $\\mathrm{{\\bfS}O_{2}}$ ，钢结构的腐蚀速率便急剧增加， $\\mathrm{{\\bar{S}O_{2}}}$ 首先被吸附在钢铁表面上与氧一起生成 $F e S O_{4}$ ，然后$\\mathrm{FeSO_{4}}$ 水解生成游离的硫酸，硫酸又加速腐蚀铁，新生成的 $\\mathrm{{\\bfFeSO_{4}}}$ 再水解生成游离酸，如此反复循环就会加速钢铁的腐蚀。  \n\n（2）防腐蚀涂料体系石油化工钢结构表面的防护涂料体系，曾大量应用氯磺化聚乙烯涂料、高氯化聚乙烯涂料等。  \n\n氯磺化聚乙烯橡胶由氯和二氧化硫混合气体对聚乙烯同时进行氯化和磺化而制得。氯磺化聚乙烯涂料通过磺酰氯基与胺固化剂交联，固化后的涂层对氧化剂、臭氧和紫外光稳定，户外保色性好，耐酸碱性能强，使用温度在 $-50{\\sim}120^{\\circ}C$ 。氯磺化聚乙烯涂料有环氧树脂、聚氨酯改性产品。氯磺化聚乙烯涂料的有机溶剂含量高，固体含量相当低，一次成膜只有$20\\sim30\\mu\\mathrm{m}$ 的干膜厚度，要达到一定的干膜厚度，需要多次施工。  \n\n高氯化聚乙烯简称HCPE，由聚乙烯高度氯化而成，氯含量超过 $60\\%$ 。以高氯化聚乙烯为主要成膜物的防腐蚀涂料，具有耐臭氧、耐酸碱、耐海水、耐油、耐老化性能。高氯化聚乙烯是单组分产品，施工方便，涂膜干燥迅速。高氯化聚乙烯涂料开发应用的主要产品系列有铁红防锈漆、云铁防锈漆、富锌防锈漆、玻璃鳞片涂料和各色高氯化聚乙烯面漆，每道漆成膜厚度在干膜 $40\\mu\\mathrm m$ 左右。  \n\n目前钢结构设备装置的防腐蚀涂料体系以重防腐蚀涂料体系为主，防腐涂层设计使用寿命在10年或10年以上，以富锌漆为底漆，环氧为中间漆，脂肪族聚氨酯为面漆。也可采用环氧涂料 $+$ 聚氨酯涂料体系，在相同的腐蚀环境下，不采用富锌底漆，要相应地增加涂膜厚度，见表3-3-43。  \n\n表3-3-43钢结构装置的涂装体系  \n\n\n<html><body><table><tr><td rowspan=\"2\">涂层</td><td colspan=\"2\">富锌漆体系</td><td colspan=\"2\">环氧体系</td></tr><tr><td>涂料产品</td><td>干膜厚度/μm</td><td>涂料产品</td><td>干膜厚度/μm</td></tr><tr><td>底漆</td><td>环氧富锌底漆或无机硅酸锌 底漆</td><td>75</td><td>高固体分环氧涂料</td><td>100</td></tr><tr><td>中间漆</td><td>环氧云铁中间漆</td><td>75</td><td>高固体分环氧涂料</td><td>100</td></tr><tr><td>面漆</td><td>聚氨酯面漆</td><td>50</td><td>聚氨酯面漆</td><td>50</td></tr></table></body></html>  \n\n富锌底漆可以选用环氧富锌底漆和无机富锌底漆。根据HG/T3668—2000，不挥发分中的金属锌含量，无机富锌底漆不低于 $80\\%$ ，有机富锌底漆（主要是环氧富锌底漆）不低于 $70\\%$ 。  \n\n无机硅酸锌底漆在石化行业的应用更多，其主要原因除了其更好的耐腐蚀性能外，还可以作为耐高温涂料，在工艺管线上有着大量应用。采用无机硅酸锌底漆时，涂覆后道环氧云铁中间漆时，要采用雾喷/统喷的技术，压迫出无机硅酸锌表面的空气，避免后道涂层产生针孔缺陷。  \n\n(3）工艺管线防腐蚀涂料在新建石化厂时，工艺管线十分复杂，有不同的介质、温度等。造成涂装设计和施工上的困难主要是不同的温度范围造成的，特别是高温管线需要耐高温涂料。在实际的涂装过程中，由于工地现场会堆满各种各样的工艺管线，要把这些管线区分开来涂装并且很有条理地堆放，在涂漆期间，由于场地、工人、管理等各种大因素，实际上是非常困难的。因此，采用无机硅酸锌底漆作为通用的防腐蚀和耐高温涂料是涂装设计上最好的选择。  \n\n无机硅酸锌底漆，以锌粉为主要防锈颜料，干膜中锌粉含量达 $80\\%$ （质量分数)，可以耐 $400^{\\circ}C$ 的高温，与改性有机硅铝粉漆配合使用，可以耐 $540^{\\circ}C$ 高温。设计干膜厚度在 $50\\cdots$ $75\\mu\\mathrm{m}$ ，不易太厚，否则会因管线的冷壁效应而引起涂膜开裂。  \n\n工艺管线的涂料系统设计选型，主要是考虑到使用温度的限制、保温与非保温以及材质的区别。  \n\n保温（有时是保冷）主要是为防止能量的损失以及防止高温对人的伤害。低于 $120^{\\circ}C$ 非保温管线表面，与一般的碳钢结构相同，可以选用环氧富锌/无机硅酸锌 $+$ 环氧涂料 $+$ 脂肪族聚氨酯面漆的配套方案。长期运行在 $120^{\\circ}C$ 的温度环境下，选用环氧涂料和聚氨酯漆，其白色或浅色涂料在 $100{\\sim}120^{\\circ}C$ 时会有变黄的可能，但是不影响其使用效果。  \n\n在 $120{\\sim}230^{\\circ}C$ 时，可以选用丙烯酸有机硅或酚醛环氧涂料。  \n\n在 $200{\\sim}400^{\\circ}C$ 时，主要可以选用无机硅酸锌底漆。在 $400\\sim600^{\\circ}\\mathrm{C}$ ，有机硅铝粉漆是主要的选择。  \n\n如果在不锈钢表面需要进行涂漆，不可以选用含锌或铝涂料，以免引起电偶腐蚀。  \n\n不同设计温度的工艺管线，以无机硅酸锌为底漆，配套方案见表3-3-44。  \n\n表3-3-44 管道及支架涂料系统配套方案  \n\n\n<html><body><table><tr><td>部位和温度范围</td><td>底漆</td><td>涂料产品</td><td>干膜厚度/μm</td></tr><tr><td>不保温碳钢包括管线中特殊阀最大操作温度93℃ (200F)</td><td>底漆 中间漆 面漆</td><td>无机硅酸锌(或环氧富锌) 厚浆型环氧 聚氨酯</td><td>75 75 50</td></tr><tr><td>不保温碳钢包括管线中特殊阀，操作温度94～204℃ (201~400°F)</td><td>底漆 面漆</td><td>无机硅酸锌 丙烯酸有机硅</td><td>75 2X25</td></tr><tr><td>不保温碳钢包括管线中特殊阀，操作温度205～482℃ (401~900°F)</td><td>底漆 面漆</td><td>无机硅酸锌 有机硅铝粉漆</td><td>75 2X25</td></tr><tr><td>保温碳钢操作温度121℃（250F），最高操作温度 121℃(250°F)</td><td>底漆 面漆</td><td>酚醛环氧 酚醛环氧</td><td>75 75</td></tr><tr><td>保温碳钢操作温度持续高于121C（250F）</td><td>底漆 底漆</td><td>无机硅酸锌 酚醛环氧</td><td>75 75</td></tr><tr><td>调节阀、安全阀和闸阀等</td><td>面漆 底漆</td><td>酚醛环氧 环氧防锈漆</td><td>75</td></tr><tr><td>保温不锈钢，常温到121℃C（250°F）</td><td>底漆</td><td>环氧涂料(不含锌、铝颜料)</td><td>50~75 100～150</td></tr><tr><td>保温碳钢和低合金钢，循环介质温度一29～120℃</td><td>底漆</td><td></td><td></td></tr><tr><td>(一20~248°F) 保温碳钢和低合金钢，循环介质温度121～482℃</td><td>底漆</td><td>环氧漆</td><td>125</td></tr><tr><td>(250~900F) 保温不锈钢，121～250℃（250～482F）</td><td>面漆</td><td>耐高温有机硅 耐高温有机硅</td><td>25 40</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 174,
+        "chunk": "# 3.贮罐防腐蚀涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 175,
+        "chunk": "# （1）贮罐的腐蚀  \n\n$\\textcircled{1}$ 贮罐外壁的腐蚀炼油厂和大型石化企业等，都建有大型的贮罐。外壁受到的主要是大气腐蚀，诸如由于大气中水分、氧气、温差变化，沿海盐雾、化工大气等腐蚀性气体的腐蚀，以及紫外线引起的涂层老化破坏等。位于风沙较大地区的贮罐，风沙中的沙或灰尘对贮罐表面覆盖层会造成机械磨蚀。  \n\n石油化工区空气中的酸性气体、受到雨水或夏季用于降温的喷淋水而引起贮罐钢铁表面液膜下的氧去极化反应。当气温周期性地下降时，溶有电解质的水分就会凝结于罐体外表面，形成连续的电解质溶液薄膜层，从而造成腐蚀。  \n\n罐体壳板由于材质，物理状态不均匀等原因，不同部位存在着电位差，外表面形成很多的微电池，引起腐蚀。顶部的腐蚀是由于直接受到紫外线照射，加上钢板在加工时存在的凹凸不平，容易积水，发生电化学腐蚀。这个问题在浮顶油罐上体现很突出。浮顶单盘的凹凸不平，最容易积水，从而引起腐蚀穿孔的事例多有发现。  \n\n随着石油工业的发展，进出口耗油的增加以及油品的转运量增大，沿海地区修建了大规模的油库。海洋大气具有很强的腐蚀性，沿海地区空气中存在着大量的氯离子和其他盐类，沉降在罐体外壁时，就会形成含有溶解盐的电解液膜。氯离子的渗透性相当强，它会造成严重的局部腐蚀。  \n\n$\\textcircled{2}$ 罐底板和边缘板的腐蚀罐底由于毛细作用，地下水上升，长期处于潮湿的环境。而且由于底板焊接，焊缝附近的防腐蚀涂层遭到破坏，这里的腐蚀会格外严重。油罐周边底板对沙垫层的压实程度明显低于油罐中心部位，沙孔隙中的氧含量不均匀，很容易造成氧浓差电池，即罐底板中心部位为阳极，导致其腐蚀状况比周边部位厉害得多。  \n\n贮罐基础以砂层和沥青砂为主要构造。罐底板坐落在沥青砂面上，由于罐中满载和空载交替，冬季和夏季温度及地下水的影响，使得沥青砂层上出现裂缝，致使地下水上升，接近罐的底板造成腐蚀。当油罐的温度较高时，罐底板周围地下水蒸发，使盐分浓度增加，增大了腐蚀程度。罐底板与砂基础接触不良，易产生氧浓差。满载和空载比较，空载时接触不良，再由于罐周围与罐中心部位的透气性有差别，也会引起氧浓差电池，这时中心部位成为阳极而被腐蚀。  \n\n罐区地中的电流是较为复杂的区域，罐区管网有阴极保护而贮罐未受保护时则可能形成杂散电流干扰影响，当周围有电焊机施工、电气化铁路、直流用电设备时则可能产生杂散电流。  \n\n边缘板在贮罐使用一段时间后，由于贮油量的载荷变化而引起罐体变形，另外就是由于环境温度的变化使底板发生膨胀和收缩，导致罐体底板与基础形成一条裂缝，该裂缝会随着油罐的运行而膨胀与收缩，这样就会给外界腐蚀介质如雨水的进人提供了通道，积水就会造成缝隙腐蚀。大角缝在焊接过程中造成的漆膜损坏，一旦腐蚀介质人侵，将会导致锈蚀而穿孔。油罐底部边缘板的腐蚀多为层状均匀腐蚀，沿底板半径方向向中心逐步发展成局部腐蚀，再向里呈点蚀。边缘板下的锈蚀深度从外周边向里大多为 $300{\\sim}500\\mathrm{mm}$ 。加热油罐的锈蚀比常温油罐要明显，大体上比常温油罐高出一倍。由于圈梁的阻隔，边缘板还是阴极保护的盲区。  \n\n如果罐体外有保温材料，一旦里面吸水，情况就会变得更糟。超细玻璃棉或岩棉保温材料为柱状纤维结构，极易吸湿。玻璃棉本身含有 $C1^{-}$ 浓度达 $1800\\mathrm{mg/L}$ ，加上沿海地区大气中的 $\\mathbb{C l}^{-}$ ，这样吸湿后的保温层反而起到助长腐蚀的趋势。  \n\n边缘板缝隙常用石棉绳填塞，再用防水胶与玻璃纤维布混合密封，这种方法的实际效果并不好，防水性能往往达不到预计效果。  \n\n使用沥青灌缝或敷沥青砂也是常用方法，但是实践证明成功防水的很少。目前较好的防水材料有封闭型异氰酸盐聚合物、弹性体聚氨酯、丙烯酸丁酯、CTPU高性能防水涂料等。  \n\n普通涂料需要定期更换，不太方便，无机硅酸锌的防腐效果虽好，但是由于积水的作用，锌粉的消耗会很快。进行喷铝可以一劳永逸地解决问题。  \n\n$\\textcircled{3}$ 保温层下的腐蚀原油罐和重质油贮罐的外面包有保温层。保温材料多为聚氨酯硬质泡沫、蛭石和岩棉等。含有大量的可溶性盐，加上外面渗进的水和里面形成的冷凝水，呈酸性，年腐蚀速率可以达到 $0.8\\mathrm{mm/a}$ 以上。保温层一旦进水，水沿着罐壁流下，在罐壁的下部形成一条水线，在此处就会形成氧浓差电池。打开保温层会发现罐上有明显的腐蚀环带。  \n\n$\\textcircled{4}$ 原油罐浮顶的腐蚀原油罐浮顶分别由顶板、底板、加强、径向隔板和环向隔板组焊而成，径向隔板和环向隔板将浮顶分成若干个舱。原油罐浮顶表面积大， $20000\\mathrm{m}^{3}$ 原油罐的表面积将近 $1300\\mathrm{m}^{2}$ ，而 $30000{\\mathrm{m}}^{3}$ 原油罐的表面积达 $\\bf{1600m^{2}}$ 以上。浮顶在生产中要上下起浮，表面受到空气污染的因素很大，一些有害气体，如 $\\mathrm{SO_{2}}$ ， $\\mathrm{H_{2}S}$ 等和水蒸气一起凝结在浮顶低洼处，形成电解液，若没有及时清除，就会造成局部防护涂层的破坏，导致浮顶局部腐蚀加剧。罐顶的油泥、铁锈以及它们形成的淤泥，在积水的情况下，就会形成氧浓差电池而发生腐蚀。受到沉积物覆盖的表面由于缺氧就会形成阳极，从而造成局部的点蚀。特别是在夏季昼夜温度和湿度的变化，金属表面处于干湿交替状态，金属锈层就会加速氧化腐蚀。浮顶腐蚀严重时，产生穿孔，致使原油泄漏到浮顶上面，油罐将不得不停用检修。  \n\n$\\textcircled{5}$ 储罐的内壁腐蚀油品本身，不管是原油、半成品油还是成品油，都没有腐蚀性，但是由于油品中有无机盐、酸、硫化物、氧、水分等腐蚀性杂质，以及在炼制过程中产生的腐蚀性介质均会对油罐造成腐蚀。  \n\n从腐蚀程度上讲，一般轻质油比重质油重，二次加工轻质油（如焦化汽油、焦化柴油和裂化汽油）比直馏轻质油重，中间产品比成品油重。油罐腐蚀严重部位是污油罐和轻质油罐（石脑油罐和汽油罐）的气相液相交界处及其气相部位，汽油罐顶的腐蚀尤为严重，其次是轻质油罐底和重质油罐（原油罐、渣油罐等）油水交界面（油罐周围1m高左右）的罐壁与罐底。  \n\n油罐底部的加热盘管，处于高含硫、高盐分污水中，受到电化学腐蚀、细菌腐蚀及垢下腐蚀很严重，其特点是斑点和坑蚀，腐蚀速率一般为 $0,4{\\sim}0,8\\mathrm{mm/a}$ ，最大可达 $2\\mathrm{mm/a}$ 。严重的情况为 $3\\sim4$ 年即穿孔破坏。  \n\n油罐壁的腐蚀较轻，为均匀腐蚀。腐蚀严重区域主要是发生在油水界面或油与空气交界处（大约为罐壁高的4/5处)，这里的腐蚀为电化学腐蚀。收发油过程中搅拌而携带到油品中的电解质是腐蚀的主要因素。由于油品中含氧量随着液面深度的增加而减少，形成氧浓差电池，上部是阴极，下部是阳极，造成罐内壁腐蚀沿液面高度变化的特点。罐壁的腐蚀与油罐的结构形式、收发油频率和速率以及所处的地理位置、主导风向等都有很大的关系。油罐罐壁腐蚀不仅会造成油罐强度的降低，而且使罐壁稳定性下降。罐壁的失稳会影响油罐的正常使用，然及油库安全。油罐的失稳大多发生在罐顶以下第二节圈板，罐体腐蚀最严重的部位通常也在这一圈板。加铅汽油罐腐蚀情况见表3-3-45。  \n\n表3-3-45 加铅汽油罐内壁的腐蚀  \n\n\n<html><body><table><tr><td>圈板层数(自上而下)</td><td>1</td><td>2</td><td>3</td><td>４</td><td>５</td><td>6</td><td></td></tr><tr><td>腐蚀速率/(mm/a)</td><td>0.27</td><td>0.39</td><td>0.33</td><td>0.25</td><td>0.24</td><td>0.21</td><td>0.18</td></tr></table></body></html>  \n\n罐顶常见点蚀等局部腐蚀，属气相腐蚀。主要受 $\\mathbf{H_{2}S}$ 1 $\\mathrm{SO_{2}}$ 、 $\\mathrm{CO_{2}}$ ， $\\mathrm{O}_{2}$ 、HCl和水蒸气的影响。当环境温度降到油气和水汽的露点以下时，就会产生露点腐蚀。当温度高于临界温度时，水蒸气很容易在罐顶内壁形成凝结水膜，而罐内含有的 $\\mathrm{\\bar{H}}_{2}\\mathrm{\\bar{S}}$ ， $\\mathrm{SO}_{2}$ ? $\\mathrm{CO}_{2}$ 以及挥发酚等杂质，会溶解在凝结水膜中产生电化学腐蚀，腐蚀率会发生突变。不同贮罐的罐顶结构不同，对腐蚀的影响也不同。油罐在收发油过程中或者静置贮油时，由于“大呼吸”和“小呼吸”的损耗，罐顶气体成分会呈有规律的变化。大呼吸损耗指油罐收发作业中液面高度变化而造成的油气损耗。其中，收油过程中发生的损耗称为收油损耗，即所谓的“大呼吸”。在发油后由于吸入空气被饱和而引起的呼吸称为回逆呼出。小呼吸损耗是指在有关静止贮油时，罐内气体空间温度和油气浓度的昼夜变化而引起的油气损耗。由于罐顶的呼吸作用，氧气不断进人罐内并很容易随凝结水的液膜扩散到金属表面。呼吸作用对罐顶的腐蚀影响很大，在贮油罐的抽吸和温度变化时所形成的呼吸作用中，雾气和空气吸入贮罐。所以罐顶的凝结水膜是含有多种腐蚀性成分的电解质溶液，导致罐顶腐蚀严重。罐顶的腐蚀表现伴有孔蚀的全面腐蚀，且油越轻腐蚀越严重。  \n\n随着装置高含硫原油加工量的不断增加，原油贮罐的腐蚀日益加重。贮罐清罐检修时，在罐体、罐底或罐顶经常可以发现麻点、凹坑，甚至被腐蚀穿孔，一旦发生事故，后果将不堪设想。经验表明，钢质贮罐如果原油中不含 $\\mathbf{H_{2}S}$ ，一般寿命为 $10\\sim15$ 年；如果含有 $\\mathrm{H}_{2}\\thinspace\\mathsf{S}$ 时寿命为 $3\\sim5$ 年。  \n\n罐底板是贮罐内腐蚀的重点所在，主要表现为电化学腐蚀。底板的腐蚀主要分布在低洼存水的部位，罐板腐蚀减薄及局部腐蚀严重，大多呈溃疡状的坑点腐蚀，很容易形成穿孔。沉积水中的氯离子、溶解氧、硫酸盐还原菌及温度对底板的腐蚀影响很大。而且在沉积物中含有盐类和有机淤泥，它的黏性抑制了氧的扩散，形成氧浓差电池。原油罐底底部的原油中会含有水（主要是海水）以及原油中含有的硫化物等腐蚀介质。罐底经常与油品接触的内壁，约 $\\ln$ 高，腐蚀呈不均匀的坑点状，是因为各种腐蚀性离子的积水以及油中沉积物所导  \n\n致的腐蚀。  \n\n浮顶罐浮盘支柱垫板的腐蚀是在操作过程中支柱对罐底的冲击造成罐底板的腐蚀穿孔。罐底焊缝区受热影响，由于钢材组织的不均匀，也会产生腐蚀。  \n\n典型的油罐腐蚀情况见表3-3-46。  \n\n表3-3-46 原油罐内部腐蚀速率  \n\n\n<html><body><table><tr><td>部位</td><td>罐底(内表面）</td><td>油相罐壁</td><td>油气或油水交界处</td><td>油罐顶</td></tr><tr><td>腐蚀速率/（mm/a)</td><td>0.2~0.3</td><td>0.1</td><td>0.2~0.3</td><td>0.1~0.2</td></tr></table></body></html>  \n\n(2）贮罐外壁防腐蚀涂料早期贮罐外壁一般选用亚麻油和醇酸树脂作为保护用涂料，比如亚麻油红丹防锈漆、醇酸红丹防锈漆、醇酸云母氧化铁中间漆和醇酸磁漆等，总的干膜厚度在 $120{\\sim}150\\mu\\mathrm{m}$ ，实际使用寿命为3年左右，严重的不到一年的使用寿命，涂层就开始粉化龟裂和剥落等。  \n\n20世纪80年代末到90年代初，开始大量使用氯磺化聚乙烯涂料。该涂料最早由日本引人我国，后来由吉化公司开发成功后，国产氯磺化聚乙烯涂料开始大量应用于钢铁冶炼厂和石油化工厂的钢铁结构表面，包括贮罐外壁的防护。该涂料有着很好的耐化工大气、耐酸碱和耐紫外线等功能，然而，由于它的体积固体分相当低，VOC含量过高，漆膜很薄，涂刷一道仅 $20\\sim30\\mu\\mathrm{m}$ ，因此抗渗透能力较低，其应用已经不适应重防腐的需要。  \n\n氯化橡胶涂料曾经是重要的钢结构防腐蚀涂料，也曾是贮罐外壁的主流配套方案。是天然橡胶或合成的聚异戊二烯橡胶在氯仿或四氯化碳中于 $80\\sim100^{\\circ}C$ 氯化而成。氯化橡胶漆膜致密而发脆，常加入氯化石蜡作为增塑剂。漆膜的水蒸气和氧气透过率极低，仅为醇酸树脂的 $1/10$ ，因此具有良好的耐水性和防锈性能。氯化橡胶在化学上呈惰性，因此具有优良的耐酸性和耐碱性。氯化橡胶涂料有着很好的附着力，它可以被自身的溶剂所溶解，所以涂层与涂层之间的附着力很好，涂层即使过了一二年，其重涂性仍然很好，可以在低温下施工应用，具有阻燃性。厚膜型可以一次喷涂达到 $80\\mu\\mathrm{m}$ 以上。由于氯化橡胶是将橡胶在 $\\mathrm{CCl_{4}}$ 中通氯后再在水中析出，其成品往往残留较多的四氯化碳，污染大气，我国在1991年加人保护臭氧层的“关于消耗臭氧层物质的蒙特利尔议定书”，已经停止和限止在氯化橡胶生产中使用四氯化碳，而代之以水相悬浮法、非四氯化碳溶剂法等新技术来生产氯化橡胶。  \n\n高氯化聚乙烯涂料也在石化厂有着广泛的应用。氯化聚乙烯（CPE）和高氯化聚乙烯（HCPE）树脂的开发始于60年代，当时采用溶剂法进行氯化，现在的水相悬浮深度氯化法已经成熟。高氯化聚乙烯涂料系列产品有高氯化聚乙烯富锌底漆、高氯化聚乙烯铁红防锈底漆、高氯化聚乙烯中间漆、高氯化聚乙烯防腐面漆和高氯化聚乙烯清漆等。  \n\n经历了几十年的实际使用，随着涂料技术的发展，加上业主对昂贵的维修费用的关注，在引人寿命周期费用分析（lifecyclecostanalyst）的概念后，为了减少维护涂装次数，目前最为常用的重防腐涂料体系是以环氧富锌底漆或无机硅酸锌底漆/环氧云铁中间漆/丙烯酸聚氨酯面漆。表3-3-47为处于ISO12944-2C4腐蚀环境下的设计使用寿命在15年以上的一个典型涂料配套体系。  \n\n表3-3-47贮罐外壁的重防腐涂料体系  \n\n\n<html><body><table><tr><td>涂层</td><td>涂料体系</td><td>干膜厚度/μm</td><td>涂层</td><td>涂料体系</td><td>干膜厚度/μm</td></tr><tr><td>底漆</td><td>环氧/无机硅酸锌底漆</td><td>75</td><td>面漆</td><td>丙烯酸聚氨酯面漆</td><td>60</td></tr><tr><td>中间漆</td><td>环氧云铁中间漆</td><td>120</td><td></td><td></td><td></td></tr></table></body></html>  \n\n以环氧富锌或无机硅酸锌底漆为主的防腐蚀涂料体系，根据贮罐所处的不同腐蚀环境，其干膜厚度在200～320μm。不同腐蚀环境下富锌底漆的干膜厚度范围在40～80μm。采用无机硅酸锌底漆作为防锈底漆，须加上一道封闭连接漆。  \n\n传统的环氧（云铁）中间漆干膜厚度通常只可以达到50um左右。而体积固体分高达$80\\%$ 的环氧涂料，包括环氧云铁，干膜厚度可一次喷涂达到 $75\\sim250\\mu\\mathrm{m}$ 中  \n\n脂肪族聚氨酯面漆在控制有机溶剂含量和提高体积固体分方面也有着很大的进展。体积固体分达 $63\\%$ 的脂肪族聚氨酯面漆，VOC仅为 $320\\mathrm{g/L}$ ，干膜厚度喷涂一道达到 $40{\\sim}80\\mu\\mathrm{m}$  \n\n贮罐外壁保温层内的防腐蚀涂料，温度 ${<}120^{\\circ}C$ ，通常采用环氧富锌底漆或环氧防锈漆。尽管无机硅酸锌底漆有着优异的保护性能，但是在温度 $60\\sim120^{\\circ}C$ 时，阴极和阳极发生逆转，反而会促进锌粉的腐蚀，这种情况下，NACE国际的意见是反对在保温层下使用无机硅酸锌涂料，如果采用了无机硅酸锌底漆，表面一定要有铝粉型涂料进行封闭。  \n\n保温采用较多的是岩棉、泡沫玻璃或硅酸盐类。这些材料有着不同的吸水性，所以必须使用不锈钢或特殊材料制成复合层来防止气体影响，阻挡水汽进人。然而，由于安装或日后使用过程中的原因，总是不可能完全阻挡水的进入，引起贮罐外壁的点蚀。在 $121\\sim250^{\\circ}C$ 的温度范围下，保温层下的防腐涂层可以采用耐高温酚醛环氧涂料，其干膜厚度在 $150\\mu\\mathrm{m}$ 以上，既耐高温、又耐酸性冷凝水的腐蚀。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 176,
+        "chunk": "# （3）贮罐内壁防腐涂层  \n\n$\\textcircled{1}$ 贮罐内壁防腐涂层的基本要求早期的贮罐内壁防腐蚀体系一般为环氧红丹防锈漆和环氧面漆，随着对贮罐内壁腐蚀的深人研究和油品化学品对涂层材料的要求，以及新型涂层材料的发展，现在对于贮罐内壁涂料的选用，主要根据不同的贮存介质、贮罐的类型、温度和压力等进行。没有哪一种涂料可能适用于所有的贮存介质。贮罐内壁涂料首先要求有很好的防腐蚀性，要有良好的耐溶剂性能。为了保证油品质量，如采用涂层防腐，在原油、汽油、航煤油及烃类、溶剂等介质中长期浸泡，漆膜无变化、不起泡、不溶胀、不剥离、不污染油品。在采用涂层防腐时，应考虑重质油罐与污水罐，内设加热器等升温造成涂层的耐温变与抗老化性能。为了油品的贮存安全，业主有时还要求采用防静电涂料。  \n\n贮罐内壁涂层系统的使用寿命，与贮罐内壁的钢材状况和所选用的涂层材料有密切关系。  \n\n钢材的点蚀程度对涂层的使用寿命有很大影响，因为点蚀后的钢材不利涂层的有效润湿和渗透，会造成漆膜的分布不均匀，并且有可能隐藏着盐分而导致起泡等涂层缺陷。  \n\n根据涂层厚度可以把贮罐内壁的涂层类型分为薄涂层、重防腐涂层和玻璃鳞片/纤维增强型衬里三大类，不同涂层的使用寿命见表3-3-48。  \n\n单位：年  \n\n表3-3-48贮罐内壁涂层使用寿命  \n\n\n<html><body><table><tr><td>钢材状况</td><td>薄涂层</td><td>重防腐涂层</td><td>玻璃鳞片/纤维增强型衬里</td></tr><tr><td>新钢材或没有任何点蚀</td><td>8</td><td>10</td><td>15</td></tr><tr><td>轻微点蚀</td><td>5</td><td>10</td><td>15</td></tr><tr><td>中等点蚀</td><td>X</td><td>10</td><td>15</td></tr><tr><td>严重点蚀(结构完整）</td><td>X</td><td>X</td><td>15</td></tr><tr><td>严重点蚀（结构薄弱）</td><td>X</td><td>X</td><td>X</td></tr></table></body></html>  \n\n薄涂层涂料主要有纯环氧涂料和酚醛环氧等，每道涂层施工干膜厚度控制在 $100\\mu\\mathrm{m}$ 左右，总膜厚在 $250\\sim300\\mu\\mathrm{m}$ a.  \n\n重防腐涂料层主要指少溶剂或无溶剂环氧涂料等，包括无溶剂玻璃鳞片涂料，设计干膜厚度在 $500{\\sim}1000\\mu\\mathrm{m}$  \n\n玻璃鳞片涂料或玻璃纤维增强型衬里，干膜厚度在 $1000{\\sim}1500{\\mu}\\mathrm{m}$ ，主要有环氧玻璃鳞片涂料、乙烯酯玻璃鳞片涂料、聚酯玻璃鳞片涂料以及无溶剂环氧玻璃纤维增强衬里等。  \n\n② 纯环氧涂料纯环氧涂料以环氧树脂为主要成膜物质，采用化学性质稳定的颜填料，聚胺为固化剂。聚胺固化的纯环氧涂料有着突出的耐溶剂性能，最常用的固化剂是脂肪胺加成物。纯环氧涂料广泛用于贮罐内壁涂层，是因为它有着多功能、宽泛的荷载性以及良好的施工性能。纯环氧涂料可以无气喷涂到很高的干膜厚度，而不会有流挂针孔等问题。但是它有着最大涂装间隔期，通常在 $23^{\\circ}C$ 时，最大涂装间隔期不能超过7天。纯环氧涂料不耐强溶剂，所以它不推荐用于装载甲醇、甲乙酮和无铅汽油。  \n\n$\\textcircled{3}$ 酚醛环氧涂料酚醛环氧涂料比纯环氧涂料具有更大范围的耐荷载性能，尤其是耐化学品性能更强，比如纯环氧涂料不耐丁醇，而酚醛环氧涂料可以装载这种苛性介质。在热水罐中，纯环氧涂料只能耐到 $40\\sim50^{\\circ}C$ ，而酚醛环氧涂料耐温可达 $95^{\\circ}C$ 8  \n\n酚醛环氧是多功能环氧树脂，用脂肪胺固化的树脂有着很高的交联密度，所以有着突出的耐化学品性能。  \n\n$\\textcircled{4}$ 无溶剂涂料无溶剂涂料包括无溶剂环氧涂料和无溶剂酚醛环氧涂料，两者的耐荷载区别与溶剂型涂料相似。无溶剂涂料还适用于原油贮罐内底板包括底板上 $1.8\\mathbf{m}$ 的腐蚀防护。  \n\n无溶剂环氧和无溶剂酚醛环氧树脂涂料由于涂层中不含溶剂，因此涂膜更为致密坚硬。在施工时可以采用双组分加热喷漆泵或一般的高压无气喷涂。由于无溶剂环氧涂料和无溶剂酚醛环氧涂料的混合使用时间非常短，常温下只有 $30\\mathrm{min}$ 左右，因此采用普通高压无气喷涂时要特别注意。  \n\n$\\textcircled{5}$ 玻璃鳞片涂料玻璃鳞片涂料在贮罐上的应用主要有环氧玻璃鳞片涂料和乙烯酯玻璃鳞片涂料两类。  \n\n环氧玻璃鳞片涂料在原油罐内壁主要应用于罐底板内表面以及往上 $1\\sim2\\ensuremath{\\mathrm{m}}$ 的罐壁，干膜厚度在 $300\\mu\\mathrm{m}$ 左右。  \n\n乙烯酯玻璃鳞片涂料由于其特殊的耐化学品性能，尤其适用于许多酸性介质，比如原油贮罐底部的酸性含硫原油与水的混合物。目前在日本，几乎所有石油贮罐内壁都采用了乙烯基酯玻璃鳞片涂料，2005年前日本要求的贮罐为7年内开罐检查无涂层质量问题，现在这一要求则提高到了10年。乙烯基酯玻璃鳞片涂料在贮罐内的涂层设计干膜厚度范围在$500{\\sim}1500\\mu\\mathrm{m},$  \n\n$\\textcircled{6}$ 无机硅酸锌涂料无机硅酸锌涂料以正硅酸乙酯为成膜物，锌粉含量达 $85\\%$ 以上。许多钢结构防腐方面应用的无机硅酸锌底漆并不适用于贮罐内壁，需要区别开来。由于锌的标准电位比钢铁低，起到了阴极保护作用。锌在腐蚀介质中起化学反应生成一层不溶性氢氧化锌以及碱式碳酸锌、碱式氯化锌和锌铁复盐，填充涂膜的空隙，使涂膜紧密地结合起来，从而延缓腐蚀，达到防锈目的。硅酸盐是以带负电荷离子或胶体粒子存在，金属表面带正电荷的铁离子将其吸附，与二氧化硅生成硅酸铁，阻滞了阴极化过程。胶体粒子吸附在金属表面，生成连续的保护涂膜，同量也起到了保护钢铁的作用。  \n\n用于贮罐内壁的无机硅酸锌涂料主要有溶剂型和水性无机硅酸锌涂料两种，干膜厚度设计分别为 $100\\mu\\mathrm{m}$ 和 $125\\mu\\mathrm{m}$ 。水性无机硅酸锌涂料以水为溶剂，是真正实现零VOC的涂料产品，特别适合于要求无闪点、安全施工的贮罐内壁。  \n\n无机硅酸锌涂料用于贮罐内壁时，要求装载介质的 $\\mathbf{pH}$ 为 $5\\sim10$ ，防止酸、碱对锌粉的侵蚀而使涂层过早失效。  \n\n$\\textcircled{7}$ 防静电涂料导静电涂料的化学组成中含有一定数量的导静电载体，如石墨粉、炭黑、镍粉、不锈钢粉、钛粉、氧化锡包覆的非金属粉（如玻璃纤维、云母、硫酸钡、钛白粉）等。成膜树脂多为环氧树脂和聚氨酯树脂等。  \n\n抗静电涂料中的导电颜料与贮罐内壁相接触，形成极多的、由导电填料粒子与铁元素直接接触的微电池。如果导电颜料的标准电极电位比钢铁的标准电极电位较负，导电颜料便成为放电子的阳极，使贮罐钢板成为接受电子的阴极而受到防腐蚀保护；反之，所用导电填料的标准电极电位比钢铁的标准电极电位较正，就会使钢铁成为腐蚀电池的阳极，使贮罐钢板的腐蚀速率大大加快，导致加速腐蚀的严重后果。石墨的标准电极电位 $+0.795\\mathrm{\\bfV}$ ，比钢铁一0.44V正得多，这就可以解释为什么许多采用炭系石墨的防静电涂料失败的根源所在，这也是目前行业内放弃炭系石墨而采用导电云母粉等作为导电颜料的主要原因。  \n\n中国石化总公司发布的《加工高含硫原油贮罐防腐技术管理规定》规定了液体石油产品的碳钢材质的贮罐内壁表面涂装涂料的方案，规定了喷铝、喷锌或无机硅酸锌涂料与导静电涂料的配套及原油罐内底侧设置牺牲阳极与涂料联合防护等措施，指导了石化系统贮罐的防护。对于某些原油贮罐罐内底侧设置牺牲阳极与涂料联合防护时，在贮罐内的罐积水区域（通常为 $1\\sim1.8\\mathrm{m}$ )，不能涂装导静电涂料，否则将加速牺牲阳极的消耗。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 177,
+        "chunk": "# 4.埋地管道外防腐涂料  \n\n(1）埋地管道的腐蚀埋地管道的外壁主要是受到土壤腐蚀，包括土壤类型、土壤电阻率、土壤含水量（湿度)、 $\\tt p H$ 、硫化物含量、氧化还原电位、杂散电流及干扰电流、微生物、植物根系等。因此在选择防腐覆盖层时，必须综合考虑其腐蚀特性。  \n\n埋地管道外防腐层的功能是通过防腐层把钢质管道的外表面与腐蚀环境隔离以控制腐蚀，减少所需要的阴极保护电流，改善电流分布。NACERP0169—1996《埋地或水下金属管道系统的外腐蚀控制》中规定了埋地管道防腐层的性能要求：  \n\n$\\textcircled{1}$ 有效的电绝缘性； $\\textcircled{9}$ 能有效地保持绝缘电阻随时间恒定  \n$\\textcircled{2}$ 有效的阻水性； 不变；  \n$\\textcircled{3}$ 涂覆于管道的方法不会对管道性能 $\\textcircled{10}$ 抗剥离性能；产生不利影响； $\\textcircled{11}$ 抗化学介质破坏；  \n$\\textcircled{4}$ 涂覆于管道上的防腐层缺陷很少； $\\textcircled{12}$ 补伤容易；  \n$\\textcircled{5}$ 与管道表面具有良好的附着力； $\\textcircled{13}$ 物理性能保持能力强；  \n$\\textcircled{6}$ 能够防止管道涂膜的缺陷随时间而 $\\textcircled{14}$ 对环境无毒；发展； $\\textcircled{15}$ 能防止地面贮存和长距离运输过程  \n$\\textcircled{7}$ 能防止针孔随时间发展； 不发生变化和降解。  \n$\\textcircled{8}$ 能抵抗装卸贮存和安装时的损伤；  \n\n目前管道的腐蚀防护可以采用双重措施，即防腐覆盖层与阴极保护（外加电流或牺牲阳极)。钢管的材质与制造因素是管道腐蚀的内因，特别是钢材的化学组分与微晶结构，非金属组分含量高，如S、P易发生腐蚀，C、Si易造成脆性开裂。微晶细度等级低，裂纹沿晶粒扩展，易发生开裂，加入微量镍、铜、铬可提高抗腐蚀性。在钢管制造过程中，表面存在缺陷如划痕、凹坑、微裂等，也易造成腐蚀开裂。  \n\n管道操作运行时，输送压力与压力波动是应力腐蚀开裂的又一重要因素。过高的压力使管壁产生过大的使用应力，易使腐蚀裂纹扩展；压力循环波动也易使裂纹扩展。当裂纹扩展达到临界状态时，管道就会发生断裂破坏，甚至引起爆炸（如输气管道)。  \n\n埋地设备和管道防腐蚀等级，应根据土壤腐蚀性等级来确定，见表3-3-49。  \n\n表3-3-49 土壤腐蚀性等级及防腐蚀等级  \n\n\n<html><body><table><tr><td rowspan=\"2\">土壤腐蚀性 等级</td><td colspan=\"5\">土壤腐蚀性质</td><td rowspan=\"2\">防腐蚀等级</td></tr><tr><td>电阻率 /n·m</td><td>含盐量 （质量分数）/%</td><td>含水量 （质量分数）/%</td><td>电流密度 /(mA/cm²)</td><td>pH</td></tr><tr><td>强</td><td><50</td><td>>0.75</td><td>>12</td><td>>0.3</td><td><3.5</td><td>特加强级</td></tr><tr><td>中</td><td>50~100</td><td>0.75~0.05</td><td>5~12</td><td>0.3～ 0.025</td><td>3.5~4.5</td><td>加强级</td></tr><tr><td>弱</td><td>>100</td><td><0.05</td><td><5</td><td><0.025</td><td>4.5~5.5</td><td>普通级</td></tr></table></body></html>\n\n注：1.其中任何一项超过表列指标者，防腐蚀等级应提高一级。2.埋地管道穿过铁路、道路、沟渠，以及改变埋设深度时的弯管处，防腐蚀等级应为特加强级。  \n\n不同的埋设土壤环境，对管道的防腐层有不同的要求，平原地区、山区、沼泽地和沿海地区等的土壤环境不同，选取的防腐层种类和涂层厚度也应有所不同。加拿大著名的管道公司NOVA对埋地管道外防腐层的最低性能要求作了量化分析，见表3-3-50。  \n\n表3-3-50NOVA对埋地管道外防腐层的最低性能要求  \n\n\n<html><body><table><tr><td>性能</td><td>试验方法</td><td>最低要求</td><td>备注</td></tr><tr><td>抗冲击</td><td>ASTM G 14</td><td>一般土壤5.6J 多石地段17J</td><td>保证搬运、施工中的机械损伤及金石壤的冲击 瑞佩公司研究直径为19mm的石砾从2m高下落产生0.56J 的冲击能</td></tr><tr><td>剪切黏结强度</td><td>ASTMD 1002</td><td>0.34MPa</td><td>抗纵向应力、钢管热胀冷缩环向应力、土壤干/湿交替应力</td></tr><tr><td>抗弯曲</td><td>NOVA 19077</td><td>>2% 2.34°/管径</td><td>ANSIB31.4，大于508mm管子的最大弯曲度30D，加上完全 余量、要求暂时弯曲变形达到一定的度数</td></tr><tr><td>硬度</td><td>ASTMD 2204</td><td>40</td><td>反映抗荷载能力，岩石、沙漠腐蚀及擦伤</td></tr><tr><td>抗穿透力</td><td>ASTM G 17</td><td>10%</td><td>反映抗静荷载能力，管子自重及回填土自重的压力及岩石穿透</td></tr><tr><td>耐土壤应力</td><td>NOVA 19076</td><td>无变化</td><td>抗黏性土干/湿交替应力</td></tr><tr><td>耐阴极剥离性能</td><td>ASTM G8</td><td>剥离半径<15mm</td><td>适应阴极保护</td></tr><tr><td>耐温</td><td></td><td>最高运行温度</td><td></td></tr><tr><td>耐水及化学介质</td><td>NOVA 19066 ASTM G 20</td><td>4级</td><td>根据土壤介质环境选化学介质为无明显影响</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 178,
+        "chunk": "# （2）埋地管道常用防腐蚀涂料  \n\n$\\textcircled{1}$ 设计规范NACERP-0169—1996《埋地或水下金属管道系统的外腐蚀控制》中推荐的管道防腐层有5种类型：煤焦油瓷漆、石蜡、预制胶带、熔结环氧涂层、聚烯烃涂层，取消了原有石油沥青。  \n\n我国石油行业制定了一系列管道防腐层技术规范，见表3-3-51。  \n\n表3-3-51 常用管道外防腐层技术规范  \n\n\n<html><body><table><tr><td>序号</td><td>防腐层种类</td><td>标准名称</td></tr><tr><td>1</td><td>石油沥青</td><td>SY/T0420—1997《埋地钢质管道石油沥青防腐层技术标准》</td></tr><tr><td>2</td><td>环氧煤沥青</td><td>SY/T0447—1996《埋地钢质管道环氧煤沥青防腐层技术标准》</td></tr><tr><td>3</td><td>煤焦油瓷漆</td><td>SY/T0379—1998《埋地钢质管道煤焦油瓷漆外防腐层技术标准》</td></tr><tr><td>4</td><td>聚乙烯胶带</td><td>SY/T0414《埋地钢质管道聚乙烯胶黏带防腐层技术标准》</td></tr><tr><td>5</td><td>挤压聚乙烯</td><td>SY/T0413—2002《埋地钢质管道聚乙烯防腐层技术标准》</td></tr><tr><td>6</td><td>环氧粉末</td><td>SY/T0315—1997《埋地钢质管道熔结型环氧粉末外涂层技术标准》</td></tr><tr><td>7</td><td>聚氨酯泡沫保温层</td><td>SY/T0415《埋地钢质管道硬质聚氨酯泡沫塑料防腐保温层技术标准》</td></tr><tr><td>8</td><td>各类有机防腐涂层</td><td>SY/T0061一2004《埋地钢质管道外壁有机防腐层技术规范》</td></tr></table></body></html>  \n\n近年来随着我国管道建设的大力发展，中国石油天然气集团公司发布了企业标准有：  \n\nQ/SYXQ8—2003《钢质管道三层结构聚乙烯防腐层技术标准》；  \n\nA/SYXQ9一2003《钢质管道熔结环氧粉末外防腐层技术标准》。  \n\n$\\textcircled{2}$ 埋地钢质管道外防腐层SY/T0061—2004《埋地钢质管道外壁有机防腐层技术规范》吸收了近年来库-部输油管道工程、陕西-北京天然气管道工程、西气东输管道工程等长输管道工程的设计、施工及检验经验，通过总结管道外壁有机防腐层的共性技术要求，并参照了NACERP0169—1996《地下或水下金属管道系统外腐蚀控制》和SY0007—1992《钢质管道及储罐腐蚀控制工程设计》编制而成。该标准规定了埋地钢质管道外壁有机防腐层设计、施工及验收的基本原则，适用于陆上油气田管道和长输管道外壁防腐层的设计、施工及验收。标准规定管道工程主体防腐层不应选用溶剂型涂料，跨越管段和地面以上管段可选用耐候性涂料。管道常用外壁有机防腐层材料可参照表3-3-52的有关规定。  \n\n表3-3-52 管道常用外壁有机防腐层材料的适用范围  \n\n\n<html><body><table><tr><td>类型</td><td>适用范围</td><td>不宜选用范围</td></tr><tr><td>石油沥青</td><td>1.长期工作温度：一10～80℃。其中：低于51℃ 时，可采用建筑石油沥青；不低于51C时，应采用管 道防腐石油沥青 2.土壤条件适宜的管道工程</td><td>1.细菌腐蚀较强的地区 2.在水下或沼泽及芦苇等深根作物发达 的地带和地形起伏较大、需冷弯的地段</td></tr><tr><td>煤焦油瓷漆</td><td>1.长期温度：-10～80°℃ 2.大多数土壤，特别是水下或地下水位高、深根作 物发达和细菌腐蚀较强的地带和人烟稀少的沙漠、形起伏较大、需冷弯的地段 戈壁等地区</td><td>1.人口稠密等环保要求较高的地段 2.石方段或碎石土壤、黏质土壤地段和地 3.寒冷气候条件下施工应用</td></tr><tr><td>聚乙烯胶黏带</td><td>1.长期温度：—10～70℃ 2.零星管道工程、管件 1.长期工作温度：—30～100℃</td><td>1.石方段、碎石土壤、黏质土壤地段 2.水下、水位高、土壤含率高的地段</td></tr><tr><td>熔结型环氧粉末</td><td>2.地形平坦、以土方为主的地段，特别适用于黏质 土壤 3.双层熔结型环氧粉末防腐层可用于高含水或石 方段 1.长期工作温度：-30～100℃，其中t≤50℃时，</td><td>1.高含水或地下水位较高地段 2.碎石土壤环境</td></tr><tr><td>聚烯烃</td><td>可采用常温型PE防腐层；t为50～70C时，可采用 高温型PE防腐层；为70～100℃时，可采用PP防 腐层 2.聚烯烃防腐层可用于各土壤和水下地段，特别 是地形起伏较大、地质状况恶劣的山地、丘陵、水网 地区、腐蚀性强及管道穿越等对机械强度要求高，不 易维护的特殊重要地段</td><td></td></tr></table></body></html>  \n\n沥青类涂层包括石油沥青和煤焦油瓷漆，施工时将熔融的沥青与加强物（如玻璃布）交替缠敷，形成多层厚涂层。其优点是价格低廉，施工工艺成熟，缺点是黏结力差，环境污染严重，适用于地质条件相对较好、土壤电阻率较高的旷野。  \n\n石油沥青在熬制前，先要破碎成粒径为 $100{\\sim}200\\mathrm{mm}$ 的块状，清除纸屑、泥土及其他杂物。缓慢加温，熬制温度控制在 $230^{\\circ}C$ 左右，最高不要超过 $250^{\\circ}C$ ，每锅沥青的熬制时间在 $4\\sim5\\mathrm{h}$ 。沥青在熬制中会散发出浓烟恶臭，对环境和人体极为有害。  \n\n煤焦油瓷漆是高温煤焦油分馏得到的重质馏分和煤沥青，添加煤粉和填料，经加热熬制所得的制品，它克服了石油沥青的缺陷，但是在较低温度环境下的冷脆却限制了它的使用范围，而且它抗外界机械力破坏强度不高，石方山区不宜使用。1985年以前在西方国家煤焦油瓷漆是用量最大的防腐涂料，我国的煤焦油瓷漆是在20世纪90年代开始大量使用的。由于在人工熬制和浇涂过程容易逸出有害物质对环境及人体健康有不利影响，其应用受到限制，已经逐渐被熔结环氧粉末涂层（FBE）和三层聚乙烯涂层（PE）所取代。  \n\n为改善其黏结力和减轻环境污染，在沥青中加入环氧树脂就制成了环氧沥青涂料。环氧煤沥青涂料从20世纪50年代开始起大量应用于埋地和水下钢结构，有着良好的应用记录。我国在20世纪70年代开始研究应用环氧煤沥青涂料，广泛用于埋地、水下的各种金属结构。与玻璃布共同形成的环氧煤沥青涂层较好满足了埋地管线防腐的需要。SY/T0447—1996《埋地钢质管道环氧煤沥青防腐层技术标准》中规定，为适应不同腐蚀环境对防腐层的要求，环氧煤沥青防腐层分为普通级、加强级和特加强级三个等级，其结构由一层底漆和多层面漆组成，面漆层间加玻璃布增强，见表3-3-53。环氧煤沥青涂料的缺点在于施工麻烦、周期长，人为和环境影响因素较大。施工时要求在 $15^{\\circ}C$ 以上，低于 $15^{\\circ}C$ 时，要使用低温固化型环氧煤沥青涂料。由于固化时间长，钢管预制厂的能耗大，生产效率低。近年来，环氧煤沥青加玻璃布的防腐层已经在很多行业开始由其他新型防腐材料所代替。石油天然气行业已经开始使用无溶剂涂料替代环氧煤沥青涂料，并且不再使用玻璃布结构。  \n\n表3-3-53 防腐层等级与结构  \n\n\n<html><body><table><tr><td>等级</td><td>结构</td><td>干膜厚度/mm</td></tr><tr><td>普通级</td><td>底漆-面漆-面漆-面漆</td><td>≥0.30</td></tr><tr><td>加强级</td><td>底漆-面漆-面漆、玻璃布、面漆-面漆</td><td>≥0.40</td></tr><tr><td>特加强级</td><td>底漆-面漆-面漆、玻璃布、面漆-面漆、玻璃布、面漆-面漆</td><td>≥0.60</td></tr></table></body></html>\n\n注：“面漆、玻璃布、面漆”应连续涂覆，也可用一层浸满面漆的玻璃布代替。  \n\nSY/T0061—2004中规定长输管线不宜选用溶剂涂料，但是在石化工厂内的埋地管道实践中采用的外防腐方案还有环氧沥青涂料、高固体分厚浆型环氧涂料、无溶剂酚醛环氧涂料等。这些涂层可能不适合于长输管线的施工应用，但是对于石化厂区的小规模管道防腐蚀施工，可以在现场进行，十分方便灵活。美国ANSI/AWWAC210—1997《钢质水管线的内外液态环氧涂层系统》可以作为相应的参考标准使用。  \n\n高固体分厚浆型环氧涂料与环氧煤沥青相比，不含沥青类致癌物、浅色、易于控制施工质量、便于维修检查、一次施工干膜厚度达 $200{\\sim}400\\mu\\mathrm{m}$ 、厚膜型施工两道即可达到规定的干膜厚度。加入铝粉或玻璃鳞片等片状防锈颜料，加强了涂膜的耐腐蚀性能。表3-3-54为高固体分环氧涂料防腐层等级。  \n\n表3-3-54 高固体分环氧涂料防腐层等级  \n\n\n<html><body><table><tr><td>等级</td><td colspan=\"2\">结构</td><td>干膜厚度/μm</td></tr><tr><td>普通级300μm</td><td>第1道 第2道</td><td>高固体分环氧涂料 高固体分环氧涂料</td><td>150 150</td></tr><tr><td>加强级400μm</td><td>第1道 第2道</td><td>高固体分环氧涂料 高固体分环氧涂料</td><td>200 200</td></tr><tr><td>特加强级600μm</td><td>第1道 第2道</td><td>高固体分环氧涂料 高固体分环氧涂料</td><td>300 300</td></tr></table></body></html>  \n\n无溶剂酚醛环氧涂料是高耐久性的、耐化学品、耐热性优良的涂料，性能好于传统无溶剂环氧涂料。长输管线外防腐主要使用的熔结型环氧和三层聚乙烯涂层，使用温度范围在$100{\\sim}120^{\\circ}C$ ，很多管线在加工操作时温度都超过了 $100^{\\circ}C$ ，有些情况下达到 $160^{\\circ}C$ 。无溶剂酚醛环氧涂料与无溶剂环氧涂料相比，提高了耐久性；增强了耐化学品性能，尤其是增强了耐高温性能。在管道修复时，由于盐分和潮湿环境，以及回填对涂层磨损冲击破坏等，现有的涂层并不适应这种严酷的腐蚀环境。  \n\n无溶剂酚醛环氧具有优异的耐热性能、优异耐久性能和优异的高温下耐阴极剥离性能，适用于加热底材表面，单道施工干膜厚度600～1200um，具有优异的耐化学品性能。温度在70～80℃时，采用传统的喷涂方式或行走喷涂机都能适应。对于操作温度超过100℃(212F，高达到160℃（320°F）的管道来说，无溶剂酚醛环氧涂料是很好选择。该涂料系统的关键是可以满足其耐热性的要求，还包括管道加工厂施工速率、涂层道数、施工中的安全和健康问题以及施工的方便性等。快干型无溶剂酚醛环氧可以施工到温度90℃的底材表面， $10\\mathrm{min}$ 后即可搬运。该产品通过双组分喷漆泵施工。  \n\n聚脲防腐涂层有着优异的物理性能、防腐性能和施工性能：固化快，几秒钟即可凝结十燥，管道连续喷涂不流淌，下管时间短，涂层无需烘烤，适宜于流水线高效率生产； $100\\%$ 固体含量，没有挥发性有机物，符合环保要求；涂层致密，无接缝，耐介质性能突出，适用于沼泽、水塘、原油、石方区等强腐蚀环境下使用；机械强度高，搬运、吊装过程中不易损伤；无需底漆，可以直接喷涂在喷砂到Sa2.5级的钢材表面；使用温度范围宽，可在$-50{\\sim}150^{\\circ}C$ 内长期使用；介电强度高达 $25\\mathrm{{kV/mm}}$ ；与阴极保护配套性良好；补口性能优良。  \n\n聚脲弹性体涂层按埋地管道防腐层的检测要求所测得的技术性能指标见表3-3-55。  \n\n表3-3-55 聚脲弹性体性能指标  \n\n\n<html><body><table><tr><td>项 目</td><td>性能指标</td><td>试验标准</td><td></td></tr><tr><td>拉伸强度/MPa</td><td>≥20</td><td>GB/T 1040</td><td></td></tr><tr><td>断裂伸率/%</td><td>≥350</td><td>GB/T 1040</td><td></td></tr><tr><td>脆化温度/℃</td><td>≥-50</td><td>GB/T 5470</td><td></td></tr><tr><td>电气强度/（MV/m）</td><td>≥25</td><td>GB/T 1408.7</td><td></td></tr><tr><td>体积电阻率/Ω·m</td><td>>1×101²</td><td>GB/T 1410</td><td></td></tr><tr><td>耐紫外线老化（336h）/%</td><td>≥80</td><td>SY/T 0413—2002</td><td>附录E</td></tr><tr><td>耐磨性能(CS17滚轮，负重1kg/1000r）/mg</td><td>≤100</td><td>ASTMD 4060</td><td></td></tr><tr><td>吸水性/%</td><td>≤3.0</td><td>ASTMD 570</td><td></td></tr><tr><td>剥离强度/（N/cm）</td><td></td><td>SY/T 0413—2002</td><td>附录G</td></tr><tr><td>20℃±5℃</td><td>≥70</td><td></td><td></td></tr><tr><td>50℃±5℃</td><td>≥50</td><td></td><td></td></tr><tr><td>阴极剥离（65CX48h）/mm</td><td>≤8</td><td>SY/T 0413—2002</td><td>附录H</td></tr><tr><td>冲击强度/（J/mm）</td><td>>8</td><td>SY/T 0413—2002</td><td>附录H</td></tr><tr><td>抗弯曲/2.5o</td><td>聚脲层无开裂</td><td>SY/T 0413—2002</td><td>附录』</td></tr><tr><td>压痕硬度（23℃±2℃）/mm</td><td>≤0.2</td><td>SY/T 0413—2002</td><td>附录F</td></tr></table></body></html>\n\n注：SY/T4013一1995《埋地钢质管道聚乙烯防腐层技术标准》。  \n\n美国水工协会规范AWWAC222—1999推荐的管道外防腐层聚脲涂层的厚度见表3-3-56。  \n\n表3-3-56 聚脲涂层厚度推荐  \n\n\n<html><body><table><tr><td>涂层级别</td><td>最小厚度/μm</td><td>涂层级别</td><td>最小厚度/μm</td></tr><tr><td>普通级 加强级</td><td>650 1500</td><td>特加强级</td><td>2000</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 179,
+        "chunk": "# 三、建筑钢结构防腐蚀涂料  \n\n市政公共设施，如大型的会展中心、体育场馆、机场航站楼、电视塔、桥梁等，都会使用到大量的钢材，以钢结构作为主要的结构形式。钢铁是现代建筑中重要的结构材料，强度高、性能稳定、韧性好、加工制作方便、适合于批量生产，并且易于控制质量、安装迅速。  \n\n一般城市环境中汽车排放的尾气、电厂以及锅炉烟肉排放的含硫烟气等；工业城市的工业大气污染，海滨城市的盐雾侵蚀；南方的城市湿热等，这些因素必然会导致钢结构遭受腐蚀。采用防腐蚀涂料进行市政公共设施建筑钢结构涂装保护是经济可行的方法，可以达到15年以上的使用寿命，如果采用金属热喷涂与重防腐涂料双重保护，可以达到25年以上的使用寿命。  \n\n防腐蚀涂料在市政公共设施建筑钢结构方面的应用，不仅要考虑到长期的使用寿命以及美观装饰性，同时还要考虑到环境保护。用于钢结构的重防腐涂料要体现性能、美感和环保法规这三者之间的最佳结合。",
+        "category": " Introduction"
+    },
+    {
+        "id": 180,
+        "chunk": "# 1.防锈底漆的选用  \n\n钢结构防腐蚀涂装体系中，防锈底漆的作用至关重要，它要对钢材有良好的附着力，并能起到优异的防锈作用。常用的防锈底漆有富锌底漆和厚浆型环氧涂料等。  \n\n（1）富锌底漆富锌漆由于富含锌粉，对钢材基底有阴极保护作用，因此是首选的防锈底漆。富锌底漆在钢结构防腐方面，目前主要有三个重要类型：环氧富锌底漆、醇溶性无机富锌底漆和水性无机富锌底漆。  \n\n$\\textcircled{1}$ 富锌底漆中锌粉的规定  \n\na.锌粉含量的要求对富锌底漆中的锌粉含量，不同国家和地区有着不同的规范要求。  \n\nBS4652：1995中规定，干漆膜中锌粉含量不能低于 $85\\%$ （质量分数）。  \n\nISO12944-5：1998，5.2条文中规定，富锌底漆，无论是有机还是无机，不挥发分中锌粉含量不得低于 $80\\%$ （质量分数），锌粉标准要符合ISO3549的规定。  \n\n$\\mathrm{HG/T3668{\\overline{{-2000}}}}$ ：不挥发分中的金属锌含量的规定，无机富锌底漆不低于 $80\\%$ ，有机富锌底漆不低于 $70\\%$  \n\nSSPCSSPC-Paint20：2002中规定两类富锌底漆，类型I为无机富锌漆，类型Ⅱ为有机富锌，并且按干膜中的锌粉重量规定了三类涂料：Level1等于或大于 $85\\%$ ；Level2等于或大于 $77\\%$ ，少于 $85\\%$ ；Level3等于或大于 $65\\%$ ，少于 $77\\%$ 。这些涂料中的主要颜料成分必须是ASTMD520所规定的金属锌粉的要求。  \n\nb．锌粉的要求用于涂料中的锌粉不可能是 $100\\%$ 的纯金属锌，它会含有一定的氧化锌、氧化铅和其他非金属成分和金属元素。按 $\\mathrm{GB}/\\mathrm{T}~6890{-2000}$ ，其化学成分见表3-3-57。  \n\n表3-3-57 锌粉的化学成分  \n\n\n<html><body><table><tr><td rowspan=\"3\">等级</td><td colspan=\"6\">化学成分/%</td></tr><tr><td colspan=\"2\">主品位≥</td><td colspan=\"4\">杂质≤</td></tr><tr><td>全锌</td><td>金属锌</td><td>Pb</td><td>Fe</td><td>Cd</td><td>酸不溶物</td></tr><tr><td>一级</td><td>98</td><td>96</td><td>0.1</td><td>0.05</td><td>0.1</td><td>0.2</td></tr><tr><td>二级</td><td>98</td><td>94</td><td>0.2</td><td>0.2</td><td>0.2</td><td>0.2</td></tr><tr><td>三级</td><td>96</td><td>92</td><td>0.3</td><td>二</td><td></td><td>0.2</td></tr><tr><td>四级</td><td>92</td><td>88</td><td>一</td><td>一</td><td>二 一</td><td>0.2</td></tr></table></body></html>  \n\nc.锌粉中的铅含量标准ASTMD520对作为涂料颜料的金属锌粉规定了3个种类。种类I中铅含量最大限量没有规定，为通用等级；种类Ⅱ规定铅含量的质量比不大于$0.01\\%$ ，为高纯度级；种类Ⅲ规定铅含量的质量比不大于 $0.002\\%$ ，属最高纯度级。  \n\n$\\textcircled{2}$ 环氧富锌底漆环氧富锌底漆以环氧树脂为基料，以聚酰胺为固化剂，以超细锌粉  \n\n为主要防锈颜料。加人一定量的铝银浆和氧化铁红，可以增加耐候性能，防止锌盐的产生。  \n典型的环氧富锌底漆配方见表3-3-58。  \n\n表3-3-58环氧富锌底漆的基本配方 单位：质量份  \n\n\n<html><body><table><tr><td rowspan=\"5\">A组分</td><td rowspan=\"5\">环氧树脂 钾长石粉 锌粉</td><td>8~10</td><td>A组分</td><td>溶剂</td><td>11~12</td></tr><tr><td></td><td>6~7 57~61</td><td>助剂 溶剂</td><td>0~1</td></tr><tr><td></td><td>Q~1 B组分</td><td></td><td>4~5</td></tr><tr><td>氧化铁红</td><td></td><td>聚酰胺固化剂</td><td>4~6</td></tr><tr><td>铝银浆</td><td>0~1</td><td></td><td></td></tr></table></body></html>  \n\n$\\textcircled{3}$ 醇溶性无机富锌底漆与环氧富锌底漆相比较，无机富锌底漆在耐热、耐溶剂、耐化学品性能以及导静电方面有着更为优异的性能。典型的醇溶性无机富锌底漆的配方见表3-3-59。  \n\n表3-3-59 典型的醇溶性无机富锌底漆  \n\n\n<html><body><table><tr><td rowspan=\"3\">A组分</td><td></td><td></td><td rowspan=\"3\"></td><td></td><td>7~9</td></tr><tr><td>硅酸乙酯</td><td>22~26</td><td>云母粉 A组分</td><td></td></tr><tr><td>酸</td><td>0. 1~0.2</td><td>溶剂</td><td>32~36</td></tr><tr><td rowspan=\"2\"></td><td>水</td><td>2~3</td><td rowspan=\"2\">B组分</td><td>助剂</td><td>0.5~0.8</td></tr><tr><td>高岭土</td><td>7~9</td><td>锌粉</td><td>20~25</td></tr></table></body></html>  \n\n无机富锌底漆的施工要求很高。钢材表面必须喷砂到 $\\operatorname{Sa2.5}$ 。醇溶性无机富锌底漆的固化是通过吸收空气中水分进行水解缩聚反应来完成的，因此无机富锌底漆在喷涂后，空气中的相对湿度最好保持在 $65\\%$ 以上。无机富锌必须在完全固化后才能涂覆后道漆，否则会引起涂膜层间分离。  \n\n无机富锌底漆表面呈多孔性，喷涂后道涂层前要求使用专门的封闭漆或采用雾喷技术。无机富锌底漆对于漆膜厚度有着严格的要求，过高的干膜厚度会导致漆膜开裂，醇溶性无机富锌底漆通常认为 $125\\mu\\mathrm{m}$ 以下安全的，水性无机富锌底漆膜厚度可以高至 $150{\\sim}200\\mu\\mathrm{m}$ ，这取决于涂料厂家的配方技术。  \n\n$\\textcircled{4}$ 水性无机富锌底漆水性无机富锌涂料，以水代替溶剂和稀释剂，不含任何有机挥发物，无毒，无闪火点，对施工人员的损害明显比溶剂型无机富锌涂料低，对环境污染小，VOC为零，没有火灾危险，在施工、贮存和运输过程中较为安全。  \n\n水性无机富锌底漆，利用空气中的二氧化碳和湿气与硅酸钾进行反应，在生成碳酸盐的同时，锌粉也同硅酸钾充分反应生成硅酸锌高聚物。其固化受温度和湿度的影响较大。水性无机富锌底漆要求喷砂到Sa3。  \n\n(2）环氧防锈底漆厚浆型改性环氧涂料也是重要的防锈底漆，它们通常含有磷酸锌或铝粉等防锈颜料，漆膜坚固耐久，对钢材的附着力强。这些产品已经在海洋环境下应用了几十年，具有很好的防腐蚀性能。  \n\n环氧磷酸锌防锈底漆的典型配方见表3-3-60。  \n\n单位：质量份  \n表3-3-60典型的环氧磷酸锌防锈漆配方  \n\n\n<html><body><table><tr><td rowspan=\"2\"></td><td rowspan=\"2\">环氧树脂</td><td rowspan=\"2\"></td><td rowspan=\"2\">19～20</td><td rowspan=\"2\">A组分</td><td rowspan=\"2\"></td><td>19~21</td></tr><tr><td>溶剂 助剂</td></tr><tr><td rowspan=\"3\">A组分</td><td>滑石粉</td><td></td><td>22～23</td><td rowspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\">1~2 5~7</td></tr><tr><td>磷酸锌</td><td></td><td>8~9</td><td>溶剂</td></tr><tr><td>氧化铁红</td><td></td><td>7~9</td><td>B组分</td><td>聚酰胺固化剂</td><td>13~15</td></tr></table></body></html>  \n\n单位：质量份  \n\n碳氢树脂改性的环氧树脂涂料有普通型、铝粉型和玻璃鳞片增强型等多种产品，单道喷涂可以达到 $100{\\sim}400\\mu\\mathrm{m}$ 的干膜厚度。典型的碳氢树脂改性环氧涂料见表3-3-61。  \n\n表3-3-61 典型的碳氧树脂改性环氧涂料  \n单位：质量份  \n\n\n<html><body><table><tr><td rowspan=\"7\">A组分</td><td>环氧树脂</td><td>18~22</td><td rowspan=\"2\"></td><td rowspan=\"2\">氧化铁红</td><td rowspan=\"2\">2~3</td></tr><tr><td></td><td></td></tr><tr><td>石油碳氢树脂</td><td>8~10</td><td rowspan=\"2\">A组分 B组分</td><td>助剂</td><td>0.5~1</td></tr><tr><td>钾长石粉 滑石粉</td><td>32~36 8~10</td><td>溶剂 聚酰胺固化剂</td><td>13~17 8~12</td></tr></table></body></html>  \n\n以改性酚醛胺为固化剂的通用耐磨环氧漆，作为真正的通用环氧防锈漆，它可以一年四季使用而无需在冬天采用低温固化剂，对于车间底漆表面、钢材、铝材、不锈钢、镀锌和热喷涂金属表面等都有良好的附着力，并且可以用醇酸、环氧、丙烯酸、聚氨酯等面漆覆涂。该产品通过 $4200h$ 的盐雾、紫外线循环试验，被认为是不需要采用富锌底漆而可以达到15年以上使用寿命的重防腐涂料。典型配方见表3-3-62。  \n\n<html><body><table><tr><td rowspan=\"3\">A组分</td><td>环氧树脂</td><td>29~33</td><td rowspan=\"3\"></td><td>溶剂</td><td>9~10</td></tr><tr><td>钾长石粉</td><td>32~36</td><td>A组分 助剂</td><td>1~2</td></tr><tr><td>氧化铁红</td><td>1~2</td><td>腰果壳油固化剂</td><td>17~19</td></tr><tr><td></td><td>铝银浆</td><td>3~4</td><td>B组分</td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 181,
+        "chunk": "# 2.中间漆的选用  \n\n在重防腐蚀涂料系统中，中间漆的主要作用是增加涂层的厚度以提高整个涂层系统的屏蔽性能。最常用的中间漆是环氧云铁中间漆，含有云铁的涂层表面粗糙，易于后道面漆的附着。这样在中间漆完成后，就能把钢结构发运到安装现场，然后在安装完毕后再涂覆面漆。但是粗糙的中间漆表面在灰尘满天飞的施工现场，也会带来后道面漆涂装时清洁的困难，推荐在钢结构预制厂内先完成第一道面漆的施工，因为面漆的表面更为光洁易于清洁。  \n\n对于云母氧化铁在环氧云铁中间漆内的含量，也有一定的要求，根据英国标准BS4652（1995年)，要达到颜料总比例的 $80\\%$ 以上。这样达到一定比例的云母氧化铁含量，进一步加强了涂料的封闭作用，相比与含很少云母氧化铁一般配方的环氧云铁中间漆，防腐蚀作用明显得到了加强。云母氧化铁片状颜料结构在涂膜中的作用如图3-3-49所示。  \n\n![](images/09d8d7ad76b43cecc2cf97e26af83c143851f7dd30769a33989995fd9b700a8e.jpg)  \n图3-3-49云母氧化铁（片状颜料）对腐蚀介质渗透的良好阻隔作用  \n\n表3-3-63为典型的环氧云铁中间漆配方，供参考。  \n\n表3-3-62 典型通用环氧通用底漆配方 单位：质量份  \n表3-3-63 典型的环氧云铁中间漆配方  \n单位：质量份  \n\n\n<html><body><table><tr><td rowspan=\"7\">A组分</td><td>环氧树脂</td><td>18~20</td><td></td><td>云母氧化铁</td><td>12~13</td></tr><tr><td>氧化铁红</td><td></td><td>A组分</td><td>溶剂</td><td>12~14</td></tr><tr><td></td><td>2~3</td><td></td><td></td><td></td></tr><tr><td>滑石粉</td><td>21~23</td><td></td><td>助剂</td><td>1</td></tr><tr><td>硫酸钡</td><td>9~10</td><td>B组分</td><td>聚酰胺固化剂</td><td>19~21</td></tr></table></body></html>  \n\n早期使用的环氧云铁中间漆的固体分在 $50\\%$ 左右，现在新推出应用的环氧云铁中间漆都在 $65\\%$ 左右，甚至 $80\\%$ 以上，这样溶剂含量比原来减少了 $15\\%\\sim30\\%$ 。高固体分环氧云铁中间漆在施工时，可以单道涂层喷涂达到 $100\\sim200\\mu\\mathrm{m}$ 的干膜厚度，而原先的低固体分的环氧云铁中间漆，一道喷涂只能达到 $50\\mu\\mathrm{m}$ 的干膜厚度。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 182,
+        "chunk": "# 3.面漆的选用  \n\n面漆的主要作用是遮蔽太阳紫外线以及污染大气对涂层的破坏作用，抵挡风雪雨水，并且要有很好的美观装饰性。钢结构表面高耐候性的防腐蚀面漆，目前使用的主要有丙烯酸聚氨酯面漆、氟碳面漆以及有机改性聚硅氧涂料等类。  \n\n(1）丙烯酸聚氨酯面漆羟基丙烯酸树脂与脂肪族多异氰酸酯预聚物配合，可以制成色浅、保光保色性优、户外耐候性好的高装饰性丙烯酸聚氨酯面漆。由于丙烯酸聚氨酯面漆没有最大重涂间隔，所以有些涂料厂家直接将其称为可覆涂聚氨酯面漆，丙烯酸聚氨酯面漆是目前钢结构防腐蚀体系中应用最为广泛的面漆。表3-3-64为典型的丙烯酸聚氨酯面漆配方，供参考。  \n\n表3-3-64典型的丙烯酸聚氨酯面漆配方 单位：质量份  \n\n\n<html><body><table><tr><td rowspan=\"4\">A组分</td><td>羟基丙烯酸树脂</td><td>44~49</td><td>A组分</td><td></td><td>1~2</td></tr><tr><td></td><td></td><td>助剂</td><td></td><td></td></tr><tr><td>钛白粉</td><td>23~27</td><td>B组分</td><td>溶剂</td><td>1~2</td></tr><tr><td>溶剂</td><td>16~20</td><td></td><td>异氰酸酯</td><td>7~8</td></tr></table></body></html>  \n\n(2）氟碳面漆以FEVE（聚氟乙烯/乙烯基醚）可溶性含氟聚合物为主要基料的氟碳面漆，可以保护下层涂料并且防止紫外线辐射。高键能的C一F键达到 $485\\mathrm{kJ/mol}$ ，比典型的有机聚合物的C—C键的键能 $358\\mathrm{kJ/mol}$ 要强得多。这意味着要更强的活化能才能破坏含氟聚合物。FEVE能用氟乙烯和乙烯基醚溶液共聚而成，给予涂料溶剂可溶性、透明度、光泽、硬度和柔韧性等。从有机溶剂的可溶性的角度来看，三氟氯乙烯（CTFE）由氟乙烯共聚而成。聚合物的羟基官能团能很容易地由羟基烷基乙烯基醚来制备，使其可以与异氰酸酯和三聚氰胺固化剂进行交联。表3-3-65为高光、亚光白色氟碳漆及氟碳清漆配方，供参考。  \n\n表3-3-65高光、亚光白色氟碳漆及氟碳清漆配方 单位：质量份  \n\n\n<html><body><table><tr><td colspan=\"2\">配 方</td><td>高光白色氟碳漆</td><td>亚光白色氟碳漆</td><td>氟碳清漆</td></tr><tr><td colspan=\"2\">氟碳树脂 溶剂乙酸丁酯</td><td>68.9</td><td>67.0</td><td>98.0</td></tr><tr><td rowspan=\"6\">颜料</td><td>消光剂</td><td>3.5</td><td>4.5 4.5</td><td>一</td></tr><tr><td>助剂1</td><td>一</td><td>0.3</td><td>一 一</td></tr><tr><td>助剂2</td><td>一 1. 1</td><td>1.2</td><td>0.5</td></tr><tr><td>助剂3</td><td>0.5</td><td>0.5</td><td></td></tr><tr><td>助剂4</td><td></td><td></td><td></td></tr><tr><td>金红石型钛白粉</td><td>1.0 25.0</td><td>1.0 25.0</td><td>1.5</td></tr><tr><td>固化剂配比</td><td>异氰酸酯</td><td>10:1</td><td>12:1</td><td>一 8:1</td></tr></table></body></html>  \n\n(3）聚硅氧烷涂料有机改性的聚硅氧烷涂料技术与聚氨酯和氟聚合物面漆相比，是低黏度、低VOC、无异氰酸酯、高耐候性的防腐面漆产品。聚硅氧烷涂料中的硅-氧键已经氧化使得它们可以耐受大气中的氧气和大多数氧化物的作用。聚硅氧烷的硅-氧键，键能高达$445\\mathrm{kJ/mol}$ ，大大高于有机聚合物典型的碳-碳键的键能 $358\\mathrm{kJ/mol}$ 。这意味着需要更强的活化能才能破坏聚硅氧烷聚合物。因此，聚硅氧烷面漆具有天性的耐大气和化学性破坏的性能。第一代商品化的聚硅氧烷面漆以氢化的环氧树脂进行改性，随后发展了第二代丙烯酸氨基甲酸乙酯和丙烯酸改性的聚硅氧烷产品。聚硅氧烷树脂的黏度很低，可以使得环氧和丙烯酸聚硅氧烷涂料有着很高的固体分。环氧聚硅氧烷涂料的体积固体分高达90%，VOC为120g/L（EPAmethod 24)。丙烯酸聚硅氧烷涂料的体积固体分设计高达72%，VOC 为$240\\mathrm{g/L}$ 。表3-3-66为典型的环氧聚硅氧烷涂料配方，供参考。  \n\n<html><body><table><tr><td rowspan=\"5\">A组分</td><td>硅氧烷树脂</td><td rowspan=\"5\">62~66 1~2</td><td rowspan=\"2\">A组分</td><td>气态硅</td><td>0.8～1.2</td></tr><tr><td>蓝颜料</td><td>溶剂</td><td>适量</td></tr><tr><td>钛白粉</td><td>B组分</td><td>氨基硅烷</td><td>5~8</td></tr><tr><td>滑石粉</td><td>22~26 2~3</td><td>聚胺</td><td>4~6</td></tr><tr><td>抗气剂</td><td>0.3~0.6</td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 183,
+        "chunk": "# 4.钢结构涂装设计  \n\n钢结构的防腐蚀涂装规格主要根据ISO12944来制订。ISO12944是目前全球公认的权威性标准，它是国际标准化组织为从事涂料防腐蚀工作的业主、设计人员、咨询顾问、涂装承包商、涂料生产企业等汇编的标准，为这些人员、单位和组织机构提供了重要的参考。  \n\n表3-3-66环氧聚硅氧烷涂料配方 单位：质量份  \n\n\n<html><body><table><tr><td rowspan=\"2\">腐蚀等级</td><td colspan=\"2\">典型环境(仅作参考)</td></tr><tr><td>外部</td><td>内部</td></tr><tr><td>C1 很低</td><td></td><td>在空气洁净的环境下有供暖设施的建筑，如办公室、商 店、学校和宾馆内部</td></tr><tr><td>C2 低</td><td>轻度的大气污染，大部分是乡村地带</td><td>有冷凝发生，没有供热设施的地方，如库房，体育馆等</td></tr><tr><td>C3 中</td><td>城市和工业大气，中等的二氧化硫污染，低 盐度沿海区域</td><td>高湿度和有些污染空气的生产场所，如食品加工厂、洗 衣场、酒厂、牛奶场等</td></tr><tr><td>C4 高</td><td>高盐度的工业区和沿海区域</td><td>化工厂、游泳池、海船和船厂等</td></tr><tr><td>C5-I 很高(工业)</td><td>高湿度和侵蚀性大气的工业区域</td><td>总是有冷凝和高湿度的建筑和区域</td></tr><tr><td>C5-M 很高（海洋）</td><td>高盐度的沿海和离岸地带</td><td>总是处于高湿、高污染的建筑物或其他区域</td></tr></table></body></html>  \n\nISO12944全面介绍了钢结构防护涂装中的所有要求，包括设计寿命、腐蚀环境、结构设计、表面处理、涂层体系、涂料产品性能、施工监理以及新建维修配套方案的制订等内容。在钢结构防腐蚀涂料系统设计时，ISO12944主要有三个步骤来完成。首先是判断钢结构的腐蚀环境，其次就是确定防腐涂层要求的使用年限，最后就是确定防腐涂层配套方案，包括产品类型和漆膜厚度。  \n\n(1）腐蚀环境的确定ISO12944-2中定义的腐蚀环境是制订防腐蚀涂装系统的指导，见表3-3-67。作为公共设施的大部分的建筑钢结构，例如体育馆、会展中心等，都处在$\\mathrm{C2\\sim\\tilde{C4}}$ 的环境中。冶金石化企业和海洋工程钢结构通常处于高腐蚀的C5-I和C5-M环境。  \n\n(2）防腐涂料系统的设计使用寿命ISO12944-1中对防腐涂料系统的设计使用寿命划分了三个耐久性范围，见表3-3-68。  \n\n表3-3-67 腐蚀定义和环境（ISO12944-2）  \n表3-3-68 涂料系统耐久性范围  \n\n\n<html><body><table><tr><td>序号</td><td>耐久性</td><td>设计寿命</td><td>序号</td><td>耐久性</td><td>设计寿命</td></tr><tr><td>1</td><td>低耐久性</td><td>5年以下</td><td>3</td><td>高耐久性</td><td>15年以上</td></tr><tr><td>2</td><td>中耐久性</td><td>5~15年</td><td></td><td></td><td></td></tr></table></body></html>  \n\n钢结构建筑要求有着较高的使用寿命，因此对于涂料系统来说，也要求具有高耐久性的使用寿命。所以对于钢结构建筑的涂装设计都是在15年以上，甚至25年以上的重防腐涂装系统。  \n\n(3）涂料系统和漆膜厚度在ISO12944-5中，对现有涂料和涂料体系的使用进行了重要定义。ISO12944-5在附录A中表格 $1{\\sim}8$ 中举例说明了基于不同黏结剂、防锈颜料、干膜厚度，配合使用的底漆、中间漆和面漆。表3-3-69列举了对应于C4腐蚀环境下，建筑钢结构在不同设计寿命下的不同涂料体系及其膜厚的对应关系。  \n\n在C4或C5腐蚀环境下，推荐使用富锌底漆，ISO12944标准中规定锌粉含量不能低于$80\\%$ （质量分数)，锌粉颜料必须满足ISO3549的要求。  \n\n在ISO12944-5中，限于制订标准时的涂料技术和涂料系统方案的取舍，不可能把所有的涂料类别都列举出来，比如环氧酯涂料和氨酯醇酸树脂、氟碳和聚硅氧烷涂料等便没有在这里体现出来。  \n\n对于漆膜厚度是根据腐蚀环境以及所期望的使用寿命来确定的，见表3-3-70。这里没有列出C1环境中的涂料系统，是因为在这种环境下腐蚀性很低，其他任何规定的涂层系统都足以对钢结构做出长久性保护。  \n\n表3-3-69ISO12944-5中对应C4的耐久性涂料系统举例  \n\n\n<html><body><table><tr><td rowspan=\"2\">编 号</td><td rowspan=\"2\">表面 处理</td><td colspan=\"3\">底漆</td><td colspan=\"3\">中间漆和面漆</td><td colspan=\"3\">涂料系统</td><td colspan=\"3\">期望的使用寿命 ISO 12944-1</td></tr><tr><td>基 料</td><td>类 型</td><td>涂层数</td><td>NT /μm</td><td>基 料</td><td>涂层数 /层</td><td>NDFT /μm</td><td>涂层数 /层</td><td>总膜</td><td>低 L</td><td>中 M</td><td>高 H</td></tr><tr><td>IS4.19</td><td>Sa 2.5 Sa 2.5</td><td rowspan=\"4\"></td><td rowspan=\"4\">Zn</td><td>１</td><td>40</td><td rowspan=\"4\">EP,</td><td>1~2</td><td>120</td><td>2~3</td><td>/μm 160</td><td></td><td></td><td></td></tr><tr><td>IS4.20</td><td>EP，</td><td>１</td><td>40</td><td>2~3</td><td>160</td><td>3~4</td><td>200</td><td></td><td></td><td></td></tr><tr><td></td><td>PUR Sa 2.5</td><td></td><td></td><td>PUR</td><td>2~3</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>IS4.21</td><td></td><td>1</td><td>40</td><td></td><td></td><td>200</td><td>3~4</td><td>240</td><td></td><td></td></tr></table></body></html>\n\n注：1.EP，环氧；PUR，聚氨酯； $z_{\\Pi}$ ，锌粉。2.环氧富锌或聚氨酯富锌底漆的膜厚可以设计为 $80\\mu\\mathrm{m}$  \n\n表3-3-70ISO12944中腐蚀环境、使用寿命和漆膜厚度的关系  \n\n\n<html><body><table><tr><td>腐蚀环境</td><td>使用寿命</td><td>干膜厚度/μm</td><td>腐蚀环境</td><td>使用寿命</td><td>干膜厚度/μm</td></tr><tr><td rowspan=\"3\">C2</td><td>低</td><td>80</td><td rowspan=\"3\">C4</td><td>低</td><td>160</td></tr><tr><td>中</td><td>120</td><td>中</td><td>200</td></tr><tr><td>高</td><td>200</td><td>高</td><td>240（含锌粉）</td></tr><tr><td rowspan=\"3\">C3</td><td>低</td><td>120</td><td>C5-I</td><td>低</td><td>280(不含锌粉） 200</td></tr><tr><td>中</td><td>160</td><td>C5-M</td><td>中</td><td>280</td></tr><tr><td>高</td><td>200</td><td></td><td>高</td><td>320</td></tr></table></body></html>\n\n注：使用含锌底漆时，锌粉含量不能低于 $80\\%$ （质量分数）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 184,
+        "chunk": "# 5.钢结构的金属热喷涂  \n\n许多大型钢结构的设计使用寿命要求在50年，甚至80年以上，单一的涂料体系是不可能达到这样的要求的。在室外大气腐蚀环境下，对钢结构进行热喷涂锌或铝涂层，结合涂料封闭，是保护钢结构长期无维护或少维护的唯一最好方法。  \n\n在腐蚀环境下，锌或铝涂层作为阳极被腐蚀，其腐蚀产物会覆盖在涂层表面，起到封闭作用。因此，热喷涂锌或铝涂层既有阴极保护作用，还会起到屏蔽作用，确保了当涂层发生破损时，能牺牲金属喷涂层，可达到20年免维护，40年少维护的有效保护。  \n\n对于金属热喷涂以及无机富锌底漆，要分别施工一道环氧封闭漆/连接漆，干膜厚度约在30um。封闭漆/连接漆的主要作用是对金属热喷涂和无机富锌底漆的多孔表面进行渗透封闭，起到防止起泡针孔的作用，也为后续中间涂层起到了良好的连接作用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 185,
+        "chunk": "# 6.钢结构重防腐涂装体系  \n\n一个复杂的有着几千甚至上万吨的钢结构建筑，要制订一个满足多方要求的防腐蚀体系是较为困难的。它涉及涂料的防腐蚀耐久性、涂层的快速干燥性、方便的施工性和绿色环保等。  \n\n对钢结构的防锈处理，采取金属热喷涂的方法，喷锌、喷铝或喷锌铝合金等方式，达到  \n\n20年以上的防腐蚀使用寿命；采用富锌底漆、无机富锌或环氧富锌底漆，干膜厚度$50\\sim80\\mu\\mathrm{m}$ ，可以达到15年以上的防腐蚀使用寿命；对于C3或C4腐蚀环境，选用重防腐厚浆型环氧涂料，干膜厚度在 $200\\mu\\mathrm{m}$ 以上，无需采用中间涂层，也可以达到15年以上的使用寿命。  \n\n高性能面漆的选用目前主要有三种类别：经济有效的丙烯酸聚氨酯面漆、超耐候性的氟碳面漆以及耐候性优异且环保的聚硅氧烷面漆。干膜厚度在 $60\\sim100\\mu\\mathrm{m}$ 之间选用。  \n\n![](images/26e31c96b915cb903826b4c099690d9e0de9e0476893b103f54e08fac587aa47.jpg)  \n图3-3-50 重防腐涂装体系  \n\n重防腐涂装体系中底漆、中间漆和面漆的选用如图3-3-50所示。  \n\n以ISO12944-2C4腐蚀环境为例，依据ISO12944-5，表3-3-71介绍了不同腐蚀环境下的防腐蚀涂装体系，使用寿命在15年以上。其中采用金属热喷涂的方案，可以达到25年以上免维护或少维护的使用寿命。腐蚀等级高的防腐蚀涂料体系用于腐蚀等级低的环境下，可以相应延长使用寿命；同样，膜厚高的防腐蚀涂料体系用于腐蚀等级低的环境下，也可以相应延长使用寿命。  \n\n表3-3-71 钢结构重防腐涂装体系  \n\n\n<html><body><table><tr><td rowspan=\"2\">腐蚀环境</td><td colspan=\"3\">ISO12944C4（沿海腐蚀环境）</td></tr><tr><td>涂层</td><td>涂料产品</td><td>干膜厚度/μm</td></tr><tr><td rowspan=\"3\">涂层系统 金属热喷涂体系</td><td>金属喷涂</td><td>锌、铝或锌铝合金</td><td>120~160</td></tr><tr><td>封闭漆</td><td>环氧封闭漆</td><td>不计厚度</td></tr><tr><td>中间漆</td><td>环氧云铁中间漆</td><td>100</td></tr><tr><td rowspan=\"3\"></td><td>面漆</td><td>脂肪族聚氨酯面漆</td><td>80</td></tr><tr><td>底漆</td><td>环氧富锌底漆</td><td>75</td></tr><tr><td>中间漆</td><td>厚浆型环氧云铁中间漆</td><td>125</td></tr><tr><td rowspan=\"3\">无机富锌重防腐体系</td><td>面漆</td><td>脂肪族聚氨酯面漆</td><td>80</td></tr><tr><td>底漆</td><td>无机富锌底漆</td><td>80</td></tr><tr><td>封闭漆 中间漆</td><td>环氧封闭漆 厚浆型环氧云铁中间漆</td><td>30</td></tr><tr><td rowspan=\"3\"></td><td>面漆</td><td>脂肪族聚氨酯面漆</td><td>100 80</td></tr><tr><td>底漆</td><td>碳氢树脂改性环氧涂料</td><td>2 X100</td></tr><tr><td>面漆</td><td>脂肪族聚氨酯面漆</td><td>80</td></tr><tr><td rowspan=\"3\">环氧重防腐蚀涂料涂装体系</td><td>底漆</td><td>通用环氧涂料</td><td></td></tr><tr><td></td><td></td><td>2X100</td></tr><tr><td>面漆</td><td>脂肪族聚氨酯面漆</td><td>80</td></tr></table></body></html>  \n\n续表  \n\n<html><body><table><tr><td>腐蚀环境</td><td colspan=\"3\">ISO12944C4（沿海腐蚀环境）</td></tr><tr><td rowspan=\"2\">环氧磷酸锌重防腐涂装体系</td><td>底漆</td><td>环氧磷酸锌防锈底漆</td><td>100</td></tr><tr><td>中间漆 面漆</td><td>环氧云铁中间漆</td><td>100 80</td></tr><tr><td rowspan=\"3\">超耐候性涂料系统</td><td>底漆</td><td>脂肪族聚氨酯面漆 环氧富锌底漆</td><td>75</td></tr><tr><td>中间漆</td><td>环氧云铁中间漆</td><td>125</td></tr><tr><td>面漆</td><td>聚硅氧烷涂料/氟碳面漆</td><td>80</td></tr></table></body></html>\n\n注：金属热喷涂表面的封闭漆；渗人金属层内部，因此实际使用中不计漆膜厚度。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 186,
+        "chunk": "# 四、港口机械与设备钢结构防护涂装",
+        "category": " Introduction"
+    },
+    {
+        "id": 187,
+        "chunk": "# 1.概述  \n\n我国现有港口150余个，2005年货物吞吐量达33.8亿吨，比2000年翻了一番多。随着《中华人民共和国港口法》的公布实施，国家加强了对港口建设的规划与管理，保障经济和社会全面协调、可持续发展；目前全国港口布局已形成环渤海、长江三角洲、东南沿海、珠江三角洲和西南沿海5个规模化、集约化、现代化的港口群体，形成煤炭、石油、铁矿石、集装箱、粮食、商品汽车、陆岛滚装和旅客运输8个运输系统。港口建设的繁荣促进了港口机械行业的极大发展。本节仅就港口机械与设备钢结构防护涂装技术简介如下。",
+        "category": " Introduction"
+    },
+    {
+        "id": 188,
+        "chunk": "# 2.港口分类与港口设备的种类  \n\n(1）港口的分类港口从地理位置和自然条件分类有：海港、河口港、河港、湖港、水库港等。按港口业务性质和用途分类有：商港、军港、工业港、渔港、油港等。  \n\n(2）港口设备的种类任何港口的运行需配套大量的港口机械与设备。根据港口的装卸能力和物流模式，所配备的设备类型也不同，可分三大类。  \n\n$\\textcircled{1}$ 集装箱及起重机械设备如集装箱岸桥、集装箱、场桥、轨道吊、轮胎吊、轨道行车、浮式起重机、龙门起重机、固定起重机等。  \n\n$\\textcircled{2}$ 装/卸船机 如装船机、卸船机、斗轮机、吸粮机、卸车机、浮吊等。  \n\n$\\textcircled{3}$ 其他如门机、固定吊、输送机、正面吊运机、跨运车、龙门吊运机、码头牵引车空箱堆高机、叉车等。  \n\n这些港口机械与设备安装并运行在港口，处于沿海大气腐蚀环境之中，某些部位甚至处于浪溅区，做好防腐涂装对确保其使用寿命至关重要。",
+        "category": " Introduction"
+    },
+    {
+        "id": 189,
+        "chunk": "# 3.港口设备所处腐蚀环境的特点  \n\n大型的港口设备通常处于海洋腐蚀环境中，而影响金属材料在海洋环境中腐蚀的因素很多，其中包括化学/电化学的（氧、水分、盐、有机化合物、污染物等）、物理的（温度、流速、压力等）和生物的因素。这些因素的作用常常是相互关联的，它们不但对不同金属的影响不一样，就是在同一海区对同一种金属的影响也因金属所处的部位（沿岸区、飞溅区、潮差区、全浸区、深海区、海泥区）不同而异。  \n\n我国海岸带由于受太平洋海洋动力因素的影响，海岸地形、气候、大陆入海河流等因素影响，形成各自特殊的海洋环境。据国家海洋局近几年的调查资料数据，我国海洋环境条件概述如下。  \n\n(1）气温 海岸带年平均气温从北至南变化在 $8.5{\\sim}25.5^{\\circ}\\mathrm{C}$ (2）日照年日照时数分布：北部多，南部少；海岛多，陆上少。  \n\n(3）降水海岸带濒临东亚季风区，受冬、夏季风及海陆分布和沿岸地形的综合影响，北部降水少，南部降水多；陆上多，海上和海岛少；迎风坡多，背风坡少。(4）湿度海岸带年平均相对湿度，从高纬度向低纬度速增，由陆地向海上速增。相对湿度的年内变化与降水量的年内变化相关，在降水集中季节，湿度增大。(5）盐度沿岸海域的盐度与外海高盐水和沿岸低盐水的消长和交汇有关，还受径流、潮流等影响。沿岸海域年平均盐度为 $28\\%\\sim33\\%$ ，最高月平均盐度为 $33.75\\%$ (海南岛)。(6）溶解氧海水中溶解氧主要来源于大气中氧的溶解，其次来自海洋植物（主要是浮游植物）光合作用产生的氧。海洋生物的呼吸作用和有机物的降解消耗溶解氧。氧在海水中的溶解取决于水温、盐度和大气压力等。海水含氧量受水温控制，冬季高，夏季低，春秋季居中。（7）酸碱度影响海岸带海水 $\\mathbf{pH}$ 的因素有盐度、 $\\mathrm{CO}_{2}$ 含量、浮游植物光合作用、河流径流量、有机质分解反应等。盐度低、 $\\mathrm{CO}_{\\mathrm{2}}$ 含量高、使 $\\mathrm{\\bf{pH}}$ 降低。浮游植物光合作用需要吸取$\\mathrm{CO_{2}}$ ，使海水中 $\\mathrm{CO_{2}}$ 减少，使 $\\mathbf{pH}$ 升高。海岸带海域因为受陆地径流等影响， $\\mathtt{p H}$ 变化较大。(8）潮汐与潮流我国沿海潮汐性质较复杂，各海区存在正规半日潮、不正规半日潮、正规全日潮、不正规全日潮四种类型，但不同海区各种潮汐类型所占主次不同。正规半日潮流每半天涨，落潮流时间大约为6h，正规日潮流每天涨，落潮时间大约各为 $\\mathrm{12h}$ 0  \n\n以上各种环境因素都对港口设备钢结构的大气腐蚀过程产生极大影响。根据ISO12944《钢结构保护涂层腐蚀性环境分类》标准，考虑到中国港口所在的海域特殊的水温、地质、气象条件，建成的港口/码头一般处于ISO12944C4～C5的沿海腐蚀环境中，属于比较严重的腐蚀环境。",
+        "category": " Introduction"
+    },
+    {
+        "id": 190,
+        "chunk": "# 4.港口机械与设备钢结构防护涂层配套体系  \n\n在考虑港口设备钢结构防护方案时，主要遵循以下原则：  \n\n$\\textcircled{1}$ 适合港口设备所处地区的气候条件、环境条件及其工况条件；$\\textcircled{2}$ 确保涂料和涂装技术的科学性及先进性；$\\textcircled{3}$ 技术上的先进性和经济性相结合，达到最佳性能/价格比。并且根据在国内外港机涂装工程的实际经验，将港口机械与设备钢结构防护涂层的防护期按所需年限设计。",
+        "category": " Introduction"
+    },
+    {
+        "id": 191,
+        "chunk": "# （1）钢结构外表面涂层配套体系  \n\n$\\textcircled{1}$ 配套1防护期设计年限为 $15\\sim20$ 年的典型配套见表3-3-72。  \n\n表3-3-72 防护期 $15\\sim20$ 年的典型配套  \n\n\n<html><body><table><tr><td>涂层</td><td>产品名称</td><td>干膜厚度/μm</td><td>涂层</td><td>产品名称</td><td>干膜厚度/μm</td></tr><tr><td>车间底漆</td><td>无机硅酸锌车间底漆</td><td>15</td><td>中间漆</td><td>环氧厚浆(云铁)漆</td><td>125</td></tr><tr><td>底漆</td><td>无机硅酸锌底漆</td><td>75</td><td>面漆</td><td>聚氨酯面漆</td><td>50</td></tr><tr><td>封闭层</td><td>环氧封闭漆</td><td>25</td><td>总膜厚</td><td></td><td>275@</td></tr></table></body></html>\n\n$\\textcircled{1}$ 车间底漆是正式涂装前工序间临时防护涂层，需二次喷砂去除，不计人总膜厚。$\\textcircled{2}$ 总膜厚根据施用环境的腐蚀等级而定。注：表面处理： $5\\equiv2.5$ 级，粗糙度 $75\\mathrm{\\sim}100\\mu\\mathrm{m},$  \n\n$\\textcircled{2}$ 配套2防护期设计年限为 $10\\sim15$ 年的典型配套见表3-3-73。  \n\n表3-3-73 防护期 $\\mathbf{10\\sim15}$ 年的典型配套  \n\n\n<html><body><table><tr><td>涂层</td><td>产品名称</td><td>干膜厚度/μm</td><td>涂层</td><td>产品名称</td><td>干膜厚度/μm</td></tr><tr><td>车间底漆</td><td>无机硅酸锌车间底漆</td><td>15</td><td>面层</td><td>聚氨酯面漆</td><td>50</td></tr><tr><td>底涂层</td><td>环氧富锌底漆</td><td>70</td><td>总膜厚</td><td></td><td>270</td></tr><tr><td>中间层</td><td>环氧(云铁）中涂漆</td><td>150</td><td></td><td></td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 192,
+        "chunk": "# ③配套3防护期设计年限为5～10年的典型配套见表3-3-74。  \n\n表3-3-74 防护期 ${\\pmb5}\\sim{\\bf10}$ 年的典型配套  \n\n\n<html><body><table><tr><td>涂层</td><td>产品名称</td><td>干膜厚度/μm</td><td>涂层</td><td>产品名称</td><td>干膜厚度/μm</td></tr><tr><td>车间底漆</td><td>无机硅酸锌车间底漆</td><td>15</td><td rowspan=\"2\">面层 总膜厚</td><td rowspan=\"2\">聚氨酯面漆或丙烯酸面漆</td><td rowspan=\"2\">2X40</td></tr><tr><td>底涂层</td><td>环氧富锌底漆</td><td>60</td></tr><tr><td></td><td></td><td>100</td><td rowspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\">240</td></tr><tr><td>中间层</td><td>厚浆环氧漆</td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 193,
+        "chunk": "# （2）钢结构内表面  \n\n$\\textcircled{1}$ 封闭式内表面配套见表3-3-75。  \n\n表3-3-75 封闭式内表面配套  \n\n\n<html><body><table><tr><td>涂层</td><td>产品名称</td><td>干膜厚度/μm</td><td>涂层</td><td>产品名称</td><td>干膜厚度/μm</td></tr><tr><td>车间底漆</td><td>无机硅酸锌车间底漆</td><td>15</td><td>底涂层</td><td>环氧富锌底漆</td><td>60</td></tr></table></body></html>\n\n$\\textcircled{1}$ 只在无机富锌车间底漆损坏部位和焊缝部位补涂。 注：表面处理St3，粗糙度 $75\\approx100\\mu\\mathrm{m}$ ·  \n\n$\\textcircled{2}$ 非封闭式内表面配套见表3-3-76。  \n\n表3-3-76 非封闭式内表面配漆  \n\n\n<html><body><table><tr><td>涂层</td><td>产品名称</td><td>干膜厚度/μm</td><td>涂层</td><td>产品名称</td><td>干膜厚度/um</td></tr><tr><td>车间底漆</td><td>无机硅酸锌车间底漆</td><td>15</td><td>中间层</td><td rowspan=\"2\">厚浆环氧漆</td><td>100</td></tr><tr><td>底涂层</td><td>环氧富锌底漆</td><td>60</td><td>总膜厚</td><td>160</td></tr></table></body></html>\n\n$\\textcircled{1}$ 车间底漆系是涂装前工序间临时防护涂层，需二次喷砂去除，不计人总膜厚。注：表面处理 $5\\sqrt{2}+5$ 级粗糙度 $75\\mathrm{\\sim}100\\mu\\mathrm{m}$  \n\n(3）配套比较这里主要比较以上所列港口机械与设备钢结构外表面三种防护漆配套体系，配套1是15～20年防护期的涂层配套，而配套2的防护期为10～15年，配套3的防护期为 $5\\mathord{\\sim}10$ 年，其主要区别在于底漆/中间漆/面漆的选配和总十漆膜厚，见表3-3-77。  \n\n表3-3-77 三种防护漆配套体系比较  \n\n\n<html><body><table><tr><td rowspan=\"2\">涂层</td><td colspan=\"3\">防护期/年</td><td rowspan=\"2\">备注</td></tr><tr><td>15~20</td><td>10~15</td><td>5~10</td></tr><tr><td rowspan=\"2\">底漆</td><td>无机富锌</td><td>环氧富锌</td><td>含锌底漆</td><td rowspan=\"2\">锌含量与防护期有直接关系</td></tr><tr><td>高含锌量</td><td>高含锌量</td><td>中含锌量</td></tr><tr><td>中间漆</td><td>含云母氧化铁</td><td>含云母氧化铁</td><td>不含云母氧化铁</td><td>云母氧化铁鳞片状结构可提高涂层封 闭性和防腐性</td></tr><tr><td>面漆</td><td>丙烯酸脂肪族聚 氨酯</td><td>丙烯酸脂肪族聚 氨酯</td><td>聚氨酯或丙烯酸</td><td>面漆品种和总干膜厚度对各种腐蚀环 境的耐久性的关系相当大</td></tr><tr><td>总干膜厚/μm</td><td>275</td><td>270</td><td>240</td><td>根据ISO12944规定总于膜厚应高 于270μm</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 194,
+        "chunk": "# 5.码头钢管桩  \n\n（1）钢管桩的腐蚀特征钢管桩是海港码头和近海设施建设中非常重要的钢结构，是钢管桩码头的承力构件。与混凝土桩相比，钢管桩承载能力大、抗压、抗拉、抗剪切力、抗震、抗风荷载能力强；其规格多，可选余地大，管径可以大到 $2100\\mathrm{mm}$ ，壁厚 $6.9\\sim25\\mathrm{mm}$ 桩长易调整，易于割桩和接桩。尽管钢管桩的单价较高，但是单桩承载力高，布桩数量少，可以缩小基础承台，施工速率快，后期处理容易，因此综合效益高。  \n\n钢管桩在海洋中有着五大腐蚀区：海 洋大气区、飞溅区、潮差区、全浸区和海 泥区，腐蚀特征如图3-3-51所示。  \n\n图3-3-51中的a线说明了钢桩在海洋环境中腐蚀最严重的部位是在平均高潮位以上的飞溅区，b线说明了在阴极保护下的腐蚀曲线。这是因为氧气供应在这一区域最为充分，氧的去极化作用促进了钢桩的腐蚀，与此同时，浪花的冲击作用对保护膜造成了破坏，加速了腐蚀。  \n\n其次腐蚀峰值（严重的部位）是在平均低潮位以下附近的海水全浸区，这也解释了为什么潮差带出现了腐蚀最低值，甚至低于海水全浸区和海底土壤的腐蚀速率。这是因为钢桩在海洋环境中，随着潮位的涨落，水线上方湿润的钢表面供氧总要比  \n\n![](images/ff0852cace0fcfd9f486e0c62e10c96fa626e898e80169e163d7b71844949d32.jpg)  \n图3-3-51 海水中钢桩的腐蚀分布图  \n\n浸在海水中的水线下方表面充分得多，而且彼此构成一个回路，由此成为一个氧浓差宏观腐蚀电池。在腐蚀电池中，富氧区为阴极，相对缺氧区为阳极，总的效果是整个潮差带中的每一点分别得到了不同程度的保护，而在平均潮位以下则经常作为阳极从而出现了另一个腐蚀峰值。这一腐蚀特征说明，涂料设计的厚度区分要在平均低潮位往下一段距离开始计算，这一距离不同的海域会有所不同。  \n\n在淡水码头中，人们也开始关注对钢管桩或钢桩的腐蚀。淡水中的水质成分对钢管桩的腐蚀起主要作用，如江河的入海口有咸淡水特征，氯离子对碳钢的腐蚀有相当大的影响。很多淡水河流受污染的影响，其水质含有腐蚀性成分，对钢管桩的腐蚀影响也很大。  \n\n(2）钢管桩的重防腐涂料钢管桩防腐处理可采用涂料、阴极保护、PE聚乙烯辐射热缩带和增加腐蚀余量等措施。  \n\n为了重防腐涂料的施工简化和阴极保护系统的有效设计，对钢管桩的防腐蚀范围通常可以分为水上段和水下段两部分，防腐蚀设计年限为 $20\\sim30$ 年。  \n\n钢管桩重防腐涂料必须抗海洋大气、海浪飞溅以及海水浸泡和海泥的腐蚀。  \n\n水上段防腐蚀可选用高固体分涂料或无溶剂涂料。涂料应具有良好的附着性、耐蚀性、耐候性、耐磨损、耐冲击性，同时涂料应能适应干湿交替变化。选用的涂料要耐盐雾、耐老化、耐湿热。应符合JTJ230、ISO12944、ISO20340或者NORSOKM501的要求。  \n\n码头钢管桩重量很大，管径 $1100\\mathrm{mm}$ 、长度 $42\\sim64\\mathrm{m}$ 的钢管桩，均重达25t，沉桩用D100锤施工一千多锤，终锤指标贯入度控制在 $5\\mathrm{mm}$ 以下。因此，钢管桩在起吊和打桩时，钢丝绳、龙口和背板对防腐涂层的刮削的剪切力和打桩冲击力都会很大。如果涂层本身韧性不够，硬度不足，附着力一般，在起吊时就会受到刮伤，或经受不住打桩时的冲击力涂层脱落，这就会造成防腐涂装失败。因此钢管桩防腐涂层的固化强度附着力要求 $\\geq8\\mathbf{MPa}$ 中  \n\n水下段多采用牺牲阳极的阴极保护与涂料联合防腐蚀措施。水下段采用的涂料应能与牺牲阳极保护相配套，具有良好的附着性、耐蚀性、耐电位性和耐碱性。涂层厚度要能满足钢管桩沉桩后12个月内尚未采取牺牲阳极阴极保护时，水下段钢管桩应无腐蚀情况，同时应满足减小阴极保护初始电流密度的要求。  \n\n钢管桩的重防腐涂料设计，由于水上水下的腐蚀速率有着明显的差异，因此重防腐涂料的厚度设计可以有所差异。为了便于阴极保护和重防腐涂料的设计，钢管桩可以简化分为水上段和水下段两个部位。水上段指从设计低水位减1.5m起以上部位，该部位包括大气区、浪溅区和水位变动区。水下段指从设计低水位减1.5m起往下至天然泥面以下1.5m的部位。  \n\n码头钢管桩重防腐涂料中，主要应用的涂料品种有环氧煤沥青涂料、聚氨酯涂料、改性环氧玻璃鳞片涂料和聚酯玻璃鳞片涂料、环氧粉末涂料等。  \n\n(1）环氧煤沥青涂料环氧煤沥青涂料是传统的防腐蚀涂料，耐海水腐蚀性强，曾经是钢管桩上的重要应用品种，主要有厚浆型环氧煤沥青涂料和无溶剂环氧煤沥青涂料两类。由于沥青是致癌物，所以欧美国家对环氧煤沥青涂料的应用进行限制，因此目前应用已经不多。  \n\n(2）聚氨酯涂料聚氨酯涂料物理力学性能良好，漆膜坚韧耐磨；附着力强；耐腐蚀性优良，漆膜耐酸碱、抗盐雾性强。用于钢管桩的聚氨酯涂料，有双组分固化型、湿固化型和无溶剂聚氨酯涂料。聚氨酯涂料的固化速率快，即使在冬天也能快速固化。  \n\n(3）玻璃鳞片涂料以具有很好的耐化学性能玻璃鳞片作为主要防锈颜料的涂料，称之为玻璃鳞片涂料，增强了防腐蚀系统和延长了耐久性。根据不同的应用环境，有环氧玻璃鳞片涂料、聚酯玻璃鳞片涂料和乙烯酯玻璃鳞片涂料等。用于码头钢管桩保护的玻璃鳞片涂料主要有改性环氧玻璃鳞片涂料和聚酯玻璃鳞片涂料。  \n\n玻璃鳞片的厚度在 $2\\sim5\\upmu\\mathrm{m}$ ，这样能保证在涂料中有数十层的鳞片排列，形成涂层内复杂、曲折的渗透扩散路径，使得腐蚀介质的扩散渗透路线变得相当曲折、弯曲，很难渗透到基材。玻璃鳞片片径纵横越大，涂层的抗渗透性能越强。玻璃鳞片把涂层分割成了许许多多的小空间，固化后收缩率小，大大降低了涂层的收缩应力，减少各接触面的残余应力，增加了附着力。  \n\n环氧玻璃鳞片涂料的一般性能同环氧树脂涂料一样。溶剂型的体积固体分在 $80\\%$ 左右，一次喷涂可以达到干膜厚度 $200{\\sim}400\\mu\\mathrm{m}$ ，无溶剂环氧玻璃鳞片涂料的固体分含量为 $100\\%$ 1不含溶剂，可以一次喷涂干膜达 $500\\mu\\mathrm{m}$ 以上。改性环氧玻璃鳞片涂料，用碳氢树脂改性低分子量环氧树脂，其突出的优点是渗透性强，具有优异的封闭性能和附着力。体积固体分高达 $80\\%$ 以上，溶剂含量少，有利于环境保护。与阴极保护有着良好的相容性。加入玻璃鳞片后，进一步增加了涂层的耐久性和耐磨性。码头钢管桩上使用改性环氧玻璃鳞片涂料，施工性能优于纯环氧玻璃鳞片涂料，冬用型可以在一 $5^{\\circ}C$ 的冬季环境温度下应用。  \n\n码头钢管桩需要长达20年的耐久性能，表面处理应该喷砂达到ISO8501-1：1988Sa2.5，表面粗糙度 $R_{\\mathrm{y}}~50{\\sim}85\\mu\\mathrm{m}$ 。改性环氧玻璃鳞片涂料是低表面处理型涂料，在漆膜碰坏部位、海上接桩部位等，由于不可能进行喷砂处理，在动力工具打磨到St3级的表面上涂漆，附着力良好，具有很好的防腐蚀性能。表3-3-78为典型的码头钢管桩改性环氧玻璃鳞片涂料体系。  \n\n表3-3-78码头钢管桩改性环氧玻璃鳞片涂料体系  \n\n\n<html><body><table><tr><td>部位</td><td>涂料名称</td><td>干膜厚度/μm</td><td>总膜厚/μm</td></tr><tr><td>碳钢管，飞溅区域</td><td>改性环氧玻璃鳞片涂料 改性环氧玻璃鳞片涂料</td><td>350 350</td><td>700</td></tr><tr><td>碳钢管，浸没区域</td><td>改性环氧玻璃鳞片涂料 改性环氧玻璃鳞片涂料</td><td>200 200</td><td>400</td></tr></table></body></html>  \n\n聚酯是有机酸和醇类的反应物，用于玻璃鳞片涂料中的聚酯主要是由不饱和二盐基酸与二羟基醇的反应物。聚酯溶于苯乙烯单体，加入催化剂和固化剂，苯乙烯开始交联，形成固体涂膜。在固化中会有实质的收缩伴以放热反应，加入玻璃鳞片以吸收这种收缩应力。聚酯玻璃鳞片涂料，固体分高达 $96\\%\\sim100\\%$ ，固化迅速，在 $23^{\\circ}C$ 时，干膜厚度 $600{\\sim}1500\\mu\\mathrm{m}$ ·只要2h就可以搬运或在上面走动。聚酯玻璃鳞片涂料耐海水的性能突出，具有高度的耐磨性能，适合直升机甲板、破冰船船壳、钢结构的潮汐飞溅区，与阴极保护相容性好。聚酯玻璃鳞片涂料在墨西哥湾海洋平台方面有着25年以上的良好应用记录。双组分喷漆泵和常规高压无气喷涂都可以进行聚酯玻璃鳞片涂料的施工。使用双组分喷漆泵，能在温度低到5℃时施工，使用常规的无气喷涂泵时，最低温度以 $10^{\\circ}C$ 以上为佳。  \n\n(4）环氧粉末涂料环氧粉末涂料漆膜坚固，耐蚀性强，耐酸、碱，抗湿热、抗盐雾。环氧粉末涂料不含有机溶剂，固体分 $100\\%$ ，减少对人体危害，对环境的污染，涂料利用率高，过喷的粉末可以回收利用。钢管桩环氧粉末涂料的施工，从表面处理、粉末喷涂、烘烤固化、冷却成品至包装，都可以在整条流水线上进行，施工速率快，减少劳动力。但是环氧粉末涂料在钢管桩上的涂装应用局限性也是明显的，流水线一次性投资大，涂料的配色比较困难，流水线喷涂设备换颜色喷涂较为困难。环氧粉末涂料用在钢管桩上的另一个缺点是对吊装打桩时造成的破损部位，无法进行修补。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 195,
+        "chunk": "# 6.港口机械与设备钢结构涂料的发展  \n\n如上所述，富锌底漆/环氧中层漆/丙烯酸脂肪族聚氨酯面漆是当前国内常用的港口机械与设备钢结构防腐涂层配套，其性能基本能满足 $10\\sim15$ 年或以上年限的防护期要求。近年来，港口设备的飞速发展推动了港机设备也向用高性能涂料方向发展。其中，高性能面漆可选用聚硅氧烷涂料和氟碳树脂涂料。氟碳树脂涂料可分为水性和溶剂型，其中溶剂氟碳面漆已在国内钢结构钢桥、大型建筑钢结构上获得成功应用。但因其固体分偏低、VOC含量高，对环境有害而受到限制，只有发展水性氟树脂涂料才能满足国际环保要求；聚硅氧烷涂料的保色和保光性远远好过聚氨酯而与氟碳相当。目前，已在石油平台、桥梁、大型建筑钢结构等领域广泛使用。聚硅氧烷面漆因固体含量高、VOC含量较低、外观装饰性好，更接近于环境友好型涂料而受到欢迎。使用聚硅氧烷树脂涂料或氟树脂涂料，其涂装配套体系和上述聚氨酯大同小异，不再赘述。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 196,
+        "chunk": "# 五、电力系统用防腐涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 197,
+        "chunk": "# 1.水电站水工金属结构防腐涂料  \n\n(1）中国蕴藏着巨大的水力发电资源水电是优质的可再生和清洁能源，也是能源开发过程中首选的投资方向。中国河流众多，径流丰沛、落差巨大，蕴藏着非常丰富的水能资源。据统计，中国河流水能资源蕴藏量6.76亿千瓦，年发电量59200亿千瓦·时；可能开发水能资源的装机容量3.78亿千瓦，年发电量19200亿千瓦·时。不论是水能资源蕴藏量，还是可能开发的水能资源，中国在世界各国中均居第一位。中国有十二大水电基地，分别是： $\\textcircled{1}$ 金沙江水电基地； $\\textcircled{2}$ 雅袭江水电基地； $\\textcircled{3}$ 大渡河水电基地； $\\textcircled{4}$ 长江上游水电基地；$\\textcircled{5}$ 乌江水电基地； $\\textcircled{6}$ 湘西水电基地； $\\textcircled{7}$ 闽、浙、赣水电基地； $\\textcircled{8}$ 澜沧江干流水电基地； $\\textcircled{9}$ 南盘江、红水河水电基地； $\\textcircled{10}$ 黄河上游水电基地； $\\textcircled{11}$ 黄河北干流水电基地； $\\textcircled{12}$ 东北水电基地。  \n\n金属钢结构的防腐在水利工程中是比较重要的一部分。以三峡工程为例，其水工结构用钢量为26.6万吨，大坝钢筋用量为32.7万吨，合计59.3万吨，需要防腐总面积高达274.6万平方米。水工钢结构的防腐的目的就是最大限度地减少金属因腐蚀造成的损失，延长其使用寿命并起到一定的装饰作用。  \n\n(2）水工金属结构腐蚀危害和防腐对象金属结构的腐蚀给国民经济带来了巨大的损失。20世纪70年代前后，许多工业发达国家相继都进行过较为系统的腐蚀调查。结果显示，腐蚀直接损失都相当严重。工业发达国家每年因腐蚀所带来的经济损失占其各国GDP的1%～5%。但其中大约1/4是可以通过改善防腐蚀措施来避免的。根据最近的由美国联邦公路局（FHWA）和NACE发起的关于腐蚀损失的研究，报告指出全美每年因金属腐蚀造成的损失超过2760亿美元。此数值甚至超过了一些国家的国内生产总值（GDP)。据估计， $40\\%$ 的美国钢产量用于替换被腐蚀的构件和设备。  \n\n葛洲坝水电厂完工于1988年12月，运行3年后，所有闸门及拦污栅普遍发生锈蚀，8年后，发现在排砂底孔工作门的面板和其他闸门上，有直径约 $\\mathsf{10m m}$ 的锈泡，锈泡处下为深度达 $2\\sim3\\mathrm{mm}$ 的凹坑。环境的腐蚀和泥沙的冲刷，加速了腐蚀的进程。有的结构，在几年内局部已经锈蚀穿了。  \n\n对于水利工程而言，金属结构的腐蚀除了经济上的损失外，更危及水工钢结构工程运行的安全性。虽然涂料的防腐不可能达到 $100\\%$ 的有效，但是通过对水工钢结构防腐的研究、涂装设计和施工，除了可以最大限度地减少腐蚀外，还可以根据涂装配套体系和工况环境条件，制订出科学有效的维护计划，为整个工程的正常运行提供保障。  \n\n水工金属钢结构防腐对象主要包括各类闸门、拦污栅、启闭机、升船机、压力钢管、清污机、埋件以及过坝通航钢结构等，统称水工钢结构。这些钢结构有的处在水下，有的暴露于大气中，有的是处于干湿交替的环境，有的被埋在地下。如图3-3-52所示是云南小湾水电站的水工金属结构布置，防腐要求的设计数值见表3-3-79。  \n\n![](images/c5b796fec4c3e8b3a9c718e58220a6c030de45a7d34e7c6cfe59271575a97a82.jpg)  \n图3-3-52 某坝后式水电站横剖面图（单位：m）  \n\n表3-3-79云南小湾水电站水工金属结构的布置及防腐工程量  \n\n\n<html><body><table><tr><td>设备名称</td><td>设备位置</td><td>腐蚀环境</td><td>水流速度 /(m/s)</td><td>防腐 年限/年</td><td>防腐材料</td><td>用钢量 /t</td></tr><tr><td>导流洞闸门/门槽</td><td>1、2#导流洞</td><td>水中、干湿交替</td><td>20</td><td>2.4、6</td><td>涂料</td><td>900</td></tr><tr><td>导流中孔闸门</td><td>导流中孔</td><td>干湿交替</td><td>35</td><td>6</td><td>涂料</td><td>400 1100</td></tr><tr><td>导流中孔门槽</td><td>导流中孔</td><td>水中、干湿交替</td><td>35</td><td></td><td>涂料</td><td>800</td></tr><tr><td>导流底孔闸门</td><td>导流底孔</td><td>干湿交替</td><td>35</td><td>6</td><td>涂料</td><td>1050</td></tr><tr><td>导流底孔门槽</td><td>导流底孔</td><td>水中、干湿交替</td><td>35</td><td>6</td><td>涂料</td><td>580</td></tr><tr><td>拦污栅</td><td>进水孔</td><td>水下</td><td>1</td><td>20</td><td>涂料、金属喷涂</td><td>1100</td></tr><tr><td>进水孔闸门</td><td>进水口</td><td>水中、干湿交替</td><td>5</td><td>20</td><td>涂料、金属喷涂</td><td>1050</td></tr><tr><td>进水口门槽</td><td>进水口</td><td>水中、干湿交替</td><td>5</td><td>20</td><td>涂料</td><td>900</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>设备名称</td><td>设备位置</td><td>腐蚀环境</td><td>水流速度 /(m/s)</td><td>防腐 年限/年</td><td>防腐材料</td><td>用钢量 /t</td></tr><tr><td>尾水闸门 尾水门槽 表孔工作闸门 表孔工作门槽 泄洪洞闸门 泄洪洞门槽</td><td>尾水洞 尾水洞 溢洪道 溢洪道 泄洪洞 泄洪洞</td><td>水中、干湿交替 水中 水中、干湿交替 干湿交替 空气中、干湿交替</td><td>10 10 25 25 30</td><td>20 20 20 20</td><td>涂料 涂料 金属喷涂 涂料</td><td>800 500 700 100</td></tr></table></body></html>  \n\n(3）水工金属结构腐蚀环境分析在制订水工钢结构防腐保护体系之前，要对其所处的腐蚀环境进行科学、系统的分析。并按照相关的标准，对腐蚀环境进行评估和分级。在此基础上，才可以设计出有效的并且能够符合防腐要求的涂装配套系统和施工方案。水工钢结构的腐蚀环境分为自然环境和运行工况两个部分。它们都直接影响到腐蚀的进程和漆膜的防腐年限。  \n\n$\\textcircled{1}$ 自然环境不同地区、不同地点的自然环境，对于水工金属结构腐蚀过程的影响不尽相同，因此，在进行涂装设计前必须对其自然条件情况调查清楚。  \n\n当前我国的水利水电工程大多建筑于西南、西北等地区山水之间，远离城市，周围空气相对干净，但由于所处地理位置和水分蒸发，常年气温偏高、湿度偏大；或昼夜温差大，极易产生凝露现象；加上近年来上、下游水体污染、酸雨等等因素的影响，自然腐蚀环境日渐严重。  \n\n以下是长江三峡水利工程所处的自然腐蚀环境。  \n\na.气温和水温三峡库区处于长江上游，北有秦岭、大巴山的阻挡，北方冷空气不易侵人，气温较高。三峡库区年平均气温为 $16.3\\{{\\sim}18.2{\\bar{\\mathrm{c}}}$ 。历年最高水温 $29.5^{\\circ}C$ ，历年最低水温一 $1.4\\dot{C}$ ，多年平均水温 $17.9^{\\circ}C$ 。  \n\nb．日照三峡库区年日照时数少，大部地区年日照时数仅有 $1200{\\sim}1600\\mathrm{h}$ 中  \n\nc.降雨（含酸雨）三峡库区山丘广布，地形崎岖，地势高低悬殊，各地降水量丰富，并且带有酸雨。但时空分布不均，年平均降雨量在 $\\bf{1100m m}$ ，日降水强度较小，约在$\\mathrm{150mm}$ 。三峡库区是我国酸雨频率较高、酸雨程度较为严重的区域之一。库区各站酸雨频率为 $60\\%\\sim100\\%$ ，大多数占 $90\\%$ 以上。  \n\nd.风年平均风速一般为 $1.0{\\sim}1.5\\mathrm{m/s}.$  \n\ne.雾三峡地区是多雾地区，西部重庆68.9天为最多，到峡谷为8.4天为最小，到坝区则有所增加，宜昌为23.2天。  \n\nf.相对湿度和蒸发库区年平均相对湿度变化范围基本在 $70\\%\\sim82\\%$ ，其中西段一般有 $79\\%\\sim82\\%$ ，东段为 $75\\%$ 左右，中段 $67\\%\\sim71\\%$ 。呈两头大，中间小的分布格局。库区内多年平均水面蒸发量在 $800{\\sim}1000\\mathrm{mm}$ 心  \n\ng.库区水质情况库区的水体 $\\mathfrak{p H}$ 值在 $\\mathfrak{E}.\\ \\mathtt{8}\\sim\\mathfrak{g}_{*}\\ 1$ ，溶解氧在 $8.0\\mathrm{mg/L}$ 。耗氧量在$1.4{\\sim}1.9{\\mathrm{mg/L}}$ 。库区的硝酸盐含量大于氨氮和亚硝酸盐。水中有铁细菌及硫酸还原菌及附着生物。  \n\nh.含砂量多年平均含沙量为 $\\mathrm{1.19\\mathrm{\\sim1.~69\\mathrm{kg/m^{3}}}}$ ，最大含沙量为 $10.5\\mathrm{{kg/m^{3}}}$ 。经过环境保护的治理，长江上游干、支流的输沙量和含沙量都在减少。  \n\n金属的腐蚀是指金属和其所处的环境间，在物理和化学的相互作用下导致金属性能的破坏。腐蚀过程受其环境因素影响十分大，在第一节腐蚀原理中有详细的说明。另外酸雨的存在，会急剧地加快金属的腐蚀进程。通过对以上的环境参数的分析，可以看出长江三峡库区处在一个较为恶劣的腐蚀环境。  \n\n$\\textcircled{2}$ 运行工况水工金属结构运行工况比较复杂，有些处于大气环境中(室内或室外)；有些处于水下(静水或动水)；有些常年经受高、中速含泥沙水流的冲磨中；或常年处于干湿交替状态下等。对于涂装设计而言，一般将水工金属结构运行工况分为以下五种状态：  \n\n$\\cdot$ 水上设备与结构——大气区；  \n$\\cdot$ 水下结构—水下区；  \n$\\cdot$ 干湿交替状态下结构—间浸区；  \n$\\cdot$ 高、中速含泥沙水流冲磨作用下的结构—一压力钢管内壁；  \n$\\cdot$ 各类埋地件——泥下区等。  \n\na.大气区对于水上设备与结构，主要考虑要耐大气腐蚀。应选择抗老化、抗紫外线的耐候型涂料配套。通常以脂肪族聚氨酯为好，其次为丙烯酸。对防护期不长的可用醇酸。  \n\nb.水下区我国大型水利水电工程大都建筑于大江大河流域，水工结构主要受到淡水的侵蚀。与海水不同，淡水的含盐量低、电阻率高（一般高达几千上万欧姆·厘米)，尽管两者 $\\mathbf{\\pH}$ 和溶解氧相差不多，但钢结构在淡水中的腐蚀速率比在盐水中低。  \n\n国内外对淡水水域中钢结构的腐蚀调查以及现场试样腐蚀试验结果表明：水工钢结构水下部分主要是在夏季水温较高时发生剧烈的局部腐蚀（锈瘤)。我国丹江口水利枢纽管理局与湖北省微生物研究所对该枢纽水工钢结构水下部分进行了五次腐蚀与微生物调查，发现在每年八月高温季节，水库水中铁细菌和硫酸盐还原菌数量较高，深孔闸门构件孔蚀较严重，暴露十年后孔蚀最大深度 $3.\\mathrm{8mm}$ ，而其锈泡中的硫酸盐还原菌数高达 $10^{5}$ 个，显著地高于同高度的水库水中的这种细菌的菌数（10个)。锈包中硫酸盐还原菌多，意味着这种细菌促进了钢结构的局部腐蚀。因此，对于水下钢结构，应选用抗水、抗菌、耐磨、高附着力的涂层配套。  \n\nc.干湿交替下间浸区在淡水环境（除含盐量较高者外）中，水线以上的间浸区，因为钢结构表面水膜的含盐量低，所以腐蚀均匀，与大气中的腐蚀速率相近，初期为 $0.03\\sim$ $0.\\ 04\\mathrm{mm/a}$ ，一年后衰退为 $0.\\ 008{\\sim}0.015\\mathrm{mm/a}$ ；而在含盐量较高的淡水中（如卡马河水氯离子和硫酸根离子相应地为 $30{\\sim}40\\mathrm{mg/L}$ 和 $50{\\sim}200\\mathrm{mg/L)}$ ，大气中钢的腐蚀较均匀，长期腐蚀速度为 $0.04\\mathrm{mm/a}$ ，而间浸区则急剧变为点蚀，其局部腐蚀速率增大到 $\\bar{0}.25\\mathrm{mm/a}$ ，为大气中的6倍。  \n\n干湿交替状态的水工结构，处于空气与水交替接触下，其腐蚀速率要比长期浸在水中严重得多。原因是该部位波浪起伏，空气中的氧不断扩散到水中，使水中溶解氧骤增，持续地产生去极化作用，并且使钢结构表面有更多的机会形成溶解氧的浓差电池而造成局部腐蚀(浓差腐蚀)。因此，水线部位是水工钢结构腐蚀最严重的区域。对于干湿交替下的钢结构应选用耐水性好、层间附着力强、耐干湿交替、耐机械摩擦等综合性能较优的涂料。  \n\nd.压力钢管受高速水流作用的压力钢管内壁涂层往往处于高度紊流状态下，其表面可能由于在以微秒计的时间内局部周期性地形成真空的空穴又突然破灭（水锤作用)，释放出大量能量而造成以机械作用为主、电化学腐蚀为辅、又互相促进的气蚀破坏；也可能是由于液体紊流或冲击造成的深坑破坏，也就是冲刷腐蚀（erosion corrosion）。当水流的泥沙含量较高时，破坏更为严重，压力钢管壁一般以底部磨损得最快。由此可见，压力钢管内壁一定要做防腐，而且宜采用超强度环氧涂料为好。  \n\ne.泥下区埋件处于江河流域泥下区，由于泥中孔隙水含氧有限，故泥下区的腐蚀最轻，大量拔桩实测结果表明其腐蚀速率为0.006～0.03mm/a，故一般不必用涂料保护。但靠近泥面处可能与水底的水下区构成氧的浓度差，浓度高的一端会充当阴极，而浓度低的，埋在土壤里的一端成为阳极，从而加剧腐蚀；而在污染流域内，泥卜区可能有大量硫酸盐还原菌，造成局部腐蚀性相对严重的情况。此外，与所处地土壤的土质化学成分有关，如土壤污染严重，应考虑涂层的耐化学品性质。一般仅需防潮、防水及漆膜牢固性。使用最多的当属环氧与沥青类涂料。  \n\n$\\textcircled{3}$ 腐蚀环境的分类对每一个环境所对应的腐蚀等级，ISO12944都推荐了相应的防腐涂料配套、表面处理以及施工的要求（详见本章第一～三节)。在设计涂装体系和编制涂装工艺时，可以参照ISO12944。  \n\n综上所述，对于某一项具体的水利水电工程的金属结构防腐涂装，首先要调查清楚工程所处地理位置的自然环境，以确定其腐蚀性环境分类类别；根据金属结构的运行工况明确其对防腐涂层性能的要求；同时了解工程设计人员对不同水工金属结构防腐寿命的要求以及相关国家标准规定等。在此基础上进行的防腐涂装系统的设计就有了科学的依据，从而保证设计的正确性和可靠性，确保水工金属结构的使用寿命和正常运行。  \n\n(4）水工金属结构防腐蚀标准在设计水工金属结构的涂装体系中，相关的标准是必不可少的，有国际标准、国家标准、行业标准以及重大项目的标准等。在开始设计涂装配套之前，必须知道该项目所参照的标准。同样，涂料的施工和检测也应按照已确定的标准执行，确保涂装的过程是按照设计的要求进行的，从而获得预期的防腐年限。以下是水工金属结构涂装常用的标准。  \n\nISO 12944 色漆和清漆——用涂料系统对钢结构进行防腐  \nGB/T 15957—1995 大气环境腐蚀性分类  \nSL 105—1995 水工金属结构防腐蚀规范  \nDL 5017 压力钢管制造安装及验收规范  \nTGPS.J 三峡三期工程涂料质量检测标准（试行）  \nJTJ 230—1988 港口工程钢结构防腐蚀技术规定  \nGB8923 涂装钢材表面锈蚀等级和除锈等级  \nGB/T 13288 表面粗糙度比较样板抛（喷）丸、喷砂加工表面  \nGB/T13312 钢铁件涂装前除油程度检验方法（验油试纸法）  \nJB/Z 350 高压无气喷涂典型工艺  \nHG/T 3668—2000 富锌底漆  \nGB 1764 漆膜厚度测定法  \nGB/T5210 涂层附着力的测定法拉开法  \nGB/T 1771 色漆和清漆耐中性盐雾性能的测定  \nGB/T1865 色漆和清漆人工气候老化和人工辐射暴露  \nGB/T 1740 漆膜耐湿热测定法  \nGB 7692 涂装作业安全规程涂漆前处理工艺安全  \nGB 6514 涂装作业安全规程涂漆工艺安全  \n\n(5）水工钢结构防腐涂料及其配套系统涂层的配套，首先要求同一涂层系统的涂料相容。一般同一涂料公司产品配套的兼容性要好于不同公司涂料产品的组合。如果一个涂层系统采用了几个公司的产品，其配套性难以保证。一旦出了质量问题，不易分析原因，也难以区分责任者。特别是目前涂料公司较多，很多涂料无统一标准，所以更需要注意。由于涂料种类和配套繁多，不能一一列举，以下只介绍目前水工金属结构常用的  \n\n一些涂料配套系统。  \n\n①临时保护涂层—车间底漆车间底漆主要用于喷砂后钢板及其他钢结构，在制作过程中起到临时保护作用，一般的保护期为3～12个月。含锌粉的车间底漆的保护时间相对于不含锌粉的保护时间要长。在选用车间底漆时，不仅要考虑到其临时防腐性能，还要考虑到车间底漆的可焊接性能、可流水线操作性和施工安全性。通常选用国际上一些检测机构和知名船级社认可的可焊接车间底漆。  \n\n$\\textcircled{2}$ 水上区与大气接触部分的结构分为室外和室内两种。室外的腐蚀环境较室内恶劣，要经受日晒雨淋。除了防腐之外，出于美观方面的考虑，室外的钢结构涂料要有良好的保光保色性能。表 $3-3=80\\sim$ 表3-3-82为常用的水上区配套。  \n\n表3-3-80 醇酸漆配套  \n\n\n<html><body><table><tr><td>涂层</td><td>涂料种类</td><td>涂装道数/道</td><td>干膜厚度/μm</td></tr><tr><td>底层</td><td>醇酸厚浆底漆</td><td>1</td><td>75</td></tr><tr><td>中层</td><td>醇酸面漆</td><td>1</td><td>35</td></tr><tr><td>面层</td><td>醇酸面漆</td><td>1 ：</td><td>35</td></tr><tr><td colspan=\"3\">总干膜厚度</td><td>145</td></tr></table></body></html>\n\n注：干膜厚度为推荐使用厚度，下同。  \n\n表3-3-81 环氧-丙烯酸漆配套  \n\n\n<html><body><table><tr><td>涂层</td><td>涂料种类</td><td>涂装道数</td><td>干膜厚度/μm</td></tr><tr><td>底层</td><td>环氧树脂底漆</td><td>1</td><td>50</td></tr><tr><td>中层</td><td>丙烯酸中层漆</td><td>1</td><td>35</td></tr><tr><td>面层</td><td>丙烯酸面漆</td><td>1</td><td>35</td></tr><tr><td colspan=\"3\">总干膜厚度</td><td>120</td></tr></table></body></html>  \n\n表3-3-82富锌-环氧-聚氨酯面漆配套  \n\n\n<html><body><table><tr><td>涂层</td><td>涂料种类</td><td>涂装道数/道</td><td>干膜厚度/μm</td></tr><tr><td>底层</td><td>富锌底漆</td><td>1</td><td>70</td></tr><tr><td>中层</td><td>环氧云铁中层漆</td><td>1</td><td>100</td></tr><tr><td>面层</td><td>聚氨酯面漆</td><td>1</td><td>50</td></tr><tr><td colspan=\"3\">总干膜厚度</td><td>220</td></tr></table></body></html>  \n\n该醇酸漆配套适用于轻微至中等腐蚀环境下钢结构，室外防护期一般 $3\\sim5$ 年，而用于室内钢结构防护期可达到 $5\\sim6$ 年，属于防腐要求不高的普通涂料配套。醇酸面漆具有良好的光泽、丰满度、柔韧性和一定的耐候性，也耐矿物油及脂肪烃类物质的泼溅。另外，醇酸漆施工简便，价格低廉。需要注意的是，醇酸涂料是氧化固化型涂料，也就是与空气中的氧气发生反应而固化成膜，所以单度涂料的厚度不应过厚，以免漆膜表层固化后，底层因无法接触足够的氧气而不能完全固化。一般单度醇酸涂料的干膜厚度不应超过 $100\\mu\\mathrm{m}$ 中  \n\n环氧-丙烯酸漆配套适用于中等至严重腐蚀条件下钢结构的中期防护。底漆可选用含有磷酸锌防锈颜料、聚酰胺固化的双组分环氧底漆。可形成坚硬、高效防锈的漆膜。可加涂环氧、聚氨酯、丙烯酸等各种面漆，配套兼容性好。丙烯酸面漆是一种以丙烯酸树脂为基料的物理干燥型面漆，具有理想的光泽、保色性，优良的耐候性，抗紫外线辐射性，耐海水，也耐脂肪烃类物质和动植物油的溅污。由于丙烯酸漆和环氧底漆的固化机理不同，一个是物理干燥型，一个是化学交联固化型，因此在施工过程中要注意丙烯酸漆和环氧底漆间的重涂间隔，如超过最大重涂间隔，一定要彻底进行合适的表面处理，  \n\n从而确保好的层间附着力。  \n\n富锌-环氧-聚氨酯面漆配套属于长效防腐涂层配套。富锌底漆一般分为环氧富锌和无机富锌两类，均以大量锌粉为防锈颜料，而主要成膜物质，前者是环氧树脂，后者为无机硅酸盐。其防腐机理基于金属锌粉对钢材表面的阴极保护作用。  \n\n中层漆采用环氧云铁漆，该漆以云母氧化铁（MIO）为防锈颜料，由于其鳞片状结构类似云母而得名，在漆膜中层层叠积排列，可有效阻挡水分、氧气及其他腐蚀性介质的渗透，延长介质的渗透时间；又因为云母氧化铁光敏性弱，化学稳定性好，因而具有较好的耐候性和抗紫外线辐射等性能；其次，环氧云铁漆涂膜表面因其片状填料的作用，形成均匀的粗糙度，有利于与底漆、面漆的黏结。  \n\n聚氨酯面漆不仅具有突出的耐候性、耐蚀、耐水、耐油及耐化学品渗透性，抗紫外线辐射、保光保色性好，而且漆膜致密坚韧、附着力强、具有较全面的物理力学性能。此外，聚氨酯漆外观装饰性能好，可有高光、半光、低光等多种选择，是目前最好的涂料品种之一。  \n\n$\\textcircled{3}$ 干湿交替状态——间浸区处于干湿交替状态下的金属结构件，如拦污栅、表孔闸门、门槽、埋件、检修门、事故门等，处于半浸没状态。在气-水交界面通常最容易引起锈蚀。随着潮涨潮落分界线常有波动，不断产生新锈。因此，一般选用耐水性好、层间附着力强、耐干湿交替、耐机械摩擦等综合性能较优的涂料，如环氧类和聚氨酯类涂料，见表3-3-83。  \n\n表3-3-83 间浸区涂料配套  \n\n\n<html><body><table><tr><td>涂层</td><td>涂料种类</td><td>涂装道数/道</td><td>干膜厚度/μm</td></tr><tr><td>底层</td><td>环氧富锌/无机富锌底漆</td><td>1</td><td>70</td></tr><tr><td>中层</td><td>环氧中层漆（MIO)</td><td>１</td><td>150</td></tr><tr><td>面层</td><td>聚氨酯面漆</td><td>1</td><td>50</td></tr><tr><td colspan=\"3\">总干膜厚度</td><td>270</td></tr></table></body></html>  \n\n$\\textcircled{4}$ 水下区和埋地区水下和埋地区防腐涂层一般采用环氧类和沥青类，要求涂料具有突出的防水防潮性和耐土壤腐蚀，典型配套见表3-3-84。  \n\n表3-3-84水下区和埋地区涂料配套  \n\n\n<html><body><table><tr><td>涂层</td><td>涂料种类</td><td>涂装道数/道</td><td>干膜厚度/μm</td></tr><tr><td>“底-面合一”</td><td>环氧煤焦油沥青涂料</td><td>１</td><td>150</td></tr><tr><td>“底-面合一”</td><td>环氧煤焦油沥青涂料</td><td>1</td><td>150</td></tr><tr><td></td><td>总干膜厚度</td><td></td><td>300</td></tr></table></body></html>  \n\n环氧煤焦油沥青漆可自作底漆，其性能兼顾环氧树脂和煤焦油沥青树脂两者的优点。具有以下几方面的特点：a.突出的耐水性和防腐性；b.良好的耐酸、耐碱和耐油性；c.附着力强、韧性好；d.价格较低，性价比优。  \n\n但由于煤焦油沥青有致癌性而逐渐被性能优异的环氧和石油树脂改性环氧涂料取代。  \n\n$\\textcircled{5}$ 压力钢管内壁涂层压力钢管内壁涂层长年经受高速/中速含泥砂流水的冲刷，因此对选择的涂料要求具有突出的耐磨、耐水和附着力强的性能。传统的做法是采用环氧沥青漆，例如，鲁布革水电站和十三陵抽水蓄能电站。随着对防腐年限要求的提高，高强度环氧漆逐渐得到广泛的应用，尤其适用于高水头、泥砂含量大的流域水电站压力钢管内涂。高强度环氧是一种由小分子量聚胺固化的高性能涂料，固化后具有优良的耐淡水、海水以及防腐蚀、耐磨蚀性能，而且涂料通常可以做成高固体分、低VOC含量，更加环保。表3-3-85和",
+        "category": " Introduction"
+    },
+    {
+        "id": 198,
+        "chunk": "# 表3-3-86分别为环氧煤焦油沥青漆和超强环氧漆配套。  \n\n表3-3-85 环氧煤焦油沥青漆配套  \n\n\n<html><body><table><tr><td>涂层</td><td>涂料种类</td><td>涂装道数/道</td><td>干膜厚度/μm</td></tr><tr><td>“底-面合一” “底-面合”</td><td>环氧煤焦油沥青涂料 环氧煤焦油沥青涂料</td><td>1 1</td><td>250</td></tr><tr><td colspan=\"3\">总干膜厚度</td><td>250 500</td></tr></table></body></html>  \n\n表3-3-86 超强环氧漆配套  \n\n\n<html><body><table><tr><td>涂层度数</td><td>涂料种类</td><td>涂装道数/道</td><td>干膜厚度/μm</td></tr><tr><td>“底-面合一”</td><td>超强环氧涂料 超强环氧涂料</td><td></td><td>250</td></tr><tr><td colspan=\"2\">“底-面合一”</td><td>1</td><td>250 500</td></tr></table></body></html>  \n\n可以通过对比试验来比较超强环氧和环氧沥青涂料的耐磨性能。试验是参照水利部“水工混凝土试验规程”—SD105—1982所规定的方法，用专用设备在高、中流速含泥砂旋转水流中进行冲磨试验。根据各试验期间试件重量变化情况及规律，评估其防护涂层的抗冲磨性能。为比较送验涂层的抗冲磨性，试验时在同样条件下，对涂有超强环氧树脂漆、环氧沥青漆的钢板，还有未涂涂料的碳钢钢板进行了测量。试验条件如下。  \n\n磨料：石英砂  \n\n流体：自来水 $+1$ %石英砂（质量）  \n\n磨粒粒径： $0.3\\sim0.1\\mathrm{mm}$ 流速 $\\div15\\mathrm{m/s}$ 试样尺寸： $50\\mathrm{mm}\\times100\\mathrm{mm}$  \n\n温度：室温  \n\n$\\textcircled{1}$ 石英砂质量比： $1/100$ 。石英砂砂径： $0.1\\mathrm{mm}$ 实验结果见表3-3-87及图3-3-53。  \n\n表3-3-87 试样经不同时间冲刷试验后试验结果（失重数据）  \n\n\n<html><body><table><tr><td rowspan=\"2\">配套体系</td><td colspan=\"10\">试验结果，失重/（g/50cm²）</td></tr><tr><td>10h</td><td>20h</td><td>30h</td><td>40h</td><td>50h</td><td>60h</td><td>70h</td><td>80h</td><td>90h</td><td>100h</td></tr><tr><td>1#超强耐磨环氧</td><td>0.1517</td><td>0.2525</td><td>0.3693</td><td>0.4881</td><td>0.5819</td><td>0.6724</td><td>0.7503</td><td>0.8211</td><td>0.8949</td><td>0.9706</td></tr><tr><td>2#普通环氧沥青</td><td>0.1726</td><td>0.3069</td><td>0.4155</td><td>0.5587</td><td>0.6908</td><td>0.8120</td><td>0.9534</td><td>1.0744</td><td>1.2098</td><td>1.3352</td></tr><tr><td>3#碳钢板</td><td>0.2588</td><td>0.4229</td><td>0.6011</td><td>0.7664</td><td>0.9812</td><td>1.1208</td><td>1.2769</td><td>1.5532</td><td>1.7107</td><td>2.0017</td></tr></table></body></html>  \n\n![](images/0054c33909e7316b74c61b197a6fb2844745e1d9f8d562f53ef20f83cfbcf251.jpg)  \n图3-3-53 三片试样失重示意图  \n\n试验结果表明， $1^{\\sharp}$ 试样超强度环氧漆耐磨性能明显优于对比样 $2^{\\sharp}$ 试样环氧沥青漆试样和 ${\\mathfrak{3}}^{\\sharp}$ 试样普通碳钢钢板。  \n\n$\\textcircled{6}$ 热喷涂金属保护由于锌、铝的电极电位比钢铁低，所以在腐蚀介质中起到阴极保护作用。金属涂层多孔，不宜单独使用。一般在金属涂层上喷涂黏度较低的涂料进行封闭，再在封闭涂层上加涂中层漆和面漆，两种涂层发挥了最佳协同效应，防腐寿命可达20年以上。但是，金属热喷涂对环境和施工工艺的要求更为严格，特别是表面处理，而且也是一种高耗能工艺，选用时需谨慎。表3-3-88为典型热喷涂和涂料复合配套体系。  \n\n表3-3-88 金属涂层和涂料复合配套  \n\n\n<html><body><table><tr><td>涂层</td><td>涂料种类</td><td>涂装道数/道</td><td>干膜厚度/μm</td></tr><tr><td>底层</td><td>喷锌或喷锌铝</td><td>1</td><td>120</td></tr><tr><td>封闭层</td><td>环氧封闭涂料</td><td>1</td><td>30</td></tr><tr><td>中层</td><td>环氧云铁中层漆</td><td>1</td><td>150</td></tr><tr><td>面层</td><td>环氧/聚氨酯面漆</td><td>1</td><td>60</td></tr><tr><td colspan=\"3\">总干膜厚度</td><td>360</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 199,
+        "chunk": "# 2.风力发电设备防腐涂料  \n\n(1）风力发电设备防腐蚀特点风力发电设备主要由桨叶、风机及塔架组成，其中塔架是需要涂装的主要部位。风力发电站所处的风场是自然条件恶劣的户外环境，常年风力在4级以上，并伴有风沙，塔架在这里会受到日光的强烈曝晒，经受风雨、冰雪的侵袭，并受到寒流与高温变化的影响。对于地处海边的塔架，还会受到水汽、盐雾的侵蚀及海水浪花的泼溅，因此极易受到腐蚀。针对风力发电站所处风场的环境特点，要求所用的涂料具有良好的耐候性、耐水性、附着力及防腐性能；漆膜坚硬、耐外力冲击等优异性能。  \n\n塔架的塔筒是主要的防腐部位。针对塔筒内外所处的腐蚀环境，塔筒内外壁分别采用不同的防腐涂装方案。目前世界上各大风电公司都有自己成熟的塔筒防腐涂装配套体系。这些配套体系都是以达到长期耐久年限为目的而进行设计的。它符合国际标准ISO12944中有关钢结构在不同的腐蚀环境下达到长期耐久年限的相应的规定和要求。塔筒外壁由于直接与外界大气自然环境接触，根据ISO12944-2《腐蚀环境分类》规定，塔筒外壁应处于在C4至C5-M腐蚀环境，即高腐蚀环境至非常高的海洋腐蚀环境，而塔筒内壁由于不直接与外部大气自然环境接触，应属于C3腐蚀环境，即中等腐蚀环境。  \n\n目前我国采用最多的涂料配套体系是环氧/聚氨酯涂料，它能确保在任何环境条件下获得最佳的防腐性。塔身外表面较少采用喷锌的处理方式，因为喷锌处理对钢材的表面处理要求高，喷砂须达到 $\\mathbf{Sa3}$ 级，表面粗糙度达到 $80\\sim100\\mu\\mathrm{m}$ ，施工难度大，投资亦大。而环氧富锌底漆不仅能提供长效的阴极保护，同时价格相对便宜，且易于施工，因此愈来愈得到广泛的应用。目前国外采用玻璃鳞片中涂漆来提高配套涂层整体的耐磨性。",
+        "category": " Introduction"
+    },
+    {
+        "id": 200,
+        "chunk": "# （2）风力发电机涂装的典型方案  \n\n$\\textcircled{1}$ 典型配套方案表 $3-3=89\\sim$ 表3-3-96仅是对涂装方案的总体介绍，用户可根据自己的实际情况和需求作相应调整。涂装系统的漆膜厚度可根据风力发电机塔架所处的腐蚀环境情况而变化（参考ISO12944—2)。  \n\n表3-3-89塔身外表面涂装方案  \n\n\n<html><body><table><tr><td colspan=\"3\">表面处理：打砂至ISO8501-1：2007的Sa2.5级，表面粗糙度达到ROGOTESTNO.3BN9a级</td></tr><tr><td>序号</td><td>涂 层</td><td>涂料品种</td></tr><tr><td>1</td><td>底漆层</td><td>环氧富锌底漆</td></tr><tr><td>2</td><td>中间漆层</td><td>双组分厚浆型环氧漆</td></tr><tr><td>3</td><td>面漆层</td><td>双组分聚氨酯面漆</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 201,
+        "chunk": "# 表3-3-90 经喷锌处理塔身外表面涂装方案  \n\n表面处理：打砂至ISO8501-1:2007的Sa3级，表面粗糙度达到ROGOTESTNO.3BN11级喷锌层厚度根据ISO2063达到 $60\\sim100\\mu\\mathrm{m}$  \n\n<html><body><table><tr><td>序号</td><td>涂层</td><td>涂料品种</td></tr><tr><td>1</td><td>底漆层</td><td>双组分环氧富锌底漆或喷锌层专用底漆</td></tr><tr><td>2</td><td>面漆层</td><td>双组分聚氨酯面漆</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 202,
+        "chunk": "# 表3-3-91 塔身内部涂装方案  \n\n表面处理：打砂至ISO8501-1：2007的 $5\\equiv2.5$ 级，表面粗糙度达到ROGOTESTNO.3BN9a级  \n\n<html><body><table><tr><td>序号</td><td>涂层</td><td>涂料品种</td></tr><tr><td>1</td><td>底漆层</td><td>环氧富锌底漆</td></tr><tr><td>2</td><td>面漆层</td><td>双组分聚氨酯面漆</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 203,
+        "chunk": "# 表3-3-92 铸铁部位涂装方案  \n\n表面处理：打砂至ISO8501-1：2007的 $\\sin2.5$ 级，并手工打磨去除铸件表面的披锋、浇冒口、毛刺等  \n\n<html><body><table><tr><td>序号</td><td>涂层</td><td>涂料品种</td></tr><tr><td>1</td><td>底漆层</td><td>双组分环氧底漆</td></tr><tr><td>2</td><td>中间漆层</td><td>双组分环氧云铁漆</td></tr><tr><td>3</td><td>面漆层</td><td>双组分聚氨酯面漆</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 204,
+        "chunk": "# 表3-3-93 轮毂延长节等部位涂装方案  \n\n表面处理：打砂至IS $\\phantom{-}38501\\mathrm{-}1_{\\sharp}2007$ 的 $5\\equiv2.5$ 级，表面粗糙度达到ROGOTESTNO.3BN9a级  \n\n\n<html><body><table><tr><td>序号</td><td></td><td>涂层</td><td>涂料品种</td></tr><tr><td>1</td><td>底漆层</td><td></td><td>无机富锌底漆</td></tr><tr><td>2</td><td>中间漆层</td><td></td><td>双组分厚浆型环氧漆</td></tr><tr><td>3</td><td>面漆层</td><td></td><td>双组分聚氨酯面漆</td></tr></table></body></html>\n\n$\\textcircled{1}$ 中间漆喷涂前，先薄薄喷一道环氧封闭底漆，起到对无机富锌底漆封闭作用，然后喷至中间层规定的厚度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 205,
+        "chunk": "# 表3-3-94 齿轮箱内部涂装方案  \n\n表面处理：打砂至 $\\mathbf{ISO\\8501-1:2007}$ 的 $5\\equiv2.5$ 级，表面粗糙度达到ROGOTESTNO.3BN10a级  \n\n\n<html><body><table><tr><td>序号</td><td>涂层</td><td>涂料品种</td></tr><tr><td>1</td><td>“底-面合一”</td><td>双组分酚醛环氧漆</td></tr><tr><td>2</td><td>“底-面合-”</td><td>双组分酚醛环氧漆</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 206,
+        "chunk": "# 表3-3-95 铝材等工件表面涂装方案  \n\n表面处理：除去铝材表面的油脂杂质等污染物，根据DIN55928标准要求用非金属磨料扫砂铝材表面以获得表面粗糙度达到 $R_{z}$ 为 $50\\mu\\mathrm{m}$ 的均匀表面  \n\n<html><body><table><tr><td>序号</td><td>涂层</td><td>涂料品种</td></tr><tr><td>1</td><td>序号</td><td>双组分环氧漆</td></tr><tr><td>2</td><td>序号</td><td>双组分聚氨酯面漆</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 207,
+        "chunk": "# 表3-3-96 电镀层表面涂装方案  \n\n表面处理：用适当的清洁剂清除油脂，用高压淡水清除盐分和其他污物，轻度喷砂以除去白锈同时将电镀层表面打磨粗糙以确保涂装良好的附着力  \n\n<html><body><table><tr><td>序号</td><td>涂层</td><td>涂料品种</td></tr><tr><td>1</td><td>序号</td><td>双组分环氧漆</td></tr><tr><td>2</td><td>序号</td><td>双组分聚氨酯面漆</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 配套的技术说明典型的风塔塔筒防腐涂装配套体系是由几种不同类型的涂层组合而成。它包括可提供电化学保护的富锌底漆，可提供屏蔽保护的环氧厚浆漆和防腐与装饰皆佳的聚氨酯面漆。  \n\na.底漆采用环氧富锌底漆。它是一种防锈性能优异的双组分、高含锌量的环氧富锌涂料。其防腐蚀机理是基于金属锌对钢板起到阴极保护的电化学作用。因为锌的电极电位为$-0.76\\mathrm{V}$ ，比铁的电极电位 $(\\mathrm{-0.409V})$ 更负。这样锌作为阳极被腐蚀，铁为阴极而受到保护。完整的环氧富锌底漆可以首先以屏蔽作用的形式保护钢板底材，屏蔽作用隔绝了钢板与腐蚀物的直接接触，在它们之间形成保护膜，当漆膜破损后，还可以对局部破损区域提供阴极保护，使得锈蚀不会蔓延开来，从而达到保护钢板底材的目的（ISO12944要求环氧富锌涂料中不挥发分中的金属锌含量要大于 $80\\%$ ）。  \n\n环氧富锌底漆干燥、复涂、施工性能优异，无论是在车间内，还是在露天环境均可进行施工并良好固化。不易受环境温度、湿度的影响，在低温条件下，采用冬用固化剂，仍可施工并固化。这实际上可大大降低业主的施工费，缩短涂装施工周期。  \n\nb.中间漆选用环氧厚浆漆。固化后，漆膜坚韧，耐海水，耐冲击，形成很好的屏蔽保护层。冬季低温施工时，可使用低温固化产品。c.面漆采用耐紫外线、不变色、耐候性好、装饰性强的聚氨酯面漆，其漆膜坚韧、耐磨、耐腐蚀，而且也耐海水和盐雾，具有优异的保光、保色、抗紫外线、抗老化等耐候性能。聚氨酯面漆以其装饰性与防腐性兼备的优点成为在严重大气腐蚀环境下钢结构长效保护的主要选用面漆。  \n\n上述涂装防护配套方案实际上是一个相辅相成的涂装配套体系，环氧富锌底漆由于有了环氧中间漆和聚氨酯面漆的屏蔽保护而隔绝了与腐蚀物质的直接接触，延长了它的保护寿命，而中间漆和面漆由于有了环氧富锌这样坚实的基础而大大提高了它们的防护性能。该防腐配套方案，以其优异的防腐性能、先进的设计理念和简便的施工性能，在防腐领域的竞争有着明显的技术领先优势。  \n\n塔筒内表面由于不会受阳光、紫外线照射，所以可不用涂装聚氨酯面漆。  \n\n对于一些特殊的材质，如热浸锌、铝材等表面，可选用与热浸锌、铝材附着良好的环氧过渡底漆。  \n\n齿轮箱内部所使用的涂料也可选择附着力非常好、具有优良的耐高温和化学品性能的酚醛环氧漆。  \n\n涂装配套体系的施工性能也是重点考虑的因素之一。从施工的角度而言，良好的施工是防腐体系成功的关键，施工的好坏直接关系到系统的防护寿命。实际上这是任何一种涂装防腐体系发挥作用的基础。因此防腐体系在满足防腐要求的前提下，要尽可能简化，易于现场施工。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 208,
+        "chunk": "# 3.火电站防腐涂料  \n\n火电厂有多种腐蚀环境，如燃煤烟气对厂房环境的污染，设备的高温绝热部位，以及各种设备装置等，大体分类如下。  \n\n$\\textcircled{1}$ 钢结构：锅炉钢结构，厂房钢结构。  \n\n$\\textcircled{2}$ 贮罐内壁。  \n\n$\\textcircled{3}$ 冷却水水管内外壁。  \n\n$\\textcircled{4}$ 高温部位。  \n\n$\\textcircled{5}$ 烟道、烟肉以及脱硫系统装置。  \n\n$\\textcircled{6}$ 冷却塔。  \n\n其中钢结构、贮罐内壁、冷却水管内外壁及高温部位的防腐涂装保护与其他章节重防腐涂装保护中描述的相近，以下只简单介绍其涂装配套，而不加详细介绍，重点介绍烟道、烟肉以及脱硫系统装置和冷却塔防腐涂装。  \n\n（1）火电厂常规部位防腐涂装$\\textcircled{1}$ 钢结构锅炉钢结构的受压件和结构件等，通常采用的防腐蚀涂料如下。a.底漆环氧富锌底漆或无机富锌底漆等。b.中间漆环氧云铁中间漆。c.面漆以聚氨酯面漆为主，也有用丙烯酸面漆等其他的面漆涂料。$\\textcircled{2}$ 火电厂的贮罐火电厂的饮用水罐和去离子水罐其配套为：酚醛环氧贮罐漆 $2x$ $125\\mu\\mathrm{m}$ 或无溶剂环氧漆 $2\\times150\\mu\\mathrm{m}$  \n\n贮罐外壁可参考大气环境的防腐蚀配套。  \n\n火电厂的燃油贮罐通常采用环氧导静电涂料或无机硅酸锌涂料，其配套为：环氧导静电涂料 $2\\times100\\mu\\mathrm{m}$ 或无机硅酸富锌底漆 $1\\times90\\mu\\mathrm{m}$ 心  \n\n$\\textcircled{3}$ 冷却水循环系统的水管涂装传统上采用环氧沥青等涂料或直接用沥青和玻璃纤维布包裹，能起到良好的保护作用。但随着环境保护意识的不断加强，沥青涂料正在淡出涂料领域，取而代之的是不含沥青的石油树脂改性环氧树脂漆的推广应用，由于改性环氧是用石油树脂改性，具有良好的润湿性能和附着力，且环氧具有良好的力学性能，能经受运输安装等碰撞，而且固体含量高，有些已经采用无溶剂涂料。无溶剂涂料的使用，有利于施工人员的健康和现场安全，因此高固体分改性环氧涂料是较为合适的涂料产品，可以用常规的施工方法和程序进行施工。高固体分改性环氧涂料在国外很多大型水电站的压力水管和火电厂的循环水管中有着成功的使用记录。  \n\n通常采用的是作为底面漆使用的厚膜型改性环氧漆两道，如：改性厚膜型环氧漆 $2x$ $250\\mu\\mathrm{m}$ 或 $2\\times300\\mu\\mathrm{m}$ d  \n\n$\\textcircled{4}$ 高温隔热部位火电厂有些设备处于高温状态，且因设备和部位不同而温度不同，需要来用不同种类的涂料与之配套。  \n\n常规使用的化学固化类涂料，如环氧树脂涂料和聚氨酯涂料产品，最大可以耐 $120^{\\circ}C$ 的高温，因此，在 $120^{\\circ}C$ 以下温度范围，可以采用通常的防腐蚀涂料系统。  \n\n醇酸铝粉耐热漆以及有机硅酸改性的醇酸树脂漆可以耐 $200^{\\circ}C$ 的高温。  \n\n保温隔热层内的防腐系统必须考虑一旦隔热层破损，里面就会积聚水汽，呈酸性的冷凝水是主要的腐蚀因素，通常采用耐热达 $230^{\\circ}C$ 的酚醛环氧树脂涂料。  \n\n无机硅酸锌涂料可以耐 $400^{\\circ}C$ 的高温，因此，只要管道温度在 $400^{\\circ}C$ 以内，完全可以把无机硅酸锌底漆作为通用的防锈底漆。  \n\n在 $500{\\sim}600^{\\circ}C$ 的高温环境下，可以使用有机硅铝粉耐热涂料。漆膜厚度通常只有 $20\\sim$ $30\\upmu\\mathrm{m}$ 厚，可以涂装两道的配套系统。  \n\n不同温度范围以及隔热部位的涂料系统见表3-3-97。  \n\n(2）脱硫系统及烟肉/烟道的防腐涂装在脱硫系统用于烟气处理以前，烟道和烟肉处于 $130{\\sim}140^{\\circ}\\mathrm{C}$ 的高温状态，所以钢制的烟肉和烟道无需考虑防腐蚀问题。  \n\n现在国家要求排放烟气必须经过脱硫装置，排出的烟气温度经过GGH（烟气换热器)加热后仍为 $80^{\\circ}C$ 左右，如果不经过GGH，排出的烟气为 $40\\sim50^{\\circ}C$ 。不论是否经过GGH，经过脱硫装置处理后排出的烟气都处在烟气冷凝的范围，从而会对烟道和烟肉造成腐蚀。因此，要求电厂对新建烟肉要进行防腐蚀保护和对旧烟肉增加防腐蚀保护涂层。  \n\n表3-3-97 高温隔热部位的涂料系统  \n\n\n<html><body><table><tr><td>温度范围/℃</td><td>涂层</td><td>涂料产品</td><td>干膜厚度/μm</td></tr><tr><td><120（适用于没有隔热层的部 位）</td><td>底漆 中间漆 面漆</td><td>环氧富锌底漆 环氧云铁中间漆 丙烯酸聚氨酯面漆</td><td>75 125 50</td></tr><tr><td><230</td><td>底漆 底/面漆 底/面漆</td><td>醇酸铝粉耐热漆 中温型有机硅耐热漆</td><td>30X2 25X2</td></tr><tr><td><400</td><td>底漆 面漆</td><td>酚醛环氧耐热漆 无机富锌底漆 有机硅铝粉耐热漆</td><td>100 75 25</td></tr><tr><td><600</td><td>底漆</td><td>有机硅铝粉耐热漆</td><td>25X2</td></tr></table></body></html>  \n\n$\\textcircled{1}$ 脱硫后的烟道和烟肉的防腐蚀保护材料烟道上使用的防腐蚀保护涂层通常有乙烯基酯涂料和乙烯基酯胶泥。  \n\n烟肉上使用的防腐蚀保护涂层通常有耐酸混凝土、耐酸玻璃砖、乙烯基酯玻璃鳞片胶泥和乙烯基酯玻璃鳞片涂料。  \n\n$\\textcircled{2}$ 乙烯基酯玻璃鳞片涂料在烟卤和烟道上的使用乙烯基酯玻璃鳞片涂料在烟肉和烟道上使用的配套系统如下。  \n\n底漆：乙烯基酯玻璃鳞片漆(铁红色)， $600\\mu\\mathrm{m}$ 或 $750\\mu\\mathrm{m}$ 面漆：乙烯基酯玻璃鳞片漆(白色)， $600\\mu\\mathrm{m}$ 或 $750\\mu\\mathrm{m}$ 中  \n\n表面处理应采用适合的磨料做喷砂处理，须达到ISO8501-1Sa2.5级，粗糙度达到ISO 8503-2中规定的粗的等级（ $75\\sim130\\mu\\mathrm{m})$ 。可采用压缩比大于 $65:1$ 的常规无气喷涂机进行施工。  \n\n$\\textcircled{3}$ 乙烯基酯玻璃鳞片涂料  \n\na.乙烯基酯树脂乙烯基酯树脂指的是以环氧化合物为母体，分子两端带有不饱和双键的一类有机酯类化合物，它们通常由不饱和一元酸与环氧化合物通过开环酯化反应而得，其在苯乙烯等交联剂中的溶液则称为环氧乙烯基酯树脂。  \n\n在前苏联的文献中将这类树脂命名为环氧（甲基）丙烯酸酯树脂，我国早期报道这类树脂的文献中曾称之为（甲基）丙烯酸环氧酯树脂，在西方国家的文献中则将这类树脂简称为乙烯（基）酯（vinylester）树脂。  \n\n乙烯基酯树脂的基本合成工艺路线如下。  \n\n![](images/131112e00f01f3dae659a039e6a6c0fa26bd5ff55dabf22c2610b23d59f334cd.jpg)  \n\n$\\textcircled{2}$ 乙烯基酯树脂的主要品种在乙烯基酯树脂的合成中，选择不同的不饱和一元酸和不同的环氧树脂，可得到不同的乙烯基酯树脂，加上采用不同的化合物改性，可制得具有各种特性的乙烯基酯树脂，因此，乙烯基酯树脂大类中有众多各具特点的衍生产品。  \n\n可采用的不饱和一元酸有丙烯酸、甲基丙烯酸、苯基丙烯酸、丁烯酸等，环氧化合物有双酚A环氧树脂及其同系物、双酚F环氧树脂、酚醛环氧树脂、四溴双酚环氧树脂、二环氧化聚氧化丙烯等。  \n\n目前最常用的品种有两类，双酚A型乙烯基酯树脂（常用的不饱和一元酸有丙烯酸、甲基丙烯酸等）和酚醛环氧类乙烯基酯树脂。  \n\n$\\bigstar$ 双酚A环氧丙烯酸类，其分子结构式为：  \n\n![](images/a8dce83ce687545a59f98b00a959913f4085602de6b822bf63a931a4081c533f.jpg)  \n\n双酚A环氧甲基丙烯酸类，其分子结构式为：  \n\n![](images/6d87cc1fd9048b0667a3d4eeefdf512ca7b7ad5c12b9817bb32c4c14a97be0d4.jpg)  \n\n酚醛环氧乙烯基酯类，其分子结构式为：  \n\n![](images/8be8eafadeb30164041b88093539539fa4411fe54170ea2fad353ab2beb7ebe3.jpg)  \n\n$\\textcircled{6}$ 乙烯基酯树脂的结构特点在以上分子结构中，苯环的结构稳定，提供刚性和热稳定性；醚键（一O—）的化学稳定性好，提高树脂的韧性和耐疲劳性；羟基（一OH）的极性给树脂以良好的浸润性和附着力。  \n\n此外，在分子结构中，双键的位置位于分子的两端，易于在固化时发生交联反应，提高了固化的程度，也对树脂的耐腐蚀性能具有相当的贡献。  \n\n由于酯基较易于水解，所以酯基在分子中的数量对漆膜的耐水性和耐腐蚀性有较大的影响，一般来说，酯基的数量越少，耐水性和耐腐蚀性就越强，据报道，一般酯基浓度少一半，耐水的时间就能增长20倍。而在乙烯基酯树脂中不仅酯基的含量较低，且酯基边上的甲基和苯乙烯基对其有一定的屏蔽作用，使之更难以水解，所以具有优良的耐腐蚀性能。  \n\n虽然可以用乙烯基酯树脂的结构本身所显示的结构特点来解释其优良的耐水解性能，也必须考虑对树脂的运用最终是由固化后的漆膜来实现的，所以也必须注重在固化过程中所形成的有苯乙烯链段参与的固化网络的高次结构对其耐腐蚀性能和耐温性能的影响。  \n\n丙烯酸酯聚合后主链上具有的醚键可自由旋转，同时具有柔性的异氰酸酯基团，从而使分子主链的柔韧性得到大大增强。  \n\n树脂固化成膜后的耐温性与其结构骨架基团的稳定性及树脂交联密度有关，在双酚A乙烯基酯树脂中含有双酚A、苯环等结构，而用酚醛环氧制得的乙烯基酯树脂除含有多个稳定的苯环结构外且端基有多个活性双键，其在成膜过程中的交联密度最大，所以其耐热温度最高，耐化学药品的腐蚀也最好。有些厂家在产品命名时也称为其耐高温乙烯基酯涂料。  \n\n$\\textcircled{c}$ 乙烯基酯树脂的固化体系乙烯基酯树脂的固化体系是通过引发剂产生的自由基激活树脂及交联剂（苯乙烯）中的双键，使树脂发生加聚反应而固化。一般采用有机过氧化物为引发剂，用钻盐或胺类化合物作为促进剂。  \n\n最常用的两种固化体系为：  \n\n$\\cdot$ 过氧化甲乙酮/环烷酸钻（或辛酸钴）；  \n$\\bullet$ 过氧化二苯甲酰/二甲基苯胺。  \n\n在实际使用时，引发剂过氧化甲乙酮、过氧化二苯甲酰均已先与邻苯二甲酸二丁酯按一定比例混合配制好；促进剂环烷酸钻、二甲基苯胺也同样用苯乙烯稀释剂配制好。一般使用配方为：  \n\n$\\cdot$ 乙烯基酯树脂100/过氧化甲乙酮 $2\\sim4,$ /环烷酸钻 $1{\\sim}4$ 中$\\cdot$ 乙烯基酯树脂100/过氧化二苯甲酰 $2\\sim4/$ 二甲基苯胺 $1{\\sim}3$  \n\n第一个配方固化速率比第二个配方快，而第二个配方后固化优于第一个配方。有报道认为第二个配方固化物的耐蚀性优于第一个配方（a)。  \n\n由于用户具体使用时环境温度、加工工艺等各不相同，会对树脂凝胶时间的长短有不同的要求，这就需要对引发剂和促进剂的品种、加入量的大小等作相应的选择和调整。需要较快固化的可选择第二个配方。需快速固化或在低温、潮湿情况下可选择复合固化体系，如乙烯基酯树脂100/过氧化甲乙酮2/环烷酸钴3/二甲基苯胺0.5，乙烯基酯树脂100/过氧化甲乙酮1/二甲基苯胺0.5/过氧化二苯甲酰1/环烷酸钴0.5。在缠绕成型时，当需要有较长凝胶时间时可采用第一个配方，并减少引发剂、促进剂的用量，如采用配方：乙烯基酯树脂100/过氧化甲乙酮1/环烷酸钻0.5，在 $20^{\\circ}C$ 时胶凝时间为 $2.5\\mathrm{h}$ 甲  \n\n对于用户来说，应根据涂料供应商的施工要求对固化剂的品种和数量进行调整，其主要依据是施工时的环境温度和底材温度，供应商将调整好的比例作为原包装发给客户使用。涂料供应商所作的标准配比的适合范围通常在 $15\\sim40^{\\circ}C$ ，通常要求施工温度不低于 $10^{\\circ}C$ 。在环境温度超过 $35^{\\circ}C$ 较高的施工环境下，还应配以 $0.02\\%$ 的二甲基苯混用作抑制剂，以避免过快的固化而影响施工。  \n\n乙烯基酯树脂涂料产品由于其双键具有较大的活性，常温下在较短的时间内就能达到较完全的固化反应，漆膜可以具有相当的性能，但如果期望漆膜达到最佳性能，常温固化后应再经 $100^{\\circ}C$ 、2h的热处理。  \n\nb.乙烯基酯玻璃鳞片涂料中的玻璃鳞片玻璃鳞片于1953年由美国欧文斯-康宁玻璃纤维公司开发，接着该公司将玻璃鳞片和环氧树脂等混合制成涂料应用于混凝土基材和钢管内衬，此后美国和日本等国家相继使用这项技术，现今玻璃鳞片涂料已成为一种有效的重防腐蚀涂料。  \n\n在乙烯基酯玻璃鳞片涂料的组成中，乙烯基酯树脂的性能起着决定性的作用，但玻璃鳞片的加人，对于乙烯基酯玻璃鳞片涂料各方面的性能都有所提高。  \n\n玻璃是无机材料，其组成决定了它具有良好的耐化学药品及抗老化性能，玻璃鳞片很薄，经过正确的施工，使得它在涂层中与底材平行排列，形成致密的防渗透屏障，使涂层中的微裂纹、微气泡相互分隔，称为曲径效应，具有大大延长腐蚀介质渗透到底材时间，提高了涂层的抗渗透性和防腐蚀保护寿命。  \n\n玻璃鳞片在涂层中还减少了涂层与底材之间的热膨胀系数差，而且也明显降低了涂层本身的硬化收缩率。一是玻璃鳞片涂层的硬化收缩率比其他涂层要低几倍至十几倍，二是玻璃鳞片在涂层中使得涂层中形成许多的小区域，降低涂层内应力的传递，有助于抑制涂层龟裂、剥落等病的出现，而且可提高涂层的附着力和耐冲击性能。  \n\n所以，玻璃鳞片在提高涂层的防腐蚀性能、耐冲击、耐磨性能、抗渗透性能以及改变涂膜应力等方面，都具有重要的贡献。但玻璃鳞片在涂料中的加入量有一定的要求，太小将导致鳞片的重叠排列不足，影响抗渗透性能；但如果过多会使得鳞片在成膜过程中不能很好地飘浮而造成无序排列，反而使得涂层的致密性降低。所以鳞片的用量有一个最佳的范围，一般配方中，玻璃鳞片的加入量在 $20\\%\\sim35\\%$ 睿  \n\n用于乙烯基酯玻璃鳞片涂料的玻璃鳞片需要考虑以下一些因素：玻璃的组成成分；玻璃鳞片的厚度；玻璃鳞片的尺寸和分布；玻璃鳞片的表面处理。  \n\n$\\cdot$ 玻璃的组成成分玻璃分为C玻璃和 $\\operatorname{E}$ 玻璃，在涂料中使用的是C玻璃。所谓C玻璃就是硼硅酸盐玻璃，以 $\\mathrm{SiO_{2}}$ ， $\\bar{\\mathrm{B}}_{2}\\bar{\\mathrm{O}}_{3}$ “ ${\\bf R}_{2}\\odot$ 为主要成分，具有热膨胀系数小、良好的热稳定性和化学稳定性。  \n\n$\\cdot$ 玻璃鳞片的厚度玻璃鳞片的厚一般为 $5\\mu\\mathrm{m}\\pm2\\mu\\mathrm{m}$ 。理论上讲，玻璃鳞片在 $1000\\mu\\mathrm{m}$ 厚度的漆膜中可达到100层以上，但根据各涂料配方的不同而不同。一般在玻璃鳞片含量为 $20\\%$ 左右的涂料配方中，可达到100层以上。玻璃鳞片的厚度直接决定了涂料涂层的曲径效应。有的玻璃鳞片的厚度远远大于 $5\\mu\\mathrm{m}$ 的规格，有些甚至达到 $25\\mu\\mathrm{m}$ 之多，不仅影响了曲径效应，更使得玻璃鳞片在漆膜中的排列不规则，这样的玻璃鳞片不适合在玻璃鳞片涂料中使用。  \n\n$\\cdot$ 玻璃鳞片的尺寸和分布玻璃鳞片的径厚比越大，平均分散系数越小，抗水蒸气透过率越低，但同时空气排除能力也越差。要对径厚比以及长度分布进行选择，通常在涂料中选择的规格为总的长度分布范围在 $10{\\sim}4000\\mu\\mathrm{m}$ ，其中 $65\\%$ 以上应在 $55\\sim330\\mu\\mathrm{m}$ 冏中  \n\n$\\cdot$ 玻璃鳞片的表面处理玻璃鳞片一般用硅烷偶联剂处理，不同型号的树脂应选用不同型号的偶联剂对玻璃鳞片进行表面处理，经过有效表面处理的玻璃鳞片能使树脂与玻璃鳞片结合紧密，减少基料中微气泡、微孔隙、分子级空穴等。而且处理过的玻璃鳞片在树脂中的飘浮性好，有利于鳞片与基体之间的平行排列，从而大大提高涂层的抗渗性和防腐性能。  \n\nc.乙烯基酯玻璃鳞片涂料的性能表3-3-98为酚醛环氧型乙烯基酯玻璃鳞片涂料的物理性能。  \n\n表3-3-98 酚醛环氧型乙烯基酯玻璃鳞片涂料的物理性能  \n\n\n<html><body><table><tr><td>项 目</td><td>性能特点</td><td>测试方法</td></tr><tr><td>拉伸强度/MPa</td><td>85</td><td>ASTMD638/ISO527</td></tr><tr><td>拉伸模量/MPa</td><td>3.0</td><td>ASTMD 638/ISO527</td></tr><tr><td>拉伸延展性/%</td><td>3</td><td>ASTM D 638/ISO 527</td></tr><tr><td>挠曲强度/MPa</td><td>130</td><td>ASTMD 790/ISO 178</td></tr><tr><td>挠曲模量/MPa</td><td>3.0</td><td>ASTMD 790/ISO 178</td></tr><tr><td>热变形温度/℃</td><td>160</td><td>ASTM D 792/ISO 1183</td></tr><tr><td>巴氏硬度</td><td>40</td><td>ASTMD 2583/EN59</td></tr><tr><td>耐磨性(1000μm×1)</td><td>108mg/1000r/17/1000g</td><td>ASTM D 4060</td></tr><tr><td>附着力（拉开法）（ChemflakeS700μm×2）</td><td>7.1MPa(在3mm厚度的钢板上）</td><td>ISO 4624</td></tr><tr><td>耐冲击性（DFT500um）3mm钢板/完全干燥</td><td>30in·lbf通过</td><td>ASTMG14</td></tr></table></body></html>\n\n注：以上数据为商业化产品的实测数据。  \n\n由于烟肉和烟道在运行过程中，脱硫烟气在运行GGH（气体热交换器）时的温度在$80^{\\circ}C$ 左右，不运行GGH时的烟气温度 $40\\sim50^{\\circ}C$ ，都会出现酸凝露现象，所以耐酸性能是必须考虑因素之一。表3-3-99为酚醛环氧型乙烯基酯玻璃鳞片涂料可接受的酸性环境。  \n\n表3-3-99酚醛环氧型乙烯基酯玻璃鳞片涂料可接受的酸性环境  \n\n\n<html><body><table><tr><td>介质</td><td>浓度/%</td><td>最高使用温度/C</td><td>介质</td><td>浓度/%</td><td>最高使用温度/℃</td></tr><tr><td rowspan=\"3\">硫酸</td><td>10</td><td>80</td><td rowspan=\"3\">盐酸</td><td>10</td><td>80</td></tr><tr><td>50</td><td>80</td><td>20</td><td>80</td></tr><tr><td>70</td><td>30</td><td>37</td><td>60</td></tr><tr><td rowspan=\"2\">硝酸</td><td>5</td><td>60</td><td rowspan=\"2\">乙酸</td><td>25~50</td><td>70~80</td></tr><tr><td>20</td><td>40</td><td>75</td><td>50</td></tr></table></body></html>  \n\n(3）乙烯基酯玻璃鳞片涂料的施工玻璃鳞片涂料的施工基本与通常的厚膜型涂料的施工要求相同，如可用常用的无气喷涂机进行，但又有其特殊的要求，列举如下。  \n\n$\\textcircled{1}$ 乙烯基酯涂料施工的钢材表面必须使用喷砂处理表面，达到 $\\mathsf{S a2.5}$ ，但粗糙度须达到75～130um。  \n\n$\\textcircled{2}$ 促进剂、引发剂和阻聚剂的加入量因温度的不同而不同，检查作业区温度，依据混合比例表计算出正确的添加剂的添加量，根据其数据准确添加并注意先后次序，同时要注意，引发剂的加人时间必须是在开始喷涂的最后时刻。  \n\n$\\textcircled{3}$ 由于乙烯基酯漆的混合后可使用时间较短，一般在常温下时 $45\\mathrm{min}$ ，如果在夏天温度较高的情况下其可使用时间则会相应缩短，如果固化凝结得太快，则会在管子和泵内凝结。建议在施工乙烯基酯涂料时准备好备用泵，一旦泵体温度较高，就换一台泵使用，并马上将使用过的泵清洗干净。  \n\n④乙烯基酯涂料在施工时漆桶中剩余的涂料不能倒入下一桶涂料中。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 209,
+        "chunk": "# 4.核电站的防腐涂装  \n\n作为一种洁净、高效能源，核能正越来越备受各国的重视。在我国也在不断地开发和利用这一高效的洁净能源。我国从20世纪70年代开始，建设的核电站有广东大亚湾核电站、岭澳核电站一期、秦山一期、秦山二期和秦山三期核电站等。现在正在开发和建设的还有岭澳核电站二期、阳江核电站、辽宁大连红沿河核电站等。由于核电站所需求环境条件和相应配套体系的特殊性，所以我国目前开发和建设或即将建设的核电站均在海边位置，所有的设备和建筑物不仅要承受阳光强烈曝晒、经受风雨，还会受到水汽、盐雾和海水潮气的侵蚀，极易受到腐蚀。长效的涂装防护系统不仅能大大延长涂层的维修周期，延长整个核电设备的使用寿命，而且对整个核电站的安全起到至关重要的作用。针对核电站的腐蚀环境特点和其特殊要求，相关设备所选用的涂装防护系统应不仅要具有良好的防腐性能，同时要求漆膜坚硬耐冲击并具有良好的耐候性、耐水性、附着力强和装饰等性能。  \n\n以大亚湾核电站为例作一介绍。室内金属构件主要采用磷酸锌环氧聚酰胺底漆/聚酰胺环氧苯酚面漆或环氧云母氧化铁涂料/高固体分环氧涂料；室外金属构件主要采用含硅或环氧富锌底漆/聚酰胺环氧乙烯中涂漆/脂族聚酯聚氨酯面漆或环氧富锌涂料，以及环氧云母氧化铁涂料。环氧云母氧化铁涂料还用于混凝土表面。  \n\n（1）核电站基本结构及其防腐涂装标准  \n\n$\\textcircled{1}$ ① 核电站基本结构和主要涂装部位核电站是利用在动力反应堆中进行的核裂变反应所产生的热能来发电或发电兼供热的动力设施。目前世界上核电站反应堆有压水堆、沸水堆、重水堆、快墟以及高温气冷堆等，但广泛使用的是压水反应堆，是目前最成熟、最成功的动力堆型。以压水反应堆核电站为例，其基本结构与运作原理如图3-3-54所示，主要由核岛、常规岛、BOP（电站配套设施）等组成。其主要涂装部位有：a.核岛内部钢结构、安全壳；b.核岛内部混凝土结构；c.常规岛、BOP钢结构/混凝土结构等；d.风道、管道；e.各类贮罐（油、水、化学品)；f埋地件；g，与液体介质接触的部位等。  \n\n![](images/766966b70424f45a67683f1fec86bd589cc17b114f02230ca6f8ab12c6c042cb.jpg)  \n图3-3-54压水式反应堆核电站快基本结构与运作原理示意图  \n\n$\\textcircled{2}$ ②核电站防腐涂装主要引用标准  \n\na.EJ/T1086—1998《压水堆核电厂用涂料漆膜在模拟设计基准事故条件下的评价试验方法》（本标准综合采用：ASTMD3911—1995《轻水堆核电厂用涂料在模拟设计基准事故条件下的性能和可修补性试验方法》和NFT30-900—1996《色漆和清漆核工业用涂料在设计基准事故条件下的性能和可修补性试验方法》)。  \n\nb.EJ/T1087—1998《压水堆核电厂用涂料耐化学介质的测定》 （本标准等效采用  \n\nASTMD3912—1995《轻水堆核电厂用涂料耐化学性的标准试验方法》。  \n\nc.EJ/T1111—2000《压水堆核电厂用涂料漆膜受 $\\boldsymbol{\\gamma}$ 射线辐照影响的试验方法》（本标准综合采用：ASTMD4082—1995《轻水堆核电厂中涂层受 $\\gamma$ 射线辐照影响的标准试验方法》和NFT30-903—1988《色漆和清漆核工业用涂料在电离辐照下稳定性的试验》》。  \n\nd.EJ/T1112—2000《压水堆核电厂用涂料漆膜可去污性的测定》（本标准等效采用：NF T30-901—1995《色漆和清漆核工业用涂料沾污敏感性和去污能力的评价试验方法》)。e.RCCM一2000（法国）《压水堆核岛机械设备设计和建造规则》。  \n\n(2）核电站防腐涂料及其涂层系统根据我国某大型核电站《核岛机械设备涂装通用技术条件》的涂层系统分类要求和提供的系统所在环境条件，结合各种涂料的性能特点，将涂料系统分为核岛内涂料和非核区涂料。  \n\n$\\textcircled{1}$ 核岛内涂料关于用于核岛内涂层系统除了防腐蚀基本要求外，主要应具备耐核辐射性能，并且要容易去污。对于其中某些设备或部位，例如核燃料的贮槽与输送管道等，还必须具有优异的耐化学腐蚀性和吸收辐射线的能力，以防止放射源周围的环境受到污染。一旦涂料系统选定之后，怎样才能确定它是否能用呢？一般都要通过以下四项试验：耐辐射性能试验；耐化学介质试验；去污染性能试验；冷却剂事故损失试验（LOCA试验)。  \n\na.核岛内涂料的试验方法  \n\n$\\cdot$ 耐辐射性能试验耐辐射性能试验一般是将涂料样板置于照射室内，用钻或 $\\gamma$ 射线的辐射设备照射，剂量选取 $5\\times10^{7}\\mathrm{rad}$ ， $1\\times10^{8}\\mathrm{rad}$ 、 $5\\times10^{8}$ rad、 $1\\times10^{9}\\mathrm{rad}$ 、 $1\\times10^{10}$ rad、 $1\\times$ $10^{11}\\mathbf{rad}$ 。按要求的时间照射之后以目测、红外光谱及电子显微镜观察、拍照等方法评价涂层表面形态的变化。该项试验方法可按国家核行业标准EJ/T1111—2000《压水堆核电厂用涂料漆膜受 $\\boldsymbol{\\gamma}$ 射线辐射影响的试验方法》执行。  \n\n对于核电站所用的涂料，一般要求至少能耐 $10^{9}\\mathtt{r a d}$ 的剂量。研究结果发现，在聚台物结构中，如果主链或支链上带有芳香环，则其耐辐射性能好，由辐射引起的降解轻微。而不带芳香环的聚合物，例如聚氯乙烯、聚四氟乙烯、聚甲基丙烯酸酯等，在核辐射作用下是不稳定的。此外，颜（填）料和各种助剂的选择对涂料的耐辐射性能也有影响。表3-3-100和表3-3-101分别列出13种涂料耐辐射的最大剂量和美国的霍洛克斯公司对6种涂料进行 $\\gamma$ 射线试验结果供参考。  \n\n表3-3-10013种涂料耐辐射的最大剂量  \n\n\n<html><body><table><tr><td>涂料</td><td>耐辐射的最大剂量/Mrad</td><td>涂料</td><td>耐辐射的最大剂量/Mrad</td></tr><tr><td>二苯基硅氧烷涂料</td><td>5000</td><td>聚氨酯涂料</td><td>1000</td></tr><tr><td>酚醛涂料</td><td>5000</td><td>三聚氰胺甲醛涂料</td><td>1000</td></tr><tr><td>环氧酚醛涂料</td><td>5000</td><td>脲-三聚氰胺涂料</td><td>500</td></tr><tr><td>催化型环氧涂料</td><td>5000</td><td>聚乙烯醇缩丁醛涂料</td><td>500</td></tr><tr><td>苯乙烯涂料</td><td>5000</td><td>硝基纤维素涂料</td><td>100</td></tr><tr><td>乙烯基咔唑涂料</td><td>4000</td><td>醋酸纤维素涂料</td><td>50</td></tr><tr><td>沥青涂料</td><td>2000</td><td></td><td></td></tr></table></body></html>  \n\n表3-3-101美国霍洛克斯公司对6种涂料进行耐 $\\gamma$ 射线辐射试验  \n\n\n<html><body><table><tr><td>涂料</td><td>耐Y射线辐射试验结果</td><td>备注</td></tr><tr><td>酚醛涂料（蓝色）</td><td>用>5×10°radY射线在50℃、100%RH条件照射下，28天后，其 耐磨性和附着力无变化</td><td></td></tr><tr><td>有机硅醇酸涂料（白色）</td><td>在10°rad射线照射下漆膜无变化，在5×10°radY射线照射下部 分发生变化</td><td></td></tr><tr><td>醇酸涂料（白色、红色）</td><td>在10°rad）射线照射下，白色和红色面漆硬化且变色（由于分子内 双键氧化所致），红色面漆附着力略差，而黑色面漆变软。总体说明耐含32%苯酐醇酸漆作面 Y射线辐射性能较差</td><td>以富锌漆作底漆，以 漆</td></tr></table></body></html>  \n\n<html><body><table><tr><td>涂料</td><td>耐Y射线辐射试验结果</td><td>备注</td></tr><tr><td>普通环氧涂料</td><td>在5X10°～10×10°radY射线照射下，涂层显著老化</td><td></td></tr><tr><td>氟乙烯涂料</td><td>在5×10°～10×10°radY射线照射下，涂层耐腐蚀性和附着力不 好，有脱落现象</td><td></td></tr><tr><td>硝基喷漆（白色）</td><td>在10°radY射线照射下，白色面漆产生多孔和变质，而红色面漆虽 末完全变质，但有些发软，黑色面漆附着力略差。总体说明耐射线 辐射性能较差</td><td>以富锌漆作底漆，以 硝基喷漆作面漆</td></tr></table></body></html>  \n\n从表3-3-100、表3-3-101可以看出，二苯基硅氧烷、酚醛与环氧酚醛、催化型环氧以及聚苯乙烯四种涂料的耐辐射性能更好。然而，究竟哪些涂料的耐辐射性能更好，各个国家和各使用者的看法不尽一致。  \n\n去污染性能 就是除污率，即：  \n\n$$\n\\mathrm{\\DI=lgDF}\n$$  \n\n除污率大则表示涂层的去污染耐核辐射涂层还必须具有很好的去污染性能。涂层经受核辐射后，表面会留下放射性污染物。所谓去污染性能，就是指污染之后的涂层表面的表层上的放射性污染物能够被消除或减少到相当低的程度。这种性能对于工作人员和设备来说都是很重要的，所以核反应堆的防事故外壳区和辅助区都有去除污染的相关规定。  \n\n去污染性能的表示方法如下。  \n\n$\\mathbf{\\delta}_{\\mathbf{\\overline{{\\Pi}}}}\\mathbf{\\Pi}_{\\mathbf{\\overline{{\\Pi}}}}\\left(\\mathbf{\\Pi}_{\\mathbf{\\overline{{\\Pi}}}}\\right)$ 去污因子DF和去污百分数 $A$  \n\n$$\nA{=}1{-}\\frac{1}{\\mathrm{DF}}\n$$  \n\n例如，当DF为20时， $A$ 为 $95\\%$ ，表示已去除了 $95\\%$ 的污染物，当DF为100时，A为 $99\\%$ ，表示已去除了 $99\\%$ 的污染物。  \n\n$\\mathbf{\\delta}_{\\mathbf{\\overline{{\\deltau}}}}$ 除污率DI：去污因子的对数性能好。不同的涂料，其去污染性能也不同。表3-3-102列出了13种涂料的涂层受 $\\mathbf{S}^{35}$ ， $\\mathbf{P}^{32}$ 核分裂物污染和经去污处理后的DI值。  \n\n续表  \n表3-3-102 几种涂料的涂层受 $5^{35}$ ， $\\mathbf{P^{31}}$ 核分裂物污染经去污处理后的DI值  \n\n\n<html><body><table><tr><td>涂层</td><td>S35</td><td>P32</td><td>核分裂物</td></tr><tr><td>氯乙烯清漆-1</td><td>2.41</td><td>0.54</td><td>1.83</td></tr><tr><td>氯乙烯清漆-2</td><td>1.86</td><td>0.45</td><td>1.45</td></tr><tr><td>氯乙烯清漆-3</td><td>2.01</td><td>0.60</td><td>1.90</td></tr><tr><td>醇溶性酚醛清漆</td><td>2.05</td><td>.0.19</td><td>1.23</td></tr><tr><td>透明喷漆</td><td>2.38</td><td>0.49</td><td>1.36</td></tr><tr><td>100%油改性酚醛清漆</td><td>2.15</td><td>0.36</td><td>0.81</td></tr><tr><td>甲基丙烯酸树脂清漆</td><td>2.00</td><td>0.43</td><td>1.37</td></tr><tr><td>大豆油改性醇酸树脂清漆</td><td>2.34</td><td>0.38</td><td>1.18</td></tr><tr><td>酚醛改性醇酸树脂清漆</td><td>2.32</td><td>0.39</td><td>0.68</td></tr><tr><td>熟油</td><td>2.01</td><td>0.55</td><td>0.55</td></tr><tr><td>氯化橡胶清漆</td><td>2.19</td><td>0.24</td><td>1.00</td></tr><tr><td>有机硅树脂清漆</td><td>2.35</td><td>0.45</td><td>0.78</td></tr><tr><td>苯乙烯丁二烯树脂清漆</td><td>2.20</td><td>0.17</td><td>0.60</td></tr></table></body></html>  \n\n涂层的去污染性能在很大程度上取决于其表面性质和表面状态，如果表面均匀、平滑、致密和坚硬，则不易吸附放射性污染物，且能耐去污剂的多次洗涤。  \n\n去污染方法一般是采用去污剂去除污染，主要有四种类型，即溶液型或胶体型洗涤剂、多价离子浓溶液和螯合物溶液、强酸及非离子型多磷酸盐（ $\\tt{p H}$ 为9.5）和阴离子型柠檬酸盐（ $\\mathbf{\\nabla}[\\mathbf{pH}$ 为3.0)。其他去污剂还有很多，如 $50\\%$ 草酸、 $35\\%$ 六偏磷酸钠和 $15\\%$ 其他物质，  \n\n配成 $1\\%$ 水溶液使用，效果很好。  \n\n去污试验方法可按国家核行业标准EJ/T1112—2000《压水堆核电厂用涂料漆膜可去污性的测定》执行。  \n\n·冷却剂事故损失试验（LOCA试验）冷却剂事故损失试验（LOCA试验）也叫做漆膜在模拟设计基准事故条件下稳定性试验（DBA试验)。试验方法可按国家核行业标准EJ/T1086—1998《压水堆核电厂用涂料漆膜在模拟设计基准事故条件下的评价试验方法》执行。  \n\n在核反应堆运转过程中，必须考虑冷却剂因事故而损失的可能性。LOCA试验方法是把试样放在高温高压容器中，将pH约为9、含3000mg/kg的硼酸水溶液喷入，经规定的周期试验后取出样板，检查评定，涂层不得有任何损坏，否则判定整个涂料系统不合格、不能用。试验中的温度、压力变化以及喷淋阶段特征曲线，如图3-3-55所示。  \n\n![](images/90d753e5411c9a935ca586ef415d079c2b386170bbd4601b89666f73bf510d74.jpg)  \n图3-3-55LOCA试验温度压力特征曲线  \n\n$\\cdot$ 耐化学介质试验核岛内常见的气体腐蚀介质有氧化氮、氯、氟等，液体腐蚀介质有硝酸、硫酸、柠檬酸等。这些腐蚀介质中最常遇到的是氧化氮和硝酸，所以要求涂料除必须耐核辐射之外，还要耐腐蚀，具有良好的化学稳定性。  \n\n耐化学介质试验方法可按国家核行业标准EJ/T1087—1998《压水堆核电厂用涂料漆膜耐化学介质的测定》执行。  \n\n除了上述四项试验必须做外，还应当注意到核岛内各种装置在不同部位所接受的辐射剂量不同（例如在靠近放射源处受到的是高能辐射，而远处受到的是低能辐射)，也应考虑不同设备和不同部位的耐热性、电绝缘性以及耐老化等其他方面的要求。  \n\nb.常用核岛内涂料及其发展趋势目前国内外常用核岛内涂料品种主要包括改性环氧涂料、酚醛环氧涂料以及聚氨酯涂料等。  \n\n目前世界上耐核辐射涂料研究主要还是下述两个方面。一方面尽可能提高其耐辐射能力，改善其耐辐射性能。已经有不少涂料能耐 $10^{9}\\mathrm{rad}$ 的剂量，有机硅涂料是目前耐辐射剂量最高的，可达 $10^{11}$ rad左右。是否还有耐更高辐射剂量的涂料，有待于进一步研究。另一方面努力寻找多性能涂料，如上所述，除了能耐辐射之外，还要能去污染和具备某些特殊性能，例如耐热和电绝缘等。现在发现以下几类涂料可能成为耐核辐射涂料的发展方向：有机硅涂料、硅亚苯基聚合物和杂环聚合物。  \n\n$\\textcircled{2}$ 非核区涂料对于非核区和处于室内或室外的大气环境(包括室内外的海洋气候)，根据  \n\nISO12944-2《腐蚀环境分类》规定分：在室外的（包括室内外的海洋气候）应是处于在C4～C5腐蚀环境，即非常高的腐蚀环境；而室内由于不直接与外部大气自然环境接触，应属于C3腐蚀环境，即中等腐蚀环境。根据以上设备和结构所处的环境条件，按照ISO12944有关长效防腐的要求，推荐以下相关部件、结构和设备的防护配套体系。  \n\n非核区域涂层系统适用的厂房和环境范围见表3-3-103，它符合国际标准ISO12944中有关钢结构在不同的腐蚀环境下达到长期耐久防护的规定。用于不同温度条件下钢铁表面、不锈钢或镀锌件表面的涂层配套系统见表3-3-104～表3-3-108，供读者参考。  \n\n表3-3-103 非核区域涂层系统适用的厂房和环境范围  \n\n\n<html><body><table><tr><td>系列代号</td><td>适用的厂房和环境</td></tr><tr><td>2-1</td><td>用于室内非核区域正常大气环境下的涂层系统（没有放射性污染，没有酸碱等腐蚀性气氛的区域）</td></tr><tr><td>2-2</td><td>用于室内非核区域内腐蚀性气氛环境下的涂层系统（没有放射性污染的区域）</td></tr><tr><td>2-3</td><td>用于厂房内的缠绕保温材料的高温设备、管道（t>120℃）</td></tr><tr><td>2-4</td><td>用于露天海洋性大气环境下的涂层系统</td></tr></table></body></html>  \n\n表面处理：打砂至国际标准ISO8501-1：1988（相当于国标GB8923—1988）的 $5\\equiv2.5$ 级，表面粗糙度达到ROGOTESTNO.3BN9a级  \n\n表3-3-104 用于钢铁表面（ $:t<=120^{\\circ}C$ ）涂层系统  \n\n\n<html><body><table><tr><td>底漆：环氧/无机富锌底漆</td><td>50~60μm</td></tr><tr><td>面漆；厚浆型环氧漆</td><td>150~200μm</td></tr></table></body></html>  \n\n表3-3-105 用于钢铁表面 $\\tan\\angle E$ ）涂层系统  \n\n\n<html><body><table><tr><td>NO.3BN9a级 底漆：铝粉耐热漆</td><td>25~30μm</td></tr><tr><td></td><td>25~30μm</td></tr></table></body></html>  \n\n<html><body><table><tr><td colspan=\"2\">表面处理：打砂至国际标准ISO8501-1：1988（相当于国标GB8923—1988）的Sa2.5级，表面粗糙度达到ROGOTEST NO.3BN9a级</td></tr><tr><td>底漆：耐热漆（锌粉）</td><td>50~60μm</td></tr></table></body></html>  \n\n表3-3-107 用于钢铁表面（ $t=120^{\\circ}C$ ， $t^{\\sum}120^{\\circ}C$ ）涂层系统  \n\n\n<html><body><table><tr><td colspan=\"2\">表面处理：打砂至国际标准ISO8501-1：1988（相当于国标GB8923—1988）的Sa2.5级，表面粗糙度达到ROGOTEST NO.3BN9a级</td></tr><tr><td>底漆：环氧/无机富锌底漆</td><td>50~70μm</td></tr><tr><td>中间漆：厚浆型环氧（云铁)漆</td><td>150～200μm</td></tr><tr><td>面漆：丙烯酸聚氨酯面漆</td><td>60~80μm</td></tr></table></body></html>  \n\n表3-3-106 用于钢铁表面（ $\\angle2=120^{\\circ}C$ ）涂层系统  \n\n\n<html><body><table><tr><td colspan=\"2\">表面处理：清除表面所有油污、污物和盐分，用砂纸打磨表面</td></tr><tr><td>底漆：环氧底漆</td><td>25~50μm</td></tr><tr><td>面漆：厚浆型环氧漆</td><td>150~200μm</td></tr></table></body></html>  \n\n表3-3-108 用于不锈钢或镀锌件等表面 $\\zeta_{L}=\\zeta_{1}20^{\\circ}C$ ）涂层系统  \n\n上述用于非核区域的涂层系统是由几种不同类型的涂层组合而成。它主要包括可提供电化学保护的环氧/无机富锌底漆，可提供屏蔽保护的环氧（云铁）厚浆漆和防腐性与装饰性  \n\n皆佳的丙烯酸聚氨酯面漆。  \n\n对于在室内环境下的钢结构和设备的防护，由于室内不遭受日晒雨淋及外部环境污染的影响较小，因此对其耐候的要求就远远低于室外结构和设备的要求，可以考虑不选择耐候性能优异的聚氨酯面漆，如环氧、丙烯酸、醇酸等面漆。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 210,
+        "chunk": "# 六、地坪涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 211,
+        "chunk": "# 1.地坪涂料概况  \n\n地坪涂料主要是指用于水泥、混凝土、石材和钢材地坪表面，对地面起装饰、保护或提供某些特殊功能的涂料。  \n\n地坪防腐与化工设备及其他防腐有共同之处，目的都是为了保护基体不受化学介质的侵蚀，但地坪防腐也有其特点：①防腐面积大；②腐蚀介质复杂，有气体、粉尘、液体多相介质作用，介质的种类也随生产中存在的介质而变化，往往是多种介质，因此腐蚀性较强；$\\textcircled{3}$ 地坪还要经受不可避免的摩擦、冲击等机械作用； $\\textcircled{4}$ 地坪腐蚀危害大，地坪一旦遭受腐蚀，可能造成地基下沉，危及设备基础、建筑物等； $\\textcircled{5}$ 施工条件差。地坪防腐难以设置防雨、挡阳措施，施工场地的温度和湿度往往难以达到较理想的范围。地坪涂料使用要求的复杂性导致了地坪涂料种类的多样性。  \n\n地坪涂料按照其功能和用途来分，主要有普通装饰性地坪涂料、耐重载地坪涂料、超耐蚀地坪涂料、防静电地坪涂料、防核辐射地坪涂料、防滑地坪涂料等。上述分类方法只是侧重了地坪涂料的某一功能，实际上地坪涂料的功能不是单一的，而是同时具有上述功能的儿种或更多。  \n\n按照地坪涂料的主要成膜物质来分，地坪涂料产品主要有以下儿种：环氧树脂地坪涂料、聚氨酯树脂地坪涂料、不饱和聚酯树脂地坪涂料、丙烯酸树脂涂料、氯化聚烯烃耐化学介质地坪涂料、聚脲弹性体地坪涂料等。在发达国家，地坪涂料经过近40年的发展，得到不断改良与更新，不同工艺、不同成膜物质、不同功能的地坪涂料不断出现，丰富了地坪涂料的种类。国内自20世纪80年代引进地坪涂料技术以来，地坪涂料行业得到了飞速发展，自普通的溶剂型薄涂地坪之后，逐步出现了砂浆型地坪、溶剂型自流平地坪、无溶剂自流平地坪、防静电地坪、防核辐射地坪、防滑地坪、装饰性极强的彩砂地坪和环氧磨石地坪、水性树脂地坪涂料等。  \n\n由于环氧地坪涂料对混凝土等多种底材的附着力优良、固化收缩率低；具有良好的耐水性、耐油性、耐酸碱性、耐盐雾腐蚀等化学特性；同时具有优良的耐磨性、耐冲压性、耐洗刷性等物理特征；在使用时不易产生裂纹且易冲洗、易维修保养。使其在工业地坪行业占有重要地位，成为地坪涂料中应用最广泛的品种。",
+        "category": " Introduction"
+    },
+    {
+        "id": 212,
+        "chunk": "# 2.环氧树脂地坪涂料  \n\n环氧树脂地坪涂料主要由成膜物质（包括环氧树脂和固化剂以及可能含有的活性稀释剂)、颜料、填料、助剂、溶剂（包括水）等物料组成。  \n\n（1）成膜物质根据地坪涂料的要求，成膜物质应具有常温固化、高粘接力、较强力学性能、耐化学品等性能。地坪涂料用环氧树脂一般有两类：一类是由双酚A和环氧氯丙烷缩聚而成的双酚A型环氧；另一类是以苯酚-甲醛缩聚而得的低分子量酚醛再与环氧氯丙烷缩聚而成的酚醛环氧。  \n\n分子量较高的固态环氧树脂一般用于溶剂型地坪涂料，其分子中含有较多羟基，可以采用聚氨酯预聚物固化成膜，也可以采用胺类固化剂与环氧基开环加成固化成膜。而在高固体分和无溶剂环氧地坪涂料配方中一般采用分子量较低的液态环氧树脂。低黏度环氧树脂分子中虽然羟基含量较少，固化速率较慢，但可制成厚膜涂料，且与固化剂混容性好，施工流平性好，多用胺类固化剂固化，固化速率可以通过加人固化促进剂来提高。在高固体分和无溶剂地坪涂料中，为了调节黏度和改善性能，也常加人活性稀释剂。液态环氧树脂也常用于溶剂型涂料。近几年，水性环氧地坪涂料以其优异的透气性和环保优势得到了快速发展，其成膜物质可以是液态环氧树脂配以具有乳化功能的水性胺类固化剂，也可以是各种分子量的水性环氧乳液配以水性胺类固化剂，该固化剂不一定需具备乳化功能，可以是水溶性的，也可以是乳液。  \n\n胺类固化剂是环氧树脂地坪涂料的主要固化剂。胺类固化剂主要有脂肪胺、脂肪胺加成物、环脂胺、环脂胺加成物、聚酰胺、聚酰胺加成物、曼尼希碱等。表3-3-109是环氧树脂地坪涂料常用胺类固化剂的性能比较。  \n\n表3-3-109 常用胺类固化剂的性能比较   \n\n\n<html><body><table><tr><td>项目</td><td>脂肪胺</td><td>脂肪胺加成物</td><td>环脂胺 浅</td><td>环脂胺加成物 浅</td><td>聚酰胺 较深</td><td>聚酰胺加成物 较深</td><td>曼尼希碱 较深</td></tr><tr><td>色泽 黏度 适用期 固化速率 流平性 耐磨性 涂层外观 粘接性 柔韧性 耐化学品 耐冲击性 熟化期</td><td>较浅 低 短 快 较差 好 油腻泛白 一般 较差 优 差</td><td>较浅 低 短 较快 一般 好 一般 一般 较差 优 差</td><td>低 较短 较快 好 好 好 较好 一般 优 一般</td><td>较低 较短 较快 好 好 好 较好 一般 优 一般</td><td>较高 长 较慢 较好 好 较好 好 好 良 好</td><td>较高 长 较慢 较好 好 较好 好 好 良 好</td><td>适中 较短 较快 一般 好 一般 较好 一般 优</td></tr><tr><td>施工性能 实例</td><td>需熟化 差 TMD (Huls)</td><td>不必熟化 一般 Ancamine 1769 (Air Products)</td><td>不必熟化 较好 HY2963 (Ciba)</td><td>不必熟化 较好 Ancamine 1618 (Air Products)</td><td>需熟化 好 Versamid 115 (Henkel)</td><td>稍熟化 好 Ancamine 1691(Air Products)</td><td>一般 稍熟化 好 T31固化剂 （华昌）</td></tr></table></body></html>  \n\n在表3-3-109所列的各种固化剂中，脂肪胺与环氧树脂反应很快，发热量大，涂膜交联密度高，耐化学品性能很好，但是性脆，耐冲击性能差。脂肪胺加成物是脂肪族多元胺与环氧树脂加成而成。用此种胺加成物时漆膜不易吸潮泛白，刺激性气味小，配漆后不必熟化就可直接使用。  \n\n环脂胺及其加成物的许多性能较脂肪胺及其加成物有较大提高，如色泽浅淡、流平性好、黏度低、光泽高、不易泛白、无诱导期，可用作无溶剂地坪涂料的固化剂。典型的如Air Products 公司的Ancamine1618，其主要组成即是环脂胺与低分子量的液态环氧树脂加成的产物。  \n\n聚酰胺树脂和酰氨基胺固化剂对湿度不敏感，在潮湿基面固化时容忍度好，但与环氧树脂的混容性不好，与环氧树脂配合后存在诱导期。用聚酰胺树脂（或酰氨基胺）同环氧树脂的加成物则可克服这一缺点。该加成物可克服表面发白现象，并且不需要诱导期。但由于这类固化剂黏度较高，它们只能配成溶液，用于溶剂型涂料中并且有较高的VOC含量。近年来，随着国外固化剂合成技术的发展，国际市场上出现了新的改性酰胺固化剂，如AirProducts公司牌号为Ancamine2353的改性聚酰胺，该产品黏度低，可用于高固体分涂料，与环氧树脂的相容性较好，提高了固化程度，较大地改善了传统聚酰胺固化物的耐溶剂性能  \n\n和抗化学品性能。  \n\n曼尼希（Mannich）碱是经曼尼希反应而合成的，由酮（或酚）、甲醛及胺三者缩合而得，产物分子中含有酚羟基，能促进固化，必要时还可以加人其他促进剂，如壬基酚、辛基酚来促进固化反应。我国涂料工业也制造此类固化剂，习惯称为“酚醛胺”，它的固化特点是即使在低温、潮湿环境下也能固化。主要缺点是固化后的涂膜较脆，为此，可在配方中加人其他化合物进行改进，国内在20世纪80年代初开发的环氧树脂固化剂T31就是这种类型，该固化剂毒性小，在潮湿性和低温下固化性能良好，在国内已经有20多年成功应用的历史，是我国室温环氧树脂固化剂的主要品种之一，在环氧地坪涂料砂浆层中应用极为普遍。  \n\n如果采用相同的曼尼希反应，而用单官能的代替多元胺，则产品是叔胺。最典型的是称为DMP-30（或称K-54）的固化剂，能促进聚酰胺、硫醇等与环氧基交联。它还能单独促进环氧树脂自身的环氧基之间互相开环交联。  \n\n随着人们对环境保护的关注，水性环氧固化剂也得到了迅速发展，国外早在20世纪70年代，就已经对水性环氧固化剂进行了开发，目前水性环氧固化剂在发达国家应用比较普遍。典型的有日本三和化学工业株式会社的水性改性聚酰胺SUNMIDEWH900和 SUN-MIDEWH1000、德国 Cognis的水稀释性改性脂肪胺Waterpoxy 751、美国Air Products 公司的改性脂肪胺乳液Anquamine701、美国Shell公司的水稀释性胺加成物EPIKURE 8537-WY-60等产品，表3-3-110是上述几种水性环氧固化剂的性能规格。  \n\n表3-3-110 水性环氧固化剂的性能规格  \n\n\n<html><body><table><tr><td>产品</td><td>黏度（25℃）/mPa·s</td><td>密度/（g/cm）</td><td>活泼H当量</td><td>固体分/%</td><td>胺值/（mgKOH/g)</td><td>色泽Gardner</td></tr><tr><td>WH900</td><td>15000~20000</td><td>1.08</td><td>225</td><td>60±2</td><td>150~180</td><td><10</td></tr><tr><td>WH1000</td><td>15000~20000</td><td>1.07</td><td>210</td><td>60±2</td><td>170~200</td><td><10</td></tr><tr><td>Anquamine701</td><td>75000</td><td>1.10</td><td>300</td><td></td><td></td><td>乳白</td></tr><tr><td>Waterpoxy 751</td><td>8500～15000</td><td></td><td>225</td><td>60.0±1.5</td><td>174～192</td><td><8</td></tr><tr><td>EPIKURE 8537-WY-60</td><td>Z~Z4(Gardner-Holdt)</td><td>1.08</td><td>174</td><td>60±1</td><td>310~360</td><td><9</td></tr></table></body></html>  \n\n近年来，由于国内水性环氧地坪涂料、水性环氧无毒防霉内墙涂料、水性环氧防腐涂料以及水性环氧粘接剂等材料的需求逐步扩大，而国外的水性环氧固化剂虽然性能良好，但价格高昂，在国内市场的推广存在一定难度。国内多家研发机构和企业对水性环氧固化剂的研制成功，顺应了市场发展的需求。表3-3-111列举了几种商业化的国产水性环氧固化剂性能规格。  \n\n表3-3-111 国产水性环氧固化剂的性能规格  \n\n\n<html><body><table><tr><td>产品</td><td>厂家</td><td>黏度（25℃） /mPa·s</td><td>密度 /(g/cm²）</td><td>活泼H 当量</td><td>固体分 /%</td><td>胺值 /(mgKOH/g)</td><td>色泽Gardner</td></tr><tr><td>WEC402</td><td>青岛海洋化工</td><td>4000~6000</td><td>1.12</td><td>216</td><td>60</td><td>170~185</td><td><8</td></tr><tr><td></td><td>研究院</td><td></td><td></td><td></td><td></td><td></td><td><8</td></tr><tr><td>HZ05B</td><td>上海汉中</td><td>4000~6000</td><td>一</td><td>285</td><td>51</td><td>1</td><td></td></tr><tr><td>HTW208</td><td>苏州圣杰</td><td>2500~6000</td><td>1.08</td><td>290</td><td>60</td><td>300～360</td><td><9</td></tr><tr><td>HGF</td><td>浙江安邦</td><td>100~200</td><td>1.08</td><td></td><td>40±1</td><td>105～115</td><td>乳白</td></tr><tr><td>GCA02</td><td>上海绿嘉</td><td>5000~8000</td><td>1.10</td><td>320</td><td>50~55</td><td>1</td><td><9</td></tr><tr><td>SP-73-50</td><td>广州秀珀</td><td>7000～9000</td><td>1.04</td><td>240</td><td>60</td><td>170~200</td><td><8</td></tr></table></body></html>  \n\n环氧活性稀释剂分为单环氧化物和多环氧化物，其分子量和黏度较低，能降低涂料黏度，溶解、分散和稀释涂料，改善涂料的流动性、施工性以及涂膜的某些物化性能，且自身含有环氧基，可直接参加固化反应，没有逸出之。通常被应用到高固体分或无溶剂环氧自流平地坪涂料中。常见的单官能环氧活性稀释剂有烯丙基缩水甘油醚（allyl glycidylether，AGE)、丁基缩水甘油醚（BGE)、苯基缩水甘油醚（PGE）和邻甲酚缩水甘油醚（CGE）等。常见的双官能环氧活性稀释剂有新戊二醇二缩水甘油醚和1,4-丁二醇二缩水甘油醚（BDGE）等。  \n\n在用水性胺类固化剂与标准液态环氧树脂复配的地坪涂料中，为了降低交联密度，改善涂膜的韧性，通常在环氧树脂组分中加入活性稀释剂，活性稀释剂还能降低漆料黏度，增加施工时固化剂组分与环氧树脂组分的易混匀性，使固化剂对环氧树脂的乳化功能更好的发挥。  \n\n在地坪涂料配方中，单官能活性稀释剂用量一般不超过环氧树脂的15%，多官能活性稀释剂用量可达到20%～25%。活性稀释剂用量太多，会降低涂膜的性能，如涂膜的硬度和耐溶剂性能等。  \n\n(2）溶剂溶剂对常温固化的环氧地坪涂料的施工期、干性等有影响。极性溶剂能加快固化速率，酮类溶剂能延长使用期限。环氧地坪涂料溶剂的选用，首先考虑其对环氧树脂的溶解性能、挥发速率，溶剂的黏度、闪点及易燃性。为安全考虑，尽可能采用较高闪点的醇、醇醚和酯类，最后还要考虑气味、来源难易及价格高低等。环氧树脂的溶解性随着分子量的增加而降低。酮类、酯类、醇醚类和氯代烃类是环氧树脂的溶剂，对环氧树脂有很好的溶解能力。芳烃和醇类不是环氧树脂的溶剂，但是芳烃和醇混合后，则可作为中等分子量树脂的溶剂，如二甲苯与正丁醇按合适比例混合后则可作为固态环氧树脂的溶剂。  \n\n此外，选用溶剂时还应注意溶剂对固化反应的作用。在环氧基与含活泼氢化合物的固化反应中，如当胺固化环氧树脂，使用酯类和酮类等氢键接受体作溶剂时，其会与固化反应体系内的氢键给予体结合，消耗氢键给予体的浓度，减慢固化反应速率。  \n\n（3）颜料、填料由于地坪涂料要经常遭受各种可能的化学介质的侵蚀，所以着色颜料应选用耐化学性能好的无机颜料，如钛白粉、氧化铬绿、氧化铁黄、氧化锌、炭黑和氧化铁系颜料等。酞菁蓝、酞菁绿等有机颜料虽存在絮凝问题，容易出现浮色、发花等现象，但由于其色彩鲜亮、着色力强、不易沉淀，耐化学性能和耐光耐候性尚可，所以在地坪涂料中也经常得到应用。  \n\n根据地坪涂料使用的特点，填料宜选用吸油量低、耐酸耐碱、硬度高的品种，同时也要考虑填料的外形尺寸、含水率等物性指标以及贮存稳定性。常用的有沉淀硫酸钡、云母粉、滑石粉和石英粉等。硫酸钡是地坪涂料常用的填料，它是一种惰性物质，这种颜料化学稳定性高，耐酸、耐碱、耐光、耐热，不溶于水，吸油量低，但密度较大，用量过多易出现沉降。石英粉的成分为二氧化硅，天然产品化学稳定性比较高，耐酸碱，不溶于水，耐高温，天然产品吸油量低，颗粒比较致密，质地硬，耐磨性强，密度适中，是比较理想的地坪涂料填充料。适量的滑石粉、云母粉的加人，不但可以增强涂层的屏蔽性能，降低漆膜开裂的可能性，而且可以提高漆料的贮存稳定性。  \n\n此外，为了达到某些特殊目的和使用要求，常在地坪涂料中加入某些具有特定功能的填料。例如，在环氧地坪涂料中加人导电颜填料，如金属粉末或金属氧化物导电粉、石墨粉、炭黑、碳纤维、导电聚合物等可以制成防静电地坪涂料；加人耐核辐射的颜料、填料，则可制成防核辐射地坪涂料。有些填料会影响固化过程，如酸性填料三聚磷酸铝加入到经酸中和成盐的水稀释性胺类固化剂-环氧体系配方中会明显延缓涂膜的干燥时间，宜引起注意。  \n\n（4）助剂地坪涂料对消泡和流平以及颜色均一性要求较严格。消泡不良可能会留下针孔和凹坑，形成腐蚀介质渗透的薄弱微区，腐蚀介质透过防腐性能较强的面漆后继续向下扩散，会加速地坪涂层的破坏。流平不好和发花会影响地坪涂料的装饰性。助剂的使用能有效消除或改善这些弊病，但还需考虑重涂性问题，有机硅类助剂或蜡的过量使用有可能降低涂层的表面张力，导致后续涂层附着不良。加人白炭黑和膨润土等触变剂，可以使涂料有良好的贮存稳定性，也有一定的防浮色发花作用。在较低的温度下施工时，应适量加人固化剂促进剂，加快固化反应速率。当用酸中和成盐的水稀释性胺类固化剂配制地坪涂料时，应选用非离子型的分散剂，因为常用的阴离子型分散剂如丙烯酸聚合物的铵盐或钠盐会和阳离子型固化剂分子发生离子中和反应，产生絮凝使分散剂失效。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 213,
+        "chunk": "# 3.环氧树脂地坪涂料的制备工艺  \n\n按涂料中分散介质的含量和分散介质的种类可以将环氧地坪涂料分为：溶剂型环氧地坪涂 料、无溶剂（少溶剂）型环氧地坪涂料、水性环氧地坪涂料。下面介绍其主要组成和制备方法。  \n\n$\\textcircled{1}$ 溶剂型环氧地坪涂料溶剂型环氧地坪涂料主要由环氧树脂、颜填料、溶剂、助剂以及与之配套的固化剂组成。在选择基料时，应注意涂膜内生成的化学键、极性基团、有效交联密度、玻璃化温度及交联固化反应速率对防腐蚀性、粘接性及物理力学性能的影响。溶剂型环氧涂料固体分不高，不宜制成厚膜涂料，否则部分溶剂有可能残留在漆膜中，引起漆膜发软。表3-3-112是一种环氧地坪色漆的参考配方。  \n\n表3-3-112 环氧地坪涂料色漆的参考配方  \n\n\n<html><body><table><tr><td>原料名称</td><td>质量分数/%</td><td>原料名称</td><td>质量分数/%</td></tr><tr><td>环氧树脂E-20</td><td>30</td><td>消泡剂</td><td>0.2</td></tr><tr><td>混合溶剂</td><td>28</td><td>混合填料</td><td>32</td></tr><tr><td>分散剂</td><td>0.4</td><td>颜料浆</td><td>9.4</td></tr></table></body></html>  \n\n如图3-3-56所示是制备上述溶剂型环氧涂料色漆的工艺流程。  \n\n![](images/b145286521bbb24a5f202de0c2cf814ccca45f892f9b801c886c4a3770115a3d.jpg)  \n图3-3-56 溶剂型环氧地坪涂料色漆生产工艺流程图  \n\n$\\textcircled{2}$ 无（少溶剂）环氧地坪涂料无（少溶剂）环氧地坪涂料中不含溶剂或含有少量的溶剂 $(<15\\%$ ，如高固体分涂料)。此类环氧地坪涂料施工挥发物少，从涂料到涂膜的转化率高，形成的涂膜致密、机械强度高、具有优异的防腐蚀性能，且可以制成厚膜涂料。无（少溶剂）环氧地坪涂料主要由低分子量的液态环氧树脂、环氧活性稀释剂、颜填料、助剂以及与之配套的固化剂（如环脂胺的环氧加成物）组成。其制备工艺与溶剂型环氧地坪涂料相仿。此类地坪涂料的典型代表是无溶剂环氧自流平地坪涂料。表3-3-113是一种无溶剂环氧自流平地坪涂料的基本技术指标。  \n\n表3-3-113 无溶剂环氧自流平地坪涂料技术指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项 目</td><td>指标</td></tr><tr><td>涂料状态</td><td>黏稠液体 锻涂</td><td>粘接强度/MPa 邵氏硬度/D</td><td>≥2</td></tr><tr><td>涂料施工方法</td><td></td><td>耐磨性（750g/500r，失重）/g</td><td>≥75 ≤0.02</td></tr><tr><td>干燥时间/h</td><td>≤6</td><td></td><td>30天轻微变色</td></tr><tr><td>表干</td><td>≤24</td><td>耐60%HSO</td><td>30天无异常</td></tr><tr><td>实干 拉伸强度/MPa</td><td>≥9</td><td>耐25%NaOH 耐3%盐水</td><td>30天无异常</td></tr><tr><td>弯曲强度/MPa</td><td>≥7</td><td>耐汽油（120*）</td><td>耐</td></tr><tr><td></td><td>≥85</td><td></td><td></td></tr><tr><td>耐压强度/MPa</td><td></td><td></td><td></td></tr></table></body></html>  \n\n无（少溶剂）环氧涂料在地坪涂装系统中主要应用在以下几个方面。  \n\na.用作高强度弹性地坪涂料：高强度无（少）溶剂型环氧弹性承重地坪涂料是由环氧树脂、颜料、填料、助剂和与之相配的固化剂等构成的双组分厚浆涂料。采用刮涂施工可形成 $0.5\\sim5\\mathrm{mm}$ 的中间承重弹性层，固化后表面光滑，承重载荷大于 ${\\mathfrak{g o M P a}}$ 西  \n\nb.用于承受重载荷耐冲击混凝土环氧地坪的加厚中间层或接缝处及修补层。  \n\nc.用作薄涂型防腐蚀地坪涂料：涂膜有效交联密度高，致密性好、抗介质渗透能力强，耐化学药品和耐蚀性优良。刷涂或辊涂施工，可用于化工厂、炼油车间、石油化工防腐、地下设施防水等场所的专用防腐地坪材料。  \n\nd.用作厚涂型环氧地坪耐磨耐蚀地坪涂料：一次施工厚度可大于 $1\\mathrm{mm}$ 。涂装后表面光滑，接近镜面效果；耐酸、碱、盐及油类介质腐蚀，特别耐强碱性能好；耐磨、耐压、耐冲击，有一定弹性；使用寿命一般在8年以上。被广泛应用于要求高度清洁、美观、无尘、无菌的电子、微电子以及实行GMP标准的制药、血液制品等行业的地坪防护。  \n\n$\\textcircled{3}$ 水性环氧地坪涂料传统的溶剂型地坪涂料存在着较多的挥发性溶剂，对人体和环境存在不同程度的危害；而且油性环氧地坪涂料和无（少）溶剂环氧地坪涂料固化成膜后漆膜较致密，地下水汽难以穿透漆膜，在潮湿基层施工时容易出现鼓泡、剥离等弊病。水性环氧地坪涂料因其具有环保、透气等优点，在近年来得到了快速发展，广泛应用于食品、医药、化妆品等行业的地坪防护以及潮湿基面的地坪防护，如用作混凝土码头防护底漆等。  \n\n水性环氧地坪涂料是双组分涂料，表3-3-114列举了一种国内市场商业化的水性环氧地坪涂料配方。  \n\n表3-3-114 水性环氧地坪涂料配方  \n\n\n<html><body><table><tr><td>配方</td><td>质量分数/%</td><td>配方</td><td>质量分数/%</td></tr><tr><td>甲组分 低分子量液态环氧树脂</td><td>90.0</td><td>钛白粉、石英粉、硫酸钡、绢云母等 润湿分散剂 消泡剂</td><td>45.0 0.6 0.3</td></tr><tr><td>活性稀释剂 乙组分 水性环氧固化剂 水</td><td>10.0 30.0</td><td>流平剂 增稠剂</td><td>0.3 0.3</td></tr></table></body></html>  \n\n根据涂料的使用要求和成本预算，调整乙组分配方中固化剂和颜料、填料，可以按要求制成底漆和面漆。甲乙两组分的配比（按甲组分包含的环氧基团的物质的量与乙组分包含的氨基活泼氢的物质的量之比计）为，甲组分：乙组分 $=(1.0{\\sim}1.2)\\ :1$ ，适度提高环氧树脂的用量，可提高漆膜的耐水性和耐腐蚀性。制得的水性环氧地坪面漆基本性能指标见表3-3-115。  \n\n表3-3-115 薄涂型水性环氧地坪涂料面漆性能指标  \n厚膜型水性环氧地坪面漆如水性环氧自流平地坪因其固化时易产生开裂、消泡困难等弊  \n\n\n<html><body><table><tr><td>项 目</td><td>指标</td><td>项 目</td><td>指标</td></tr><tr><td>干燥时间/h</td><td></td><td>耐冲击性/kgf·cm</td><td>50通过</td></tr><tr><td>表干</td><td>3</td><td>耐洗刷性/次</td><td>≥10000</td></tr><tr><td>实干</td><td>18</td><td>耐10%NaOH</td><td>30天无变化</td></tr><tr><td>铅笔硬度/H</td><td>2</td><td>耐10%HCI</td><td>10天无变化</td></tr><tr><td>附着力/级</td><td>0</td><td>耐润滑油（机油）</td><td>30天无变化</td></tr><tr><td>耐磨性（750g/500r，失重）/g</td><td>≤0.02</td><td></td><td></td></tr></table></body></html>  \n\n病，用量远不及薄膜型的水性环氧地坪面漆。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 214,
+        "chunk": "# 4.其他类型地坪涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 215,
+        "chunk": "# （1）聚氨酯地坪涂料  \n\n聚氨酯涂料作为地坪涂料，除了具有良好的防腐蚀性外，还有好的耐候性和装饰性，但它的价格较贵些，有些聚氨酯涂料中含有相当多的游离异氰酸酯，吸入人体有害健康，必须做好防护措施；含异氰酸酯的涂料很活泼，遇水或潮气会凝胶，因此贮存时必须封闭。施工操作不慎易引起层间剥离、起泡等弊病。所以制造和施工时必须严格遵守操作规程。  \n\n美国材料试验协会（ASTM）将聚氨酯涂料按其组成和成膜机理将其分为五大类： $\\textcircled{1}$ 氨基甲酸酯改性油涂料（单组分）； $\\textcircled{2}$ 湿固化聚氨酯涂料（单组分）； $\\textcircled{3}$ 封闭性聚氨酯涂料（单组分）； $\\textcircled{4}$ 催化固化型聚氨酯涂料（双组分）； $\\textcircled{5}$ 羟基固化型聚氨酯涂料（双组分）。  \n\n在地坪涂料中应用最广泛是双组分羟基固化型和湿固化型，  \n\n$\\textcircled{1}$ 双组分羟基固化型聚氨酯地坪涂料此类涂料分为含羟基和异氰酸酯基的甲、乙两组分，分别贮存。使用前将两组分混合涂布，使异氰酸酯基与羟基反应，形成聚氨酯高聚物。这类双组分聚氨酯涂料是所有聚氨酯涂料中产量最大、应用最广、调节适应性宽、最具代表性的品种，色漆通常为羟基组分。作为双组分聚氨酯地坪涂料用的羟基组分，一般有环氧树脂、丙烯酸树脂、聚酯、聚醚等树脂。  \n\n$\\textcircled{2}$ 单组分潮气固化型聚氨酯地坪涂料单组分潮气固化型聚氨酯涂料是含有—NCO封端的预聚物，通过与空气中的潮气反应生成胺释放出 $\\vec{\\mathrm{CO}_{2}}$ (该步反应较慢)，生成的胺继续与异氰酸酯反应交联成脲键固化成膜（该步反应比较快）。  \n\n单组分潮气固化聚氨酯涂料施工方便，操作时间长，可在相对湿度为 $50\\%\\sim90\\%$ 、温度最低为 $o^{\\circ}C$ 的环境中施工；固化成膜后，涂膜内含有大量的氨酯键和脲键，因此漆膜有耐磨、耐腐蚀、耐化学品、耐油、耐水、附着力强、柔韧性好等优良特点，单组分潮气固化聚氨酯清漆的机械耐磨性往往比双组分聚氨酯清漆好，硬度较低时，耐磨性更优。在国内，此种涂料被大量用于地坪涂装体系的封闭底漆和罩面清漆，使用效果良好。但是潮气固化型聚氨酯在空气湿度低时干得慢，有时需添加催干剂。由于该涂料需要吸潮固化，所以漆膜不宜涂布太厚，一方面涂布过厚不利于吸潮固化；另一方面不利于 $\\mathrm{CO_{2}}$ 逸出，形成气泡，施工时应引起注意。  \n\n(2）不饱和聚酯树脂地坪涂料用多元醇和多元酸缩聚而成的产物称为聚酯，如果原料中含有一定数量的不饱和多元酸，则产物为不饱和聚酯。如果不饱和聚酯再加以单体稀释（如苯乙烯）即可制成无溶剂的不饱和聚酯涂料。这种涂料在引发剂和促进剂的作用下，能交联固化成不熔不溶的漆膜。  \n\n不饱和聚酯涂料具有良好的耐溶剂、耐水、耐多种化学药品性以及优良的耐磨性，可做成无溶剂地坪涂料，表面光滑亮洁，近年来在地坪涂料领域得到了较大发展，特别是用作无溶剂鳗涂（或刮涂）自流平地坪涂料。但由于涂膜的交联密度大，漆膜较脆，抗冲击性能差；固化收缩率较环氧树脂大，因而附着力也较差，与混凝土的粘接强度低，一般为1.5MPa左右（环氧树脂地坪大于2MPa)；且漆膜不易修补，因而其在地坪行业的用量远不及环氧树脂地坪涂料。  \n\n(3）乙烯基酯树脂地坪涂料乙烯基酯树脂一般是由环氧树脂（双酚A型、双酚F型、酚醛型等）与不饱和一元酸（如丙烯酸、甲基丙烯酸、丁烯酸、油酸等）开环反应制得，产物有时称为环氧丙烯酸酯树脂，或称之为不饱和环氧树脂，习惯上称为乙烯基酯树脂。乙烯基酯树脂（vinylester）的特征为：端基含乙烯酯基（如HzC-C-C-O—），而聚合物主链是 $\\scriptstyle\\mathbf{H_{2}C=C-C-O-\\atop\\mathbf{\\downarrow}}$ 环氧树脂的母体。  \n\n乙烯基酯树脂耐酸、碱、油类、醇类多种化学介质，不耐的介质有：丙酮、液氨、苯、三氯乙烯、三氯酚、吡啶、酚、苦味酸、二氯甲烷、乙基溴等。  \n\n由于乙烯基酯树脂可制成无溶剂涂料，且具有极佳的耐酸、耐碱性和较好的韧性，其延伸率可达 $6\\%$ ，适合制成高度耐蚀、耐磨的玻璃鳞片重防腐地坪涂料及慢涂型厚浆地坪涂料，具有轻质、高强、耐冲击、耐磨、抗渗等优点，使其在重防腐地坪领域，如化工厂、有色冶金、机械工厂、电镀、电池厂、钢铁厂等地坪防护扮演着举足轻重的角色。  \n\n（4）氯化聚烯烃耐化学介质地坪涂料大量含氯原子的聚烯烃作为主要成膜物质制得的地坪涂料具有优良的耐化学腐蚀性、耐候性以及高的起始光泽，加上聚烯烃本身的价格较低，是地坪涂料工业中新型的成膜物质，可以制成底漆、面漆，用作室内外混凝土地坪的防护涂料。这类聚合物中的含氯量一般为 $40\\%\\sim65\\%$ ，大部分为单组分挥发自干型涂料，也可以制成交联型涂料。常见的氯化聚烯烃主要有聚乙烯、聚丙烯、聚氯乙烯等的氯化物以及其相应的共聚物的氯化物、氯磺化聚乙烯等。最近国内也推出氯醚树脂（氯乙烯/乙烯异丁基醚共聚物)，该树脂制成的涂料避免了普通氯化高聚物涂料需引人增塑剂引起的长久使用而使涂膜变脆现象，耐久性得到提高。  \n\n(5）聚脲弹性体地坪涂料聚脲弹性体涂料为双组分产品：一组分为色漆组分，主要由端氨基聚醚、液态胺扩链剂、颜料以及助剂组成；另一组分为异氰酸酯组分。其固化反应为：  \n\n它使用了端氨基聚醚和胺扩链剂作为活泼氢组分，与异氰酸酯组分的反应活性极高，无需任何催化剂，即可在室温（甚至 $0^{\\circ}C$ 以下）瞬间完成反应。此类地坪涂料具有优异的理化性能，如拉伸强度可达 $27.5\\mathrm{MPa}$ ，伸长率可达 $100\\%$ ，柔韧性、耐磨性、耐老化、防腐蚀性能均优异等。同时还具有突出的耐介质性能，除二甲基甲酰胺、二氯甲烷、氢氟酸、浓硫酸、浓硝酸、浓磷酸等强溶解、强腐蚀介质外，它可耐受绝大部分腐蚀介质的长期浸泡。除此之外，还具有良好的温变稳定性，可在 $120^{\\circ}C$ 下长期使用，可承受 $350^{\\circ}C$ 的短时热冲击，也能在高硬度情况下保持优异的低温韧性。  \n\n聚脲弹性体涂料在地坪领域可以用作制药、食品、饮料等生产车间和仓库地面的弹性耐磨保护层；要求防炫目、消光、防滑的高级运动场、羽毛球场、跑道等耐磨面层涂料，在这类场合应用时还可以通过喷涂直接获得表面具有均匀颗粒的“麻面”涂层。也可用于停车场、人行通道、过街天桥等高防滑性场合。  \n\n(6）丙烯酸酯地坪涂料丙烯酸酯涂料是用丙烯酸酯或甲基丙烯酸酯单体通过加聚反应生成的聚丙烯酸酯树脂制成。由于丙烯酸酯树脂对光的主吸收峰处在太阳光谱范围之外，所以用它制成的丙烯酸酯涂料具有特别优良的耐光性及耐户外老化性能，能长期保持原有的光泽和色泽，不易分解变黄；此外还有较好的耐弱酸、弱碱、盐、油脂、洗涤剂等化学品的沾污及腐蚀性能，但耐磨性、耐冲击性能不及环氧和聚氨酯地坪涂料，目前正被广泛地用于室内外休闲场地及轻度使用的地面装饰材料。如各类工厂、办公室等要求不高的场所，无重压及化学溶剂的仓库、厂房，但在地下水汽较重的场合不适用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 216,
+        "chunk": "# 5.地坪涂层系统设计与施工  \n\n(1）地坪涂层系统设计由于地坪涂料的使用情况和施工环境复杂多变，因此需要针对具体使用环境和客户要求对涂层系统进行专门设计。涂层系统的设计一般需要考虑以下因素。  \n\n$\\textcircled{1}$ 涂料的基本性能指标所选涂料的基本性能指标应尽量满足中华人民共和国化工行业标准的地坪涂料标准HG/T3829—2006。水性地坪涂料和弹性地坪涂料不适应该标准。  \n\n$\\textcircled{2}$ 地坪涂层的使用环境一方面应充分考虑地坪在使用期间酸、碱、盐、溶剂、油、海水、淡水、风砂等介质对地坪的侵蚀影响，所选涂料应对腐蚀介质具有较强的抗性，如环氧树脂地坪涂料、聚氨酯地坪涂料、乙烯基酯树脂地坪涂料、氯化聚烯烃地坪涂料和聚脲弹性体地坪涂料等对化学介质都具有较好的抗性，但抗性的侧重点不一样，需要根据实际情况做出最佳选择；另一方面应考虑机械、载荷对地坪的碾压、冲击和磨蚀影响，涂层的设计强度应能满足使用要求。此外，如果基层的含水率长期较高，就还需要考虑涂料对潮湿的敏感性和涂层的透气性，不透气的涂层容易被地下水汽顶起而鼓泡剥离、脱落。如没做防水层的一楼潮湿地面宜施工具有透气性的水性环氧地坪涂料。  \n\n③涂层的造价和目标使用寿命使用寿命是根据地坪使用环境、地坪涂层造价、维护或翻新难易来确定的。长效涂层一般施工要求较高，涂层较厚，造价也较高，维护或翻新相对困难。普通薄涂型地坪造价低廉，容易维护和翻新，但是容易损坏，使用寿命不长，一般为3～5年。无溶剂环氧自流平地平和聚氨酯自流平地坪造价高，但能提供装饰效果好、耐化学介质、耐冲击和碾压的涂层，使用寿命相对较长，可超过10年。  \n\n④各涂层的配套性为获得使用性能良好的地坪涂层，如良好的附着力及耐腐蚀性、耐久性、抗重压性能等，施工时往往需要将底漆、中层漆和面漆配套协同使用，并制定最适当的施工工艺，以满足多重性能要求。如图3-3-57所示是一种典型的地坪涂层结构剖面图。  \n\n![](images/be9746b568fb1acdf71f9517de4ff6d1247421a3c246a1d8893e5502c0b87350.jpg)  \n图3-3-57一种典型的地坪涂层结构示意图  \n\na.底涂 基面经过表面处理后，第一道工序是涂布底漆，这是涂料施工过程中最基础的工作。底涂的目的是在基面与随后的涂层之间创造良好的结合力，补强基础，稳固基面残留的尘粒，且对基面的潮气和碱起一定的封闭作用。油性底漆漆膜  \n\n致密，对基面有较好的封闭效果，但其透气性差，当应用于潮湿基面时，容易出现漆膜被地下水汽压力顶起而剥离的情况。水性底漆漆膜没有油性的那么致密，一般具有微孔结构，能释放地下聚集的水汽压力，在潮湿基面也能取得较好的应用效果。如双组分水性环氧底漆对混凝土基面具有良好的附着力，近年来在潮湿混凝土基面取得了较广泛的应用。根据基面材质和表面状况正确地选择底漆品种及其涂布工艺，能起到提高涂层性能、延长涂层寿命的作用。地坪底漆应与基材有良好的附着力；本身具有良好的机械强度；对底材具有良好的保护性能和不起坏的副作用；能为以后的涂层创造良好的基础，不能含有能渗人上层涂膜引起弊病的组分；更要具有良好的施工性、干燥性。  \n\nb.中涂在地坪涂装体系中，中涂层是介于底涂和面涂之间的涂层，砂浆层和腻子层都属于中涂层，一般由多道组成。中涂层一方面可以找平基面，对基面实行进一步加工；另一方面可以增加漆膜厚度，提高承载能力与涂层使用寿命。中涂层不能对基面和底漆产生不良影响，如咬底、侵蚀等，且不能含有能渗人面涂层引起病的组分；具有一定的机械强度，如耐压强度、弯曲强度、拉伸强度等；具有良好的施工性、干燥性和打磨性。涂层如需抗重压，可在涂层间铺设增强材料，如玻璃纤维布。如果基面较平整且无需耐重压，可不施工砂浆层，而直接施工腻子层找平基面，这样造价会比较经济，但使用年限会比施工了砂浆层的涂装系统短。中涂层用的涂料应与所用的底漆和面漆配套，具有良好的附着力，耐久性应与面漆相适应。如果要求涂层能释放地下水汽压力时，底涂层、中涂层和面层还需具有透气性。但水性中涂和面涂的耐压强度不及无溶剂产品，一般为40MPa左右，而无溶剂产品的耐压强度可达 $\\mathrm{\\bar{80MPa}}$ ，故在需耐重压的场所不适宜采用水性涂料地坪。  \n\nc.面涂面漆的漆膜一般较致密，能抵挡化学介质和溶剂的侵蚀，耐磨性好，且具有良好的力学性能，能展现色彩，有良好的装饰效果与防护性能。面漆不应含有能溶解或溶胀中层涂料的成分，其强度和化学抗性应能满足设计要求，且具有良好的重涂性，以便于修补。  \n\n$\\textcircled{5}$ 工期要求过长的施工时间会影响生产经营的进程，给生产单位带来损失。如果要求地坪涂料在指定的工期内完工，则需要考虑所选涂料的干燥时间以及涂层的施工道数对工期的影响。  \n\n$\\textcircled{6}$ 涂料的毒性在地下隧道或其他较封闭环境以及人群聚集区施工时，宜选择毒性和气味较小的无溶剂地坪涂料或水性环氧地坪涂料。  \n\n涉及地坪涂层设计的各因素大部分是相互制约和相互影响的，设计者应综合用户使用要求、使用环境、施工要求、成本预算等因素，并做现场勘查后与用户充分沟通，仔细权衡，分析利，制定合理方案，以求地坪涂层系统达到最佳性价比，最大程度地满足使用要求。  \n\n(2）地坪涂料的施工准备基面处理、施工环境要求和基本施工工具是地坪涂层系统施工的共同要求，故先单独介绍。  \n\n$\\textcircled{1}$ 基面处理一般来说，地坪涂料施工要求基面坚实、干燥、干净无浮尘、无油脂旧涂料等异物、平坦而不光滑、无缺陷。  \n\n基面的强度现场可以用钢丝刷摩擦，也可以用回弹仪做混凝土强度测试，或用小铁锤敲打基面来判定，基面的强度应大于C20为宜，基层强度过低，涂料固化后易拉开基层，且不耐重压和冲击。强度较差的基层须重新铺设水泥砂浆找平层，找平层厚度应大于 $30\\mathrm{mm}$ 以防重压后砂浆层碎裂、脱块。若基层有空鼓，须将空鼓处切除，重新浇注水泥砂浆或用无溶剂环氧砂浆修补。  \n\n基层若含有水分，会降低涂层与基层的粘接强度，引起涂层鼓泡和脱层。含水率可用含水率测试仪器进行测定，施工油性或无溶剂地坪涂料时，一般要求控制在 $6\\%$ 以下。也可按ASTM4263规定的方法，取 $45\\mathrm{cm}\\times45\\mathrm{cm}$ 的塑料薄膜平放在混凝土表面，用胶带纸密封四周边，16h后，薄膜下出现水珠或混凝土表面变黑，说明混凝土基层过湿，不宜施工。但施工水性地坪涂料时对含水率的要求可以放宽。  \n\n基面存在的灰尘、蜡、旧涂料、油污、油渍、松散的颗粒和浮浆等异物须通过洗涤、火烤、溶解、铲削、喷丸、打磨、吸尘等手段尽量除尽，以免引起涂膜外观和附着不良。  \n\n基面存在的较浅裂缝可用电动切割机沿着裂缝部分切开lcm左右宽度的 $v$ 形槽，然后将槽内粉尘吸扫干净后用树脂砂浆填补。原有的沉降缝应予以保留，在界面处可浇注弹性PU或弹性环氧胶。伸缩缝一般用环氧腻子填补平整，若面积过大，可在 $30\\sim50\\mathrm{m}$ 间隔保留伸缩缝并灌注弹性PU或弹性环氧胶。  \n\n严格来说，所有混凝土基面在底涂之前须进行喷砂抛丸或打磨吸尘处理，以提供一个干净坚硬的表面。当基层为瓷砖面、水磨石、耐磨骨料基面时，需用喷砂机或铲削机打毛地面，以增加涂层对基面的附着力，然后吸尘。  \n\n在底涂前，应通过现场检测工具对工作面进行全面细致的检查，并做好详细记录。地面施工属隐蔽工程，基层面状况务必调查清楚、记录完整。基面的尺寸要单独标明在图纸上，单位应精确到厘米。  \n\n为了防止施工边缘部分沾污及保持完全直线（或与不涂部分的分界线）应贴护面胶带。这道工序在底涂、中涂及面涂施工之前都要仔细完成。  \n\n$\\textcircled{2}$ 环境要求通常地坪涂料施工的环境要求为：施工期间和涂膜实十以前，湿度要求$45\\%\\sim85\\%$ ，温度需在 $15\\sim35^{\\circ}C$ ，基材表面温度应高于露点 $3^{\\circ}C$ 以上，以防基材及湿膜表面凝结水汽，影响涂层附着力和表面效果。  \n\n在相对湿度超过 $85\\%$ 时，涂装的涂层质量多数比较差，容易出现泛白、裂纹、剥落等病。特别是施工水性环氧地坪涂料时，湿度过高或通风不良都会导致固化不良，引起涂膜发白、浮色和强度下降等病。当然个别特殊涂料可以例外，如地坪涂装常用的湿固化型聚氨酯涂料，它是利用大气中的水分进行固化，在气候干燥时，可能还要加湿，才能使固化正常进行。温度过低，许多双组分涂料的固化反应历程减慢或停止，会严重影响地坪涂料的固化性能，如固化过程延长，甚至不能完全固化，涂膜性能严重降低，如强度、硬度降低，耐磨性变差，直接影响使用寿命。对于无溶剂自流平涂料的影响则更大，表现为涂料黏度成倍增长，流动、流平性能变差，施工时产生刀痕等缺陷。气温太高，不利于施工人员身体保护，且气温太高时，无溶剂自流平涂料的适用期会明显缩短，涂料很快增稠并干结报废，甚至出现暴聚现象。  \n\n$\\textcircled{3}$ 常用施工工具  \n\na.主要工具打磨机、喷砂机、工业电动吸尘机、手提式电动磨光机、铁锤、刀、手提式电动搅拌机。b.其他工具及材料电子秤、照明灯、接线板、 $25\\sim36\\mathrm{cm}$ 的角抹、钉鞋、带齿消泡辊筒、漆刷、辊筒、锯齿刀、橡胶刮板、护面胶带等。(3）地坪涂料的施工工艺一般来讲，地坪涂层由底漆、中涂层、面漆构成。三个涂层是相互关联协同作用的，只有当三个涂层分别得到正确施工，才能使涂层系统体现预期的良好整体性能。  \n\n涂布底漆时一般应注意以下几个事项$\\textcircled{1}$ 含颜料、填料的底漆在使用前和使用过程应注意搅拌均匀。  \n\n$\\textcircled{2}$ 底漆涂膜厚度根据底漆品种确定，应注意控制。涂布应均匀、完整、无露底，表面无浮尘及松散砂粒。  \n\n$\\textcircled{3}$ 注意遵守干燥的规范。在底涂上如涂含有强溶剂的涂料时，底漆必须干透，以免出现咬底等漆病。  \n\n$\\textcircled{4}$ 要在表面处理以后严格按照规定的时间及时涂布底漆。还要根据底漆品种规定的条件在底漆干燥后规定的时间范围内涂下一道漆。过早涂布可能引起咬底及底漆中溶剂挥发困难导致漆膜干燥时间延长、固化不良、鼓泡等情况；涂布过迟可能引起层间附着不良，且过迟涂布易由于粉尘积累或其他污染影响表观。  \n\n$\\textcircled{5}$ 为增加下一道涂层与底漆间的附着力，可在涂布前将底漆打磨。  \n\n涂布底漆的方法一般可采用辊涂、刷涂和喷涂。刷涂施工效率较低，一般在边角处施工采用。最常采用的是辊涂，效率高。  \n\n施工中涂层时，应根据客户要求的施工厚度和产品干燥性能控制好每道涂层的厚度。施涂溶剂型和水性砂浆层时，不能一道施工过厚，否则有可能出现因溶剂挥发困难导致涂层长时间发软，不但延误工期，而且涂层固化性能差。  \n\n刮涂是砂浆层和腻子层最常见的施工方法。根据砂浆漆料的黏度情况有时也可采用馒涂施工。如果要求砂浆层施工厚度在3mm以上，多采用无溶剂砂浆料，用压砂工艺施工，用抹光机抹平，该工艺可一次施工达3～5mm，免去了多次涂布的烦琐工序。  \n\n由于砂浆层表面较粗糙，孔隙较多，一般需刮腻子找平，填补空隙。中涂施工完毕后，表面应平整无孔隙，因孔隙中的空气有可能在施工面漆时与面漆进行置换，表现为面漆施工完毕后出现气泡、漆膜塌陷等弊病。  \n\n为了获得良好表观效果的面层，中涂层完工以后一般需要打磨、吸尘，再涂布面漆。  \n\n根据面漆的施工厚度选择合适的施工方法，施工薄型地坪面漆时一般采用辊涂或刷涂，涂布应均匀，当涂层遮盖率差的亦不应以增加厚度来弥补，而是应当分儿次来涂装。施工厚型地坪面漆（如自流平面漆）时一般采用馒刀馒涂。当施工的面漆厚度居于两者之间，其厚度不足以满足自流平条件时，常采用喷涂，可获得较好的表面效果。  \n\n面漆涂布和干燥方法应依据施工环境和涂料品种而定，应涂在确认无缺陷和干透的中间层或底漆上。原则上第二道面漆应在第一道面漆干透后方可涂布。面漆（特别是薄型地坪面漆）应用细筛网或纱布仔细过滤，涂漆和干燥时场所应干净无尘。  \n\n地坪涂料施工完毕以后需自然养护，以使涂膜达到较高的固化程度和性能，一般养护期为一周。养护期间不能遭遇化学介质、水以及各种机械碾压和冲击。  \n\n根据实际应用中地坪涂层设计的特点，将地坪涂层系统分为普通薄型地坪 $(0.2\\sim$ $0.5\\mathrm{mm}^{\\prime}$ 、普通厚型地坪 $(1\\sim3\\mathrm{mm})$ 、特种工艺地坪三类。  \n\n$\\textcircled{1}0,2{\\sim}0,5\\mathrm{mm}$ 普通薄型地坪此类地坪涂层较薄，施工快捷，耗漆量少，造价低廉，容易翻新和修补，能提供装饰、防潮、防尘、防渗、使地面易清洁等功能，耐一般化学品腐蚀，使用寿命一般为 $3\\sim5$ 年，是普通工业地坪防护最常用的地坪类型。普遍应用于电器、电子、机械、食品、医药、化工、烟草、饲料、纺织、服装、家具、塑料、文体用品等承受轻度载荷的制造车间水泥或水磨石地面。具体施工工序如下。  \n\na.按前述要求进行基面处理  \n\nb.涂布底漆一道。要求施涂均匀，无漏涂，底漆施工完后表面无粉尘及松散砂粒。在离墙、柱、设备较近的地方辊涂时应慢速推动辊筒，以防止涂料飞溅沾污其他表面。对吸油量较大的区域应补涂底漆。涂料用量： $0.10{\\sim}0.22\\mathrm{kg/m^{2}}$ 。底漆养护时间需根据底漆类型和干燥情况来确定，一般为 $4\\sim12\\mathrm{h}$ 中  \n\nc.刮涂腻子两道。腻子一般是在施工现场在漆料中临时掺入 $100\\sim400$ 目的石英粉和（或）滑石粉调配而成。腻子应抹平，不透底，无浮砂，表面无砂眼。涂料用量随粉料的粗细和基面粗糙程度变化而变化，一般为 $0.15{\\sim}0.25\\mathrm{kg/m}^{2}$ 。腻子层干至打磨时不粘磨片时可以进行打磨，吸尘。做到无粉尘、颗粒及刮刀痕迹。  \n\nd.涂布色漆（面漆）两道。此类色漆一般为溶剂型色漆，用量为 $0,2{\\sim}0,3\\mathrm{kg/m^{2}}$ 。如为无溶剂或少溶剂色漆时，面层厚度会增大，涂料用量为 $0,3{\\sim}0,4\\mathrm{kg}/\\mathrm{m}^{2}$ 。要求无漏涂、露底，表面平滑无施工痕迹，颜色均匀，表面光泽一致。  \n\ne.施涂罩面清漆一道。用量为 $0.\\ 08\\sim0.\\ 12\\mathrm{kg/m^{2}}$ 。此道工序可根据实际情况选用或不用。施涂罩面清漆一般会延长涂层的使用寿命。  \n\n$\\textcircled{2}1\\sim3\\mathrm{mm}$ 普通厚型地坪此类地坪除具备普通薄型地坪的一般功能外，且耐磨性好，耐冲击和重载荷，但耗漆量较大，造价相对较高。此类地坪可根据客户要求和实际应用情况设计不同厚度和涂料品种。例如，当选用薄涂型环氧-聚氨酯面漆时，适应于要求耐磨性强、耐一定冲击性的电器、电子、机械（如汽车、摩托车、电梯、自行车等)、通讯设备、仪器仪表、食品、药品、化工、烟草、饲料、纺织、饮料、服装、家具、塑料、文体用品等制造车间地面，特别是需要跑叉车、汽车、重手推车的走道。当选用环氧自流平面漆时，适应于要求高度清洁、美观、无尘、无菌的电子、微电子以及实行GMP标准的制药、血液制品等行业的地坪防护。当选乙烯基脂树脂涂料设计整个涂层时，特别适用于化工厂、有色冶金、机械工厂、电镀、电池厂、钢铁厂等对防腐蚀有苛刻要求的地坪防护。具体施工工序如下。  \n\na.基面处理。  \n\nb.涂布底漆一道。  \n\nc.刮涂或涂砂浆中层漆。施工砂浆层时，根据设计厚度在溶剂型漆料中现场掺人要求规格的石英砂分批次刮涂，因涂料中含有溶剂，每次刮涂不能太厚（一般不超过1mm），因为太厚的砂浆层不能完全干透，导致地坪早期强度不够，抗压性能差。也可以用无溶剂漆料加入石英砂调配成自流平砂浆刮涂或馒涂。砂浆层施工要求石英砂分布均匀，表面平实，无突起、无漏刮，尤其是不能留下刀痕，以减少打磨次数；在前一层砂浆未完全固化之前，不能施工下一层砂浆，否则易起泡；每刮一层砂浆，待其完全固化后，视涂层的平整度决定是否打磨，如需打磨，可用吸尘打磨机或手磨机打磨，要求打磨后的砂浆面平实、无突起，打磨完毕后清理干净。  \n\nd.刮涂腻子一道或两道。最后一层封闭腻子完全固化后，应将腻子面层打磨平实光滑，不能有一点突起或一丝孔隙，打磨完毕后彻底清扫灰尘。  \n\ne.涂布按设计要求的面漆一道或两道，  \n\n$\\textcircled{3}$ 特种工艺地坪  \n\na.环氧玻璃钢地坪环氧玻璃钢地坪是在涂层中夹杂铺衬一层或多层玻璃布的复合式地坪，此类地坪的抗压强度、拉伸强度、弯曲强度都得到明显提升，适应于强度要求高的水泥地面或防强酸、强碱等化学品腐蚀的地面及排水沟、碱水池等场所。其施工工序如下。  \n\n基面处理。  \n\n$\\cdot$ 刮涂高固含环氧底漆一道。底漆干至不粘鞋可进行下一道工序。  \n\n$\\cdot$ 采用逐层铺衬或一次多层玻璃布连续辅衬。将按比例调好的环氧玻璃钢漆和固化剂辊涂于地上，铺上玻璃纤维布，再用辊筒粘漆整平，边角部位用毛刷，涂料用量一布一油 $0.35\\cdots$ $0.4\\mathrm{kg/m^{2}}$ 。采用逐层铺衬时，上下层为垂直方向；采用一次多层玻璃布连续辅衬时，上下层接缝要错开，每层玻璃布均要贴实、不留气泡、不起皱褶，每幅布之间的搭接宽度不小于 $5\\mathrm{cm}$  \n\n·刮高固含环氧腻子一遍，干燥后打磨。要求用手动打磨机打磨，采用 $60\\sim80$ 目的砂纸片，做到无气泡、无布须、无砂眼，平整。  \n\n$\\cdot$ 涂高固含量玻璃钢漆 $1\\sim2$ 遍，也可以表面做环氧自流平面漆。要求表面平滑光亮，不透底，不露玻璃纤维布或玻璃纤维丝。  \n\nb. $3\\mathrm{mm}$ 以上环氧压砂厚型地坪采用压砂工艺的厚型环氧地坪硬度高，固化收缩率小，耐酸、碱、盐及其他化学溶剂腐蚀，使用寿命长，一般可达15年以上。适应于要求耐强力冲击、耐腐蚀的机械厂、码头、货物电梯口、车道、化工厂、电子厂等地坪的防护。其施工工序如下。  \n\n$\\cdot$ 基面处理。  \n\n$\\cdot$ 刮涂高固含量底漆一道。涂料用量为 $0.20{\\sim}0.25\\mathrm{{kg/m^{2}}}$  \n\n$\\cdot$ 按设计厚度压砂。将无溶剂环氧漆料按规定配比混合并搅拌均匀，掺人石英砂中搅拌均匀后倒在地上[其中漆料与砂的重量配比为 $1:(6\\sim8)]$ ，用钉耙将调好的砂浆耙开并用刮刀抹平，然后用抹光机对砂浆进行抹压，机器处理不到之处用手工操作。要求做到表面平整、砂粒均匀、无浮砂和刀痕。  \n\n$\\cdot$ 灌浆。将调好的无溶剂环氧漆倒于地面，用刮刀刮开，使涂料足够渗入砂浆层。根据  \n\n砂浆层厚度及灌浆效果决定灌浆次数。  \n\n$\\cdot$ 打磨吸尘。  \n$\\cdot$ 刮涂环氧腻子两道。  \n$\\cdot$ 手动打磨机细磨，吸尘，清洁地面。  \n\n·涂布色漆1～2道。色漆为溶剂型薄涂色漆时，一般施工两道色漆后再施涂一道罩面清漆。色漆为环氧自流平涂料时一般只需施工一道。  \n\n地坪漆施工结束后，把现场交给客户时，应向客户提醒如下保养及维护方法，以便能保持地面良好的质量状态和延长地坪的使用时间。  \n\n$\\cdot$ 地坪应经常进行清洁。存留在地面砂粒或其他坚硬颗粒可加速地坪的磨损和对地坪造成刮伤，清洁时可用柔软扫帚或拖布。  \n\n·当有严重污垢时，宜使用抹布用中性清洁剂清洗，然后充分干燥，打一层薄蜡。  \n\n$\\cdot$ 当酸、碱等化学药品溅溢地面时，应及时用抹布擦净后用水清洗，如果是调味料、油等则用抹布擦拭即可。  \n\n光滑的涂层可用养护蜡定期保养，永葆美观",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 217,
+        "chunk": "# 七、耐温防腐涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 218,
+        "chunk": "# 1.耐温防腐涂料概述  \n\n高温腐蚀是指在高温环境条件下，材料表面与各类环境介质在界面之间发生化学反应或电化学反应，在材料表面形成反应物质，并对材料的结构及性能产生破坏。随着航空、航天、能源、化工、冶金、电力、机械、轻工等行业的发展，对材料的使用性能也越来越高，一些设备、管道由于腐蚀介质的存在而发生腐蚀，尤其是一些设备的高温部件，如燃烧器、加热器、各种车辆的排气管、消声器、发动机、热交换器、石油裂解设备、高温蒸汽管道等，在高温和腐蚀介质的作用下会发生迅速腐蚀。因此，对于材料，特别是一些金属材料，如何在高温腐蚀环境达到保障性能的目的是一个艰巨的任务。而在各种高温防腐蚀技术中，使用涂料进行防护，由于其简易性及可操作性得到了各方的青睐，从而得到最广泛的应用。在这里定义的耐温防腐涂料一般是指在 $200\\%$ 以上，漆膜不变色、不脱落，仍能保持适当的物理力学性能的涂料。根据使用环境的不同，防护目的的差别，目前国内外各涂料厂商开发出的耐温防腐涂料种类繁多，性能各异。但是从总体来讲，一般可分为有机高温防腐涂料、无机高温防腐涂料和有机-无机复合高温防腐涂料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 219,
+        "chunk": "# 2.耐温防腐涂料分类  \n\n(1）有机高温防腐涂料有机高温防腐涂料根据基料的不同，主要包括杂环类聚合物涂料（如聚酰亚胺类、聚酰胺酰亚胺类、聚苯硫醚类、聚醚矾类等）和元素类有机聚合物涂料（如有机硅类、有机氟类、有机钛类和聚硼硅氧烷类等）两大类。杂环类聚合物应用在高温涂料上国内外已经过多年的发展，主要用于高温绝缘方面，但是其价格昂贵，贮存性不好，对颜料要求严格；有机氟涂料虽然其高温防腐性能优越，但不容易溶解于溶剂，即使溶解，其固体含量低、成膜薄、施工不方便，而且有机氟涂料力学性能不太理想；有机钛涂料发展较晚，制备复杂，在工业化领域的发展较为有限。以上聚合物用于耐温防腐蚀涂料，由于自身性能的限制或者成本方面的考虑，并没有得到广泛的推广，所以通常使用的高温防腐涂料主要以有机硅聚合物作为基料。有机硅聚合物作为基料用于耐温涂料，由于其分子链中硅-氧键的共价键键能比普通有机高聚物中碳-碳键的共价键键能高，在受热时热稳定性较好，显示了较为优异的耐热性。而且有机硅聚合物价格相对较低，用于涂料时施工性能较好，因此在有机高温防腐蚀涂料领域，有机硅聚合物得到了最广泛的应用。但是也需要看到的是有机硅聚合物作为涂料的基料使用时，其通气性良好，导致了防腐蚀性不太高，如果要使有机硅涂料达到既耐热又有良好的防腐蚀性能，还需要许多的改进之处。  \n\n(2）无机高温防腐涂料目前无机耐高温防腐蚀涂料主要分为以聚硅酸乙酯为基料、以水溶性硅酸盐为基料、以二氧化硅溶胶为基料及水溶性磷酸盐为基料的四种体系。由于这几类无机材料的耐热性可达400～1000℃甚至更高，并且具有耐燃性好、硬度高等特点，在用作耐温防腐蚀涂料时与防锈颜料、锌粉等配合使用，具有优异的耐温耐腐蚀性。其中以硅酸乙酯为基料的耐高温防腐蚀涂料得到最广泛的应用。硅酸乙酯再经过水解、聚合，最后成为不含有机物的二氧化硅交联聚合物，由于其结构和二氧化硅相似，具有良好的耐热、防腐、耐化学药品性。以硅酸乙酯为黏结剂的无机富锌涂料目前大量被用作车间底漆作为临时保护的防腐蚀涂料用。但是，无机耐温防腐蚀涂料在使用中也存在看一些自身无法克服的劣势，例如：漆膜较脆，延展性差，厚涂时漆膜易开裂，未完全固化前耐水性不好，对底材表面处理要求严格等。  \n\n(3）有机-无机复合高温防腐涂料由于有机高温防腐涂料和无机高温防腐涂料各有优缺点，有机-无机复合高温防腐涂料顺势而生。近年来有许多关于采用有机树脂与无机涂料进行匹配或化学改性的有机-无机复合型高温防腐涂料的报道，如向有机硅高温涂料中加人玻璃、陶瓷材料，其作用原理是：当有机硅涂层在受热条件下分解、炭化，失去足够的粘接性能时，玻璃陶瓷料熔化并接替有机硅树脂继续起对颜料和填料的黏附作用。复合的玻璃料要求其熔点与有机硅树脂受热分解温度相适应，采用适当比例的高、中、低熔点的玻璃料，能获得高温附着力好、有光泽、耐腐蚀、耐冲击的涂层。这种复合涂料的成膜物为有机无机高分子的复合体，与有机聚合物和无机颜填料所组成的涂膜复合体不同。  \n\n另外，还有通过在水溶性硅酸盐中引人有机树脂、水溶性甲基硅酸钠、聚醋酸乙烯、聚丙烯酸酯等乳液或加人水溶性尿素树脂、蛋白质类酪素、树脂状粉末（有机硅树脂、丙烯酸树脂、环氧树脂、聚酯、三聚氰胺树脂、松香等)；在硅酸乙酯水解物中加人醇溶性聚乙烯醇缩丁醛或乙基纤维素，用硅酸乙酯水解物与多元酸在酸存在下进行酯交换生成聚醚硅酸酯、硅酸乙酯水解物和含乙氧基、甲氧基、羟基的硅中间体，在酸催化下进一步水解引入部分有机硅组分；通过与有机高分子接枝共聚或加入硅烷偶联剂、悬浮剂、碱金属氢氧化物、磷酸盐、有机树脂乳液等方法改进硅溶胶漆膜性能等方法。但是，要获得工业化的大规模应用，仍然有大量的研究工作需要完成。",
+        "category": " Introduction"
+    },
+    {
+        "id": 220,
+        "chunk": "# 3.配方设计  \n\n耐温防腐涂料的使用环境是特定的，主要面对如何在高温环境下阻隔腐蚀介质侵蚀底材的要求。这就要求在设计配方时必须选择既有良好的耐温性又能兼顾防腐蚀要求的材料。在涂料的成分构成中，如何选择合适的基料是决定配方是否成功的关键。  \n\n（1）基料的选择选择耐温防腐涂料的基料时，由于其使用目的的限制，可供选择的树脂不多，得到大规模工业化使用的就更少。有机硅树脂基于其优异的耐温性和施工性，成为国内外涂料公司开发这类涂料时共同的选择。  \n\n有机硅树脂作为耐温防腐蚀涂料最大优势是其良好的耐高温性能，这主要是由于其独特的分子结构所致。硅在元素周期表上正好位于碳的下方，但是有机硅的Si—X键和C—X键的相似点很少，见表3-3-116。  \n\n表3-3-116 有机硅Si- $\\mathbf{X}$ 键的性能比较  \n\n\n<html><body><table><tr><td rowspan=\"2\">元素（X)</td><td colspan=\"2\">键长/A</td><td colspan=\"2\">离子性/%</td></tr><tr><td>Si--X</td><td>C-X</td><td>Si-X</td><td>C-X</td></tr><tr><td>Si</td><td>2.34</td><td>1.88</td><td>一</td><td>12</td></tr><tr><td>C</td><td>1.88</td><td>1.54</td><td>12</td><td>一</td></tr><tr><td>H</td><td>1.47</td><td>1.07</td><td>2</td><td>4</td></tr><tr><td>0</td><td>1.63</td><td>1.42</td><td>50</td><td>22</td></tr></table></body></html>\n\n注： $1\\mathring{\\mathrm{A}}=\\bar{0},1\\mathrm{nm}$  \n\n有机硅树脂中硅-氧键的共价键键能比普通有机高聚物中碳-碳键的共价键键能大，硅-氧键中硅原子与氧原子的电负性相差大，因此硅-氧键极性大，有 $51\\%$ 离子化倾向，其键能也比较大为 $452\\mathrm{kJ/mol}$ （108kcal/mol)。对硅原子上连接的烃基有偶极性感应影响，提高了所连烃基对氧化作用的稳定性，比普通有机高聚物上这种相同基团的稳定性要高很多，即Si--O—Si链对所连烃基基团的氧化能起到屏蔽作用：有机硅高聚物中的硅原子和氧原子形成 $\\operatorname{d-p}\\pi$ 键，增加了高聚物的稳定性及其键能，也增加了其热稳定性；普通有机高聚物的碳-碳主链受热氧化，很容易断裂成低分子物，而有机硅高聚物中硅原子上连接的烃基受热氧化后，生成高度交联且更加稳定的Si—O—Si链，能防止其主链的断裂降解；受热氧化时，有机硅高聚物表面生成了富含Si—O—Si链的稳定保护层，减轻了对高聚物类别的影响。  \n\n有机硅树脂的选择在很大程度上受到最终应用时环境温度的影响，但是漆膜的硬度也需重点考虑，平衡这两个参数可以实现最佳的涂料性能。如何判断有机硅树脂的这两项参数，需要从分子机构出发：一般来说，在有机硅单体中，三官能度单体提供交联点，二官能度单体增进柔韧性，表现在聚合物中，其密度对外观的影响如下式所示。  \n\n![](images/5d37a09d0ef323a62dd5f8cc939ed72f89999839faeb81f1f9d60fdc05d069d4.jpg)  \n\n具体表现在聚合物结构中侧基R和硅原子Si的比率变化对物理性能的影响见表3-3-117。  \n\n表3-3-117 有机硅聚合物物理性能变化  \n\n\n<html><body><table><tr><td rowspan=\"2\">性能</td><td colspan=\"9\">R/Si</td></tr><tr><td>1.0</td><td>1.1</td><td>1.2</td><td>1.3</td><td>1.4</td><td>1.5</td><td>1.6</td><td>1.7</td><td>2.0</td></tr><tr><td>固化速率</td><td>快</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>慢</td></tr><tr><td>硬度</td><td colspan=\"7\">硬</td><td rowspan=\"3\">软 好</td></tr><tr><td>柔韧性</td><td>差</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>热失重</td><td>小</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>抗开裂性</td><td>差</td><td></td><td></td><td></td><td>→好</td><td></td><td>中等</td><td></td><td>大</td></tr></table></body></html>  \n\n在有机硅分子结构中侧基主要构成为甲基（methyl）和苯基（phenyl），总体来讲侧基与硅原子比率变化会造成聚合物物理性能的变化，但具体到侧基的品种不同也会对聚合物性能造成影响。在合成聚合物时，适量的二甲基单体赋予合成树脂一定柔韧性，但在配方中的摩尔分数不宜太高，因为过高将影响树脂的强度，而且导致没有交联的低分子环体增多，这对应合成链状的有机硅中间预聚体是不希望的。而苯基单体含量高的树脂具有热稳定性好、坚韧性好、热塑性大、在空气中耐氧化作用能力强及热老化时能长期保持柔韧性，且可提高有机硅与环氧树脂的混容能力。  \n\n纯有机硅树脂在耐热性方面具有优异的表现，但是由于纯有机硅树脂需高温烘干$(250{\\sim}300^{\\circ}\\mathrm{C})$ ，固化时间长，大面积施工不便，并且对底材的附着力及耐有机溶剂性能差，温度较高时漆膜的机械强度差等方面的缺陷导致纯有机硅树脂在使用中仍旧存在着许多问题。为了解决这些方面的问题，工业化生产或者具体应用中常常使用醇酸树脂、聚酯树脂、聚氨酯树脂、丙烯酸树脂、环氧树脂等通过物理共混合化学改性等方法对有机硅树脂进行改性。在涂料中如何根据具体的使用目的选择合适的硅树脂时，一般推荐使用较软、更具弹性的树脂配制用于较高温度范围的涂料，推荐使用具有出色热硬度的刚性树脂用于中等温度范围的涂料。国外的著名有机硅树脂供应商都会提供从不同性能的纯有机硅树脂到改性有机硅树脂等各种牌号的产品，表3-3-118为商用有机硅公司推荐的产品。在应用时可以根据使用的目的选择不同性能的树脂。  \n\n表3-3-118 商用有机硅树脂主要牌号  \n\n\n<html><body><table><tr><td>编号</td><td>清漆类型</td><td>特性</td></tr><tr><td>1</td><td>纯有机硅树脂</td><td>200℃烘干固化，最大韧性树脂</td></tr><tr><td>2</td><td>纯有机硅树脂</td><td>150℃烘干固化，硬质漆膜</td></tr><tr><td>3</td><td>纯有机硅树脂</td><td>室温固化，漆膜稍脆</td></tr><tr><td>4</td><td>纯有机硅树脂</td><td>高温下有光泽，有稍微损失，相容性好</td></tr><tr><td>5</td><td>纯有机硅树脂</td><td>150℃烘干固化，漆膜硬，耐热，高温下有少量烟生成</td></tr></table></body></html>  \n\n使用有机硅树脂可以满足耐热性的要求，但是不同的使用环境决定了单纯依靠有机硅树脂来满足所有要求是不现实的，前面提到可通过与其他树脂共混改性或化学改性来达到提高有机硅树脂使用环境的要求。例如：在加人酚醛和三聚氰胺树脂的有机硅树脂可以提高硬度；在丙烯酸中加人可提高其干燥性；在环氧树脂中提高耐腐蚀性；在醇酸树脂中提高坚韧度等。  \n\n在耐温防腐蚀领域里，使用有机硅树脂改性环氧树脂是一个具有广阔前景的方向。环氧树脂分子结构是大分子链上含有环氧基，由于所采用的原料、生成环氧基的方法以及应用目的不同，所得到的环氧树脂的种类也不同，其中最主要、最常用的是双酚A型环氧树脂（E型)，约占环氧树脂总量的 $90\\%$ ，防腐涂料所用的环氧树脂主要也是这一类。其结构式如下：  \n\n![](images/ccc412e15fb14bee6bec00057e7eb5d0e9293b34f62c20c1b2bda6ad2e39b45f.jpg)  \n\n从以上环氧树脂的结构式中可以看出，分子中的某些结构特点对树脂的最终性能起到重要作用，如：  \n\n醚键 -C-0-C- 良好的耐化学性甲基 —CH3 韧性羟基 -OH 粘接性芳烃结构 高温性能和刚性  \n\n环氧改性有机硅树脂集环氧树脂和有机硅树脂的优良性能为一体，弥补了各自的缺陷，具有优良的防腐性、耐高温性、电绝缘性，特别是对底材的附着力、耐介质性能较有机硅树脂有很大的提高，广泛用于航空、航天、核工业、兵器、电子领域，是特种涂料用有机树脂中用途最广的品种之一。  \n\n环氧改性有机硅树脂的方法有两种：一是冷拼法（物理法)，即以相容性好的有机硅树脂（即高苯基含量的有机硅树脂）与环氧树脂冷拼混合而成；二是热缩聚法（化学法)，即以环氧树脂的活性官能团（即羟基）与适当的有机硅中间体的烷氧基或羟基（见下式）在一定条件下进行缩聚反应。  \n\n![](images/69e7597ce99fa9e6ff750bc3d498b8d95cd97e49b3f00ae6ae45e675a4ea7d19.jpg)  \nR为甲基、苯基；X为烷基、氢  \n\n改性用的环氧树脂一般采用中等分子量的环氧如E-35、E-20、E-12等，它们具有适中的羟基和环氧基。反应在溶剂中进行，常用的溶剂有环已酮、异佛尔酮、甲基环己酮等。树脂合成中主要是硅中间体中的乙氧基或羟基与环氧树脂中的羟基反应，含乙氧基的硅中间物与环氧树脂反应生成乙醇，而含羟基的硅中间物则生成水，反应式表示如下。  \n\n![](images/437b485ec7b35da73ee5a41379f69a6eab56522686dd491929c9b6f39c0b015e.jpg)  \n\n在适当范围内控制有机硅和环氧树脂的比例，可得到不同的共聚物，由表3-3-119可以看出随着有机硅比例的提高，共聚物的聚合时间缩短，耐温性能得以改善，但是树脂的固化成膜性能却明显下降；随着环氧树脂的比例增加，共聚物的防腐性、固化性能及物理力学性能提高，而耐温性能下降。  \n\n表3-3-119 环氧有机硅比例对树脂性能的影响  \n\n\n<html><body><table><tr><td rowspan=\"2\">性能</td><td colspan=\"4\">有机硅/环氧树脂(质量比）</td></tr><tr><td>40/60</td><td>50/50</td><td>60/40</td><td>70/30</td></tr><tr><td>聚酰胺为固化剂的固化时间/h</td><td>2</td><td>4</td><td>5</td><td>T</td></tr><tr><td>附着力/级</td><td>１</td><td>１</td><td>2</td><td>2</td></tr><tr><td>耐热性250℃，2h，漆膜外观</td><td>漆膜变深黄，失光</td><td>漆膜稍变黄，稍 失光</td><td>漆膜颜色基本无 变化，无失光</td><td>漆膜颜色无变化， 无失光</td></tr><tr><td>反应温度及终点时间</td><td>180°℃,55min</td><td>180°℃,45min</td><td>180°C,45min</td><td>180°℃,40min</td></tr></table></body></html>  \n\n近年来，国内外对有机硅改性树脂进行了大量研究，对于不同结构、不同比例的树脂对最终性能的影响积累了大量的数据。各大有机硅树脂供应商提供了种类繁多的有机硅中间体（表3-3-120)，涂料配方设计者在进行配方设计时，可以根据使用目的及供应商所提供树脂的性能指标，灵活选择适合自己的树脂。  \n\n表3-3-120 商用硅树脂中间体选择指南  \n\n\n<html><body><table><tr><td>编号</td><td>物理形态 （固体含量）/%</td><td>官能团</td><td>活性</td><td>典型应用</td></tr><tr><td>1</td><td>片状固体 (100)</td><td>硅烷醇</td><td>可与含羟基的醇酸树脂、酚醛 树脂、环氧树脂和其他有机树脂 反应</td><td>反应性有机硅树脂中间体，用于彩色保养和建 筑面漆、乙基电器面漆、卷材漆和高温装饰漆。与 其他硅树脂混合，用于改善硬度。与有机树脂混 合，改善耐候性和耐热性</td></tr><tr><td>2</td><td>液体 (90)</td><td>甲氧基</td><td>反应</td><td>活性有机硅中间体，用于卷材漆、电器装饰和其 与活性羟基的有机树脂体系|他需要提高耐热性和耐候性的装饰。通常与饱和 聚酯或无油醇酸树脂反应，形成有机硅改性共 聚物</td></tr><tr><td>3</td><td>液体 (90)</td><td>甲氧基</td><td>与活性羟基的有机树脂反应</td><td>活性有机硅中间体，用于卷材漆、电器装饰和其 他需要提高耐热性和耐候性的装饰。通常与饱和 聚酯树脂反应，形成20%～50%有机硅含量的硅 改性聚酯共聚物</td></tr><tr><td>4</td><td>液体 (100，活化）</td><td>甲氧基</td><td>与含活性羟基的有机树脂 反应</td><td>用于提高丙烯酸乳液耐候性的活性有机硅中间 体。与其他在碱性条件下稳定的乳液系统一样， 表现良好</td></tr></table></body></html>  \n\n(2）颜料、填料的选择及使用颜料、填料在涂料上的应用具有重要意义，通过添加不同种类的颜料、填料可以改善漆膜的某些性能，例如：提高漆膜力学性能、增加耐腐蚀性、耐候性、耐温性等；同时添加颜料、填料还可以达到降低成本的目的。  \n\n涂料的耐热性问题是一个复杂问题，它不仅与树脂（基料）有关，同时与颜料、填料等也有着紧密的关系。因在高温下使用的涂料，其颜料的选用具有特殊性，如有机硅涂料可在 $200{\\sim}250^{\\circ}\\mathrm{C}$ 连续使用， $300^{\\circ}C$ 时间断使用；但在加入耐热性的颜料、填料后，其耐热性可提高到在 $400{\\sim}600^{\\circ}\\mathrm{C}$ 长期工作；加人某些颜填料，还可使有机硅涂料耐 $700\\sim$ $800^{\\circ}C$ 的高温。  \n\n具体在耐温防腐蚀涂料上如何选择合适的颜料、填料是一个实际的问题，表3-3-121列出了一些常用颜填料在有机硅树脂中使用时对耐温性的影响。  \n\n表3-3-121 颜料、填料对有机硅树脂耐温性的影响  \n\n\n<html><body><table><tr><td>颜色</td><td>颜料</td><td>漆膜性能</td></tr><tr><td rowspan=\"7\">体质颜料</td><td>云母粉</td><td>提高硅树脂的耐温性，耐温性在300℃下超过1000h</td></tr><tr><td>滑石粉</td><td>提高硅树脂的耐温性，耐温性在300℃下超过1000h</td></tr><tr><td>硅石</td><td>提高硅树脂的耐温性和机械强度，耐温性在300℃下超过1000h</td></tr><tr><td>黏土</td><td>耐温性达250℃，在300℃下1000h，划格法显示10/100面积脱落</td></tr><tr><td>高岭土</td><td>耐温性可达250℃，在300℃下100h后漆膜剥落</td></tr><tr><td>硫酸钡</td><td>可以提高漆膜的强度，但是温度超过300℃后出现裂纹</td></tr><tr><td>其他</td><td>碳酸钙、硫酸钙、氧化镁可以被使用，但是耐温性会下降</td></tr><tr><td rowspan=\"4\">白色颜料</td><td>二氧化钛</td><td>漆膜（颜料/树脂=1/1)在300℃下100h产生裂纹和剥落，在250℃经过1000h，划格法显示</td></tr><tr><td>氧化锌</td><td>70/100面积脱落。但是与氧化锌联合使用则显示较好的结果 遮盖力较二氧化钛弱，但是耐温性提高，可以经受300℃下1000h而不产生裂纹和剥落</td></tr><tr><td>锌钡白</td><td>在250℃下显示了氧化锌相同的性能，但是超过300℃性能变差</td></tr><tr><td>硫化锌</td><td>耐热性较差，在250℃下1000h产生裂纹和剥落</td></tr><tr><td>红色颜料</td><td>铁红</td><td colspan=\"2\">耐热性随铁含量的升高而降低；铁含量在5%时，在300℃经过400h剥落产生；含量20%时， 300C经过100h产生；250℃则不会发生</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>颜色</td><td>颤料</td><td>漆膜性能</td></tr><tr><td rowspan=\"5\">黑色颜料</td><td>炭黑</td><td>300℃经过较长时间发生褪色，根据不同的型号程度有所不同；涂料趋向于产生触变性，炭黑 在树脂中不易分散</td></tr><tr><td>石墨</td><td>温度超过300℃时均显示优异的耐热性</td></tr><tr><td>氧化铁</td><td>超过250℃后，铁黑转化为铁红，漆膜也转为红色</td></tr><tr><td>二氧化锰</td><td>有极佳的耐热性，能够在300℃下使用，但色调不佳，漆膜呈现褐色</td></tr><tr><td>黑色陶瓷</td><td>逮盖力较差，但是色调较好，耐热性可以达到300℃</td></tr><tr><td rowspan=\"3\">绿色颜料</td><td>铬绿</td><td>250℃时无变化，300℃经过100h发生开裂</td></tr><tr><td>钻绿</td><td>250℃时无变化，300C经过100h发生开裂</td></tr><tr><td>吉勒特绿</td><td>温度升到200℃时显示较佳的色调，超过200℃时发生褪色</td></tr><tr><td>黄色颜料</td><td>钛黄</td><td>显示优异的耐温性，300℃经过500h无剥落发生，但是有轻微的褪色发生；250℃时没有变化</td></tr><tr><td rowspan=\"3\">蓝色颜料</td><td>钴蓝</td><td>300℃时显示优异的耐热性，颜色与光泽上的变化较小</td></tr><tr><td>普鲁士蓝</td><td>降低树脂的性能，在温度超过250℃时颜色变黑</td></tr><tr><td>酥菁蓝</td><td>虽然不会影响树脂的性能，但是只能在200℃下使用，超过250℃时，显著的褪色出现</td></tr><tr><td>银色颜料</td><td>铝粉</td><td>铝粉可以显著地改善树脂的耐热性和附着力；使用铝粉的银色涂料能够在600C的高温下长 期使用。浮型和非浮型没有明显的不同，但是浮型有较佳的防腐性</td></tr></table></body></html>  \n\n颜料、填料的选择是一个具体问题，其用量是另一个问题。这是因为颜料、填料在涂料中的用量存在着一个极限值，当用量超过这个极限时，涂膜的许多性能会发生突变，涂料设计的一个重要参数就是颜料体积浓度PVC（pigmentvolume concentration），利用它可以判断涂层的大致性能。颜料体积浓度PVC是Asbeck于1949年提出的，指涂料中颜、填料的体积与配方中所有非挥发性组分的总体积之比，如式（3-3-14）所示。  \n\nPVC值的选取是根据其与临界颜料体积浓度CPVC的关系而定的，正确的处理实际PVC与CPVC之间的关系对涂料的制备、涂装工艺和涂层的性能有着直接的联系。  \n\n一般涂料的设计中要求 $\\mathrm{PVC}{<}\\mathrm{CPVC}$ 。临界颜料体积浓度CPVC表示漆膜中颜料的最高含量、基料最低含量而保持漆膜完整不透的数值。当 $\\mathrm{PVC}=\\mathrm{CPVC}$ 时，涂层中形成了双连续的网络，即高聚物和颜料都是连续的，这种结构状态会使涂层（漆膜）的各种性能（如抗渗透性、起泡性、光泽、遮盖力、防蚀性）等发生突变。当PVC大于CPVC时，由于树脂量的不足，颜料体积太大，基料不足以包覆颜料、填料间的空隙，涂层不再连续致密。通常CPVC值用ASTMD281吸油法在强力研磨下求得，计算公式如下  \n\n$$\n\\mathrm{CPVC}{=}\\frac{1}{1+\\mathrm{IPZ}\\mathrm{\\i}\\mathrm{\\j}\\mathrm{\\/H}\\mathrm{\\perp}}\\times100\\%\n$$  \n\n式中吸油量一—以每毫升颜料耗用亚麻仁油的体积表示， $\\mathrm{mL}$  \n\n设计各种涂料时，不论屏蔽型或缓蚀型，PVC和CPVC的概念都很重要，它是一个基础数据。实际涂料配方中，采用的PVC值略低于CPVC值。一般 $\\mathrm{PVC/CPVC}=0.\\ 8\\sim0.\\ 9$ 0总之，涂料配方设计中，存在一个最优PVC范围，可以通过实验确定。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 221,
+        "chunk": "# 4.漆膜耐热性的评定  \n\n在完成配方设计后，如何在实验室测试耐温防腐涂料的各项性能，是衡量一个配方是否成功的基本条件。以下几项漆膜耐温性试验是耐热防腐涂料的特征性试验项目。  \n\n(1）漆膜耐热性能的测定按《漆膜耐热性测定法》[GB1735—1979（1989）」，将三块涂漆样板放置于已调节到按产品标准规定温度的鼓风恒温烘箱内。一块涂漆样板留作比较。待达到规定时间后，将涂漆样板取出，冷却至温度 $25^{\\circ}C$ ，与预先留下的一块涂漆样板比较，检查其有无起层、皱皮、鼓泡、开裂、变色等现象。如没有以上现象，则为合格。  \n\n(2）循环加热/防腐蚀测试在正常施工温度下制作涂料试板，然后放入烘炉中以$20^{\\circ}C/\\operatorname*{min}$ 的速率加热到目标温度稳定。在达到目标温度后，保持8h，然后自然冷却到环境温度。三个加热/冷却循环后，将试板用于各种防腐蚀性能测试(加速和自然老化试验)。  \n\n(3）循环加热/干湿循环（导管测试）一个被涂覆后的导管被放在加热托盘上（温度梯度为 $60\\sim450^{\\circ}C$ ）加热。一个循环经过8h的加热，16h的自然冷却到室温，然后将导管浸人1L $1\\%$ 的 $\\mathbf{NaCl}$ 溶液中，进行30个循环。  \n\n(4）基于ASTMD2485的热循环涂料试板以3天为一个周期进行热循环/淬火试验，每一个循环温度都比上一个目标温度提高。热循环后的试板用于盐雾试验和自然老化试验检测耐腐蚀性能。这个试验中的淬火是为了测试漆膜的耐热冲击性。  \n\n(5）热循环/浸泡试验这个试验和循环加热/防腐蚀测试操作近似，不同之处在于完成热循环后的试板浸泡在 $95^{\\circ}C$ 的盐水 $(1\\%$ 的 $N a C l$ 和去离子水）中。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 222,
+        "chunk": "# 八、机车涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 223,
+        "chunk": "# 1.概述  \n\n随着国民经济的快速发展，铁路运输量大幅度增加，在各类交通运输中其客运量一直位居首位，占 $50\\%$ 以上。我国铁路客车多次提速，车型更新换代，从普通客车，到豪华空调车，再到城际快速列车；从电气化铁路到磁悬浮列车建成通车以及正在建设的京沪高速列车，都对列车这一钢铁庞然大物的防护涂装提出了更高的要求，以满足广大旅客对铁路客车在方便快捷、乘坐舒适、视觉美观等多方面的要求。  \n\n(1）列车腐蚀环境的特殊性飞速奔驰的列车车厢，受到各种气候环境的侵袭，而作为列车车体主要材质的钢铁，其腐蚀过程主要是大气腐蚀——一种典型的电化学腐蚀，是在水和氧同时存在时才能发生，因在高温高湿条件下或受到盐类和酸性离子（如NaCI、 $\\mathrm{SO}_{2}$ $\\mathrm{CO_{2}}$ 等）的侵蚀而加剧；而在寒冷、干燥条件下减缓。实际上，在沙漠和零摄氏度以下的地区钢铁几乎不生锈。大气中各种各样的腐蚀因素，如温度、湿度、日光、降雨（雪）量、风沙以及污染物质等，均对钢铁腐蚀有影响。而列车这个钢铁庞然大物与一般巨大的钢结构（如桥梁、电站等）不同，遭受的气候环境随时随地变化着。例如从兰州开往广州的列车，头一天运行在西北沙漠地带，第二天就进入东南温湿地区，这就是列车腐蚀环境的特殊性。此外，列车提速后，风沙对列车涂层的摩擦磨损十分严重，加剧了气候环境对列车的腐蚀。  \n\n(2）国内列车涂料的相关标准我国铁道部和有关业务部门，对列车防腐蚀问题比较重视，先后制定并颁布了多项行业标准，并下发了相关文件。从涂料的选择到涂装工艺，特别是表面预处理；从涂料检测方法到涂装质量检查和验收规程等，均做出明确的要求和规定，形成了比较完备的列车用涂料与涂装技术标准体系。其中主要的行业标准如下。  \n\nTB/T2260—2001铁路机车车辆用防锈底漆  \nTB/T2393—2001铁路机车车辆用面漆  \nTB/T2393—2001附录A铁路机车车辆用中间涂层用涂料技术条件  \nTB/T2393—2001附录B铁路机车车辆用腻子技术条件  \nTB/T2707—1996铁路货车用厚浆型醇酸漆技术条件  \nTB/T2932一1998铁路机车车辆阻尼涂料供货技术条件  \nTB/T2879.1—1998铁路机车车辆涂料及涂装——涂料供货技术条件  \n\nTB/T2879.2—1998铁路机车车辆涂料及涂装——涂料检验方法TB/T 2879.3—1998 铁路机车车辆涂料及涂装——金属及非金属材料表面处理技术条件TB/T2879.4—1998铁路机车车辆涂料及涂装——货车防护和涂装技术条件TB/T2879.5—1998铁路机车车辆涂料及涂装——客车和牵引动力车的防护和涂装技术条件TB/T2879.6—1998铁路机车车辆涂料及涂装——涂装质量检查和验收规程  \n\n铁路机车车辆种类很多，按用途大致可分为牵引动力的机车、旅客列车（简称客车）及货车三类。铁路机车车辆用涂料与涂装工艺比较复杂，主要有预涂车间底漆、防锈底漆、腻子、中涂漆、面漆、货车用厚浆漆、车体内木器用清漆、车体内表面用为降低噪声的阻尼涂料、车内壁与地板用耐磨、耐冲击重防腐涂料以及双层客车的不饱和聚酯玻璃钢板材与坐椅上用的阻燃涂料等。由于篇幅限制，以下重点介绍铁路客车车辆外表面用涂料与涂装技术。",
+        "category": " Introduction"
+    },
+    {
+        "id": 224,
+        "chunk": "# 2.铁路机车车辆用涂料  \n\n(1）车间底漆车间底漆（shopprimer），又称预涂底漆，是在钢材喷射除锈后，需进行冷热加工、组成钢结构前的这段时间内，为防止钢材生锈而涂装的一种工序间防锈底漆。这种底漆除应具有工序间防锈功能外，还应具有可焊性（具体可参见第四章车间底漆部分)。  \n\n常用车间底漆是硅酸锌车间底漆，它是一种双组分含锌无机锌底漆。主要用于喷砂后钢板及其他钢结构的短期保护，其户外保护期为 $3\\sim12$ 个月。在钢结构组装完成后，通常需要重新喷砂，去除车间底漆，并及时喷涂配套底漆。  \n\n(2）铁路车辆用防锈底漆铁路车辆目前使用的防锈底漆主要品种有：无机富锌底漆、环氧富锌底漆、环氧酯底漆及双组分环氧底漆等。经过多年的发展，已基本定型为：以锌粉、磷酸锌、云母氧化铁、氧化铁棕为防锈颜料；以环氧、酚醛、醇酸及聚氨酯为基料的防锈底漆系列。其中高防锈性能的富锌底漆主要用于出口车和高级客车，醇酸、酚醛防锈底漆主要用于旧车修理，而普通新造车则多采用环氧酯底漆、双组分环氧底漆及聚氨酯底漆。我国铁道行业参照国际铁道联盟UC842系列标准，制定并颁布了铁道车辆用防锈底漆行业标准TB/T2260—2001《铁路机车车辆用防锈底漆》，其主要技术要求见表3-3-122。  \n\n表3-3-122 铁路机车用防锈底漆技术条件（TB/T2260—2001）  \n\n\n<html><body><table><tr><td>项 目</td><td>指标</td><td>项 目</td><td>指标</td></tr><tr><td colspan=\"2\" rowspan=\"3\">漆膜颜色和外观</td><td>颜色符合需方 弯曲性能/mm</td><td>< 2</td></tr><tr><td>要求，漆膜平整、 杯突试验/mm</td><td>4.0</td></tr><tr><td rowspan=\"2\">无明显颗粒 划格试验/级</td><td rowspan=\"2\">≤ 1</td></tr><tr><td colspan=\"2\">不挥发物含量/%</td></tr><tr><td colspan=\"2\" rowspan=\"2\">流出时间/s</td><td rowspan=\"2\">60</td><td rowspan=\"2\"></td><td rowspan=\"2\">50</td></tr><tr><td rowspan=\"2\">耐冲击性/kg·cm</td></tr><tr><td></td><td>≥ 20</td><td></td><td>无起泡，不生锈；</td></tr><tr><td colspan=\"2\">细度/μm 一般颜料</td><td>50</td><td rowspan=\"4\">耐盐雾性（500h) 1.5倍时，成膜性</td><td rowspan=\"4\">十字划痕处锈蚀宽 度≤2mm（单向） 膜厚为所需值</td></tr><tr><td colspan=\"2\" rowspan=\"3\">铁棕颜料、铁红颜料</td><td>≤</td><td></td></tr><tr><td>≤</td><td>70 4</td></tr><tr><td>≤ ≤</td><td>4 施工性能</td></tr></table></body></html>  \n\n(3）铁路车辆用腻子腻子是由漆料（干性油、合成树脂等）和填料、颜料调制成的一种膏状涂料，用于干燥后的头道底漆或二道底漆上面，起到填坑、找平的作用；用于客车外表面涂装中，保证外表面面平整度，以得到很好的外观装饰效果。TB/T2393—2001附录B《铁路机车车辆用腻子技术条件》将腻子分为普通腻子（如油性腻子、醇酸腻子等）和不饱和聚酯腻子（俗称“原子灰\"）两类。其主要技术要求见表3-3-123。  \n\n表3-3-123铁路车辆用腻子技术条件TB/T2393—2001附录B  \n\n\n<html><body><table><tr><td colspan=\"2\">项 目</td><td rowspan=\"2\">指标 无结皮、硬块、白点</td><td colspan=\"2\">项 目</td></tr><tr><td colspan=\"2\">外观 目测</td><td>划格试验/级</td><td>≤1</td></tr><tr><td colspan=\"2\">腻子膜颜色和外观</td><td>平整、不流挂、无颗粒、无</td><td>柔韧性/mm</td><td>≤100</td></tr><tr><td colspan=\"2\"></td><td>裂纹、无气泡，色调不定</td><td>涂刮性</td><td>易涂刮、不产生卷边现象</td></tr><tr><td rowspan=\"3\">稠度/cm 实于时间/h</td><td></td><td>9~16</td><td>打磨性</td><td>易打磨、不粘砂纸、无明显白点</td></tr><tr><td>普通腻子</td><td>≤24</td><td>耐冲击性/cm</td><td>≥15</td></tr><tr><td>不饱和聚酯腻子</td><td>≤4</td><td>耐水性试验</td><td>优秀</td></tr></table></body></html>  \n\n不饱和聚酯腻子是一种双组分高固体分、催化固化的填平涂料。固化干燥迅速、质地细腻、附着力好、填平打磨性能优异。一次刮涂可比一般腻子层厚！ $(1\\sim5\\mathrm{{mm})}$ ，不会产生外干内不干的现象，体积收缩率很小，干后无塌陷现象，而且无溶剂挥发，对环境污染小，不仅适用于铁路车辆涂装，也广泛用于汽车涂层修补及各类机械产品涂装。  \n\n(4）铁路车辆用中涂漆中涂漆也称中间漆，是由合成树脂、颜（填）料、助剂及溶剂等组成。通常中间漆的颜（填）料分比较高，颜基比较大，主要功能是增加底、面漆之间的附着力，改善面漆的丰满度，增大漆膜厚度，以增强漆层体质。而涂层的厚度直接影响涂层的性能和使用寿命。当然，使用寿命越长越好，但考虑到各种因素，一般主张采取 $5\\sim10$ 年的设计，比较可靠和现实。  \n\n涂层的厚度对使用寿命非常重要。实验已证明，在一定的腐蚀环境下，当涂层配套确定后，涂层厚度与保护寿命呈直线关系。而在实际涂装中，难以将底漆或面漆喷得过厚，而且也不经济，为了提高涂层的厚度一般通过中涂层来实现（表3-3-124)。  \n\n表3-3-124铁路车辆用中涂层技术条件TB/T2393—2001附录A   \n\n\n<html><body><table><tr><td>项</td><td>目</td><td>指标</td><td>项 目</td><td>指标</td></tr><tr><td>漆膜颜色和外观</td><td></td><td>符合颜色要求，表面 色调均匀一致，无颗施工性能 粒、针孔、气泡、皱皮</td><td></td><td>每道干膜厚度为要求 的1.5倍时，成膜良好</td></tr><tr><td>细度/μm</td><td>≤</td><td>30</td><td>弯曲试验/mm</td><td>2</td></tr><tr><td>流出时间/s</td><td></td><td>25</td><td>杯突试验/mm</td><td>4.0</td></tr><tr><td>双组分涂料适用期/h</td><td>≥</td><td>4</td><td>划格试验/级 ≤</td><td>1</td></tr><tr><td rowspan=\"2\">干燥时间/h</td><td>表干 ≤</td><td>4</td><td rowspan=\"2\">耐冲击性/cm</td><td rowspan=\"2\">50</td></tr><tr><td>实干</td><td>24</td></tr></table></body></html>  \n\n(5）铁路车辆用面漆根据列车腐蚀环境的特殊性，铁路车辆外表面用面漆应具有较好的耐候性，即具有较好的保光、保色性；列车长途运行可能会经过几个气候区，所用面漆应能适应寒冷、湿热等不同气候环境的变化；考虑到列车外表面经常清洗，要求面漆漆膜具有一定的耐酸、碱和耐各种不同的清洗剂；列车，特别是高速车风驰电制般运行，要求所用面漆漆膜具有较好的耐磨和耐冲击等力学性能；列车，特别是高档车对外表面面漆涂层的外观装饰性要求较高，色调明快、漆膜丰满。  \n\nTB/T2393—2001《铁路机车车辆用面漆》将认可使用的面漆分为两类：I类——用于一般要求的机车车辆外表面涂装，主要为醇酸类涂料；Ⅱ类——用于要求较高的机车车辆外表面涂装，主要为聚氨酯类涂料。其主要技术条件见表3-3-125。  \n\n表3-3-125 铁路车辆用面漆技术条件（TB/T2393—2001）  \n\n\n<html><body><table><tr><td colspan=\"2\" rowspan=\"2\">项 目</td><td rowspan=\"2\">单位</td><td colspan=\"3\">技术指标</td></tr><tr><td>I类</td><td></td><td>Ⅱ类</td></tr><tr><td colspan=\"2\">漆膜颜色和外观</td><td rowspan=\"2\">一 皱皮</td><td colspan=\"3\">符合颜色要求，表面色调均匀一致，无颗粒、针孔、气泡、</td></tr><tr><td>流出时间</td><td></td><td>≥25</td><td>≥20</td></tr><tr><td colspan=\"2\">细度 黑色</td><td>μm g/m²</td><td>≤20 ≤45</td><td></td><td>≤20 ≤45</td></tr><tr><td colspan=\"2\" rowspan=\"7\">遮盖力</td><td>灰色 绿色</td><td>g/m²</td><td>≤65</td><td>≤65</td></tr><tr><td>蓝色</td><td>g/m²</td><td>≤65</td><td>≤65</td></tr><tr><td>白色</td><td>g/m²</td><td>≤85</td><td>≤85</td></tr><tr><td></td><td>g/m²</td><td>≤120</td><td>≤120</td></tr><tr><td>红色</td><td>g/m²</td><td>≤150</td><td>≤150</td></tr><tr><td>黄色</td><td>g/m²</td><td>≤150</td><td>≤150</td></tr><tr><td colspan=\"2\">双组分涂料适用期</td><td>h</td><td>一</td><td>≥4</td></tr><tr><td>干燥时间</td><td>表干 实干</td><td>h h</td><td>≤4 ≤24</td><td>≤4</td></tr><tr><td colspan=\"2\">施工性能</td><td></td><td colspan=\"2\">≤24 每道干膜厚度为要求的1.5倍时，成膜良好</td></tr><tr><td colspan=\"2\">弯曲性能</td><td></td><td colspan=\"2\"></td></tr><tr><td colspan=\"2\"></td><td>mm</td><td>≤2</td><td>≤2</td></tr><tr><td colspan=\"2\">杯突试验</td><td>mm</td><td>≥4.0</td><td>≥4.0</td></tr><tr><td colspan=\"2\">划格试验</td><td>级</td><td>≤1</td><td>≤1</td></tr><tr><td colspan=\"2\">耐冲击性</td><td>cm</td><td>≥50</td><td>≥50</td></tr><tr><td colspan=\"2\">光泽</td><td>%</td><td>≥85</td><td>≥85</td></tr><tr><td colspan=\"2\">硬度</td><td></td><td>≥0.25</td><td>≥0.50</td></tr><tr><td colspan=\"2\">耐水性 耐汽油性</td><td>h h</td><td>≥12</td><td>≥24</td></tr><tr><td rowspan=\"3\">耐酸碱性</td><td>HzSO(3%)</td><td></td><td>≥6 ≥15</td><td>≥24 ≥30</td></tr><tr><td>NaOH(2%)</td><td>mm mm</td><td></td><td>≥30</td></tr><tr><td>HAC(5%)</td><td>mm</td><td>≥15</td><td>≥30</td></tr><tr><td colspan=\"2\">耐热性 耐人工气候加速试验</td><td>h</td><td>120℃±2℃≥1</td><td>150℃±2C≥1h</td></tr><tr><td colspan=\"2\"></td><td>h</td><td>200h≤2级</td><td>1000h≤2级</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 225,
+        "chunk": "# 3.铁路车辆用涂料配套  \n\n（1）一般涂料配套  \n\n$\\textcircled{1}$ 底漆 环氧酯底漆。  \n\n$\\textcircled{2}$ 腻子 环氧酯腻子。  \n\n$\\textcircled{3}$ 中间漆和面漆 醇酸面漆。  \n\n$\\textcircled{4}$ 特点涂料的配套性强，可适应各种列车涂装工艺要求，成本较低。比较适合涂装普通客车、货车，并方便用于列车的段修（手刷性能较好）。  \n\n（2）中级涂料配套  \n\n$\\textcircled{1}$ 底漆 环氧酯底漆。  \n\n$\\textcircled{2}$ 腻子 环氧酯腻子。  \n\n$\\textcircled{3}$ 中间漆和面漆 丙烯酸改性磁漆  \n\n$\\textcircled{4}$ 特点涂料的配套性强，可适应各种列车涂装工艺要求，成本适中。比较适合于追求较低成本而又满足高装饰保护要求的列车制造厂和车辆段，但涂装工艺要求比较严格，不  \n\n太适合于手刷涂装，且耐溶剂性能较差。  \n\n（3）高级涂料配套  \n\n$\\textcircled{1}$ 底漆 环氧底漆。  \n\n$\\textcircled{2}$ 腻子 不饱和聚酯腻子。  \n\n$\\textcircled{3}$ 中间漆 环氧厚浆漆或环氧云铁中间漆。  \n\n$\\textcircled{4}$ 面漆 丙烯酸脂肪族聚氨酯  \n\n$\\textcircled{5}$ 特点涂料的配套性要求较高，对列车涂装工艺也有较高要求，成本较高。综合性能十分优异，耐候性很好。适合涂装装饰保护要求较高的高档车（高速车、公务车、出口车等)，是自前国内各列车制造厂用于涂装高档车的常用配套。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 226,
+        "chunk": "# 4.铁路车辆用涂料展望  \n\n与其他防腐涂料一样，铁路车辆用涂料也向低有机溶剂挥发（VOC）、水性化、高固体分（VS）等类环保型涂料以及一些高性能功能型涂料方向发展。  \n\n（1）水性涂料水性涂料从20世纪40年代开始就以乳胶漆的形式成功地应用于建筑业，20世纪70年代化学工程师成功地使黏结剂分散粒子降到微米以下，从而带来了水性涂料的重大突破，使其可以形成更加紧密、难以渗透的漆膜，甚至可以和传统的溶剂型涂料性能相媲美，为低VOC环保型涂料开创出一条新路。已成功用于其他重防腐领域的水性环氧富锌底漆、水性环氧中间漆及水性聚氨酯磁漆，可考虑用于铁路车辆涂料体系。此配套体系防腐性能、耐候性能优异，保光保色性好，表面不易沾污、耐冲击、耐化学品和清洗剂，适合应用于铁路机车与客车的涂装。  \n\n(2）高固体分涂料和无溶剂涂料有机溶剂用于溶解或稀释黏结剂，便于涂料生产与施工，一旦涂装完成，它就变成了一种公害。通过研制低黏度的黏结剂，或引人像黏结剂一样能参与交联的被称之为“活性稀释剂”的单体，就能制造出高固体分涂料和无溶剂涂料。相对水性漆而言，当前推广高固分涂料在国内更现实。  \n\n$\\textcircled{1}$ 配套一  \n\na.底漆 高固体分环氧富锌底漆。  \n\nb.面漆 高固体分聚氨酯面漆。  \n\n此配套体系漆膜坚韧、耐冲击、耐腐蚀、耐化学品、保光、保色性好、不易沾污、易于清洗。适合涂装对机械强度要求高，维修期较长的机车、客车、罐车及货车。  \n\n$\\textcircled{2}$ 配套二  \na.底/面漆合一型。  \nb.无溶剂超强环氧漆， $100{\\sim}200\\mu\\mathrm{m}$  \n\n此配套体系适合涂装要求耐磨性和耐化学品性较高的罐车、漏斗车及平板车。可用高压无空气喷涂，VOC排放为零。  \n\n(3）高性能涂料-——聚硅氧烷与氟碳涂料近几年来人们在聚硅氧烷涂料和氟碳涂料作为聚氨酯涂料的更新换代产品方面进行了大量的研究。目前，这两类高档涂料均开始在防腐涂装中使用，铁路机车也开始尝试这方面的应用，曾做过氟碳面漆的相关涂装试验（详细情况，参见本章第二节)。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 227,
+        "chunk": "# 九、工程机械涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 228,
+        "chunk": "# 1.工程机械涂装概述  \n\n工程机械是一种户外工作机械，长期暴露在大气中，沿海地区还要经受盐雾的侵蚀、建  \n\n设工地的岩尘、煤灰和污染、石块的冲击等，施工工况十分恶劣。以往用户对于工程机械产品强调的是内在质量，现在则已经不再局限于内部质量和性能的满足，对外观质量也提出了很高的要求。",
+        "category": " Introduction"
+    },
+    {
+        "id": 229,
+        "chunk": "# 2.工程机械涂料  \n\n工程机械产品不仅要有可靠的性能，随着市场竞争的激烈加剧，工程机械正朝向高装饰、高防护性的方向发展。根据工程机械产品的工作性质和工况，其使用的涂料涂膜应具有附着力强、机械强度高、耐磨及耐腐蚀性能优异、光泽度高、耐候性好等特点，并具有涂装生产效率高、施工性能好及经济性好的优点。  \n\n1991年底我国机械行业发布了JB/T5946—1991《工程机械涂装通用技术条件》标准。该标准规定了工程机械产品涂装的通用技术要求、试验方法与检验规则，包括涂料要求、涂层部位与涂层颜色规定及涂装施工要求等。  \n\n工程机械产品的涂层主要由底漆、中涂、面漆组成。使用的涂料分为底漆、中涂漆、面漆。底漆是用于保护车体钢件的涂料，具有耐腐蚀性能优异、力学性能好、毒性低，对工程机械的底材有优异的防护；中涂漆能极好地填充打磨砂痕，易打磨，平整度好，能提高面漆的光泽及丰满度；面漆具有高装饰性，外观光亮、丰满、鲜艳性好，并具有很好的保光保色性能。所选用的各涂层涂料应有良好的配套性。",
+        "category": " Introduction"
+    },
+    {
+        "id": 230,
+        "chunk": "# (1）底漆  \n\n$\\textcircled{1}$ 选用的底漆性能及技术指标底漆对于工程机械产品的防锈蚀性能十分重要，随着工程机械业的迅猛发展和市场竞争的加剧，在工程机械方面对底漆的要求是防锈性能好、附着力强、机械强度高，耐盐水；易涂刷、易打磨、不流挂，能适应多种涂装方式；与各种常用腻子，中涂和面漆有很好的配套性，施工方便；污染小，价格适宜。  \n\n对于防锈底漆的具体性能要求见表3-3-126。  \n\n表3-3-126 底漆的性能要求指标  \n\n\n<html><body><table><tr><td>序号</td><td>项目</td><td>参考技术要求</td><td>检测方法</td></tr><tr><td>1</td><td>黏度(涂-6杯）/s</td><td rowspan=\"3\">≥45 ≤60</td><td rowspan=\"3\">GB 6753.4 GB 6753.1 GB 1726—1989</td></tr><tr><td>2</td><td>细度/μm 速盖力/（g/m²）</td></tr><tr><td>3</td><td>≤100</td></tr><tr><td>4 5</td><td>固体分含量/% 冲击强度/kgf·cm</td><td rowspan=\"2\">≥60 ≥50 划格0级</td><td>GB 6571 GB 1732</td></tr><tr><td>6</td><td>附着力</td><td>GB 9286</td></tr><tr><td></td><td rowspan=\"2\">耐硝基漆性</td><td rowspan=\"2\">划圈1级 不起泡、不膨胀、不渗色</td><td rowspan=\"2\">GB1720 GB 2239-91. 4.11</td></tr><tr><td></td></tr><tr><td>8</td><td>耐盐水性（3%NaCl)</td><td rowspan=\"2\">168h不起泡、不生锈 168h不起泡、不生锈、不脱落 168h，1级</td><td rowspan=\"2\">GB 1763 GB 1733 GB1771</td></tr><tr><td>9</td><td>耐水性（25℃） 耐盐雾性</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 231,
+        "chunk": "# $\\textcircled{2}$ 常用底漆介绍  \n\na.环氧富锌车间底漆以环氧树脂为基料，加入超细锌粉、防锈填料、溶剂、助剂，采用聚酰胺树脂作固化剂。具有阴极保护作用，防锈性能优异、附着力好、耐热、焊接、切割等烧损面积小，不影响焊接性能，并具有耐油、耐水等特性。主要用于经抛丸或喷砂后的板材或钢结构件的临时保护底漆。  \n\nb.铁红环氧底漆由快干环氧树脂、铁红、防锈颜料、助剂、混合溶剂等经研磨调配而成。具有干燥速率快、涂膜物理力学性能优良、耐水与防锈能力强以及良好的附着力等  \n\n特点。  \n\nc.环氧富锌底漆由环氧树脂、超细锌粉、溶剂、助剂，采用聚酰氨树脂作固化剂。具有阴极保护作用，防锈性能优异、附着力好、耐水、耐油。适用于经抛丸或喷砂的钢铁表面。  \n\nd.聚氨酯底漆由改性丙烯酸树脂聚合物及不变黄异氰酸酯固化剂，配以防锈颜料及填充物等组成。具有优异的耐水及耐海水性，耐磨性优良，极佳的耐油性及防锈性能，漆膜坚韧且附着力强等特点。  \n\ne.环氧酯底漆由改性快干环氧酯树脂、防锈颜料及填充物等组成。具有漆膜坚韧、附着力好，耐化学品性优良，耐磨性、耐水性、耐海水性好，极好的填充性等特点。  \n\nf.醇酸底漆由醇酸树脂、特殊树脂及防锈颜料等构成。附着力强、防锈性能好，耐海水性及耐油性好，施工性能好，且价格低廉，但与质量要求较高的中间涂层或面漆层配套性较差，因此，目前在工程机械行业的应用逐渐减少。",
+        "category": " Introduction"
+    },
+    {
+        "id": 232,
+        "chunk": "# (2）中涂漆  \n\n$\\textcircled{1}$ 中涂漆的性能和技术指标 中涂漆的具体性能和技术指标见表3-3-127。  \n\n表3-3-127 中涂漆性能及技术指标  \n\n\n<html><body><table><tr><td>序号</td><td>项 目</td><td>参考技术要求</td><td>检测方法</td></tr><tr><td>1</td><td>黏度(涂-6杯)/s</td><td>≥45</td><td>GB 6753.4</td></tr><tr><td>2</td><td>细度/μm</td><td>≤60</td><td>GB 6753.1</td></tr><tr><td>3</td><td>遮盖力/(g/m²)</td><td>≤100</td><td>GB 1726—1989</td></tr><tr><td>4</td><td>固体分含量/%</td><td>≥60</td><td>GB 6571</td></tr><tr><td>5</td><td>冲击强度/kgf·cm</td><td>≥50</td><td>GB 1732</td></tr><tr><td>6</td><td>附着力</td><td>划格1级</td><td>GB 9286</td></tr><tr><td>T</td><td>耐硝基漆性</td><td>不起泡、不膨胀、不渗色</td><td>GB 2239—1991</td></tr><tr><td>00</td><td>耐盐水性(3%NaCI)</td><td>168h不起泡、不生锈</td><td>GB1763</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 常用中涂漆  \n\na.环氧中涂漆由快干环氧树脂、颜料及填充物、助剂、溶剂精制而成，采用聚酰胺树脂作固化剂。具有干燥快、耐水与防锈能力强及良好的附着力与研磨性。  \n\nb.云铁环氧中涂漆由环氧树脂、鳞片状云母氧化铁、铝银浆、防锈颜料、各种助剂、溶剂、固化剂等组成。含有较高的防锈颜料成分，成膜后能平行定向排列成“鱼鳞片状”的搭接结构，具有较高的封闭性、耐热性、防腐性、耐候性和广泛的配套性。  \n\nc.聚氨酯中涂漆由改性丙烯酸树脂聚合物及不变黄聚异氰酸酯固化剂、防锈颜料及填充物精制而成。具有良好的物理、化学和力学性能，与底层、面漆层间均有良好的结合力，可增加面漆的光泽度及丰满度。  \n\nd.环氧聚酯中涂漆由环氧树脂、丙烯酸树脂聚合物、氨类固化剂、防锈颜料及填充物精制而成。具有良好的物理、化学和力学性能，与底层、面漆层间均有良好的结合力，可增加面漆的光泽度及丰满度。  \n\ne.环氧酯中涂漆由快干环氧酯树脂、颜料及填充物精制而成。具有干燥快、耐水、防锈能力强、附着力及研磨性好等特点。  \n\nf.丙烯酸环氧中涂漆由热塑型丙烯酸树脂及环氧树脂聚合物及颜料填充物精制而成。具有干燥快、配套性好、附着力强及打磨性好等特点。  \n\n(3）腻子  \n\n① 原子灰由特种不饱和树脂聚合物、过氧硬化剂及研磨性填充物配制而成。具有附着力强，质地细腻无光，与硬化物混合性好，干燥快，耐溶剂，可重叠刮涂，不会龟裂、龟缩等特性。广泛用于汽车、摩托车、工程机械、木制品及其他金属、非金属制品凹凸不平、缝隙、各类缺陷的填补与表面装饰填充物。  \n\n②喷涂原子灰由特种不饱和树脂聚合物、过氧硬化剂及研磨性填充物配制而成。可使用喷枪喷涂，作业效率高、方便。其特性、用途与普通原子灰相同。  \n\n$\\textcircled{3}$ 过氯乙烯腻子具有快干、坚硬、附着力好、易打磨、有优良的耐水性、耐油性，但不宜多次重复刮涂。可用于铸件、木器、钢铁件表面的填补。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 233,
+        "chunk": "# (4）面漆  \n\n$\\textcircled{1}$ 选用的面漆性能及技术指标 面漆性能及技术指标见表3-3-128。  \n\n表3-3-128 面漆性能及技术指标  \n\n\n<html><body><table><tr><td>序号</td><td>项 目</td><td>参考技术要求</td><td>检测方法</td></tr><tr><td>1</td><td>外观</td><td>无异物、无硬块，易搅拌的均匀液体</td><td>GB 3186</td></tr><tr><td>2</td><td>固体分含量/%</td><td>≥55</td><td>GB 6571</td></tr><tr><td>3</td><td>细度/μm</td><td>≤20</td><td>GB 6753.1</td></tr><tr><td>4</td><td>遮盖力/（g/m²）</td><td>≤120</td><td>GB 1726</td></tr><tr><td>5</td><td>光泽度(60°)</td><td>≥90</td><td>GB 1743</td></tr><tr><td>6</td><td>附着力</td><td>划格1级</td><td>GB9286</td></tr><tr><td>7</td><td>柔韧性</td><td>≤2</td><td>GB 1731</td></tr><tr><td>8</td><td>硬度</td><td>≥0.65</td><td>GB/T 1730</td></tr><tr><td>9</td><td>冲击强度/kg*cm</td><td>≥50</td><td>GB 1732</td></tr><tr><td>10</td><td>耐水性(25C)</td><td>168h不起泡、不起皱、不脱落、允许漆膜变白，2h恢复</td><td>GB/T1733</td></tr><tr><td>11</td><td>耐酸性（浸人5%HSO）</td><td>12h不起泡、不起皱、不脱落</td><td>GB 9274.5</td></tr><tr><td>12</td><td>耐醇性（浸人50%乙醇溶液）</td><td>4h不起泡、不起皱、漆膜无异常</td><td>GB 9274.5</td></tr><tr><td>13</td><td>耐磨性（750g/500r）</td><td>≤0.03</td><td>GB 1768</td></tr><tr><td>14</td><td>人工耐老化1000h</td><td>无明显龟裂，变色≤3级，失光率≤15%</td><td>GB1865</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 常用面漆介绍  \n\na.丙烯酸面漆由丙烯酸树脂、增塑剂、耐候性颜料、助剂、混合溶剂等经研磨调配而成。具有优良的附着力、耐候性、保光保色性，漆膜耐久、抗腐蚀性能。  \n\nb.丙烯酸聚氨酯面漆以羟基丙烯酸树脂为基料，加入颜料、助剂等研磨而成，以异氰酸酯树脂作为固化剂。具有优异的漆膜力学性能，耐化学品性和保光、保色性，漆膜光泽度高、丰满度好，流平性好，固体分含量高，一次喷涂即可达到工艺要求的漆膜厚度。  \n\nc.醇酸树脂面漆由中油度醇酸树脂及耐候性钛白粉精制而成。漆膜光泽度高，柔韧性好，附着力强，耐油性、耐水性好，施工性能优良，但耐候性较差，不适用于耐候性要求高的产品。传统工程机械大多采用醇酸面漆，随着人们对工程机械外观质量要求的提高，生产厂家已越来越少使用该漆种。  \n\n(5）涂层质量要求JB/T5946—1991虽然未对上述底漆、中间漆、腻子及面漆规定单层技术指标要求，但对配套涂层的质量进行了规定，见表3-3-129。  \n\n表3-3-129 工程机械产品涂层质量要求（JB/T5946—1991）  \n\n\n<html><body><table><tr><td>序号</td><td>指标项目</td><td>质量要求</td><td>试验方法</td></tr><tr><td>1</td><td>涂膜颜色</td><td>与标准色样样板相同</td><td rowspan=\"3\">GB/T 1729</td></tr><tr><td>2</td><td>涂膜外观</td><td>应光滑平整，无鼓泡、裂纹、漏涂、剥落，各色漆相互不得沾染，交界清晰</td></tr><tr><td>3</td><td>涂膜光泽度</td><td>对外观有直接影响的表面，涂膜光泽度不小于80%</td></tr><tr><td>4</td><td>干膜厚度/μm</td><td>80～120</td><td>GB/T 1764</td></tr><tr><td rowspan=\"2\">5</td><td rowspan=\"2\">力学性能</td><td>冲击强度：490N·cm</td><td>GB/T 1732</td></tr><tr><td>柔韧性：1～2mm</td><td>GB/T 1731</td></tr><tr><td>6</td><td>耐候性</td><td>硬度：>0.3 使用一年后，涂膜应平整（不起泡、不开裂，轻微粉化)允许失光不大于</td><td>GB/T1730 GB/T 1865</td></tr><tr><td>7</td><td>耐水性</td><td>50%，允许变色</td><td></td></tr><tr><td>8</td><td>耐中性盐雾化</td><td>浸在室温蒸馏水中24h，合格 100h，合格</td><td>GB/T 1733 GB/T 1771</td></tr><tr><td>9</td><td>附着力(划圈法)/级</td><td>1~3</td><td>GB/T1720</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 234,
+        "chunk": "# 3.涂装工艺  \n\n工程机械品种繁杂，规格多样，体积大，重量大，结构复杂，不同的产品有其不同的生产特点，使用环境也不尽相同，因此涂装工艺各有特点。涂装过程的运输系统必须考虑到上、下线的方便及工序运输平稳、可靠，工人喷漆作业简便易行。  \n\n尽管工程机械品种大而杂，根据产品的结构特点，在涂装工艺设计时，可以分为薄板覆盖件涂装、大型结构件涂装、整机涂装。传统的涂装工艺是零部件完成底漆、中涂漆的涂装，然后进行装配、试车，合格后再进行表面清洗、刮腻子、打磨、屏蔽、喷涂面漆，这样的工艺方法，可以不怕零部件在装配、运输等过程中的磕碰、漆膜碰伤等，从而保证整机表面颜色的一致性；但在整机喷涂时需要大量的屏蔽工作。  \n\n随着物流水平的不断提高，整机涂装正朝着简易化方向发展，即零部件底漆、中涂漆、面漆的涂装在整机装配前已经完成，整机试车合格后，仅需根据整机的表面状态进行局部修饰。  \n\n（1）薄板覆盖件的涂装工艺工程机械薄板覆盖件指用厚度 $4\\mathrm{mm}$ 以下的热轧或冷轧钢板制造，由于钢材表面锈蚀、氧化皮及加工成型过程中产生的油污等，为了保证其得到良好的漆膜附着力和漆膜质量，零部件喷漆前均需进行预处理，并保证达到预处理质量要求。基本工艺流程包括预处理、电泳、底漆涂装、刮涂腻子、打磨和喷涂中涂漆或面漆等。  \n\n工程机械薄板覆盖件种类繁多，形状各异，表面油污、锈蚀、氧化皮等附着，严重影响漆膜附着力及喷漆后的外观，降低涂装的防护和装饰性。因此，可根据覆盖件的种类、使用要求等进行酸洗、磷化后，选择采用电泳涂装或直接喷涂底漆、中涂漆或面漆。如驾驶室、机罩等采用酸洗、磷化后进行电泳涂装再喷涂中涂漆或面漆；而如油箱，酸洗、磷化后选择直接喷涂底漆、中涂漆或面漆。  \n\n(2）大型结构件涂装工艺工程机械结构件形状复杂，外形尺寸大，如装载机的前车架、后车架、铲斗、动臂等，挖掘机的回转平台、行走架、大臂、斗杆、铲斗等。大型结构件涂装工艺设计应考虑“先进、实用、经济、可靠”，并力求做到高水平、高质量、高效率，机械化、自动化程度高。涂装工艺如下。  \n\n机加工孔保护 $\\bf\\Pi^{*}$ 上件 $\\nrightarrow$ 抛丸清理 $\\rightarrow$ 吹风 $\\nsim$ 喷底漆 $\\nsim$ 流平 $\\blacktriangledown$ 烘干 $\\rightarrow$ 局部刮涂腻子、干燥、打磨 $\\twoheadrightarrow$ 清理、吹风 $\\blacktriangleleft$ 内表面喷面漆（外表面喷中涂漆） $\\blacktriangledown$ 流平 $\\rightarrow$ 烘干 $\\nsim$ 下件 $\\mathbf{-}$ 去屏蔽、清  \n\n理 $\\twoheadrightarrow$ 防锈 $\\rightarrow$ 交库  \n\n(3）整机涂装工艺整机装配、调试合格后，由于在装配及运输过程中存在零部件表面磕碰，以及企业协作化生产的发展，为了保证表面颜色一致，减少物流配送、零部件包装防护的投人，就采用整机喷涂的涂装工艺。整机涂装的工艺流程如下。  \n\n整机调试合格后清洗 $\\rightarrow$ 干燥（自干或烘干） $\\nrightarrow$ 局部刮腻子、打磨 $\\cdot+$ 吹风、清洗 $\\twoheadrightarrow$ 吹水、烘干 $\\nsim$ 屏蔽 $\\twoheadrightarrow$ 上线、轮胎保护 $\\mathbf{\\nabla}\\rightarrow$ 水旋喷漆室（双工位） $\\nrightarrow$ 热风干燥（双工位） $\\rightarrow$ 强冷 $\\rightarrow$ 下线 $\\rightarrow$ 整理精饰 $\\nrightarrow$ 检查  \n\n随着用户对外观质量要求的提高，整机表面的颜色已呈现多样化，已从单一颜色向多色转变，即所谓的套色，但为了降低整机涂装生产的周转时间，套色表面一般安排在零部件涂装时完成，待整机其他表面喷漆时再用胶带、纸等进行屏蔽。  \n\n(4）涂装质量管理涂装质量管理是保证工程机械涂层质量、延长涂层寿命的重要环节，可分为涂料本身的质量控制和涂装工艺过程工序质量控制及成膜后产品的管理加以解决。  \n\n涂料本身质量是获得优良涂层的保证，一般根据工程机械所选用的涂料产品技术标准，按照使用单位与涂料生产单位制定的技术协议指标进行测试，要求涂料厂家应有随货质量检验合格报告，加强进厂检验，并不定期进行如曝晒性能试验或委托权威检测机构对主要漆膜性能进行检测。  \n\n涂装工艺过程主要由预处理、喷漆、烘干等主要工序组成。预处理质量控制是整个涂装工程中最基础的工作。经抛丸处理的零件表面应呈金属本色，达 $\\mathrm{{Sa2.5}}$ 级要求，不得有残存氧化皮、粘砂、锈迹等；经酸洗、磷化处理的零件，表面应无氧化皮、锈迹、脏物、油污、酸碱残液等，磷化膜应结晶致密、连续、均匀，不能有氢脆、严重挂灰、结晶疏松等缺陷；经打磨的表面不能有浮锈、氧化皮、焊渣、油污等。喷漆施工应在清洁、干燥、空气流通、光线充足的专用喷漆室内进行，室内温度最好控制在 $10\\sim35^{\\circ}C$ ，相对湿度不大于 $85\\%$ ，如相对湿度太高，应进行除湿处理，必须严格控制施工黏度、喷涂距离、喷雾搭接幅度等，严格按照工艺要求进行，避免出现流挂、露底、咬底、橘皮、颗粒、缩孔等漆膜病；在烘干过程应适当控制升温速率、烘干温度，保证烘干环境的清洁，漆膜未干燥前不许溅到水滴等，避免出现起皱、失光、针孔、起泡、变色、龟裂等。  \n\n随着工程机械生产批量的加大，许多厂家都采用社会化生产协作的方式扩大生产规模，协作厂家的涂装质量对产品的外观质量有很大影响。因此，应与协作厂家针对生产的零部件制定相应的涂装工艺要求及保护包装协议，运输过程要有合适的工装器具，减少漆膜磕碰。严格要求按双方确认的色板同步组织生产。  \n\n在关注涂装生产过程的质量控制的同时，必须采取有效措施对涂装后的产品加以防护，如喷涂漆膜防护涂料；对运输过程中的漆膜磕碰应及时用同类涂料进行补涂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 235,
+        "chunk": "# 参考文献  \n\n[1］曹楚南．中国材料的自然环境腐蚀．北京：化学工业出版社，2005．1.  \n[2]柯伟，中国工业与自然环境腐蚀调查，腐蚀与防护．2004．25（1).  \n[3]曾荣昌，韩恩厚，材料的腐蚀与防护，北京：化学工业出版社，2006．5.  \n[4]李荣俊．金属防锈及其试验方法，北京：机械工业出版社，1993．9.  \n[5] 任晓云，李建三．桥梁工程中的腐蚀问题，中山大学学报论丛．2002．22（3).  \n[6］李国莱等．重防腐涂料．北京：化学工业出版社，1999.  \n[7］江磐，张俊智．纳米材料在涂料中应用前景预测，中国化工报，2005．3．8.  \n[8] 杨振波，杨忠林，郭万生，第三届国际防腐及防腐蚀涂料技术研讨会论文集：新型鳞片状金属颜料及其应用，珠  \n\n海：中国化工学会、全国涂料工业信息中心，2005.05.[9]金晓明，郑添水．鳞片状锌基环氧富锌底漆的研究．材料保护，1999，4：25-26.[10]Kurt Zimmerman, Zinc Fine Flakes for Corosion Protection. European Coating Journal， 1991，(1).[11］朱洪．富锌底漆中锌粉的分析研究．涂料工业，1998，28（2)：38-41.[12］徐国强．水性工业防腐涂料．涂料工业，2001，（6).[13]沈岳，AidmondtM.，王健，适用于重防腐体系的高性能水性涂料，中国涂料、2005，（6).[14]L.利斯伯．拉逊．输气管道内壁涂漆的经济性．涂料工业、2000，（11).[15］徐国强，李荣俊，林绍基，重防腐蚀聚硅氧烷涂料．涂料工业，2004，34，（8）.[16］吴海军，陈艾荣，桥梁结构耐久性设计方法研究．中国公路学报，2004，17（3).[17］吴贤官．建设工程涂装质量管理．北京：化学工业出版社，2004.[18］杜洪彦等，混凝土的腐蚀机理与新型防护方法．腐蚀科学与防护技术，2001，13（3).[19］刘一芳等，混凝土的环境腐蚀机理浅析，煤矿安全，2005．36（4).[20] 易伦雄．钢结构桥梁防腐蚀涂装体系的选择，桥梁建设，1999（2）.[21]林绍基，李荣俊．桥梁钢箱梁防腐涂装中预涂富锌底漆与热喷镀锌或铝两种工艺比较，涂料工业，2001（10).[22] 陈阶亮．桥梁钢结构防腐蚀技术探析．钢结构，2002（05).[23］刘新，桥梁混凝土结构的防护涂装技术．中国涂料，2004（12).[24］李荣俊．当前我国防腐涂装工程中若干问题的讨论．现代涂料与涂装，2007，10（8).[25］洪乃丰，钢筋混凝土基础设施的腐蚀与全寿命经济分析法，建筑技术，2002，（4).[26]Christopher L. Farschon，Robert A.Kogler.Field Testing Maintenance Overcoating System for Bridges. JPCL1997，(01).[27］纪云岭，张敬武，张丽．油田腐蚀与防护技术．北京：石油工业出版社，2006.[28］俞蓉蓉，蔡志章，地下金属管道的腐蚀与防护．北京：石油工业出版社，1998.[29］卢绮敏等．石油工业中的腐蚀与防护．北京，化学工业出版社，2001.[30］宋天博．我国埋地钢质管道使用环氧粉末涂层的情况．腐蚀与防护，2006，27（7).[31］龚树鸣．长输天然气管道外防腐涂层选择，石油天然气．2001，（3).[32]董宝山，埋地保温管道的腐蚀调查，腐蚀与防护，2006，27（12).[33］余存烨，油罐内防腐设计、化工设备与管道，2001，（5).[34］宋广成．油罐内壁防蚀防静电涂料与涂层结构，石油工程建设，2000，（1).[35］倪玉德．FEVE氟碳树脂与氟碳涂料．北京：化学工业出版社，2006.[36]许莉莉，机场建中长效防腐蚀新配套设计方案及涂装过程的质量控制，上海涂料，2006（8).[37]Lori Huffman， Harold Hower. The Emergence of Polysiloxanes As Protective Coatings. JPCL，2003，（8).[38]Ko Kei jman. The Use of Novel Siloxane Hybrid Polymers in Protective Coatings. PCE,1996 (7).[39］MahindaPradeep，李荣俊．中国港口机械与设备钢结构防护涂装．中国涂料，2005，（6）.[40］李荣俊，刘礼华，水工钢结构防腐涂料与涂装．现代涂料与涂装．2007，（2).[41]Jorge E. Costa & Leandro Etcheverry Corrosion Control Technology. PCL. 2006，(3).[42]曾德龙，卜建欣，三峡金属结构防腐蚀措施研究，中国三峡建设，2003，（2).[43]核工业第二研究设计院，《核岛机械设备涂装通用技术条件》2004，09（内部资料).[44］战凤昌，李悦良，专用涂料，北京：化学工业出版社，1988.[45］林安，周苗根，功能性防腐蚀涂料及应用，北京：化学工业出版社，2004.",
+        "category": " References"
+    },
+    {
+        "id": 236,
+        "chunk": "# 海洋涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 237,
+        "chunk": "# 一、船舶涂料概况",
+        "category": " Introduction"
+    },
+    {
+        "id": 238,
+        "chunk": "# 1.船舶涂料的特性  \n\n船舶结构复杂，其各个部位保护要求不同，因而所需涂料也就各不相同。由于船舶涂装有其自身的特点，因此船舶涂料具备如下特征。  \n\n$\\textcircled{1}$ 船舶的庞大决定了船舶涂料必须能在常温下干燥固化  \n\n$\\textcircled{2}$ 船舶涂装施工的面积大，因此涂料应适合于高压无气喷涂作业。  \n\n$\\textcircled{3}$ 由于船舶涂装施工工作量大，而且个别部位施工比较困难，因而希望一次涂装能达到较高的膜厚，故往往需要厚膜型涂料。  \n\n$\\textcircled{4}$ 船舶的水下部位及海水压载舱通常需要使用阴极保护，因此，用于这些部位的涂料需要有较好的耐电位性、耐碱性。  \n\n$\\textcircled{5}$ 船舶从防火安全角度出发，要求机舱内部、上层建筑内部的涂料不易燃烧，且一旦燃烧时也不应释放出过量的烟。因此，硝基漆、氯化橡胶漆均不适宜作为船舶舱内装饰涂料。  \n\n$\\textcircled{6}$ 化学品船经常装载不同的化学物质，各种化学物质其腐蚀性不同，因而化学品船其舱室涂料要求有宽广的耐化学物质特性。  \n\n$\\textcircled{7}$ 船舶的货物舱经常要装载可食用的物品，因而所施工的涂层不能污染物品，满足食物安全要求。$\\textcircled{8}$ 船舶的饮水舱涂料要满足饮水健康要求。",
+        "category": " Introduction"
+    },
+    {
+        "id": 239,
+        "chunk": "# 2.船舶涂料的分类和要求  \n\n船舶涂料可根据基料类型、使用部位、作用特点、施工方式等不同方法进行分类。目前比较通用的分类是按其使用部位分类。表3-4-1列出了船舶涂料主要分类和基本要求。  \n\n此外，根据其基料类型的不同，船舶涂料还划分为常规涂料和高性能涂料两类。以油脂类、醇酸树脂、酚醛脂及一些天然树脂为基料的船舶涂料，是早期发展和应用的涂料，称之为常规涂料。而以各种耐水性好、耐化学性好的合成树脂为基料，多数制成厚膜型的船舶涂料，是近年来不断发展和日益广泛获得应用的涂料，称之为高性能涂料。  \n\n表3-4-1船舶涂料的分类和基本要求  \n\n\n<html><body><table><tr><td>部位</td><td>名称</td><td>基本要求</td><td>涂料类型</td><td>备注</td></tr><tr><td>钢板 预 处理</td><td>车间底漆</td><td>1.干燥快 2.耐热性 3.低毒性 4.与后续涂料的兼容性</td><td>1.磷化底漆（聚乙烯醇缩丁 醛树脂) 2.环氧富锌底漆 3.环氧铁红底漆</td><td>无机硅酸锌底漆为常用车间 底漆</td></tr><tr><td></td><td>船底防锈漆</td><td>5.独立的预认证 1.优异的防锈性 2.耐冲击 3.耐磨 4.与阴极保护的相容性</td><td>4.无机硅酸锌底漆 1.氯化聚烯烃防锈漆 (1)橡胶类船底防锈漆 (2)氯醋树脂防锈漆 (3)高氯化聚乙烯防锈漆 (4)氯醚树脂防锈漆 2.沥青船底防锈漆</td><td>(1)、(2)两项已不常用；沥青类 涂料由于健康原因正在淘汰；第4 项分为改性环氧及纯环氧</td></tr><tr><td>船底连接漆</td><td></td><td>连接船底防锈漆和船底防</td><td>3.环氧沥青船底防锈漆 4.环氧类船底防锈漆 1.环氧沥青连接漆</td><td>沥青类涂料由于健康原因正在</td></tr><tr><td></td><td>船底防污漆</td><td>污漆 1.防止海生物在船体的生长 2.稳定的防污性能 3．对环境无污染</td><td>2.乙烯环氧连接漆 1.接触型防污漆 2.扩散型防污漆 3.基料可溶型防污漆 4.水解自抛光型防污漆</td><td>淘汰 按IMO规范要求，防污漆不应 含有机锡</td></tr><tr><td>水 水线漆 线</td><td></td><td>1.防锈性 2.耐候性 3.耐干湿交替性 4.耐摩擦、耐冲击</td><td>5.低表面能、不含杀虫剂防 污漆 1.氯化橡胶水线漆 2.丙烯酸树脂水线漆 3．乙烯基树脂水线漆 4.环氧水线漆</td><td>由于对环保的影响，溶剂法氯 化橡胶水线漆逐渐被淘汰</td></tr><tr><td>以 下 涂 料</td><td>船壳底漆</td><td>5.与阴极保护相容 船壳漆主要用于船舶干舷，上 层建筑外部和室外船装件 防锈性</td><td>5.水线防污漆 1.醇酸船壳漆 2.氯化橡胶船壳漆 3.丙烯酸树脂船壳漆 4.聚酯树脂船壳漆 5.乙烯基树脂船壳漆</td><td>由于对环保的影响，溶剂法氯 化橡胶船壳漆逐渐淘汰</td></tr><tr><td>船壳面漆</td><td></td><td>耐候性</td><td>6.环氧树脂船壳漆 1.醇酸面漆 2.环氧面漆 3.丙烯酸面漆 4.聚氨酯面漆</td><td></td></tr><tr><td>甲板漆</td><td></td><td>1.防腐蚀 2.耐磨 3.耐油</td><td>5.聚硅氧烷面漆 1.醇酸甲板漆 2.氯化橡胶甲板漆 3.环氧甲板漆</td><td>由于对环保的影响，溶剂法氯 化橡胶甲板漆逐渐淘汰</td></tr><tr><td>货舱漆</td><td></td><td>4.防滑 1.耐磨 2.耐冲击 3.光滑易清洗</td><td>4.甲板防滑漆 1.环氧货舱漆 2.耐磨环氧货舱漆</td><td></td></tr><tr><td>机舱室漆</td><td>4.谷物证书 低播烟</td><td></td><td>1.醇酸漆 2.环氧漆</td><td></td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>部位</td><td>名称</td><td>基本要求</td><td>涂料类型</td><td>备注</td></tr><tr><td rowspan=\"3\">液 舱 涂 料</td><td>压载水舱涂料</td><td>1.优异的防锈性 2.与阴极保护的相容性 3.快干，有利施工 4.浅色，易检查</td><td>1.环氧沥青压载舱漆 2.改性环氧压载舱漆 3.纯环氧压载舱漆</td><td>按IMOPSPC要求进行预认 证；沥青类涂料由于健康原因正 在被淘汰</td></tr><tr><td>饮水舱涂料</td><td>饮水舱涂料卫生证书</td><td>1.纯环氧饮水舱涂料 2.酚醛环氧饮水舱涂料</td><td>通常用无溶剂环氧涂料</td></tr><tr><td>油舱涂料</td><td>耐油</td><td>1.石油树脂漆 2.环氧沥青漆 3.环氧树脂漆 4.无机锌涂料</td><td>沥青类涂料由于健康原因正在 被淘汰</td></tr><tr><td></td><td>化学品舱涂料</td><td>1.满足FDA要求 2.适用不同化学品 3.易清洗</td><td>1.纯环氧涂料 2.酚醛环氧涂料 3.无机锌涂料</td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 240,
+        "chunk": "# 二、车间底漆",
+        "category": " Introduction"
+    },
+    {
+        "id": 241,
+        "chunk": "# 1.车间底漆概述  \n\n车间底漆（shop primer）又称钢材预处理底漆（prefabrication primer)，是钢材（钢板或型钢）经喷砂处理除锈后在车间流水线上喷涂于金属表面的快干底漆，以防止其在加工、组装等过程期间产生锈蚀，从而大大减轻分段或船台涂装时的除锈工作量。  \n\n带有喷漆室的离心抛丸车间在船体钢结构建造中已经非常普遍。钢板在离心抛丸室自动清洗掉锈和氧化皮，然后几分钟之内在喷漆室涂上车间底漆或其他的临时保护底漆。再在几分钟之内，钢板就可以运送到贮存处或制造区域。因此，大批量的钢板可以在切割和焊接成大的或复杂的分段以前以非常低的成本地进行冲砂和喷漆。  \n\n如图3-4-1所示为典型的车间底漆生产线，该生产线一般分为四个区域：加热、喷砂/清洁、车间底漆喷涂及干燥区。钢板由传送带输送而通过各个区域。  \n\n![](images/c0f1f265247da73c840b454833c8d52f68767f1ecb6dd6f68f9b80dc01c80446.jpg)  \n图3-4-1 车间底漆流水线",
+        "category": " Introduction"
+    },
+    {
+        "id": 242,
+        "chunk": "# 2.车间底漆的性能  \n\n与通常的涂层不同，车间底漆有以下几个特点。  \n\n$\\textcircled{1}$ ① 车间底漆是一种临时保养性的底漆，在分段涂装时它可以除去，也可以保留，主要取决于涂装时车间底漆涂层本身的完好性和第一层涂装的涂料对表面处理的具体要求。为此，车间底漆的膜厚将不计入涂层的总膜厚之内。  \n\n$\\textcircled{2}$ 钢材涂有车间底漆以后，在焊接、切割时，该底漆可不必除去。③由于正式涂装时车间底漆可以保留，故车间底漆要能与各种涂料配套应用。$\\textcircled{4}$ 车间底漆的喷涂是在自动化流水线上进行的。由于施工上的这些特点，决定了车间底漆应具备与一般涂料所不同的性能。最重要的特点如下。$\\textcircled{1}$ 可以使用自动设备，喷涂方便。$\\textcircled{2}$ 必须对喷砂过的钢铁有极好的附着力。$\\textcircled{3}$ 快干，在喷涂 $3\\mathrm{\\sim}5\\mathrm{min}$ 后不粘辊道即可搬运。$\\textcircled{4}$ 必须有足够的机械强度和柔韧性，以防搬运和制造过程中的损坏。$\\textcircled{5}$ 应有优良的防腐性能。$\\textcircled{6}$ 可以复涂大多数类型的涂料。$\\textcircled{7}$ 有优良的耐水、化学和溶剂性能。$\\textcircled{8}$ 不影响钢板的切割速率。$\\textcircled{9}$ 不影响焊接的质量。$\\textcircled{10}$ 加热时不产生有毒气体。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 243,
+        "chunk": "# 3.车间底漆的种类  \n\n车间底漆的诞生始于20世纪40年代末50年代初。最初开发的品种是以聚乙烯醇缩丁醛为基料的PVB车间底漆，又称磷化底漆。  \n\nPVB车间底漆对于钢材的焊接和切割无任何不良影响，干性快，其表面能涂覆各种有机型涂料，价格也较低廉，在20世纪50年代获得广泛应用，至今国外仍有一些船厂在继续沿用。但该漆在室外保养期较短（一般为3个月），热加工时损伤面积较大，耐电位性能较差，不适合装有阴极保护系统的船体水下部位，故应用受到一定的限制。  \n\n为了弥补PVB车间底漆的不足，20世纪60年代初开发了环氧富锌底漆（zinc rich ep-oxy primer)。环氧富锌底漆以环氧树脂为基料，以聚酰胺树脂为固化剂，以金属锌粉为主要防锈颜料。通常干漆膜中锌粉含量在 $87\\%\\sim92\\%$ 。由于锌粉颗粒相互接触，能起到类似镀锌层的电化学保护作用，因此环氧富锌底漆具有很好的防锈性能，其室外保养期为 $6\\sim9$ 个月。此外，该漆耐热性较好，热加工时损伤面较小。但环氧富锌底漆由于锌粉含量多，电焊、切割等热加工时，释放较多的氧化锌烟尘，对人体健康带来影响，易导致“锌热病”，且对切割速率和质量亦有一定影响。环氧富锌漆的另一个缺点是在其表面不能涂覆常规的油性漆和油基漆，尤其是船体水下部位，会导致漆基中油料的皂化，使涂层起泡、剥离。  \n\n20世纪60年代中期，为克服环氧富锌的端，开发了环氧无锌底漆（non zinc epoxyprimer)，也称为环氧铁红底漆（iron oxide epoxy primer)。环氧铁红车间底漆以环氧树脂为基料，聚酰胺树脂为固化剂，氧化铁红为主要防锈颜料。由于不含锌，热加工时无氧化锌烟尘产生。对面漆也无选择性，并且具有良好的耐溶剂性和化学稳定性，特别适合作为装载石油制品的运输船（成品油船）的货油舱部位钢材的预处理底漆。  \n\n该漆防锈性能低于环氧富锌底漆而略高于磷化底漆，室外保养期约为4个月。其另一个缺点是干性稍差，抛丸预处理流水线必须安装烘干设备。  \n\n20世纪70年代初出现了无机锌底漆（inorganic zincprimer），亦称硅酸锌底漆（zincsilicateprimer）或无机硅酸锌底漆。  \n\n无机锌底漆用作车间底漆的多是醇溶性自固型。其以硅酸乙酯为基料，锌粉为主要防锈颜料，依靠吸收空气中的水分水解缩聚，并与锌、铁反应形成硅酸锌、铁复合盐类而紧密附着于钢铁表面。相对铁来讲金属锌为阳性（即锌比铁先腐蚀从而保护铁)，但是锌将在比铁较低的温度下先熔化（锌在420℃熔化，铁在1500℃熔化)，并且锌将在906℃时沸腾。因此，在焊接涂有硅酸锌车间底漆的钢板时，金属锌将汽化而使焊接弧不稳定，如果锌蒸气被截留在焊缝内将导致气孔。基于这种原理，无机硅酸锌车间底漆中的金属锌含量正趋于减少，如第一代无机硅酸锌车间底漆锌含量通常为60%～70%，第二代无机硅酸锌车间底漆锌含量通常为 $40\\%\\sim50\\%$ ，第三代无机硅酸锌车间底漆锌含量通常为 $20\\%\\sim30\\%$  \n\n无机锌底漆作为车间底漆有许多突出的优点，不仅有优良的防锈性，室外保养期可达$6\\sim9$ 个月，而且于性快、力学性能好、耐热性能优异、热加工损伤面积小、耐溶剂性能强，是目前应用较广的一种车间底漆。但其焊接、切割时仍有一定量的氧化锌烟尘发生（比环氧富锌底漆则少很多)，还需加强个体劳动保护。  \n\n上述四种车间底漆是迄今为止国内外车间底漆的主要品种，这些车间底漆主要的性能特点详见表3-4-2。  \n\n表3-4-2 各种车间底漆性能比较  \n\n\n<html><body><table><tr><td rowspan=\"2\">性能</td><td rowspan=\"2\">PVB车间底漆</td><td rowspan=\"2\">环氧无锌底漆</td><td rowspan=\"2\">环氧富锌底漆</td><td colspan=\"3\">无机锌底漆</td></tr><tr><td>高锌</td><td>中锌</td><td>低锌</td></tr><tr><td>主要成分</td><td>PVB</td><td>环氧树脂十 氧化铁红</td><td>环氧树脂十 锌粉</td><td>硅酸乙酯十 锌粉</td><td>硅酸乙酯十 锌粉</td><td>硅酸乙酯十 锌粉</td></tr><tr><td>典型干膜厚/μm</td><td>20~30</td><td>20~30</td><td>20~25</td><td>15~20</td><td>15~20</td><td>15~20</td></tr><tr><td>干燥时间</td><td>一般</td><td>一般</td><td>一般</td><td>快</td><td>快</td><td>快</td></tr><tr><td>防锈蚀期/月</td><td>3~4</td><td>3~5</td><td>6~9</td><td>9~12</td><td>6~9</td><td>3~6</td></tr><tr><td>耐化学品</td><td>差</td><td>很好</td><td>好</td><td>优异</td><td>很好</td><td>很好</td></tr><tr><td>耐热破坏</td><td>差</td><td>一般</td><td>一般</td><td>好</td><td>很好</td><td>优昇</td></tr><tr><td>耐溶剂性</td><td>一般</td><td>好</td><td>好</td><td>优异</td><td>优异</td><td>优异</td></tr><tr><td>耐电位性</td><td>差</td><td>好</td><td>优异</td><td>优异</td><td>优异</td><td>优异</td></tr><tr><td>焊接性能</td><td>一般</td><td>一般</td><td>一般</td><td>一般</td><td>很好</td><td>优异</td></tr><tr><td>切割性能</td><td>很好</td><td>好</td><td>一般</td><td>好</td><td>很好</td><td>很好</td></tr><tr><td>安全与健康</td><td>很好</td><td>很好</td><td>很差</td><td>一般</td><td>很好</td><td>很好</td></tr></table></body></html>  \n\n除了上述四种车间底漆以外，20世纪80年代末至90年代初，国外推出了新一代耐高温的无机锌车间底漆。这种新型的无机锌底漆在原有的无机锌车间底漆的基础上，采用超耐热树脂对硅酸乙酯进行改性，采用一部分耐热防锈颜料与锌粉共用，旨在降低车间底漆中锌粉含量和提高其耐热性。  \n\n耐高温无机锌车间底漆比传统型无机锌车间底漆耐热性能大大提高，从将能耐 $400^{\\circ}C$ 的高温提高到能耐 $800^{\\circ}C$ 的高温，这样在电焊和火工校正部位涂层烧损的面积将大大减少。另外含锌量降低不仅降低了热加工区氧化锌烟尘产生的量，对工人健康有利，同时也降低了经过一段时间室外暴露后车间底漆表面白色锌盐的发生量。烧损面的减小和锌盐的减少则可大大降低二次除锈的工作量。这对于劳动力缺乏和劳动力价格昂贵的某些造船国家来说具有积极的意义。目前这种耐高温无机锌车间底漆虽然其价格比传统型无机锌车间底漆高约 $30\\%$ 中但在某些国家（如日本、韩国）已在逐步扩大应用。  \n\n为了提高安全、环保及生产效率，水溶性无机硅酸锌车间底漆已在一些国家开始使用。水溶性无机硅酸锌车间底漆通常是指基于碱性硅酸钠、硅酸钾或硅酸锂为基料的车间底漆。其 $\\mathbf{pH}$ 通常为 $_{11\\sim12}$ ，这样高的 $\\mathbf{pH}$ 对涂料施工是一个挑战。降低 $\\mathbf{pH}$ 通常有以下方法：  \n\n$\\textcircled{1}$ 增加锌粉含量；$\\textcircled{2}$ 调整碱性硅酸盐的含量，如加入硅胶体等［保持一定的金属氧化物 $\\mathrm{MeO_{2}}$ 与 $\\mathrm{SiO_{2}}$ 的  \n\n摩尔比， $(1:2){\\sim}(1:8.5)]$ ！  \n\n但由于受到成本和现有流水线设计的限制，水溶性无机硅酸锌车间底漆还未得到广泛的应用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 244,
+        "chunk": "# 4.常用车间底漆  \n\n多年来，整个工业界都在尽力提高生产效率和建造质量—缩短造船/建筑周期及更高效率的切割和焊接。此外，目前的物流技术可以做到JIT式的生产，从而消除了对大量钢材库存的要求。而且，现代的车间底漆必须满足目前已提高的对健康和环保的要求，特别是在切割和焊接操作时候的要求。这些改变的生产方式和物流方式，以及对健康方面提高了的注意力，人们已经倾向于使用可以低漆膜厚度涂装、锌含量减少的无机硅酸锌车间底漆。  \n\n(1）第二代无机硅酸锌底漆第二代无机硅酸锌底漆中的锌含量占干膜质量的$40\\%\\sim50\\%$ 。填料替代锌粉而用来提高焊接的速率和质量。减少的锌含量仍然提供可以接受的腐蚀保护。在切割和焊接时产生的氧化锌烟雾也减少了，从而，减少了产生“锌热”的危险。  \n\n(2）第三代无机硅酸锌底漆第三代无机硅酸锌底漆中的锌含量占干膜质量的 $20\\%\\sim$ $30\\%$ 。低锌含量的无机硅酸盐车间底漆是车间底漆技术的最新产品，它可以提供极高的焊接速率和适合的切割速率。  \n\n第三代无机硅酸锌底漆的耐磨性和干燥性能同高锌含量的无机硅酸锌涂料一样。尽管具有低锌含量，第三代无机硅酸锌底漆的防腐性能依然良好。由于无机硅酸锌涂料的无机性质，它使钢材有极高的焊接速率，焊接的烧焦宽度很小，反面烧焦的情况也减少了。所有这些优点，使低锌车间底漆成为欧洲和远东地区所有主要船厂首选的车间底漆。  \n\n硅酸乙酯的反应机理是反复的水解最后固化，而反复水解的树脂又和锌离子反应生成聚合硅酸锌和乙醇，乙醇快速挥发，因而硅酸乙酯是高挥发有机物的涂料，最后形成只含有无机物的矩阵形式，如图3-4-2所示。  \n\n![](images/6f2347f0df9ac6782a35537d5f46b80438d2b7018b20c5bef3ded87ba2082915.jpg)  \n图3-4-2 有机物的矩阵形式  \n\n事实上，富锌体系是牺牲锌粉控制电子转移的一种涂料，锌粉的作用是提供阳极，钢板是作为阴极而被保护。在合适的电解液中，电子从锌粉转移到了钢板而被保护，锌粉作为阳极而被氧化。从微观上来讲，所有的电化学反应是铁和铁之间，铁和锌之间不同电势，但是由于铁和锌之间的电势要远高于铁和铁之间的电势，因而锌作为阳极有保护作用。这个涉及的复锌力学性能的原理和电镀是相同的。一旦锌粉与空气中的 $\\mathrm{CO_{2}}$ ， $\\mathrm{{\\bfS}O_{2}}$ 或盐分中的氯离子接触生成锌的各种盐类，均为难溶的碱式盐，会填充涂层中的空隙，而保护下层的锌粉粒子难以进一步作用，进而保护钢材表面。  \n\n![](images/e9e3e4c0f4c092f80a321358f871a7c50ca8c4c5ca2d0d8ca66e41b77228b84c.jpg)  \n图3-4-3带强负电的锌粉漆在活跃钢板表面的短回路  \n\n如图3-4-3所示是带强负电的锌粉漆在活跃钢板表面的短回路，钢板整个变成阴极而锌作为阳极，在恶劣的环境中锌被腐蚀，但是钢板没有，这种锌粉漆在钢板表面是强制的电路，因此，钢铁必须进行很好的表面处理。  \n\n通常正硅酸乙酯锌粉漆一般为双组分涂料，硅酸酯组分为主要成膜物。正硅酸乙酯活性较小，作为基料必须进一步水解。正硅酸乙酯水解可以酸或碱作为催化剂，以酸为催化剂反应比较慢，容易控制，同时还可以稳定活性大的硅烷醇基团，从而提高贮存稳定性。  \n\n![](images/84aca09667481abcc97e2255730834f5d40dbe03065a75b4568b4990de22f2b1.jpg)  \n图3-4-4使用水和硅酸乙酯量得出的水解程度  \n\n一般来说硅酸已酯的稳定性与活性要两者兼顾。反应终点一般用碱液进行测定。方式是在有刻度的试管中加入主剂，然后再加入碱性溶液，将试管正反摇动，测试其胶化时间。水解程度可以参照图3-4-4。  \n\n硅酸乙酯锌粉底漆的典型配方见表3-4-3。  \n\n表3-4-3硅酸乙酯锌粉底漆的典型配方  \n\n\n<html><body><table><tr><td>A组分</td><td>质量分数/%</td><td>B组分</td><td>质量分数/%</td></tr><tr><td>二甲苯 醇类溶剂 增稠剂 锌粉 分散剂</td><td>10~12 18~20 0.2~0.4 45~50 0.3~0.5</td><td>硅酸乙酯40 醇类溶剂 混合酸 水</td><td>30~35 60~65 0.4~0.6 2~3</td></tr><tr><td>其他填料 合计</td><td>16~18 100.0</td><td></td><td>100.0</td></tr></table></body></html>  \n\n配比为A：B=2：1，B组分生产的时候，注意要控制胶化时间。正常工艺是：将40%的正硅酸乙酯、醇放入罐内，搅拌均匀，然后慢慢滴加入酸化水，此反应是放热反应，一般控制在 $0.5\\sim1\\mathrm{h}$ 内滴加完成，然后放置过夜，测试水解程度用碱性溶液，如时间超过控制范围，可以追加补人酸化水，然后再放置 $4\\sim8\\ensuremath{\\mathrm{h}}$ 进行测试。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 245,
+        "chunk": "# 5.检验和质量控制  \n\n为了得到理想的结果，严格地遵循车间底漆的涂装工艺是非常重要的。关键的因素如下： $\\textcircled{1}$ 检查冲砂或喷射介质的污染状况； $\\textcircled{2}$ 测试含尘量； $\\textcircled{3}$ 检测喷钢板上污染程度（盐、油和脂）； $\\textcircled{4}$ 在喷射清理以前用水和清洁剂除去污染物； $\\textcircled{5}$ 控制喷射的标准（ $\\mathrm{\\bf{Sa2.5})}$ ； $\\textcircled{6}$ 检查钢板温度和空气温度； $\\textcircled{7}$ 检测漆膜厚度； $\\textcircled{8}$ 测试硅酸锌的固化程度。  \n\n车间底漆施工过程中常见问题及解决方法见表 $3-4=4$ 心  \n\n表3-4-4 车间底漆施工过程中常见问题及解决方法  \n\n\n<html><body><table><tr><td>观察的问题</td><td>可能的原因</td><td>解决方法</td></tr><tr><td>枪嘴堵塞</td><td>锌粉/填料堵塞枪嘴</td><td>用过滤筛网过滤 施工中保持搅拌</td></tr><tr><td>漆膜偏薄</td><td>覆盖不够</td><td>增加泵压 使用大号枪嘴 降低钢板行进速率</td></tr><tr><td>漆膜偏厚</td><td>覆盖太多</td><td>降低泵压 使用小号枪嘴 增加钢板行进速率</td></tr><tr><td>不规则的喷幅</td><td>枪嘴堵塞 枪嘴破损 泵压太低</td><td>用稀释剂和软刷清洗 更换枪嘴 增加泵压</td></tr><tr><td>喷幅边缘散射</td><td>泵压太大</td><td>调低泵压</td></tr><tr><td>喷幅边缘卷曲</td><td>泵压太低 喷枪距离太远</td><td>调高泵压 减少喷枪距离</td></tr><tr><td>干喷</td><td>钢板温度和空气温度太高</td><td>减少预加热 用慢挥发稀释剂</td></tr><tr><td>漆膜滑辊破损</td><td>漆膜干燥慢</td><td>提高预加热</td></tr><tr><td>过早锈蚀</td><td>干膜厚度偏低 不均匀覆盖 干喷 漆膜滑辊破损</td><td>见上解决方法</td></tr></table></body></html>  \n\n如今，喷涂的车间底漆的漆膜厚度非常低，甚至低到 $12\\sim15\\mu\\mathrm{m}$ 。因此，保养好设备和正确地调整喷嘴以均匀地喷涂整个表面是非常重要的。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 246,
+        "chunk": "# 6.健康和环保  \n\n涂料产品是由许多化学物质组成的。这表明在涂装时它能带来一定的健康危害。使用车间底漆造成的人体危害主要可分为如下： $\\textcircled{1}$ 混合和施工时的溶剂接触； $\\textcircled{2}$ 切割和焊接时的烟雾接触。  \n\n当混合施工时，必须遵守以下的安全警告。  \n\n$\\textcircled{1}$ 车间底漆必须在封闭的系统里进行施工和干燥以保持厂区内有低的溶剂含量。$\\textcircled{2}$ 溶剂会溶解皮肤中的脂肪而使皮肤变得干燥，这会导致皮肤开裂并感染。因此，必须使用丁睛橡胶手套以保护皮肤。  \n\n$\\textcircled{3}$ 不要用溶剂或稀释剂清洗手和皮肤。  \n$\\textcircled{4}$ 混合和施工时要戴好防护眼镜以防止液体飞溅。  \n$\\textcircled{5}$ 避免在高浓度溶剂的空气中长时间的呼吸。  \n③在超过溶剂暴露极限的环境里，操作者必须佩戴正确的、被鉴定的呼吸器。  \n?参考涂料供应商对每一个产品包装上的标签的备注和相关的安全技术指数。  \n\n当钢板和型材用来加工时，要进行切割和焊接。危害健康的烟雾在生产期间将会产生。因此，所有的车间底漆要在认可的机构进行测试，评估焊接和切割时的健康危害。表3-4-5是两种常见车间底漆的测试结果。  \n\n表3-4-5 气体污染物在呼吸区域的含量  \n\n\n<html><body><table><tr><td rowspan=\"2\">物质</td><td rowspan=\"2\">OEL</td><td colspan=\"2\">高锌含量车间底漆</td><td colspan=\"2\">中锌含量车间底漆</td></tr><tr><td>火焰切割</td><td>电焊</td><td>火焰切割</td><td>电焊</td></tr><tr><td>氧化锌/（mg/m²）</td><td>5.0</td><td>4.04</td><td>3.84</td><td>0.86</td><td>1.02</td></tr><tr><td>丙烯醛/（mg/m）</td><td>0.25</td><td>0.04</td><td>0.06</td><td>0.02</td><td>0.05</td></tr><tr><td>一氧化碳/（mg/m²）</td><td>50</td><td>ND</td><td>4</td><td>ND</td><td>ND</td></tr><tr><td>一氧化氮/（mg/m3）</td><td>25</td><td>1.3</td><td>ND</td><td>1.0</td><td>ND</td></tr><tr><td>二氧化氮/（mg/m）</td><td>3</td><td>ND</td><td>ND</td><td>0.1</td><td>ND</td></tr></table></body></html>\n\n注：OEL为职业暴露极限；ND为未检测出。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 247,
+        "chunk": "# 三、船底防锈漆",
+        "category": " Introduction"
+    },
+    {
+        "id": 248,
+        "chunk": "# 1.概述  \n\n船底防锈漆是指涂装在船体水下部位外表面，对船体金属基体材料起防腐蚀功能的涂料。该部位长期浸于严重腐蚀环境的海水之中，因此采用船底防锈漆是防止船底钢板腐蚀的最经济合理和最有效的方法。船舶在建造完成投人航运后，与船舶其他部位不一样，不论是处于航行还是处于港口码头停泊时，都不可能对船底的涂料体系进行维修保养工作，因此要求船底防锈漆具有一定的使用寿命。一般以进坞维修的时间间隔为设计使用寿命。由于在实际使用中，船底防锈漆并不是直接与海水接触，而是在船底防锈漆的外面还要涂装船底防污漆，因此要求船底防锈漆与船底防污漆配套使用。为了使得船底防锈漆与船底防污漆结合良好，有时需要在它们之间采用一道连接漆，这里也将连接漆包括在船底防锈漆体系中。  \n\n目前绝大多数钢质船舶都采用阴极保护措施（外加电流系统或者牺牲阳极系统)，因此要求船底防锈漆与阴极保护系统相适配，也就是在应用中要求能耐一定的阴极保护电位。",
+        "category": " Introduction"
+    },
+    {
+        "id": 249,
+        "chunk": "# 2.船底防锈漆的种类  \n\n船底防锈漆可分为沥青系、油改性系等低档的船底防锈漆；环氧沥青系、氯化橡胶系和氯化橡胶沥青系、乙烯系和乙烯沥青系的中档船底防锈漆；以及环氧系的高档船底防锈漆。早期的船底防锈漆中多含有沥青类树脂，如煤焦沥青，并与其他树脂，主要是环氧树脂、乙烯树脂和氯化橡胶树脂配制为环氧沥青涂料、乙烯沥青涂料和氯化橡胶沥青涂料等，由于煤焦沥青本身渗水性很小，具有优良的耐水性能，是一种价廉物美的涂料成膜物质，加上环氧树脂或其他树脂的优异的粘接性能，使得环氧沥青涂料和其他树脂的沥青涂料成为一类防腐蚀性能优异、价格低廉、涂装方便的船底防锈漆品种。单一的沥青系船底防锈漆，采用软化点为 $40\\sim60^{\\circ}C$ 的煤焦沥青，与防锈颜料配合而成，涂装时对钢板表面的处理要求较低，一般应用在小吨位、低要求的船舶船底部位。由于煤焦沥青防锈漆的耐阴极保护电位低（ $\\mathrm{.-0.8\\mathrm{\\sim}\\mathrm{-0.85V)}}$ ，很容易在有装置阴极保护设备的船舶上应用时，造成沥青系船底防锈漆漆膜的起泡和剥落。另一个主要原因是由于沥青树脂本身的对涂装施工人员和其他相关人员的健康影响，含沥青的船底防锈漆的应用也逐渐减少，几乎已不在中大型船舶上使用。  \n\n氯化橡胶系和乙烯系船底防锈漆都是单组分，依靠涂料中溶剂挥发而成膜的船底防锈漆，也包括它们与煤焦沥青混合改性的品种，如氯化橡胶沥青防锈漆和乙烯沥青防锈漆。  \n\n在20世纪 $60\\sim90$ 年代，氯化橡胶系和乙烯系涂料在制造和使用上得到了迅速发展，已成为当时船底防锈漆的主要品种。由于它们都是单组分涂料，涂装方便、涂膜十燥迅速，较少受到环境气候的影响，尤其是低温的影响。特别是在厚膜型氯化橡胶涂料开发成功和高压无气喷涂技术应用受到船厂的欢迎，使得氯化橡胶船舶漆在造船工业上应用有了突飞猛进的发展。  \n\n氯化橡胶是将天然橡胶溶解于四氯化碳中，通入氯气反应而成。反应后可获得含氯量为$62\\%\\sim67\\%$ 的氯化橡胶树脂白色粉末产品。一般氯化橡胶按其溶液黏度的大小分成若干规格，如国产的产品有黏度值 $\\mathrm{5\\sim10mPa\\cdot\\s.}$ ， $11{\\sim}20\\mathrm{mPa}\\cdot\\mathrm{~s~}$ 1 $21{\\sim}40\\mathrm{mPa}\\cdot\\mathrm{~s~}$ 和 $40\\mathrm{{mPa}\\cdot\\ e}$ 以上。通常用于涂料的是前两种。  \n\n由于氯化橡胶树脂中不含酯键，分子结构饱和，配制的涂膜透水率低、耐化学品腐蚀性好，尤其是耐海水性优良，从60年代起，作为重防腐蚀涂料广泛应用于造船、港湾钢结构工程中。  \n\n氯化橡胶系防锈漆是由氯化橡胶树脂、增塑剂、防锈颜料、体质填料、触变剂、其他助剂以及溶剂组成。单一氯化橡胶分子中含有许多六元环，因此其涂膜硬脆，必须配加增塑剂进行改性，涂料中最常用的是氯化石蜡，还有邻苯二甲酸酯类、磷酸二苯酯及干性油等。除以氯化橡胶作为主要成膜物质外，还可与其他树脂混合改性，如醇酸树脂、聚氨酯树脂、环氧树脂、酚醛树脂、丙烯酸树脂、煤焦油沥青等。通常氯化橡胶树脂与氯化石蜡的配合比在$70:30$ 时，漆膜的坚韧性和附着力综合性能最好。  \n\n氯化橡胶本身无毒、无臭，对环境无害，但在氯化橡胶树脂的生产工艺中，因溶解橡胶的四氯化碳会在成品中有 $3\\%\\sim8\\%$ 的残留，进而发挥到大气中，会对人体造成毒害和破坏大气的臭氧层。为了保护地球的臭氧层，1995年在联合国主持下通过了蒙特利尔公约(Montreal)，公约规定了禁止和限制使用破坏地球臭氧层的四氯化碳、氟里昂等化学物质。我国是该公约的签字国，从2005年起，国家环保总局规定了在氯化橡胶生产过程中限制和停止使用四氯化碳，到2010年完全停止使用四氯化碳。一些大的氯化橡胶生产厂已停产或减产，使得氯化橡胶树脂产品数量减少。目前氯化橡胶船底防锈漆的应用也在减少。一些厂家正在改进生产工艺，有的减少氯化橡胶树脂产品中四氯化碳的含量，有的采用新的含氯聚合物树脂替代氯化橡胶，还有的采用一种新型封闭循环设备生产，该生产工艺已符合Mont-real协议的要求。我国从80年代就开始了水相法制造氯化橡胶的探索和研究工作。经过氯化橡胶生产厂家与船舶漆生产厂家合作应用开发研究，目前水相法制备的氯化橡胶铝粉防锈漆在防锈漆的基本物理性能和防锈性能方面已可满足船舶漆生产厂的产品的技术要求，与国产和进口的四氯化碳溶剂法制备的氯化橡胶性能相同。  \n\n目前氯化橡胶船底防锈漆与乙烯防锈漆作为环氧类的船底防锈漆和船底防污漆的连接漆在普遍使用，漆膜厚度在 $30\\mu\\mathrm{m}$ 左右。  \n\n为了替代环氧沥青船底防锈漆中的沥青成分，一类改性环氧防锈漆成为新一代的替代品种。改性环氧船底防锈漆（或称为漂白焦油环氧涂料）是应用如古马隆树脂与环氧树脂混合的品种。由于防锈性能与环氧煤沥青船底防锈漆相同，不含煤焦沥青，因此无沥青的毒性问题。  \n\n自60年代起，几十万吨的超级油轮、海上石油钻采平台和大型港工钢结构设施的大量出现，需要长效、高性能的防锈漆进行防腐蚀保护，环氧沥青漆和纯环氧防锈漆相继问世。环氧沥青系防锈漆兼备了环氧树脂的优秀的粘接能力和煤焦沥青树脂的防水性能，成为一类应用最为广泛的船底防锈漆和船舶压载水舱的防锈漆。  \n\n环氧沥青系防锈漆漆膜坚韧，与钢板的附着力优良，漆膜耐阴极保护电位可达一1.1V。漆膜耐盐水浸泡性和热盐水浸泡性能优良。而且对钢板表面处理的要求不是很司刻，在船舶、海洋工程、管道工程中的水下和地下的钢结构防腐涂料应用厂泛。  \n\n由于环氧沥青涂料中的煤焦沥青含有较强的致癌物质，且由于涂层本身颜色为深黑，在封闭环境中涂装施工时不易检查涂层的涂装质量，它们已在船舶压载水舱应用中受到限制。同样由于从安全和环境保护要求考虑，环氧煤焦沥青船底防锈漆在大型船舶上的使用也在减少，逐渐为不含煤焦沥青的环氧系船底防锈漆所替代。  \n\n为了进一步提高船底防锈漆的使用寿命，减少船舶防锈漆的品种，方便造船厂的涂装施工管理，一类称为“通用型环氧防锈漆”的品种正在逐步扩大应用。这是一类纯环氧类的船舶防锈漆，它们既可以作为船底防锈漆应用，又可以作为船舶内舱和船体上层建筑等部位的防锈漆使用，这类环氧型的防锈漆为双组分涂料，固体分高，一道涂膜厚（通常在 $125\\upmu\\mathrm{m}$ 以上)，附着力高（一般高于 $\\mathbf{3.0MPa}^{\\cdot}$ )，耐干湿交替，耐阴极保护电位性能好。已成为船底防锈漆的主流产品。  \n\n环氧系船底防锈漆是当今造船业最常用的一类船底防锈漆，为双组分涂料，固体分高，涂膜厚；附着性好；耐化学药品腐蚀；而且涂膜耐阴极保护性能好。各种环氧系船底防锈漆的组成及特点见表3-4-6。  \n\n表3-4-6 环氧系船底防锈漆  \n\n\n<html><body><table><tr><td rowspan=\"2\">品种名称</td><td colspan=\"3\">组成</td><td rowspan=\"2\">特点</td></tr><tr><td>主要成膜物质</td><td>防锈颜料</td><td>固化剂</td></tr><tr><td>环氧沥青船底防 锈漆</td><td>环氧树脂十煤焦 沥青</td><td>铝粉、云母粉等</td><td>物等</td><td>附着性好，耐水性好，可制成厚浆型 聚酰胺，胺加成涂料，一次可得200um以上的干膜 厚，可与各类车间底漆相容，价格低。 煤焦沥青含有致癌物质</td></tr><tr><td>改性环氧船底防 锈漆</td><td>环氧树脂十碳氢 石油树脂</td><td>铝粉、云母粉等</td><td>聚酰胺、腰果油改 物等</td><td>性能与环氧沥青防锈漆相似，表面 性酚醛胺、胺加成容忍性好，不使用煤焦沥青，不存在毒 性问题</td></tr><tr><td>纯环氧船底防 锈漆</td><td>半固体、液态环氧 树脂</td><td>铝粉、云母粉等</td><td>聚酰胺、腰果油改 物等</td><td>附着性好，耐碱，耐干湿交替，与各 性酚醛胺、胺加成类车间底漆配套，可制成厚浆漆料，耐 阴极保护电位性能好，漆膜柔性好</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 250,
+        "chunk": "# 3.最新的船底防锈漆国家标准的主要技术内容  \n\n为了提高我国船舶船底防锈漆和防污漆的技术水平，与国际同类产品相适应，2006年已将原国家标准GB/T13351—1992《船底防锈漆通用技术条件》和GB/T6822—1986《船底防污漆通用技术条件》合并成为一个新国家标准，标准名称为《船体防污防锈漆体系》，标准中船底防锈漆部分的主要内容如下。  \n\n（1）防锈漆体系组成和分类说明  \n\n$\\textcircled{1}$ 组成船体防锈漆体系可以是多道的单一防锈漆产品，也可以是由防锈底漆和防锈面漆组成的体系。$\\textcircled{2}$ 分类说明a．型别按照防锈漆的成膜机理，防锈漆可分成下面两种型别。  \n\n·I型船底防锈漆由两种组分构成，在涂装施工前按照规定比例，均匀混合两种组分，经过一定时间的预反应后即可进行涂装施工，通过两种组分反应固化而于燥成膜。  \n\n·Ⅱ型船底防锈漆为单组分，涂装施工后，通过漆膜内的溶剂挥发而干燥成膜。  \n\nb.类别（仅适用于I型）按照防锈漆成膜时对固化温度的要求不同，分成两类。  \n\n$\\cdot1$ 类通常在 $10^{\\circ}C$ 和 $10^{\\circ}C$ 以上固化成膜的I型防锈漆。  \n$\\bullet2$ 类通常在 $10C$ 以下固化成膜的I型防锈漆。  \n\nc.有效使用期 完整的船体防锈漆体系的有效使用期分成三种级别。  \n\n$\\cdot$ 一级防锈有效期 防锈有效期在五年和五年以上的防锈漆体系。  \n$\\cdot$ 二级防锈有效期 防锈有效期在三年和三年以上，五年以下的防锈漆体系。  \n$\\cdot$ 三级防锈有效期 防锈有效期在三年以下的防锈漆体系。  \n\n(2）技术要求  \n\n$\\textcircled{1}$ 船底防锈漆体系的一般要求  \n\na.安全说明书作为船底防锈漆的产品，应符合相关材料的安全说明书（MSDS）的要求。  \n\nb.船底防锈漆的技术性能标准规定的船底防锈漆产品应均匀一致，配套应用，并能与车间底漆互相配套。涂料的技术性能应符合表3-4-7的规定。涂料制造方按表3-4-7的规定提供涂料技术性能要求。  \n\n表3-4-7 船底防锈漆的技术性能  \n\n\n<html><body><table><tr><td>序号</td><td>检测项目</td><td>防锈漆</td><td>序号</td><td colspan=\"2\">检测项目</td><td>防锈漆</td></tr><tr><td>1</td><td>不挥发分</td><td>①</td><td>5</td><td>干燥时间/h</td><td>表干</td><td>①</td></tr><tr><td>2</td><td>密度</td><td>##</td><td></td><td></td><td>实干</td><td>≤24</td></tr><tr><td>3</td><td>黏度</td><td>①</td><td>6</td><td colspan=\"2\">适用期</td><td>##</td></tr><tr><td>4</td><td>闪点</td><td>①</td><td rowspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\"></td></tr><tr><td></td><td rowspan=\"2\"></td><td rowspan=\"2\"></td></tr><tr><td></td><td colspan=\"2\"></td><td></td><td></td></tr></table></body></html>\n\n$\\textcircled{1}$ 按产品的技术要求。$\\textcircled{2}$ 适用期针对适用于多组分的船底防锈漆I型。  \n\nc.毒性涂料产品不含有石棉或含有石棉的颜料以及国家有关部门禁用的化学物质。  \n\nd.在容器中状态在用机械混合器搅拌 $5\\mathrm{min}$ 之内，涂料应该很容易地混合成均匀的状态。涂料应无坚硬的沉底、结皮、起颗粒或其他不适合使用的现象。  \n\ne.贮存稳定性·原封、未开桶包装的涂料按照GB/T6753.3方法试验，在自然环境条件下贮存1年后（或按照产品技术要求)，或者在加速条件下贮存30天后，应该在5min之内很容易地混合成均匀的状态。  \n\nf.涂料的施工性船底防锈漆的施工方法应符合船舶涂料的通常涂装方法，如高压无气喷涂、空气喷涂、辊涂和刷涂。应具有良好的流动性和涂布性。湿膜不应出现流挂，干燥后的漆膜应平滑、均匀。  \n\n$\\textcircled{2}$ 船底防锈漆体系的涂层与配套的防污漆配套性能  \n\na.与配套的船底防污漆进行浅海浸泡试验后，防锈涂层应无剥落或片落。b.与配套的船底防污漆进行动态模拟试验后，防锈涂层应无剥落和片落。c.在与配套的船底防污漆进行与阴极保护相容性试验后，试验的涂料应不剥落、片落、起泡、溶解或其他损坏。$\\textcircled{3}$ 船底防锈漆体系的涂层性能a.附着力船体防锈漆体系与基体材料的附着力，是船底防锈漆最主要的力学性能，附着力的测量方法采用GB/T5210--2006中的直接拉开法。一级和二级防锈漆体系应大于3.0MPa，三级防锈漆体系应大于或等于2.0MPa（ⅡI型沥青系除外）。  \n\nb.耐浸泡性船底防锈漆体系在进行浸泡试验时，漆膜不应产生破坏、针孔锈点和起泡。试验方法和程序如下。  \n\n$\\cdot$ 试样尺寸和试样制备 $150\\mathrm{mm}\\times300\\mathrm{mm}\\times3\\mathrm{mm}$ ，表面粗糙度 $R_{\\bar{\\mathbf{a}}}$ 为 $40\\sim80\\mu\\mathrm{m}$ ，制板及试验条件按 $\\mathrm{GB/T~10834}$ 规定进行。  \n\n$\\cdot$ 试验程序及评定涂漆样板经20个周期（每周期7天）浸泡试验（或至失效前)，每周期均记录涂层情况。如果在20个周期后，涂层情况完好，则用软布和目来水轻擦表面，室温干燥 $48\\mathrm{h}$ ，经表面处理后，用涂层体系涂面漆一道（如适合，则涂底漆一道、面漆一道），重涂每块试板一侧面中心向上的 $1/3$ ，并封边 $13\\mathrm{mm}$ 。状态处理7天，然后增加5个周期全浸试验。在重涂侧面上，后加涂层的附着力判定减少至原来涂层层间附着力的一半视为失效。  \n\nc.抗起泡性（适用于I型）船底防锈漆体系的热盐水浸泡试验是一种加速腐蚀试验的方法。采用两个阶段进行热盐水的浸泡。第一个周期在 $88^{\\circ}C\\pm3^{\\circ}C$ 盐水或天然海水中浸泡14天，取出样板，洗涤、干燥，然后用金刚砂布（ $100^{\\sharp}$ ）手工轻磨每块样板其中的一面，对磨面再清洗、于燥，再涂面漆一道，干燥7天后，进行第二周期试验。样板浸人 $38^{\\circ}C\\pm2^{\\circ}C$ 盐水或天然海水中浸泡14天，取出样板，检查并记录起泡程度（边缘向内 $\\delta\\mathrm{mm}$ 不计)。要求漆膜完整，不应出现起泡。  \n\nd.耐阴极剥离试验（适用于I型）船底防锈漆体系应与船舶的阴极保护方法相适应，试验方法按照GB/T7790方法进行。试样的剥离面积应符合标准规定的要求。  \n\n为了符合实际，船底防锈漆和防污漆一同作为防污防锈漆体系应用，经受船舶阴极保护系统的影响作用，因此要求船底防锈漆与船底防污漆配套进行阴极保护相容性试验。  \n\n试验要求如下：每种防锈防污漆体系制备四块试样，试板尺寸为 $250\\mathrm{mm}\\times150\\mathrm{mm}\\times$ $2\\mathrm{mm}$ 。每块试板在涂装前用M5、长 $\\mathbf{\\l}0\\mathbf{mm}$ 的铜螺钉、铜螺母和铜垫片，把一条长度为$600\\mathrm{mm}$ 、线芯直径为 $\\mathtt{l m m}$ 的带塑料绝缘层的铜导线的一端固定在试板的连接孔上。铜导线另一端与镁阳极连接。阳极表面与试板中心位置的电阻应小于 $0.01\\Omega$ 。用环氧胶密封试板的导线连接端孔。按照防锈漆和防污漆的配套要求依次进行涂装。在涂装后的试样中心位置对涂层开一个人造漏涂孔，该孔是一个去掉全部涂层、裸露金属基体的、直径为 $\\mathsf{f m m}$ 圆孔，孔洞部位应暴露出底材金属的光泽。按照GB/T7790防锈漆耐阴极剥离性的试验方法进行阴极保护相容性试验。其中两块试样连接镁阳极，另两块试样作为对照试样，不与镁阳极连接。试验周期为30天。试验结束后，检查每块试样的人造漏涂孔周围涂层附着力降低（即涂层剥离）、剥落、起泡或其他涂层破坏的现象。  \n\n(3）船底防锈漆体系产品的检验船舶船体防污防锈漆产品检验分为型式检验和出厂检验。型式检验为周期检验，出厂检验为每批次检验。项目要求和方法见表3-4-8。  \n\n表3-4-8 船底防锈漆体系检验项目  \n\n\n<html><body><table><tr><td>序号</td><td>检验项目</td><td>出厂检验</td><td>型式检验</td><td>序号</td><td>检验项目</td><td>出厂检验</td><td>型式检验</td></tr><tr><td>１</td><td>不挥发分</td><td>X</td><td>V</td><td>7</td><td>耐浸泡性</td><td>X</td><td></td></tr><tr><td>2</td><td>密度</td><td></td><td></td><td>8</td><td>抗起泡性</td><td>X</td><td></td></tr><tr><td>3</td><td>黏度</td><td></td><td></td><td>9</td><td>耐阴极剥离性</td><td>X</td><td>V</td></tr><tr><td></td><td>闪点</td><td>X</td><td></td><td>10</td><td>适用期</td><td>X</td><td></td></tr><tr><td>5</td><td>干燥时间</td><td></td><td></td><td>11</td><td>贮存稳定性</td><td>X</td><td></td></tr><tr><td>6</td><td>附着力</td><td>X</td><td>√</td><td></td><td></td><td></td><td></td></tr></table></body></html>\n\n注： $u_{i}=v^{i,j}$ 为进行；“×”为不进行。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 251,
+        "chunk": "# 四、船底防污漆",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 252,
+        "chunk": "# 1.船底防污漆概述  \n\n防污涂料通常称为船底防污漆或简称防污漆，是防止海洋附着生物污损、保持船底光洁、光滑的一种专用涂料。  \n\n防污漆在使用寿限内，通过不断地释放所含防污剂，在海水与涂层的界面处形成含一定毒料浓度的微层，从而防止了污损生物幼体对船壳的附着。防污剂必须具备广谱的杀菌能力以防止种类如此繁多的污损生物附着于船壳之上。在世界各海域中有8000多种植物和59000多种海洋动物，其中有600多种附着植物和18000多种附着动物。这些附着生物的幼虫或孢子能够漂浮或游动，发育到了一定阶段后，就在船底、水下结构物或岸边岩石等物体上附着、定居并进一步繁殖。  \n\n海洋生物大量附着在船底上，对船舶将带来很大的危害，它们不仅将增加船舶的自重、减少船舶的载重，同时将大大增加船体粗糙程度。如图3-4-5所示为船舶航运燃料消耗与船体表面粗糙度的关系。  \n\n![](images/d560b75b6995581b996a5c3583bd8dde97dbd71e5781adc639fb9e3ecfcb611c.jpg)  \n图3-4-5 燃料消耗与表面粗糙度的关系  \n\n有资料表明，船底污损严重时，其海洋生物堆积层可达十多厘米厚，每平方米质量达20余千克，这对于近万平方米船底的船舶来说将增重200余吨。造成船舶的航速降低和燃油消耗的增加。船底污损达 $5\\%$ ，燃料将增耗 $10\\%$ ；船底污损达 $10\\%$ ，燃料将增耗 $20\\%$ 曲船底污损大于 $50\\%$ ，燃料将增耗 $40\\%$ 以上。  \n\n假设全球所有船只都污损达到 $50\\%$ ，按燃料增耗 $40\\%$ 计算，会发现：  \n\n$\\textcircled{1}$ 全球船舶将多燃耗70.6亿吨燃油；  \n\n$\\textcircled{2}$ 同时将额外释放2.1亿吨的 $\\mathrm{CO}_{2}$ 及560万吨的 $\\mathrm{{\\bar{S}O_{2}}}$ 0这样将给船东极大地增加运营成本，同时严重影响人们赖以生存的环境(温室效应及酸雨等)。  \n\n海洋生物如果附着于军舰底部，将影响军舰的航速，附着在声呐罩上，则干扰声呐的侦察性能，这些都将大大削弱军舰的战斗力。  \n\n可见海洋生物的污损对舰船具有巨大的危害性。防止海洋生物污损的方法有涂装防污漆防污、电解海水防污、超声波防污等方法。但到目前为止，无论从经济上还是从效果上，防污漆防污仍被认为是唯一可广泛应用的方法。  \n\n有机锡（TBT）的使用对海洋生物造成的危害引起人们的普遍不安，新的法规限制TBT及对海洋环境构成污损的毒料的使用，船舶涂料工业随之而发生着显著的变化，多年来人们致力于开发在性能方面足以与含锡涂料相媲美的新产品。同时也在很大程度下减少了对环境的危害。  \n\n防污漆的发展大体可划分为三个阶段：传统的常规防污漆；先进的有机锡共聚物自抛光防污漆；现代无锡自抛光防污漆及无毒低表面能防污漆。表3-4-9列示了防污漆发展的历史。  \n\n表3-4-9 防污漆发展历史  \n\n\n<html><body><table><tr><td>时 间</td><td>防污漆类型</td><td>基料</td><td>防污剂</td></tr><tr><td>20世纪50年代前</td><td>传统型防污漆</td><td>松香</td><td>CuzO</td></tr><tr><td>20世纪50～60年代</td><td>长效型防污漆</td><td>松香/乙烯基树脂 松香/氯化橡胶</td><td>Cuz O</td></tr><tr><td>20世纪60年代后期</td><td>长效型防污漆</td><td>松香/乙烯基树脂 松香/氯化橡胶</td><td>CuzO/TBTO</td></tr><tr><td>20世纪70年代中期</td><td>自抛光防污漆</td><td>TBT-共聚物（低膜）</td><td>CuO/TBTO</td></tr><tr><td>20世纪80年代早期</td><td>自抛光防污漆</td><td>TBT-共聚物（高膜)</td><td>CuzO/TBTO</td></tr><tr><td>20世纪80年代中期</td><td>自抛光防污漆</td><td>TBT-共聚物（低锡）</td><td>CuzO/TBTO</td></tr><tr><td>20世纪80年代后期</td><td>扩散型防污漆</td><td>共聚物</td><td>CuzO/TBTO，其他防污剂</td></tr><tr><td>20世纪90年代早期</td><td>无锡自抛光防污漆</td><td>共聚物</td><td>CuzO/有机防污剂</td></tr><tr><td>20世纪90年代后期</td><td>低表面能</td><td>有机硅</td><td>不含防污剂</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 253,
+        "chunk": "# 2.污损生物种类  \n\n污损通常用来描述在海洋作业的建造设施上所生成的海洋植物以及海洋动物。浸在海水中的物体表面都会受到海洋生物体的污损。这些海洋生物体附着在船舶表面并且不断增长，将导致其表面粗糙程度的显著增加，那么当船舶航行时，由于航行阻力的增大，导致耗油量的增加。这样，为了降低船舶耗油量，防止海洋生物生长，就变得较为重要了。  \n\n据估计，大约有4500种海洋生物会侵蚀海洋设施。根据这些生物体生长成熟后的大小，可以分成两类。  \n\n$\\textcircled{1}$ 大型污损物，包括植物和动物。  \n\n$\\textcircled{2}$ 微型污损物，它一般指动物分泌的黏液以及微小的海洋生物体等。  \n\n在这些物种中，有一些依靠自身游动或者被水流带动而随波逐流；而其他很多物种，则必须依附于坚硬的物体表面，以便繁衍生息。许多生物体移动缓慢，大多数静止型生物体会在季节性产卵期产出数量巨大的精子及卵子。精、卵在水中结合成为受精卵，因此精子的巨大数量使卵子受精的概率大大增加了。在多数情况下，这些受精卵将发育成为幼虫。海洋植物并不会产生类似的幼虫，而会产生漂浮或是自行游动的类似于种子的“孢子”。  \n\n污损有多种类型，它们的生物性特征也有所不同。污损的过程是复杂的，它取决于地理、气候、季节和物理因素。在船底常见的附着生物有藤壶、牡蛎、贻贝、树枝虫、海鞘、绿藻、碣藻、浒苔、花筒等数十种。其中藤壶、牡蛎、贻贝等在船底附着之后，生长迅速。在生长过程中将产生一种张力，能剪开和破坏漆膜。同时这些生物还会分泌出有机酸，这些将大大加速船底钢板的腐蚀。  \n\n有机生物体的类型及繁殖密度随着海水的温度、盐度以及光照强度的不同而有所不同。如果把时间和地理因素纳人考虑范围，那么我们把海洋划分成许多区域。在南、北半球的极带地区，盛夏前后的光及温度都很适合污损有机生物体的生长与繁衍。  \n\n在南、北半球的温带地区，污损有机生物体的生长适宜期从春天开始到早秋结束。而对于亚热带和热带地区，它们的生长适宜期可贯穿全年。并且某些种类的生物体在某些特定的  \n\n时间会更具生命活力。  \n\n在某些特定的地区，上升洋流和离岸风会带动某些矿物质营养进人上层洋面，而那里是多数海洋生物的聚居场所。洋流能够改变一个地区。在毗邻大陆的浅水区域，污损生物体大量生长，它们的生长速率往往都高于远离陆地的公海。因为在公海上，阳光只能照到海水中  \n\n![](images/28c60e301b7ed8b5d0e41585eb2c6b3f3fe74aee0af82cec9f026918df0ce0b9.jpg)  \n图3-4-6 相似膜孔苔虫（polyzoa）在青岛海域附着情况  \n\n的某一深度，而不能照到海底。综上所述，相对于公海，沿海岸的海水更容易受到污损的威胁。  \n\n我国海岸线长达18000多千米，各海区海生物的繁殖时间、品种、数量等均有不同。如图3-4-6所示为相似膜孔苔虫在青岛海域附着情况。  \n\n据不完全统计，我国海洋生物的种类有千余种，其中软体动物类800余种；植物藻类200余种。绝大部分生长在海岸及港湾处，生物的幼虫或孢子漂浮、游动发育到一定阶  \n\n段后，就在物体上附着定居下来，在 $4\\sim10$ 月份附着、繁殖速率最快。附着生物主要有两大类：藻类，如菊花藻、绿藻、褐藻等；软体动物类，如牡蛎、贻贝、海鞘、藤壶、苔藓虫、石灰虫等。藻类的生长主要依靠光合作用、海水中的无机盐及微生物；软体动物的生长主要依靠水体中的有机质、微生物及水体中的溶解氧。不同海区水质状况的区别导致了生物生长的差异。  \n\n船底常见海洋附着生物如图3-4-7所示。  \n\n![](images/e1feb86f51ede500a767c392043d663dd05dcbb77ff46be5a99849721d372a16.jpg)  \n(a）藤壶（acorn barnacle)  \n\n藤壶特别适合于在浮动的物体上过着浮游生活，藤壶不但能附着在礁石上，而且能附着在船体上，任凭风吹浪打也冲刷不掉。有些藤壶即使在船速10节时也能在船壳实施附着。藤壶在每一次脱皮之后，就要分泌出一种黏性的藤壶初生胶，这种胶含有多种生化成分和极强的黏合力，从而保证了它极强的吸附能力。藤壶长有高钙质的、行动不便的外壳。水下清理或铲刮不能将它根除，残留物会促进进一步的污损。藤壶分布甚广，几乎任何海域的潮间带至潮下带浅水区，都可以发现其踪迹  \n\n![](images/11aff2283e3c82ba8570ded76b30c4fff39bd3a914a0b977b7b53df5ed20da55.jpg)  \n(b）鹅颈藤壶（gooseneck barnacle)  \n\n![](images/0695919449b1f61f050b345306ec27aa8fa9f1de4309410f2ea45958ac857079.jpg)  \n\n![](images/4217d7ca4c9f75ba63d4e3344a28c7a15fbd11e411265956bab04dc0de641289.jpg)  \n(c）始贝（mussel)  \n\n贻贝俗称海红，是用足丝固着生活的。它不但固着在岩石上，有的也固着在浮简或船底上面。我国北部沿海、浙江沿岸、福建厦门沿岸都有分布  \n\n![](images/b55db3ed62c785fa955ac1f63f75498fea3d4dd230122aefc961f7721e39b9d7.jpg)  \n(d）牡蛎（oyster)  \n\n牡蛎是营固着生活的软体动物，用壳固着在其他物体上，体外受精，幼虫浮游，固着变态成稚贝。我国南北沿海均有分布  \n\n![](images/a0d34cf5be3a94ef746bf6c819f9c6a2bffa5b3821af9c6ae3f30e2f2f2c2d83.jpg)  \n\n(e)水（hydroids/tubularia)  \n\n水熄纲动物中除水、某些简等极少数种为单体生活之外，其余绝大多数种类为群体生活。多数种在沿海生活，少数栖于淡水。外貌像植物，常被误认为是海藻，与海葵是近亲；触手用于捕捉食物。沿海常见的数枝媳（obelia）就是群体生活的代表，其群体呈树状，从几厘米到十几厘米，固着在岩石、海藻及船舶的平底上  \n\n中界中心#i  \n\nH  \n\n![](images/922d7d25cc477f4f06dc6511ac5b7df6e1be25728372cd7970de50732552f52e.jpg)  \n(g）海鞘（sea spuirt)  \n\n海鞘形状很像植物，有的像茄子，有的像花朵，有的像茶壶。广泛分布于世界各大海洋中，从潮汐到千米以下的深海都有它的足迹。它以特有的本领附着于船舰底部，数量又多，所以影响船只速度，消耗油量；还会附着堵塞水下管道，影响水流畅通，造成危害  \n\n(f）苔动物（polyzoa)  \n\n苔藓动物群体水生，多数固着在贝壳、其他动物的外骨骼、岩石、浮筏、船底等硬物上，呈被覆结壳状、块状、胶块状或灌木丛状。苔藓虫靠无性出芽生殖构成直立或被覆的群体，因此又叫群虫（polyzoa）  \n\n![](images/29a8c222847462aa208ef0bffaa83859364273f513dc2feaa481676ce0b18e97.jpg)  \n1 i.   \n（h）多毛虫/石灰虫（serpulavermicularis）在附着的多毛环虫中以石灰质栖管的龙介虫（石灰虫）和螺旋虫危害最大。龙介虫多附着于岩石、贝类、珊瑚、海藻叶片和其他硬物上，是主要附着污损生物之一  \n\n![](images/85dec6b82c3401616e469e3c7367763cc3c4f09df0f13d2c63b9ccf3b35f4d9f.jpg)  \n（i）海藻/海草（algae/seaweeds）  \n\n绝大多数植物性海生物是褐色海藻和绿色海藻。它是由微小的孢子沉积生长而成。植物性海生物生长需要阳光，通常生长在可见阳光的区域，如水线周围和以下几米。通常船底不会发生这种污损  \n\n![](images/f0fa261b98e0808bd0636ee405a524a042dd39502fee0095ac79873759f7810e.jpg)  \n（j）细菌性海生物（slime）  \n细菌性海生物，微生物黏膜（slimefilm）或初级黏膜（primaryslime）：由细菌或单细胞硅藻分泌黏液积聚而形成。具有非常低的表面粗糙度，难于控制  \n图3-4-7 船底常见海洋附着生物",
+        "category": " Introduction"
+    },
+    {
+        "id": 254,
+        "chunk": "# 3.防污漆的特性和组成  \n\n（1）防污漆的特性船底防污漆是一种防止海生物污损的特种涂料，具有一般涂料截然不同的特性与组成。防污漆的主要特性如下。  \n\n$\\textcircled{1}$ 在一定时间内能防止海洋附着生物附着的效能。  \n\n$\\textcircled{2}$ 漆膜中含有一定量的能杀伤附着海生物的防污剂，这些防污剂能连续不断地逐步向海水渗出。  \n\n$\\textcircled{3}$ 与防锈漆相反，漆膜具有一定的透水性，以保持防污剂的连续渗出。  \n\n$\\textcircled{4}$ 与防锈漆之间有良好的附着力，防污漆本身层与层之间亦应有良好的附着力，要求层间稍能互溶。  \n\n$\\textcircled{5}$ 漆膜有良好的耐海水冲击性，在长期浸水条件下不起泡、不脱落。  \n\n$\\textcircled{6}$ 经航行一定时间后，希望有不同程度的抛光性。  \n\n（2）防污漆的组成防污漆的组成与一般涂料有所不同，由防污剂、渗出助剂、基料、颜料、助剂和溶剂等组成。其中防污效果与防污剂的种类、含量、可溶性成分的用量以及基料的类型等都有很大的关系。  \n\n$\\textcircled{1}$ 防污剂防污剂必须能在海水中微溶，对海洋附着生物有杀伤力。传统的防污剂有氧化亚铜、有机锡、有机锡高聚物（毒料与基料同一体）以及氧化汞、DDT、有机铅、铜粉等。  \n\na.氧化亚铜（CuzO）是防污漆中最为重要、应用最多的防污剂，能有效杀伤海洋附着生物而对人体低毒。微溶的氧化亚铜所释放的Cu+进入海生物幼虫或孢子体内，具有凝固蛋白质的作用，从而杀伤海生物起到防污作用。氧化亚铜还是现今最为广泛使用的防污剂。尽管氧化亚铜对人体的危害不大，其LD5o属低毒化学品。但对一些种类的鱼和鲸的毒性指标大于 $24\\mathrm{h}$ 。此外，铜的化合物还可能析出并沉淀在海底泥中形成永久性污染。资料显示在苏伊士运河中 $\\mathbb{C}\\mathbb{1}^{2+}$ 的含量超过正常海水的20多倍。所以长远来看铜化合物作为防污剂也会被逐渐限制使用。  \n\nb.有机锡防污剂在20世纪50年代开始得到认知，至 $70\\sim80$ 年代间用量日益增多，并开发出有机锡和氧化亚铜的复合防污剂，大大提高防污漆性能。其中以三丁基氟化锡（TBTF)、三丁基氧化锡（TBTO）和三苯基氟化锡（TPTF）效果最好。有机锡化合物对防止海藻的污损有高效，对藤壶也有效，可称为宽谱防污剂。有机锡对海洋附着生物的杀伤力约为氧化亚铜的10倍，氧化亚铜对附着生物致死的临界渗出率为 $\\mathrm{10{\\sim}20\\mu g/(c m^{2}\\cdot\\Delta d)}$ 而有机锡的临界渗出率只需 $1{\\sim}2\\mu\\mathbf{g}/(\\mathbb{c m}^{2}\\cdot\\mathrm{d})$ 。有机锡防污漆比起氧化亚铜防污漆来说还有一突出优点，即在被污染的海水里不会发黑失效，而氧化亚铜为主的防污漆在被污染的海水里会受到 $\\mathrm{H_{2}S}$ （动植物腐败后的产物或工业污水污染结果）的作用而发黑失效，这是由于生成了不溶性的黑色硫化亚铜的结果。  \n\n$$\n\\mathrm{Cu_{2}O+H_{2}S\\longrightarrow C u_{2}S\\Psi+H_{2}O}\n$$  \n\n有机锡防污剂对海生物有危害，已被禁止使用。  \n\nc.20世纪70年代以后开发了有机锡高聚物，这是防污漆划时代的突破。有机锡高聚物是使防污剂和基料合二为一的新材料，由甲基丙烯酸、三丁基氧化锡（TBTO）及丙烯酸甲酯反应制得，它既是防污剂又是成膜物质（基料)，依靠水解释放出有机锡分子，并形成水溶性物质，其特点是防污剂释放速率均匀，防污剂的利用效率高。  \n\n同样，由于有机锡对海生物有危害，有机锡聚合物也已被禁止使用。  \n\nd.氧化汞对海洋附着生物有很强的杀伤力， $\\mathrm{Hg^{2+}}$ 与 $\\vec{\\mathrm{{Cu}^{+}}}$ 一样，进人海生物幼虫或孢子体内具有凝固蛋白质的作用。但 $\\mathrm{HgO}$ 对人体的毒性也很大，并造成环境污染，因此被禁止使用。e.DDT对杀死藤壶有特效，但对其他海洋附着生物的杀害作用却很小，因此在防污漆中作辅助毒料，以提高防污漆的防污效果。但它的加入会增加漆膜封闭性，影响 $\\mathrm{Cu^{+}}$ 的渗出率，其用量一般占配方的 $2\\%\\sim4\\%$ 。现仅在小渔船防污漆中使用。由于DDT对人体危害较大，故在防污漆制造中被淘汰。  \n\nf.有机铅毒料具有渗毒料平稳、持久及长效的特点，采用三丁基乙酸铅制造防污漆有效期可达五年之久。但有机铅对人体的毒性较大，又会污染海水，故已无实际应用。  \n\ng.防污漆中有时还使用金属铜粉、环烷酸铜、油酸铜、无水硫酸铜等作为辅助毒料，以补充和调节 $\\cos0$ 或有机锡的不足。这些化合物在防污漆也很少有应用。  \n\n由于对人体及环境的影响，很多早期使用的防污剂已被或逐渐被淘汰。化学家们正全心致力于筛选新型、对人体及环境无害或低危害的防污剂。表3-4-10为现今防污漆中常用的防污剂。  \n\n表3-4-10 现今防污漆中常用的防污剂  \n\n\n<html><body><table><tr><td>商品名</td><td>名称</td><td>大致用量/%</td><td>化学文摘号CAS.No.</td></tr><tr><td>Copper Omadine</td><td>吡啶硫酮铜(CPT)</td><td>3~5</td><td>14915-37-8</td></tr><tr><td>Zinc Omadine</td><td>吡啶硫酮锌(ZPT)</td><td>3~5</td><td>13463-41-7</td></tr><tr><td>Zineb</td><td>二硫代碳酸盐（代森锌）</td><td>4~7</td><td>12122-67-7</td></tr><tr><td>Sea Nine-211</td><td>4,5-二氯-2-辛基-3(2H)-异噻唑酮</td><td>3~10(30%溶液)</td><td>64359-815</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>商品名</td><td>名称</td><td>大致用量/%</td><td>化学文摘号CAS.No.</td></tr><tr><td>Diuron</td><td>敌草隆</td><td>5</td><td>330-54-1</td></tr><tr><td>Irgarol</td><td>均三嗪（triazines）</td><td>5</td><td></td></tr><tr><td>Copper Thiocynate</td><td>硫氰酸亚铜</td><td>15~20</td><td>1111-67-7</td></tr><tr><td>Skybio 1100</td><td>三氯苯基马来酰亚胺（TCPM）</td><td>5~20</td><td>13167-25-4</td></tr><tr><td>Cuprous Oxide</td><td>氧化亚铜</td><td>30~45</td><td>1317-39-1</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 基料防污漆的基料分为可溶性基料与不溶性基料两个部分。  \n\na.可溶性基料采用可溶性基料的目的是为了便于防污剂的渗出。可溶性基料传统上主要采用松香。松香在微碱性的海水中溶解速率较快，涂于玻璃片上的松香薄膜，在流动海水中的溶解速率为100ug/（cm²·d）以上。松香具有脆性，需与不溶性基料配合使用，既可改善漆膜的塑性，又可改变松香在海水中的溶解度，以控制防污剂渗出的速率。  \n\n有机锡高聚物既是防污漆又是可溶性基料，以有机锡高聚物制成的自抛光防污漆将在后文作专题介绍。  \n\n近年来世界各国重视开发不含有机锡的自抛光涂料采用的基料为可水解的、具有一定亲水性的丙烯酸酯聚合物。  \n\nb.不溶性基料为了改善防污漆的性能，常常需加人不溶性基料。这类基料主要有沥青、氯化橡胶、氯醋三元共聚树脂、丙烯酸树脂等。  \n\n$\\textcircled{3}$ 颜料防污漆中颜料的作用是改善漆膜的力学性能和调节防污剂的渗出率。最常用和最重要的颜料是氧化锌。氧化锌在海水中微溶，本身稍具防污性。氧化锌与氧化亚铜共用可提高漆膜力学性能，亦能提高铜离子的渗出率。其他常用颜料有铁红、滑石粉等。铁红可提高漆膜力学性能，但对铜离子的渗出率有一定的抑制作用，故用量不宜太多。滑石粉对于改善沉淀性有一定作用，它的加人使防污漆贮存一段时间后罐内的沉淀较为松软而易于揽匀。  \n\n![](images/5ebbbd44473d16c8993f88864d6771a3dd9abc1015435ff08d250ed7bc06f86d.jpg)  \n图3-4-8 含铜防污漆的作用机理  \n\n$\\textcircled{4}$ 溶剂防污漆内所用的溶剂主要取决于所用的不溶性基料的品种。常用的是 $200^{\\#}$ 煤焦溶剂、二甲苯、环已酮等。  \n\n$\\textcircled{5}$ 助剂防污漆内的助剂主要有起增厚作用的触变剂、起稳定作用的稳定剂及防沉剂等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 255,
+        "chunk": "# 4.防污漆的防污机理  \n\n防污漆的作用机理是防污漆漆膜与海水接触后，其中含有的防污剂离子或分子，如氧化亚铜防污剂中的 $\\mathrm{Cu^{+}}$ 逐步向海水溶解，在漆膜表面形成一层厚度为十几微米的有毒溶液的微薄层，微薄层内的有毒离子或分子能排斥或杀死企图停留到漆膜上的海洋附着生物的幼虫和孢子，以达到防止污损的作用，如图3-4-8所示。“微薄层”内的毒料由于水流的作用会不断流失，尤其是船在航行的时候流失更快，需要从漆膜内不断渗出新的毒料，以补充流失的毒料并保持薄层内的毒料浓度。  \n\n防污漆中防污剂向海水溶解的速率以渗出率表示，定量单位以μg/（cm²·d）表示。  \n\n防止海洋附着生物污损所要求的最低限度的渗出率为临界渗出率。各种毒料的临界渗出率各不相同，Cu+为10μg/（cm²·d)，而有机锡则为1～2μg/(cm²·d)。复合毒料中各种毒料的临界渗出率，均可因其他毒料的存在而低于各自单一渗出时的临界渗出率。防污漆的渗出率应当控制调节，如渗出率低于临界渗出率，则不足以防止海生物的附着。而渗出率高于临界渗出率太多，又会造成毒料的浪费和缩短防污漆的寿命。因此，性能好的防污漆，应该在长时间内有一平稳的、稍高于临界渗出率的渗出速率。  \n\n控制和调节防污漆的渗出率是一个复杂的问题。一般来说提高防污漆中防污剂的用量或提高可溶性基料的用量，减少不溶性基料的用量，可以提高防污漆的渗出率。反之则可降低渗出率。对于自抛光聚合物防污漆来说，控制丙烯酸类高聚物的组成或聚合度亦可控制防污漆的抛光速率，即控制防污剂的渗出率。另外，在自抛光防污漆中往往还增加其他防污剂（常见的为增加氧化亚铜）以增加毒性，降低丙烯酸高聚物的抛光率要求。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 256,
+        "chunk": "# 5.防污漆的类型  \n\n根据防污漆的防污性能、结构及防污剂渗出方式，防污漆可分为传统型防污漆、有机锡共聚物自抛光型防污漆、无锡自抛光防污漆和无防污剂（无毒）防污涂料。传统型防污漆又可分为溶解型、接触型和扩散型。防污漆也可按其作用机理分为水合型和水解型。水合型防污漆通常以物理作用机理为主，而水解型防污漆则以化学反应作用机理为主。其中溶解型、接触型、扩散型通常属于水合型防污漆，自抛光共聚物型属于水解型防污漆。  \n\n(1）传统型防污漆传统型防污漆可分为溶解型、接触型、扩散型三类。  \n\n$\\textcircled{1}$ 溶解型防污漆溶解型防污漆以松香为可溶性基料，多以氧化亚铜、氧化汞（已淘汰）、DDT（被淘汰）等为防污剂，为控制其防污剂的渗出率和改善漆膜的力学性能，还需有一部分不溶性基料，如沥青、氯化橡胶、油性基料等。  \n\n由于基料是以可溶性的松香为主，防污漆在海水中其防污剂和基料将同时逐渐溶解在漆膜表面形成防污的薄层，而漆膜则不断露出新鲜面，使原来在内部的防污剂也会慢慢成为表层毒料而向海水释放。从这一观点上看，溶解型防污漆应该有一个平稳的毒料渗出率，但事实并非如此。由于溶解型防污漆中还含有不溶性基料，当漆膜外层的可溶性基料溶解后，这些不溶性基料仍然存在，形成一层阻碍膜，通常称之为“皂化层（leachinglayer)”，这将影响内层可溶性基料的溶解速率。另外，可溶性防污漆的防污剂往往主要采用氧化亚铜， $\\operatorname{Cu}^{+}$ 在海水中会被海水中的氧气氧化成 $\\mathrm{Cu^{2+}}$ ，并进一步生成碱式碳酸铜等不溶性铜盐沉积于防污涂层表面，使渗出率降低。因此，溶解型防污漆往往是一开始有很高的渗出率，随着时间推延渗出率不断降低，当降到临界渗出率以下时，防污漆就失效。一般溶解型防污漆的防污能力在 $1{\\sim}3$ 年。  \n\n$\\textcircled{2}$ 接触型防污漆接触型防污漆的基料为不溶性树脂，防污剂亦以氧化亚铜为主，有时增加一些辅助防污剂如氧化汞（已淘汰）、DDT（被淘汰）等。  \n\n由于这类防污漆的基料为不溶性树脂，为使防污剂能够不断渗出，必须使防污剂颗粒紧密排列，以达到面层防污剂溶于海水后形成的空隙使内层的防污剂能从空隙中排向海水，为此，防污剂的含量很高。  \n\n为使防污剂紧密排列，毒料的体积至少占 $52.4\\%$ (四方堆积)，最多为 $74\\%$ （六方堆积)。  \n\n接触型防污漆在理论上不必加上可溶性基料，但这样需要大量的防污剂，使防污漆成本很高，又因初期渗出率太高而后期内层防污剂难以排出，造成很大浪费。因此，实际上接触型防污漆中都含有一定量的可溶性基料（松香)，既可调节防污剂渗出率，又可降低防污剂用量，降低防污漆的成本。  \n\n显而易见，由于内层的防污剂将从前层涂膜的空隙中挤出去，接触型防污漆的渗出率是前期大、后期小，呈日益下降的趋势。但接触型防污漆的防污剂含量大大高于溶解型防污漆，因此其防污能力亦要高一些，一般可达两年或更多一些时间。  \n\n$\\textcircled{3}$ 扩散型防污漆扩散型防污漆多以有机锡（已淘汰）或有机铅（已淘汰）为防污剂，以乙烯树脂或氯化橡胶树脂为基料，并有一部分可溶性基料。涂层有一定的透水性，当涂层浸入海水中，海水将渗透到涂层内部，促使防污漆与基料溶胀，形成固溶体，从内部向表面扩散，进而使防污漆与基料的固溶体溶于海水，释放毒料。扩散型防污漆的渗毒机理与溶解型防污漆有些相似，故有的资料中亦将其归为溶解型防污漆。但通常将以无机防污剂\\* $\\mathtt{(C u20}$ ， $\\mathrm{HgO};$ ）为主的归为溶解型，而以有机防污剂为主的归为扩散型。  \n\n(2）有机锡共聚物自抛光型防污漆自20世纪70年代开发出有机锡共聚物以来，船舶防污漆技术进人了一个创新时代。有机锡共聚物通常由甲基丙烯酸、三丁基氧化锡（TBTO）与丙烯酸甲酯反应而成。含有机锡共聚物的防污漆为水解型防污漆，其中有机锡共聚物既为防污剂又作为基料，通过有机锡共聚物在海水中水解，释放出有机锡防污剂，同时基料亦成为可溶性的物质溶解于海水之中。漆膜在水流不断作用下，水解反应不断进行，不断暴露出新鲜面，因此其毒料渗出率非常平稳。由于漆膜凸起的部位受水流作用力较大，水解速率较快，而凹进的部位则水解速率较慢，因而漆膜将日趋光滑，故将这种防污漆称为自抛光共聚物防污漆。有机锡共聚物自抛光防污漆在海水中的水解机理如图3-4-9所示。  \n\n![](images/69cd0b0ac8fefe5e8716a7d50b1813c6ab355fd2ff70b5727ec1c87b1548bf94.jpg)  \n图3-4-9有机锡共聚物自抛光防污漆水解机理  \n\n自抛光共聚物防污漆有以下几个优点。$\\textcircled{1}$ 防污剂渗出率平稳，防污寿命长，防污效果和漆膜厚度成正比，有效防污寿命最长  \n\n可达五年。  \n\n② 在航行中，漆膜在水流作用下自身有抛光作用，可减少船体的粗糙度和航行阻力，能大量节约燃料。  \n\n$\\textcircled{3}$ 具有耐干湿交替性能，除作为船底防污漆外，还可作为水线防污漆。  \n\n④维修方便，船舶进坞作涂层维修时，在原有自抛光防污漆的基础上，可以直接涂装新的自抛光防污漆，不必像其他防污漆需要先涂封闭漆才能继续涂防污漆。  \n\n(3）无锡自抛光防污漆以有机锡共聚物为主体的自抛光防污漆由于其众多优点而被厂泛应用，20世纪末世界上采用自抛光防污漆的深海船只的比例已超过 $60\\%$ 。然而，大量应用的自抛光防污漆所释放的有机锡化合物的毒性对海洋中非目标海生物，包括生态学上和商业上的重要生物如荔枝螺、牡蛎、蚶、贻贝等带来了意想不到的伤害，影响到它们的发育、繁殖和生存，并且会通过海水进入海洋生物体内后进入人的体内，损害人体的生殖和免疫系统。因此，20世纪80年代初法国首先宣布禁止使用有机锡含量大于 $3\\%$ （按质量）的防污漆来涂装所有的小艇和总长小于 $25\\mathrm{m}$ 的海船。在1985年以后，美国、英国、日本、德国、瑞士等国相继禁止或限制有机锡的使用，1987年12个欧洲共同体国家也一致同意在 $25\\mathrm{m}$ 以下船体上禁止使用有机锡防污漆。2001年国际海事组织（IMO）已通过了在船舶防污漆中禁止使用有机锡的《国际控制有害船底防污系统公约》（AFS公约)。从此，无锡自抛光防污漆就日益发展。  \n\n目前世界各国开发的无锡自抛光防污漆品种繁多，按照其防污机理可以分为三大类：水合型、水解型和复合型。  \n\n$\\textcircled{1}$ 水合型无锡自抛光防污漆水合型无锡自抛光防污漆也称为可控释放聚合物（CDP）防污漆。它是一种将传统的溶解型防污漆技术和长效的接触/扩散型防污漆技术有机地结合的新型防污漆。CDP型防污漆常常具有较高的松香含量。一直到20世纪30年代，CDP防污漆还仅属于一般的溶解型防污漆。20世纪40年代后期，伴随着合成石油树脂的涌现，化工公司开发这些新树脂用以改进可溶树脂架构而使成膜体系具有更优的性能和耐久性，不断地改进形成如今的CDP型防污漆，其共同点是这些产品的树脂体系含较高的松香或改性松香 $(>50\\%)$ 。水合型无锡自抛光防污漆通常以疏水性的合成树脂和可溶性的松香树脂为主要成膜材料，以氧化亚铜为毒料，并添加了一些降解速率快的杀虫剂。它是通过松香与海水的水合反应，释放毒料；通过合成树脂的疏水性控制涂层的消耗。尽管从理论上讲这些防污漆迟早会溶解和抛光掉，但实际上这种情形不会发生，因为漆膜因不溶性铜盐及松香杂质、不溶性树脂的集结而变得越来越难溶。皂化层的变厚使得CDP防污漆的使用寿命立面最长为三年，平底比三年更长些（取决于船只航行状况和涂装配套）。  \n\n多数船舶涂料商都拥有各自的CDP型防污漆，但描述各异，典型的如：“溶蚀（eroding）”、“消融（ablative)”、“抛光（polishing）”、“水合（hydration）”、“离子交换（ion exchange)”、“水解(hydrolysable activated)”，“自抛光（self polishing)”。  \n\n水合型无锡自抛光防污的抛光机理为涂层表层中的松香与海水发生水合反应，并释放毒料后，涂层表层的疏水树脂会形成蜂窝状的、高低不平的坡峰。这些竖起的坡峰强度低，在海水的冲刷下会被折断，这样不断地反应，不断地折断，从而达到自抛光的目的。这种抛光的形式也称为“机械抛光”，其抛光机理如图3-4-10所示。  \n\n水合型无锡自抛光防污漆的特点如下。  \n\na、固体含量高，通常可达到 $60\\%$ ，理论涂布率高。  \n\nb.价格便宜。  \n\n![](images/fb2ccdaada006c34986fccd3972bc4f43e31b64ecbae7bcb3d2e1e6663308913.jpg)  \n图3-4-10水合型无锡自抛光防污漆的抛光机理  \n\nc.具有较高的松香含量，防污效果受海水的温度影响，海水温度较低时，防污效果会降低。  \n\nd.皂化层较厚，通常为 $75\\mu\\mathrm{m}$ 左右。因此，船舶进坞修理时，必须采用高压淡水冲洗，以便彻底地清除皂化层，否则新的涂层会出现气泡、剥落等现象，影响涂层的防污效果。  \n\ne.由于涂层中松香的含量高，涂层过厚时，容易龟裂。  \nf.涂层无自光滑性能，在使用过程中粗糙度会增加。  \ng.防污期限一般为36个月左右。  \n常用的水合型无锡自抛光防污漆（CDP）参考配方见表3-4-11。  \n\n表3-4-11 常用水合型无锡自抛光防污漆（CDP）参考配方  \n\n\n<html><body><table><tr><td>原料名称</td><td>质量分数/%</td><td>原料名称</td><td>质量分数/%</td></tr><tr><td>二甲苯</td><td>19.50</td><td>铁红</td><td>4.50</td></tr><tr><td>防沉剂</td><td>2.00</td><td>氧化锌</td><td>20.00</td></tr><tr><td>松香液</td><td>12.00</td><td>杀虫剂</td><td>7.00</td></tr><tr><td>增塑树脂</td><td>2.00</td><td>氧化亚铜</td><td>30.00</td></tr><tr><td>丙烯酸树脂</td><td>3.00</td><td>合计</td><td>100.00</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 水解型无锡自抛光防污漆水解型无锡自抛光防污漆是一种以新型丙烯酸聚合物为主要成膜树脂，以氧化亚铜和有机防污剂，如羟基吡啶硫铜或羟基吡啶硫锌为主要毒料的防污漆。  \n\n目前常用的水解型无锡自抛光防污漆所用共聚物有丙烯酸甲硅烷聚合物（silylacrylate）、丙烯酸铜聚合物（copper acrylate）及丙烯酸锌聚合物（zinc acrylate）。  \n\n这种新型的自抛光丙烯酸类共聚物，其与海水的反应机理与有机锡自抛光防污漆类似（图3-4-11和图3-4-12)，在涂料表面产生可溶解的薄层，使漆膜随时间而抛光。氧化亚铜和其他可降解毒料物理分散于漆料中。当树脂在涂料表面水解时，防污剂均匀地释放，在涂料表面形成一定浓度的毒料层而防止污损。一旦毒料扩散于水中，氧化亚铜迅速失去毒性，而其他防污剂则在光照或细菌作用下分解，分解后的物质毒性甚微。  \n\n与有机锡自抛光共聚物防污漆一样，水解型无锡自抛光防污漆通过在海水中水解反应，或离子交换反应，达到有效、均匀地控制毒料的释放和获得自抛光、自光滑的功效。  \n\n![](images/a5f28c1138aeeabced86476220c07bae269344b77b551a7094c864f6b9201285.jpg)  \n图3-4-11 丙烯酸甲硅烷共聚物无锡自抛光防污漆水解机理  \n\n→暴露在海水中的有机硅共聚物漆膜——水解反应形成亲水表面—亲水表面溶解于海水，而又形成“新”的亲水表面水解反应表达式如下。  \n\n![](images/285aa08062f469a36f3ea328eca6ebd5ce607d73f25eecccb0adb5602940d2db.jpg)  \n图3-4-12丙烯酸铜/丙烯酸锌无锡自抛光防污漆水解机理$X$ 为丙烯酸铜或丙烯酸铜锌这类共聚物其水解反应与TBT共聚物和有机硅共聚物相似",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 257,
+        "chunk": "# a.丙烯酸铜型  \n\n聚合物-COO-Cu— $\\scriptstyle\\mathrm{{R}=}\\displaystyle\\rightharpoonup$ 聚合物一 $\\mathrm{\\bf{\\cdot}\\mathrm{COO^{-}+C u^{--}R^{+}}}$ （不可溶） （可溶）",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 258,
+        "chunk": "# b.丙烯酸锌型  \n\n聚合物— $\\mathrm{COO-Zn(\\mathfrak{s})-X+N a^{+}=}$ 聚合物—( $\\mathtt{\\backslash O O\\mathrm{-}N a^{+}\\left(s\\right)+Z n^{2+}+X^{-}}$ (不可溶） （可溶）  \n\nc.丙烯酸硅烷型  \n\n聚合物—COO- $\\mathrm{SiR_{3}(s)+N a^{+}+C l^{-}=\\cosh}$ 聚合物—COO—Na+(s)+R SiCl(aq)（不可溶） （可溶）  \n\n水解型无锡自抛光防污漆抛光机理如图3-4-13所示。  \n\n![](images/e47d00fae236309a2d37c0aea35e1dda334b7e0be74bbefbb61008de7d0ff4dd.jpg)  \n图3-4-13 水解型无锡自抛光防污漆的抛光机理  \n\n水解型无锡自抛光防污漆的特点如下。  \n\na.皂化层较薄，通常为25μm左右。船舶进坞修理时，不需要特别的高压淡水冲洗，  \n这可降低坞修的成本。b.固体含量相对较低，通常为 $40\\%\\sim50\\%$ 0c.能满足速度大于20海里/h、航行率大于90%的船舶（如快速集装箱船、液化气船)  \n的防污需要。d.船舶在航行中，能自光滑，降低涂层表面的粗糙度，节约燃油。e.价格较水合型的无锡自抛光防污漆贵。f.防污性能预测性强，防污期限可达60个月。  \n\n水解型无锡自抛光防污漆自光滑的功效在实际应用中得到了充分体现。如图3-4-14所示为两艘相同大小的集装箱船分别涂装CDP（水合型）和SPC（水解型）两种不同类型防污漆其燃油消耗情况。在航行初期似乎比较近似，但随着航行时间的增加，由于水合型无锡自抛光防污漆（CDP）在船的立面产生藻类污损，其油耗发生显著的增加。  \n\n![](images/4bb73ebc97f64228114e0fc1148dc0d19b104b0fdb2f3f764f7382e8d530f137.jpg)  \n图3-4-14水解型与水合型无锡自抛光防污漆耗油率比较注：--CDP为水合型无锡自抛光防污漆；——SPC为水解型无锡自抛光防污漆。  \n\n常用的水解型无锡自抛光防污漆（SPC）参考配方见表3-4-12。  \n\n表3-4-12 常用水解型无锡自抛光防污漆（SPC）参考配方  \n\n\n<html><body><table><tr><td>原料名称</td><td>质量分数/%</td><td>原料名称</td><td>质量分数/%</td></tr><tr><td>二甲苯</td><td>3.50</td><td>颜料</td><td>2.5</td></tr><tr><td>防沉剂</td><td>2.00</td><td>氧化亚铜</td><td>45.00</td></tr><tr><td>增塑树脂</td><td>3.50</td><td>杀虫剂</td><td>3.50</td></tr><tr><td>丙烯酸共聚物树脂</td><td>40.00</td><td>合计</td><td>100.00</td></tr></table></body></html>  \n\n$\\textcircled{3}$ 复合型自抛光防污漆（hybridCDP/SPC）复合型无锡自抛光防污漆是一种将水合型无锡自抛光防污漆技术和水解型无锡自抛光防污漆技术融合一体的防污漆。它的主要特点如下。  \n\na.固体含量高，通常可达到 $60\\%$ ，理论涂布率高。  \nb.价格适中。  \nc.皂化层通常为 $45\\mu\\mathrm{m}$ 左右。  \nd.最长防污期限为 $36\\sim60$ 个月（根据不同的船舶部位、航行速度和在航率确定）。  \n常用的复合型自抛光防污漆（hybridCDP/SPC）参考配方见表3-4-13。  \n\n表3-4-13 常用复合型自抛光防污漆参考配方  \n\n\n<html><body><table><tr><td>原料名称</td><td>质量分数/%</td><td>原料名称</td><td>质量分数/%</td></tr><tr><td>二甲苯</td><td>8.0</td><td>丙烯酸共聚物树脂</td><td>10.0</td></tr><tr><td>防沉剂</td><td>2.5</td><td>颜料+氧化锌</td><td>16.0</td></tr><tr><td>松香液</td><td>15.0</td><td>氧化亚铜</td><td>35.0</td></tr><tr><td>丙烯酸树脂</td><td>5.0</td><td>杀虫剂</td><td>5.0</td></tr><tr><td>增塑树脂</td><td>3.5</td><td>合计</td><td>100.00</td></tr></table></body></html>  \n\n(4）无防污剂（无毒）防污涂料从环保角度讲，最理想的是不需要释放防污剂而达到防污效果的产品。低表面能防污涂料是利用涂料表面具有低表面能的物理性能，使海洋生物难以附着或者附着不牢，在船舶航行时利用水的剪切力作用或用专门的清理设备很容易清除附着生物的一种防污涂料，主要是指基于有机硅树脂及氟碳树脂的无毒污损物易脱落型防污涂料（non-toxic fouling release coatings)。这类涂料不含毒剂，符合环保要求。20 世纪70年代前后低表面能防污涂料得到了发展。在80年代中期，含有机硅的低表面能防污涂料首次在实船上进行施工。之后有机硅低表面能防污涂料得到了进一步推广，其应用越来越广泛。  \n\n低表面能防污涂料自身性质对防污效果影响很大。研究表明，要达到良好的防污效果，最好能满足以下条件： $\\textcircled{1}$ 低表面能，可以防止海洋生物的最初附着； $\\textcircled{2}$ 低弹性模量，可以使污损物倾向于以剥离方式脱落，需要较小的外力； $\\textcircled{3}$ 适宜的厚度，以控制界面的断裂； $\\textcircled{4}$ 光滑的表面； $\\textcircled{5}$ 较差的分子流动性，足够多的侧链表面活性基团。有机氟聚合物具有极低的表面能，因而成为易脱落型防污涂料的最佳候选者。可是，仅仅表面能低还不够，还需满足上述的其他条件。聚四氟乙烯（PTFE）的表面能是最低的，理应具有最好的防污效果，但由于其表面多孔，实际上防污性能很差。而有机硅的临界表面能虽然高于氟树脂，但由于价廉，同时只要严格控制有机硅涂层的厚度及弹性模量，就可以提高其防污性能，因而得到广泛研究及应用。目前基于实际应用的研究主要集中在以改性聚二甲基硅氧烷树脂为基料和以硅橡胶为基料的涂料合成上。由于施工方便，室温液态硫化硅橡胶常用作制备有机硅涂料。硫化后的硅橡胶作为有机硅涂料的成膜物质，具有较低的表面能，对许多有机物质无黏着性，同时耐水耐潮湿，有良好的抗化学药品性能。经环氧树脂改性的室温硫化硅橡胶双组分防污涂料，经海上挂片18个月，无海生物附着且涂层不脱落。有机硅低表面能涂层与基体之间的附着力一般较差，在保证低表面能防污性能的前提下，从工艺上采用多层复合体系可增强附着力。同时，表面改性技术、等离子体技术及纳米技术的应用可以改善其相容性、增加强度等，使有机硅树脂的应用更加活跃。结合氟树脂和有机硅树脂的优异特性，最近开发出一种新型的低表面能防污涂料——氟代聚硅氧烷，代表产品有：PNFHMS（polynonafluorohexylemethyl siloxane）及 PTFPMSLpoly（triflu-oropropylmethylsiloxane)]，其结构式如图3-4-l5所示。线型的聚硅氧烷骨架上带有氟碳侧基，—CFg在涂膜中将取向表面，既具有线型聚硅氧烷的高弹性及高流动性，又具有氟碳基团的超低表面能特性。分子链中—CHCHz一是必须的，它可以增加分子对水及热的稳定性。其中对防污不利的因素—CHzCFz—偶极子被限制在表面之下，而正好对增加附着力有利。  \n\n![](images/4e8abf605d1fe1469dc935bb2a0b67b3b7448e983131730f71a2ac0d697c7ce1.jpg)  \n图3-4-15 氟代聚硅氧烷  \n\n无毒有机硅涂料具有憎水性和低表面能。因动物性海生物会利用它的分泌物黏附在物体的表面，这种分泌物通常由亲水性的物质组成。所以这种涂料能使海生物的附着降低到最低的程度。一旦附着，也很容易通过船的航行或较低水压水冲洗而去除掉。大量的实船试验证实，无毒低表面能有机硅涂料具有如下优点：①具有良好的防污性能及节油性能；②无毒料释放到海里，坞修过程中也不会产生含毒料的污水和废砂；③在全世界范围内使用将不受到限制； $\\textcircled{4}$ 防污期可达 $5\\sim10$ 年； $\\textcircled{5}$ 降低坞修费用（与典型的含有杀虫剂的防污漆相比）；$\\textcircled{6}$ 因不含铜，故可以使用于铝壳船。  \n\n不足之处在于：该品种涂料一般适合于船速较高（ $15\\sim30$ 节），活动频率较高的船只，诸如班轮（cruise liners）、冷藏船（reefers）、集装箱班轮（container liners）、液化气船(LNG carriers）、车辆船（vehicle carriers)）、滚装船（roro ferries）、渡船（ferries）等，而不太适合于原油轮（crude oil tankers）、化学品轮（chemicalproduct tankers）、货船（bulkcarriers）等船速较慢，活动频率相对较低的船只。该产品价格也比较昂贵且施工比较烦琐。但开发环境友好型防污涂料是21世纪海洋防污涂料的发展方向之一。一种性能优异的防污涂料应该是防污效果好、防污时间长、经济且对环境影响小。无毒自抛光防污涂料、低表面能防污涂料和含生物活性物质的防污涂料正受到人们的重视，而低表面能防污涂料即无毒污损物易脱落型防污涂料是未来发展的方向之一。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 259,
+        "chunk": "# 6.防污漆防污性能测试方法  \n\n船底防污漆防污性能测试方法是防污漆研究工作、配方筛选、产品改进和成品质量控制的关键。常用的防污漆防污性能测试方法如下。  \n\n$\\textcircled{1}$ 抛光速率测定（polishing rate determination）。 $\\textcircled{2}$ 静态条件下，铜/锌/三丁基锡释放速率测定（determination of copper/zinc/tributyl tin release rate under static conditions)。 $\\textcircled{3}$ 静态、动态循环条件下，铜/锌/三丁基锡释放速率测定（determinationof copper/ zinc/tributyl tin release rates under cyclic static and dynamic conditions)。  \n\n④ 铜/锌释放速率测定（ASTM D 5106—1996改版）（determination of copper & zinc release rates by modification of ASTM D 5l06—1996)。  \n\n$\\textcircled{5}$ 皂化层检查（leachedlayer examination）。$\\textcircled{6}$ 水线循环测试（boottop cycling）。$\\textcircled{7}$ 防污性能测定（assessment of antifouling performance）（防污漆样板浅海浸泡试验  \n方法GB5370—1985)。$\\textcircled{8}$ 曝晒和贮存对防污性能的影响（effect of exposure and storage on antifouling per-  \nformance)。$\\textcircled{9}$ 水介质长期浸泡性能（behaviour on permanent immersion in aqueous media)。$\\textcircled{10}$ 冷流悬挂重力法（cold flow-hangingweightmethod）。  \n\n(1）防污漆抛光速率测定抛光速率的实验室测定是防污漆最重要的测试规程之一，它是计算涂层系统厚度和预测使用寿命的关键。抛光速率的知识也有助于理解涂料功能的类型（即属于抛光系统还是腐蚀系统)。实际上，抛光速率因船速、船的活动范围、水温和盐度而改变。在测定防污涂料的抛光速率时需要考虑所有这些因素，如不同的速度（包括速度为零)；不同的浸没温度；不同的浸没介质；不同的膜厚。  \n\n为了正确地表示磨损行为的特性，在静态和动态条件下测定作为浸没时间函数的膜厚损失是非常重要的。  \n\n$\\textcircled{1}$ 设备  \n\na.合适的涂布设备（例如管式涂布器、杆式涂布器或合适的喷涂设备）。  \nb.大小合适的有机玻璃盘（最常用的为9in、12in和16in， $\\mathtt{l i n}{=}2.54\\mathrm{cm}$ ，下同)。  \nc.“干和湿”的砂纸用于磨盘。  \nd.激光外形测定仪。  \ne.防污涂料搅拌工具，例如调刀。  \n\nf.浸泡设施。  \n\n$\\textcircled{2}$ 步骤9in、12in和16in的有机玻璃盘是最常见的用作抛光速率测定基材。其他基材如鼓式转盘也可使用，但使用率少些。将测试样品（涂料）涂布到有机玻璃盘或鼓式转盘上。在最初的膜厚度被测定后（一般用激光表面光度仪)，或者将测试件附加到转轴(或鼓式转盘)，然后旋转（作动力学测定)，或者放置在罐内（作静力学测定)。经过必需的时间后，将测试件移开。经过适当的干燥期之后再次测定膜厚。在规定的温度和转速条件下，测试样品的抛光速率是由初始的与浸泡后的膜厚度差除以浸泡时间（以天计）来给出。该值乘以30得到最终的抛光速率，单位为 $\\mu\\mathrm{m}/$ 月。应该指出，每项测试必须包括相应的对照涂料。对于所有的测试来说，一般可以选择抛光速率稳定的防污涂料用作标准对照。  \n\n$\\textcircled{3}$ 测试样品的涂布可用不同的方法将测试样品涂布到盘子上。最常用的方法是用管式涂布器涂布，但根据预期进行的测试，也可采用杆式涂布器、传统喷涂和无气喷涂。如图3-4-16所示为测试样品涂布示意图。  \n\n如图3-4-17所示旋转前后一个典型的测试样板的示意图，它表示浸泡后如何被彻底抛光和离开标记测定边缘的距离是如何标记的。  \n\n$\\textcircled{4}$ 抛光盘的测定用非接触式激光外形测定仪测定浸泡前后测试条的厚度。可在样板长度上任何一点对所有的测试样品进行测试。从盘边缘开始的抛光距离是与不同的旋转速度对应的。表3-4-14是当盘的旋转速度为 $749\\mathbf{r}/\\operatorname*{min}$ 时与离盘边缘的各个点距离相对应的速度值。  \n\n![](images/5773c82eb34b6a7007f18f26475e2ceeb82d47a75e62211b9d7273410f232c07.jpg)  \n图3-4-16 涂有16条测试样品的$12\\mathrm{in}$ 盘子的典型排列  \n\n![](images/ae13337de9bcd3828068578474fb881f46b3d708ad1589e6728254a36ad3d62e.jpg)  \n图3-4-17 测试样板示意图  \n\n表3-4-14转盘不同距离处的速度  \n\n\n<html><body><table><tr><td colspan=\"2\">9in盘</td><td colspan=\"2\">12in盘</td></tr><tr><td>距离位置 /cm</td><td>速度 /（海里/h）</td><td>距离位置 /cm</td><td>速度 /（海里/h）</td></tr><tr><td>2 3 4 5 6</td><td>14.56 13.01 11.47 9.93 8.38</td><td>2 3 4 5 6 7 8 9 10</td><td>20.44 18.89 17.35 15.81 14.26 12.72 11.18 9.63 8.09</td></tr></table></body></html>\n\n注： $\\mathrm{1in{=}2.54c m}$  \n\n以下列举了一些常用的测试方法。  \n\na.静力学抛光速率将盘在设定的时间内浸泡，无需任何转动。在预先确定的时间间隔内取出盘子，洗涤、干燥并再次测定。所测得的抛光速率为测试期内的静力学抛光速率。由于静力学抛光速率值小，这些测试往往需要运行12个月。为了掌握静力学抛光速率是否随时有任何的变化，应制备多个同样的盘来浸没不同的时间。  \n\nb.动力学抛光速率将盘在设定的时间内浸泡并以一个固定的速度转动。在预先确定的时间间隔内取出盘子，洗涤、干燥并再次测定。所测得的抛光速率为测试期内的动力学抛光速率。为了掌握动力学抛光速率是否随时有任何的变化，应制备多个同样的盘来浸泡不同的时间。  \n\nc.转动速度与抛光速率的相互关系测定转动速度与抛光速率相互关系最常用的方法是，如上所述制备一个12in的盘，在与三个不同速度沿样板相应的三个不同的位置（一般为2cm、5cm和7cm）测定膜厚。浸泡盘子，以一个设定的速度和设定的时间内转动，之后取出盘子，在与原先测定位置相同的点再次测定膜厚。所测得的抛光速率为与测试点速度相应的动力学抛光速率。  \n\n为了掌握动力学抛光速率是否随时间并因不同的转动速度会有任何的变化，应制备多个同样的盘来浸泡不同的时间。  \n\nd.抛光速率的恒定测试b是在转动条件下测定整个测试期内抛光速率最常规的方法。另有一个类似的方法包含移出盘、测定和再浸没，接着再移出盘并再测定同一个盘，该盘每次移出后将防污涂层完全干燥，这就是所谓的干燥后抛光速率的恒定性测定。  \n\n(2）防污性能的评估（防污漆样板浅海浸泡试验方法）本测试是在静态条件下实施的，这对于防污涂料来说是最为恶劣的条件，这个测试可以看做是潜在产品的筛选测试。  \n\n$\\textcircled{1}$ 设备合适的测试样板，如船用胶合板，规格为 $24\\mathrm{in}\\times24\\mathrm{in}$ $(61\\mathrm{cm}\\times61\\mathrm{cm})$ ；涂布设备，如刷子、无气喷涂设备、防护胶带。  \n\n$\\textcircled{2}$ 材料测试用涂料样品，适合用于涂刷测试样板底漆的防腐涂料，标准防污样品作为对照，适合用于标记和样板封边的防污漆。  \n\n$\\textcircled{3}$ 步骤  \n\na.底材建议采用船用胶合板，但也可使用其他材料诸如钢、轻合金、玻璃纤维等。  \n\nb.底漆系统施工用无气喷涂、刷子或辊子涂布标准系统，选择时必须考虑材质和长期浸泡后对该材质的影响因素(例如：船用胶合板会膨胀，因此底漆系统必须具有弹性)。  \n\nc.样板的涂布布局样板上的涂布布局取决于实验的地点、浮筏的类型和涂料的数量。典型的涂布布局如图3-4-18所示。  \n\nd.防污漆的涂布用无气喷涂法、刷子或辊子根据涂布草图在测试样板上涂布。通常至少涂布两层防污漆，以便达到足够的涂装厚度，降低防污抛光/侵蚀并暴露出底漆的风险，并遮盖瑕疵，如头道漆上的小孔。  \n\n![](images/83c6af562825b9f4d1f5be4b59caced4a16e5bbf1365cf43b6de547c50f62f38.jpg)  \n图3-4-18 涂布草图（正面/反面）  \n\n④防污评估每隔一定时间（如两个月，在污损高峰期检查频率要高，而冬天检查频率低）检查每块测试样板上每种涂装的样品。通过目测的生物体种类和数量评估污损情况，以评估粘泥、附着粘泥、褐藻、海草、藤壶、水虫等的生长情况。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 260,
+        "chunk": "# 7.防污漆各国的立法状态  \n\n含有生物杀灭剂的防污漆被归类于生物杀灭产品，并在很多国家作为杀虫剂受到控制。尽管由于经济和环境原因，生物杀灭的防污漆产品对于船舶工业是重要的，这些被认为危害环境或对人体健康有危险性的产品将会被逐渐淘汰。当评价防污漆对人和环境的安全性时，主要考虑因素有：  \n\n$\\textcircled{1}$ 对于不属于预定目标有机体的影响；  \n$\\textcircled{2}$ 生物杀灭剂在环境里存留的时间；$\\textcircled{3}$ 在海洋食物链的积累；  \n$\\textcircled{4}$ 施工过程中的安全性。  \n\n截至2007年5月，防污漆各国的立法状态如下。  \n\n加拿大所有在加拿大使用的防污漆需要在政府部门登记（加拿大卫生部)。限制：  \n\n$\\textcircled{1}$ 根据加拿大法律含TBT的防污漆完全禁止使用；  \n$\\textcircled{2}$ 所有登记的含铜防污漆浸出率必须小于 $40\\mu_{\\mathrm{E}}$ 铜/ $(\\mathrm{cm}^{2}\\cdot\\mathrm{d})$ 。  \n\n美国  \n\n$\\textcircled{1}$ 所有在美国使用的防污漆需要同时在联邦级别的美国环保署（USEPA）和各州的政府部门登记。$\\textcircled{2}$ 防污漆中铜的使用由美国环保署作为合格性再注册决定（RED）过程的一部分进行评估。$\\textcircled{3}$ 美国州级部门和美国环保署同时评估美国政府船只使用的防污漆对于环境的铜排放。$\\textcircled{4}$ 加利福尼亚海港和码头的水中铜含量已引起关注。防污漆被认为是这些地区铜的主要来源。在一些地区（如加州的圣地亚哥游艇码头区域等）已经确立了长期的时间表来实现含铜防污漆在游艇上的最终逐步淘汰。  \n\n限制：  \n\n$\\textcircled{1}$ 美国环保署的所有TBT防污漆的登记已经被取消；$\\textcircled{2}$ 在美国大型造船厂使用防污漆需遵守危险性空气污染物的国家排放标准（NESHAP)，即防污漆中的挥发有机危险性空气污染物（VOHAP）的含量必须小于 $400{\\scriptstyle{\\overline{{\\mathbf{g}}}}/\\mathbf{L}}$ 面中$\\textcircled{3}$ 在加利福尼亚，某些空气质量区域对游艇防污漆的挥发性有机化合物（VOC）设置了最大等级。  \n\n欧盟各国在英国、瑞典、马耳他、荷兰、爱尔兰、比利时、芬兰和奥地利使用防污漆必须根据各国杀虫剂法律进行登记。  \n\n欧盟生物杀灭产品指令（98/8/EC）目前已生效，同时已启动一个关于所有提交待批准防污用生物杀灭剂的评估。根据生物杀灭产品指令，如果一种生物杀灭剂被认为是可接受的，欧盟各成员国将会对含该生物杀灭剂的防污漆产品申请进行评估。如果防污漆产品被评估为是可接受的，可以进行产品登记，登记过的产品被允许销售和使用。被认为是不可接受的产品将被驱逐出欧洲市场。在市场上所有产品被评估之前的过渡期里，指令要求防污漆生产商在欧盟各国市场通报防污漆产品的详细资料。  \n\n限制：  \n\n$\\textcircled{1}$ 根据营销与使用指令（76/769/EEC)，自2003年1月1日起在欧盟所有国家禁止对所有船舶使用TBT防污漆；$\\textcircled{2}$ 基于欧共体规章No.782/2003，自2003年1月7日起对于悬挂欧盟国家国旗的所有船只禁止使用含TBT防污漆；$\\textcircled{3}$ 自2008年1月1日起所有涂装TBT防污漆的船禁止进人欧盟港口和海港；$\\textcircled{4}$ 总吨位数在 $400\\t$ 以上的悬挂欧盟国家国旗的船只必须被调查并携带符合该指令的证书，长度超过 $24\\mathbf{m}$ 且总吨位数小于400t的船只必须遵守指令进行自我认证。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 261,
+        "chunk": "# 瑞典  \n\n$\\textcircled{1}$ 在瑞典，对仅在波罗的海运营的商船使用含铜防污漆产品必须达到平均铜浸出率小于 $55\\mu\\mathrm{g}$ 铜/ $(\\mathrm{cm}^{2}\\cdot\\mathrm{d})$ 。  \n\n$\\textcircled{2}$ 禁止在波罗的海的游艇上使用含铜防污漆。  \n\n$\\textcircled{3}$ 在瑞典西海岸地区用于游艇的防污漆产品遵守铜浸出速率限制，即必须达到在浸泡后前14天小于 $200\\mu\\mathbf{g}$ 铜/ $\\mathbf{\\bar{c}m^{2}}$ 和在浸泡后前30天小于 $\\mathbf{350}\\mu\\mathbf{g}$ 铜。  \n\n丹麦  \n\n$\\textcircled{1}$ 在游艇上使用防污漆必须标明铜浸出率，同瑞典西海岸一样（见上）。  \n$\\textcircled{2}$ 禁止在游艇防污漆中使用“Irgarol1051”和“Diuron”。  \n\n英国 禁止在防污漆中使用生物杀灭剂“Irgaroll051”和“Diuron”。  \n\n荷兰 禁止在防污漆中使用“Diuron”  \n\n日本  \n\n$\\textcircled{1}$ 在日本造船厂使用的防污漆都应该是无TBT的，并在日本涂料制造商协会（JPMA)进行登记。  \n\n$\\textcircled{2}$ 所有在防污漆里使用的物质必须登记在日本通报物质目录（METI名单）上。  \n\n限制：在日本禁止使用TBT防污漆。  \n\n中国  \n\n$\\textcircled{1}$ 所有在中国使用的和进口的用于防污漆的物质必须在政府机关登记在中国现有物质目录上。  \n\n$\\textcircled{2}$ 所有在中国香港使用的防污漆必须进行登记。  \n\n韩国所有在韩国使用的用于防污漆的物质必须登记人韩国现有化学品目录。  \n\n新加坡、马来西亚、越南、泰国、印度尼西亚和印度根据杀虫剂/生物杀灭剂法律，迄今尚无关于防污漆登记程序。  \n\n澳大利亚根据杀虫剂法律，所有在澳大利亚使用的防污漆需要在国家登记部门注册。  \n\n限制：禁止使用含TBT防污漆。",
+        "category": " Introduction"
+    },
+    {
+        "id": 262,
+        "chunk": "# 8.船舶防污涂料的发展方向  \n\n面对造船的快速发展和激烈的市场竞争，涂料发展商开始把主要精力集中到产品的更新换代上，让新产品更能适应国际造船涂装的新要求，更能适应我国当前积极推进的快速造船的理念。  \n\n从20世纪90年代中期起，国际海事组织（IMO）从船舶海上航行安全及海洋环境保护角度出发，对船舶涂装做出了一系列的规定。  \n\n2001年10月，国际海事组织（IMO）在伦敦通过了《国际控制有害船底防污系统公约》（International Convention on the Control of Systems on Ships Harmful Antifouling）（简称AFS公约）和《及早和有效实行国际控制有害船底防污系统公约》、《本组织有关国际控制有害船底防污系统公约的未来工作》、《船底防污系统的认可和试验方法》、《促进技术合作》等几项决议，以及MEPC102（48）决议通过的船舶防污底系统检验和发证指南。这就意味着一向效果显著、被船东广为接受的有机锡自抛光防污漆将被强行退出历史舞台，开发和推广高效经济型的无锡自抛光防污漆迫在眉睫。  \n\n近年来高性能、环保、安全型船舶涂料得到了大量应用。有机锡防污漆多年来一直在船舶航行中防止海生物的生长占有统治地位。进人20世纪80年代，应用开始受到限制。国际海事组织（IMO）决定从2008年起有机锡防污漆被全面禁用，并于2003年起禁止施用。  \n\n自2003年1月1日全球禁用有机锡防污漆（TBT）施工生效后，高效无锡自抛光防污漆已得到广泛应用。如JOTUN 的 Sea Quantum（甲硅烷基丙烯酸聚合物型，silyl acrylatepolymer)，IP 的 Intersmooth SPC（丙烯酸铜型聚合物型，copper acrylate polymer)，Sigma的AlphaGen 及 Chugoku 的 Sea GroundPrix（丙烯酸锌型聚合物型，zinc acrylate polymer）等。但其主要成分为氧化亚铜。其长期大量使用必将对海洋环境造成影响。无氧化亚铜防污漆已问世但未形成主流。开发低毒、无毒、无金属的防污漆是将来发展的必然趋势。  \n\n低表面能有机硅树脂防污漆是这一领域应用最活跃的，已有大量实际应用。但其还存在许多应用的限制，如船速影响，力学性能差，与基材的附着力差，维修困难，且价格昂贵。因而只用于一些特殊船舶及其部位，如快速集装箱船、LNG船、滚装船及船的螺旋桨等。克服这些限制，及对现有有机硅树脂进行改性是扩大其进一步发展的方向。  \n\n其他无毒防污漆也有大量报道，如纤维植绒无毒防污漆，其核心技术是纤维植绒的防污原理，产品可使少量海藻和其他沾污物在船舶航行时自行剥落。防污性能具有多效性、持久性和无毒性。还有如陆生植物按树、辣椒素、海洋动物/植物等，以及无毒导电防污漆，但还很少应用到实船上，还都在研究探索中。",
+        "category": " Introduction"
+    },
+    {
+        "id": 263,
+        "chunk": "# 五、船壳/甲板漆",
+        "category": " Introduction"
+    },
+    {
+        "id": 264,
+        "chunk": "# 1.船壳漆  \n\n船壳漆涂刷于船壳及舰船或海上石油平台上层建筑。这些部位受到强烈变化的海洋气候影响，如日光、风雨、盐雾等的侵蚀，海浪及海水中蒸发的水汽的腐蚀作用，远洋船只在不同的气候海域中航行，或炎热或寒冷，如此苛刻的海洋环境会使得船壳表面变色、褪色、腐蚀、磨损，如果采用不合适的涂料系统进行大量的、频繁的修补，随着时间的推移，会导致涂料发生堆积，从而丧失系统的完整性并引发潜在剥落。所以对船壳漆的要求是：耐大气曝晒、耐干湿交替、与防护底漆和旧漆膜之间有良好的附着力。  \n\n国家标准《船壳漆通用技术条件》GB/T6745—2008在1986版的基础上更新了原有项目的测试方法，增加了干燥时间、耐冲击性、光泽、耐盐水性、耐盐雾性、耐人工气候老化性指标，更能全面地考核船壳漆所必须具备的性能，其技术要求见表3-4-15。  \n\n表3-4-15 船壳漆技术要求  \n\n\n<html><body><table><tr><td colspan=\"2\">项 目</td><td>指标</td></tr><tr><td colspan=\"2\">涂膜外观 细度/μm</td><td>正常 ≤ 40</td></tr><tr><td colspan=\"2\">不挥发物含量（质量分数）/% 表干 干燥时间/h</td><td>50 ≤ 4</td></tr><tr><td colspan=\"2\">实干 耐冲击性 柔韧性/mm</td><td>≤ 24 通过 1</td></tr><tr><td colspan=\"2\">附着力（拉开法）/MPa 耐盐水性（天然海水或人造海水，27℃士6℃，48h） 耐盐雾性（单组分漆400h，双组分漆1000h）</td><td>M 3.0 漆膜不泡、不脱落、不生锈 漆膜不起泡、不脱落、不生锈</td></tr><tr><td colspan=\"2\">耐人工气候老化性（紫外UVB-313，300h或商定；或者氙灯，500h或 商定)/级</td><td>漆膜颜色变化≤4 粉化≤2 裂纹0</td></tr><tr><td colspan=\"2\">耐候性（海洋大气曝晒，12个月)/级</td><td>漆膜颜色变化≤4 粉化≤2 裂纹0</td></tr></table></body></html>\n\n随着船舶工业的蓬勃发展，传统的涂料提供的保护和装饰寿命有限，所以通过近十年不  \n\n断的技术创新，新的、长效使用的装饰涂料和体系能提供装饰性好、耐候性和保光、保色性佳的综合装饰性能和防腐保护的涂层体系，以此满足不同船舶的需求。  \n\n(1）单组分船壳漆主要有醇酸漆、丙烯酸漆和氯化橡胶漆。共同的特点是价格低廉，低表面处理，使用方便，刷、辊、喷涂皆可，可作为新造、维修用漆，也作为在航保养船壳漆的主要品种。  \n\n$\\textcircled{1}$ 醇酸船壳漆单纯的醇酸树脂船壳漆初始光泽好，附着力好，施工方便，价格低廉。缺点是易失光、粉化，与醇酸防锈底漆配套使用，在近海的小型船舶上，使用较多。  \n\n醇酸防护底漆主要有醇酸铝粉、醇酸铁红、醇酸磷酸锌底漆。  \n\n为了获得更加完善的性能，可用其他的树脂对醇酸树脂进行改性，如有机硅改性醇酸、丙烯酸改性醇酸、氯化聚合物改性醇酸等。  \n\n有机硅改性醇酸涂料既保留有醇酸树脂漆室温固化和涂膜物理、力学性能好的优点，又具有有机硅树脂耐热、耐紫外线老化及耐水性好的特点，是一种综合性能优良的涂料。最早的改性方法是将有机硅树脂直接加到反应达到终点的醇酸树脂反应釜中即可。通过这样简单的混合，醇酸树脂的室外耐候性大大改进。另一种改性方法是制备反应性的有机硅低聚物，用以和醇酸树脂上的自由羟基进行反应；也可将有机硅低聚物作为多元醇与醇酸树脂进行共缩聚。通过化学反应改性的醇酸树脂耐候性更好。如用醇解法制成的羟基封端醇酸预聚体与以水解法或异官能团法制成的有机硅预聚体进行缩聚反应合成出 $(\\mathrm{A}{\\mathrm{-}}\\mathrm{B})_{n}$ 型结构的有机硅-醇酸嵌段共聚物，并以该嵌段共聚物为基料制成清漆；该清漆综合性能优良，既具有醇酸树脂清漆的室温固化、漆膜柔韧性、冲击强度和附着力好的优点，又大大提高了耐热、耐大气老化和抗水介质腐蚀等性能。有机硅改性醇酸船壳漆是美国海军的舰船船壳漆多年来采用的主要品种之一。  \n\n$\\textcircled{2}$ 丙烯酸船壳漆丙烯酸船壳漆初始光泽好，保色、保光性好，白漆不易泛黄，施工方便，价格适中。缺点是由于其热塑性，高温时变软，失去光泽，耐沾污性差。有人尝试采用氯化聚烯烃改性丙烯酸树脂，醇酸改性丙烯酸的路线去改善性能。改性后的丙烯酸树脂可获得良好的综合性能，其与醇酸、氯化聚合物以及经济型的环氧防腐底漆配套的涂层体系，较多的在近海船舶使用。  \n\n$\\textcircled{3}$ 氯化橡胶船壳漆氯化橡胶船壳漆作为一种性能优异的防腐材料，单组分，快干，无复涂间隔，施工方便，并且耐水性和耐大气老化性能良好，与氯化橡胶防腐蚀底漆配套使用，获得广泛的应用，已有数十年的历史。但传统的生产氯化橡胶工艺中采用 $\\mathrm{CCl_{4}}$ 作溶剂，由于其是消耗臭氧层物质，我国履行蒙特利尔保护大气臭氧层公约，在2009年全部停止溶剂法氯化橡胶生产线，国内有关厂家一直在开发水相法取代溶剂法来生产其替代物，目前水相法的制备工艺正在逐步完善。高氯化聚乙烯、氯醚、氯醋等氯化聚合物类的船舶涂料产品在近海船舶上也是比较重要的产品，但溶解度有限，难以提高体积固含量，涂装道数增多，需进行改性，促进与相关树脂的相容性，以获得良好综合性能。但在一些跨国的船舶涂料厂商产品名录中该类产品已不出现。  \n\n(2）双组分船壳漆环氧船壳漆、脂肪族聚氨酯船壳漆与各类环氧防腐底漆配合，因其较长的使用寿命成为深海船舶市场的主打产品。  \n\n$\\textcircled{1}$ 环氧船壳漆环氧树脂漆膜坚韧、耐磨、寿命较长。但在UV照射下分子链降解而导致漆膜粉化、失光、颜色差异等不良耐候性的表现，从而装饰性稍差，但功能性并没有较大的影响。施工时需注意温度和涂装间隔的要求。环氧树脂结构中含有的羟基和环氧基，可以用其他树脂改性，如经过丙烯酸改性的环氧船壳漆，通过QUV加速老化和自然曝晒，其保光、耐候性大大提高，延长复涂间隔，用于不可使用异氰酸酯固化的场合。表3-4-16为",
+        "category": " Introduction"
+    },
+    {
+        "id": 265,
+        "chunk": "# 典型的环氧船壳漆配方。  \n\n表3-4-16 典型的环氧船壳漆配方   \n\n\n<html><body><table><tr><td>组分</td><td>配方</td><td>质量分数/%</td><td>组分</td><td>配方</td><td>质量分数/%</td></tr><tr><td rowspan=\"5\">A组分</td><td>环氧树脂</td><td>30</td><td rowspan=\"2\">A组分</td><td>着色颜料</td><td>1</td></tr><tr><td>钛白粉 硫酸钡</td><td>10</td><td>乙醇</td><td>0.3</td></tr><tr><td>325目滑石粉</td><td>18 10</td><td>混合溶剂</td><td></td><td>30</td></tr><tr><td>有机膨润土</td><td>0.5</td><td rowspan=\"2\">B组分</td><td>聚酰胺树脂</td><td>66</td></tr><tr><td>改性氰化麻油</td><td>0.2</td><td>二甲苯</td><td>34</td></tr></table></body></html>\n\n注：配比为A组分：B组分 $=5:1$ （质量比）。  \n\n环氧船壳漆通常的配套为：  \n\n环氧云铁底漆 $125\\mu\\mathrm{m}\\times2$ 环氧各色船壳漆 $40\\mu\\mathrm{m}\\times1$  \n\n$\\textcircled{2}$ 聚氨酯船壳漆以脂肪族异氰酸酯和含羟基丙烯酸树脂为基料，添加耐候性颜料和助剂等组成的双组分聚氨酯船壳漆，与环氧防锈漆配套，比环氧型船壳漆在装饰性和耐久性方面更优良，是目前大型商船广泛采用的船壳配套体系，漆膜坚韧，具有良好的耐冲击、耐磨性能；耐候、保光、保色性强，装饰性好，同时具有良好的耐化学品、耐水性能。表3-4-17为典型的聚氨酯船壳漆配方。  \n\n表3-4-17 典型的聚氨酯船壳漆配方   \n\n\n<html><body><table><tr><td>组分</td><td>配方</td><td>质量分数/%</td><td>组分</td><td>配方</td><td>质量分数/%</td></tr><tr><td rowspan=\"3\">A组分</td><td>金羟基丙酸树脂</td><td></td><td rowspan=\"2\">A组分</td><td></td><td></td></tr><tr><td></td><td>5425</td><td>酰胺改性氢化麻油</td><td>10. 5</td></tr><tr><td>硫酸钡</td><td>10</td><td>B组分 75%缩二脲</td><td>100</td></tr></table></body></html>\n\n注：配比为 $\\mathbf{A}:\\bar{\\mathbf{B}}{=}10:1$ （质量比）。  \n\n聚氨酯船壳漆的典型配套为：  \n\n环氧防护底漆 $2\\times125\\mu\\mathrm{m}$ ·聚氨酯漆 $1\\times50\\mu\\mathrm{m}$  \n\n聚氨酯漆对醇类、水汽敏感，在生产和施工过程中需加以注意。如生产的原材料必须密封保存，保持干燥；选用含水率低的溶剂。在生产聚氨酯系列产品之前，必须保持设备的清洁，干燥，不能含有水分，环氧和醇类等物质均可能影响涂料的生产，生产过程中控制环境相对湿度不大于 $75\\%$ ，生产完成时必须立即包装，且整个包装过程应采用氮气保护，以避免水分的吸人。  \n\n聚氨酯船壳漆施工中要注意以下事项。  \n\na.注意温度、湿度等环境条件，低温、高湿及施工时或施工后立即发生冷凝，可能会  \n导致漆膜失光，性能损失。b.注意与环氧底漆之间较短的复涂间隔，在需要延长复涂间隔的需求时，建议安排一  \n道过渡涂层。c.注意聚氨酯面漆在深色底漆的表面的遮盖力。d.在维修时，聚氨酯船壳漆可直接施工在经彻底淡水清洗和去除油脂的旧涂层上，但  \n需铲除疏松或片状脱落的涂层，使待复涂的表面处于完整且牢固附着的状况。$\\textcircled{3}$ 聚硅氧烷面漆近年来聚硅氧烷技术得到了快速发展，它利用有机-无机混接技术，  \n使两种材料形成一个具有共价键的聚合物网络，如氢化环氧改性聚硅氧烷、丙烯酸改性聚硅  \n\n氧烷、丙烯酸脲烷改性聚硅氧烷等，其最终产物结合了有机物（易加工、力学性能好及室温固化等）与无机物的最佳特性（情性、硬度、附着力和耐化学品性，耐高温、耐候、耐紫外线等)。其中有机、无机在混接树脂中的比例对获得平衡的综合性能非常关键，既具有良好的防腐蚀能力，又具有极好的耐受UV光照降解的能力。有机改性的程度太低，会有潜在的开裂、附着力的欠缺；太高，则达不到所需求的保光保色性能。聚硅氧烷的硅-氧键键能高达 $445\\mathrm{kJ/mol}$ ，大大高于有机聚合物典型的碳-碳键的键能 $358\\mathrm{kJ/mol}$ ，这意味着需要更强的活化能才能破坏聚硅氧烷聚合物。因此，聚硅氧烷面漆具有优异的耐大气和化学性破坏的性能，从而提高使用期的装饰能力，具有杰出的保光、保色性，极长的使用寿命。有人在试验室根据ASTMG53—1993做两种涂料的加速老化比较试验（QUV-A)，结果显示，聚氨酯涂料在 $2000\\mathrm{{h}}$ 时还能保持初始光泽的 $75\\%$ $4500\\mathrm{h}$ 光泽只剩下原先的 $10\\%$ 左右，而后者在 $4500\\mathbf{h}$ 仍能保持初始光泽的 $75\\%$ ， $8000\\mathrm{h}$ 仍达到 $45\\%$ 左右。  \n\n表3-4-18为双组分环氧聚硅氧烷面漆配方。  \n\n表3-4-18双组分环氧聚硅氧烷面漆配方  \n\n\n<html><body><table><tr><td>组分</td><td>名称</td><td>质量分数/%</td><td>组分</td><td>名称</td><td>质量分数/%</td></tr><tr><td rowspan=\"5\">A</td><td>硅氧烷树脂</td><td>64.4</td><td rowspan=\"2\">A</td><td>气相二氧化硅</td><td>1.0</td></tr><tr><td>颜料</td><td>1.6</td><td>溶剂</td><td>适量</td></tr><tr><td>钛白粉</td><td>24.5</td><td></td><td></td><td></td></tr><tr><td>滑石粉</td><td>2.0</td><td>B</td><td>氨基硅烷</td><td>7.0</td></tr><tr><td>抗气剂</td><td>0.5</td><td></td><td>端氨基聚醚</td><td>5.0</td></tr></table></body></html>  \n\n该配方在 $25^{\\circ}C$ 时有良好的施工性能，混合使用期大于4h，干燥时间4h，最小复涂间隔为 $\\beta\\ln$ 。该典型聚硅氧烷涂料的实验室试验结果见表3-4-19。  \n\n表3-4-19 聚硅氧烷涂料的实验室试验结果  \n\n\n<html><body><table><tr><td>检验项目</td><td>测试结果</td><td>标准</td><td>检验项目</td><td>测试结果</td><td>标准</td></tr><tr><td>附着力（拉脱法）/MPa</td><td>>20</td><td>ASTM D4541</td><td>耐盐雾性/h</td><td>1000</td><td>ASTM B117—1995</td></tr><tr><td>耐磨性（泰伯尔法）</td><td>1000</td><td>ASTM D4060</td><td>冷凝试验/h</td><td>2160</td><td>ASTM D4585</td></tr><tr><td>柔韧性（125干膜）/mm</td><td>25</td><td>ISO 1519—1973</td><td>耐冲击（1.5mm钢板）/（kgf·m）</td><td>0.57</td><td>ASTM D2794</td></tr><tr><td>耐大气曝晒</td><td>优</td><td>ISO 12944-5</td><td></td><td></td><td></td></tr></table></body></html>  \n\n相对于常规的面漆产品，聚硅氧烷漆可制成厚浆、高固体分涂料，环氧改性的聚硅氧烷可达 $100\\%$ 的固含量，丙烯酸改性的稍低些，也会在 $70\\%$ 以上。喷涂一道膜厚可达 $125\\mu\\mathrm{m}$ 与高性能环氧防护底漆配合，整个体系只需两道涂层，就可超过常规的锌粉底漆/环氧云铁中间漆/聚氨酯面漆涂层体系的保护寿命，从而降低涂装成本，提高生产效率。  \n\n如典型的配套体系：  \n\n高性能环氧防护底漆 $1\\times150\\mu\\mathrm{m}$ 聚硅氧烷面漆 $1\\times125\\mu\\mathrm{m}$  \n\n聚硅氧烷面漆具有耐机械磨损及良好的边缘保护性能。通常甲板和船周围以及水线部位是易受破坏的区域，货物装卸、护材的磨损、锚链及钢丝绳的磨损，传统的涂料系统对此提供的保护有限，造成了锈蚀，并影响了船舶外观形象，应用聚硅氧烷体系会有较大程度的改善。  \n\n配方中对原材料的选择有限制，如钛白粉表面不同的 $\\mathsf{p H}$ 会影响硅氧烷树脂的缩合反应，导致体系黏度变化；作为固化剂组分的氨基硅烷或氨基硅烷/胺类混合物对潮气敏感，长期的存放会被微量的催化剂和潮气所影响。聚硅氧烷的烷氧基团的水解缩聚反应，使得它对潮气非常敏感，所以与聚氨酯漆的生产要求一样，注意防止潮气的侵人，在生产、包装过程中采用氮气保护，且生产设备制造完毕，必须马上清洗。在施工时，注意不要长时间的暴露在空气中。一般干膜厚度控制在100～150um，太薄，润湿性差，易出现针孔等缺陷，影响其外观，甚至漆膜性能；太厚，会有开裂的风险。涂装时注意涂装间隔的要求。  \n\n聚硅氧烷是高固体分、低VOC产品；同时固化剂不含异氰酸酯，对人危害低，是适应环保发展要求的高性能产品，突出的长期装饰性能增强了营运者的形象并控制了未来的维修费用。相对其他类型面漆，聚硅氧烷面漆相对价格昂贵，主要是针对那些特别注重营运者形象和优良保护资产的船舶提供的解决方案，如政府用船舶、客轮、科考船等，还有维修不便的海上钻井平台，结合了防腐蚀与美观性的双重特点，耐用性出色。  \n\n表3-4-20为主要船壳面漆品种的性能比较。  \n\n表3-4-20 主要船壳面漆品种的性能比较  \n\n\n<html><body><table><tr><td>性能</td><td>聚硅氧烷面漆</td><td>环氧面漆</td><td>PU面漆</td><td>丙烯酸面漆</td><td>氯化橡胶面漆</td><td>醇酸面漆</td></tr><tr><td>耐机械磨损</td><td>好</td><td>好</td><td>一般</td><td>差</td><td>一般</td><td>差</td></tr><tr><td>耐溶剂和化学品溅液</td><td>好</td><td>好</td><td>好</td><td>差</td><td>差</td><td>差</td></tr><tr><td>耐粉化</td><td>极好</td><td>差</td><td>很好</td><td>好</td><td>一般</td><td>一般</td></tr><tr><td>初始光泽</td><td>极好</td><td>好</td><td>极好</td><td>好</td><td>一般</td><td>很好</td></tr><tr><td>保光性</td><td>极好</td><td>差</td><td>很好</td><td>好</td><td>一般</td><td>好</td></tr><tr><td>保色性</td><td>极好</td><td>差</td><td>很好</td><td>好</td><td>一般</td><td>一般</td></tr><tr><td>易清洁</td><td>极好</td><td>一般</td><td>很好</td><td>一般</td><td>一般</td><td>好</td></tr></table></body></html>  \n\n（3）其他船壳漆  \n\n$\\textcircled{1}$ 氟碳船壳漆除上述介绍的船壳漆类型外，目前还进行氟碳超耐候性面漆的研发。氟碳材料是近年备受关注的新型材料，具有极其优异的耐候性、耐沾污性、耐化学品性、耐溶剂性等优良的特性，以氟碳树脂及含氟聚氨酯等改性材料作为面漆的基料，对于海上石油钻井平台等长期处于海洋气候极其苛刻的腐蚀环境下，又不能容易维修，可进行长效的保护，目前需解决的是该类型施工性差，固含量偏低的问题。  \n\n$\\textcircled{2}$ 水性船壳漆开发高固体分、低VOC含量的环境友好型产品将成为各企业研发的重点，虽然水性船壳漆的技术难关，如耐水性、耐老化性、相应的配套底漆等有待提高，但会是一种发展趋势，成为人们关注和努力的目标。  \n\n(4）船壳漆颜填料的选择以上各种类型的船壳漆，树脂在性能中起着决定作用，但作为防锈、着色的颜填料组分在船壳漆配方中也同样需关注，选用耐光老化、耐水性、着色力强的颜料，以及一些特殊功能的颜料能赋予船壳漆附加的功能。  \n\n金红石型钛白粉性能稳定，有很好的耐候与抗粉化性能，作为船壳漆中最广泛使用的白色颜料，随着纳米技术发展，现在有纳米级钛白颜料的研发，据介绍其纳米微粒还可以改善涂料的流变性，提高涂层的附着力、硬度、光洁度和耐老化性，同时具有紫外光吸收的功能。  \n\n铅系、铬系的颜料因其防锈功能、耐光老化性能优异，着色力持久，价廉，长期以来，获得较广泛的应用，但随着对其危害性的认识，环保法规的日益完善，其将日益受限。  \n\n目前新型的高性能、特殊功能的颜料也在逐步地被用在船壳漆配方中，赋予特殊功能。如添加特殊的活性颜料，可与锈蚀物反应成无色的混合物，突出真正需要修补的腐蚀区域，保持良好的装饰性能。  \n\n利用配方中独特的颜料体系或是功能性颜料解决近红外光谱吸收容易产生热集聚的现象，可降低材料表面的温度，减少船舶所需的能耗，可在舰船的船壳、甲板、上层建筑以及其他一些特定的区域采用具有红外反射功能的颜料组成的该类太阳热反射涂料，也称低太阳能吸收涂料，符合环保节能降耗的要求，是未来发展的趋势。具有此功能的颜料，如巴斯夫最新研发的功能性黑颜料Lumogen?，能在近红外 $750\\sim2500\\mathrm{nm}$ 光谱反射一半的太阳光，切断了热聚集，使构造组分能够保持低温，并且能提供极好的抗热性能、着色力和迁移稳定性，具有很好的抗化学品性和物理效果，以及好的分散性和一般溶剂的不溶性。  \n\n在面漆中复配的颜料体系相比于传统颜料体系具有较高的热反射率，采用无机和有机颜料的复配体系，在配方中摒弃对太阳光吸收率高的黑颜料，使之具有较低的太阳能吸收性能。海洋化工研究院研制的HJ-507热反射船壳漆和SRD-06型热反射甲板漆就采用了颜料的复配体系，能有效地降低船体表面的温度，尤其在炎热区域，目前在海军舰船上获得较广泛的应用。  \n\n云母氧化铁、铝粉等均为片状颜料，在涂膜中和底材平行重叠排列，可以有效地阻止腐蚀介质渗透。对阳光反射能力强，减缓涂膜老化。不仅防锈性能好，在面漆中使用可以提高耐候性，所以在水上部位的防腐底漆中有较广泛的应用。  \n\n此外在船壳漆中各种功能助剂的选用，诸如润湿剂、分散剂、流平剂、消泡剂，甚至紫外线吸收剂等，在配方中的用量虽少，却能赋予更完善的漆膜性能。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 266,
+        "chunk": "# 2.甲板漆  \n\n甲板漆应用于船舶、海上石油钻采平台的甲板部位，其处于与船壳漆同样的海洋大气的腐蚀环境。不同之处在于甲板处于日光的垂直照射时间长，甲板上船员行走及设备移动等对涂层的磨损很大。所以对甲板漆的要求是：与底材、层间具有良好的附着力，不得脱落；耐海洋性气候好；耐磨性、耐洗刷性和耐冲击性能；足够的柔韧性适应船板冷热的伸缩；对防滑漆来说，摩擦系数大，防滑性好。  \n\n《甲板漆通用技术条件》GB/T9261—2008国家标准，在1988版的基础上更新了原有项目的测试方法，增加了不挥发物含量、干燥时间、耐冲击性、耐人工气候老化性指标，更能全面地考核甲板漆所必须具备的性能。甲板漆的技术要求见表3-4-21。  \n\n表3-4-21 甲板漆的技术要求  \n\n\n<html><body><table><tr><td colspan=\"2\">项 目</td><td>指标</td></tr><tr><td colspan=\"2\">涂膜外观 不挥发物含量（质量分数）/%</td><td>正常 50</td></tr><tr><td>干燥时间/h</td><td>表干 实干 ≤</td><td>4 24</td></tr><tr><td colspan=\"2\">耐冲击性</td><td>通过</td></tr><tr><td colspan=\"2\">附着力/MPa 耐磨性（500g/500r）/mg</td><td>M 3.0</td></tr><tr><td colspan=\"2\">耐盐水性（天然海水或人造海水，27℃士6℃，48h）</td><td>100</td></tr><tr><td colspan=\"2\">耐柴油性（其中介质为0*柴油，48h）</td><td>漆膜不起泡、不脱落、不生锈 漆膜不起泡、不脱落</td></tr><tr><td colspan=\"2\">耐十二烷基苯磺酸钠（1%溶液，48h）</td><td>漆膜不起泡、不脱落</td></tr><tr><td colspan=\"2\">耐盐雾性（单组分漆400h，双组分漆1000h） 耐人工气候老化性（紫外UVB-313，300h或商定；或者氙灯，500h或 商定）/级</td><td>漆膜颜色变化≤4 粉化≤2</td></tr><tr><td colspan=\"2\">耐候性（海洋大气曝晒，12个月）/级</td><td>漆膜颜色变化≤4 粉化≤2</td></tr><tr><td colspan=\"2\">防滑性（干态摩擦系数）</td><td>裂纹0 ≥0.85</td></tr></table></body></html>  \n\n甲板漆通常是指由具有防腐作用的底漆与耐候作用的面漆组成的涂层体系。有些船舶会采用与船壳、上建部位一致的涂层配套体系。以前甲板漆划分为“通用型”和“防滑型”两大类，现在趋于不明确划分，通常将树脂种类和防滑性能综合，如环氧甲板漆、环氧防滑甲板漆、聚氨酯防滑甲板漆等。以下根据涂料的组分划分为单组分甲板漆和双组分甲板漆来介绍。  \n\n(1）单组分甲板漆在近海的小型船舶中比较普遍使用的经济适用型甲板漆有醇酸甲板漆、氯化橡胶甲板漆。  \n\n$\\textcircled{1}$ 醇酸甲板漆的常规配套 醇酸铁红/灰 $2\\times75\\mu\\mathrm{m}$ 醇酸面漆 $1\\times50\\mu\\mathrm{m}$ $\\textcircled{2}$ 氯化橡胶甲板漆的常规配套 氯化橡胶铁红或铝粉防锈底漆 $2\\times75\\mu\\mathrm{m}$ 氯化橡胶/丙烯酸面漆 $1\\times50\\mu\\mathrm{m}$  \n\n氯化橡胶甲板漆的耐水、耐候、耐碱性均较好，对表面处理要求低，适用于多种底材，无复涂间隔，可被氯化橡胶、丙烯酸面漆复涂，易于维修和在航保养。氯化橡胶型比醇酸型的使用期限虽长，仍不能满足大型油轮及石油钻进平台的要求，并且由于环保法规的限制，2009年以后氯化橡胶树脂需要适合的替代物。  \n\n(2）双组分甲板漆双组分的甲板漆主要有环氧聚酰胺甲板漆、聚氨酯甲板漆类型等，可适用于不同的需求。  \n\n$\\textcircled{1}$ 环氧甲板漆目前在大型商船、新造船、海上钻井平台上较普遍采用的甲板漆为环氧类型，该热固型体系反应后很硬且耐磨，直接施工于表面处理过的底材，也可复涂在无机富锌底漆或过渡漆表面，其中常用的为厚浆型环氧云铁防锈漆。片状结构的云母氧化铁在涂层中可有效防止水汽渗透，起屏蔽作用，且是耐磨的颜料。厚浆型的甲板漆漆膜坚韧、附着力强、耐水、耐油、耐化学品，体积固含量高，每道涂层干膜可达 $125\\mu\\mathrm{m}$ 以上，通常在其表面配合丙烯酸、环氧、聚氨酯面漆，具有较长的使用期限。有些情况可单独作为甲板漆。改性环氧防腐底漆由于和底材、旧涂层良好的附着力以及低表面处理的要求而大量应用在维修和保养过程中，也有基于成本的考虑在新造船过程中选用。  \n\n表3-4-22为环氧厚浆甲板漆参考配方。  \n\n表3-4-22 环氧厚浆甲板漆参考配方  \n\n\n<html><body><table><tr><td>组分</td><td>配方</td><td>质量分数/%</td><td>组分</td><td>配方</td><td>质量分数/%</td></tr><tr><td rowspan=\"5\">A组分</td><td>E-42环氧树脂</td><td>28</td><td rowspan=\"2\">A组分</td><td>有机膨润土</td><td>0.8</td></tr><tr><td>滑石粉</td><td>25</td><td>二甲苯、丁醇</td><td></td></tr><tr><td>氧化铁红</td><td>10</td><td rowspan=\"2\"></td><td></td><td>19</td></tr><tr><td>硫酸钡</td><td>17</td><td>聚酰胺树脂</td><td>66</td></tr><tr><td>改性氢化麻油</td><td>0.2</td><td>B组分</td><td>二甲苯</td><td>34</td></tr></table></body></html>\n\n注：配比为A组分：B组分 $\\mathbf{\\delta}=\\hat{\\mathbf{6}}:1$ （质量比）。  \n\n环氧甲板漆的常规配套体系如下。  \n\n底漆 环氧云铁防护漆 $2\\times125\\mu\\mathrm{m}$ 面漆 环氧面漆、聚氨酯面漆 $1\\times50\\mu\\mathrm{m}$ 具有耐磨性能的环氧防护底/面漆 $2\\times150\\mu\\mathrm{m}$  \n\n②聚氨酯类型甲板漆聚氨酯类型甲板漆配套体系通常采用防腐底漆、厚涂聚氨酯弹性中间层、聚氨酯面漆的综合体系，该体系赋予涂层优良的耐冲击性，能适应重载冲击和环境温差引起的热胀冷缩，具有极好的弹性和韧性，良好的耐介质、耐大气老化和耐磨性，以及较舒适的踩踏感觉。  \n\n随着船舶的多功能性的需求，一些大中型舰船、客轮、海巡、救助船、远洋科考船等都配备直升机，对甲板漆的防滑、耐冲击等性能有了更高的要求，可参考2001年制定的国军标《直升机甲板防滑漆规范》GJB5066—2001。对于飞行甲板防滑漆则要求更高的性能，如耐加速腐蚀性、防滑性、耐磨损性以及阻燃性等要求，在美军标MIL-PRF-24667B中分门别类，指标明确。聚氨酯类型甲板漆在美国海军舰艇甲板已广泛应用，具有良好的耐受性，如酸、碱、盐、油脂、燃油等介质和耐冲击能力。配套体系为具有防腐蚀作用的底漆一道，再加上具有防滑作用的厚涂面漆，面漆厚度均超过 $\\mathbf{lmm}$ 。涂层道数少，施工简便。  \n\n在国内目前较典型的聚氨酯型防滑涂层如海洋化工研究院的HF-05直升机起降甲板防滑漆，由双组分聚氨酯型的底漆、弹性中涂漆和面漆三部分组成，并配以防滑粒料的防滑体系，涂层具有良好的弹性和柔韧性，能耐受温变引起钢板形变，避免漆膜缺陷，使用寿命达5年以上。  \n\n(3）甲板防滑粒料对于有防滑性能要求的甲板漆通常是在涂层中添加防滑介质，赋予漆膜防滑能力，增大摩擦力，减少磨损，防止人员滑倒。特别是在风浪大、船体摇动、甲板潮湿时会造成潜在的危险性的增加。常选用的防滑粒料是不规则的硬质或软质的颗粒，按其材质分为两类： $\\textcircled{1}$ 合成有机材料，如聚氯乙烯、聚乙烯、聚丙烯树脂粒子、聚氨酯树脂粒子、橡胶粒子等惰性高分子； $\\textcircled{2}$ 无机物，如硅石粉、石英砂、玻璃片、碳化硅、结晶氧化铝、云母等。无机物粒料性能稳定，硬度高，常被用于外甲板。特别是金刚石级硬度的氧化铝型耐磨粒料，在干、湿、油状态下的摩擦系数几乎不变，耐热喷气、耐化学品性好，且附着力好，在军用防滑甲板漆中应用。  \n\n防滑粒料一般单独存放，也可放在其中一个组分中（有沉降的风险)。在使用时可直接掺入涂料中机械混合后施工或最后一道涂料施工后且未固化时喷洒在面漆上，让防滑粒料牢固地嵌在漆膜中。  \n\n（4）防滑甲板漆的施工  \n\n$\\textcircled{1}$ 底材的表面处理所有待涂表面一般应进行喷砂（抛丸）除锈，按GB8923的规定达到 $\\mathsf{S a2.5}$ 级，除去所有油或油脂、可溶性污染物以及其他外来物质，以清洁、干燥表面。对于预涂无机富锌底漆的新造船及以前涂装过同种涂料的甲板部位，若底材保护良好，可采用机械清理和扫砂的方法，处理破坏的漆膜表面，即可进行涂装。对于修理船涂装不同种类涂料时，应进行严格的除锈工作，要求达到St3或 $\\mathrm{{Sa2.5}}$ 级，除锈后的甲板应具有一定的粗糙度，以达到与底材良好的附着力。局部修补可采用手工或动力工具清理至少至St2的标准，且选用对底材、旧涂层有良好的附着力，并且低表面处理要求的品种。  \n\n$\\textcircled{2}$ 底漆的施工 底漆可采用刷、辊、喷涂的常规施工方式。  \n\n$\\textcircled{3}$ 防滑面漆的施工一般商用船舶的防滑漆施工，边施工面漆边进行人工抛撒防滑粒料，随后薄薄施工一层面漆，干后扫除多余的未黏附上的防滑粒料。  \n\n对前述提到的具有高性能的环氧或聚氨酯防滑涂层，将防滑粒料加人混合的防滑漆中进行机械混合，在使用期内，用辊涂施工厚的防滑涂层，注意边界的彼此交叠。  \n\n对于高性能聚氨酯类防滑甲板涂料的中间层的施工，由于中间层为高固体分厚涂涂料，采用刮涂与辊涂相结合的方法施工。实干后24h内涂装面漆，在施工面漆时人工抛撒防滑粒料，扫除多余的未黏附上的防滑粒料，24h后涂装最后一道面漆。  \n\n（5）甲板漆的发展方向  \n\n$\\textcircled{1}$ 高固体分、低VOC、无溶剂的环境友好型甲板漆是防滑涂料的发展方向。美国防滑涂料军标MIL-PRF-24667B中制定的指标，不仅有对防滑的要求，更突出了对环保的要求，其中涉及VOC的要求、颜料和添加剂中的金属含量（如锑、砷、钡等）以及结晶二氧化硅含量与有害物质毒性等，这些要求也适应环保的趋势。  \n\n$\\textcircled{2}$ 具有低太阳能吸收的甲板漆的使用。由于大面积的甲板区域受到阳光的直接曝晒，会吸收来自太阳的红外线辐射热能，使得甲板下的温度上升，采用该功能甲板漆，可以降低材料表面的温度，减少空调的负荷和营运费用，为船员和敏感的电器设备提供更加舒适的工作环境。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 267,
+        "chunk": "# 六、各种舱室漆",
+        "category": " Introduction"
+    },
+    {
+        "id": 268,
+        "chunk": "# 1.压载水舱漆  \n\n(1）概述压载水舱是船舶内舱中相当特殊的一类舱室，舱室结构复杂、空间狭小，使得表面处理和涂装工作十分困难。由于处于舱室内高温、高湿和海水的严重的腐蚀环境，使得压载水舱的防腐蚀涂层在较短时间内很容易发生裂纹、剥落和失效，进而引起压载水舱船体结构腐蚀，因此被认为是影响船舶安全的重要因素之一。一些重大船舶事故，追其原因与压载水舱严重的腐蚀导致结构强度大幅下降有着密切的关系，因此怎么强调压载水舱保护涂料的重要性都不会过分。为此这一问题一直受到国际海事组织（internationalmaritimeorganization，IMO）的关注。1995年11月IMO以A.798（19）号决议通过了《专用海水压载舱防腐系统的选择、应用和维护指南》，以改进散货船和油船安全。  \n\n2002年12月IMO下属的海上安全委员会（MSC）的第76届会议上根据散货船综合安全评估（FSA）研究的结果，决定制定强制的压载舱保护涂层性能标准，作为控制散货船风险的措施之一，并且组织成立了以各国船级社、船东、造船界、涂料生产厂商和相关国际行业组织的联合工作组，经过多次深人和广泛的讨论，在2006年12月的MSC第82届会议上最终通过，并于2008年7月1日起对500总吨及以上的国际航行船舶成为强制性要求。压载舱保护涂层性能标准是以IMO的MSC第82次会议上通过的MSC.215（82）决议的附件2《所有类型船舶专用海水压载舱和散货船双舷侧处所保护涂层性能标准》（简称PSPC）表示的。  \n\n(2）压载水舱漆的种类由于压载水舱的严重腐蚀环境和结构特点，在新船投人航运后，又是非常难于进行周期维护的部位，因此要求具有长效的可靠使用寿命。  \n\n早期的船舶压载水舱保护涂料多含有沥青类树脂，如煤沥青或煤焦油沥青，并与其他树脂，主要是环氧和聚氨酯树脂配制为环氧沥青涂料、聚氨酯沥青涂料等，由于沥青树脂本身具有优良的耐水性能，加上环氧树脂或聚氨酯树脂的优异的黏结性能，使得环氧沥青涂料和聚氨酯沥青涂料成为一类防腐蚀性能优异的压载水舱保护涂料。但是由于两个主要的原因，使得含沥青系压载水舱涂料退出了在压载水舱部位的应用：一是沥青树脂的黑色颜色的原因，这类防腐涂料的颜色均为深黑色，不易发现早期的涂层破坏所引起的基体钢板的锈蚀问题；二是沥青树脂本身的对涂装施工人员和其他相关人员的健康影响。  \n\n另一类涂料称为“软涂料”，如羊毛脂涂料，也在压载水舱部位中应用过，这类软涂层是一种不会干燥成膜、类似于防锈油脂类的物质。由于涂层不干和相当柔软，在受到轻微的机械冲击，甚至于用手指就可以擦除。应用在压载水舱时，往往在海水进出口周围很容易被冲刷掉。它们一般只作为锈蚀钢板表面的临时性防腐保护。通常 $1\\sim2$ 年就需要重新涂覆。目前该类涂料已受到各船级社限制应用在船舶压载水舱部位，涂料生产厂商正在采用“半硬干涂层”来取代它。  \n\n“半硬干涂层”是一类防腐涂层。该类涂层在干燥后，仍处于柔软的状态，虽然它们涂装在压载水舱部位后，不会受到海水的流动而被冲刷掉，但是仍不能干燥到可以任意接触或在上面行走的状态，一般也只作为锈蚀钢板表面的临时性防腐保护。  \n\n目前船舶压载水舱涂料主要的应用种类是环氧类的硬涂层，根据国外有关的船舶涂料检验实验室对部分船舶漆厂家的压载舱涂料性能检验结果来看，厚膜环氧型的硬涂层具有优良的附着力和耐模拟摇摆试验舱的加速试验，因此在PSPC标准中将环氧型压载水舱涂料作为优选类型来规定。  \n\n(3）船舶压载舱保护涂层性能标准的主要技术内容PSPC标准强制执行的日期从2008年7月1日起以后签订合同船舶，或者2009年1月1日开始建造的船舶，或者2012年交付使用的船舶。适用于所有500吨以上船舶。其中保护涂层的主要技术要求如下。  \n\n$\\textcircled{1}$ 涂料体系必须通过第三方的认可。$\\textcircled{2}$ 环氧类涂料（或其他类型涂料）两道，干膜厚 $320\\mu\\mathrm{m}$ ，两道涂层之间要有颜色差别，并且面漆要求浅色，例如浅灰色、米黄色、米色、泳池蓝/绿色。$\\textcircled{3}$ 认可的涂料体系性能必须达到如下要求之一。a.通过PSPC 标准附录1，或者相当的试验，其涂层的生锈和起泡要符合最小的要求。b.或者保护涂层体系在实船上已使用5年以上，涂层仍保持“良好（good)”状态。$\\textcircled{4}$ PSPC标准附录1的技术要求。a.环氧涂料体系在进行模拟试验前必须达到的要求，见表3-4-23。  \n\n表3-4-23 环氧涂层基本要求  \n\n\n<html><body><table><tr><td>试验项目</td><td>要求</td><td>备注</td></tr><tr><td>红外鉴定 密度 涂层空隙率</td><td>树脂和固化剂 树脂和固化剂 90V，无针孔</td><td>图谱 ISO 2811—1974 电火花检测仪</td></tr></table></body></html>  \n\nb.环氧涂料体系必须通过压载舱条件的模拟摇摆舱试验和冷凝舱试验，模拟摇摆舱的装置示意图和试验要求见图3-4-19和表3-4-24。  \n\n![](images/0cea159f4f1fde92d53af3a2afd4717dd77c84af1b2b4dbb0b9ea0c0b0142122.jpg)  \n图3-4-19 压载舱涂层试验的摇摆舱  \n\n表3-4-24 模拟摇摆舱试验  \n\n\n<html><body><table><tr><td>试样规格</td><td>200mmX 400mmX3mm</td></tr><tr><td>试样预处理</td><td>喷砂达到Sa2.5级，喷涂无机锌车间底漆 车间底漆在沿海环境中暴露至少2个月 暴露后轻喷砂或高压水清洗 涂装试验涂料体系</td></tr><tr><td>试验条件</td><td>模拟舱环境条件： 海水（35℃天然或人造海水）14天 干燥(空舱环境)7天 循环试验</td></tr><tr><td>试验时间/天</td><td>180</td></tr><tr><td>试样数量</td><td>5(1#~5#) 1：50℃，加热12h×20℃，冷却12h；循环浪溅海水</td></tr><tr><td>各试样试验要求</td><td>2：与锌阳极配套试验，试样开8mm人造开孔，循环浸泡海水 3#：试样背面20℃冷却，循环浪溅海水 4#：循环浪溅海水 5#：70℃干热暴露180天</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 269,
+        "chunk": "# c.试样在模拟摇摆舱试验后要求达到的技术指标见表3-4-25。  \n\n表3-4-25 试验结果要求  \n\n\n<html><body><table><tr><td>试验项目</td><td>性能要求</td><td>检测标准</td></tr><tr><td>起泡</td><td>无起泡</td><td>ISO 4628/2</td></tr><tr><td>锈蚀</td><td>Ri0级(0%)</td><td>ISO 4628/3</td></tr><tr><td>针孔</td><td>0</td><td>90V</td></tr><tr><td>附着力/MPa</td><td>>3.5</td><td>ISO 4624</td></tr><tr><td>内聚破坏/MPa</td><td>≥3.0</td><td>ISO 4624</td></tr><tr><td>阴极保护电流/（mA²/m²）</td><td><5m</td><td>从锌阳极质量损失计算</td></tr><tr><td>阴极剥离距离/mm</td><td><8</td><td>从人造开孔处计</td></tr><tr><td>人工划痕处涂层剥离/mm</td><td><8</td><td>从划痕处计</td></tr><tr><td>U形件</td><td>无涂层裂纹、剥落等缺陷</td><td>在U形件任何位置和焊缝处</td></tr><tr><td>柔韧性</td><td>2%的伸长率（仅作为资料性数据）</td><td>参照ASTMD4145（3mm钢板，300μm涂层，在 150mm芯轴上弯曲）</td></tr></table></body></html>  \n\nd.冷凝舱试验要求：冷凝舱底部水温 $40^{\\circ}C$ ， $\\mathrm{RH100\\%}$ ，试验时间180天。冷凝舱的试验装置示意图如图3-4-20所示。  \n\ne.冷凝舱试验后要求涂层达到的技术指标见表3-4-26。  \n\n表3-4-26 冷凝舱试验要求  \n\n\n<html><body><table><tr><td>项目</td><td>依据本标准表3-4-23涂装的环氧基系统的验收标准</td><td>替代系统的验收标准</td></tr><tr><td>样板起泡</td><td>无起泡</td><td>无起泡</td></tr><tr><td>样板锈蚀</td><td>Ri0级(0%)</td><td>Ri0级(0%)</td></tr><tr><td>针孔数量</td><td>0</td><td>0</td></tr><tr><td>附着力</td><td>>3.5MPa，基材和涂层间或各道涂层之间的脱开 面积在60%或以上</td><td>>5.0MPa，基材和涂层间或各道涂层之间的脱开面 积在60%或以上</td></tr><tr><td>内聚力</td><td>>3.0MPa，涂层中的内聚破坏面积在40%或以上</td><td>>5.0MPa，涂层中的内聚破坏面积在40%或以上</td></tr></table></body></html>  \n\n从上述技术数据来看，要达到15年预期使用期效的环氧保护涂料其性能要求是相当高的，第一，要求是高固体分厚膜型涂料，一道干膜厚达到 $160\\mu\\mathrm{m}$ ，要高于目前一般的厚膜涂料（ $100\\sim$ $125\\mu\\mathrm{m})$ 。第二，由于船舶压载舱的内部空间比较狭小，而且有许多加强筋板和型钢，在这样的空间中采用高压无气喷涂施工方法，要求涂层的厚度很好地控制在每道 $160\\mu\\mathrm{m}$ 范围，除要求实施涂装的工人技术水平高外，对涂料本身在较大范围内不流挂的性能也要求高。第三，保护涂层的防腐蚀性能，要求在 $35\\sim50^{\\circ}C$ 的海水环境中暴露具有优良的耐腐蚀性，并在180天模拟舱试验后，主人造划痕处的涂层的剥离距离要求小于 $\\mathrm{{8mm}}$ ；对涂层的综合性能要求很高。  \n\n![](images/feb8dd58beb462d5e61dfda6b95699ff59e520948e88a2d8b494514963547033.jpg)  \n图3-4-20 冷凝舱的试验装置示意图  \n\n(4）压载舱涂料标准的涂层性能指标比较比较IMO的压载舱保护涂层性能标准与国标 $\\mathrm{GB/T\\6823-1986}$ 《船舶压载舱漆通用技术条件》的技术要求，仅对涂料本身的要求有许多不同之处，列举主要不同，见表3-4-27。  \n\n表3-4-27IMO的PSPC标准与GB/T6823—1986的比较   \n\n\n<html><body><table><tr><td>项目名称</td><td>PSPC</td><td>GB/T 6823—1986</td><td>备注</td></tr><tr><td>预期设计寿命/年</td><td>15</td><td>无</td><td></td></tr><tr><td>涂料种类</td><td>环氧或者相当的</td><td>不规定</td><td>采用红外谱图核对</td></tr><tr><td>密度</td><td>规定</td><td>不规定</td><td></td></tr><tr><td>面漆颜色</td><td>较浅</td><td>不规定</td><td>更便于检查</td></tr><tr><td>附着力/MPa</td><td>>3.5</td><td>≥3.0</td><td>模拟加速试验后</td></tr><tr><td>耐冲击性</td><td>不规定</td><td>3J落锤冲击后，无裂纹，无 剥落</td><td></td></tr><tr><td>耐盐雾性</td><td>180天模拟舱试验</td><td>600h，1级</td><td>试验时间和条件均不同</td></tr><tr><td>耐盐水性</td><td>180天模拟摇摆舱试验，35℃</td><td>21天，25℃</td><td>试验时间和条件均不同</td></tr><tr><td>耐热盐水性</td><td>无</td><td>80℃±2℃,2h</td><td></td></tr><tr><td>冷凝试验</td><td>180天模拟冷凝舱试验</td><td>无</td><td></td></tr><tr><td>耐阴极保护性</td><td>Zn阳极，180天，人工划痕处 涂层剥离<8mm</td><td>无</td><td>与实际使用条件一致</td></tr><tr><td>柔韧性</td><td>3mm 钢板，300μm涂层，在 150mm芯轴上弯曲</td><td>无</td><td>作为资料性数据参考使用</td></tr><tr><td>与车间底漆配套性</td><td>有具体试验要求</td><td>文字上要求和常用的车间底 漆配套</td><td>具体化，可操作性，可检查性</td></tr></table></body></html>  \n\n目前国标GB/T6823—1986《船舶压载舱漆通用技术条件》正在修订之中，可以预计新修订的国标GB/T6823《船舶压载舱漆通用技术条件》将会很大部分依据IMO的PSPC标准的内容。但是两者强调的重点是不一样的，国标 $\\mathrm{GB/T\\6823}$ 强调的是压载水舱的涂料体系，IMO的PSPC标准强调的是船舶压载水舱的涂装过程的控制。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 270,
+        "chunk": "# 2.饮水舱漆  \n\n饮水舱漆用于船舶饮水舱、淡水舱和各种淡水柜。饮水舱漆除了应具有良好的附着力、力学性能、防锈性能和耐水性能之外，还要求其漆膜无毒、无味、无臭，对其贮存的清水没有污染，对人体健康无影响，其水质必须符合国家饮用水的标准，选用的品种需获得有关卫生当局的认可、发证。  \n\n在20世纪50年代以前，全世界的船舶饮水舱部位几乎不涂漆或采用涂抹或喷涂水泥浆壁。但经多年实践证明，水泥浆干涸后性脆，当其受到冲击和振动后容易开裂剥落，饮水会被污染。因此目前大部分船舶的饮水舱采用涂料进行保护，一小部分小型民船和输水管道仍沿用水泥涂抹或喷涂防护的方法。用于饮水舱涂料的树脂主要有氯化橡胶、氯乙烯与醋酸乙烯共聚物、氯乙烯与偏氯乙烯共聚物、二乙烯基乙炔共聚物、环氧树脂、聚氨基甲酸酯、十性油与酚醛树脂混合物以及过氯乙烯等。  \n\n（1）饮水舱漆的主要品种  \n\n$\\textcircled{1}$ 乙烯系饮水舱漆乙烯系树脂为基料的饮水舱涂料在世界各国都获得应用和发展。常采用氯乙烯与偏氯乙烯共聚物为基料制成饮水舱涂料，其常用涂层之一就是有一道底漆和三道面漆组成。由于高溶剂含量，该体系已不常用。  \n\n$\\textcircled{2}$ 炔烯共聚物饮水舱漆二乙烯基乙炔共聚物也可用于饮水舱漆，但其缺点十分明显；气味较大且稳定性较差。这类涂料有铁红底漆、铝粉底漆等多个品种。有相关报告称该系饮水舱漆防锈效果可达4年。  \n\n$\\textcircled{3}$ 氯化橡胶饮水舱漆以氯化橡胶基料的饮水舱漆， $20\\mathrm{min}$ 指触干， $30\\mathrm{min}$ 硬干，隔1h可涂下一道。该种涂料涂在磷化底漆上，也可直接在钢板上涂3道面漆。  \n\n由于制造氯化橡胶树脂的原料之一 $\\mathrm{CCl_{4}}$ 直接破坏大气层，所以近年来氯化橡胶树脂产量急剧下降，导致该种饮水舱漆现在在市场上基本绝迹。  \n\n$\\textcircled{4}$ 环氧树脂饮水舱漆环氧树脂在国外早已被广泛地用来涂装饮水舱。环氧树脂饮水舱漆的组成通常是采用低分子量环氧树脂，而固化剂则多为聚酰胺或胺加成物。环氧树脂饮水舱漆有普通型和厚浆型两种环氧涂料，使用时需底面漆配套，其涂装方法举例如下。  \n\n表面处理后喷涂环氧富锌底漆一道，环氧树脂饮水舱底漆一道，环氧树脂饮水舱面漆两道。涂装完毕干燥一周后用 $50^{\\circ}C$ 的淡水浸泡，清洗三次就可以使用。  \n\n由于以上用的均为溶剂型涂料，其残留溶剂很难完全去除，因而会对水质有影响。从目前来看，饮水舱漆向无溶剂双组分的环氧树脂漆方向发展，作为一种新型的高性能涂料，从目前所掌握的资料来看，世界上各著名船舶涂料公司均有生产，其固体含量大多数都在$95\\%\\sim100\\%$ ，一次成膜干膜在 $200\\sim300\\mu\\mathrm{m}$ ，无溶剂环氧树脂饮水舱漆气味小，对封闭的空间如狭小通风不良的舱室施工尤为有利。涂层坚固，耐水性好，还具有一定的耐化学物质及耐磨性，并且能满足欧洲等发达国家的VOC规则。因此使用无溶剂环氧能节约成本并产生非常可观的经济效益和环保效应。",
+        "category": " Introduction"
+    },
+    {
+        "id": 271,
+        "chunk": "# （2）饮水舱漆原料的选择  \n\n$\\textcircled{1}$ 树脂饮水舱涂料是直接关系到人体健康的涂料，所以用于饮水舱的任何涂料都必须经卫生或有关部门检测，批准后方能使用。为了保证饮水舱的水质符合国家要求。在配方设计中除了要考虑涂料的耐水性和施工性能之外，还要注意各组成部分的毒性问题。关于涂料所使用的基料的毒性现有的数据较少，一般来说，大部分树脂如果不含残余的单体、水溶性稳定剂等物质则可认为是无毒的。因此饮水舱涂料所用树脂应补充净化以除去单体。某些环氧树脂漆之所以有毒是因为其中残存有环氧氯丙烷和二酚基丙烷单体，研究表明饮水舱用的环氧树脂向水中迁移的环氧氯丙烷临界允许浓度为 $0.1\\mathrm{{mg/L}}$ 水。聚二乙烯乙炔涂料含有毒性的单体———二乙烯基乙炔和四聚体以及有毒的抗氧剂等，因此涂这种涂料的水舱放出的水要经过炭滤器后才可以饮用。就卫生健康而言用于饮水舱的基料以氯化橡胶、氯乙烯与醋酸乙烯共聚物或偏氯乙烯共聚物、环氧树脂为好。  \n\n$\\textcircled{2}$ 颜料和填料一般饮水舱涂料配方中推荐可使用的料有钛白粉、氧化铁系颜料、滑石粉、重晶石粉、云母粉、高岭土、各种天然硅酸盐等无毒颜料、填料。如需采用富锌底漆时必须检测水中的可溶性锌盐含量。铅系颜料（如红丹)、铬酸锌、铬酸钙等铬酸系颜料由于自身有毒，同时能部分溶于水中，所以是绝对禁止使用的。  \n\n$\\textcircled{3}$ 溶剂因为部分溶剂能长期滞留在漆膜中，所以涂漆的水舱中其水质与使用的溶剂毒性有直接的关系。因此必须采用毒性小的溶剂如：乙醇、正丁醇、丙酮、甲乙酮、松香水等，理想的是不含溶剂。  \n\n$\\textcircled{4}$ 助剂（增塑剂）采用低毒性的增塑剂有：苯甲二酸二辛酯、葵二酸二辛酯、柠檬酸三乙酯、乙酰甘油酯、酒石酸二乙酯等。  \n\n饮水舱表面经施工干燥后，一般需要用淡水浸泡，清洗3次。在舱内长期贮存的饮用水对漆膜产生的溶胀侵蚀作用，会引起漆膜的脱落和微生物对饮用水的污染，因此在出口处有时装有紫外线杀菌器进行消毒处理并附有过滤装置。此外饮水舱的一般卫生处理方法还有高锰酸钾处理法和漂白粉处理法。  \n\n(3）水质分析对饮用水进行水质分析是检验饮用水的水质是否符合国家饮用水卫生标准的一个重要措施，对涂有饮水舱漆的水，除了要满足常规水质分析项目外，还要研究涂料在水中的溶出物、溶出量以及溶出变化规律。同时必要的话还要进行动物毒理试验以提供全面的水质资料。在确保符合饮用水卫生标准的情况下方能作为一种新型涂料用于饮水舱内壁。以下就环氧饮水舱漆水质分析举例说明。  \n\n$\\textcircled{1}$ 水样的制备首先设置模拟实船钢质水柜两个，内壁按饮水舱条件分别涂刷环氧聚酰胺饮水舱漆、环氧酮亚胺饮水舱漆两个品种，室温干燥一周后在无污染的卫生监督下装人一批自来水1t，供水质分析及毒性试验用。同时要存放同一批自来水一并作为化学分析对照用水（日本浸泡面积为 $230\\mathrm{cm}^{2}/\\mathrm{L}$ 水，我国食品业浸泡面积为 $500c m^{2}/L$ 水)。  \n\n$\\textcircled{2}$ 常规水质分析及涂料释放物分析涂漆的水柜在贮存自来水90天内定期做常规水质分析及涂料溶出物分析，结果见表3-4-28和表3-4-29。  \n\n表3-4-28 常规水质分析  \n\n\n<html><body><table><tr><td>检测项目</td><td>国家卫生部标准</td><td>环氧聚酰胺漆水柜的水</td><td>环氧酮亚胺漆水柜的水</td></tr><tr><td>水温/℃</td><td></td><td>5~19</td><td>5~19</td></tr><tr><td>嗅</td><td>无</td><td>无</td><td>无</td></tr><tr><td>味</td><td>无</td><td>无</td><td>无</td></tr><tr><td>色度/度</td><td><20</td><td>14~16</td><td>14~16</td></tr><tr><td>浑浊度/(mg/L)</td><td>5</td><td>2.9~3.2</td><td>2.9~3.1</td></tr><tr><td>pH</td><td>6.5~9.5</td><td>6.7</td><td>6.7</td></tr><tr><td>总硬度/度</td><td><25</td><td>8.4~8.8</td><td>8.4-8.8</td></tr><tr><td>溶解氧/(mg/L)</td><td></td><td>3.7~8.3</td><td>3.6~8.6</td></tr><tr><td>余氯/(mg/L)</td><td><0.3</td><td>0~0.1</td><td>0~0.1</td></tr></table></body></html>  \n\n表3-4-29 涂料释放物分析  \n\n\n<html><body><table><tr><td>检测项目</td><td>国家饮用标准 /X10-§</td><td>环氧聚酰胺漆 /X10-</td><td>环氧酮亚胺漆水柜 /X10-§</td></tr><tr><td>氯化物</td><td><1. 0</td><td>未检出</td><td>未检出</td></tr><tr><td>氰化物</td><td><0.05</td><td>未检出</td><td>未检出</td></tr><tr><td>砷</td><td><0.04</td><td>未检出</td><td>未检出</td></tr><tr><td>硒</td><td><0.01</td><td>未检出</td><td>未检出</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>检测项目</td><td>国家饮用标准 /X10-6</td><td>环氧聚酰胺漆 /X10-5</td><td>环氧酮亚胺漆水柜 /X10-6</td></tr><tr><td>汞</td><td><0.001</td><td>未检出</td><td>未检出</td></tr><tr><td>铬 铅</td><td><0.01</td><td>未检出 未检出</td><td>未检出 未检出</td></tr><tr><td>铁</td><td>≤0.1 <0.3</td><td>痕量～0.12</td><td>0. 048~0.17</td></tr><tr><td>锰</td><td><0.1</td><td>未检出</td><td>未检出</td></tr><tr><td>铜</td><td><0.1</td><td>未检出</td><td>0.012～0.04</td></tr><tr><td>锌</td><td>≤1</td><td>0.134~0.83</td><td>0.6～1.0</td></tr><tr><td>挥发酚类</td><td><0.002</td><td>未检出</td><td>未检出</td></tr><tr><td>亚硝酸胺</td><td>未作规定</td><td>未检出</td><td>未检出</td></tr><tr><td>氨氮</td><td>未作规定</td><td></td><td></td></tr><tr><td>有机胺加成物</td><td>未作规定</td><td></td><td></td></tr><tr><td>环氧氯丙烷</td><td>未作规定</td><td>5X10-9</td><td>1X109</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 272,
+        "chunk": "# $\\textcircled{3}$ 毒理试验 以浸泡养金鱼观察生长情况见表3-4-30。  \n\n表3-4-30 金鱼观察试验结果  \n\n\n<html><body><table><tr><td>测试时间</td><td>环氧聚酰胺组金鱼体长 /cm</td><td>环氧酮亚胺组金鱼体长 /cm</td><td>对照组金鱼体长 /em</td></tr><tr><td>试验前</td><td>3.0</td><td>3.0</td><td>3.0</td></tr><tr><td>试验后30天</td><td>3.1</td><td>3.1</td><td>3.1</td></tr><tr><td>试验后60天</td><td>3.4</td><td>3.4</td><td>3.4</td></tr><tr><td>试验后90天</td><td>3.8</td><td>3.7</td><td>3.7</td></tr></table></body></html>  \n\n病理检查结果：金鱼消化道黏膜均完整。心、肝、肾各组织无明显异常现象。  \n\n以上几项结果表明环氧聚酰胺饮水舱漆、环氧酮亚胺饮水舱漆均符合国家卫生部颁发的生活饮用水卫生标准要求，这两种饮水舱漆可以用于饮水舱内表面。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 273,
+        "chunk": "# 3.成品油舱漆  \n\n成品油舱通常指成品油船的货油舱，成品油船也称为石油产品运输船，确切地说有狭义与广义之分，狭义是指装载和运输石油精制品的船舶，而广义的概念则是指装载和运输石油精制品、石油化学制品以及化学合成产品等的船舶。在这里则取其广义的概念。  \n\n（1）装载对象的特殊性成品油轮装载对象大致分为以下几大类。  \n\n$\\textcircled{1}$ 石油提炼产品包括汽油、发动机燃料油、煤油、柴油、石脑油等精炼油类；重油、沥青、红油等黑色石油提炼产品；润滑油、机油等。  \n\n$\\textcircled{2}$ 石油化学制品该类装载对象有烷烃（脂肪族）类化合物和苯、甲苯、二甲苯等芳 香族（芳烃）类化合物。  \n\n$\\textcircled{3}$ 化学合成制品类包括有机化学物一—醇类、酮类、胺类、醚类、酯类等；碱性化学物——磷酸钠、苛性碱等；酸性化学物—醋酸、脂肪酸等。  \n\n$\\textcircled{4}$ 天然油脂类 包括各种动物油、植物油等。  \n\n$\\textcircled{5}$ 其他一些食用类 包括蜂蜜、果汁、酒类等。  \n\n上述装载对象，有的具有很强的溶解性和渗透性，有的具有很强的腐蚀性，有的则和被食用物品接触，因此它们对涂层提出了很高的要求。更为甚者，作为一级油轮的成品油舱在空载时往往被兼作压载舱，这样货物与海水的交替装载使舱内的涂层处于一种十分严酷的腐蚀环境，所以，必须具备特殊性能的涂料才能当此重任。  \n\n（2）成品油舱漆的品种作为成品油舱漆，必须具备以下性能。  \n\n① 化学结构致密，能抵抗各种装载对象的溶解、渗透和腐蚀，并且不会污染所装载的货物。  \n\n②具有优良的耐海水性能和耐货物-海水交替装载的性能，即使是涂层吸附了一部分货物，本身发生了溶胀，也不会出现遇水剥落现象，或失去原来的抗水能力，而在货物卸下后，溶胀的涂层会恢复原有的状态和性能。  \n\n$\\textcircled{3}$ 涂层沾上货物或其他污物后清洗容易，并且涂层应具有一定的耐热性能，以抵抗货物的加热和热水清洗。  \n\n目前世界上用来作为成品油舱的涂料品种一般都是环氧类（纯环氧和酚醛环氧类）、无机硅酸锌类及聚氨酯类涂料。这些类型的涂料各有各的特点，目前为止还没有一种涂料能适应所有种类的货物。涂料的选择应该根据船舶的主要装载对象来确定。一般来说供应成品油舱漆的厂家会提供耐载荷清单（cargoresistancelist），表明其涂料对各种载荷的抵抗能力，由此可选择应该使用的涂料。表3-4-31为各类涂料的耐载荷参考清单。  \n\n表3-4-31 成品油舱涂料的耐载荷清单  \n\n\n<html><body><table><tr><td rowspan=\"2\">涂料</td><td colspan=\"2\">环氧类成品油舱漆</td><td rowspan=\"2\">聚氨酯类 成品油舱漆</td><td rowspan=\"2\">无机硅锌类 成品油舱漆</td></tr><tr><td>纯环氧类</td><td>酚醛环氧类</td></tr><tr><td>丙酮(酮类)</td><td></td><td>一</td><td>△</td><td></td></tr><tr><td>航空汽油</td><td>十</td><td></td><td></td><td>+</td></tr><tr><td>乙醇(醇类)</td><td>一</td><td>△</td><td>△</td><td>+</td></tr><tr><td>脂肪类石油溶剂</td><td>+</td><td>+</td><td>十</td><td>+</td></tr><tr><td>烷烃</td><td>十</td><td>+</td><td>+</td><td>+</td></tr><tr><td>烯烃</td><td>+</td><td>+</td><td>△</td><td>+</td></tr><tr><td>烷基苯</td><td>+</td><td></td><td>△</td><td>十</td></tr><tr><td>动物油脂</td><td>△</td><td>△</td><td></td><td>△</td></tr><tr><td>芳香族石油溶剂</td><td>+</td><td>+</td><td>+</td><td>+</td></tr><tr><td>谷类</td><td></td><td>十</td><td></td><td>+</td></tr><tr><td>酯类</td><td>△</td><td>△</td><td>△</td><td>△</td></tr><tr><td>乙醚（醚类）</td><td>一</td><td>一</td><td>+</td><td>+</td></tr><tr><td>花生油</td><td>△</td><td></td><td>△</td><td>+</td></tr><tr><td>牛乳</td><td>△</td><td>△</td><td>△</td><td>一</td></tr><tr><td>石脑油</td><td>+</td><td>十</td><td></td><td>+</td></tr><tr><td>石油</td><td>△</td><td>+</td><td>+</td><td>△</td></tr><tr><td>砂糖液</td><td></td><td>十</td><td>△</td><td>一</td></tr><tr><td>海水</td><td>+</td><td>+</td><td>+</td><td>△</td></tr></table></body></html>\n\n注：1.该表摘自于International Paint公司和日本中国涂料的“cargo resistance list”。2. $+$ 表示适合； $\\Delta$ 表示有条件适合；一表示不适合。  \n\n$\\textcircled{1}$ 环氧类成品油舱漆环氧类成品油舱漆大致可分为纯环氧类、酚醛环氧类、环氧沥青类。由于健康问题，环氧沥青类已逐步淘汰。所以现在主要有纯环氧和酚醛环氧两类环氧成品油舱漆。  \n\n环氧树脂因含有极性极高而不易水解的脂肪羟基和醚键使其不仅与被涂物面的附着力好，而且耐化学品性高。当配方选择适宜时则具优良的耐水、耐油、耐溶剂等性能，且对白油也不会污染，因此环氧类涂料国内外广泛用作油、水舱涂料。  \n\n环氧类成品油舱漆在施工时，漆膜厚度不能低于 $250\\mu\\mathrm{m}$ ，但也不要超过 $500\\mu\\mathrm{m}$ ，一般膜厚控制在 $300\\mu\\mathrm{m}$ 。漆膜太厚，会造成漆膜过脆进而漆膜的剥落。表3-4-32为各类环氧成品油舱漆的要求及总体性能。  \n\n表3-4-32 环氧成品油舱漆的要求和性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">环氧油舱漆类型</td><td rowspan=\"2\">涂装道数 /道</td><td rowspan=\"2\">干膜厚度 /μm</td><td rowspan=\"2\">表面处理</td><td rowspan=\"2\">施工温度</td><td colspan=\"3\">防腐蚀性能</td></tr><tr><td>化学品</td><td>溶剂</td><td>水</td></tr><tr><td>聚酰胺固化环氧</td><td>2</td><td>300</td><td>Sa2.5</td><td>不小于10℃</td><td>良好</td><td>良好</td><td>良好</td></tr><tr><td>胺加成物或多胺固化环氧</td><td>3</td><td>250</td><td>Sa2.5</td><td>不小于10℃</td><td>优良</td><td>良好</td><td>良好</td></tr><tr><td>异氰酸酯固化环氧</td><td>3</td><td>250</td><td>Sa2.5</td><td>0℃</td><td>良好</td><td>良好</td><td>优良</td></tr><tr><td>胺固化酚醛改性环氧</td><td>3</td><td>300</td><td>Sa2.5</td><td>15℃施工加热，60～80℃热固化</td><td>最佳</td><td>良好</td><td>良好</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 聚氨酯类成品油舱漆聚氨酯类成品油舱涂料是由聚酯、聚醚、多元醇或羟基丙烯酸树脂与异氰酸酯预聚物构成的双组分涂料，适用于运载石油品、溶剂等。  \n\n聚氨酯类涂料有以下优点：  \n\na.能在低温（ $0^{\\circ}C$ 下）固化；  \nb.耐石油溶剂，对航空煤油质量无影响；  \nc.有全面的耐化学品性能；  \nd.耐动植物脂肪酸。  \n\n聚氨酯类成品油舱涂料的缺点在于该类产品气味大，对人体有害，另外由于成品油舱环境条件差，所以施工困难。为减少施工道数国外正开发厚浆型、无溶剂型聚氨酯类涂料。  \n\n$\\textcircled{3}$ 无机硅酸锌类成品油舱漆通常使用的无机硅酸锌类成品油舱漆是由锌粉、硅酸锌或磷酸锌、硅酸乙酯等组成。该涂料机械强度高，具有良好的耐腐蚀、耐海水、耐油、耐中性化学品 $\\mathrm{\\Phi}_{\\mathrm{{\\tiny{PH}=5\\sim9}}}$ 、中性溶剂的性能。但不耐含酸碱性的装载物，因为所有酸碱性物品都会腐蚀锌。目前使用的品种有水溶性无机锌粉底漆和溶剂性无机锌粉底漆。表3-4-33为两种无机锌漆的比较。  \n\n无机锌粉漆施工时干膜厚度不能过厚，一般控制在 $70\\mathrm{\\sim}100\\mu\\mathrm{m}$ ，过厚会引起龟裂。  \n\n表3-4-33 无机锌漆的比较  \n\n\n<html><body><table><tr><td rowspan=\"2\">无机硅酸锌油 舱漆类型</td><td rowspan=\"2\">干性</td><td rowspan=\"2\">表面处理</td><td rowspan=\"2\">车间底漆的适应性</td><td colspan=\"5\">防腐蚀性能</td></tr><tr><td>耐油</td><td>耐原油</td><td>耐白油</td><td>耐酸碱</td><td>耐水</td></tr><tr><td>硅酸钠(水性)</td><td>快</td><td>Sa3</td><td>适用于无机锌底漆</td><td>优良</td><td>不适用于含硫多的原油</td><td>良好</td><td>劣</td><td>优异</td></tr><tr><td>硅酸乙酯(溶剂型）</td><td>快</td><td>Sa2.5</td><td>适用于无机锌底漆</td><td>优良</td><td>不适用于含硫多的原油</td><td>良好</td><td>劣</td><td>良好</td></tr></table></body></html>  \n\n(3）成品油舱涂装的特殊性成品油舱涂装常称作“特涂”，需要以下特定的施工条件。  \n\n$\\textcircled{1}$ 必须在船上作整体涂装  \n\na.成品油舱漆都是致密的化学固化型涂料，这些涂料有严格的复涂间隔期，超过了涂装复涂间隔期在其表面继续涂装，则涂层间附着力不够，易发生层间剥离现象。从分段涂装到整体合拢后修补，间隔时间很长，必然大大超出了复涂间隔期，因此修补区域与原涂层的交界处往往很难附着好。  \n\nb.分段涂装后，往往堆放在露天，时间一长，涂层质量必受影响，尤其在漆膜完全固化前，如遇下雨、大雾、落霜等天气更易破坏涂膜。  \n\nc.分段涂装后在运输、吊装时难免损伤涂层，而且分段预涂装工作不大可能做到$100\\%$ ，合拢后往往需进行烧焊工作，加上分段数量多，焊缝修补工作量大，焊缝的涂装又是特殊涂装中的关键性工作，大量的焊缝修补涂装，很难保证其涂装质量。  \n\n$\\textcircled{2}$ 必须严格进行温度和露点管理  \n\na.由于成品油舱漆都是双组分化学固化型涂料，故其干燥受周围环境的温度影响很大，尤其是环氧类成品油舱漆在环境温度低于 $10^{\\circ}C$ 时固化速率很慢，低于 $5^{\\circ}C$ 大多数品种几乎停止固化。所以要求施工中，漆膜固化环境温度应尽量高于10℃。另外在夏季，温度过高同样会影响涂装质量，同时也会使喷砂后的钢材很快返锈，所以温度管理十分必要。  \n\nb.比温度管理更重要的是露点管理。所谓露点是指在该环境的温度和相对湿度的条件下，环境温度若下降到物体表面刚刚开始结露时的温度，这一温度即该环境条件下的露点。  \n\nc.涂装作业时的湿度对涂层的性能会带来重大影响，一般涂装作业都要求环境的相对湿度在 $85\\%$ 以下，而对于特殊涂装来说，如单纯规定环境湿度在 $85\\%$ 以下是远远不够的，将会发生不少麻烦，甚至产生差错与失误。一般涂装中被涂物体（如分段）表面的温度与大气的温度差别不大，所以当环境相对湿度在 $85\\%$ 以下时，表面不会发生结露现象。而成品油舱涂装不同，由于整船涂装一般都是在船体漂浮在水面的状态时进行，钢板浸水的部位，其温度低于大气的温度，几乎与外界水温相等，其表面很容易发生结露。尤其是舱内温度与外界水温相差悬殊时（舱内温度大大高于水温)，结露现象则难以避免。这是特殊涂装中一个很突出的困难问题，需要通过去湿和实现露点管理来解决。所谓露点管理，则是：判别被涂物表面温度与露点之间的差距，以确定能否进行涂装（一般要求是被涂表面的温度应当高于露点温度 $3^{\\circ}C$ 以上)；被涂物表面温度接近露点或低于露点时，应当通过改变环境条件（降温、去湿）或提高被涂表面温度，创造合适的涂装条件。这就是露点管理所要解决的问题。  \n\n为了适应整体涂装和温度、露点管理，还需要采用许多特殊的设备和特定的施工工艺，这也是成品油舱漆施工的关键所在。  \n\n$\\textcircled{3}$ 表面处理的特殊性众所周知，涂装质量的好坏，最关键的环节在于表面处理的质量。而成品油船由于装载特殊的货物，需要在特定的条件下施工，涂装特殊的涂料，就需要认真地进行表面处理。与一般涂装不同，有以下特定的要求。  \n\na.结构性处理在分段组装前应当对所有尖锐的自由边缘作倒角处理，达到边缘呈$R{=}2\\operatorname*{mm}$ 左右的圆角状态。在分段组装后，应对所有由于切割焊接所引起的表面不平整处进行补焊、磨光等处理，以求得到良好、光滑的被涂表面状态。  \n\nb.整体喷砂处理在整体涂装前，分段进行喷砂处理。要求在车间底漆受破坏的区域达到 $\\mathrm{Sa2}.5\\sim3$ 级，粗糙度在 $40\\sim75\\mu\\mathrm{m}$ 。车间底漆完好区域，应达到 $70\\%\\sim80\\%$ 的车间底漆被除去。因此，对磨料、施工工艺以及脚手架搭建等均有特定的要求。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 274,
+        "chunk": "# 4.润滑油/燃油舱漆  \n\n除了上述的成品油舱外，还有燃油舱、润滑油舱、污油舱等。  \n\n(1）燃油舱燃油舱一般不需要涂料保护。为了防止舱壁在建造过程中的锈蚀，减少封舱加油前的清洁工作量，常在分段阶段涂装一道石油树脂漆（亦称干性防锈油)。石油树脂漆是由石油树脂溶于烃类溶剂中获得，一般固体含量为 $50\\%$ 左右，涂于钢材表面能干燥成膜，当燃油舱开始装油以后，漆膜将逐步溶于燃油，舱壁将直接接触燃油而不致腐蚀。  \n\n石油树脂在烃类溶剂中很容易溶解，和许多树脂混溶性良好，由于结构中不含极性基团，因此有良好的抗水性、耐酸碱性。  \n\n石油树脂抗氧化性能欠佳，因此必须加入少量的抗氧剂。常用的抗氧剂为胺类或酚类化合物，其用量为石油树脂的 $0.5\\%\\sim2\\%$ 0  \n\n石油树脂漆由于不含有防锈颜料，故防锈性能欠佳，保护期限较短，燃油舱也可涂装一道车间底漆加以保护。表3-4-34为石油树脂燃油舱涂料的参考配方。  \n\n表3-4-34石油树脂燃油舱涂料参考配方  \n\n\n<html><body><table><tr><td>组成</td><td>质量分数/%</td><td>组成</td><td>质量分数/%</td></tr><tr><td>石油树脂</td><td>50.0</td><td>溶剂</td><td>45.0</td></tr><tr><td>助剂</td><td>5.0</td><td>合计</td><td>100.0</td></tr></table></body></html>  \n\n(2）润滑油舱润滑油舱可像燃油舱一样采用石油树脂漆进行临时性保护，而更好的保护方法是用纯环氧类涂料保护，尤其是主机滑油循环舱，其贮藏的油质要求高，通常采用纯环氧涂料保护。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 275,
+        "chunk": "# 5.货舱漆  \n\n货舱漆用于船舶货舱内部。要求附着力良好、有较高的耐磨性能，要易于修补，各涂层的涂装间隔时间应符合产品技术要求。  \n\n大型的散装货轮，在往返途中单向装运货物，难免有空船或装货不足的现象，因此必须在中间一个货舱内注入海水来压舱，这样货舱上所涂的涂料就必须像压载水舱一样能耐海水浸泡。所以货舱兼作压载舱时，货舱漆应有优良的耐水性能和抗腐蚀性能。  \n\n用于装载散装谷物食品货舱的货舱涂料，必须具有对谷物无毒性、无污染。应符合“中华人民共和国食品卫生法（试行)”（1982）中有关条例，并取得相关当局的认可证书。在国际上，装载谷物货舱的货舱漆，通常需要达到FDA规定。  \n\n作为货舱的保护涂料大致有三种类型： $\\textcircled{1}$ 醇酸类； $\\textcircled{2}$ 改性环氧类； $\\textcircled{3}$ 纯环氧类。  \n\n醇酸类货舱漆一般用于经济型、小型船的应用；改性环氧类货舱漆由于其对底材的容忍性，常用于货舱的维修；而纯环氧类由于其出色的性能，常用于新造船。  \n\n用于装载散装谷物食品货舱的货舱涂料的配方中颜填料必须无毒性，一般采用如铝粉、钛白粉、氧化铁红、滑石粉等颜填料。  \n\n完整的货舱漆配套系统由车间底漆、防锈漆、中间层漆及面漆组成。在涂货舱漆前，裸露钢板的表面处理应符合GB8923的规定。按货舱漆的不同品种，其除锈等级须分别达到喷、抛射除锈 $S a2{\\sim}2\\frac{1}{2}$ 级，手工机械除锈 $S_{t2\\sim3}$ 级。",
+        "category": " Introduction"
+    },
+    {
+        "id": 276,
+        "chunk": "# 七、船舶漆的涂装  \n\n“船舶涂装”是指将涂料施涂到船舶钢材表面的工艺操作过程。它不仅包括涂装前涂料的配套选择、待涂表面的预处理、涂装设备的选用、涂装工艺和涂装过程的检测等，而且还包括涂装过程中污染的处理、个人防护和设备的保养维修等系列涂装管理工作。因此说直接影响“船舶涂装”涂膜质量的三个要素是涂装材料、涂装工艺和涂装管理。  \n\n(1）涂装材料选用涂料时，一般从涂料的作业性能、涂膜性能、经济效果等方面综合考虑。一般采用吸取他人经验或通过试验确定等方法。由于前几章已系统地论述过，所以本章对涂料选用不再述说。  \n\n(2）涂装工艺获得优质涂膜的必要条件是充分发挥涂装材料性能的涂装工艺。涂装工艺包括涂装技术的合理性和先进性；涂装设备和涂装工具的先进性和可靠性；涂装环境条件以及涂装操作人员的技能、素质等。  \n\n(3）涂装管理涂装管理是确保涂装工艺的实施，达到涂装目的和涂膜质量的重要条件。涂装管理包括工艺管理、设备管理、工艺纪律管理、现场环境管理、人员管理等。涂装管理是现代涂装过程中必不可少的环节。  \n\n涂装三要素是相互依存的制约关系，忽视哪一方面都不可能达到涂装目的和获得优质的涂膜。",
+        "category": " Introduction"
+    },
+    {
+        "id": 277,
+        "chunk": "# 1.船舶涂装钢材表面处理  \n\n在船舶漆的涂装工序中，底材涂装前的表面除锈处理质量直接影响到涂层保护性能。表3-4-35为经验总结的涂层性能因素。  \n\n表3-4-35各种因素对涂层寿命的影响  \n\n\n<html><body><table><tr><td>影响因素</td><td>影响程度/%</td><td>影响因素</td><td>影响程度/%</td></tr><tr><td>表面处理质量</td><td>49.5</td><td>涂料种类</td><td>4.9</td></tr><tr><td>膜厚（道数）</td><td>19.1</td><td>其他因素</td><td>26.5</td></tr></table></body></html>  \n\n表面除锈处理不仅指除去钢材表面的铁锈，而且还包括除去覆盖在钢材表面的氧化皮，旧涂层以及沾污的油脂、灰尘、残留焊渣等污物；此外，钢材经表面处理后还形成一定的表面粗糙度。所以，钢材表面处理的质量主要是指上述污物的清洁程度和处理后表面所形成的粗糙度的大小。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 278,
+        "chunk": "# （1）钢材表面处理质量的评定  \n\n①国家标准《涂装前钢材表面锈蚀等级和除锈等级》按国家标准GB8923（与相应的ISO、SSPC标准等同）可将未涂装过的钢材表面原始锈蚀程度分为四个“锈蚀等级”，将未涂装过的钢材表面除锈后的质量分为若干个“除锈等级”。钢材表面的“锈蚀等级”和“除锈等级”均可用文字叙述和典型样板的照片共同确定。  \n\na.锈蚀等级国家标准根据钢材表面氧化皮覆盖程度和锈蚀状况将其原始锈蚀程度分为四个等级，分别以A、B、C、和D表示，如图3-4-21所示。  \n\n![](images/1a0781f61a5c819388b90c573d4e3fd604a17c5948f199e4c54cab6feecb80bd.jpg)  \n图3-4-21 钢板原始等级（照片源自SSPC）  \n\nA全面的覆盖着氧化皮而几乎没有铁锈的钢材表面。  \nB已发生锈蚀，并且部分氧化皮已经剥落的钢材表面。  \nC氧化皮已因锈蚀而剥落，或者可以刮除，并有少量点蚀的钢材表面。  \n\nD氧化皮已因锈蚀而全面剥落，而且已普遍发生点蚀的钢材表面。  \n\nb.除锈等级国家标准对喷丸（砂）或抛丸除锈、手工和动力工具除锈以及火焰除锈的钢材表面清洁度规定了除锈等级，并且分别以字母“Sa”、“St”和“F1”表示。  \n\n喷射或抛射除锈分四个等级—Sal、Sa2、Sa2.5和Sa3。  \n\nSal级：轻度喷砂除锈，表面应无可见的油脂、污物、附着不牢的氧化皮、铁锈、涂料涂层和杂质。  \n\nSa2级：彻底的喷砂除锈，表面应无可见的油脂、污物、氧化皮、铁锈，油漆涂层和杂质基本清除，残留物应附着牢固。  \n\n$\\mathbf{S}\\mathbf{a}\\bar{2}\\frac{\\mathbf{\\Omega}1}{\\mathbf{\\Omega}2}$ 级：非常彻底的喷砂除锈，表面应无可见的油脂、污物、附着不牢的氧化皮、铁锈、涂料涂层和杂质，残留物痕迹仅显示点状或条纹状的轻微色斑。  \n\nSa3级：喷砂除锈至钢材表观洁净，表面应无油脂、氧化皮、铁锈、涂料涂层和杂质，表面具有均匀的金属光泽。  \n\n$\\cdot$ 手工或动力工具除锈，分两个等级 1 St2和St3。  \n\nSt2：彻底的手工和动力工具除锈，表面应无可见的油脂、污物、附着不牢的氧化皮、铁锈、涂料涂层和杂质。  \n\nSt3：非常彻底的手工和动力工具除锈，同St2，但应比St2处理得更彻底，金属底材呈现金属光泽。  \n\n$\\cdot$ 火焰除锈只设一个等级—F1（钢材表面应无氧化皮、铁锈、涂料涂层等附着物，任何残留物的痕迹仅为表面变色不同颜色的暗影)。  \n\n$\\textcircled{2}$ 船舶专业标准“船体二次除锈评定等级”全国船舶标准化技术委员会发布的船舶专业标准“船体二次除锈评定等级”将二次除锈前的钢材表面状态分为三类。  \n\nW——-涂有车间底漆的钢材经焊接作业后，重新锈蚀的表面。  \nF——涂有车间底漆的钢材经火工矫正后，重新锈蚀的表面。  \nR——涂有车间底漆的钢材因暴露或擦伤，重新锈蚀的表面，或附有白色锌盐的表面。  \n二次除锈的手段可分为手工或动力工具除锈和喷射或抛射除锈两类。  \n\na.手工或动力工具除锈的质量等级设有三个等级—-—P1、P2和P3。  \n\n·P1用动力钢丝刷和动力砂纸盘彻底地清除锈和其他污物，仅留有轻微的痕迹，经清理后，表面应具有金属光泽。  \n\n·P2用动力钢丝刷、动力砂纸盘或用上述工具清除几乎所有的锈和其他污物，但局部仍可看见少量锈迹。  \n\n·P3用动力钢丝刷、动力砂纸盘或手工工具清除浮锈和其他污物。  \n\nb.喷射或抛射除锈的质量等级设有三个等级——b1、b2和bs。  \n\n·b1 以喷射磨料的方式彻底地清除锈和其他污物，仅留有轻微的痕迹。  \n\n·b2以喷射磨料的方式除去几乎所有的锈和其他污物，但局部仍可看见少量锈迹。  \n\n·bs以轻度喷射磨料的方式清除锈、锌盐和其他污物，但表面上允许留有车间底漆和少量锈迹。  \n\n(2）表面粗糙度的评定国际标准ISO8503用来评定喷射除锈后钢材表面粗糙特征，该标准由四个部分组成。其中ISO8503-2（比较样块法）是目前国际上最常用和最简便的一种评定方法。我国国家标准和该标准均采用表面粗糙度基准比较样块以直观或触摸方式进行比较来判断喷射清理过的表面粗糙度。如图3-4-22所示为比较样块的示意图，图3-4-22(a)为喷砂表面粗糙度比较样块，它是反映喷射棱角砂类磨料（GRIT）而获得的表面粗糙特征的样块，所以该样块又称为G样块；图3-4-22（b）为喷丸表面粗糙度比较样块，它是反映喷射丸类磨料（SHOT）而获得的表面粗糙特征的样块，所以该样块又称为S样块。  \n\n![](images/4d785038e9e56cfa988fafb633e978f8f0582e4150d8a4241d04033d9f491921.jpg)  \n图3-4-22 比较样块示意图  \n\n评定表面粗糙度的步骤是：先清除待测钢材表面的浮灰和碎屑，然后根据喷射清理所用的磨料，选择合适的表面粗糙度比较样块（G或S样块）将其与被测表面的某一区域形成对照，依次将被测表面与样板上的四个部分进行目测比较，必要时可用放大倍数不大于7倍的放大镜观察，确定比较样块上高于和低于被测表面粗糙度的部分。再根据表3-4-36就可得出被测表面粗糙度的等级。  \n\n表3-4-36 表面粗糙度的等级划分  \n\n\n<html><body><table><tr><td rowspan=\"2\">级别</td><td rowspan=\"2\">定义</td><td colspan=\"2\">粗糙度参数值Ry/μm</td></tr><tr><td>丸类磨料(SHOT)</td><td>棱角砂类磨料(GRIT)</td></tr><tr><td>细细</td><td>钢材表面所呈现的粗糙度小于样块区域1所呈现的粗 糙度</td><td><25</td><td><25</td></tr><tr><td>细</td><td>钢材表面所星现的粗糙度等同于样块区域1，或介于区 域1和区域2所呈现的粗糙度</td><td>25~40</td><td>25~60</td></tr><tr><td>中</td><td>钢材表面所呈现的粗糙度等同于样块区域2，或介于区 域2和区域3所呈现的粗糙度</td><td>40~70</td><td>60~100</td></tr><tr><td>粗</td><td>钢材表面所呈现的粗糙度等同于样块区域3，或介于区 域3和区域4所呈现的粗糙度</td><td>70～100</td><td>100~150</td></tr><tr><td>粗粗</td><td>钢材表面所呈现的粗糙度大于或等同于样块区域4所呈 现的粗糙度</td><td>> =100</td><td>>=150</td></tr></table></body></html>  \n\n如目测评定有困难，也可采用触摸法对被测表面的粗糙度做出正确的评定。方法是用指甲背面或夹在拇指和食指间的木质触针在被测表面和样块表面交替划动，根据触觉来判定表面粗糙度的等级。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 279,
+        "chunk": "# 2.船舶涂料涂装工艺  \n\n由于船舶建造的特定工艺程序不同于一般工业产品的生产，决定了船舶涂装工艺也应与造船工艺程序相适应，而又不同于一般工业产品涂装的特定的工艺程序。通常造船的整个过程中，涂装工作（包括表面处理）可分为以下工艺阶段：①钢材预处理和涂装车间底漆；$\\textcircled{2}$ 分段涂装； $\\textcircled{3}$ 船台涂装； $\\textcircled{4}$ 码头涂装； $\\textcircled{5}$ 坞内涂装； $\\textcircled{6}$ 装件涂装。  \n\n这里将重点对后五部分进行论述。  \n\n(1）分段涂装工艺分段涂装是船舶涂装中最主要和最基本的一环，除了特种船舶的特殊部位（如成品油舱的货油舱)，船体的各个部位，在分段阶段都要进行部分或全部涂层的涂装。船体分段有平面分段和立体分段两大类。立体分段结构比较复杂，表面处理与涂装工作的难度亦高一些。  \n\n分段涂装作业时应注意以下几点。  \n\n$\\textcircled{1}$ 分段的搁置应尽量避免高空作业和顶向作业，应有利于表面处理（二次除锈）作业时的磨料清理，有利于人员进出和通风换气，必要时应增设工艺孔和分段。露天作业时，应避免周围污染源的影响，避免涂装作业时产生的粉尘，漆雾对周围可能产生的污染。  \n\n$\\textcircled{2}$ 分段涂装作业前，要确认船体结构是否完整，焊接、火工校正、焊接清理工作是否结束，特别是分舱标记，水线水尺等标记是否焊好，机电管系的预装工作是否完成等，以避免涂装结束后再进行上述工作而破坏涂层。  \n\n$\\textcircled{3}$ 分段涂装前，对分段的大接缝、尚未进行密性试验的焊缝以及不该涂漆的部分与构件（如外板或液舱内已装好的牺牲阳极，外加电流保护用的电板等)，应用胶带或其他包裹材料进行遮蔽。  \n\n$\\textcircled{4}$ 分段涂装结束，应在涂层充分干燥后才能启运。对分段中非完全开的舱室，应测定溶剂气体的浓度，在确认达到规定的合格范围以内才能启运。  \n\n$\\textcircled{5}$ 分段上船台前，与墩木相接触的部位的涂层必须充分干燥。墩木处必须上一层耐溶剂性能好的聚乙烯或聚酯薄膜（一般厚度为 $0.1\\mathrm{mm}$ 左右)，以免墩木擦伤涂层。  \n\n(2）船台涂装工艺船台涂装是指分段在船台上合拢以后直至船舶下水前这一过程中的涂装作业。该阶段涂装主要工作内容为分段间大接缝修补涂装、分段涂装后由于机械原因或焊接、火工原因引起的涂层损伤部位的修补以及船舶下水前必须涂装到一定阶段或全部结束的部位的涂装。建造进度许可的话，可以对某些牺装工作完整性较好的舱室作完整性涂装。船台涂装应特别注意以下问题。  \n\n$\\textcircled{1}$ 船台涂装作业以及后面将介绍的码头涂装与坞内涂装均为露天作业，要尽量利用好天气抓紧工作并严格做好环境的温度和湿度管理。  \n\n$\\textcircled{2}$ 分段间的大接缝及分段阶段未作涂装的密性焊缝，应在密性试验结束以后进行修补涂装。  \n\n$\\textcircled{3}$ 修补涂装时修补区域的涂料品种、层数、每层的膜厚要与周围涂层一致，并按顺序涂装。修补区域的周围涂层要事先打磨成坡度，叠加处要注意平滑，避免高低不平。  \n\n$\\textcircled{4}$ 如船舶下水后直到交船不再进坞，则水线以下的部位（包括水线、水尺）应涂装完整。船底与船台墩木或支柱接触的部位要进行移墩修涂，以保证这些部位涂层完整。  \n\n$\\textcircled{5}$ 船体外板的脚手架、下水支架，往往有一部分焊在外板上，下水前需切割清除，磨平焊脚，做好修补涂装。  \n\n$\\textcircled{6}$ 船体外板涂装时，对牺牲阳极、声呐探测器、螺旋桨、外加电流保护用的电极等不需要涂装的部分，应做好遮蔽，避免被涂料污染。  \n\n(3）码头涂装工艺码头涂装是船舶下水到交船前停靠在码头边进行装作业阶段的涂装。除了必须在坞内进行的涂装作业外，该阶段应该对全船各个部位作好完整性涂装。  \n\n由于码头装作业的特点，涂装时必须注意以下事项。  \n\n$\\textcircled{1}$ 船体外板水线以上区域，应在临近交船前涂装（亦可在进坞时涂装)。涂装前，为防止干舷旁排水孔流出的污水对涂装作业的影响，应设置适当的临时导水管导流，或以木栓塞住排水孔，直至涂装结束，漆膜完全干燥为止。  \n\n$\\textcircled{2}$ 不同涂层的交界处（如水线区与干舷区之间）为防止不同涂层不合理叠加而引起渗色，咬底等病，应当按生产设计规定的正确顺序进行叠接。  \n\n$\\textcircled{3}$ 液舱内部（除特涂舱室)，大多在分段阶段已完成涂装，在船台阶段往往由于装工程的原因来不及修补，故多数在码头阶段修补涂装，由于液舱往往分布在船底部、、或船两侧，船舶下水后有部分舱壁的外侧浸于水中，故舱内容易结露，所以要采取措施（如通风，除湿)，杜绝潮湿表面涂装，实在难以避免结露的部位，要留待进坞时涂装。  \n\n$\\textcircled{4}$ 机舱内部情况较为复杂，大多在分段阶段已作好涂装，码头阶段仅作修补和最后一道面漆。机舱设备在系泊试验动车以后，油水难免流人舱底，增加了清洁工作的难度，所以舱底涂层修补工作应赶在试车前结束为宜。  \n\n$\\textcircled{5}$ 甲板分为室内甲板和露天甲板两类。由于码头栖装阶段甲板上人员频繁，又往往堆积较多材料等物品。所以甲板涂装应越接近交船越好。施工时应分区域进行，不影响通行。施工好的表面在涂层完全干燥以前要严禁人员通过，涂层干燥后最好铺上覆盖物，避免过多踩踏，影响交船时的整洁与美观。  \n\n(4）坞内涂装工艺坞内涂装主要是对船体水线以下区域进行完整性涂装，也做一些码头装阶段来不及进行的涂装工作。船舶下水时因为离交船期还有一段时间，船底防污漆一般不应涂装结束，故进坞时往往还需要涂装 $2\\sim3$ 道防污漆。坞内涂装需注意以下事项。  \n\n$\\textcircled{1}$ 船舶下水后到进坞这一段时间，水线以下区域会受到水域内各种物质的污染。涂装前应先用高压水枪认真清洗，除去污泥、杂物，若有油腻沾污，则应用溶剂擦净。有些水域含有较多 $\\mathrm{{\\bar{S}}_{i}^{\\ast}}\\bar{\\bigcirc}_{2}$ 会导致下水前已涂装好的防污漆发黑，则应以砂皮纸磨去发黑严重的部位。如船体表面有海生物附着，则应轻轻刮除，刮除时要避免损伤已有的涂层。  \n\n$\\textcircled{2}$ 船舶一进坞就应将压载水放干净，否则在外板上会凝结水珠，影响涂装。  \n\n$\\textcircled{3}$ 与坞内墩木接触的地方，在整体涂层施工结束后，如涂层不足，原则上应作移墩处理，然后逐道修补涂装。但由于整体涂层刚刚施工完毕，涂层还不十分坚硬，移墩可能会导致新的涂层压伤，所以有些船东不希望移墩，此时可不做移墩处理。但应向船东提交一份坞墩布置图，以便船东可在下次进坞时，要求船坞方面排墩时避开这些部位，补足所缺涂层。避免坞内涂装时移墩的最好方法是在船舶下水前，将船底平底区的中心区域(坞墩密集区)的涂层施工完毕。  \n\n$\\textcircled{4}$ 外板部区域的涂层易被锚链擦伤，肿部区域则易被码头边楞木擦伤，这些擦伤部位往往产生锈蚀，进坞时要重新除锈、补漆。由于补漆工作从头做起，涂层较多，需较长时间，故一进坞就应抓紧这方面工作。  \n\n$\\textcircled{5}$ 水线、水尺、船名、港籍名以及船壳外的各种标记应仔细刷涂，在出坞放水前完全干燥。  \n\n$\\textcircled{6}$ 坞内涂装时，舷旁排水孔的处理方法与码头涂装一样。  \n\n(5）装件涂装工艺船舶装件种类很多，有些如杆、舱口盖、起货杆等大型装件，也有许多如管系附件、电缆导架、扶手、栏杆等小型装件。  \n\n大型装件，往往采用经过预处理并涂有车间底漆的钢材制成，其涂装往往与船体涂装相似，经过二次除锈，然后逐层涂装；小型装件，往往采用酸洗除锈后，或镀锌，或直接涂装防锈底漆。  \n\n所有船舶装件，上船安装前，多数涂上底漆，面漆一般会等到安装后再涂装。这是由于在安装过程中难免因焊接或机械原因损伤涂层，且面漆与周围船体结构同时涂装会有较好的外观效果。装件的涂装应注意以下事项。  \n\n$\\textcircled{1}$ 所有船舶装件，除规定不必涂装的之外（如不锈钢制品、有色金属制品、部分镀锌件等)，上船安装前，都必须事先经过表面处理和涂好防锈底漆（有的则可以涂完面漆)，不允许未经表面处理和涂装的钢质装件上船安装。  \n\n②装件上船安装前所涂的底漆，原则上应该与其所安装的部位的底漆相同，如上船安装前已涂装好面漆，则所涂面漆除涂装说明书有特别规定外，一般应和周围的面漆相同。  \n\n$\\textcircled{3}$ 外购设备或一般装件，应在订购前向制造厂商提供表面处理和涂装的技术要求，  \n对涂料品种、膜厚、颜色等应做出认真仔细的规定，必要时前往检查验收。$\\textcircled{4}$ 装件上船安装后会发生局部涂层破坏，应当用同类型的涂料做好逐层修补。$\\textcircled{5}$ 对一些安装范围广泛、通用性较强的装件，为避免所涂底漆与今后安装部位面漆  \n涂装不配套，可涂通用性较强的环氧类底漆。$\\textcircled{6}$ 装件安装后，最终与周围一起涂装面漆时，要注意保护好不该涂漆的部位。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 280,
+        "chunk": "# 3.船舶涂料涂装工具  \n\n船舶的涂装工具以高压无气喷涂为主，也有使用手工涂刷和辊涂的。在进行船舱内部涂装时一般先手工刷涂，在肋骨背面等不宜进行喷涂和容易漏喷的地方进行涂装，称为预涂，然后再进行全面喷涂。手工涂刷工具主要有漆刷、漆辊、钢皮刮刀、牛角刮刀、塑料刮板及橡皮刮刀等。  \n\n高压无气喷涂的主要设备为高压无气喷涂机或称高压喷漆泵。船厂一般采用的压缩空气驱动泵可分为内阀配气机构型和外阀配气机构型两类。其压力比有多种类型，可分别适用于各种不同材科和不同黏度的涂科。喷涂法施上须掌握以下一些操作技巧。  \n\n（1）用配套的稀释剂将涂料调至适合喷涂的黏度。(2）空气压力最好控制在 $0.3{\\sim}0.4\\mathrm{MPa},$ ，压力过小，漆液雾化不良，表面会形成麻点；  \n压力过大易流挂，且漆雾过大，既浪费材料又影响操作者的健康。对厚膜型涂料，压力要适  \n当提高。(3）喷嘴与物面的距离一般以 $300{\\sim}400\\mathrm{mm}$ 为宜。过近易流挂；过远漆雾不均匀，易  \n出现麻点，且喷嘴距物面远漆雾在途中飞散造成浪费。距离的具体大小，应根据涂料的种  \n类、黏度及气压的大小来适当调整。慢干漆喷涂距离可远一点，快干漆喷涂，距离可近一  \n点；黏度稠时可近一点，黏度稀时可远一点；空气压力大时，距离可远一点，压力小时可近  \n一点。所谓近一点远一点是指 $10\\sim50\\mathrm{mm}$ 之间小范围的调整，若超过此范围，则难以获得  \n理想的漆膜。(4）喷枪可作上下、左右移动，以均匀速度运作，喷嘴要平直于物面喷涂，尽量减少斜  \n向喷涂。当喷到物面两端时，扣喷枪扳机的手要迅速的松一下，使漆雾减少，因为物面的两  \n端，往往要接受两次以上的喷涂，是最容易造成流挂的地方。(5）喷涂时要下一道压住上一道，一般控制 $50\\%$ 的压枪，这样可保证漆膜厚度均匀及  \n不会出现漏喷现象。在喷涂快干漆时，需一次按顺序喷完。补喷效果不理想。(6）在室外空旷的地方喷涂时，要注意风向（大风时不宜作业)，操作者要站在顺风方  \n向，防止漆雾被风吹到已喷好的漆膜上造成难看的粒状表面。(7）喷涂的顺序是：先难后易，先里后外，先高处后低处，先小面积后大面积。这样就  \n不会造成后喷的漆雾飞溅到已喷好的漆膜上，破坏已喷好的漆膜。表3-4-37为高压无气喷涂堂日故陪与排除的方法  \n\n表3-4-37 高压无气喷涂常见故障与排除的方法  \n\n\n<html><body><table><tr><td>故障现象</td><td>产生的原因</td><td>排除的方法</td></tr><tr><td>泵产生空吸动作，无涂料输出</td><td>1.管路中吸人空气 2.柱塞泵座处钢球粘住，滤网堵塞 3.柱塞未拧紧而松动，脱落 4.涂料黏度大吸不进柱塞泵内 5.管路接头泄露严重</td><td>1.打开放泄阀，放去空气 2.拆下清洗 3.重新安装 4.添加溶剂或进行涂料加热 5.重新安装</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>故障现象</td><td>产生的原因</td><td>排除的方法</td></tr><tr><td rowspan=\"2\">气压不足</td><td>1.进风压力不足 2.密封圈磨损</td><td>1.风压应大于0.4MPa 2.更换密封圈</td></tr><tr><td>3.柱塞缸零件产生内外泄露 4.缸体及活塞杆磨损</td><td>3.检查，针对性调整 4.更换磨损部件</td></tr><tr><td>压力波动大</td><td>1．喷嘴太大 2.柱塞单向阀动作失灵 3.贮压器等有关零件产生泄露</td><td>1．选用适合的喷嘴 2.清洗或更换单向阀的钢球 3.检查，针对性维修</td></tr><tr><td>上汽缸不动作</td><td>1.配气机构动作失灵 2.进风压力与风量均不够 3.配气滑阀排气口结冰堵塞</td><td>1.清洗与修正配气零件，并润滑 2.检查管路零件尺寸与安装方向 3.空气加热或加防冻润滑剂</td></tr><tr><td>雾化不良</td><td>1.漆压不高 2.涂料黏度太大 3.喷嘴损坏</td><td>1.调整压力比，清除管路泄露 2.适当添加溶剂或进行中间加热 3.更换喷嘴</td></tr><tr><td>喷嘴堵塞</td><td>1.涂料结皮或过滤不良 2.设备及管路清洗不良 3.喷枪清洗不良</td><td>1.加强涂料过滤 2.拆洗设备及管路 3.拆洗喷枪、喷嘴</td></tr><tr><td>喷枪漏漆</td><td>1.喷枪针形阀磨损 2.密封材料损坏 3.顶针复位弹簧失效</td><td>1.研磨或更新针形阀 2.更新密封材料 3.更新顶针复位弹簧</td></tr><tr><td>压力标值很高但无涂料输出</td><td>4.调节螺母位置不当 1.高压软管堵塞 2.喷枪通道被堵 3.中间加热器内涂料过热堵塞</td><td>4.调整螺母位置 1.检查、清洗、更换高压软管 2.按第六项方法处理 3.拆开并清理残存变质涂料</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 281,
+        "chunk": "# 4.涂层缺陷及修正  \n\n涂料在施工过程中，由于操作不当、干燥及固化期间的环境条件变化或者是涂料自身质量的影响，都会产生种种缺陷。有些缺陷，在涂料施工到基材表面后立即产生，称之为湿膜缺陷；另外一些缺陷，是在涂层干燥及固化阶段以及涂层投入服务使用后产生，最终在涂层干燥状态下可以观察到的，称之为干膜缺陷。  \n\n涂料从生产厂家生产出来，直至其被施工在工件表面，才达到其真正的使用目的。从这种意义上讲，只有施工完毕的涂料才是真正意义上的成品。而涂层的缺陷，无论从实践经验而来，还是相关机构的调查结论来看， $80\\%\\sim90\\%$ 的涂层缺陷都是由于在施工中的不当操作造成的。这些不当的操作存在于表面处理、涂料的施工、干燥及固化期间对温湿度的控制等整个涂装过程。而不当的操作，可能是由于操作人员的技术水平不足、责任心缺乏；或者是由于设备的故障或不足等因素造成。  \n\n以下主要就常见的涂层缺陷的成因、外观状态以及修复方法进行介绍，以求在对涂料的使用过程中，注意控制涂装的各个施工环节，避免产生涂层缺陷；同时当涂层缺陷产生时，可以帮助找到造成缺陷的原因，避免产生更多的涂层缺陷；以及采用合适的方式方法进行修复。  \n\n涂料施工中，常见的涂层缺陷通常有：漏涂，膜厚过低；流挂、帘状流挂或流淌；橘皮；干喷或过喷；针孔；起泡；鱼眼；皱纹/抬起；渗出和碳化；发花；渗透压水泡；针状锈蚀；开裂；分层；粉化；渗色；空泡。  \n\n(1）漏涂或漆膜厚度过低涂料施工时，后道涂层未遮蔽前道涂层或底材，从而在涂层施工完毕后可观察到前道涂层或底材的颜色的状况，称之为漏涂或漆膜厚度过低，如图3-4-23  \n\n![](images/006d833cecea7fedd18f5ac2050dedefd9abd465cb8c78926afbdb3187b1db0f.jpg)  \n图3-4-23 手工电焊缝预涂时的漏涂  \n\n所示。  \n\n漏涂或漆膜过薄经常会发生在结构较为复杂或通行不便的部位、不规整的表面，诸如：夹角、型材反面、过焊孔、老鼠孔、电焊缝和火工切割边缘等部位。这种缺陷通常可直接通过目测观察，对于狭小或复杂的区域，常常可借助小镜子观察。  \n\n涂料施工中，无论是刷涂、辊涂还是喷涂，都会出现这种缺陷。施工中未按规定的膜厚要求进行涂覆是造成该缺陷的主要原因。刷涂时控制漆刷中涂料的含量、刷子行进的速度及力度以及在遇到不规整的表面时，采用点压的方法都可以极大地避免该缺陷的产生。而在辊涂时除了要确保辊筒中涂料的含量及行进的速度和力度外，由于辊筒在涂料施工时先天的不足，无法很好地润湿表面，特别在不规整的部位，往往结合刷涂可以有效地避免漏涂的产生。大面积进行喷涂时，首先对于难以喷涂的部位进行预涂，然后在施工中采用50%接枪和/或十字交叉喷涂的工艺都能有效地避免漏涂和膜厚过低。当然，如果在施工过程中，借助湿膜测厚仪随时监控施工的湿涂层厚度和在复杂的结构区域使用小镜子可以有效地降低膜厚过薄或漏涂的现象。  \n\n一且出现漏涂或膜厚过低的现象，通常可对这些部位进行补涂。在补涂之前，需要注意表面的状况，如表面受到污染、产生粉化或超过覆涂间隔等情况发生，进行恰当的处理以确保补涂的涂层的附着力是非常必要的。  \n\n(2）流挂、帘状流挂和流涂料施工到垂直的基材表面后，由于重力的影响向下流动形成悬垂状突起状况称之为流挂，如图3-4-24所示。  \n\n根据程度的不同可分为流挂、帘状流挂和流淌。  \n\n流挂一般而言是分散的条状或水滴状突起。如果流挂连接成片状形成像窗帘般的褶皱，称为帘状流挂。而当涂料完全从基材上脱离，露出基层，称为流淌。  \n\n从涂料的角度而言，如果涂料本身的黏度比较低，在施工中极易产生流挂的现象。  \n\n有时由于底材温度过高或者过低，即使在常温下不会产生流挂的膜厚，也会出现流挂。夏天高温时，暴露于室外的钢材表面可以达到 $40\\sim60^{\\circ}C$ 的高温，而此时的空气温度可能在$30\\sim40^{\\circ}C$ ，涂料施工到这种表面，涂层接触底材的区域可能达到与钢材同样的温度，而表层与空气接触的区域与空气温度接近。温度高的底层，黏度下降，流动性增强，此时表层黏度相对较高的湿膜就会滑动流淌形成流挂。当温度过低时，同样会出现类似的黏度差而造成流挂，只不过正好相反，如图3-4-25所示。  \n\n很多时候，上述两种情况，可以通过调整涂料施工的技艺和工艺来避免和控制。但是如果施工的技艺和工艺不当，即使在正常的条件下也会产生流挂的缺陷。这也是产生流挂最常见的原因。  \n\n在涂料施工时，一次给予过高的湿膜厚度，涂层的自重超过其与基材的黏附力，就会形成流挂。这往往是在喷涂时喷枪行走的速度过慢、喷嘴距离基材表面太近造成的。  \n\n有些时候，喷涂压力过高，湿膜受到压力的推动也会形成流挂。  \n\n另一种情况是在涂料中添加了过多的稀释剂，人为地降低涂料的黏度，增加其流动性而造成施工中易于产生流挂。  \n\n![](images/60c1d184d21cffed25e367c5f6e1efce434ab2679ceb5fc840baf29ca31ae0e1.jpg)  \n\n涂料施工时发现存在流挂，应当及时地调整喷涂压力、 $i=\\frac{1}{2}$ 图342流挂走枪速度、喷嘴与基材的距离等喷涂技艺，注意控制稀释比率。如已经存在流挂，在湿膜状态时，可以使用漆刷拉平突起，或者使用边缘平直的玻璃板等刮除过多的涂料；漆膜干燥后发现的流挂，可以采用手工砂纸或动力磨机磨平表面，然后重补涂同种涂料。  \n\n(3）橘皮涂层干燥后，表面呈现凹凸不平的橘子皮的外观，称为橘皮。橘皮现象常见于高黏度、厚浆型的涂料。有些涂料黏度很高，自流平性能不佳，诸如：聚酯玻璃鳞片涂料和高固体分的环氧涂料，在施工时如果没有合适的喷涂设备或压力，非常容易观察到橘皮的现象。而在低温条件下，涂料的黏度会增高，此时即使在常温下适宜喷涂的涂料，也会出现橘皮现象，如图3-4-26所示。  \n\n涂料施工到基材表面干燥之前，由于重力的作用，湿膜会流动融合成平整的涂层。如果在其完全融合之前，漆膜就已干燥的话，表面会形成凹凸起伏的状况。同理，如果涂料自身所含的溶剂或添加的稀释剂挥发速率较快，漆膜未流平之前已干燥，同样会形成橘皮。另一方面，当喷涂设备不良或喷涂压力不足时，涂料无法充分雾化成微滴，而是成团状接触到基材，因而无法恰当的流平，也会形成橘皮现象。喷嘴太过靠近基材表面时，喷嘴处的压力会推动湿膜，造成局部的漆膜堆积而形成橘皮的外观。  \n\n![](images/15ade9bc65595c2b95c1b22fa76b33e58ccb3363a261684769528df6d5cf0164.jpg)  \n图3-4-25大气环境下温度差导致流挂的产生  \n\n![](images/cf8717d871ee7b781b8ae5c6f563fce9eae5b9ea9821bae66867da0a3f927ae6.jpg)  \n\n针对上述情况，如果涂料本身黏度过高，可以通过加人适量的稀释剂调整，降低黏度，增加涂层的流动性，避免和减少橘皮现象。除此之外，根据不同的温度条件选用合适的稀释剂、控制涂层干燥的时间以及保持良好的喷涂技艺都可以起到减少和避免该类缺陷产生的机会。  \n\n一旦发现有橘皮现象的产生，在涂层完全干燥后，采用手工砂纸或动力磨机打磨处理的方式，磨除表面的粗糙层并  \n\n补涂同种涂料。  \n\n(4）干喷/过喷涂料在喷涂过程中，在接触到基材表面时喷嘴处雾化的微滴已经干燥，形成的颗粒状的漆粉会黏附在基材或湿膜表面，最终会形成粗糙的砂纸状外观，这种情况称为于喷或过喷，如图3-4-27所示。  \n\n干喷的形成主要取决于雾化的微滴从喷嘴到涂漆面的干燥过程，这是由多种因素造成的。  \n\n从涂料本身而言，主要在于其本身所含溶剂或所添加的稀释剂的挥发速率过快。  \n\n而当环境温度较高同时相对湿度低和/或多风的天气，也会造成溶剂挥发速率增加，涂料的干燥速率加快。  \n\n很多时候可以在施工时通过调整施工工艺和选择合适的设备来减少涂料自身和环境条件的不利影响。反之，如果施工工艺和设备状况不佳，即使是合适的涂料和环境条件下也会形成干喷。更多时候，由于喷涂施工的技艺不良，非常容易造成干喷的缺陷。  \n\n![](images/26f913cad80993466d6398ba41feb301ecc14bdba78065b56fdb265612bd9e75.jpg)  \n图3-4-27干喷  \n\n对于一些小构件或管件，喷涂时的干喷是相当难以控制的，很多时候采用刷/辊涂的方法可以获得更好的效果。对于一些复杂的大体量构件，在开始喷涂之前应当仔细考虑喷涂的  \n\n线路，可以避免干喷产生。  \n\n同时，喷涂施工人员应当注意控制喷涂技巧。喷嘴距离涂漆面过远，雾滴在空气中的飞行距离延长，抵达表面前干燥的可能性也大大增加。同理，如果在喷涂时，雾化的扇面不是垂直于涂漆面，则扇面远端的雾滴在空气中的行进线路也延长了，因而易于造成干喷的现象。  \n\n干喷的产生会对涂装工件的外观造成影响，更严重的是如果后续涂层直接覆盖在干喷表面时，松动的干喷颗粒会导致后续涂层的附着力缺陷，出现开裂或分层的现象。  \n\n因而，在覆涂后续涂层时，对干喷表面进行恰当的处理，可以确保整个涂层系统的良好黏附而达到既定的防护要求。针对不同类型的涂层有可能需要采用不同的方法进行处理。当施工无机锌涂料产生严重的干喷现象时，建议喷砂去除整个涂层然后重新施工该涂层。而对于诸如丙烯酸、氯化橡胶等物理干燥的涂层，由于其本身可以轻易地重溶于溶剂中，因而只要在表面施工一定量的溶剂或稀释剂，溶解干喷颗粒和涂层，使其重新融为一体即可。对于氧化干燥和化学固化涂层表面的干喷，一般可以采用合适的方法清除表面的干喷颗粒，臂如：使用砂纸打磨的方法，然后施工后续涂层或重新在表面覆涂同种涂层。  \n\n![](images/c1ab066388bd58188bd4ac412710ca3c36a37cc0d64adac01e95a7ecf856ea04.jpg)  \n图3-4-28 针孔  \n\n（5）针孔涂层施工完毕后，表面出现微细的小孔，就像使用缝衣针在纸上扎出的小孔，称为针孔，如图3-4-28所示。  \n\n针孔的出现主要是由两方面的原因造成的：一方面，如果涂料本身的流平性不好，施工到表面后，没有充分地融合在一起，留出的缝隙就形成了针孔；另一方面，如果涂层内部包含空气、溶剂，受热后会膨胀，逸出干燥的涂层表层，其逸出的通路形成针状的小孔。而在粗糙表面，例如：无机锌涂层、混凝土、干喷的表面等，施工涂料时，如果涂料自身的润湿性欠佳，无法充分渗透到孔隙中，会把空气包容在涂层下，当温度上升时，空气会膨胀逸出，同样会形成针孔。  \n\n从施工工具的角度而言，使用辊筒时最易产生针孔，因为辊筒施工容易夹带空气，而且对不平整的表面的润湿性差。使用刷涂时，应当避免堆积过厚的涂料，特别是黏度和流平性较差的产品。喷涂时，正常条件下一般不会产生针孔的现象。但在高温多风的天气条件下尽可能避免使用挥发性高的稀释剂。另外当然需要控制恰当的喷涂技术，避免喷嘴距离涂漆面过近或者是喷涂压力过高。当施工过程中出现针孔时，添加稀释剂降低涂料的黏度，增加湿膜的流动性通常是一种解决的方法。  \n\n而一旦在漆膜干燥后观察到针孔时，可以采用打磨的方式，磨除有针孔的涂层。针孔有时仅出现在面层，有些时候可能穿透几度涂层直至底材，因而磨除的原则以看不到针孔为止。去除针孔后，根据磨除的涂层道数，补涂相应的涂层。  \n\n（6）起泡涂层表面顶起小空泡，在光线的照射下可以看到鼓起的顶端呈现半透明或透明的膜。通常，气泡的尺寸都不大，如图3-4-29所示。  \n\n起泡与针孔的成因在一定程度上是一样的，都是由于在涂层内包含溶剂或空气，当温度上升时，气体膨胀造成的。  \n\n![](images/599549d8c3f3a07b3379134c2e4e833ed45b065bdac8910e9715bf8d47f98228.jpg)  \n图3-4-29 起泡  \n\n区别在于起泡时的漆膜未被顶穿，而针孔出现时，漆膜表层已经顶穿，如果气泡顶部的透明或半透明的膜产生塌陷形成凹坑，也称为火山坑。另外，如果涂料施工在多孔隙的表面，诸如无机锌涂层、混凝土和干喷等表面，也容易产生起泡的现象。  \n\n施工时，容易造成漆膜表层干燥速率高于涂层内部的因素都易会引起起泡现象。这些因素有：单涂层膜厚过高、通风量过大（自然条件下的大风）等。  \n\n起泡现象产生意味着涂层中存在空泡，也就是说漆膜的有效厚度在这些部位降低了，形成了防护的弱点区域。同时，如果在覆涂后续涂层前，不消除这些气泡的话，起泡的现象可能会在后道涂层的同一部位重复出现。  \n\n在实际施工中，为了避免起泡的产生，应当避免单涂层施工过高的湿膜厚度，如果需要在多孔隙的基材表面施工时，可以选用联结漆或者采用雾喷的工艺以排除孔隙中的空气，避免起泡现象的发生。而一旦在涂层干燥后观察到起泡，可以采用打磨的方式清除气泡，然后重新补涂同种涂料。  \n\n(7）鱼眼鱼眼与火山坑都是属于一种坑状缺陷。相对而言，鱼眼的尺寸一般要大于火山坑，而且如果仔细观察，在鱼眼坑的中心部位可以观察到颗粒状或点状的污染物，围绕该污染物的区域可明显地观察到基材未被充分润湿，如图3-4-30所示。  \n\n鱼眼的形成大多是由于基材表面存在污染物，此类污染会降低基材表面的张力因而使涂层无法润湿。常见的污染物是油/脂。随着有机硅涂料作为防污漆在市场上推广和应用得更为广泛，在实践中有可能也会遇到表层遭遇有机硅污染而形成鱼眼的情况。当然还存在其他可能的污染物。另一种造成鱼眼的情况是在非常光滑的表面施工涂料，就像在玻璃表面洒水水膜会收缩而形成空隙。  \n\n![](images/c091202d2d2652cbe5da857d5ef359a94ab42f581912754f4194ea489670e710.jpg)  \n图3-4-30鱼眼  \n\n实际施工中遇到鱼眼的现象，首先应判明成因，如是由于污染物造成的应当彻底去除受到污染的表层，必要时可以结合化学溶剂清除污染物。同时应当找到污染源以免产生更多的鱼眼。如果成因是由于前道涂层表面过于光滑，则应当采用打毛表面的方式消除光泽，增加两度涂层之间的结合力。  \n\n![](images/5c10049c37dc4e610131df9e66bb8a8160fb20f12b6636b952dccd560e983782.jpg)  \n图3-4-31防污漆膜厚 过高导致起皱  \n\n(8）皱纹/抬起涂层起皱，当皱纹发展到一点程度时会从基层表面脱开但不会完全脱落形成抬起。如图3-4-31所示。  \n\n涂层系统不兼容是形成皱纹和抬起的主要原因。强溶剂类型的涂料覆盖在弱溶剂类型的涂层表面时，强溶剂会溶解或造成前度弱溶剂类型的涂层溶胀，从而底层涂层膨胀远大于后道涂层，造成起皱。当后道涂层无法承受底层膨胀的力量时，会产生开裂并从底层脱离或连带底层一起脱离基材。  \n\n有些时候，厚涂层在低温大风的天气条件下，表层的溶剂会较快挥发，表层干燥速率快，而内部的涂层可能长时间处于液态或黏态。所以在温度变化幅度比较大时，也会出现起皱的现象。  \n\n在维护和保养项目中，点喷砂区域周边的原有涂层，由于受到喷砂时磨料的撞击而丧失附着力，新的涂层覆盖在其表面后，涂层干燥时的收缩应力会拉离松动的涂层而造成抬起的状况，通常称为翘皮。  \n\n![](images/673ad48b2e92a542bd9cbc234322c8dd80f5b5c9da007374e0b79ee8cf7a746f.jpg)  \n图3-432胺渗出  \n\n出现皱纹和抬起时，需要彻底清除皱纹和抬起的涂层并补涂相应的涂层系统。  \n\n(9）渗出和碳化涂层完全硬干后，接触表面仍然有粘手的感觉，同时会在涂层表面观察到闪亮粘手的小点。这种状况主要会出现于环氧涂料中，环氧涂料中的胺类固化剂析出到涂层表面，形成胺渗出。析出的胺类固化剂与环境中的二氧化碳和水汽进一步反应生成白色的碳酸铵。因此，胺渗出的表面有时也会观察到白色的痕迹。如图3-4-32所示。  \n\n胺类固化剂之所以会从涂层中析出，主要在于涂层湿膜开放的时间过长。涂层中固化介质的密度小于涂层中的其他物质，因此如果胺类固化介质与主剂的反应速率过于缓慢，则有机会导致胺类固化剂浮出涂层而形成胺渗出。  \n\n涂层在于燥过程中如果相对湿度过高，会阻碍涂层中的溶剂及稀释剂的挥发，减缓涂层内反应速率，增加胺渗出的机会。密闭空间施工时，如果通风不良，挥发的溶剂蒸气由于密度大于空气而会沉积在地势低的区域，在这些区域阻止溶剂继续挥发，而造成胺渗出。低温条件下，化学反应速率减缓，胺渗出的概率也大大增加。  \n\n在施工中，为了减少或避免产生胺渗出，涂料施工前，给予一定的熟化时间是一种不错的解决方法。  \n\n如果胺渗出已经出现，当然在无后续涂层并对其外观可以接受的情况下可以不作处理。如需覆涂后续涂层，胺渗出会造成后续涂层剥落的缺陷，因而必须彻底清除。由于胺类固化剂及其生成的碳酸铵通常是水溶性的，所以采用温水擦洗是最佳的清除方法。  \n\n(10）发花涂层在面干之前接触到水分，当涂层干燥后，水分被封闭在表层而形成乳白色的痕迹，称为发花，如图3-4-33所示。  \n\n这种情况经常出现在涂料施工完毕后下雨、起雾等降水的条件下。有时涂料施工完毕后表面产生冷凝现象也会造成发花。在实际应用中，冷凝现象可能是由于压载舱中的压载水未排除，或者在水下施工，也会由于涂料中采用了挥发性高的溶剂和/或稀释剂，溶剂挥发的过程是一种散热过程，从底材带走热量降低底材温度，从而导致冷凝现象。  \n\n![](images/88321e9adc2549c418c75824ad09b40f9edcb772dc9e4a98e7c42386281941e9.jpg)  \n图3-4-33压载水未排尽造成船壳表面冷凝造成发花  \n\n![](images/2814c6688d155aba70ba18a460a146e69157f05d6c635fadb01b6336f9dad2e1.jpg)  \n1图3-4-34由焊接烟尘 造成的渗透压水泡  \n\n另一种情况是空气中的污染物如二氧化硫和氨会在涂层表面形成白色的硫酸铵，亦会造成发花的缺陷。  \n\n发花现象产生后，使用淡水冲洗或溶剂擦拭的方法往往无法获得好的效果，因为这些发花的产物并非水溶性的。应当使用打磨处理的方法清除表层乳白状的缺陷区域，然后补涂同系统的涂料。  \n\n(11）渗透压水泡涂层在服务过程中，如果其两边存在浓度不同的液体时，浓度低的液体会渗透过漆膜去稀释浓度高的部分直至两边的浓度达到一样。在这个渗透过程中会产生人们称为渗透压的力。涂层如果施工在受到盐分污染的表面，然后投人服务使用，环境中的低浓度的水分会渗透过漆膜稀释盐分，造成盐分部位的水体体积增加。最终会把涂层顶起而形成鼓泡。这种泡中常常含有液体，称为渗透压水泡，如图3-4-34所示。  \n\n盐分的来源有很多渠道，在工业上，环境条件中的盐雾、含锌涂层形成的锌盐、水溶性的焊接烟尘以及空气中的污染物等。  \n\n因而在涂层施工前应当确保基材表面不受盐分的污染，可以在将来避免渗透压水泡的产生。  \n\n渗透压水泡可能会出现在底材上，也有可能出现在涂层和涂层之间。在修补渗透压水泡时，铲除水泡然后用淡水冲洗以清除内部的盐分。避免同一位置将来又出现渗透压水泡。  \n\n(12）针状锈蚀钢材表面出现的针眼状点蚀称为针状锈蚀。针状锈蚀往往与针孔伴生。针孔如果穿透涂层直至底材，暴露一定时间后，底材在环境条件的作用下而产生腐蚀，如图3-4-35所示。  \n\n涂层如果覆涂在干喷的表面以及多孔隙的表面，无法充分润湿底材，导致底材无法受到涂层的防护而暴露于环境中，从而生成锈蚀。另外涂层施工膜厚太薄或产生漏涂也会造成针孔状的锈蚀。  \n\n![](images/5bf65d7735e8dfab3ae9df902c1fb4ed21a502227531bcbfa1ff750a528af2e8.jpg)  \n图3-4-35 针状锈蚀  \n\n出现针状锈蚀后需要采用合适的方式和方法清除锈蚀并重新补涂合适的涂层。  \n\n(13）开裂涂层表面产生裂纹。根据裂纹的深度和宽度，开裂可以分为细裂纹、裂开、鳄皮状裂纹和泥裂。  \n\n$\\textcircled{1}$ 细裂纹涂层表面的发丝状裂纹，通常只出现在表面，深度也很浅，其尺寸通常为微米级的，如图3-4-36所示。  \n\n![](images/5edfea6d09e4b8bbf07e34a958e604058d4dbaee158d1beef86480785fdbe140.jpg)  \n图3-4-36 防污漆表面的细裂纹  \n\n![](images/b7de211872a7e539dd7d0cf55d10442a534833447fea539f7292f2992b2e3920.jpg)  \n图3-4-37 膜厚过高而造成的裂开  \n\n$\\textcircled{2}$ 裂开其宽度要明显大于细裂纹，通常为毫米级别，有可能只出现在表层，也有可能深达底材，如图3-4-37所示。  \n\n$\\textcircled{3}$ 鳄皮状裂纹此种裂纹的宽度要远远大于其深度，通常出现在面层，在裂开的缝隙中可以观察到底道涂层的颜色，如图3-4-38所示。  \n\n$\\textcircled{4}$ 泥裂涂层具有连续的开裂纹路，同时裂缝边缘会有翘起的现象，形成如湖泥开裂的状态，如图3-4-39所示。  \n\n涂层开裂的产生是由漆膜内部的应力集中而造成的。积聚的应力是由许多因素形成的。涂料构成的树脂本身在干燥和固化过程中会出现应力聚集的现象。涂层厚度过高也会有应力积聚的现象。因而所有的涂料施工都应当控制其膜厚不超过规定的限值。当温度变化时，涂层的热胀冷缩也会导致涂层开裂。特别是在底层涂层较软而面层较硬时，更易受到温度的影响。这有可能发生于整个系统中的底漆较软而面漆较硬，或者是同一度涂层的表面干燥而内部为液态或黏态的情况下。  \n\n![](images/2e37c22bd228e66a742b4f23f73d4ae54b8de526bafcaf9a9cd7618440cf0f12.jpg)  \n图3-4-38 氯化橡胶底漆表面覆涂醇酸面漆  \n\n店89010只日  \n\n![](images/d59b83bcd5825cd3f2fd2e605f2c471ccd17fa1b6610d9a0bf644b6fde472716.jpg)  \n图3-4-39 无机硅酸锌漆膜过高造成泥裂  \n\n除了涂层内部本身的应力以外，如果涂层接触到的外部应力超过其能承受的极限，也会产生开裂的现象。如果涂层施工在松动的表层，例如旧的无锡防污漆表面存在的空穴层、干喷的表面以及当醇酸类的涂层覆盖在含锌层表面时产生的皂化层等。一旦存在外部的应力或者涂层在干燥和固化的收缩应力都会导致开裂。开裂会随着时间的推移而发展，最终导致涂层从基材上剥离、脱落。  \n\n就常见的开裂类型而言，细裂纹通常出现在厚涂层表面，特别是在冬季低温条件下，涂层的干燥和固化速率减缓，涂层的表面暴露于温度变化中而更易形成。鳄皮裂纹通常是由于涂层系统底面涂层不兼容造成的。无机锌涂层对于膜厚比较敏感，如果超过一定的厚度，极易产生泥裂。  \n\n开裂产生后，针对不同的裂纹形式需要采用不同的处理方法。  \n\n细裂纹通常只需要磨除表面的开裂，然后重新补涂同种涂料。  \n\n裂开的现象需要磨除至看不到裂纹，并根据磨除的情况补涂同系统的涂层。  \n\n鳄皮状裂纹，首先需要清除开裂的涂层，通常是面层涂层。然后需要根据底道涂层选择兼容的面层重新施工。  \n\n如果无机锌发生泥裂，就需要采用喷砂的方式清除开裂的涂层并重新施工合适厚度的无机锌涂层。  \n\n(14）分层分层是指涂层从底材或其他涂层剥离及脱落，或者是涂层自身断开而呈片状剥离和脱落。其中前一种分层现象称为附着力缺陷，后一种称为内聚力缺陷。  \n\n附着力的缺陷常常是由于涂料施工前表面存在污染物，例如灰尘、油脂等。其他的一些松动物质也会造成后道涂层的分层现象，包括：干喷、粉化层、胺渗出和无锡防污漆的空穴层等。某些涂层完全干燥或固化后表面非常坚硬和光滑，后道涂层施工在这种表面无法达到很好的润湿效果，因此会造成分层的隐患。常用的焦油环氧、高光泽的聚氨酯和完全固化的化学固化涂层都有可能产生此种隐患。除了上述因素以外，如果涂层系统配套兼容性不佳，也有造成分层的可能性，例如在物理干燥的涂层表面施工醇酸涂层或其他强溶剂的涂料、前面提到的在含锌涂层表面施工醇酸涂层。各分层如图3-4-40～图3-4-43所示。  \n\n相对于附着力缺陷多半由外因造成，内聚力缺陷更多是由于涂层本身的性能缺陷形成，或者是由于单道涂层的膜厚过高。  \n\n![](images/f89faa18181a845db23b272b4e51a35ef9114c76433c0afae613db7bcb289517.jpg)  \n\n![](images/67d83a7c38d0a4e66e344ab17d93640933d97a8c61faf88f1e2801a3e81144c7.jpg)  \n\n![](images/23e17bc52ac962008b52926418125c2501e3784424fcaaa4942246a87fac4e0e.jpg)  \n图3-4-40涂层覆盖在油脂上造成分层  \n图3-4-41镀锌件表面施工醇酸涂料  \n\n![](images/6b6413c9bef46264e3596b3352c56c6d7b95575a31216dae6edc9a2e2aac12c3.jpg)  \n图3-4-42焦油环氧施工后覆涂间隔过长  \n图3-4-43 焦油环氧粉化  \n\n一旦出现涂层分层的现象，首先应当使用恰当的检测方法，例如：十字划格法或拉离测试来确定附着力弱点的部位和范围，然后通过合适的方法清除分层的涂层和附着力差的涂层，补涂同系统的涂料。  \n\n(15）粉化涂层暴露于环境中一段时间后，表面产生粉尘颗粒状物质，同时涂层表面的光泽会降低，此时即为涂层表面产生了粉化现象，如图3-4-43所示。  \n\n粉化主要是由于涂层表面受到环境条件的影响，例如：太阳光线中的紫外线照射、风化和其他一些因素，导致树脂退化，涂层中的颜料、填料暴露出来。在施工过程中如果涂料未充分混合，成膜时树脂无法良好地包容颜料、填料也会造成颜料、填料外浮而形成粉化。常用的涂料类型中，环氧类的产品，最易产生粉化现象。  \n\n表层的粉化物质如不经处理直接覆涂后续涂层，很容易造成后道涂层开裂和剥落，因而应当采取打磨或高压淡水冲洗的方法彻底清除。  \n\n(16）渗色涂层施工一定时间后，由于底层材料的影响而造成面漆颜色的改变称为渗色，如图3-4-44所示。  \n\n渗色通常是由底层涂层中的颜料溶解于后道涂层，而迁移到面漆涂层，影响其颜色。此列颜料中，最常见的是焦油和沥青。如果底漆为含焦油和沥青的产品，覆盖面漆后，底漆中的焦油和沥青会迁移到面漆，从而在面漆表面形成棕色或深浅不一的色斑，影响面漆的外观。  \n\n一个比较特殊的例子是水性涂料施工后，相对湿度过高，涂料中的水分会造成钢材锈蚀，同时这些锈蚀会从底材渗透到面层，改变面层的颜色。  \n\n渗色的产生一般而言只是影响到涂层的美观效果，对于涂层防护性能的影响不大，当然上述水性涂料的例子不在其列。如果的确需要去除渗色的影响，通过简单的封闭涂层处理只能延缓渗色的产生时间，但不能根本解决问题。有效的方法是彻底地去除渗色源，然后施工不会产生渗色的涂层系统。  \n\n![](images/bd3d8ccd8af15a41a8f06a20a8fe7836ca8187a6bdbcdc9e8002ccc2c643bad0.jpg)  \n图3-4-44 焦油环氧表面覆涂白色面漆  \n\n![](images/c86cc81718beb64bf85207f04b7ea729ae0e57e0827ce7eb8a79eb1b64858d34.jpg)  \n图3-4-45 漆膜切开后在放大镜下观察  \n\n(17）空泡上述提到的种种缺陷都是可以通过肉眼直接观察的涂层缺陷。空泡这类涂层缺陷无法通过肉眼辨别，需要借助放大镜来进行观察。涂层在干燥和固化阶段，溶剂未充分挥发而沉陷在涂层内，在涂层内形成空泡。此类缺陷通常是由于单涂层膜厚过高、通风不良、高湿度或稀释剂添加量过多造成的，如图3-4-45所示。  \n\n这种缺陷虽然不会马上造成影响，但是空泡的存在降低了涂层的有效厚度，在涂层服务中将缩短涂层的服务寿命。  \n\n修补这种缺陷的方法是完全去除原有的涂层，施工恰当的涂层系统。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 282,
+        "chunk": "# 一、集装箱涂料简介",
+        "category": " Introduction"
+    },
+    {
+        "id": 283,
+        "chunk": "# 1.集装箱及其发展历史  \n\n集装箱是在航运过程中逐渐形成的一种运输工具，作为一种方便快捷的运输方式，它的出现可以说是航运史上的一次革命。现代意义的集装箱最早出现于1956年，它是一种可以实现水陆联运的铝质卡车车厢，而后在美国开始规模化的集装箱生产制造。后来随着经济和物流的发展，集装箱的生产中心转移到欧洲。20世纪70年代中期，日本的集装箱制造业随经济的发展变得非常繁荣，70年代末至80年代初期，迅速崛起的韩国和中国台湾成为集装箱制造的主流区域。从20世纪80年代起，世界集装箱制造的重心转移到了中国，截至2006 年底，全世界集装箱的制造量达到280万标准箱，而其中的94%是由中国的工厂制造的，这充分说明，中国已经成为世界集装箱制造和集散的中心，集装箱用涂料也从以往的船舶涂料的一个分支而逐渐自成体系。",
+        "category": " Introduction"
+    },
+    {
+        "id": 284,
+        "chunk": "# 2.集装箱的分类和结构  \n\nISO 668给集装箱下了这样的定义：集装箱是一种运输设备，应满足下列要求。  \n\n$\\textcircled{1}$ 具有足够的强度和耐久特性，可长期反复使用。  \n$\\textcircled{2}$ 适用于一种或多种运输方式，途中转运时，箱内货物不需换装。  \n\n$\\textcircled{3}$ 适用于快速装卸装置作业，尤其是便于从一种运输方式装换到另一种运输方式。  \n\n$\\textcircled{4}$ 便于箱内装满货物和卸空。  \n\n$\\textcircled{5}$ 具有 $\\bf{1m^{3}}$ 及其以上的容积。  \n\n(1）集装箱的分类按照集装箱的尺寸，即体积的大小，ISO 668把通用的集装箱分为10ft、20ft、30ft、40ft、45ft高箱几种（ $\\therefore\\mathrm{lft}=0.30\\mathrm{m}$ ，下同)，表3-4-38为第一系列国际标准集装箱规格。集装箱按照用途可以分为干货箱、冷藏箱和特种箱，特种箱包括保温集装箱、罐式集装箱、折叠箱、航空集装箱等许多种。干货集装箱的材质主要为耐候钢，冷藏箱可使用铝合金板或不锈钢板。不同尺寸的集装箱对涂料要求没有差别，但不同用途的集装箱对涂料的要求却有很大的差别，以下主要以干货集装箱为例，介绍集装箱涂料的相关内容。  \n\n表3-4-38第一系列国际标准集装箱规格  \n\n\n<html><body><table><tr><td rowspan=\"2\">规格/ft</td><td rowspan=\"2\">箱型</td><td colspan=\"2\">长</td><td colspan=\"2\">宽</td><td colspan=\"2\">高</td><td colspan=\"2\">最大总重量</td></tr><tr><td>公制 /mm</td><td>英制 /ft、in</td><td>公制 /mm</td><td>英制 /ft、in</td><td>公制 /mm</td><td>英制 /ft、in</td><td>/kg</td><td>/lb</td></tr><tr><td rowspan=\"2\">45</td><td>1EEE</td><td rowspan=\"2\">13716</td><td rowspan=\"2\">45′</td><td rowspan=\"2\">2438</td><td rowspan=\"2\">8′</td><td>2896</td><td>9'6\"</td><td rowspan=\"2\">30480</td><td rowspan=\"2\">67200</td></tr><tr><td>1EE</td><td>2591</td><td>8′6\"</td></tr><tr><td rowspan=\"4\">40</td><td>1AAA</td><td rowspan=\"4\">12192</td><td rowspan=\"4\">40′</td><td rowspan=\"6\">2438</td><td rowspan=\"6\">8′</td><td>2896</td><td>9'6″</td><td rowspan=\"4\">30480</td><td rowspan=\"2\">67200</td></tr><tr><td>1AA</td><td>2591</td><td>8'6\"</td></tr><tr><td>1A</td><td>2438</td><td>8</td></tr><tr><td>1AX</td><td><2438</td><td><8'</td></tr><tr><td rowspan=\"4\">30</td><td>1BBB</td><td rowspan=\"4\">9125</td><td rowspan=\"4\">29′11.25\"</td><td rowspan=\"4\"></td><td>2896</td><td>9′6\"</td><td rowspan=\"4\">25400</td><td rowspan=\"4\">56000</td></tr><tr><td>1BB</td><td>2591</td><td>8'6\"</td></tr><tr><td>1B</td><td>2438</td><td>8'</td></tr><tr><td>1BX</td><td><2438</td><td><8′</td></tr><tr><td rowspan=\"3\">20</td><td>1CC</td><td rowspan=\"3\">6058</td><td rowspan=\"3\">19′10.5\"</td><td rowspan=\"3\">2438</td><td>2591</td><td>8′6\"</td><td rowspan=\"3\">24000</td><td rowspan=\"3\">52900</td></tr><tr><td>1C</td><td>2438</td><td>8′</td></tr><tr><td>1CX</td><td><2438</td><td><8'</td></tr><tr><td rowspan=\"2\">10</td><td>1D</td><td rowspan=\"2\">2991</td><td rowspan=\"2\">9'9.75\"</td><td rowspan=\"2\"></td><td>2438</td><td>8′</td><td rowspan=\"2\">10160</td><td rowspan=\"2\"></td></tr><tr><td>1DX</td><td><2438</td><td><8'</td></tr></table></body></html>  \n\n(2）集装箱的结构目前制造量最大的是干货箱，其结构在ISO830中有明确的规定，40ft箱的结构和各主要部位的中英文名称如图3-4-46所示。",
+        "category": " Introduction"
+    },
+    {
+        "id": 285,
+        "chunk": "# 3.集装箱的使用环境  \n\n大部分的海运集装箱是采用水陆联运的方式进行运输的，其使用范围可能遍及全球。因此集装箱的使用环境既有内陆、沿海，也有海上，环境的温差也会很大，可能会从一 $40\\sim$ 50℃。有些其他类型的集装箱，如铁路集装箱，虽然不会经由海路运输，但是由于常常会在沿海港口城市滞留，其防腐蚀要求也和海运集装箱相差不多。由于集装箱的结构特点，构成集装箱的板材大部分厚度为1.6mm，这就要求集装箱涂料体系既要首先满足防腐要求，又要同时兼顾美观和移动变形的要求。  \n\n电一  \n\n![](images/3e2a488b002d50a909120f52c26c50b7927b246a735798e9ccae87bf8bb6c580.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 286,
+        "chunk": "# 4.集装箱涂料的评价标准  \n\n目前尚无关于集装箱涂料的具体的国际或国家标准，中国的集装箱工业协会制定的行业标准是目前有效的集装箱涂料标准（JH/TE01—2008）。业内通常认可美国的K.T.A.实验室关于集装箱涂料的评价标准，该标准要求集装箱涂料要通过八个项目的十三种试验，总评分需超过120分（满分为130分）。K.T.A.实验室的检测项目和指标见表3-4-39。  \n\n表3-4-39K.T.A.实验室对集装箱漆的评价项目一览表  \n\n\n<html><body><table><tr><td>序号</td><td>评价项目</td><td>实验方法</td><td>评价方法、要求</td><td>指标</td><td>得分</td></tr><tr><td rowspan=\"3\">1</td><td rowspan=\"3\">耐磨性：失重/g</td><td rowspan=\"3\">ASTM D1044</td><td rowspan=\"3\">1000r,250g,CS10 号轮</td><td>0~10</td><td>10</td></tr><tr><td>11~25</td><td>8</td></tr><tr><td>>25</td><td>6</td></tr><tr><td rowspan=\"5\">2</td><td rowspan=\"5\">耐腐蚀性 平均腐蚀等级 加速线锈蚀</td><td rowspan=\"5\">ASTM B117 5%盐雾600h</td><td rowspan=\"5\">ASTM D1654</td><td>0</td><td>10 8</td></tr><tr><td>1.0mm</td><td></td></tr><tr><td>2.0mm</td><td></td></tr><tr><td>3.0mm</td><td>6</td></tr><tr><td>4.0mm 5.0mm</td><td>５ 4</td></tr><tr><td rowspan=\"5\">耐腐蚀性 平均起泡等级</td><td rowspan=\"3\">ASTM B117 起泡数量 5%盐雾600h</td><td rowspan=\"3\">ASTM D1654</td><td>6.0mm</td><td>3</td></tr><tr><td>无 1~2</td><td>10 8</td></tr><tr><td>3~7 8~10</td><td>7 6 4</td></tr><tr><td rowspan=\"2\">加速老化性能 变色</td><td>ASTME42 600h</td><td>ASTM D2244</td><td>26~40 △E≤2 △E≥3</td><td>3 10 6</td></tr><tr><td>加速老化性能 失光 600h</td><td>ASTM E42 ASTM D523</td><td>0~10% 11%~24% ≥25%</td><td>10 8</td></tr><tr><td rowspan=\"5\">4</td><td rowspan=\"3\">柔韧性</td><td rowspan=\"3\">ASTM D1731 12.7cm轴，180° 弯曲后</td><td>原来</td><td>无开裂 轻微开裂</td><td>6 10 5</td></tr><tr><td>600h加速曝晒后</td><td>开裂 无开裂 轻微开裂</td><td>1 10 ５</td></tr><tr><td></td><td></td><td></td></tr><tr><td rowspan=\"5\">5</td><td rowspan=\"5\">对底材的附着力</td><td rowspan=\"5\">DIN053151</td><td rowspan=\"5\">原来</td><td>开裂 无脱落</td><td>1</td></tr><tr><td>5%脱落</td><td>10 8</td></tr><tr><td>15%脱落</td><td>6</td></tr><tr><td>35%脱落</td><td>4</td></tr><tr><td>50%脱落</td><td>2</td></tr><tr><td rowspan=\"5\"></td><td rowspan=\"5\"></td><td rowspan=\"5\">600h加速曝晒后</td><td>无脱落</td><td></td></tr><tr><td>5%脱落</td><td>10</td></tr><tr><td>15%脱落</td><td>8 6</td></tr><tr><td>35%脱落</td><td></td></tr><tr><td>50%脱落</td><td>4 2</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>序号</td><td>评价项目</td><td>实验方法</td><td>评价方法、要求</td><td colspan=\"2\">指标</td><td>得分</td></tr><tr><td>6</td><td>耐盐水性</td><td>浸于5%NaCl 中168h 25C</td><td></td><td colspan=\"2\">无变化 轻微变化 起泡和/或其他漆病</td><td>10 6 2</td></tr><tr><td rowspan=\"6\">7</td><td rowspan=\"6\">耐冲击性</td><td rowspan=\"6\">ASTM D2794</td><td rowspan=\"3\"></td><td>60lbf·in以上</td><td>70kgf·cm以上</td><td>10</td></tr><tr><td>50～59lbf ·in</td><td>63~74kgf ·cm</td><td>8</td></tr><tr><td>40～49lbf ·in</td><td>50～62kgf·cm</td><td>6</td></tr><tr><td></td><td>40lbf ·in以下50kgf·cm以下</td><td>4</td></tr><tr><td rowspan=\"3\">600h加速曝晒后</td><td>60lbf·in以上</td><td>70kgf·cm以上</td><td>10</td></tr><tr><td>50~59lbf ·in63~74kgf·cm</td><td></td><td>8</td></tr><tr><td>40~49lbf·in</td><td>50～62kgf·cm</td><td>6</td></tr><tr><td rowspan=\"6\">8</td><td rowspan=\"4\">漆膜硬度</td><td rowspan=\"3\">ASTM D3363 铅笔耐划性</td><td rowspan=\"2\">氧化和催化成膜</td><td colspan=\"2\" rowspan=\"2\">40lbf·in以下 6H</td><td>50kgf·cm以下 4</td></tr><tr><td>10</td></tr><tr><td colspan=\"2\">5H 4H 3H</td><td>6 4 2</td></tr><tr><td rowspan=\"2\">挥发成膜</td><td colspan=\"2\">4H 3H</td><td>10 8</td></tr><tr><td rowspan=\"2\">2H H</td><td colspan=\"2\"></td></tr><tr><td rowspan=\"2\"></td><td colspan=\"2\"></td><td>4</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 287,
+        "chunk": "# 二、集装箱涂料的配套方案和集装箱涂料  \n\n集装箱的涂料配套方案一般由箱东制定，不同种类的集装箱对涂料的要求是不同的，其中对防腐要求最严格的应该为海运干货箱，下面以基本的干货箱用涂料配套为例加以说明。",
+        "category": " Introduction"
+    },
+    {
+        "id": 288,
+        "chunk": "# 1.基本配套  \n\n干货箱的外表面通常采用环氧富锌底漆十环氧中间漆 $+$ 丙烯酸外面漆的涂装配套体系；内表面采用环氧富锌底漆 $+$ 环氧内面漆；底架部位有的采用环氧富锌漆 $+$ 沥青漆，有的则采用和外表面相同的配套。现在也有些箱东在干货箱上开始采用聚氨酯面漆。  \n\n典型的配套体系见表3-4-40和表3-4-41。  \n\n表3-4-40 集装箱涂料配套方案（一）  \n\n\n<html><body><table><tr><td>部 位</td><td>度数</td><td>涂料种类</td><td>涂膜厚度/μm</td><td>总膜厚/μm</td></tr><tr><td rowspan=\"3\">外表面</td><td>第一度：车间底漆</td><td>环氧富锌漆</td><td>10</td><td rowspan=\"3\">125</td></tr><tr><td>第二度：富锌底漆</td><td>环氧富锌漆</td><td>20</td></tr><tr><td>第三度：中间漆</td><td>改性环氧漆</td><td>40</td></tr><tr><td rowspan=\"3\">内表面</td><td>第四度：外面漆</td><td>丙烯酸面漆</td><td>55</td><td rowspan=\"3\">80</td></tr><tr><td>第一度：车间底漆</td><td>环氧富锌漆</td><td>10</td></tr><tr><td>第二度：富锌底漆</td><td>环氧富锌漆</td><td>20</td></tr><tr><td rowspan=\"3\">底架</td><td>第三度：内面漆</td><td>改性环氧漆</td><td>50</td><td rowspan=\"3\">235</td></tr><tr><td>第一度：车间底漆</td><td>环氧富锌漆</td><td>10</td></tr><tr><td>第二度：富锌底漆 第三度：沥青漆</td><td>环氧富锌漆 腊质沥青漆</td><td>25 200</td></tr></table></body></html>  \n\n表3-4-41 集装箱涂料配套方案（二）  \n\n\n<html><body><table><tr><td>部位</td><td>度数</td><td>涂料种类</td><td>涂膜厚度/μm</td><td>总膜厚/μm</td></tr><tr><td rowspan=\"4\">外表面</td><td>第一度：车间底漆</td><td>环氧富锌漆</td><td>10</td><td rowspan=\"4\">125</td></tr><tr><td>第二度：富锌底漆</td><td>环氧富锌漆</td><td>20</td></tr><tr><td>第三度：中间漆</td><td>改性环氧漆</td><td>40</td></tr><tr><td>第四度：外面漆</td><td>聚氨酯漆</td><td>55</td></tr><tr><td rowspan=\"3\">内表面</td><td>第一度：车间底漆</td><td>环氧富锌漆</td><td>10</td><td rowspan=\"3\">80</td></tr><tr><td>第二度：富锌底漆</td><td>环氧富锌漆</td><td>20</td></tr><tr><td>第三度：内面漆</td><td>改性环氧漆</td><td>50</td></tr><tr><td rowspan=\"3\">底架</td><td>第一度：车间底漆</td><td>环氧富锌漆</td><td>10</td><td rowspan=\"3\">235</td></tr><tr><td>第二度：富锌底漆</td><td>环氧富锌漆</td><td>25</td></tr><tr><td>第三度：沥青漆</td><td>腊质沥青漆</td><td>200</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 289,
+        "chunk": "# 2.集装箱用涂料  \n\n(1）环氧富锌底漆环氧富锌底漆是一种典型的防腐涂料。其原理是利用金属锌的牺牲阳极反应起到对钢铁底材的防护作用。金属锌的标准电极电位为 $(-0.76\\ensuremath{\\mathrm{V}})$ ，金属铁的电极电位为（一0.44V)。当这两种金属组成回路并有电解质存在时，就会形成所谓的原电池，金属锌会作为阳极而不断消耗。钢铁表面涂上富锌漆以后，在底材表面出现损伤时，外界腐蚀性电解质（海水、盐雾等）首先会腐蚀消耗金属锌从而使底材得到保护，同时锌作为牺牲阳极形成的氧化产物，可以对涂层起到一定的封闭作用，加强涂层对底材的保护，防止锈蚀的进一步扩展。  \n\n$\\textcircled{1}$ 富锌漆配方体系在进行环氧富锌漆的配方设计时，满足箱东对锌粉含量的要求是配方的基础，其次还要考虑到干燥性、防沉性等问题。通常采用双酚A型环氧树脂、多元氨或聚酰胺类固化剂。由于锌粉含量较高，配方的PVC值也很高，大部分会超过CPVC以保证锌粉粒子的充分接触。为了防止贮存和运输过程中产生沉淀，加入触变助剂是必须的。另外微量的水也会和活泼的金属锌反应产生氢气而发生“胀罐”，一般要加入脱水剂来防止这一问题的发生。典型的集装箱用环氧富锌底漆配方见表3-4-42。环氧富锌底漆的技术指标见表3-4-43。  \n\n表3-4-42 典型的集装箱用环氧富锌底漆配方  \n\n\n<html><body><table><tr><td>原料</td><td>配方量/质量份</td><td>原料</td><td>配方量/质量份</td></tr><tr><td>双酚A型环氧树脂</td><td>11</td><td>二甲苯</td><td>16</td></tr><tr><td>锌粉</td><td>65</td><td>脱水剂</td><td>1</td></tr><tr><td>滑石粉</td><td>3</td><td>聚酰胺树脂</td><td>3</td></tr><tr><td>膨润土</td><td>1</td><td></td><td></td></tr></table></body></html>  \n\n表3-4-43 环氧富锌底漆的技术指标（JH/TE01一2008）  \n\n\n<html><body><table><tr><td>项目</td><td>要求</td><td>项目</td><td></td><td>要求</td></tr><tr><td>涂料外观</td><td>搅拌后无硬块，呈均匀状态</td><td>混合体积固体分/%</td><td>45</td><td></td></tr><tr><td>细度(方法A)/μm</td><td>60</td><td>附着力</td><td>1级</td><td></td></tr><tr><td>重涂间隔/min ≤3</td><td></td><td>柔韧性/mm</td><td>3</td><td></td></tr><tr><td>半硬干燥时间（80℃烘烤）/min≤</td><td>5</td><td>耐冲击性/kgf·cm</td><td>50</td><td></td></tr></table></body></html>  \n\n$\\textcircled{2}$ 环氧富锌底漆的锌粉含量干燥漆膜中锌粉含量的多少是衡量锌粉漆防腐性能的一个关键指标。由于锌粉的价格数倍于富锌漆中的其他颜填料，因此锌粉含量成为影响集装箱涂料成本的一个重要因素。在保证使用寿命的前提下，到底多少锌粉含量合适，在这个问题上行业内一直在争论，国内外也有很多标准。经过多年的探讨，目前行业内趋于认同的锌粉含量标准为SSPC-PAINT20：2002中所描述的LEVEL2，即 $\\geq77\\%$ ， $<85\\%$ ；和LEVEL3，即 $\\geq65\\%$ ， $<77\\%$ 中  \n\n$\\textcircled{3}$ 富锌底漆锌粉含量的检测对于富锌漆中锌粉含量的检验，现在国际上有两种应用比较广泛的方法，即化学分析法（ASTMD521）和差示扫描量热法（ASTMD6580）。化学分析法主要使用洗涤的方法先将富锌漆中的锌粉分离出来，然后用化学方法滴定，计算出锌粉含量。这种方法适合于液态涂料中锌粉含量的检测。对固化后漆膜中的锌粉含量检验结果往往不准确，这主要是由于涂膜中的高分子物质难以和锌粉分离，对测量过程及其结果有很大的干扰作用。  \n\n用差示扫描量热法（differential scanning calorimetry 简称DSC）测量涂膜中的锌粉含量具有快速简便、测量数据准确的特点，已经逐渐在行业内被广泛应用。其原理是在温度程序控制下，测量输给试样物质和参比物质的功率差与温度关系的一种技术。这种技术可分为功率补偿式差示扫描量热法和热流式差示扫描量热法。  \n\n④富底漆干膜厚度的检测作为防腐蚀底漆，环氧富锌漆一般涂于喷砂或抛丸处理后的钢板表面，而在流水线上，在富锌底漆还没有完全干燥的情况下很快（通常在10min以内）又要涂装下一度环氧漆，目前的普通测厚仪难以在富锌漆尚未完全干燥的状态下准确测量其厚度，因此富锌底漆的漆膜厚度的测量成为一个难题。由于富锌底漆的特殊作用，是否漏涂或者膜厚是否达到标准直接关系到集装箱将来使用中的防腐性能，特别是涂膜破损后的防止锈蚀扩散性能。这就使得各利益方非常关心富锌漆漆膜厚度的测量及其影响因素。目前常用的测量富锌漆干膜厚度的方法有以下三种。  \n\na.普通磁力膜厚仪由于钢板的粗糙度在25～40μm，底材表面粗糙度对富锌漆膜厚的测量会产生影响。如果用在光滑零板上校准过的磁力膜厚仪测量箱体上的富锌漆的膜厚是不准确的。应该采取用与底材相同粗糙度的零板校准膜厚仪，或者在相同的涂装条件下将富锌漆喷涂于光滑马口铁板上的办法来测量富锌漆的干膜厚度。  \n\nb.破坏性涂层测厚仪（PIG）破坏性涂层测厚仪（PIG）是一种类似显微镜的监测仪器，它由割刀和光学放大设备组成，割刀的作用是将漆膜严格按照与涂膜表面呈一定的角度剖开。光学设备将剖面放大并显示在有刻度屏幕上，这个数值已经通过转换屏幕上的标尺换算成了实际的膜厚。割刀的最大优点是可以在表面涂有其他漆膜的情况下测量富锌漆的膜厚，并且可以同时测量多种涂层的膜厚。缺点是会破坏漆膜。  \n\n![](images/add7ffe86fdb937925f720b508ac6c95df60e5d3e76044338ac3f4c59568feaf.jpg)  \n图3-4-47超声波测厚仪的工作原理测定方法：ASTME797—1995涂层厚度 $\\circleddash$ （速度 $x$ 通过时间）/2  \n\nc.超声波测厚仪超声波测厚仪是近几年出现的一种膜厚测量仪器，其原理是利用超声波在不同介质里的反射速度不同，通过精确计量反射时间来测量膜厚。它可以在不破坏漆膜的情况下实现对其他漆膜之下的富锌漆涂膜厚度的检查，也可以测量多层涂膜的厚度。其工作原理如图3-4-47所示。  \n\n由于超声波的特性，当富锌漆中的锌粉含量不同时，即使涂膜的厚度相同，超声波在涂膜中的反射时间也是不同的（因为不同锌粉含量的富锌漆的涂膜密度是有差别的)，仪器显示的涂膜厚度也是不一样的，这就要求对各个厂家生产的不同品种的富锌漆制定不同的基准曲线，也就增加了测量结果的不确定性，制约了这种方法的广泛使用。  \n\n(2）环氧中间漆与其他重防腐漆一样，集装箱用的环氧漆主要由环氧树脂、聚酰胺类固化剂和颜填料、助剂等组成，具有非常好的屏蔽效果。大家都知道，环氧漆的耐候性不好，装饰性较差，因此在外表面必须要加涂面漆来满足耐候性和装饰性的要求。因此对中间漆而言，除了防腐效果以外，其他方面的要求不是很苛刻。环氧中间漆的作用如下。  \n\n$\\textcircled{1}$ 作为富锌漆和面漆的过渡层，增强层间附着力，进而增强这个系统的密着性。  \n\n$\\textcircled{2}$ 具有良好的屏蔽性能，防止腐蚀性离子侵人到富锌漆或者底材。  \n\n$\\textcircled{3}$ 具有一定的硬度和韧性，既能防止运输过程中的碰撞摩擦，又能保证在适当的变形范围内整个涂层不发生开裂。  \n\n为了便于检查，防止漏涂，中间漆的颜色一般要与富锌漆有明显的区别，而为了防止因面漆遮盖不良而露底，中间漆和面漆的颜色差别又不宜过大。中间漆一般为一次涂装成膜，对厚涂性的要求很高。环氧中间漆的配方见表3-4-44，各种技术参数见表3-4-45。  \n\n<html><body><table><tr><td>原料</td><td>用量/质量份</td><td>原料</td><td>用量/质量份</td></tr><tr><td>环氧树脂</td><td>20</td><td>膨润土</td><td>1</td></tr><tr><td>体质颜料</td><td>46</td><td>聚酰胺固化剂</td><td>8</td></tr><tr><td>铁红</td><td>2</td><td>二甲苯</td><td>16</td></tr><tr><td>钛白</td><td>3</td><td>丙酮</td><td>4</td></tr></table></body></html>  \n\n表3-4-45 集装箱环氧中间漆各项指标（JH/TE01—2008）  \n\n\n<html><body><table><tr><td>项 目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>涂料外观</td><td>搅拌后无硬块，是均匀状态</td><td>附着力</td><td>1级</td></tr><tr><td>细度/μm ≤</td><td>60</td><td>柔韧性/mm</td><td>3</td></tr><tr><td>半硬干燥时间(80℃烘烤)/min≤</td><td>15</td><td>耐冲击性/kgf·cm</td><td>50</td></tr><tr><td>混合体积固体分/% M</td><td>50</td><td>M</td><td></td></tr></table></body></html>  \n\n(3）环氧内面漆对集装箱来说，虽然箱体内部通常是密闭的，但是为了装卸和检查货物的方便，要求涂膜有一定的装饰性。另外由于货物在装卸过程中要经常摩擦和撞击箱体内表面，所以也要求内面漆有一定的耐磨和耐冲击性；同时由于集装箱材料的保温性能差，在遇到大的温差时箱内的水蒸气会在漆膜表面结露，使得内面的腐蚀环境变得严酷；由于集装箱会装载食品，箱东都要求内面漆的漆膜无毒，并要有FDA证书；和中间漆一样，内面漆也要做成厚浆型，才能保证在涂装过程中不会产生流挂。综合这些因素，内面漆要选用环氧漆，并且在环氧的含量、PVC和颜填料的选择方面内面漆的要求反而要高一些。  \n\n典型的环氧内面漆的配方见表3-4-46，各项技术参数见表3-4-47。  \n\n表3-4-44 集装箱环氧中间漆典型配方  \n表3-4-46 集装箱环氧内面漆典型配方  \n\n\n<html><body><table><tr><td>原料</td><td>用量/质量份</td><td>原料</td><td></td><td>用量/质量份</td></tr><tr><td>环氧树脂</td><td></td><td>20</td><td>聚酰胺固化剂</td><td>9</td></tr><tr><td>体质颜料</td><td></td><td>40</td><td>二甲苯</td><td>16</td></tr><tr><td>铁红</td><td>10</td><td>丙酮</td><td></td><td>4</td></tr><tr><td>膨润土</td><td>1</td><td></td><td></td><td></td></tr></table></body></html>  \n\n表3-4-47 集装箱环氧内面漆技术指标（JH/TE01—2008）  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项 目</td><td>指标</td></tr><tr><td>涂料外观</td><td>搅拌后无硬块，呈均匀状态</td><td>混合体积固体分/%</td><td>50</td></tr><tr><td>涂膜颜色</td><td>颜色色差符合标准样板</td><td>附着力 柔韧性(方法B)/mm</td><td>1级</td></tr><tr><td></td><td>范围，△E≤2</td><td>≤ 耐冲击性/kgf·cm</td><td>3 50</td></tr><tr><td>细度/μm ≤ 半硬干燥时间(80℃烘烤）/min≤</td><td>60</td><td></td><td></td></tr><tr><td></td><td>15</td><td></td><td></td></tr></table></body></html>  \n\n(4）外面漆常用的集装箱外面漆有氯化橡胶、热塑型丙烯酸和聚氨酯三类。  \n\n在20世纪末的20年中，氯化橡胶面漆的使用很广泛。但是随看蒙特利尔公约生效，制造过程中会产生四氯化碳的氯化橡胶被禁止生产，虽然有不产生四氯化碳的水相法生产新工艺的出现，但因其性能略差，使氯化橡胶逐渐退出，丙烯酸和聚氨酯类涂料从21世纪初逐渐成为集装箱外面漆的主要成膜物质。  \n\n$\\textcircled{1}$ 氯化橡胶外面漆氯化橡胶外面漆通常采用氯化橡胶树脂或氯化聚乙烯树脂为主要成膜物质，可以与长油度醇酸树脂拼用，此外还可采用氯化石蜡等作为增塑剂。集装箱面漆的光泽要求一般在 $10\\sim20$ ( $50^{\\circ}$ 角），对于使用后的保色保光率也有一定要求，因此选择增塑剂时要注意，否则会出现早期的光泽降低及褪色。颜料通常选择耐候性比较好的无机颜料，有机颜料应选择比较高档的菁类、喹丫啶酮红等。  \n\n氯化橡胶面漆在施工中存在的最大问题是修补时的色差和咬底，这些问题的主要根源在于拼入的醇酸树脂，因为氯化橡胶树脂树脂是溶剂挥发干燥型，而醇酸树脂是氧化干燥型，在烘烤下线以后实际上醇酸树脂的氧化聚合反应还没有完全结束，这时候如果在一定的时间范围内对膜厚不足或伤损部位进行修补就会出现咬底。解决的办法是调整使用较弱的稀释剂，或者控制堆场修补的时间。按照经验，咬底通常发生在下线后的 $\\beta\\sim16\\mathrm{h}$ 内，所以修补工作应该安排在刚刚下线后或者下线后的次日进行。  \n\n$\\textcircled{2}$ 丙烯酸外面漆丙烯酸面漆在防腐性能上稍逊于氯化橡胶面漆，但是其装饰性能和施工性能却是比较优越的，近几年来逐步全面替代了氯化橡胶面漆。丙烯酸集装箱面漆一个常见的缺点是如果树脂选用不当会出现硬度不够、漆膜发软的问题。丙烯酸面漆的参考配方和性能见表3-4-48和表3-4-49。  \n\n表3-4-48 丙烯酸面漆参考配方  \n\n\n<html><body><table><tr><td>原料</td><td>用量/质量份</td><td>原料</td><td>用量/质量份</td></tr><tr><td>热塑性丙烯酸树脂</td><td>30</td><td>钛白粉</td><td>10</td></tr><tr><td>膨润土</td><td>1</td><td>二甲苯</td><td>40</td></tr><tr><td>体质颜料</td><td>19</td><td></td><td></td></tr></table></body></html>  \n\n表3-4-49 丙烯酸面漆技术指标（JH/TE01—2008）  \n\n\n<html><body><table><tr><td>项 目</td><td>指标</td><td>项 目</td><td>指标</td></tr><tr><td>涂料外观 涂膜颜色</td><td>搅拌后无硬块，呈均匀状态 颜色色差符合标准样板</td><td>混合体积固体分/% 附着力</td><td>40 1级</td></tr><tr><td>细度/μm ≤</td><td>范围，△E≤2 40</td><td>柔韧性(方法B)/mm 耐冲击性/kgf·cm</td><td>3 50</td></tr><tr><td>半硬干燥时间（80℃烘烤）/min≤</td><td>15</td><td></td><td></td></tr></table></body></html>  \n\n$\\textcircled{3}$ 聚氨酯面漆聚氨酯面漆因其优异的耐候性和装饰性，已经逐渐被箱东接受和采用。随着箱厂施工条件的改善，施工流水线上的湿度和温度都可以有效控制，这给聚氨酯漆的使用提供了有利条件。目前在配方设计上的关键点是要适应箱厂快速的生产节奏。避免因中间漆和面漆的不匹配造成的开裂、针孔、橘皮等一系列漆病。  \n\n(5）底架漆在集装箱的贮存和运输过程中，其底架部位长期处在海水和潮气中，其腐蚀环境是比较严酷的，另外底架部位遭受的冲击等损伤机会也比其他部位多，因此底架漆的防腐性能要高于一般部位的涂装配套，由于底部都是无法看到的，底架漆对装饰性没有要求。考虑到这些需要，很久以来沥青漆一直是集装箱底架漆的首选。沥青漆多采用石油沥青作为主要成膜物，具有很好的防腐、防水、防潮和抗化学药品性能，但是不耐日光曝晒，装饰性能差。现在的集装箱底架漆通常称为蜡质沥青漆，加人石蜡的目的主要是调整漆膜的表面状态，改善其流平性和施工性。由于石油沥青的组成比较复杂，甚至每个批次的黏度都不相同，因此配方中要根据需要加人适量的树脂，以使每批沥青漆的指标趋于稳定。底架漆要求干膜厚度要达到 $200\\mu\\mathrm{m}$ 以上，需要添加大量的触变剂，从成本上考虑膨润土比较合适。沥青底架漆的参考配方见表3-4-50，沥青底架漆的性能参数见表3-4-51。  \n\n表3-4-50 沥青底架漆参考配方  \n\n\n<html><body><table><tr><td>原料</td><td>用量/质量份</td><td>原料</td><td></td><td>用量/质量份</td></tr><tr><td>沥青</td><td></td><td>35</td><td>树脂</td><td>5</td></tr><tr><td>石蜡</td><td></td><td>8</td><td>膨润土</td><td>2</td></tr><tr><td>无机填料</td><td></td><td>20</td><td>溶剂</td><td>30</td></tr></table></body></html>  \n\n表3-4-51沥青底架漆技术指标（JH/TA02《集装箱用沥青底漆》）  \n\n\n<html><body><table><tr><td>项目名称</td><td>技术指标</td><td>项目名称</td><td>技术指标</td></tr><tr><td>不挥发物/%</td><td>≥60</td><td rowspan=\"3\">耐冲击试验/cm 低温试验（一40℃，于膜 200μm)/h</td><td rowspan=\"3\">≥40 48，无开裂，不脱落</td></tr><tr><td>流挂性（湿膜）/μm</td><td>≥500 ≤4</td></tr><tr><td>干燥时间（表干）/h 盐雾试验（干膜200um）/h</td><td>高温试验（100℃，干膜 96，不流淌，允许轻微变硬、变色</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 290,
+        "chunk": "# (6）其他辅助涂料  \n\n$\\textcircled{1}$ 木地板漆集装箱的地板为特制的多层胶合木板。其表面一般会刷涂清漆以达到保护和装饰的效果。目前使用的地板清漆种类较多，有环氧类、聚氨酯类和氨酯油等。规范一般要求地板漆膜厚为 $100\\upmu\\mathrm{m}$ ，和内面漆一样，各种类型的地板漆都要有FDA证书。目前大部分的地板都是采用预涂涂料的方式，地板漆的涂装也是采用大规模的批量生产，有的甚至也采用自动涂装的方式。这就要求涂装后要尽快干燥，便于尽快把地板堆码起来以节省空间，同时漆膜要有足够的硬度和耐磨性，以保证地板的正常使用。另外由于木制地板表面的多孔性，气泡是地板漆施工时最常见的漆病，在配方设计时应特别注意。  \n\n$\\textcircled{2}$ 冷藏箱发泡黏结漆冷藏集装箱的箱体为了阻断热量传递，要在两层不锈钢板间作聚氨酯发泡绝缘层，为了保证绝缘层与钢板间的有效附着，通常在两者之间涂以过渡底漆，这种底漆被称为发泡黏结剂。通常，发泡黏结剂与钢板的附着力要达到5MPa以上，这个指标一般要高于普通的环氧漆，要选用特殊的环氧树脂。  \n\n$\\textcircled{3}$ 标志漆每个集装箱都有标有箱东名称和相关信息的标贴，过去采用PVC材料贴在箱体表面。近几年来，为了降低成本，有些箱东开始采用在表面喷涂涂料作为标志。标志漆的品种和外面漆基本相同，考虑到标志漆采用空气喷涂的方式，且没有烘干条件，标志漆的干燥速率要比外面漆快一些。标志漆的典型配方见表3-4-52。  \n\n表3-4-52 丙烯酸标志漆配方  \n\n\n<html><body><table><tr><td>原料</td><td>用量/质量份</td><td>原料</td><td>用量/质量份</td></tr><tr><td>热塑性丙烯酸树脂</td><td>30</td><td colspan=\"2\">钛白粉</td><td>10</td></tr><tr><td>膨润土</td><td>1</td><td colspan=\"2\">二甲苯</td><td>40</td></tr><tr><td>体质颜料</td><td>19</td><td colspan=\"2\"></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 291,
+        "chunk": "# 三、集装箱生产线及对涂料性能的要求和影响  \n\n随着集装箱制造技术的进步和规模生产的进一步要求，年产30万箱的集装箱工厂已经出现，对涂料的要求也进一步提高，主要集中在干燥性能等方面，同时对涂料的稳定性也提出了更高的要求，由于生产速率的大大提高，意味着调试涂料的短短过程中就会产生大量的、有质量问题的箱子，这是箱厂不能接受的。因此涂料质量的稳定性是对现代集装箱涂料最基本也是最严格的要求。",
+        "category": " Introduction"
+    },
+    {
+        "id": 292,
+        "chunk": "# 1.集装箱厂涂装生产线的配置  \n\n如图3-4-48所示是集装箱工厂典型的涂装流水线配置图，各工位的职能如下。  \n\n$\\textcircled{1}$ 部装、总装线将板材、型材焊接成规定的集装箱箱体。$\\textcircled{2}$ 验光房通过光照，检查焊道是否有漏焊现象。$\\textcircled{3}$ 二次打砂房对焊道部位重新打砂。$\\textcircled{4}$ OK站清理焊渣飞溅以及对焊道进行修整。$\\textcircled{5}$ 富锌漆预涂工位对顶梁、底梁、门框等部位进行预涂。$\\textcircled{6}$ 富锌漆喷涂工位对门板和前端以及箱内进行手工喷涂富锌漆，外侧板和外顶板进行自动喷涂。$\\textcircled{7}$ 中间漆喷涂/内面漆预涂工位箱外进行中间漆喷涂，其中门板和前端进行手工喷涂，侧板和顶板进行自动喷涂，箱内顶梁、底梁、门框等部位进行内面漆预涂。$\\textcircled{8}$ 中间漆流平/内面漆顶板喷涂工位箱外中间漆流平，箱内顶板喷涂内面漆。$\\textcircled{9}$ 流平房中间漆、内面漆流平。$\\textcircled{10}$ 低温烘房对箱外中间漆进行烘烤，以利于外面漆喷涂。$\\textcircled{1}$ 内面漆侧板喷涂工位箱内侧板喷涂内面漆。$\\textcircled{12}$ 横移工位将集装箱平移至指定位置，以进行下一工位操作，同时箱内、箱外涂料流平。$\\textcircled{13}$ 外面漆/底架漆预涂工位箱外顶梁、底梁、门框等部位进行外面漆预涂，箱内底横梁进行底架漆预涂。$\\textcircled{14}$ 外面漆喷涂工位进行外面漆喷涂，其中门板和前端进行手工喷涂，侧板和顶板进行自动喷涂。$\\textcircled{15}$ 烘房使外面漆表干，以利于进行下一工位操作。$\\textcircled{16}$ 分界线房对门框、R角等部位分色。$\\textcircled{1}$ 烘房使箱内、箱外涂料烘烤干燥。$\\textcircled{18}$ 强制冷却房以吹扫冷空气的方法，使箱体温度降至室温，以利于下一工位的操作。$\\textcircled{19}$ 修补工位对箱体进行检查，对缺陷处进行修补，次工位可以测量膜厚。$\\textcircled{24}$ 美装线进行铺地板、贴标、门锁杆和门封胶条的安装、通风罩的安装与标牌、打密封胶等装饰性工作，以及底架漆喷涂和水密实验等工作。  \n\n$\\textcircled{21}$ 出箱口对箱体进行最后一次检查，并将集装箱放置于堆场。  \n\n![](images/1082eb403a5775f7fd23527c7585b8df847519f39fc8612c5c09d69ce413bf3d.jpg)  \n中中合好十力果系有有年1: 「 H",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 293,
+        "chunk": "# 2.集装箱涂料施工工艺  \n\n不同的集装箱生产线对涂料的要求也不同，尤其是烘房的布局形式和箱子的停留时间不同，对涂料施工后的初期干燥、溶剂释放、流平性等的要求也有很大的差别。常见的流挂、针孔、漆雾、橘皮和干燥不良等漆病，往往与生产线的布置不合理有关。这种情况通常要通过反复调整设备参数和涂料稀释剂种类及稀释比例来加以改进。近几年来，随着集装箱制造厂的集团化和产能的不断提高，旧工厂逐渐被淘汰，新工厂的设计已经渐趋合理，涂料在各集装箱厂的适应性也加强了。  \n\n通常，各箱东、箱厂和涂料商都会对集装箱的生产过程中涂料的施工过程进行严格的检验与控制，制定详细而严格有效的涂料施工工艺流程，是保证整个施工过程质量的重要措施，施工工艺一般从涂料规格、底材处理、涂料施工、漆膜检测等各方面进行严格的规定，下面详细介绍集装箱施工管理的整个过程。  \n\n(1）涂料规格表涂料规格表规定了涂料和涂装相关的一些技术参数，包括涂料品种、干/湿膜厚度、兑稀率、调漆黏度、干燥条件、枪嘴尺寸、泵压等，不同的箱型会有所区别，不同的箱东的涂料规格要求也不尽相同，表3-4-53是一典型集装箱的涂料规格。  \n\n表3-4-53 典型集装箱的涂料规格  \n\n\n<html><body><table><tr><td>位置</td><td>涂料品种</td><td></td><td>干膜厚度/μm湿膜厚度/μm稀释比例/%</td><td></td><td>岩田杯黏度/s</td><td>枪嘴型号</td><td>干燥条件</td><td>泵压力/MPa</td></tr><tr><td rowspan=\"5\">外 表 面</td><td>环氧富锌底漆</td><td>10</td><td>21</td><td>130~150</td><td>最低7 最高9</td><td>821 619</td><td>最低80℃ 最高100℃</td><td>0.15~0.25</td></tr><tr><td>环氧富锌底漆</td><td>20</td><td>42</td><td>25</td><td>最低10 最高15</td><td>421 419</td><td>自然干燥</td><td>0.3~0.5</td></tr><tr><td>环氧中间漆</td><td>40</td><td>60</td><td>15~40</td><td>最低20 最高45</td><td>621 619</td><td>最低30℃ 最高50℃</td><td>0.3~0.5</td></tr><tr><td>丙烯酸面漆</td><td>55</td><td>125</td><td>15~40</td><td>最低50 最高70</td><td>621 619</td><td>最低65℃ 最高85℃</td><td>0.3～0.5</td></tr><tr><td>环氧富锌底漆 内</td><td>10</td><td>21</td><td>130～150</td><td>最低7 最高9</td><td>821 619</td><td>最低80℃ 最高100℃</td><td>0.15～0.25</td></tr><tr><td>表 面</td><td>环氧富锌底漆</td><td>20</td><td>42</td><td>25</td><td>最低10 最高15</td><td>421 419</td><td>自然干燥</td><td>0.3~0.5</td></tr><tr><td></td><td>环氧内面漆</td><td>50</td><td>74</td><td>15~40</td><td>最低20 最高45</td><td>421 419</td><td>最低65℃ 最高85℃</td><td>0.3~0.5</td></tr><tr><td rowspan=\"2\">底 架</td><td>环氧富锌底漆</td><td>10</td><td>21</td><td>130~150</td><td>最低7 最高9 最低10</td><td>821 619</td><td>最低80℃ 最高100℃</td><td>0.15~0.25</td></tr><tr><td>环氧富锌底漆</td><td>25</td><td>53</td><td>25</td><td>最高15</td><td>419</td><td>自然干燥</td><td>0.3~0.5</td></tr><tr><td>沥青漆</td><td></td><td>200</td><td>400</td><td>0~5</td><td></td><td></td><td>自然干燥</td><td></td></tr></table></body></html>\n\n注：1.涂料黏度一般会随环境温度变化而变动，因此温度变化时要及时调整黏度已达到满意的施工效果。2.整体干膜厚度的变化会影响漆膜的干燥时间。3.湿膜厚度的数据是计算值，仅供参考，最后验收时应以于膜厚度为准。4.在 $20\\%$ 时富锌漆的混合使用期限为 $8h$ ，中间漆和内面漆为6h，超过混合期限的涂料禁止使用。  \n\n(2）环氧富锌漆混合工艺要求由于富锌漆通常为双组分且锌粉含量高，涂装前由于大量兑人稀释剂造成黏度很低，极易沉降而造成涂膜中的锌粉含量不均匀，这就需要富锌漆在整个喷涂过程中均保持不间断的有效搅拌。因此对混合用容器、搅拌器形式、混合方式、揽拌时间等做出严格规定是保证富锌漆质量的一个重要内容。  \n\n$\\textcircled{1}$ 对富锌漆混合罐的要求为了保证富锌漆的混合搅拌效果，应采用两个混合罐串联的方式，A罐用于预混，B罐用于向系统供漆。两个混合罐的容积一般不能小于 $100\\mathrm{L}$ 。为保证较好的混合效果，富锌漆的装量应少于混合罐高度的2/3。  \n\n由于富锌漆的密度较大，非常容易出现较硬的沉淀物，因此应先使用特定的三刃搅拌器在原包装桶中将主剂搅拌均匀后再倒入混合罐。混合罐中也同样应采用单三刃搅拌器，但揽拌桨直径要大些，以便在直径更大的混合罐中取得好的混合效果。  \n\n混合罐A中的搅拌器应该位于混合罐的中央，搅拌器的转速，车间底漆为1200～${2000}\\mathrm{{r}/\\mathrm{{min}}}$ ，中间漆和内面漆为 $1400{\\sim}2400\\mathrm{r/min}$ 。罐底应有 $5^{\\circ}\\sim10^{\\circ}$ 的坡度，以便于涂料流动，防止锌粉沉积。为了保证搅拌效果，搅拌桨应位于罐底圆柱体的基线上。罐底要有阀门以便于调节和控制富锌漆流人混合罐B的速率。A罐至B罐的涂料管路和喷漆泵的涂料吸人管之间应保持最远的距离。  \n\n$\\textcircled{2}$ 富锌漆混合步骤a.打开富锌漆主剂桶。  \n\nb.用便携式搅拌器在原包装桶中将富锌漆主剂搅拌 $1{\\sim}2\\mathrm{min}$  \n\nc.打开固化剂包装桶。  \n\nd.将固化剂倒人已经搅拌均匀的主剂中。  \n\ne.再将主剂和固化剂混合搅拌 $1\\sim2\\mathrm{min}$ 睿f.将混合搅拌均匀的富锌漆倒人混合罐A中。  \n\ng.如果富锌漆的需求量大，重复上述步骤加人多桶富锌漆。  \n\nh.用少量溶剂清洗使用过的主剂和固化剂包装桶以使残留的涂料能够被全部使用，这样既可减少浪费又可保证涂料的配合当量比准确。  \n\ni.将清洗包装桶的溶剂也倒入混合罐A中。  \n\nj.再将混合罐A搅拌 $2\\sim3\\mathrm{min}$ ，使富锌漆和溶剂充分混合。然后打开控制阀门让搅拌均匀的富锌漆流人混合罐 $\\mathbf{B}$ 0  \n\nk.搅拌混合罐B内的富锌漆 $2\\mathrm{\\sim}3\\mathrm{min}$ ，同时备好喷漆泵。  \n\n1.保持连续搅拌，开始喷漆。并在整个喷漆作业过程中一直保持搅拌。  \n\nm.当混合罐中的富锌漆快使用完毕时，重复上述a～j的操作，重新配好富锌漆并放入混合罐B。  \n\n$\\textcircled{3}$ 工作间歇后的搅拌在喷漆施工中经常会出现因设备维修、工人吃饭休息、工艺节奏等原因造成短暂的工作间歇，在恢复操作后应注意以下几点。  \n\na.富锌漆有混合使用期限要求，超过混合使用期，涂料的性能会受到影响，严重的会产生结胶，造成设备和材料的报废，因此在工作间歇时一定要考虑到混合使用期限。预计间歇超过混合使用期的应清除设备和管路中的涂料。富锌漆的混合使用期限和温度有关，温度升高，混合使用期将缩短，具体的数据参考涂料供应商的技术参数。  \n\nb.在超过 $10\\mathrm{min}$ 的工作间歇后，应对富锌漆充分搅拌 $\\mathsf{10m i n}$ 以上方可再进行喷漆施工。在条件允许的情况下，施工间歇期间应尽量对已经混合好的富锌漆保持持续搅拌，以防止锌粉发生沉降。  \n\n(3）板材的底材处理所有板材必须选用ISO8501规定的A级板，并且不能有油污、灰尘、腐蚀或其他污物。如发现上述杂质应用溶剂清洗并用干净的抹布擦干或用气流吹干。  \n\n磨料应采用以下材料并按要求的比例混合均匀：8抛头喷砂机磨料使用 ${\\bf S}230:{\\bf G}40=$ $6:4$ ；16抛头喷砂机使用 $\\mathrm{S280:G25}$ ：钢丝段 $=5\\div3:2$ ，并且应经常加入新的磨料。线速度为 $10\\mathrm{m/min}$ 8  \n\n喷砂等级为ISO8501规定的 $\\mathrm{\\bfSa~2.~5}$ 级，粗糙度控制在 $25\\sim45\\mu\\mathrm{m}$ （Rugo test ${\\mathfrak{3}}^{\\#}$ N9a～$\\mathrm{N10b)}$ ，喷砂密度应大于 $75\\%$ ，清洁度应达到三级。  \n\n板材处理后要马上喷涂车间底漆。用专用稀释剂将富锌漆黏度调整至 $7\\sim95$ (岩田杯)，并用气动搅拌充分搅匀。调整喷漆泵压力至适当值（通常为 $0.15{\\sim}0.25\\mathrm{MPa})$ 。并选择合适的枪嘴。调漆罐应该加盖，防止进入杂质。喷漆房的门应关闭，通风系统应开启。喷漆房、调漆间以及所有的照明设施应该定期清理，保持整洁。要注意涂料的混合使用期限（通常为$20C$ 下 $\\mathrm{8h}$ )，必须在混合使用期限内将涂料使用完毕。板材涂装车间底漆后应加热干燥，以保证堆码时板材之间不粘连，干燥温度应控制在 $80\\sim100^{\\circ}C$ ，使用热风循环加热。漆膜应干燥至半硬，出烘房后应采用冷风降温。检查涂膜的厚度，如果发现漏底应立即用空气喷枪修补，漆膜厚度应该控制在 $10{\\sim}20\\mu\\mathrm{m}$ o  \n\n应确认钢板表面漆膜已完全干燥，漆膜表面无油、无水、无尘，没有脚印。已涂车间底漆的钢板的贮存期限通常为15天，超过15天或者表面出现锌盐的钢板应重新进行喷砂处理。  \n\n(4）型材的处理与板材一样，钢材必须选用ISO8501规定的A级，并且不能有油污、灰尘、腐蚀或其他污物。如发现上述杂质应用溶剂清洗并用干净的抹布擦干或用气流吹干。型材必须在8抛头喷砂机上进行处理，磨料比例为 $\\mathrm{S280:}\\ \\mathrm{G25}\\ :$ ：钢丝段 $=5:3:2$ ，应经常补充新的磨料。线速度 $3\\mathrm{m/min}$ 。喷砂等级、粗糙度、喷砂密度和清洁度的要求与板材相同。  \n\n型材的富锌漆施工工艺与板材基本相同，喷砂处理完的型材应放在托架上喷漆，不允许堆码或斜靠在一起，喷漆时喷枪和工件的距离应为 $30\\sim50\\mathrm{cm}$ ，注意不易喷涂的部位要特别注意。  \n\n所有工件应采用人工喷涂，喷涂完一面后停止喷漆，自然干燥（确保环境温度高于$5^{\\circ}C$ ）后再分别涂其他面。涂料未半硬干前不得移动工件。  \n\n检查涂膜的厚度，如果发现漏底应立即用空气喷枪修补，测量膜厚时应特别留心边角部位的膜厚。  \n\n型材的贮存条件与板材相同。  \n\n(5）二次喷砂处理喷涂车间底漆后的板材和型材组装成集装箱后，需要对焊道等部位进行喷砂处理，这个过程叫做二次喷砂，其目的一方面是为了清除焊道和周围的氧化物和飞溅等；另一方面是为了释放应力。实践证明，大部分旧箱子的腐蚀都发生在焊道部位。因此做好二次喷砂处理非常重要。  \n\n二次喷砂前，应磨平尖锐和不平的焊道，清除焊渣、飞溅及杂物。用干净的刷子蘸溶剂清除油污，并用压缩空气吹干。由于二次喷砂通常为人工操作，应确保喷砂作业时的照明和防尘，磨料应采用 $\\mathtt{S230:G40}$ ：钢丝段 $=5\\div3\\div2$ ，并混合均匀。喷砂等级也为ISOSa2.5级。粗糙度为 ${\\bf N}\\9\\mathrm{a}\\mathrm{\\sim}{\\bf N}10{\\mathrm{b}}$ （Rugo test ${\\mathfrak{3}}^{\\sharp}$ )，密度、清洁度等与一次喷砂相同。  \n\n(6）二次喷砂OK站和富锌漆预涂通常在OK站进行补焊、清除杂物、吹扫磨料等工作。应检查是否存在喷砂不合格或漏喷，若发现应该及时补喷。在此处只允许少量的补焊，如果补焊过多应重新返回进行喷砂。要用溶剂清除所有的污物，并用压缩空气吹干或用干净的抹布擦干。清理完毕后应按照要求对难以涂到或容易漏涂的部位进行富锌漆的预涂，预涂用的富锌漆黏度要合适，刷子要经常更换，一次配漆量不要过多，以免超过混合使用期限。具体的预涂操作顺序如下。  \n\n$\\textcircled{1}$ 首先刷涂低处的焊道。  \n\n$\\textcircled{2}$ 底架喷漆前应先在地坑内用刷涂或空气喷涂的方法预涂其焊道。  \n\n$\\textcircled{3}$ 最后刷涂顶部的焊道。  \n\n(7）流水线富锌漆施工在此工序要涂装内面、外面和底架部位的富锌漆。通常富锌漆的涂装都采用人工无空气喷涂的方式，具体的要求如下。  \n\n涂料黏度调整至10～15s，并保持持续搅拌。调漆罐要有防尘措施，喷漆时应关闭喷漆房门并打开风扇保持通风。枪嘴尺寸为419，泵压0.3～0.5MPa，停止喷漆作业时，喷枪的枪嘴应浸于溶剂之中，防止干结。由于富锌漆的颜色较暗，要经常清理照明灯保证足够的亮度，以便于检查涂膜状态。  \n\n内面富锌漆涂装的步骤是先喷涂焊道然后进行全面涂装。保持喷涂距离为 $30\\sim50\\mathrm{cm}$ 喷枪移动方向要始终与被涂板面平行。  \n\n外面富锌漆喷涂的基本顺序也是先涂装焊道再进行全面涂装，先涂装顶板冉涂装侧板。顶板预涂完成后，为了防止漆雾附着，应由两名工人站在平台上，面对面地喷涂顶板。当喷涂门媚和前上梁等高处的部件时，应站在高凳上或梯子上，保证喷枪和被涂部位保持在同一高度上，这样可以保证喷涂的膜厚均匀。  \n\n喷涂完成后应在 $5^{\\circ}C$ 以上的环境中至少停置 $5\\mathrm{min}$ ，让溶剂挥发，以利于涂装下一度环氧漆。  \n\n(8）环氧中间漆的施工中间漆施工时，绝大多数工厂的生产线采用自动喷涂顶板和侧板，手工喷涂前端和门板的方式，涂料的黏度应调整至 $20\\sim45{\\bf s}$ ，泵压应控制在 $0.3\\sim$ $0.5\\ensuremath{\\mathbf{M}}\\ensuremath{\\mathbf{Pa}}$ ，首先按照要求进行预涂。  \n\n对于人工喷涂的部位，应特别注意底侧梁、顶侧梁、角柱和前等部位的膜厚要达到要求。为确保膜厚稳定，工人操作时要保持足够和稳定的喷涂距离，移动时要始终保持与被涂平面平行。涂装门和前上梁等高处的部件时，应站在高凳上，以保证枪距稳定膜厚均匀。  \n\n对于自动喷涂的部分，要经常检查喷涂机的工况和清洁，及时清除漆雾并确认枪嘴尺寸。随着喷涂的进程枪嘴会逐渐磨损，所以每个班次都应定期检查湿膜厚度的变化，以掌握枪嘴的磨损程度，枪嘴过大时应及时更换。  \n\n(9）环氧内面漆施工内面漆目前主要是采用人工喷涂的方式，由于箱体处于半封闭状体，对工人危害比较大。现在有效的保证工人呼吸的方式是采用送气式面罩，这种面罩的特点是用一根气管将新鲜的压缩空气送到封闭的面罩内供工人呼吸，由于面罩内有正压，环境中的漆雾和溶剂就不容易进人面罩内，其缺点是气流的噪声很大，需要采用护耳等来防止听力损伤。  \n\n环氧内面漆的喷涂工艺要求与环氧富锌漆喷涂内面时基本相同。  \n\n(10）中间漆和内面漆的静置和干燥中间漆涂装完毕，应适当干燥后再涂装面漆，通常会有 $10\\mathrm{min}$ 左右的静置时间，便于溶剂挥发，然后进人烘房，烘房的温度为 $30\\sim50^{\\circ}C$ 曹停留时间应保持 $15\\mathrm{min}$ 0  \n\n在夏季气温较高时烘房也可以不开，只作为静置室使用。  \n\n(11）面漆的施工和环氧中间漆一样，面漆也采用自动和人工喷涂相结合的方式。面漆的黏度应调整至 $50\\sim70\\mathrm{s}$ ，其他要求和环氧中间漆基本相同。  \n\n(12）外面漆的干燥外面漆的干燥工序是涂料施工工艺中非常重要的一个阶段。由于在喷涂外面漆时，中间漆和富锌漆都还没有完全干燥，因此这个工序不仅仅是外面漆的干燥，还包括了中间漆、内面漆甚至环氧富锌漆的干燥，其干燥机理是比较复杂的。  \n\n面漆的烘房是集装箱涂装线的关键设备，烘房的排布方式和生产能力往往决定整个生产线的能力。典型的烘房为通道式，生产速率是设计烘房长度的一个重要参数。  \n\n例如箱厂一条生产线要保证每班 $10h$ 生产100台40ft箱。那么生产每台40ft箱所需要时间为 $\\mathfrak{f m i n}$ 中  \n\n按照烘干要求 $80^{\\circ}C$ 下 $15\\mathrm{min}$ ，就需要3个40ft箱位，也就是说，烘方的长度不能小于$3\\times12.2{=}36.6(\\mathrm{m})$ 0  \n\n如果产能提高一倍，即达到10h班产200台40ft箱，则烘房的最小长度也要加倍到 $73.2\\mathrm{m}$ d  \n\n对于集装箱的内表面，环氧漆是面漆，其下层的环氧富锌漆也和其性质相似，冉加上坏氧内面漆已经在中间漆烘房得到了适当的干燥，通常中间漆的十燥情况都是非常好的，但是有些水平的平面，如底侧梁的上表面，由于多次喷漆的影响，局部的膜厚较高，往往也会产生于燥不良的情况，而影响地板的装配进度，在施工时要控制这些部位的膜厚不要超出标准太多，通常控制在标准膜厚的2.5倍以内。  \n\n(13）底架漆的施工目前大部分的底架采用沥青漆，沥青漆也采用高压无气喷涂方式。由于底架部位没有装饰性要求，主要的控制参数就是膜厚要满足要求和不要产生流挂。为了保证施工方便，沥青漆的施工工位通常都有地坑。由于沥青漆的黏度受温度的影响较大，施工温度要控制在 $15\\sim35^{\\circ}C$ ，否则容易产生流挂和雾化不良。  \n\n对于和外表面涂料配套相同的底架，施工时可以参考外表面涂料的施工工艺。  \n\n(14）地板漆的施工集装箱用地板漆有环氧清漆和聚氨酯清漆，也有为遮盖木材缺陷而设计的深色半透明清漆。地板漆施工通常采用辊涂的方法在流水线之外提前涂装好，即采用人工用辊刷的施工方式，为了保证膜厚要反复涂装 $2\\sim4$ 次。地板漆的重要指标是干燥性。涂装过程中气泡是常见的病，防止气泡的办法除在涂料设计时加人消泡剂之外，施工过程中应该采用短毛辊刷和调整黏度的方式。为了提高涂装效率现在很多箱厂也采用了淋涂和辊涂相结合的自动涂装方式。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 294,
+        "chunk": "# 四、常见的涂膜病及解决方法  \n\n和其他涂料一样，集装箱涂料在施工过程中也不可避免地产生一些漆病。与一般涂料不同的是，由于是流水线施工，出现漆膜病后必须马上进行调整，而且现在的生产速率一般不允许停线来修整漆膜病或调整涂料，因此出现漆膜病后必须用最快和最简单的办法尽快调整，否则就会给箱厂造成巨大的经济损失，这一点是在设计集装箱涂料时必须要考虑的。现将几种常见漆病的形成原因和解决办法总结如下。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 295,
+        "chunk": "# 1.流挂  \n\n造成流挂原因通常有三个：由于各种原因导致的涂膜过厚、涂料本身的触变性不够及涂料的调整和环境温度的问题。  \n\n除了富锌漆以外，集装箱涂料都是厚膜型涂料，在涂料设计时都会考虑要有较高的抗流挂性。但是为了获得比较好的表面状态，涂料的流平性能必须要好。所以涂料配方设计时均衡厚膜性和其他性能的关系是解决流挂问题的关键。另外有些施工参数的变化会使涂膜厚度趋于增加，调整这些工艺参数也可以解决施工过程中产生的流挂。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 296,
+        "chunk": "# 2.针孔  \n\n总体来讲，针孔主要是漆膜表面封闭过快而底层溶剂没有完全挥发所致，涂膜过厚、静置时间过短、过度通风和加热升温过快等都会造成针孔。搅拌时混入的气泡过多也容易产生针孔。另外一种针孔实际上是因为涂料流平不好和对底材润湿不良引起的。根据不同的原因，应该采用对应的办法来解决。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 297,
+        "chunk": "# 3.缩孔  \n\n缩孔是由于涂料和底材（或底层油漆）的表面张力差造成的，当涂料的表面张力过高时，涂料不能完全润湿底材，就会产生缩孔。当涂料有缩孔的趋势时，细小的杂质也会加重缩孔的产生。底层的污染和过度干燥都会造成出现缩孔。集装箱生产过程中产生缩孔的原因是多方面的，也是非常复杂的，除了油污、水和灰尘以外，其他工艺过程中使用的油、蜡和助剂都可能会产生缩孔。解决缩孔有效的办法是加人硅油类助剂，但是注意要先将硅油溶入溶剂中再加入涂料里，而且要控制加入量。值得注意的一点是，加入硅油类防缩孔助剂后，面漆的表面能会降低，往往会影响标贴对箱体的附着力。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 298,
+        "chunk": "# 4.橘皮  \n\n橘皮通常是施工时产生的装饰性的缺陷，主要是由于涂料流平性不好造成的。直接的原因是涂料黏度过高，不易流平；喷涂压力过低，雾化不好等原因造成的，橘皮会影响涂料的光泽和外观。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 299,
+        "chunk": "# 5.泛白  \n\n泛白是热塑性外表面漆常见的病，主要是因为涂料在挥发干燥过程中表面温度降低，如果遇到周边空气湿度过大，水汽就会在涂膜表面凝结，一部分水也会进人漆膜，因难以散发而出现白色。另一部分则会附在漆膜表面，占据涂膜表面的位置，当水挥发后造成涂膜表面微观上的不平整，对光线形成漫反射而呈现表观上的白色。泛白的现象有的随着涂膜干燥进程，水汽挥发而变轻，有些则难以恢复。不严重的泛白可以通过在其表面喷涂一层溶剂的方法将涂膜表面“溶平”或将水分带走。严重的泛白须打磨处理重新修补。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 300,
+        "chunk": "# 6.开裂  \n\n施工刚结束后的开裂通常是因为涂膜间张力的差别造成，易见于不同类型涂料覆涂时。除了配方设计的原因以外，内外层干燥速率的不匹配是造成开裂的主要原因。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 301,
+        "chunk": "# 7.附着不良  \n\n由于底材处理工艺和涂料配套都是比较成熟的，集装箱涂料出现附着不良的概率不高。只有当钢板被油污等严重污染或表面存在大量灰尘杂质时才会出现大面积的脱落。其他附着力降低的情况与施工过程中的干燥和底层漆膜的处理有关。  \n\n集装箱生产过程中常见的漆膜病和解决措施见表3-4-54。  \n\n表3-4-54集装箱涂料常见的漆膜病和解决措施  \n\n\n<html><body><table><tr><td>漆膜病</td><td>产生原因</td><td>解决措施</td></tr><tr><td rowspan=\"5\">流 挂</td><td>涂膜厚度过厚： 控制不当造成涂膜厚度过厚； 喷涂枪嘴型号不合理，扇幅宽度过窄或出漆量过大； 车速过慢； 枪口距被涂物距离过近；</td><td>控制涂膜厚度在合理范围内； 选择合适的枪嘴； 提高车速在合理的范围内； 增加枪口距被涂物距离；</td></tr><tr><td>喷涂压力过高 施工黏度过低（兑稀率过高）</td><td>降低喷涂压力 提高施工黏度（减小兑稀率）</td></tr><tr><td>钢板打砂密度及粗糙度过低</td><td>提高钢板打砂密度，打砂粗糙度控制在合理范围内</td></tr><tr><td>溶剂挥发速率过慢： 溶剂本身挥发速率过慢； 环境温度低造成溶剂挥发过慢</td><td>使用快干稀释剂，提高溶剂挥发速率</td></tr><tr><td>涂料本身抗流挂性过差</td><td>提高涂料抗流挂性，如加人防流挂助剂等</td></tr></table></body></html>  \n\n续表  \n\n<html><body><table><tr><td>漆膜病</td><td>产生原因</td><td>解决措施</td></tr><tr><td rowspan=\"7\">针 孔</td><td>搅拌或喷涂产生的气泡喷涂至钢板表面，气泡破 裂后涂膜不能及时流平</td><td>在涂料混合搅拌后，静置一段时间至容器内气泡完全 消失，或在涂料中加人消泡助剂减少气泡的产生</td></tr><tr><td>涂膜表干过快，底层溶剂挥发不畅； 溶剂挥发过快，造成表干过快； 底漆或中间漆溶剂挥发过慢，面漆表干后，下层涂 料溶剂仍未挥发完全； 涂膜厚度过厚，表层涂料已经表干，下层涂料溶剂</td><td>选择合适挥发速率的溶剂，使上层涂料溶剂挥发不至 过快，而下层涂料溶剂挥发不至过慢； 控制涂膜厚度在合理的范围内；</td></tr><tr><td>仍未挥发完全； 通风过度造成涂膜表干过快； 流平工位过少，造成流平时间不足，进人烘房后涂 膜表干，但下层溶剂仍未挥发完全； 初期烘烤温度过高</td><td>降低施工后空气表面流通速率，如降低风机功率等； 增加流平时间； 降低初期烘烤温度，如设置低温烘房保证溶剂挥发， 而后进人高温烘房保证涂膜干燥</td></tr><tr><td>涂料不能完全覆盖基材或下层涂膜，形成露底式 针孔现象； 施工黏度过高(兑稀率过低)； 喷涂压力过低； 车速过快； 枪嘴型号选择不当，造成雾化程度不良；</td><td>调整施工黏度、喷涂压力、车速及枪嘴距被涂物距离 至合理范围； 选择合适的枪嘴型号； 清洗或更换无空气喷涂机压缩泵过滤网；</td></tr><tr><td>枪嘴距被涂物距离过远； 无空气喷涂机压缩泵过滤网堵塞，造成出漆量 不足； 涂料本身对基材或下层涂膜的润湿性差</td><td>增加涂料对基材或下层涂料的润湿能力，如加人润湿 分散剂等</td></tr><tr><td>污染造成的缩孔； 基材或下层涂膜被污染造成表面张力过大，至使 上层涂料施工后产生缩孔； 杂质的混人，如油污或水等，导致涂料施工后，局</td><td>注意基材的清洁度，严格防止杂质对基材、下层涂膜 或涂料的污染</td></tr><tr><td>部表面张力过大，从而产生缩孔 下层涂料干燥过度，造成下层涂料表面张力过大</td><td>降低下层涂料的烘烤温度或烘烤时间，使上下层涂料</td></tr><tr><td rowspan=\"5\"></td><td>在制造涂料过程中，低表面张力助剂，如有机硅类</td><td>之间产生“互溶\"现象，从而避免缩孔现象的产生 加入适宜的流平助剂，降低涂料的表面能，从而减少</td></tr><tr><td>消泡剂或流平剂，加人量过大，从而产生缩孔</td><td>缩孔现象的发生，但如由于加人低表面张力的消泡剂或 流平剂产生的缩孔现象，应减少或避免使用此类助剂</td></tr><tr><td>溶剂与涂料的互溶性差</td><td>增加溶剂的溶解性</td></tr><tr><td>施工黏度过高(兑稀率过低) 喷涂压力过低</td><td>降低施工黏度，增加兑稀率 提高喷涂压力</td></tr><tr><td></td><td>降低车速</td></tr><tr><td rowspan=\"11\">橘 皮</td><td>车速过快</td><td></td></tr><tr><td>枪嘴型号选择不当，造成雾化程度不足</td><td>选择合适的枪嘴型号</td></tr><tr><td>喷枪距被涂物距离过远</td><td>降低喷枪距被涂料距离</td></tr><tr><td>溶剂挥发速率过快</td><td>降低溶剂的挥发速率，使用慢干型稀释剂</td></tr><tr><td>通风过度</td><td>降低施工后空气表面流通速度，降低风机功率</td></tr><tr><td>流平工位过少，造成流平时间不足，就进人烘房</td><td>增加流平时间或降低初期烘烤温度</td></tr><tr><td></td><td>增加基材或下层涂膜烘烤后的冷却时间</td></tr><tr><td>基材或下层涂料温度过高</td><td></td></tr><tr><td></td><td></td></tr><tr><td>涂料本身流平性差</td><td>在涂料中加人流平助剂</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>漆膜病</td><td>产生原因</td><td>解决措施</td></tr><tr><td rowspan=\"3\">泛 白</td><td>溶剂挥发速率过快</td><td>降低溶剂的挥发速率，使用高沸点溶剂或慢干型稀 释剂</td></tr><tr><td>相对湿度过大，如下雨等</td><td>在相对湿度较大时，应尽量避免未完全干燥的涂膜直 接暴露在空气中，在下雨天气时，对已完全干燥的涂膜 也应加以遮盖</td></tr><tr><td>涂料本身抗水性差</td><td>在涂料中加人增加表面抗水性的表面助剂 增加中间漆的烘烤时间和烘烤温度，或增加中间漆流</td></tr><tr><td rowspan=\"2\">开 裂</td><td>底层涂料与面层涂料在成膜过程中收缩率差别过 大或软硬程度差别过大造成的开裂，如底层涂料在 还未达到表干的程度就喷涂面漆（尤其是双组分聚 氨酯面漆），即“湿碰湿”施工，由于面漆在干燥过程 中收缩程度大于底层涂料，从而造成开裂现象的 发生</td><td>平时间，或在中间漆中加人快干稀释剂，在喷涂面漆时， 使用中间漆达到或超过表干程度，防止开裂现象的 发生； 增加钢板的打砂粗糙度，增加底材对涂膜的附着能 力，防止开裂</td></tr><tr><td>环境温度过低，当集装箱处于生产线时，涂膜处于 相对较高的温度下，骤然放至温度过低的室外，由于 “热胀冷缩”造成涂膜开裂</td><td>集装箱在出箱口增加放置时间，防止骤冷</td></tr><tr><td></td><td>表层涂料过脆，在集装箱搬运过程中，由于磕碰， 造成涂膜开裂 涂膜对基材的附着不良；</td><td>在表层涂料中加人增韧助剂，防止涂膜过脆 严格防止钢板污染，有必要时，对钢板进行清洗或火</td></tr><tr><td rowspan=\"2\">附 着 不 良</td><td>钢板被大面积污染，如油污等； 钢板打砂粗糙度不良或打砂密度过低； 打砂后的钢板未及时喷涂富锌底漆或富锌漆喷涂 膜厚不足，致使钢板发生锈蚀</td><td>烧除油； 增加对钢板的打砂密度和打砂粗糙度； 钢板打砂后及时喷涂富锌漆，并控制富锌漆膜厚不致 过低，对已发生锈蚀的钢板，应重新打砂并进行富锌漆 的喷涂</td></tr><tr><td>涂膜层间附着不良； 底层涂料干燥过度； 面漆完全干燥后进行修补时，未对下层涂料进行 重新打磨； 下层涂料中含有过多的低表面张力助剂</td><td>缩短面层涂料与底层涂料的施工间隔，必要时采用 “湿碰湿”的施工工艺； 对已完全干燥的涂膜进行修补时，应重新打磨； 减少涂料中低表面张力的使用量</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 302,
+        "chunk": "# 五、集装箱涂料、涂装的发展趋势  \n\n目前集装箱在我国已经成为一个重要的产业，而且在今后一段时间内应该一直呈现较稳定的需求趋势，集装箱涂料也已成为涂料行业的一个重要分支，因此探讨集装箱涂料的发展趋势对涂料行业的可持续发展也有一定的意义。  \n\n集装箱制造作为一个劳动密集型的重要产业，随着社会的进步，其产业工人的安全和对周围环境的影响已越来越受到重视。在集装箱制造过程中，涂料是对工人身体健康和周围环境威胁最大的污染源之一，另外由于食品安全越来越被人们重视，集装箱内涂料对所装载的食品是否会造成污染也越来越成为人们担忧的问题，因此开发环保型的集装箱用涂料是今后行业的方向。",
+        "category": " Introduction"
+    },
+    {
+        "id": 303,
+        "chunk": "# 1.环保底架漆  \n\n集装箱的底架部位，由于长期处于高湿环境且大部分时间会被海水浸泡，腐蚀条件最为苛刻，目前大部分还采用涂刷沥青漆的涂料配套。母庸置疑，沥青漆作为一种传统的涂料在成本上有巨大的优势，而且其防水、防渗透的功能也较好。但是由于其对人体的毒性，且沾污后难以清洗，在很多行业已经被淘汰，在集装箱制造行业停用沥青漆已经成为环保安全的当务之急。目前有的箱东已经在底架部位采用与箱体同样的涂料配套，但成本相对较高。2000年起，一些涂料公司相继研制成功了集装箱用环保底架漆，这种底架漆由改性环氧树脂和特殊的防腐颜料及助剂构成，固体含量可达到 $85\\%$ 以上，不含有毒物质且单箱成本与沥青漆相当。经过几年实际应用后，其底架和地板没有任何腐蚀和改变。因此，可以断定，不远的将来这种环保型涂料就会投人使用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 304,
+        "chunk": "# 2.水性涂料  \n\n由于水性涂料早已被欧美的用户所接受，所以大部分欧美的箱东都希望能在不久将来采用水性涂料作为集装箱的防腐与装饰。目前集装箱制造厂也正在致力于水性集装箱涂料的应用推进工作。已经有多家涂料制造商和箱厂共同探讨水性集装箱涂料的开发工作。目前要克服的有如下难题。  \n\n$\\textcircled{1}$ 如何适应现在的集装箱生产节奏由于水的蒸发潜热很大，在低温高湿的条件下干燥速率不及溶剂型涂料，而且往往还会产生“闪锈”问题。要达到最佳性能，应该对三度漆都要进行烘烤，这是现在的施工速率所不允许的。  \n\n$\\textcircled{2}$ 废水的处理问题在清洗设备，尤其是喷漆房中漆渣漆雾的收集过程中，将会产生废水，由于各集装箱厂的涂装线都是按油性涂料设计的，没有相应的废水处理设施，其投资和运行费用也应该重新进行评估。  \n\n$\\textcircled{3}$ 成本问题水性树脂的价格一般都高于油性树脂，因此其成本较高，这是最难以突破的地方。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 305,
+        "chunk": "# 3.新的涂料配套系统  \n\n鉴于水性锌粉漆开发上存在的困难，有的公司已经提出了新的两度型集装箱涂料配套系统，这种配套，由于少了一度涂料，施工速率、成本等问题就得到了解决。目前主要的方法是在底漆中加人特殊的防锈颜料和助剂，基本能满足防腐要求。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 306,
+        "chunk": "# 4.无溶剂或高固体涂料  \n\n与欧美不同，日本的学者认为，水性涂料虽然减少了对空气的污染，但是由于其在生产和施工中会产生废水，这些废水如处理不当，对环境的污染是远大于油性涂料的。因此在日本更倾向于使用无溶剂或高固体分涂料。在20世纪80年代日本就已开始这方面的研究，但遗憾的是随着集装箱制造业很快地转移到中国，这种技术没有得到应用。现在随着中国经济的发展，给无溶剂及高固体分集装箱涂料又提供了新的舞台。",
+        "category": " Introduction"
+    },
+    {
+        "id": 307,
+        "chunk": "# 5.其他新型集装箱涂料  \n\n作为一个过渡阶段，目前很多日本箱东倾向于使用弱溶剂涂料来解决环保问题；使用低气味涂料解决装载食品的集装箱内面的污染担忧问题。弱溶剂涂料主要是通过改进树脂的制造技术，使环氧树脂等能够和烃类溶剂相容，减少、醇、醚类溶剂，从而减少对环境的污染。而低气味涂料则主要是控制芳香族溶剂的使用，从而减少涂料施工后一段时间内箱体内存在的溶剂气味对装载食品的影响。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 308,
+        "chunk": "# 6.集装箱涂装工艺的现代化  \n\n随着科学技术的不断进步，经历了集装箱工业初创、发展和成熟各个阶段的中国集装箱业一直在苦苦思考实现集装箱涂装自动化的方法。实现涂装工艺的全自动化，不仅可以大幅度提高生产效率，同时还能将涂装工人从繁重的体力劳动和严重的职业危害中解脱出来。真正实现经济的持续、和谐和高速发展。  \n\n到目前为止，已经至少有一家工厂设计了自动化的涂装线并投入生产。这条流水线的构思和流程的设计思路打破了过去从手工喷涂工艺延续下来的箱体固定、喷涂设备移动的模式。采用固定绝大部分涂装设备，利用集装箱在流水线上的行走实现箱体和喷涂设备的相对移动。这样不仅省掉了喷漆时箱位需要停留的时间，更重要的是由于减少了喷涂设备的移动，省去了大量的传动装置，使故障率大幅度降低，提高了设备运行的可靠性，也解决了过去的半自动涂装设备由于废漆雾难以清理而造成的设备行走抖动和卡死的问题。  \n\n该设备的主要特点是用大量的喷嘴交叉排布，外面漆喷涂装置呈门形，内面则呈楔形，朝向箱体的部位共排布枪嘴。利用光电装置探测箱体，实现自动开关枪。前端设置了和箱体相同的高度行车，行车上垂直排枪嘴，通过有限的横向移动来实现喷涂。  \n\n很明显，该套自动喷涂系统有如下的优点： $\\textcircled{1}$ 生产节奏快； $\\textcircled{2}$ 自动化程度高； $\\textcircled{3}$ 能减少涂料的浪费； $\\textcircled{4}$ 自动喷涂保证了涂膜厚度的均一。  \n\n但是目前阶段也存在一些缺点有待克服，首先，由于使用了大量的枪嘴，当某一个或几个枪嘴出现堵枪时，整个涂装线就需要停下来以便调整或更换枪嘴，这样会严重影响涂装效率，为了减少堵枪，就要求整个喷漆系统保持良好的清洁，也对涂料的细度和杂质含量提出更高的要求。另外，大量的枪嘴同时喷涂时，喷出的气流会互相干扰，造成漆膜的不均匀，这是一个非常复杂的问题，解决起来也比较困难。但是不管存在什么困难，集装箱涂料的自动喷涂是大势所趋，也是行业发展的最终方向。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 309,
+        "chunk": "# 第三节 海洋工程重防腐涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 310,
+        "chunk": "# 一、海洋油气资源开发及海洋工程简史  \n\n人类对海洋资源的利用已有几千年的历史。海洋总面积约3.6亿平方米，占地球表面积的 $70.9\\%$ 。海洋是一个巨大的资源宝库，拥有潜力巨大的矿产资源、生物资源、水资源、能源和空间资源，因而成为人类发展经济并从事相应科学技术开发的重点领域。海洋工程即是指人类为开发和利用海洋资源，利用海洋空间建立各种工程技术设施和海上运输设施。上述设施通常称为海洋工程结构，常见的包括海上钻井平台、固定生产平台、海洋工程船舶及其他运输船舶等。这里所讨论的“海洋工程”将限定于为海洋油气资源开发活动服务的各类海洋油气工业装备的建造、安装和维护，包括油气勘探、钻井、生产、油气输送所需的各种固定式和移动式生产平台、移动式钻井平台、钻井船、海上浮式贮油轮等海洋钢结构。  \n\n19世纪末期，最早的海上石油开采活动出现于美国加州的水深仅为数米的滨海地带，使用的是木桩搭建的简易钻井架。1947年，世界上第一座钢质的、在陆上预先拼装的固定式钻井/生产平台由』．RayMcDermott船厂为Superior 石油公司在路易斯安那外海建成投产，这也标志着海洋工程进入了一个新的历史阶段：预拼装。  \n\n在第二次世界大战结束后，战争期间所发展的大规模生产能力和大量的科研成果转移到民用领域，为海洋油气资源开发和海洋工程提供了发展所需的必要支持。海洋油气开采也逐步从水深十余米的浅海向数十米乃至数百米的深海扩张。1956年，世界上第一座采用齿轮齿条提升机构的自升式移动钻井平台“蝎子”号建成投人使用，可在水深约50m的海域作业。1961年，Continental、Union、Shell和Superior 公司联合投资的第一座专门设计建造的钻井船CUSS1号诞生，可从事深水的钻井和完井作业。而作为油气生产主力的固定式导管架平台也从数十米的水深逐步扩展为数百米水深。  \n\n科技进步促进了海洋工程的发展，为海洋油气资源开发迈向千米以上的深海提供了技术保障。自20个世纪60年代开始，半潜式钻井平台、半潜式生产平台、张力腿平台、SPAR、浮式生产贮油轮、深海机器人、海底完井、海底管线、3维地质勘探等新技术层出不穷，深水油气开采在技术和经济层面都不再是可望而不可即的梦想。进入21世纪，全球经济保持较快地增长势头。受到全球能源需求增长和能源价格高起的推动，以墨西哥湾和北海为代表的海洋油气资源开发正在全球方兴未艾，巴西、西非、东南亚、印度洋、中国海、澳大利亚…众多的海洋油气田正处于开发之中，海洋工程行业也随之迎来了新的黄金时期。  \n\n全球海洋工程的版图上最主要的国家和地区包括美国（休斯敦和墨西哥湾沿岸，各类海洋设施的设计，固定式生产平台、浮式生产设施、上部模块和海底设施的建造和安装)，挪威和英国（北海沿岸，各类海洋设施的设计，固定式生产平台、浮式生产设施、上部模块和海底设施的建造和安装)，意大利和法国（各类海洋设施的设计和总包)，以及新加坡和韩国(各类移动式钻井平台和浮式生产设施的建造和改装)。随着需求的增长，一些以往在海洋工程领域涉猎不多的国家和地区，特别是中国和中东的迪拜也投人了大量资源扩充了这方面的能力。以中国为例，自2000年以来所建造的海洋油气设施数量已远远超过了在此之前20多年间的总数。",
+        "category": " Introduction"
+    },
+    {
+        "id": 311,
+        "chunk": "# 二、海洋工程结构物分类  \n\n海洋工程结构物包括了海洋油气资源开发活动，即油气勘探、钻井、生产、油气输送所需的各种固定式和移动式生产平台、移动式钻井平台、钻井船、海上浮式贮油轮等海洋钢结构。了解各种类型的海洋工程结构物及其运作模式和使用环境将有助于人们理解其所面临的防腐蚀挑战并选择正确的解决方案。",
+        "category": " Introduction"
+    },
+    {
+        "id": 312,
+        "chunk": "# 1．钻井平台  \n\n钻井（drilling）是石油天然气勘探以及生产至关重要的一个环节。钻井平台根据其结构形式和作业能力通常可以分为以下几类：钻井驳船（drillingtender）、自升式钻井平台(jack-up drilling platform）、半潜式钻井平台（semi-submersible drilling platform）、钻井船（drilling ship）、生产平台附属钻机模块（platformrig）。",
+        "category": " Introduction"
+    },
+    {
+        "id": 313,
+        "chunk": "# 2.浮式生产设施  \n\n生产是海洋油气开发最主要的一个阶段，即通过前期地质勘探、试钻、钻井和油田生产设施的建造和安装，正式进入油气开采的长期阶段。这个阶段的关键设施就是各类生产装置，包括浮式的和固定式。浮式生产设施（FPU）顾名思义是利用浮体（hull）漂浮于海上，通过系驳系统（mooring）定位，由钢质管线（riser）与海底油井连接进行海底油气汲取并通过上部模块（topside）进行生产处理的设施，常用于深水油气田或贮量较小的边际油气田。主要包括外形通常为船形浮式生产贮油轮（图 3-4-49，FPSO——floating，production，storage，offload-ing)、由竖直的柱状浮体和水平的横向浮体构成的张力腿生产平台（tension leg platform TLP)、半潜式生产平台（semi-sub production platform）和柱状生产平台（SPAR）组成。",
+        "category": " Introduction"
+    },
+    {
+        "id": 314,
+        "chunk": "# 3.固定式生产平台  \n\n固定式生产平台（fixed platform）是最早出现也是最常见的海洋油气生产设施。其基本功能是通过钢质管线汲取海底油气并进行简单处理，然后输送至附近的浮式生产贮油轮或通过海底管线送至大陆终端，同时向海底油层注人高压水或气体以保持或提高油气流量和采出率。固定式生产平台的基本特点是“固定”，在油气田资源枯竭前不会移动或拆除，整个  \n\n寿命周期高达 $25\\sim30$ 年，甚至有最高达到70以上的预期寿命。  \n\n固定式生产平台的基本特征是露出海平面以上的包括生产和生活模块的平台部分固定于以海床为支撑的钢质或混凝土结构。具体可以分为导管架平台（jacketplatform）、顺应式平台（complianttower）、混凝土重力平台（gravity platform）等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 315,
+        "chunk": "# 4.海底系统  \n\n海底系统是当代海洋油气开发体系中不  \n\n![](images/9b7ab40f99a631ec783b9b1b021abd2cc710a6eddae7852aade064a054d90a0d.jpg)  \n图3-4-49 海洋石油FPSO  \n\n可或缺的一个关键系统。海底系统通常与固定式或浮动生产设施配套使用，将多个较小的海底油气田连为一体并与生产设施连通，以节省生产设施昂贵的建造和安装投资。  \n\n![](images/816c72d784f4e84b90b8ea1b8de4da32d7876374768f793a12429e52188b5764.jpg)  \n图3-4-50 平台主要结构及腐蚀环境分区  \n\n海底系统由6大主要部分构成：油/气井、采油树、集线器与线撬、管线与跳线、脐带以及控制系统。",
+        "category": " Introduction"
+    },
+    {
+        "id": 316,
+        "chunk": "# 三、海洋的腐蚀环境  \n\n海洋工程装置的腐蚀环境要比一般的远洋船舶严酷得多。海洋平台在外海作业，没有防浪堤等港口设施的保护，每天都要承受海风、海浪、潮流的作用。海洋结构复杂庞大，大都从海底一直伸展到数十米以上的高空，腐蚀环境复杂。在甲板以下的管桩式结构，焊接点多，部位集中，而不像船舶的壳体那样易于保护。海上平台不能自航，生产平台不能移动，因此不易进坞维修。海洋工程装置一旦发生腐蚀事故，后果将会是十分严重的。1980年挪威位于北海的AlexanddrL.Kielland半潜式生活平台，因一根撑杆发生腐蚀疲劳而导致整个平台在 $15\\mathrm{min}$ 内倾翻，造成123人死亡和失踪。  \n\n海洋平台的不同区位所受腐蚀环境不尽相同。以固定式导管架式桩基平台为例，其结构从上自下可以分为井架、甲板及其甲板组件、甲板腿、导管架和钢桩五个部分，如图3-4-50所示。这些部位分别位于海洋大气区、飞溅区、潮差区、全浸区和海泥区五个部分。对于海上平台的腐蚀环境条件可以参见表3-4-55。  \n\n表3-4-55 海上平台腐蚀环境条件  \n\n\n<html><body><table><tr><td>区域</td><td>环境条件</td></tr><tr><td>海洋大气区</td><td>风带来细小的海盐粒子。影响腐蚀性的因素是海盐含量、湿度、风速、雨量、温度和太阳辐照等</td></tr><tr><td>飞溅区</td><td>潮湿、氧气充分的表面，海水飞溅，无海生物污损</td></tr><tr><td>潮差区</td><td>周期性沉浸、供氧充分，有海生物污损</td></tr><tr><td>全浸区</td><td>浅海区：海水通常为氧饱和，海生物污损，海水流速，水温，污染等 深海区：氧含量不一，温度接近0°℃，海水流速低，pH比表层低 大陆架：无植物污损，动物污损也大大减少，氧含量降低，水温较低</td></tr><tr><td>海泥区</td><td>存在细菌，如硫酸盐还原菌，海底沉积物的特征和性状不同</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 317,
+        "chunk": "# 1.海洋大气区  \n\n海洋大气与内陆大气有着明显的不同。海洋大气湿度大，易在钢铁表面形成水膜；海洋大气中盐分多，它们积存钢铁表面与水膜一起形成导电良好的液膜电介质，是电化学腐蚀的有利条件，因此海洋大气比内陆大气对钢铁的腐蚀程度要高 $4\\sim5$ 倍。在渤海海上石油平台测得的裸钢腐蚀率数据达到 $\\bar{1}\\cdot0\\mathrm{mm/a}$ 9  \n\n导管架桩基平台，甲板腿以上构件，包括生活区、生产区和钻井架等，主要在海洋大气中工作，长期经受风吹、雨淋、日晒和海水盐雾的作用。尤其是在甲板下部，由于长期处于潮湿状态，氧气供应充分，是该区腐蚀最严重的部位。这是因为阴面的尘埃和海盐沉积不易冲掉，而且老的菌类生物在阴面更有活性，它们会保持水汽和盐分，增强腐蚀性。",
+        "category": " Introduction"
+    },
+    {
+        "id": 318,
+        "chunk": "# 2.飞溅区  \n\n海洋飞溅区的腐蚀，除了海盐含量、湿度、温度等大气环境中的腐蚀影响因素外，还要受到海浪的飞溅，飞溅区的下部还要受到海水短时间的浸泡。飞溅区的海盐粒子量要远远高于海洋大气区，浸润时间长，干湿交替频繁。碳钢在飞溅区的腐蚀速率要远大于其他区域，在飞溅区，碳钢会出一个腐蚀峰值，在不同的海域，其峰值距平均高潮位的距离有所不同。  \n\n在青岛海域碳钢位于平均高潮位以上 $0.5{\\sim}1.2\\mathrm{m}$ 处以及腐蚀峰值区测，暴露1a的最大点蚀深度在 $0.36{\\sim}1.75\\mathrm{mm}$ ；暴露4a时，钢的局部腐蚀最大深度在 $\\mathrm{2.20{\\sim}3.50m m}$ ；暴露8a后，大多数钢已经穿孔（厚度 $6\\sim8\\mathrm{mm})$ 。渤海海中使用 $10a$ 的海上平台测得飞溅区的腐蚀速度在 $\\bar{0},45\\mathrm{mm/a}$ ，同时有不少深度在 $2\\mathrm{mm}$ 以上的腐蚀坑。  \n\n导管架桩基平台、甲板腿下部和导管架上部在海水飞溅区。在高潮线以上飞溅区，表面长期遭受飞溅海水的不断冲击，周期性地被海水湿润，氧气供应充分，并且还要经受狂风巨浪和浮冰的冲击，因此该部位是平台腐蚀最严重的地方。  \n\n各海区的飞溅区的范围和腐蚀的严重程度各不相同。墨西哥湾约在高潮位以上 $2\\mathrm{m}$ ，阿拉斯加湾可达高潮位以上 $9\\mathrm{m}$ ，我国对四个海区港湾内的测试表明约在 $0\\sim2.4\\mathrm{m}$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 319,
+        "chunk": "# 3.潮差区  \n\n从高潮位到低潮位的区域称为潮差区。在潮差区的钢铁表面经常和饱和了空气的海水相接触。由于潮流的原因钢铁的腐蚀会加剧。在冬季有流冰的海域，潮差区的钢铁设施还会受浮冰的撞击。  \n\n试验表明在潮差区，碳钢的初始腐蚀速率要比全浸区大，但是暴露数年后，腐蚀速率会明显下降，甚至低于全浸区和海泥区的腐蚀率，但是局部的腐蚀深度要比全浸区严重。  \n\n随着潮位的涨落，水线上方湿润的钢表面供氧总要比浸在海水中的水线下方钢表面充分得多，而且彼此构成一个回路，由此成为一个氧浓差宏观腐蚀电池。腐蚀电池中，富氧区为阴极，相对缺氧区为阳极，总的效果是整个潮差带中的每一点分别得到了不同程度的保护，而在平均潮位以下则经常作为阳极而出现一个明显的腐蚀峰值。  \n\n在防腐蚀工程设计时，通常把潮差区和飞浸区作为一个区域进行综合考虑，这样可以方便进行施工、维修和阴极保护等各方面工作。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 320,
+        "chunk": "# 4.全浸区  \n\n全浸区全浸于海水中，比如导管架平台的中下部位，长期浸泡在海水中。钢铁的腐蚀会受到溶解氧、流速、盐度、污染和海生物等因素的影响，由于钢铁在海水中的腐蚀反应受氧的还原反应所控制，所以溶解氧对钢铁腐蚀起着主导作用。  \n\n在渤海4号平台使用12年后进行的一次检测发现低潮位附近的构件有多处腐蚀穿孔，  \n\n推算其腐蚀速率达 $\\bar{0},\\bar{6}\\mathrm{mm/a}$ 以上  \n\n海水的流速对于钢铁来说，除了冲刷作用外，主要起着对钢铁表面供氧的作用，腐蚀速率会随着流速的增加而加快，当流速增加到6m/s时，腐蚀速度达到最大值。  \n\n盐度对腐蚀的影响主要是它的导电性，海水一般含盐在3%～3.5%，是良好的电解质溶液。占海盐离子总量的50%以上的氯离子，对钢铁的腐蚀更为显著。  \n\n温度、污染和海生物等因素对钢铁的腐蚀也有一定的影响。海生物的污损，如台鲜虫、石灰虫、藤壶和海藻等，对碳钢的腐蚀影响较大。污损海生物能阻碍氧气向腐蚀表面扩散，从而对钢的腐蚀有一定的保护作用。但是由于污损层的不渗透性和外污损层中嗜氧菌的呼吸作用，使钢表面形成缺氧环境，有利于硫酸盐还原菌的生长。  \n\n引起海水中钢铁结构腐蚀破坏的主要危险不在于钢铁厚度的平均减薄，而在于严重的局部腐蚀和腐蚀疲劳。  \n\n第七二五研究所在南海榆林海域从1984年12月 $\\sim2000$ 年12月进行了为期16年的海洋环境钢铁暴露试验。在深度为 $0.5\\sim1.5\\mathrm{m}$ 的全浸区，钢样上长满了丛生的海生物，附着厚度在 $2\\sim3\\mathrm{cm}$ ，最厚达 $10\\mathrm{cm}$ 左右。内层主要为牡蛎、石灰虫、苔藓虫，外层主要为藤壶。腐蚀产物为多层硬壳黑锈，腐蚀多为斑状、坑状和溃疡型局部腐蚀。A3钢每年的腐蚀率达到 $0.072\\mathrm{mm/a}$ ，16年的平均腐蚀深度达到 $2.42\\mathrm{mm}$ ，最大达到 $3.79\\mathrm{mm}$ 。对比美国在巴拿马运河海域进行的16年试验，QQ-S-741低碳钢的腐蚀率为 $0.\\ 073\\mathrm{mm/a}$ ，局部腐蚀深度平均值为 $2,29\\mathrm{mm}$ ，最大为 $3.94\\mathrm{mm}$ 。两个试验的结果非常接近。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 321,
+        "chunk": "# 5.海泥区  \n\n海泥区位于全浸区以下，主要由海底沉积物构成。海底沉积物的物理性质、化学性质和生物性质随海域和海水深度的不同而不同。  \n\n海泥实际上是海水饱和的土壤，它是一种比较复杂的腐蚀环境，既有土壤的腐蚀特点，又有海水的腐蚀行为。海泥区含盐度，电阻率低，但是供氧不足，所以一般的钝性金属的钝化膜是不稳定的。  \n\n海泥中含有的硫酸盐还原菌，会在缺氧环境下生长繁殖，会对钢材造成比较严重的腐蚀。  \n\n沙质泥的特点是海沙表层比较空，属于半开放性，孔隙一般都要大于海泥中的孔隙率。孔隙大，包含的海水就多，由于海水中的溶解氧的去极化作用，钢的腐蚀速率也就越大，孔隙率的多少是钢铁在不同类型海泥中产生不同腐蚀速度的原因之一。",
+        "category": " Introduction"
+    },
+    {
+        "id": 322,
+        "chunk": "# 四、海洋工程防腐蚀涂料的发展  \n\n腐蚀发生的机理和要素多种多样，相应的防腐技术也有各自不同的类型。对于钢结构防腐，最常见的是采用防腐蚀涂层防护并辅之以阴极保护。  \n\n过去100年来，海洋工程结构物的防腐技术从航运业的海洋船舶防腐技术取得了相当多的经验和支持。可以说，在当代深水油气资源开发大规模展开之前的数十年间，海洋工程结构物防腐仅仅是跟随海洋船舶防腐的步伐。  \n\n随着船舶涂料的发展，厚浆型环氧漆、长效防污漆等新的涂料品种不断在远洋航运业得到应用，同时也逐步推广到海洋工程结构物防腐领域。但船舶涂料与海洋工程防腐涂料的使用环境虽然总体上类似，其保护对象的工况或使用模式却有着显著的区别。因此，在实际使用过程中人们最终发现，简单地将海洋工程涂料与船舶涂料等同起来是一种片面的理解。  \n\n尽管用于海洋油气资源开发的海洋工程结构物与用于远洋运输的海洋船舶的使用环境类似，都是出于茫茫大海之上，但其运作模式的不同决定了它们在防腐需求方面的不容忽视的差异。明确这一点是讨论当代海洋工程涂料的前提。  \n\n与海洋船舶一样，海洋工程结构物存在水下部分和水上部分，也包括不同的功能区域和内部舱室。因此，其所采用的防腐涂料同样要应对海流、海浪拍击、浮冰、严寒、酷暑、海洋大气中的盐分、强烈的紫外线、作业时的机械碰撞、机械磨损、溅泼的化学物质、局部高温等各种恶劣环境因素的影响。海洋船舶的维修计划较短，通常都是 $3\\sim5$ 年就会进坞检修，根据腐蚀情况对船壳和货舱等部位的涂层进行局部维修或大修。与此不同的是，各种类型的海洋工程结构物或在整个寿命周期（可长达 $25\\sim30$ 年甚至更长）结束前固定于某一海域，或虽可移动但一个作业周期从数月到数年不等。而无论是计划内的或是计划外的对涂层缺陷的海上维修都涉及高昂的停工损失、昂贵的运输和施工成本以及海上施工条件限制带来的过高的施工难度等问题，甚至于有些设施如海底模块的涂层失效是无法用常规手段加以修补的。因此相对于船舶涂料而言，海洋工程防腐涂料首先要满足的是长期的可靠的防腐防护：设计寿命长—通常为15年以上（高性能、高膜厚、高表面处理的涂层体系)、可靠性高（可靠的涂料技术和产品质量控制）以及全寿命周期成本低（初始投资与后续维修费用的最佳结合)。  \n\n与同期船舶类似，最早的海洋钻井/生产平台防腐采用的是沥青和亚麻油等天然原料稍加处理后制成的涂料。其防腐性能并不能真正满足需求，同时由于自身物理/化学特性，如色泽、热塑性和长期氧化反应等，限制了此类涂料在海洋环境下的长期使用。  \n\n在20世纪 $40\\sim50$ 年代，随着乙烯树脂和环氧树脂的诞生，这些新型涂料开始在海洋工程结构物上得到推广应用。与此前的油性醇酸漆相比，新的乙烯漆和环氧漆不依赖氧气固化，而是随着溶剂挥发进行物理固化或发生化学交联从而形成坚韧的漆膜，并且漆膜不会像醇酸漆那样在使用过程中进一步与大气发生氧化反应而脆化，长期防腐性能得到了较大的提升。  \n\n乙烯共聚物系统的特点是其低体积固体分，这意味着不能单道施工形成较厚的漆膜厚度，它的最大干膜厚度在 $50\\mu\\mathrm{m}$ 左右，要达到 $250\\sim300\\mu\\mathrm{m}$ 的干膜厚度，通常要 $5\\sim7$ 道涂层，很明显施工费用是相当高的。这种多道涂层的热塑性树脂系统，以无机硅酸锌作为底漆，防腐蚀效果很好。墨西哥湾的温度和湿度都相当高，非常有利于无机硅酸锌的固化。值得注意的是，在墨西哥湾，聚乙烯醇缩丁醛/铬酸锌洗涤底漆，即磷化底漆，直接涂在钢材表面，然后再覆涂多道乙烯系统，也取得了很好的效果。早期的乙烯涂料当时还没有受到卫生、安全和环境的要求限制。随着时间的推移，多道涂层系统的费用增加，开始采用较低分子量乙烯树脂来获得高固体分，厚浆型只需更少涂层道数的乙烯树脂涂料，但是其每道漆的干膜厚度也只能施工到 $70\\mathrm{\\sim}80\\mu\\mathrm{m}$ 。丙烯酸树脂和乙烯树脂的混用系统也开始应用。这些类型的涂料很多公司都有成功的应用，比如在墨西哥湾的Gulf、Philips、Exxon 公司，以及在北海的Statoil公司等。  \n\n早期的环氧系统是基于中等分子量环氧树脂的，最初的交联剂采用低分子量脂肪胺。这些环氧树脂涂料典型的体积固体分在 $40\\%\\sim45\\%$ ，每道涂层的干膜厚度在 $50\\sim75\\mu\\mathrm{m}$ ，总的干膜厚度在 $200{\\sim}250\\mu\\mathrm{m}$ 。无机硅酸锌底漆与这些系统配合使用，可以增强防止漆膜下锈蚀蔓延的性能和提高整体耐蚀性能。在水下部位和飞溅区，多道系统的环氧煤沥青涂料，取代了纯乙烯树脂涂料，典型的干膜厚度为 $300\\sim500\\mu\\mathrm{m}$  \n\n在北海的海上油气开采，与墨西哥湾相比，在20世纪60年代末，有着一系列的全新问题：高大而且持续的浪涌，盐雾飞喷几乎一直处于潮湿状态，低温施工环境，白天低于 $5^{\\circ}C$ $(40^{\\circ}\\mathbf{F})$ ，晚间固化温度低于冰点；更大的建筑结构物，不同建造程序。北海地区的海洋工程对无机硅酸锌底漆的应用缺乏经验，主要采用环氧富锌底漆，采用氯化橡胶涂料作为乙烯树脂涂料的替用产品。  \n\n氯化橡胶涂料如同早先的乙烯材料一样有着相同的问题，最大的问题就是热塑性、热降解和耐候性，而且也对油脂敏感。最终这些氯化橡胶面漆表面还要涂特殊的表面容忍性涂料，这样才可以提高其耐油性。  \n\n在水下部位和飞溅区，非常厚的环氧包覆层系统开始普遍应用，厚度在3000～$6000\\mu\\mathrm{m}$ ，这些涂料可以用标准型无气喷涂进行多道涂层施工，也可以用特制的设备进行单道涂层施工。聚酯玻璃鳞片涂料在水下部位和飞溅区也得到了应用，典型的涂膜厚度为两道共计 $1500\\mu\\mathrm{m}$ 。1971年开发的北海地区的Ekofisk油气田，聚酯玻璃鳞片涂料有着长达30年以上的非常成功的防腐蚀应用。  \n\n到20世纪70年代，用于墨西哥湾的系统开始使用现在还是常规系统的防腐蚀涂料体系，然后是波斯湾和北海地区，比如含有富锌的涂料、厚浆型环氧涂料和聚氨酯涂料等。这种类型的系统保留了很多年。触变剂技术允许开发出厚浆型环氧涂料，减少了总体涂层道数，羟基丙烯酸聚氨酯不同于紧密的聚酯交联的聚氨酯面漆，耐久性强、可覆涂面漆开始得到发展。  \n\n到了20世纪90年代，两大压力迫使采用高固体分涂料系统：减少有机溶剂的挥发(VOC法规)；减少涂层道数（施工费用问题)。海洋工程防腐蚀涂料技术从一开始发展应用，到现在提高得非常快。由于海洋工程建造施工过程变得越来越快，要求涂料具有环境容忍性，减少施工涂层道数，提高并满足了环保、健康和安全方面的要求。相比于传统的海洋工程涂料系统，现在的重点是要满足生产过程在所有的气候下，快速固化，快速搬运，重涂和过厚的可容忍性，施工性能要好。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 323,
+        "chunk": "# 五、海洋工程防腐涂料  \n\n经过数十年的不断研究和实践，当代海洋工程防腐涂料已发展成为一个比较健全的高性能涂料体系。海洋工程防腐涂料可以简单地按功能划分为三个类型： $\\textcircled{1}$ 防腐底漆/中间漆(环氧类、富锌类、醇酸类等)； $\\textcircled{2}$ 面漆（醇酸、环氧、丙烯酸、聚氨酯、聚硅氧烷等);$\\textcircled{3}$ 特殊功能型涂料（防污漆、耐高温漆、防滑涂料等）。",
+        "category": " Introduction"
+    },
+    {
+        "id": 324,
+        "chunk": "# 1.防腐蚀底漆/中间漆  \n\n海洋工程结构物的共同特点是功能繁多、结构复杂。针对不同的功能区域或部位，存在不同的防护需求。但除了极少数特殊部位以外，防腐蚀底漆/中间漆都是涂层系统不可或缺的组成部分，通过对底材的屏蔽、阴极保护或钝化作用成为海洋工程防腐蚀涂层体系的基础。  \n\n屏蔽型底漆和中间漆，主要是不含锌粉或缓蚀颜料的环氧树脂涂料和片状颜料，如铝粉、玻璃鳞片、云母氧化铁等，可以增强涂层的对水和氧的屏蔽性能。  \n\n富锌底漆主要分有机富锌底漆（主要指环氧富锌底漆）和无机富锌底漆两大类。富锌底漆中锌粉含量须占干膜厚度的 $80\\%$ （质量分数），锌粉须满足ASTMD520、ISO3549的要求。富锌底漆在飞溅区和其他浸没区因其自我牺牲作用，更易出现涂膜缺陷，因此不推荐用于这些部位而要使用其他涂层材料。  \n\n(1）碳氢树脂改性环氧涂料（mastic epoxy）涂层坚韧致密，附着力强，防水性能和耐磨性能出众。由于采用了小分子量的树脂，碳氢树脂改性环氧涂料具有优异的渗透性（在常用涂料中仅次于油性醇酸树脂)，对于表面处理较差的底材如机械动力打磨至St2或高压水喷射除锈的钢材都有良好的附着力和防腐蚀效果，因此为海上维修作业提供了极大的便利。同时也适用于各类新建海洋工程结构物。  \n\n(2）纯环氧底漆采用纯环氧树脂并添加各种功能颜料的纯环氧底漆在海洋工程防腐领域有着广泛的应用。良好的防水性和耐化学品性能使得纯环氧底漆成为压载舱、淡水舱、原油舱和化学品舱的理想选择。由于漆膜同时具有优秀的机械强度和耐磨性能，纯环氧底漆也普遍用于各种水下和大气环境中的外露部位作为防腐蚀底漆。但纯环氧底漆由于树脂分子量较大，对底材表面处理等级要求较高（通常要求喷砂处理)，因此常用于新建项目而非维修保养。  \n\n(3）环氧玻璃鳞片涂料在碳氢树脂改性环氧涂料或纯环氧底漆中添加适量的玻璃鳞片（约占颜料总重量的 $25\\%$ ，可以显著增强漆膜的机械强度和韧性，进而提升漆膜的耐冲击和耐磨性能。同时，漆膜中平行排列的玻璃鳞片大大延长了水汽穿透涂层的路径，降低水汽渗透率，从而提升了涂料的防水性能。因此，环氧玻璃鳞片涂料常用于腐蚀环境恶劣、机械磨损严重的部位，如海洋结构物的飞溅区、露天甲板、直升机甲板等，或要求较长的有效防腐设计寿命的情形下。  \n\n(4）酚醛环氧液舱涂料具有极佳的耐化学品性能，可以抵御绝大多数常见的化学品包括特定的酸碱的腐蚀，适用于对化学品舱、污油舱、原油舱、污水处理舱等腐蚀环境苛刻的液舱保护。酚醛环氧液舱涂料施工条件严格，对底材结构处理、表面处理、清洁度和含盐量、底材温度、环境温度和湿度、涂装间隔、通风等均有严格要求。  \n\n(5）环氧富锌底漆借助于锌粉提供的阴极保护作用能极大地提升涂层的防腐蚀性能。通常单涂层施工 $50\\sim75\\mu\\mathrm{m}$ ，结合环氧中间漆和面漆系统，可以为海洋工程结构物的大气环境中部位提供15年以上的有效保护。环氧富锌底漆施工简便，对过高的膜厚不敏感，在冬季施工下可换用低温固化剂，因此在海洋工程防腐领域得到了广泛应用。需要注意的是，由于在碱性环境下锌的损耗速度急剧增大，环氧富锌底漆不推荐用于水下部位和飞溅区。  \n\n（6）无机硅酸锌底漆采用正硅酸乙酯结合高纯度锌粉制备，漆膜中锌粉通过正硅酸乙酯与底材通过化学键结合，对底材提供可靠的阴极保护。海洋工程领域采用的无机硅酸锌底漆通常单涂层施工 $75\\mu\\mathrm{m}$ ，结合环氧中间漆和面漆系统，可以为海洋工程结构物的大气环境中部位提供20年以上的有效保护。无机硅酸锌底漆对酸碱敏感，但对有机溶剂抵抗力非常优秀，也常用作装载有机溶剂包括甲醇在内的液舱单涂层防腐。无机硅酸锌底漆施工条件苛刻，最高膜厚通常不能超过 $125\\mu\\mathrm{m}$ ，否则容易出现龟裂。对底材的结构处理、表面处理、底材温度、环境温度和湿度（固化过程需水分参与反应，大气湿度要高）等均有严格要求。尽管防腐性能优异，施工方面的局限性限制了无机硅酸锌底漆的使用，除了少数设计寿命极长的项目或腐蚀环境及其恶劣的部位，通常被环氧富锌所替代。与环氧富锌类似，无机硅酸锌也不适用于水下部位和飞溅区。  \n\n（7）醇酸底漆采用多元醇、多元酸与脂肪酸制备而成醇酸树脂，依靠不饱和脂肪酸基与空气中的氧气反应氧化聚合。防水性能一般，通常用于结构物内部干燥区域如生活区或机舱等腐蚀和缓的部位。单组分，施工简便，对施工时的环境温度不敏感，对表面处理要求较低，因而也得到较多应用。  \n\n(8）水性涂料水性无机硅酸锌底漆，利用空气中的二氧化碳和湿气与硅酸钾进行反应，在生成碳酸盐的同时，锌粉也同硅酸钾充分反应成为硅酸锌高聚物。其固化受温度和湿度的影响较大。水性无机富锌底漆要求喷砂到Sa3。水性无机富锌涂料，以水为溶剂和稀释剂，不含任何有机挥发物，无毒，无闪点，对环境污染小，VOC为零，没有火灾危险，在施工、贮存和运输过程中较为安全。水性无机硅酸锌涂料可以厚膜施工 $100{\\sim}200\\mu\\mathrm{m}$ 的干膜厚度，而不会开裂，适用于最严酷的腐蚀等级ISO12944C5-I工业和C5-M海洋腐蚀环境。  \n\n水性环氧防锈底漆是双组分快干型水性环氧防腐底漆/中间漆，可以在低至5C时固化。含有活性防腐颜料和闪锈阻剂。用作钢材、铝材、镀锌钢材和热喷锌表面的底漆/中间漆，其表面上可涂覆水性丙烯酸、水性环氧和合适的溶剂型涂料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 325,
+        "chunk": "# 2.面漆  \n\n（1）醇酸面漆醇酸面漆是一种单组分的、经济性的长油度有光面漆，可以调出多种色彩，具有良好的初始光泽，并且具有良好的重涂性能。醇酸面漆的体积固体含量适中（约$50\\%)$ ，通常可以涂覆到 $40\\sim50\\mu\\mathrm{m}$ 的干膜厚度。醇酸面漆的干燥通过溶剂的挥发和氧化反应来完成。要避免单道涂层涂覆过厚，否则会引起干燥和起皱的问题。有机硅醇酸面漆，与其他涂料相比，有着很好的户外耐久性能，失光变色和粉化等程度要轻得多。有机硅醇酸面漆与纯醇酸树脂面漆相比，其耐候性和耐热性方面有很大的提高。在干性油醇酸树脂中的活性羟基与硅树脂中间体的羟基进行反应，用化学的方法使醇酸树脂和硅酸树脂两者共聚。在海洋工程中，醇酸面漆主要用于机舱、生活区域等。  \n\n(2）环氧面漆环氧树脂的耐水性和耐化学品性能优良，漆膜坚硬。由于环氧含有醚键，漆膜经阳光照射后会降解断链，失去光泽，然后粉化。因此，环氧不宜用作室外面漆。环氧面漆为双组分，聚酰胺固化涂料，可以调配出多种颜色供选用。环氧面漆可以用作大多数高性能防腐蚀涂料系统之上的坚韧面漆，而无需高性能的装饰性面漆的场合。环氧面漆有着良好的耐磨性能而且耐化学品的泼溅，广泛应用于甲板、贮藏室地板等部位。环氧面漆耐很多化学品，尽管耐化学品的程度与化学品接触涂料的时间长短以及多少有很大关系。大多数传统的环氧面漆，有着相对良好的初始光泽，但是暴露于阳光下，涂料表面会由于紫外线的作用而退化，这会导致表面呈现粉末状，这种效应称之为“粉化”。  \n\n(3）丙烯酸面漆是氯化橡胶面漆的替代品，有优异的保色保光性能，而且漆膜光亮丰满，耐腐蚀性好。丙烯酸面漆是快干型，单组分，氯化石蜡改性的丙烯酸面漆，可以调配出多种颜色供选用。丙烯酸面漆有良好的光泽与颜色保持性，重涂性能突出。它可以重新溶解，因此在自身重涂时有着很好的附着力。丙烯酸面漆的体积固体分通常较低，因此有着极高的VOC含量。由于丙烯酸面漆是热塑性的，长时间接触温度时：大于 $40^{\\circ}C$ （ $\\mathrm{104^{\\circ}F}$ ）漆膜会软化凹陷，随着温度的降低，力学性能才会恢复。  \n\n(4）脂肪族聚氨酯面漆为双组分，采用羟基丙烯酸聚氨酯与脂肪族异氰酸酯固化反应，作为装饰性面漆用于需要高光泽，高耐久面漆的场合，用于高性能防腐涂料系统上面。聚氨酯面漆与其他面漆，如环氧、单组分丙烯酸和醇酸面漆等相比，有着突出的光泽保持性能。聚氨酯由丙烯酸树脂的羟基和脂肪族异氰酸酯的异氰酸基相反应交联。异氰酸酯也能与高湿大气中或底材表面的湿气起反应。与水反应会释放出二氧化碳，导致起泡等不良漆膜外观。干燥环境下，聚氨酯面漆可以耐受 $120^{\\circ}C$ ( $248^{\\circ}\\mathrm{F})$ 高温，然而，老化后会有所发黄。当长效的颜色保持性非常重要时，建议最大操作温度不要超过 $80^{\\circ}C$ ( $\\mathrm{~\\~}[\\mathrm{~\\}7\\mathrm{{6}^{\\circ}{F}})$ 0  \n\n(5）双组分丙烯酸面漆作为高性能面漆，特别适用于在要求不能喷涂含有异氰酸酯固化剂的聚氨酯面漆，对健康和安全特别注重的场合。双组分内烯酸面漆是羧化丙烯酸与环氧树脂交联的高性能面漆，其反应过程由丙烯酸链上的氨基所催化。由于环氧和胺的同时存在，其耐久性能不如高质量的丙烯酸脂肪族聚氨酯面漆那样好，在长期暴露于紫外线下时，耐黄变和光泽保持性要差一些。环氧丙烯酸面漆可以用于大多数高性能防腐蚀涂料系统之上。环氧丙烯酸面漆有着很好的施工性能、良好的早期耐水渍耐湿气性能，可以在温度低到$-5^{\\circ}C$ ( $23^{\\circ}\\mathrm{F}$ ）时施工。  \n\n(6）聚硅氧烷面漆进行有机改性后形成的无机-有机聚合物面漆，是低VOC、无异氰酸酯、高耐候性的涂料产品。聚硅氧烷是以Si一O键为主的聚合物，键能高达 $445\\mathrm{kJ/mol}$ 大大高于有机聚合物典型的碳-碳键的键能 $358\\mathrm{\\mathbfkJ/mol}$ 。这意味着需要更强的活化能才能破坏聚硅氧烷聚合物。Si一O键已经氧化使得它们可以耐受大气中的氧气和大多数氧化物的作用。通过比较，有机树脂，如环氧和醇酸树脂，体现出很早的粉化和褪化，而聚氨酯和丙烯酸也会在 $3\\sim5$ 年褪色和失光。因此，聚硅氧烷面漆具有天性的耐大气和化学性破坏的性能。第一代商品化的聚硅氧烷面漆以氢化的环氧树脂进行改性。随后发展了第二代丙烯酸氨基甲酸乙酯和丙烯酸改性的聚硅氧烷产品。聚硅氧烷树脂的黏度很低，可以使得环氧和丙烯酸聚硅氧烷混合涂料有着很高的固体分。环氧聚硅氧烷涂料的体积固体分高达 $85\\%\\sim90\\%$ ，丙烯酸聚硅氧烷涂料的体积固体分设计为 $70\\%$ 以上。体积固体分 $70\\%$ 的涂料产品更可以控制湿膜厚度，这有助于防止潜在的过喷涂而减少损耗。  \n\n（7）水性丙烯酸面漆有安全而易于使用的特性，改性丙烯酸水性涂料技术可以提供良好的防腐蚀保护和耐磨性能，同时提供良好的耐候性能、挠曲性、耐水性和耐紫外线性能。水性丙烯酸面漆可以满足颜色稳定性的要求、很低的积灰程度以及优异的耐黄变性能。因此，由于水性丙烯酸面漆突出的保色保光性能，可以长期维持良好的视觉外观，无需经常重涂，大大降低了材料和施工方面的维护费用。水性面漆良好的外观和坚韧的保护性能，兼有经济性能和易于施工的性能。它可以在完全的水性系统表面作为面漆使用，也能用于某些溶剂型系统表面，形成混合型系统。水性丙烯酸面漆VOC含量很低，约在 $100\\mathrm{g/L}$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 326,
+        "chunk": "# 3.特殊功能型涂料  \n\n(1）防污漆防污漆用来阻止海洋生物，如藤壶、牡蛎、海藻、水云、浒苔对船舶和海洋结构物上附着污损。在20世纪.70年代开始发展起来的以TBT为毒料和基料的自抛光防污漆，曾经是相当有效的大量使用的主要防污漆。然而，大量使用含TBT的后果带来了严重的环保问题。释放出来的有机锡对海洋生物危害极大，影响到它们的发育繁殖和生存。2000年国际海事组织IMO确定了在2003年1月全面禁止含TBT的防污漆的使用，到2008年1月，船壳表面不再含任何含TBT的防污漆。  \n\n无锡自抛光共聚物防污漆使用丙烯酸共聚物，通过在海水中的水解或离子交换来对毒料释放起作用。这种丙烯酸共聚物系统的反应与早先的TBTSPC防污漆有着非常相似的毒料渗出机理。丙烯酸共聚物技术的无锡SPC系统防污漆皂化层很薄，在漆膜的横截面中，可以观察到大颗粒的氧化亚铜，这是防污漆中主要使用的毒料，配合以羟基吡啶硫酮铜/锌(copper/zincpyrithione）辅助毒料，它不会在海洋环境中积聚。这种反应只在防污漆的靠近表层的部位发生，通过聚合物系统的疏水性来防止海水过度地渗透漆膜。  \n\n由于海洋工程结构物不同于航行的船舶，因此对于防污漆的选择有着特殊的要求，主要是依靠水流的作用来抛光防污漆表面从而防止海生物的附着，因此要选择特殊设计的静止建筑物表面防污漆。  \n\n(2）甲板防滑涂料超强环氧防滑耐磨涂料是由高固体分环氧树脂涂料基料、固化剂和高强度耐磨磨料三个组分组成，设计用于干燥、潮湿或油滑条件下以高膜厚达到耐久性、耐磨损和防滑特性。由于超强耐磨磨料混合在漆料中进行喷涂，因此钢板在喷砂后首先要喷涂一道防锈底漆，厚度在 $150{\\sim}300\\upmu\\mathrm{m}$ 。底漆硬干后再喷涂超强环氧防滑耐磨涂料，施工工具不能使用普通的喷涂设备，而要使用重力式漏斗喷枪。喷涂过后表面呈粗糙状，固化后可以在上面喷涂环氧或聚氨酯面漆，以获得所需要的面漆颜色。  \n\n(3）耐高温涂料平台上生产设备和配管，大多数工作温度为常温，常用的涂层系统基本上均可使用。加热器、压缩机或其他设备的某些表面的温度可能会很高。如果这些表面需涂层，可以采用特定的高温涂层。  \n\n低于 $120^{\\circ}C$ 非保温管线表面，与一般的碳钢结构相同，可以选用环氧富锌/无机硅酸锌配以环氧涂料中间漆和脂肪族聚氨酯面漆的配套方案。长期运行在 $100{\\sim}120^{\\circ}C$ 的温度环境下，选用环氧涂料和聚氨酯漆，其白色或浅色涂料会有变黄的可能，但是不影响其使用效果。  \n\n在 $120{\\sim}230^{\\circ}C$ 时，可以选用丙烯酸有机硅或酚醛环氧涂料。在温度 $200{\\sim}400^{\\circ}C$ 时，主要可以选用无机硅酸锌底漆。在 $400{\\sim}600^{\\circ}\\mathsf C$ ，有机硅铝粉漆是主要的选择。  \n\n(4）金属喷涂层金属喷涂层包括铝/铝合金和锌/锌合金，作为特殊用途用于大气区，例如火炬臂上。好的表面处理和清洁度是必要的。表面处理要求达到NACENo.2/SSPC$\\mathrm{10/Sa~2\\frac{1}{2}}$ 或 NACE No.1/SSPC 5/Sa 3。  \n\n热喷涂施工符合NORSOKM501中的质量要求。每道涂层应该均匀施工于整个表面。涂层多道施工，喷涂行枪之间要有搭幅。涂层要附着牢固，表喷涂后要均匀，没有块状、松散的飞溅滴落金属、气泡、灰分、其他缺陷和局部的漏涂。  \n\n金属喷涂层在大气区、飞溅区以及高温区可以用有机涂层进行封闭。封闭层可以稀释以便能渗入金属喷涂层孔隙内部。封闭层的颜色要与金属喷涂层有所区别，以方便目测检查。使用温度低于 $120^{\\circ}\\mathrm{C}\\left(248^{\\circ}\\mathrm{F}\\right)$ ）可以使用环氧涂料，高于其温度可以使用有机硅涂料。  \n\n更多的有关金属热喷涂的施工要求可以参考NACENo.12/AWS（5）C2.23M/SSPC-CS 23.00。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 327,
+        "chunk": "# 4.镀锌涂层  \n\n对于复杂钢构件，用通常的方法施加涂层费用会很高，而且也困难，而热浸镀锌会是一种有效的方法。护栅、扶栏、梯子、仪表盒、设备撬座及其他类似形状的构件可用镀层保护。像其他含锌涂层一样，镀锌层在酸性和碱性环境中也会受到损坏，不应接触水泥、钻井泥浆或井中酸性介质。在飞溅区和全浸区，镀型层作为阳极受到腐蚀，会很快穿透或失效。这些区域应使用其他类型的材料或在镀锌层的上面再覆盖一层涂层。镀锌金属可以用合适的底漆或面漆覆盖，以改善其抗化学特质和盐水的侵蚀性。  \n\n热浸镀锌根据ISO1461进行。结构部位和装配钢材表面最小的膜厚度要求为 $125\\mu\\mathrm{m}$ 和$900g/\\mathrm{m}^{2}$ 。结构部位要喷射清理后才能进行热浸镀锌。需要额外的涂层时，可以选用NOR-SOKM501中的涂料系统No.6。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 328,
+        "chunk": "# 六、海洋工程防腐蚀涂料性能要求  \n\n海洋工程防腐蚀涂料性能要求的主要标准目前主要有三个： $\\textcircled{1}$ ISO 20340《Paints andVarnishes-Performance Requirements for Protective Paint Systems for Offshore and Re-lated Structures》色漆和清漆——-离岸和相关结构防护涂料系统的性能要求； $\\textcircled{2}$ NORSOKM501《Surface Preparation and Protective Coatings》表面处理和防护涂料； $\\textcircled{3}$ NACESP0108《Corrosion Control of Offshore Structures by Protective Coatings》离岸结构的防护涂料腐蚀控制。",
+        "category": " Introduction"
+    },
+    {
+        "id": 329,
+        "chunk": "# 1.ISO 20340  \n\n海洋工程及其油气设施，其腐蚀环境最为恶劣，必须对其进行特别的关注：一方面要有效地对腐蚀进行控制而延长其使用寿命；另一方面要减少安全风险和操作费用。自从ISO12944制定以来，对于C5-M和 $\\cdot\\operatorname{Im}2$ 腐蚀环境下的防护涂料应用，一直具有争议。经过多年  \n\n的讨论，2003年正式通过了ISO20340，其具体阐述了海洋工程及其相关结构的腐蚀防护。但它与ISO12944又有着内容上关联，比如腐蚀环境和等级、结构设计、表面处理和涂料施工及其监督执行等。  \n\nISO20340主要涉及的内容为海洋工程现场施工、涂料、防护涂料系统和涂料系统的性能测试等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 330,
+        "chunk": "# （1）涂料系统的基本性能  \n\n标准中对涂料的性能测试方法和要求有着非常详尽的规定，在大气环境和浸水环境下的涂料系统基本性能要求见表3-4-56。在海洋工程方面，所用涂料系统都需要通过第三方独立试验室按该要求的测试验证。  \n\n表3-4-56ISO20340涂料系统和基本性能要求  \n\n\n<html><body><table><tr><td>底材</td><td colspan=\"7\">碳钢喷射清理：Sa2或Sa3；表面粗糙度：中等（G)</td><td></td><td>热浸镀锌金属喷涂层</td></tr><tr><td>腐蚀环境等级</td><td colspan=\"3\">C5-M</td><td colspan=\"4\">Im2</td><td>C5-M</td><td>C5-M</td></tr><tr><td>第一道涂层</td><td>Zn(R)无机Zn(R)有机</td><td></td><td>其他底漆</td><td>Zn(R)无机</td><td>Zn(R)有机</td><td colspan=\"2\">其他</td><td></td><td></td></tr><tr><td>NDFT/μm≥</td><td>60</td><td>40</td><td>60</td><td>60</td><td>40</td><td>60</td><td>200</td><td></td><td></td></tr><tr><td>涂层道数</td><td>4（包括 连接漆)</td><td>3</td><td>3</td><td>4（包括 连接漆)</td><td>3</td><td>3</td><td>2 1</td><td>2</td><td>2（包括 连接漆）</td></tr><tr><td>涂层系统 NDFT/μm ≥</td><td>280</td><td>300</td><td>350</td><td>330</td><td>350</td><td>450600800</td><td></td><td>200</td><td>200</td></tr></table></body></html>\n\n在进行涂料性能测试(ISO4628,ISO15711以及划线处腐蚀)前，必须根据ISO4624进行附着力拉开法测试，以下测试数据可以作为要求达到的测试值  \n\n<html><body><table><tr><td>拉开法测试</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>(ISO 4624老化</td><td>3</td><td>3</td><td>4</td><td>3</td><td>3</td><td>4</td><td>6</td><td>8</td><td>2</td><td>1</td></tr><tr><td>前）</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>\n\n$\\textcircled{1}$ 金属涂层的厚度根据ISO1461（热浸镀锌）或ISO2063（金属涂层钢材）以及ISO12944-4：1988中第12条（热浸镀锌）或第13条（金属涂层钢材）中准备的涂层。$\\textcircled{2}$ Zn（R）为富锌底漆，符合ISO12944-5。  \n\n(2）鉴别测试每一种涂料鉴别必须进行两种鉴别测试： $\\textcircled{1}$ 指纹识别（fingerprint）；$\\textcircled{2}$ 定期批量测试。  \n\n指纹识别是为了确保所供应涂料的一致性。黏结剂的性能（红外线光谱和功能团含量）要在树脂、颜料和溶剂分离后进行。特征测试的示例见表3-4-57，更能精确地测试涂料成分的其他测试方法也可以采用。  \n\n表3-4-57 指纹识别示例  \n\n\n<html><body><table><tr><td colspan=\"2\">颁发日期</td><td>基料</td><td>固化剂</td></tr><tr><td colspan=\"2\">涂料名称</td><td></td><td></td></tr><tr><td colspan=\"2\">涂料生产商名称</td><td></td><td></td></tr><tr><td colspan=\"2\">批号</td><td></td><td></td></tr><tr><td colspan=\"2\">生产日期</td><td></td><td></td></tr><tr><td></td><td>测试方法</td><td>测试结果范围</td><td>测试结果范围</td></tr></table></body></html>  \n\n主要参数  \n\n\n<html><body><table><tr><td>黏结剂含量（质量分数）/%</td><td>见参考目录</td><td>±2)</td><td></td><td>±2)</td></tr><tr><td>颜料含量，包括填料(质量分数）/%</td><td>见参考目录</td><td>±2)</td><td></td><td>r ±2)</td></tr></table></body></html>  \n\n续表  \n\n可选参数  \n\n\n<html><body><table><tr><td>红外线光谱</td><td>见参考目录</td><td></td><td></td></tr><tr><td>不挥发分（质量分数）/%</td><td>ISO 3251</td><td></td><td>±2)</td></tr><tr><td>密度/(g/mL)</td><td>ISO2811的适当部分</td><td>±0.05)</td><td>（ ±0.05)</td></tr><tr><td>灰分/%</td><td>见参考目录</td><td>±3)</td><td>（ ±3)</td></tr></table></body></html>  \n\n<html><body><table><tr><td rowspan=\"2\">颜料含量 （质量分数）/%</td><td rowspan=\"2\">金属锌/总锌粉量 铁 磷</td><td rowspan=\"2\">见参考目录</td><td>(±1)</td><td>( ±1)</td></tr><tr><td>±1) ( ±1)</td><td>（ ±1)</td></tr><tr><td rowspan=\"4\">功能团含量</td><td>铝 环氧</td><td>A</td><td>(±1)</td><td>( ±1) （ ±1)</td></tr><tr><td>羟基</td><td></td><td></td><td></td></tr><tr><td>酸</td><td>见参考目录</td><td></td><td></td></tr><tr><td>胺</td><td></td><td></td><td></td></tr></table></body></html>\n\n注：测试方法要经各方同意。  \n\n涂料生产商被要求对涂料进行定期批量测试，并把测试结果提供给采购者。测试项目至少包括密度（ISO2811）和不挥发分（ISO3251)，见表3-4-58。  \n\n表3-4-58 定期批量测试（最终的产品检测）  \n\n\n<html><body><table><tr><td colspan=\"2\">颁布日期</td><td colspan=\"2\">生产日期</td></tr><tr><td colspan=\"2\">涂料名称</td><td colspan=\"2\">产品手册编号</td></tr><tr><td colspan=\"2\">批号</td><td colspan=\"2\">材料安全手册编号</td></tr><tr><td>测试项目</td><td>测试方法</td><td>测试结果</td><td>规范误差</td></tr><tr><td>密度/（g/mL)</td><td>ISO2811适合的部分</td><td></td><td>(±0.05)</td></tr><tr><td>不挥发分（质量分数）/%</td><td>ISO 3251</td><td></td><td>(±2)</td></tr></table></body></html>\n\n注：若密度大于 $z_{\\mathrm{B}}/\\mathrm{mL}$ ，如 $Z\\bar{\\boldsymbol{\\mathrm{n}}}\\hat{\\mathcal{(\\mathbf{R})}}$ ，相关误差为 $\\pm0.1\\upmu/\\mathrm{mL}$ 鼎  \n\n(3）涂料性能测试进行涂料性能测试的试板准备要根据ISO1514执行。试板的类型、数量、准备和状态根据ISO12944-6以及涂料厂商的要求执行。除非另有约定，试板至少要准备三块，尺寸为（ $300\\times90\\times5)$ mm。  \n\n试板的性能测试要求见表3-4-59。其他的可选测试要求也可进行，比如说耐冲击性、耐磨性和耐开裂性等。实际的测试项目要由相关各方同意进行。  \n\n表3-4-59 质量鉴定测试  \n\n\n<html><body><table><tr><td rowspan=\"2\">测试</td><td rowspan=\"2\">划痕</td><td rowspan=\"2\">环境腐蚀 等级C5-M</td><td colspan=\"3\">环境腐蚀等级Im2</td></tr><tr><td>飞溅区</td><td>潮差区</td><td>永久性浸水区</td></tr><tr><td>耐老化(ISO11507和ISO7253)/h</td><td>是</td><td>4200</td><td>4200</td><td>4200</td><td>一</td></tr><tr><td>阴极剥离(ISO15711)/月</td><td>按ISO15711的要求</td><td>一</td><td>一</td><td>6</td><td>6</td></tr><tr><td>海水浸泡(ISO2812-2)/h</td><td>是</td><td>一</td><td></td><td>4200</td><td>4200</td></tr></table></body></html>\n\n标准的耐老化试验（图3-4-51)，一个循环为持续一周（168h)，它包括：$\\textcircled{1}$ 72h暴露于紫外线和水，根据ISO11507进行；$\\textcircled{2}$ $72\\mathrm{h}$ 盐雾试验，根据ISO7253进行；  \n\n$\\textcircled{3}$ 24h低温暴露。  \n\n![](images/d45b23255dc4639dab474a2d4ab6fbc55695c2f719cb5b3be879ea0589115e8c.jpg)  \n图3-4-51 老化试验示意图  \n\n除了这种标准程序外，如果另有约定的话，第7天的低温暴露可以代之以常温暴露，试验室条件 $(23\\pm2)^{\\circ}C$ ，RH $(50\\pm5)\\%$ 0  \n\n试板的评定根据ISO12944-6进行，方法和要求见表3-4-60。至少要三块试板中两块达到要求才能通过质量评定测试。  \n\n表3-4-60 试板的评定要求  \n\n\n<html><body><table><tr><td>评定方法</td><td>质量评定前的要求</td><td colspan=\"2\">质量评定后的要求</td></tr><tr><td>ISO 4624拉开法</td><td>相关各方都要同意：参考防护涂料 系统的示意</td><td colspan=\"2\">拉开值至少达到原始的50%（2周保养后的评定，见 ISO 12944-6)</td></tr><tr><td>ISO 4628-2(起泡）</td><td></td><td>0(S0)</td><td>质量鉴定测试后立即评定</td></tr><tr><td>ISO 4638-3(锈蚀）</td><td></td><td>RiQ</td><td>质量鉴定测试后立即评定</td></tr><tr><td>ISO 4628-4（开裂）</td><td></td><td>0(S0)</td><td>质量鉴定测试后立即评定</td></tr><tr><td>ISO 4628-5(剥落)</td><td></td><td>0(S0)</td><td>质量鉴定测试后立即评定</td></tr><tr><td>ISO 4628-6(粉化)</td><td></td><td>0(S0)</td><td>如果有要求</td></tr><tr><td>划痕处腐蚀</td><td></td><td colspan=\"2\">2mm宽划痕，M<3mm 0.05mm宽划痕，M<1mm</td></tr><tr><td>阴极剥离ISO15711</td><td>6mm直径的小孔；完全露出钢板</td><td colspan=\"2\">相等直径<20mm，没有剥离</td></tr></table></body></html>\n\n注：试板距边缘 $10\\mathrm{mm}$ 处发生的任何缺陷不考虑在内。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 331,
+        "chunk": "# 2. NORSOK M501  \n\n挪威的NORSOK标准是目前海洋工程防腐蚀涂装最为严格的涂装规范，目前执行的是NORSOKM501Rev.5，June2004。在北海区域的石油天然气工业一向有着自己的涂装规格书。它们包括了自己所认可的一系列产品和供应厂家。另外，这些规格书并不是一成不变的。对于新工程，通常都由主要承包商和顾问公司来建立一个新的规格书。一系列的现场使用报告以及实验室对于不同品种涂料的性能测试，一直被参考引用来完善发展涂装规格。NORSOKM501中关于涂料特性的测试方法和要求则直接引用了ISO20340。  \n\nNORSOKM-501包括一个推荐的涂料系统以及预处理要求、施工要求、检测方法等一些可接受的标准规范。NORSOKM-501标准已经被认为是北海海洋工程涂装中质量的一个标志性提高和发展。在很大程度上，它减少了涂装方面的整体费用。  \n\nNORSOK标准适用的涂料系统在其标准附录A的表格中有说明（后续有详尽说明）。其中涂料系统No.1、3B、4、5和7应根据标准中第10条款进行资质认可（表3-4-61)。对于那些资质预认证的涂料系统，规定的涂料系统只是示例，如果满足本NORSOK标准的要求，替代的涂料系统也可使用。然而，对于涂料系统No.1和7，附录A中的涂层道数和涂层漆膜厚度是最低要求，应该进行资质预认证测试。另外，任何在户外或自然通风区域的防火保护涂料必须要有预先的资质测试。面漆的颜料应该根据附录B，压载水舱和淡水舱中应  \n\n该使用浅颜色。  \n\n当车间底漆作为完整涂料系统的一部分时，应通过相应的测试  \n\n表3-4-61NORSOKM501涂料系统资质认可测试要求  \n\n\n<html><body><table><tr><td>测试</td><td>接受标准</td></tr><tr><td>海水浸泡，ISO20340 下列涂料系统要求测试： 1.涂料系统No.3B和7； 2.涂料系统No.1用于潮差区或飞溅区</td><td>根据ISO20340 根据ISO20340</td></tr><tr><td>耐老化试验，ISO20340 程序A 下列涂料系统要求测试： 1.涂料系统No.1、No.3B、No.4、No.5A和5B； 2.涂料系统No.7用于潮差区或飞溅区</td><td>增补要求： 1.粉化（见ISO4628-6）最大等级2，只适用于涂料系统No.1； 2.附着力（见ISO4624）最小5.0MPa，最大50%原始数据的减小； 3.没有机械处理时的重涂，附着力至少达到5.0MPa； 4.涂料系统No.5A和No.5B的附着力（见ISO4624），原始数据最 大50%的减小，对于水泥基的产品至少2.0MPa，对于环氧基产品，至 少3.0MPa; 5.完整的耐老化试验后，须报告涂料系统No.5A.的吸水情况</td></tr><tr><td>阴极剥离，ISO20340 涂料系统No.3B和No.7； 涂料系统No.1用于潮汐和飞溅区</td><td>根据ISO20340</td></tr></table></body></html>  \n\n注：1.可接受标准考虑为至少的性能要求。2.附着力测试必须用液压式测试仪进行。对于涂料系统No.4，附着力测试可在未暴露于上述测试环境的没有防滑磨  \n料的试板上进行。3.在NORSOK标准中，划痕处腐蚀可接受标准为 $2\\mathrm{mm}$ 宽。这样，对于本NORSOK标准来说，在ISO20340中规  \n定的 $0.05\\mathrm{mm}$ 可以忽略，试板尺寸可以减小到 $75\\mathrm{mm}\\times150\\mathrm{mm}\\times5\\mathrm{mm}$ 4.涂料系统No.3B对于压载水舱来说，要求通过DNV Classification Note 33.1class B1的认可，才被认为有资格  \n使用。5.涂料系统No.5A的测试厚度为 $\\bar{5}\\mathrm{mm}$ 6.涂料系统No.5A和5B在测试时不能有加强结构7.涂料系统No.5A和5B在测试时不能有面漆涂层。",
+        "category": " Introduction"
+    },
+    {
+        "id": 332,
+        "chunk": "# 3.NACE SP0108  \n\n用于海洋工程的重防腐涂料必须通过所有测试，并由第三方检测单位进行检测。如果在通常检测后涂料配方有所改变，涂料系统需要重新由第三方进行检测。  \n\n指纹识别在海洋工程重防腐涂料中显得相当重要，与NORSOKM501一样，NACESP0108同样引人了这一涂料性能检测方法（表3-4-62)，以确保涂料品质的稳定。如果该项测试是由涂料生产商自己进行的，须由QA/QC经理或高级技术经理所认可。  \n\n表3-4-62 涂料材料的指纹识别  \n\n\n<html><body><table><tr><td>编号</td><td>性能</td><td>组分</td><td>公差</td><td>标准</td></tr><tr><td>１</td><td>密度/（g/cm3）</td><td>A 和B,每个组分</td><td>±0.05</td><td>ASTM D1475</td></tr><tr><td>2</td><td>固体分（质量分数）/%</td><td>A组分和B组分的混合</td><td>±2</td><td>ASTM D2369</td></tr><tr><td>3</td><td>颜料成分（质量分数）/%</td><td>A 和B,每个组分</td><td></td><td>涂料制造商的指导</td></tr><tr><td>4A</td><td>FTIR-ATR扫描，有颜料</td><td>A和B，每个组分</td><td></td><td>涂料制造商的指导</td></tr><tr><td>4B</td><td>红外扫描(IR)，无颜料</td><td>A和B，每个组分</td><td></td><td>ASTM D2621</td></tr></table></body></html>  \n\n大气区和飞溅区的涂料测试方案见表3-4-63，这些涂料用于碳钢表面的新建或维修系  \n\n统，适用温度最大 $120^{\\circ}C$ (248F)。  \n\n表3-4-63 大气区和飞滩区涂料系统的测试方案  \n\n\n<html><body><table><tr><td rowspan=\"2\">涂料性能</td><td rowspan=\"2\">表面处理</td><td colspan=\"2\">大气区，甲板</td><td colspan=\"2\">飞溅区</td></tr><tr><td>新建结构</td><td>维修</td><td>新建结构</td><td>维修</td></tr><tr><td rowspan=\"3\">锈蚀蔓延</td><td>NACE No.2 /SSPC-SP 10</td><td>NACE TM0404</td><td>NACE TM0304</td><td>NACE TM0404</td><td>NACE TM0304</td></tr><tr><td>200mg/m氯离子</td><td>不测</td><td>NACE TM0304</td><td>不测</td><td>NACE TM0304</td></tr><tr><td>潮湿</td><td>不测</td><td>不测</td><td>不测</td><td>NACE TM0304</td></tr><tr><td>边缘保持</td><td>砂纸</td><td>NACE TM0404</td><td>NACE TM0304</td><td>NACE TM0404</td><td>NACE TM0304</td></tr><tr><td>热循环</td><td>NACE No. 2 /SSPC-SP 10</td><td>NACE TM0404</td><td>NACE TM0304</td><td>NACE TM0404</td><td>NACE TM0304</td></tr><tr><td>柔韧性</td><td>NACE No. 2 /SSPC-SP 10</td><td>NACE TM0404</td><td>NACE TM0304</td><td>NACE TM0404</td><td>NACE TM0304</td></tr><tr><td>冲击强度（仅适用 于甲板和小艇卸载)</td><td>NACE No.2 /SSPC-SP 10</td><td>ASTM G14</td><td>ASTM G14</td><td>ASTM G14</td><td>ASTM G14</td></tr><tr><td rowspan=\"3\">浸水</td><td>NACE No.1 /SSPC-SP 5</td><td>不测</td><td>不测</td><td>不测</td><td>NACE TM0304</td></tr><tr><td>200mg/m²氯离子</td><td>不测</td><td>不测</td><td>不测</td><td>NACE TM0304</td></tr><tr><td>潮湿</td><td>不测</td><td>不测</td><td>不测</td><td>NACE TM0304</td></tr><tr><td rowspan=\"3\">阴极剥离</td><td>NACE No.1</td><td>不测</td><td>不测</td><td>ASTM G14</td><td>NACE TM0304</td></tr><tr><td>/SSPC-SP 5 200mg/m²氯离子</td><td>不测</td><td>不测</td><td>不测</td><td>NACE TM0304</td></tr><tr><td>潮湿</td><td>不测</td><td>不测</td><td>不测</td><td>NACE TM0304</td></tr></table></body></html>  \n\n压载水舱、空舱、海水舱和外部全浸区用于碳钢表面的涂料系统，包括新建和维修系统，测试方案见表3-4-64。  \n\n表3-4-64压载水舱、空舱、海水舱和外部全浸区涂料系统的测试方案  \n\n\n<html><body><table><tr><td rowspan=\"2\">涂料性能</td><td rowspan=\"2\">表面处理</td><td colspan=\"2\">压载水舱、空舱、海水舱</td><td>外部全浸区</td></tr><tr><td>新建</td><td>维修</td><td>新建</td></tr><tr><td>边缘保持</td><td>砂纸</td><td>NACE TM0104</td><td>NACE TM0104</td><td>NACE TM0204</td></tr><tr><td rowspan=\"3\">耐水</td><td>NACE No. 1/SSPC SP5</td><td>NACE TM0104</td><td>NACE TM0104</td><td>NACE TM0204</td></tr><tr><td>100mg/m²氯离子</td><td>不测</td><td>NACE TM0104</td><td>不测</td></tr><tr><td>潮湿</td><td>不测</td><td>NACE TM0104</td><td>不测</td></tr><tr><td rowspan=\"3\">阴极剥离</td><td>NACE No.1/SSPC SP5</td><td>NACE TM0104</td><td>NACE TM0104</td><td>NACE TM0204</td></tr><tr><td>100mg/m²氯离子</td><td>不测</td><td>NACE TM0104</td><td>不测</td></tr><tr><td>潮湿</td><td>不测</td><td>NACE TM0104</td><td>不测</td></tr><tr><td>体积稳定</td><td>漆膜不限</td><td>NACE TM0104</td><td>NACE TM0104</td><td>NACE TM0204</td></tr><tr><td>老化稳定</td><td>NACE No.1/SSPC SP5</td><td>NACE TM0104</td><td>NACE TM0104</td><td>NACE TM0204</td></tr><tr><td>漆膜开裂</td><td>NACE No. 1/SSPC SP5</td><td>NACE TM0104</td><td>NACE TM0104</td><td>不测</td></tr><tr><td rowspan=\"3\">热湿循环（仅适用 于FPSO)</td><td>NACE No.1/SSPC SP5</td><td>NACE TM0104</td><td>NACE TM0104</td><td>不测</td></tr><tr><td>100mg/m²氯离子</td><td>不测</td><td>NACE TM0104</td><td>不测</td></tr><tr><td>潮湿</td><td>不测</td><td>NACE TM0104</td><td>不测</td></tr></table></body></html>  \n\n用于大气区和飞溅区；压载水舱、空舱和海水舱以及外部全浸区的涂料系统可接受标准见表3-4-65。  \n\n表3-4-65海洋工程结构涂料测试可接受标准  \n\n\n<html><body><table><tr><td>涂料性能</td><td>测试方法</td><td>可接受标准</td></tr><tr><td rowspan=\"2\">锈蚀蔓延</td><td>NACE TM0304</td><td><3.5mm（0.14in）非富锌底漆系统 <1.4mm(0.6in）富锌底漆系统</td></tr><tr><td>NACE TM0404</td><td>划痕处和边缘处，不起泡/生锈/开裂/剥落</td></tr><tr><td rowspan=\"2\">边缘保持</td><td>NACE TM0104</td><td></td></tr><tr><td>NACE TM0204</td><td>邻近边缘处平面上干膜厚度的测量，大于平均干膜厚度的50%</td></tr><tr><td rowspan=\"2\"></td><td>NACE TM0304</td><td></td></tr><tr><td>NACE TM0404</td><td></td></tr><tr><td rowspan=\"2\">热循环</td><td>NACE TM0304 NACE TM0404</td><td>无开裂</td></tr><tr><td>NACE TM0304</td><td></td></tr><tr><td rowspan=\"2\">柔韧性</td><td>NACE TM0404</td><td>>1%，最低使用温度时</td></tr><tr><td>ASTM G14</td><td></td></tr><tr><td>冲击强度</td><td></td><td>>5.6J（50in·1bf），甲板和小艇卸载飞溅区</td></tr><tr><td rowspan=\"4\">浸水</td><td>NACE TM0104</td><td><7mm(0.8in）剥离</td></tr><tr><td>NACE TM0204</td><td>划痕处和边缘处，不起泡/生锈/开裂/剥落</td></tr><tr><td>NACE TM0304 NACE TM0404</td><td></td></tr><tr><td></td><td></td></tr><tr><td rowspan=\"4\">阴极剥离</td><td>NACE TM0104</td><td><7mm(0.8in）剥离</td></tr><tr><td>NACE TM0204</td><td></td></tr><tr><td>NACE TM0304</td><td>划痕处和边缘处，不起泡/生锈/开裂/剥落</td></tr><tr><td>NACE TM0404</td><td></td></tr><tr><td rowspan=\"2\">体积稳定</td><td>NACE TM0104</td><td>可选②</td></tr><tr><td>NACE TM0204</td><td></td></tr><tr><td rowspan=\"2\">老化稳定</td><td>NACE TM0104</td><td>>50%</td></tr><tr><td>NACE TM0204</td><td></td></tr><tr><td>厚膜开裂 热湿循环（仅适用于FPSO）</td><td>NACE TM0104</td><td>没有开裂 <3.5mm(0.14in)</td></tr></table></body></html>\n\n$\\textcircled{1}$ 湿剥离测试用于评价涂料的浸水性能。$\\textcircled{2}$ 该方法为可选方案，如果业主要求该测试，可接受标准由业主和涂料供应商相互协商。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 333,
+        "chunk": "# 七、海洋工程防腐涂料系统",
+        "category": " Introduction"
+    },
+    {
+        "id": 334,
+        "chunk": "# 1.NORSOK推荐涂料系统  \n\nNORSOKM501是海洋工程中防腐蚀涂装的最具权威性的行业标准，是北海地区海洋工程防腐蚀表面处理主要采用的标准。在北海地区海洋工程使用的涂料系统，必须按NOR-SOKM501的要求通过相应的测试，取得资格认可。在其附录中，推荐的典型涂料配套方案分述见表3-4-66。  \n\n表3-4-66NORSOKM501推荐的涂料方案  \n\n\n<html><body><table><tr><td>施工部位</td><td>表面处理</td><td>涂料系统</td><td>干膜厚度 MDFT/μm</td></tr><tr><td>涂料系统No.1(应进行预认证） 碳钢，操作温度<120℃ 钢结构，设备、贮槽、管道和阀门（未安装）的外 表面</td><td>清洁度：ISO8501-1 Sa 2 粗糙度：ISO8503中等 别级G(50~85μm,R,5)</td><td>1道富锌底漆 至少3道涂层 完整涂层 最小干膜厚度</td><td>60 280</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>施工部位</td><td>表面处理</td><td>涂料系统</td><td>干膜厚度 MDFT/μm</td></tr><tr><td rowspan=\"2\">涂料系统No.2A 用于所有操作温度>120℃的碳钢表面 涂料系统No.2A或2B，用于以下碳钢物件： 所有舱室、贮槽、管路； 燃烧井架和吊臂； 底部甲板的反面，包括管道；飞溅区救生艇站 上的护套，是可选区域（由各个项目所决定）</td><td rowspan=\"2\">清洁度：ISO 8501-1， Sa 2 粗糙度：ISO8503中等 级别G(50~85μm,R,5)</td><td>系统No.2A： 喷铝或铝的合金 封闭</td><td>200</td></tr><tr><td>系统No.2B： 喷锌或锌的合金 连接漆 中间漆 面漆</td><td>100 125 75</td></tr><tr><td>碳钢舱室内表面： 涂料系统No.3A饮用水舱； 涂料系统No.3B压载水舱/内部有海水的隔舱； 涂料系统No.3C稳定的原油、柴油和冷凝舱； 涂料系统No.3D加工贮罐<0.3MPa，<75℃； 涂料系统No.3E加工贮罐<7MPa，<80°℃； 涂料系统No.3F加工贮罐<3MPa，<130℃； 涂料系统No.3G贮藏甲醇、乙二醇酸等</td><td>清洁度：ISO8501-1， Sa 2 粗糙度：ISO8503中等 级别G(50~85μm,R,5)</td><td colspan=\"2\">No.3A：溶剂型环氧3X100或无溶剂环 氧2X300 No.3B：符合DNVB1要求 No.3C：平底和舱壁以上1m以及顶部和 上部1m处 No.3D;无溶剂或溶剂环氧 No.3E：溶剂型或无溶剂环氧或酚醛环氧 No.3F：无溶剂酚醛环氧 No.3G：无机硅酸锌50～90μm</td></tr><tr><td>涂料系统No.4 走道，逃生通道和搁置区域 涂料系统1可以用于其他甲板区域</td><td>清洁度：ISO 8501-1， Sa 2 粗糙度：ISO8503中等 级别G(50~85μm,R5)</td><td>防滑环氧层 浅色磨料粒径1～5mm</td><td>3000</td></tr><tr><td>涂料系统No.5A 环氧类防火保护层</td><td>清洁度：ISO 8501-1，Sa 2## 粗糙度：ISO8503中等 级别G(50～85μm,R5)</td><td>①1道环氧底漆 或者 ②1道环氧富锌底漆 1道环氧连接漆 总的干膜厚度</td><td>50 60 25 85</td></tr><tr><td>涂料系统No.5B 水泥基的防火保护层</td><td>清洁度：ISO8501-1， 粗糙度：ISO 8503中等 级别G(50~85μm,Ry5) Sa2</td><td>1道环氧富锌底漆 1道双组分环氧 总的干膜厚度</td><td>60 200 260</td></tr><tr><td>涂料系统No.6 需要涂漆的未绝缘不锈钢 需要涂漆的铝材</td><td>用非金属无氯磨料扫 砂，表面粗糙度25～45μm</td><td>1道环氧底漆 1道双组分环氧 1道面漆 总的干膜厚度</td><td>50 100 75 225</td></tr><tr><td>涂料系统No.7 浸水区和飞溅区的碳钢以及不锈钢</td><td>2道双组分环氧</td><td></td><td>350</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 335,
+        "chunk": "# 2.NACESP0108—2008推荐涂料系统  \n\n为了方便沟通和识别，不同部位的涂料系统规定了不同的字母和阿拉伯数字的编号，不同字母的含义如下：C（碳钢)；M（维修)；N（新建)；O（其他表面，如非铁金属）；S(不锈钢)。  \n\n(1）大气环境下的涂料系统大气区涂层系统需考虑当地的气候环境，比如气温和相对湿度，以保证涂料在规定的时间内可以固化，还要考虑到其混合使用寿命和重涂间隔。典型的大气环境涂料系统，新建结构系统见表3-4-67，维修系统见表3-4-68。耐紫外线面漆系统可以选用聚氨酯、聚硅氧烷和氟碳涂层。  \n\n表3-4-67大气环境下碳钢表面新建结构的涂料系统  \n\n\n<html><body><table><tr><td>服务范围</td><td>涂层</td><td>涂层系统</td><td></td><td>干膜厚度/μm(mil）目标干膜厚度/μm(mil)</td></tr><tr><td></td><td>1</td><td>富锌底漆</td><td>50~75(2~3)</td><td>75(3)</td></tr><tr><td>CN-1</td><td>2</td><td>环氧</td><td>125~175(5~7)</td><td>125(5)</td></tr><tr><td></td><td>3</td><td>聚氨酯</td><td>50~75(2~3)</td><td>75(3)</td></tr><tr><td>大气区 -50~120℃</td><td>1</td><td>环氧底漆</td><td>125~175(5~7)</td><td>125(5)</td></tr><tr><td></td><td>2</td><td>环氧底漆</td><td>125~175(5~7)</td><td>125(5)</td></tr><tr><td>(-58～248 °F)</td><td>3</td><td>环氧面漆</td><td>50~75(2~3)</td><td>75(3)</td></tr><tr><td>有或没有绝热层</td><td>1</td><td>金属热喷铝涂层</td><td>250～375(10~15)</td><td>250(10)</td></tr><tr><td></td><td>2</td><td>稀释的封闭层(环氧)</td><td>不计入干膜厚度</td><td>无额外干膜厚度</td></tr><tr><td></td><td>3</td><td>封闭层(环氧)</td><td>不计人干膜厚度</td><td>无额外干膜厚度</td></tr><tr><td>CN-2</td><td>1</td><td>无机硅酸富锌底漆</td><td>50~75(2~3)</td><td>75(3)</td></tr><tr><td>大气区</td><td>2</td><td>有机硅丙烯酸</td><td>25～50(1~2)</td><td>50(2)</td></tr><tr><td>120~150℃</td><td>1</td><td>金属热喷铝涂层</td><td>250~375(10~15)</td><td>250(10)</td></tr><tr><td>(248~302F) 没有绝热层</td><td>2</td><td>稀释的封闭层（有机硅丙烯酸或酚醛环氧）</td><td>不计人干膜厚度</td><td>无额外干膜厚度</td></tr><tr><td></td><td>3</td><td>封闭层（有机硅丙烯酸或酚醛环氧）</td><td>不计人干膜厚度</td><td>无额外干膜厚度</td></tr><tr><td>CN-3</td><td></td><td>酚醛环氧</td><td>100~125(4~5)</td><td>125(5)</td></tr><tr><td>大气区</td><td>2</td><td>酚醛环氧</td><td>100~125(4~5)</td><td>125(5)</td></tr><tr><td>120~150°℃</td><td>1</td><td>金属热喷铝涂层</td><td>250~375(10~15)</td><td>250(10)</td></tr><tr><td>(248~302 F)</td><td>2</td><td>稀释的封闭层(有机硅丙烯酸或酚醛环氧）</td><td>不计人干膜厚度</td><td>无额外干膜厚度</td></tr><tr><td>有绝热层</td><td>3</td><td>封闭层(有机硅丙烯酸或酚醛环氧)</td><td>不计入干膜厚度</td><td>无额外干膜厚度</td></tr><tr><td></td><td>1</td><td></td><td>250~375(10~15)</td><td></td></tr><tr><td>CN-4</td><td>2</td><td>金属热喷铝涂层 稀释的封闭层(有机硅)</td><td>不计人干膜厚度</td><td>250(10) 无额外干膜厚度</td></tr><tr><td>大气区</td><td>3</td><td>封闭层(有机硅)</td><td>不计人干膜厚度</td><td>无额外干膜厚度</td></tr><tr><td>150~450℃</td><td></td><td></td><td></td><td></td></tr><tr><td>(302~842 F) 有/没有绝热层</td><td>1</td><td>无机硅酸富锌底漆</td><td>50~75(2~3)</td><td>75(3)</td></tr><tr><td></td><td>2</td><td>有机硅</td><td>25~50(1~2)</td><td>50(2)</td></tr><tr><td rowspan=\"12\">CN-5 甲板和地板 轻载和一般负载</td><td>3</td><td>有机硅</td><td>25~50(1~2)</td><td>50(2)</td></tr><tr><td>1</td><td>富锌底漆</td><td>50~75(2~3)</td><td>75(3)</td></tr><tr><td>2</td><td>高固体分环氧</td><td>125~175(5~7)</td><td>125(5)</td></tr><tr><td>3</td><td>防滑环氧</td><td>125~175(5~7)③</td><td>125(5)</td></tr><tr><td>4</td><td>聚氨酯</td><td>50~75(2~3)</td><td>75(3)</td></tr><tr><td>1</td><td>环氧底漆</td><td>125~175(5~7)</td><td>125(5)</td></tr><tr><td>2</td><td>高固体分环氧</td><td>125~175(5~7)</td><td>125(5)</td></tr><tr><td>3</td><td>防滑环氧②</td><td>125~175(5~7)@</td><td>125(5)③</td></tr><tr><td>4</td><td>聚氨酯</td><td>50~75(2~3)</td><td>75(3)</td></tr><tr><td>1</td><td>金属热喷铝涂层</td><td>250~375(10~15)</td><td>250(10)</td></tr><tr><td>2</td><td>封闭层(聚氨酯)</td><td>不计人干膜厚度</td><td>无额外干膜厚度</td></tr><tr><td>１</td><td>厚浆型环氧防滑涂层</td><td>卖方规格书</td><td>卖方规格书</td></tr><tr><td>CN-6</td><td>1</td><td>富锌底漆</td><td>50~75(2~3)</td><td>75(3)</td></tr><tr><td>甲板和地板</td><td>2 3</td><td>高固体分环氧</td><td>200~300(8~12)</td><td>250(10)</td></tr><tr><td>重载和直升机甲板</td><td></td><td>环氧防滑涂层②</td><td>200~300(8~12)</td><td>250(10)</td></tr><tr><td></td><td>4</td><td>聚氨酯安全标记</td><td>50~75(2~3)</td><td>75(3)</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>服务范围</td><td>涂层</td><td>涂层系统</td><td>干膜厚度/μm（mil)</td><td>目标干膜厚度/μm（mil)</td></tr><tr><td rowspan=\"7\">CN-6 甲板和地板 重载和直升机甲板</td><td>1</td><td rowspan=\"2\">环氧底漆</td><td rowspan=\"2\">125~175(5~7) 200~300(8~12)</td><td>125(5)</td></tr><tr><td>高固体分环氧</td><td>250(10)</td></tr><tr><td>3 4</td><td>环氧防滑涂层 聚氨酯安全标记</td><td>200~300(8~12)@ 50～75(2~3)</td><td>250(10)③ 75(3)</td></tr><tr><td>1</td><td>铝/氧化铝预合金热喷涂涂层</td><td>300~400(12~16)</td><td>300(12)</td></tr><tr><td>2</td><td>封闭层(聚氨酯)</td><td>不计人干膜厚度</td><td>无额外干膜厚度</td></tr><tr><td>1</td><td>厚浆型环氧防滑涂层</td><td>卖方规格书</td><td>卖方规格书</td></tr><tr><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n$\\textcircled{1}$ 封闭金属热喷铝涂层表面孔隙的封闭层不应计人现在热喷铝涂层的干膜厚度。允许使用稀释的封闭漆，施工下道漆前，干燥时间 $>30\\mathrm{min}$  \n\n$\\textcircled{2}$ 防滑砂在施工前要和液体涂料相混合，以保证对砂粒的良好润湿性。细砂可用于环氧防滑涂层的施工。  \n\n$\\textcircled{3}$ 干膜厚度应该在防滑砂加人前进行计算。  \n\n④金属喷铝层的喷枪参数以及喷枪要调整好获得所需要的表面具有防滑性。尽管金属喷铝层含有固有的坚硬耐磨氧化铝粒子，应使用合金铝丝，含有 $90\\%$ 的铝和 $10^{9\\times6}$ 甚至更高比例的氧化铝。  \n\n表3-4-68大气环境下碳钢表面维修涂料系统  \n\n\n<html><body><table><tr><td>使用范围</td><td>涂层</td><td>涂层系统</td><td>干膜厚度 /μm(mil)</td><td>目标干膜厚度 /μm(mil)</td></tr><tr><td>CM-1 冷凝水管系</td><td>1</td><td>水下固化环氧①</td><td>375~750(15~30)</td><td>500(20)</td></tr><tr><td rowspan=\"8\">CM-2 大气区 120~150°℃ (248~302 F) 有/没有绝热层</td><td>１</td><td>环氧底漆</td><td>125~175(5~7)</td><td>125(5)</td></tr><tr><td>2 3</td><td>高固体分环氧 聚氨酯</td><td>125~175(5~7)</td><td>125(5)</td></tr><tr><td></td><td></td><td>50~75(2~3)</td><td>75(3)</td></tr><tr><td>1</td><td>有机富锌底漆</td><td>50~75(2~3)</td><td>75(3)</td></tr><tr><td>2 3</td><td>环氧</td><td>125~175(5~7)</td><td>125(5)</td></tr><tr><td>聚氨酯</td><td></td><td>50~75(2~3)</td><td>75(3)</td></tr><tr><td>1 2</td><td>湿固化聚氨酯底漆 湿固化聚氨酯</td><td>75~125(3~5)②</td><td>100(4)</td></tr><tr><td>3</td><td>湿固化聚氨酯</td><td>75～125(3~5)② 75~125(3~5)②</td><td>100(4) 100(4)</td></tr><tr><td>CM-3 大气区</td><td>1 2</td><td>酚醛环氧 酚醛环氧</td><td>100~125(4~5) 100～125(4~5)</td><td>125(5)</td></tr><tr><td>120~150°℃ (248~302 F)</td><td>1</td><td>硅基厚浆型涂料</td><td></td><td>125(5)</td></tr><tr><td>有/没有绝热层</td><td>2</td><td>硅基厚浆型涂料</td><td>100~200(4~8) 100~200(4~8)</td><td>150(6) 150(6)</td></tr><tr><td>CM-4 大气区</td><td>1</td><td>有机硅</td><td>25～50(0.5~1)</td><td>25(1)</td></tr><tr><td>150~450°℃ (302~842°F)</td><td>2</td><td>有机硅</td><td>25~50(0.5~1)</td><td>25(1)</td></tr><tr><td>有/没有绝热层</td><td>1 2</td><td>硅基厚浆型涂料②</td><td>100~200(4~8)</td><td>150(6)</td></tr><tr><td rowspan=\"5\">CM-5 甲板和地板一 重载和直升机</td><td></td><td>硅基厚浆型涂料③</td><td>100~200(4~8)</td><td>150(6)</td></tr><tr><td>1</td><td>环氧底漆</td><td>125~175(5~7)</td><td>125(5)</td></tr><tr><td>2</td><td>高固体分环氧</td><td>125~175(5~7)</td><td>125(5)</td></tr><tr><td>3</td><td>环氧防滑涂层</td><td>125~175(5~7)</td><td>125(5)</td></tr><tr><td></td><td></td><td></td><td>75(3)</td></tr><tr><td>甲板</td><td></td><td></td><td></td><td></td></tr><tr><td rowspan=\"4\"></td><td>4</td><td></td><td></td><td></td></tr><tr><td></td><td>聚氨酯</td><td>50~75(2~3)</td><td></td></tr><tr><td>1</td><td>厚浆型环氧防滑涂层</td><td></td><td></td></tr><tr><td></td><td></td><td>卖方规格书</td><td>卖方规格书</td></tr></table></body></html>  \n\n<html><body><table><tr><td>使用范围</td><td>涂层</td><td>涂层系统</td><td>干膜厚度/μm（mil）</td><td>目标干膜厚度/μm（mil）</td></tr><tr><td rowspan=\"4\">CM-6 甲板和地板—重载和直升机</td><td>1</td><td>环氧底漆</td><td>200~250(8~10)</td><td>250(10)</td></tr><tr><td>2</td><td>环氧防滑涂层</td><td>200~250(8~10)</td><td>250(10)</td></tr><tr><td>3</td><td>聚氨酯安全标记</td><td>50~75(2～3)</td><td>75(3)</td></tr><tr><td>1</td><td>厚浆型环氧防滑涂层</td><td>卖方规格书</td><td>卖方规格书</td></tr></table></body></html>\n\n$\\textcircled{1}$ 对于潮湿管系，可以用水下固化环氧涂料进行刷涂，也可使用至少 $\\mathtt{l.1m m}$ （ $45\\mathrm{mil})$ 厚度的石蜡或矿脂油缠绕带。$\\textcircled{2}$ 湿固化聚氨酯在其固化过程中需要湿气和二氧化碳反应。如果太厚，会产生很多气泡。必须严格遵循干膜厚度的要求。$\\textcircled{3}$ 这是一种新型的耐高温涂料，用于绝热层下防腐维修。该涂层含有硅，但不属于硅树脂涂料。$\\textcircled{4}$ 防滑砂在施工前要和液体涂料相混合，以保证对砂粒的良好润湿性。细砂可用于环氧防滑涂层的施工。$\\textcircled{5}$ 干膜厚度应该在防滑砂加入前进行计算。  \n\n海洋工程上要用到大量的不同型号的不锈钢，为了防止缝隙腐蚀和应力腐蚀破裂，不锈钢也需要用涂料来进行保护。典型的不锈钢表面保护用涂料系统见表3-4-69。  \n\n表3-4-69不锈钢表面保护用涂料系统  \n\n\n<html><body><table><tr><td>使用范围</td><td>涂层</td><td>涂层系统</td><td>干膜厚度/μm(mil)</td><td>目标干膜厚度/μm（mil）</td></tr><tr><td>SM-1 水冷凝管，仅用于维修①</td><td>1</td><td>水下固化涂料</td><td>375~750(15~30)</td><td>500(20)</td></tr><tr><td>SN-2/SM-2 大气区 50~120℃（—58~248F)</td><td>1 2</td><td>环氧底漆 聚氨酯</td><td>150~200(6~8) 50~75(2~3)</td><td>200(8) 75(3)</td></tr><tr><td rowspan=\"4\">SN-3/SM-3 大气区 120~150°℃(248~302°F)</td><td>1</td><td>酚醛环氧</td><td>100~125(4~5)</td><td>125(5)</td></tr><tr><td>2</td><td>酚醛环氧</td><td>100~125(4~5)</td><td>125(5)</td></tr><tr><td>1</td><td>厚浆型硅基涂料</td><td>100~200(4~8)</td><td>150(6)</td></tr><tr><td>2</td><td>厚浆型硅基涂料</td><td>100~200(4~8)</td><td>150(6)</td></tr><tr><td rowspan=\"5\">SN-4/SM-4 大气区 150~450℃(302~842F)</td><td>1</td><td>有机硅</td><td>25~50(1~2)</td><td>50(2)</td></tr><tr><td>2</td><td>有机硅</td><td>25～50(1~2)</td><td>50(2)</td></tr><tr><td>1</td><td>厚浆型硅基涂料</td><td>100~200(4~8)</td><td>150(6)</td></tr><tr><td>2</td><td>厚浆型硅基涂料</td><td>100~200(4~8)</td><td>150(6)</td></tr><tr><td>1</td><td>金属热喷铝涂层（TSA）</td><td>50~100(2~4)</td><td>75(3)</td></tr></table></body></html>  \n\n续表  \n表3-4-70非铁金属表面的典型大气区涂料系统（新建和维修）  \n\n\n<html><body><table><tr><td>使用范围</td><td>涂层</td><td>涂层系统</td><td>干膜厚度/μm(mil)</td><td>目标干膜厚度/μm(mil)</td></tr><tr><td>ON-1/OM-1 铝质直升机甲板——防滑</td><td>1 2 3</td><td>环氧底漆 环氧防滑涂层 聚氨酯 (>0℃[32F])或者防滑瓦系统 (<0℃[32F])</td><td>125~175(5~7) 150~200(6~8) 50~75(2~3)</td><td>125(5) 150(6) 75(3)</td></tr><tr><td>热浸镀锌涂层 大气区 50~120℃（—58~248F)</td><td>1 2</td><td>环氧底漆 聚氨酯面漆</td><td>150~200(6~8) 50~75(2~3)</td><td>150(6) 75(3)</td></tr></table></body></html>\n\n$\\textcircled{1}$ 对于潮湿管系，可以用水下固化环氧涂料进行刷涂，也可使用至少 $1.1\\mathrm{mm}$ $45\\mathrm{mil})$ ）厚度的石蜡或矿脂油缠绕带。表3-4-70为用于非铁金属表面的典型大气区涂料系统。  \n$\\textcircled{1}$ 铝质甲板变形相对较大，需要使用很柔韧的涂料系统，特别是在寒冷气候下，可以使用更为柔韧的防滑瓦系统。  \n\n(2）飞溅区保护涂料系统推荐的飞溅区涂料系统见表3-4-71（新建）和表3-4-72（维修)。环氧涂料通常采用玻璃鳞片来增强其屏蔽性能和机械强度，聚氨酯面漆因其耐水性不佳因此不用于飞溅区。采用硫化氯丁橡胶涂层时，厚度范围在 $6\\sim13\\mathrm{mm}$ 0 $(0.25\\sim0.50\\mathrm{in})$ 中通常在车间内进行涂覆。金属热喷铝涂层（TSA）厚度在 $200{\\sim}250\\mu\\mathrm{m}$ 1 $(8\\mathrm{\\sim}10\\mathrm{mil})$ ，用环氧涂料进行封闭，为了防止热循环的冲击，TSA的厚度要控制在较窄的范围内。  \n\n表3-4-71 典型的飞滩区碳钢表面新建涂料系统  \n\n\n<html><body><table><tr><td>使用范围</td><td>涂层</td><td>涂料系统</td><td>干膜厚度/μm（mil) (除非另有说明)</td><td>目标干膜厚度 /μm(mil)</td></tr><tr><td rowspan=\"6\">CN-7 飞溅区 <60℃(140F)</td><td>1 2</td><td>环氧玻璃鳞片涂层 环氧玻璃鳞片涂层</td><td>450~550(18~22) 450~550(18~22)</td><td>500(20) 500(20)</td></tr><tr><td>1</td><td>热喷铝涂层</td><td>200~250(8~10)</td><td>250(10)</td></tr><tr><td>2</td><td>稀释的封闭层(环氧)</td><td>不计人干膜厚度</td><td>无额外干膜厚度</td></tr><tr><td>3</td><td>封闭层(环氧)</td><td>不计人干膜厚度</td><td>无额外干膜厚度</td></tr><tr><td>1</td><td>底漆</td><td>25~50(1~2)</td><td>25(1)</td></tr><tr><td>2</td><td>黏结剂</td><td>25~50(1~2)</td><td>25(1)</td></tr><tr><td rowspan=\"6\">CN-8 飞溅区 >70℃(158F)&<100℃(212F)</td><td>3</td><td>氯丁橡胶</td><td>6～13mm(0.25~0.50in)</td><td>最终用户规格书</td></tr><tr><td>1</td><td>底漆</td><td>25~50(1~2)</td><td>25(1)</td></tr><tr><td>2 3</td><td>黏结剂</td><td>25~50(1~2)</td><td>25(1)</td></tr><tr><td></td><td>氯丁橡胶</td><td>6～13mm(0.25~0.50in)</td><td>最终用户规格书</td></tr><tr><td>1</td><td>底漆</td><td>25~50(1~2)</td><td>25(1)</td></tr><tr><td>2</td><td>黏结剂</td><td>25~50(1~2)</td><td></td></tr><tr><td>飞溅区 >100℃(212F)&<130℃(266F)</td><td>3</td><td>EPDM橡胶</td><td>6~13mm(0.25~0.50in)</td><td>25(1) 最终用户规格书</td></tr></table></body></html>\n\n$\\textcircled{1}$ 平均表面粗糙度至少 $75\\mu\\mathrm{m}$ （ $\\mathrm{\\sf3mil})$ $\\textcircled{2}$ 允许稀释的封闭层在施工下道涂层干燥 $>30\\mathrm{min}$ ，不计人干膜厚度。$\\textcircled{3}$ 使用温度 $570^{\\circ}C$ 0 $\\mathbf{\\dot{\\tau}}_{\\mathrm{158\"F}},$ ，氯丁橡胶可仅使用炭黑颜料，具有更好的耐热性。$\\textcircled{4}$ 乙烯丙烯二烯（烃）弹性体（ethylene propylene diene elastomer）。  \n\n由于飞溅区在低潮位时才能进行维修保养，时间非常短，适合使用单道涂层。由于表面经常是潮湿的，涂料系统须适用于这种潮湿表面。由于飞溅区维修相当困难，因此除了液体环氧涂料外，也有一些商业化应用的非涂料系统的实践应用。  \n\n表3-4-72 典型的飞溅区碳钢表面维修涂料系统  \n\n\n<html><body><table><tr><td>使用范围</td><td>涂层</td><td>涂层系统</td><td>干膜厚度/μm(mil)</td><td>目标干膜厚度/μm（mil）</td></tr><tr><td rowspan=\"6\">CM-7飞溅区 <60℃(140F)</td><td>1</td><td>低表面处理环氧涂层</td><td>300～2000(12~80)</td><td>卖方规格书</td></tr><tr><td>1</td><td>环氧底漆</td><td>125~175(5~7)</td><td>125(5)</td></tr><tr><td>2</td><td>环氧玻璃鳞片</td><td>200~500(8~20)</td><td>375(15)</td></tr><tr><td>1 1</td><td>环氧玻璃鳞片 水下固化环氧</td><td>450~550(18~22)</td><td>500(20)</td></tr><tr><td>2</td><td>底漆</td><td>卖方规格书</td><td>卖方规格书</td></tr><tr><td>3</td><td>两层玻璃纤维外保护套</td><td></td><td></td></tr></table></body></html>\n\n$\\textcircled{1}$ 平均表面粗糙度至少 $75\\mu\\mathrm m$ $\\mathrm{\\bar{3}m i l})$ $\\textcircled{2}$ 卖方对其产品有特定的推荐干膜厚度。  \n\n(3）全浸区保护涂料系统典型的外部全浸区防腐系统同时使用牺牲阳极和防护涂料，涂料系统可有效减少牺牲阳极的数量或质量。用于外部全浸区的保护涂料系统见表3-4-73（新建）和表3-4-74（维修）。  \n\n表3-4-73典型的外部全浸区新建结构碳钢表面防护涂料系统  \n\n\n<html><body><table><tr><td>使用范围</td><td>涂层</td><td>涂层系统</td><td>干膜厚度/μm(mil)</td><td>目标干膜厚度/μm（mil）</td></tr><tr><td rowspan=\"4\">CN-10 外部浸没区 <60℃(140 F)</td><td>1</td><td>高固体分环氧</td><td>150~200(6~8)</td><td>175(7)</td></tr><tr><td>2</td><td>高固体分环氧</td><td>150~200(6~8)</td><td>175(7)</td></tr><tr><td>1</td><td>金属热喷铝涂层</td><td>250~375(0~15)</td><td>300(12)</td></tr><tr><td>2 3</td><td>稀释的封闭层(环氧) 封闭层(环氧)</td><td>不计人干膜厚度 不计人干膜厚度</td><td>无额外干膜厚度 无额外干膜厚度</td></tr></table></body></html>\n\n$\\textcircled{1}$ 通常安装牺牲阳极与保护涂料系统一起使用。$\\textcircled{2}$ 在施涂下道封闭层前，允许稀释的封闭层干燥 $>30\\mathrm{min}$ 。封闭层不应增加现有金属热喷铝涂层的厚度。  \n\n表3-4-74典型的全浸区碳钢表面维修涂料系统  \n\n\n<html><body><table><tr><td>使用范围</td><td>涂层</td><td>涂层系统</td><td>干膜厚度/μm(mil)</td><td>目标干膜厚度/μm(mil)</td></tr><tr><td>CM-8 外部浸没区 <60℃(140 F)</td><td>1</td><td>水下固化环氧①</td><td>500~1000(20~40)</td><td>卖方规格书</td></tr></table></body></html>\n\n$\\textcircled{1}$ 水下固化环氧涂料相当的困难，阴极保护系统（CP）是很好的可选方案。  \n\n(4）压载水舱涂料系统压载水舱是黑暗封闭的空间，无溶剂或高固体分环氧涂料更适合于这种环境下的应用，并使用浅色面漆系统以方便目测检查。多道涂层系统须用同一配方技术，仅颜色不同，这样可以减少因溶胀收缩而导致的层间附着力风险。典型的新建和维修压载水舱涂料系统见表3-4-75和表3-4-76。对于环氧涂料系统，总干膜厚度在375～500μm$(15\\sim20\\mathrm{mil})$ ，多道涂（一般两道以上）具有更好的漆膜完整性和更少的漏涂点。施工两道预涂层可以在焊缝和尖角处达到更好的漆膜覆盖性。  \n\n深水海洋结构的空舱在使用过程中可能会成为海水压载舱，因此最好使用与压载水舱同样的涂料系统。  \n\n表3-4-75 典型的新建结构碳钢表面压载水舱涂料系统  \n\n\n<html><body><table><tr><td>使用范围</td><td>涂 层</td><td>涂层系统</td><td>干膜厚度/μm（mil）</td><td>目标干膜厚度/μm(mil)</td></tr><tr><td>CN-11 压载水舱 <60℃(140 F)</td><td>1 2 3</td><td>高固体分环氧 预涂 高固体分环氧</td><td>125~175(5~7) 125~175(5~7) /</td><td>125(3) 125(3)</td></tr></table></body></html>\n\n$\\textcircled{1}$ 压载水舱是黑暗的，浅色面漆帮助易于目测检查。  \n\n表3-4-76 典型的碳钢表面压载水舱维修涂料系统  \n\n\n<html><body><table><tr><td>使用范围</td><td>涂层</td><td>涂层系统</td><td>干膜厚度/μm(mil)</td><td>目标干膜厚度/μm（mil)</td></tr><tr><td>CM-9</td><td>1</td><td>高固体分环氧</td><td>200~250(8~10)</td><td>200(8)</td></tr><tr><td>压载水舱</td><td>2</td><td>预涂</td><td>一</td><td>一</td></tr><tr><td><60℃(140 F)</td><td>3</td><td>高固体分环氧</td><td>200~250(8~10)</td><td>200(8)</td></tr></table></body></html>\n\n$\\textcircled{1}$ 压载水舱是黑暗的，浅色面漆帮助易于目测检查。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 336,
+        "chunk": "# 八、海洋工程涂装质量要求  \n\n有关海洋工程的涂装施工和质量检查，在NORSOKM501中有相应的说明，在石油公司的内部质量控制文件中对此也会有详细规定。",
+        "category": " Introduction"
+    },
+    {
+        "id": 337,
+        "chunk": "# 1.涂装公司和人员的资质  \n\n按NORSOK标准履行防腐蚀涂装工作的涂装公司，应该证明其具有在组织、计划和在  \n\n类似规模与复杂的项目方面的经验。  \n\n涂装操作者，如喷砂工、涂漆工等，应有相关的技术资质。对健康和安全危害、使用保护用具、涂料材料、混合和稀释、罐藏寿命，表面要求等，具备各方面的相关知识。  \n\n金属喷涂工，按NORSOKM501标准，在工作开始前，操作者应该通过表3-4-77中预先资质考核。  \n\n表3-4-77 金属喷涂工的资质考核  \n\n\n<html><body><table><tr><td>考核</td><td>接受标准</td></tr><tr><td>涂层的目测检查，所有的试板要在不使用 放大镜和使用10×放大镜的情况下进行 检验</td><td>热喷涂施工工具符合DIN32521的规定。每道涂层应该均匀施工于整 个表面。涂层多道施工，喷涂行枪之间要有搭幅 涂层要附着牢固，喷涂后表面要均匀没有块状、松散的飞溅滴落金属、气</td></tr><tr><td>膜厚和外形检测（见注2）</td><td>泡、灰分、其他缺陷和局部的漏涂 在所有的样本表面，最小200μm（ISO19840)</td></tr><tr><td>附着力（见注3）ISO4624，所有试板都要 被测试。样品的检测将在破裂后判断其失效 原因</td><td>单点测量都要大于9.0MPa，如果在胶黏剂/涂层界面处失效，需要重新 检测</td></tr></table></body></html>\n\n注；1.概要：检测材料必须是生产中可比较级别材料。涂层的施工要按照本NORSOK标准和建议的程序进行。2.样品的形状测试：一个 $\\mathbf{1500mm}$ 长的T、I或H型钢，高约 $\\bar{7}50\\mathrm{mm}$ ，厚 $\\mathrm{13mm}$ 。其他样品切割成长 $1500\\mathrm{mm}$ ，真径 $\\mathsf{50m m}$ 的管件。3.附着力测试样品：准备5个样品用于附着力测试，按ISO4624进行，板厚至少 $5\\pi m$  \n\n防火保护层的操作者，包括泵机的操作者，都要经过涂料生产商的资质培训和考核程序。在焊钉焊接前，电焊工以及相关焊接程序也要按涂料生产商的程序进行资质考核。如果操作者或焊钉焊接人员没有在12个月内进行过相关材料的工作，在工作开始前须证明其接受相关培训。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 338,
+        "chunk": "# 2.监理、领班和质检人员的资质  \n\n涂装施工后的涂层系统是否符合规格书的要求，须通过涂层系统的检验来证实。海洋工程涂装检验员的要求必须是FROSIO或NACE持证检验员。在涂装中检验钢构件表面温度与露点的温差，喷涂设备和压力，喷涂技术，涂料使用程序，每一层的干膜厚度，固化和干燥时间，最终涂层质量。  \n\n涉及防火保护的监理、领班或QC人员，根据防火材料厂商的程序，要接受额外的培训或认证。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 339,
+        "chunk": "# 3.表面处理  \n\n(1）预喷砂处理锐边、棱条、角和焊缝等要倒圆或打磨平滑 $(R\\mathbf{\\equiv}2\\mathbf{mm})$ 。  \n\n硬质表面层，比如火工切割表面等应该在喷射清理前打磨去除。  \n\n喷砂处理前，表面必须没有任何杂质，比如焊渣、残余物、裂片、油脂和盐分等，所有的表面应该用清洁的淡冲洗。  \n\n喷砂清理操作前，所有油脂污染应该按SSPCSP1去除。  \n\n任何主要表面缺陷，特别是表面重皮或疤痕等对涂料系统有害的缺陷，应该去除。  \n\n所有焊缝应该被检查，如果有必要，在最终喷砂前进行修补。表面气孔、空洞等，应该打磨或电焊修补。  \n\n(2）喷射清理 喷射用磨料要干燥，清洁，不含对涂料性能有害的杂质。  \n\n喷射用磨料的颗粒大小要能够产生符合涂料系统的表面处理粗糙度要求 (锚形轮廓)。表面轮廓根据ISO8503评定等级。喷射用磨料要采用棱角砂。  \n\n不锈钢材料、镀锌件或铝材表面表面要进行有机涂层保护时，采用无氯非金属材料，如采有氧化铝磨料进行喷砂处理，表面粗糙度控制在 $R_{\\Bar{z}}$ 为 $20\\sim30\\mu\\mathrm{m}$ 。镀锌件表面喷砂时不能破坏其锌层。用于不锈钢喷射的磨料其电导率不能高于 $150\\mu\\mathrm{S}/\\mathrm{cm}$ 费  \n\n喷射清理后的表面的清洁度根据ISO8501-1进行评估。  \n\n(3）喷射后最终表面状况喷射清洁后待涂漆表面，要满足规格书的要求。  \n\n待涂漆表面要清洁、干燥，没有油脂，达到了规定的粗糙度和清洁，直至第一道涂层施工。  \n\n灰尘、喷射用磨料等，喷射清理后要清除掉，其粒径和数量不能超过ISO8502-3中规定的2级。  \n\n喷射表面可溶性杂质的可接受最大值按ISO8502-6用蒸馏水取样，按照ISO8502-9测量其电导率。NORSOKM501规定相应的NaCI含量不得高于 $20\\mathrm{mg/m^{2}}$ 。NACE SP0108的要求见表3-4-78。  \n\n表3-4-78NACESP0108可溶性氯离子总含量最高限值  \n\n\n<html><body><table><tr><td>涂层使用范围</td><td>新建</td><td>维修</td></tr><tr><td>飞溅区，外部浸没区，压载水舱/（mg/m²）</td><td>20</td><td>20</td></tr><tr><td>大气区/（mg/m²）</td><td>20</td><td>50</td></tr><tr><td>不锈钢/（mg/m²）</td><td>20</td><td>20</td></tr></table></body></html>  \n\n碳钢表面，要求喷砂到 $\\mathsf{S a2.5}$ 。如果有必要，还要检查氧化皮的残存量，可以使用放大镜检查，或者采用ASTMA3807.2条的硫酸铜检测法进行化学检测。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 340,
+        "chunk": "# 4.质量检测和检查要点  \n\n海洋工程在防腐涂装过程中的质量检测和检查要点，以及可接受标准，可以参考NOR-SOKM501中的规定，见表3-4-79。  \n\n表3-4-79NORSOKM501的测试和检查要点  \n\n\n<html><body><table><tr><td>试验类型</td><td>方法</td><td>频率</td><td>可接受标准</td><td>结论</td></tr><tr><td>环境条件</td><td>环境和钢板温度 相对湿度 露点</td><td>每个班次开始前 每班次至少两次</td><td>根据规定要求</td><td>不能进行喷砂或 涂漆</td></tr><tr><td>目测检查</td><td>目测检查锐边、焊接飞 溅、锈蚀等通讯等</td><td>100%所有表面</td><td>没有缺陷，见规定 要求</td><td>缺陷修正</td></tr><tr><td>清理程度</td><td>a. ISO 8501-1 b. ISO 8502-3</td><td>a.100%目测检查所 有表面 b.局部检查</td><td>a.根据规定要求 b.最大数量和大小 为2级</td><td>a.重新喷砂 b.重新清理测试， 直到可以接受</td></tr><tr><td>盐分测试</td><td>ISO 8502-6 ISO 8502-9</td><td>局部检查</td><td>最大电导率相当于 NaCl:20mg/m²</td><td>用饮用水重复清洗， 重新测试直到可以 接受</td></tr><tr><td>粗糙度</td><td>比较样板或铁笔测试 (ISO 8503)</td><td>每一部位，或每10m² 一次</td><td>根据规定</td><td>重新喷砂</td></tr><tr><td>固化试验（硅 酸锌)</td><td>ASTM D4752</td><td>每一部位，或每 100m²一次</td><td>4~5级</td><td>固化认可</td></tr><tr><td>涂层目测检查</td><td>目测判断固化、污染、溶 剂残留、针孔/起泡、流挂 和表面缺陷</td><td>每一道涂层的100% 表面</td><td>根据规定要求</td><td>缺陷修正</td></tr><tr><td>漏涂点检测</td><td>NACE RP0188</td><td>按涂料系统规格书</td><td>无漏涂点</td><td>修正，重新测试</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>试验类型</td><td>方法</td><td>频率</td><td>可接受标准</td><td>结论</td></tr><tr><td>漆膜厚度</td><td>ISO 19840 光滑表面校正</td><td>ISO 19840</td><td>ISO19840和涂料系 统产品数据手册</td><td>修正、额外涂层或适 当重涂</td></tr><tr><td>附着力</td><td>ISO 4624 使用自动中心拉力设 备，涂层完全固化后进行</td><td>局部检查</td><td>见注释</td><td>涂层拒收</td></tr></table></body></html>  \n\n注：1．对于涂料系统No.2A，在CPT过程中，附着力必须至少 $\\mathfrak{g}_{\\star}\\mathbb{o}\\mathbf{M}\\mathbf{Pa};$ ；在生产过程中，单点附着力测试必须达  \n到至少 $\\boldsymbol{{\\bar{7}}}.\\boldsymbol{0}\\mathbf{M}\\mathbf{\\bar{Pa}}$ 2.对于涂料系统No.2B，金属涂层在CPT过程中，附着力必须至少 $\\bar{\\mathcal{I}},\\bar{\\Theta}\\mathrm{MPa}$ ；完整涂层系统No.2B附着力测试内  \n聚力须达到至少 $\\mathsf{5.0M P a}$ 鼎3.对于涂料系统No.3A、3C、3D、3E、3F和3G，最大 $30\\%$ 的 CPT值减少可以接受。绝对值至少 $\\mathsf{\\Pi}_{5\\mathrm{{MPa}}}$ 费4.防火保护上的喷涂，可接受内聚力读数减少为CPT值的最大 $50\\%$ 。水泥基产品绝对最小值至少 $\\pmb{\\mathcal{\\hat{Z}}},\\emptyset\\mathbf{M}\\mathbf{P\\Bar{a}}$ ，环氧基  \n产品 ${\\mathsf{5}}\\circ{\\mathsf{O M P a}}$ 中5.剩下的涂料系统，平均附着力值减少为CPT附着力的 $50\\%$ ，生产过程中涂层的绝对附着力值最小 $\\boldsymbol{\\mathsf{5}},\\boldsymbol{\\mathsf{O M P a}}$ 6",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 341,
+        "chunk": "# 参考文献  \n\n[1」注国平，船舶深科与葆装技不，第乙版，北京：化学上业出版社，Z006.  \n[2]Jotun Shop Primer Application Handbook （佐敦内部资料).  \n[3］陆伯岑，欧伯兴．水相法氯化橡胶的性能试验，第三届国际防腐及防腐蚀涂料技术研讨会，珠海：常州涂料研究院，2005.5.  \n[4]GB/T6822—2008．船体防污防锈漆体系.  \n[5] 徐国强，黄运成，新型无锡自抛光防污漆，涂料工业，2000，（10）.  \n[6] 王健，环境保护与船舶防污漆技术，国际船艇，2002，（9）.  \n[7］李慧娟，王国建，船舶防污涂料的研究与发展，上海涂料，2005，（1).  \n[8] WangJian，美国防腐工程师协会（NACE）国际船舶涂料论坛．上海，2007，11.  \n[9]金晓鸿，材料开发与应用，2006，（4).  \n[10] Yebra D M. Progress in Organic Coatings， 2004，（5).  \n[11] A. M. Berendsen. Marine painting manual. UK： Graham $8$ Trotman， 1989.  \n[12] GB/T6745—2008.《船壳漆》通用技术条件.  \n[13] 涂料工艺编委会．涂料工艺．第3版．北京：化学工业出版社，1997.  \n[14] 徐国强、李荣俊．重防腐蚀聚硅氧烷涂料．涂料工业，2004，（8).  \n[15] GB/T9261—2008.《甲板漆》通用技术条件.  \n[16] 张学卿等，防滑涂料的发展状况．现代涂料与涂装，2002.（3）.  \n[17] 朱万章．摩擦与防滑涂料．涂料工业，2002，（8).  \n[18] 虞兆年．防腐蚀涂料和涂装．北京：化学工业出版社，2002.  \n[19] 王健，刘会成，刘新．防腐蚀涂料和涂装．北京：化学工业出版社，2006.  \n[20] 战凤昌．专用涂料．北京：化学工业出版社，1996.  \n[21］刘登良，海洋涂料与涂装技术，北京：化学工业出版社，2002.  \n[22] 王学峰等．集装箱管理与装箱工艺．上海：同济大学出版社，2006.  \n[23]Marc Levinson.The Box:How the Shipping Container Made the World Smaller and World Economy Bigger.Prin-ceton: Princeton University Press， 2006.  \n[24］周龙祥，王绍忠．埋岛油田的腐蚀现状与防腐蚀技术，黄渤海海洋，2001，19（3).  \n[25]余越泉．导管架平台防腐技术研究．中国海洋平台，2001，16（4).  \n[26]刘大扬，李文军，魏开金，钢在南海榆林海域暴露16年的腐蚀，舰船科学技术，2001，（2).  \n[27]郭公玉，张经磊，侯保荣，杨芳英，钢在中国北部海区海泥中的腐蚀，电化学，2001，7（4).  \n[28]孔爱民，富锌涂料在海洋平台中的应用分析和选择．腐蚀与防护，2007，27（9).  \n[29］蒋官澄，黄春，张国荣，海上油气设施腐蚀与防护，北京：中国石油大学出版社，2006.  \n[30]刘新，防腐蚀涂料与涂装应用，北京：化学工业出版社，2008.  \n[31]Olaf Doble.Coating Selectionin the Norwegian Offshore Industry:Where，What and Why?JPCL，2004，（4).  \n[32]MikeMitchellJ.Alookat work intheU.Son Specifications forCoatings forOffhore Structures.JPCL2005，（3).  \n\n![](images/82c6063ded119048e2c338d1acc93854586f4909311ffc784c561242eea438ca.jpg)",
+        "category": " References"
+    },
+    {
+        "id": 342,
+        "chunk": "# 1.预涂卷材的定义  \n\n预涂卷材是在成卷的金属薄板上涂覆涂料或层压上塑料薄膜后，以成卷或单张形式出售的有机材料/金属复合板材，也称为有机涂层钢板、预涂层钢板、彩色涂层钢板、塑料复合钢板等。用户可以直接将其加工成型，做成各种产品和部件，无需再进行涂装工序，从而大大简化了金属薄板制品总的生产工艺。  \n\n预涂卷材采用集中生产，省去了产品制作过程中的复杂的涂装工序，因此大大降低了各类制造业成本，通过采用预涂技术，薄板制品的成本可以降低 $5\\%\\sim10\\%$ ，节省能源约15%～20%，尤其是节约了薄板制品的预处理和涂装设备的大量投资，并且改善了加工企业的环境和工人的劳动条件。",
+        "category": " Introduction"
+    },
+    {
+        "id": 343,
+        "chunk": "# 2.预涂卷材的基板  \n\n预涂卷材用的基板主要有冷轧钢板、电镀锌钢板、热镀锌钢板、合金化热镀锌钢板、热镀锌-铝钢板、热镀铝-锌钢板、热镀铝钢板、铝板和不锈钢板等，其中前三种是最常用的。热镀锌钢板根据锌花种类还可以细分为大锌花板、小锌花板和无锌花板。通常根据用途可采用不同的基板类型，对用于腐蚀性较强的室外环境的卷材，一般采用有锌花的热镀锌钢板；对用于室内、腐蚀性要求较低，但对外观要求较高，如家电、装饰用卷材，一般采用冷轧钢板、电镀锌钢板或无锌花热镀锌钢板。",
+        "category": " Introduction"
+    },
+    {
+        "id": 344,
+        "chunk": "# 3.预涂卷材的组成  \n\n预涂卷材是由基板（包括镀层，例如镀锌层)、预处理层（磷化膜、铬化膜及钝化膜)、涂层和保护层（保护膜或蜡层等）组成。正面涂层一般由底漆和面漆组成，对有些要求较低的应用，也有采用单涂层体系，而对装饰性要求较高的应用，也有采用三涂层体系的；正面也可以采用覆膜技术，如聚氯乙烯（PVC）膜和聚对苯二甲酸乙二醇酯（PET）膜。背面一般为单涂层，对要求较高的应用，也可采用底漆和面漆组成的二涂层体系。预涂卷材组成如图3-5-1所示。",
+        "category": " Introduction"
+    },
+    {
+        "id": 345,
+        "chunk": "# 4.预涂卷材的历史  \n\n预涂卷材技术起源于美国，19世纪末和20世纪初建筑业的发展推动了钢铁在建筑及钢结构中的应用，钢铁需要涂装以提供装饰和防腐性，从而推动了预涂卷材技术的开发。第一条连续预涂卷材生产线1936年在美国建立，是用醇酸树脂漆涂装厚0.3mm、宽50mm的钢带，其线速 $12\\mathrm{m/min}$ ，生产1t预涂钢卷需要约12h。用于制百叶窗板和挡风墙，以取代木制品。  \n\n![](images/f86832a50c1e6ce9079748af1cc361c075e6468183f6c08776955038798b3eb6.jpg)  \n图3-5-1 典型的预涂卷材组成示意图  \n\n20世纪50年代，预涂卷材在美国获得快速发展，大量应用于建筑业和家电产品。20世纪60年代，卷材生产线线速已可以达到 $75\\mathrm{m/min}$ ，预涂钢带宽度可达到 $1.50\\mathrm{m}$ 以上。到20世纪末，美国已有约180条预涂卷材生产线（包括卷钢和卷铝)，最高线速可达到$250\\mathrm{m/min}$ ，年生产420万吨预涂卷材。  \n\n20世纪60年代，预涂卷材技术引人欧洲，到2005年，欧洲的预涂卷材产量已达到近14亿平方米。  \n\n中国在20世纪60年代初开始预涂卷材的研制工作，主要是聚氯乙烯（PVC）覆膜板；进人20世纪80年代，中国的预涂卷材的研制和技术开发进人了一个新的发展阶段。1983年，国家科委将彩色涂层钢板列为国家“六五”科技攻关项目，由当时的冶金工业部、化学工业部和轻工业部组织所属有关单位联合开发，在自主开发的同时，又开始陆续引进国外先进的生产技术和设备。预涂卷材可以广泛应用于建筑、家电、家具、汽车制造等行业，近年来，我国经济持续快速增长，带动了建筑、家电、家具和汽车制造等行业的快速发展，这为彩钢板提供了广阔的市场和应用空间，使我国的彩钢板生产进人高速发展期，从而推动了彩钢板涂料的快速发展。到2005年，中国的彩涂线数量已达到了约200条，年生产预涂卷材约300万吨。如图3-5-2所示为 $1987\\sim2005$ 年，中国预涂卷材生产线数量和产量示意图。据全国涂料工业信息中心统计，2006年，中国卷材涂料产量已达到了约10万吨。  \n\n![](images/301ae5e12597d7f89c348dec1245b274422ccf0bf5408f8473f883f92c4ace34.jpg)  \n图3-5-2近年来中国预涂卷材生产线数量和产量示意图",
+        "category": " Introduction"
+    },
+    {
+        "id": 346,
+        "chunk": "# 5.预涂卷材的特点  \n\n预涂卷材得以高速发展，就是由于它具有良好的经济效益，能适应社会经济发展的需要。它既具有有机涂料的良好的着色性、防腐性和装饰性，又具有钢板的高强度和易加工性，是一种高效、环保、节能钢材，是钢铁工业的一种深加工产品。同时它也是涂料涂装领域的一项巨大革新，实现了从传统的先成型加工、后涂装向先涂装、后成型加工的转变。它的主要特点如下。  \n\n$\\textcircled{1}$ 预涂卷材涂装质量高，通过将制成品涂装变成原料基板的连续涂装，既便于表面处理及涂装质量的控制，又不存在易产生棱边死角的涂装缺陷，从而可以得到最佳的涂装质量。  \n\n$\\textcircled{2}$ 预涂卷材涂装效率高，现在，国内建筑用预涂卷材涂装线线速一般为$40{\\sim}200\\mathrm{m/min}$ ，家电用预涂卷材涂装线线速一般为 $20{\\sim}40\\mathrm{m/min}$ ，而国外最高线速已接近$250\\mathrm{m/min}$ ，生产板宽达到了 $1.8\\mathrm{m}$ 以上，一条生产线的年生产能力就可达到50万吨以上。  \n\n$\\textcircled{3}$ 预涂卷材涂装能耗低，具有节能的特点，涂膜固化时，涂装好的平板在烘炉中通过，炉容利用率比成品涂装高，并且烘烤时挥发的溶剂能收集并引入燃烧器烧，将热能再利用，总能耗只有成品涂装的 $1/5{\\sim}1/6$ 中  \n\n$\\textcircled{4}$ 采用预涂卷材技术，对环境污染少，符合环保要求，烘烤时挥发的溶剂通过集中烧处理后排放，大大减少有机溶剂向大气中的释放。例如广州彩色带钢厂从美国万宾（MERBAN）公司引进的彩色涂层钢板生产线，在固化和废气处理方面采用了先进技术；涂层固化采用高频感应加热的方式，热量由内向外传递，有利于溶剂挥发。烘炉升温快，加热时间短；机组废气中有机溶剂的回收装置是由与感应固化炉配套的液氮贮罐、三级热交换装置组成，通过这种技术，可以回收固化炉废气中所含有机溶剂的 $99\\%$ 左右。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 347,
+        "chunk": "# 6.预涂卷材的用途  \n\n预涂卷材发展到现在，其应用已经从最初的建筑业拓展到现在的电器、运输、家具和办公用品等诸多领域。  \n\n在建筑业可用作工业厂房、公用设施及住宅的屋顶、外墙和内部隔墙。由于其重量轻（表3-5-1)，对相同面积的屋顶或墙面采用预涂卷材构件比用混凝土构件可减少 $80\\%\\sim95\\%$ 的运输和吊装量；同时可使房架、支柱及基础材料用量及工程量都相应降低。  \n\n表3-5-1预涂卷材构件与混凝土构件重量比较  \n\n\n<html><body><table><tr><td>构件</td><td>材料</td><td>重量/（kg/m²）</td></tr><tr><td>普通屋顶板</td><td>预涂卷材 预应力混凝土板、水泥砂浆找平层十二毡二油绿豆砂</td><td>11 195~200</td></tr><tr><td>隔热屋顶板</td><td>预涂卷材、100矿渣棉 隔热性相当的轻质混凝土</td><td>30 150</td></tr><tr><td>隔热墙板</td><td>双层预涂卷材夹隔热材料 隔热性相当的轻质混凝土 隔热性相当的普通混凝土</td><td>25~40 150 350</td></tr><tr><td>隔热悬墙</td><td>预涂卷材、矿渣棉隔热层、纤维板或石膏板 隔热性相当的混凝土或砖墙</td><td>35~40 350~500</td></tr></table></body></html>  \n\n在电器产品中的应用也愈来愈宽。例如冰箱面板和侧板；视听产品如影碟机、功放、刻录机、数字电视机顶盒等；空调外壳；洗衣机外壳；取暖器、热水器外壳；厨房用具如微波炉等。  \n\n在运输领域可用作汽车车身板、引擎罩、可用螺栓固定的汽车内用部件和路标等。  \n\n用于家具和办公用品，可制作成各种隔断、橱柜、灯具外壳、窗帘杆、晾衣架等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 348,
+        "chunk": "# 7.预涂卷材行业协会和组织  \n\n预涂卷材行业最知名的国际性行业组织有美国卷涂协会（NationalCoilCoatingAssoci-ation，NCCA）和欧洲卷涂协会（European Coil Coating Association，ECCA）。  \n\nNCCA成立于1962年，总部设在克里夫兰，目前有160个成员单位，致力于提高行业的知名度，促进卷涂涂装工艺的进步，为业内人士提供信息和交流平台。  \n\nECCA成立于1967年，总部在布鲁塞尔，现有会员单位超过了200家，遍布18个国家和地区，并有很多欧洲以外的非欧盟会员，其成员包括预涂卷材生产厂、原材料（如涂料)、卷材和设备生产商。近年来，中国也有许多卷材相关企业加人了ECCA，如宝钢、上海涂料公司、江苏鸿业涂料科技产业有限公司、立邦中国有限公司、贝科工业涂料有限公司(BECKER）等。ECCA是以科学为目的的国际非盈利性组织，致力于推广预涂卷材技术的发展，其目标为：  \n\n①制定质量性能标准（包括测试方法的改进）；  \n$\\textcircled{2}$ ②提高预涂卷材技术的优势，尤其是在环保、成本及质量方面的优势；  \n③促进在工艺、产品、加工和市场方面的发展；  \n$\\textcircled{4}$ ④为专业设计与特定应用编制培训教程，增强人们对预涂卷材技术的认识；  \n$\\textcircled{5}$ 提供信息交流平台；  \n$\\textcircled{6}$ 与政府进行联系沟通；  \n?提供与其他行业协会和专业团体的联络。  \n\n中国目前虽然还未建立预涂卷材专门的行业组织，但是中国化工学会涂料涂装专业委员会和全国涂料工业信息中心从2003年以来每年都举办一次国际彩板及涂料涂装技术研讨会，收集和发表最新的预涂卷材涂料和涂装、原材料及设备等方面的文章，中国钢铁协会对这一会议也十分支持，提供了许多高质量的论文和主题演讲。该会议为中国预涂卷材行业的发展提供了一个非常好的信息交流平台。  \n\n![](images/07be13d00d07e2c0388201334f5e42828746eb35c24fe7db9a50b8d36c97ad96.jpg)  \n\n预涂卷材是以带钢等为基板进行连续生产，在生产过程中，基板表面经过各种预处理后涂覆涂料，每次涂覆后都要将涂料烘烤固化，再进行下一道涂料的施工。因此，通常以涂覆和烘烤的次数来定义机组的类型。通用的二涂二烘型连续生产线工艺如图3-5-3所示。  \n\n![](images/8cd44c58850790ff6ea2657af1840691f9cf26daf9f03e9275a80ea4fb3557e8.jpg)  \n图3-5-3二涂二烘型涂层带钢连续生产线设备布置示意 1—开卷机；2—切剪；3—人口活套；4—脱脂槽；5—化成处理槽；6—1\\*辊涂机； 7—1\\*加热炉；8,11—冷却器；9—2\\*辊涂机；10—2\\*加热炉；12—平整机； 13—出口活套；14—涂蜡机；15—切剪；16—卷取机  \n\n其工艺流程为：开卷→切头→缝合（或焊接）→去毛刺→磨刷→脱脂处理→挤干→活套→磷化处理（或表面调整）→水洗→挤干→钝化处理→挤干→第一次涂覆→第一次烘烤 $-\\cdot$ 冷却 $-\\cdot$ 吹干 $\\rightarrow$ 第二次涂覆 $\\nsim$ 第二次烘烤 $-\\cdot$ 压花或印花 $\\rightarrow$ 冷却 $\\rightarrow$ 吹干 $-\\alpha$ 涂蜡 $-$ 卷取。  \n\n对要求较高的应用，也有采用三次连续涂覆的生产线，三涂三烘型预涂生产线工艺如图3-5-4所示。  \n\n![](images/22f11421cb8b4d0e30c6fc6bce93aadaf348c0709d3f9c1c666291e8ff065824.jpg)  \n图3-5-4三涂三烘型带钢涂层连续生产线设备布置示意1一开卷机；2-活套塔；3-表面处理槽；4-1辊涂机；5-1#烘烤炉；6-2辊涂机；7-2烘烤炉；8-3\\*辊涂机；9-3烘烤炉；10-调质轧制机；11-平整辊；12—活套塔；13-涂蜡机；14-卷取机  \n\n其工艺流程为：开卷→切头→缝合（或焊接）→活套→脱脂处理→冲洗→表面磨刷→磷化处理（或表面调整）→钝化处理→干燥→初涂→1炉烘烤固化→冷却→干燥→中涂→2#炉烘烤固化→冷却→干燥→精涂→3炉烘烤固化→冷却→干燥→调质轧制→1#张力平整→2张力平整→活套→涂蜡→烘干→卷取。  \n\n在上述预涂卷材生产工艺流程中，可以发现，无论是采用二涂还是三涂，整个机组可以分为四大部分，即引人段、预处理段、涂装段和引出段。  \n\n引人段包括开卷、切头、去毛刺、缝合（或焊接）和贮料活套等设备，将原料卷材松开并连接起来，以便连续、匀速地为机组供应基板。  \n\n预处理段包括脱脂（酸洗或碱洗、冷热水漂洗）、吹干、磷化或铬化、钝化和吹干等。其作用是清洗基板并进行表面处理，以提高防腐蚀性和对上层涂膜的附着力。  \n\n涂装段是机组的核心部分，包括涂覆、烘烤、冷却、贴膜、压花或印花等工艺设备。初涂（底漆）一般采用二辊涂装，精涂机（面漆）采用二辊或三辊涂装。涂料涂覆时，涂覆辊转向和基板运行方向一致时，称为正涂式，反向时称为逆涂式。常用的辊涂方式为逆涂法，如图3-5-5所示。冷却系统是用来使前道涂层冷却，以适应下一道涂层的施工工艺要求。贴膜、压花或印花等是根据产品的特定用途而采用。涂装段产生的废气集中收集到烧炉中燃烧，产生的热量用于补充固化烘炉炉热量，实现回收利用。  \n\n![](images/cb22fbd9466e7454ef79286b1b7f4e5f81836669fd0059f2dbd00c8530def548.jpg)  \n图3-5-5 常用的辊涂方式  \n\n涂装要求较高的大多采用三辊涂装；二辊逆向涂装通常用于涂覆较薄的涂层，如底漆和涂装要求一般的素色面漆。  \n\n引出段包括加覆保护膜或涂蜡、活套、张力辊、卷取机和卸卷小车等。加覆保护膜或涂蜡是为了保护涂装好的卷材，避免表面刮伤，在家电用卷材涂装中常用加覆保护膜的方法，涂蜡常用于建筑用卷材。卷取机用于卷取成品。建筑用卷材成品通常以钢卷形式出售，而家电用卷材成品大多是以单张形式出售，生产车间中通常还要再另设裁板工序，对涂好的卷材进行开卷、裁切，根据产品用途裁切成一定的规格和尺寸。",
+        "category": " Introduction"
+    },
+    {
+        "id": 349,
+        "chunk": "# 第三节 底材的预处理  \n\n预涂卷材的基板在涂装前都要进行预处理，包括脱脂（酸洗或碱洗、冷热水漂洗）、吹干、表面调整、磷化或铬化、钝化和吹干等。其目的：一是提高其耐腐蚀性；二是提高有机涂层与基板的附着力。典型的预处理工艺流程如图3-5-6所示。  \n\n传统的反应型预处理工艺流程  \n\n<html><body><table><tr><td colspan=\"2\">50~60℃ 清洗</td><td></td><td colspan=\"2\">清洗</td><td colspan=\"2\">50~60℃ 水洗</td><td colspan=\"2\">50~60℃ 水洗</td><td colspan=\"2\">40~50℃ 碱性氧化</td><td colspan=\"2\">40~50℃ 去离子水洗去离子水洗</td><td colspan=\"2\">40~50℃</td><td colspan=\"2\">30~45℃ 钝化</td></tr><tr><td></td><td>槽1</td><td></td><td>相2</td><td></td><td>槽3</td><td></td><td>槽4</td><td></td><td>槽5</td><td></td><td>槽6</td><td></td><td>槽7</td><td></td><td>槽8</td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>\n\n槽5工艺：喷淋或浸渍，处理时间 $5\\mathrm{\\sim}155_{\\circ}$ 槽8工艺：喷淋，处理时间 $5\\mathrm{-}15\\mathrm{s}.$  \n\n无水预处理工艺流程  \n\n![](images/0bd2272c23a0344ead5f676c7803a9ca18a1168cf2217a9e65cafbb6a241c92e.jpg)  \n图3-5-6 典型的预处理工艺流程  \n槽6工艺：辊涂，处理时间 $0\\cdots25$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 350,
+        "chunk": "# 一、脱脂  \n\n基板加工时，为了润滑、防腐蚀，在板材表面要涂覆润滑油脂，如矿物油或脂肪油，如果这些油脂残留在基板表面，就会影响涂层与基板的附着力，因此必须进行脱脂处理，用清洗介质除去表面黏附的油污。  \n\n要根据基板的种类和状态选用不同的清洗方法，主要有碱洗、酸洗以及先碱洗再酸洗等。采用碱洗的最多，对不同金属基板，应采用不同浓度的碱性清洗液，对冷轧钢板，清洗液碱浓度在 $1\\%\\sim2\\%$ ，对镀锌、铝、合金钢板，浓度要低一些。酸性清洗液的去污能力不如碱性清洗液，但酸性清洗液具有一定的腐蚀作用，可以除去基板表面的氧化膜，使其活化，而且使基板表面粗糙，有助于提高有机涂层的附着力。  \n\n碱性清洗液的主要成分有强碱，如氢氧化钠，提供强皂化能力；弱碱，如碳酸钠，皂化能力较弱，但可以起缓冲作用，维持碱度；硅酸钠也是弱碱，既可起缓冲作用，也可起到软化硬水的作用；磷酸盐如三聚磷酸钠也具有调节碱度和软化硬水的能力；弱碱也可以选用硼酸盐如焦硼酸盐，加水水解后可以形成硼酸和游离碱，起缓冲剂作用。除了碱性成分，碱性清洗液中还可加人络合剂和表面活性剂。络合剂用于络合水中的钙、镁等硬化离子，常用的为三聚磷酸盐，对硬度高的水，可以使用柠檬酸、EDTA（乙二胺四乙酸）等。清洗液中用的表面活性剂主要为有机乳化剂，如非离子型或阴离子型乳化剂，加人后可以降低油-水界面张力，提高清洗液的清洗效果。  \n\n脱脂处理时，应适当提高温度，可以提高洗涤效果，但温度也不能过高，过高反而降低去污能力，一般控制在 $70{\\sim}90^{\\circ}C$ ，如果清洗液中使用乳化剂，温度应适当降低。  \n\n现代预涂卷材生产线一般采用喷淋清洗法，基板在行进过程中经过脱脂处理槽时，清洗液通过喷嘴以一定压力和喷淋量喷向基板表面，将基板洗净。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 351,
+        "chunk": "# 二、表面调整处理  \n\n表面调整处理操作于钝化处理之前，作用是使基板活化，缩短化学转化膜成膜时间，改善转化膜质量。  \n\n表面调整处理通常采用含有胶质钛盐的溶液浸渍基板，随即进行化学转化处理。胶质钛盐颗粒作为结晶的细化剂在基板表面形成大量的晶核，使无数晶体同时开始成长，从而能在较短时间内形成细密结晶的磷酸盐转化膜。这种溶液的稳定性差，随着运行时间的延长，其$\\mathbf{pH}$ 会下降，从而会影响使用效果。表面调整液对基板的腐蚀速率越大，其失效越快。要得到稳定有效的表面调整效果，调整液的 $\\mathbf{pH}$ 要保持稳定，可以加入适量的碳酸盐，起缓冲作用。例如，采用含 ${\\bar{5}}{\\mathrm{mg/L}}$ 钛离子、 $\\mathrm{184mg/L}$ 磷酸根离子、 $49\\mathrm{mg/L}$ 焦磷酸根离子和 $50\\mathrm{mg/L}$ 碳酸根离子的表面调整处理液对冷轧钢板进行处理后，再进行磷化处理，可以得到均匀致密的磷酸盐转化膜。  \n\n对电镀锌表面，在用铬酸盐处理前，可以用含有络合剂和钛离子或锆离子的、 $\\mathrm{\\bf{pH}}$ 为$12.0{\\sim}13.5\\$ 的碱性表面调整液活化处理，例如用含 $70g/\\mathrm{L}$ 氟钛酸（ $\\mathrm{\\bfH_{2}T i F_{\\vec{6}}}^{\\prime}.$ ）（浓度为$40\\%)$ ， $60\\mathrm{g/L}$ 乙二胺四乙酸四钠盐、 $140_{\\mathrm{{E}}}/\\mathrm{{L}}$ 氢氧化钠和 $730\\mathrm{g/L}$ 水的溶液喷淋电镀锌钢板后，再用铬酸盐处理，可提高转化膜的附着性和耐腐蚀性。  \n\n对热镀锌钢板，热镀锌镀层凝固时表面会选择性氧化形成 $20\\sim30\\mathrm{nm}$ 厚的氧化膜，这层膜的电化学活性比较差，在以辊涂方式铬化处理时，会阻碍铬化处理液与基板表面的化学反应，因此需要采用酸性的含镍离子的溶液对表面进行活化调整处理，得到一个较粗糙、活性较高的表面。含镍离子的表面调整液的 $\\mathbf{pH}$ 和温度对基板的腐蚀速率及镍的附着量的影响较大，随 $\\mathfrak{p H}$ 升高，基板的腐蚀速率和镍的附着量都呈下降趋势；随着温度的升高，基板的腐蚀速率和镍的附着量都呈上升趋势。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 352,
+        "chunk": "# 三、化学转化处理  \n\n不同基板应该选用不同的化学转化处理方式。  \n\n以喷淋或浸渍方式处理冷轧钢板时大多选用氧化铁-磷酸盐型转化液，它是含有磷酸、碱金属磷酸盐及氧化剂如氯酸盐、硝酸盐和钼酸盐等的酸性溶液，反应形成氧化铁/磷酸盐的无定形转化膜。处理温度 $40\\sim75^{\\circ}C$ ，成膜时间 $5\\sim20\\mathrm{s}$ ，膜厚约 $0.3\\mathrm{g}/\\mathrm{m}^{2}$ 。但这类转化膜耐腐蚀性较差，还需再用铬酸盐处理。在这类处理液中添加氟化物氧化剂后，也可用于处理铝和锌基板表面。  \n\n对镀锌钢板可以选用磷酸盐、铬酸盐和复合金属氧化物型转化液。  \n\n磷酸盐处理液中一般含磷酸、磷酸锌及硝酸盐、镍和氟化物氧化剂等，反应形成一种主要成分为锌的磷酸盐的结晶性膜。处理温度 $65^{\\circ}C$ ，成膜时间 $5\\sim20\\mathrm{s}$ ，膜厚约 $\\bf{2.0{g}/\\bar{m}^{2}}$ ，还需再用铬酸盐处理。  \n\n复合氧化物型转化液是含碱类络合物以及钻、镍和铁等重金属离子的溶液，反应形成的膜的组成主要为含铁、钻和镍的锌的氧化物，处理温度40～70℃，处理时间5～20s，膜厚约0.1～0.3g/m²，这类转化膜耐腐蚀性较差，还需再用铬酸盐处理。这类转化液也可用于处理镀锌-铁和锌-铝合金板。  \n\n反应型铬酸盐-复合氧化物型转化液是含有铬酸和氧化剂如氟化物和钼酸盐的酸性溶液，反应形成无定形膜，主要含磷酸铬（三价铬化合物，致密性好）和铬酸铬（三价和六价铬复合氧化物， $x\\mathrm{Cr}_{2}\\mathrm{O}_{3}\\cdot y\\mathrm{CrO}_{3}\\cdot z\\mathrm{H}_{2}\\mathrm{O}$ ，具有自修复作用，耐腐蚀性好)，处理温度 $20\\sim60^{\\circ}C$ 4处理时间 $3\\sim15{\\mathrm{s}}$ 。这种转化液也可用于处理铝板，但这种转化膜中含有六价铬离子，因此带有这种转化膜的铝板不能用于制造食品和饮料罐，可以通过在转化液中加入磷酸，使六价铬转化成三价铬的方法克服这一缺点。  \n\n在以辊涂法转化处理时，对镀锌钢板、合金化镀锌钢板及锌铝合金钢板等，可采用铬酸盐类转化液。该处理液中含有与铬酸铬类似的成分，还添加有树脂和二氧化硅粒子作为黏度调节剂，提高膜的强度和致密性，在处理过程中没有化学反应，形成的表面膜结构由不溶性三价铬化合物和可溶性六价铬化合物组成，前者构成膜的骨架，后者填充于骨架内部，经这种铬酸盐处理的金属表面，耐腐蚀性可以大大提高。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 353,
+        "chunk": "# 四、环保型处理液  \n\n近年来，人们对环保越来越重视，含铬处理液虽然因为性能优异而广为采用，但其中含有大量六价铬，这是一种强致癌物质，并且在自然环境中很难降解，欧盟从2006年7月开始正式实施的ROHS指令（关于在电子电气设备中限制使用某些有害物质的指令）中对六价铬提出了明确的最高限量，材料中的六价铬含量不得超过 $\\mathrm{1000mg/kg}$ 。我国近年来也陆续颁布了一些对涂料中有害元素限量的强制性标准，其中包括对六价铬含量的限制。这些都无疑推动了预卷材生产厂家开始采用无六价铬的环保型预处理液。  \n\n中国钢研科技集团公司开发出了三价铬环保型处理液，将氧化铬（ $\\mathrm{CrO_{3}}$ ）溶于水中，并添加适当的无机酸如硝酸，加热至 $70^{\\circ}C$ 以上，使用还原剂如醇类将溶液中的六价铬还原为三价铬（六价铬含量 ${<}10\\mathrm{mg/kg})$ ，然后在还原液中加入硅溶胶和助剂，控制溶液 $\\mathbf{pH}$ 为$1.5\\sim2.5$ ，得到墨绿色的三价铬环保型预处理剂溶液。用该预处理液辊涂处理镀锌钢板，处理温度为 $<75^{\\circ}C$ ，形成的转化膜含铬量 $70\\mathrm{\\sim}150\\mathrm{mg/m^{2}}$ （双面）时最佳。该处理液制备的转化膜耐腐蚀性良好，与基板和涂层都具有良好的附着力，性能与传统预处理液相当，且不增加成本。  \n\n德国凯密特尔公司（Chemetall）开发出的无铬预处理液GardoTP10475，有双组分型，也有单组分型，其主要成分为钛/锆盐、磷酸盐和少量的树脂，可用于热镀锌、电镀锌、镀锌铝和冷轧钢板等各种基板。GTP10475的主要成分和作用见表3-5-2。该处理液涂覆工艺可以采用淋涂或辊涂。  \n\n表3-5-2GTP10475的主要成分和作用  \n\n\n<html><body><table><tr><td></td><td>成分</td><td>主要作用</td></tr><tr><td>钛/锆盐</td><td></td><td>保证与涂层的结合力和耐腐蚀性能与基板表面反应成膜 增加耐腐蚀性能</td></tr><tr><td>磷酸盐</td><td></td><td>辅助钛/锆成膜</td></tr><tr><td>聚合物树脂</td><td></td><td>增加与涂层的结合力</td></tr></table></body></html>  \n\n德国汉高公司（Henkel）开发出的无铬预处理液Granodine1455，为单组分型，含特殊的水溶性有机聚合物、钛/锰离子等成分，适用于热镀锌、电镀锌、镀锌铝、镀铝锌、铁锌合金、镀铝、冷轧钢板和不锈钢板等各种基板。采用辊涂施工，烘烤时板温要求 $40^{\\circ}C$ 以上。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 354,
+        "chunk": "# 第四节 预涂卷材涂料概述",
+        "category": " Introduction"
+    },
+    {
+        "id": 355,
+        "chunk": "# 一、预涂卷材涂料的特点和性能要求  \n\n预涂卷材涂料既要满足预涂卷材的生产工艺要求，又要满足卷材的加工使用方面的要求。  \n\n预涂卷材涂装采用连续辊涂生产工艺，其主要特点是基板行进速度快、涂料采用辊涂涂覆方式、涂膜短时高温烘烤、出炉后迅速降温。预涂卷材涂料必须要满足这些涂装工艺的要求。第一，预涂卷材涂料的施工黏度有一定要求，为了满足辊涂施工要求、保证一定的涂膜厚度和流平性，溶剂型卷材涂料一般的施工黏度为 $50\\sim100s$ （涂-4杯， $25^{\\circ}C$ )。由于卷材涂料施工黏度较高，为了保证足够的流平性，避免出现缩孔等涂膜缺陷，一般涂料中的流平剂用量较高。第二，预涂卷材涂料不能有明显的触变性（剪切稀释性)。辊涂施工时，基板与各辊子的运转速度不同（带料辊、涂覆辊和调节辊都有不同的转速)，它们之间所带的涂料会受到一定的剪切力，在这种情况下，涂料应仍保持原来的黏度，不能因触变而发生黏度下降，否则如果涂料黏度因受剪切作用而明显降低，会使辊子上附着不住所要求的涂料量，影响涂覆效果。第三，涂膜固化一般采用高温短时烘烤固化，烘烤温度一般在 $250\\sim400^{\\circ}\\mathrm{C}$ 烘烤时间 $20\\sim60\\mathrm{s}$ ，基板峰值温度（PMT，可用示温纸或测温枪在线测得）一般为 $204\\sim$ $249^{\\circ}C$ ；此外，涂覆后湿膜的闪干时间短，一般只有几秒到几十秒，所以预涂卷材中高沸点溶剂用量要比一般涂料高，否则会造成起泡、针孔和流平不好等缺陷。通常选用较高沸点的醇醚类、酮类和高沸点芳烃类、酯类溶剂等。第四，为了满足涂装要求，预涂卷材涂料要有一定的固化性能，固化速率太快，容易产生起泡、针孔、流平差等表面缺陷；固化速率不够，涂膜不能完全固化，影响涂膜的物化性能，不能满足加工和使用要求。  \n\n预涂卷材涂料产品根据用途一般分为三类，即：底漆、面漆和背漆。预涂卷材为多涂层体系，一般基材正面涂装一道底漆和一道面漆，背面涂装一道背面漆，有时在背面漆下也涂装一道底漆。对底漆、面漆和背漆有不同的性能要求。如图3-5-7所示列出了预涂卷材用底漆、面漆和背漆的主要性能要求。  \n\n![](images/9daaaa117872853339ca464bb7490e6ab4e1aaad3400c71380394fc63526476f.jpg)  \n图3-5-7彩钢板涂层体系及主要性能要求",
+        "category": " Introduction"
+    },
+    {
+        "id": 356,
+        "chunk": "# 二、预涂卷材涂料的组成  \n\n预涂卷材涂料由树脂、颜料、填料、溶剂和助剂组成。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 357,
+        "chunk": "# 1.树脂  \n\n预涂卷材涂料分为底漆、面漆和背面漆。  \n\n底漆根据所用基料树脂主要分为环氧体系和聚酯体系两大类，以氨基树脂或封闭异氰酸酯树脂为交联树脂（固化剂)。具体可分为聚酯-聚氨酯、聚酯-氨基、环氧-聚氨酯、环氧-氨基等。通过树脂改性以及品种的合理选用，也可以将环氧树脂与聚酯树脂混合使用，氨基树脂与封闭异氰酸酯树脂也可以混合使用，以进一步提高涂膜性能。建筑用预涂卷材对防腐性能要求较高，底漆中大多采用环氧-聚氨酯体系，以大分子环氧或改性环氧树脂为主体树脂；对家电等对加工性能要求较高的用途，环氧体系由于柔韧性较差，往往不能满足要求，因而大多采用以聚酯为主的体系，在这种体系中，可以拼用适量的环氧树脂，以提高防腐性能。  \n\n背面漆大多采用单涂层，涂膜较薄，而同时又要求高柔韧性、较好的耐MEK性能和较好的耐盐雾性能；对有些应用如制备泡沫夹心板时，背面漆还需适应发泡工艺要求，对发泡材料黏附性要好；应用于家电彩板时，背面漆的加工性能要求要高于建筑用彩板，有时还要求背面漆具有良好的导电性。与底漆类似，背面漆也主要分为环氧和聚酯两大类。前者以大分子环氧树脂（如609、1001和Epon1009等）或改性环氧树脂为主体树脂，以氨基树脂或封闭异氰酸酯为固化剂；后者以聚酯树脂为主体树脂，以氨基树脂或封闭异氰酸酯为固化剂，在这种体系中，为了提高性能，往往还要拼用适量的环氧树脂。  \n\n卷材涂料用面漆的种类较多，主要有：聚酯面漆、聚乙烯基类面漆、丙烯酸树脂类面漆、氟碳面漆和有机硅改性树脂类面漆等。  \n\n在卷材涂料用面漆中，（玻璃化温度）聚酯树脂涂料是用量最大的品种，通过选择不同的多元酸、多元醇制备不同 $T_{\\mathrm{~g~}}$ 、不同分子量的线型或支链型聚酯树脂。聚酯面漆配制时，可以通过混合不同 $T_{\\tilde{\\mathrm{~g~}}}$ 、不同分子量的聚酯树脂，灵活地调控获得优异的漆膜性能。对聚酯树脂的组成选择耐候性的组分，并通过加入适宜的位阻胺光稳定剂和紫外线吸收剂以及适宜的交联剂，可以制成耐候性十分接近于氟树脂而优于有机硅改性聚酯的涂料，用于户外用建材。  \n\n除聚酯面漆以外，卷材涂料面漆中用得最多的是聚乙烯基类树脂涂料，包括PVC有机溶胶和塑溶胶面漆以及不含氯的分散体涂料。PVC有机溶胶和塑溶胶是将溶胶级的聚氯乙烯粉末分散在有机溶剂和增塑剂中或只分散在增塑剂中的分散体，前者称为有机溶胶，后者称为塑溶胶。不含氯的分散体涂料是将其他高聚物粉末如聚酯、聚烯烃、聚丙烯酸酯等在增塑剂中形成的塑溶胶等，实际上是一种溶液分散型涂料，树脂溶液一般由端羟基聚酯或聚丙烯酸酯和封闭多异氰酸酯和溶剂组成。  \n\n第三类是丙烯酸面漆，溶剂型热固性丙烯酸涂料是早期彩钢板面漆的主要品种之一，以后随着聚酯面漆的发展，逐渐被其取代。目前在以铝材为基板的预涂卷材（卷铝）用涂料中使用较多；或者是用作聚偏二氟乙烯（PVDF）涂料中的改性树脂，提高颜料分散性能和与底材的附着力。  \n\n第四类是氟碳面漆。氟聚物分散体涂料具有优异的室外耐久性、耐化学品性和适宜的力学性能，特别适用于耐候性要求高的室外用建筑彩涂板市场。用于卷材的氟碳面漆可以分为热固型与热塑型两大类。热固型涂料中氟树脂分子中含有羟基等活性基团，成膜时可以通过活性基团与氨基树脂、聚氨酯树脂反应交联固化，这类涂料中应用最成功的FEVE 树脂，如日本旭硝子的商品名为LUMIFLON与大日本油墨商品名为FLUONATE的产品。也可以采用含有端羟基的全氟聚醚型氟碳卷材涂料，以脂肪族封闭异氰酸酯为固化剂。  \n\n热塑性氟树脂涂料应用最广泛的为PVDF。PVDF为结晶体聚合物，其不含活性基团，基本结构单元为 $\\mathrm{CH}_{2}\\mathrm{CF}_{2}$ ，PVDF不能单独用作涂料，通常要加入热塑性丙烯酸树脂。该类涂料中，以氟聚物粒子与丙烯酸树脂预先热熔融得到的混合物为成膜基料。其中，氟聚物为被分散相，丙烯酸聚合物溶液为连续相。应用于建筑彩板的PVDF 树脂以瓦特公司（Pannwalt）开发的KYNAR500和苏威公司（Solvay Solexis）的HYLAR5000为代表。  \n\n第五类是有机硅改性树脂类面漆，如有机硅改性聚酯和有机硅改性丙烯酸树脂涂料。有机硅改性聚酯中，硅氧烷含量通常为15%～50%（质量分数)，制备的涂料形成的涂膜具有优异的自洁、保光、保色、不粉化性，且坚韧耐磨，非常适用于制备耐久型卷材面漆。预涂卷材涂料用有机硅改性聚酯树脂一般采用含羟基的聚酯与烷氧基的硅（氧）烷或含硅羟基的硅（氧）烷经缩合反应而制备。此外，也可以将含官能基的硅烷或硅氧烷与过量的多元醇缩合，然后再与多元羧酸反应。有机硅改性丙烯酸树脂可以通过丙烯酸硅氧烷大单体与丙烯酸树脂合成的常用单体共聚制备。热固性有机硅改性聚酯树脂性能优异，成本适中，因此国内外主要卷材涂料研究单位和生产厂商都有此类产品。如上海振华造漆厂研制出的有机硅聚酯卷材涂料，人工老化试验达到 $2000\\mathrm{h}$ ，其具有优异的户外耐候性、保光和保色性。常州涂料化工研究院研制出的有机硅改性聚酯耐久卷材涂料，人工加速老化试验 $2000\\mathrm{h}$ 以上（失光、变色和粉化均为1级），QUV-B（313灯）试验 $\\boldsymbol{\\mathfrak{f o o h}}$ 以上不失光(1级)。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 358,
+        "chunk": "# 2.颜料  \n\n预涂卷材涂料用颜料要求具有较高的耐热性和耐久性，对家电用涂料，还有较高的环保和安全方面的要求。  \n\n颜料的选择首先要满足卷材涂料施工条件的要求。由于卷材涂料涂装固化条件为高温短时固化，烘烤温度一般为 $250\\sim400^{\\circ}C$ ，要求涂料选用耐热性好的颜料，高温烘烤时不会出现变色；其次，对建筑外用涂料，要求颜料有较好的耐候性；对家电用涂料，要求使用环保型颜料，不能含有铬、镉、铅等有害重金属。例如，在建筑用卷材涂料中常用的无机着色颜料铬黄、镉黄、钼铬红、镉红等，在家电用卷材涂料中就不能使用，而只能使用有机颜料、钒酸秘、铁红、铁黄等不含有害重金属的无机颜料。常用的有机颜料有酥菁类、喹吖啶酮类、DPP（二酮-吡咯-吡咯）类和苯并咪唑酮类等。  \n\n近年来，安全无毒的无机陶瓷复合颜料由于其优良的耐候性、耐热性、耐化学品性和耐光性，越来越受到人们的关注。  \n\n现在，卷材涂料中效应颜料如珠光颜料和非浮型铝粉浆等的使用也越来越多。由于卷材涂料一般为二涂层体系，不涂覆罩光清漆层，因此，对卷材涂料用的铝粉要求较高，通常需要采用包覆型铝粉，才能满足对涂层的耐碱性要求；此外，由于采用辊涂施工，且涂膜非常薄，因此要求使用的铝粉有较窄的粒径分布，粒径分布太宽时，过粗的粒子容易在涂覆的板面上拉出条纹，影响装饰效果。  \n\n现代社会越来越重视节能，这就要用到隔热颜料、填料，主要有红外反射（IRR）颜料和隔热填料。白色颜料和金属颜料如铝粉有较高的红外反射效果。深色IRR颜料例如巴斯夫开发的商品名为Paliogen@L0086和Sicopal@K0095的黑色IRR颜料；德固莎公司（ $\\bf\\delta D e^{-}$ gussa）的Eclipse°黑10201、10202、10203、10204；Eclipse°棕10221、10222；Eclipse°绿10241等。其他的IRR颜料如有机和无机或复合无机颜料（CICPs)，例如，C.I.颜料黑28（一种铜铬锈矿组成物）、C.I.颜料黑30（一种含镍、镁、铬和铁的尖晶石）、C.I.颜料绿17（含铬和铁）等。隔热屏蔽材料如云母、隔热陶瓷、玻璃珠等可以屏蔽吸收的热量，阻止热量的传导。  \n\n对用于底漆的防锈、防腐颜料，建筑用卷材涂料中仍广泛使用铬酸锶、铬酸锌等传统的防腐颜料。但对家电用卷材涂料，这些就不能使用，必须选用安全无毒的类型，如磷酸锌、钼酸锌、硼酸锌、改性偏硼酸钡、三聚磷酸铝、纳米碳酸钙以及一些新型的、沉积于载体上的离子型防锈颜料等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 359,
+        "chunk": "# 3.助剂  \n\n涂料中助剂用量虽少，但对涂料和涂膜的性能影响非常大。卷材涂料中常用的助剂有润湿分散剂、流平剂、固化催化剂、附着力促进剂、消光剂、增硬增滑助剂和光稳定剂等。  \n\n卷材涂料产品的颜色品种多，对色差要求非常高。为了帮助颜料的润湿、分散和稳定，需要加人润湿分散剂，常用的有高分子聚合物类分散剂，如汽巴公司的EFKA-4010、EF-KA-4046、EFKA-4060、EFKA-4080 等；德国毕克公司（BYK）的Disperbyk-170和 Dis-perbyk-185 等；Avecia 公司的 Solsperse32500等。低分子量不饱和羧酸聚合物类分散剂，如德国毕克公司（BYK）的BYK-P104、BYK-P104S和台湾德谦公司的904、904S等。另外，汽巴公司和毕克公司开发出的一种新型的、由受控自由基聚合技术制备的高分子型分散剂，如 EFKA-4310和 EFKA-4320、Disperbyk-2009、Disperbyk-2020 和 Disperbyk-2025等，可以用于制备无树脂或极低树脂含量的通用色浆，这种色浆浓度高、通用性强，可以节省仓储空间和研磨成本。  \n\n卷材涂料施工时，如果流平性不好，在辊涂时会产生辊痕，有时还会出现缩孔，必须添加防缩孔剂和流平剂，以得到更佳的流平效果和改善表面缺陷。卷材涂料中聚丙烯酸酯类防缩孔剂、流平剂使用最多，这类产品有毕克公司的Byk-390、Byk-354、Byk-356、Byk-358等；汽巴公司的Efka-8385；美国首诺公司（Solutia）的Modaflow 2100等。其他常用的流平剂有溶剂类防缩孔、流平剂产品，例如德国毕克化学公司（BYK）的Byketol-OK、Byke-tol-Special等。醋丁纤维素类也是一种较好的流平剂，丁酰基含量越高，流平效果越好。主要品种有美国伊斯曼公司（EASTMAN）的CAB551-0.01等。有机硅树脂类防缩孔、流平剂产品有毕克公司的Byk-331、Byk-306、Byk-310、Byk-320等和埃夫卡公司的Efka-3031等，但是有机硅类流平剂易稳泡，且在高温下易分解，易在烘道、漆膜上残留，从而造成重涂差、缩孔等表面缺陷，因此在卷材涂料中的使用越来越少，一般很少单独使用。氟系表面活性剂也是一种很好的防缩孔、流平剂，产品有汽巴埃夫卡公司的氟碳改性聚丙烯酸酯产品Efka-3777、Efka-3772和Efka-3600等。  \n\n为适应涂装时的固化条件，卷材涂料中往往要加人一定量的固化催化剂，一般在以氨基树脂为交联剂的涂料中加人酸催化剂，在以多异氰酸酯树脂为交联剂的涂料中使用的交联催化剂主要有叔胺类、金属有机化合物类如二月桂二丁基酸锡（DBTDL）及有机麟化合物。酸催化剂产品有金氏公司（King）的NACURE1051、K-CURE1040和NA-CURE 5225等；毕克公司的BYK-450；德固莎公司（Degussa）的DYNAPOLCATA-LYST1203等。异氰酸酯交联催化剂有汽巴精化（Ciba）的HY960叔胺类催化剂；卜内门化学工业公司（ICI）的AmietolM12胺类催化剂；德谦公司的DBTDL和KL-2有机锡类催化剂等。  \n\n卷材涂料中，为了改进对底材的附着力，往往使用附着力促进剂。有树脂类附着力促进剂，例如台湾德谦公司的ADP附着力促进树脂、拜耳公司（BAYER）的HMP附着力促进树脂、德固莎公司（Degussa）的EP2310、LTH和LTW附着力促进树脂等。硅烷偶联剂类附着力促进剂如道康宁公司（DowCorning）的Z-6030、Z-6032、Z-6340等；通用公司（GE）的Silquest系列硅烷偶联剂产品等。钛酸酯偶联剂烃附着力促进剂如常州江南助剂厂的JN-115A等。  \n\n建筑用预涂卷材涂料产品通常要求中光或低光，需要使用消光剂。常用的消光剂产品为无定形二氧化硅，它们可以用蜡进行表面处理，也可以不处理。例如GRACE（格雷斯）公司的SyloidED 44、C-807和C-809 等；INEOS Silicas（英力士）的GasilHP 260和HP-270等和东洋制铁化学株式会社的MicloidML-391A等。  \n\n预涂卷材成品在收卷时，面漆和背面漆均会承受一定的相对滑动，在卷材后加工成型和使用过程中易受到外界的摩擦和划伤，为了保护漆膜的外观和完整，除了要提高涂膜本身的硬度外，也可以借助加人增硬增滑助剂来改善涂膜表面的滑爽性，降低摩擦力，提高涂膜的抗划伤性。常用的增硬增滑助剂有聚四氟乙烯蜡，如MicroPowders，Inc.（微粉公司）的Fluo HT、美国杜邦公司的ZonylMPl200和美国三叶公司（Shamrock Technologies，Inc.）的 Shamrock SST-3等；聚四氟乙烯-聚乙烯蜡如微粉公司的Polyfluo150和三叶公司的ShamrockFS-511等。  \n\n为了提高建筑用卷材涂料的耐候性，往往要加入光稳定剂，常用的有紫外线吸收剂，如汽巴公司的天来稳 $\\textcircled{19}928$ ；位阻胺类光稳定剂，如天来稳 $\\textcircled{19}292$ ，两者往往拼合使用，汽巴公司推出了一种苯并三唑类紫外线吸收剂与位阻胺混合类型的光稳定剂天来稳 $\\textcircled{18}5060$ ，可以单独使用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 360,
+        "chunk": "# 4.溶剂  \n\n溶剂影响涂料的贮存稳定性、黏度、流动性和流平性，也会影响漆膜的外观和性能。溶剂选择时应考虑溶剂的溶解性（溶解度参数)、沸点、挥发速率和表面张力等基本特性，同时还要考虑到安全和环保因素。  \n\n酯、酮、醇醚类等含氧溶剂，溶解性好，是所谓真溶剂；烃类等不含氧溶剂，溶解性不如含氧溶剂，称为稀释剂，其价格一般比含氧溶剂便宜，可以降低成本。溶解度参数 $\\delta$ 是表述各种溶剂对树脂的溶解能力的通用方法，溶解度参数越接近的物质相溶性越好，从而可以设计出合适的混合溶剂。在涂料常用溶剂中，醇类的 $\\delta$ 值是 $22.50\\sim26.60$ 、酮类的是$16,37{\\sim}20,46.$ 、醚类的是 $18.41\\sim20.46$ 、芳烃的是 $16.37\\sim18.41$ 、脂肪烃的是 $14.32\\sim$ 16.37。混合溶剂的 $\\delta$ 值可以近似地用各组分溶剂的 $\\delta$ 值及其体积分数 $\\psi$ 的乘积之和来表示，即： $\\delta_{\\mathrm{mix}}=\\phi_{1}\\delta_{1}+\\psi_{2}\\delta_{2}+\\psi_{3}\\delta_{3}+\\cdots+\\psi_{n}\\delta_{n},$  \n\n混合溶剂的沸点和挥发速率必须适合预涂卷材高温、快速的烘烤工艺特点。溶剂的挥发方式对于得到好的漆膜外观和满意的漆膜性能十分重要。在成膜过程的湿阶段，混合溶剂的实际组成在不断变化，挥发性快的溶剂在混合溶剂中的比例会越来越少，剩下挥发性慢的溶剂。所以在混合溶剂中真溶剂的挥发性必须低于稀释剂的挥发性，以保持黏度逐渐增大的漆膜仍有好的流平性，否则会造成漆膜缺陷。预涂卷材涂料是在高温下快速固化成膜，选择混合溶剂应同时考虑所用溶剂的沸点和挥发速率。刚辊涂上的湿漆膜经极短时间闪干后立即进人温度高达 $200^{\\circ}C$ 以上的烘炉，如马上有大量溶剂逸出，会造成漆膜缩孔和流平不好，同时还要防止漆膜接近完全固化时还有较多残留溶剂逸出而造成起泡和针孔。因此要求所用混合溶剂在烘烤过程中的逸出速率要与基板温度（PMT）变化和漆膜的固化过程相适应。一般卷材涂料应选用沸点 $140{\\sim}240^{\\circ}C$ 的溶剂。  \n\n涂料的表面张力是影响涂料制造和施工的重要因素之一。树脂溶液的表面张力低时，对颜料的润湿分散和漆浆的稳定有利，也有利于涂料对底材的润湿和流平。溶剂型涂料，一般成膜树脂的表面张力高于溶剂的表面张力，成膜过程中随着溶剂的逸出，漆膜中树脂浓度逐渐增大，表面张力也不断上升，当这种变化不均匀时，会产生缩孔、橘皮等漆膜缺陷。所以在平衡各项因素的前提下，应尽可能选用表面张力低的溶剂。各类溶剂的表面张力范围：醇类 $21.4\\sim35.1\\mathrm{mN/m}$ 、酯类 $21.2\\sim28.5\\mathrm{mN/m}$ 、酮类 $22.5\\sim26.6\\mathrm{mN/m}$ 、乙二醇醚类$26.6{\\sim}34.8\\mathrm{mN/m}$ 、乙二醇醚酯类 $28.2{\\sim}31.7{\\mathrm{mN}}/{\\mathrm{m}}$ 、芳烃类 $\\mathrm{28.0{\\sim}30.0m N/m}$ 、脂肪族烃类 $18.0{\\sim}28.0\\mathrm{mN}/\\mathrm{m}$  \n\n选择溶剂还要充分考虑安全和环保问题。尽管卷材涂料施工过程中烘炉中逸出的大量含溶剂废气能回收利用，基本没有环保问题，这也是水性涂料在卷材涂料中的应用非常少的原因之一。但在涂料生产和使用过程中仍有安全和环保问题，必须符合现行和即将执行的有关政策法规。例如，在家电用预涂彩板中，已经有用户提出不能使用含有例如萘、葱等稠环芳烃类物质的溶剂。这样，原先卷材涂料中大量使用的重芳烃类高沸点溶剂如S-150#、$\\scriptstyle5-200^{\\#}$ 或乙二醇醚及其醚酯的使用将会受到限制。  \n\n卷材涂料中常用的溶剂见表3-5-3。  \n\n表3-5-3预涂卷材涂料常用溶剂及其主要参数  \n\n\n<html><body><table><tr><td>名称或品牌</td><td>表面张力/(mN/m)</td><td>沸点/℃</td><td>8/×10(J/m²)1/2</td><td>相对挥发速率</td></tr><tr><td>环己酮</td><td>34.5</td><td>155.0</td><td>20.25</td><td>0.25</td></tr><tr><td>异佛尔酮</td><td>1</td><td>215.2</td><td>18.62</td><td>0.03</td></tr><tr><td>乙二醇丁醚</td><td>27.4</td><td>170.6</td><td>18.21</td><td>0.1</td></tr><tr><td>乙二醇乙醚醋酸酯</td><td>31.8</td><td>156.3</td><td>17.8</td><td>0.24</td></tr><tr><td>丙二醇甲醚醋酸酯</td><td></td><td>145~146</td><td></td><td>一</td></tr><tr><td>二丙酮醇</td><td>31.0</td><td>166.0</td><td>18.82</td><td>0.15</td></tr><tr><td>DBE</td><td>35.6</td><td>190~230</td><td></td><td></td></tr><tr><td>二甲苯</td><td>31.48</td><td>135.0</td><td>18.00</td><td>0.68</td></tr><tr><td>Solvesso 100</td><td>34.0</td><td>157～174</td><td>17.6</td><td>0.19</td></tr><tr><td>Solvesso 150</td><td>34.0</td><td>188~210</td><td>17.39</td><td>0.04</td></tr><tr><td>Solvesso 200</td><td>36.0</td><td>226~279</td><td>17.80</td><td>0.04</td></tr><tr><td>S-100A</td><td>34.0</td><td>155~175</td><td>17.60</td><td>一</td></tr><tr><td>S-150</td><td>34.0</td><td>195~245</td><td>17.39</td><td></td></tr><tr><td>S-200</td><td>34.0</td><td>215~280</td><td>17.80</td><td></td></tr></table></body></html>\n\n$\\textcircled{1}$ 相对挥发速率以醋酸丁酯为1。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 361,
+        "chunk": "# 三、预涂卷材涂料性能的影响因素",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 362,
+        "chunk": "# 1.涂膜的附着力和内聚力对性能的影响  \n\n涂膜的附着力是指涂膜与被涂底材表面结合在一起的坚牢程度，它产生于涂料中聚合物的分子极性基团与被涂底材表面极性分子的极性基团之间的相互吸引力和物理结合力。涂膜的内聚力是使涂膜中粒子黏结在一起形成连续完整涂膜的能力，它产生于涂膜内部相邻分子之间的相互吸引力。附着力和内聚力同时影响着涂膜的性能，附着力不好，涂膜易从底材剥落而失效。内聚力不够时，涂膜本身易破坏，产生裂纹等。在预涂卷材涂膜的T弯试验中，要对样板弯折，并以一定黏性的胶带纸粘拉，观察其有无裂纹及脱落。若出现裂纹意味着涂膜内聚力的破坏；而涂膜如果被胶带纸粘掉，即意味着与底材间的附着力不够。  \n\n（1）附着力的主要影响因素附着力受底材的品种和表面状态影响较大。通过对底材进行合适的表面处理可以大大提高涂膜的附着力。同时降低涂料的表面张力、提高润湿性以及增加涂料的极性也可以提高附着力。卷材涂料中常通过加人附着力促进剂提高对底材的附着力即是基于这原理。对底面复合涂膜，还要考虑底漆膜与面漆膜之间的层间附着力，其中底漆的影响更大，即有所谓底漆的二次交联问题。底漆膜在第一次烘烤时的交联程度不能太高，否则底漆膜太致密，会影响与面漆之间的层间附着力。而如果控制底漆基料树脂中的官能团，使之具有不同的反应活性，底漆固化时活性高的官能团先反应，使底漆膜部分交联固化，然后活性略低的官能团在面漆烘烤固化时再第二次进行交联反应，而使底漆完全固化，从而提高底面层间附着力。  \n\n(2）涂膜内聚力的主要影响因素影响涂膜内聚力因素主要有：涂料的颜基比、树脂特  \n\n性、涂膜的厚度及固化交联等。  \n\n颜料的加入会降低涂膜的内聚力。以卷材涂料中最常用的两种颜色的面漆：白灰和海蓝为例，在同样的基料体系中，白灰的T弯往往不如海蓝，一般要差1～2T，这正是由于白灰的颜基比要比海蓝高得多，它的内聚力降低，从宏观力学性能上就表现为T弯性能的降低。更进一步，当达到或超过临界颜料体积浓度（CPVC）时，涂膜的内聚力会急剧降低，因为涂膜中颜料太多，结构松散，没有足够的基料树脂将它们黏合在一起，导致内聚力降低。此外在颜料分散时加入合适的分散剂提高润湿分散性，有助于涂膜内聚力的提高。  \n\n提高基料树脂分子量，可提高涂膜的内聚力。提高树脂官能度从而提高交联密度也可以提高涂膜内聚力。基料树脂的玻璃化温度 $(T_{\\Vec{\\mathbf{g}}}$ ）影响涂膜的内聚力。当外界温度处于高于涂膜 $T_{\\tilde{\\mathbf{g}}}$ 的条件时，涂膜内的自由体积增加，涂膜更柔软。涂膜在低于其 $T_{\\mathrm{~E~}}$ 的温度下受力后的形变为脆裂，如果是观察 $\\boldsymbol{\\Upsilon}$ 弯性能，即涂膜会产生裂纹。  \n\n涂层膜厚提高，内聚力提高。在宏观上即表现为随膜厚提高，涂膜的力学性能如 $\\boldsymbol{\\Upsilon}$ 弯和耐擦拭性能等提高。  \n\n涂料固化时，由于溶剂的蒸发以及交联反应的发生，往往会发生体积收缩，释放内应力，而保持涂膜的内聚力。卷材涂料底漆中常用的环氧树脂体系，由于其中的羟基基团的存在，与底材的附着力很好，但其内聚力低，体积收缩小，只有通过龟裂释放应力。表现在T弯性能上，即环氧底漆往往更容易产生裂纹。如果涂膜附着力很好且内聚力高，涂膜则不容易产生裂纹，如果受到外部应力，一般涂膜会丧失附着力，表现在T弯性能上，涂膜更容易粘掉，而不易产生裂纹。  \n\n底漆交联程度不能太高，如果底漆交联太好，漆膜太坚硬，加上底漆颜基比往往很高，其内聚强度较低时，不能抵御面漆涂膜体积收缩时释放的应力，容易造成底漆膜开裂。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 363,
+        "chunk": "# 2.面漆的交联密度对性能的影响  \n\n预涂卷材涂料中面漆的交联密度对涂膜的一些重要性能如耐MEK擦拭性、耐沾污性、硬度、T弯及耐划伤性等有较大的影响。一般而言，交联密度提高，涂膜的致密程度提高，从而使涂膜的耐MEK擦拭性、耐沾污性、硬度及耐划伤性提高，而T弯性能往往可能会下降。  \n\n影响面漆涂膜的交联密度的因素主要有基料树脂的官能度、支链化程度、交联树脂用量、固化条件等。基料树脂官能度提高，如果有足够的交联树脂与之交联反应，涂膜就越致密。树脂支链化程度越高，越容易形成网状结构，涂膜越致密，交联密度越高。交联树脂种类对得到的涂膜的交联密度也有一定的影响。卷材涂料中最常用的交联剂为氨基树脂（特别是甲醚化三聚氰胺树脂）和封闭型多异氰酸酯化合物，对同样的基料树脂，以氨基树脂固化的涂膜的交联密度一般比以封闭型异氰酸酯树脂固化的涂膜高。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 364,
+        "chunk": "# 四、预涂卷材涂料的性能检验标准  \n\n中国现有与预涂卷材及卷材涂料相关的性能检验标准主要由中国钢铁工业协会提出，由宝山钢铁股份有限公司负责起草，于2006年8月1日实施的GB/T12754—2006“彩色涂层钢板及钢带”和GB/T13448—2006“彩色涂层钢板及钢带试验方法”这两个国家标准；由中国石油和化学工业协会提出，常州涂料化工研究院等负责起草，于2007年3月1日实施的HG/T3830—2006“卷材涂料”化工行业标准。“彩色涂层钢板及钢带”标准中对建筑内、外用（家电及其他用途可参考使用）彩色涂层钢板及钢带的术语和定义、分类和代号、尺寸、外形、重量、技术要求、检验和试验、包装、标志及质量证明书等作了明显规定。  \n\n“彩色涂层钢板及钢带试验方法”中对彩色涂层钢板及钢带的涂层性能的测定和评价方法作了规定。“卷材涂料”化工行业标准对卷材涂料产品的定义、分类、要求、试验方法、检验规则和包装标志等作了规定，适用于采用连续辊涂方式涂覆在建筑用金属板上的液体有机涂料。涂覆在其他用途（如家电等）金属板上的液体有机涂料可参照使用。  \n\n表3-5-4为“彩色涂层钢板及钢带”标准规定的各类型基板在不同腐蚀性环境中推荐使用的公称镀层重量；表3-5-5为“彩色涂层钢板及钢带”标准规定的预涂卷材涂料的一些性能要求。  \n\n表3-5-4各类型基板在不同腐蚀性环境中推荐使用的公称镀层重量  \n\n\n<html><body><table><tr><td>基板类型</td><td colspan=\"3\">公称镀层重量（使用环境的腐蚀性）</td></tr><tr><td></td><td>低</td><td>中</td><td>高</td></tr><tr><td>热镀锌基板</td><td>90/90</td><td>125/125</td><td>140/140</td></tr><tr><td>热镀锌铁合金基板</td><td>60/60</td><td>75/75</td><td>90/90</td></tr><tr><td>热镀铝锌合金基板</td><td>50/50</td><td>60/60</td><td>75/75</td></tr><tr><td>热镀锌铝合金基板</td><td>65/65</td><td>90/90</td><td>110/110</td></tr><tr><td>电镀锌基板</td><td>40/40</td><td>60/60</td><td></td></tr></table></body></html>\n\n注：使用环境的腐蚀性很低和很高时，镀层重量由供需双方在订货时协商。  \n\n表3-5-5预涂卷材涂料的一些性能要求（一）  \n\n\n<html><body><table><tr><td rowspan=\"2\">面漆种类</td><td rowspan=\"2\">铅笔硬度</td><td rowspan=\"2\">耐中性盐雾试验/h</td><td colspan=\"2\">紫外灯加速老化试验/h≥</td></tr><tr><td>UVA-340</td><td>UVB-313</td></tr><tr><td>聚酯 硅改性聚酯</td><td></td><td>480 600</td><td>600</td><td>400</td></tr><tr><td>高耐久聚酯</td><td>HB</td><td>720</td><td>720 960 1800</td><td>480 600 1000</td></tr></table></body></html>  \n\n对弯曲、反向冲击等试验则分为低、中、高三级，分别作了规定，见表3-5-6。  \n\n表3-5-6 预涂卷材涂料的一些性能要求（二）  \n\n\n<html><body><table><tr><td>级别（代号）</td><td>T弯值/T ≤</td><td>冲击/kgf·cm</td></tr><tr><td>低(A)</td><td>5</td><td>6</td></tr><tr><td>中(B)</td><td>3</td><td>9</td></tr><tr><td>高(C)</td><td>1</td><td>12</td></tr></table></body></html>  \n\n根据HG/T3830—2006“卷材涂料”化工行业标准，将卷材涂料按使用功能分为底漆、背面漆和面漆。根据建筑用彩涂板正面实际使用时对耐久性的要求，又将面漆分为通用型和耐久型。通用型产品适用于一般用途的建筑内外用彩涂板，如室内装饰用吊顶板、屋面板、墙面板以及耐久性要求较低的外墙面板等；耐久型产品适用于耐久性要求较高的外用彩涂板，如门窗、外屋面板和墙面板等。其产品性能应满足表3-5-7的要求。  \n\n表3-5-7 卷材涂料性能要求  \n\n\n<html><body><table><tr><td rowspan=\"2\">项 目</td><td colspan=\"3\">指标</td></tr><tr><td>底漆</td><td>背面漆</td><td>面漆</td></tr><tr><td>在容器中状态</td><td></td><td></td><td>通用型 耐久型 搅拌后均匀无硬块</td></tr><tr><td>黏度(涂-4杯）</td><td></td><td></td><td>商定 60(浅色漆)</td></tr><tr><td>质量固体含量/%</td><td>45</td><td>55</td><td>50(深色漆) 45(闪光漆）</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td rowspan=\"3\">项 目</td><td colspan=\"4\">指标</td></tr><tr><td rowspan=\"2\">底漆</td><td rowspan=\"2\">背面漆</td><td colspan=\"3\">面漆</td></tr><tr><td>通用型</td><td></td><td>耐久型</td></tr><tr><td>体积固体含量/%</td><td>25</td><td>35</td><td colspan=\"3\">40(浅色漆） 35(深色漆）</td></tr><tr><td>细度/μm ≤ 涂膜外观</td><td></td><td></td><td colspan=\"3\">35(闪光漆) 25 正常</td></tr><tr><td>耐溶剂(MEK)擦拭/次 M</td><td></td><td>50</td><td colspan=\"3\">100 50（闪光漆）</td></tr><tr><td>涂膜色差 光泽（60°)/单位值 铅笔硬度（擦伤）/H 反向冲击强度④/kgf·cm</td><td></td><td>2H 60</td><td colspan=\"3\">商定 商定 H 90</td></tr><tr><td>T弯/T ≤ 杯突/mm 划格附着力（间距1mm）/级 耐划痕1200g</td><td></td><td>5 4.0</td><td colspan=\"3\">3 6.0 0</td></tr><tr><td>耐酸性</td><td></td><td></td><td colspan=\"3\">通过 无变化</td></tr><tr><td>耐中性盐雾</td><td></td><td></td><td colspan=\"3\">480h，允许轻微变色，起泡等 480h，允许轻微变色，起泡 级≤2（S3），无其他漆膜病态</td></tr><tr><td>耐人工老化</td><td></td><td></td><td>现象</td><td>等级≤2（S3），无其他漆膜病 态现象</td></tr><tr><td></td><td></td><td></td><td>600h，无生锈、起泡、开裂、变</td><td>960h，无生锈、起泡、开裂、</td></tr><tr><td>荧光紫外UVA-340</td><td></td><td></td><td>色≤2级，粉化≤1级 400h，无生锈、起泡、开裂、变</td><td>变色≤2级，粉化≤1级 600h，无生锈、起泡、开裂、</td></tr><tr><td>荧光紫外UVB-313</td><td></td><td></td><td>色≤2级，粉化≤1级 800h，无生锈、起泡、开裂、变</td><td>变色≤2级，粉化≤1级 1500h，无生锈、起泡、开裂、</td></tr><tr><td>氙灯</td><td></td><td></td><td>色≤2级，粉化≤1级</td><td>变色≤2级，粉化≤1级</td></tr></table></body></html>  \n\n对用于家电等特殊用途的预涂彩板，根据用途不同，各个生产厂家都有各自的产品标准。例如某公司对家用电冰箱所用预涂彩板验收标准见表3-5-8。  \n\n表3-5-8家用电冰箱预涂彩板某企业验收标准  \n\n\n<html><body><table><tr><td colspan=\"2\">项目</td><td>要求</td></tr><tr><td>外观</td><td>色点 斑点状/线状杂质 凹痕、皱纹/条纹痕迹 鱼眼状缩孔 油污 基材缺陷 擦伤</td><td>直径<0.5mm的色点不超过2个，且两色点之间的间距>400mm 直径<0.7mm且长度<3mm的杂质不超过2个，且间距>400mm 自然光下，用肉眼正视，无明显凹痕、条纹痕迹 无 无 无</td></tr></table></body></html>\n\n$\\textcircled{1}$ 浅色是指以白色涂料为主要成分，添加适量色浆后配制成的浅色涂料形成的涂膜所呈现的浅颜色，按GB/T15608—-1995中4.3.2规定明度值为 $\\frac{18}{4}\\sim9$ （三刺激值中的 $\\mathtt{Y_{D E5}\\geq31,25)}$ 暨$\\textcircled{2}$ 闪光漆是指含有金属颜料或珠光颜料的涂料。$\\textcircled{3}$ 特殊品种除外，如闪光漆、PVDF类涂料、含耐磨助剂类涂料等。$\\textcircled{4}$ $\\textcircled{4}1\\mathrm{kgf}\\cdot\\mathrm{cmss}0.098\\mathrm{J},$ .$\\textcircled{5}$ 三种试验方法中任选一种。  \n\n续表  \n\n<html><body><table><tr><td colspan=\"2\">项目</td><td>要求</td></tr><tr><td>力学性能</td><td>硬度（三菱铅笔）/H 杯突/mm 弯曲/mm 附着力(级)</td><td>≥2 6 2 ≤2</td></tr><tr><td>耐温性、 耐湿性、 耐化学品性</td><td>冲击强度/kgf·cm 耐低温性 耐沸水性 耐候性 耐硫酸 耐氢氧化钠 耐石油和汽油? 盐雾 耐湿性</td><td>40 E≤1.0，涂膜无分离现象 △E≤1.0，涂膜无收缩、裂痕、皱纹、剥离或显著变色 △E≤1.0，涂膜无变化 E≤1.0，涂膜无变化 涂膜无变化 E≤1.0，无起泡现象 涂膜无变化 十字切口边的锈蚀蔓延不超过2mm</td></tr></table></body></html>  \n\n$\\textcircled{1}$ 硬度：WOLFF-WILBOURN型硬度计，负荷 $750g$ 的小车上固定一支铅笔（或手握铅笔)，铅笔的轴与水平轴线成 $45^{\\circ}$ 夹角。铅笔头垂直于砂纸在砂纸上磨平，然后小车（或手握铅笔）在漆膜表面滑动几厘米，用棉球擦掉漆膜上的墨迹，要求硬度2H的铅笔不能在漆膜上留下划痕。  \n\n$\\textcircled{2}$ 耐低温性：在 $0^{\\circ}C\\pm1^{\\circ}C$ 环境下1h后，在曲率半径为 $1.0\\mathrm{mm}\\pm0.1\\mathrm{mm}$ 的轴棒上涂层面朝上和朝下弯折90°后目视观察，无裂纹、起皱及剥落等现象。  \n\n$\\textcircled{3}$ 耐沸水性：将试片完全浸人沸水中2h，然后放人自来水中冷却 $5\\mathrm{min}$ $\\textcircled{4}$ 耐候性：试片置于阳光下 $\\mathrm{\\t{o0h}}$ 或在温度 $120^{\\circ}C\\pm10^{\\circ}C$ 恒温箱中放置 $3h$ $\\textcircled{5}$ 耐湿性：在温度 $60^{\\circ}C\\pm2^{\\circ}C$ ，相对湿度 $98\\%$ 的恒温箱中放置 $\\mathsf{100h}$ 后取出检查。  \n\n$\\textcircled{5}$ 耐硫酸：试片室温下在 $5\\%$ 的硫酸中浸泡5h后取出观察。  \n\n$\\textcircled{7}$ 耐氢氧化钠：试片室温下在 $5\\%$ 的氢氧化钠中浸泡1h后取出观察。  \n\n$\\textcircled{8}$ 耐石油和汽油：试片室温下在 $100\\%$ 的石油和汽油中浸泡8h后取出观察。  \n\n$\\textcircled{9}$ 耐盐雾：按GB/T10125进行，浓度 $5\\%=\\frac{17}{2}$ 的盐雾状态中， $35^{\\circ}C$ 、60h 内，十字切口边的锈蚀蔓延应不超过 $2\\mathrm{mm}$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 365,
+        "chunk": "# 五、预涂卷材涂料的性能检验方法  \n\nGB/T13448—2006“彩色涂层钢板及钢带试验方法”中对彩色涂层钢板及钢带涂膜性能的测定和评价方法作了明确的规定。HG/T3830—2006“卷材涂料”化工行业标准中对卷材涂料产品的性能检验试验方法也作了明确规定，该标准中，特别对卷材涂料特有的性能，如耐溶剂（MEK）擦拭性和T弯试验方法作了明确规定和详细的阐述。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 366,
+        "chunk": "# 第五节 预涂卷材用底漆",
+        "category": " Introduction"
+    },
+    {
+        "id": 367,
+        "chunk": "# 一、预涂卷材底漆概述  \n\n在防腐蚀涂料中，底漆是整个涂层系统中极重要的基础，涂层的许多性能如对底材的附着力、复合漆膜的防腐性能等的好坏等，很大程度上取决于底漆的好坏；其他的如力学性能中的T弯性能、耐MEK擦拭性能、杯突性能等受底漆影响也很大。  \n\n开发高性能的预涂卷材底漆，对改善整个预涂卷材的加工性能起着非常关键的作用，对不同的底材和配套面漆往往需要使用不同的底漆，以使复合涂膜充分发挥性能要求。  \n\n底漆根据所用基料树脂主要分为环氧体系和聚酯体系两大类，根据交联树脂的不同又可分为聚酯聚氨酯、聚酯氨基、环氧聚氨酯、环氧氨基等。这两大类底漆都各有优点，但也都  \n\n存在明显的不足之处。因此又开发出了所谓“通用型底漆”，综合性能优于前两者。三类常见底漆的特性对比见表3-5-9。  \n\n表3-5-9 三类常见底漆特性对比  \n\n\n<html><body><table><tr><td>项目</td><td>环氧底漆</td><td>聚酯底漆</td><td>通用底漆</td></tr><tr><td>基料树脂</td><td>环氧</td><td>以支链小分子聚酯为主， 可适当拼用合适的环氧树脂</td><td>以中高分子聚酯为主，可适当拼用合适的 环氧树脂</td></tr><tr><td>交联剂</td><td>氨基树脂 封闭异氰酸酯树脂</td><td>氨基树脂 封闭异氰酸酯树脂</td><td>氨基树脂 封闭异氰酸酯树脂</td></tr><tr><td>优点</td><td>与底材特别是金属底材的 湿附着力好 耐盐雾性能好 所需烘烤温度可比聚酯 略低</td><td>柔韧性略优于环氧树脂 成本较低</td><td>与底材的附着力好 柔韧性优异 耐盐雾性能好 与面漆的配套性能好，层间附着力优异 底材适应性强 适宜的烘烤温度范围宽</td></tr><tr><td>缺点</td><td>柔韧性差 由于可交联官能团较多， 底漆膜太硬，导致与面漆的 层间附着力不够 适宜的烘烤温度范围窄， 过烘烤性差 底材适应性差</td><td>柔韧性和附着力一般 底漆膜较致密，与面漆的 层间附着力、配套性能一般 适宜的烘烤温度范围窄，能有时不如环氧底漆 过烘烤性差 底材适应性差</td><td>底漆膜的交联程度较低，耐MEK擦拭性</td></tr><tr><td>用途</td><td>加工性能要求一般的建筑 彩钢板</td><td>加工性能要求一般的建筑 彩钢板</td><td>门窗、家电彩板等对加工性要求很高的产 品以及作为PVDF面漆的专用配套底漆</td></tr></table></body></html>  \n\n因此，不同类型的底漆各有优点，但也都存在不足之处，应根据具体用途合理选用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 368,
+        "chunk": "# 二、预涂卷材底漆的组成  \n\n预涂卷材底漆由树脂、颜料、填料、助剂和溶剂组成。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 369,
+        "chunk": "# 1.预涂卷材底漆用树脂  \n\n卷材底漆用基料树脂主要为环氧和聚酯，交联树脂主要为氨基树脂和封闭异氰酸酯。卷材底漆常用环氧树脂、聚酯树脂牌号及参数见表3-5-10～表3-5-12。  \n\n表3-5-10卷材底漆常用环氧树脂牌号及参数  \n\n\n<html><body><table><tr><td>商品牌号</td><td>生产厂家</td><td>环氧当量/（g/eq)</td><td>软化点/℃</td></tr><tr><td>EPICLON HM-091</td><td>无锡迪爱生环氧有限公司</td><td>2200～2900</td><td>135~150</td></tr><tr><td>EPICLON 7050</td><td>无锡迪爱生环氧有限公司</td><td>1750～2100</td><td>一</td></tr><tr><td>EPIKOTE 1009</td><td>壳牌（SHELL)</td><td>2273~3846</td><td>一</td></tr><tr><td>EPIKOTE 1007</td><td>壳牌（SHELL)</td><td>1500～2000</td><td>一</td></tr><tr><td>NPES-907</td><td>南亚塑胶工业股份有限公司</td><td>1500~1800</td><td>120～130</td></tr><tr><td>NPES-907L</td><td>南亚塑胶工业股份有限公司</td><td>1400~1600</td><td>115~125</td></tr><tr><td>NPES-909</td><td>南亚塑胶工业股份有限公司</td><td>1800~2500</td><td>130～150</td></tr><tr><td>NPES-909H</td><td>南亚塑胶工业股份有限公司</td><td>2100~2500</td><td>135~150</td></tr><tr><td>NPES-607</td><td>南亚塑胶工业股份有限公司</td><td>1650～1900</td><td>120~135</td></tr><tr><td>NPES-609A</td><td>南亚塑胶工业股份有限公司</td><td>2400~3000</td><td>135～150</td></tr><tr><td>NPES-609D</td><td>南亚塑胶工业股份有限公司</td><td>2600~3500</td><td>135~150</td></tr><tr><td>YD-019</td><td>南亚塑胶工业股份有限公司</td><td>2500～3100</td><td>125~140</td></tr><tr><td>YD-019K</td><td>南亚塑胶工业股份有限公司</td><td>2500~3800</td><td>120~150</td></tr><tr><td>YD-020L</td><td>南亚塑胶工业股份有限公司</td><td>3500~4300</td><td>135~145</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>商品牌号</td><td>生产厂家</td><td>环氧当量/（g/eq）</td><td>软化点/C</td></tr><tr><td>SM 609</td><td>江苏三木集团有限公司</td><td>2831~4000</td><td>130～150</td></tr><tr><td>SM 1009</td><td>江苏三木集团有限公司</td><td>2222~2941</td><td>130~150</td></tr><tr><td>EP 307</td><td>氰特(CYTEC)</td><td>1400~1900</td><td>一</td></tr><tr><td>EP 309</td><td>氰特(CYTEC)</td><td>2400~3500</td><td>一</td></tr><tr><td>DER 668</td><td>深圳立骅合成树脂</td><td>2000～3000</td><td>130～148</td></tr><tr><td>DER 667</td><td>深圳立驿合成树脂</td><td>1600~2000</td><td>120~135</td></tr><tr><td>DER 669</td><td>深圳立骅合成树脂</td><td>3500~5500</td><td>140～160</td></tr><tr><td>DER669E</td><td>深圳立骅合成树脂</td><td>2500~4000</td><td>140～160</td></tr></table></body></html>  \n\n表3-5-11国产卷材底漆常用聚酯树脂牌号及参数  \n\n\n<html><body><table><tr><td>商品牌号</td><td>生产厂家</td><td>固含量 /%</td><td>酸值（以树脂固体计） /(mg KOH/g)</td><td>羟值（以树脂固体计） /(mg KOH/g)</td></tr><tr><td>3316</td><td>江苏三木集团有限公司</td><td>55.0±1.0</td><td>≤8</td><td>40</td></tr><tr><td>3920-1</td><td>江苏三木集团有限公司</td><td>60.0±1.0</td><td>≤7</td><td>70</td></tr><tr><td>BL-0717</td><td>深圳立合成树脂</td><td>70±1</td><td>5.6±1.5</td><td>一</td></tr><tr><td>LF-7211-1</td><td>深圳立驿合成树脂</td><td>70±1</td><td>5.6±1.5</td><td></td></tr><tr><td>BL-07171M</td><td>深圳立合成树脂</td><td>70±1</td><td>4~7</td><td></td></tr></table></body></html>  \n\n表3-5-12进口卷材底漆常用聚酯树脂牌号及参数  \n\n\n<html><body><table><tr><td>商品牌号</td><td>生产厂家</td><td>固含量 /%</td><td>酸值（以树脂固体计） /(mg KOH/g)</td><td>羟值(以树脂固体计） /(mgKOH/g)</td><td>T/℃</td><td>分子量</td></tr><tr><td>SH970</td><td>DSM</td><td>40</td><td>0~4</td><td>5</td><td>67</td><td>15000</td></tr><tr><td>SH973</td><td>DSM</td><td>40</td><td>8~10</td><td>5</td><td>65</td><td>20000</td></tr><tr><td>SH974</td><td>DSM</td><td>40</td><td>0~2</td><td>5</td><td>47</td><td>15000</td></tr><tr><td>SN800</td><td>DSM</td><td>60</td><td>0~4</td><td>20</td><td>27</td><td>6000</td></tr><tr><td>SN905</td><td>DSM</td><td>60</td><td>0~8</td><td>20</td><td>51</td><td>5000</td></tr><tr><td>ES-300</td><td>SK化工</td><td>100</td><td>一</td><td>1~5</td><td>17</td><td>26000</td></tr><tr><td>ES-410</td><td>SK化工</td><td>100</td><td>一</td><td>4~8</td><td>47</td><td>16000</td></tr><tr><td>ES-450</td><td>SK化工</td><td>100</td><td>一</td><td>4~8</td><td>52</td><td>18000</td></tr><tr><td>ES-901</td><td>SK 化工</td><td>100</td><td>一</td><td>4~8</td><td>68</td><td>21000</td></tr><tr><td>ES-910</td><td>SK化工</td><td>100</td><td>/</td><td>7~11</td><td>65</td><td>15000</td></tr><tr><td>ES-955</td><td>SK化工</td><td>100</td><td>一</td><td>9~15</td><td>58</td><td>12000</td></tr><tr><td>ES-960</td><td>SK化工</td><td>100</td><td>一</td><td>15~23</td><td>18</td><td>7500</td></tr><tr><td>ES-980</td><td>SK化工</td><td>100</td><td>一</td><td>13~21</td><td>23</td><td>12000</td></tr><tr><td>L205</td><td>degussa</td><td>一</td><td><3</td><td>5~10</td><td>67</td><td>15000</td></tr><tr><td>L210</td><td>degussa</td><td>一</td><td><3</td><td>5</td><td>63</td><td>20000</td></tr><tr><td>L411</td><td>degussa</td><td>一</td><td><3</td><td>5</td><td>47</td><td>16000</td></tr><tr><td>LH820</td><td>degussa</td><td>50</td><td><3</td><td>20</td><td>55</td><td>5000</td></tr><tr><td>LH833</td><td>degussa</td><td>50</td><td><3</td><td>35</td><td>55</td><td>4000</td></tr><tr><td>LH818</td><td>degussa</td><td>50</td><td><3</td><td>20</td><td>35</td><td>6000</td></tr><tr><td>LH910</td><td>degussa</td><td>60</td><td><3</td><td>25</td><td>10</td><td>5000</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 370,
+        "chunk": "# 2.预涂卷材底漆用颜料、填料  \n\n底漆中，防腐颜料、填料的品种和用量以及基料树脂与防腐颜料、填料的相互作用对涂料的稳定性、物理力学性能，尤其是涂层的耐蚀防腐性能具有相当大的影响。因此在卷材底漆中必须合理地选择颜料、填料品种及其粒径。颜料、填料在防腐涂料体系中发挥的作用有：化学防锈，如红丹、锌铬黄等；物理屏蔽，如云母、玻璃鳞片等；屏蔽日光紫外线对漆膜的破坏，如炭黑、云母氧化铁；调节颜料体积浓度，提高漆膜的附着力，如滑石粉、沉淀硫酸钡等；调节涂料的流变性，如气相二氧化硅；提高涂料的耐热性，如铝粉。有的防腐颜料、填料还可以同时起到上述几种作用。  \n\n有机高分子防腐层的腐蚀破坏主要有两种形式：化学腐蚀破坏和物理破坏。防腐失效通常是在物理破坏的基础上引起的，其外界因素主要是介质的渗透。此外，钢结构的残余应力及热应力也是引起腐蚀破坏的重要因素。  \n\n卷材底漆中常用的防腐颜料有铬酸盐类颜料、磷酸锌、碱式硅铬酸铅、三聚磷酸铝、钼酸锌、改性偏硼酸钡等。常用的填料有沉淀硫酸钡、滑石粉、气相二氧化硅等。常用的遮盖颜料有钛白、氧化锌等。铬酸盐类颜料可以提供铬酸根离子，配制成涂料后，在钢铁表面上起钝化作用，从而起到防锈、防腐蚀的功能，主要品种有锌铬黄、锶铬黄、钡铬黄、钙铬黄等，但这类颜料含有铬等有害重金属，主要用于建筑外用涂料。无毒的防腐颜料有改性偏硼酸钡、磷酸锌、三聚磷酸铝、钼酸锌和硼酸锌等以及其他一些新型无毒防锈颜料，如格雷斯（GraceDavison）开发出的一种新型的商品名为SHIELDEX的无毒防锈颜料，可适用于卷材底漆，这是一种基于钙离子交换型无定形二氧化硅凝胶的防锈颜料，与各种树脂体系及其他防锈颜料有很好的相容性，通过与金属底材的直接或间接的相互作用可以减缓其腐蚀速率。另一种无毒防腐颜料是由有机取代的磷酸或有机取代的麟酸或麟酸基羧酸的多价金属盐组成，包括钙、锌、钡、锶或镁等，这种金属盐类在水中的溶解度很低；磷酸或麟酸可以被一个或多个有机基团取代，如烷基、链烯基、环烷基、芳烷基、杂环、稠环等；对金属底材具有较好的防腐性能。Sachtleben Chemie GmbH研制出了一种无毒的具有防腐性能的二氧化钛颜料，它是以钛白颜料为载体，在外面包覆具有防腐性能的无机材料，然后再进行有机处理，使颜料具有优异的分散性能。这种颜料的特点之一是它的粒径非常小，约 $0.3\\sim$ $0.4\\mu\\mathrm{m}$ ，比一般的防腐颜料要小得多；其次，这种颜料具有很好的遮盖力，与金红石型钛白相当，其防腐性能相当于磷酸锌。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 371,
+        "chunk": "# 3.预涂卷材底漆用助剂  \n\n涂料中加人助剂可以改进生产工艺，改善施工条件，提高产品质量，赋予特殊功能，是涂料不可缺少的组成部分。预涂卷材底漆中除了要用到一些常用助剂如润湿分散剂、防缩孔、流平剂、附着力促进剂及固化催化剂等，还可加入一些底漆特有的助剂如防沉助剂、附着力促进剂和腐蚀抑制、防锈剂。  \n\n一般卷材底漆用颜填料含量较高，易出现颜料沉降现象，因此需要加人适量防沉助剂，防止颜料沉降。常用的防沉助剂主要有：有机膨润土，气相二氧化硅等。商品牌号例如：临安涂料助剂厂生产的各类有机膨润土。维乐斯（RHEOX）公司的BENTONE系列及美国洛克伍德公司（ROCKWOOD）的有机膨润土。德固萨公司、卡博特公司（CABOT）的气相二氧化硅类流变控制助剂。  \n\n为了改进对底材的附着力，可以加入附着力促进剂。  \n\n(1）树脂类附着力促进剂含有羟基、羧基、醚键或氯代树脂、磺酰氨基等溶剂型树脂，与一般树脂有较好的混容性，又与底材可形成一定的化学结合，因而在漆膜与底材间形成化学结合力。这些助剂自身又在漆膜中通过互溶、缠绕等作用与漆膜结合在一起，因而提高了附着力。产品例如：德谦（上海）化学有限公司的ADP附着力促进树脂；拜耳公司（BAYER）的HMP附着力促进树脂；德固萨公司（Degussa）的EP 2310、LTH、LTW 附着力促进树脂等。  \n\n(2）硅烷偶联剂类附着力促进剂加有少量硅烷偶联剂的涂料，在涂布施工后，硅烷向涂料与度材的界面迁移，遇到无机表面的水分，可水解生成硅醇基，再与底材表面上的羟基形成氢键或缩合成Si—O—M（M代表无机界面）共价键。同时，硅烷各分子间的硅醇基又相互缩合形成网状结构的覆盖膜。含有硅烷的涂料中可以形成硅烷与漆基相互渗透的网状结构，增强内聚力和耐水侵蚀的稳定性。产品例如：道康宁公司（DowCorning）的Z-6030、Z-6032、Z-6340等；通用公司（GE）的Silquest系列硅烷偶联剂产品等。  \n\n(3）钛酸酯偶联剂烃附着力促进剂无机底材往往是由于表面吸附了一层水而影响附着力，单异丙氧基钛酸酯的结构通式为 $i–\\mathrm{C_{3}}\\mathrm{H_{7}O T i R_{3}}$ 。其中 $\\scriptstyle\\mathbf{R}$ 为长链脂肪酸酯基、磷酸酯基等，分子中的异丙基也易与无机底材表面的吸附水经水解而结合，形成化学键，R基也易与漆料中聚合物分子或发生化学反而结合，或经缠绕而物理结合，从而起附着力促进作用。这类产品例如：常州江南助剂厂的JN-115A等。  \n\n卷材底漆中可以加入腐蚀、抑制剂、防锈剂，其提高涂层防腐蚀能力的作用机理是：$\\textcircled{1}$ 提高涂层与底材的附着力； $\\textcircled{2}$ 提高涂层对水汽的屏蔽作用； $\\textcircled{3}$ 选用对钢材具磷化、钝化、缓蚀作用的活性颜料体系及助剂； $\\textcircled{4}$ 选用比铁的电极电位更低的材料如铝、锌等金属粉末，形成牺牲阳极而达到阴极保护作用等。硅烷偶联剂和钛酸酯偶联剂是通过提高涂层与基材之间的附着力而提高涂层耐腐蚀能力。有机氮碱类防锈剂的作用是与可溶的杂多酸反应生成不溶的杂多酸氮碱络盐，促使活泼的铁锈稳定，常用的有铬酸胍、氨基胍、磷二苯胍等。此类防锈剂用量仅为颜料、填料的 $3\\%\\sim5\\%$ 时即可明显提高涂层的防腐蚀能力。产品例如：江苏泰兴涂料助剂化工厂的JTY防锈助剂、湖北十堰新欣表面处理技术开发公司的SA 涂料缓蚀剂及德国汉高公司的 $\\mathrm{ALCOPHOR^{\\textregistered}827}$ 等。含钡、含锌、含铅的防锈剂的作用是提高介质的碱性，降低氧的临界浓度，也可以起氧化作用，将活性的亚铁离子氧化成铁离子，以形成氢氧化铁的保护层。产品例如：道康宁公司的DowCorning 84、Dow Corning85等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 372,
+        "chunk": "# 三、环氧类底漆  \n\n交联后的环氧树脂漆膜含有许多羟基和醚键，与金属底材有强的极性结合力。金属发生腐蚀时阴极部位呈碱性，如果涂膜不含酯键就不会被皂化破坏。环氧树脂中不含酯键，因此常用作卷材底漆基料树脂。为了使其具有良好的柔韧性和加工成型性，预涂金属卷材底漆一般要用高分子量环氧树脂，交联剂可采用氨基树脂或封闭型多异氰酸酯，两种交联剂也可以混合使用。  \n\n以封闭型多异氰酸酯固化的环氧底漆称为环氧-聚氨酯底漆。这种底漆是目前国内所用卷材最常用的底漆品种之一。这种底漆中，用封闭二异氰酸酯聚醚预聚物作为交联剂，固化609环氧树脂成膜，采用聚醚是因为醚键的柔韧性和耐水解性比酯键好。典型的环氧聚氨酯底漆配方见表3-5-13。  \n\n表3-5-13 典型的预涂卷材环氧聚氨酯底漆配方   \n\n\n<html><body><table><tr><td>原料</td><td>规格</td><td>用量/g</td><td>原料</td><td>规格</td><td>用量/g</td></tr><tr><td>EPIKOTE1009环氧</td><td>50%溶液</td><td>37.8</td><td>Efka-4010</td><td>汽巴-埃夫卡公司</td><td>1.2</td></tr><tr><td>封闭异氰酸酯固化剂</td><td>50%溶液</td><td>12.6</td><td>ADP附着力促进剂</td><td>德谦公司</td><td>1.2</td></tr><tr><td>锌铬黄</td><td>工业</td><td>4.2</td><td>Efka-3777</td><td>汽巴-埃夫卡公司</td><td>0.5</td></tr><tr><td>锶铬黄</td><td>工业</td><td>6.3</td><td>二甲苯</td><td>工业</td><td></td></tr><tr><td>磷酸锌</td><td>工业</td><td>4.2</td><td>环已酮</td><td></td><td>10.5</td></tr><tr><td>钛白</td><td>工业</td><td>10.5</td><td></td><td>工业</td><td>10.5</td></tr><tr><td>有机膨润土</td><td>临安涂料助剂厂</td><td>0.5</td><td colspan=\"2\">总计</td><td>100.0</td></tr></table></body></html>  \n\n以氨基树脂固化的环氧底漆称为环氧-氨基底漆。高分子量环氧树脂的羟基含量高，羟基残留太多会导致涂膜的耐水性差。利用氨基树脂特别是脲醛树脂与羟基反应，可得到良好的附着性、高韧性和高耐化学品性的漆膜。典型的环氧氨基底漆配方见表3-5-14。  \n\n表3-5-14典型的预涂卷材环氧氨基底漆配方   \n\n\n<html><body><table><tr><td>原料</td><td>规格</td><td>用量/g</td><td>原料</td><td>规格</td><td>用量/g</td></tr><tr><td>EPIKOTE 1009环氧</td><td>50%溶液</td><td>37.8</td><td>ADP附着力促进剂</td><td>德谦公司</td><td>1.2</td></tr><tr><td>脲醛树脂</td><td>60%溶液</td><td>10.5</td><td>Byk-450</td><td>毕克公司</td><td>0.5</td></tr><tr><td>锌铬黄</td><td>工业</td><td>7.7</td><td>Efka-3777</td><td>汽巴-埃夫卡公司</td><td>0.5</td></tr><tr><td>锶铬黄</td><td>工业</td><td>5.6</td><td>二甲苯</td><td>工业</td><td>11.3</td></tr><tr><td>钛白</td><td>工业</td><td>11.9</td><td>环已酮</td><td>工业</td><td>11.3</td></tr><tr><td>有机膨润土</td><td>临安涂料助剂厂</td><td>0.5</td><td>总计</td><td></td><td></td></tr><tr><td>Efka-4010</td><td>汽巴-埃夫卡公司</td><td>1.2</td><td colspan=\"2\"></td><td>100.0</td></tr></table></body></html>  \n\n用分子量 $10000{\\sim}300000$ 的高分子线型环氧树脂可以制成热塑性底漆，其力学性能优于热固性环氧底漆，可用作PVC塑溶胶的底漆。  \n\n江苏鸿业涂料科技产业有限公司开发出了一种聚酰胺改性的大分子量环氧聚氨酯树脂，制备得到一种自交联型卷材底漆，与面漆配套性好，适应低温固化。首先以苯酚将甲苯二异氰酸酯中的至少 $60\\%$ 的NCO基团封闭。同时使环氧树脂与聚酰胺反应，用聚酰胺中的氨基打开环氧环，聚酰胺与环氧树脂摩尔比为 $1/2\\sim2/5$ ，最后在上述环氧聚酰胺加成物中加人上述聚氨酯封闭物，得到聚氨酯改性环氧聚酰胺树脂。  \n\n可以通过将环氧树脂改性提高其柔韧性，例如可以在催化剂存在下使脂族或芳族二元环氧化合物（A）与每分子中含两个芳族羟基（酚羟基）的化合物（B）反应。得到的改性环氧树脂平均环氧当量为 $350{\\sim}30000$ 。应用于卷材涂料时，（A）中脂族二元环氧化合物应占二元环氧化合物总量的 $10\\%\\sim50\\%$ ，改性环氧树脂的环氧当量应为 $1400{\\sim}3000$ 。适合的脂肪族二元环氧化合物如二元含活泼氢脂肪族化合物的二缩水甘油醚类、聚氧化烯二醇缩水甘油醚等。适合的芳族二元环氧化合物如双酚或多酚的二缩水甘油醚类等。上述改性环氧树脂可以用各种氨基树脂及封闭型多异氰酸酯树脂等交联。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 373,
+        "chunk": "# 四、聚酯类底漆  \n\n聚酯底漆的防腐蚀性一般不如环氧底漆，但力学性能优于环氧底漆，是预涂卷材底漆的另一个主要品种。  \n\n以氨基树脂固化的聚酯底漆称为聚酯-氨基底漆，再用环氧树脂改性，能改善漆膜的加 工成型性及防腐性能。以封闭异氰酸酯固化的聚酯底漆称为聚酯-聚氨酯底漆，其切口防腐 蚀性能要优于氨基固化体系。  \n\n典型的预涂卷材聚酯底漆配方见表3-5-15。  \n\n表3-5-15 典型的聚酯底漆配方  \n\n\n<html><body><table><tr><td rowspan=\"2\">原料</td><td rowspan=\"2\">规格</td><td colspan=\"2\">用量/g</td></tr><tr><td>聚酯聚氨酯底漆</td><td>聚酯氨基底漆</td></tr><tr><td>SH 974</td><td>40%</td><td>50.5</td><td>53.7</td></tr><tr><td>封闭异氰酸酯固化剂</td><td>50%</td><td>10.1</td><td>一</td></tr><tr><td>脲醛树脂</td><td>60%</td><td>一</td><td>6.3</td></tr><tr><td>锌铬黄</td><td>工业</td><td>4.2</td><td>4.2</td></tr><tr><td>锶铬黄</td><td>工业</td><td>6.3</td><td>6.3</td></tr></table></body></html>  \n\n续表  \n\n<html><body><table><tr><td rowspan=\"2\">原料</td><td rowspan=\"2\">规格</td><td colspan=\"2\">用量/g</td></tr><tr><td>聚酯聚氨酯底漆</td><td>聚酯氨基底漆</td></tr><tr><td>磷酸锌</td><td>工业</td><td>4.2</td><td>4.2</td></tr><tr><td>钛白</td><td>工业</td><td>10.5</td><td>10.5</td></tr><tr><td>防沉剂（膨润土）</td><td>工业</td><td>0.5</td><td>0.5</td></tr><tr><td>Efka-5066</td><td>汽巴-埃夫卡公司</td><td>1.2</td><td>1.2</td></tr><tr><td>ADP附着力促进剂</td><td>德谦公司</td><td>1.2</td><td>1.2</td></tr><tr><td>Efka-3777</td><td>汽巴-埃夫卡公司</td><td>0.5</td><td>0.5</td></tr><tr><td>二月桂酸二丁基锡</td><td>工业</td><td>0.1</td><td>一</td></tr><tr><td>Byk-450</td><td>毕克公司</td><td>一</td><td>0.5</td></tr><tr><td>二甲苯</td><td>工业</td><td>5.3</td><td>5.5</td></tr><tr><td>环己酮</td><td>工业</td><td>5.4</td><td>5.4</td></tr><tr><td colspan=\"2\">总计</td><td>100.0</td><td>100.0</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 374,
+        "chunk": "# 五、高性能卷材底漆  \n\n开发高性能的预涂卷材底漆对改善整个预涂卷材的加工性能起着非常关键的作用。因此国内外主要卷材涂料研究单位和生产厂商都对此类产品研究都非常重视。如常州涂料化工研究院开发的HY-C-101高性能聚酯聚氨酯底漆，采用以特殊工艺合成的中高分子量聚酯树脂为基料树脂，以氨基树脂和特殊改性的封闭型聚氨酯树脂为交联剂，还加人特殊改性的环氧树脂，提高了力学和耐盐雾性能，涂料的膜厚适应性、烘烤条件适应性和底材适应性强。  \n\n上海振华造漆厂开发了一种用于建筑彩涂板的与氟碳面漆配套的环保型含氟卷材涂料，即环保型含氟底漆。其配方组成（质量分数）如下：氟树脂 $10\\%\\sim30\\%$ ，丙烯酸树脂$10\\%\\sim30\\%$ ，钛白粉 $10\\%\\sim20\\%$ ，防锈颜料 $5\\%\\sim15\\%$ ，助剂 $2\\%\\sim3\\%$ 及有机溶剂 $30\\%\\sim$ $50\\%$ 。该含氟底漆以丙烯酸树脂为载体，PVDF树脂（聚偏二氟乙烯树脂）与丙烯酸树脂共混熔融成膜，添加少量助剂，经高温烘烤固化成为柔韧的漆膜。由于氟碳面漆中也含有同样结构的PVDF树脂，因此涂装面漆时，底漆与面漆中的氟树脂同时熔融，互相渗透固化成膜，整个涂层的致密性更好。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 375,
+        "chunk": "# 六、水性底漆  \n\n采用水性涂料可以减少有机溶剂的用量，具有节能和环保的优点，是涂料工业的发展方向之一。但在预涂卷材生产过程中，烘炉中的有机溶剂能回收利用且几乎没有残余溶剂排入大气，已经符合环保要求。由于水的蒸发热比有机溶剂大，漆膜烘烤固化时需要更多的热量；高温水蒸气易腐蚀烘炉和排气管路，因此在卷材涂装中水性涂料用得不多，即使在欧洲也只有 $1{\\sim}2$ 条水性卷涂线。  \n\n水性卷材底漆中，基料含有可热固化的、水分散型聚氨酯聚合物及可热固性的或热塑性的可成膜的水分散型聚合物，通过两者的协同作用，底漆的性能可以更好，这些性能包括柔韧性和耐冲击、底漆对金属底材和面漆的附着力、耐化学性和防腐性、耐潮气和耐水性及室外耐久性等。热固化的、水分散型聚氨酯聚合物中，聚氨酯聚合物可以是聚酯聚氨酯、有机硅改性聚氨酯、环氧酯改性聚氨酯、丙烯酸聚氨酯等。一般聚氨酯聚合物中含有支链羧基及羟基，用于使聚合物在水中分散、稳定及交联固化。例如最常用的聚酯聚氨酯聚合物，是由多异氰酸酯、多元醇、多羟基羧酸及二元酸制备而得到含支链羧基的聚合物，中和后即可分散于水中。使用封闭型异氰酸酯时，聚氨酯聚合物可以加热固化自交联，聚氨酯聚合物也可以用其他的交联剂如氨基树脂交联固化。聚氨酯聚合物用量通常为基料总质量的 $10\\%\\sim$ $85\\%$ 。聚氨酯聚合物与交联剂的用量可以根据性能调整，较好的聚氨酯聚合物用量为基料总质量的 $15\\%\\sim25\\%$ ，交联剂用量占基料总质量的 $10\\%\\sim20\\%$ 。基料相中还含有热固化（热固型或热塑型）水分散型聚合物，如丙烯酸乳液聚合物或共聚物，适用的水性乳液聚合物有改性丙烯酸聚合物如苯丙乳液、水性聚酯、硅丙乳液、聚氯乙烯、环氧化合物、环氧酯、醋酸乙烯酯及丙烯酸丁酯共聚物、丙烯酸乙酯-甲基丙烯酸甲酯共聚物等。水性乳液聚合物用量通常为基料总质量的 $15\\%\\sim90\\%$ 甲",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 376,
+        "chunk": "# 第六节 预涂卷材用面漆",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 377,
+        "chunk": "# 一、预涂卷材用面漆概述  \n\n预涂卷材用面漆的种类较多，主要有：聚酯面漆、聚乙烯基类面漆、有机硅改性聚酯面漆、丙烯酸类面漆和氟碳面漆等。五类面漆的特性见表3-5-16。  \n\n表3-5-16 常见面漆的特性  \n\n\n<html><body><table><tr><td>特性</td><td>聚酯面漆</td><td>聚乙烯基类面漆</td><td>丙烯酸面漆</td><td>氟碳面漆</td><td>有机硅面漆</td></tr><tr><td>树脂 体系</td><td>异氰酸酯</td><td>PVC有机溶胶、塑 聚酯/氨基或封闭溶胶及不含氯的高聚 物（聚酯、聚烯烃、丙闭异氰酸酯 烯酸等)的分散体</td><td>丙烯酸/氨基或封</td><td>四氟乙烯、聚偏二 氟乙烯、四氟乙烯-乙 烯基醚共聚物和多氟 聚醚等</td><td>有机硅改性聚酯/ 氨基或封闭异氰酸酯</td></tr><tr><td>优点</td><td>性价比高 综合性能好</td><td>PVC塑溶胶为热塑 性，树脂分子量高，加 工性优异，可厚膜涂 装，可压花</td><td>良好的抗沾污性、 抗划伤性和高的光 泽、硬度以及优异的 耐候性和耐化学性</td><td>极好的耐候性、耐 溶剂性、耐化学品性、 耐磨性和加工性以及 抗沾污性</td><td>耐候性好、抗沾污 性和加工性较好</td></tr><tr><td>缺点</td><td></td><td>PVC塑溶胶耐候性 不好</td><td>柔韧性差，加工 性差</td><td>价格较高</td><td>价格较高，硬度 较低</td></tr><tr><td>用途</td><td>普通建筑及家电 彩板</td><td>厚膜涂装 要求压花等具特殊 装饰效果的彩板</td><td>PVDF 和不含氯的 分散体涂料的共用 组分 加工性要求不高的 平面用途如卷铝漆等</td><td>耐候性要求极高的 外用建筑彩板 具有特殊要求（自 清洁性等)的彩板</td><td>耐候性要求较高的 外用建筑彩板 书写板等特殊用途 的彩板</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 378,
+        "chunk": "# 二、聚酯类面漆  \n\n在卷材涂料用面漆中，聚酯树脂涂料是用量最大的品种，通过选择不同的多元酸、多元醇制备不同 $T_{\\tilde{\\mathbf{\\deltaB}}}$ 、不同分子量的线型或支链型聚酯树脂，作为基料树脂。聚酯面漆配制时，可以通过混合不同 $T_{\\mathrm{g}}$ 、不同分子量的聚酯树脂灵活地调控得到的漆膜的性能，通过对聚酯树脂的组成选择耐候性的组分，并通过加入适宜的位阻胺光稳定剂和紫外线吸收剂以及相适应的交联剂，可以制成耐候性十分接近于氟树脂而优于有机硅改性聚酯的涂料，用于户外用建材。  \n\n卷材面漆常用聚酯树脂牌号及参数见表3-5-17和表3-5-18。  \n\n表3-5-17 国产卷材面漆常用聚酯树脂牌号及参数  \n\n\n<html><body><table><tr><td>商品牌号</td><td>固含量/%</td><td>酸值（以树脂固体计）/（mgKOH/g）</td><td>羟值(以树脂固体计)/(mgKOH/g)</td></tr><tr><td>7360</td><td>60.0±1.0</td><td>≤8</td><td>40</td></tr><tr><td>305Y</td><td>60.0±1.0</td><td>≤7</td><td>50</td></tr><tr><td>307B</td><td>60.0±1.0</td><td>≤10</td><td>85</td></tr><tr><td>3360A</td><td>60.0±1.0</td><td>≤6</td><td>80</td></tr><tr><td>3360</td><td>60.0±1.0</td><td>≤8</td><td>80</td></tr><tr><td>3395</td><td>60.0±1.0</td><td>≤8</td><td>80</td></tr><tr><td>3910</td><td>60.0±1.0</td><td>≤8</td><td>60</td></tr><tr><td>3913</td><td>60.0±1.0</td><td>≤5</td><td>85</td></tr><tr><td>3922</td><td>80.0±1.0</td><td>≤12</td><td>100</td></tr><tr><td>3920-3</td><td>60.0±1.0</td><td>≤7</td><td>70</td></tr><tr><td>3971</td><td>60.0±1.0</td><td>≤8</td><td>60</td></tr><tr><td>K-5329</td><td>70±1</td><td>4~8</td><td></td></tr></table></body></html>\n\n$\\textcircled{1}$ 为深圳立骅合成树脂产品，其余为江苏三木集团有限公司产品。  \n\n表3-5-18 进口卷材面漆常用聚酯树脂牌号及参数  \n\n\n<html><body><table><tr><td>商品牌号</td><td>生产厂家</td><td>固含量 /%</td><td>酸值（以树脂固体计） /(mg KOH/g)</td><td>羟值（以树脂固体计） /(mgKOH/g)</td><td>T/C</td><td>分子量</td></tr><tr><td>SN801</td><td>DSM</td><td>65</td><td>0~4</td><td>45</td><td>23</td><td>3000</td></tr><tr><td>SN811</td><td>DSM</td><td>60</td><td>8~12</td><td>120</td><td>-6</td><td>2500</td></tr><tr><td>SN830</td><td>DSM</td><td>60</td><td>3~6</td><td>30</td><td>26</td><td>4500</td></tr><tr><td>SN804</td><td>DSM</td><td>65</td><td>0~4</td><td>45</td><td>一</td><td>一</td></tr><tr><td>SN831</td><td>DSM</td><td>60</td><td>2~5</td><td>33</td><td>25</td><td>5000</td></tr><tr><td>SN833</td><td>DSM</td><td>55</td><td>3~5</td><td>20</td><td>一</td><td>一</td></tr><tr><td>SN844</td><td>DSM</td><td>60</td><td>0~4</td><td>35</td><td>19</td><td>4000</td></tr><tr><td>SN847</td><td>DSM</td><td>70</td><td>6~10</td><td>75</td><td>一</td><td></td></tr><tr><td>SN886</td><td>DSM</td><td>60</td><td>2~6</td><td>33</td><td></td><td></td></tr><tr><td>ES-600</td><td>SK化工</td><td>100</td><td>一</td><td>16~20</td><td>52</td><td>7000</td></tr><tr><td>ES-710</td><td>SK化工</td><td>100</td><td>一</td><td>23~27</td><td>37</td><td>10000</td></tr><tr><td>VPE 6104/60MPAC</td><td>CYTEC</td><td>60</td><td>≤8</td><td>60</td><td>一</td><td>一</td></tr><tr><td>VPE 6128/70SNABG</td><td>CYTEC</td><td>70</td><td>8~12</td><td>60</td><td>一</td><td>一</td></tr><tr><td>PE 6163/666SNABG</td><td>CYTEC</td><td>66</td><td>≤8</td><td>一</td><td>一</td><td></td></tr><tr><td>223</td><td>GALSTAFF</td><td>60±2</td><td>22</td><td>85.8</td><td>一</td><td>一</td></tr><tr><td>224</td><td>GALSTAFF</td><td>70±2</td><td>15</td><td>46.2</td><td>一</td><td></td></tr><tr><td>226</td><td>GALSTAFF</td><td>69±2</td><td>15</td><td>52.8</td><td>一</td><td></td></tr><tr><td>228</td><td>GALSTAFF</td><td>70±2</td><td>15</td><td>52.8</td><td>一</td><td></td></tr><tr><td>233</td><td>GALSTAFF</td><td>75.0±1.5</td><td>14~20</td><td>148.5</td><td>一</td><td>一</td></tr><tr><td>LH818</td><td>degussa</td><td>50</td><td><3</td><td>20</td><td>35</td><td>6000</td></tr><tr><td>LH826</td><td>degussa</td><td>55</td><td><3</td><td>20</td><td>30</td><td>6000</td></tr><tr><td>LH829</td><td>degussa</td><td>60</td><td><3</td><td>35</td><td>25</td><td>3000</td></tr><tr><td>LH830</td><td>degussa</td><td>60</td><td><3</td><td>35</td><td>20</td><td>4000</td></tr><tr><td>LH822</td><td>degussa</td><td>55</td><td><3</td><td>20</td><td>15</td><td>6000</td></tr><tr><td>LH832</td><td>degussa</td><td>60</td><td><3</td><td>35</td><td>15</td><td>4000</td></tr><tr><td>LH831</td><td>degussa</td><td>70</td><td>5</td><td>50</td><td>15</td><td>2000</td></tr><tr><td>LH908</td><td>degussa</td><td>65</td><td>5</td><td>40</td><td>15</td><td>3000</td></tr><tr><td>LH828</td><td>degussa</td><td>70</td><td>10</td><td>50</td><td>10</td><td>2000</td></tr></table></body></html>\n\n典型的聚酯面漆配方见表3-5-19。  \n\n表3-5-19 典型的聚酯面漆配方（白漆及蓝）  \n\n\n<html><body><table><tr><td rowspan=\"2\">原料</td><td rowspan=\"2\">规格</td><td colspan=\"2\">用量/g</td></tr><tr><td>白漆</td><td>蓝漆</td></tr><tr><td>LH828 Efka-5010</td><td>德固萨，70% 汽巴-埃夫卡分散剂</td><td>19.9 1.3</td><td>16.0 一</td></tr><tr><td>Efka-4080</td><td>汽巴-埃夫卡分散剂</td><td></td><td>1.0</td></tr><tr><td>Efka-6220</td><td>汽巴-埃夫卡分散剂</td><td>一</td><td>0.1</td></tr><tr><td>R-706</td><td>杜邦，金红石型钛白</td><td>32.6</td><td>13.4</td></tr><tr><td>酞菁蓝</td><td>BGS</td><td>一</td><td>3.3</td></tr><tr><td>混合溶剂</td><td>工业 研磨至细度≤15um后，加人以下物料，高速分散下搅拌均匀</td><td>11.7</td><td>13.4</td></tr><tr><td colspan=\"4\"></td></tr><tr><td>LH-828 Cymel 303</td><td>德固萨，70% HMMM,98%</td><td>18.3 6.0</td><td>29.8 7.2</td></tr><tr><td>HP-260</td><td></td><td></td><td></td></tr><tr><td>MP-1200</td><td>德谦，消光粉</td><td>1.6</td><td>1.9</td></tr><tr><td></td><td>杜邦，聚四氟乙烯蜡</td><td>0.3</td><td>0.4</td></tr><tr><td>Byk-450</td><td>毕克公司，固化催化剂</td><td>1.3</td><td>1.2</td></tr><tr><td>Efka-8385</td><td>汽巴-埃夫卡流平剂</td><td>0.3</td><td>0.4</td></tr><tr><td>Efka-3600</td><td>汽巴-埃夫卡流平剂</td><td>0.1</td><td>0.1</td></tr><tr><td>混合溶剂</td><td>工业</td><td>6.6</td><td>11.8</td></tr><tr><td colspan=\"2\">总计</td><td>100.0</td><td>100.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 379,
+        "chunk": "# 三、聚乙烯类面漆  \n\n除聚酯面漆以外，卷材涂料面漆中用得最多的是聚乙烯基类，包括PVC有机溶胶和塑溶胶面漆以及不含氯的分散体涂料。塑溶胶可以厚膜涂装，保温性能好，在气候寒冷的北方地区应用较多。PVC有机溶胶和塑溶胶是将溶胶级的聚氯乙烯粉末分散在有机溶剂和增塑剂中，或只分散在增塑剂中的分散体，前者称为有机溶胶，后者称为塑溶胶。不含氯的分散体涂料是将其他高聚物粉末如聚酯、聚烯烃、丙烯酸等在增塑剂中形成的塑溶胶，实际上是一种溶液分散型涂料，树脂溶液一般由端羟基聚酯或丙烯酸和封闭多异氰酸酯及溶剂组成。  \n\n一种不含氯的聚烯烃树脂分散体及涂料的制备方法举例如下：取100份聚烯烃聚合物[PO，由 $90\\%$ 乙烯-丙烯酸共聚物与 $10\\%$ 马来酸改性的EPM橡胶（乙烯-丙烯橡胶）组成」与43份环氧树脂（双酚A型，环氧当量 $875\\sim1000\\mathrm{g/eq}$ ，分子量 $>700\\mathrm{g/mol};$ 在 $130\\sim$ $140^{\\circ}C$ 下用捏合机混合均匀；加人21份环氧稀释剂（ $\\mathbf{1}:\\mathbf{1}$ 的己二醇二缩水甘油醚和单缩水甘油醚)，混合均匀得到均匀的玻璃状熔融体；冷却至 $90^{\\circ}C$ ，继续捏合混合，当冷至聚烯烃熔融温度以下，出现相分离，聚烯烃以非常小的粒径沉淀出来，分散于树脂稀释溶液中；加人21份环氧稀释剂，在 $90^{\\circ}C$ 捏合并继续冷却，得到软浆状分散体。分散的聚烯烃平均粒径$5\\mu\\mathrm{m}$ 。将该分散体制备成塑溶胶的方法为：取186份聚烯烃分散体，与108份 $1:1$ 的己二醇二缩水甘油醚和单缩水甘油醚、74份己二醇二缩水甘油醚、29份邻苯二甲酸二异壬酯、80份滑石粉、6份 $N,N-(4-$ 甲基-间亚苯基）双 $(N^{\\prime},N^{\\prime}$ -二甲基脲)、17份双氰胺与0.08份黑色颜料在 $60^{\\circ}C$ 在混合机中混合均匀，得到玻璃浆状产物，其熔融温度不超过 $70^{\\circ}C$ 。塑溶胶可施工于各种底材（如钢板、铝板、镀锌钢板等）上，膜厚 $1.5\\sim2\\mathrm{mm}$ （普通卷材涂膜的底面总膜厚不超过 $30\\mu\\mathrm{m}\\mathrm{\\vec{\\mathrm{n}}.\\mu\\mathrm{m}\\vec{\\mathrm{n}}.}$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 380,
+        "chunk": "# 四、丙烯酸类面漆  \n\n溶剂型热固性丙烯酸涂料是早期彩钢板面漆的主要品种之一，以后随着聚酯面漆的发  \n\n展，逐渐被其取代。现在主要用作PVDF和不含氯的分散体涂料的共用组分以及加工性要求不高的平面用途如卷铝等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 381,
+        "chunk": "# 五、耐久型面漆  \n\n建筑用卷材应用领域的不断拓展，对卷材涂料提出更高的要求，推动了高性能卷材涂料的开发。现在，无论是机场、体育馆等大型的公共设施，还是高级办公楼、超级市场、工业厂房，已经越来越多地采用预涂彩钢板，这些建筑都希望涂料有更长的使用期，即需要涂装耐久型涂料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 382,
+        "chunk": "# 1.耐久型聚酯面漆  \n\n采用耐久性、耐化学性好的聚酯合成原料，如以脂肪族或脂环族原料取代芳香族原料，可以制备高耐久型聚酯树脂（通常简称为SDP或HDP树脂)。通过减少对紫外线的吸收改善了耐候性，再辅以适宜的交联树脂和耐久性好的颜填料及助剂，制备的高耐久性聚酯卷材涂料具有优异的耐候性，同时保持优异的力学性能，且配方及合成工艺、施工等更接近于普通聚酯树脂涂料，具有一定的价格优势，因而成为高耐久性卷材涂料的发展方向之一。这类产品例如上海振华造漆厂研制出的耐久聚酯卷材面漆，人工加速老化试验UVA（340灯）达到 $2000\\mathrm{{h}}$ 以上、UVB（313灯）达到 $\\boldsymbol{\\mathrm{1000h}}$ 以上。SK化工有限公司研制出的SKYBON$\\mathrm{ES-SDP}$ 耐久高分子量饱和聚酯，综合性能优异，人工老化试验（氙灯老化）1500h保光率$75\\%$ 以上。常州涂料化工研究院研制出的耐久型聚酯面漆，老化性能优异，UVB（313灯)试验结果达到 $1000\\mathrm{h}$ 以上（失光、变色均为一级，无粉化等涂膜破坏现象）。  \n\n耐久型聚酯树脂的制备：在带有温度计、搅拌和回流冷凝器的反应容器中加人 $297.5\\mathrm{g}$ 环己烷二甲酸、 $50.5\\dot{\\mathbf{g}}$ 己二酸、 $207.48$ 新戊二醇、 $44.5\\mathrm{g}$ 三羟甲基丙烷、 $0.6\\dot{\\mathrm{g}}$ 二月桂酸二丁基锡和 $\\widehat{\\mathfrak{f}}\\widehat{\\mathfrak{f}}_{\\mathbf{\\Xi}}$ 二甲苯，以 $3\\sim5\\mathrm{h}$ 升温至 $220^{\\circ}C$ 并保温回流脱水反应至酸值 ${<}3\\mathrm{mg}~\\mathrm{KOH/g}$ 脱水量约 $74.6g$ ，降温至 $<160^{\\circ}C$ ，加人兑稀溶剂 $282.9\\underline{{\\sigma}}$ ，得到耐久型聚酯树脂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 383,
+        "chunk": "# 2.氟碳面漆  \n\n氟聚物分散体涂料具有优异的室外耐久性、耐化学品性和适宜的力学性能，特别适用于耐候性要求高的室外用建筑彩板市场。  \n\n用于卷材的氟碳面漆可以分为热固型与热塑型两大类。  \n\n热固型涂料中氟树脂分子中含有羟基等活性基团，成膜时可以通过活性基团与氨基树脂、聚氨酯树脂反应交联固化，这类涂料中应用最成功的FEVE树脂，其以三氟氯乙烯为基本结构单元，乙烯基乙醚和氟烯烃单元交替连接，赋予涂层优异的耐候性和耐化学性。氟烯烃单元保护了不稳定的乙烯基醚结构单元，使其免受氧化侵蚀；侧链利用乙烯基醚提供树脂溶解性、硬度、柔韧性和化学交联活性；侧链羟基提供交联点；侧链羧基提高树脂与底材的附着，同时提高了颜料在树脂中的分散性。FEVE树脂如日本旭硝子的商品名为LUMI-FLON与大日本油墨商品名为FLUONATE的产品。  \n\n以FEVE交联型氟树脂作为基料制备喷涂铝材的厂家目前国外有PPG，国内有两家，即上海衡峰氟碳材料有限公司和无锡万博涂料化工有限公司。PPG采用日本旭硝子公司的LF-600X氟树脂、上海衡峰采用日本大金公司的常温及中温固化的PTFE 型交联氟树脂，采用三喷一烘湿碰湿工艺以及板温 $180^{\\circ}\\mathrm{C}\\times15\\mathrm{min}$ 的工艺，产品质量符合现行国家标准要求。无锡万博涂料化工有限公司自行合成了喷涂铝型材及板材氟涂料所需交联型氟树脂，产品质量全部按AAMA2605—1998标准进行检验，达到标准要求。  \n\n热塑性氟树脂涂料应用最广泛的为PVDF，PVDF为结晶体聚合物，其不含活性基团，基本结构单元为CHCF2，基本不溶于非极性溶剂，仅在较高温度能溶于少数极性强溶剂，PVDF不能单独用作涂料，通常要加人热塑性丙烯酸树脂，提高颜料分散性能和与底材的附着力。该类涂料中，以氟聚物粒子与丙烯酸树脂预先热熔融得到的混合物为成膜基料，其中，氟聚物为被分散相，丙烯酸聚合物溶液为连续相。  \n\n应用于建筑彩板的PVDF树脂以瓦特（Pannwalt）公司开发的KYNAR500和苏威  \n(Solvay Solexis）的Hylar5000为代表。氟碳涂料制造商需获得这两家公司的质量许可才能  \n生产PVDF 氟涂料，涂装厂也需获得涂料制造商所需的生产许可才能从事PVDF 氟碳涂装。国外氟碳树脂及涂料主要生产厂商见表3-5-20。  \n\n表3-5-20 氟碳树脂及涂料主要生产厂商  \n\n\n<html><body><table><tr><td>树脂类型</td><td>氟涂料类型</td><td>代表产品</td><td>生产公司</td><td>备注</td></tr><tr><td>PVDF</td><td>一</td><td>Kynar 500</td><td>瓦特</td><td>生产树脂</td></tr><tr><td>PVDF</td><td>一</td><td>Hylar 5000</td><td>苏威</td><td>生产树脂</td></tr><tr><td>一</td><td>PVDF/丙烯酸涂料</td><td>Duranar（三涂色漆）</td><td>PPG</td><td>热熔型涂料</td></tr><tr><td>一</td><td>PVDF/丙烯酸涂料</td><td>DuranarXL（四涂金属漆）</td><td>PPG</td><td>热熔型涂料</td></tr><tr><td>一</td><td>PVDF/丙烯酸涂料</td><td>FluroponClassicⅡ（二涂珠光）</td><td>Valspar</td><td>热熔型涂料</td></tr><tr><td>一</td><td>PVDF/丙烯酸涂料</td><td>FluroponPremiere（三涂色漆）</td><td>Valspar</td><td>热熔型涂料</td></tr><tr><td>一</td><td>PVDF/丙烯酸涂料</td><td>Fluroceram</td><td>BASF</td><td>热熔型涂料</td></tr><tr><td>一</td><td>PVDF/丙烯酸涂料</td><td>Spray Trinar</td><td>AKZO</td><td>热熔型涂料</td></tr><tr><td>FEVE</td><td>一</td><td>LF-600x</td><td>旭硝子</td><td>交联型树脂</td></tr><tr><td>一</td><td>FEVE</td><td>Duranar EX（二涂）</td><td>PPG</td><td>交联型涂料</td></tr></table></body></html>  \n\n氟树脂的性能见表3-5-21。  \n\n表3-5-21PVDF树脂的典型性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">性能</td><td colspan=\"3\">典型数据</td></tr><tr><td>Kynar 500(瓦特)</td><td>Hylar5000（苏威）</td><td>FR-921(3F)</td></tr><tr><td>熔点/℃</td><td></td><td>150～160</td><td>156~161</td></tr><tr><td>相对密度 熔融黏度（232℃，100s-1）/×10-1Pa·s</td><td>29000~33000</td><td>1.75~1.76</td><td>1.75~1.77 熔体流动速率1.0～6.0g/10min</td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td>外观</td><td>白色粉末，无杂质</td><td></td><td>白色粉末</td></tr><tr><td>气味</td><td></td><td>无味</td><td>无味</td></tr><tr><td>吸水率/%</td><td></td><td>≤0.5</td><td>含水率≤0.1</td></tr><tr><td>纯度</td><td>≥99.5%PVDF</td><td></td><td></td></tr><tr><td>热分解温度/℃</td><td></td><td>382~393</td><td>316</td></tr></table></body></html>  \n\nKynar 500和Hylar5000性能基本相当，均承诺如果涂料中基料总量（质量）的70%为PVDF（其余30%为丙烯酸树脂）则性能保证满足AAMA2605—1998标准。交联型FE-VF树脂的比较见表3-5-22。  \n\n表3-5-22 交联型FEVE树脂的比较  \n\n\n<html><body><table><tr><td>项目</td><td>LF-552(旭硝子)</td><td>LF-600x(旭硝子)</td><td>WF-401（无锡万博）</td></tr><tr><td>特征</td><td>柔韧级</td><td>柔韧级</td><td>耐温级</td></tr><tr><td>应用领域</td><td>卷材涂料</td><td>卷材涂料</td><td>氟碳喷涂铝材</td></tr><tr><td>T/C</td><td>20</td><td>20</td><td>20~25</td></tr><tr><td>OHV/(mg KOH/g)</td><td>52</td><td>50</td><td>50±10</td></tr><tr><td>AV/(mg KOH/g)</td><td>5</td><td>0</td><td>0~8</td></tr><tr><td>固体含量/%</td><td>40</td><td>50</td><td>50</td></tr><tr><td>相对密度</td><td>1.06</td><td>1.08</td><td>1.05～1.10</td></tr><tr><td>溶剂</td><td>Solvesso150/环已酮</td><td>二甲苯</td><td>醋酸丁酯/二甲苯/环已酮</td></tr></table></body></html>  \n\n从上面数据比较，不同厂家树脂差别不大，氟含量均在 $25\\%$ 以上。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 384,
+        "chunk": "# 3.有机硅改性聚酯面漆  \n\n从成本和性能综合考虑，适用于卷材涂料的有机硅树脂主要为有机硅改性聚酯树脂，其硅氧烷含量通常为 $15\\%\\sim50\\%$ （质量分数)。有机硅改性聚酯具有优异的耐污染、耐候性，其粘接性好、固化快，可适应预涂卷材涂装要求，非常适用于制备耐久型卷材面漆。由其制备的涂料形成的涂膜具有优异的自洁、保光、保色、不粉化性，且坚韧耐磨。  \n\n有机硅改性聚酯可以分为冷拼和热反应两种方法，前者是将有机硅树脂和聚酯树脂机械混合，然后加入交联剂、颜料和助剂等制备涂料，烘烤固化成膜。后者是使聚酯树脂和有机硅中间体加热反应，先制备有机硅改性聚酯树脂，以其为基料树脂制备涂料。冷拼法为物理混合，在提高耐候性和保光保色性上不如热反应法。  \n\n热反应制备的有机硅改性聚酯树脂根据桥联结合方式，可分为Si—C型和Si—O—C型两种。前者由含羧基的有机硅（氧）烷与多元醇反应制备，但因原料昂贵、工艺复杂，至今尚未工业化生产。后者通过含羟基的聚酯与含烷氧基的硅（氧）烷或含硅羟基的硅（氧）烷经缩合反应而制备，原料易得，生产工艺简便，因而被广泛应用。其反应式为：  \n\n$$\n\\mathbf{\\lambda}=\\mathbf{SiOR+HOC=}\\mathbf{\\lambda}=\\mathbf{SiOC}=+\\mathbf{ROH}\n$$  \n\n$$\n\\mathrm{\\equiv}\\mathrm{SiOH+HOC=\\mathrm{\\longrightarrow\\equiv}S i O C=+H_{2}O}\n$$  \n\n此外，将含官能基的硅烷或硅氧烷与过量的多元醇缩合，然后再与多元羧酸反应，也可以制得Si—O—C型有机硅改性聚酯树脂。  \n\n热固性有机硅改性聚酯树脂性能优异，成本适中，因此国内外主要卷材涂料研究单位和生产厂商都有此类产品。如上海振华造漆厂研制出的有机硅聚酯卷材涂料，人工老化试验达到 $2000\\mathrm{h}$ ，其具有优异的户外耐候性、保光和保色性。常州涂料化工研究院研制出的有机硅改性聚酯耐久卷材涂料，人工加速老化试验 $2000\\mathrm{h}$ 以上（失光、变色和粉化均为1级），QUV-B（313灯）试验 ${\\mathfrak{E}}{\\boldsymbol{0}}{\\boldsymbol{0}}{\\mathbf{h}}$ 以上不失光(1级)。国外一些知名卷材涂料生产厂商如贝格(BECKER)、金刚化工（KCC）也都有有机硅改性聚酯型耐久涂料产品。  \n\n有机硅改性聚酯树脂的制备：在带有温度计、搅拌和回流冷凝器的反应容器中加人$212.4\\dot{\\mathbf{g}}$ 间苯二甲酸、 $220.1\\mathrm{g}$ 环已烷二甲酸、31.1g己二酸、 $277.0\\mathbf{g}$ 新戊二醇、 $58.4\\mathrm{\\AA}$ 三羟甲基丙烷、 $0.4\\mathbf{g}$ 二月桂酸二丁基锡和 $80\\mathbf{g}$ 二甲苯，以 $3\\sim5\\mathrm{h}$ 升温至 $220^{\\circ}C$ 并保温回流脱水反应至酸值 ${<}3\\mathrm{mg}~\\mathrm{KOH/g}$ ，降温至 $<160^{\\circ}C$ ，加人混合溶剂（ $\\mathsf{S}\\mathrm{-}150^{\\sharp}$ ：DBE：丙二醇甲醚醋酸酯 $=6\\div2:2,$ $609,3{\\mathrm{g}}$ 兑稀；加人硅氧烷中间体DC3074（道康宁） $213.9\\mathbf{g}$ 、钛酸四异丙酯 $0.5\\mathrm{g}$ ，升温至 $160{\\sim}180^{\\circ}\\mathrm{C}$ 脱醇反应 $\\mathbf{\\hat{l}}\\sim2\\mathbf{h}$ ，取样观察至树脂透明为终点。  \n\n![](images/dc4ab9df99f23f3198c6e9b2e3a7363c186c7162782fa4e2be17f3c3e2e98896.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 385,
+        "chunk": "# 一、背漆概述  \n\n背面漆主要是在卷材的背面起防护作用。背漆大多采用单涂层，要求较高的应用中也有采用带底背漆的二涂层体系的。背漆一般涂膜较薄，在装饰性和户外耐久性方面要求不高，但要求抗划伤性、抗粘连性和加工性、较好的耐MEK和耐盐雾性能。用于一些特殊用途时，背漆还需要具有一些特殊的性能要求。例如对有些应用如制备泡沫夹芯板时，需要背漆有良好的耐贴发泡层性能，彩板发泡用粘接剂通常为双组分聚氨酯类型，一个组分为异氰酸酯，另一组分为羟基化合物，两组分混合发生交联反应；粘接强度主要取决于表面的活性基团的数量，活性基团越多，粘接强度越高；背漆常用体系中，环氧聚氨酯的发泡粘接性能最好。应用于家电彩板时，往往还要求背漆具有良好的导电性，如用于数字电视机顶盒等视听类产品时，要求背面电阻 $<20\\Omega$ 。有些应用中，采用镀锌钢板为基板，可以直接在背面涂覆耐指纹涂料，获得所需的耐指纹性和防腐保护性能。  \n\n普通的卷材背漆主要分为环氧和聚酯两大类。环氧背漆又分为普通坏氧背漆和改性坏氧背漆。如江苏鸿业涂料有限公司生产的HY-C-05背漆属于普通环氧背漆，HY-E-05背漆属于改性环氧背漆。另一大类为聚酯背漆。  \n\n各类常见背漆的特性见表3-5-23。  \n\n表3-5-23 各类背漆的特性  \n\n\n<html><body><table><tr><td>特性</td><td>普通环氧背漆</td><td>改性环氧背漆</td><td>聚酯背漆</td></tr><tr><td>树脂体系</td><td>高分子环氧/封闭异氰酸 酯或氨基树脂</td><td>改性环氧/封闭异氰酸酯或氨基树脂</td><td>聚酯/氨基或封闭异氰酸酯</td></tr><tr><td>优点</td><td>贴发泡层性好 耐盐雾性好</td><td>反应活性高，耐MEK擦拭性能好 硬度高，耐划伤性好 贴发泡层性好 耐盐雾性好</td><td>柔韧性优于环氧 成本较低</td></tr><tr><td>缺点</td><td>反应活性低 柔韧性差</td><td>成本较高 柔韧性差</td><td>耐MEK擦拭性能差 聚酯/氨基背漆贴发泡层性能较差</td></tr><tr><td>用途</td><td>加工性要求一般的建筑 彩板</td><td>加工性要求较高的建筑或家电彩板</td><td>不需要贴发泡层的建筑或家电彩板</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 386,
+        "chunk": "# 二、环氧背漆  \n\n环氧背漆所用环氧树脂要求与底漆基本相同，也是采用大分子环氧或改性环氧树脂。典型的环氧背漆配方见表3-5-24。  \n\n表3-5-24 典型的环氧背漆配方  \n\n\n<html><body><table><tr><td>原料</td><td>规格</td><td>环氧聚氨酯背漆用量/g</td></tr><tr><td>EPIKOTE 1009环氧</td><td>50%溶液</td><td>37.8</td></tr><tr><td>封闭异氰酸酯固化剂</td><td>50%溶液</td><td>12.6</td></tr><tr><td>R-902</td><td>钛白，杜邦公司</td><td>17.6</td></tr><tr><td>锌铬黄</td><td>工业</td><td>2.5</td></tr><tr><td>三聚磷酸铝</td><td>工业</td><td>5.0</td></tr><tr><td>有机膨润土</td><td>临安涂料助剂厂</td><td>0.5</td></tr><tr><td>Efka-8512</td><td>汽巴-埃夫卡公司，分散剂</td><td>0.5</td></tr><tr><td>Syloid C-807</td><td>格雷斯公司，消光粉</td><td>0.8</td></tr><tr><td>Efka-3777</td><td>汽巴-埃夫卡公司，流平剂</td><td>0.3</td></tr><tr><td>二甲苯</td><td>工业</td><td>11.2</td></tr><tr><td>环己酮</td><td>工业</td><td>11.2</td></tr><tr><td colspan=\"2\">总计</td><td>100.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 387,
+        "chunk": "# 三、聚酯背漆  \n\n近年来，聚酯背漆的应用越来越多，包括聚酯聚氨酯背漆和聚酯氨基背漆。  \n卷材背漆用聚酯树脂牌号及参数见表3-5-25和表3-5-26。  \n\n表3-5-25 江苏三木公司卷材背漆用聚酯树脂牌号及参数  \n\n\n<html><body><table><tr><td>商品牌号</td><td>固含量/%</td><td>酸值（以树脂固体计）/（mgKOH/g）</td><td>羟值（以树脂固体计）/(mgKOH/g）</td></tr><tr><td>305Y</td><td>60.0±1.0</td><td>≤7</td><td>50</td></tr><tr><td>307B</td><td>60.0±1.0</td><td>≤10</td><td>85</td></tr><tr><td>3316</td><td>55.0±1.0</td><td>≤8</td><td>60</td></tr><tr><td>3360A</td><td>60.0±1.0</td><td>≤6</td><td>80</td></tr><tr><td>3317</td><td>60.0±1.0</td><td>≤8</td><td>80</td></tr><tr><td>3395</td><td>60.0±1.0</td><td>≤8</td><td>80</td></tr><tr><td>3920-2</td><td>60.0±1.0</td><td>≤7</td><td>70</td></tr><tr><td>3913</td><td>60.0±1.0</td><td>≤5</td><td>85</td></tr><tr><td>3922</td><td>80.0±1.0</td><td>≤12</td><td>100</td></tr><tr><td>3920-1</td><td>60.0±1.0</td><td>≤7</td><td>70</td></tr><tr><td>3966</td><td>60.0±1.0</td><td>≤6</td><td>100</td></tr></table></body></html>  \n\n表3-5-26进口卷材背漆常用聚酯树脂牌号及参数  \n\n\n<html><body><table><tr><td rowspan=\"2\">商品牌号</td><td rowspan=\"2\">生产厂家</td><td rowspan=\"2\">固含量 /%</td><td rowspan=\"2\">酸值（以树脂固体计）</td><td rowspan=\"2\">羟值（以树脂固体计） /(mg KOH/g)</td><td rowspan=\"2\">T/C</td><td rowspan=\"2\">分子量</td></tr><tr><td>/(mgKOH/g)</td></tr><tr><td>SN822</td><td>DSM</td><td>70</td><td>3~6</td><td>80</td><td>17</td><td>2500</td></tr><tr><td>SN887</td><td>DSM</td><td>65</td><td>0~8</td><td>90</td><td>一</td><td>一</td></tr><tr><td>LH832</td><td>degussa</td><td>60</td><td><3</td><td>35</td><td>15</td><td>4000</td></tr><tr><td>LH908</td><td>degussa</td><td>65</td><td>5</td><td>40</td><td>15</td><td>3000</td></tr><tr><td>LH828</td><td>degussa</td><td>70</td><td>10</td><td>50</td><td>10</td><td>2000</td></tr><tr><td>LH727</td><td>degussa</td><td>65</td><td>10</td><td>100</td><td>10</td><td>2000</td></tr></table></body></html>  \n\n典型的聚酯背漆配方见表3-5-27。  \n\n表3-5-27 典型的聚酯背漆配方  \n\n\n<html><body><table><tr><td rowspan=\"2\">原料</td><td rowspan=\"2\">规格</td><td colspan=\"2\">用量/g</td></tr><tr><td>聚酯聚氨酯底漆</td><td>聚酯氨基底漆</td></tr><tr><td>SN 822</td><td>70%</td><td>22.3</td><td>25.8</td></tr><tr><td>EPIKOTE 1001</td><td>环氧，60%溶液</td><td>9.0</td><td>10.0</td></tr><tr><td>封闭异氰酸酯固化剂</td><td>50%</td><td>14.0</td><td>一</td></tr><tr><td>Cymel 325</td><td>84%，氨基树脂，氰特公司</td><td>一</td><td>7.1</td></tr><tr><td>锌铬黄</td><td>工业</td><td>2.8</td><td>3.0</td></tr><tr><td>三聚磷酸铝</td><td>工业</td><td>5.6</td><td>6.0</td></tr><tr><td>R-902</td><td>钛白，杜邦公司</td><td>19.6</td><td>21.0</td></tr><tr><td>有机膨润土</td><td>临安涂料助剂厂</td><td>0.5</td><td>0.6</td></tr><tr><td>Efka-8512</td><td>汽巴-埃夫卡公司</td><td>0.6</td><td>0.7</td></tr><tr><td>Syioid C-807</td><td>格雷斯公司，消光粉</td><td>0.9</td><td>1.0</td></tr><tr><td>Efka-3777</td><td>汽巴-埃夫卡公司</td><td>0.5</td><td>0.8</td></tr><tr><td>二月桂酸二丁基锡</td><td>工业</td><td>0.1</td><td>一</td></tr><tr><td>N-3225</td><td>毕克公司</td><td>一</td><td>0.8</td></tr><tr><td>混合溶剂</td><td>工业</td><td>24.1</td><td>17.2</td></tr><tr><td colspan=\"2\">总计</td><td>100.0</td><td>100.0</td></tr></table></body></html>  \n\n带底背面漆多为聚酯氨基体系，配方组成与聚酯氨基面漆类似，  \n\n在用于家电板时，在许多情况下，要求背漆具有导电性能，常州涂料化工研究院通过特殊的改性环氧树脂的合成以及特殊的导电颜料的选用，开发出了一种具有优异的导电性能而且成本较低的导电背漆，该导电涂料属于添加型导电涂料，涂层导电机理主要是渗流作用和隧道效应。渗流作用是导电粒子相互接触产生的导电作用，导电粒子数量增加，涂膜导电性能越好。导电粒子成膜后粒子间有绝缘性聚合物包覆，导电粒子之间，通过聚合物薄层的导电机理主要是量子力学的隧道效应，当两个导电粒子之间的非导电层很薄时，在电场作用下，电子越过很低的势垒（或者说经过隧道）而流动的现象称为隧道效应。利用这两种导电机理制备的导电涂料在含铁磁性底材上的电阻值可 $-20\\Omega$ 。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 388,
+        "chunk": "# 第八节 卷铝涂料  \n\n国内市场上习惯根据基板种类将预涂卷材分为两大类，以钢板为基板的称为卷钢，其所用涂料称为卷钢涂料；以铝板为基板的称为卷铝，其所用涂料称为卷铝涂料。彩铝辊涂生产线产品为各类彩色涂层铝卷，其主要用于加工铝塑复合板和天花吊顶板等，应用于建筑装饰、轻工、办公、家具等行业，用于室内外墙壁、廊柱、顶棚、卫生间、厨房和家具、橱柜、百叶窗、门窗及广告牌、幕墙、橱窗等的装饰装潢。产品必须满足装饰性、成型性、抗腐蚀性和耐候性等要求。",
+        "category": " Introduction"
+    },
+    {
+        "id": 389,
+        "chunk": "# 一、卷铝及铝塑复合板生产工艺  \n\n与彩钢板相似，铝卷材的涂装生产线也主要由三大部分组成，即人口段（开卷和接片等）、工艺段（包括前处理、涂料涂装和涂料固化）和出口段（后处理及收卷）三大工艺部分。典型的卷铝及铝塑复合板生产艺流程如图3-5-8和图3-5-9所示。  \n\n![](images/39dd6cfb065213fe16918363d0081a289cc5c0d94d389f8fa6ca5956ea674b1d.jpg)  \n图3-5-8二涂二烘铝卷涂装生产线工艺流程图  \n\n![](images/c1827dfb33caa93373b4e4e803454be73edbc747cb10b0cb17f8eda974cdff9e.jpg)  \n图3-5-9 铝塑复合板生产线工艺流程图  \n\n典型的铝卷涂装线及铝塑板生产线技术参数见表3-5-28和表3-5-29。  \n\n表3-5-28典型的铝卷涂装线技术参数  \n\n\n<html><body><table><tr><td>项目</td><td>薄板线</td><td>厚板线</td><td>双涂线</td></tr><tr><td>功能</td><td>在铝板或铝箔上连续辑涂 将涂料固化后收成一卷</td><td>在铝板上连续辊涂各种颜 各种颜色的聚酯/PE涂料，色的聚酯/PE涂料，将涂料 固化后收成一卷</td><td>在钢板上连续二次辊涂各种 颜色的聚酯/PE、氟碳/PVDF 涂料，将涂料二次固化后收成</td></tr><tr><td>涂装铝板厚度/mm</td><td>0.03~0.15</td><td>0.15~0.70</td><td>一卷 0.30~0.80</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>项目</td><td>薄板线</td><td>厚板线</td><td>双涂线</td></tr><tr><td>涂装铝板宽度/mm</td><td>1000～1300</td><td>1000～1600</td><td>1000～1600</td></tr><tr><td>涂装速度/（m/min）</td><td>10～25</td><td>10～25</td><td>10～25</td></tr><tr><td>涂层干膜厚度/μm</td><td>(12±1)~(18±1)</td><td>≥18</td><td>≥25</td></tr></table></body></html>  \n\n表3-5-29 典型的铝塑板生产线技术参数  \n\n\n<html><body><table><tr><td>项目</td><td>窄板线</td><td>宽板线</td></tr><tr><td>功能</td><td>将彩色铝涂板与PE材料通过高分</td><td>将彩色铝板与PE材料通过高分子原料 子原料加热、加压工艺情况下连续合在加热、加压工艺情况连续合成各种规格</td></tr><tr><td>铝塑复合板厚度/mm</td><td>成为各种规格的铝塑复合板材 1~4</td><td>的铝塑复合板材 3~5</td></tr><tr><td>铝塑复合板宽度/mm</td><td>1000~1240</td><td>1000～1600</td></tr><tr><td>彩涂铝板及底板厚度/mm</td><td>0.03~0.50</td><td>0.20～0.50</td></tr><tr><td>铝塑复合线线速度/（m/min）</td><td>1.5~2.5</td><td>1.5~2.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 390,
+        "chunk": "# 1.卷铝的前处理  \n\n预处理工段主要包括热碱脱脂、热水清洗、化学处理和钝化处理几个工序。预涂卷铝基板表面会残留防锈油脂、润滑剂以及氧化膜等，在运输过程中还可能黏附其他物质，如果不去除这些油脂及黏附物，会对卷铝的涂装和使用造成影响。另外，在清洁干净的基板表面需要经过化学处理以生成稳定的转化膜，从而提高基板的耐腐蚀性及对涂料的附着力。  \n\n(1）热碱脱脂预涂线线速较快，因此所用的脱脂剂一般浓度较高，典型的脱脂剂含有氢氧化钠（NaOH)、碳酸钠（ $\\mathrm{(Na_{z}C O_{3})}$ 、水玻璃（ $\\mathrm{{Na}_{2}\\mathrm{{SiO}_{3})}}$ 、磷酸盐等组分。热碱脱脂工序一般分两步处理以确保基板表面清洗干净，大多采用喷淋刷洗的方式。  \n\n(2）热水清洗热水清洗主要是将基板表面残留的脱脂剂清洗干净，保证这些残留物能溶解于其中，以防止脱脂剂对基板造成二次污染。大多采用浸洗和喷淋刷洗的方式。水质最好硬度不要太高，否则，水中的矿物质会在基板表面生成矿斑。  \n\n(3）钝化处理钝化处理是通过加压喷淋、浸涂或辊涂等方式使钝化剂在基材表面形成转化膜。一般采用加压喷淋的方式，钝化液在使用过程中产生的泥渣往往会堵塞喷孔，从而影响喷淋效果。浸涂的方式虽然解决了这一问题，但钝化液的消耗量较大。以上两种方法在实际操作中都需要用水冲洗多余的钝化液，就会产生废水的回收和净化问题，辊涂是最好的钝化施工方式，具有涂布均匀、经济实用、不需淋洗等优点。铝板一般采用铬酸盐/氧化物型处理剂，含有铬酸盐、铬酸、磷酸及促进剂氟化物和钼酸盐等。如需处理食品和饮料用铝板，处理剂中必须加入磷酸。  \n\n典型的铝卷材板处理方法例如十箱法操作工艺： $60^{\\circ}C$ 碱洗 $\\nrightarrow$ 室温水洗两遍 $\\rightarrow$ 铬酸室温处理 $\\nsim$ 室温水洗两遍 $\\nsim$ 转化膜处理（ $\\langle50\\sim55^{\\circ}\\mathrm{C}\\rangle\\rightarrow$ 室温水洗 $+70^{\\circ}C$ 水洗 $360{\\sim}95^{\\circ}C$ 干燥。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 391,
+        "chunk": "# 2.涂料涂装及固化  \n\n主要设备包括辊涂机和烘道。一般采用正面或正反面涂装的工艺。卷铝涂料也可分为底漆、面漆（包括清漆，即罩光漆）和背漆。  \n\n与彩钢板不同，一般卷铝普遍为单涂层，在高档或要求高的场合才会用到底漆加面漆的二涂层体系。  \n\n(1）涂装辊涂机分为二辊机和三辊机。二辊机主要由漆槽、提料辊、涂布辊、传动辊组成。三辊机多一个控制辊，用于调节由提料辊转移到涂布辊上的涂料的量，对于准确控制涂漆量有一定的作用。可以通过调节辊筒的转动速率及辊筒之间的辊速比获得好的涂装质量。  \n\n(2）固化为了保证有足够的固化时间，要求烘炉有一定长度。烘炉主要由烘道、加热设备、尾气收集设备组成。应根据生产线速不同调整烘炉温度，达到规定的板面温度(PMT)。加热设备根据生产线所在地区的能源情况而定，主要有燃气方式及电加热方式两种。尾气收集装置主要包括预热氧化装置、焚烧室和热交换床等。处理尾气采用焚烧的方法，生产线产生的尾气引人预热氧化装置进行净化和热处理，产生溶剂热风，将产生的溶剂热风和燃料气一起引人焚烧室燃烧，经过燃烧，含有有机溶剂的尾气转变成水和二氧化碳，产生的热量通过热交换装置被回收利用，使得最终排放到空气中的尾气中有害气体含量大大降低。  \n\n(3）涂装工艺与彩钢板相似，预涂卷铝按涂料的涂装道数也可分为三涂、二涂及单涂三种。按涂布辊和传动辊的转动方向可分为顺涂和逆涂两种。涂布辊的转动方向：和基板的进行方向相同的涂布方式为顺涂，反之为逆涂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 392,
+        "chunk": "# 3.后处理  \n\n后处理段是对生产出的卷铝做进一步的加工，提供更好的防护和装饰效果，如贴膜、印花、压花和压型等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 393,
+        "chunk": "# 二、卷铝涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 394,
+        "chunk": "# 1.底漆  \n\n底漆需要提供防腐蚀性、与铝卷底材和面漆的结合力，同时与面漆配套涂膜体系要满足机械加工和耐溶剂擦拭等性能要求。对铝卷底材，涂膜的耐盐雾性要求不如钢铁底材，但要求有一定的耐碱性。底漆与铝卷材的附着力结合类型，主要是吸附结合和机械结合。吸附结合又可分为分子吸附（物理吸附）和化学吸附。分子吸附由分子力——范德华力引起，化学吸附是涂装材料与铝板表面生成共价键而产生的吸附力。机械结合主要是指涂层与铝卷材以机械的方式结合，有机涂层与铝卷材的结合主要是嵌合作用，通常铝卷材表面通过前处理后（转化膜涂层后）增加基体的比表面，达到了表面相对粗化，增大了接触面积和孔隙，提供了使有机涂层嵌合在基体表面的机会，增强了有机涂层与基材的锚合附着力。  \n\n用于铝底材的底漆树脂体系例如环氧聚氨酯、环氧聚酯氨基、环氧聚酯聚氨酯、聚酯氨基、丙烯酸聚氨酯等。  \n\n卷铝底漆常用树脂类型及参数见表3-5-30。  \n\n表3-5-30 卷铝底漆用树脂牌号及参数  \n\n\n<html><body><table><tr><td>牌号</td><td>生产厂商</td><td>类型</td><td>固含量/%</td><td>酸值 /（mgKOH/g)</td><td>羟值 /(mgKOH/g)</td><td>T/C</td></tr><tr><td>L411</td><td>degussa</td><td>聚酯</td><td>100</td><td><3</td><td>5</td><td>47</td></tr><tr><td>LH 818</td><td>degussa</td><td>聚酯</td><td>50</td><td><3</td><td>20</td><td>35</td></tr><tr><td>SN 800</td><td>DSM</td><td>聚酯</td><td>60</td><td>0~4</td><td>20</td><td>一</td></tr><tr><td>6150</td><td>江苏三木集团有限公司</td><td>环氧改性聚酯</td><td>50.0±1.0</td><td>≤10</td><td></td><td>一</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 395,
+        "chunk": "# 2.面漆  \n\n面漆要求具有优异的硬度、抗划伤性、表面装饰效果及耐候性等。面漆一般为单层涂装，有些应用如采用金属闪光面漆时，可以再加上一道罩光清漆，进一步提高面漆的装饰和保护作用。  \n\n卷铝面漆主要有聚酯面漆、丙烯酸面漆和氟碳面漆等。  \n\n聚酯面漆具有良好的柔韧性、附着力，适用于内墙用铝塑复合板面板（辊涂)、铝天花面背（辊涂）、铝单板面板（喷涂）等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 396,
+        "chunk": "# 卷铝面漆用聚酯树脂牌号见表3-5-31。  \n\n表3-5-31卷铝面漆常用聚酯树脂牌号及参数  \n\n\n<html><body><table><tr><td>牌号</td><td>生产厂商</td><td>固含量 /%</td><td>酸值 /(mg KOH/g)</td><td>羟值 /(mgKOH/g)</td></tr><tr><td>ETERKYD 5060-R-60-1</td><td>长兴化学工业有限公司</td><td>59~61</td><td><5</td><td>一</td></tr><tr><td>3360</td><td>江苏三木集团有限公司</td><td>60.0±1.0</td><td>≤8</td><td>80</td></tr><tr><td>3966</td><td>江苏三木集团有限公司</td><td>60.0±1.0</td><td>≤6</td><td>100</td></tr></table></body></html>  \n\n典型的卷铝聚酯面漆的涂料及涂膜性能见表3-5-32和表3-5-33。  \n\n表3-5-32 卷铝聚酯面漆性能  \n\n\n<html><body><table><tr><td>项目</td><td>技术指标</td><td>检验标准</td></tr><tr><td>颜色及外观 细度/μm</td><td>按客户要求，无结块 ≤25(银色除外）</td><td>GB/T 1724--1989</td></tr><tr><td>相对密度</td><td>银色系列1.10±0.20 深色系列1.20±0.20 浅色系列1.30±0.20</td><td></td></tr><tr><td>黏度（25℃，涂-4杯）/s</td><td>120±10</td><td>GB/T 1723—1993</td></tr><tr><td>固体分（质量分数）/%</td><td>银色系列≥50 深色系列≥55 浅色系列≥60</td><td>GB/T 1725—1989</td></tr></table></body></html>  \n\n表3-5-33 卷铝聚酯面漆涂膜性能指标  \n\n\n<html><body><table><tr><td>项 目</td><td>技术指标</td><td>检验标准</td></tr><tr><td>色差△E</td><td>银色：目测无明显色差 素色≤0.5，银色≤1.0</td><td>一 色差仪</td></tr><tr><td>干膜厚度/μm 光泽（60°) MEK/次 密着性/级 柔韧性/T</td><td>≥16 依客户要求 ≥100 0 ≤3 ≥5 ≥2 无变化</td><td>GB/T 17748—1999 GB/T 17748—1999 NCCA II -18 GB/T 17748—1999 GB/T 17748—1999 GB/T 17748—1999 GB/T 17748—1999 GB/T 17748—1999 GB/T 17748—1999 GB/T 17748—1999 一 一 11</td></tr></table></body></html>  \n\n丙烯酸卷铝面漆具有良好的附着力和耐候性，适用于内墙用铝塑复合板面板（辊涂）、柔性风管（辊涂)、百叶窗面背（辊涂)、小五金（喷涂）等涂装。三木公司卷铝用丙烯酸树脂牌号及参数见表3-5-34。  \n\n表3-5-34 卷铝用丙烯酸树脂牌号及参数  \n\n\n<html><body><table><tr><td>牌号</td><td>固含量/%</td><td>T/C</td><td>酸值/(mg KOH/g)</td><td>羟值/(mg KOH/g)</td></tr><tr><td>BS-960AU-60</td><td>50±1</td><td>一</td><td>12</td><td>一</td></tr><tr><td>BS 9417B</td><td>60±1</td><td>40</td><td>一</td><td>125</td></tr><tr><td>BS 998D</td><td>60±1</td><td>5</td><td>8</td><td>110</td></tr></table></body></html>  \n\n<html><body><table><tr><td>牌号</td><td>周含量/%</td><td>T/C</td><td>酸值/（mgKOH/g)</td><td>羟值/（mgKOH/g)</td></tr><tr><td>BS 8072</td><td>70±1</td><td>5</td><td>8</td><td>110</td></tr><tr><td>BS-988-2</td><td>55±2</td><td>一</td><td>≤10</td><td>二</td></tr><tr><td>EA1622(水性）</td><td>60±1</td><td>-20</td><td>一</td><td>一</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 397,
+        "chunk": "# 典型的丙烯酸卷铝面漆的涂料及涂膜性能见表3-5-35。  \n\n表3-5-35 丙烯酸卷铝面漆性能  \n\n\n<html><body><table><tr><td>项目</td><td>技术指标</td><td>检验标准</td></tr><tr><td>颜色及外观 细度/μm</td><td>按客户要求，无结块 ≤25(银色除外）</td><td>GB/T 1724—1989</td></tr><tr><td>相对密度</td><td>银色系列1.10±0.20 深色系列1.20±0.20</td><td></td></tr><tr><td>黏度(25℃，涂-4杯）/s</td><td>浅色系列1.30±0.20 120±10</td><td>GB/T 1723—1993</td></tr><tr><td>固体分（质量分数）/%</td><td>银色系列≥50 深色系列≥55 浅色系列≥60</td><td>GB/T 1725-1989</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 398,
+        "chunk": "# 丙烯酸卷铝面漆涂膜性能指标见表3-5-36。  \n\n表3-5-36 丙烯酸卷铝面漆涂膜性能指标  \n\n\n<html><body><table><tr><td>项 目</td><td>技术指标</td><td>检验标准</td></tr><tr><td>色差△E</td><td>银色：目测无明显色差 素色≤0.5，银色≤1.0</td><td>色差仪</td></tr><tr><td>干膜厚度/μm 光泽（60°) MEK/次 密着性/级 柔韧性/T 冲击强度/J</td><td>≥16 依客户要求 ≥50 0 ≤4 ≥5 ≥2 无变化 无变化</td><td>GB/T 17748—1999 GB/T 17748—1999 NCCAII -18 GB/T 17748—1999 GB/T 17748—1999 GB/T 17748—1999 GB/T 17748—1999 GB/T 17748—1999 GB/T 17748—1999 GB/T 17748—1999 一 一</td></tr></table></body></html>  \n\n氟碳卷铝面漆耐候性和涂层综合性能优异，适用于外墙用铝塑复合板面板涂装。典型的氟碳卷铝面漆的涂料及涂膜性能见表3-5-37和表3-5-38。  \n\n续表  \n表3-5-37 氟碳卷铝面漆性能  \n\n\n<html><body><table><tr><td>项目</td><td>底漆</td><td>素色面漆</td><td>金属面漆</td><td>罩光漆</td></tr><tr><td>外观</td><td>淡黄色或灰色液体</td><td>按客户要求，各种彩色液体</td><td>银色液体</td><td>透明液体</td></tr><tr><td>细度/μm</td><td>25</td><td>25</td><td></td><td>25</td></tr><tr><td>黏度(25℃，涂-4杯)/s≥</td><td>100</td><td>100</td><td>100</td><td>100</td></tr><tr><td>固含量/%</td><td>55</td><td>50</td><td>40</td><td>40</td></tr><tr><td>施工黏度(25℃，涂-4杯)/s</td><td>60±10</td><td>70±10</td><td>80±10</td><td>80±10</td></tr><tr><td>干膜厚/μm</td><td>10±2</td><td>18±2</td><td>15±2</td><td>8±2</td></tr><tr><td>固化条件（PMT)/℃</td><td>216~224</td><td>232～241</td><td>232~241</td><td>232～241</td></tr><tr><td>烘烤时间/s</td><td>60</td><td>90</td><td>90</td><td>90</td></tr></table></body></html>  \n\n表3-5-38 氟碳卷铝面漆涂膜性能  \n\n\n<html><body><table><tr><td>项 目</td><td>技术指标</td><td>检验标准</td></tr><tr><td>光泽（60°）)</td><td>依客户要求</td><td>GB/T 9754—1988</td></tr><tr><td>MEK/次</td><td>≥200</td><td>NCCA II -18</td></tr><tr><td>干附着力/级</td><td>0</td><td>GB/T 9286—1998</td></tr><tr><td>湿附着力/级</td><td>0</td><td>GB/T 9286-1998</td></tr><tr><td>沸点附着力/级</td><td>0</td><td>GB/T 9286—1998</td></tr><tr><td>T弯/T</td><td>≤2</td><td>GB/T 17748—1999</td></tr><tr><td>耐冲击(5J)</td><td>通过</td><td>GB/T 17748—1999</td></tr><tr><td>铅笔硬度/H</td><td>≥2</td><td>GB/T 6739—1996A</td></tr><tr><td>耐磨性（落砂试验）/L/μm</td><td>≥5.0</td><td>ASTM D968—1993A</td></tr><tr><td>耐酸性（5%盐酸，体积分数）/h</td><td>48h无异常</td><td>GB/T 17748—1999</td></tr><tr><td>耐碱性（5%氢氧化钠，质量分数）/h</td><td>48h无异常</td><td>GB/T 17748—1999</td></tr><tr><td>耐30*汽油/h</td><td>48h无异常</td><td>GB/T 17748—1999</td></tr><tr><td>耐沾污(5次循环)/%</td><td>≤5</td><td>GB/T 9757—2001附录A</td></tr><tr><td>耐沸水/h</td><td>2h无异常</td><td>GB/T 1733—1993 乙</td></tr><tr><td>耐砂浆性/h</td><td>24h无异常</td><td>GB/T 1766—1995</td></tr><tr><td>耐硝酸性（30min），△E</td><td>≤5.0</td><td>GB/T 5211.20—1999</td></tr><tr><td>耐洗涤剂性/h</td><td>72h无异常</td><td>GB/T 9274—1988甲</td></tr><tr><td>耐窗洗液性/h</td><td>24h无异常</td><td>GB/T 9274—1988丙</td></tr><tr><td>耐盐酸性/min</td><td>15min无变化</td><td>GB/T 9274—1988丙</td></tr><tr><td>耐洗刷性（双向）/次</td><td>≥12000</td><td>GB/T 9266—1988</td></tr><tr><td>耐湿热性/h</td><td>4000 起泡程度\"少量\"以下， 起泡大小\"No.8\"以下</td><td>GB/T 1740—1989 评级ASTMD714—2002</td></tr><tr><td>耐盐雾性/h</td><td>4000 划级处破坏≥7级， 未划线区≥8级</td><td>ASTM B117—2003 评定按ASTMD1654—1992</td></tr><tr><td>耐人工加速老化/h</td><td>4000 △E≤5.0；失光≤2级 粉化、白色≤1级；其他≤2级</td><td>GB/T 1865—1997 评级GB/T1766—1995</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 399,
+        "chunk": "# 3.背面漆  \n\n背面漆要求有一定的耐候性、硬度和抗划伤性  \n\n卷铝背面漆的性能要求不高，基料树脂可以采用醇酸或环氧改性聚酯，以氨基或封闭异氰酸酯固化。三木公司卷铝背漆常用基料树脂牌号及参数见表3-5-39。  \n\n表3-5-39卷铝背漆常用基料树脂牌号及参数  \n\n\n<html><body><table><tr><td>牌号</td><td>类型</td><td>固含量/%</td><td>酸值/（mgKOH/g)</td><td>羟值/（mg KOH/g)</td></tr><tr><td>3620</td><td>醇酸树脂</td><td>60.0±1.0</td><td>≤5</td><td>130</td></tr><tr><td>3818-70</td><td>醇酸树脂</td><td>70.0±1.0</td><td>≤12</td><td>120±15</td></tr><tr><td>9355</td><td>豆油改性醇酸树脂</td><td>55.0±1.0</td><td>≤10</td><td>80</td></tr><tr><td>6150</td><td>环氧改性聚酯</td><td>50.0±1.0</td><td>≤10</td><td></td></tr></table></body></html>\n\n$\\textcircled{1}$ 生产厂商为江苏三木集团有限公司。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 400,
+        "chunk": "# 第九节 卷材涂料新进展  \n\n自改革开放以来，中国的国民经济飞速发展，卷材涂料作为一种新型的高性能、环保、  \n\n高效和节能技术新产品，其技术和市场也得到了快速发展，出现了许多新产品和新技术。",
+        "category": " Introduction"
+    },
+    {
+        "id": 401,
+        "chunk": "# 一、家电用卷材涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 402,
+        "chunk": "# 1.家电用卷材涂料简介  \n\n家电正在迈人“彩色时代”。随着人们生活水平的提高，同生活息息相关的家电产品也开始追求时尚的外观，在我国家电业的发展历程上，大件家电按照通常的色调被分为“黑电”和“白电”两大系列，“黑电”包括彩电、音响组合、影碟机、家庭影院等视听类家电，而“白电”则包括冰箱、洗衣机、空调等冰洗、制冷类家电。现如今这种传统的分类已经跟不上时代的步伐，从几年前开始出现的银色系彩电、金色系家庭影院，到现在的卡通多彩系列小家电，再到彩色面板的空调、冰箱等，五颜六色的家用电器正在逐渐成为主流产品。外观设计、色彩与家庭装修的搭配逐渐成为消费者购买家电时的重要考虑因素。这种变化从某种程度上促进了家电涂装方式的变革。  \n\n传统的家电涂装主要有喷粉、贴膜两种，家电侧板主要是喷粉，而面板则主要是以喷粉、贴膜为主。喷粉属“后涂装”工艺，其涂膜厚、成本高、效率低、花色品种单一，已无法满足日新月异的家电市场需求。而家电涂装采用预涂彩板技术可以满足市场的多样化要求。  \n\n随着卷材涂料研发的不断深人以及预涂卷材涂料自身的环保和经济优势，除用于建筑板外，国外开始研究家电板用卷材涂料，并已大量用于各种家电产品。国内各卷材涂料研究单位对此类产品也加快了研究步伐。家电用彩涂板分为贴膜板和预涂彩板两大类。  \n\n贴膜板主要有VCM板（贴PVC膜的板）和ECM板（贴PET膜的板），VCM板是在预钝化处理的钢板上涂上胶黏剂后，在一定的温度下层压PVC膜而制备，由于PVC膜中含有氯和增塑剂而存在环保问题，出口现已受到限制；ECM板则是在预钝化处理的钢板上辊涂一定膜厚的底漆，快速强制高温烘烤固化（一般板温PMT范围 $204{\\sim}241^{\\circ}\\mathrm{C},$ ）后，迅速层压PET薄膜而制备，由于不存在环保问题，ECM板可以作为VCM板的更新换代产品。PET贴膜板的好坏除了取决于膜的质量，受底漆的影响也很大，特别是对底漆与底材之间的附着力以及膜与底漆之间的层间附着力要求比较高，因此要求开发专用的PET贴膜用底漆。  \n\n家电用预涂彩板（PCM板）是将成卷的金属薄板涂上涂料，迅速强制烘烤固化成膜后，根据不同用途裁切成不同尺寸后出售的一种有机材料/金属复合板材。用户可以直接将它加工成型，做成各种部件或产品，组装或安装后便是成品，而无需再涂装，从而大大简化了金属薄板制成品的生产工艺。  \n\n预涂彩板符合环保要求，又具有良好的经济效益，它采用连续涂装，简化了生产工艺，节省了投资和运转费用，可以得到最佳的涂装质量。金属薄板生产效率高，涂漆的金属薄板连续通过烘炉使漆膜固化，炉容的利用率明显高于成品或部件涂漆后的烘烤固化，同时烘烤过程中产生的含有机溶剂的烘炉废气可以收集烧变成热能再利用，有利于节能环保。  \n\n家电产品属于耐用消费品，面对的绝大部分是家庭消费者，所以对家电板的外观要求非常严格，几乎不能存在一点缺陷。此外，相对于传统的建筑板，家电板要求更高的加工性能。如T弯，建筑板通常是小于等于3T（胶带粘不掉，允许有裂纹)；而家电上有些部位需要对折，即要求零T弯（无裂纹，粘不掉)。同时家电板要求具有较好的抗划伤性，这就需要树脂体系在硬度和柔韧性之间把握更好的平衡。家电板与建筑板使用的基板不同，建筑板大多采用镀锌钢板，而家电板基板品种比较多，以冷轧钢板为主，也有使用无锌花热镀锌钢板和电镀锌钢板的。不同的底材，其防腐机理也不同，因此需要采用不同的底漆。同时家电板制品大多用于居民的日常使用，有较高的环保要求，因此不能使用在建筑板涂料中广为使用的含铬等重金属的防腐颜填料，为得到优良的耐盐雾性能，必须在技术上有突破。除了选用合适的防腐颜料、填料，还需要根据不同底材的防腐机理选用合适的基料体系。  \n\n预涂板按正面涂装道数划分，目前主要有一涂一烘（基板上直接涂装面漆)、二涂二烘(在基板上涂装底漆和面漆）和三涂三烘(在基板上涂装底漆和面漆，再涂装一层罩光清漆)三种方式。三涂层体系在外观、表面抗划伤性和防腐性能方面要好于单涂层，但在加工性能上要差一些。如T弯，单涂层和二涂层能达到0T，但三涂层就很难达到。  \n\n相对于传统的建筑板，家电板最主要的特点是高装饰性和高加工性能以及优良的抗划伤性与严格的环保要求。由于家电板的上述特点，对家电板涂料（包括底、面、背漆配套的系统涂层）的性能要求非常高，普通的卷材涂料（建筑板）很难达到家电板的要求。此外，家电板品种繁多，不同品种的用途对家电板涂料有不同的要求。因此对家电板涂料而言，绝不是一个或几个配方就能满足要求的。不同用途的家电板的大概的性能要求见表3-5-40。  \n\n表3-5-40不同用途家电板的性能要求  \n\n\n<html><body><table><tr><td>品种</td><td>柔韧性</td><td>耐污染性</td><td>硬度</td><td>耐化学性</td><td>耐候性</td><td>防腐性</td></tr><tr><td>微波炉</td><td>5</td><td>4</td><td>3</td><td>2</td><td>2</td><td>3</td></tr><tr><td>冰箱</td><td>3</td><td>5</td><td>5</td><td>4</td><td>2</td><td>3</td></tr><tr><td>空调机</td><td>3</td><td>3</td><td>4</td><td>4</td><td>5</td><td>5</td></tr><tr><td>视听产品</td><td>4</td><td>3</td><td>4</td><td>3</td><td>2</td><td>3</td></tr></table></body></html>\n\n注： $\\bar{5}=$ 要求最高， $1=$ 要求最低。  \n\n因此，应当根据不同的用途设计不同的配方，增强针对性。",
+        "category": " Introduction"
+    },
+    {
+        "id": 403,
+        "chunk": "# 2.家电用卷材底漆涂料  \n\n传统的卷材底漆采用环氧聚氨酯、环氧氨基、聚酯聚氨酯和聚酯氨基体系。环氧体系湿附着力好、耐盐雾性能优异，但漆膜柔韧性太差，不能满足家电板用涂料要求。聚酯体系中根据聚酯树脂分子量大小，可以分为中小分子聚酯和中高分子聚酯两大类，在家电板底漆中常用的是后者，这也是目前国外家电板底漆中最常用的一种类型，即以线型或少量支链化的中、高分子聚酯树脂为基料树脂，以氨基树脂或封闭异氰酸酯树脂为固化剂的体系。这类体系的突出特点是柔韧性优异、附着力好。  \n\n针对家电彩钢板的市场要求，常州涂料化工研究院开发出了高加工性的HY-JD-101系列家电板专用底漆，由中高分子量聚酯树脂、特制改性树脂、氨基树脂和聚氨酯树脂、合适的助剂和环保型防腐颜填料组成。这种底漆与面漆的配套性好，力学性能特别是柔韧性优异，防腐性好，在冷轧钢板上与适宜面漆的复合涂膜的中性盐雾试验也可达到 $240\\mathbf{h}$ 以上（划叉处单边锈蚀 $\\leqslant2\\mathrm{mm}$ ，划线区以外无变化)，可以满足家电彩钢板的加工要求。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 404,
+        "chunk": "# 3.家电用卷材面漆涂料  \n\n面漆要求具有高装饰性、高加工性能以及优良的抗划伤性能，家电板面漆绝大多数都是采用聚酯体系，以氨基树脂或封闭异氰酸酯固化。但是单一的树脂体系往往不能满足这种较高的性能要求，在各项性能上很难综合平衡，往往是硬度高了、可提高耐划伤性，但柔韧性、T弯性能很差；反之，提高了柔韧性，硬度又会下降很多，因此很难达到家电板涂料的要求。家电彩板面漆的树脂体系要比传统的建筑彩板涂料复杂一些，需要开发一系列不同分子量、不同支化程度和不同玻璃化温度 $(T_{\\perp}$ ）的聚酯树脂，通过树脂比例及交联剂类型和用量的调整，可将树脂的高柔韧性和高硬度有机地结合起来，得到坚韧的涂膜。同时，采用这种方法，配方的灵活性高，很容易通过配方调整得到适应不同性能要求的家电板用预涂卷材涂料，从而形成系列化产品。  \n\n现代社会，人们越来越追求个性化，带动了家电彩板面漆研究开发的多样化。一种方法是在涂料中加入一定用量的各种纹理助剂，例如粒子状的丙烯酸聚合物微球、氧化铝纤维、玻璃纤维、二氧化硅粉、云母粉和聚酰胺粉末（可以预先以聚乙烯和聚四氟乙烯蜡等处理)，既可以得到特殊的纹理效果，又可以提高耐候性、耐划伤性和耐磨性；还可以在家电卷材面漆常用的聚酯/氨基、聚酯/封闭异氰酸酯体系中加入叔胺类化合物如三甲胺、三乙胺、 $N$ N-二甲基环已胺、 $N,N-$ 二甲基氨基乙醇、N，N-二乙基氨基乙醇、二乙醇胺等，获得纹理效果。另一种方法是通过采用特殊的涂装工艺，也可以得到外观和性能均优异的涂层。例如将镀锌钢板打磨抛光后预处理、涂覆底漆和面漆，可以得到具有仿抛光不锈钢外观效果且性能优异的涂层。此外，家电彩板涂装线设计时往往都带有压花或印花工艺段，可以通过压花或印花工艺压印出花纹，获得具有特殊纹理效果的涂覆板。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 405,
+        "chunk": "# 4.家电用卷材背漆涂料  \n\n背漆的主要作用是在背面起防护作用，要求漆膜有良好的防腐蚀性、抗划伤性、抗粘连性和加工性，但在装饰性和户外耐久性方面要求不高。  \n\n背漆大多采用单涂层，膜较薄，而同时又要求高柔韧性、较好的耐MEK性能和较好的耐盐雾性能，对许多应用中还需要背漆有良好的耐贴发泡层性能，应用于家电彩板时，往往还要求背漆具有良好的导电性，因此高性能的背漆技术含量相当高。  \n\n常州涂料化工研究院开发了一种新型背漆，以聚酯接枝改性环氧聚氨酯树脂为基料树脂，辅以适宜的交联树脂、颜料、填料和助剂。配制的背漆综合了环氧、聚酯和聚氨酯树脂的各自优点，既有优异的力学性能（附着力、柔韧性、硬度、耐划伤性)，又有良好的耐盐雾性和耐贴发泡层性能，能够满足需要高加工性能的建筑和家电彩钢板背漆的要求。其主要特点是开发了一种聚酯改性环氧聚氨酯树脂，通过接枝方法将聚酯树脂和多异氰酸酯引人环氧树脂中，在树脂中引入了氨酯键，利用环氧基团引人伯羟基，提高树脂的反应活性。聚酯树脂的引人可以改善漆膜的柔韧性，氨酯键的引入提高了漆膜的交联密度、附着力和耐盐雾性，反应活性的提高可以提高漆膜的交联密度，提高硬度、附着力、耐划伤性和耐贴发泡层性能。  \n\n在许多情况下，家电板要求背面具有导电性能，常州涂料化工研究院通过特殊的改性环氧树脂的合成以及特殊的导电颜料的选用，开发出了一种具有优异的导电性能而且成本较低的导电背漆。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 406,
+        "chunk": "# 二、汽车用卷材涂料  \n\n汽车彩涂钢板是卷材涂料未来的一个重要的应用领域，但是应用于汽车行业的预涂彩钢板性能要求相当高，需要满足汽车制造的特殊要求，如高耐腐蚀性、优良的可焊接性、良好的成型性和优良的涂装性等。  \n\n根据汽车涂装和卷材涂装工艺的特点，汽车预涂板的发展过程将是一个逐步取代的过程，其取代过程如图3-5-10所示。  \n\n第一步是取代阴极电泳层和中涂层，制备的预涂板冲压成型后，再以传统的喷涂方法涂装底色漆和罩光清漆层；第二步是取代阴极电泳层、中涂层和底色漆层，制备的预涂板冲压成型后，再以传统的喷涂方法涂装罩光清漆层；第三步是完全取代现有的汽车涂装体系，全部采用预涂板，无需喷涂过程。  \n\n但是，汽车预涂板距离实际应用还有许多技术难点需要克服。例如需开发可焊接的底漆，涂覆有可焊接的防腐底漆的钢板可以无需电泳涂装过程。PPG开发的可焊接底漆，含有由含环氧基团的聚合物与含有磷酸基团（亚磷酸、磷酸或麟酸）的化合物的反应产物、固化剂组成的树脂基料、导电颜料（锌、铝、铁、石墨、钨和不锈钢等）和水或有机溶剂，涂覆在底材上并固化后具有可焊接性；PPG开发的另一种可焊接底漆，含有环氧官能材料（环氧树脂）与含磷材料（磷酸或麟酸）或含胺材料（可用各种伯胺、仲胺、叔胺，较好的含有至少一种烷基醇胺）的至少一种的反应产物、导电颜料和水或溶剂。  \n\n![](images/30ff79a4dd165945062a4515eec6ba8ce19fc159707996c5cb5da89320fe8e2c.jpg)  \n图3-5-10 预涂汽车钢板逐步取代过程示意图",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 407,
+        "chunk": "# 三、食品罐用卷材涂料  \n\n金属食品罐头通常都涂覆有机涂层，以满足卫生性、耐腐蚀性和抗化学反应性能的要求。涂装于食品及饮料罐内壁的涂层材料必须是无毒的或在丢弃或回收利用时不会产生污染物，它们必须承受罐头加工蒸煮过程中产生的蒸汽、加热、罐头内容物中的盐类及酸类。  \n\n金属罐内表面涂装主要用环氧系、乙烯基系和聚酯系涂料，罐外表面主要用丙烯酸酯系和聚酯系涂料。传统的罐头内壁涂料原料主要采用以双酚类化合物为原料的环氧树脂，涂层性能优异。但最近的研究结果表明其有可能会影响人体内分泌系统，因此，今后，在食品领域，如罐头内壁涂料中将避免使用双酚类原料。  \n\n传统的金属包装生产材料多采用冷轧薄钢板、热轧薄钢板或镀锌薄钢板等，在生产过程中必不可少地要进行表面处理、涂漆、烘干等工艺过程，不仅成本高，而且质量难以保证，环境污染也较为严重。为了环境保护和降低成本，一种较好的方法是把钢卷板原料进行统一的预涂装，金属包装厂用预涂后的钢卷板直接制造包装物，不用后涂装，从而大大简化了金属包装物的生产过程。  \n\n由于环保问题日益受到人们的重视，覆膜预涂板在食品用罐中越来越多地被采用。主要为聚对苯二甲酸乙二醇酯（PET）膜和聚丙烯（PP）膜，覆膜板具有优异的加工性和耐腐蚀性，适用于制作加工变形量大和内装高腐蚀性物品的深冲罐与焊接罐。聚酯覆膜对食品中香味的吸收率小，可以使罐内食品中各种成分保持预期的平衡关系，使之长期处于良好状态。此外，用覆膜钢板制罐，可采用干式成型，无需过量的润滑剂，可以避免由清洗润滑剂而造成大量废水污染环境。因此，覆膜钢板可提高食品容器性能，降低生产成本，将成为继家电覆膜彩板后预涂卷材涂料的另一个较大的应用领域。  \n\n金属包装用预涂卷材涂料必须同时满足预涂卷材的生产工艺及金属包装产品加工使用两方面的特点。  \n\n预涂卷材生产工艺是快速辊涂施工，为保证漆膜厚度及流平性，要求有一定的施工黏度。在生产线上，底板行进速度很快，涂料在炉内烘烤时间很短，就要求涂料在底板温度(PMT) $260^{\\circ}C$ 以下 $30\\sim60{\\mathrm{s}}$ 内完全固化。另外涂漆后的闪蒸时间很短，所以要选用挥发速率合适的溶剂，以免起泡、产生针孔及流平性不好，通常采用高沸点溶剂。  \n\n从对漆膜性能的要求看，涂层为底、面漆各一道。底漆应有好的防腐性及对底材和面漆的附着力，面漆应有好的遮盖力和装饰性。还要求在产品加工成型时漆膜不开裂、不脱落，并在装配、运输及使用时能耐碰撞和划伤。即漆膜要同时具有较好的柔韧性及硬度，还要有优异的耐候性和防腐蚀性。  \n\n底漆可以采用环氧聚氨酯、环氧氨基、聚酯聚氨酯、聚酯氨基等。  \n\n面漆可以采用聚酯氨基、聚酯聚氨酯、塑溶胶和有机溶胶、以氯乙烯-醋酸乙烯共聚物为主要成膜物的乙烯类树脂涂料、丙烯酸涂料（特别是电子束固化的丙烯酸涂料)、氟碳涂料等。  \n\n预涂卷材在包装领域可替代木材和纸板制作普通包装箱；替代普通薄钢板制作金属容器，如钢桶、钢罐和小型桶等，具有加工简单、节约能源、减少污染的优点；替代马口铁制造商品包装盒，美观高雅，成本低廉；替代玻璃瓶等制造用于食品、饮料、罐头等的包装，提高了包装的安全性；用于制造大型包装产品，如集装箱、集箱桶等，可简化加工过程，从而降低成本、节约能源、减少污染。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 408,
+        "chunk": "# 四、隔热卷材涂料  \n\n世界上人口的快速增长和工业的快速发展都导致了有限资源消耗越来越大。开发节能产品成为人们的共识。开发节能隔热预涂卷材涂料符合涂料的发展趋势。建筑物采用隔热卷材，在夏天可以有效地降低对太阳光能量的吸收，在冬天可以有效地防止室内热量的散失，从而可以降低空调运行成本，降低电力消耗，节省能源。实验表明，采用隔热卷材，与采用非隔热卷材相比，在夏天，可使室内温度平均低约 $8^{\\circ}C$ ，在冬天，可使室内温度平均高约 $6^{\\circ}C$ 0.",
+        "category": " Introduction"
+    },
+    {
+        "id": 409,
+        "chunk": "# 1.隔热卷材涂料的性能要求  \n\n隔热卷材用作外用建筑材料，要求涂料具有： $\\textcircled{1}$ 美观、装饰性； $\\textcircled{2}$ 耐久性、耐候性；$\\textcircled{3}$ 防腐蚀性； $\\textcircled{4}$ 良好的加工性； $\\textcircled{5}$ 环保无毒； $\\textcircled{6}$ 有效节省能源。",
+        "category": " Introduction"
+    },
+    {
+        "id": 410,
+        "chunk": "# 2.隔热卷材涂料的隔热机理  \n\n夏天和冬天的隔热机理不同。夏天，隔热主要有两条途径。一是要减少太阳光能量的吸收。太阳光谱中与涂料相关的部分，波长从 $300{\\sim}2500\\mathrm{nm}$ ，各个不同的波长有不同的辐射强度。其中， $300{\\sim}400\\mathrm{nm}$ 为紫外线部分，占有约 $5\\%$ 的太阳光能量，虽然这部分能量所占比例很小，但对涂膜的降解起着相当大的作用。 $400{\\sim}700\\mathrm{nm}$ 的可见光部分，占有约 $44\\%$ 的太阳光能量。 $700{\\sim}2500\\mathrm{nm}$ 为近红外部分，占有到达地面的太阳光总能量的一半以上。因此对隔热涂料，要求尽可能控制紫外线部分和近红外区域的吸收，减少了紫外线部分的吸收可以减缓涂膜的降解，减少红外区域的吸收可以减少涂膜对太阳光中的热量的吸收，起隔热作用。而对可见光部分，通过不同波长的光的反射可以得到不同的涂膜的颜色和光泽。二是要减少室外热量对室内的热传导。这就要求隔热涂料自身热导率极小、导热性差即隔热性能优。  \n\n另一方面，在冬天，室内虽有人和物体辐射热量，但热值很小，促使室内温度高于室外主要热量来源于供暖，这对隔热涂料的反射光能力不作要求，可以利用其导热系数小、导热性差即隔热性能优的特点，避免室内热量的散失而起到节能作用。  \n\n根据上述原理，隔热预涂卷材应至少由三层组成，共同起隔热作用：外层隔热涂膜、基材和内层隔热涂膜。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 411,
+        "chunk": "# 3.隔热卷材涂料的组成  \n\n基于上述机理，隔热卷材涂料中，除了需要仔细选择树脂体系以达到预涂卷材所需的机械加工性能外，还应当根据不同的隔热机理加人不同的隔热材料及助剂，起到隔热屏蔽作用。  \n\n(1）正面涂料受卷材涂装线限制，根据现有的卷材涂装条件，卷材单面最多只能涂覆三层，即采用三涂三烘工艺，因此考虑正面涂料由三涂层组成。  \n\n$\\textcircled{1}$ 面漆为了尽可能减少涂膜降解，涂膜对紫外线部分（ $300\\sim400\\mathrm{nm})$ ）必须是透明的，或者说是尽可能减少吸收。为此，除了应该选择耐候性好的基料树脂和颜料外，还可加人适量紫外光吸收剂和光稳定剂。对可见光区域 $(400{\\sim}700\\mathrm{nm})$ ，应根据颜料和光泽的需要反射和散射一定的可见光部分。涂膜应尽可能反射近红外区域！ $(700-2500\\mathrm{nm})$ ，这可以通过使用红外反射颜料实现。  \n\n红外反射（IRR）颜料是一种新型的颜料。红外反射颜料具有选择吸收波段性，它可以部分或全部吸收可见波段，而产生各种颜色，甚至黑色，但对近红外区辐射，IRR颜料可以大量反射，从而大大减少了涂膜对太阳光能量的吸收。自然界中的深绿色的树叶就是一种天然的红外反射体，这是由于叶绿素这种天然的红外反射物质的存在。德固萨公司（De-gussa）等已经开发出了许多品种的IRR颜料，如Eclipse°黑10201、10202、10203、10204；Eclipse°棕10221、10222；Eclipse绿10241等。Ferro 也开发出了各种颜色的IRR颜料产品，具有较高的红外反射率。其他的IRR颜料如有机和无机或复合无机颜料（CICPs)，CICPs具有优异的耐候性、化学稳定性和遮盖力，例如，C.I．颜料黑28（一种铜铬锈矿组成物)，C.I．颜料黑30（一种含镍、镁、铬和铁的尖晶石）、C.I．颜料绿17（含铬和铁）等。  \n\n白色颜料可以反射 $60\\%\\sim70\\%$ 的太阳光能量，包括可见光和近红外区域，而普通的黑色颜料只能反射 $5\\%$ 的太阳光能量，所以采用浅色涂层有利于节能，如果要使涂层的颜色更丰富多彩，应尽可能使用IRR颜料。  \n\n$\\textcircled{2}$ 中涂尽管面漆已反射大部分的太阳光能量，涂膜仍会吸收部分能量，因此要求中间涂膜的热导率很小，在涂料中可以通过加人隔热屏蔽材料如云母、隔热陶瓷、中空玻璃珠等屏蔽吸收的热量，阻止热量的传导。  \n\n$\\textcircled{3}$ 底漆底漆如普通建筑用卷材底漆，提供优良的防腐性能、附着性能和加工性能等。  \n\n(2）背面涂料背面涂料由底漆和面漆组成，对背面隔热涂料所需的性能要求与正面涂料有所不同。背面涂膜不需要反射太阳光，只要求有良好的隔热性能，即要求涂膜的热导率很低。可以在面漆中加人隔热材料如云母、隔热陶瓷、玻璃珠等而起热能屏蔽作用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 412,
+        "chunk": "# 五、纳米材料的应用  \n\n纳米科技是20世纪80年代末、90年代初才逐步发展起来的新兴学科领域，但它的迅猛发展将在21世纪促使几乎所有的工业领域包括涂料工业产生一场革命性的变化。近年来，在纳米粉体在涂料中的应用也越来越多。  \n\n上海大学施利毅教授等发明了一种用于卷材涂料的纳米功能粉体分散液，由纳米功能粉体、分散助剂、有机聚合物树脂和溶剂组成，是一种用于卷材涂料中提高涂料综合性能的新型分散液。其制备方法是：用经适当表面处理剂处理的纳米功能粉体、一定量有机聚合物树脂及分散助剂为主要成分，采用球磨、砂磨、高速乳化及振荡多项分散工艺，使其分散，制得分散液。该分散液在卷材涂料配漆过程中按一定比例加人，均匀混合后可提高卷材涂料的综合性能。施利毅教授等还发明了一种高耐腐蚀性纳米复彩钢板涂料，在聚酯型涂料中，加人 $2\\%\\sim$  \n\n15%（质量分数）经适当有机表面处理剂处理的纳米级功能粉体，该纳米级功能粉体包括纳米氧化钛、氧化硅、氧化锌、氧化镍、氧化铝、氧化铬、氧化锰中的一种或两种的组合；将该纳米粉体先在少量聚酯树脂中采用球磨、砂磨、高速乳化的特殊分散工艺，使其均匀分散，制得浆液，然后将该浆液涂料本体聚酯树脂均匀混合，最终可得到高耐磨腐蚀性纳米复合彩钢板涂料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 413,
+        "chunk": "# 六、特殊功能性彩板用卷材涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 414,
+        "chunk": "# 1.耐指纹彩钢板涂料  \n\n镀锌钢板在家电行业中广泛应用，但在家电产品制造过程中，操作者的手不可避免地会与钢板表面接触而留下明显的指纹印或掌印，光的反射和吸收状态就会发生变化，较之无指纹部分，有指纹部分扩散反射光会减少而发黑，影响美观，同时留有指纹的钢板还容易引发锈蚀，影响产品质量。通过在钢板上涂覆耐指纹涂料，就可以解决这一问题。最早的耐指纹涂料是铬酸盐、硅酸盐处理剂，以后，随着产品要求的不断提高，开发出了无毒、性能更优异的专用耐指纹涂料。如上海宝钢集团公司研制出了一种水性耐指纹涂料，以水溶性改性聚丙烯酸酯乳液为主（含 $2\\%\\sim15\\%$ 有机硅溶胶)，加有 $5\\%\\sim10\\%$ 链烷水合物。宝钢公司研制的另一种水性耐指纹涂料中，含 $60\\%\\sim80\\%$ 的水性丙烯酸树脂、 $2\\%\\sim10\\%$ 的二氧化硅、$7\\%\\sim20\\%$ 的聚四氟乙烯和 $2.5\\%\\sim10\\%$ 的聚乙烯蜡。日本巴可莱新株式会社研制出的一种耐指纹涂料，由硅烷偶联剂、有机聚合物和蜡组成。日本帕卡濑精株式会社（原译巴可莱新）研制了一种可以在金属材料表面形成具有优良耐蚀性、耐指纹性、耐变黑性、涂料密合性等的涂膜的表面处理用组合物和表面处理方法。该金属材料表面处理用组合物含有水性介质和下述成分： $\\textcircled{1}$ 从 $\\mathbf{M}\\mathbf{\\bar{n}}$ 离子、 $C O$ 离子、 $Z_{\\Pi}$ 离子、 $\\mathbf{M}_{\\mathbf{E}}$ 离子、Ni离子、Ti离子、V离子和$z_{\\mathrm{{r}}}$ 离子中选择的金属离子； $\\textcircled{2}$ 具有至少4个氟原子和从Ti、Zr、Si、Hf、Al和B中选择的元素的氟代酸； $\\textcircled{3}$ 具有从含活性氢的氨基、环氧基、乙烯基、硫基和甲基丙烯酰氧基中选择的反应性官能团的硅烷偶联剂； $\\textcircled{4}$ 把从阳离子型或非离子型的聚氨酯树脂、丙烯酸树脂、环氧树脂、聚酯树脂和聚酰胺树脂中选择的树脂作为树脂成分的水系乳化树脂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 415,
+        "chunk": "# 2.抗菌彩钢板涂料  \n\n聚合物涂料施工于底材上可以改善外观，防止底材受外界环境、生物和机械的破坏，还可提供其他的功能性，要求涂层保持清洁，不沾灰、不发霉，在使用期内防止其他污染物的黏附。由于化学和生物污染会导致保护涂层的装饰性和功能性的损失，从而使涂膜经常要维护保养，例如室外建筑涂层会由于霉菌污染而形成令人不悦的肮脏的外观。霉菌污染会影响节能型弹性屋顶建筑材料的太阳光反射能力，表面霉菌的滋生也会明显影响涂层的保护性能，导致底材的结构破坏。  \n\n尽管导致霉菌滋生的机理不同，都要求涂层能提供长期的防止化学品和微生污染物附着的能力，以维持涂层的装饰性和保护性。  \n\n目前开发的抗菌材料灭菌原理有两种类型：一是依靠金属离子灭菌；二是靠光催化剂灭菌。  \n\n金属离子灭菌原理：当细菌和金属离子接触时，金属离子进入细菌内和使细菌增殖的酶结合，使酶失去活性，达到防菌抗菌目的。金属离子中应用最多的是银系、铜系和锌系。  \n\n光催化剂灭菌中典型的为利用光催化剂二氧化钛在太阳或荧光紫外线照射时，空气中的氧和水分形成活性氧，光催化剂具有使有机物质氧化分解的能力，此外，锐钛矿结晶结构的二氧化钛在太阳光、荧光中紫外线照射时，表面产生活性羟基、氧等，起很强的氧化作用，使细菌分解，起到杀菌作用。这种类型的抗菌有光条件下可以即刻起作用，但在没有光的情  \n\n况下，会影响杀菌效果。  \n\n通过将抗菌材料混合于有机涂料中并涂覆于基板上即可形成具有独特抗菌性的抗菌彩钢板。  \n\n抗菌彩钢板可以广泛应用于制作家用电器、冷库、冷藏车、医疗设备、建筑墙体材料、食品加工设备等，起抗菌、防霉、消毒、除臭、防藻等功能。  \n\nKlesse等人提出了一种解决涂层表面微生物污染增长的方法：在涂料组成物中加人特殊的含有具有防微生物活性的聚合物助剂。聚合物中含有带季铵盐的乙烯基单体作为杀菌活性组分。分子量非常大， $M_{\\mathrm{w}}=20000{\\sim}500000$ 0  \n\n为了解决涂层的防微生物污染问题，关键部分为涂层的表面，需要在液态涂料组成物中加人具有防污染特性且适用于各种组成和用途的组合物，包括用于非常低的 $T_{\\mathrm{{g}}}$ 的聚合物。  \n\nLauer等人通过在涂料组成物中加入平均粒径 $\\mathtt{1\\sim50n m}$ 的聚合物纳米粒子（PNP）而提高涂层的防微生物污染性能，PNPs中含有 $1\\%\\sim100\\%$ 的至少一种多乙烯基不饱和单体，PNP粒径较好的为 $1{\\sim}30\\mathrm{nm}$ ，最好为 $1\\sim10\\mathrm{nm}$ 。其具有特定的组成或支链官能团，由于其粒径非常小，其表面积更高，可以提高干燥或固化后的表面所需的官能性的效率，可以改善耐微生物附着性。PNPs可以用于改进涂料组成物的表面性能，如提高表面硬度或韧性，减少表面降解，或降低表面能以减少涂层对粒子的吸附，有助于涂层的清洁或自清洁性。  \n\nMyers等人发明了一种抗菌涂覆金属板，涂料中含有抗菌助剂和树脂组合物，所用抗菌助剂的无机抗菌粒子为载有金属成分的氧化物和沸石粉末，无机抗菌核粒子带有具抗菌功能的金属或金属化合物表面层。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 416,
+        "chunk": "# 3.抗静电彩钢板涂料  \n\n在微电子、电控等行业中，静电感应产生的电压可能会引起系统的误动作，甚至能使半导体等耐电压低的器件损坏。通过在涂装钢板用的涂料中加人导电材料，例如金属粉末、导电石墨、锡和锌等的氧化物以及导电聚合物等，可以增加涂膜的导电性，制备抗静电钢板。抗静电预涂钢板的表面电阻一般可降至 $10^{6}\\sim10^{8}\\Omega$ ，而普通预涂钢板的电阻一般 ${\\tt>}10^{15}\\Omega$ 鼎",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 417,
+        "chunk": "# 七、环保卷材涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 418,
+        "chunk": "# 1．粉末涂料  \n\n粉末涂料和涂装技术是20世纪中期开发的一项新技术、新工艺，具有节省能源、减少污染、工艺简单、易实现工业自动化、涂层性能优异等特点。半个多世纪以来，伴随制造工艺和涂装技术的改进和发展，其年平均增长速率高达 $8\\%$ 以上，远高于涂料整体增长速率，长期以来得到各国的重视，尤其是进人21世纪以来，人类对环境保护更加重视，对挥发性有机物（VOC）和有害空气污染物（HAPS）向大气排放量的限制日益严格，对有限资源如何节省等问题日益关注。  \n\n粉末涂料和涂装技术与预涂卷材涂装技术的结合利用完全符合涂料的发展方向。热固性粉末涂料具有优异的耐候性、耐划伤性和其他的物化性能，其完全不含溶剂，过喷粉的回收再利用使其应用于卷材涂装比溶剂型涂料更有优势，采用粉末预涂可以使施工更简便。这是因为：粉末涂料出厂后无需进一步调配，无需稀释和调整黏度；粉末涂料可直接加入进料系统；所有过喷粉末均可从涂装线尾部的集料斗内回收再利用；无需仓库堆放凌乱的漆桶，降低成本；不存在漆液的溢流问题和专用盛漆装置；无溶剂排放和无火灾隐患等。  \n\n此外，采用粉末预涂技术可以拓展预涂卷材涂装技术的基材选择范围，粉末涂料可以很容易地施涂于液体涂料难以施工的打孔的金属板和装饰金属板。  \n\n正是由于粉末预涂技术的突出优点，欧美、日本等发达国家都把这一技术列为涂料的发展方向之一，特别是可应用于印花金属制品、穿孔金属制品和有纹络表面等当前卷材涂装难以涉及的新市场，形成新的市场增长点。  \n\n但由于预涂技术是采用金属薄板的连续涂装，固化时间短，根据不同的生产线，一般要求涂料能在 $20\\sim60\\mathrm{s}$ 内快速固化。这就要求粉末涂料快速固化，红外线技术、电感应技术、热对流技术、NIR技术等的综合使用可以使粉末涂料快速聚合。如果使用电感应加热固化，可使粉末涂料在20s内充分交联成膜，也可使用红外线加热技术在 $60s$ 内固化。可以根据不同的线速要求设计不同的加热方式达到要求： $\\textcircled{1}$ 低速涂装线（最高 $20\\mathrm{m/min}.$ ）采用传统的电晕/摩擦静电喷涂技术和红外线/热对流固化技术； $\\textcircled{2}$ 中速涂装线 $(20{\\sim}60\\mathrm{m/min})$ 采用粉末旋杯或新开发的TF粉末刮板技术以及红外线/热对流/电感应/NIR等固化技术； $\\textcircled{3}$ 高速涂装线（ $\\mathrm{\\bf\\ddot{6}0m/m i n}$ 以上）采用电感应加热固化，涂装线速可超过 $100\\mathrm{m/min}$ 0  \n\n实现高速粉末卷材涂装，除了涂装技术的改进外，粉末涂料配方设计也需要不断的进步。为了满足预涂卷材的性能要求，卷材粉末涂料是以聚酯体系和聚氨酯体系为主。  \n\n合肥荣事达工业包装装潢有限公司开发的中速卷材粉末涂料，基固化条件为$275^{\\circ}C/2\\mathrm{min}$ ，涂装线加热混合采用红外与热对流方式，采用摩擦枪喷涂。涂料为聚酯型，树脂玻璃化温度 $55^{\\circ}C$ 以上，软化点 $105\\mathrm{\\sim}115^{\\circ}\\mathrm{C}$ ，数均分子量 $5000{\\sim}8000$  \n\n巴斯夫公司（BASF）开发了一种粉末浆卷材涂料，它的优点是可以采用传统的熔融挤出方法制备粉末浆涂料。首先合成端羟基或端羧基的聚酯树脂，端羧基聚酯树脂酸值 $20\\sim$ $40\\mathrm{mg\\KOH/g}$ ，端羟基聚酯树脂羟值 $40{\\sim}100\\mathrm{mg}\\ \\mathrm{KOH/g}$ ，聚酯树脂可以是线型的，也可以部分支链化。固化剂一般选用常温下为固态的类型。对端羟基聚酯树脂，固化剂选用氨基树脂和封闭异氰酸酯树脂；对端羧基聚酯树脂，固化剂可选用含环氧官能团的环氧树脂和丙烯酸树脂，以及多环氧化合物如三缩水甘油基异氰脲酸酯（TGIC）等。粉末浆涂料组成物中的粉末树脂（包括固态的固化剂）的玻璃化温度或软化点为 $40\\sim60^{\\circ}C$ 。粉末涂料制备时，将树脂和固化剂干研磨至粒径 $20\\mathrm{\\sim}30\\mu\\mathrm{m}$ 后加人水性介质中，如需要还可加人颜料或填料。在水性介质中除了水，还可以预先加入分散剂、流变助剂、催化剂、消泡剂等助剂。然后将此粉末浆料以合适的分散设备研磨得到平均粒径 $3\\sim6\\mu\\mathrm{m}$ 的粉末浆涂料。  \n\n与传统的粉末涂料制备技术相比，采用粉末浆技术有许多优点。降低粉末涂膜的膜厚和改善涂膜的外观的方法之一是降低粉末的粒径，粉末涂料粒径越小，涂膜光泽和平滑性越好，施工的膜厚可以更均匀、更薄，但是采用传统的粉末制备方法，粒径降到一定程度（如低于 $5\\mu\\mathrm{{m}}^{\\prime}$ ）时很容易造成粉尘危害，而且研磨太细的粒子很容易产生黏结，而采用粉末浆技术就可以解决这一问题，它兼具了粉末涂料和水性涂料的特点。  \n\n德固萨公司（DegussaAG）开发了一种聚氨酯粉末涂料组成物。树脂体系为聚酯树脂和封闭异氰酸酯树脂。合成了端羟基的对苯二甲酸型聚酯树脂，其羟值30～100mg$\\mathrm{\\bfKOH/\\bar{g}}$ ，数均分子量 $1200{\\sim}5000$ ，熔点 $75\\sim100^{\\circ}C$ 。聚酯合成可以采用酯交换方法或酯化方法。封闭异氰酸酯制备时，封闭剂采用 $E-$ 己内酰胺，反应在无溶剂条件下在进行，反应温度90～130°℃。然后将聚酯树脂、封闭异氰酸酯和其他的颜填料、助剂混合，用传统的熔融挤出方法制备粉末涂料。  \n\n美国MSC开发的热固型聚酯预涂粉末涂料，涂膜膜厚可达 $20\\mu\\mathrm m$ 以下，机械加工性能优异，硬度高、外观好。  \n\n美国FirstPrecisionLLC开发了Powder CoilTM粉末卷材涂料的高速涂装和固化生产工艺，综合采用了PowderJet@ow 粉末涂料喷涂技术，加上AdPhos NIR近红外光固化技术和杜邦公司AlestaSpeedRay-Tec红外固化粉末卷材涂料，可以使生产线的速度超过  \n\n$100\\mathrm{m/min}$ ，粉末涂料的固化时间仅为 $5\\sim20{\\mathrm{s}}$ 中",
+        "category": " Introduction"
+    },
+    {
+        "id": 419,
+        "chunk": "# 2．水性涂料  \n\n受涂装工艺限制，水性涂料在卷材中的应用不多，即使在欧美等发达国家，也只有很少的几条水性涂料卷涂生产线。MorimotoOsamu等人发明了一种罐头内壁涂装及金属板材涂装用的水性预涂卷材涂料，其树脂组成物为聚酯和酚醛树脂，具有极好的固化性能、柔韧性、耐蒸煮性和耐萃取性。其中聚酯树脂是通过分子中含酸酐的化合物开环和加成反应得到，其数均分子量 $5000{\\sim}100000$ ，酸值 $150\\sim800\\mathrm{eq/106g}$ ，以碱性化合物中和得到水分散性。酚醛树脂是采用可溶性酚醛树脂，作为交联剂。  \n\nLaskin发明了一种水性卷材底漆，其基料中含有可热固化的、水分散型聚氨酯聚合物及可热固性的或热塑性的、可成膜的水分散型聚合物，通过两者的协同作用底漆的性能可以更好，这些性能包括柔韧性和冲击、底漆对金属底材和面漆的附着力、耐化学品性和防腐性、耐潮气和耐水性及室外耐久性等。  \n\nLeibelt，Ulrich 等人发明了一种自交联型金属容器用水性卷材涂料，其具有优异的附着力和柔韧性，内用不会影响容器内食品或饮料的味道。其由环氧树脂、水分散性丙烯酸树脂、颜料、填料、防腐剂和水性介质组成。  \n\nAsahina 等人发明了一种用于建筑外用、食品罐及卷材的含水性聚氨酯多元醇的水性涂料，所提供的水性聚氨酯多元醇分子中含有羟基、氨基甲酸酯基和亲水基团，其分子中平均羟基含量 $3\\sim20$ 、羟值 $10{\\sim}200\\mathrm{mg}\\ \\mathrm{KOH/g}$ 、氨基甲酸酯／（羟基 $+$ 亲水基）为 $1\\sim2$ 、数均分子量 $1000{\\sim}20000$ 8  \n\nWind 等人发明了一种水性食品饮料罐内用预涂卷材涂料，其VOC含量低且不含甲醛。该水性涂料中含环氧丙烯酸树脂水性分散体和聚合物活性稀释剂。  \n\nO'Brien 等人发明了一种包装容器用预涂卷材涂料，含有由环氧乙烷官能度为 $0.5\\sim5$ 的环氧乙烷官能烯烃的加成聚合反应产物、酸值 $30{\\sim}500\\mathrm{mg}\\ \\mathrm{KOH/g}$ 的酸官能聚合物和叔胺组成的水性分散体。  \n\nShimada等人发明了一种金属罐用水性预涂卷材涂料，该涂料中所用水性树脂制备是使数均分子量至少9000且环氧当量不超过9000的芳香族环氧树脂、数均分子量小于9000且环氧当量不超过5000的芳香族环氧树脂和玻璃化温度至少 $100^{\\circ}C$ 的含羧基丙烯酸树脂部分酯化反应得到丙烯酸改性环氧树脂，用碱中和后分散于水性介质中。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 420,
+        "chunk": "# 八、结论  \n\n彩钢板涂料经过数十年的发展，已经形成了较完善的涂料体系，有了广泛的应用。随着科技的进步，各种建筑涂料、海洋涂料、特种功能涂料、低污染化涂料等应用领域中的新技术均可引入彩钢板涂料中，从而不断扩展和提高其应用环境和功能性。  \n\n目前国内尚处于彩钢板应用的成长期，主要关注于普通建筑用彩钢板，而随着市场竞争全球化趋势的加快，高装饰性、高性能、低污染和功能性彩钢板涂料及彩钢板将成为必然的发展方向。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 421,
+        "chunk": "# 参考文献  \n\n[1］涂料工艺编委会．涂料工艺：下册．第3版，北京：化学工业出版社，1997.  \n[2]朱立，徐小连编著，彩色涂层钢板技术，北京：化学工业出版社，2005.  \n[3]张启富，黄建中编著，有机涂层钢板，北京：化学工业出版社，2003.  \n[4]］俞剑峰，岳远广，江社明，江巍，欧阳展鸿等．第5届国际彩板及涂料涂装技术研讨会论文集，昆明常州涂料化工18研究院，2007.  \n［5］上海汉高股份公司，上海凯密特尔化学品有限公司，SK化工（苏州）有限公司，力同化工（佛山）有限公司，王利群，吴奎录，刘谦，夏振华、司俊芳．第4届国际彩板及涂料涂装技术研讨会论文集．上海：常州涂料化工研究院，2006.  \n[6]Temtchenko 等．US 6242557.2001-06-05.  \n[7］李大鸣，王利群等，有机硅改性聚酯型耐久卷材面漆的研制，涂料工业，2007，37（12)：30-32.  \n[8]肖佑国，祝福君编著、预涂金属卷材及涂料、北京：化学工业出版社，2003.  \n[9］王利群，李大鸣等，预涂卷材涂料的性能影响因素．涂料工业，2005，35（1)：4-6.  \n[10]GB/T 12754—2006.  \n[11]HG/T 3830--2006.[12] Bamber Michael. EP 0634460. 1995-01-18.  \n[13］胡靖玮，罗志刚等．卷材用环氧聚氨酯底漆的研制．涂料工业，2003，33（2)：1-2.  \n[14]Richard Alla Hickner 等．GB 2121804A. 1984-01-04.  \n［15］俞剑峰等．CN1702128.2005-11-30.  \n[16]Laskin. US 4103050. 1978-07-25.[17] Marinow. US 6756450. 2004-06-29.  \n［18］杨小青等．高耐候卷材涂料用聚酯树脂．涂料工业，2006，36（12)：35-37.[19]Nguyen，Diep 等．US 6699933.2004-03-02.[20］申龙，戴毅刚等．建筑用彩色涂层板发泡粘接性探讨．涂料工业，2006，36（1)：59-61.[21］冯春苗等．家电板用黑色导电背漆的研制，涂料工业，2006，36（10)：29-31.[22］夏范武，许君栋等、高耐久涂料用交联型氟涂料，涂料工业，2005，35（11)：54-59.  \n［23］李大鸣．国内家电用彩板市场及家电板涂料研究进展．涂料技术与文摘，2007，28（11)：5-7.  \n［24］王利群，陈义庆，张连伟．第3届国际彩板及涂料涂装技术研讨会论文集，常州：常州涂料化工研究院，2005.[25]Hane Takashi等．JP 07-292316.1995-11-07.[26]Hoehne，Joerg 等．US 6933047．2005-08-23.  \n[27]Wamprecht，Christian 等．US 6863863．2005-03-08.  \n[28]Tulls，Bryan等．US 7125613.2006-10-24.  \n[29]Bend Meuthen.Safe working environmentsOnecomponent PUR systems for coilcoating.ECJ，24，(3):34-45.[30］Gray，RalphC等．US 6750274.2004-06-15.  \n[31]Berger，Valentin等．US 6777034．2004-08-17.[32]Morimoto Osamu 等．EP 1273626A1.2003-01-08.[33］刘相华，王国栋．食品罐用有机涂层板．轧钢，2001，18（2)：47-49.[34]James Thomas Maxted，张俊智，Beverly A．Graves．第2届国际彩板及涂料涂装论坛论文集．常州：常州涂料化工研究院，2004.[35］施利毅，周莉等．CN1884406.2006-12-27.［36］施利毅，钟庆东等．CN1569992.2005-01-26.  \n［37］魏涨渠，朱建强等．CN1118790．1996-03-20.[38］戴毅刚，张剑萍．CN1239728．1999-12-29.［39］河上克之，中村充等．CN1311063．2001-09-05.［40］中村充，河上克之等．CN1614089.2005-05-11.[41]Lauer等．EP 1371690A2.2003-12-17.[42]Klesse 等．US 6194530.2001-02-27.  \n[43]Myers 等．US 6929705.2005-08-16.[44]Sacharski等．UP 6360974.2002-03-26.  \n[45]Leibelt，Ulrich 等．US 6008273.1999-12-28.[46]Asahina 等．US 7012115. 2006-03-14.[47]Wind 等．US 7037584.2006-05-02.  \n[48]O'Brien 等．US 7189787.2007-03-13.[49]Shimada等．US 6514619.2003-02-04.",
+        "category": " References"
+    },
+    {
+        "id": 422,
+        "chunk": "# 塑料涂料  \n\n塑料涂料顾名思义即是用于塑料表面进行涂装的涂料，在塑料表面涂装可以达到以下目的。  \n\n(1）提高塑料制品的装饰性，降低制品的制作成本塑料制品的着色过去传统的做法是借助于色母粒。色母粒的成本因颜料成本高而普遍较高，同时色母粒着色时颜料用量大，因而造成色母粒着色时的色料成本也普遍偏高。  \n\n(2）提高塑料制品的使用寿命塑料制品一般对光及水等较敏感，而通过选择高耐候的涂层可以显著提高塑料制品的使用寿命。  \n\n(3）赋予塑料制品某些特殊功能例如电磁波屏蔽——用于笔记本电脑外壳，防霉、阻燃、导电等。  \n\n目前使用塑料涂料对塑料基材进行涂装普及到各个领域。如汽车、机械、日用品、电子、化工玩具等。据有关资料介绍仅在国内用汽车塑料涂料就占汽车用涂料的16%（包括抗石击涂料)，《化学周刊》披露伦敦一家研究机构提供情报，未来一段时间内西欧市场塑料涂料的需求年均增速达 $3.4\\%$ 。2008年西欧塑料涂料的需求总量将达到12.4万吨/年。而根据相关资料信息，近几年西欧塑料涂料的年消费量约占全球 $25\\%$ 的市场。塑料涂料在中国及亚洲的新兴工业化国家具有极大的发展空间。  \n\n近年来塑料涂料也像其他类型涂料一样，在高装饰性、功能化、低成本化和环境友好型等方面进行同步改善。塑料涂料的特征如下。",
+        "category": " Introduction"
+    },
+    {
+        "id": 423,
+        "chunk": "# 1.塑料涂料的高装饰性  \n\n塑料涂料除了在光泽、丰满度方面的进一步发展外，其新感觉化在许多地方是一个趋势。如砂面、绒面、光致变色、随角异色、裂纹、皱皮等一系列原先只出现在金属涂料中的涂膜效果，现在几乎在塑料涂料中均有体现，甚至得到了更多的发展。",
+        "category": " Introduction"
+    },
+    {
+        "id": 424,
+        "chunk": "# 2.塑料涂料的功能性  \n\n涂层功能化研究涉及弹性、韧性、耐磨性等。实现这些功能大多是依靠对助剂及填充料的选择来完成。如掺入导电粉体引人抗静电功能，掺入磁粉形成电子屏蔽现象，加人高硬度填料增强涂膜耐磨性，补充高分子增韧剂提高涂膜韧性及耐磨性等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 425,
+        "chunk": "# 3.塑料涂料的低成本化  \n\n塑料采用涂料涂装与采用色母粒着色、模具、精密化工艺路线相比，在材料的外装饰性上产生的成本要低很多。然而随着市场竞争的不断深化，塑料涂装成本的控制成为一个相当紧迫的问题。为此一些有助于提高性能的低价原材料逐渐被涂料生产者所采用，如纳米级填充物、高长径比的短纤维状填充物等。这些填充料可部分取代过去为改善性能而引入的增  \n\n韧剂，还可减少抗划痕助剂的使用。  \n\n![](images/524e83658d66bad20f869aa233bfdf4f227226d58e9fac53f1470b7d0d3a4e82.jpg)  \n\n塑料与钢铁、木材、水泥一起共同构成了现代工业四大基础材料，在国民经济中占有重要地位。塑料具有材料综合性能优异、加工方便、生产和使用中可以显著节约能源等优点，使其被广泛应用于工农业生产和日常生活当中。",
+        "category": " Introduction"
+    },
+    {
+        "id": 426,
+        "chunk": "# 一、塑料的组成与分类  \n\n塑料因其聚合物不同而品种繁多，且每一品种又具有多种牌号。为了便于识别和使用，需对之进行分类。常用的分类方法有如下几种。  \n\n（1）根据塑料的来源分 天然树脂、合成树脂(2）根据制造树脂的化学反应类型分 加聚型塑料、缩聚型塑料。  \n\n树脂合成的加聚反应是指在一定的条件下，单体分子的活性链发生相互作用，“加聚”成一条大分子链的过程；而缩聚反应是靠单体中的可反应基团等来反应的，其反应是逐步缩合的，并伴有水、氨、甲醇、氯化氢等某种小分子物质析出。  \n\n(3）根据聚合物链之间在凝固后的结构形态分非结晶型（无定型)、半结晶型、结晶型。  \n\n结晶型塑料在凝固时，有晶核到晶粒的生成过程，形成一定的形态结构，如聚乙烯、聚丙烯、尼龙等。无定型塑料在凝固时，没有晶核的形成、晶核的成长过程，只是自由的大分子链的“冻结”，如聚苯乙烯、聚氯乙烯、有机玻璃、聚碳酸酯等。  \n\n(4）从应用角度来区分通用塑料、工程塑料两大类。其中，工程塑料中又可细分出特种工程塑料以及用在特殊场合的功能塑料，如医用塑料、光敏塑料、珠光塑料、导磁塑料、离子体塑料等。  \n\n(5）按塑料成型方法来分有模压塑料、层压塑料、注塑塑料、挤塑塑料和吹塑塑料、浇注塑料、反应注射模塑材料等。(6）从化学结构及其基本行为分热固性塑料、热塑性塑料两大类，这是比较科学的分类法。  \n\n热固性塑料成型前是可溶可熔的，即为可塑的，在一定的温度和压力条件下，经历一定时间的固化，能成型为不溶不熔的物质。常用的热固性塑料品种有酚醛树脂、脲醛树脂、三聚氰胺树脂、不饱和聚酯树脂、环氧树脂、有机硅树脂、聚氨酯等，见表3-6-1。  \n\n表3-6-1 热固性塑料分类  \n\n\n<html><body><table><tr><td>交联方式</td><td>树脂种类</td><td>交联方式</td><td>应用领域</td></tr><tr><td>CHzOH缩水交联</td><td>酚醛树脂、三聚氰氨树脂</td><td>加热</td><td>用在耐热性领域</td></tr><tr><td>R NHz—CH-CH—R 0</td><td>环氧树脂</td><td>常温或加热</td><td>路板和电子元件的铸封</td></tr><tr><td>CNO+HO(R-OH) 或HN—R—NHz</td><td>聚氨酯、聚脲</td><td>常温或加热</td><td>常用于低温绝缘性好的环境</td></tr><tr><td>CH—CH—-</td><td>酸不和酯、酸丙基树脂丙烯</td><td>聚化学引发和光引发</td><td>玻璃钢</td></tr><tr><td>其他交联方式</td><td>有机硅树脂</td><td>加热</td><td>电子元器件材料</td></tr></table></body></html>  \n\n热塑性塑料是指在特定温度范围内可反复加热软化和冷却硬化（成型）的塑料，或者说是反复可溶可熔、可以多次成型的塑料。常用的品见表3-6-2。  \n\n表3-6-2 热塑性塑料分类  \n\n\n<html><body><table><tr><td>结构类型</td><td>树脂的种类</td></tr><tr><td>聚烯烃类</td><td>结晶型：聚乙烯、聚丙烯、聚甲基戊烯、聚丁二烯、聚丁烯 非结晶型：苯乙烯、聚丁二烯、聚丁二烯-苯乙烯</td></tr><tr><td>乙烯基类</td><td>聚氯乙烯、聚乙酸乙烯、聚甲基丙烯酸甲酯、聚乙烯-乙酸乙烯共聚物、聚四氟乙烯、聚偏氟乙烯、 AS、ABS、ACS、离子聚合物等</td></tr><tr><td>其他线型聚合物类</td><td>聚甲醛、聚酰胺、聚碳酸酯、聚苯醚、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚丙炔、聚 矾、聚酰亚胺、氯化聚醚、氟塑料、线型聚酯等</td></tr><tr><td>纤维索类</td><td>硝基纤维素、醋酸纤维素、乙基纤维素等</td></tr></table></body></html>  \n\n由于用途不同、改性方法不同又衍生出不同种类的塑料。例如：硬质塑料、软质塑料、薄膜等；泡沫塑料；开孔闭孔泡沫塑料；由玻璃纤维或碳纤维增强的塑料——玻璃钢（GFRP)；由钙系填料增强改性的钙塑材料；以及塑料与其他材料复合的塑料合金等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 427,
+        "chunk": "# 二、塑料的特性  \n\n塑料材料品种很多，其性能也大不相同。有的以高强度著称，有的以耐腐蚀优先，有的侧重于电气绝缘性等。尽管塑料品种较多，性能差别大，然而，塑料材料与其他材料相比，仍具有共同特性，其表现主要为如下几个方面特点。",
+        "category": " Introduction"
+    },
+    {
+        "id": 428,
+        "chunk": "# 1.质轻  \n\n塑料都比较轻，各种泡沫塑料的相对密度在 $0.01{\\sim}0.05$ ，普通塑料的相对密度一般在$0.9\\sim2.3$ 。在要求减轻自重的用途中，塑料材料有着特殊重要的意义。例如，波音707、747飞机上大量采用聚碳酸酯这种塑料材料就是为了减轻自重。在运输机械用材上，塑料的比例不断增加，尤其是结构泡沫塑料和纤维增强塑料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 429,
+        "chunk": "# 2.电气绝缘性好  \n\n在电性能方面，塑料包含着极其宽广的指标范围。体积电阻率高达 $10^{16}\\sim10^{20}\\Omega\\cdot\\mathrm{cm}$ 电介电损耗低到 $10^{-4}$ 。总体来说，大多数塑料在低频、低压条件下具有良好的电气绝缘性，不少塑料即使在高频、高压条件下也能作为电气绝织材料和电容器介质材料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 430,
+        "chunk": "# 3.隔热性能好  \n\n塑料的热导率极小，比金属小上百倍甚至上千倍，是热的不良导体或绝热体，因而常被用作绝热保温材料。泡沫塑料的热导率与静止的空气相当。因此，聚苯乙烯、聚氨酯等许多泡沫塑广泛应用于冷藏、建筑、节能装置和其他绝热工程。",
+        "category": " Introduction"
+    },
+    {
+        "id": 431,
+        "chunk": "# 4.机械强度范围宽  \n\n塑料的机械强度范围宽广，从柔顺到坚韧甚至到刚、脆都有。大多数塑料的制品的刚度与木材相近。不同塑料材料的机械强度差别很大；拉伸强度从 $10{\\sim}50\\ensuremath{\\mathbf{MPa}}$ 甚至更大的都有。塑料的比强度接近或超过传统的金属材料的比强度。因此，普通塑料特别适用于受力不大的结构件。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 432,
+        "chunk": "# 5.成型加工性能好  \n\n塑料成型加工方便，例如用塑料做的机器零件，可以不需经过铸造、铣、刨等工序，只要一次成型即可。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 433,
+        "chunk": "# 6.减振、消音作用强  \n\n许多塑料由于柔软而富于黏弹性，当受到外界的机械冲击振动或频繁的机械波作用时，塑料内部产生黏弹内耗，将机械能转变为热能而散发。因此，工程上常利用塑料（尤其泡沫塑料）材料作为减振和消音材料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 434,
+        "chunk": "# 7.耐磨性能好  \n\n大多数塑料摩擦系数很小，有些塑料还具有优良的减摩、耐磨和自润滑特性。许多工程塑料制品的摩擦零件可以在各种液体摩擦、边界摩擦相干摩擦等条件下有效地工作。有些塑料的耐磨性为许多金属材料所不及。例如，各种氟塑料以及用氟塑料增强的聚甲醛、聚酰胺塑料就是良好的耐磨材料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 435,
+        "chunk": "# 8.透光性及其防护性能良好  \n\n不少塑料如聚苯乙烯、聚氯乙烯、聚碳酸酯和丙烯酸类塑料是无定形的 (或很少结晶)。有些塑料（如聚酯、尼龙等）虽然结晶度较高，但其晶粒可以控制得很小，所以，许多塑料制品可以做成透明或半透明材料。其中聚苯乙烯和丙烯酸类塑料和玻璃一样透明，常用作特殊环境下玻璃的替代品。利用聚丙烯、聚乙烯等塑料薄膜既透光又保暖的特性，大多用于保护农作物。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 436,
+        "chunk": "# 9.结晶性  \n\n塑料、合成纤维和合成橡胶均为高分子合成材料。其中，合成纤维分子结晶性高（分子排列规范)、配向性大；合成橡胶为非结晶性的弹性材料；而塑料处于合成纤维和橡胶的中间的位置。  \n\n塑料有无结晶性对漆膜附着关系极大。即结晶性高则漆膜附着差，这就是为什么涂装前必须进行表面处理，或者选用特殊的专用底漆的原因。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 437,
+        "chunk": "# 10.塑料改性  \n\n与金属材料相比，塑料的比强度、耐热系数相对较小；而电阻率、热膨胀系数相对较高。这就是为什么要加入玻璃纤维或碳纤维以及无机填料，或者制成复合材料以便改进和调整其性能，满足不同用途的需求。",
+        "category": " Introduction"
+    },
+    {
+        "id": 438,
+        "chunk": "# 11.常用性能指标  \n\n塑料的拉伸强度、相对伸长、耐冲击、耐热性四个指标是最常用的性能指标，也是必须与涂料相匹配的、最基本的特性指标。通常，拉伸强度高的其耐热性较好；耐冲击性好的其相对伸长较高。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 439,
+        "chunk": "# 12.电阻及导电性  \n\n热塑性塑料的体积电阻率一般 $>10^{13}\\Omega\\cdot\\mathrm{~m~}$ ，热固性塑料的体积电阻率比热塑性塑料稍低。因此实际上往往加入防静电剂或者与无机填料复合后成型以降低其带静电性。但是防静电剂往往容易迁移至塑料表面而有害于漆膜的附着。这是必须特别留意之处。  \n\n由于塑料表面带静电后，容易吸附灰尘等杂物而影响涂层的附着并产生涂装缺陷。在有条件的地方，最好采用电晕放电，使空气预先除尘，并严格涂装室的湿度管理以确保塑料制  \n\n品少带电或不带电，提高涂装质量。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 440,
+        "chunk": "# 13.表面张力  \n\n塑料的表面张力与金属不同，塑料一般是低表面能的表面，不利于涂料的附着。塑料的表面特征是涂料附着的关键，以后将详细叙述。",
+        "category": " Introduction"
+    },
+    {
+        "id": 441,
+        "chunk": "# 14.溶解度参数  \n\n塑料的溶解度参数即塑料涂料中溶剂和树脂的相容性，也是影响涂装质量的关键因素之一。在第二节中将详细讨论。",
+        "category": " Introduction"
+    },
+    {
+        "id": 442,
+        "chunk": "# 15.残余应力  \n\n塑料加工成型后的残余应力对涂料的附着和涂装缺陷会有一定的影响。  \n\n综上所述，塑料由于它的优良的、多样的实用性，故在工农业生产、日常生活、国防以及科技领域中获得相当广泛的应用。  \n\n然而，塑料也有许多缺陷、主要有如下几方面。  \n\n$\\textcircled{1}$ 热性能差。塑料的许多性能对温度的依赖性十分显著，即在不太高的温度之下，足以改变大分子热运动方式和聚集态结构，从而影响到塑料几乎所有的性能。因此，使用温度范围不宽和耐热性较差，是塑料突出的问题。  \n\n$\\textcircled{2}$ 塑料的强度低，刚度则更低  \n\n$\\textcircled{3}$ 不易成型尺寸精密的制品。  \n\n$\\textcircled{4}$ 塑料制品在使用过程中易产生蠕变冷流、疲劳和结晶等现象。导热性不良和热膨胀系数大。",
+        "category": " Introduction"
+    },
+    {
+        "id": 443,
+        "chunk": "# 三、常用塑料性能简介  \n\n1.ABS（丙烯腈-丁二烯-苯乙烯共聚物）  \n\n（1）特性ABS是不透明的非晶型树脂，加工性非常好。可注射、挤出、压延、热成型。还可进行机加工、焊接、粘接、涂漆和电镀等：在二次加工中，ABS是所有塑料中最易电镀的品种。主要缺点是耐候性差，室外长期暴露易老化变色，从而降低了冲击强度和硬度。此外，ABS还易溶于醛、酮、酯等有机溶剂中。  \n\n(2）典型应用范围汽车（仪表板，工具舱门，车轮盖，反光镜盒等)、电冰箱、大强度工具（头发烘干机，搅拌器，食品加工机，割草机等)、电话机壳体、打字机键盘、娱乐用车辆（如高尔夫球手推车）以及喷气式雪撬车等。表3-6-3是国内通用ABS牌号和性能。  \n\n表3-6-3 国内通用ABS牌号和性能  \n\n\n<html><body><table><tr><td>型号</td><td>熔体指数</td><td>特性与用途</td></tr><tr><td>通用型</td><td></td><td>冲击强度较高，可作机壳及零部件</td></tr><tr><td>701</td><td>1~1.4</td><td>冲击强度中等，可作家具，收录机零件</td></tr><tr><td>301</td><td>1.3~2.3</td><td>冲击强度略低，可作杂品、玩具、灯具</td></tr><tr><td>101.102</td><td>1.5~3</td><td>流动性好，可注射大型和复杂形状制品</td></tr><tr><td>高流动性F3</td><td>3~4.5</td><td>高刚性，冲击强度较高，可挤出板、管、棒</td></tr><tr><td rowspan=\"2\">挤出型E7 挤出型E3、E1</td><td>0.8~1.2</td><td rowspan=\"2\">冲击强度中等，可挤出型材及真空成型壳体</td></tr><tr><td>0.5~1.8</td></tr></table></body></html>  \n\n续表  \n\n<html><body><table><tr><td>型号</td><td>熔体指数</td><td>特性与用途</td></tr><tr><td>耐热型T5</td><td>0.1</td><td>耐热性最好，可作热工仪器盘、耐热机壳</td></tr><tr><td>耐热型T2</td><td>0.9~1.3 0.5~1.5</td><td>耐热性次之，可作纺织器材。纱管低温韧性好，可作低温使用的部件</td></tr><tr><td>耐寒型G8 难燃型VI</td><td>9~12</td><td>阻燃V0级，可作防火的部件</td></tr><tr><td>高耐冲型H08</td><td>0.5</td><td>高耐冲性能，可作反坦克地雷外壳等</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 444,
+        "chunk": "# 2.聚乙烯（PE)  \n\n（1）高密度聚乙烯（PE-HD，相对密度0.95）  \n\n$\\textcircled{1}$ 特性PE-HD的高结晶度导致了它的高密度、高拉伸强度、高温扭曲温度、高黏性以及化学稳定性。PE-HD比PE-LD有更强的抗渗透性。PE-HD的耐冲击强度较低。燃烧时放出臭气，但无烟，耐水、耐化学药品优异，不透水和空气。难以盛放涂料和油墨，不耐热和大气老化。  \n\n$\\textcircled{2}$ 典型应用范围电冰箱容器、存储容器、家用厨具、密封盖等。  \n\n(2）低密度聚乙烯（PE-LD，相对密度0.92)  \n\n$\\textcircled{1}$ 特性分子量较低，分子链有支链，结晶度较低 $(55\\%\\sim60\\%)$ ，故密度小，质地柔软，透明性较HDPE好；耐冲击、耐低温性极好，但耐热性及硬度都低。不耐紫外光，在$100^{\\circ}C$ 加热逐渐劣化。难附着涂料和油墨。  \n\n$\\textcircled{2}$ 典型应用范围用于制作农用食品及工业包装用薄膜，电线电缆包覆及涂层，合成纸张等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 445,
+        "chunk": "# 3.聚丙烯（PP)  \n\n聚丙烯是以丙烯为单体聚合制得的聚合物，常温下为白色蜡状半透明颗粒，它比聚乙烯更透明更轻，相对密度为0.90。聚丙烯分子链中按甲基在空间的排列情况可分为三类，即无规聚丙烯（APP)、等规聚丙烯（IPP)、间规聚丙烯（SPP)，APP主要用于塑料改性时的添加剂，SPP主要用于弹性体，IPP产量在三种结构中占 $95\\%$ 0  \n\n（1）特性聚丙烯的结晶度一般为 $50\\sim70$ ，晶态相对密度为0.935。非晶态相对密度为0.850，熔点 $170^{\\circ}C$ ，热变形温度为 $150^{\\circ}C$ ，可在 $110^{\\circ}C$ 使用。聚丙烯的拉伸强度比聚乙烯、聚苯乙烯和ABS为高，制品硬度也较PE为高。其突出优点为具有较高韧性和耐弯曲疲劳。聚丙烯介电常数小，绝缘性能优异，不吸潮，对酸、碱、盐和众多有机溶剂均很稳定。聚丙烯的主要缺点是制品收缩率高，易翘曲，由于分子链中含有众多的叔碳原子，因而制品耐光、热性差。难以附着涂料和油墨。PP树脂的主要性能见表3-6-4。  \n\n表3-6-4PP树脂的主要性能  \n\n\n<html><body><table><tr><td>项目</td><td>标准型</td><td>耐冲击型</td><td>双轴拉伸膜</td></tr><tr><td>相对密度</td><td>0.9</td><td>1.04</td><td>0.9</td></tr><tr><td>拉伸强度/MPa</td><td>34.32</td><td>19.61</td><td>98.07</td></tr><tr><td>硬度（M.Rockwell)</td><td>98</td><td>82</td><td>一</td></tr><tr><td>热变形温度/C</td><td>115</td><td>100</td><td>一</td></tr><tr><td>耐电压/(kV/mm)</td><td>30</td><td>30</td><td>30</td></tr><tr><td>吸水率/% <</td><td>0.03</td><td>0.03</td><td>0.03</td></tr><tr><td>相对伸长率</td><td>600</td><td>500</td><td>60</td></tr></table></body></html>  \n\n(2）典型应用范围应用于汽车工业（主要使用含金属添加剂的PP：挡泥板、通风管、风扇等)、器械（洗碗机门衬垫、干燥机通风管、洗衣机框架及机盖、冰箱门衬垫等)、日用消费品（草坪和园艺设备如剪草机和喷水器等）。",
+        "category": " Introduction"
+    },
+    {
+        "id": 446,
+        "chunk": "# 4.聚氯乙烯（PVC)  \n\n聚氯乙烯是以氯乙烯单体经加成聚合反应而制成的热塑性线型树脂，未加其他配方的单一聚氯乙烯树脂难以形成实用材料，因而聚氯乙烯总要配以增塑剂、稳定剂等助剂组成材料。聚氯乙烯是世界上产量仅次于聚乙烯的树脂，通过不同的配方，可制成管材、板材、型材、薄膜、纤维、人造革等产品。  \n\n（1）特性聚氯乙烯为白色粉末状固体，不溶于水、酒精和汽油。它没有明显的熔点，$130^{\\circ}C$ 可软化， $140^{\\circ}C$ 开始分解。分解速率随温度升高而增加，共熔化流动温度为 $180^{\\circ}C$ 左右，熔化后的PVC流动性很差，因而难以直接进行挤出或注射成型。加入增塑剂后会明显改善其流动性，当增塑剂含量 $<10\\%$ 时得到硬质PVC制品， $>30\\%$ 时得到软质PVC制品。喷涂涂料时若溶剂使用不当，增塑剂易渗出。  \n\n(2）典型应用范围可用于供水管道、家用管道、房屋墙板、商用机器壳体、电子产品包装、医疗器械、食品包装等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 447,
+        "chunk": "# 5.聚苯乙烯（PS）  \n\n聚苯乙烯是以苯乙烯为单体聚合制成的塑料，为无色透明的粒状树脂。无臭无味，相对密度1.05，熔化温度 $150\\sim180^{\\circ}\\mathrm{C}$ ，分解温度 $300^{\\circ}C$ 。  \n\n(1）特性刚性高，表面硬度大，透明性好，耐冲击性差。PS对化学药品很稳定，不吸潮。聚苯乙烯的介电损耗小，耐电弧，是优异的电子工业材料。  \n\n(2）典型应用范围聚苯乙烯（PS）是一种多功能塑料，广泛应用于食品包装、CD盒、绝缘板、商业机器设备、资讯器材、家电、消费性产品等许多日常生活领域中（表3-6-5)。  \n\n表3-6-5 通用及耐冲击级苯乙烯特性及用途  \n\n\n<html><body><table><tr><td colspan=\"2\">类 别</td><td>特性</td><td>用 途</td></tr><tr><td rowspan=\"4\">通用级聚苯乙烯GPPS</td><td>915F</td><td>高流动级TPR混炼</td><td>TPR混炼用等</td></tr><tr><td>818</td><td>挤出级，高分子量，高强度，耐热性佳</td><td>OPS/PSP挤板制品等</td></tr><tr><td>866</td><td>射出级，透明度良好，耐热性佳</td><td>容CD 盒,家电制品、家庭五金、化妆品</td></tr><tr><td>861</td><td>射出级，透明度良好，耐热性佳</td><td>家电制品、家庭五金、化妆品容器灯 饰、玩具</td></tr><tr><td rowspan=\"3\">耐冲击级聚苯乙烯HIPS</td><td>661</td><td>中耐冲击度，高光泽，高流动性</td><td>家电制品、玩具、文具</td></tr><tr><td>616</td><td>超高耐冲击强度，挤出级，耐热性佳</td><td>挤板制品、线轴、浮球</td></tr><tr><td>666</td><td>超高耐冲击强度，射出级，高流动性</td><td>计算机外设制品、家电制品、文具</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 448,
+        "chunk": "# 6.聚酰胺（PA)  \n\n聚酰胺是一种主链上含有重复酰氨基的聚合物，其合成方法多为两种单体的缩合反应，商品名为尼龙。  \n\n(1）特性耐油性和耐化学溶剂性好，难燃、无毒、易染色、易吸水。聚酰胺具有耐磨和自润滑的特性，强度、韧性和硬度均较高，可在一 $40\\sim100^{\\circ}C$ 下长期工作，其性能会依碳原子数目的多少而变化。聚酰胺的加工工艺性较好，熔体黏度低、流动性高、加工温度范围广，可用注射、挤出、浇注、挤拉等方法成型各种工程塑料制品，还可进行二次加工。聚酰胺主要缺点是吸水率高、制品的后收缩率大。因此PA在加工前需在100℃左右干燥。  \n\n(2）典型应用范围聚酰胺常用在机械、仪器仪表、汽车等行业中的轴承、齿轮、凸轮、泵、闸门、垫圈、油箱、油管、拉链等工业用品中。",
+        "category": " Introduction"
+    },
+    {
+        "id": 449,
+        "chunk": "# 7.聚碳酸酯（PC)  \n\n聚碳酸酯是一种无味、无臭、无毒、透明的无定形热塑型材料，是分子链中含有碳酸酯的一类高分子化合物的总称，简称PC。因制品性能、加工性能及经济因素等的制约，目前仅有双酚A型的芳香族聚碳酸酯投入工业化规模生产和应用。一般结构式可表示：  \n\n$$\n\\left.\\left[o-\\bigcup\\limits_{i=1}^{\\mathrm{{CH}_{3}}}\\right]-\\bigcup\\limits_{i=1}^{\\mathrm{{O}_{i}}}\\right\\}_{n}^{0}\n$$  \n\n$\\pmb{\\mathscr{n}}$ 约为140  \n\n（1）特性相对密度为1.20，熔点为 $220{\\sim}230^{\\circ}C$ ，可溶于二氯甲烷、间甲酚、环己酮和二甲基酰胺等，在乙酸乙酯、四氢呋喃和苯中溶胀。突出表现在其具有优良的力学性能、热性能和电性能，特别是其冲击韧性很高，具有高透明度和耐蠕变性，尺寸稳定性好，可在$-60{\\sim}120^{\\circ}C$ 长期使用。  \n\n(2）典型应用范围双酚A型聚碳酸酯是目前产量最大、用途最广的一种聚碳酸酯，也是发展最快的工程塑料之一。作为工程塑料广泛用于透明材料、电器零部件、医疗器械和机械罩壳等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 450,
+        "chunk": "# 8.聚甲醛树脂（POM)  \n\n聚甲醛是甲醛的均聚物和共聚物的总称，由于共聚甲醛分子链中引人了C一C键，从而隔断了缩醛链，使其耐碱、耐热水的性能大大增加，因此国内外的聚甲醛树脂以共聚甲醛为主。  \n\n(1）特性聚甲醛是一种没有侧链、结晶度高的线型聚合物，外观为白色有光泽的颗粒，易燃烧，有良好的耐油性，但不耐酸、碱和紫外线。  \n\n聚甲醛的拉伸强度可达 $\\mathrm{70MPa}$ ，可在 $104^{\\circ}C$ 下长期使用，脆化温度为一 $40^{\\circ}C$ ，吸水性较小。但聚甲醛的热稳定性较差，耐候性较差，长期在大气中曝晒会老化。  \n\n聚甲醛的力学性能相当好，它具有较高的强度的弹性模量，摩擦系数小，耐磨性能好。聚甲醛还具有高度抗蠕变和应力松弛的能力。聚甲醛尺寸稳定性好，吸水率很小，所以吸水率对其力学性能的影响可以不予考虑。聚甲醛有较好的介电性能，在很宽的频率和温度范围内，它的介电常数和介电损耗角正切值变化很小。  \n\n(2）典型应用范围由于聚甲醛是一种力学性能优异的工程塑料，因而广泛应用于机械、电子、仪表、化工、纺织、农业等部门，常用的加工方法是注射、挤出、吹塑、喷涂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 451,
+        "chunk": "# 9.酚醛树脂及塑料（PF)  \n\n酚醛树脂是以酚类化合物与醛类化合物缩聚而制得的树脂，结构式如下。  \n\n![](images/7425c398e9e48647fc4183abdd0f57b9d97a2b4f70ac15351d7868a43cf304d5.jpg)  \n\n其中以苯酚和甲醛制得的酚醛树脂用量最大，在酚醛树脂中添加各种助剂所得到的塑料称为酚醛塑料，是热固性塑料的主要品种。  \n\n(1）特性不溶解于水，溶于丙酮、酒精等有机溶剂中。能耐弱酸和弱碱，遇强酸发生分解，遇强碱发生腐蚀。  \n\n<html><body><table><tr><td>密度/（g/cm²）</td><td>1.50</td><td>冲击强度/（kJ/m²）</td><td>>5.0</td></tr><tr><td>比容/（mL/g)</td><td>2.0</td><td>弯曲强度/MPa</td><td>>58.8</td></tr><tr><td>收缩率/%</td><td>0.5～1.0</td><td></td><td></td></tr></table></body></html>  \n\n酚醛塑料的优点是耐热性高（ $\\cdot150^{\\circ}C$ 下长期工作)，尺寸稳定性高，电气绝缘性能优异，机械强度好，耐化学腐蚀，因而常用作电气绝缘、耐热、耐磨及防腐蚀材料。  \n\n酚醛塑料的主要缺点是性脆，耐电弧性差和吸湿率较高，常用聚酰胺、聚氯乙烯、丁晴橡胶与酚醛树脂共混，以提高其机械强度和韧性，改善吸水率高的缺点。  \n\n(2）典型应用范围一般酚醛树脂常用玻纤增强，或用环氧树脂、聚乙烯醇缩丁醛与其混合，改善其脆性。此外还可用有机硅对其改性，以提高其耐热性和高温绝缘性。主要用于制造瓶盖、纽扣等日常生活用品及一般机器按钮、零件等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 452,
+        "chunk": "# 10.聚甲基丙烯酸甲酯（PMMA)——有机玻璃  \n\n有机玻璃是一种用途广泛的产品，其结构式可表示为：  \n\n![](images/fe9d585ba7cfdc2756a5813b9a5ce12762c46bd4bb19514747a3d18e3b9fea6c.jpg)  \n\n主要性能如下：  \n\n相对密度 $1,18\\sim1,19$ 透光率 $\\int\\frac{\\theta}{2}x^{2}d x^{2}$ 热变形温度/C $\\geq78^{5}C$ ≤15mm拉伸强度/MPa 60 ≥15mm冲击强度/MPa 1.2  \n\n91  \n\n有机玻璃能溶解于苯、二甲苯、丙酮、氯仿等溶剂中，而甲醇、乙醇等有机物能使有机玻璃表面膨胀或粗糙发毛。  \n\n(1）特性透明性优异，耐候性好，耐水，耐盐水，耐弱酸，不耐碱和有机溶剂。成型性良好电气性能优异，硬度高，表面光泽度高。 $100^{\\circ}C$ 可变形，耐冲击性能下降。  \n\n(2）典型应用范围有机玻璃具有以上优良性能，使它的用途极为广泛。除了在飞机上用作座舱盖、风挡和弦窗外，也用作吉普车的风挡和车窗、大型建筑的天窗（可以防破碎)、电视和雷达的屏幕、仪器和设备的防护罩、电讯仪表的外壳、望远镜和照相机上的光学镜片。  \n\n用有机玻璃制造的日用品琳琅满目，如用珠光有机玻璃制成的纽扣，各种玩具、灯具也都因为有了彩色有机玻璃的装饰作用，而显得格外美观。有机玻璃在医学上还有一个绝妙的用处，那就是制造人工角膜。",
+        "category": " Introduction"
+    },
+    {
+        "id": 453,
+        "chunk": "# 11.聚氨酯（PU)  \n\n主链含—NHCOO—重复结构单元的一类聚合物，英文缩写PU，由异氰酸酯（单体)与羟基化合物聚合而成。  \n\n(1）特性由于含强极性的氨基甲酸酯基，不溶于非极性溶剂，具有良好的耐油性、韧性、耐磨性、耐老化性和黏合性。用不同原料可制得适应较宽温度范围 $(-50\\sim150^{\\circ}\\mathrm{C})$ ）的材料，包括弹性体、热塑性树脂和热固性树脂。热塑性为橡胶状，耐油，耐磨耗。高温下不耐水解，亦不耐碱性介质。PU树脂的主要性能见表3-6-6。  \n\n表3-6-6 PU树脂的主要性能  \n\n\n<html><body><table><tr><td>项目</td><td>标准级</td><td>软泡</td><td>项目</td><td>标准级</td><td>软泡</td></tr><tr><td>相对密度</td><td>1.2</td><td>0.04</td><td>硬度（邵氏硬度A)</td><td>60</td><td>一</td></tr><tr><td>拉伸强度/MPa</td><td>58.8</td><td>0.196</td><td>吸水率/%</td><td>0.7</td><td>一</td></tr><tr><td>相对伸长/%</td><td>500</td><td>200</td><td></td><td></td><td></td></tr></table></body></html>  \n\n（2）典型应用范围有泡沫塑料、弹性体、涂料、胶黏剂、纤维、合成革、防水保温以及铺装材料等多种产品形式，广泛应用于交通运输、建筑、机械、电子设备、家具、食品加工、纺织服装、合成皮革、石油化工、水利、国防、体育、医疗等领域。",
+        "category": " Introduction"
+    },
+    {
+        "id": 454,
+        "chunk": "# 12.塑料合金  \n\n(1)ABS/NYLON  \n\n$\\textcircled{1}$ 特性耐热及抗化学品性、流动性佳、低温冲击性、低成本。  \n\n$\\textcircled{2}$ 用途汽车车身护板、引擎室零组件、连接器、动力工具外壳。  \n\n(2)ABS/PVC  \n\n$\\textcircled{1}$ 特性PVC增加防火性、降低成本，ABS提供耐冲击性。  \n\n$\\textcircled{2}$ 应用家电用品零组件、事务机器零组件  \n\n(3)ABS/PC  \n\n①特性增加ABS耐热尺寸稳定性、改善PC低温、后壁耐冲性、降低成本。  \n\n②应用打字机外壳、文字处理器、计算机设备的外壳、医疗设备零组件、小家电零组件、电子器材零组件、汽车头灯框、尾灯外罩、食物餐盘。  \n\n(4)ABS/SMA  \n\n$\\textcircled{1}$ 特性增加耐热性、流动性、涂装性佳。  \n\n$\\textcircled{2}$ 应用电子零组件、罩子、家电器材零组件。  \n\n（5）PPO/PS或PPE/PS  \n\n①特性改善PPO和PPE加工性、降低吸湿性、降低成本、提高PS热性和冲击性。  \n\n②应用汽车零组件、仪表板、手套箱、连接器、车轮盖、风罩、保险开关盒、计算机外壳、通信器材罩壳零组件、医疗器材零组件。  \n\n(6)ABS/Polysulfone  \n\n①特性PSF提供耐热性、抗化学品性，ABS改善PSF加工性、降低成本。  \n\n$\\textcircled{2}$ 应用家电烤箱控制键、汽车车窗摇把、食品餐盘。  \n\n(7)PC/PBT  \n\n①特性PBT改善耐溶剂及耐候龟裂性、PC提供尺寸稳定性及耐冲击性。  \n\n$\\textcircled{2}$ 应用汽车防撞板  \n\n(8)PC/PET  \n\n①特性PET改善耐候及耐溶剂性、UV安定性、PC提供良好耐冲击性。  \n\n②应用医疗器材、血液透析零件、汽车零件、汽车防撞板、头盔、雪靴。",
+        "category": " Introduction"
+    },
+    {
+        "id": 455,
+        "chunk": "# 第二节 塑料涂料的附着力  \n\n塑料品种很多，既有像ABS（丙烯睛-丁二烯-苯乙烯）共聚物表面能较高的塑料，也有表面能较低的聚烯烃塑料，还有聚合物复合材料如玻璃钢等，但它们与木材、水泥、钢铁相比，都是表面能低的物质，因此涂料在塑料制品表面的附着力是塑料涂料的关键问题。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 456,
+        "chunk": "# 一、塑料制品的表面张力及液体在聚合物表面润湿和铺展的基本条件",
+        "category": " Introduction"
+    },
+    {
+        "id": 457,
+        "chunk": "# 1.塑料制品的表面张力  \n\n金属表面具有500～5000mN/cm的表面张力，是高能表面，易于附着。而塑料表面张力小于 $100\\mathrm{mN/cm}$ ，属于难于附着的低能表面。与附着密切相关的表面物理化学特性是润湿、铺展、表面极性和粗糙度。而润湿的基础是塑料制品表面和涂料的表面张力的关系。  \n\n作为聚合物的塑料的表面张力 $\\gamma_{s}$ 不可能直接测定。比较常用的是Zisman的临界表面张  \n\n![](images/b3d43a53a1adebc7140e315d5ddc045dfd0f3245a3d28c3d65e9fe600d7dbe2d.jpg)  \n图3-6-1固体表面液滴的接触角示意图  \n\n力 $\\gamma_{c}$ 的评价方法。它是采用已知表面张力的不同液体、在同一固体表面测定它们液滴的接触角，将表面张力对cosθ作图（图3-6-1)，再将直线外推，当$\\cos\\theta{=}1$ ( $\\scriptstyle{\\vec{\\theta}}=={\\vec{0}}$ ）时即得该固体的临界表面张力，而不是固体真正的表面张力。它们通常测定不同表面张力的液体再被测塑料表面的接触角后，采用外推作图  \n\n求得。从实际应用角度来看，人们通常以 $\\gamma_{\\mathrm{c}}$ 作为参考数据为多。聚合物固体的临界表面张力 $\\gamma_{\\varepsilon}$ 见表3-6-7。  \n\n表3-6-7聚合物固体的临界表面张力 $\\gamma_{\\mathrm{e}}$ 单位： $\\mathrm{mN/cm}$   \n\n\n<html><body><table><tr><td>聚合物名</td><td></td><td>聚合物名</td><td></td></tr><tr><td>聚甲基丙烯酸全氟辛酯</td><td>10.6</td><td>聚苯乙烯</td><td>33.0</td></tr><tr><td>聚全氟丙烯</td><td>16.2</td><td>聚乙烯醇</td><td>37.0</td></tr><tr><td>聚四氟乙烯</td><td>18.5</td><td>PMMA</td><td>39.0</td></tr><tr><td>聚甲基硅氧烷</td><td>20.7</td><td>PVC</td><td>39.0</td></tr><tr><td>聚三氟乙烯</td><td>22.0</td><td>聚偏二氯乙烯</td><td>40.0</td></tr><tr><td>聚偏氟乙烯</td><td>25.0</td><td>PBT</td><td>43.0</td></tr><tr><td>聚三氟氯乙烯</td><td>31.0</td><td>尼龙-66</td><td>46.0</td></tr><tr><td>聚乙烯</td><td>31.0</td><td></td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 458,
+        "chunk": "# 2.液体在聚合物表面润湿和铺展的基本条件  \n\n涂料在底材上附着的必要条件是其在固体表面的润湿和铺展。如图3-6-1所示，液滴在平滑表面上达到平衡后，Young式成立。  \n\n$$\n\\gamma_{\\mathrm{{S}}}=\\gamma_{\\mathrm{{SL}}}+\\gamma_{\\mathrm{{L}}}\\cos\\theta\n$$  \n\n式中 $\\gamma_{5}$ ——固体的表面张力；$\\gamma_{\\mathrm{{L}}}$ ——液体的表面张力；YsL— 固体和液体的界面张力；$\\theta$ 液体的接触角。  \n\n铺展功 $\\omega_{\\mathrm{i}}$ 表示铺展前后表面张力之差，决定液体在表面的润湿和铺展状况。  \n\n$$\n\\omega_{\\mathrm{i}}=\\gamma_{\\mathrm{L}}\\cos\\theta{=}\\gamma_{\\mathrm{S}}-\\gamma_{\\mathrm{SL}}\n$$  \n\n当 $\\omega_{i}>0$ 时发生自发铺展， $\\omega_{\\mathrm{i}}<0$ 时液滴回缩。为了使 $\\omega_{i}>0$ ，即 $\\gamma_{5}>\\gamma_{\\mathrm{SL}}$ ，但一般 $\\gamma_{\\mathrm{SL}}\\ll$ $\\gamma_{\\mathrm{L}}$ ，可以近似表达为 $\\gamma_{\\mathrm{S}}{>}\\gamma_{\\mathrm{L}}$ ，即液体的表面张力必须小于固体的表面张力是润湿和铺展的必要条件。因此，必须了解聚合物固体和涂料两者的表面张力。涂料的表面张力可以按ASTMD1331-56（1980）的方法进行测定。而聚合物的表面张力往往取其临界表面张力作为参考。但是由于 $\\gamma_{c}$ 受多种因素的影响，在实用中，人们往往希望采用简便可靠的测试方法。其中有ASTMD2578—1984的“润湿张力测定方法”，该法主要用以评价涂料和油墨对PE和PP的适用性。此方法对于薄膜彩印相当实用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 459,
+        "chunk": "# 二、溶解度参数  \n\n溶解度参数 $\\delta$ 是物质最一般的特性之一。它以内聚能的平方根来表示：  \n\n$$\n\\delta{=}\\left(\\frac{\\Delta E}{V}\\right)^{0.5}\n$$  \n\n式中 $\\Delta E$ —分子内聚能， $\\mathrm{J}/\\mathrm{mol}$  \n\n$V$ -——分子容积， $\\scriptstyle{\\mathrm{mL}}/{\\mathrm{mol}}$ 口  \n\n塑料的高分子底材、涂料的树脂、溶剂的溶解度参数对于涂料在塑料底材上的附着是非常重要的物性指标。只有在高分子底材与涂料树脂混容良好的场合下才能得到良好的附着。目前对于 $\\delta$ 的认识，无论理论上还是实践中尚不完备，有下面几种表达式。  \n\n在混合热力学方程中表达为：  \n\n$$\n\\Delta G{=}\\Delta H{-}T\\Delta S\n$$  \n\n式中 $\\Delta G$ 混合自由能变化；$\\Delta\\bar{H}$ 混合热变化；$\\Delta S$ 混合变化；$T$ —热力学温度。  \n\nT△S通常为正值，聚合物混合 $\\Delta S$ 变化不大。只有当 $\\Delta H{<}T\\Delta S$ 或 $\\Delta\\bar{H}$ 为负值， $\\Delta G$ 为负，混合才能自发进行。但是 $\\Delta H$ 为负值只有少数情况，例如硝基纤维素和PVAC、PM-MA，以及丁晴橡胶和PVC那样的组合才会发生。当分子之间相互作用不大的场合下，按Hildebrand 公式：  \n\n$$\n\\Delta{H}{=}V_{\\mathrm{m}}V_{1}V_{2}(\\hat{\\sigma}_{1}{-}\\hat{\\sigma}_{2})^{2}\n$$  \n\n式中 $V_{\\mathfrak{m}}$ 一 混合体系的总体积；  \n\n$V_{1}$ + $V_{\\mathrm{~2~}}$ ——成分1、2的体积；  \n\n$\\tilde{\\partial_{1}}$ ， $\\delta_{2}$ ———成分1、2的溶解度参数。  \n\n由式（3-6-5）可知，当 $\\delta_{1}=\\delta_{2}$ 时， $\\Delta H$ 达到最小值，即这个 $\\delta$ 值近似于附着的最佳条件。  \n\n近年来许多研究者试图建立液体表面张力和 $\\boldsymbol{\\hat{\\partial}}$ 之间关系，例如Lee提出如下公式：  \n\n$$\n\\gamma_{1}=\\kappa\\partial^{n}V^{\\frac{1}{3}}\n$$  \n\n式中V—分子容积；  \n\n$k^{2}$ + $n$ ——与液体种类有关的常数。  \n\n在一定温度和条件下， $\\delta_{\\mathrm{S}}=\\delta_{\\mathrm{L}}$ ，相应于 $\\gamma_{\\mathrm{{S}}}=\\gamma_{\\mathrm{{L}}}$ ，即界面张力为零时达到润湿和附着的最佳条件。在这里， $\\delta$ 由色散力、偶极力和氢键三种成分结合而成：  \n\n$$\n\\delta^{2}=\\delta_{\\mathrm{a}}^{2}+\\delta_{\\mathrm{b}}^{2}+\\delta_{\\mathrm{c}}^{2}\n$$  \n\n但是溶解度参数理论主要建立在分子间作用力以色散力为主的基础上，在由强相互作用，如氢键结合的酸基、羟基等情况，可能发生 $\\Delta H$ 即放热混合的情况，理论可能发生偏差。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 460,
+        "chunk": "# 三、提高漆膜附着的途径",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 461,
+        "chunk": "# 1.涂料性质的改进  \n\n(1）降低黏度涂料渗入底材表面的凹陷和孔隙可提高漆膜在底材表面上的附着，因而降低涂料的黏度可以提高流动性和渗人性，从而提高附着。  \n\n(2）降低涂料的表面张力表面张力低，则对底材的润湿好，良好的润湿是良好附着的前提，降低黏度也包含降低表面张力，因为溶剂的表面张力低于成膜聚合物的表面张力。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 462,
+        "chunk": "# 2.底材的表面处理  \n\n涂料与底材的结合是两者相互作用的结果，所以底材的表面状态对漆膜的附着有同样重要的地位。底材表面处理是为了改善表面状态，主要是提高润湿张力，形成适合于漆膜附看的表面。塑料制品的表面处理的方法很多，不同的塑料可采用不同的方法。和其他材料一样，在进行表面处理之前要对塑料表面进行清洗，包括消除静电、除去灰尘，用溶剂洗去油污和脱模剂以及打磨平整表面等。在已清洁的塑料表面可采用多种方法改性，卜一节将逐一介绍。  \n\n归纳起来，涂料和塑料制品欲达到良好的附着必须满足如下的条件。  \n\n$\\textcircled{1}$ 涂料应具有良好的流变特性。施工时低黏度，流动性和流平性好、不流淌、不流挂。$\\textcircled{2}$ 涂料的表面张力必须尽可能地小于塑料底材的表面张力。因此，必须从涂料树脂、  \n溶剂体系及底材三者综合进行考虑评价。$\\textcircled{3}$ 涂料体系的溶解度参数调整到与底材接近并在允许的程度内溶解或溶胀底材，形成  \n相混界面层，同时又不会导致成膜后产生收缩应力。$\\textcircled{4}$ 涂料如能与底材表面发生化学键合，成强极性基团结合对于良好的附着最为理想。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 463,
+        "chunk": "# 3.使用附着增进剂—偶联剂  \n\n偶联剂的作用是介人漆膜和底材之间，形成底材/偶联剂/漆膜两个界面，这两个界面均有较高的亲和性，甚至化学键，从而增进了附着。  \n\n偶联剂的分子有两端，一端可与底材相互作用，另一端可与涂料作用，偶联剂可作为底材的预处理，也可直接加入涂料中，但以预处理的效果更显著。涂料用偶联剂品种见表3-6-8，目前以硅烷类使用较广。  \n\n表3-6-8一些涂料用偶联剂  \n\n\n<html><body><table><tr><td>类型</td><td>无机基团</td><td>有机基团</td><td>稳定性</td><td>潮气敏感性</td><td>溶剂溶解性</td></tr><tr><td>硅烷</td><td>—OR</td><td>多种</td><td>很稳定</td><td>差</td><td>优良</td></tr><tr><td>钛酸酯</td><td>-OR</td><td>多种</td><td>尚可</td><td>差</td><td>优良</td></tr><tr><td>锆酸酯</td><td>-OR</td><td>多种</td><td>尚可</td><td>差</td><td>优良</td></tr><tr><td>锆铝酸酯</td><td>—OH,-Cl</td><td>多种</td><td>很稳定</td><td>优良</td><td>尚可</td></tr><tr><td>磷酸烷基酯</td><td>-OR</td><td>烷基/芳基</td><td>良好</td><td>尚可</td><td>良好</td></tr></table></body></html>  \n\n硅烷类偶联剂对潮气非常敏感，故不宜用于水性涂料。它对硅酸盐底材有非常优良的附着增进效果，故常用于硅酸盐制品的表面处理。  \n\n聚烯烃类塑料润湿张力很低，表面上活性点很少，甚至没有活性点，因此漆膜对其附着很差，而施加各种表面处理后，活性消失很快而难以施工。因而大多以氯化聚烯烃（含氯量约$30\\%$ ）或其顺丁烯二酸酐的改性物的甲苯溶剂以薄涂层作为底材或漆膜间的附着增进过渡层。  \n\n归纳起来，涂料和塑料制品欲达到良好的附着必须满足如下的条件。  \n\n$\\textcircled{1}$ 涂料应具有良好的流变特性。施工时低黏度，流动性和流平性好，不流淌、不流挂。$\\textcircled{2}$ 涂料的表面张力必须尽可能地小于塑料底材的表面张力。因此，必须从涂料树脂、  \n溶剂体系及底材三者综合进行考虑评价。$\\textcircled{3}$ 涂料体系的溶解度参数调整到与底材接近并在允许的程度内溶解或溶胀底材，形成  \n相混界面层，同时又不会导致成膜后产生收缩应力。$\\textcircled{4}$ 涂料如能与底材表面发生化学键合或强极性基团结合，对于良好的附着最为理想。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 464,
+        "chunk": "# 4.评价塑料涂层的附着力的方法  \n\n与其他表面一样，评价涂层在塑料表面的附着力，主要采用划圈法、划格法、剪切力法和拉开法进行测定，划圈法和划格法具有较大的局限性，它与涂层的柔韧性和硬度有极大的关系，适用于同类的树脂涂料和柔软涂料附着力的评价，但不适合不同类型涂料附着力的评定。最直接的涂层附着力评价方法是拉开法，可直接从读数和涂层破坏形式上进行判定。读数大小直接决定了涂层附着力的大小，同时还可从其破坏形式进行补充判断，用拉开法测定时，涂层和塑料底材之间有四种基本情况。  \n\n(1）涂层内聚破坏表面为缺口处两面都有均匀涂料附着，说明与底材附着力大于涂层内聚力，附着情况良好。(2）涂层与底材界面破坏表面为缺口处底材没有任何涂层附着，说明与底材附着情况不好，需要改进表面处理方法或重新选择涂料。(3）上述两种混合破坏表面为缺口处两面局部存在涂料附着，底材局部没有涂层附着，说明与底材附着情况不甚良好。(4）底材内聚破坏表面为缺口处涂料面粘有底材，底材面被局部破坏，说明涂层与底材附着力大于底材内聚力，附着情况良好。  \n\n此外，还有涂层本身没有完全剥落的情况，主要是由于胶黏剂选择不当或涂层本身难以粘接引起的，要重新选择胶黏剂或进行适当处理（如打磨、溶剂擦洗等）后重新测定。  \n\n![](images/08d4a9f15c15635cf1042a86c491ad061af55569656368d873bcac0a5b760d5f.jpg)  \n\n塑料制品种类繁多，形状各异，批量大小不一，选择相适应的涂装工艺时必须充分考虑涂装技术，其中也包括表面处理方法的实用性、经济性等。此外，近年来人们对环境保护意识日益增强，有的国家开始立法限制和禁止有毒有害物资的使用和排放。因此，选择表面处理的方法还应考虑它们的环境适应性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 465,
+        "chunk": "# 一、塑料的常规处理方法",
+        "category": " Introduction"
+    },
+    {
+        "id": 466,
+        "chunk": "# 1.（热）溶剂处理法  \n\n溶剂处理塑料制品底材表面是最简单和最有效的物理处理方法之一。选择适当的溶剂对底材表面处理工艺可达到以下目的：  \n\n① 清除表面聚集的增塑剂、脱模剂、防静电剂、润滑剂、抗氧化等弱界面层（weakboundary lay， WBL);  \n\n$\\textcircled{2}$ 高分子底材中残留的低分子低聚物和单体；  \n\n$\\textcircled{3}$ 表面氧化分解和或紫外线老化后的粉化、分解产物；  \n\n④ 热溶剂溶蚀部分非结晶性表面产生增加粗糙度的效果或使处理后底材表面适度溶胀，有利于底材和涂料互溶层与涂层界面结合更牢固。  \n\n为了更好地发挥溶剂处理的效果，可以把溶剂处理和涂装同时进行，即首先把涂装物加热，然后浸渍于已加热的涂料中进行涂装。例如把聚丙烯板以丙酮、二甲苯（1：1)的混合溶剂擦拭后，按所定的条件加热，而后再在加热的涂料中浸渍，取出后在室温放置20min，最后在50℃进行30min干燥。用此方法处理后，涂饰不同涂料的附着力列于表3-6-9。  \n\n表3-6-9 溶剂处理对附着力的影响  \n\n\n<html><body><table><tr><td colspan=\"2\">溶剂</td><td>70天（常温）</td><td>15s(50℃)</td><td>15s(70℃)</td><td>15s(87C)</td></tr><tr><td>氯化溶剂</td><td>四氯乙烯 三氯乙烯 1,2-二氯乙烯 五氯乙烷 二氯戊烷 1,2,4-三氯乙烯</td><td>P P P 一 一 一</td><td>F P P P P P P</td><td>F G F(60℃) F P P</td><td>E E 一 E F P</td></tr><tr><td>芳香族溶剂</td><td>1-氯丁二烯 苯 甲苯</td><td>一 P P</td><td>P P</td><td>P F F</td><td>P E F</td></tr><tr><td>脂肪族溶剂</td><td>VM&P石脑油 环已烷 200#汽油 十氢化蔡(C1oH1s)</td><td>P P P 一</td><td>P G P P</td><td>F G P F</td><td>F G P E</td></tr><tr><td>其他</td><td>松节油 丁醇 醋酸丁酯 乙二醇乙醚 甲基异戊基酮</td><td>P P P</td><td>P P P P P</td><td>P P P P P</td><td>P P P P P</td></tr></table></body></html>\n\n注：用氯化橡胶（ $:\\mathrm{Per/on~}s{\\mathrm{-}}\\bar{\\tilde{\\varepsilon}}\\bar{0}.$ ）涂料涂刷常温干燥，切割剥离实验。P代表全部剥落； $\\bar{\\mathbf{F}}$ 代表大部分剥落；G代表少量剥落；E代表不剥落。  \n\n表3-6-10 用聚丙烯加热浸渍涂装对各种涂料的附着力  \n\n\n<html><body><table><tr><td rowspan=\"2\">类 别</td><td colspan=\"3\">30°℃</td><td colspan=\"3\">60℃</td><td colspan=\"3\">100℃</td></tr><tr><td>10s</td><td>60s</td><td>180s</td><td>10s</td><td>60s</td><td>180s</td><td>10s</td><td>60s</td><td>180s</td></tr><tr><td>高固体喷漆</td><td>XX 0/100</td><td>X 0/100</td><td>△ 0/100</td><td>△ 0/100</td><td>△ 15/100</td><td>△ 23/100</td><td>100/100</td><td>。 100/100</td><td>100/100</td></tr><tr><td>丙烯酸清漆</td><td>100/100</td><td>100/100</td><td>100/100</td><td>100/100</td><td>100/100</td><td>100/100</td><td>100/100</td><td>0 100/100</td><td>100/100</td></tr><tr><td>氯乙烯树脂涂料</td><td>XX 0/100</td><td>XX 0/100</td><td>XX 0/100</td><td>X 0/100</td><td>X 0/100</td><td>X 0/100</td><td>100/100</td><td>100/100</td><td>。 100/100</td></tr><tr><td>脂肪酸改性环氧树脂涂料</td><td>XX 0/100</td><td>XX 0/100</td><td>XX 0/100</td><td>X 0/100</td><td>O 56/100</td><td>O 76/100</td><td>100/100</td><td>100/100</td><td>100/100</td></tr><tr><td>脂肪酸改性聚氨酯树脂涂料</td><td>XX 0/100</td><td>XX 0/100</td><td>XX 0/100</td><td>XX 0/100</td><td>XX 0/100</td><td>XX 0/100</td><td>O 78/100</td><td>O 75/100</td><td>O 88/100</td></tr><tr><td>苯乙烯改性醇酸树脂涂料</td><td>XX 0/100</td><td>XX 0/100</td><td>XX 0/100</td><td>XX 0/100</td><td>X 0/100</td><td>X 0/100</td><td>100/100</td><td>。 100/100</td><td>。 100/100</td></tr></table></body></html>\n\n注：1.上段表示划线实验，下段表示切割粘贴实验；2.划线实验符号： $\\odot$ 没有异常；○少量剥落； $\\Delta$ 部分剥落； $x$ 大部分剥落； $x^{*}x^{*}$ 全部剥落。  \n\n从表3-6-10可以看出被涂物在加热到 $100^{\\circ}C$ 时可得到最好的涂料附着性，浸渍时间延长要比被涂物的温度升高效果更为明显。用此方法可使未处理的聚丙烯表面也得到相当于表面处理过的附着力。  \n\n对于大多数热塑性底材来说，由于对极性溶剂的溶解性较好，最安全的溶剂体系是醇类溶剂体系，例如甲醇、乙醇、异丙醇使用最多。混合溶剂系列可以参考如下的组合。  \n\n(1）ABS、HIPS、PS底材用甲醇、异丙醇（IYA）或防静电剂，把塑料底材上的污秽、灰尘、油渍、脱模剂和指纹措拭十净。  \n\n(2）聚氯乙烯板材（PVC）邻苯二甲酸二辛酯/乙酸甲酯/乙酸乙酯、邻苯二甲酸二辛酯/甲乙酮/二氧六环、异佛尔酮/乙酸/甲醇、甲乙酮/环己烷/环氧丙烷。  \n\n(3）聚碳酸酯（PC) 二氯甲烷/二氯乙烯。  \n\n（4）聚酰胺二氯甲烷-苯酚，它对聚酰胺具有一定的溶解力，即是说，溶剂体系对高分子底材具有溶解性的为好。  \n\n(5）聚甲醛对甲基苯磺酸 $0.3\\%$ 、二氯乙烷 $95.7\\%$ 、二氧六环 $3.0\\%$ 心  \n\n(6）形状复杂的聚烯烃制品常用溶剂为三氯乙烯溶液，温度为 $65\\sim75\\mathrm{^\\circC}$ 时用溶剂蒸气加以浸蚀后，快速涂饰，时间宜控制在 $30\\sim60s$ ，否则浸蚀后的表面很快就会恢复。通常用三氯乙烯为溶剂的树脂液作为溶剂蒸气的来源。  \n\n值得注意的是使用溶剂处理，尤其是热溶剂处理，往往会使底材产生细小裂纹，或称之为溶裂，所以热固性塑料一般不发生皱裂。只有像聚苯乙烯、聚甲基丙烯酸甲酯、聚碳酸酯这些热塑性塑料才会发生皱裂。  \n\n关于皱裂发生的原因，目前尚未十分清楚，但考虑可能有以下原因。  \n\n(1）塑料内部低分子量成分和未反应的单体很容易被溶剂从表面抽出，产生的间隙被溶剂浸人，间隙压力增高。另一方面由于间隙被溶剂浸透，造成塑料的凝聚力下降，无论哪种溶剂浸人，都会使溶剂的强度下降。这是因浸人的溶剂会使原来的应力释放，而产生新的应力作用。如果塑料中没有能被抽提出来的物质，即使溶剂浸入塑料也不会产生皱裂。  \n\n(2）由于树脂不均一成分被溶剂浸人，而在塑料内部生成溶剂的吸收膜。随着溶剂吸收的分子数增加，产生的压力增高，最后大于塑料的拉伸力而产生割裂。  \n\n(3）在成型的过程中产生的内应力，原因是： $\\textcircled{1}$ 模具设计的不合理； $\\textcircled{2}$ 物料进人模具，由于温度不够，不能保证均一的流动性； $\\textcircled{3}$ 闭膜后的锁模压力不够。  \n\n以上诸多因素都会使成型品产生内应力，内应力越高，越容易产生皱裂。  \n\n如果在溶剂处理前，先进行退火处理以除去塑料内部的残余应力，那么结果就好得多。此外，如用醇系溶剂处理，产生裂纹的可能性会大大降低。  \n\n溶剂处理根据塑料制品批量大小、形状及其涂装工艺要求而采取从最简单的擦洗、浸泡至高温蒸煮等不同方法。值得注意的是处理温度对最终效果影响很大。通常从 $50\\sim90^{\\circ}C$ （视溶剂体系的沸点而定)，在较高的温度下，短时间内即可达到较好的效果。但是高温处理对安全生产和环境保护带来了更高的要求。  \n\n由于大多数溶剂对操作工人有害并且污染环境，尤其是氯代烃对大气的臭氧层危害很大。人们不断地寻求溶剂处理的代替方法。近年来使用表面活性剂与水处理方法进展很快，但是目前尚不能完全代替溶剂处理方法。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 467,
+        "chunk": "# 2、化学处理法  \n\n又称化学氧化法。对塑料表面进行氧化液处理的有聚乙烯（LDPE)、聚苯乙烯（PS）和ABS塑料等。其配方如下：重铬酸钾（ $\\mathrm{K}_{2}\\mathbb{C}\\mathbf{r}_{2}\\mathbb{O}_{7}$ ） $4.3\\%$ ；浓硫酸（ $\\mathbf{H_{2}S O_{4}}$ ） $88.4\\%$ 0水 $7.3\\%$ 0  \n\n用此溶液处理 $10\\mathrm{\\sim}12\\mathrm{min}$ ，处理温度为 $40\\sim45^{\\circ}C$ ，即刻用清水冲洗干净，让其自干或在$50\\sim60^{\\circ}C$ 烘箱中烘干。  \n\n表面粗糙度是影响涂装效果的一个重要因素。表3-6-11列出了在显微镜下观察到用前处理液处理后的聚乙烯塑料表面的粗糙度、实际润湿角的变化情况。  \n\n表3-6-11 不同前处理条件下的表面状况  \n\n\n<html><body><table><tr><td>前处理条件</td><td>表面状况</td><td>8' /(°)</td></tr><tr><td>未前处理</td><td>一</td><td>84</td></tr><tr><td>25°℃,3min</td><td>生成0.08～0.10μm、深约0.08μm的孔穴</td><td>70</td></tr><tr><td>70℃,3min</td><td>生成0.10～0.12μm、深约0.10μm的孔穴</td><td>55</td></tr><tr><td>25℃,10min</td><td>生成0.10～0.18μm、深约0.10μm的孔穴</td><td>52</td></tr><tr><td>70℃,10min</td><td>生成0.15～0.30μm、深约0.15μm的孔穴</td><td>45</td></tr><tr><td>25℃,30min</td><td>生成0.20～0.35μm、深约0.15μm的孔穴</td><td>39</td></tr><tr><td>70°℃,30min</td><td>生成0.30～0.50μm、深约0.15μm的孔穴</td><td>31</td></tr><tr><td>90°℃,30min</td><td>生成0.40～0.50μm、深约0.20μm的孔穴</td><td>27</td></tr><tr><td>90°℃,60min</td><td>生成p0.40～0.53μm、深约0.20μm的孔穴</td><td>25</td></tr><tr><td>90℃,90min</td><td>生成0.46～0.55μm、深约0.20μm的孔穴</td><td>22</td></tr></table></body></html>  \n\n从表3-6-11中可以看出，聚乙烯塑料表面随着处理温度的升高和时间的延长，其表面粗糙度加大，实际润湿角降低；但当时间大于 $30\\mathrm{min}$ ，温度高于 $70^{\\circ}C$ 时，则两者的变化不是很明显。所以，前处理时间应控制在 $30\\mathrm{min}$ 温度 $70^{\\circ}C$ 为宜。  \n\n对于聚烯烃而言，广泛采用硫酸-铬酸混酸处理法可达到最佳的效果。这是因为聚苯乙烯分子主要由苯环组成，苯环很容易磺化而引人磺酸基，从而改变了表面的极性。  \n\nABS塑料经脱脂后也可用较稀的铬酸和硫酸液处理，配方为：  \n\n铬酸 $(\\mathrm{H}_{2}\\mathrm{CrO}_{4})/(\\mathrm{g}/\\mathrm{L})$ 420 硫酸（相对密度 $1.83)/i\\mathrm{mL/L})$  \n\nABS塑料在此溶液中浸泡处理 $4\\mathrm{\\sim}12\\mathrm{min}$ ，温度为 $60\\sim70^{\\circ}C$ ，用水洗净、干燥。  \n\n聚酯和聚碳酸酯可以用1，6-己二胺，或 $N,N-$ -二甲基丙二胺等脂肪胺进行处理，由于反应导人—OH和R—NH—，不仅改进了表面的极性和可润湿性，同时也大大增强了它们表面的可染色性。聚甲醛的化学试剂处理一般采用对甲基苯磺酸、磷酸、过硫酸铵、铬酸等酸性或氧化性的酸处理液进行，聚甲醛中的主键为醚键，通过氧化降解醚键，可以引人羟基和羧基等基团从而改变其表面的润湿性和涂层附着力。聚酰胺制品可以采用磷酸处理，将聚酰胺制品浸人 $30^{\\circ}C$ 1 $40\\%$ 的磷酸液中 $\\mathtt{l o m i n}$ ，然后水洗并干燥。  \n\n化学试剂处理的目的在于通过氧化等反应在塑料制品底材表面引人极性的亲水性基团或者其他反应性官能团，同时经表面侵蚀生成多孔型结构，其结果改进了涂料对底材表面的润湿性和附着力。在印刷作业时，可以改进底材的印刷适应性、染色性；化学镀膜条件下可以改善金属膜的附着性和密着性等。  \n\n化学试剂处理法总是伴随着处理液以及随后的清洗液的“三废”处理问题。因此寻找更加环境适应性的处理剂及其处理工艺是主要的开发方向，例如过氧化氢（ $\\mathrm{H}_{2}\\mathrm{O}_{2}$ ，双氧水)处理法、臭氧表面处理等基本上不产生废水。  \n\n用化学试剂处理时特别注意处理液的组成、处理温度、时间等条件应按照不同的塑料制品、涂装要求、涂装工艺进行优化。一般的连续处理工艺是将制品挂在传送链上，依次通过浸渍槽、强化反应槽、水洗槽、干燥室。此外应指出经过处理后的塑料制品必须尽快进行涂装，以免长时间放置后表面失活，更不得用手直接去接触已经处理好的表面。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 468,
+        "chunk": "# 3.底涂处理法  \n\n溶剂处理或化学试剂处理方法从经济、涂装工艺和设备及环境等诸多方面考虑，均不是很理想的处理方法。采用底漆涂装以改变一些难以附着的塑料制品的表面状态是最经济的选择之一。目前采用底涂处理的塑料有：PP、改性PP、PE 等的涂装，多是采用底涂处理方法。市场上可以选择的底漆主要有氯化聚烯烃、改性或接枝改性的氯化聚烯烃、共聚或接枝改性的聚烯烃、丙烯酸酯等成膜物的品种。而且，近年来还不断有新的品种开发出来。但是到目前为止，依靠底漆尚不能完全达到十分满意的表面改性的程度。因此又开发出在塑料制品的表面涂布聚合物单体，再采用种种方法进行表面聚合改性的方法。  \n\n高耐磨耗、耐划伤硬涂层紫外光固化成膜技术可以作为实例。它们均由二官能性的甲基丙烯酸酯（如二乙二醇二甲基丙烯酸酯、已二醇甲基丙烯酸酯等）、三官能性的甲基丙烯酸酯（三羟甲基丙烷三甲基丙烯酸酯）以及四～五官能性的丙烯酸酯单体组成的，经涂布在塑料制品表面再进行紫外光固化即可得到与底材表面结合牢固的涂层。  \n\n表面聚合改性方法还可以用于塑料制品的表面防结露处理。将单体涂覆于制品表面后，采用适当方法聚合后形成具有防结露特性的聚合物涂层。例如将甲基丙烯酸羟乙酯与乙二醇二丙烯酸酯混合物涂布后， $150^{\\circ}C$ 热处理 $5\\mathrm{min}$ 即可生成具有防结露效果的涂层。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 469,
+        "chunk": "# 4.表面活性剂处理法  \n\n表面活性剂处理法其目的与溶剂处理基本上是相同的，主要是除去表面上灰尘、迁移至制品表面的各种助剂、表面加工剂等油脂类杂质。与溶剂处理法相比，表面活性剂除去无机杂质更加方便，也更容易。而溶剂处理法除去油脂类等杂质效果更好。但是制品表面往往是无机杂质和有机杂质混合存在与附着的，这样一来，必须求得配方优化。有时采用表面活性剂处理的另外一个优点是它们是以水溶液的状态使用的，因此对环境的污染较轻。  \n\n常用的表面活性剂有以下几种类型，  \n\n(1）阴离子型表面活性剂 $\\textcircled{1}$ 高级脂肪酸金属盐（金属皂）； $\\textcircled{2}\\alpha$ -烯烃的硫酸盐； $\\textcircled{3}$ 烷 基取代苯磺酸盐等。 (2）非离子型表面活性剂 $\\textcircled{1}$ 高级醇的聚氧乙烯加成物或聚氧乙烯； $\\textcircled{2}$ 烷基取代苯酚聚 氧乙烯加成物； $\\textcircled{3}$ 二羟乙基取代的脂肪酸酰胺等。 (3）两性表面活性剂 $\\textcircled{1}$ 氨基酸型两性洗涤剂； $\\textcircled{2}$ 甜菜碱型两性洗涤剂； $\\textcircled{3}$ 脂肪醇聚氧 乙烯硫酸盐等。  \n\n表面活性剂能同时赋予塑料防静电性、润湿性和附着性。作为表面处理使用的表面活性剂可以采用表面涂布或在塑料加工时加人，成型后再析出，并迁移至表面的方法。采用加人法，势必需要相当数量的表面活性剂才能达到目的。这样必然影响到塑料制品的自身特性。表面涂布法的问题在于改性后的表面性质难以长期保持。为此可以采用在处理后的表面上迅速涂覆上面漆，或将高分子材料与表面活性剂一起涂布等方法加以解决。值得提出的是，在塑料中表面添加剂的用量以能在表面形成单分子膜为宜。用量太少则表面改性不完全；如果用量太多则表面形成弱界面层反而降低附着力，而且会影响到制品本身的特性。此外添加剂随着时间向塑料表面迁移的量以及添加剂在塑料表面聚集的状态也影响漆膜附着力。  \n\n对于聚烯烃塑料，添加 $0.1\\%\\sim0.4\\%$ 的聚乙二醇单硬脂酸酯、聚氧乙烯月桂酸酯可以产生良好的防晕效果。如果将非离子表面活性剂与三乙醇胺磷酸酯合用其效果更好。山梨醇月桂酸酯和聚氧乙烯山梨醇单油酸酯等量混合后添加的方法可以适用与聚氯乙烯塑料的防晕处理。  \n\n表面活性剂处理广泛地应用于塑料制品的防静电处理。它们包括添加表面活性剂的内部防静电法和表面涂布的外部防静电法。作为添加法可以采用阴离子型、阳离子型、两性及非离子型表面活性剂。其中阳离子型和两性表面活性剂的防静电效果较佳，而且阴离子表面活性剂一般与塑料的相容性较差，所以从热稳定性、相容性和防静电性三方面总和考虑使用非离子型较多。具体品种和用量应根据不同塑料加工条件来决定。在外部涂布表面活性剂防静电方法遇到的主要是防静电作用寿命期短的问题。人们已经提出种种方案以延长防静电层的有效期。例如，可将表面活性剂分散在亲水性的丙烯酸树脂中进行涂布；也可以进行表面活性剂防静电处理后，再涂布一层有机硅的保护层，即用烷氧基硅烷类的偶联剂进行表面处理可以保证防静电层的持续作用。  \n\n通常用溶剂清除塑料表面的油脂、脱膜剂以及渗出的脱模剂。用溶剂处理法效果虽然不错，但是由于环境压力增大，人们越来越多地采用表面活性剂的水系清洗剂进行表面处理。PP 和PE等聚烯烃的溶解参数为8.0左右；而油脂、有机硅脱膜剂等溶解度参数为 $7\\sim9$ 彼此相近，因此在塑料制品表面具有较强的附着力。采用单一的表面活性剂处理难以完全将其清除，如果在清洗剂配方中加人碱性物质，增加油脂的乳化作用，同时加人固体无机物质以附加对塑料制品表面的机械磨蚀作用并增加表面粗糙度，从而可以大大提高处理的效果。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 470,
+        "chunk": "# 5.表面接枝处理法  \n\n聚合物单体或低聚物在塑料表面进行化学反应的接枝处理，从而改进塑料制品表面的润湿性，形成附着紧密的表面层，进一步增强涂层的附着力也是塑料表面改性处理的很有效的手段。  \n\n表面接枝处理方法的选择范围很大，主要分为以下几类。 $\\textcircled{1}$ 以表面活性化为目的的表面接枝；②在接枝反应前制品表面未进行活化处理；③与其他表面活性化处理同时进行接枝化处理。  \n\n根据表面接枝所需能量来源可分为： $\\textcircled{1}$ 采用催化剂的化学方法； $\\textcircled{2}$ 光、放射线照射；$\\textcircled{3}$ 放电等。  \n\n根据接枝反应完成的方式可分为： $\\textcircled{1}$ 气相接枝反应； $\\textcircled{2}$ 液相接枝反应。  \n\n将上述各种不同的方式相互组合后可以得到适应不同目的的接枝处理的实施方案。下面举例说明。  \n\n将聚乙烯制品置于封管中，通人含有 $0.29\\%$ 臭氧( $\\mathrm{\\DeltaO_{3}}$ ）的氧气，在室温下处理一定时间后，减压下（1.333Pa）再通人丙烯睛蒸气。经过冷却在制品表面冷凝产生一层丙烯晴膜，然后控制一定温度进行丙烯睛与聚乙烯表面接枝反应，这种处理方法叫做气相前处理的接枝表面处理。  \n\n液相接枝反应往往添加无机离子作为催化剂。例如在4价铈存在下用醋酸乙烯处理羊毛（天然聚酰胺）进行表面接枝处理，或者在4价铈和3价铬共同存在下用甲基丙烯酸甲酯处理生丝（天然聚酰胺）进行表面接枝处理后可以极大地改变它们的表面可染色性及提高其印染涂层的附着力。  \n\n聚烯烃类树脂分子量分布较宽，其塑料在成型过程中，低分子量树脂被挤在成型品表面形成弱表面层，如果使表面层低分子树脂进行接枝共聚增大分子量，增大次价键力，就会增大固体表面张力Ys。具体办法是在光敏剂的存在下用USM方法，如在塑料表面涂拭光敏剂苯甲酮，而后以UV射线照射，使塑料表面分子分子量增殖，因而增加了表面机械力Ys，降低了润湿角，增大了涂料的润湿性，为涂料附着创造了条件。  \n\nUSM方法是利用光敏剂、二苯基酮和UV射线，照射初期在聚烯烃表面生成自由基，若采用聚乙烯，则可以通过它自身的反应或是一定程度地与空气中的氧生成自由基，塑料表面的分子被引发之后由于空气中的氧不是太多，最终的结果是被引发的分子产生偶联，为涂料润湿创造了条件。表3-6-12列出了火焰处理及光敏照射对涂料的附着力。  \n\n表3-6-12 火焰处理及光敏剂UV照射对基材的影响  \n\n\n<html><body><table><tr><td>处理方法</td><td>增加s（临界表面张力）</td><td>增加s（固体表面张力）</td><td>实际表面变化</td></tr><tr><td>火焰处理</td><td>有影响</td><td>很少</td><td>改善润湿性，只是有限增加力学性能</td></tr><tr><td>紫外线光敏处理</td><td>很少</td><td>有影响</td><td>增加力学性能，只是有限增加润湿性</td></tr></table></body></html>  \n\n表3-6-13和表3-6-14列出了由USM方法处理后的表面，水的接触角和不同涂料的附着情况。  \n\n表3-6-13USM方法用于聚乙烯的结果  \n\n\n<html><body><table><tr><td rowspan=\"2\">紫外线照射 /s</td><td rowspan=\"2\">水的接触角 /C)</td><td colspan=\"3\">涂膜破坏/%</td></tr><tr><td>聚氨酯漆</td><td>丙烯酸漆</td><td>环氧树脂漆</td></tr><tr><td>无</td><td>69</td><td>100</td><td>100</td><td>100</td></tr><tr><td>20</td><td>66</td><td>10</td><td>0</td><td>0</td></tr><tr><td>40</td><td>62</td><td>0</td><td>0</td><td></td></tr><tr><td>80</td><td>49</td><td></td><td></td><td></td></tr></table></body></html>\n\n$\\textcircled{1}$ 5kW灯，以对苯甲酮为光敏剂， $2\\%$ 二氯甲烷溶液，表面涂光敏剂之前擦拭二氯甲烷。$\\textcircled{2}$ 在 $100C$ ， $30\\mathrm{min}$ 固化。$\\textcircled{3}$ 在 $70^{\\circ}C$ ， $20\\mathrm{min}$ 固化。$\\textcircled{4}$ 在 $100^{\\circ}C$ 1 $15\\mathrm{min}$ 固化。  \n\n表3-6-14USM方法用于聚丙烯的结果  \n\n\n<html><body><table><tr><td rowspan=\"2\">紫外线照射 /s</td><td rowspan=\"2\">水的接触角 /(°)</td><td colspan=\"3\">涂膜破坏/%</td></tr><tr><td>聚氨酯漆</td><td>丙烯酸漆</td><td>环氧树脂漆</td></tr><tr><td>无</td><td>98</td><td>100</td><td>100</td><td>100</td></tr><tr><td>20</td><td>82</td><td>5</td><td>15</td><td>25</td></tr><tr><td>40</td><td>83</td><td></td><td></td><td>5~10</td></tr><tr><td>80</td><td>90</td><td></td><td>0</td><td>0</td></tr></table></body></html>\n\n$\\textcircled{1}\\sim\\textcircled{4}$ 条件同表3-6-13。  \n\n从表3-6-13和表3-6-14中可以看出聚乙烯在20s就发生偶联，而聚丙烯在 $40\\sim805$ 偶联，这可能与光敏剂的溶剂有关，溶剂的润湿也起着重要的作用，适用于聚乙烯的对聚丙烯就不一定适合，然而照射的时间长一些比较好。  \n\n经接枝处理后的表面活性层的机械强度和耐化学品处理的强度都是很优异的。这一点与溶剂法和表面活性剂处理法所得到的表面耐受性有很大的区别。接枝处理后的表面层与涂料的附着力根据处理强度，选用单体类型及配套涂料的品种可以达到最优的组合。例如，聚乙烯用甲基丙烯酸甲酯在 $y$ 射线下气相接枝处理后，与环氧涂料的附着力优异。此外，如果在接枝单体中引入可与涂料成膜物反应的管能团，那么经接枝处理后的表面层对涂料的润滑和附着性将进一步得到改善。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 471,
+        "chunk": "# 6.紫外光（UV）照射处理法  \n\n前面在表面接枝处理中讨论了在光敏剂存在下经紫外线照射使塑料表面分子分子量增加，从而提高固体表面张力Ys，改善涂膜的附着力。这里讲的紫外线处理不用光敏剂而是直接以紫外线照射，利用空气中的氧的作用，使塑料表面产生极性基团增加临界表面张力$\\boldsymbol{\\gamma}_{\\mathrm{c}}$ 来降低涂料的接触角，提高涂膜的附着力。  \n\n（1）聚乙烯的紫外线处理将市售的聚乙烯或聚丙烯板用洗涤剂水溶液清洗 $5\\sim10\\mathrm{min}$ 水洗 $\\mathfrak{f o m i n}$ ，丙酮清洗 $2{\\sim}5\\operatorname*{min}$ ，苯洗 $2\\sim5\\mathrm{min}$ 后干燥 $5h$ ，保存在充氮气容器中待处理。紫外光处理用的光源为石英汞灯，其最大强度波长为 $253.7\\mathrm{nm}$ ，聚乙烯实验板离光源 $20\\mathsf{c m}$ 照射过程中聚乙烯表面温度保持在 $80\\sim90^{\\circ}C$ ，照射时间为 $\\mathrm{3min{\\sim}3h}$ 0  \n\n用苯、苯甲醛、硝基苯、 $20\\%$ 的 $\\mathrm{K_{2}C O_{3}}$ ， $50\\%$ 的 $\\mathrm{{K}_{2}\\vec{C}O_{3}}$ 五种液体对紫外线处理过的聚乙烯、照射时间与接触角的关系如图3-6-2所示。从图中可以看出一般的紫外线处理对几种液体接触角影响都不大，如处理前临界表面张力 $\\bar{s}_{\\bar{c}}$ 为 $0.03\\ensuremath{\\mathbf{N}}/\\ensuremath{\\mathrm{m}}$ ，处理 $30\\mathrm{min}$ 后为 $0.034\\mathbf{N}/$ $\\mathtt{m}$ ，到 $180\\mathrm{min}$ 后为 $0.035\\mathbf{N}/\\mathrm{m}$ ，变化很小。  \n\n![](images/49d7f95283cdbb975c72229587e366723fda65856475255f25ff98be7df4fbad.jpg)  \n图3-6-2 紫外灯光源的分光特性  \n\n![](images/4fbe02b0d1dac28dce70683cad6fd34c6e2a5b8621f6630f6dc024ab1637cd4f.jpg)  \n图3-6-3 紫外线照射处理后的接触角变化  \n\n紫外线照射处理中光源的波长对处理效果影响很大。直观地来看，聚乙烯板在硬质玻璃  \n容器中用紫外线照射环境（气体氛围）与紫外光的波长对处理效果也有关系。如图3-6-3表  \n示在空气和氨气中，不同波长紫外光照射处理聚乙烯后，用环氧-聚酰胺胶黏剂测试表面粘接强度的变化情况。  \n\n![](images/0c6b7368718388d32cff41018e1781d93fcf4353d2c0d98d91e928f6f1adc37b.jpg)  \n图3-6-4PE经紫外线照射处理后表面粘接强度的变化$1\\dot{\\mathrm{A}}{=}\\hat{\\mathsf{0}}.1\\mathrm{nm}$ ， $1\\mathrm{psi}{=}6.\\ 9\\mathrm{kPa}$  \n\n如图3-6-4所示，在1000s照射时间下，紫外光波长越长处理效果越显著。特别是在空气中从波长 $180\\sim$ $300\\mathrm{nm}$ 粘接强度急剧下降。因此用紫外光照射处理聚乙烯必须使用 $250\\mathrm{nm}$ 以下的短波长的紫外光，从操作控制上看以在氮气中处理更可靠。  \n\n(2）聚酯薄膜的紫外线处理紫外线处理对聚酯薄膜是最为有效的，应用也是比较多的。图3-6-5显示的是聚酯薄膜经紫外线处理后，几种液体接触角下降的情况。处理条件是光源与试片距离为 $\\mathfrak{s c m}$ ，真空度为 $13.33\\mathrm{Pa}$ ，处理时间为 $5\\mathrm{min}$ 。从图3-6-5中可以看出照射时间不到$10\\mathrm{min}$ 几种液体的接触角明显下降。从图3-6-6可以看出经过 $\\mathbf{\\bar{lomin}}$ 后聚酯薄膜的临界表面张力 $\\mathbf{5}_{\\mathbb{G}}$ 由 $0.04\\mathbf{N}/\\mathbf{m}$ 增加到 $0.047\\mathbf{N}/\\mathbf{m}$ ，这样就为涂料的附着创造了条件。  \n\n![](images/bf23cdfa236bb70849aee34e6466031b0ef23d25cde9936d04784dfec02458c0.jpg)  \n图3-6-5相对于各种紫外光照射表面的液体接触角口水； $\\cdot$ 甘油；乙二醇； $\\blacktriangledown$ 二缩三乙二醇； $\\boxed{\\pmb{\\bigtriangledown}}$ 磷酸三甲酚  \n\n![](images/c6ba64a241e565dc3d990d2ff78f18d84030ac601c2d9f7e605d5ebd8d8272d5.jpg)  \n图3-6-6 紫外线照射后临界表面张力 $\\delta_{e}$ 的变化  \n\n聚酯薄膜先用 $0.2\\%$ 洗涤剂水溶液、清水、蒸馏水依次洗过干燥后备用。用170W的低压汞灯处理，表面距离为 $8\\mathrm{cm}$ ，照射时间为 $5\\mathrm{min}$ 。同时进行 $80^{\\circ}C$ ， $37\\%N a\\mathrm{OH}$ 溶液处理和有机钛烷酯的偶联剂处理做对比实验。与 $\\mathbf{NaOH}$ 溶液处理结果相比，紫外光照射处理的效果超过两倍以上，而偶联剂处理的效果甚微。  \n\n聚酯经紫外线处理后表面粗糙度有明显变化，表面的结晶度有明显下降，且照射时间越长，表面结晶度降低越大。聚酯经紫外光照射后化学结构的变化如下。  \n\n从上述反应可以看出聚酯表面导人了羟基，从而增强了与涂料官能基的作用，进而增强了涂膜的附着力。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 472,
+        "chunk": "# 7.等离子表面处理法  \n\n等离子体（plasma）接触表面处理也称为电处理，由于产生等离子体的方式不同及表面处理方法不同分为辉光放电处理、电晕处理、等离子体喷枪表面处理、等离子表面聚合处理等。  \n\n等离子体状态下的气体施加以一定的电压后，气体中存在的少数自由电子得以加速，当其能量达到 $5{\\sim}10\\mathrm{eV}$ 之后就与附近的原子或分子碰撞，其结果可能从原子或分子中飞出电子，从而产生离子；也可能产生自由基；在此过程中产生的电子与原来的电子一样可以再加速进一步引起原子或分子解离或者令其处于激发状态。以自由基生成为例：  \n\n$$\n\\bar{\\mathrm{O}}_{2}\\longrightarrow\\mathrm{O}\\cdot+\\bar{\\mathrm{O}}\\cdot\n$$  \n\n$$\n\\begin{array}{c}{{\\mathrm{N}_{\\bar{z}}\\longrightarrow\\mathrm{N}\\cdot+\\mathrm{N}\\cdot}}\\\\ {{\\mathrm{H}_{\\bar{z}}\\mathrm{O}\\longrightarrow\\mathrm{OH}\\cdot+\\mathrm{H}\\cdot}}\\\\ {{\\mathrm{CH}_{4}\\longrightarrow\\mathrm{CH}_{3}\\cdot+\\mathrm{H}\\cdot}}\\end{array}\n$$  \n\n与加速电子发生碰撞后的原子或分子或者发生解离，或者接受能量后处于激发状态，经过电子轨道间的跃迁就可能产生紫外线。例如氧在下述变化过程中产生紫外光 $(h\\nu)$ 0  \n\n$$\n{\\mathrm{He+e^{*}}}{\\longrightarrow}{\\mathrm{He^{*}~+e}}\\stackrel{{\\prime}}{\\longrightarrow}{\\mathrm{He~}}{\\leftarrow}+{\\mathrm{He~}}{\\leftarrow}+{\\mathrm{e}}\n$$  \n\n其他的原子或分子均可经历类似的过程。这样一来，等离子体中可能存在： $\\textcircled{1}$ 加速的高能电子，失去能量的电子； $\\textcircled{2}$ 处于激发状态的中性原子及分子； $\\textcircled{3}$ 解离后的分子或原子自由基； $\\textcircled{4}$ 解离后的带电分子或原子(离子)； $\\textcircled{5}$ 解离过程中生成的紫外线； $\\textcircled{6}$ 未反应的中性原子和分子。  \n\n等离子体中存在的高能量和高反应活性的自由基、离子及紫外线等可以引起塑料表面的高分子聚合物发生一定的氧化、降解、聚合等反应。它们是等离子体表面处理的基础。首先必须采用适当的设备和装置来产生等离子体。处理的结果与设备的工作参数（电压、电极间隙、频率)、气体成分（ $|\\mathbf{O}_{2}|$ 、 $\\mathbf{N}_{2}$ 、 $\\mathrm{{\\bf{H}}_{2}O)}$ 、环境和工作条件（温度、湿度、时间）等关系很大。下面分别就几种常用的等离子体处理方法加以讨论。  \n\n(1）辉光放电处理辉光放电装置是在一个减压容器内，放上互相平行的平板电极，将被处理的塑料置于电极中央，通电后产生放电和等离子体对塑料进行表面处理。辉光放电处理是在低压情况下使用平行的平面电极放电对被处理物质进行放电处理。在被处理物质的表面可以生成带极性的官能团，从而提高被处理表面的临界表面张力 $s_{c}$ ，改善其被润湿性能。  \n\n![](images/2a822c275ec16262aa178ca1f0252c38e032721c7f52856b59615d49606cf585.jpg)  \n图3-6-7辉光放电处理装置1一电极（电极间距 $15c m,$ ；2—高分子试件；3—支架；4—抽真空管；5—真空管  \n\n一般实验室装置可用耐热玻璃，大型装置通常用金属容器，内部安装电极，被处理物质放入容器中，将容器内部抽真空 $13.33\\sim$ $133.3\\mathrm{Pa}$ ，而后通人所需气体，通电即产生等离子。处理时间可根据气压大小决定，如图3-6-7所示为实验室辉光放电处理装置。  \n\n影响辉光放电处理效果的主要因素有所用气体的成分、放电时的电压大小和放电处理时间。以下以辉光放电装置对聚乙烯（PE)、聚四氟乙烯（PTFE）处理为例进行介绍。  \n\n$\\textcircled{1}$ 对PE的处理实验结果  \n\na.气体成分如图3-6-8所示为对聚乙烯在 $N_{2}$ 和 $\\mathbf{A}\\mathbf{r}$ 中的辉光放电处理的ESCA光谱图，由图可以看出经过处理在Ar中生成含氧的活性基团，在 $N_{2}$ 中既生成含氧基团也生成含氮基团，比未处理的结合能力明显提高。  \n\nb.放电时电压对聚乙烯的放电处理时的气压条件进行试验，以处理后聚乙烯对不同液体的润湿角表示的结果如图3-6-9所示。从中可以看出放电时电压在0.1torr！ $\\mathrm{(13,33Pa)}$ 左右效果最好，对于水、无机盐的水溶液、溶剂等接触角变得很小。而在极性溶剂硝基苯中产生非常容易润湿的表面。比这个压力高或低，处理结果都会降低。  \n\nc.放电时间在0.1torr（ $\\mathrm{13.33Pa}$ ）气压下放电，1s即可得到满意结果。  \n\n![](images/854be63e2521d8b77bacedb56ebc2275fc3c53c32ba421292b710b8d83f2e831.jpg)  \n图3-6-8聚乙烯在 $N_{\\frac{3}{2}}$ 和 $\\mathbf{A}\\mathbf{r}$ 中辉光放电处理的ESCA光谱图  \n\n![](images/082d0ef549e0a753e2844575004d031873fb3889232b283b37df1f9a8c2e1030.jpg)  \n图3-6-9 对放电处理聚乙烯液体的接触角（放电时间1s）  \n\n$\\textcircled{2}$ 对PTFE的处理试验结果  \n\na.气体成分聚四氟乙烯（PTFE）在 $\\mathbf{N}_{2}$ 和 $\\mathbf{A}\\mathbf{\\tau}$ 中得到的处理效果如图3-6-10所示。  \n\nb.放电时气压和放电时间图3-6-11表示放电处理后的聚四氟乙烯对水的润湿角变化，图3-6-12表示放电后的聚四氟乙烯的临界表面张力的变化，可以看出放电时气压在0.3torr$(40\\mathbb{P a})$ ，以下，处理时间少于 $10s$ ，可获得良好的效果。  \n\n(2）电晕处理辉光放电时在低压状况下在平行的电极间放电，电晕放电则是在针状或刀形对极间放电，在期间置人被处理物体。电晕处理与辉光处理本质上的不同之处并不明确。辉光放电是在密闭的容器内，低气压进行，而电晕放电是在大气压下进行，设备简单，投资少，用于聚烯烃薄膜、薄板的表面处理最为理想。可根据被处理材料是否具有导电性来选择相应的处理装置，如图3-6-13(a）所示为被处理物质不导电情况下的装置，与被处理物质接触的辊简覆盖有诱电体材料，电极为棒状。若被处理薄膜为导电体时则使用如图3-6-13（b）所示的装置，图3-6-13(a）在辊筒状电极上覆盖有诱电体材料，其目的是为防止电晕成为电弧状。作为诱电材料是在使用时能耐高压，很少被臭氧劣化，可以涂布薄膜、诱电率高而电损失少等性质的材料。如图3-6-14所示为不同种类的电极，如图3-6-15所示是可抽真空的电晕放电处理装置。  \n\n![](images/02002e340fc94a99c7085528d4e4e86f2a970de896a69609c63af951c116b347.jpg)  \n图3-6-10聚四氟乙烯在 $N_{z}$ 和 $\\mathbf{A}\\mathbf{r}$ 中辉光放电处理的ESCA光谱图  \n\n![](images/a5cc8f2f1e3444f8188ba51f0c9042ec9663162b8ca564d5fb96894141186c24.jpg)  \n图3-6-11水对经放电处理的聚四氟乙烯的润湿放电时真空度：a为 ${10}\\mathrm{m}\\mathrm{m}{\\mathrm{H}}{\\mathrm{g}}$ ，b为 ${\\mathrm{1mmHz}}$ 中 $E$ 为 $\\bar{\\bf0},15\\mathrm{mmHz}$ ，d为 ${\\bar{0}},{\\bar{0}}5{\\bar{\\mathrm{mriHz}}}$ ·e为 $0,03\\mathrm{mmHz}$ ，f为未处理聚四氟乙烯， $\\mathrm{1mmHg=133,32Pa}$  \n\n![](images/288d6714da879a7937525e4d835af8131178f27a25a31b353e952e7d61d25cad.jpg)  \n图3-6-12聚四氟乙烯放电处理后的 $\\bar{s}_{\\bar{c}}$ 变化放电时真空度：a为 $\\mathrm{10mmH}\\bar{\\mathrm{g}}$ ，b为 $\\mathbf{immH}_{\\mathbf{B}}$ ，c为 $0.15\\mathrm{mmHz}$ ，d为 ${\\bar{0}}_{*}{\\bar{0}}5{\\mathrm{mmHg}}$ 1e为 $\\bar{0},\\bar{0}\\bar{1}\\bar{\\mathrm{mmHg}}$ ，f为未处理聚四氟乙烯， $\\mathrm{1mmHg=133,32Pa}$  \n\n![](images/387ad2e33d1035d626a63e46852f51fe5ee4ff1fbb8f3b678b90a43194c95787.jpg)  \n图3-6-13 电晕放电处理装置  \n\n![](images/f9df1d8e9a61f4a6618b140903f45b89bd50dab570da86becc326bf5ded1a6d0.jpg)  \n图3-6-14电极的种类 1一刀形电极；2—板形电极；3—辊筒电极； 4一覆盖诱电体辑筒电极  \n\n![](images/d061cfa60001ab8faa32c2c251e155ae5210a760208f9ea5ae653dfb65357c15.jpg)  \n图3-6-15 可抽真空的电晕放电处理装置A一处理薄膜；B—反应器；C—反应室；D—不锈钢电极；E一绝缘层  \n\n电晕放电特别适用于塑料薄膜的表面处理，广泛应用于塑料薄膜彩印的前处理。PP、PE及聚酯膜，在印刷机的工作条件下，由于薄膜处于电极和注射辊筒之间的连续放电作用，处理时间很短，可以达到良好的效果。聚乙烯处理与电晕处理的气体氛围关系很大。氧气、空气和$C O_{2}$ 在较短时间内（ $(<10.5)$ 可以将 $\\mathbf{\\sigma}_{\\bar{\\mathbf{\\mathcal{S}}}_{\\overline{{\\mathbb{C}}}}}$ 提高到 $40\\mathrm{mN/cm}$ 以上，达到很好的润湿效果。但在惰性气体中进行电晕放电处理其结果就不同了。以对油墨的附着强度为例，如图3-6-16所示。  \n\n![](images/8ee474ff5c1b480e684d9df4fe5992b68937a0048d1d0fa208a0887c315e5deb.jpg)  \n图3-6-16聚乙烯薄膜电晕处理时，气体氛围对油墨的附着强度、临界表面张力、对水的接触角的影响  \n\n$$\n1\\mathbf{kgf}/\\mathbf{cm^{2}}=98.07\\mathbf{kPa}\n$$  \n\n在氮气中随时间增加，表面润湿性的改善速率较慢，如果在氮气中混入少量水蒸气，放电效果大为改进。  \n\n电晕放电的效果与温度也有一定的关系。聚乙烯在空气中进行放电处理的温度和放电时间的影响如图3-6-17所示。  \n\n![](images/da16a76427dc1407428dad8d9613e233307bd5b283dae6e70d5917fda4a71feb.jpg)  \n图3-6-17 聚乙烯薄膜电晕处理时，温度对油墨附着强度、临界表面张力、接触角（水）的影响  \n\n在短时间处理过程中，温度高则处理效果好，表面特征变化较快，但是随着时间延长，其表面张力和涂层附着强度下降，这可能是表面过渡降解后形成了弱界面层（WBL）的缘故。  \n\n![](images/0de8f0e9134f02f2243b973a10d9311ac5e396425f9b493e7bff2f68f2ffa816.jpg)  \n图3-6-18 聚乙烯通过等离子喷射处理后的润湿及粘接性变化  \n\n（3）等离子喷枪处理 等离子喷枪处理是指使用电弧焊接机的电源和等离子发生用焊枪组合的装置进行表面处理的方法。通过大电流电弧放电，使氩等离子在空气中以喷射状放出，对塑料进行表面处理，此外还有低温非平衡状态下的低压射流处理方法。  \n\n经大电流放电产生的氩等离子处理的聚乙烯表面对于水的接触角变化如图3-6-18所示。电弧放电时的电流越大，等离子喷射发生口距离试样越近，对水的润湿性就越好。氧乙炔火焰处理只能使其对水的接触角为 $10^{\\circ}$ 左右。等离子射流处理的亲水化与单纯热处理的机械装置不同。以聚乙烯为例，粘接性也可提高到实用水平。  \n\n各种熟料等离子射流处理面的粘接性及对水的接触角值列于表3-6-15。虽然看起来聚四氟乙烯或聚丙烯等得到了很大改善，但还未达到实用水平。对于其他塑料可以看到相当大的效果。这种办法的最大特点就是处理的时间短，1s就可完成。  \n\n表3-6-15 部分塑料经等离子射流处理前后的性能变化  \n\n\n<html><body><table><tr><td rowspan=\"2\">塑料</td><td colspan=\"2\">与水接触角8/(°)</td><td colspan=\"2\">粘接强度/kPa</td></tr><tr><td>处理前</td><td>处理后</td><td>处理前</td><td>处理后</td></tr><tr><td>聚四氟乙烯</td><td>104</td><td>69</td><td>0</td><td>1471</td></tr><tr><td>聚丙烯</td><td>81</td><td>65</td><td><490.3</td><td>4216.9</td></tr><tr><td>聚乙烯</td><td>81</td><td>21</td><td>1078.7</td><td>13042.8</td></tr><tr><td>聚氯乙烯</td><td>68</td><td>27</td><td>11179.6</td><td>11571.8</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td rowspan=\"2\">塑料</td><td colspan=\"2\">与水接触角8/(°)</td><td colspan=\"2\">粘接强度/kPa</td></tr><tr><td>处理前</td><td>处理后</td><td>处理前</td><td>处理后</td></tr><tr><td>聚甲醛</td><td>69</td><td>29</td><td>5393.7</td><td>8531.8</td></tr><tr><td>聚碳酸酯</td><td>62</td><td>30</td><td>6374.3</td><td>16279</td></tr><tr><td>聚酰胺</td><td>60</td><td>24</td><td>5982.1</td><td>14906.1</td></tr><tr><td>ABS</td><td>80</td><td>36</td><td>16769.4</td><td>19907.5</td></tr><tr><td>丙烯酸树脂</td><td>67</td><td>42</td><td>1569.1</td><td>7845.3</td></tr><tr><td>酚醛树脂</td><td>61</td><td>20</td><td>23634</td><td>33146.5</td></tr></table></body></html>  \n\n等离子射流处理是相当激烈的表面处理，处理面处理效果达到稳定需要一些时间，从图  \n\n3-6-19可以看出处理后一天就会发生 $10^{\\circ}$ 左右的疏水化，以后就没什么变化了。  \n\n（4）等离子体聚合表面改性对于塑料表面的改性，可采用在其表面制作非常薄的高分子膜，利用这种薄膜的特性进行表面改性的方法。等离子聚合可以制作普通方法不能合成的新材料，因而能将塑料改为具有全新表面性质的塑料。这样塑料可以避免受到涂料各种成分的影响，而且还能使之成为涂膜附着良好的表面层。由于涂膜成分不会受到塑料的影响，就可以根据对涂膜性能的需求来改变组成以及选择涂料的品种。  \n\n这种高分子薄膜的制作，首先要利用放电现象让有机化合物（单体）等离子化，可以选择辉光放电和电晕放电两种形式。通常为了减少单体的热分解采用低压下辉光放电方式较多。作为反应装置既可以采用传统的内置电极将单体离子化的设备，也可以采用无电极方式的高频感应式电源放电方式。在离子化的时候可以是单体自身等离子化，也可以是通过载体气体引入单体，先将载体等离子化后再活化单体的方法。  \n\n![](images/68dbc4f11dfc3f940b9af6d652e68820bb687d7160860d55a20c5256d4354356.jpg)  \n图3-6-19聚乙烯经离子射流处理后的亲水性随时间变化其接触角的变化情况  \n\n聚合膜的形成速率受多种因素影响，从设备的什么位置导人单体、怎样安排排气的组合都会影响聚合膜的形成速率。单体和载体的流动方向、聚合膜形成的扩散状态也会使其改变聚合速率。此外载体的种类也有很大影响。对于聚乙烯膜生成速率来说有 $\\mathrm{N_{2}>A r>H_{2}}$ ，另外载体的分子量及物理性质也有一定关系。  \n\n在等离子聚合中，即使单体没有不饱和双键等特殊结构也可以形成聚合膜。自聚合效率和速率会受到单体性质的影响，现将聚合效率和单体种类的关系列于表3-6-16。从表中数据可以看出丙烯腈、氯苯、苯乙烯等容易聚合，然后是萘、对二甲苯、甲苯、苯胺、乙烯、乙炔等。  \n\n表3-6-16 单体种类和聚合速率  \n\n\n<html><body><table><tr><td rowspan=\"2\">单体种类</td><td colspan=\"2\">聚合速率</td><td rowspan=\"2\">单体种类</td><td colspan=\"2\">聚合速率</td></tr><tr><td>/[g/(kW·h)]</td><td>/[mol/(kW·h)]</td><td>/Eg/(kW·h)]</td><td>/[mol/(kW·h)]</td></tr><tr><td>氯苯</td><td>75</td><td>0.67</td><td>六甲基苯</td><td>28</td><td>0.17</td></tr><tr><td>苯乙烯</td><td>69</td><td>0.66</td><td>噻吩</td><td>13.5</td><td>0.16</td></tr><tr><td></td><td>62</td><td>0.48</td><td>四氟乙烯</td><td>12</td><td>0.12</td></tr><tr><td>丙烯睛</td><td>55</td><td>1.04</td><td>乙烯</td><td>11</td><td>0.39</td></tr><tr><td>p-二甲苯</td><td>45</td><td>0.42</td><td>乙炔</td><td>9</td><td>0.35</td></tr><tr><td>甲苯</td><td>38</td><td>0.41</td><td>三氯苯</td><td>5.5</td><td>0.03</td></tr><tr><td>苯胺</td><td>38</td><td>0.41</td><td>丙烷</td><td>5.2</td><td>0.12</td></tr></table></body></html>  \n\n等离子聚合反应速率与单体分子量大小、单体的分压、载气的分压多种因素有关。对于不饱和烃的聚合速率的相关数据列于表3-6-17。  \n\n表3-6-17等离子聚合不饱和烃聚合速率与单体和载体分压的关系  \n\n\n<html><body><table><tr><td>单体</td><td>分子量</td><td>a(g/cm²,min,torr²）</td><td>bX10-1(torr-1)</td></tr><tr><td>4-乙烯基吡啶</td><td>105</td><td>16.4</td><td>4.5</td></tr><tr><td>苯乙烯</td><td>104</td><td>12.1</td><td>8.0</td></tr><tr><td>乙烯基甲苯</td><td>118</td><td>11:4</td><td>6.6</td></tr><tr><td>2-乙烯基吡啶</td><td>105</td><td>10.4</td><td>5.0</td></tr><tr><td>丙烯睛</td><td>53</td><td>7.2</td><td>9.9</td></tr><tr><td>丁二烯</td><td>54</td><td>4.4</td><td>5.0</td></tr><tr><td>丙烯酰胺</td><td>57</td><td>3.2</td><td>5.9</td></tr><tr><td>四氟乙烯</td><td>42</td><td>1.6</td><td>一</td></tr><tr><td>氯乙烯</td><td>63</td><td>0.97</td><td>1.4</td></tr><tr><td>乙烯</td><td>28</td><td>0.32</td><td>一</td></tr></table></body></html>  \n\n$$\nU{=}a p_{\\mathrm{\\scriptscriptstyleM}}^{2}(1{+}b p_{\\mathrm{\\scriptscriptstyleX}})\n$$  \n\n式中 $U$ —聚合速率；${\\dot{p}}_{\\mathbb{M}}$ ——单体压力；${p}_{\\mathbf{X}}$ ——氮气压力。  \n\n从表3-6-17中的数据可以看出，聚合速率与单体压力关系很大，不饱和烃单体分子量越大，聚合速率越大。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 473,
+        "chunk": "# 二、表面应力的消除  \n\n塑料制品大多数是经过加热状态下的挤压或模塑加工成型的，有时加工温度可达到$150{\\sim}200^{\\circ}C$ 。在不均一的冷却过程中可能在制品的局部和表面产生残余应力，或者对于某些结晶性倾向高的塑料来说还会产生局部结晶化。残余应力和结晶化都不利于脱离的润湿和涂层的附着。它们在某些情况下不能用一般的表面处理方法加以消除。  \n\n消除表面应力来改变结晶性最简单和最有效的方法是采用退火的方法，即将塑料制品加热到一定温度后，再慢慢冷却以达到消除表面应力的目的。退火可以与表面活性剂处理或溶剂处理相互结合起来实施。具体方法和步骤可以根据制品的实际状态进行设计。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 474,
+        "chunk": "# 三、表面处理的评价方法  \n\n塑料制品经过表面处理后是否达到了改进脱离和印刷油墨的润湿性及其附着力的目的，直观来说可以采用常规的测定表面粗糙度、涂层附着力的各种方法进行判断。但是要深人的对各种处理方法进行总的评价，优化处理条件就必须采用各种仪器分析方法对被处理表面的化学状态和物理形态进行分析，同时测定有关参数进行定量的评估。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 475,
+        "chunk": "# 1.表面的化学状态  \n\n表面处理的主要目的之一在于使情性的塑料（PP、PE、PTFE等）表面活化，产生可与涂料成膜物产生化学键合或氢键结合的官能团。因此表面分析的作用在于确定证明活性官能团的存在及其表面的分布。  \n\n（1）元素和官能团的表面分析  \n\n$\\textcircled{1}$ 表面的元素分析可以采用：Auger电子分光光度法（AES)；光电子分光法（ES-  \n\nCA)；X射线分析法（XMA）；二次离子质量分析法（SIMS)；离子散射光谱法（ISS）。  \n\n$\\textcircled{2}$ 元素在表面的分布可采用XMA法测定。  \n\n$\\textcircled{3}$ 元素从表面向纵方向的分布可采用SIMS、ISS、AES、ESCA等方法测定被侵蚀表面的状态。④官能团的种类的确认方法：ESCA；红外吸收光谱（IR）；傅里叶转换红外光谱(FT-IR)。目前大多数采用高灵敏度、高速度的、傅里叶转换红外光谱的全反射或局部反射型仪器分析。③官能团的定量主要由红外吸收光谱法、傅里叶转换红外光谱定量法或化学分析法完成。（2）润湿性的评价表面改性和活化首先表现在润湿性的改善上。表征表面可润湿性的主要参数是表面对液体（溶剂、涂料等）的接触角和表面的临界表面张力Y。前面已经讨论只有当L（涂料的表面张力）小于Y时才会发生涂料对表面的润湿，比Y小得越多，润湿越彻底。  \n\n接触角可以采用常规的液滴形状法、气泡形状法、前进和后退润湿板法等实验方法测定。测定出液体的接触角，即可推算出。  \n\n润湿自由能： $\\gamma_{\\mathrm{{LCOS}}}\\delta_{\\varepsilon}$ 液体对固体的润湿功： $W_{\\sharp}[\\gamma_{\\mathrm{{L}}}(\\cos\\delta+1)]$ 液体在固体上的铺展功： $W_{\\textrm{s}}[\\gamma_{\\textrm{L}}(\\cos\\partial/-1)],$  \n\n测定出不同液体在被处理表面上的接触角8，以及对coSo作图并外推后即可测定出从处理表面的临界表面张力 $\\gamma_{c}$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 476,
+        "chunk": "# 2.表面的物理状态  \n\n许多表面处理方法都会对制品的表面产生一定程度的侵蚀作用，其结果产生一定的表面粗糙度。它对于涂料的润湿和涂层的附着力影响很大。表面过于粗糙对润湿不利；另一方面，适当的表面粗糙度同时也增大了表面面积，增强了涂料表面锚固作用，从而有利于附着。表面粗糙度可以采用电子显微镜照相的方法很容易进行评价。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 477,
+        "chunk": "# 第四节 塑料用涂料的分类  \n\n塑料的种类繁多，在工业、农业、汽车、家电等各个领域的应用日趋广泛，因此塑料用涂料也随之得到了发展。正是由于塑料用涂料的品质完善，使得塑料的用途得到了延伸。由于塑料的种类、表面性质、塑料制品应用的环境不同以及施工工艺的需要，所以对涂料和涂膜性能的要求也不同。因此同一种塑料需要多种涂料为之服务，反之不同种类的塑料往往也可以使用同一涂料涂饰。应用于金属、木材和其他基材的涂料大多都可以选来应用塑料表面的涂饰，但不是直接拿来用，而是要根据被涂塑料表面性质和对涂膜性能要求进行必要的改进或重新设计。",
+        "category": " Introduction"
+    },
+    {
+        "id": 478,
+        "chunk": "# 一、塑料用涂料选择基本原则  \n\n由于塑料底材的多样性，选择最佳的涂料体系和涂装工艺以达到最佳的使用效果和经济性是一项相当困难的任务。首先必须了解以下四方面的事实：  \n\n$\\textcircled{1}$ 塑料的化学组成，主要聚合物的结构、形态，热塑性还是热固性的树脂；  \n\n$\\textcircled{2}$ 成型加工方法；  \n\n$\\textcircled{3}$ 塑料制品的最终用途、使用环境条件以及产品所期望达到的性能要求；  \n\n$\\textcircled{4}$ 制品中所混加的单体材料、补强剂、着色剂及其他结构和辅助材料。  \n\n在上述事实的基础上再考虑塑料制品的涂装工艺，即将涂料种类与涂装方法、涂装工程一并结合起来才能得出合理的选择。",
+        "category": " Introduction"
+    },
+    {
+        "id": 479,
+        "chunk": "# 1.根据被涂塑料性质选择涂料  \n\n塑料为高分子材料，不同的塑料有着不同的结构和性质，为塑料选用涂料时应注意以下几点。  \n\n(1）确认塑料的种类是热塑性塑料还是热固性塑料。如果是热塑性塑料，再涂料的选择上就会方便一些，只考虑溶剂的溶蚀问题。但是热固性塑料的塑料表面已没有极性点，通常塑料要进行表面处理，以提高涂膜附着力。  \n\n(2）热塑性塑料需要考虑以下问题。  \n\n$\\textcircled{1}$ 若确认是热塑性塑料，还要认定是结晶性或非结晶性的塑料以及材料的极性大小。若是非极性或是结晶度较高的材料，涂料附着力就较差，应该考虑材料的表面处理以提高涂膜的附着力。  \n\n$\\textcircled{2}$ 热塑性塑料一般耐溶剂性较差，要根据塑料的溶解度参数选择适当的涂料和稀释剂。像聚苯乙烯（PS)、聚碳酸酯（PC）对溶剂都非常敏感，可选择以醇为主要溶剂的涂料或是水性涂料。  \n\n(3）塑料的热变形温度与烘烤温度。为了提高功效或是涂膜固化需要一定的温度，制品涂漆后需要在一定的温度下烘烤干燥，这就要求掌握被涂塑料的热变形温度，只能在低于热变形温度下干燥。可根据制品的热变形温度大小来选择相应的涂料。对于热变形温度低的塑料可选择挥发性涂料，如ABS、PS 等热变形温度低的塑料可选择自干的丙烯酸树脂涂料或是常温固化的丙烯酸聚氨酯涂料。对于热变形温度高的塑料，像氨基塑料、酚醛塑料，可以选择烘烤固化的涂料，如丙烯酸氨基涂料、有机硅改性涂料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 480,
+        "chunk": "# 2.根据塑料制品对涂膜性能的要求来选择涂料  \n\n塑料用涂料按用途可分为内用、外用及特殊用途涂料。  \n\n对于户内制品使用涂料多注重装饰效果，但对理化性能也还是有一定要求。例如电视机壳用的涂料，对涂膜要求具有一定的耐醇性和耐磨耗性；对玩具用的涂料，要求涂膜无毒性。对于已着色的塑料则要求涂料有足够的遮盖力。在装饰方面还可以通过不同施工方法制成金属装饰效果、木材装饰效果、假大理石装饰效果、晶纹、斑纹等装饰效果。在装饰性涂膜上面，往往根据制品的需要用丝网印刷、移印等方法印刷上文字或图案。这样要求涂膜对油墨有良好的黏合性。内用涂料通常可以考虑使用热塑性涂料，如聚氨酯醇酸、丙烯酸、丙烯酸硝基等涂料。  \n\n户外使用的塑料用涂料，除保证一定的装饰效果外，更重视涂膜的防护效果。长期的户外使用要求涂膜有很好的保光保色性，要求耐湿热、耐盐雾、耐紫外线、耐划伤等户外使用性能。如摩托车部件、户外检测仪器壳体、安全帽、汽车外壳等暴露在户外的塑料制品，表面涂饰通常选择耐候性的双组分脂肪族聚氨酯涂料、交联型丙烯酸涂料或低温固化氨基涂料。  \n\n此外一些特殊性能的需要，如聚苯乙烯、有机玻璃透明度很好，但表面硬度不高、易划伤，则需要透明度高、硬度高的涂料，如有机硅改性丙烯酸涂料来保护塑料表面。",
+        "category": " Introduction"
+    },
+    {
+        "id": 481,
+        "chunk": "# 3.根据施工工艺要求选择涂料  \n\n一般涂料的施工方法几乎都能用到塑料表面涂装，喷涂是塑料涂装的主要方法，使用场合十分广泛。近期又出现了静电喷涂、热喷涂、高压无空气喷涂及自动机械手喷涂。为适应不同的喷涂方式，涂料溶剂的极性、挥发速率和沸程都要做相应的调整。此外还有其他涂装方法，如浸涂、流涂、辊涂、淋涂等。为了涂膜的性质避免出现浮色、流挂以及保证涂料的使用期，涂料的组成及与之配套的溶剂都需要做相应的调整。  \n\n涂料的于燥方式对涂膜的性能也起着重要的作用，许多高性能的涂料都依赖看先进的十燥手段。一般的挥发性涂料，为了提高涂膜的性能和生产效率，也都使用塑料允许的十燥温度（一般为 $50{\\sim}60^{\\circ}C$ ）烘干，如交联型热固化涂料要在 $100\\sim150^{\\circ}C$ 下烘干。一些高硬度、耐磨、耐划伤的有机硅改性涂料、丙烯酸环氧涂料、聚酯等涂料使用紫外线固化、电子束固化可得到高性能涂膜。当使用这些固化方式时，涂料的组成和稀释剂的组成都要配合干燥工艺的变化加以变化。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 482,
+        "chunk": "# 二、主要塑料底材用涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 483,
+        "chunk": "# 1.ABS塑料用涂料  \n\nABS塑料可选择的涂料范围比较宽，可根据涂膜性能的要求选择挥发性涂料，如丙烯酸酯涂料、环氧涂料、醇酸涂料、硝基漆涂料、氨酯油涂料；也可选择双组分转化型涂料，如丙烯酸聚氨酯涂料。这些涂料都可以制成有光、丰光、各色金属质感以及橡胶软性质感涂料。ABS塑料涂料主要是由树脂、颜料、涂料助剂经研磨，调入有机混合溶剂组成。它的性能、用途和技术指标介绍见表3-6-18。  \n\n表3-6-18ABS塑料涂料的性能特点  \n\n\n<html><body><table><tr><td>项 目</td><td>AP-1塑料黑漆</td><td>塑-1清漆</td><td>塑-1各色磁漆</td><td>丙烯酸金 属闪光漆</td><td>丙烯酸彩 色透明漆</td></tr><tr><td>特性</td><td>能常温干燥，漆膜坚 硬耐磨，防潮</td><td>漆膜光亮，坚硬耐 磨，附着力好</td><td>漆膜颜色鲜艳，耐 水耐磨，附着力好</td><td>漆膜光亮，耐磨， 附着力好</td><td>漆膜光亮透明， 耐磨性好</td></tr><tr><td>用途</td><td>用于ABS、PC、PVC、 HIPS、塑料涂装</td><td>用于ABS、PS、塑 料涂装</td><td>用于ABS、PS、塑 料涂装</td><td>用于ABS、塑料 涂装</td><td>用于ABS、塑 料涂装</td></tr><tr><td>外观</td><td>黑色</td><td>透明</td><td>各色</td><td>各色</td><td>透明</td></tr><tr><td>硬度</td><td>0.6</td><td>0.5</td><td>0.5</td><td>0.6</td><td>0.6</td></tr><tr><td>光泽度</td><td><10</td><td></td><td>8~14</td><td>10~15</td><td></td></tr><tr><td>耐水性/h</td><td>24</td><td>24</td><td>24</td><td>24</td><td>24</td></tr><tr><td>耐醇性/h</td><td>60</td><td>20</td><td>20</td><td>50</td><td>50</td></tr></table></body></html>  \n\nABS塑料用涂料举例。  \n\n【例1】 热塑性丙烯酸树脂涂料  \n\n鉴于热塑性丙烯酸树脂树脂的干燥速度快、易施工等特点，广泛应用于ABS、PS、HIPS、聚丙烯酸酯、脲醛和酚醛等塑料的涂装，是目前塑料涂装工业应用最多的涂料品种。其施工性能与涂层性能严重受溶剂体系的制约。为了保证涂膜对塑料有足够的附着力和不溶蚀塑料表面，不同季节使用的溶剂体系及不同底材使用的溶剂体系皆不相同，见表3-6-19和表3-6-20。  \n\n随着我国国民经济及工业的发展，对塑料的涂层性能要求越来越高，例如：高耐醇性、镀银效果、立体花纹效果等的高装饰性，利用上述树脂，通过纤维素和氯醋树脂改性，添加效果颜料可以得到高耐磨的特殊效果塑料涂料（表3-6-21)。  \n\n单位： $14\\%$ 单位： $g_{\\phi}^{\\prime}$  \n\n表3-6-19不同季节丙烯酸塑料涂料的溶剂体系  \n\n\n<html><body><table><tr><td>原料</td><td>夏季稀料</td><td>春秋季稀料</td><td>冬季稀料</td><td>原料</td><td>夏季稀料</td><td>春秋季稀料</td><td>冬季稀料</td></tr><tr><td>丁醇</td><td>35</td><td>30</td><td>25</td><td>醋酸乙酯</td><td></td><td>40</td><td>45</td></tr><tr><td>醋酸丁酯</td><td>20</td><td></td><td></td><td>环已酮 甲苯</td><td>5 15</td><td></td><td></td></tr><tr><td>丙酮</td><td></td><td>15</td><td>25</td><td></td><td></td><td></td><td>5</td></tr><tr><td>二丙酮醇</td><td>25</td><td>15</td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n表3-6-20 不同底材用丙烯酸塑料涂料的溶剂体系  \n\n\n<html><body><table><tr><td>原料</td><td>注塑密度低的 ABS塑料</td><td>正常ABS塑料</td><td>原料</td><td>注塑密度低的 ABS塑料</td><td>正常ABS塑料</td></tr><tr><td>丁醇</td><td>5</td><td>10</td><td>醋酸乙酯</td><td>10</td><td>10</td></tr><tr><td>醋酸丁酯</td><td>15</td><td>30</td><td>120*溶剂汽油</td><td>5</td><td></td></tr><tr><td>丙酮</td><td>20</td><td>15</td><td>异丙醇</td><td>20</td><td>15</td></tr><tr><td>二丙酮醇</td><td>25</td><td>15</td><td>环己酮</td><td></td><td>5</td></tr></table></body></html>  \n\n表3-6-21ABS塑料用耐醇擦涂料  \n\n\n<html><body><table><tr><td>树脂配方</td><td>含量/%</td><td>树脂配方</td><td>含量/%</td></tr><tr><td>丙烯酸树脂</td><td>55</td><td>其他助剂</td><td>1</td></tr><tr><td>氯醋树脂</td><td>3</td><td>醋酸丁酯</td><td>10</td></tr><tr><td>纤维素树脂</td><td>5</td><td>CAC</td><td>8</td></tr><tr><td>银粉</td><td>9</td><td>醋酸乙酯</td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 484,
+        "chunk": "# 【例2】 聚氨酯涂料在塑料涂装中的应用  \n\n聚氨酯涂料因漆膜坚硬、光泽度高、耐化学品性强、弹性高等特点广泛用于ABS、PVC、PC、聚氨酯等塑料的涂装。涂料配方与喷涂用稀料见表3-6-22和表3-6-23。  \n\n表3-6-22 用于ABS上的铝粉聚氨酯漆配方  \n\n\n<html><body><table><tr><td>成分</td><td>含量/%</td><td>成分</td><td>含量/%</td></tr><tr><td>FS-2050:GD-71=1:1</td><td>55</td><td>BYK-P104S分散剂</td><td>0.5</td></tr><tr><td>闪光铝粉</td><td>7~9</td><td>201P沉剂</td><td>3~5</td></tr><tr><td>CAB381-0.5溶液（25%）</td><td>20</td><td>溶剂</td><td>13</td></tr><tr><td>流BYK-331</td><td>0.3~0.5</td><td>固化剂N-75</td><td>10</td></tr></table></body></html>  \n\n表3-6-23 用于ABS上的铝粉聚氨酯漆稀料配方  \n\n\n<html><body><table><tr><td>成分</td><td>含量/%</td><td>成分</td><td>含量/%</td></tr><tr><td>醋酸丁酯</td><td>30~50</td><td>丁醚</td><td>20~30</td></tr><tr><td>丙酮</td><td>10~40</td><td>CAC</td><td>10~20</td></tr></table></body></html>  \n\n上述漆的质量指标如下。  \n\n$\\textcircled{1}$ 铅笔硬度 $(70^{\\circ}C$ ， $30\\mathrm{mm})$ ： $\\geq\\mathrm{HB}$ 0  \n(7天)： ${\\tt\\geq}2\\tt{H}$ 9  \n$\\textcircled{2}$ 附着力(划格法)： $100\\%$ 0  \n$\\textcircled{3}$ 柔韧性： $1\\mathrm{mm}$ 0  \n$\\textcircled{4}$ 抗冲击强度： $50\\mathrm{kgf}\\cdot\\mathrm{cm}$ 心  \n施工参考：喷涂黏度 $13\\sim15{\\mathrm{s}}$ ，喷涂压力 $0.4{\\sim}0.6\\mathrm{MPa}.$ 8  \n\n【例3】紫外光固化涂料应用举例  \n热可塑性树脂铝粉底漆 $+\\boldsymbol{\\mathrm{UV}}$ 罩光试验参考配方见表3-6-24和表3-6-25。使用原料如下。  \n\n表3-6-24 铝粉底漆试验配方  \n\n\n<html><body><table><tr><td>Hypomer VP-UA-M6</td><td>丙烯酸酯聚合物</td><td>德谦化学</td></tr><tr><td>Hypomer AC-7435</td><td>热可塑性丙烯酸树脂</td><td>德谦化学</td></tr><tr><td>Hypomer AC-7407</td><td>热可塑性丙烯酸树脂</td><td>德谦化学</td></tr><tr><td>T-8970</td><td>铝浆</td><td>德谦化学</td></tr><tr><td>Levaslip 432</td><td>硅酮（聚硅氧烷）流平剂</td><td>德谦化学</td></tr><tr><td>Levaslip 875</td><td>硅酮（聚硅氧烷）流平剂</td><td>德谦化学</td></tr><tr><td>Desettle 201P浆</td><td>溶剂型防沉剂（固体分20%）</td><td>德谦化学</td></tr><tr><td>CAB-381-0.5</td><td>醋酸丁酸纤维素（固体分20%）</td><td></td></tr><tr><td>HDDA</td><td>1,6-己二醇二丙烯酸酯</td><td></td></tr><tr><td>TMPTA</td><td>三羟甲基丙烷三丙烯酸酯</td><td></td></tr><tr><td>1173</td><td>2-甲基-2-羟基-1-苯基-丙酮</td><td></td></tr><tr><td>Thinner</td><td>Xy1/NBAc/PMAc=4/3/1</td><td></td></tr></table></body></html>  \n\n单位： $\\%$   \n\n\n<html><body><table><tr><td>原料</td><td>添加量</td><td>添加量</td></tr><tr><td>Hypomer AC7435</td><td>50.0</td><td></td></tr><tr><td>Hypomer AC7407</td><td>一</td><td>50.0</td></tr><tr><td>T-8970</td><td>6.0</td><td>6.0</td></tr><tr><td>CAB-381-0.5(20%) 432</td><td>15.0 0.3</td><td>15.0 0.3</td></tr><tr><td>201P(20%)</td><td>10.0</td><td>10.0</td></tr><tr><td>Thinner</td><td>18.7</td><td>18.7</td></tr><tr><td>合计</td><td>100.0</td><td>100.0</td></tr></table></body></html>  \n\n表3-6-25UV罩光清漆试验配方单位：%  \n\n\n<html><body><table><tr><td>原料</td><td>添加量</td></tr><tr><td>VP-UA-M6</td><td>58.7</td></tr><tr><td>TMPTA</td><td>15.0</td></tr><tr><td>HDDA</td><td>21.5</td></tr><tr><td>1173</td><td>4.5</td></tr><tr><td>875</td><td>0.3</td></tr><tr><td>合计</td><td>100.0</td></tr></table></body></html>  \n\n罩光面漆基本性能如下。  \n\n$\\textcircled{1}$ 固化速率： $3\\mathrm{m/min}$ （条件：灯距 $10\\mathrm{cm}$ ，功率5kW)。 $\\textcircled{2}$ 在铝粉底漆上的附着力（百格法)：0级。 $\\textcircled{3}$ 硬度： $\\mathsf{2H}$ 。 $\\textcircled{4}80^{\\circ}C\\times4h$ 恒温水试验：涂膜基本无变化。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 485,
+        "chunk": "# 2.聚苯乙烯及其共聚物塑料用涂料  \n\n聚苯乙烯简称PS，其质地坚硬、化学性能和电绝缘性能优良，易于成型。制品色彩鲜艳、表面光亮，广泛应用于电气、仪表、包装、装潢和生活用品方面。但是其缺点是耐热性差和质脆，为此开发了一系列以苯乙烯为基础的改性聚苯乙烯，主要品种有通用性聚苯乙烯(GPPS)、高抗冲聚苯乙烯，也称改性聚苯乙烯（HIPS）和发泡聚苯乙烯（可发性聚苯乙烯，EPS)。除上述聚苯乙烯及其共聚物外还有由丙烯睛、氯化聚乙烯、苯乙烯三元共聚的ACS塑料，由丙烯睛、丙烯酸酯和苯乙烯三元共聚的AAS、MBS、SMA等热塑性塑料，下面介绍HIPS塑料用涂料，PS和其他改性的PS可参考HIPS适用的涂料进行配方设计及选择适用的涂料。  \n\n聚苯乙烯溶解度参数为 $8.6{\\sim}8.7~(\\mathrm{cal/cm^{3}})^{1/2}$ ，热变形温度为 $63\\sim93^{\\circ}C$ 。对聚苯乙烯及其改性聚苯乙烯尤其是发泡聚苯乙烯对溶剂非常敏感。酮、酯、芳烃都能溶蚀塑料，为此在配制混合溶剂时尽可能多地使用醇类溶剂或是烷烃溶剂以及相应可溶的树脂制备涂料。漆膜可以是常温干燥或强制干燥，强制干燥温度应在 $60^{\\circ}C$ 以下。可选用的涂料可以是挥发型涂料，如丙烯酸硝基涂料；也可以是常温固化的不饱和聚酯涂料以及环氧丙烯酸的光固化涂料。以下举例说明。",
+        "category": " Introduction"
+    },
+    {
+        "id": 486,
+        "chunk": "# 【例1】用于聚苯乙烯塑料的丙烯酸清漆  \n\n丙烯酸清漆含有甲基丙烯酸烷基（ $\\mathrm{:c_{1}}$ ）酯 $60\\%\\sim98\\%$ 、甲基丙烯酸烷基 $C C_{2}\\sim C_{4}$ ）酯$1\\%\\sim40\\%$ 、甲基丙烯酸烷基（ $C_{8}\\sim C_{22}$ ）酯 $1\\%\\sim20\\%$ ，其分子量为 $5000{\\sim}50000$ 、玻璃化  \n\n转变温度 $60\\sim95^{\\circ}C$ 的共聚物。  \n\n实例：将200：100：700（单体配料比）的甲基丙烯酸特丁酯-甲基丙烯酸十二烷基酯-甲基丙烯酸甲酯共聚物（50.3%的不挥发分，分子量25000）100质量份与铝粉浆（65%的不挥发分）10质量份混合，稀释，喷涂在聚苯乙烯上，并在60℃下烘烤30min，与未涂漆的样品相比较，形成的漆膜耐磨蚀100次和耐甲醇摩擦40次，而由 $100:100:80$ 的甲基内烯酸丁酯-甲基丙烯酸十二烷基酯-甲基丙烯酸甲酯共聚物（分子量4500）制备的涂层，其上述指标分别为20次和10次。  \n\n【例2】 HIPS塑料用丙烯酸硝基涂料  \n\n该涂料树脂部分是由丙烯酸树脂（甲基丙烯酸甲酯：丙烯酸丁酯：丙烯腈 $=19:20:5$ 共聚物）和硝化棉组成。  \n\n稀料组成：HIPS塑料容易被溶剂溶蚀，为了保证涂膜对塑料有足够的附着力和不溶蚀塑料表面，在不同季节施工应选用不同的稀料（表3-6-26）。  \n\n表3-6-26 三种稀料组成 单位：质量份  \n\n\n<html><body><table><tr><td>项目 配方</td><td>夏季稀料</td><td>6#稀料</td><td>冬季稀料</td><td>项目 配方 原料</td><td>夏季稀料</td><td>6#稀料</td><td>冬季稀料</td></tr><tr><td>原料 丁醇</td><td>30</td><td>20</td><td>25</td><td>醋酸乙酯</td><td></td><td>40</td><td>45</td></tr><tr><td>醋酸丁酯</td><td>20</td><td></td><td></td><td>环己酮</td><td>5</td><td></td><td></td></tr><tr><td>丙酮</td><td></td><td>25</td><td>25</td><td>甲苯</td><td>20</td><td></td><td>5</td></tr><tr><td>二丙酮醇</td><td>25</td><td>15</td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\nHIPS塑料硝基纤维素涂料配方举例（见表3-6-27）。  \n\n单位： $\\%$  \n\n表3-6-27HIPS等塑料硝基涂料配方  \n\n\n<html><body><table><tr><td rowspan=\"3\">原料</td><td colspan=\"5\">品种</td></tr><tr><td>中蓝</td><td>大红</td><td>光黑</td><td>白漆</td><td>银黑</td></tr><tr><td></td><td>64.98</td><td>57.98</td><td>45.88</td><td>42.97</td></tr><tr><td>45%丙烯酸树脂 硝化棉液（1/2s）</td><td>60.99 13</td><td>13.93</td><td>11.20</td><td>9.77</td><td>1.2</td></tr><tr><td></td><td></td><td></td><td>8.25</td><td></td><td>6</td></tr><tr><td>消光剂 R-820钛白</td><td>5.87</td><td></td><td></td><td>14.35</td><td></td></tr><tr><td>铁蓝</td><td>5.28</td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td>1.27</td><td></td><td>1.83</td></tr><tr><td>中色素炭黑</td><td></td><td></td><td></td><td></td><td>4.7</td></tr><tr><td>进口铝粉浆</td><td></td><td>6.09</td><td></td><td></td><td></td></tr><tr><td>3132大红粉</td><td></td><td>15</td><td>21.30</td><td></td><td></td></tr><tr><td>6#稀料 合计</td><td>14.86 100</td><td>100</td><td>100</td><td>30 100</td><td>36.3 100</td></tr></table></body></html>  \n\n以上不同颜色涂料，丙烯酸树脂与硝化棉固体比为 $7:1$ 心 ${\\hat{6}}^{\\sharp}$ 稀料配方为：丁醇 $20\\%$ ·丙酮 $25\\%$ ，二丙酮醇 $15\\%$ ，醋酸乙酯 $40\\%$  \n\n该涂料丙烯酸树脂中无强酸单体，故可以用来制造金属感铝粉漆，涂膜质量与日本进口涂料相当。该涂料若用于涂饰ABS制件时，可增大硝化棉用量，即丙烯酸树脂比硝化棉固体为 $3:1$ ，以提高漆膜硬度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 487,
+        "chunk": "# 3.聚烯烃-PE、PP、EVA用涂料  \n\n氯化聚烯烃及改性氯化聚烯烃涂料主要用于喷涂聚烯烃包括聚乙烯（PE)、聚丙烯(PP)、高乙烯含量 $(70\\%$ ）的乙烯-醋酸乙酯树脂（EVA）及乙烯、丙烯、丁二烯的二元、三元共聚物等。其中PP在汽车零配件中用量日益增大，PP和PE制品用量在所有塑料制品中是最大的，对它们的涂装需求日益增大。  \n\n聚烯烃的特征在干其结晶度高，耐溶剂性强，表面极性和表面能低，涂膜难于附看。因此采用适当的表面前处理进行表面改性是必要的，再采用底漆和面漆配套方案或者采用底面合一的涂装方案进行涂装。  \n\n作为底漆应与底材有相似的分子结构、近似的溶解度参数，还应与面漆有良好的层间附着力。近年来适用于PP和PE 的底漆开发十分活跃，其主要的成膜物体系有如下几类。  \n\n(1）氯化聚烯烃具有不同氯化程度的氯化PP、氯化PE、氯化EVA可单独或混合使用作为底漆成膜物。其中氯化度低的对底材附着力好，氯化度高的对面漆附着力好。目前氯化聚烯烃及改性氯化聚烯烃的品种较多，如中国台湾德谦公司有如下的型号与种类（表3-6-28)。  \n\n表3-6-28中国台湾德谦公司的氯化聚烯烃及改性氯化聚烯烃  \n\n\n<html><body><table><tr><td>性质与配比</td><td>分子量</td><td>氯含量/%</td><td>软/硬质</td><td>改性</td></tr><tr><td>PPC</td><td>80000</td><td>27</td><td>硬</td><td>无</td></tr><tr><td>CY-9124</td><td>60000</td><td>24</td><td>硬</td><td>1.6%马来酸</td></tr><tr><td>HM-21P</td><td>45000</td><td>21</td><td>硬</td><td>1.6%马来酸</td></tr><tr><td>P-5551</td><td>一</td><td>24</td><td>硬</td><td>丙烯酸</td></tr><tr><td>DX-526P</td><td>100000</td><td>26</td><td>软</td><td>无</td></tr><tr><td>M-28P</td><td>75000</td><td>20</td><td>软</td><td>1.4%马来酸</td></tr><tr><td>F-2P</td><td>75000</td><td>20</td><td>软</td><td>1.6%马来酸</td></tr><tr><td>CP-7540</td><td>50000~90000</td><td>5~10</td><td>软</td><td>丙烯酸</td></tr></table></body></html>\n\n氯化聚丙烯及其改性氯化聚丙烯与聚氨酯面漆配套用于喷涂汽车保险杠。  \n\n【例1】  \n\n$\\textcircled{1}$ 施工工艺  \na.PP灰底自干 $10\\mathrm{min}$   \nb.铝粉或白色面漆自干 $\\mathtt{I o m i n}$ 中  \nc.罩光漆 $80^{\\circ}\\mathrm{C}\\times45\\mathrm{min}$ ，放置5天后测试耐温水、耐汽油性能。$\\textcircled{2}$ 性能测试要求  \na．耐温水 $40^{\\circ}C\\times10$ 天不起泡，不脱落，附着力为 $0\\sim1$ 级。b.耐沸水 $100^{\\circ}C\\times2\\mathrm{h}$ 不起泡，不脱落，附着力为 $0{\\sim}1$ 级。$\\textcircled{3}$ 配方  \na.底漆树脂CP-7540拼CY-9124树脂，底漆配方见表3-6-29。  \n\n表3-6-29PP塑料汽车保险杠底漆配方 单位：%  \n\n\n<html><body><table><tr><td>组分</td><td>灰浆</td><td>调漆</td><td>总配方</td></tr><tr><td>混合树脂</td><td>27.0</td><td rowspan=\"4\">70</td><td>48.5</td></tr><tr><td>钛白粉R902</td><td>30.0</td><td>15</td></tr><tr><td>滑石粉1200目</td><td>14</td><td>7</td></tr><tr><td>HP-260</td><td>3</td><td>1.5</td></tr><tr><td>FW-200</td><td>0.4</td><td rowspan=\"3\">29.4</td><td>0.2</td></tr><tr><td>XYL/NBAc=2/1</td><td>20.6</td><td>25</td></tr><tr><td>流平剂</td><td>1</td><td>0.5</td></tr><tr><td>消泡剂</td><td></td><td rowspan=\"2\">0.6</td><td>0.3</td></tr><tr><td>流变剂</td><td>4</td><td>2</td></tr><tr><td>合计</td><td>100</td><td>100</td><td>100</td></tr></table></body></html>\n\nb.面漆树脂FS-2060B（白漆/铝粉)，面漆配方见表3-6-30和表3-6-31。  \n\n表3-6-31PP塑料汽车保险杠铝粉漆  \n\n\n<html><body><table><tr><td>组 分</td><td>白浆</td><td>调漆</td><td>总配方</td></tr><tr><td>FS-2060B 钛白粉R-902</td><td>37</td><td>80</td><td>58.5</td></tr><tr><td rowspan=\"4\">9250 XYL/NBAc/MEK/PMA=5/2/2/1</td><td>50 1</td><td></td><td>25.0</td></tr><tr><td></td><td></td><td>0.5</td></tr><tr><td>12</td><td>19.6</td><td>15.8</td></tr><tr><td></td><td>0.4</td><td>0.2 12.7</td></tr><tr><td>N-75 合计</td><td>100</td><td>100</td><td></td></tr></table></body></html>  \n\n表3-6-30PP塑料汽车保险杠白面漆 单位：%  \n单位：%   \n\n\n<html><body><table><tr><td></td><td>组成</td><td>总配方</td></tr><tr><td>FS-2860A</td><td></td><td>40</td></tr><tr><td>FS-4365A</td><td></td><td>40</td></tr><tr><td>XYL/NBAc/MEK/PMA=5/2/2/1</td><td></td><td>19.5</td></tr><tr><td>495</td><td></td><td>0.4</td></tr><tr><td>879</td><td></td><td>0.1</td></tr><tr><td>N-75</td><td></td><td>27</td></tr><tr><td>合计</td><td></td><td>100</td></tr></table></body></html>  \n\n单位： $19\\%$   \n\n\n<html><body><table><tr><td>组成</td><td>总配方</td></tr><tr><td>FS-2060B</td><td>55</td></tr><tr><td>国产铝浆 20%CAB-381-0.5</td><td>7.5</td></tr><tr><td></td><td>16.5</td></tr><tr><td>APW</td><td>2</td></tr><tr><td>XYL/NBAc/MEK/PMA=5/2/2/1</td><td>10</td></tr><tr><td>EAC</td><td>6.7</td></tr><tr><td>消泡剂</td><td>0.3</td></tr><tr><td>铝银定位剂</td><td>2</td></tr><tr><td>N-75</td><td>11.2</td></tr><tr><td>合计</td><td>100</td></tr></table></body></html>\n\nc.罩光树脂 $\\mathrm{FS–2860A/FS–4365A=1/1}$ ，罩光漆配方见表3-6-32。  \n\n【例2】 PP专用的水性底漆  \n\n水是所有溶剂中表面张力最大的一种，而聚烯烃是塑料中表面张力最低的，所以水性涂料对聚烯烃底材的润湿是最突出的问题。通常要求预处理后，底材的表面张力 ${>}4\\times10^{-4}\\mathrm{N}/$ cm，再经过配方设计，尽可能降低水性涂料的表面张力。作为成膜物，目前主要选用氯化聚烯烃，同时加入一定量的有机溶剂，配方见表3-6-33。  \n\n表3-6-32 PP塑料汽车保险杠  \n表3-6-33 PP专用的水性底漆  \n\n\n<html><body><table><tr><td>组成</td><td>配比/质量份 一</td><td>组成</td><td>配比/质量份</td></tr><tr><td>氯化聚烯烃（CI18%）</td><td>31.25</td><td>水</td><td>46.67</td></tr><tr><td>二甲苯</td><td>18.75</td><td>乳化剂</td><td>1.6</td></tr></table></body></html>  \n\n将上述组分在乳化器中乳化成固体含量为 $40\\%$ 的乳液，取该乳液90质量份与5质量份聚氨酯水分散体混合后，喷涂在PP板上， $40^{\\circ}C$ 下干燥 $15\\mathrm{min}$ ，可得附着良好的底漆，再罩以聚氨酯面漆。  \n\n聚烯烃经过共混方法可以显著地改进其表面极性，例如PP钙塑材料，PE与其他极性树脂（氯化聚乙烯、PVC、丙烯酸酯共聚物等）共混后，可以直接进行涂装。  \n\n(2）接枝改性的聚烯烃二元或三元、四元共聚烯烃可以用马来酸酐和丙烯酸单体进行接枝改性而引人极性基团。例如将HybrarHVS-3（氢化苯乙烯-异戊二烯-苯乙烯三元嵌段共聚物） $\\mathbf{105g}$ 与 $3.4\\dot{6}\\dot{\\mathrm{g}}$ 马来酸酐或与 $12.84\\mathrm{g}$ 丙烯酸羟丙酯，在过氧化二叔丁基存在下于$165^{\\circ}C$ 接枝共聚 $2\\mathrm{h}$ 。所得树脂可直接涂于聚丙烯板上，不需用含氯烃溶剂进行预处理。  \n\n(3）表面蒸汽沉积镀膜用的底漆表面镀膜用的底漆要求较好的耐热性、高光泽性、高硬度。一般可采用紫外光固化的涂料，为提高对PP的附着力，可用氯化聚烯烃进行改性。表面蒸汽沉积镀膜用的底漆见表3-6-34。  \n\n表3-6-34 表面蒸汽沉积镀膜用的底漆  \n\n\n<html><body><table><tr><td>组成</td><td></td><td>配比/质量份</td><td>组成</td><td>配比/质量份</td></tr><tr><td>氯化聚烯烃（CI<25%）</td><td></td><td>1</td><td>丙烯酸乙-二环戊氧乙基酯</td><td>5</td></tr><tr><td>二季戊四醇六丙烯酸酯</td><td></td><td>45</td><td>丙烯酸预聚物</td><td>30</td></tr><tr><td>氢化双酚A二丙烯酸酯</td><td></td><td>15</td><td>二甲苯</td><td>200</td></tr></table></body></html>  \n\n涂料涂于PP板上，用紫外线固化后可进行铝蒸气的沉积。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 488,
+        "chunk": "# 4.PVC用涂料  \n\n聚氯乙烯是产量很大的通用型塑料，具有优异的耐水性、耐候性。根据所含的增塑剂的种类和用量的不同可以制成从硬质PVC到软质PVC（如农用薄膜）的系列化产品，用途十分广泛，从化工厂的各种液体贮槽、晾水塔、大型仪器外壳、各类管道，以至于玩具、地板块、各种薄膜等。选择适用于PVC涂料的关键在于考虑PVC所用的增塑剂的种类、用量及迁移速率。增塑剂迁移至PVC的表面被涂层吸收后，一方面使涂层树脂溶胀和软化，令其表面耐沾污性下降；另一方面由于增塑剂的迁移导致PVC本身变硬和脆性增加而影响其使用性能。  \n\n对于涂料用的成膜物树脂既要求与PVC有相近的溶解度参数和弹性模量，从而具有良好的附着力；又要求它们与增塑剂没有相容性，不被增塑剂溶胀，并具有优良的封闭型，而对于溶剂和稀释剂的基本要求是对增塑剂没有溶解和萃取能力。近年来PVC工艺开发和使用了一些低分子量低聚物增塑剂代替迁移性和溶解力强的邻苯二甲酯类增塑剂，例如氯含量$20\\%\\sim30\\%$ 的氯化聚乙烯等，这给涂料的选择带来了更大的空间。  \n\n【例1】PVC挤出品用环氧改性丙烯酸/多异氰酸酯涂料（表3-6-35）  \n\n表3-6-35PVC挤出品用环氧改性丙烯酸/多异氰酸酯涂料  \n\n\n<html><body><table><tr><td colspan=\"2\">原料名称</td><td>配比（质量分数）/%</td><td colspan=\"2\">主要性能指标</td></tr><tr><td>主剂</td><td>环氧改性丙烯酸树脂（50%） 钛白粉(金红石型) 滑石粉（1250目） 膨润土 各种助剂</td><td>70 22 5 1.5 1.5</td><td>附着力(划格法)/级 铅笔硬度/H 表干时间/min 实干时间/h 耐盐雾/h</td><td>0 2 3 24 1000</td></tr><tr><td>固化剂</td><td>合计 多异氰酸酯</td><td>100 12</td><td></td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 489,
+        "chunk": "# 【例2】 聚氯乙烯农用薄膜用乳胶涂料  \n\n这种具有良好的耐土壤性和抗扯强度的农用薄膜，是用含活性基团的水分散性交联剂的丙烯酸聚合物乳胶涂覆增塑的聚氯乙烯薄膜而制造的。  \n\n实例：有甲基丙烯酸甲酯59质量份、甲基丙烯酸丁酯33质量份、甲基丙烯酸羟乙酯6质量份和甲基丙烯酸2质量份制取的 $20\\%$ 聚合物乳胶，含 $1\\%$ 三羟甲基丙烷聚缩水甘油醚（I）交联剂。用此乳液涂覆 $0.\\dot{0}15\\mathrm{mm}$ 厚的增塑氯乙烯薄膜，涂层厚 $5\\mu\\mathrm{m}$ + $130^{\\circ}C$ 烘干 $50\\mathbf{s}$ 中此薄膜抗扯强度为 $1200\\mathrm{g/cm^{2}}$ ，最初透明度 $92\\%$ ，户外试验两年后为 $78\\%$ ；而使用不含I的乳胶涂覆时，分别为 $630g/\\mathrm{cm}^{2}$ ， $92\\%$ 和 $68\\%$ 中",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 490,
+        "chunk": "# 5.聚碳酸酯用涂料  \n\n聚碳酸酯由于其优良的力学性能和较高的耐热性以及成型加工的尺寸稳定性，广泛地应用于仪器仪表的结构件。尤其是近年来光盘行业飞速发展，主要采用PC板作底材，从而对其涂料提出很高的要求。它们主要应具备极好的透明性、耐磨性、耐划伤性以及抗冲击性  \n\n能。因此主要以耐划伤的硬涂层涂料为主，下面举例说明。",
+        "category": " Introduction"
+    },
+    {
+        "id": 491,
+        "chunk": "# 【例】 聚碳酸酯的保护涂料  \n\n涂料溶液的制备方法是：滴加 $600\\mathbf{g}31\\%$ 的水性胶体二氧化硅分散体于 $500\\mathbf{g}$ 甲基三甲氧基硅烷中，并在 $\\mathrm{\\ttPH}=3\\sim\\hat{6}$ 下搅拌 $4\\ h$ ，然后用 $100g$ Ⅱ兑稀。这种面漆在 $100^{\\circ}C$ 下烘烤$60\\mathrm{min}$ ，所获得的板涂层附着力（划痕法和附着胶带法检验）为 $100\\%$ ，ASTMD1925泛黄指数开始时为2.1，在老化机试验 ${\\mathfrak{G}}{\\mathfrak{O}}{\\mathfrak{O}}{\\mathbf{h}}$ 后，上述值分别为 $100\\%$ 和4.5。这种老化机试验条件是黑板温度 $(63\\pm3)^{\\circ}C$ ，相对湿度 $(63\\pm3)\\%$ ，每小时喷雾 $12\\mathrm{min}$ 。但是不用上述底漆涂覆的板附着力为0。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 492,
+        "chunk": "# 6.聚丙烯酸酯用涂料  \n\n聚甲基丙烯酸甲酯（PMMA）俗称有机玻璃，是聚丙烯酸酯塑料中用量最多的品种。对于PMMA适用的涂料，尤其是航空用的有机玻璃上适用的涂料要求极好的透明性、耐划伤性及耐大气老化性。因此，主要应选用耐划伤硬涂层的品种为宜。例如常温固化双组分的丙烯酸聚氨酯涂料、有机硅烷系列涂料以及近年来迅速发展的有机氟树脂涂料。后者由四氟乙烯或偏氟氯乙烯与带羟基的单体（如4-羟基丁基乙烯醚）及其他乙烯单体经三元或四元共聚得到低分子量的含羟基含氟多元醇，再与缩二脲或HDI三聚体固化剂交联固化后可得到硬度高、耐划伤性好以及拒水、拒油、高透明性的涂层。而且其耐候性达人工老化 $1000\\mathbf{h}$ 以上，透明性保持 $95\\%$ 以上。  \n\n聚丙烯酸酯塑料的另一个重要用途是制作透镜，为此需要涂覆保护性的耐划伤、耐化学品且高度透明的涂层。它们一般由硅氧烷酯及其水解产物、胶态的金属氧化物或其复合粒子$\\mathrm{Al(ClO_{4})_{3}}$ 等组成。  \n\n例如：在 $30\\mathrm{min}$ 内将适量盐酸 $(0,05\\mathrm{mol/L})$ ）滴加到组成为（3-缩水甘油丙基）三甲氧基硅烷 $100\\mathbf{g}$ 、二乙氧基（3-缩水甘油丙基）甲基硅烷 $125\\mathrm{{g}}$ 、异丙醇 $100{\\sim}200\\mathbf{g}$ 的混合物中，保持 $50\\%$ 反应1h，将产物冷却后与 $300\\mathrm{g\\WO_{3}{-}S n O_{2}}$ 溶胶混合于 $20^{\\circ}C$ 陈化16h，用乙醇和乙基溶纤剂稀释涂装， $60\\mathrm{min}$ 后所得涂层附着力（划格法） $100/100$ ，干燥性、耐划伤性和耐溶剂性良好。  \n\n作为一般用途的聚丙烯酸酯塑料的应用范围很广，从照明灯具、日用杂货、汽车和摩托车零件到家用电器等。为了满足此类的装饰和保护目的大多数采用单组分的丙烯酸酯涂料，选择涂料品种时主要应注意溶剂对底材的侵蚀性及快干性。至于装饰性要求较高的场合可以选用丙烯酸聚氨酯涂料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 493,
+        "chunk": "# 7.脲醛和酚醛塑料用涂料  \n\n脲醛和酚醛塑料是最早得到工业化应用的热固性塑料，制品主要用来制作电器和电绝缘部件。脲醛树脂的热变形温度低，主要适用常温于燥或 $60\\sim80^{\\circ}C$ 加热干燥的涂料。由于脲醛树脂的价廉特性决定了涂装的要求不高，一般采用空气干燥型的醇酸漆、丙烯酸酯清漆或硝基漆以及酸催化的低温氨基醇酸烘漆等。  \n\n酚醛树脂具有优良的耐热性、电绝缘性及易成型加工性、突出的机械强度和价格方面的优势，近年来不仅使用量未下降，反而越来越多地替代工程塑料在汽车和电气工业中得到使用。酚醛树脂的模塑品、纤维增强酚醛制品（玻璃钢）以及阻燃和耐燃、特种功能制品正在不断开发出来。  \n\n尽管酚醛制品可以采用通用型的氨基醇酸烘漆在 $120^{\\circ}C$ ? $30\\mathrm{min}$ 条件下固化，但由于热收缩难以得到满意的光泽。最好在 $100^{\\circ}C$ 以下，加入有机酸催化剂进行固化为宜。对于装饰性要求较高的场合，可以采用双组分聚氨酯涂料涂装，具有代表性的是钓鱼竿及其涂装。目前市场上出售的钓鱼竿大部分是由玻璃纤维增强的酚醛树脂经热压成型，经涂底漆和二道浆打磨后，涂装各色丙烯酸聚氨酯或聚酯聚氨酯面漆、防滑手柄漆等制成。  \n\n【例】 酚醛泡沫塑料表面保护涂层  \n\n脆的泡沫塑料产品用活性高的聚氨酯组分喷涂后，可改进它的耐磨性。  \n\n实例：切割泡沫酚醛树脂块制成的盒，用两罐装聚酯涂料喷涂：其中一组分为等量的聚对苯二甲酸乙二醇酯和一缩二乙二醇（含 $0.6\\%$ 二月桂酸二丁基锡)；另一组分为95.4质量份粗MDI和5.2质量份邻苯二甲酸二丁酯。使用时按 $1:1$ （体积比）混合，喷涂后形成$\\mathrm{1.5mm}$ 的涂层。涂装后用作隔离鱼货箱，而装在没有涂装的盒内的鱼被酚醛树脂碎片污染。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 494,
+        "chunk": "# 8.聚酯塑料用涂料  \n\n聚酯树脂分为饱和聚酯和不饱和聚酯两大类，因此适用于它们的涂料分为饱和聚酯塑料用涂料和不饱和聚酯塑料用涂料。  \n\n(1）饱和聚酯塑料用涂料饱和聚酯塑料可以选用的涂料范围很宽，如聚酯聚氨酯涂料、环氧聚酯涂料、丙烯酸聚酯光固化涂料。  \n\n【例】 聚酯塑料用环氧光固化涂料（质量份）  \n\n该涂料含 $60{\\sim}95$ 质量份环氧树脂和 $5\\sim40$ 质量份热塑性饱和聚酯（平均分子量为 $2500\\sim$ 30000)，还有 $0.1\\%\\sim10\\%$ 按阳离子机理引发的光聚合引发剂。该涂层可附着，挠曲和抗冲击。  \n\n实例（质量份)：将含3，4-环氧环已烷羧酸酯(环氧当量 $131{\\sim}143\\$ ）65份，20份醋酸乙酯，20份1，4-丁二醇二缩水甘油醚（环氧当量 $125\\sim143;$ 、15份Vylon500（聚酯，分子量 $20000{\\sim}25000)$ ，0.5份有机硅表面活性剂和3份PP33（引发剂）的涂料涂覆在聚酯上，再经紫外线固化便制得平整光滑的涂层。  \n\n(2）不饱和聚酯塑料用涂料玻璃钢制品一般表面十分粗糙，需要很厚的涂层才能形成表面平整的涂膜，往往需要涂底漆甚至需要刮腻子。此外还可以使用模内成型注射涂饰，所用的涂料多为交联型涂料、环氧改性聚酯涂料、丙烯酸聚氨酯涂料、聚氨酯聚酯涂料、氨基醇酸涂料。涂料干燥方式可以是常温交联、烘烤交联，也可以是紫外线固化。  \n\n【例】 纤维增强塑料模制品用底漆  \n\n对纤维增强塑料模制品及其涂层有优良附着力的单包装底漆，含有环氧改性的聚酯树脂(平均双键数 $\\geqslant1.8\\$ ）和无机填料。例如将 $392{\\tt g}$ 马来酸酐和 $258\\mathbf{g}$ 丙二醇制得的不饱和聚酯，用 $\\mathbf{156g}$ 甲基丙烯酸缩水甘油酯（I）处理，并稀释在 $500\\mathbf{g}$ 苯乙烯内，即环氧改性聚酯（Ⅱ）（I含量为12.5%）（Ⅱ）70质量份、滑石粉30质量份、硬脂酸锌0.1质量份和叔丁基过苯甲酸酯1.2质量份组成的涂料，在纤维增强的不饱和聚酯板上形成光滑的涂层；该涂层对板的附着力（日本工业标准K-5400，划格）为 $10/10$ ，对氨基醇酸三聚氰胺面涂层的附着力为 $10/10$ （上述值是在 $40^{\\circ}C$ 和 $100\\%$ 相对湿度条件下 $240\\mathrm{h}$ 后检验获得，或在人工老化机内暴露 $600\\mathrm{h}$ 检验获得的)。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 495,
+        "chunk": "# 9.尼龙底材用涂料  \n\n尼龙（聚酰胺)、PBT（聚对苯二甲酸丁二醇酯）是优良的工程塑料，其耐热性和物理力学性能可满足汽车及电气制品的要求。它们的表面结晶度高，为了提高涂层的附着力，进行表面的前处理是必要的。作为底涂可选用双组分聚氨酯底漆，再配套丙烯酸聚氨酯面漆。PBT的涂装还可以选用单组分丙烯酸酯接枝的氯化聚烯烃涂料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 496,
+        "chunk": "# 【例】  \n\n组成  \n\n<html><body><table><tr><td>组成</td><td>配比/质量份</td><td>组成</td><td>配比/质量份</td></tr><tr><td>甲基丙烯酸月桂酯</td><td>14</td><td>甲基丙烯酸</td><td>1</td></tr><tr><td>苯乙烯</td><td>10</td><td>过氧化苯甲酰</td><td>3</td></tr></table></body></html>  \n\n将上述单体混合物，于80～100℃滴加到氯化聚烯烃的甲苯溶液中［CI含量27%的氯化聚丙烯的 $30\\%$ 甲苯液44质量份，高氯化聚乙烯（CI含量 $67\\%$ ）的 $30\\%$ 申苯液20质量份，反应并稀释至 $40\\%$ 固体分，该树脂液可制备清漆、色漆。涂装于聚酯表面后于 $80^{\\circ}C$ 干燥 $10\\mathrm{min}$ ，可得附着力100/100（划格法）的涂层。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 497,
+        "chunk": "# 10.其他特殊功能涂料  \n\n（1）导静电涂料塑料本身是电绝缘体，由于摩擦容易产生静电，轻者使其表面吸收灰尘而不耐脏；严重时，例如对于贮存有机溶剂和油品的容器来说，液体摩擦器壁可能产生静电火花引起着火。为了防止静电应保持表面电阻 $10^{6}\\sim10^{8}\\Omega$ 。一种办法是在塑料加工时加人导电填料以降低制品的体积电阻和表面电阻。这样势必要加入相当多的导电颜料，不仅影响制品性能，也直接与成本有关。另外一种办法是涂装导静电涂料以降低塑料制品的表面电阻。  \n\n石墨-炭黑、磷化铁、导电云母或导电氧化物为通用的导静电填料。导静电涂料一般不适用于塑料制品，因为它们的填充度较高，机械强度差，与塑料底材匹配性差。塑料用导电涂料大多在成膜物中引入防静电的官能团，使其具有永久性的防静电作用，如一 $N^{+}$ ${\\bf R}_{3}$ Cl—、季铵盐、小分子聚氧乙烯链、磺酸盐、羟酸盐等阴离子以及酰胺官能团等强极性分子结构。具体举例如下：  \n\n【例1】  \n\n<html><body><table><tr><td>组成</td><td>配比/质量份</td><td>组成</td><td>配比/质量份</td></tr><tr><td>丙烯酸树脂成膜物</td><td>80</td><td>LiClO4</td><td>15</td></tr><tr><td>四甘醇二甲醚</td><td>5</td><td>醋酸乙酯</td><td>720</td></tr></table></body></html>  \n\n将上述组成溶解后，涂于PMMA树脂板上，于室温下干燥后即可。涂膜抗静电性好，雾影0.5。  \n\n【例2】含 $N,N-$ 二甲基丙烯酰胺的光固化涂料  \n\n由季戊四醇三丙烯酸酯、甲基丙烯酸缩水甘油酯、聚氨酯丙烯酸酯、光敏剂与抗静电剂（含 $N{\\geqslant}1$ 丙烯酰基的酰胺、胺或其磷酸酯）等组成，经紫外光固化后可得到优良的导静电涂层。  \n\n【例3】  \n\n<html><body><table><tr><td>组成</td><td>配比/质量份</td><td>组成</td><td>配比/质量份</td></tr><tr><td>甲基丙烯酸丁酯</td><td>60~65</td><td>乙二醇单乙醚</td><td>200</td></tr><tr><td>甲基丙烯酸异辛酯</td><td>30</td><td>过氧化苯甲酰</td><td>0.5</td></tr><tr><td>甲基丙烯酸乙-羟基-丙基-3-三甲胺氯化物</td><td>10</td><td></td><td></td></tr></table></body></html>  \n\n将上述组成于 $80\\approx90^{\\circ}C$ 、溶液聚合 $5\\sim6\\mathrm{h}$ 后即得导静电树脂液。涂于塑料板上可得透明涂膜，当 $20\\mu\\mathrm{m}$ 厚时，其表面电阻为 $5\\times10^{7}\\Omega$  \n\n(2）防火涂料防火涂料可分为膨胀型和非膨胀型两种，按溶剂类型又可分为溶剂型和水性两种。防火涂料由基料、颜料和填料、阻燃剂以及膨胀防火助剂组成。塑料用防火涂料属于饰面型防火涂料，由于塑料是可燃基材，又需要一定的装饰效果。因此要求防火涂料即能防火阻燃又具有塑料制品要求的一定的装饰性和物理化学性能。膨胀型和非膨胀型都可以用来作塑料用防火涂料。下面列出饰面防火涂料配方供参考，见表3-6-36～表3-6-39。  \n\n塑料用涂料通常要求具有一定的装饰性和必要的理化性能，而且要求涂层不宜太厚。然而防火涂料的阻燃剂达不到一定量就起不到阻燃效果，为了减少阻燃剂的用量应尽可能地使用含氮或含卤素树脂作基料，这些树脂本身难燃且能释放灭火性气体或分解阻燃的活性基团，这样就可以在保证塑料用涂料拥有的性能前提下来达到防火的目的。  \n\n表3-6-36 非膨胀（溶剂）型饰面防火涂料  \n\n\n<html><body><table><tr><td>原料</td><td>配比/%</td><td>原料</td><td>配比/%</td></tr><tr><td>过氯乙烯树脂</td><td>13</td><td rowspan=\"3\">丙酮 乙酸丁酯</td><td>14</td></tr><tr><td>松香改性苯酚甲醛树脂</td><td>10</td><td>13</td></tr><tr><td>氯化联苯</td><td>2 甲苯</td><td>47</td></tr></table></body></html>  \n\n表3-6-37 非膨胀（乳液）型饰面防火涂料  \n\n\n<html><body><table><tr><td>原料</td><td>配比/%</td><td>原料</td><td>配比/%</td></tr><tr><td>乙酸乙烯-丙烯酸酯共聚乳液</td><td>23.60</td><td>羟乙基纤维素</td><td>0.24</td></tr><tr><td>锑白</td><td>1.32</td><td>六偏磷酸钠（1%水溶液）</td><td>6.00</td></tr><tr><td>金红石型钛白</td><td>20.00</td><td>阴离子型润湿分散剂</td><td>0.43</td></tr><tr><td>瓷土</td><td>5.00</td><td>消泡剂</td><td>1.00</td></tr><tr><td>碳酸钙</td><td>10.00</td><td>防霉剂</td><td>0.05</td></tr><tr><td>云母粉</td><td>5.55</td><td>二乙二醇单丁醚乙酸酯</td><td>1.00</td></tr><tr><td>五溴甲苯</td><td>0.66</td><td>水</td><td>25.15</td></tr></table></body></html>  \n\n表3-6-38 膨胀（溶剂）型饰面防火涂料  \n\n\n<html><body><table><tr><td>原料</td><td>配比/%</td><td>原料</td><td>配比/%</td></tr><tr><td>乙烯共聚树脂(PlioliteVT)</td><td>20.49</td><td>三聚氰胺</td><td>4.29</td></tr><tr><td>Phos-chek/30</td><td>23.15</td><td>双季戊四醇</td><td>8.57</td></tr><tr><td>氯化石蜡（含氯70%）</td><td>8.57</td><td>矿油精</td><td>23.79</td></tr><tr><td>钛白</td><td>11.14</td><td></td><td></td></tr></table></body></html>  \n\n表3-6-39 膨胀（乳液）型饰面防火涂料  \n\n\n<html><body><table><tr><td>原料</td><td>配比/%</td><td>原料</td><td>配比/%</td></tr><tr><td>氯偏共聚乳液</td><td>21</td><td>钛白</td><td>12</td></tr><tr><td>聚磷酸铵</td><td>56(磷酸铵）</td><td>OP-10(玉米糊精)</td><td>53</td></tr><tr><td>季戊四醇</td><td>15.9</td><td>羟甲基纤维素</td><td>藻航酸钠0.6</td></tr><tr><td>三聚氰胺</td><td>双氰胺10</td><td>水</td><td>75</td></tr></table></body></html>  \n\n(3）内膜涂装用涂料近年来内膜涂装在塑料加工中发展迅速。它是将涂料涂装在模具内壁，在塑料模压成型的过程中同时完成塑料制品的表面涂装。  \n\n这类涂料大多是粉末涂料，可采用静电喷涂工艺将其涂装在金属模具上，再进行塑料模塑，往往塑料成型温度较高，粉末再成型过程中部分固化成膜，成型后再加热即可完成固化。由于模塑时压力很高，十分有利于塑料与涂层的表面附着。而且模具本身光洁度很高，涂层的表面十分光洁，光泽度高。根据塑料底材的性质可以选用环氧、环氧-聚酯、聚酯、丙烯酸酯-聚氨酯等多种粉末涂料，也可采用粉末分散型的涂料进行涂装。例如用含有间苯二甲酸-马来酸酐-丙二醇共聚物的 $40\\%$ 溶液100质量份、聚酯粉末150质量份及分散剂1质量份的组合物进行内膜涂装，然后进行不饱和聚酯剥离增强塑料板材的模塑，所得产品的光泽度为93，附着力100/100（划格法）。  \n\n（4）防结露涂料雾化现象可以认为是在一定温度的空间里，当温度降至露点以下所形成的细小露珠吸附在物体表面的现象。解决雾化主要有以下几种方法。  \n\na.在塑料薄膜中添加少量含结晶水的盐类，白天温度高失去结晶水，夜晚温度低水 蒸气凝聚到薄膜表面而后被吸收到内部，类似室内墙壁，这样防止了结露，解决了雾化 问题。  \n\nb.增大塑料表面疏水性，即使表面结露也只会形成粗大的水滴，不久就会脱落，从而保持了透明薄膜的透明性。为此可在塑料表面涂饰含表面张力小的有机硅或氟的涂料，增大制品表面的疏水性。  \n\nc.从相反的角度考虑，增大塑料表面的亲水性，使塑料表面对水有良好的润湿性，对水的接触角变小，这样即使凝露，液滴很快扩展摊平形成水膜，就不会形成光的漫反射。  \n\n解决塑料防雾化的方法很多，这里主要介绍通过表面涂饰来解决防雾化的方法。  \n\n【例1】 透明塑料或剥离膜上用的防止露水凝结的涂料  \n\n防止露水凝结和耐划痕涂料组分对透明塑料或有机玻璃有高的附着力，包括带有甲基硅烷基的聚乙烯醇和有无机填料的水溶性聚合物乳液。  \n\n例如： $0.25:99.75$ （摩尔比）乙烯基三甲氧基硅烷-乙烯醇共聚物（皂化度 $98\\%$ ，聚合度2000）的 $10\\%$ 溶液100质量份和 $75:1:24$ 乙烯-顺丁烯二酸-醋酸乙烯共聚物 $40\\%$ 水乳液5质量份相混合，涂在聚酯薄膜上，厚度为 $5\\mu\\mathrm{m}$ ，在 $105^{\\circ}C$ 干燥 $10\\mathrm{min}$ ，浸在 $0.25\\mathrm{mol}/$ $\\mathbf{L}$ 硫酸中，用水洗涤，在 $150^{\\circ}C$ 热处理1min后得产品。划格法附着力100/100，硬度5H，在 $40^{\\circ}C$ 饱和水蒸气中放10s，往返10周期后没有露水形成。  \n\n【例2】 用于多种塑料透明防雾化涂料  \n\n防雾化涂料包含聚乙烯吡咯烷酮（I）、聚二甲基丙烯酰胺，或乙烯基吡咯烷酮与不带同异氰酸酯反应的官能团的 $a$ -烯烃的共聚物、多异氰酸酯预聚物、可与聚合物和预聚物的反应产物化学结合的表面活性剂以及有机溶剂。在固化时，表面活性剂与亲水的聚合物——异氰酸酯聚合物结合，因此表面活性剂不会被提取出来，使底材具有耐久的防雾性。例如：将$2.5{\\dot{\\mathbf{g}}}$ I溶解在 $\\mathrm{100mL75:25}$ 的二丙酮醇-环已烷混合溶剂中，将该溶液与 $1.0\\mathbf{g}$ 硫代丁二酸二辛酯表面活性剂和 $5.\\ 0\\mathbf{g}$ Tycel7351异氰酸酯预聚物混合，然后涂布在底材上，于 $21.1\\dot{\\mathrm{{C}}}$ 下固化 $24\\mathrm{h}$ ，所得涂层是透明、无色、硬且耐划伤的，将其冷却到 $0^{\\circ}C$ 再置于沸水上面不起雾。该涂料对聚碳酸酯、聚酯、聚甲基丙烯酸甲酯和醋酸纤维素等底材附着力优良。  \n\n(5）塑料真空镀金属膜用涂料塑料虽然可以在很多场合替代金属，但是无论是装饰效果还是使用效果均缺乏金属质感。采用真空镀膜将金属融化后，在真空状态下将金属以分子或原子形态沉积在塑料表面形成 $<10\\mu\\mathrm{m}$ 厚的金属膜；或者是采用溅射法—用高能射线轰击金属表面，令金属原子飞出而沉积在塑料表面，成膜后可以得到金属装饰效果的塑料制品。镀膜的关键决定底漆和面漆的质量及施工工艺。对塑料真空镀膜底漆和面漆的性能要求如下。  \n\n$\\textcircled{1}$ 对真空镀膜的底漆性能要求。  \n\na.底漆应具有塑料用涂料的基本性能，即不溶蚀塑料表面并对塑料表面有 $100\\%$ 的附着力。b.底漆的细度要小于 $3\\mu\\mathrm{m}$ ，涂膜不能有看得见的细小微粒和其他涂膜缺陷。c.涂膜要平整光亮和有足够的丰满度。d.底漆对已镀上的铝、铜、不锈钢、镍、铬等金属膜有足够的结合力。e.挥发型的底漆涂膜要 $100\\%$ 地干燥，交联型的涂膜要反应完全，在真空下不能有能被抽取出来的溶剂、没反应完全的单体和低分子物。f.对于使用增塑剂量大的聚氯乙烯塑料、醋酸纤维素涂膜必须具有足够的硬度以防止增塑剂被抽提出来。  \n\ng.对于深色的塑料（如酚醛塑料）应涂饰白色或浅色的底漆，以免影响镀膜的色泽。  \n\n具备上述性能的涂料生产出来以后，要经过过滤纸真空抽滤，要使树脂细度在 $3\\mu\\mathrm{m}$ 以下。底漆在施工时，室内空气需经过过滤，绝对不允许涂膜表面有颗粒。涂漆后的工件涂膜完全干燥，送至真空室时，手不能触摸漆膜，要保证漆膜的干净。  \n\n底漆的选择一方面决定于被涂塑料的种类；另一方面还取决于产品的价值。一般像玩具、服装饰件涂料可选档次低一些，而像汽车、仪器部件、卫生洁具部件涂料选择档次要高一些。塑料件软化温度低的不允许使用烘烤型涂料，可以选择常温交联的聚氨酯涂料、胺固化环氧涂料，对于耐溶剂敏感的涂料可以选用以醇为主要溶剂的丙烯酸涂料。如果工件形状允许的话还可以使用紫外固化的环氧丙烯酸涂料、有机硅涂料。底漆尽可能使用交联型涂料，这样面漆的选择就会方便一些。  \n\n$\\textcircled{2}$ 对真空镀膜的面漆要求金属镀膜很薄，容易被划伤和氧化，必须涂饰一层具有保护性的透明面漆。a．对金属镀膜具有 $100\\%$ 的附着，不能穿过镀膜对底漆溶蚀，而破坏了镀膜平整。b.涂膜必须具有优良的物理性能（如耐划伤、耐磨耗）和良好的化学性能（如耐水、耐候性等)。c.涂膜透明、丰满度高、能良好地显示原金属光泽，并且能够以透明颜料染色不改变涂膜的颜色。  \n\n值得注意的是镀膜后的工件应立即涂饰面漆，否则工件落上尘土是无法清除的。面漆的选择要与底漆配套。在涂饰面漆时依然要注意施工环境的清洁，以免污染涂膜。  \n\n【例1】 塑料真空镀膜喷镀前用底漆  \n\n100质量份硝基纤维素（I）和104质量份聚异氰酸酯的混合物可用作塑料、剥离或陶瓷制件上金属喷镀前的底漆。实例（质量份）：ABS树脂板用I143份、甲苯200份、二甲苯500份、甲乙酮800份、甲基异丁基酮150份和DesmodurL752份的混合物涂覆，在$80^{\\circ}C$ 干燥 $30\\mathrm{min}$ 生成 $10\\mu\\mathrm{m}$ 厚的涂层，用不锈钢粉真空镀到 $40\\mathrm{nm}$ ，再用丙烯酸聚氨酯涂面漆，在 $65^{\\circ}C$ 干燥 ${\\mathfrak{G O m i n}}$ 生成的涂层对底材有优良的附着力，且耐热性良好（ $80^{\\circ}C$ ，5h)。  \n\n【例2】 塑料表面用金属闪光涂料  \n\n一种赋予塑料制品表面优良的金属闪光的廉价方法，它包括等离子体预处理、底涂层、金属沉积和面漆涂装四步。例如聚丙烯样品经甲醇洗涤，真空干燥 $24\\mathrm{h}$ 后用 $(2450\\pm50)$ $\\mathbf{MHz}$ 微波等离子体在133.32Pa压力的氧下预处理，然后喷涂EXP1007（聚氨基甲酸酯)干燥后形成 $10\\mu\\mathrm{m}$ 的膜，在经阴极真空喷镀上一层 $45\\mathrm{nm}$ 的Hastelloy的膜，然后喷涂EXP1155（丙烯酸氨基甲酸酯聚合物)，干后形成 $10\\mu\\mathrm{m}$ 的面漆。生成的涂层具有优良的金属闪光性，在 $80^{\\circ}C$ 下5h和 $40^{\\circ}C$ 下浸水150h后附着力均好。  \n\n【例3】 塑料膜上金属镀层的保护涂层  \n\n实例（质量份)：用聚（甲氧甲基）三聚氰胺（ $60\\%$ ）245份、丙烯酸树脂（ $50\\%$ ，含$4\\%$ 的羟基）200份、硝化棉90份、甲乙酮-甲苯-醋酸丁酯混合溶剂450份和对-甲苯磺酸$(40\\%$ ）15份组成的挥发型漆，在塑料膜（ ${\\scriptstyle\\left(12\\sim100\\mu\\ m\\right.}$ ）金属层 $(0,\\bar{0}2{\\sim}0,08\\mu\\mathrm{m})$ 上制备保护涂膜 $(2\\sim20\\mu\\mathrm{m})$ 。用热熔性黏合剂将该塑料膜粘在PVC 膜（ $(50\\sim250\\mu\\mathrm{m})$ ）上。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 498,
+        "chunk": "# 第五节 塑料涂料的涂装  \n\n塑料制品涂装的目的与金属、木材等其他底材涂装并无原则上的差别，都是满足制品对保护、装饰和特殊功能性的要求，达到延长使用寿命、美观、增加制品附加值的目的。但是与金属和木材底材涂装不同之处在于，塑料制品基本上不存在腐蚀的问题，但同时出现了底材附着力的问题。其次，塑料制品由于化学结构、加工方法和组成的多样性又决定了其表面状态的多样性，这就增加了涂装中表面处理的分量。从涂装方法的选择上，由于大多数热塑性塑料的热变形温度较金属和木材低得多，因此对烘烤漆和热固化涂料的涂装又有一定的限制。此外，塑料制品大多都不导电，所以选择静电喷涂有一定的困难。塑料制品还有一大特点是品种繁多，既有大批量可上线涂装的品种，也有小批量的适合手工操作的品种。这样就给涂装设计和涂料品种的选择带来一定困难。  \n\n现在涂料和涂装是密不可分的整体。涂料只有采用适当的涂装方式才能在制品上形成符合要求的涂层。现在的涂装设计就是包含了涂装工艺和涂料选择这样一个系统和完整的观点。涂料供应商必须与用户和涂装工艺师密切配合，根据涂装要求，设计和提供能够满足涂装工艺、性价比适中的涂料，并且按照实际情况，提供优良的技术服务，随时调整配方以获得最佳的涂装效果。  \n\n被涂覆产品的工业化大规模生产，刺激了涂料生产技术的发展。一方面要提供高品质的涂料；另一方面要求提供的涂料能满足规模化快速流水线的施工特性要求，促使涂料施工方法和涂装技术不断地创新和提高。涂装生产也由手工作业进人高效工业化生产方式，并由空气喷涂、浸涂、淋涂、辊涂等一般高效机械化涂装作业进一步发展到高压无气喷涂、自动喷涂、静电喷涂、粉末涂装、电泳涂装等现代工业涂装新技术。  \n\n现代涂料与涂装技术更主要还是来自环境保护法的限制而激发产生的，由于一般溶剂性涂料施工固体分低，它们大规模应用导致了严重的大气污染。自 $^{i i}{\\hat{6}}{\\hat{6}}^{\\prime\\prime}$ 法规颁布以后，世界发达国家都制定了各自的法规，这样普通溶剂性树脂漆的生产面临着严峻的挑战，各类环保性涂料和涂装方法应运而生。因此，现代工业涂料和工业化涂装技术是按照：高效率 $\\nrightarrow$ 优质，高效→公共社会性（经济安全性、低污染性、节能、省资源等几个方面）这一过程发展的。",
+        "category": " Introduction"
+    },
+    {
+        "id": 499,
+        "chunk": "# 一、塑料涂料涂装施工方法  \n\n塑料涂装多采取喷涂的方式。喷涂使用许多不同种类的设备；它们将液体全部雾化成液滴。液滴大小取决于喷枪和涂料的类型，其变量包括空气压力和液压、液体流动、表面张力、黏度以及在静电喷涂情况下的电压。喷涂系统的选择受投资成本考虑、涂料利用效率、劳动力成本、被涂物尺寸和形状所影响，而这些只是其他许多变量中的一部分。涂料配方必须要按具体的喷涂设备和条件来确立。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 500,
+        "chunk": "# 1.空气喷涂  \n\n目前塑料件的喷涂方法主要是采用空气喷涂，空气喷涂是靠压缩空气流使涂料出口处产生较大的负压，涂料自动流出并在压缩空气气流的冲击混合下被充分雾化，漆雾在气流推动下射向工作表面而沉积的涂漆方法。这种方法是最古老的喷涂方法，但仍在使用，当今的塑胶喷涂还是以空气喷涂为主。  \n\n空气喷涂的特点为： $\\textcircled{1}$ 涂装效率高，每小时可喷涂 $50\\mathrm{\\sim}100\\mathrm{m}^{2}$ ； $\\textcircled{2}$ 涂膜厚度均匀，光滑平整，外观装饰性好； $\\textcircled{3}$ 适应性强，对各种涂料和各种材质的底材，各种形状的塑件都适应。  \n\n空气喷涂的缺点为： $\\textcircled{1}$ 稀释剂用量大； $\\textcircled{2}$ 涂料利用率低，一般不超过 $50\\%$ 中空气喷涂所用的喷枪主要分为吸上式、重力式和压送式三种，在喷涂车间生产线所用的一般为压送式喷枪，其轻巧灵活，出漆量可根据涂料压力进行较大幅度的调整，可供多把喷枪同时作业，可满足各种特殊的生产作业，生产连续性较好。而给塑胶产品涂层补漆或小规模生产则选用其余两种喷枪。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 501,
+        "chunk": "# 2.无空气喷枪  \n\n对于无空气喷枪来说，是将涂料在高压（ $\\mathrm{5\\sim35MPa},$ ）下从喷嘴口压出来，此涂料作为“薄片”形式由喷嘴口出来。当此薄片从喷嘴口离开而展布，流动不动时就产生线丝，接看进一步分裂成液滴，雾化受此薄片与所邻接触的空气之间相对速率（相对速率越高，液滴就越小）、黏度（黏度越高，粒径越大）、压力（压力越高，粒径越小）和表面张力（表面张力越低，粒径就越小）所控制。扇面形状或喷涂图形受喷嘴口尺寸和形状的影响。还可采用空气助喷的无空气喷枪，雾化为无空气但有外部气流帮助扇形图形定形，将较小的液滴限制在喷枪图形之内，手提无空气喷枪和机器人无空气喷枪均有出售。  \n\n由无空气喷枪喷出来的液滴要比有空气喷枪喷出来的液滴大得多，其为 $70\\sim150\\mu\\mathrm{m}$ 而与之相比较有空气喷枪为 $20\\sim50\\mu\\mathrm{m}$ 。无空气喷枪产生所谓的鱼尾喷涂，即对其扇形之内具有相当均一液滴分布的喷雾液滴扇形来说有相当尖锐的边缘。相反，由空气喷枪出来的扇形在其边缘呈羽状，也就是说，其扇形边缘处的液滴数目在减少，而有十分宽阔的空间。由于这些差异的结果，人们采用空气喷枪通常能达到比采用无空气喷枪更加均一的涂膜厚度，空气助喷的无空气施工可得到两者中间的结果。  \n\n用无空气喷枪要比用空气喷枪能更加迅速地涂装涂料，可更快地进行生成。然而，当涂装效率增加时，涂装过高的涂层厚度的可能性也会增加，特别在涂装具有复杂形状的物体时，过高的漆膜厚度不仅是浪费，而且也会导致流挂。由于没有伴随粒子的压缩空气流，又因为液滴粒径一般较大，所以在无空气喷枪中要比空气喷枪中有较少的溶剂从雾化粒子中挥发出来。一般在配置采用无空气喷涂施工的涂料时需要较高相对挥发速率的溶剂。  \n\n在无空气喷枪里没有空气流则减少了对不规则物体喷人闭合凹口的问题。反之，喷到凹口部分其另一端是开口则用空气喷枪容易，因为空气流有助于带走粒子。无空气喷涂设备对一些水性塑料涂料会产生问题，在高压下有更多的空气溶解于水中，当压力被释放出脱离喷枪时，空气就会以气泡的形式出现，气泡被截留在漆膜里会造成针孔现象。  \n\n气溶胶涂料罐是无空气喷涂装置的一个类型。一种液化气体，通常是丙烷，它供给压力迫使涂料从喷嘴孔出来，由于压力相当低，故必然使涂料黏度降低到能达到适当雾化。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 502,
+        "chunk": "# 二、塑料制品表面处理  \n\n塑料表面处理分为一般处理、化学处理和物理处理三种处理方式，前面已经详细叙述了各种表面处理方法，本节着重介绍塑料的一般涂装工艺流程。  \n\n塑料成型加工时，脱膜剂或其他油污会转移到制品表面，成型后的塑料件由于存在内应力，遇到溶剂会产生开裂，由于塑料为不良导体，易静电聚集黏附灰尘，因此塑料件涂漆前应进行退火、脱脂和除尘处理。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 503,
+        "chunk": "# 1.退火处理  \n\n将塑料件加热到稍低于热变形温度保持一段时间，一般控制在比塑料热变形温度低$10^{\\circ}C$ 的温度下进行，消除残余的内应力。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 504,
+        "chunk": "# 2.脱脂处理  \n\n根据油污性质和生产批量大小可分别采取细砂纸打磨（ $\\phantom{-}1200{\\sim}2000$ 目）、溶剂擦拭以及水基清洗剂洗涤等措施。一般性污垢，采用溶剂擦拭，对溶剂敏感的塑料（如ABS、聚苯乙烯）则采用快挥发性的低碳醇和低碳烃（如甲醇、乙醇、己烷等)，对溶剂不敏感的塑料可以用芳烃类溶剂，这样也可以除去塑料底材上大部分的灰尘。塑件大批量脱脂清洗可采用中性或弱碱性水基清洗剂，最好采用中性清洗剂，因碱性清洗剂漂洗不净会残留于表面，影响涂膜附着力和导致其他外观缺陷。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 505,
+        "chunk": "# 3.除尘处理  \n\n在空气喷枪口设置电极高压电晕放电产生离子化压缩空气，能方便有效地消除聚集的静电，灰尘自然也就容易被吹离塑件表面，这类静电除尘装置已经较多用于塑料件涂装线上。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 506,
+        "chunk": "# 三、涂膜干燥类型  \n\n涂膜涂覆于物件表面以后，由液体或疏松粉末状态转化成致密完整的固态薄膜的过程，即为涂料的成膜，也称为涂料的干燥和固化。涂料的成膜是要靠物理和化学作用实现的，通过外界的条件或温度的升高使涂层中的有机溶剂挥发出来形成致密的涂膜为热塑性涂料，是利用物理作用成膜的。而通过涂层中的两种组分或多种组分在温度或其他条件影响下反应交联成聚合物的为热固性涂料，系利用化学作用成膜的。涂料干燥方法分为自然干燥（自干型)、烘干和辐射固化三类，自干型涂装在常温大气环境中靠溶剂挥发或氧化聚合或固化而干燥成膜，但其缺点为干燥时间周期太长，环境中的灰尘及杂质易黏附在涂层表面产生垃圾，且生产效率太低。所以现行塑料涂装流水线多采用加热干燥成膜，主要是对自干型涂料实施强制或对耐热性差的材质表面涂膜进行干燥，干燥温度通常在 $50\\sim80^{\\circ}C$ 可使涂膜固化时间大大缩短，减少对环境中灰尘等杂质的黏附，以满足工业化流水线生产作业需要。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 507,
+        "chunk": "# 四、塑胶漆涂膜的性能测试  \n\n塑胶漆涂膜的性能测试分为涂膜外观、流平性、橘纹、光泽度、鲜艳性、颜色、涂膜硬度、抗冲击性、柔韧性、附着力测试、耐磨性、耐水性、耐醇擦拭、耐化学性、耐湿热性、耐盐雾性、大气老化试验等。塑胶制品表面涂覆漆膜完全干透后着重测试的性能为附着力测试及耐醇擦拭等，涂装企业可根据对漆膜的性能要求不同测试各项性能指标。  \n\n例如：海尔、海信家电外壳的涂装就是采用空气喷涂，其工艺流程如下。  \n\n塑料件退火处理 $\\nrightarrow$ 用乙醇和白电油去除塑料件上的脱模剂 $\\rightarrow$ 静电除尘 $\\nrightarrow$ 挂件 $\\twoheadrightarrow$ 空气喷涂 $-60\\sim70^{\\circ}C$ 烘烤干燥 $\\twoheadrightarrow$ 性能检测（主要检测涂膜外观、附着力、耐醇擦）。  \n\n在涂料和涂膜的检测中，涂膜厚度是一个很重要的控制项目内容。在涂膜施工过程中，由于涂后漆膜厚度不均或厚度未达到规定要求，均对涂层的性能产生重大的影响。所以要严格控制这个关键环节，认真进行厚度检测。  \n\n目前，测定漆膜厚度有各种方法和相应的仪器，根据实际情况和要求选用相应的方法与仪器进行测定。  \n\n(1）湿膜厚度的测定湿膜厚度的测定，必须在漆膜制备后立即进行，以免由于挥发性溶剂和蒸发而使漆膜发生收缩现象。目前常用的湿膜厚度计有轮规、梳规和Pfund湿膜计三种。  \n\n$\\textcircled{1}$ 轮规是由两个相等的圆盘和中间夹装一个偏心圆组成。当三个圆盘的外周在一处相切时，此处间隙为零，相对处间隙最大。圆盘外侧有刻度，以指示不同的间隙值，其结构如图3-6-20所示。测试时，轮规必须垂直被测表面，不能左右晃动，否则所测值有误差。轮规在涂层表面滚动时，最好由间隙最大处开始，湿膜不受推动挤压，所测值比较准确。若从零开始，湿膜受到推挤，所测值产生误差而偏大。  \n\n![](images/dd1e2c18cc3a957c6f39c5e252fb03c570f61a9294d622102c5875f8fdfcd716.jpg)  \n图3-6-20 轮规测厚示意图 1—轮规；2—底板；3—涂层  \n\n![](images/f8d2e9b027c7f5681a0ab83feb8a77be0ecdf29637950f55acaa554e1fb5551e.jpg)  \n图3-6-21 梳规测量原理示意图 1—底板；2—梳规；3—涂层  \n\n$\\textcircled{2}$ 梳规是一种由金属或塑料薄板制成的方形或矩形，四边均有不同规格表示涂层厚度值的简易测厚仪器。其测厚原理如图3-6-21所示。测厚时，将梳规垂直放在被测物表面上，梳规每一边的两端均在同一水平面上，而中间各齿的底边距水平面有依次递升的不同间隙，有具体数字标示。检测时，总有一部分齿被漆膜粘湿，而最后一个被粘湿的齿与未被粘湿的齿之间的读数，就是被测湿漆膜的厚度。  \n\n$\\textcircled{3}$ Pfund湿膜计是由一个凸面透镜L（曲率半径为 $\\mathsf{250m m}$ ）和两个金属圆管所组成。使用时用手缓慢地将管往下压，以使装在底部透镜 $\\mathbb{L}$ 通过湿膜接触底板表面，量取涂料在透镜难黏附部分的直径。按式（3-6-9）计算，即可得出湿膜厚度 $h$ d  \n\n$$\nh{=}\\frac{D^{2}\\times1000}{16r}{=}0,25D^{2}\n$$  \n\n式中 $D$ —黏附部分直径， $\\mathbf{mm}$ 透镜的曲率半径，为 $250\\mathrm{mm}$ $h$ 湿膜厚度， $\\mu\\ m$  \n\n这种测法， $L$ 镜面上由于表面张力的缘故，因而所测得湿膜厚度与实际的湿膜厚度稍有差别，需要引人系数进行修正。  \n\n以上三种膜厚度计从实际应用来看，以轮规较为理想，既能在实验室使用，也能在现场进行测定，使用简便，读数准确。Pfund湿膜厚度计虽然也较为准确，但操作和计算较烦琐。梳规成本低廉，携带方便，但误差较大，只能用于施工现场对湿膜厚度作粗略测定。  \n\n(2）干膜厚度的测定在实际工作中大量遇到的是干膜的测量，测量的方法较多，但都有一定的局限性。塑料涂膜厚度按工作原理来分，主要是以下两种。  \n\n$\\textcircled{1}$ 机械测量法中以往常用杠杆千分尺或千分表测量漆膜厚度。优点是使用时不受底材性质的限制和漆膜中导电或导磁颜料的影响，测量精度较高，可达 $\\pm2\\mu\\mathrm{m}$ 。但只能对较小面  \n\n积的样板进行测量，为消除和减少误差，必须多次测量，手续烦琐，不如磁性法测厚仪简便。  \n\n$\\textcircled{2}$ ISO2808—1974《漆膜厚度的测定法》标准中推荐使用显微镜法，其测试原理如图3-6-22所示。该法是用一定角度的切割工具，将涂层切出 $v$ 形缺口直到底材，然后用带有标尺的显微镜测定 $a^{\\prime}$ 和 $\\boldsymbol{b}^{\\prime}$ 的厚度。标尺的分度已通过校准系数换算成相应的 $a$ 和  \n\n![](images/058f8a9d2bfc2e25efa9440fc8a55cb5624a7506d4397cd60cbc61ba2cfe1596.jpg)  \n图3-6-22 显微镜测厚法示意图1-面漆；2—底漆；3—底材  \n\nb的实际厚度 $(\\mu\\mathrm{m})$ 0  \n\n此法的最大优点是除能测定总漆膜厚度外，还能测出多层漆系统的每层厚度，同时可以在任何底材上进行，其不足之处是使漆膜遭到局部破坏。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 508,
+        "chunk": "# 五、最新塑胶涂装方法",
+        "category": " Introduction"
+    },
+    {
+        "id": 509,
+        "chunk": "# 1.光固化涂料及工艺  \n\n光固化涂料分不饱和聚酯和丙烯酸聚酯、丙烯酸聚氨酯，其优点由于利用 $200{\\sim}450\\mathrm{nm}$ 近紫外光快固化 $(1\\sim2\\mathrm{min})$ ，塑料固化升温较小，不会造成塑料的热变形，且能量利用率高达$95\\%$ ，能耗仅是热固化 $1/10$ ，且涂层非常平整。由于固化时间短，可减少环境中杂质和灰尘沾附在涂层表面。光固化涂料是无溶剂涂料，作业过程中散发的活性稀释剂量很少，大气污染低，固化设备简单，占地少，采取高速流水线生产，效率高，成品堆放场地小。但此工艺不适合复杂形状的塑件，因紫外光线照射不到的部位不能固化，遮盖力大的面漆也不适合，涂层深处固化不完全。但此涂装方法对平整的塑件表面上的高亮度罩光清漆尤为适用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 510,
+        "chunk": "# 2.VIC涂料的氨蒸气快固化工艺  \n\nVIC涂料是将普通的双组分聚氨酯涂料，另用叔胺组分作为催化剂构成。施工时采用三孔专业喷枪，使叔胺在喷枪口汽化并与涂料雾粒充分混合，在喷到工件表面后的片刻时间内，涂膜即固化。低温需稍做闪干后处理，便能除去剩余溶剂，总固化时间很短，仅为几分钟，固化效率可与光固化相比，但它可用遮盖率强的高颜料分色漆，且在三维空间的任意部位都能均匀固化完全，涂层性能与光固化涂膜同样优良，特别适合于高速流水线生产，或消除环境灰尘对涂膜外观的损害。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 511,
+        "chunk": "# 3.IMC涂料和膜内注射涂装技术  \n\n在 SMC膜压成型以后，将模具稍微抬起，高压注人IMC（膜内注射涂料)，高压紧闭模具，使IMC充分扩展开，然后于 $140{\\sim}150^{\\circ}C$ 硬化后脱模，塑件外表面非常平整光滑。  \n\n此类IMC主要是不饱和聚酯型涂料，采用过氧化物引发剂，配成使用期为 $5\\sim15$ 天的单包装涂料，使注射机相对比较简单，设备费较低，维护费也较少，比常规的喷涂-热固化设备费和运行费低得多。它以较低代价可得到高质量的装饰性产品，且模压件可立即包装或送去组装。  \n\n由于IMC也是无溶剂涂料，作业过程中无活性稀释剂散发，因而无环境污染，同时涂料利用率很高，免除繁重的涂装作业，该技术极其先进。  \n\n此技术早期（20世纪70年代）用于SMC的填孔，后用来涂底漆，现在已用作SMC涂覆高装饰性面漆。除用于SMC涂漆外，也可在BMC、LPM、RIM、GMT和注塑件等方面进行应用。但对于热塑性材料，单包装的IMC的 $140\\sim150^{\\circ}C$ 固化温度对注射模具来说太高，因此它只能采用双组分聚氨酯的IMC，它在 $80^{\\circ}C$ 就能硬化涂层，硬化温度与模具温度相适应。但双组分IMC 的模内注人设备较复杂，价格昂贵，并带来一系列其他问题，因此注塑件的IMC涂装技术还没有得到应用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 512,
+        "chunk": "# 4.模内粉末涂料及涂装  \n\n粉末涂料的固化温度很高，若直接涂于塑件表面再固化，塑件将严重变形甚至降解。  \n\n该涂装技术是先将粉末涂料涂于金属模具上，然后按常规方法塑料成型，再在较高温度和压力下，使粉末涂料部分固化、脱模后，将塑件稍微加热便使涂层固化完全。  \n\n随着塑料涂料品种的不断增多，塑料涂装技术也朝着更先进、更环保、更经济的方向发展。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 513,
+        "chunk": "# 六、塑胶漆膜缺陷及分析  \n\n在塑胶涂料施工过程中或施工成膜后会因各方面原因产生许多种缺陷，本节涉及最主要的几种缺陷，并尽可能地讨论其产生原因及消除或尽量减少其发生的方法。塑胶涂料的许多缺陷是与表面张力现象相关的，表面张力产生的原因是：液体表面分子分布不对称，界面上液体的力与液体内的力不同，表面的分子具有更高的自由能，相当于每单位面积上移去表面层分子所需的能量。表面张力作用使液体缩成球，因为球的表面积/体积比率是最小的。如果两个不同表面张力液体相互接触，低表面张力的液体会覆盖住较高表面张力的液体，因为这样总表面自由能更低。这种流动是表面张力差推动的流动，有些人称为表面张力梯度推动的流动。涂料能均匀稳定地涂覆于塑胶件表面的最主要条件为涂料的表面张力必须小于被涂覆物的表面张力。  \n\n下面将常见的涂装缺陷、产生原因和解决措施汇总于表3-6-40。  \n\n表3-6-40 涂膜常见问题及其解决方法  \n\n\n<html><body><table><tr><td>缺陷类型</td><td>产生原因</td><td>解决措施</td></tr><tr><td>缩孔现象</td><td>低表面张力的小颗粒或小液滴杂物溶解在湿膜中产生 一个局部的表面张力差，流体由低表面张力处流向高表 面张力处，结果在流体表面形成凹陷，也称为Marangoni|增加流平 效应，最终出现边缘隆起、中心下陷成圆形的缩孔</td><td>使用助剂降低涂料表面张力以减少缩孔</td></tr><tr><td>橘纹现象</td><td>塑料工件温度太高，喷涂室内空气流速太快，溶剂挥发 太快，喷涂时出漆量太小或喷涂距离不适，喷枪雾化不 良，漆雾颗粒过大，涂料黏度过大，底材粗糙等</td><td>严格控制各工艺参数；调整涂料黏度；对 底材进行适当处理 尽可能地提高罩光清漆的厚度并延长闪 干流平时间</td></tr><tr><td>咬底现象</td><td>底材塑件在注塑时压力不足导致塑件局部密度不一 致，存在一定的内应力，而涂料中有机溶剂的极性和溶解 力较强时，涂料中的强溶剂会咬进塑件内，出现咬底现象</td><td>在不影响涂料溶解性的情况下尽量减弱 稀释剂的极性和溶解力；在涂膜咬底的部 位用细砂纸打磨一遍后再喷上一道涂料； 在涂装过程中先将底材易咬底的部位薄薄 喷涂，最后将此处和另外部位一同涂覆成 均匀涂膜</td></tr><tr><td>颗粒现象</td><td>涂料细度不够；压缩空气未过滤或过滤不当；涂料变 质，如漆基析出或反粗，颜料分解不佳或产生凝聚，有机 颜料析出，闪光色漆中铝粉分散不良等</td><td>严把涂料质量关，使用前必须过滤；对于 少数微细颗粒，来用1500自以上水砂纸打 磨修饰，颗粒过大时或面积大时用800目 水砂纸打磨重新喷涂</td></tr><tr><td>底漆与清漆层间 附着力问题</td><td>第一道底漆的表面张力低于第二道罩光清漆</td><td>塑胶底漆在生产过程中的表面张力不应 太低，能与底材咬合最佳为止，并使面漆对 底漆的润湿性良好，两层涂膜要有一定厚 度的界面层</td></tr><tr><td>针孔现象</td><td>清漆精制不良，内部存在杂质；涂料挥发过快，且用量较 多；涂料表面张力过大，黏度高，流动性差，气泡释放困难；溶剂如CAC、环已酮等可减少针孔现象； 被涂覆塑料件未冷却，闪干时间过短，使湿膜中溶剂急剧|加人适量流平剂以降低涂料表面张力减少 蒸出；涂膜喷涂太厚且表干过快；作业环境温度太高或喷针孔现象；延长闪干时间；成膜后自然静置 涂时有水分带人涂料中；闪干不充分，烘烤升温过快：涂料 长时间搅拌，形成无数细微空气泡；颜料分散不良</td><td>严格控制涂料质量；加人挥发性慢的强 一段时间再进人带有温度梯度的烘道进行 烘烤；控制搅拌时间；加人合适的分散剂</td></tr><tr><td>气泡和气孔问题</td><td>气孔是涂膜干燥过程中滞留于涂膜的气泡强行突破涂 膜逸出时留下的泡孔。未破而使涂层隆起的称为气泡。 气泡可以是涂料揽拌时形成的空气泡，或者是干燥时溶|中加入合适的助剂使气泡破裂 剂急剧挥发形成的溶剂气泡</td><td>严格控制搅拌强度：在涂料的制作过程</td></tr></table></body></html>  \n\n续表  \n\n<html><body><table><tr><td>缺陷类型</td><td>产生原因</td><td>解决措施</td></tr><tr><td>发花现象</td><td>在涂膜干燥过程中，由于表面张力差驱动的对流所造|填料的粒径要匹配；通过仔细选择润湿、分 成的颜料分离效应。颜料和填料粒径差、体系中各物质 散剂以缩小颜料、填料与涂料体系之间的 的表面张力差以及各物质的亲水亲油平衡值（HLB)</td><td>仔细选择颜料、填料，使所选用的颜料、 表面张力差并使各物质的亲水亲油平衡值 从分匹配</td></tr><tr><td>浮色现象</td><td>颜料的密度和大小不同 颜料絮凝 湿膜厚、基料黏度低和溶剂挥发速率慢</td><td>避免絮凝；采用低密度细颜料；用挥发更 快的溶剂和黏度更高的基料</td></tr><tr><td>露底现象</td><td>涂料遮盖力差；涂料兑得太稀或喷涂的湿膜太薄、喷涂 膜厚不均匀</td><td>涂料使用前，将沉降的颜料充分搅起；严 格控制正常喷涂手法进行喷涂；中涂颜色 最好与面漆相近</td></tr><tr><td>发白现象</td><td>施工车间的湿度过高；溶剂挥发速率过快；喷枪的压缩 空气含有水、油等</td><td>安装湿度调节器以控制环境湿度；加人适 量高沸点、慢挥发强溶剂以调整溶剂配方；除 去压缩空气中的水分，定期排放空气压缩机 和油水分离机的油水。将塑料工件加热到 高于环境温度10℃也可以减弱发白现象</td></tr><tr><td>铝粉漆色调不 均匀</td><td>金属闪光涂料中铝粉含量太低，遮盖力较差，涂料的定 膜能力差；涂膜的表干时间太长；底色漆喷的薄厚不均匀 或者漏喷、现露底色；“湿碰湿”工艺的间隔时间太短；喷 涂时空气压力太低，涂料雾化不良或空气压力太高，使片 状铝粉变形</td><td>在铝粉涂料中加入铝粉定位剂或醋酸纤 维素酯；调整相应的工艺时间；闪光铝粉漆 应该采用较低施工固体分和施工黏度喷 涂，使用专用喷枪均匀喷薄，以约8um干 膜厚度喷涂二道，并经充分闪干后再喷涂 清漆</td></tr><tr><td>落现象）</td><td>底材沾有脱模剂、油污、水或太光滑等；底涂层放置太 附着力问题（剥久，重涂间隔周期太长或涂层烘烤过度；底、面涂料不配 套；底漆涂层含有硅油类助剂、表面张力过低；塑料表面选择适宜的底、面涂料和预涂底漆 的预涂底漆品种选用不当</td><td>对底材或旧涂膜进行适宜的表面处理；</td></tr><tr><td>慢干和返黏现象</td><td>涂料中溶剂挥发性差；底漆未干透就涂面漆；施工湿度 「太大，气温太低；涂料中混人其他杂质或催干剂添加量不 够；固化剂配比错误</td><td>严格控制施工工艺和施工环境；加人适 宜的催干剂</td></tr><tr><td>涂膜光泽低</td><td>涂料中树脂之间、树脂与助剂之间混容性差，涂膜雾浊 而失光。颜料分散不良，涂料细度差或色漆的颜料体积 浓度较高，树脂含量低。溶剂的溶解性差。底材粗糙多 孔，对涂料吸收量大。采取打底漆进行封闭处理。底涂|漆工艺参数或选用较细的水砂纸湿打磨； 层粗糙不平整，或打磨用的砂纸太粗。烘房内空气污浊， 或烘烤温度过高而失光。面漆或罩光清漆喷涂的太薄。整体装饰性都有极大的好处 面漆或罩光清漆未干就抛光修饰</td><td>加人适宜的润湿分散剂；采用溶解性好 的溶剂；采取打底漆进行封闭处理；调整涂 增加面漆的厚度，对提高光泽度、平整度和</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 514,
+        "chunk": "# 参考文献  \n\n[1] 欧阳国恩，实用塑料材料学，长沙：国防科技大学出版社，1991：8-9.  \n[2] 常州轻工业学校，安徽轻工业学校合编，塑料材料学，北京：中国轻工业出版社，2001：2-4.  \n[3] 刘登良编著，塑料橡胶涂料与涂装技术，北京：化学工业出版社，2001：38-40；110-111；189-192.  \n[4] 梁增田编著，塑料用涂料与涂装．北京：科学技术文献出版社，2006：371-374；379-386.  \n[5] 蔡柏龄编著．家电涂料与涂装技术．北京：化学工业出版社，2002：177；401-403.  \n[6]孙立水．李少香，塑料涂装技术及涂膜缺陷与对策，中国涂料，2006，21（5)：47-49.",
+        "category": " References"
+    },
+    {
+        "id": 515,
+        "chunk": "# 木用涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 516,
+        "chunk": "# 第一节 木用涂料沿革  \n\n中国的木用涂料，新中国成立前规模较小，新中国成立后得到发展。至20世纪80年代末，产品的研发及生产已具相当水平。品种齐全，应用广泛，但总量不大。  \n\n20世纪90年代初，改革开放后的房地产业、家具业的飞速发展，构筑了木用涂料庞大的终端市场。民营企业、外资企业迅速进人这个新领域，短短几年，使木用涂料的方方面面有了巨变。  \n\n在这个发展过程中，木用涂料在专业化、系列化、规范化、标准化几方面成绩斐然。  \n\n中国木用涂料在产量及品质方面基本上可跟上国内家具业发展的速度，到2007年中国成为世界第一大家具出口国的时候，木用涂料当年就为家具业提供了近70万吨的产品。（同期统计：全球木用涂料约250万吨，欧洲70万吨，美国20万吨)。按功能分类，木用涂料与建筑涂料、汽车涂料、重防腐涂料一样，成为国内增长最快的品种之一，市场份额占了中国涂料总销量 $10\\%$ 以上，是中国涂料产品中一个重要的专业门类。  \n\n木用涂料现在产品结构合理，系列分类齐全；在产品品种、原料应用、配方设计、系列配套、生产工艺、功能等方面，与国外产品同比差别不大。",
+        "category": " Introduction"
+    },
+    {
+        "id": 517,
+        "chunk": "# 第二节木材与木质材料的特性及涂装前的基本要求  \n\n木器和木家具是由各种材料通过一定的结构技术制作而成的。制作木器和木家具的木材和木质材料按其用途，一般可分为结构材料、装饰材料和辅助材料等三大类。木材是制作木器和木家具的一种传统材料，至今仍占重要地位。随着我国木材综合利用率的提高，木质材料得到迅速的发展，也广泛地应用于木器和木家具的制作中。",
+        "category": " Introduction"
+    },
+    {
+        "id": 518,
+        "chunk": "# 一、木材的特性",
+        "category": " Introduction"
+    },
+    {
+        "id": 519,
+        "chunk": "# 1．木材的种类  \n\n木材是自然界分布较广的材料之一，也是制作木器和家具的主要原材料。木材种类很多，一般可分为两大类，即针叶材和阔叶材。  \n\n(1）针叶材（又称软材）树干通直而高大，纹理平直，材质均匀，木质轻软，易于加工，强度较高，表观密度及胀缩变形小，耐腐蚀性强。因木材不具导管（即横切面不具管孔)，故又称为无孔材。常见的针叶材有红松、落叶松、白松、云杉、冷杉、铁杉、柳杉、红豆杉、杉木、柏木、马尾松、华山松、云南松、花旗松、智利松、辐射松等。  \n\n(2）阔叶材（又称硬材）树干通直部分一般较短，材质较硬，难加工，较重，强度大，胀缩翘曲变形大，易开裂，常用作尺寸较小的构件，有些树种具有美丽的纹理与色泽，适于作家具、室内装修及胶合板等。由于阔叶材种类繁多，习惯上亦统称为杂木。因木材具有导管（即横切面具有管孔)，故又称为有孔材。常用的阔叶材树种有水曲柳、白蜡木、木、榆木、杨木、木（色木)、枫香（枫木)、枫杨、桦木（白桦、西南桦)、酸枣、漆树、黄连木、冬青、木（冬瓜木)、栗木、木、锥木（拷木)、泡桐、鹅掌楸、楸木、黄杨木、榉木、山毛榉（水青冈、麻栎青冈)、青冈栎、木（蒙古栎)、麻栎、橡木（栎木）、橡胶木、樱桃木、胡桃木（核桃木、山核桃)、樟木（香樟)、楠木、擦木、柳桉、红柳桉、柚木、桃花心木、阿比东、龙脑香、门格里斯（康巴斯)、塞比利（沙比利)、紫檀、黄檀、酸枝木、香木、花梨木、黑檀（乌木)、鸡翅木、铁力木等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 520,
+        "chunk": "# 2.木材的三个切面  \n\n木材是由大小、形状和排列各异的细胞组成。木材的细胞所形成的各种构造特征，可通过木材的三个切面来观察。树干的三个标准切面为横切面、径切面和弦切面。如图3-7-1所示为木材的三个切面。  \n\n![](images/0cdba7272aed0a3429949d489955b0821eca6e803c56464be918a8a4a530e040.jpg)  \n图3-7-1 木材的三个切面  \n\n(1）横切面横切面是与树干轴向或木材纹理方向垂直锯切的切面。在这个切面上，年轮呈同心圆状，木材纵向细胞或组织的横断面形态和分布规律以及横向组织木射线的宽度、长度方向等特征，都能清楚地反映出来。横切面较全面地反映了细胞间的相互联系，是识别木材最重要的切面，也称基准面。  \n\n(2）径切面径切面是与树干轴向相平行，沿树干半径方向（即通过髓心）所锯切的切面。在该切面上，年轮呈平行条状，并能显露纵向细胞的长度方向和横向组织的长度及高度方向。  \n\n(3）弦切面弦切面是与树干轴向相平行，不通过髓心所锯切的切面。在该切面上，年轮呈“V”字形花纹，并能显露纵向细胞的长度方向及横向细胞或组织的高度和宽度  \n\n方向。  \n\n在木制品和家具生产加工中，通常所说的径切板和弦切板，与上述的径切面和弦切面有一定的区别。如图3-7-2所示，在木材生产和流通中，借助横切面，将板厚中心线与生长轮  \n\n切线之间的夹角在 $60^{\\circ}\\sim90^{\\circ}$ 的板材称为径切板：将板厚中心线与生长轮切线之间的夹角在 $0^{\\circ}\\sim30^{\\circ}$ 的板材称为弦切板；介于 $30^{\\circ}\\sim60^{\\circ}$ 的板材称为普通用材。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 521,
+        "chunk": "# 3.木材的物理特性  \n\n（1）木材中的水分 日常生活中，木质门窗水湿后会关闭不上、盆桶失水后会产生缝隙、实木地板太干时产生的缝隙及其太湿时产生的局部隆起、  \n\n![](images/1a0d8aa5dc5967f30c3c1a2d8f1badbaee3717e6c4c4b8006f211f4db704181f.jpg)  \n图3-7-2 径切板和弦切板  \n\n实木家具在使用过程中因失水而至结合部件松动脱落、木材使用过程中出现的虫蛙和腐朽等问题，都与木材中的水分含量不合理有关系。水分对木材本身性质、木材贮运保存、木材使用性能及以木质材料为基材的人造板性能和加工工艺等均有很大的影响，因此充分理解木材中水分对木材的加工、涂装及利用的影响有着重要意义。  \n\n$\\textcircled{1}$ 水分存在的状态木材中的水分按其存在的状态可分为自由水（毛细管水）、吸着水和化合水三类。以游离态存在于木材细胞的胞腔、细胞间隙和纹孔腔这类大毛细管中的水叫自由水，它包括液态水和腔内水蒸气两部分；以吸附状态存在于细胞壁中微毛细管的水称吸着水；与木材细胞壁组成物质呈化学结合的水称化合水。  \n\n$\\textcircled{2}$ 木材含水率木材干与湿主要取决于其水分含量的多少，通常用含水率来表示。木材中水分的重量和木材自身重量之比称为木材的含水率。木材含水率分为绝对含水率和相对含水率两种。以全干木材的重量为基准计算含水率称为绝对含水率，以湿木材的重量为基准计算的含水率称为相对含水率。  \n\n木材是一种多孔性的材料，含水率的高低，不仅影响着木器和家具使用过程中的翘曲和开裂的形变，而且对涂装作业的影响也很大，特别是在涂饰单组分硝基涂料（NC）或双组分聚氨酯涂料（PU）时，由于木材含水率高而在涂饰过程中产生大量气泡是很常见的涂膜缺陷，因此含水率是一个重要的质量控制项目。  \n\n$\\textcircled{3}$ 木材纤维饱和点木材纤维饱和点是指木材胞壁含水率处于饱和状态而胞腔无自由水时的含水率。它具有非常重要的理论意义和实用价值。纤维饱和点的含水率因树种、温度以及测定方法的不同而存在差异，其变异范围为 $23\\%\\sim33\\%$ ，但多种木材的纤维饱和点的含水率平均为 $30\\%$ 。因此通常以 $30\\%$ 作为各个树种纤维饱和点含水率的平均值。  \n\n纤维饱和点是木材多种材性的转折点，就大多数木材力学性质而言，如含水率在纤维饱和点以上，其强度不因含水率的变化而有所增减。当木材干燥含水率减低至纤维饱和点以下时，其强度随含水率的减低而增加，两者成一定的反比例关系，只是韧性和抗劈力不显著。  \n\n木材的含水率在纤维饱和点以上时，无论含水率增加或减少，除重量有所不同外，木材完全无收缩或膨胀，外形均保持最大尺寸，体积不变。当木材含水率减低至纤维饱和点以下时，随着含水率的增减，木材发生膨胀或收缩。含水率减少愈多，收缩率愈大，两者呈一定直线关系。至绝干时，收缩至最小尺寸。  \n\n$\\textcircled{4}$ 木材的吸湿性木材吸湿性是指木材随周围气候状态（温度、相对湿度或水蒸气相对压力）的变化，由空气中吸收水分或向空气中蒸发水分的性质。当空气中的水蒸气压刀大于木材表面水蒸气压力时，木材能从空气中吸收水分，把这种现象叫做吸湿；反之木材中水分向空气中蒸发叫做解吸。如图3-7-3所示为吸湿与解吸曲线。  \n\n![](images/18ce607db618ab4c7a4c66f0ef2c738feea19300f0701750f9331c07eaf4c66b.jpg)  \n图3-7-3 吸湿与解吸曲线  \n\n$\\textcircled{5}$ 平衡含水率木材长期暴露在一定温度和相对湿度的空气中，最终会达到相对恒定的含水率，即吸湿（木材从空气中吸收水分）与解吸（木材中水分向空气中蒸发）的速度相等，此时木材所具有的含水率称平衡含水率。平衡含水率随不同地区、不同季节的大气温度和湿度的不同而异。我国北方地区年平均平衡含水率约为 $12\\%$ ，南方约为 $18\\%$ ，长江流域约为 $15\\%$ 。国际上以 $12\\%$ 为标准平衡含水率，研究表明：相对湿度每升高 $1\\%$ ，木材的吸湿率便增加 $0.121\\%$ ，而温度每降低 $1^{\\circ}C$ 时，木材的吸湿率仅增加 $0.071\\%$ 。木材平衡含水率与空气湿度和空气温度关系如图3-7-4所示，由此即可查出一定温度、湿度条件下的平衡含水率。  \n\n（2）木材的干缩与湿胀 湿材因干燥而缩减其尺寸与体积的现象称之为干缩；干材因吸收水分而增加其尺寸与体积的现象称之为湿胀。干缩和湿胀现象主要在木材含水率小于纤维饱和点的情况下发生，当木材含水率在纤维饱和点以上，其尺寸、体积是不会发生变化的。  \n\n木材的干缩湿胀在不同的方向上是不一样的，如图3-7-5所示。木材纵向的干缩率仅为$0.1\\%\\sim0.3\\%$ ；径向为 $3\\%\\sim6\\%$ ；弦向为 $6\\%\\sim$ $12\\%$ 。可见，横向干缩较纵向要大几十倍至上百倍，横向干缩中弦向约为径向的两倍。三个方向干缩大小顺序为弦向、径向和纵向。  \n\n木材的干缩湿胀随树种、密度以及晚材率的不同而异。针叶材的干缩较阔叶材要小；软阔叶材的干缩较硬阔叶材要小；密度大的树种干缩值越大；晚材率越大的木材干缩值也越大。  \n\n干缩和湿胀是木材的固有性质，干缩和湿胀会使木制品的外形尺寸变化。干燥后的木材尺寸会随着周围环境湿度、温度的变化而变化，生产和生活中常会见到木制品发生翘曲、变形、开裂等现象，如地板、木门窗湿胀后，不仅会出现地板隆起、门窗关不上等现状，而且还会降低其力学性能。  \n\n![](images/ad9311b51ab4f61d446c843f982ea896957116b0a550d75b3a9760be81e4c144.jpg)  \n图3-7-4 温度、相对湿度和平衡含水率的关系",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 522,
+        "chunk": "# 4.木材的化学特性  \n\n(1）木材的化学成分木材由天然形成的有机物构成，属于高分子化合物。木材细胞的组成成分可分为主要成分和次要成分两种，主要组成成分是纤维素、半纤维素和木素；次要成分有树脂、单宁、香精油、色素、生物碱、果胶、蛋白质等。在木材的组织结构中，纤维素的含量约为 $50\\%$ ，半纤维素的含量为 $20\\%\\sim30\\%$  \n\n（2）木材的抽提物木材中的抽提物是指用水、酒精、乙醚、苯、丙酮等有机溶剂浸提出来的物质，这里的抽提物是广义的，指除组成木材细胞壁结构物质以外的所有木材内含物。抽提物的含量随树种、树龄、树于位置以及树木生长的立地条件不同而不同，含量少者约为 $1\\%$ ，多者高达 $10\\%\\sim40\\%$ ，一般在$5\\%$ 左右。许多木材抽提物是在边材转化心材过程中形成的，它们不是木材细胞壁的组成部分，但存在于细胞腔和细胞壁的微毛细管或者木材的特殊细胞中。  \n\n![](images/6b1d4b77eabe6c0814bea22ca130c866a516ca62937086505088aca4671a08d4.jpg)  \n图3-7-5 木材各个方向干缩的差异  \n\n当用化学药品处理木材的时候，木材中的抽提物对化学物品的反应是不同的。例如，当用不饱和聚酯涂饰花梨木材质的表面时，由于花梨木中含有酚类抽提物，这种酚类抽出物可阻止不饱和聚酯涂料组成中的活性单体苯乙烯的聚合，使不饱和聚酯涂料的干燥性变差。另外，在松木中含有松节油等抽提物，同样也会影响涂饰在其表面上的油性清漆的干燥性。  \n\n木材中的抽提物除延缓干燥时间外，还可能因为涂料中通常使用酮类、酯类、醇类等强溶剂而溶解木材中的某些色素，使涂膜原有的颜色改变，有时还可影响涂膜层的光泽。因此，在对木材表面进行涂装作业以前，常常需要对木材表面进行必要的漆前处理。  \n\n(3）木材的pH木材酸碱性质是其重要化学性质之一，它与木材的胶合性能、变色、着色、涂饰性能以及对金属的腐蚀性等加工工艺密切相关。研究表明，绝大多数木材呈弱酸性，这是由于木材中含有醋酸、蚁酸、树脂酸以及其他酸性抽提物，木材在贮存过程中，也不断产生酸性物质。有人根据木材的酸碱性质将 $\\mathfrak{p H}$ 小于6.5的木材称为酸性木材，而把pH大于6.5的木材称为碱性木材，极少数木材或者心材属于碱性木材。木材的$\\mathsf{p H}$ 随树种、树干部位、生长地域、采伐季节、贮存时间、木材含水率以及测试条件和测试方法等因素的变化而有差异。例如，同一株树木不同部位的 $\\mathbf{pH}$ 有变化，边材与芯材的$\\mathbf{pH}$ 相差明显。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 523,
+        "chunk": "# 二、木质材料的特性  \n\n木器和家具常用的木质材料主要包括木质人造板和木质贴面材料。天然木材由于生长条件和加工过程等方面的原因，不可避免地存在着各种缺陷，同时，木材加工也会产生大量的边角余料，为了克服天然木材的缺点，充分合理地利用木材，提高木材利用率和产品质量，木质人造板得到了迅速发展和应用。另外，木质人造板应用在木器和家具制作过程中，需要用各种木质贴面和封边材料作表面装饰及边部封闭处理，也进一步促进了木质贴面材料的发展和应用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 524,
+        "chunk": "# 1.木质人造板  \n\n木质人造板是将原木或加工剩余物经各种加工方法制成的木质材料。其种类很多，目前在家具生产中常用的有胶合板、刨花板、纤维板、细木工板、空心板、多层板以及层积材和集成材等。人造板具有幅面大、质地均匀、表面平整、易于加工、利用率高、变形小和强度大等优点。  \n\n（1）胶合板胶合板是原木经旋切或刨切成单板，涂胶后按相邻层木纹方向互相垂直组坏胶合而成的多层（奇数）板材。其主要特性如下。  \n\n$\\textcircled{1}$ 幅面大、厚度小、容重轻、木纹美丽、表面平整、不易翘曲变形、强度高等优良 特性。  \n\n$\\textcircled{2}$ 胶合板的最大经济效益之一是可以合理地使用木材，它用原木旋切或创切成单板生产胶合板代替原木直接锯解成的板材使用，可以提高木材利用率。每 $2.2\\mathrm{m}^{3}$ 原木可生产 $\\mathrm{1m^{3}}$ 胶合板；生产 $1\\mathrm{m}^{3}$ 胶合板，可代替相等使用面积的 $4.3\\mathrm{m^{3}}$ 左右原木锯解的板材使用。  \n\n$\\textcircled{3}$ 胶合板在使用性能上要比天然木材优越，它的结构（结构三原则：对称原则、奇数层原则、层厚原则）决定了它的各向物理力学性能比较均匀，克服了天然木材各向异性等缺陷。  \n\n$\\textcircled{4}$ 胶合板可与木材配合使用，适用于木器和家具上大幅面的部件，不管是出面还是作衬里，都比较合适。  \n\n$\\textcircled{5}$ 由于胶合板是把原木切成薄片并经纵横交叉胶合而成，所以表面木毛较多，涂装之前须经过打磨处理。  \n\n$\\textcircled{6}$ 生产胶合板时，胶黏剂常会沾污胶合板板面，从而影响涂装作业时的着色和涂膜的附着力，涂装前必须将沾污的胶黏剂打磨去除。  \n\n$\\textcircled{7}$ 胶合板在生产过程中，由于上胶不匀，会出现脱胶、表面凹凸不平或起壳现象，有碍于木器和家具的生产质量及涂装时的表面平整，因此选材时必须仔细检查。  \n\n另外，胶合板分类的方法很多，其中按照胶合板使用的胶黏剂耐水和耐用性能、产品的使用场所，可分为室内型胶合板和室外型胶合板两大类，或如下四类。  \n\na.I类胶合板耐气候、耐沸水胶合板，具有耐久、耐气候、耐沸水和抗菌性能。常用酚醛树脂胶或三聚氰胺树脂胶或性能相当的胶生产，主要适合用于室外场所的木器和家具。  \n\nb.Ⅱ类胶合板耐水胶合板，具有耐水、短时间耐热水和抗菌性能，但不耐煮沸。常用脲醛树脂胶或性能相当的胶生产，主要适合用于室内场所的木器和家具。  \n\nc.Ⅲ类胶合板耐潮胶合板，只具有耐受大气中潮气和短时间耐冷水性能。常用低树脂含量的脲醛树脂胶、血胶或性能相当的胶生产，主要适合用于一般性能要求的木器和家具。  \n\nd.IV类胶合板不耐水胶合板，不具有耐水、耐潮性能。一般用豆胶等生产，只适用于室内场所或一般用途。  \n\n(2）刨花板刨花板是利用小径木、木材加工剩余物（板皮、截头、刨花、碎木片、锯屑等)、采伐剩余物和其他植物性材料加工成一定规格和形态的碎料或刨花，并施加胶黏剂后，经铺装和热压制成的板材，又称碎料板，其主要特性如下。  \n\n$\\textcircled{1}$ 幅面尺寸大、表面平整、结构均匀、长宽同性、无生长缺陷、不需干燥、隔音隔热性好、有一定强度、利用率高等。  \n\n$\\textcircled{2}$ 刨花板是利用小径木和碎料，可以综合利用木材、节约木材资源、提高木材利用率。每 $1.3{\\sim}1.8\\mathrm{m}^{3}$ 废料可生产 $\\bf{1m^{3}}$ 刨花板；生产 $\\mathrm{1m^{3}}$ 刨花板，可代替 $3\\mathrm{m}^{3}$ 左右原木锯解的板材使用。  \n\n③容重大、平面抗拉强度低、厚度膨胀率大、边部易脱落、不宜开棒、握钉力低、切削加工性能差、游离甲醛释放量大、表面无木纹等。  \n\n$\\textcircled{4}$ 须经二次加工装饰（表面贴面或涂饰）后广泛用于板式家具生产和建筑室内装修。  \n\n另外，刨花板分类的方法也很多，其中按照结构来分可分为单层结构刨花板、三层结构刨花板、渐变结构刨花板。单层结构刨花板的拌胶刨花不分大小粗细地铺装压制而成，饰面较困难；三层结构刨花板的外层是细刨花，胶量大，芯层是粗刨花，胶量小，家具生产中常用；渐变结构刨花板的刨花由表层向芯层逐渐加大，无明显界限，强度较高，常用于家具及室内装修。  \n\n(3）纤维板纤维板是以木材或其他植物纤维为原料，经过削片、制浆、成型、干燥和热压而制成的板材，常称为密度板。其分类方法也较多，按密度可分为：软质纤维板（密度小于 $0.4\\mathrm{g/cm^{3}}.$ )、中密度纤维板（密度 $0.4{\\sim}0.8\\mathrm{g/cm^{3}})$ 、高密度纤维板（密度一般为 $0.8\\sim$ $0.9\\mathrm{g/cm^{3}}.$ )，其主要特性如下。  \n\n$\\textcircled{1}$ 软质纤维板密度不大、物理力学性能不及硬纤板，主要在建筑工程中用于绝缘、保温和吸音、隔音等方面。  \n\n$\\textcircled{2}$ 中密度纤维板和高密度纤维板幅面大、结构均匀、强度高、尺寸稳定变形小、易于切削加工（锯截、开棒、开槽、砂光、雕刻和铣型等）、板边坚固、表面平整、便于直接胶贴各种饰面材料、涂饰涂料和印刷处理，是中高档木器、家具制作及室内装修的良好材料。  \n\n(4）细木工板细木工板俗称木工板，它是将厚度相同的木条，同向平行排列拼合成芯板，并在其两面按对称性、奇数层以及相邻层纹理互相垂直的原则各胶贴一层或两层单板而制成的实心覆面板材，所以细木工板是具有实木板芯的胶合板，也称实心板，其主要特性如下。  \n\n$\\textcircled{1}$ 细木工板的结构稳定，不易变形，加工性能好，强度和握钉力高，是木材本色保持最好的优质板材，广泛用于家具生产和室内装饰，尤其适于制作台面板和座面板部件以及结构承重构件。  \n\n$\\textcircled{2}$ 与实木板比较：细木工板幅面尺寸大、结构尺寸稳定、不易开裂变形；利用边材小料、节约优质木材；板面纹理美观、不带天然缺陷；横向强度高、板材刚度大；板材幅面宽大、表面平整一致。  \n\n$\\textcircled{3}$ 与“三板”比较：与胶合板相比，原料要求较低；与刨花板、纤维板相比，质量好、易加工；与胶合板、刨花板相比，用胶量少、设备简单、投资少、工艺简单、能耗低。  \n\n另外，细木工板的分类方法也较多，其中按照耐水性可分为以下两类。  \n\na.I类胶细木工板具有耐久、耐气候、耐沸水和抗菌性能，常用酚醛树脂胶或三聚氰胺树脂胶或性能相当的胶生产，主要用于室外场所。  \n\n，b.Ⅱ类胶细木工板具有耐水、短时间耐热水和抗菌性能，但不耐煮沸，常用脲醛树脂胶或性能相当的胶生产，主要用于室内场所及家具。  \n\n（5）空心板空心板是由轻质芯层材料（空心芯板）和覆面材料所组成的空心复合结构板材。家具生产用空心板的芯层材料多由周边木框和空芯填料组成。在家具生产中，通常把在木框和轻质芯层材料的一面或两面使用胶合板、硬质纤维板或装饰板等覆面材料胶贴制成的空心板称为包镶板。其中，一面覆面的为单包镶；两面覆面的为双包镶，其主要特性如下。  \n\n$\\textcircled{1}$ 芯层材料或空心芯板多由周边木框和空芯填料组成，其主要作用是使板材具有一定的充填厚度和支承强度。周边木框的材料主要有实木板、刨花板、中密度纤维板、多层板、层积材、集成材等。空芯填料主要有单板条、纤维板条、胶合板条、牛皮纸等制成的方格形、网格形、波纹形、瓦楞形、蜂窝形、圆盘形等。  \n\n$\\textcircled{2}$ 在空心板中，覆面材料起两种作用，一种是起结构加固作用，另一种是起表面装饰作用。它是将芯层材料纵横向联系起来并固定，使板材有足够的强度和刚度，保证板面平整丰实美观，具有装饰效果。  \n\n$\\textcircled{3}$ 空心板具有重量轻、变形小、尺寸稳定、板面平整、材色美观、有一定强度，是家具生产和室内装修的良好轻质板状材料。  \n\n(6）单板层积材单板层积材（简称LVL）是把旋切单板多层顺纤维方向平行地层积胶合而成的一种高性能产品。其主要特性如下。  \n\n$\\textcircled{1}$ 可利用小径材、弯曲材、短原木生产，出材率可达 $60\\%\\sim70\\%$ （而采用制材方法只有 $40\\%\\sim50\\%)$ ，提高了木材利用率。  \n\n$\\textcircled{2}$ 由于单板（一般厚度为 $2\\mathord{\\sim}12\\mathrm{mm}$ ，常用 $2\\sim4\\mathrm{mm}$ ）可进行纵向接长或横向拼宽，因此可以生产长材、宽材及厚材。  \n\n$\\textcircled{3}$ 可以实现连续化生产，  \n\n$\\textcircled{4}$ 由于采用单板拼接和层积胶合，可以去掉缺陷或分散错开，使得强度均匀、尺寸稳定、材性优良。  \n\n$\\textcircled{5}$ 可方便进行防腐、防火、防虫等处理。  \n\n$\\textcircled{6}$ 可作板材或方材使用，使用时可垂直于胶层受力或平行于胶层受力。  \n\n(7）集成材集成材是将木材纹理平行的实木板材或板条在长度或宽度上分别接长或拼宽（有的还需再在厚度上层积）胶合形成一定规格尺寸和形状的木质结构板材，又称胶合木或指接材。  \n\n集成材能保持木材的天然纹理，强度高、材质好、尺寸稳定不变形，是一种新型的功能性结构木质板材，广泛用于建筑构造、室内装修、地板、墙壁板、家具和木质制品的生产中。具有小材大用、劣材优用；构件设计自由；尺寸稳定性高、安全系数高；可连续化生产；投资较大、技术较高等特点。",
+        "category": " Introduction"
+    },
+    {
+        "id": 525,
+        "chunk": "# 2.木质贴面材料  \n\n随着木器和家具生产中各种木质人造板的应用，需用各种贴面和封边材料作表面装饰和边部封闭处理。木质贴面材料主要有天然薄木、人造薄木、单板等，其主要起表面保护和表面装饰两种作用。  \n\n薄木是一种具有珍贵树种特色的木质片状薄型饰面或贴面材料。采用薄木贴面工艺悠久历史，能使零部件表面保留木材的优良特性并具有天然木纹和色调的真实感，至今仍是深受欢迎的一种表面装饰方法。  \n\n(1）薄木特点与分类薄木是家具制造与室内装修中最常采用的一种高级木质贴面材料，其可以从制造方法、形态、厚度等来进行分类。  \n\n$\\textcircled{1}$ 按制造方法分  \n\na.锯制薄木采用锯片或锯条将木方或木板锯解成的片状薄板（根据板方纹理和锯解方向的不同又有径向薄木和弦向薄木之分)。  \n\nb.刨切薄木将原木剖成木方并进行蒸煮软化处理后再在创切机上刨切成的片状薄木(根据木方剖制纹理和刨切方向的不同又有径向薄木和弦向薄木之分)。  \n\nc.旋切薄木将原木进行蒸煮软化处理后在精密旋切机上旋切成的连续带状薄木（弦向薄木)。  \n\nd.半圆旋切薄木在普通精密旋切机上将木方偏心装夹旋切或在专用半圆旋切机上将木方进行旋切成的片状薄木（根据木方夹持方法的不同可得到径向薄木或弦向薄木)，是介于刨切法与旋切法之间的一种旋制薄木。  \n\n$\\textcircled{2}$ 按薄木形态分  \n\na.天然薄木由天然珍贵树种的木方直接刨切制得的薄木  \n\nb.人造薄木由一般树种的旋切单板仿照珍贵树种的色调染色后再按纤维方向胶合成木方后制成的刨切薄木。  \n\nc.集成薄木由珍贵树种或一般树种（经染色）的小方材或单板按薄木的纹理图案先拼成集成木方后再刨切成的整张拼花薄木。  \n\n$\\textcircled{3}$ 按薄木厚度分  \n\na.厚薄木 厚度 $>0.5\\mathrm{mm}$ ，一般指 $0.5{\\sim}3\\mathrm{mm}$ 厚的薄木。  \n\nb.薄型薄木厚度 $<0.5\\mathrm{mm}$ ，一般指 $0.2{\\sim}0.5\\mathrm{mm}$ 厚的薄木。  \n\nc.微薄木厚度 $<0.2\\mathrm{mm}$ ，一般指 $0.05\\sim0.2\\mathrm{mm}$ 且背面黏合特种纸的连续卷状薄木或成卷薄木。  \n\n$\\textcircled{4}$ 按薄木花纹分  \n\na.径切纹薄木 由木材早晚材构成的、相互大致平行的条纹薄木。  \n\nb.弦切纹薄木 由木材早晚材构成的大致呈山峰状的花纹薄木。  \n\nc.波状纹薄木由波状或扭曲纹理产生的花纹薄木，又称琴背花纹、影纹，常出现在木(枫木)、桦木等树种中。  \n\nd.鸟眼纹薄木由纤维局部扭曲而形成的似鸟眼状的花纹，常出现在木（枫木）、桦木、水曲柳等树种中。  \n\ne.树瘤纹薄木由树瘤等引起的局部纤维方向极不规则而形成的花纹，常出现在核桃木、木（枫木)、法桐、栎木等树种上。  \n\nf.虎皮纹薄木由密集的木射线在径切面上形成的片状泛银光的类似虎皮的花纹，木射线在弦切面上呈纺锤形，常出现在栎木、山毛榉等木射线丰富的树种中。  \n\n(2）科技木科技木是以普通木材为原料，采用计算机虚拟与模拟技术设计，经过高科技手段制造出来的仿真甚至优于天然珍贵树种木材的全木质新型表面装饰材料。它既保持了天然木材的属性，又赋予了新的内涵。一般常将人造薄木和集成薄木等统称为科技木，也称工程木。  \n\n科技木既可仿真那些日渐稀少且价格昂贵的天然珍贵树种，又可以创造出各种更具艺术感的美丽花纹和图案。科技木与天然木相比，具有如下特点。  \n\n$\\textcircled{1}$ 色泽丰富、品种多样科技木产品经计算机设计，可产生不同的颜色及纹理，色泽更加光亮、纹理立体感更强、图案充满动感和活力。  \n\n$\\textcircled{2}$ 成品利用率高科技木克服了天然木的自然缺陷，产品没有虫洞、节疤和色变等天然缺陷。科技木产品因其纹理的规律性、一致性，不会产生天然木产品由于原木不同、批次不同而使纹理、色泽不同。  \n\n$\\textcircled{3}$ 产品发展潜力大随着国家禁伐措施和天然林保护政策的实施，可利用的珍贵树种日渐减少，使得科技木产品是珍贵树种装饰材料的替代品。  \n\n$\\textcircled{4}$ 装饰幅面尺寸宽大科技木克服了天然木径级小的局限性，根据不同的需要可加工成不同的幅面尺寸。  \n\n$\\textcircled{5}$ 加工处理方便易于加工及防腐、防蛀、防火（阻燃）、耐潮等处理。",
+        "category": " Introduction"
+    },
+    {
+        "id": 526,
+        "chunk": "# 三、木制品应为涂装提供的条件  \n\n使用各种天然木材、木质人造板和木质贴面材料，通过产品设计、小样试验、大样开料、贴面拼合、表面处理等程序，就成为一件合格的“白坯”，就可以进入最后的涂料涂装的工序了。前一阶段统称为“木工制作”，后一阶段称为“涂料涂装”。两个阶段都完成了，木制品就可以作为一件合格产品进人市场。  \n\n“木工制作”为“涂料涂装”这个后工序提供前提，主要体现在几个方面。  \n\n（1）提供有利于涂装的几何结构包括白坏的几何形状、几何尺寸都要有利于涂装的涂布和涂料的附着。(2）提供有利于涂装的漆前处理包括白坏的被涂面的平整度、光滑度及清洁度。(3）提供有利于涂装的工业化进程白坯在涂装过程中，既要满足单件产品在手工涂装时容易搬运、容易转动、容易放置的要求；又要满足大批量生产时产品能上自动生产线、能自动涂装、自动打磨的条件，最终提高涂装的自动化程度和成本优化。（4）提供有利于家具与涂料的“表里合一”的条件家具设计与制造中应当具备在涂装之后能强化产品功能的基础；应当具备与涂料结合之后能充分展示产品风格的内在理念。  \n\n家具与涂料、家具与涂装，绝不能被视为个别的个体。家具设计一旦决定了其产品风格，就要由涂装去实现、去展示。家具产品一旦决定了其市场定位，就要由涂料去保障、去增值。两者必须有机地形神结合，才能产生一件好家具，这是人们努力的方向。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 527,
+        "chunk": "# 第三节 木用涂料的品种及分类",
+        "category": " Introduction"
+    },
+    {
+        "id": 528,
+        "chunk": "# 一、木用涂料的品种  \n\n常用木用涂料有六大类，即硝基涂料（NC)、聚氨酯涂料（PU)、不饱和聚酯涂料(UPE)、紫外光固化涂料（UV）、酸固化涂料（AC）及水性涂料（W）。其中前三种是按成膜物质来命名，UV、AC两种是依据其固化条件来命名，W涂料是因为用水作为溶剂或是稀释介质，因而有别于所有使用有机溶剂的“溶剂型涂料”而被命名为“水性涂料”。",
+        "category": " Introduction"
+    },
+    {
+        "id": 529,
+        "chunk": "# 1.硝基涂料（NC）  \n\n硝基涂料亦称硝化纤维素涂料或NC涂料，主要原料是硝化纤维素。  \n\n硝基涂料具有一系列优异的理化性能，一是表干迅速，硝基涂料属于挥发干燥型涂料，依靠溶剂挥发来使涂层固化成膜，涂布之后的NC涂膜，它的溶剂完全挥发了，漆膜就实干了。它在常温条件下仅需10～15min即可表干，因而两次涂饰之间的时间大大缩短。二是涂膜破损后易修复，硝基涂料属于可逆性涂料，即完全实干的涂膜仍能被原溶剂溶解，因此当漆膜受到损伤时极易修复得和原来基本一致，看不出修补痕迹。三是涂膜装饰性能优良，涂膜色浅、透明度高、坚硬耐磨，有较好的机械强度和一定的耐水性及耐腐蚀性，广泛应用于高级家具、高级乐器、工艺品等的涂装。四是施工极为方便，可刷涂，亦可喷涂、淋涂、浸涂、辊涂，且涂料可使用时间较长，不易变质报废，密封  \n\n保存可多次使用。  \n\n当然，与其他涂料相比，硝基涂料涂膜的耐热、耐寒、耐光、耐碱性较差，在使用过程中较易损伤，由于涂料本身固体分低，施工后有大量有害气体挥发污染环境，这些不利因素都会制约其发展。在家具领域，硝基涂料目前主要用于美式涂装系列产品，也是家装涂料的一个重要品种。",
+        "category": " Introduction"
+    },
+    {
+        "id": 530,
+        "chunk": "# 2.聚氨酯涂料（PU)  \n\n聚氨酯涂料是指涂料成膜后漆膜中含有相当数量的氨酯键（—NHCOO—）的涂料，亦称PU涂料。而双组分聚氨酯涂料是目前我国市场上最主要的木用涂料品种之一，其成膜机理是异氰酸酯与羟基发生化学交联反应成膜。市售双组分聚氨酯涂料一般分为主剂、固化剂及稀释剂三组分，其中主剂是采用含羟基基团的各类树脂配制而成，固化剂则是含有异氰酸酯的预聚物树脂。使用时，主剂和固化剂按涂料制造厂家要求的比例混合，冉加入适量的稀释剂调整施工黏度，即可进行涂装。  \n\n由于聚氨酯涂料干燥成膜时发生了化学反应，因而具有一些普通挥发型涂料无法相比的优良性能。一是力学性能好：对各种木质基材表面有优良的附着力，漆膜坚韧，硬度高，有相当好的柔韧性，因而具有极高的耐摩擦和耐冲击性。二是化学性能好：漆膜固化后不易被溶剂再溶解，耐化学药品、抗污染性极好。漆膜受热不容易软化，漆膜耐候性、持久性能好。三是装饰性能好：漆膜透明度、丰满度、保光保色性优异。当然与其他涂料相比，聚氨酯涂料的涂膜质量受施工条件和施工环境影响较大，主要表现在：主剂和固化剂的配比有严格要求，如果配比不当，明显影响漆膜最终性能；喷涂施工过程中较易起泡；使用芳香族固化剂时，干膜易泛黄；重涂时要注意层间间隔时间，重涂前要均匀打磨，否则会影响涂层附着力；另外，涂料中微量的游离异氰酸酯（TDI）对人体有毒，一定程度上影响施工人员身体健康，并污染涂装环境。",
+        "category": " Introduction"
+    },
+    {
+        "id": 531,
+        "chunk": "# 3.不饱和聚酯涂料（UPE）  \n\n不饱和聚酯涂料，亦称UPE涂料，是指以气干型不饱和聚酯树脂为主要成膜物质的涂料，综合物化性能优异。由于该类漆中所用活性稀释剂是不饱和单体（如苯乙烯)，既能作为溶剂溶解不饱和聚酯，作为稀释剂起到调整稠度的作用，又能在涂装时作为活性单体参与不饱和聚酯反应，固化成膜，所以UPE是一种无溶剂涂料，一次可成厚膜，涂料固体分高，在木用涂装时特别适合作底漆，能使面漆表现出高丰满度。正是由于这些优点，UPE漆近年来在木用领域中获得较大发展。  \n\n不饱和聚酯涂料属于多组分涂料，市售UPE涂料包括涂料主剂（不饱和聚酯树脂为主）、引发剂（俗称白水）、促进剂（俗称蓝水）及稀释剂。主剂一般是含有一定数量的不饱和二元酸的聚酯树脂与某些特殊单体（如苯乙烯、烯丙基醚等）的混合物；白水则通常是指各种过氧化物和过氧化氢化合物溶液，它们能够分解生成自由基参与化学反应；蓝水的种类也很多，通常是一些环烷酸盐等。不饱和聚酯涂料固化的基本原理是引发剂与促进剂反应后先分解生成自由基，引发不饱和树脂中的双键发生游离基反应，最终交联固化成膜。促进剂的作用是加速引发剂的分解，加快反应速率。  \n\n不饱和聚酯涂料具有许多优异的性能，表现在：UPE涂料一般不含普通的挥发性溶剂，不释放大量有毒害气体，不污染环境；一次施工可获得较厚涂膜；可在常温条件下干燥；漆膜丰满度好、硬度高、光泽高等。不足之处是不饱和聚酯涂料成膜时收缩较大，成膜后涂膜一般较脆，易开裂；木质基材处理要求严格，否则影响附着力；配好的涂料可使用时间短、可操作时间短；特别要强调的是，蓝、白水大量直接接触非常危险，易燃、易爆，因此蓝、白水一定要分开存放，并按要求正确使用，否则易引起爆炸和火灾。",
+        "category": " Introduction"
+    },
+    {
+        "id": 532,
+        "chunk": "# 4.紫外光固化涂料（UV）  \n\n紫外光固化涂料，亦称UV涂料，是通过紫外线照射湿膜，引发自由基反应，从而使漆膜快速干燥的一类涂料。UV涂料主要成膜物质有不饱和聚酯树脂、丙烯酸环氧树脂、丙烯酸聚氨基甲酸酯树脂等，添加一定量的光引发剂、阻聚剂、助剂、低黏度的活性单体稀释剂、体质颜料等混合而成。  \n\n由于UV涂料固体分近 $100\\%$ ，一次可得高厚度漆膜，含有机溶剂极少，对环境污染低；干燥迅速，便于大批量生产，且涂料使用时浪费损耗极低，涂装作业空间场所减少；漆膜硬度高，具优良的耐溶剂性、耐药品性、耐摩擦性等。当然UV涂料使用时，一是在着色工艺时要慎选着色剂，避免紫外光照射产生褪色及涂料变黄情形；二是漆膜层间重涂需充分打磨，否则会产生附着不良的情况；三是UV涂料对人体会有刺激，长期接受紫外光的照射也会影响涂装人员的身体健康，要加强安全防护措施。另外，UV涂料通常采用辊涂或淋涂，较适合大平面基材的涂装。",
+        "category": " Introduction"
+    },
+    {
+        "id": 533,
+        "chunk": "# 5.酸固化涂料（AC)  \n\n酸固化涂料，简称AC涂料，一般用氨基树脂与醇酸树脂混合而成主漆，使用时加人有机酸（如对甲苯磺酸）为触媒（催化剂)，使其能在室温下反应干燥成膜。酸固化涂料具有一系列优异物化性能，干燥快，其涂膜经修整后平滑丰满，透明度和光泽度高，硬度高，坚韧耐磨，附着力强，机械强度高，并有一定的耐热、耐寒、耐水、耐油、耐化学品性能。酸固化涂料用于木家具涂装，在北欧及东南亚地区用得较为普遍。其缺点是涂料中含有游离甲醛，味道大，强烈刺激作业者眼鼻，同时涂料具酸性，易腐蚀金属基材。",
+        "category": " Introduction"
+    },
+    {
+        "id": 534,
+        "chunk": "# 6.水性涂料（W)  \n\n水性涂料是指以水为分散介质的涂料，一般分为水乳型和水溶性两大类，其中水乳型使用较为广泛。水乳型主要品种有聚氨酯分散体（PUD)、纯丙烯酸乳液（PA)、丙烯酸-聚氨酯改性乳液（PUA）等，包装形式分为单组分、双组分。目前水性木用涂料使用的树脂主要有水性醇酸、丙烯酸乳液或分散体、水性聚氨酯分散体、水性丙烯酸聚氨酯分散体、双组分水性聚氨酯分散体等，配漆时用上述树脂配合水、增稠剂、添加剂调制而成。水性涂料调漆方便，施工适用期长，易修补，基本安全无毒，漆膜柔韧性、附着力较好。特别是随着国家环保法规对VOC的限制，人们环保和健康意识的增强，溶剂型涂料受到前所未有的挑战，水性涂料日益受到重视。当然水性涂料固含量偏低，一次无法得到高厚膜的涂装，漆膜在耐溶剂性、耐药品性、耐热性、漆膜硬度及手感方面与传统 NC、PU相比有一定差异，涂料单价亦偏高。但W将与UPE、UV等一样，是中国涂料发展的大方向。  \n\n水性涂料成膜机理与溶剂型涂料在原理上是一致的，与涂料所选择的连接料树脂体系密切相关，同样有挥发干燥、交联固化、加热固化、UV固化等，但因为水性涂料中的特殊溶剂“水”的存在，使得其固化机理变得更复杂一些。如水溶性双组分聚氨酯涂料，在其成膜过程中包括可挥发物（溶剂、水）的挥发、多元醇和多异氰酸酯粒子的共凝结、多异氰酸酯和水的反应、多元醇和多异氰酸酯的反应等，这些反应将伴随涂料干燥的整个过程。  \n\n表3-7-1是木用涂料几个主要品种的性能特点的综合。  \n\n表3-7-1 木用涂料主要性能特点  \n\n\n<html><body><table><tr><td>品种</td><td>主要 用途</td><td>时间</td><td>指触干 指压干 时间</td><td>打磨 性</td><td>施工 性</td><td>涂料 气味</td><td>丰满 度</td><td>附着 力</td><td>硬度</td><td>耐溶 剂性</td><td>耐热 性</td><td>施工 安全</td><td>环保 性</td><td></td><td>涂料 单价</td></tr><tr><td>NC</td><td>底、面</td><td>5~10</td><td>约1</td><td>②</td><td>②#</td><td></td><td>③</td><td></td><td>③</td><td>B~H</td><td>#</td><td>④</td><td>#</td><td></td><td>低</td></tr><tr><td>PU</td><td>底.面</td><td>5~10</td><td>4~8</td><td>②</td><td>②</td><td>③</td><td>②</td><td>②#</td><td></td><td>HB~2H</td><td></td><td>③#</td><td>③</td><td>③</td><td>中</td></tr><tr><td>UPE</td><td>底</td><td>5~10</td><td>约4</td><td>③</td><td>③</td><td>④#</td><td>②</td><td></td><td>②</td><td>H~3H</td><td>②#</td><td>②</td><td>③</td><td>②</td><td>中</td></tr><tr><td>UV</td><td>底、面</td><td>瞬间</td><td>约0.5</td><td>③</td><td>②</td><td></td><td>②</td><td>③</td><td></td><td>≥2H</td><td>②#</td><td>#</td><td></td><td>②</td><td>高</td></tr><tr><td>AC</td><td>底面</td><td>20</td><td>1.5</td><td>②</td><td>③</td><td>④</td><td>?</td><td>②</td><td></td><td>H</td><td>③</td><td>②</td><td>③</td><td></td><td>中</td></tr><tr><td>W</td><td>底、面</td><td>20~30</td><td>4~5</td><td>③</td><td>③</td><td>①#</td><td>④#</td><td>③</td><td></td><td>B~HB</td><td></td><td>##</td><td>①</td><td>①</td><td>高</td></tr></table></body></html>\n\n注： $\\textcircled{1}$ 表示非常好； $\\textcircled{2}$ 表示很好； $\\textcircled{3}$ 表示好； $\\textcircled{4}$ 表示一般； $\\textcircled{5}$ 表示差。",
+        "category": " Introduction"
+    },
+    {
+        "id": 535,
+        "chunk": "# 二、木用涂料产品分类  \n\n木用涂料按产品系列可分为主要产品和配套产品。",
+        "category": " Introduction"
+    },
+    {
+        "id": 536,
+        "chunk": "# 1．主要产品  \n\n主要产品指由各涂料厂自行设计配方生产的产品，不同厂家生产的同一类型产品，性能差异可以很大。几个主要产品在木用涂装的实际使用中用量也是最多的。  \n\n（1）腻子腻子是一种厚浆状、黏稠性的涂料，主要由大量体质颜料与树脂等黏结材料混合调制而成。腻子专门用来填充白坯表面如缝隙、凹陷等，其主要作用就是填充，使白坯平整，便于下一步涂装。  \n\n常用的木器涂装用腻子有猪血灰腻子、硝基腻子、不饱和聚酯腻子、水性腻子等，相对 而言不饱和聚酯腻子和水性腻子应用较广，而猪血灰腻子则在中低档家具涂装中使用。  \n\n不饱和树脂腻子又称原子灰，是由不饱和聚酯树脂、粉料、苯乙烯等材料制成，包括主体灰和引发剂组成双组分填充材料。具有常温固化、干燥速率快、附着力强、易打磨、定型后平整、干硬、牢固等特点，广泛使用于汽车、机车、机床等工业品涂装，也大量用于家具如实色漆的基材填充处理，以及用于地板、室内外装修。  \n\n猪血灰腻子是用猪血、水、填充粉料混合搅拌后制得，靠猪血灰里面的血红蛋白氧化于结获得较好的硬度和打磨性，具有附着力好、施工方便、配制容易等特点，是一种资源易得、成本较低的腻子。缺点是干固后易吸潮，如一次性厚刮，干后易开裂、脱落。另外，由于腻子层厚，刮涂量、打磨量大，材料损耗多，影响其综合成本。  \n\n硝基腻子是由硝化棉、合成树脂、增韧剂、颜填料和有机溶剂混合制得。硝基腻子具有干燥快、易刮涂、易打磨的特点，适于木材表面作填平细孔和嵌缝用，可反复多次刮涂，浪费较少也很安全，但硬度和附着力一般，用于硝基底面配套体系较合适。  \n\n水性腻子的特点是所用的稀释剂是水，无毒、无刺激性气味，安全、环保，施工简便，打磨性和附着力也很好，价廉，目前应用渐渐增多，大有取代其他腻子之势，但水性腻子干燥较慢。水性腻子的主要品种是水性乳液腻子（俗称水灰)，是木用腻子中应用较广泛的一种。  \n\n(2）封闭底漆封闭底漆是底漆的一种，在木用涂装中亦称头道底漆。常用的有虫胶漆、NC封闭底漆、PU封闭底漆及UV封闭底漆及水性封闭底漆。  \n\n封闭底漆主要作用：作为头道底漆使用直接涂布于基材白坏上，干后轻磨。它能提高基材强度，有效清除木刺；阻隔木材中的水分及挥发性物质向表层扩散，减缓木材的吸湿、散湿，防止起泡，减缓木材变形，保持木材造型；封闭底漆可改善后续涂层的流平、光泽、丰满度、硬度等涂装效果，保证干燥过程的正常进行；如涂装于腻子及二道底漆上，或对填充后的基材进行封闭，可防止上层涂料向木材或底层渗人而产生下陷，可节约后续涂层的涂布量；采用专用于柚木及红木等油性木材封闭的特殊封闭底漆，可保证漆膜在硬木上具有良好的附着力；当贴纸家具贴纸后，先喷封闭底漆，可避免涂料向纸内渗透，增强涂料的附着力，提高面漆丰满度。封闭底漆的涂布方式可喷、刷、浸或擦涂。  \n\n(3）底漆底漆是指介于素材、腻子、着色剂与面漆之间的一个重要产品，位于涂膜面漆以下，封闭底漆以上的涂层，又称中涂底漆。木用涂料中底漆的品种很多，一般分为透明底漆和实色底漆。底漆的作用是填平，支撑面漆，保障丰满度。  \n\n对底漆性能的评估，可从以下方面去考虑：底漆与基材的附着力、对基材及腻子的填充性、自身流平性、漆膜的强度、漆膜透明度（清底漆)）、漆膜遮盖力（有色底漆）、抗发白性、黄变性、底漆与面漆配套性、施工性能、干燥速率、打磨性能等。  \n\n（4）面漆面漆是涂布于基材最上层的产品，是涂膜中最外层的涂层，对木制品起主要的装饰和保护作用。漆膜的性能指标，如硬度、光泽、色彩、手感、透明度、丰满度、平整度、耐擦伤、耐黄变、耐老化性能等都主要从面漆上体现出来。面漆品质及涂装质量直接影响整个涂装效果。  \n\n面漆一般可分为透明清面漆、透明有色面漆和实色面漆。根据漆膜表面光泽度高低不同，可分为高光面漆、亮光面漆、半光（亚光）面漆、无光面漆等。  \n\n(5）固化剂固化剂是用于反应型涂料交联的重要产品，在干燥过程中按规定比例添加于主剂中，与主剂产生化学反应而使其干燥硬化，最终给漆膜提供优异的物化性能。  \n\n木用涂料中，双组分聚氨酯涂料的固化剂种类较多，可分为：一是采用TDI单体为原料的固化剂，它的预聚物泛黄严重，应用不多，常见的品种是TDI与三羟甲基丙烷的加成物，多用于聚氨酯普通底漆及面漆，一般不耐黄变；二是采用HDI单体为原料的加成物，如拜耳公司的N-75，由于其耐黄变性能好，常用于高档聚氨酯如耐黄变清漆、白漆等；三是以IPDI单体为原料的固化剂，由于IPDI是一种环脂肪族异氰酸酯，因其耐候性能优良，通常用于高档聚氨酯漆，固化速率要比HDI固化剂快一些；四是混合固化剂，市售固化剂有很多是涂料厂自行调配的混合固化剂，主要用各种固化剂产品按不同组合、不同比例调配而成。混合固化剂调配的形式主要有：国产的与进口的混合、加成物与三聚体混合、甚至以上几种产品的全混合。厂家用这种方法去调整漆膜的耐黄变性、干燥速率、适用期、游离TDI含量、NCO含量、固体分等，当然也调整产品的成本。混合固化剂在通用涂装用固化剂中的用量最大，适应性最好。  \n\n加人了固化剂的双组分涂料必须在其适用期内使用完毕。",
+        "category": " Introduction"
+    },
+    {
+        "id": 537,
+        "chunk": "# 2.配套产品  \n\n木用涂料的配套产品是指除主要产品外，涂装中经常要使用的辅助产品。其中有些是市售产品，由涂料厂购人后分装、配套出售，因此不同的涂料厂使用的产品可能是一样的。有的配套产品使用量不大，但其对涂装的重要性及影响是很大的。  \n\n(1）蓝、白水不饱和聚酯涂料中含有不饱和双键，使用时加入强氧化剂——过氧化物作为引发剂，因其呈水白色而俗称“白水”。白水能生成自由基，引发涂料中不饱和键产生链式反应，直至干燥成膜。常用的白水有过氧化甲乙酮等。  \n\n在不饱和聚酯涂料涂装中，为了获得理想的反应速率，除上述引发剂外，还要加人强还原剂作为促进剂，用以提高反应速率。目前常用的还原剂因其外观呈蓝紫色，而俗称“蓝水”，常用蓝水有环烷酸盐类的环烷酸钴等。  \n\n在不饱和聚酯涂料涂装时，一般按产品说明书或施工需要将主剂和稀释剂先混合均匀，然后再分成相等的两份，分别加入需要量的蓝水或白水，各自充分搅拌均匀。喷涂时再分别取两种混合液按1：1比例混合调匀后施工，即混即用。混合好的漆，必须在规定的时间内使用完，否则会因超过适用期，涂料胶化而造成浪费。  \n\n另外，在使用蓝、白水时还要特别注意安全。蓝水和白水直接接触会发生剧烈化学反应，甚至发生起火、爆炸，因此在保管、贮存或远距离运输时，要特别注意不能将两者堆放在一起，必须分开放置。  \n\n(2）着色剂在透明涂装中，分别有本色涂装、底着色、面着色、中层及面修色等方法。在以上方法的涂装中，现场着色是非常重要的一环，专供现场着色使用的各种着色剂，也就成为重要的配套产品。与涂料厂生产有色涂料时所用的各种着色材料不同，在木用涂装中用于调整色彩效果的着色材料统称为着色剂。前者只用于涂料的着色，而后者则用于底材的着色，也可在涂装现场加人涂料中用于修色。前者用于涂料，后者用于涂装。色彩的调整是木用涂装中一项复杂而又非常重要的工作，尤其是透明涂装，需要进行基材着色来表现木材特有的木纹，增加美感，有时甚至通过多层着色，来表现色调的丰富程度和层次感，获取整体的色感效果，提高涂装后产品的附加值。  \n\n涂料厂提供给用户的着色剂一般分为两类。一类是色精，属染料型着色剂，是将染料溶解于溶剂中再与其他材料调配而成，有很好的着色力和透明度，主要用在透明涂装的基材上面或加人清漆中。染料型着色剂色彩鲜艳，亮丽，但有些品种的耐候性较差。选择优质染料，这个问题可以解决，因此，产品很成熟并形成系列。另一类是色浆，属颜料型着色剂，主要用于遮盖木材造成不透明着色或半透明效果。和染料型着色剂相比，颜料型着色剂耐候性要好得多，色调丰富，使用无机颜料的着色剂耐候性更好，但色泽鲜艳度较低。  \n\n着色剂的调配很复杂，通常根据客户的色样调配，必须要由专业人员予以调配试色；好的涂装着色，要由有丰富经验的涂装师，合理使用着色材料，用多种方法、手法去“造色”；除此之外，还与木材的特点有很大关系，涂装前，必须根据白坏原生底色及木质特性对基材颜色加以调整、处理；涂装着色所用各类涂料和着色剂，最好为同一厂家配套产品，以保证附着力和配套性。  \n\n(3）稀释剂稀释剂是木用涂料中最重要的配套产品，稀释剂可降低木用涂料的黏度，使之能适合不同的生产方法和施工方法。稀释剂还影响涂料涂装后的十燥速率，尤其是当环境温度发生变化时更加明显，因此木用涂料厂家除提供涂料主剂外，同时提供配套稀释剂。木用涂料配套稀释剂，除了通用型的产品之外，还有夏用稀释剂（施工环境温度高于 $30^{\\circ}C$ 时使用)，挥发速率较慢；冬用稀释剂(施工环境温度低于 $20^{\\circ}C$ 时使用）挥发速率稍快，以满足不同施工环境温度的需要。  \n\n(4）防发白水在高温、高湿环境下施工，漆膜表面有时会出现霜状白点，严重时成片，干固后使透明漆膜不透明，使实色漆膜变色。为了解决这个问题，在调配涂料时，按规定加入一定量的防发白水，搅拌均匀后再喷涂就可有效防止发白现象的发生。防发白水一般由醇醚类、醚酯类、酮类和酯类等溶剂混合而成。  \n\n加人防发白水时，等量代替原来要加入的稀释剂，以保证喷涂黏度不会大幅波动。最好的方法是先将防发白水按比例与稀释剂调配好，再将这种混合稀释剂按正常量加人到漆料中。  \n\n防发白水不能过量使用，对NC漆而言，把原来稀释剂的 $25\\%$ 用防发白水来取代，这是极限量，如果加人 $25\\%$ 的防发白水代替了稀释剂，仍然发白，就应停止施工。否则，加人过量防发白水，虽然不发白了，但会使漆膜不干，粘连。一次性喷涂太厚的湿膜，虽然温、湿度不高，也会泛白，这时应把湿膜厚度减薄，单纯依靠防发白水，不一定能解决问题。  \n\n(5）催干剂催干剂是涂料工业的主要助剂。一般来说，木用涂料在制造时已视需要加入了一定量的催干剂，施工时不需要再加，只有在气候较低的环境下或有特殊要求时，才可由家具厂按需要适当补加催干剂，以加速涂层干燥。但催干剂用量不能过多，否则会导致干膜过脆、附着力不良、失光、日后龟裂等漆病。  \n\n(6）慢干水在木用涂料的涂装中，因为干速过快，会产生很多问题，如气泡、橘皮、针孔、失光、发白、附着力不好等，严重影响涂装效果。市售产品中，为了预防上述漆病的发生，配套稀释剂在夏天都已经把溶剂的挥发速率调了下来，一般情况下并不需要加人慢干水。为家具厂的涂装现场配备慢干水，是为了应付突发酷热天气，涂装环境异常，需要减慢湿膜干速时才使用。慢干水一般是由沸点高于 $150^{\\circ}C$ 的高沸点酮、醇酯、醇醚类溶剂混合而成，挥发速率较慢。可适当调整涂料的干燥速率，预防发生不良漆病。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 538,
+        "chunk": "# 第四节 木用涂料产品基础配方及原理",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 539,
+        "chunk": "# 一、腻子  \n\n腻子的主要作用就是填孔，辅助填平，弥补底材的缺陷，改善涂装质量。木用涂料中腻子分为两类：嵌补腻子和填孔腻子。嵌补腻子即人们常说的腻子，其作用主要是填大孔，如木材本身的缺陷、钉眼等，因此嵌补腻子要稠、厚，对较大的缝隙、缺陷能有效地填充；嵌补腻子同时对木材要有较好的附着力，不易脱落。填孔腻子，也叫填充剂，主要是对木材的表面管孔进行填充，防止底漆的渗陷，减少底漆的用量，降低涂装成本，改善涂装效果。因此，填孔腻子黏度不能太稠及干燥太快，要容易刮涂。  \n\n常用腻子有：猪血灰腻子、硝基腻子、不饱和聚酯腻子、UV腻子、水性腻子等品种。",
+        "category": " Introduction"
+    },
+    {
+        "id": 540,
+        "chunk": "# 1.猪血灰腻子  \n\n(1）猪血灰腻子猪血灰腻子一般作为嵌补腻子使用。在20世纪90年代初，我国家具制造业刚起步的时候，使用非常广泛，主要用于贴纸家具贴纸之前的底材处理或实色底漆的底材处理。附着力好、硬度高、干燥快、易打磨、成本低。  \n\n随着技术的进步，木质底材的质量得到了较大的提高。猪血腻子的用量越来越少。但是，在古迹修复等工程中，仍然会使用到。猪血灰腻子配方及生产工艺见表3-7-2。  \n\n表3-7-2 猪血灰腻子配方及生产工艺   \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数）/%</td><td>生产工艺</td></tr><tr><td>新鲜猪血</td><td>100</td><td>100目滤网过滤除去杂质</td></tr><tr><td>生石灰氧化钙</td><td>2~3</td><td>加入水中，水尽量少，搅拌，熟化，100目滤网过滤 将熟化后的生石灰(CaO)溶液，边搅边加人滤过的猪血中，待猪血由鲜</td></tr><tr><td>滑石粉</td><td>100～150</td><td>红变为咖啡色，停止加人石灰水，备用 使用前，将滑石粉加入处理好的猪血中，边加人边手工搅拌，至黏度合适</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 541,
+        "chunk": "# (2）配方调整  \n\n$\\textcircled{1}$ 原料选择猪血必须是新鲜猪血，采集回来应立即处理，否则腐败变质不能使用。  \n\n填料一般需用 $400\\sim800$ 目的滑石粉。氧化钙必须现场加水配置使用，石灰（ $C a O_{2}^{3}$ ）转化为石灰水 $\\left[\\mathrm{Ca(OH)_{2}}\\right]$ 溶液。放置时间过长，有效的石灰水 $\\boldsymbol{\\left[\\mathrm{Ca(OH)_{2}}\\right.}$ 溶液』会与空气中的$\\mathrm{CO}_{2}$ 发生反应，变成无用的石灰水 $[C a C O_{3}$ 溶液］。 $\\mathrm{Ca(OH)_{2}}$ 溶液在制备时浓度要尽量高，因此处理生石灰（CaO）时水量要适当。  \n\n$\\textcircled{2}$ 指标调整如果作为嵌补腻子使用，需要多加滑石粉等填料，做得稠厚一些；如果作为填孔腻子使用，填料可适当少加，做得稀薄一些，便于刮涂施工。  \n\n$\\textcircled{3}$ 技术难点猪血的熟化是腻子质量的关键。猪血和石灰水的比例是技术关键点。石灰水比例高，则腻子硬度高；石灰水比例低，则腻子硬度低。好的猪血腻子，加人滑石粉后，应该是青绿色的。太绿，说明加人的石灰水太多，硬度高，难打磨，容易离层；色太浅，说明加入的石灰水少，则硬度不够。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 542,
+        "chunk": "# 2.硝基腻子  \n\n（1）硝基透明腻子 配方、性能及生产工艺见表3-7-3～表3-7-5。  \n\n表3-7-3 硝基透明腻子配方及生产工艺   \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数）/%</td><td>生产工艺</td></tr><tr><td>硝化棉溶液(1/2s) 醋酸丁酯：丁醇：二甲苯：硝化棉=44： 11:11:34</td><td>50</td><td>投人分散缸，开动搅拌机，中速搅拌</td></tr><tr><td>醇酸树脂（60%）</td><td>15</td><td>加人</td></tr><tr><td>422马来酸酐树脂溶液（50%）</td><td>10</td><td rowspan=\"2\">加人</td></tr><tr><td>增塑剂DOP</td><td>1</td></tr><tr><td>硬脂酸锌PLB</td><td>2</td><td>慢慢加人，分散均匀</td></tr><tr><td>滑石粉（1250目）</td><td>22</td><td>慢慢加人，分散均匀；高速分散10～15min，温度 控制在50℃以下，至细度合格，40目滤布包装</td></tr></table></body></html>  \n\n表3-7-4 硝基透明腻子性能指标   \n\n\n<html><body><table><tr><td>项目</td><td>性能指标</td><td>项目</td><td>性能指标</td></tr><tr><td>外观</td><td>乳状半透明黏稠液体</td><td>实干时间/h</td><td>≤1</td></tr><tr><td>细度/μm</td><td>≤100</td><td>刮涂性</td><td>易刮涂</td></tr><tr><td>固体含量/%</td><td>60</td><td>有机挥发物含量</td><td>符合GB18581</td></tr><tr><td>表干时间/min</td><td>≤10</td><td>重金属含量</td><td>符合GB18581</td></tr></table></body></html>  \n\n表3-7-5 改性树脂溶解及工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数)/%</td><td>生产工艺</td></tr><tr><td>二甲苯</td><td>50</td><td>称量，投人分散缸</td></tr><tr><td>422马来酸酐树脂溶液</td><td>50</td><td>加人，搅拌15～20min，使其溶解完全，200目过滤，备用</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 543,
+        "chunk": "# (2）配方调整  \n\n$\\textcircled{1}$ 原料选择硝基腻子一般由硝化棉溶液、短油度豆油醇酸树脂、硬脂酸锌、填料组成。滑石粉可以选择800目或更粗的产品，有良好的填充性和透明度。硝化棉一般选用1/2的硝化棉或几种规格硝化棉的搭配使用，预先溶解成30%。增塑剂目前大部分采用的是邻苯二甲酸盐，如邻苯二甲酸二丁酯（DBP)、邻苯二甲酸二辛酯（DOP)。随着环保标准的提高，此类增塑剂逐渐被限制应用。可以采用环氧大豆油等环保型增塑剂代替。粉料的含水量要控制，最好在 $0.2\\%$ 以下。  \n\n② 指标调整硝化棉和树脂是主要的成膜物质。其比例决定了腻子的技术指标和施工性能。硝化棉和醇酸树脂（按固含量比）的比例为 $1:(0.8\\sim1)$ 较为合适。422马来酸酐树脂是为了降低腻子的黏度，提高施工固含，同时改善腻子的刮涂性能。硝化棉多，硬度好；硝化棉少，硬度低。但硝化棉过少，上层底漆施工后容易“咬底”。加人滑石粉，可以提高腻子的填充性，但会影响腻子的透明度，应根据腻子的用途决定添加量。增塑剂的作用是为了调节漆膜的柔韧性，过多或过少都会影响漆膜的性能。硬脂酸锌最好选用酸值较低的产品，好的硬脂酸锌应该溶解于二甲苯。加人硬脂酸锌仅仅为了改善打磨性，加量要根据不同的配方试验确定，过多会严重影响漆膜的性能，如附着力、透明度、储存稳定性等。膨润土的加入量约为配方量的 $1\\%\\sim1.5\\%$ ，既可以防止滑石粉的沉降，也可以提高腻子的刮涂性，改善物料沉降和贮存稳定性。  \n\n$\\textcircled{3}$ 技术难点配方关键是硝化棉与其他树脂的比例，固含比率是硝化棉：树脂 $\\b=$ $1:(0,8\\sim1)$ ，比例过低则涂膜的硬度不够，耐干热性不好；过高则涂膜的刮涂性不好，容易卷边。马来酸酐树脂加入可以降低黏度，改善施工性能，但是加人过量会影响涂膜的黄变性、贮存稳定性和耐干热性，因此加人量要合适。  \n\n$\\textcircled{4}$ 生产注意事项硝基腻子在生产过程中，最好采用夹套缸生产，物料温度控制在$50^{\\circ}C$ 以下，否则，贮存过程中容易变黄、发黑、锈桶。投料时，最好边分散边投人后续物料，否则容易引起颗粒。  \n\n$\\textcircled{5}$ 腻子施工时的注意事项硝基腻子一般采用刮涂施工。不可一次性厚涂。干后打磨时一定要将木径上的腻子打磨干净，以免喷涂底漆特别是PU底漆时咬底。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 544,
+        "chunk": "# 3.不饱和聚酯（UPE）腻子  \n\n（1）不饱和聚酯（UPE）腻子的参考配方不饱和聚酯腻子分为两种：一种为实色腻 子；另一种为透明腻子。实色腻子又叫原子灰。历来都由汽车涂料广或专业厂家研制。木用 涂料厂只生产UPE透明腻子。不饱和聚酯透明腻子的配方、生产工艺及性能见表3-7-6和 表3-7-7。  \n\n表3-7-6不饱和聚酯透明腻子配方及生产工艺   \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数)/%</td><td>工艺</td></tr><tr><td>气干型UPE树脂（70%） 防绿化剂 苯乙烯 阻聚剂（对苯二酚，10%醋酸乙酯溶液） 蓝水（6%异辛酸钻） 分散剂</td><td>38 0.6 10 0.1 0.6 0.5</td><td>按序投人，先中速分散均匀</td></tr><tr><td>滑石粉（800目） 硬脂酸锌PLB</td><td>45 3</td><td>高速分散10～15min，检测细度，40目滤网过滤</td></tr></table></body></html>  \n\n表3-7-7 不饱和聚酯透明腻子性能指标  \n\n\n<html><body><table><tr><td>项目</td><td>性能指标</td><td>项目</td><td>性能指标</td></tr><tr><td>原漆外观 漆膜外观 黏度/mPa·s</td><td>搅拌均匀，无硬块 打磨后无缺陷 20000~50000</td><td>刮涂性 可打磨时间/h</td><td>易刮涂 ≤4</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 545,
+        "chunk": "# （2）配方调整  \n\n$\\textcircled{1}$ 原料选择市售的UPE树脂分为两类：因吸氧单体的不同分为烯丙基醚类和双环戊二烯类。前者表干性能好，易打磨，硬度略差；后者表干性能略差，硬度较前者高。两者都可以作UPE透明腻子。苯乙烯主要作活性稀释剂，既可以降低黏度，又可以参与最后交联形成漆膜。阻聚剂主要提高产品生产和贮存稳定性，延缓或防止胶化。防沉剂主要选用SiOz，防沉稳定性较好。苯乙烯使用前要进行含水量测试，以保持腻子的贮存稳定性。滑石粉一般选用400目或800目。  \n\n$\\textcircled{2}$ 指标调整树脂的表干性能决定腻子的打磨性。硬脂酸锌的加入也会改善漆膜的打磨性。滑石粉的增加可以改善打磨性，但过多影响透明腻子的透明度。与透明底漆不同，腻子的滑石粉可以选择较粗，如400目或800目。  \n\n$\\textcircled{3}$ 技术难点UPE透明腻子的贮存稳定性主要取决于树脂和苯乙烯的稳定性。因此，在生产UPE透明腻子的时候添加阻聚剂（如对苯二酚或与其他复配）改善其贮存稳定性。  \n\n$\\textcircled{4}$ 生产过程注意的问题生产UPE腻子最好采用捏合机生产，避免物料温度过高。使用高速分散机时，最好使用夹套缸，用 $7^{\\circ}C$ 或 $12^{\\circ}C$ 的水循环冷却，注意监控物料温度不超过$50\\%$ ，否则会严重影响产品的贮存稳定性。苯乙烯的光学稳定性较差，生产UPE腻子时应该避免光线直射。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 546,
+        "chunk": "# 4.UV腻子  \n\n(1）UV透明腻子UV一般只有透明腻子，大多作为填孔腻子使用。一般使用于中纤板、木皮填孔或找平以保证UV底漆的施工质量。UV透明腻子的配方、生产工艺及性能见表3-7-8和表3-7-9。  \n\n表3-7-8UV透明腻子配方及生产工艺   \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数）/%</td><td>生产工艺</td></tr><tr><td>双官能团丙烯酸单体 环氧丙烯酸树脂</td><td>2.3 75</td><td>按序加人，中速搅拌均匀</td></tr><tr><td>消泡剂 分散剂</td><td>0.2 0.5</td><td>加人，中速搅拌均匀</td></tr><tr><td>滑石粉800目</td><td>20</td><td>加人，高速搅拌分散至细度合格，≤100μm</td></tr><tr><td>光敏剂</td><td>2</td><td>加人，搅拌均匀，30目滤网过滤包装</td></tr></table></body></html>  \n\n表3-7-9UV透明腻子性能指标   \n\n\n<html><body><table><tr><td>项目</td><td>性能指标</td><td>项目</td><td>性能指标</td></tr><tr><td>原漆状态</td><td>搅拌均匀无硬块</td><td>固化速率（一支汞灯，80W/</td><td>5~20</td></tr><tr><td>细度/μm 旋转黏度/mPa·s</td><td>≤70 7000~15000</td><td>cm)/(m/min) 漆膜外观</td><td>平整</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 547,
+        "chunk": "# (2）配方调整  \n\n$\\textcircled{1}$ 原料选择低聚物有环氧丙烯酸酯、聚氨酯丙烯酸酯、聚酯丙烯酸酯、聚醚丙烯酸酯等。丙烯酸单体主要有单官能度丙烯酸单体、双官能度丙烯酸单体、多官能度丙烯酸单体。官能度高，反应速率快、漆膜硬度高、不好打磨，漆膜较脆；官能度低，反应速率慢、漆膜硬度软、易打磨、漆膜韧性好。UV使用的助剂一般为无溶剂助剂，消泡剂如BYK-057，分散剂如BYK161等。滑石粉主要是为了提高漆膜的填充性和打磨性，由于UV的施工固含量极高，可达到 $100\\%$ ，所以对粉料的透明度要求较高。光引发剂主要使用的是自由基光引发剂：裂解型自由基光引发剂（如汽巴的1173）和夺氢型自由基光引发剂（如二苯甲酮)。一般选用两种光引发剂的组合和活性胺类光敏剂搭配使用。  \n\n$\\textcircled{2}$ 技术难点低聚物是主要的成膜物质，其组成决定了漆膜的主要性能。不同低聚物和单体的搭配很重要。要根据低聚物的性能选择单体，优势互补。如低聚物硬度低，可选高官能度单体，提高硬度；如树脂硬度高，可选低或中等官能度产品，改善韧性。UV腻子不要加入在PU和NC涂料里改善打磨性的硬脂酸锌，因为硬脂酸锌在分散过程中容易带来气泡，很难消除，影响施工性能。  \n\n$\\textcircled{3}$ 生产注意事项由于UV使用的单体都有自聚倾向，故应避免光线直射、物料分散时温度切勿过高。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 548,
+        "chunk": "# 5.水性腻子  \n\n(1）水性腻子水性腻子的质量要求：干燥快、填孔性好、附着力好、容易刮涂、打 磨。水性腻子的配方、生产工艺及性能见表3-7-10和表3-7-11。  \n\n表3-7-10 水性腻子配方及生产工艺   \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数）/%</td><td>生产工艺</td></tr><tr><td>水</td><td colspan=\"2\">18.6 加人</td></tr><tr><td>胺中和剂(氨水)</td><td rowspan=\"2\">0.8 6.0 3.5</td><td rowspan=\"2\">加人，搅拌均匀，至pH为8～9</td></tr><tr><td>防冻剂(丙二醇) 成膜剂</td></tr><tr><td>防腐防霉剂</td><td>0.3 0.8</td><td></td></tr><tr><td>防沉剂 重质碳酸钙（800目）</td><td>45.00 10.00</td><td>慢慢投人，搅拌至完全溶解 投人，高速分散至均匀</td></tr><tr><td>滑石粉（800目） 水性乳液</td><td>15.00</td><td rowspan=\"2\">缓慢加人，分散均匀</td></tr><tr><td></td><td></td></tr></table></body></html>  \n\n表3-7-11 水性腻子性能指标   \n\n\n<html><body><table><tr><td>检验项目</td><td>性能指标 =</td><td>检验项目</td><td>性能指标</td></tr><tr><td>固含/%</td><td>67</td><td>刮涂性</td><td>易刮涂，不卷边</td></tr><tr><td>表干/min</td><td>43</td><td>贮存稳定性</td><td>无异常</td></tr></table></body></html>  \n\n(2）配方调整水性腻子的树脂一般选用聚醋酸乙烯乳液，性价比高。氨水的作用主要是调节体系的pH，利于羟乙基纤维素的溶解；丙二醇的加人可以改善水性腻子的低温冻融稳定性；成膜助剂的加人，可以降低乳液的成膜温度，利于腻子的干燥；重质碳酸钙的加人是为了提高腻子的填充性；滑石粉可以改善腻子的打磨性。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 549,
+        "chunk": "# 二、封闭底漆  \n\n封闭底漆又称封固底漆、头度底漆。封闭底漆的主要品种：虫胶漆、PU普通封闭漆、PU封油用封闭底漆、PU透明有色封闭底漆、UV封闭底漆。",
+        "category": " Introduction"
+    },
+    {
+        "id": 550,
+        "chunk": "# 1.虫胶漆  \n\n虫胶又叫紫胶、紫胶茸、雪纳（shellac）、泡力水（polish)，是一种很好的封闭性物质，能起到封闭和隔离作用，它具有封闭性好、干燥快、施工方便、可刷、可喷的特点。虫胶漆的溶解方法：可以取虫胶片1份，加入到4份工业酒精中，溶解后，使其固含量保持在20%～25%。虫胶漆的使用：在家具涂饰工艺中，虫胶漆常作为NC漆的封闭隔离底漆和着色、修色的黏合料来使用，一般采用刷涂施工。乐器行业仍然使用虫胶漆来制作小提琴，特别是高档的小提琴，工艺代代传承，代代创新，其天然色泽非合成材料能比。",
+        "category": " Introduction"
+    },
+    {
+        "id": 551,
+        "chunk": "# 2.PU普通封闭底漆  \n\n（1）PU普通封闭底漆 配方、生产工艺和性能见表 $3-7-12\\sim$ 表3-7-14。  \n\n表3-7-12PU普通封闭底漆配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>组成</td><td>原料及规格</td><td>组成</td></tr><tr><td>羟基丙烯酸树脂（65%）</td><td>25</td><td>丙二醇甲醚醋酸酯</td><td>5</td></tr><tr><td>二甲苯</td><td>49.8</td><td>醋酸乙酯</td><td>10</td></tr><tr><td>醋酸丁酯</td><td>10</td><td>有机锡（10%）</td><td>0.2</td></tr></table></body></html>\n\n注：依次投人，低速搅拌均匀，200目过滤包装。  \n\n表3-7-13 有机锡T-12（ $\\angle10^{\\circ},\\beta_{0}^{\\prime},$ ）溶液的配方  \n\n\n<html><body><table><tr><td>原料及规格</td><td>组成(质量分数)/%</td><td>原料及规格</td><td>组成（质量分数）/%</td></tr><tr><td>T-12</td><td>10</td><td>二甲苯</td><td>90</td></tr></table></body></html>\n\n注：生产工艺为依次加人，搅拌均匀。  \n\n表3-7-14PU普通封闭底漆性能指标  \n\n\n<html><body><table><tr><td>项目</td><td>性能指标</td><td>项目</td><td>性能指标</td></tr><tr><td>外观</td><td>水白色至浅黄色透明液体</td><td>表干/min</td><td>≤20</td></tr><tr><td>黏度(涂-4#杯)/s</td><td>9~15</td><td>实干/h</td><td>≤4</td></tr><tr><td>细度/μm</td><td>0~10</td><td>固含量/%</td><td>13~17</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 552,
+        "chunk": "# (2）配方调整  \n\n$\\textcircled{1}$ 原料选择常用的树脂有椰子油酸短油度醇酸树脂、豆油酸短油度醇酸树脂、合成脂肪酸醇酸树脂、羟基丙烯酸树脂。PU封闭底漆选用的溶剂一般为中等挥发速率的溶剂，太快会影响涂料的施工和封闭效果，太慢会溶解底材中的一些酚类物质，影响封闭漆的干燥。选用的溶剂分子量较小，利于较快速地渗透人基材中。固化剂一般选用TDI加成物和三聚体。助剂一般选用消泡剂或少量底材润湿剂。  \n\n$\\textcircled{2}$ 指标调整PU封闭底漆的固含量一般控制在 $15\\%$ 以下，固化剂的固含控制在$45\\%\\sim50\\%$ ，配比控制在主漆：固化剂 $\\mathbf{\\delta}=4:1$ 。一般不需另外加人稀释剂，视封闭的要求也可以用稀释剂稀释后喷涂、刷涂。  \n\n$\\textcircled{3}$ 技术难点一般来说，丙烯酸树脂的封闭性好于醇酸树脂。豆油酸短油度醇酸树脂较椰子油短油度醇酸树脂、合成脂肪酸醇酸树脂干燥快，但如果固化剂选用得好，后者的封闭性更好。加成物固化剂的反应速率比三聚体快，封闭性更好。如果选用合成脂肪酸或椰子油树脂，固化剂可以拼用一部分TDI三聚体固化剂。  \n\n$\\textcircled{4}$ 使用的注意事项PU封闭底漆与固化剂混合后，最好是在4h用完。如果混合物黏度超过原始黏度的两倍，则不宜再使用。固化剂最好配套使用，以免影响使用效果。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 553,
+        "chunk": "# 3.PU封油用封闭底漆  \n\nPU封油用封闭底漆一般选用单组分的TDI/MDI聚合物，适用于油性木如红木、柚木等。一般市售的有：聚醚和TDI的加成物，MDI的聚合物，也有TDI和TMP的加成物。由于这类化合物可以与底材里的酚类等含羟基化合物反应，所以可以有效地封闭底材并防止油脂向外渗出，有效地加强底材与上面涂层的附着力。PU封油封闭底漆对水较为敏感，分装时最好加人脱水剂及充氮气，市售产品可以直接分装出售，配套稀释剂擦涂、刷涂、喷涂均可。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 554,
+        "chunk": "# 4.PU透明有色封闭底漆  \n\n（1）PU透明有色封闭底漆PU透明有色封闭底漆即含有染料的封闭底漆。PU透明有色封闭底漆一般直接喷涂于底材上，兼具封闭底漆和着色的作用，修色主要  \n\n是底着色的一种重要手段。结合后面的面修色可以使天然的、质量不是很好的木皮变得美观，大大增加其经济价值。PU透明有色封闭底漆配方、生产工艺及性能见表3-7-15和表3-7-16。  \n\n表3-7-15PU透明有色封闭底漆配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数）/%</td><td>原料及规格</td><td>比例（质量分数）/%</td></tr><tr><td>羟基丙烯酸树脂（65%）</td><td>25</td><td>胺催干剂(二甲基乙醇胺)</td><td>0.2</td></tr><tr><td>甲苯</td><td>47.1</td><td>黑色染料</td><td>0.3</td></tr><tr><td>醋酸丁酯</td><td>10</td><td>黄色染料</td><td>0.7</td></tr><tr><td>醋酸乙酯</td><td>10</td><td>棕色染料</td><td>0.7</td></tr><tr><td>PMA</td><td>6</td><td></td><td></td></tr></table></body></html>\n\n注：生产工艺为按序投人，中速揽拌均匀。  \n\n表3-7-16PU透明有色封闭底漆性能指标  \n\n\n<html><body><table><tr><td>项目</td><td>性能指标</td><td>项目</td><td>性能指标</td></tr><tr><td>外观</td><td>透明有色液体， 符合标准版</td><td>固含量/% 密度（25℃）/（g/cm3）</td><td>13~17 0.8~1.2</td></tr><tr><td>细度/μm</td><td>20</td><td></td><td></td></tr></table></body></html>  \n\n(2）配方调整树脂一般选用羟基丙烯酸树脂，封闭性能较好。加人染料溶液调色。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 555,
+        "chunk": "# 5.UV封闭底漆  \n\nUV封闭底漆，一般采用水性树脂，辊涂施工，红外或蒸汽烘干。这主要是为了保持UV涂料在线施工，快速高效的特点，所采用的树脂一般为含水脂肪族聚氨酯丙烯酸酯或脂肪族聚氨酯丙烯酸水溶液，分装出售。此类树脂具有良好的柔韧性和木材润湿性，且在UV固化前可重新乳化，不容易粘辊，便于施工及清理。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 556,
+        "chunk": "# 三、底漆",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 557,
+        "chunk": "# 1.品种  \n\n木用涂料的六大品种都有底漆，而且各自都有透明底漆和实色底漆。与前述的各种封闭底漆不同，此处所指的底漆是真正意义上的“中涂底漆”。  \n\n木用涂料底漆按成膜物质来分，常用品种主要有硝基（NC)、双组分聚氨酯（PU）、不饱和聚酯（UPE)、酸固化（AC)、紫外光固化（UV）和水性（W）共六大类，它们均有透明底漆和实色底漆，其中硝基（NC)、双组分聚氨酯（PU)、水性（W）多用于刷涂和喷涂，不饱和聚酯（UPE)、酸固化（AC）多用于喷涂，紫外光固化（UV）主要用于辊涂和淋涂，另外，硝基（NC)、双组分聚氨酯（PU)、不饱和聚酯（UPE)、酸固化（AC）也常用于静电喷涂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 558,
+        "chunk": "# 2.底漆的作用  \n\n在涂装过程中，底漆主要起填平、增厚、减少面漆用量、全面提高面漆各种性能的作用，实色底漆同时还有提供遮盖力和着色作用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 559,
+        "chunk": "# 3.底漆的品质要求  \n\n底漆的品质要求为： $\\textcircled{1}$ 填平性好； $\\textcircled{2}$ 操作方便，流平性好，不起泡； $\\textcircled{3}$ 容易砂磨，不粘砂纸； $\\textcircled{4}$ 透明底漆透明性好，实色底漆有较好的遮盖力； $\\textcircled{5}$ 符合国标和行标。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 560,
+        "chunk": "# 4.配方原理  \n\n(1）硝基底漆硝基底漆主要由硝化棉、醇酸树脂、增塑剂、混合溶剂和颜填料等组成。其主要优点为漆膜干燥快，施工后15min左右可表干，2h可砂磨，4h左右可叠放；漆膜易被溶剂溶解，易修复；其缺点是固含量低，一次涂饰的涂膜薄，为达一定厚度，需多道涂装，费工时；施工环境受湿度的影响大，潮湿天气易发白。  \n\n$\\textcircled{1}$ 基础配方 硝基底漆基础配方见表3-7-17。  \n\n表3-7-17 硝基底漆基础配方  \n\n\n<html><body><table><tr><td>原料名称 硝化棉 1/4S</td><td>规格</td><td>硝基透明底漆/%</td><td>硝基白底漆/%</td><td>硝基黑底漆/%</td></tr><tr><td>马来酸树脂 醇酸树脂 增塑剂 稀释剂 助溶剂 真溶剂 真溶剂 真溶剂 防沉剂 消泡剂 润湿分散剂 钛白粉 炭黑</td><td>1303 11-70D DOP 甲苯 异丁醇 乙二醇单丁醚 醋酸丁酯 醋酸乙酯 A-630X BYK141 BYK103 R-706</td><td>18 5 18 4 10 5 2 19.1 10 0.3 0.3 0.2 1</td><td>14 一 14 3 10 3 2 10.6 5 0.5 0.3 0.5 10 一</td><td>14 14 2 10 5 2 12.6 10 0.5 0.3 0.5 2</td></tr><tr><td>流平剂</td><td>BYK306</td><td>6 0.1</td><td>2 25 0.1</td><td>2 25 0.1 100.00</td></tr><tr><td>合计 性能指标</td><td>黏度（25℃）/×10-Pa·s 固含量/% 表干/min 指压干/min</td><td>100.00 1300 44.0 7</td><td>100.00 9800 62.7 8</td><td>4200 56.0 9 17</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 配方调整  \n\na.原材料的选择和油漆主要性能指标的调控在硝基底漆中，常用的硝化棉主要有1/8S、1/4S、1/2S、30S，其黏度由低到高，柔韧性由差到好，硬度和打磨性由好到差，耐候性由差到好。1/4S、1/2S常单独使用，也可与1/8S、30S搭配使用以满足不同的性能要求。马来酸树脂在硝基底漆中作为硬树脂可提供好的光泽和打磨抛光性，较高的硬度和增加不挥发固体分，但其缺点是耐候性差、耐寒性差、柔韧性差并易开裂。醇酸树脂主要使用不干性短油度醇酸树脂，它能改善硝基底漆的附着力、柔韧性、耐候性、光泽和丰满度，但硬度和打磨性则相应下降。硬脂酸锌的加人会明显改善底漆的打磨性，但添加量过大会影响层间附着力。颜料、填料的加入决定底漆的遮盖力、透明度和填充性。  \n\nb.技术难点在硝基底漆中，硝化棉、硬树脂、醇酸树脂三者之间的比例是配方调整的关键。它决定了底漆的干速、附着力、硬度、柔韧性、耐冲击强度和耐温变性。另外，配方中溶剂的选择也是难点。选用溶剂时需考虑其溶解力、挥发速率和挥发平衡。快、中、慢的组分用量要平衡，真溶剂、助溶剂与稀释剂之间的平衡也很重要。否则，易引起气泡、橘  \n\n皮、慢干等缺点。  \n\n$\\textcircled{3}$ 产品制备硝基底漆的生产通常分四个工序进行：硝化棉及硬树脂的溶解；颜填料的研磨分散；调漆及配色；过滤包装。常用的生产设备为高速分散机，颜料的研磨分散需用到球磨机、砂磨机、三辊机。颜料做成色浆后在调漆及配色过程中加入，填料则可在调漆过程中用高速分散机直接分散，两个过程均需注意漆料的黏度，黏度太稀可能会导致分散不均匀而有颗粒。调配好的产品用 $120\\sim150$ 目的滤网过滤包装。  \n\n(2）双组分聚氨酯底漆双组分聚氨酯底漆主要包括由醇酸树脂或内烯酸树脂、颜料、填料、混合溶剂、涂料助剂等组成的主剂和由异氰酸酯等组成的固化剂。施工时主剂与固化剂按$2:1$ 比例混合，用配套稀释剂调整施工黏度。其主要优点为固含量高，填充性好，漆膜硬度高，耐化学品污染；其缺点是部分固化剂中有游离异氰酸酯单体，有毒性；价格偏高。  \n\n$\\textcircled{1}$ 基础配方 双组分聚氨酯底漆基础配方见表3-7-18。  \n\n表3-7-18 双组分聚氨酯底漆基础配方  \n\n\n<html><body><table><tr><td>原料名称</td><td>规格</td><td>PU透明底漆/%</td><td>PU白底漆/%</td><td>PU黑底漆/%</td></tr><tr><td colspan=\"5\">A组分</td></tr><tr><td>醇酸树脂 润湿分散剂 防沉剂 消泡剂 钛白粉 炭黑 硬脂酸锌 滑石粉 流平剂 稀释剂 真溶剂</td><td>3735-60 BYK103 A-630X BYK052 R-706 MP-100 PLB 1250目 BYK306 二甲苯</td><td>75 0.2 0.5 0.3 一 一 2 13 0.2 3.8</td><td>40 0.5 0.5 0.3 18 一 2 28 0.2 5.5 5</td><td>45 0.5 0.5 0.3 一 2 2 38 0.2 6.5 5</td></tr><tr><td colspan=\"5\">醋酸丁酯 5</td></tr><tr><td>合计 TDI加成物 TDI三聚体 溶剂</td><td>L-75 HRB 醋酸丁酯 二甲苯</td><td>100.00 B组分 20 10 12.25 7.5</td><td>100.00 20 5 14.75 10</td><td>100.00 20 5 14.75</td></tr><tr><td>稀释剂 脱水剂 合计 性能指标</td><td>BF-5 黏度（25℃）/mPa·s 固含量/% 表干/min 指压干/h 可打磨时间/h</td><td>0.25 50.00 2000 60.0 11 1.5 3</td><td>0.25 50.00 5500 72.1 6 1.0 2</td><td>10 0.5 50.00 6800 69.1 9 1.0 2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 561,
+        "chunk": "# $\\textcircled{2}$ 配方调整  \n\na.原材料的选择和主要性能指标的调控在双组分聚氨酯底漆中，常用的树脂主要有不干性短油度的大豆油醇酸树脂或椰子油醇酸树脂，高档的也会使用羟基丙烯酸树脂。其耐候性由差到好，色泽由深到浅。双组分聚氨酯底漆的干速和耐候性除与树脂本身性能有关外，还取决于固化剂的种类。分散剂、防沉剂、消泡剂、流平剂等助剂的选择原则是除其本身应起的作用外，应与体系有较好的相容性，不影响涂料的层间附着力。硬脂酸锌的加人会明显改善底漆的打磨性，但添加量过大会影响层间附着力。颜填料的加人决定底漆的遮盖力、透明度和填充性。  \n\nb.技术难点在双组分聚氨酯底漆中，干速与附着力、柔韧性、耐候性、耐温变性之间的关系和平衡是配方调整的难点。双组分聚氨酯底漆的干速主要取决于配方所用的树脂和固化剂，调节底漆干速的方法有许多种，固化剂中增加TDI三聚体的含量，主剂中加人有机锡或胺类催化剂均可以提高底漆的干速。有机锡类通常催化OH-NCO反应体系，特别是避免羟基副反应的应用中。叔胺作催化剂主要催化异氰酸酯和水反应生成二氧化碳。在潮气固化型聚氨酯体系中，用有机胺类催化剂是比较合适的，但在普通PU涂料中副作用比较明显，主要是有化学性气泡导致涂膜暗泡、容易迁移导致涂膜白化、影响涂膜耐水性能。许多家具厂对底漆均要求快干，但干速并非越快越好，干得越快，涂料反应所产生的内应力积聚越大，如没有很好释放，则漆膜会变脆，附着力、柔韧性、耐温变性变差，严重的会出现漆膜脱层和开裂现象。另外，加入胺类催干剂会使漆膜严重变黄，从而影响耐黄变性。有机锡催干剂虽不影响耐黄变性，但许多环保法规中已禁用。  \n\n$\\textcircled{3}$ 产品制备双组分聚氨酯底漆的生产通常分三个工序进行：颜料、填料的研磨分散；调漆及配色；过滤包装。常用的生产设备为高速分散机，颜料的研磨分散需用到球磨、砂磨、三辊机。生产过程中，颜料通常预先做成色浆后在调漆及配色过程中加入，钛白粉和填料则可在调漆过程中用高速分散机直接分散，两个过程均需注意漆料的黏度，黏度太稀可能会导致分散不均匀而有颗粒。调配好的产品用 $120\\sim150$ 目的滤网过滤包装。  \n\n(3）气干型不饱和聚酯底漆气干型不饱和聚酯底漆主要由不饱和聚酯树脂、颜料、填料、苯乙烯、涂料助剂等组成。施工时以蓝水作促进剂，以白水作引发剂。其主要优点为固含量高，丰满度好，硬度高，可一次性厚涂；其缺点是操作较麻烦，适用期较短。蓝白水的使用、贮存要非常注意安全，且蓝白水的比例、质量不好时会引起漆膜颜色变化，整个湿膜的干燥过程极易受环境的温度和湿度的影响。  \n\n$\\textcircled{1}$ 基础配方 不饱和聚酯底漆基础配方见表3-7-19。  \n\n表3-7-19 不饱和聚酯底漆基础配方  \n\n\n<html><body><table><tr><td>原料名称</td><td>规格</td><td>UPE透明底漆/%</td><td>UPE白底漆/%</td><td>UPE黑底漆/%</td></tr><tr><td>气干型不饱和聚酯树脂 蜡型不饱和聚酯树脂</td><td>2307 6688</td><td>55 15</td><td>25 20</td><td>25 20</td></tr><tr><td>分散剂 防沉剂</td><td>BYK163 A-630X</td><td>0.2</td><td>0.2</td><td>0.2</td></tr><tr><td>消泡剂</td><td>BYK057</td><td>0.5</td><td>0.5</td><td>0.5</td></tr><tr><td>钛白粉</td><td>R-706</td><td>0.3</td><td>0.3</td><td>0.3</td></tr><tr><td></td><td></td><td>一</td><td>8</td><td></td></tr><tr><td>炭黑</td><td>MP-100</td><td>一</td><td>一</td><td>2</td></tr><tr><td>硬脂酸锌</td><td>PLB</td><td>2</td><td>2</td><td>2</td></tr><tr><td>滑石粉</td><td>800目</td><td>10</td><td>28</td><td>28</td></tr><tr><td>透明粉</td><td>1250目</td><td>5</td><td>一</td><td></td></tr><tr><td>碳酸钙</td><td>1000目</td><td>一</td><td>10</td><td>一</td></tr><tr><td>活性稀释剂</td><td>苯乙烯</td><td></td><td>2.7</td><td>10</td></tr><tr><td>流平剂</td><td>BYK354</td><td>10.2</td><td></td><td>9.7</td></tr><tr><td>阻聚剂/缓聚剂</td><td>对苯二酚（1%HQ)</td><td>0.3</td><td>0.3</td><td>0.3</td></tr><tr><td>合计</td><td></td><td>1.5 100.00</td><td>2.0</td><td>2.0</td></tr><tr><td></td><td>黏度（25℃）/×10-Pa*s</td><td>1100</td><td>100.00 6500</td><td>100.00</td></tr><tr><td></td><td>固含量/%</td><td>70.6</td><td></td><td>4800</td></tr><tr><td></td><td></td><td></td><td>82.75</td><td>77.53</td></tr><tr><td>性能指标</td><td>胶化时间(25℃)</td><td>19</td><td>45</td><td>67</td></tr><tr><td></td><td>表干/min</td><td>27</td><td>26</td><td>34</td></tr><tr><td></td><td>可打磨时间/h 贮存稳定性(70℃，3d)</td><td>5.5 无沉淀结块</td><td>3.0 无沉淀结块</td><td>3.4 无沉淀结块</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 配方调整  \n\na.原材料的选择和涂料主要性能指标的调控在不饱和聚酯底漆中，常用的是气干型不饱和聚酯，但有时也加人少量蜡型（厌氧型）不饱和聚酯，主要作用是降成本。当然两者间的混容性要好。好的气干型树脂在较差的环境如低温或高湿条件下仍然能表现出良好的干燥性，加人蜡型树脂后会影响干速，但却带来贮存稳定性好的优点，掌握好比例最重要。分散剂、防沉剂、消泡剂、流平剂等助剂的选择原则是除其本身应起的作用外，应与体系有较好的相容性，不影响涂料的干速、层间附着力和贮存稳定性。硬脂酸锌的加人会明显改善底漆的打磨性，但添加量过大会影响层间附着力。颜料、填料的加人决定底漆的遮盖力、透明度和填充性。透明粉是目前市场中PU、UPE、NC 等涂料产品的新型填充料。其折射率与大部分树脂的折射率接近，因此用透明粉作填充料，同比传统填充料滑石粉，涂料产品的透明性明显提高。在不饱和聚酯底漆中加入透明粉，主要是为了获得更好的透明度，同时又有很好的填充性，成本更优。阻聚剂或缓聚剂的加人主要是使底漆有良好的贮存稳定性，同时在施工时提供一定的适用期，避免反应太快从而造成浪费和出现橘皮及针孔现象。  \n\nb.技术难点在不饱和聚酯底漆中，阻聚剂或缓聚剂的选用与干速、贮存稳定性之间的关系是配方调整的难点。因不饱和聚酯底漆的贮存稳定性受温度影响较大，其本身又能发生自聚反应，所以配方中必须加人一些阻聚剂或缓聚剂，但阻聚剂或缓聚剂的加入又会影响涂料的干速，如何平衡成了配方调整的关键。夏天温度高，不饱和聚酯底漆易胶凝，可适当增加阻聚剂或缓聚剂的加入量，并将其置于阴凉处贮存。此时环境温度高，虽增加用量，但不会减慢干速。冬天温度低，可适当减少阻聚剂或缓聚剂的加人量，能提高不饱和聚酯底漆的干速。虽减少用量，但不明显影响贮存稳定性。  \n\n$\\textcircled{3}$ 产品制备不饱和聚酯底漆的生产通常分三个工序进行：颜填料的研磨分散；调漆及配色；过滤包装。常用的生产设备为双轴高速分散机，不饱和聚酯底漆的整个生产过程必须控制好漆液的温度，一般控制在 $50^{\\circ}C$ 左右，温度太高会影响涂料的贮存稳定性甚至胶凝。调配好的产品用 $120\\mathrm{\\sim}150$ 目的滤网过滤包装。  \n\n$\\textcircled{4}$ 酸固化底漆酸固化底漆主要由丁醚化氨基树脂、醇酸树脂、颜料、填料、混合溶剂、涂料助剂等组成。使用时再按比例加入酸催化剂和稀释剂。其主要优点为操作容易，干燥快，固含量高，丰满度好，耐化学污染、耐磨性、耐黄变性优良；其缺点是气味大，氨基树脂中含有残存的游离甲醛，树脂在进行缩聚反应固化成膜时也有甲醛释放；抗裂性差、易开裂；酸催化剂有一定的腐蚀性。  \n\n$\\textcircled{1}$ 基础配方 酸固化底漆基础配方见表3-7-20。  \n\n$\\textcircled{2}$ 配方调整  \n\na.原材料的选择和涂料主要性能指标的调控在酸固化底漆中，脲醛树脂和醇酸树脂的配合相当重要，其配合得当与否对漆膜的质量带来很大影响。脲醛树脂赋予漆膜以硬度、光泽等性能，醇酸树脂赋予漆膜以弹性和附着力等性能。要根据醇酸树脂的油度长短、油的种类、对漆膜的质量要求等多种因素综合考虑它们之间的配比。一般认为浅色或白色由于颜料分比较高，脲醛树脂比例可适当偏低些，深色可以偏高些。如要求漆膜光亮丰满、坚韧耐磨等特殊性能，脲醛树脂用量可更高甚至超过醇酸树脂用量，总之，脲醛树脂用量必须根据成本和质量进行平衡。在脲醛树脂和醇酸树脂的配合中要注意两种树脂的混容性。混容性不好直接影响漆膜的光泽和透明度。在酸固化底漆中，颜料、填料的选择也很关键，与酸能反应的颜料、填料不能选用，否则会与作为催化剂的酸反应造成慢干或不干现象。在酸固化底漆配方中，丁醇或异丁醇要保持一定的比例，一般控制在 $5\\%$ 以上，否则氨基树脂本身会继续缩聚，黏度上升，从而影响产品的贮存稳定性。  \n\nb.技术难点在酸固化底漆中，脲醛树脂和醇酸树脂的选择及配比是配方调整的关键，它决定产品的基本性能。酸的加人量应适当，如果加人过多，干燥虽然很快，但漆膜很易变脆，甚至日久会产生裂纹；如加人过少，则干燥较慢。  \n\n$\\textcircled{3}$ 产品制备酸固化木器底漆生产设备和要求与双组分聚酯底漆基本一致。颜料、填料的分散需注意漆料的黏度，黏度太稀可能会导致分散不均匀而有颗粒。另外，因酸对金属具有一定的腐蚀性，生产和包装必须使用塑料工具和容器。  \n\n表3-7-20 酸固化底漆基础配方  \n\n\n<html><body><table><tr><td>原料名称</td><td>规格</td><td>AC透明底漆/%</td><td>AC白底漆/%</td></tr><tr><td colspan=\"4\">主剂</td></tr><tr><td>醇酸树脂</td><td>3370D</td><td>36</td><td>30</td></tr><tr><td>丁醚化脲醛树脂 防沉剂</td><td>582-60 A-630X</td><td>42 1</td><td>35 1</td></tr><tr><td>分散剂</td><td>BYK103</td><td>0.3</td><td>0.5</td></tr><tr><td>消泡剂</td><td>BYK141</td><td>0.2</td><td>0.3</td></tr><tr><td>钛白粉</td><td>R706</td><td>一</td><td>15</td></tr><tr><td>滑石粉</td><td>800目</td><td>10</td><td>10</td></tr><tr><td>稀释剂</td><td>甲苯</td><td>4</td><td>3</td></tr><tr><td>稀释剂</td><td>异丁醇</td><td>6.6</td><td>5</td></tr><tr><td>流平剂</td><td>BYK306</td><td>0.2</td><td>0.2</td></tr><tr><td>合计</td><td></td><td>100.00</td><td>100.00</td></tr></table></body></html>  \n\n酸催化剂  \n\n\n<html><body><table><tr><td>对甲苯磺酸 溶剂 合计</td><td>PTSA 甲醇</td><td>5 5</td><td>5 5</td></tr><tr><td>性能指标</td><td>黏度/mPa·s 固含量/% 表干/min 可打磨时间/h</td><td>10 3000 60.5 25 4</td><td>10 20000 67 20 3.5</td></tr></table></body></html>  \n\n(4）紫外光固化底漆紫外光固化底漆主要由光固化树脂、活性稀释剂、光敏剂、颜料、填料和涂料助剂等组成。其主要优点为十速快、固化时间短，无溶剂、高固体、基本无公害，涂膜性能优良；其缺点是能源利用率低，需专用的固化设备，适于大平面而不适合复杂形状部件的涂装。  \n\n$\\textcircled{1}$ 基础配方 紫外光固化底漆基础配方见表3-7-21。  \n\n表3-7-21 紫外光固化底漆基础配方  \n\n\n<html><body><table><tr><td>原料名称</td><td>规格</td><td>UV辊涂透明底漆/%</td><td>UV辊涂白底漆/%</td></tr><tr><td>环氧丙烯酸酯</td><td>CN104A80</td><td>30</td><td>28</td></tr><tr><td>聚酯丙烯酸酯</td><td>CN2261</td><td>30</td><td>15</td></tr><tr><td>活性稀释剂</td><td>SR306</td><td>15.7</td><td>10.7</td></tr><tr><td>活性稀释剂</td><td>SR351</td><td>1</td><td>10</td></tr><tr><td>消泡剂</td><td>BYK055</td><td>0.3</td><td>0.3</td></tr><tr><td>分散剂</td><td>BYK103</td><td>0.5</td><td>1</td></tr><tr><td>滑石粉</td><td>1250目</td><td>20</td><td>10</td></tr><tr><td>钛白粉</td><td>R706</td><td>一</td><td>20</td></tr><tr><td>光敏剂</td><td>1173</td><td>3.5</td><td>3</td></tr><tr><td>光敏剂</td><td>184</td><td></td><td>2</td></tr><tr><td>合计</td><td></td><td>100.00</td><td>100.00</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>原料名称</td><td>规格</td><td>UV辊涂透明底漆/%</td><td>UV辊涂白底漆/%</td></tr><tr><td rowspan=\"5\">性能指标</td><td rowspan=\"2\">黏度（25℃）/×10-Pa·s 涂布量/（g/m²）</td><td>2500</td><td>3500</td></tr><tr><td>30</td><td>30</td></tr><tr><td rowspan=\"3\">固化速率/(m/min)</td><td>10</td><td>5</td></tr><tr><td>固化条件</td><td>1支中压汞灯80W/cm</td><td>1支中压汞灯，1支灯，80W/cm</td></tr><tr><td>附着力/级</td><td>1</td><td>1</td></tr><tr><td rowspan=\"3\"></td><td>铅笔硬度</td><td>H</td><td>H</td></tr><tr><td>耐磨性（750g，500r)</td><td>0.02</td><td>0.02</td></tr><tr><td></td><td></td><td></td></tr></table></body></html>  \n\n$\\textcircled{2}$ 配方调整  \n\na.原材料的选择和涂料主要性能指标的调控在紫外光固化底漆中，产品的基本性能（包括硬度、柔韧性、附着力、光学性能、耐老化性能等）主要由低聚物树脂决定，常用的树脂主要包括不饱和聚酯、环氧丙烯酸树脂、聚氨酯丙烯酸树脂、聚酯丙烯酸树脂、聚醚丙烯酸树脂、丙烯酸酯官能化的聚丙烯酸树脂等。各种树脂均有其特性，可根据要求选择。  \n\n活性稀释剂主要有单官能团、双官能团、多官能团三种。单官能团活性稀释剂具有转化率高、体积收缩少、固化速率低、交联密度低、黏度低等特点。但是，很多单官能团活性稀释剂由于分子量较低，因此挥发性较大，相应地毒性与气味也大，而且易燃。双官能团活性稀释剂的固化速率比单官能团活性稀释剂的快，成膜交联密度增加，同时仍保持良好的稀释性。随着官能团的增加，分子量增大，因而其挥发性较小，气味较低。因此双官能团（甲基）丙烯酸酯类单体广泛应用于光固化涂料的配制。多官能团活性稀释剂含有3个或3个以上的丙烯酸酯或甲基丙烯酸酯活性基团，具有光固化速率快、固化产物硬度高、脆性大、挥发性低、黏度较大、稀释效果差等特点。其通常主要不是用来降低体系黏度，而是针对使用要求调节某些性能，如加快固化速率、增加干膜的硬度及提高其耐刮性等。  \n\n在紫外光固化木器底漆中，光引发剂主要使用自由基聚合光引发剂，主要分为两大类：裂解型光引发剂和夺氢型光引发剂。裂解型光引发剂多以芳基烷基酮衍生物为主。比较有代表性的包括苯偶姻衍生物、苯偶酰缩酮衍生物（Irgacure651）、二烷氧基苯乙酮、 $a$ 羟烷基苯酮（Darocurll73、Irgacure184）、 $a$ -胺烷基苯酮、酰基磷氧化物、芳基过氧酯化物、卤代甲基芳酮、有机含硫化合物、苯甲酰甲酸酯等。夺氢型光引发剂，一般以芳香酮结构为主，还包括某些稠环芳烃，它们具有一定吸光性能。  \n\nb.技术难点在紫外光固化木器底漆中，低聚物树脂的选择是配方调整的关键，它决定了固化后产品的基本性能。表3-7-21中环氧丙烯酸酯在固化速率、涂层性能、附着性能方面表现优异，聚酯丙烯酸酯可改善固化膜的韧性和耐冲击强度，对提高附着力有益。使用TPGDA和TMPTA活性稀释剂，涂料黏度较低，便于涂料向木材的微孔渗透，固化后涂层与木质纤维的有效接触面积加大，附着力提高。  \n\n$\\textcircled{3}$ 产品制备紫外光固化木器底漆生产设备和要求与不饱和聚酯底漆基本一致。分散颜料、填料时必须控制好漆液的温度，一般控制在 $50^{\\circ}C$ 左右，温度太高会影响涂料的贮存稳定性。生产时避光照射。  \n\n(5）水性底漆水性底漆主要由水性树脂乳液、颜填料和水性助剂等组成。其主要优点为减少了对人体有害的有机溶剂排放，有利于保护环境；以水为溶剂，减少了火灾的隐患。其缺点是综合性能不能满足高装饰性家具的涂装要求，价格偏贵。  \n\n$\\textcircled{1}$ 基础配方单组分水性底漆基础配方见表3-7-22，双组分水性底漆基础配方见表3-7-23。  \n\n表3-7-22 单组分水性底漆基础配方   \n\n\n<html><body><table><tr><td>原料名称</td><td>规格</td><td>单组分水性透明底漆/%</td><td>单组分水性白底漆/%</td></tr><tr><td>水性树脂乳液 润湿剂 分散剂</td><td>AC2514 Tego270 Tego750W</td><td>75 0.3 一</td><td>53 0.5 0.8</td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td>成膜助剂 防冻融剂</td><td>TEXANOL 丙二醇</td><td>8 2</td><td>8 2</td></tr><tr><td>消泡剂</td><td>Tego830</td><td>0.5</td><td>0.9</td></tr><tr><td>增稠剂</td><td>RM5000</td><td>1.1</td><td>1. 1</td></tr><tr><td>硬脂酸锌浆</td><td>PERENOL 1097A</td><td>2</td><td>2</td></tr><tr><td>钛白粉</td><td>R706</td><td>一</td><td>12</td></tr><tr><td>碳酸钙</td><td>800目</td><td></td><td>8</td></tr><tr><td>滑石粉</td><td></td><td></td><td></td></tr><tr><td>稀释剂</td><td>1250目</td><td>一</td><td></td></tr><tr><td>胺中和剂</td><td>水</td><td>10.9</td><td>6.5</td></tr><tr><td>合计</td><td>AMP-95</td><td>0.2</td><td>0.2</td></tr><tr><td></td><td>黏度（25℃）/X10-3Pa·s</td><td>100.00 330</td><td>100.00 1400</td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td>细度/μm</td><td>30</td><td>50</td></tr><tr><td></td><td>固含量/%</td><td>34.9</td><td>49.8</td></tr><tr><td>性能指标</td><td>表干/min</td><td>48</td><td>52</td></tr><tr><td></td><td>可打磨时间/h</td><td>4.4</td><td>4.8</td></tr><tr><td></td><td>附着力/级</td><td>1</td><td>１</td></tr><tr><td></td><td>贮存稳定性(50°℃/7d)</td><td>无异常</td><td>无异常</td></tr></table></body></html>  \n\n表3-7-23 双组分水性底漆基础配方  \n\n\n<html><body><table><tr><td>原料名称</td><td>规格</td><td>双组分水性透明底漆/%</td><td>双组分水性白底漆/%</td></tr><tr><td colspan=\"4\">A组分</td></tr><tr><td>水性树脂乳液</td><td>XP2470</td><td>73.0 12.8</td><td>50 9.5</td></tr><tr><td>稀释剂 水 胺中和剂</td><td>AMP95</td><td>0.2</td><td>0.2</td></tr><tr><td>润湿剂</td><td>TEGO 270 TEGO750W</td><td>0.3</td><td>0.5</td></tr><tr><td>分散剂</td><td></td><td>0.4</td><td>0.8</td></tr><tr><td>消泡剂</td><td>TEGO 810</td><td>0.5</td><td>0.9</td></tr><tr><td>流变改性剂</td><td>RM-5000</td><td>0.8</td><td>1.1</td></tr><tr><td>钛白粉</td><td>R706</td><td></td><td>17</td></tr><tr><td>碳酸钙</td><td>800目</td><td></td><td>13.7</td></tr><tr><td>滑石粉</td><td>1250目</td><td>10.0</td><td>6</td></tr><tr><td>透明粉 防沉剂</td><td>JY-W25 A200</td><td></td><td>0.3</td></tr><tr><td>硬酯酸锌浆</td><td>PERENOL 1097A</td><td>2</td><td></td></tr><tr><td>合计</td><td></td><td>100.00</td><td>100.00</td></tr><tr><td colspan=\"4\">B组分</td></tr><tr><td>固化剂</td><td>XP2487</td><td>22</td><td>15</td></tr><tr><td>合计</td><td></td><td>122</td><td>115</td></tr><tr><td>性能指标</td><td>黏度（25℃)/KU 细度/μm 固含量/% 表干/min 可打磨时间/h 附着力/级</td><td>70 35 46.5 55</td><td>80 50 62 58</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 配方调整  \n\na.原材料的选择和涂料主要性能指标的调控在水性木器漆中，常用的水性树脂主要有水性醇酸树脂、水性丙烯酸树脂、水性聚氨酯树脂、水性聚氨酯-丙烯酸共聚树脂和双组分水性聚氨酯。各种树脂均有其特性，可根据要求选择。水性醇酸树脂的涂膜光泽高，具有良好的柔韧性和耐冲击性能，但耐水性较差；水性丙烯酸树脂光泽高，保光性、保色性和耐候性好；水性聚氨酯-丙烯酸共聚树脂耐化学性、耐沾污性、耐溶剂性较好；水性聚氨酯树脂，不含游离的异氰酸酯，无毒，可室温固化成膜，加工容易，施工方便，其力学性质可与溶剂型媲美。水性木器漆的黏度和贮存稳定性主要靠增稠剂来调节，选择时除了考虑其增稠效率和对涂料流变性的控制以外，还应考虑其他的一些因素，如与体系的相容性、耐水性等，使涂料具有最佳的施工性能、最好的涂膜外观和最长的使用寿命。在水性木器漆中，成膜助剂的选择也很重要，它直接影响漆膜的性能。理想的成膜助剂具有同树脂良好的相容性、具有适宜的水溶解性和挥发性以及良好的水解稳定性。水性木器漆中消泡剂的选择除了具有消泡作用外，同时还不应该与颜料发生反应，在消泡的同时，不存在缩孔、针孔、失光、厚边、丝纹等副作用。  \n\nb.技术难点在水性木器漆中，成膜助剂的选择、增稠剂的选择和消泡剂的选择是关键。成膜助剂与乳液相容性不好，直接影响涂料的透明性，严重的会造成乳液絮凝甚至破乳。成膜助剂的加入量影响涂料的最低成膜温度和干燥速率。增稠剂影响涂料的防沉性能和流变性。选择不当会造成沉淀结块和橘皮、缩边现象。消泡剂主要消除生产和施工时所产生的气泡。选择不当会造成缩孔、针孔现象。  \n\n$\\textcircled{3}$ 产品制备水性木器底漆生产所用设备和油性漆基本一致，在生产过程中，消泡剂的加入最好分两次搅拌添加，即在颜料、填料分散时和调漆时分别加人。增稠剂最好用水和共溶剂稀释后添加，加人时要稳而慢，避免增稠剂浓度局部过高而造成过度增稠或絮凝。成膜助剂都是强溶剂，对乳液有较大的凝聚性，应用水稀释后边搅拌边缓慢加入，防止局部过浓形成液态凝聚而破乳。水性色浆生产时 $\\mathbf{pH}$ 值调节在 $7\\sim8$ ，投料过程要在搅拌状态下进行，防止材料局部浓度高结块结粒。注意温度控制，防止凝胶，结块损坏设备和出废品。生产前后用乙醇清洗砂磨机，防止污染和生锈。水性色浆使用于配制色漆，事前要进行与乳液，成膜助剂，基材润湿剂的相容性试验，防止破乳。在配漆中，适宜于后添加，防止色浆与基料在重新竞聚中破坏自身的离子稳定性。注意成品漆黏度控制，过低易沉降，过高易在施工中过度稀释，造成漆病。成品漆 $\\mathbf{pH}$ 调节在 $7\\sim8$ 0",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 562,
+        "chunk": "# 四、面漆  \n\n面漆是涂装的最后一道，是最出“风头”的一道涂层。木用涂料的面漆产品，要兼具装饰性及保护功能。面漆在光泽上分为亮光、半光、亚光。在涂装上又分为全封闭、半封闭、全开放，以体现多角度的全面的装饰效果。  \n\n目前，木器涂装主要使用的面漆有硝基漆、聚氨酯漆、紫外光固化涂料等，水性漆目前还没有大量使用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 563,
+        "chunk": "# 1.硝基面漆  \n\n(1）硝基清面漆按光泽分类：硝基亮光清面漆和硝基亚光清面漆；按装饰性分：硝基透明清面漆、硝基透明有色清面漆、硝基实色面漆。",
+        "category": " Introduction"
+    },
+    {
+        "id": 564,
+        "chunk": "# $\\textcircled{1}$ 硝基亮光清面漆",
+        "category": " Introduction"
+    },
+    {
+        "id": 565,
+        "chunk": "# a．基本配方 配方、生产工艺及性能见表3-7-24～表3-7-26。  \n\n表3-7-24 硝基亮光清面漆配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>组成（质量分数）/%</td><td>生产工艺</td></tr><tr><td>422马来酸酐树脂溶液（50%）</td><td>12</td><td rowspan=\"5\">按序投人，中速分散8～10min，搅拌均匀</td></tr><tr><td>硝化棉溶液（1/2s），醋酸丁酯：丁醇：二 甲苯：硝化棉=44：11：11：34</td><td>55.3</td></tr><tr><td>邻苯二甲酸二丁酯增塑剂</td><td>4</td></tr><tr><td>短油度豆油醇酸树脂（70%）</td><td>9</td></tr><tr><td>混合溶剂（二甲苯·醋酸丁酯：丁醇= 40:30:30)</td><td>18.2</td></tr><tr><td>流平剂</td><td>0.3</td><td>加人，高速分散均匀</td></tr><tr><td>消泡剂 醋酸丁酯</td><td>0.2 1</td><td>调整黏度</td></tr></table></body></html>  \n\n表3-7-25422马来酸酐树脂的溶解及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>组成（质量分数）/%</td><td>生产工艺</td></tr><tr><td>二甲苯</td><td>50</td><td>称量，投人分散缸</td></tr><tr><td>422马来酸酐树脂溶液</td><td>50</td><td>加入，中速搅拌15～20min，待溶解完全，200目过滤，备用</td></tr></table></body></html>  \n\n表3-7-26 硝基亮光清面漆性能指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项 目</td><td>指标</td></tr><tr><td>原漆外观</td><td>搅拌均匀，无硬块 500~1200</td><td>耐热性</td><td>无异常 ≤750</td></tr><tr><td>旋转黏度/mPa·s 细度/pm</td><td>≤10</td><td>挥发性有机物/（g/L) 苯含量/(g/L)</td><td>≤0.5</td></tr><tr><td>表干时间/min</td><td>≤10</td><td>三苯含量/%</td><td>≤40</td></tr><tr><td>实干时间/h</td><td>≤1</td><td>耐碱性</td><td>无异常</td></tr><tr><td>回黏性/级</td><td>≤2</td><td>耐污染性</td><td>无异常</td></tr><tr><td>铅笔硬度/HB</td><td>≤1</td><td>耐水性</td><td>无异常</td></tr><tr><td>光泽/%</td><td>≥70</td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 566,
+        "chunk": "# b.配方调整  \n\n$\\cdot$ 原料选择硝基亮光清面漆一般采用豆油脂肪酸树脂、硝化棉、增塑剂、混合溶剂、助剂等组成。一般使用1/4s或高黏度的硝化棉，预先制成 $25\\%\\sim30\\%$ 的溶液。树脂一般选用短油度豆油醇酸树脂，也有使用麻油树脂、椰子油醇酸树脂、羟基丙烯酸树脂的，光泽会更高；如果对耐黄变要求不高，加入一部分马来酸酐树脂或醛酮树脂，可以降低涂料的黏度，提高漆膜的丰满度，马来酸酐树脂和醛酮树脂可以用二甲苯溶解成 $50\\%$ 的溶液备用。添加增塑剂是为了提高漆膜的韧性，过去一般采用邻苯二甲酸二丁酯或邻苯二甲酸二辛酯，随着环保要求的提高，自前采用环氧大豆油等替代品。  \n\n$\\cdot$ 指标调整硝化棉和醇酸树脂是主要成膜物质，其比例决定漆膜的性能。醇酸树脂多、填料多，则填充性好，但是漆膜偏软，漆膜的耐热性能不好。配方中加入马来酸酐树脂是为了降低黏度，提高施工固含，达到提高丰满度，改善施工性能的目的。马来酸酐树脂加入最大的副作用是漆膜的耐黄变性变差。  \n\n硝基漆是挥发干燥型产品，因此尽量选用挥发性适中的溶剂，如醋酸丁酯和丁醇，应加人适量的慢干溶剂如BCS、丙二醇甲醚、丙二醇乙醚等。  \n\n·生产硝基漆的注意事项醇酸树脂和硝化棉溶液混合时要边搅拌边慢慢加人，再加人溶剂时，最好将几种溶剂预先混合后才加人；如果分开加，最好先加入真溶剂（能够溶解硝化棉的溶剂)，再加人其他溶剂（单独不能溶解硝化棉的溶剂)，以免硝化棉析出。硝化棉的溶剂极性较高，选用触变剂的时候，应做稳定性试验，一般选用二氧化硅，稳定性较好。  \n\n$\\textcircled{2}$ 硝基亚光清面漆  \n\na.硝基亚光清面漆配方、生产工艺及性能见表3-7-27和表3-7-28。  \n\n表3-7-27 硝基亚光清面漆配方及生产工艺  \n\n\n<html><body><table><tr><td>组 分</td><td>组成（质量分数）/%</td><td>生产 工艺</td></tr><tr><td>硝化棉溶液(1/2s)，醋酸丁酯：丁醇：二甲苯：硝 化棉=44:11:11:34</td><td>40</td><td rowspan=\"7\">依次加人，中速搅拌均匀 缓慢加人，高速分散15～18min</td></tr><tr><td>邻苯二甲酸二丁酯</td><td>2</td></tr><tr><td>短油度豆油酸醇酸树脂（70%）</td><td>-24</td></tr><tr><td>422马来酸酐树脂溶液（50%）</td><td>10</td></tr><tr><td>分散剂</td><td>0.1</td></tr><tr><td>混合溶剂（二甲苯：醋酸丁酯：丁醇=40：30：30）</td><td>22</td></tr><tr><td>消光粉 聚乙烯蜡</td><td>0.8</td></tr><tr><td>流平剂</td><td>1 0.1 加人，中速搅拌均匀</td></tr></table></body></html>  \n\n表3-7-28 硝基亚光清面漆性能指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>原漆外观</td><td>搅拌均匀，无硬块</td><td>耐热性</td><td>无异常</td></tr><tr><td>旋转黏度/mPa·s</td><td>500～1200</td><td>挥发性有机物/（g/L)</td><td>≤750</td></tr><tr><td>细度/μm</td><td>≤30</td><td>苯含量/%</td><td>≤0.5</td></tr><tr><td>表干时间/min</td><td>≤10</td><td>三苯含量/%</td><td>≤40</td></tr><tr><td>实干时间/h</td><td>≤1</td><td>耐碱性</td><td>无异常</td></tr><tr><td>回黏性/级</td><td>≤2</td><td>耐污染性</td><td>无异常</td></tr><tr><td>铅笔硬度/HB</td><td>≤1</td><td>耐水性</td><td>无异常</td></tr><tr><td>光泽/%</td><td>商定</td><td></td><td></td></tr></table></body></html>  \n\nb.配方调整一般选用 $1/2\\mathrm{s}$ 或更高黏度的硝化棉预制成 $30\\%$ 的溶液。硝基漆可以使用使用国产消光粉。硝基面漆的溶剂一般采用酯类、醇类、醇酯类、芳香烃类溶剂，一般不使用酮类，特别是环已酮等沸点较高的强溶剂，以免产生“咬底”等病。由于美国、欧盟等对邻苯二甲酸盐的限制使用，硝基漆增塑剂可用对苯二甲酸盐类或环氧大豆油类的增塑剂。  \n\nc.生产注意事项  \n$\\cdot$ 物料应该慢慢加人、混合。  \n$\\cdot$ 硝化棉的分散温度不能过高，否则会使产品贮存稳定性变差。  \n\n（2）硝基透明有色面漆  \n\n$\\textcircled{1}$ 硝基有色透明面漆硝基透明有色面漆由清漆和染料调配而成，按用户要求调色，因多为浅色，较易操作。喷涂有色面漆一般用于中低价木制品或家装。硝基透明有色亚光面漆配方、生产工艺及性能见表3-7-29和表3-7-30。  \n\n表3-7-29 硝基透明有色亚光面漆配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数）/%</td><td colspan=\"3\">生产工艺</td></tr><tr><td>二甲苯</td><td>8</td><td rowspan=\"11\">加人，中速搅拌均匀 慢慢加人，高速分散15min，至细度≤25μm 加人，调色，至符合标准样。200目过滤，包装</td></tr><tr><td>醋酸丁酯</td><td>14.04</td></tr><tr><td>422马来酸酐树脂溶液（50%）</td><td>8</td></tr><tr><td>豆油酸短油度醇酸树脂（70%）</td><td>23</td></tr><tr><td>邻苯二甲酸二辛脂(DOP)</td><td>4</td></tr><tr><td>硝化棉溶液（1/2s)，醋酸丁酯：丁醇：二</td><td>39</td></tr><tr><td>甲苯：硝化棉=44：11：11：34 消泡剂</td><td>0.2</td></tr><tr><td>流平剂</td><td>0.3</td></tr><tr><td>防沉浆</td><td>0.2</td></tr><tr><td>消光粉</td><td>1.5</td></tr><tr><td>棕色染料</td><td>0.34</td></tr><tr><td>红色染料</td><td>0.72</td></tr><tr><td>黄色染料</td><td>0.7</td></tr></table></body></html>  \n\n表3-7-30 硝基透明有色亚光面漆性能指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项 目</td><td>指标</td></tr><tr><td>原漆外观</td><td>搅拌均匀，无硬块， 颜色符合标准板</td><td>光泽/% 耐热性</td><td>商定 无异常</td></tr><tr><td>旋转黏度/mPa·s</td><td>500~1200</td><td>挥发性有机物/（g/L)</td><td>≤750</td></tr><tr><td>细度/μm</td><td>≤30</td><td>苯含量/%</td><td>≤0.5</td></tr><tr><td>表干时间/min</td><td>≤10</td><td>三苯含量/%</td><td>≤40</td></tr><tr><td>实干时间/h</td><td>≤1</td><td>耐碱性</td><td>无异常</td></tr><tr><td>回黏性/级</td><td>≤2</td><td>耐污染性</td><td>无异常</td></tr><tr><td>遮盖力/（g/m²）</td><td>≤100</td><td>耐水性</td><td>无异常</td></tr><tr><td>铅笔硬度/HB</td><td>≤1</td><td></td><td></td></tr></table></body></html>  \n\n$\\textcircled{2}$ 配方调整  \n\na.原料选择透明染料市售形式分染料溶液、色粉两种。染料溶液一般为厂家将金属络合染料溶解于溶剂中，以液体供应，一般染料浓度为 $30\\%$ ；色粉有染料色粉和透明氧化铁两种。  \n\nb.指标调整染料的透明度较透明氧化铁好。进口的色粉溶解后着色力、颜色鲜映性好。透明氧化铁的耐候性明显好于染料。染料一般用于室内装饰，透明氧化铁一般可以用于户外。  \n\n(3）硝基实色面漆按光泽分：硝基亚光实色面漆、硝基亮光实色面漆。按颜色分：硝基白面漆、硝基黑色面漆、硝基其他色面漆等。  \n\n$\\textcircled{1}$ 基本配方 硝基白色亚光面漆配方、生产工艺和性能见表3-7-31～表3-7-33。  \n\n$\\textcircled{2}$ 配方调整树脂可以选择豆油酸醇酸树脂，也可以选择椰子油醇酸树脂。钛白粉一般选用金红石型钛白粉。有时为了突出配方的耐黄变性，422马来酸酐树脂可以改用醛酮树脂。硝基亮光白面漆配方、生产工艺及性能见表3-7-34和表3-7-35。  \n\n表3-7-31 硝基白色亚光面漆配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数）/%</td><td>生产工艺</td></tr><tr><td>硝化棉溶液（1/2s)，醋酸丁酯：丁醇：二 甲苯：硝化棉=44：11：11：34</td><td>52</td><td rowspan=\"8\">依次加人，中速搅拌均匀</td></tr><tr><td>邻苯二甲酸二辛酯（DOP)</td><td>3</td></tr><tr><td>豆油酸短油度醇酸树脂（70%）</td><td>10.2</td></tr><tr><td>422马来酸酐树脂溶液（50%）</td><td>4</td></tr><tr><td>钛白色浆（60%）</td><td>24.2</td></tr><tr><td>流平剂</td><td>0.2</td></tr><tr><td>消泡剂</td><td>0.3</td></tr><tr><td>混合溶剂（二甲苯：醋酸丁酯：丁醇= 40:30:30)</td><td>4.5</td></tr><tr><td>消光粉</td><td>0.6</td></tr></table></body></html>  \n\n表3-7-32 白色浆的研磨配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数)/%</td><td>生产工艺</td></tr><tr><td>醇酸树脂</td><td>31.5</td><td rowspan=\"3\">按序加人，开动分散机搅拌5～8min，搅拌均匀</td></tr><tr><td>PMA</td><td>2.7</td></tr><tr><td>二甲苯</td><td>4.0</td></tr><tr><td>分散剂</td><td>1.8</td><td></td></tr><tr><td>钛白粉</td><td>60</td><td>慢慢加人，分散均匀</td></tr></table></body></html>  \n\n表3-7-33 硝基白色亚光面漆性能指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项 目</td><td>指标</td></tr><tr><td>原漆外观</td><td>搅拌均匀，无硬块</td><td>光泽/%</td><td>商定</td></tr><tr><td>旋转黏度/mPa·s</td><td>500～1200</td><td>耐热性</td><td>无异常</td></tr><tr><td>细度/μm</td><td>≤30</td><td>挥发性有机物/（g/L)</td><td>≤750</td></tr><tr><td>表干时间/min</td><td>≤10</td><td>苯含量/%</td><td>≤0.5</td></tr><tr><td>实干时间/h</td><td>≤1</td><td>三苯含量/%</td><td>≤40</td></tr><tr><td>回黏性/级</td><td>≤2</td><td>耐碱性</td><td>无异常</td></tr><tr><td>遮盖力/（g/m²）</td><td>≤100</td><td>耐污染性</td><td>无异常</td></tr><tr><td>铅笔硬度/HB</td><td>≤1</td><td>耐水性</td><td>无异常</td></tr></table></body></html>  \n\n表3-7-34 硝基亮光白面漆配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例 （质量分数）/%</td><td>原料及规格</td><td>比例 （质量分数）/%</td></tr><tr><td>白色浆(60%)</td><td>21</td><td>甲苯</td><td>3.87</td></tr><tr><td>短油度豆油醇酸树脂（70%）</td><td>14</td><td>硝化棉溶液（1/2s），醋酸丁酯：丁醇：</td><td>44</td></tr><tr><td>邻苯二甲酸二辛酯（DOP） 422马来酸酐树脂溶液（50%）</td><td>3 12</td><td>二甲苯：硝化棉=44：11：11：34</td><td></td></tr><tr><td>丁醇</td><td>2</td><td>消泡剂</td><td>0.13</td></tr></table></body></html>\n\n注：生产工艺为按序加人，中速搅拌均匀。200目过滤包装。  \n\n表3-7-35 硝基亮光白面漆性能指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项目</td><td>指标</td></tr><tr><td>原漆外观</td><td>搅拌均匀，无硬块</td><td>光泽/%</td><td>70～100</td></tr><tr><td>旋转黏度/mPa·s</td><td>500~1200</td><td>耐热性</td><td>无异常</td></tr><tr><td>细度/μm</td><td>≤30</td><td>挥发性有机物/(g/L)</td><td>≤750</td></tr><tr><td>表干时间/min</td><td>≤10</td><td>苯含量/%</td><td>≤0.5</td></tr><tr><td>实干时间/h</td><td>≤1</td><td>三苯含量/%</td><td>≤40</td></tr><tr><td>回黏性/级</td><td>≤2</td><td>耐碱性</td><td>无异常</td></tr><tr><td>遮盖力/（g/m²）</td><td>≤100</td><td>耐污染性</td><td>无异常</td></tr><tr><td>铅笔硬度/HB</td><td>≤1</td><td>耐水性</td><td>无异常</td></tr></table></body></html>  \n\n③配方调整硝基亮光白面漆一般选用椰子油短油度醇酸树脂、丙烯酸树脂等色泽较浅的树脂制备，产品的白度较好，耐黄变性也好。钛白粉一般选用金红石型钛白粉，遮盖力好。改性树脂，一般选用醛酮树脂而不是马来酸酐树脂，以保证耐黄变性。硝基亮光黑面漆配方、生产工艺及性能见表 $3-7-36\\sim$ 表3-7-38。  \n\n表3-7-36 硝基亮光黑面漆及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例 （质量分数）/%</td><td>原料及规格</td><td>比例 （质量分数）/%</td></tr><tr><td>422马来酸酐树脂溶液（50%）</td><td>18</td><td rowspan=\"3\">炭黑浆（16.5%） 硝化棉溶液（1/2s)</td><td>18</td></tr><tr><td>增塑剂（DOP)</td><td>2</td><td></td></tr><tr><td>甲苯</td><td>1.2</td><td>醋酸丁酯：丁醇：二甲苯：硝化棉= 58</td></tr><tr><td>醋酸丁酯</td><td>1.6</td><td>44+11:11:34</td><td></td></tr><tr><td>正丁醇</td><td>1</td><td>消泡剂</td><td>0.2</td></tr></table></body></html>\n\n注：生产工艺为按序加人，中速分散均匀。200目过滤包装。  \n\n表3-7-37 炭黑浆的研磨配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例(质量分数)/%</td><td>生产工 艺</td></tr><tr><td>聚酯树脂</td><td>46</td><td rowspan=\"4\">按序加人，开动分散机搅拌5～8min，搅拌均匀</td></tr><tr><td>PMA</td><td>12.3</td></tr><tr><td>二甲苯</td><td>12.3</td></tr><tr><td>分散剂</td><td>12.9</td></tr><tr><td>炭黑</td><td>16.5</td><td>慢慢加人，分散均匀。研磨至细度合格</td></tr></table></body></html>  \n\n表3-7-38 硝基亮光黑面漆性能指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项 目</td><td>指标</td></tr><tr><td>原漆外观：黑色黏稠液、无机械杂质 旋转黏度/mPa·s 固体含量/% 细度/μm</td><td>搅拌均匀，无硬块 800～2500 ≥35 ≤30</td><td>光泽/% 耐热性 挥发性有机物/（g/L） 苯含量/%</td><td>70～100 无异常 ≤750 ≤0.5</td></tr></table></body></html>  \n\n$\\textcircled{4}$ 配方调整硝基黑色亮光漆可以选用豆油酸短油度树脂、麻油短油度醇酸树脂、椰子油短油度醇酸树脂等制备。炭黑一般选用高色素炭黑，遮盖力强。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 567,
+        "chunk": "# 2.聚氨酯面漆  \n\n聚氨酯面漆可以分为PU透明清面漆、PU透明有色面漆、PU实色面漆；按光泽分为PU亮光面漆、PU亚光面漆。  \n\n（1）PU亮光面漆亮光面漆可以分为PU亮光实色面漆、PU亮光清面漆。  \n\n$\\textcircled{1}$ PU亮光清面漆PU亮光清面漆配方、生产工艺及性能见表3-7-39和表3-7-40。  \n\na.原料选择亮光清面漆选用的树脂通常为 $C_{8}\\sim C_{9}$ 的合成脂肪酸醇酸树脂、丙烯酸树脂单独使用或搭配使用，也有选用麻油或麻油酸醇酸树脂、豆油酸短油度树脂、椰子油短油度醇酸树脂等。  \n\n表3-7-39PU亮光清面漆配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>组成（质是分数）/%</td><td>生产工艺</td></tr><tr><td>合成脂肪酸树脂（75%） 环己酮</td><td>66 1</td><td rowspan=\"3\">按序投人，中速分散5～10min</td></tr><tr><td>醋酸丁酯</td><td>2</td></tr><tr><td>二甲苯</td><td>3</td></tr></table></body></html>  \n\n表3-7-40PU亮光清面漆性能指标  \n\n\n<html><body><table><tr><td>检验项目</td><td>性能指标</td><td>检验项目</td><td>性能指标</td></tr><tr><td>外观</td><td>水白色至浅黄色透明黏 稠液体，无机械杂质</td><td>耐干热性/级 耐酸性</td><td>≤2 无异常</td></tr><tr><td>细度/μm</td><td>≤10</td><td>耐碱性</td><td>无异常</td></tr><tr><td>固体含量/%</td><td>65±2</td><td>耐醇性</td><td>无异常</td></tr><tr><td>表干/min</td><td>≤30</td><td>耐污染性</td><td></td></tr><tr><td>实干/h</td><td>≤24</td><td>醋</td><td>无异常</td></tr><tr><td>附着力/级</td><td>1</td><td>茶</td><td>无异常</td></tr><tr><td>光泽/%</td><td>95</td><td>有害物质限量</td><td>符合GB18581</td></tr><tr><td>铅笔硬度/H</td><td>≥1</td><td></td><td></td></tr></table></body></html>  \n\nb.指标调整主漆选用两个混容性好的树脂搭配，如合成脂肪酸醇酸树脂和羟基丙烯酸树脂。丙烯酸树脂提供良好的干速和光泽，合成脂肪酸树脂提供良好的丰满度；也可以选择饱和聚酯树脂，丰满度和干燥性俱佳，只是成本较高。流平剂建议选用高分子聚合物流平剂和有机硅流平剂搭配，既可以有良好的短波流平，也可以有较好的长波流平。催于剂是为了更好地提高反应速率，加量要合适，过多则容易产生针孔等漆膜病，过少起不到加速干燥的作用。固化剂和树脂的比例以异氰酸根（—NCO）和羟基（一OH）的比例确定，一般以异氰酸根：羟基 $=(1{\\sim}1.2):1$ （重量比）为宜。耐黄变的亮光漆一般采用丙烯酸树脂体系、不黄变的HDI、IPDI固化剂。  \n\nc.技术难点针孔和暗泡的原因基本一致，都是由于干燥的不均匀引起，但解决的方式不同：夏季出现针孔和暗泡，最直接的解决方法是施工时加人挥发较慢的溶剂或适量的消泡剂；暗泡出现在低温时，最有效的方法是使用较为快干的固化剂。不同表面张力的助剂可以改善溶剂的挥发，减弱上述病的发生。生产亮光清漆时，分散时间一定要充分，否则容易造成物料分散不均匀而引起漆病。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 568,
+        "chunk": "# $\\textcircled{2}$ PU亮光实色面漆  \n\na，PU亮光白面漆配方、生产工艺及性能见表3-7-41和表3-7-42。  \n\n表3-7-41PU亮光白面漆配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数）/%</td><td>原料及规格</td><td>比例(质量分数)/%</td></tr><tr><td>白色浆（60%)</td><td>53.3</td><td>醋酸丁酯</td><td>2.3</td></tr><tr><td>羟基丙烯酸树脂（65%）</td><td>39.8</td><td>消泡剂</td><td>0.5</td></tr><tr><td>PMA</td><td>3.7</td><td>流平剂</td><td>0.4</td></tr></table></body></html>\n\n注：生产工艺为按序投人，中速搅拌 $15\\cdots20\\mathrm{min}$ ，200目过滤。检验包装。  \n\n表3-7-42PU亮光白面漆性能指标  \n\n\n<html><body><table><tr><td>项目</td><td>指标</td><td>项 目</td><td>指标</td></tr><tr><td>光泽/%</td><td>95~100</td><td>游离甲苯二异氰酸酯（TDI/%</td><td>≤0.7</td></tr><tr><td>漆膜外观</td><td>平整光滑</td><td>可溶性铅/(mg/L)</td><td>≤90</td></tr><tr><td>在容器中状态</td><td>搅拌后均匀无硬块</td><td>可溶性镉/(mg/L)</td><td>≤75</td></tr><tr><td>细度/μm</td><td>≤20</td><td>可溶性铬/(mg/L)</td><td>≤60</td></tr><tr><td>旋转黏度/mPa·s</td><td>500~1500</td><td>可溶性汞/(mg/L)</td><td>≤60</td></tr><tr><td>固体含量/%</td><td>≥65</td><td>耐干热性</td><td>≤2</td></tr><tr><td>遮盖力/(g/m²)</td><td>≤80</td><td>耐磨性/g</td><td>≤0.035</td></tr><tr><td>表干时间/min</td><td>≤30</td><td>耐水性</td><td>24h无异常</td></tr><tr><td>实干时间/h</td><td>≤24</td><td>耐碱性</td><td>无异常</td></tr><tr><td>附着力</td><td>≤1</td><td>耐醇性</td><td>无异常</td></tr><tr><td>铅笔硬度(擦伤)</td><td>≥F</td><td>耐醋污染性</td><td>无异常</td></tr><tr><td>光泽(60°)/%</td><td>90~100</td><td>耐茶污染性</td><td>无异常</td></tr><tr><td>挥发性有机化合物（VOC）含量/ (g/L)</td><td>≤600</td><td>贮存稳定性</td><td>无异常</td></tr><tr><td>苯含量/%</td><td>≤0.5</td><td>耐黄变性E*(如标识耐黄变)</td><td>≤3</td></tr><tr><td>甲苯和二甲苯总含量/%</td><td>≤40</td><td></td><td></td></tr></table></body></html>  \n\n$\\cdot$ 原料选择亮光白面漆用树脂一般选用椰子油短油度醇酸树脂、合成脂肪酸醇酸树脂、羟基丙烯酸树脂、饱和聚酯树脂等色泽较浅的材料。固化剂可以选择TDI加成物、TDI三聚体、HL三聚体、HDI三聚体及它们的混合物。  \n\n$\\cdot$ 指标调整固化剂选择视主剂所用树脂而定。如果选椰子油或麻油短油度醇酸树脂，固化剂应选用TDI加成物固化剂，否则丰满度不好；如果选用合成脂肪酸树脂或饱和聚酯树脂，可以选择TDI三聚体和加成物混合固化剂。耐黄变体系一般主剂选用合成脂肪酸或饱和聚酯树脂，采用TDI三聚体和HDI三聚体的混合固化剂；也可以选择HL型的固化剂搭配HDI三聚体固化剂，耐黄变更好。固化剂和涂料的配比以异氰酸根和羟基的比例确定。一般以当量比异氰酸根：羟基 $=1:1$ 为宜。固化剂多，硬度高，干燥快，但漆膜较脆；固化剂少，硬度较低，干燥略慢，但韧性好。  \n\n$\\cdot$ 技术难点针孔和暗泡是亮光白漆较易出现的弊病。针孔通过调整溶剂解决；暗泡需通过较好的干燥平衡的配方解决。  \n\nb.配方调整PU亮光黑面漆树脂一般选用麻油短油度醇酸树脂、豆油酸短油度醇酸树脂或几种树脂拼用；如果要求丰满度更高，可以选用合成脂肪酸、热固性丙烯酸树脂或两种树脂拼用。固化剂可以选择TDI加成物或TDI加成物与三聚体拼用，提高干燥速度。炭黑一般选用高色素炭黑，遮盖力强。PU亮光黑面漆配方、生产工艺及性能见表3-7-43和表3-7-44。  \n\n表3-7-43PU亮光黑面漆配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例(质量分数）/%</td><td>生产工艺</td></tr><tr><td>麻油短油度醇酸树脂（50%） 流平剂 消泡剂</td><td>54.4 0.2</td><td>按序加人，中速搅拌均匀，200目过滤包装</td></tr></table></body></html>  \n\n表3-7-44PU亮光黑面漆性能指标  \n\n\n<html><body><table><tr><td>检验项目</td><td>性能指标</td><td>检验项目</td><td>性能指标</td></tr><tr><td>旋转黏度（25C）/mPa·s</td><td>100～150 搅拌后均</td><td>苯含量/% 甲苯和二甲苯总含量/%</td><td>≤0.5 ≤40</td></tr><tr><td>在容器中状态</td><td>匀无硬块</td><td>游离甲苯二异氰酸酯(TDI)/%</td><td>≤0.7</td></tr><tr><td>细度/μm</td><td>0~20</td><td>可溶性铅/（mg/L）</td><td>90</td></tr><tr><td>漆膜外观</td><td>平滑，柔和</td><td>可溶性镉/（mg/L）</td><td>75</td></tr><tr><td>光泽（60°）/%</td><td>40~60</td><td>可溶性铬/（mg/L)</td><td>60</td></tr><tr><td>漆膜外观</td><td>平滑，柔和</td><td>可溶性汞/（mg/L)</td><td>60</td></tr><tr><td>固体含量</td><td>≥50</td><td>耐干热性/级</td><td>≤2</td></tr><tr><td>遮盖力/（g/m²）</td><td>≤30</td><td>耐磨性</td><td>≤0.05</td></tr><tr><td>表于干燥时间/min</td><td>≤30</td><td>耐水性</td><td>无异常</td></tr><tr><td>实干干燥时间/h</td><td>≤24</td><td>耐碱性</td><td>无异常</td></tr><tr><td>附着力</td><td>≤1</td><td>耐醇性</td><td>无异常</td></tr><tr><td>铅笔硬度(擦伤）</td><td>≥F</td><td>耐醋污染性</td><td>无异常</td></tr><tr><td>光泽（60°）/%</td><td>90～100</td><td>耐茶污染性</td><td>无异常</td></tr><tr><td>挥发性有机化合物（VOC)含量/（g/L）</td><td>≤600</td><td></td><td></td></tr><tr><td></td><td></td><td>贮存稳定性</td><td>无异常</td></tr></table></body></html>  \n\n(2）PU亚光面漆PU亚光面漆分为PU亚光透明清面漆、PU亚光透明有色清面漆、PU亚光实色面漆。  \n\n一般来说，称五分光以上的亚光面漆为半光面漆，三分至五分光泽的面漆为亚光面漆，三分光以下光泽的面漆为无光面漆。以下配方均以五分光为例说明。  \n\n$\\textcircled{1}$ PU亚光清面漆按光泽分PU半光清面漆、PU亚光清面漆、PU无光清面漆。PU亚光清面漆各项指标见表3-7-45～表3-7-48。  \n\n表3-7-45PU亚光清面漆配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例(质量分数)/%</td><td>生产工艺</td></tr><tr><td>豆油酸短油度醇酸树脂（60%） PMA 醋酸丁酯</td><td>33.2 4 8</td><td>按序投人，中速搅拌均匀</td></tr><tr><td>分散剂 玻璃粉</td><td>0.3 5</td><td>慢慢加人，转高速分散10～15min</td></tr><tr><td>豆油酸短油度醇酸树脂（60%） 消泡剂</td><td>30 0.2</td><td>加人，中速搅拌均匀</td></tr><tr><td>聚乙烯蜡 消光粉</td><td>1 3</td><td>慢慢加入，高速分散15～20min，测细度≤35um</td></tr><tr><td>聚酰胺蜡</td><td>3</td><td>投人，高速分散5～10min</td></tr><tr><td>硝化棉溶液（1/2s)，醋酸丁酯：丁醇：二 甲苯：硝化棉=44：11：11：34</td><td>10</td><td rowspan=\"3\">投入，中速搅拌均匀。抽样检验 200目过滤包装</td></tr><tr><td>流平剂</td><td>0.3</td></tr><tr><td>醋酸丁酯</td><td>2</td></tr></table></body></html>  \n\na.原料选择树脂一般选用豆油酸短油度醇酸树脂、椰子油短油度醇酸树脂、饱和聚酯树脂。改性树脂主要是硝化棉、氯醋树脂、醛酮树脂、醋酸丁酸纤维素（CAB)。亚粉一般选择GRACE的亚粉，如ED系列、C906/C907、7000或DEGUSSA的OK系列。国产的亚粉也可使用。蜡粉一般选择聚乙烯蜡或氟改性的蜡。溶剂一般选用二甲苯、醋酸丁酯、环己酮、PMA等。功能性填料选用玻璃粉。固化剂选用三聚体和加成物的混合物，增加消光能力，减少亚粉用量，提高产品的透明度。  \n\n表3-7-46PU亚光清面漆性能指标  \n\n\n<html><body><table><tr><td>项目</td><td>性能指标</td><td>项目</td><td>性能指标</td></tr><tr><td>原漆状态 细度/μm 光泽/% 漆膜外观 固体含量/% 表干干燥时间/min</td><td>搅拌后均匀无硬块 ≤35 45~55 平滑、柔和 ≥48 ≤30 ≤24</td><td>苯含量/% 甲苯和二甲苯总含量/% 游离甲苯二异氰酸酯(TDI)/% 耐干热性 耐碱性 耐醇性 耐醋污染性 耐茶污染性</td><td>≤0.05 ≤40 ≤0.7 24h无异常 无异常 无异常 2h无异常 2h无异常 无异常</td></tr></table></body></html>  \n\n表3-7-47PU亚光清面漆固化剂  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例(质量分数）/%</td><td>原料及规格</td><td>比例（质量分数）/%</td></tr><tr><td>TDI加成物（60%）</td><td>62.4</td><td>醋酸丁酯</td><td>9.6</td></tr><tr><td>TDI三聚体（50%）</td><td>22</td><td>二甲苯</td><td>6</td></tr></table></body></html>\n\n注：生产工艺为加人，通 $N_{z}$ ；中速搅拌均匀，200目过滤包装。  \n\n表3-7-48PU亚光清面漆固化剂性能指标  \n\n\n<html><body><table><tr><td>项目</td><td>性能指标</td></tr><tr><td>外观（目测）</td><td>透明液体、无机械杂质</td></tr><tr><td>色泽Pt-Co号</td><td>≤150</td></tr><tr><td>黏度(涂-4杯)/s</td><td>10~30</td></tr><tr><td>NCO含量/%</td><td>7~8</td></tr><tr><td>不挥发物含量/%</td><td>50±2</td></tr><tr><td>游离TDI含量/%</td><td>≤1.8</td></tr></table></body></html>  \n\nb.配方调整PU亚光清面漆树脂一般选用豆油或豆油酸短油度醇酸树脂、椰子油醇酸树脂或饱和聚酯树脂。椰子油树脂一般用于耐黄变体系。硝化棉、氯醋树脂的加入可以改善体系的溶剂释放性，提高消光能力，改善漆膜性能。蜡粉改善漆膜的手感和滑度，提高漆膜的抗刮伤能力，同时提高漆膜的防水性能，但加入量过大会影响漆膜的透明性，一般加人量为 $1\\%\\sim3\\%$ 。防沉剂的作用有两个：一是改善产品的贮存稳定性，防止填料的沉降；二是改善产品施工时的立面喷涂性能，加人量要兼顾，一般为 $1\\%\\sim3\\%$ 。多则平面流平变差，少则立面喷涂容易流挂。玻璃粉的加入能增加漆膜的硬度，抵御软物刮伤的能力，但必须和蜡粉配合使用才能达到最佳效果，加入量一般在 $5\\%\\sim10\\%$ 。固化剂和涂料的配比一般设定为 $0.5:1$ ，要保证当量比异氰酸根：羟基 $=(0,8\\sim1)\\ :1$ ，需通过调整固化剂的固含来满足。耐黄变的亚光清主要使用在浅色底材上。对涂料的要求不仅耐黄变性能较好，而且涂料本身的颜色也要浅。一般采用丙烯酸体系制备，采用HDI系列固化剂。  \n\nc.技术难点消光粉的选择很关键，用不同表面处理方法制取的亚粉折射率不同，表现出来的透明度不同。固化剂的选择和混合比例直接影响产品的施工性能及装饰性能。亚光清低温“发花”实际上是一种局部的起皱现象。因为起皱，所以亮亚不匀形成“发花”。可以换用挥发较快的稀释剂，也可以通过调整配方，拼用TDI三聚体等较为快干的固化剂解决。当然解决“发花”的最有效方法是使用低温烘烤设备，使漆膜干燥条件变得可控及一致。  \n\nd.PU亚光清面漆的施工注意事项PU亚光清面漆一般以喷涂施工为主。如果要刷涂，则需使用较为慢干的稀释剂。涂膜厚度要适中，一般干膜控制在 $20\\sim30\\mu\\mathrm{m}$ 。有些家具厂一味想通过厚涂面漆改善涂装效果，不仅不能达到目的，可能会引起如成本上升、附着力变差、开裂等病，实在是得不偿失。施工时，尽量均匀一致，否则容易亮亚不匀，影响涂装效果。  \n\n$\\textcircled{2}$ PU透明亚光有色清面漆  \n\na.基本配方PU透明亚光有色清面漆配方、生产工艺及性能见表3-7-49和表3-7-50。  \n\n表3-7-49PU透明亚光有色清面漆配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数）/%</td><td>生产工艺</td></tr><tr><td>豆油酸短油度醇酸树脂（60%） 醋酸丁酯 二甲苯 分散剂</td><td>44 8 1.2 0.2</td><td>按序投人，中速搅拌均匀</td></tr><tr><td>消光粉 豆油酸短油度醇酸树脂（60%）</td><td>3.5 20</td><td>慢慢投人，待粉料完全混人，高速搅拌15～ 20min至细度合格</td></tr><tr><td>防沉浆（30%） 消泡剂 流平剂 硝化棉溶液（1/2s），醋酸丁酯：丁醇：二</td><td>1.5 0.3 0.3</td><td>按序加入，中速搅拌均匀</td></tr><tr><td>甲苯：硝化棉=44：11：11：34 PMP</td><td>11 3</td><td></td></tr><tr><td>醋酸丁酯 棕色染料</td><td>5.3 0.3</td><td></td></tr></table></body></html>  \n\n表3-7-50PU透明亚光有色清面漆性能指标  \n\n\n<html><body><table><tr><td>检验项目</td><td>性能指标</td><td>检验项目</td><td>性能指标</td></tr><tr><td>原漆状态 细度/μm 光泽（60°)/% 漆膜外观：平滑，柔和 旋转黏度/mPa·s</td><td>搅拌后均匀无硬块 ≤30 45~55 颜色符合标准版 1500~3000 40~50 ≤30 ≤24</td><td>苯含量/% 甲苯和二甲苯总含量/% 游离甲苯二异氰酸酯（TDI/% 耐干热性/级 耐磨性/g 耐水性 耐碱性 耐醇性</td><td>≤0.50 ≤40 ≤0.7 ≤2 ≤0.05 无异常 无异常 无异常</td></tr></table></body></html>  \n\nb.配方调整PU透明亚光有色清面漆一般由亚光清漆基料和络合染料组成，一般浅色的产品染料浓度在 $3\\%\\sim5\\%$ ，较深色的产品染料浓度在 $5\\%\\sim8\\%$ 。常用的色精有黄、红、黑、棕等几种色，就可以调出多种颜色产品。  \n\nPU亚光有色透明面漆的施工方式为喷涂。  \n\n$\\textcircled{3}$ PU亚光实色面漆PU亚光实色面漆分白色、黑色和其他彩色实色亚光漆。  \n\na.基本配方PU亚光白面漆配方、生产工艺及性能见表 $3-7-51\\sim$ 表3-7-54。  \n\n表3-7-51PU亚光白面漆配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数）/%</td><td>生产工艺</td></tr><tr><td>钛白浆（65%）</td><td>45 35</td><td rowspan=\"4\">按序加人，中速分散8～10min，使其均匀</td></tr><tr><td>短油度豆油酸醇酸树脂（60%） 二甲苯</td><td>4</td></tr><tr><td>醋酸丁酯</td><td>3</td></tr><tr><td>消泡剂</td><td>0.3</td></tr><tr><td>聚乙烯蜡</td><td>1</td><td>缓慢加人，边揽边加，高速分散15～20min</td></tr><tr><td>消光粉 流平剂BYK310</td><td>8 0.3</td><td></td></tr><tr><td>有机锡T-12（10%）</td><td>0.3</td><td>加人，中速搅匀。过滤包装</td></tr></table></body></html>  \n\n表3-7-52PU亚光白面漆的性能指标  \n\n\n<html><body><table><tr><td>检验项目</td><td>性能指标</td><td>检验项目</td><td>性能指标</td></tr><tr><td>外观</td><td>水白至浅黄色透明黏稠 液体，无机械杂质</td><td>耐干热性/级 耐酸性</td><td>≤2</td></tr><tr><td>细度/μm</td><td>≤30</td><td>耐碱性</td><td>无异常 无异常</td></tr><tr><td>固体含量/%</td><td>58±2</td><td>耐醇性</td><td>无异常</td></tr><tr><td>表干/min</td><td>≤30</td><td>耐污染性</td><td></td></tr><tr><td>实干/h</td><td>≤24</td><td>醋</td><td>无异常</td></tr><tr><td>附着力(划格法)/级</td><td>≤1</td><td>茶</td><td>无异常</td></tr><tr><td>光泽/%</td><td>商定</td><td>有害物质限量</td><td>符合GB18581</td></tr><tr><td>铅笔硬度/H</td><td>≥1</td><td></td><td></td></tr></table></body></html>  \n\n表3-7-53PU亚光白面漆固化剂配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例(质量分数)/%</td><td>原料及规格</td><td>比例(质量分数）/%</td></tr><tr><td>TDI加成物(60%) 醋酸丁酯</td><td>83 16.7</td><td>脱水剂</td><td>0.3</td></tr></table></body></html>\n\n注：生产工艺为按序加入分散缸，通 $N_{2}$ ；中速搅拌均匀。  \n\n表3-7-54PU亚光白面漆固化剂性能指标  \n\n\n<html><body><table><tr><td>检验项目</td><td>性能指标</td><td>检验项目</td><td>性能指标</td></tr><tr><td>外观</td><td>水白至浅黄色透明黏稠液体，无机械杂质</td><td>固体含量/%</td><td>50±2</td></tr><tr><td>细度</td><td>≤10</td><td>F-NCO/%</td><td>≤1.8</td></tr><tr><td>NCO/%</td><td>7~8</td><td></td><td></td></tr></table></body></html>  \n\n$\\cdot$ 原料选择树脂一般选用豆油酸短油度醇酸树脂、椰子油短油度醇酸树脂或饱和聚酯树脂、羟基丙烯酸树脂。改性树脂一般选用氯醋树脂、CAB。钛白粉一般选用金红石型钛白粉，如杜邦的R706、 $\\mathbb{R902}$ 等；亚粉可以选用国产亚粉或进口亚粉。助剂选用有机硅消泡剂、流平剂和有机锡催干剂。固化剂可以选择TDI加成物或TDI加成物与TDI三聚体的混合物。  \n\n$\\cdot$ 配方调整豆油酸树脂耐黄变性一般，颜色深，一般用于不耐黄变体系；椰子油醇酸树脂、饱和聚酯、丙烯酸树脂颜色浅、耐黄变性好，一般用于要求耐黄变如白色体系。普通的亚光实色面漆，固化剂用TDI加成物或TDI加成物与三聚体的混合物可以满足需要。浅色亚光面漆一般采用耐黄变体系，固化剂选用TDI三聚体与HDI加成物或三聚体的混合物作固化剂，达到耐黄变要求。与PU亚光清面漆类似，配方中加入一定的聚乙烯等蜡粉可以改善漆膜的耐刮伤和手感。  \n\n·技术难点 色浆的制备和稳定性是色漆与调色的难点。  \n\nb.配方调整PU亚光黑面漆一般选用豆油酸醇酸树脂，改性树脂可以采用硝化棉、氯醋树脂等。炭黑一般选用高色素炭黑研磨成色浆备用，色浆的树脂与涂料的主体树脂相容性要好。PU亚光黑面漆配方、生产工艺及性能见表3-7-55和表3-7-56。  \n\n表3-7-55PU亚光黑面漆配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数）/%</td><td>生产工艺</td></tr><tr><td>二甲萃 醋酸丁酯 流平剂 消泡剂 分散剂</td><td>5.5 3.2 0.3 0.2 0.2</td><td>按序加人，中速搅拌均匀</td></tr><tr><td>聚乙烯蜡 消光粉 醋酸丁酯</td><td>0.8 4 0.6</td><td>加人，高速分散15～20min</td></tr><tr><td>炭黑浆（16.5%） 硝化棉溶液（1/2s），醋酸丁酯：丁醇：二</td><td>34</td><td rowspan=\"3\">加人，中速搅拌均匀</td></tr><tr><td>甲苯：硝化棉=44：11：11：34</td><td>9</td></tr><tr><td>醋酸丁酯</td><td>3</td></tr></table></body></html>  \n\n表3-7-56PU亚光黑面漆性能指标  \n\n\n<html><body><table><tr><td>项目</td><td>性能指标</td><td>项目</td><td>性能指标</td></tr><tr><td>旋转黏度（25℃）/mPa·s 在容器中状态 细度/μm 漆膜外观 光泽（60°）/% 固体含量/% 遮盖力/（g/m²）</td><td>1000~3000 搅拌后均匀无硬块 0~40 平滑，柔和 40~60 ≥40 ≤30</td><td>甲苯和二甲苯总含量/% 游离甲苯二异氰酸酯（TDI)/% 可溶性铅/（mg/L） 可溶性镉/(mg/L) 可溶性铬/(mg/L) 可溶性汞/(mg/L) 耐干热性/级 耐磨性/g 耐水性</td><td>≤40 ≤0.7 ≤90 ≤75 ≤60 ≤60 ≤2级 ≤0.05 无异常</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 569,
+        "chunk": "# 3.地板漆  \n\n目前市售的木质地板大多是在工厂涂装好的，使用时直接铺砌安装。所用涂料大多是UV涂料。部分家庭装修仍会使用地板漆，一般为PU聚氨酯涂料，分高光和亚光两种。施工方式多为刷涂，在素身地板铺砌、磨平、清洁后涂布。  \n\n亮光地板漆和前面所述PU亮光清面漆大致相同，但是，由于施工方式为刷涂，所以配方体系里应该加人一定的抑泡剂。  \n\n单组分潮固化型地板漆，树脂类型为聚醚和TDI的预聚物。一般将市售产品分装或加入消泡剂搅拌均匀包装出售。  \n\n亚光地板漆和一般的亚光清配方体系类似，但是由于使用于地板，对使用的树脂和相应固化剂的要求会更高且会加人一些抗划伤助剂，如蜡粉等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 570,
+        "chunk": "# （1）基本配方 基本配方及性能见表3-7-57～表3-7-60。  \n\n表3-7-57PU亚光地板漆配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数）/%</td><td>生产工艺</td></tr><tr><td>短油度豆油酸醇酸树脂（60%） 二甲苯 醋酸丁酯 分散剂</td><td>43 1.4 6</td><td>按序投入，中速搅拌均匀</td></tr><tr><td>聚乙烯蜡 消光粉 短油度豆油醇酸树脂（60%）</td><td>0.2 1.5 5.5 20</td><td>投入，高速分散10～15min，至细度合格</td></tr><tr><td>防沉浆（30%） 硝化棉溶液（0.5s，30%）</td><td>1.5 11</td><td></td></tr><tr><td>流平剂 消泡剂</td><td>0.3 0.3</td><td>加人，中速搅拌均匀，至细度合格，过滤包装</td></tr></table></body></html>  \n\n表3-7-58PU亚光地板漆性能指标  \n\n\n<html><body><table><tr><td>检验项目</td><td>性能指标</td><td>检验项目</td><td>性能指标</td></tr><tr><td>原漆状态 细度/μm 光泽（60°)/% 漆膜外观 旋转黏度/mPa·s</td><td>搅拌后均匀无硬块 ≤30 45~55 平滑，柔和 1500~3000 40~50</td><td>苯含量/% 甲苯和二甲苯总含量/% 游离甲苯二异氰酸酯(TDI)/% 耐干热性/级 耐磨性/g 耐水性 耐碱性</td><td>≤0.50 ≤40 ≤0.7 ≤2 ≤0.05 无异常 无异常</td></tr></table></body></html>  \n\n表3-7-59 地板漆固化剂配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例(质量分数）/%</td><td>原料及规格</td><td>比例(质量分数)/%</td></tr><tr><td>TDI加成物（60%）</td><td>70</td><td>醋酸丁酯</td><td>29.5</td></tr><tr><td>TDI三聚体（50%）</td><td>10</td><td>脱水剂</td><td>0.5</td></tr></table></body></html>\n\n注：生产工艺为加人分散缸，通 $N_{2}$ ；中速揽拌均匀。200自过滤包装。  \n\n表3-7-60地板漆固化剂性能指标  \n\n\n<html><body><table><tr><td>项目</td><td>性能指标</td><td>项目</td><td>性能指标</td></tr><tr><td>外观（目测）</td><td>透明液体、无</td><td>不挥发物含量/%</td><td>48±3</td></tr><tr><td></td><td>机械杂质</td><td>游离TDI含量/%</td><td>≤1.8</td></tr><tr><td>色泽Pt-Co号 NCO含量/%</td><td>≤150 6~8</td><td>黏度(涂-4杯）/s</td><td>10~30</td></tr></table></body></html>  \n\n(2）配方调整地板漆对耐刮伤和耐磨耗的要求较高，漆膜的韧性和硬度要高。选用的主体树脂柔韧性要好，羟值较高，一般在 $3\\%$ 以上，固化剂的固含不能太低，否则交联度低硬度不够。由于地板漆一般涂膜较厚，因此要选择透明度较好的消光粉，以免漆膜浑浊。对  \n\n于刷涂的地板漆，可加人抑泡剂，以免刷涂时起泡。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 571,
+        "chunk": "# 4.聚氨酯美术漆  \n\n美术漆是具有特殊装饰效果的涂料。20世纪90年代初甚为流行。常用于木器涂装的产品有：闪光漆、仿皮漆（也叫砂面漆)、锤纹漆、贝母漆、裂纹漆等。  \n\n(1）基本配方聚氨酯仿皮漆配方、生产工艺及性能见表3-7-61和表3-7-62。  \n\n表3-7-61 聚氨酯仿皮漆配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例数质量</td><td>生产工艺</td><td>原料及规格</td><td>分例数质</td><td>生产工艺</td></tr><tr><td>麻油短油度醇酸树脂（50%）</td><td>33.9</td><td></td><td>流平剂</td><td>0.2</td><td></td></tr><tr><td>防沉浆（30%）</td><td>2.6</td><td></td><td>微粉蜡</td><td>6.4</td><td></td></tr><tr><td>防沉浆（10%，膨润土浆）</td><td>1.3</td><td></td><td>滑石粉（1250目)</td><td>15.8</td><td></td></tr><tr><td>二甲苯</td><td>3.7</td><td></td><td>醋酸丁酯</td><td>1.1</td><td></td></tr><tr><td>有机锡T-12溶液(10%)</td><td>0.2</td><td></td><td>炭黑浆（16.5%)</td><td>34</td><td></td></tr></table></body></html>  \n\n表3-7-62 聚氨酯仿皮漆性能指标  \n\n\n<html><body><table><tr><td>项目</td><td>性能指标</td><td>项目</td><td>性能指标</td></tr><tr><td>旋转黏度/mPa·s 在容器中状态 漆膜外观 固体含量/% 遮盖力/（g/m²）</td><td>1000~3000 搅拌后均匀无硬块 符合标准板 ≥60 ≤30 ≤30</td><td>可溶性铅/(mg/L) 可溶性镉/（mg/L) 可溶性铬/(mg/L) 可溶性汞/(mg/L) 耐干热性/级 耐磨性/g 耐水性</td><td>90 75 60 60 ≤2 ≤0.05 无异常 无异常</td></tr></table></body></html>  \n\n(2）配方调整仿皮漆一般为亚光效果。树脂可以选择豆油酸短油度醇酸树脂、麻油短油度醇酸树脂。蜡粉粗细决定了砂面效果，通常选一种蜡粉或两种搭配使用。仿皮漆的耐刮伤很好，可用于办公台的涂装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 572,
+        "chunk": "# 5.紫外光固化涂料（简称UV涂料）  \n\nUV涂料是木用涂料领域发展最快的品种之一。在木家具上的使用也越来越受到青睐。它的固化速率快，使用高速生产线，效率高。涂膜性能优良，具有较好的抗刮伤、抗溶剂、抗沾污的性质。  \n\nUV涂料目前最常用的面漆产品是UV辊涂亚光清面漆(1）UV辊涂亚光清面漆UV辊涂亚光清面漆配方、生产工艺及性能见表3-7-63和表3-7-64。(2）配方调整  \n\n①原料选择树脂可以选用环氧丙烯酸树脂、聚氨酯丙烯酸树脂。单体可以选单官能度、双官能度、三官能度、六官能度的丙烯酸单体。亚光粉可选用较粗粒径的消光粉，如GRACE的ED3、C807等。助剂选用无溶剂的流平剂和消泡剂。光引发剂主要使用的是自由基型光引发剂，一般选用裂解型和夺氢型搭配使用。  \n\n表3-7-63UV辊涂亚光清面漆配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数）/%</td><td>生产工艺</td></tr><tr><td>TMPTA DPGDA 光引发剂二苯甲酮 光引发剂184 双酚A环氧丙烯酸树脂 聚氨酯丙烯酸树脂</td><td>13 21.7 3 2 30 17</td><td>按序加人，中速搅拌8～10min，均匀</td></tr><tr><td>分散剂 消泡剂 蜡粉 消光粉 光引发剂</td><td>0.8 0.5 3 6 3</td><td>边揽边加人，高速分散15～18min。检测细度</td></tr></table></body></html>  \n\n表3-7-64UV辊涂亚光清面漆性能指标  \n\n\n<html><body><table><tr><td>项目</td><td>性能指标</td><td>项目</td><td>性能指标</td></tr><tr><td>细度/μm 黏度（涂-4杯）/s 容器中状态</td><td>≤40 60~100 搅拌后呈均匀状态 商定</td><td>硬度（摆杆）/（din/s） 耐磨性/g 复合层耐水性</td><td>0.5~200 ≤0.03 72h不起泡、不起皱、 不脱落、无异常变化</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 指标调整UV辊涂涂料是高固体分涂料，施工固含达 $95\\%$ 以上。将不同树脂和单体搭配使用才能保证优良的施工性能和漆膜性能。如环氧树脂硬度高，但黏度也高，可以保证漆膜硬度，价格便宜；聚氨酯树脂硬度低，黏度低，能提高柔韧性也可降低黏度，改善施工性能，但价格高；不同光引发剂的搭配使用，才能防止氧阻聚的影响，使得表干和实干都达理想。如二苯甲酮和活性胺体系的搭配，胺引发剂促进表面干燥，二苯甲酮保证深层干燥。  \n\n$\\textcircled{3}$ 技术难点不同材料的配套使用，兼顾施工性能和漆膜性能，同时保证较好的性价比。不同引发剂的搭配比例，兼顾表面干燥和深层干燥。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 573,
+        "chunk": "# 6．木用水性涂料  \n\n木用水性面漆主要有单组分和双组分两种。  \n\n(1）单组分水性面漆单组分水性面漆分清面漆和实色漆；按光泽分又分为亮光和亚光面漆。以下是相关产品的参考配方。  \n\n$\\textcircled{1}$ 单组分亮光清面漆 见表3-7-65。  \n\n表3-7-65 单组分亮光清面漆配方及生产工艺   \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数）/%</td><td>生产工艺</td></tr><tr><td>ALBERDINGK CUR99</td><td>41</td><td rowspan=\"6\">按序缓慢加人，中速搅拌均匀</td></tr><tr><td>ALBERDINGK AC2514</td><td>41</td></tr><tr><td>TEGO FOAMEX 800</td><td>0.8</td></tr><tr><td>BYK346</td><td>0.3</td></tr><tr><td>二丙二醇甲醚(DOW)</td><td>2</td></tr><tr><td>二丙二醇丁醚(DOW)</td><td>3</td></tr><tr><td>去离子水</td><td>7.3</td><td></td></tr></table></body></html>  \n\n续表  \n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数）/%</td><td>生产 工艺</td></tr><tr><td>AQUACER539(BYK)</td><td>4</td><td rowspan=\"2\">加人，搅拌均匀</td></tr><tr><td>BYK333</td><td>0.1</td></tr><tr><td>DSX 1514(COGNIS)</td><td>0.5</td><td>缓慢加人，搅拌均匀，200目滤布过滤包装</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 单组分亮光白面漆 见表 $3-7-66\\sim$ 表3-7-69。  \n\n表3-7-66 单组分水性亮光白面漆及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数）/%</td><td>原料及规格</td><td>比例（质量分数）/%</td></tr><tr><td>ALBERDINGK CUR99</td><td>20</td><td>二丙二醇丁醚</td><td>3</td></tr><tr><td>ALBERDINGK AC2514</td><td>40</td><td>去离子水</td><td>4.4</td></tr><tr><td>BYK093</td><td>0.5</td><td>钛白浆（75%)</td><td>25</td></tr><tr><td>TEGO ARIEX902W</td><td>0.2</td><td>BYK333</td><td>0.1</td></tr><tr><td>二丙二醇甲醚</td><td>3</td><td>DSX1514</td><td>0.5</td></tr></table></body></html>\n\n注：生产工艺为按序缓慢加人，中速揽拌均匀。200目滤布过滤包装。  \n\n表3-7-67 水性钛白色浆  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数）/%</td><td>生产工艺</td></tr><tr><td>去离子水</td><td>15.9</td><td rowspan=\"3\">按序加入，高速分散至细度合格</td></tr><tr><td>TEGODISPERS735W</td><td>5</td></tr><tr><td>TIOz DUPONT R-706</td><td>75</td></tr><tr><td>TEGO 902W</td><td>0.1</td></tr></table></body></html>  \n\n表3-7-68 单组分水性亚光清面漆配方及生产工艺   \n\n\n<html><body><table><tr><td>原料名称</td><td>比例(质量分数）/%</td><td>生产工艺</td></tr><tr><td>水性树脂（AC2514，ALBERDINGK)</td><td>79.8</td><td>称量投人，启动慢速搅拌</td></tr><tr><td>润湿剂270(TEGO)</td><td>0.3</td><td rowspan=\"8\">按序，缓慢加人</td></tr><tr><td>分散剂750W(TEGO)</td><td>0.5</td></tr><tr><td>成膜助剂 TEXANOL</td><td>2</td></tr><tr><td>DPNB(DOW)</td><td>3</td></tr><tr><td>DPM(DOW)</td><td>3</td></tr><tr><td>丙二醇</td><td>2</td></tr><tr><td>消泡剂（830，TEGO)</td><td>0.7</td></tr><tr><td>增稠剂（RM-5000,ACRYSOL,ROHM&HASS)</td><td>0.8</td></tr><tr><td>亚粉（SY7000，GRACE)</td><td>2.5</td></tr><tr><td>蜡浆（BYK513)</td><td>4.0</td><td rowspan=\"3\">慢慢加人，中速分散至细度合格 按序，缓慢投人，中速搅拌均匀</td></tr><tr><td>去离子水</td><td>1.0</td></tr><tr><td>防沉剂（BYK420)</td><td>0.2</td></tr><tr><td>胺中和剂（AMP95）</td><td>0.2</td><td>加人，调整pH</td></tr></table></body></html>  \n\n表3-7-69 单组分水性亚光清面漆性能指标  \n\n\n<html><body><table><tr><td>检验项目</td><td>性能指标</td><td>检验项目</td><td>性能指标</td></tr><tr><td>黏度(25℃)/mPa*s</td><td>600</td><td>光泽(60°)/%</td><td>55</td></tr><tr><td>细度/μm</td><td>25</td><td>附着力/级</td><td>１</td></tr><tr><td>固含量/%</td><td>36.9</td><td>贮存稳定性(50℃，7d)</td><td>无异常</td></tr><tr><td>表干/min</td><td>45</td><td></td><td></td></tr></table></body></html>  \n\n$\\textcircled{3}$ 单组分水性亚光白面漆 见表3-7-70和表3-7-71。  \n\n表3-7-70 单组分水性亚光白面漆配方及生产工艺   \n\n\n<html><body><table><tr><td>原料名称</td><td>比例(质量分数）/%</td><td>生产工艺</td></tr><tr><td>水性树脂（AC2514，ALBERDINGK）</td><td>53</td><td>称量投人，启动慢速</td></tr><tr><td>润湿剂270（TEGO) 分散剂750W(TEGO)</td><td>0.5 3.5</td><td rowspan=\"8\">按序，缓慢加人</td></tr><tr><td>成膜助剂TEXANOL</td><td>2</td></tr><tr><td>DPNB(DOW)</td><td>3</td></tr><tr><td>DPM(DOW)</td><td>1.5</td></tr><tr><td>丙二醇</td><td>2</td></tr><tr><td>消泡剂（830，TEGO)</td><td>0.8</td></tr><tr><td>增稠剂(RM-5000,ROHM&HASS)</td><td>0.7</td></tr><tr><td>钛白粉</td><td>25</td></tr><tr><td>亚粉（SY7000，GRACE)</td><td>1.3</td></tr><tr><td>蜡浆（BYK513)</td><td></td><td>慢慢加入，中速分散至细度合格</td></tr><tr><td>去离子水</td><td>3.0 3.1</td><td>按序，缓慢投人，中速搅拌均匀</td></tr><tr><td></td><td></td><td></td></tr><tr><td>防沉剂（BYK420)</td><td>0.4</td><td></td></tr><tr><td>胺中和剂（AMP95）</td><td>0.2</td><td>加人，调整pH</td></tr></table></body></html>  \n\n表3-7-71 单组分水性亚光白面漆的性能指标  \n\n\n<html><body><table><tr><td>检验项目</td><td>性能指标</td><td>检验项目</td><td>性能指标</td></tr><tr><td>黏度(25℃)/mPa·s</td><td>2500</td><td>光泽(60°)/%</td><td>53</td></tr><tr><td>细度/μm</td><td>35</td><td>附着力/级</td><td>1</td></tr><tr><td>固含量/%</td><td>50.2</td><td>贮存稳定性(50℃，7d)</td><td>无异常</td></tr><tr><td>表干/min</td><td>48</td><td></td><td></td></tr></table></body></html>  \n\n$\\textcircled{4}$ 配方调整单组分水性面漆乳液与水性各类助剂的相容性要好、对颜料、填料有较好的分散性，对木质基材上有很好的润湿性。成膜助剂的搭配使用，主要根据乳液的 $\\textstyle{\\mathcal{T}}_{\\tilde{\\mathbf{g}}}$ 值，适当选用水溶性和微水溶的溶剂搭配，改善乳胶粒子在水油两相中溶解性，使成膜更有效。通常将最低成膜温度（MFFT）调控在 $8^{\\circ}C$ 。颜料、填料分散，选择易分散型颜料和消光粉，使用高分子润湿分散剂，用增稠剂调节分散液的黏度便于高速分散，有效对颜料、填料解絮凝及稳定体系。为了面漆有较好的手感，选用了易于添加的蜡浆。  \n\n（2）双组分水性面漆  \n\n$\\textcircled{1}$ 双组分水性清面漆 见表3-7-72～表3-7-74。  \n$\\textcircled{2}$ 双组分水性亮光白面漆 见表3-7-75。  \n$\\textcircled{3}$ 双组分亚光白面漆 见表3-7-76和表3-7-77。  \n\n表3-7-72双组分水性亮光清面漆配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例(质量分数)/%</td><td>生 产 工艺</td></tr><tr><td colspan=\"3\">A组分</td></tr><tr><td>ALBERDINGK U9800 BYK024 DEHYDRAN1620</td><td>85.3 0.6 0.4 5.0</td><td>按序加人，高速分散均匀。200目滤布过滤包装</td></tr><tr><td>WATER BOTCHERS BORCHI GOL LA50 DSX2000</td><td>8.2 0.3 0.2</td><td></td></tr><tr><td colspan=\"3\">B组分</td></tr><tr><td>BAYERBAYHYDUR 305</td><td>20</td><td>直接分装</td></tr></table></body></html>  \n\n表3-7-73 双组分水性亚光清面漆配方及生产工艺  \n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数）/%</td><td>生产 工 艺</td></tr><tr><td colspan=\"3\">A组分</td></tr><tr><td>水</td><td>15.8</td><td>加人</td></tr><tr><td>胺中和剂（AMP95） 润湿剂（TEGO270) 分散剂（TEGODISPER750W) 消泡剂（TEGOFOAMEX810) 流变剂[ACRYSOLRM-5000(ROHM&HASS)]</td><td>0.2 0.3 0.4 0.6 0.6</td><td>缓慢加人，搅拌均匀</td></tr><tr><td>钛白粉（DUPAND，R706) 亚粉(SY7000,GRACE) 水性树脂乳液（BAYERXP2470）</td><td>5.0 73.0</td><td>投人，中速分散至细度合格</td></tr><tr><td>蜡浆（BYK-513) 防沉剂（BYK420）</td><td>4.0 0.1</td><td>缓慢加人，搅拌均匀</td></tr><tr><td colspan=\"3\"></td></tr><tr><td>固化剂（XP2487，BAYER)</td><td>B组分 28</td><td>直接包装</td></tr></table></body></html>  \n\n表3-7-74双组分水性亚光清面漆性能指标  \n\n\n<html><body><table><tr><td>检验项目</td><td>性能指标</td><td>检验项目</td><td>性能指标</td></tr><tr><td>黏度（25C）/KU</td><td>68</td><td>光泽(60°)/%</td><td>52</td></tr><tr><td>细度/μm</td><td>25</td><td>附着力/级</td><td>1</td></tr><tr><td>固含量/%</td><td>37.8</td><td>贮存稳定性（50℃，7d)</td><td>无异常</td></tr><tr><td>表干/min</td><td>55</td><td></td><td></td></tr></table></body></html>  \n\n表3-7-75 双组分水性亮光白面漆配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数）/%</td><td>生产工艺</td></tr><tr><td></td><td>A组分</td><td></td></tr><tr><td>水 NATROSOL 250 HBR 50%DEMA IN WATERDEUCHEM</td><td>128.5 1.2 1.5</td><td rowspan=\"3\">按序加人，高速分散至细度合格</td></tr><tr><td>NOPCO SN5027 COGNIS H140 Du Pond TI-PURE R902</td><td>6.0 6.0 0.8</td></tr><tr><td>DEGUSSA901W ROHM&HASSKATHON LXE</td><td>1.0 200</td></tr></table></body></html>  \n\n续表  \n\n表3-7-76 双组分水性亚光白面漆配方及生产工艺  \n\n\n<html><body><table><tr><td>原料及规格</td><td>比例（质量分数）/%</td><td>生产工艺</td></tr><tr><td>BAYER XP2546 TEXANOL</td><td>580 22</td><td rowspan=\"3\">低速搅拌下，缓慢加人。200目滤布过滤包装</td></tr><tr><td>BYK024</td><td>3.0</td></tr><tr><td>BASF WE1</td><td>40</td></tr><tr><td>ROHM&HASSRM5000</td><td>6.0</td><td></td></tr><tr><td>ROHM&HASS</td><td>4.0 1000</td><td></td></tr><tr><td>合计</td><td></td><td></td></tr><tr><td></td><td>组分B</td><td></td></tr><tr><td>BAYERBAYHYDURXP2547</td><td>200</td><td>直接分装</td></tr></table></body></html>  \n\n<html><body><table><tr><td>原料名称</td><td>比例（质量分数）/%</td><td>生产工艺</td></tr><tr><td colspan=\"3\">组分A</td></tr><tr><td>水</td><td>3.2</td><td>加人</td></tr><tr><td>胺中和剂AMP95</td><td>0.2</td><td rowspan=\"5\">依次缓慢加人，搅拌均匀</td></tr><tr><td>润湿剂TEGO270</td><td>0.5</td></tr><tr><td>分散剂TEGODISPER750W</td><td>3.5</td></tr><tr><td>消泡剂TEGOFOAMEX 810</td><td>0.8</td></tr><tr><td>流变改性剂ACRYSOLRM-5000ROHM&HASS</td><td>0.6</td></tr><tr><td>钛白粉R706Du Pond</td><td>25</td><td rowspan=\"2\">慢慢投人，分散至细度合格</td></tr><tr><td>亚粉GRACE</td><td>2.8</td></tr><tr><td>水性树脂乳液BAYERXP2470</td><td>60</td><td rowspan=\"4\">缓慢投人，分散至细度合格</td></tr><tr><td>蜡浆BYK-513</td><td>3.0</td></tr><tr><td>防沉剂BYK420</td><td>0.4</td></tr><tr><td></td><td>组分B</td></tr><tr><td colspan=\"3\"></td></tr><tr><td>固化剂XP2487BAYER</td><td>23</td><td>直接包装</td></tr></table></body></html>  \n\n表3-7-77双组分水性亚光白面漆性能指标  \n\n\n<html><body><table><tr><td>检验项目</td><td>性能指标</td><td>检验项目</td><td>性能指标</td></tr><tr><td>黏度（25C）/KU</td><td>75</td><td>光泽（60°)/%</td><td>48</td></tr><tr><td>细度/μm</td><td>35</td><td>附着力/级</td><td>1</td></tr><tr><td>固含量/%</td><td>54.8</td><td>贮存稳定性(50℃,7d)</td><td>无异常</td></tr><tr><td>表干/min</td><td>58</td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 574,
+        "chunk": "# 7.助剂  \n\n在涂料生产过程中已经加入各种助剂解决配方、施工中的可能发生的问题。这里所指的“助剂”，是涂料厂另外配置、作为产品出售于家具厂的。要提供指导配方及方法，专供家具厂在涂装中发生异常情况时现场使用，以便家具厂更直接、更方便地解决问题。  \n\n(1）慢干水高温时，由于溶剂的挥发速率加快，漆膜表干太快，会造成漆膜流平不好、起针孔、气泡等弊病，加入慢干水可以有效地缓解和解决问题，慢干水的加人量一般不超过加人稀释剂量的 $25\\%$ ，过多会造成漆膜慢干、附着力不好等病。慢干水的溶解力要适中，太强容易咬底；太弱，对涂料的溶解性不好。一般选用醇酯类溶剂如PMA、PMP，  \n\n俗称慢干水。  \n\n(2）防发白水漆膜发白的原因是涂料在高温、高湿的环境下施工，由于溶剂的挥发过快，漆膜表面温度瞬间下降，造成空气中的水分凝结于漆膜，水与涂料不相容，造成视觉上的发白。防发白水的作用就是减慢挥发速率： $\\textcircled{1}$ 防止水分冷凝在漆膜上； $\\textcircled{2}$ 有时漆膜发生轻微发白，之后能复原透明，原因是漆膜有些溶剂与水相溶，挥发时把水带走，但是发白严重时就不可能复原； $\\textcircled{3}$ 防发白水应使用高沸点、与水相溶的溶剂，如乙二醇丁醚、内二醇甲醚、丙二醇乙醚； $\\textcircled{4}$ 防发白水使用时等量代替稀释剂，极限量为稀释剂的 $25\\%$ 心  \n\n(3）流平剂流平剂的作用主要有两个： $\\textcircled{1}$ 处理高温情况下的漆膜流平不好的问题；$\\textcircled{2}$ 解决由于环境因素引起的缩孔等问题。一般选用较强的降低表面张力的有机硅助剂，如TEGO的450、410等。为方便使用，一般以醋酸丁酯稀释成 $20\\%$ 的溶液使用。加量要适当，以解决问题的最低量为合适。  \n\n(4）消泡剂消泡剂的作用主要是为了解决高温施工时，漆膜出现的起泡等病，一般选用消泡能力较强的有机硅消泡剂，如BYK057、BYK066N等。为方便使用，一般稀释成$5\\%\\sim10\\%$ 的溶液。  \n\n(5）催干剂催干剂一般用于PU体系，一般为有机锡（如二月桂酸二丁基锡、辛酸亚锡）或胺类化合物（如二甲基乙醇胺)。常用的是二月桂酸二丁基锡，常用的牌号如美国气体产品有限公司的T-12等，一般以醋酸丁酯稀释成 $10\\%$ 的溶液使用，使用时注意环保限用要求。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 575,
+        "chunk": "# 五、固化剂",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 576,
+        "chunk": "# 1.概述  \n\n木用涂料中，双组分聚氨酯涂料是最重要的品种。2008年，中国木用涂料总销量达到70万吨，其中双组分聚氨酯涂料占 $70\\%$ 以上。双组分聚氨酯涂料分为甲乙两组分，分别包装贮存。甲组分是异氰酸酯的聚合物，种类很多，但都含有不同数量的异氰酸酯基团(—NCO)，统称为固化剂。例如TDI的加成物或HDI的三聚体等。乙组分则含有不同数量的羟基（一OH）基团，称为主剂，以各种醇酸树脂和丙烯酸树脂为主，使用时将甲乙组分按比例混合均匀，涂布后交联成膜，形成大分子的聚氨酯高聚物—一装饰性、功能性俱佳的干膜。  \n\n木用涂料为何选用聚氨酯呢？原因之一是家具的基材限制了涂料的施工与固化条件。家具的基材通常都是木材、中纤板等，这些材料均不耐高温，温度稍高即容易变形、开裂，同时，通常家具部件的体积较大，较难使用设备烘烤，因此要求相应的涂料产品都能室温干燥。原因之二是聚氨酯涂料可以满足人们对于家具涂装的视觉、触觉等要求。家具与人的日常生活紧密接触，因此对涂膜表面效果的要求高，涂料必须具有很高的装饰性，例如丰满度、平整性、硬度等，与其他室温固化的涂料品种（例如热塑性丙烯酸酯涂料）相比，聚氨酯涂料在装饰性上具备得天独厚的优势。原因之三是聚氨酯涂料可以在不同底材的家具上施工应用。由于家具底材种类丰富，例如中纤板贴纸、中纤板贴木皮，木皮包括樱桃木、橡木、黑胡桃、榉木等，还有实木家具，木材的来源不同，含水率、密度、油脂含量均不同，木材本身的硬度差别也很大。由于材质的变化多端，对涂料的要求也不尽相同。聚氨酯涂料能够室温干燥，具有良好的装饰性能，能很好地满足家具涂料对于表面效果的追求，羟基组分和固化剂组分的可调性强，可以满足不同木材的涂装需求，聚氨酯涂料的综合性能优异，性价比高，因此木用涂料选择双组分聚氨酯也就不足为奇了。  \n\n在我国的木用涂料发展之初，其固化剂产品主要来自德国、意大利和中国台湾地区。后来，国内涂料厂家开始自行研制并生产固化剂，主要用于为自身产品配套销售。在木用涂料整体发展过程中，固化剂的产量、性能不断提高，品种越趋合理，基本上满足了国内市场的需求。  \n\n但这种由粗糙技术和简陋设备生产出来的固化剂，它的硬伤就是游离TDI含量太高。随着市场对产品环保要求越来越高，以及国家环保法规对游离TDI含量的限制，各种进口固化剂开始在木用涂料的高端领域和新产品中扮演主要角色。进口产品销量的大幅提高，反过来又极大地刺激了国产固化剂的研发、精制并取得新的发展。  \n\n聚氨酯涂料的发展与家具的发展是相互促进的，家具行业的技术进步和设计创新促使了聚氨酯涂料新产品的发展，涂料的发展反过来又提高了家具的附加值，涂料品种在增加，施工性能要求适应性更广，施工环境要求宽容度更大，由于要提高施工效能而使用了新设备、新工艺。以上种种，无一不为固化剂本身的全面发展提供了极大的动力。",
+        "category": " Introduction"
+    },
+    {
+        "id": 577,
+        "chunk": "# 2.木用涂料聚氨酯固化剂的分类方法  \n\n木用涂料聚氨酯固化剂常用分类方法是根据原材料异氰酸酯单体种类、生产过程中的聚合方法或产品的物化性能进行分类。  \n\n(1）按照原材料异氰酸酯类单体的不同分类，可以分为TDI固化剂、HDI固化剂、IP-DI固化剂和混合固化剂，例如TDI和HDI的混合固化剂等。单体种类不同，固化剂性能特点各异。  \n\n(2）按照生产过程中采用的聚合方法的不同，可以分为预聚物、加成物、三聚体和缩二脲。预聚物是醇酸树脂、油的醇解物等分子量较大的含羟基组分与异氰酸酯单体通过加成反应合成。加成物是由二异氰酸酯单体与小分子多元醇通过加成反应合成而得，是以氨酯键联结的多异氰酸酯。三聚体是三个二异氰酸酯单体自聚而成，成为含异氰脲酸酯的多异氰酸酯。缩二脲的典型工业产品是由 $\\mathsf{3m o l}$ 的HDI单体和1mol的水反应生成的具有三官能度的多异氰酸酯。  \n\n(3）按照固化剂的物化性能进行划分，如耐黄变固化剂、快干固化剂、环保固化剂等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 578,
+        "chunk": "# 3.木用涂料聚氨酯固化剂的合成与性能特点  \n\n(1）木用涂料选用TDI固化剂的原因固化剂生产中应用最广泛的异氰酸酯单体是甲苯二异氰酸酯（TDI)。据统计，2008年中国木用聚氨酯涂料50万 $\\sim60$ 万吨，根据中国聚氨酯涂料的使用习惯，漆与固化剂的比例通常为 $1:1$ （亮光）或 $2:1$ （亚光或底漆)，即2008年木用固化剂的用量为10万 ${\\sim}15$ 万吨，其中TDI固化剂的使用比例高达 $95\\%$ 以上。  \n\n木用聚氨酯涂料之所以选择TDI类型固化剂，其原因如下。  \n\n$\\textcircled{1}$ 目前中国木用涂料市场以中价、中下价产品为主力，对原材料成本的控制，限制了其他昂贵的异氰酸酯单体的大量使用。因此，TDI是目前需求量大、性价比高的异氰酸酯单体。  \n\n$\\textcircled{2}$ 与HDI和IPDI相比，TDI固化剂的常温自干性能优异，符合家具的涂装要求。  \n\n$\\textcircled{3}$ 与MDI单体相比，TDI固化剂的耐黄变性好，相容性佳，施工性能更优异（主要是适用期较长)，贮存稳定性能好（MDI易结晶、发白)，漆膜的透明性等装饰性能好。因此，MDI单体虽然价格有优势，但在木用涂料中甚少使用。  \n\n$\\textcircled{4}$ 技术进步提高了TDI固化剂的综合性能。十几年来，行业内积累了丰富的固化剂研发、生产和应用经验。例如针对TDI的耐黄变性不足，通过主剂、助剂、合成方法的改善以及应用经验的提高，漆膜的耐黄变性也在不断提高。对游离TDI单体含量的限制，促使  \n\n不断创新，开发出符合国标要求的产品。  \n\nTDI固化剂主要有加成物和三聚体两种，对加成物而言，由于国产产品和进口产品的性能差异较大，因此以下从进口TDI加成物、国产TDI加成物和TDI三聚体三个方面进行论述。  \n\n(2）进口TDI加成物固化剂TDI加成物合成的化学反应示意图如图3-7-6所示。  \n\n![](images/d8ca375f248a8e3b315067a09be9fc3b99caa300a8928fb3f32bb5b0faeb3002.jpg)  \n图3-7-6TDI与TMP的加成反应示意图  \n\n理想的TDI加成物固化剂是3molTDI和lmolTMP的加成产物，含有三个可参与交联的NCO基团。但是因为苯环上不同取代位置上的NCO基团的反应选择性不同，以及反应温度、催化剂和副反应等的影响，所以TDI加成物固化剂是由一系列具有不同分子量的物质组成的混合物，其特点是具有一定的分子量分布。在木用涂料中为了调节产品性能、成本以及生产工艺，通常会加人其他的二元醇，例如新戊二醇、丙二醇、1，4-丁二醇和1,3-丁二醇等，这就使得情况更为复杂，分子量分布更宽，GPC图上甚至会出现多峰分布。德国专利GP886818（A）中采用了三羟甲基丙烷和1，4-丁二醇以及1，3-丁二醇的混合多元醇，并在TDI大大过量的情况下合成TDI的加成物，采用TDI过量的方法降低了扩链反应发生的可能性，使产品的分子结构更接近理想结构。进口固化剂虽然分子量分布在理想范围内的组分含量很高，但是也还有少量组分的分子量超出了这个范围，其原因是由于薄膜蒸发时的高温处理导致的副反应，从而导致链的枝化或扩展，如图3-7-7所示。，  \n\n![](images/e2fbac9ca29378412e5a4947180fd89a50ae65d00a5faadcb682136e1f736ef2.jpg)  \n图3-7-7 氨基甲酸酯和NCO基团的副反应  \n\n进口TDI加成物固化剂在我国聚氨酯木用涂料的发展中起着重要的作用，一方面促进了聚氨酯涂料在我国的快速发展；另一方面促进了我国固化剂生产的技术进步。  \n\n进口TDI加成物固化剂的代表产品是德国BAYER公司的DesmordurL75，其进人中国市场的时间早，被广大的涂料配方工程师所接受，因此TDI的加成物也被称为L型固化剂。其他类似的进口产品还有意大利SAPICI公司的POLURENEAD以及中国台湾日胜公司（EVERMORECHEMICAL）的 $\\mathrm{SC~75~LT}$ ，都属于芳香族的多异氰酸酯固化剂。  \n\n$\\textcircled{1}$ 进口TDI加成物固化剂特点  \n\n由于采用先进的生产方法，这一类型的固化剂的普遍特点如下。  \n\na.游离 TDI含量低。其产品技术指标是低于 $0.5\\%$ C $75\\%$ 固含)，实际检测结果往往低于 $0.3\\%$ ，新的产品技术指标中，游离TDI含量低于 $0.1\\%$ o  \n\nb.NCO基团含量高，是目前市面上最接近理论值（根据配方不同，该值为 $14.4\\%$ 左右）的一类产品。NCO基团含量高，与同一涂料配用时，需要的固化剂量可适当减少，成本降低。  \n\nc.柔韧性好，虽然表面看来，木用涂料对柔韧性的要求不如金属涂料高，容易被忽略，但该性能与漆膜的抗开裂性能紧密相关，所以显得同样重要。  \n\nd.初干稍慢，实干较快，会在后文详述·  \n\ne.与硝化棉、二甲苯等的相容性较好，漆膜的透明度较高，调整配方时较灵活且成本降低。进口固化剂与二甲苯的相容性可以达到1：10，而国产固化剂为 $1:5$ 左右。  \n\n$\\textcircled{2}$ 进口TDI加成物固化剂的生产由于NCO基团与羟基的反应选择性不足，少量的TDI没有参与反应而残留在体系之中。在施工和干燥时，挥发的游离TDI会对人体健康和环境产生危害。国外从20世纪50年代开始采用薄膜蒸发法生产，产品的游离TDI含量在 $0.5\\%$ 以下（固体分 $75\\%$ ，近几年来更是达到 $0.2\\%$ 甚至更低。  \n\n例如英国专利GB886818（A）的报道，该工艺首先在TDI大量过量的情况下加入多元醇反应$(60\\sim70^{\\circ}\\mathrm{C})$ ，反应产物通过管状预热器7加热到一定温度后（ $\\mathsf{150^{\\circ}C}$ 以上)，经过闪蒸仪8初步分离游离TDI，然后进人薄膜蒸发器14分离，分离后的产品经兑稀后即为最终产品。所采用的薄膜蒸发法设备与工艺流程如下图3-7-8所示。配方见表3-7-78。  \n\n![](images/0be9afcb46e4b9bea9d653c9e9bffa737dbbd32f8a5987267405d19ae6a8538d.jpg)  \n图3-7-8 薄膜蒸发设备与流程  \n\n1,2—物料罐；3，4一物料泵；5—三通阀；6—进  \n料管；7一预热器；8—闪蒸仪；9，16—冷凝器；10—真空缓冲罐；11，17—TDI管道；12，18—TDI收集罐；13一物料管道：14一薄膜蒸发器；15—产品收集罐  \n\n表3-7-78薄膜蒸发处理前固化剂的合成配方  \n\n\n<html><body><table><tr><td>组分</td><td>用量/mol</td><td>组分</td><td>用量/mol</td></tr><tr><td>TDI</td><td>20</td><td>1,3-丁二醇</td><td>1</td></tr><tr><td>三羟甲基丙烷</td><td>1.4</td><td>1,4-丁二醇</td><td>0.2</td></tr></table></body></html>  \n\n根据表3-7-78，NCO/OH的摩尔比为6，分离前游离TDI含量计算值为66.37%。  \n\n合成温度 $60^{\\circ}C$ ，基本工艺与其他固化剂的合成相同。分离温度 $180^{\\circ}C$ ，压力 $\\phantom{+}6\\widehat{6}.7\\mathrm{Pa}$ 分离后产品中未检测出游离TDI，NCO含量为18.3%，仅比理论值低5%。该专利认为控制温度和停留时间是控制副反应的关键。  \n\n采用薄膜蒸发法处理游离TDI的进口固化剂的代表产品及指标规格见表3-7-79。  \n\n(3）国产TDI加成物固化剂国产TDI加成物经过了两个发展阶段，并以2001年作为分界线。2001年前的国产TDI固化剂的游离TDI含量非常高，通常达到5%～10%。2001年国家颁布了GB18581，对游离TDI含量进行了限制并强制执行，推动了配方及工艺的改进，现在国产TDI加成物固化剂的游离TDI含量大都能降低到2%以下，最低可达到1%以下，但不稳定。  \n\n表3-7-79 进口固化剂代表产品及技术指标  \n\n\n<html><body><table><tr><td rowspan=\"2\">技术指标</td><td>BAYER</td><td colspan=\"2\">SAPICI</td><td>日胜</td></tr><tr><td>DESMODUR L75</td><td>AD</td><td>AD75-01</td><td>SC-75 LT</td></tr><tr><td>溶剂</td><td>醋酸乙酯</td><td>醋酸乙酯</td><td>醋酸乙酯</td><td>醋酸乙酯</td></tr><tr><td>NCO/%</td><td>13.0±0.5</td><td>13.0±0.5</td><td>13.0±0.5</td><td>13.0±0.5</td></tr><tr><td>游离TDI/% <</td><td>0.5</td><td>0.5</td><td>0.1</td><td>0.5</td></tr><tr><td>固含量/%</td><td>75</td><td>75</td><td>75</td><td>75±2</td></tr><tr><td>黏度（23℃）/mPa·s</td><td>1600</td><td>1200~1300</td><td>1200~1300</td><td>1600 ±400</td></tr><tr><td>色泽(GARDNER) <</td><td>１</td><td>1</td><td>1</td><td>1</td></tr></table></body></html>  \n\n国内通常采用后三聚法降低游离TDI含量。后三聚法也称三聚法，是在TDI与羟基组分的加成反应完成后，再加人三聚催化剂对残留单体进行三聚反应，达到降低游离TDI的目的。但是，实际情况并非如此简单，要对加成反应后的残留单体进行三聚并使游离TDI达到较低的水平，在配方设计和原材料选择上必须进行系统试验，摸索最佳条件，从而得到理想结果。  \n\n$\\textcircled{1}$ 后三聚法原理简介后三聚法去除游离TDI与传统的TDI三聚体的合成均利用了异氰酸酯的三聚反应，两相比较，前者具有以下的特点。  \n\na.加成反应后，可供聚合的游离TDI的浓度低，为 $5\\%\\sim10\\%$ ，在这种情况下再进行三聚反应，就使得游离TDI的三聚反应程度很低。即便进行了后三聚反应，这 $5\\%\\sim10\\%$ 的游离TDI也不可能全部聚合掉。反映到成品的游离TDI含量上，就是国产的用后三聚法生产的加成物固化剂比传统的三聚体固化剂的要高。  \n\nb.参与三聚反应的不仅仅是游离的TDI分子，TDI和多元醇的加成物也会发生这种三聚反应，体系中存在几种不同的三聚反应，包括游离TDI自聚、TDI和多元醇的加成物自聚以及游离TDI和加成物的共聚，从而导致固化剂的分子量增加、分子量分布变宽、黏度增加。  \n\nc.加成物中的NCO基团由于空间位阻效应导致反应活性较低，三聚反应速率较慢。  \n\n基于以上特点，在利用后三聚法降低游离TDI含量时，为了提高体系中游离TDI自聚反应活性，降低加成物参加三聚的概率，应注意以下几点。  \n\na.NCO/OH摩尔比的控制这个比例通常在 $2.0{\\sim}2.10$ ，合适的比例是进行三聚的必要条件，比例太高，在提高成本的同时，成品的游离TDI的含量会偏高；比例偏低时，会导致黏度增加快，反应终点难控制。  \n\nb.TMP和其他二元醇的比例控制加人二元醇的目的是为了提高体系的相容性和降低体系的黏度，提高传质效果，从而为三聚反应创造良好的条件。  \n\nc.催化剂的选择由于游离TDI发生自聚的反应活性比加成物的活性大，最好选择温和的催化剂，尽量使游离TDI聚合，降低加成物参与三聚的概率，更加有利于降低游离TDI的含量。如果催化剂的活性太强，反应速率太快，会导致加成物中NCO基团参与三聚反应的比例增加，不利于游离TDI含量的降低。  \n\n$\\textcircled{2}$ 国产TDI加成物固化剂的性能特点与进口固化剂相比，国产固化剂具有如下的特点。  \n\na.游离TDI含量较高，通常 $1\\%\\sim2\\%$ 以下。  \n\nb.NCO含量低，通常 $9\\%\\sim10\\%$ C $60\\%$ 固含量)，三聚催化剂的加人和反应时间的延长会导致更多的副反应发生，NCO含量降低。  \n\nc.容易被消光，这是国产固化剂的最大优势。由于木用涂料中亚光漆的比例较高，因此，固化剂对最终光泽的影响成为一个主要的指标。容易被消光的固化剂，主剂中需要消光粉的用量降低，成本降低的同时可以弥补固化剂本身透明度不足的缺陷。  \n\nd.初干很快，实干稍慢。进口固化剂和国产固化剂在干燥性能上的不同将在后文详述。e．与硝化棉、二甲苯等的相容性差。f.黏度大，原因是加成物之间或加成物与游离TDI之间发生三聚反应。$\\textcircled{3}$ 配方示例典型的后三聚法TDI加成物固化剂配方见表3-7-80，配方中 $\\mathrm{{NCO/OH=}}$ $2.0{\\sim}2.1$ ，三羟甲基丙烷与1，3-丁二醇之比为 $1.3{\\sim}1.6$ 0  \n\n表3-7-80 后三聚法TDI加成物配方  \n\n\n<html><body><table><tr><td>加料顺序</td><td>组分</td><td>用量/%</td><td>加料顺序</td><td>组 分</td><td>用量/%</td></tr><tr><td rowspan=\"2\">A</td><td>醋酸丁酯 甲苯二异氰酸酯</td><td>20 42~52</td><td>C</td><td>1,3-丁二醇 二月桂酸二丁基锡(DBTL)</td><td>3~8</td></tr><tr><td>抗氧剂</td><td>0~1</td><td>D</td><td>三聚催化剂</td><td>0~0.2 0~0.2</td></tr><tr><td rowspan=\"2\">B</td><td>醋酸丁酯</td><td>20</td><td>E 磷酸</td><td></td><td>0~0.2</td></tr><tr><td>三羟甲基丙烷</td><td>6~9</td><td>总计</td><td></td><td>100</td></tr></table></body></html>  \n\n生产工艺：B组分投人脱水釜，升温回流脱水1h，降温到 $60^{\\circ}C$ 以下备用。将A组分投人反应釜，启动搅拌，通人干燥的氮气，并升温到 $50^{\\circ}C$ 保温。开始滴加脱水液，控制反应釜温度不超过 $55\\mathrm{{^\\circC}}$ ，滴加时间 $\\mathrm{1\\sim2h}$ 。滴加完毕后在 $50^{\\circ}C$ 保温 $\\mathrm{2h}$ ，然后升温到 $65^{\\circ}C$ 保温$\\ln$ 。降温到 $50^{\\circ}C$ 。 $c$ 组分投人脱水釜后，开始滴加该组分，控制反应釜温度不超过 $55\\mathrm{^\\circC}$ 中1h内滴加完毕。升温到 $65^{\\circ}C$ 保温4h，取样检测游离TDI和NCO含量。加人 $\\mathbf{D}$ 组分，并保温，每半小时检测一次NCO含量，当NCO含量达到 $10.0\\%$ 以下时，加人E组分，搅拌$0.5\\mathrm{h}$ 。降温，过滤，包装。指标见表3-7-81。  \n\n表3-7-81 国产固化剂技术指标  \n\n\n<html><body><table><tr><td>指标</td><td>范围</td><td>指标</td><td>范围</td></tr><tr><td>NCO含量/%</td><td>9~10</td><td>游离TDI含量/%</td><td>1.0～2.0</td></tr><tr><td>固含量/%</td><td>58~62</td><td>色泽(Pt-Co比色)</td><td><100</td></tr><tr><td>黏度/mPa·s</td><td>1500~3000</td><td>外观</td><td>透明黏稠液体</td></tr></table></body></html>  \n\n该固化剂是一个典型的后三聚法处理游离TDI的配方，多元醇反应后，游离TDI含量为 $6\\%\\sim8\\%$ ，再经三聚处理后，游离TDI含量为 $1\\%\\sim2\\%$ ，达到国标GB18581的标准要求。可作为通用的加成物固化剂使用，用于亚光面漆时，有很好的被消光性能，用于底漆时具有较好的打磨性。  \n\n(4）改性TDI加成物固化剂木用涂料中，TDI加成物固化剂的使用量最大，从标准配方和工艺出发，为了适应国内市场的需要，为了降低成本，调节性能，对其改性意义很大，也很普遍。为了阐述的需要，同时也由于后三聚法以及低分子多元醇调节这两种方法的普遍使用，不将其作为改性的方法进行阐述，并已在前文中的标准产品中说明。改性TDI加成物的方法主要有两种：一是聚酯改性；二是MDI代替TDI作为多异氰酸酯组分使用。后者将在“固化剂的发展”中介绍，以下仅介绍聚酯改性的TDI加成物固化剂。  \n\n聚酯改性TDI加成物固化剂是采用低分子量的聚酯，代替部分的三羟甲基丙烷合成的。采用聚酯改性的TDI固化剂优点是成本降低、柔韧性好、相容性佳、光泽高，还可以采用二甲苯等价格便宜和极性低的溶剂作为稀释剂；缺点是NCO含量低，要达到同样的交联密度，需要用较大量的固化剂，但其硬度却不会同步提高。利用这个特点，把聚酯改性的TDI加成物应用于聚氨酯底漆中，可提高底漆对基材的附看力和柔韧性。  \n\n$\\textcircled{1}$ 聚酯改性TDI加成物固化剂原理由于聚酯树脂中含有的羟基基团与TDI中的NCO基团具有良好的反应性，因此可以用于固化剂的改性。用于改性的聚酯，其羟值通常要求在 $200\\mathrm{mg}~\\mathrm{KOH/g}$ (按 $100\\%$ 固含量计）以上，羟基平均官能度为 $z{\\sim}3$ ，酸值小于 $\\mathrm{1mg}$ $\\mathrm{\\bfKOH/\\bar{\\bfg}}$ ，同时要求黏度低、色泽浅。  \n\n聚酯和小分子多元醇的比例可以根据性能需要进行调整。降低聚酯树脂的用量，增加多元醇的用量，可以提高固化剂的干性、打磨性和硬度；反之，则可以提高漆膜的柔韧性、透明性和光泽。  \n\n用聚酯改性TDI加成物时，工艺上要注意聚酯树脂应首先和TDI反应，然后才能加入多元醇继续反应，这是由于聚酯树脂的官能度不均匀，部分官能度较高，会导致产物的支化度高，同时，聚酯树脂中的羟基反应活性降低，因此，为了反应的顺利进行以及生产安全性，聚酯树脂应该先与TDI反应。  \n\n聚酯改性的TDI加成物同样可以采取后三聚法降低产品中的游离TDI含量。  \n\n$\\textcircled{2}$ 聚酯改性TDI加成物固化剂性能特点  \n\na.聚酯改性TDI加成物固化剂最大的特点是成本低，原因之一是聚酯树脂可采用廉价的多元醇，不必使用价格较高的三羟甲基丙烷；原因之二是聚酯树脂的羟基当量较高，需要的 TDI的用量少；原因之三是可以采用二甲苯代替醋酸丁酯。  \n\nb.NCO含量低，通常为 $5\\%\\sim8\\%$ +  \nC 可用较多的二甲苯稀释。  \nd. 固化后漆膜的柔韧性好、光泽较高。$\\textcircled{3}$ 示例  \n.改性用聚酯半成品配方与生产工艺  \n$\\cdot$ 配方 改性用聚酯树脂配方见表3-7-82。  \n\n表3-7-82 改性用聚酯树脂配方  \n\n\n<html><body><table><tr><td>序号</td><td>组分</td><td>用量/%</td><td>序号</td><td>组分</td><td>用量/%</td></tr><tr><td rowspan=\"4\">A</td><td>月桂酸</td><td>5~20</td><td>B</td><td>季戊四醇</td><td>3~15</td></tr><tr><td>乙二醇</td><td>3～10</td><td>C</td><td>苯甲酸</td><td>2~10</td></tr><tr><td>次磷酸</td><td>0.2</td><td></td><td>二甲苯</td><td>1~2</td></tr><tr><td>苯酐</td><td>15~30</td><td>D</td><td>醋酸丁酯</td><td>40~50</td></tr></table></body></html>\n\n注：酸树脂常数 $k=1,04$ ；理论羟值为 $200\\mathrm{mg}\\ \\mathrm{KOH/g}$  \n\n$\\cdot$ 生产工艺反应釜设置为回流关闭状态，打开卧式冷凝器冷却水。将组分A中的物料投人反应釜，通氮气，流量 $\\mathrm{10m^{3}/h}$ ，升温到 $60^{\\circ}C$ 后开搅拌，此时物料全部熔融。投人组分B，继续升温到 $130^{\\circ}C$ ，物料熔融后，加入组分C，保持升温速率 $1\\mathrm{{{C}/\\operatorname*{min}}}$ 。 $170^{\\circ}C$ 时开始出水，控制馏温 $\\leqslant102^{\\circ}C$ 。温度达到 $220^{\\circ}C$ 时开始保温，取样检测酸值和黏度，每小时取样检测一次。酸值 ${\\leqslant}20\\mathrm{mg}\\ \\mathrm{KOH/g}$ 时，加入回流二甲苯D，反应釜设置为回流状态，保温回流，每小时检测酸值一次。酸值 $\\leqslant5\\mathrm{mg\\KOH/g}$ 时，升温到 $230\\%$ ，保温回流，取样检测酸值，每小时检测一次，酸值 $\\leqslant1\\mathrm{mg}\\ \\mathrm{KOH/g}$ 时降温。 $180^{\\circ}C$ 时加人醋酸丁酯兑稀，搅拌均匀。过滤包装备用。树脂指标如下。  \n\n$N V/\\frac{\\theta}{\\theta}=\\frac{1}{2}$  \n\n色泽（Fe-Co比色）  \n\nb.聚酯改性TDI加成物固化剂配方与生产工艺$\\cdot$ 配方 聚酯改性TDI加成物固化剂配方见表3-7-83。  \n\n表3-7-83 聚酯改性TDI加成物固化剂配方  \n\n\n<html><body><table><tr><td>序号</td><td>组分</td><td>用量/%</td><td>序号</td><td>组分</td><td>用量/%</td></tr><tr><td>A</td><td>TDI</td><td>25~35</td><td>D</td><td>DBTL</td><td>0～0.2</td></tr><tr><td>B</td><td>醋酸丁酯 聚酯半成品</td><td>25 20~30</td><td>E F</td><td>二聚催化剂 磷酸</td><td>0~0.2 0~0.2</td></tr><tr><td>C</td><td>丙二醇</td><td>3~7</td><td>G</td><td>醋酸丁酯</td><td>15~30</td></tr></table></body></html>  \n\n$\\cdot$ 生产工艺  \n\n投A入反应釜，通入干燥的氮气， $2\\pi^{3}/\\mathrm{{h}}$ ，开搅拌并升温至 $40^{\\circ}C$ 中  \n\n投B人高位槽，升温至 $60^{\\circ}C\\pm2^{\\circ}C$ ，滴加入反应釜。滴加时控制反应釜温度 $\\leq45^{\\circ}C$ ；滴加完毕后再 $60^{\\circ}C$ 保温 $\\ln$ ，降温至 $50\\%$ 0滴加C， $60^{\\circ}C$ 保温 $\\mathtt{4h}$ 。加人 $\\mathrm{~D~}$ ， $60^{\\circ}C$ 保持 $\\ln$ ，测NCO。加 $\\mathbf{E}$ ，保温1h后测NCO，每小时测一次，待NCO降至 $7.3\\sim7.6$ 时合格。加 $\\mathbf{F}$ ，搅拌 $0.5\\mathrm{h}$ 0加 $G$ ，兑稀，搅拌均匀，过滤包装。该固化剂可以用于聚氨酯底漆中。  \n\n（5）TDI三聚体固化剂  \n\n$\\textcircled{1}$ TDI三聚体固化剂原理 TDI三聚体的理想分子结构如图3-7-9所示。  \n\n三个TDI分子以异氰脲酸酯相连接，形成一个新的六元环结构。实际反应条件下，体系中会生成其他的副产物如五聚体、七聚体等。TDI的三聚反应是一个亲核反应，路易斯碱、离子性试剂均可作为反应的催化剂。反应中催化剂的亲核基团进攻异氰酸酯基团上的碳正离子。可用的催化剂种类很多，包括叔胺、金属羧酸盐等，目前常用的是叔胺类的催化剂，例如DMP-30等。选择催化剂的一个重要原则就是适宜的聚合速率，聚合速率不能太快，否则反应无法控制，聚合速率太慢，则影响生产效率。使用的催化剂在反应完毕后应该可以通过适当的方法去除或失活，提高产品的贮存稳定性。  \n\n![](images/95f714c13b6762ff4c4634f87774843f2e8e45e59e90ecf3e8a579abf93f775d.jpg)  \n图3-7-9TDI三聚体理想结构图R是TDI的分子结构，并带一个NCO基团  \n\n$\\textcircled{2}$ TDI三聚体固化剂的性能特点由于TDI三聚体分子中存在大量的刚性的六元环的结构，因此，TDI三聚体固化剂的玻璃化温度高、硬度高；又由于存在五聚体、七聚体等更高形式的聚合物，三聚体的平均官能度提高，固化后漆膜的交联密度高、耐划伤性好；六元环中的位阻效应会阻止异氰脲酸酯的氧化，漆膜的耐黄变性比加成物好。但如果单独使用三聚体作为固化剂，漆膜太脆，因此三聚体固化剂通常与加成物配合使用，改善TDI加成物的硬度、耐划伤性等。  \n\na.基本配方 TDI三聚体的代表产品以及性能指标见表3-7-84。  \n\n表3-7-84TDI三聚体技术指标  \n\n\n<html><body><table><tr><td rowspan=\"2\">指标</td><td>BAYER</td><td>SAPICI</td><td>日胜</td></tr><tr><td>DESMODUR IL BA</td><td>HR.B</td><td>SC550IL</td></tr><tr><td>固含量/% NCO含量/% 游离TDI含量/% 黏度（25℃）/mPa·s</td><td>50 8 一 1600</td><td>50 7.8~8.2 0.5 700～1200</td><td>50 7.3~8.3 1 150±100</td></tr></table></body></html>  \n\nb.生产工艺将组分A的所有原料投人反应釜，通氮气，开启揽拌，升温到65℃，保温，每半小时检测NCO含量一次，当NCO含量为8.0%～8.5%时合格，加人磷酸搅拌$10\\mathrm{min}$ ，降温。过滤包装即可。该固化剂的技术指标见表3-7-86。  \n\n$\\textcircled{3}$ 配方示例 三聚体固化剂配方见表3-7-85。  \n\n表3-7-85 三聚体固化剂配方  \n\n\n<html><body><table><tr><td>序号</td><td rowspan=\"3\">组分</td><td rowspan=\"3\">用量/%</td><td>序号</td><td>组分</td><td>用量/%</td></tr><tr><td>醋酸丁酯（氨酯级） 甲苯二异氰酸酯</td><td>49.5 50</td><td>磷酸（85%）</td><td>0~0.2</td></tr><tr><td>催化剂 抗氧剂</td><td colspan=\"2\">0～0.2 总计 0~0.2</td><td>100</td></tr></table></body></html>  \n\n表3-7-86 TDI三聚体技术指标  \n\n\n<html><body><table><tr><td>性能</td><td>指标</td><td>性能</td><td>指标</td></tr><tr><td>NCO含量/%</td><td>8.4</td><td>游离TDI含量/%</td><td>0.8</td></tr><tr><td>固含量（120℃，1h）/%</td><td>50</td><td>外观</td><td>透明液体</td></tr><tr><td>色泽（Pt-Co比色）</td><td>50</td><td></td><td></td></tr></table></body></html>  \n\n该三聚体可以作为通用的TDI三聚体使用，具有硬度高、耐划伤性好等优点。  \n\n$\\textcircled{4}$ TDI三聚体的改性与TDI加成物固化剂一样，为了满足漆膜性能的要求，也会对三聚体进行改性。改性的目的是为了提高三聚体的相容性、透明性等。改性的方法可以在三聚体合成的最后阶段加入部分的醇，以提高三聚体的相容性和柔韧性；也可以先让TDI与醇反应，然后再进行三聚。与标准的TDI三聚体相比较，经此方法改性的TDI三聚体，其NCO含量和黏度均有所下降。  \n\n目前，用于改性的醇通常都是醇醚类物质，例如乙二醇丁醚、丙二醇甲醚、丙二醇丁醚、二乙二醇丁醚等。原因是这些醇都是一元醇，不会引起扩链，同时含醚键的、柔软的长链分子结构引入三聚体后，降低了分子极性，提高了相容性。改性后的三聚体还有一个特点就是降低了体系的玻璃化温度，表干速率介于加成物固化剂和三聚体之间。  \n\n改性三聚体的代表产品是SAPICI的POLURENEAC510和 $60\\mathrm{T}$ ，其技术指标见表3-7-87。  \n\n表3-7-87SAPICI改性三聚体技术指标  \n\n\n<html><body><table><tr><td>指标</td><td>60T</td><td>AC510</td><td>指标</td><td>60T</td><td>AC510</td></tr><tr><td>溶剂</td><td>醋酸丁酯</td><td>醋酸丁酯</td><td>色泽(Fe-Co比色）</td><td>1</td><td>1</td></tr><tr><td>NCO含量/%</td><td>9.5~9.9</td><td>7.0～7.4</td><td>游离TDI含量/% <</td><td>0.5</td><td></td></tr><tr><td>固含量（120℃，1h）/%</td><td>60</td><td>50</td><td>黏度（23℃）/mPa·s</td><td>1200~2000</td><td>50~300</td></tr></table></body></html>  \n\nAC510与硝化棉、丙烯酸树脂和二甲苯、甲苯等具有良好的相容性，柔韧性好。与AC510相比， ${\\mathfrak{s o T}}$ 除与丙烯酸树脂的相容性略差外，其他基本相同。  \n\n(6）HDI固化剂HDI固化剂是除TDI固化剂之外在木用涂料中应用较多的一种。HDI是脂肪族的多异氰酸酯，用其合成的固化剂，耐黄变性能优异、黏度低。通常用于浅色透明涂装、浅色实色涂装中。HDI固化剂主要的商品形式是三聚体和缩二脲，两者比较，三聚体固化后漆膜的硬度略高、黏度较低、稳定性更好。  \n\n$\\textcircled{1}$ HDI缩二脲HDI单体在一定条件下有控制地与水反应生成HDI缩二脲（图3-7-10)。由于HDI单体的挥发性和毒性均高，故常以缩二脲的形式来使用。缩二脲由三分子HDI和一分子水经缩聚反应而生成。  \n\n![](images/aec5c48f29cc3a2aad28bc9cbb87c32622f1771c75995e2dc06bcab3a056e424.jpg)  \n图3-7-10 HDI缩二脲结构  \n\n由于羰基旁有两个活泼氢原子，反应可以更深人地进行下去，生成二缩二脲、三缩二脲、四缩二脲等产物。因此HDI缩二脲的商品是这些缩二脲的混合物，由于含脲结构的、高分子量的多异氰酸酯的存在，溶液变得不透明甚至浑浊，在反应时，还会生成带着脲基的、分子量更高的多元异氰酸醋类。表3-7-88是商品缩二脲的产品组成。缩二脲生产工艺如下。  \n\n表3-7-88 缩二脲组成  \n\n\n<html><body><table><tr><td>组分名称</td><td>质量分数/%</td><td>组分名称</td><td>质量分数/%</td></tr><tr><td>HDI单体</td><td>0.1</td><td>三缩二脲</td><td>9.5</td></tr><tr><td>单缩二脲</td><td>44.5</td><td>四缩二脲</td><td>5.4</td></tr><tr><td>二缩二脲</td><td>17.4</td><td>高分子量化合物</td><td>23.1</td></tr></table></body></html>  \n\n少量的六亚甲基二异氰酸酯（HDI）和水在静态混合器中连续地进行混合后随即送人两个串联的反应釜中。并将HDI连续地从贮槽加人反应釜中。第一个反应釜的温度保持在170℃，第二反应釜的温度为150℃，两个反应釜都用夹套蒸汽加热。每个反应在釜内均配置了两个串联的冷凝器，以防止HDI随反应中放出的二氧化碳一起逸去。过滤后的液体在真空薄膜蒸发器中进行蒸发，以回收没有起反应的HDI。从蒸发器底部排出的液态缩二脲仅含 $0.3\\%$ 的 $\\mathrm{\\DeltaHDI}$ 。用溶剂将此产物配制成 $75\\%$ 固体含量的最终产物。  \n\n典型产品是DESMODURN75、POLURENE M75 等，技术指标见表3-7-89。  \n\n表3-7-89 HDI缩二脲技术指标  \n\n\n<html><body><table><tr><td rowspan=\"2\">指标</td><td>BAYER</td><td>SAPICI</td><td rowspan=\"2\">指标</td><td>BAYER</td><td>SAPICI</td></tr><tr><td>N75</td><td>M75</td><td>N75</td><td>M75</td></tr><tr><td>溶剂</td><td>MPA/二甲苯</td><td>MPA/二甲苯</td><td>黏度（23℃）/mPa·s</td><td>250±75</td><td>150~310</td></tr><tr><td>NCO含量/%</td><td>16.2~16.8</td><td>16~17</td><td>色泽（Fe-Co比色）</td><td></td><td><1</td></tr><tr><td>固含量（100℃，2h）/%</td><td>75</td><td>75</td><td>游离单体含量/% <</td><td>0.5</td><td>0.2</td></tr></table></body></html>  \n\n② HDI三聚体 HDI三聚体的基本原理与TDI三聚体相一致。HDI三聚体和缩二脲相比，三聚体在干燥、硬度和耐候性方面具备明显的优势。DESMODURN3390是BAYER公司HDI三聚体，而 POLURENEMT90 是 SAPICI的产品，CORONATE HX-90B 是NPU产品。具体技术指标见表3-7-90。  \n\n表3-7-90 HDI三聚体技术指标  \n\n\n<html><body><table><tr><td>指标</td><td>DESMODUR N3390</td><td>CORONATE HX-90B</td><td>MT 90</td></tr><tr><td>溶剂</td><td>醋酸丁酯/100*溶剂油</td><td>醋酸丁酯</td><td>醋酸丁酯/100*</td></tr><tr><td>NCO含量/%</td><td>19.3~19.9</td><td>18.2~19.8</td><td>19~21</td></tr><tr><td>固含量（100℃，2h）/%</td><td>90</td><td>89~91</td><td>90</td></tr><tr><td>色泽（GARDNER) <</td><td>1</td><td>一</td><td>1</td></tr><tr><td>游离单体含量/% 八</td><td>0.15</td><td>一</td><td>0.2</td></tr><tr><td>黏度（23℃）/mPa·s</td><td>400～700</td><td>130~560</td><td>400~700</td></tr></table></body></html>  \n\nHDI固化剂无论是三聚体还是缩二脲，其干燥速率都较慢，特别是在低温施工时。解决的方法有三种：  \n\na.加催于剂，有机锡类催干剂对HDI固化剂的干燥速率有明显作用；  \nb. $50^{\\circ}C$ 以下低温烘烤；  \nc.与TDI三聚体混配后使用。  \n\n(7）混合型固化剂混合型固化剂是两种不同的异氰酸酯单体经化学反应后合成的产品。主要有HDI和TDI的混合三聚体。  \n\nHDI和TDI两种单体活性差别较大，在 $80^{\\circ}C$ 条件下与辛醇反应 $\\mathsf{5m i n}$ 后，前者转化率为 $23\\%$ ，后者为 $90\\%$ 。在HDI/TDI三聚体中，理想结构是1分子HDI及2分子TDI共同组成，六亚甲基处于异氰脲酸酯环中间，阻断了“共轭双键”效应，从而大大提高了抗泛黄性，因此若想接近理想状态，必须加大HDI单体的量，以增加这种低反应活性分子的反应机会，但这样就为后处理带来了较多的麻烦。如图3-7-11所示是HDI/TDI混合三聚体的理想结构。  \n\n![](images/ea80cdf9f5f111937a0bb1259436eb8b92e55fbad704b83090695c8212208b9e.jpg)  \n图3-7-11 HDI/TDI混合三聚体的理想结构  \n\nHDI/TDI混合固化剂的特点：与纯芳香族异氰脲酸酯相比较，混合固化剂的耐光性、保光性特别好，耐黄变性远远高于TDI三聚体，接近HDI缩二脲。它不需要与特殊的聚酯/醇酸配合，却可以在复杂的气候条件下保持其良好的保光性。漆膜干燥固化快，配漆后适用期长。在实际施工中还常常将HDI/TDI三聚体和HDI缩二脲混拼使用，以期获得比HDI缩二脲更为快干的。耐候性也比较好的漆膜。  \n\nHDI/TDI混合三聚体的技术指标见表3-7-91。  \n\n表3-7-91HDI/TDI混合三聚体技术指标  \n\n\n<html><body><table><tr><td>指标</td><td>Desmodur HL BA</td><td>OK. D. S</td><td></td></tr><tr><td>溶剂 NCO含量/%</td><td>醋酸丁酯 10.5</td><td rowspan=\"3\">醋酸丁酯</td><td>10~11 60</td></tr><tr><td>固含量（100℃，2h）/% 色泽（GARDNER)</td><td>60 <1</td><td><1</td></tr><tr><td>游离单体含量/%</td><td>一</td><td>HDI<0.1 TDI<0.4</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 579,
+        "chunk": "# 4.成膜过程中的固化交联机理  \n\n(1）交联反应聚氨酯涂料中，固化剂主要提供能够常温固化交联、成膜的物质基础。  \n\n异氰酸酯基团和羟基基团的交联反应是主反应，促使漆膜逐步干燥。交联反应的示意式如图3-7-12所示。  \n\n(2）与水的反应除了上述主要的交联反应之外，木用聚氨酯涂料由于受施工环境、底材的影响还有可能发生其他的副反应，主要是异氰酸酯与水以及多酚的反应。  \n\n水分的来源有以下几种$\\textcircled{1}$ 空气中的水分 特别是在潮湿天气下，其  \n\n![](images/48ef303163ae07824c056409fea0af1262483d35cb598ee33ff16eab5a9ad35f.jpg)  \n图3-7-12 聚氨酯漆膜固化交联机理  \n\n影响更为严重。  \n\n$\\textcircled{2}$ 涂料中的水分包括溶剂中含有的微量水分、生产过程中带入的水分。  \n$\\textcircled{3}$ 底材中的水分底材特别是木材本身都会有一定的游离水。  \n$\\textcircled{4}$ 施工设备中带来的水分例如喷涂所用的压缩空气中也会含有一定的水分。  \n\n异氰酸酯与水的反应示意图如图3-7-13所示。  \n\n反应分两步进行，第一步是水与NCO基团的反应，生成的中间产物是胺，第二步是生成的胺与NCO基团继续反应，并最终生成脲。由于胺与NCO的反应速率很快，所以起决定作用的是反应的第一步。  \n\n从该反应的示意式中，可以得出如下结论。  \n\n$\\textcircled{1}$ lmol水分子与 $2\\mathrm{mol}$ 的异氰酸酯反应，考虑到两者分子量的差异，可以认为少量的水参与反应将会导致固化剂的较大损失。  \n\n![](images/ac6d7aa79a200d20b7f946438c5afe2f6935931368175c294f9ea52a507cc1d1.jpg)  \n图3-7-13 异氰酸酯与水反应  \n\n$\\textcircled{2}$ 异氰酸酯与水反应，最终生成脲，同时产生二氧化碳气体。如果生成的二氧化碳不能及时从漆膜中逸出，会导致针孔、暗泡、气泡等漆膜病。  \n\n为了更清晰地阐述这个问题，可以进行简单的计算。  \n\n假设1m的涂布面积上的涂料总量是100g，含水率0.1%，则总含水量是0.1g即$0,0056\\mathrm{mol}$ 。根据图3-7-12的反应式，水的物质的量与二氧化碳的物质的量相同。  \n\n在标准条件下二氧化碳的体积 $\\mathbf{\\Lambda}=0.0056\\times22.4=0.1254(\\mathrm{L})=125.4(\\mathrm{~r~}$ nL)。  \n\n假设生成的气泡的直径为 $1\\mathrm{mm}$ ，则最终产生的气泡总数 $=125.4/(4\\pi\\times R^{3}/3)=30000$ （个)。  \n\n从以上的简单推导可以看出少量水分对聚氨酯涂料的重要影响，对于聚氨酯涂料而言，良好的消泡、脱泡能力是非常重要的，特别是在湿度高的环境下施工更要注意水分的不良影响。  \n\n(3）其他副反应对于木用涂料而言，底材中还会含有酚类物质，木材的处理过程中也有可能会带入其他活性物质，都会与聚氨酯固化剂中的异氰酸酯基团反应，消耗有效的NCO 基团，对漆膜的效果产生不利的影响，主要是附着力、透明度、抗开裂性以及黄变等。  \n\n(4）交联反应特点与加成物固化剂的合成相比，成膜过程中的交联反应具有如下的特点：  \n\n$\\textcircled{1}$ 交联反应发生的温度较低，都是在常温或低温烘烤下进行 $(\\leq50^{\\circ}C)$  \n\n$\\textcircled{2}$ 交联反应进行时，溶剂含量逐渐降低，漆膜的固含量越来越高；  \n\n$\\textcircled{3}$ 交联反应与外部环境接触多，受外界的影响大，例如湿度、温度等；  \n\n$\\textcircled{4}$ 交联反应发生时，分子量提高非常迅速。  \n\n以上特点决定聚氨酯漆膜中羟基组分和异氰酸酯组分的反应是不完全的，漆膜中既有残留的羟基，同时残留的NCO基团也会存在很长一段时间，据红外光谱的跟踪检测，即使在干燥30天后，漆膜中残留的NCO基团仍然显示较强的吸收峰。  \n\n(5）漆膜干燥固化过程聚氨酯漆膜的固化大致可以分为三个阶段，第一阶段是伴随大量溶剂的挥发，部分异氰酸酯基团与羟基树脂的交联，即表干阶段，通常15～60min；第二阶段以异氰酸酯基团和羟基树脂的交联为主，伴随部分溶剂的挥发，即实干阶段，通常4～48h；第三阶段是漆膜的充分固化交联阶段，漆膜达到完全干燥并表现出最佳性能。这一阶段持续的时间比较长，通常需要3个月以上时间。第一阶段以溶剂挥发为主，第二阶段以液相-液相交联反应向液相-固相、固相-固相交联反应的转变为主，第三阶段以固相-固相的交联反应为主。由于受分子运动的影响，固相-固相反应进行得很缓慢。为使漆膜达到最佳的交联密度，漆膜的表干时间不宜太快，否则交联密度降低，影响漆膜性能。  \n\n因此，在设定一个固化剂的配方时，必须考虑以下因素。  \n\n$\\textcircled{1}$ 施工环境的温度、湿度。  \n$\\textcircled{2}$ 溶剂体系对漆膜固化的影响。  \n$\\textcircled{3}$ 加成物和三聚体固化特点的差异。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 580,
+        "chunk": "# 5.木用涂料固化剂配方技术的难点透析  \n\n(1）进口固化剂和国产固化剂灵活搭配使用进口固化剂采用薄膜蒸发法处理游离TDI，国产固化剂采用后三聚法降低游离TDI，两种不同方法制得的产品性能差异较大。前者初干速率慢而实干较快，光泽高，与其他树脂的相容性好，韧性强，同等情况下漆膜光泽高。后者分子量大且分布不均匀，初干速率较快而实干较慢，易被消光，黏度大，相容性差，低温施工有开裂倾向。  \n\n在实际配方调整中，应将两种固化剂适当搭配，以达到性能和环保要求的综合平衡。例如，用于亚光漆的固化剂，可以增加国产固化剂的比例，以降低消光粉的用量，达到降低成本和提高漆膜透明度的目的；而用在亮光漆的固化剂，可以增加进口固化剂的比例，提高漆膜的光泽和透明度；在冬季气温较低的情况下，也应该增加薄膜蒸发法固化剂的比例，提高干燥性能。原因是它的玻璃化温度较低，流动性好，NCO和OH更容易交联，避免了固化不良、漆膜开裂等病。这一点从图3-7-14和图3-7-15也可以得到验证。  \n\n![](images/ed74929d29ce06909fee2ab1099aceb142b9810a53f4bf415c3f3918d6b469a1.jpg)  \n图3-7-14 进口TDI加成物固化剂加DSC图  \n\n![](images/621779453ac18cebd54840c6712928fe8c3a4b23d24a813135120d175cf53a76.jpg)  \n图3-715国产TDI加成物固化剂DSC图 $\\begin{array}{r l}{\\frac{1}{9}}&{{}:}\\\\ {\\quad\\cdot-\\quad}&{{}\\quad\\cdot}\\end{array}$  \n\n从上述两个图中可以看出，薄膜蒸发法固化剂加成物的玻璃化温度比三聚法高约20℃。因此，当环境温度较低时，建议采用进口固化剂，或在混合固化剂中加大其比例，此时加人少量的催干剂例如有机锡，能提高漆膜的交联能力，达到较佳的漆膜性能。  \n\n必须避免走人一种误区，认为三聚法固化剂加成物的干燥速率比薄膜蒸发法快，从而在冬季气温较低，漆膜固化不良时，就错误地加人更多的三聚法固化剂加成物，其结果是不仅不能解决问题，反而会导致问题更为严重。原因是三聚法固化剂加成物的玻璃化温度高、分子量大，漆膜表干时间短，所谓的干燥其实是“假干”，漆膜表干后，分子运动受阻，分子碰撞概率减小，交联反应难于进行，实干就很慢。而薄膜蒸发法固化剂由于玻璃化温度较低，即使在冬季的低温天气下，NCO和OH仍可进行交联反应，实干不会慢，当然需要的时间要比高温下要长。  \n\n由图3-7-16、图3-7-17和表3-7-92可以明显看出，两种产品在分子量以及分子量的分布上有明显的差异，薄膜蒸发法产品的分子量较低，分布也较为均匀，而三聚法产品的分子量较高，分布宽，呈多峰分布。  \n\n![](images/252b90c1baa37e719bf633a7d24b994108be9f1dc6ad21bace8ef5866a931685.jpg)  \n图3-7-16 进口TDI加成物固化剂的GPC图  \n\n![](images/5cac21ffb7048764b99fa1312038a4ca516ae15b115af9fb6dddda1f71b58bee.jpg)  \n图3-7-17 国产TDI加成物固化剂的GPC图  \n\n表3-7-92 两种TDI固化剂加成物的产品指标对比  \n\n\n<html><body><table><tr><td>指标</td><td>进口产品</td><td>国产产品</td></tr><tr><td>色泽（Pt-Co比色）</td><td>40~100</td><td>40~100</td></tr><tr><td>黏度/mPa·s</td><td>2000±500</td><td>2000±500</td></tr><tr><td>固含量/%</td><td>75</td><td>60</td></tr><tr><td>游离TDI含量/%</td><td>0.5</td><td>2.0</td></tr><tr><td>与二甲苯的容忍性 NCO含量/%</td><td>V 3 12.5~13.5</td><td>10 8.8~9.1</td></tr></table></body></html>  \n\n(2）游离TDI的矛盾统一由于反应的选择性不足，聚氨酯固化剂中残留的TDI在漆膜干燥的过程中挥发出来，危害人体健康。根据GB18581的规定，全漆中游离TDI含量应低于 $0.7\\%$ ，虽然此标准要求不高，但仍然有部分不达标的产品在市面销售。目前符合国标的产品分为两类：一是采用薄膜蒸发去除游离TDI的产品，以BAYER为代表的国外品牌；二是采用化学法去除游离TDI的产品，以国内厂家为主。两种类型的产品在性能上有一定的差异，其原因是薄膜蒸发法是采用物理的方法快速进行处理的，产品前后分子量变化小。  \n\n所谓的化学法一般是通过后三聚的方法降低游离TDI的含量，但同时体系的分子量也迅速增加，玻璃化温度升高。  \n\n除对环境的影响之外，游离TDI对漆膜性能的影响有正面的也有负面的。  \n\n负面影响：游离TDI含量高时，漆膜黄变倾向大，如果含量超过 $5\\%$ ，气味较大。  \n\n正面影响：通常游离TDI含量高的固化剂与醇酸、硝化棉等其他树脂的相容性明显提高，漆膜柔韧性提高，漆膜开裂倾向降低。当然，不能因为这个原因而故意保持高含量的游离TDI。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 581,
+        "chunk": "# (3）开裂问题  \n\n$\\textcircled{1}$ 聚氨酯涂料漆膜开裂病描述涂料干燥后，漆膜表面出现细小裂缝的弊病称之为漆膜开裂，但是漆膜老化过程中产生的开裂则不在这里讨论的范围以内。开裂一旦发生，往往是从涂装工件的边角或接口的位置开始出现，并有逐步向中心部位扩散的趋势。  \n\n$\\textcircled{2}$ 聚氨酯涂料漆膜开裂特点  \n\na.开裂病的出现有一定的地域性，一般黄河以北出现开裂的概率大，黄河以南出现开裂的概率小。  \n\nb.漆膜所处的环境温差越大，出现开裂的概率越高；温差越小，出现开裂的概率越低。  \n\nc.固化剂中三聚体使用的比例越大，出现开裂的概率越高。  \n\nd.底材湿度越高，出现开裂的概率越大。  \n\ne.配套底漆干燥慢，面漆干燥越快，出现开裂的概率越大。  \n\nf.通常出现开裂病的时间是在涂装施工一个月内出现，最快隔夜即会出现。  \n\ng.施工温度越低，出现开裂的概率越高。  \n\nh.曲面出现开裂的概率大，而平面出现开裂的概率小。  \n\n$\\textcircled{3}$ 漆膜开裂原因分析聚氨酯涂料漆膜的开裂问题在近几年逐渐变得严重，其表观原因：一是客户对干燥速率的过分追求，配方工程师被迫加人更多的三聚体固化剂或其他玻璃化温度较高的组分，导致漆膜的初干速率过快；二是涂装时一次喷涂的湿膜越来越厚；三是低温施工时，固化条件不佳，导致漆膜出现“假干”现象。  \n\n聚氨酯漆膜开裂的内在原因，归根到底，是漆膜内应力的原因。  \n\na.应力和内应力应力是物体受外因而变形时，在物体内各部分之间产生相互作用的内力，以抵抗外因的作用，并力图使物体从变形后的位置回复到变形前的位置。在所考察的截面某一点单位面积上的内力称为应力。  \n\n物体在不受外力作用的情况下，内部固有的应力叫内应力，它是由于物体内部各部分发生不均匀的塑性变形而产生的。  \n\n当内应力超过漆膜承受的极限时，就会导致漆膜断裂或开裂。  \n\nb.漆膜内应力产生的原因 漆膜内应力产生的原因很多，大致有以下几种。  \n\n$\\cdot$ 体积变化产生的内应力当基材与漆膜的体积变化不一致时，就会产生内应力。例如，中国北方的家具厂内通常有暖气设施，用来提高漆膜的固化速率，但家具的运输途中，则气温很低。从家具的固化到运输，环境温度急剧变化，基材和漆膜的体积收缩不一致，如果产生的内应力超过漆膜的极限应力就会导致开裂。这种开裂的现象通常在黄河以北地区出现，黄河以南地区很少出现。消除体积变化产生的内应力主要是提高漆膜的柔韧性。  \n\n$\\cdot$ 分子构型变化产生的内应力聚氨酯涂料在干燥过程中，溶剂不断挥发，分子链的形状变化趋势是由溶液里的舒展状态逐渐变成干膜中的线团状。当溶剂挥发速率很快时，会导致内应力急剧增加，如果产生的内应力超过漆膜的极限应力，就会导致漆膜开裂。然而，在漆膜固化过程中，异氰酸酯和羟基的交联会起到固定分子链的作用，阻止链的卷曲，降低内应力的产生。因此，提高漆膜的交联速率以及交联密度，可以有效防止开裂的产生。例如，在中国北方低温干燥的条件下施工，由于湿度较低，溶剂挥发速率仍然较快，但是漆膜的交联速率很慢，这种情况下，漆膜出现开裂病的概率也就相应增加了。  \n\n$\\cdot$ 温度高低的交替变化产生交变应力例如，评估漆膜开裂性能的时候，会人为地将测试样板在高、低温循环放置，便于观察开裂现象。温度的周期性变化导致内应力也随之，变化。  \n\n$\\cdot$ 相分离产生的内应力聚氨酯涂料体系中，含羟基组分和异氰酸酯组分由于内聚能的差异，在本质是不完全相容的，两者之间存在一定的相分离现象。固化剂中的氨基甲酸酯或脲基具有较高的内聚能，具有彼此缔合的趋势。含羟基组分由于内聚能较低，也有彼此聚集的倾向。  \n\n$\\textcircled{4}$ 漆膜开裂产生的原因与防治根据以上的原因分析，漆膜在施工固化后，会受到由于不同原因而产生的各种内应力作用。开裂产生的本质原因是由于漆膜受到一种或几种不同的内应力的共同作用。但不是所有的内应力都会导致漆膜开裂，只当漆膜内应力超过漆膜的极限应力时，才会出现开裂。这种开裂会导致漆膜表面整体性的同时开裂，往往比较少见，常见的是局部开裂，其原因是由于漆膜的应力集中产生的。  \n\n所谓应力集中就是施加在漆膜表面的外力，使得材料内部产生的应力会因各种原因在某些部位成倍地集中，致使这些地方承受不了而率先发生断裂。应力集中的地方主要有：几何上的不连续处，如家具的边角、孔、空洞、缺口、沟槽等；漆膜组分和材质的不连续处，如多组分、多相材料等；载荷上的不连续处，受力不均；漆膜表面温度分布不均匀处。由此造成材料的某个小体积中，应力比平均应力大得多，如超过极限应力，漆膜就会发生开裂。木用涂料中，漆膜开裂发生的位置通常是在家具的边、角或曲面等位置也就是这个原因。  \n\n防止漆膜的开裂：一是减少内应力的产生；二是内应力产生后，可以进行有效地应力松弛；三是防止内应力集中。具体如下。  \n\na.减少漆膜内应力的产生提高漆膜的柔韧性，当基材和漆膜体积变化不一致时，漆膜良好的柔韧性可以提高漆膜的抗开裂性。  \n\n漆膜的完全固化可以提供更多的交联点，从而在漆膜固化和溶剂挥发的过程中，对分子链的形变形成约束，降低内应力的产生，例如烘烤（ $50^{\\circ}C$ ）可以大大提高漆膜的交联密度，降低开裂风险。  \n\n低温施工时，TDI三聚体固化剂的加人会提高漆膜开裂的风险。原因之一是TDI三聚体固化剂的玻璃化温度高，溶剂挥发后，漆膜即处于固相状态中，分子运动速率迅速降低，NCO和羟基反应的反应速率降低，从而导致交联密度降低；原因之二是溶剂挥发后，分子链由舒展状态逐步变成线团状，内应力逐步积累，遇到温度变化等外来诱因的话，加上交联密度不足，就有可能导致开裂，特别是在底材的边角处以及缝隙位置。相反如果在这种条件下，加入的固化剂是TDI加成物，其玻璃化温度较低，可供交联反应进行的有效时间较长，分子运动速率快，碰撞概率大，固化更完全，漆膜不易开裂。因此在低温施工时，不能通过加入TDI三聚体固化剂的方法来提高漆膜的干燥速率，而是要通过提高固化温度、固化时间和加人催干剂以及位阻胺等手段来提高漆膜的固化程度。  \n\n如果要求面漆有很高的硬度，配套底漆应该选择柔韧性较好的，降低基材和面漆之间的内应力的产生，达到防止开裂的目的。  \n\nb.有效的应力松弛应力松弛是在恒定的温度和形变保持不变的情况下，聚合物内部的应力随时间增加而衰减的现象。将涂装后的工件在 $50^{\\circ}C$ 烘烤，可以有效释放内应力，达到抗开裂的目的。  \n\nc.防止应力集中应力集中总是在漆膜的薄弱处出现，并导致开裂概率增加。  \n\n·基材处理，如果基材有裂缝存在，应先用腻子填平，并充分干燥，而不能依赖底漆。  \n$\\cdot$ 降低漆膜缺陷，如气泡、针孔等。  \n$\\cdot$ 提高对基材的润湿性和附着力。  \n$\\cdot$ 薄涂多次的施工方法。  \n\n(4）NCO/OH比例NCO/OH的比例在木用聚氨酯涂料中实际的范围很宽，通常为$1.0{\\sim}1.2\\$ 。通用的原则是对于底漆而言，应保留部分羟基，提高底漆和面漆的层间附着力(前提是面漆要带人多余的NCO基团)；对面漆而言，NCO过量，可以提高漆膜的硬度、耐划伤性等。在前文聚氨酯涂料的干燥机理中已经了解到，聚氨酯涂料的干燥过程中，一方面由于水的存在会消耗部分NCO；另一方面，由于NCO和OH不可能全部交联，而是有部分残留在漆膜中。因此，在聚氨酯木用涂料中，NCO/OH的比例虽然并不像汽车漆那样严格控制，但还是应该遵循上述基本原则。  \n\n根据国内消费的习惯，聚氨酯木用涂料通常的施工比例是重量的整数比，主剂：固化剂 $=1:0.5$ 或 $1:1$ ，更常见的是，对于底漆和亚光清漆，通常采用主剂：固化剂 $=1:0.5$ 的比例，而对于亮光漆，通常采用主剂：固化剂 $=1:1$ 的比例。其原因是为了施工方便。要做到这一点，可以通过调整主剂中树脂的加人比例、固化剂的固体分、固化剂的NCO含量和施工黏度最后得到合适的NCO/OH比例。  \n\n(5）溶剂应用问题出于成本控制的目的，固化剂中常加入甲苯、二甲苯等溶剂，但由于国家法规的限制，三苯含量受限，苯类溶剂用量减少。目前主要采用醋酸乙酯、醋酸仲丁酯、碳酸二甲酯等溶剂与醋酸丁酯拼用，控制成本、溶解性和挥发速率的平衡。几种溶剂的物理常数见表3-7-93。  \n\n表3-7-93几种溶剂的物理常数  \n\n\n<html><body><table><tr><td>性能</td><td>醋酸正丁酯</td><td>醋酸乙酯</td><td>醋酸仲丁酯</td><td>碳酸二甲酯</td></tr><tr><td>分子量</td><td>116</td><td>88</td><td>116</td><td>90</td></tr><tr><td>沸点/℃</td><td>126</td><td>77.1</td><td>1112.3</td><td>90.2</td></tr><tr><td>熔点/℃</td><td>-77.9</td><td>-83.6</td><td>－98.9</td><td>2~4</td></tr><tr><td>密度/（kg/ma）</td><td>0.8825</td><td>0.9003</td><td>0.86</td><td>1.073</td></tr><tr><td>相对挥发速率</td><td>1</td><td>5.25</td><td>1.8</td><td>3.35</td></tr><tr><td>20℃蒸气压/kPa</td><td>1.33</td><td>9.7</td><td>2.0</td><td>6.27</td></tr><tr><td>汽化热/(J/g)</td><td>309.4</td><td>366.5</td><td>一</td><td>一</td></tr><tr><td>比热容/[J/(g·K)]</td><td>1.91</td><td>1.92</td><td>1.92</td><td>一</td></tr><tr><td>闪点（开杯）/℃</td><td>33</td><td>4</td><td>31</td><td>21.7</td></tr><tr><td>折射率</td><td>1.3951</td><td>1.3723</td><td>1.3894</td><td>1.3697</td></tr><tr><td>溶解度参数/</td><td>8.5</td><td>9.1</td><td>一</td><td>10.4</td></tr><tr><td>黏度（20℃）/mPa·s</td><td>0.734</td><td>0.449</td><td>一</td><td>0.664</td></tr><tr><td>水中的溶解度/（g/L）</td><td>一</td><td>80</td><td>30</td><td>139</td></tr></table></body></html>  \n\n醋酸乙酯：由于乙醇是可再生原料，与丁醇相比，价格更低，市场供应稳定。溶解能力与醋酸丁酯接近，常用来部分代替醋酸丁酯。但是，醋酸乙酯的挥发速率快，汽化热高，如用量太多，则干燥过程中漆膜表面的温度下降大，容易造成漆膜发白等病，特别是在夏季施工时，漆膜发白、针孔和透明度下降等问题很容易出现。因此醋酸乙酯在配方中的用量不宜超过 $20\\%$ ，同时需要注意施工环境温度。  \n\n醋酸仲丁酯：与醋酸丁酯相比，采用的生产工艺和原材料不同，价格差异较大，但其溶解性与醋酸丁酯接近，挥发速率则较快。醋酸仲丁酯的用量可以比醋酸乙酯大，但仍需要与醋酸丁酯等混合使用。  \n\n在木用涂料中使用时存在的问题：一是气味问题，涂料气味大，涂装后气味残留的时间长；二是发白问题，全部采用醋酸仲丁酯，漆膜也有发白的倾向，但比醋酸乙酯好。  \n\n碳酸二甲酯：毒性低，对极性弱的树脂溶解性较好，对极性强的树脂需与其他溶剂配合使用。  \n\n$\\textcircled{1}$ 作为固化剂的稀释溶剂碳酸二甲酯甲基上的氢与固化剂中NCO基团具有极弱的反应性，长期存放是会导致固化剂的胶化或变黄，因此，该溶剂不推荐用于固化剂的稀释。  \n\n$\\textcircled{2}$ 作为树脂的稀释溶剂要求在较低的兑稀温度下进行，因为碳酸二甲酯的两个酯键在高温下会发生酯交换反应。  \n\n$\\textcircled{3}$ 主要推荐在主剂和稀释剂中使用由于碳酸二甲酯的密度较大，比通常的树脂和溶剂的密度都要大，在漆膜干燥过程中，不能彻底挥发，造成漆膜容易出现发白、硬度低等弊病。因此，碳酸二甲酯的用量必须经过严格试验来确定，达到成本和性能的平衡。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 582,
+        "chunk": "# 6.混合固化剂  \n\n混合固化剂是用不同的固化剂产品按需混合，进口与国产、TDI与HDI、加成物与三聚体或以上的任意组合，以满足各种需要。配方灵活多变、生产简易，且实用性很强。  \n\n（1）混合固化剂配方示例$\\textcircled{1}$ 通用配方 见表3-7-94。  \n\n表3-7-94 通用配方  \n\n\n<html><body><table><tr><td>组成</td><td>质量分数/%</td><td>组成</td><td>质量分数/%</td></tr><tr><td>国产TDI加成物</td><td>55</td><td>丙二醇甲醚丙酸酯</td><td>5</td></tr><tr><td>DESMODUR L75</td><td>30</td><td>吸水剂</td><td>0.2</td></tr><tr><td>二甲苯</td><td>9</td><td>催干剂</td><td>0.002</td></tr></table></body></html>\n\n$\\textcircled{1}$ 国产TDI固化剂采用三聚法处理，固含量为 $60\\%$ ，NCO含量为 $9.4\\%$ ，游离TDI含量为 $1.4\\%$ ，溶剂组成为醋酸丁酯：丙二醇甲醚丙酸酯 $\\fint\\mathop{=}3:1$ ，下同。$\\textcircled{2}$ 吸水剂是Borchers公司的Additve $\\boldsymbol{\\mathsf{T I}},$ 晶$\\textcircled{3}$ 催干剂是美国气体产品有限公司产品 $T-12$ ，下同。  \n\n该配方可以用于聚氨酯的底漆和面漆中，既可以在冬天使用，也可以在夏季高温环境下施工，具有良好的通用性。  \n\n$\\textcircled{2}$ 快干固化剂配方 见表3-7-95。  \n\n表3-7-95 快干固化剂配方  \n\n\n<html><body><table><tr><td>组成</td><td>质量分数/%</td><td>组成</td><td>质量分数/%</td></tr><tr><td>国产TDI加成物</td><td>60</td><td>醋酸丁酯</td><td>10</td></tr><tr><td>国产TDI三聚体</td><td>22</td><td>吸水剂</td><td>0.2</td></tr><tr><td>二甲苯</td><td>6</td><td>催干剂</td><td>0.002</td></tr></table></body></html>\n\n$\\textcircled{1}$ 国产三聚体固化剂固含量为 $50\\%$ ，NCO含量为 $9.3\\%$ ，游离TDI含量为 $0.9\\%$ ，溶剂为醋酸丁酯。下同。  \n\n该配方主要用于亚光面漆中，具有干燥快、易消光的优点。  \n\n$\\textcircled{3}$ 低成本配方 见表3-7-96。  \n\n表3-7-96 低成本配方   \n\n\n<html><body><table><tr><td>组成</td><td>质量分数/%</td><td>组 成</td><td>质量分数/%</td></tr><tr><td>改性TDI三聚体</td><td>41</td><td>二甲苯</td><td>14</td></tr><tr><td>聚酯改性TDI加成物</td><td>41</td><td>醋酸丁酯</td><td>4</td></tr></table></body></html>\n\n$\\textcircled{1}$ 改性TDI三聚体固含量为 $50\\%$ ， $N(\\mathrm{CO}$ 含量为 $8.7\\%$ ，溶剂组成为醋酸丁酯：二甲苯 $=1:4$ $\\textcircled{2}$ 聚酯改性TDI加成物固含量为 $50\\%$ 。 $N\\mathbb{C}\\mathbb{O}$ 含量为 $5.5\\%$ ，游离TDI含量为 $1.2\\%$ ，溶剂组成为醋酸丁酯：二甲 苯：醋酸乙酯 $=2:1:2$ 费  \n\n该配方主要用于底漆配方中，具有成本低、兼顾打磨和柔韧性的特点。成本降低主要是通过溶剂的调整以及采用了便宜的聚酯改性TDI加成物。  \n\n$\\textcircled{4}$ 低成本耐黄变固化剂配方 见表3-7-97。  \n\n表3-7-97 低成本耐黄变固化剂配方  \n\n\n<html><body><table><tr><td>组成</td><td>质量分数/%</td><td>组成</td><td>质量分数/%</td></tr><tr><td>BAYER DESMODUR L 75</td><td>30</td><td>丙二醇甲醚丙酸酯</td><td>6</td></tr><tr><td>N3390?</td><td>46</td><td>吸水剂</td><td>0.2</td></tr><tr><td>醋酸丁酯</td><td>9</td><td>催干剂</td><td>0.002</td></tr></table></body></html>\n\n$\\textcircled{1}$ BARYER公司产品，TDI加成物。$\\textcircled{2}$ BARYER公司产品，HDI三聚体。  \n\n该固化剂具备良好的耐黄变性，同时兼顾了产品成本。通过TDI加成物提高HDI固化剂的干燥性能，同时耐黄变性提高。注意生产和包装过程中均应保持氮气环境，防止质量事故。  \n\n$\\textcircled{5}$ 高耐黄变固化剂 见表3-7-98。  \n\n表3-7-98 高耐黄变固化剂配方  \n\n\n<html><body><table><tr><td>组成</td><td></td><td>质量分数/%</td><td>组成</td><td>质量分数/%</td></tr><tr><td>O. K. D. S</td><td></td><td>37</td><td>吸水剂</td><td>0.2</td></tr><tr><td>N3390 醋酸丁酯</td><td></td><td>22 41</td><td>催干剂</td><td>0.002</td></tr></table></body></html>\n\n$\\textcircled{1}$ SAPICI公司产品。$\\textcircled{2}$ BAYER公司产品。  \n\n该固化剂具备优异的耐黄变性，适合耐黄变性要求高的浅色漆或作为户外用途。注意生产和包装过程中均应保持氮气环境，防止质量事故。  \n\n以上示例仅供参考，实际应用中，应根据具体的性能要求和使用环境，灵活调整。  \n\n(2）混合固化剂生产工艺混合固化剂配方的主要组分包括各种异氰酸酯组分、混合溶剂、催干剂和吸水剂。生产工艺则比较简单，几种组分的物料混合搅拌均匀即可。难点是防止水的副作用、设备的清洁、产品的贮存稳定性和包装。  \n\n设备清洁是非常重要的，活性物质的污染增加了固化剂的胶凝风险。设备清洗主要采用溶剂例如醋酸丁酯搅拌清洗，判定标准是清洗后的溶剂不发白、清澈透明即可。还有一种方法是将清洗后的溶剂按照 $1:10$ 的比例加人到要生产的固化剂中，混合均匀后，溶液透明即可，如果出现发白、浑浊即表明设备清洗不达标。  \n\n固化剂中如果有水，会导致贮存稳定性变差，常见的是胀罐，胀罐是由于水和NCO基团反应后释放出二氧化碳所致。防止水的污染主要有三种手段：  \n\n$\\textcircled{1}$ 溶剂脱水用于固化剂生产的溶剂，其含水率必须达到氨酯级水平。溶剂脱水可以采用升温回流的方式，通常回流 $\\mathrm{1}\\mathrm{\\sim}\\mathrm{2h}$ ，溶剂的含水率可以得到有效降低。  \n\n$\\textcircled{2}$ 通入氮气在固化剂混合过程中，通人氮气是防止空气中水分影响的有效方法，不仅在配料缸中通入氮气，包装桶中也要通入氮气，对没有用完的固化剂材料，最好也能通入氮气保护。不同的异氰酸酯单体类型对水的敏感程度不同，MDI、HDI和后三聚法TDI加成物固化剂对水都非常敏感，生产设备需要密封和氮气保护，桶装的原材料最好一次用完。  \n\n$\\textcircled{3}$ 加入吸水剂吸水剂优先与水反应，从而降低水分对固化剂的影响。但吸水剂只能解决少量水分带来的问题，起主要作用的还是溶剂脱水和氮气保护。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 583,
+        "chunk": "# 7.固化剂的发展  \n\n聚氨酯固化剂的发展从以下几个方面进行简单介绍。  \n\n（1）异氰酸酯单体的应用发展目前，国内聚氨酯固化剂主要使用的是TDI类型的固化剂，原因是TDI固化剂的优异性能和价格较低。但由于石油价格的不稳定因素以及国产TDI的产能限制，目前聚氨酯固化剂中二苯甲烷二异氰酸酯（diphenylmethane diisocya-nate）MDI的应用研究越来越广。MDI分子式为 $\\mathrm{C_{15}\\ H_{10}\\ N_{z}O_{2}}$ ，分子量250.26。MDI有2,4-位和 $4,4^{\\prime},$ -位两种异构体。纯MDI是指 $4,4^{\\prime}$ -位异构体纯度达 $98\\%$ 以上的产品。 $4,4^{\\prime}.$ -二苯甲烷二异氰酸酯的结构式为：  \n\n$$\n\\mathrm{ocv-}\\bigcirc-\\mathrm{CH}_{2}-\\bigcirc-\\mathrm{NCO}\n$$  \n\nMDI纯度达 $99.5\\%$ 以上时，室温下是呈白色或微黄色固体，熔化后为无色或微黄色液体，溶于丙酮、苯、甲苯、氯苯、硝基苯、煤油、乙酸乙酯等，色度 $(\\mathbf{APHA}){\\leqslant}30$ ，凝点$38\\sim39^{\\circ}C$ ，沸点 $190^{\\circ}C$ ( $0.67\\mathrm{kPah}$ 下)，相对密度( $50^{\\circ}C$ ）1.19，动力黏度（ $50^{\\circ}C$ ）4.7mPa·s，闪点 $213^{\\circ}\\mathrm{C}$ ，燃点 $220^{\\circ}C$ ，NCO基团含量 $33.6\\%$ 。纯MDI极易与水发生反应，生成不溶性的脲类化合物并放出二氧化碳，造成涨桶并致浑浊。因此，在贮存过程中必须保证容器的严格干燥、密封，并充干燥氮气保护。  \n\n采用MDI作为异氰酸酯单体合成的固化剂，其特点如下：  \n\n$\\textcircled{1}$ 由于MDI结构中含有两个苯环，耐黄变性比TDI差；  \n$\\textcircled{2}$ 由于其结构对称，固化剂与其他树脂特别是硝化棉的相容性较差；  \n$\\textcircled{3}$ 由于两个NCO基团的反应活性无差异，游离MDI的含量较大；  \n$\\textcircled{4}$ 干燥速率比TDI固化剂慢；  \n③贮存稳定性比TDI固化剂差，微量水分对MDI固化剂的贮存安定性影响巨大。  \n\nMDI主要应用于聚氨酯发泡行业中，相关文献报道也较多，例如，CN1724576、CN1232555C、CN100372880C、CN 1878816A、CNI00368454C、CN 1256359C等，但在涂料中的应用还不多见。  \n\n中国专利CN1116327C中公开了一种涂料固化剂：三羟甲基丙烷与麻油进行醇解反应，醇解产物与4，4'-二苯基甲烷二异氰酸酯反应得到涂料固化剂。但由于麻油的颜色再加上高温醇解，所得产物色泽较深。中国专利CN1116328C中公开了一种由三羟甲基丙烷与 $4,2^{\\prime}$ -二苯基甲烷二异氰酸酯及 $4,4^{\\prime}.$ -二苯基甲烷二异氰酸酯混合物反应得到的聚氨酯涂料固化剂，其中，4,2'-二苯基甲烷二异氰酸酯的用量占整个用量的40%～60%（质量分数)。  \n\n中国专利（CN10029535.6）介绍了一种MDI固化剂的合成方法，反应的第一步是MDI与三羟甲基丙烷反应，由于此时MDI过量较多，MDI中第二个NCO基团反应的概率降低；反应的第二步是加入计量的仲醇，例如二丙二醇，由于仲醇的反应活性低，一定程度上提高了反应的选择性。产品具有贮存稳定性好、与羟基丙烯酸树脂及醇酸树脂混合后相容性好、施工寿命长等特点。  \n\n配方与工艺见表3-7-99。  \n\n表3-7-99 MDI固化剂配方  \n\n\n<html><body><table><tr><td>组成</td><td>质量分数/%</td><td>组成</td><td>质量分数/%</td></tr><tr><td>三羟甲基丙烷</td><td>26.8</td><td>醋酸丁酯</td><td>316.1</td></tr><tr><td>二苯基甲烷二异氰酸酯</td><td>262.5</td><td>二丙二醇</td><td>26.8</td></tr></table></body></html>  \n\n将三羟甲基丙烷与二丙二醇分别在105～115℃下真空脱水2～4h待用，三羟甲基丙烷 需保持在熔融状态。三羟甲基丙烷和二丙二醇之比为 $6:4$ 中  \n\n氮气保护下，将262.5kg的二苯基甲烷二异氰酸酯及316.1kg的醋酸丁酯放人反应容器中并搅拌均匀，维持温度在 $60^{\\circ}C$  \n\n将熔融的三羟甲基丙烷缓慢滴加到反应釜中，滴加过程中反应器内保持揽拌以使物料混合和反应都均匀，滴加时间为 $90\\mathrm{min}$ ，滴加完毕后继续在揽拌状态下于 $60^{\\circ}C$ 下反应 $\\mathtt{4h}$ 0  \n\n然后将二丙二醇缓慢滴加到反应器中，滴加过程中反应器内保持揽拌以使物料混合和反应均匀，滴加时间为 $2\\mathrm{h}$ ，滴加完毕后继续在搅拌状态下于 $60^{\\circ}C$ 下反应4h，降温至 $40^{\\circ}C$ 出料。  \n\n产品指标：外观清澈透明，色泽为20号铂钻色，NCO基团含量 $7.3\\%$ ，黏度 $120\\mathrm{mPa}\\cdot\\mathrm{s}_{\\mathrm{a}}$  \n\n$\\textcircled{1}$ 贮存性能测试  \n\n$=5^{\\circ}C$ 贮存30天，外观清澈透明，色泽小于20号（ $P t-C O$ 比色）。  \n\n· $50\\%$ 贮存30天，外观清澈透明，色泽小于50号（ $P_{t-C_{0}}$ 比色)，NCO基团含量为 $7\\%$ 4 $25\\mathrm{{^\\circC}}$ 黏度为 $\\mathrm{140mPa\\cdot_{s}}$ 0  \n\n· $25^{\\circ}C$ 贮存一年，外观清澈透明，色泽小于50号（ $P t-C o$ 比色)，NCO基团含量为$7.1\\%$ 中 $25C$ 时的黏度为 $135\\mathrm{{mPa}\\cdot{\\ s}}$ 0  \n\n$\\textcircled{2}$ 相容性测试将制得的固化剂 $57.5\\mathrm{g}$ 与羟基丙烯酸树脂 $170g$ 混合均匀后得到混合液，羟基丙烯酸树脂选用德国拜耳公司的DesmophenA $450~\\mathrm{BA}/\\mathrm{X}$ ，混合液清澈透明；将第一实施例中制得的固化剂 $57.5\\mathrm{g}$ 与醇酸树脂 $63.7\\mathrm{g}$ 混合均匀后得到混合液，醇酸树脂选用意大利SAPICI公司的AP572，下同，混合液清澈透明。  \n\n$\\textcircled{3}$ 可使用时间测试可使用时间定义：漆、固化剂与稀释剂混合至施工黏度后放置，黏度增加一倍所需要的时间为可使用时间。  \n\n将固化剂 $57.5\\mathrm{g}$ 与羟基丙烯酸树脂 $170\\mathbf{g}$ 混合均匀后得到混合液，用醋酸正丁酯将该混合物黏度调至岩田杯 $12\\mathrm{s}$ ， $30^{\\circ}C$ 可使用时间为 $2\\mathrm{h}$ 中  \n\n将固化剂 $57.5\\mathrm{g}$ 与醇酸树脂 $63.7g$ 混合均匀后得到混合液，用醋酸正丁酯将该混合物黏度调至岩田杯 $12\\thinspace\\mathrm{s}$ 中 $30^{\\circ}C$ 可使用时间为 $2.5\\mathrm{h}$ 0  \n\n$\\textcircled{4}$ 漆膜性能测试将固化剂 $57.5\\mathrm{g}$ 与 $170\\mathbf{g}$ 羟基丙烯酸树脂混合均匀，制得涂料漆膜，该涂料漆膜的性能如下：表干时间 $25\\mathrm{min}$ ；实干时间 $24\\mathrm{h}$ ；漆膜附着力1级；漆膜柔韧性  \n\n$1\\mathrm{mm}$ ；漆膜耐冲击性 $50\\mathrm{cm}$ ；漆膜硬度 $\\mathsf{\\Omega}2\\mathrm{H\\Omega}$ 0  \n\nMDI固化剂在发展中遇到的主要问题除了上述MDI的固有特点引起的技术难点之外，还需要克服客户的施工习惯，例如可使用时间短、干燥较慢以及建立游离MDI测试方法的国家标准。  \n\n![](images/5194fbe9863430758de8034aa53b75898bd9d41493c61a499a331d8f9ad14081.jpg)  \n图3-7-18 薄膜蒸发器基本结构  \n\n(2）薄膜蒸发处理游离TDI技术简介与国内进展薄膜蒸发处理游离TDI技术一直是制约我国聚氨酯涂料发展的瓶颈之一。2002年5月1日，GB18581的强制实施，国产固化剂游离TDI的含量得到有效控制，为 $1\\%\\sim2\\%$ （固含量 $60\\%)$ 。同时上海拜耳也将薄膜蒸发处理游离TDI的固化剂引人国内生产。与此同时，国内生产厂家也在进行薄膜蒸发技术的相关研究工作。  \n\n薄膜蒸发器基本结构如图3-7-18所示  \n\n薄膜蒸发器是在金属壁的内侧分布一层薄的液体层或膜，金属壁的另一侧提供热源，其特点不仅是膜层本身很薄，而且是由搅拌设备产生和搅拌这层薄膜的。这种机械搅拌的装置就是人们所说的转子，转子必须能够处理和带动高黏度的物料的运动。薄膜蒸发器有三个基本的工作原理：液体流动、传热和传质（图3-7-19)。  \n\n由于转子的搅拌作用，薄膜蒸发器内部液体的流动模式非常复杂。通常转子的线速度为 $\\bar{9}\\mathrm{\\sim}12\\mathrm{m/s}$ 。转子叶片前进方向附近的液体受叶片的推动而呈波浪形移动，称为波浪区；两个转子叶片的中间段是较为均匀的薄膜区（厚度 ${\\bar{0}},5{\\sim}3,5\\mathrm{mm})$ ，当液体流动到第二个转子叶片时，受到限制和挤压，形成强烈的湍流，称为湍流挤压区。三个区域在相邻的两个转子叶片之间重复出现。转子的能量主要消耗在克服液体的内摩擦和湍流。通常需要的能量是 $1600{\\sim}3000\\mathrm{W/m}^{2}$ 。转子的高速剪切可以降低液体的表观黏度，从而提高液体内部的传质和传热。  \n\n薄膜蒸发器可采用夹层式饱和蒸汽或热油加热。物料和蒸发器内壁之间的热传递效率决定了设备的尺寸和蒸发器的效率。物料的蒸发潜热、热导率、黏度、沸点升高和表面张力决定了总热交换效率。  \n\n![](images/01c17734a052bcce56444661594a4cff85f6f846bdbff3857519f44da46c6131.jpg)  \n图3-7-19 薄膜蒸发器基本原理 a一内壁；b—转子叶片； c—叶片和内壁间隙即膜厚 1—薄膜区；2—波浪区；3—挤压区  \n\n薄膜蒸发器中，由于热交换效率高，如果加热介质和物料温差为80～100℃，则蒸发器内壁接触物料部分的温度仅比TDI的沸点温度高10～20℃。因此，传质效率而不是传热效率决定了薄膜蒸发器的尺寸和分离效率。分离时，挥发性的TDI分子从膜的内部转移到界面然后蒸发。TDI分子在膜的内部的运动依靠分子扩散或涡流扩散实现。由于分子扩散的速率非常慢，而且随着黏度增加，分子扩散的速率显著下降，因此，TDI的分子运动主要由涡流扩散来决定。增加膜的湍流可以增加涡流扩散系数，薄膜蒸发中，涡流扩散系数数量级为 $10^{-6}\\mathrm{{m}^{2}/\\mathrm{{s}}}$ ，是分子扩散的 $1000{\\sim}10000$ 倍。  \n\n薄膜蒸发分离技术在制药、石化等行业有着广泛的应用基础，然而，在其他行业运用成熟的技术为什么不能用来分离游离TDI呢？这中间的难题在哪里呢？薄膜蒸发处理游离TDI技术是配方技术、设备和工艺的综合技术，国内的技术人员对于配方和工艺有很好的研究，但对设备的研究不够透彻和精通，而设备设计和制造人员对配方设计又不熟悉，造成设备和配方技术的脱节，不能形成一个有效的整体，特别是对固化剂的进料量、蒸发器转子转速、膜厚、物料行程、二次蒸汽压力、温度、停留时间等与固化剂的特点结合时对分离效率的影响缺乏足够的理论计算和支持，同时对固化剂的固有性质和特点缺乏基础数据支持，例如固化剂黏度与温度和稳定性的关系、TDI分子从固化剂中的逸出行程、分离转子对传质效率的影响等，这种复合型人才以及基础理论研究是目前涂料行业所急需的。  \n\n薄膜蒸发处理固化剂中游离TDI技术的难点可以从配方、工艺和设备三个方面考虑。  \n\n$\\textcircled{1}$ 配方难点  \n\na.在无溶剂或TDI存在时，固化剂在常温下呈固态，需要升到较高的温度才具有流动性，温度的变化及不均匀会影响整个体系的传质与传热效果。配方研究必须尽量降低体系的黏度，提高流动性，从而提高分离效率。  \n\nb.提高固化剂的高温稳定性，避免黄变、胶化以及NCO基团损失。  \n\nc.流动性、稳定性和分离时间的辩证统一。一定的温度是保证分离效率和快速流动的必要条件，而温度过高的话，固化剂的稳定性变差，因此，合适的条件必须是在最短的时间内完成分离，同时保证固化剂的性能稳定，避免变化和NCO基团的损失等的产生。  \n\n$\\textcircled{2}$ 工艺难点  \n\na.真空泵中可能含有极少量的活性杂质，真空泵系统与TDI的蒸气相连通，少量的TDI进人真空泵系统是不可避免的，进入真空泵的TDI会破坏真空泵的密封性和极限真空。减少TDI蒸气进人真空泵必须严格控制冷阱的温度或者选择合适的真空泵。  \n\nb.如何保证设备的连续运行。残留在设备内壁上的固化剂长时间后会胶化，导致设备需要经常维修和保养。  \n\n$\\textcircled{3}$ 设备难点  \n\na.确保转子外径和壳体的内径同心，才能保证设备运行的稳定性。  \n\nb.内壁和转子叶片间隙的精确控制，这也是整个薄膜蒸发体系最为关键的参数。精确的间隙保证了均匀的膜厚分布和热传递的稳定性及均匀性，最终达到涡流传质的稳定性，从而确保分离效率和分离效果。  \n\nc.壁厚的精确控制，才能保证热传递的均匀性。  \n\nd.转子动平衡的精确控制，是设备长期稳定运行的先决条件。  \n\ne.转子和壳体局部膨胀的影响，同样也是影响设备稳定运行和分离效率的重要因素。  \n\n通过以上技术难点的分析，可以知道薄膜蒸发技术在分离游离TDI时是非常困难的，不能套用其他行业的现有技术，必须在原有技术基础上进行改进。  \n\n(3）水性化发展与单组分水性聚氨酯分散体涂料相比，双组分的水性聚氨酯涂料由于存在NCO基团和羟基的交联，漆膜力学性能得到提高，特别是耐化学品性、硬度和耐划伤性等有很大的提高。双组分水性聚氨酯涂料对固化剂的要求： $\\textcircled{1}$ 固化剂在水中具有快速、良好的分散能力； $\\textcircled{2}$ 足够的NCO基团含量； $\\textcircled{3}$ 低黏度，无溶剂存在时固化剂具备好的流动性。  \n\n双组分水性聚氨酯固化剂主要有两种：一种是采用疏水性但黏度特别低的聚异氰酸酯；第二种是采用亲水改性的自乳化的聚异氰酸酯。  \n\n但是低黏度的疏水性聚异氰酸酯，必须使用合适的有机共溶剂，并在高剪切力（如高速分散）下，才能掺入水分散体中。而采用亲水改性的聚异氰酸酯，借用简单的手动搅拌，即可获得不含共溶剂的基料与固化剂的均匀混合物。  \n\n亲水性的多异氰酸酯固化剂制备主要有两种方法，一是外乳化法，即加人适当的外乳化剂，将油溶性的多异氰酸酯分散在水中。第二种方法是内乳化法，即多异氰酸酯与亲水性的改性物反应，从而使得分子中具备了亲水基团，原本疏水的多异氰酸酯就具有足够的亲水性。目前采用外乳化的方法已经很少使用，更多的是采用亲水改性的方法。  \n\n脂肪族或脂环族聚异氰酸酯如HDI或IPDI三聚体，与不足量的单官能度聚环氧乙烷聚醚醇的反应，生成含有聚醚氨基甲酸酯型非离子型乳化剂的聚异氰酸酯混合物，结构见下图：  \n\n![](images/c2134fd4450b5209e9aaf6704e5714cf2b5008a508f984c438292f2769d76afd.jpg)  \n\n具有上述结构的多异氰酸酯很容易分散在水中，无需施加高的剪切力。采用这种方法改性的多异氰酸酯固化剂有Bayhydur 3100以及Bayhydur 401-70。采用这种改性方法得到的水性聚氨酯固化剂称为第一代水性聚氨酯固化剂。  \n\n从上图中可以看出，为了进行亲水改性，需要将部分NCO基团与聚醚羟基进行反应，消耗了一定量的NCO基团，导致体系平均官能度降低，因而得到的漆膜具有较低的交联密度，耐化学品性降低。  \n\n为了提高多异氰酸酯的官能度，改进产品性能，又发展了脲基甲酸酯化的方法，其原理如上中的氨基甲酸酯上的氢具有一定的反应活性，可能继续与NCO基团反应，生成如下结构的物质：  \n\n![](images/c73d07897c7e951e64cb49cdf7315a00d9025ea8c6d7e12ba5bdfc3c81fbdeb6.jpg)  \n\n上图是第二代水性聚氨酯固化剂的结构示意图。可以看出，与第一代产品比较，第二代产品的官能度不仅比第一代产品高，而且比改性之前的聚氨酯固化剂产品的官能度提高。因此较小的改性量即可达到良好的水分散性，其漆膜性能更佳，特别是耐水性和耐化学品性。属于这种改性方法的产品有Bayhydur304、Bayhydur305。  \n\n第一代和第二代产品的共同点是都采用了聚醚作为亲水基团，由于聚醚亲水能力的限制，需要提高聚醚含量，才能确保足够的水分散性。但是聚醚含量的提高，又会导致漆膜干燥时间延长，硬度降低，同时耐水性下降。为了克服聚醚改性带来的缺点，发展了第三代水性聚氨酯固化剂。  \n\n第三代水性聚氨酯固化剂采用3-(环己氨基)-1-丙烷磺酸（CAPS）进行改性。CAPS结构如下：  \n\n![](images/2d7283096c0405bbe95c3004fa7992f9a13c5459d6616f6245209996d24eb397.jpg)  \n\nCAPS上的氨基与NCO基团反应，叔胺中和磺酸基团后，生成的磺酸脲衍生物是极好的乳化剂，产品结构见下图：  \n\n![](images/1c1f8a6734b7be3f74eabb4b942dbf895a5591d6abc42a89dcb6c7298c4f1eb7.jpg)  \n\nCAPS改性的多异氰酸酯具有很好的贮存稳定性，不浑浊，即使含有很少的磺酸盐基团时，也可在水中得到分散很好的乳液。其漆膜干燥速度、硬度和耐化学品性方面与通用溶剂型聚氨酯涂料接近。  \n\n第三代水性聚氨酯固化剂有BayhydurXP2570、BayhydurXP2487等。其产品技术指标见表3-7-100。  \n\n表3-7-100水性双组分聚氨酯固化剂技术指标  \n\n\n<html><body><table><tr><td>性能</td><td>Bayhydur XP 2570</td><td>Bayhydur XP 2487</td><td>性能</td><td>Bayhydur XP 2570</td><td>Bayhydur XP 2487</td></tr><tr><td>NCO基团含量/%</td><td>20.6±0.5</td><td>22.5±0.5</td><td>色泽 <</td><td>100</td><td>150</td></tr><tr><td>黏度（23℃）/mPa·s</td><td>3500±1000</td><td>570～730</td><td>游离单体含量/% <</td><td>0.3</td><td>0.5</td></tr></table></body></html>  \n\n聚氨酯固化剂在不断的技术进步和技术创新中走到了今天，从购买固化剂发展到了生产固化剂，从高游离TDI发展到了较低的游离TDI含量，从TDI的应用到HDI、MDI的研究应用，可以说，是家具涂料的发展带动了中国聚氨酯涂料的整体发展。但是，如何继续降低聚氨酯固化剂中游离TDI的含量，仍然是摆在人们面前的一大难题，期待在不远的将来，薄膜蒸发技术在我国能够得到长足的发展，从而使固化剂的整体性能提升到另一个高度。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 584,
+        "chunk": "# 8.聚氨酯固化剂生产和加工中的职业卫生  \n\n本书中《聚氨酯漆》一章中已经对聚氨酯涂料生产和使用过程中的主要劳动保护方法等内容进行了阐述，本节重点介绍相关法规对聚氨酯涂料的要求。  \n\n（1）欧盟指令对异氰酸酯单体和含异氰酸酯单体固化剂的标签要求根据欧盟法规，二异氰酸酯单体如HDI、IPDI、 $\\mathbf{H}_{\\mathrm{I2}}\\mathbf{M}\\mathbf{D}\\mathbf{I}$ 、TDI和MDI被列于欧盟指令67/548/EEC危险物质分类、包装和标签指令的附件I中，因此，它们必须遵守标准化强制性分类和欧盟范围的标志。  \n\n根据欧盟指令67/548/EEC的要求，TDI被列为剧毒物，危险标志为 $\\mathrm{T^{+}}$ ，骷髅图；HDI和 $\\mathbb{H}_{\\mathrm{12}}\\mathbb{M}\\mathrm{DI}$ 被列为有毒物，危险标志 $\\mathrm{\\DeltaT}$ ，骷髅图；IPDI被列为有毒物和对环境危险，危险标志N，树和鱼；MDI被列为有害物，危险标志 $\\mathbf{X}\\mathbf{\\bar{n}}$ ，St，斜十字。上述异氰酸酯单体的刺激作用具有相同的标签 $(\\mathrm{R36}/37/38\\$ ：刺激眼睛、呼吸系统和皮肤）。  \n\n多异氰酸酯固化剂根据欧盟指令1999/45/EEC危险制剂进行分类。基于脂肪族二异氰酸酯HDI、IPDI和 $\\mathrm{\\bf{H}}_{12}\\mathrm{\\bf{MDI}}$ 的聚异氰酸酯产品中残留单体含量高于 $0.5\\%$ ，应标记为有害且具有 $\\mathbf{X}\\mathbf{n}$ 危险标志；对于含有芳香族二异氰酸酯TDI和MDI的聚异氰酸酯产品，当单体含量高于 $0.1\\%$ 时，需要此种标识。欧洲油漆、油墨和艺术油彩生产商协会（CEPE）制订了以下信息用于表示装有含异氰酸酯基团涂料的容器：“含异氰酸酯固化剂和所制备的涂料可刺激皮肤和呼吸道，引起过敏化和过敏反应。在产品使用过程中和使用以后，确保用新鲜空气进行不断通风。不要吸人蒸气。喷涂时应佩戴呼吸保护器。患有过敏性和呼吸道疾病的人员，禁止从事含有这些涂料物质的工作。”  \n\n基于MDI的产品，在应用和职业卫生方面具有一定的特殊性，原因是MDI固化剂产品中，单体含量比较高，但是MDI单体的蒸气压比TDI等要低几个数量级。研究表明，MDI具有致癌可能性。在TRGS905（德国危险物质技术规则）被归类为3类致癌物（可疑致癌物)。动物试验表明，MDI浓度超过 $0.2\\mathrm{mg}/\\mathrm{m}^{3}$ 时，会引起肺功能衰退和呼吸道敏感。  \n\n（2）工作场所空气中异氰酸酯浓度测定采用适当的试剂将异氰酸酯转变为稳定的衍生物，然后借助色谱法进行定性和定量。俘获剂以溶液状态存在于空气采集器中。几种常用的方法如下：  \n\nTDI、HDI，DFG方法2：空气采集器（N-4-硝基苄基 $\\mathbf{\\nabla}\\cdot\\mathbf{N}-\\mathbf{\\nabla}\\cdot\\mathbf{n}\\cdot$ -丙胺盐酸盐的甲苯溶液）或涂有N-4-硝基苄基- $\\mathbf{\\partial}\\cdot\\mathbf{N}\\mathbf{-n}\\cdot$ -丙胺盐酸盐的玻璃纤维过滤器。  \n\n基于脂肪族二异氰酸酯的聚异氰酸酯，DFG方法1：涂有N-4-硝基苄基- $\\mathbf{\\partial}\\cdot\\mathbf{N}\\mathbf{-}\\mathbf{\\bar{n}}$ -丙胺盐酸盐的玻璃纤维过滤器；基于芳香族二异氰酸酯的聚异氰酸酯，DFG方法2；涂有N-4-硝基苄基- $N-n$ -丙胺盐酸盐的玻璃纤维过滤器，衍生的异氰酸酯通过高效液相色谱进行分离，并采用光度测定法进行定量。  \n\n(3）聚氨酯涂料加工和施工过程中的劳动保护必须采取合适的措施例如车间设计、抽风、通风以及个人劳动保护以保证作业人员的安全。  \n\n患有下述疾病的人员不能从事与异氰酸酯接触的工作，这些疾病包括过敏症、哮喘、支气管炎或其他慢性呼吸道疾病。  \n\n如在使用涂料工作过程中以及工作以后，出现咳嗽、胸闷或类似哮喘病症，应避免再次接触。  \n\n强烈建议佩戴安全眼镜。如喷涂气雾进人眼睛，应立即用大量水冲洗，然后就医。避免接触溶剂。  \n\n(4）固化剂残余物处理聚氨酯固化剂的残余物最好通过烧处理。少量的异氰酸酯可用表3-7-101中的混合溶液进行处理。  \n\n表3-7-101 中和聚异氰酸酯残余物的混合溶液  \n\n\n<html><body><table><tr><td>混合物A</td><td>质量份</td><td>混合物B</td><td>质量份</td></tr><tr><td>水 碳酸钠</td><td>88</td><td>洗涤剂</td><td>2</td></tr><tr><td>洗涤剂</td><td>10 2</td><td>混合物C</td><td></td></tr><tr><td>混合物B</td><td></td><td>工业醇(乙醇或丁醇等) 水</td><td>50 45</td></tr><tr><td>水 浓氨水</td><td>90 8</td><td>浓氨水</td><td>5</td></tr></table></body></html>  \n\n聚异氰酸酯与上述混合物反应后，生成不溶性的聚脲，它无生理影响。使用过的容器也需要采用上述溶液进行处理，然后废弃。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 585,
+        "chunk": "# 六、稀释剂  \n\n木用涂料六大类产品中，每一类都有自己特定的、对应的稀释剂，要配套使用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 586,
+        "chunk": "# 1.稀释剂的作用  \n\n稀释剂在涂料应用中主要起着溶解和稀释涂料，调节涂料的黏度使之便于施工。在木用涂装中，由于是室温干燥或低温烘烤，稀释剂在涂膜干燥过程中会影响涂膜形成时的流动特性，如流平性、抗流挂性等，也影响涂膜的最终物理性能。在UPE和UV稀释剂中，作为活性稀释剂参与成膜反应，它影响着涂料的固化速率和漆膜的各种性能。活性稀释剂按其每个分子所含反应性基团的多少，可分为单官能团活性稀释剂、双官能团活性稀释剂和多官能团活性稀释剂。在木用涂装中，还经常用到一类成本低廉的稀释剂，主要用来洗枪用，俗称洗枪水。",
+        "category": " Introduction"
+    },
+    {
+        "id": 587,
+        "chunk": "# 2.配方机理  \n\n（1）基础配方 见表3-7-102和表3-7-103。  \n\n表3-7-102NC、PU稀释剂基础配方  \n\n\n<html><body><table><tr><td>原料名称</td><td>规格</td><td>NC夏用稀释剂/%</td><td>NC冬用稀释剂/%</td><td>PU夏用稀释剂/%</td><td>PU冬用稀释剂/%</td></tr><tr><td>稀释剂</td><td>甲苯</td><td>25</td><td>35 20</td><td>58</td><td>30</td></tr><tr><td>稀释剂 真溶剂</td><td>二甲苯 醋酸丁酯</td><td>30 22</td><td>17</td><td>12</td><td>28 22</td></tr><tr><td>真溶剂</td><td>醋酸乙酯</td><td></td><td>5</td><td></td><td></td></tr><tr><td>助溶剂</td><td>正丁醇</td><td>10</td><td>10</td><td></td><td></td></tr><tr><td>真溶剂</td><td>防白水</td><td>5</td><td>5</td><td></td><td></td></tr><tr><td>真溶剂</td><td>MIBK</td><td>00</td><td>80</td><td>5</td><td>5</td></tr><tr><td>真溶剂</td><td>PMA</td><td>一</td><td></td><td>25</td><td>15</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>原料名称</td><td>规格</td><td>NC夏用稀释剂/%</td><td>NC冬用稀释剂/%</td><td>PU夏用稀释剂/%</td><td>PU冬用稀释剂/%</td></tr><tr><td rowspan=\"5\">性能指标</td><td>外观</td><td>清晰、透明、</td><td>清晰、透明、</td><td>清晰、透明、</td><td>清晰、透明、</td></tr><tr><td></td><td>无机械杂质</td><td>无机械杂质</td><td>无机械杂质</td><td>无机械杂质</td></tr><tr><td>水分</td><td>不显浑浊</td><td>不显浑浊</td><td>不显浑浊</td><td>不显浑浊</td></tr><tr><td>颜色</td><td>15(Pt-Co)</td><td>15(Pt-Co)</td><td>15(Pt-Co)</td><td>15(Pt-Co)</td></tr><tr><td>酸值/(mg KOH/g)</td><td>0.04</td><td>0.06</td><td>0.06</td><td>0.05</td></tr><tr><td rowspan=\"2\"></td><td>白化性</td><td>漆膜不发白</td><td>漆膜不发白</td><td></td><td></td></tr><tr><td>胶凝数</td><td>23.0</td><td>22.0</td><td></td><td></td></tr></table></body></html>  \n\n表3-7-103UPE、AC、UV、洗枪水基础配方  \n\n\n<html><body><table><tr><td>原料名称</td><td>功能说明</td><td>UPE稀释剂/%</td><td>AC稀释剂/%</td><td>UV稀释剂/%</td><td>洗枪水/%</td></tr><tr><td>稀释剂 稀释剂 真溶剂 助溶剂 真溶剂 真溶剂 真溶剂 真溶剂</td><td>甲苯 二甲苯 醋酸乙酯 异丁醇 防白水 丙酮 MIBK PMA</td><td>30 一 一 一 20 一 一</td><td>一 86.1 一 5.6 8.3 一 一 一</td><td>一 一 一 一 一 一</td><td>25 15 30 1 一 25 一 5</td></tr><tr><td>活性稀释剂</td><td>TPGDA</td><td>50 一</td><td>一 一 100.00</td><td>1 100 100.00</td><td>一 一</td></tr><tr><td>合计 性能指标</td><td>外观 水分</td><td>100.00 清晰、透明、无机械杂质 不显浑浊</td><td>不显浑浊</td><td>清晰、透明、无机械杂质 清晰、透明、无机械杂质清晰、透明、无机械杂质 不显浑浊</td><td>100.00 不显浑浊</td></tr></table></body></html>  \n\n(2）配方调整  \n\n$\\textcircled{1}$ 原材料的选择和稀释剂主要性能指标的调控在木用涂料稀释剂中，常用的溶剂主要有芳香烃、醇类、酮类、酯类、醇醚及醚酯类溶剂。在设计配方时，首先应十分重视溶剂的气味、对人体的毒性、空气污染限制和安全性。对于具有令人不愉快气味的溶剂、对人体毒性大的溶剂、易燃易爆的溶剂和不符合空气污染法限制的溶剂应尽量不选用。其次应充分考虑各组分溶剂的溶解力、黏度、挥发速率、表面张力和电阻率。  \n\n$\\textcircled{2}$ 技术难点在木用涂料稀释剂中，各种挥发速率不同、溶解力不同的溶剂平衡是配方调整的难点。干燥的涂膜是在溶剂挥发过程中形成的。如果挥发太快，涂膜流平性差，对底材没有很好地润湿，从而影响附着力，同时漆膜会发白。如果挥发太慢，则干燥时间延长，立面喷涂时容易流挂。  \n\n溶剂平衡是指涂料在成膜过程中，混合溶剂的各组分相对挥发速率要与溶剂组成保持对应。换言之，从涂膜中挥发出的混合溶剂蒸气的组成与混合溶剂的组成要大体保持一致。如果溶解力强的溶剂组分比其他组分会发得快，则在干燥后期树脂可能析出，涂膜表面产生颗粒，相反溶解力强的组分挥发得太慢，又因树脂有阻滞与其结构相似的溶剂挥发的特性，会增加该溶剂在涂膜中的残留量。  \n\n在日常应用中，NC和PU稀释剂又根据天气的变化分为夏用和冬用稀释剂，夏天温度高，溶剂挥发快，配方中慢干溶剂可适当增加，使漆膜有足够的时间保证流平性；冬天温度低，溶剂挥发慢，配方中快干溶剂可适当增加，以提高油漆的干燥速率。市场上也常见到一些低价稀释剂，是将废溶剂蒸馏后调配而成，因废溶剂的成分千变万化，该类稀释剂质量极不稳定，严重影响涂料的最终效果，因此稀释剂一般建议与涂料配套使用。在UPE 稀释剂配方中，有些溶剂能加速活性稀释剂苯乙烯的自聚，因此调整配方时必须做热贮存试验，适当时可加人部分阻聚剂以保证稳定性。  \n\n(3）产品制备稀释剂的生产一般采用可调速的搅拌机，容器最好采用密闭的，以避免生产过程中溶剂的挥发。生产过程中确保各组分搅拌均匀，调配好的产品用 $120\\sim150$ 目的滤网过滤包装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 588,
+        "chunk": "# 七、蓝、白水  \n\n蓝、白水为不饱和聚酯漆的配套产品促进剂和引发剂的俗称。在木用不饱和聚酯漆中，常用的促进剂（蓝水）主要有环烷酸钴和异辛酸钻，引发剂（白水）主要有过氧化环己酮（CHP）和过氧化甲乙酮（MEKP）。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 589,
+        "chunk": "# 1．蓝、白水的作用  \n\n$\\textcircled{1}$ 引发剂（白水）的主要作用能分解产生高度活性的自由基，自由基攻击聚酯分子链中的不饱和双键和交联单体（如苯乙烯)，使之活化，从而发生交联反应。  \n\n$\\textcircled{2}$ 促进剂（蓝水）的主要作用通过氧化还原反应，使引发剂分解产生高度活性的游离基。环烷酸钻与过氧化氢化合物产生自由基的作用如下。  \n\n$$\n\\mathrm{ROOH}+\\mathrm{Co^{2+}}\\longrightarrow\\mathrm{RO}\\bullet+\\mathrm{Co^{3+}}+\\mathrm{OH^{-}}\n$$  \n\n接着在下一步反应中，重新生成环烷酸钴。  \n\n$$\n\\mathrm{Co^{3+}+R O O H\\longrightarrow C o^{2+}+R O O\\cdot+H^{+}}\n$$  \n\n此反应循环重复进行，直到过氧化氢化合物完全分解。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 590,
+        "chunk": "# 2.配方机理  \n\n(1）引发剂的选用引发剂的主要作用是能分解产生自由基以引发交联固化过程。表达引发剂活性大小的方法主要有半衰期、临界温度和活性氧含量。  \n\n在选用引发剂时首先要使引发剂的特性和不饱和树脂的反应性相配合。树脂反应性强，就要采用活性较高的引发剂使树脂固化周期缩短，树脂反应性弱就要选用活性较低的引发剂相配合，以免自由基产生过快，在树脂固化过程中不能充分生效，而到后期又缺少引发剂。其次要考虑涂料的可使用时间（适用期或胶凝时间）。  \n\n因木用不饱和聚酯漆属常温固化型，所以必须配以活性较高并能与促进剂发生氧化还原反应释放出自由基的引发剂。两种应用最广的常温固化用引发剂为过氧化甲乙酮（MEKP）和过氧化环己酮（CHP)。两种引发剂名为过氧化物，实为氢过氧化物，而且是多种氢过氧化物的混合物。随制造工艺不同，其成分与性能也常有变异。过氧化甲乙酮常以邻苯二甲酸二甲酯的溶液状提供，过氧化环已酮常混合于邻苯二甲酸二丁酯或磷酸三甲酯中，以 $50\\%$ （质量分数）浓度的糊状物提供。过氧化环己酮的适用温度为 $0\\sim25^{\\circ}C$ ，其优点是放热峰温度较低，对固化温度的敏感性弱，固化应力小，在透明板材中颜色稳定。过氧化甲乙酮的固化温度范围 $15\\sim25^{\\circ}C$ ，其优点是价格低、性能好、使用方便、和树脂容易混容。  \n\n在同样促进剂用量下，增加引发剂量，就可提高放热峰温度，减少固化时间。相反，减少引发剂用量，就可降低放热峰温度，延长固化时间。引发剂用量不变，但环境温度改变，会显著影响固化时间。引发剂的常用量为 $1\\%\\sim2\\%$ (质量分数)。由于过氧化甲乙酮性质不稳定，即使在液态室温下也会缓慢分解放出气体，有着火危险，故在运输中需注意安全。  \n\n(2）促进剂的选用促进剂是指在聚酯固化过程中能单独使用以促进引发剂分解的活化剂。常用的促进剂有金属化合物促进剂和叔胺促进剂。金属化合物，特别是异辛酸钴和环烷酸钴，是当前应用最广的优良促进剂。主要用于氢过氧化物与混合过氧化物引发剂。采用钻促进剂对加速树脂的固化反应的效果很显著，但适用期明显缩短。如恒定引发剂用量，随着钻促进剂的用量增加，活化点增多，放热峰温度提高，固化时间缩短，反之，放热峰温度下降，固化时间延长。叔胺类促进剂用于促进过氧化物引发剂，能在常温下固化。最常用的是二甲基苯胺、二乙基苯胺、二甲基对甲苯胺。不饱和聚酯树脂用叔胺促进、过氧化引发系统时，固化后逐渐变黄，也常常产生微细裂纹。钻-氢氧化物引发系统则对反应条件的适应性较宽，反应固化不足时，以后还能继续固化。所以在木用不饱和聚酯漆中，一般采用钴-氢氧化物引发系统。  \n\n(3）蓝白水与主剂的配比和原则（根据不同温度调节蓝白水的配比）UPE透明底漆相对UPE实色底漆来说，树脂含量要多，相应调漆时蓝、白水加入量要大些。引发剂（白水）、促进剂（蓝水）的使用量随气温而变，夏季气温高，引发剂和促进剂的用量可耐减；而冬季气温低，固化慢，可耐情增加引发剂和促进剂的用量，但促进剂用量增加会使漆膜颜色变深，不利于浅色透明涂饰；表3-7-104中列举了促进剂、引发剂随气温变化而作调整的参考用量。  \n\n表3-7-104不同温度下引发剂（白水）、促进剂（蓝水）的加入量  \n\n\n<html><body><table><tr><td rowspan=\"2\">加人量</td><td colspan=\"6\">涂装环境温度/C</td></tr><tr><td>5~10</td><td>10~15</td><td>15~20</td><td>20~25</td><td>25~30</td><td>30~35</td></tr><tr><td>UPE主剂/g</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td></tr><tr><td>促进剂(蓝水)/g</td><td>2.8~3.2</td><td>2.4~2.8</td><td>2.0~2.4</td><td>1.6~2.0</td><td>1.2~1.6</td><td>0.8~1.2</td></tr><tr><td>引发剂(白水)/g</td><td>3.0~3.5</td><td>2.6~3.0</td><td>2.2~2.6</td><td>1.8~2.2</td><td>1. 4~1.8</td><td>1. 0~1. 4</td></tr><tr><td>UPE稀释剂/g</td><td>30~50</td><td>30~50</td><td>30~50</td><td>30~50</td><td>30~50</td><td>30~50</td></tr></table></body></html>  \n\n(4）配方调整蓝、白水的用量主要取决于树脂的反应性、可使用时间（适用期）、温湿度和固化速率。促进剂用量不变，增加引发剂量，可使用时间（适用期）缩短，固化速率加快。引发剂用量不变，增加促进剂量，同样可使用时间（适用期）缩短，固化速率加快。在低温时，为加快固化速率，主要增加引发剂用量；在湿度高时，为加快固化速率，主要增加促进剂用量。是否反应完全可根据漆膜的颜色来判定。反应完成得好，漆膜应呈浅粉红色；反应完成得不好，漆膜会呈浅绿色。蓝、白水的实际用量需根据施工时的环境条件而定。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 591,
+        "chunk": "# 3.蓝、白水使用注意事项  \n\n(1）在使用蓝、白水时，两者绝不能直接混合，否则会造成激烈反应，甚至爆炸。蓝水和白水必须隔离放置。使用时可以往漆中先加人蓝水，混合好后，再加入白水。实际应用时常见的调漆方法为：UPE底漆分成相同重量的两份，分别置于两个调漆桶中，一个桶加入蓝水，另一个桶加入白水，分别加入等量的UPE稀释剂搅拌均匀；也可以先用稀释剂将涂料均匀调稀，再按上法分别加入蓝、白水，更易分散均匀。喷涂时两边取相同量，混匀喷涂；UPE底漆分开加入蓝、白水后在一定的存放时间内可连续使用：UPE底漆加蓝水≤$\\mathtt{12h}$ ，UPE底漆加白水 $\\leqslant4h$ 睿  \n\n(2）白水应贮存于阴冷干燥处，保存在原贮存容器中，与其他材料隔开。不能直接接触细分散的有机材料及金属粉末。  \n\n(3）必须十分小心防止白水进人眼中。在操作中使用白水时，应戴眼镜。一旦误入眼睛，要立即用大量清水冲洗，再用药物处理。皮肤接触后，要立即用水冲洗，再用保护油脂涂覆。  \n\n(4）清洁用的碎布及沾有白水的纸、木屑等要放在外面，在严密监视下烧掉。绝不要放  \n\n在废物箱中，或随便遗弃，因有自燃危险。  \n\n(5）白水有泄漏时，要用无机吸收物如沙子、硅藻土等擦去，并立即移出室外。不能用碎布、纸、锯末等可燃物吸走，否则易起火。如不得已而用锯屑时，要立即移出室外处理。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 592,
+        "chunk": "# 八、着色材料  \n\n木制品在外形设计相同的前提下，可以适合不同消费群体的需求，这在很大程度上取决于表面色彩，不同的表面色彩效果可以获得不同人群的喜爱。色彩是一种心里感觉，就木用涂料色彩而言，青年人喜欢浅色，因为浅色有明快的感觉；老年人喜欢深色，深色表达其内心处事的稳重。因此，青年人青睐浅本色、浅柚木色木器，老年人喜爱深柚木色、仿红木色木器。  \n\n木材是一种多孔性结构的天然高分子化合物，具有特殊的外观花纹，在木材表面进行彩色透明涂饰，就是为了更好地显示木材表面的这种天然花纹。在现代木器生产中，表面涂饰仍以能显露木材原始花纹的涂饰为主，就是大量采用中密度纤维板为基材的家具生产中，其表面也贴有原木薄皮或仿木纹的木纹纸，然后再进行彩色透明涂饰；不透明彩色涂饰，即实色涂装，在黑、白木制品中，以及在儿童家具、橱柜产品中具有一定的市场，但总量不多。  \n\n木用涂料的着色材料，要适应被着色底材的千差万别，要能满足千变万化的着色方法，要表现出千姿百态的最终着色效果，因而衍生出一系列特点各异的着色产品。",
+        "category": " Introduction"
+    },
+    {
+        "id": 593,
+        "chunk": "# 1.木用涂料着色材料的作用  \n\n着色是木制品涂装的关键，它对木制品的装饰质量起着重要作用。木制品透明着色涂饰由管孔着色、材面着色和涂膜修色三部分组成，在操作工艺上，管孔着色、材面着色和涂膜修色常分步完成，特别是在使用具有美丽花纹的大孔径木材时，通过分步着色更能获得色调丰富、有层次的色彩效果。  \n\n(1）木材着色的作用木材着色包括材面着色和管孔着色，统称为基础着色（底着色)。材面着色是为了统一木材表面的色彩；管孔着色是为了突出木材导管、管孔的美丽花纹。管孔色通过填孔着色完成，因此管孔着色剂既需要填充性、遮盖力，又要有着色力，色泽深于涂膜色，这样管孔色就与涂膜色形成了一定的反差，使材面的花纹更加突出，以表现木制品表面色彩的活泼性。材面色在要求不太高的场合常在管孔填孔着色时同时完成，因为在擦涂填孔着色剂时对材面也有一定的着色作用。而在要求高的场合，材面色则是先于填孔着色完成，材面色一般较浅。  \n\n(2）涂膜修色的作用涂膜修色是根据需要在涂装现场把不同类型的着色材料加入到清漆中，薄喷后使涂膜带上浅而均匀的色泽，涂膜色是木制品表面色彩的主色调，通常做在表层清漆的下层，它与木表面的着色和管孔色交相辉映，既突出了木表面的天然花纹，又给木制品悦目的色彩，因此涂膜修色常在填孔着色和材面着色后完成。",
+        "category": " Introduction"
+    },
+    {
+        "id": 594,
+        "chunk": "# 2.着色材料的主要品种  \n\n(1）颜料类着色材料将颜料分散在树脂中制成色浆，加入根据施工及层间附着性能要求所配制的基料，经过充分的混合制成颜料类着色剂，与染料类着色剂相比，其鲜艳度、透明度稍差，但耐光性、耐候性好，不易发生色迁移。如采用透明或半透明性颜料，其鲜艳度、透明度则会大大提高。颜料类着色剂按功能可分为格丽斯（oilstain）、木纹宝（woodstain）以及普通色浆。  \n\n$\\textcircled{1}$ 格丽斯（oil stain）着色剂格丽斯是一种半透明着色剂，又称仿古釉彩，业内俗称格丽斯（glaze)。它是美式涂装中最重要的着色剂，它可使家具变得陈旧，又可显现木材纹理，除整体着色外，还可以制作假木纹。常用格丽斯有大红、红棕、咖啡、梨黄、黑棕、黑、咖啡、透明黄、金黄、柠檬黄、白等多种颜色。常用格丽斯色浆的配方见表3-7-105。常用透明格丽斯的配方见表3-7-106。  \n\n表3-7-105 常用格丽斯色浆的配方  \n\n\n<html><body><table><tr><td>类别</td><td>620</td><td>630</td><td>640</td><td>650 660</td><td>670</td><td>Van Dyke Byown</td><td>灯黑101/ 特黑100</td><td>PR170 红</td><td>PY12 黄</td></tr><tr><td>长川GL100超长油度醇酸 树脂</td><td>30</td><td>30</td><td>30</td><td>30 30 13.8</td><td>30 13.8</td><td>30</td><td>30</td><td>30</td><td>30</td></tr><tr><td>150*溶剂汽油 Disperbyk-106分散剂</td><td>14.1 9.6</td><td>14.1 9.6</td><td>14.1 9.6</td><td>14.I 9.6 9.6</td><td>9.6</td><td>20.2 8.5</td><td>33.7</td><td>38.4</td><td>50.2</td></tr><tr><td>Disperbyk-182分散剂 防结皮剂(甲乙酮) 有机膨润土SD-1</td><td>0.3 1</td><td>0.3 1</td><td>0.3 1</td><td>0.3 0.6 1 1</td><td>0.6 1</td><td>0.3 1</td><td>16 0.3</td><td>6.3 0.3</td><td>4.5 0.3</td></tr><tr><td>620安巴粉 630安巴粉</td><td>45</td><td>45</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>640安巴粉 650安巴粉 660安巴粉 670安巴粉</td><td></td><td></td><td>45</td><td>45 45</td><td>45</td><td>40</td><td></td><td></td><td></td></tr></table></body></html>\n\n$\\textcircled{1}$ 均为美国洛克伍德公司产品。  \n\n表3-7-106 常用透明格丽斯的配方  \n\n\n<html><body><table><tr><td>名称</td><td>用量/%</td><td>名称</td><td>用量/%</td></tr><tr><td>长川GL100超长油度醇酸树脂</td><td>20</td><td>防结皮剂(甲乙酮)</td><td>0.2</td></tr><tr><td>150*溶剂汽油</td><td>38.3</td><td>有机膨润土SD-1</td><td>1</td></tr><tr><td>Disperbyk-AT-203分散剂</td><td>0.5</td><td>滑石粉</td><td>40</td></tr></table></body></html>  \n\n格丽斯配方原理：格丽斯是由专用色浆、滑石粉、 $200^{\\sharp}$ 溶剂汽油、芳烃类溶剂和防沉剂、催干剂及防结皮剂等组成。早期的格丽斯专用色浆是在吹制亚麻仁油或氧化干燥型超长油度醇酸树脂中加人适量防沉剂、催干剂、防结皮剂、安巴色粉及氧化铁系颜料研磨而成，如客户要求颜色艳丽一些，可专配少许色泽艳丽的有机颜料色浆，如有机红、有机黄等。格丽斯之所以采用吹制亚麻仁油和超长油度醇酸树脂，是因为它们对颜料的润湿性好、干燥慢、容易擦涂，所用溶剂也不会溶解下层的底漆；但这类基料的层间附着力差，要精心选择擦色树脂和填料及生产工艺，达到擦涂性能和层间附着力的平衡，所以使用时要注意。  \n\n一般在透明格丽斯中加人 $40\\%\\sim50\\%$ 的格丽斯色浆并调至需要的颜色，再按格丽斯：稀释剂 $=1:(0.2{\\sim}0.4)$ 比例加人格丽斯稀释剂，搅拌均匀后进行施工。通常采用擦涂或刷涂，通过控制格丽斯残留量来达到颜色有深有浅的效果。为了着色均匀，在施工格丽斯之前，可先喷一道头道底漆。由于格丽斯干燥很慢，用画圈法将其推人到木材的导管中去，然后再顺着木纹的方向擦拭，亦可用繁毛刷顺木纹方向来回反复刷涂，刷匀残留的格丽斯，获得所希望的颜色并透露出木材的天然纹理。刷涂法均采用“干刷”，所谓干刷，就是采用干燥的鬃毛刷，用毛尖蘸取格丽斯直接刷涂，为了避免毛刷蘸色太多，也可以在格丽斯的表面上蒙一层纱布，把它做成印泥状。有时它会与画明暗的工艺相结合，使颜色形成深浅不同的层次。格丽斯一般要待干 $\\mathbf{\\tau}_{1\\sim2\\mathbf{h}}$ 后再喷涂二道底漆，以避免出现霉点。  \n\n不含着色颜料的透明格丽斯，又称为格丽斯透明主剂，用它封闭木材端面和素材较易着色处，再涂布格丽斯着色剂，可使着色一致；还可用它来调整和配制格丽斯着色剂。  \n\n$\\textcircled{2}$ 木纹宝（woodstain）着色剂木纹宝着色剂就是木材管孔着色剂，业内俗称木纹宝。在木制品管孔着色中为了突出木材导管、管孔的美丽花纹，需要通过填孔着色完成，这种着色剂既需要遮盖力，又要有着色力，使用各种颜料，利用颜料的遮盖力、良好的耐光及耐候性、不渗色等性质可以制成这种木材管孔着色剂。常用木纹宝着色剂的配方见表3-7-107。  \n\n表3-7-107 常用木纹宝着色剂的配方  \n\n\n<html><body><table><tr><td>名称</td><td>用量/%</td><td>名称</td><td>用量/%</td></tr><tr><td>醇酸树脂 溶剂（二甲苯、150*汽油、PMA、DBE)</td><td>2~10 82~42</td><td>滑石粉 色浆或染料液（或拼用）</td><td>10~50 5</td></tr></table></body></html>  \n\n木纹宝配方原理：利用填料和颜料强烈的填充性，加入少量的色浆或染料液后又具备了一定的着色性能，可以制成能强烈突出木材导管、管孔花纹的木材管孔着色剂木纹宝。它用于底着色时，展色剂带着颜料一起填人到木材的导管中去，由于其中使用一些透明填料，又具有强烈的填充作用。该着色剂的透明度在染料与颜料之间，同时具有有机染料的鲜艳度和颜料的耐光、耐候性，一般采用擦涂法施工，可根据展色剂选择稀释剂，通常为醚类、酯类、溶剂汽油等，也可用NC或PU稀释剂。  \n\n$\\textcircled{3}$ 色浆  \n\na.溶剂型色浆将颜料分散在溶剂、助剂及木用树脂组成的系统中，通过研磨分散达到体系稳定的合格色浆，用于配制木用色漆，适合儿童家具、玩具、橱柜等木制品的彩色不透明（实色）涂饰。通常选择低色迁移、符合木用涂饰环保要求的颜料，考虑企业产品结构的特点，应用和本企业核心产品良好相容的木用树脂为颜料载体树脂，可以兼顾到企业主要产品的实色配色使用。  \n\n木用涂装中，透明色木纹涂装增长很快，彩色实色漆应用不多，其销量只占木用涂料的百分之几，彩色色浆需求量不大。因此在木用涂料厂中，色浆配方的制定，可以打破各自为政的旧方法，而统一由一个部门制备色浆供各工艺工程师选用，有利于色浆稳定、降低成本。木用涂料色浆配方见表3-7-108。  \n\n表3-7-108 木用涂料色浆配方 单位：%（质量分数）  \n\n\n<html><body><table><tr><td>颜料指数</td><td>颜料</td><td>颜料含量</td><td></td><td>52%有数成</td><td>颜料物行</td><td>颜生料物行</td><td>防沉淀剂</td><td>溶剂含量</td><td>相对密度</td></tr><tr><td>PW6</td><td>钛白</td><td>65</td><td>17</td><td>3.1</td><td></td><td></td><td>0.4</td><td>11.5</td><td>1.98</td></tr><tr><td>PBK7</td><td>炭黑</td><td>18</td><td>40</td><td>14</td><td></td><td></td><td></td><td>28</td><td>1.10</td></tr><tr><td>PB15:2</td><td>酞菁蓝</td><td>18</td><td>29</td><td>7.6</td><td>0.4</td><td></td><td></td><td>45</td><td>1.06</td></tr><tr><td>PG7</td><td>酞菁绿</td><td>24</td><td>40</td><td>16.2</td><td>0.5</td><td></td><td></td><td>19.3</td><td>1.16</td></tr><tr><td>PR101</td><td>氧化铁红</td><td>55</td><td>20</td><td>10.6</td><td></td><td></td><td>0.9</td><td>13.5</td><td>1.85</td></tr><tr><td>PY42</td><td>氧化铁黄</td><td>50</td><td>18</td><td>7</td><td></td><td></td><td>0.8</td><td>24.2</td><td>1.60</td></tr><tr><td>PV23</td><td>二嗪紫</td><td>10</td><td>68</td><td>4.5</td><td></td><td></td><td></td><td>17.5</td><td>1.09</td></tr><tr><td>PR146</td><td>永固桃红</td><td>16</td><td>38</td><td>9.2</td><td></td><td>1.0</td><td></td><td>35.8</td><td>1.07</td></tr><tr><td>PR170</td><td>偶氮红</td><td>25</td><td>30</td><td>14.5</td><td></td><td></td><td></td><td>30.5</td><td>1.09</td></tr><tr><td>PY12</td><td>联苯胺黄</td><td>15</td><td>30</td><td>11</td><td></td><td>1.1</td><td></td><td>42.9</td><td>1.04</td></tr><tr><td>PY139</td><td>异吲哚啉黄</td><td>27</td><td>38</td><td>10.4</td><td></td><td></td><td></td><td>24.6</td><td>1.15</td></tr><tr><td>PO16</td><td>联苯胺橙</td><td>21</td><td>44</td><td>12.5</td><td></td><td>1.4</td><td></td><td>21.1</td><td>1.09</td></tr><tr><td>PR122</td><td>喹吖啶酮红</td><td>15</td><td>44</td><td>9.6</td><td></td><td></td><td></td><td>45.5</td><td>1.05</td></tr></table></body></html>  \n\nb.水性色浆随着木用涂料的水性化发展，水性木器涂装在使用颜料着色时要求配套水性色浆。木用水性色浆的配方原理和木用溶剂型色浆相似，只是用丙二醇、己二醇或水性化树脂代替了溶剂型色浆中的颜料载体树脂，并使用水油通用分散剂或水性分散剂稳定颜料。由于水性木用涂料处于初级发展阶段，水性木用涂料色浆用量有限，目前业内大多选择专业水性色浆进行水性木用涂料的调配色。  \n\n(2）染料类着色材料在木制品的透明涂饰工艺中，材面着色和涂膜修色使用的透明看色剂不能对基材有遮盖力，需要均匀、透明又清晰地表现材面的木材花纹，但同时要求与木孔色有较大的反差，能更好突出材面花纹，这只能使用既具着色力而无遮盖力的透明着色剂，有机染料具备了这一特性。染料型着色剂俗称色精，是用染料溶解在溶剂中制成。根据所用溶剂可分为溶剂型、醇溶型及水溶型。  \n\n配方原理：配制有机染料透明着色剂时，应根据有机染料的溶解特点，选择其在某溶剂中溶解度的 $70\\%\\sim80\\%$ 用量，分别溶解在有机溶剂（环己酮、丙二醇甲醚醋酸酯、醋酸丁酯、二甲苯、乙醇等）或水中，过滤后配制成一定染料含量 $(10\\%\\sim30\\%$ ）的生产调色用的原色色精或供销售用的色精产品。  \n\n染料的溶解和染料的化学成分、溶剂性质以及温度等因素紧密相关，溶解染料时要仔细选择染料和溶剂，还应当考虑贮存温度的变化以及区域使用温度的变化对染料溶解度的影响，实际配制的染料液浓度一般要低于溶解度。  \n\n色精使用时一般加入 $3\\%\\sim5\\%$ 至透明底漆中配成某材面色的有色透明底漆，或加人$3\\%\\sim5\\%$ 至清面漆中配成某涂膜色的有色透明清漆，然后用喷涂法或刷涂施工。也可以不用漆料，只用着色剂配成材面色后用较多的稀释剂稀释，均匀地快速喷涂或刷涂于材面上进行基础着色，或常将着色剂加在稀薄的硝基漆或PU清面漆中，喷涂在经砂光的底漆面上进行涂膜修色。  \n\n用于透明着色剂的有机染料必须满足如下要求： $\\textcircled{1}$ 耐光性能好； $\\textcircled{2}$ 透明度高； $\\textcircled{3}$ 易溶解； $\\textcircled{4}$ 染色力强； $\\textcircled{5}$ 着色均匀； $\\textcircled{6}$ 对上层涂膜不渗色。  \n\n用于木材透明涂饰的常用染料类着色剂有如下几类。  \n\n$\\textcircled{1}$ 溶剂型着色剂溶剂型着色剂是将染料溶解于有机溶剂中的一类着色剂，涂饰木面不起毛、不膨胀、富于渗透性，可直接获得艳丽的色彩。在溶解好的染料溶液中有时可加入少量的油性树脂或具黏结力的材料，既适用于做基础着色又适用于涂膜修色，这样的溶剂型着色剂具有对基材附着力强、不易脱落又封闭好的特点。  \n\n溶剂型着色剂的有机染料主要是油溶性染料和分散性染料。  \n\na.油溶性染料着色剂常用的油溶性金属络合染料着色剂的配方见表3-7-109。  \n\n表3-7-109 常用的油溶性金属络合染料着色剂的配方 单位： $g_{\\mu}$   \n\n\n<html><body><table><tr><td>染料名称</td><td>红色精</td><td>黄色精</td><td>黑色精</td><td>橙色精</td><td>蓝色精</td><td>绿色精</td></tr><tr><td>Vali Fast 红 Zapon黄 Savinyl黑</td><td>40</td><td>20</td><td>8</td><td>20</td><td></td><td></td></tr></table></body></html>\n\n注：Zapon为巴斯夫染料；Vali为东方染料（日本）；Savinyl为科莱恩染料。  \n\n使用能溶解于油脂、蜡或其他有机溶剂而不溶于水的有机染料，具有色彩鲜艳、高透明度、着色力强的特点。用于木制品透明涂饰工艺的染料主要是金属络合类的红、黄、黑、橙、蓝和绿，这是目前应用最为普遍的油性着色剂。  \n\n·制造工艺在溶剂中投人染料，低速分散30min后静置过夜，检测细度合格（小于 $10\\mu\\mathrm m$ ）后用400目滤网过滤包装。  \n\n·特点经过筛选的此类金属络合染料制成的色精，易溶解、杂质少，颜色饱和度高，具有较好的耐光性能。  \n\n制造油溶性染料着色剂时，应精心选择染料，经过细致的试验，确认所选择的染料具有良好的溶解性，在贮存过程中颜色安定，使用中耐候性好，才能保证颜色的稳定性。  \n\nb.分散性染料着色剂 常用的分散性染色剂的配方见表3-7-110。  \n\n单位：%  \n\n表3-7-110 常用的分散性染料着色剂的配方  \n\n\n<html><body><table><tr><td>材料名称</td><td>分散红着色剂</td><td>分散黄着色剂</td><td>材料名称</td><td>分散红着色剂</td><td>分散黄着色剂</td></tr><tr><td>N,N-二甲基酰胺</td><td>26.09</td><td>29.85</td><td>硝基清漆</td><td>4.35</td><td>5.97</td></tr><tr><td>环己酮</td><td>34.78</td><td>35.82</td><td>分散红3B</td><td>4.35</td><td></td></tr><tr><td>醋酸丁酯</td><td>30.41</td><td>23.88</td><td>分散黄RGFL</td><td></td><td>4.48</td></tr></table></body></html>  \n\n使用不溶于水，经分散性助剂作用后才溶解水，才能对纤维性物质进行染色的分散性染料，由于色彩鲜艳，色牢度强，透明度高而不易褪色，多用于涂膜修色，但价格高。  \n\n$\\textcircled{2}$ 醇溶型着色剂 醇溶型着色剂的常用配方见表3-7-111。  \n\n表3-7-111 醇溶型着色剂的常用配方（质量分数）：醇溶性染料 $0.1\\%\\sim3\\%$ 乙醇（甲醇） $1000\\%$ ；脱色虫胶  \n\n\n<html><body><table><tr><td>名称</td><td>用量</td><td>名称</td><td>用量</td></tr><tr><td>醇溶性染料</td><td>0.1~3</td><td>脱色虫胶</td><td>30</td></tr></table></body></html>  \n\n醇溶型着色剂是一类能溶于醇类溶剂而不溶于水的有机染料，这类有机染料多为碱性染料、偶氮染料和磺酰胺化染料。  \n\n醇溶型着色剂使用乙醇为溶剂，由于乙醇和木材的亲和力好，故其着色力高，渗透性能强、色彩鲜艳。由于乙醇快速挥发，故多采用喷涂；但乙醇中含有一定量的水分，易使木纤维竖立，出现木毛现象；乙醇挥发迅速、干燥快，又容易造成着色发花，若刷涂，要求快速操作。为了增加醇溶型着色剂对木材的粘接强度，常用虫胶液作着色黏合剂。配制醇溶型着色剂时，先将有机染料溶解于乙醇中，然后再加入虫胶液，如用于浅色着色剂时，需使用脱色虫胶液。  \n\n③水溶型着色剂水溶型着色剂是以水为溶剂，配以能溶于水的酸性染料或直接染料组成，水溶型着色剂具有不易燃烧、价格低廉的特点，使用水溶型着色剂的缺点是会增加木材的水分，使木材表面的纤维因吸水膨胀而起毛，在涂装成膜时易产生气孔、粒子、漆膜发白等缺陷。  \n\n水溶型着色剂主要用于底着色，大多使用在热水中容易溶解的酸性染料和直接染料，其溶解温度多在 $80^{\\circ}C$ 以下，使用这类染料易在 $50\\sim60^{\\circ}C$ 的温度下溶解。  \n\n常用的酸性染料品种有：酸性橙、酸性棕RH、酸性大红GR、酸性黑10B、弱酸性黑等。  \n\n一般水溶型着色剂配成染料浓度 $10\\sim20\\mathbf{g}/\\mathrm{L}$ 液体使用。使用水溶型着色剂时的最大缺陷是涂饰时容易发花、起毛，这主要由于木材表面含有油污、木材材面组织结构不均匀、木材表面不光洁、涂饰不均匀等因素造成。可采用喷涂法进行水性着色，色彩较均匀，或少蘸多刷进行刷涂；也可以在着色剂中加人 $15\\%$ 左右醇类溶剂，以帮助着色剂均匀扩散。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 595,
+        "chunk": "# 3.木用涂料着色剂的质量控制  \n\n（1）木用涂料着色剂的着色材料要根据具体的着色要求精心选择，通常选择高透明度、高色牢度、低色迁移的染料配制染料型着色剂，一般选择中等耐光、耐候、高遮盖力、高着色力、无色迁移的颜料配制颜料型着色剂，而有特殊耐光性能需要时，也可以使用高耐光性颜料配制着色剂。这样从着色材料上保证了木用涂料着色剂的质量。  \n\n（2）木用涂料着色剂的质量控制细度：15～40um（底着色剂）；15～20um（修色剂、面调色）。贮存稳定性能：6～10月。附着力：保证层间附着，不脱落。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 596,
+        "chunk": "# 第五节 木用涂料产品的涂装应用",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 597,
+        "chunk": "# 一、现场调配  \n\n对终端产品如家具而言，木用涂料只是半成品，要针对不同涂装目的和需求做好涂装前的各项准备，尤其是对涂料的检查和调配，使其顺利进人后续的涂装生产。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 598,
+        "chunk": "# 1.涂料使用前的检查  \n\n木用涂料施工前的检查非常重要。检查主要包括仔细阅读涂料厂家提供的产品说明书；检查涂料名称、编号、批号、生产日期，看产品是否配套及有无过期和异常现象等；按涂料厂提供的技术参数检查技术指标是否正常；施工注意事项及特殊操作要求；必要时可模拟批量生产要求，做小板测试涂料的施工性能及重要漆膜性能，以便完善后续施工工艺参数。此外，根据涂料品种的性能，准备好施工中需要采取的必要的安全措施。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 599,
+        "chunk": "# 2.调配与静置  \n\n涂料贮存一段时间后，有时会分层，漆中的颜料、填料及其他粉料容易发生沉淀、结块、浮色，所以施工前要充分搅拌均匀。对于多组分的涂料，要严格按照操作规程或产品说明书上规定的比例进行调配，充分搅拌。如果涂料一次性调配的量较大，可采用机械搅拌装置。无论量多少，调配好的涂料在搅拌之后都应该静置一段时间再使用，主要目的是消泡。双组分涂料配漆后静置时间至少要15min。调配好的涂料在使用过程中，不可能一次用完，备用涂料里的颜料、填料或亚粉受重力影响会再次下沉，因此每次取用都要先行搅拌。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 600,
+        "chunk": "# 3.调整涂料黏度  \n\n黏度是木用涂料施工的一个关键指标。不同的涂料、不同的施工工艺、不同的涂装设备、不同的环境温湿度等，要求的施工黏度均可能不同，也就是说加人稀释剂的量并非恒定，须因不同情况而改变。稀释剂要求同厂产品、同种产品配套使用。气候、环境变化，有时需往稀释剂中添加部分发白水或慢干水来调节干燥速率。  \n\n调配好的交联反应型涂料必须在适用期内用完。如果涂装中有较长时间的停顿，要重新检测黏度及搅拌。为了保证涂料的性能和不造成浪费，少量多次、保持新鲜是调配的原则。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 601,
+        "chunk": "# 4.涂料过滤除去杂质  \n\n木用涂料在使用时，首先是充分搅拌，加人各组分配漆，再搅拌，调整黏度，最后必须用过滤方法滤去杂质。过滤底漆的滤网规格为80～150目，过滤免磨底漆、面漆和清漆的滤网规格为200～300目。小批量施工时，通常用手工方式过滤，使用大批量涂料时可用机械  \n\n方式过滤。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 602,
+        "chunk": "# 5.涂料颜色调整  \n\n在涂装时，有时需要在现场对原有色漆、清漆进行调色处理，此时，用于调色的各种材料，最好用与被调产品同一厂家、同一品种的产品。必要时应少量调试甚至喷板对色，确认没问题后再进行批量调色。调色时同样要充分搅拌并静置。  \n\n木用涂料现场调配的主要技术参数见表3-7-112，  \n\n表3-7-112木用涂料施工调配主要参数一览表  \n\n\n<html><body><table><tr><td>品种</td><td>配比(重量比)</td><td>施工固含 /%</td><td>适用期 /h</td><td>适宜温度 /℃</td><td>适宣湿度 /%</td><td>施工方式</td></tr><tr><td>NC</td><td>漆·稀[1：（1～1.5)]</td><td>15~30</td><td>不限制</td><td>15~35</td><td>35~85</td><td>浸涂、刷涂、喷涂（包括 静电喷涂、手工喷涂、电脑 自动喷涂)、辊涂、淋涂</td></tr><tr><td>PU</td><td>漆·固·稀 封闭底漆[1：0.25：（1～2）] 底漆[1：0.5；(0.5～8)] 面漆[1·（0.5～1.0）：（0.6～ 1.2)]</td><td><10 35~70 35～70</td><td>2~4</td><td>15~35</td><td>35~85</td><td>剧涂、喷涂（手喷、电脑 喷涂)、辊涂（底漆，不常 用)、淋涂(底、面）</td></tr><tr><td>UPE</td><td>漆：白水：蓝水：稀[100：（0.8～ 1.8)·(0.5~1.2):(20~30)]</td><td>70～100</td><td>0.5以内</td><td>15~35</td><td>35~85</td><td>手工喷涂、淋涂</td></tr><tr><td>UV</td><td>漆·稀[1:（0.3～0.5）]</td><td>70~100</td><td>不限制（避 光，有效期内)</td><td>15~35</td><td>35~85</td><td>辊涂UV底、喷PU面、 淋涂UV面、喷涂UV底、 喷涂UV面</td></tr><tr><td>AC</td><td>漆·酸·稀[1：（0.05～0.1）： (0.3~0.7)]</td><td>30~50</td><td>24</td><td>15~35</td><td>35~85</td><td>喷涂</td></tr><tr><td>W</td><td>单组分 漆·水[1：(0.1～0.3)] 双组分 漆·固·水[1：0.15：（0.1～ 0.2）]</td><td>15~35</td><td>不限制（单 组分，有效期 内);2～4（双 组分)</td><td>15~35</td><td>35～85</td><td>擦涂、刷涂、浸涂、喷涂</td></tr></table></body></html>\n\n注：调漆工具：漆桶、搅棒、台秤、秒表、黏度杯、温湿度计。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 603,
+        "chunk": "# 二、涂料产品底面漆配套原理  \n\n正确选择涂料体系、正确进行底面漆的搭配，对涂装效果和涂膜性能有重大影响，也会影响涂装质量、施工效率及施工成本。  \n\n涂料封闭底漆主要防止涂料被基材吸收，封锁基材的油分、水分，以免影响附着力，防止漆膜下陷。封闭底漆黏度较低，对基材的有良好的渗透性。封闭底漆还可胶固基材木纤维，打磨去除木毛便可得到平滑的表面。  \n\n底漆是漆膜骨架重要组成部分，因各种底漆的特点、配套性、施工性都有很大的差异，所以采用不同底漆就会有不同的涂装效果。面漆是涂装的最后工序。由于面漆实际上是在底漆上的重涂，很讲究层间附着力及施工操作，因而底、面搭配显得尤其重要。搭配合理，面漆才能发挥出最后、最好的效果。在不同体系涂料的搭配使用方面，要特别注意各种涂料的性能特点，合理配套，否则，容易出现诸如咬底、离层、龟裂等问题。如用NC底漆，就不宜用其他类型的面漆，只能配NC面漆。  \n\n底、面漆配套选择及评价可参照表3-7-113。  \n\n表3-7-113 底、面漆配套选择及评价  \n\n\n<html><body><table><tr><td>底层</td><td>面层</td><td>评价</td><td>涂膜效果</td></tr><tr><td>NC</td><td>NC</td><td>②</td><td>宜做开放效果</td></tr><tr><td>PU</td><td>NC</td><td>特</td><td>极大提高NC丰满度，适用于易损坏的木制品（如木门）及要保持NC味道的木制品</td></tr><tr><td>AC</td><td>AC</td><td>②</td><td>国内少用</td></tr><tr><td>AC</td><td>PU</td><td>②</td><td>国内少用</td></tr><tr><td>PU</td><td>PU</td><td>②</td><td>漆膜丰满度、光泽和手感都好，最普遍采用的配套</td></tr><tr><td>UPE</td><td>UPE</td><td></td><td>理论上没问题，实际上很少用气干型不饱和涂料做面漆，蜡型不饱和不在本讨论范围</td></tr><tr><td>UPE</td><td>PU</td><td>①</td><td>经典配套</td></tr><tr><td>UV</td><td>UV</td><td>#</td><td>应用广泛及未来发展趋势，效率好、环保</td></tr><tr><td>UV</td><td>PU</td><td>③</td><td>视工艺需要选择，搭配没问题，要解决好前快后慢的问题</td></tr><tr><td>W</td><td>W</td><td>①</td><td>未来发展趋势</td></tr><tr><td>W</td><td>PU,NC</td><td>特</td><td>视工艺需要选择</td></tr></table></body></html>\n\n注： $\\textcircled{1}$ 表示最好； $\\textcircled{2}$ 表示好； $\\textcircled{3}$ 表示可用；特表示特殊情况下使用。  \n\n$\\textcircled{2}$ 的评价是好，NC底NC面，相同体系，且底面的干速、施工容易的特点统一，应用非常广泛，特别用于美式涂装及家居装修中；AC底AC面，在采用AC漆的时候，这个配套也很普遍；AC底PU面，既发挥了AC底快干的优点，又通过PU面提高装饰性；PU底PU面，是目前国内家具涂装中应用最为广泛的配套，底面同体系，干速同步，加上PU漆的高装饰性，当然是绝佳搭配。  \n\n$\\textcircled{3}$ 的评价是可用，UV底PU面的配套没有问题，要注意的是，底漆的生产效率远高于面漆，如何合理安排生产，或前后怎样衔接是关键。如果从效率上讲，UV底UV面最高。选择UV底PU面，主要是发挥PU面的高装饰性效果，或者说是综合PU漆和UV漆各自的优点。  \n\n$\\textcircled{1}$ 的评价，一方面UV底UV面，W底W面这两种配套，除了本身性能、效果、配套均无问题外，环保因素是其被力荐的又一个重要原因，又好又环保，所以最好；另一方面，UPE底PU面，不考虑UV涂装的话，是公认的“经典配套”。如果做实色涂装、全封闭透明涂装，这个配套均是“第一选择”。选UPE为底，是因为它可一次性厚涂，PU底要达到这个厚度，一般要涂三次。同时UPE打磨性好，稍显不足的是操作较烦琐，收缩性大。PU作面，仍然是因为其不可替代的、自然味道的装饰性（与打磨、抛光后的效果不同)。最好的底漆，配最好的面漆，配套性又没有问题，评价自然最经典、最好。  \n\n特殊情况下使用的两种配套：W底、PU或NC作面，在家装时可考虑使用。有时可解决着色不均匀、施工期短等问题。PU底加NC面，这里的PU可视为封闭底漆，也可视为真正的PU底漆。封闭底漆可把NC托起来，大大提高NC丰满度，减少涂装道数及时间，用于木门涂装时，如选用PU底漆NC面漆，托起效果更好，木门表面保持NC特性，作为易损坏的表面，容易进行无痕修补。  \n\n表3-7-113是指导性的，当要根据实际情况灵活运用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 604,
+        "chunk": "# 三、木用涂装常用涂装工艺",
+        "category": " Introduction"
+    },
+    {
+        "id": 605,
+        "chunk": "# 1.木器制品常见涂装效果  \n\n木器制品的涂装效果，主要受漆膜厚度和漆膜光泽影响。以透明涂装而言，从漆膜厚度分析，可分为以下几种。  \n\n（1）开放式涂装（开孔涂装）木材导管孔呈开口状态的薄膜涂装。涂装沿着木材导管孔的内壁形成一层薄的涂膜，涂装中一般不将导管孔填实，涂装后的表面管孔仍然显露，强化木质天然质感。  \n\n(2）全封闭涂装（闭孔涂装）涂装中用填孔剂与涂料将木材导管孔全部填满填实填牢，上面涂膜做厚，如经研磨抛光可获得丰满、厚实、高光的镜面效果。  \n\n(3）半开放涂装介于开孔与闭孔装饰的中间型涂装，即在涂装中使用填孔剂，适当填孔，又不完全填满，表面呈现半开孔状，管孔内部涂膜较开孔涂装厚，其防污、防湿及防水的效果较佳。此法有利于显现各树种的木纹。  \n\n（4）天然植物油涂装北欧部分国家流行选用易渗透的涂料（多为油性漆）涂装实木家具，涂料施工后充分渗透至木材内部，而木材表面仅有极薄的膜或几乎没有涂膜，此时最能显现木材特有的天然质感。但是由于几乎没有膜，故其保护作用较差，制品表面极易受污染与损伤。  \n\n漆膜表面光泽亦会影响最终涂装效果。漆膜光泽一般分三类。  \n\n（1）亮光涂装如镜面效果，涂膜丰满厚实，由于光线的全反射而具极高光泽，涂面光芒四射，使制品显得豪华高贵，充分显现涂膜的厚实感。  \n\n(2）半光涂装如三分光、五分光（半光)、七分光等不同比例的光泽表现。使用不同光泽的面漆，并结合相应材质、颜色、被涂物的形状、涂装膜厚等因素，可形成各具特色的、不同风格的装饰效果。  \n\n(3）亚光（无光）涂装因光线的散射而呈现无光泽的沉稳感，虽有涂膜但少了厚重感，如亚光、开孔或半开孔涂装，涂膜相对较薄，虽有涂装，但表现的是轻快、高雅的感觉，其涂装过程与常规涂装无异，仅仅是面漆不同。也可以不使用头道及二道底漆，而直接以消光面漆涂装，涂层干后，打磨后再上一次亚光面漆，此法多用于美式仿古家具。  \n\n与透明涂装相比，实色涂装的特点是基材选择更广泛，丰满度高，同样可用高光泽、半光或亚光表现出不同品味。其中中性色黑白灰多用于办公及商业用品，彩色则多用于橱柜中。除此之外尚有多种美术涂装效果用于家具的局部点缀及家装中。可根据不同需要选用不同的涂料，用不同的涂装工艺获得不同的涂膜效果，展示不同的涂装风格。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 606,
+        "chunk": "# 2.传统涂装主要涂装工艺  \n\n传统涂装六种涂装工艺  \n\n(1）中纤板实色涂装工艺中纤板-水灰或其他腻子-封闭-底漆(PU或UPE)-实色面漆(亮光或亚光)，见表3-7-114。  \n\n表3-7-114 中纤板PU实色涂装工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">施工条件</td><td colspan=\"3\">底材：中纤板 涂料：PU实色漆 施工温度25℃、湿度75%以下</td></tr><tr><td>序号</td><td>工序</td><td>材料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>１</td><td>中纤板</td><td>砂纸</td><td>手磨、机磨</td><td>将白坯打磨平整，去污痕</td></tr><tr><td>2</td><td>腻子</td><td>专用腻子(如水灰)</td><td>刮涂</td><td>刮涂平整，宜薄刮</td></tr><tr><td>3</td><td>打磨</td><td>砂纸</td><td>手磨、机磨</td><td>打磨平整</td></tr><tr><td>4</td><td>封闭</td><td>PU封闭底漆</td><td>刷、喷、擦</td><td>对底材进行有效封闭，干后轻磨</td></tr><tr><td>5</td><td>实色底漆</td><td>PU或UPE底漆</td><td>喷涂，可湿碰湿</td><td>底漆与面漆的颜色最好接近，对提高 遮盖力有很大帮助；注意湿碰湿第一遍 施工时宜薄涂</td></tr><tr><td>6</td><td>实色面漆（亮光或亚光）</td><td>PU实色面漆</td><td>喷涂</td><td>均匀平整</td></tr></table></body></html>\n\n注：1.中纤板：清除板上的油污和胶印。2.腻子：用水灰或其他腻子刮涂 $1{\\cdots}2$ 次，将基材填平，干透后打磨干净，不宜厚涂。3.封闭：用PU封闭漆，喷涂、擦涂、刷涂均可，其目的是对底材进行封闭，增加底漆对基材的附着力，防止漆膜下陷，干后轻磨。4.底漆：可选用PU或UPE实色底漆，按标准配比施工，均匀喷涂，需要时PU漆可选用湿碰湿工艺。5.面漆：PU面漆，按标准配比调到 $12.5$ 的施工黏度喷涂。  \n\n(2）中纤板贴纸涂装工艺中纤板-刮腻子-打磨-贴纸-PU或UPE透明底漆-修色-清面漆（亮光或亚光)，见表3-7-115。  \n\n表3-7-115 中纤板贴纸涂装工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">底材：中纤板贴纸 施工条件 涂料：PU或UPE 施工温度25℃，湿度75%以下</td><td colspan=\"3\"></td></tr><tr><td>序号</td><td>工序</td><td>材 料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>1</td><td>中纤板</td><td>砂纸</td><td>手磨、机磨</td><td>白坯打磨平整，去污痕</td></tr><tr><td>2</td><td>刮腻子</td><td>专用腻子(如水灰、猪血灰等)</td><td>刮涂</td><td>刮涂平整，宜薄刮</td></tr><tr><td>3</td><td>打磨</td><td>砂纸</td><td>手磨、机磨</td><td>打磨平整</td></tr><tr><td>4</td><td>贴纸</td><td>各色木纹纸</td><td>手贴、机贴</td><td>无气泡、无皱纹、整齐-致，7h后实干</td></tr><tr><td>5</td><td>底漆</td><td>PU或UPE透明底漆</td><td>喷涂</td><td>PU底漆湿碰湿两遍或UPE底漆两遍</td></tr><tr><td></td><td>面修色</td><td>透明封闭底漆或面漆加色</td><td>喷涂</td><td>由浅人深均匀着色</td></tr><tr><td>7</td><td>面漆</td><td>PU面漆</td><td>喷涂</td><td>均匀喷涂，注意过滤、防尘</td></tr></table></body></html>\n\n注：1.中纤板：清除白坯板上的油污和胶印，便于将纸贴平整。2.刮腻子：用水灰等来填补板材的钉眼、拼缝和缺陷，打磨平整，尽量减少因板材的缺陷而影响贴纸的平整度。3.贴纸：贴纸后要求无气泡、无皱纹、整齐一致，需干燥7h以上。4.底漆：PU或UPE透明底漆，按标准配比施工，喷涂均匀。PU底要稀一些，UPE之前要用PU封闭。5.面修色：用透明封闭底漆或面漆自行加色，或用已调好颜色的透明封闭底漆或面漆修色。由浅入深均匀着色。6.面漆：PU面漆，按标准配比调到适宜稠度喷涂。  \n\n(3）中纤板贴木皮的全封闭涂装工艺中纤板-贴木皮-封闭（可选择)-底着色（按照需要选择使用：有色水灰、有色士那、木纹宝、格丽斯)-封闭（可选择)-PU或UPE透明底漆-修色-清面漆（亮光或亚光)，见表3-7-116。  \n\n(4）中纤板贴木皮的半开放涂装工艺中纤板-贴木皮-封闭（可选择)-底着色-封闭（可 选择)-PU或UV透明底漆-PU透明面漆，见表3-7-117。  \n\n表3-7-116 中纤板贴木皮的全封闭涂装工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">施工条件</td><td colspan=\"3\">底材：中纤板贴木皮 涂料：PU、NC 或UPE 施工温度25℃，湿度75%以下</td></tr><tr><td>序号</td><td>工序</td><td>材料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>1</td><td>中纤板</td><td>砂纸</td><td>手磨、机磨</td><td>去污迹、白坯打磨平整</td></tr><tr><td>2</td><td>贴木皮</td><td>各种木皮，胶水</td><td>手贴、机贴</td><td>贴平整，待干时间要足够</td></tr><tr><td>3</td><td>封闭（可选择）</td><td>PU封闭底漆</td><td>刷、喷、擦</td><td>对底材进行有效封闭，干后轻磨</td></tr><tr><td>4</td><td>底着色</td><td>选择有色水灰、有色士 那、木纹宝、格丽斯等着色 材料</td><td>刮涂、擦涂、喷涂</td><td>着色均匀，颜色主要留在木眼里面，木径部分 残留要少</td></tr><tr><td>5</td><td>封闭(可选择)</td><td>PU封闭底漆</td><td>刷涂、喷涂</td><td>对底材、颜色进行有效封闭，保护底色，增加 附着力，3～4h后可轻磨，切忌磨穿及把底色 打花</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>序号</td><td>工序</td><td>材料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>6</td><td>底漆</td><td>PU或UPE透明底漆</td><td>喷涂、可湿碰湿</td><td>干后要彻底打磨平整，忌磨穿</td></tr><tr><td>7</td><td>修色</td><td>士那/面漆加色</td><td>喷涂</td><td>由浅人深均匀着色</td></tr><tr><td>8</td><td>面漆</td><td>清面漆(亚光或亮光)</td><td>喷涂</td><td>均匀喷涂</td></tr></table></body></html>\n\n注：1.中纤板；清除中纤板油污和胶印，对高档板式家具还需进行定厚砂光，才能进行贴木皮。2.贴木皮：将木皮贴平整，以机器贴为主，一些边角可以人工贴或者用实木线条来取代。  \n\n3.封闭底漆（可选择）：去木毛、防渗陷、增加附着力。  \n\n4.底着色：按照需要选用有色水灰、有色士那、木纹宝、格丽斯等着色材料，采用刮涂、擦涂、喷涂等施工方式，颜色要擦拭均匀。  \n\n5.封闭底漆（可选择)：再用PU封闭漆封闭，喷涂均匀，其目的是对底色进行保护，以避免在喷涂底漆后出现浮色的现象；还能增加底漆的附着力，防止下陷。封闭底干后必须轻磨，以免磨穿及把底色打花。可选择的意思是二选一或二选二，最少一次。  \n\n6.PU或UPE透明底漆：PE透明底漆，按标准配比施工，喷涂均匀。  \n\n7.修色：参照色板来修色，原则是先里面后外面，先难后易，由浅人深均匀着色。  \n\n8.面漆：PU面漆，按标准配比调到12s施工黏度喷涂。  \n\n9.“士那”即“sealer”的音译，“seal”意思是封闭。“sealer”意思是“封闭底漆”或“封闭剂”，“有色士那”是指“透明有色封闭剂”或“透明有色封闭底漆”，下同。  \n\n表3-7-117 中纤板贴木皮的半开放涂装工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">施工条件</td><td colspan=\"3\">底材：中纤板贴木皮 涂料：PU、NC、UV或UPE 施工温度25℃，湿度75%以下</td></tr><tr><td>序号</td><td>工序</td><td>材料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>1</td><td>中纤板</td><td>砂纸</td><td>手磨、机磨</td><td>去污迹、白坯打磨平整</td></tr><tr><td>2</td><td>贴木皮</td><td>各种木皮，胶水</td><td>手贴、机贴</td><td>贴平整，待干时间要足够</td></tr><tr><td>3</td><td>封闭(可选择)</td><td>PU封闭底漆</td><td>喷、涂、刷</td><td>砂磨去木毛、防渗陷、增加附着力</td></tr><tr><td>4</td><td>底着色</td><td>按照需要选择使用有色 士那、木纹宝、格丽斯等着 色材料</td><td>刮涂、擦涂、喷涂</td><td>着色均匀，颜色主要留在木眼里面，木径部 分残留要少</td></tr><tr><td>5</td><td>封闭(可选择)</td><td>PU底得宝</td><td>刷涂、喷涂</td><td>对底材、颜色进行有效封闭，保护底色，增 加附着力，3～4h后可轻磨</td></tr><tr><td>6</td><td>底漆</td><td>PU或UV透明底漆</td><td>喷涂</td><td>根据开放效果再加一道底漆，中间须打磨， 5～8h手打磨</td></tr><tr><td>7</td><td>面漆</td><td>面漆</td><td>喷涂</td><td>均匀喷涂</td></tr></table></body></html>\n\n注：1.中纤板：底材打磨处理，要平整，去除污迹、胶印。对高档板式家具还需定厚砂光，才能进行贴木皮。  \n\n2.贴木皮：木皮选取木眼粗、深、纹理清晰，着色前用铜刷，沿木材导管方向刷导管，清除染迹、灰渍及扩充木，使木材纹理突出、清晰。  \n\n3.底着色：选用士那、木纹宝或格丽斯等着色材料来对底材着色，以突显木材纹理；用木纹宝来做底着色半开放工艺时，需将木纹宝调稀一些，以免填平木眼。  \n\n4.封闭：在着色前对板材进行封闭时，采取喷涂、擦涂、刷涂均可，其目的是防止下陷和便于均匀着色；为避免颜色上不去的问题，封闭不宜厚，封闭底漆应适当调稀，但边角、木材的端头部分要封闭厚一些，以避免在底着色时出现着色不匀的现象。着色后进行封闭时，不要把产品颜色擦花，所以必须喷涂，其目的是对底色进行保护，以避免在喷涂底漆后出现浮色的现象；还能增加底漆的附着力，防止下陷。可选择的意思是二选一或二选二，最少一次（与表3-7-114同）。  \n\n5.底漆：PU底漆或改性PU底漆适合开放效果，黏度控制在 $12\\approx145$ （涂-2杯）喷涂；UV透明底漆辊涂 $1\\sim2$ 遍视木眼的深浅来定)。  \n\n6.面漆：面漆的施工黏度控制在 $10\\sim125$ (涂-2杯)，以亚光为主。  \n\n(5）实木底着色全封闭的透明涂装工艺实木-腻子-封闭（可选择)-底着色-封闭（可选择)-PU/UPE透明底漆-打磨-PU透明面漆（变化工艺可得开孔或封闭不同程度效果)，见表3-7-118。  \n\n表3-7-118 实木底着色全封闭的透明涂装工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">施工条件</td><td colspan=\"3\">底材：实木 涂料：NC、PU或UPE 施工温度25℃，湿度75%以下</td></tr><tr><td>序号</td><td>工序</td><td>材 料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>1</td><td>实木</td><td>砂纸</td><td>手磨、机磨</td><td>去污迹、白坯打磨平整</td></tr><tr><td>2</td><td>刮腻子</td><td>选择非油性有色腻子</td><td>刮涂</td><td>打磨时木眼里的腻子填实，外边的腻 子均要磨干净</td></tr><tr><td>3</td><td>封闭(可选择)</td><td>PU封闭底漆</td><td>喷、涂、刷</td><td>去木毛、防渗陷、增加附着力</td></tr><tr><td>4</td><td>底着色</td><td>按照需要选择使用有色水灰、 有色士那、木纹宝、格丽斯等着色刮涂、擦涂、喷涂 材料</td><td></td><td>着色均匀，颜色主要留在木眼里面，木 径部分残留要少</td></tr><tr><td>5</td><td>封闭（可选择）</td><td>PU封闭底漆</td><td>刷涂、喷涂</td><td>对底材、颜色进行有效封闭，保护底 色，增加附着力，3～4h后可打磨</td></tr><tr><td>6</td><td>底漆</td><td>透明底漆</td><td>喷涂、可湿碰湿</td><td>底漆层间干燥要足够</td></tr><tr><td>7</td><td>打磨</td><td>砂纸</td><td>手磨、机磨</td><td>打磨均匀平整</td></tr><tr><td>8</td><td>面漆</td><td>面漆</td><td>喷涂</td><td>均匀喷涂</td></tr></table></body></html>\n\n注：1.实木：清除白坏板上的油污和胶印，以避免在底着色时，产生着色不匀的现象。  \n\n2.刮腻子：进行底着色工艺时，腻子一般选择刮水性腻子较多；若刮涂油性腻子，一般采取面着色工艺，因油性腻子不易底着色。  \n\n3.底着色：根据所需做的表面效果及施工要求可选用不同的着色材料，用PU格丽斯进行底着色，其着色性比较好，也易于擦拭，填充性比木纹宝差；木纹宝是既能填充又能着色；而士那则既能底着色又能进行面修色，便于修补磨穿的底色。  \n\n4.封闭：在着色前对板材进行封闭时，采取喷涂、擦涂、刷涂均可，其目的是防止下陷和便于均匀着色；为避免颜色上不去的问题，封闭不宜厚，封闭底漆应适当调稀，但边角、木材的端头部分要封闭厚一些，以避免在底着色时出现着色不匀的现象。着色后进行封闭时，不要把产品颜色擦花，所以必须喷涂，其目的是对底色进行保护，以避免在喷涂底漆后出现浮色的现象；还能增加底漆的附着力，防止下陷。可选择的意思是二选一或二选二，最少一次（与表3-7-114同）。  \n\n5.底漆：PU或UPE透明底漆，按标准配比施工，喷涂均匀。  \n\n6.面漆：PU面漆，按标准配比调到12s喷涂。  \n\n(6）红木家具封闭加生漆涂装工艺红木-补色-封油士那-腻子（有色木灰)-打磨-着色封油士那（可选择)-打磨-修色-PU底漆-打磨-面漆（大漆）五遍，见表3-7-119。红木涂装亦可全部用大漆。  \n\n表3-7-119 红木家具封闭加生漆涂装工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">施工条件</td><td colspan=\"3\">底材：红木 涂料：PU，大漆 施工温度25℃，湿度80%左右</td></tr><tr><td>序号</td><td>工序</td><td>材料</td><td>施工方法 施工要点</td></tr><tr><td>１</td><td>红木</td><td>砂纸</td><td>手磨、机磨 去污迹，顺木纹打磨平整、光滑</td></tr><tr><td>2</td><td>补色</td><td>PU修色剂</td><td>擦涂 使白坯的颜色基本一致</td></tr><tr><td>3</td><td>封油士那</td><td>封油士那</td><td>用封油士那封闭，天那水对稀，厚薄适中；可视基 刷涂或措涂 材含油量的多少，适当增加1～2遍封油士那</td></tr></table></body></html>  \n\n$$\n\\cdot\\cdot\\cdot\\cdot\\cdot\\cdot\\cdot\\cdot\n$$  \n\n续表  \n\n\n<html><body><table><tr><td>序号</td><td>工序</td><td>材料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>4</td><td>腻子(有色底灰)</td><td>有色木灰</td><td>刮涂</td><td>刮有色木灰两遍，3h后打磨</td></tr><tr><td>5</td><td>打磨</td><td>砂纸</td><td>手磨</td><td>除木毛、木刺，光滑无亮点</td></tr><tr><td>6</td><td>着色</td><td>有色士那着色</td><td>擦涂</td><td>均匀着色</td></tr><tr><td>T</td><td>封油士那(可选择)</td><td>封油士那</td><td>刷涂或措涂</td><td>用封油士那封闭</td></tr><tr><td>80</td><td>打磨</td><td>砂纸</td><td>手磨</td><td>平整、光滑</td></tr><tr><td></td><td>修色</td><td>PU修色剂</td><td>喷涂</td><td>颜色均匀一致</td></tr><tr><td>10</td><td>底漆</td><td>PU透明底漆</td><td>喷涂</td><td>湿碰湿一次，第一道涂膜要薄，待干时间要足够</td></tr><tr><td>11</td><td>打磨</td><td>砂纸</td><td>手磨</td><td>平整、光滑</td></tr><tr><td>12</td><td>面漆</td><td>大漆</td><td>喷涂，指、擦4～8遍</td><td>均匀涂布，使膜面光泽一致，手感细腻</td></tr></table></body></html>  \n\n注：1.红木：用砂纸顺木纹打磨平整、光滑，清除污迹。2.补色：使白坯的颜色基本一致。3.封油士那：对底材进行封闭，避免树脂、单宁等物质渗出而影响涂装效果。确保大漆不往下陷，确保附着力。4.有色底灰：填平木眼、毛孔，彻底打磨平整，只留木眼，不留木径；若一遍没有填平，还可以多刮几次有色底  \n灰；注意一定要把木径表面打磨干净并彻底清理余灰。5.打磨：除木毛、木刺，光滑无亮点。打磨平整、光滑。6.封油士那：二次封闭，对底材、有色底灰进行封闭，增加底漆对基材的附着力，有助于防止漆膜下陷。此工序可  \n根据实际情况可省去。封油士那有别于普通士那。专用于油性木。7.打磨：打磨平整、光滑。8.修色：颜色均匀一致。9.底漆：按标准配比施工，喷涂均匀。10.打磨：打磨平整、光滑。11.面漆：生漆、大漆一般采取的施工方式是措涂，一般需 $4\\sim8$ 次，方可达到质量要求。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 607,
+        "chunk": "# 3.实用涂装推荐工艺  \n\n除上述六种常见工艺之外，实际生产时，针对不同的风格、不同涂装需要、不同生产条件、不同底材、不同原材料及辅料，会选多种多样的涂装工艺，下面列出一些常见实用涂装工艺，供参考。  \n\n(1）实用工艺一中纤板NC实色涂装工艺：中纤板-腻子-封闭-打磨-底漆-打磨-底漆-打磨，见表3-7-120。  \n\n表3-7-120 中纤板NC实色涂装工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">施工条件</td><td colspan=\"4\">底材：中纤板 涂料：NC实色漆 施工温度25℃、湿度75%以下</td></tr><tr><td>序号</td><td>工序</td><td>材料</td><td></td><td>施工方法</td><td>施工要点</td></tr><tr><td>1</td><td>白坯处理</td><td>砂纸</td><td></td><td>手磨、机磨</td><td>将白坯打磨平整，去污痕</td></tr><tr><td>2</td><td>刮腻子</td><td>各类腻子</td><td>刮涂</td><td></td><td>打磨时木眼里的腻子填实，外边的腻子要磨干净</td></tr><tr><td>3</td><td>打磨</td><td>砂纸</td><td></td><td>手磨</td><td>打磨平整，光滑无亮点</td></tr><tr><td>4</td><td>封闭</td><td>用虫胶漆、NC漆或PU封闭漆封闭</td><td>刷、喷、擦</td><td></td><td>对底材进行封闭</td></tr><tr><td>5</td><td>打磨</td><td>砂纸</td><td></td><td>手磨</td><td>轻磨</td></tr><tr><td>6</td><td>底漆</td><td>实色NC底第一遍</td><td>喷涂1～2道</td><td>喷涂均匀</td><td></td></tr><tr><td>7</td><td>打磨</td><td>砂纸</td><td>手磨、机磨</td><td>彻底打磨平整</td><td></td></tr></table></body></html>  \n\n续表  \n\n<html><body><table><tr><td>序号</td><td>工序</td><td>材料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>8</td><td>底漆</td><td>实色NC底第二遍</td><td>喷涂2～4道</td><td>要有足够厚度</td></tr><tr><td>9</td><td>打磨</td><td>砂纸</td><td>手磨</td><td>先用320*打磨，再用600*轻磨去砂痕</td></tr><tr><td>10</td><td>面漆</td><td>实色NC面第一遍</td><td>喷涂</td><td>注意喷涂均匀</td></tr><tr><td>11</td><td>打磨</td><td>砂纸</td><td>手磨、轻磨</td><td>打磨平滑无亮点，切忌磨穿</td></tr><tr><td>12</td><td>面漆</td><td>实色NC面第二遍</td><td>喷涂2～4道</td><td>要有足够厚度</td></tr></table></body></html>\n\n注：1.封闭底漆：在打磨封闭底漆后最好用PU或UPE腻子刮补中纤板截面。2.底漆：NC实色底漆施工黏度可调整在 $16\\sim185$ ，用雾化效果好的喷涂工具，黏度可调到 $20\\sim245$ 进行喷涂。3.打磨：第一遍面漆后打磨所选用的砂纸粒度要合适，而且打磨时力度一定要掌握好。4.面漆：用配套的面漆稀释剂调到12s施工黏度喷涂。  \n\n(2）实用工艺二实木本色涂装工艺：实木-封闭-打磨-刮腻子-打磨-底漆-打磨-底漆-打磨-面漆-打磨-面漆，见表3-7-121。  \n\n表3-7-121 实木本色涂装工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">施工条件</td><td colspan=\"3\">底材：实木 涂料：PU、NC或UPE</td></tr><tr><td>序号</td><td>工序</td><td>施工温度25℃，湿度75%以下 材料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>1</td><td>白坯打磨</td><td>砂纸</td><td>手磨、机磨</td><td>去污迹、白坯打磨平整</td></tr><tr><td>2</td><td>封闭</td><td>PU封闭底漆</td><td>刷涂、喷涂、擦涂</td><td>对底材进行封闭，3～4h后可打磨</td></tr><tr><td>3</td><td>打磨</td><td>砂纸</td><td>手磨</td><td>轻磨、消除木毛</td></tr><tr><td>4</td><td>刮腻子</td><td>PU透明腻子</td><td>刮涂</td><td>填平木眼，3h后可打磨</td></tr><tr><td>5</td><td>打磨</td><td>砂纸</td><td>手磨、机磨</td><td>彻底打磨平整，多余腻子清除干净</td></tr><tr><td>6</td><td>底漆</td><td>PU透明底漆</td><td>喷涂、可湿碰湿</td><td>均匀喷涂，5～8h后可打磨</td></tr><tr><td></td><td>打磨</td><td>砂纸</td><td>手磨、机磨</td><td>彻底打磨平整</td></tr><tr><td>8</td><td>底漆</td><td>PU透明底漆</td><td>喷涂、可湿碰湿</td><td>均匀喷涂，5～8h打磨</td></tr><tr><td>9</td><td>打磨</td><td>砂纸</td><td>手磨、机磨</td><td>彻底打磨平整</td></tr><tr><td>10</td><td>面漆</td><td>PU清面漆</td><td>喷涂</td><td>均匀喷涂，8～10h后轻磨</td></tr><tr><td>11</td><td>打磨</td><td>砂纸</td><td>手磨</td><td>轻磨颗粒，切忌打穿</td></tr><tr><td>12</td><td>面漆</td><td>PU清面漆</td><td>喷涂</td><td>均匀喷涂</td></tr></table></body></html>\n\n注：1.刮腻子：腻子要刮平、填实。也可以用配套的稀释剂调稀后进行擦涂。2.底漆：当使用NC底漆时，要多涂 $1\\sim2$ 遍获得一定厚度的涂膜。3.面漆：用配套的面漆稀释剂调到12s施工黏度喷涂。  \n\n(3）实用工艺三实木底着色开放透明涂装工艺：实木-封闭-打磨-着色-底漆-打磨-修色打磨-面漆，见表3-7-122。  \n\n表3-7-122 实木底着色开放透明涂装工艺  \n\n\n<html><body><table><tr><td colspan=\"2\" rowspan=\"2\">施工条件</td><td rowspan=\"2\">底材：实木 涂料：PU、NC或UPE 施工温度25℃，湿度75%以下</td><td rowspan=\"2\"></td><td rowspan=\"2\"></td></tr><tr><td colspan=\"3\"></td></tr><tr><td>序号</td><td>工序</td><td>材料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>1</td><td>白坯</td><td>砂纸</td><td>手磨、机磨</td><td>去污迹、白坯打磨平整</td></tr><tr><td>2</td><td>封闭</td><td>PU封闭底漆</td><td>刷涂、喷涂</td><td>对底材进行封闭，3～4h后可打磨</td></tr><tr><td>3</td><td>打磨</td><td>砂纸</td><td>手磨</td><td>轻磨、消除木毛</td></tr></table></body></html>  \n\n<html><body><table><tr><td>序号</td><td>工序</td><td>材料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>4</td><td>着色</td><td>格丽斯等着色材料</td><td>擦涂</td><td>擦涂可加放适量慢干水，也可采用喷涂方式着色</td></tr><tr><td>5</td><td>底漆</td><td>透明底漆</td><td>喷涂</td><td>根据开放效果如要加一道底漆的话，中间须打磨，5～8h手打磨</td></tr><tr><td>6</td><td>打磨</td><td>砂纸</td><td>手磨、机磨</td><td>彻底打磨平整，切忌打穿</td></tr><tr><td>7</td><td>修色</td><td>清面漆(配好)：色精</td><td>喷涂</td><td>可适当用稀料调稀，技巧是由浅人深</td></tr><tr><td></td><td>打磨</td><td>砂纸</td><td>手磨</td><td>轻磨颗粒，不可打穿、也可省去此工序</td></tr><tr><td>9</td><td>面漆</td><td>面漆</td><td>喷涂</td><td>均匀喷涂</td></tr></table></body></html>\n\n注：1.如果要做面修色，可在 ${}^{44}{\\mathfrak{g}}^{n}$ 工序后进行修色。2.面漆：用配套的面漆稀释剂调到12s施工黏度喷涂。  \n\n(4）实用工艺四实木面着色透明（半透明)、开放（半开放）涂装工艺：实木-封闭-打磨-透明底漆-打磨-透明底漆-打磨-透明有色面漆，见表3-7-123。  \n\n表3-7-123 实木面着色透明（半透明）涂装工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">底材：实木 施工条件</td><td colspan=\"3\">涂料：PU、NC或UPE 施工温度25℃，湿度75%以下</td></tr><tr><td>序号</td><td>工 序</td><td>材料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>1</td><td>白坯</td><td>砂纸</td><td>手磨、机磨</td><td>去污迹、白坯打磨平整</td></tr><tr><td>2</td><td>封闭</td><td>PU封闭底漆</td><td>刷涂、擦涂</td><td>对底材进行封闭，3～4h后可打磨</td></tr><tr><td>3</td><td>打磨</td><td>砂纸</td><td>手磨</td><td>轻磨、消除木毛</td></tr><tr><td>4</td><td>底漆</td><td>透明底漆(PU、NC或UPE均可)</td><td>喷涂、可湿碰湿</td><td>均匀喷涂，5～8h手工打磨</td></tr><tr><td>5</td><td>打磨</td><td>砂纸</td><td>手磨、机磨</td><td>彻底打磨平整</td></tr><tr><td>6</td><td>底漆</td><td>透明底漆(PU、NC或UPE均可)</td><td>喷涂、可湿碰湿</td><td>同“4”</td></tr><tr><td>7</td><td>打磨</td><td>砂纸</td><td>手磨、机磨</td><td>彻底打磨平整</td></tr><tr><td>8</td><td>透明有色面漆</td><td>PU透明面漆</td><td>喷涂</td><td>厚度务必均匀，如NC底对应NC透明 有色面漆</td></tr></table></body></html>\n\n注：1.透明面着色漆：用配套的面漆稀释剂调到12s施工黏度喷涂。2.半开放或全开放、透明或半透明效果的影响因素是：漆膜总厚度、打磨程度、颜色的浓淡。  \n\n(5）实用工艺五红木家具纯生漆涂装工艺：红木-刮腻子-打磨-上色-补色-上底漆-打磨-上面漆，见表3-7-124。  \n\n续表  \n表3-7-124 红木家具纯生漆涂装工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">底材：红木 施工条件 涂料：生漆</td><td colspan=\"3\"></td></tr><tr><td>序号</td><td>工序</td><td>施工温度25℃，湿度80%左右 材 料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>1</td><td>白坯</td><td>砂纸</td><td>手磨、机磨</td><td>清除木毛、木刺</td></tr><tr><td>2</td><td>刮腻子</td><td>生漆灰(生漆、填充料、适量水的混合物)</td><td>刮涂</td><td>填平、填实木眼</td></tr><tr><td>3</td><td>打磨</td><td>砂纸</td><td>手磨</td><td>除净木径上的灰迹，使木纹纹理清晰</td></tr><tr><td>4</td><td>上色</td><td>PU修色剂</td><td>擦涂（2～3道)</td><td>使颜色基本一致</td></tr><tr><td>5</td><td>补色</td><td>PU修色剂</td><td>擦涂（1～2道)</td><td>使颜色基本一致</td></tr><tr><td>6</td><td>上底漆</td><td>稍稠的加有粉料的生漆</td><td>刷、擦8～10道</td><td>表面均匀一致</td></tr><tr><td>7</td><td>打磨</td><td>砂纸</td><td>手磨</td><td>打磨平整，光滑</td></tr><tr><td>8</td><td>上面漆</td><td>生漆</td><td>措、擦8~10道</td><td>按要求</td></tr></table></body></html>\n\n注：1.刮灰：生漆遇铁会变黑，因此刮灰用的刮子要以塑料、铜、不锈钢等材质较好，最好用牛角刮子。2.面漆：上面漆应用纯棉质纱线，不能用化纤或含化纤的丝线。  \n\n(6）实用工艺六藤制家具常用透明涂装工艺：白坯干燥-白坯前处理-染色-封闭-打磨上面漆，见表3-7-125。  \n\n表3-7-125 藤制家具常用透明涂装工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">施工条件</td><td colspan=\"4\">底材：藤质基材 涂料：PU、NC 施工温度25℃，湿度75%以下</td></tr><tr><td>序号</td><td>工序</td><td>材料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>1</td><td>白坯干燥</td><td>烘干设备</td><td>日光或烘干</td><td>藤条清洁干净后经日晒或烘烤干燥</td></tr><tr><td>2</td><td>白坯前处理</td><td>硫磺、漂白水</td><td>烟熏、浸泡</td><td>硫黄烟熏主要防虫蛀；对色质及质量差的藤皮、芯还 须进行漂白处理；防霉、防裂处理，并除去青皮；经过高 温杀菌消毒处理后，再用机器把藤条拉成一定长短和 粗细规格的藤</td></tr><tr><td>3</td><td>染色</td><td>酸性染料或油溶性染料</td><td>喷涂</td><td>用酸性染料或油溶性染料涂装1～2遍，染色均匀一 致，颜色要淡雅</td></tr><tr><td>4</td><td>封闭</td><td>PU封闭底漆</td><td>喷涂</td><td>对底材进行封闭，漆要尽可能调稀一些，可视需要多 做一遍封闭</td></tr><tr><td>5</td><td>打磨</td><td>砂纸</td><td>手磨</td><td>轻磨、消除木毛</td></tr><tr><td>6</td><td>上面漆</td><td>清面漆</td><td>喷涂</td><td>均匀喷涂施工，涂料要尽可能调稀一些，可视需要多 做一两遍面漆</td></tr></table></body></html>\n\n注；1.藤条在干燥前必须进行清洗干净；藤条材料比较容易长虫、生霉，故必须用硫黄、漂白水等处理。2.藤材颜色一般不太均匀，故染色是藤家具涂装非常重要的一道工序，染色时颜色不能太深，要求染后颜色均匀一致。3.藤家具上漆时要注意，涂料要尽可能调稀一些，宁愿薄涂多遍。4.藤家具也来用浸涂工艺，但所用涂料及工艺过程有不同。  \n\n(7）实用工艺七中纤板木门实色常用涂装工艺：白坏-打磨-封闭-打磨-底漆-打磨-底漆-打磨-面漆，见表3-7-126。  \n\n表3-7-126 中纤板木门实色常用涂装工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">施工条件</td><td colspan=\"3\">底材：中纤板 涂料：PU、NC或UPE 施工温度25℃，湿度75%以下</td></tr><tr><td>序号</td><td>工序</td><td>材 料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>1</td><td>白坯打磨</td><td>砂纸</td><td>手磨、机磨</td><td>去污迹、白坯打磨平整，增加附着力</td></tr><tr><td>2</td><td>刮腻子</td><td>各类腻子</td><td>刮涂</td><td>打磨时木眼里的腻子填实，外边的腻子均要 磨干净</td></tr><tr><td>3</td><td>封闭</td><td>PU封闭底漆</td><td>刷涂、喷涂</td><td>对底材进行封闭，可视需要多做一遍封闭，待 干3~4h</td></tr><tr><td>4</td><td>打磨</td><td>砂纸</td><td>手磨、机磨</td><td>打磨均匀</td></tr><tr><td>5</td><td>底漆</td><td>专用PU、UPE、NC木门实色底漆喷涂、刷涂</td><td></td><td>均匀施工，待干3～4h</td></tr><tr><td>6</td><td>打磨</td><td>砂纸</td><td>手磨、机磨</td><td>打磨均匀、平整</td></tr><tr><td>7</td><td>底漆</td><td>专用PU、UPE、NC木门实色底漆</td><td>喷涂、刷涂</td><td>均匀施工，层间待干5～8h</td></tr><tr><td>8</td><td>打磨</td><td>砂纸</td><td>手磨、机磨</td><td>打磨均匀、平整</td></tr><tr><td>9</td><td>面漆</td><td>专用PU、NC木门实色面漆</td><td>喷涂</td><td>按标准配比，均匀喷涂</td></tr></table></body></html>\n\n注：1.白坯打磨：去污迹、打磨要平整以增加附着力。2.封闭：木门涂装时，封闭工序不能省，必要时多做 $1\\sim2$ 遍底漆。3.打磨：层间打磨非常重要，否则会影响漆膜附着力。4.底漆、面漆：底面漆建议使用厂家的木门专用底面漆。  \n\n(8）实用工艺八实木门全封闭透明涂装常用工艺：白坏打磨-封闭-打磨-刮腻子-打磨底漆-打磨-底漆-打磨-面漆-打磨-面漆，见表3-7-127。  \n\n表3-7-127 实木门全封闭透明涂装常用工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">底材：实木 施工条件</td><td colspan=\"3\">涂料：PU、NC或UPE 施工温度25℃，湿度75%以下</td></tr><tr><td>序号</td><td>工序</td><td>材料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>1</td><td>白坯打磨</td><td>砂纸</td><td>手磨、机磨</td><td>去污迹、白坯打磨平整</td></tr><tr><td>2</td><td>封闭</td><td>PU封闭底漆</td><td>刷涂、喷涂、擦涂</td><td>对底材进行封闭，3～4h后可打磨</td></tr><tr><td>3</td><td>打磨</td><td>砂纸</td><td>手磨</td><td>轻磨、消除木毛</td></tr><tr><td>4</td><td>刮腻子</td><td>PU透明腻子</td><td>刮涂</td><td>填平木眼，3h后可打磨</td></tr><tr><td>5</td><td>打磨</td><td>砂纸</td><td>手磨、机磨</td><td>彻底打磨平整，多余腻子清除干净</td></tr><tr><td>6</td><td>底漆</td><td>专用PU、UPE、NC木门透明底漆</td><td>喷涂、可湿碰湿</td><td>均匀喷涂，5～8h后可打磨</td></tr><tr><td>7</td><td>打磨</td><td>砂纸</td><td>手磨、机磨</td><td>彻底打磨平整</td></tr><tr><td>8</td><td>底漆</td><td>专用PU、UPE、NC木门透明底漆</td><td>喷涂、可湿碰湿</td><td>均匀喷涂，5～8h打磨</td></tr><tr><td>9</td><td>打磨</td><td>砂纸</td><td>手磨、机磨</td><td>彻底打磨平整</td></tr><tr><td>10</td><td>面漆</td><td>专用PU、UPE、NC木门透明面漆</td><td>喷涂</td><td>均匀喷涂，8～10h后轻磨</td></tr><tr><td>11</td><td>打磨</td><td>砂纸</td><td>手磨</td><td>轻磨颗粒，切忌打穿</td></tr><tr><td>12</td><td>面漆</td><td>专用PU、UPE、NC木门透明面漆</td><td>喷涂</td><td>均匀喷涂</td></tr></table></body></html>  \n\n(9）实用工艺九中纤板橱柜实色涂装工艺：白坯打磨封闭-打磨-刮腻子-打磨-底漆-打磨-底漆-打磨-面漆-抛光，见表3-7-128。  \n\n表3-7-128 中纤板橱柜实色常用涂装工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">施工条件</td><td colspan=\"3\">底材：三聚氰氨贴面中纤板(单面白色) 涂料：PU、UPE、PE、NC</td></tr><tr><td>序号</td><td>工序</td><td>施工温度25℃，湿度75%以下 材料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>1</td><td>白坯处理</td><td>砂纸</td><td>手工或机磨</td><td>中纤板面打磨平整、增加附着力</td></tr><tr><td>2</td><td>封闭</td><td>PU封闭底漆</td><td>刷、喷</td><td>整个面板进行封闭，可视需要多做一遍封闭</td></tr><tr><td>3</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>打磨均匀、平整</td></tr><tr><td>4</td><td>刮腻子</td><td>原子灰</td><td>刮涂</td><td>中纤板面满刮腻子</td></tr><tr><td>5</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>打磨均匀、平整</td></tr><tr><td>6</td><td>底漆</td><td>用PU、UPE、NC橱柜实色底漆</td><td>喷、刷涂</td><td>均匀施工</td></tr><tr><td></td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>打磨均匀、平整</td></tr><tr><td>8</td><td>底漆</td><td>用PU、UPE、NC橱柜实色底漆</td><td>喷、刷涂</td><td>均匀施工</td></tr><tr><td>9</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>打磨均匀、平整</td></tr><tr><td>10</td><td>面漆</td><td>用PU、NC橱柜实色面漆</td><td>喷涂</td><td>按标准配比，均匀喷涂</td></tr><tr><td>11</td><td>抛光</td><td>抛光蜡</td><td>手工或机械</td><td>完全干透后，选取合适抛光蜡进行抛光</td></tr></table></body></html>\n\n注：1.木门属比较特殊的木制品，涂饰面全部是见光面，所以，尽量做到防止木门的变形和开裂，拆封的半成品应在第一时间内做完封闭底漆，防止基材吸收空气中的水分变形。2.底漆：尽量使用UPE透明底漆，对木门的形变稳定有很大帮助。  \n注：1.腻子：腻子应选用原子灰，以保证良好的附着力，刮涂时应薄刮，填孔即可。2.附着力：这种工艺如用划格法测试底、面漆之间的附着力，结果不会有问题，但实际生产中常采用刀片挑的方法来测试，对于附着力的要求更高，为此常常在面漆与UPE底漆之间做一层PU亚光清面漆过渡层，来提高层间附着力。3.面漆抛光时间的选择：传统的面漆要经过 $48h$ 于燥才能抛光；面漆经过常温干燥3h，再 $50^{\\circ}C$ 干燥12h也可以直接抛光。4.第一遍面漆与第二遍面漆的湿碰湿时间为 $\\mathbf{1},\\mathsf{5}\\cdots\\mathsf{2h}$ ，如间隔时间过短，则碰第二遍面漆时易产生橘皮现象。  \n\n(10）实用工艺十实木或中纤板贴木皮PU底NC面底着色全封闭透明涂装工艺：实木或中纤板贴木皮-封闭-打磨-底着色-封闭-打磨-底漆-打磨-底漆-打磨-修色-打磨-清面漆（亮光或亚光)，见表3-7-129。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 608,
+        "chunk": "# 表3-7-129实木或中纤板贴木皮PU底NC面底著色全封闭涂装工艺  \n\n<html><body><table><tr><td colspan=\"2\">施工条件</td><td colspan=\"3\">底材：实木、中纤板贴木皮 涂料：封闭底漆、透明底漆、调色金油、清面漆 施工温度25℃、湿度75%以下</td></tr><tr><td>序号</td><td>工序</td><td>材 料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>1</td><td>白坯处理</td><td>砂纸</td><td>手工或机磨</td><td>去胶印、污渍、毛刺，打磨平整</td></tr><tr><td>2</td><td>封闭</td><td>PU封闭底漆</td><td>刷、喷</td><td>去毛刺，平衡底着色均匀度，3～4h后 打磨</td></tr><tr><td>3</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>去毛刺、打磨平整</td></tr><tr><td>3</td><td>着底色</td><td>P有色士那、木纹宝(填充剂)、</td><td>擦涂</td><td>干套稀释剂调整到合适施工浓度，擦涂，</td></tr><tr><td>4</td><td>封闭</td><td>PU封闭底漆（可选择）</td><td>喷涂</td><td>保护底色，增加附着力，3～4h后打磨</td></tr><tr><td>3</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>打磨平整</td></tr><tr><td>5</td><td>底漆</td><td>PU或UPE透明底漆</td><td>喷、淋涂</td><td>按标准配比调漆施工</td></tr><tr><td>5</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>打磨均匀、平整，切勿磨穿</td></tr><tr><td>6</td><td>底漆</td><td>PU或UPE透明底漆</td><td>喷涂、淋涂</td><td>按标准配比调漆施工</td></tr><tr><td>5</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>打磨均匀、平整，切勿磨穿</td></tr><tr><td>7</td><td>修色</td><td>调色金油加油性色精或PU 透明面漆加油性色精</td><td>喷涂</td><td>按标准配比调漆施工</td></tr><tr><td>5</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>干后轻磨，切勿磨穿</td></tr><tr><td>8</td><td>清面漆</td><td>NC清面漆</td><td>喷涂</td><td>按标准配比调到12s施工黏度喷涂</td></tr></table></body></html>  \n\n(11）实用工艺十一中纤板贴木皮全PU透明面着色涂装工艺：中纤板（贴木皮)-封闭-打磨-底漆-打磨-底漆-打磨-修色-打磨-清面漆（亮光或亚光)，见表3-7-130。  \n\n表3-7-130中纤板贴木皮透明面着色涂装工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">施工条件</td><td colspan=\"4\">底材：中纤贴木皮 涂料：封闭底漆、透明底漆、调色基料、清面漆 施工温湿度25℃，75%以下</td></tr><tr><td>序号</td><td>工序</td><td>材 料</td><td>施工方法</td><td>施工要点</td><td></td></tr><tr><td>1</td><td>白坯处理</td><td>砂纸</td><td>手磨机磨</td><td>去污渍、毛刺，打磨平整</td><td></td></tr><tr><td>2</td><td>封闭</td><td>PU封闭底漆</td><td>刷、喷</td><td></td><td>对底材有效封闭，3～4h后打磨</td></tr><tr><td>3</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>去毛刺、打磨平整</td><td></td></tr><tr><td>4</td><td>底漆</td><td>PU透明底漆</td><td>喷涂、淋涂</td><td></td><td>按标准比例调配，喷涂均匀</td></tr></table></body></html>\n\n注：1.白坏处理：要平整光洁。2.封闭底漆：帮助底着色均匀着色，增加层间附着力。3.底着色：先按照顺时针或逆时针圈擦，然后顺木纹擦拭干净。4.封闭底漆：可视需要选择。5.底漆：按标准配比施工。如要做全封闭效果，底漆可湿碰湿喷涂两遍。干后打磨，切勿磨穿。6.修色：可用调色金油加油性色精调色，也可用PU清面漆加油性色精调色，黏度要适宜，最好调到 $9\\approx105$ 进行修色施工。7.清面漆：NC亮光或亚光清面漆，按标准配比调到合适施工黏度（通常为12s)，均匀喷涂。  \n\n续表  \n\n\n<html><body><table><tr><td>序号</td><td>工序</td><td>材料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>5</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>打磨均匀、平整，切勿磨穿</td></tr><tr><td>6</td><td>底漆</td><td>PU透明底漆</td><td>喷涂</td><td>按标准比例调配，湿碰湿喷涂两遍</td></tr><tr><td>7</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>打磨均匀、平整，切勿磨穿</td></tr><tr><td>8</td><td>修色</td><td>PU清面漆调油性色精调色</td><td>喷涂</td><td>按标准比例调配，根据颜色要求调色</td></tr><tr><td>9</td><td>打磨</td><td>砂纸</td><td>手工</td><td>轻轻打磨，切勿磨穿</td></tr><tr><td>10</td><td>清面漆</td><td>PU清面漆</td><td>喷涂</td><td>按标准配比调到合适施工黏度(通常为12s)，均匀喷涂</td></tr></table></body></html>\n\n注：1.贴木皮：中密度纤维板贴各种木皮，注意选择合适木皮黏结剂。2.贴木皮主要工序：裁剪板料-砂光（最好是定厚砂光）-挑选木皮-裁皮-缝皮-调胶-涂胶-贴皮-热压。然后铣边-封边-排孔-拉槽-木制砂光，再转给涂装车间进行涂装。  \n\n3.白坏处理：要平整光洁。  \n\n，封闭底漆：有利于除去毛刺，封闭基材，增加层间附着力，干后要打磨。  \n\n5.底漆一遍：PU透明底漆，按标准配比施工，不宜厚喷，干后打磨，切勿磨穿。  \n\n6.底漆二遍：PU透明底漆，按标准配比施工，可湿碰湿喷涂两遍，干后打磨，切勿磨穿  \n\n7.修色：调色金油加油性色精调色，也可以用PU清面漆加油性色精调色，黏度要合适，最好调到 $9\\sim105$ 进行喷值施工。  \n\n8.清面漆：PU亮光或亚光清面漆，按标准配比调节合适施工黏度（通常为12s），均匀喷涂。  \n\n(12）实用工艺十二实木地板透明底着色全封闭涂装工艺：实木地板-做底色（水性)-封闭(可选择)-打磨-PU单组分或双组分地板漆 (亮光或亚光)-打磨-PU单组分或双组分地板漆（亮光或亚光)，见表3-7-131。  \n\n表3-7-131 实木地板透明底着色全封闭涂装工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">施工条件</td><td colspan=\"3\">底材：实木地板 涂料：着色剂、封闭底漆、PU地板漆 施工温湿度25℃，75%以下</td></tr><tr><td>序号</td><td>工序</td><td>材 料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>1</td><td>白坯处理</td><td>砂纸</td><td>手工或机磨</td><td>去污渍、毛刺，打磨平整</td></tr><tr><td>2</td><td>做底色</td><td>水性着色剂</td><td>刷涂、喷涂</td><td>着色均匀，颜色主要是浸润进人到木材表层里</td></tr><tr><td>3</td><td>封闭</td><td>PU封闭底漆</td><td>刷涂、喷涂</td><td>对底材、底色进行有效封闭和保护，增加附着 力，3～4h后可轻磨</td></tr><tr><td>4</td><td>打磨</td><td>砂纸</td><td>手工</td><td>轻轻打磨，切勿磨穿露白</td></tr><tr><td>5</td><td>面漆</td><td>PU(单组分或双组分)地板漆</td><td>刷涂、喷涂</td><td>按标准配比调到合适施工黏度（通常为12s)， 刷、喷均匀到位</td></tr><tr><td>6</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>均匀打磨</td></tr><tr><td>7</td><td>面漆</td><td>PU（单组分或双组分）地板漆</td><td>刷涂、喷涂</td><td>按标准配比调到合适施工黏度（通常为12s)， 刷、喷均匀到位</td></tr></table></body></html>\n\n注：1.白坯处理：砂光时注意到位，顺纹砂光，不可漏砂。2.着底色：按照需要选择水性着色材料，可采用刷涂、辊涂、喷涂、浸涂等施工方式，颜色要相对均匀。  \n\n3.封闭底漆：有效封闭基材、底色，增加层间附着力，  \n\n4.地板漆：单组分潮固化PU地板漆，双组分PU地板漆，按标准配比调到合适施工黏度（通常为12s)，刷、喷均匀到位。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 609,
+        "chunk": "# （13）实用美术漆涂装工艺  \n\n$\\textcircled{1}$ 中纤板闪光漆涂装工艺中纤板-封闭-打磨-刮腻子-打磨-实色底漆-打磨-闪光漆-清面漆（亮光或亚光），见表3-7-132。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 610,
+        "chunk": "# 表3-7-132 中纤板闪光漆涂装工艺  \n\n<html><body><table><tr><td colspan=\"2\">施工条件</td><td colspan=\"3\">底材：中纤板 涂料：封闭底漆、实色底漆、闪光漆、清面漆 施工温湿度25℃，75%以下</td></tr><tr><td>序号</td><td>工序</td><td>材料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>1</td><td>白坯处理</td><td>砂纸</td><td>手工或机磨</td><td>去污渍、毛刺，打磨平整</td></tr><tr><td>2</td><td>封闭</td><td>PU封闭底漆</td><td>刷涂、喷涂</td><td>对底材有效封闭，3～4h后打磨</td></tr><tr><td>3</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>去毛刺、打磨平整</td></tr><tr><td>4</td><td>刮腻子</td><td>PU或UPE腻子</td><td>刮涂</td><td>填平截面、钉眼、导管</td></tr><tr><td>5</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>去毛刺，腻子干透再打磨平整，木径上面要打磨 干净</td></tr><tr><td>6</td><td>实色底漆</td><td>PU或UPE实色底漆</td><td>喷涂</td><td>按标准比例调配，喷涂均匀</td></tr><tr><td>7</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>打磨均匀、平整，切勿磨穿</td></tr><tr><td>8</td><td>闪光漆</td><td>PU闪光漆</td><td>喷涂</td><td>按标准比例调配，漆膜表干后喷清面漆</td></tr><tr><td>9</td><td>清面漆</td><td>PU清面漆</td><td>喷涂</td><td>按标准配比调到合适黏度（通常为12s）施工，待 闪光漆表干后，再喷涂清面漆</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 中纤板裂纹漆涂装工艺中纤板-封闭-打磨-刮腻子-打磨-实色底漆-打磨-透明底漆-裂纹漆-透明面漆（亮光或亚光)，见表3-7-133。  \n\n表3-7-133 中纤板裂纹漆涂装工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">施工条件</td><td colspan=\"3\">底材：实木、中纤 油漆：封闭底漆、实色底漆、清底漆、裂纹漆、清面漆； 施工温湿度25℃、75%以下</td></tr><tr><td>序号</td><td>工序</td><td>材 料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>1</td><td>白坯处理</td><td>砂纸</td><td>手工或机磨</td><td>去污渍、毛刺，打磨平整</td></tr><tr><td>2</td><td>封闭</td><td>PU封闭底漆</td><td>刷涂、喷涂</td><td>对底材有效封闭，增加附着力</td></tr><tr><td>3</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>去毛刺、打磨平整</td></tr><tr><td>4</td><td>刮腻子</td><td>PU或UPE腻子（可选择）</td><td>手工</td><td>填平截面、钉眼</td></tr><tr><td>5</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>去毛刺，腻子干透再打磨平整，木径上面要打 磨干净</td></tr><tr><td>6</td><td>实色底漆</td><td>PU或UPE实色底漆</td><td>喷涂</td><td>按标准配比施工，喷涂均匀</td></tr><tr><td>7</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>打磨均匀、平整，切勿磨穿</td></tr><tr><td>8</td><td>透明底漆</td><td>NC清底漆</td><td>喷涂</td><td>调整到合适的施工黏度喷涂，漆膜厚度越均 匀越好，干后不要打磨</td></tr></table></body></html>\n\n注：1.白坏处理：要平整光洁，棱角圆滑。2.封闭底漆：有利于除毛刺，有效封闭基材，增加层间附着力。3.刮腻子：主要是满刮填平截面及木材导管，干后打磨平整。4.实色底漆：PU或UPE实色底漆，根据面漆颜色效果配套选用实色底漆，按标准配比施工，干后打磨光滑，切勿磨穿。5.闪光漆：PU闪光漆，按标准比例调配施工，表干后喷涂清面漆，注意在喷涂清面漆之前不能打磨。6.清面漆：PU亮光或亚光清面漆，按标准配比调到合适黏度（通常是12s）进行施工，待闪光漆表干后均匀喷涂，浅色效果最好选用耐黄变清面漆。  \n\n续表  \n\n<html><body><table><tr><td>序号</td><td>工序</td><td>材料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>9</td><td>裂纹漆</td><td>NC裂纹漆</td><td>喷涂</td><td>调整到合适的施工黏度喷涂，漆膜厚薄越均 匀越好，干后不要打磨</td></tr><tr><td>10</td><td>透明面漆</td><td>NC清面漆(亮光或亚光)</td><td>喷涂</td><td>调整到合适的施工黏度（通常为12s黏度）进 行喷涂施工</td></tr></table></body></html>\n\n注：1．白坯处理：要平整光洁。  \n\n2.封闭底漆：有利于除去毛刺，有效封闭基材。  \n\n3.刮腻子（可选择）：主要是填充截面的较大缺陷。  \n\n4.实色底漆：PU或UPE实色底漆，可根据效果需要选择配套的实色底漆颜色，按标准配比施工，干后打磨，切勿磨穿。  \n\n5.清底漆：NC清底漆是裂纹漆的基础漆，漆膜厚薄越均匀越好，干后不要打磨。  \n\n6.裂纹漆：NC实色裂纹漆，调整到合适的施工黏度喷涂，漆膜厚薄越均匀越好，干后不要打磨；裂纹显现时间大约为 $3\\cdots5\\operatorname*{min}$ ，一般来说，如想获得粗或深的裂纹，可适当增加漆膜厚度，或提高裂纹底漆的厚度；反之如想获得细或浅的裂纹，则要降低漆膜厚度，或控制裂纹底漆的厚度。  \n\n7.清面漆；NC亮光或亚光清面漆，调整到合适黏度（通常为 $\\mathrm{12s)}$ 进行喷涂施工，白色效果最好选用耐黄变清面漆。  \n\n$\\textcircled{3}$ 中纤板锤纹漆涂装工艺中纤板-封闭-打磨-刮腻子-打磨-PU或UPE实色底漆-打磨锤纹漆-清面漆（亮光或亚光)，见表3-7-134。  \n\n表3-7-134中纤板锤纹漆涂装工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">施工条件</td><td colspan=\"3\">底材：中纤板 涂料：封闭底漆、实色底漆、锤纹漆、清面漆 施工温湿度25℃，75%以下</td></tr><tr><td>序号</td><td>工序</td><td>材料及配比</td><td>施工方法</td><td>施工要点</td></tr><tr><td>1</td><td>白坯处理</td><td>砂纸</td><td>手工或机磨</td><td>去污渍、毛刺，棱角打磨圆滑</td></tr><tr><td>2</td><td>封闭</td><td>PU封闭底漆</td><td>刷涂、喷涂</td><td>对底材有效封闭，增加附着力</td></tr><tr><td>3</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>去毛刺、打磨平整</td></tr><tr><td>4</td><td>刮腻子</td><td>PU或UPE腻子</td><td>手工</td><td>嵌补填平截面、补钉眼</td></tr><tr><td>5</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>去毛刺，腻子干透再打磨平整，木径上面要打磨干净</td></tr><tr><td></td><td>实色底漆</td><td>PU或UPE实色底漆</td><td>喷涂</td><td>按标准配比施工，喷涂均匀</td></tr><tr><td>7</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>打磨均匀、平整，切勿磨穿</td></tr><tr><td>8</td><td>锤纹漆</td><td>NC锤纹漆</td><td>喷涂</td><td>调到适合黏度，喷涂均匀，膜厚一致、锤纹均匀</td></tr><tr><td>9</td><td>清面漆</td><td>NC清面漆</td><td>喷涂</td><td>按标准调到合适黏度(通常为12s)施工，均匀喷涂</td></tr></table></body></html>\n\n注：1.白坯处理：棱角要磨得比较圆润。2.封闭底漆：有效封闭基材底色，增加腻子对基材的附着力。  \n\n3.刮腻子：主要是填充横截面的缺陷。  \n\n4.实色底漆；PU或UPE实色底漆，可根据锤纹漆的色彩配套选择实色底漆的颜色，按标准配比施工，干透后打磨。  \n\n5.锤纹漆：NC锤纹漆，按所需效果要求调整施工黏度。  \n\n6.清面漆：NC清面漆，按标准调到合适黏度（通常为12s）施工，均匀喷涂。  \n\n锤纹漆中有形成锤花的硅油，喷涂过锤纹漆的喷房、喷枪以及喷涂中用过的其他设备、工具、部件的清洗非常关键如有疏忽，在喷涂其他涂料时极易出现“缩孔”。  \n\n$\\textcircled{4}$ 中纤板贝母漆涂装工艺中纤板处理-封闭-打磨-刮腻子-打磨-白色底漆-打磨-贝母漆-清面漆（亮光)，见表3-7-135。  \n\n$\\textcircled{5}$ 中纤板油丝（蜘蛛网）漆涂装工艺中纤板-封闭-打磨-刮腻子-打磨-PU实色底漆-打磨-NC透明底漆-油丝漆-仿古漆-NC清漆（亮光或亚光)，见表3-7-136。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 611,
+        "chunk": "# 表3-7-135 中纤板贝母漆涂装工艺  \n\n<html><body><table><tr><td colspan=\"2\" rowspan=\"2\">施工条件</td><td colspan=\"3\">底材：中纤板 涂料：封闭底漆、实色底漆、贝母漆、清面漆</td></tr><tr><td>施工温湿度25℃，75%以下</td><td>施工方法</td><td></td></tr><tr><td>序号 1</td><td>工序 白坯处理</td><td>材料 砂纸</td><td>手工或机磨</td><td>施工要点 去胶印、污渍、毛刺，打磨平整</td></tr><tr><td>2</td><td>封闭</td><td>PU封闭底漆</td><td>刷涂、喷涂</td><td>对底材封闭，3～4h后打磨</td></tr><tr><td>3</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td></td></tr><tr><td>4</td><td>刮腻子</td><td>PU或UPE腻子</td><td>手工</td><td>去毛刺、打磨平整</td></tr><tr><td>5</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>填平截面、补钉眼，干透后打磨</td></tr><tr><td>6</td><td>白色底漆</td><td>PU或UPE白色底漆</td><td>喷涂</td><td>去木毛，腻子干透再打磨平整，木径上面要打磨干净</td></tr><tr><td>7</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>按标准比例调配，喷涂均匀</td></tr><tr><td>8</td><td>贝母漆</td><td>PU贝母漆</td><td>喷涂</td><td>打磨均匀、平整，切勿磨穿 按标准比例调配，采用先喷后点的施工方法，漆膜厚</td></tr><tr><td>9</td><td>清面漆</td><td>PU清面漆</td><td>喷涂</td><td>度越均匀越好，漆膜表干后，即可喷清面漆 按标准配比调到合适黏度（通常12s）施工，待贝母 漆表干后喷涂</td></tr></table></body></html>  \n\n6.清面漆：PU耐黄变亮光清面漆，按标准配比调到合适黏度（通常12s）施工，待贝母漆表干后喷涂。  \n\n表3-7-136 中纤板油丝（蜘蛛网）漆涂装工艺  \n\n\n<html><body><table><tr><td colspan=\"2\" rowspan=\"2\">施工条件</td><td colspan=\"3\">底材：中纤板 涂料：PU封闭底漆、PU实色底漆、油丝漆、仿古漆、清面漆</td></tr><tr><td>施工温湿度25℃，75%以下 材料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>序号 １</td><td>工序 白坯处理</td><td>砂纸</td><td>手工或机磨</td><td>去胶印、污渍、木毛、木刺，打磨平整</td></tr><tr><td>2</td><td>封闭</td><td>PU封闭底漆</td><td>刷涂、喷涂</td><td>对基材进行封闭，3～4h后打磨</td></tr><tr><td>3</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>去木毛，增加层间附着力</td></tr><tr><td>4</td><td>刮腻子</td><td>PU或UPE腻子</td><td>手工</td><td>嵌补填平基材、补钉眼</td></tr><tr><td>5</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>去木毛，腻子干透再打磨平整，木径上面要打磨干净</td></tr><tr><td>6</td><td>PU实色底漆</td><td>PU或UPE实色底漆</td><td>喷涂</td><td>按标准配比调配，喷涂均匀</td></tr><tr><td>7</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>打磨干整，切勿磨穿</td></tr><tr><td>8</td><td>NC透明底漆</td><td>NC清底漆</td><td>喷涂</td><td>均匀到位</td></tr><tr><td>9</td><td>油丝漆</td><td>NC实色或透明漆</td><td>喷涂</td><td>调节合适黏度、施工气压，关闭喷枪风围进行施工</td></tr><tr><td>10</td><td>仿古漆</td><td>NC格丽斯</td><td>手工擦涂</td><td>调整合适黏度，用干刷做效果</td></tr><tr><td>11</td><td>NC清面漆</td><td>NC清面漆(亮光或亚光)</td><td>喷涂</td><td>调整到12s黏度喷涂</td></tr></table></body></html>\n\n注：1.白坯处理：要平整光洁。2.封闭底漆：有利于除去木毛刺，有效封闭基材，增加附着力。3.刮腻子：主要是填充截面的较大缺陷。4.白色底漆：PU或UPE白色底漆，一般多数选用白色，按标准配比施工，干后打磨，切勿磨穿。5.贝母漆：PU贝母漆，按标准比例调配，采用先喷后点的施工方法，首先按常规喷涂方法喷涂，漆膜厚度越均！越好，接着调整合适的气压、出漆量，喷涂成均匀的“点”状，漆膜会自然形成七彩的贝壳效果，表干后喷涂清面漆。主意：在喷涂清面漆之前不能打磨。  \n注：1.白坯处理：要平整光洁。2.封闭底漆：有利于除去木毛刺，有效保护基材。3.刮腻子：主要是填充截面的较大缺陷。4.实色底漆：PU或UPE实色底漆，可根据效果需要选择配套的实色底漆颜色，按标准配比施工，干后打磨不要磨穿。5.做透明底漆：NC清底漆，为于刷效果起架桥作用。6.油丝漆：普通的NC清、实色面漆，调整到合适的施工黏度、喷涂施工气压，关闭喷枪风围喷涂成蜘蛛网丝状效果。7.清面漆：NC亮光或亚光清面漆，按标准配比调到合适黏度（通常为 $125$ ）施工，白色效果选用耐黄变清面漆。  \n\n③中纤板仿木纹涂装工艺基材-封闭-打磨-刮腻子-打磨-木纹底漆-打磨-木纹底漆-打磨-木纹漆-清底漆-打磨-清面漆（亮光或亚光)，见表3-7-137。  \n\n表3-7-137 中纤板仿木纹涂装工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">施工条件</td><td colspan=\"4\">底材：中纤板 涂料：封闭底漆、实色底漆、木纹漆、透明底漆、清面漆 施工温湿度25℃，75%以下</td></tr><tr><td>序号</td><td>工序</td><td>材料</td><td>施工方法</td><td>施工要点</td><td></td></tr><tr><td>1</td><td>白坯处理</td><td>砂纸</td><td>手工或机磨</td><td>去胶印、污渍、毛刺，打磨平整</td><td></td></tr><tr><td>2</td><td>封闭</td><td>PU封闭底漆</td><td>刷涂、喷涂</td><td>对底材有效封闭，3～4h后打磨</td><td></td></tr><tr><td>3</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>去毛刺、打磨平整</td><td></td></tr><tr><td>4</td><td>刮腻子</td><td>PU或UPE 腻子</td><td>刮涂</td><td></td><td>按标准配比调灰，填平截面、补钉眼</td></tr><tr><td>5</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td></td><td>去毛刺，腻子干透再打磨平整，木径上面要打磨干净</td></tr><tr><td>6</td><td>木纹底漆</td><td>PU或UPE实色底漆</td><td>喷涂、淋涂</td><td></td><td>按要求选择底漆颜色，按标准配比调漆施工</td></tr><tr><td></td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>打磨均匀、平整，切勿磨穿</td><td></td></tr><tr><td>00</td><td>木纹底漆</td><td>PU或UPE实色底漆</td><td>喷涂、淋涂</td><td></td><td>按要求选择底漆颜色，按标准配比调漆施工</td></tr><tr><td>g</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>打磨均匀、平整，切勿蘑穿</td><td></td></tr><tr><td>10</td><td>木纹漆</td><td>PU拉纹漆</td><td>手工、机械</td><td></td><td>按要求拉纹、刷纹、印刷木纹。干后涂透明底漆</td></tr><tr><td>11</td><td>底漆</td><td>PU透明底漆</td><td>喷涂、淋涂</td><td>按标准配比调漆施工</td><td></td></tr><tr><td>12</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>打磨均匀、平整，切勿磨穿</td><td></td></tr><tr><td>13</td><td>清面漆</td><td>PU清面漆</td><td>喷涂</td><td></td><td>按标准配比调到合适施工黏度喷涂(通常为12s)</td></tr></table></body></html>\n\n注：1.白坯处理：要平整光洁。2.封闭底漆：有利于除去木毛刺，有效封闭基材，增加层间附着力。3.刮腻子：按标准配比调腻子，主要是填好截面的较大缺陷。4.木纹底漆：PU或UPE色底漆，按要求选择底漆颜色，按标准配比调漆施工。  \n\n$\\textcircled{7}$ 实木火烧工艺实木-实木火烧-打磨-封闭底漆-打磨-底漆-打磨-面漆，见表3-7-138。  \n\n表3-7-138 实木火烧工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">施工条件</td><td colspan=\"3\">底材：各类木材 涂料：封闭底漆、PU漆 施工温湿度25℃，75%以下</td></tr><tr><td>序号</td><td>工序</td><td>材料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>1</td><td>白坯处理</td><td>砂纸</td><td>喷灯</td><td>用喷灯进行火烧，将表面木孔烧深，达到火烧的原始效果</td></tr><tr><td>2</td><td>打磨</td><td>砂纸</td><td>手磨</td><td>磨掉较厚的碳素，让木材表面留较自然的火烧痕</td></tr><tr><td>3</td><td>封闭</td><td>PU封闭底漆</td><td>刷、喷</td><td>对底材的碳渍有效封闭，3～4h后打磨</td></tr><tr><td>4</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>将表面浮尘磨平滑</td></tr><tr><td>５</td><td>底漆</td><td>PU透明底漆</td><td>刷、喷(湿碰湿)</td><td>按涂料厂要求调配并施工，湿碰湿第一遍要薄喷，底漆施工 后要待干8～10h打磨</td></tr><tr><td>6</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>顺木纹凹凸面进行打磨，切勿磨穿</td></tr><tr><td>7</td><td>面漆</td><td>PU清面漆</td><td>喷涂</td><td>按标准配比调到合适施工黏度喷涂(通常为12s)</td></tr></table></body></html>\n\n注：1.进行实木火烧工艺时，一般要在专用区域进行，注意防火安全，2.根据效果要求来控制火烧程度，火烧后如有较厚的炭层必须打掉。3.涂料层间打磨时切勿磨穿。  \n\n③静电喷涂工艺静电喷涂在木家具的制造上应用日益增多，主要是针对异形件的涂装（表3-7-139)。利用家具厂原有吊线生产线的条件，只需改造喷涂设备，就可极大地提高产能与效率。木制品工件进行静电涂装工艺时，一是要让工件接地，并作为正极，不能让涂料雾化设备作为正极，以免导致安全事故；二是要控制木材的含水率在 $8\\%\\sim12\\%$ ，使工件能作为导体而实施静电涂装。正负两极间的电流值一般控制为 $20\\sim50\\mu\\mathrm{A}$ 。当木材含水率偏低时，可使木材通过水蒸气来提高木材含水率，或在静电涂装之前，用手喷枪先将被涂工件喷水 $1\\sim2$ 次。  \n\n表3-7-139 木制品静电喷涂工艺  \n\n\n<html><body><table><tr><td colspan=\"2\">施工条件</td><td colspan=\"3\">底材：各类木材 涂料：NC透明底漆、NC清面漆 施工温湿度25℃，75%以下</td></tr><tr><td>序号</td><td>工序</td><td>材料</td><td>施工方法</td><td>施工要点</td></tr><tr><td>１</td><td>白坯处理</td><td>砂纸</td><td>手磨或机磨</td><td>可用240目或320目砂纸打磨</td></tr><tr><td>2</td><td>底漆</td><td>NC透明底漆</td><td>静电喷涂</td><td>控制合适黏度，充分干燥再打磨</td></tr><tr><td>3</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>均匀打磨，选用合适砂纸</td></tr><tr><td>4</td><td>底漆</td><td>NC透明底漆</td><td>静电喷涂</td><td>控制合适黏度，充分干燥再打磨</td></tr><tr><td>5</td><td>打磨</td><td>砂纸</td><td>手工或机磨</td><td>均匀打磨，选用合适砂纸</td></tr><tr><td></td><td>面漆</td><td>NC清面漆</td><td>静电喷涂</td><td></td></tr></table></body></html>\n\n注：1.静电喷涂一般用于异形件的涂装。2.保证工件的均匀导电，必要时可先对工件薄薄地喷一遍导电稀释剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 612,
+        "chunk": "# （14）实用美式涂装工艺流程  \n\n$\\textcircled{1}$ 美式涂装概述200年前的美国人，当他们举家西迁时，原本的家具在无路可行的葬葬荒原上磕磕碰碰，斑痕累累。这些见证了美国西部大开发的旧家具，在今天就成了美国人的古董家具，现今美国人拥有一件祖母用过的旧家具，一定要放在居室最醒目的位置，从而显示注重文化和历史的象征。仿造早期美国这些古旧家具叫做美式家具，它的涂装方式业界统称为美式涂装。美式家具的涂装以单一色为主，表面涂装的涂料也多为暗淡的亚光，希望家具显得越旧越好。以仿古为特点的美式家具，表现出了富足的美国人对历史的怀旧以及追求浪漫生活的情结。  \n\n从风格上看，美式家具可分为三大类：一是仿古风格，造型典雅，但不过度装饰，是美式家具的典型代表作；二是新古典风格，自由粗犷，以舒适实用和多功能为主，营造返朴归真的境界；三是乡村风格，摒弃奢华，回归乡村，体现日出而作、日落而息的宁静与闲适。",
+        "category": " Introduction"
+    },
+    {
+        "id": 613,
+        "chunk": "# $\\textcircled{2}$ 美式涂装工艺流程  \n\na.常见美式涂装效果工艺 见表3-7-140。  \n\n表3-7-140 常见美式涂装效果工艺  \n\n\n<html><body><table><tr><td>施工条件</td><td colspan=\"5\">基材：樱桃木、橡木、松木、桦木、木、水曲柳等实木底材 温湿度：温度25C，湿度75%</td></tr><tr><td>序号</td><td>工序名称</td><td>材料</td><td>施工方式</td><td>摘要</td><td>干燥时间</td></tr><tr><td>1</td><td>白坯打磨</td><td>砂纸</td><td>机磨、手磨</td><td>去污迹、白坯打磨平整</td><td></td></tr><tr><td>2</td><td>破坏处理</td><td></td><td>人工</td><td>虫孔、敲打、锂边等，用240\"砂纸打磨</td><td></td></tr><tr><td>3</td><td>底色调整</td><td>红水、绿水</td><td>喷涂</td><td>局部喷涂</td><td>5min</td></tr><tr><td>4</td><td>不起毛着色剂</td><td>调色</td><td>喷涂</td><td>均匀喷涂，中湿</td><td>5min</td></tr></table></body></html>  \n\n<html><body><table><tr><td>序号</td><td>工序名称</td><td>材料</td><td>施工方式</td><td>摘要</td><td>干燥时间</td></tr><tr><td>5</td><td>杜洛斯着色剂</td><td>调色</td><td>喷涂</td><td>均匀喷涂，重湿</td><td>20min</td></tr><tr><td>6</td><td>封固底漆</td><td>底漆十天那水，</td><td>喷涂</td><td>均匀喷涂，根据底材及需要的着色效果 调整喷涂黏度</td><td>30min</td></tr><tr><td>7</td><td>打磨</td><td>砂纸</td><td>人工</td><td>轻磨，注意不要砂穿</td><td></td></tr><tr><td>8</td><td>NC格丽斯</td><td>格丽斯调色</td><td>擦拭</td><td>擦中等干净，毛刷整理并用0000钢丝 绒抓明暗</td><td>1~2h</td></tr><tr><td>9</td><td>NC透明底漆</td><td>底漆十天那水</td><td>喷涂</td><td>14～16s底漆，均匀喷涂</td><td>1~2h</td></tr><tr><td>10</td><td>打磨</td><td>砂纸</td><td>人工</td><td>打磨平整</td><td></td></tr><tr><td>11</td><td>刷金粉</td><td>金粉漆的金粉</td><td>毛刷</td><td>刷在雕刻处</td><td>10min</td></tr><tr><td>12</td><td>乙烯基类透明底漆</td><td></td><td>喷涂</td><td>16s，只喷涂于刷金部位</td><td>30min</td></tr><tr><td>13</td><td>NC透明底漆</td><td>底漆十天那水</td><td>喷涂</td><td>14～16s底漆，均匀喷涂</td><td>1~2h</td></tr><tr><td>14</td><td>打磨</td><td>砂纸</td><td>人工</td><td>打磨平整</td><td></td></tr><tr><td>15</td><td>打干刷</td><td>格丽斯调色</td><td>毛刷</td><td>做效果</td><td>30min</td></tr><tr><td>16</td><td>NC透明底漆</td><td>底漆十天那水</td><td>喷涂</td><td>14～16s底漆，均匀喷涂</td><td>1~2h</td></tr><tr><td>17</td><td>打磨</td><td>砂纸</td><td>人工</td><td>打磨平整</td><td></td></tr><tr><td>18</td><td>布印</td><td>调色</td><td>人工</td><td>棉布全面拍打并用0000#钢丝绒整理</td><td>10min</td></tr><tr><td>19</td><td>马尾</td><td>格丽斯调色</td><td>人工</td><td></td><td>10min</td></tr><tr><td>20</td><td>喷点</td><td>天那水+调色剂</td><td>喷涂</td><td></td><td>10min</td></tr><tr><td>21</td><td>NC透明面漆</td><td>底漆十天那水</td><td>喷涂</td><td>12～14s,喷涂均匀</td><td>1~2h</td></tr><tr><td>22</td><td>灰尘漆</td><td>灰尘漆</td><td>喷涂</td><td>除破坏与沟槽处留适量外，其余的擦拭 干净</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 614,
+        "chunk": "# b.中纤板仿古白美式涂装效果工艺 见表3-7-141。  \n\n续表  \n表3-7-141 中纤板仿古白美式涂装效果工艺  \n\n\n<html><body><table><tr><td rowspan=\"2\">施工条件</td><td colspan=\"5\">基材：中纤板</td></tr><tr><td>温度25℃，湿度75%</td><td>材料</td><td>施工方式</td><td>摘要</td><td>干燥时间</td></tr><tr><td>序号 １</td><td>工序名称 白坯打磨</td><td>砂纸</td><td>机磨、手磨</td><td>去污迹、白坯打磨平整</td><td></td></tr><tr><td>2</td><td>破坏处理</td><td></td><td>人工</td><td>虫孔、敲打、链边等，用240*砂纸打磨</td><td></td></tr><tr><td>3</td><td>NC白底漆</td><td>底漆十天那水</td><td>喷涂</td><td>14～16s,喷涂均匀</td><td>1~2h</td></tr><tr><td>4</td><td>打磨</td><td>砂纸</td><td>人工</td><td>打磨平整</td><td></td></tr><tr><td>5</td><td>NC白底漆</td><td>底漆十天那水</td><td>喷涂</td><td>12～14s,均匀喷涂</td><td>1~2h</td></tr><tr><td>6</td><td>裂纹漆</td><td>裂纹漆十天那水</td><td>喷涂</td><td>局部不规则喷涂</td><td>30min</td></tr><tr><td>7</td><td>打磨</td><td>砂纸</td><td>人工</td><td>对裂纹漆处打磨</td><td></td></tr><tr><td>8</td><td>NC透明底漆</td><td>底漆</td><td>喷涂</td><td>10～12s，先喷涂裂纹漆处，后全面均</td><td>1h</td></tr><tr><td>9</td><td>NC格丽斯</td><td>格丽斯调色</td><td></td><td>匀喷湿</td><td></td></tr><tr><td>10</td><td>乙烯基类透明底漆</td><td></td><td>擦拭</td><td>擦中等干净，毛刷整理</td><td>1~2h</td></tr><tr><td>11</td><td>打磨</td><td>乙烯基类底漆</td><td>喷涂</td><td>16s，全部均匀喷湿</td><td>30min</td></tr><tr><td>12</td><td>刷金粉</td><td>砂纸 金粉漆十金粉</td><td>人工 毛刷</td><td>打磨平整 刷在雕刻处</td><td>10min</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>序号</td><td>工序名称</td><td>材料</td><td>施工方式</td><td>摘要</td><td>干燥时间</td></tr><tr><td>13</td><td>乙烯基类透明底漆</td><td>乙烯基类底漆</td><td>喷涂</td><td>16s，只喷涂于刷金部位</td><td>30min</td></tr><tr><td>14</td><td>打磨</td><td>砂纸</td><td>人工</td><td>打磨平整</td><td></td></tr><tr><td>15</td><td>布印</td><td>调色剂</td><td>人工</td><td>棉布全部拍打并抓明暗</td><td>10min</td></tr><tr><td>16</td><td>打干刷</td><td>格丽斯调色</td><td>毛刷</td><td></td><td>30min</td></tr><tr><td>17</td><td>NC透明面漆</td><td>底漆十天那水</td><td>喷涂</td><td>14s,均匀喷涂</td><td>1~2h</td></tr><tr><td>18</td><td>喷点</td><td>调色</td><td>喷涂</td><td></td><td>10min</td></tr><tr><td>19</td><td>NC透明面漆</td><td>面漆十天那水</td><td>喷涂</td><td>12～14s,喷涂均匀</td><td>1~2h</td></tr><tr><td>20</td><td>灰尘漆</td><td>灰尘漆</td><td>喷涂</td><td>除破坏与沟槽处留适量外，其余的擦 拭干净</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 615,
+        "chunk": "# c.新美仿古涂装工艺 见表3-7-142。  \n\n表3-7-142 新美仿古涂装工艺   \n\n\n<html><body><table><tr><td>施工条件 温度25℃，湿度75%</td><td colspan=\"5\">基材：中纤板贴木皮、实木</td></tr><tr><td>序号</td><td>工序名称</td><td>材料</td><td>施工方式</td><td>摘要</td><td>干燥时间</td></tr><tr><td>1</td><td>白坯打磨</td><td>砂纸</td><td>机磨、手磨</td><td>去污迹、白坯打磨平整</td><td></td></tr><tr><td>2</td><td>杜洛斯着色剂</td><td>调色</td><td>喷涂</td><td>参照色板一次性喷湿，亦可采用NGR (不起毛着色剂)着色</td><td>20min</td></tr><tr><td>3</td><td>NC透明底漆</td><td>底漆十天那水</td><td>喷涂</td><td>均匀喷涂，根据底材及需要的着色效 果调整喷涂黏度</td><td>30min</td></tr><tr><td>4</td><td>打磨</td><td>砂纸</td><td>人工</td><td>轻磨，注意不要砂穿</td><td></td></tr><tr><td>5</td><td>NC格丽斯</td><td>格丽斯十稀释剂</td><td>擦拭</td><td>擦中等干净，毛剧整理并用0000\"钢 丝绒抓明暗</td><td>1~2h</td></tr><tr><td>6</td><td>NC透明底漆</td><td>底漆十天那水</td><td>喷涂</td><td>14～16s底漆，均匀喷涂</td><td>1~2h</td></tr><tr><td>7</td><td>打磨</td><td>砂纸</td><td>人工</td><td>打磨平整</td><td></td></tr><tr><td>8</td><td>打干刷、刷边</td><td>格丽斯十稀释剂</td><td>毛刷、人工</td><td>轻干刷效果，突出明暗对比，0000钢 丝绒整理，简单轻微刷边</td><td>30min</td></tr><tr><td>9</td><td>NC透明底漆</td><td>底漆十天那水</td><td>喷涂</td><td>14～16s底漆，均匀喷涂</td><td>1~2h</td></tr><tr><td>10</td><td>打磨</td><td>砂纸</td><td>人工</td><td>打磨平整</td><td></td></tr><tr><td>11</td><td>布印</td><td>调色</td><td>人工</td><td>棉布全面拍打并用0000#钢丝绒整理</td><td>10min</td></tr><tr><td>12</td><td>马尾</td><td>格丽斯调色</td><td>人工</td><td></td><td>10min</td></tr><tr><td>13</td><td>喷点</td><td>天那水十调色剂</td><td>喷涂</td><td></td><td>10min</td></tr><tr><td>14</td><td>NC透明面漆</td><td>底漆十天那水</td><td>喷涂</td><td>13～14s,喷涂均匀</td><td>1~2h</td></tr><tr><td>15</td><td>打磨</td><td>砂纸</td><td>人工</td><td>打磨平整</td><td></td></tr><tr><td>16</td><td>NC透明面漆</td><td>底漆十天那水</td><td>喷涂</td><td>12～13s,喷涂均匀</td><td>1~2h</td></tr></table></body></html>  \n\n$\\textcircled{3}$ 美式涂装主要工序本文提到的很多材料名称，施工的技术名词，都是遵循家具行业内多年的习惯用法，多源于台湾家具界。  \n\na.破坏处理（physicaldistress）破坏主要是模仿产品在长期使用或存放过程中出现的风蚀、风化、虫蛀、碰损以及人为破坏等留下的痕迹，是美式涂装中增加工件仿古效果的一道重要的加工工序。  \n\n常见的破坏处理包括用锉刀在产品边缘锂出锉刀痕；用钉子或螺丝钉钉在木制把手上，敲打木材表面形成类似虫蛀小孔的效果；用铁丝串好的螺丝串、螺帽、螺杆、铁锤、锉刀柄等工具对木材表面进行敲打或划伤；用雕刻刀做出挖槽、虫线等效果；对工件的角、棱等凸起的地方进行倒角、倒边，模仿风蚀、风化或被人经常触摸留下的光滑无棱的效果。  \n\n进行破坏处理时要注意尽量避开产品有疤节或较为坚硬的地方；尽量避开产品的拼接处；大破坏要首先考虑产品有缺陷的地方；要注意顺木纹方向；破坏效果要自然、协调、逼真。  \n\nb.素材调整（blending of substrates）在家具的制作过程中，经常会将不同颜色或不同树种的木材搭配于同一家具中，造成了家具自身素材的颜色差异。而通过涂装工艺把素材的不同颜色调整为相对统一的颜色的过程就叫做素材调整。  \n\n绿水（equalizer）是用于素材调整的一种浅绿色或黄绿色的修色剂，如喷涂于红色木材部分，使木材显现出棕色或淡灰白的中性颜色。红水（sap stain）是用于素材调整的一种浅红色或红棕色的修色剂，如喷涂于白色、浅白色、青色或黑色木材部分，使木材显现出浅红或红棕色。  \n\n进行素材调整要注意红、绿水可以根据底材颜色要求进行局部喷涂或局部加重喷涂；以较大面积的底色为准，调整小面积的颜色至接近。  \n\nc.底材着色有三种材料可选用：不起毛着色剂（NGRstain），用各色染料加到不起毛着色剂、稀释剂里调配而成，多为酒精性质，常用于美式涂装的底层色喷涂。其性能特点是不膨胀木毛，可渗人木材表层、内部而显现出非常好的透明度。使用不起毛着色剂时要注意：一是大面喷涂要均匀；二是通常喷涂方式可分为轻湿、中湿和重湿，喷湿程度的不同对色彩渗透程度和最后的颜色效果有一定影响；三是注意不要喷得太湿，以免产生底色开花现象。  \n\n杜洛斯底色（Duro stain)，是由杜洛斯主剂加入染料或颜料调配而成，是一种较为常用的底色漆，可以单独对底材进行底着色，喷涂施工，也可以和不起毛着色剂相结合，用于不起毛着色剂之后喷涂。其性能特点是，染料型杜洛斯颜色渗透性强，透明度高，能更好地展现木材纹理。颜料型杜洛斯具有柔和的透明底色格调，可掩饰一些木材颜色差异的变化，涂装效果较朦胧。使用时要注意均匀喷涂；通常喷涂方式可分为轻湿、中湿和重湿等，喷湿程度的不同以及杜洛斯主剂的干速，对色彩渗透程度和最后的颜色效果有一定影响；注意不要喷得太湿，以免产生底色开花现象；颜料型杜洛斯底色使用前注意均匀搅拌；如需要，喷涂前可加人少量的NC漆调配，以便于对色。  \n\n渗透性着色剂（penetratingstain）是用渗透性溶剂加人专用色浆和少量仿古漆颜料色浆而成，可以单独对底材进行底着色用，也可以和不起毛着色剂相结合，用于不起毛着色剂之后的喷涂。其性能特点是可使木材导管突显金黄色或青棕色，让导管颜色更为突出；主要用于加深木材纹理的清晰性，增加层次，常用于深木眼底材。使用时，要注意全面均匀喷涂；通常喷涂方式可分为轻湿、中湿和重湿等，喷湿程度的不同对色彩渗透程度和最后的颜色效果有一定影响；注意不要喷得太湿，以免产生底色开花现象；注意不可以用于底漆或有色底漆之上，否则会导致附着力不良；使用前注意搅拌均匀。  \n\nd.封固底漆（washcoat）封固底漆又叫头度底漆、洗涤底漆，施工现场常常采用NC透明底漆与天那水按一定的比例稀释、调配而成，黏度通常在 ${\\mathfrak{g}}{\\sim}{\\bf1}{\\bar{z}}{\\bf s}$ 。其作用一是起到“封固”作用，保护底色；二是用封闭程度来控制仿古漆的残留量。  \n\n使用时，要注意均匀喷涂，要让底材充分湿润；采用黏度较低的胶固底漆可以得到较脏的仿古漆颜色效果；采用黏度较高的胶固底漆得到的仿古漆颜色效果则显得干净；使用的胶固底漆黏度太高时，会阻碍仿古漆渗人木材导管，致使颜色看起来较呆板、无层次感。  \n\ne.擦NC格丽斯（glaze）格丽斯又叫仿古漆，是一种半透明的颜料着色剂，通常作为美式涂装的中层色。其性能特点：一是本身具半透明性，增强漆膜颜色的层次感；二是具有强烈的仿古效果，使家具更具古典韵味；三是易于施工，可擦涂、刷涂、喷涂、打毛刷、抓明暗；四是可用来制作其他各种仿古效果，如假木纹、牛尾、刷边等。  \n\n使用时，要注意格丽斯擦涂之后不要抹得太干净，通常会根据需要而残留一部分，并可以通过抓明暗、打干刷等方法以加强色彩的明暗、层次对比和仿古效果；格丽斯通常用于胶固底漆之后，一般不直接用于白坏，以免产生附着力和着色不匀的不良现象；但格丽斯也不宜残留过多，并且应要完全干燥后才能上喷底漆，以避免产生发白或附着力不良现象；为避免家具木材端头吸人过量格丽斯而发黑，可在擦拭格丽斯前先擦涂透明格丽斯或刷涂一遍NC透明底漆；各种格丽斯成品色可满足绝大多数色彩需要，格丽斯色浆主要用于颜色微调。  \n\nf.抓明暗（hili）抓明暗是“层次”的意思，是在产品着色过程中用钢丝绒（通常用型$0000^{\\pm}$ ）按一定的规律抓出一些颜色较浅的部分，使产品颜色呈现出明暗对比的层次感。  \n\n注意抓明暗通常在格丽斯或布印之后；针对颜色浅或木纹间隙大的地方并顺木纹方向抓；抓明暗时要做到“两头轻中间重”；不能穿越拼接线；抓明暗可以用毛刷进行整理，使抓明暗边缘更加柔和。  \n\ng.刷金、刷银刷金、刷银指的是通过小毛刷把调配好的金粉漆或银粉漆刷涂于家具雕花、饰条等部位，以突出艺术修饰，使之更具有价值和引人注目。金、银粉各有多种不同的色相及粗细规格，注意金银粉的粗细、色调的准确；刷金、刷银后需要在刷金、刷银部位喷涂一遍乙烯基树脂类透明底漆以保证附着力；用乙烯基树脂类透明底漆调配的金、银粉漆刷涂后不易擦掉。  \n\nh.打于刷（drybrush）打干刷指的是通过毛刷用格丽斯在家具产品表面的边缘、拐角处或雕花处做出阴影、刷边等特有的效果，以加强产品的层次、艺术感、强化仿古效果。  \n\n打干刷时，要注意格丽斯黏度要调整适当；毛刷上不要一次性黏附太多的格丽斯；干刷部位要求颜色过渡自然；刷边多在家具的破坏、突起、边缘等地方，并且呈一定的倾斜方向。  \n\ni.牛尾（cowtail）牛尾主要模仿马或牛的尾巴扫过家具后留下的痕迹，以加强产品的仿古效果和艺术性。常见的“抹油马尾”是用小毛刷或钢丝绒绳蘸上适量格丽斯通过“刷”或“甩”出来。  \n\n牛尾操作是要注意工具大小、长短要适用；格丽斯色彩深浅适中；避开产品有疤节的地方；牛尾的长短、粗细要自然。  \n\nj.布印修色（padding stain）布印属于美式涂装中的面层色，通常用布印稀释剂调配酒精性色精，通过棉布拍打、擦拭或喷涂而达到加深产品的颜色、增强产品的层次感及仿古效果。  \n\n注意，布印可以通过棉布拍打、擦拭达到局部着色的效果，也可以通过喷枪喷涂达到全面着色的效果；喷枪喷涂布印只适合较浅的上色，色深了会影响到产品的色彩层次感；布印棉布拍打后需要用 $0000^{\\sharp}$ 钢丝绒整理，便之色彩过渡自然；喷枪喷涂布印后可以通过 $0000^{\\sharp}$ 钢丝绒把抓明暗重新整理出来。  \n\nk.喷点（spatter）喷点通常是一种深色着色剂，多为黑色、深咖啡色，用来模仿“苍蝇”的痕迹，以增强产品的仿古效果。酒精点多为布印点，特点是较大的点中间色浅，四周色深；天那水点多为面漆加色浆或染料加天那水调配而成，特点是喷上工件后干了不易擦  \n\n掉，所以喷这一类的点需要很小心。  \n\n喷点时要注意喷枪的调节：需用上壶枪，枪摆幅度合适、气量最小、油量根据点的大小调节；注意点的大小、颜色、疏密控制，注意点的变形。  \n\n1.灰尘漆（dustywax）灰尘漆也叫发霉漆，通常用于产品的沟槽、破坏等处，以模仿产品使用时间久远，沟槽里聚积灰尘或发霉的效果。  \n\n灰尘漆可局部、全部，刷涂或喷涂，并要将多余的部分擦干净；灰尘漆喷涂或刷涂时，前一遍面漆一定要确保干透，否则灰尘漆会无法擦干净；涂布灰尘漆后可上涂面漆，也可不上涂面漆，两者效果各异；灰尘漆上涂面漆后色相会有所变化；灰尘漆后一般不要修色或多次喷漆，否则会影响到仿古效果。  \n\nm.裂纹漆在美式涂装中，通常会通过使用局部的、不规则的裂纹漆效果来模仿产品在经过漫长的时间或风化日蚀所产生的自然裂纹。  \n\n注意裂纹的大小可以通过裂纹漆喷涂的厚度来调整；为了增强仿古效果，通常需要对裂纹漆进行部分磨穿，并通过后期的格丽斯加深颜色对比。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 616,
+        "chunk": "# 第六节木用涂装常见问题的现象、原因及处理  \n\n影响木用涂料涂装质量的因素很多，包括涂料本身品质、基本特点、工艺配套、涂装环境、涂装设备、涂装技术、现场管理等，下面分别加以讨论。",
+        "category": " Introduction"
+    },
+    {
+        "id": 617,
+        "chunk": "# 一、涂料涂装前常见漆病的预防及处理",
+        "category": " Introduction"
+    },
+    {
+        "id": 618,
+        "chunk": "# 1.黏度  \n\n涂装前对涂料的黏度调整是非常重要的，过高会造成湿膜太厚，干后涂膜起皱、流平不好、起泡，过低会造成涂膜流挂。在遵守厂家提供的调配比标准外，还应根据冬夏室温变化进行调整，最好每次调完漆后，对已调稀的漆进行黏度测试，这样才可保证每次喷涂黏度的统一。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 619,
+        "chunk": "# 2.适用期  \n\n指反应型涂料的可使用时间。掌握好涂料的可使用时间是非常重要的，调配好的涂料，一定要在适用期内用完，否则不能使用或胶化报废。平时涂装前，首先了解已选用涂料的最佳适用期，然后知道自己在适用期这段时间内能用掉多少涂料，最后才决定每次配多少涂料，特别是UPE涂料适用期非常短，而且UPE涂料干燥后，在器具上附着很好，很难清洗。配漆的原则是少量多次。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 620,
+        "chunk": "# 3.返粗  \n\n已分散好了的含有颜料、填料涂料放置一段时间后，内含的颜料、填料又重新聚集，致使喷涂后涂膜有许许多多颗粒在表面，返粗一般是涂料自身的问题、涂料厂家生产工艺不好或使用不合格的原材料所致。在涂装过程中，发现返粗的现象，立即停止操作，检查涂料的细度。情况不严重的，待已涂装的涂膜干后，用粗号砂纸打磨至光滑即可。但要注意，不要凡在涂膜表面发现粗粒，就立即断言“返粗”。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 621,
+        "chunk": "# 4.结块  \n\n涂料中结块现象，一般是因为涂料已发生了部分反应、涂料中使用大量不合格粉质、超  \n\n过贮存期、生产过程出问题而形成的。开罐检查、涂装时发现涂料有结块现象就应立即停止操作。找出原因及解决办法后再决定是否继续使用，可用手动或机械对已结块涂料进行搅拌，如块状物被打散、分散均匀，经过滤、检测、试喷均合格的，才可正式使用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 622,
+        "chunk": "# 5.沉淀  \n\n沉淀一般是由于放置时间太长或涂料体系中各物质密度不一样所致，产生原因是原料选择、生产过程出问题，超过贮存期的产品更易产生此问题。一般来说，除清漆外，任何涂料都会出现沉淀现象，只是好涂料和差涂料在沉淀程度和发生时间不一样而已。沉底通常有两种现象：一是软沉淀，软沉淀根据厂家在包装桶上的提示，使用前正确搅拌均匀就可；二是硬沉淀，硬沉淀很难搅起或根本搅不起，硬沉底涂料有点类似结块，不要用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 623,
+        "chunk": "# 6.分层  \n\n分层一般也有几种现象：一种就是沉淀，粉质全沉底，上面是树脂和溶剂，此时和解决沉淀方法一样经搅拌、过滤、试喷，能用的才用；另一种是实色涂料内各色分层，此时也是由于各色颜料密度不一样所致，差别越大，越易分层。一般来说通过较好的搅拌，就可再用。有时调配好的备用漆低黏度时也容易分层，所以每次使用前先要把涂料搅拌均匀，不然会涂装出各种缺陷的涂膜来。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 624,
+        "chunk": "# 7.浮色  \n\n涂装前的涂料浮色一般是由于各色颜料粒子分散状态有差异，密度相差较大所致，密度很小的颜料粉或染料直接浮在涂料上面，此现象通过认真搅拌一般都可解决。但浮色严重时在干膜上也会有反映，谨慎使用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 625,
+        "chunk": "# 8.清漆色泽  \n\n一般来说，对清漆而言，不更换原材料和改变制造工艺，不同批次产品在外观色泽上即使出现差异，也不会太明显。当批次间色差明显时，会影响到漆膜颜色，尤其是在浅色贴纸涂装工艺时，影响较大。导致不同批次产品色差，通常是涂料制造过程中树脂色泽不同、生产过程不洁、包装物不洁所致，因此必须严格控制涂料的制造工艺。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 626,
+        "chunk": "# 9.清漆浑浊  \n\n涂料开罐后或调配后，外观有时会呈现出浑浊或不清透的现象。如果是产品开罐时外观浑浊，主要从涂料本身去找原因，注意产品贮存条件或包装罐等是否存在异常；如果产品主剂正常，发生浑浊是在涂料调配后，则多从辅助材料或施工工具、施工环境上去寻找原因。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 627,
+        "chunk": "# 二、涂料涂装过程中常见漆病的预防及处理  \n\n家具厂在涂装生产过程中，常常面对各种漆病，极大地影响家具生产效率、导致不合格率高，返工量大。",
+        "category": " Introduction"
+    },
+    {
+        "id": 628,
+        "chunk": "# 1.漆膜泛白 (或发白)  \n\n(1）异常现象涂料在干燥过程中或干燥后漆膜呈现出乳白色或木纹、底材底色不清晰的现象，严重时甚至会无光、发浑。  \n\n(2）产生原因在高温高湿环境下施工；涂料或稀料中含有水分；施工中油水分离器出现故障，水分带人涂料中；格丽斯未干；手汗沾污工件或水磨后工件未干；一次性过分厚涂；基材含水率过高；打磨后放置时间过长，水分吸附在漆膜表面；含粉量偏高的底漆厚涂于深色板材上等。  \n\n(3）预防或处理措施尽量避免在高温高湿环境下施工；控制基材含水率，必须充分干燥后才能进行涂装；涂料或稀料在贮藏和涂装施工过程中要避免带人水分；定期检查并清除油水分离器中的水分；格丽斯未干不进行下一阶段涂装；热天施工时要防止操作员手汗沾污工件；如水磨后，则要等工件完全干透后再行涂装；尽量避免一次性厚涂；层间打磨后放置时间不应太长，以免水分吸附在漆膜表面，应尽快进行下一工序的喷涂；含粉量高的底漆避免厚涂于深色板材上等。  \n\n喷涂后发现泛白（或发白)，可加入防发白水，用一定量的防发白水代替原用稀释剂，比例从少到多，少量解决问题，就不用多量，防发白水的极限用量是原稀释剂的 $25\\%$ 。正确方法是调漆前先把防发白水与稀释剂按需要量调配，搅匀，再加入到涂料中。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 629,
+        "chunk": "# 2.起泡或针孔  \n\n（1）异常现象是涂层在施工过程中漆膜表面呈现圆形的凸起形变，一般产生于被涂面与漆膜之间，或两层漆膜之间；气泡是一种在涂膜中存在的细胞状的病态，若涂料在涂装过程和涂膜干燥过程中气泡破裂但又不能最终流平，则形成针孔；针孔是一种在涂膜中存在类似于用针刺成的细孔的病态。  \n\n(2）产生原因木材含水率高；没有封闭或封闭不好；木眼过深；油性或水性腻子未完全干燥或底层涂料未干时就涂饰面层涂料；稀释剂选用不合理，挥发太快；涂料中带人水分；一次涂装过厚；施工黏度偏高；固化剂添加量过多；施工温度过高，表干过快；对流强烈，造成表干过快；喷枪操作不当。  \n\n（3）预防或处理措施控制木材的含水率小于 $12\\%$ ；尽量多地使用封闭底漆，对于深木眼板材更要进行封闭；应在腻子、底层涂料充分干燥后，再施工面层涂料；添加慢干水，调整挥发速率；严格避免涂料带人水分；薄涂多遍，尤其是底漆和亮光面漆；适量调低施工黏度；按比例添加固化剂；避免在 $35\\mathrm{{^\\circC}}$ 以上施工，如不可避免，则可加人适量慢干水；改造喷房通风环境；加强喷涂人员操作培训等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 630,
+        "chunk": "# 3.缩孔或跑油  \n\n(1）异常现象漆膜流平干燥后存在的若干大小不等、不规则分布的圆形小坑（火山口）的现象。  \n\n(2）产生原因涂层表面被油、蜡、手汗等污染；有油水被空气带入涂料中；环境被污染；涂料本身被污染；喷涂的压缩空气含油或水；被涂物面过于光滑；双组分涂料有时配调不均，也会出现收缩现象；涂料不配套。  \n\n(3）预防或处理措施避免涂层表面被油、蜡、手汗等物污染；处理好油水分离器，放掉空压机内的水；切断污染源；更换涂料；定期清理油水分离器；表面进行打磨预处理；配漆后充分调匀静止后，再进行涂装；涂料配套要合原则等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 631,
+        "chunk": "# 4.咬底  \n\n(1）异常现象漆膜在干燥过程中或干燥后出现上层涂料溶胀下层涂料，使下层涂料脱 离底层产生凸起、变形甚至剥落的现象。  \n\n(2）产生原因上下层涂料不配套；下层涂料一次喷涂太厚；下层未干透就施工上层涂料；上层涂料中含太多强溶剂；涂膜表面被污染。  \n\n(3）预防或处理措施要根据涂装需要选好合适的涂料品种，并注意上下层涂料配套性能；下层涂料不能一次性喷涂太厚，以免底层干燥时间过长或不干；下层涂料要充分干燥，才能进行下步涂装工艺；一般上层涂料的稀释剂中，强溶剂不能过多，以免造成对下层漆膜  \n\n的损伤；漆膜表面有污染物应清除干净后再施工等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 632,
+        "chunk": "# 5.慢干或不干  \n\n（1）异常现象涂料施工后干燥速率异常，出现慢干或不干。  \n\n(2）产生原因PU漆固化剂未加或加量不够；施工时温度太低或湿度太高；处理发白时，防发白水添加过量；板材有油污或油脂含量高；涂料不配套；一次性喷涂太厚；层间间隔时间太短；面漆表干太快，面干底不干。  \n\n(3）预防或处理措施按配比添加固化剂；提高室内施工温度或延长干燥时间；防发白水的添加量要合适；当板材油污或油脂含量较高时，用溶剂清洗后再用封闭底漆进行封闭处理；涂料要配套使用；涂装时不能一次性喷涂太厚，并保证足够的层间干燥时间；调整好面漆的干燥时间，避免面干底不干等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 633,
+        "chunk": "# 6.颗粒  \n\n（1）异常现象干膜表面颗粒较多，颗粒形同痱子般的凸起，手感粗糙、不光滑。  \n\n(2）产生原因涂料本身有粗粒；涂料未经过滤即使用；调油后放置太久；涂料稀释剂溶解力差，涂料施工黏度太高；施工工具不洁；打磨时灰尘处理不干净；除尘系统不好，作业环境较差；喷枪气量、油量未调好。  \n\n(3）预防或处理措施选用合格的涂料产品；调好的涂料使用前必须经过过滤后才用，且控制调漆量，以免放置时间过长；稀释剂溶解力度及加入量要合适；施工工具必须清洁干净，并保持好喷房环境卫生；打磨工序要注意除尘，保证除尘系统的效果，正确操作喷枪。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 634,
+        "chunk": "# 7.失光  \n\n(1）异常现象失光是指有光漆在固化成漆膜后没有光泽，或光泽不好，不均匀的现象。  \n\n(2）产生原因高温高湿天气容易引起失光；喷涂气压太大，油量太小；施工黏度太低，稀释剂添加太多；稀释剂挥发速率太快，导致失光；配错固化剂；亚光漆未搅拌均匀即行涂刷；涂膜太薄，流平不好。  \n\n(3）预防或处理措施加入适量慢干水，控制涂布量，恶劣天气停止施工；控制好喷涂气压、油量；减少稀释剂的添加量；选用慢干稀释剂或添加慢干水；配套使用固化剂；亚光漆配漆前要搅拌均匀；保证漆膜厚度足够等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 635,
+        "chunk": "# 8.流挂  \n\n（1）异常现象涂料施涂于垂直面上时，由于其抗流挂性差而使湿漆膜向下移动，表面出现下滴、下垂、漆膜不平的现象。  \n\n(2）产生原因被涂物表面过于光滑；涂料施工黏度低；一次性喷涂涂层过厚；喷涂距离太近，喷枪移动速度太慢；凹凸不平或物体的棱角、转角、线角的凹槽处，容易造成涂刷不均厚薄不一，较厚处就要流淌；施工环境温度过低，漆膜于得慢；物体基层表面有油、水等污物与涂料不相容，影响粘接，造成漆膜下垂；涂料中含重质颜料过多，部分涂料下垂。  \n\n(3）预防或处理措施施工黏度保持正常；严禁一次性厚涂；调整施工环境温度；物体表面应处理平整、光洁，清除表面油、水等污物；选择合适涂料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 636,
+        "chunk": "# 9.橘皮  \n\n(1）异常现象涂膜表面呈现出许多半圆形突起，形似橘皮状斑纹。(2）产生原因稀释水加人过多；每次喷漆太多太厚，重喷时间不当；施工环境温度过  \n\n高或过低；物面不平、不洁、基材形状复杂及含有油水；施工操作不当。  \n\n(3）预防或处理措施按比例加稀释剂；如需较厚涂膜应多次薄喷，每次间隔以表干为宜，每道涂膜不宜过厚；环境温度过高或过低时不宜施工；处理好喷涂表面，不得有水和油；正确施工等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 637,
+        "chunk": "# 10.色分离  \n\n(1）异常现象色漆施工后漆膜出现色泽不均匀、深浅不一或不规则之现象。  \n\n(2）产生原因下层色漆未干透即涂上层漆；稀释剂溶解力不够；施工前揽拌不充分；涂料颜料选择不当或分散不良；漆料本身质量劣。  \n\n(3）预防或处理措施提升操作技能；控制漆膜厚度，下层充分干透后再涂上层漆；选用合格稀释剂；施工前充分搅拌；选用质量优良之涂料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 638,
+        "chunk": "# 11.起皱  \n\n（1）异常现象在施工面漆或面漆干燥时，漆膜表面收缩，形成皱纹现象。  \n\n(2）产生原因涂料干速过快，涂膜干燥不均匀；一次性厚涂，表里干燥不一致；施工环境温度过高；底漆未干透即施工面漆；固化剂使用不当或异常；底层漆打磨不均匀。  \n\n(3）预防或处理措施调整涂料施工干速；控制涂膜均匀一致；控制好环境的温度；底层漆充分干燥后再涂面漆；选择正确固化剂；底层漆打磨均匀。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 639,
+        "chunk": "# 12.干膜砂痕重  \n\n（1）异常现象涂装完成后，能清晰地看到底层漆打磨过的砂痕或基材着色打磨过的砂痕痕迹。  \n\n(2）产生原因基材被逆向打磨；砂纸太粗；底层漆未完全干透就打磨；涂料干速过慢；面漆涂膜太薄；打磨后未清洁干净，影响上层漆之润湿。  \n\n(3）预防或处理措施基材打磨时一定要顺木纹方向打磨；先用合适砂纸，选用粗砂纸打磨，再换细砂纸；正确使用封闭漆，底层漆必须完全干透再打磨，并除去漆粉灰尘；选用干速正常的施工涂料；如底层漆膜不够，可再加一遍底漆；面漆要足够厚；定期检查并更换打磨砂纸。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 640,
+        "chunk": "# 13.发汗  \n\n(1）异常现象漆膜表面析出漆基的一种或多种液态组分的现象，渗出液呈油状且发黏称为发汗或渗出。  \n\n(2）产生原因素材表面处理不好，基材含蜡、矿物油、其他油类；涂膜未干就涂装下一道或进行打磨；漆膜有经加热强制干燥，但通风不良。  \n\n(3）预防或处理措施喷涂前要处理好素材表面；涂料颜基比要合适，树脂含量较少的涂料，漆膜避免放在潮湿与气温高的环境；涂膜干透后再涂装下一道或进行打磨；加热强制干燥时，同时要通风好。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 641,
+        "chunk": "# 14.起霜  \n\n（1）异常现象涂膜表面呈现许多冷霜状或烟雾状细小颗粒的现象，称为起霜或起雾，一般是在喷涂后 $1{\\sim}2$ 天或数周后，整个或局部的漆膜上罩上一层类似梅子成熟时的雾状的细颗粒，常在清漆中出现。  \n\n(2）产生原因喷涂时湿度大、风大，环境中有污染性气体，而潮气是主要原因；往往抗水的漆膜会把大气中吸收的水分积聚在表面形成起雾。其他原因还有喷涂时室温变化太  \n\n大；固化剂加人太多；用快干溶剂太多；涂料本身问题。  \n\n(3）预防或处理措施避免喷涂时在湿度大、风大等环境中进行，喷涂后也要注意防潮、防烟、防煤气等；要注意保持室温恒定；固化剂不要加得过多；用相对慢十的溶剂等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 642,
+        "chunk": "# 三、涂料涂装之后常见漆病的预防及处理  \n\n涂料在涂装之后，常出现的一些漆病如下。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 643,
+        "chunk": "# 1.黄变  \n\n(1）异常现象涂膜干燥后，经过一定时间（有时时间很短）会出现变黄的现象，尤以透明本色漆做在浅色板材和白色漆之上最为明显，有均匀黄变，也有斑状黄变。  \n\n(2）产生原因涂料本身不耐黄变；耐黄变涂料错配不耐黄变固化剂；板材被漂白处理过，残留表面的氧化物导致漆膜迅速黄变；阳光直射或存放在高温下，漆膜黄变加快。  \n\n(3）预防或处理措施根据涂装需要选用耐黄变涂料并保证配套使用耐黄变固化剂；经过漂白处理的板材要清洗干净，干燥并进行封闭处理，再进行下道涂装工序；尽量避免阳光直射或存放在高温环境下等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 644,
+        "chunk": "# 2.漆膜下陷  \n\n(1）异常现象 涂料在涂装成型后涂膜逐渐出现凹陷不平整的现象。  \n\n(2）产生原因白坏刮涂腻子时，填充不良或基材含水过高造成；封闭漆未用或未用好；底漆厚度不够；底漆未充分干燥打磨；配漆比例不对，一次喷涂太厚等。  \n\n（3）预防或处理措施基材含水率一定控制在适宜范围才能进行涂装；选用填充性能好的腻子，尤其是深木眼板材；一定要做好基材的封闭；底漆涂膜厚度应足够，必要时可多做一二遍底漆；底漆必须充分干燥；层间干燥时间足够才进行打磨；PU主固要配套且固化剂量要足够等等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 645,
+        "chunk": "# 3.泛白 (后期)  \n\n(1）异常现象涂料施工时未见异常，放置一定时间后，漆膜慢慢由透明转向不透明、浑浊，进而漆膜出现泛白（后期)，这种现象在家装木家具涂装中经常发生。  \n\n(2）产生原因基材含水率偏高；水性腻子未干透就进行下道工序；打磨后被汗手或带污渍的清洁布污染；水磨未干透就进行下道工序；未对基材正反面进行有效封闭；涂料本身配方原因。  \n\n(3）预防或处理措施严格控制基材含水率；水性腻子一定要干透；涂装操作打磨后要用于净布料清洁板面，并戴手套操作，避免被含有油渍、水、蜡或其他的有机物质污染；水磨后要充分干燥；家装木家具涂装时，基材正反面都要做封闭漆，换另外一种涂料做对比试验。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 646,
+        "chunk": "# 4.光泽不均  \n\n（1）异常现象 漆膜表面光泽不均匀，或有亮点。  \n\n(2）产生原因喷涂操作不当，压枪搭接部分过多或偏少；出漆量不平稳，有堵枪现象；高温高湿环境施工；晾干房条件不佳，通风条件差；涂料本身质劣；搅拌不均匀。  \n\n(3）预防或处理措施培训提升操作技能，正确使用喷枪；施工前检查喷涂设备是否正常，进行必要的清洗；控制好施工环境的温湿度；改善喷房或晾干房条件，增加通风设施；选择质量稳定的涂料产品。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 647,
+        "chunk": "# 5.回粘  \n\n(1）异常现象漆膜干燥后，漆膜部分或全部一段时间后发生软化、粘手、不干的现象，打磨粘砂纸，影响下一道工序，不能码堆。  \n\n(2）产生原因涂料慢干，溶剂含量过多，施工后未能充分挥发出来；反应性涂料固化剂量不足；漆膜表面可能受污染；晾干房通风不良；高湿环境施工；底层漆未十透即涂面漆；漆膜厚涂，未干透包装；涂料本身质量问题。  \n\n(3）预防或处理措施控制涂料慢干溶剂的加入量；涂料固化剂按施工比例添加；改善晾干房通风条件；控制施工环境的温度湿度；底层漆干透后才上面漆；严禁一次性厚涂，漆膜必须充分干透再包装；选择合格涂料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 648,
+        "chunk": "# 6.漆膜脱落或附着力不良  \n\n（1）异常现象 漆膜脱落、剥落、起鼓、起皮等病态现象。  \n\n(2）产生原因底、面漆不配套，造成层间附着力欠佳；没有使用封闭底漆，底材过于光滑或不干净；PU漆层间未打磨或打磨不彻底；实色漆刮涂腻子过厚；所用的擦色剂（如木纹宝等）附着力不好；面漆修色停留时间过长；漆膜太薄；一次性喷涂太厚；干燥时间过快。(3）预防或处理措施选择配套的底漆、面漆；底材要打磨至一定的粗糙度，基材用封闭底漆做好封闭；层间打磨至表面毛玻璃状；薄刮腻子，表面打磨彻底，腻子只填木眼，不填木径；选用附着力好的擦色剂，且着色后进行封闭；面漆修色时，间隔时间不要过长；底层要处理好。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 649,
+        "chunk": "# 7.开裂  \n\n（1）异常现象漆膜表面出现深浅大小各不相同的裂纹，如从裂纹处能见到下层表面，则称为“开裂”；如漆膜呈现龟背花纹样的细小裂纹，则称为“龟裂”。  \n\n(2）产生原因漆膜干燥太快；一次性厚涂；固化剂加人过多；底材自身开裂，导致漆膜开裂；腻子刮涂过厚，打磨不彻底；环境不好，昼夜温差过大；涂料本身耐候性差；未经封闭的软木类底材，喷上较稀涂料，漆膜也会发生开裂。  \n\n(3）预防或处理措施固化剂按比例添加并搅拌均匀；先处理底材开裂问题再处理涂料；薄刮腻子，打磨彻底，使腻子只填木眼，不填木径；保持温度平衡，避免温差过大；注意涂料的适用范围，换用合格涂料，做好封闭。  \n\n在家具涂装生产工序中，为了减少涂装事故发生，可重点关注以下工序，如基材含水率控制、基材先封闭、填木眼腻子类产品选择及干透打净、重视打磨/水磨/砂纸型号、要按正确比例配漆、配漆一定要搅拌均匀、配漆后要静止放置 $15\\mathrm{\\sim}20\\mathrm{min}$ 、配漆后要过滤、施工黏度要适当、注意稀释剂（冬夏）选用、注意涂料适用期、控制漆膜厚度、漆膜打磨后控制好重涂间隔时间、未用完涂料盖严、涂膜彻底干透/实干包装等，只要能做到这些，许多常见的漆病就可避免。涂装缺陷的现象及其原因一览见表3-7-143。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 650,
+        "chunk": "# 四、木用涂料涂装管理与涂装难题",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 651,
+        "chunk": "# 1.涂装管理  \n\n针对涂装中存在的各种问题，必须在涂装生产管理中加以克服和解决。  \n\n涂装五要素包括涂装材料、涂装设备、涂装环境、涂装工艺和涂装管理。涂装材料是指涂装生产过程中使用的化工材料及辅料，包括各种涂料产品，如封闭漆、底面漆、固化剂、助剂、蓝水、白水、稀释剂等，以及砂纸、黏合剂、砂布等辅料；涂装设备是指涂装生产过程中使用的设备及工具，包括打磨设备、喷涂设备、洁净吸尘设备、涂装运输设备、试验仪器设备等；涂装环境是指涂装设备内部以外的空间环境，从空间上讲应该包括涂装车间（厂房）内部和涂装车间（厂房）外部的空间；涂装工艺包括工艺方法、工序、工艺过程等；涂装管理包括人员管理、生产（经营）管理、技术及质量管理、设备管理、材料管理、现场管理等。  \n\n1   \n仅一  \n\n\n<html><body><table><tr><td rowspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\">★★★★★***</td><td rowspan=\"2\"></td><td colspan=\"6\"></td><td colspan=\"10\"></td><td colspan=\"6\"></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>工具操作做封干燥涂膜</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td rowspan=\"10\"></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>☆☆</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>浑浊</td><td>★</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td rowspan=\"13\"></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>★★★☆★★★★☆★☆★★★★★★★★☆</td><td>★★★☆★☆★★★★★★☆★★</td><td>★★☆★☆★★★★☆★★</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>★</td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>☆☆—☆一☆</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ATT</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td></table></body></html>  \n\n涂装管理“十条”指的是在涂装生产管理中，着重从功能设计、效果设计、品种选定、施工工艺、操作设备、厂房布置、环保处理、质量检验、人员培训及经济核算十个方面综合去考虑，从而保证在不同的环境条件下，合理地整合涂装资源，并达到既定的涂装目标。",
+        "category": " Introduction"
+    },
+    {
+        "id": 652,
+        "chunk": "# 2.涂装难题  \n\n除了“三分涂料，七分木工”之外，笔者还赞成这句话：“三分涂料，七分涂装”。在木用涂装中，尤其如此。  \n\n由于基材是木制品，木用涂装产生的独特问题很多。木材受本身含水率及外界温、湿度的影响，其几何尺寸对涂装的适应程度都变化很大。在外界条件不好的时候，例如极端气候出现时，尽管采取很多措施，施工环境仍然与当时、当地的恶劣条件相差不大。受温度、湿度、粉尘等的影响，施工难度加大，但对表面装饰性的要求却越来越高。虽然可以低温烘烤，但应用并不广泛，有很多产品由于各种原因无法进行强制干燥，使湿膜的整个干燥过程不能在理想的掌控之中。  \n\n在以上条件下，漆膜从湿膜至实干的漫长过程中，产生的如气泡、泛白、暗泡、渗陷、离层等现象，几成“顽疾”。人为地要求、提高漆膜的干燥速率，是导致各种漆病越趋严重的另一重要原因。因为要返工、重涂，处理问题产品和不合格品，导致成本升高、工时损耗、延迟交货、质量下降、诚信受损等严重后果，但很多人对此并无足够的认识。因此，有效地防止漆病的出现，才是最主要的。这是涂料行业和家具企业面临的共同课题。  \n\n![](images/0e6aa446f773166c6419a626ab40e61c2b60a9bf99ea0fb23fbaecc42ec693c2.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 653,
+        "chunk": "# 一、木用涂料需要控制的指标  \n\n木用涂料作为装饰保护材料使用，其本身是半成品，它所形成的涂膜是高聚物材料，该涂膜不能独立存在，必须黏附在其他被涂物件（如木质家具等）上才能成为材料。所以木用涂料及其涂膜既具有一般聚合物材料的通性，又有与一般聚合物材料不同的特性。最主要的是涂膜必须适应被涂物件材质性能的要求，与被涂物件结合成为一体。  \n\n木用涂料的性能包括木用涂料产品本身的性能及其涂膜的性能两部分。",
+        "category": " Introduction"
+    },
+    {
+        "id": 654,
+        "chunk": "# 1.木用涂料产品本身的性能  \n\n木用涂料产品本身的性能包括涂料原始状态的性能（即在罐中的性能）和木用涂料的施工性能。  \n\n木用涂料原始状态的性能主要控制如下指标：原漆外观或在容器中状态（包括原漆是否有结皮、浮色、分层、增稠、沉淀、结块等内容)、颜色、透明度、黏度、细度、密度、固体含量、遮盖力等项目。  \n\n木用涂料的施工性能主要控制如下指标：涂刷性、可使用时间（或称适用期)、流平性、防流挂性、重涂性、干燥时间、使用量等项目。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 655,
+        "chunk": "# 2.木用涂料涂膜的性能  \n\n木用涂料涂膜的性能主要控制如下指标：漆膜外观（包括漆膜是否有起泡、针孔、缩孔、颗粒、橘皮、起皱、开裂等现象)、颜色、光泽、回黏性、抗粘连性、附着力、硬度、打磨性、耐冲击性、耐磨性、耐划伤性、耐液体介质（一般包括醇、水、酸、碱、茶、醋及其他污染物）、耐干热性、耐湿热性、耐黄变性等项目。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 656,
+        "chunk": "# 二、有关木用涂料性能的国家标准和行业标准  \n\n随着木用涂料的不断发展，其品种不断增加，应用范围不断扩大，市场上木用涂料产品的品质也参差不齐，为了更好地引导该类产品的良性发展，提升木用涂料的整体质量水平，近十年来，涂料行业有关专家制定了木用涂料的相关国家标准和行业标准。最具代表性的标准有：HG/T2454—2006《溶剂型聚氨酯涂料（双组分）》、HG/T3828—2006《室内用水性木器涂料》、HG/T3655--1999《紫外光（UV）固化木器涂料》和HG/T3383-—2003《硝基漆稀释剂》等行业标准，GB/T23998—2009《室内装饰装修用溶剂型硝基木器涂料》和GB/T23995—2009《室内装饰装修用溶剂型醇酸木器涂料》。",
+        "category": " Introduction"
+    },
+    {
+        "id": 657,
+        "chunk": "# 1.HG/T2454—2006《溶剂型聚氨酯涂料（双组分）》  \n\nHG/T2454—2006《溶剂型聚氨酯涂料（双组分）》是由HG/T2454—1993《聚氨酯清漆（分装)》、HG/T2660—1995《各色聚氨酯磁漆（双组分）》、HG/T3608—1999《聚酯聚氨酯木器漆》三份标准合并修订而成，该标准于2006年7月发布，于2007年3月实施。该标准适用于以含反应性官能团的聚酯树脂、醇酸树脂、丙烯酸树脂等主要成膜物，以多异氰酸酯树脂为固化剂的双组分常温固化型金属表面用涂料和室内用木器涂料。  \n\n该标准根据溶剂型聚氨酯涂料的两个主要应用领域，分为两个类型，I型为室内用木器涂料，Ⅱ型为金属表面用涂料，且室内用木器涂料又分为家具厂和装修用面漆、地板用面漆和通用底漆。其中I型（室内用木器涂料）产品应符合表3-7-144的技术要求。  \n\n表3-7-144I型（室内用木器涂料）产品技术要求  \n\n\n<html><body><table><tr><td colspan=\"3\" rowspan=\"2\">项目</td><td colspan=\"2\">指标</td><td colspan=\"2\"></td></tr><tr><td>家具厂和装修用面漆</td><td colspan=\"2\">地板用面漆</td><td>通用底漆</td></tr><tr><td colspan=\"3\">在容器中状态</td><td colspan=\"5\">搅拌后均匀无硬块</td></tr><tr><td colspan=\"3\">施工性</td><td colspan=\"5\">施涂无障碍</td></tr><tr><td colspan=\"3\">遮盖率(色漆)</td><td>商定</td><td colspan=\"2\"></td><td colspan=\"2\"></td></tr><tr><td colspan=\"3\" rowspan=\"2\">干燥时间/h ≤</td><td></td><td></td><td colspan=\"3\">一 1</td></tr><tr><td>表干 实干</td><td colspan=\"3\">24</td></tr><tr><td colspan=\"3\">涂膜外观</td><td colspan=\"5\">一</td></tr><tr><td colspan=\"3\">贮存稳定性(50℃，7d)</td><td colspan=\"5\">正常(涂膜均匀，无流挂、发花、针孔、开裂和剥落等涂膜病态)</td></tr><tr><td colspan=\"3\">打磨性</td><td colspan=\"5\">无异常[试验结果与贮存前比无明显变化（主剂允许变色）]</td></tr><tr><td colspan=\"3\">光泽(60°)/%</td><td colspan=\"4\">一</td><td>易打磨</td></tr><tr><td colspan=\"3\">铅笔硬度(擦伤) M</td><td colspan=\"4\">商定</td><td>一</td></tr><tr><td colspan=\"3\">附着力（划格间距2mm）/级 ≤</td><td colspan=\"4\">F</td><td></td></tr><tr><td colspan=\"3\">耐干热性[（90±2)℃，15min]/级</td><td colspan=\"4\">I ：</td><td></td></tr><tr><td colspan=\"2\">耐磨性(750g，500r)/g</td><td>≤</td><td colspan=\"3\">2</td><td></td><td>一</td></tr><tr><td colspan=\"3\">耐冲击性</td><td>0.050 一</td><td></td><td>0.040 涂膜无脱落、无开裂</td><td></td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td colspan=\"2\" rowspan=\"2\">项 目</td><td colspan=\"3\">指 标</td></tr><tr><td>家具厂和装修用面漆</td><td>地板用面漆</td><td>通用底漆</td></tr><tr><td colspan=\"2\">耐水性(24h)</td><td rowspan=\"6\">无异常（涂膜未出现起泡、开裂、剥落、明显变色、明显光泽 变化)</td><td rowspan=\"6\"></td><td></td></tr><tr><td colspan=\"2\">耐碱性(2h)</td><td></td></tr><tr><td colspan=\"2\">耐醇性(8h)</td><td></td></tr><tr><td colspan=\"2\" rowspan=\"3\">醋 耐污染性（1h) 茶</td><td></td></tr><tr><td></td></tr><tr><td></td></tr><tr><td rowspan=\"4\">耐黄变性(168h)E</td><td>一级 清漆</td><td colspan=\"3\">3.0</td></tr><tr><td>二级</td><td colspan=\"3\">6.0</td></tr><tr><td>色漆</td><td colspan=\"3\">3.0</td></tr></table></body></html>\n\n$\\textcircled{1}$ 该项目仅限于标称具有耐黄变等类似功能的产品。",
+        "category": " References"
+    },
+    {
+        "id": 658,
+        "chunk": "# 2.HG/T3828—2006《室内用水性木器涂料》  \n\nHG/T3828—2006《室内用水性木器涂料》于2006年7月首次发布，2007年3月实施。该标准适用于聚氨酯类、丙烯酸酯类、丙烯酸-聚氨酯类以及其他类型的常温干燥型单组分或双组分水性木器涂料。水性木器涂料按实际用途及使用功能分为A、B、C、D四类。  \n\nA类：地板用面漆———工厂涂装和家庭涂装等所有木质地板用面漆。B类：家具用面漆——工厂涂装木质家具用面漆。C类：装修用面漆——除A、B类以外的木质表面用面漆，主要用于门套、窗套、扩墙板等的涂装。D类：底漆、中涂漆—所有可与各类面漆配套使用的木器用底漆、中涂漆。主要技术要求见表3-7-145。  \n\n表3-7-145 室内用水性木器涂料技术要求  \n\n\n<html><body><table><tr><td colspan=\"3\">项 目</td><td colspan=\"3\">指 标 A类 D类</td></tr><tr><td colspan=\"3\">在容器中状态</td><td colspan=\"3\">B类 C类 搅拌后均匀无硬块</td></tr><tr><td colspan=\"3\">细度/μm ≤</td><td colspan=\"3\">清漆、透明色漆：35 35</td></tr><tr><td colspan=\"3\"></td><td colspan=\"2\">色漆：40</td><td>60 清漆、透明色漆：30</td></tr><tr><td colspan=\"3\">不挥发物（双组分为主剂）/%</td><td colspan=\"3\">30 色漆：40 单组分30；双组分60</td></tr><tr><td rowspan=\"2\">干燥时间 贮存稳定性(50℃，7d)</td><td rowspan=\"2\">实干/h</td><td>表干/min</td><td colspan=\"4\">单组分6；双组分24</td></tr><tr><td colspan=\"2\"></td><td colspan=\"3\">无异常（试验后如揽拌后均匀无硬块为无异常）</td></tr><tr><td colspan=\"3\">耐冻融性</td><td colspan=\"4\">不变质</td></tr><tr><td colspan=\"3\">涂膜外观</td><td colspan=\"4\"></td></tr><tr><td colspan=\"3\">光泽(60°)</td><td colspan=\"3\">正常</td><td>一</td></tr><tr><td colspan=\"3\"></td><td colspan=\"2\">商定</td><td>一</td></tr><tr><td colspan=\"3\">打磨性</td><td colspan=\"2\">一</td><td>易打磨</td></tr><tr><td colspan=\"3\">硬度(擦伤)</td><td colspan=\"3\">B 一</td></tr><tr><td colspan=\"3\">附着力（划格间距2mm）/级</td><td>涂膜无脱</td><td colspan=\"2\">1</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td colspan=\"2\" rowspan=\"2\">项 目</td><td colspan=\"3\">指 标</td></tr><tr><td>A类 B类</td><td>C类</td><td>D类</td></tr><tr><td colspan=\"2\">抗粘连性（500g，50℃/4h）</td><td>MM:A-0 MB:A-0</td><td>一</td><td></td></tr><tr><td colspan=\"2\">耐磨性（750g，500r）/g</td><td colspan=\"3\">0.030 一</td></tr><tr><td colspan=\"2\">耐划伤性(100g)</td><td>未划伤</td><td></td><td>一</td></tr><tr><td rowspan=\"2\">耐水性</td><td>耐水性(24h)</td><td colspan=\"2\">无异常</td><td></td></tr><tr><td colspan=\"2\">耐沸水性（15min）</td><td>无异常</td><td></td></tr><tr><td colspan=\"2\">耐碱性(50g/L NaHCOs,1h)</td><td colspan=\"2\">无异常</td><td>一</td></tr><tr><td colspan=\"2\">耐醇性(50%，1h)</td><td colspan=\"2\">无异常</td><td></td></tr><tr><td rowspan=\"2\">耐污染性（1h)</td><td>醋</td><td colspan=\"2\">无异常</td><td>一</td></tr><tr><td>绿茶</td><td colspan=\"2\">无异常</td><td></td></tr><tr><td colspan=\"2\">耐干热性[（70±2）℃，15min]/级</td><td colspan=\"3\">≤ 2 一</td></tr><tr><td colspan=\"2\">耐黄变性（168h)△E*</td><td colspan=\"3\">3.0</td></tr><tr><td colspan=\"2\">总挥发性有机化合物（TVOC）/（g/L）</td><td colspan=\"3\">300</td></tr><tr><td rowspan=\"4\">重金属（清漆除外）/（mg/kg）</td><td>可溶性铅 ≤</td><td colspan=\"3\">90</td></tr><tr><td>可溶性 ≤</td><td colspan=\"3\">75</td></tr><tr><td>可溶性铬 ≤</td><td colspan=\"3\">60</td></tr><tr><td>可溶性汞 ≤</td><td colspan=\"3\">60</td></tr></table></body></html>\n\n$\\textcircled{1}$ 用于工厂涂装且对此项无要求的产品可不做该项。$\\textcircled{2}$ 该项自仅限标称具有耐黄变等功能的产品。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 659,
+        "chunk": "# 3.HG/T3655—1999《紫外光（UV）固化木器涂料》  \n\n该标准于1999年6月首次发布，2000年6月实施。该标准适用于木质地板、家具或其他木器的装饰与保护用紫外光固化漆。该标准中规定了底漆和面漆的技术要求，详见表3-7-146。  \n\n表3-7-146 紫外光（UV）固化木器涂料技术要求  \n\n\n<html><body><table><tr><td rowspan=\"2\">项 目</td><td>指</td><td>标</td></tr><tr><td>底漆</td><td>面 漆</td></tr><tr><td>在容器中状态</td><td colspan=\"3\">搅拌后呈均匀状态</td></tr><tr><td>细度/μm ≤</td><td colspan=\"3\">70 有光10；半光和无光35</td></tr><tr><td></td><td colspan=\"3\">商定</td></tr><tr><td>固化速率</td><td colspan=\"3\">平整</td></tr><tr><td>漆膜外观 光泽(60°)</td><td colspan=\"3\"></td></tr><tr><td>M 划格试验，级</td><td>一 2</td><td>有光90；半光和无光商定</td><td>2</td></tr><tr><td>< 硬度</td><td>0.60</td><td>有光0.60；半光和无光0.50</td><td></td></tr><tr><td>复合层耐水性(72h)</td><td colspan=\"3\">不起泡，不起皱，不脱落</td></tr><tr><td>复合层耐醇性(8h）</td><td colspan=\"3\">不起泡，不起皱，不脱落</td></tr><tr><td>耐磨性（750g，500r）/g</td><td colspan=\"3\"></td></tr><tr><td>复合层耐干热性[（90士2)℃]/级 ≤</td><td colspan=\"3\">一 0.030 2</td></tr></table></body></html>  \n\n该标准中的“复合层”是指：在底材上涂布底漆干燥打磨后，底漆上涂布光固化面漆，再按要求固化所得的涂膜。其底漆可以是紫外光固化类底漆，也可以是非紫外光固化类底漆。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 660,
+        "chunk": "# 4.HG/T3378—2003《硝基漆稀释剂》  \n\n该标准于2004年1月发布，2004年5月实施，是由HG/T3378—1987《X-1、X-2硝基漆稀释剂》修订而成。该标准适用于由酯、醇、酮、芳烃类等混合溶剂配制而成的稀释剂。  \n\n该标准中产品分I型和Ⅱ型硝基漆稀释剂，其中I型产品的酯、酮溶剂比例较高，溶解性能较好，可用作硝基清漆、磁漆、底漆稀释；Ⅱ型产品的酯、酮溶剂比例较低，溶解性能稍差，可用作要求不高的硝基漆及底漆的稀释，或作清洗硝基漆施工工具及用品等。其技术要求详见表3-7-147。  \n\n表3-7-147 硝基漆稀释剂产品技术要求  \n\n\n<html><body><table><tr><td rowspan=\"2\">项 目 ≤</td><td>指</td><td>标</td><td></td></tr><tr><td>I型</td><td>Ⅱ型</td><td></td></tr><tr><td>颜色（铁钻比色计）/号</td><td colspan=\"3\">1</td></tr><tr><td>外观和透明度</td><td>清澈透明，无机械杂质</td><td></td><td></td></tr><tr><td>酸值/(mgKOH/g)</td><td>0.15</td><td>0.20</td><td></td></tr><tr><td>水分</td><td colspan=\"3\">不浑浊，不分层</td></tr><tr><td>胶凝数/mL</td><td>20</td><td></td><td>18</td></tr><tr><td>白化性</td><td>漆膜不发白及没有无光斑点</td><td>一</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 661,
+        "chunk": "# 5.GB/T23998—2009《室内装饰装修用溶剂型硝基木器涂料》  \n\n该标准是2008年首次组织起草，于2008年9月报批的推荐性国家标准，2009年6月批准发布，2010年2月实施。该标准适用于以硝酸纤维素为主要成膜物，加人醇酸树脂、改性松香树脂、丙烯酸树脂等改性而成的木器涂料。产品适用于室内装饰装修（含工厂化涂装）用木制品表面的保护及装饰。该标准中将溶剂型硝基木器涂料分为面漆和底漆，其主要技术要求详见表3-7-148。  \n\n表3-7-148 室内装饰装修用溶剂型硝基木器涂料技术要求  \n\n\n<html><body><table><tr><td rowspan=\"2\"></td><td rowspan=\"2\">项 目</td><td rowspan=\"2\"></td><td>指</td><td>标</td></tr><tr><td>面漆</td><td></td><td>底漆</td></tr><tr><td colspan=\"3\">在容器中状态</td><td colspan=\"3\">搅拌后均匀无硬块</td></tr><tr><td rowspan=\"2\">细度/μm</td><td rowspan=\"2\"></td><td>≤</td><td>40</td><td colspan=\"2\">60</td></tr><tr><td>表干/min</td><td>20</td><td colspan=\"2\"></td></tr><tr><td rowspan=\"2\">干燥时间 涂膜外观</td><td>≤ 实干/h</td><td></td><td>2</td><td colspan=\"2\"></td></tr><tr><td></td><td></td><td>正常</td><td colspan=\"2\"></td></tr><tr><td colspan=\"3\">回黏性/级 ≤</td><td>2</td><td colspan=\"2\">二 一</td></tr><tr><td colspan=\"3\">打磨性</td><td>一</td><td colspan=\"2\">易打磨</td></tr><tr><td colspan=\"4\">光泽(60°)</td><td>商定</td><td colspan=\"2\">二</td></tr><tr><td colspan=\"4\">铅笔硬度（擦伤） M</td><td>B</td><td colspan=\"2\"></td></tr><tr><td colspan=\"4\">附着力/级(划格间距2mm） ≤</td><td colspan=\"3\">2</td></tr><tr><td colspan=\"4\">耐干热性[（90±2）℃，15min]/级 ≤</td><td colspan=\"3\">2</td></tr><tr><td colspan=\"4\">耐水性(24h)</td><td>无异常</td><td colspan=\"2\">一</td></tr><tr><td colspan=\"4\">耐碱性（50g/LNaHCO3,1h)</td><td>无异常</td><td colspan=\"2\">一</td></tr><tr><td rowspan=\"2\">耐污染性(1h)</td><td colspan=\"2\">醋</td><td colspan=\"2\"></td><td colspan=\"2\">一</td></tr><tr><td>茶</td><td></td><td colspan=\"2\">无异常 无异常</td><td colspan=\"2\">一 一</td></tr></table></body></html>  \n\n6.GB/T23995—2009《室内装饰装修用溶剂型醇酸木器涂料》该标准于2008年9月报批的推荐性国家标准，2009年6月批准发布，2010年2月实施。标准适用于以醇酸树脂为主要成膜物，通过氧化干燥成膜而成的溶剂型木器涂料。其主要技术要求见表3-7-149。  \n\n表3-7-149 室内装饰装修用溶剂型醇酸木器涂料技术要求  \n\n\n<html><body><table><tr><td colspan=\"2\">项</td><td>目</td><td>指标</td><td colspan=\"2\">项 目</td><td>指标</td></tr><tr><td colspan=\"2\">在容器中状态</td><td>搅拌后均匀无硬块</td><td>光泽(60°)</td><td colspan=\"2\"></td><td>商定</td></tr><tr><td colspan=\"2\">细度/μm</td><td>40</td><td></td><td colspan=\"2\">附着力/级(划格间距2mm) ≤</td><td>１</td></tr><tr><td rowspan=\"2\">干燥时间</td><td>表干/h</td><td>00</td><td colspan=\"2\">耐干热性[（70±2)℃，15min]/级</td><td>2</td></tr><tr><td>实干/h</td><td>24</td><td colspan=\"2\">耐水性(24h)</td><td>无异常</td></tr><tr><td rowspan=\"2\">贮存稳定性</td><td>结皮性(24h)</td><td>不结皮</td><td colspan=\"2\">耐碱性（50g/L的NaHCO,1h)</td><td>无异常</td></tr><tr><td>沉降性(50°℃，7d)</td><td>无异常</td><td colspan=\"2\"></td><td>无异常</td></tr><tr><td>涂膜外观</td><td colspan=\"2\">正常</td><td rowspan=\"2\">耐污染性(1h)</td><td>醋 茶</td><td></td></tr><tr><td colspan=\"2\"></td><td></td><td>无异常</td></tr></table></body></html>",
+        "category": " References"
+    },
+    {
+        "id": 662,
+        "chunk": "# 7.GB/T23997—2009《室内装饰装修用溶剂型聚氨酯木器涂料》  \n\n该标准2009年6月批准发布，2010年2月实施。该标准适用于以含反应性官能团的聚酯树脂、醇酸树脂、丙烯酸树脂等为主要成膜物，以多异氰酸酯树脂为固化剂的双组分常温固化型室内用木器涂料。其主要技术要求中除铅笔硬度外，其他项目与HG/T2454—2006《溶剂型聚氨酯涂料（双组分）》中的I型（室内用木器涂料）产品完全一致，家具厂和装修用面漆的铅笔硬度要求不低于HB，地板用面漆的铅笔硬度要求不低于F。  \n\n8.GB/T23999—2009《室内装饰装修用水性木器涂料》  \n\n该标准2009年6月批准发布，2010年2月实施。该标准适用于聚氨酯类、丙烯酸酯类、丙烯酸-聚氨酯类以及其他类型的常温干燥型单组分或双组分水性木器涂料。与HG/T3828—2006《室内用水性木器涂料》标准相比，该标准只取消了总挥发性有机化合物和可溶性重金属（铬、镉、铅、汞）项目，其他项目和内容与HG/T3828—2006《室内用水性木器涂料》完全一致。",
+        "category": " References"
+    },
+    {
+        "id": 663,
+        "chunk": "# 三、木质家具标准中对涂膜性能的要求  \n\n木质家具主要由木质基材、基材表面的涂膜或软、硬质覆面材料以及其他配件组成，在其标准中技术要求主要包括基材的尺寸要求、形状要求、用料要求、木工要求、涂饰要求、理化性能要求（针对漆膜涂层和软、硬质覆面）、五金配件及安装要求和力学要求。下面介绍几种常用的木质家具标准中对涂饰及涂膜理化性能的要求。",
+        "category": " Introduction"
+    },
+    {
+        "id": 664,
+        "chunk": "# 1.GB/T3324一2008《木家具通用技术要求》  \n\n该标准适用于木家具产品的通用技术要求，其他家具的木质件可参照执行。  \n该标准中规定的漆膜外观及理化性能要求详见表3-7-150。  \n\n表3-7-150木家具表面漆膜外观及理化性能要求  \n\n\n<html><body><table><tr><td>检验项目</td><td>试验条件及要求</td><td colspan=\"2\">项目分类</td></tr><tr><td rowspan=\"4\">漆膜外观</td><td></td><td>基本</td><td>一般</td></tr><tr><td>同色部件的色泽应相似</td><td></td><td>√</td></tr><tr><td>应无褪色、掉色现象</td><td>√</td><td></td></tr><tr><td>涂层不应有皱皮、发黏或漏漆现象 涂层应平整光滑、清晰，无明显粒子、胀边现象；应无明显加工痕迹、划痕、雾光、</td><td>√</td><td>√</td></tr></table></body></html>  \n\n<html><body><table><tr><td>检验项目</td><td>试验条件及要求</td><td colspan=\"2\">项目分类</td></tr><tr><td rowspan=\"2\">耐液性</td><td></td><td>基本</td><td>一般</td></tr><tr><td>10%碳酸钠溶液，24h，应不低于3级</td><td>√</td><td></td></tr><tr><td>耐湿热</td><td>10%乙酸溶液，24h，应不低于3级</td><td></td><td></td></tr><tr><td></td><td>70℃，20min，应不低于3级</td><td>√ √</td><td></td></tr><tr><td>耐干热</td><td>70℃，20min，应不低于3级</td><td>√</td><td></td></tr><tr><td>附着力</td><td>涂层交叉切割法，应不低于3级</td><td>√</td><td></td></tr><tr><td>耐冷热温差</td><td>3个周期，应无鼓泡、裂缝和明显失光</td><td></td><td></td></tr><tr><td>耐磨性</td><td>1000r，应不低于3级 冲击高度50mm，应不低于3级</td><td>√</td><td></td></tr><tr><td>耐冲击</td><td></td><td></td><td></td></tr><tr><td>耐香烟灼烧</td><td>应无脱落状黑斑、裂纹、鼓泡现象</td><td></td><td></td></tr></table></body></html>\n\n注：“ $\\#^{\\#}$ 记号表示该单项中有2个以上（含2个）检验内容，若有一个检验项目不符合要求时，应按一个不合格计数。若某缺陷明显到足以影响产品质量时则作为基本项目判定。  \n\n检验结果判定：基本项目全部合格，一般项目不合格项不超过4项，判定该产品为合格品。达不到合格品要求的为不合格品。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 665,
+        "chunk": "# 2.QB/T2530—2001《木制柜》  \n\n该标准适用于木制柜产品，不适用于厨房家具，也不适用于多功能组合柜中不属于柜类功能的产品。  \n\n（1）涂饰要求整件产品、成套产品色泽不应有明显色差；表面漆膜不应有皱皮、发黏和漏漆现象；不涂饰部位应保持清洁；涂饰部位不应掉色、褪色；正视面（包括面板）涂层应平整、光滑、清晰；漆膜实干后应无明显木孔沉陷；其他部位涂层手感光滑；无明显粒子、胀边和不平整；涂层应无明显加工痕迹、划痕、雾光、白棱、鼓泡、油白、流挂、缩孔、刷毛、积粉和杂渣。  \n\n(2）理化性能 详见表3-7-151。  \n\n续表  \n表3-7-151 木制柜表面漆膜理化性能要求  \n\n\n<html><body><table><tr><td colspan=\"2\">项</td><td colspan=\"3\">指 标 值</td></tr><tr><td rowspan=\"2\"></td><td>目</td><td>A级</td><td>B级</td><td>C级</td></tr><tr><td>10%碳酸钠，24h</td><td>1级</td><td>2级</td><td>3级</td></tr><tr><td colspan=\"2\">30%乙酸，24h 耐湿热</td><td>80℃，二级</td><td>70℃，二级</td><td>70℃，三级</td></tr><tr><td colspan=\"2\">耐干热</td><td>85℃，二级</td><td>80℃，二级</td><td>80°℃，三级</td></tr><tr><td colspan=\"2\">附着力/级</td><td>1</td><td>2</td><td>3</td></tr><tr><td colspan=\"2\">耐磨(2000r)/级</td><td>1</td><td>2</td><td>3</td></tr><tr><td colspan=\"2\">耐冷热温差</td><td colspan=\"3\">3周期，无鼓泡、裂缝和明显失光</td></tr><tr><td colspan=\"2\">耐冲击（冲击高度50mm）/级</td><td>1</td><td>2</td><td>3</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 666,
+        "chunk": "# 3.QB/T2383—1998《餐桌餐椅》  \n\n该标准适用于主要材料由木材或木质人造材料或（或）金属材料构成的产品，其他材料构成的产品可参照执行。本标准不适用于桌椅连为一体的餐桌和餐椅。  \n\n(1）涂饰要求按 $\\mathrm{GB}/\\mathrm{T}~3324{-}1995$ 中要求。  \n（2）涂层理化性能 详见表3-7-152。  \n\n表3-7-152 餐桌餐椅表面涂层理化性能要求  \n\n\n<html><body><table><tr><td colspan=\"2\">项 目</td><td>技术要求</td><td>项 目</td><td>技术要求</td></tr><tr><td rowspan=\"3\">耐液性/级</td><td>10%碳酸钠，24h</td><td rowspan=\"3\">3</td><td>附着力/级</td><td>2</td></tr><tr><td>30%乙酸，24h</td><td>耐磨(1000r)/级</td><td>2</td></tr><tr><td>15%氯化钠，24h</td><td>耐冷热温差</td><td>3周期，无鼓泡、裂纹和</td></tr><tr><td colspan=\"2\">耐湿热（85℃）/级</td><td>2</td><td></td><td>明显失光</td></tr><tr><td colspan=\"2\">耐干热（90℃）/级</td><td>2</td><td>耐冲击(冲击高度50mm）/级</td><td>3</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 667,
+        "chunk": "# 4.QB/T3916—1999《课桌椅》  \n\n该标准适用于大、中学教学用的课桌、椅。木质件漆膜理化性能要求详见表3-7-153。  \n\n表3-7-153 课桌椅中木质件漆膜理化性能要求  \n\n\n<html><body><table><tr><td>项目</td><td>技术要求</td><td>项 目</td><td>技术要求</td></tr><tr><td>耐水(蒸馏水80h)/级</td><td>2</td><td>附着力（间距2mm）/级</td><td>2</td></tr><tr><td>耐30%乙酸(24h)/级</td><td>2</td><td>耐磨（400r)/级</td><td>2</td></tr><tr><td>耐10%碳酸钠（8h）/级</td><td>2</td><td>耐冷热温差，温度（40士2）℃，</td><td>3周期，无鼓泡、裂纹</td></tr><tr><td>耐湿热（70C，15min）/级</td><td>2</td><td>（-20±2)℃，相对湿度98%～99%</td><td>和明显失光</td></tr><tr><td>耐干热（80C，15min）/级</td><td>2</td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 668,
+        "chunk": "# 四、通用检验方法  \n\n上述国家标准和行业标准中涉及的指标约三十项，其中有些指标项已有相当成熟的检验方法，并以推荐性国家标准或行业标准的形式发布实施，有些指标项还没有相应的国家标准或行业标准的检验方法，但在行业内有通用的检验方法，具体情况详见表3-7-154。  \n\n表3-7-154 检测项目与检测方法标准对照表  \n\n\n<html><body><table><tr><td>指标名称</td><td>检验方法标准代号及名称</td></tr><tr><td>外观和透明度</td><td>GB/T1721—2008《清漆、清油及稀释剂外观和透明度测定法》</td></tr><tr><td>颜色(铁钻比色计)</td><td>GB/T1722—1992《清漆、清油及稀释剂颜色测定法（甲法）》</td></tr><tr><td>细度</td><td>GB/T1724—1979《涂料细度测定法》 GB/T6753.1—2007《色漆、清漆和印刷油墨研磨细度的测定》</td></tr><tr><td>黏度</td><td>GB/T1723--1993《涂料粘度测定法》 GB/T9269—-1988《建筑涂料黏度的测定斯托默黏度计法》 GB/T7193.1—1987《不饱和聚酯树脂黏度测定方法》 GB/T2794—1995《胶黏剂黏度的测定》</td></tr><tr><td>遮盖力</td><td>GB/T9757—2001中5.7《溶剂型外墙涂料》 GB/T1726—1979（1989）《涂料遮盖力测定法》</td></tr><tr><td>不挥发分</td><td>GB/T1725—2007《色漆、清漆和塑料不挥发物含量的测定》</td></tr><tr><td>干燥时间</td><td>GB/T1728—1979《漆膜、腻子膜干燥时间测定法》</td></tr><tr><td>光泽</td><td>GB/T9754—2007《色漆和清漆不含金属颜料的色漆漆膜的20°、60°和85°镜面光泽的测定》 GB/T4893.6—1985《家具表面漆膜光泽测定法》</td></tr><tr><td>附着力</td><td>GB/T1720—1979《漆膜附着力测定法》 GB/T9286—1998《色漆和清漆漆膜的划格试验》 GB/T4893.4—1985《家具表面漆膜附着力交叉切割测定法》</td></tr></table></body></html>  \n\n$$\n,\n$$  \n\n续表  \n\n\n<html><body><table><tr><td>指标名称</td><td>检验方法标准代号及名称</td></tr><tr><td>硬度</td><td>GB/T1730—2007《色漆和清漆 摆杆阻尼试验》 GB/T6739—2006《色漆和清漆铅笔法测定漆膜硬度》</td></tr><tr><td>耐湿热性</td><td>GB/T4893.2—2005《家具表面耐湿热测定法》</td></tr><tr><td>耐干热性</td><td>GB/T4893.3—2005《家具表面耐千热测定法》</td></tr><tr><td>耐磨性</td><td>GB/T1768—2006《色漆和清漆耐磨性的测定旋转橡胶砂轮法》 GB/T4893.8—1985《家具表面漆膜耐磨性测定法》</td></tr><tr><td>打磨性</td><td>GB/T1770—2008《涂膜、腻子膜打磨性测定法》</td></tr><tr><td>耐冲击性 面积冲头)》</td><td>GB/T20624.2—2006《色漆和清漆快速变形（耐冲击性）试验第2部分 落锤试验（小</td></tr><tr><td>回黏性</td><td>GB/T4893.9—1985《家具表面漆膜摘冲击测定法》 GB/T1762—1980《漆膜回粘性测定法》</td></tr><tr><td>耐划伤性</td><td>GB/T9279—2007《色漆和清漆划痕试验》</td></tr><tr><td>耐水性</td><td></td></tr><tr><td>耐醇性</td><td></td></tr><tr><td>耐 耐酸性</td><td>GB/T9274—1988《色漆和清漆耐液体介质的测定》</td></tr><tr><td>液 性 耐碱性</td><td>GB/T4893.1—2005《家具表面耐冷液测定法》</td></tr><tr><td>耐污染性(醋，茶)</td><td></td></tr><tr><td>其他液体介质</td><td></td></tr><tr><td>耐冻融性</td><td>GB/T9268—2008《乳胶漆耐冻融性的测定》</td></tr><tr><td>耐冷热温差</td><td>GB/T9755—2001中5.5《合成树脂乳液外墙涂料》 GB/T4893.7—1985《家具表面漆膜耐冷热温差测定法》</td></tr><tr><td>耐香烟灼烧</td><td>GB/T17657—1999《人造板及饰面人造板理化性能试验方法中4.40的规定》</td></tr><tr><td>水分</td><td>HG/T3858—2006《稀释剂、防潮剂水分测定法》</td></tr><tr><td>胶凝数</td><td>HG/T3861—2006《稀释剂、防潮剂胶凝数测定法》</td></tr><tr><td>白化性</td><td>HG/T3859—2006《稀释剂、防潮剂白化性测定法》</td></tr><tr><td>贮存稳定性</td><td>GB/T6753.3—1986《涂料贮存稳定性试验方法》</td></tr><tr><td>抗粘连性</td><td>GB/T23982—2009《木器涂料抗粘连性测定法》</td></tr><tr><td>耐黄变性</td><td>GB/T23983—2009《木器涂料耐黄变性测定法》</td></tr><tr><td>总挥发性有机化合物</td><td>详见：六、木用涂料生产，施工，成膜后的有害物质标准及测试方法中（五）</td></tr><tr><td>可溶性重金属</td><td></td></tr><tr><td>在容器中状态</td><td>无</td></tr><tr><td>涂膜外观</td><td>无</td></tr><tr><td>固化速率</td><td>无</td></tr><tr><td>酸值（NC稀释剂）</td><td>无</td></tr><tr><td>NCO含量（聚氨酯固化剂）</td><td>无</td></tr></table></body></html>  \n\n现简单介绍还没有现成国家标准或行业标准的指标项的通用测试方法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 669,
+        "chunk": "# 1.在容器中状态（原漆外观）  \n\n打开容器，目测或用调刀或搅拌棒触及原漆表面，观察有无结皮、浮色、分层等现象，  \n\n然后用调刀或搅拌棒插人容器底部检查是否有沉淀、结块现象，再用调刀或搅拌棒搅拌涂料，检查是否有增稠现象，如有沉淀则观察沉淀是否容易搅拌均匀。  \n\n通常允许容器底部有沉淀，若经搅拌易于混合均匀，则评为“搅拌后均匀无硬块”。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 670,
+        "chunk": "# 2.漆膜外观  \n\n按产品标准中规定选用底材和施工方式进行施工后，放置规定的时间后，将样板在散射日光下目视观察，如果涂膜均匀，无流挂、发花、橘皮、起皱、起泡、针孔、缩孔、颗粒、开裂和剥落等涂膜病态，则评为“正常”。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 671,
+        "chunk": "# 3.固化速率  \n\n按产品标准规定涂漆后，可用单一的紫外灯或生产线固化装置（按产品标准中规定）进行固化，单一紫外灯固化时以所需的固化时间（单位为s）来表示固化速率，以生产线固化装置固化时以生产线的运转速度（单位为m/min）来表示固化速率，漆膜是否固化的判断按GB/T1728—1979（1989）中第3章的甲法进行。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 672,
+        "chunk": "# 4.硝基漆稀释剂的酸值  \n\n用感量为0.01g的天平在 $250\\mathrm{mL}$ 磨口瓶中称取 $25\\sim35\\mathrm{g}$ 试样，加人 $20{\\sim}30\\mathrm{mL}$ 刚用氢氧化钾标准溶液中和好的乙醇，加酚酞批示剂 $2\\cdots3$ 滴，加盖摇匀，立即用 $0.\\ 02{\\sim}0.\\ 04\\mathrm{mol/L}$ 的氢氧化钾标准溶液滴定至试液呈粉红色，于10s内不消失为终点。  \n\n酸值以氢氧化钾（KOH）的质量分数AV表示，数值以毫克每克（mg/g）表示，按式(3-7-1）计算。  \n\n$$\n\\mathbf{AV}{=}V c M/m\n$$  \n\n式中V- 测定试样所消耗的氢氧化钾标准溶液的体积， $\\mathrm{mL}$ C 氢氧化钾标准溶液的浓度， $\\mathrm{\\mol/L}$ M——氢氧化钾的摩尔质量，g/mol，M=56.109g/mol;m--—所取试样的质量， $\\tilde{\\textbf{g}}$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 673,
+        "chunk": "# 5.聚氨酯固化剂中NCO含量  \n\n(1）原理利用二丁胺与NCO基团快速定量反应的原理，用过量二丁胺跟NCO基团反应，再用HCI滴定过量的二丁胺来定量计算NCO基团的含量。  \n\n(2）仪器与试剂电子天平：感量 $0,001\\mathbf{g}$ ；乙酸乙酯 (分析纯)； $1\\%$ 溴甲酚绿-乙醇指示剂； $0,5\\mathrm{mol/L}$ HCl-乙醇溶液； $1\\mathrm{mol/L}$ 二丁胺-甲苯溶液（取 $129\\mathrm{g}$ 重蒸无水二丁胺，用无水甲苯稀释至 $1000\\mathrm{ml}$ ，摇匀，备用)。  \n\n(3）测定步骤称取试样 $\\mathrm{1\\sim3g}$ （准确至 $0,001\\mathbf{g}$ ，NCO含量大于 $20\\%$ 时称样 $\\mathbf{1}_{\\mathbf{E}}$ 左右）于 $250\\mathrm{mL}$ 的三角瓶中，加人 $20\\mathrm{mL}$ 乙酸乙酯，充分溶解，用瓶颈加液器(或移液管)准确加入 $\\boldsymbol{10}\\mathrm{ml.}$ 二丁胺-甲苯溶液，充分摇匀，不需放置（仲裁时放置 $20\\mathrm{min})$ ，加人3滴溴甲酚绿-乙醇指示剂（如用电位滴定仪滴定时不需加指示剂，由仪器直接判断滴定终点)，用 $0.5\\mathrm{mol/L}$ 的盐酸-乙醇标准溶液滴定至颜色由纯蓝色变成黄色为终点，同时做空白试验。  \n\n（4）NCO含量计算  \n\n$$\n\\pmb{X}(\\llcorner\\llcorner)=\\frac{(\\pmb{V}_{0}-\\pmb{V}_{1})c\\times4.202}{m}\n$$  \n\n式中 $V_{0}$ 空白耗用HCI-乙醇标准溶液的体积， $\\mathrm{mL}$  \n\n$V_{1}$ ——试样耗用HCI-乙醇标准溶液的体积， $\\mathrm{mL}$ c——HCl-乙醇标准溶液浓度， $\\mathrm{\\mol/L}$ 771 试样的质量，g。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 674,
+        "chunk": "# 五、特殊指标和特殊检测方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 675,
+        "chunk": "# 1.破坏性检验项目的非破坏性测定方法  \n\n在木质家具行业，成品漆膜理化性能的测试绝大部分项目都是破坏性测试，如直接检测成品的理化性能，将会破坏家具，导致测试成本增加，并造成浪费。为了解决这一问题，可以采用如下方式进行操作，既可以检测到家具漆膜的理化性能，又不会破坏家具。  \n\n找一块或几块尺寸合适（适合于测试要求）、材质与木质家具材质一致的板材，作为测试用试板，将该试板和家具按完全相同的施工方式并尽可能同时进行施工，也就是说按同样的方式进行底材处理，涂布底漆和面漆时将试板置于被涂实件旁，在涂布实件的同时完成试板的涂布，然后在相同的环境条件下干燥漆膜。这样，测试用试板上漆膜的理化性能巴经相当接近该家具实件表面漆膜的理化性能，然后将试板用来作破坏性检测，达到代替实物检测的目的。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 676,
+        "chunk": "# 2.木质涂料涂膜耐温变性（即耐冷热循环）  \n\n涂膜耐温变性是指涂膜经受从高温、高湿到低温急速变化情况下，抵抗被破坏的能力，是检测因涂膜在骤冷、骤热情况下发生变化而引起的开裂、起泡、脱皮等破坏现象。  \n\n通用检测方法是在高温 $60^{\\circ}C$ （或 $40^{\\circ}C$ ， $80^{\\circ}C$ )、高湿（相对湿度 $98\\%\\sim99\\%$ ）条件下保持一定时间（一般为1h）后，再在低温一 $20^{\\circ}C$ 放置一定时间（一般为1h)，并要求试板从一种温度条件变化到另一种温度条件所花的时间不超过 $2\\mathrm{min}$ ；每经过三个循环将试板放于温度为 $(20\\pm2)^{\\circ}C$ 、相对湿度 $60\\%\\sim70\\%$ 的条件下静置 $\\mathrm{18h}$ ，然后检查漆膜表面；如此经过若干次循环（一般采用以3为倍数的循环周期数)，最后观察涂膜变化的情况。  \n\n具体的温度、放置时间和循环次数应根据产品标准规定进行。  \n\n试板涂饰完工后至少存放10天，并达到完全干燥后，于满足温度为 $(20\\pm2)^{\\circ}C$ 、相对湿度 $60\\%\\sim70\\%$ 的环境条件的试验室内状态调节 $\\mathtt{24h}$ 后，方可进行试验。  \n\n测试仪器：有恒温恒湿箱和低温冰箱的组合；也有近年来发展起来的高低温交变试验箱。  \n\n测试方法标准：GB/T4893.7—1985《家具表面漆膜耐冷热温差测定法》。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 677,
+        "chunk": "# 3.亚光清漆重涂性能评价方法  \n\n(1）问题提出的背景亚光清漆在家具涂装中应用广泛，在涂布过程中如果没有很好的涂装和干燥环境，将导致漆膜表面出现颗粒或其他表观缺陷，从而影响家具的美观。目前的情况是：家具厂会对涂布了亚光清漆的家具进行涂膜表观指标的验收，把涂膜外观不符合要求的家具判为不合格并进行返工。通常的返工方式是将涂膜表面进行打磨，再重新喷涂。如此返工后的家具可能解决了前面出现的问题，但往往会出现透明度和光泽变化大或透明度和光泽不均匀的问题，严重影响套装产品的配套性，故客户对亚光清漆的重涂性能提出了明确的要求：要求重涂后透明度和光泽变化越小越好。  \n\n(2）重涂后透明度和光泽变化的原因亚光清漆是由树脂、消光粉、溶剂和助剂等组成，产品的透明度和光泽与产品配方密切相关，也与涂布时涂膜的厚度有直接的关系，涂膜越厚，透明度越差，涂膜厚度的变化也会导致光泽的变化。  \n\n由于重涂前不能完全将旧涂膜打磨掉，重涂后，相对于不重涂的合格产品，涂膜的厚度会增加，故会导致返工与不返工产品之间涂膜光泽和透明度的差异，对套装产品而言，这是不能接受的。如打磨不均匀，则单件产品本身的不同部位，也会出现涂膜的光泽和透明度不均匀的现象。  \n\n不同的亚光清漆产品由于配方不同，遇到上述问题而重涂后，透明度和光泽的变化程度也不同。  \n\n(3）亚光清漆重涂性的评价亚光清漆重涂性主要评价其重涂前后光泽和透明度的变化，从而筛选出变化小、重涂性好的产品。  \n\n涂膜的光泽已经有成熟的测试方法和仪器，分别测定重涂前后的涂膜的光泽，即可计算出其光泽的变化率。但是，亚光清漆产品重涂前后透明度变化的测定就没有既定的检验方法和标准。下面所述是木家具涂装中特有的新方法。  \n\n（1）测试原理及评价在相同的底材（透明聚酯膜）上涂布相同湿膜厚度的涂料，干后，用反射率测定仪测量涂膜的反射率，从而计算出对比率，对比率值越小，则透明度越好，反之亦然；在测试后的涂膜上重涂一次相同厚度的涂料，待干后，再用同样的方式测定重涂后涂膜的对比率，重涂前后对比率之差的绝对值越小，则重涂性越好。  \n\n（2）仪器及底材  \n\n$\\textcircled{1}$ 底材：底材采用未经处理的无色透明聚酯膜（耐溶剂好，透明度好，批次之间基本没有透明度差别)，厚度为 $30\\sim50\\mu\\mathrm{m}$ ，尺寸不小于 $100\\mathrm{mm}\\times150\\mathrm{mm}$ 。  \n\n$\\textcircled{2}$ 涂膜涂布器： $400\\mu\\mathrm{m}$ 的漆膜涂布器。  \n\n$\\textcircled{3}$ 反射率测定仪：一台精度 $0.1\\%$ 的反射率测定仪。  \n\n$\\textcircled{4}$ 岩田2号杯。  \n\n$\\textcircled{5}$ 秒表。  \n\n(3）试验方法  \n\n$\\textcircled{1}$ 底材的准备在至少 $\\mathfrak{f m m}$ 厚的平玻璃板上，滴几点 $200^{\\#}$ 溶剂汽油，将聚酯膜铺展在上面。 $200^{\\#}$ 溶剂汽油的表面张力使聚酯膜紧贴在玻璃板上面。不能弄湿聚酯膜的上表面，在聚酯膜与玻璃板之间不能存留气泡。必要时可用洁净白绸布指拭聚酯膜表面将聚酯膜与玻璃板之间的气泡消除。  \n\n$\\textcircled{2}$ 试板制备将亚光清漆产品按规定的施工配比配制，并将其黏度调整到： $(20\\pm1)\\:s$ （岩田2号杯，温度 $25^{\\circ}\\mathrm{C})$ 。配好产品后，用 $400\\mu\\mathrm{m}$ 的涂膜涂布器在聚酯膜上均匀涂布一遍，并将涂过漆的聚酯膜固定在平整的表面上，在水平条件下干燥。  \n\n$\\textcircled{3}$ 干燥条件试板应在温度 $(23\\pm2)^{\\circ}C$ 和相对湿度（ $(65\\pm5)\\%$ 的条件下至少干燥 $24\\mathrm{h}$ 才可进行反射率测定。  \n\n$\\textcircled{4}$ 首涂对比率的测定在反射率测定仪的黑、白陶瓷板上，滴上几滴 $200^{\\#}$ 溶剂汽油，从玻璃板上取下干燥好的试板，使其紧贴在黑、白陶瓷板上，不能弄湿测试样板的上表面，在试板与黑、白陶瓷板之间不能存留气泡。然后分别在紧贴黑、白陶瓷板的试板上至少6个位置上测量试板的反射率，记为 $R_{\\mathrm{B}}$ (黑板）、 $R_{\\mathbb{W}}$ （白板)，分别去除所录数据的最大值和最小值后，取余下四个数值的平均值，再计算每张试板的首涂对比率 $R_{\\mathrm{B}}/R_{\\mathrm{W}}$ 0  \n\n$\\textcircled{5}$ 重涂对比率的测定按 $\\textcircled{1}\\sim\\textcircled{2}$ 的方式在测完对比率的试板上，重涂一次，再按 $\\textcircled{3}\\sim$ $\\textcircled{4}$ 的要求进行试板的干燥和对比率的测试。  \n\n$\\textcircled{6}$ 结论分别计算首涂和重涂的对比率，评价自身的透明度；计算首涂和重涂的对比率之差，并取绝对值，评价重涂性，并得出结论。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 678,
+        "chunk": "# 4.木用涂料产品中控过程中的几个特别项目  \n\n在质检中控过程中，木用涂料产品的受控指标有十几个之多，如果不能有效中控，无疑会产生大量的返工产品及不合格品，加大库存量。  \n\n下面几项中控项自是由实际总结得出：  \n\n（1）PU亚光清漆之外观、光泽的中控  \n\n$\\textcircled{1}$ ①外观在质检的过程中，漆膜的外观很好，自然没有问题。但如果外观出现异常，就必须判断是涂料本身问题，还是制板过程中外来因素的影响。例如，PU亚光清漆的测试板出现微粒时，是亚光清漆本身问题，还是外来粉尘，就往往难下结论。  \n\n$\\textcircled{2}$ 解决办法找一同型号产品的合格留样，与被测样同时、同条件制板并作平行测试对比测试结果，较易得出正确结论。  \n\n$\\textcircled{3}$ 结果分析按上述方式进行检测，可能出现的结果及相应的分析判定见表3-7-155。  \n\n表3-7-155 测试结果分析  \n\n\n<html><body><table><tr><td rowspan=\"2\">试样</td><td colspan=\"4\">结果</td></tr><tr><td>A</td><td>B</td><td>C</td><td>D</td></tr><tr><td>留样</td><td>好</td><td>好</td><td>不好</td><td>不好</td></tr><tr><td>被测样</td><td>好</td><td>不好</td><td>好</td><td>不好</td></tr><tr><td>结论</td><td>好(合格)</td><td>不好（不合格）</td><td>好(合格)</td><td>待定（见备注2)</td></tr><tr><td>准确度/%</td><td>100</td><td>100</td><td>100</td><td></td></tr><tr><td>备注</td><td colspan=\"4\">如出现结果C时，可判被测样合格，但需进一步确认留样的质量是否发生了变化 如出现结果D时，不能直接判定被测样的质量好坏，需重复测试一次确认留样的质量是否发 生了变化，如留样质量变坏，则判被测样不合格；如留样质量没有变坏，则需进一步对比留样和 被测样试板上微粒的严重程度，如被测样的试板上微粒更严重，则判被测样不合格，否则，判被 测样合格</td></tr></table></body></html>  \n\n讨论：以上方法在工作量不增加太多的前提下，使人们的判断更快、更准确。  \n\nPU亮光清漆、亮光色漆在同样问题上可用同样方法去解决。但亮光产品有一个细度项目可供佐证，亮光产品细度小，如细度合格，则试样的外观微粒就有很大可能来自环境，判断就容易了。亚光漆则不然，本身细度较大，难以做出以上对比。因此，上述方法对亚光产品都是极好的针对性措施，故以亚光清漆为例。另一个要留意的问题是，留作平行样的合格留样，要确保合格并定期更新。  \n\n亚光清漆的光泽本身较低，检测时如产生相同的绝对误差，其相对误差比亮光漆大很多。因此，其准确性尤显重要。  \n\n$\\textcircled{1}$ 被测板的光泽，除了配方原因外，还与膜厚、漆膜干燥过程的温、湿度、通风条件有关。$\\textcircled{2}$ 严格控制上述过程，并在相同条件下用不同批次的产品同步制板，同步检测，使误差缩小并易于判断，利于有效中控。  \n\n(2）PU亚光清漆的贮存稳定性  \n\n$\\textcircled{1}$ 做配方过程的贮存稳定性数据只作参考。大生产的留样，贮存期满后一定要进行复检（尽管产品已售出)。如发现严重问题，停止大生产，返回中试或小试程序，重调配方或工艺。  \n\n$\\textcircled{2}$ 贮存稳定性的检测项目包括：防沉性、防结块、返粗情况。亚光清漆在贮存时的轻度沉淀、分层是允许的，但一定要分清哪一种情况最终会影响涂料的使用。  \n\n(3）水性木器漆水性木器漆的漆膜经常会出现缩孔。检测中有一个现象，刚生产好的产品立即送样检测，无缩孔。但同一样品，静置一天后再检测，可能会出现缩孔，原因不明。为稳妥起见，建议水性木器漆的产品，静置一二天后再进行缩孔试验。注意找出规律和真正原因。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 679,
+        "chunk": "# 六、木用涂料生产、施工、成膜后的有害物质标准及测试方法  \n\n在我国绿色化学成为发展方向的今天，涂料领域发展的主要趋势是减少溶剂的使用，以制造更高固体分的涂料和以水为主要挥发性组分的涂料。但水性涂料还不能完全取代溶剂型涂料，在涂料产业中，溶剂型涂料的生产仍占有绝大部分比例。  \n\n针对溶剂型木用涂料的环境问题，2001年我国颁布了装饰装修用溶剂型木器涂料有害物质限量的国家强制性标准（GB18581—2001），对VOC、苯类溶剂、游离TDI和可溶性重金属含量做出了限制。为了提高涂料生产企业对溶剂型涂料往低毒、环保方向开发的积极性，又接着制定了相对环境行为较好的、对人体危害性相对较小的环境标志产品技术要求。不仅规定了有害物质限量要求，还明确规定了禁止人为添加的有害物质类别。",
+        "category": " Introduction"
+    },
+    {
+        "id": 680,
+        "chunk": "# 1.木用涂料在生产过程中的有害物质控制  \n\n为了满足强制性国家标准和环境标志产品技术要求，在木用涂料的生产过程中，禁止人为添加如下物质。  \n\n$\\textcircled{1}$ 乙二醇醚及其酯类，主要包括乙二醇甲醚、乙二醇甲醚醋酸酯、乙二醇乙醚、乙二 醇乙醚醋酸酯、二乙二醇丁醚醋酸酯。  \n\n$\\textcircled{2}$ 邻苯二甲酸酯类，主要包括邻苯二甲酸二异辛酯（DEHP)、邻苯二甲酸二正丁酯(DBP)、邻苯二甲酸丁苄酯（BBP)、邻苯二甲酸二异壬酯（DINP)、邻苯二甲酸二辛酯(DOP)。  \n\n$\\textcircled{3}$ 正己烷。  \n\n$\\textcircled{4}$ 异佛尔酮（3，5，5-三甲-2-甲-环己烯基-1-酮)。  \n\n$\\textcircled{5}$ 苯。  \n\n$\\textcircled{6}$ 卤代烃，主要包括二氯甲烷、二氯乙烷、三氯甲烷、三氯乙烷、四氯化碳。  \n\n$\\textcircled{7}$ 可溶性重金属及其化合物，主要包括可溶性铅、可溶性镉、可溶性铬、可溶性汞及其化合物。重金属化合物主要来源于涂料生产用原材料中的颜料及某些助剂。  \n\n近年来，各国都在控制或禁止重金属及其化合物的使用，如欧共体生态标准99/10/EC规定：不准使用镉、铅、铬（V）、汞、砷及其化合物；德国“蓝色天使”标准（Low-Pol-lutantVarnishes.Januaryl997）规定：不得使用含铅、镉、铬（V）及其化合物作为原料中的杂质，铅 $\\leq0.02\\%$ 0  \n\n$\\textcircled{8}$ 甲醇。  \n$\\textcircled{9}$ 甲醛及甲醛的聚合物。",
+        "category": " Introduction"
+    },
+    {
+        "id": 681,
+        "chunk": "# 2.木用涂料在施工过程中的有害物质  \n\n木用涂料在施工过程中会释放出挥发性有机化合物，挥发性有机化合物会对环境产生污染并加大室内有机污染物的负荷，严重时会使人引起头疼、咽喉痛等症状，危害人体健康。根据涂料中挥发性有机化合物的挥发特性，按照施工状态可把挥发过程简单地划分为两阶段，第一阶段为“湿”阶段，在此阶段内挥发速率极快，在数小时内即可挥发出总量的$90\\%$ 以上；第二阶段为“干”阶段，此阶段内挥发速率大大降低，并逐渐减少。所以在“湿”阶段要特别注意施工环境的通风及人员的防护。由于这一挥发特性，施工后的涂膜经一星期养护后，挥发出的有机化合物就极少了。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 682,
+        "chunk": "# 3.木用涂料在成膜后的有害物质  \n\n木用涂料在成膜后的有害物质主要是可溶性重金属及其化合物，以及残留的、未曾挥发完的极少量的挥发性有机化合物。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 683,
+        "chunk": "# 4.木用涂料的有害物质限量标准  \n\n为了减少溶剂型木器涂料对使用者和环境的不良影响，2001年我国颁布实施了国家强制性标准GB18581—2001《室内装饰装修材料溶剂型木器涂料中有害物质限量》，该标准已于2008年进行修订；2006年颁布了推荐性环境保护行业标准HJ/T303—2006《环境标志产品技术要求家具》；2007年颁布了推荐性环境保护行业标准HJ/T414——2007《环境标志产品技术要求室内装饰装修用溶剂型木器涂料》；2008年制定并报批了国家强制性标准《室内装饰装修材料水性木器涂料中有害物质限量》。现简单介绍上述标准的主要内容。  \n\n(1）GB18581—2001《室内装饰装修材料溶剂型木器涂料中有害物质限量》GB18581—2001标准规定了室内装饰装修用硝基漆类、聚氨酯类和醇酸漆类木器涂料中对人体有害物质容许限值的技术要求、试验方法、检验规则、包装标志、安全涂装及防护等内容。它适用于室内装饰装修用溶剂型木器涂料（即以有机物作为溶剂的木器涂料)，其他树脂类型和其他用途的室内装饰装修用溶剂型涂料可参照使用。该标准不适用于水性木器涂料。其有害物质限量要求详见表3-7-156。  \n\n表3-7-156GB18581—2001《室内装饰装修材料溶剂型木器涂料中有害物质限量》  \n\n\n<html><body><table><tr><td colspan=\"2\" rowspan=\"2\">项 目</td><td colspan=\"3\">限 量值</td></tr><tr><td>聚氨酯类涂料</td><td>硝基类涂料</td><td>醇酸类涂料</td></tr><tr><td colspan=\"2\">挥发性有机化合物（VOC)含量/（g/L) ≤</td><td>光泽(60°)≥80，600 光泽(60°)<80，700</td><td>≤750</td><td>≤550</td></tr><tr><td colspan=\"2\">苯含量/% ≤</td><td colspan=\"3\">0.5</td></tr><tr><td colspan=\"2\">甲苯和二甲苯总和/% ≤</td><td>40</td><td>45</td><td>10</td></tr><tr><td colspan=\"2\">游离甲苯二异氰酸酯含量/%</td><td>0.7</td><td></td><td></td></tr><tr><td rowspan=\"4\">重金属（限色漆）/(mg/kg） ≤</td><td>可溶性铅</td><td colspan=\"3\">90</td></tr><tr><td>可溶性镉</td><td colspan=\"3\">75</td></tr><tr><td>可溶性铬</td><td colspan=\"3\">60</td></tr><tr><td>可溶性汞</td><td colspan=\"3\">60</td></tr></table></body></html>\n\n$\\textcircled{1}$ 按产品规定的配比和稀释比例混合后测定。如稀释剂的使用量为某一范围时，应按照推荐的最大稀释量稀释后进行测定。$\\textcircled{2}$ 如产品规定了稀释比例或由双组分组成时，应分别测定各组分中的含量，再按产品规定的配比计算混合后涂料中的总量。如稀释剂的使用量为某一范围时，应按照推荐的最大稀释量进行计算。$\\textcircled{3}$ 如聚氨酯漆类规定了稀释比例或由双组分组成时，应先测定固化剂（含甲苯二异氰酸酯预聚物）中的含量，再按产品规定的配比计算混合后涂料中的含量。如稀释剂的使用量为某一范围时，应按照推荐的最小稀释量进行计算。  \n\n2008年全国涂料和颜料标委会组织修订了GB18581，对其中的范围、项目、限量值、测试方法都进行了修订，其报批稿中确定的适用范围是：该标准适用于室内装饰装修和工厂化涂装用聚氨酯类、硝基类和醇酸类溶剂型木器涂料（包括底漆和面漆）及各类溶剂型腻子。不适用于辐射固化涂料和PE腻子。其有害物质限量要求详见表3-7-157。  \n\n表3-7-157GB18581报批稿中有害物质限量的要求  \n\n\n<html><body><table><tr><td rowspan=\"2\" colspan=\"2\">项 目</td><td colspan=\"2\">限</td><td rowspan=\"2\">量 值</td><td colspan=\"2\"></td></tr><tr><td>聚氨酯类涂料</td><td>硝基类</td><td>醇酸类</td><td>腻子 (不适于PE腻子)</td></tr><tr><td colspan=\"2\">挥发性有机化合物(VOC）含量/(g/L)</td><td>面漆 光泽(60°)≥80，≤580；</td><td>底漆 ≤670</td><td>涂料 ≤720</td><td>涂料 ≤500</td><td>≤550</td></tr><tr><td colspan=\"2\">苯/%</td><td colspan=\"2\">光泽(60°)<80,≤670</td><td>≤0.3</td><td></td><td></td></tr><tr><td colspan=\"2\">甲苯、二甲苯、乙苯总和/%</td><td colspan=\"6\"></td></tr><tr><td colspan=\"2\">游离二异氰酸酯总和（TDI+HDI/%</td><td colspan=\"2\">≤30 ≤0.4</td><td>≤30</td><td>≤5 一</td><td>≤30</td></tr><tr><td colspan=\"2\">甲醇/%</td><td colspan=\"2\"></td><td>≤0.3</td><td></td><td>≤0.3(限硝基类腻子）</td></tr><tr><td colspan=\"2\">卤代烃/%</td><td colspan=\"6\"></td></tr><tr><td rowspan=\"5\">重金属（限色漆，腻子和醇 酸清漆）/（mg/kg）</td><td>可溶性铅</td><td colspan=\"6\">≤0.1</td></tr><tr><td>可溶性</td><td colspan=\"6\">≤90</td></tr><tr><td></td><td colspan=\"6\">≤75</td></tr><tr><td>可溶性铬</td><td colspan=\"6\">≤60</td></tr><tr><td>可溶性汞</td><td colspan=\"6\">≤60</td></tr></table></body></html>\n\n$\\textcircled{1}$ 按产品规定的配比和稀释比例混合后测定。如稀释剂的使用量为某一范围时，应按照推荐的最大稀释量稀释后进行测定。$\\textcircled{2}$ 如聚氨酯漆类规定了稀释比例或由双组分或多组分组成时，应先测定固化剂（含游离二异氰酸酯预聚物）的含量，再按产品规定的配比计算混合后涂料中的含量。如稀释剂的使用量为某一范围时，应按照推荐的最小稀释量进行计算。$\\textcircled{3}$ 包括二氯甲烷、二氯乙烷（1,1-二氯乙烷，1,2-二氯乙烷）、三氯甲烷（1,1,l-三氯甲烷，1,1,2-三氯甲烷）、三氯乙烷、四氯化碳。  \n\n(2）GB24410—2009《室内装饰装修材料水性木器涂料中有害物质限量》2008年全国涂料和颜料标委会组织起草了《室内装饰装修材料水性木器涂料中有害物质限量》强制性国家标准，并已于2008年9月完成报批，该标准规定了室内装饰装修用水性木器涂料和木器用水性腻子中对人体和环境有害的物质容许限量要求、试验方法、检验规则、包装标志、涂装安全及防护等内容，它适用于室内装饰装修和工厂化涂装用水性木器涂料以及木器用水性腻子。该标准的有害物质限量要求详见表3-7-158。  \n\n表3-7-158《室内装饰装修材料 水性木器涂料中有害物质限量要求》  \n\n\n<html><body><table><tr><td colspan=\"3\">项 目</td><td colspan=\"2\">限量值</td></tr><tr><td colspan=\"3\"></td><td>涂料</td><td>腻子</td></tr><tr><td colspan=\"3\">挥发性有机化合物含量 ≤ 苯系物（苯、甲苯、乙苯和二甲苯总和)/(mg/kg) ≤</td><td>300g/L</td><td>60g/kg</td></tr><tr><td colspan=\"3\">乙二醇醚及其酯类(乙二醇甲醚、乙二醇甲醚醋酸酯、乙二醇乙醚、乙二醇乙醚醋酸酯、二</td><td colspan=\"2\">300</td></tr><tr><td colspan=\"3\">乙二醇丁醚醋酸酯总和）/（mg/kg） ≤</td><td colspan=\"2\">300</td></tr><tr><td colspan=\"3\">游离甲醛/（mg/kg)</td><td colspan=\"2\">≤ 100</td></tr><tr><td rowspan=\"4\">可溶性重金属（限色漆和腻子)/(mg/kg） ></td><td colspan=\"2\">铅</td><td colspan=\"2\">90</td></tr><tr><td colspan=\"2\">≤</td><td colspan=\"2\">75</td></tr><tr><td colspan=\"2\">铬</td><td colspan=\"2\">60</td></tr><tr><td colspan=\"2\">汞</td><td colspan=\"2\">60</td></tr></table></body></html>\n\n$\\textcircled{1}$ 对于双组分或多组分组成的涂料，应按产品规定的配比混合后测定。水不作为一个组分，测定时不考虑稀释配比。  \n\n(3）HJ/T414—2007《环境标志产品技术要求室内装饰装修用溶剂型木器涂料》该标准于2007年12月发布，2008年4月实施。该标准规定了室内装饰装修用溶剂型木器涂料环境标志产品的定义和术语、基本要求、技术内容和检验方法，它适用于室内装饰装修用的硝基类、聚氨酯类、醇酸类溶剂型面漆和底漆。不适用于辐射固化类涂料。  \n\n$\\textcircled{1}$ 该标准中列出的禁用物质详见表3-7-159。  \n\n表3-7-159HJ/T414—2007中禁用物质清单   \n\n\n<html><body><table><tr><td>禁用种类</td><td>禁用 物质</td></tr><tr><td>乙二醇醚及其酯类</td><td>乙二醇甲醚、乙二醇甲醚醋酸酯、乙二醇乙醚、乙二醇乙醚醋酸酯、二乙二醇丁醚醋酸酯</td></tr><tr><td>邻苯二甲酸酯类</td><td>邻苯二甲酸二正丁酯(DBP)、邻苯二甲酸二辛酯(DOP)</td></tr><tr><td>烷烃类</td><td>正己烷</td></tr><tr><td>酮类</td><td>3,5，5-三甲基-2-环己烯基-1-酮（异佛尔酮)</td></tr><tr><td>卤代烃类</td><td>二氯甲烷、二氯乙烷、三氯甲烷、三氯乙烷、四氯化碳</td></tr><tr><td>芳香烃</td><td>苯</td></tr><tr><td>醇类</td><td>甲醇</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 该标准中有害物质限量要求详见表3-7-160。  \n\n表3-7-160HJ/T414—2007《涂料中有害物质限量要求》  \n\n\n<html><body><table><tr><td colspan=\"2\" rowspan=\"2\">项 目</td><td colspan=\"2\">硝基类溶剂型涂料</td><td colspan=\"3\">聚氨酯类溶剂型涂料</td><td colspan=\"2\">醇酸类溶剂型涂料</td></tr><tr><td>面漆</td><td>底漆</td><td>面漆</td><td>面漆</td><td>底漆</td><td>色漆</td><td>清漆</td></tr><tr><td colspan=\"2\">光泽（人射角60°）/%</td><td></td><td></td><td>≥80</td><td><80</td><td></td><td>一</td><td></td></tr><tr><td colspan=\"2\">VOC/(g/L) ≤</td><td colspan=\"2\">700</td><td>550</td><td>650</td><td>600</td><td>450</td><td>500</td></tr><tr><td colspan=\"2\">苯（质量分数）/% ≤</td><td colspan=\"7\">0.05</td></tr><tr><td colspan=\"2\">甲苯十二甲苯十乙苯（质量分数)/%</td><td colspan=\"7\">25 25</td></tr><tr><td rowspan=\"4\">可溶性重金属/（mg/kg） ≤</td><td rowspan=\"4\">铅(Pb) 镉（Cd) 铬(Cr) 汞（Hg) 固化剂中游离甲苯二异氰酸酯(TDI)（质量分</td><td colspan=\"5\" rowspan=\"2\">90 75</td><td rowspan=\"2\"></td><td rowspan=\"2\">5</td></tr><tr><td></td></tr><tr><td></td><td></td><td>60 60</td><td></td><td></td></tr><tr><td colspan=\"2\">≤ 甲醇/（mg/kg） ≤</td><td>500</td><td colspan=\"2\">0.5</td><td colspan=\"2\"></td></tr></table></body></html>\n\n$\\textcircled{1}$ 按产品规定的配比和稀释比例混合后测定。如稀释剂的使用量为某一范围时，应按照推荐的最大稀释量稀释后进行测定。$\\textcircled{2}$ 可溶性重金属测试仅限于色漆。  \n\n(4) $\\mathrm{GB}\\times\\mathsf{X X X}-\\mathsf{X X X X}$ 《玩具用涂料中有害物质限量》2008年全国涂料和颜料标委会组织起草了《玩具用涂料中有害物质限量》强制性国家标准，并已于2008年9月完成报批，该标准规定了玩具用涂料中对人体和环境有害的物质容许限量的要求、试验方法、检验规则和包装标志等内容，适用于各类玩具用涂料。该标准的有害物质限量要求详见表3-7-161。  \n\n(5）HJ/T303—2006《环境标志产品技术要求家具》该标准于2006年11月发布，2007年2月实施。该标准适用于室内家具与配件，包括可移动的、手提式或固定到墙壁上的家具与配件产品，用于布置房间的产品以及室内用的门。  \n\n标准中对涂料的有害物质限量如下。  \n\n表3-7-161玩具用涂料中有害物质限量要求  \n\n\n<html><body><table><tr><td colspan=\"2\">项 目</td><td>要求</td></tr><tr><td colspan=\"2\">铅含量/（mg/kg）</td><td>≤ 600</td></tr><tr><td rowspan=\"7\">可溶性元素/（mg/kg）</td><td>锑(Sb)</td><td>60</td></tr><tr><td>砷(As)</td><td>25</td></tr><tr><td>钡（Ba)</td><td>1000</td></tr><tr><td>镉(Cd)</td><td>75</td></tr><tr><td>铬（Cr)</td><td>60</td></tr><tr><td>铅(Pb)</td><td>90</td></tr><tr><td>汞（Hg)</td><td>60</td></tr><tr><td rowspan=\"4\">邻苯二甲酸酯类 ≤</td><td>硒（Se) 邻苯二甲酸二异辛酯(DEHP)、</td><td>500</td></tr><tr><td>邻苯二甲酸二正丁酯（DBP）和</td><td>0.1</td></tr><tr><td>邻苯二甲酸丁苄酯(BBP)总和 邻苯二甲酸二异壬酯(DINP)、</td><td></td></tr><tr><td>邻苯二甲酸二异癸酯（DIDP）和 邻苯二甲酸二辛酯(DOP)总和</td><td>0.1</td></tr><tr><td colspan=\"2\">挥发性有机化合物（VOC)含量/（g/L）</td><td>720</td></tr><tr><td colspan=\"2\">苯/%</td><td>≤ ≤ 0.3</td></tr><tr><td colspan=\"2\">甲苯、乙苯和二甲苯总和/%</td><td>30</td></tr></table></body></html>  \n\n$\\textcircled{1}$ 按产品明示的配比混合各组分样品，并制备厚度适宜的涂膜。在产品说明书规定的干燥条件下，待涂膜完全干燥后，对干涂膜进行测定。粉末状涂料直接进行测定。  \n\n$\\textcircled{2}$ 液体样品，先按规定的方法测定其含量，再折算至干膜中的含量。粉末状涂料或于涂膜样品，按规定的方法测定其含量。  \n\n$\\textcircled{3}$ 仅适用于溶剂型涂料。按产品明示的配比和稀释比例混合后测定。如稀释剂的使用量为某一范围时，应按照推荐的最大稀释量稀释后进行测定。  \n\n$\\textcircled{1}$ 木质材料使用的水性木器漆必须达到HJ/T201—2005《环境标志产品技术要求水性涂料》的要求。  \n\n$\\textcircled{2}$ 产品中不得添加含有以下物质的颜料、胶黏剂和添加剂：卤代有机物、邻苯二甲酸酯、可分解成致癌芳香胺的偶氮类化合物、铅、锡、镉、六价铬、汞及其化合物。  \n\n木质材料使用的溶剂型涂料应满足的表3-7-162要求。  \n\n表3-7-162 木质材料使用的溶剂型涂料的有害物质限量要求  \n\n\n<html><body><table><tr><td>项 目</td><td colspan=\"2\">限 值</td></tr><tr><td>VOC</td><td>光泽（60°)≥80;550g/L</td><td>光泽（60°)<80,650g/L</td></tr><tr><td>苯</td><td colspan=\"2\">不得人为添加，由原材料中带入的苯的含量应小于2000mg/kg</td></tr><tr><td>甲苯、二甲苯、卤代烃</td><td colspan=\"2\">不得人为添加，由原材料中带人的甲苯和二甲苯的总含量应小于200000mg/kg，原材料 中带人的卤代烃的总含量应小于20000mg/kg</td></tr><tr><td>重金属</td><td colspan=\"2\">不得人为添加，由原材料中带入的铅、镉、六价铬、汞、砷及其化合物，由原材料中带人的 重金属总含量应小于500mg/kg</td></tr><tr><td>游离异氰酸酯（TDI或HDI） 含量</td><td colspan=\"2\">聚氨酯漆中游离异氰酸酯（TDI或HDI)含量应小于5000mg/kg</td></tr></table></body></html>\n\n$\\textcircled{1}$ 按产品规定的配比和稀释比例混合后测定。如稀释剂的使用量为某一范围时，应按照推荐的最大稀释量稀释后进行测定。： $\\textcircled{2}$ 如产品规定了稀释比例或产品有双组分或多组分组成时，应分别测定稀释剂和各组分中的含量，再按产品规定的配比计算混合后涂料中的总量。如稀释剂的使用量为某一范围时，应按照推荐的最大稀释量进行计算。$\\textcircled{3}$ 如产品规定了稀释比例或产品有双组分或多组分组成时，应先测定固化剂中的含量，再按产品规定的配比计算混合后涂料中的总量，如稀释剂的使用量为某一范围时，应按照推荐的最小稀释量进行计算。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 684,
+        "chunk": "# 5.木用涂料的有害物质限量标准中各指标项的测试方法  \n\n上述国家标准和行业标准中涉及的指标项，其中有些已有相当成熟的检验方法，并以推荐性国家标准或行业标准的形式发布实施，有些还没有相应的国家标准或行业标准的检验方法，但在相应的限量标准中有详细的介绍，具体情况详见表3-7-163。  \n\n表3-7-163检测项目与检测方法标准对照  \n\n\n<html><body><table><tr><td>项 目</td><td>标准代号和名称</td><td>备 注</td></tr><tr><td>游离甲苯二异氰酸酯(TDI)</td><td>GB/T18446—2001气相色谱法测定氨基甲酸酯预聚物和涂 料溶液中未反应的甲苯二异氰酸酯（TDI）单体</td><td></td></tr><tr><td>游离二异氰酸酯总和（TDI+HDI)</td><td>GB/T18446—2009《色漆和清漆用漆基- 一异氰酸酯树脂中 单体二异氰酸酯的测定》</td><td>2008年报批</td></tr><tr><td>游离甲醛</td><td>GB18582—2008中附录C</td><td></td></tr><tr><td>可溶性重金属</td><td>GB18582—2008中附录D</td><td></td></tr><tr><td>其他项目</td><td>按相应有害物质限量标准中方法进行</td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>第八节 木用涂料与涂装的发展</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 685,
+        "chunk": "# 一、家具的发展  \n\n中国是家具生产大国，但不是家具生产的强国。中国家具设计风格混乱，受外国影响大，民族的东西还没有建立起来，家具业十分注意并努力解决这个问题。2009年，家具业身处国际金融风暴的漩涡之中，出口订单锐减，行业格局大变，市场前景动荡，家具业在发展中正在寻找自己的方向，未来5～10年，家具业不再以量的扩张，而是以质的提高为主要特征。家具产品差异化要加强，少品种、大批量会变成多品种、小批量，由粗放型的发展向自主创新型转变。中国家具业是本土轻工业的一根主要支柱，家具业的今天，成绩斐然，家具业的明天，依然会光辉灿烂。同时也一定会对涂料行业提出更高的要求。  \n\n涂料业作为家具业的服务行业，在上述形势下，一定要适应家具业的变化，处理好家具设计与涂料涂装、家具制造与涂料涂装这个重要的关系。",
+        "category": " Introduction"
+    },
+    {
+        "id": 686,
+        "chunk": "# 二、底材应用  \n\n中纤板、刨花板这些符合环保方向的产品，在努力减少游离甲醛的基础上，前景看好，需求量大。发展软木家具势在必行。松、杉、柏、桧这类软木，还有桐、枫这类软硬中间的材料，其在家具上的应用日益增多，尤以松木制品为最，这是有战略意义的。涂料与涂装在适应软木家具制作方面正在不断努力。能把软木变硬木，就能进一步解决木材画乏的问题。木材学的专家已经做了很多工作。  \n\n贴纸会继续保持在低端。实木包括红木会发展在中、高端，但会受资源制约。木质贴面材料始终是最好的方向，很环保，很适合不同种类家具的使用，能够通过与涂料和涂装的结合，把各种风格、效果充分展示出来。科技木的应用使贴面材料更具发展空间。",
+        "category": " Introduction"
+    },
+    {
+        "id": 687,
+        "chunk": "# 三、木用涂料的发展  \n\n虽然NC涂料固含量低，溶剂挥发量大，不太符合环保要求，耐候性不太好，不能户外使用，但其优良的综合性能、优异的性价比，便捷的施工性能使这个品种保持生机。未来一段时间NC涂料不会被淘汰，仍将在家具、美式涂装、家装领域中发挥重要作用。如能在减少苯类溶剂使用、提高固体含量方面取得进步就更好。世界木器涂料中NC漆的现状及发展大体也是如此，在美式家具、家装方面前景不错。  \n\n双组分PU涂料是木用涂料的主力，在中国，PU双组分涂料的高需求及使用起码能保持20年以上，只有水性涂料的发展才有可能代替它。  \n\n双组分PU涂料用固化剂，国内自产仍然是主要渠道，有效地降低游离TDI的含量是固化剂的当务之急。  \n\n双组分PU涂料在配方和应用上的另一个大问题是干燥速度。涂料生产厂家迫于用户要求，不断地采用各种手段去提高PU漆的干燥速度，由此带来涂装过程中的很多问题，例如：发白、离层、暗泡、渗陷、开裂。被动地去解决这些问题，难度很大，效果不佳。相对比国外的木用涂装，我国的漆病从种类到程度都超出常见范围。双组分PU涂料的干燥速度，从目前情况来看，已经到了不能再快的时候了。想要再加快干燥速度，提高生产效率的同时又要减少漆膜缺陷，保证涂装质量，唯一途径是使用低温烘烤设备。“统一干燥条件，控制干燥速度”是双组分PU涂料发展要遵循的一个方向。  \n\nUPE涂料应该发挥在底漆中的优势，在高档家具中应用会越来越多。UV木用涂料，在技术进步的支持下，如新的（UV-PU）双固化体系的研发，UV生产线的不断改进，UV漆的发展会有新的高潮。  \n\n植物油改性产品在木用涂料中以新军姿态出现，它符合保护环境、贴近自然、追求淡雅效果的要求。用各种方法改性的植物油，多制成单组分的木用产品，这些产品易被木质材吸收，渗透性好，干膜较薄又光泽柔和，表现油润但不臃肿。用简易方法（如擦涂）涂装，可涂布出极具本色的高雅效果。改性植物油的产品，在家具家装、室内户外等木制品的应用上前景不可小靓。  \n\n水性木用涂料在国内发展至今，仍然处在起步阶段。它的进一步发展，要视未来政府环保法规对溶剂型涂料有无更严格的限制 $\\sin^{2}=$ 要看水性木用涂料本身性价比的提高，还要看家具购买者对用水性木用涂料涂装的家具有无更高认知及迫切需求。  \n\n水性木用涂料在中国的发展，还受到另一个条件的制约，这就是它的干燥状态受环境因素的影响。在自然条件下，干燥气候对水性木用涂料的成膜过程非常有利。但在国内，情况不太理想。就气候环境而言，对水性木用涂料的应用条件，渤三角地区最好，长三角地区居中，珠三角地区最差。理想的干燥条件如西北地区，经济总量不够。家具制造业最发达的珠江三角洲、长江三角洲，气候条件又不理想。水性木用涂料在中国的应用推广，注定要比溶剂型涂料面临更多的问题。 ？  \n\n一如果能使用低温烘烤设备，则上述的地区性差异将消失，极有利于水性涂料在木用领域的应用，这一点将对水性木用涂料在中国的发展起重要影响。  \n\n用于装修的木用涂料，尽管应用于所有场合，但都简称家装涂料。家装涂料脱胎于家具涂料，从最初把家具涂料中的合适产品用于装修，发展到后来特为家装设计、制造专用产品。家装涂料现在已发展出不少品种，但尚未形成系列。  \n\n家装涂料有两个变化值得注意：一是从刷涂向喷涂转移，以前现场施工全是刷涂，现在则尽量喷涂，喷不了才刷，当然总体上说还是刷涂多；二是木构件部分，包括壁柜、木线、隔断、墙裙等，从现场制作向工厂预制转移，其中包括木作和涂装。  \n\n这两个变化有一个共同特点，就是在这种情况下使用的涂料，从技术指标、特别是施工性能方面又返回去更接近于家具涂料。  \n\n从环保角度而言，家装涂料比家具涂料更严格，原因是它在现场制作时排放的有害气体很难收集、控制，装修现场投人使用之后有害物质的缓慢释放也被密切关注。  \n\n总之，家装涂料现处于初始发展阶段，要增加更多专用产品，技术指标、特别是施工性能要充分适应家装特点。硝基、水性是首选品种，双组分或单组分PU在家装上的应用前景很好。与家具涂料一样，家装涂料必须完成在专业化、系列化、规范化、标准化方面的蜕变才可能有生命力。以上一切，都要建立在遵循有关环保法规的基础之上。目前，家装涂料在市场上的实际用量十倍于家具涂料，对它的发展没有理由不给予足够的重视。  \n\n中国的木用涂料，与发达国家相比已很接近，但仍有差距，具体表现在：原料选用原则、配方设计基础、生产精细程度、施工应用水平。这几方面问题存在的原因是进行过程中自身技术水平不够、干扰因素太多所致。国内的木用涂料企业，经过十几年的发展，有些已到“瓶颈”阶段。木用涂料在中国一定会得到更大的发展，但以上所涉及的问题应当很好地解决。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 688,
+        "chunk": "# 四、木用涂装的发展  \n\n传统家具的真正价值不是在底材上，而是在工艺上。重视木用涂装，做好包括选用涂料、白坏制作、工艺设计、设备配套、涂装过程、质量控制的所有环节，才能通过涂装提升家具的附加值。  \n\n在涂料选用、底面配套方面坚持合理原则，不能只强调成本。涂装设备方面，各种涂装生产线的投人使用越来越多，越来越先进，包括UV涂装线，PU、NC自动涂装线，静电涂装线等。既有利于漆膜干燥，又有利于环保，将是涂装进步的有力保障。  \n\n涂装风格：在我国流行多年的地中海风格，即与美式涂装相比，漆膜稍厚、光泽稍高的效果，仍将受到欢迎并保持延续。亚光、简单美式涂装会继续发展。  \n\n木用涂装的发展面临最大的难题是涂装过程的控制。涂装环境本身已复杂多变，但又片面地追求涂装速度，随意加快漆膜干燥过程，是导致漆膜缺陷越来越多、产品返工量大的根本原因。要用各种办法，创造全天候的施工条件，让涂装过程、成膜过程变得理性和可控，才能最终降低综合成本。  \n\n“统一干燥条件、控制干燥速度”是涂料与涂装发展的保障。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 689,
+        "chunk": "# 五、综述  \n\n家具产品最终要向“美术化、实木化、高档化、个性化”方向发展，要能够把“人本性、安全性、环保性、智能性”充分体现在产品中。材料、木工、涂料、涂装、市场、法规，多种因素缺一不可。这是一个整体，只有把其中的每一个环节都做好，木用涂料和家具工业才能携手提升到新的高度。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 690,
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+        "category": " References"
+    },
+    {
+        "id": 691,
+        "chunk": "# 粉末涂料  \n\n粉末涂料的含义不仅在于粉末涂料的产品为粉末状态的，即使在涂装过程也是以粉末状态来使用的，只有在烘烤成膜时它才有一个熔融形成液态的过程。粉末涂料是没有挥发分的，成膜物为100%的涂料，理论上产品的利用率近乎100%；由于没有液态介质的挥发，没有环境污染，具有良好的生态环保性（ecology)；粉末涂料一次性就可形成较厚的涂层，涂覆简便，易进行流水线作业，成膜过程可控制在十几分钟以内，因而成膜效率非常地高，具有极高的生产效率（efficiency)；粉末涂料的力学性能和抗化学腐蚀性能优异，具有优异的涂膜性能（excellency）；粉末涂料的使用能够节约能源，节约资源，利用率可达99%，使用安全，具有突出的经济性（economy)；因此，人们称粉末涂料是具有“四E”性的涂料。  \n\n粉末涂料的发展始于20世纪50年代初期，由前联邦德国克纳萨克·格里塞恩公司于1952年发明了乙烯类树脂（PVC）的热塑性粉末涂料。随后聚乙烯（PE)、尼龙等热塑性粉末涂料相继问世。20世纪50年代后期，壳牌化学公司第一个研发出了热固性环氧粉末涂料，但由于分散均匀程度过差，性能并不理想。直到1962年，壳牌化学公司在英国和荷兰的实验室开发了挤出工艺，从而改善了其分散均匀性差的问题，该工艺沿用至今，依然是粉末涂料的最主要的生产工艺。早期的粉末涂料涂装是使用流化床装置，先将被涂工件预热，热工件在流化床中将雾化的粉末粒子熔结黏附于表面形成一定厚度的黏附层，再经烘烤熔融流平，形成连续的涂膜。1962年，第一台用于有机粉末涂料的静电涂装设备在法国诞生，这一发明对于高装饰性的热固性粉末涂料的使用和发展起到了关键作用，使得粉末涂料的涂层达到了“薄涂”的目的，而且涂层更加均匀。不仅如此，这一发明还给今后的美术型粉末涂料品种的开发和使用奠定了基础。  \n\n由于环氧树脂/双氰胺体系的粉末涂料涂层受紫外光辐射的影响，涂层在日光照射下很快粉化被破坏，加之其抗黄变性能较差，因而该体系粉末涂料只能用于户内，且在黄变性能要求不高的产品上使用。为克服以上问题，1970 年荷兰的ScadoBV公司和比利时的UCB公司相继开发了三聚氰胺/聚酯体系的粉末涂料，与此同时Huneke也发布了环氧和聚酯混合型树脂体系的粉末涂料的研究成果。而真正具有实际意义的技术突破是1971年荷兰的ScadoBV公司开发的使用端羧基聚酯树脂与双酚A型环氧树脂共混融的体系（混合型）和羧基聚酯与异氰脲酸三缩水甘油酯（TGIC）体系（纯聚酯型）的粉末涂料，这两种粉末涂料体系不仅克服了环氧树脂/双氰胺体系的不耐黄变和装饰性效果较差的问题，而且羧基聚酯/TGIC体系优异的户外耐久性使之成为最重要的户外使用的粉末涂料产品。时至今日，这两种体系的粉末涂料依然占有最重要的地位。同一时期，德国的Bayer公司和BASF公司开发了热固性丙烯酸树脂体系的粉末涂料，虽然在欧洲没能形成销售市场，但在日本得到了很好的发展和应用。20世纪80年代，羟基聚酯树脂/异氰酸酯体系的粉末涂料在美国和日  \n\n本市场形成了相应的规模。  \n\n我国是在70年代开始进行粉末涂料研发工作，发展较为缓慢，80年代是我国家用电器大发展的时期，在这一庞大的粉末涂料应用市场的激发下，于80年代后期国内通过引进外资、进口较先进的粉末涂料生产设备和应用设备，国内的粉末涂料开始进入规模化的发展。与此同时粉末涂料所使用的羧基聚酯也在进行国产化的发展，在这一阶段粉末涂料助剂（流平剂、TGIC固化剂等）也开始了工业化的发展。进人90年代后，我国的粉末涂料进人了高速发展的阶段，特别是在90年代后期，无论是粉末涂料的生产和使用方面，还是粉末涂料的原材料、生产设备以及粉末涂料的涂装设备方面的质量和技术日趋成熟，工业规模也迅速扩大。即使进人21世纪后国内的粉末涂料产量依然保持较快速度的增长，已成为全球最大的粉末涂料生产国。从国内的粉末涂料品种结构来看，环氧树脂/聚酯树脂混合型占 $53\\%$ ，聚酯树脂/TGIC型占 $23\\%$ ，聚酯树脂/羟烷基酰胺型占 $4\\%$ ，纯环氧型占 $19\\%$ ，其他体系为 $1\\%$  \n\n国内具有自主知识产权的粉末涂料和涂装技术非常少。虽然目前我国粉末涂料的产量居世界第一，然而产品质量和技术水平却不高。随着我国经济和科技水平的发展以及对环境保护要求的提高，粉末涂料的使用范围也会越加宽广，粉末涂料将向着低能耗、高性能、高附加值方向发展。",
+        "category": " Introduction"
+    },
+    {
+        "id": 692,
+        "chunk": "# 1.粉末涂料的分类  \n\n由于粉末涂料出现的时间和它的形态及使用时的特殊性，实际上它已是十八大类涂料以外的又一个特殊的类别了。粉末涂料以其主要成膜物的性质再分成热塑型和热固型两类；或以主要成膜物的种类分成聚乙烯型、环氧型、环氧聚酯混合型、聚酯型、聚氨酯型、丙烯酸型等；或以涂膜使用环境分为户内型、户外型等；或以涂膜外观分为消光型、高光型、美术型等。这些分类方法主要是在不同的情况下强调产品的性能和用途。粉末涂料的生产厂家一般还是以成膜物的种类分类，以方便产品的命名和管理。",
+        "category": " Introduction"
+    },
+    {
+        "id": 693,
+        "chunk": "# 2.热塑性树脂和热固性树脂的意义和特性  \n\n以热塑性树脂为主要成膜物的粉末涂料是热塑性粉末涂料；以热固性树脂为主要成膜物的粉末涂料是热固性粉末涂料，如图3-8-1所示。  \n\n![](images/8acbdc709420def00f2ab68f6f25844e5a613805f8f9171c159f402929fbd116.jpg)  \n图3-8-1 热塑性树脂和热固性树脂  \n\n![](images/948ef2cbbd725a8c62c99adea32bcc189c355cd068537125e5b49eebffc2d564.jpg)  \n\n以热塑性树脂（准确名称应称为聚合物，人们习惯称为树脂）为主要成膜物的粉末涂料称为热塑性粉末涂料。热塑性树脂具有加热熔化、冷却变硬（这一过程可重复进行）的特性，人们就是利用其这一特性来生产粉末涂料并使之成膜的。从理论上来讲，只要是玻璃化温度（指树脂由玻璃态向黏弹态转化时的温度，用T。表示）高于涂膜使用环境温度一定程度的热塑性树脂都可用于粉末涂料。然而由于粉末涂料加工工艺条件和成膜条件的限制，以及对涂膜性能的要求，对树脂的选用还是有相应要求的。对于热塑性粉末涂料来说，成膜树脂的分子量足够大和有一定高的结晶度时才能保证涂膜具有一定的机械强度，如此一来却给粉末涂料的生产和涂膜性能带来了一些缺点，如熔融温度高、颜料添加量小、着色力低、耐溶剂性差以及和金属的附着力差而必须使用底漆等。然而热塑性粉末涂料的制作和使用方法比较简单，成膜过程不涉及复杂的固化机理。有些产品的特殊性能，如聚氯乙烯产品具有柔润的手感和性价比、聚偏二氟乙烯产品的重防腐性和超耐候性、尼龙（聚酰胺）产品的耐磨性等，而使得一些产品在目前依然得到了很好的应用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 694,
+        "chunk": "# 一、乙烯基类粉末涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 695,
+        "chunk": "# 1.聚氯乙烯（PVC）粉末涂料  \n\n聚氯乙烯粉末涂料的主要成膜物是聚氯乙烯树脂，它的结构式为 $\\mathrm{\\longrightarrow}\\mathrm{CFI_{2}}\\mathrm{\\longrightarrow}\\mathrm{CHCl}\\mathrm{\\rightarrow}\\$ ，是由氯乙烯单体（VCM）通过自由基聚合而成的高分子化合物，是含有少量不完整晶体的无定形聚合物。常规商品PVC的玻璃化温度为 $80\\sim85^{\\circ}C$ ，无定形态密度（ $25^{\\circ}C$ ）为$1.385\\mathrm{g/cm^{3}}$ ，晶体密度（ $25\\%$ ）为 $1.52\\mathrm{g/cm^{3}}$ 。生产的PVC分子量一般在5万 ${\\sim}12$ 万，具有较大的多分散性，分子量随聚合温度的降低而增加，无固定熔点， $80\\sim85^{\\circ}C$ 开始软化，$130^{\\circ}C$ 变为黏弹态， $160{\\sim}180^{\\circ}\\mathrm{C}$ 开始转变为黏流态。有较好的力学性能，拉伸强度 ${\\mathfrak{f o m P a}}$ 左右，冲击强度 $5\\mathrm{\\sim}10\\mathrm{kJ/m^{2}}$ 。有优异的介电性能。PVC支化度较小，但对光和热的稳定性差，在 $100^{\\circ}C$ 以上或经长时间阳光曝晒，就会分解而产生氯化氢，并进一步自动催化分解，引起变色，物理力学性能也迅速下降，在实际应用中必须加人稳定剂以提高对热和光的稳定性。PVC材料在实际使用中经常加入稳定剂、润滑剂、辅助加工剂、色料、抗冲击剂及其他添加剂。PVC材料具有不易燃性、高强度、耐气候变化性以及优良的几何稳定性。PVC对氧化剂、还原剂和强酸都有很强的抵抗力。然而它能够被浓氧化酸如浓硫酸、浓硝酸所腐蚀并且也不适用与芳香烃、氯化烃接触的场合。PVC 在加工时熔化温度是一个非常重要的工艺参数，如果此参数不当将导致材料分解的问题。PVC的流动特性相当差，其工艺范围很窄。特别是大分子量的PVC材料更难以加工（这种材料通常要加入润滑剂改善流动特性)，因此通常粉末涂料使用的都是小分子量的PVC材料。PVC 的收缩率相当低，一般为$0.2\\%\\sim0.6\\%$ 。PVC的生产方法有悬浮聚合法、乳液聚合法和本体聚合法等，以悬浮聚合法为主，约占PVC总产量的 $80\\%$ 左右。单体的来源：乙烯法、石油法和电石法（我国的方法主要还是电石法)。树脂的质量以粒度和粒度分布、分子量和分子量分布、表观密度、孔隙度、鱼眼、热稳定性、色泽、杂质含量及粉末自由流动性等性能来表征。PVC对光、氧、热都不好，很容易发生降解，引起PVC制品颜色的变化，变化顺序为：白色 $\\twoheadrightarrow$ 粉红色 $\\nrightarrow$ 淡黄色 $\\nrightarrow$ 褐色 $\\twoheadrightarrow$ 红棕色 $\\nrightarrow$ 红黑色 $\\twoheadrightarrow$ 黑色。PVC树脂的脆性比较大，在粉末涂料生产时必须加入增塑剂以降低其脆性，从而改善涂膜的柔韧性和耐冲击性能。但同时也降低了涂膜的拉伸强度、模量和硬度。通过仔细选择增塑剂的种类和用量可以使硬度和柔韧度之间达到一个平衡点。增塑剂加量超过一定值时，将会影响粉末贮存的稳定性。增塑剂的种类有邻苯二甲酸酯类、磷酸酯类、脂肪族二元酸酯类、液态聚合物或低聚物和多元醇酯类等。增塑剂的选用要求具有与树脂高的相容性、低的挥发性、小的迁移性和油水抽出性，并能耐高低温、耐燃、无毒又价廉，往往单独使用一种增塑剂不能完全满足上述要求，所以在选用品种时要注意，有时可考虑两种增塑剂并用。PVC粉末涂料通常使用邻苯二甲酸二辛酯、邻苯二甲酸二异辛酯或链长在C15～C25的氯化石蜡作增塑剂。一般来说，分子量较小的增塑剂迁移性和渗性较强，对粉末涂料贮存稳定性的影响也较大；分子量较大的增塑剂增塑效率不太高，耐低温性相对较差。  \n\n由于PVC热稳定性差，它在空气下100℃时就开始有轻微降解，150℃时则降解加剧，放出能起进一步催化降解作用的氯化氢。如果不抑制氯化氢的产生则继续降解，直到聚氯乙烯大分子被裂解成各种小分子为止，因此对聚氯乙烯树脂来说必须添加适当的热稳定剂。热稳定剂按化学结构可分为碱式铅盐、金属皂类、有机锡、复合稳定剂等主稳定剂和环氧化物、亚磷酸酯等副稳定剂，主副稳定剂之间配合使用常能起到协同作用，通常在每百份树脂中加 $4\\sim5$ 份热稳定剂。无机铅盐稳定剂是最早的PVC有效热稳定剂，至今仍占重要地位，它们有廉价和有效的优点。但它又有硫污（与硫生成黑色PbS)、毒性的缺点。有机锡则有非硫污和制品透明的优点，硫醇锡对PVC有很高的稳定效果。钡/镉和钡/镉/锌复合稳定剂是当前重要的一类稳定剂，它们具有协同效应。所谓协同效应是指两种热稳定剂配合使用时的热稳定效果明显地大于各自单独使用时所能得到效果的总和。  \n\n在PVC粉末涂料的配方中经常添加润滑剂，它们不仅影响粉末涂料的加工行为而且还影响产品的性能。润滑剂的首要作用是提高被加工体系的熔融流动性，其次是在粉末涂料生产过程中降低物料与设备的摩擦，促进材料在挤出机中的输送。润滑剂分为内润滑剂和外润剂，内润滑剂一般是带有极性基的小分子有机化合物，它们能与PVC分子较好地相容，这些小分子能够均匀地分布于PVC分子结构单元之间，从而使得PVC分子间的移动更加容易，提高PVC物料的流动性，减小物料在摩擦和剪切时所产生的热量，消除融体温度的波动。内润滑剂有长链的脂肪酸、硬脂酸钙、烷基化脂肪酸和长链的烷基胺等。外润滑剂通常是无极性或者极性较低的有机化合物，熔点在 $60\\sim95^{\\circ}C$ 。其特点是烃链长，与PVC的相容性差。外润滑剂在一定温度和压力作用下融化并向熔体表面析出，并在融体与金属之间形成一种界膜，该界膜可以降低融熔物料对挤出设备的黏附力。外润滑剂有脂肪酸酯、合成蜡和低分子量聚乙烯等。还有一些物质具有内润滑剂和外润滑剂共同的作用，它们一般是含有极性基团、分子量相对较大的高级脂肪酸的衍生物，如某些高级脂肪醇等。外润滑的用量一般控制在PVC量的 $0.8\\%\\sim1.5\\%$ （包括稳定剂中的金属皂类)。外润滑用量过多会延长物料的塑化进程，降低生产效率；用量太少，易使涂膜发脆。内部润滑剂的选择使用应根据其他助剂以及挤出设备的具体情况灵活掌握，其加人量应少于外部润滑剂。  \n\nPVC粉末涂料配方要根据其应用技术要求，即外观、颜色、物理、化学性能来设计。一般要求PVC分子量在 $10000{\\sim}20000$ ，分子量太大，涂装工件预热温度就高，稳定剂的要求就高，选择合适稳定剂，是PVC粉末涂料生产的关键。  \n\n基本配比如下（质量份）：  \n\n<html><body><table><tr><td>聚氯乙烯</td><td>1000</td><td>抗氧剂</td><td>3~4</td></tr><tr><td>增塑剂</td><td>350~450</td><td>颜料、填料</td><td>100～300</td></tr><tr><td>热稳定剂</td><td>30～50</td><td></td><td></td></tr></table></body></html>  \n\n早期PVC粉末涂料的生产就是简单的物料混合过筛即可，这种方法虽然简单、设备投资少，但形成的涂膜效果不理想。随后采用的熔融挤出后再磨粉的方法现在依然在采用。由于PVC颗粒很难粉碎，常温粉碎难以达到较小的粒径，生产效率也不高，而目前所采用的深冷磨粉工艺很好地解决了这一问题。PVC粉末涂料基本生产过程如图3-8-2所示。  \n\n![](images/a43e5c55b82321a1bc1372f0b29e7dcd6cb96f0a1f962c45fdb55b2adc358d9f.jpg)  \n图3-8-2PVC粉末涂料基本生产过程  \n\n目前，PVC粉末涂料应用范围已不再那么广泛，然而它的好的耐腐蚀性和耐洗涤性、减噪性、耐低温性、柔滑的手感、良好的介电性等，使得该产品依然有相应的市场，如洗碗机、冰箱网架、汽车内饰及手柄、安全带扣、金属丝架和金属网、金属家具以及电气和电子工业等方面。",
+        "category": " Introduction"
+    },
+    {
+        "id": 696,
+        "chunk": "# 2.聚偏二氟乙烯（PVDF）粉末涂料  \n\nPVDF是透明或是半透明的结晶性聚合物，结晶度 $68\\%$ 左右，氟含量 $59\\%$ ，分子量25万 ${\\sim}100$ 万。PVDF涂膜抗冲击强度高、耐磨耗、耐蠕变、韧性好，表面摩擦力很低、不结冰、对流体吸收非常弱，具有较高的耐热性，不燃性，长期使用温度为一 $-40\\mathrm{\\sim}150^{\\circ}C$ ，具有突出的耐气候老化性、耐臭氧、耐辐照、耐紫外光，且介电性能优异。耐腐蚀性能优良，室温下不被酸、碱、强氧化剂、卤素所腐蚀。  \n\nPVDF是由偏二氟乙烯的自由基聚合反应得到的，用过氧化物作为引发剂，或者是和齐格勒-纳塔（Ziegler-Natta）催化剂一起使用。不同的专利描述了多种偏二氟乙烯聚合的方法，包括乳液聚合、悬浮聚合和溶液聚合法。聚偏二氟乙烯是重复单元结构为$-\\mathrm{CH_{2}}-\\mathrm{CF_{2}}-$ 、有规则的头尾衔接结构 $\\underline{{\\mathsf{f C F}_{2}}}\\mathrm{-CH}_{2}\\underline{{\\mathsf{T}}}$ 的高分子聚合物，氢原子和氟原子在空间上是相互对称的，这使聚合物分子之间的交联力得到加强。聚偏二氟乙烯是一种熔点在 $158{\\sim}197^{\\circ}C$ 的结晶聚合物，它存在两种不同的晶体结构：一种是所谓的 $\\alpha-$ 型，具有螺旋形构造；另一种是具有平面锯齿构造的 $\\beta$ -型。聚偏二氟乙烯的多晶型现象是其具有相当宽的熔点范围，而且熔点难以准确定义的原因。相对较高的熔点使聚偏二氟乙烯可以持久地应用在从 $-40{\\sim}150^{\\circ}C$ 这个相对较宽的温度范围之内，这个温度范围和聚偏二氟乙烯的玻璃化温度和熔点的最低限相符合。  \n\n聚偏二氟乙烯的特点是具有好的力学和冲击性能，以及非常好的耐磨性能与优秀的柔韧性和硬度相结合，它可以抵抗大多数腐蚀性化学品，如酸、碱、强氧化剂等的侵袭，同时它也不溶于涂料工业中常用的溶剂。一些高极性的溶剂只能临时软化聚偏二氟乙烯涂膜的表面，能够破坏聚偏二氟乙烯涂膜的仅有的化学品是发烟硫酸和强溶剂 $N,N-$ 二甲基乙酰胺。聚偏二氟乙烯符合美国食品药物管理局（FDA）的要求，可以作为应用于食品加工工业的材料以及获准与食品相接触。  \n\n聚偏二氟乙烯粉末涂料曾经被认为是具有异常性质的材料，这些性质包括低摩擦和磨损、憎水和憎油性、极好的室外耐候性、优秀的柔韧性、抗腐蚀和粉化、抗化学品和抗富含${\\bf S}{\\bf O}_{2}$ 的强腐蚀性的工业气体，由于极低的吸附污染的性质，聚偏二氟乙烯涂膜很容易保持清洁。聚偏二氟乙烯的这些特殊的性质是由于F—C键之间只有很小的极化现象，这也是以聚偏二氟乙烯为基料的涂层具有低表面能的原因。F—C键的非常高的键能 $(477\\mathrm{kJ/mol})$ 使聚偏二氟乙烯具有额外的耐候性。聚偏二氟乙烯能够单独作为基料制造粉末涂料，特别是对耐候性有特殊要求的情况下，但在实际应用中并不完全这样，主要的原因包括薄涂时由于聚偏二氟乙烯的高黏度而导致针孔、对金属相当差的附着力和相对较高的价格。  \n\n为了改善聚偏二氟乙烯的熔融流动性、对金属的附着力和涂膜的美观，通常将丙烯酸树脂加人到PVDF中。PVDF基料中经常加入30%的丙烯酸树脂，更高的丙烯酸树脂含量将使涂膜的耐候性降低，尽管如此涂膜的性能仍然优于到目前为止所知的其他人造的有机涂料材料。  \n\n聚偏二氟乙烯粉末涂料的光泽较低，在30%士5%的范围之内（60°)，这也许是聚偏二氟乙烯粉末涂料在应用范围中用于装饰目的受到限制的原因。  \n\nPVDF粉末涂料的生产过程和其他粉末涂料没有什么不同，这个过程包括用单或双螺杆挤出机将预混合树脂和颜料的挤出，随后是造粒和粒子的干燥，下一步是冷冻粉碎和过筛以获得 $50\\mu\\mathrm{m}$ 以下的颗粒。  \n\nPVDF非常低的表面能使涂膜具有低污染性，但同时也是导致对底材附着力差的原因。一般来说这是热塑性粉末涂料的共同缺点，但对于PVDF来说显得尤为突出。像前面提到的那样，PVDF和丙烯酸树脂的混合物能够改善附着力，但即使这种情况下，将PVDF 粉末涂料直接用于金属底材也是不可取的。为了获得好的附着力，PVDF粉末涂料使用了一种环氧底漆。也有在聚氨酯底漆上涂覆PVDF粉末的报道。  \n\n1974年的一份美国专利介绍了一种克服附着力差的问题的方法。这种方法使用了PVDF的体系的两层涂膜。第一层底漆是这样生产的：将粒径范围在 $60\\sim200$ 自的PVDF颗粒和 $150\\sim325$ 目的硅石粉（士）物理混合。通过暴露在 $100^{\\circ}C$ 的水汽中测量涂膜的附着力，将涂膜产生水泡的时间作为评价体系附着力性质的相关参数，时间范围为 $7\\sim480\\mathrm{h}$ ，分别对应于不含硅石粉（士）的底漆和PVDF/硅石的比率为100/40或更高的底漆。对另一种用同样粒度的石墨代替硅石的底漆的试验得到了同样的结果。  \n\n尽管用PVDF作为基料涂覆的卷材涂层通常给出20年的质量保证，但对于含有 $30\\%$ 丙烯酸树脂的PVDF粉末涂料，给出的是10年内最大失光率为最初光泽的 $50\\%$ 的质量保证。  \n\nPVDF粉末涂料在建筑方面的应用主要是用在有纪念意义类型的建筑上，建筑屋顶的方格、墙壁的包覆层、突出的铝材的门窗框架等部分的表面是其主要的应用场所。  \n\n粉末涂料用聚偏氟乙烯的特性黏度在 $0.6{\\sim}1.2\\mathrm{dL}/\\mathrm{g}$ 是比较理想的。如果大于 $1.2\\mathrm{d}\\mathrm{L}/\\mathrm{g}$ 时熔融性差，小于 $0.6\\mathrm{d}\\mathrm{L}/\\mathrm{g}$ 时涂膜强度下降。  \n\n此材料价格较贵，但是由于易于涂覆和耐化学药品性好，所以经济上还是可行的。主要用于化工耐蚀衬里等的涂覆。  \n\nPVDF粉末涂料涂层的施工，作为极端化学耐蚀涂膜，推荐用两层系统。这样可消除PVDF的收缩问题（即由于它的情性而难以像其他聚合物一样与底材附着），其热膨胀系数大约是钢铁的十倍 $(12\\times10^{-5}^{\\circ}\\mathsf{C}^{-1})$ 。第一层一般是由PVDF、填充剂、颜料和黏合剂配成。这个涂层对钢铁附着很好，还能使由于热膨胀造成的最大应力点，从聚合物/钢分界面移至聚合物深层内，从而可以被弥散而松弛下来。第二层是纯PVDF，能给出最大的化学耐蚀性。这样在化学耐蚀性和附着性方面是无比优越的。在某些情况下可用单一层，可以是底层或面层之一，如对化学耐蚀性要求不高的地方或是很坚硬而热循环小的基体。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 697,
+        "chunk": "# 二、聚烯烃粉末涂料  \n\n聚烯烃（polyolefin，PO）是烯烃的均聚物和共聚物的总称，主要包括聚乙烯、聚丙烯和聚1-丁烯及其他烯烃类聚合物。用于粉末涂料的聚烯烃主要是聚乙烯和聚丙烯。作为没有极性、高分子量的结晶聚合物，聚烯烃以C—C链为骨架，它们在韧性、耐化学和溶剂性方面有着独一无二的平衡。非常明显，以这类材料为基料的保护性涂层极具吸引力。然而它们不溶于涂料工业中常用的溶剂的性质使它们只能用于粉末涂料中。事实上，在20世纪50年代初期出现的、以流化床施工的粉末涂料中，其中之一便是聚乙烯粉末涂料。  \n\n，用液氮冷却或酒精浸泡可以使聚乙烯和聚丙烯脆性增强，一些技术正是基于这一点来获得更细的粉末。另外一些聚合过程生产的聚乙烯直接是很细的粉末，但高压聚乙烯是一种固体树脂而必须磨碎制造粉末。  \n\n作为一种情性材料，聚烯烃对金属或其他底材的附着力差。因此在成功使用聚乙烯和聚丙烯粉末涂料之前，底材表面必须涂一层底漆或者在粉末涂料中加入附着力促进剂来改善附着力。人们发明了丙烯酸共聚体的聚合物，这类聚合物与聚烯烃特别是聚丙烯混合的时候，能过获得具有很好的附着力的一层涂膜。这些聚合物呈小颗粒状，颗粒大小在适合粉末涂料的粒子尺寸范围之内，密度和聚丙烯相似，使用时可以简单地用跟斗混合机与聚丙烯粉末涂料混合。对有色体系， $15\\%$ 的添加量就可以使树脂与大多数底材有很好的附着力。透明丙烯涂料只需 $5\\%\\sim10\\%$ 的添加量就可以得到满意的效果。为了改善聚烯烃的附着力，人们对聚烯烃作了大量的改性研究。有些情况下，这个过程是将聚乙烯或聚丙烯与含有羧酸基团的附着力改性剂的简单混合过程。  \n\n聚乙烯和聚丙烯粉末涂料以耐溶剂性好而著称。因此聚乙烯和聚丙烯粉末涂料一个非常重要的用途是用在化学容器、管道和运输不同化学物质及溶剂的管线上。",
+        "category": " Introduction"
+    },
+    {
+        "id": 698,
+        "chunk": "# 1.聚乙烯粉末涂料  \n\n聚乙烯是最结构简单的高分子聚合物，也是应用最广泛的高分子材料，它是由重复的一 $\\mathrm{CH_{2}}$ 一单元连接而成的。聚乙烯通过乙烯 $\\mathrm{CH_{2}=C H_{2}}$ 加聚而成。聚乙烯的性能取决于它的聚合方式。几乎在常温常压下，在有机化金属化合物四氯化钛-三乙基铝「 $\\mathrm{TiCl_{4}}=$ $\\mathrm{Al}(\\mathrm{C}_{2}\\mathrm{H}_{5})_{3}]$ 催化条件下进行Ziegler-Natta聚合而成的是高密度聚乙烯（HDPE)。这种条件下聚合的聚乙烯分子是线型的，所得聚乙烯具有立体规整性好、密度高、结晶度高等特点。如果是在高压力（ $1000\\sim2000\\mathrm{atm}$ ， $\\mathrm{1atm=101325Pa)}$ 、高温( $190\\sim$ $210^{\\circ}C)$ 、过氧化物催化条件下自由基聚合，生产出的则是低密度聚乙烯（LDPE)，低密度聚乙烯由于在反应过程中的链转移反应，在分子链上生出许多支链。这些支链妨碍了分子链的整齐排布，因此结晶度、密度较低，而且分子量分布宽。高密度聚乙烯质地硬，而低密度聚乙烯相对软一些。此外，还有一种中压聚合法，即用负载于硅胶上的铬系催化剂，在环管反应器中，使乙烯在中压下聚合，生产高密度聚乙烯。各种聚乙烯的性能见表3-8-1。  \n\n表3-8-1 各种聚乙烯的性能  \n\n\n<html><body><table><tr><td>性能</td><td>高压工艺</td><td>中压工艺</td><td>Ziegler工艺</td></tr><tr><td>结晶度/%</td><td>65</td><td>95</td><td>85</td></tr><tr><td>相对刚性</td><td>1</td><td>4</td><td>3</td></tr><tr><td>软化温度/℃</td><td>104</td><td>127</td><td>124</td></tr><tr><td>拉伸强度/MPa</td><td>13. 79</td><td>37.92</td><td>24.13</td></tr><tr><td>伸长率/%</td><td>500</td><td>20</td><td>100</td></tr><tr><td>相对冲击强度</td><td>10</td><td>3</td><td>4</td></tr><tr><td>密度/（g/cm3）</td><td>0.92</td><td>0.96</td><td>0.95</td></tr></table></body></html>  \n\n聚乙烯具有优良的力学性能、绝缘性、耐寒性、化学稳定性、吸水性和透气性低，无毒。聚乙烯抗多种有机溶剂，抗多种酸、碱腐蚀，但是不抗氧化性酸，例如硝酸。在氧化性环境中聚乙烯会被氧化。然而，不同方法生产的聚乙烯树脂在分子量分布、支链的数量和长度以及结晶度等方面的不同而使得各种聚乙烯的性质有所不同，也造成了对应所制造的粉末涂料产品的性能和用途有所不同。这类树脂的结晶点可看做是树脂的交联点，因此，结晶度高的聚乙烯树脂所制成的粉末涂料有较高的刚性、硬度和机械强度以及耐化学腐蚀性能等。  \n\n相反，结晶度低的聚乙烯树脂这方面的性能都有所下降，软化点和熔融温度也相对较低，而透明性较好。表3-8-2是不同的聚乙烯树脂制成的粉末涂料涂膜的性能（结晶度越高密度越高，结晶度越低密度越低）。  \n\n表3-8-2应用在粉末涂料方面的不同类型聚乙烯的性能  \n\n\n<html><body><table><tr><td>性能</td><td>低密度</td><td>中密度</td><td>高密度</td></tr><tr><td>耐酸性</td><td>好</td><td>非常好</td><td>非常好</td></tr><tr><td>耐含氧酸性</td><td>侵蚀</td><td>缓慢侵蚀</td><td>缓慢侵蚀</td></tr><tr><td>耐碱性</td><td>好</td><td>非常好</td><td>非常好</td></tr><tr><td>耐有机溶剂性</td><td>好</td><td>好</td><td>好</td></tr><tr><td>耐溶剂</td><td>低于60℃</td><td>低于60°℃</td><td>低于80℃</td></tr><tr><td>透明性</td><td>透明</td><td>透明</td><td>不透明</td></tr><tr><td>晶体熔点/℃</td><td>108~126</td><td>126~135</td><td>126~136</td></tr><tr><td>耐热（连续使用）/C</td><td>82~100</td><td>104~121</td><td>121</td></tr><tr><td>密度/（g/cm3）</td><td>0.910～0.925</td><td>0. 926~0.940</td><td>0. 941~0.965</td></tr><tr><td>伸长率/%</td><td>90~800</td><td>50~600</td><td>15~100</td></tr></table></body></html>  \n\n聚乙烯树脂有较高的结晶度和内聚力，因而聚乙烯粉末涂料对底材的附着力差。在使用聚乙烯粉末涂料前必须对底材预涂底漆（一般为热固性底漆）或在聚乙烯粉末涂料制作时加人附着力促进剂，如含羧基的丙烯酸共聚物等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 699,
+        "chunk": "# 2.聚丙烯粉末涂料  \n\n聚丙烯所具有的许多优良性质使其成为制造粉末涂料的有多方面用途的材料，其涂层优良的表面硬度能够耐划伤和摩擦，本质上不受大多数化学品的影响，有着杰出的耐溶剂性。在常温下和聚乙烯相比较，聚丙烯的脆性稍大一点，这是由于后者比前者玻璃化温度相对较高（高 $25\\sim35^{\\circ}C$ ）所引起的，而玻璃化温度则取决于结晶程度。  \n\n根据聚丙烯分子链的立体结构，可将其分为三种类型。  \n\n（1）无规聚丙烯，其结构无序，它是通过阳离子聚合而成的无定形、软而发黏的树脂。而通过阴离子聚合的聚丙烯有全同结构和间同结构两种结构类型，如图3-8-3所示。  \n\n![](images/d0148d00a8657ee1dbfe8f69661233f2c484287a8d21cf0293e02677a36109da.jpg)  \n图3-8-3 阴离子聚合的聚丙烯结构  \n\n(2）全同结构聚丙烯和间同结构聚丙烯的有序结构使其结晶度大为提高，结果是聚丙烯的机械强度提高、耐溶剂性和耐化学性增强。  \n\n(3）阴离子聚合得到的主要是全同结构聚丙烯，它是工业化生产的最轻的塑料之一，密度只有 $0.9\\mathrm{g/cm^{3}}$ 。工业级的等规聚丙烯的熔点范围为 $165\\sim170^{\\circ}\\mathrm{C}$ ，而 $100\\%$ 的全同结构聚丙烯的熔点为 $183^{\\circ}C$ 睿  \n\n工业级产品的脆性和耐冲击性可以通过与其他烯烃的共聚而得到显著改善。市场上相当数量的聚丙烯含有 $2\\%\\sim5\\%$ 的乙烯，结果是使聚合物的柔韧性、耐冲击性和透明度增强，同时使熔点稍微降低。  \n\n聚丙烯树脂是结晶型聚合物，没有极性，具有韧性强、耐化学药品和耐溶剂性能好的特点。国产树脂的企业标准见表3-8-3。  \n\n表3-8-3粉末用聚丙烯树脂的企业标准  \n\n\n<html><body><table><tr><td>项 目</td><td>PP4018</td><td>PP5004</td><td>PP5028</td></tr><tr><td>熔融指数/（g/10min）</td><td>10.1~16.05</td><td>2.5~4.0</td><td>7.0~10.0</td></tr><tr><td>己烷可提取率/%</td><td>2</td><td>2</td><td>2.5</td></tr><tr><td>拉伸屈服强度/MPa</td><td></td><td></td><td></td></tr><tr><td>一级品</td><td>30</td><td>30</td><td>30</td></tr><tr><td>二级品</td><td>28</td><td>28</td><td>28</td></tr><tr><td>颗粒总灰分量/（mg/kg）</td><td></td><td></td><td></td></tr><tr><td>一级品</td><td>500</td><td>500</td><td>500</td></tr><tr><td>二级品</td><td>600</td><td>600</td><td>600</td></tr><tr><td>污染度/(斑点/25g)</td><td>≤</td><td></td><td></td></tr><tr><td>一级品</td><td>10</td><td>10</td><td>10</td></tr><tr><td>二级品</td><td>10</td><td>15</td><td>15</td></tr></table></body></html>  \n\n聚丙烯不活泼，几乎不附着在金属或其他底材上面。因此，用作保护涂层时，必须解决附着力问题。如果添加极性强、附着力好的树脂等特殊改性剂时，对附着力有明显改进。聚丙烯涂膜附着力和温度之间的关系表是随着温度的升高，涂膜附着力将相应下降。聚丙烯和丙烯酸的接枝共聚物（聚丙烯占共聚物 $75\\%\\sim98\\%$ ）是一种良好的聚丙烯粉末涂料。  \n\n表3-8-4 聚丙烯粉末涂料（T-03）性能  \n\n\n<html><body><table><tr><td>项 目</td><td>性能指标</td></tr><tr><td>外观</td><td>色泽基本一致，松散，无结块</td></tr><tr><td>粒度</td><td>74~180μm，筛余物≤4%</td></tr><tr><td>熔体流动速率</td><td>5~16g/10min，230℃，负荷21600g</td></tr><tr><td>熔融温度下挥发分含量/%</td><td>≤0.7(熔融温度160℃±2℃）</td></tr><tr><td>固化条件</td><td>200°℃±5℃，塑化30～60min</td></tr><tr><td>固化条件</td><td>静电喷涂（或流化床)→预塑化[（200±5)C/5～10min]→第二次静电喷涂（或流化 床)-→塑化[（200±5)C/30～60min]→冷水冷却</td></tr></table></body></html>  \n\n表3-8-5聚丙烯粉末涂料的涂膜性能  \n\n\n<html><body><table><tr><td>项目</td><td>性能</td><td>项 目</td><td>性能</td></tr><tr><td>60°光泽</td><td>55%</td><td>耐1%盐水</td><td>很好</td></tr><tr><td>冲击强度（Gardner 法）/N·cm</td><td>843.3</td><td>耐盐雾</td><td>很好</td></tr><tr><td>硬度（Sward法）</td><td>22</td><td>耐稀硫酸</td><td>很好</td></tr><tr><td>耐磨性（ASTMD963-31）</td><td>70L/25.4μm</td><td>耐浓硫酸</td><td>好</td></tr><tr><td>锥形挠曲试验</td><td>合格</td><td>耐稀盐酸</td><td>很好</td></tr><tr><td>电绝缘性</td><td>1440V/25.4μm</td><td>耐浓盐酸</td><td>好</td></tr><tr><td>介电常数</td><td>2.4~2.42</td><td>耐稀、浓醋酸</td><td>很好</td></tr><tr><td>耐100%RH</td><td>很好</td><td>耐稀、浓氢氧化钠</td><td>很好</td></tr><tr><td>耐沸水</td><td>好</td><td>耐稀、浓氨水</td><td>很好</td></tr><tr><td>连续使用最高温度/℃</td><td>60</td><td>耐汽油</td><td>很好</td></tr><tr><td>间断使用最高温度/C</td><td>80</td><td>耐烃类</td><td>良好</td></tr><tr><td>最低使用温度/C</td><td>10～—30</td><td>耐酯、酮</td><td>差</td></tr><tr><td>拉伸强度/MPa</td><td>14.7～24.5</td><td>耐稀酸（10%）</td><td>很好</td></tr><tr><td>伸长率/%</td><td>200～400</td><td>耐稀碱（10%）</td><td>很好</td></tr><tr><td>邵氏硬度</td><td>30~55</td><td>毒性</td><td>低毒</td></tr><tr><td>铅笔硬度</td><td>5B</td><td></td><td></td></tr></table></body></html>  \n\n聚丙烯结晶体熔点为 $167^{\\circ}C$ ，在 $190{\\sim}232^{\\circ}\\mathrm{C}$ 热熔融附着，用任意方法都可以涂装。一般用流化床涂覆，被涂物在 $250{\\sim}390^{\\circ}\\mathrm{C}$ 预热，涂装后的熔融烘烤温度为 $180\\sim250^{\\circ}C$ ，最大涂膜厚度可达 $375\\mu\\mathrm{m}$ 。静电喷涂法涂装，其涂膜厚为 $170\\sim200\\mu\\mathrm{m}$ ，熔融烘烤温度为 $180\\sim$ $250^{\\circ}C$ 。为了得到最合适的附着力、冲击强度、光泽和柔韧性，应在热熔融附着以后立即迅速冷却。聚丙烯是结晶聚合物，结晶的大小取决于从熔融状态冷却的速率，冷却速率越快，结晶越小，表面缺陷少，可能得到细腻而柔韧的表面。聚丙烯粉末的稳定好，在稍高温度下贮存时，也不发生胶化或结块的倾向。聚丙烯可以得到水一样透明涂膜。其涂料性能、涂膜的物理力学性能和耐化学药品性能见表3-8-4 和表3-8-5。聚丙烯涂膜的耐化学药品性能比较好，但不能耐硝酸那样的强氧化性酸。  \n\n虽然聚丙烯不适用于装饰，但加人一些颜料和稳定剂以后，保光性和其他性能会同时有所改进。一般情况下，涂膜曝晒6个月后，保光率只有 $27\\%$ ，然而添加紫外线稳定剂后，涂膜保光率可达 $70\\%$ 。聚丙烯粉末涂料主要用于家用电器部件和化工厂的耐腐蚀衬里等。聚丙烯粉末国内很少有厂家生产。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 700,
+        "chunk": "# 三、尼龙粉末涂料  \n\n尼龙是在二胺与二酸或氨基酸本身缩聚反应形成的聚合物，因此又称之为聚酰胺。由于结构的规则性，大多数商业类型的聚酰胺是晶体材料，有着相对精确的熔点。与脂肪族的晶体型聚酯相比，聚酰胺的熔融温度要高得多，这是由于酰氨基是强极性基团以及聚合物内部存在氢键的结果。和预想的一样，聚酰胺的熔点随酰胺基团的含量增加而升高。低熔点的聚酰胺被优先选择来制造粉末涂料，尼龙-11的熔点相对较低（ $\\cdot185^{\\circ}C^{\\prime}$ )，和尼龙-12（熔点$178^{\\circ}C$ ）一起，在广泛的聚酰胺品种中这两种聚酰胺被用作粉末涂料的基料。尽管尼龙-6、尼龙-66和尼龙-610容易得到和价格相对低廉，但由于它们的熔点分别为 $215C$ 、 $250^{\\circ}C$ 和$210^{\\circ}C$ ，并没有被粉末涂料生产者所接受。  \n\n尼龙-11是氨基十一酸自缩聚的产物，尼龙-12是由12-内酰胺的自聚反应获得的。尼龙-11和尼龙-12两者在常用的有机溶剂中都几乎不溶解，但即使在室温下也很容易受到苯酚、蚁酸、无机酸以及类似的化合物的腐蚀。在较高的温度下，它们可溶于乙醇和卤代烃的混合溶液、硝基乙醇和氯化甲醇的混合物中。  \n\n在室温下，尼龙-11（理化性能见表3-8-6）和尼龙-12有很好的耐水性，即使在沸水中也是如此。它们的耐碱性能相当好，但总体来讲，尼龙在酸介质中的稳定性不是太好。在1956年，欧洲最早出现了尼龙粉末，是以尼龙-11作为基料的。尼龙粉末的一些独特性能使其具有其他粉末无法比拟的优势。这种尼龙粉末的特点是具有非常高的硬度，低温下耐冲击性能仍然突出，非常低的摩擦系数和异乎寻常的抗摩擦性能使尼龙粉末成为减少金属之间摩擦噪声的优良涂层。优异的绝热性能也是尼龙粉末另一个杰出特点。另外尼龙的这些性质大多数在非常宽的工作温度范围内都能保持。尼龙粉末涂料对实践中常用的溶剂都表现出了非常优异的耐性，对低浓度的有机酸、无机盐和碱的耐腐蚀性也相当不错，这也许是由于氨基易于形成强氢键的缘故。尼龙-11潜在的稳定性能使得这种材料不但在户内性能方面，而且在户外应用方面也引人注目，即应用在要求耐候与耐化学、防潮、高冲击性能、抗磨损性、耐用性结合在一起的场所也是如此。目前没有全面的尼龙-11的耐候性数据，尼龙涂层在耐候性方面性能优异，具有十年以上的使用寿命。  \n\n流化床法是尼龙粉末涂覆最常用的方法。用流化床一次涂覆的厚度就可以达到 $200\\sim$ $700\\mu\\mathrm{m}$ 。根据悬挂工件的传送带的速率和工件的质量，尼龙-11的熔融温度在 $200{\\sim}230^{\\circ}C$ 中最常用的温度是220℃。使用静电喷涂法可以得到薄的涂层，正负电极都可以，然而，人们注意到使用正电极在给定的时间内可以沉积更多的粉末。使用电压在 $30{\\sim}70\\ensuremath{\\mathrm{kV}}$ 的、其他类型粉末所用的常规喷涂设备，都可以用来喷涂尼龙粉末。用静电喷涂法得到的涂层的厚度通常在 $100{\\sim}150\\mu\\mathrm{m}$ 0  \n\n表3-8-6 尼龙-11涂膜理化性能  \n\n\n<html><body><table><tr><td>项目</td><td>性能</td><td>项目</td><td>性能</td></tr><tr><td>熔点/C 密度/（g/cm） 流化床浸涂前预热温度/C</td><td>178 1.02 260~380 0~5min/200~230℃</td><td>耐磨性（Taber's CS-17,1kg，1000 次)/mg 埃力克森值/mm 弯曲（Gardnerp6棒） 光泽（60℃）/% 5~10min/200~230℃ 骤冷 慢冷</td><td>5 >13 合格 84 7</td></tr></table></body></html>  \n\n我国采用尼龙粉末涂料有着较长的历史，1964年以来在纺织、机械、造船等行业采用火焰喷涂、直接喷涂、流化床涂覆等工艺来涂布尼龙粉末，从而修补磨损的机械零件、机床设备导轨等。近几年来，尼龙粉末涂料引起了各个行业的广泛兴趣和重视，一则尼龙粉末涂料品种有了发展；二则除了火焰喷涂等工件外，尼龙粉末静电喷涂也试验成功，从而尼龙粉末涂料的应用有了较大发展。如植保机械的铝泵体零件，机床设备和仪器设备的导轨，印刷机钢墨辊，农机具和机械零件维修，织布机的轴，货车，医院设备主轴等零件，水力机械抗泥沙磨损用的非金属涂层等的应用，均取得了预期的效果。  \n\n尼龙粉末涂料无毒、无气味、无味道和不受真菌侵蚀、不利于细菌繁殖的性质使其成为应用在食品工业中机械部件和管路的涂覆，或者是应用在与食品直接接触部位的涂装。尼龙-11为基料的粉末涂料获得了所有工业国家应用在饮料和食品方面的许可。  \n\n尼龙粉末涂料的另外一个重要的优点是优异的耐冲击性，而且耐冲击性能够在很宽的温度范围内保持不变（从 $-38\\mathrm{\\sim}150^{\\circ}\\mathrm{C})$ 。在空气中，尼龙粉末涂料可以持续耐 $80^{\\circ}C$ 的温度；当没有空气存在的情况下，可以在 $150^{\\circ}C$ 下持续使用。  \n\n尼龙粉末涂料的低摩擦系数、优秀的耐磨性、抗污染性使它们可以应用在汽车轮毂、摩托车框架、建筑项目、行李推车、金属家具、安全装置、运动器材、农用工具等方面上。  \n\n阀杆和底座、水泵房、耐油的盘碟、家用洗衣机的内壁、粗的管道等这些物件上用尼龙粉末涂装后具有优异的耐溶剂性以及耐弱碱和清洁剂。  \n\n尼龙粉末涂料的另一个用途是做各种器材、工具的把手上。不但尼龙的耐磨和耐涂鸦性是其应用在此类用途上的重要因素，而且它们的低导热性给予把手一种温暖的感觉，这就使得这种材料在工具把手、门把手、方向盘等方面的应用引人注目。  \n\n随着尼龙粉末品种增加，尼龙粉末已出现了复合改性的低熔点粉末等新产品，它们的出现，不仅提高了尼龙的附着强度，增加了抗腐蚀性能，而且使尼龙粉末施工出现了低温化的趋向，为节约能源，缩短工时创造了条件，可以看到尼龙粉末涂料的新品种不断出现。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 701,
+        "chunk": "# 四、热塑性聚酯粉末涂料  \n\n热塑性聚酯粉末涂料是热塑性聚酯树脂、颜料、填料和流动控制剂等成分，经熔融混合、冷却、粉碎和分级过筛得到。聚酯树脂由各种二元羧酸、二元醇经缩聚反应而合成。这种粉末涂料可用流化床浸涂法或静电粉末喷涂法施工。但多用于流化床涂覆，以求得较厚的涂膜。涂膜对底材的附着力、涂料的贮存稳定性、涂膜的物理机械性能和耐化学药品性能都比较好，特别具有优良的绝缘性和户外耐候性、韧性、耐久性、耐磨性。典型的树脂和涂膜性能见表3-8-7。  \n\n表3-8-7典型的热塑性聚酯树脂和涂膜性能  \n\n\n<html><body><table><tr><td>项目</td><td>性能</td><td>项目</td><td>性能</td></tr><tr><td>树脂密度/（g/cm3）</td><td>1.33</td><td>涂膜冲击强度/N·cm</td><td>1. 09 X 103</td></tr><tr><td>树脂软化点/C</td><td>70</td><td>涂膜耐候性（户外1年保光率）/%</td><td>90~95</td></tr><tr><td>60°光泽/%</td><td>90～100</td><td>涂膜人工老化试验（850h）</td><td>很好</td></tr><tr><td>涂膜拉伸强度/MPa</td><td>53.7</td><td>涂膜耐盐雾试验（划伤，1200h）</td><td>侵蚀3mm（侵蚀</td></tr><tr><td>涂膜伸长率/%</td><td>2~4</td><td></td><td>6mm涂膜剥离）</td></tr><tr><td>涂膜耐磨性（Taber,CS-17）/g</td><td>0.06</td><td>涂膜耐盐雾试验（未划伤，2000h）</td><td>无变化</td></tr><tr><td>涂膜邵氏硬度</td><td>0.83</td><td>涂膜浸10%硫酸、盐酸</td><td>一个月无变化</td></tr><tr><td>涂膜铅笔硬度</td><td>F~H</td><td>涂膜浸25℃水11周</td><td>无变化</td></tr></table></body></html>  \n\n日本用于流化床浸涂的热塑性聚酯粉末涂料和涂膜性能见表3-8-8，供参考和比较。  \n\n表3-8-8 流化床浸涂粉末和涂膜性能（热塑性聚酯）  \n\n\n<html><body><table><tr><td colspan=\"2\">试验项目</td><td colspan=\"2\">热塑性聚酯</td><td rowspan=\"2\">试验方法</td></tr><tr><td colspan=\"2\"></td><td>白色</td><td>黑色</td></tr><tr><td colspan=\"2\">底材 前处理 前处理</td><td>钢板（3mm、2mm） 脱脂 380℃/5min</td><td>复合线材（3mm、4mm、5mm） 脱脂 350℃/5min-</td><td></td></tr><tr><td>流浸加工条件 膜厚/μm</td><td>浸渍 后加热条件 冷却</td><td>6s 90℃/10min 自然冷却 700</td><td>2s 90℃/10min 自然冷却 400</td><td></td></tr><tr><td colspan=\"2\">平整性 光泽 硬度 耐冲击性/kgf·cm</td><td>O Q 77 77 >30</td><td></td><td>60°光泽 邵氏硬度 杜邦冲击器(球径1/2) 180°剥离 5%盐水浸渍20℃/30d 日光型老化机</td></tr></table></body></html>\n\n注：O表示优良；表示尚可。  \n\n这种粉末涂料主要用于涂装钢管、变压器外壳、贮槽、马路安全栏杆、户外标识文字、货架、家用电器、机器零部件的涂装；另外还用于防腐蚀和食品加工有关设备。这种粉末涂料的缺点是耐热性和耐溶剂性较差。  \n\n![](images/4eaec60d312d5858ccdfe91242cbbfb29fd43d94a105d9743cb2f5ef2582cf32.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 702,
+        "chunk": "# 一、纯环氧型粉末涂料  \n\n将环氧树脂作为成膜物是第一个用来生产热固性粉末涂料的，首先出现的热固性粉末涂料品种就是纯环氧型粉末涂料。考虑到粉末涂料的生产加工性、产品贮存稳定性、成膜性能等方面的因素，一般选用分子量在1000～4000，软化点在90℃左右的双酚A型环氧树脂作为主要成膜物，即国内牌号为E-12或604型环氧树脂。  \n\n粉末涂料用环氧树脂的生产分为“两步法”和“一步法”。“两步法”的环氧树脂即先将环氧氯丙烷和双酚A通过滴加氢氧化钠溶液制成小分子量的环氧树脂，再与双酚A进行二次反应制成所需要的中等分子量环氧树脂。“两步法”生产的环氧树脂具有分子量分布窄、歧化反应低、化学杂质少等优点，用于制作高性能粉末涂料或绝缘、防腐粉末涂料，但价格较高。“一步法”环氧树脂又分为“溶剂一步法”和“水洗一步法”，“溶剂一步法”是首先将双酚A和氢氧化钠溶液以及部分溶剂溶解后加人环氧氯丙烷进行反应制成中等分子量的环氧树脂，加入溶剂溶解环氧树脂使之成为低黏度溶液，再进行水洗脱除无机杂质，最后进行真空脱溶剂。用此方法有控制反应较容易、有机杂质含量低、树脂溶液因黏度低而易水洗且水洗温度低、树脂色泽浅、无机杂质脱除较彻底等优点。“水洗一步法”没有加溶剂的过程，随着合成反应的进行物料黏度增大，反应不易控制，歧化反应较多，有机杂质含量较大。而在水洗时由于树脂黏度较高使得无机杂质脱除较困难，也会造成无机杂质含量较大。我国绝大多数的环氧树脂生产厂家都使用的是“水洗一步法”生产的604型环氧树脂。  \n\n粉末涂料是用环氧树脂的环氧值在0.11～0.13eq/100g或环氧当量在910～770g/eq范围的固态树脂。这种环氧树脂的技术指标包括外观、环氧值（或环氧当量）、可水解氯值（或有机氯值)、无机氯值、软化点、挥发分等。这些指标的意义和在粉末涂料中的作用或影响如下。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 703,
+        "chunk": "# 1.粉末涂料用环氧树脂  \n\n（1）环氧值环氧值和环氧当量（参见本书环氧树脂内容）是用来进行理论上的固化剂用量计算的数值，是设计配方时固化剂用量的计算依据。也可以用它来判断固化体系交联密度的大小，在相同体系的系列中进行交联密度的比较。  \n\n双酚A型环氧树脂的环氧基百分含量及环氧树脂分子量的计算式如下：  \n\n(2）水解氯值（或有机氯值）在环氧树脂合成反应过程中，由于副反应使树脂分子中含有的氯为环氧树脂的有机氯，其含量即为有机氯值，即每100g环氧树脂中含有的有机氯原子的摩尔数。单位为“mol/100g”。双酚A环氧树脂的有机氯分为水解氯和不可水解氯，但水解氯会对环氧树脂的固化行为与固化产物的性能产生不良影响，因而其含量是环氧树脂一项十分重要的特性指标。标准HG 2-741—1972和GB4618—1984中有机氯的测定方法其实是水解氯的测定方法（水解氯又称为易皂化氯和活性氯)。此外，有机氯值高，还说明环氧树脂在合成时，歧化反应高，分子量分布较宽。水解氯含量指标：一般产品0.004～$0.005\\mathrm{mol}/100\\mathrm{g}$ 。高纯度产品：小于 $0.002\\mathrm{mol}/100\\mathrm{g}$ ；超高纯度产品：小于 $0.001\\mathrm{mol}/100\\mathrm{g}.$ 当水解氯超过 $0.01\\mathrm{mol}/100\\mathrm{g}$ 时，固化的涂膜性能将受到影响。  \n\n(3）无机氯值无机氯值是指每100g环氧树脂中含有的氯离子的mol数。单位为$^{\\mathrm{si}}\\mathrm{mol/100g^{\\mathrm{37}}}$ 。环氧树脂中的无机氯离子是残留的氯化钠形成的。无机氯值的高低反映的是树脂生产后期清洗程度的好坏。无机氯含量高说明环氧树脂含水溶性杂质多，这将影响涂膜的介电性能、耐腐蚀性和耐久性。  \n\n水解氯和无机氯值除使用 $^{\\mathrm{s}}\\mathrm{mol}/100\\mathrm{g}^{\\mathrm{,,}}$ 单位表示外，有的企业还用质量分数表示，即质量百分比含量，它们之间的换算关系为：  \n\n质量百分比含量 $=\\frac{\\mathrm{mol}}{100\\mathrm{g}}\\times$ 氯的原子量（35.45）  \n\n环氧树脂中残存的氯以三种形式出现：氯离子、可水解氯和不可水解氯，氯离子是残留的氯化钠离子，后两种是反应的副产物  \n\n(4）软化点对于非结晶的材料，固-液的转变是一个由软化进而熔融的渐变过程，没有一个确定的转变温度，通常引出“软化点”的概念，这里的软化点是指固-液转变临界温度。对于环氧树脂来说，由于树脂的分子量不是单一值，是在一定范围内呈分布状态的，因此树脂没有一个确定的熔点，但是有一个较大变形的温度，称之为树脂的软化点。在同种类树脂中，通过软化点的数值可以比较出树脂平均分子量的大小。通过对同类树脂软化点和反应性官能团含量的对比分析，也可以粗略地判断出树脂分子量分布的情况。软化点的高低对物料在挤出机的混炼效果和涂膜的流平性有一定影响，软化点低的环氧树脂较利于物料的混炼和涂膜的流平。  \n\n(5）挥发分有的环氧树脂在合成过程中加有有机溶剂（如巴陵石油化工有限责任公司环氧树脂事业部的相关产品和广州宏昌电子材料有限公司的相关产品等)，并且在反应结束后都要进行水洗过程，真空脱除不彻底会造成环氧树脂挥发分含量高，可能会造成涂膜针孔的情况。一般环氧树脂的挥发分，按质量分数应小于等于 $0.6\\%$ 为宜。  \n\n(6）玻璃化温度（ $T_{\\mathrm{g}}$ ）E-12（604型）环氧树脂属于中等分子量的环氧树脂，其玻璃化温度随树脂的分子量的大小而呈现出高低对应的，很少有未固化环氧树脂玻璃化温度的报道，据我国一家著名环氧树脂生产企业提供的检测数据，它们的相应产品的玻璃化温度是 $50\\sim53^{\\circ}C$ ，该公司的产品在粉末涂料长期应用过程中，并未在贮运、存放、磨粉及制成品的运贮过程中造成结块的主要影响因素。若发现环氧树脂在正常贮运、存放情况下就发生结块情况的属不正常现象。环氧树脂的熔融黏度较低，加之其分子结构中含有的羟基基团，因而在混合型粉末涂料体系中，环氧树脂用量越大越利于颜料的分散和涂膜的流平。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 704,
+        "chunk": "# 2.粉末涂料的环氧树脂固化剂  \n\n环氧树脂的固化剂有很多品种，但作为粉末涂料的固化剂要考虑易加工性、与环氧树脂的混容性、加工的稳定性、贮存稳定性和粉末涂料的使用性等。经常使用的有如下产品。  \n\n(1）双氰胺分子式 $\\mathrm{C_{2}H_{4}N_{4}}$ ，分子量84.08，含有四个活泼氢原子，理论当量为21.02。双氰胺为白色菱形结晶性粉末，熔点 $207\\sim210^{\\circ}C$ 。对环氧树脂理论使用量可按式(3-8-4）计算。  \n\n双氰胺的分子量×环氧值$100_{\\mathrm{g}}$ 环氧树脂双氰胺的用量=双氰胺活泼氢的数量（个）  \n\n例如：某双氰胺含量 $99.4\\%$ ，那么 $100\\mathbf{g}$ 环氧树脂双氰胺的用量 $=21.02\\times99.4\\%\\times$ 环氧值。然而，在实际配方中则要高于理论量的 $15\\%$ 左右，这可能是由于双氰胺与环氧树脂的混容性差且熔点高于固化温度造成的。双氰胺固化环氧树脂的条件为 $160^{\\circ}\\mathrm{C}/\\bar{6}0\\mathrm{min}$ 或$180^{\\circ}\\mathrm{C}/30\\mathrm{min}$ 。目前双氰胺主要用于纯环氧的纹理型粉末涂料产品中。  \n\n(2）加速双氰胺和改性双氰胺将双氰胺与固化促进剂，如咪唑或咪唑衍生物按一定比例的混合物称为加速双氰胺，这种复合固化剂虽然能够降低环氧树脂的固化温度和缩短固化时间并改善了固化后涂膜的机械强度，但依然不能改善固化剂与树脂的混容性，也就改善不了涂膜表面光洁度的缺陷。采用芳香族二胺如 $4+4^{\\prime}=$ 二氨基二苯甲烷（DDM)、 $4,4^{r}$ -二氨基二苯醚（DDE)、 $4,4^{\\prime}.$ -二氨基二苯矾（DDS)、对二甲苯胺（DMB）等分别与双氰胺反应制得其衍生物称之为改性双氰胺或叫取代双氰胺，这种引入苯环后的双氰胺衍生物的熔点较低，与双酚A型环氧树脂的相容性与双氰胺相比明显增加。这种改性双氰胺的固化温度均低于双氰胺，而且涂膜表面的光洁度大有改善。  \n\n(3）咪唑类包括咪唑、2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑等。咪唑类固化剂是一类高活性固化剂，在中温下短时间即可使环氧树脂固化，因此其与环氧树脂组成的单组分体系贮存期较短，在粉末涂料中并不把它们作为单独的固化剂使用，而是把它们作为固化促进剂使用（一般是固体的2-甲基咪唑和2-苯基咪唑)。这类物质对双氰胺、酸酐、酚醛和羧基醇酸树脂与环氧树脂的固化均具有良好的固化促进作用。  \n\n(4）其他改性多元胺2-苯基-2-咪唑啉：粉末涂料行业称之为 $\\times\\times31$ 的固化促进剂。其抗黄变比2-甲基咪唑稍好，但促进固化效率比2-甲基咪唑低。此外还用它来合成环氧树脂粉末的消光固化剂。  \n\n2-苯基-2-咪唑啉与芳香族多元酸盐：将均苯四甲酸酐或偏苯三甲酸酐水解后与等物质的量的2-苯基-2-咪唑啉反应生成的单胺盐固化剂即为常用的消光固化剂，前者是68型，后者是55型。  \n\n这类物质的结构中都含有叔胺，属于碱性固化促进剂，具有不同程度的固化促进作用。  \n\n(5）多元酸粉末涂料中最重要的就是端羧基聚酯树脂，在以后内容进行专门讲述。此外还有作为两步固化消光的小分子多元酸聚合物，如六安市捷通达化工有限公司的SA2068和奉化南海药化公司的XG628。这类固化剂在配方用量计算时都可参照在介绍环氧树脂时所用的计算公式。此外，还有一些脂肪族多元酸作为环氧丙烯酸树脂的固化剂，如月桂二酸等。  \n\n(6）多元酚使用苯酚和甲醛缩合的酚醛树脂作为粉末涂料环氧树脂的固化剂，此类固化剂是较早开发的环氧固化剂之一，品种也较多。酚醛树脂的反应活性基团主要是酚羟基，含量以羟值表示，即每 $100_{\\mathsf{E}}$ 酚醛树脂所含羟基的当量值，配方计算用量按如下公式  \n\n环氧值 酚醛固化剂质量 $\\fallingdotseq$ 环氧树脂质量× 酚醛固化剂羟值  \n\n酚醛树脂固化剂与环氧树脂的反应速率较快，可达到 $200^{\\circ}C$ 时 $2\\mathrm{min}$ 固化，虽然反应活性高，但配置的粉末涂料具有很好的贮存稳定性。酚醛环氧粉末涂料具有较好的耐温性能和极好的耐腐蚀、耐溶剂、耐化学性能。但颜色较深，不能做浅色产品；抗紫外线性能差，不能用于户外，主要作为地下管道防腐蚀等粉末涂料。  \n\n(7）酸酐使用酸酐固化的环氧粉末涂料具有耐热性、机械强度和电性能优良，因而用来生产电器绝缘粉末涂料。即使含有一个酐环的酸酐也能够固化环氧树脂。原则上，邻苯二甲酸酐、偏苯三甲酸酐和均苯四甲酸酐等都可以固化环氧树脂，但由于它们具有挥发性和熔点较高加之具有毒性，一般不单独使用，而是把偏苯三甲酸酐与多元醇进一步酯化后的产品作为固化剂使用，如乙二醇双偏苯三甲酸酐酯，其软化点为 $70\\sim80^{\\circ}C$ 。  \n\n![](images/507d86a2c7f4aa18ff79a2378df00527ef79d7918705ba335ea5228ec61ca173.jpg)  \n乙二醇双偏苯三甲酸酐酯  \n\n(8）二酰肼类的固化剂二酰肼类的固化剂最常见的有：己二酸二酰肼、间苯二酸二酰肼和癸二酸二酰肼（俗称癸肼)。最常用的品种为癸二酸二酰肼，熔点 $185{\\sim}190^{\\circ}C$ 。癸二酸二酰肼分子式为：  \n\n$$\n\\begin{array}{c c}{{\\mathrm{O}}}&{{\\mathrm{O}}}\\\\ {{{\\mathchoice{\\mathrm{NH}}{\\mathrm{H}}{\\mathrm{H}}{\\mathrm{H}}{\\mathrm{H}}{\\mathrm{H}}{\\mathrm{-}}{\\mathrm{NH-}}{\\mathrm{C-}}{\\mathrm{(CH}_{2})}_{8}{\\mathrm{-}}{\\mathrm{C-}}{\\mathrm{NH-NH-NH}}_{2}}}}\\end{array}\n$$  \n\n粉末涂料中癸二酸二酰肼用量为环氧树脂的 $7\\%$ 左右，固化条件一般为 $180^{\\circ}\\mathrm{C}/15\\mathrm{min}$ 或$170^{\\circ}\\mathrm{C}/20\\mathrm{min}$ 导  \n\n癸肼是长碳链结构，所以固化产物柔韧性较好，机械强度优良，泛黄性小，其涂膜的综合性能优于双氰胺固化体系，适宜制备浅色和白色粉末涂料。  \n\n因癸肼在应用时流动性差，故流平剂用量可适当多些，也可采用复合流平剂，以改善流平效果。目前，主要应用于电器绝缘方面的粉末涂料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 705,
+        "chunk": "# 二、环氧/聚酯混合型粉末涂料  \n\n饱和的端羧基聚酯树脂，既是环氧树脂的固化剂，并且在粉末涂料加工和成膜过程中也担当了重要的颜料分散和成膜作用。在配方中，羧基聚酯树脂的用量与环氧树脂用量相当，以致后来开发的较低羧基含量的聚酯树脂在配方中的用量比环氧树脂还要多，因而也可将环氧树脂看做是聚酯树脂的固化剂。这种环氧树脂和聚酯树脂互为固化剂，又同时作为成膜物质的粉末涂料体系，称之为环氧/聚酯混合型粉末涂料。聚酯树脂中的羧基与环氧树脂中的环氧基所发生的交联反应是加成聚合反应，反应中没有小分子产生，因此涂膜的外观可以做得很丰满，具有很高的装饰性。  \n\n粉末涂料用聚酯树脂多由芳香族羧酸与多元醇反应制成饱和的聚酯树脂。端羧基聚酯树脂的通式为：HOOC— $\\cdot\\mathbf{R}^{\\prime}$ —(OOC—R—COO—R')—COOH。  \n\n合成过程：先将多元醇和一部分多元酸反应生成端羟基聚酯，再与剩余的多元酸反应成为端羧基聚酯树脂。可根据需要合成出不同羧基含量的聚酯树脂，与环氧树脂采用不同的质量比进行搭配使用。  \n\n聚酯树脂主要的技术指标有外观、酸值或羟值、软化点、黏度和玻璃化温度等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 706,
+        "chunk": "# 1.外观  \n\n主要反映的是树脂的颜色和透明性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 707,
+        "chunk": "# 2.酸值  \n\n聚酯树脂酸值的大小是树脂中反应活性基团—羧基含量高低的指标，同时也能够反映出固化物交联密度的大小（酸值高羧基含量大交联密度大)。对于同一品种聚酯树脂来说，酸值的高低还反映出分子量的小与大。酸值是用来计算固化剂用量的指标依据，对于环氧聚酯混合型体系的粉末涂料来说，环氧树脂和聚酯树脂互为固化剂，那么在设计配方时两者的用量可按照以下公式来计算。  \n\n环氧树脂的数量(kg/g)=聚酯树脂的数量(kg或g）×聚酯树脂的酸值(mg KOH/g) 561×环氧树脂的环氧值（eq/g）  \n\n聚酯树脂酸值的不同，则与环氧树脂有不同的质量配比，人们依照这种配比变化将聚酯树脂大概分为50/50、60/40、70/30、80/20等型号。  \n\n表3-8-9是不同酸值的聚酯树脂在制作粉末涂料时的差别。  \n\n表3-8-9 不同酸值的聚酯树脂在制作粉末涂料时的差别  \n\n\n<html><body><table><tr><td rowspan=\"2\">性能</td><td colspan=\"3\">聚酯树脂与环氧树脂的比例</td></tr><tr><td>50/50</td><td>60/40</td><td>70/30</td></tr><tr><td>对颜料的剪切分散性能</td><td></td><td>十</td><td></td></tr><tr><td>对颜料的润湿分散性能</td><td>十</td><td></td><td>一</td></tr><tr><td>柔韧性</td><td>十</td><td>十十</td><td>十+</td></tr><tr><td>化学稳定性</td><td>十</td><td>十+</td><td>十+</td></tr><tr><td>粉碎性能</td><td>+十</td><td>++</td><td>+</td></tr><tr><td>静电喷涂时的带电性能</td><td></td><td>+</td><td>十</td></tr><tr><td>摩擦带电性能</td><td></td><td>+</td><td>++</td></tr><tr><td>高光应用</td><td>+</td><td>+</td><td>一</td></tr><tr><td>低光应用</td><td></td><td>++</td><td>++</td></tr><tr><td>边角覆盖性</td><td>+~i</td><td></td><td></td></tr><tr><td>附着性能</td><td>++</td><td>十+</td><td></td></tr><tr><td>耐溶剂性能</td><td>++</td><td></td><td>+-</td></tr><tr><td>耐酸性</td><td>+十</td><td>十+</td><td></td></tr><tr><td>耐碱性</td><td>十</td><td></td><td>++</td></tr><tr><td>耐磨性</td><td>+</td><td></td><td>+g =r</td></tr><tr><td>抗损伤性能</td><td>十十</td><td>十</td><td></td></tr><tr><td>耐洗涤剂性能</td><td>++</td><td>十+</td><td></td></tr><tr><td>耐涂抹性能</td><td></td><td>++</td><td>+</td></tr><tr><td>铅笔硬度</td><td>一 +</td><td>一 +</td><td></td></tr><tr><td>室内抗黄变性能</td><td>+</td><td></td><td>+</td></tr><tr><td>耐污染性</td><td>+</td><td></td><td>十+</td></tr><tr><td></td><td></td><td>+</td><td>+</td></tr></table></body></html>\n\n注： $^+$ 为性能加强；一为性能降低。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 708,
+        "chunk": "# 3.软化点  \n\n参照环氧树脂的软化点项",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 709,
+        "chunk": "# 4.黏度  \n\n树脂黏度对加工性能的影响表现在挤出时树脂对颜料的剪切、润湿和混合溶解过程。一方面，树脂在较大的剪切应力下对颜料会有较好的分散，物料在挤出过程中的剪切应力 $\\tau$ 与树脂的黏度 $\\mu$ 有以下关系： $\\tau{=}{\\mu D}$ ，式中， $D$ 为剪切速率。从关系式中可以看出树脂的黏度大则较利于颜料的剪切分散。另一方面，颜料的分散还有树脂对颜料的浸润过程，也就是说可以把颜料的聚集团表面看做是无数个毛细管，那么液体渗人毛细管的速度 $U$ 如下式：  \n\n$$\nU{=}\\frac{K r}{\\mu}\n$$  \n\n式中 $r$ ——毛细孔的半径；$\\mu t$ 1 熔体树脂的黏度；  \n\nK-—与树脂表面张力有关的常数。  \n\n因此，当颜料聚集团的空隙在一定的情况下，润湿速度主要取决于基料树脂的黏度，黏度越低润湿越快。经验表明，在高剪切速率下，剪切分散作用较明显；在如挤出设备这种中低剪切速率下，润湿分散作用则显得较重要。  \n\n在成膜方面，由于黏度是流动的阻力，于是黏度大的树脂流动速度较慢，或者说达到某一流平程度时所需用的时间较长，因而，树脂黏度低更利于粉末涂料成膜时的流平。  \n\n未固化聚酯树脂的黏度对固化后涂膜性能的影响则表现在聚酯树脂的分子量方面，对于这些聚合度较低的聚合物，树脂的黏度 $\\mu$ 与其数均分子量 $M_{\\mathfrak{n}}$ 符合如下关系式： $\\mathbb{k}^{\\mu=}$ $A\\lg M_{\\mathrm{n}}+B$ ，式中，A、B是和聚合度有关的常数，聚合度越高A值越大，树脂的数均分子量越大，其黏度呈 $A$ 次幂的级数增大。对于热固性树脂来说，固化后的分子量高，则耐热性、强度等性能好；固化后的分子量低，则耐热性、强度等性能较差。而未固化树脂的分子量大的，固化后的热固性树脂的分子量相应也大，其强度和耐性就高；未固化树脂的分子量小的，固化后的热固性树脂的分子量相应也小，其强度和耐性就低。  \n\n此外，研究表明：未固化聚酯树脂的分子量越小，要想使固化后的涂膜达到合适的强度时，固化剂的用量越接近理论值，也就是说此时的聚酯树脂与固化剂的配比量对涂膜性能的影响很敏感；反之，随着聚酯树脂的分子量的加大，在保证固化涂膜的强度下，聚酯树脂与固化剂之间的计量的宽容度越大。  \n\n综上所述，聚酯树脂的黏度值应考虑各方面性能的平衡，或针对某些性能来控制其黏度（分子量）的大小。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 710,
+        "chunk": "# 5.玻璃化温度 $T_{_{\\mathrm{~g~}}}$  \n\n固体聚酯在这一温度前后，热膨胀系数发生了转变。对于未固化的聚酯树脂来说，可以把玻璃化温度理解为树脂的玻璃态与树脂的高弹态相互转变时的温度。树脂在玻璃态时是脆性的，易粉碎而不发生粘连，在高弹态时则会发生粘连现象。粉末涂料在生产中的冷却、磨粉以及产品的贮运时一定要考虑这一指标。聚酯树脂分子的主、侧链结构和数均分子量 $M_{\\mathfrak{n}}$ 大小都会影响到它的玻璃化温度。聚合物数均分子量与玻璃化温度的关系式：  \n\n$$\nT_{\\mathrm{g}}=T_{\\mathrm{g}_{\\mathrm{cs}}}-{\\frac{A}{M_{\\mathrm{n}}}}\n$$  \n\n式中 $\\boldsymbol{A}$ —常数；  \n\n$T_{\\mathrm{g_{oo}}}$ —数均分子量 $M_{\\mathfrak{n}}$ 最大时的玻璃化温度。  \n\n由于人们在日常工作中往往使用黏度体现分子量的大小，而在常用聚酯树脂的分子量范围内(分子的聚合度较小)，聚酯树脂的黏度 $\\mu$ 与聚酯树脂的重均分子量 $M_{\\mathrm{w}}$ 的关系为 $\\log\\mu=$ $\\mathbb{l}_{\\mathrm{{g}}}M_{\\mathbb{w}}+K$ ( $\\bar{K}$ 为常数)，也就是说黏度和重均分子量成正比，常用聚酯的 $M_{\\mathrm{w}}/M_{\\mathrm{n}}=2\\sim5$ 由此可以看出，玻璃化温度随聚酯树脂黏度的变化比较复杂：一方面受到聚酯树脂结构的影响，即常数 $A$ ；另一方面还受到分子量分布离散度的影响，因此黏度大的聚酯树脂不一定玻璃化温度就高。在实践当中也发现有时将聚酯树脂黏度值的幅度提高较大时，玻璃化温度的增加并不明显。相反，同品种聚酯树脂的玻璃化温度的增高而黏度增大是很明显的，这在生产和选用聚酯树脂时应注意。  \n\n聚酯树脂的玻璃化温度对粉末涂料生产（特别是磨粉）和贮运显得十分重要，玻璃化温度较低的聚酯树脂会使材料稍遇温度升高就具有弹性而不好磨粉，或在贮运过程中容易结块造成产品不好使用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 711,
+        "chunk": "# 6.挥发分  \n\n粉末涂料使用的饱和聚酯树脂是熔融法工艺生产的，不使用溶剂，反应的生成水在后期  \n\n抽真空也能够除去，因此聚酯树脂的挥发分很低。  \n\n依据聚酯树脂酸值高低的变化而形成50/50、60/40、70/30等不同型号的聚酯树脂，在粉末涂料生产、成膜以及对涂膜的性能方面表现出了一定的差异。热固性的聚酯树脂是具有一定官能度和分子量的聚合物，其官能度 $F_{\\mathtt{n}}$ 与数均分子量 $M_{\\mathfrak{n}}$ 的关系如下。  \n\n$$\nF_{\\mathrm{n}}{=}\\frac{A_{\\mathrm{v}}M_{\\mathrm{n}}}{56100}\n$$  \n\n式中A——聚酯树脂的酸值。  \n\n从式（3-8-9）中可以看出，当官能度基本不变的情况下，聚酯树脂的酸值越低，它的数均分子量越大，因而其表现出来的熔融黏度也越大。低酸值的聚酯树脂使得体系的熔融黏度变大，加之低熔融黏度的环氧树脂的用量减少，在粉末涂料加工性能较差、往往造成挤出混炼不均匀，力学性能变差（如70/30的体系)；成膜方面表现在表面丰满度和流平性降低。  \n\n环氧/聚酯混合型粉末涂料具有很好的综合性能，由于含有环氧树脂成分，主要应用于户内使用产品的涂装，在装饰性的粉末涂料涂装领域替代了绝大部分的纯环氧体系的粉末涂料，是目前产量最大的粉末涂料品种。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 712,
+        "chunk": "# 三、纯聚酯型粉末涂料  \n\n由于环氧树脂不能够较长期地耐受紫外线照射，人们就使用其他的交联剂固化聚酯树脂，使体系的涂膜能够在很大程度上增加对紫外线的耐受性，应用于户外产品的涂装，这就是人们称之为纯聚酯型的粉末涂料。根据固化剂的不同，作为主要成膜物的聚酯树脂可制成端羧基的聚酯树脂，也可以制成端羟基的聚酯树脂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 713,
+        "chunk": "# 1.TGIC固化的纯聚酯粉末涂料  \n\nTGIC（又称三缩水甘油基三聚异氰酸酯、异氰脲酸三缩水甘油酯）是目前使用最广泛的、用于户外粉末涂料的羧基聚酯固化剂。  \n\nTGIC的熔融温度 $120^{\\circ}C$ ，黏度（ $120^{\\circ}C$ ) $0.\\ 058{\\sim}0.\\ 065\\mathrm{Pa}\\ {\\cdot}\\ \\mathbf{s},$ ，环氧当量 $102{\\sim}109\\mathrm{g/eq}$ ，热和光稳定性及耐候性优良，固化后的力学性能和电性能好，与聚酯树脂有很好的相容性，具有优良的透明度。与其对应使用的是端羧基聚酯树脂。对于官能度大约为2的双酚A型环氧树脂交联剂的端羧基聚酯树脂的官能度要大一些，而TGIC的官能度是3，那么被它固化的端羧基聚酯的官能度则要小，才能保证体系有适当的交联密度和固化速率。此外，选用不同的多元醇和多元酸合成的聚酯树脂在耐候性等方面会有差异，表3-8-10是不同的多元酸和多元醇对树脂性能的影响。  \n\n表3-8-10不同的多元酸和多元醇对树脂性能的影响  \n\n\n<html><body><table><tr><td>类别</td><td>活性</td><td>官能度</td><td>交联密度</td><td>黏度</td><td>T</td><td>韧性</td><td>冲击性</td><td>耐候性</td><td>硬度</td></tr><tr><td>对苯二甲酸 间苯二甲酸</td><td>十</td><td rowspan=\"6\"></td><td rowspan=\"6\"></td><td rowspan=\"6\"></td><td rowspan=\"6\"></td><td>+</td><td>+</td><td></td><td>+</td><td rowspan=\"2\">+</td></tr><tr><td></td><td>一</td><td>一</td><td>一</td><td>一</td></tr><tr><td></td><td>十</td><td>一</td><td>+</td><td>+</td><td>一</td></tr><tr><td></td><td>十</td><td></td><td></td><td>+</td><td>+ + +</td></tr><tr><td></td><td>+</td><td>+</td><td>一</td><td>一</td><td>一</td></tr><tr><td>乙二醇 丙二醇</td><td>+</td><td></td><td>+</td><td>一</td><td>+</td></tr><tr><td>己二醇</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td>一</td><td>+</td><td></td><td></td><td></td></tr><tr><td>三羟甲基丙烷</td><td>+</td><td></td><td>+</td><td></td><td>+</td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td>+</td><td></td><td></td><td></td><td>二</td><td></td><td></td><td></td></tr></table></body></html>\n\n注： $^+$ 为性能增强；一为性能降低。  \n\nTGIC的计算公式如下。  \n\nTGIC 的用量(kg或g)=羧基聚酯的重量(kg或g)×羧基聚酯的酸值(mg KOH/g)561×TGIC固化剂的环氧值（当量/100g）  \n\nTGIC可以和聚酯树脂形成溶液状态，造成聚酯的玻璃化温度 $T_{\\mathrm{~g~}}$ 降低，TGIC对聚酯树脂的用量每 $1\\%$ 降低其玻璃化温度 $2\\%$ ，一般情况下TGIC的用量是树脂的 $7\\%$ ，因此，使用TGIC固化的聚酯树脂的玻璃化温度应高于 $60^{\\circ}C$ 才能保证正常的磨粉和粉末贮藏的稳定性。  \n\n虽然TGIC 是综合性能非常优异的固化剂，但由于其具有毒性，许多国家限制了它的使用。另一种TGIC的衍生物——三 $\\beta$ 甲基缩水甘油基异氰脲酸酯则可以替代TGIC作为固化剂，商品名称为MT239。  \n\n从分子结构上来看，每个缩水甘油基与三聚异氰脲酸酯连接的亚甲基上都引入了一个甲基，此结构虽然降低了固化剂的毒性，但由于空间阻位的作用，也降低了环氧基的反应活性。除此之外，它依然保持了TGIC的其他性能。  \n\n其他含有活性环氧基团的固化剂还有偏苯三甲酸三缩水甘油酯和对苯二甲酸二缩水甘油酯混合物。  \n\n常温下偏苯三甲酸三缩水甘油酯（简称TML）是液体形态，对苯二甲酸二缩水甘油酯（简称DGT）则为结晶固体。两者虽然低毒，但都有一定的刺激性。DGT的官能度为2，单独使用则造成DGT使用量偏大，使得聚酯树脂的 $T_{\\mathrm{{g}}}$ 有较大的降低。为降低固化剂的用量，人们把TML（官能度为3）与DGT制成 $1:3$ 的混合物，商品名称PT910；或 $2:3$ 的混合物，商品名称PT912。其中把DGT作为TML的载体。PT910或PT912 和端羧基聚酯树脂固化后的涂膜性能与TGIC相当，但使用这两种固化剂都会降低聚酯的 $T_{\\mathrm{g}}$ ，降低粉体的贮存性能。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 714,
+        "chunk": "# 2. $\\beta$ 羟烷基酰胺固化的纯聚酯粉末涂料  \n\n$\\beta$ 羟烷基酰胺（简称HAA）固化剂是一种较新的户外羧基聚酯固化剂，分子结构中有四个活性羟基基团，与羧基发生脱水缩聚反应。最常用的是化学名称为 $N,N,N^{\\prime},N^{\\prime},$ 四 $C\\beta$ 羟乙基）己二酰胺，商品名称是XL552，国内的牌号为T105。  \n\n由于产品纯度问题或加有添加剂，羟烷基酰胺固化剂的实际当量按 $82\\sim100$ 计算。 $\\beta$ 羟烷基酰胺固化剂用量的理论计算公式为：  \n\n羚基聚酯用、羧基聚酯酸值、羟烷基酰胺 羟烷基酰胺固化_量（kg或g）（mgKOH/g） 固化剂当量 剂用量(kg或g) 56100  \n\n羟烷基酰胺与聚酯树脂的羧基发生的是缩合反应，也就是说它们在固化时有水分子产生，厚涂时涂膜表面容易产生针孔现象。  \n\n$\\beta$ 羟烷基酰胺固化剂具有用量少、固化温度低（ $150^{\\circ}C$ 即开始反应)、产品品质一致性好、无毒等优点。但抗泛黄性不佳，具有挥发性，涂膜光泽不易做高，其他性能与TGIC 体系相当。由于没有有效的固化促进剂，固化速率不易调整，只能通过选择不同的聚酯来实现胶化时间的变动。针对这种固化剂产生针孔和烘烤黄变的问题，人们通过添加一些抗黄变助剂等物质来改善这些缺陷，并将这种外加助剂的产品称之为 $\\mathbf{T}105\\mathbf{M}$ 0  \n\n通过羟烷基酰胺的结构式可以看出，该固化剂的官能度为4，因此与之配套的聚酯树脂的官能度要比用于TGIC的还要低，才能达到合适的交联密度和胶化时间。  \n\n另一种化学名称为 $N,N,N^{\\prime},N^{\\prime}$ 四 $(\\beta$ 羟丙基）己二酰胺的羟烷基酰胺固化剂，商品牌号为QM1260。  \n\n从结构式可以看出，QM1260与XL552的差异是在羟烷基上各多了个甲基，但由此提高了它的抗黄变性。  \n\n目前，许多聚酯树脂的生产厂家相继开发了针对羟烷基酰胺固化剂的低官能度专用聚酯树脂，某些厂商生产的专用聚酯以解决了光泽不高的缺陷。此外，在粉末涂料配方中使用非安息香脱气剂对烘烤黄变也有一定的益处。相比使用TGIC体系的粉末涂料，除前面所述的情况外，在耐候性方面没有什么区别，只是在较高温度的情况下，羟烷基酰胺体系的粉末涂料在耐湿气、耐水性、耐洗涤液方面稍有不足。羟烷基酰胺具有增加粉末颗粒带电性的作用，往往容易造成粉末的厚喷涂而形成静电堆积现象，使涂膜流平变差，必要时可加人一定量的抗静电助剂来控制粉末的带电量，防止厚喷涂现象。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 715,
+        "chunk": "# 3.多异氰酸酯固化的纯聚酯粉末涂料（聚氨酯粉末涂料）  \n\n把端羟基的饱和聚酯树脂作为主要成膜物，用封闭的异氰酸酯作固化剂制成的粉末涂料即所谓的聚氨酯粉末涂料。此时的聚酯树脂是含有羟基活性基团、具有一定官能度和分子量的聚合物。与羧基聚酯树脂相反，在聚酯合成配方中的多元醇过量，生产出来的就是羟基聚酯树脂，端羟基聚酯树脂的表达式为：HO一 $\\mathbf{\\cdotR^{\\prime}}$ -(OOC—R—COO- $\\mathbf{\\nabla}\\cdot\\mathbf{R^{\\prime}}$ )n-OH。  \n\n树脂中反应活性基团羟基含量的多少是计算固化剂用量的指标，也是固化体系交联密度的指标，用羟值来表示，即单位质量的样品中所含羟基的量。和酸值一样，所用单位是$\"\\mathrm{mg}\\mathrm{KOH/g\"}$ ，其中的 $\\mathrm{^{6e}m g\\ K O H^{\\prime\\prime}}$ 是度量羟基的单位。表面看， ${}^{\\mathrm{s}}\\operatorname{mg}\\ \\mathrm{KOH}^{\\mathrm{s}}$ 似乎与羟基毫无关系，这是为了计算上的方便，把羟基折算成KOH表示，按OH与KOH的计量关系， $\\mathrm{1mol~KOH}$ 中含有 $\\mathrm{{1mol~OH}}$ ，则 $\\mathrm{{1mol~OH}}$ 折算成 $1\\mathrm{mol\\KOH}$ ，就等于是 $56.1\\mathrm{g}$ 或者是$56100\\mathrm{mg~KOH}$ 。反过来 $1\\mathrm{mg\\KOH}$ 与 $1/56100\\mathrm{mol}$ 的羟基相当。因此用 ${}^{\\mathrm{{se}}}\\mathrm{{mg}\\ K O H^{\\prime\\prime}}$ 作为度量羟基的单位时， $1\\mathrm{mg}\\ \\mathrm{KOH}$ 的羟基就是 $1/56100\\mathrm{mol}$ 的羟基，并用羟值来计算固化剂的用量。  \n\n固化羟基聚酯最重要也是应用最普遍的一类固化剂就是用己内酰胺封闭的异佛尔酮二异氰酸酯（IPDI）多元醇的低聚物或自封闭异佛尔酮二异氰酸酯聚合物。它们都是脂环族异氰酸酯的衍生物，具有优异的户外使用性能。前者最具代表性的商品是Degussa公司的BF1530等。后者是Degussa公司的BF1540或其改进的BF1300和拜耳公司的LS2147等。  \n\n己内酰胺封闭的IPDI低聚物以BF1530为代表，它的玻璃化温度约 $50^{\\circ}C$ ，熔融温度在$75\\sim90^{\\circ}C$ ，解封温度是 $160{\\sim}170^{\\circ}\\mathrm{C}$ ，异氰酸酯基（NCO）的含量为 $15\\%$ ，游离的NCO基团含量小于 $1\\%$ 。  \n\n自封闭异佛尔酮二异氰酸酯聚合物的代表产品是BF1540等。BF1540的熔融范围是$105{\\sim}115^{\\circ}\\mathsf C$ ，总NCO含量是 $15.4\\%$ ，游离NCO含量小于 $1\\%$ ，在固化时 $98\\%$ 的缩脲二酮转化成IPDI与聚酯中的羟基进行交联反应。这种固化剂的优点是交联反应没有副产物。此类固化剂在 $120^{\\circ}C$ 是不会发生预交联的，可使用粉末的通用设备来生产。  \n\n计算异氰酸酯固化剂用量的关键指标是异氰酸酯基（NCO）的含量，固化剂用量的理论计算公式为：  \n\n异氰酸酯固化剂_0.0749×羟基聚酯的数量(kg或g)×羟基聚酯的羟值(mgKOH/g)的用量（ $|\\mathbf{kg}|$ 或g) 异氰酸酯固化剂中异氰酸酯基的含量（%）  \n\n异氰酸酯固化剂的实际用量达到理论用量的 $80\\%$ 就能很好的固化。  \n\n己内酰胺封闭的IPDI低聚物在固化反应过程中封闭剂已内酰胺被解封并释放出来，因此，应用此类固化剂的粉末涂料不宜于厚涂装，以避免涂膜产生针孔或气泡。用己内酰胺封闭的IPDI低聚物作固化剂制成的粉末涂料在使用时产生烟雾，不利于环保，然而，也正是封闭剂—己内酰胺，在解封到脱出膜层这一阶段起到了溶剂的作用，降低了熔融涂层的黏度，使涂膜流动的更加平整，以至于这种粉末涂料的涂膜能达到溶剂型涂膜的流平程度。而自封闭的IPDI聚合物既不存在挥发的问题，涂膜流平也没那么好。  \n\n由于BF1540的官能度小于2，因此其反应活性低，固化物交联密度不高，造成涂膜机械强度和耐溶剂等耐化学性能不太好。而经过改进的BF1300等产品的官能度可达到2.0，用改进的固化剂制成的粉末涂料在200℃固化8min，涂膜具有很好的力学性能，用1%的洗涤液于74℃浸泡500h，或90℃水中浸泡500h，涂膜的保光率依然超过80%。  \n\n用于多异氰酸酯固化的羟基聚酯中羧基基团的含量会影响涂膜的某些性能。据研究表明，含有羧基的羟基聚酯固化后的涂膜在耐盐雾性会受到影响，且涂膜在过烘烤时易发生黄变。  \n\n多异氰酸酯固化的纯聚酯粉末涂料具有极好的装饰性和力学性能，其耐化学性能和耐水性也很好，但在低温情况下容易开裂。该体系在制作消光粉末涂料方面具有非常大的潜力，不仅可以做到光泽的重复性好，而且表面硬度、机械强度和耐候性能都非常优异。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 716,
+        "chunk": "# 四、丙烯酸型粉末涂料  \n\n使用含有活性官能团丙烯酸聚合物制成的粉末涂料既为热固性丙烯酸型粉末涂料。生产丙烯酸树脂的主要单体是 $C_{4}\\sim C_{8}$ 的丙烯酸酯和甲基丙烯酸酯，通过与功能单体共聚合的方法很容易引入不同的官能团。比如丙烯酸、甲基丙烯酸是引人羧基；丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯是引人羟基；甲基丙烯酸缩水甘油酯（GMA）是引入环氧基等。  \n\n由于丙烯酸类单体的反应性能相差很大，因而导致各单体在共聚时在分子链上的分布不均匀，功能基团也不能像前面所说的聚酯树脂那样可以位于分子的链端，它们在高分子链上是随机分布的，并且分子链中支化点间的位置不易控制，这样就导致某些分子链上官能团的含量和位置及官能度都不确定，甚至某些聚合物分子的整个链段都没有官能团，或聚合物中另一些分子链上有很多官能团。由于聚合物中不含官能团的那部分分子（包括低官能度的分子）对涂膜力学性能的贡献不大，再加上过高官能度的那部分分子所形成交联聚合物的交联密度过大而影响了涂膜的力学性能，其综合结果是交联涂膜的柔韧性低、耐冲击性能差。  \n\n绝大部分得到实际应用的丙烯酸粉末涂料是含有环氧官能团的丙烯酸树脂作基料，以长链的二元酸作固化剂，如葵二酸或月桂二酸。固化剂中的脂肪长链为固化涂膜提供了一定的柔韧性和耐冲击性，但是远低于其他通用粉末涂料体系所能达到的程度。  \n\n目前国内在实际应用方面是将含有环氧官能团的丙烯酸树脂与TGIC或羟烷基酰胺固化剂配合，通过对羧基聚酯树脂的双固化用以制造户外消光粉末涂料。然而这种体系的粉末涂料，在力学性能、耐候性，特别是表面抗磨损性方面都不及传统的TGIC或羟烷基酰胺体系的粉末涂料。  \n\n国外的文献专利还报道了含羧基的内烯酸树脂与TGIC固化剂配合，用于生产透明的和有色的粉末涂料，据称力学性能、光泽和耐候性能都较好。而使用羟基丙烯酸树脂作基料，用己内酰胺封端的IPDI———己二醇加成物作固化剂，所得到的涂膜具有较好的柔韧性、光泽、耐化学品性和耐溶剂性。  \n\n国外一家公司使用羟基丙烯酸树脂与羟基聚酯树脂的混合物与封闭的异氰酸酯交联制作粉末涂料，据报道，这种混合体系的方法既解决了单独使用丙烯酸树脂的缺陷，也提高了单纯的异氰酸酯/聚酯体系的户外耐久性。这家公司还开发了使用羟基丙烯酸树脂和双酚A型环氧树脂组合的粉末涂料，这一体系融合了丙烯酸树脂的耐紫外线、坚硬等性能，以及环氧树脂的柔韧性和耐化学药品性。虽然涂膜的耐冲击性不如一般的聚酯/环氧混合体系的好，但作为一般性的要求已经足够了，而其他性能比如硬度、耐划伤性和耐磨损性已经明显超过了普通的聚酯/环氧混合型粉末涂料。  \n\n丙烯酸粉末涂料开发的初衷是基于丙烯酸树脂在溶剂型涂料中表现出来的优异的耐紫外线性能、透明性和耐烘烤黄变性而应用于汽车的外用涂装方面的，然而由于其涂膜机械强度不理想，而且它的耐光性能也达不到溶剂型涂料的水平，因此，它的实际应用市场并不大。最新的进展显示，纯丙烯酸粉末涂料的耐候性有了很大的改善，虽然涂膜的流平性还不够理想，但迫于环保的压力，一些国际知名的轿车生产商已经在尝试使用丙烯酸粉末涂料对整车进行涂装了，而且粉末涂料方面的科技人员依然在进行着改进产品性能方面的工作，并且通过粉末涂料颗粒的细微化而改善涂膜的平整度方面有了进展。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 717,
+        "chunk": "# 五、其他类型粉末涂料及辐射固化的粉末涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 718,
+        "chunk": "# 1.不饱和聚酯树脂粉末涂料  \n\n不饱和聚酯树脂是指线型分子链中含有一定量不饱和双键的聚酯树脂，这种树脂是通过双键的自由基聚合来进行交联固化反应。树脂分子中是通过使用一定量的不饱和二元酸或不饱和二元醇引人不饱和双键，由于不饱和二元醇的来源和价格问题，一般都使用不饱和二元酸，如顺丁烯二酸（酐）或其反式结构的富马酸来生产不饱和聚酯树脂。通过不饱和二元酸和饱和二元酸（用于调整不饱和双键在分子中的含量）与饱和二元醇进行酯化缩聚而制成不饱和聚酯树脂。不饱和聚酯树脂可通过有机胺或有机金属钻盐引发固化，快速固化时还需要加入一定量的过氧化合物，如过氧化苯甲酰或过氧化酮等催化剂，但这样会使粉末涂料的贮存稳定性不好。不饱和聚酯树脂的交联固化是自由基聚合反应，是放热反应过程，因此不饱和聚酯粉末涂料不仅可以做到低温（ $120^{\\circ}C$ ）固化，即使在涂膜较厚的情况下也能完全固化。使用引发剂和催化剂体系的不饱和聚酯树脂粉末涂料除了在模具的模内使用外，在其他方面的实际应用很少见，这可能是由于不饱和聚酯树脂厌氧固化造成涂膜表面强度不够好的缘故。目前，对不饱和聚酯树脂粉末涂料报道较多的是应用于紫外线（UV）固化的产品。用于紫外线固化的不饱和聚酯树脂粉末涂料中只需要加人光引发剂，而不需要加人对贮存稳定性有害的过氧化物催化剂，这样使得该体系的粉末涂料能够做到既有非常好的贮存安全性能又能做到使涂膜充分的流平并同时实现低温固化。由于紫外线对厚层涂装不能够很好的固化，这限制了不饱和聚酯树脂粉末涂料厚层涂装优势的发挥。  \n\n在不饱和聚酯树脂中引入抗厌氧固化的烯丙基(如含有烯丙基的酸或醇参与酯化缩聚)，以解决不饱和体系的厌氧固化问题，这种抗厌氧固化的不饱和聚酯树脂粉末涂料有可能在厚层涂膜涂装和低温固化领域（如在MDF的涂装方面）得以发挥作用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 719,
+        "chunk": "# 2.有机硅树脂粉末涂料  \n\n有机硅树脂（更正确地称为聚硅氧烷）主要用于耐高温 $c>200^{\\circ}C$ ）粉末涂料，有机硅树脂主链硅氧键（Si一O）具有较高的键能，所以耐热性优异，是耐热粉末涂料最常用的一种树脂。粉末涂料用硅树脂是高分子聚合物，其中含有甲基和（或）苯基取代基团。工业上合成硅树脂的单体是下列甲基和苯基取代硅烷。  \n\n$M e_{3}\\cdot5i[1\\cdot]$ 三甲基氯硅烷 $\\mathrm{Me}_{2}\\mathrm{Si}\\tilde{\\mathrm{Cl}}_{2}$ 二甲基二氯硅烷$\\mathrm{Ph}_{2}\\mathrm{SiCl}_{2}$ 二苯基二氯硅烷 $\\mathrm{PhSiCl_{3}}$ 苯基三氯硅烷$\\mathbf{PhSi(Me)Cl_{Z}}$ 苯基甲基二氯硅烷 $\\mathbf{MeSiCl_{3}}$ 甲基三氯硅烷  \n\n有机硅树脂主要是以二氯硅烷和三氯硅烷混合物水解而形成硅烷醇混合物缩聚而成，三氯硅烷用以提供支链化。在缩聚反应中剩余的未反应的硅醇基在以后的成膜时发生缩合或与其他聚合物进行交联反应。  \n\n有机硅树脂中甲基与苯基的比例决定树脂的性能，这种比例与树脂性能的关系见表3-8-11。  \n\n表3-8-11有机硅树脂中甲基与苯基的比例与树脂  \n\n\n<html><body><table><tr><td>高甲基有机硅树脂</td><td>高苯基有机硅树脂</td></tr><tr><td>固化时较低重量损耗</td><td>固化时较大重量损耗</td></tr><tr><td>较快固化速率</td><td>较长贮存稳定性</td></tr><tr><td>较高耐紫外线稳定性</td><td>较高热稳定性</td></tr><tr><td>较低温度柔韧性</td><td>较大耐氧化性</td></tr><tr><td>与其他树脂有较低的相容性</td><td>与其他树脂有较高的相容性</td></tr></table></body></html>  \n\n有机硅树脂可单独用来生产粉末涂料，对耐温要求不太高的粉末涂料也可与其他树脂共混的方法制作，但要使用苯基/甲基树脂比较高的有机硅树脂，以解决它们之间的相容性。颜料、填料种类对耐热性能也有很大影响，应注意选用。有机硅粉末涂料用于换热器、消声器、排气烟肉、发动机和烧烤设备等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 720,
+        "chunk": "# 3.用于辐射固化的粉末涂料  \n\n使用热固化的粉末涂料，由于固化成膜温度高 $(>150^{\\circ}C)$ ，使得它们在热敏材料上的使用受到限制，如木材、复合中密度板（MDF)、塑料和纸制品等。这类材料要求涂层在低于$150^{\\circ}C$ 的情况下固化成膜，虽然以羧酸/环氧为固化体系的粉末涂料也能在 $150^{\\circ}C$ 以下被催化固化，但此时，粉末涂料在平衡贮存稳定性、熔融流动性和固化之间的关系就成了问题，而辐射固化的粉末涂料则有效地解决了这之间的矛盾。  \n\n(1）紫外射线（UV）固化的粉末涂料UV固化的粉末涂料喷涂于物体上，首先被红外射线（IR）熔化（这样就不会使基材过热)，粉末粒子熔结成为连续的涂膜，再通过UV辐射，在光引发剂的作用下涂膜交联固化。由于将粉末的熔化过程与固化过程分开，因而就能够使用常规设备进行粉末涂料的制造，也能确保粉末在常温条件下稳定地贮存，同时达到在较低温度下成膜固化。  \n\n环氧树脂可通过使用络合阳离子盐作为光引发剂在紫外线照射下进行阳离子聚合。目前应用最多的则是不饱和聚酯树脂、不饱和丙烯酸酯与不饱和聚酯的混合物、丙烯酸改型的不饱和聚酯等，这类树脂在UV射线照射下，通过光引发剂进行双键的自由基聚合实现交联固化。  \n\nUV固化的粉末涂料在含有颜料的产品（如红色或黄色）上的使用存在不足，此外，光引发剂的品种、用量及紫外光源和固化时的温度都会影响到涂膜的固化。  \n\n国外的一些树脂生产商，如DSM和前UCB都开发了用于UV固化粉末涂料的不饱和树脂，并已经有了工业方面的应用，但数量不是很大。  \n\n用于UV固化的中密度复合木板（MDF）和金属上使用的粉末涂料配方及其涂膜性能见表3-8-12。  \n\n目前，国外一些研发机构正在开发第二代UV固化的树脂，比如通过提高树脂的结晶度等手段进一步提高粉末的贮存稳定性，降低熔结温度，提高粉末的熔融流动性。人们对UV固化的粉末涂料前景还是比较乐观的。  \n\n表3-8-12中密度复合木板和金属上使用的粉末涂料配方及其涂膜性能  \n\n\n<html><body><table><tr><td>组成</td><td>MDF 用透明粉</td><td>MDF 用白色粉</td><td>金属用透明析</td></tr><tr><td>不饱和聚酯树脂/%</td><td></td><td></td><td></td></tr><tr><td>MDF用乙烯基醚（VE）/%</td><td>16.7</td><td>13.8</td><td>45.2</td></tr><tr><td>金属用乙烯基醚（VE）/%</td><td></td><td></td><td>1.0</td></tr><tr><td>α-HAP光引发剂</td><td>1.0</td><td>1.0</td><td></td></tr><tr><td>BAPO/%</td><td></td><td>2.0</td><td>0.7</td></tr><tr><td>流平剂/%</td><td>0.7</td><td>0.7</td><td></td></tr><tr><td>钛白粉%</td><td></td><td>15.0</td><td></td></tr><tr><td>固化工艺</td><td></td><td></td><td>120s/100°℃</td></tr><tr><td>中波红外熔化</td><td>120s/100°℃</td><td>V灯 120s/100°℃</td><td>1600mJ/cm²H灯</td></tr><tr><td>UV固化</td><td>1600mJ/cm² H灯</td><td>4000ml/cm²</td><td></td></tr><tr><td>性能</td><td></td><td>好</td><td>好</td></tr><tr><td>涂膜流平性</td><td>好</td><td></td><td>好</td></tr><tr><td>外观</td><td>好</td><td>好 +十</td><td></td></tr><tr><td>耐甲乙酮</td><td>十十</td><td>++</td><td>++</td></tr><tr><td>耐丙酮</td><td>++ 188</td><td>149</td><td>90</td></tr><tr><td>摆杆硬度/s</td><td>0</td><td>0</td><td>0</td></tr><tr><td>附着力/级</td><td></td><td></td><td>>6</td></tr><tr><td>杯突/cm</td><td></td><td></td><td>40</td></tr><tr><td>耐冲击强度/in·lb</td><td></td><td></td><td></td></tr></table></body></html>\n\n注：1in=2.54cm，1lb=0.45kg。  \n\n(2）近红外射线（NIR）固化的粉末涂料1998年，国外开发了粉末涂料近红外固化技术，这种高强度的近红外辐射的强度比传统的中短波红外灯高几个数量级，能深深地穿透粉末涂层，可实现从粉末熔融到涂膜固化在数秒内完成。近红外固化的粉末涂膜具有非常好的外观，这是由于近红外加热速率非常高，加热又均匀的缘故。 ．北  \n\nH /I I近红外加热的优势在于有很高的粉末涂层穿透能力，使涂膜从内到外同时固化；非币回的加热速率，大大缩短了固化时间，减少了固化能耗，使产品使用具有更高的效率；对于较厚涂层和有色涂层的固化没有品种限制。粉末涂料固化技术比较见表3-8-13。  \n\n表3-8-13 粉末涂料固化技术比较  \n\n\n<html><body><table><tr><td>性能</td><td></td><td>2~3mi外固化</td><td>1~20近红外固化</td></tr><tr><td>熔融和固化时间</td><td>20~传统低温固化</td><td></td><td></td></tr><tr><td>最高表面温度/℃</td><td>140~160</td><td>100~120</td><td>100～200(由基材决定)</td></tr><tr><td>首选的固化机理</td><td>加聚反应、缩聚反应</td><td>链式加聚反应</td><td>加聚反应</td></tr><tr><td>对膜厚的限制</td><td>无</td><td><100μm</td><td>无 无颜色限制、各种光泽、美</td></tr><tr><td>目前可用产品范围</td><td>产品 各种颜色、各种美术型</td><td>美术型产品 特定颜色、各种光泽、某些</td><td>术、金属效果</td></tr><tr><td>较厚底材是否需要穿透加热</td><td>是</td><td>香</td><td>否(但由基材决定)</td></tr><tr><td>价格</td><td>低</td><td>高</td><td>中等</td></tr><tr><td>用于热敏基材的可行性</td><td>低</td><td>高</td><td>中等</td></tr><tr><td>在非金属材料上应用的可</td><td>非常有限</td><td>是</td><td>是</td></tr><tr><td>行性 基材形状限制</td><td>无</td><td>形状 仅仅是平面或简单三维</td><td>仅仅是平面或简单三维形状</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 721,
+        "chunk": "# 第三节 热固性粉末涂料的生产技术",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 722,
+        "chunk": "# 一、粉末涂料的配方及原材料",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 723,
+        "chunk": "# 1.粉末涂料的组成  \n\n粉末涂料没有溶剂，其组成结构比较简单，基本上可分为以下几种。  \n\n$\\textcircled{1}$ 成膜物质树脂，它是涂料成膜的基础，又叫基料。树脂是黏结颜填料形成坚韧连续膜的主要组分。  \n\n$\\textcircled{2}$ 助剂用以增加粉末涂料的成膜性，改善或消除涂膜的缺陷，或使涂膜形成纹理。  \n\n$\\textcircled{3}$ 颜料 赋予粉末涂料遮盖性和颜色。  \n\n$\\textcircled{4}$ 填料在一定情况下增加粉末涂料涂膜的耐久性和耐磨性，降低涂膜的收缩率和降低成本。  \n\n$\\textcircled{5}$ 功能组分 赋予涂膜某种特殊功能，如导电、伪装、阻燃等。  \n\n粉末涂料的成膜物质的性质决定了粉末涂料的主要性质和用途，人们选用合适的成膜物以及相应的固化剂来满足不同环境下使用材料的涂装，如户内、户外、海岛、高原等。成膜物的介绍请参照前两节的内容。",
+        "category": " Introduction"
+    },
+    {
+        "id": 724,
+        "chunk": "# 2.粉末涂料配方的要点  \n\n(1）配方总体颜填料量配方中的颜填料量在实际使用时是以重量来计算的，然而在分析问题时应考虑颜填料体积浓度（PVC）的因素，也就是说颜填料的体积占涂料总体积的百分比是直接体现粉末涂料产品许多性能的一个参数。这个数值的大小关系到粉末涂料生产时的混炼效果、流平性、纹理的效果、上粉率和材料成本。PVC 值越大，颜填料的分散就越困难、越不完全，粉末涂料熔融流动的温度越高，而且熔融时的流动性也越差，不利于涂膜的流平。颜填料体积浓度的表达式为：",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 725,
+        "chunk": "# 颜填料体积 颜填料体积浓度= 颜料体积+树脂体积  \n\n从式(3-8-13）中可以看出来，只要知道了各种材料的密度就可以算出配方的颜填料体积浓度，而实际上并不这么简单。首先是各种材料的密度难以全面准确地掌握，再者，实际生产时无法把颜填料分散到最小粒径状态并使树脂对颜填料完全润湿。因此，在实际应用当中很难得到准确地PVC值。然而可以通过颜填料的密度进行定性的判断，这对配方的设定非常重要，而且在配方的分析过程中具有理论方面的指导作用。  \n\n由于粉末涂料的颜填料量涉及的方面比较广，因此在配方设计上就要全面的平衡。在做美术粉时，还要考虑粉末涂料的熔融温度和熔融流动性的控制；在做高光粉时，就要考虑粉末涂料的熔融温度与其固化反应温度两者的差别要足够大，使粉末涂料在熔融状态的时间足够长而达到涂膜流平的目的。随着颜填料的体积浓度增加到一定程度时，就会产生一系列的影响。首先是在挤出混炼时树脂对颜填料分散程度的影响，随着颜填料体积浓度的增加，一方面增加了树脂对颜填料的分散量，另一方面也增大了体系黏度，也就是说增大了剪切阻力，不利于分散。其次，随着颜填料体积浓度的增加，片料的硬度也会加大，对磨粉产生影响。再者，由于粉末涂料生产工艺和挤出设备条件所限，颜填料粒子不可能完全被树脂所润湿分散，而随着颜填料的增加这种情况会越严重，在破碎和磨粉时颜填料裸露在外的机会就越大，则影响粉末颗粒的带电上粉率，还会在成膜时增加流平的过程以及产生针孔或细纹。颜填料体积浓度的增大还会使粉末涂料成膜时，形成熔融流动的温度提高而缩短了流平时间，还增大了熔融体系的黏度，也不利于涂膜的流平。  \n\n(2）粉末涂料遮盖力和颜色实际上就是根据不同的颜色，确定钛白粉或炭黑的用量，当保证粉末涂料在一定膜厚而不显露底材的情况下，遮盖颜料的用量应尽量低，从而也使调色颜料用量最少，既降低了颜料体积浓度也降低了材料成本。  \n\n粉末涂料颜料的选用和颜色调整对粉末涂料非常重要，颜料的选用不仅涉及粉末产品的应用性能，还涉及粉末涂料的成本及粉末产品与样品颜色的一致性。正确选用颜料的品种，避免颜料的性能与粉末产品的要求不符，以至于造成产品成本的提高或造成产品性能达不到要求。  \n\n(3）粉末涂料的配方结构粉末涂料成膜物、固化剂、助剂的选用及用量的大小涉及涂膜的流平、光泽和涂膜的力学性能、化学性能、产品的使用性能，这些材料的选用和用量决定了粉末涂料配方的结构，这些材料使用的不合理或不匹配将导致粉末涂料出现除颜色以外的一系列问题，在生产中把这方面的调整称为配方结构的调整。  \n\n配方结构包括：树脂与固化剂的配比用量、树脂占配方总量的比例（或颜填料占配方总量的比例)、各助剂占配方总量的比例等方面。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 726,
+        "chunk": "# 3.粉末涂料助剂  \n\n粉末涂料助剂是用以增加粉末涂料的成膜性，改善或消除涂膜的缺陷，或使涂膜形成纹理的材料。助剂是起辅助作用的材料，其种类和品种繁多，选用时一定要注意各助剂产生的作用，切不可乱用和滥用，使配方做到简单有效。粉末涂料的助剂大约分以下几种。  \n\n（1）流平剂粉末涂料使用的流平剂是低表面张力的丙烯酸聚合物。进口流平剂如PV-88、PLP100和ModaflowⅡ、ModaflowⅡl、2000、6000等系列都是丙烯酸共聚物吸附在白炭黑的固体粉末，纯流平剂的含量大约在 $60\\%$ ；国产流平剂由于受到技术和工艺水平的限制，产品都是丙烯酸的均聚物一—聚丙烯酸正丁酯（液态)，这一情况造成了产品的缺陷——单独使用会形成涂膜缩孔，因此，随后又做出表面张力更低的丙烯酸均聚物——聚甲基丙烯酸甲酯（固态，商品牌号701）来弥补前者的缺陷。从701的起源和作用来看，笔者认为它应归类为流平剂，为区别于普通固体流平剂，人们按习惯将它称作增光剂，而实际上它才是真正的固体（态）流平剂。在平面粉体系中，液流（纯流平剂）的正常用量为配方总量的 $0.4\\%\\sim0.6\\%$ ；701的用量为配方总量的 $0.5\\%\\sim1.5\\%$ ，过量使用会造成表面橘皮和失光现象。  \n\n(2）固化促进剂固化促进剂是加速树脂与固化剂反应、缩短固化时间、降低固化温度的组分。这种促进剂有酸性和碱性两类，酸性有三氟化硼络合物、氯化亚锡、辛酸亚锡等；碱性包括大多数有机叔胺、咪唑化合物等。不同类型的固化促进剂应用于不同的固化体系，即使同类型的固化促进剂对不同物质的促进固化效果也不相同。前面曾讲过咪唑及其衍生物作为环氧树脂体系固化的促进剂，此外还有季铵盐和季盐等，它们对聚酯/TGIC体系同样有效。有机叔胺虽然也对羟基/异氰酸酯体系有促进作用，但人们还是常使用有机锡化合物作为该体系的固化促进剂。羧基/羟烷基酰胺体系没有什么有效的固化促进剂。聚酯树脂的生产厂已在树脂生产时加有一定量的固化促进剂，基本已满足粉末涂料产品的使用，粉末涂料生产者如需进一步缩短固化时间或降低固化温度必须先做好试验工作，同时还要注意粉  \n\n末涂料的贮存稳定性。  \n\n(3）消光剂除前面所提到过的68和55型的消光固化剂以及GMA聚丙烯酸消光树脂和多元酸消光剂外，目前使用最广的是所谓的“有限反应消光剂”，即为市面上所说的物理消光剂，具体物质不详，一般认为是有机阴离子金属盐分散在聚乙烯蜡等载体中。一般具有较好的抗泛黄性能，有的产品能做到低于10%的光泽度。这类消光剂也分为户内、户外产品，但都对聚酯具有选择性，生产使用前一定要做好试验工作。此外，这类消光剂对酰胺类的材料较敏感，如T105、EBS等材料，当有这些材料存在时，其消光效果会大打折扣。由于这种消光剂是有限反应，配方中可忽略其化学用量的计算(也因此将其称为物理消光剂)。随其用量的增加，涂膜光泽降低，到一个极限后随消光剂的增加涂膜光泽不会有变动或略有升高。固化温度对光泽有一定的影响。此外，前面所提到的多元酸固化剂作为户外消光粉是通过两步反应进行消光，由于多元酸固化剂要消耗一定量的TGIC，配方中TGIC的用量较大，夏季会发生粉末结块情况。  \n\n(4）紫外光吸收剂、光稳定剂和抗氧剂初人行业的人员往往把这三者物质相混淆，特别是前两者。虽然它们都能提供聚合物分子的抗降解和涂层的耐老化性能，但机理并不相同。  \n\n紫外线吸收剂是将日光中的紫外部分的光能吸收并转化为热能的物质，通过这种转化，消除太阳光对涂层的损害。这类物质主要是羟苯基苯并三唑的衍生物等。  \n\n光稳定剂是能够通过捕捉高分子材料分子中产生的自由基来阻止聚合物分子的光化学降解作用的物质。这类物质一般是受阻胺，主要有四甲基哌啶的衍生物。  \n\n抗氧化剂又称热稳定剂，是被用来防止在过烘烤中涂层黄变的一类物质。一般情况下它们是空间位阻型抗氧化剂和抗水解的有机亚磷酸盐的混合物。  \n\n紫外线吸收剂和光稳定剂在协同使用时防光泽降低、防分解（粉化）、防变色的效果比单一使用要好得多。紫外线吸收剂的用量是树脂量的 $1\\%\\sim1.5\\%$ ，而光稳定剂的用量一般是树脂量的 $0.5\\%\\sim2\\%$ ，这类助剂只有和树脂均匀混合时的效果最佳，因此一般的树脂生产供应商已在户外用树脂中加有一定量的这类助剂。抗氧化剂的添加有个最大限量，一般是配方总量的 $0.2\\%\\sim0.5\\%$ ，过量加人反而不利。  \n\n(5）抗表面划伤和增滑剂涂膜的表面划伤包含有硬物划伤、擦伤和耐磨性等含义。要提高涂膜抗划伤、耐磨性能，就必须使涂膜表面具备足够的抗拉、抗压应力，也就是其表面所表现的柔韧及刚性要很高且很合理的平衡点。在刚性与柔性的结合上，一方面是通过保证固化后聚合物的分子量要足够大，使涂膜具有足够的强度；另一方面还要选择好具有合适结晶度及弹性的树脂作为成膜物。提高抗摩擦、抗划伤的另一个办法是增大涂层表面的滑爽性，使物体接触涂层表面时，滑动倾向大于划伤倾向。滑爽性是指低的表面摩擦阻力，可通过增加涂膜表面的细腻光滑性，以及加人能够在涂膜表面形成润滑膜的一类助剂来解决或改善涂膜抗表面划伤的问题，而这类助剂就是所谓的增滑剂。常见的增滑剂有聚乙烯蜡、改性的聚丙烯蜡和聚偏二氟乙烯与聚乙烯蜡的混合物等，这类蜡迁移至涂膜表面可使涂膜表面的动态摩擦系数大幅度降低，达到抗划伤的目的。这类助剂的添加量在配方总量的 $0.3\\%$ 以下时粉末涂料涂膜具有重涂性。  \n\n(6）纹理剂能使涂膜表面形成纹理的助剂称之为纹理剂。粉末涂料常用的纹理剂大概可分为如下几类：其一是和粉末涂料主体系不同的表面张力的低表面张力物质，此类材料包括CAB（即有合适玻璃化温度或黏度的醋酸丁酸纤维素）、加工成固体形态的具有一定粒径分布的流平剂以及含有一定比例硅油成分的物质等，通过不同的配方或工艺来做成具有凹凸或缩点的立体纹理，这就是人们常说的浮花剂或点花剂；其二是使粉末涂料体系产生触变性的有机或无机的触变助剂，使粉末粒子在低剪切速率下只熔融而不流动或有限流动，从而形成砂纹纹理，这类材料包括有机膨润土、气相二氧化硅、滑石粉、高岭土以及一些高吸油量或具有片层状结构的填料，此外还有一些有机触变剂，如一些氟蜡、丙烯酸共聚物的金属盐等有机离子聚合物；其三是具有一定触变性或与体系有不同熔融温度的颗粒（与粉末涂料进行后拼混)，形成多色的或凸出的颗粒点，这可以是某一种高熔点的聚合物，也可以是另一种粉末涂料；其四是本身具有挥发性或在固化反应产生挥发分的材料，当涂膜固化反应到一定黏度范围的时候，通过助剂（或反应产生的小分子物质）的挥发形成细小褶皱的纹理（即绵绵纹)，产品是一种有挥发性的有机铝化合物（如南海奉化的605-1A和六安捷通达的SA208）以及具有一定挥发性的烷烃蜡，前者用于纯环氧型纹理粉，后者可用于环氧/聚酯混合型的体系，具有反应挥发物的是四甲氧基甲甘脲固化羟基聚酯体系，该体系的绵绵粉可用于户外。通过不同的纹理助剂，再结合不同的配方和生产工艺，纹理粉可以做出丰富多彩的产品。  \n\n（7）抗粉末结块和粉体流动助剂具有足够大的比表面积（ $200\\mathrm{m}^{2}/\\mathrm{g}$ 左右）或足够小粒径（ $\\scriptstyle10\\sim40\\mathrm{nm})$ ）的气相二氧化硅或氧化铝，与挤出片料按 $0.1\\%\\sim0.3\\%$ 的加量拌和后一起磨粉，使气相二氧化硅或氧化铝粒子与粉末粒子形成高度分散，这种高度分散的气相二氧化硅或氧化铝粒子在粉末涂料粒子之间形成了隔离层，从而起到了粉末涂料的抗结块作用。而作为极小隔离层的气相二氧化硅或氧化铝粒子还起到了“滚珠轴承”的作用，提高了粉末涂料的粉体流动性。虽然这种共同磨粉的方法会多消耗一些助剂，但这是目前最有效的方法。  \n\n（8）脱气剂和“消泡剂”最常用的脱气剂是安息香，它作为一种“固体溶剂”使涂膜持续不断地展开（流动)，有足够长的时间让空气等小分子低温挥发物质从涂膜中逃逸出去。由于含有易烘烤黄变的杂质，在浅色粉中的用量受到限制，特别是在羟烷基酰胺体系中。安息香配合其他具有脱气功能的助剂共同使用则涂膜表面丰满的效果更明显，这些材料是具有一定表面活性剂作用或分散作用的助剂，包括一些复合聚乙烯蜡、酰胺蜡和氢化麻油等。此外，这些较高沸点的具有表面活性剂的助剂，在返锈工件和铸件上具有较高温度挥发物的封闭抑制作用，表面看是起到了“消泡”作用，而实际上是利用其高沸点和表面活性剂的作用流人孔隙中对高温挥发的物质起到封闭作用。  \n\n(9）增电剂（包括摩擦增电剂）能够改善粉末涂料粒子的带电程度的助剂。这类助剂在粉末涂料粒子带电不多时，如颜料、填料较高的情况下，能够改善和增加粉末涂料粒子带电荷的程度，效果好的助剂可作为摩擦枪用粉的摩擦增电剂。这类材料主要是一些含氮的化合物，特别是在粉末涂料体系中无反应影响的位阻胺化合物或其低聚物，而且物质中含氮量越高，增加带电效果越好。典型的应用例子就是羟烷基酰胺体系的粉末涂料，其带电性能要比不使用羟烷基酰胺的粉末体系高很多（还因其用量也大，基本在配方量的 $2\\%$ 以上)。此外，氧化铝在和粉末挤出片料一起粉碎后也能够增加粉末涂料粒子的带电性。  \n\n(10）抗静电剂和电荷控制剂抗静电剂和电荷控制剂都是可以降低粉末涂层或粉末粒子表面电阻率的助剂，尽管两者的作用类似，但应用的目的是不同的。前者是用来增加涂层的导电性以增加涂层向地面传送静电的能力；后者是用于控制粉末涂料粒子的带电性能和带电量以增加粉末粒子的带电速率从而增加粉末的上粉率以及克服法拉第效应所产生的粉末和工件吸附差的现象。有些物质，如季铵盐，既能起到增电剂的作用，也能够能起到抗静电剂和电荷控制剂的作用，只是用量不同而已。抗静电剂和电荷控制剂有个极限用量，例如在使用静电枪的时候，粉末的电阻率应在 $10^{12}\\Omega\\cdot\\mathrm{m}$ 左右，如果粉末的导电性太强，它们就会很  \n\n快地失去电荷从而对工件不吸附。  \n\n(11）颜料分散助剂颜料分散剂就是表面活性剂，它们在粉末涂料加工挤出和成膜过程中起到两方面的作用：增加树脂对颜料的润湿速率和程度；降低颜料聚集团的聚集能使树脂更容易将颜料分散。由于粉末涂料生产加工的特点，任何配料时所加入的颜料分散剂的效果都会大打折扣，这是由于分散剂与树脂或颜料的任何一方都不能够形成均质或高分散状态，这种不均匀状态使得分散剂加多后反而造成物料挤出时的“打滑”的情况出现，削弱或消除了物料的剪切分散作用，反而降低了颜料的分散性，这种情况主要反映在较难分散的炭黑和有机颜料上。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 727,
+        "chunk": "# 4.颜填料的选用  \n\n颜料是不溶性的细颗粒粉状物质。在粉末涂料的成分中，颜料是其重要的组成部分。它赋予涂膜的遮盖性、色彩；改进涂料的应用性能；改善涂膜的性能特性和（或）降低成本。颜料的分类方法有多种，从化学组成来分类可分成无机颜料和有机颜料两大类。或分成白色颜料、彩色颜料、体质颜料和功能性颜料四个类别。从生产制造角度来分类又可分为钛系颜料、铁系颜料、铬系颜料、铅系颜料、锌系颜料、金属颜料、有机合成颜料等，这种分类方法，往往一个系统就能代表一个专业生产行业，具有实用意义。国内外通常是以颜色分类的，如著名的《染料索引》及我国的国家标准。大部分颜料依据颜料索引号都能找出对应的物质，可依据其物质的性质对该颜料的基本性能有所了解并作为选用的一个依据。  \n\n由于在粉末涂料的生产和使用时不仅要经过高温过程，而且颜料在基料中分散的时间也非常短暂，加之粉末涂料涂装的产品使用环境的不同以及考虑粉末涂料产品的经济性问题，因而在设计粉末涂料配方时，颜料的选用是非常重要的。  \n\n(1）白色颜料大部分粉末涂料中都含有白颜料，白颜料不仅用于白色产品中，还用于各种较浅颜色的彩色产品中，在颜色中作为调节颜色明度的一种颜料，并在白色和浅彩色的粉末涂料中提供大部分的遮盖力。理想的白颜料理应不会吸收任何可见光，有高散射系数。因为控制散射能力的主要因素是颜料与基料之间折射率的差异，所以折射率是白颜料的关键性能。表3-8-14是粉末涂料常用的白色颜料及其指标。  \n\n表3-8-14粉末涂料常用的白色颜料及其指标  \n\n\n<html><body><table><tr><td>性能</td><td>金红石钛白粉</td><td>锐钛型钛白粉</td><td>氧化锌</td><td>立德粉</td></tr><tr><td>化学性质</td><td>极为稳定</td><td>极为稳定</td><td>两性化合物</td><td>不耐酸</td></tr><tr><td>相对密度</td><td>4.2</td><td>3.9</td><td>5.6</td><td>4.3</td></tr><tr><td>折射率</td><td>2.71</td><td>2.52</td><td>2.11</td><td>1.84</td></tr><tr><td>吸油量/%</td><td>≤20</td><td>≤22</td><td>14</td><td>14</td></tr><tr><td>相对不透明度/%</td><td>100</td><td>81</td><td>26</td><td>13</td></tr></table></body></html>  \n\n无论从化学性质还是从光学性质看，钛白粉，特别是金红石钛白粉是目前最好的白色颜料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 728,
+        "chunk": "# (2）黑色颜料  \n\n$\\textcircled{1}$ 炭黑色素炭黑从生产方法方面分类基本上可分为槽法炭黑、炉法炭黑和热裂法炭黑三种；从着色力或黑度方面分类可分为高色素炭黑、中色素炭黑和低色素炭黑三种，不同的生产方法所制造炭黑产品的性质、性能和成本（价格）有很大的区别。炭黑的应用范围主要依其粒径而决定，生产方法的不同炭黑的粒径范围也不同，如图3-8-4所示。  \n\n![](images/3de352b2e2636cd3062fd6489a77c9a026923319cdbdf4c44abc9927f383cda4.jpg)  \n图3-8-4 各种炭黑粒径的相对大小  \n\n随着技术的进步，一些炉法炭黑也能够达到槽法炭黑的质量水平而作为色素炭黑使用。  \n\n炭黑是烃类不完全燃烧生成的颗粒，加上炭黑粒子很细微，因此在炭黑粒子的表面还结合有酚基、鼠基、羧基和内酯基等含氧基团，这些含氧官能团则影响着炭黑表面的pH。含氧官能团多的，如槽黑，表面呈酸性（pH在3～5)；含氧官能团少的，如炉黑，表面呈中性或微碱性（pH≥7)。这对色素炭黑的分散性即对涂膜表面的光泽和流平的影响非常重要。此外，炭黑粒子表面的极性，特别是氧化后的炭黑极性增加（虽然增加了分散性)，但吸湿性也大大增加，这在贮运和使用中应引起足够的重视。  \n\n色素炭黑依据生产方法和粒径规定了如下划分，见表3-8-15。  \n\n表3-8-151 色素炭黑依据生产方法和粒径进行的划分  \n\n\n<html><body><table><tr><td>名称</td><td>国际通用代码</td><td>名称</td><td>国际通用代码</td></tr><tr><td>高色素槽黑</td><td>HCC</td><td>中色素炉黑</td><td>MCF</td></tr><tr><td>高色素炉黑</td><td>HCF</td><td>低色素炉黑</td><td>LCF</td></tr><tr><td>中色素槽黑</td><td>MCC</td><td></td><td></td></tr></table></body></html>\n\n① 由于低色素炭黑的范围过宽，有人也把它分为两类，即普通色素炉黑（RCF)，粒径范围28～40nm；低色素炉黑(LCF)，粒径范围41～70nm。  \n\n色素用炭黑分类见表3-8-16。炭黑性质对涂料性能的影响见表3-8-17。  \n\n表3-8-16 色素用炭黑分类  \n\n\n<html><body><table><tr><td>炭黑类型</td><td>粒径范围/nm</td><td>黑度指数</td><td>表面积范围/（m²/g)</td></tr><tr><td>HCC</td><td>10~14</td><td>260~188</td><td>1100~695</td></tr><tr><td>MCC</td><td>15~27</td><td>175~150</td><td>275～115</td></tr><tr><td>MCF</td><td>17~27</td><td>173~150</td><td>235～100</td></tr><tr><td>LCF</td><td>28~70</td><td>130~60</td><td>65～20</td></tr></table></body></html>\n\n$\\textcircled{1}$ 黑度指数：数值越高炭黑颜料的黑度越高。  \n\n当粒径减小或表面积增大时  \n\n\n<html><body><table><tr><td></td><td>增加，光的吸收更多，反射更少，使人觉得更黑</td></tr><tr><td>黑度</td><td>增加，基料需要量较多，自由流动的基料量减少</td></tr><tr><td>黏度</td><td></td></tr><tr><td>分散性 光泽</td><td>降低，粒子间引力增大，需要更多的能量破坏附聚体 降低，较高的基料需要量，涂层中共光反射的基料量减少</td></tr></table></body></html>  \n\n表3-8-17 炭黑性质对涂料性能的影响  \n\n\n<html><body><table><tr><td>黑度</td><td>增加</td></tr><tr><td>黏度</td><td>降低 对于大多数基料而言，表面酸度增加，相当于加人一种有效的分散润湿剂，颜料被基料润湿的</td></tr><tr><td>分散性</td><td>增加 阻力得以降低，有助于基料渗透到颜料粒子中去</td></tr><tr><td>光泽</td><td>增加</td></tr></table></body></html>  \n\n当炭黑结构增大时  \n\n\n<html><body><table><tr><td>黑度</td><td>降低，纤维状聚集体增多，相当于较粗粒子的效果</td><td></td><td></td></tr><tr><td>黏度</td><td>增加，基料需要量较多，自由流动的基料量减少</td><td></td><td></td></tr><tr><td>分散性</td><td>增加，由于黏度的增加，产生更大的剪切力破坏附聚体</td><td></td><td></td></tr><tr><td>光泽</td><td>降低，基料需要量增加，涂层表面上自由基料减少</td><td></td><td></td></tr></table></body></html>  \n\n粉末涂料应依据不同黑度的要求选择相应粒径的炭黑，根据粉末涂料加工时螺杆挤出分散性差的特点，应选用分散性好、对涂膜流平好的炭黑，即表面 $\\mathbf{pH}$ 较低的炭黑。  \n\n$\\textcircled{2}$ 氧化铁黑简称铁黑，分子式 $\\mathrm{Fe_{3}O_{4}}$ 或 $\\mathrm{Fe}_{2}\\mathrm{O}_{3}\\cdot\\mathrm{FeO}$ ，化学名称为四氧化三铁，相对密度4.73，遮盖力和着色力都很高，对光和大气的作用十分稳定，不溶于碱，微溶于稀酸，在浓酸中完全溶解，耐热性较差，在较高的温度下生成红色的氧化铁，在 $200^{\\circ}C$ 时转变为 $\\gamma_{\\mathrm{-Fe_{2}O_{3}}}$ ，在 $300^{\\circ}C$ 以上则转变为 $\\beta\\mathrm{{Fe}_{2}O_{3}}$ 。因此，氧化铁黑在粉末涂料中很少使用。  \n\n(3）红色颜料",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 729,
+        "chunk": "# $\\textcircled{1}$ 无机红色颜料  \n\na．铁红分子式 $\\mathrm{Fe}_{\\mathrm{2}}\\mathrm{O}_{\\mathrm{3}}$ 。具有优良的颜料性能，有很高的遮盖力（仅次于炭黑)，较好的耐化学稳定性（只溶于热浓酸)，耐热性高，很好的耐光性和耐候性，毒性极小。由于生产方法的不同，铁红的有不同的晶形（有立方形、球形、针形、六角形、菱形)，而粒径不同其色相等方面也有不同。铁红粒子的大小与颜色、着色力、遮盖力、比表面积及吸油量的关系见表3-8-18。  \n\n当炭黑表面酸度增加时  \n表3-8-18铁红粒子的大小与各种性能的关系  \n\n\n<html><body><table><tr><td>铁红类型</td><td>１</td><td>2</td><td>3</td><td>4</td><td>5</td><td>6</td><td>7</td><td>8</td></tr><tr><td>颗粒尺寸/μm</td><td>0.09</td><td>0.11</td><td>0.12</td><td>0.17</td><td>0.22</td><td>0.3</td><td>0.4</td><td>0.7</td></tr><tr><td>色调变化</td><td colspan=\"8\">黄红相→向蓝相变化→红紫相</td></tr><tr><td>着色力</td><td colspan=\"8\">大 小 ”</td></tr><tr><td>遮盖力</td><td colspan=\"8\">小 大 小</td></tr><tr><td>比表面积</td><td colspan=\"8\">大 小</td></tr><tr><td>吸油量</td><td colspan=\"8\">大 小</td></tr></table></body></html>  \n\n相同色相的铁红，针形的要比球形的着色力、遮盖力高，因为针形铁红粒子有比较高的散射能力。  \n\n铁红的用途很广，生产方法也很多，产品质量要求相差很大。干法生产的铁红虽然价低，但润湿性差，难于分散，不适用于粉末涂料。湿法生产中以硝酸盐法的铁红使用性能最好，但价高。混酸法次之，再次者为硫酸盐法。  \n\n由于氧化铁红价廉、稳定性高，在粉末涂料上使用非常厂泛，  \n\nb.钼铬红钼铬红是一种含有钼酸铅（ $\\mathrm{PbMoO_{4}}$ )、铬酸铅（ $\\mathrm{PbCrO_{4}}$ ）和硫酸铅$(\\mathrm{PbSO_{4}}$ ）颜色较鲜明的橘红色至红色颜料。着色力、遮盖力性能优良，耐热性非常好。在实际使用中，钼铬红颜料晶体的晶形易发生变化，使色泽会改变，耐光和耐候性不太好，通过对其表面进行二氧化硅致密包膜处理的产品则可用于户外。钼铬红含有重金属，在使用方面一定要注意。  \n\n$\\textcircled{2}$ 有机红色颜料有机红色颜料品种繁多，色相有黄相红、正红、蓝相红和暗红等。大多数是偶氮红颜料，而传统的偶氮颜料着色力较强，耐热性、耐光性和遮盖力都不太好，颜料迁移性较强，不适合粉末涂料使用。有些偶氮色淀品种能耐温 $180^{\\circ}C$ 左右，如颜料红#48： $1{\\sim}4$ 等，可适当地用于户内粉末涂料中，但由于颜料较细，耐光性和分散性都不太好，不过其价格低廉，其中颜料红 $\\#48\\div1$ 为鲜艳的黄相红，其他的为不同程度蓝相的红色，其中颜料红 $\\#48:4$ 的性能较好一点。大部分的偶氮色酚AS都有较好的耐性，颜色有黄相红、正红和蓝相红，有些耐光性能好的可用于对耐光性能要求不高的户外粉末涂料，粉末涂料常用的有颜料红 $\\yen170$ 的F5RK和F3RK等，其价格相对比较适中，前者为稍发暗的正红色相，而后者为黄相红。一些高性能有机颜料红则更适合在粉末涂料中使用，如缩合偶氮类、吡咯并吡咯类(DPP)、葱醒类及喹吖啶酮类和花系红等，它们具有较高的耐温性能，优秀的耐光和耐候性，经过表面处理后，其分散性和遮盖力比普通的偶氮颜料大为提高，但价格也相对较高。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 730,
+        "chunk": "# （4）黄色和橙色颜料",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 731,
+        "chunk": "# $\\textcircled{1}$ 无机黄色颜料  \n\na.铅铬黄目前，国内的铅铬黄颜料一般有五个品种，即柠檬铬黄、浅铬黄、中铬黄、深铬黄和橘铬黄，每个品种各厂家的颜色标准略有不同。柠檬铬黄色泽鲜艳，带绿相，着色力较中铬黄差；浅铬黄是纯正的浅黄色相，比柠檬铬黄要深些，着色力比柠檬铬黄稍好；中铬黄主要成分基本上是铬酸铅 $\\mathrm{{\\bfPbCrO_{4}}}$ 。其色泽饱和纯正，深浅适中，因而得此名，由于中铬黄性能优越，价格低廉，直至目前，依然是用量最大的黄色颜料；深铬黄比中铬黄色泽深、暗，遮盖力比重铬黄要好；橘铬黄是铅铬黄系颜料中红相最重的颜料。  \n\n铅铬黄颜料具有遮盖力强、耐热性好、着色力高、易分散和价格低廉等优点。然而由于含有铅和六价铬，使用上受到限制，不能用于玩具、文体用具等产品上，也是被欧盟RoHS指令所禁用的。柠檬铬黄和浅铬黄由于晶形的不稳定不能用于户外，耐热性也较差。即使是后三种铅铬黄，未经过表面包膜处理的产品，户外耐久性也很差，而经过二氧化硅致密包膜的产品则可用于户外，且耐热性也大大提高（耐热可达 $300^{\\circ}C$ )，但着色力和遮盖力均有所下降。  \n\nb.氧化铁黄颜料氧化铁黄又称羟基铁简称铁黄。化学式为 $\\mathrm{Fe_{2}O_{3}\\cdot H_{2}O}$ 或FeOOH，色泽为褐黄色，着色力接近中铬黄，具有良好的颜料性能。无毒性，耐光性能优良，可用于户外。耐温性能稍差， $150{\\sim}200^{\\circ}C$ 时开始脱水，当温度在 $270{\\sim}300^{\\circ}C$ 时脱水迅速，并转变为铁红（ $\\left(\\mathrm{Fe}_{2}\\mathrm{O}_{3}\\right)$ 。近几年，随着对有毒害颜料的禁用和限用，加之氧化铁黄低廉的价位，其地位越来越重要，特别是对于粉末涂料行业。  \n\nc.钒酸秘/钼酸秘黄化学式为 $4\\mathrm{BiVO_{4}\\cdot3B i_{2}M o O_{4}}$ ，是钒酸秘和钼酸秘两种不同的结晶结合而成。钒酸/钼酸铋黄的色光和着色力都接近于铅铬黄颜料，色泽鲜艳，具有优良的耐光性、耐候性和化学稳定性，分散性高，毒性很低，可作为无铅颜料。适应于做高性能户外粉末涂料，但价格较高。  \n\n② 有机黄色和橙色颜料大部分有机黄和有机橙色颜料是偶氮类的颜料，与偶氮类的红色颜料一样，传统或经典的单偶氮黄色和橙色颜料大多不适合粉末涂料使用。而偶氮颜料中联苯胺类的颜料由于分子量较大，和一些取代基团的作用，耐温性能较高，有些品种用于户内粉末涂料中以替代含重金属的铅铬黄颜料。常用于粉末涂料的联苯胺类的黄色颜料有：颜料黄 $^{\\#}\\mathrm{~13~}$ 、颜料黄 $^{\\sharp}14$ 、颜料黄 $\\sharp_{\\mathrm{~81~}}$ 和颜料黄 $\\sharp_{83}$ 等。但联苯胺类颜料在 $200^{\\circ}C$ 以上会分解出有毒的苯胺，因此有些国家禁止使用。苯并咪唑酮的偶氮颜料黄和颜料橙这类新型颜料的性能非常优异，可满足户外粉末涂料的使用，如颜料黄 $^{\\ddagger}\\mathrm{151}$ 、颜料黄 $\\#154$ 和颜料橙 $\\#36$ 等。此外，其他高性能黄色和橙色颜料还有缩合偶氮类、四氯异吲哚啉酮类、葱醒类等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 732,
+        "chunk": "# (5）蓝色颜料  \n\n$\\textcircled{1}$ 无机蓝颜料——群青粉末涂料常使用的无机蓝颜料是群青，主要作为调色颜料使用。群青是以硅酸盐为主要原料，经高温烧而形成的一种多元素、多成分、无毒的无机颜料。具有极好的耐光性、耐碱性、耐热性、耐候性，但易被酸的水溶液所破坏。国外已生产的有蓝色、紫色、红色的群青品种，我国现只有蓝色。蓝色群青色调艳丽、清新，非其他蓝色所比拟，但着色力较低。  \n\n$\\textcircled{2}$ 有机蓝色颜料———-酞菁蓝颜料酞菁蓝主要组成是细结晶的铜酞菁。它具有鲜明的蓝色，耐光、耐热、耐酸、耐碱、耐化学品的性能优良，着色力强，是粉末涂料中最常用的蓝色颜料。根据粗菁蓝在颜料化时的加工方法不同，有如下几个品种。  \n\na．不稳定 $\\alpha$ 型酥菁蓝（颜料蓝 $^\\sharp15\\cdot$ ）色光呈红相，遇高温（ ${}:>200^{\\circ}C$ ）发生“结晶”现象，颜色会发生变暗和褪色，不太适用于粉末涂料。国产酥菁蓝B、BX属于此类。  \n\nb.抗结晶 $\\alpha$ 型酞菁蓝（颜料蓝 $\\#15:1$ ）亦称稳定 $\\alpha$ 型酞菁蓝，色光同上，能够耐高温，但不抗絮凝，在粉末涂料使用时，涂膜常会产生“蓝点”现象。国产酥菁蓝BS 属此类。  \n\nc.抗结晶、抗絮凝 $\\alpha$ 型酰菁蓝（颜料蓝 $\\sharp_{15}:2\\rangle$ ）色光同上，耐高温，不絮凝。适用于粉末涂料。  \n\nd. $\\beta$ 型菁蓝（颜料蓝 $\\#_{\\textrm{l5}}:3)$ 能耐高温，色光呈绿相，不抗絮凝。国产牌号有BGS、颜料蓝4GN等。  \n\ne.抗结晶、抗絮凝 $\\beta$ 型酰菁蓝（颜料蓝 $\\sharp_{15}:4\\big>$ ）色光同上，耐高温，不絮凝。适用于粉末涂料。  \n\nf.e型酞菁蓝（颜料蓝 $\\sharp_{15}:6,$ ）色相呈大红光，稳定性、分散性优异，着色力比 $\\alpha$ 型酞菁蓝高 $25\\%$ 目",
+        "category": " Introduction"
+    },
+    {
+        "id": 733,
+        "chunk": "# （6）绿色颜料  \n\n$\\textcircled{1}$ 无机绿色颜料粉末涂料中有时使用氧化铬绿，用于调色，该颜料能用于户外，可利用其较高的对红外线反射作用而应用于伪装涂料。无机绿色颜料在粉末涂料中极少有人使用。  \n\n$\\textcircled{2}$ 献菁绿颜料献菁绿的化学组成是多卤代铜献菁，主要代人的卤素是氯和漠。商品酥菁绿G（颜料绿 $\\sharp_{7}$ ）含 $\\mathbf{14\\approx15}$ 个氯原子，即多氯代铜酥菁，色光呈蓝光的绿色。献菁绿$G$ 不存在同质多晶构造，在高温下不会发生“结晶”现象，但有“絮凝”倾向，需要加入添加剂以制得抗絮凝的产品，这种抗絮凝的菁绿颜料才更加适合粉末涂料的应用。  \n\n卤代铜菁被一定数量的溴原子取代时，其色光会偏黄，溴原子取代得越多，色光越黄。酞菁绿3G、6G（颜料绿 $\\sharp_{35}\\cdot$ ）的化学组成就是多氯、多溴代铜菁，色光呈黄光绿色。  \n\n酞菁绿3G含溴原子4～5个，氯原子8～9个；酥菁绿6G含溴原子9～10个，氯原子2～3个。酞菁绿 $3\\bar{\\bf G}$ 、6G的着色力比酰菁绿G要低，其他性能相似，价格较费。  \n\n（7）紫色颜料粉末涂料最常用的紫色颜料就是咔唑二嗪紫，或叫永固紫（颜料紫$\\#\\ 23)$ 。永固紫有突出的着色强度以及优异的耐热、耐渗性和良好的耐光牢度，色相呈蓝光紫色。在与献菁蓝一起拼混调色后仍能保持良好的耐光牢度，即使在冲淡后的浅色时也具有令人满意的耐候性能。微量的永固紫颜料还用作白色粉末涂料的吊色，冲压树脂的黄相，起增白剂的作用。  \n\n颜料紫 $\\yen19$ 是喹吖啶酮类的颜料，各项耐性优异，色相呈红光紫色，色相发暗程度低，常作为调色颜料使用，可用于户外产品中，这两种颜料的价格较贵。  \n\n（8）体质颜料（填料）体质颜料是指起填充作用的颜料。主要有碳酸钙、硫酸钡、滑石粉、高岭土、云母粉、硅灰石、二氧化硅等这些无机填料。体质颜料的折射率与基料树脂的折射率相近，几乎没有什么遮盖力。有些体质颜料由于其颗粒性质和粒子表面性质的特殊性，也能起到助剂或功能性的作用。  \n\n$\\textcircled{1}$ 碳酸钙碳酸钙分为轻质碳酸钙（又叫沉淀碳酸钙）和重质碳酸钙。轻质碳酸钙以石灰石（ $C a C O_{3}$ ）为原料，经烧而成为石灰（CaO)，再与水反应生成氢氧化钙$\\left[\\mathrm{Ca}(\\mathrm{OH})_{2}\\right]$ ，再与二氧化碳（ $\\mathrm{CO}_{2}$ ）反应生成碳酸钙，通过工艺控制而形成不同粒径的产品，即沉淀（轻质）碳酸钙和更细的微细、超细碳酸钙。重质碳酸钙是直接将石灰石或方解石等进行细微分化后分级而分成不同重质碳酸钙产品，目前，已能将其微分至 $1\\mu\\mathrm m$ 以下的细度(即所谓的高光钙)，称为重质细微碳酸钙。碳酸钙使用的安全性是被广泛认可的，现已大量地用于粉末涂料，廉价的碳酸钙不仅降低粉末涂料的成本，同时替代硫酸钡以减少产品中可溶性钡的含量。碳酸钙经表面处理后又形成了另一个品种——活性碳酸钙。早期用硬脂酸盐对碳酸钙进行活化，近期已使用到了整合剂或偶联剂等较新的活化剂（表面处理剂）来进行处理，从而提高了活化碳酸钙的使用性能和使用范围，但成本也有所提高。  \n\n$\\textcircled{2}$ 硫酸钡  \n\na.沉淀硫酸锁白色斜方晶体，相对密度4.5（ $\\mathrm{15^{\\circ}C})$ ，化学性质稳定。工业上采用芒硝-黑灰法生产，即将破碎的重晶石（ $\\mathrm{\\cdotBaSO_{4}}$ ）粉用还原剂煤（C）还原成硫化钡（BaS)，硫化钡制成溶液后与芒硝 $\\mathrm{\\langleNa_{2}S O_{4}}$ ）溶液反应生成硫酸钡的沉淀。沉淀硫酸钡的粒径细，分散性好，对光泽的影响较小。沉淀硫酸钡在分离和洗涤工序中，很可能由于设备或工艺问题造成可溶性锁超标，因此，在使用时应多加注意。  \n\nb.重晶石粉主要成分是硫酸钡，相对密度 $4.3\\approx4.7$ ，是直接将重晶石矿粉碎成细颗粒的产品。早期的重晶石粉主要用于压井和涂料腻子，现在则越来越精细化了。其质量主要取决于矿石的品位和颗粒的细度，较细的对光泽影响较小，较粗的可作为消光填料使用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 734,
+        "chunk": "# $\\textcircled{3}$ 其他体制颜料  \n\na.滑石粉又称含水硅酸镁，分子式为 $3\\mathrm{MgO\\cdot4SiO_{2}\\cdot H_{2}O}$ ，由滑石矿直接粉碎而成。粒子呈针状结晶，有滑腻感，有一定的触变性，对粉末涂料的熔融流动性有较大的影响，常用于纹理粉。  \n\nb.高岭土又称瓷土，又被误称为陶土。分子式为 $\\mathrm{Al_{2}O_{3}}\\cdot\\mathrm{SiO_{2}}\\cdot n\\mathrm{H_{2}O}$ ，具有六角形片状结构，粒子具有酸性活化点，对粉末涂料的熔融流动性有一定的影响，可作为纹理粉填料。  \n\nc.云母粉由复杂的硅酸盐类组成，粒子为鳞片状，耐热、耐酸碱性优良，对粉末涂料的熔融流动性有影响，一般在耐温和绝缘粉末涂料中使用，可作为纹理粉的填料用。  \n\nd.二氧化硅分子式为 $\\mathrm{{SiO}_{2}}$ ，由于其在橡胶中有类似炭黑补强的功能又称白炭黑，是  \n\n无定型二氧化硅。按生产方法可分为沉淀白炭黑和气相白炭黑。常使用气相白炭黑作为粉末涂料的松散和抗结块助剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 735,
+        "chunk": "# 5.消光粉末涂料  \n\n光泽是评估一个表面时得到的视觉印象，主要是光线与物品表面的物理性能相互作用的结果，反射率是涂层表面反射光线的能力，其所能反射的光的多少和反射状态则取决于涂层表面的平整性和粗糙度以及颜色与透明性，以反射光与入射光的比值来表示，称为该材料表面的反射比或反射率 $(\\%)$ ，称之为光泽度。如图3-8-5所示的就是光线照射到涂膜后，不同粗糙度涂膜的表面对光反射的状态，从而形成涂膜光泽度的变化。  \n\n![](images/543db188e98efad58dca2221bc6f2b99ebd75c76a59487e30fa85089b4df913f.jpg)  \n图3-8-5不同粗糙度涂膜的表面对光的反射状态  \n\n涂膜表面的粗糙密度及粗糙的立体程度越大，则涂膜表面对光线的漫反射程度就大，涂膜表现出来的光泽就低。粉末涂料就是通过各种手段使涂膜表面形成一定的粗糙度而达到消光的目的。  \n\n粉末涂料的消光方法有两种，即物理方法和化学方法。  \n\n(1）物理方法一将颜料、填料的加入量高于颜料的临界体积浓度（CPVC)，可以形成表面不规则的涂膜，从而达到消光的目的。使用这种方法不仅涂膜流平不好，而且涂膜的机械强度也会变差，光泽也不能消得很低。使用粒径较粗的（平均粒径为 $20\\sim40\\mu\\mathrm{m}$ ）填料，如机械粉碎的重晶石粉或石灰石粉作为消光填料，使配方颜料体积浓度小于CPVC，以保证涂膜有很好的流平性和机械强度，但光泽最低只能达到 $60\\%(60^{\\circ})$ 左右。  \n\n(2）物理方法二在配方中加人无化学反应活性的、与基料体系不相容的蜡等材料，如石蜡、聚乙烯蜡或聚丙烯蜡，或者是它们的混合物，用以产生涂膜表面不均一的效果。因为蜡可以在粉末固化时迁移到涂膜表面，形成一种细小的“微滴”状表面，以达到使反射光线散射的效果。然而，当蜡加量较多时，涂膜表面会有蜡析出，深色涂膜会有发白现象，并且这种方法也不能把涂膜光泽降到很低的程度，一般消光程度达到 $50\\%$ （ $60^{\\circ}$ 角）以上的光泽度。  \n\n粉末涂料使用物理消光方法很难达到低光效果，人们通过各种“化学”的方法，利用粉末不同步固化的原理是粉末涂料的涂膜表面形成一定的粗糙度而达到消光的目的，有些化学反方法能够使涂膜的光泽降得很低。  \n\n(1）化学方法—————干混法两种不同体系的粉末涂料混到一起后常会有干扰失光的情况发生，人们利用产生这一现象的原理将两种具有不同反应速率或含有不相容类型的粉末干混合，或将两种粉末的挤出物共粉碎制成消光粉末涂料。两种固化温度不同、反应速率不同体系的粉末在成膜时，反应温度低或固化速率高的先行固化，反应温度高或固化速率低的再后期固化，两者形成一定的界面使涂膜表面形成粗糙状态。由于是分子聚集团之间形成的界面，所以这种粗糙度的尺寸相对比较大，涂膜表面不够细腻，而且光泽度最低只能够达到  \n\n20%（60°)。例如：将高光的聚酯/TGIC=90/10的粉末与聚酯/TGIC=96/4的粉末共混合，或聚酯/HAA=90/10的粉末与聚酯/HAA=96.5/3.5的粉末共混，也可将聚酯十TGIC+固化促进剂的粉末与聚酯十HAA的粉末共混合，两种粉末的反应速率相差越大，涂膜的光泽越低。  \n\n也有将两种不同熔体黏度、不同表面张力或混容性相差较大的粉末进行干混，使之形成干扰成膜导致消光。如干混高光的混合型粉末和聚酯/TGIC的粉末、混合型粉末和纯环氧型粉末、聚氨酯和聚酯/TGIC粉末等。  \n\n以上的消光方法总是要做两种不同的粉末，既费时又费工，而且很难获得均匀的半光效果，光泽的重复性也不太好。  \n\n(2）化学方法二——一步法将两种不同固化温度或反应速率的组分配制在一起，共同挤出制粉，一步生产的消光方法。  \n\n$\\textcircled{1}$ 一步法方法一只使用一种成膜树脂，用两种不同反应温度或反应速率的固化剂对其进行双固化交联反应。最经典的要算用均苯四甲酸或偏酐与2-苯基-2-咪唑啉（环胱）所形成的盐作为双酚A环氧树脂双固化的消光固化剂。这种消光固化剂既含有与环氧进行低温快速固化的仲胺基团，又含有与环氧进行高温慢速反应的羧基基团。将环氧树脂与消光固化剂等材料配制一起，经挤出、粉碎制成粉末涂料。该涂料在烘烤过程中，盐分解成为它们各自的原始物质，即环胱和多元酸。环与部分的环氧树脂发生反应，使粉末预固化，成为具有一定柔韧而光亮的涂层。当烘烤温度继续升高时，反应活性相对低得多的羧基会进一步与环氧发生反应，使涂膜产生体型收缩。这种收缩受到之前预固化的牵制，分子链只能有限的活动，结果，这种受限的收缩在涂膜表面上形成了具有一定密度的、极细小的收缩点，从而达到消光的目的。如果在此基础上加人一定量的环胖，则会形成高光涂层，此时的环氧只与环眯发生反应，而其中的羧基并没有反应，这证实了消光固化剂的消光机理。当减少消光固化剂的用量，并补充相应部分的羧基基团（如羧基聚酯树脂)，这样就降低了这种收缩的密度，从而使涂膜光泽升高。由于这种收缩点所形成粗糙度的尺寸是分子级的，因而消光涂膜的表面看不出任何纹理，涂膜表现出非常细腻的效果，光泽最低可做到 $5\\%(60^{\\circ})$ 0  \n\n此外，还可以用GMA丙烯酸树脂和TGIC（或HAA）与羧基聚酯进行双固化交联而达到消光的目的。  \n\n$\\textcircled{2}$ 一步法方法二使用一种固化剂与活性官能团含量不同的两种成膜树脂交联固化，从而达到消光的目的。如用封闭的异氰酸酯固化剂与羟值差别较大的两种聚酯树脂配合形成双固化交联，用来制作消光粉末，光泽最低可做到 $20\\%(60^{\\circ})$ 以下。  \n\n也可通过使用一种树脂，再加人具有和树脂相同官能团的反应物质与固化剂实现快速聚合反应以达到双固化消光的目的。如羧基聚酯树脂与TGIC，再加人能与TGIC快速聚合反应的多元酸组分，可制成光泽 $15\\%(60^{\\circ})$ 左右的粉末涂料。  \n\n使用两种固化剂或两种树脂的双固化方法形成消光涂膜的表面粗糙度的尺寸介于干混法与消光固化剂法这两者之间，涂膜表面的细腻性一般。  \n\n$\\textcircled{3}$ 一步法方法三在一般的高光粉末的体系中加人某种高熔点的固化促进剂，这种固化促进剂如同颜填料一样分散在树脂基料里，在烘烤过程中形成微局部的催化固化反应，粉末的成膜物在固化促进剂周围形成许多个不连续的快速固化点，与周围正常固化反应形成双固化，达到消光的目的。要使快速固化点尽可能地在表面形成，必须先把这种固化促进剂与蜡制成母料形式，由于蜡与树脂不易相容，粉末在烘烤时母料会迁移到涂成表面。由于固化促进剂对各反应物质的质量不产生影响，因此有人把这种母料称之为“物理消光剂”或“有限反应消光剂”。这类“消光剂”对成膜树脂有较强的选择性，这可能与“消光剂”和树脂的相容程度及聚酯树脂的黏度有关。目前，这种“消光剂”能将混合型的粉末光泽做到10%（60°）以下，并且涂膜表面较细腻，涂膜的流平性和其他性能不受影响。  \n\n用化学手段使粉末涂料达到消光目的的方法还有很多，基本上都是形成不同步固化，在体系中形成非相容相，从而使涂膜表面形成一定程度的粗糙面，造成涂膜不同程度的消光效果。各种方法都有它的优点和局限性，当意识到这点后，就可以从中选取合适的方法为自己的应用服务，以便最大范围地减少消光粉末出现在生产中和使用方面的问题。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 736,
+        "chunk": "# 6.橘型纹理粉末涂料  \n\n橘型美术粉末涂料是指皱纹、锤纹、浮花纹和用填料法做的砂纹等粉末涂料。这类纹理粉其纹理的形成有个共同点一—都是在成膜过程中，利用表面张力的不平衡，或在表面张力不平衡状态下固化成膜而形成纹理的。以这种方式形成的美术型粉末涂料，涵盖了大部分纹理粉末涂料的类型。  \n\n(1）粉末涂料的成膜过程粉末由静电吸附在工件上，受热升温到某一温度时开始熔融，由于粉末的熔融有先后，加之各组分混溶和分散程度的差别，使得熔融物表面产生张力差，又由于热量的交换和在表面张力差的作用下，熔融液体产生无数个细小湍流（贝纳德窝），如图3-8-6所示。  \n\n随着温度的上升和时间的延续，粉末继续熔融、湍流、表面张力向平衡驱动一一进行流平，凸凹的贝纳德窝逐步变大，并在某一温度下，树脂开始发生交联反应，涂料的黏度开始增加，又随着温度的升高和时间的延续，粉末涂料的黏度越来越大，湍流和表面张力平衡的速率也越来越慢直至停止，粉末涂料开始出现胶凝状态，再随着温度的升高或保温时间的延续，树脂的交联反应趋于停滞——成膜。  \n\n（2）纹理的形成从上面的图示和过程来看，所谓橘型纹理粉，其纹理就是某种程度贝纳德窝的定型，通过人为的各种手段对贝纳德窝深浅大小的定型控制，就形成了不同深浅（立体感）和大小的橘型纹理。在实际生产中，通过加人适量的低表面张力的材料来控制贝纳德窝的形成和形状大小，如固体流平剂、混溶一定量硅油的固体树脂、CAB等，来保持凹处的低表面张力点，从而加大凸凹的表面张力差，并延长这种不平衡的时间。既然要形成这种点，因而低表面张力的材料就不能加得过多，否则它们会形成连续的分子层，使涂膜趋于流平——立体感变差。反过来也不能加得太少，这样低表面张力的凹点拉得太开，湍流时回流的物料填补不了凹处，会使涂膜出现缩孔。  \n\n![](images/3c46dc199c0d2333aa085912eadf96cbb81edff4e1b24aa4e165903cf3e8f525.jpg)  \n图3-8-6 贝纳德窝  \n\n$\\textcircled{1}$ 皱纹由于颜料、填料较均匀地分散在树脂中，在形成贝纳德窝时，物料呈较均匀湍流，从而形成单一色的凸凹纹理。如果在设定配方时，选用分散性不好的颜料（特别是有机颜料）表面会出现发花和浮色现象，这是因为湍流时，一部分未分散的细颜料被带到了较高表面张力的凸处，而粗的颜料沉积到底层。也可用此方法来大概检测一下颜料的分散性。  \n\n$\\textcircled{2}$ 锤纹银粉经挤出后，一部分的鳞片状被破坏，在形成贝纳德窝时，一部分细的银粉被湍流带到凸处，形成深色、粗的沉积到底层，在凹处形成金属感稍强的浅色。有时，为了增强湍流和延长湍流的时间，内加一点流平剂，这样就会使凹凸间的表面张力差变小，这不仅使更多的细银粉被迁移到凸处，也使深色处面积增加，同时增大了凸凹间的色差。  \n\n③浮花纹其原理和过程与锤纹相同。由于它后混有外浮颜料，不仅对粉末熔融的情况影响较大，也对湍流的影响较大，特别是浮拼色颜料，粒径要细、匀，密度相差不要过大。  \n\n④ 砂纹这里是指用填料和触变助剂做的砂纹，其原理类似皱纹。关键是控制粉末从熔融到胶凝的时间，也就是说贝纳德窝刚形成就得定型。这个时间越短纹理就越小，因粉末未形成多的熔融和大的湍流，一般不需加低表面张力的纹理剂。  \n\n(3）橘型粉纹理的影响因素和控制方法既然橘型粉的纹理是贝纳德窝形成的，那么影响贝纳德窝的大小和贝纳德窝湍流时间的因素就是影响橘型粉纹理的因素。  \n\n$\\textcircled{1}$ 纹理剂就是人为形成和控制贝纳德窝低表面张力凹点的原料，分内加、外加两种。内加型纹理剂参与挤出，在粉末的内部形成分散，因而对这种材料的熔点和分子量的分布有一定的要求。熔点太低，纹理剂极易分散，纹理剂用量稍少一点，就会出现缩孔，再稍多一点，又有可能使纹理立体感变差，不好控制。熔点太高，则不易分散，造成纹理不均匀，有时还会形成局部缩孔。内加纹理剂对其本身的粒径没什么要求。用这种方法做的纹理粉，工艺简单、纹理较稳定，但纹理大小的调整范围不大，易受外界干扰产生缩孔。外加型纹理剂是掺在底粉里，再经混合制成纹理粉。因此纹理剂粒径的大小、粒径分布的大小，纹理剂和底粉混合时的强度及混合时间的长短都会对纹理产生影响，加之纹理剂的颗粒是多次聚积团，很不稳定，因而在生产中一定要注意工艺控制、纹理剂的加量、纹理剂的批次等之间的稳定或调整。由于外加纹理剂的方法对纹理的影响因素多，因此稳定性不好，对操作人员的要求也高。然而由于其变数多，纹理调整的范围也大得多，纹理可小如芝麻、大如硬币。这种纹理剂的品种也多，可选用较低表面张力的纹理剂，加大贝纳德窝的表面张力差，增加粉末纹理的立体感。  \n\n$\\textcircled{2}$ 粉末的胶凝时间从前面所述粉末的成膜过程可以看出，粉末的状态是固-液-固的变化（简单来看)，贝纳德窝是在粉末的熔融状态即液态时形成的，随着湍流和表面张力差的平衡过程的延续，贝纳德窝的直径由小变大，同时其凸凹的差别由小变大，再由大变小，该变化持续至粉末胶凝时停止（这种流动变化是在胶凝前还是在胶凝时停止还不清楚)。所以，粉末的胶凝时间短，则纹理小；粉末的胶凝时间长，则纹理大；时间再长，则纹理的立体感就差了。粉末的胶凝时间太短或太长都不利于纹理的形成。  \n\n$\\textcircled{3}$ 聚酯的胶凝时间聚酯胶凝时间的长短是和粉末胶凝时间相对应的，各聚酯生产厂家在聚酯内所加催化或促进助剂的品种和量有所不同，材料换用时要注意。  \n\n$\\textcircled{4}$ 催化助剂 可缩短粉末的胶凝时间，使纹理变小。  \n\na.温度温度对粉末纹理的影响既是非常重要的，也是非常复杂的。与其说温度对粉末纹理有什么影响，倒不如说热能量、热能效和各物质对热量传导的影响，当然，这些都具体表现在温度上。橘型粉末的纹理是在粉末熔融至胶凝这一阶段形成的，而贝纳德窝也只有在涂层呈液体状态下才可有之，贝纳德窝的大小是随时间的延续而加大的。因此，橘型粉末的纹理是受粉末初始熔融的温度、粉末初始反应的温度及其速率、粉末的胶凝时间所影响。  \n\nb.粉末的受热过程粉末涂料附着在金属工件上进人烘炉，由于粉末涂料是非导热体，在热空气对流或（和）辐射的作用下，粉末表面受热融化，再通过对流将热能向粉末内层传递（接触工件-一面的粉末层的热传递比较复杂，在下面“被涂工件”再说明)，加之在粉末熔融的过程还伴随着固化反应和胶凝的过程，因此说温度对纹理的影响是较复杂的。  \n\n$\\textcircled{5}$ 配方一是配方的颜料、填料量，配方颜料、填料用量大，会使粉末初始熔融温度高，缩短了贝纳德窝流动过程的时间，粉末纹理小；或者是吸油量大的颜料、填料（如炭黑、有机颜料、沉淀碳酸钙、滑石粉等）加量较大也会如此。二是树脂体系（基料体系），树脂体系的不同，则影响到粉末固化反应温度和熔融状态持续时间的不同，如纯环氧树脂（双氰胺固化剂）体系，初始固化温度比混合型要高，其熔融状态相对较长，形成贝纳德窝的过程就长，因而形成的纹理就较大。前面所述“聚酯的胶凝时间”也有所涉及。  \n\n$\\textcircled{6}$ 粉末的粒径简单地说，由于粉末热量的传递是由表面开始的，粒径小使得吸热面积大，这样热效率就低；粒径大使得吸热面积小，热效率就高。再者，贝纳德窝的初始形态也和粒径的大小有关，粒径小则窝小，粒径大则窝大。  \n\n$\\textcircled{7}$ 喷涂的厚薄由于粉末涂料的热量传递是靠熔融状态下对流传递的，粉末堆积得厚，热量传递得就慢，粉末熔融的过程就长，贝纳德窝流动的过程就长些，加之贝纳德窝的形成是有一个空间的。粉末堆积得薄，热量传递得就快，粉末熔融的过程就短，贝纳德窝流动的过程就短些。所以，相同的纹理粉，喷涂厚则纹理大；喷涂薄则纹理小。  \n\n$\\textcircled{8}$ 被涂工件 被涂工件的影响可分为两种情况。  \n\na.工件的材质不同的材质的热导率是不一样的，从有关资料里可以查到。  \n\nb.对于工件的厚度和涂覆状态方面例一：薄板单面喷涂（如配电箱柜等)，当粉末表面受热的同时工件也受热，并迅速传导热量至粉末的另一面，粉末双面受热，融化较快，使之熔融状态时间较长，相对纹理较大。例二：厚板单面喷涂（包括某些铸件等)，由于工件的热容量很大，粉末即使熔融彻底，但因为工件接触粉末处的温度较低，此时粉末的热量向工件传递，消耗了粉末的热能，使粉末熔融过程时间延长，缩短了彻底熔融的时间，贝纳德窝展不开，而使粉末的纹理变小。还有类似这种情况的喷涂：对柱状和管状工件形成包覆喷涂的，都会造成粉末在受热时向工件传递热量，使粉末的热能效降低，从而缩短了粉末形成熔融状态的时间，使粉末的纹理变小。  \n\n$\\textcircled{9}$ 烘烤条件无论是烘箱还是烘道都为粉末固化提供一个热源，而这种热量的传递一是对流、二是辐射，因此烘箱或烘道的热效率应尽量要好，而且热空气的循环对流也要充分。烘箱或烘道的热效率高，粉末受热好，粉末的熔融时间就长，纹理就大；烘箱或烘道的热效率低，粉末受热差，粉末的熔融时间就短，纹理就小。  \n\n以上，从贝纳德窝理论的角度阐述了橘型粉末纹理形成的机理。而控制这些纹理的形状、大小要对粉末的熔融温度、固化反应温度、胶凝时间等因素应有一个全面的把握，加上对粉末涂料成膜过程的认识，才能全面地掌握其规律。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 737,
+        "chunk": "# 7.金属和珠光粉末涂料  \n\n(1）金属颜料金属颜料是不同形态的粉末状金属，是颜料中的特殊种类。常见的金属粉有铝粉、锌粉、铜锌合金粉和不锈钢粉等。球形的金属粉末金属光泽和遮盖力差，几乎没有颜料性能。而金属颜料是鳞片状的粉末，具有明亮的金属光泽和颜色，在涂料成膜时，鳞片状的金属粉末粒子能像落叶铺地一样的与被涂物平行，多层排列，互相连接形成遮盖，并表现出相应的金属色泽。鳞片状的金属粉末必须经过表面处理才具有分散性、遮盖力等颜料特性。  \n\n$\\textcircled{1}$ 铝粉颜料表面经包覆处理的鳞片状铝粉，具有明亮的银白色，俗称银粉。鳞片状铝粉的片径与厚度的比值是厚径比，而铝片粒子的表面越光洁，其厚径比值越大，则金属亮度越高，金属感越强；其厚径比值越高，粒径越小，则遮盖力越好。铝粉颜料根据表面处理不同，则有漂浮型（浮型）和非漂浮型（非浮型）之分。  \n\n混有浮型铝粉的粉末涂料在成膜过程中，由于铝粉表面的疏油性，铝粉向有空气层的表面漂浮，并形成与空气和涂层界面平行的方式排列，粉末涂层熔融流动的时间越长，则会有越多的铝粉向涂层表面漂移富集，此时铝粉在涂膜中所表现的利用率较高。相反的情况下，由于涂层的熔融流动时间较短，则有较多的铝粉粒子留在了涂层中间而没有形成表面排列。此时，若想达到近似于前者涂层的表面效果，铝粉用量就要增加，表现出铝粉的利用率不高。浮型铝粉在涂层表面的漂浮现象相似于木板在水中的漂浮，铝粉漂浮在涂膜的表层，此时这类涂膜表面的抗划伤、耐磨性、耐污性和耐候性不会太好。  \n\n非漂浮型铝粉则不会在涂层表面形成漂浮现象。相反，它们在成膜过程中沉积在涂层的底部或悬浮在涂层中间。因此非浮型铝粉的遮盖力和金属感没有浮型铝粉强，但会产生金属光泽的闪烁点（这可能是铝片在涂层中不同的排列形成的光反射差)。由于非浮型铝粉基本上包含在了涂膜的内部，因而涂膜的抗划伤性、耐磨性、耐污性和耐候性较好。  \n\n闪光铝粉是一种特殊的非浮型铝粉，它的鳞片呈规则的“圆饼”状，并且鳞片的粒度分布范围狭窄，表面光洁度高，从而形成整齐的、高强度的金属光泽反射。粒径较大的闪光效果较强，铝粉中非圆饼状粒子含量越低闪光率越高。  \n\n铝粉颜料中只有用二氧化硅包覆的铝粉才具有较好的耐候性，如对耐候性有更高的要求时，就要使用致密的二氧化硅包覆的铝粉。  \n\n$\\textcircled{2}$ 铜锌粉（铜金粉）铜锌粉颜料具有各种不同色光、细度和特性。根据铜锌合金含量的不同，可分为青光铜锌粉（含铜量 $75\\%\\sim80\\%)$ ，又叫绿金粉；青红光铜锌粉（含铜量$84\\%\\sim86\\%)$ ，又称浅金粉；红光铜锌粉（含铜量约 $88\\%$ ，又称红光金粉。  \n\n铜锌粉颜料粒子表面均包覆一层有机膜，既减轻粉的密度又增加其表面张力，使铜锌粉颜料在涂层中具有漂浮性，其遮盖性原理与铝粉颜料的原理一样。铜锌粉在潮湿和高温下易氧化，其色泽转暗，但经特殊包覆处理的铜锌粉可耐高温和耐候。  \n\n(2）珠光颜料云母钛珠光颜料根据它反射光的色相分为三大类：银白类、彩虹（幻彩）类和着色类。较粗大的云母钛珠光颜料粒径会产生星光闪烁的金属视感，而粒径较细小的则呈现类似丝绸或软缎般的、细腻柔和的珍珠光泽。  \n\n一般的云母钛珠光颜料耐光、耐候性较好，可用于户外粉末涂料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 738,
+        "chunk": "# 二、粉末涂料的生产工艺",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 739,
+        "chunk": "# 1.粉末涂料生产工序过程  \n\n粉末涂料生产工艺过程分为四个工序：配、混料工序；热混炼、挤出工序；冷却、破碎工序；磨粉、筛分工序。前两道工序，其目的就是要使成膜树脂相互溶解均匀，并使颜料、填料在树脂中分散得足够均匀。而后两道工序，就是如何粉磨好。因此，粉末涂料就生产和产品控制而言就是两个要点：如何使粉末涂料的各种原材料混合分散均匀，使其具备涂料的性能；如何将混合分散好的物料加工成合适粒度的粉料，以利于涂装使用。  \n\n粉末涂料的生产流程及操作要点如图3-8-7所示。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 740,
+        "chunk": "# 2.涂料的生产设备及其结构和工作原理  \n\n热固性粉末涂料的生产设备一般分为四个部分：配料设备、混炼挤出（分散）设备、冷却破碎设备和磨粉设备。  \n\n（1）配料设备常用的配料设备一般分两类：不带破碎装置的配料罐；带破碎装置的配料罐。如图3-8-8和图3-8-9所示。  \n\n![](images/15f47839ba1e3c7f30699a43f254bc01304305b32d934472831c1fdd3897ede5.jpg)  \n图3-8-7热固性粉末涂料的工艺流程和操作要点  \n\n![](images/6bb50f613f6ed78b9c64f8d210ce6a5cde5c5f749fb592f3d035c677e3e8b421.jpg)  \n该混料罐没有搅拌桨，无破碎装置，只靠自身的翻转，将罐体内的物料提升和下落进行物料的混合  \n\n![](images/c0d1454bc0d837a2916874a1128ce52304c1149a96520876c57fcef24f9678df.jpg)  \n图3-8-8不带破碎装置的配料罐  \n图3-8-9 带破碎装置的配料罐  \n\n![](images/d6f6ff96068ccf81ba09049009c1f79ea349e28f0dda79f8308d8c722c2e0df9.jpg)  \n该混料罐也无破碎装置，在自身翻转的同时，罐的一头还配有一个低速搅拌桨用以出料，水平中轴上配有螺旋推进器，以加大混料强度。目前，这类的设备主要用于美术粉及银粉的拼混等用途  \n图3-8-10 翻转式高速混料机  \n\n该混料罐下部装有水平转动的并有一定斜面的桨叶，桨叶将物料水平搅动，并在离心力的作用下物料趋向罐体内壁。同时，桨叶的斜面将物料向上推抛，物料再顺着罐体侧壁的斜面向内翻动。与此同时，侧面的破碎刀片高速旋转，将树脂打碎。该混料罐混料强度大、效率高，是目前最常用的混料设备  \n\n翻转式高速混料机（图3-8-10）是目前比较新型的设备。这种混料机与前一种设备反向思维的设计使得该设备的一次投料量和生产效率大大提高。有了翻转的动作，在投料量增大的同时也不会使混料效果变差。FHJ系列翻转式混料机如图3-8-11所示。  \n\n(2）混炼挤出设备自20世纪60年代壳牌化学公司在欧洲开发了粉末涂料的挤出工艺后，该工艺一直沿用至今天，一般分为单螺杆挤出机（图3-8-12）和双螺杆挤出机（图3-8-13)。  \n\n单螺杆挤出机螺筒的内壁与螺杆的外缘以及螺筒内的三排阻尼销钉和螺杆上的凹槽，在螺杆转动时形成对物料的剪切和混炼，进口设备的螺杆还同时具有明显的往复运动（冲程在  \n\n![](images/ff8bdaf75187c9e0175f8915de82fd75884e323a393eb7989f769e9ba661f4b5.jpg)  \n\n![](images/9408faa61dd34c32517b26e79e7b4a8c2851225e4610dc3983bc21715e036cbc.jpg)  \n图3-8-11FHJ系列翻转式混料机  \n图3-8-12 单螺杆挤出机结构图  \n\n![](images/590c9a8a20c1e96941c252b9a1a73beca8677e7e8c1c6499a83375ec498dbb01.jpg)  \n图3-8-13 双螺杆挤出机结构图  \n\n1一主电机（螺杆的动力电机）；2一变速齿轮箱（螺杆的传动装置）； 3一进料电机；4—料斗；5—螺旋进料器；6—螺杆进口料斗； 7-操控仪表盘；8—挤出螺筒  \n\n5cm以上)，以增强物料的混炼效果。单螺杆挤出机的螺杆扭矩相对较小，因而螺杆可以做得较长，使挤出物料在螺筒内的存留时间较长，加之螺杆的转动和往复的运动，这种通过增加树脂对颜料、填料浸润时间和增大物料的剪切流动的方式，使物料的混炼更加充分。由于单螺杆的螺筒内部结构间隙相对较大，因而挤出物料的胶化粒子极少。然而，国产单螺杆设备在许多方面达不到进口设备的条件，进口设备价格昂贵，因而国内使用这类设备的粉末涂料生产厂家和数量不多。  \n\n主电机的调速分为电磁调速和变频调速，从而控制螺杆的转速。螺筒上还有加热、水冷和温控等装置。  \n\n双螺杆挤出机的传动结构和螺杆结构都较复杂，两个螺杆的转动方向相同，从而使剪切程度加大，如图3-8-14所示。  \n\n双螺杆的结构相对也较复杂，组合变动也较多，螺杆结构如图3-8-15所示。  \n\n无论是单螺杆还是双螺杆，它们都有一个送料段，机器挤出物料量的大小就由它的粗细、长短及螺杆的转速决定。单螺杆的混炼长度、间隙及往复地幅度决定其混炼效果。而对于双螺杆来说其螺块部分的排布结构、长短、间隙等则决定机器的混炼效果的好坏。  \n\n(3）冷却破碎设备 (压片破碎机) 冷却破碎设备如图3-8-16所示。  \n\n![](images/ac81716c318164e5465d26016c549a5616af97c62e4e61344eb9c404828b8b7f.jpg)  \n图3-8-14双螺杆挤出机的传动结构和螺杆结构  \n\n![](images/9c60d0abfd2c0d782cb24089d3f05f14e80fdb496d2f42c8e06986a63ad66283.jpg)  \n图3-8-15螺杆结构  \n\n1一送料段（即螺旋进料器）；2一过渡段（或预混炼段）；3一混炼段；4一加强混炼段  \n\n![](images/3abd054c53fadf005e800dbcb7867910801d3a8b8571285c731e31d94ce84763.jpg)  \n图3-8-16 冷却破碎设备  \n\n①结构由机架、压辊、输送带、冷风机和破碎辊等组成。②用途该机对熔融状物料可轧成厚度1.5mm左右的片状，在输送过程中经护罩上方的冷风机风冷后，破碎成片状。  \n\n![](images/29298ba62956cf086c1b95ea89a1b07b16cd94df193e443acd46901580fc2318.jpg)  \n图3-8-17 磨粉筛粉设备  \n\n(4）磨粉筛粉设备磨粉筛粉设备如图3-8-17所示。进料器将料斗中的料片送人ACM磨机，在高速转动主磨盘上的击柱冲击和物料冲击衬瓦，以及物料相互冲击下被粉碎，并在引风力和副磨的作用下分离，细微粉经管道进入旋风分离器进行粗细粒径的分离，超细微粉进人带虑袋的回收箱，被分离出去，其余的粉末旋沉至旋风分离器的底部，被关风排料器翻排到下面的旋风筛进料器，并送人旋风筛过滤分离，粗粉从另一头排出回收。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 741,
+        "chunk": "# 3.生产工艺原理及控制方法  \n\n根据热固性粉末涂料生产设备系统的结构，一般把生产工艺过程分为四个工序：配、混料工序；热混炼、挤出工序；冷却、破碎工序；磨粉、筛分工序。前两道工序，其目的就是要使成膜树脂相互溶解，并使颜料、填料在树脂中分散得足够均匀。而后两道工序，就是如何将粉磨好。因此，粉末涂料就生产和产品控制而言两个要点：如何使粉末涂料的各种原材料混合分散均匀，使其具备涂料的性能；如何将混合分散好的物料加工成合适粒度的粉料，以利于涂装使用。  \n\n（1）配、混料工序粉末涂料的原料基本上是固体物料，因此物料的混合就是不同物质间固相的混合，目的是使这一固相体系形成均匀的堆积，以利于下道工序——混炼、挤出进行。  \n\n首先是配料的计量器具和称量误差。在规定的误差范围内，使用合适称量精度的计量工具，使各物料的计量误差达到要求，特别是在称量颜料的时候。例如：对着色力强的颜料称量的相对误差应控制在 $0.5\\%$ 以内，其他材料的相对误差也不要超过 $1\\%$ 。误差要求得越高，对计量器具的精度要求就越高，操作难度就相应加大。主要还是考虑某种原料的误差量能否对产品品质造成影响来订出各物料允许的误差值[相对误差 $\\equiv$ （测量值一真值)/真值 $\\%7$ 费  \n\n其次是投料顺序，各种材料的投料顺次不同会在一定程度上影响物料混合的均匀程度和效率，在使用不同的配料设备时，应依据其工作原理来制定相应的投料顺序和配料工艺。对于无破碎装置的混料设备，应先把大颗粒的树脂和助剂破碎成 $1.5\\mathrm{mm}$ 以下的粒度，再进行计量、投料。对投料质量少的材料要进行预分散处理，以保证小料能均匀混合。如使用有破碎装置的配料罐[图3-8-11(b)］，其搅拌桨在底部，因此要先投颗粒大的物料，因粒径大的物料有利于力的传导，所以先投树脂利于物料的混合，如果先投粒径细的物料，则会在水平桨叶下部形成混合死角。另外还要注意小料的预分散。  \n\n配料时投料量的掌握，对于如图3-8-10和图3-8-11(a）所示的配料设备，一般来说投入物料的表观体积要占罐体容积的 $70\\%$ 以内，否则就没有足够的空间进行物料的混合。罐体的转速也不能过快，较大的离心力会影响物料的下坠。对如图3-8-11（b）所示的混料罐，投料量就要考虑底部的搅拌桨叶能否将被混物料抛起，投料过多（不仅要注意物料表面的高度，而且还要注意物料的密度因素)，物料的立向回转运动不充分，影响混料的均匀程度。  \n\n破碎粒度，一般来讲，粒度越细、混合时间越长，物料混合得越均匀，越利于挤出混炼的均匀。但是，物料太细，则不利于物料在螺杆内的传送，不仅容易形成传送死角，而且还增加物料对设备的黏附量。相反，树脂颗粒太大，在挤出时会加长树脂的熔融时间，将影响树脂间的混容程度以及树脂对颜填料的分散程度。在不影响物料传输的情况下，物料（主要是树脂）的粒径应尽量小，一般要在 $1.5\\mathrm{mm}$ 以内。  \n\n(2）混炼、挤出工序粉末涂料树脂等材料的相互溶解以及树脂对颜料、填料的分散就是在这个过程进行的。料斗内的物料被螺旋进料器送人螺筒，螺杆的螺旋进料器将物料送进加有一定温度的螺筒后，树脂开始熔融，进而树脂间开始溶解并对颜料、填料进行润湿。螺杆上的捏合块在螺筒内的转动对物料产生的剪切力强化了溶解和润湿过程。  \n\n图3-8-18是一张50螺杆的照片，用双螺杆其中的一根来解释。实际上螺杆的工作部分可简单地分为送料段，即图3-8-18中的1；混炼段，即图3-8-18中的2十3。该段又可分为过渡段2（又称预混炼段）和混炼段3。首先，混合好的固体物料经1段的螺旋进料器向前传送进人2段，物料在1段时的温度不宜过高，否则树脂融化形成的黏附层会使进料螺旋的凹槽变浅，影响送料。物料在进入2段时，树脂在此被加热并开始融化，此时树脂并未完全融化，为了减小物料传送及螺杆转动的阻力，捏合块的排列呈螺旋推进器状，其排布方向与送料螺旋的排布方向一致（图3-8-19)。螺筒内的物料经1段螺旋对后续物料的输送，挤压前面的物料进入3段，在温度作用和捏合块的搅动、剪压下，物料中的树脂完全熔化，并对颜料、填料进一步润湿混合。前物料再经后续物料的推挤排出螺筒，进入后工序。  \n\n![](images/0530ba8d987ff9b367fddae12ac066cb59c6cc271add358aef0a2391ed8df996.jpg)  \n图3-8-1850螺杆  \n\n![](images/ad56dc7da2980bdd222dbc820c0d5baf7aeda59ba59ac4ffe4da247125656c93.jpg)  \n图3-8-19 捏合块的排布方向  \n\n物料在整个螺筒内的输送，完全是通过送料段的螺旋进料器进行的，因此，它的工作状态和形状对于一台挤出机生产量的影响是关键的。送料段的长短是影响此台挤出机生产量大小的一个方面；螺杆转速快慢，也对应着生产量的大小；螺距的大小也对应着生产量的大小；螺杆的粗细、螺旋凹槽的深浅反映了物料输送截面积的大小，也影响到挤出机生产量的大小。2、3段的长度、捏合块的厚薄以及捏合块的排布也对挤出机的生产量有影响，2段的排布是一种最小阻力的排布。2、3段的长度是决定物料混炼效果的重要方面，螺块的厚薄和排布形态也影响物料的混炼效果。总之，间隙小、物料输送的阻力大则混炼效果好。但同时，还要注意物料固化的安全。在图中，3段里有一小段4，就是为了加大阻力，增加混炼效果。  \n\n一台挤出机，它的生产量、混炼效果和物料在挤出时的固化安全方面三者是相互制衡的。也可以用一台挤出机，通过选用不同结构形状的螺杆来达到不同的生产目的。所以，螺杆直径小并不意味着生产量一定小。而螺杆的长径比与其混炼效果并非一定是对应一致的。  \n\n由于设备的差异和产品的多样性，各工艺参数应有一些不同，但是要有一定的原则。  \n\n① 螺筒的温度靠近进料口的温度，在不使螺杆的螺旋进料器黏结物料的情况下越高越好，这样既不会使螺旋凹槽变浅，影响物料的输送，也利于树脂在螺杆的过渡段尽快地融化。靠近出料口的温度，在不使挤出物料发生固化反应（或胶化）的情况下越高越好，这样树脂的黏度低，流动阻力小，分散体系易形成复杂流动，利于树脂间的溶解及其对颜料、填料的分散。  \n\n②螺杆转速螺杆的转速越高，螺杆中的捏合块产生的剪切速率越大，越利于树脂对颜料、填料的分散，但同时，物料的传输速率也越快，物料在螺筒内的混炼时间也就短，很可能会造成分散程度不足，特别是对于短螺杆的设备而言。由于挤出设备的品种多，性能差异比较大，螺杆的转速要依据不同情况来确定。一般来说，混炼段较长的螺杆转速应高一些，混炼段较短的螺杆转速应低一些，最好根据涂膜表面的效果来确定。  \n\n$\\textcircled{3}$ ③挤出机的给料量挤出机料斗的进料器最大值以螺筒进料口不积料为准，最小值以螺筒温度值的稳定性为准，要使螺筒温度波动的范围和频率尽量低。这里需要注意的是，物料在螺筒内传送过程中带走了螺筒内的部分热量，起到了一部分温度调节的作用。挤出机是中低剪切分散设备，因而浸润分散作用显得更重要，这就要求物料在挤出过程的黏度较低时对物料分散更有利。  \n\n(3）冷却、破碎工序这道工序就是利用材料的热塑性以及压片辊把热的物料挤压成薄片，使其能快速冷却。此工序有两个调整参数：压片厚度和钢带传送速率。料片越薄越利于散热，但易被钢带上的冷却风扇吹得飞溅起来，一般控制料片的厚度在 $1{\\sim}1.~5\\mathrm{mm}$ ，而后再调整传送带速率，不致使压片辊上过度积料。建议将螺筒的冷却水系统与压片辊的冷却水系统分开，以保证压片辊冷却水温尽量低。  \n\n该设备的最重要的是冷却功能，因此，压片辊的冷却性能是该设备最关键的性能之一。早期的压片辊只是有两头轴心通水的、简单的圆筒辊，由于空气压力的作用，辊内的冷却水不能够充满，压片辊的冷却效率不高，设备产能不大。现在，一般的设备厂家把压片辊做成夹套结构，使压片辊的表面的传热效率有所提高。此外，设备厂家还通过加大压片辊的直径和长度或加增水冷循环机来增加冷却效果，如辊筒式压片机，辊筒式压片机的特点；同常规的压片机相比，长度可缩短2/3，冷却的效率可以提高20%。物料通过压片辊初步冷却后，再经过传送钢带进一步冷却。总之，压片破碎设备就是要把挤出机挤出的热物料尽可能地冷却到最低温度，以利于磨粉工序的进行，料片的温度越低，越有利于磨粉温度的控制。  \n\n(4）磨粉、筛分工序该工序按设备结构的组成可分为六个重要部分：引风机、除尘集尘箱（超细粉柜)、磨机、旋风分离器、关风排料器和旋风过滤器。引风机产生的负压气流是磨粉体系物料传送的主要动能来源，也是磨体冷却气流动能的来源。当料斗的螺旋进料器将片料送入磨机里，基于高速旋转磨盘产生的冲击粉碎作用，物料在击柱和衬瓦（齿圈）以及物料相互冲击下完成微粉过程。进人分级区的，具有一定粒径的颗粒同时受到风机引力和由于分级器旋转产生的离心力的作用。对于粒径微小的颗粒，当风机引力大于分级器旋转产生的离心力，这些粒径微小的颗粒（粒径小的颗粒质量轻，动能小，离心力就小；粒径大的颗粒质量重，动能大，离心力就大）在风机引力的作用下进人成品粉管道。粒径较大的颗粒在离心力的作用下进入粉碎区，进行再粉碎，如图3-8-20所示。  \n\n![](images/1447ebdf1b87c52eac2e66c308f455e1c117cbb961f069460aae3d261655c501.jpg)  \n图3-8-20磨粉、筛分工作原理（曲线表示气流走向，箭头表示物料走向） 1—击柱磨盘（主磨)；2—磨机体壳；3—回流板；4—分级器叶片（副磨)；5—分级器轴；6—成 品粉室（接成品管道)；7—粗细粉分离区；8—进料器；9—衬瓦（齿圈）；10—主磨传动皮带  \n\n气流将成品粉通过管道送人旋风分离器，气流在旋风分离器里形成旋转风带动物料旋转，物料颗粒在这里又产生一个离心力。和在磨机的原理一样，粒径小的颗粒其离心力小，被气流吸人超细粉管道里进人回收柜，较粗的成品粉在离心力的作用下，向分离器的内壁运动，同时在重力和风压的作用下降到底部，如图3-8-21所示。  \n\n![](images/6f6380d6d28c125b92c7485ad376214ccbb0b00300b56a3e94677b55cc96b79a.jpg)  \n图3-8-21旋风分离器 的组成及内部气流 1一简体；2—锥体；3—进气 管；4—排气管；5—排料口； 6—外旋流；7—内旋流； 8—二次流；9一回流区  \n\n，关风排料器将成品粉翻转到下面的旋风筛的螺旋进料器里，送入旋风筛中进行筛分。而粉末的过筛也是利用粉末颗粒旋转产生的离心力进行的。  \n\n该工序在生产过程有四个可调整的参数—一进料速度、分级器（副磨）转速、引风量和主磨转速。主磨转速即粉碎脊柱的线速度，物料是通过在一定速度下形成的撞击而破碎的，因此脊柱的线速度越高，产生的冲击能量越大，粉碎效率越高，磨粉细度越高。物料在磨膛内的撞击分为与设备的撞击和物料之间的撞击，前一方式的撞击更利于物料的破碎，后一种撞击则粉碎效率较低，而进料速度大则会增加物料间撞击的概率，使磨粉效率降低，磨粉效果变差。此外，还有两个控制值一一磨粉温度、粒径分布数值和一个关键动力——气流量。所以，该工序就是通过冲击粉碎，以气流为动力，粒度分布和磨粉温度为工作标准进行进料量和副磨转速的调整配合的过程。这一过程的核心就是力——冲击力、粉末颗粒旋转产生的离心力与气流形成的吸力。由于粉末颗粒的离心力和颗粒的动能有关，而颗粒的运动速度越大其动能越大，通过调整分级器转速大小来控制进人成品粉管道粉末颗粒的细或粗，具体的数值最好依据粒度分析仪所测的结果来确定。气流风量的调控则涉及磨机内部环境的温度、粒径分布和成品率。对于磨机来说，风量大利于降温；对于旋风分离器来说，风量大则产生的回流风也越大，对细微粉的抽吸率越大，粒径分布较窄，产量较大；风量小则旋风风速低，超细粉的损耗就要小些，产量较低。调整风量的同时，一定要照顾到磨机的温度。当以上两个参数确定下来后，就可以根据磨机的工作温度来调整进料量，如果磨机温度高，就应该减少进料量。还有一个问题需要提醒大家：由于配方或品种的不同，会造成片料的硬度不同，在相同参数条件下，物料被粉碎的粒度会不一样。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 742,
+        "chunk": "# 三、粉末涂料生产及产品质量控制",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 743,
+        "chunk": "# 1.生产过程中的质量控制  \n\n在粉末涂料生产过程中，人、机、料、法、环等各环节都可能会出现某些差异，这些差异往往会造成产品质量上的偏差，工艺人员需要通过各种手段对生产过程进行质量监控才能保障最终产品质量达到合格。  \n\n(1）配混料的质量控制配料工序的配混料完成后，物料要经过打样试验来确定配料的质量情况。打样物料的取样数量要视挤出机的情况而定，关键是要基本消除前次打样物料及清机物料对颜色和配方结构所造成的影响。打样制板后要对涂膜的颜色、光泽、流平性（或纹理)、不熔性粒子、耐冲击强度、柔韧性、粉末胶化时间、熔融流动性等方面进行检测，出现问题及时调整。  \n\n(2）磨粉的质量控制磨粉生产过程中首先要调控的是粉末的粒径分布。不同的粉末涂料产品有不同的粒径分布要求，此外，气候的变化对磨粉粒径分布的影响比较大，因此，不仅从开始磨粉时就要对粉末粒径分布进行调整，当磨粉环境波动时也要随时对其进行监控。粉末流动性是与粉末的粒径分布、抗结块助剂及粉末的密度相关的指标，在调整粉末粒径分布的同时还要通过调整抗结块剂的用量来控制粉末的流动性。在磨粉的全过程当中，要随时用标准筛对粉末的筛余物进行监控，以防止漏筛、破筛的情况发生。  \n\n(3）粉末后拼混的质量控制涉及后拼混的产品，每批投料都要进行打样制板检测，保证涂膜外观达到合格。  \n\n生产过程的质量控制主要是涂膜外观、物理性能的检测控制和部分粉体性能的控制，粉末制成后还需进一步的质量检测。  \n\n（4）粉末涂料的质量指标和测试方法  \n\n$\\textcircled{1}$ 粉末涂料的胶凝时间在一定温度下粉末涂料从干态固体转变成胶状所需要的时间（以 ${}^{i i}{}_{\\mathbf{S}}{}^{y}$ 测定)。粉末涂料必须经过适当的固化才能获得性能优异的粉末涂膜。粉末涂料的胶化时间与其化学性能有关，可用以预测粉末涂料在给定的固化条件（时间或温度）下是否能够很好地固化。在预热到规定测试温度的金属板上，取被测样品约 $0.5\\mathrm{g}$ ，当粉末熔化时立即启动秒表，并开始用搅棒搅动物料，搅棒应使用热容量低的材料制作。当感觉物料变稠后，在搅动的同时每隔 $2\\div35$ 将搅棒从熔化的物料向上拉起约 $10\\mathrm{mm}$ 拉出丝状物，以丝状物拉断或不能拉出丝时为计时终点，所记录的时间就是凝胶时间。胶化时间是表示在某一温度下，粉末涂料固化速率的数据，与粉末涂料熔融黏度的关系不明显，但能在一定程度上表示粉末涂料的熔融流动程度，特别是对美术粉纹理大小的控制具有实际意义。该试验对粉末涂料配方设计和生产质量控制人员非常有用。  \n\n$\\textcircled{2}$ 粉末涂料的倾斜板流动性在一定温度下熔融态粉末涂料在倾斜、平整的玻璃板表面流动的距离，以 $^{\\mathrm{{sf}}}\\mathrm{{mm}}^{y}$ 表示。对于粉末涂料在未固化状态下的流动流平性要求取决于固化粉末涂料的施工状况，如果固化的涂膜表面平整性非常好，对粉末涂料的流平性要求相对较高；如果涂装具有锐边的工件，则粉末涂料的流动时间要求可以相对较短。斜板流动试验为人们提供了一种方法，借以比较两种粉末在未固化时的流动特性。倾斜板流动性能够反映出粉末涂料的熔融黏度，与胶凝时间数据配合分析用于配方的调整，能较好地平衡粉末涂料的流平性与边角覆盖性，粉末涂料的化学特性对涂膜平整性也有影响。该试验对粉末涂料配方设计和生产质量控制人员非常有用。  \n\n$\\textcircled{3}$ 粉末涂料的密度在一定温度和压力条件下粉末材料密度与水密度的比值。液体置换比重瓶法是最经济的测定方法。使用 $50\\pi L$ 的比重瓶，置换液可使用正已烷或庚烷等对粉末不溶解及溶胀性小的液体，可通过抽真空的方法除去置换液与粉末间的空气。粉末涂料的密度与它的喷涂性能有很大关系，密度过小则粉末容易飞扬，密度过大不易上粉，而且会发生附着于工件的粉末掉落的现象。  \n\n$\\textcircled{4}$ 粉末涂料的相容性在涂装不同颜色和化学组成的粉末涂料时，对其相容性有一定要求。不同的粉末涂料间由于化学组成、反应活性、熔融特性的不同造成它们之间不相容。不相容的粉末混合时将导致光泽、表面外观、物理性能的变化以及颜色污染。建议在涂装粉末涂料之前先检查粉末的相容性，而不是在涂装线上发现这一问题。将两种待测的粉末按如下的比例进行混合：100/0；99.9/0.1；99/1；90/10；50/50；10/90；1/99；0.1/99.9;$0/100$ ，分别进行喷样检查，可通过描绘光泽曲线来确定粉末涂料的相容程度。  \n\n$\\textcircled{5}$ 粉末涂料的粒径分布粉末涂料的粒径分布和平均粒径对粉末涂料的施工性能和固化后粉末涂膜外观影响很大。遗憾的是没有最佳粒径分布或平均粒径，对每一项涂装作业而言，最佳粒径分布或平均粒径均因被涂工件的构形、所需涂膜厚度、所需涂膜外观、粉末涂料的化学特性和涂装设备的不同而不同。使用激光粒径分布仪能够较精确而快速地测定粉末  \n\n涂料的粒径分布，生产上常通过激光粒径分布仪的分析结果来指导磨粉工艺的控制和调整。  \n\n![](images/e480f366fd6782bafaeb185505c1c2053f77a804cb4455454258c81dac568075.jpg)  \n图3-8-22 测试流动性的仪器  \n\n$\\textcircled{6}$ 粉末涂料的输送和喷雾特性在一定的载气压力、温度和流速下粉末自由、均匀、连续流动的能力。粉末涂料的传输和喷涂性能很大程度上取决于粉末的流动性和结块性。该方法比用于评估粉末流动性的流动角方法更有意义。流动角测定法是测定粉体在水平面上形成的锥体与水平面之间的夹角。流动性好的粉末其流动角比流动性差的粉末小。使用流动角方法的端是很难获得精确  \n\n的测定结果，原因在于该方法测定的是粉末，而实际涂装采用的是粉末/空气混合物。测试流动性能的仪器包括壁上有一个环形开口的流化容器、测试容器中粉末高度的装置以及流过开口处粉末的称量装置，如图3-8-22所示。  \n\n通入一定压力的空气后容器中粉末的流化粉层的高度与通气之前静止分层的高度差越大，则粉末的流化性能越好，单位时间内从开口处流出的粉末越多则粉末的流动性越好。  \n\n$\\textcircled{7}$ 粉末涂料加速稳定性试验粉末涂料必须容易流化且能自由流动以便于涂装。另外，粉末涂料必须经过熔融、流平、固化（热固型粉末涂料）形成装饰性和保护性令人满意的粉末涂膜。对热固性粉末涂料而言，用户可根据加速贮存稳定性试验预测粉末涂料的物理和化学稳定性，确定粉末涂料在不同温度和时间下的长期适用性，还可以预测热固性粉末涂料的物理稳定性。将装有粉末涂料的容器在加载一定负荷的情况下放人恒温箱中，在规定温度下贮存一定时间后观察粉末结块的情况，并通过制作涂膜样板进行理化性能的测试，与试验前的数据进行比对、评判。  \n\n$\\textcircled{8}$ 粉末涂料的沉积率（上粉率）工件表面沉积的粉末涂料与喷向工件的粉末量之比，通常用百分率表示沉积率或上粉率。现场施工经验表明，新粉的一次上粉率越高，则涂装生产效能越好。因此如果有一种实验室方法比较两种以上粉末涂料的一次上粉率将是非常有利的，下列试验方法可以实现这一目的。非常有意义的是该试验方法确定了喷涂施工性能已知的对照粉末，正确的方法是受试粉末涂料在同一实验室和基本相同的时间内得到的试验结果与对照粉末的结果比较，而不同实验室的测定结果无可比性。  \n\n本方法规定了在已知大气温度和湿度条件下，以已知流速将荷电粉末喷涂在由铝箔包覆的5个相同钢管的中间中的一个上，测定沉积在中间钢管上的粉末质量，由此计算沉积效率。此操作在一个空气萃取室中完成。  \n\na.钢管装置钢管装置由5个内径为25mm、长度500mm的钢管组成，每个管子的一端都钻有一个孔，以便管子能垂直悬挂。每根钢管应适当接地。 C  \n\nb.铝箔 为清洁铝箔，工业级。  \n\nc.悬挂装置悬挂装置用于使5根钢管能等距离并排垂直悬挂，管与管之间的中心距为 $95\\sim105\\mathrm{mm}$ 。  \n\nd.粉末喷涂系统由一把适宜的电晕喷枪或一把摩擦喷枪与一个适宜的粉末收集装置安装在一个空气萃取室中而组成。  \n\ne.绝缘挡罩或粉末收集装置该装置应足够大以避免在试验前后从喷枪喷出的粉末落在钢管上，且能够灵便地在试验期间移走。  \n\nf.取样 建议取 $2\\mathrm{kg}$ 样品。  \n\ng.操作步骤在温度（23士2)℃和相对湿度20%～70%条件下进行一式两份试样的平行试验。用铝箔将5根钢管包住，使顶部和底部边缘折人管子中以保证良好的电接触。用天平称量用于中间管子上的铝箔，准确至 $0.1\\mathrm{g}$ 0  \n\n测定粉末流动速率：利用喷粉系统将粉末喷涂到一个预先称重的清洁袋中，用计时器控制喷粉时间为60s，再称量带有粉末的清洁袋，准确至0.1g。计算粉末流动速率，以“g/min”计。  \n\n$\\cdot$ 当使用电晕喷枪时，调节喷粉装置的控制阀，使粉末流动速率达到 $(150,0{\\pm}7.5)\\mathrm{g/min},$  \n\n注：在此操作期间必须关闭高压。  \n\n$\\cdot$ 当使用摩擦喷枪时，调节空气压力至 $300\\mathbf{kPa}$ （3bar），并测定粉末流动速率。  \n\n$\\cdot$ 将装有5根钢管的悬挂装置放人喷涂室中。  \n\n$\\cdot$ 将喷枪安装并调平在萃取室中，使喷枪能瞄准中间钢管的中心位置，喷枪距钢管的位置以能使喷出的粉末覆盖中心钢管长度约 $60\\%$ ，记录该距离值。保证通过萃取室通道的空气流在 $0.4{\\sim}1.0\\mathrm{m/s}$ ，且空气流的流动方向与喷涂方向平行。  \n\n当使用窄的锥形喷枪时很难覆盖钢管长度的 $60\\%$ ，在试验报告中应记录所有不同之处。  \n\n$\\cdot$ 将绝缘挡罩置于喷枪和钢管之间。  \n\n$\\cdot$ 打开开关使粉末流出，使用电晕喷枪时，应调节电压使实际喷枪电压在适当的极性时为 $(60\\pm1)~\\mathrm{{\\kV}}$ 量  \n\n注：在这一点上应抓住机会对不同电压进行试验，以便对设备和粉末做出更深层的评价。  \n\n$\\cdot$ 除去绝缘挡罩，使粉末没有波动地、稳定地喷涂在钢管上达 $(6.0\\pm0.5)\\mathrm{{s}}$ ，在这一阶段最后，立即将绝缘挡罩再次放置在喷枪和钢板之间，关闭喷枪。  \n\n$\\cdot$ 从悬挂装置上小心取下中间钢管，不要敲掉任何粉末。将其置于已调至一定温度的烘箱中烘烤，调节的温度要使粉末涂料能在 $5\\mathrm{\\sim}10\\mathrm{min}$ 内融化。  \n\n不要使粉末涂料经过固化过程，因为这能导致损失。  \n\n$\\cdot$ 从烘箱中取出带铝箔的钢管并使之冷却，从管子上取下铝箔并称重，准确至 $0.1\\mathrm{g}$ 中注：为了避免粉末损失，可以在一个已称重的塑料袋中取下铝箔。  \n\n结果计算：按式（3-8-14）计算沉积效率 $E$ ，用质量分数表示。  \n\n$$\n\\scriptstyle{E={\\frac{m_{\\mathrm{p}}\\times60\\times100}{P_{\\mathrm{f}}t}}}\n$$  \n\n式中 $m_{\\mathrm{p}}$ 沉积在铝箔上的粉末质量，g；$t$ 喷涂时间，s；$P_{f}$ 粉末流动速率， $\\bar{\\bf g}/\\bar{\\bf m}\\dot{\\bf i}\\bar{\\bf n}$ 口",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 744,
+        "chunk": "# 2.粉末涂料产品技术标准  \n\n粉末涂料品质的高低是通过其产品技术标准来体现的，人们通过各种手段测得的一些具体数据（性能指标)，并通过这些数据来判定产品的性能水平。在粉末涂料的技术标准中，通过三个方面的内容来体现粉末涂料产品的装饰性、防护性和产品的使用性能。这三个方面就是：涂膜的物理性能标准；涂膜的化学性能标准；粉末涂料的使用性能标准。  \n\n(1）涂膜的物理性能标准体现的是产品成膜后的外观和力学性能，内容有：涂膜外观、硬度、附着力、光泽、耐冲击强度、柔韧性、抗慢渗入、拉伸强度（杯突试验）、耐磨性等。  \n\n(2）涂膜的化学性能标准体现的是产品成膜后的耐化学品的腐蚀性能，内容有：耐温性、耐水性、耐盐液性、耐盐雾性、耐酸液性、耐碱液性、耐油性、耐溶剂性、耐紫外线照射性等。  \n\n(3）粉末涂料的使用性能标准体现的是产品成膜前的贮存和喷涂使用的性能，内容有：抗结块性、密度、固化条件、粉末粒度、粉末的流动性、上粉率等。  \n\n粉末涂料的各种性能指标是在规定的测试条件下，并使用规定的测试设备和方法（即测试方法标准）进行的，这样的结果才有通用性和可比性。  \n\n热固性粉末涂料产品化工行业标准HG/T2006—2006内容见表3-8-19。  \n\n表3-8-19热固性粉末涂料产品化工行业标准  \n\n\n<html><body><table><tr><td rowspan=\"3\">项 目</td><td colspan=\"6\">指 标</td></tr><tr><td></td><td colspan=\"2\">室内用</td><td></td><td colspan=\"2\">室外用</td></tr><tr><td>合格品</td><td></td><td>优等品</td><td>合格品</td><td></td><td>优等品</td></tr><tr><td>在容器中状态</td><td colspan=\"3\">色泽均匀，无异物，呈松散粉末状</td><td colspan=\"3\">色泽均匀，无异物，呈松散粉末状</td></tr><tr><td>筛余物（125μm）</td><td colspan=\"3\">全部通过</td><td colspan=\"3\">全部通过</td></tr><tr><td>粒径分布</td><td colspan=\"3\">商定</td><td colspan=\"3\">商定</td></tr><tr><td>胶化时间</td><td colspan=\"3\">商定</td><td colspan=\"3\">商定</td></tr><tr><td>流动性</td><td colspan=\"3\">商定</td><td colspan=\"3\">商定</td></tr><tr><td>涂膜外观</td><td colspan=\"3\">涂膜外观正常</td><td colspan=\"3\">涂膜外观正常</td></tr><tr><td>硬度(擦伤)</td><td>F</td><td>H</td><td>F</td><td colspan=\"3\">H</td></tr><tr><td colspan=\"7\">附着力/级</td></tr><tr><td>耐冲击性/cm</td><td></td><td>50</td><td></td><td></td><td colspan=\"2\">1</td></tr><tr><td>光泽(60°)≤60 光泽(60°)>60</td><td>≥40 50</td><td>正冲50，反冲50</td><td></td><td>≥40 50</td><td colspan=\"2\">50 正冲50，反冲50</td></tr><tr><td>弯曲试验/mm 光泽(60°)≤60</td><td></td><td>2</td><td></td><td></td><td colspan=\"2\"></td></tr><tr><td>光泽(60°)>60</td><td>≤4 2</td><td>2</td><td></td><td>≤4 2</td><td colspan=\"2\">2 2</td></tr><tr><td>杯突/mm</td><td></td><td></td><td></td><td></td><td colspan=\"2\"></td></tr><tr><td>光泽(60°)≤60 光泽(60°)>60</td><td></td><td>6</td><td></td><td>4</td><td colspan=\"2\">6</td></tr><tr><td></td><td>6</td><td>8</td><td>6</td><td></td><td colspan=\"2\">8</td></tr><tr><td>光泽(60°)</td><td></td><td>商定</td><td></td><td>商定</td><td></td></tr><tr><td>耐碱性（5%NaOH)</td><td colspan=\"2\">168h无异常</td><td></td><td colspan=\"2\">商定</td></tr><tr><td>耐酸性(3%HCI)</td><td></td><td>240h无异常</td><td></td><td colspan=\"2\">240h无异常 500h无异常</td></tr><tr><td>耐沸水性(时间商定）</td><td></td><td>无异常</td><td></td><td>无异常</td><td></td></tr><tr><td>耐湿热性</td><td colspan=\"2\">500h无异常</td><td></td><td colspan=\"2\">500h无异常 1000h无异常</td></tr><tr><td></td><td></td><td>500h</td><td></td><td>500h</td><td></td></tr><tr><td>耐盐雾性</td><td colspan=\"2\">划线处：单向锈蚀≤2.0mm 未划线区：无异常</td><td></td><td colspan=\"2\">划线处：单向锈蚀≤2.0mm 未划线区：无异常 500h 800h</td></tr><tr><td>耐人工气候老化性</td><td></td><td></td><td>变色≤2级 失光≤2级 无粉化、起泡、开裂、 剥落等异常现象</td><td>剥落等异常现象</td><td>变色≤2级 失光≤2级 无粉化、起泡、开裂、</td></tr><tr><td>重金属/(mg/kg) ≤</td><td></td><td></td><td></td><td colspan=\"2\"></td></tr><tr><td>可溶性铅</td><td></td><td>90 75</td><td colspan=\"2\"></td><td>90</td></tr><tr><td>可溶性镉</td><td></td><td colspan=\"2\"></td><td colspan=\"2\"></td></tr><tr><td>可溶性铬</td><td></td><td>60</td><td colspan=\"2\"></td><td>75</td></tr><tr><td></td><td>≤</td><td colspan=\"2\"></td><td colspan=\"2\"></td><td>60</td></tr><tr><td>可溶性汞</td><td>≤</td><td colspan=\"2\">60</td><td colspan=\"2\"></td><td>60</td></tr></table></body></html>\n\n$\\textcircled{1}$ 光泽 $(60^{\\circ})=30$ 单位值时不考察涂膜失光情况。  \n\n![](images/c05b15c1d732b234040294949d967d01d5952a111d2d5a0e639b4baa9adda025.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 745,
+        "chunk": "# 一、表面处理  \n\n在大多数情况下，粉末涂料涂装的底材是金属制品，为了获得优良的涂膜和优异的产品质量，在涂装前对被涂工作表面进行的准备工作称为涂装前表面处理，简称前处理。前处理工作主要包括以下三个方面。  \n\n$\\textcircled{1}$ 从被涂工作表面去除各种污垢，如除油（也称脱脂)、除锈以保证涂膜的理化性能和产品的质量。常见的污垢有：金属的腐蚀产物（如铁锈、氧化皮）、焊渣、灰尘、碱渍、油污、旧涂膜等。在涂装前如果不除尽这些污垢，则不仅影响涂膜的附着力、耐腐蚀性能、耐潮湿性能、产品外观，而且锈蚀会在涂膜内部继续蔓延，严重时涂膜会成片脱落。  \n\n$\\textcircled{2}$ 对经过清洗的工件的表面进行各种化学处理，以提高涂膜的耐腐蚀性和涂膜与工件表面的附着力。如对钢铁件进行磷化处理、对铝件进行氧化处理。  \n\n$\\textcircled{3}$ 采用机械的办法消除工件的机械加工缺陷，调整工件表面的粗糙度，以提高产品的外观质量和附着力。如平整工件表面的凸凹不平和毛刺、用喷涂砂方法增加表面的粗糙度。  \n\n根据被涂装材质的不同，前处理的方法也有所差别，以下就不同材质的前处理方法分别论述。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 746,
+        "chunk": "# 1.钢材的表面处理  \n\n(1）表面清洗通过对钢材表面的清洗以除去其表面的油污、浮锈、氧化皮或其他附着物，清洗的方法大概分为以下几种。  \n\n$\\textcircled{1}$ 机械清洗机械方法主要是去除工件表面的浮锈、氧化皮和残留的漆皮等干性污物。如使用钢丝刷、砂布或砂纸、打磨轮等工具对工件表面进行机械打磨，或使用空气喷砂或机械抛丸的方法对工件表面进行冲磨。机械处理后，工件表面形成一定的粗糙度，利于涂膜的附着。而喷砂和抛丸的方法不仅清理效率高，还能在表面形成均匀的粗糙度，可确保涂膜在工件表面具有优良的附着力和外观。工件经喷砂和抛丸处理后，其表面处于很高的化学活性状态，会很快发生锈蚀，因此工件必须立即进行涂装。  \n\n$\\textcircled{2}$ 化学清洗工件在制造过程中，由于防锈和机械加工的需要经常接触各种防锈油、润滑油、拉延油和抛过磨光机等，这种表面有油或油脂的工件不能直接进行喷砂等方法处理，因为喷砂不能彻底清除油污，反而会污染研磨材料，因此在喷砂等机械处理前必须除净工件表面的油或油脂。此外，如油污去除不干净还会影响到工件后期的表面化学转化（磷化）层和粉末涂料的涂装质量。可用有机溶剂、碱液、表面活性剂等去除工件表面的油污。有机溶剂适合去除所有的油或油脂，而碱液适合去除动植物油和油脂，但对中性矿物油的去除效果不佳。表面活性剂的品种繁多，特别是新型表面活性剂可有效地清除各种油污。表面活性剂可配合碱液在低碱情况下对工件表面进行去油处理，使除油后容易水洗干净，更利于后期磷化的质量。除油的方法有浸渍法、喷射法、电解法、超声波法等。作为涂装前处理最常见的是前两种。浸渍法要求在较高浓度及温度的工作情况下操作，同时要求有适当的搅拌等机械作用，以明显提高洗净效果。它可以使用较多的阴离子表面活性剂。喷射法是以较低浓度的清洗液进行强烈喷射，因而不宜采用易起泡的阴离子表面活性剂，可以在较低浓度、较低温度下进行工作，两者的优缺点见表3-8-20。  \n\n表3-8-20 浸遗法与喷射法的优缺点  \n\n\n<html><body><table><tr><td>项目</td><td>浸渍法</td><td>喷射法</td></tr><tr><td>优点</td><td>1.可用于外形复杂、具有封闭内腔的工件，但要注意避 免造成气泡和残留清洗液 2.设备结构比较简单，维护工作量较小 3.用于清洗除油时不易生成过多的泡沫，故允许含较多</td><td>1.处理时间较短，处理温度与浓度也可较低 2.由于具有强烈的机械作用，清洗效果较好，磷化膜的 结晶也较细致 3.工作环境好，劳动强度低</td></tr><tr><td>缺点</td><td>1.处理时间较长，处理所需的温度与浓度也较高 2.清洗的效果较差，磷化膜的结晶也较粗 3.工件环境差，劳动强度高</td><td>1.不适宜用于封闭内腔的工件 2.维护工作量大 3.容易生成大量泡沫，在清洗除油时，要使用低泡或无 泡表面活性剂</td></tr></table></body></html>  \n\n对于高熔点的油污，去油处理的温度也需提高以降低油污的黏度，否则油污不易清除彻底。  \n\n以上清除方法并不能够除去工件表面的锈蚀物和氧化皮，清除锈蚀物和氧化皮除前面所介绍的机械方法外，还可通过酸洗的方法进行化学除锈。用作除锈酸洗液的有无机酸和酸性较强有机酸，盐酸和硫酸除锈效率高，除锈彻底，可常温进行除锈处理，成本低，但容易造成工件“过蚀”现象。而磷酸或有机酸这类中等或温和的除锈剂则不易造成工件的过蚀，所处理的工件表面清洁度高，能采用喷淋的方式进行除锈处理，但除锈效率低、成本高，对锈蚀严重的工件处理效果不佳。在除锈过程后，工件常常很快返锈，在酸洗液中加人缓蚀剂则会降低返锈现象。同时，为了防止二次生锈及将残酸带人磷化工序，除锈后的工件必须中和处理后才能进人下道工序，中和槽液为 $3{\\sim}5{\\mathrm{g/L}}\\ \\mathrm{Na_{2}C O_{3}}$ 水溶液。  \n\n(2）钢材表面的磷化工件经过前面一系列的表面处理后，需通过化学反应在其表面生成一层非金属的、不导电的、多孔的磷酸盐薄膜，这一过程称之为钢材的磷化处理，生成的薄膜称为磷化膜。磷化膜具有多孔性，涂料可以渗人这些孔隙中，因而能显著地提高涂膜的附着力。此外，磷化膜又能使金属表面由优良导体转变为不良导体，从而抑制了金属表面微电池的形成，有效地阻碍了涂膜的腐蚀，可以成倍地提高涂层的耐蚀性和耐水性，所以磷化膜已被公认为是涂层最良好的基底。因此，磷化处理已成为涂装表面处理工艺中不可缺少的一个环节。  \n\n钢材表面形成的磷化膜有三种类型：铁系磷化、锌系磷化和锰系磷化。  \n\n$\\textcircled{1}$ 铁系磷化铁系磷化膜很薄，膜重大多数在 $0,3{\\sim}0,5{\\bf g/m^{2}}$ ，很少达到 $\\mathrm{{1g/m^{2}}}$ 。铁系磷化膜组成为三价铁的磷酸盐与三氧化二铁，颜色从蓝色到褐色。  \n\n铁系磷化处理液的主要成分是酸式碱金属磷酸盐（如磷酸二氢钠、磷酸二氢铵），还含有碱金属的多聚磷酸盐（如三聚磷酸钠）及少量的催化剂促进剂和添加剂。  \n\n在磷化处理工艺上，铁系磷化具有反应速率快，处理时间短，处理温度低，工艺幅度大，槽液的酸度低，磷化淤渣少，因而对设备要求不高，药品消耗少，成本低。如果选用合适的表面活性剂，可组成除油磷化“二合一”，从而可简化磷化处理工艺。但由于铁系磷化膜很薄，它的耐蚀性不及锌系磷化膜，所以主要应用于对耐蚀性要求不高的工件。  \n\n$\\textcircled{2}$ 锌系磷化锌系磷化膜重在 $\\mathrm{1{\\sim}6g/m^{2}}$ 。涂装用磷化膜重在 $\\mathrm{1{\\sim}3g/m^{2}}$ ，系薄膜型。膜的组成，主要成分是锌、铁的磷酸盐，颜色从灰色到灰褐色。  \n\n锌系磷化处理液主要成分是磷酸二氢锌、磷酸三聚磷酸钠及催化剂、促进剂、减渣剂等添加剂。  \n\n锌系磷化由于配方的不同，工艺参数差别极大。就涂装而言，目前采用中温磷化，薄膜型，故反应速率快、时间短、温度低、淤渣较少，但锌系磷化不能组成除油磷化“二合一”，故工艺过程较多。锌系磷化膜的质量优于铁系膜，所以汽车涂装、家电电器涂装等均采用锌系磷化。  \n\n$\\textcircled{3}$ 锰系磷化锰系磷化因处理时间长、温度高、浓度大、膜厚而松，涂装行业现已不用，多用于润滑、防蚀等方面。  \n\n涂装用磷化膜要求：膜重一般在 $\\mathrm{1\\sim5g/m^{2}}$ ，相当于膜厚 $0.\\mathrm{\\}6\\sim3.5\\mu\\mathrm{m}$ ，同时磷化膜的结晶细致、均匀、连续、致密、附着力好、硬度大、孔隙率低。以上三种类型磷化膜的特性见表3-8-21。  \n\n表3-8-21 磷化膜的特性  \n\n\n<html><body><table><tr><td>磷化膜类型</td><td>磷化膜颜色</td><td>沉积量/(g/m²）</td><td>厚度/um</td><td>孔隙率/%</td><td>铅笔硬度</td></tr><tr><td>磷酸铁Fe（PO）z·8HO</td><td>蓝色</td><td>0.1~0.5</td><td>0.1~0.5</td><td>0.1~0.5</td><td>H</td></tr><tr><td>磷酸锌铁 ZnzFe(PO）2·4HzO</td><td>中灰色</td><td>10~30</td><td>5~15</td><td>0.05～0.4</td><td>HB</td></tr><tr><td>磷酸锌Zn（PO）·4HzO</td><td>灰色</td><td>2~10</td><td>1~5</td><td>0.05~0.5</td><td>HB~H</td></tr><tr><td>磷酸锌钙 ZnzCa(PO）2·2HO</td><td>浅灰色</td><td>1.5~6</td><td>1~3</td><td>0.05~0.4</td><td>HB~H</td></tr><tr><td>磷酸锰Mn(HPO）z</td><td>深灰色</td><td>8~40</td><td>3~25</td><td>0.5~3</td><td>HB~H</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 747,
+        "chunk": "# 2.铝及铝合金的表面处理  \n\n铝是一种特殊金属，它能在自身表面形成一层氧化膜，在一定程度上能防止腐蚀。然而这种保护还不足以让铝材在一般环境条件下维持长久的生命力。而在铝中加入镁、铜、锌等元素制成铝合金后，机械强度提高了，但抗腐蚀性能下降了。此外，氧化铝并不是粉末涂料或其他涂料的良好基材，通常有机涂层在铝材上的附着力非常差，因此，需要经过化学处理使铝的表面生成一层均匀的、多孔性的氧化膜，使其对有机涂层具有吸附性，从而增大接触面积，增强涂膜的附着力，这样也提高了铝的抗腐蚀性能。  \n\n和钢材一样，在对铝材进行化学处理前，为了除去表面的污垢、油、油脂和腐蚀物，必须先经过清洗步骤。  \n\n(1）表面除油铝及其合金不像黑色金属那样能耐强碱的侵蚀，所以要注意清除铝制品表面的油污，不能采用强碱配置的清洗剂清洗，一般宜采用有机溶剂除油法，表面活性剂除油法，或由磷酸钠、硅酸钠、碳酸钾、碳酸钠等碱性盐配置的弱碱性清洗液清洗。为了改善清洗效果，通常还要加人润湿剂。  \n\n(2）化学氧化铝制工件的化学氧化工艺与钢铁件的磷化工艺相似。生成的氧化膜有较好的吸附力，是涂装的良好底层。它们的不同之处是铝的化学氧化膜薄，其厚度为 $0.5\\sim$ $4\\mu\\mathrm m$ ，不能形成厚膜，质软不耐磨，故其防腐蚀性差，不宜单独使用。化学氧化的溶液有碱性和酸性两种。  \n\n$\\textcircled{1}$ 碱性溶液氧化法 此法所得氧化膜质软、疏松，容易碰坏磨损。  \n\n溶液配方及工艺条件举例：  \n\n<html><body><table><tr><td>无水碳酸钠NaCO/(g/L）</td><td>50</td><td>槽液温度/℃</td><td>80～100</td></tr><tr><td>铬酸钠NazCrO/(g/L)</td><td>15</td><td>氧化时间/min</td><td>15~20</td></tr><tr><td>氢氧化钠NaOH/(g/L)</td><td>2~2.5</td><td></td><td></td></tr></table></body></html>  \n\n处理的零件需立即用水冲洗，然后再进行钝化和涂装，否则时间长会影响涂膜的结合力。由于其性能较差一般很少使用。  \n\n$\\textcircled{2}$ 磷酸盐、铬酸盐氧化法此法又称阿罗丁氧化法。该氧化膜的质量比用碱性溶液所得氧化膜的好，抗腐蚀性也好。  \n\n溶液配方及工艺条件举例：  \n\n磷酸 $\\mathrm{H_{3}P O_{4}/(g/L)}$ $50\\sim50$ 硼酸 $\\mathrm{{H_{3}B O_{3}}/(\\varepsilon_{B}/L)}$ 1\\~1.2铬酐 $\\mathrm{CrO_{3}/(g/L)}$ 20\\~25 槽液温度/ $q$ 30～36氟化氢铵 $\\mathrm{NH_{4}H F_{2}/(g/L)}$ $3\\sim3.5$ 氧化时间/ $\\mathbf{\\dot{min}}$ 3\\~6磷酸氢二铵 $(\\mathrm{NH_{4}})_{\\textrm{\\scriptsize H P O_{4}/(g/L)}}$ $2\\sim2.5$  \n\n为了提高抗蚀性能，可以进行钝化处理。  \n\n用此法获得的氧化膜，其外观为无色或彩虹色。膜的厚度 $3\\sim4\\mu\\mathrm{m}$ ，与基体金属的结合力好，膜层致密，且耐磨，工件尺寸无显著变化。  \n\n$\\textcircled{3}$ 铝及其合金的非铬化处理铬酸盐法是最适合涂饰建筑物中所用铝制材料表面处理的方法。但是由于铬酸盐中的六价铬的毒性问题，促使人们去寻找无铬的替代品对铝材进行表面处理。如使用氟氢酸和六氟锆酸（ $\\mathrm{H_{2}Z r F_{\\hat{5}}}$ ）或六氟钛酸（ $\\mathrm{H_{2}T i F_{5}}$ ）组成的处理液对清洗过的铝材进行表面处理，经这种溶液处理后，在铝材表面转化沉积成非常薄的（大约$0.01\\mu\\mathrm{m})$ 、几乎无色的膜层，它们分别由铝-锆络合物或铝-钛络合物组成，这种转化膜的防腐蚀性能与铬酸盐氧化膜的防腐蚀性能类似。此外，还有以铈化学为基础的铈酸盐处理法。这些新处理方法的数据和经验还在积累当中。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 748,
+        "chunk": "# 3.锌及锌合金的表面处理  \n\n锌一般是以钢材表面镀锌、喷锌或以铸件形式作为被涂装基材而使用的。与铝的情况相似，暴露在大气条件下的锌能自已钝化形成氧化锌或碳酸锌薄层。但是这层“白锈”保护时间不长久，尤其是在工业腐蚀性气体的环境中更加不好，锌在腐蚀进程中，表面缓慢地形成灰白色的粉末薄层。即使是将粉末涂料直接涂覆在新制得的氧化锌或碳酸锌的镀锌钢材表面，锌也可以和涂料基料中的羧基发生反应生成锌皂，从而降低了涂料对基材表面的附着力。为使涂层与锌表面结合牢固，就要使锌的表面粗糙并形成一层防止锌与基料反应的保护膜。和铝一样，锌在形成转化膜的处理之前应对其表面做清洗处理。  \n\n(1）锌的表面清洗锌的清洗技术和方法与铝基本相同，使用碱性盐和表面活性剂或有机溶剂即可。只有当锌的表面存有大量污物时，才可以加人少量的苛性钠以提高清洗液的清洗作用，不过这样会引起锌表层的一些腐蚀，但会改善基材与粉末涂层的附着力。也可以使用弱酸性的清洗液除去锌表面的氧化物。  \n\n(2）转化膜的形成锌表面形成转化膜的主要方式是磷酸锌的转化，用磷酸盐处理剂可在锌表面生成一层锌盐磷化膜，其机理与钢材的磷化处理一样。游离的磷酸与锌的表面作用生成不溶性的磷酸锌 $Z n_{3}(\\mathrm{PO}_{4})_{2}$ ，致密地覆盖在锌的表面。磷化膜的附着量通常为 $\\mathrm{1}\\mathrm{\\sim}\\mathrm{5g/m^{2}}$ 睿这种膜与基材结合紧密，呈结晶颗粒排列，在表面形成细小的凹凸面并均匀地分布在整个表面。这对涂膜的附着很有利，并阻止锌与基料的皂化反应，防止了磷化膜内层锌的进一步腐蚀，显著提高了涂层的耐久性。在磷酸盐处理剂中加入氢氟酸、氟化物等能进一步优化磷化膜的质量。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 749,
+        "chunk": "# 二、粉末涂料的涂装  \n\n相对于液态涂料来说，粉末涂料的涂装具有能自动控制涂层厚度、极少有流挂问题、边角覆盖力好、加工动力费用和总生产成本低、操作人员培训费用低、涂料利用率接近100%、能满足严格的环保法规等优势。粉末涂料的涂装就是使用各种方法将粉末附着在被  \n\n涂工件上，再经过加温熔融成膜或固化成膜。粉末涂料的涂装方法可分为：流化床法、静电流化床法、静电喷涂法和火焰喷涂法等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 750,
+        "chunk": "# 1.流化床法  \n\n流化床涂装工艺是在粉末涂装中较早实施的方法之一。我国早在20世纪60年代初就开始对热固性环氧粉末进行了流化床涂装研究，并取得了成功。当时主要应用于机电产品，如对电机的绝缘涂层和防腐涂层等。近年来随着粉末及其涂装技术的发展，又广泛地应用在家用电器、生活电器、钢结构件等方面。应用的原料也由原来的环氧粉末发展到尼龙、聚酯、聚乙烯、聚氯乙烯等更多的粉末品种。  \n\n流化床涂装工艺的方法是将空气或某种情性气体吹入容器底部，使粉末涂料翻动达到“流化状态”。空气通过多孔性透气板，成为均匀分布的细散气流使粉末翻动，每个粉粒先上升后下降。这种流动粉体的性质很像液体。放人其中的物体如同沉人液体中。但这种流态化粉末与液体的特性仍然存在很大的不同，例如当一段管子被水平地放人液体中，其内壁就会立即被润湿，但在粉管中流化状态的粉末就变得静止不动了。这是因为粉粒的行动主要是上下方向的，水平方向移动很少。  \n\n流化床的工作原理是用均匀的细散空气流通过粉末层，使粉末微粒翻动呈流态化。气流和粉末建立平衡后，保持一定的界面高度。将需涂覆的工件预热后，放人流态化粉末中，即可得到均匀的涂层，最后加热固化（流平）成膜。  \n\n流化床主要是由气室、微孔透气隔板和流化槽三部分组成。如图3-8-23所示是一种较为常见的桶形流化床结构。  \n\n流化床法属于热熔涂装工艺，能否形成均匀涂层的关键在于控制好粉末的流化状态。流化床法涂装设备简单，操作容易，不需要粉末的循环使用装置。  \n\n环氧粉末涂料采用流化床热熔敷工艺，实现了微电机、中小电机、分马力电机的转子和定子铁芯的粉末熔槽绝缘，取代了传统的聚酯薄膜、青壳纸复合槽绝缘工艺，既降低了绝缘层厚度，又提高了工效，还为自动化嵌线创造了必要的条件。  \n\n![](images/4bb1fa38a1913bcf3fc5f31dc822ddcf80c22a3275395e2eb5e0bee4664ba639.jpg)  \n图3-8-23 常见的桶形流化床结构  \n\n此外，流化床粉末涂装还在电力电容器、电容器外壳、电感线圈、变压器铁芯、电阻器、接线盒、小型蓄电池等电器产品的绝缘防潮上得到了广泛的应用，增强了产品的耐湿热、耐老化、耐高低温、耐冲击性和三防性能，显著地提高了产品的可靠性。流化床涂装生产线立体示意图如图3-8-24所示。 5",
+        "category": " Introduction"
+    },
+    {
+        "id": 751,
+        "chunk": "# 2.静电喷涂法  \n\n静电涂装技术是粉末涂料应用在金属制品中最常采用的操作方法。这种方法的基本原理是依靠通过喷枪的压缩空气作为干粉的推动力，粉末在喷枪中被充上静电，粉末粒子在静电喷枪向被涂工件的移动是受带电粒子与工件形成的电场力和气流推力的共同作用形成的。粉末粒子作为绝缘材料使得静电电荷停留在粒子表面并附着在工件上，即使静电枪与工件之间的电场除去后，这些带电的粉末粒子仍然能靠电荷的引力牢固地吸附在工件的表面，以保证粉末粒子在熔结前对工件的吸附，这对粉末的冷涂装很重要。未吸附到工件上的过喷粉末可通过回收设备收集和循环再用，使粉末涂料具有高的利用率（可达98%）。  \n\n![](images/ebed3a67759b927c2e5d911fe28864d654b9043551a5dab3dfeb6df50cf78894.jpg)  \n图3-8-24 流化床涂装生产线立体示意图  \n\n（1）高压静电喷枪（电晕喷枪）这种喷枪是对粉末涂料粒子进行充电用得最广泛的装置。在喷枪内至少有一个电极与高压静电发生器连接，为粉末粒子提供电荷。高压静电喷涂中，高压静电是由高压静电发生器供给的。工件在喷涂时应先接地，在净化的压缩空气作用下，粉末涂料由供粉器通过输粉管进入静电喷粉枪。喷枪头部装有金属环或极针作为电极，金属环的端部具有尖锐的边缘，当电极接通高压静电后，尖端产生电晕放电，在电极附近产生了密集的负电荷。粉末从静电喷粉枪头部喷出时，捕获电荷成为带电粉末，在气流和电场作用下飞向接地工件，并吸附于其表面上。  \n\n粉末静电喷涂过程中，粉末所受到的作用力可分为粉末自身重力、压缩空气推动力和静电场引力。粉末借助空气推力和静电场引力，克服自身重力，吸附于工件表面，经固化（塑化）后形成固态涂膜。  \n\n从粉末静电吸附情况来看，大体上可分为以下三个阶段，如图3-8-25所示。  \n\n![](images/c4f940e4415f20ead5e5e2801643e5a5c65650acfc081d4e3d590d17ade279a2.jpg)  \n图3-8-25 粉末静电吸附情况  \n\n图3-8-25(a）为第一阶段，带负电荷的粉末在静电场中沿着电力线飞向工件，粉末均匀地吸附于正极的工件表面；图3-8-25（b）为第二阶段，工件对粉末的吸引力大于粉末之间相互排斥的力，于是粉末密集地堆积，形成一定厚度的涂层；图3-8-25（c）为第三阶段，随着粉末沉积层的不断加厚，粉层对飞来的粉粒排斥力增大，工件对粉末的吸引力因粉层对粉末的排斥力相等时，继续飞来的粉末就不再被工件吸附了。  \n\n吸附在工件表面的粉末经加热后，就能使原来“松散”堆积在表面的固体颗粒熔融固化（塑化）成膜。  \n\n静电喷枪不仅能使粉末带电，通过喷嘴形状的改变，还可控制喷出粉末云雾的尺寸、形状和密度（图3-8-26)。此外，可根据调整静电发生器的电压调整粉末在工件上的附着量，在一定范围内喷涂电压增大，粉末附着量增加。但当电压超过90kV时，粉末附着量反而随电压的增加而减少。  \n\n![](images/664a61bd2c638f9e207671e5f253a4eb8331c48a947107f3e79ed7b3b71f8a72.jpg)  \n图3-8-26 喷嘴系列及喷漆形状  \n\n高压静电的输入方式分为枪外供电和枪内供电两种。枪外供电是将高压静电发生器放在枪体外面，高压静电通过金属电缆输送到喷枪内放电针上。枪内供电是将高压静电发生器微型化，置于枪内，称为枪内供电式。这就使静电喷涂设备整体体积缩小，节省一根高压电缆，使喷枪使用灵巧，而且操作安全，减少高压泄漏。  \n\n高压静电喷枪在静电喷涂时会产生“反离子化”现象，即粉末在工件上的沉积过程中，随着厚度的增加，被涂工件表面的负电子（或正电离子）和负（或正）的带电粒子不断聚集，涂层之间的电势也在增加。当这种电势增加到超过击穿电压的程度时，粉末附着层的表面或内部将发生局部的放电现象，由于粉末涂料是以堆积形式附着在工件表层的，这种局部放电时部分粉末粒子形成了与静电枪电极相反的离子，并沿着电力线向枪头方向移动而脱离工件，使电吸附的粉末堆积层破裂。“反离子化”现象所造成最大的影响是使涂膜变得不均匀，产生“橘皮”现象。研究发现，高压静电喷涂时，粉末在形成第一层沉积时即产生“反离子化”现象，时间大约在喷涂后1s的时候。  \n\n此外，高压静电枪对几何形状复杂的工件喷涂时，枪口和工件之间形成的电场很不均衡（图3-8-27)，产生的法拉第效应使工件凹陷处上粉较困难。  \n\n![](images/2587f344a1e347cdd2bee6738d8eb4de34995440bbf09d133c77d981fcc2f554.jpg)  \n图3-8-27 电场分布  \n\n(2）摩擦静电喷枪若选用恰当的材料作为喷枪枪体，粉末在压缩空气的推动下与枪体内壁以及输粉管内壁发生摩擦而使粉末带电，带电粉末粒子离开枪体飞向工件并吸附于工件表面。其工作原理如图3-8-28所示。  \n\n![](images/364d57dc60380b338f8730f85f69effa4af9b2aecdbabc80512800cb6c5269b6.jpg)  \n图3-8-28 摩擦静电喷涂原理图  \n\n该方法不需要高压静电发生器。在摩擦静电系统中，枪体通常使用电阴性材料。两物体摩擦时，弱电阴性材料产生正电，强电阴性材料则产生负电。喷涂时由于粉末粒子之间的碰撞以及粉末与强电阴性材质制作的枪体之间的摩擦使粉末粒子带上正电荷，而枪体内壁则产生负电荷，此负电荷通过接地电缆引入大地。带正电的粉末粒子在气流的作用下飞向工件并被吸附在工件表面上，经固化后形成涂膜，从而达到涂装目的。喷涂时粉末所带的电荷不是由外电场提供的，而是粉末与枪壁发生摩擦带上的。  \n\n喷出枪口的带电粉末粒子形成一个空间电荷，电场强度取决于空间电荷密度和电场的几何形状，即决定于粉末粒子的带电量、粉末在气粉混合物中所占比例和喷枪口的喷射图形。由喷枪喷出的气粉混合物因气流的扩散效应和同种电荷的斥力，气粉混合物体积逐渐膨胀，电荷密度下降，电场减弱。电场减弱的方向与气流方向一致，粉末的受力方向与气流方向相同。当粉末离开枪体后，粉末移动的动力主要是空气，粉末粒子能够到达工件的每个角度，并与工件产生很好的附着效应，形成致密的粉末涂层。由于不存在外电场，摩擦静电喷涂法能较好地克服法拉第屏蔽效应。  \n\n由于摩擦枪具有不同于高压枪的带电方式和电场，因此在静电喷涂中显示出其独特的优点：高压静电喷涂时，粉末所带的电荷来自高压静电发生器，而摩擦枪的粉末带电主要是因粉末和枪体摩擦而产生的，这就省去了高压静电发生器，从而节约了设备投资；摩擦枪内无金属电极，喷涂中不会出现电极与工件短路引起火花放电，从而消除了引起粉尘燃烧、爆炸的事故隐患；摩擦枪不接高压电缆，枪头移动空间范围广，喷涂操作比较方便，且不受喷涂距离变化的影响，喷枪离工件距离远些或近些，喷涂效果相近；小型工件或形状比较复杂的工件表面用摩擦枪喷涂时，效果好得多，比高压静电枪更为适用。粒径较大的粉末表面积大，比较利于摩擦带电，而较细的粉末则不利于摩擦带电。试验数据表明，在摩擦静电喷涂时，反电离现象发生在喷枪启动后 $10\\sim20\\mathrm{s}$ ，这就可能提高工件的一次上粉率。  \n\n摩擦枪的不足之处有下面几点：因为摩擦静电是通过摩擦枪体而获得的，为了保证较好的静电效果，就需要对摩擦枪的芯阀定期更换，同高压静电枪相比，喷枪的使用寿命较短；因为适用于摩擦枪喷涂的粉末品种受到限制，有些粉末品种的摩擦带电效果较差，例如聚乙烯粉末涂料的摩擦带电效果就不理想，所以粉末涂料的应用场合受到限制；与高压静电喷枪相比，粉末摩擦带电量不充足，粉末的附能力要弱一些；摩擦静电喷涂工艺，对环境、气源的要求比较严格，某种程度上限制了它的应用范围。  \n\n电晕喷枪与摩擦喷枪喷涂效果示意如图3-8-29所示，电晕喷枪和摩擦喷枪的性能对比见表3-8-22。  \n\n![](images/88cff1da5157ffe0dc0e794274a778b9dc05f464029d65ebc453df69d3bee514.jpg)  \n图3-8-29 电晕喷枪与摩擦喷枪喷涂效果示意  \n\n表3-8-22电晕喷枪和摩擦喷枪的性能对比  \n\n\n<html><body><table><tr><td>性能</td><td>电晕喷枪</td><td>摩擦喷枪</td><td>性能</td><td>电晕喷枪</td><td>摩擦喷枪</td></tr><tr><td>摩擦粉末</td><td>+</td><td>+</td><td>空气消耗量</td><td>较低</td><td>较高</td></tr><tr><td>不适于摩擦用的粉末</td><td>+</td><td>O</td><td>通路</td><td>十</td><td>++</td></tr><tr><td>渗透能力</td><td>+</td><td>++</td><td>磨损</td><td>+</td><td>一</td></tr></table></body></html>\n\n注： $++$ 代表极好； $^+$ 代表好；一代表较差；○代表不适用。  \n\n(3）静电流化床法静电流化床涂装工艺是静电涂装技术与流化床工艺相结合的一种工艺。工件在常温下涂覆，克服了流化床涂覆在高温下操作的缺点，同时又发挥了流化床设备简单、操作方便、易于实现机械化、自动化生产的优点。根据电晕放电原理，在静电流化床床身的粉末中放置一个接负高压的电极。当电极接上足够高的负电压时，就产生电晕，附近的空气被电离产生大量的自由电子。电极埋在粉末中，粉末在电极附近不断上下运动，捕获电子成为负离子粉末，这种负离子粉末就能被吸附到带正电的工件上去。静电流化床法与静电喷涂法相比，特点是：设备结构简单，集尘装置和供粉系统要求低，粉末屏蔽容易解决，易实现自动化生产。对于涂覆形状较为简单的工件，具有效率高、设备小巧、投资少、操作简便等突出优点。但是，这种方法涂覆的工件，顺着流化床床身方向会产生涂层不均匀现象。当制造大型静电流化床设备时，不但使操作工艺变得复杂，设备结构也将失去简易这一重要优点，反而变得复杂昂贵。因此，静电流化床工艺主要用于线材、带材、电器、电子元件等形状比较简单的小零件的粉末涂覆。  \n\n静电流化床的结构和一般流化床基本相同，不过作为涂覆室的床身和气室需要绝缘性能良好的塑料如聚氯乙烯板或有机玻璃板制成。设计结构上要保证高压电极对地和操作者有良好的绝缘。静电流化床的结构有多种样式，但基本原理相同，如图3-8-30所示的配有控制电极的静电流化床，它的特点是粉末下面有两组对称的棒形充电电极，在工件上面还有一个接地的控制电极，借助控制电极来调整工件的涂覆质量。实际上它是起着调节床身内空间电场的分布和强度，使被涂工件的各个部位处于一个均匀的电场中。这样就能使工件获得较好的涂覆质量。  \n\n![](images/074a150fab4b3d8c276dc3ca65f19403e5fe02beab6ab2c84709cc4982215adf.jpg)  \n图3-8-30 配有控制电极的静电流化床1—控制电极；2—长形零件；3—充电电极  \n\n静电流化床涂装时，涂层达到一定厚度后，容易发生“反离子化”现象，使涂层产生麻坑和边角崩落现象，在操作时应注意控制涂装工艺。  \n\n静电流化床的气态粉末流速低于粉末喷涂的速率，而且部分未被吸走的粉末受重力的作用仍然降落于流化床内，只有小部分较细粉末被集尘器回收，集尘器中含尘气体的粉末浓度很低。由于集尘气流的含尘浓度低，粉粒细，不宜用旋风扩散式除尘器，也不必采用二级回收装置。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 752,
+        "chunk": "# 3.火焰喷涂法  \n\n粉末火焰喷涂法又称为粉末热熔融射喷涂法。火焰喷涂的工作原理是用压缩空气将粉末涂料从火焰喷枪嘴中心吹出，并以高速通过从喷嘴外围喷出的火焰区域，使其成为熔融状态喷射黏附到工件上。火焰喷枪是火焰喷涂施工的主要装置，火焰喷涂原理图如图3-8-31所示。  \n\n![](images/be6b444cd32453ab2e4403842fdb028f4ce8555d80b9f4ca7a1cd0223c9b5e58.jpg)  \n图3-8-31 火焰喷涂原理图  \n\n塑料粉末借助输送气体从枪头中心的铜管喷出，当粉末穿过火焰区时受热熔融射粘于工件上，同时工件也被预热，因此附着于工件上的粉末颗粒能够相互融合形成光滑涂膜。为了防止枪嘴喷出的粉末直接与高温的燃气火焰接触而变质老化，在火焰与粉流之间设计有气体隔离区域，将两者分开并可调节粉末熔融的合适温度。这股环形气流同时还可冷却喷枪嘴中心的铜管，使其不会因温度高熔化粉末而造成喷嘴堵塞。火焰喷枪的燃烧火焰一般采用氧气和乙炔气的混合气体。输送粉末和冷却保护气体采用脱水除油的压缩空气或氮气。  \n\n火焰喷涂涂装法主要用于金属表面涂装聚乙烯、尼龙、氯化聚醚等热塑性粉末涂膜。可用于化工设备、化工池槽、机械零件、板材、线材等方面。适宜用作防腐蚀涂层、耐磨涂层和一般装饰性涂层。当前粉末火焰喷涂方法正在受到人们的关注。它主要有以下特点：设备简单，价格低廉，可以在生产作业现场施工，不像静电涂装和流化床涂装那样必须有成套涂装设备；一次喷涂可得到较厚的涂膜；可以涂装大型工件。粉末涂装对被涂的工件必须进行固化或塑化工序，大工件就受到烘炉尺寸的限制，火焰喷涂则可将粉末直接熔粘于工件表面，因此，对贮藏罐、框架等大型工件的施工有其独特的优势，在设备维修上也有较大潜力。  \n\n目前，除火焰喷涂技术还没有被广泛采用外，静电喷涂、流化床和静电流化床的涂装技术都有了成熟的实际应用。各种涂装技术都有各自的特点，表3-8-23是不同涂装技术特性的比较。  \n\n表3-8-23 不同涂装技术特性的比较  \n\n\n<html><body><table><tr><td>工件的特性</td><td>静电喷涂</td><td>流化床和静电流化床</td><td>火焰喷涂</td></tr><tr><td>尺寸</td><td>比较大</td><td>比较小</td><td>无限制</td></tr><tr><td>材质</td><td>金属导体</td><td>不一定是导体</td><td>不一定是导体</td></tr><tr><td>耐温性</td><td>比较高</td><td>高</td><td>无关</td></tr><tr><td>涂层外观</td><td>高</td><td>低，不适合装饰目的</td><td>低，不适合装饰目的</td></tr><tr><td>涂层厚度</td><td>涂膜比较薄</td><td>能形成均匀的高厚度涂膜</td><td>能形成高厚度涂膜，均匀性取决于操作</td></tr><tr><td>涂料类型</td><td>热塑性和热固性</td><td>热塑性和热固性</td><td>热塑性</td></tr><tr><td>换色</td><td>困难</td><td>比较难</td><td>容易</td></tr><tr><td>设备投资</td><td>中至高</td><td>低</td><td>非常低</td></tr><tr><td>劳动力强度</td><td>低，因为高度自动化</td><td>中等，取决于自动化</td><td>比较高</td></tr><tr><td>能量消耗</td><td>只需后加热</td><td>预热和后加热</td><td>低，不需要预热和后加热</td></tr><tr><td>涂料损耗</td><td>非常少</td><td>非常少</td><td>取决于工件几何形状</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 753,
+        "chunk": "# 4.供粉器、喷粉室和粉末回收循环系统  \n\n(1）供粉器供粉器的作用是给喷枪提供粉流，是喷涂工艺中的一个关键设备。它的功能是将粉末连续、均匀、定量地供给喷枪，是粉末静电喷涂取得高效率、高质量的关键部件。  \n\n目前，使用的供粉器一般有3种结构类型，即机械式、压力式和抽吸式，如图3-8-32所示。  \n\n机械式供粉器的特点是能定量、精确地供粉，供粉精度可达 $2\\%\\sim3\\%$ ，它是通过调整转盘和螺杆的速度来控制供粉量大小。机械式供粉器对涂膜厚度的波动性影响较小，由于它是以机械式传动方式供粉，供粉量大小主要取决于转盘和螺杆的速度。机械式供粉器可用于多支喷枪的喷涂流水线。这类供粉器的缺点是结构比较复杂，机械传动部分密闭性要求高，粉末易卡住机械传动零件，制作成本也高，故一般较少采用。  \n\n压力式供粉器是一个密封性结构。其原理是：经过油水分离净化后的压缩空气从进气管进入，在喇叭口下（内有一道槽及4个倾斜角为 $45^{\\circ}$ 的出气小通道）形成旋流，从而使粉末成为雾化状态随气流从出粉口输送至喷粉枪。供粉器内喇叭头会随着粉末减少而自动下降。调节压缩空气的压力就可以改变供粉量的大小。压力式供粉器的容积一般在 $15\\sim25\\mathrm{L}$ 。由于它是密封结构，不能连续加粉。因此，只能作单件喷粉使用，不能在喷涂流水线中使用。而其突出优点是可大大提高喷粉量，达到 $1\\mathrm{kg/min}$ 以上，有些场合下喷涂作业可起到特殊作用。压力式供粉器使用的空气压力一般为 $0.10{\\sim}0.15\\mathrm{MPa}$ 8  \n\n抽吸式流化床供粉器是利用文丘里泵的抽吸作用来输送粉末的，其原理是在压缩空气通过（正压输送）的管路中设置文丘里射流泵（亦称之为粉泵)，空气射流会使插人粉层的吸粉管口产生低于大气压的负压，处于该负压周围的粉末就被吸人管道中，并被射流加速，再从管道中输送粉末至喷枪。但是，在粉末吸入口的周围会产生粉末空穴，造成缺粉现象。因此，必须解决供粉器中的粉末不断向吸粉口流动的问题，使喷出的粉雾均匀、连续。流化床内的粉末具有类似液体流动的特性，这样就保证粉末能不断向吸粉口流动。应用最多的是纵向抽吸式流化床供粉器，一次气流（主气流）射人粉泵后，吸粉管口产生负压，将流化床内粉末吸至输粉管中。二次气流（稀释气流）用于调节喷出的粉末几何图形大小，同时使粉末的雾化性能更好。这种供粉器的优点是：供粉均匀、稳定；供粉桶密封性能好；可以将几支粉泵置于同一个供粉桶；粉泵内清理积粉方便；供粉精度高。  \n\n![](images/77bdbb64a6588912f5835c87f9eb9cda85a500a3ff0ded3e9cb83c36b2df3f95.jpg)  \n\n图3-8-32 供粉器类型  \n\n1—卡子；2，5—进气管；3，4—出粉管；6-喇叭；7—粉筒身  \n\n(2）喷涂室喷涂室又称喷粉柜，它是实施粉末喷涂的操作室，其制作的材料、形式和尺寸直接关系到产品喷涂的质量。喷粉柜可用金属板制成，也可用塑料板加工。选用哪种材料制作喷粉柜，主要根据经济性、耐久性和便于施工等因素来考虑。不同材料制作的喷粉柜的优缺点见表3-8-24。  \n\n表3-8-24不同材料制作的喷粉柜的优缺点  \n\n\n<html><body><table><tr><td>选用材料</td><td>优点</td><td>缺点</td></tr><tr><td>冷轧钢板</td><td>1.加工容易 2.牢固，便于运输和修理 3.安全</td><td>1.带电粉末易附着板壁，体积大 2.静电喷涂效率下降 3.产生火花放电机会增大</td></tr><tr><td>塑料</td><td>1.粉末不易附着内壁 2.粉末容易清扫 3.可小型化 4.火花放电时安全 5.喷涂效率高</td><td>1.制造困难 2.容易损坏</td></tr><tr><td>钢板塑料复合材料</td><td>1.粉末不易附着内壁 2.粉末容易清扫 3.可小型化 4.打火少，安全 5.喷涂效率不受影响 6.喷粉柜机械强度高</td><td>1.价格比金属高 2.加工难度比钢材大</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 754,
+        "chunk": "# 不同材质的喷粉室使用效果如图3-8-33所示。  \n\n![](images/b7eb36a360ee54625c572da60ed487d398e936de3a6498d1cc7f5398a0249b6b.jpg)  \n图3-8-33 不同材质的喷粉室使用效果  \n\n喷粉柜的大小取决于工件的大小、传送速率和喷枪的粉量。通常情况下喷枪数量少，粉末喷涂能力偏低。喷粉室内选择多少支喷枪主要取决于工件的形状、喷涂表面积、传输链速度和单班产量等因素。选用喷粉柜时应考虑到便于清理粉末和粉末的换色，以及粉末回收时的风速和风量等因素。风量应掌握在不能将喷涂于工件表面的粉末涂层吹掉，不能让粉末从喷粉室开口部位飞扬出去，减少粉末的浪费和环境污染。喷粉柜内粉末浓度应低于该粉末爆炸极限的下限。  \n\n(3）粉末回收装置粉末涂料在静电喷涂过程中，工件的上粉率大约为 $50\\%\\sim70\\%$ ·有 $30\\%\\sim50\\%$ 的粉末飞扬在喷涂室中或散落在喷涂室底面，这一部分粉末必须通过回收装置收集，经重新过筛后，送回供粉桶回用，否则，不仅浪费粉末涂料，还会污染环境，带来公害，危害操作人员的健康。  \n\n粉末回收装置的种类较多，选用什么样的粉末回收系统，必须从产品的结构形状、生产批量、作业方式、粉末品种和换色频率等因素来综合考虑。  \n\n$\\textcircled{1}$ 旋风布袋二级回收器该二级回收装置主要包括旋风分离器的一级回收和布袋除尘器的二级回收，如图3-8-34所示。该回收器第一级旋风分离器与喷粉柜相连接，它收集了  \n\n![](images/b16e9a791a1dfe4310d12b24e085df30f9c14cf3275b140e978f6fd5f5a2ce63.jpg)  \n图3-8-34 旋风布袋二级回收器  \n\n1—供粉桶；2—出粉管（接喷枪）；3—喷枪；4—回收管道；5—旋风分离器；6—超细粉回收柜（二级回收柜）  \n\n大部分的回收粉末，占粉末回收总量的70%～90%；第二级袋式回收器起到帮助旋风分离器提高回收率的作用，同时将第一级回收除不掉的细粉全部回收。这种二级回收器的总除尘效率可达 $99\\%$ 以上。  \n\n该回收器对旋风分离器和布袋除尘器的底下部回收粉末的处理，或者是利用喷室底部下抽屉贮存回收，或者是借助压缩空气造成喷室底部积粉呈紊流状态，然后被喷室内安全气流吸走回收。前者多见于小型喷室，后者多见于大、中型喷室。  \n\n$\\textcircled{2}$ ②无管道式回收器无管道式回收器如图3-8-35所示，该回收器的滤芯3安装在喷室1后面的回收、除尘柜2中，过滤后的粉末落在粉末回收容器6中，再经文丘里泵5返回喷枪回用。其最大特点是省去了管路系统，把操作室及回收设备聚合成一体，结构紧凑。这种回收器可以做成与喷室分开的装置，配以轮子后就可以方便地同喷室组合或拆开，大大有利于快速换色的涂装施工。  \n\n![](images/7b6c207477787b50717f393a9e8af8bbdf89e2c52e9e4dccb14f306799f586d5.jpg)  \n图3-8-35 无管道式回收器  \n\n1—喷室；2—回收、除尘柜；3—滤芯；4一脉冲吹喷；5—文丘里泵；6—粉末回收容器；7一喷枪；8—引风  \n\n而使用多旋风分离器的二级回收装置（图3-8-36）可使粉末使用和回收率进一步提高。这种列管式小旋风分离器和滤芯过滤二级回收装置，回收装置和喷粉室直接连接。  \n\n(4）干燥固化设备涂装生产工艺中，涂层的固化是十分重要的工序之一，在粉末静电喷涂工艺中，涂层的固化是不可缺少的工序。涂层的干燥固化要消耗大量的能量，因此研究先进的涂层固化工艺，设计和选择合理的干燥固化设备，减少能耗，降低成本，是推动粉末涂装技术发展的重要途径之一。  \n\n粉末涂装工艺中，工件经过除油、除锈、磷化等表面处理工序以后必须经过烘干，除去工件表面的水分，以保证粉末涂层固化以后的结合力。一般烘干温度为100～120℃，烘干时间应视工件的复杂程度、材质、壁厚等因素确定，对于一般薄壁板状零件烘干时间通常为8～10min，粉末涂层的固化温度为180～220℃，固化时间亦应视工件的复杂程度、材质、壁厚等因素确定，薄壁板状零件粉末涂层固化时间通常为20min。粉末涂料的品种不同、配方不同，其固化温度与固化时间也会有所不同。由于粉末涂层固化温度比较高，固化时间也比较长，因此消耗能量比较大，在一定程度上限制了粉末涂装更为普遍的应用。世界各国都在竞相研究低温短时间快速固化的粉末涂料，但是目前国内生产的各种热固性粉末的固化温度一般高于160℃，固化时间不少于15min。对于一些热塑性粉末涂料（例如聚乙烯、聚丙烯、聚酰胺等）采用流化床涂覆工艺时，还需将工件预先加热到一定温度，通常预热到250～360℃后，将工件浸入流化状态的粉末中，使粉末熔融后黏附在工件表面，然后对工件进行熔融塑化处理，其处理温度为 $180{\\sim}220^{\\circ}C$ ，固化时间 $15\\sim25\\mathrm{min}$ 。粉末涂料被涂覆在工件表面，必须经过一定温度和时间的烘烤，才能使粉末熔融流平、交联固化成均匀的涂层。不同的粉末有各自不同的熔融、流平和交联固化温度。粉末的固化温度一般是由粉末生产厂商在粉末生产出厂时规定的。施工中烘烤温度过低，粉末涂料熔融流平、交联固化不足，会造成涂层表面粗糙、光亮度差、附着力差，强度和硬度都会下降。如果烘烤温度过高，轻则造成涂层失色，重则使涂层焦化，机械强度严重下降。  \n\n![](images/9b665f721dfee4d8023540eee7aea516b38fb118d5d4e96f5ff069c4f4060dd9.jpg)  \n图3-8-36 多旋风分离器的二级回收装置  \n\n对烘炉或烘道的要求：烘炉或烘道装有保温和热风循环装置，可以使整个烘炉或烘道内温度均匀。工件置于烘箱内必须让工件与工件之间留有足够的孔隙以保证热空气的流通，从而防止工件涂膜产生上半部已经固化（塑化）完全而下半部处于“夹生”状态，或下半部完全固化（塑化)，而上半部已经“热过头”。因为烘炉或烘道中上半部温度总是高于下半部的温度，只有配备了热风循环装置后，才能克服上述端。另外，在喷室和烘道之间采用联动装置较为理想。工件在喷涂完毕后，通过传动部件自动进入烘道，避免发生工件间相互碰撞，采用流水线作业，不仅提高生产效率，产品质量也可以得到保证。  \n\n(5）涂装生产中常见涂膜病和产生的原因 见表3-8-25。  \n\n表3-8-25 涂装生产中常见涂膜病和产生的原因  \n\n\n<html><body><table><tr><td>涂膜缺陷</td><td>产生原因</td></tr><tr><td>2.温度过高 涂膜光泽不足或失光</td><td>1.固化时烘烤时间过长 3.烘箱内混有其他有害气体 4.工件表面过于粗糙 5.前处理方法选择不妥</td></tr><tr><td>涂膜变色</td><td>6.供粉或回收系统中不同粉末的干扰 1.多次反复烘烤 2.烘箱内混有其他气体 3.固化时烘烤过度</td></tr></table></body></html>  \n\n续表续表  \n\n<html><body><table><tr><td>涂膜缺陷</td><td>产生原因</td></tr><tr><td>涂膜表面橘皮</td><td>1.喷涂的涂层厚薄不均 2.粉末雾化程度不好，喷枪有积粉现象 3.固化温度偏低 4.粉末受潮，粉末粒子太粗</td></tr><tr><td></td><td>5.工件接地不良 6.涂膜太薄 1.工件表面处理不当，除油不净 2.气源受污染，压缩空气除油、除水不彻底</td></tr><tr><td>涂膜产生凹孔</td><td>3.工件表面不平整 4.受硅尘或其他杂质污染 1.工件表面处理后，水分未彻底干燥，留有前处理残液</td></tr><tr><td>涂膜出现气泡</td><td>2.脱脂、除锈不彻底 3.底层挥发物未去净 4.工件表面有气孔 5.粉末涂层太厚</td></tr><tr><td>涂层不均匀</td><td>1.粉末喷雾不均匀 2.喷枪与工件距离过近 3.高压输出不稳 1.磷化膜太厚</td></tr><tr><td>涂膜冲击强度和附着力差</td><td>2.固化温度太低，时间过短，使固化不完全 3.金属底材处理不干净 4.涂覆工件浸水后会降低附着力</td></tr><tr><td>涂膜产生针孔</td><td>1.空气中含有异物，残留油污 2.喷枪电压过高，造成涂层击穿 3.喷枪与工件距离太近，造成涂层击穿 4.涂层太厚</td></tr><tr><td>涂膜表面出现颗粒</td><td>5.粉末挥发分高 1.喷枪堵塞或气流不畅</td></tr><tr><td>粉层脱落 4.喷粉时空气压力过高 5.粉末有吸湿现象（使用HAA体系的粉末）</td><td>2.喷枪雾化不佳 3.喷粉室内有粉末滴落 4.有其他杂物污染工件表面 1.工件表面处理不好，除油除锈不彻底</td></tr><tr><td>6.粉末粒径太粗、喷涂太厚 1.烘烤温度偏低，时间过短或未达到固化条件 涂膜物理力学性能差 2.固化炉上、中、下温差大</td><td>2.高压静电发生器输出电压不足 3．工件接地不良</td></tr></table></body></html>  \n\n<html><body><table><tr><td>涂膜缺陷</td><td>产生原因</td><td></td></tr><tr><td rowspan=\"2\">粉末飞扬、吸附性差</td><td>1.静电发生器无高压产生或高压不足 2.工件接地不良</td><td></td></tr><tr><td>3.气压过大</td><td></td></tr><tr><td rowspan=\"3\"></td><td>4.回收装置中风道堵塞</td><td></td></tr><tr><td>5.粉末粒径过细</td><td></td></tr><tr><td>1.气压不足，气量不够</td><td></td></tr><tr><td rowspan=\"3\">喷粉量减少</td><td>12.气压过高，粉末与气流的混合体中空气比例过高</td><td></td></tr><tr><td>3.空气中混有水气和油污</td><td></td></tr><tr><td>4.喷枪头局部堵塞</td><td></td></tr><tr><td rowspan=\"4\">喷粉量时高时低</td><td>1.粉末结块</td><td></td></tr><tr><td>2.粉末混有杂质，引起管路阻塞</td><td></td></tr><tr><td>3.粉末密度大</td><td></td></tr><tr><td>4.气压不稳定 5.供粉管中局部阻塞</td><td></td></tr><tr><td rowspan=\"4\">喷粉管阻塞 5.粉末受热或受压结块</td><td>1.由于喷粉管材质缘故，粉末容易附着管壁</td><td></td></tr><tr><td>2.输出管受热，引起管中粉末结块</td><td></td></tr><tr><td>3.输粉管弯折、扭曲</td><td></td></tr><tr><td>4.粉末中混有较大的颗粒杂质</td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 755,
+        "chunk": "# 三、展望  \n\n粉末涂料已经被市场广泛地接受，而且被认为是涂料行业中环境友好型体系之一。粉末涂料今后的发展趋势主要有以下几个方面。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 756,
+        "chunk": "# 1．市场方面  \n\n在生产金属板的预涂领域，粉末卷材涂料具有十燥速率快、生产效率高、涂膜性能好、节省费用、环保效果好等优点，市场前景非常看好。  \n\n迫于环保压力和环保观念的进步，使用粉末涂料对汽车表面整车涂装的尝试有了初步的进展，欧洲几大轿车生产厂商不同程度地开始使用透明粉末涂料对一部分整车表面进行罩光涂装。然而，粉末涂料要想全面进入这个巨大市场必须解决涂膜流平性差、固化温度高、涂装换色难等诸多问题。  \n\n粉末涂料在热敏基材上的涂装是一个潜在的巨大市场，如木材（特别是中密度纤维板材）、塑料、玻璃钢等材料的表面涂装。虽然已经有了这方面的实际应用（如紫外线固化的粉末涂料和近红外固化的粉末涂料)，但市场应用尚待规模化。  \n\n此外，建筑用钢筋防腐粉末涂料和管道防腐粉末涂料在国外已经有三十余年的应用历史，但在国内依然存在一个不容忽视的市场。",
+        "category": " Introduction"
+    },
+    {
+        "id": 757,
+        "chunk": "# 2.粉末涂料方面  \n\n据专家预测，由于聚酯树脂优良的性价比，以聚酯树脂为主要成膜物的热固性粉末涂料依然占有粉末涂料产品的主导地位。在改进和提高粉末涂料的性能方面，主要还是通过对成膜物和交联剂的改进，使用新的二元醇，如2,2,4-三甲基-1,3-戊二醇、2-乙基-1，3-已二醇，2,2-二乙基-1，3-丙二醇、2-正丁基-2-乙基-1，3-丙二醇用以改进聚酯树脂的耐沸水性和耐碱性。开发耐候性能接近PVDF的超耐候性聚酯树脂仍然是今后努力的目标。开发和使用半结晶聚合物作为基料将使粉末涂料的熔融黏度更低，从而改善粉末涂料涂膜严重的橘皮效果。低能耗高产出的理念将使人们进一步追求粉末涂料的低温固化，即在100～110℃条件下固化，以及同时具有好的贮存稳定性和好的涂膜流平性。针对卷材粉末涂料的快速固化（固化速率应在60s以内）也是业内人士努力的方面，以适应100m/s以上高线速的金属板材生产线。超薄粉末涂料（即涂膜厚度在30～50um）今后依然是人们关注的一个方面。某公司的超薄涂粉末涂料是通过在粉末中加入特殊的纳米添加剂解决了粉末涂料粒径在超细微状态不结团的难题，从而达到粉末细微、薄涂的目的，并已实现了工业化生产。如何提高超细微粉末的生产效率和产能是其今后要解决的问题。今后，某些新的聚合物技术应用于粉末涂料行业后，将会使粉末涂料发生革命性的变革。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 758,
+        "chunk": "# 3.生产和应用方面  \n\n使用超临界二氧化碳作溶剂对粉末涂料的原料进行混合，后经喷雾塔喷雾形成粉末颗粒的粉末涂料新的生产工艺已经实现了中试工厂的生产过程。这种新工艺不仅适用于传统的粉末涂料配方，同时也适用于低熔点、高反应活性的配方体系，这种工艺生产的粉末涂料的粒径分布窄，粉末粒子外观基本呈圆球状态，而这种球形状态的粉末粒子的物理贮存性能更加稳定。此外，经挤出机挤出的熔融状态的粉末物料在 ${\\bar{Z}}{\\bar{0}}{\\bar{0}}{\\bar{0}}{\\bar{0}}\\mathbf{Hz}$ 的超声驻波场雾化成粉末，也能生产出粒度分布窄的球形粉末。使用悬浮法进行丙烯酸本体聚合，控制悬浮粒径在$10\\mu\\mathrm{m}$ 以上，通过喷雾干燥等过程可直接制得丙烯酸粉末清漆，但这种工艺比较复杂。  \n\n新的涂装和固化技术除前面所介绍的UV和近红外固化技术会进一步得到发展外，电磁刷———一种类似磁鼓复印原理的涂装技术应能够适应高线速卷材的涂装，这种技术还可以满足超薄粉末的涂装。  \n\n准确预测粉末涂料的发展是十分困难的，但无论如何，粉末涂料对环保的贡献以及所带来的优势对这一商业市场极具吸引力，粉末涂料的发展道路还会继续走下去。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 759,
+        "chunk": "# 参考文献  \n\n[1]王锡春，姜英涛主编．涂装技术．北京：化学工业出版社，1986.  \n[2]王德中主编．环氧树脂生产与应用．第二版．北京：化学工业出版社，2001.  \n[3]［美]ZenoW．威克斯，Frank N.琼斯，S.Peter柏巴斯著．有机涂料科学和技术．经良、姜英涛等译．北京：化学工业出版社，2003.  \n［4]朱骥良，吴申年主编．颜料工艺学，第二版．北京：化学工业出版社，2004.  \n[5]Ir.Pieter Gillsde Lange.Powder Coatings:chemistry and technology.Hannover Vincentz Network，2004.  \n[6］［澳大利亚]』.谢尔斯，T.E朗编著．现代聚酯，赵国操等译．北京：化学工业出版社，2007.",
+        "category": " References"
+    },
+    {
+        "id": 760,
+        "chunk": "# 1 航空航天涂料  \n\n特种涂料是衡量一个国家涂料工业发展技术水平的重要标志之一。其用量与工业涂料和建筑涂料相比较要少得多，但它的应用涉及面广，且用量逐渐增多。据预测，到2010年，我国特种涂料需求量将达到80万 ${\\sim}120$ 万吨。目前，我国的特种涂料从无到有、从小到大，品种逐年增加，水平不断提高，特种涂料种类已经形成了几十个门类、数百个品种，涵盖了耐高低温、消融隔热、绝热保温、温控、阻燃、生化、光学、耐辐照、示温、吸声、吸波、减阻尼、防污、耐磨蚀、润滑、重防腐、超耐候等应用领域。航天、航空涂料是特种涂料中最重要的品种。  \n\n航天、航空涂料是指用于各种飞行器（飞机、导弹、火箭、卫星、飞船等）的专用涂料，航天、航空涂料的技术发展与航天、航空工业的发展密切相关。飞行器的变化日新月异，已经从最初的运输功能向其他特殊功能扩展。同时就其运输功能（民航）来说，也向大型化、高速化发展；而且除运输功能外，飞行器（战机、火箭、导弹）在军事工业的应用、发展，显得更加突飞猛进和重要。还有随着人类活动空间不断向外层空间扩展，航天器（火箭、卫星、飞船）技术也在迅猛发展，同样需要并促进涂料技术的发展。也就是说，航天、航空涂料除了传统的保护、装饰功能外，其重要性更大程度是体现在其特殊功能性，如耐高温、耐烧蚀隔热、耐磨蚀、耐辐照、隐身、防腐蚀等性能更为重要，所以航天、航空涂料的技术水平在一定程度上代表着一个国家航空工业的发展水平。  \n\n航天、航空涂料在过去被赋予浓厚的军事色彩，多年来一直处于技术保密和封闭的状态，特别是发达国家对我国实行军事用途技术的封锁政策。但我国依靠自主研发，使航天、航空涂料完全实现了自给自足，且技术水平达到国际先进水平。  \n\n我国卫星、“神舟”飞船、“嫦娥”奔月等空间高新技术的发展，对航天、航空涂料提出了更高的要求，也促进了该技术的快速发展。我国快速发展空间技术的主要目的是服务于国民经济的发展，当然，针对目前所处的复杂国际环境，为了维护领土完整和为经济建设保驾护航，发展与之相适应的国防军事技术是非常必要的，也具有极其重要的意义。  \n\n航天、航空涂料所涉及的涂料品种较多，为叙述方便，将航天涂料与航空涂料分别叙述，一般，航空是飞行器在大气层以内飞行，而航天是指在大气层以外的飞行。所以航空涂料通常指的是飞机（民机、军机）用涂料，它的主要种类是以飞机蒙皮涂料、雷达罩涂料等为主要代表；而航天涂料通常是各种飞行器（火箭、导弹、卫星、飞船和空间站)用涂料。当然，这样划分是相对的，在很多情况下二者并无严格区别，而且很多涂料可以相互通用。  \n\n本章分三部分，主要介绍飞机蒙皮涂料、消融隔热涂料和隔热保温涂料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 761,
+        "chunk": "# 一、飞机蒙皮涂料的现状及趋势  \n\n飞机蒙皮涂料可分为外蒙皮和内蒙皮涂料，通常情况下，着重考虑外蒙皮的涂装与防护，内蒙皮一般不作严格要求。  \n\n综观国外航空涂料发展水平，欧美、俄罗斯和日本等工业发达国家居世界前列。20世纪中期以来，醇酸涂料因其性能缺陷，已完全为环氧、丙烯酸、聚氨酯涂料所代替。到20世纪末21世纪初，氟硅、氟碳材料技术逐步被应用到飞机蒙皮涂料上。氟硅、氟碳材料虽然具有优越的性能，但是其技术成熟度仍不能达到大规模生产和应用的要求，其成本也相对较高，目前，只局限于小批量试用。另外，水性涂料技术成为涂料发展大趋势，如水性环氧、水性聚氨酯和水性氟硅、水性氟碳等，遗憾的是该技术实现真正意义上的水性化尚待时日。还有，高固体涂料、粉末涂料、辐射固化涂料也是重要的研究和发展方向。",
+        "category": " Introduction"
+    },
+    {
+        "id": 762,
+        "chunk": "# 1.飞机蒙皮涂料国外发展情况  \n\n美国海军在20世纪70年代用丙烯酸作为飞机的面漆在F-105飞机上得到全部使用，效果良好。聚氨酯漆作为飞机的面漆是航空涂料的发展方向。在美国，有三家最大的飞机涂料生产厂，分别是Finch油漆化学公司、Steling喷漆公司和美国油漆公司，他们都生产双组分聚氨酯作为航空涂料面漆。品种有六亚甲基二异氰酸酯缩二脲和HMDI（二环已基甲烷二异氰酸酯）作为固化剂组分（B组分)。T-3反潜艇飞机、B-52轰炸机上的聚氨酯面漆（底漆为环氧聚酰胺、中间层为聚氨酯橡胶）寿命长达5年。寿命长、耐擦洗，可节省飞机的维修费用。在大型运输机C-130、C-121和直升机上也大量使用。这种涂料作为大型客机B-707和B-747的面漆，自20世纪70年代一直沿用至今。  \n\n英国欧洲航空公司在20世纪70年代就用聚氨酯涂料作为飞机面漆，代替环氧和其他合成树脂，其涂层寿命延长50%。使用2年不需重涂，5年重涂一次，比原来的漆使用寿命延长了1.5～2年。他们也认为聚氨酯涂层光泽好，外观平滑，可减少飞行阻力，从而降低了燃料消耗。荷兰、德国也仍以聚氨酯涂料作为飞机面漆。  \n\n聚氨酯涂料由于其涂层光泽高、丰满、平滑，可减少飞行阻力，从而降低燃油的损耗，并且耐机油和耐湿热性远远优于丙烯酸漆。20世纪80年代以来，国外对聚氨酯涂料的发展和应用迅速增加。但双组分自干型涂料，使用不如单组分更方便，而且游离单体一—异氰酸酯对人体呼吸道有刺激作用，以及实干时间较长，保光、保色性不如丙烯酸涂料，所以美国空军仍部分采用丙烯酸涂料。  \n\n国外一般采用环氧树脂及其改性的涂料作飞机蒙皮底漆。如采用环氧树脂为基体树脂、聚异氰酸酯类硬化剂和环氧类硅氧烷偶联剂制成的环氧底漆涂在飞机表面，与聚氨酯类面漆相匹配组成飞机蒙皮涂层。能经受骤冷骤热、风雨冰雪等严酷环境的侵蚀、在各种环境下不会起皮、剥离，解决了涂层与机身的附着难题（见美国专利US3，954，693)。  \n\n美国Akzo-Nobel公司开发成功的“10P20-44”型高固体环氧底漆，可与高固体聚氨酯面漆相配合，用作飞机外部防各种液压油的底漆，具有优异的抗腐蚀特性和与聚氨酯面漆的良好的附着匹配性能，被美国长滩波音公司、美国Douglas aircraftcompany公司等用作军",
+        "category": " Introduction"
+    },
+    {
+        "id": 763,
+        "chunk": "# 用、民用飞机蒙皮底漆。  \n\n美国Douglas aircraftcompany公司1994年7月6日发布了关于“环氧底漆的材料规范DMS2104E”，并于1995年3月5日补充公布了符合该公司“环氧底漆”的要求的产品或来源的“DMSQPL2104”规范，该技术规范对环氧底漆性能要求如表3-9-1所列。  \n\n表3-9-1 环氧底漆的技术性能  \n\n\n<html><body><table><tr><td>检测项目</td><td>DMS2104</td></tr><tr><td>黏度（Zahn-2杯）/s</td><td>混合后底漆15～22</td></tr><tr><td>漆膜外观</td><td>漆膜应均匀、光滑，无粗粒、缩孔、气泡</td></tr><tr><td>使用寿命</td><td>混合后8h，黏度上升至≤5s，涂层附着力不下降，并能通过耐液压油试验</td></tr><tr><td>耐液压油</td><td>30d后铅笔硬度≥HB，附着力不下降</td></tr><tr><td>耐腐蚀性（加速试验）</td><td>2000h腐蚀痕迹距划线处≤3.2mm</td></tr><tr><td>可脱除性</td><td>2～6h内涂层应能从底材上脱除</td></tr><tr><td>打磨性</td><td>易打磨，无辊痕和划痕</td></tr><tr><td>第3类溶剂滞留性</td><td>漆膜经7d室温干燥后，残留的溶剂不大于原溶剂含量的1%</td></tr></table></body></html>  \n\n国外飞机蒙皮环氧底漆采用美军标“MIL-P-23377F， $\\mathbf{G}^{\\#}$ 标准“Ahigh solid two-com-ponent corrosion inhibitive epoxy primer”加以评定。  \n\n美国海军将环氧树脂底漆和聚氨酯面漆组成标准涂层系统。根据其飞机近30年实际使用的情况看，这种涂层系统具有非常优良的附着力、耐蚀性及耐久性，其寿命可长达 $4\\sim6$ 年。美国海军针对环氧飞机蒙皮底漆申请了专利（表3-9-2)。  \n\n表3-9-2环氧飞机蒙皮底漆的相关专利  \n\n\n<html><body><table><tr><td>专利号</td><td>专利标题</td><td>申请日期</td><td>授权日期</td><td>专利权人</td></tr><tr><td>US5,202,367</td><td>Epoxy self-priming topcoat</td><td>1991年5月13日</td><td>1993年4月13日</td><td>US NAVY</td></tr><tr><td>US5,130,361</td><td>Epoxy self-priming topcoat</td><td>1991年8月2日</td><td>1992年7月14日</td><td>US NAVY</td></tr><tr><td>US5,059,640</td><td>Epoxy resin coating compsns providing good corro- sion resistance</td><td>1990年9月28日</td><td>1991年10月22日</td><td>US NAVY</td></tr></table></body></html>  \n\n随着航空工业的不断发展，飞机航行速度不断提高，空气与机身剧烈摩擦而产生的气动热随之提高（马赫数 $M=2,2$ 时为 $150^{\\circ}C$ ； $M=2,5$ 时为 $220^{\\circ}C$ ； $M=3$ 时为 $320^{\\circ}C:$ 。因此，对大马赫的飞机来说，能长期经受 $220\\%$ 以上的耐高温航空漆是非常重要的问题。美国航空材料试验室研制的有机硅涂料在 $315^{\\circ}C$ 下可短期使用。采用专门研制的有机硅底漆和配套材料，在不锈钢和钛合金底材上涂覆，经暴晒试验表明，性能良好，能耐各种机油，经在XB-70飞机和导弹上使用，结果满意。  \n\n日本在航空涂料领域考虑到聚氨酯树脂面漆耐温限度为 $150^{\\circ}C$ ，长期使用可能会造成热劣化，日本特殊涂料公司与日本富士重工业公司共同开发了一种有机硅树脂改性聚氨酯树脂，并拼用耐高温颜料，所制成的涂料经使用效果优良。美国在未来的航空战机中亦将采用一种用含羟基氟树脂与异氰酸酯结合的含氟聚氨酸酯涂料，将大大提高航空涂料的保护性能和使用寿命。更高航速飞机所需的耐高温涂料，希望寄托于新型有机硅和芳香环树脂的应用。由开环缩聚制成的带羟基的星形齐聚物具有狭窄的分子量分布，借此可合成带支链的星形聚合物，可精确控制相对分子质量、官能度以及功能性羟基的位置和反应性，得到的聚氨酯涂料在相同相对分子质量下比线型结构聚氨酯涂料在固体含量及性能方面具有优势，可制成使用效果良好的低VOC双组分聚氨酯清漆。  \n\n如英国Desoto公司于20世纪90年代初就研制出氟树脂作为飞机蒙皮涂料，使用寿命达到20年，比现用的聚氨酯涂料寿命增加1倍，  \n\n为超音速运输机防护而研制生产的聚酰亚胺树脂是目前用于高速飞机最有希望的耐高温蒙皮漆。但制造工艺复杂，毒性大，尚未能推广。  \n\n随着环境保护提出的更加严格的要求，飞机涂料也面临着挥发性有机化合物（VOC）限值要求的挑战。美国已经对航空涂料的VOC含量作了限制，并进行了无溶剂、高固体分涂料以及水性涂料等方面的大量研究，已制成使用效果良好的低VOC双组分聚氨酯清漆。尚存在润湿性、流平性等问题，正在飞机上做试验，尚未进入商业飞机的应用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 764,
+        "chunk": "# 2.飞机蒙皮涂料国内进展情况  \n\n新中国涂料工业真正开始迈出发展的第一步，是于1956年从苏联方面引进了156项援建项目开始，所有生产设备和技术全部来自苏联。到20世纪60年代中后期，由于国际局势发生变化，我国航空、航天工业完全依赖苏联的局面才得以改善，在短短几年内就完成了完全自主化的转变，并取得世人瞩目的成就。由于过分依赖进口，我国虽然建立了涂料工业体系，但是涂料新技术特别是特种涂料技术的研究、开发基本属于空白，鉴于此情况，于1969 年化学工业部在全国抽调大量技术骨干，成立了化工部涂料研究所，专门从事涂料基础研究和军工（特种）涂料的配套研制和生产，自成立以来，成功满足了我国航空、航天等军工行业对特种涂料的急需，填补了国内空白。  \n\n60年的风雨历程，航空、航天涂料伴随中国航空、航天工业的发展，在不断的发展和进步，迄今为止，航空、航天涂料基本实现了中国制造。  \n\n我国飞机蒙皮涂料始于20世纪50年代，以C01-7长油醇酸漆为主，固化后的漆膜平整光滑、坚牢、光泽好、丰满度高，但漆膜耐水性差。醇酸涂料由于其稳定成熟的工艺和较低成本，良好的施工性能，曾经起到积极的作用。  \n\n20世纪70年代，我国航空涂料开始发展，北方涂料工业研究设计院（原化工部涂料工业研究所）、北京621所、天津油漆厂均投入大量人力、物力进行研究。丙烯酸清漆、丙烯酸改性聚氨酯磁漆、聚氨酯磁漆和有机硅改性聚氨酯漆的产品相继研究成功，并均广泛用于制造军用新飞机的表面涂装。  \n\n20世纪90年代以来，我国航空航天工业得到较快发展，带动了航空、航天涂料的发展。国内生产企业和研究机构在引进、借鉴国外先进技术的基础上，自主研发系列飞机蒙皮涂料，主要有如下四类：  \n\n$\\textcircled{1}$ 聚酯聚氨酯体系（高光）；  \n$\\textcircled{2}$ 脂肪族丙烯酸聚氨酯体系（无光，光泽 $60^{\\circ}\\leqslant10\\%)$ $\\textcircled{3}$ 有机硅改性聚酯聚氨酯体系（无光，光泽 $60^{\\circ}\\leqslant10^{\\circ}/\\sqrt{0}$ ；$\\textcircled{4}$ 含氟丙烯酸聚氨酯体系。  \n\n品种涵盖飞机蒙皮涂层、标志、迷彩和透波等应用要求，达到GJB和MIL标准，在国内军机和民机多种机型上得到成功应用，底漆普遍采用环氧聚氨酯涂料，满足国内飞机生产、涂装和修补的需要。  \n\n为了适应海洋性环境要求，对机用涂层提出严格的“三防”要求，天津灯塔、北方涂料工业研究设计院等研制、生产的氟丙烯酸涂料、各色含氟脂肪族聚氨酯涂料，均以通过国家权威机构和航空行业检验中心的检验和认证，其中涂层耐盐雾和耐湿热试验达到5000h以上，耐霉菌试验小于1级，人工加速老化试验300h无粉化、龟裂，且综合性能优良，在航空、电子等行业得到成功应用。北方涂料工业研究设计院最新研制的“飞机用水基结构抗腐蚀防护涂料”为水性环氧涂层，为某重点型号配套研制的防腐底涂层，技术水平达到国内  \n\n领先。  \n\n目前，国内仍然还是以采用环氧底漆和聚氨酯（聚酯、丙烯酸和各种改性聚酯）面漆体系的飞机蒙皮涂料为主要品种，其技术性能达到国际先进水平，其主要用途为军机，民机蒙皮涂料基本上是采用国外进口产品，少量仅局限于修补用途，这与我国民航制造工业的发展有关，随着“大飞机”项目的实施，民机蒙皮涂料将会得到快速发展。",
+        "category": " Introduction"
+    },
+    {
+        "id": 765,
+        "chunk": "# 二、飞机蒙皮涂料的作用",
+        "category": " Introduction"
+    },
+    {
+        "id": 766,
+        "chunk": "# 1.装饰和标识作用  \n\n飞机在装配完成时，表面是一块一块铝板和千万个铆钉，还夹杂一些不是铝板制成的飞机外表面件，因此外表面颜色参差不齐。可是在大型机场上看到的各型飞机具有不同色彩和光泽非常美观，这就是涂料所赋予的装饰作用，费用不高、效果很好。  \n\n选择彩色的涂料涂装成鲜明的、流畅的彩带图案，给人一种美的感觉。还可以画出各国公司的标志，起到识别飞机的作用。同时还利用色彩的不同，在飞机表面作出种种小的标志，标明是哪个系统位置或一些注意事项，这有利于地面维护工作。  \n\n另外，飞机蒙皮涂料的光泽也是一个重要指标，在早期很多军用飞机都采用高光，到20世纪80年代末90年代初，基于视觉效果和隐身的要求，飞机蒙皮涂料均提出无光要求，美军标规定飞机蒙皮涂料的光泽 $(60^{\\circ})$ 小于 $10\\%$ ，甚至达到零，W04-89各色有机硅聚酯聚氨酯无光磁漆、W04-80无光迷彩漆、W86-70无光标志漆和S04-19各色聚氨酯无光磁漆的光泽均可以达到 $5\\%$ 以下，且综合性能优良，已经得到很好的应用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 767,
+        "chunk": "# 2.防护作用  \n\n现代飞机几乎 $100\\%$ 是用铝合金作蒙皮，如不用涂层保护，就很快被腐蚀而缩短飞机的使用寿命。因此，飞机的各个部位都必须用适当的非金属材料加以保护，涂料就是其中的一大类。航空涂料性能的好坏直接关系到一架飞机的使用期限。此外，飞机作为交通工具时，其外观状态亦显得很重要，一架外观漂亮完美的客机和处处可见漆皮脱落的飞机对乘客的感官和心理刺激显然不同，前者给人以安全、舒适的感觉，而后者则很容易令人感到不舒服，进而产生不安全感。所以，飞机蒙皮涂料防护和装饰作用显得非常重要。  \n\n另外，由于飞机的飞行条件复杂多变，要经受上空、地面、日晒、雨淋、阴雾、冰霜以及冰等冷热、砂石和光辐射的冲击。当飞机在远距离飞行或在机场着落时，会遇到各种各样的气候条件。受日光照射的静止飞机，其黑色涂层的表面温度可达到 $90^{\\circ}C$ 以上。近代高速飞机的表面，受动力热作用时，表面温度可达到 $130^{\\circ}C$ 。在高速飞行时，涂层受阳光和紫外线的辐照，起飞和降落时受酸雨腐蚀和飞机的剧烈振动等问题，要求涂料必须具有良好的附着力、耐候性、柔韧性、耐磨性和硬度。飞行周期中出现的循环凝聚条件十分重要，在飞机结构中难于触及的部位能受到水的作用，这种水往往含有溶解盐类或有一些飞机带人的油、燃料等。这些液体中有许多成分会使漆膜脱落，其中腐蚀性较大的是各种润滑油、燃料油和化冰液。因此，飞机对涂层性能的要求比其他交通工具对涂层要求更为苛刻，适用于飞机蒙皮的涂料及其修补涂料，必须是具备特种性能的涂料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 768,
+        "chunk": "# 3.隐身、伪装作用  \n\n飞机蒙皮涂料除了装饰、标识和防护（耐各种航空介质、日晒、雨淋、阴雾、冰霜以及冰霍等冷热、砂石和光辐射的冲击）等基本作用外，隐身、伪装作用日益显得重要和迫切。  \n\n伪装就是利用飞机蒙皮涂料层的色彩变化和对近红外的不同吸收反射，达到隐蔽自己和迷惑敌人的目的。迷惑敌人不仅包括肉眼的观察而且包括各种侦察器材，如夜视仪、红外照相以及空中和卫星照相等，这些侦察器材发展很快、精度很高，一些微小目标都可以捕捉到，即使如此，利用表面涂料的伪装技术，仍为各国军事部门采用和重视，并还在不断发展。  \n\n随着侦察器材和手段的发展、广泛电磁波谱范围内探测能力的提高，反侦察隐身、伪装技术已包含可见光隐身、红外隐身、（雷达）电磁波隐身等。传统涂层色彩和图案变化伪装隐身已经无法满足现代反侦察技术发展的要求，隐身、伪装由可见光发展到近红外等电磁波谱多波段区域，不仅要求颜色和外形与背景相协调，而且要在电磁波谱多谱段反射光谱与背景相一致，特别是飞机活动范围大、背景千变万化，单一的隐身特征难以达到隐身、伪装的目的。  \n\n伪装涂料使用方便，成本低。采用迷彩伪装技术不仅可使伪装目标与背景色调、亮度一致，而且还可以改变外形，因此各国都很重视涂料的伪装技术，国外还发展了双重变形迷彩图案，以对付不同距离的侦察。  \n\n上述通过色彩和图案的变化达到蒙皮涂料的伪装效果，是一种被动的隐身技术，随着探测技术日新月异的发展，这种隐身方式已经远远无法满足战机、武器的战术性能要求。由于探测技术的发展，促进了主动隐身技术的迅速发展。主动隐身技术就是利用自身具有隐身功能的材料，来达到隐身的目的。  \n\n隐身涂层朝着兼容米波、厘米波、毫米波、红外、激光等多波段范围隐身发展，国外先进的多功能隐身涂层在可见光、近红外、远红外、 $\\mathrm{{8mm}}$ 波和 $3\\mathrm{mm}$ 波五波段一体化方面已取得较大进展。下面介绍几种先进的隐身技术。  \n\n(1）传统吸波涂料（如铁氧体、炭基铁等） 并在此基础上持续改进。  \n\n(2）纳米吸波材料该材料对电磁波的透射率及吸收率比微米粉要大得多，同时具备频带宽、兼容性好、质轻和厚度薄等特点。欧美、俄罗斯和日本等国家都把纳米材料作为新一代隐身材料加以研究和探索。目前世界军事发达国家正在研究覆盖厘米波、毫米波、红外、可见光等波段的纳米复合材料。  \n\n(3）多晶铁纤维隐身涂料20世纪80年代中后期，美国和日本等国家大力开展多晶铁纤维吸波涂料的研究。研究表明，这种涂料具有吸收频带宽、密度小、吸波性好等优点。据称，该涂料已用在法国战略导弹与再入式飞行器上。美国研制的吸波涂料中使用了直径为$0.26\\mu\\mathrm{m}$ ，长度为 $6,5\\mu\\mathrm{m}$ 的多晶铁纤维。多晶炭基铁纤维吸收涂料已在F/A-18E/F和A/F-117X飞机上使用。国外开发了系列陶瓷纤维，主要有碳化硅纤维、三氧化二铝纤维、四氮三硅和硼硅酸铝纤维。据报道，美国用陶瓷基复合材料制成的吸波材料和吸波结构，加到F-117隐身飞机的尾喷管后，可以承受 $1093^{\\circ}C$ 的高温。法国Alcole公司采用由玻璃纤维、碳纤维和芳酰胺纤维组成的陶瓷复合纤维制造出无人驾驶隐身飞机。  \n\n（4）导电高聚物吸波涂料具有良好的微波电、磁损耗性能，引起世界各国的重视。目前，美国Hunstvills公司研制出一种苯胺与氰酸盐晶须的混合物透明吸波涂料，该材料在涂层内分布均匀，不必增加厚度来提高隐身频带宽度，特别适合对老飞机的隐身改装。此外，其透明特性适用于座舱盖、导弹窗口及夜视红外装置窗口的隐身，减少雷达回波。飞行器和武器某些特殊部位，如头锥、发动机进气道和喷嘴等部位需要耐高温、耐高速热气流的冲击，为满足这些特殊部位的隐身要求，目前国内外正在积极开发耐高温吸波材料。  \n\n(5）手征吸波涂料这是一种新型吸波材料，是在基体中掺人一种或多种不同特征参数的手征物质。美国、法国和俄罗斯非常重视手征材料研究，在微观机理研究方面已取得较大进展，并验证了其旋波特性；实验室内已能制出微小面积的均匀薄膜样品，目前正在尝试制造面积更大、实用的薄膜。  \n\n(6）智能吸波材料这是20世纪80年代发展起来并备受重视的高新技术材料，能感知和分析从不同方位到达飞行器表面的各种主动式探测信号，瞬时调节该表面的电磁波与光学特性，以获得隐身效果。据报道美国空军将不同导电率的多层薄膜联结在一起，获得在功能上与分层介质吸波涂层类似的蒙皮结构，并将各种机载电子装置、传感器等嵌人蒙皮内以取代传统的雷达天线，从而构成智能蒙皮涂料。这样飞机表层不仅能承受载荷和维持外形，而且具有通信、隐身、电子对抗、火控、飞控等功能，部分或全部替代原来离散的电子设备，增加功能，减轻质量，提高生存能力。  \n\n(7）等离子体隐身技术该技术是将隐身技术应用于航天武器系统中的新型技术之一。俄罗斯20世纪90年代中期开始研究等离子体减阻技术。通过在飞机机体周围布设等离子发生器，飞行中释放出等离子体不仅能使飞机减小阻力 $30\\%$ 以上，而且能起到显著的隐身作用。90年代末期该项技术完成实验，目前正加紧发展第三代等离子发生器。该技术最大的特点是等离子体的隐身效果可随雷达波长的增加而增加，而涂层隐身材料的隐身效果随波长的增加而降低。这种隐身技术不仅解决了吸波涂层厚度和质量方面的局限性，具有吸波频带宽、吸收率高、使用简单和时间长等优点，而且能满足局部高反射需求，尤其适用于导弹的隐身。  \n\n以上所述，隐身技术及隐身材料大多数是作为结构材料来应用的，似乎与本节内容并不相符，和传统意义上的飞机蒙皮涂料存在较大的区别，但是，隐身技术和隐身材料正在不断应用于飞机蒙皮涂料，并得到重视，特别是新兴的隐身材料作为一个主要组分，加入到涂料中，使得飞机蒙皮涂料具有优异的隐身功能，而且涂料具有工艺简单、成本低的优点。基于此，隐身技术、隐身材料和涂料技术结合，可大幅度降低飞机结构设计和材料成型的难度及成本。  \n\n飞机蒙皮涂料在不断提高装饰、防护性能的基础上，隐身技术是其重要的发展方向，这具有非常重要的军事意义，这也是涂层材料和武器统一化的发展方向。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 769,
+        "chunk": "# 4.其他作用  \n\n飞机蒙皮涂料除了上述主要作用之外，涂料技术向多功能复合型的方向发展，人们总是希望能够用一种涂料可以实现多种需求，当然，在实际应用中很难做到这一点，只能尽可能满足主要性能要求的同时，兼顾其他辅助功能。所以，在涂料配方设计时，选择一定的树脂、颜料和某些特定材料，可以使涂料在特定条件下具有特定的功能，起到特殊作用。这也是对蒙皮涂料性能功能多样化、复合化的要求，也是飞机蒙皮涂料的一种发展趋势。  \n\n(1）表观温度调节作用利用涂层具有低热导率、高反射和高辐射性能，对调节蒙皮温度起一定作用。如飞机以 $\\scriptstyle M=2$ 速度飞行时，机身表面温度约为 $120^{\\circ}C$ ，若面漆涂层具有$75\\%$ 的反射率和 $80\\%$ 的发射率，对表面最终温度可降低 $10^{\\circ}C$ 。如果对于高马赫飞行的飞机来说，其作用会更加显著，这对飞机蒙皮材料性能和调节机舱内温度来说，具有重要意义。  \n\n(2）阻尼作用飞机高速飞行时受到气流阻力、气动升温，会导致产生阻力、振动、升温、噪声等不利影响因素，除了在结构设计应充分考虑减少这些不利因素的负面影响外，飞机蒙皮涂料的阻尼作用也是一种好的补充方法。涂料的阻尼作用就是在各种金属板表面上具有减振、隔声、绝热和一定密封性能。当高分子材料处于高弹态时，分子链段运动表现出很大的高弹性变形和很高的力学内耗。由于链段运动需要一定的时间来克服分子间的黏性摩擦。在这种情况下，外力取消后，形变不能立即恢复；这种滞后现象使材料具有高内耗性；利用这一特性，将高分子材料，如丙烯酸树脂，加人适当的颜料和填料，如金属铝粉、片状无机填料和石棉绒等使涂料具有隔热和隔声作用。发泡型阻尼涂料还具有消声效果，在一定条件下吸收声能可达 $90\\%$ 以上。实用结果表明，阻尼涂料是一种理想的声波衰减材料，它只需要其他消声材料（如超细玻璃棉板）的1/3厚度，便可达到同样的隔音效果。  \n\n(3）示温作用当干燥涂层被加热到一定温度时，涂层发生颜色变化来指示温度，达到测量温度的目的；这种指示温度的涂料被称为示温涂料。由于这种涂料使用方便，不需要任何特殊的测量仪表，对一些高速转动的部件如发动机涡轮盘、涡轮叶片、压气机叶片、火焰筒和飞行中的飞机蒙皮外表等部位在飞行时不便于使用温度计，都可以用示温涂料测温。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 770,
+        "chunk": "# 三、飞机蒙皮涂料的组成",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 771,
+        "chunk": "# （一）飞机蒙皮涂料的成分  \n\n飞机蒙皮涂料同所有涂料一样，其组成分为成膜物树脂、颜填料、溶剂和助剂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 772,
+        "chunk": "# 1.成膜物树脂  \n\n飞机蒙皮涂料的成膜物树脂，经历了几代更新，油基树脂涂料为第一代，醇酸树脂涂料为第二代，纯合成树脂如聚酯、聚酰胺、环氧、丙烯酸、聚氨酯等树脂为第三代，有机硅、有机氟树脂及其改性产品为第四代。后面重点介绍第三、第四代品种。",
+        "category": " Introduction"
+    },
+    {
+        "id": 773,
+        "chunk": "# 2.颜填料  \n\n颜填料包括着色、防锈、耐温等颜料和填料，选用要求和普通涂料的相同，为适用于飞机的某些特殊部位的某些特殊要求，如夜间发光，则应加人特殊颜料，如荧光颜料、夜光粉等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 774,
+        "chunk": "# 3.溶剂和助剂  \n\n溶剂是辅助材料，其功能和选用原则和普通涂料基本相同。  \n\n助剂对改善涂料的生产工艺，改进涂料的施工工艺，防止漆膜病态，改进和提高涂料的性能，可以起到事半功倍、画龙点睛之功效，是涂料中量少但不可缺少的重要组分之一。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 775,
+        "chunk": "# （二）飞机蒙皮底漆  \n\n飞机蒙皮底漆应具有优良的附着力、防腐蚀性，耐机用液体性，与飞机蒙皮面漆有良好的配套性与层间黏结性，还应具有良好的耐热性、耐冲击性和弹性。环氧树脂底漆基本能达到这些要求。  \n\n丙烯酸底漆具有室温快干、防霉性好的特点。在我国目前主要采用B06-1、B06-2锌黄（锶黄）丙烯酸树脂底漆。这些产品配方与工艺在有关专著中均可查到。  \n\n环氧树脂底漆、聚氨酯树脂及改性底漆应用最广，其中环氧涂料由于其优良的性能和低成本的优点，是普遍采用的飞机蒙皮底漆品种。",
+        "category": " Introduction"
+    },
+    {
+        "id": 776,
+        "chunk": "# 1.环氧改性氨基醇酸底漆  \n\n（1）配方（质量分数/%）  \n\n\n<html><body><table><tr><td>组分</td><td>铁红</td><td>锌黄</td><td>组分</td><td>铁红</td><td>锌黄</td></tr><tr><td>氧化铁红</td><td>8.5</td><td></td><td>601环氧树脂液（50%）</td><td>8</td><td>8</td></tr><tr><td>锌黄</td><td>25.5</td><td>25.5</td><td>短油度豆油醇酸树脂</td><td>37</td><td>37.5</td></tr><tr><td>浅铬黄</td><td>一</td><td>8</td><td>三聚氰胺甲醛树脂</td><td>12</td><td>12</td></tr><tr><td>滑石粉</td><td>8</td><td>8</td><td>环氧漆稀释剂</td><td>1</td><td>1</td></tr></table></body></html>  \n\n(2）生产工艺将颜料、填料和醇酸树脂混合，搅拌均匀，经研磨至细度合格，再加人环氧树脂液和三聚氰胺甲醛树脂、环氧漆稀释剂，充分调匀，过滤包装。  \n\n(3）技术要求 技术指标见表3-9-3。  \n\n表3-9-3环氧改性氨基醇酸底漆技术指标  \n\n\n<html><body><table><tr><td>项 目</td><td>技术指标</td><td>检测方法</td></tr><tr><td>漆膜颜色和外观</td><td>铁红、锌黄色、漆膜平整</td><td></td></tr><tr><td>黏度（涂-4杯）/s</td><td>45~70</td><td>GB/T 1723—1993</td></tr><tr><td>细度/μm</td><td>不大于50</td><td>GB 1724—1989</td></tr><tr><td>干燥时间（120℃±2℃）/h</td><td>不大于1.5</td><td>GB 1728—1989</td></tr><tr><td>柔韧性/mm</td><td>1</td><td>GB/T 1731—1993</td></tr><tr><td>冲击强度/cm</td><td>50</td><td>GB/T 1732—1993</td></tr><tr><td>附着力(划圈法)/级</td><td>1</td><td>GB/T 1720—1989)</td></tr><tr><td>耐水性(浸96h)</td><td>不起泡、不生锈</td><td>GB/T 1733—1993</td></tr></table></body></html>  \n\n(4）用途用于烘烤的各种金属表面做底漆，其中铁红色用于钢铁表面，锌黄色用于铝合金表面。  \n\n通用环氧聚酰胺底漆及常用的环氧树脂品种及牌号见有关专著。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 777,
+        "chunk": "# 2.环氧聚氨酯底漆  \n\n（1）配方（质量分数 $(\\%)$  \n\n组分一（色浆)：  \n\n环氧 $501(50)\\%$ $20\\sim30$ 沉淀硫酸钡 5\\~15钛白粉 $\\cdot-15$ 气相二氧化硅 1\\~3锌铬黄 $12\\sim25$ 助剂 适量滑石粉 $I0\\sim30$ 稀释剂 适量云母粉 $8\\sim25$  \n\n控制指标：细度 ${\\leqslant}20\\mu\\mathbf{m}$ ，固体分控制在 $50\\%\\pm2\\%$ 9  \n\n组分二（固化剂)：  \n\nTDI 10\\~30 TMP 5～10   \nN-210 $15\\sim30$ 溶剂 50  \n\n(2）性能指标 见表3-9-4。  \n\n表3-9-4环氧聚氨酯底漆的技术指标  \n\n\n<html><body><table><tr><td colspan=\"3\">项 目</td><td>技术指标</td></tr><tr><td rowspan=\"2\">容器中状态</td><td colspan=\"2\">组分一</td><td>无结块、结皮、粗颗粒，有沉淀可搅拌均匀</td></tr><tr><td colspan=\"2\">组分二</td><td>清澈透明，无水分、污物</td></tr><tr><td rowspan=\"2\" colspan=\"2\">固体分/%</td><td colspan=\"2\">组分一</td></tr><tr><td colspan=\"2\">组分二</td><td>58±2 50±2</td></tr><tr><td colspan=\"4\">漆膜外观</td></tr><tr><td rowspan=\"2\">干燥时间 常温/h ≤</td><td colspan=\"2\">表干</td><td>漆膜平整均匀，无粗颗粒、气泡、针孔和其他缺陷 0.5</td></tr><tr><td colspan=\"2\">实干</td><td>24</td></tr><tr><td colspan=\"4\">咬底（分别在喷底漆1h、4h和18h后喷面漆）</td></tr><tr><td colspan=\"3\">适用期/h</td><td>不咬底 ≥</td></tr><tr><td colspan=\"3\">光泽(60°)/%</td><td>6</td></tr><tr><td colspan=\"3\">≤ 细度/μm ≤</td><td>10</td></tr><tr><td rowspan=\"3\">附着力</td><td colspan=\"2\">划圈法/级</td><td>20 2</td></tr><tr><td rowspan=\"2\">胶带法</td><td>≤ 单层底漆</td><td>不从金属底材上剥落</td></tr><tr><td>底面配套</td><td>不从金属底材上剥落，也不从底面漆之间剥落</td></tr></table></body></html>\n\n控制指标： $\\mathrm{NCO}{=}5.0\\%{\\pm}0.2\\%$ 0  \n\n续表  \n\n\n<html><body><table><tr><td colspan=\"3\">项 目</td><td>技术指标</td></tr><tr><td colspan=\"3\" rowspan=\"2\">摆杆硬度</td><td>0.55</td></tr><tr><td rowspan=\"2\">≤ 2</td></tr><tr><td colspan=\"3\">柔韧性/mm 耐合成润滑油4109[（121士2）℃×24h]</td></tr><tr><td colspan=\"3\" rowspan=\"2\">耐液压油（YH-10YH-12)[(66±1)CX24h]</td><td>不起泡、不脱落、不发软，允许轻微变色 不起泡、不脱落、不发软，允许轻微变色</td></tr><tr><td></td></tr><tr><td colspan=\"3\">耐热性[（175±2）℃×75h+（210±2）CX4h]</td><td>不起泡、不脱落，允许轻微变色</td></tr><tr><td colspan=\"2\">耐湿热性</td><td>漆膜外观</td><td>不脱落、不起泡</td></tr><tr><td colspan=\"2\">[RH=94%~98%，（49±2)℃×30d]</td><td>胶带附着力</td><td>底漆不应从金属底材上剥落</td></tr><tr><td colspan=\"3\">耐水性(38C×4d)</td><td>不起泡、不脱落、不起皱 放至盛有12mol/L盐酸水溶液的干燥器中4h，转人23℃±</td></tr><tr><td colspan=\"3\">丝状腐蚀</td><td>2C（RH85%～91%）500h。漆膜表面划两条交叉直线至底 材，不出现涂层下的丝状腐蚀</td></tr><tr><td colspan=\"3\">耐盐雾性（5%NaCl盐雾箱中35℃×1000h）</td><td>漆膜表面划两条交叉直线至底材，漆膜无鼓泡，基本无腐蚀</td></tr><tr><td rowspan=\"2\">配套性</td><td colspan=\"2\">耐冲击性/cm ≥</td><td>50</td></tr><tr><td colspan=\"2\">胶带附着力</td><td>漆膜应不脱落分层</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 778,
+        "chunk": "# （三）飞机蒙皮面漆  \n\n目前，采用的飞机蒙皮面漆主要为2KU聚氨酯涂料，其羟基树脂一般为丙烯酸树脂、聚酯及其改性树脂、有机硅树脂，采用聚氨酯固化剂（如缩二脲等）交联固化，以满足不同需求。飞机蒙皮高光白漆的配方、飞机蒙皮涂层的技术要求见有关涂料专著。  \n\n氟碳树脂-聚氨酯飞机蒙皮涂料是近年新发展的品种，选择含羟基氟碳树脂、HDI缩二脲或三聚体为主成分，其涂料的制备：将选定的氟碳树脂、钛白粉、炭黑、绢云母、滑石粉、助剂、消光粉、混合溶剂按一定比例混合均匀，砂磨到细度小于 $10\\mu\\mathrm{m}$ 后出料，用混合溶剂调配成固含量 $50\\%\\pm2\\%$ ，即为淡灰色氟碳飞机蒙皮涂料色浆。  \n\n氟碳飞机蒙皮涂料配漆及性能检测：将上述色浆与固化剂按 $4:1$ 混合均匀，制板，室温固化7d后检测，性能见表3-9-5。  \n\n表3-9-5氟碳飞机蒙皮涂料的性能  \n\n\n<html><body><table><tr><td colspan=\"2\">检测项目</td><td>指标</td><td>检测结果</td></tr><tr><td colspan=\"2\">在容器中状态</td><td>均匀黏稠液体</td><td>合格</td></tr><tr><td rowspan=\"2\">干燥时间/h</td><td>表干</td><td>2</td><td>2</td></tr><tr><td>实干</td><td>48</td><td>48</td></tr><tr><td colspan=\"2\">光泽(60°)/%</td><td>≤10</td><td>4</td></tr><tr><td colspan=\"2\" rowspan=\"2\">铅笔硬度 附着力/级</td><td>≥2H</td><td>3H</td></tr><tr><td>1</td><td>1</td></tr><tr><td colspan=\"2\">柔韧性/mm</td><td>1</td><td>1</td></tr><tr><td colspan=\"2\">耐冲击性/cm</td><td>50</td><td>50</td></tr><tr><td colspan=\"2\">耐水性(500h)</td><td>不起泡、不脱落</td><td>不起泡、不脱落</td></tr><tr><td colspan=\"2\">耐油性（浸于120号航空汽油96h)</td><td>不起皱、不发黏</td><td>不起皱、不发黏</td></tr><tr><td colspan=\"2\">耐盐雾性（1000h）</td><td>不起泡、不脱落</td><td>不起泡、不脱落</td></tr><tr><td colspan=\"2\">耐湿热性（1000h）</td><td>不起泡、不脱落</td><td>不起泡、不脱落</td></tr><tr><td rowspan=\"2\">耐人工老化性 (1000h)/级</td><td>粉化</td><td>1</td><td>1</td></tr><tr><td>变色</td><td>1</td><td>1</td></tr><tr><td colspan=\"2\">涂层耐湿变性（10次）</td><td>无异常</td><td>无异常</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 779,
+        "chunk": "# （四）飞机雷达罩用弹性聚氨酯涂料  \n\n飞机雷达罩处于飞行器头、锥部，是重要的通信、制导部件，一般为玻璃钢制件，雷达罩涂料作为一种特殊的飞机蒙皮涂料，除了满足普通飞机蒙皮涂料要求外，雷达罩、天线罩涂层还应具有：  \n\n$\\textcircled{1}$ 优良的耐候、耐热、耐蚀、耐磨和耐介质性能；  \n$\\textcircled{2}$ 优良介电性能、抗静电性能和透波性能；  \n$\\textcircled{3}$ 应具备施工方便、便于维修，与复合材料底材附着良好的性能。  \n\n雷达、天线罩涂料应为弹性体，如橡胶、弹性聚氨酯等。氯丁橡胶是最早的雷达天线罩涂料品种，用于亚音速飞机，其耐温极限为 $90^{\\circ}C$ ；弹性聚氨酯涂料用于 $M{<}2$ 的超音速飞机雷达罩保护，可长期耐温 $175\\%$ ，短期 $210^{\\circ}C$ ；由偏氯乙烯和全氟丙烯共聚的氟橡胶涂料，可长期耐温 $260^{\\circ}C$ 。但是，随着飞机的飞行速度不断提高，即使是氟橡胶涂料也不能适用，所以必须研制性能更好的雷达罩保护涂料。  \n\n目前，国内普遍应用的一种飞机雷达罩用弹性聚氨酯涂料是先制备线型的预聚物，再用芳香族二胺如4，4-二氨基-3，3-二氯二苯甲烷（简称MOCA）或间二胺等来固化，由于MO-CA分子结构中含有苯环结构，易于泛黄，影响涂层性能，可用氢化MOCA替代，就是将其分子结构中的苯环氢化形成六元环结构，可以克服上述缺陷，已有工业产品。  \n\n北方涂料工业研究设计院自20世纪80年代以来，为适应国内战机和武器发展的急需，成功研制了多个品种的雷达、天线罩涂层，并得到成功应用。主要有弹性聚氨酯涂料、硅改性聚酯聚氨酯涂料，用于飞机雷达罩；耐高温无机涂料用于导弹天线罩。上述品种涵盖了$550^{\\circ}C$ 以内所有温度条件下的使用要求。",
+        "category": " Introduction"
+    },
+    {
+        "id": 780,
+        "chunk": "# （五）飞机蒙皮伪装与隐身涂料  \n\n军用飞机一半采用防可见光侦察和防近红外侦察的伪装涂料，其他伪装涂料仅使用于飞机局部部位，如防雷达波侦察、防紫外线侦察、防中红外侦察等伪装涂料。  \n\n第一次世界大战期间，军用飞机已开始用伪装涂料进行防可见光伪装。当时是简单的单一保护色，上面是深色，下面是浅色。第二次世界大战中，伪装技术已发展到多色变形迷彩伪装，而且适应的波段也由可见光逐渐地向近红外区发展。这些目前已成为战时隐蔽的常规手段。  \n\n最新报道，作为目前全力研制的唯一隐形作战飞机，F-22战斗机代表着隐形技术最新水平。F-22战斗机机翼周围、尾翼和机身周围的大角度边缘使用了雷达波吸收结构技术，而在机舱门和驾驶舱的边缘使用了雷达波吸收涂层。此外，战斗机表面的大部分面积涂上了一层导电金属层，可以防止雷达电磁波穿透飞机表面，表皮之上覆盖着波音公司研制的伪装外层可以隐蔽战斗机的红外信号。可见，飞机隐身主要是针对雷达波、红外可见光等侦察手段。",
+        "category": " Introduction"
+    },
+    {
+        "id": 781,
+        "chunk": "# 1.伪装原理  \n\n可见光侦察是通过目标与背景的颜色差别来发现目标的。防可见光侦察的伪装就是消除目标与背景的颜色差别。物体表面的颜色是通过色彩和亮度来表示的。影响物体表面的颜色是由表面材料的光谱反射性能、粗糙程度和空间位置3个物理因素决定的，因此在防可见光侦察的伪装中，要想减少或消除目标与背景的颜色的差别，应该设法减少或消除目标与背景光谱反射系数的差异，也就是使表面材料与背景光谱反射性能相近；将目标表面加工成近似于背景的漫反射面，使目标表面与背景有相似的粗糙程度；缩小目标与背景的空间位置差异。  \n\n消除或减少目标和背景的颜色差别，是通过基料和颜料的组合来实现的，为了提高其效果，必须考虑伪装色在目标表面上分布情况，设计出合理的迷彩图案。飞机是活动目标，宜采用多色变形迷彩涂装，这样在近距离上，使飞机的视觉轮廓、形状受到歪曲，在远距离上，也能因空间混色起到迷彩伪装效果。迷彩图案的设计对提高伪装效果是重要的，它必须遵守几个原则：①迷彩斑点的颜色必须符合背景斑点的颜色；②必须保证迷彩斑点间的亮度对比K≥0.4，防止迷彩斑点之间近距离混色；③迷彩斑点的轮廓线是不规则的，是多种多样的； $\\textcircled{4}$ 迷彩斑点是不对称的。  \n\n近红外光是可见光波的延续，是不可见光波，它不存在颜色的色彩差别问题。利用近红外光发现目标的依据是目标和背景的亮度差别，防近红外光的伪装就是消除或减少目标与背景的亮度差别。  \n\n雷达波隐身涂料则主要通过颜料的选择、调整，达到吸收雷达波的功效。",
+        "category": " Introduction"
+    },
+    {
+        "id": 782,
+        "chunk": "# 2.涂料配制  \n\n（1）可见光及红外隐身涂料飞机蒙皮伪装涂料，既要具有前述蒙皮涂料的保护性能，又要具有特有的伪装性能，它必须和背景有相应的光谱反射性能，也即和背景的颜色（色彩和亮度）差别很小，另外在阳光、湿气、热和机用液体等介质作用下，迷彩图案及其颜色应该是稳定的，涂层应为平光或无光的表面。  \n\n飞机是活动目标，背景颜色复杂。通常采用绿色、天蓝色、灰色、米黄色、驼色、雪白色等颜色的涂料，构成多色变形迷彩图案，使之与背景颜色相适应。除植物绿色背景外，其他颜色背景的光谱反射率，在可见光和近红外光范围内均变化很小，均易调制，而调制与植物光谱反射性能相适应的绿色涂料，是实施防可见光伪装和防近红外光伪装，尤其是防近红外光伪装的关键。  \n\n任何植物的光谱反射率都具有标准叶绿素光谱反射曲线的特征。标准叶绿素曲线如图3-9-1所示。  \n\n![](images/86160bda92caf720d5d830a76df63bf197f7662939b0fb3a26502ecad9e7cffb.jpg)  \n图3-9-1 标准叶绿素曲线  \n\n以如图3-9-1所示曲线为标准，对各种单色颜料进行选择、组合，找出接近这个标准曲线的绿伪装色的颜料组合来。同理也可以配制出其他色彩的伪装色的颜料组合。  \n\n调制出接近植物绿色背景是麻烦的，在选择颜料时，首先是颜料或颜料组合在$550\\mathrm{nm}$ 附近，具有植物绿色色调的特征峰。再者在 ${\\hat{6}}80\\mathbf{nm}$ 的附近是植物绿色背景光谱反射曲线的红色特征区的边缘，所选颜料组合而成的伪装色在此点的反射率一般只能稍  \n\n高于或不高于 $\\mathrm{550nm}$ 附近绿色特征峰。这样调制的组合颜料，加入适当的基料，就可制成符合伪装要求的涂料来。  \n\n单一绿色颜料的光谱反射系数都较低，与天然植物光谱反射系数相差很大，故必须采用组合颜料，否则难以达到伪装目的。  \n\n据报道，美国FERRO公司的无机颜料具有与标准叶绿素光谱反射曲线极其相似的特征，用其配制可见光和远红外隐身涂料，有比较明显的效果。FERRO公司颜料品种见表3-9-6。  \n\n为提高漆膜的硬度、力学性能、耐磨性等，还要加人一些体质颜料。体质颜料的加入，还可以降低漆膜光泽，甚至完全消光。实践表明滑石粉和二氧化硅是理想的体质颜料。  \n\n(2）雷达波隐身涂料雷达波隐身涂料主要是颜填料（吸波剂）的选择，吸波剂主要从  \n\n表3-9-6FERRO公司颜料产品介绍  \n\n\n<html><body><table><tr><td>FERRO公司牌号</td><td>组成</td><td>商品牌号</td></tr><tr><td>CV1717ANDcj1717Brown</td><td>ZnFe</td><td>Pigment Yellow119</td></tr><tr><td>Uptol000Degrees C</td><td></td><td></td></tr><tr><td>CV4900/CJ4900Yellow</td><td>TiNiSb</td><td>Pigment Yellow53 Pigment Yellow24</td></tr><tr><td>CJ1118Yellow</td><td>TiSbCr</td><td></td></tr><tr><td>CV6733Green</td><td>TiNiZnCo</td><td>Pigment Green50</td></tr><tr><td>CJ2332Blue</td><td>CoAl</td><td>Pigment Blue28</td></tr><tr><td>CJ2300Blue</td><td>CoCrZnAl</td><td>Pigment Blue36</td></tr><tr><td>CJ2320Blue</td><td>CoCrAl</td><td>Pigment Blue36</td></tr><tr><td>CJ6322Turquoise</td><td>CrCoAl</td><td>Pigment Blue36</td></tr><tr><td>CJ3304Black</td><td>CuCr</td><td>Pigment Black28</td></tr></table></body></html>  \n\n下面三个方面选择，  \n\n$\\textcircled{1}$ 纳米材料系列无机纳米粒子一个很成功的应用例子就是制备军事隐身涂料，这要归因于纳米超细粉体具有较大的比表面积，且具有较好的吸收特性，能吸收电磁波，同时又因为纳米粒子粒径小于红外和雷达波长，对波的透过性很大，使红外和雷达探测到的信号大为减弱，很难被发现。因此，可应用于军事上的隐身技术。再加上在微波的辐射下，纳米材料中原子、电子运动加剧，促使磁化，使电子能转化为热能，从而增加了对磁波的吸收。法国科学家将黏接剂和纳米填充材料（由Co，Ni合金与SiC纳米颗粒组成）制成宽频微波吸收涂层，对 $50\\mathrm{MHz}{\\sim}50\\mathrm{GHz}$ 范围内电磁波具有良好的吸收性能。赵东林曾系统地报道了雷达波吸收剂研究进展并详细介绍了一些纳米粒子作为电磁波吸收剂，用于纳米层在隐身技术上的应用。纳米 $Z_{\\mathrm{{nO}}}$ 在这方面具有很好的功效。研究了随着频率增加， $\\mathrm{Fe_{3}O_{4}}$ 在 $1\\sim$ ${\\mathrm{1000MHz}}$ 频率范围的电磁波吸收效能增加，且纳米粒径越小，吸收效能越高。  \n\n$\\textcircled{2}$ 超细微系列 含超细微的Fe、Cu的涂层作吸波剂。  \n\n$\\textcircled{3}$ 导电性超短纤维系列 以碳纤维、石墨纤维、不锈钢纤维作为吸波材料。  \n\n(3）复合涂层根据需要不同，可制成分别满足可见光、红外隐身涂料和雷达波吸收涂料，若将两个涂层复合，可制得满足上述全部要求的隐身涂层。红外隐身和雷达隐身涂层复合时，应该根据二者的特性，将雷达隐身涂层作为内涂层，红外隐身涂层作为外涂层。  \n\n隐身涂层的基料树脂大多数是透明的，对光谱的反射一般没有多大影响，原则上任何一种有机树脂都可以作为伪装涂料的基料，但是由于其他性能的要求，并不是所有树脂都可以作为隐身涂层的成膜物，仍要遵从飞机蒙皮涂料成膜物的选用原则。目前各国飞机的伪装涂料大多采用丙烯酸树脂、聚氨酯树脂，随着飞机性能的提高，高性能的有机氟树脂、氟硅树脂以及相应的水性树脂也逐步被采用。  \n\n其他成分如助剂和溶剂的选择，和飞机蒙皮涂料选材的要求相同。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 783,
+        "chunk": "# 四、飞机蒙皮涂料施工  \n\n飞机蒙皮涂料的施工顺序：首先进行表面处理、干燥后，马上喷涂底漆，如属返修情况，则应先进行脱漆处理；待底漆完全实干后，打磨并擦洗干净，喷涂面漆；最后进行标志漆的施工。  \n\n飞机蒙皮涂料的主要作用是防腐保护、装饰以及其他特殊功能（如隐身、透波等)，“三分漆，七分用”，要达到预期的效果，正确施工十分重要。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 784,
+        "chunk": "# 1.飞机蒙皮的表面处理  \n\n飞机蒙皮多为铝合金材料。铝合金工件的表面处理方法，目前主要采用化学氧化和阳极  \n\n氧化两种，经氧化处理后，铝合金表面形成一层致密均匀的氧化膜，这对于提高铝合金蒙皮的抗腐蚀能力和提高飞机蒙皮底漆的附着力，具有很明显的效果，所以，表面处理质量的好坏，直接影响飞机蒙皮涂层的质量。  \n\n飞机铝合金蒙皮，在涂漆前为了提高其抗腐蚀性，都要在铬酸中进行化学氧化或钝化处理，而底漆中也大都使用铬酸盐颜料，那是因为铬酸盐遇水能很好地释放出铬酸根离子$C F O_{4}^{-}$ )，它将铝合金蒙皮表面封闭起来，达到防腐蚀的作用。  \n\n化学氧化形成的氧化膜活性大，应尽快进行清洗和干燥后，立即进行蒙皮底漆的施工保护，而且化学氧化工艺工序较长，多采用阳极氧化处理。  \n\n另外，飞机返修，必须进行旧漆的脱漆处理，脱漆方法有机械脱漆和化学脱漆两种。一般采用化学脱漆，在化学脱漆后，局部再辅以砂纸、钢刷等打磨机械脱漆。将脱漆剂刷涂、喷涂于旧涂层，待旧涂层在脱漆剂的作用下溶胀、软化后，便可除去。  \n\n脱漆剂可分为碱性脱漆剂、酸性脱漆剂和溶剂型脱漆剂，溶剂型脱漆剂又可分为卤代烃和非卤代烃两种，脱漆剂可制成液体状和糊状，可用于不同工件面。目前，国内脱漆剂的品种和质量均很好，可根据具体情况选用即可。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 785,
+        "chunk": "# 2.飞机蒙皮底漆涂料的选用原则  \n\n$\\textcircled{1}$ 民用飞机和军用飞机对飞机蒙皮涂层性能要求不尽相同，民用客运飞机应选择高装饰性涂料，如丙烯酸类涂料；而军用飞机则注重特殊功能的要求，如耐高温、隐身和抗蚀等性能的重要性要远远高于对装饰性能的要求。  \n\n$\\textcircled{2}$ 飞机飞行环境不同，涂层性能要求也不相同。飞机飞行环境经常处于海洋性和湿热地区，涂层应具有耐水、耐潮湿、耐盐雾、防霉等优良性能，如聚氨酯类涂料、水性环氧涂料等；而在沙漠和高寒地区，涂层耐老化（太阳光)、耐冲蚀（冰粒、砂石）性能要好。  \n\n$\\textcircled{3}$ 根据飞机类型不同，选用相应的飞机蒙皮涂层。  \n\n$\\textcircled{4}$ 飞机蒙皮涂料的底、面配套性能良好，如环氧底漆和聚氨酯面漆就是非常成功的应用实例；同时，还应注重施工、性价比和环保等问题，这一点非常重要。",
+        "category": " Introduction"
+    },
+    {
+        "id": 786,
+        "chunk": "# 3.施工与涂膜病态防治  \n\n涂料的组成、品种不同，施工方法也不同。随着现代科学技术的发展，新型涂料品种的不断出现，飞机涂漆的施工方法也有很大改进，正在朝着连续化、自动化、机械化方向发展。  \n\n飞机蒙皮涂料施工方法主要有刷涂法、空气喷涂法、高压无空气喷涂法、双口喷枪喷涂法、静电喷涂法等。  \n\n涂料在施工时经常会出现某些异常现象，使涂膜出现一些病，如流挂、咬底、渗色、表面粗糙起粒、发花、发白、起霜、色泽不匀、发汗、橘皮、起泡、漆膜发黏等，不预防与及时排除，就会影响涂层质量。飞机涂料的施工和涂膜病态的防治，参见有关涂料专著。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 787,
+        "chunk": "# 五、飞机蒙皮涂料展望  \n\n随着飞机逐步大型化，追求飞行高速和飞行空间不断扩大（高度和范围)，飞机的功能（特别是战机）已经不仅仅限于运输功能，战机的快速、灵活机动和战场生存能力显得尤为重要，这不仅对飞机结构设计提出了更高的要求，同时作为飞机蒙皮涂料有了更高、更新的性能要求。还有人们节能、环保意识的增强，对军用特种涂料也相应提出了环保、低成本、高性能和多功能复合的要求。  \n\n针对上述要求，笔者认为飞机蒙皮涂料未来的发展方向应该集中在以下三个方面。",
+        "category": " Introduction"
+    },
+    {
+        "id": 788,
+        "chunk": "# 1.高性能成膜物树脂的开发和应用  \n\n飞机飞行速度接近3马赫数以上时，目前的树脂品种已很难满足耐温性能要求，必须用新的耐高温、热稳定性好的树脂来代替，各国对航空涂料的耐高温基料——改性有机硅、含氟涂料、聚酰亚胺、铝-硼-硅烷、聚苯并咪唑等耐高温聚合物大力进行研究。含氟树脂涂料、改性有机硅树脂漆、聚酰亚胺树脂漆已在超音速飞机上试用，从聚酰亚胺树脂附着力好、热稳定性高、抗氧化等特点看，只要进一步实现低温固化（50℃以下)，该漆将是高速飞机上最有希望的航空涂料品种。",
+        "category": " Introduction"
+    },
+    {
+        "id": 789,
+        "chunk": "# 2.新材料的应用  \n\n随着材料制备技术的发展，大量新材料不断涌现出来，为飞机蒙皮涂料的发展提供了新的发展空间，其中纳米材料在可见光与红外波段和隐声材料方面赋予了蒙皮涂料的全新性能。",
+        "category": " Introduction"
+    },
+    {
+        "id": 790,
+        "chunk": "# 3.有机/无机杂化纳米复合技术应用  \n\n传统的飞机铝合金蒙皮表面处理采用重铬酸盐或三氧化二铬钝化处理，增加涂层附着力和防腐性能，但六价铬毒性大，废物难以处理。欧美等国飞机制造公司采用溶胶-凝胶技术，实现有机/无机杂化纳米复合，进行无铬的表面处理，减少了对环境的污染，并且涂层的附着力和防腐性能优于六价铬表面处理的涂层。  \n\n有机/无机杂化纳米复合蒙皮涂层，表面含纳米 $-\\bf{S i O_{2}}$ 结构，在低高空中的原子氧作用下，涂层会被加热，可使涂层表面产生再流平作用，对涂膜表面的损伤有起自修复功能，提高飞机蒙皮涂层的耐久性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 791,
+        "chunk": "# 一、概述",
+        "category": " Introduction"
+    },
+    {
+        "id": 792,
+        "chunk": "# （一）国外进展情况  \n\n消融隔热涂层（ablativeinsulationcoating）作为一种特种功能性涂层，是随着航天技术和军事工业的发展而兴起的防热材料，在航天技术的发展中起着不可替代的作用。主要用于飞行器的头锥部、弹体外表面、发动机燃烧室衬里以及发射场各种设备保护的防热保护等。  \n\n消融和烧蚀是同一概念，因为人们的习惯不同而叫法不同，本文以采用“消融”为多，也有“烧蚀”的提法。  \n\n飞行器（火箭、导弹、宇宙飞船等）冲出大气和返回地面时，其头锥部表面在几秒至几分钟内将承受 $11000{\\sim}16700^{\\circ}\\mathrm{C}$ 的高温；固体火箭发动机燃烧室工作时处在 $5\\sim20\\ensuremath{\\mathrm{MPa}}$ ， $1000\\cdots$ $3000^{\\circ}C$ 高温高压环境下，火箭、导弹发射时产生 $1000{\\sim}3000^{\\circ}\\mathrm{C}$ 的高温尾焰，这种苛刻条件已经远远超过许多金属结构材料所能承受的极限，所以对上述环境下设备和部件采用妥善的防护、隔热保护是极其必要的，同时消融涂层材料具有成本低、施工简单和卓越的防消融、隔防热性能，从一开始就得到重视和普遍应用，并取得了显著成效。  \n\n有机消融隔热涂料在航天器上的应用可追溯到20世纪50年代末期。1959年Emersion电器公司首先将牌号为Therm-lage的防热涂料系列用于保护火箭发动机的喷嘴和共振抑制器。1960年美国Dyna-Therm化学公司研制成功阿特拉斯（ATLAS）导弹发射台周围电缆及防护设施保护用的D-65高温防热涂料。该涂料是由韧性的聚氨酯为基漆，添加磷、硼酸盐制成的。该涂层具有优良的柔韧性和隔热性能，在实际中获得应用。1961年美国又先后研制出D-100、Pyroshield、Hel-Met、CT-803、CT-804等高温消融涂料。以上是国外常规用消融涂料的代表性品种，性能一般，密度都在 $1.0g/\\mathrm{cm}^{3}$ 以上，只适用于亚音速飞行条件。为了减轻飞行器的质量和能耗，20世纪60年代中期开始进入低密度消融涂层发展时期。1963年美国软木公司制成低密度（ $(0,53\\sim0.54\\mathrm{g/cm^{3}}$ ）的消融型弹性片，用于民兵（Minuteman）导弹壳体防热。1965年美国通用电器公司制成可耐瞬时 $2760^{\\circ}C$ 高温的硅橡胶泡沫涂料。1966年出现了将 $\\mathrm{SiO_{2}}$ 微球添加到有机硅树脂中制成的组合型（syntactictype）低密度泡沫涂层。1969年美国采用低密度聚氨酯泡沫涂层作为阿波罗（Apollo）宇宙飞船返回大气的防热保护获得成功。这个时期消融涂层的特点是密度低、隔热性好，但不能满足高气动剪切、高热流条件下的防热保护。  \n\n20世纪70年代以来，为了满足反弹道导弹在低空超音速飞行防热的需要，开始研制高性能的涂层。1973年用于奈克-Ⅲ型反弹道导弹的防热涂料研制成功。“高性能拦截导弹”的研制采用 $3.2\\mathrm{mm}$ 厚改性酚醛橡胶层作为防热材料，这是用涂料保护低空超音速飞行器新的发展。随着航天飞机的兴起，对防护材料提出了更高要求，不仅要有优良的防热性能，而且要求反复使用，这是消融型有机材料难以满足的。哥伦比亚号航天飞机是采用 $5\\mathrm{i}0_{2}$ 防热瓦作为“再入”时防热保护的。这是近几年来防热材料变一次为多次使用的重大突破。Tcnupilwc公司（BigThreeIndustries的分公司）用 $100\\%$ 的有机硅树脂生产了一种牌号为Ppyrommark2500的涂料，无论在大气层或太空中，都能经受 $2500^{\\circ}C$ 的高温。美国双子星座号宇宙飞行仓的防热层是道康宁（DowCorning）生产的 $16.5\\mathrm{mm}$ 厚的玻璃纤维增强的有机硅树脂，在飞行中经受了进人火星大气层时摩擦生热（温度大约 $2700^{\\circ}C$ ）的考验。",
+        "category": " Introduction"
+    },
+    {
+        "id": 793,
+        "chunk": "# （二）国内研究进展  \n\n国内在消融隔热涂料方面的研究及应用始于20世纪70年代，当时应我国航天事业的发展要求，卫星、导弹配套的特种涂料也相继研究成功，主要品种有：原化工部涂料研究所研究的高温热反射涂料、2262隔热涂料、2262-2隔热涂料、高温电缆绝热漆、高温绝热带、涂3-8高温绝热涂层和涂3-7高温绝热涂层；上海涂料研究所研制的6831隔热涂料、聚氨酯泡沫内壁隔热涂料。70年代末，（原）化工部涂料所研究成功的YJ66-A消融防热涂料，用于高超音速飞行器表面的防隔热保护，是我国消融涂料研究的重大突破。80年代初，原化工部涂料所研制NHS-55舰船用高温防热涂料，解决了舰船发射远程导弹发射系统的防热问题和涂层耐冷热交变的难题；DG-71后挡板防热涂料，解决了水下发射导弹燃气发动机后挡板的防热问题。另外兵器研究所研究成功的战术火箭燃烧室用防热涂料GT-401，其性能优于国内GA-67和前苏联的V-58。上海涂料所研制的 $37^{\\sharp}$ 、 $7013^{\\#}$ 、7015#涂料，以及隔热涂料和 $7953^{\\sharp}$ 修补涂料，分别在各型号军工产品中获得应用。  \n\n20世纪90年代，由于国内大环境的影响，在军工特种涂料的研究及应用方面的工作明显放慢了步伐，几乎处于停滞的状态。到21世纪初这种现状才得以改变，随着我国航天和国防工业的发展，消融隔热涂料的研发呈现一种喷发的趋势，众多研究机构（大学、研究院所）都积极展开相关研究工作，有许多报道，研究主要集中在涂层应用性能以及耐烧蚀、高性能树脂研究等方面。  \n\n总之，消融涂层由原来的聚乙烯基树脂、聚氨酯（泡沫）树脂、酚醛树脂、环氧树脂、有机硅树脂、环氧有机硅（酚醛）树脂、硅（氟、聚氨酯、三元乙内等）橡胶等有机消融隔热涂层体系，逐步向无机（超无机）体系发展；隔热机理逐步多元、复合化，涂层隔热防护性能逐步提高。",
+        "category": " Introduction"
+    },
+    {
+        "id": 794,
+        "chunk": "# 二、消融材料",
+        "category": " Introduction"
+    },
+    {
+        "id": 795,
+        "chunk": "# （一）无机材料",
+        "category": " Introduction"
+    },
+    {
+        "id": 796,
+        "chunk": "# 1.难熔金属材料  \n\n难熔金属及其合金具有熔点高、耐高温和抗腐蚀性强等突出优点，应用领域涉及固体火箭发动机、重返大气层的航天器和航天核动力系统，涉及的材料包括钨、多孔钨、钼、钼、、锯、钛等合金。美国从20世纪60年代初开始将其列为重要的空间材料之一而进行大力研究，相继研制出锻造钼合金、旋压钨-石墨纤焊件、多孔钨渗银等多种材料和制品。目前研究和使用较多的是钨渗铜喉衬，由钨粉烧结成多孔钨骨架，再经高温熔渗铜，形成钨渗铜二元假合金。为了进一步提高钨渗铜材料的性能，在钨基体中加人少量HfC（碳化铪)、$Z_{\\mathrm{{r}}}C$ 等进行弥散强化来提高钨的强度、抗热震性和微观结构及其在高温下的稳定性。美国某导弹第一级喷管采用了大型钨喉衬，HS-303A卫星上远地点发动机喷管也采用了钨喉衬。",
+        "category": " Introduction"
+    },
+    {
+        "id": 797,
+        "chunk": "# 2.陶瓷基复合材料  \n\n由于陶瓷在高温下具有良好的抗氧化性和高熔点、高强度而受到广泛重视，其低的热导率和高的耐冲刷性，很适宜作耐冲刷的绝热材料。如碳纤维增强陶瓷：Cf（铜）/ $\\mathrm{\\bfSi_{3}N_{4}}$ ， $\\mathbf{Cf}/\\protect$ SiC、 $\\mathrm{Cf/SiO_{2}}$ ? $\\mathrm{Cf/Al_{2}O_{3}}$ ，以及陶瓷纤维增强陶瓷： $\\mathrm{{Al}_{2}\\mathrm{{O}_{3}/\\mathrm{{Cf}}}}$ 1 $\\mathrm{SiCf/SiO_{2}}$ ， $\\mathrm{SiO}_{2}/\\mathrm{SiO}_{2}$ 0这些材料中应用于火箭喷管的有 $\\mathrm{{Al}_{2}\\mathrm{{O}_{3}/\\mathrm{{Cf}}}}$ 、Cf/SiC，可作叶片有内、外喷管瓣等。二维SiCf/SiC可作燃气舵。目前法国在陶瓷基复合材料生产方面处于世界领先水平，具有制造“使神号”航天飞机用SiCf/SiC和Cf/SiC大型部件的能力。Cf/SiC复合材料是制作抗烧蚀表面隔热板的较佳候选材料之一，它具有质轻耐用的特点。欧洲目前正集中研究载人飞船及可重复使用的飞行器的可简单装配的热结构及防热材料，其中Cf/SiC复合材料是一种重要材料体系，并已达到很高的生产水平。在美国，用Cf/SiC复合材料制备的TPS可用于航天操作工具和航天演习工具，Al-liedsignal复合材料公司生产的复合材料在高温环境测试中显示出优异的性能。波音公司通过测试热保护系统大平板隔热装置，也证实了Cf/SiC复合材料具有优异的热机械疲劳特性。",
+        "category": " Introduction"
+    },
+    {
+        "id": 798,
+        "chunk": "# 3.石墨材料  \n\n常压下不熔化， $3700^{\\circ}C$ 下升华，强度随温度上升而增加，温度上升至 $2500^{\\circ}\\mathrm{C}$ 后强度才开始下降，石墨具有较高的化学稳定性、较好的耐烧蚀性和耐冲刷性能。用作抗烧蚀的石墨有多晶石墨和热解石墨，多晶石墨强度较低，抗热震性能较差，因此其应用受到限制。热解石墨是由气相炭沉积在基体上制成的，相比多晶石墨而言，强度和抗烧蚀性能要好些。将热解石墨涂覆于多晶石墨上的喉衬也在一些高性能推进剂的发动机上成功使用，如Phoenix喷管、Condor喷管和北极星A3导弹第二级喷管的喉衬都采用热解石墨。但用热解石墨作喉衬，工艺复杂、成本高，可靠性较差。  \n\n目前，一种新型石墨渗铜抗烧蚀材料在喉衬材料中的应用已受到重视。它是由石墨基体微孔中渗人铜的一种复合材料，其强度高于常规石墨，密度小于钨渗铜，价格便宜。适合于战术导弹、喷管喉衬选用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 799,
+        "chunk": "# 4.碳/碳复合材料  \n\n$C/C$ 复合材料是一种碳纤维增强碳基体的复合材料，具有高强度，尤其是高温强度稳定、抗热冲击性能好、耐烧蚀性好，是最理想的喷管材料。美国是最早开展C/C喷管材料研究的国家之一。20世纪60年代，美国就展开了2DC/C喉衬材料的研究。从70年代起，又发展了高密度3D与4DC复合材料喉衬。法国从1969年开始实施C/C喉衬材料的发展计划，并于1972年将2DC/C喉衬装在SRM中首飞成功。80年代末，法国开发了一种称Novel-tex结构的超细三向预制件编织技术，制成材料的剪切强度是普通复合3DC/C材料的$3\\cdots4$ 倍，近来，Novel-tex预制件编织向4D、5D、6D多维结构发展，进一步提高了材料性能。前苏联从70年代初开始研究 $C/C$ 复合材料，到80年代中期已经投入应用，其大型的$C/C$ 延伸锥制品在尺寸方面领先于西方国家，目前，俄罗斯已能生产大型C/C喉衬，内径达 $800\\mathrm{mm}$ ，外径达 $1000\\mathrm{mm}$ 8  \n\n目前， $c/c$ 复合材料正向着降低成本，进一步提高性能和拓宽应用领域的方向发展。法国、俄罗斯等国研究了将TaC（碳化钮）、HfC、ZrC等难熔化合物渗透到C/C复合材料中，制取抗冲击、耐烧蚀 $C/C$ 复合材料喉衬。另外，提出在C/C复合材料表面涂覆HfC等难熔碳化物，有望大大降低C/C复合材料烧蚀率，承受更高燃气温度或延长工作时间。美国已开发出一种混合涂覆 $\\mathrm{HfC}+\\mathrm{SiC}$ 的C/C复合材料。苏联已成功地制备了HfC、TaC涂层的喉衬，并通过固体火箭发动机点火试验演示了它的能力。这些材料在航空航天、地空导弹等上的应用，见表3-9-7。  \n\n表3-9-7C/C喉衬材料应用  \n\n\n<html><body><table><tr><td>发动机</td><td>织物类型</td><td>喉径/mm</td><td>密度/（g/cm3）</td><td>喉部烧蚀率/(mm/s)</td></tr><tr><td>美国STAR30ESRM</td><td>3D</td><td>76.23</td><td>二</td><td>0.99</td></tr><tr><td>美国TUSSRM-1</td><td>3D</td><td>164.59</td><td>1.90</td><td>一</td></tr><tr><td>美国/法国SEP/CSDRSM</td><td>4D</td><td>54.86</td><td>1.91</td><td>0.065</td></tr><tr><td>美国/法国全复合材料RSM</td><td>4D</td><td>65.10</td><td>1.90</td><td>0.072</td></tr><tr><td>法国MAGE-I级SRM</td><td>4D</td><td>75.00</td><td>一</td><td>0.155</td></tr><tr><td>美国侦察兵第二级SRM</td><td>4D</td><td>91.6</td><td>1.88</td><td>一</td></tr><tr><td>美国MX各级SRM</td><td>3D</td><td>一级381</td><td>1.88~1.92</td><td>0.328</td></tr><tr><td>美国侏各级SRM</td><td>3D</td><td>一</td><td>一</td><td>一</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 800,
+        "chunk": "# （二）复合耐烧蚀材料  \n\n由于酚醛树脂的产炭率较高，为 $57\\%\\sim55\\%$ ，且一些新研制出的改性酚醛树脂成炭率已达 $70\\%$ 以上，且酚醛树脂在热解时可生成一种具有环形结构、抗烧蚀性能优异的中间产物，完全炭化后的炭化层致密、稳定，所以，这种最早问世的合成树脂不仅是最早用于喷管的烧蚀材料，迄今仍在耐烧蚀材料领域扮演着重要的角色。树脂基烧蚀材料往往采用“复合模压”、“复合缠绕”工艺，在燃气冲刷严重的部位使用耐烧蚀性能优异的树脂基材料，如碳（石墨）/酚醛。而在烧蚀较缓和急需隔热的部件使用耐烧蚀性能稍逊而隔热性能较好的材料，如高硅氧/酚醛复合材料、石棉/酚醛复合材料甚至玻璃纤维/酚醛复合材料等。表3-9-8给出了一些树脂基烧蚀复合材料在固体火箭发动机喷管上的应用情况。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 801,
+        "chunk": "# （三）有机消融隔热材料  \n\n有机消融隔热材料可以分为以下几类。  \n\n（1）玻璃钢制品是以有机高聚物为黏结剂，以无机纤维如 $\\mathrm{SiO}_{2}$ 、碳纤维、硼纤维等，或者有机纤维为骨架材料，经过浸渍、加热、加压固化成型的结构隔热材料。如导弹的壳体、头锥、喉衬等都可以采用该类产品制造。  \n\n表3-9-8树脂基烧蚀复合材料的应用  \n\n\n<html><body><table><tr><td>材料</td><td>应用实例</td></tr><tr><td>碳（石墨）/酚醛（带缠）</td><td>里安-5运载火箭固体助推器喷管；日本M-3G2火箭；M-V火箭各级发动机喷管；H-2火箭 轨道助推器、北极星A3及潘兴第一级的收敛段和扩散段；凤凰导弹的扩张段前部；海神 C3第一级扩散段、近喉人口段与喉衬；260SL-3喷管收敛段、扩张段前部与中部、潜人段前 部及喉衬；航天器固体助推器的喷管扩张段；哥伦比亚号、大力神-4、阿里安-3、阿里安-4、阿</td></tr><tr><td>碳（石墨）/酚醛（模压）</td><td>助推器喷管 凤凰导弹收敛段及长尾管；民兵第一级扩张段后部；民兵第一级收敛段与嵌人段前部</td></tr><tr><td>碳（石墨）/酚醛（花瓣铺层）</td><td>海神C3第一级近喉部人口段、收敛段头帽</td></tr><tr><td>高硅氧/酚醛（带缠）</td><td>凤凰导弹收敛段，长尾段，扩张段前部、后部；潘兴第一级的喉衬背壁；民兵第二级扩散段 前部、后部；海神C3第一级收敛段、嵌人段；260SL-3发动机嵌人段中部与扩张段后部，潜人</td></tr><tr><td>高硅氧/酚醛（模压）</td><td>段后部，扩张段中部、前部、喉衬背壁 秃鹰的扩张段；民兵第二级的后尘延伸段背壁；海神C3第一级喉村背壁</td></tr><tr><td>石棉/酚醛（模压）</td><td>秃鹰长尾管、收敛段与喉衬背壁；响尾蛇IC喉衬背壁、扩张段；北极星A3收敛段与喉衬 背壁</td></tr><tr><td>石棉/酚醛（带缠）</td><td>北极星A3扩张段；潘兴第一级收敛段；民兵第二嵌人段前部</td></tr><tr><td>玻璃/酚醛</td><td>260SL-3发动机喷管潜人段前部及收敛段</td></tr></table></body></html>  \n\n(2）蜂窝夹心结构材料是以薄玻璃钢为蜂窝结构的隔板，内部填充低密度空心微珠或有机泡沫而成。“阿波罗”号宇宙飞船的指挥舱就是用该材料制成的。  \n\n(3）可剪贴的弹性贴片是由弹性树脂或橡胶加人消融性和耐高温填料压制而成。可用于导弹表面和固体火箭发动机燃烧室衬里等部位的隔热保护。  \n\n(4）有机消融涂层由于涂料具有施工简单、应用范围适应性强，最主要的是涂层的消融隔热性能优于其他材料，所以，得到广泛的应用。  \n\n烧蚀涂料的发展有两个显著的特点：一是基料大都选用有机树脂及弹性体；二是质量向低密度方向发展，且这两方面经常是相互结合的。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 802,
+        "chunk": "# 三、消融隔热涂层的作用机理  \n\n消融隔热涂层，是指涂层在高温下消融过程中发生物理、化学的吸热反应带走热量，达到隔热和保护设备的目的。自然界中陨石坠入地球就是依据自身消耗防热的原理到达地球的，消融涂层隔热的机理也是一样的。  \n\n笔者认为消融隔热涂层的作用可以分为两部分来实现，一是通过涂层消融隔热来达到被保护设备处于正常工作温度范围；二是涂层具有良好的被消融和抗消融的能力，来达到被保护设备不被高温气流冲蚀。  \n\n消融隔热涂层是由物理吸热和化学吸热构成。物理吸热过程包括熔融、汽化、升华、反射和辐射等方式，化学吸热过程除高聚物降解、裂解等吸热方式外，涂层组成之间还可以发生吸热的化学反应，典型的反应如下所示。  \n\n$$\n\\mathrm{SiO}_{2}+\\mathrm{C}\\Longrightarrow\\mathrm{SiO}+\\mathrm{CO}+62.~8\\times10^{4}\\mathrm{J}/\\mathrm{mol}\n$$  \n\n$$\n\\mathrm{SiO}_{2}+2\\mathrm{C}\\Longrightarrow\\mathrm{Si}(\\not\\exists\\vec{\\mu})+2\\mathrm{CO}+64.4\\times10^{4}\\mathrm{J}/\\mathrm{mol}\n$$  \n\n$$\n\\mathrm{SiO}_{2}+3\\mathrm{C}\\longmapsto\\mathrm{SiC}(\\mathrm{\\textcircled{H}})+2\\mathrm{CO}+51.3\\times10^{4}\\mathrm{J}/\\mathrm{mol}\n$$  \n\n$$\n{\\mathrm{SiC}}+2{\\mathrm{SiO}}_{2}=3{\\mathrm{SiO}}+{\\mathrm{CO}}+13.7\\times10^{5}{\\mathrm{J/mol}}\n$$  \n\n$$\n\\mathrm{O}_{2}+\\mathrm{Si}(\\sharp\\sharp)\\longleftrightarrow2\\mathrm{SiO}(\\sharp)+61.5\\times10^{4}\\mathrm{J}/\\mathrm{mol}\n$$  \n\n上述化学反应的吸热量远远高于高聚物自身分解所带走的热量，是同质量高聚物裂解吸热量的5.8倍，这对于消融隔热涂层的配方设计具有重要的指导意义。  \n\n另外，在上述过程中产生的小分子气体，增厚了滞留边界层，大大降低涂层的传热效率；还有高聚物裂解炭化和无机填料熔融炭化形成多孔蜂窝状的炭化层，进一步可以降低传热效率。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 803,
+        "chunk": "# （一）烧蚀作用— 一热屏蔽的物理原理  \n\n一些聚合物和聚合组分具有惊人的吸热、散热和隔热的能力，通常每消耗一定量的这类材料，便可带走大量的热量，我们把这一过程叫做“烧蚀作用”。  \n\n烧蚀过程是相当复杂的，多年来采用两种方法研究：一种是解析预测方法，即利用计算机程序法去求得描述过程的多元联立微分方程的数字解；第二种方法是实验室（模拟）试验，有时是在实际飞行中进行试验，从经验中来说明个别烧蚀机理及其与外界环境的关系。  \n\n材料在烧蚀过程中的许多重要的物理化学特性现已可以确定。刚开始加热时，烧蚀聚合物吸收能量并向内部传导，热量向内部传递的速度与表面温度有关，由于耐烧蚀化合物的热导率很低，故热扩散总是很慢，因此，表面的热量便不断积蓄而使温度迅速升高，直至聚合物材料开始发生汽化。最初挥发出来的通常是水及残存的稀释剂或是一些低分子量的聚合物。温度继续升高，聚积的热量使聚合物主链的侧基裂解，最后使主链上的化学键也开始断裂，于是聚合物内部便开始进行竞争反应。如果聚合物链上取代基的消去作用比链的裂解作用占优势，那么原来链的结构将以炭的形式保留下来，这就是所谓炭化作用。通过炭化作用，烧蚀聚合物在表面上形成炭化层，这种炭化层可以将内层不稳定的聚合物与高温环境隔离起来，从而减缓下层材料的加热速度（这是由于它具有很高的表面红外线发射比，能通过辐射作用将大部分的热量消散出去)；同时，炭化表面层继续起着十分重要的吸热作用，如它将与材料裂解所生成的烃类等气体和残存的增强剂（为提高烧蚀材料抗磨蚀性能，一般聚合物都要配以高性能的增强剂如碳化纤维、玻璃纤维等）进行第二次吸热反应（参看下面热化学原理)。在大多数情况下，新生成的炭化层至少在短期内会附着在未起变化的底层材料上。随着烧蚀过程的进行在所生成的炭化层下面的未起变化的材料也开始高温裂解了，并形成一个降解层。在降解层中所生成的气体依靠自身的压力穿过逐渐老化的焦炭表层，气体和灼热的焦炭相互促进了热化学反应的进一步发生，如氧化和分解反应等。整个烧蚀过程的各种反应及辐射作用即形成了有效的热功当量屏蔽作用保护了底材。炭化组分的烧蚀过程如图3-9-2所示。  \n\n![](images/7e56d511b378f52e7798da0a125418d10a4e7916442c91fc3ecf7c32d04136bf.jpg)  \n图3-9-2 炭化组分烧蚀过程的物理描述  \n\n当聚合物会熔化或者含有可熔化的组分时，那么在熔点还要吸收熔化潜热，接着开始熔融并形成一个液化层。若熔化的材料的黏度很低，则气-液界面会因气动剪切力的作用立刻被吹散，只能留下一层极薄的液体薄膜；若熔化物的黏度很高，则它能附着在表面上直至吸  \n\n收了足够的热量开始蒸发时为止，在这种情况下需要吸收额外的蒸发潜热，这时表面的温度与液体的蒸发温度一致。然而在大多数情况下，熔融烧蚀过程既具有流体性能又有液膜的蒸发作用，究竞哪一种机理占优势，主要取决于周围环境参数（如剪切力、热流量等）和熔融物温度-黏度的依赖关系，如图3-9-3所示。  \n\n如果在炭化聚合物组分中加入纤维或填料，则烧蚀过程将有所变化。例如，尼龙织品填料可在炭化表层下的溶解层中发生熔化和蒸发作用，使原来被纤维占据的地方成为空穴，从而形成一种多孔性的炭化层，这种炭化层在机械力的作用下很容易被磨蚀掉。玻璃纤维的  \n\n![](images/cdf8862d4c0df21f63b12d70d2b7d5b32473a6246d80e9415a38c2355840403d.jpg)  \n图3-9-3 玻璃纤维增强酚醛树脂的烧蚀过程  \n\n耐烧蚀机理又不同于尼龙织品，因为有机树脂或其炭化的残渣在烧蚀过程中由于化学和机械力的作用比玻璃纤维更易除去，因此在表面上便遗留下许多游离的玻璃纤维，随着烧蚀过程的进行，纤维熔化，在表面上形成许多小液滴、不规则旋进的小圆环或形成一种液化薄膜。当采用碳质纤维织品作填料时，因为它能极好地固定炭化组分，所以在热解过程中能形成一种高强度的炭化层并牢固地附着在底层上。与尼龙和玻璃纤维织品不同，碳质纤维受高温的影响很小，只有在进行热化学反应，如氧化反应时才能将它除去。  \n\n从热物理学的观点来看，烧蚀作用是一种有规则的加热和传质过程，在这个过程中由于表层材料的不断消耗而带走了大量的热能；由周围环境所输人的热能通过多种机制进行吸收、隔热和消散。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 804,
+        "chunk": "# （二）成炭型与升华型烧蚀聚合物热化学反应 热屏蔽的化学原理  \n\n上面从物理角度阐明了烧蚀材料在烧蚀过程中的隔热作用原理。下面再从热化学角度来论述烧蚀材料热屏蔽作用原理。  \n\n从烧蚀过程的物理描述可知，聚合物烧蚀隔热主要通过两种手段：炭化层通过再辐射作用隔热及分解气化吸热。以前者为主者称成炭型烧蚀材料，以后者为主者称升华型烧蚀材料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 805,
+        "chunk": "# 1.成炭型烧蚀材料  \n\n用高纯度二氧化硅纤维增强的热固型酚醛树脂是典型的成炭型烧蚀材料，已被广泛地用于宇宙飞船。下面就以此系统为例说明成炭型烧蚀材料的热化学过程。  \n\n上述烧蚀材料暴露在某种高热通量的环境中时，可能发生各种化学反应，包括树脂生成气体和焦炭的热解反应(1类)，生成气体的再次热反应(2类)，气体和焦炭的再次热反应(3类）以及焦炭和增强剂之间的反应（4类)。其中，第4类反应具有最大的吸热效应，如表3-9-9所示。由表可见，碳-氧化硅反应时，发现加入少量铁时，碳与二氧化硅的反应速度将增加550倍，为此将过渡金属和金属氧化物加到酚醛-二氧化硅组成中的方法得到了发展，二氧化硅/酚醛树脂烧蚀反应的标准热熔变化见表3-9-9。  \n\n二氧化硅和碳质材料之间的反应是通过气态中间体，即一氧化硅的方式进行的，反应物接触面积大，所以反应速率较快。气态一氧化硅可由若干种反应形成，如二氧化硅分解反应：  \n\n接着这些气体一氧化硅与固体碳发生如下的反应：  \n\n表3-9-9 烧蚀反应的标准热变化 $:25^{\\circ}C$ r  \n\n\n<html><body><table><tr><td>编号</td><td>类别</td><td>反 应</td><td>H/(cal/mol)</td></tr><tr><td>1</td><td>1</td><td>树脂的热解反应</td><td>+265</td></tr><tr><td>2</td><td>2</td><td>CH4（气)C(固)+H（气）</td><td>十17889</td></tr><tr><td>3</td><td>2</td><td>CH（气)+9H（气)6CH（气）</td><td>—127154</td></tr><tr><td>4</td><td>3</td><td>C（固）+CO（气）2CO（气）</td><td>+41220</td></tr><tr><td>5</td><td>3</td><td>C(固)+HO(气)CO(气)+H（气)</td><td>+31382</td></tr><tr><td>6</td><td>4</td><td>SiO（固)+C(固）SiO（气)+CO（气）</td><td>+150214</td></tr><tr><td>7</td><td>4</td><td>SiO(固)+2C(固)Si(液)+2CO(气）</td><td>+154000</td></tr><tr><td>8</td><td>4</td><td>SiO（固)+3C(固)SiC(固)+2CO（气)</td><td>+122518</td></tr><tr><td>9</td><td>4</td><td>SiC(固)+2SiO（固)3SiO（气)+CO（气）</td><td>+328124</td></tr><tr><td>10</td><td>4</td><td>SiO（固)+Si(液)—2SiO（气）</td><td>+146910</td></tr></table></body></html>\n\n$\\textcircled{1}1\\mathrm{cal}=4.1840\\tilde{\\mathrm{J}},$ 晶$\\textcircled{2}$ 在 $1000^{\\circ}\\mathbf{F}$ （ $537.8\\%$ ）进行热解反应时的数据。$\\textcircled{3}$ $2\\sim10$ 反应中的 $\\Delta H25^{\\circ}\\mathrm{C}$ 数值是根据JANAF热化学表中的数据和美国标准局的资料计算而得。  \n\n另外，从反应热和反应热力学角度考虑，在二氧化硅-酚醛树脂系统中，在较低温度下有可能进行表3-9-9中第8项反应；而在较高温度下则在可能进行如下的反应：  \n\n整个反应的结果与表3-9-9中反应6的结果是一样的。这些过程的总效应是使高温区域中的焦炭完全蒸发，从而达到热屏蔽作用。  \n\n向碳-二氧化硅各级组织加人铁或氧化铁以后，就可把它看成是一个Fe-C-Si-O的四元系统。细铁粉分散在整个酚醛-二氧化硅组织后，可以获得一种铁、二氧化硅和碳的致密混合物。热解时，当温度刚高于铁-碳的低共熔温度 $1153^{\\circ}\\mathrm{C}$ 时，易形成一种液态的铁溶液。在碳-二氧化硅系统中液态铁的存在，为反应物在该反应系统中的传递提供了另一种可能的机理，即此时炭可以通过液体介质传送到二氧化硅的表面上，从而有利于硅-碳吸热反应进行。  \n\n如果向酚醛-二氧化硅组织中添加的不是铁而是氧化铁，那么氧化铁就有被还原的可能性。全部反应可以写成：  \n\n$$\n3\\mathrm{Fe_{2}O_{3}+C}\\mathop{\\longrightarrow}2\\mathrm{Fe_{3}O_{4}+C O}\n$$  \n\n$$\n\\mathrm{Fe_{3}O_{4}+C=3F e O+C O}\n$$  \n\n$$\n\\mathrm{FeO+C}\\Longrightarrow\\mathrm{Fe+CO}\n$$  \n\n$$\n\\mathrm{Fe_{2}O_{3}+3C}\\Longrightarrow\\mathrm{2Fe+3CO}\n$$  \n\n这些反应亦都为吸热反应，反应热可用FANAF热化学表所提供数据进行计算，其结果列于表3-9-10中。  \n\n表3-9-10 FANAF热化学数据  \n\n\n<html><body><table><tr><td>反应编号</td><td>反 应</td><td>H1500x/(cal/mol)</td></tr><tr><td>11</td><td>3FeO+C2FeO+CO</td><td>+28653</td></tr><tr><td>12</td><td>FeO+C3FeO+CO</td><td>+40713</td></tr><tr><td>13</td><td>FeO+C=Fe+CO</td><td>+35610</td></tr><tr><td>14</td><td>FezO+3C—2Fe+3CO</td><td>+109913</td></tr></table></body></html>  \n\n如果氧化铁分散得很好，则可保证它与炭紧密地接触，因此还原反应进行得很快。氧化铁在焦炭层中被还原成铁，而树脂则被认为完全热解成炭和还原气了。这些反应吸收了大量热，从而大大降低了这种涂料在高能环境中的炭化深度（Fe及其他过渡金属化合物亦能起这种作用，效果比 $\\mathrm{Fe}_{2}\\mathrm{O}_{3}$ 差)，即提高了热屏蔽作用。  \n\n从上例可见，烧蚀材料隔热的基础是产生一系列吸热反应，添加剂的强化基础亦是强化吸热反应。成炭型烧蚀聚合物应具备的首要条件是热解后要能形成炭化层，而且希望其炭化层能牢固地附着在下层材料上，即有抗化学腐蚀（氧化）和机械磨损（颗粒的摩擦，气动剪切力、外部气压的负荷等）性能。一般具备这种性质的聚合物的链中都含有环状结构（芳环或杂环)、梯形结构、有高交联度的结构或由其他元素（如硅）组成的结构，即一般都含热稳定性结构。聚合物热稳定性愈高，则其成炭率也愈高。在一般情况下，聚合物成炭率愈高，其所形成的焦炭层强度和附着力亦愈高。热固性酚醛树脂是最早使用的成炭型烧蚀材料，使用广泛，现在又发现了许多成炭率比它更高的聚合物，不同烧蚀树脂的焦炭产率见表3-9-11。  \n\n表3-9-11 不同烧蚀树脂的焦炭产率  \n\n\n<html><body><table><tr><td>聚合物</td><td>结 构</td><td>焦炭产率/%</td></tr><tr><td>聚亚甲基苯（苯二甲醇 固化）</td><td>CH2 CHz</td><td>77.0</td></tr><tr><td>聚苯并咪唑</td><td>之工</td><td>73.9</td></tr><tr><td>对苯基苯酚-酚醛树脂</td><td>OH OH CH CH—-</td><td>70.0</td></tr><tr><td>联酚醛树脂</td><td>OH OH HOCH2 CHzOH</td><td>65.1</td></tr><tr><td>聚酰胺-酰亚胺</td><td>O= =0</td><td>65.0</td></tr><tr><td>蔡亚甲基二羟基酚醛</td><td>OH OH CH2 CHz CH2 CH2 HO- OH</td><td>63.4</td></tr><tr><td>聚酰亚胺</td><td>O 0 O =0</td><td>63.0</td></tr><tr><td>酚醛</td><td>OH CHz- CH2</td><td>60.0</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 806,
+        "chunk": "# 2.升华型烧蚀材料  \n\n这类烧蚀材料的烧蚀过程不是在表面而是在内部进行的，烧蚀以后在表面上也没有炭质残渣生成，通常称作内烧蚀材料。这种材料主要是由一种多孔的、耐高温的、连续的基体（如多孔性陶瓷）和一种能在高温气化的填充材料（升华型烧蚀聚合物）所组成。升华型聚合物吸收热量的物理变化和化学反应包括：  \n\n$\\textcircled{1}$ 解聚蒸发作用（吸热化学反应）；  \n$\\textcircled{2}$ 热解蒸发作用（吸热化学反应）；  \n$\\textcircled{3}$ 熔化蒸发作用（相变吸热）。  \n\n在分子结构上有利于解聚的聚合物特别适合作升华型烧蚀材料，通常烯类单体的双键的一个碳原子上同时有两个取代基，聚合热 $\\Delta H_{\\mathfrak{p}}$ 、最高聚合温度 $T_{\\perp}$ 较低者易解聚（聚四氟乙烯例外，其 $\\Delta H_{\\mathfrak{p}}$ 1 $T_{0}$ 较高，但仍易解聚，这主要是C—F键能大于C—C键之故)；分子中有配位性强的元素，相距 $5\\sim6$ 个原子，有利成稳定环（如六元环）时易解聚。如聚甲基丙烯酸甲酯、聚己内酰胺等。  \n\n$$\n\\begin{array}{c c}{{\\mathrm{CH_{3}}}}&{{\\mathrm{CH_{3}}}}\\\\ {{\\mathrm{\\underline{{{I}}}\\underline{{{\\Sigma}}}\\underline{{{\\Sigma}}}}}}&{{\\mathrm{\\underline{{{\\Pi}}}\\underline{{{\\Sigma}}}\\underline{{{\\Sigma}}}\\underline{{{\\Sigma}}}\\underline{{{\\Sigma}}}\\underline{{{\\Sigma}}}\\underline{{{\\Sigma}}}\\underline{{{\\Sigma}}}\\underline{{{\\Sigma}}}\\underline{{{\\ O}}}\\mathrm{OH_{3}}}}}\\\\ {{\\mathrm{\\underline{{{\\Gamma}}}\\underline{{{\\Sigma}}}O O C H_{3}}}}&{{}}\\end{array}\n$$  \n\n$$\n\\begin{array}{r}{\\begin{array}{r}{\\mathrm{\\underline{{\\sf\\CHN}}(\\mathrm{\\mathbf{CH}_{2})}}_{5}\\mathrm{\\underline{{CO}}}\\mathrm{\\underline{{\\sf\\vec{J}}}}_{\\mathrm{\\underline{{n}}}}\\quad\\mathrm{\\longleftrightarrow\\atop\\mathrm{\\mathbf{CH}}_{2}\\mathrm{\\-\\-CH}_{2}}\\mathrm{\\underline{{\\underline{{\\zeta}}}}\\mathrm{\\underline{{H}}}}_{\\mathrm{\\underline{{n}}}}}\\end{array}}\\end{array}\n$$  \n\n聚合物经热解后生成的产物（包括单体在内）都是挥发性化合物，如聚乙烯、聚苯乙烯等，亦可采用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 807,
+        "chunk": "# 四、消融隔热涂料的配方设计原则  \n\n消融隔热涂层应该具有优越耐高温性能、良好的消融性能和阻隔热传递的性能，在进行配方设计时应紧密结合消融隔热涂层的作用机理和应用环境来确定最优化的涂料配方。作为消融隔热涂层而言，不仅要具有良好的耐温性能，更重要的是良好的消融、隔热性能。涂层消融隔热作用可分为三部分：一是涂层在烧蚀初期低温可分解组分发生消融产生气体小分子，带走大量的热；二是各组分分解残留物之间发生高吸热的化学反应；三是涂层形成低热导率炭化层阻隔热的传递。  \n\n笔者研制的以环氧有机硅树脂为基料树脂，配以低温消融填料、耐高温填料以及助剂等，制备的消融隔热涂层，经过模拟试验和实际应用，在很高温度（火焰、气动等）的作用下，试验前期涂层隔热效果非常明显，例如，乙炔-氧火焰温度 $1400^{\\circ}C$ ，涂层厚度 $3.0\\mathrm{mm}$ 在 $15\\sim20\\mathrm{s}$ 以内样板背面的温度基本不会升高；在 $20\\sim45\\mathrm{s}$ 时间段，样板背面温度缓慢升高，呈加速升温状态，升温速度大概为 $0.5{\\sim}2.0^{\\circ}\\mathrm{C}/s$ ，在25s内升温幅度在 $25\\sim35^{\\circ}C$ ；45s后样板背面温度稳定快速升高，特别是在60s后，温度急速升高，样板背面升温幅度可达$80^{\\circ}C$ 以上，即考虑环境温度样板背面可达到 $100^{\\circ}C$ 以上。  \n\n所以我们认为，涂层消融隔热性能是至关重要的，特别是对于导弹、火箭等发射时，较短时间几秒到几十秒内，对装置防隔热保护非常重要。  \n\n消融隔热涂料在配方设计时应遵循以下原则。  \n\n$\\textcircled{1}$ 基料树脂应具有良好的耐高温、耐烧蚀性能，以及良好的力学性能和防护性能；$\\textcircled{2}$ 填料在消融隔热涂层中起到无可替代的作用，为了满足涂层隔热、烧蚀性能，应是多种填料配合使用，在不同温度段发挥各自的作用；  \n\n③在配方设计时应该特别重视添加剂的选择、利用，适当的添加剂可以显著改善涂料及涂层的性能。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 808,
+        "chunk": "# 五、消融隔热涂层的组成  \n\n消融隔热涂料是由基料、颜料、填料、溶剂以及助剂等组成，作为特殊用途的涂料，各组成有别于普通涂料组成，例如，用于消融隔热涂料的成膜物树脂，除了具有作为涂料成膜物树脂的基本性能之外，最重要的应该具有良好的耐高温及耐烧蚀性能。由于消融隔热涂层的特殊功能要求，选用的颜料要符合着色、防腐和耐高温、耐烧蚀要求，要有功能性填料来配合使用，以满足涂层消融和耐高温要求，这在前面已有涉及，不再重复。后面重点介绍成膜物树脂。  \n\n消融隔热涂料可以分为有机消融涂料和无机消融涂料两大类。无机基料一般为硅酸盐、磷酸盐类；有机成膜物有环氧树脂、酚醛树脂、聚氨酯树脂、有机硅及其改性产品、聚苯及杂环树脂、乙烯树脂以及特种橡胶（硅橡胶、氟橡胶、氯化橡胶）等。由于无机烧蚀涂层在大面积施工时容易开裂、返黏，其作用机理也不同，多用于结构的沟、缝等局部使用。而有机烧蚀涂层具有施工性能良好、易修复，涂层力学性能优，耐热冲击性能优良，密度低，而且涂层经烧蚀后可形成一定程度的发泡涂层，具有更为优越的隔热效果等优点。所以，有机烧蚀涂层的应用更为广泛。这里只介绍有机消融隔热涂层。  \n\n有机消融涂料根据成膜物树脂在高温条件下发生的消融过程可以分为成炭型、成硅型和无残留型树脂，树脂种类及特点见表3-9-12。  \n\n表3-9-12 树脂种类及特点  \n\n\n<html><body><table><tr><td>类型</td><td>特点</td><td>树脂品种</td><td>性能</td></tr><tr><td rowspan=\"3\">成炭型</td><td rowspan=\"3\">高温炭化后可形成高比 例的炭化层</td><td>酚醛树脂</td><td>耐温性能和消融性能良好，成炭率60%以上，低温 脆性，附着力差，不能常温固化</td></tr><tr><td>环氧树脂</td><td>力学性能好、可室温固化，耐温性能和消融性能不如 酚醛树脂</td></tr><tr><td>聚苯及杂环树脂</td><td>成炭率高（1000℃下82%），消融性能优异，但溶解 性差，施工困难，固化温度高</td></tr><tr><td>成硅型</td><td>高温裂解后残留物主要</td><td>聚氨酯树脂及泡沫 有机硅树脂</td><td>耐磨、耐候、耐化学品好，室温快速固化，但高气动剪 切条件下消融性能欠佳 优异的耐热性，但纯有机硅树脂有附着力差、高温烘</td></tr><tr><td>无残留型</td><td>为硅质化合物 高温下树脂可全部分解 成小分子，不残留任何 物质</td><td>聚四氟乙烯 聚甲基丙烯酸甲酯 聚苯乙烯</td><td>烤固化等缺点；环氧改性有机硅树脂可以克服其不足 其隔热效果有限</td></tr></table></body></html>  \n\n有机合成树脂的种类很多，但并不是所有的有机合成树脂都能够应用于消融隔热涂层，选用的合成树脂应该具有良好的热稳定性和在高温下良好的抗消融性。  \n\n聚合物的热稳定性能现在还没有一个严格的定义，往往是根据其实际应用的角度来划分。聚合物的热稳定性一般采用时间和温度来描述。有人认为可以在 $200^{\\circ}C$ 长期使用，在$500^{\\circ}C$ 间歇使用，而在 $500{\\sim}1000^{\\circ}C$ 的超高温下可以保持几秒到十几秒不发生降解的聚合物，就可以称之为热稳定聚合物；而另外一种说法则认为，聚合物在情性气体中 $175^{\\circ}C$ 保持$\\mathtt{30000h}$ ， $250^{\\circ}C$ 保持 $1000\\mathbf{h}$ ，在 $500^{\\circ}C$ 保持 $\\mathtt{1h}$ 或者 $700^{\\circ}C$ 保持 $5\\mathrm{min}$ ，其力学性能没有明显变化的聚合物便是热稳定聚合物。表3-9-13是几种树脂结构与耐热性能之间的关系。  \n\n提高聚合物的耐热性，可根据马克三角原理，即增加高分子链的刚性、提高结晶度和高度交联。上述的几种高聚物具有典型的结构特征，完全可以代表耐热树脂的特性，遵循这些原则，结合实际应用，制备技术性能满足要求的树脂。  \n\n表3-9-13 几种聚合物的耐热特性  \n\n\n<html><body><table><tr><td>聚合物名称</td><td>结构式</td><td>耐热性/℃</td></tr><tr><td>聚四氟乙烯</td><td>(FC—CFz）</td><td>250</td></tr><tr><td>聚马来酰亚胺</td><td>0 0 H H H H</td><td>220</td></tr><tr><td>有机硅聚均苯四酰亚胺</td><td>0 CH3 CH3 (CH）-ESi-O—Si}。(CH） CH CH 0</td><td>300</td></tr><tr><td>苯基硅氧烷(梯形）</td><td>CH5 CH5 CHs O O 0 Q</td><td>300～525</td></tr><tr><td>聚苯</td><td>CH5 C6Hs C6H</td><td>570（短期）</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 809,
+        "chunk": "# 1.有机硅  \n\n由于有机硅产品具有较低的玻璃化温度和较高的耐热、耐老化、耐辐射性能和独特的低温韧性，同时与填料及其他树脂混溶性好，可室温固化，制成的涂层又有良好的耐烧蚀性，所以国内外都广泛采用有机硅树脂作为烧蚀涂料和其他烧蚀材料的基本成膜物。  \n\n1963年，惠普尔（Whippe）对硅橡胶烧蚀材料在不同热流下进行了试验，结果表明，有机硅弹性体在 $108{\\sim}700\\mathrm{kcal/(m}^{2}\\cdot\\mathrm{s})$ 热流下具有较好的烧蚀性能，尤其是密度较低者性能最好。1965年，美国通用电气公司研制成功一种名日RTV-757的触变型硅橡胶泡沫屋，它具有良好的耐热和隔热性能。在纸板上涂一薄层后，在 $5000^{\\circ}\\mathrm{F}$ $2780^{\\circ}C$ ）耐60s，背温仅由 $22^{\\circ}C$ 升至 $29\\%$ ，被保护的鲜花不枯萎，其性能优于以前的品种。此后，以有机硅树脂为基本成膜物的烧蚀涂料相继取得了一系列专利。  \n\n1975年，我国某研究所以甲基、苯基聚硅氧烷为基料，云母、三氧化二铬、硼酸、二氧化钛、滑石粉为添加剂配制的烧蚀涂料，于 $2300^{\\circ}C$ 使用30s，背面非金属材料保持完好。  \n\n美国发往火星的“海盗”号飞船，其登陆舱舱身和外露部件均使用一种硅橡胶为成膜物的涂料。涂料为浅灰色，可以反射太阳的热量，内舱的外壁黏结上一层0.5in（ $\\mathrm{{1in=}}$ $0.0254\\mathrm{m}^{\\cdot}$ ）厚的有机硅树脂中的酚醛-玻璃珠-软木的绝热层，以防护其外壁在进人火星大气层时由摩擦产生的热量（温度大约 $1482.2\\%$ ）而招致的破坏，在星际飞行中都得到了广泛的应用。  \n\n有机硅的产品主要有四大类种，即硅油、硅烷偶联剂、硅橡胶和硅树脂，用于耐烧蚀的涂料是后两种。  \n\n(1）硅橡胶硅橡胶是一种类似硅油的高分子量的线型聚合物。通常按照固化机理可以分为三类。  \n\n① 第一类游离基交联的硅橡胶，这就是通常所说的高热硫化型硅橡胶。它是利用有机过氧化物于高温下在链之间形成亚乙基桥实现固化的。  \n\n$\\textcircled{2}$ 第二类 带有活性端基如硅醇基的线型或高度分支的聚合物链的交联。  \n\n![](images/991605327146a2edc55571af7f2440abc33e743ac6be3d7139d386f560c42f01.jpg)  \n\n这类硅橡胶约占整个硅橡胶的2/3多，室温固化的硅橡胶又分成两类，即双组分的和单组分的。  \n\na.双组分的室温固化硅橡胶是硅橡胶问世最早的一类。它主要由含硅醇端基的聚合物组分和交联剂如硅酸乙酯或烷基三烷氧基硅烷及催化剂如辛酸亚锡、二丁基二月桂酸锡等组成。只有当两个组分混合以后才会发生固化。固化的时间在室温下可以数小时或数天，温度较高则固化加快，现将适合于用作耐烧蚀涂料的双组分硅橡胶列于表3-9-14。  \n\n表3-9-14航空、导弹用的室温固化硅橡胶的主要性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">商品名</td><td rowspan=\"2\">类型</td><td rowspan=\"2\">外观</td><td rowspan=\"2\">氏A</td><td rowspan=\"2\">拉伸强</td><td rowspan=\"2\">伸长率</td><td rowspan=\"2\">活化期</td><td colspan=\"2\">固化时固化性完全圈化时间</td><td rowspan=\"2\">用途</td></tr><tr><td></td><td></td></tr><tr><td>325</td><td rowspan=\"8\"></td><td>白</td><td>68</td><td>22</td><td>100</td><td>8</td><td>65.6℃ (150°F),2h</td><td>65.6°℃ (150F),4h</td><td>用于重返飞船热屏蔽和 绝缘涂料</td></tr><tr><td>20-103</td><td>淡黄</td><td>50</td><td>32</td><td>130</td><td>2</td><td>24h</td><td>48h</td><td>用作烧蚀和绝缘涂料及 加压密封剂</td></tr><tr><td>90-006</td><td>红</td><td>50</td><td>43</td><td>150</td><td>0.5</td><td>1h</td><td>24h</td><td>用作烧蚀和绝缘涂料及</td></tr><tr><td>90-031</td><td>红</td><td>52</td><td>39</td><td>150</td><td>0.5</td><td>1h</td><td>24h</td><td>加用作封和绝缘涂料及 加压密封剂</td></tr><tr><td>93-037</td><td>白</td><td>70</td><td>35</td><td>40~50</td><td>1~5</td><td>70℃ (158F),4h</td><td>70℃ (158F),4h</td><td>用作可喷涂的烧蚀涂料</td></tr><tr><td>93-072</td><td>白</td><td>35</td><td>53</td><td>325</td><td>2</td><td>24h</td><td>72h</td><td>用作抗冲击和烧蚀涂料</td></tr><tr><td>92-009</td><td>单 半透明</td><td>40</td><td>42</td><td>600</td><td><1</td><td>24h</td><td>72h</td><td>用作调温涂料和防热涂料</td></tr><tr><td>92-024</td><td>平组分 灰</td><td>33</td><td>56</td><td>675</td><td><2</td><td>24h</td><td>7d</td><td>密封剂和烧蚀涂料</td></tr></table></body></html>  \n\nb.单组分室温固化硅橡胶所用的交联剂是一种可水解的多官能度的硅酮或硅氧烷，只有当它与空气中的湿气反应以后才显示出活性，与聚合物结合形成交联网而固化。因此它的固化速率是相对湿度和温度的函数。在较高的温度和湿度下， $\\bf{10m i n}$ 之内便可形成表面膜，$20\\mathrm{min}$ 后便可指触干，因为有机硅系统对于许多气体都有很高的渗透性，所以单组分的硅橡胶在一定的时间内可以固化到中等的深度，用人工的方法提高温度和湿度可以加速固化，但  \n\n相对湿度太高反而会妨碍它彻底固化  \n\n由道康宁公司所生产的几种单组分的适合于作涂料的室温固化硅橡胶的主要性能如表3-9-15所列。  \n\n表3-9-15 在烧蚀状态下几种有机硅橡胶的性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">聚合物类型</td><td rowspan=\"2\">相对 密度</td><td rowspan=\"2\">热导率 /[Btu/(h·ft·F)]</td><td colspan=\"2\">低热通量 40Btu/(ft² ·s)</td><td colspan=\"2\">高热通量 800Btu/(ft²·s)</td></tr><tr><td>质量损失速率 /[1b/(ft²·s)]</td><td>烧蚀速率 /(μm/s)</td><td>质量损失速率 /[lb/(ft²·s)]</td><td>烧蚀速率 /(μm/s)</td></tr><tr><td>室温固化的甲基硅橡胶(液体)</td><td>1.47</td><td>0.18</td><td>0.0046</td><td>15</td><td>0.60</td><td>1975</td></tr><tr><td>室温固化甲基硅橡胶</td><td>1.3</td><td>0.14</td><td>0.0074</td><td>27.5</td><td></td><td></td></tr><tr><td>室温固化的甲基硅橡胶(海绵状)</td><td>1.1</td><td>0.10</td><td>0.0079</td><td>42.2</td><td></td><td></td></tr><tr><td>热固化甲基硅橡胶</td><td>1.11</td><td>0.16</td><td>0.007</td><td>25.0</td><td>0.5</td><td>2000</td></tr><tr><td>室温固化甲基苯基硅橡胶</td><td>1.20</td><td>0.15</td><td>0.0048</td><td>19.25</td><td>0.49</td><td>2000</td></tr><tr><td>室温固化甲基苯基硅橡胶</td><td>1.42</td><td>0.19</td><td>0.0046</td><td>15.75</td><td></td><td></td></tr><tr><td>室温固化甲基苯基硅橡胶（苯 基含量高)</td><td>1.34</td><td>0.15</td><td>0.008</td><td>30.0</td><td>0.16</td><td>575</td></tr><tr><td>热固性甲基苯基硅橡胶（苯基 含量高)</td><td>1.28</td><td>0.12</td><td>0.007</td><td>25.0</td><td>0.13</td><td>500</td></tr></table></body></html>\n\n注： $1\\mathrm{ft}{=}0.3048\\mathrm{m}$ ；1lb=0.4536kg； $t/{'}\\mathrm{C}={\\frac{5}{9}}(t/{'}\\mathrm{F}-32)$ ； $\\mathtt{1B t u=1O S5,0E J}$ 目  \n\n这类产品在固化过程中还会有一些副产物生成，如含有硅酸乙酯的双组分在固化时会有乙醇放出，单组分在固化时也有少量的挥发物放出来，如几种常用的系统中乙酰氧基硅烷会放出醋酸，酮硅烷会产生酮，酰胺基硅烷会放出相应的羧酸氨化物，而硅胺烷则主要放出胺，所以在选择应用时应当考虑所放出的这些副产物的臭味、化学特性和毒性造成的影响。  \n\n$\\textcircled{3}$ 第三类具有不同官能基的聚合物在可控制的速度下相互反应。如甲硅烷基与硅原子上的乙烯基或烯丙基在含铂的催化剂存在下进行氢硅烷化加成反应。  \n\n$$\n\\begin{array}{r}{\\begin{array}{c c c}{\\mathbf{R}}&{\\mathbf{R}^{2}}&{\\mathbf{R}^{2}}\\\\ {\\longrightarrow\\underset{\\mathbf{R}^{1}=\\mathrm{CH}=\\mathrm{CH}_{2}\\mathrm{~+~\\underset{\\mathbf{R}^{1}=\\mathrm{~\\sum~\\left\\{~\\sum~\\left\\{~\\sum~\\left\\{~\\sum~\\alpha~\\alpha~\\alpha~\\overset{\\alpha~\\right\\}~}{~}}~}}{\\mathrm{R}^{3}}~\\mathrm{Re}^{-\\mathrm{i\\mathrm{\\mathrm{R}}^{\\mathrm{R}}}}~\\mathrm{Re}^{\\mathrm{i\\mathrm{R}}}}}{\\mathrm{R}^{1}}}}&{\\underset{\\mathbf{R}^{1}}{\\mathrm{\\mathrm{R}}^{2}}}&{\\mathbf{R}^{2}}\\\\ {\\mathbf{R}^{1}}&{\\mathbf{R}^{3}}&{\\mathbf{R}^{1}}\\end{array}\\right.}\\end{array}\n$$  \n\n这类硅橡胶的固化速度对温度十分敏感，通常是双组分的。在施工以后，其固化过程于室温下是逐渐进行的，而如果加热到 $100^{\\circ}C$ 左右，则固化过程可在数分钟内完成。  \n\n硅橡胶在高温绝热和烧蚀涂料中应用很普遍。如飞机上接近发动机舱的蒙皮保护涂料，火箭排气喷管周围的保护涂料，以及发射台上各种装置和设备的保护涂料。也可用于火箭外壳和喷管之间的保护涂料和飞船重返大气时的保护涂料。  \n\n（2）有机硅树脂这类聚合物和硅橡胶不同的地方是硅树脂中具有很高的潜在交联度。因此在完全固化以后会形成一种较硬和弹性很小的产物，其玻璃转化温度约 $200^{\\circ}C$ ，所以为了施工应用方便和为了防止过早固化，必须将树脂制成溶液的形式。  \n\n根据硅原子上取代基的不同，可以获得各种性能的树脂。例如当甲基的含量高时，树脂具有很好的挠曲性、防水性、低温挠曲性、耐化学性、耐电弧性、抗热冲击、保光性、快干性和紫外光及红外光稳定性等。而如果苯基含量高的话，则树脂具有很好的热稳定性、抗氧化性、热塑性、抗热老化性，机械强度高、气干性能好和溶解度高等特点。表3-9-16中列出了硅原子上各种取代基在 $250^{\\circ}C$ 的空气中半数基团被氧取代所需要的时间。  \n\n有机硅树脂一直被用作高温下使用的涂料成膜物，当加有铝粉颜料以后，可以在550℃的高温下用作金属烟因和类似设备的长期保护涂料。  \n\n表3-9-16 硅原子上各种取代基的热稳定性  \n\n\n<html><body><table><tr><td>硅原子上的基团类型</td><td>在250℃空气中占半数基团 被氧取代所需要的时间/h</td><td>硅原子上的基团类型</td><td>在250℃空气中占半数基团 被氧取代所需要的时间/h</td></tr><tr><td>苯基</td><td>>100000</td><td>壬基</td><td>8</td></tr><tr><td>甲基</td><td>>10000</td><td>癸基</td><td>12</td></tr><tr><td>乙基</td><td>6</td><td>十二烷基</td><td>8</td></tr><tr><td>丙基</td><td>2</td><td>十八烷基</td><td>26</td></tr><tr><td>丁基</td><td><2</td><td>环己基</td><td>40</td></tr><tr><td>戊基</td><td>4</td><td>乙烯基</td><td>101</td></tr></table></body></html>  \n\n有机硅树脂虽有很好的热稳定性和电性能，但它的附着力差、弹性不好，并且耐化学性差，如耐酸、耐碱、耐溶剂性、固化性能。为了制取有全面性能的聚合物，通常采用各种树脂改性的方法，达到扬长避短、提高性能的效果。  \n\n$\\textcircled{1}$ 有机硅玻璃树脂美国Cwens-Illinois公司研制出一类高度交链的有机硅树脂，这种树脂是由三官能度有机硅单体如甲基三乙氧基硅烷或苯基三乙氧基硅烷一起进行水解并预聚物时产物的胶化，为此，所用单体需预先进行精制以降低其酸度。为了避免预聚物胶化，可在预硫化时加人少量六甲基二硅氮烷控制预聚物的酸度。  \n\n这种树脂透明、极硬，是用作耐磨表面涂层的优良材料，现已用于波音707超高速飞机和洛克希德1011三星喷气机的风挡涂层，避免了因航空玻璃树脂的拉伸有机玻璃板经几分钟后就模糊不清，而涂层为玻璃树脂的则虽经8h连续试验仍然清晰可见。该涂层可以保持甚至改进透明材料的光学性能，而且可以保护有机玻璃、聚碳酸酯等基材不受有机溶剂的侵蚀。  \n\n② 硅亚苯醛基聚合物美国联合碳化公司研究了一类含有亚苯基亚苯醚链节的有机硅聚合物。其结构式如下：  \n\n$$\n\\left[\\begin{array}{c c c c c}{\\mathbf{C}\\mathbf{H}_{3}}&{\\mathbf{C}\\mathbf{H}_{3}}&{\\mathbf{C}\\mathbf{H}_{3}}&{\\mathbf{C}\\mathbf{H}_{3}}&{\\mathbf{C}\\mathbf{H}_{3}}&{\\mathbf{C}\\mathbf{H}_{3}}\\\\ {-(\\mathbf{K}_{3}^{\\prime}-\\mathbf{C})-0-\\bigcup_{=}^{\\infty}-\\bigcup_{=}^{\\infty}-\\underset{\\stackrel{\\mathrm{CH}_{3}}{\\mathrm{CH}_{3}}}{\\overset{\\mathrm{Hi.}}{\\big{\\big{\\big{\\big{\\mathrm{CH}}_{3}}}}}}(\\underset{\\mathrm{CH}_{3}}{\\big{\\big{\\big{\\big{\\big{\\big{S H}}_{3}}}}}}+\\underset{\\stackrel{\\mathrm{CH}_{3}}{\\big{\\big{\\big{\\big{\\big{\\mathrm{CH}}_{3}}}}}}}{\\overset{\\mathrm{Hi.}}{\\big{\\big{\\big{\\big{\\big{\\mathrm{CH}}_{3}}}}}}}+\\underset{\\stackrel{\\mathrm{Hi.}}{\\big{\\big{\\big{\\big{\\big{\\mathrm{SH}}_{3}}}}}}}{\\big{\\big{\\big{\\big{\\big{\\big{\\mathrm{CH}}_{3}}}}}}}-\\underset{\\stackrel{\\mathrm{Hi.}}{\\big{\\big{\\big{\\big{\\big{\\mathrm{SH}}_{3}}}}}}}{\\big{\\big{\\big{\\big{\\big{\\big{\\big{\\mathrm{H}}_{3}}}}}}}}}\\right]}\\end{array}\\right]\n$$  \n\n该聚合物是由端基为硅醇基的亚苯基和亚苯醚基单体和含乙烯基的单体在碱性催化剂的存在下共缩合而成的。这是一种热固性的聚合物，固化温度为100～250℃。取决于所用固化催化剂的分解温度。所得为一种无规共聚物，其分子量约为 $1000000{\\sim}3000000$ 费  \n\n这种聚合物具有优良的耐Y射线的降解作用和高的拉伸强度，经4×108rad（lrad=10mGy）的射线照射以后，弹性不变。并可在250℃的温度下长期使用。因此这种聚合物可广泛用在有 $\\gamma$ 射线辐射的地方作涂料和封闭剂的组成。  \n\n$\\textcircled{3}$ 硅亚苯基聚合物普通的硅亚芳基聚合物均为无规结构，当硅氧烷链节增长时会相应地降低其热稳定性。而当亚芳基键节增长时，又提高了聚合物的结晶度，限制了其在低温范围的使用。采用有规亚芳基聚合物就可以克服这一矛盾。一般采用亚芳基二硅醇和环氮氧烷共聚合而得。亚基芳二硅醇可以由钠缩合法或格氏试剂法制得，环硅氮氧烷可由 $a_{2},\\phi$ 二氯硅氧烷和胺在石油醚中反应而制得。  \n\n美国国家航空和宇宙航行局对一系列有规硅亚芳基聚合物进行了研究。其中最典型的是亚苯基有规聚合物，如  \n\n$$\n\\frac{\\Gamma(\\dot{\\mathrm{H}}_{3}}{\\mathrm{[}\\dot{\\mathrm{Si}}}\\langle\\stackrel{\\mathrm{CH_{3}}}{\\mathrm{[}\\dot{\\mathrm{~\\sum~}}}+\\stackrel{\\mathrm{CH_{3}}}{\\mathrm{[}\\dot{\\mathrm{~\\sum~}}}])_{4}+\\mathrm{CH_{3}N H_{2}}}{\\mathrm{CH_{3}}}\n$$  \n\n反应物在 $160{\\sim}180^{\\circ}\\mathrm{C}$ 反应 $4\\sim8\\ensuremath{\\mathrm{h}}$ 所得聚合物的玻璃转化温度可达 $-72^{\\circ}C$ ，最低可达$-80^{\\circ}C$ ，热稳定性在 $500^{\\circ}C$ 以上，而无规硅芳基聚合物的热稳定性只能达到 $380^{\\circ}\\mathrm{C}$ 左右。一般二甲基硅氧烷链节超长其挠曲性增加，而热稳定性下降。在亚芳基中亚苯醚基的热稳定性比亚苯基好。这类聚合物是制造化学稳定的、力学性能好和耐热涂料所不可缺少的材料。  \n\n美国海军航空系统对硅亚苯基聚合物在高速飞机上用作抗雨腐蚀涂料的应用研究方面进行了大量的工作。例如，采用1，4-双(二甲基羟基硅基)苯与双(二甲基氨基)二甲基硅烷可制成一种能在室温下固化的极强的弹性体，其玻璃转化温度为一 $62^{\\circ}C$ ，反应如下所示。经试验这种涂料的弹性比氯丁橡胶和聚氨酯都好，并可在 $250^{\\circ}C$ 下稳定。  \n\n![](images/b85d98eaee14c7eacec88cc95d26c8db62854cbec669c046847f46622888aa40.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 810,
+        "chunk": "# 2.酚醛树脂  \n\n酚醛树脂从20世纪60年代起就作为耐高温和耐烧蚀材料应用的主要品种之一，它具有价格低廉、工艺性良好的优点，至今仍用作树脂基烧蚀材料的主要成膜物树脂之一。随着空间技术的迅速发展，对耐烧蚀材料的树脂基体耐热性和耐烧蚀性提出了更高的要求，一般酚醛树脂难以满足这些要求，因此改性和合成新型结构的酚醛树脂就成了耐烧蚀材料研究的热点。  \n\n采用芳烃（甲苯、二甲苯、苯、萘等)、硼酸、磷化合物（磷酸、磷酸锆、氯化氧磷等)、钼酸、马来酰亚胺、有机硅、胺（三聚氰胺、苯胺等)、酚噻嗪、苯并嗪等化合物改性，在酚醛树脂分子结构中引人官能团，经加成、环化、开环、聚合等合成了含新结构单元的耐烧蚀酚醛树脂，使其具有固化时不放出或少量放出小分子、热稳定性优异、残炭率高的特点。其中有机硅改性酚醛树脂的复合涂层，最高温度可达 $820^{\\circ}C$ ，而残炭率还大于 $70\\%$ 改性明显，为合成新型的耐烧蚀酚醛树脂开辟了新的途径。也为其发展指出了新方向。相关报道较多，这里不再赘述。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 811,
+        "chunk": "# 3.环氧有机硅树脂  \n\n环氧树脂具有优越的物理机械性能和防腐蚀能力，并且具有良好的工艺性能，但环氧树脂的耐热性能要逊于有机硅树脂和酚醛树脂。虽然双酚A型环氧树脂的分子结构中含有大量苯环，从结构上来看，似乎符合耐热性树脂的要求，可是由于其分子中的化学键主要由C—C、C—O以及C—H等化学键组成，这是树脂耐热性能有限的根本原因；这是环氧树脂很少单独作为消融隔热涂料的成膜物树脂的原因之一；另外一个重要的原因是环氧树脂的烧蚀成碳率很低，只有20%以下，故通常是和其他有机树脂配合使用，充分利用环氧树脂优越的力学性能、防腐蚀性能和工艺性能，以弥补像有机硅树脂、酚醛树脂等存在的不足。环氧树脂与多种树脂都具有良好的相容性，但为了得到最佳性能，多采用有机硅改性、酚醛树脂改性。  \n\nGeradol等人研究了环氧树脂改性结果和消融性能之间的关系，发现热塑性酚醛树脂改性环氧树脂性能良好。同时，新型环氧固化剂的研究和选择也十分重要，Robert等人用磷酸酰胺为固化剂，其消融性能优于酚醛-碳的复合制品；Poul用磷钼酸和含羟基的磷酸酯作为环氧化酚醛树脂的固化剂，得到的产品在林德（Lindetorch）火焰下检验，其性能不亚于酚醛尼龙材料。  \n\n环氧树脂经有机硅改性后可显著提高其消融防热性能，Engel采用硅树脂和环氧树脂冷拼后制得反弹道导弹的外部防热涂料；国内如Yj-66A、NHS-55等防热涂料，均得到极为优异的综合性能，可以代替酚醛树脂，已经获得成功的应用，相关研究单位并在此基础上进行了大量的改性研究，进一步提高了涂层的隔热、耐烧蚀和力学性能，并在国内最新型号武器上获得应用。这里重点介绍有机硅改性环氧涂料。  \n\n（1）有机硅改性环氧树脂的现状有机硅改性环氧树脂是特种涂料用树脂中用途最广的品种之一，其发展和使用已有较长历史，各国对有机硅改性环氧树脂的研究也非常活跃，已有不少品种及型号。国外以道康宁公司为代表。其主要品种见表3-9-17。使用环境涵盖了$120{\\sim}760^{\\circ}C$ 温度范围，树脂品种系列化，可以满足不同环境的使用要求。  \n\n表3-9-17 美国道康宁公司环氧树脂改性有机硅树脂品种  \n\n\n<html><body><table><tr><td>使用温度</td><td>有机硅比例/%</td><td>产品商业牌号</td></tr><tr><td>425～540°C(800~1000°F)</td><td>90~100</td><td rowspan=\"4\">Dow Corning @ 805 Resin(Soft)</td></tr><tr><td>540～760℃(1000～1400°F)</td><td>100</td></tr><tr><td>315~425℃(600~800°F)</td><td>50~90</td></tr><tr><td>425～540℃(800~1000F)</td><td>90~100</td></tr><tr><td>540～760°℃（1000～1400°F)</td><td>100</td><td rowspan=\"3\">Dow Corning  806 Resin(Hard)</td></tr><tr><td>315~425℃(600~800F)</td><td>50~90</td></tr><tr><td>120~200℃(250~400°F)</td><td>15~30</td></tr><tr><td></td><td></td><td rowspan=\"2\">Dow Corning ? 840 Resin</td></tr><tr><td>200～315℃(400~600°F)</td><td>30~50</td></tr></table></body></html>  \n\n国内原化工部涂料研究所最早开展这方面的研究和应用，形成了几个环氧改性有机硅树脂品种，其技术水平与国外产品相当，多年来一直处于国内领先的地位。20世纪80年代后期，由于受国内大环境的影响，该技术所需的主要原材料（如苯基甲基烷氧基硅烷）出现无货源的局面，致使国内在这方面的研究工作一直处于一种停滞的状态。直到21世纪初，该领域的研究和应用重新得到重视，国内很多单位都展开环氧有机硅树脂的研究和应用工作，代表性的有北方涂料工业研究设计院（原化工部涂料研究所)，海洋化工研究院和中船725所等单位。  \n\n随着技术的发展、新型原材料的出现和工艺改进，环氧有机硅树脂的合成工艺路线也得到相应的发展，以耐热性能为主的树脂性能进一步得到提高。随着技术进步和工艺成熟，产品的性能稳定、成本下降，环氧有机硅树脂的应用不仅仅局限于军工领域的应用，还可以推广应用于民用行业。  \n\n(2）有机硅改性环氧树脂的合成途径制备有机硅改性环氧树脂有如下4种途径。  \n\n①环氧丙醇与烷氧基聚硅氧烷（有机硅树脂的烷氧基与环氧丙醇的羟基反应）脱醇反应。  \n\n$$\n\\equiv\\mathrm{SiOR~+~\\underbrace{CH_{2}-C H C H_{2}O H}_{O}~{\\longrightarrow~\\underbrace{C H_{2}-C H C H_{2}O S i=\\Gamma+R O H}_{O}}}\n$$  \n\n该途径是以 $\\mathbf{Si-OC}$ 键引入环氧结构，产品耐水性差。  \n\n$\\textcircled{2}$ 缩水甘油烯丙醚与含氢聚硅氧烷（含氢有机硅树脂）起加成反应。 $\\begin{array}{r}{\\begin{array}{c c}{\\equiv\\S\\mathrm{i}\\mathrm{-}\\mathrm{H}+\\underbrace{\\mathrm{CH}_{2}\\mathrm{-}\\mathrm{CH}\\mathrm{CH}_{2}\\mathrm{CH}_{2}\\mathrm{CH}\\mathrm{-}\\mathrm{CH}_{2}}_{\\mathrm{O}}\\longrightarrow\\underbrace{\\mathrm{CH}_{2}\\mathrm{-}\\mathrm{CH}\\mathrm{CH}_{2}\\mathrm{OCH}_{2}\\mathrm{CH}_{2}\\mathrm{Si}\\equiv\\mathrm{0}}_{\\mathrm{O}}}\\end{array}}\\end{array}$  \n\n$\\textcircled{3}$ 过乙酸与乙烯基有机硅树脂的不饱和双键起氧化反应。  \n\n$$\n\\mathrm{CH_{2}}\\mathrm{-CH\\mathrm{-}R\\mathrm{-}\\Sigma\\Sigma\\Sigma}\\mathrm{-}\\mathrm{+}\\mathrm{CH_{3}C O O O H\\mathrm{-}\\Sigma\\Sigma\\Sigma}\\mathrm{CH_{2}\\mathrm{-}C H\\mathrm{-}R\\mathrm{-}\\Sigma\\Sigma}\\mathrm{+}\\mathrm{CH_{3}C O O H}\n$$  \n\n$\\textcircled{4}$ 双酚A型环氧树脂与含Si—OR、Si-OH基团的聚硅氧烷起缩合反应，主要有以下3种形式。  \n\na.含Si一OR的聚硅氧烷与环氧树脂中的C—OH发生脱醇反应。  \n\nb.聚硅氧烷中的Si—OH与环氧树脂的C一OH发生脱水反应，  \n\nc.聚硅氧烷中的 $s_{\\mathrm{i}}\\mathrm{-}\\mathrm{-}\\mathrm{OH}$ 与环氧树脂中的环氧基发生开环反应。  \n\n$$\n-\\frac{1}{\\Gamma}\\Bigg\\downarrow0\\mathrm{\\bfH_{\\ell}}+\\mathrm{\\bf\\Phi}\\mathrm{CH_{2}}\\mathrm{-}\\mathrm{CH-R}\\longrightarrow-\\frac{1}{1}\\mathrm{-}0\\mathrm{-}\\mathrm{CH_{2}-C H-R}\n$$  \n\n前三种改性途径制备的有机硅改性环氧树脂实际应用已不大，在工业一般采用第四种途径，根据实际使用要求选择适宜的环氧树脂与有机硅树脂进行共缩聚反应，制得的有机硅改性环氧树脂具有原料易得、方法简单的优点。  \n\n目前，常用的 ${\\mathfrak{f o s}}{\\mathfrak{s}}^{*}$ 环氧改性有机硅树脂和HW-28环氧改性有机硅树脂是硅氧烷的羟基（或烷氧基）与环氧树脂的仲羟基缩合反应化合物。这类环氧有机硅树脂分子中保留环氧基，可选用环氧树脂固化剂使其进行交联固化。  \n\n(3）化学改性与物理共混的区别树脂改性还可以采用冷拼法，将环氧树脂与有机硅树脂直接混合，现在很多报道的环氧改性有机硅树脂的应用就是采用冷拼技术。通过该方法得到的环氧有机硅树脂性能得到改善，可以满足一些环境条件下的使用。笔者曾经做过相关大量的对比研究工作，将某些市售的环氧有机硅树脂与自制的环氧有机硅树脂进行了性能比较发现，二者在常规性能方面差异不是很大，但是在耐温性能、耐温以后的力学性能以及耐烧蚀性能等方面，化学改性的环氧有机硅性能明显优于物理共混的环氧有机硅树脂。而且，二者在胶化点上（胶化点测定条件：250℃士2℃）也存在明显差异，前者的胶化点在20min以上，甚至难以测定，而化学改性的环氧有机硅树脂的胶化点为3min以内，且该指标是树脂合成时的终点控制指标。  \n\n采用物理共混与化学改性两种方法得到的环氧有机硅树脂的清漆性能比较见表3-9-18。  \n\n表3-9-18 两种改性方法得到的环氧有机硅树脂的清漆性能比较  \n\n\n<html><body><table><tr><td rowspan=\"2\">序号</td><td colspan=\"2\" rowspan=\"2\">检验项目</td><td colspan=\"2\">技术指标</td></tr><tr><td>冷拼法</td><td>化学共聚法</td></tr><tr><td>1</td><td colspan=\"2\">树脂液外观</td><td>浅黄色、微浑近透明</td><td>浅黄色透明</td></tr><tr><td>2</td><td colspan=\"2\">固体分/%</td><td>50±2</td><td>75±2</td></tr><tr><td>3</td><td colspan=\"2\">干燥时间(实干)/h</td><td>2.5</td><td>1.5</td></tr><tr><td>4</td><td colspan=\"2\">附着力/级</td><td>1</td><td>1</td></tr><tr><td>5</td><td colspan=\"2\">柔韧性/mm</td><td>1</td><td>１</td></tr><tr><td>6</td><td colspan=\"2\">冲击强度/cm</td><td>50</td><td>50</td></tr><tr><td rowspan=\"5\">7</td><td rowspan=\"5\">260°℃，4h后</td><td>附着力/级</td><td>2~3</td><td>1</td></tr><tr><td>柔韧性/mm</td><td>无法测定</td><td>2~3</td></tr><tr><td>冲击强度/cm</td><td>≤20</td><td>40~50</td></tr><tr><td>颜色</td><td>几乎呈黑色</td><td>浅茶色</td></tr><tr><td></td><td></td><td></td></tr></table></body></html>  \n\n烧蚀防热涂料性能比较如下。  \n\n$\\textcircled{1}$ 颜基比都为 $1:1$ 左右，相同的填料体系，以及其他添加剂也相同。  \n\n$\\textcircled{2}$ 操作条件相同，但是，配料时发现冷拼树脂黏性差，不能很好地浸润包裹填料，而化学改性树脂则不存在此现象。  \n\n$\\textcircled{3}$ 化学改性树脂涂料在 $\\mathtt{24h}$ 后即可基本实干，可打磨，而冷拼树脂涂料 $72\\mathrm{h}$ 后涂膜仍发黏，涂膜发软不能打磨， $80\\%$ 烘 $\\mathtt{12h}$ 后方可打磨。  \n\n$\\textcircled{4}$ 打磨时化学改性树脂涂层较硬和密实，而冷拼树脂涂层则较疏松。  \n\n$\\textcircled{5}$ 线烧蚀率和质量烧蚀率（烧蚀时间30s）线烧蚀率（ $\\bf{m m}/{s})$ ：化学改性树脂涂层0.067冷拼树脂涂层0.20  \n\n质量烧蚀率 $[{\\bf g}/(\\mathrm{cm}^{2}\\cdot{\\bf s})]$ ：化学改性树脂涂层0.012冷拼树脂涂层0.025  \n\n$\\textcircled{6}$ 烧蚀后涂层状态化学改性树脂涂层炭化层密实，有细小熔珠，驻点较浅，打磨时感到炭化层坚硬，有一定强度；而冷拼树脂涂层的炭化层明显呈疏松状，熔珠较大且多，驻点也较深，打磨时明显感到炭化层软，几乎呈粉状，基本失去强度。  \n\n在涂层厚度相近、烧蚀时间相同情况下，化学改性树脂涂层表面形成炭化层，而下面的涂层可以基本保持不被烧蚀，仍可很好地保护基材，冷拼树脂涂层整个都会被烧蚀，烧蚀后涂层无保护作用。  \n\n两种树脂性能比较结论如下：  \n\n$\\textcircled{1}$ 两种树脂常温条件下的力学性能相当；  \n$\\textcircled{2}$ $260^{\\circ}C$ ，4h后冷拼树脂的力学性能下降非常厉害；  \n$\\textcircled{3}$ 烧蚀后，两种涂层性能差别很大。  \n试验结果表明，冷拼树脂不宜作为耐高温烧蚀涂料的基料树脂使用。  \n\n![](images/9fff77612e305b9082f88fe1493a8db33c2886667eb8c396c7442fa71ffd61c7.jpg)  \n\n1.1 -",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 812,
+        "chunk": "# 一、概述  \n\n上一节已经介绍了消融隔热涂料，它是通过“牺牲”自身来达到隔热和保护基材的目的，但是，还存在另一种情况，就是涂料使用环境不允许涂料发生消融作用，或者使用环境的温度条件远远达不到涂料发生消融所需要的温度条件，这时消融型隔热涂料就不能适应；这就需要一种特殊涂料——隔热保温涂料，就是本节将要介绍的内容。",
+        "category": " Introduction"
+    },
+    {
+        "id": 813,
+        "chunk": "# 1.隔热保温涂料的分类及用途  \n\n目前，隔热保温涂料的分类还没有一个统一的标准，根据涂料隔热保温的机理可以将其分为消融型、反射辐射型、低热导率阻隔型和贮热型。根据隔热涂料采用的成膜物的不同可分为有机隔热保温涂料和无机隔热保温涂料。  \n\n隔热保温涂料可用于军用飞机、火力发电厂、高温设备以及建筑物、贮运设备等。建筑用隔热保温涂料是近年来新兴的功能涂料品种，具有很好的实用价值和前景。隔热保温涂料涂覆于各种设备表面，可满足相应的使用环境条件要求，其关键作用是降低基体的温度，保证设备在高温下正常运行。所以隔热保温涂料的研究和应用得到极度重视。",
+        "category": " Introduction"
+    },
+    {
+        "id": 814,
+        "chunk": "# 2.隔热保温涂料的作用机理  \n\n消融型隔热保温涂料的作用机理在上一节已有详细叙述，这里只叙述反射辐射型、低热导率阻隔型和贮热型三种涂料的作用机理。  \n\n(1）反射、辐射机理任何物质都具有反射或吸收一定波长电磁波的特性，反射型涂料的基本原理是通过涂料中颜料、填料的粒子将可见光和红外反射到外部空间，从而降低物体自身温度，对于反射型隔热涂料而言，涂料反射性能与厚度没有关系。  \n\n辐射型隔热保温涂料，是通过辐射形式把吸收的电磁波（热）以一定波长发射到外部空间中去，从而达到良好的隔热保温效果。  \n\n由于辐射型隔热涂料是通过将吸收的热转化为热反射电磁波辐射出去，从而达到隔热的目的，因此，该类涂料的技术关键是选用具有高热发射率的物质，如FeO3、MnOz、CoO3和CuO等金属氧化物掺杂形成的具有反尖晶石结构的物质，其具有热发射率高的特征，是重要的辐射型隔热填料，也是实现涂料隔热的主要方法和手段。研究表明，辐射型散热主要是以红外辐射的形式，在波长为8～13.5μm的范围内，涂料的发射率尽可能高，就可以将物体表面的热量以红外辐射的形式高效地发射到外部空间，达到很好的隔热目的。  \n\n通过在硅酸盐结晶相中加人AlzO3、TiOz等金属氧化物粉末作为填料，制备的辐射型隔热涂料，其在5～15um的波段内，红外辐射能量大于85%。  \n\n(2）低热导率阻隔型涂料作用机理热导率（）是物体或材料传导热量能力的大小，入越大，物体的导热性能越好；入越小，隔热性能越好。一般材料的热导率在0.03～3.50W/(m·K)，而只有入小于0.25W/（m·K）才被用于隔热材料。  \n\n热导率是材料结构的函数，与材料的内部结构有关。如材料的密度越大，其导热性越好，热导率越大。对于含有空隙的材料，其热导率决定于材料的空隙率与空隙特征。由于静止空气的热导率极小，所以一般来说，空隙率越大、密度越小，其热导率越小。具有细微和封闭空隙的材料比空隙粗大且连通的材料的热导率小。  \n\n材料的热导率是一个与材料厚度无关的值，为了度量一定厚度材料（如隔热涂料的干膜）的隔热性能，需要引人热阻的概念。热阻是热导率的倒数，表示热量通过厚度为d的材料层所受到的热传递阻力为R（m·K/W)=d/入。热阻的定义用于确定隔热涂料的厚度，具有实际意义。  \n\n众所周知，在常温下静止空气的热导率约为 $0,023\\mathbf{W}/(\\mathbf{m}\\cdot\\mathbf{K})$ ，认为是最小的，其他材料（隔热涂料）的热导率不可能小于 $0.023\\mathbf{W}/(\\mathbf{m}\\cdot\\mathbf{K})$ ，但是，随着纳米技术的出现，这一传统的认识在理论上已经不能成立。因为当涂膜中气孔的直径达到纳米级时（如小于$50\\mathrm{nm})$ ，气孔内的空气分子不能对流，也不能像一般静止空气中的分子那样进行布朗运动，即被完全吸附在气孔壁上而不能自由运动，这样的气孔相当于真空状态。如果保持涂料的体积密度及其中的气孔直径足够小，则可以使得涂料的分子振动传热和对流传热接近于0；另一方面，众多足够小的微孔使得涂料界面的数量趋向于无穷多，可以使涂料内部有非常多的反射界面，从而使辐射传热效率趋近于0。从理论上讲涂料的热导率可以趋近于0。因此有可能得到热导率 $\\leqslant0.023\\mathbf{W}/(\\mathbf{m}\\bullet\\mathbf{K})$ 的隔热涂料。  \n\n对于涂料成膜物基体来说，空心玻璃微珠的引人，将会使涂层的热导率更为显著降低。另外，由于采用空心玻璃微珠为填料，形成多空隙的涂层，增加涂层厚度，即就是增加热阻，同样可以达到很好的隔热效果。  \n\n(3）贮热型作用机理贮热型隔热保温涂料的作用机理就是将外界的热量吸收，贮存于涂层内部，从而实现隔热的目的。微观上讲就是在涂料中加人某些特殊物质（如 $\\mathrm{Fe}_{3}\\mathrm{O}_{4}$ 等)，该类物质可以吸收热量而发生能级跌迁，从低能级跃迁到高能级的变化，从而达到隔热的目的。这类隔热涂料是最近几年才见相关报道，主要是用于玻璃贴膜，对太阳光（热）进行反射和隔热，如汽车玻璃反光隔热涂料，也可以用于隐身技术。很显然，由于是通过涂料中的特殊物质吸收并贮存热，其隔热效果是很有限的，对于直接有热源加热的环境下并不适用，所以这类隔热涂料也不作为本节讨论的重点。  \n\n上述对隔热涂料的几种作用机理分别加以简介，但在实际应用中并无严格的界限，往往是多种机理的综合利用，比如反射辐射型隔热涂料同样也有阻隔和贮热机理的运用，只不过是反射辐射隔热的作用效果最为明显，反之亦然。同时，单一的隔热机理都具有各自的优点和局限性，而且因为材料本身的特性和技术工艺条件的限制，很难达到其最为理想的隔热状态和效果，所以，需要多种隔热机理的综合应用，以能扬长避短、优势互补，这也是隔热保温涂料发展的一个方向。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 815,
+        "chunk": "# 二、热控涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 816,
+        "chunk": "# （一）热控涂料的定义、应用和分类",
+        "category": " Introduction"
+    },
+    {
+        "id": 817,
+        "chunk": "# 1.定义  \n\n一个典型的航天器要经历一 $200{\\sim}100^{\\circ}\\mathrm{C}$ 以上的轨道飞行环境，它的工作时间长达几天甚至几年，为保证航天器（卫星、飞船等）的结构及设备在如此恶劣环境下正常工作，必须采取隔热保温（热控）措施，隔热保温涂料是其中应用最为广泛和效果最为显著的一类材料。这里所用的隔热保温涂料即热控涂料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 818,
+        "chunk": "# 2.应用  \n\n航天器热控技术和热控材料是航天技术的重要组成部分，热控技术可以分为主动热控和被动热控两大类；热控材料的种类非常多，半个多世纪以来得到广泛重视和迅速发展，已经  \n\n![](images/511eeba3a28c3dbc4b694df13be6d53ef5c81a7a06933d04be51f85b6e052288.jpg)  \n图3-9-4典型航天器应用热控材料的部位及要求1一天线（低a/涂层）；2一顶绝缘盖（铝-聚酯树脂  \n多层隔热层）；3一飞行实验器（低a/e涂层）；4一太阳传感器（真空沉积铝）；5一隔热桁条（铝箔条加黑涂料）；6一太阳电池方阵底板（玻璃纤维蜂窝结构或导热绝缘涂层）；7一电子元件（黑色涂层和导电底座）；8一仪器平台（高辐射率底面的蜂窝板）；9一热百叶窗（非磁性双金属弹簧）；10一绝热带（铝-聚酯树脂或化合物多层隔热层）；11一太阳电池方阵（带滤光膜的盖玻片及减反射涂层）；12一级间结构（铝箔及玻璃纤维多层隔热）  \n\n研究出了多种热控涂料系统，并广泛应用于航天器的各个部位，如图3-9-4所示，在航天技术的发展中起到了非常重要的作用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 819,
+        "chunk": "# 3.分类  \n\n热控涂料根据材料的性质，可分为金属、无机非金属和有机热控涂料三大类；根据涂料制备工艺方法又可以分为真空沉积薄膜、化学和电化学镀膜、等离子喷涂涂料、熔融烧结以及普通涂料等众多类型，其中普通涂料类热控涂料具有热控效果良好、制备和施工工艺简单可靠、易修复和成本低的优点，得到了广泛的应用。各种热控涂料的重要光学性质 as、E和 $\\alpha_{\\S}/\\varepsilon$ 的范围如图3-9-5所示。  \n\n航天器的热控技术可分为：主动热控和被动热控。热控涂料（Thermalcontrol coatings）是空间飞行器被动热控系统的重要组成部分，其原理是通过调节物体表面的太阳吸收率（as）和红外辐射率（e）来控制物体的热量平衡，属被动式温控。例如在太空中表面镀金的物体受太阳光垂直照射时，其表面平衡温度为425℃，而当物体表面涂有太阳吸收辐射比为as/e=0.25的热控涂料后，其表面平衡温度为5℃。因此航天器表面需涂覆热控涂料，以保证星体安全和星内仪器的正常工作。航天器表面的温度T同热控涂料对太阳的吸收率（as）成正比，和热控涂料的热发射率（e）成反比，T=S(as/∈)1/4，所以正确选择热控涂料的as/e值，是保证航天器处于正常工作温度范围的重要途径。  \n\n热控涂料是根据物质的反射、辐射特性制备而成的，所以根据涂料的吸收辐射比，可以将其分为以下4类。  \n\n（1）低吸收辐射比涂料 低吸收辐射比涂  \n\n料是指涂料具有较低αs和较高值，包括白色有机涂料、白色硅酸盐涂料和金属镀层等，以及附有上述涂料（膜）的塑料薄膜、有机玻璃、石英玻璃和铈玻璃等，这类薄膜和玻璃统称为“二次表面镜”。另外，还有铝合金表面的光亮阳极化膜、AlO3的等离子喷涂料等。  \n\n(2）高吸收辐射比涂料是指具有较高as和较低e值的涂料，主要包括黑色有机涂料、真空沉积干涉膜和黑镍、黑铬、黑铜等电镀层等。  \n\n(3）平吸收涂料该类涂料在所有波长范围内均具有较低的αs和e值，二者之比接近于1。一般的铝粉漆就属于此类型。  \n\n(4）平吸收辐射比涂料 4该类涂料在所有波长范围内均具有较高的αs和e值，二者之比接近于1。铝合金黑色阳极化膜以及一般的黑色涂料均属于此类型。  \n\n![](images/ad076513b13643d8f15e13f55b60568325068d27ca2336a53c699c817dad7c41.jpg)  \n图3-9-5 各种热控涂料的光学性质",
+        "category": " Introduction"
+    },
+    {
+        "id": 820,
+        "chunk": "# （二）热控涂料的组成  \n\n热控涂料主要由成膜物、颜填料和助剂组成，涂覆施工后形成一种光反射、散射热控涂料材料，它借助于其中的细微颜填料粒子对太阳光的反射、散射作用「当颜填料粒子的直径小于人射光波长的1/10时，根据雷利赫（Rayleigh）定律，光将是弥散的」和涂料的红外辐射特性，通过调节涂料的 $\\alpha_{5}$ 和 $\\ E$ 值，就可以达到热控的自的。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 821,
+        "chunk": "# 1.颜填料  \n\n对于热控涂料来说，颜填料不仅是涂料的重要组成部分，而且可通过颜填料的选择，调节涂料的光学性质，是实现涂料热控效果的关键。对于需要低吸收/发射比 $(\\alpha_{S}/E)$ 的热控涂料而言，颜填料应该具有低吸收、高发射、高纯度和高化学稳定性。  \n\n(1）氧化物氧化物有氧化铝，氧化钛，氧化锌，氧化镁，氧化硅，氧化锆，氧化钙，  \n氧化镧，氧化铪，氧化锡，氧化钇，氧化锑，氧化铍，氧化，氧化铈，氧化锯，氧化  \n钼等。(2）硅酸盐硅酸盐有硅酸锆，硅酸镁，硅酸钙，锂铝硅酸盐，钠铝硅酸盐，镁铝硅酸  \n盐等。(3）钛酸盐钛酸盐有钛酸锌，钛酸钡，钛酸锶，钛酸钙，钛酸锂，钛酸镧，钛酸  \n\n等。  \n\n(4）其他其他包括钨酸盐，锡酸盐，锯酸盐，钼酸盐，锆酸盐，硫酸盐，硫化锌，尖晶石，莫来石，透辉石，橄榄石等。  \n\n在进行颜填料选择时，在满足光性能的基础上，颜填料在空间环境下的稳定性也是至关重要的，大部分颜填料经过真空紫外辐照后会引起严重变色，表3-9-19中列出了一些无机颜填料的抗震真空辐照能力以及可见光范围内（波长为 $400{\\sim}600\\mathrm{nm},$ ）的典型反射率。  \n\n表3-9-19 无机颜填料的抗辐照及光学性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">材料</td><td colspan=\"2\">辐照条件</td><td colspan=\"2\">反射率/%</td></tr><tr><td>ESH</td><td>太阳参数</td><td>400nm</td><td>600nm</td></tr><tr><td rowspan=\"2\">Alz O(a型)</td><td>0</td><td></td><td>100.0</td><td>100.0</td></tr><tr><td>180</td><td>3</td><td>74.0</td><td>91.5</td></tr><tr><td rowspan=\"2\">AlO(Y型)</td><td>0</td><td></td><td>93.5</td><td>90.0</td></tr><tr><td>75</td><td>1.5</td><td>49.5</td><td>82.5</td></tr><tr><td rowspan=\"2\">AlzO·2SiO2·2HzO</td><td>0</td><td></td><td>73.0</td><td>84.5</td></tr><tr><td>180</td><td>3</td><td>46.5</td><td>60.0</td></tr><tr><td rowspan=\"2\">AlzO·2SiOz</td><td>0</td><td></td><td>78.0</td><td>87.0</td></tr><tr><td>200</td><td>3</td><td>65.0</td><td>81.0</td></tr><tr><td rowspan=\"2\">3AlO·2SiO+SiOz</td><td>0</td><td></td><td>84.5</td><td>86.5</td></tr><tr><td>180</td><td>3</td><td>75.5</td><td>84.5</td></tr><tr><td rowspan=\"2\">Sbz O3</td><td>075</td><td></td><td>92.5</td><td></td></tr><tr><td></td><td>1.5</td><td></td><td>96. 5</td></tr><tr><td rowspan=\"2\">CaSiO(合成)</td><td>0</td><td></td><td>86.0</td><td>90.0</td></tr><tr><td>75</td><td>1.5</td><td>58.0</td><td>81.0</td></tr><tr><td rowspan=\"2\">CaSiO (硅灰石）</td><td>0</td><td></td><td>92.5</td><td>94.5</td></tr><tr><td>75</td><td>1.5</td><td>81.0</td><td>91.5</td></tr><tr><td rowspan=\"2\">MgAlzO4</td><td>0</td><td></td><td>97.5</td><td>97.0</td></tr><tr><td>75</td><td>1.5</td><td>70.0</td><td>92.5</td></tr><tr><td rowspan=\"2\">Mg0</td><td>0</td><td></td><td>98.5</td><td>98.5</td></tr><tr><td>75</td><td>1.5</td><td>71.0</td><td>92.5</td></tr><tr><td rowspan=\"2\">MgOSiO·nHzO</td><td></td><td></td><td>89.0</td><td>92.0</td></tr><tr><td>180</td><td>3</td><td>62.0</td><td>73.5</td></tr><tr><td rowspan=\"2\">2MgOSiOz</td><td>0</td><td></td><td>33.0</td><td>59.0</td></tr><tr><td>1036</td><td>1.5</td><td>35.5</td><td>60.0</td></tr><tr><td rowspan=\"2\">SiO2</td><td>0</td><td></td><td>88.5</td><td>92.5</td></tr><tr><td>75</td><td>1.5</td><td>77.5</td><td>90.0</td></tr><tr><td rowspan=\"2\">SiOz</td><td>0</td><td></td><td>92.0</td><td>93.5</td></tr><tr><td>180</td><td>3</td><td>87.5</td><td>93.0</td></tr><tr><td rowspan=\"2\">SnOz</td><td>0</td><td></td><td>88.0</td><td>90.0</td></tr><tr><td>300</td><td>3</td><td>78.5</td><td>88.0</td></tr><tr><td rowspan=\"2\">ZrOz</td><td>0</td><td></td><td>92.5</td><td>97.0</td></tr><tr><td>75</td><td>1.5</td><td>65.5</td><td>90.5</td></tr><tr><td rowspan=\"2\">ZrO2</td><td>0</td><td>3</td><td>88.0</td><td>95.5</td></tr><tr><td>180</td><td></td><td>33.0</td><td>73.5</td></tr><tr><td rowspan=\"2\">ZrSiO4</td><td>0</td><td>3</td><td>86.5</td><td>92.5</td></tr><tr><td>180</td><td></td><td>65.0</td><td>84.5</td></tr><tr><td rowspan=\"2\">ZnS</td><td>07</td><td>1.5</td><td>91. 0</td><td>94. 5</td></tr><tr><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n高南曾采用直观方法对国产各种颜填料进行真空紫外辐照试验筛选。试验方法：将颜填料置于铜或铝制小盘中，盖上石英玻璃片，进行真空紫外辐照试验，真空度 $3\\times10^{-4}\\sim9x$  \n\n10-5Torr（1Torr=133.322Pa)，500W高压汞灯辐照50h后，观察其变色情况。结果如表3-9-20所示。其中锆英石和碳酸钙最稳定，氧化锌、氧化硅和氧化锆次之，其余颜填料变色均比较严重。  \n\n表3-9-20 颜填料粉末紫外辐照试验结果  \n\n\n<html><body><table><tr><td rowspan=\"2\">颜填料</td><td rowspan=\"2\">纯度</td><td colspan=\"2\">紫外辐照前后的颜色变化</td><td rowspan=\"2\">变化级别</td></tr><tr><td>辐照前</td><td>辐照后</td></tr><tr><td>A1O3</td><td>α型99.99%</td><td>白</td><td>灰</td><td>大</td></tr><tr><td>MgO</td><td>由镁条熏制</td><td>白</td><td>灰</td><td>大</td></tr><tr><td>SnO2</td><td>CP级，99.5%</td><td>白</td><td>灰</td><td>大</td></tr><tr><td>CeOz</td><td>CP-3级，96%</td><td>浅黄</td><td>棕</td><td>大</td></tr><tr><td>PbO</td><td>CP-3级，98%</td><td>黄</td><td>黑</td><td>大</td></tr><tr><td>TiO2</td><td>CP-3级，98.5%</td><td>乳白</td><td>深灰</td><td>大</td></tr><tr><td>CaO</td><td>AR-2级</td><td>白</td><td>灰</td><td>大</td></tr><tr><td>ZrO2</td><td>≥99%</td><td>灰白</td><td>灰</td><td>中</td></tr><tr><td>ZrSiO4</td><td>锆英石</td><td>米色</td><td>米色</td><td>小</td></tr><tr><td>ZrSiO4</td><td>锆英石</td><td>灰</td><td>灰</td><td>小</td></tr><tr><td>CaCO3</td><td>AR级，≥99%</td><td>白</td><td>白</td><td>小</td></tr><tr><td>ZnO</td><td>CP级，98.5%</td><td>白</td><td>灰白</td><td>中</td></tr><tr><td>SiO</td><td>99.75%</td><td>白</td><td>淡黄</td><td>中</td></tr><tr><td>KO·3SiOz</td><td>一</td><td>白</td><td>灰白</td><td>中</td></tr></table></body></html>  \n\n研究认为，天然混合型矿物的抗真空紫外辐照的能力要好于人工合成的化合物，例如天然硅灰石的抗辐照性能要比合成的硅酸钙好，当然也有例外，如氧化锌和氧化锡则相反。某些含水矿物如高岭土和滑石经过高温烧后可以提高其稳定性，但是氧化铝、氧化锆和锆英石在 $1000^{\\circ}C$ 烧16h，对其稳定性影响不大。同一种物质由于结晶形态不同，其稳定性差别也比较大。  \n\n颜填料的稳定性和光学性能对于热控涂料而言，是至关重要的，人们为了获得低 $\\alpha_{\\mathrm{S}}/\\varepsilon$ 比的热控涂料，对颜填料在热控涂料中降解机理、防止光降解的措施、采用人工合成单晶和超纯的多晶物质作颜料、为提高颜料的热稳定性进行热处理等做了大量的研究工作，已经取得了令人满意的结果。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 822,
+        "chunk": "# 2.成膜物  \n\n成膜物树脂是涂料的基本组成部分，一是有机成膜物，如聚硅氧烷、环氧树脂、丙烯酸树脂等；二是无机成膜物，如水玻璃（硅酸钾、硅酸钠、硅酸锂等）、硅胶、磷酸盐、锂酸盐和钛酸盐等。作为热控涂料的成膜物应该具有很高的热稳定性。一般来说，无机成膜物的稳定性要优于有机成膜物，其缺点是应用不如有机成膜物方便，表面清洗比较困难，所以二者各有优缺点，可根据实际情况选择，如果将二者复合，则可以相互弥补各自的不足。  \n\n常用的无机成膜物为水玻璃，其中高模数的硅酸钾比较稳定，研究和应用比较成熟。随着应用要求的提高和技术的发展，其他无机成膜物的研究和应用也得到长足的发展。表3-9-21列出了硅酸钾的主要性能。",
+        "category": " Introduction"
+    },
+    {
+        "id": 823,
+        "chunk": "# 3.助剂、溶剂等辅助物质  \n\n在涂料的制备过程中，添加适量助剂、溶剂等辅助物质可以改善涂料性能，具有非常重要的作用。其选择和应用的原则和普通涂料大同小异，应该根据具体情况而定。  \n\n表3-9-21 硅酸钾的主要性能  \n\n\n<html><body><table><tr><td>组成</td><td>数值</td><td>组 成</td><td>数值</td></tr><tr><td>KO含量（质量分数）/%</td><td>11.38</td><td>模数比</td><td>1:3.28</td></tr><tr><td>SiOz含量（质量分数）/%</td><td>23.83</td><td>铁含量（质量分数）/%</td><td>0.27</td></tr><tr><td>总固体含量（质量分数）/%</td><td>35.21</td><td>铜含量（质量分数）/%</td><td><4X10-*</td></tr><tr><td>相对密度</td><td>1.331</td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 824,
+        "chunk": "# （三）热控涂料的应用  \n\n处在轨道中的卫星或飞船要受到强烈的太阳辐射（因为是在真空中）、地球所反射的阳光和地球发射的红外线的作用，如不加以适当的控制，船体的温度将会在 $\\pm200^{\\circ}C$ 的范围内变动，故必须进行热控处理，以满足飞船表面的特殊光学性能，即阳光的吸收率 $\\alpha_{5}$ 和红外线发射率 $\\ E$ 的比值 $\\alpha_{S}/\\varepsilon$ 应足够低。在这方面涂料具有相当大的优势，因为它的成本低，施工应用方便，质量轻。  \n\n(1）高温涂料的应用高温涂料除在光学性能方面应具有低的吸收率和高的发射率之外，还应在高真空的宇宙环境中对强烈的紫外光、电子和质子流以及极端的温度循环具有足够的稳定性。在大多数的情况下，用于这一目的的涂料要满足阳光吸收率 $\\alpha_{5}=0,10$ ，红外线发射率 $e=0,\\ 90$ 以上，在空间环境中5年以后降解 $5\\%$ 以下。因此研究和发展这类涂料的关键，是如何使这种涂料在宇宙环境中长时间地（数月甚至数年）保持真空光学性能和物理机械性能。经过大量的试验以后发现，以二甲基有机硅树脂最好，其次是丙烯酸树脂和醇酸树脂。有机硅树脂涂料不仅耐紫外光、容易施工、挠曲性好，而且还具有很高的红外线发射率。但在紫外线的长期照射下会渐渐变脆，这是需要改进的。  \n\n除了有机成膜物以外，人们对无机成膜物也进行了广泛的研究，发现一些硅酸盐、磷酸盐、低温玻璃料等都可应用，其中以碱性硅酸盐最容易获得有使用价值的高纯度，并且与各种颜料具有很好的混溶性。在碱性硅酸盐中，硅酸锂、硅酸钠和硅酸钾都可以用，但其中以硅酸钾的纯度较高，应用较广泛。这类无机成膜物的特点是在宇宙环境中具有极好的稳定性，但它的附着力、挠曲性和施工性能不如有机成膜物好。  \n\n颜料和成膜物中的杂质对其稳定性也有相当大的影响。因此对颜料进行表面处理，以及如何提高纯度便引起了人们的普遍重视。表3-9-22列出了以硅酸钾为成膜物，锆石为颜料的涂料中杂质对稳定性的影响。  \n\n表3-9-22 锆石处理方式对涂料稳定性的影响  \n\n\n<html><body><table><tr><td>颜料</td><td>基料</td><td>颜料的处理</td><td>as初始值</td><td>紫外线(太阳照)/h</td><td>as最后值</td></tr><tr><td>ZrSiO(400目）</td><td>NazSiO</td><td>未处理</td><td>0.23</td><td>350</td><td>0.28</td></tr><tr><td>ZrSiO4 (Opaxs)</td><td>K2SiO</td><td>未处理</td><td>0.19</td><td>400</td><td>0.23</td></tr><tr><td>ZrSiO (Ultrox500)</td><td>KzSiO</td><td>未处理</td><td>0.16</td><td>300</td><td>0.20</td></tr><tr><td>ZrSiO (Ultrox)</td><td>KSiO</td><td>硝酸浸取-烧</td><td>0.10</td><td>350</td><td>0.21</td></tr><tr><td>ZrSiO(Ultrox)</td><td>KSiO</td><td>盐酸浸取-爆烧</td><td>0.10</td><td>350</td><td>0.22</td></tr><tr><td>ZrSiO(Ultrox500)</td><td>KSiO</td><td>盐酸浸取-般烧</td><td>0.12</td><td>600</td><td>0.18</td></tr></table></body></html>\n\n注：颜基比为 $4:1$ ，固体分 $80\\%$ P  \n\n同样，经过处理的氧化锌在真空中对紫外线的稳定性也比其他的颜填料的要好。有研究表明，在氧化锌的粒子表面有铁的杂质存在可以使有机硅成膜物受到保护。此外用硅酸盐如硅酸钾处理氧化锌也可以获得同样的效果。目前有机硅氧化锌涂料、硅酸钾二氧化锆涂料等  \n\n都在卫星的高温中得到了应用。  \n\n尽管高温涂料在稳定性方面仍存在一定的问题，但它用在面积较大和开头极为复杂的表面，如空间发射天线上却有突出的优越性。  \n\n(2）薄膜高温涂料的应用为了解决稳定性的问题，人们对薄膜高温涂料进行了广泛的研究。这种系统的外层是石英、二氧化硅、三氧化二铝、全氟乙烯丙烯共聚物和其他聚合物材料，然后用真空蒸发镀膜的方法将铝、银、金、铜、铬、镉、铂和锗等金属涂在外层薄膜上作为反射表面。这种系统兼有普通涂料的成膜物和颜料所具有的辐射和吸收的双重性质。因为金属膜的太阳吸收系数（ $:\\alpha_{\\mathrm{S}}$ ）基本上与外层膜的厚度无关，而红外辐射系数（）则可阻碍外层膜厚度的增加而增大，所以利用改变外层膜的物质类型、厚度和复合方法，便有可能制备出几乎任意的 $\\alpha_{5}/\\varepsilon$ 值的调温涂料。据报道，美国已有近200颗人造卫星是采用薄膜涂料来进行调温的。例如， $\\mathbf{A}_{\\mathbf{\\overline{{{g}}}}}$ （或A1）膜在太阳光谱的整个波长范围内，具有很高的反射率，对太阳光的吸收系数非常低， $\\alpha_{\\mathrm{{S}}}=0,050$ ，而石英玻璃则表现出很高的红外辐射特性，在 $295\\mathrm{K}$ 时，其 $\\varepsilon=0,81$ ，因此涂料的 $\\alpha_{S}/\\bar{\\varepsilon}$ 比值约为0.062，比目前所采用的任何一种调温涂料的 $\\alpha_{S}/\\varepsilon$ 比值都要低。所以是一类极有前途的材料。  \n\n这类薄膜调温涂料的种类很多，最常见的有Al-SiO、 $\\mathbf{Al-SiO_{2}}$ ， $\\mathbf{Al-Al_{2}O_{3}}$ ， $\\mathbf{Al-Al_{2}O_{3}}-$ .$\\mathrm{5iO_{2}}$ 、Al-Ge-SiO、AI-SiOz-Ge、Ge-SiO-AI-SiO、 $\\mathrm{Pt\\mathrm{-}S i O_{2}\\mathrm{-}P t\\mathrm{-}S i O_{2}}$ 等薄膜涂料和光学阳光反射器（简称OSR系统）。  \n\n薄膜调温涂料的最大优点是在空间环境中的稳定性极好。其缺点是造价很高，施工麻烦，特别是在那些极其曲折或不规则的表面上施工更困难。与普通调温涂料相比，其质量也较大，几种调温涂料的质量比较见表3-9-23。  \n\n表3-9-23 几种调温涂料的质量比较  \n\n\n<html><body><table><tr><td>涂层系统</td><td>质量比较/(g/m²）</td><td>涂层系统</td><td>质量比较/(g/m²)</td></tr><tr><td>OSR(200μm熔石英)</td><td>490（包括黏合剂的质量）</td><td>TiOz/硅胶（150μm）</td><td>230</td></tr><tr><td>OSR(100μm熔石英)</td><td>270（包括黏合剂的质量）</td><td>ZnO/KSiO(125μm)</td><td>210</td></tr></table></body></html>  \n\n国内某研究机构于20世纪80年代，以有机硅改性聚己内酯为成膜物研制的GF-1耐高温热反射涂料，成功应用于某型号航天器，该涂料热控效果和综合性能均满足使用要求。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 825,
+        "chunk": "# （四）热控涂料性能的影响因素  \n\n影响热控涂料性能的因素主要可以分为两大类，一是涂料制备工艺参数；二是涂料使用环境参数对涂料光学性能和稳定性的影响。  \n\n下面主要介绍工艺参数对涂料稳定性的影响。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 826,
+        "chunk": "# 1.颜料纯度  \n\n颜料纯度对于涂料性能有很大的影响，以氧化锌为例，表3-9-24列出了不同纯度的氧化锌反射率的变化。  \n\n表3-9-24氧化锌纯度对反射率的影响  \n\n\n<html><body><table><tr><td rowspan=\"2\">氧化锌纯度</td><td colspan=\"2\">反射率/%</td></tr><tr><td>440nm</td><td>660nm</td></tr><tr><td>优级纯</td><td>95.0</td><td>99.0</td></tr><tr><td>分析纯</td><td>93.50</td><td>98.0</td></tr><tr><td>化学纯</td><td>88.0</td><td>95.0</td></tr></table></body></html>  \n\n由表3-9-24可以看出，氧化锌纯度越高，其反射性能越好，而且经真空辐照试验后，其反射率变化也不大；随氧化锌纯度的提高，其抗紫外辐照能力也相应提高，空间稳定性越好。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 827,
+        "chunk": "# 2.颜料热处理条件  \n\n颜料通过适当的热处理工艺，一方面可以降低涂料的太阳吸收率，更为重要的是提高了涂料的抗紫外辐照能力。这可能是长时间的烧使得颜料中的极少量的杂质挥发，晶粒长大，减少了晶体结构中的缺陷，从而提高了其抗紫外辐照能力，如热处理后的氧化锌在红外光谱范围内反射率增加。也可能是由于在较长波段范围内入射光线被大颗粒氧化锌散射，因此降低了涂料对太阳的吸收率。实际上大多数氧化物经热处理后，用其作为颜料的涂料稳定性均得到不同程度的改善。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 828,
+        "chunk": "# 3.成膜物树脂的影响  \n\n前已叙述，成膜物可分为有机和无机两大类，无极成膜物的稳定性要优于有机成膜物，但是有机成膜物因为具有使用方便、力学性能优异等无极成膜物所不具备的优势，故有机成膜物作为热控涂料的黏结剂仍占重要的位置，其中以聚甲基硅氧烷为主要代表。常用有机成膜物的抗紫外辐照能力如表3-9-25所示。  \n\n表3-9-25 树脂种类对热控涂料性能的影响  \n\n\n<html><body><table><tr><td>树脂种类</td><td>丙烯酸树脂</td><td>聚氨酯</td><td>加成型硅树脂</td><td>甲基硅树脂</td></tr><tr><td>αs</td><td>0.25</td><td>0.24</td><td>0.16</td><td>0.12</td></tr><tr><td></td><td>0.83</td><td>0.87</td><td>0.89</td><td>0.85</td></tr><tr><td>as/E</td><td>0.30</td><td>0.28</td><td>0.18</td><td>0.14</td></tr></table></body></html>\n\n注：其中颜基比为 $1\\div2$  \n\n表3-9-25显示，不同树脂制备的热控涂料相比较，有机硅热控涂料的 $\\alpha_{5}/E$ 较小，这是因为有机硅材料的透光性较好。另外，在空间环境条件下，有机硅材料的稳定性好，因为在$300\\mathrm{mm}$ 以上紫外光的能量高于 $376.6\\mathrm{kJ/mol}$ ，而有机聚合物分子的键能一般在 $250{\\sim}418\\mathbf{kJ}/\\mathrm{mol}$ .大部分高分子键会发生断裂，其结果使有机热控涂料变脆、皱缩、附着力下降，形成光吸收中心，使涂料吸收带移向长波，最终导致涂料的 $\\alpha_{\\mathrm{{S}}}$ 值增高，影响涂料的热控性能。  \n\n有机硅树脂的种类很多，影响其应用的因素也很多，归纳起来主要有两方面的原因，一是固化方式；二是结构因素。  \n\n$\\textcircled{1}$ 固化方式根据有机硅涂料固化成膜机理，可以分为加成型硅树脂和缩合型硅树脂。近年来，人们研究发现，热控涂料的质量损失（TML）和可凝挥发物（CVCM）两项指标非常重要，由于缩合型有机硅树脂在固化的过程中因为会有 $\\mathbf{Si-OH}$ 1 $\\mathbf{Si}{\\mathrm{-}}\\mathbf{H}$ 交联点，不可避免地会产生一些小分子，因而很难制得低TML和CVCM的热控涂料。而采用加成型硅树脂，制备热控涂料在固化过程中无小分子放出，涂料的抗收缩性好。可望制得高性能的热控涂料。  \n\n$\\textcircled{2}$ 有机硅树脂结构影响有机硅树脂的主链为Si一O结构，其侧链基团不同，对其性能的影响也不尽相同。有机硅树脂是具有高度交联结构的热固性聚硅氧烷体系，侧链基团主要为甲基、苯基、烷氧基、乙烯基及氢基，加成型有机硅树脂侧链引人乙烯基及氢基，作为加成反应的活性基团，但是应尽量减少最终产品的活性基团残留浓度（因为一 $\\mathbf{\\nabla}\\cdot\\mathbf{H}$ 一 $-\\mathrm{CH}{=}\\mathrm{CH}_{2}$ 基团在紫外光的作用下，会发生降解反应，生成有色物质，使涂料的 $a_{5}$ 增加）。另外，研究表明，含苯基和烷氧基的有机硅树脂耐紫外光的能力较差，而具有高度透过紫外  \n\n光能力的甲基有机硅树脂性能较好。  \n\n在聚甲基有机硅树脂中，CH3/Si摩尔比越低，涂料αs越低，其结构越接近石墨，耐紫外性能越佳（见表3-9-26)，但是CH/Si摩尔比过低，涂料的脆性随之增大，一般认为，$\\mathrm{CH_{3}/S i}$ 的摩尔比为1.38最佳。  \n\n表3-9-26真空紫外辐射对甲基有机硅的影响  \n\n\n<html><body><table><tr><td>CH3/Si摩尔比</td><td>紫外辐射等量太阳/h</td><td>as/%</td></tr><tr><td>2</td><td>1460</td><td>18.6</td></tr><tr><td>1.46</td><td>1460</td><td>15.0</td></tr><tr><td>1.38</td><td>1460</td><td>8.7</td></tr><tr><td>1.33</td><td>1460</td><td>0</td></tr></table></body></html>\n\n$\\textcircled{1}$ 成膜物为甲基硅树脂，填料为 $\\mathtt{S P S O O Z n}$ ，填料体积分数为 $50\\%$ 嘟  \n\n无机成膜物主要有磷酸盐和硅酸盐，从真空辐照试验后的光学性质变化看，二者的差别并不是很大，但是考虑综合性能，碱金属硅酸盐性能较磷酸盐性能要好些。碱金属硅酸盐中，以硅酸钾为成膜物的热控涂料，其太阳吸收率低于硅酸钠涂料；相同的碱金属硅酸盐，模数越高，其涂料的太阳吸收率越小，而抗紫外辐照能并无明显变化。研究认为，模数为3.3的硅酸钾的性能更好。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 829,
+        "chunk": "# 4.颜基比对涂料光学性能的影响  \n\n颜基比是涂料制备的一个重要的控制参数。对热控涂料而言，涂料中颜料的含量直接影响到其 $\\alpha_{5}$ ， $\\bar{E}$ 以及 $\\alpha_{S}/\\varepsilon$ ；不仅如此，颜基比还会影响涂料其他性能，如力学性能。一般来讲，高颜基比对增大涂料反射率和降低吸收率是有利的；但并不是越高越好，否则会导致涂料力学性能严重下降，所以，颜基比应该控制在达到涂料综合性能平衡的最佳点，应根据所选用的成膜物、颜料的种类，以及涂料具体应用技术要求来确定最佳的颜基比。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 830,
+        "chunk": "# 5.研磨方式对涂料性能的影响  \n\n涂料分散设备有三辊、砂磨和球磨等。试验证实，球磨较其他研磨方式的效果要好，特别是针对以有机硅和硅酸钠等为成膜物的耐温涂料，通常是采用球磨研磨为佳。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 831,
+        "chunk": "# 三、耐高温隔热保温涂料  \n\n顾名思义，该类涂料有两方面的重要性能，一是耐高温，二是隔热。这种涂料主要用于高温环境并要求具有隔热效果的设备、仪器等，如航空发动机叶片、发动机外壳、导弹弹头、弹体过渡段、喷管和其他局部防热部位。",
+        "category": " Introduction"
+    },
+    {
+        "id": 832,
+        "chunk": "# （一）国内外研究现状",
+        "category": " Introduction"
+    },
+    {
+        "id": 833,
+        "chunk": "# 1.国外研究现状  \n\n(1）俄罗斯俄罗斯研制的隔热材料具有密度小、质轻、热导率低、不着火等优点，与基材有良好的相容性和较高的附着力，主要用于导弹弹头、弹体过渡段、喷管和其他局部防热部位。这种轻质隔热材料是利用氯化硫酸聚乙烯作为基体，并加入不同填料，如氧化硅和不同的轻质空心小球，如玻璃空心小球、酚醛空心小球、碳空心小球、丙烯酸酯空心小球， $\\omega{\\mathrm{-}}\\mathrm{SiO_{2}}$ 和Ni-酚醛复合空心小球等，以 $80:20$ 的比例混合，加人固化剂和活性剂后在 $50\\sim60^{\\circ}C$ 下固化，得到密度 $\\rho{<}1.0\\mathrm{g/cm^{3}}$ 的轻质隔热涂料，可使工作温度提高到 $600^{\\circ}C$ (表3-9-27)。  \n\n表3-9-27 俄罗斯的几种中、轻质隔热材料性能  \n\n\n<html><body><table><tr><td>品种</td><td rowspan=\"2\">1#</td><td rowspan=\"2\">2#</td><td rowspan=\"2\">3#</td><td rowspan=\"2\">4#</td></tr><tr><td>性能</td><td></td></tr><tr><td>密度/（g/cm²）</td><td>0.20～0.24</td><td>0.30～0.40</td><td>0.50~0.60</td><td>0.45~0.60</td></tr><tr><td>热导率/[W/（m·K)]</td><td>0.04~0.06</td><td>0.06~0.08</td><td>0.10~0.15</td><td>0.08～0.10</td></tr><tr><td>比热容/[kJ/（kg·K）]</td><td>1.30~0.80</td><td>1.50～1.80</td><td>1.10~1.50</td><td>1.50～2.0</td></tr><tr><td>拉伸强度/MPa</td><td>>0.4</td><td>>0.5</td><td>>1.4</td><td>>1.3</td></tr><tr><td>伸长率/%</td><td>>5</td><td>≥5</td><td>>8</td><td>>120</td></tr></table></body></html>  \n\n(2）美国、法国和日本等国20世纪80年代美国空军火箭推进研究所研制出“低价格隔热材料”，价格在25美元/加仑左右，用于“民兵”发射并整修以及要求进行有效防护的发射装置。美国陆军战略防御司令部的SaylesD.C.博士认为：用软木或二氧化硅作填料的酚醛树脂、环氧树脂、聚四氟乙烯、环氧聚氨酯材料是发动机壳体常用的外防热材料，代表了80年代末到90年代初的技术水平；代表未来技术水平的发动机外防热材料是聚二甲基硅氧烷。因为外部环境温度在- $-148.9\\sim287.8^{\\circ}\\mathrm{C}$ 范围内，只有聚二甲基硅氧烷材料几乎是完全稳定的。  \n\n法国宇航公司已经开发出多种防热材料体系，其中一种是由硅树脂和中空二氧化硅颗粒制成，密度 $\\rho{=}0,\\delta\\bar{\\mathrm{g}}/\\mathrm{cm}^{3}$ ，热导率 $\\lambda{=}0.1{\\sim}0.145\\mathbf{W}/(\\mathbf{m}\\cdot\\mathbf{K})$ ，可用喷枪喷涂，用于 Huy-gens航天探测器中。  \n\n日本三菱重工发明了由环氧树脂、空心 $\\mathrm{{5iO_{2}}}$ 微球、无机纤维等制成的卫星搭载体、推进器外隔热防护层。日本宇宙开发事业团先后采用酚醛环氧树脂加空心微球（ $\\mathrm{SiO}_{\\lambda}$ 微球、酚醛微球）及聚硅氧烷加空心微球制成适于火箭导弹流线型外壳的热防护层。",
+        "category": " Introduction"
+    },
+    {
+        "id": 834,
+        "chunk": "# 2.国内研究现状  \n\n我国这方面的研究起步较晚，而且研究多集中于环氧树脂/空心微珠混合体系。  \n\n胡金锁等研制的隔热材料是以环氧树脂为基体，石棉、硅藻土、氧相二氧化硅等为填料，用于星平台和弱载电子设备的隔热防护，效果很好。  \n\n卢嘉德等以中空玻璃珠为隔热填料、芳纶短纤维为增强材料，氯磺化聚乙烯橡胶为基体研制的外防护涂料的密度为 $0.65\\mathrm{g/cm^{3}}$ ，热导率为 $0.125\\mathbf{W}/(\\mathbf{\\Omega}\\mathbf{m}\\cdot\\mathbf{K})$ ，其隔热性和工艺性良好。  \n\n牛国良研制出以聚氨酯/环氧树脂为基体、中空玻璃微珠为填料的隔热材料，其综合性能和工艺性能良好，用于固体火箭发动机壳体的外隔热防护。  \n\n何敏采用紫外光固化技术对有机硅改性环氧丙烯酸酯体系进行快速紫外固化，然后加人中空玻璃微球，制备的隔热材料具有较低的热导率 $\\left[0.252\\mathbf{W}/(\\mathbf{m}\\cdot\\mathbf{K})\\right]$ 和较低的密度，而且对基材的附着力和韧性良好，主要用于发动机壳体的热防护。",
+        "category": " Introduction"
+    },
+    {
+        "id": 835,
+        "chunk": "# （二）组成  \n\n耐高温隔热涂料根据所用成膜物和成膜方式的不同，可以分为有机耐高温隔热涂料、无机耐高温隔热涂料和陶瓷涂料三大类。有机耐高温隔热涂料的耐高温性能有限，但是具有制备和应用简单方便，易清洗、修复，成本低等优点；而无机耐高温隔热涂料和陶瓷涂料的耐高温性能远远高于有机涂料，但是其工艺较复杂，需高温固化成膜，不易清洗，成本相对较高。所以，应根据具体不同应用条件，而采用相应的涂料类型，以更好地适应使用要求。  \n\n陶瓷涂料已经不属于传统意义上的涂料，不在此涉及。在这里只讨论有机耐高温隔热涂料和无机耐高温隔热涂料的组成及特性。",
+        "category": " Introduction"
+    },
+    {
+        "id": 836,
+        "chunk": "# 1.成膜物  \n\n耐高温隔热涂料由成膜物、填料以及溶剂、助剂组成。  \n\n成膜物可分为有机和无机成膜物，有关内容已在本章前节中介绍，这里不再赘述。  \n\n有机成膜物主要考察其耐热性能，常用的有聚氨酯树脂、环氧树脂、酚醛树脂、聚酰业胺树脂、有机硅树脂及聚二甲基硅氧烷、聚矾树脂、聚苯树脂及杂环树脂、橡胶等，以及各种改性树脂，如环氧改性有机硅树脂、酚醛环氧树脂、乙烯基环氧酚醛树脂等，各种树脂的耐温性能有差异，应根据实际情况选用。一般纯有机树脂的耐温低于300℃，配以耐温填料有机涂料可达到 $700\\%$ ，甚至更高。  \n\n无机成膜物有碱金属硅酸盐、磷酸盐、钠铝硅酸盐和锂酸盐等，耐温性能可达到$1000^{\\circ}C$ 以上，使用时着重考虑其力学性能。",
+        "category": " Introduction"
+    },
+    {
+        "id": 837,
+        "chunk": "# 2.填料  \n\n填料是隔热保温涂料的主要组成部分，选择适当的填料作为隔热材料，是实现涂料隔热性能的主要手段。  \n\n根据涂料性能要求，隔热填料应具有密度和热导率小、热稳定性能好等特点，所以填料的性能起到决定性的影响。一般认为，在同样的条件下，隔热材料的单位面积质量与材料的$o\\lambda C_{\\phi}$ 值成正比（其中 $p$ 为材料密度， $\\lambda$ 为材料的热导率， $C_{p}$ 为材料的比热容)。由于各种隔热材料随温度变化比热容 $C_{p}$ 变化不大，因此材料的隔热性能主要取决于填料的热导率 $\\lambda$ 和密度 $p$ 。热导率越低和密度越小，材料隔热性能越好。  \n\n另外，材料的隔热性能还取决于材料的结构状态和空隙率。非金属无机材料的结构状态有晶体结构、微晶结构和玻璃态结构。结构状态不同的材料，其热导率差别很大。由于空气的热导率比一般固体物质小得多，所以选用多孔性材料可以大大降低热导率。由此可见，通过改变材料结构状态和增加材料空隙率的方法，不仅可以大大降低材料的热导率，减少材料的容量，而且可以明显提高材料的隔热性能，已有的研究结果也证明了这一结论。  \n\n(1）低热导率填料不同填料热导率差别很大，部分常用填料的热导率见表3-9-28。  \n\n表3-9-28 部分常用填料的热导率  \n\n\n<html><body><table><tr><td>热导率范围 /CW/(m·K)]</td><td>填料（热导率/[W/(m·K）])</td></tr><tr><td>低于10</td><td>芳纶纤维(0.04～0.05)，碳酸钙(2.4～3)，陶瓷球(0.23)，玻璃纤维(1)，氧化镁(8～32)，气相二 氧化硅(0.015)，二硫化钼(0.13～0.19),，PAN基碳纤维（9～100)，熔凝二氧化硅(1.1)，砂(7.2～</td></tr><tr><td>10~29</td><td>13.6)，滑石粉(0.02)，二氧化钛(0.065），蛭石粉(0.062～0.065） 氧化铝（20.5～29.3)，沥青基碳纤维(25～100）</td></tr><tr><td>100～199</td><td>石墨（110～190)，镍（158)</td></tr><tr><td>高于200</td><td>铝片和铝粉(204），氧化(250），氮化硼(250～300），铜（483），金（345），银（450）</td></tr></table></body></html>  \n\n由表3-9-28可以看出，适用于隔热涂料的填料在第一行，同时，根据实际应用经验，填料的密度越小、其热导率也相应越小，这里密度是堆积密度而非填料的真实密度，这样更为准确，也是因为填料的形态同样是热导率的影响因素，一般认为同一种填料粒径越小、热导率越低。  \n\n(2）空心结构填料空心结构填料是近年来新兴的隔热材料，因为其特殊的球形空心结构，具有低热导率、低密度、低吸油量、易分散、流动性好、稳定性好的优点，是目前首选的隔热填料。主要有空心玻璃微珠、空心陶瓷微珠、空心 $\\mathrm{{\\bfSiO_{2}}}$ 微珠、中空酚醛微球、碳空心微球、丙烯酸酯空心微球以及空心纤维粉等。中科院化学所研制的空心酚醛微球应用于我国航天飞船上已获得成功。  \n\n空心玻璃微珠和空心陶瓷微珠的性质见表3-9-29。  \n\n表3-9-29空心玻璃微珠和空心陶瓷微珠的性质  \n\n\n<html><body><table><tr><td>名称</td><td>主要组成</td><td>堆积密度/（g/cm²）</td><td>热导率/[W/（m·K)]</td><td>吸油量/（g/cm3）</td></tr><tr><td>玻璃徽珠</td><td rowspan=\"2\">SiOz和AlzO3</td><td>0.06～0.18</td><td>0.07~0.12</td><td>0.4~0.5</td></tr><tr><td>陶瓷微珠</td><td>0.3~0.5</td><td>0.058~0.1</td><td>0.4~0.5</td></tr></table></body></html>  \n\n试验中发现，由于其密度低，很容易上浮。为了解决这问题，-一是采用密度较大的空心陶瓷微珠部分代替，二是选用合适偶联剂进行表面预处理，两种方法结合，可得到满意的效果。球状填料比片状、针状或不规则形状的填料更具有较好的流动性，由于圆球状的物体是各向同性的，在干燥成膜过程中，不会产生因取向造成不同部位收缩率不一致的弊病。  \n\n(3）纤维类填料芳纶纤维等具有很低的热导率 $[0,04\\sim0.05\\mathbf{W}/(\\mathbf{m}\\cdot\\mathbf{K})]$ ，特别是空心纤维其热导率更低，是非常好的低热导率隔热材料，应用非常广泛。但用于涂料体系中，导致涂料体系黏度急剧增大，混料和施工比较困难，使用中应该注意这一问题，纤维在模压和浇注成型材料中应用较多。主要有有机纤维和无机纤维，性能良好。  \n\n（4）新型隔热填料随着技术的发展和环保要求的提高，传统有机溶剂型涂料，逐步向无机化方向发展。前面提及的陶瓷涂料不属于传统意义上的涂料，但并无绝对的界限。如有机硅耐高温涂料，在经过高温固化或者高温处理（ $600^{\\circ}C$ 以上）后，由于其特有的“二次成膜”机理的作用，涂料已经具有类似于无机或者陶瓷涂料的特征和性能，呈现出一种亚状态。涂料的耐温性能和隔热性能要求不断提高，纯粹意义上的有机涂料已经很难满足技术发展的要求，向无机化过渡势在必行。将性能优良的陶瓷粉成功应用于涂料技术中，即可以避免陶瓷涂料工艺复杂、成本高的缺陷，是很好的发展方向。  \n\n目前，陶瓷粉的研究开发主要集中在稀土锆酸盐。Vassen等合成了 $\\mathrm{\\bar{Sr}Z r{O_{3}}}$ ， $\\mathrm{{BaZrO_{3}}}$ 和 $\\mathbb{L}\\mathrm{a}_{2}\\mathbb{Z}\\mathrm{r}_{2}\\mathbb{O}_{7}$ 三种陶瓷粉，并对其热物理性能进行了研究，结果表面在 $1200^{\\circ}\\mathrm{C}$ 下， $\\mathrm{La}_{2}\\mathrm{Zr}_{2}\\mathrm{O}_{7}$ 表现出优异的热稳定性、抗热振性和低热导率；Maloney等人采用固相法合成了 $\\hat{\\mathrm{Gd}}_{2}{\\sf Z r}_{2}\\hat{\\mathrm{O}}_{7}$ T$\\mathrm{Sm}_{2}\\mathrm{Zr}_{2}\\mathrm{O}_{7}$ 和 $\\mathbf{Nd}_{2}\\mathbf{Zr}_{2}\\mathbf{O}_{7}$ 等稀土锆酸盐，并测定了其热物理性能；XuQiang等人采用固相法在 $1600^{\\circ}C$ 下合成了 $\\mathrm{Dy}_{2}\\mathrm{Zr}_{2}\\mathrm{O}_{7}$ 陶瓷粉，对其热导率和热膨胀系数进行了研究；周宏明等人采用共沉积-烧法制备了 $\\mathrm{Dy}_{2}\\mathrm{Zr}_{2}\\mathrm{O}_{7}$ 陶瓷粉，该方法优于固相法，成本低、质量稳定。  \n\n以氧化铈和氧化钇复合稳定的氧化锆空心球形喷涂粉末，具有向心度高、性能稳定、杂质含量低、不吸潮等优点，该粉体材料属国内首创，其性能指标达到20世纪90年代初的国际先进水平。  \n\n由清华大学等单位共同研制的复合稀土铅酸盐低导热隔热的陶瓷涂料材料，获得成功应用，将其喷涂于部件表面可形成一层耐高温的低导热材料，能在 $1200^{\\circ}C$ 以上长时间使用，可广泛用于航天航空等高端领域。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 838,
+        "chunk": "# 3.微孔隔热涂料技术  \n\n涂料制备是涂料应用中非常关键的技术之一。针对隔热保温涂料而言，在组成确定以后，由于其物性是确定的，所以涂料隔热性能取决于各成分综合效果。随着纳来隔热理论的出现，传统的隔热理论受到挑战，根据最新隔热机理，在理论上讲，涂料材料的热导率可以低于静止空气的热导率 $[0.023\\mathbf{W}/(\\mathbf{m}\\cdot\\mathbf{K})]$ ，甚至可以趋近于0。这对隔热保温涂料技术提出了新的挑战和发展机遇。  \n\n实现该目的主要有两个方面的技术支撑。  \n\n① 纳米级空心结构的填料，孔径在50nm以下，主要有空心微珠和空心纤维，粒径分布窄，微孔结构封闭，性能稳定。  \n\n② 涂料微发泡技术，形成无穷多的纳米级、封闭发泡结构。关键是发泡剂在涂料中的分散状态，液体发泡剂应该呈分子级分散；固体发泡剂颗粒粒径应该在10nm以下，甚至更小。另外，发泡条件也是至关重要的，是有效、均匀地形成孤立、封闭微孔的重要保证条件。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 839,
+        "chunk": "# 四、小结  \n\n第一，要克服发展的瓶颈——有机成膜物树脂的高性能化。具有非常优异性能的有机树脂的开发已初见端倪，但因合成技术尚需进一步成熟，尚需降低成本，才可进人实际应用。随着技术发展，这一限制一定终将会得到解决。  \n\n第二，以纳米材料为代表的新型隔热材料的不断开发和应用，将会进一步提高涂料隔热保温性能。  \n\n第三，多种隔热机理结合于一种隔热保温涂料中，各自的特点发挥到极致，优势互补，使得涂料隔热保温效果更为显著。  \n\n第四，多微孔涂料因其卓越的隔热性能，将是今后研究的一个重要方向，但是目前仍处于理论认识的阶段，缺乏实际应用验证。国家如加强这方面的研发，使理论的认识成为现实，那将是隔热技术发展的飞跃。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 840,
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+        "category": " References"
+    },
+    {
+        "id": 841,
+        "chunk": "# 机床涂料与涂装  \n\n金属切削机床、锻造机械、铸造机械、木工机械、纺织机械、印刷机械、重型机械等，其部件大多是铸铁件或铸钢件，它们的生产工艺基本类似，故其涂装工艺也基本类似。",
+        "category": " Introduction"
+    },
+    {
+        "id": 842,
+        "chunk": "# 一、涂装的作用",
+        "category": " Introduction"
+    },
+    {
+        "id": 843,
+        "chunk": "# 1.防护作用  \n\n金属切削机床等机械产品的非机械加工面，为避免其在贮运过程和使用过程中受到锈蚀与损伤，通常采用涂漆来防护，以达到延长使用寿命的目的。",
+        "category": " Introduction"
+    },
+    {
+        "id": 844,
+        "chunk": "# 2.装饰作用  \n\n选择合理的涂料、美观大方的色彩，将金属切削机床等机械装饰起来。其目的：  \n\n$\\textcircled{1}$ 美观大方的色彩可以减少操作者的视力疲劳，以利提高劳动效率；  \n$\\textcircled{2}$ 美观大方的装饰效果是提高产品竞争能力，扩大销售的重要条件；  \n$\\textcircled{3}$ 美观大方的外观能激发操作者的爱惜意识，从而可以延长机械产品使用期限。",
+        "category": " Introduction"
+    },
+    {
+        "id": 845,
+        "chunk": "# 二、机床涂装作业特点  \n\n金属切削机床等机械的涂装作业具有如下特点。  \n\n$\\textcircled{1}$ 金属切削机床等机械产品，由于品种、型号、规格较多，外形各异，使其涂装作业具有多品种、小批量的特点，因此难以像汽车涂漆那样采用自动涂装生产线。一般来说，这些机械产品的涂装以手工作业为主。在一些大型企业中，对于某些规格型号产品的部件，比如防护罩等，由于具有通用性强、外形简单、批量较大等有利条件，采用自动粉末涂装工艺。  \n\n$\\textcircled{2}$ 金属切削机床等机械产品，其部件大多是铸件，鉴于目前我国铸造水平，铸件表面平整度较差，为提高产品的装饰质量，较多地使用各种腻子来填平铸件表面的缺陷。因此，腻子的刮涂与打磨在整个产品涂装工作中占有相当大的比重。  \n\n$\\textcircled{3}$ 金属切削机床等机械产品，其涂装件上的机械加工面都有一定的精度要求，所以，这些部件的涂漆不宜选用烘烤型涂料（如粉末涂料)，以免高温引起机械加工部位的热变形而影响产品精度。故这些机械产品一般选用自干型涂料。  \n\n$\\textcircled{4}$ 金属切削机床等机械产品，由于外形复杂、机身既重又大、运转困难，影响静电喷",
+        "category": " Introduction"
+    },
+    {
+        "id": 846,
+        "chunk": "# 漆等一些新涂装技术的采用。  \n\n![](images/4bec93b625da7aa8f6fec5fbdc23263a923bb1bcb8f8317f6208336de970e15f.jpg)  \n\n机床等机械产品的外观质量主要决定于涂装质量，而涂装质量的关键在于涂料的质量和它的装饰性能。所以正确、合理选择涂料是保证机床涂装质量的重要条件。",
+        "category": " Introduction"
+    },
+    {
+        "id": 847,
+        "chunk": "# 一、机床涂装用涂料选用原则  \n\n机床等机械产品涂装用材料要根据其生产工艺特点选择。其有下列基本考虑原则。",
+        "category": " Introduction"
+    },
+    {
+        "id": 848,
+        "chunk": "# 1.选用的底漆、腻子、面漆及稀料要配套  \n\n涂料配套是保证涂装质量的重要条件，如果不配套，容易使漆膜发生剥落、开裂、咬起等病。配套有“同性配套”与“异性配套”之分。  \n\n所谓“同性配套”就是所用的底漆、腻子、面漆等材料，它们所含的树脂、溶剂相同。层与层之间融合性好，和底漆、腻子、面漆构成一个整体。如机床采用过氯乙烯底漆、过氯乙烯腻子、过氯乙烯磁漆，这些材料所含的主要树脂为过氯乙烯树脂，溶剂为过氯乙烯稀料。  \n\n所谓“异性配套”就是漆层采用不同的涂料，尽管它们所含的主要树脂不同，但它们之间亲和性好，结合在一起形成良好的附着力，形成的漆膜不至于咬起、揭皮、剥落、开裂等。如在磷化底漆上喷过氯乙烯底漆，在过氯乙烯腻子上喷聚氨酯磁漆等。虽然它们的主要树脂不同，但它们互相亲和，结合在一起不致发生咬起、揭皮、开裂等弊病。",
+        "category": " Introduction"
+    },
+    {
+        "id": 849,
+        "chunk": "# 2.要选用常温自干型或常温固化型涂料  \n\n机床等机械产品，其涂漆件上的机械加工面有一定的精度要求。由于在高温条件下会使部件产生热变形而影响机加工的精度，所以，这些机械，特别是精度要求高的机械产品，其涂装用材料一般要选用常温自干型或常温固化型涂料。  \n\n常用的常温自干型涂料有过氯乙烯漆、丙烯酸改性漆、聚氨酯漆等。常用的常温固化型涂料有原子灰、环氧漆等。  \n\n由于机床等机械产品的生产周期的不均衡性，要求漆膜干燥时间要快，根据ZB』50012《机床涂料技术条件》的规定，选用的底漆、面漆表干不超过0.5h，实干不大于2h，腻子实干不大于4h。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 850,
+        "chunk": "# 3.所用涂料要具有优异的防护性能  \n\n机床等机械产品，一般需6～7年时间才进行大修，所以要求涂装这些机械的涂料的防护性能要耐 $5\\sim7$ 年，方可适应。  \n\n湿热是造成机床等机械涂层破坏的气候因素，所以选用的涂料要有良好的耐湿热性能。  \n\n机床等机械产品在加工部件或零件时，免不了在漆膜上沾上润滑油或金属切削加工液，所以选用的涂料要能耐机械润滑油与金属切削加工液的侵蚀作用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 851,
+        "chunk": "# 4.所用面漆要有良好的外观装饰性能  \n\n装饰性能好坏直接影响机床等机械产品的外观质量。  \n\n装饰性能好坏主要表现在漆膜光泽(平光漆)、花纹均匀性(美术漆)、丰满度、色彩格调等方面。  \n\n根据ZBJ50012《机床涂装技术条件》规定：采用平光漆涂装的中、小机床面漆光泽，出口的要大于85%，内销的要大于75%；而采用平光漆涂装的大、重型机床面漆光泽，出口的要大于 $80\\%$ ，内销的要大于 $70\\%$ 0",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 852,
+        "chunk": "# 5.更换涂料要先试验后采用  \n\n凡需采用新涂料或更换涂料品种时，必须用新涂料做成与产品涂层相同的涂层试片，按ZBJ50012《机床涂装技术条件》规定，进行耐湿热、耐盐雾、耐机油与耐切削液试验和目然暴露试验，各项性能指标达到要求后方可采用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 853,
+        "chunk": "# 二、机床涂装常用涂料  \n\n现将机床涂装常用的涂料品种介绍如下。",
+        "category": " Introduction"
+    },
+    {
+        "id": 854,
+        "chunk": "# （一）底漆  \n\n机床涂装常用的底漆有锌黄、铁红过氯乙烯底漆与磷化底漆，为提高涂层的附着力近来又开发出双组分固化型的环氧、丙烯酸铁红底漆等，虽未普及但得到越来越多的应用。其品种、性能等见表3-10-1。各底漆的技术指标见表3-10-2～表3-10-5。  \n\n表3-10-1 机床涂装用底漆品种与性能  \n\n\n<html><body><table><tr><td>名称</td><td></td><td>G06-3锌黄过氯乙烯底漆G06-4锌黄、铁红过氯乙烯底漆</td><td>G06-5过氯乙烯二道底漆</td><td>X06-1磷化底漆</td></tr><tr><td>组成</td><td>由过氯乙烯树脂、氯 化橡胶、颜料、增韧剂及 溶剂组成</td><td>由过氯乙烯树脂、醇酸树 脂、颜料、增韧剂及溶剂组成</td><td>由过氯乙烯树脂、醇酸 树脂、颜料、增韧剂、体质 颜料及混合溶剂组成</td><td>由聚乙烯醇缩丁醛树脂 防锈颜料、乙醇、丁醇混合 溶剂调成组分I，与组分 Ⅱ（磷化液）混合使用</td></tr><tr><td>性能</td><td>对钢、铝合金、镁合金 有较好的附着力</td><td>具有一定的防锈性及耐化 学性能，但附着力稍差，≤2级</td><td>漆膜干燥快，填孔性 好，有一定机械强度</td><td>能增强涂层与金属的附 着力，防止金属锈蚀</td></tr><tr><td>用途</td><td>用于打底漆</td><td>用于打底漆</td><td>用于填孔补隙</td><td>用于有色与黑色金属底 层防锈涂料</td></tr><tr><td>配套稀料</td><td colspan=\"3\">X-3过氯乙烯漆稀释剂</td><td>组分I：组分Ⅱ=4:1</td></tr><tr><td>配套性</td><td colspan=\"3\">可与各种过氯乙烯漆及改性过氯乙烯漆、过氯乙烯腻子、磷化底漆及聚氨酯漆等 配套</td><td>可与环氧、过氯乙烯、醇 酸等多种底漆配套</td></tr><tr><td>施工要求</td><td colspan=\"2\">1.可喷涂，也可刷涂。 2.在相对湿度大于70%场合下施工，需加入F-2过氯乙烯防潮剂</td><td></td><td>可喷涂，也可刷涂</td></tr></table></body></html>  \n\n表3-10-2G06-3锌黄过氯乙烯底漆  \n\n\n<html><body><table><tr><td>技术要求名称</td><td>指 标</td></tr><tr><td>漆膜外观及颜色</td><td>黄色，色调不定，漆膜平整，无显著粗粒</td></tr><tr><td>黏度（涂-4黏度计）/s 固体含量/%</td><td>50~80</td></tr><tr><td>干燥时间/h</td><td>39 ≤</td></tr><tr><td>表干</td><td></td></tr><tr><td>实干</td><td>0.5 2</td></tr><tr><td>柔韧性/mm</td><td>1</td></tr><tr><td>冲击强度/N·cm</td><td>500</td></tr></table></body></html>  \n\n<html><body><table><tr><td>技术要求名称</td><td>指 标</td></tr><tr><td>附着力/级 耐湿热（40℃±2℃，相对湿度95%以上）/d 耐盐雾（40℃±2℃，3%氯化钠水溶液）/d 耐人工海水(25℃，3%氯化钠水溶液浸渍）/d</td><td>1 21 21 21</td></tr><tr><td>耐蒸馏水/d 质量标准</td><td>21 Q/GHTB 47—91</td></tr></table></body></html>  \n\n表3-10-3G06-4锌黄、铁红过氯乙烯底漆  \n\n\n<html><body><table><tr><td>技术要求名称</td><td>指 标</td></tr><tr><td>漆膜外观及颜色 黏度（涂-4黏度计）/s 固体含量/%</td><td>锌黄、铁红色调不定，漆膜平整无粗粒 60~140</td></tr><tr><td></td><td></td></tr><tr><td>锌黄</td><td>40</td></tr><tr><td>铁红</td><td>45</td></tr><tr><td>干燥时间/min</td><td>≤</td></tr><tr><td>实干</td><td></td></tr><tr><td>柔韧性/mm</td><td>60</td></tr><tr><td>附着力/级别</td><td>≤ 1</td></tr><tr><td>耐盐水性 锌黄（浸48h）</td><td>2</td></tr><tr><td>铁红(浸24h）</td><td>不起泡、不生锈，允许轻微变色 不起泡、不生锈，允许轻微变色</td></tr><tr><td>复合涂层耐酸性(浸30d）</td><td>不起泡、不脱落</td></tr><tr><td>复合涂层耐碱性(浸20d）</td><td>不起泡、不脱落</td></tr><tr><td>质量标准</td><td>ZBG 51065—87</td></tr></table></body></html>  \n\n续表  \n表3-10-4G06-5过氯乙烯二道底漆  \n\n\n<html><body><table><tr><td>技术要求名称</td><td colspan=\"6\">标 指</td></tr><tr><td>漆膜颜色及外观</td><td colspan=\"6\">色调不定，无显著粗粒</td></tr><tr><td>黏度（涂-4黏度计）/s 固体含量/% 干燥时间/min 表干 实干 冲击强度/N·cm 硬度 附着力/级</td><td>115~250 V ≤ 30 180 400 ≥ ≤ 3</td><td>60~160 41 20 60 400 3</td><td>40~140 42 60 0.4</td><td>70~150 120 300 3</td><td>≥60 30 120 500</td><td>40~120 120 300</td></tr><tr><td>耐油性（32*机械油）/h 质量标准</td><td>G/H12- 117—91</td><td>Q/GHTB- 48—91</td><td>Q/HJ 1.28—91</td><td>滇 QKY 038-90</td><td>QI/ DW 02G</td><td>一 QB /ZQBJ</td></tr><tr><td>产地</td><td>北京</td><td>上海</td><td>杭州</td><td>昆明</td><td>08—90 大连</td><td>005—90 郑州</td></tr></table></body></html>  \n\n表3-10-5X06-1磷化底漆  \n\n\n<html><body><table><tr><td>技术要求名称</td><td>指</td><td></td></tr><tr><td>原液颜色与外观</td><td>黄色半透明黏稠液体（I）</td><td></td></tr><tr><td>漆膜外观</td><td>无色至微黄透明液体（Ⅱ） 黄绿色半透明</td><td></td></tr><tr><td>黏度（涂-4黏度计）/s</td><td>30～70</td><td></td></tr><tr><td>干燥时间（实干）/min</td><td>30</td><td></td></tr><tr><td>柔韧性/mm</td><td></td><td></td></tr><tr><td>冲击强度/N·cm</td><td>1 500</td><td></td></tr><tr><td>耐盐水性(3h)</td><td>无锈蚀</td><td></td></tr><tr><td>附着力/级</td><td>1</td><td></td></tr><tr><td></td><td></td><td></td></tr><tr><td>磷化液（Ⅱ）含磷酸/%</td><td>15~16</td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 855,
+        "chunk": "# （二）腻子  \n\n机床涂装常用的腻子有过氯乙烯腻子、原子灰等。其品种、性能等见表3-10-6。各种腻子的技术指标见表3-10-7～表3-10-11。  \n\n表3-10-6 机床涂装用腻子品种与性能   \n\n\n<html><body><table><tr><td>名称</td><td>G07-3各色过氯乙烯腻子</td><td>G07-4过氯乙烯腻子</td><td>G07-5各色过氯乙烯腻子</td></tr><tr><td>组成</td><td>由过氯乙烯树脂、改性醇酸树脂、 颜料、助剂及溶剂组成</td><td>由过氯乙烯树脂、颜料、填料、增 塑剂及溶剂组成</td><td>由过氯乙烯树脂、颜料、助剂、 溶剂等组成</td></tr><tr><td>性能</td><td>快干、坚硬、附着力好、易打磨并 有良好的耐水性与耐油性</td><td>干燥快、易刮涂、易打磨、附着 力好</td><td>干燥快、填平性好、易打磨</td></tr><tr><td>用途</td><td colspan=\"3\">用于铸件、钢件表面填平</td></tr><tr><td>配套稀料</td><td colspan=\"3\">X-3过氯乙烯漆稀释剂</td></tr><tr><td>配套性</td><td>可与过氯乙烯底漆、醇酸底漆、硝 基底漆与环氧底漆，过氯乙烯漆、酚 醛漆、醇酸漆及硝基漆配套使用</td><td>可与过氯乙烯底漆、过氯乙烯磁 漆及过氯乙烯改性磁漆、聚氨酯磁 漆等配套使用</td><td>可与过氯乙烯底漆、过氯乙烯 磁漆及过氯乙烯改性磁漆、聚氨 酯磁漆等配套使用</td></tr><tr><td>施工要求</td><td>1.以刮涂为主，但不宜多次重复 涂刮。 2.黏度偏高，可用X-3稀料调节 至合适黏度</td><td>1.过稠，可用X-3稀料调节至合 适黏度。 2.每次刮涂厚度不超过0.5mm</td><td>1.过稠，可用X-3稀料调节至 合适黏度。 2.填嵌时，切忌反复刮涂。</td></tr><tr><td>名称</td><td>G07-6过氯乙烯头道腻子</td><td>G07-6灰过氯乙烯二道腻子</td><td>3.每次刮涂厚度不超过0.5mm 过氯乙烯补漆腻子</td></tr><tr><td>组成</td><td>由过氯乙烯树脂、颜料、增塑剂及</td><td>由过氯乙烯树脂、顺丁烯二酸酐 树脂、颜料、增塑剂及溶剂组成</td><td>由过氯乙烯树脂、干性油、颜料</td></tr><tr><td>性能</td><td>溶剂组成 干燥快、易刮涂、附着力好</td><td>干燥快、易打磨、附着力好</td><td>及溶剂组成 易打磨、可干磨、可湿磨</td></tr><tr><td>用途 着力</td><td>用于增强过氯乙烯二道腻子的附</td><td>用于金属部件的填平或整平之用</td><td>用于填平较大的凹陷</td></tr><tr><td colspan=\"4\"></td></tr><tr><td>配套稀料 配套性</td><td>可与铁红过氯乙烯底漆、过氯乙烯底漆、醇酸底漆、过氯乙烯面漆、 烯二道腻子配套使用</td><td>X-3过氯乙烯漆稀释剂 可与过氯乙烯头道腻子、过氯乙 过氯乙烯改性面漆和聚氨酯面漆等 配套使用</td><td>可与过氯乙烯底漆、醇酸底漆、 过氯乙烯面漆、过氯乙烯改性面 漆、聚氨酯面漆等配套使用</td></tr><tr><td>施工要求</td><td>1.采用刮涂法施工。 2.过稠可用X-3稀料调节至合适 黏度。 3.每次刮涂的厚度不超过0.3mm黏度</td><td>1.可采用刮涂法施工。 2.必须刮在涂有头道腻子的层上。 3.过稠可用X-3稀料调节至合适陷较深，可分次刮涂，刮平为止</td><td>每次刮涂在5mm以下为宜，凹</td></tr></table></body></html>  \n\n表·3-10-7G07-4过氯乙烯腻子  \n\n\n<html><body><table><tr><td>技术要求名称</td><td>指</td><td>标</td></tr><tr><td colspan=\"2\">干燥时间（实干)/h</td><td></td></tr><tr><td colspan=\"2\">打磨性 易于打磨</td><td>良好</td></tr><tr><td colspan=\"2\">质量标准 QJ/SYQ 02. 0808—89</td><td>津Q/HG 3744—91</td></tr></table></body></html>  \n\n表3-10-8G07-5各色过氯乙烯腻子  \n\n\n<html><body><table><tr><td>技术要求名称</td><td colspan=\"4\">指标</td></tr><tr><td>腻子膜颜色和外观</td><td colspan=\"4\">色调不定，平整光滑无粗粒</td></tr><tr><td>涂层干后外观 固体含量/% 干燥时间(实干)/h</td><td>一 80 3</td><td>一 80 3</td><td>一 80 3</td><td>不起泡、不裂纹 一 5 一</td></tr><tr><td>柔韧性/mm 涂刮性</td><td colspan=\"4\">1 一 一 能自由涂刮不回卷</td></tr><tr><td>耐热性（65～70℃）/h</td><td>3</td><td>一</td><td>6</td><td>一</td></tr><tr><td>打磨性 耐油性（浸于32*机械油）/h</td><td>易打磨不粘砂纸 一</td><td>一 24</td><td>一 24</td><td>一</td></tr><tr><td>质量标准 产地</td><td>Q/JZQ 071—90 金华</td><td>Q/3201-NQJ-060—91 南京</td><td>赣Q/OH104—80 江西</td><td>XQ/G-51-0138—90 西安</td></tr></table></body></html>  \n\n表3-10-9G07-6过氯乙烯头道腻子  \n\n\n<html><body><table><tr><td></td><td>技术要求名称</td><td>指 标</td></tr><tr><td>颜色 干燥时间/h</td><td></td><td>灰色 3</td></tr><tr><td>涂刮性 打磨性</td><td></td><td>不应有卷边现象 易打磨</td></tr><tr><td>质量标准</td><td></td><td>QJ/SYQ 02.0807—89</td></tr></table></body></html>  \n\n表3-10-10 G07-7灰过氯乙烯二道腻子  \n\n\n<html><body><table><tr><td>技术要求名称</td><td>指 标</td></tr><tr><td>腻子膜颜色及外观</td><td colspan=\"2\">灰色，色调不定，无显著粗粒</td></tr><tr><td>固体含量/% M 干燥时间（实干)/h</td><td>70 3</td><td>70 2.5</td></tr><tr><td>柔韧性/mm 耐热性（68℃±2℃自干)/h</td><td>1 3</td><td>一 6</td></tr><tr><td>打磨性 涂刮性</td><td>打磨后，漆膜平整，无未研细之颜料或其他杂质 涂刮时不回卷</td><td></td></tr><tr><td>质量标准</td><td>重QCYQG51156—91</td><td>QJ/DQ02.G10—90</td></tr><tr><td>产地</td><td>重庆</td><td>大连</td></tr></table></body></html>  \n\n表3-10-11 机床用原子灰技术指标  \n\n\n<html><body><table><tr><td>技术要求名称</td><td>指 标</td></tr><tr><td>在容器中的状态</td><td>固化剂：有一定黏度不致流，色泽均匀一致，不分层，不结块 主剂：表面无结皮，搅拌时应色泽一致，无杂质异物，无沉底和揽不开的结块。</td></tr><tr><td>混合性</td><td>应该容易均匀混合</td></tr><tr><td>适用期</td><td>混合均匀后，能使用时间应可调在25℃士1℃时为15～40min</td></tr><tr><td>涂刮性</td><td>易涂刮，不卷边</td></tr><tr><td>干燥时间</td><td>25℃±1C在4h以内</td></tr><tr><td>涂膜外观</td><td>表面平整，收缩小，孔、纹路、气泡不明显，无肉眼可见裂纹</td></tr><tr><td>打磨性</td><td>可以打磨</td></tr><tr><td>耐冲击性</td><td>3.92N·m(40kgf·cm)</td></tr><tr><td>对上下涂层的配套性</td><td>与标准样板比较，无明显差异，并应有良好的结合力</td></tr><tr><td>贮存稳定性</td><td>根据地区要求选择使用，贮存有效期应不低于0.5年</td></tr><tr><td>稠度(指主剂）</td><td>11~13em</td></tr></table></body></html>  \n\n原子灰是由不饱和聚酯树脂、颜料、体质颜料加入多种助剂经混合研磨而成的双组分腻子。  \n原子灰涂层主要具有以下几个方面的特点。  \n\n$\\textcircled{1}$ 干燥快，可缩短施工周期。  \n\n原子灰一次可涂刮任意厚度，都能迅速干燥。特别是对表面缺陷大的铸件，可大大地缩短涂装施工周期。  \n\n$\\textcircled{2}$ 收缩性小，利于漆层表面平整。  \n\n我们通常使用的过氯乙烯腻子，其溶剂挥发率都在 $20\\%$ 以上，收缩性大，因此漆件表面不容易填补平整。而原子的主要成分是不饱和聚酯，固体含量高，收缩性小（收缩率在$2\\%$ 之内)，因此填平性好。  \n\n$\\textcircled{3}$ 涂层牢固，耐油性好。  \n\n原子灰涂层附着力强、坚硬、耐油。因此采用原子灰填补缺陷，可使漆层牢固，以避免或减少漆层起泡现象。  \n\n$\\textcircled{4}$ 可与多种漆种配套，便于选用涂料。  \n\n原子灰与过氯乙烯漆、丙烯酸漆、醇酸树脂漆、环氧树脂漆以及硝基漆等涂料，都具有良好的结合力，配套适应性好，便于用户根据本单位需要选用其他配套涂料品种。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 856,
+        "chunk": "# （三）面漆  \n\n机床涂装常用的面漆有过氯乙烯漆、改性过氯乙烯漆、过氯乙烯锤纹漆、丙烯酸漆及聚氨酯漆等。其品种见表3-10-12，性能与施工要求见表3-10-13，其技术指标见表 $3{-}10{-}14\\sim$ 表3-10-25。  \n\n表3-10-12 机床涂装用面漆品种  \n\n\n<html><body><table><tr><td>类 别</td><td>品 种</td></tr><tr><td>过氯乙烯漆</td><td>G04-12各色过氯乙烯机床磁漆、过氯乙烯机床内腔漆</td></tr><tr><td>改性过氯乙烯漆</td><td>G04-18各色改性过氯乙烯磁漆、改性过氯乙烯机床漆</td></tr><tr><td>过氯乙烯锤纹漆</td><td>G16-31过氯乙烯锤纹漆（分装）、G16-32各色过氯乙烯锤纹漆（分装）</td></tr><tr><td>丙烯酸漆</td><td>B04-11各色丙烯酸磁漆、各色丙烯酸硝基磁漆</td></tr><tr><td>聚氨酯漆</td><td>S04-7各色聚氨酯磁漆（分装）</td></tr></table></body></html>  \n\n11-111   \n\n\n<html><body><table><tr><td></td><td></td><td>表 3-10-13 机床涂装用面漆性能与施工要求</td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td>由过氯乙烯树脂、醇酸树脂、颜料、增塑剂等组成Ⅱ组</td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td>配套性</td><td>腻子配套使用 可与过氯乙烯底漆、醇酸底漆、过氯乙烯腻子、醇酸</td><td>可与G06-4铁红过氯乙烯底漆配套使用</td><td>套使用 可与过氯乙烯底漆、过氯乙烯腻子和醇酸底漆、醇酸腻子</td></tr><tr><td>施工要求</td><td>1.喷涂施工。 喷涂 2.用过氯乙烯稀料调整到施工黏度15～25s，进行</td><td>1.以喷涂为主，也可刷涂。 2.用X-3稀释剂调整到施工黏度15～25s，进行喷涂</td><td>1.喷涂施工。 3.施工黏度：14~16s。 2.I组与Ⅱ组，以1：3质量比例配制，搅拌均匀后施工。</td></tr><tr><td>品种</td><td>改性过氯乙烯机床漆</td><td>G16-31过氯乙烯锤纹漆（分装）</td><td>4.配漆及施工过程，与水、酸、酸、(类接触</td></tr><tr><td>组成</td><td>由过氯乙烯树脂、合成聚氨酯、增韧剂、颜料组成</td><td>由过氯乙烯树脂、醇酸树脂、酚醛树脂、增韧剂、溶剂组</td><td>由过氯乙烯树脂、松香改性树脂、颜料、增韧剂组成。</td></tr><tr><td>性能</td><td>候性慢迅速，外观平整光滑，有较高的光泽，有较好的耐</td><td>成、腰光、非浮、松调和均匀使用</td><td>时加入骤氨酸性、粉测和均使用纹清断</td></tr><tr><td>配套稀料</td><td>X-3过氯乙烯漆稀释剂 可与过氯乙烯底漆和过氯乙烯腻子配套使用</td><td>X25过氯乙烯低、素醇酸底漆、腻子配套使用</td><td>可与过氯乙烯、套使用</td></tr><tr><td>施工要求</td><td>噬途糖岛相对混度大于 85%以上要如 F2 </td><td>2.喷涂层次为两次，施工黏度第二次要比第一次稠一些。</td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td>品种</td><td></td><td></td><td>由性内组</td></tr><tr><td>性能</td><td>干燥快，漆膜丰满、色彩鲜艳、光亮，保光保色性</td><td>漆膜平整光滑、干燥较快，有良好的保色性能，有优良的</td><td>漆膜光泽高、丰满、保光保色性好、能耐湿热、耐机油、</td></tr><tr><td>配套性</td><td>配套稀料好耐机激乙耐酸、耐剂或 BG稀释剂 可与过氯乙烯底漆、腻子和醇酸底漆、腻子配套</td><td>耐候性与耐化学性稀释剂</td><td>切削渡丙烯酸漆稀释剂</td></tr><tr><td>使用</td><td>1.喷涂施工。</td><td>可与过氯乙烯底漆、腻子配套使用 1.喷涂施工。</td><td>子配套硬基底漆、过氯乙烯底漆、环氧底漆、氨基底漆及</td></tr><tr><td>施工要求</td><td>2.使用前要搅匀。 3.施工黏度15～23s</td><td>2.施工现场相对湿度大于85%时，要加F-2防潮剂。 3.施工黏度15~23s。</td><td>1.喷涂施工。 2.施工黏度15～23s</td></tr><tr><td></td><td>甲肉酸脂发其共乘脂、过氧乙稀树脂、</td><td></td><td></td></tr><tr><td>性能</td><td></td><td>干燥快、颜色鲜艳、保光保色性好、光泽高、附着力好、耐机</td><td>、组成</td></tr><tr><td></td><td>常温干燥，有较好的保光保色性和三防性能</td><td></td><td>常温固化成膜，有较好的附着力和良好的防腐性、耐</td></tr><tr><td>配套料</td><td>5 丙烯酸素乙释剂漆、铁红环氧底漆及腻了配套使用</td><td>过氯乙激受红腺酸底波及胍子配套使用</td><td>71素氯乙糖释排发服子配套使用</td></tr><tr><td>1.喷涂施工为主。</td><td></td><td>1.以喷涂施工为主，也可刷涂、浸涂。</td><td>1.可喷涂，也可刷涂与浸涂。</td></tr><tr><td>施工要求</td><td>2.施工黏度14~20s。 3.使用前要充分搅匀</td><td>2.施工黏度18~22s。</td><td>2.忌用醇类、胺类及含水分的溶剂。</td></tr><tr><td></td><td></td><td>3.使用前要充分搅匀，不能与其他性质的漆混合使用</td><td>3.配好的漆要在6h内用完。 4.施工黏度15～20s</td></tr></table></body></html>  \n\n表3-10-14G04-12各色过氯乙烯机床磁漆  \n\n\n<html><body><table><tr><td>技术要求名称</td><td colspan=\"3\"></td><td colspan=\"3\">标</td></tr><tr><td>漆膜颜色及外观</td><td colspan=\"6\">符合标准样板及其色差范围，漆膜平整光滑</td></tr><tr><td>黏度（涂-4黏度计）/s</td><td>25~80</td><td>25~80</td><td>30~90</td><td>40~60</td><td>25~80</td><td>25～60</td></tr><tr><td>固体含量/%</td><td></td><td></td><td>31</td><td>30</td><td>31</td><td></td></tr><tr><td>红色</td><td>24</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>蓝色</td><td>24</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>黑色</td><td>24</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>黄色</td><td>31</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>白色</td><td>31</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>遮盖力（干膜计)/(g/m²）</td><td></td><td>90</td><td>65</td><td>60</td><td>90</td><td>70</td></tr><tr><td>红色</td><td>80</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>黄色</td><td>90</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>蓝色</td><td>60</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>白色</td><td>70</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>黑色</td><td>20</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>硬度</td><td>0.4</td><td>0.3</td><td>0.4</td><td>0.5</td><td>0.3</td><td>0.4</td></tr><tr><td>光泽/%</td><td></td><td>70</td><td>80</td><td>90</td><td>70</td><td>80</td></tr><tr><td>红色、黄色、蓝色、白色、黑色</td><td>70</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>干燥时间/min 表干</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td><td></td></tr><tr><td></td><td>120</td><td>180</td><td>60</td><td>120</td><td>180</td><td></td></tr><tr><td>实干</td><td>500</td><td>500</td><td></td><td></td><td></td><td>90</td></tr><tr><td>冲击强度/N·cm</td><td>1</td><td></td><td>500</td><td>500</td><td>500</td><td>500</td></tr><tr><td>柔韧性/mm</td><td></td><td>1</td><td>1</td><td>1</td><td></td><td>1 3</td></tr><tr><td>附着力/级</td><td>3</td><td>3</td><td>3</td><td>2</td><td>3</td><td></td></tr><tr><td>磨光性(打磨后以光泽计)/%≥</td><td>80</td><td>60</td><td></td><td></td><td></td><td></td></tr><tr><td>红色</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>黄色</td><td>65</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>蓝色</td><td>70</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>白色</td><td>65</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>黑色</td><td>80</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>耐水性(25℃士1℃蒸馏水)/h</td><td>24</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>耐油性(浸于32\"机械油）/h</td><td></td><td></td><td>24</td><td></td><td>12</td><td></td></tr><tr><td>耐冷却液/h</td><td></td><td></td><td>24</td><td></td><td></td><td></td></tr><tr><td>耐切削液/d</td><td></td><td></td><td></td><td>7</td><td></td><td></td></tr><tr><td>质量标准</td><td>XQ/G-51- 0142-90</td><td>重QCYQ 51147—91</td><td>Q(HG)HY 02491</td><td>QJ/DQ 02.G06—90</td><td>QB/ZQ BJ004—91</td><td>QJ/ZQ 01.08-04—90</td></tr><tr><td>产地</td><td>西安</td><td>重庆</td><td>广州</td><td>大连</td><td>郑州</td><td>遵义</td></tr></table></body></html>  \n\n表3-10-15 过氯乙烯机床内腔漆  \n\n\n<html><body><table><tr><td>技术要求名称</td><td>指</td><td>标</td><td>技术要求名称</td><td>指</td><td>标</td></tr><tr><td>漆膜颜色及外观 黏度（涂-4黏度计）/s 干燥时间 ≤ 表干/min 实干/h</td><td>符合标准样板及其色差范围，平整光滑 70~150</td><td>30 4 5 质量标准</td><td>冲击强度/N·cm 附着力/级 ≤ 固体含量/% 耐油性（32*机械油）/h</td><td>500 3 46 24</td><td></td></tr></table></body></html>  \n\n表3-10-16G04-18各色改性过氯乙烯磁漆  \n\n\n<html><body><table><tr><td>技术要求名称</td><td>指 标</td></tr><tr><td>外观，组分I 浅黄色至棕黄色透明液体 硬度</td><td>技术要求名称 指 标 0.4</td></tr><tr><td>组分Ⅱ 各色黏稠液体 遮盖力/(g/m²）</td><td></td></tr><tr><td></td><td>80</td></tr><tr><td>固体含量（组分Ⅱ）/% 干燥时间(实干)/h</td><td>37~41 红色</td></tr><tr><td>2 黄色</td><td>90</td></tr><tr><td>光泽/% W 白色</td><td>蓝色 60</td></tr><tr><td>80 白色</td><td>70</td></tr><tr><td>其他各色 90 柔韧性/mm</td><td>黑色 20</td></tr><tr><td>1 附着力/级</td><td>≤ 2</td></tr><tr><td>冲击强度/N·cm 500</td><td>质量标准 QJ/SYQ 02.0809-89</td></tr></table></body></html>  \n\n表3-10-17 改性过氯乙烯机床漆  \n\n\n<html><body><table><tr><td>技术要求名称</td><td>指 标</td><td>技术要求名称</td><td>指</td><td>标</td></tr><tr><td>颜色及外观</td><td>符合标准样板色差范围，漆膜平整光滑</td><td>硬度</td><td>0.4</td><td></td></tr><tr><td>黏度（涂-4黏度计，25℃）/s</td><td>40~60</td><td>附着力/级 ≤</td><td>2</td><td></td></tr><tr><td>固体含量/%</td><td>32</td><td>柔韧性/mm</td><td>1</td><td></td></tr><tr><td>干燥时间 ≤</td><td></td><td>光泽/%</td><td>90</td><td></td></tr><tr><td>表干/min</td><td>20</td><td>冲击强度/N·cm</td><td>500</td><td></td></tr><tr><td>实干/h</td><td>1.5</td><td>质量标准</td><td>QJ/SYQ 02.0811—89</td><td></td></tr></table></body></html>  \n\n表3-10-18G16-31过氯乙烯锤纹漆  \n\n\n<html><body><table><tr><td>技术要求名称</td><td></td><td>指</td><td>标</td><td></td><td></td></tr><tr><td>漆膜颜色及外观</td><td colspan=\"5\">符合标准样板及其色差范围，锤纹均匀、清晰</td></tr><tr><td>黏度（不加铝粉浆，涂-4黏度计）/s 固体含量（不加铝粉浆）/% 柔韧性/mm ≤</td><td>30 一 1</td><td>20~50 25</td><td>25~80 一 2</td><td>30~90 一 1</td><td>60~120 一 1</td><td>40~80 25</td></tr><tr><td>干燥时间/h 表干 实干</td><td>1 24</td><td>0.5 2</td><td>0.5 2</td><td>0.5 2</td><td>1 24</td><td>0.5 1</td></tr><tr><td>花纹/mm² 冲击强度/N·cm</td><td>一 500 一</td><td>1 1</td><td>一 300 0.3</td><td>一 500 0.25</td><td>一 100</td><td>1 一</td></tr><tr><td>硬度 附着力/级 耐油性（32机油）/h</td><td>3 一</td><td>1</td><td>2 24</td><td>3 一</td><td>3 一</td><td>一 一</td></tr><tr><td>耐冷却液性/h</td><td></td><td>一</td><td>24</td><td>一</td><td>一</td><td>一</td></tr><tr><td>质量标准</td><td>Q/STL 35-91</td><td>Q/GHTB- 50—91</td><td>Q(HG)HY 026—91</td><td>Q/H12 118-91</td><td>津Q/HG NQJ-138—91</td><td>Q/3201-</td></tr></table></body></html>  \n\n表3-10-19G16-32各色过氯乙烯锤纹漆（分装）  \n\n\n<html><body><table><tr><td>技术要求名称</td><td>指标</td><td>技术要求名称</td><td>指标</td></tr><tr><td>颜色及外观 黏度（涂-4黏度计）/s</td><td>符合标准样板 30</td><td>干燥时间/h 表干</td><td>1</td></tr><tr><td>柔韧性/mm 附着力/级 ≤</td><td>1</td><td>实干 质量标准</td><td>24 XQ/G-51-0140—90</td></tr></table></body></html>  \n\n表3-10-20G04-20各色丙烯酸过氯乙烯机电磁漆  \n\n\n<html><body><table><tr><td>技术要求名称</td><td>指 标</td><td>技术要求名称</td><td>指 标</td></tr><tr><td>漆膜颜色及外观 黏度（涂-4黏度计）/s 固体含量/% 红色、蓝色、黑色 其他色 遮盖力/（g/m²） ≤ 黑色</td><td>符合标准样板及色差范围，漆膜平整光滑 30~90 28 33 30</td><td>干燥时间/min 表干 实于 硬度 冲击性/N·cm 附着力/级</td><td>15 120 0.4 500 2</td></tr><tr><td>蓝色 白色 红色、黄色 光泽/%</td><td>120 60 80 90</td><td>细度/μm 耐机油性（32*机械油）/h 耐切削液/h 质量标准</td><td>35 24 72 津Q/HG3188--91</td></tr></table></body></html>  \n\n表3-10-21 各色过氯乙烯丙烯酸外用磁漆  \n\n\n<html><body><table><tr><td>技术要求名称</td><td></td><td>指 标</td></tr><tr><td>漆膜颜色及外观</td><td colspan=\"3\">符合标准样板及其色差范围，漆膜平整光滑</td></tr><tr><td>附着力/级 黏度(涂-4黏度计）/s</td><td>2 40～100</td><td>2 25~80</td><td>2 40~80</td></tr><tr><td>固体含量/% W 红色、蓝色、黑色</td><td>28</td><td>28</td><td>30</td></tr><tr><td>其他各色 遮盖力/(g/m²） ≤</td><td>33</td><td>33</td><td>35</td></tr><tr><td>黑色</td><td>30</td><td>20</td><td>20</td></tr><tr><td>深复色</td><td>40 50</td><td>30</td><td>40 50</td></tr><tr><td>浅复色</td><td></td><td>50</td><td></td></tr><tr><td>白色、正蓝色</td><td>60</td><td>60</td><td>60</td></tr><tr><td>红色</td><td>80</td><td>80</td><td>80</td></tr><tr><td></td><td>80</td><td></td><td>90</td></tr><tr><td>黄色</td><td>120</td><td>90</td><td></td></tr><tr><td>蓝色</td><td></td><td>100</td><td>一</td></tr><tr><td>干燥时间/min ≤</td><td></td><td></td><td></td></tr><tr><td>表干</td><td>15</td><td></td><td>20</td></tr><tr><td>实干</td><td>120</td><td>一</td><td>90</td></tr><tr><td>硬度</td><td>0.4</td><td>0.5</td><td>0.4</td></tr><tr><td>柔韧性/mm</td><td>一</td><td>1</td><td>1</td></tr><tr><td>冲击强度/N·cm</td><td>500</td><td>500</td><td>500</td></tr><tr><td>光泽/%</td><td>90</td><td></td><td></td></tr><tr><td></td><td></td><td>90</td><td>90</td></tr><tr><td>黑色 其他各色</td><td></td><td>80</td><td>80</td></tr><tr><td>磨光性/%</td><td></td><td></td><td></td></tr><tr><td>黑色</td><td></td><td>80</td><td>一</td></tr><tr><td></td><td></td><td>70</td><td></td></tr><tr><td>其他各色</td><td></td><td></td><td></td></tr><tr><td>耐水性(25℃±1℃蒸馏水)/h</td><td>24</td><td>24</td><td>24</td></tr><tr><td>质量标准</td><td>津Q/HG 3189—91</td><td>Q/WST-JC015—90</td><td>XQ/G-51-0152—90</td></tr><tr><td>产地</td><td>天津</td><td>武汉</td><td>西安</td></tr></table></body></html>  \n\n表3-10-22 各色丙烯酸硝基磁漆  \n\n\n<html><body><table><tr><td>技术要求名称</td><td colspan=\"2\"></td><td>指 标</td><td colspan=\"2\"></td></tr><tr><td>漆膜颜色及外观</td><td colspan=\"5\">符合标准样板及其色差范围，平整光滑</td></tr><tr><td>黏度（涂-4黏度计）/s 固体含量/%</td><td>55～200</td><td>55~200</td><td>50~80</td><td>50～150</td><td>25～150</td></tr><tr><td>浅色</td><td>38</td><td>38</td><td>38 一</td><td></td><td></td></tr><tr><td>深色</td><td>34</td><td>34</td><td></td><td>1</td><td>1 一</td></tr><tr><td>红色、蓝色、黑色</td><td>一</td><td>一</td><td>一</td><td>34</td><td></td></tr><tr><td>其他色</td><td></td><td></td><td>一</td><td>38</td><td>一</td></tr><tr><td>轻质</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td>一</td><td></td><td>34</td></tr><tr><td>重质</td><td></td><td></td><td></td><td>一</td><td>38</td></tr><tr><td>干燥时间/min</td><td>≤</td><td></td><td></td><td></td><td></td></tr><tr><td>表干</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td></tr><tr><td>实干</td><td>50 M</td><td>50</td><td>50</td><td>50</td><td>60</td></tr><tr><td>硬度</td><td>0.55</td><td>0.55</td><td>0.5</td><td>0.6</td><td>0.6</td></tr><tr><td>柔韧性/mm</td><td>≤ 2</td><td>2</td><td>2</td><td>1</td><td>1</td></tr><tr><td>附着力/级</td><td>2</td><td>2</td><td>2</td><td>2</td><td>2</td></tr><tr><td>冲击强度/N·cm</td><td>M 500</td><td>500</td><td>500</td><td>500</td><td>500</td></tr><tr><td>光泽/%</td><td>80 Q/3201-NQJ-</td><td>Q/320500</td><td></td><td>Q/WQJ</td><td>75 Q/GHTB</td></tr><tr><td>质量标准</td><td>1112—91IⅡ</td><td>ZQ26-90</td><td>Q/HQB 97—90</td><td>01.057—91</td><td>090--91</td></tr><tr><td>产地</td><td>南京</td><td>苏州</td><td>哈尔滨</td><td>芜湖</td><td>上海</td></tr><tr><td>黏度（涂-4黏度计）/s 光泽/%</td><td colspan=\"2\">80~120 90</td><td colspan=\"3\">55～200</td></tr><tr><td>黑色</td><td colspan=\"2\"></td><td colspan=\"3\">85</td></tr><tr><td>其他色</td><td colspan=\"2\"></td><td colspan=\"3\">80</td></tr><tr><td>干燥时间/min ≤</td><td colspan=\"2\"></td><td colspan=\"3\"></td></tr><tr><td>表干</td><td colspan=\"2\">10</td><td colspan=\"3\"></td></tr><tr><td></td><td colspan=\"2\"></td><td colspan=\"3\">10</td></tr><tr><td>实干</td><td colspan=\"2\">100</td><td colspan=\"3\">50</td></tr><tr><td>柔韧性/mm</td><td colspan=\"2\">2</td><td colspan=\"3\">一</td></tr><tr><td>冲击强度/N·cm</td><td colspan=\"2\">400</td><td colspan=\"3\"></td></tr><tr><td>硬度</td><td colspan=\"2\">W 0.45</td><td colspan=\"3\">一</td></tr><tr><td>附着力/级</td><td colspan=\"2\">≤ 2</td><td colspan=\"3\"></td></tr><tr><td>固体含量/%</td><td colspan=\"2\">35</td><td colspan=\"3\"></td></tr><tr><td>红色、黑色、深蓝色、紫红色、蓝色</td><td colspan=\"2\"></td><td colspan=\"3\">34</td></tr><tr><td>其他色</td><td colspan=\"2\"></td><td colspan=\"3\">38</td></tr><tr><td>遮盖力/（g/m²） ≤</td><td colspan=\"2\"></td><td colspan=\"3\"></td></tr><tr><td>黑色</td><td colspan=\"2\"></td><td colspan=\"3\"></td></tr><tr><td></td><td colspan=\"2\"></td><td colspan=\"3\">20</td></tr><tr><td>白色</td><td colspan=\"2\"></td><td colspan=\"3\">60</td></tr><tr><td>黄色</td><td colspan=\"2\"></td><td colspan=\"3\">80</td></tr><tr><td>质量标准</td><td colspan=\"2\">Q(HG)HY 059—92</td><td colspan=\"3\">Q/STL 062—91</td></tr><tr><td></td><td colspan=\"2\"></td><td colspan=\"3\"></td></tr><tr><td>产地</td><td colspan=\"2\">广州</td><td colspan=\"3\">石家庄</td></tr></table></body></html>  \n\n表3-10-23 B04-11各色丙烯酸磁漆  \n\n\n<html><body><table><tr><td>技术要求名称</td><td colspan=\"3\">指 标</td></tr><tr><td>漆膜颜色及外观</td><td colspan=\"3\">符合标准样板及其色差范围，漆膜平整光滑</td></tr><tr><td>黏度(涂-4黏度计)/s</td><td></td><td>≥25</td><td>60~90</td></tr><tr><td>白色 其他色</td><td>80~160 30~160</td><td></td><td></td></tr></table></body></html>  \n\n表3-10-24 各色丙烯酸磁漆  \n\n\n<html><body><table><tr><td>技术要求名称</td><td colspan=\"3\">指 标</td></tr><tr><td>漆膜颜色及外观</td><td colspan=\"3\">符合标准样板及其色差范围，漆膜平整光滑</td></tr><tr><td>固体含量/% M 铝色</td><td>26</td><td>31</td><td>20</td></tr><tr><td>深蓝色、红色、黑色</td><td>32</td><td>26</td><td></td></tr><tr><td>白色</td><td>38</td><td>31 31</td><td></td></tr><tr><td>其他色</td><td>34</td><td></td><td></td></tr><tr><td>干燥时间</td><td>30</td><td>20</td><td>90</td></tr><tr><td>表干/min</td><td></td><td></td><td></td></tr><tr><td>实干/h</td><td>2</td><td>1.5</td><td>24</td></tr><tr><td>硬度</td><td>0.5</td><td>0.4</td><td>0.4</td></tr><tr><td>附着力/级 ≤</td><td>2</td><td>一</td><td>一</td></tr><tr><td>冲击强度/N·cm</td><td>一</td><td>500</td><td>350</td></tr><tr><td>柔韧性/mm ≤</td><td>3</td><td>1</td><td>1</td></tr><tr><td>耐水性/h</td><td>24</td><td>一</td><td>24</td></tr><tr><td>耐机油/h</td><td>24</td><td>一</td><td>24</td></tr><tr><td>遮盖力/（g/m²）</td><td>一</td><td></td><td>一</td></tr><tr><td>红色</td><td></td><td>80</td><td></td></tr><tr><td></td><td></td><td>90</td><td></td></tr><tr><td>白色、黄色</td><td></td><td></td><td></td></tr><tr><td>蓝色</td><td></td><td>100</td><td></td></tr><tr><td>黑色</td><td></td><td>20</td><td></td></tr><tr><td>浅复色</td><td></td><td>50</td><td></td></tr><tr><td>深复色</td><td></td><td>40</td><td></td></tr><tr><td>质量标准</td><td>Q/GHTB-070—91</td><td>QJ/DQ02.B01—90</td><td>XQ/G-51-0159—90</td></tr><tr><td>产地</td><td>上海</td><td>大连</td><td>西安</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>技术要求名称</td><td colspan=\"4\">指 标</td></tr><tr><td>漆膜颜色及外观</td><td colspan=\"4\">符合标准样板及其色差范围，漆膜平整光滑</td></tr><tr><td>黏度（涂-4黏度计）/s</td><td>40~80</td><td>40~120</td><td></td><td>60~90</td></tr><tr><td>固体含量/%</td><td></td><td>36</td><td></td><td>一</td></tr><tr><td>黑色、红色、蓝色</td><td>26</td><td></td><td></td><td></td></tr><tr><td></td><td>31</td><td></td><td></td><td></td></tr><tr><td>其他各色</td><td></td><td>1</td><td></td><td>20</td></tr><tr><td>细度/μm 光泽/%</td><td>≤</td><td></td><td></td><td>90</td></tr><tr><td>黑色</td><td>90</td><td>90</td><td></td><td></td></tr><tr><td></td><td>80</td><td>80</td><td></td><td></td></tr><tr><td>其他各色</td><td>≤ 2</td><td></td><td>2</td><td>2</td></tr><tr><td>附着力/级</td><td>0.4</td><td></td><td>0.4</td><td>0.3</td></tr><tr><td>硬度</td><td></td><td>1</td><td>一</td><td>1</td></tr><tr><td>柔韧性/mm 冲击强度/N·cm</td><td>> 500</td><td></td><td>400</td><td>500</td></tr><tr><td>遮盖力/（g/m²）</td><td>≤</td><td></td><td></td><td></td></tr><tr><td>白色</td><td>60</td><td></td><td></td><td>110</td></tr><tr><td>黄色</td><td>120</td><td></td><td></td><td>140</td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td>绿色</td><td>20</td><td></td><td></td><td>55</td></tr><tr><td>黑色</td><td></td><td>80</td><td></td><td>40</td></tr><tr><td>大红色</td><td></td><td>50</td><td></td><td>140</td></tr><tr><td>浅复色</td><td></td><td>40</td><td></td><td></td></tr><tr><td>深复色</td><td></td><td></td><td></td><td>一</td></tr><tr><td>深蓝色</td><td>100</td><td></td><td></td><td>80</td></tr><tr><td>于燥时间/min</td><td>≤</td><td></td><td></td><td></td></tr><tr><td>表干</td><td></td><td>20</td><td>30</td><td>180</td></tr><tr><td>实干</td><td>90</td><td></td><td>120</td><td>600</td></tr></table></body></html>  \n\n<html><body><table><tr><td>技术要求名称</td><td colspan=\"3\">指 标</td></tr><tr><td>漆膜颜色及外观</td><td colspan=\"3\">符合标准样板及其色差范围，漆膜平整光滑</td></tr><tr><td>耐水性/h 耐机油（浸32机油中）/h</td><td>24 24</td><td>一 一</td><td>24 25</td></tr><tr><td>质量标准</td><td>重QCYQG51077—89</td><td>Q/GHTB-073—91</td><td>Q/320500ZQ 27—90</td></tr><tr><td>产地</td><td>重庆</td><td>上海</td><td>苏州</td></tr></table></body></html>  \n\n表3-10-25S04-7各色聚氨酯磁漆（分装）  \n\n\n<html><body><table><tr><td>技术要求名称</td><td>指 标</td></tr><tr><td>漆膜颜色及外观 黏度（涂-4黏度计）/s</td><td colspan=\"3\">符合标准色差样板，漆膜平整光滑 40~100</td></tr><tr><td>固体含量/%</td><td colspan=\"3\">W</td></tr><tr><td>红色</td><td></td><td>35</td><td></td></tr><tr><td>灰色</td><td></td><td>45</td><td></td></tr><tr><td>干燥时间/h</td><td></td><td></td><td></td></tr><tr><td>实干</td><td></td><td></td><td>24</td></tr><tr><td>烘干(100°℃)</td><td></td><td></td><td>1</td></tr><tr><td>硬度</td><td></td><td>M</td><td>0.4</td></tr><tr><td>柔韧性/mm</td><td></td><td>3</td><td></td></tr><tr><td>光泽/%</td><td></td><td>M 80</td><td></td></tr><tr><td></td><td></td><td>≤ 2</td><td></td></tr><tr><td>附着力/级</td><td></td><td>24</td><td></td></tr><tr><td>耐水性/h</td><td></td><td></td><td></td></tr><tr><td>质量标准</td><td></td><td></td><td>Q/GHTB-108-92</td></tr><tr><td>产地</td><td></td><td>上海等</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 857,
+        "chunk": "# （四）辅助材料  \n\n续表  \n\n\n<html><body><table><tr><td>二甲苯</td><td>100</td></tr><tr><td>丙酮</td><td>200</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 858,
+        "chunk": "# 1.稀释剂  \n\n，机床涂装常用稀释剂有：X-3过氯乙烯漆稀释剂、X-25过氯乙烯锤纹漆稀释剂、X-5丙烯酸漆稀释剂及7001聚氨酯漆稀释剂。  \n\n（1）X-3过氯乙烯漆稀释剂  \n$\\textcircled{1}$ 配比 $(\\log/\\mathbf{t})$   \n乙酸丁酯 180  \n乙酸乙酯 40  \n甲苯 560  \n\n$\\textcircled{2}$ 主要技术指标 见表3-10-26。  \n\n表3-10-26X-3过氯乙烯漆稀释剂主要技术指标  \n\n\n<html><body><table><tr><td>技术要求名称</td><td>指标</td></tr><tr><td>颜色/号 ≤ 外观和透明度 酸值/（mgKOH/g） 水分</td><td>1 清澈透明、无悬浮物 0.15 不浑浊</td></tr><tr><td>白化性 质量标准</td><td>W 30 漆膜不应发白及没有无光斑点 ZBG 52002--89</td></tr></table></body></html>\n\n$\\textcircled{3}$ 施工要点 主要用于过氯乙烯清漆、磁漆、底漆、腻子等，不能混入其他稀释剂，  \n\n特别是醇类与汽油等。  \n\n（2）X-5丙烯酸漆稀释剂$\\textcircled{1}$ 主要技术指标 见表3-10-27。  \n\n表3-10-27X-5丙烯酸漆稀释剂主要技术指标  \n\n\n<html><body><table><tr><td>技术要求名称</td><td colspan=\"6\">指</td></tr><tr><td>外观和透明度</td><td colspan=\"6\">清澈透明、无悬浮物、无机械杂质</td></tr><tr><td>颜色/号 ≤</td><td>1</td><td>1</td><td>1 1</td><td>1</td><td>1</td><td>1</td></tr><tr><td colspan=\"9\">水分 不浑浊</td></tr><tr><td>酸值/(mgKOH/g) 胶凝数/mL</td><td>0.1 M 一</td><td>0.1 3</td><td>0.1 2</td><td>0.2 2</td><td>一 一</td><td>0.15 2</td><td>2</td></tr><tr><td>产地</td><td></td><td>北京</td><td>青岛</td><td>天津</td><td>上海</td><td>昆明 石家庄</td><td>西安</td></tr></table></body></html>  \n\n<html><body><table><tr><td>② 施工要点主要用于稀释各种丙烯酸漆，不能与不同品种的涂料和稀释剂混合使用。</td></tr><tr><td>(3）X-25过氯乙烯锤纹漆稀释剂</td></tr><tr><td>①配比(kg/t)</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 主要技术指标 见表3-10-28。  \n\n表3-10-28X-25过氯乙烯锤纹漆稀释剂主要技术指标  \n\n\n<html><body><table><tr><td>技术要求名称</td><td colspan=\"3\">指 标</td></tr><tr><td>外观和透明度</td><td colspan=\"3\">清澈透明、无悬浮物</td></tr><tr><td>颜色/号 ≤</td><td>1</td><td>1</td><td>1</td></tr><tr><td>水分</td><td></td><td>不浑浊</td><td></td></tr><tr><td>胶凝值/mL 挥发性/倍</td><td>40 北京</td><td>40 9~18 重庆</td><td>西北</td></tr></table></body></html>  \n\n$\\textcircled{3}$ 施工要点该稀释剂为过氯乙烯锤纹漆专用稀料，施工前可分次小量将铝银浆调至均匀，无团粒状物，把调稀的铝银浆加人漆料中，再加人适量的本稀释剂，并搅拌均匀后使用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 859,
+        "chunk": "# （4）7001聚氨酯漆稀释剂",
+        "category": " Introduction"
+    },
+    {
+        "id": 860,
+        "chunk": "# $\\textcircled{1}$ 主要技术指标 见表3-10-29。  \n\n表3-10-297001聚氨酯漆稀释剂主要技术指标  \n\n\n<html><body><table><tr><td>技术要求名称</td><td>指标</td><td>技术要求名称</td><td>指标</td><td></td></tr><tr><td>外观</td><td>清澈透明、无悬浮物</td><td>酸值/(mgKOH/g)</td><td>≤0.2</td><td></td></tr><tr><td>颜色/号</td><td>1</td><td>溶解性</td><td>无沉淀凝结</td><td></td></tr><tr><td>水分</td><td>不浑浊</td><td>质量标准</td><td>Q/GHTB-121—91</td><td></td></tr></table></body></html>  \n\n$\\textcircled{2}$ 施工要点该稀释剂用于聚氨酯清漆、磁漆、底漆等。施工时，按工艺配比要求混合均匀，严禁与其他不同品种漆料、稀释剂混合使用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 861,
+        "chunk": "# 2.防潮剂  \n\n机床涂装常用的防潮剂是F-2过氯乙烯漆防潮剂，它在相对湿度较大的气候条件下可防止过氯乙烯漆漆膜发白。它有较高的稀释能力，与过氯乙烯漆稀释剂配合使用。若单独使  \n\n用，将会影响漆膜的干燥时间与颜色等。  \n\nF-2过氯乙烯漆防潮剂的技术指标如表3-10-30所示。  \n\n表3-10-30F-2过氯乙烯漆防潮剂  \n\n\n<html><body><table><tr><td>技术要求名称</td><td>指标</td><td>技术要求名称</td><td>指标</td></tr><tr><td>透明度</td><td>透明、无悬评物</td><td>胶数/mL</td><td>漆膜不呈白雾及无光班点</td></tr><tr><td>挥发性/倍</td><td>≤14</td><td>质量标准</td><td>ZBG 52007-87</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 862,
+        "chunk": "# 第三节 机床涂装工艺  \n\n机床涂装工艺包括机床零、部件涂装，机床钣金件涂装与成品机床涂装三部分内容，现分述如下。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 863,
+        "chunk": "# 一、机床零、部件涂装工艺",
+        "category": " Introduction"
+    },
+    {
+        "id": 864,
+        "chunk": "# （一）机床零、部件涂装前的表面处理  \n\n涂装前的表面处理是机床零、部件涂装工艺中很重要的一环，它关系到涂层的附着力、涂层的使用寿命和涂层的装饰性。若处理不妥，将会留下隐患，致使涂层起泡、开裂、剥落，这不仅造成经济、时间和人力的浪费，同时有损机床产品的声誉。  \n\n机床零、部件大多为铸铁件，铸铁件结构比钢件疏松，而且表面多气孔、针孔，因此铸铁件不宜酸洗。铸铁件通常是大件采用喷丸方法处理，小件采用滚筒处理。",
+        "category": " Introduction"
+    },
+    {
+        "id": 865,
+        "chunk": "# 1.抛丸、喷丸处理  \n\n喷丸处理是用专用喷枪利用压缩空气将金属弹丸高速喷射在被处理的铸件表面，利用弹丸的冲击和摩擦作用，将铸铁表面的氧化皮、铁锈、型砂等脏物处理干净。  \n\n机床铸铁部件在喷丸室内的工作台上不断转动。  \n\n金属弹丸材料有铁丸和钢丸两种，弹丸直径为1.0～3.0mm。喷丸处理的压力为$0.4{\\sim}0.6\\mathrm{MPa}$ 0  \n\n国产喷丸清理设备型号、主要技术规格见表3-10-31～表3-10-33。  \n\n表3-10-31 喷丸器  \n\n\n<html><body><table><tr><td rowspan=\"2\">产品名称</td><td rowspan=\"2\">型号</td><td colspan=\"4\">技术参数</td><td rowspan=\"2\">电机功 率/kW</td><td rowspan=\"2\">重量 /t</td><td rowspan=\"2\">外形尺寸 (长×宽×高)/mm</td></tr><tr><td></td><td>容量/m²喷丸量/（kg/h)</td><td>喷枪数量/个</td><td>喷嘴直径/mm</td></tr><tr><td rowspan=\"2\">喷丸器</td><td>Q214</td><td>0.14</td><td>1000~1500</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td>１2</td><td>10</td><td></td><td>0.8</td><td>2400× 716× 1816</td></tr></table></body></html>  \n\n表3-10-32 抛、喷丸清理室  \n\n\n<html><body><table><tr><td rowspan=\"2\">产品名称</td><td rowspan=\"2\">型号</td><td colspan=\"3\"></td><td rowspan=\"2\">电机</td><td rowspan=\"2\">重量/t</td><td rowspan=\"2\">(长外尺)/mm</td></tr><tr><td>台车载重/t</td><td>工件技大参数/mm</td><td>生产率/(t/h)</td></tr><tr><td>抛、喷</td><td>Q765</td><td>5</td><td>2000X 2000X1000</td><td></td><td>65.1</td><td>17</td><td>7000X5000X7250</td></tr><tr><td rowspan=\"3\">丸清 理室</td><td>Q7605</td><td></td><td>3000X1300</td><td>6~8</td><td>38.5</td><td>14</td><td>6600X4700×8219</td></tr><tr><td>Q7630</td><td>30</td><td>4000X2000</td><td></td><td>108.2</td><td>37.8</td><td>9168X7680×10874</td></tr><tr><td>Q7630N</td><td></td><td></td><td></td><td>112.2</td><td>45</td><td>9418×7467×10900</td></tr></table></body></html>  \n\n表3-10-33 抛丸清理机  \n\n\n<html><body><table><tr><td rowspan=\"2\">产品名称</td><td rowspan=\"2\">型号</td><td colspan=\"3\">技术参数</td><td rowspan=\"2\">电机功 率/kW</td><td rowspan=\"2\">重量/t</td><td rowspan=\"2\">外形尺寸 （长×宽×高）/mm</td></tr><tr><td>直径转台 /mm</td><td>最大载重量 /kg</td><td>清理件最大 尺寸/mm</td></tr><tr><td rowspan=\"5\">转台 抛丸 清理机</td><td>Q3516 Q3525A</td><td>1600</td><td>1500</td><td>350X400</td><td>37</td><td>9.24</td><td>5647×3098×5605</td></tr><tr><td rowspan=\"5\">Q3516 Q3518</td><td></td><td>600</td><td>700×250</td><td>18.9</td><td></td><td>2825×2800X4200</td></tr><tr><td>1800</td><td></td><td>1600×500</td><td>53.24</td><td>10</td><td>4400×3578X5060</td></tr><tr><td>2500</td><td>1500</td><td>1000X600</td><td>17.6</td><td>5.1</td><td>3138×3015×4402</td></tr><tr><td></td><td>1000</td><td>1000×500</td><td>25.9</td><td>5.86</td><td>3317×3000X6410</td></tr><tr><td>Q3525B Q366</td><td></td><td></td><td>2500×1900</td><td>74.2</td><td>28.8</td><td>6972×5050×7331</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 866,
+        "chunk": "# 2.电动砂轮处理  \n\n要使铸件表面的毛刺、浇冒口等缺陷平整，常需借用手提电动砂轮机来修整，个别小毛刺也可用锂刀凿子之类手工工具予以修整。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 867,
+        "chunk": "# （二）机床零、部件涂装工艺要求",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 868,
+        "chunk": "# 1．机床零、部件涂装工艺要求  \n\n$\\textcircled{1}$ 涂装前要对工件进行检查，对表面凹凸不平处要用工具对其进行修整，表面的污物要予以去除。  \n\n$\\textcircled{2}$ 底漆刷或喷、浸要均匀，底漆在使用前必须充分搅拌均匀，稀释至适当黏度。  \n\n$\\textcircled{3}$ 经过机械加工后的零、部件，涂漆前需用金属清洗剂或洁净的工业汽油进行淋洗或刷洗，要彻底去除表面的油污及其他脏物。  \n\n$\\textcircled{4}$ 填补铸件凹陷的填坑腻子（原子灰)，使用时要按产品使用说明加入适量固化剂。使用前必须充分搅拌均匀。  \n\n$\\textcircled{5}$ 过氯乙烯腻子，每次刮涂不宜太厚，每次刮涂厚度一般为 $0.5\\mathrm{mm}$ ，每次刮涂需待上道腻子干燥后进行。  \n\n$\\textcircled{6}$ 过氯乙烯腻子干燥后才能打磨，每次打磨后需彻底清除表面的磨浆、粉尘。  \n\n$\\textcircled{7}$ 水磨时，为避免机床零、部件加工表面产生锈蚀，宜采用防锈水进行打磨。防锈水参考配方：  \n\n<html><body><table><tr><td>组分</td><td>质量分数</td><td>组分</td><td>质量分数</td></tr><tr><td>“ 硼酸</td><td>1.0%</td><td>香精</td><td>0.003%</td></tr><tr><td>三乙醇胺</td><td>0.2%</td><td>自来水</td><td>余量</td></tr></table></body></html>  \n\n$\\textcircled{8}$ 经打磨后，若有金属外露现象时，应补刷配套底漆。  \n\n$\\textcircled{9}$ 最后一道腻子打磨清理干净后，需喷（刷）涂过氯乙烯二道底漆，以提高漆膜的平整度与提高漆膜光泽。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 869,
+        "chunk": "# 2.机床零、部件涂装典型工艺  \n\n机床零、部件涂装典型工艺见表3-10-34。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 870,
+        "chunk": "# 3.原子灰施工要点  \n\n$\\textcircled{1}$ 原子灰是双组分腻子，使用时必须加人适量的固化剂，并将两者充分调拌均匀，才能使其正常干燥。  \n\n$\\textcircled{2}$ 使用时必须用多少调配多少，以免腻子固化不能涂刮，造成浪费。  \n\n表3-10-34 机床零、部件典型涂装工艺  \n\n\n<html><body><table><tr><td rowspan=\"2\">工序号</td><td rowspan=\"2\">工</td><td rowspan=\"2\">工序内容</td><td colspan=\"2\">材料与工具</td><td colspan=\"2\">施工黏度（15～</td><td rowspan=\"2\">70%以下）/h</td><td rowspan=\"2\">质量要求</td><td rowspan=\"2\">备注</td></tr><tr><td>材料</td><td>工具</td><td>刷</td><td>喷</td></tr><tr><td>1</td><td>清理去锈</td><td>铁将工件表 起、镜边、披锋等</td><td>钢丸等</td><td>或抛丸 等设备</td><td></td><td></td><td></td><td>迹、表面无锈 呈金，表面平整，</td><td></td></tr><tr><td>2</td><td>清理</td><td>粒、去表面的砂</td><td>压缩空气</td><td></td><td></td><td></td><td></td><td>1.表 粒、铁丸等脏物</td><td>有用污业 汽油清洗</td></tr><tr><td>3</td><td>检查</td><td>一</td><td>X06-1乙</td><td></td><td></td><td></td><td></td><td>按工序1～2 的质量要求检查</td><td></td></tr><tr><td>4</td><td>涂底漆</td><td>零、部件内外 表面要及时涂刷</td><td></td><td>毛喷具、</td><td>25~3018~25</td><td></td><td>0.5~1</td><td>污、外表面无油</td><td></td></tr><tr><td>5</td><td>检查</td><td></td><td></td><td></td><td></td><td></td><td></td><td>按工序4质量 要求检查</td><td></td></tr><tr><td>6</td><td>清洗</td><td>用金属清洗剂 工业内沈金属清 之油污、铁屑等</td><td></td><td>毛刷</td><td></td><td></td><td></td><td>污内外毒面无油</td><td></td></tr><tr><td colspan=\"2\">7 覆涂底漆</td><td>底外表面覆涂</td><td colspan=\"2\">底过氯乙烯 喷、</td><td colspan=\"2\">25～300.5~1</td><td>0.5~1</td><td>1.涂刷均匀， 无流得沾污已</td><td></td></tr><tr><td>8</td><td>填平缺陷</td><td>行较大缺陷先进</td><td>原子灰等</td><td>刮板</td><td></td><td></td><td>1~2</td><td>加工表面 基本填平缺陷</td><td></td></tr><tr><td>9</td><td>第子</td><td>全面刮腻子</td><td>腻过氯乙烯刮板、</td><td></td><td></td><td></td><td>4~6</td><td>1.刮涂平均厚 度不超过 去m子</td><td></td></tr><tr><td>10</td><td>第二</td><td>继续全面刮涂</td><td>腻过氯乙烯</td><td>刮板、</td><td></td><td></td><td></td><td>飞刺 不超途平均厚度</td><td>根据零、部 件不同情况可 刮涂次数，以</td></tr><tr><td>11</td><td colspan=\"2\">打磨 打磨腻子层</td><td colspan=\"2\">2</td><td colspan=\"3\"></td><td>表面基本平整</td><td>刮至成型为准</td></tr><tr><td>12</td><td>刮继子</td><td>续利腻子继</td><td>腻过氯乙烯</td><td>子磨 刮板、</td><td></td><td colspan=\"2\">1~2</td><td>1.刮涂平均厚 度不超过 0. 5mm;</td><td></td></tr><tr><td>13</td><td>打磨</td><td>磨平腻子层</td><td>水20纸~ 240子机腻</td><td></td><td></td><td></td><td>表面 何形状</td><td>1．表面平整、 光2边角整齐； 3.保持工件几</td><td>底漆</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td rowspan=\"2\">工序号</td><td rowspan=\"2\">工序名称</td><td rowspan=\"2\">工序内容</td><td colspan=\"2\">材料与工具</td><td colspan=\"2\">施工黏度（15～ 25℃，相对湿度 70%以下，涂-4</td><td rowspan=\"2\">干燥时间 (15～25℃， 相对湿度 70%以下）/h</td><td rowspan=\"2\">质量要求</td><td rowspan=\"2\">备注</td></tr><tr><td>材料</td><td>工具</td><td>黏度计）/s 刷喷</td><td></td></tr><tr><td>14</td><td>涂二 道底漆</td><td>全面喷(刷)涂 1～2道过氯乙烯 二道底漆</td><td>过氯乙烯 二道底漆</td><td>喷具</td><td></td><td>15~18</td><td>1~2</td><td>1.喷漆前腻子 表面清洁、干燥； 2.喷(刷)涂均 匀、无流挂、粗糙</td><td>非涂漆面 要保护</td></tr><tr><td>15</td><td>找补</td><td>用腻子找补局 部漆层缺陷处</td><td>过氯乙烯 腻子</td><td>刮板、 铲刀</td><td></td><td></td><td>1~3</td><td>补平缺陷</td><td></td></tr><tr><td>16</td><td>打磨</td><td>磨平全部漆层</td><td>0#~1*砂 布、260#~280# 水砂纸</td><td></td><td></td><td></td><td></td><td>平整、光滑</td><td></td></tr><tr><td>17</td><td>喷面漆</td><td>全面涂刷1～2 道过氯乙烯漆</td><td>过氯乙烯 磁漆</td><td>喷具</td><td></td><td>15~18</td><td>1~2</td><td>1.喷漆前漆层 表面清洁、干燥； 2.喷涂均匀、 无流挂、粗糙</td><td></td></tr><tr><td>18</td><td>内腔涂漆</td><td>涂刷内腔磁漆</td><td>过氯乙烯 机床内腔漆</td><td></td><td>25~30</td><td></td><td>1~2</td><td>1．涂刷均匀； 2.颜色一致</td><td></td></tr><tr><td>19</td><td>清理</td><td>清除非涂漆面 的漆皮及污物</td><td>金属清洗 剂、工业汽 油、棉纱</td><td></td><td>毛刷</td><td></td><td></td><td>表面清洁、外露 加工面及孔内无 漆皮、腻子等污物</td><td></td></tr><tr><td>20</td><td>检查</td><td></td><td></td><td></td><td></td><td></td><td></td><td>1．漆层平整、 光滑，色泽均匀 一致； 2.无明显缺 陷，保持工件几 何形状； 3.漆膜无流</td><td></td></tr><tr><td>21</td><td>转装配</td><td></td><td></td><td></td><td></td><td></td><td></td><td>挂、起泡 一</td><td></td></tr></table></body></html>  \n\n$\\textcircled{3}$ 原子灰固化时间的快慢，可根据气温变化，用固化剂的量来调节，一般条件下$20\\%$ 左右）每100份原子灰，加固化剂 $2\\%\\sim3\\%$ 。夏季气温高，固化剂用量可在 $1\\%\\sim$ $2\\%$ ；而冬季气温低，固化剂用量可在 $3\\%\\sim5\\%$ 0  \n\n$\\textcircled{4}$ 涂刮原子灰的底漆层必须干燥，与金属表面的结合力良好，并保证底漆表面无油污等，以免影响涂层的结合力，造成漆层脱落。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 871,
+        "chunk": "# 二、机床钣金件涂装工艺  \n\n机床等机械产品有部分部件，如皮带轮罩壳、挡板等，一般采用薄钢板冲压或焊接而成，这些薄钢板制成的部件，若采用喷丸处理容易使其变形、损伤、损坏，像这类部件通常采用化学处理方法清除表面锈蚀、污物等。对于采用粉末涂装的钣金件其涂装工艺按通用粉末涂装工艺要求进行，请参见有关章节，此处不再赘述。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 872,
+        "chunk": "# 1.表面处理工艺要求  \n\n$\\textcircled{1}$ 钣金件上无锈迹，而有油污的可用金属清洗剂去油污，若有轻锈和油污可米用“二合一”、“三合一”或“四合一”等金属涂漆前表面处理剂进行除油、除锈、磷化处理；若锈蚀较重的，则要进行酸洗、中和处理。  \n\n$\\textcircled{2}$ 去油污、去锈蚀后的钣金部件要及时清洗、干燥，水干之后要及时涂上磷化底漆或直涂配套底漆。$\\textcircled{3}$ 除油清洗液、除锈液、酸洗液、中和液、磷化液等要定期检验、补充和更换。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 873,
+        "chunk": "# 2.钣金件的化学处理与涂漆典型工艺  \n\n钢板件化学前处理及涂漆典型工艺见表3-10-35。  \n\n表3-10-35 钢板件化学前处理及涂漆典型工艺  \n\n\n<html><body><table><tr><td>工序号</td><td>工序名称</td><td>工 序内容</td><td>材料与设备</td><td>质量要求</td></tr><tr><td>1</td><td>清洗去油</td><td>清除工件表面的油污</td><td>金属清洗剂等</td><td>表面干净、无油污</td></tr><tr><td>2</td><td>水洗</td><td>洗去工件表面的清洗剂等</td><td>冷水，pH6~7</td><td>无残留清洗剂</td></tr><tr><td>3</td><td>除锈</td><td>除去工件表面的氧化皮、锈迹</td><td>硫酸或盐酸</td><td>1.表面无氧化皮、锈迹； 2.表面星金属本色</td></tr><tr><td>4</td><td>水洗</td><td>洗去工件表面的酸液及锈污</td><td>冷水，pH6～7</td><td>冲洗干净</td></tr><tr><td>5</td><td>中和</td><td>中和工件表面残留的酸液</td><td>碱水，pH>10</td><td>无残留酸液</td></tr><tr><td>6</td><td>水洗</td><td>洗去工件表面残留的碱液</td><td>冷水，pH6～7</td><td>无残留碱液</td></tr><tr><td>7</td><td>磷化</td><td>将工件表面进行磷化处理</td><td>磷化液等</td><td>表面呈一层均匀磷化膜</td></tr><tr><td>8</td><td>水洗</td><td>彻底洗去工件表面的磷化液</td><td>冷水</td><td>彻底清洗干净</td></tr><tr><td>9</td><td>涂底漆</td><td>内外表面浸(刷)涂底漆</td><td>过氯乙烯底漆</td><td>1.涂刷均匀、无流挂； 2.无露底</td></tr><tr><td>10</td><td>刮腻子</td><td>全面刮1～2道腻子</td><td>过氯乙烯腻子</td><td>刮平表面</td></tr><tr><td>11</td><td>打磨</td><td>打磨腻子层</td><td>1#～2#砂布、 220#～240#水砂纸</td><td>1.表面平整； 2.打磨后有金属外露时，需及时补刷 底漆</td></tr><tr><td>12</td><td>喷二道底漆</td><td>全面喷(刷)涂1～2道二道底漆</td><td>过氯乙烯二道底漆</td><td>1.涂漆前表面清洁、干净； 2.涂刷均匀，无流挂、粗糙</td></tr><tr><td>13</td><td>找补</td><td>用腻子找补不平处</td><td>过氯乙烯腻子</td><td>补平缺陷为准</td></tr><tr><td>14</td><td>打磨</td><td>磨平全部漆层</td><td>260*～280*水砂纸</td><td>平整、光滑</td></tr><tr><td>15</td><td>喷面漆</td><td>全面喷涂1～2道面漆</td><td>过氯乙烯磁漆等</td><td>1.喷漆前表面清洁、干燥； 2.喷涂均匀</td></tr><tr><td>16</td><td>检查</td><td></td><td></td><td>1.漆层平整、光滑，色泽均匀一致； 2.无明显缺陷； 3.漆膜无流挂、起泡</td></tr><tr><td>17</td><td>转装配</td><td></td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 874,
+        "chunk": "# 三、成品机床涂装工艺",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 875,
+        "chunk": "# （一）成品机床涂装工艺要求  \n\n$\\textcircled{1}$ 成品机床涂漆前，必须彻底清洗、擦净漆层表面的油污、腻子、粉尘等，以保证涂  \n\n漆层的附着力。  \n\n$\\textcircled{2}$ 凡在装配过程中产生的漆层碰伤处，需仔细铲除至周围漆层牢固及无机油渗透为止，并修铲成一定坡度，以便填补与打磨。  \n\n$\\textcircled{3}$ 总喷面漆时，需将全面漆层磨至光滑、平整、均匀状态。  \n\n$\\textcircled{4}$ 喷漆时采用的压缩空气，必须用油水分离器除去压缩空气中的水分和油污，油水分离器需经常排污清理。  \n\n$\\textcircled{5}$ 喷涂二道底漆和面漆时，必须将漆料充分搅拌均匀，稀释至施工黏度，并过滤后使用。  \n\n$\\textcircled{6}$ 喷漆时，施工现场相对湿度大于 $70\\%$ 时，容易造成漆膜发白、失光，为防止漆膜发3、失光，可加人适量防潮剂，选用的防潮剂要与漆料配套。  \n\n$\\textcircled{7}$ 机床涂漆完毕，需待漆膜干燥后送去装箱出厂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 876,
+        "chunk": "# （二）成品机床涂装典型工艺  \n\n成品机床涂装典型工艺见表3-10-36。  \n\n表3-10-36 成品机床涂漆典型工艺  \n\n\n<html><body><table><tr><td rowspan=\"2\">工序号</td><td rowspan=\"2\">工序名称</td><td rowspan=\"2\">工序内容</td><td colspan=\"2\">材料与工具</td><td colspan=\"2\">施工黏度（15～ 25℃，相对湿度 70%以下，涂-4</td><td rowspan=\"2\">于燥时间 (15～25°℃， 相对湿度 70%以下） /h</td><td rowspan=\"2\">质量要求</td></tr><tr><td>材料</td><td>工具</td><td>黏度计)/s 刷</td><td>喷</td></tr><tr><td>1</td><td>清洗</td><td>用压缩空气及工业汽油 清除和擦去铁屑、油污等 脏物</td><td>压缩空 气、工业汽 油、棉纱</td><td>毛刷</td><td></td><td></td><td></td><td>内外表面无油污、 铁屑等脏物</td></tr><tr><td>2*</td><td>修铲漆 层及补刷 底漆</td><td>将碰坏漆层修成一定坡 度，并用砂布打磨，若有金 属外露应补刷底漆</td><td>过氯乙烯 底漆</td><td>铲刀、 毛刷</td><td>25~30</td><td></td><td>0.5~1</td><td>不能漏铲、漏刷 底漆</td></tr><tr><td>3</td><td>检查</td><td></td><td></td><td></td><td></td><td></td><td></td><td>按工序1、2质量要 求检查</td></tr><tr><td>4</td><td>找补腻子</td><td>陷腻子找补痰，层 为准</td><td>过氯乙烯 腻子等</td><td>刮板、 铲刀</td><td></td><td></td><td>2~4</td><td>过1每次找补不宜 2.分次填平缺陷</td></tr><tr><td>5</td><td>打磨</td><td>打磨找补腻子处</td><td>1#~1# 2 砂布</td><td>磨腻 子机</td><td></td><td></td><td></td><td>磨平，并擦去浮粉</td></tr><tr><td>6</td><td>除油 包纸</td><td>非涂漆面涂黄油、贴纸或 盖专用防护罩</td><td>黄油、 纸等</td><td>专用防 护罩等</td><td></td><td></td><td></td><td>涂漆面不得沾有 黄油</td></tr><tr><td>7</td><td>第一次 喷漆</td><td>全面喷涂1～2道过氯乙 烯漆</td><td>过氯乙烯 二道底漆或 面漆</td><td>喷具</td><td></td><td>16~18</td><td>0.5~1</td><td>1.喷涂前表面要 清洁干净； 2.喷涂要均匀，无 流挂</td></tr><tr><td>8</td><td>找补</td><td>用腻子找补漆层缺陷处</td><td>过氯乙烯 腻子</td><td>刮板</td><td></td><td></td><td>1~2</td><td>找补齐全</td></tr><tr><td>9</td><td>打磨</td><td>磨平漆层</td><td>0#~1#砂布 或220#~240# 水砂纸</td><td>磨腻 子机</td><td></td><td></td><td></td><td>表面平整</td></tr><tr><td>10</td><td>第二次 喷漆</td><td>全面喷涂面漆</td><td>过氯乙烯 面漆等</td><td>喷具</td><td></td><td>16~18</td><td>0.5~1</td><td>1.喷涂前表面要 清洗干净； 2.喷涂要均匀，无 流挂</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td rowspan=\"2\">工 序 号</td><td rowspan=\"2\">工序名称</td><td rowspan=\"2\">工序内容</td><td colspan=\"2\">材料与工具</td><td colspan=\"2\">施工黏度（15～ 25℃，相对湿度 70%以下，涂-4 黏度计)/s</td><td rowspan=\"2\">干燥时间 （15~25℃ 相对湿度 70%以下） /h</td><td rowspan=\"2\">质量要求</td></tr><tr><td>材料</td><td>工具</td><td>刷</td><td>喷</td></tr><tr><td>11</td><td>检查</td><td></td><td>0#~1#砂</td><td></td><td></td><td></td><td></td><td>表面平整、无缺陷</td></tr><tr><td>12</td><td>打磨</td><td>打磨全部漆层</td><td>布或240#～ 280#水砂纸</td><td></td><td></td><td></td><td></td><td>表面平整、无缺陷</td></tr><tr><td>13</td><td>总喷漆</td><td>全面喷涂面漆</td><td>过氯乙烯 面漆等</td><td>喷具</td><td></td><td>13~17</td><td>2~4</td><td>1.喷涂要均匀，无 流挂； 2.每次喷涂需待前 次漆膜表干后进行； 3．每次喷涂不宜 过厚</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 877,
+        "chunk": "# 四、机床一次涂装工艺  \n\n我国传统的机床涂装工艺方法一般都是先进行零、部件涂漆，经整机装配完工后再进行整机涂漆的两次涂装法，有的甚至采用两次整机涂漆，这种工艺方法不仅重复劳动、原材料消耗量大、加重环境污染，而且对机床涂漆质量以及机床精度都会带来不良的影响。因此，国外工业发达国家已广泛用一次涂装工艺。近几年来，我国也有不少机床厂，例如济南第一机床厂、杭州机床厂、南京机床厂等单位，他们在与国外合资生产的加工中心、数控机床等产品中采用一次涂装工艺，并且取得了宝贵的经验。实践证明，一次涂装具有许多优越性，是一种先进的涂装技术，是机床涂装的发展方向。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 878,
+        "chunk": "# （一）一次涂装的概念及工艺路线  \n\n所谓一次涂装，即指机床涂装零件在机加工后涂装，并使涂漆质量达到预定的质量要求，经验收人库或转入装配，不再进行整机涂漆；也可将机床涂漆件经机加工及涂漆后进行部件预装（修整外形、配钻孔、定位等）再进行部件补漆，然后再总装；或将零件机加工预装、修外形，再拆下零件涂漆后总装。  \n\n以上具体做法根据各单位情况而有所区别，但总的概念是总装后不再进行整机全喷漆，而只对个别损坏的涂漆面进行局部修补。大致工艺路线可参照以下3种。",
+        "category": " Introduction"
+    },
+    {
+        "id": 879,
+        "chunk": "# 1.零件一次涂漆  \n\n前处理涂底漆 $\\Bumpeq$ 机加工 $\\left.-\\cdot\\right.$ 预装（修整外形等） $\\cdot\\mathbf{\\delta}$ 拆卸零部件 $\\nrightarrow$ 涂漆 $\\nrightarrow$ 复装 $\\rightarrow$ 开车调试 $\\rightarrow$ 局部修补漆。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 880,
+        "chunk": "# 2.部件补漆  \n\n前处理涂底漆 $\\nrightarrow$ 机加工 $\\cdot^{+}$ 涂漆 $\\cdot-$ 部件预装（修外形等） $\\rightarrow$ 部件修补漆 $\\twoheadrightarrow$ 总装调试 $\\twoheadrightarrow$ 局部修补漆。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 881,
+        "chunk": "# 3.零、部件涂漆  \n\n前处理涂底漆→机加工→涂漆→预装（修外形等）→开车调试→零、部件拆卸涂漆→总装 $\\nsim$ 局部修补漆。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 882,
+        "chunk": "# （二）一次涂装的优越性  \n\n①一次涂漆是由整机复漆改为分体零件或部件涂漆为主，刮涂及打磨腻子施工方便，零件的边缘、棱角拐角处容易喷涂。所以整机装配后边线接缝清晰，避免接合面油漆连在一起而造成零件拆装时产生漆层脱落现象；螺孔、接管及机床标牌等清洁整齐。保证机床涂漆外观质量。  \n\n② 由于整机总装后只作局部修补，大大减少了涂漆工作量，避免因刮、磨腻子而产生的粉尘、砂子、棉纱等杂物对机床清洁度的影响，同时避免涂漆施工中对机床电器元件及精密零件的损坏，保证了机床精度及开箱合格率。  \n\n$\\textcircled{3}$ 减少涂漆工序，节省人工、材料，缩短涂漆周期。  \n\n$\\textcircled{4}$ 减少有害气体对环境的污染。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 883,
+        "chunk": "# （三）一次涂装需具备的条件  \n\n$\\textcircled{1}$ 涂漆件表面平整度好。  \n\n$\\textcircled{2}$ 特别是面漆材料，必须具备附着力强、硬度高、耐摩擦、保光保色性能好、漆膜光滑，漆膜表面的油污容易被清除而漆膜不变色、不失光。另外，所用面漆可抛光打蜡，以便于小面积修补。选用硬度好，表面光滑，便于清洗而不变色、不失光的面漆，是实行一次涂装的必备条件。  \n\n$\\textcircled{3}$ 工艺路线合理、漆面防护措施落实。要实施一次涂装，必须根据本单位的具体情况，制订切实可行的工艺路线。特别要加强生产环节中的管理，采取有效措施，防止涂漆面在吊运和装配过程中的损坏。这是实现一次涂漆的关键。  \n\n$\\textcircled{4}$ 保证面漆色泽一致。一次涂装零、部件涂漆时，这些零、部件多数是分批涂漆的，有的间隔时间长，因此容易产生前后批漆件漆膜的色差及漆膜厚薄不一致。因此配漆时必须严格掌握颜色一致，以保证整机涂漆颜色及光泽的均匀一致。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 884,
+        "chunk": "# （四）一次涂装的修补方法  \n\n一次涂漆总装后难免个别部位的漆面被损坏。需要根据不同的情况，采用不同的修补方法。具体方法大致可分三种。  \n\n(1）整面修补指某些漆面损坏范围较大，需要整个面喷涂。一般可将非涂表面先用胶带纸封闭起来，封口选在接合面分界线或角尺转变处，以便于分割。喷涂层不宜过厚，一般不超过 $0.15\\mathrm{mm}$ 0  \n\n(2）局部修补指某些漆面较大，而被损坏范围却很小，则对该面只作局部修补。一般是将损坏部位的周围用胶带纸封闭起来，封口范围大于损坏面。损坏面的周围漆膜更要薄，然后用抛光膏（或金刚粉）抛光，以消除喷漆接痕。  \n\n(3）点状修补指损坏面微小，用口径小的喷漆枪，并将其调节到较小的出漆量及出气量，作局部点状喷涂或用笔修补。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 885,
+        "chunk": "# 五、美术漆及其涂装工艺  \n\n美术漆包括锤纹漆、橘纹漆、皱纹漆、裂纹漆、金属闪光漆、复色漆、斑纹漆，此外还  \n\n有石纹漆、木纹漆、花基漆、彩纹漆等。在机床行业中锤纹漆和楠纹漆的应用较为厂泛，新近又开发出具有结构花纹自动成型特点的橘型结构漆，在行业中逐步推厂应用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 886,
+        "chunk": "# （一）锤纹漆  \n\n锤纹漆有自于型和烘干型两类。常用的自干型有硝基锤纹漆和过氯乙烯锤纹漆；烘十型有氨基锤纹漆和丙烯酸锤纹漆，近几年来应用较多的是双组分聚氨酯锤纹漆。",
+        "category": " Introduction"
+    },
+    {
+        "id": 887,
+        "chunk": "# 1．施工原理  \n\n配制锤纹漆的关键颜料是铝粉。锤纹漆应用的铝粉是无叶展性的，以保证铝粉能沉入漆膜底层形成锤纹。将铝粉和甲苯或二甲苯一起加热回流几小时，即成无叶展性的脱浮铝粉。  \n\n锤纹漆形成的原理主要是使漆液喷溅后表面形成凹状点。在这基础上，漆点中的铝粉旋转着下沉，由于漆点中的溶剂挥发，使铝粉一边下沉一边又作旋转运动，同时漆点中的清漆和颜料形成分界线。喷涂的各个漆点在物体表面已流展到互相连接，颜料在它的最外边缘，形成了一个个色圈分界线。这样各个漆点中的铝粉就旋转成一个个浅碟子似的旋涡。清漆略浮于铝粉上面，使得这些旋涡显现闪烁着金属光泽和均匀美丽的锤纹。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 888,
+        "chunk": "# 2.施工方法  \n\n(1）一般喷涂法将漆液调稠至适合施工黏度后，过滤，再喷到工件上，使之显现花纹，形成锤纹膜。一般喷涂法又可分为一层喷涂法和两层喷涂法。  \n\n一层喷涂法是在喷好一般底层漆的工件上，只喷一层锤纹漆。采用一层喷涂法必须使用固体含量较高的锤纹漆，不然，锤纹就显太单薄，不美观。此法多用于小型不规则的零件。  \n\n两层喷涂法是在工件上喷两层锤纹漆，第一层主要是打底，第二层才喷溅锤纹。通常将第二层喷涂叫“溅喷”，即漆液要一点一点地“溅”到工件上。亦称第二次喷溅为“点花”。  \n\n喷涂大、中型机床时，以采用两层喷涂法施工较好。有特殊装饰要求的可以喷三层或四层，以使漆膜更丰满柔和，但是不论喷几层，在最后一层均需“溅喷”。  \n\n(2)溶解喷涂法将锤纹漆先像普通漆那样喷涂，只要求漆膜厚薄均匀，不求锤花与否。一般是连续喷两层（中间间隔 $10\\mathrm{\\sim}15\\mathrm{min})$ ，使漆膜均匀无漏底。再静置 $15\\sim20\\mathrm{min}$ 待漆膜接近表干时，再喷清洁的该锤纹漆稀释剂。将稀释剂喷成分散的点子，洒落在喷好的漆膜上。通过这些稀释点子将漆膜溶解又再挥发的过程，形成锤纹花纹。溶解喷涂法对采用烘干型氨基锤纹漆喷大面积设备效果很好，所得锤纹花比其他喷涂法花纹更大、更清晰。若用自干型锤纹漆，效果较差。因为自干型锤纹漆的漆膜表干后，比未经烘干的氨基漆膜要难溶得多。  \n\n喷涂锤纹漆时，必须注意下面几点。  \n\n$\\textcircled{1}$ 要将漆料喷成雨点似的洒到工件上。一般说来，漆点大的出现的锤纹就大，而且清晰，但漆点过大或过稠，会出现橘皮、光泽不好等毛病；漆点过密也会出现锤纹不清现象。  \n\n$\\textcircled{2}$ 在喷涂时，洒落到工作面上的漆点要均匀、大小近似，这样得到的锤纹大小也近似，而且锤纹花界线均匀美观。  \n\n$\\textcircled{3}$ 第一层漆的厚薄要适宜，过厚时会造成锤纹花界线模糊不清；过薄时铝粉旋沉性不佳，锤纹不明显，漆膜不丰满，光泽亦差。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 889,
+        "chunk": "# (3）洒硅法  \n\n$\\textcircled{1}$ 施工方法及原理在工件上先喷一层锤纹漆，待漆膜表干后，薄薄喷洒一层硅水，然后再喷一层锤纹漆，它是利用“硅水”的微小珠粒对铝粉和漆料的强烈排斥，形成了以“硅水”珠滴为圆心逐渐凹下的锤窝。与此同时，由于溶剂挥发，使铝粉下沉，便产生有金  \n\n属光泽的锤纹。  \n\n②“硅水”的配制将硅油配成0.1%～0.5%的汽油溶液再加人10%左右二甲苯即成。选用汽油作溶剂，是因为它对漆膜溶解力不强，挥发又较快；加入二甲苯可防止洒硅时垂直面上的“硅水”珠滴发生流挂现象。  \n\n“硅水”中硅油浓度对锤纹漆深浅程度影响。硅油浓度过大时，喷出的锤纹花窝太深，有损美观装饰效果；硅油浓度太小，则覆漆时硅水珠滴被“淹没”，使锤纹花形不完整。  \n\n对于像机床一类较大的物件，硅油浓度以 $0.5\\%$ 为好。硅水参考配方如下：  \n\n硅油  \n\n90%  \n\n二甲苯  \n\n$\\textcircled{3}$ 洒硅法的优缺点洒硅法和点花施工比较，有如下优点：显露花纹迅速，施工速度快；锤花的大小和深浅都均匀、整齐，且锤感强，花界明显清晰；垂直面及圆柱形的工件，只要掌握好洒硅喷涂技术，也可获得与平面喷涂同样的效果，解决了大型构件及笨重物体喷涂锤纹漆的技术难关；补漆方便且快速，补漆不会产生像点花法那样有明显分界面的缺陷；施工设备和技术简单，操作较易掌握。  \n\n缺点是因硅水是无色液体，洒硅时往往不易看清枪路，而致漏洒或重洒。施工时应严加注意。  \n\n(4）漆膜的修补如果工件上锤纹漆膜有破损处，在罩清漆之前应作修补。但不能像普通磁漆那样对着破损处补喷一枪，若这样补枪，周围会产生难看的乱点迹印。锤纹漆修补漆膜有以下3种方法。  \n\n$\\textcircled{1}$ 用毛笔涂刷漆膜破损处 当破损面积不大时，这种修补并不显眼，效果很好。  \n\n$\\textcircled{2}$ “植皮法”当破损面积较大时，可将单幅锤纹漆漆膜剪成相应大小，并在要修补的部位用毛笔均匀涂刷一层薄的锤纹漆漆料，随即将剪好的漆膜粘上去，就像医生“植皮”似的，效果尚好。  \n\n单幅锤纹漆的制备：将锤纹漆喷在清洁干燥的玻璃上，待漆膜充分干燥后，浸在清洁水中，几小时后或次日就能将漆膜完整地撕下，备作“植皮”修补用。  \n\n$\\textcircled{3}$ 整幅喷涂大面积破损时，若整幅平面再喷一次，效果较好。在点花前，选定棱角面或其他部件交接处作分界线，将分界线以外完好的表面用硬纸板遮挡好，以免漆点溅染，然后再进行点花喷涂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 890,
+        "chunk": "# 3.施工要点  \n\n(1）漆料黏度的调节喷涂前，必须先将漆液搅拌均匀，再用专用的稀释剂将锤纹漆调稀、过滤。稀释剂的加人量一定要掌握好，过多，漆点小，漆膜中由于大量稀释剂，铝粉便可继续扩散，致使锤纹变平暗。稀释剂加得太少时，漆点过大，又难以扩散，铝粉难以沉降和旋转成浅碟形，颜料也难以形成色圈，使锤花不清晰、不完整。  \n\n稀释剂的加人量要根据施工时气温的变化加以调整。一般稀释剂用量约为 $10\\%\\sim30\\%$ T漆液黏度以 $30\\sim50{\\mathrm{s}}$ 为宜。  \n\n此外在有底漆或腻子层的工件上直接喷锤纹漆时，由于底漆、腻子会吸收一部分稀释剂，所以稀释剂加入要适当多一些。  \n\n(2)喷枪的选择和调节目前较普遍使用的是吸上式喷枪，如PQ-1型的（对嘴式）、PQ-2型（扁嘴式)。形状不复杂的大型设备可采用PQ-2型的扁嘴枪。扁嘴枪喷出的漆雾像一把打开的折扇，喷幅大小可以随意调节，最宽叶幅可达 ${500}\\mathrm{mm}$ 左右。喷幅宽，漆液落点均匀，速度快。扁嘴枪的漆嘴口径需在 $1.5\\mathrm{mm}$ 以上，这样才易形成花纹，其锤纹花直径可达 $4\\sim8\\mathrm{mm}$ 。中小型机床采用对嘴式喷枪，出气嘴和出漆嘴口径要加大至 $2.5\\sim3\\mathrm{mm}$ ，这样喷涂时出漆量大，漆点也大，特别是喷硝基锤纹时花纹较大，形成的锤花直径可达$4\\sim6\\mathrm{mm}$ 电  \n\n喷涂距离喷枪出漆嘴与地面的距离，对烘干型锤纹漆应保持 $300{\\sim}400\\mathrm{mm}$ ；自十型锤纹漆保持在 $150{\\sim}200\\mathrm{mm}$ 。同时喷嘴应尽量垂直物面为宜。  \n\n(3）喷枪运行速度气压偏大，运枪速度宜稍快；气压偏小，运枪速度宜稍慢，喷涂$\\ln$ 长约为 $3\\sim5\\mathrm{s}$ 。硝基锤纹漆喷涂时宜慢一点，氨基锤纹漆喷涂时略快一点。  \n\n(4）喷涂次序先喷物体上部，后喷下部；先喷次要表面，后喷主要表面。这样可以避免扩散的漆点溅到主要表面上。对小型物件和单件，按主、次面摆整齐，逐面进行喷涂。  \n\n(5）开枪与收枪的位置开枪和收枪必须在物面的空方起落。喷涂时要防止一个面未完，枪罐内已无漆料，因此要根据面积大小保持枪罐内有足够的漆液量。主要表面点花时，必须一次喷完，不能中途停枪，开枪和收枪均不能任意起落，否则物面两端部位的锤花会散乱难看。主要正面及平面可用向前推进喷涂法，这样整个物面的锤纹花才均匀、美观。  \n\n(6）点花时间的掌握喷完第一层锤纹漆后，隔上一段时间，用手指轻轻试探，当漆膜不黏手，但又有黏手的感觉时，进行点花最好。间隔的时间因气温不同而有差异。一般情况下，夏天约 $5\\mathrm{\\sim}10\\mathrm{min}$ ，冬天约 $15\\sim30\\mathrm{min}$ 。点花太早，形成的花纹散乱，且在花纹中夹杂很多蜘蛛网丝似的色线；点花太迟，所得花纹平暗，甚至锤花不完整。  \n\n(7）压缩机气压的调节气压最适合为 $0.2{\\sim}0.3\\mathrm{MPa}$ （不宜超过0.3MPa)。在这个范围内喷涂，锤花清晰、效果好。气压小些，喷出的漆点大，锤花亦大，否则漆点变细，锤花就小。这在喷最后一层点花时尤其要注意。  \n\n(8）施工场所的通风不宜在大风或开风扇的场所喷漆，否则风力会把喷出的漆点吹得毫无规则地洒到工件上，同时溶剂挥发过快，影响锤花的完整。施工场所的通风可采用抽风措施或采用水帘式喷漆柜。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 891,
+        "chunk": "# （二）橘纹漆  \n\n橘纹漆是一种较新颖的美术漆，近些年来，国外比较流行这类漆。  \n\n所谓橘纹漆，是漆膜外观具有像橘子皮一样的花纹，故称橘纹漆（或称橘型漆）。橘纹漆多用于加工中心、数控机床、仪器、仪表、电子计算机等的涂装，使其显得更加幽雅、美观。  \n\n常用橘纹漆有双组分聚氨酯橘纹漆、氨基橘纹漆、热塑性丙烯酸橘纹漆、丙烯酸硝基橘纹漆等。  \n\n橘纹漆漆膜外观，有密集型花点和疏散型花点，其中花点又有大小之分，根据产品的具体要求来选择，一般大型机床适用密集型或疏散型的大点花纹，而小型机床等产品适用密集型的小点花纹。  \n\n喷涂橘纹漆大部分都使用国产PQ-1型喷漆枪，也可使用PQ-2型普通喷枪。  \n\n橘纹漆施工注意事项如下。  \n\n$\\textcircled{1}$ 橘纹漆使用前要搅拌均匀，用专用稀释剂调整黏度，并用200目铜筛 (或丝绢网)过滤备用。喷漆黏度控制，喷涂第一道一般黏度为 $25\\sim305$ ，以达到均匀盖底的目的；喷涂第二道黏度一般在 $40\\sim60{\\mathrm{s}}$ ，这道漆是达到花纹要求的关键。  \n\n$\\textcircled{2}$ 喷涂橘纹漆一般多数采用PQ-1型嘴喷枪，喷涂大花纹喷嘴口径要大一些，一般喷涂第一道时，选用喷枪的喷嘴口径为 $\\$1,5sim2\\mathrm{mm}$ ，喷涂第二道时，喷枪的喷嘴口径为Φ2\\~3mm。  \n\n$\\textcircled{3}$ 喷涂橘纹漆使用压缩空气的压力比喷普通喷漆的压力要低，一般喷第一道压力为  \n\n$0.3{\\sim}0.4\\mathrm{MPa}$ ；喷第二道压力为 $0.2{\\sim}0.25\\mathrm{MPa}$ 喜  \n\n④若喷涂氨基橘纹漆，第一道喷完后要在35～45℃条件下烘烤10～15min，取出后降至室温，当漆膜表干后，再喷第二道。喷涂完后待表干，放入烘箱，升温60～80℃，恒温1h即可出箱。使用热塑丙烯酸橘纹漆、丙烯酸硝基橘纹漆或聚氨酯双组分橘纹漆等自干型漆，都要待第一道表干后再喷第二道。  \n\n$\\textcircled{5}$ 喷涂第二道橘纹漆的走枪方式，要同喷涂第二道锤纹漆一样，采用向前推进的方式作溅点喷涂。若要求涂膜表面橘纹花点突出，喷第二道时可将橘纹漆的黏度调整到80s左右；如要求涂膜像人造革状的花纹，可在喷完第二道漆的基础上，再喷涂一道稀释剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 892,
+        "chunk": "# （三）橘型结构漆  \n\n橘型结构漆是一种特殊效果的高档工艺美术漆。其施工后的漆膜能自动形成立体感极强的均匀凹凸漆面，其装饰效果华贵、典雅大方。因此，对机床产品具有良好的表面装饰和保护效果。",
+        "category": " Introduction"
+    },
+    {
+        "id": 893,
+        "chunk": "# 1.产品特点  \n\n(1）机械性能好采用丙烯酸聚氨酯双组分固化体系，因此漆膜不但坚硬耐磨，且柔韧性好，耐冲击、耐碰撞，具有优良的保护性能。  \n\n(2）装饰效果好橘纹结构均匀，立体感强。漆膜丰满，手感光滑，色彩丰富，豪华靓丽。  \n\n(3）省工省料均匀凹凸的漆面可有效地遮盖涂漆面的瑕疵，因此能较大地减少油漆施工的工作量。  \n\n(4）施工性好可采用常用喷漆工具施工。既不会出现高黏度喷涂时常见的漆面粗糙或 者流平现象，也避免了随漆膜厚度而引起的橘纹结构大小不均匀的病。  \n\n此外，对于在洁净车间和大型产品的涂装时不宜采用喷涂操作的场合，橘型结构漆也可以辊涂施工，有较好的效果。  \n\n(5）低毒害本产品以进口原料配制，保证了有害游离单体严格低于国际标准，不会出现常见的因固化剂刺激黏膜引起的咽喉不适症状。  \n\n(6）环保节能本产品一般不加稀释剂，采用较高黏度喷涂。因此，有效含量高，挥发溶剂量少，飞散的漆雾也少，不仅减少了漆雾对施工人员的身体伤害，也降低了对空气的污染，有利于环保。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 894,
+        "chunk": "# 2.技术指标  \n\n橘型结构漆技术指标见表3-10-37。  \n\n表3-10-37 橘型结构漆技术指标  \n\n\n<html><body><table><tr><td>项 目</td><td>指标</td><td>检验方法</td></tr><tr><td>硬度</td><td>≥1H</td><td>GB/T 6739</td></tr><tr><td>附着力/级</td><td>≤2</td><td>GB/T 1720</td></tr><tr><td>柔韧性/mm</td><td>1</td><td>GB/T 1731</td></tr><tr><td>冲击强度/kgf·cm</td><td>50</td><td>GB/T 1732</td></tr><tr><td>干燥速率</td><td>表干不大于20min 实干不大于24h</td><td></td></tr><tr><td>出厂黏度</td><td colspan=\"2\">50~80s(涂-4杯)</td></tr></table></body></html>\n\n注： $\\mathrm{ikgf}{=}9.80665\\mathrm{N},$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 895,
+        "chunk": "# 3.橘型结构漆施工工艺  \n\n(1)表面准备橘型结构漆具有较好的立体装饰效果，可有效地遮盖涂漆面的瑕疵，因此能较大地减少表面准备的工作量，原则上可免高光漆必需的水磨工序，但要求较细致的干磨操作，保证待涂表面平整，边角和线条规范清晰。  \n\n(2）材料准备橘型结构漆必须与橘型漆专用固化剂以及专用稀释剂配合使用，喷涂前根据待涂面大小估算用漆量再行配漆，配漆量应遵循少量多次的原则，以免浪费。  \n\n橘型结构漆与橘型结构漆专用固化剂的标准配比为 $8:1$ （质量比），实际使用时可根据需要和经验适当增减，但幅度不宜过大。配漆时，必须首先采取有效方法（比如用较粗的棍棒搅拌、将漆桶来回翻滚，以及将桶内漆料全部倒出冲兑等方法)，务必使原桶内漆料上下混合均匀，方可使用，否则容易出现漆膜病态。然后将漆配以固化剂搅拌均匀后即可喷涂，一般情况下不需稀释剂。若气温太高或为调节装饰花纹大小可加入少量专用稀释剂。  \n\n(3）工具准备橘型结构漆采用常规空气喷涂，气源为经过除水、除油后的压缩空气，施工工具采用常规PQ-1或PQ-2型空气喷涂枪，在空气源压力为 $4\\sim6\\mathrm{kgf}$ 下喷涂即可达到较好的花纹效果，为达到最好装饰效果，推荐采用7孔或11孔高雾化PQ-2型喷枪。对于小面积涂漆或小型设备，喷枪孔径宜选用 $1.5\\sim1.8\\mathrm{mm}$ ，对于大面积涂漆或大型设备，喷枪孔径应选用 $2.0{\\sim}2.5\\mathrm{mm}$ 。辊涂工具常采用羊毛辊。  \n\n(4）喷涂操作橘型结构漆的喷涂操作与常规平面漆的操作基本相同。原则上喷两道：第一道薄喷盖底，第二道喷涂控制花纹。特殊情况比如补漆时也可一次厚喷成型。喷涂时，应先通过旋紧气阀调低气量、控制扳机力度试喷，得到的橘型结构以点状为主，再逐渐旋出气阀加大气量以调高出漆量得到所需的凹凸橘型结构，切不可一次喷涂过厚以免出现漆膜病态。保持匀速走枪以得到大小均匀的橘型结构。采用十字喷涂方式可提高涂膜均匀性，但横喷和竖喷的相隔时间必须要尽可能的短，以使两层之间良好融合形成均匀清晰的花纹。一般情况下，调低油漆黏度、远距离薄喷能得到细小花纹，反之，提高油漆黏度、近距离厚喷得到的橘型花纹较大。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 896,
+        "chunk": "# 六、机床涂装中常见的漆膜病及防止方法  \n\n机床涂装过程中，由于表面处理不当，施工工艺欠妥及施工环境影响，至使漆膜出现起泡、剥落、发白、失光等病。  \n\n漆膜出现病，不仅影响机床外观质量，同时又降低漆膜的防护性能，所以在涂装施工中应尽量避免出现各种弊病，提高机床涂装质量。机床涂装常出现的弊病及防止方法见表3-10-38。  \n\n表3-10-38机床涂装可能出现的漆膜葬病及防止方法  \n\n\n<html><body><table><tr><td>序号</td><td>漆膜病态</td><td>产生原因</td><td>防止方法</td></tr><tr><td>1</td><td>刷痕（漆膜上 留有刷子的刷 痕)</td><td>1.涂料黏度太稠； 2.使用的毛刷干硬</td><td>1.加稀料调整至适宜黏度； 2.调换新毛刷； 3.刷子用完之后要洗净妥善保管</td></tr><tr><td>2</td><td>粗糙（表面不 光滑，起颗粒）</td><td>1.毛刷中夹带砂尘或砂尘落在漆内；使用前要过滤； 2.漆料黏度过稠； 3.喷枪离工件过远； 4.压缩空气压力不够； 5.底层打磨不仔细</td><td>1.毛刷、漆桶等用具要保管好，不要粘夹砂尘，漆料 ：2.加稀料调整黏度； 3.控制好喷枪与工件间的距离； 4.压缩空气保持在0.3～0.5MPa; 5.用砂纸仔细打磨； 6.漆皮要去掉</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>序号</td><td>漆膜病态</td><td>产生原因</td><td>防止方法</td></tr><tr><td>3</td><td>流挂(在垂直 表面上，部作分 生流淌现象)</td><td>1.喷枪离工件过近； 2.喷枪走速太慢； 3.选用的料干燥速度太慢； 5.毛刷蘸漆太多； 6.漆膜太厚</td><td>1.控制喷枪与工件之间距离，一般为20～25cm最 合适； 2.控制走枪速度； 3.选择于燥速度快的涂料； 4.调整适宜的黏度； 5.控制蘸漆量； 6.控制漆膜厚度</td></tr><tr><td></td><td>橘皮(漆膜表 面像橘皮，有许 多半圆状突起)</td><td>1.涂料本身流平性差； 2.涂料黏度过稠； 3.底部打磨不仔细； 4.喷枪出漆量过多</td><td>1.加适量硅油，改善涂料的流平性能； 2.调整涂料黏度； 3.仔细打磨； 4.调整气压，调节喷枪出漆量</td></tr><tr><td>5</td><td>光发白（漆膜无</td><td>施工环境的相对湿度大于70%</td><td>1.加防潮剂（注意要配套)； 相2.用红外线灯加热施工场地提高环境温度，以降低 3.将工件适当预热</td></tr><tr><td></td><td>失光(漆膜刚 干燥时有光泽， 但过几小时或数 星期之后光泽慢 慢消失的现象)</td><td>1.底层打磨不光滑； 2.漆料本身光泽差； 3.涂料黏度过稀； 4.连续喷涂，致使腻子层吸收磁漆中 的树脂 1.金属表面处理不干净，残留有锈迹、</td><td>1.采用水磨或汽油磨，提高打磨质量； 2.选择光泽好的聚氨酯改性过氯乙烯漆等来涂装； 3.调整涂料施工黏度； 4.施工过程中，保证各层涂料的干燥时间</td></tr><tr><td></td><td>起泡（漆膜表夹闭在腻子内； 面大小不同的圆 形突出物)</td><td>污物； 2.刮涂腻子时，刮涂速度过快，将空气 3.腻子质量不好； 4.使用石膏腻子，或在腻子中添加石 膏粉； 5.腻子一次刮涂太厚，阻碍腻子中溶 剂挥发</td><td>1.金属表面处理要干净； 2.注意涂刮工艺，腻子要薄刮，分多次刮涂； 3.若腻子质量欠佳，可加些磁漆调和后使用，与造 漆厂商量改进腻子质量； 4.禁止使用石膏腻子和在腻子中自行加入石膏粉 及其他填料； 5.要薄刮，第二道腻子应待第一道腻子干燥后才 刮涂</td></tr><tr><td>8</td><td>揭皮(漆膜成 张揭下来)</td><td>1.底层表面油污等清洗不干净； 2.材料不配套； 3.漆料本身附着力欠佳</td><td>1．底层表面油污等要清洗干净； 2.材料要配套； 3.第二层要待第一层已干，而实际尚未干透时就喷 为佳； 4.选择附着力好的涂料</td></tr><tr><td>9</td><td>开裂（漆膜裂 开)</td><td>1.腻子刮涂太厚； 2.在腻子中加人过量的其他填料； 3.材料不配套</td><td>1.腻子要分多次薄刮； 2.不要在腻子中自行掺人其他填料； 3.材料要配套</td></tr><tr><td>10</td><td>塌陷变形 (漆膜干后凹陷 下去)</td><td>采用溶剂型腻子填坑时，一次用量过 多，腻子干燥后收缩而引起凹陷</td><td>1.采用化学型固化腻子(如原子灰等)来填坑； 2.若用溶剂型腻子填坑时，要分多次薄刮，逐步 填平 1.与造漆厂商量解决；</td></tr><tr><td>11</td><td>针孔(漆膜上 的圆形小圈，中心 有固体粒子，周围 为凹人圆圈的现 象)</td><td>1.涂料中的颜料与树脂湿润性不好； 2.漆料中夹有水汽或尘灰; 3.喷嘴过小或压缩空气压力过大； 4.环境气温大于30℃时</td><td>2.漆料使用时要过滤； 3.压缩空气要经油水分离器分离； 4.压缩空气压力控制在0.3～0.5MPa为妥； 5.调换喷嘴</td></tr><tr><td>12</td><td>脱落（漆膜开 裂而失去附着力 而剥落)</td><td>1.金属表面处理不干净； 2.材料不配套、不适应； 3.腻子层太厚； 4.层间不干净</td><td>1.金属表面处理必须干净； 2.工件要涂X06-1磷化底漆或经磷化处理； 3.材料要配套、要适应； 4．腻子层不宜太厚； 5.层间的污物要清洗干净</td></tr></table></body></html>  \n\n我国机床漆膜经常发生的弊病是起泡、失光等，其中，以起泡居多。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 897,
+        "chunk": "# 1.起泡  \n\n漆膜表面大小不同的圆形突起物，在漆膜病态上称之为起泡，是漆膜在高温高湿环境中容易出现的现象，其起源大多是施工问题与材料质量问题。  \n\n就材料而言，底漆与面漆一般本身不易起泡，而造成起泡的材料主要是腻子。  \n\n腻子是用于填补铸件凹陷、气孔、擦伤等缺陷而采用的填料。它由漆基、填料和体质颜料等组成的稠厚有色黏膏，机床行业使用最多的是过氯乙烯腻子。  \n\n腻子质量不好，是造成漆膜起泡、开裂的主要原因。腻子质量不好的原因一方面是油漆制造厂所用的原料质量不好或制造工艺事故等原因所致，另外，在施工时，为了贪图好刮易磨，在腻子中任意加人一些石膏之类的其他填料，从而破坏了腻子原来的配方，降低了质量，而引起起泡开裂，甚至产生剥落。使用石膏腻子起泡情况更为明显，这是由于石膏凝固时，多余的水分一部分蒸发了，而另一部分水分则渗人底层，透过底漆使铸件表面产生锈蚀，并放出氢气。  \n\n$$\n3\\mathrm{Fe}+4\\mathrm{H_{2}O}\\longrightarrow\\mathrm{Fe_{3}O_{4}}+4\\mathrm{H_{2}}~\\uparrow\n$$  \n\n氢气夹带另一部分水汽、残留溶剂等，向外膨胀，导致漆膜起泡。  \n\n为了控制质量不好的腻子投人生产使用，以致造成起泡、开裂，在每批腻子进货后，应抽样检验。对质量不好的过氯乙烯腻子，为了减少浪费，决定投人使用时，要对腻子进行必要的处理。处理方法：使用时，加适量过氯乙烯面漆，搅拌均匀，然后使用。加人适量面漆可以改善腻子的质量。  \n\n过氯乙烯腻子不宜刮涂太厚，厚了影响腻子内的溶剂挥发，容易导致漆膜塌陷、起泡、开裂，甚至剥落。ZBJ50012《出口机床涂漆技术条件》要求：“腻子应分多次刮涂，每次尽量薄刮\\*”如果铸件表面凹陷、突起严重，可预先进行凿平、打磨等机械方法处理，不能完全依赖于腻子来填平。刮平要严格按工艺操作，每层要薄刮，每次刮涂均需待上层腻子干燥后进行，避免未干透的腻子中的溶剂挥发积聚而造成起泡。  \n\n对于化学固化的腻子，它不是靠溶剂挥发而干燥固化的，而是起交联反应而固化，所以，每次刮涂厚度不受限制，任意厚度均可。  \n\n在生产中一般用砂布（纸）打磨腻子表面，来检查腻子干透或未干透。若砂布（纸）不粘即为干透。  \n\n表面处理不好也是漆层起泡的重要原因之一。一般铸件从铸造车间出来之后，铸件上常残留有炉渣、氧化皮等污物，如果不及时进行彻底清理便作涂装施工，必将成为漆层起泡的祸根。  \n\n铸件表面处理的方法有喷丸（砂)、钢丝刷擦除等处理方法。目前使用最多、最有效的是喷丸处理。解剖分析一些机床漆层气泡，发现大多是铸件表面处理不善而造成的。所以，铸件在涂漆前，一定要用喷丸处理，其他方法处理都不甚理想。  \n\n由于铸铁在相对湿度大于 $65\\%$ 时容易生锈，所以当环境湿度大于 $65\\%$ 的情况下，喷丸处理后的铸件要及时刷涂底漆。有新产生锈蚀的铸件与锈迹未去净的铸件一样，是不能刷底漆的，即使刷上了底漆，也不能防止漆层的起泡，因为锈迹以及它隐附着的潮气在底漆层下还能慢慢地蔓延，时间一长，锈迹扩展而造成起泡。  \n\n综上所述，机床漆层起泡的原因主要是腻子质量不好和表面处理不善所致。  \n\n钢板件漆膜的起泡也较为常见，其原因大多是酸洗后中和不好，部分残留的余酸未清除干净而造成的，也有水洗后未及时干燥而引起锈蚀，这些细小的锈点及隐附其上的水分在漆层内逐渐蔓延而引起起泡。钢板件很少使用腻子，起泡原因多为去油、除锈、酸洗、中和不善而引起，所以只要严格按操作工艺规程去做，再辅以磷化处理，钢板件漆层起泡现象可以避免。  \n\n此外，铝合金制件的油漆层起泡现象也较为普遍。一方面因为铝制件质地疏松多孔，溶剂、水汽等极易潜伏；另一方面一般底漆与铝件的结合力较差，特别是过氯乙烯底漆与铝件的结合力更差，容易产生起泡。所以一般推荐采用锌黄底漆，但锌黄底漆沉底严重，使用时不易调和，故实际效果差。为了解决这个问题建议采用X06-1乙烯磷化底漆。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 898,
+        "chunk": "# 2.失光  \n\n漆膜光泽是评价机床外观质量的重要指标，特别是出口机床，对这个指标要求较高，据ZBJ50012《出口机床涂漆技术条件》规定：光泽度≥85%。  \n\n我国有些机床漆膜光泽比较低，这主要与采用的漆种有关，当然与施工工艺也有一定的关系。在施工上采用水磨、调稀黏度、增加喷涂次数，也可获得较高的光泽，但比较费工费料。  \n\n目前机床使用的过氯乙烯漆，其光泽较低，所以各地油漆制造厂对过氯乙烯漆进行了改性，以提高其光泽。目前，其较好的漆有改性过氯乙烯机床漆、丙烯酸改性过氯乙烯漆、过氯乙烯丙烯酸外用磁漆、聚氨酯磁漆等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 899,
+        "chunk": "# 第四节 机床色彩格调  \n\n机床涂装的色彩格调是衡量机床外观质量的重要指标之一。凡色彩格调新颖的机床，容易吸引用户的购买欲望，可以达到扩大营销之目的；机床色彩也是美化车间环境，给劳动者以美的享受，有利于提高工作效率。所以合理选择色彩格调，正确配置色彩是一项很重要、且很有意义的工作。",
+        "category": " Introduction"
+    },
+    {
+        "id": 900,
+        "chunk": "# 一、机床色彩格调选择原则",
+        "category": " Introduction"
+    },
+    {
+        "id": 901,
+        "chunk": "# 1.机床色彩要明快  \n\n机床是机械加工工具，它的色彩格调要与车间环境相适应，色彩要明快，但不宜过于鲜艳，以免造成操作者的视力疲劳。",
+        "category": " Introduction"
+    },
+    {
+        "id": 902,
+        "chunk": "# 2.色彩以灰色为主格调  \n\n国内外的机床大多选择灰色为主调；其中以绿灰居多，也有采用蓝灰、奶黄色的，色彩要庄重大方。",
+        "category": " Introduction"
+    },
+    {
+        "id": 903,
+        "chunk": "# 3.要根据机床形状及产品特点  \n\n另外，还要根据使用场合与人们的喜好等具体情况选择色彩。如中、小型机床用色要浅些，重、大型机床用色一般要深些。又如生活在热带地区的人需要凉爽，一般选用冷色，而生活在北方寒冷地区的人需要暖和，一般喜欢暖色。",
+        "category": " Introduction"
+    },
+    {
+        "id": 904,
+        "chunk": "# 二、机床色彩配置原则",
+        "category": " Introduction"
+    },
+    {
+        "id": 905,
+        "chunk": "# 1.单色或组合色  \n\n机床可以采用单色涂装，也可以采用组合色涂装，采用组合色涂装要注意两项原则。  \n\n(1）下深上浅的格调颜色深浅能给人以轻重感，深者重、浅则轻。下深上浅的组合能给操作者一种稳定感、安全感，有利于劳动者提高生产效率。  \n\n(2）色界要自然，不能强制两种色的界线要根据机床的外形结构特点，取其自然界线，不要“强制”划界。另外，两色配置要协调、和谐，要以给人舒适、美观为原则。",
+        "category": " Introduction"
+    },
+    {
+        "id": 906,
+        "chunk": "# 2.显示读数仪表  \n\n显示读数仪表一般采用无光漆或橘纹漆，减少视力疲劳，以利操作者读数。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 907,
+        "chunk": "# 3.平光漆与美术漆  \n\n平光漆与美术漆，机床都可采用，一般说来中、大重型机床以选用平光漆为主，仪表机床与小型机床以选用美术漆为主，选用的美术漆主要是锤纹漆与橘纹漆。无论选用什么漆，都要考虑提高机床装饰性能和给操作者以舒适为原则。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 908,
+        "chunk": "# 三、世界各地对色彩的爱好与禁忌  \n\n世界上不同的国家和地区对色彩的好恶和习惯不同，一般说来，绿、蓝、红、黄四种颜色能为世界广大地区接受，除个别地区外，对这四种颜色表示爱好。现将部分国家与地区对颜色的爱好与禁忌情况列于表3-10-39。  \n\n表3-10-39 世界部分国家与地区对颜色的爱好与禁忌情况  \n\n\n<html><body><table><tr><td>洲别</td><td colspan=\"2\">国家与地区</td><td>爱好颜色</td><td>禁忌颜色</td></tr><tr><td>亚</td><td>中 内地 国 阿富汗 韩国 朝鲜</td><td>香港和澳门地区</td><td>红、黄、绿 红、绿、黄和鲜艳色 红、绿 红、绿、黄和鲜艳色 红、绿、黄和鲜艳色</td><td>黑、白 黑、灰 黑。灰</td></tr><tr><td>洲</td><td>印度 日本 巴基斯坦 马来西亚 新加坡 泰国 缅甸 斯里兰卡 阿拉伯联合酋长国</td><td>沙特阿拉伯</td><td>绿、黄、红、橙及鲜艳色 柔和色 绿、金色 红、橙及鲜艳色 红、绿、黄 鲜艳色 红、黄 绿、白 绿、蓝 绿、蓝 黑</td><td>黑、灰 黑、白、灰 黑、深灰、和黑白相间 黑 黑 黑 黑 黄 粉红、紫、黄 粉红、黄、紫</td></tr><tr><td>北 美 洲</td><td>土耳其 叙利亚 美国 加拿大</td><td>红、白、绿 青、蓝、绿、红、白 鲜艳色彩 素净色彩</td><td></td><td>黄、紫、粉红</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>洲别</td><td></td><td></td><td>国家与地区</td><td></td><td>爱好颜色</td><td>暗淡色、紫</td><td></td><td>禁忌颜色</td><td></td><td></td></tr><tr><td>非</td><td>埃及 博茨瓦纳 乍得 埃塞俄比亚 加纳 马达加斯加 突尼斯 摩洛哥</td><td></td><td></td><td></td><td>鲜明色 蓝、黑、白、绿 白、粉红、黄 鲜艳色 明亮色</td><td>黑、红 黑 黑 黑 白 红、黑</td><td></td><td></td><td></td><td></td></tr><tr><td>洲</td><td>尼日利亚 贝宁 南非 毛里塔尼亚 俄罗斯</td><td></td><td></td><td></td><td>明亮色 绿、白、红 绿、红、黑、鲜艳色 红、白、蓝 绿、黄 红、白、绿</td><td></td><td>红、黑</td><td></td><td></td><td></td></tr><tr><td>欧</td><td>奥地利 法国 英国 荷兰 爱尔兰 挪威 瑞士 葡萄牙</td><td></td><td></td><td></td><td>红、黄、蓝 淡雅色彩 橙、蓝 红、蓝、绿 红、黄、蓝 无特殊爱好</td><td>黑 墨绿 黑</td><td></td><td></td><td></td><td></td></tr><tr><td>洲</td><td>丹麦 捷克 斯洛伐克 德国 希腊 罗马里亚 意大利 比利时 瑞典</td><td></td><td></td><td></td><td>红、白、蓝 红、白、蓝 红、白、蓝 鲜艳色 绿、蓝、黄 红、白、绿、黄 醒目颜色 蓝 黑、绿、黄</td><td>黑 黑 红、红黑相间 黑 黑 紫 蓝</td><td></td><td></td><td></td><td></td></tr><tr><td>拉 丁 美 洲</td><td>墨西哥 阿根廷 哥伦比亚 圭亚那 尼加拉瓜 秘鲁 委内瑞拉 古巴 巴拉圭</td><td></td><td></td><td>红、白、绿 黄、绿、红 红、蓝、黄 明亮色 红、紫、黄、鲜艳色 黄 鲜艳色 鲜明色</td><td></td><td>黑紫 蓝、白、蓝平行条色 蓝、红</td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n$\\textcircled{1}$ 涂膜必须美观大方、外观平整、色泽均匀一致；  \n\n$\\textcircled{2}$ 涂膜不允许有流挂、起泡、发白、划痕等病态；  \n\n$\\textcircled{3}$ 部件装配结合面之涂层，必须牢固、界线分明，边角线条清楚、整齐，不同颜色的漆不得相互沾染。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 909,
+        "chunk": "# 2.用光泽计进行光泽度检测  \n\n采用平光漆涂装的机床，要用光泽计，按GB1743标准进行测定，光泽度要求见表3-10-40。  \n\n表3-10-40 机床涂装光泽度  \n\n\n<html><body><table><tr><td rowspan=\"2\">机床类别</td><td colspan=\"2\">销售类别</td></tr><tr><td>出口</td><td>内销</td></tr><tr><td>中、小型机床</td><td>不少于85%</td><td>不少于75%</td></tr><tr><td>大、重型机床</td><td>不少于75%</td><td>不少于70%</td></tr></table></body></html>  \n\n若采用美术漆进行涂装的机床，不测光泽度，美术漆的膜要丰满，花纹要均匀一致。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 910,
+        "chunk": "# 二、涂层耐温热试验  \n\n机床涂层有耐候要求，所以机床涂层要进行模拟耐候试验，主要进行耐湿热试验。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 911,
+        "chunk": "# 1．试验设备  \n\n调温调湿试验箱。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 912,
+        "chunk": "# 2.试片  \n\n采用 $70\\mathrm{{mm}\\times150\\mathrm{{mm}\\times6\\mathrm{{mm}}}}$ 规格的TH20或 $\\mathrm{TH15}\\sim33$ 的铸铁片，按机床涂装工艺制 成机床涂层试片，每次试验不少于3片。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 913,
+        "chunk": "# 3.试验条件  \n\n将试片悬挂在试验箱内，并保持适当距离。箱内温度控制在 $47^{\\circ}C\\pm2^{\\circ}C$ ，相对湿度在$95\\%$ 以上，在上述条件下连续试验8h，然后打开箱门，让其自然降温降湿， $24\\mathbf{h}$ 为一循环周期，连续试验21周期。试验期间，每3天检查一次。  \n\n试验结果按表3-10-41进行评定。  \n\n表3-10-41 漆膜质量评定标准  \n\n\n<html><body><table><tr><td>级别</td><td>漆膜损坏程度</td></tr><tr><td>良好</td><td>1.轻微失光(5%～20%)； 2.轻微变色； 3.漆膜状态良好，没有起泡、开裂、脱落、生锈等病</td></tr><tr><td>合格</td><td>1.较明显失光（21%～50%）； 2.较明显变色； 3.漆膜表面有轻微、个别的微泡（占总面积10%以下），没有中、大泡</td></tr><tr><td>不合格</td><td>1.严重失光（50%以上)； 2.严重变色（色调改变）； 3.明显成片的微泡（占总面积10%以上），或出现中、大泡； 4.生锈、开裂、脱落等严重损坏者</td></tr></table></body></html>\n\n注：1.镀片四周边缘 $\\mathsf{5m m}$ 内及因外来因素引起的损坏现象不计。2.漆膜损坏现象只要达到表中规定的等级中任何一条，即属该等级；如有跨级现象，则按较差的那一级评定。3.起泡程度的分级，以泡的直径为衡量标准；微泡直径小于 $1\\mathrm{mm}$ ；中泡直径为 $1\\sim5\\mathrm{mm}$ ;大泡直径大于 $\\mathrm{5mm}$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 914,
+        "chunk": "# 三、涂层耐工作介质试验  \n\n机床在工作中，其涂层不可避免要沾上机床润滑油、切削液等工作介质，涂层要能耐这些工作介质，所以涂层质量检验要进行耐工作介质试验。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 915,
+        "chunk": "# 1.涂层耐工作介质试验方法  \n\n涂层耐工作介质试验方法见表3-10-42。  \n\n表3-10-42 涂层耐工作介质试验  \n\n\n<html><body><table><tr><td>试验内容</td><td>介质</td><td>方法</td><td>温度</td><td>试件数</td><td>时间</td></tr><tr><td>耐机油试验</td><td>32#机械油</td><td rowspan=\"2\">半浸（即试片一半 浸人介质，另一半露</td><td rowspan=\"2\">常温</td><td rowspan=\"2\">不少于3件</td><td rowspan=\"2\">21d</td></tr><tr><td>耐切削液试验</td><td>切削液试液配比： 亚硝酸钠0.3% 碳酸钠0.5% 自来水余量</td></tr></table></body></html>\n\n注： $^{*}32^{\\sharp}$ 机械油”即以前称的 $^{i i}20^{\\sharp}$ 机械油”。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 916,
+        "chunk": "# 2.评定标准  \n\n经试验后，用干净的棉纱指干试片，用眼睛观察漆膜表面有无起泡、脱落、开裂等损坏现象，无上述损坏现象，则为合格。允许有轻度失光、变色。  \n\n评定时，三块平行试片中以两块情况接近者为准。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 917,
+        "chunk": "# 参考文献  \n\n[1］王锡春等编著．涂装技术，北京：化学工业出版社，1988.  \n[2]张俊臣主编．涂料及涂料用无机颜料，第3版，北京：化学工业出版社，2002.  \n[3]汪国平编著，工业涂料与涂装技术丛书：船舶涂料与涂装技术．第2版，北京：化学工业出版社，2006.  \n[4]上海市化轻公司油漆供应部编，化工产品应用手册：涂料颜料，上海：上海科学技术出版社，1990.  \n[5］机械产品涂装技术手册编写组编，机械产品涂装技术手册，北京：机械工业出版社，1996.  \n［6]［美］ZenoW．威克斯，Frank．N．琼斯，S.Peter 柏巴斯著．有机涂料科学和技术．经良，姜英涛等译，北京：化学工业出版社，2002.  \n[7］涂料工艺编委会编．涂料工艺．第3版．北京：化学工业出版社，2001.",
+        "category": " References"
+    },
+    {
+        "id": 918,
+        "chunk": "# 防火涂料1",
+        "category": " Introduction"
+    },
+    {
+        "id": 919,
+        "chunk": "# 第一节 防火涂料概述  \n\n防火涂料是指涂覆于基材表面，能降低被涂材料表面的可燃性、阻滞火灾的迅速蔓延，或是涂覆于结构材料表面，用于提高构件耐火极限的一类物质。它具有普通涂料的装饰性，更重要的是涂料本身具有的特性决定了它具有防火保护功能，在火灾发生时能够阻止燃烧或对燃烧迅速扩展有延滞作用，从而使人们有充分的时间进行火灾扑救工作（将火灾制止于初始阶段)。  \n\n防火涂料除了具有普通涂料的装饰作用和对基材提供物理保护外，还需要具有阻燃耐火的特殊功能，要求它们在高温下具有一定的防火隔热效果，要达到这个目的，防火涂料应具备一些基本条件。",
+        "category": " Introduction"
+    },
+    {
+        "id": 920,
+        "chunk": "# 1.防火隔热性能  \n\n这就要求防火涂料在高温下具有一定的防火隔热效果，保护建筑物结构或限制火灾的蔓延扩大，提供30min至数小时的耐火时间，以便给消防人员赢得抢救时间，以确保建筑结构安全，保障国家和人民生命财产的安全。",
+        "category": " Introduction"
+    },
+    {
+        "id": 921,
+        "chunk": "# 2.对被保护基材无腐蚀性或破坏性  \n\n这就要求防火涂料具有适宜的酸碱性，因为强酸性和强碱性都会降低基材的力学性能。酸对木材有水解作用，破坏木材的纤维结构，降低木材的机械强度；对钢材有腐蚀性，降低钢材的机械强度。防火涂料对被保护基材应具有较高的黏结牢度而不脱落。木材黏结剂标准规定黏结剂的pH不应低于3.5，因此防火涂料的pH不应低于3.5，否则其对木基材的黏结强度下降。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 922,
+        "chunk": "# 3.适当的黏度和流动性  \n\n一定的流动性能保证防火涂料均匀地分布于基材表面，使其具有一定的黏结作用和装饰作用。适当的黏度则是保证防火涂料有良好的润湿性，保证涂层有足够的数量不致使涂料液流失或涂层过厚。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 923,
+        "chunk": "# 4.良好的使用性能  \n\n通过化学或物理作用，防火涂料涂层固化后能达到所要求的各种物理性能（如胶合板的剪切强度，刨花板的平面抗拉、吸水厚度膨胀等)，并具有一定的耐老化性能。防火涂料最好是阻燃效果好，且无毒，燃烧时不产生浓烟和毒气，使用性能稳定、方便，如适用期长、常温固化、固化时间短等。防火涂料原料来源广泛、价格低廉，为高效率生产和降低生产费  \n\n用创造条件。  \n\n防火涂料有不同的分类方法，主要有以下几种。  \n\n（1）按性质分类油性防火涂料；水性防火涂料。  \n(2）按机理分类 膨胀型防火涂料；非膨胀型防火涂料。  \n（3）按应用分类 饰面型防火涂料(不透明防火涂料、透明防火涂料)；钢结构防火涂料（膨胀型防火涂料、非膨胀型防火涂料)；电缆防火涂料；隧道防火涂料；预应力混凝土楼板防火涂料。(4）按应用场所分类封闭场所（船舱)；开场所。  \n(5）按应用环境分类 室内；室外。  \n(6）按化学性质分类有机防火涂料；无机防火涂料；有机、无机复合型防火涂料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 924,
+        "chunk": "# 第三节 防火涂料的防火机理  \n\n严格意义上来讲，上述所有的防火涂料都可归纳为膨胀型防火涂料和非膨胀型防火涂料。下面就膨胀型防火涂料和非膨胀型防火涂料的防火机理加以论述。  \n\n从燃烧的条件知道，要使燃烧不能进行，必须将燃烧的三个要素（可燃物、氧气、热源）中的任何一个要素隔绝开来。因此防火涂料之所以可以防火，可以归纳为以下几点：  \n\n①防火涂料本身具有难燃性或不燃性，使之被保护的可燃性基材不直接与空气接触而延缓基材着火燃烧；  \n\n②防火涂料遇火膨胀发泡，生成隔热、隔氧的致密膨胀层，封闭被保护基材，阻止基材着火燃烧；  \n\n③防火涂料遇火受热分解释放出不燃性的情性气体，冲淡被保护基材受热分解出的易燃气体和空气中的氧气，抑制燃烧；  \n\n④ 燃烧被认为是游离基引起的连锁反应。而含氮、磷的防火涂料受热分解放出一些活性自由基团，与有机自由基结合，中断连锁反应，降低燃烧速度。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 925,
+        "chunk": "# 1.膨胀型防火涂料的膨胀发泡机理  \n\n膨胀型防火涂料的防火效果主要是由以下几点因素所控制：绝热效果，利用膨胀炭层，阻止热量传递；  \n膨胀吸热，涂膜在高温下发生软化熔融蒸发膨胀及碳源的分解吸收了大量的热；  \n隔绝氧气，膨胀炭层形成覆盖作用；  \n稀释空气中氧气的浓度，不燃气体释出。  \n目前膨胀型防火涂料又分为有机型和无机型。  \n\n（1）有机膨胀型防火涂料的主要作用机理膨胀型防火涂料中通常含有：a.脱水成炭催化剂（酸源），一般指无机酸或能在燃烧加热时生成酸的物质，如磷酸、硫酸、硼酸及磷酸酯等物质，释放出的无机酸要求沸点高，而氧化性不太强；b.成炭剂（碳源)，一般是含碳丰富的多羟基化合物，可以单独或在催化剂作用下脱水成炭，如季戊四醇以及多乙二醇和酚醛树脂等；c.发泡剂（气源)，一般指含氮的多碳化合物，在受热条件下释放出惰性气体，如三聚氰胺、尿素、双氰胺、聚酰胺、脲醛树脂等。从机理上讲，膨胀炭层的形成一般要经过以下过程（图3-11-1）：  \n\n![](images/f15b81909edb48ec568c1792c1ed657f6ebb33b77f0c90e4e2936f923b7c84a5.jpg)  \n图3-11-1 膨胀炭层形成过程  \n\n膨胀型防火涂料受热时，成炭剂在催化剂作用下脱水成炭，炭化物在发泡剂分解的气体作用下形成膨松、有封闭结构的炭层。  \n\n在整个过程中，要求催化剂分解放出酸类物质、成炭剂脱水炭化、发泡剂分解产生气体三个步骤在变化的温度、时间、速度方面要基本协调一致。  \n\n该炭层可以阻止基材与热源间的热传导，另外多孔炭层可以阻止气体扩散，同时阻止外部氧气扩散至基材表面。膨胀型防火涂料的防火效果主要取决于成炭反应、膨胀反应及炭层结构。  \n\n$\\textcircled{1}$ 成炭反应膨胀型防火涂料受热时发生无机酸与多羟基化合物的反应。以APP（聚磷酸铵）和PER（季戊四醇）的反应为例，成炭反应过程分几步进行。首先 $210^{\\circ}C$ 时APP长链断裂而生成磷酸酯键，失去水和氨后，可以生成环状磷酸酯。反应最终产物的结构决定于初始PER/APP的摩尔比。此外，PER在APP作用下可能发生分子内脱水生成醚键。若继续升高温度，通过炭化反应，磷酸酯键几乎完全断裂，生成不饱和富碳结构，反应中可能有Diels-Alder反应，使得环烯烃、芳烃及稠烃结构进人焦炭结构。  \n\n$\\textcircled{2}$ 膨胀反应膨胀炭层的最后体积以及封闭小室的形状将决定于成炭时放出气体数量以及成炭物的黏度。发泡必须满足气体释放过程与炭化过程相匹配。尿素便不能与APP-PER体系很好匹配。虽然尿素可以释放 $70\\%$ 的气体，但它的分解温度 $\\langle150\\sim240^{\\circ}\\mathrm{C}$ ）与膨胀炭层形成温度（APP-PER体系） $280{\\sim}320^{\\circ}C$ 相比太低。三聚氰胺作为发泡剂的作用机理更为复杂。首先在 $250{\\sim}380^{\\circ}C$ 可以发生下列反应：  \n\n$$\n2C_{3}\\small\\mathrm{H_{6}N_{6},\\longrightarrow C_{6}\\mathrm{H_{9}N_{11},~}}\\mathrm{eC_{6}\\mathrm{H_{6}N_{10},~}}\\mathrm{eC_{6}\\mathrm{H_{3}N_{9}}}\n$$  \n\n这些反应产物比三聚氰胺有更好的热稳定性。挥发的三聚氰胺及其聚合过程中产生的氨气都可以起到膨胀作用。此外，三聚氰胺和聚磷酸铵在体系中会相互作用，三聚氰胺的热行为将会改变，生成三聚氰胺焦磷酸盐和聚磷酸盐。其热降解在 $650^{\\circ}C$ 接近完成，形成可以稳定耐热到 $950^{\\circ}C$ 的白色剩余物。据推测该剩余物为PN化合物。以上过程都有三聚氰胺、水分及氨气放出。所以三聚氰胺磷酸盐不仅有膨胀作用，而且参与构造炭层。  \n\n另外，炭化反应生成的PER磷酸酯以及PER醚结构在加热时也会出现膨胀现象。  \n\n该体系根据其机能包括脱水催化剂、炭化剂和发泡剂三部分。三者缺一不可，它们在膨胀发泡和阻火隔热过程中起着“协和”效应。下面分别对其作一详细介绍。  \n\n$\\textcircled{1}$ 脱水催化剂凡是受热能分解产生具有脱水作用的酸的化合物，均可作为防火涂料的脱水成炭催化剂，如磷酸、硫酸、硼酸等的盐、酯和酰胺类化合物。磷酸的铵盐是最常用的脱水成炭催化剂，这类物质在高温下能脱氨生成磷酸，继而生成聚磷酸，聚磷酸能与多羟基化合物发生强烈的酯化反应并脱水，引发膨胀过程。作为膨胀型防火涂料的关键组分，脱水催化剂的主要功用是促进和改进涂层的热分解进程，促进形成不易燃的三维炭层结构，减少热分解产生的可燃性焦油、醛、酮的量；促进产生不燃性气体反应的发生。  \n\n表3-11-1列出了一些磷酸铵盐、酯、酰胺的物理化学性质。  \n\n但磷酸铵、磷酸氢二铵及磷酸二氢铵这些低分子的化合物，较易溶于水，在涂料成膜时会发生重结晶，结晶颗粒沉析在涂层表面上，不仅严重影响了涂层的外观，而且会使涂层在使用中由于外界条件的变化而发生性能变化，使其防火性能大大下降。为此，早期作为脱水催化剂的磷酸氢二铵和磷酸二氢铵，其使用逐渐减少。现在普遍采用聚磷酸铵（APP)、磷酸铵镁和磷酸三聚氰胺（MP)、磷酸脲、磷酸胍、磷酸三甲苯酯、烷基磷酸酯、硼酸盐等物质。  \n\n表3-11-1 一些脱水催化剂的物理化学性质  \n\n\n<html><body><table><tr><td>名称</td><td>分子式</td><td>相对分子 质量（单元）</td><td>磷含量 /%</td><td>分解温度 /C</td><td>溶解度 /(g/100g水）</td></tr><tr><td>磷酸氢二铵</td><td>(NH)HPO4</td><td>132</td><td>23.5</td><td>87</td><td>40.8</td></tr><tr><td>磷酸尿素</td><td>CO(NH)z·HPO</td><td>156</td><td>19.6</td><td>130</td><td>52.0</td></tr><tr><td>磷酸二氢铵</td><td>(NH)HPO4</td><td>115</td><td>26.9</td><td>150</td><td>27.2</td></tr><tr><td>磷酸胍尿素</td><td>CHNO·HPO</td><td>200</td><td>15.5</td><td>191</td><td>一</td></tr><tr><td>聚磷酸铵</td><td>(NH4)n+2P,O3n+1</td><td>97</td><td>32</td><td>212</td><td>1.5</td></tr><tr><td>磷酸三聚氰胺</td><td>CH6N6 ·HPO4</td><td>224</td><td>一</td><td>300</td><td>一</td></tr><tr><td>焦磷酸三聚氰胺</td><td>2(CHN)·HPO7</td><td>430</td><td>二</td><td>一</td><td></td></tr></table></body></html>  \n\nAPP是膨胀型涂料中最常用的脱水催化剂，聚磷酸铵的分子式为 $(\\mathrm{NH_{4}})_{n+2}\\mathrm{P}_{\\bar{n}}\\mathrm{O}_{3n+1}$ （通式)，当 $\\scriptstyle{\\bar{n}}$ 足够大时可写作（ $\\mathrm{\\bfNH_{\\ell}P O_{3}})_{n}$ ，结构式如下  \n\n$$\n\\begin{array}{c}{{\\mathrm{{~\\small~\\displaystyle~\\displaystyle~\\int~}}}}\\\\ {{\\mathrm{{~\\cal~H}_{4}N-O-P-o-\\displaystyle~\\int~}}}\\\\ {{\\mathrm{{~\\small~\\displaystyle~\\int~}}}}\\\\ {{\\mathrm{{~\\small~\\displaystyle~\\sum~}}}}\\\\ {{\\mathrm{{~\\small~\\displaystyle~\\sum~}}}}\\\\ {{\\mathrm{{~\\small~\\cal~NH}_{4}~\\small~\\displaystyle~\\ N H_{4}~}}}\\end{array}\\begin{array}{c}{{\\mathrm{{~\\small~\\displaystyle~O~}~}}}\\\\ {{\\left|}}\\\\ {{\\mathrm{{~\\small~P-O-\\displaystyle~\\int~}}}}\\\\ {{\\mathrm{{~\\small~\\displaystyle~\\int~}}}}\\\\ {{\\mathrm{{~\\small~\\displaystyle~O~}~}}}\\\\ {{\\mathrm{{~\\small~\\displaystyle~NH}_{4}~}}}\\end{array}\\right.}}\\end{array}\n$$  \n\n当 $\\eta=10\\sim20$ ，相对分子质量约为 $1000{\\sim}2000$ ，当 $n>20$ 时，相对分子质量 $>2000$ 。聚磷酸铵（简称APP）是白色（结晶或无定形）粉末，系无分支的长链聚合物，随聚合度$(n)$ 的不同可分为水溶性（ $_{;n=10\\sim20},$ ）和水不溶性（ $n{\\geq}20!$ ）两种。常用结晶态APP为水不溶性长链状聚磷酸铵盐，有 $\\mathbf{I}\\sim\\mathbb{V}$ 五种变体。APP含磷、氮量高，P-N系产生协同效应，阻燃效果好；产品热稳定性好，分解温度高于 $250^{\\circ}C$ ，约 $750^{\\circ}C$ 全部分解；水溶性低，吸潮性小，产品细度可达300目以上，相对密度小，约为1.24，分散性好；产品接近中性，化学稳定性好，可与其他任何物质混合不起化学反应，用于涂料、橡胶、塑料等物料中不影响物料的理化性能；毒性低， $\\mathrm{LD}{\\geq}10\\mathrm{g}/\\mathrm{kg}$ ，使用安全，是一种最重要的高效磷系无机阻燃剂。APP的水解速率与粒子的大小、 $\\mathfrak{p H}$ 以及温度有关，当粒径从 $1\\mathrm{mm}$ 增加到 $3\\mathrm{mm}$ 时水解速率降低 $2\\sim3$ 倍。溶解度（磷钼蓝比色法， $20^{\\circ}C$ ，2h）为 $0.9g/100g\\ \\mathrm{H}_{2}\\mathrm{O}$ ， $\\mathfrak{p H}$ ( $10\\%$ APP悬浮液）为5.8， $\\mathbf{P}$ 含量（重量法）为 $27.36\\%$ $\\langle w_{\\mathrm{P_{z}O_{5}}}=62.70\\%\\rangle$ 费 $N$ 含量（Kjeldahl法）为$12.3\\%$ 。热分析为 $34^{\\circ}\\mathrm{C}\\rightarrow80^{\\circ}\\mathrm{C}\\rightarrow134^{\\circ}\\mathrm{C}$ 时吸热， $271^{\\circ}\\mathrm{C}\\twoheadrightarrow349^{\\circ}\\mathrm{C}\\twoheadrightarrow377^{\\circ}\\mathrm{C}$ 时放热， $100^{\\circ}C$ 时质量减轻 $7.5\\%$ ， $400^{\\circ}C$ 时质量减轻 $41\\%$ ， $578^{\\circ}C$ 时质量减轻 $50\\%$ 0  \n\nAPP的阻燃作用与其他磷酸铵盐相同，却不存在其他磷酸铵盐的缺点。由于其热稳定性好，含 $\\mathbf{P}$ 和 $N$ 量更高，水溶性低、不吸潮等优点，使其得到广泛的应用。APP阻燃剂与炭化剂（季戊四醇等)、发泡剂（三聚氰胺等）并用于膨胀型防火涂料中，遇火受热分解，首先生成磷酸，在 $300^{\\circ}C$ 以上 $\\mathrm{H_{3}P O_{4}}$ 极不稳定，进一步脱水生成聚磷酸或聚偏磷酸，使炭化剂脱水炭化，发泡剂鼓泡，放出不燃气体，涂膜炭化膨胀，形成蜂窝状隔热层，阻燃效果显著。  \n\n炭化层覆盖于基材表面，隔绝空气，使燃烧室息，而且其导热性差，能阻止火焰蔓延；放出的水蒸气、氨、HCI等不燃气体，能降低体系的温度，稀释空气中的氧浓度。APP制成的防火涂料成膜性好，涂膜理化性能优良，不吸潮，经水浸渍后阻燃效果不变，能使用于潮湿环境中。  \n\nAPP常与其他阻燃剂并用，其阻燃作用优于单独使用，常用的并用体系如 $\\mathrm{APP+}$ 甲醛+Mg(OH)2；APP+Al(OH)3；APP+BaCl；APP+尿素；APP+磷酸胍；APP+甲醛 $+$ 双氰胺； $\\mathbf{APP+Sb_{2}O_{3}}$ 等。当APP的聚合度 $n<20$ 时，在水中溶解度（ $20^{\\circ}C^{\\prime}$ ）药为10～30g/100gHzO，是最佳的木材浸渍剂，常压下浸渍马尾松、红松等材料，吸收药剂量达 $25\\sim35\\mathrm{kg/m^{3}}$ 时，处理过的材料氧指数达30以上。用合适的分散剂和乳化剂把氢氧化铝等阻燃剂和APP混合配成防火阻燃液可处理木材、木制品、纸张、纸板、织物等易燃纤维材料，其阻燃效果极佳。  \n\n聚合度在 $20\\sim400$ 范围内，其耐水性较差，分散的涂料组分经过一段时间后，容易发生相分离和沉淀，故成膜后耐水性较差；聚合度在 $500\\sim800$ 范围内，涂料组分的稳定性及成膜后的耐水性比较好，这在水性涂料中的表现尤为显著。此外，在防火涂料的研究和工业生产中，选择脱水催化剂应综合考虑脱水催化剂的水溶性、热稳定性、阻燃元素磷的含量和原材料价格等因素。  \n\n$\\textcircled{2}$ 成炭剂当涂层遇到火焰或高温作用时，在催化剂的作用下，炭化剂脱水炭化形成炭层。炭化剂主要有：a，碳水化合物，如淀粉、葡萄糖；b.多元醇化合物，如山梨醇、季戊四醇（PER)、二季戊四醇（DPE)、三季戊四醇；c.树脂性物质，如尿素树脂、氨基树脂、聚氨酯树脂、环氧树脂等。炭化剂的有效性一方面决定于它的碳含量和羟基的数目，碳含量决定其炭化速度，羟基含量决定其脱水和成泡速率，表3-11-2列出了几种炭化剂及其物理性质，一方面采用高碳含量、低反应速率的物质作炭化剂较为适宜；另一方面则取决于它们的分解温度，如采用APP作为脱水催化剂时，就应该采用热稳定性较高的季戊四醇（PER）或二季戊四醇（DPE）与之配用，若此时选用淀粉作为炭化剂，则不能形成理想的膨胀炭层。王国建等研究了季戊四醇和淀粉为炭化剂时涂料的防火性能，结果见表3-11-3。可见，虽然淀粉和季戊四醇的含碳量和羟基含量相差不大，但后者的防火效果明显好于前者，原因是淀粉的分解温度约为 $150^{\\circ}C$ ，远远低于聚磷酸铵的分解温度 $(212^{\\circ}C)$ ，在聚磷酸铵热分解之前，淀粉早已分解并产生大量的可燃性焦油，因此，淀粉与聚磷酸铵配合使用，不能形成理想的发泡层。而季戊四醇的分解温度高达 $280^{\\circ}C$ 左右，它能在由聚磷酸铵热分解产生的酸的作用下脱水成炭，最终形成良好的膨胀发泡层。所以，炭化剂与脱水成炭催化剂在分解温度上的匹配与否是形成理想膨胀发泡层的关键。二季戊四醇（DPE）成炭效果优于季戊四醇（PER)，但由于季戊四醇（PER）价格较低，使其使用更广泛。  \n\n表3-11-2几种炭化剂及其物理性质  \n\n\n<html><body><table><tr><td>名称</td><td>分子式</td><td>相对分子质量（单元）</td><td>碳含量/%</td><td>羟基含量/%</td><td>反应指数/(g/100g)</td></tr><tr><td>蔗糖</td><td>CsHs(OH)s</td><td>180</td><td>40</td><td>56</td><td>2.3</td></tr><tr><td>山梨醇</td><td>C6Ho(OH)s</td><td>184</td><td>40</td><td>55</td><td>3.08</td></tr><tr><td>淀粉</td><td>(CHoOs)</td><td>162</td><td>44</td><td>52.4</td><td>2.1</td></tr><tr><td>季戊四醇</td><td>C(CHOH)4</td><td>136</td><td>44</td><td>50</td><td>一</td></tr><tr><td>二季戊四醇</td><td>CH1s(OH)6</td><td>127</td><td>50</td><td>42.8</td><td>2.5</td></tr></table></body></html>  \n\n表3-11-3不同炭化剂对涂料防火性能的影响  \n\n\n<html><body><table><tr><td rowspan=\"2\">炭化剂</td><td rowspan=\"2\">碳含量 /%</td><td rowspan=\"2\">羟基含量 /%</td><td colspan=\"2\">小室燃烧法</td><td colspan=\"2\">煤气灯燃烧法</td></tr><tr><td>质量损失</td><td>成炭体积</td><td>试背面出现</td><td>膨胀高度/mm</td></tr><tr><td>淀粉</td><td>44</td><td>52.4</td><td>8.5</td><td>30.6</td><td>325</td><td>5</td></tr><tr><td>PER</td><td>44</td><td>50.0</td><td>2.4</td><td>4.8</td><td>945</td><td>18</td></tr></table></body></html>\n\n注：以氯乙烯-偏氯乙烯高聚物为胶黏剂，以APP为脱水成炭剂，以MEL为发泡剂。$\\textcircled{3}$ 发泡剂常用的发泡剂有三聚氰胺、尿素、脲醛树脂、双氰胺、聚酰胺、蜜胺、聚  \n\n脲、氯化石蜡等，它们在受热分解时释放出不燃性气体（如HCl、NH3、HzO等)，使涂层膨胀形成海绵状炭层。有时，为了加强防火涂料的阻燃效果，采用两种或多种发泡剂并用，如防火涂料中同时使用含氯与含磷阻燃剂，不仅可以从固相到气相广泛抑制燃烧的进行，而且由于氯、磷燃烧时生成PCl3、POCl等化合物，产生阻燃协同效应。  \n\n在实际过程中，一般选取三聚氰胺（MEL）为主发泡剂，而作为增塑剂的氯化石蜡(CP）以及作为脱水催化剂的聚磷酸铵（APP)，也可以起部分发泡作用。选择各组分时要注意发泡剂分解产生气体、脱水催化剂分解放出磷酸等物质、炭化剂脱水炭化这3个步骤在发生变化的温度方面基本上协调一致。如果发泡剂的分解温度比脱水成炭催化剂低得多，分解产生的气体就会在涂层成炭层之前逸出而不能起到膨胀发泡作用；而如果发泡剂的分解温度比脱水成炭催化剂高得多，则分解产生的气体会将已形成的炭化层顶起吹掉，也不能形成良好的发泡层。一些发泡剂分解温度见表3-11-4。  \n\n表3-11-4 一些发泡剂的分解温度  \n\n\n<html><body><table><tr><td>项 目</td><td>双氰胺</td><td>三聚氰胺</td><td>胍</td><td>甘氨酸</td><td>尿素</td><td>氯化石蜡</td></tr><tr><td>分解温度/C</td><td>210</td><td>250</td><td>160</td><td>233</td><td>130</td><td>190</td></tr><tr><td>不燃性气体</td><td colspan=\"4\">NH、CO、HO</td><td colspan=\"2\">HCI、CO、HzO</td></tr></table></body></html>  \n\n表3-11-5列出了不同发泡剂对涂料防火性能的影响。可见，采用分解温度较高的聚磷酸铵作脱水成炭催化剂时，选择分解温度较高的三聚氰胺或六亚甲基四胺作为发泡剂，涂料的防火性能较好，而用分解温度较低的尿素作发泡剂，防火性能就要差得多。虽然尿素可以释放 $70\\%$ 的气体，但它分解温度（ $\\mathrm{130\\sim240^{\\circ}C}$ ）与膨胀炭层形成的温度（APP-PER体系）$280{\\sim}320^{\\circ}C$ 相比太低，与膨胀体系不匹配，而三聚氰胺在 $250\\sim380^{\\circ}C$ 分解产生气体，与膨胀体系相匹配，适宜作APP-PER体系合适的发泡源。但如果选择分解温度较低的磷酸二氢铵（分解温度 $150^{\\circ}C$ ）作为脱水成炭催化剂、尿素为发泡剂进行试验，涂料的防火性能明显提高（失重为 $4.8{\\mathrm{g}}$ ，炭化体积为 $23.6\\mathrm{cm}^{3}$ ，发泡高度为 $10\\mathrm{mm}$ ，背面出现焦斑时间为495s)。因此，发泡剂的选择要注意与催化剂相适应。  \n\n表3-11-5 不同发泡剂对涂料防火性能的影响  \n\n\n<html><body><table><tr><td rowspan=\"2\">发泡剂</td><td rowspan=\"2\">降解 温度 /℃</td><td colspan=\"3\">小室燃烧法</td><td colspan=\"3\">煤气灯燃烧法</td></tr><tr><td>质量损失 /g</td><td>成炭体积 /cm3</td><td>阻火 等级</td><td>试样背面出现 焦斑的时间/s</td><td>炭层高度 /mm</td><td>膨胀表面</td></tr><tr><td>三聚氰胺</td><td>250</td><td>2.4</td><td>4.8</td><td>1</td><td>945</td><td>18.0</td><td>好而均匀</td></tr><tr><td>尿素</td><td>160</td><td>8.2</td><td>35.6</td><td>2</td><td>270</td><td>4.0</td><td>大且不均匀</td></tr><tr><td>六亚甲基四胺</td><td>190</td><td>4.6</td><td>24.6</td><td>1</td><td>710</td><td>11.0</td><td>较大但均匀</td></tr></table></body></html>  \n\n事实上，膨胀型阻燃体系是比较复杂的，各组分的选择不同，形成的炭质结构也各不相同，对于常见的APP-PER-MEL体系，Vandersal等人认为其炭层形成主要经历了以下几步反应。  \n\n![](images/a9e3fd1455d77af8c3720da24002efbfc88ccfa9045114119b1afcc7f43dfd7c.jpg)  \n\n重复上述反应，可能生成下述结构。  \n\n![](images/9070952938d2f9c41f431c3d58810858204c17c317f9411a002049875901eb6e.jpg)  \n\n最终的产物结构取决于PER/APP的初始比。在实际反应中，PER在APP的影响下可以发生分子内脱水成醚键，若继续升高温度，通过炭化反应，磷酸酯键几乎完全断裂，生成不饱和的富碳结构，由该结构的聚合和交联反应生成炭层，这一步反应中可能有Diels-Alder反应，使得环烯烃、芳烃及稠环结构进入焦炭结构。形成的富碳物质在发泡源（三聚氰胺及其聚合过程产生的氨气）以及自身产生的气体作用下形成膨胀炭层。膨胀炭层的最后体积以及封闭小室的形状将取决于成炭时放出气体数量以及成炭物的黏度。此外，反应中还会伴有以下可有效捕获氢自由基、有效抑制燃烧自由基的反应和胺组分受热分解产生不燃气体的反应。  \n\n$$\n\\mathrm{PO}\\cdot+\\mathrm{H}\\cdot\\longrightarrow\\mathrm{HPO}\n$$  \n\n$$\n\\mathrm{HPO}\\cdot+\\mathrm{H}\\cdot\\longrightarrow\\mathrm{H}_{\\vec{z}}+\\mathrm{PO}\\cdot\n$$  \n\n$$\n\\mathrm{PO}\\cdot+\\mathrm{OH}\\cdot\\longrightarrow\\mathrm{HPO}\\cdot+\\dot{\\mathrm{O}}\\cdot\n$$  \n\n$$\n2\\mathrm{C_{3}H_{6}N_{6}}\\longrightarrow\\mathrm{C_{6}H_{9}N_{11}}+\\mathrm{NH_{3}}\n$$  \n\n$$\n\\mathrm{C_{6}H_{9}N_{11}{\\longrightarrow}C_{6}H_{6}N_{10}+N H_{3}}\n$$  \n\n$$\n\\mathrm{C_{5}\\ H_{6}N_{10}}\\mathrm{~\\longrightarrow~}\\mathrm{C_{6}\\ H_{3}N_{9}}+N H_{3}\n$$  \n\n(2）无机膨胀型防火涂料的主要作用机理有机型膨胀阻燃体系具有涂层美观、附着力好等特点，但其阻火时易产生烟雾和不同程度地放出毒性气体，成本也较高，于是，以硅酸盐为主体的无机膨胀型防火涂料便应运而生。它以水玻璃为基料和发泡基体，添加其他材料所组成，涂层遇到火焰及高温作用时，碱金属硅酸盐所含的结晶水及水玻璃中氧链上羟基的脱水作用而使涂层共熔变软、并且黏度较大，这时由于分解产生的气体不能自由地排出使涂壁产生气泡，形成了具有隔热功能的多孔质体——硅酸盐泡沫状隔热层。无机膨胀阻燃涂料阻火时具有如下特点：a.阻火时不产生毒性气体和烟雾；b.产生的硅酸盐泡沫状隔热层强度高，能有效地抵抗火焰热流的冲击作用，阻火性能比较突出；c.以水玻璃、无机矿物等为原料，成本低，原料来源广，易于制备；d.生产、使用过程无污染。但该类涂料防水性差，浸泡在水中或受雨水淋洗，涂层易脱落。  \n\n无机膨胀型防火涂料主要由成膜剂、发泡剂、成炭剂、脱水剂、防火填料及颜料等组成。成膜剂主要有水玻璃、硅溶液胶体和磷酸盐等，一般选用价格便宜、来源广泛的水玻璃；发泡剂常用的有磷酸铵盐、氯化石蜡、三聚氰胺等。但选择时应注意与成膜剂的匹配，如磷酸铵盐和水玻璃容易沉淀板结，氯化石蜡和成膜剂的混溶不好；成炭剂常采用季戊四醇、淀粉等，这些多羟基化合物和脱水催化剂反应生成多孔结构的炭化层；脱水剂常采用磷酸的铵盐、磷酸酯及三聚氰胺等来促进涂层分解；防火填料，其种类很多，主要有氢氧化铝、高岭土、硼砂、滑石粉、碳酸钙等。这些原料在受热分解时一方面要吸收大量热量；另一方面，如硼砂、氢氧化铝、碳酸钙等会不断产生大量的水汽或二氧化碳，在材料周围形成情性屏障，减缓燃烧速度。从以硅酸盐为主体的无机膨胀型防火涂料的研究历史来看，该类涂料的研究发展形成了下列几种类型。  \n\n$\\textcircled{1}$ 水合硅酸盐型这类涂料由水玻璃、水合水玻璃、固体水玻璃、无水水玻璃及少量填料组成。硬化涂层的主要成分为各种水合硅酸盐，水合硅酸盐中的结合水影响体系的熔程。该种涂料受热时，涂层在大于100℃时开始熔融，随着温度升高，涂层液化，结合水变成水蒸气。由于熔融的硅酸盐具有较高的黏度，水蒸气不能自由地排出而包含在黏稠的熔体中，便形成薄壁的气泡，涂层形成泡沫状结构，达到阻火、隔热的目的。随着温度进一步升高，硅酸盐泡沫层会熔缩，继而熔落。因此，水合硅酸盐型涂层后期阻火能力欠佳，这类涂料多用于木构件、织物、电缆等制品的防火保护。  \n\n表3-11-6为水合硅酸盐膨胀型防火涂料的配方及防火性能，  \n\n表3-11-6水合硅酸盐膨胀型防火涂料的配方及防火性能  \n\n\n<html><body><table><tr><td>配 方</td><td>用量/份</td><td colspan=\"3\">防火性能</td></tr><tr><td>水玻璃 硼砂</td><td rowspan=\"5\">335 3 5 5 5</td><td>涂层厚度/mm</td><td>１</td><td>2</td></tr><tr><td>季戊四醇</td><td>着火时间/min</td><td>10</td><td>12</td></tr><tr><td>三聚氰胺 钛白粉</td><td>着火温度/℃</td><td>610</td><td>630</td></tr><tr><td>ATH 滑石粉</td><td>膨胀高度/cm</td><td>3.0</td><td>3.8</td></tr><tr><td>氧化锌 水</td><td>阻燃时间/min</td><td>11</td><td>16</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 耐水硅酸盐型以水玻璃为成膜物质的硅酸盐膨胀型防火涂料，未改性的水玻璃涂层存在如下缺点：a.遇水时显示出强碱的性质，会使金属钝化，造成配套底漆破坏；b.由于碱金属硅酸盐在成膜过程中随着水分蒸发，不断析出二氧化硅，并自行缩合成硅氧链网状结构的涂膜，碱金属离子存在于结构中，一旦涂膜遇水，碱金属离子很快地溶解于水，涂膜也随之溶解，造成涂料耐水性较差。为改进水合硅酸盐型防火涂料的防水性能，可对膨胀阻燃体系进行如下改性处理：a.加热固化，将涂层在 $250\\sim300^{\\circ}C$ 烘烤1h，可提高防水性；b.改性水玻璃，通过引人某种增水基团取代水玻璃分子中的钠离子，提高耐水性；c.涂刷罩面层，在涂层表面干燥后，再涂刷一道罩面层，如甲基硅醇钠；d.固化剂固化，加入固化剂，一方面与碱金属离子发生反应生成水不溶化合物，另一方面促进 $\\mathrm{{\\bfSiO_{2}}}$ 胶体缩合成疏水性涂膜。常用的无机固化剂有缩合磷酸盐、聚磷硅酸盐、氟硅酸钠等。  \n\n$\\textcircled{3}$ 无机高、低温发泡复合型低温发泡涂层由NS-I与改性水玻璃配制而成，NS-I为增稠剂，其主要成分为无定形二氧化硅，可以与水玻璃发生反应，起到增稠水玻璃的作用，同时生成水合硅酸盐。  \n\n硬化涂层的主要成分为含多羟基的硅烷醇大分子及各种水合硅酸盐，它的膨胀、阻火过程与水合硅酸盐型相似。黄永勤、范春山、陈功智对低温发泡层进行热分析及模拟阻火试验观察显示了其膨胀、阻火历程。图3-11-2～图3-11-4所示分别为低温发泡涂层的DTA 曲线、TG-DTG曲线、模拟阻火实验曲线。由图3-11-2、图3-11-3曲线可以看出，涂层在$60\\sim90^{\\circ}C$ 吸热并失重，表明失去水分，从 $160^{\\circ}C$ 开始涂层强烈吸热并伴有失重现象，涂层产生低共熔，膨胀发泡。  \n\n图3-11-4低温发泡涂层的模拟阻火实验曲线表明，涂层发泡时，增厚至原涂层的 $10\\sim$ 20倍。因涂层起泡，发挥隔热作用，试件升温趋势减缓，阻火曲线斜率下降。温度继续上升，在 $490{\\sim}530^{\\circ}\\mathrm{C}$ 有一吸热峰，但无失重现象，为NS-I引起的相变。温度升至 $680^{\\circ}C$ 以上时出现宽的吸热峰，但无质量减少，表明形成的泡沫状隔热层开始熔缩，泡层变薄，阻火性能下降。低温发泡涂料配制简单，无需先将水玻璃加工成水合水玻璃或粉碎成无水水玻璃，而是直接将几种粉料与水玻璃混合，进行涂刷。  \n\n![](images/f4c8bd19f13c52d4e2a091e78942f9346c5ed0578c81f1179446b73223fc2d58.jpg)  \n图3-11-2 低温发泡涂层的DTA曲线  \n\n![](images/b467ddd2c5566795511b6afacaf659e7dbd671840e2132c08566856e6508922e.jpg)  \n图3-11-3 低温发泡涂层的TG-DTG曲线  \n\n![](images/14ca3c0c2bad197b0ab5625f4879332d5df5c2caa1a651c0e4f049b426f88250.jpg)  \n图3-11-4 低温发泡涂层的模拟阻火实验曲线  \n\n![](images/c3f24e145d329b22bffa34d3ad30f1dc43dec40a6bc7fd6de408d7440347ed08.jpg)  \n图3-11-5 高温发泡涂层的DTA曲线  \n\n高温发泡体系由水玻璃、玻璃料、发泡剂（BC-30）和耐温填料组成。由其DTA（见图3-11-5）曲线、TG-DTG曲线（见图3-1l-6）可见，在 $60\\sim90^{\\circ}C$ 涂层失去水分，在 $160\\sim$ $800^{\\circ}C$ 时涂层吸热并伴随着失重，涂层失去因水玻璃凝结带来的结合水及各种填料含有的结晶水， $800^{\\circ}C$ 以后，涂层吸热、失重非常缓慢，涂层开始熔融并膨胀发泡。图3-11-7的模拟阻火试验显示了高温发泡涂层的膨胀及阻火过程。由图可见，涂层受热至 $800\\sim820^{\\circ}C$ 时，膨胀发泡发挥隔热作用，试件的升温趋势减缓。  \n\n复合涂层由高、低温发泡层和隔离层组成，具有图3-11-8所示的结构。模拟实验曲线（见图3-11-9）显示了它的发泡和阻火过程。当涂层遇火时，低温发泡涂层首先膨胀、阻火，随着火焰温度升高，低温发泡涂层开始熔缩时，高温发泡层开始膨胀、阻火，复合涂层集中了两种涂料的优点，有效地提高了阻火效果，比较好地解决了硅酸盐涂层高温易熔滴的技术难题。该种复合涂料经国家固定灭火系统和耐火构件质量监督监测中心测试，涂层厚度为$4.5\\mathrm{mm}$ 时，在不同荷载条件下，使钢结构的耐火极限分别达到 $84\\operatorname*{min}$ 和 $135\\mathrm{min}$ 。但由于涂层为多层结构，涂刷工艺较复杂。  \n\n除以硅酸盐为主体的无机膨胀型防火涂料以外尚有以磷酸和氢氧化铝等在一定条件下反应，并配以阻燃剂及其他助剂而制成的一种无机膨胀型防火涂料 $\\operatorname{E}60-1$ 涂料。由于磷酸盐代替涂料中通用的硅酸盐，既能起到基料所要求的黏结性，又能在膨胀型防火体系中起发泡催化剂的作用。磷酸盐黏结剂的种类很多，根据所含金属不同其性能亦有差别，但是，含铝的磷酸盐强度和黏结性都较优良，而且作为生成磷酸铝盐的氢氧化铝无毒无味，价廉易得，适合作防火涂料的基料。该涂料在基料的研究和复合阻燃剂的应用上有创新，解决了无机防火涂料的耐水问题，其防火性能优异，理化性能、耐候性好，使用性能稳定，无环境污染，生产成本较低，适用于木材、纤维板、胶合板、塑料、玻璃钢等可燃基材的防火保护和装修。  \n\n![](images/1da7b9bc6fa1df94ad6c8fa817aef798ac85b50a5dd0cadf67ef1f65914baaf2.jpg)  \n图3-11-6 高温发泡涂层的TG-DTG曲线  \n\n![](images/9b4aae157b428bb8a3c4bfad648444d3856956c5ccf47c0fcedf732551725753.jpg)  \n图3-11-7 高温发泡层的模拟阻火实验曲线  \n\n![](images/1d1cc153ba365de38d0da2cb4779652f8d4575b8c3d24b45c1b92b34708b7f3e.jpg)  \n图3-11-8复合涂层结构  \n\n![](images/ace080b78bdfeea90683ae72a68cb5c200e42af621c284cd976c6d28399ba141.jpg)  \n图3-11-9 复合发泡层的模拟阻火实验曲线  \n\n下面为E60-1膨胀型无机防火涂料配方：  \n\n<html><body><table><tr><td>原材料</td><td>用量/%</td></tr><tr><td>基料（系氢氧化铝、磷酸和水反应制得）</td><td>40</td></tr><tr><td>复合阻燃剂</td><td>25</td></tr><tr><td>氧化铝（工业品，AlO>64%）</td><td>5</td></tr><tr><td>钛白粉（R101）</td><td>4</td></tr></table></body></html>\n\n$\\textcircled{1}$ 复合阻燃剂可从如下的品种及用量（100份基料中加入阻燃剂的份数）的组合中选择：  \n\n<html><body><table><tr><td>原材料 用量/%</td></tr><tr><td>脲醛树脂（工业品）</td></tr><tr><td>尿素（工业品） 6</td></tr><tr><td>增塑剂（工业品） 5</td></tr><tr><td>水（自来水） 10</td></tr></table></body></html>  \n\na.三氯乙基磷酸酯5，三聚氰胺8，滑石粉10；  \n\nb.三聚氰胺8，滑石粉10；  \n\nc.四溴双酚A5，三聚氰胺8，三氧化二10。  \n\n(3）有机、无机复合膨胀型防火涂料的防火作用机理无机材料作为主要成膜物质的防火涂料，其阻燃性优于有机防火涂料，但其耐水性等物理性能较差，如果能将二者结合起来，就可得到性能优良的有机、无机复合型防火涂料。  \n\n$\\textcircled{1}$ 水玻璃、有机物复合型这类涂料由水玻璃、有机物及各种填料组成，可分如下两种。  \n\na.水玻璃、玉米淀粉、CMC 混合涂料这种涂料在加人玉米淀粉、CMC之后，在水玻璃强碱性介质作用下，淀粉、CMC均发生熟化作用，形成了糊精等产物，改进了涂料的成膜性能，这两种碳水化合物遇热炭化、失水也会促进体系发泡。但这种涂料适用期在2h左右，且易结块，涂层不够平整，涂层发泡时，有少量烟雾冒出。  \n\nb.水玻璃、有机水乳液复合涂料这种涂料由水玻璃、水乳液和各种填料组成，乳液可选用聚醋酸乙烯、聚氯乙烯、聚甲基丙烯酸酯等聚合物乳液。水玻璃涂层经聚合物改进后，提高了涂层的耐水性和涂膜的装饰性，但随之而来的问题是涂层发泡时会产生少量烟雾和有害气体，配制的涂料稳定性欠佳，易凝胶。  \n\n上述两种涂料的涂层阻火时，泡沫层均以水合硅酸盐为主体，存在着泡层高温熔滴的技术难题，目前，仍主要用于木构件的防火保护。  \n\n$\\textcircled{2}$ 涂料中添加有机固化剂型在涂料中添加固化促进剂可以提高防火涂料的耐水性，常用的有机固化剂有三乙醇胺、乙二醛、甲基硅烷醇酸钠、甲基硅油（聚二甲基硅氧烷液体)。将它们预先制成乳化液，再与防火涂料混溶在一起，形成无机-有机复合型防火涂料。邹光中等人将甲基硅油与无机硅酸盐防火涂料混溶在一起，依据GB12441—2005做的耐水性实验，由结果可见，添加硅油可明显提高防火涂料的耐水性能。这是由于有机硅的加人，可部分取代钠水玻璃分子两端的钠离子或填充在—Si—O—Si—网状结构的间隙中，屏蔽残存的羟基，从而提高涂料的耐水性。同时还可知，干燥时间越长，涂层遇水不脱落时间也越长，硅油添加量越多，耐水性能越好。但硅油添加过多，会降低涂料稳定性，并会增加成本，实验结果显示以加入 $1.0\\%\\sim1.5\\%$ 硅油为宜。  \n\n$\\textcircled{3}$ 磷酸铝-丙烯酸复合膨胀型按配比量取磷酸和氢氧化铝，加入去离子水，搅拌至呈完全的乳液状，制得磷酸铝乳液。将磷酸铝乳液按比例趁热加人到丙烯酸乳液中，搅拌并控温在 $80^{\\circ}C$ 左右，至没有回流产生，即制得磷酸铝-丙烯酸复合乳液。按配方将阻燃剂加人去离子水和消泡剂，搅拌均匀再加人其他助剂，快速搅拌成糊状后，将其缓缓注入磷酸铝-丙烯酸复合乳液中，降温并恒温在 $40^{\\circ}C$ 左右，继续搅拌至无沉淀，即制得磷酸铝-丙烯酸复合膨胀型防火涂料。  \n\n(4）新型可膨胀石墨阻燃体系P-C-N、P-C-N-CI膨胀阻燃体系存在着耐高温性、耐老化性及耐水性较差等问题，为改善这个缺陷，有研究者将上述膨胀阻燃体系与可发生物理膨胀的可膨胀石墨配合使用，形成的复合阻燃膨胀体系由基料、P-C-N、P-C-N-CI膨胀阻燃体系、颜填料、可膨胀石墨、水或溶剂及其他助剂组成。当涂层受热时，涂层中的脱水催化剂首先开始分解，形成大量无机酸，成炭剂在酸的作用下失水炭化，在发泡剂的作用下形成泡沫炭层。而后，在高温或火焰作用下，配方中的可膨胀石墨在涂层中受热膨胀，形成“蠕虫”炭体。每个可膨胀石墨单体的膨胀倍率可高达 $100{\\sim}300$ ，形成的膨胀炭体耐氧化、耐高温，大量的膨胀炭体覆盖在基材上，可同样起到难燃性海绵状炭质层的保护作用。等于在已经形成的膨胀炭层上面又附加了一个炭体层，整个膨胀体系形成一个比原涂层厚几十倍至几百倍的难燃性海绵状炭质层，从而大大提高了涂料的耐火性能。  \n\n从膨胀炭层的内部结构来看，防火涂料的膨胀炭层中有两种结构的炭：石墨结构炭和类石墨结构炭。化学膨胀产生的膨胀炭层中是类石墨结构的炭，可膨胀石墨形成的炭体是石墨结构炭，有更好的热稳定性。但石墨结构炭分子间是层状的结构，彼此缺乏有效联系，而聚合物形成的类石墨炭有一定的交联作用。两者共同形成的交联炭结构可耐足够长时间的高温灼烧而不会损坏，保证了涂料的耐火性能。但耐火性能并不好，原因有待继续探讨。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 926,
+        "chunk": "# 2.非膨胀型防火涂料的防火隔热原理  \n\n非膨胀型防火涂料遇火时涂层基本上不发生体积变化，形成釉状熔融保护层。它能起隔绝氧气的作用，使氧气不能与被保护的易燃基材接触，从而避免或降低燃烧反应。继续加热，黏稠涂层脱水并与其他填料的高温凝聚相产物一起形成隔氧的釉状涂层。釉状涂层中常常含有吸热载体，热容较高、升温速度较慢，但因涂层结构致密，有利于接触传热，但这类涂料所生成的釉状保护层热导率往往较大，隔热效果较膨胀型涂层差，其作用原理有以下几个方面。  \n\n(1）吸热降低基材温度防火涂料在受热时，由于涂料体系中的阻燃剂发生分解吸热反应，使基材温度延缓上升，起到延缓和阻止可燃基材燃烧或性能下降的作用。防火涂料的吸热作用主要表现在如下一些方面。  \n\n① 无机阻燃剂的分解吸热防火涂料组成中为了提高涂料的防火性能，同时又能减少燃烧过程中有毒、有害气体的产生，常选用添加无机阻燃剂。无机阻燃剂主要有氢氧化铝、氢氧化镁以及高岭土、蒙脱土、黏土等无机填料。  \n\na.氢氧化铝 氢氧化铝受热分解出 $\\mathrm{\\bfAl_{2}O_{3}}$ 和水，反应式如下  \n\n$$\n2\\mathrm{Ad(OH)_{3}}\\xrightarrow{\\mathrm{fill~�\\vec{m}_{*}}}\\mathrm{Al_{2}O_{3}}+3\\mathrm{H_{2}O}\n$$  \n\n在 $240{\\sim}500^{\\circ}C$ 范围内测得的数据表明，该反应的吸热量为 $1967.2\\mathrm{kJ/kg}$ ，吸热是氢氧化铝阻燃剂的最主要作用。氢氧化铝的TGA-DTA图谱（见图3-11-10）明显地显示出其失水吸热的3个阶段。  \n\n![](images/fa4e65e96155c1fde6b874495bf2a51b93fe1b84b36542d7ee8c11257d3c578d.jpg)  \n图3-11-10 氢氧化铝的TGA-DTA图谱  \n\n![](images/6b0d75f289d9693c19a0210e94723565aab139dccb831fec2e6444a536861de1.jpg)  \n图3-11-11 氢氧化镁的TGA-DTA图谱  \n\nb.氢氧化镁图3-11-11为氢氧化镁的TGA-DTA图谱氢氧化镁约在 $340^{\\circ}C$ 开始逐渐吸热并按如下反应进行分解  \n\n$$\n\\mathbf{Mg(OH)_{2}}{\\xrightarrow{\\mathbf{j}\\mathbf{\\}\\mathbf{\\equiv}\\mathbf{j}\\mathbf{\\equiv}}}\\mathbf{Mg}\\mathbf{O}+\\mathbf{H_{2}O}\n$$  \n\n$430^{\\circ}C$ 时分解吸热达到顶峰， $490^{\\circ}C$ 时分解吸热完毕，留下氧化镁。在吸热分解反应中，氢氧化镁的吸热量为 $44.8\\mathrm{kJ/mol}$ ，吸热是氢氧化镁抑制燃烧的主要原因。  \n\nc.高岭土、蒙脱土、黏土等无机填料高岭土、蒙脱土、黏土等具有良好的耐热、耐酸碱性，且廉价易得，添加在涂料中，一方面能起到阻燃充填剂的作用，另一方面，它能改善涂层的物理机械性能。近年来由于纳米技术和表面处理技术的发展使其在防火涂料配制过程中的分散性得到改善，在涂料成膜阶段可均匀地分布在基材表面，因而能有效地发挥其防火作用。下面以改性高岭土为例分析其冷却阻燃作用。  \n\n高岭土是自然界存在的一种水合硅酸铝矿物，其分子式为 $\\mathrm{Al_{2}O_{3}\\cdot2S i O_{2}\\cdot2H_{2}O}$ 结构式为 $\\mathrm{{\\bfAl_{4}}(S i_{4}O_{10})(O H)_{8}}$ 。高岭土在受热温度接近 $500^{\\circ}C$ 时，晶体结构中的水分逸出， $650^{\\circ}C$ 左右完成脱羟基，这时水合铝硅酸盐变成主要由三氧化二铝和二氧化硅形成的偏高岭石，温度继续升高，偏高岭石经过硅铝尖晶岩相，最终产物是莫来石和无定形二氧化硅。  \n\n整个受热过程如下  \n\n$$\n\\mathrm{Al_{2}O_{3}\\bullet2S i O_{2}\\bullet2H_{2}O\\xrightarrow{500\\sim700\\mathbb{T}}\\bullet A l_{2}O_{3}\\bullet2S i O_{2}+2H_{2}O}\n$$  \n\n$$\n2(\\mathrm{Al_{2}O_{3}\\cdot2S i O_{2}})\\xrightarrow{9254\\mathrm{C}}2\\mathrm{Al_{2}O_{3}}\\cdot3\\mathrm{SiO_{2}}+\\mathrm{SiO_{2}}\n$$  \n\n硅尖晶石  \n\n$$\n\\mathrm{2Al_{2}O_{3}\\bullet3S i O_{2}\\xlongequal{4100\\mathbb{C}}2(A l_{2}O_{3}\\bullet S i O_{2})+S i O}\n$$  \n\n硅尖晶石 似莫来石  \n\n$$\n3(\\mathrm{Al}_{2}\\mathrm{O}_{3}\\cdot\\mathrm{SiO}_{2})\\xrightarrow{1100^{\\circ}\\mathrm{C}}3\\mathrm{Al}_{2}\\mathrm{O}_{3}\\cdot2\\mathrm{SiO}_{2}+\\mathrm{SiO}_{2}\n$$  \n\n从受热过程中看出，涂料中的高岭土受热分解出水蒸气，并能吸收大量的热，而其中的$\\mathrm{\\bfAl_{2}O_{3}}$ 也是一种吸热的情性载体。因此，通过降低了热量向基材的传递与水蒸气的冲稀作用以及熔融涂层隔氧作用一起提高了涂层的防火性能。  \n\n$\\textcircled{2}$ 含硼阻燃剂含硼阻燃剂的阻燃作用一是能形成玻璃态无机膨胀涂层，二是生成的硼酸盐能促进成炭，三是高温下吸热、发泡及冲稀可燃物的功效。如硼酸加热脱水吸热可用下式表示  \n\n$$\n2\\mathrm{H_{3}B O_{3}\\xrightarrow{130\\mathrm{-}200\\mathrm{C}}\\ 2\\mathrm{HBO_{2}\\xrightarrow{260\\mathrm{-}270^{\\circ}C}\\ B_{2}O_{3}}}\n$$  \n\n作为重要阻燃剂和抑烟剂的硼酸锌水合物，分子式为 $\\mathrm{2Zn0\\bullet3B_{2}O_{3}\\bullet3.5H_{2}O}.$ ，在 $290\\sim$ $450^{\\circ}C$ 之间放出 $13.5\\%$ 的水，并吸收 $503\\mathrm{kJ/kg}$ 的热量，在无卤体系中，含水硼酸盐主要是以脱水机理进行阻燃。当含硼阻燃剂与卤素阻燃剂合用时，尽管具有多重阻燃作用，但同样存在脱水吸热作用，反应方程式显示了含硼阻燃剂的脱水吸热功能。  \n\n$\\textcircled{3}$ 含硅化合物防火涂料的无机成膜物质有水玻璃、硅酸盐（ $\\mathrm{Li5iO_{3}}$ ， $\\mathbf{K}_{2}\\mathbf{SiO_{3}}$ p$\\mathrm{{Na}_{2}\\mathrm{{SiO}_{3}}}$ )、硅溶胶等含硅化合物。当水玻璃和水合硅酸盐迅速加热时，由于硅氧链上的羟基缩合而迅速脱水。图3-11-12为硅酸盐防火涂料的DTA曲线，由此可见存在吸热降温功效。  \n\n![](images/391667123888d789c354670b3afc33c31d1c2de82e443894046328cb90fcf026.jpg)  \n图3-11-12 硅酸盐防火涂料的DTA曲线  \n\n![](images/055546a483023226e68b965fba01e28d5162e9d277bcc176cb3c548db019fff4.jpg)  \n图3-11-13 聚磷酸铵的TG-DTA图谱  \n\n$\\textcircled{4}$ 含磷无机阻燃剂磷酸二氢铵、磷酸氢二铵等含磷无机阻燃剂受热分解时均具有吸热、稀释可燃气体的作用。但由于小分子铵盐热稳定性差、易迁移、吸潮，因此目前在防火涂料中已被聚磷酸铵所取代。聚磷酸铵在防火涂料中主要作为膨胀型阻燃成分的脱水剂及发泡剂，它的阻燃作用主要是形成膨胀炭层，但在受热过程中，由于聚磷酸铵分解，同样存在有利于阻燃的吸热过程。图3-11-13 为聚磷酸铵的TG-DTA图谱。由图可见，在 $296\\sim$ $415^{\\circ}C$ 1 $653{\\sim}715^{\\circ}C$ 范围内均存在明显的分解吸热峰。  \n\n$\\textcircled{5}$ 含氮阻燃剂目前已获得广泛应用的含氮阻燃剂有三聚氰胺及其衍生物（三聚氰胺氰尿酸盐、磷酸盐、硼酸盐、肌盐、双氰胺盐），它们既可以作为混合膨胀型阻燃剂的组分，也可单独使用。这类阻燃剂主要通过分解吸热及生成不燃性气体发挥作用。如三聚氰胺在$250{\\sim}450^{\\circ}C$ 范围内发生分解，吸收大量的热；三聚氰胺的氰尿酸盐在 $440{\\sim}450^{\\circ}\\mathrm{C}$ 分解吸热，而将其加入在醋酸乙烯酯乳液、丙烯酸酯乳液及橡胶乳液中制得的涂料，不但阻燃性能好，而且其涂膜密着性和平滑性均优。  \n\n此外，卤-锑协同过程中会产生吸热作用，生成的SbX；在火焰的上空结成液滴或固体微粒，其壁效应吸收大量热能，有利于促使燃烧速度减缓或停止。  \n\n(2）燃烧连锁反应的抑制、中止防火涂料中添加的卤素阻燃剂、卤-锑协同阻燃剂主要是通过在气相中使燃烧中断或延缓链式燃烧反应而发挥阻燃作用，有机磷系阻燃剂除符合凝聚相阻燃机理外，也可在气相抑制燃烧的连锁反应。  \n\n$\\textcircled{1}$ 卤素阻燃剂卤素阻燃剂在受热分解时能产生HX气体，HX会与燃烧链式反应中活泼的H·、O·、HO·发生反应，生成活性较低的X·自由基，致使燃烧减缓或中止，链中止反应的反应式如下  \n\n$$\n\\mathrm{H}\\mathbf{X}+\\mathrm{H}\\cdot\\mathbf{\\longrightarrow}\\mathrm{H}_{2}+\\mathbf{X}\\cdot\\mathbf{\\longrightarrow}\n$$  \n\n$$\n{\\mathrm{H}}\\mathbf{X}+{\\boldsymbol{\\mathrm{O}}}\\bullet\\longrightarrow\\mathbf{H}{\\boldsymbol{\\mathrm{O}}}\\bullet+\\mathbf{X}\\bullet \n$$  \n\n$$\n\\mathrm{H}\\mathrm{X}+\\mathrm{H}\\mathrm{O}\\cdot\\longrightarrow\\mathrm{H}_{\\bar{z}}\\mathrm{O}+\\mathrm{X}\\cdot\n$$  \n\n氯系阻燃剂与溴系阻燃剂的链中止机理相同，但由于溴的阻燃元素质量高，H—Br的键能小于 $\\mathrm{\\DeltaH{-}C l}$ 的键能，捕获自由基的能力更强，溴系阻燃剂比氯系阻燃剂的阻燃效果更好。  \n\n$\\textcircled{2}$ 卤-锑协同阻燃体系卤素阻燃剂与锑系阻燃剂共同使用可增加阻燃的附加作用，这个作用又称为协同效应。卤-锑协同在高温下的反应式如下  \n\n$$\n\\begin{array}{r}{{\\mathrm{Sb}}_{2}\\mathrm{O}_{3}\\left({\\bf s}\\right)+6{\\mathrm{HCl}}({\\bf g})\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad}\\\\ {\\mathrm{Sb}_{2}\\mathrm{O}_{3}\\left({\\bf g}\\right)+2{\\mathrm{HCl}}({\\bf g})\\frac{250\\mathbb{C}}{\\sqrt{6}0\\mathrm{Cl}}\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad}\\\\ {\\mathrm{Sb}\\mathrm{OCl}({\\bf s})\\frac{245\\sim280\\mathbb{C}}{\\pi}\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad}\\\\ {\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad}\\\\ {\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad}\\\\ {\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad}\\\\ {\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad}\\\\ {\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad}\\\\ {\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad}\\\\ {\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad}\\\\ {\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad}\\\\ {\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad}\\\\ {\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\quad\\\n$$  \n\n反应中的 $\\mathrm{\\bar{S}b X_{3}}$ 在燃烧区内可捕获燃烧链式反应中活泼的 $\\mathtt{H}\\cdot\\$ 、O·、HO·，抑制或中止燃烧反应。  \n\n$$\n\\mathrm{SbX_{3}+H\\bullet\\longrightarrow H X+S b X_{2}\\bullet}\n$$  \n\n$$\n\\mathrm{SbX_{3}\\longrightarrow X\\bullet+S b X_{2}\\bullet}\n$$  \n\n$$\n\\mathrm{SbX_{3}+C H_{3}\\ \\bullet\\longrightarrow C H_{3}X+S b X_{2}\\ }\\ .\n$$  \n\n$$\n\\mathrm{SbX}_{z}\\bullet+\\mathrm{H}\\bullet\\longrightarrow\\mathrm{SbX}\\bullet+\\mathrm{H}\\mathbf{X}\n$$  \n\n$$\n\\mathrm{SbX}_{2}\\bullet+\\mathrm{CH}_{3}\\bullet\\longrightarrow\\mathrm{CH}_{2}\\mathbf{X}\\bullet+\\mathrm{Sb}\\mathbf{X}\\bullet+\\mathbf{H}\\ ^{\\prime}\n$$  \n\n$$\n\\mathrm{SbX\\cdot+H\\bullet\\longrightarrowSb+HX}\n$$  \n\n$$\n\\mathrm{SbX}\\cdot+\\mathrm{CH_{3}}\\\\cdot\\longmapsto\\mathrm{Sb}+\\mathrm{CH_{3}X}\n$$  \n\n$\\mathrm{SbX_{3}}$ 缓慢分解释放出的 $\\mathbf{X}\\cdot\\mathbf{\\partial}$ 能按如下反应式与燃烧反应气相中的自由基结合，抑制或中止燃烧。  \n\n$$\n\\begin{array}{r l}&{\\mathbf{X}\\bullet+\\mathrm{CH}_{3}\\bullet\\longrightarrow\\mathrm{CH}_{3}\\mathbf{X}}\\\\ &{\\qquad\\mathbf{X}\\bullet+\\mathrm{H}\\bullet\\longrightarrow\\mathrm{H}\\mathbf{X}}\\\\ &{\\qquad\\mathbf{X}\\bullet+\\mathrm{HO}_{2}\\bullet\\longrightarrow\\mathrm{H}\\mathbf{X}+\\mathrm{O}_{2}}\\\\ &{\\qquad\\quad\\mathrm{H}\\mathbf{X}+\\mathrm{H}\\bullet\\longrightarrow\\mathrm{H}_{2}+\\mathbf{X}\\bullet}\\\\ &{\\qquad\\mathbf{X}\\bullet+\\mathbf{X}\\bullet+\\mathsf{M}\\longrightarrow\\mathbf{X}_{2}+\\mathsf{M}}\\\\ &{\\qquad\\mathbf{X}_{2}+\\mathrm{CH}_{3}\\bullet\\longrightarrow\\mathrm{CH}_{3}\\mathbf{X}+\\mathsf{X}}\\end{array}\n$$  \n\nO·可与锑反应生成氧化锑，后者可捕获气相中的 $\\mathrm{~\\bf~H~}$ ·及 $\\mathrm{HO}\\cdot$ ，使燃烧得到抑制或中止，反应式如下  \n\n$$\n\\mathrm{Sb}{+}\\mathrm{O}\\cdot{+}\\mathrm{M}\\longrightarrow\\mathrm{SbO}\\cdot{+}\\mathrm{M}\n$$  \n\n$$\n\\mathbf{SbO\\bullet+2H\\bullet+M}\\longrightarrow\\mathbf{SbO\\bullet+H}_{2}+\\mathbf{M}\n$$  \n\n$$\n\\mathrm{SbO\\cdot+H\\cdot\\longrightarrowSbOH}\n$$  \n\n$$\n\\mathrm{\\bfSbOH{+}H O\\cdot{\\bf\\sigma}\\xrightarrow{}S b O\\cdot{+}H_{2}O}\n$$  \n\n$\\textcircled{3}$ 有机磷系阻燃剂有机磷系阻燃剂热解所形成的气态产物中含有PO·，它可以抑制H·及HO·，因此可在气相区抑制燃烧的连锁反应。  \n\n$$\n\\mathrm{H_{3}P O_{4}\\longrightarrow H P O_{2}+P O\\cdot+_{2}^{.}}\n$$  \n\n$$\n\\mathrm{PO}\\cdot+\\mathrm{H}\\cdot\\longrightarrow\\mathrm{HPO}\n$$  \n\n$$\n\\mathrm{HPO+H}\\mathrel{\\mathop:}\\longrightarrow\\mathrm{H}_{2}\\mathrel{+}\\mathrm{PO}\\mathrel{\\mathop:}\n$$  \n\n$$\n\\mathrm{PO}\\cdot+\\mathrm{HO}\\cdot\\longrightarrow\\mathrm{HPO}+\\mathrm{O}\\cdot\n$$  \n\n卤-磷协同体系与卤-体系相似，据认为卤化磷或卤氧化磷是燃烧自由基的捕获剂，但目前证据不足。  \n\n此外，膨胀型阻燃体系也可能在气相发挥阻燃作用，如磷-氮-碳体系遇热可能产生NO和 $\\mathrm{\\DeltaNH_{3}}$ ，而极少量的NO和 $\\mathrm{NH_{3}}$ 也能使燃烧赖以进行的自由基化合而导致链反应中止。  \n\n(3）情性气体的覆盖、稀释作用不同的阻燃剂其阻燃机理可能是不同的，同一种阻燃剂往往是通过一种或多种阻燃效应同时在起作用。阻燃剂在发挥上述阻燃作用的同时，还不同程度地存在情性气体的覆盖、稀释作用。  \n\n$\\textcircled{1}$ 卤素阻燃剂卤素阻燃剂受热后释放出的HX，不仅可以捕捉燃烧反应的自由基，它们也是难燃性气体，可以稀释空气中的氧，且由于HX的密度大于空气的密度，在可燃基材表面能形成覆盖保护层，减缓或中止燃烧。  \n\n$\\textcircled{2}$ 卤-锑协同阻燃体系卤-锑协同阻燃体系的覆盖、稀释作用与卤素阻燃剂相似，生成的 $\\mathrm{SbX_{3}}$ 首先是燃烧气相中自由基的捕获剂，其次， $\\mathrm{5bX_{3}}$ 的密度大，覆盖在基材表面可以隔绝基材与氧的接触。卤-锑协同阻燃体系正是由于多种阻燃作用并存，使其阻燃效果非常显著。  \n\n$\\textcircled{3}$ 含氮阻燃剂含氮阻燃剂早期主要是以无机铵盐形式使用。无机铵盐热稳定性差，受热时释放出 $\\mathrm{\\DeltaNH_{3}}$ ， $\\mathrm{CO}_{2}$ （碳酸铵)、HCI（氯化铵）和 $\\mathrm{H}_{2}\\mathrm{O}$ 等不燃气体，它们可以稀释空气中的氧浓度、降低可燃基材分解出的可燃气体的浓度，发挥阻燃作用。  \n\n新型氮系阻燃剂三聚氰胺在 $250{\\sim}380^{\\circ}\\mathrm{C}$ 可以发生下列反应，生成多种缩聚物并释放出$\\mathbf{NH}_{3}$ ，挥发的三聚氰胺及氨气都可以起到稀释作用。  \n\n$$\n2\\mathrm{C_{3}\\ H_{6}N_{6}\\xrightarrow{-N H_{3}}C_{6}\\ H_{9}N_{11}\\xrightarrow{-N H_{3}}C_{6}\\ H_{6}N_{10}\\xrightarrow{-N H_{3}}C_{6}\\ H_{3}N_{9}}\n$$  \n\n三聚氰胺的磷酸盐受热分解，在 $650^{\\circ}C$ 热降解接近完成，生成焦磷酸盐和聚磷酸盐并释放出水蒸气，盐参与构成炭层，水蒸气起稀释氧和可燃气体的作用。反应式如下  \n\n$$\n\\mathrm{C_{3}H_{6}N_{6}\\bullet H_{3}P O_{4}\\xrightarrow{\\mathbf{-H}_{2}O}C_{3}H_{6}N_{6}H_{4}P_{2}O_{7}\\xrightarrow[]{\\mathbf{-H}_{2}O}(C_{3}H_{6}N_{6}H P O_{3})_{n}}\n$$  \n\n膨胀型阻燃剂受热升温分解产生的不燃气体如 $\\mathrm{\\bfNH_{3}}$ ， $\\mathrm{CO_{2}}$ ， $\\mathtt{H}_{2}\\mathtt{O}$ 等可稀释空气中的氧及可燃气体的浓度。  \n\n$\\textcircled{4}$ 含磷无机阻燃剂小分子的含磷无机阻燃剂如磷酸二氢铵、磷酸氢二铵等受热分解均会生成不燃性气体 $\\mathrm{\\DeltaNH_{3}}$ ，而自前广泛使用的聚磷酸铵遇热首先分解生成 $\\mathrm{NH_{3}}$ ，分解出的磷酸缩合生成偏磷酸及聚偏磷酸并释放出水蒸气。APP受热的变化过程如下  \n\n$$\n(\\mathrm{NH_{4}})_{n+2}\\mathrm{P}_{n}\\mathrm{O}_{n+3}\\xrightarrow[-\\mathrm{H}_{2}\\mathrm{O}]{-\\mathrm{NH}_{3}}\\mathrm{EH}_{3}\\mathrm{PO}_{4}\\xrightarrow[-\\mathrm{H}_{2}\\mathrm{O}]{-\\mathrm{H}_{2}\\mathrm{O}}_{3}\\xrightarrow[-\\mathrm{HPO}_{3}]{}\\mathrm{CHPO}_{3}.\n$$  \n\n$\\textcircled{5}$ 其他阻燃剂无机阻燃剂、含硼阻燃剂等受热分解产生的水合水吸热汽化不仅产生冷却作用，产生的水蒸气还具有稀释作用。  \n\n防火涂料的组成一般为基料、阻燃剂、增强填料、溶剂、颜料、助剂六大部分。下面重点介绍基料（基体树脂）和阻燃剂。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 927,
+        "chunk": "# 一、基体树脂  \n\n能用于制备防火涂料的树脂有很多，但在实际中往往不会单独使用一种树脂。单一树脂作基料的防火涂料其涂膜有许多缺陷，如涂料的光泽差，不挥发分含量低，耐候性、耐水性、柔韧性差等。因此经常采用几种树脂混合使用，相互之间取长补短，以获得性能理想的涂膜。  \n\n可用作防火涂料基料的树脂和粘接剂种类繁多、性能各异，下面重点介绍一些目前在防火涂料中常用的树脂基料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 928,
+        "chunk": "# （一）溶剂型涂料用树脂",
+        "category": " Introduction"
+    },
+    {
+        "id": 929,
+        "chunk": "# 1.丙烯酸树脂  \n\n丙烯酸树脂是丙烯酸酯或甲基丙烯酸酯和其他不饱和单体进行加成聚合而制得的共聚树脂。相对分子质量一般在 $75000{\\sim}120000$ 。其结构示意如下：  \n\n优点：聚丙烯酸树脂不吸收紫外线，不容易水解，所以耐气候性能比较突出，化学稳定性、耐水性、耐腐蚀性亦堪称优秀，无色透明，保色保光，耐酸、耐碱，对颜料的黏结能力大，施工性能良好。此外它的配方比较灵活，可与许多官能性单体共聚获得具有广泛物性和用途的共聚物。缺点：拉丝性一—丰满度差；对热敏感；耐溶剂差。极性过强。  \n\n近年来丙烯酸树脂广泛地应用在饰面型防火涂料、钢结构防火涂料、电缆防火涂料、塑料防火涂料等的研制中。",
+        "category": " Introduction"
+    },
+    {
+        "id": 930,
+        "chunk": "# 2.环氧树脂  \n\n环氧树脂是大分子主链上含有醚键和仲醇基，同时两端含有环氧基团的一类聚合物的总称，是热固性树脂中用量最大、应用最广的品种。环氧树脂中含有独特的环氧基，以及羟基、醚键等活性基团和极性基团，因而具有许多优异的性能。与其他热固性树脂相比较，环氧树脂的种类和牌号最多、性能各异。环氧树脂固化剂的种类更多，再加上众多的促进剂、改性剂等，可以进行多种多样的组合。从而能获得各种各样性能优异的、各具特色的环氧固化体系和固化物。作为防火涂料粘接剂使用的一般为低分子量液状环氧树脂（相对分子质量为 $340{\\sim}700)$ ，其分子结构式为  \n\n![](images/dfadaa35912314ef04b3dfdf37dcb322b6596bfefa7dd103fce5b630b33fec9f.jpg)  \n环氧基团  \n\n(1）优点①力学性能好。环氧树脂具有很强的内聚力，分子结构致密。②黏结性能优异。在环氧树脂结构中含有脂肪族羟基、醚基和极活泼的环氧基。羟基和醚基都有高度的极性，使环氧树脂分子能在邻界面产生电磁引力，而环氧基团能与介质表面的自由基起反应形成化学键，所以环氧树脂的粘接力特别强。它对大部分材料如木材、金属、玻璃、塑料、橡胶、皮革、陶瓷、纤维等都有良好的粘接性能，故有“万能胶”之称，只对少数材料如聚苯乙烯、聚氯乙烯、赛璐珞等粘接性较差。 $\\textcircled{3}$ 固化收缩率小。一般为 $1\\%\\sim2\\%$ 。所以其产品尺寸稳定，内应力小，不易开裂。 $\\textcircled{4}$ 工艺性好。环氧树脂固化时基本上不产生低分子挥发物，所以可低压成型或接触压成型。配方设计的灵活性大，可设计出适合各种工艺性要求的配方。 $\\textcircled{5}$ 电性能好。是热固性树脂中介电性能最好的品种之一。 $\\textcircled{6}$ 稳定性好。不含碱、盐等杂质的环氧树脂不易变质。 $\\textcircled{7}$ 固化后的环氧树脂，具有优良的耐化学腐蚀性、耐热性、耐酸碱及良好的电绝缘性，因而用它来配制的膨胀型防火涂料不仅具有优良的附着力、防腐蚀性、抗化学品性、硬度、柔韧性及坚牢度等性能，而且可以应用于户外，此外，耐烃类火灾的能力较普通膨胀型防火涂料好得多。树脂可在 $150\\sim200^{\\circ}\\mathrm{C}$ 温度下长期使用，耐寒性可达$-55^{\\circ}C$ 。树脂可贮存一年以上不变质。  \n\n(2）缺点热固性树脂，固化是通过加入固化剂来实现的。另外固化后涂层较脆。",
+        "category": " Introduction"
+    },
+    {
+        "id": 931,
+        "chunk": "# 3.氯化聚烯烃树脂  \n\n(1）氯化橡胶氯化橡胶是由天然橡胶经过炼解或异戊二烯橡胶溶于四氯化碳中，通氯气而制得的白色多孔性固体物质。也可水相法制的，通常含氯量在 $62\\%\\sim67\\%$  \n\n氯化橡胶呈白色粉末状，溶液黏度因橡胶降解程度而异。易溶于芳烃、卤烃、酯类和酮类，脂肪烃是其稀释剂。漆膜特性：由于分子结构规整、饱和、极性小，无活性化学基团，故漆膜化学稳定性高，耐酸、碱、盐、氯化氢、硫化氢、二氧化硫等化学品侵蚀，但不耐浓硝酸和氢氧化铵；长期与动物油、植物油和脂肪接触，漆膜软化和膨胀。其特点如下。  \n\n$\\textcircled{1}$ 对光、热不稳定， $130^{\\circ}C$ 以上时开始分解，在潮湿条件下 $60^{\\circ}C$ 就开始分解，所以使用温度低于 $60^{\\circ}C$ 。  \n\n$\\textcircled{2}$ 水、水蒸气通过率低，抗渗透性好。  \n\n$\\textcircled{3}$ 无毒、快干、单组分，不受施工温度限制。  \n\n$\\textcircled{4}$ 附着力好，无层间附着问题$\\textcircled{5}$ 含氯量高，因此阻燃性好，且在潮湿条件下可防霉。  \n\n$\\textcircled{6}$ 单独用于涂料时，漆膜较脆，制漆时需加人增塑剂或其他塑性好的树脂，低分子量的增塑剂，如氯化石蜡、氯化联苯或邻苯二甲酸酯类，常因其往表面迁移和亲水性而影响涂层性能。  \n\n$\\textcircled{7}$ 合成氯化橡胶时采用四氯化碳作溶剂，其成品也往往含有一定量的游离的四氯化碳，破坏大气中的臭氧层，目前从世界范围内正在禁止溶剂法的氯化橡胶的生产。正在大力发展水相法的氯化橡胶，但水相法氯化橡胶较溶剂法的氯化橡胶的性能尚有一定的差距。  \n\n(2）聚偏氯乙烯树脂（PVDC）聚偏氯乙烯树脂，又称聚偏二氯乙烯树脂、氯偏树脂，分子式为 $(\\mathrm{C}_{2}\\mathrm{H}_{2}\\mathrm{Cl}_{2})_{n}$ ，相对分子质量为 $20000{\\sim}10000000,$ 0  \n\n聚偏氯乙烯树脂很难燃烧，其燃烧火焰呈黄色，端部呈绿色。密度（ $30^{\\circ}C$ ）为 $1.7\\cdots$ $1,875\\mathrm{g/cm^{3}}$ ，软化点为 $185\\sim200^{\\circ}C$ ，分解温度为 $210{\\sim}215^{\\circ}C$ ，含氯量为 $72\\%$ ，表观密度为$0.5{\\sim}0.6\\mathrm{g/cm^{3}}$ ，挥发物（ $105^{\\circ}C$ ，1h) $<0.4\\%$ 。由于分子结构的对称性使它有高度的结晶性，密度为 $1.70\\mathrm{g/cm^{3}}$ （薄膜 $1.68\\mathrm{g/cm^{3}}$ ，纤维 $\\mathrm{1.75g/cm^{3}};$ ，吸水性 $<0.1\\%$ 。PVDC对很多气体和液体具有很低的透过率是其最大的特点，这种特性是由其分子结构的高密度性和高结晶性决定的。PVDC热分解时分两步进行：先是生成共轭双键，然后炭化。聚偏氯乙烯树脂热收缩率大，在热、紫外线、离子辐射（ $a$ 射线、 $\\gamma$ 射线）、碱性介质、催化金属或盐类作用下分解反应生成CI或HCl。在室温下不溶于一般溶剂。聚偏氯乙烯树脂具有不受细菌、昆虫侵蚀的优点，能耐多种溶剂，在含氧和氯代溶剂中易溶胀。产品结构分为原始状态水性乳液和干燥的树脂粉末两种形式。聚偏氯乙烯树脂难燃，无毒性，离火即灭，燃烧时软化，炭化时膨胀，裂解时放出有毒性单体和氯化氢。聚偏氯乙烯树脂在防火涂料中主要起基料（粘接剂）、阻燃剂的作用，成膜后透水透气率低，耐油。故其防火涂料还具有防潮、防水及防腐等性能。用于配制的防火阻燃液对木材、木制品、纸张、纸板、织物等易燃纤维材料的表面阻燃处理，处理后的纤维材料由易燃材料变为难燃材料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 932,
+        "chunk": "# （二）膨胀防火涂料成炭、发泡体系用原料  \n\n膨胀防火体系主要由酸源、碳源、发泡剂等组成。可用于膨胀型防火涂料的膨胀防火体系的阻燃原料种类繁多，性能各异，本节中所谈到膨胀防火体系的阻燃原料只限于当前用得比较多的品种。  \n\n(1）尿素选用工业品。尿素在水、稀酸、稀碱溶液中很不稳定，在稀碱中加热至$50^{\\circ}C$ 以上时分解出氨气，在稀酸中分解出二氧化碳。  \n\n$$\n\\mathrm{NH_{2}\\ C O N H_{2}}+2\\mathrm{NaOH}\\longrightarrow2\\mathrm{NH_{3}}+\\mathrm{Na_{2}\\ C O_{3}}\n$$  \n\n$$\n\\mathrm{NH_{2}C O N H_{2}}+H_{2}S O_{4}+H_{2}O\\longrightarrow(N H_{4})_{2}S O_{4}+C O_{2}\n$$  \n\n尿素易吸湿而结块影响使用，所以尿素应存放在干燥且有防潮设施的库房内。  \n\n尿素是一种重要的化工原料，主要在水性防火涂料的配方中起发泡剂的作用。  \n\n（2）三聚氰胺是由双氰胺或尿素合成的，为白色粉末状结晶，分子式为 $\\mathrm{C_{3}N_{3}(N H_{2})_{3}}$ 7相对分子质量为126.091，熔点 $345^{\\circ}C$ ，在沸水中的溶解度为 $5\\%$ ，冷水中仅为 $0.5\\%$ ，易溶于甲醛、乙醇、苯酚、丙酮和烧碱水溶液中。与盐酸、硫酸、乙酸、草酸等作用生成盐。三聚氰胺在防火涂料中主要起发泡剂、阻燃剂的作用。  \n\n(3）二氰二胺 选用工业品。  \n\n(4）碳酸氢铵 选用工业品。  \n\n(5）磷酸氢二铵选用工业品。近年来已逐渐为聚磷酸铵所代替，目前磷酸氢二铵在防火涂料中只起辅助作用。  \n\n(6）聚磷酸铵（APP）是白色（结晶或无定形）粉末，当 $n$ 足够大时分子式与结构式可写作（ $\\mathrm{\\bf{NH_{4}P O_{3}}})_{n}$ ， $n=10\\sim20$ 相对分子质量约为 $1\\dot{0}00\\sim2000$ ， $n>20$ 相对分子质量 $>$ 2000，系无分支的长链聚合物，随聚合度 $(n)$ 的不同可分为水溶性（ $_{(n=10\\sim20)}$ ）和水不溶性 $m>20\\AA$ ）两种。常用结晶态APP为水不溶性长链状聚磷酸铵盐，有 $I\\sim V$ 五种变体。  \n\nAPP含磷、氮量高，P-N系产生协同效应，阻燃效果好；产品热稳定性好，分解温度高于 $250^{\\circ}C$ ，约 $750^{\\circ}C$ 全部分解；水溶性低，吸潮性小， $\\bf{10g}$ APP在 $15^{\\circ}C$ 时溶于 $100\\mathbf{g}$ 水中，产品细度可达300目以上，相对密度小，约为1.24，分散性好；产品接近中性，化学稳定性好，可与其他任何物质混合而不起化学变化，用于膨胀型防火涂料中不影响其理化性能，是一种最重要的高效磷系无机阻燃剂。聚磷酸铵是目前在膨胀型防火涂料中应用最广泛、用量最大的一种无机阻燃添加剂，在防火涂料中主要起成炭发泡层形成的催化剂、发泡剂、阻燃剂的作用。  \n\nAPP常与其他阻燃剂并用，其阻燃作用优于单独使用，常用的并用体系如 $\\mathrm{\\bfAPP+}$ 甲醛 $+\\mathbf{Mg}(\\mathrm{OH})_{2}$ ； $\\mathbf{APP+Al(OH)_{3}}$ ； $\\mathrm{APP+BaCl_{2}}$ ； $\\mathrm{APP+}$ 尿素； $\\mathrm{APP+}$ 磷酸胍；： $\\mathbf{APP+}$ 甲醛 $+$ 双氰胺； $\\mathbf{APP+Sb_{2}O_{3}}$ 等。当 APP的聚合度 $n{<}20$ 时，水溶解度（ $20^{\\circ}C^{\\prime}$ ）约为 $10\\sim$ $30\\mathrm{g/100g~H_{2}O}$ ，是最佳的木材浸溃剂，常压下浸渍马尾松、红松等材料，吸收药剂量达$25{\\sim}35\\mathrm{kg/m^{3}}$ 时，处理过的材料氧指数达30以上。用合适的分散剂和乳化剂把氢氧化铝等阻燃剂和APP混合配成防火阻燃液可处理木材、木制品、纸张、纸板、织物等易燃纤维材  \n\n料，其阻燃效果极佳。  \n\n（7）磷酸二氢铝 选用工业品。  \n\n(8）季戊四醇是一个含有4个伯羟基的四元醇，为白色结晶，分子式为C5H12O4。易被一般有机酸酯化，与稀烧碱溶液同煮无反应。15℃时1g季戊四醇可溶于18mL水中。季戊四醇溶于乙醇、甘油、乙二醇、甲酰胺，不溶于丙酮、苯、四氯化碳、乙醚和石油醚等。  \n\n季戊四醇不同于甘油，它是固体而且熔点很高，醇解时要加入催化剂，所需温度也稍高，为 $230{\\sim}250^{\\circ}C$ 。季戊四醇用于防火涂料中主要起成炭剂（碳源)、阻燃剂的作用，是膨胀型防火涂料最重要的成炭剂之一，并可提高防火涂料的柔韧性。季戊四醇中羟基的含量为 $48\\%$ 。  \n\n(9）丙三醇选用工业品。又称甘油，为无色、透明、无臭、味甜的黏稠液体。丙三醇用于防火涂料中主要起炭化剂（碳源)、阻燃剂的作用，也可在防火涂料中起分散剂和渗透剂及流平剂的作用。常用于膨胀型透明防火涂料中。  \n\n（10）淀粉为白色、无臭、无味粉末，分子式为（ $\\{\\mathsf{C}_{\\hat{\\mathsf{G}}}\\mathsf{H}_{1\\bar{\\mathsf{O}}}\\odot_{\\bar{\\mathsf{S}}}\\}_{n}$ ，密度为 $1.499\\sim$ $1.513{\\mathrm{g/cm^{3}}}$ 。有吸湿性，不溶于冷水、乙醇和乙醚。热水中有 $10\\%\\sim20\\%$ 可溶（直链淀粉)。支链淀粉大部分不溶。  \n\n淀粉用于防火涂料中主要起成炭剂（碳源）、阻燃剂的作用，常用于膨胀型透明防火涂料中。  \n\n(11）三乙醇胺选用工业品。三乙醇胺用于防火涂料中主要起成炭剂（碳源）、发泡剂的作用，也可在防火涂料中起表面活性剂、稳定剂、乳化剂、润滑剂等的作用，有时为固化剂组分之一。常用于膨胀型透明防火涂料中。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 933,
+        "chunk": "# 二、阻燃剂  \n\n下面介绍在防火涂料和防火阻燃液中目前用得比较多的部分阻燃剂产品。",
+        "category": " Introduction"
+    },
+    {
+        "id": 934,
+        "chunk": "# （一）无机阻燃剂",
+        "category": " Introduction"
+    },
+    {
+        "id": 935,
+        "chunk": "# 1.三氧化二锑阻燃剂  \n\n三氧化二锑，简称氧化锑，分子式为 $\\mathrm{{\\bfSb_{z}O_{3}}}$ ，相对分子质量为291.5，在常温下为白色结晶粉末，受热时呈黄色。三氧化二锑典型的化学组成为 $\\mathrm{Sb_{2}O_{3}}\\ 98\\%\\sim99\\%$ ， $\\mathrm{Sb}_{2}\\mathrm{O}_{4}$ $1.5\\%$ $F e_{2}O_{3}0.01\\%$ 、As $0.35\\%$ 1 $\\mathrm{Pb}0.1\\%$ 、 $\\textrm{\\textbf{S}0.1\\%}$ 。平均粒径为 $1\\sim3\\mu\\mathrm{m}$ ，密度为$5.67\\mathrm{g/cm^{3}}$ ，熔点为 $656^{\\circ}C$ ，沸点为 $1425^{\\circ}C$ ，熔化热为 $54.4{\\sim}55.3\\mathrm{kJ/mol}$ ，蒸发热为 $36.3\\sim$ $37.\\ 2\\mathrm{kJ/mol}$ 。它是在防火涂料中应用较广的一种无机阻燃型添加剂，单独使用时阻燃效果较低，若与磷酸酯、卤化物配合使用，有良好的协同效应，阻燃效果显著提高。两者反应可生成卤化锑（ $\\mathrm{\\SbCl_{3}}$ ）和卤氧化锑（SbOCI)，它们挥发时能吸热，同时产生气体隔绝氧气和稀释可燃气体浓度。在燃烧区域里，卤化锑还能热分解成氧化。  \n\n$$\n3{\\bf S}{\\bf b}_{2}{\\bf O}_{3}+6\\mathrm{RCl}\\longrightarrow6{\\bf S}{\\bf b}{\\bf O}{\\bf C}1\n$$  \n\n$$\n5{\\mathrm{SbOCl}}\\longrightarrow\\mathrm{Sb}_{4}\\mathrm{O}_{5}\\mathrm{Cl}_{2}+\\mathrm{SbCl}_{3}\n$$  \n\n$$\n4{\\bf S b}_{4}\\mathrm{O}_{5}\\mathrm{Cl}\\longrightarrow5{\\bf S b}_{3}\\mathrm{O}_{\\sharp}\\mathrm{Cl}+{\\bf S}\\mathrm{bCl}_{3}\n$$  \n\n$$\n3S\\mathrm{b}_{3}\\mathrm{O}_{4}\\mathrm{Cl}\\longrightarrow4S\\mathrm{b}_{2}\\mathrm{O}_{3}+S\\mathrm{bCl}_{3}\n$$  \n\n反应产生的卤化梯（ $\\mathrm{\\SbCl_{3}}$ 或 $\\mathrm{\\SbBr_{3}}$ ）除具有隔氧和冲淡可燃气体作用外，还能捕获气相自由基（H·和 $\\mathrm{OH^{-})}$ ，促使炭化物的形成。  \n\n氧化锑用于木材、木制品、纸张、纸板、织物等易燃纤维材料的表面阻燃技术处理的防火阻燃液中主要起阻燃剂的作用；用于防火涂料中主要起阻燃剂和颜料的作用。氧化锑主要作为协效剂与含卤素化合物配合，在它们的热分解过程中起阻燃作用，并可取代部分卤素化合物。SbO3与卤系化合物的协效作用与磷-卤等元素的阻燃协效作用相比，它具有配料少、防火涂料的防火耐燃性好、对防火涂料和纤维材料的物理性能无影响等特点。SbO3与有机元素不同，不具自然挥发性，在受火甚至在持续的火焰作用下，不会分解成为气体化合物而烧失，以它的稳定性可以起到经久耐燃的作用，从而使防火涂料具有高效隔热的防火性能。另外氧化锑在涂料中的应用可使涂料具有许多良好性能，其折射率较高，近似于ZnO，具有遮盖力，粒径较小，吸油量也不大，在大多数树脂中呈现惰性。因此以氧化锑和卤素化合物配合可以制造既有高效隔热防火性能又有良好装饰性能的防火涂料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 936,
+        "chunk": "# 2.氢氧化铝阻燃剂  \n\n氢氧化铝又称水合氧化铝，分子式为Al(OH)3，或AlO·3HO，相对分子质量为78，外观为白色粉末，细度为325目或 $625\\sim1250$ 目，真密度为 $\\mathrm{2.42g/cm^{3}}$ ，堆密度（轻装）为$1.1{\\sim}0.25\\mathrm{g}/\\mathrm{cm}^{3}$ ，堆密度（重装）为 $\\mathrm{1.4\\sim0.45g/cm^{3}}$ ，硬度（莫氏）为 $5\\sim3.5$ ，比热容为2.82J/(g·℃)。氢氧化铝阻燃剂的使用量在无机阻燃剂中占有很大比重，氢氧化铝阻燃剂具有热稳定性好、无毒、不挥发、不析出、不产生腐蚀性气体、发烟量少等优点，而且资源丰富，价格便宜。阻燃剂用的氢氧化铝的化学成分（质量百分比)：含 $\\mathrm{{Al(OH)_{3}}~99.~5\\%}$ ，纯Al(OH)3中的HzO含量应为34.6%，工业品的灼热一般质量减少34%。AlO3≥64%，$\\mathrm{Na_{2}O}{\\leqslant}0,2\\%$ ， $\\mathrm{SiO_{2}\\leqslant0.2\\%}$ ， $\\mathrm{Fe_{2}O_{3}}{\\leqslant}0.035\\%$ ， $c u\\leqslant0.001\\%$ ， $\\mathrm{Mn}{\\leqslant}0.001\\%$ 。  \n\n氢氧化铝受热分解成 $\\mathrm{{Al}_{2}\\mathrm{{O}_{3}}}$ 和水，反应式如下：  \n\n$$\n\\mathrm{2Al(OH)_{3}\\xrightarrow{j\\mathrm{i}[j\\nearrow]}A l_{2}O_{3}+3H_{2}O}\n$$  \n\n氢氧化铝是一个极重要的阻燃剂，它不仅有受热分解吸热、放出结晶水汽化及冷却、稀释可燃性气体等阻燃作用，还有消烟、捕捉有害气体的作用。氢氧化铝用于木材、木制品、纸张、纸板、织物等易燃基材的表面阻燃技术处理的防火阻燃液中，主要起阻燃剂和消烟剂的作用；用于防火涂料中也主要起阻燃剂和消烟剂作用，在受火甚至在持续的火焰作用下不会分解成为气体化合物而烧失，以它的稳定性可以起到经久耐燃的作用，从而使防火涂料具有高效隔热防火性能。氢氧化铝虽然价廉、易得，并能起到减少毒气和烟雾的作用，但与有机类阻燃剂相比，要达到同样阻燃效果，需要添加的量较大，这样往往会影响涂料的其他物理力学性能。因此用它作阻燃剂时，一般不单独使用，多与其他类型阻燃剂配合使用。氢氧化铝其白度较高、粒径较细、折射率较低，经表面处理可由亲水性变成亲油性，增强与树脂的亲和力，亦可作为防火涂料的体质颜料使用，这样就能得到价格便宜、性能较好的防火涂料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 937,
+        "chunk": "# 3.氢氧化镁阻燃剂  \n\n氢氧化镁，分子式为 $\\mathbf{Mg(OH)}_{\\Xi}$ ，相对分子质量为58.3。氢氧化镁约在 $40^{\\circ}C$ 开始逐渐吸热并按如下反应进行分解。  \n\n$$\nM g(O H)_{2}\\mathrm{\\stackrel{-}{\\longrightarrow}M g O+H_{2}O}\n$$  \n\n$430^{\\circ}C$ 时达到顶峰， $490^{\\circ}C$ 时分解完结，留下氧化镁。在吸热分解反应中，氢氧化镁的吸热量为 $44.8\\mathrm{kJ/mol}$ ，在 $300^{\\circ}C$ 以下是稳定的，这是它具有阻燃作用的原因。  \n\n氢氧化镁和氢氧化铝同样具有无烟、无毒、无腐蚀性、安全价廉等优点，而且氢氧化镁开始释放水的温度高于氢氧化铝开始释放水的温度。氢氧化镁用于防火涂料中主要起阻燃剂和发泡剂、消烟剂的作用，在火焰和高温作用下，不会分解成为气体化合物而烧失，以它的稳定性可以起到经久耐燃的作用，从而使防火涂料具有高效的隔热防火性能。",
+        "category": " Introduction"
+    },
+    {
+        "id": 938,
+        "chunk": "# 4.水合硼酸锌（FB阻燃剂）  \n\n水合硼酸锌（FB阻燃剂)，分子式为 $\\mathrm{2ZnO\\bullet3B_{2}O_{3}\\bullet3.5H_{2}O}$ ，相对分子质量为434.5，白色结晶形粉末，熔点为 $980^{\\circ}C$ ，相对密度为2.8，折射率为1.58，不溶于水和一般有机溶剂，可溶于氨水生成络盐，热稳定性好，在 $300\\%$ 以上开始失去结晶水，粒度细，平均粒径为 $2\\sim$ $10\\mu\\mathrm{m}$ ，含 $\\mathrm{ZnO~}37\\%\\sim40\\%$ ， $\\mathrm{B}_{2}\\mathrm{O}_{3}~45\\%\\sim49\\%$ ， $\\mathrm{H_{2}O13.5\\%}{\\sim}15.5\\%$ ，失结晶水温度 $\\geq300^{\\circ}C$ ·粒度（325目筛余物） $\\leqslant1\\%$ ，含水量 $\\leqslant1\\%$ ，为无毒、无污染的无机阻燃剂。  \n\n硼酸锌与卤素阻燃剂RX混合使用，当接触火源时，生成气态卤化硼和卤化锌，并释放出结晶水。  \n\n$$\n2Z_{\\mathrm{n}}\\mathrm{O}\\cdot3\\mathrm{B}_{2}\\mathrm{O}_{3}\\cdot3.5\\mathrm{H}_{2}\\mathrm{O}+22\\mathrm{R}\\mathrm{X}\\longrightarrow2\\mathrm{Zn}\\mathrm{X}_{2}+6\\mathrm{B}\\mathrm{X}_{3}+11\\mathrm{R}_{2}\\mathrm{O}+3.5\\mathrm{H}_{2}\\mathrm{O}\n$$  \n\n同时燃烧时产生的HX继续与硼酸锌反应生成卤化硼和卤化锌。  \n\n$$\n\\mathrm{2ZnO\\bullet3B_{2}O_{3}\\bullet3.5H_{2}O+22H X\\mathrm{-}\\bullet2Z n X_{2}+6B X_{3}+14.5H_{2}O}\n$$  \n\n上述反应产生的卤化硼和卤化锌可以捕捉气相中反应活性物质HO·和 $\\mathtt{H}\\cdot\\mathtt{\\Gamma}$ ，干扰、中断燃烧的链反应，在固相中促进生成致密而又坚固的炭化层。同时在高温下硼化物在可燃物表面形成玻璃状固熔物包覆于纤维材料表面，既可隔热，又可隔绝空气。硼酸锌在 $300^{\\circ}C$ 以上时陆续释放出大量的结晶水，起到吸热、降温和消烟的作用。硼酸锌为无机添加型阻燃剂，由于它无毒性、低水溶性、高热稳定性、粒度细、分散性好，故在阻燃领域中的用途广泛。一般可和氧化锑 $\\left[\\mathrm{FB}:\\mathrm{Sb}_{\\mathrm{\\ell}}\\mathrm{O}_{3}=\\left(1\\mathord{\\sim}3\\right):1\\right]$ 复配加到氯丁橡胶、氯化树脂、氯化聚乙烯等含卤素树脂配制的防火涂料中，或与含卤素的其他阻燃剂如氯化石蜡、十溴二苯醚、四溴双酚A、六溴环十二烷等一起使用。硼酸锌除了作为阻燃剂外，还可用作固相抑烟剂。日常火灾中人员死亡很大程度上是由于吸人大量的烟尘导致室息死亡，硼酸锌具有良好的抑烟性能。当三氧化二锑和硼酸锌的质量比为 $1:(1\\sim2)$ 时，其阻燃抑烟综合性能最好。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 939,
+        "chunk": "# （二）有机阻燃剂",
+        "category": " Introduction"
+    },
+    {
+        "id": 940,
+        "chunk": "# 1.四溴双酚A  \n\n四溴双酚A（TBA或TBBPA)，又称 $4,4^{\\prime}.$ （1-甲基亚乙基)双（2，6-二溴苯酚)，相对分子质量为543.85，四溴双酚A为白色结晶型粉末。熔点为 $175{\\sim}181^{\\circ}\\mathrm{C}$ ，不溶于水，溶于碱的水溶液及乙醇、丙酮、苯、冰醋酸等有机溶剂中。含溴量为 $57\\%\\sim58\\%$ ，水分 $\\leqslant$ $0.2\\%$ 。开始分解温度 $240^{\\circ}C$ ， $295^{\\circ}C$ 时迅速分解，使用时加工温度在 $220^{\\circ}C$ 以内为宜。溴含量较高，属于反应型阻燃剂，亦可做添加型阻燃剂使用。可用于环氧树脂、酚醛树脂、聚苯乙烯树脂、不饱和聚酯树脂、聚氨酯树脂等配制的防火涂料中，主要起阻燃剂的作用，同时四溴双酚A还可以作为纸张、纤维的表面阻燃处理的防火阻燃液中的阻燃剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 941,
+        "chunk": "# 2.氯化石蜡-42  \n\n氯化石蜡-42，又称氯蜡-42，分子式为 $\\begin{array}{r}{\\mathbb{C}_{25}\\ \\bar{\\mathrm{H}}_{45}\\ \\mathrm{Cl}_{7}}\\end{array}$ ，相对分子质量为594，为金黄色、琥珀色黏稠液体，不易燃易爆，挥发性极微，能溶于大多数有机溶剂，不溶于水和乙醇。相对密度 $(d)$ 为 $1.16\\sim1.17$ ，受热分解，分解温度大于 $110^{\\circ}C$ ，含氯量为 $40\\%\\sim44\\%$ ，酸值$\\leqslant0.10\\mathrm{mgKOH/g}$ ，折射率（ $25\\%$ ）为 $1.492\\sim1.496$ ，凝固点为- $-30\\sim-33\\bar{\\mathrm{C}}$ ，黏度$(25^{\\circ}C$ ）为 $200{\\sim}300\\mathrm{mPa}\\cdot\\mathbf{s}$ ，耐酸类、弱碱或盐水溶液。氯蜡-42升温超过 $150^{\\circ}C$ 或加碱与醇类溶液共沸可脱去氯化氢，生成高级链烯烃类；氯化石蜡加水在温度超过 $\\mathrm{150^{\\circ}C}$ 下开始发生水解反应。氯化石蜡-42属于难燃品，无爆炸危险，自燃点 $357^{\\circ}C$ ，是卤素阻燃剂系列之一。由于氯化石蜡具有与聚氯乙烯类似的结构，阻燃性和电绝缘性良好，挥发性低，因此普遍用于PVC电缆、软管、板材、人造革、薄膜的增塑阻燃剂。氯化石蜡可配制于丁苯橡胶、丁晴橡胶、氯丁橡胶、聚氨酯树脂等防火涂料中，起阻燃剂和增塑剂的作用。可以用于织物、木材、纸张和其他材料的表面阻燃处理，以降低其可燃性。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 942,
+        "chunk": "# 3.氯化石蜡-50  \n\n氯化石蜡-50，又称氯蜡-50、氯化石油-50，分子式为 $\\mathbf{C}_{15}\\mathbf{H}_{\\Xi\\bar{6}}\\mathbf{C}\\mathbf{l}_{\\bar{5}}$ ，相对分子质量为420，为浅黄色清澈黏稠液体，无味无毒，不溶于水，微溶于醇，易溶于苯、醚。密度（ $25\\mathrm{^\\circC}$ ）为$1.235{\\sim}1.255\\mathrm{g/cm^{3}}$ ，黏度（ $25^{\\circ}C$ ）为 $12{\\sim}16\\mathrm{Pa}\\cdot\\mathrm{s}$ ，折射率（ $20^{\\circ}C$ ）为 $1.505{\\sim}1.515$ ，凝固点在一 $30^{\\circ}C$ 以下，比热容为 $1.34\\mathrm{J}/(\\mathrm{g}\\cdot\\mathrm{K})$ ，含氯量为 $50\\%\\sim54\\%$ ，酸值 $\\leqslant0.71\\mathrm{mgKOH/g}$ ，热分解温度 $\\geq120^{\\circ}C$ 。升温超过 $150^{\\circ}C$ 或加碱与醇类溶液共沸可脱去氯化氢，生成高级链烯烃类；氯化石蜡加水在温度超过 $\\mathrm{150^{\\circ}C}$ 时开始发生水解反应。  \n\n氯化石蜡等系列产品（除氯烃-13以外）均耐酸、耐碱和耐盐水溶液。比较容易溶于矿物油类、润滑油类、有机氯溶剂类，醚类、酯类、环己醇、麻油和其他植物油中。它们可与天然橡胶、氯化橡胶、合成橡胶、聚酯树脂和醇酸树脂类配伍使用。  \n\n氯化石蜡-50起阻燃作用的同时还具有增塑作用，因此成为最重要的增塑剂，是邻苯二甲酸二丁酯、邻苯二甲酸二辛酯、磷酸三甲苯酚酯的代用品或辅助助剂，通常本品在增塑混合物中的含量可达增塑剂总量的 $30\\%\\sim50\\%$ 。氯烃-50还具有抗老化的作用。以本品为基础配制的防火阻燃液，对织物、纸张、帆布等易燃纤维材料的表面进行阻燃处理，可使其具有耐火、耐候性，增强了抗老化性，减少了主要增塑剂的逸度，降低了气味，提高了制品的机械强度和耐用性。氯烃-50用于防火涂料和防火阻燃液中主要起阻燃剂、增塑剂及抗老化剂的作用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 943,
+        "chunk": "# 4.氯化石蜡-60  \n\n氯化石蜡-60，又称氯蜡-60、氯烃-60，分子式为 $\\mathrm{C_{15}\\ H_{\\bar{2}\\bar{3}}C l_{\\bar{9}}}$ ，系高含氯量液体氯化石蜡，为透明浅黄液体。密度（ $25^{\\circ}C$ ）为 $\\mathrm{1.36{\\sim}1.37g/\\mathrm{cm}^{3}}$ ，黏度（ $25^{\\circ}C$ ）为 $40\\mathrm{{Pa}\\cdot\\mathbf{s}}$ 。含氯量为 $60\\%$ ，热稳定性较好，化学稳定性较好，耐酸、耐弱碱和耐盐水溶液。温升超过 $150^{\\circ}C$ 或加碱与醇类溶剂共沸时可脱去氯化氢，生成高级链烯烃类，在 $150^{\\circ}C$ 时与水接触易产生水解作用。  \n\n氯化石蜡通常用作阻燃添加剂，除了提高塑料、橡胶的耐火性外，还可作为防火涂料的阻燃添加剂和增塑剂。同时在织物阻燃整理中可作为防火剂和增塑剂使用。用于木材、木制品、纸张、纸板、织物等易燃纤维材料的表面阻燃技术处理，起阻燃剂、增塑剂的作用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 944,
+        "chunk": "# 5.氯化石蜡-70  \n\n氯化石蜡-70，又称氯蜡-70、氯烃-70，分子式为 $\\mathbf{C}_{25}\\mathbf{H}_{30}\\mathbf{C}\\mathbf{l}_{22}$ ，相对分子质量为 $1060\\sim$ 1100，本品是一种外观白色或浅琥珀色粉末。结晶为树脂状透明脆性固体，手捏搓有松香般黏滞感。含氯量为 $70\\%$ ，软化点 $>95^{\\circ}C$ ，相对密度为 $1.66{\\sim}1.7$ ，粒度50目，不溶于水和低级醇，有限度的溶于高级醇、丙酮和苯类溶剂，溶于四氯化碳等氯代溶剂，与许多高聚物材料有良好的相容性。引人各类树脂和其他高聚物中可提高难燃性，改善流动性。  \n\n本品和其他氯蜡产品的化学性质类似，当氯化石蜡-70升温超过 $150^{\\circ}C$ 时，稳定性开始逐渐变差。随着温度升高，热稳定性表现为 $175^{\\circ}C/4h$ 有 $1\\%$ 氯化氢开始逸出。对光和热比较敏感，是一种良好的有机氯卤阻燃剂。用于防火涂料中主要起阻燃剂的作用。可作为织物和包装材料的表面阻燃处理剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 945,
+        "chunk": "# 6.磷酸三（2-氯乙）酯  \n\n磷酸三(2-氯乙)酯，又称三(2-氯乙基)磷酸酯，分子式为C6HzOClP，相对分子质量为285.50，  \n\n磷酸三(2-氯乙)酯为淡黄色油状液体。溶于醇、酮、酯、氯仿、四氯化碳等溶剂，不溶于脂肪族烃。水中溶解度（20℃）为4.64%，沸点（1.33kPa）为194℃，黏度（20℃）为34～47mPa·s，凝固点为一64℃，热分解温度为240～280℃，水解稳定性良好，在氢氧化钠水溶液中少量分解。  \n\n磷酸三(2-氯乙)酯属添加型阻燃剂，同时含有磷和氯，阻燃效果显著。广泛用于防火涂料中，主要起阻燃剂的作用，还可改善涂料的耐水性、耐酸性、耐寒性与抗静电性，特别是用于透明防火涂料中，使防火涂料固化后涂膜透明，能保持基材原有纹理和色泽，并有好的防火隔热性能。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 946,
+        "chunk": "# 7.磷酸三（2，3-二氯丙）酯  \n\n磷酸三(2,3-二氯丙)酯，又称三(2,3-二氯丙基)磷酸酯，分子式为CgH15O4ClP，相对分子质量为430.90。  \n\n本品为浅黄色黏稠液体，相对密度（25℃）为1.5129，自燃温度为513.9℃，着火点为282.2℃，闪点为251.7℃，沸点（0.53kPa）>200℃，凝固点为－6℃，230℃开始分解，水中溶解度（30℃）为0.01%，水在其中溶解度为0.98%。可溶于氯化溶剂（如全氯乙烯)，黏度（23℃）为1850mPa·s。磷含量为7.2%，氯含量为49.1%。本品不易挥发及水解，对紫外线稳定性良好。  \n\n磷酸三(2,3-二氯丙)酯也属添加型阻燃增塑剂。可用于聚氯乙烯树脂、不饱和聚酯树脂、环氧树脂、酚醛树脂、聚氨酯树脂等配制的防火涂料，在防火涂料中起阻燃剂和增塑剂的作用，其防火涂料有较好的防火隔热性、防霉性、耐磨性、耐污染性、耐水性、耐候性、耐辐射性和电气性能，挥发性小。可用于木材、木制品、纸张、纸板、织物等易燃材料的表面防火阻燃技术处理。",
+        "category": " Introduction"
+    },
+    {
+        "id": 947,
+        "chunk": "# 8.磷酸三丁酯  \n\n磷酸三丁酯，又称三丁基磷酸酯，分子式为C2H27OP，相对分子质量为266.38，磷酸三丁酯为无色无臭液体。色泽（APHA）为15，酸度（以磷酸计）为0.01%，相对密度（20℃）为0.973～0.978，动力黏度（25℃）为3.5～12.2mPa·s，凝固点为一80℃，沸点为289℃，着火点为204℃。微溶于水、甘油、乙二醇，可溶于大多数有机溶剂。本产品属添加型阻燃增塑剂，有一定阻燃和消泡效果。用于防火涂料中主要起阻燃剂、增塑剂、消泡剂的作用。用于透明防火涂料中，使防火涂料固化后涂膜透明，能保持基材原有纹理和色泽。可用于木材、木制品、纸张、纸板、织物等易燃材料的表面防火阻燃技术处理。  \n\n![](images/6422b989ad72e1ea272479057ab3f5c0e44c862291b5087ab8b2953270e81505.jpg)  \n\n在设计防火涂料配方时，除要满足防火涂料特性及质量指标要求外，还应适应防火涂料不同施工方式的要求。不仅要考虑主要成膜物、阻燃添加剂和增强填料，还要重视辅助成膜物——溶剂、助剂的选择，在设计有色防火涂料配方时还要重视颜料的选择。  \n\n防火涂料配方设计即配方组成的确定，主要包括原料选择（基料、阻燃添加剂、增强填料、颜料、溶剂、助剂等）及各种原料之间的合理配比选择。在防火涂料配方设计时，应在众多因素中抓住主要因素，即以主要成膜物（基料）的选择作为原料第一步选择的重点。首先要根据产品用途、技术要求、施工应用条件、被保护对象以及被保护物形状、干燥方式初步确定一种基料进行试验，或者固定一种阻燃体系及配比来优选各种基料。先逐步对阻燃添加剂、溶剂和增强填料（填充剂）的类型进行选择，依次再进行基料与其之间的配比选择等。  \n\n一般防火涂料配方设计主要有下列几个内容： $\\textcircled{1}$ 各种基料类型的选择； $\\textcircled{2}$ 各种阻燃添加剂及增强填料类型的选择； $\\textcircled{3}$ 各种溶剂类型的选择； $\\textcircled{4}$ 各种助剂类型的选择； $\\textcircled{5}$ 各种颜料类型的选择； $\\textcircled{6}$ 各种原料配比的选择； $\\textcircled{7}$ 防火涂料实验研究配方的确定； $\\textcircled{8}$ 防火涂料的生产配方的确定。  \n\n为了考察防火涂料在不同气候条件下的适应性，还应将试生产的防火涂料在不同气候条件地区的实际工程中应用，进行试用及观察，以取得良好应用效果。这也是防火涂料配方设计的特点。  \n\n在防火涂料配方设计的具体方法上，可以充分利用先进的检测仪器，借助正交设计等优选方法，达到提高配方设计的效率及可靠性的目的。在防火涂料配方设计中，还应注意下列问题：  \n\n$\\textcircled{1}$ 了解各种原料（包括基料、阻燃剂、颜料、填料、溶剂、助剂等）的性能及来源、质量、检验方法和价格，能否相互配合这一点是相当重要的；  \n\n$\\textcircled{2}$ 了解防火涂料的主要生产工艺及设备情况，使配方设计与生产工艺及设备更紧密结合，使生产效率提高，产品质量稳定；  \n\n$\\textcircled{3}$ 配方设计不仅要考虑质量指标，同时要考虑产品成本，要充分利用国内各种资源，尽量使用价格低、资源丰富的原料，达到以最低的成本制造出最好质量产品的目的。  \n\n防火涂料的用途不同，其防火机理基本上都是非膨胀型和膨胀型。  \n\n下面利用钢结构防火涂料的配方设计作一典型介绍。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 948,
+        "chunk": "# 一、钢结构防火涂料的配方设计  \n\n国内一般把钢结构防火涂料根据不同的防火机理分为厚型钢结构防火涂料、薄型钢结构防火涂料和超薄型钢结构防火涂料。笔者认为这种分法并不科学，还是应该分为非膨胀型钢结构防火涂料和膨胀型钢结构防火涂料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 949,
+        "chunk": "# （一）非膨胀型钢结构防火涂料的配方设计  \n\n非膨胀型钢结构防火涂料又叫钢结构防火隔热涂料。所谓非膨胀型钢结构防火涂料是指涂层使用厚度在 $8\\sim50\\mathrm{mm}$ 的涂料。这类钢结构防火涂料的耐火极限为 $1.0\\sim3\\mathrm{h}$ 0这类钢结构防火涂料是用合适的粘接剂，再配以无机轻质材料、增强材料等组成，施工多采用喷涂，一般是应用在耐火极限要求在2h以上的钢结构建筑上。在火灾中涂层基本不膨胀，依靠材料的不燃性、低导热性和涂层中材料的吸热性来延缓钢材的温升，保护钢构件。非膨胀型（厚型）钢结构防火涂料按使用环境分为室内和室外两种类型。这种涂料其涂层外观装饰性不理想。非膨胀型钢结构防火涂料技术性能及指标见表3-11-7。  \n\n表3-11-7非膨胀型（厚型）钢结构防火涂料技术性能及指标  \n\n\n<html><body><table><tr><td colspan=\"2\">室 内</td><td colspan=\"2\"></td><td colspan=\"2\">室 外</td></tr><tr><td>检验项目</td><td>经搅拌后呈均匀稠厚流体状</td><td>技术指标</td><td>检验项目</td><td>技术指标</td><td></td></tr><tr><td colspan=\"2\">在容器中的状态 干燥时间(表干)/h 外观与颜色 初期干燥抗裂性 黏结强度/MPa 抗压强度/MPa 干密度/（kg/ma） 耐水性/h 耐冷热循环性/次</td><td colspan=\"2\">态，无结块 ≤24 允许出现1～3条裂纹，其宽度 应≤1mm ≥0.04 ≥0.3 ≤500 ≥24涂层应无起泡、脱落现象 ≥15涂层应无开裂、起泡、剥落 现象</td><td colspan=\"2\">干燥时间(表干)/h 外观与颜色 初期干燥抗裂性 黏结强度/MPa 抗压强度/MPa 干密度/（kg/m²） 耐曝热性/h 耐湿热性/h 耐冷热循环性/次 耐酸性/h</td><td colspan=\"2\">≤24 允许出现1～3条裂纹，其宽度应 ≤1mm ≥0.04 ≥0.5 ≤650 ≥720涂层应无起泡，脱落现象 ≥504涂层应起泡、脱落现象 ≥15涂层应无开裂、起泡、剥落 现象 ≥300涂层应无开裂、起泡、剥落 现象</td></tr><tr><td rowspan=\"2\">耐火 性能</td><td colspan=\"2\">涂层厚度(不大于)/mm</td><td>25±2</td><td colspan=\"2\">耐碱性/h 涂层厚度（不大于）/mm 耐火</td><td>≥30涂层应无起泡、明显的变 质、软化现象</td><td>25±2</td></tr><tr><td colspan=\"3\">耐火极限（不低于）（以I36b或I40b 标准工字钢梁做基材）/h</td><td>2.0</td><td colspan=\"2\">耐火极限（不低于）（以I36b或I40b 性能 标准工字钢梁做基材)/h</td><td>2.0</td></tr></table></body></html>  \n\n与其他类型的钢结构防火涂料相比，它除了具有水溶性防火涂料的一些优点之外，由于它从基料到大多数添加剂都是无机物，因此它还具有成本低廉、燃烧时发烟小等特点。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 950,
+        "chunk": "# 1.室内非膨胀型钢结构防火涂料  \n\n室内厚涂型钢结构防火涂料价格较低，它主要由无机黏结剂，再配以无机轻质材料、增强材料组成。该类钢结构防火涂料施工采用喷涂，一般多应用在耐火极限要求2h以上的室内钢结构上，如高层民用建筑的柱、一般工业与民用建筑中的支承多层的柱。由于非膨胀型防火涂料受火时，涂层基本上不发生体积变化，而依靠构成涂层的材料自身的低导热性和隔热性对钢构件起屏障和防止热辐射的作用，避免火焰和高温直接进攻钢构件。要达到高等级耐火性能，因而涂层外观装饰性相对较差。  \n\n可用于该类钢结构防火涂料基料的无机粘接剂有碱金属硅酸盐类、磷酸盐类等。钠盐中由于存在游离的碱金属离子，空气中的酸性气体如 $\\mathrm{CO}_{2}$ 等要与其发生反应，如果单用其作为涂料的基料会使涂膜不耐水不耐潮，并且耐候性差，涂层易出现开裂、脱粉等不良现象。因此如果采用硅酸钠作为钢结构防火涂料的基料，其关键技术之一是对其进行改性，即解决对游离的碱金属离子的抑制问题。目前解决这个问题的途径大多采用氟硅酸盐、硼酸盐、有机高分子聚合物等对其进行改性，将其面型结构转变，形成一种体型的网状结构将碱金属离子固定下来。当这一过程完成后，碱金属离子就不再与 $\\mathrm{CO_{2}}$ 反应，从而改善涂膜的理化性能。  \n\n磷酸盐类粘接剂也是常用的无机粘接剂，用它作为防火涂料的基料，可以避免碱性氧化物与空气中的酸性气体反应，从而提高涂料的耐候性、耐水性等理化性能。其种类较多，根据其所含的金属不同，其性能也不同，一般认为强度 $\\mathrm{Al>Mg>Ca}$ ， $Z n{\\mathrm{>Ba}}$ 14耐水性 Ca、 $\\mathrm{Zn}{>}\\mathrm{Mg}{>}\\mathrm{Al}{>}\\mathrm{Fe}$ 、Cu;粘接性 $\\mathrm{Al{>}M g>}\\mathrm{Ca}>\\mathrm{Cu}>\\mathrm{Zn}$  \n\n但是其M/P的摩尔比（M指金属，P是磷）对涂料的贮存稳定性、与钢基材的附着力、耐水性都有直接影响。因此在以磷酸盐为基料的钢结构防火涂料的研制中，基料物质的摩尔比的控制是很重要的。另外厚涂型钢结构防火涂料由于涂层厚而用量多，在研究其配方中应注意加人一些轻质材料和高效隔热骨料。  \n\n在非膨胀型防火涂料中，碳酸钙可以使涂料增稠、加厚，起到填充和补平的作用，所以在厚涂型防火涂料中通常添加轻质碳酸钙，以降低防火涂料的干密度。一般轻质碳酸钙填加量可达 $20\\%$ 左右。碳酸钙对增塑剂、稳定剂、润滑剂和其他添加剂没有大的吸收作用，其价廉、无毒、高白度、资源丰富、易于在配方中混合及性质较为稳定（ $800^{\\circ}C$ 以上才分解)，可部分取代昂贵的白颜料，因而大量用于防火涂料中作填料和增强材料，起骨架、阻燃剂和体质颜料的作用。碳酸钙用于防火涂料中，增加了涂膜的冲击强度，提高了防火涂料的韧性及弹性；降低收缩，具有优良的色牢度；可改进防火涂料表面质量；改进稳定性和抗老化性。  \n\n非膨胀型钢结构防火涂料根据生产厂家的不同而情况各异，有的是单组分包装，有的是双组分包装，双组分包装的在现场按比例调配后使用；有的是干粉料，在现场加水调配使用；也有的是三组分包装，即分底层、中间层和面层涂料。由于该涂料用量大，所以目前大多数是采用干粉料包装，在现场加水配制使用。该类涂料具有密度轻、热导率低、耐热性好、无味无毒、耐水等优点。  \n\n下面列出室内厚型钢结构防火涂料的两个典型配方，并分别加以介绍。  \n\n（1）配方一$\\textcircled{1}$ 配方分为甲、乙两组分。  \n\n甲组分  \n\n<html><body><table><tr><td>原料名称</td><td>含量/%</td><td>原料名称</td><td>含量/%</td></tr><tr><td>硅溶胶</td><td>15~25</td><td>氯偏乳液</td><td>8~15</td></tr><tr><td>硅酸铝纤维</td><td>5~10</td><td>助剂</td><td>0~5</td></tr><tr><td>轻质碳酸钙</td><td>15~25</td><td>水</td><td>30~40</td></tr><tr><td>乙组分</td><td></td><td></td><td></td></tr><tr><td>膨胀珍珠岩</td><td>35~50</td><td>硅藻土</td><td>15~20</td></tr><tr><td>粉煤灰空心微珠</td><td>30~40</td><td></td><td></td></tr></table></body></html>  \n\n$\\textcircled{2}$ 介绍此配方以硅溶胶和氯偏乳液为黏结剂，配以高效隔热骨料（如膨胀蛭石）、轻质材料（如微珠、膨胀珍珠岩等）和化学助剂搅拌混合而成，具有防火隔热性好、冲击强度好和性能稳定、无气味、无毒以及对环境无污染等优点。在火灾中涂层不膨胀，依靠材料的不燃性、低导热性和吸热性来延缓钢材的温升，保护钢件。主要适用于影剧院、宾馆、体育馆、写字楼、礼堂、百货大楼、发电厂及大跨度厂房等建筑物中的隐蔽钢结构，喷涂于表面起防火保护作用，提高了钢结构的耐火极限。  \n\n（2）配方二$\\textcircled{1}$ 配方云母粉膨胀蛭石  \n\n<html><body><table><tr><td>原料名称</td><td>含量/%</td><td>原料名称</td><td>含量/%</td></tr><tr><td>水泥</td><td>25~40</td><td>膨胀珍珠岩</td><td>10～20</td></tr><tr><td>玻璃纤维</td><td>5~10</td><td>空心微珠</td><td>15~20</td></tr></table></body></html>  \n\n助剂  \n\n$$\n0\\sim3\n$$  \n\n$\\textcircled{2}$ 介绍此配方为单组分，使用方便，加适量水调和均匀即可  \n\n这类产品如我国国内的SD-2钢结构防火涂料、FN-LG钢结构防火涂料，当涂层厚度分别为 $27.6\\mathrm{mm}$ 和 $39.5\\mathrm{mm}$ 时，耐火极限可达 $2.28\\hbar$ 和 $2.53\\mathrm{h}$ ；国外的产品如英国GraceCon-struction Products（格雷斯建材产品）的 Monokete Fire-proofing UK-6 钢结构防火涂料，涂层厚度为 $47.7\\mathrm{mm}$ ，耐火极限为2.5h；美国美商华人企业股份有限公司的AD钢结构防火涂料，涂层厚度为 $33.7\\mathrm{mm}$ ，耐火极限为 $\\mathrm{3h}$ 。可护固欧洲有限公司的CAFCOBLAZESHIELDⅡ钢结构防火涂料，涂层厚度为 $18\\mathrm{mm}$ 和 $34\\mathrm{mm}$ 时，耐火极限为 $\\mathbf{1.88h}$ 和3.8h；该公司的CAFCO300钢结构防火涂料，涂层厚度为 $35\\mathrm{mm}$ ，耐火极限为4.5h，涂层厚度为$41\\mathrm{mm}$ ，耐火极限可达5h以上。最早进入国内市场的国外钢结构防火隔热涂料是英国的P20涂料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 951,
+        "chunk": "# 2.室外非膨胀型（厚涂型）钢结构防火涂料  \n\n指适合于室外环境使用的非膨胀型（厚涂型）钢结构防火涂料，其价格比室内厚涂型钢结构防火涂料高一些，主要用于建筑物室外和石化企业露天钢结构等。这类钢结构防火涂料的基料是耐候性好的合成树脂或有机高分子聚合物乳液与无机基料复合而成，再配以阻燃剂、轻质材料、增强材料组成。室外钢结构防火涂料配方示例如下  \n\n<html><body><table><tr><td>原料</td><td>用量（质量分数）/%</td><td>原料</td><td>用量（质量分数）/%</td></tr><tr><td>高分子聚合物乳液</td><td>15～20</td><td>无机轻质材料</td><td>25~40</td></tr><tr><td>硅溶胶</td><td>5~10</td><td>颜料</td><td>3~8</td></tr><tr><td>添加剂</td><td>1~3</td><td>水</td><td>适量</td></tr></table></body></html>  \n\n室外非膨胀型钢结构防火涂料的成膜物质有无机成膜物质，如硅溶胶是一种理想的无机成膜物，它是由水玻璃经过酸处理、电渗析及离子交换等方法去掉钠离子后得到的超微粒子聚硅酸分散体，具有一旦成膜就不再溶解的特性。但由于它在成膜过程中体积收缩大，因而容易引起涂层开裂、硬脆。有机成膜物质有水性有机树脂或拼用的有机乳液，如丙苯乳液、丙烯酸系列乳液等，涂层的力学性能可以大大改善。室外钢结构防火涂料的阻燃添加剂的选择与其他钢结构防火涂料类似，但要适应室外的环境条件，对耐水、耐候、耐化学腐蚀性能等的要求更苛刻。  \n\n国内有SWH室外钢结构防火隔热涂料、STI-B露天钢结构防火涂料。SWH室外钢结构防火隔热涂料由无机基料、有机树脂、耐火绝热材料加水搅拌混合而成，可广泛用于化工厂、炼油厂、石油钻井平台和油（气）罐支承及电线电缆栈桥等露天钢结构的防火保护。涂料中不含苯类溶剂和有害物质，无刺激性气味，单组分包装，直接喷涂施工，操作简便，耐水、耐化学腐蚀、耐冻融循环等性能突出。STI-B露天钢结构防火涂料由高效绝热骨料、无机基料等为主要原料，加入部分防火添加剂和化学助剂混合而成，可用于露天建筑物钢构件起防火保护作用。  \n\n英国的JA60-4（H类）非膨胀型钢结构防火涂料按工艺要求除锈并涂上防火涂料，在野外进行了实验。耐紫外线照射实验，经测试用200W紫外线灯光连续照射 $240\\mathrm{h}$ ，涂层表面未见任何粉化现象；耐火实验，用 $800^{\\circ}C$ 以上的高温火焰对涂上防火层的型钢进行阻燃实验，共进行 $120\\mathrm{min}$ ，涂层表面遇火不燃烧，仅出现局部炭化，冷却后剥开防火层，型钢和槽钢完好无损。工程完工后，经过数月恶劣气候条件的考验，涂层完好如初，未出现裂纹、脱落、鼓包等现象，外观良好。JA60-4室外非膨胀型钢结构防火涂料的技术指标与国标对  \n\n比见表3-11-8。  \n\n表3-11-8JA60-4（H类）室外非膨胀型钢结构防火涂料的技术指标与国标对比  \n\n\n<html><body><table><tr><td rowspan=\"2\">检验项目</td><td colspan=\"2\">技术指标</td></tr><tr><td>JA60-4</td><td>WH(GB 149072002)</td></tr><tr><td colspan=\"2\">在容器中的状态</td><td>经搅拌后呈均匀稠厚流体状态，无结块</td><td>经揽拌后呈均匀稠厚流体状态，无结块</td></tr><tr><td colspan=\"2\">干燥时间（表干)/h</td><td>12</td><td>≤24</td></tr><tr><td colspan=\"2\">外观与颜色</td><td></td><td></td></tr><tr><td colspan=\"2\">初期干燥抗裂性</td><td>一般不出现裂纹，如有1～3条裂纹，其 宽度应≤1mm</td><td>允许出现1～3条裂纹，其宽度应≤1mm</td></tr><tr><td colspan=\"2\">黏结强度/MPa</td><td>0.25</td><td>≥0.04</td></tr><tr><td colspan=\"2\">抗压强度/MPa</td><td>0.4</td><td>≥0.5</td></tr><tr><td colspan=\"2\">干密度/（kg/m3）</td><td>≤450</td><td>≤650</td></tr><tr><td colspan=\"2\">耐曝热性/h</td><td></td><td>≥720，涂层应无起层、脱落、空鼓、开裂 现象</td></tr><tr><td colspan=\"2\">耐湿热性/h</td><td></td><td>≥504，涂层应无起层、脱落现象</td></tr><tr><td colspan=\"2\">耐冻融循环性/次</td><td>≥15，涂层应无开裂、脱落、起泡现象</td><td>≥15，涂层应无开裂、脱落、起泡现象</td></tr><tr><td colspan=\"2\">耐酸性/h</td><td></td><td>≥360，涂层应无起层、脱落、开裂现象</td></tr><tr><td colspan=\"2\">耐碱性/h</td><td></td><td>≥360，涂层应无起层、脱落、开裂现象</td></tr><tr><td colspan=\"2\">耐盐雾腐蚀性/次</td><td></td><td>≥30，涂层应无起泡、明显的变质、软化 现象</td></tr><tr><td rowspan=\"2\">耐火 性能</td><td>涂层厚度(不大于)/mm</td><td>20 30</td><td>25±2</td></tr><tr><td>耐火极限（不低于）以 I36或I40b标准工字钢梁 做基材/h</td><td>2.0 3.0</td><td>2.0</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 952,
+        "chunk": "# （二）膨胀型钢结构防火涂料的配方设计  \n\n国内把涂层使用厚度在 $3\\sim7\\mathrm{mm}$ 的钢结构防火涂料称为薄涂型钢结构防火涂料，把使用厚度在 $1\\sim3\\mathrm{mm}$ 的钢结构防火涂料称为超薄涂型钢结构防火涂料。实际上这两类防火涂料严格意义上都应该称为膨胀型钢结构防火涂料。  \n\n膨胀型钢结构防火涂料作为特种涂料，不仅组成复杂，而且性能包括发生火灾前和火灾后两个层面，也较普通涂料更为复杂。在膨胀型钢结构防火涂料基料的研究中，对于基料的选用主要应考虑两个问题，一个是基料与防火助剂之间的协调性；另一个是涂料的室温自干性。  \n\n用于膨胀型钢结构防火涂料的热塑性树脂包括：氯乙烯树脂、丙烯酸树脂、高氯化聚乙烯树脂、氯化橡胶等。热塑性树脂存在一个熔融软化温度，当外界温度在熔融软化温度以上时，涂层容易软化熔融。熔融的树脂黏度逐渐减小，使涂层与基材或涂层与涂层之间的黏附力减小。当处于涂层发泡剂的分解温度时，树脂的黏度已经很小，严重影响了涂层与基材之间的附着力，涂层的流动程度太大而产生流淌，在涂层即将发泡、炭化之际，涂层出现脱落现象。超薄型钢结构防火涂料的涂层较薄、树脂含量较高，树脂的熔融软化温度与发泡剂分解温度相差太大时，对涂层的防火性能有不利影响。因此，如果采用热塑性树脂作为膨胀型钢结构防火涂料的基料时，一般要求树脂的熔融软化温度与脱水成炭催化剂和发泡剂的分解温度以及炭化剂的炭化温度之间不能相差太大，要有良好的匹配。  \n\n防火涂料中采用单一树脂作为基质树脂时其性能往往不好，采用两种甚至几种树脂混用的复合树脂作为防火涂料的基质树脂，可以制备性能全面的防火涂料。例如，高氯化聚乙烯树脂具有优异的难燃性，软化温度较高，用其制备的防火涂料的耐火极限温度很高，但是也存在着涂层较脆、附着力不高、遇火燃烧时炭化层易开裂等现象。例如，采用高氯化聚乙烯为主要基料，加人自干性聚丙烯酸树脂和少量丁醇醚化氨基树脂进行改性，结果发现涂层的柔韧性、附着力大大提高，遇火开裂的现象也基本消除。  \n\n目前，膨胀型防火涂料树脂中，应用最广泛的是内烯酸树脂，因为内烯酸树脂的熔融温度与脱水成炭催化剂聚磷酸铵最相匹配。  \n\n钢结构防火涂料的另一关键组分一——阻燃添加剂，对涂料的防火性能影响也是巨大的。对于阻燃剂，要求它必须能与基料相互配合，在受火时组分之间协调一致，膨胀发泡形成均匀、坚固、致密的防火隔热层。可用于该类钢结构防火涂料的阻燃剂种类繁多，性能各异。在研究过程中，要根据形成膨胀发泡体系的原理，进行复合阻燃剂的筛选。最后与基料进行配伍，摸索和研究合理的配比，使防火涂料达到最佳防火效果。阻燃剂是防火涂料具备防火阻燃特性的关键成分，对防火涂料的性能有至关重要的影响。通过热重和差热分析，对防火涂料的隔热性、发泡性、最佳协调性和装饰性及涂层厚度、发泡层高度、密度、硬度与耐火极限的关系等进行实验研究。另外膨胀型防火涂料研究中关键技术之一是如何解决涂料隔热性好、经久耐烧的问题。  \n\n目前国内外防火涂料的发展趋势是涂层超薄、装饰性强、施工方便、防火性能高、应用范围广，因此，对涂料的粘接力和耐水性有较高的要求。涂料除应具有较好的防火隔热性能、粘接力好、强度高，能经受高低温循环的影响外，涂层还应具有良好的耐水性、耐介质腐蚀性和不易脱落、贮存稳定、装饰性好、施工方便等特点。  \n\n下面把膨胀型钢结构防火涂料的各组分的作用及配方作一介绍。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 953,
+        "chunk": "# 1.基体树脂  \n\n基体树脂对膨胀型防火涂料的性能有重大的影响，它与其他组分配伍，既保证了涂层在正常条件下具有各种使用性能，又能在火焰灼烧或高温作用下帮助形成具有难燃性和优异的膨胀发泡效果的炭化层。  \n\n常见用于防火涂料的树脂有：丙烯酸树脂、氯化橡胶、高氯化聚乙烯树脂、醇酸树脂等。选择树脂的原则是涂料形成的膨胀层密实，涂料加工容易，涂料施工方便。  \n\n对不同的树脂作基体成膜物的防火涂料进行对比试验，结果如表3-11-9所示。  \n\n表3-11-9 使用不同树脂的对比情况  \n\n\n<html><body><table><tr><td>树脂名称</td><td>溶剂</td><td>发泡效果</td><td>炭化层质量</td><td>发烟量</td><td>理化性能</td></tr><tr><td>丙烯酸树脂</td><td>脂肪烃</td><td>较好</td><td>坚固、致密</td><td>很少</td><td>合格</td></tr><tr><td>氯化橡胶</td><td>二甲苯</td><td>好</td><td>较疏松</td><td>较多</td><td>合格</td></tr><tr><td>HCPE树脂</td><td>二甲苯</td><td>好</td><td>较坚固</td><td>较多</td><td>合格</td></tr><tr><td>改性HCPE</td><td>二甲苯</td><td>较好</td><td>坚固、致密</td><td>较少</td><td>合格</td></tr><tr><td>醇酸树脂</td><td>二甲苯</td><td>好</td><td>孔大不均</td><td>较少</td><td>合格</td></tr></table></body></html>  \n\n由上表可以看出，丙烯酸树脂防火涂料和改性HCPE树脂防火涂料的炭化层质量最高，防火性能最好，但HCPE树脂在发挥防火效能时发烟量较大，考虑到含氯树脂易产生氯化氢等二次毒性气体，不宜用于非开体系，因此，对于钢结构防火涂料而言，选择用丙烯酸树脂为本研究涂料的树脂成膜物，并对其进行改性，以提高涂料的整体效果。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 954,
+        "chunk": "# 2.催化剂的选择和筛选  \n\n催化剂是一种能在一定温度下分解出强酸性物质的材料，这些强酸性物质在一定温度下能脱去涂层内成炭剂的水分，使形成不易燃烧的具有高保温效果的炭化层。不同催化剂的对比情况见表3-11-10。  \n\n表3-11-10 使用不同催化剂的对比情况  \n\n\n<html><body><table><tr><td>名称</td><td>耐水性</td><td>加工性能</td><td>发泡效果</td></tr><tr><td>磷酸二氢铵</td><td>较差</td><td>较差</td><td>好</td></tr><tr><td>聚磷酸铵</td><td>一般</td><td>较好</td><td>较好</td></tr><tr><td>改性聚磷酸铵</td><td>较好</td><td>较好</td><td>较好</td></tr><tr><td>磷酸三聚氰胺</td><td>较好</td><td>较好</td><td>最好</td></tr></table></body></html>  \n\n目前国内外所采用的催化剂主要有磷酸氢二铵、磷酸二氢铵、聚磷酸铵、磷酸三聚氰胺等，选择的原则是耐水性、加工性及发泡性的好坏。对钢结构防火涂料而言，涂层必须要有良好的耐水性，因此磷酸氢二铵、磷酸二氢铵不在考虑范围内，磷酸三聚氰胺的水溶性较聚磷酸铵要小，且其兼具催化和发泡的双重作用，但成本较高、原料的来源渠道少。因此选择聚磷酸铵为主催化剂。但是聚磷酸铵在涂料的使用上存在着一些自身难以克服的缺点：与聚合物相容性差，抗渗析性差，一旦渗出聚合物表面，聚磷酸铵在潮湿的环境中易吸湿而水解、水溶，影响涂料的耐候、发泡性能等。为了提高含聚磷酸铵防火涂料在湿、热环境下的耐久性，必须降低聚磷酸铵的水溶性。主要从如下两个方面进行改进。  \n\na.采用特殊的技术和工艺改性成炭催化剂，火灾发生过程中，膨胀涂料形成梯度发泡，大大提高防火涂料的防火性能。  \n\nb.对原材料进行表面处理。采用微胶囊技术（MC）对APP进行包覆处理，使APP表面涂有包覆材料，从而改变APP的性能。根据所需的阻燃基料种类，选择合适的囊材，MC化的阻燃剂加人后增加与聚合物的相容性，从而减少和消除阻燃剂对涂料性能的不利影响。可用于包覆材料的种类很多，一般选用耐热性较高的聚脲、三聚氰胺树脂等耐热性高的树脂。  \n\n经表面处理的聚磷酸铵与没进行处理的聚磷酸铵相比：水溶性明显降低，与树脂的相容性、分散性明显提高。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 955,
+        "chunk": "# 3.成炭剂的选择  \n\n成炭剂是涂层在高温下形成不易燃三维空间结构的泡沫炭化层的物质基础，对泡沫炭化层起骨架作用。成炭剂在分解温度上要和催化剂相匹配。成炭剂的有效性取决于分子中羟基及碳原子的含量，羟基的数量大，成炭剂被脱水的速度相对较快。但成炭剂本身的亲水性高，所以并非羟基的数量越高越好。碳原子含量高、分子大，对最终形成的炭化层的强度及致密性有利。成炭剂的种类有很多，如季戊四醇、二季戊四醇、淀粉等，分别试验，结果对比如表3-11-11所示。  \n\n表3-11-11 不同成炭剂的对比  \n\n\n<html><body><table><tr><td>名称</td><td>耐水性</td><td>分散性</td></tr><tr><td>淀粉</td><td>差</td><td>好</td></tr><tr><td>季戊四醇</td><td>较好</td><td>较好</td></tr><tr><td>二季戊四醇</td><td>好</td><td>较好</td></tr></table></body></html>  \n\n使用淀粉作成炭剂，涂层的耐水性问题不易解决，而二季戊四醇由于其价格原因，在国内也很少用，一般选用季戊四醇。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 956,
+        "chunk": "# 4.发泡剂  \n\n膨胀型防火涂料的特点是涂层遇热时，能放出不燃性的气体，如氨、二氧化碳、水蒸气、卤化氢等，使涂层膨胀起来，并在涂层内形成蜂窝状泡沫结构。这些是靠发泡剂来实现的。发泡剂的分解温度是决定它是否适用的关键，分解温度过低，气体在成炭前逸出起不到作用；分解温度过高，产生的气体会把炭层顶起或吹掉，不能形成良好的炭质泡沫层。因此不同的多元醇和脱水成炭催化剂，采用的发泡剂也应该有所区别。常用的发泡剂有三聚氰胺、双氰胺、聚磷酸铵、氯化石蜡、磷酸铵盐、氨基树脂等，为了提高涂料的综合性能，一般采用复合发泡体系。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 957,
+        "chunk": "# 5.自身具有热膨胀特性的材料的选择  \n\n某些材料（如可膨胀珍珠岩、蛭石、改性石墨等）本身具有热膨胀特性，将其和涂料体系有机地结合在一起，可形成物理化学膨胀型防火涂料体系。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 958,
+        "chunk": "# 6.无机颜料、填料  \n\n对膨胀型防火涂料来说，含无机填料的比例较少，因其含量过高，会影响涂层的发泡高度，从而达不到隔热的目的，但少量颜料、填料却不可少，因其可使泡沫层更致密、强度更好，从而提高其防火性能。防火涂层一般施工厚度大，较低的颜料组分已能满足遮盖力的要求，故不需采用较多的无机颜料、填料，常用的着色颜料有钛白粉、氧化锌、铁黄、铁红等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 959,
+        "chunk": "# 7.无机隔热材料的添加  \n\n经过长期对膨胀炭层防火隔热性能的研究表明，膨胀层厚度与耐火极限并不完全成正比关系。原因与膨胀层的强度有关，若膨胀层疏松强度低，则随着其厚度的增加，其自身稳定性就越来越差，膨胀层就很容易从基材上坠落，使基材暴露于火焰中，起不到防火保护作用。因此提高膨胀炭层的防火隔热能力必须提高膨胀层强度。经过大量的试验探索得出，某些无机隔热材料的添加对膨胀层的补强十分有效，可以提高膨胀炭层在高温环境下的强度，保持炭层的完整致密。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 960,
+        "chunk": "# 8.无卤素阻燃剂的补偿  \n\n根据防火涂料的其他阻燃机理，添加其他无卤化学阻燃剂或填料型阻燃剂，如三氧化二锑、硼酸锌、氢氧化铝、氢氧化镁等阻燃剂，用于提高在涂层中膨胀组分发挥防火作用前涂层的阻燃能力，同时根据协效阻燃机理，这些阻燃剂的加人也显著提高了膨胀炭层的阻燃隔热能力。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 961,
+        "chunk": "# 9.溶剂  \n\n选择毒性低的、对人体刺激小的，具有合适挥发速度的混合溶剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 962,
+        "chunk": "# 10.配方设计  \n\n在设计膨胀型防火涂料配方时，要根据涂层正常使用条件和施工条件、涂层所受的高温火焰条件及其阻燃能力等性能要求进行设计。其基本原则如下。  \n\n(1）质量分数在膨胀型防火涂料组成中，起膨胀作用的组分（包括颜料、填料）的比例很大。一般要占总重量的 $50\\%\\sim80\\%$ ，黏合剂和添加剂约为 $20\\%\\sim30\\%$ ，溶剂占 $10\\%\\sim$ $20\\%$ 。另外起膨胀作用的三种化学物质，不是以任意比例相配合的，一般情况下，大多数配方的催化剂比为 $40\\%\\sim60\\%$ ，炭化剂为 $20\\%\\sim30\\%$ ，发泡剂为 $20\\%\\sim30\\%$ 要  \n\n(2）组分之间的配合要得到高效的炭化层，涂层中有机树脂的熔融温度、发泡剂的分解温度及泡沫炭化的温度必须配合恰当。当涂层受热时，首先是成膜剂软化熔融，引起整个涂层的软化、塑化，这时发泡剂达到分解温度，释放出不燃性气体，并使涂层膨胀成泡沫层，同时脱水催化剂分解生成磷酸、聚磷酸呈熔融的黏稠体作用于泡沫层，使涂层中的含羟基有机物发生脱水成炭反应，当泡沫达到最大体积时，泡沫凝固炭化，使生成的多孔的海绵状炭化层定形，泡沫的发泡效率取决于组分之间反应速率的协调配合。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 963,
+        "chunk": "# 11.研磨工艺对防火性能的影响  \n\n不同的研磨工艺制备的膨胀型防火涂料其膨胀层的细腻均匀性、致密结实性差别很大，因此需选择合适的研磨工艺。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 964,
+        "chunk": "# 12.基本配方  \n\n膨胀型钢结构防火涂料参考配方如下：  \n\n原料名称 含量（质量分数）/% 原料名称 含量（质量分数）/%合成树脂 $10\\sim20$ 颜填料 $5\\sim30$ 聚磷酸铵及衍生物 $10\\approx30$ 助剂I 1季戊四醇 $5\\sim10$ 助剂Ⅱ 2三聚氰胺 $5\\sim10$ 混合溶剂 10\\~30",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 965,
+        "chunk": "# （三）环氧膨胀型型钢结构防火涂料的配方设计  \n\n大家都知道露天钢结构应选用适合室外用的黏结力强、强度高、耐水、耐腐蚀、耐冻融、耐湿热和抗老化性能好的钢结构防火涂料。国外在室外或潮湿环境下大多采用环氧类防火涂料，特别是在有烃类火灾危险的结构中广泛采用。  \n\n环氧膨胀型防火涂料较厚型防火涂料相比，第一，表面更光滑，表面不易产生灰尘，易清洁，这对于应用到食品厂及制药厂及医院非常重要；第二，膨胀涂料的涂膜较厚型的薄得多，占用空间小；第三，膨胀涂料使用更方便；第四，膨胀涂料的装饰性更好；第五，厚型防火涂料对机械撞击更敏感；第六，厚型防火涂料不适合应用于化学环境中。总之，厚型防火涂料虽然不存在有些活性成分在潮湿的环境条件下会慢慢析出影响防火效果的问题，但仍存在自重大、影响建筑外观的问题，更严重的是由于涂得太厚，黏结强度不够，历经风吹雨淋，容易开裂，水汽易进人，几乎没有能够达到三年以上而不出现脱落的（目前仍是石化、石油行业存在的一个老大难问题)。因此，虽然环氧类防火涂料比厚型防火涂料贵得多，发达国家仍然大量使用厚型防火涂料。目前国外厚型防火涂料几乎完全被环氧防火涂料取代，特别是在海军、海洋设施、军事及商用飞机、石化、石油及海上石油平台、弹药库及导弹发射架等领域。  \n\n美国的Underwriters实验室已经对环氧防火涂料进行了检验和评价认为其完全适合于户外。通过加速老化来判定此类防火涂料经过很长时间仍保持防火性能，试验方法是UL1709。挪威的NorwegianNORSOKM501还进行了浸泡和冻融循环检验。  \n\nNu-Chem公司采用Thermo-Lag技术，研制生产了“升华涂料”系列，如Thermo-Lag220、Thermo-Lag3000 等。Nullifire公司推出了System E 系列环氧膨胀型防火涂料，德国的Permatex公司、美国的Textron公司等，均有环氧膨胀型防火涂料。  \n\n选择环氧树脂作为成膜剂，还有一个重要的原因，那就是环氧树脂可以作为膨胀型防火涂料的成炭剂（碳源)。传统理论认为，成炭剂是形成三维空间结构不易燃的泡沫炭化层的物质基础，对泡沫炭化层起着骨架的作用，它们是一些含高碳的多羟基化合物，如淀粉、季戊四醇、二季戊四醇、三季戊四醇、含羟基的树脂等。通过大量的实验证实环氧树脂可以作为成炭剂，也可以与脱水催化剂反应生成多孔结构的炭化层。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 966,
+        "chunk": "# 二、环氧防火涂料的基本配方及检测方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 967,
+        "chunk": "# （一）基本配方  \n\n环氧膨胀型型钢结构防火涂料的基本配方如下：  \n\n<html><body><table><tr><td>原料名称</td><td>含量/%</td><td>原料名称 含量/%</td></tr><tr><td>环氧树脂</td><td>10~20 碳酸钙</td><td>5~10</td></tr><tr><td>聚磷酸铵及衍生物</td><td>5~10</td><td>钛白粉 5~10</td></tr><tr><td>季戊四醇</td><td>2~3</td><td>助剂I 1</td></tr><tr><td>三聚氰胺</td><td>5~10 助剂Ⅱ</td><td>2</td></tr><tr><td>三苯基磷酸酯</td><td>5~10</td><td>活性稀释剂 5~10</td></tr><tr><td>硼酸锌</td><td>3~5 固化剂</td><td>适量</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 968,
+        "chunk": "# （二）检测方法  \n\n对室外用环氧膨胀型防火涂料防火性能方面，现阶段国内没有相应的检测标准，国外同类产品大多通过UL1709和DNVNORSOKM501的相关检测。  \n\n在英国，除了《建筑规范》有一些要求外，对结构钢组件（在没有气体、油类和化学危险品的场所)，目前还没有其他进行更进一步试验的法定要求。特别是针对爆炸和（或）烃类火影响后果的实验或许可，也没有具体的规定要求。其他欧洲国家和美国，情况也与此相似，而且这些国家只有国家标准规定的纤维素火实验。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 969,
+        "chunk": "# 1.气体爆炸实验  \n\n在 ${\\sqrt[[object Object]]{1^{n}}}$ 世贸中心事故中，先发生爆炸，然后起火，消防设施丧失了对下面结构的保护作用，这就要求膨胀型防火涂料必须在爆炸过程中和爆炸发生后都能保持完好并黏附在钢材上。所以，Leigh'sPaints 就采用了一种Advantica 技术（以前英国的一种气体技术）来进行气体爆炸实验，以评价薄薄一层膨胀型防火涂料抵御爆炸的能力。  \n\n气体爆炸实验是将一些涂有Firetex膨胀型防火涂料的预制构件组装成的钢柱放在一个 $182\\mathrm{m}^{2}$ 的爆炸室内。平均最大超压1697mbar（ $1\\mathrm{bar}=10^{5}\\mathrm{Pa})$ ，平均持续时间 $104\\mathrm{ms}$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 970,
+        "chunk": "# 2.烃类火实验  \n\n在已经进行过气体爆炸实验和没有进行气体爆炸实验的对照试样上都装上热电偶，并在对照试样上也涂上相同的膨胀型涂料，干膜厚度为进行过爆炸实验试样的 $5\\%$ 以内。  \n\n将这两种试样进行同样的火灾实验，加热条件按照1987年版BS476标准第20部分附录D的规定进行。这里规定了一个模拟烃类燃料燃烧过程温度变化的温度曲线。这个温度曲线介于精确测定的烃类温度曲线和实际燃烧室中的温度曲线之间。  \n\n烃类火一般比纤维素火更猛烈（见图3-11-14)，这一点从BS476标准第20部分的曲线中也可以看出。  \n\n，国外许多国家如美国、英国、荷兰等国的研究单位，已分别制定了不同的烃类火升温曲线，上述几种升温曲线的数据比较见表3-11-12。从该表看出，烃类火的温升要比标准火快得多， $\\mathbf{\\mathrm{10min}}$ 时大约为标准火温升的 $1,48\\sim1.82$ 倍， $90\\mathrm{min}$ 时大药为标准火温升的 $1.17\\cdots$ 1.32倍。  \n\n![](images/706783c80220232c67a9a45fbc575d39a738a13d7690287869e62118dd169fc1.jpg)  \n图3-11-14 烃类火与纤维素火的升温曲线比较  \n\n表3-11-12几种升温曲线温升比较  \n\n\n<html><body><table><tr><td rowspan=\"2\">火类型</td><td rowspan=\"2\" colspan=\"2\">升温曲线</td><td colspan=\"5\">不同时间对应炉内温升/℃</td></tr><tr><td>10min</td><td>30min</td><td>60min</td><td>90min</td><td>120min</td></tr><tr><td>标准火</td><td colspan=\"2\">国际标准ISO834</td><td>659</td><td>821</td><td>925</td><td>986</td><td>1029</td></tr><tr><td rowspan=\"2\">烃类火</td><td>美孚石油公司 英国Warrington 研究中心</td><td>大型火灾 中型火灾</td><td>1000 975</td><td>1100 1140</td><td>1150 1190</td><td>1150 1200</td><td></td></tr><tr><td>荷兰Delfte国 家研究院</td><td>大型火灾 中型火灾</td><td>1200 1000</td><td>1300 1130</td><td>1350 1180</td><td>1300 1200</td><td>1200</td></tr></table></body></html>  \n\n由于国内设备条件等因素所限，目前还没有按烃类火升温曲线和GB14907—2002标准规定的方法对钢梁进行耐火极限试验。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 971,
+        "chunk": "# 第六节 防火涂料的发展",
+        "category": " Introduction"
+    },
+    {
+        "id": 972,
+        "chunk": "# 1.新型树脂的研究  \n\n我国防火涂料的发展较国外工业发达国家晚 $10\\sim20$ 年，水性膨胀型防火涂料的研究刚刚起步，目前问世的水性膨胀型防火涂料较溶剂型防火涂料在防火隔热效果、附着力、装饰性及耐水性方面有很大差距，在很多领域不能代替溶剂型的使用。与国外水性膨胀型防火涂料的发展有较大差距。国内目前生产的膨胀型防火涂料多是以传统乳液为成膜物，如苯丙乳液、纯丙乳液、硅丙乳液、弹性乳液等作为成膜物。这类成膜物制备的膨胀型防火涂料由于发泡较慢、发泡不均匀、发泡持续时间短、泡层不致密、炭化物较少、炭化层厚度较低、炭化不彻底等缺点，造成防火隔热效果不够理想。这也是影响水性膨胀型防火涂料性能的主要原因。因此几十年来研究人员一直致力于研制出一种高性能的水性成膜物用于膨胀型防火涂料。  \n\n丙烯酸乳液作为水性膨胀型防火涂料最重要的成膜物，国内外研究人员对水性丙烯酸乳液进行了很多的改性工作。其中几种比较典型的方法有：交联法（包括自交联和外交联），但由于该方法的使用有很大的局限性，且存在乳液使用麻烦、涂膜质量难以保证的端，难以实现大规模的应用；共混法，即将丙烯酸乳液与有机聚合物的共混，是当前改善乳液性能的方法之一，但共混法对乳液性能的提高并不明显。从20世纪90年代开始在聚合工艺中出现了杂化乳液聚合，其典型工艺为将目标树脂（杂化树脂）溶解在丙烯酸单体中，经过预乳化至微乳（平均粒径500nm左右），再采用乳液聚合工艺得到成膜性能优良、稳定的杂化乳液。这些杂化乳液的性能远远高于两种树脂乳液共混，达到或接近化学结构改性的效果。目前国外已经出现的杂化乳液有聚氨酯/丙烯酸杂化乳液，醇酸/丙烯酸杂化乳液，环氧/丙烯酸杂化乳液等，都已申请专利并投入生产，国内的醇酸/内烯酸杂化乳液，环氧/内烯酸杂化乳液也有相关专利。新近合成的一种新型丙烯酸树脂/丙烯酸酯本体杂化乳液用于膨胀型防火涂料，其耐水性、发烟量、炭层强度皆有很大提高。",
+        "category": " Introduction"
+    },
+    {
+        "id": 973,
+        "chunk": "# 2.P-C-N体系中的新组分的研究及表面处理  \n\n现已研制出新型阻燃剂及补强剂，纳米复合材料阻燃剂。  \n\n加阻燃剂旨在增加涂层的阻燃能力，并在组分的配合下实现涂层的难燃化，最好还须具有一定的抑烟效果。纳米材料和纳米技术的发展，对高性能防火涂料的研制提供了有力支持。因为纳米粒子的特殊效应，赋予涂料许多优异的性能，如可以提高树脂本身的阻燃性、耐候性、耐水性等，提高阻燃剂的效率，从而减少涂料中防火助剂的用量，对提高防火涂料体系的耐候性、耐水性以及其他理化性能有极大的帮助。纳米氢氧化铝镁（LDH)，是一类具有层状结构的双羟基复合金属氧化物，是无机镁铝系功能材料。LDH片层上有羟基，层间有结晶水、碳酸根。由于这个特殊的组成和结构，LDH受热分解时吸收大量的热，能降低阻燃体系燃烧时的温度；分解释放出的水蒸气和二氧化碳能稀释、阻隔可燃气体；LDH经 $500{\\sim}600^{\\circ}\\mathrm{C}$ 高温分解后形成多孔、比表面积极大的碱性复合金属氧化物（LDO)，能吸附涂料燃烧生成的有害气体特别是酸性气体，同时还可吸附、凝集炭的极小微粒，起着抑烟作用。  \n\n通过TGA分析得知LDH与聚磷酸铵和季戊四醇、三聚氰胺膨胀阻燃体系在热降解反应时，LDH脱去层间水蒸气和二氧化碳及层面上的羟基后产生带有富碱性位置点与断裂的聚磷酸铵分子间发生反应，取代断裂的聚磷酸铵分子间的 $\\mathrm{{NH_{4}^{+}}}$ ，释放出 $\\mathrm{\\DeltaNH_{3}}$ 和 $\\mathrm{H_{2}O}$ ，在聚磷酸铵分子间形成交联，产生黏度更大的聚磷酸，因此在聚磷酸铵的裂解过程中可能减少氧化磷的释放，这样就能够生成和残留更多的黏稠状聚磷酸产生脱水、交联、成炭、隔热等作用，同时促进涂料脱水成炭，有利于阻燃性能的提高。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 974,
+        "chunk": "# 3.有待发展和解决的问题  \n\n(1）安全性问题薄型和超薄型防火涂料的膨胀阻燃体系大多为P-N体系，即其膨胀阻燃体系包括三大部分：酸源、碳源和气源。酸源即各种磷酸盐类，目前用得最多的为多聚磷酸铵（简称APP)、磷酸三聚氰胺等；碳源即各种含碳丰富的有机物如多元醇、氯化（或溴化）石蜡、淀粉等，目前用得最多的是季戊四醇或双季戊四醇，辅以少量氯化石蜡；气源是遇火后能放出不燃性气体，从而将碳源吹制成蜂窝状炭质层的物质，通常是各种胺类，如尿素、双氰胺、胍等，目前用量最多的是三聚氰胺，其成膜基料为各种有机树脂或乳液，如氯偏乳液等。从以上常见组分可以看出，防火涂料遇火产生膨胀从而对基材起到保护作用的同时，其阻燃成分有可能释放出诸如 $\\mathbf{NH_{3}}$ 、HCN、HX、 $\\mathbf{NO}_{2}$ + $C0$ 1 $\\bar{\\mathbf{Cl}}_{2}$ ， $\\mathbf{Br}_{2}$ 等有毒气体。如果这些气体的浓度超过了人体的耐受极限，便会对未逃离火场人员以及消防灭火人员产生危害，这是应引起重视的问题。而目前有关防火涂料的国家标准中并未考虑防火涂料遇火后产生有毒气体的种类、限量以及对人体的危害程度。  \n\n(2）防火涂料的耐久性包括两个方面的含义：一是涂层与基材的黏结力，即防火涂料是否容易随时间的延长而出现剥落、粉化等现象；二是涂层的防火性能是否持久，即经过若干年后其耐火极限是否明显降低，这一点的危害较之前者更具有隐蔽性，更应引起重视。由于室外环境条件较之室内更加恶劣和复杂，因此室外用钢结构防火涂料，特别是薄型钢结构防火涂料的耐久性问题尤为重要。虽然我国对某些室外用薄型钢结构防火涂料也做过有关耐久性方面的考察，但大多是将涂覆钢结构防火涂料的构件露天放置，经过 $2\\sim3$ 年观察其是否出现脱落、粉化、开裂等现象，而并未对其耐火极限重新考察。以有机组分为主的薄型和超薄型钢结构防火涂料无论是用于室外还是室内，其有机组分都可能产生分解、降解、老化等问题，从而使涂层剥落、粉化或失去防火性能。  \n\n(3）测试方法存在的问题钢结构防火涂料作为一类功能性涂料，其性能主要包括两大方面：一是理化、力学性能，它反映了涂料抵抗水及冷热变化、干湿变化、振动、荷载等各种环境因素的能力，以及其与基材的黏结牢固程度；二是其耐火性能，它表示涂料抵抗火灾侵袭的能力，以耐火极限表示，即将规定的构件，涂以规定厚度的防火涂料，按时间-温度标准曲线进行耐火试验，以构件从受火作用起至失去支持能力或完整性被破坏为止所用的时间，它是防火涂料的主要指标。耐火试验中，构件所加荷载和升温曲线是试验的两个重要条件。相同的构件，施加同样的荷载若采用不同的升温曲线所测得的耐火极限是不同的。我国防火涂料产品的耐火极限试验的升温曲线是按ISO834时间-温度标准曲线进行升温的，试验中是以木质纤维为燃烧介质，通常称为标准火；而在石化工程中是以油、气等为燃烧介质，通常称为烃类火。英国、美国、荷兰等许多国家，已分别制定了不司的烃类火升温曲线（见图3-11-15）。  \n\n![](images/df960386d3da40b8c3c32d13cefdc62b3442c5a084ec0809db28a1e851a1a673.jpg)  \n图3-11-15几种升温曲线比较1一荷兰Delfte国家研究院（烃类火）；2一英国Warrington研究中心（烃类火）；3一美孚石油公司（烃类火）；4一国际标准ISO834（标准火）  \n\n由图3-11-15可以看出，烃类火的温升要比标准火快得多。因此，同样耐火极限的防火涂料因其应用环境不同、受火类型不同，对基材的保护作用也就不同。如石化企业的火灾往往是由于设备和管道内的可燃介质发生漏、滴等，在遇火时而引发，属烃类火，因而其支承设备、管道的框架、支架和管架等钢结构材料所用的防火涂料的耐火极限应以烃类火的升温曲线来测试，才更接近实际。  \n\n(4）标准滞后的问题钢结构防火涂料标准的制定与执行往往由于各种原因而滞后于产品的生产与使用，这就使得防火涂料的生产与销售容易出现无据可依的局面，部分劣质产品鱼目混珠，为钢结构材料的安全使用带来隐患。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 975,
+        "chunk": "# 4.防火涂料的评估方法研究  \n\n产品的标准和评估方法给防火涂料的研究开发、推广应用和产品质量的监督管理提供了统一的技术依据，但由于材料在高温条件下的复杂性，单一的评价方法很难表征防火涂料的阻燃特性，特别是随着科学技术的发展，对阻燃材料的评价的目标是力求实验结果与实际情况之间具有较好的关联性。  \n\n为了全面地表征一项阻燃产品，从阻燃体系的各种原材料开始到阻燃制成品在不同环境条件下，在不同温度受热条件下，直至不同燃烧状态下的气相和凝聚相的分解产物都要进行分析，并进行与实际使用性能有关的评价，即要从阻燃产品的外观色泽开始，直至分解气体的毒性都要进行分析、鉴定和评价，因此，必须综合地运用各种分析测试方法。  \n\n先进的涂料检测技术目前对防火涂料的常规检测仅在于外观、颜色、光泽、黏度、表干时间、固体含量、硬度、冲击强度、黏结强度、耐水性等宏观检测来评价防火涂料性能。将各种仪器分析方法，例如X射线分析仪、X射线光电子光谱仪、自动电子光谱仪、离子微分析仪、傅里叶红外光谱、紫外光谱仪、红外光谱仪、核磁共振仪、色差计、锥形量热仪、热分析仪、扫描电镜等现代化仪器用于涂膜性能测试，可深入到内部测试其结构和界面状态，进行微观控制，这对研究产品的阻燃机理，产品配方的设计、研制、改性，产品烟和毒性气体的释放、火模型化研究以及高分子产品在阻燃领域的研究、开发和应用都具有很大的促进作用。  \n\n（1）锥形量热仪（CONE）与大型实验结果相关性好，是火灾科学中最具代表性的测试方法。可评价防火涂料产品和被保护材料的燃烧性和阻燃性，研究和评价烟及毒气的释放，优化防火涂料配方，研究产品和被保护材料的阻燃机理，确定被保护材料的轰燃时间及建立火灾模型。  \n\n(2）热分析法由于防火涂料的受热期间几乎处于不断变化的动态体系，因此可利用热分析技术研究防火涂料随温度的变化，其质量及热效应的变化情况，与其他测试技术联合可以分析阻燃体系的微观阻燃机理，为评价防火涂料的阻燃性能提供有效的手段并为选择合理配方提供重要的依据。  \n\n(3）红外光谱分析法依靠对光谱与化学结构关系的理解，通过与标准图谱的对照，灵活运用基团特征吸收峰及其变迁规律，逐步推导出所研究物质的正确结构。可用于确定涂料产品的结构和研究涂料涂层的阻燃历程，与热分析技术联用可用于研究防火涂料的微观阻燃机理。近年来红外光谱分析法在阻燃科学研究中占有越来越重要的地位。  \n\n(4）光电子能谱分析法通过分析物质的化学结合能以及材料在热燃烧时的热流量，对未知样品所含的元素进行鉴定，同时通过波形解析获得有关官能团种类和数量的信息。可结合红外光谱确定阻燃体系各物质的结构，确定不同组成的膨胀型阻燃剂形成炭层的成分及对阻燃效果的影响。  \n\n(5）扫描电镜分析法可进行微区成分分析，分辨率高、成像立体感强、视场大。可研究防火涂料及其燃烧后形成炭层的表观形貌、防火涂料各组分之间的相容性，研究防火涂料的炭层结构及其组成成分，研究不同组成的膨胀型阻燃体系对膨胀型防火涂料成炭过程的影响。  \n\n(6）X射线衍射分析法利用衍射波的两个基本特征——衍射线在空间分布的方位（衍射方向）和强度，与晶体内原子分布规律（晶体结构）的密切关系，来实现材料成分、结构分析。可进行原材料物相分析，防火涂料形成炭层的物相分析，与其他分析测试技术联用，研究防火涂料的反应历程。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 976,
+        "chunk": "# 5.防火涂料的检验评价方法  \n\n各类防火涂料产品的性能检测按下列国家标准进行。  \n\n$\\textcircled{1}$ 国家标准饰面型防火涂料通用技术条件（GB12441—2005）。  \n$\\textcircled{2}$ 公共安全行业标准电缆防火涂料通用技术条件（GA181—1998)。  \n$\\textcircled{3}$ 国家标准钢结构防火涂料（GB14907—2002）。  \n$\\textcircled{4}$ 钢结构防火涂料应用技术规范（CECS24：90）。  \n$\\textcircled{5}$ 公共安全行业标准建筑构件防火喷涂材料性能试验方法（GA110—1995)。  \n$\\textcircled{6}$ 公共安全行业标准预应力混凝土楼板防火涂料通用技术条件（GA98—1995)。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 977,
+        "chunk": "# 参考文献  \n\n［1］徐晓楠，周政懋，防火涂料，北京：化学工业出版社，2004.  \n［2］覃文清，李风．材料表面涂层防火阻燃技术，北京：化学工业出版社，2004.  \n［3］刘新，时虎，钢结构防腐蚀和防火涂装，北京：化学工业出版社，2005.  \n[4]王国建，许乾慰，邱军，防火涂料科学与技术，北京：中国石化出版社，2007.  \n[5]Handbook of Fire Retardant Coatings and Fire Testing Services.PennsylvaniaTechnomicPublishing Company，Inc，1994.  \n[6] 王华进，王贤明，刘登良，一种丙烯酸树脂膨胀型防火涂料的研制及应用，中国涂料，1996，（6）：40-42.  \n[7］徐峰，邹侯招，国内外无机防火涂料的应用与发展．化学建材，2002，（1)：15-17.",
+        "category": " References"
+    },
+    {
+        "id": 978,
+        "chunk": "# 道路交通标线涂料  \n\n道路交通标线涂料（以下简称标线涂料）是应用于交通领域里的专用涂料，用以划设引导汽车和行人流动的道路交通标线（以下简称标线)，标线的颜色主要是白色和黄色。利用标线涂料划设的各种醒目的标线所起到的标识作用，可以规范引导繁忙的车流和人流，使之各行其道，道路交通得以有序进行，提高了交通运输的流量和行车及行人的安全性，所以标线是道路交通管理中最基本、最经济、最有效的交通安全设施之一，此外，形形色色的标线划设在高速公路和城乡道路上，还起到美化道路的效果。  \n\n![](images/8f1966bbc823fc01e9a0a6486d00dac2e34b0aa9dc34a705703686c02f27bf90.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 979,
+        "chunk": "# 1.标线涂层应有鲜明的标识性  \n\n标线最主要的作用是规范和引导车辆和行人顺序前进，因此必须具有鲜明的标识性，依据国家标准GB2893—2008《安全色》对工业企业、交通运输、建筑、消防、仓库、医院及剧场等公共场所使用的信号和标志的明确规定，为使其具有鲜明的标识性，标线涂层的颜色应该满足GB2893—2008的要求。",
+        "category": " Introduction"
+    },
+    {
+        "id": 980,
+        "chunk": "# 2.标线涂层最好具有反光性  \n\n夜间行车，光靠车辆本身的照明所能看清的距离有限，如果标线涂层具有反光性能，司机就能看到前方更远距离的标线，按照标线所指示的方向顺利前进。国家标准GB/T16311—2005《道路交通标线质量要求和检测方法》规定：新划设的白色反光标线的逆反射系数应不小于150mcd/（lx·m²），黄色反光标线的逆反射系数应不小于100mcd/(lx·m²）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 981,
+        "chunk": "# 3.标线涂层的不粘胎干燥时间要短  \n\n道路施工的特殊性决定了在新修的道路上进行标线施工时，工期短；在维修的道路上施工时，要边施工，边通车。为了尽快开放交通，减少交通堵塞，希望标线涂层的不粘胎干燥时间要短。交通行业标准JT/T280—2004《路面标线涂料》规定：热熔标线涂料涂层的不粘胎干燥时间不得超过3min，溶剂普通型及水性普通型标线涂料涂层的不粘胎干燥时间不得超过15min。溶剂反光型和水性反光型标线涂料涂层的不粘胎干燥时间不得超过10min。双组分普通型、反光型、突起型标线涂料涂层的不粘胎干燥时间不得大于 $35\\mathrm{min}$ 0",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 982,
+        "chunk": "# 4.与路面的附着力好、经久耐磨、使用寿命长  \n\n标线涂层与路面应有较好的附着力与耐磨性，才能承受车轮的碾压及泥沙的冲刷和风沙  \n\n的拍打、磨损。标线的划设需要封闭道路、中断交通，标线的使用寿命越长，也就减少了标线重涂中断交通的次数。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 983,
+        "chunk": "# 5.良好耐候性  \n\n标线涂层是在露天环境下使用的，需经受得住各种恶劣气候的影响和冷热温度的变化及紫外线的辐射。",
+        "category": " Introduction"
+    },
+    {
+        "id": 984,
+        "chunk": "# 6.标线涂层要有一定的抗滑能力  \n\n标线划设在路面上，是路面的组成部分，汽车的车轮要在上面碾压，行人在其上行走，因此要求标线涂层要具有抗滑能力。",
+        "category": " Introduction"
+    },
+    {
+        "id": 985,
+        "chunk": "# 7.热熔标线涂层应有足够的抗压强度  \n\n热熔标线涂料的涂层厚达2.5mm，如果抗压强度不够，在重达几吨、几十吨甚至更重载重车的碾压下就有可能碎裂，并引起标线涂层逐步脱落；也有可能在夏季高温的作用下，被车轮碾压变形。根据交通行业标准JT/T280—2004《路面标线涂料》的规定：热熔标线涂层的抗压强度应 $\\geq12\\mathrm{{MPa}}$ 0  \n\n![](images/ab4a54ed343f5cb5f9f00b421513b029bc2bd390a7ef1aa13911b381876714b4.jpg)  \n\n我国现有标线涂料的主要品种见表3-12-1。  \n\n表3-12-1 我国现有标线涂料的主要品种  \n\n\n<html><body><table><tr><td>序号</td><td>种类</td><td colspan=\"2\">型号 玻璃珠的使用</td><td>状态</td><td>需量</td></tr><tr><td>1</td><td rowspan=\"3\">热熔</td><td>普通型</td><td>不用玻璃珠</td><td rowspan=\"3\">粉粒状</td><td>较少</td></tr><tr><td>2</td><td>反光型</td><td>涂料内含18%～25%玻璃珠，施工时再面撒玻璃珠</td><td>最多</td></tr><tr><td>3</td><td>突起型</td><td>涂料内含18%～25%玻璃珠，施工时再面撒玻璃珠</td><td>渐多</td></tr><tr><td>4</td><td rowspan=\"3\">溶剂</td><td>普通型</td><td>不用玻璃珠</td><td rowspan=\"2\">液态</td><td>较多</td></tr><tr><td>5</td><td>反光型</td><td>涂料内不含玻璃珠，施工时面撒玻璃珠</td><td>较少</td></tr><tr><td>6</td><td rowspan=\"2\">水性</td><td>普通型</td><td>不用玻璃珠</td><td></td></tr><tr><td>7</td><td>反光型</td><td>涂料内不含(或含18%～25%)玻璃珠，施工时再面撒玻璃珠</td><td></td><td>较少</td></tr><tr><td>8</td><td rowspan=\"3\">双组分</td><td>普通型</td><td>不用玻璃珠</td><td rowspan=\"3\">液态</td><td>渐多</td></tr><tr><td>9</td><td>反光型</td><td>涂料内不含（或含18%～25%）玻璃珠，施工时再面撒玻璃珠</td><td>较少</td></tr><tr><td>10</td><td>突起型</td><td>涂料内含18%～25%玻璃珠，施工时再面撒玻璃珠</td><td>渐多 较少</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 986,
+        "chunk": "# 第三节 标线涂料的组分、配方和生产",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 987,
+        "chunk": "# 一、热熔标线涂料  \n\n热熔标线涂料是由以热塑性树脂（C5石油树脂、改性松香树脂等）为主要成膜物，配以颜料、填料、反光材料、助剂等经混合机充分混匀制成，呈粉粒状。施工时，需加热到180～220℃熔融流动后，采用热熔划线机将涂料施工于路面，在自然环境条件下，3min内  \n\n固化成膜，属于物理于燥型。  \n\n目前，在日本、亚太地区、北美、欧洲等地区热熔标线涂料的用量占所需标线涂料的一半以上，我国用量高达70%以上。主要用在高速公路、国道、城市主干线等交通流量大的道路上。其特点是涂层的厚度可达2mm左右，使用寿命长，涂料中可预混玻璃珠，施工时再面撒玻璃珠，因而保证了标线的夜间反光性能良好，另外其标线涂层的不粘胎干燥时间短(3min以内)，涂料中不含有机溶剂，以上的这些优点使热熔标线涂料在标线涂料市场上有较高的市场占有率。但是该品种也有缺点，施工时需要加热至 $180\\sim220^{\\circ}C$ ，消耗能源，加热还存有安全隐患。此外，这类涂料的涂层较厚，被磨损的旧标线要重涂时，需要清除旧线，很费工时。",
+        "category": " Introduction"
+    },
+    {
+        "id": 988,
+        "chunk": "# 1.热熔标线涂料的原材料及其功能  \n\n热熔标线涂料的原材料及其功能见表3-12-2。  \n\n表3-12-2 热熔标线涂料的原材料及其功能  \n\n\n<html><body><table><tr><td>序号</td><td>组分</td><td>功能</td><td>原材料名称</td></tr><tr><td>1</td><td>树脂</td><td>作为涂层的主要成膜物，起粘接作用。施 工时，能将涂料的各组分粘接在一起，形成 均匀的涂层，同时又渗透到路面，使涂层牢 固地粘接在路面上</td><td>C5石油树脂；改性松香树脂；乙烯-醋酸乙 烯酯树脂（EVA）；聚乙烯蜡（PE）</td></tr><tr><td>2</td><td>颜料</td><td>给涂层着色，使涂层醒目，并具有遮盖力</td><td>钛白粉；氧化锌；锌钡白；包膜中铬黄；炭 黑；氧化铁黑</td></tr><tr><td>3</td><td>填料</td><td>充填涂料，使涂层丰满。改善涂料的施工 性能，提高涂层的强度和耐磨性等。降低涂 料的成本</td><td>不同粒径级配的碳酸钙；石英砂；滑石粉</td></tr><tr><td>4</td><td>增塑剂</td><td>用量很少，却能改善涂料的黏度以及涂层 的柔韧性和低温的抗裂性</td><td>邻苯二甲酸二辛酯(DOP);邻苯二甲酸二 丁酯（DBP）；矿物油；大豆色拉油；长油度醇 酸树脂</td></tr><tr><td>5</td><td>反光材料</td><td>使涂层具有逆反射性能。施工时面撒在 涂层的玻璃珠使施工后标线能即时反光，而 预混在涂料内的玻璃珠则在面撒玻璃珠磨 损脱落后，逐步被磨露出反光面，继续起到</td><td>玻璃珠</td></tr><tr><td>6</td><td>触变剂</td><td>反光作用 改变热熔涂料熔融状态的流动性</td><td>有机膨润土；气相二氧化硅</td></tr><tr><td>7</td><td>其他助剂</td><td>提高涂层的耐候性</td><td>紫外线吸收剂</td></tr><tr><td>8</td><td>防滑骨料</td><td>赋予涂层抗滑性能</td><td>粒径为1.2～4.0mm的陶瓷粒；石英砂； 烧铝矾土</td></tr></table></body></html>  \n\n从上表可以看出，树脂是标线涂料最关键的组分，其质量的好坏，直接影响到标线涂料的性能。热熔标线涂料大多选用的是 $C_{5}$ 石油树脂，其耐候性好，颜色浅，涂层柔韧性较好。20世纪80年代初，我国刚开始生产热熔标线涂料时，主要是用从日本进口的 $C_{5}$ 石油树脂以及国产的改性松香树脂。90年代初，中国和美国合资生产的 $C_{5}$ 石油树脂质量稳定，得到较多的应用，近几年一些国产 $C_{5}$ 石油树脂问世，并得到逐步应用。其价格较低，但还需在今后的应用中不断提高加热稳定性和贮存稳定性及色度等方面的性能，走好树脂国产化的道路。改性松香树脂价格较低、资源较丰富，所配制的涂料抗污性较好，但是耐候性差，涂层柔韧性较差，需在今后的应用中继续改进。  \n\n反光玻璃珠在我国有较多的厂家生产，不但能满足国内需要，而且还有部分出口。  \n其他原材料如钛白粉、填料、增塑剂等国内均有生产，能满足需要。  \n\n目前我国的热熔标线涂料基本采用刮涂的方法施工。  \n\n2.热熔反光标线涂料的参考配方（质量分数）  \n\n\n<html><body><table><tr><td>树脂</td><td>14%~20%</td><td>颜料</td><td>2%~7%</td></tr><tr><td>聚乙烯蜡（PE)</td><td>1%~3%</td><td>石英砂</td><td>15%～20%</td></tr><tr><td>乙烯-醋酸乙烯酯树脂（EVA）</td><td>1%~3%</td><td>玻璃珠</td><td>18%~25%</td></tr><tr><td>增塑剂</td><td>0.8%~1.8%</td><td>碳酸钙</td><td>余量</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 989,
+        "chunk": "# 3.热熔喷涂型反光标线涂料的参考配方  \n\n热熔喷涂型反光标线涂料是在上述热熔反光标线涂料的基础上，通过调整配方中的填料的粒径级配、树脂和增塑剂的用量，使热熔标线涂料的施工黏度达到喷涂所需要的黏度要求，然后通过划线机的离心辊高速甩出法或用喷枪低压喷涂法将涂料划设在路面上。喷涂的涂层厚度为1mm左右，涂层较刮涂法施工薄，因而适用于平整度较差的路面，如稀浆封层的路面，较薄的标线涂层划设在路面上，仍能基本保持道路表面的构造深度，从而使标线与路面的抗滑性能相近。  \n\n这种涂料的优点是它所划设的标线一旦被磨损，需要重涂的时候，磨薄的旧标线涂层不必清除，直接在旧线上施工即可，省去了清除旧标线涂层的繁重工序。  \n\n这种涂料的另一优点是用料省，约为刮涂施工的一半，施工的速度快一倍。实际使用中热熔喷涂型与热熔刮涂型的性能对比见表3-12-3。  \n\n表3-12-3 喷涂与刮涂的热熔涂料划设标线的性能价格比较  \n\n\n<html><body><table><tr><td>序号</td><td>项目</td><td>刮涂施工</td><td>喷涂施工</td></tr><tr><td>1</td><td>施工速度/(km/h)</td><td>1.5~2.0</td><td>3.0~4.0</td></tr><tr><td>2</td><td>抗滑性能</td><td>差</td><td>较好</td></tr><tr><td>3</td><td>二次涂覆难易程度</td><td>难(要清除旧标线）</td><td>易</td></tr><tr><td>4</td><td>涂膜厚度/mm</td><td>1.5~2.5</td><td rowspan=\"2\">0.7~1.2 2.0~2.5</td></tr><tr><td>5</td><td>涂料用量/（kg/m²）</td><td>4.5~5.0</td></tr></table></body></html>\n\n注：系试验数据，在实际现场施工时会有些出人，仅供参考。  \n\n热熔喷涂型反光标线涂料的参考配方（质量分数）如下：  \n\n\n<html><body><table><tr><td>树脂</td><td>20%~25%</td><td>颜料</td><td>2%~7%</td></tr><tr><td>聚乙烯蜡（PE)</td><td>1%~3%</td><td>石英砂</td><td>15%~20%</td></tr><tr><td>乙烯-醋酸乙烯酯树脂（EVA)</td><td>1%~3%</td><td>玻璃珠</td><td>18%~25%</td></tr><tr><td>增塑剂</td><td>1%~2%</td><td>碳酸钙</td><td>余量</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 990,
+        "chunk": "# 4.热熔突起反光标线涂料的参考配方  \n\n热熔突起反光标线涂料是在热熔反光标线涂料的基础上增加助剂，调整配方中的树脂与增塑剂的用量而制成的。施工时，采用振动标线划线机划设的标线涂层具有突起的圆形或方块形或棱条形等突起结构（见图3-12-1)，当汽车的轮胎碾压到这些突起部分时，就会使汽车产生轻微的振动和响声，引起司机的警觉。因此划设在弯道、坡道、长直道和隧道以及高架路的外侧边缘线和在公路的出入口、禁止超越路段等地段，能提示司机注意安全。一般的反光标线雨夜会被雨水淹没，标线就丧失了逆反射作用，而突起反光标线的突起部分却能露出水面，使标线在雨夜仍有逆反射作用，有利交通安全。据日本北海道警察局统计，划设了突起反光标线以后，交通安全事故的人员死亡率下降了 $77\\%$ 0  \n\n![](images/dff7d6ba82627c8404a639a81c376c646b7c393e8b3882398afa4a9fac27cb9a.jpg)  \n图3-12-1雨夜突起结构型反光标线与常规标线的反光示意图  \n\n热熔突起反光型标线涂料的参考配方（质量分数）如下：  \n\n<html><body><table><tr><td>树脂</td><td>14%~20%</td><td>石英砂</td><td>15%~20%</td></tr><tr><td>聚乙烯蜡（PE）</td><td>1%~3%</td><td>玻璃珠</td><td>18%~25%</td></tr><tr><td>乙烯-醋酸乙烯酯树脂（EVA）</td><td>1%~3%</td><td>助剂</td><td>适量</td></tr><tr><td>增塑剂</td><td>0.5%~1.0%</td><td>碳酸钙</td><td>余量</td></tr><tr><td>颜料</td><td colspan=\"3\">2%~7%</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 991,
+        "chunk": "# 5.热熔标线涂料的生产工艺  \n\n热熔标线涂料是由树脂、颜料、填料、增塑剂、反光材料等原材料混合而成，生产的设备是  \n\n混合机。生产的关键是将各种原材料混合均匀，不允许有偏析。其生产工艺流程见图3-12-2。  \n\n因为热熔标线涂的原材料有 $98\\%$ 以上是固体物质，仅少量的液态物质，在上述生产工艺流程中，要依次投料，液态增塑剂的称量和混合要特别注意，要把它们混合均匀。为使增塑剂能够均匀地分布在大量的粉料中，一般采用喷洒的方法。  \n\n减少粉尘污染是热熔标线涂料生产工艺流程中必须引起注意的重要环节，加强除尘，确保生产工人的健康。  \n\n![](images/7681d15800c6920d62b24f9f4d90b89a3a58b43682f296aacbe45c3faedeef37.jpg)  \n图3-12-2 热熔标线涂料生产工艺流程图",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 992,
+        "chunk": "# 二、溶剂标线涂料  \n\n溶剂标线涂料是由树脂（丙烯酸树脂、醇酸树脂、氯化橡胶等）配以颜料、填料、助剂和溶剂，经分散、研磨后制成，呈液态。施工时，划线机的喷枪将涂料高压无气喷涂到路面上，在自然环境条件下， $15\\mathrm{min}$ 内，待溶剂挥发干燥形成涂膜，属于物理干燥型。  \n\n早在20世纪70年代和80年代的初期，我国所划设的标线采用的溶剂涂料是酯胶漆，这种漆的标线涂层不耐磨，在交通流量大的路段上，使用寿命仅一个月左右。此后用过少量的环氧标线涂料，尔后逐步采用性能较好的氯化橡胶标线涂料，它具有涂层不粘胎、干燥时间短、与路面的附着性较好、标线涂层耐磨等优点，从而得到应用。80年代末，新开发出的热塑性丙烯酸树脂，以其耐候性较好、色泽浅、干燥快速和柔韧性较好等取得优势，在我国的溶剂标线涂料中获得广泛应用。  \n\n溶剂标线涂料在常温的晴天即可施工。涂料中的溶剂（约占 $30\\%$ ）经挥发干燥后，即形成标线涂层。施工方法既可刷涂也可辊涂。后来发展用有气的喷涂，但施工的涂层薄，施工速度比手工刷涂快速，但施工时雾化涂料对施工人员及周围的环境有较大的污染。直到80年代初期，才开始将高压无气喷涂应用于溶剂标线涂料的施工。该方法是将涂料预先加压，然后再喷涂，减少了施工时雾化涂料的污染，增加了涂层的厚度，并提高了施工效率。  \n\n溶剂普通型标线涂料划设的标线不反光，而溶剂反光型标线涂料划设的标线可具有反光功能，其特点是固体含量高达 $70\\%$ 以上，施工标线涂层的厚度可厚达 $0.8\\mathrm{\\mm}$ （湿膜)，从而使面撒的玻璃珠能够黏附在标线涂层上，在夜间形成反光。涂层厚，也就耐磨；溶剂含量少，对环境的污染就小。但是这种涂料的黏度较高，为了使涂料在施工时有合适的喷涂黏度，需要将涂料预热到 $60\\sim80^{\\circ}C$ 后再施工。",
+        "category": " Introduction"
+    },
+    {
+        "id": 993,
+        "chunk": "# 1.溶剂标线涂料的原材料及其功能  \n\n溶剂标线涂料的原材料及其功能见表3-12-4。  \n\n表3-12-4溶剂标线涂料的原材料及其功能  \n\n\n<html><body><table><tr><td>序号</td><td>组分</td><td>功能</td><td>原材料名称</td></tr><tr><td>1</td><td>合成树脂</td><td>是涂料的主要成膜物，起粘接作用。施工 时，形成均匀的涂层，并渗透到路面，牢固地粘 接在路面上</td><td>丙烯酸树脂；氯化橡胶；醇酸树脂；环氧 树脂</td></tr><tr><td>2</td><td>溶剂</td><td>调整涂料的黏度</td><td>甲苯；二甲苯；乙酸乙酯；乙酸丁酯；丙 酮；乙醇</td></tr><tr><td>3</td><td>颜料</td><td>给涂层着色，使涂层醒目，并具有遮盖力。 提高涂层的耐候性和机械强度</td><td>钛白粉；氧化锌；锌钡白；铬黄；氧化铁 红；大红；菁蓝、氧化铁黑</td></tr><tr><td>4</td><td>填料</td><td>充填涂料，使涂膜丰满。改变涂层的强度和 耐磨性等。降低涂料的成本</td><td>碳酸钙；滑石粉；沉淀硫酸钡</td></tr><tr><td>5</td><td>增塑剂</td><td>用量很少，改善涂层的柔韧性</td><td>邻苯二甲酸二辛酯（DOP）；邻苯二甲 酸二丁酯(DBP)；大豆色拉油；氯化石蜡</td></tr><tr><td>6</td><td>防沉淀剂</td><td>防止涂料在贮存过程中颜料、填料沉淀结块</td><td>有机膨润土；气相二氧化硅</td></tr><tr><td>7</td><td>分散剂</td><td>提高颜料的分散效果</td><td>聚氧乙烯（PEO）/聚氧丙烯（PPO)/聚氧 乙烯(PEO)三嵌段共聚物（F108）</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 994,
+        "chunk": "# 2.溶剂标线涂料的参考配方（质量分数）  \n\n树脂 $20\\%\\sim40\\%$ 分散剂 0.6%溶剂 10%\\~15% 防沉淀剂 0.3%增塑剂 2%\\~5% 滑石粉 12%颜料 10%\\~15% 碳酸钙 余量在设计配方时，只有颜基比合理，才能保证标线涂层的附着性和耐磨性。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 995,
+        "chunk": "# 3.溶剂标线涂料的生产工艺流程  \n\n使用的生产设备是高速分散机和砂磨机。生产过程是，先用高速分散机把颜料、填料和树脂、溶剂等混合均匀，然后再用砂磨机进一步将其混合研磨。生产工艺流程见图3-12-3。  \n\n![](images/3cce22bd2f3a98c9177425b64a98926be0e357d5ef950586503dae7f6b177186.jpg)  \n图3-12-3 落剂标线涂料的生产工艺流程图  \n\n由于溶剂标线涂料的生产过程中伴有大量的极易挥发的有机溶剂，易燃易爆，且污染环境，损害操作人员的身体健康，必须注意车间的通风，以利排除有机挥发溶剂。各种生产设备应尽量密封，各种电机、开关、照明设施等要备有防爆装置。  \n\n为了在调漆时便于添加防沉淀剂，可预先将其制成预凝胶。预凝胶的参考配方如下（质量分数)：  \n\n<html><body><table><tr><td>有机膨润土</td><td>10% 工业酒精</td><td>3%</td></tr><tr><td>甲苯</td><td>87% 分散剂</td><td>0.3%</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 996,
+        "chunk": "# 三、水性标线涂料  \n\n现有的水性标线涂料是以水为分散介质，以丙烯酸聚合物乳液为成膜物，再配上颜料、填料、助剂等组成，经物理干燥成膜。它解决了常温溶剂标线涂料中因含有挥发性有机化合物（VOC）含量高的问题，从而保护了环境。它源于20世纪80年代的美国，当时颁布了新的环保法规，为达到环保要求而研制成功的，在美国和加拿大应用较多。近年来，我国也研制开发了水性标线涂料，并开始用在高速公路和城市道路上。",
+        "category": " Introduction"
+    },
+    {
+        "id": 997,
+        "chunk": "# 1.水性标线涂料的原材料及其功能  \n\n水性标线涂料的原材料及其功能见表3-12-5。  \n\n表3-12-5水性标线涂料的原材料及其功能  \n\n\n<html><body><table><tr><td>序号</td><td>组分</td><td>功能</td><td>原材料名称</td></tr><tr><td>１</td><td>乳液</td><td>涂料的主要成膜物并起粘接作用。施工时，能 将涂料的各组分粘接在一起，形成均匀的涂层，同 时又渗透到路面，使涂层牢固地粘接在路面上</td><td>丙烯酸聚合物乳液</td></tr><tr><td>2</td><td>颜料</td><td>给涂层着色，使涂层醒目，并具有遮盖力</td><td>钛白粉；氧化锌；锌钡白；铬 黄；氧化铁红；氧化铁黑；献菁蓝</td></tr><tr><td>3</td><td>填料</td><td>充填涂料，使涂膜丰满。改变涂料的施工性能， 涂层的强度和耐磨性等。降低涂料的成本</td><td>碳酸钙；石英粉；滑石粉</td></tr><tr><td>4</td><td>增稠剂</td><td>控制涂料黏度，调节流变性</td><td>羟乙基纤维素</td></tr><tr><td>5</td><td>分散剂</td><td>润湿和稳定颜料、填料的分散</td><td>阴离子分散剂</td></tr><tr><td>6</td><td>消泡剂</td><td>控制泡沫，改善涂料性能</td><td>矿物油类</td></tr><tr><td>7</td><td>表面活性剂</td><td>稳定涂料体系，润湿底材</td><td>非离子型CF-10;X-405</td></tr><tr><td>8</td><td>成膜助剂</td><td>帮助聚合物成膜</td><td>Texanol@</td></tr><tr><td>9</td><td>反光材料</td><td>使标线涂层具有逆反射性能</td><td>玻璃珠</td></tr><tr><td>10</td><td>其他助剂</td><td>提高涂层的耐候性</td><td>紫外线吸收剂</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 998,
+        "chunk": "# 2.水性标线涂料的参考配方（质量分数）  \n\n乳液 $30\\%\\sim40\\%$ 石英粉 10%\\~15% 水 $10\\%\\approx30\\%$ 乙醇 1%\\~3% 表面活性剂 $0.2\\%\\sim0.3\\%$ 成膜助剂 1.5%\\~3.0% 消泡剂 $0.3\\%\\approx0.5\\%$ 增稠剂 $0.1\\%\\approx0.5\\%$ 颜料 $5\\%\\cdots15\\%$ 防霉防腐剂 $0.1\\%\\sim0.3\\%$ 碳酸钙 40%\\~50% 氨水(工业氨水) 调节pH为 $9.5\\sim10$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 999,
+        "chunk": "# 3.水性标线涂料的生产工艺流程  \n\n生产过程主要是用高速分散机，把乳液、颜料、填料、助剂等充分搅拌分散均匀。具体  \n\n![](images/cd2bc70168aa466fa80e23ccbfa6b8d2bf91240c5bc8f19fbb4c1172bd79b846.jpg)  \n图3-12-4水性标线涂料的生产工艺流程  \n\n水性标线涂料的生产过程中，最关键的是控制好分散速度和合适的投料顺序，并要准确称量用量较少的助剂。投料的顺序是在搅拌的状态下，先加人乳液、水、表面活性剂及消泡剂，随后再加颜料、填料等，使之充分搅拌分散均匀。在调漆过程中，缓慢加人成膜助剂、增稠剂、防霉防腐剂、乙醇等，最后加氨水调整涂料的 $\\mathbf{\\bar{pH}}$ 中",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1000,
+        "chunk": "# 四、双组分标线涂料  \n\n双组分标线涂料是由树脂、颜料、填料、助剂等制成涂料的主要部分，施工时，加人按一定比例的固化剂调和后，树脂与固化剂发生交联反应，化学交联成膜。这种标线涂层具有与路面较好的附着力，与玻璃珠有较强的粘接强度，耐磨性能好等优点。标线的不粘胎干燥时间（即涂料的固化时间）与涂层的厚度无关，而是取决于固化剂的用量以及施工环境的温度等因素。  \n\n双组分标线涂料常用的成膜物树脂类型有：活性丙烯酸树脂、环氧树脂、聚氨酯树脂等，固化剂有过氧化二苯甲酰（BPO）、低分子聚酰胺树脂、活性脂肪族多元胺等。  \n\n目前应用较多的以活性丙烯酸树脂为成膜物的喷涂型双组分标线涂料的参考配方（质量分数）如下：  \n\nA组分 B组分 树脂Degaroute $\\mathbb{G}\\mathbb{G}\\mathbb{G}1$ $40\\%$ Degaroute 663 $40\\%$ 增塑剂Degaroute@W3 $2\\%$ Degaroute? W3 $2\\%$ Disperbyk 163 $0.3\\%$ Disperbyk 163 $0.3\\%$ Byk 410 $0.1\\%$ Byk 410 $0.1\\%$ 颜料 $2\\%\\sim10\\%$ 颜料 2%\\~10% 细填料 $47.5\\%$ 细填料 47.6%  \n\nA组分和B组分的比例是 $1:1$ 。施工前，B组分需添加 $4\\%$ 固化剂过氧化二苯甲酰（BPO)。喷涂的标线厚度约 $0.6\\mathrm{mm}$ （干膜)。  \n\n使用活性丙烯酸树脂作为基料还可以配制双组分突起型反光标线涂料，所划设的标线能使汽车产生振动感，雨夜反光效果好。  \n\n喷涂型双组分标线涂料的生产工艺流程如图3-12-5所示，生产过程中要注意将A组分和B组分严格分开，固化剂过氧化二苯甲酰易燃易  \n\n![](images/d6f61a69391dd656230acefa16c2311f9406672f41900c8ca8bbde445122cac1.jpg)  \n图3-12-5 双组分标线涂料的生产工艺流程  \n\n爆，要妥善保管。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1001,
+        "chunk": "# 五、路面防滑涂料  \n\n路面本身就具有一定的抗滑能力，而在路面铺设防滑涂料可提高路面的抗滑能力，可铺设在一些事故多发地段和弯道、上下坡道及停车场、高速公路收费站等。其颜色可采用醒目的红色，还有蓝色和绿色等，以引起司机的警觉，注意减速行驶，明显提高交通安全性。图3-12-6为铺设在北京南三环路上的防滑路面。  \n\n![](images/f5cd7d28375abc25372251d8f5b6be06380fc554bba37265e9b7f1a8271e5d53.jpg)  \n图3-12-6 铺设在北京南三环路上的防滑路面  \n\n路面防滑涂料由基料及防滑骨料组成。基料可以是石油树脂、改性松香树脂、丙烯酸树脂、丙烯酸聚合物乳液等，其成膜机理为物理干燥型。如果基料是双组分环氧树脂或活性丙烯酸树脂及聚氨酯等，则需加固化剂才能成膜，成膜的机理是化学交联型。防滑骨料可以是陶瓷颗粒、金刚砂、烧铝矾土、石英砂等耐磨硬质材料。骨料的粒径一般不大于4mm，涂层的厚度一般为2～4mm。路面防滑涂料铺设的防滑涂层的抗滑能力用摆式摩擦系数测定仪测量，单位是BPN。涂层的抗滑能力分为普通防滑型（45～55BPN)；中等防滑型（55～70BPN)；高防滑型（ $\\geq70$ BPN）三个等级。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1002,
+        "chunk": "# 第四节 标线涂料的标准和检测  \n\n要生产出优质的标线涂料，就要在严把原材料质量关的基础上，做好生产全过程的质量控制，做好每一项性能测试，控制好涂料的各项性能指标。还要通过路用试验来验证配方的合理性和实用性。鉴于我国的幅员辽阔，气候变化多端，使用条件各异，北方地区使用效果良好的标线涂料不一定适用于南方地区，同样的西部干旱地区的标线涂料不一定适用于东部湿热地区，为此就要对标线涂料的某些性能指标做出相应的调整，以满足不同地区、不同季节、不同使用条件的需要。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1003,
+        "chunk": "# 一、标线涂料的标准  \n\n目前，我国标线涂料的标准为交通行业标准JT/T280—2004《路面标线涂料》及公共安全行业标准GA/T298—2001《道路标线涂料》。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1004,
+        "chunk": "# 1.热熔标线涂料的标准  \n\n热熔标线涂料的交通行业标准和公共安全行业标准如表3-12-6和表3-12-7所列。  \n\n表3-12-6 热熔标线涂料的交通行业标准  \n\n\n<html><body><table><tr><td colspan=\"2\">检测项目</td><td colspan=\"2\">普通型</td><td>反光型</td><td>突起型</td></tr><tr><td colspan=\"2\">密度/（g/cm²）</td><td colspan=\"4\">1.8~2.3</td></tr><tr><td colspan=\"2\">软化点/C</td><td colspan=\"4\">90~125 ≥100</td></tr><tr><td colspan=\"2\">涂膜外观</td><td colspan=\"4\">干燥后，应无皱纹、斑点、起泡、裂纹、脱落、粘胎现象，涂膜的颜色和外观应与标准 板差别不大</td></tr><tr><td colspan=\"2\">不粘胎干燥时间/min</td><td colspan=\"4\">≤3</td></tr><tr><td rowspan=\"2\">色度性能（45°/0°）</td><td>白色 黄色</td><td colspan=\"4\">涂料的色品坐标和亮度因数应符合表3-12-13和图3-12-7规定的范围</td></tr><tr><td></td><td colspan=\"4\">23℃±1℃时，≥12； ≥12</td></tr><tr><td colspan=\"2\">耐磨性（200r/1000g后减重）/mg</td><td colspan=\"4\">50℃±2℃时，≥2 ≤80（JM-100橡胶砂轮）</td></tr><tr><td colspan=\"2\">耐水性</td><td colspan=\"4\">在水中浸24h应无异常现象</td></tr><tr><td colspan=\"2\">耐碱性</td><td colspan=\"4\">在氢氧化钙饱和溶液中浸24h无异常现象</td></tr><tr><td colspan=\"2\">玻璃珠含量/%</td><td colspan=\"4\">18~25</td></tr><tr><td colspan=\"2\">流动度/s</td><td colspan=\"4\">35±10</td></tr><tr><td colspan=\"2\">涂层低温抗裂性</td><td colspan=\"4\">一10℃保持4h，室温放置4h为一个循环，连续做三个循环后应无裂纹</td></tr><tr><td colspan=\"2\">加热稳定性</td><td colspan=\"4\">200～220℃在搅拌状态下保持4h，应无明显泛黄、焦化、结块等现象</td></tr><tr><td colspan=\"2\">人工加速耐候性</td><td colspan=\"4\">经人工加速耐候性试验后，试板涂层不产生龟裂、剥落；允许轻微粉化和变色，但色 品坐标应符合表3-12-13和图3-12-7规定的范围，亮度因数变化范围应不大于原样板</td></tr></table></body></html>  \n\n表3-12-7 热熔标线涂料的公共安全行业标准  \n\n\n<html><body><table><tr><td colspan=\"2\">种类</td><td colspan=\"2\">热熔型涂料</td></tr><tr><td colspan=\"2\">项目</td><td>A B</td></tr><tr><td colspan=\"2\">相对密度</td></tr><tr><td>软化点/℃</td><td colspan=\"2\">90～140</td></tr><tr><td>涂层颜色及外观</td><td>涂层冷却后应无皱纹、斑点、起泡、裂纹、脱落及表面无发黏等现象，颜色范围应 符合GB/T8416的规定</td></tr><tr><td>不粘胎干燥时间/min</td><td colspan=\"2\">≤3</td></tr><tr><td>抗压强度/Pa</td><td colspan=\"4\">≥1.2×10²</td></tr><tr><td>耐磨性/mg</td><td colspan=\"4\">≤60(200r/1000g磨耗减重）</td></tr><tr><td>白色度</td><td colspan=\"4\">≥65 在氢氧化钙饱和溶液中浸泡18h应无开裂、起泡、孔隙、剥离、起皱及严重变色等</td></tr><tr><td colspan=\"2\">耐碱性</td><td colspan=\"2\">异常现象</td></tr><tr><td>加热残留分/%</td><td colspan=\"2\">≥99</td></tr><tr><td rowspan=\"2\">逆反射系数/[mcd/（lx·m2）]</td><td>白色</td><td>≥200</td></tr><tr><td>黄色</td><td>≥100</td></tr></table></body></html>\n\n注：A一普通型热熔标线涂料；B一反光型热熔标线涂料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1005,
+        "chunk": "# 2.溶剂标线涂料的标准  \n\n溶剂标线涂料的交通行业标准和公共安全行业标准见表3-12-8和表3-12-9。  \n\n表3-12-8 溶剂标线涂料的交通行业标准  \n\n\n<html><body><table><tr><td colspan=\"2\">检测项目</td><td>普通型</td><td colspan=\"2\">反光型</td></tr><tr><td colspan=\"2\">容器中状态</td><td colspan=\"3\">应无结块、结皮现象，易于搅匀</td></tr><tr><td colspan=\"2\">黏度</td><td>≥100s(涂-4杯)</td><td></td><td>80~120(KU值）</td></tr><tr><td colspan=\"2\">密度/（g/cm3）</td><td>≥1.2</td><td colspan=\"2\">≥1.3</td></tr><tr><td colspan=\"2\">施工性能</td><td colspan=\"5\">空气或无空气喷涂（或刮涂)施工性能良好</td></tr><tr><td colspan=\"2\">加热稳定性</td><td colspan=\"5\">应无结块、结皮现象，易于搅匀，KU值不小于140</td></tr><tr><td colspan=\"2\">涂膜外观</td><td colspan=\"5\">干燥后，应无发皱、泛花、起泡、开裂、粘胎等现象，涂膜颜色和外观应与标准板差 异不大</td></tr><tr><td colspan=\"2\">不粘胎干燥时间/min</td><td colspan=\"3\">≤15</td><td>≤10</td></tr><tr><td rowspan=\"2\">遮盖率/%</td><td>白色</td><td colspan=\"2\"></td><td colspan=\"2\">≥95</td></tr><tr><td>黄色 白色</td><td colspan=\"3\">≥80</td></tr><tr><td rowspan=\"2\">色度性能（45°/0°)</td><td>黄色</td><td colspan=\"3\">涂料的色品坐标和亮度因数应符合表3-12-13和图3-12-7规定的范围</td></tr><tr><td>耐磨性（200r/1000g后减重）/mg</td><td colspan=\"3\">≤40(JM-100橡胶砂轮）</td></tr><tr><td colspan=\"3\">耐水性</td><td colspan=\"3\">在水中浸24h应无异常现象</td></tr><tr><td>耐碱性</td><td colspan=\"2\"></td><td colspan=\"3\">在氢氧化钙饱和溶液中浸24h应无异常</td></tr><tr><td>附着性(划圈法)</td><td colspan=\"2\"></td><td colspan=\"3\">≤4级</td></tr><tr><td>柔韧性/mm</td><td colspan=\"2\"></td><td colspan=\"3\"></td></tr><tr><td>固体含量/%</td><td colspan=\"2\"></td><td>≥60</td><td colspan=\"2\">5 ≥65</td></tr></table></body></html>  \n\n表3-12-9 溶剂标线涂料的公共安全行业标准  \n\n\n<html><body><table><tr><td colspan=\"2\">种类</td><td colspan=\"3\">常温型标线涂料</td><td colspan=\"3\">加热型标线涂料</td></tr><tr><td colspan=\"2\">项目</td><td>A</td><td></td><td>B</td><td>A</td><td colspan=\"2\">B</td></tr><tr><td colspan=\"2\">容器中状态</td><td colspan=\"6\">应无结块、结皮现象，易于揽匀</td></tr><tr><td colspan=\"2\">稠度(KU值)</td><td colspan=\"2\">≥60</td><td colspan=\"4\">≥75</td></tr><tr><td colspan=\"2\">施工性能</td><td colspan=\"4\">刷涂、空气或无空气喷涂施工性能良好</td><td colspan=\"3\">加热至40～60C时无空气喷涂施工性能良好</td></tr><tr><td colspan=\"2\">漆膜颜色和外观</td><td colspan=\"6\">应无发皱、泛花、起泡、开裂、发粘等现象，颜色范围应符合GB/T8416的规定</td></tr><tr><td colspan=\"2\">不粘胎干燥时间/min</td><td colspan=\"6\">≤15 ≤10</td></tr><tr><td rowspan=\"2\">遮盖力/（g/m²）</td><td>白色</td><td colspan=\"6\">≤190</td></tr><tr><td>黄色</td><td colspan=\"6\">≤200</td></tr><tr><td colspan=\"2\">固体含量/%</td><td colspan=\"6\">≥60</td></tr><tr><td colspan=\"2\">附着力(划圈法)</td><td colspan=\"6\">≤5级 ≤4级</td></tr><tr><td colspan=\"2\">耐磨性/mg</td><td colspan=\"6\">≤40(200r/1000g磨耗减重）</td></tr><tr><td colspan=\"2\">耐水性</td><td colspan=\"6\">漆膜经蒸馏水24h浸泡后应无开裂、起泡、孔隙、起皱等异常现象</td></tr><tr><td colspan=\"2\">耐碱性</td><td colspan=\"6\">在氢氧化钙饱和溶液中浸泡18h，应无开裂、起泡、孔隙、剥离、起皱及严重变色等异常现象</td></tr><tr><td colspan=\"2\">漆膜柔韧性</td><td colspan=\"6\">经5mm直径圆棒屈曲试验，应无龟裂、剥离等异常现象 玻璃珠应均匀附</td></tr><tr><td colspan=\"2\">玻璃珠撒布试验</td><td></td><td>在漆膜上 玻璃珠应有90%</td><td></td><td>一</td><td colspan=\"2\">玻璃珠应均匀附在漆膜上 玻璃珠应有90%以上牢固</td></tr><tr><td colspan=\"2\">玻璃珠牢固附着率</td><td></td><td></td><td>以上牢固附着率</td><td></td><td colspan=\"2\">附着率</td></tr><tr><td>逆反射系数 /[mcd/(lx·m²）]</td><td>白色</td><td></td><td>≥200</td><td></td><td></td><td colspan=\"2\">≥200</td></tr><tr><td></td><td>黄色</td><td></td><td>≥100</td><td></td><td></td><td colspan=\"2\">≥100</td></tr></table></body></html>\n\n注：A—普通型；B一反光型。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1006,
+        "chunk": "# 3.双组分标线涂料的交通行业标准  \n\n双组分标线涂料的交通行业标准见表3-12-10。  \n\n表3-12-10双组分标线涂料的交通行业标准  \n\n\n<html><body><table><tr><td colspan=\"2\"></td><td>普通型</td><td>反光型</td><td colspan=\"3\">突起型</td></tr><tr><td colspan=\"2\">容器中状态</td><td colspan=\"5\">应无结块、结皮现象，易于搅匀</td></tr><tr><td colspan=\"2\">密度/（g/cm）</td><td colspan=\"5\">1.5~2.0</td></tr><tr><td colspan=\"2\">施工性能</td><td colspan=\"5\">按生产厂的要求，将A、B组分按一定比例混合揽拌均匀后，喷涂、刮涂施工性能良好</td></tr><tr><td colspan=\"2\">涂膜外观</td><td colspan=\"5\">涂膜固化后应无皱纹、斑点、起泡、裂纹、脱落、粘贴等现象，涂膜颜色与外观应 与样板差别不大</td></tr><tr><td colspan=\"2\">不粘胎干燥时间/min</td><td colspan=\"5\">≤35</td></tr><tr><td colspan=\"2\">白色 色度性能（45°/0°) 黄色</td><td colspan=\"5\">涂膜的色品坐标和亮度因数应符合表3-12-13和图3-12-7规定的范围</td></tr><tr><td colspan=\"2\">耐磨性（200r/1000g后减重）/mg</td><td colspan=\"5\">≤40(JM-100橡胶砂轮）</td></tr><tr><td colspan=\"2\">耐水性</td><td colspan=\"5\">在水中浸24h应无异常现象</td></tr><tr><td colspan=\"2\">耐碱性</td><td colspan=\"5\">在氢氧化钙饱和溶液中浸24h应无异常</td></tr><tr><td colspan=\"2\">附着性（划圈法）</td><td colspan=\"5\">≤4级（不含玻璃珠）</td></tr><tr><td colspan=\"2\">柔韧性/mm</td><td colspan=\"2\">5(不含玻璃珠)</td><td></td><td></td></tr><tr><td colspan=\"2\">玻璃珠含量/%</td><td colspan=\"2\"></td><td>18~25</td><td>18~25</td></tr><tr><td colspan=\"2\">人工加速耐候性</td><td colspan=\"5\">经人工加速耐候性试验后，试板涂层不允许产生龟裂、剥落；允许轻微粉化和变色，但 色品坐标应符合表3-12-13和图3-12-7规定的范围，亮度因数变化范围应不大于原样板 亮度因数的20%</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1007,
+        "chunk": "# 4.水性标线涂料的交通行业标准  \n\n水性标线涂料的交通行业标准见表3-12-11。  \n\n表3-12-11 水性标线涂料的交通行业标准  \n\n\n<html><body><table><tr><td colspan=\"2\">检测项目</td><td>普通型</td><td>反光型</td></tr><tr><td colspan=\"2\">容器中状态</td><td colspan=\"2\">应无结块、结皮现象，易于搅匀</td></tr><tr><td colspan=\"2\">黏度</td><td>≥70(KU值)</td><td>80～120(KU值)</td></tr><tr><td colspan=\"2\">密度/（g/cm3）</td><td>≥1.4</td><td>≥1.6</td></tr><tr><td colspan=\"2\">施工性能</td><td colspan=\"2\">空气或无气喷涂(或刮涂)施工性能良好</td></tr><tr><td colspan=\"2\">漆膜外观</td><td colspan=\"2\">应无发皱、泛花、起泡、开裂、粘贴等现象，涂膜颜色和外观应与样板差异不大</td></tr><tr><td colspan=\"2\">不粘胎干燥时间/min</td><td>≤15 ≤10</td></tr><tr><td rowspan=\"2\">遮盖率/%</td><td>白色</td><td colspan=\"2\">≥95</td></tr><tr><td>黄色</td><td colspan=\"2\">≥80</td></tr><tr><td rowspan=\"2\">色度性能（45°/0°）</td><td>白色</td><td colspan=\"2\" rowspan=\"2\">涂料的色品坐标和亮度因数应符合表3-12-13和图3-12-7规定的范围</td></tr><tr><td>黄色</td></tr><tr><td colspan=\"2\">耐磨性（200r/1000g后减重）/mg</td><td colspan=\"2\">≤40(JM-100橡胶砂轮）</td></tr><tr><td colspan=\"2\">耐水性 耐碱性</td><td colspan=\"2\">在水中浸24h应无异常现象</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>检测项目</td><td>普通型</td><td>反光型</td></tr><tr><td>冻融稳定性</td><td colspan=\"2\">在一5℃士2℃的条件下放置18h后。立即置于23℃士2℃条件下放置 6h为一个周期，三个周期后应无结块、结皮现象，易于搅匀</td></tr><tr><td>早期耐水性</td><td colspan=\"2\">在温度为23℃±2℃、湿度为90%士3%的条件下，实干时间≤120min</td></tr><tr><td>附着性（划圈法）</td><td>≤5级</td><td></td></tr><tr><td>固体含量/%</td><td>≥70</td><td>≥75</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1008,
+        "chunk": "# 二、标线涂料特定的检测项目",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1009,
+        "chunk": "# 1.不粘胎干燥时间  \n\n为了使标线施工后能尽快开放交通，要求涂层能快速干燥。JT/T280—2004《路面标线涂料》规定的各种类型的标线涂层不粘胎时间如表3-12-12所示。  \n\n表3-12-12各种类型的标线涂层不粘胎干燥时间 单位：min  \n\n\n<html><body><table><tr><td colspan=\"2\">溶剂</td><td rowspan=\"2\">热熔</td><td rowspan=\"2\">双组分</td><td colspan=\"2\">水性</td></tr><tr><td>普通型</td><td>反光型</td><td>普通型</td><td>反光型</td></tr><tr><td>≤15</td><td>≤10</td><td>≤3</td><td>≤35</td><td>≤15</td><td>≤10</td></tr></table></body></html>  \n\n标准规定的测试方法是：在水泥石棉板（ $\\mathrm{200mm\\times150mm\\times5mm}$ ）上涂布厚 $300\\mu\\mathrm{m}$ 宽 $80\\mathrm{mm}$ 的带状涂层，用不粘胎时间测定仪测不粘胎干燥时间。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1010,
+        "chunk": "# 2.抗压强度  \n\n$2\\mathrm{mm}$ 左右厚的热熔型标线涂层要承受各种车辆的频繁的碾压以及夏季高温的考验，必须有足够的抗压强度防止涂层被压碎、脱落及变形。标准规定的测试方法是：将熔融的热熔涂料浇制成 $20\\mathrm{{mm}\\times20\\mathrm{{mm}\\times20\\mathrm{{mm}}}}$ 抗压试块三块，在标准试验温度下放置$24\\ln$ 后做抗压实验，用精度不低于0.5级的电子万能材料试验机进行测定，以适当的速度预加负荷 $10N$ ，然后以 $30\\mathrm{{mm}/\\mathrm{{min}}}$ 速度加载，并开始记录试验机压头的位移，直到试块破坏为止，记录破坏时的荷载，计算抗压强度。标准规定：热熔普通型和热熔反光型的抗压强度应 $\\geq12\\ensuremath{\\mathrm{MPa}}$ ；热熔突起型在 $23^{\\circ}C\\pm1^{\\circ}C$ 时应 $\\geq12\\ensuremath{\\mathrm{MPa}}$ ，在 $50^{\\circ}C\\pm2^{\\circ}C$ 时应 $\\geq2\\mathrm{MPa}$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1011,
+        "chunk": "# 3.玻璃珠含量  \n\n如表3-12-6所示，热熔反光标线涂料内应含有 $18\\%\\sim25\\%$ 的玻璃珠，以确保使用中的标线能够持续反光。标准规定测定热熔反光标线涂料中的玻璃珠含量的方法是：用醋酸乙酯与二甲苯混合溶剂溶解除去涂料中的有机部分———树脂等，然后用稀盐酸溶解除去涂料中的无机部分（如填料、颜料等)，直到涂料中的玻璃珠和石英砂被完全分离出来，洗净、烘干、除去混人的石英砂，称量所含玻璃珠，计算玻璃珠含量。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1012,
+        "chunk": "# 4.低温抗裂性  \n\n由于热熔标线涂料施工的标线涂层较厚，约 $2\\mathrm{mm}$ ，在低温条件下容易开裂，需要做低温抗裂性试验，标准规定：试样在 $-10^{\\circ}\\mathbb{C}\\pm2^{\\circ}\\mathbb{C}$ 低温条件下保持4h，然后在室温下放置4h，以此为一个循环，连续做三个循环后应无裂纹。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1013,
+        "chunk": "# 5.加热稳定性  \n\n热熔标线涂料在施工时需要加热至180～220℃，若涂料中的树脂耐高温差，经长时间的高温加热就会分解变色，从而影响涂料的色度性能及其他性能。标准规定：热熔标线涂料在 $200{\\sim}220^{\\circ}\\mathrm{C}$ 搅拌情况下保持4h后，应无明显泛黄、焦化和结块现象。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1014,
+        "chunk": "# 6.冻融稳定性  \n\n冻融稳定性是检测水性标线涂料在低于 $0^{\\circ}C$ 的环境条件下的贮存稳定性，标准规定：试样在一 $5^{\\circ}C\\pm2^{\\circ}C$ 的加盖铁筒内保持 $18\\mathrm{h}$ ，然后立即在 $23^{\\circ}C\\pm2^{\\circ}C$ 条件下放置6h，以此为一个循环，连续做三个循环后应无结块、结皮现象，易于搅匀。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1015,
+        "chunk": "# 7.早期耐水性  \n\n水性标线涂料的早期耐水性是指刚施工后，未完全干燥涂层的耐水性。标准规定的检测方法是：将试样放在温度为 $23^{\\circ}C\\pm2^{\\circ}C$ 、相对湿度为 $90\\%\\pm3\\%$ 的高低温湿热试验箱内，每隔 $5\\ \\mathrm{min}$ 用指触法测涂层的实干时间，不超过 $120\\ \\mathrm{min}$ 为合格。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1016,
+        "chunk": "# 8.色度性能  \n\n标线涂料的颜色主要是白色和黄色，其色度性能按GB2893《安全色》检测，所用的仪器是 $\\mathbb{D}_{65}$ 标准光源照明，观察条件为 $45^{\\circ}/0^{\\circ}$ 的色彩色差计，检测的结果用色品坐标和亮度因数表示。标准规定：所测的色品坐标 $(x,y)$ 值应落在图3-12-7中的框内。  \n\n![](images/a061b434f51874507018d00b1deb17db39b2c52864d885873a924e98f708dbe7.jpg)  \n图3-12-7 标线涂层的色度范围图  \n\n标准规定：白色标线涂料的亮度因数 $\\geqslant0.75$ ；黄色标线涂料的亮度因数 $\\geqslant0,45$ （见表3-12-13)。  \n\n表3-12-13标线涂料颜色范围（标准照明体D65，照明观测条件45°/0°，视场角2°）  \n\n\n<html><body><table><tr><td rowspan=\"2\">颜色</td><td rowspan=\"2\"></td><td colspan=\"8\">色 品 坐 标</td><td rowspan=\"2\">亮度因数</td></tr><tr><td></td><td>y</td><td>工</td><td></td><td>I</td><td></td><td>工</td><td></td></tr><tr><td rowspan=\"2\">普通材料色</td><td>白</td><td>0.350</td><td>0.360</td><td>0.300</td><td>0.310</td><td>0.290</td><td>0.320</td><td>0.340</td><td>0.370</td><td>≥0.75</td></tr><tr><td>黄</td><td>0.519</td><td>0.480</td><td>0.468</td><td>0.442</td><td>0.427</td><td>0.483</td><td>0.465</td><td>0.534</td><td>≥0.45</td></tr><tr><td rowspan=\"2\">逆反射材料色</td><td>白</td><td>0.350</td><td>0.360</td><td>0.300</td><td>0.310</td><td>0.290</td><td>0.320</td><td>0.340</td><td>0.370</td><td>≥0.35</td></tr><tr><td>黄</td><td>0.545</td><td>0.454</td><td>0.487</td><td>0.423</td><td>0.427</td><td>0.483</td><td>0.465</td><td>0.534</td><td>≥0.27</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1017,
+        "chunk": "# 三、按普通涂料常规检测的检测项目  \n\n按普通涂料常规检测的检测项目见表3-12-14。  \n\n表3-12-14 按普通涂料常规检测的检测项目  \n\n\n<html><body><table><tr><td>序号</td><td>检测项目</td><td>依据的标准</td><td>适用涂料种类</td></tr><tr><td>1</td><td>检测环境的温湿度</td><td>GB/T9278《涂料试样状态调节和试验的温湿度》</td><td>所有类型</td></tr><tr><td>2</td><td>涂料在容器中的状态</td><td>GB/T3186《涂料产品的取样》</td><td>溶剂、双组分、水性 （热熔除外）</td></tr><tr><td rowspan=\"2\">3</td><td rowspan=\"2\">黏度</td><td>GB/T1723《涂料黏度测定法（涂-4黏度计法）》</td><td>溶剂普通型</td></tr><tr><td>GB/T9269《建筑涂料黏度的测定斯托默黏度计法》</td><td>溶剂反光型及水性</td></tr><tr><td>4</td><td>固体含量</td><td>GB/T1725《涂料固体含量测定法》</td><td>常温溶剂型、水性</td></tr><tr><td>5</td><td>密度</td><td>GB/T6750《色漆和清漆密度的测定》</td><td>常温溶剂、双组分、 水性</td></tr><tr><td>6</td><td>软化点</td><td>GB/T9284《色漆和清漆用漆基软化点测定法 环球法》</td><td>热熔</td></tr><tr><td>7</td><td>附着力</td><td>GB/T1720《漆膜附着力测定法》</td><td>溶剂、双组分普通型、 水性普通型</td></tr><tr><td>8</td><td>柔韧性</td><td>GB/T1731《涂膜柔韧性测定法》</td><td>溶剂普通型和反光 型、双组分普通型</td></tr><tr><td>9</td><td>耐水性</td><td>GB/T1733《涂膜耐水性测定法》</td><td>所有类型</td></tr><tr><td>10</td><td>耐碱性</td><td>GB/T9265《建筑涂料涂层耐碱性的测定》</td><td>所有类型</td></tr><tr><td>11</td><td>耐磨性</td><td>GB/T1768《漆膜耐磨性测定法》</td><td>所有类型</td></tr><tr><td>12</td><td>人工加速耐候性</td><td>GB/T16422.1《塑料实验室光源曝露试验》</td><td>热熔和双组分</td></tr></table></body></html>  \n\n标线涂料在不断发展，检测标线涂料的方法和手段及仪器也不断更新，相应地显现检测标准的不完善和不足，需要予以修订和补充。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1018,
+        "chunk": "# 四、标线涂料的实用性能考核  \n\n通过上述的标线涂料的试验室检测，对其性能好坏有一个基本判断，但是由于实际路用的情况（温度、湿度、光照、施工工艺、路面状况、车流量等）千变万化，往往会影响标线的实际使用寿命，特别是在不同的路面上的附着性能、耐磨性、耐老化性能和标线的持续反光性等有较大的变化，最好通过试验室检测和路用试验的配合考察来考验标线涂料配方的合理性和实用性。  \n\n美国的罗门哈斯公司欧洲试验中心就在法国的地中海城市—尼斯设有专门考核标线涂层使用性能的试验路，将该公司研制的不同配方和不同性能的水性标线涂料施工在同一条试验路上，定期观察标线涂层的磨损、逆反射系数、粉化、开裂和变色等情况的变化。德国联邦公路局的BAST试验室把全德国的各种品牌的标线涂料划设在环道试验室的环道上进行对比，从而优选出好的涂料产品。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1019,
+        "chunk": "# 第五节 标线施工材料的合理选用  \n\n据粗略估计，现在我国每年新修和维修用的标线涂料用量在15万吨以上，如何使各种标线施工材料（包括标线涂料和反光标线用玻璃珠）得到合理的使用，不产生浪费现象，首先需要进行合理的选用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1020,
+        "chunk": "# 一、各种标线涂料的性能和优缺点对比  \n\n为了使涂料生产厂家能生产出多种适用的标线涂料，用户能选用合理的标线涂料，现将国内外各种不同类型的标线涂料的性能和优缺点作一详细对比，列于表3-12-15。  \n\n表3-12-15各种标线涂料的性能和优缺点对比  \n\n\n<html><body><table><tr><td>涂料类型</td><td>涂层厚度</td><td>使用寿命</td><td>施工温度</td><td>不粘胎干燥时间</td><td>优点</td><td>缺点</td></tr><tr><td>热熔喷涂型</td><td>0.7~1.2</td><td>较长</td><td>≥10</td><td>≤3</td><td>重涂易；施工快；可 反光</td><td>需耗能，加热至 170~220℃</td></tr><tr><td>热熔刮涂型</td><td>1.5~2.5</td><td>长</td><td>≥10</td><td>≤3</td><td>涂层厚，耐磨；可 反光</td><td>重涂难；需耗能，加 热至170~220℃</td></tr><tr><td>突起型</td><td>突起高度3~7； 基底1~2， 也可无基底</td><td>长</td><td>≥10</td><td>≤3</td><td>雨夜反光优良；有振 动效果</td><td>重涂难；施工费料； 造价高</td></tr><tr><td>溶剂普通型</td><td>0.3~0.8①</td><td>短</td><td>≥5</td><td>≤15</td><td>造价低，施工快</td><td>使用寿命短；有机挥 发溶剂（VOC）含量高； 不具反光</td></tr><tr><td>溶剂反光型</td><td>0.3~0.8①</td><td>较短</td><td>≥5</td><td>≤10</td><td>（VOC）含量较低；可 反光</td><td>涂料需加热至70℃ 有机挥发溶剂左右；施工设备要求有 加热系统；施工较溶剂 普通型复杂；含有少量 有机挥发溶剂</td></tr><tr><td>水性</td><td>0.3~0.8①</td><td>中等</td><td>≥10</td><td>普通≤15 反光≤10</td><td>环保好；不含有机挥 发溶剂；反光好；与玻 璃珠的粘接力较强</td><td>对施工环境的温度 和湿度有一定要求</td></tr><tr><td>双组分</td><td>0.4~2.5</td><td>中等</td><td>≥10</td><td>≤35</td><td>与路面及玻璃珠的 粘接力较强；反光好；别是涂料和固化剂的 环保好</td><td>施工规范要求严，特</td></tr><tr><td>防滑型</td><td>3~5</td><td>长</td><td>≥10</td><td>依塗料的</td><td>防滑，减少交通事 作额用色，醒红、超到提 绿等多种颜色</td><td>用量准确及混合均匀 造价高</td></tr></table></body></html>\n\n$\\textcircled{1}$ 湿膜厚度值。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1021,
+        "chunk": "# 二、标线使用性能室内模拟试验结果  \n\n德国联邦公路研究所（BAST）的R.Keppler教授提交的论文《德国的道路标线系统试验》，提供了该所自1989～2004年总共15年的1954组不同类型的白色道路标线使用性能室  \n\n内模拟试验数据，详见表3-12-16。  \n\n表3-12-16不同类型的白色道路标线使用性能室内模拟试验数据  \n\n\n<html><body><table><tr><td>标线材料种类</td><td>溶剂含量/%</td><td>施工方法</td><td>试验总数</td><td>试验结果满意数</td><td>满意率/%</td><td>排序</td></tr><tr><td>冷塑型涂料（双组分 反应树脂)</td><td><1</td><td>喷涂、刮涂、挤压</td><td>304</td><td>188</td><td>61.8</td><td>１</td></tr><tr><td>乙预成裂标（聚氨</td><td>0</td><td>冷压、≤50℃热压</td><td>151</td><td>79</td><td>52.3</td><td>2</td></tr><tr><td>高固体分水性涂料</td><td><1</td><td>刮涂、挤压</td><td>17</td><td>8</td><td>47.0</td><td>3</td></tr><tr><td>普通水性涂料</td><td><1</td><td>喷涂</td><td>251</td><td>107.</td><td>42.6</td><td>4</td></tr><tr><td>溶剂类涂料</td><td><25</td><td>喷涂</td><td>775</td><td>259</td><td>33.4</td><td>５</td></tr><tr><td>热熔类涂料</td><td>0</td><td>喷涂、刮涂、挤压</td><td>456</td><td>116</td><td>25.5</td><td>6</td></tr><tr><td>总计</td><td></td><td></td><td>1954</td><td>757</td><td>38.7</td><td></td></tr></table></body></html>  \n\n表3-12-16所列数据是在室内的环道磨损模拟试验装置上试验得到的，试验全面考核了不同类型的白色道路标线的使用性能，包括耐磨性、持续反光性、不粘污性、附着力和裂纹状况等。  \n\n从表3-12-16可以看出：当前我国生产量最大、使用最多的热熔和溶剂标线涂料的使用性能模拟试验结果并不理想，满意率低；而满意率最高、性能最好的是冷塑型标线涂料（双组分反应树脂)。冷塑型标线涂料在我国刚开始研制，试生产和试用，水性标线涂料已开始生产并应用。所以，我们应在学习国外先进技术的基础上，根据我国的具体情况，开发品质优良的新品种，使我国的标线品种多样化。  \n\n表3-12-16反映的数据与我国实际使用情况有相当大的差距，也有可能说明：  \n\n$\\textcircled{1}$ 德国R.Keppler教授试验的模拟程度不高，所以与我国的使用数据差距大；  \n\n$\\textcircled{2}$ 我国生产的标线涂料产品与德国的同类产品的质量和性能有很大的差别，因而不具可比性；  \n\n$\\textcircled{3}$ 表3-12-16的数据毕竟是室内模拟试验的数据，没有耐紫外线辐射和风吹雨打等气候考验的试验数据，所以与实际使用情况有一定的差别；  \n\n$\\textcircled{4}$ 紫外线辐射和气候变化因素可能是影响标线涂层使用寿命的最主要的原因之一，其影响程度的大小，有待实际考核。  \n\n为了取得更为可靠的数据，应积极开展我们自己的模拟试验，模拟符合我国的实际路况、车况、气候条件等情况，做出真正有参考价值的模拟试验数据，为合理选用标线涂料提供可靠的依据。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1022,
+        "chunk": "# 三、标线涂料的合理选用  \n\n选用的标线涂料应该是施工性能好，划制的标线视认性好，能持续反光，有较长的使用寿命，性能价格比高，且符合环保要求。  \n\n针对标线不同的使用条件，对于不同的地区、不同的道路、不同功能的标线，可选用不一样的标线涂料。在综合参考表3-12-15 的各种道路交通标线涂料的性能和优缺点对比的基础上，还可参考以下建议。  \n\n(1）高速公路的实线可采用热熔喷涂型或双组分和水性标线涂料因为高速公路上的车辆行车规范，实线受车轮的碾压较少，而对标线的反光性能要求较高。热熔喷涂型涂料能够满足此要求，且性能价格比最高，可优先选用。双组分和水性涂料的涂膜与路面和玻璃珠的粘接力强，反光性能优良，较耐磨。该类涂料喷涂在路面上，基本保持路面原有的结构和抗滑性能。  \n\n(2）各种道路的实线和人行横道线可采用热熔反光标线涂料因为实线和人行横道线受碾压次数频繁，标线的磨损相对要大。热熔反光标线涂料施工的标线涂层厚，能够承受较大的交通流量，可以保证标线在较长时间内正常使用，因而减少了为重涂标线，而在通车条件下施工作业的危险。  \n\n(3）弯道及上下坡道等事故多发地带可采用防滑涂料采用防滑涂料铺筑的路面，涂层的抗滑摆值可高达70BPN以上，从而防止车轮在这些路面上打滑，同时防滑涂料采用了亮丽的色彩，可提高司机的警觉性，注意减速缓行，减少了交通事故。防滑涂料还可用在高速公路的收费站出入口和停车场等需要加强防滑的路面。热熔标线涂料划设的人行横道线虽然耐磨，但是涂层表面较滑，若在涂层表面植人防滑骨料，可以提高人行横道的抗滑性能，保证行人的安全。  \n\n(4）在长直道、隧道、桥梁、高速公路的行车道的边缘线、高速公路进出口的禁止超越地段采用突起反光标线涂料一且车轮碾压在突起反光标线涂料划设的标线上，标线的突起结构就会使车身产生轻微振荡，同时发出振动响声，提醒司机注意车辆不要跑偏。此外，这种标线的突起部分能够使标线在雨夜仍有较好的逆反射性能。突起反光标线涂料的种类有热熔突起型和双组分突起型等。  \n\n（5）无路灯照明的道路采用反光标线我国高速公路的交通安全设施（反光标志、反光标线、护栏、护网等）齐全，标线采用反光标线涂料划设，使夜间行驶的汽车通过前大灯灯光的照射，可以看清前方的标线，从而保证高速公路上行车安全。而一些县、乡的普通道路上的标志和标线等安全设施少，没有路灯照明，而且机动车辆和其他车辆混合行驶，路况复杂，夜间行车存在安全隐患，为了防止事故的发生，标线最好是划设为反光的，并增设反光标志牌等交通安全设施。  \n\n(6）地下停车场可采用不含有机挥发溶剂的水性及双组分标线涂料地下停车场是在通风不良的地下室内，为了防止污染，可采用不含有机挥发溶剂的水性及双组分标线涂料划设标线。  \n\n（7）旧路面要采用标线使用寿命与路面翻修时间相当的标线涂料旧路面本身的表面状况不佳，使用不久就得翻修，如果采用耐久性长的标线涂料，易出现标线的使用寿命大于路面使用寿命的现象，在经济上是不合算的，可选用标线使用寿命与路面翻修时间相当的标线涂料。  \n\n作为标线涂料的生产厂家、道路安全设施的设计者、标线施工队，要了解标线涂料的发展趋势，开发各种性能的多品种涂料，要熟悉标线涂料的合理使用，以划设既经济合理又实用的标线。  \n\n需要特别强调的是，这里所提出的合理选用标线涂料的建议不是一成不变的，是具有时段性的，即随着时间的推移，标线涂料生产厂家将会不断推出新的更好的标线涂料，以满足道路对各种类型和不同功能标线的需求，老产品也不断更新换代，因而本文提出的使用标线涂料的合理化建议必须不断修订、补充和完善。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1023,
+        "chunk": "# 四、标线用玻璃珠的正确选择和使用  \n\n标线用玻璃珠（下简称玻璃珠）分为面撒型和预混型两种，面撒型玻璃珠用于反光标线涂料施工时面撒在标线涂层上，起到即时反光作用。预混型玻璃珠是在制备反光标线涂料时，作为涂料配方组成的一部分混合在涂料内，在标线的使用过程中起连续反光作用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1024,
+        "chunk": "# 1.玻璃珠的逆反射原理  \n\n玻璃珠是反光标线的主要反光元件，其逆反射原理见图3-12-8。当汽车的前照灯光照射到镶嵌在标线涂层的外露玻璃珠表面时，光线折射进入玻璃珠内，到达玻璃珠的底部与标线涂层接触面后，被涂层反射折回，通过玻璃珠表面折射返回到司机的眼里。由于标线涂层上的若干玻璃珠同时产生折射，就形成了一束反射光，使司机能够在即使没有路灯照明的夜间也能看清前方的标线，循道而行。玻璃珠的这种能够使反射光线从靠近人射光线的反方向返回的反射称为逆反射，而且当人射光线的方向在较大范围内变化时，仍能保持这种性能。  \n\n影响反光标线的逆反射效果的主要因素是玻璃珠的性能、玻璃珠的植人状态和玻璃珠的撒布量。  \n\n![](images/2b539ca7e0cfaa717b085077811629a5ac217751f2b883e5728296934312d1d6.jpg)  \n图3-12-8 玻璃珠的逆反射原理",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1025,
+        "chunk": "# 2.玻璃珠的性能要求  \n\n根据交通行业标准JT/T446—2001《路面标线用玻璃珠》的规定：  \n\n$\\textcircled{1}$ 玻璃珠外观应为无色透明的球体，表面光洁圆整，玻璃珠内应无明显气泡或杂质；$\\textcircled{2}$ 有缺陷的玻璃珠如椭圆形珠、不圆的颗粒、失透的珠、熔融粘连的珠、有气泡的或有杂质等的玻璃珠质量之和应小于玻璃珠总质量的 $30\\%$  \n\n$\\textcircled{3}$ 玻璃珠的密度应在 $\\ensuremath{\\mathrm{2.4}}\\ensuremath{\\mathrm{\\sim2.6}}\\ensuremath{\\mathrm{g/cm^{3}}}$ 范围内；  \n$\\textcircled{4}$ 玻璃珠的折射率不应小于1.50；  \n$\\textcircled{5}$ 玻璃珠的耐水性测试时，玻璃珠表面不应呈现发雾现象；  \n$\\textcircled{6}$ 玻璃珠中磁性颗粒的含量不得大于 $0.1\\%$ 等。  \n\n需要提醒的是，目前国内生产的玻璃珠主要有三种，反光标线用的、研磨介质用的、喷丸抛光用的。反光标线用的强调玻璃珠的折射率、成圆率和粒径级配，研磨用的强调玻璃珠硬度，而抛光用的强调玻璃珠的强度，因此，不同用途的玻璃珠不能混用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1026,
+        "chunk": "# 3.玻璃珠的分类  \n\n（1）面撒型玻璃珠面撒型玻璃珠是施工反光标线时，立即在标线涂层上面撒布的玻璃珠。面撒型玻璃珠的粒径大小是级配的（见图3-12-9)。不同大小的玻璃珠配合在一起，能够使它们牢固地固定在涂层里。在通车过程中，露在标线涂层表面的，起即时反光作用的大粒径玻璃珠逐步被磨损脱落，中小粒径的玻璃珠就会陆续被磨露出来，继续起到反光作用。如果施工时面撒型玻璃珠的撒布量太少，标线的反光强度不够；面撒型玻璃珠撒布量太多，标线的反光强度也不够。原因是：过多的玻璃珠堆积在涂层上会影响玻璃珠正常反光，易吸附灰尘，使标线变成灰黑色。玻璃珠合理的撒布量是 $0.3{\\sim}0.4\\mathrm{kg/m^{2}}$ ，此时的玻璃珠呈一层",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1027,
+        "chunk": "# 均匀态分布在标线涂层上，  \n\n![](images/7bcd4bd247b932c3454ad51e03d7a0307e305ec524387731d090f5300a32d633.jpg)  \n图3-12-9 面撒玻璃珠粒径分布  \n\n(2）预混型玻璃珠预混型玻璃珠是在涂料生产时预先混合在涂料里的，其粒径也是大小级配的（见图3-12-10)。  \n\n![](images/d522718fe3e73a3e5bc1095767f04b4462737c1d9fbf7dac284290d62bc4401b.jpg)  \n图3-12-10 预混玻璃珠粒径分布",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1028,
+        "chunk": "# 4.玻璃珠的正确植入  \n\n理想的植人应该如图3-12-8所示，标线涂层的表面上撒布的玻璃珠颗粒有1/2～2/3的体积埋入标线涂层内，使玻璃珠能够露出足够的反射面，以获得良好的逆反射效果，且玻璃珠有一半以上的体积植人涂层里，确保其与涂层牢固结合。当标线涂层被磨耗时，表面的玻璃珠会逐步脱落，埋人涂层内部的不同粒径级配的玻璃珠依次逐渐被磨出并显露反光面，使标线能够继续保持反光性能。使用热熔反光标线涂料施工时，要使玻璃珠理想地植人热熔涂料的涂层里，就必须掌握好熔融涂料的温度。如果熔融涂料的温度过高、涂料的黏度过低，使面撒的玻璃珠大部分沉降在标线涂层的底部，则标线涂层的表面没有玻璃珠的反光面，因而标线就无法进行逆反射；如果熔融涂料的温度过低，涂料的黏度过高，面撒的玻璃珠会大部分浮在标线涂层的表面，不能很好地植入标线涂层内，经过车轮的碾压和风吹雨打，玻璃珠会很快脱落，标线在短时间内就失去逆反射作用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1029,
+        "chunk": "# 5.调整面撒玻璃珠的粒径大小  \n\n施工时，要根据不同的地区和季节调整面撒玻璃珠粒径的各个档次的比例，以获得最佳使用效果。通常在南方和夏季，选用较多的大粒径玻璃珠，在北方和冬季，选用较多的小粒径玻璃珠，但仍应保持标准规定的玻璃珠级配挡数，不能因缺挡及比例不合理而影响标线的连续反光性能和玻璃珠在涂层上的粘接力。  \n\n此外，新开发的水性标线涂料和双组分标线涂料与玻璃珠的粘接力强，可以粘牢较大粒径的玻璃珠。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1030,
+        "chunk": "# 6.面撒玻璃珠的合适用量  \n\n并不是标线涂层上撒布的玻璃珠越多，标线的反光效果就越好，实际上堆积在标线涂层上过多的玻璃珠会因为没粘牢，而很快脱落掉，起不到反光效果，反而造成浪费。过多的玻璃珠堆积在标线涂层的表面，还会国积灰尘，使标线的颜色在白天看上去是灰黑色的，影响视认效果，晚上的反光效果也差。如果标线涂层面撒的玻璃珠太少，反光点少，标线的反光效果自然就差。通常每平方米标线的面撒玻璃珠的合适用量为0.3～ $0.3\\sim$ 0.4kg，而对于热熔反光标线涂料，除了面撒玻璃珠以外，在其配方里还预混有质量分数为18%～25%的玻璃珠，使标线保持良好的持续反光性能。美国州际道路工作者协会的标准AASHTOM-249中规定，预混的玻璃珠含量高达30%～40%。划设好的反光标线可用5倍的放大镜观察玻璃珠撒布情况，应该是分布均匀、没有结团和成块的现象。国家标准GB/T16311《道路交通标线质量要求和检测方法》规定：新划设的白色反光标线的逆反射系数应不小于150mcd/（lx·m2），黄色反光标线的逆反射系数应不小于100mcd/$(\\ln\\cdot\\mathrm{\\boldmath~m^{2}~})$ a",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1031,
+        "chunk": "# 7.表面处理面撒玻璃珠  \n\n由于面撒玻璃珠是无机化合物，而标线涂料是有机化合物，为了提高二者的亲和力，使撒布的玻璃珠牢固地黏附在标线涂层上，可对玻璃珠进行表面偶联处理。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1032,
+        "chunk": "# 8.混入防滑骨料  \n\n为了提高标线的抗滑能力，可以在面撒玻璃珠内混入防滑骨料，随玻璃珠一起面撒在标线涂层上。  \n\n以上所述的玻璃珠的正确使用大部分是针对热熔反光标线而言的，随着标线涂料新品种的不断开发成功，双组分反光标线涂料、水性反光标线涂料已陆续得到应用，因为这些涂料对玻璃珠的粘接力强，可粘接粒径较大的玻璃珠，所以本节所述的玻璃珠的粒径级配要随涂料的种类而变。再如目前我国反光标线用的玻璃珠的折射率为1.5，建议今后在重要的路段可配用折射率n≥1.7或n≥1.9的玻璃珠，以提高标线的反光性能，减少行车安全事故。总之，本节所述的玻璃珠的正确使用方法要随涂料种类的变化、玻璃珠的发展及对标线性能要求而变，决不是一成不变的。  \n\n![](images/00d3a29a504d2fc809199258988e0cfce63b391d3e1f2a08c0c4737878f7981f.jpg)  \n\n标线涂料的施工，就是由专业的施工人员使用标线施工设备，把工程所用的标线涂料按设计施工图纸和施工规范施工在路面上，划设成标线。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1033,
+        "chunk": "# 一、标线施工的特点",
+        "category": " Introduction"
+    },
+    {
+        "id": 1034,
+        "chunk": "# 1.施工现场的流动范围大  \n\n标线施工的现场是流动的，不是固定在某一地点，是边施工边移动的，这就要求做好施工前的准备工作，涂料和燃气要备足，施工安全管理所需的安全锥和路栏以及指示路标、旗帜、警示灯等安全管理用具要备够，划线机要预先调试好，并预先熟悉施工图纸，制订好施工规范及质量保证措施，到现场就能施工，不要仓促上阵，避免因准备不足而耽误作业时间和影响施工质量。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1035,
+        "chunk": "# 2.施工人员的危险性大  \n\n在道路上划设标线，要受来往车辆的影响。在新修好尚未通车的道路上施工，需要和其他施工单位协调好；在已通车的道路上施工，要防止交通堵塞和发生交通安全事故。通常是半幅路面通车，半幅路面施工。有时为了不阻断交通，不得不在晚上施工。为此，在施工作业区要设置“前方正在施工”的标志，提醒司机和行人注意绕行。设置安全锥、临时标线等划出施工范围，确保施工区的安全。施工车上应安装警示灯，引起来往车辆的注意。施工人员必须穿上反光安全服装，设置专职的安全员，建立安全保障体系，确保施工人员的安全。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1036,
+        "chunk": "# 3.施工环境复杂多变  \n\n标线的施工是露天作业的，会受到日晒、风吹、雨淋、雪飘、沙尘的干扰，车辆的来回穿梭和多变的环境对标线的施工质量和施工人员的安全都有影响，施工队伍必须会随时应对各类突发事件。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1037,
+        "chunk": "# 4.施工工期短促  \n\n标线的施工是新建道路工程的最后一道工序，所留的工期极短，或者根本不留工期，边通车边施工，赶工期几乎成了标线施工的通病。在旧路上复涂标线也一样，为减少阻断交通的时间，希望施工的时间越短越好。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1038,
+        "chunk": "# 二、市售标线涂料的选择依据  \n\n根据设计要求选择的涂料性能应该符合有关标准，所选用的涂料应附有该批次涂料的自检报告和质保单。对于不同地区和不同的施工季节要选用与之相适宜的涂料。就热熔标线涂料而言，为防止涂层早期开裂，用在温差大的西北地区青海省的涂料，就一定要选用柔韧性好的；如果用在四季分明的上海市，在秋冬季节也要用柔韧性好的涂料。总之，选用市售的标线涂料应该是质量可靠、性能价格比高的，符合当地使用条件。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1039,
+        "chunk": "# 三、标线的分类",
+        "category": " Introduction"
+    },
+    {
+        "id": 1040,
+        "chunk": "# 1.按标线的材料分类  \n\n按标线的材料分为： $\\textcircled{1}$ 溶剂型涂料标线； $\\textcircled{2}$ 热熔型涂料标线； $\\textcircled{3}$ 水性涂料标线； $\\textcircled{4}$ 双组分涂料标线； $\\textcircled{5}$ 预成型标线带标线。目前市场用得最多的是热熔型涂料标线和溶剂型涂料标线，水性涂料标线和双组分涂料标线因对环境污染小而日受欢迎。预成型标线带是用聚氯乙烯或聚氨酯等高分子材料在工厂用机器压制而成，以带状成卷供应。施工时，可配合标线涂料的施工，将标线带预制成各种图形和符号直接粘贴在路面上。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1041,
+        "chunk": "# 2.按标线的功能分类  \n\n按功能分为普通标线，反光标线和突起结构型振动反光标线。普通标线即不具反光性能的标线，可用在有路灯照明的城市道路；高速公路及无照明条件的道路应该选用反光标线；突起结构型振动反光标线在车轮压线时，能够使车辆产生轻微振动且在雨夜也能够反光，通常用于道路边缘线及一些需要提示的地方。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1042,
+        "chunk": "# 3.按标线的设置方式分类  \n\n按设置方式分为纵向标线，横向标线和其他标线。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1043,
+        "chunk": "# 四、标线质量的基本要求  \n\n标线的设计应符合GB5768的规定。所使用的标线涂料应符合有关国家标准和行业标  \n\n准的要求，具有与路面附着力强、干燥迅速以及良好的耐磨性、耐候性、不粘污性、抗滑性等特性。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1044,
+        "chunk": "# 五、标线划设的工序",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1045,
+        "chunk": "# 1.封闭交通  \n\n封闭交通为的是使施工区成为不受外界干扰的、安全的、独立的区域，为此必须用反光标志锥桶、隔离护栏、临时标线等划定施工范围，并树立“前方道路施工”的标志牌。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1046,
+        "chunk": "# 2.清扫路面  \n\n路面的灰土、砂石和水分是影响标线涂层与路面附着性能和涂层质量的主要因素，必须打磨清扫干净。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1047,
+        "chunk": "# 3.划标准线定位  \n\n按施工图纸要求，用钢卷尺准确测量，并划出划线机赖以定位的标准线。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1048,
+        "chunk": "# 4.准备涂料和玻璃珠  \n\n按各种标线涂料的特殊要求，准备好待划的涂料和玻璃珠。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1049,
+        "chunk": "# 5.划设标线  \n\n调整划线机各部件，待试划正常后，即可按定位好的标准线划设标线。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1050,
+        "chunk": "# 6.检验  \n\n检查标线的质量，对有缺陷和不合格的标线及时修补。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1051,
+        "chunk": "# 7.开放交通  \n\n待标线涂层不粘胎后，即可撤走施工设备和材料，撤除封闭交通的安全设施，开放交通。  \n\n在标线施工前，一定要进行试划。以热熔涂料为例，首先要调整好斗槽、撒珠设备到正常状态，调节好热熔釜内的熔料温度，使熔融涂料达到合适的黏度，以保证涂料有良好的施工性能，与路面和玻璃珠良好的粘接性能和反光性能。当涂料和施工设备调试好以后，才能正式划线施工。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1052,
+        "chunk": "# 六、各种标线涂料的施工设备、施工参数和注意事项",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1053,
+        "chunk": "# 1.热熔标线涂料的施工  \n\n（1）热熔标线涂料的施工设备热熔标线涂料的施工设备主要由热熔釜和划线车组成，划线车包括涂覆器、玻璃珠撒布器和行走机构等。热熔釜是涂料施工前的预热设备，将固态粉粒状的热熔标线涂料在不断的搅拌下，加热至 $180\\sim220^{\\circ}C$ 熔融成流动态。热熔釜除有容量大小外，还分为单缸和双缸两种。加热的燃料大部分是用液化石油气也有用柴油的。搅拌的方式有液压式的也有机械式的。熔融的涂料在贮料罐内保温待用。  \n\n热熔标线涂料划线车的涂覆器有刮涂型和喷涂型两种。刮涂型的涂覆是依靠熔融涂料的重力，从料斗门成带状流出，由料斗门的底刀片和侧刀片控制流出涂层的厚度，在行走机构的配合下，划设出所需厚度和宽度的标线涂层。涂层的厚度一般为 $1.5{\\sim}2.5\\mathrm{mm}$ ，宽度一般为 $\\mathtt{150m m}$ ， $200\\mathrm{mm}$ 和 $450\\mathrm{mm}$ 等。  \n\n喷涂型划线车的涂覆器有离心喷涂型、有气喷涂型和螺旋喷涂型三种。离心喷涂型的原理是靠双轴齿轮高速旋转所产生的离心力将涂料甩出；有气喷涂型是靠压缩空气使涂料的出口产生负压，将涂料吸出，喷涂到需要划设标线的路面上；螺旋喷涂型是利用螺旋泵将熔融的涂料垂直往下推压，通过阀门下部的窄长的缝隙中挤出，形成帘状涂料喷涂层。  \n\n热熔突起划线车施工时，依靠特殊的模具将具有触变性的热熔涂料（有一定的流平性，又能使施工形成的突起结构具有良好的保型性）一次成型划设在路面上。  \n\n玻璃珠撒布器有重力式和喷撒式两种。  \n\n行走机构有用人力的手推划线车，自带动力的自行式划线车和施工设备放在汽车上的车载式划线车三种。  \n\n以上所述的热熔标线涂料的施工设备应根据施工设计要求、工程量的大小、工程的质量要求选用。  \n\n(2）热熔标线涂料的施工参数各种施工参数见表3-12-17～表3-12-19。  \n\n表3-12-17 热熔刮涂型标线涂料的施工参数  \n\n\n<html><body><table><tr><td rowspan=\"2\">涂层厚度/mm</td><td>涂料用量</td><td>面撒玻璃珠用量</td><td>工时费</td><td>设备折旧费</td><td>管理费</td><td>单位成本</td></tr><tr><td colspan=\"2\">/(kg/m²)</td><td colspan=\"4\">/（元/m²）</td></tr><tr><td>1.5~2.5</td><td>3~5</td><td>0.3～0.4</td><td>4~5</td><td>2.5</td><td>1.3</td><td>28~35</td></tr></table></body></html>\n\n注：各厂产品质量各异，施工水平差别大，市场价格变化巨测，以上数据仅供参考。  \n\n表3-12-18 热熔喷涂型标线涂料的施工参数  \n\n\n<html><body><table><tr><td rowspan=\"2\">涂层厚度/mm</td><td>涂料用量</td><td>面撒玻璃珠用量</td><td>工时费</td><td>设备折旧费</td><td>管理费</td><td>单位成本</td></tr><tr><td colspan=\"2\">/(kg/m²)</td><td colspan=\"4\">/（元/m²）</td></tr><tr><td>0.7~1.5</td><td>2.4~3.0</td><td>0.3~0.4</td><td>4~5</td><td>3</td><td>1.5</td><td>25~28</td></tr></table></body></html>\n\n注：各厂产品质量各异，施工水平差别大，市场价格变化巨测，以上数据仅供参考。  \n\n表3-12-19 热熔突起型标线涂料的施工参数  \n\n\n<html><body><table><tr><td rowspan=\"2\">涂层厚度/mm</td><td>涂料用量</td><td>面撒玻璃珠用量</td><td>工时费</td><td>设备折旧费</td><td>管理费</td><td>单位成本</td></tr><tr><td colspan=\"2\">/(kg/m²)</td><td colspan=\"4\">/（元/m）</td></tr><tr><td>基线1～2 突起部分3～7</td><td>6~8</td><td>0.3~0.4</td><td>8~10</td><td>6</td><td>3.5</td><td>80～120</td></tr></table></body></html>\n\n注：各厂产品质量各异，施工水平差别大，市场价格变化巨测，以上数据仅供参考。  \n\n(3）热熔标线涂料施工的注意事项热熔标线涂料应在晴天施工，施工的地表温度应在$10^{\\circ}C$ 以上。由于热熔标线涂料的施工是加热进行的，因此控制涂料加热的温度是关键，若施工环境的温度偏高，则熔料的温度可以适当降低；若施工环境的温度偏低，则熔料的温度可以适当提高。通过调整加热温度来调节涂料的黏度，使熔融的涂料按所需的厚度涂覆，确保涂层有良好的线形，撒布的玻璃珠牢固地黏附在涂层上，并有良好的反光性能。涂料在熔融过程中不能长期处在高温加热状态，否则将会使涂料的颜色变深，树脂裂解变质。高温加热作业要注意防火、防烫伤。因为涂覆的底漆含有机挥发溶剂，易燃，待底漆干透后才能施工热熔涂料，要防止燃气管路的泄漏。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1054,
+        "chunk": "# 2.溶剂标线涂料的施工  \n\n（1）溶剂标线涂料的施工设备  \n\n$\\textcircled{1}$ 溶剂普通型标线涂料的施工设备溶剂普通型标线涂料施工所用的设备主要是喷涂划线机，没有划线机时也可以人工刷涂或辊涂。涂料的喷涂分低压有气喷涂和高压无气喷涂  \n\n两种。  \n\n低压有气喷涂划线机由空气压缩机、油水分离器、喷枪、连接胶管和贮料罐、行走机构等组成。因为其施工时气雾污染严重，施工效率低，现在很少应用。  \n\n高压无气喷涂划线机由动力源、高压泵、稳压器、过滤器、输漆管、喷枪、贮料罐、行走机构等组成。其原理是利用高压泵将涂料加压至 $10{\\sim}25\\ \\mathrm{MPa}$ ，通过喷枪高速喷涂到路面上，形成标线。高压无气喷涂的优点是施工效率高，涂料利用率高，对环境污染小，能喷较高黏度的涂料，施工的标线涂层较厚，边缘整齐美观。  \n\n$\\textcircled{2}$ 溶剂反光型标线涂料的施工设备溶剂反光型标线涂料的施工设备也是高压无气喷涂划线机，但是由于该涂料的固体含量高达 $70\\%$ 以上，黏度高，需增加一套加热系统，将涂料加热到 $50{\\sim}80^{\\circ}C$ ，使涂料的黏度达到高压无气喷涂所要求的范围内，施工的标线涂层厚，能牢固黏附玻璃珠。  \n\n(2)溶剂标线涂料的施工参数普通型和反光型的施工参数分别见表3-12-20和表3-12-21。  \n\n表3-12-20 溶剂普通型标线涂料的施工参数  \n\n\n<html><body><table><tr><td rowspan=\"2\">涂层湿膜厚度/mm</td><td>涂料用量</td><td>工时费</td><td>设备折旧费</td><td>管理费</td><td>单位成本</td></tr><tr><td>/(kg/m²)</td><td colspan=\"4\">/（元/m²）</td></tr><tr><td>0.3~0.5</td><td>0.4~0.5</td><td>2~3</td><td>2</td><td>1.5</td><td>11~15</td></tr></table></body></html>\n\n注：各厂产品质量各异，施工水平差别大，市场价格变化巨测，以上数据仅供参考。  \n\n表3-12-21 溶剂反光型标线涂料的施工参数  \n\n\n<html><body><table><tr><td rowspan=\"2\">涂层湿膜厚度 /mm</td><td>涂料用量</td><td>面撒玻璃珠用量</td><td>工时费</td><td>设备折旧费</td><td>管理费</td><td>单位成本</td></tr><tr><td colspan=\"2\">/(kg/m²）</td><td colspan=\"4\">/（元/m²）</td></tr><tr><td>0.3~0.8</td><td>0.8～1.0</td><td>0.3～0.4</td><td>3~5</td><td>3</td><td>1.5</td><td>15~18</td></tr></table></body></html>\n\n注：各厂产品质量各异，施工水平差别大，市场价格变化回测，以上数据仅供参考。  \n\n(3）溶剂标线涂料施工的注意事项溶剂标线涂料的施工应在晴天，地表的温度在 $0^{\\circ}C$ 以上。溶剂标线涂料的挥发性有机化合物含量高达 $30\\%$ 左右，除了污染环境外，易燃，特别是稀释剂，要注意保管。施工的涂料要搅拌均匀后才能使用，不同厂牌和型号的涂料不能混用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1055,
+        "chunk": "# 3.水性标线涂料的施工  \n\n(1）水性标线涂料的施工设备水性标线涂料的施工设备与溶剂标线涂料的施工设备相同，采用高压无气喷涂。因为水性涂料是碱性的，故施工设备接触涂料的部位要采用不锈钢制作。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1056,
+        "chunk": "# （2）水性标线涂料的施工参数 见表3-12-22。  \n\n表3-12-22水性反光型标线涂料的施工参数  \n\n\n<html><body><table><tr><td rowspan=\"2\">涂层湿膜厚度/mm</td><td>涂料用量</td><td>面撒玻璃珠用量</td><td>工时费</td><td>设备折旧费</td><td>管理费</td><td>单位成本</td></tr><tr><td colspan=\"2\">/(kg/m²)</td><td colspan=\"4\">/（元/m²）</td></tr><tr><td>0.3~0.8</td><td>0.8～1.0</td><td>0.3~0.4</td><td>3~5</td><td>3.5</td><td>1.5</td><td>18~22</td></tr></table></body></html>\n\n注：各厂产品质量各异，施工水平差别大，市场价格变化回测，以上数据仅供参考，  \n\n(3）水性标线涂料施工的注意事项水性标线涂料的施工对施工环境条件有较严格的要求，地表的温度不能低于 $10^{\\circ}C$ ，对湿度也有限制，涂料不允许长时间搅拌和高速搅拌。一般不允许用水稀释涂料，以防涂料破乳。施工中途停顿，为防喷嘴堵塞，要将喷嘴浸入 $5\\%$ 的氨水中。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1057,
+        "chunk": "# 4.双组分标线涂料的施工  \n\n（1）双组分标线涂料的施工设备 双组分标线涂料施工使用的设备有以下两种。  \n\n① 喷涂型双组分标线涂料划线机由于双组分标线涂料是仅在施工时才将两种不同的A、B组分混合而成的，因此其喷涂施工设备比通常的喷涂设备多一个A、B两组分混合问题。目前有喷枪内混合和喷枪外混合两种形式，喷枪内混合技术是将加压后的A、B两种组分从喷嘴喷出之前就按比例进行充分混合，然后从喷枪喷出，形成标线涂层。喷枪外混合技术是将加压后的A、B两种组分分别由各自的喷嘴中喷出，在接触到路面的瞬间高压雾化混合，形成标线涂层。  \n\n$\\textcircled{2}$ ② 双组分突起型标线涂料划线机双组分突起型标线涂料的划线机是一种离心式的涂料甩出设备。施工时，将两种组分的涂料装在容器里充分搅拌，打开料斗阀门，将已经充分搅匀的混合料流到低速旋转的转子上(俗称狼牙棒)，依靠转子旋转的离心力，将涂料甩到路面上，形成了形状各异的、独立的不规则点状突起结构的标线涂层。  \n\n(2）双组分标线涂料的施工参数 反光型和突起型施工参数分别见表3-12-23和表3-12-24。  \n\n表3-12-23 双组分反光型标线涂料的施工参数  \n\n\n<html><body><table><tr><td rowspan=\"2\">涂层厚度/mm</td><td>涂料用量</td><td>面撒玻璃珠用量</td><td>工时费</td><td>设备折旧费</td><td>管理费</td><td>单位成本</td></tr><tr><td colspan=\"2\">/(kg/m²)</td><td></td><td colspan=\"3\">/（元/m²）</td></tr><tr><td>0.5~0.7</td><td>0.8~1.0</td><td>0.3～0.4</td><td>3~5</td><td>3</td><td>2.5</td><td>45~50</td></tr></table></body></html>\n\n汪：各厂产品质量各异，施工水平差别大，市场价格变化巨测，以上数据仅供参考。  \n\n表3-12-24双组分突起型反光标线涂料的施工参数  \n\n\n<html><body><table><tr><td rowspan=\"2\">突起部分高度/mm</td><td>涂料用量</td><td>面撒玻璃珠用量</td><td>工时费</td><td>设备折旧费</td><td>管理费</td><td>单位成本</td></tr><tr><td colspan=\"2\">/(kg/m²)</td><td></td><td colspan=\"3\">/（元/m²）</td></tr><tr><td>3~7</td><td>2~3</td><td>0.3~0.4</td><td>3~5</td><td>3</td><td>1.5</td><td>100～130</td></tr></table></body></html>\n\n注：各厂产品质量各异，施工水平差别大，市场价格变化巨测，以上数据仅供参考。  \n\n(3）双组分标线涂料施工的注意事项双组分标线涂料施工要求地表的温度在0℃以上，涂层的不粘胎干燥时间仅与温度和固化剂的用量有关，而与涂层的厚度无关。固化剂加入到B组分后要充分搅拌，已加有固化剂的B组分要尽快使用，在23～25℃时可以保存1～2d。在高温的天气只能保存几小时。A、B两组分性能各异，要严格分开，不能混用， $_{1\\sim2\\mathrm{d}}$ 包括其管道。涂料忌明火，施工完毕要及时清洗设备。  \n\n![](images/17721b33a54357d11d3194c69616b01c9ab7355c334a7426fdcefdae821ba99f.jpg)  \n\n在选择好达标的标线涂料和面撒玻璃珠后，将划线机调试好，按设计图纸及施工规范就可以进行标线施工。施工时要按GB/T16311一2005《道路交通标线质量要求和检测方法》做好自检，严格控制整个工程的施工质量，就能做出优质标线工程。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1058,
+        "chunk": "# 一、标线施工质量的要求",
+        "category": " Introduction"
+    },
+    {
+        "id": 1059,
+        "chunk": "# 1.标线的外观  \n\n标线应具有良好的视认性，宽度一致、边缘整齐、线形规则、线条流畅。首先，放线要  \n\n准确，涂料的黏度合适，防止意外振动，划出的标线外观就好。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1060,
+        "chunk": "# 2.标线的形状位置  \n\n标线的位置与设计位置横向允许偏差为土30mm。复划标线时，新标线与旧标线应基本重合，位置偏差范围为士5mm。只要放样正确，划线车不发生颠簸，施工人员认真操作，标线的位置基本不会偏离。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1061,
+        "chunk": "# 3.标线的几何尺寸及允许偏差  \n\n纵向标线和横向标线的长度、宽度和虚线的纵向间距偏差应符合表3-12-25的规定。  \n\n表3-12-25 标线尺寸允许偏差 单位：mm  \n\n\n<html><body><table><tr><td>项目</td><td>尺寸</td><td>允许偏差</td><td>项 目</td><td>尺寸</td><td>允许偏差</td></tr><tr><td rowspan=\"5\">长度</td><td>6000</td><td>0~30</td><td rowspan=\"2\">宽度</td><td>200</td><td>0~8</td></tr><tr><td>5000</td><td>0 ~25</td><td>150</td><td>0~8</td></tr><tr><td>4000</td><td>0~20</td><td>100</td><td>0~8</td></tr><tr><td>3000</td><td>0~15</td><td>9000</td><td>±30</td></tr><tr><td>2000</td><td>0~10</td><td>6000</td><td>士20</td></tr><tr><td rowspan=\"4\">宽度</td><td>1000</td><td>0~10</td><td>虚线的纵向间距</td><td>4000</td><td>±20</td></tr><tr><td>450</td><td>0~10</td><td></td><td>3000</td><td>±15</td></tr><tr><td>400</td><td>0~10</td><td></td><td>2000</td><td>±15</td></tr><tr><td>300</td><td>0~10</td><td></td><td>1000</td><td>±10</td></tr></table></body></html>  \n\n需要提醒注意的是：表中所列的标线宽度和实线的长度只有正误差，不允许有负误差，其目的在于确保标线有足够的视认面积和宽度，保证行车安全。  \n\n其他标线的尺寸允许偏差不大于 $5\\%$ 。其他标线设置角度的允许偏差为士3°。标线的端线与边线应垂直，其允许偏差为 $\\pm5^{\\circ}$ 中  \n\n为了确保测量数据的准确性，应用钢卷尺丈量。只要划线时认真作业，严格控制标线的几何尺寸，就能施工出合格的标线。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1062,
+        "chunk": "# 4.标线的厚度要求  \n\n一般标线的厚度范围见表3-12-26。  \n\n单位：mm  \n\n表3-12-26 标线的厚度范围  \n\n\n<html><body><table><tr><td>序号</td><td>标线种类</td><td>标线厚度范围</td><td>备注</td></tr><tr><td>１</td><td>溶剂型涂料标线</td><td>0.3~0.8</td><td>湿膜</td></tr><tr><td>2</td><td>热熔型涂料标线</td><td>0.7~2.5</td><td>干膜</td></tr><tr><td>3</td><td>水性涂料标线</td><td>0.3~0.8</td><td>湿膜</td></tr><tr><td>4</td><td>双组分涂料标线</td><td>0.4~2.5</td><td>干膜</td></tr><tr><td>5</td><td>预成型标线带标线</td><td>0.3~2.5</td><td></td></tr></table></body></html>  \n\n从上表可以看出，热熔型涂料标线的标线厚度范围为 $0.7{\\sim}2.5\\mathrm{mm}$ ，其中包括热熔喷涂施工的标线厚度为 $0,7{\\sim}1.2{\\mathrm{mm}}$ ，热熔刮涂施工标线厚度为 $1.5{\\sim}2.5\\mathrm{mm}$ 。只要施工前调试好划线机及控制好施工速度，标线涂层的厚度是不难控制的。标线涂层的厚度不是越厚越好，实际情况是太厚的涂层会使压线的车辆产生颠簸，影响行车安全。  \n\n突起结构型振动反光标线涂层突起部分的高度为 $3\\sim7\\mathrm{mm}$ ，若有基线，基线的厚度为$1\\sim2\\mathrm{mm}$ 。突起结构型振动反光标线涂层的突起部分易塌陷，选用优质涂料是关键。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1063,
+        "chunk": "# 5.标线的色度性能要求  \n\n标线涂层的颜色基本为白色或黄色，其色品坐标和亮度因数应符合GB2893《安全色》的要求，在表3-12-13和图3-12-7规定的范围内。符合要求的颜色应该是亮丽的，白天看上去标识明显，视认性好，晚上反光强度高。  \n\n标线的色度性能不合格往往是涂料配方中的颜料没配好，或者是热熔涂料被过度加热以及底层沥青渗色等因素造成的，施工时，热熔涂料的加热温度要控制好，刚铺好的路面不要马上划线。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1064,
+        "chunk": "# 6.标线的反光性能要求  \n\n白色反光标线的初始逆反射系数应不小于 $150\\mathrm{mcd}/(\\mathrm{l}\\mathrm{x}\\cdot\\mathrm{m}^{2})$ ；黄色反光标线的初始逆反射系数应不小于 $100\\mathrm{mcd/(lx\\cdotm^{2})}$ 。玻璃珠的折射率、成圆率、粒径级配和玻璃珠的用量对标线的逆反射系数有决定性影响，选用优质玻璃珠和合理的撒布量及正确的植入状态就显得非常重要。撒布时要防风，使玻璃珠均匀下落。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1065,
+        "chunk": "# 7.标线的抗滑性能要求  \n\n要使标线具有抗滑能力，可在标线施工时，在标线涂层里配以抗滑骨料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1066,
+        "chunk": "# 二、热熔标线涂层缺陷形态、产生原因和防止措施  \n\n标线涂层产生缺陷的原因很多，必须先仔细观察缺陷的形态，根据缺陷的特征，找到产生的原因，制定确实可行的防止措施，切忌主观武断。缺陷产生的原因不外乎与原材料质量（涂料、玻璃珠、底漆等)；施工工艺（熔融温度、搅拌情况、喷涂的压力和流量、原材料用量等)；施工机械故障；路面的材质（水泥或沥青)；路面状况（开裂、高低不平、太软等)；环境气候条件（气温、湿度、风、雨、雪等)；路面交通等因素有关。热熔标线涂层缺陷形态、产生原因和防止措施见表3-12-27。  \n\n表3-12-27 热熔标线涂层缺陷形态、产生原因和防止措施  \n\n\n<html><body><table><tr><td>缺陷形态</td><td>产生原因</td><td>防止措施</td></tr><tr><td>颜色不正</td><td>1.紫外线照射使颜料变色； 2.涂料长期贮存变质； 3.涂料熔融温度过高； 4.热熔釜的边角和底部的烧焦物混人； 5.玻璃珠撒布过多，积聚灰尘； 6.涂层未干，过早开放交通，涂层沾染污物； 7.沥青路面渗色 1.玻璃珠质量差，折射率低，成圆率低，粒</td><td>1.使用耐紫外线颜料； 2.注意保质期，涂料不能长期贮存； 3.涂料熔融温度不超过许可值，熔料时要充分搅拌； 4.熔料前要清理干净热熔釜； 5.玻璃珠撒布要适量； 6.标线涂层不粘胎后，再开放交通； 7.刚完工的沥青路面不要马上划线</td></tr><tr><td>逆反射效果差</td><td>径的级配不合理； 2.涂层面撒的玻璃珠太少，反光点减少；面 撒的玻璃珠太多，堆积的玻璃珠影响光 线的逆反射； 3.施工时风力大，使面撒的玻璃珠被吹离 标线区； 4.涂料色度偏暗； 5.施工时涂料黏度过高，玻璃珠粘不牢，过 早脱落： 6.施工时涂料黏度过低，玻璃珠沉底； 7.涂料中预混的玻璃珠不够</td><td>1.使用合格的玻璃珠； 2.玻璃珠撒布量要合适、均匀； 3.风力大不宜施工，若要施工则应采取防风措施，在 玻璃珠撒布器上加防风罩； 4.选用颜色符合标准的涂料； 5.调低涂料的黏度； 6.调高涂料的黏度； 7．选用合格的涂料</td></tr></table></body></html>  \n\n续表  \n\n<html><body><table><tr><td>缺陷形态</td><td>产生原因</td><td>防止措施</td></tr><tr><td rowspan=\"6\">起皮脱落</td><td>1．涂料中的树脂含量不够； 2.涂料受潮；</td><td>1.选用合格的涂料； 2.涂料的保管要注意通风防潮；</td></tr><tr><td>3.涂料长期贮存变质；</td><td>3.注意保质期，涂料不能长期贮存；</td></tr><tr><td></td><td></td></tr><tr><td>4、水泥路面未涂底漆或底漆用量不够；</td><td>4.涂够渗透性好的底漆；</td></tr><tr><td>5.路面未清扫干净；</td><td>5.路面清扫干净；</td></tr><tr><td>6．新修水泥路面上有浮碱； 7.施工环境温度低于5℃；</td><td>6.用机械方法彻底清除新修水泥路面上的浮碱； 7.施工环境温度高于5℃施工；</td></tr><tr><td rowspan=\"6\">横向裂纹</td><td>8.除雪机和防滑链的机械损伤； 9.融雪剂的侵蚀</td><td>8.防止被除雪机和防滑链机械损伤； 9.选用合适的融雪剂</td></tr><tr><td></td><td></td></tr><tr><td>1.春、秋季施工使用夏季用涂料，因而涂层 不够柔软；</td><td>1．采用合适季节用涂料；</td></tr><tr><td>2．沥青路面未压实</td><td></td></tr><tr><td></td><td>2.沥青路面压实后施工</td></tr><tr><td>1.紫外线辐射； 2.昼夜和四季的温差造成涂层周期性膨胀</td><td>1.选用耐候性好的涂料； 2.选用韧性好的涂料</td></tr><tr><td>不规则裂纹</td><td>收缩 1.路面潮湿，形成水蒸气气泡后被压成圆形</td><td>1.路面干燥后再施工；</td></tr><tr><td>圆形裂纹 刮涂施工时表面</td><td>裂纹； 2.底漆的低沸点成分挥发形成微气泡，压 裂而成</td><td>2.选用合格的底漆，待底漆彻底干透后再划设标线</td></tr><tr><td>纵向条纹</td><td>1.涂料内混有过烧结块渣或异物、石子等； 2.料斗槽口有缺损 1.涂料斗槽振动；</td><td>1.清除涂料中的杂物； 2.修补料斗槽口中的缺损</td></tr><tr><td>刮涂施工时表面 横向条纹</td><td>2.路面不平整； 3.涂料黏度太大； 4.涂层太薄</td><td>1.排除引起料斗槽振动的原因； 2.施工时注意随时调整； 3.调低涂料的黏度； 4.适当加厚涂层</td></tr><tr><td>刮涂施工时表面 不平</td><td>1.涂料的流平性不好； 2.路面微凹； 3.涂料未拌匀； 4.涂料未完全熔化； 5.涂料过烧，有机成分裂解和挥发</td><td>1.调整涂料的流平性； 2.选用流平性好的涂料，并加大涂料用量； 3.拌匀涂料； 4.涂料熔化完全；</td></tr><tr><td>标线形状扭曲 变形</td><td>1.沥青软化，路面变形； 2.涂层未干或太软，被车轮碾压变形</td><td>5.控制好熔料的温度不过烧 1.注意对沥青路面的施工； 2.不过早开放交通，选用抗压强度合格的涂料</td></tr><tr><td>起泡</td><td>1.路面潮湿，水蒸气挥发； 2.底漆未干，溶剂挥发</td><td>1．路面干燥后再施工； 2.底漆干透后再施工</td></tr><tr><td>突起型的突起部 分脱落</td><td>涂层柔韧性差，不耐冲击</td><td>选用合格的涂料</td></tr><tr><td>突起型的突起部 分被压扁</td><td>1.暴晒温度高，涂层抗压强度不够； 2.暴晒温度高，沥青路面变软</td><td>1．选用高温不变软的涂料； 2.对高温变软的沥青路面不宜使用热熔突起型涂料</td></tr></table></body></html>  \n\n三、溶剂、水性和双组分标线涂层缺陷形态、产生原因和防止措施溶剂、水性和双组分标线涂层缺陷形态、产生原因和防止措施见表3-12-28。  \n\n表3-12-28 溶剂、水性和双组分标线涂层缺陷形态、产生原因和防止措施  \n\n\n<html><body><table><tr><td>缺陷形态</td><td>产生原因</td><td>防止措施</td></tr><tr><td>颜色不正</td><td>1.沥青路面渗色； 2.涂层未干，过早开放交通，涂层沾染污物； 3.涂料长期贮存变质； 4.紫外线照射使颜料变色； 5.双组分标线涂料的固化剂添加比例过大； 6.玻璃珠撒布过多，积聚灰尘</td><td>1.刚完工的沥青路面不要马上划线； 2.涂层不粘胎后，再开放交通； 3.注意保质期，涂料不宜长期贮存； 4.使用耐紫外线颜料； 5.严格控制固化剂用量； 6.玻璃珠撒布要适量</td></tr><tr><td>逆反射 效果差</td><td>1.玻璃珠质量不好，折射率低，成圆率低，粒 径级配不合理； 2.涂层玻璃珠太多或太少； 3.玻璃珠埋在涂层太深，反光面没有露出或 露出太少； 4.玻璃珠浮在涂层表面，没有粘牢，很快被车 轮磨掉</td><td>1.使用合格的玻璃珠； 2.玻璃珠撒布量要合适、均匀； 3.玻璃珠植人的状态要合适，不能太深； 4.玻璃珠植人的状态要合适，不能太浅 1.选用合格的涂料；</td></tr><tr><td>起皮脱落</td><td>1.涂料中的树脂含量不够； 2.涂料长期贮存变质； 3.路面未清扫干净； 4.路面潮湿； 5.水性涂料施工环境温度低于10℃； 6.融雪剂的侵蚀</td><td>2.注意保质期，涂料不能长期贮存； 3.路面彻底清扫干净，对水泥路面要打磨残碱； 4.路面干燥后再施工； 5.环境温度高于10℃施工； 6.选用合适的融雪剂</td></tr><tr><td>使用寿命短</td><td>1.涂料配比不合理，树脂用量过少； 2.涂层厚度不够； 3.路面清扫不干净</td><td>1.选用合格的涂料； 2.严格按规范施工，保证涂层厚度； 3.彻底打磨和清扫路面 1.改用合适的喷嘴；</td></tr><tr><td>标线边缘不整齐</td><td>1.喷嘴大小不合适； 2.喷嘴磨损； 3.喷涂压力太低； 4.稀释剂使用过量 1.喷嘴大小不合适； 2.喷嘴磨损；</td><td>2.换新喷嘴； 3.调高喷涂压力； 4.调整涂料黏度至适合喷涂 1.改用合适的喷嘴； 2.换新喷嘴；</td></tr><tr><td>标线厚度不均匀</td><td>3.喷涂压力太低； 4.涂料的黏度太高； 5.涂料输送管路不畅通 1.喷嘴大小不合适； 2.喷嘴磨损；</td><td>3.调高喷涂压力； 4.调低涂料的黏度； 5.疏通涂料输送管路，特别要注意双组分涂料的A、 B两组分要严格分开 1.改用合适的喷嘴；</td></tr><tr><td>标线形状扭曲变形</td><td>3.喷涂压力太低； 4.涂料的黏度太高； 5.涂料输送管路不畅通； 6.沥青软化，路面变形； 7.涂层未干或太软时就开放交通，被车轮碾压变形</td><td>2.换新喷嘴； 3.调高压力； 4.调低涂料的黏度； 5.疏通涂料输送管路； 6.注意对沥青路面的施工； 7．不过早开放交通</td></tr></table></body></html>  \n\n在标线施工质量控制的人、机、料、施工工艺诸因素中，人是第一要素，完善质量管理体系，选用优质涂料，使用维修良好的、调试好的划线机，严格按照规定的施工工艺作业，就能够施工出质量合格的标线。一般认为，施工标线质量的好坏，“三分靠涂料，七分靠施工”。GB/T16311—2005《道路交通标线质量要求和检测方法》是现场施工的质量控制标准，是标线施工方的自检及监理现场监督检查的依据。  \n\n![](images/f146e8497df8a89ace12f55ebfeed834fd98a53b8f422f8ba1655d1d43e5e584.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1067,
+        "chunk": "# 一、新开发的标线涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 1068,
+        "chunk": "# 1.环保的热熔标线涂料  \n\n热熔标线涂料生产过程中，铬黄颜料的扬尘污染是很严重的，我国已有采用在颜料外包一层硅或硅化物保护膜的包膜处理，可以减少铬黄粉尘的污染。还有将涂料的纸质包装袋或编织袋改用可熔化成涂料成分的包装袋，在施工现场，直接将成袋涂料连包装一起投人热熔釜里熔化，就有效地避免了由投料产生的粉尘污染。  \n\n用有机黄颜料和钛黄代替铬黄，也能解决热熔标线涂料的污染问题。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1069,
+        "chunk": "# 2.蓄能发光标线涂料  \n\n我国研制的蓄能发光标线涂料里掺有可蓄能无机化合物，靠吸收太阳光或灯光的能量，贮存后再释放发光。使用在路面上，能在黑夜无路灯和车灯照明下自发光。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1070,
+        "chunk": "# 3.不加固化剂的环氧标线涂料  \n\n国外研制的不加固化剂的热塑性环氧标线涂料在施工时，只需将涂料加热到220～250℃，用刮涂或喷涂的方法都能划设标线。其除了具有环氧涂料的与路面附着性好、与玻璃珠粘接好等优点外，不粘胎干燥时间短（5～10min)，在地表温度为－5℃时也能施工。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1071,
+        "chunk": "# 4.铝热剂标线涂料粉  \n\n国外研制的铝热剂标线涂料粉是一种方便的标线涂料，只需将标线涂料粉撒在需要划设的位置，用镁引燃标线粉，化学反应产生热量，将反应产物和标线粉的其他成分熔化混合，形成标线涂层，黏附在路面上。标线粉由FeO3粉、Al粉、TiOz粉、石英粉、玻璃珠等组成，用镁引燃后的化学反应式如下：  \n\n$$\n\\mathrm{Fe_{2}O_{3}+2A l=\\Delta A l_{2}O_{3}+2F e}\n$$  \n\n这种标线涂料粉是黄色的，可作为特殊环境条件下应急的标线材料、划设临时标线，易清除。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1072,
+        "chunk": "# 5.雨水覆盖下仍能逆反射的标线  \n\n国外研制的一种折射率特殊的逆反射材料，植人标线涂层后，雨夜里，司机能看清汽车大灯照射到的、被雨水覆盖的标线。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1073,
+        "chunk": "# 二、国外有关标线涂料的技术标准",
+        "category": " Introduction"
+    },
+    {
+        "id": 1074,
+        "chunk": "# 1．欧洲标准  \n\n欧洲标准是由各参与国国家标准局（奥地利、比利时、捷克共和国、丹麦、芬兰、法国、希腊、冰岛、爱尔兰、意大利、卢森堡、荷兰、挪威、葡萄牙、西班牙、瑞典、瑞士、英国等）共同组成的欧洲标准委员会（CEN）制订的标准，标准有三种正式文本（英文、法文、德文)。前面冠以EN，执行时再在EN前冠上所在国家的代号，如英国加BS，德国加DIN等。词头为prEN表示尚在拟订中，ENV则表示标准的初稿。  \n\n$\\textcircled{1}$ EN 1423 Roadmarking materials—Drop on materials—Glassbeads， antiskid aggregates andmixtures of thetwo《道路标线材料——面撒材料——玻璃珠、抗滑骨料及其混合》。  \n\n$\\textcircled{2}$ EN 1424 Roadmarking materials-—Premix glassbeads《道路标线材料——预混玻璃珠》。  \n\n$\\textcircled{3}$ EN 1436 Roadmarking materials—Performance for roadusers《道路标线材料——路用性能》。  \n\n$\\textcircled{4}$ EN 1824 Roadmarking materials—Road trials《道路标线材料——路试》。  \n\n$\\textcircled{5}$ EN 13197 Roadmarking materials—Wear simulators《道路标线材料——磨损模拟试验机》。  \n\n$\\textcircled{6}$ prEN 1871 Roadmarking materials-—Physical properties《道路标线材料———物理性能》。  \n\n$\\textcircled{7}$ prEN 12802 Roadmarking materials—Laboratery methods and identification《道路标线材料——试验方法和压痕》。  \n\n$\\textcircled{8}$ prEN 132l2 Roadmarking materials—Requirement for the factory production control《道路标线材料——工厂生产控制要求》。  \n\n$\\textcircled{9}$ prENV l3459-1 Roadmarking materials—Quality control Part 1 Sampling and testingfrom storage《道路标线材料——质量控制——第一节库中取样和试验》。  \n\n$\\textcircled{10}$ prENV 13459-2 Roadmarking materials——Quality control Part 2 Guidelines for preparing quanlity plans for the application of roadmarking products《道路标线材料—质 量控制—第二节标线施工的质量计划制定指南》。  \n\n$\\textcircled{11}$ prENV 13459-3 Roadmarking materials-Quality control Part 3 Performance in use《道路标线材料——质量控制——第三节使用性能》。",
+        "category": " References"
+    },
+    {
+        "id": 1075,
+        "chunk": "# 2.美国标准  \n\n美国全国性的标线涂料标准主要由美国材料与试验协会（American Society For Testingand Material，ASTM）制定，还有美国州际道路与运输工作者协会（AmericanAssociationof State Highway and Transportation Oficials，AASHTO）等制定的，各州也单独制定自己的地方标准。  \n\n（1）ASTM标准ASTM标准的编号顺序为ASTM $+$ 以字母为代码的分类 $+$ 标准的序号十制定年份 $+$ 标准名称。  \n\n$\\textcircled{1}$ ASTMD713—-90（1998）《道路标线涂料施工时用的试验方法》。  \n\n$\\textcircled{2}$ ASTMD868—85（1998）《道路标线涂料渗色程度的试验方法》。  \n\n$\\textcircled{3}$ ASTM D913—88 （Reapproved 1993） Standard Test Method for Evaluating degreeof Resistance toWear of TrafficPaint《评定标线涂料耐磨性的试验方法》。  \n\n$\\textcircled{4}$ ASTM D1l55—-89 （Reapproved 1994） Standard Test Method for Roundness ofGlassSpheres《玻璃珠圆度的试验方法》。  \n\n$\\textcircled{5}$ ASTM D1214--89 （Reapproved 1994） Standard Test Method for Sieve Analysis ofGlassSpheres《玻璃珠筛分的试验方法》。  \n\n$\\textcircled{6}$ ASTMD2205—85（1994）《道路标线涂料试验方法的选用指南》。  \n$\\textcircled{7}$ ASTMD3451—92（1992）《聚合物粉末和粉末涂料的试验方法》。  \n$\\textcircled{8}$ ASTMD4061—94（1994）《平面涂层逆反射性能的试验方法》。  \n$\\textcircled{9}$ ASTMD4796—88（1994）《热塑型交通标线材料粘接强度的试验方法》。  \n\nASTMD4960—89（1998）《评定热塑型交通标线材料颜色的试验方法》。  \n\n(2）AASHTO 标准AASHTO制定的有关标志和标线涂料及其试验方法的标准的编号为：M69；M220；M237；M247；M248；M249；M277；M290；M300；R31；T157;T237； $\\mathrm{T250}$ 0① AASHTO M247—02 Glass Beads Used in Traffic Paints《交通标线涂料用玻璃珠》。② AASHTO M248—91（2000）Ready-mixed white and yellow traffic paints《白色和黄色溶剂型交通标线涂料》。③ AASHTO M249—98 white and yellow reflective thermoplastic striping material（solidform）《白色和黄色反光热塑型交通标线涂料（固态）》。",
+        "category": " References"
+    },
+    {
+        "id": 1076,
+        "chunk": "# 3.澳大利亚标准  \n\nAS 2009—2001 Glass beads for roud-marking materials《道路标线用玻璃珠》。",
+        "category": " References"
+    },
+    {
+        "id": 1077,
+        "chunk": "# 4.英国早期标准（以下早期标准应用面较广）  \n\n$\\textcircled{1}$ BS 873 Part 1： 1983 Road traffic signs and internally illuminated bollards.Part 1Methodsoftest《道路交通标志和发光安全标柱第一节试验方法》。$\\textcircled{2}$ BS 873 Part 6： 1983 Road trafic signs and internally illuminated bollards. Part 6Specification for retroreflective and non-retroreflective signs《道路交通标志和发光安全标柱第六节逆反射和无逆反射标志的性能要求》。$\\textcircled{3}$ BS3236《热熔路面标线涂料》。$\\textcircled{4}$ BS 6044：1987Pavementmarkingpaints《路面标线涂料》。$\\textcircled{5}$ BS 6088: 198l Solid glass beads for use with road marking compounds and for otherindustrialuses《用于混合标线涂料和其他工业用途的实心玻璃珠》。",
+        "category": " References"
+    },
+    {
+        "id": 1078,
+        "chunk": "# 5.日本标准  \n\n$\\textcircled{1}$ JISK5665《道路标线涂料》。  \n$\\textcircled{2}$ JISR3301《道路标线涂料用玻璃珠》。",
+        "category": " References"
+    },
+    {
+        "id": 1079,
+        "chunk": "# 三、中国、日本、英国、美国热熔反光标线涂料标准的对比  \n\n中国、日本、英国、美国热熔反光标线涂料标准的对比见表3-12-29。  \n\n表3-12-29中国、日本、英国、美国热熔反光标线涂料标准的对比  \n\n\n<html><body><table><tr><td>项目</td><td colspan=\"2\">性能</td><td>中国 JT/T 280—2004</td><td>日本 JISK 5665—1992 3种</td><td>英国 BS 3236</td><td>美国 AASHTO M249</td></tr><tr><td rowspan=\"7\">物 理 特 性</td><td colspan=\"2\">密度/（g/cm3）</td><td>1.8~2.3</td><td>2.3以下</td><td></td><td>≤2.15</td></tr><tr><td colspan=\"2\">软化点/℃</td><td>90~125</td><td>80以上</td><td>≥65</td><td>102.5±9.5</td></tr><tr><td colspan=\"2\">流动度/s</td><td>35±10</td><td></td><td></td><td></td></tr><tr><td colspan=\"2\">不粘胎干燥时间/min</td><td>≤3</td><td>≤3</td><td></td><td>10℃±2℃,≤2min 32℃±2℃,≤10min</td></tr><tr><td rowspan=\"3\">亮度因数（45°/0°）</td><td rowspan=\"2\">白色</td><td>≥0.75</td><td rowspan=\"2\">≥0.75</td><td>工厂取样≥0.70</td><td rowspan=\"2\">≥0.75</td></tr><tr><td></td><td>工地取样≥0.65 工厂取样≥0.60</td></tr><tr><td>黄色</td><td>≥0.45</td><td></td><td>工地取样≥0.55</td><td>≥0.45</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>项目</td><td>性能</td><td>中国 JT/T 280—2004</td><td>日本 JIS K 5665—1992</td><td>英国 BS 3236</td><td></td><td>美国 AASHTO M249</td></tr><tr><td rowspan=\"7\">物 理 特 性</td><td>黄色度（限白色）</td><td></td><td colspan=\"2\">3种 0~0.1</td><td></td><td>≤0.12</td></tr><tr><td>抗压强度/MPa</td><td>≥12</td><td colspan=\"2\">≥12</td><td></td><td></td></tr><tr><td>粘接强度/psi</td><td></td><td colspan=\"2\"></td><td></td><td>≥180</td></tr><tr><td>低温抗裂性</td><td>-10℃X4h+室温4h， 三循环后无裂纹</td><td colspan=\"2\"></td><td></td><td>-9.4℃±1.7℃ 无裂纹</td></tr><tr><td>加热稳定性</td><td>200～220℃X4h在 搅拌状态下无明显</td><td></td><td>白色</td><td>200℃×6h亮度 因数≥65 200℃X6h亮度</td><td rowspan=\"2\"></td></tr><tr><td></td><td>泛黄、焦化、结块</td><td>200以下（双臂荷载各</td><td>黄色</td><td>因数≥55</td></tr><tr><td rowspan=\"4\">化学特性</td><td>耐磨性失重/mg</td><td>≤80(荷载1000g，200r)</td><td colspan=\"2\">250g，200r)</td><td></td><td></td></tr><tr><td>耐水性</td><td>浸水24h无异常 浸Ca(OH)2饱和</td><td colspan=\"2\">浸水24h无异常 浸Ca(OH)饱和溶液</td><td colspan=\"2\"></td><td></td></tr><tr><td>耐碱性</td><td>溶液24h无异常 人工加速耐候</td><td colspan=\"2\">18h无异常</td><td colspan=\"2\"></td><td></td></tr><tr><td>耐候性</td><td>性试验不产生 龟裂、剥落。亮度 因数变化不大 于原样的20%</td><td colspan=\"2\">12个月不产生龟裂、 剥落。颜色和亮度因 数变化不大</td><td colspan=\"2\"></td><td></td></tr><tr><td rowspan=\"4\">涂料成分组成</td><td>合成树脂/%</td><td></td><td colspan=\"3\"></td><td>18~22</td><td>≥18(限白色）</td></tr><tr><td>颜料/%</td><td></td><td colspan=\"3\"></td><td>≥6(限白色）</td><td>≥10(限白色)</td></tr><tr><td>玻璃珠/%</td><td>18~25</td><td colspan=\"3\">1号15～2号20～3号25 18 23 以上</td><td>20</td><td>30~40</td></tr><tr><td>非挥发物/%</td><td></td><td colspan=\"3\">≥99</td><td></td><td></td></tr></table></body></html>\n\n注： $\\mathrm{1psi=6894,76Pa}$ 量  \n\n从上表我们可以看出各国标准的特点是：  \n\n$\\textcircled{1}$ 中国标准与日本标准相近；  \n$\\textcircled{2}$ 美国、英国为保证涂料的成膜质量，对涂料组成中的合成树脂及颜料的质量分数有限定；$\\textcircled{3}$ 美国、日本为保证白色标线的色度，另外用黄色度来限定；  \n$\\textcircled{4}$ 美国涂料中的玻璃珠含量很高，达 $30\\%\\sim40\\%$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1080,
+        "chunk": "# 四、欧洲标准ZTVM02手册对反光标线材料的最低要求  \n\n$\\textcircled{1}$ 反光标线的白天逆反射系数应不小于 $150\\mathrm{med}/(\\mathrm{l}\\mathrm{x}\\cdot\\mathrm{m}^{2})$ （R3级）；  \n$\\textcircled{2}$ 潮湿环境下反光标线的白天逆反射系数应不小于 $35\\mathrm{mcd}/(\\mathrm{l}\\mathrm{x}\\cdot\\mathrm{m}^{2})$ ）（RW2级）；$\\textcircled{3}$ 标线涂层耐车轮碾压的次数应不小于200万次（H4级）；  \n$\\textcircled{4}$ 标线涂层的湿膜厚度应不小于 $0.6\\mathrm{mm}$   \n$\\textcircled{5}$ 标线涂层的抗滑摆值应不小于45BPN（S1级）；  \n$\\textcircled{6}$ 标线涂层的不粘胎干燥时间 $\\leqslant20\\mathrm{min}$   \n$\\textcircled{7}$ 标线的使用寿命≥保用期的 $90\\%$ 0",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1081,
+        "chunk": "# 五、标线涂料的发展趋势  \n\n综上所述，可以预料，标线涂料的国内发展趋势将可能为以下方向。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 1082,
+        "chunk": "# 1.强调环保  \n\n环境污染问题已成为我国经济高速发展的绊脚石，危害人们健康的重要因素之一，因而备受重视，水性标线涂料是减少环境污染的首选。  \n\n防止涂料中重金属的中毒是涂料界不争的课题，无铅、无铬、无镉的标线涂料将成为主流，美国联邦标准FED-STD141C已规定涂料中铅的含量（质量分数）应 $\\leq0.06\\%$ ，六价铬的含量用美国联邦标准试验规范TT-P-1952D测试应为阴性。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1083,
+        "chunk": "# 2.注重节能  \n\n能源的枯竭，迫使人们必须注意节约能源，不需加热的、性能优异的标线涂料将会有广阔的市场。国外的冷塑型标线涂料已应用得较多，我国还有待进一步研制配方和施工工艺及相应的配套施工设备，并使原材料国产化，开发出适合我国国情的冷塑型标线涂料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1084,
+        "chunk": "# 3.标线多功能化  \n\n一般标线的功能是给人们提供视觉效应，提醒注意交通安全，而突起结构振动反光标线除了白天和黑夜甚至在雨夜也能提供视觉效应外，还能提供动感、听觉（振动颤音）等功能，从而提高了标线的警示效果，目前已在一些需要警示的路段获得推广应用。估计不久的将来，具有磁性导航功能，自动引导车辆循序前进的智能标线将会问世。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1085,
+        "chunk": "# 4.能低温施工  \n\n标线工程往往是道路工程的扫尾工程，档期多在秋冬岁末，气候较冷，而涂料的施工温度至少 $10C$ 以上，为此我国已研制在低温条件下施工的标线涂料，如能在 $0^{\\circ}C$ 以上施工的水性标线涂料和双组分喷涂聚脲标线涂料等，聚脲标线涂料的涂层遇水会发涩，增加涂层的抗滑能力。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1086,
+        "chunk": "# 5.标线能长效  \n\n标线的使用寿命长，就能减少标线重涂的次数，减少封闭交通的次数和施工的危险。纳米标线涂料如果能够克服成本的劣势，将会得到应用。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 1087,
+        "chunk": "# 6.讲究性价比  \n\n在大力核算经济效益的今天，标线涂料的性价比就显得非常重要了，就目前阶段对热熔标线涂料而言，改用喷涂施工，能够提高划设标线的性能价格比，估计在公路养护中将会得到较多的应用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1088,
+        "chunk": "# 7.要求防滑  \n\n标线的防滑要求已逐渐被人们重视，而路面防滑涂料在交通安全保障工程中显现了其重要的地位，一些危险路段已纷纷铺设防滑路面，路面防滑涂料的需求量将日趋旺盛。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1089,
+        "chunk": "# 8.标准日臻完善  \n\n目前我国的标线涂料标准还有一些不够完善的地方，还有一些不便操作的试验，影响了标线涂料的质量控制。可以相信，随着标线涂料标准的日臻完善，我国标线涂料的质量将会得到大幅度的提高。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 1090,
+        "chunk": "# 9.注意路用试验  \n\n依靠实验室检测不能完全反映标线涂料的实际使用性能，只有路用试验才能真正考核标线涂料的综合使用性能。今后的标线涂料改进和新品种的开发，应注意更多地依靠路用试验。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1091,
+        "chunk": "# 10.大工程新要求  \n\n2010年上海世界博览会等许多即将开工的大型工程项目和新型道路建设工程将会对标线涂料提出更多、更新、更高的要求，将会研制出更多、更好的标线涂料适应新形势发展的需要。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1092,
+        "chunk": "# 参考文献  \n\n[1]全国道路標標示業協会．路面標示八下7，东京：共立速记印刷株式会社，平10（1998).  \n[2]Kappler R. Tests for Road Marking Systems. Cologne: Federal Highway Research Institute,2003.  \n[3] En l436: 2000 Road Marking Materials-Performance for Road Users.  \n[4]杜利民，郑家军，何勇．道路标线材料及应用．北京：人民交通出版社，2007.  \n[5]朱桂根，倪耀中，朱建新．ZRPH-1型双功能划线机的设计，见：云南省科学技术交流中心．现代道路与桥隧工程．北京：原子能出版社，2007：183-186.  \n[6]王毅明，道路交通标线施工工艺，见：云南省科学技术交流中心．现代道路与桥隧工程．北京：原子能出版社，2007： 131-137.  \n[7］杜玲玲，杨继宏．道路交通标线涂料的性能要求和检测．中国涂料，2007，22（7)：13-18.  \n[8]杜玲玲．我国公路建设用涂料的新动向．中国涂料年鉴，2005：6-21.  \n[9]杜玲玲，窦小燕，杜利民．道路交通标线涂料的合理使用．中国涂料，2004，（6)：36-39.  \n[10] 杜玲玲，杜利民，黄非．德国、法国道路交通标线涂料的应用考察．中国涂料，2004，（5）：38-45.  \n[11]杜玲玲，窦小燕，陈敏．道路交通标线玻璃珠的合理使用．公路交通科技，2004，21（11)：118-121.  \n[12]杜玲玲．提高道路标线质量的关键问题．公路交通科技，2003，20（6)：153-155.  \n[13］杜玲玲．水性道路标线涂料的发展与待解问题，中国涂料，2002，2：12-13.  \n[14]杜玲玲，李兴仁．国外道路标线材料的发展趋势．公路交通科技，2000，17（6)：64-66.  \n\n![](images/9277277d7d65addd85c5ed21b6994586a4393daaa664cacbb8d27aaf075dd0fa.jpg)",
+        "category": " References"
+    },
+    {
+        "id": 1093,
+        "chunk": "# 一、概述  \n\n随着工业专业化的发展，越来越多的涂料工厂向树脂生产工厂采购各种树脂，自己生产的品种逐渐减少。  \n\n涂料工厂无论用自制树脂或外购树脂，都是先制成漆料，然后再配制成清漆或色漆。树脂和漆料依据品种的不同有不同的生产工艺。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1094,
+        "chunk": "# 1.树脂生产工艺  \n\n树脂生产按其反应机理有缩聚型树脂和加成聚合型树脂，反应机理不同，生产过程也不同。在本书前面章节中对各种树脂的生产过程已分别作了叙述。综合起来，涂料工厂经常生产的树脂品种可归纳为下列3种有代表性的生产工艺。  \n\n(1）以醇酸树脂为代表的树脂生产工艺醇酸树脂是涂料工厂生产最多的，也是当前最主要的品种。它的生产过程包括醇解、酯化、兑稀和净化等阶段和工序。生产方式通常为间歇式，间歇式溶剂法的生产工艺流程如图4-1-1所示。  \n\n醇酸树脂的醇解和酯化反应的温度都在200℃以上，一般达到250℃左右。反应过程有4%左右的水生成，需要脱出。采用溶剂法，回流物量约8%。反应达到终点时需要快速停止反应。反应物一般稀释成一定浓度的树脂溶液。反应过程容易生成胶粒杂质，最后需要净化。  \n\n醇酸树脂间歇式工艺适用于各种规模的生产。大批量生产现在普遍采用仪表控制，正在推广集散控制系统（DCS）控制的生产方式。  \n\n醇酸树脂间歇式工艺在经过必要的调整以后，可以生产通过酯化反应生成的缩聚型树脂的其他品种，如聚酯树脂和环氧酯树脂。  \n\n(2）以氨基树脂为代表的树脂生产工艺涂料用氨基树脂也是涂料工厂经常自己生产的树脂品种。它的生成反应也是缩聚反应，但反应温度较低，约在 $100^{\\circ}C$ 左右。也有大量水分蒸出，在醚化过程中还要大量蒸出丁醇。因此需要抽真空降压操作。典型的合成工艺流程如图4-1-2所示。  \n\n![](images/b91f98c57414d154f172763fd561c33e506f789eb7e9e706c78726d2d15f39f4.jpg)  \n图4-1-1 醇酸树脂工艺流程  \n\n1-液体苯酐计量罐；2-液体原料计量罐；3,5—冷凝器；4—分水器；6—兑稀（稀释）罐；   \n7—反应釜；8—高温齿轮泵；9—内齿泵；TR—温度记录；TRCA—温度记录、调节、报警  \n\n![](images/34a931f102b3ae7123364f81091d8cc533448fed16557b38bbc54d8db6fbcd8a.jpg)  \n图4-1-2氨基树脂工艺流程1一反应釜；2—冷凝器：3一蒸出物接收器；4一原料计量罐；5—废水贮罐；6—网筛；7一中间贮罐；8一过滤器  \n\n![](images/7359b48a4b9ae3b79629eec2a85657a53cc17204b761c9631d11eb78875c88bc.jpg)  \n图4-1-3丙烯酸乳液工艺流程1-反应釜；2—冷凝器；3—单体混合罐；4—单体滴加罐；5—助剂滴加罐；6—网筛；7-调节釜：8一过滤器  \n\n物料通过计量加入反应釜1中，升温进行甲基化反应，降温放置，分水，再进行醚化，蒸出水分，并在适当真空度下蒸出丁醇，调整到控制的固体分、黏度等指标，经过网筛6，送人中间贮罐7，再经检测合格后，过滤贮存。蒸馏出的水分和丁醇数量约占总投料量的30%左右。因蒸出速度较快，故需要冷凝面积较大的冷凝器2和蒸出物接收器3，并附有计量装置。产品得率约为投料量的 $45\\%$ 左右。  \n\n因为反应温度低，通常可用蒸汽加热。因为蒸出物料的量大，所以比醇酸树脂生产时所用的冷凝器的面积要大。同时抽真空设备为生产过程所必需。  \n\n(3）以丙烯酸树脂和乳液为代表的树脂生产工艺丙烯酸树脂属于加成聚合型树脂，用溶剂聚合方法可以得到树脂溶液，用乳液聚合方法则得到树脂乳液。这种树脂的生产工艺过程（如图4-1-3所示，以丙烯酸乳液为例）是先将约占总量一半的水乳化液投人反应釜1中，丙烯酸单体在单体混合罐3中混合，压人单体滴加罐4中，引发剂配成溶液通过助剂滴加罐5分批加入反应釜中，通常用热水加热反应釜，至规定温度，在搅拌下滴加单体，加完保温，直至反应完成，放入调节釜7，进行检验和调整，然后过滤贮存。  \n\n这类树脂或乳液生产工艺特点是：物料是分批陆续加入反应釜，回流量少，反应温度低，但温度控制严格，以防爆聚。  \n\n从以上3种代表性生产工艺，可以看出在加料方式上有分批加人、分批滴加和基本上全部物料一次投加等不同方式；反应温度有高（ $250^{\\circ}C$ 左右）有低（ $100^{\\circ}C$ 左右)；反应过程有一次升温的，也有升温降温反复进行的；反应过程中物料蒸馏分离量有多有少等差别。因此它们的生产装置也不尽相同，以适应生产的需要。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1095,
+        "chunk": "# 2.漆料生产工艺  \n\n漆料作为液态清漆和色漆的半成品，它的生产工艺有两种形式。一种是将固体或液体树脂溶解于相应的溶剂中，例如环氧树脂漆、硝基漆、过氯乙烯漆等产品的漆料，这种称为树脂溶解制备漆料的工艺比较简单，即将树脂加人溶解釜内，在搅拌状况下使树脂溶解，可以是常温，也可以加热升温以加速溶解，然后经过净化，贮存于贮罐中备用。另外一种是热炼法，由几种不同品种的成膜物质在一定温度下炼制成漆料，如脂胶漆料、酚醛树脂漆料和热制法沥青漆料都采用这种工艺。它包括配料、热炼、稀释和净化 $4$ 个工序。树脂、油经计量装入热炼釜中，迅速升温至规定温度（一般为 $270{\\sim}280^{\\circ}\\mathrm{C})$ ，保持一定时间（根据漆料油度长短而定)，达到规定黏度后迅速输送至稀释罐（用真空抽送或泵送）中，降温后用相应溶剂稀释，经净化后送至贮罐。这种工艺特别强调快速升温和快速降温，热炼装置要能满足这种要求。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1096,
+        "chunk": "# 3.清漆生产工艺  \n\n清漆为涂料产品的一大类，依据所用成膜物质而分别命名。通常是由漆料加适当助剂配制而成，例如酚醛清漆是由酚醛漆料加入催干剂和适量溶剂配制而成，工艺较简单。有的是与漆料分开制备，有的则在漆料制备时，于净化之后，即送到清漆配制釜，按配方比例加入应加的物料，搅拌均匀，经过检验，即可包装成为成品。清漆配制通常在常温下进行。  \n\n综合以上所述，树脂、漆料和清漆的生产装置主要是树脂和漆料的反应设备、稀释设备、净化设备、漆料的树脂溶解设备和清漆的配制设备，此外还有与之配套的配料、计量、加热、输送、贮存设备等。本节重点介绍其中的反应、稀释、加热和净化设备。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1097,
+        "chunk": "# 二、反应装置  \n\n树脂和漆料生产的核心装置是反应装置。间歇式生产工艺的反应装置包括配有搅拌器的反应釜和相应的加料、冷凝回流装置等，根据生产品种不同，在装置形式和包含内容上略有差别。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1098,
+        "chunk": "# 1.反应釜的种类  \n\n反应釜是反应装置的主体设备。对反应釜有不同的分类命名方法。如前所述，反应釜可按生产的产品命名为醇酸树脂反应釜、氨基树脂反应釜、乳液反应釜等。可按所进行的反应，称为醇解釜、酯化釜、聚合釜等。也可按反应温度的高低，称为高温树脂反应釜（150～300℃）和低温树脂反应釜（60～150℃）。有的按反应釜加热的方式，称为直接火加热反应釜、电阻远红外加热反应釜、工频电感加热反应釜等。习惯上多从制造材质上进行分类命名，主要有碳钢反应釜、复合钢板反应釜、不锈钢反应釜和塘玻璃反应釜4类。  \n\n碳钢反应釜由于易生锈和不耐化学介质腐蚀，又有使反应产物颜色加深的病，现在已基本不用。复合钢板反应釜所用复合钢板是由一层不锈钢板和一层碳钢板热轧而成，它主要用在采用工频电感应加热的场合，与物料接触的是不锈钢，碳钢层主要用于电感应加热。  \n\n使用最广的是不锈钢反应釜和塘玻璃反应釜。  \n\n(1）不锈钢反应釜制作反应釜的不锈钢大多是铬镍奥氏体型不锈钢，不能淬火强化，无磁性，塑性、韧性、工艺性能及耐腐蚀性能良好。碳含量不大于 $0.03\\%$ 的超低碳不锈钢还有很好的抗晶间腐蚀性能。含钼的奥氏体型不锈钢在有机酸和某些还原性酸中有更好的耐蚀性。  \n\n制作反应釜的不锈钢热轧钢板，其主要牌号为0Cr19Ni9和 $\\mathrm{0Cr18Ni12Mo_{2}}$ ，相当于进口钢材牌号304和316。  \n\n不锈钢反应釜坚固耐用，既可用于制造高温树脂反应釜，也可以用于制造低温树脂反应釜。它具有下列特点。  \n\n$\\textcircled{1}$ 不锈钢的力学性能好，只要设计合理，可承受较高的工作压力，也可承受加料时小块固体物料的冲击。  \n\n$\\textcircled{2}$ 耐热性能好，工作温度范围广（ $-196\\mathrm{\\sim}600^{\\circ}\\mathrm{C})$ 。在较高温度下不会氧化起皮，可用于直接火加热。  \n\n$\\textcircled{3}$ 具有很好的耐腐蚀性能，不生锈。  \n\n$\\textcircled{4}$ 传热效果比塘玻璃反应釜好，升温和降温的速度较快。  \n\n$\\textcircled{5}$ 有良好的加工性能，可按工艺要求，制成各种不同形状和结构的反应釜。还可以将釜壁打磨抛光，使放料时不挂料，也便于清洗。  \n\n不锈钢反应釜的缺点是价格高，比塘玻璃反应釜要贵很多。此外，在耐腐蚀性能方面也有局限性，如在接触卤族元素（氟、氯、溴等）时会产生晶间腐蚀，因此，不锈钢反应釜不能在有卤族元素介质存在的情况下工作。  \n\n(2）塘玻璃反应釜糖玻璃反应釜俗称塘瓷反应釜或塘瓷釜，是将含有二氧化硅的玻璃质釉涂于低碳钢制成的容器表面，经高温（约 $800{\\sim}900^{\\circ}\\mathrm{C}$ ）烧结而成。形成的塘玻璃衬里耐腐蚀性能好，能耐一般无机酸、有机酸、弱碱液 $(\\ 60^{\\circ}C$ ， $\\mathsf{p H}\\leqslant\\pmb{1}2)$ 、有机溶剂等介质的腐蚀，但不耐氢氟酸、高浓度强碱及温度高于 $180^{\\circ}C$ 的浓磷酸的腐蚀。此外，塘玻璃衬里硬度高，耐磨，像玻璃一样光滑，不易黏附物料，容易清洗。  \n\n但是，由于糖玻璃反应釜毕竟是用两种不同物理性能的材料复合而成，且玻璃釉质脆性大，因此它在耐压、耐温、抗机械冲击等方面还是有许多不足之处。  \n\n$\\textcircled{1}$ 允许工作压力有限制一般釜内为 $\\Hat{0}_{*}2\\mathbf{M}\\mathbf{P}\\mathrm{a}$ （轴封为软填料密封）或 $\\mathrm{0.39\\mathord{\\sim}1M P a}$ （轴封为单端面或双端面机械密封)，夹套为 $\\mathrm{0.59MPa}$ 。由于塘玻璃设备的法兰密封及轴封的严密程度要比非糖玻璃设备差（因烧结时变形所致)，所以它也不宜用于真空度大于$80k\\mathbf{Pa}$ 的工作场合。  \n\n$\\textcircled{2}$ 允许工作温度有限制 通常只能在 $200^{\\circ}C$ 以下使用。  \n\n$\\textcircled{3}$ 温度急剧变化时，瓷釉层可能出现破损按中国国家标准，糖玻璃设备的耐温差急变性数值是：冷冲击不大于 $110^{\\circ}C$ ，热冲击不大于 $120^{\\circ}C$ 0  \n\n$\\textcircled{4}$ 瓷釉层很脆，抗机械冲击能力很低要严防重物、工具掉落釜中，在安装搅拌器时要防止由于转向不对而脱扣坠落。不许碰撞或锤击塘玻璃设备。  \n\n③传热较慢，而且导电性差物料在釜内运动时容易造成静电荷的积聚。因此，必须采取有效的防静电措施。  \n\n基于上述缺点，糖玻璃反应釜主要适用于较低温度下反应的树脂生产，如氨基树脂、乳液，以及反应介质呈酸性的情况下。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1099,
+        "chunk": "# 2.反应釜的结构  \n\n（1）概述 反应釜从形式上有开式和密闭式之分。  \n\n表4-1-1 反应釜组成  \n\n\n<html><body><table><tr><td>容器部分</td><td>机械部分</td></tr><tr><td>釜盖（上封头，包括人孔、视镜等开孔） 简体</td><td>传动装置[包括电机、减（变）速机构或液压马达、联轴器及机架]</td></tr><tr><td>釜底（下封头，包括放料口、放料阀）</td><td>搅拌装置（包括搅拌器、搅拌轴及附件）</td></tr><tr><td>传热结构（各种形式夹套或蛇管，可兼有）</td><td>轴封装置</td></tr><tr><td>支座</td><td></td></tr><tr><td>保温层</td><td></td></tr></table></body></html>  \n\n开式反应釜结构比较简单，由筒体和筒底（下封头）组成，一般装有活动釜盖，传动和揽拌装置为可移动式。在树脂、漆料生产中，除个别品种外，现在广泛使用密闭式反应釜。除特殊注明外，下面讨论的反应釜就指密闭式反应釜。  \n\n反应釜通常由容器部分和机械部分组成，如表4-1-1所示。这两部分可由多个不同专业生产厂分工制造，然后进行组装，以达到优质、高效、降低成本的目的。  \n\n图4-1-4为醇酸树脂反应釜的结构。该反应釜的主体由筒体和釜底（下封头）、釜盖（上封头）组成，其传热结构是外有夹套、内有蛇管。利用导热油进行加热和冷却。釜盖上安装传动装置和轴封装置，它们带动揽拌器运转并防止轴封处泄漏。釜盖上设置人孔、视镜、加料孔、出气孔、取样孔及温度计孔等。支座、放料阀及保温层，图中未标出。  \n\n（2）筒体与封头除了直径很小时用无缝钢管做筒体的情况外，容器公称直径是指筒体的内径。其数值多为 $100\\mathrm{mm}$ 的整数倍，可按有关标准选取。筒体大多用钢板卷成圆筒，再焊接而成。反应釜筒体的高度与内径的比值称为长径比（即 $H/T$ ，见图4-1-7)，通常推荐值约为 $1\\sim1.3$ 。它与反应釜容积大小及产品品种等因素有关。不同的加热方式，也对反应釜的长径比提出了不同的要求。如用直接火加热釜底，要求釜底面积大些，则长径比要稍小。如果需要通过筒体部分加热的，长径比需要大些。  \n\n![](images/c0dcc15adb14d67bbce8e03923b92f87ce85f127538f9c34ba64405d34048269.jpg)  \n图4-1-4 醇酸树脂  \n\n反应釜（导热油加热）结构1—减速机（带电机）；2—机架；3一填料箱；4—上封头；5—打沫翅；6一夹套；7一搅拌轴；8一蛇管；9一搅拌器；  \n\n10—简体；11—下封头  \n\n反应釜的封头主要有椭圆形封头和碟形封头两种（见图4-1-5)。碟形封头是一种带圆弧折边的球形封头。碟形封头的深度较椭圆形封头浅，如目前国内标准的碟形封头R=T，$r{=}0.15T$ ，其曲面高度 $h_{1}=0,226T$ 。它的受力情况比椭圆形封头略差。椭圆形封头为半个旋转椭球面再加上一段直边。由于椭圆曲线的曲率变化是连续的，所以受力情况较好。国内标准椭圆形封头取长轴与短轴之比为2，也就是封头曲面高度等于封头内径的$1/4$ ，目前国内这两种封头的直边高度 $h_{2}$ 依据封头直径选取。封头直径 $T\\leqslant2\\ensuremath{\\mathrm{m}}$ ， $\\bar{h}_{2}$ 取 $25\\mathrm{mm}$ ； $T>2\\mathbf{m}$ $h_{2}$ 取 $\\mathsf{40m m}$ 心  \n\n![](images/655e5c9cbc160803044fd71ec6b54dd4d11cbe46e4cfb0f0f0afee41b0c047f0.jpg)  \n图4-1-5 反应釜用封头  \n\n不同用途的反应釜，釜盖开孔数量不同。图4-1-6为醇酸树脂反应釜的釜盖开孔示意。反应釜盖的开孔配置，也随釜盖直径的大小及出料方式的不同而有差异。如釜盖直径较小，布孔位置不足，可一孔多用。如在人孔盖上设视镜；在进料孔上设置一个水平总管，供几种原料管路并联连接等。若布孔位置富余，为操作方便，除人孔外可再设置手孔。对直接火加热的反应釜，为安全计，都不在釜底开孔接管，出料采用一-  \n\n个插底管，利用真空或气压从釜盖上出料。取样大多用插人液面下的取样管借助真空取样，也有从釜体下部侧壁取样的。因为温度控制特别重要，  \n一般留两个管孔，可装两支不同的温度计。  \n\n反应釜的筒体与釜底（下封头）都是焊接的，所有内部的焊缝都要打磨，以免挂料。筒体与釜盖（上封头）的连接，常用两种方式——法兰连接和焊接。法兰连接的釜盖可拆开，便于反应釜的检查、清洗和检修，但其制造成本高，增加了泄漏的可能性。而且若长期不拆卸，螺栓、螺母都锈住了，拆卸起来很困难。所以一般只推荐在小容积$(\\leq3m^{3}$ ）的反应釜中使用。  \n\n现在不用大法兰的焊接式反应釜使用较普遍。由于没有大法兰，釜盖上必须开设人孔，以便检修。搅拌器如不能通过人孔装卸，应制成可拆卸式结构。人孔应是带回转盖的快开结构，开启轻便，以方便工人操作，减轻体力劳动强度。  \n\n（3）反应釜的容积计算及装料系数 目前国内通用的反应釜由圆柱形筒体外加上、下两个标准椭圆形封头组成（见图4-1-7）。  \n\n简体的容积容易计算，封头的容积可以从有关手册查出，也可由下式计算：  \n\n![](images/5e442c73e78ebd917cd5e129712adc51899ac8ff5d217889ba3d810ba9435ce9.jpg)  \n图4-1-6 醇酸树脂反应釜的釜盖开孔示意  \n\n1—人孔；2-视镜；3，4—温度计口；5—加料口；6—灯孔；7一情性气体人口；8—排空口；9一回流液入口；10一搅拌轴（轴封）口；11—蒸汽出口（接冷凝器）；12一真空压力表口；13，14一取样口（或有一个备用口）  \n\n$$\nV_{1}=\\frac{\\pi}{24}T^{3}=0.1309T^{3}\n$$  \n\n式中 $V_{1}$ -—不计人直边 $h_{2}$ 的椭圆形封头容积， $\\mathbf{m^{3}}$ $T$ —封头内径， $\\mathbf{m}$  \n\n在此基础上，就不难求出反应釜的全容积：  \n\n$$\nV{=}\\frac{\\pi}{4}T^{2}(H{+}2h_{\\bar{z}}){+}\\frac{\\pi}{12}T^{3}\n$$  \n\n式中 $V$ —反应釜的全容积， $\\mathbf{m^{3}}$ ·$H$ —筒体高度， $\\mathbf{m}$ $h_{2}$ 封头直边高度， $\\mathbf{m}$ 中  \n\n例如一个内径为 $2.2\\mathrm{m}$ ，筒体高度为 $2.3\\mathrm{m}$ ，封头直边高度为 $40\\mathrm{mm}$ 的反应釜，按上式计算，求得全容积为 $\\mathrm{11.84m^{3}}$ 0  \n\n反应釜的容积，分为全容积、公称容积（额定容量）及有效容积（装料容积）3种。全容积系反应釜筒体和上、下封头容积之和，公称容积或额定容量一般不包括釜盖（上封头）的容积。有效容积指装料容积，它与全容积之比称装料系数。如物料在反应过程中星多泡沫或沸腾状况时，只能取 $0.5\\sim$ 0.65；泡沫不多、搅拌形成的旋涡不大时，装料系数可达 $0.7\\sim0.75$ ；反应平稳时，装料系数可取 $0.8\\sim$ 0.85。通常装料系数大多取 $0.6\\sim0.8$ 。  \n\n![](images/5a7c8f8f71d20e010c941f77a0ffceb71372c9f88ce5a9ea932eba2762bf52d0.jpg)  \n图4-1-7 反应釜结构",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1100,
+        "chunk": "# 3.反应釜的传热结构  \n\n反应釜中物料在反应过程中要吸热或放热，有时还要反复进行。反应釜作为传热容器，使外来热源传人以加热物料，或使物料的热能用热载体吸收以冷却物料。依据热源不同，反应釜釜体可设计成不同形式。  \n\n反应釜加热有两种形式，即直接加热和间接加热。直接加热，如燃料燃烧的直接火加热、电阻远红外加热或工频电感加热，都是直接对釜底和筒体进行加热。间接加热，使用气相或液相热载体对反应釜进行加热，如蒸汽加热和导热油加热。间接加热的反应釜，就要设置各种形式的传热结构。釜体外部最常用的是普通夹套和半管夹套，釜体内部常用蛇管（盘管)。为了增加传热面积，有的釜内设置了传热挡板。这些传热结构，如通人冷却水等冷却介质，即可用于冷却。  \n\n(1）普通夹套简称夹套。夹套的高度应不超过釜内液面的高度，以免形成“干烧”，使釜内物料形成局部过热或结焦现象。为了适应反应釜内物料不同的液面高度，同时也为了更方便地调节加热面积的大小，也可将夹套设计成2段或3段。这种设计，特别适用于原料分批加入的反应釜。国内大型的醇酸树脂反应釜，有的夹套为3段（包括釜底在内)，有的设计成2段。经验表明，适当降低夹套位置，将夹套设计成2段是恰当的。  \n\n夹套的宽度大多为 $50\\mathrm{mm}$ 1 $10\\mathrm{m^{3}}$ 以上的大型反应釜，夹套宽度可放大至 $\\mathbf{100mm}$ 左右。为了提高传热效果，常在夹套内设置螺旋导流板（见图4-1-8)。螺旋导流板与釜壁或夹套壁的间隙要尽量小些，以免热载体走“捷径”。螺旋导流板提高了热载体的流速，提高了夹套侧流体的对流传热系数，并使热载体在夹套内均匀分布，防止产生“死角”。  \n\n为了减小由于简壁与夹套壁温度不同而产生的温差应力，常在高温树脂反应釜的上部夹套中设置膨胀节，底部夹套由于封头有一定的补偿能力，不再设置膨胀节。  \n\n在夹套内通入气态或液态热载体，简体承受外来压力，带夹套的筒体要按外压容器考虑，厚度要经过计算。在操作中一定要注意控制夹套内的压力不得超过设计规定值，否则筒  \n\n体将会被压疱。  \n\n![](images/779a28aa9d8260e843cf7d9769b6287ed3ddc4a1192d4d5004abbd368715644b.jpg)  \n图4-1-8 螺旋导流板  \n\n![](images/0a3cb3b05c673d001da632ffd32f9244984a5429820b922129ebcf2ed335c506.jpg)  \n图4-1-9 半管夹套结构  \n\n(2）半管夹套又称螺旋半圆管夹套，其结构如图4-1-9所示。半管可用整管切割或板材成型而成。由于加工能力提高了，近年来半管夹套获得了比较广泛的应用。  \n\n半管夹套有3个特点。  \n\n$\\textcircled{1}$ 可减小设备壁厚，节省材料由于带有夹套的反应釜的简体和封头要按外压容器设计，其壁厚较大。而半管反应釜，由于半管尺寸小，加上焊上的半管大大增强了刚性和承压能力，无论筒体或封头均不必按外压容器设计，壁厚大为减小。如容积为 $12\\mathbf{m^{3}}$ 的醇酸树脂反应釜（导热油加热)，夹套反应釜筒体的名义壁厚为 $16\\mathrm{mm}$ ，釜底为 $20\\mathrm{mm}$ ，而半管反应釜筒体和封头的名义壁厚都只需 $10\\mathrm{mm}$ 0  \n\n$\\textcircled{2}$ 提高传热效率由于半管的流道截面积小，热载体流速大，因而对流传热系数也大，提高了传热效率。这一特点适用于液相热载体。  \n\n$\\textcircled{3}$ 节约能量半管的总容积比夹套的总容积小得多。仍以 $12\\mathrm m^{3}$ 醇酸树脂反应釜为例，夹套的总容积为 $\\mathsf{1.8m^{3}}$ ，而半管的总容积仅为 $0.2\\mathbf{m^{3}}$ ，二者相差8倍。有的反应釜在生产过程中，要反复进行升温和降温。夹套热载体容量大，在反复升温、降温过程中，就要多消耗一些能量。  \n\n半管反应釜的缺点：一是制造难度较大，费工，所以虽然省了一些材料，但总的造价仍与夹套反应釜相近；二是容易产生泄漏。其原因是因为焊缝太多，焊接质量要求高。特别是反复进行加热和冷却的反应釜，由于温差应力的影响，容易产生焊缝裂纹。  \n\n由于半管反应釜发生焊缝泄漏的可能性和概率要比夹套反应釜大，所以半管反应釜最宜用于液相热载体加热和冷却的低温树脂反应釜及只作加热用的高温树脂反应釜。有的树脂反应釜的半管夹套只用于导热油加热，冷却专门用釜内蛇管通水冷却。  \n\n(3）蛇管也称盘管，为浸人式传热装置。设置蛇管的目的，对已有夹套或半管夹套的反应釜来说，是为了加大传热面积，加快升、降温速度，或专作冷却用；对一些没有或无法设置各种形式夹套的反应釜（如电阻远红外加热或工频电感加热的反应釜）来说，它可以起到冷却和辅助加热的作用。一般反应釜容量大于 $\\mathrm{{6m^{3}}}$ 时，在已有夹套的基础上，可考虑增设蛇管。  \n\n蛇管大多盘成与釜壁呈同心圆的螺旋状，大多为单列。图4-1-4所示的醇酸树脂反应釜内的蛇管即为单列蛇管，分上、下两段，便于调节。由于蛇管在反应釜内，万一泄漏可能引发大事故，因此要做到绝对安全可靠。必须注意以下两点。  \n\n$\\textcircled{1}$ 保证设计、制造质量蛇管应设计成能承受较高的压力。质量应经严格的检验。  \n\n② 蛇管支撑要牢固蛇管应紧固在牢靠的支架上，支架必须与釜壁焊接。因为当釜内物料剧烈搅拌时，任何松动会使蛇管发生振动，并与支架摩擦，天长日久，就能将蛇管磨漏。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1101,
+        "chunk": "# 4.反应釜的搅拌  \n\n搅拌是涂料生产中重要的单元操作，搅拌装置是反应釜的重要组成部分。搅拌能起到液液或液-固相间充分混合或分散的作用，从而达到强化传热、加速溶解和化学反应等目的。在树脂生产过程中，合理地利用搅拌，对提高产品的质量和缩短反应时间都有重要的意义。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1102,
+        "chunk": "# (1）搅拌的基本原理  \n\n$\\textcircled{1}$ 总体流动与湍流脉动搅拌槽内液体运动的方式，不外是周向（切向）流动、径向流动和轴向流动以及这3种流动的组合，这些流动统称为总体流动。从流体力学原理得知，流体做湍流运动时，除总体流动外，还存在着湍流脉动（或称湍动)。所以搅拌槽内处于湍流状态的液体，同时有总体流动和湍流脉动存在。这是物料得以均匀混合的两个因素。总体流动是液体以一定的方向并在较大范围内的宏观流动，它可以使混合液体破碎成较大的液团，从而使槽内各部分物料得到初步的混合。湍流脉动是液体质点在很小距离内做不规则的微观流动，它是由平均流动与大量不同尺寸、不同强度的旋涡运动叠加而成，高速旋转的旋涡与液团之间会产生很大的相对运动和剪切力，液团在这种剪切力作用下被破碎得更加细小，液团中的被分散物进一步细分，从而达到更小尺度上的均匀混合。  \n\n总体流动的大小可用容积循环速率来衡量，它是指单位时间内直接由桨叶排出的液体量及夹带液体一起运动的液体量，与搅拌器的类型、直径、转速及液体的黏度等因素有关。  \n\n湍流脉动的强弱程度（湍流强度）与液体离开桨叶时的速度头有关。速度头越大，液体的湍动越强，这股液体与搅拌槽内其他液体之间的速度梯度和剪切力也越大。速度头也称动压头，可表示为 $\\tau e^{2}/2g$ ， $\\tilde{w}$ 为流速 $(m/s)$ ， $\\boldsymbol{\\mathbf{\\mathit{g}}}$ 为重力加速度 $(\\mathrm{m}/\\mathrm{s}^{2})$ 。湍流强度与液体的单位体积消耗的能量 $N/V$ 有着密切的关系， $N/V$ 越大，液体的湍动越强。  \n\n总之，一个混合过程一方面是通过主体流动达到一定的调匀度，另一方面通过湍流脉动进一步降低分隔尺度，使之从微观上去看也更加均匀了。  \n\n$\\textcircled{2}$ 打漩现象当搅拌桨叶置于搅拌槽中心位置（大多如此），槽内液体黏度不高，且搅拌桨叶的转速足够高时，槽内液体都会产生切向流动，甚至使全部液体围绕着搅拌轴团团转。槽内液体在离心力作用下涌向槽壁，使周边部分的液面上升，中心部分的液面自然下降，于是形成一个大旋涡（见图4-1-10)。搅拌桨叶的转速越高，旋涡的深度越深。这种流动形态叫“打漩”。  \n\n![](images/3694643cdc2215396ba3184e12468b9497fdf6f0997d234166a23f4ff6fb4fec.jpg)  \n图4-1-10 打漩现象  \n\n打漩时混合效果不好，特别是靠近中心处，不同液体层之间，几乎无速度梯度，形成了所谓“固体回转部”的不良混合区。此外，旋涡的形成使容器的容积利用率降低，严重时还会吸人空气，使液体中混人气泡，并使搅拌轴受液流冲击，搅拌器振动加剧。因此，在一般情况下都要抑制打漩。  \n\n抑制打漩的方法主要有两种，一种是搅拌轴偏置，另一种最常用的方法是在搅拌槽内设置挡板。  \n\n$\\textcircled{3}$ 挡板挡板的作用，一是改变了搅拌槽内液体运动的方向，使切向流动变为轴向流动和径向流动（见图4-1-11)，抑制了打漩现象。二是液流在挡板后形成许多无规则的旋涡(见图4-1-12)，增大了被揽拌液体的湍流强度。总之，挡板的设置改善了搅拌效果。  \n\n设置挡板的缺点是功率消耗成倍地增加，也给清洗搅拌槽带来一些麻烦。  \n\n挡板的数量、大小及安装方式也会影响搅拌槽内液体的流动状态和搅拌功率消耗。  \n\n挡板宽度W通常为槽（内）径 $T$ 的 $1/10{\\sim}1/12$ ，当液体黏度较高时也可减小至槽径 $T$ 的 $1/20$ 。挡板的长度可这样决定，其上端一般略高于液面，下端要伸到槽底。挡板的数量视槽径的大小而异，小直径槽可用 $2{\\sim}4$ 个，大直径槽可用 $4\\sim8$ 个，以用4个居多。宽度为槽径1/10的4块挡板，一般已够用，并称之为“标准挡板条件”。  \n\n![](images/50e05f878fe861582d89eb2429128de0bb7f8931d2e6d455c9087e2ca365ef79.jpg)  \n图4-1-11 挡板对流型的影响  \n\n![](images/301f8b2a307746abd80c4b96824456978d528d7375222f637c04eb9d13d623dc.jpg)  \n图4-1-12 挡板安装方式  \n\n挡板沿槽壁均匀分布，垂直安装，挡板的安装方式如图4-1-12所示。挡板离壁距离一般为挡板宽度W的 $0.2\\sim1$ 倍。当槽内有传热蛇管时，其支架也起到挡板的一部分作用。  \n\n![](images/67751199cc433e0ad24ed422e2838c144a3b6505c809cf8d0af0717c7f765cc3.jpg)  \n\n图4-1-13 浆式搅拌器  \n\n随着液体黏度的增大，液体的黏性能抑制打漩。从液体黏度大于 $5\\mathrm{Pa}\\cdot\\mathbf{s}$ 开始，可减小挡板宽度；当液体黏度超过 $12\\mathrm{Pa}\\cdot\\mathbf{s}$ 后，已无需安装挡板。  \n\n(2）反应釜常用的搅拌器树脂反应釜常用的搅拌器有以下几种形式一桨式、推进式、涡轮式、三叶后掠式、锚式和框式、框板式。它们各有其自身的特点，只有在充分了解这些特点的基础上，才能更好地加以选用。  \n\n$\\textcircled{1}$ 桨式搅拌器桨式搅拌器可以说是最简单的搅拌器。通常它只有2个叶片，根据叶片是垂直安装或倾斜安装分为平桨（直叶）和斜桨（斜叶)，如图4-1-13所示。  \n\n平桨式搅拌器主要造成周向流动和径向流动，液体沿轴向的混合效果较差，而斜桨式搅拌器可产生一定的轴向流动。根据搅拌器所产生的流型，习惯上常把它们主要分为两类—径向流搅拌器(叶轮)和轴向流搅拌器（叶轮)。前者使液体主要在搅拌器（叶轮）半径和切线方向上流动；后者使液体主要在与搅拌轴平行的方向上流动。如上述平浆搅拌器属径向流叶轮，而斜桨式搅拌器一般纳入轴向流叶轮范畴。也有一些特例，如用于高黏度液体搅拌的锚式和框式搅拌器，主要使液体产生周向运动，可不归人上两类。  \n\n桨式搅拌器以及后面要介绍的其他形式搅拌器，其桨叶端部适宜的圆周速度与被搅拌的液体介质黏度有关，黏度高时速度要低，黏度低时速度可高些。它们之间的关系可参考表4-1-2。  \n\n表4-1-2浆端圆周速度与介质黏度的最适宜关系  \n\n\n<html><body><table><tr><td>搅拌器形式</td><td>介质黏度 /Pa·s</td><td>适宜的桨端圆周速度 /(m/s)</td><td>搅拌器形式</td><td>介质黏度 /Pa·s</td><td>适宜的桨端圆周速度 /(m/s)</td></tr><tr><td rowspan=\"2\">桨式</td><td>1~4</td><td>3.0~2.0</td><td>推进式</td><td>1~2</td><td>16.0~4.0</td></tr><tr><td>4~8 8~15</td><td>2.5～1.5 1.5～1.0</td><td></td><td>1~4</td><td>3.0~2.0</td></tr><tr><td rowspan=\"2\">涡轮式</td><td>1~5</td><td>7~4.2</td><td>锚式和框式</td><td>4~8 8~15</td><td>2.0～1.5 1.5~1.0</td></tr><tr><td>5~15 15~25</td><td>4.2~3.4 3.4~2.3</td><td></td><td>15~100</td><td>约1.0</td></tr></table></body></html>  \n\n桨式搅拌器的转速一般不高，约为 $20\\mathrm{\\sim}100\\mathrm{r/min}$ ，可适应的最高介质黏度为 $50\\mathrm{Pa}\\cdot\\mathbf{s}_{\\mathrm{a}}$ 其桨叶直径 $D$ 与槽径 $T$ 之比为 $0.35\\sim0.9$ ，介质黏度低时取较小值，黏度高时取较大值。桨宽 $B$ 与桨径 $D$ 之比为 $0.1{\\sim}0.25$ 0  \n\n桨式搅拌器主要用于固体溶解、防止固体沉降及对混合要求不是太高的场合。由于它通常桨径较大，转速较低，因此对液体的剪切作用比较弱，换言之，它不适用于以分散为主要目的的操作。  \n\n桨式搅拌器的优点是结构简单，制作和安装容易，造价低，所以至今仍不时被采用。它也可用于高黏度液体的搅拌，此时应选用较低的转速和较大的桨径，为了促使液体上下交换，可采用多层桨叶。为了平衡，相邻两层桨叶常取交叉布置。此外，也可采用一种变形的桨式搅拌器（见图4-1-14）。  \n\n![](images/ef3c03ad2b30fdfcbd8a1b70a7957cb70d1ac9491f8c1bf0194378ff73a421ea.jpg)  \n图4-1-14 变形的桨式搅拌器  \n\n$\\textcircled{2}$ 推进式搅拌器又称旋桨式搅拌器。传统的推进式搅拌器有三瓣叶片，外形像船用螺旋桨。  \n\n推进式搅拌器一般转速较高（常为 $200{\\sim}1750\\mathrm{r/min})$ ，叶轮尺寸较小，通常叶轮直径D仅为槽径 $\\boldsymbol{\\mathcal{T}}$ 的 $10\\%\\sim33\\%$ 。它不能用于过高的黏度， $2\\sim3\\mathrm{Pa}\\cdot\\mathrm{~s~}$ 已是上限。  \n\n推进式搅拌器的特点是排出液体的能力强，消耗功率相对较小，它不宜用于要求较高切应力的分散和反应等操作，在反应釜上应用很少。它主要用于液-液体系的混合，使温度均一化以及在低浓度固-液体系中防止淤浆沉降等。  \n\n$\\textcircled{3}$ 涡轮式搅拌器涡轮式搅拌器也称透平式搅拌器。它的结构按中心部分有无圆盘而分为两类。一类是有一个圆盘安装在轮毂上，叶片再安装在圆盘上的，称为圆盘式涡轮搅拌器；另一类是没有圆盘，叶片直接安装在轮毂上的，称为开启式涡轮搅拌器。叶片的形状有直的和弯的，叶片的安装角度又有垂直和倾斜的区别。这样就一共形成了常用的6种式样的涡轮（见图4-1-15）。  \n\n在上述涡轮中，叶片垂直安装的称径向流涡轮，如图4-1-15中的 $(a)\\sim(c)$ 和(e)；叶片倾斜安装的称轴向流涡轮，如图4-1-15(d）和(f)。径向流涡轮旋转时把液体从轴向吸人而向与轴垂直的方向（径向）排出。当槽内有挡板时，排出液流遇到槽壁后上、下分开，使槽内形成上、下循环的流型（见图4-1-11)。这种叶轮功率消耗大，切应力强，又具有较大的排出能力。因此它适用于既要有强的剪切力，又要有一定循环流量的场合，如在液-液体系用于乳化、乳液聚合、悬浮聚合、萃取等；在固-液体系用于固体溶解、悬浮液制备等，在气-液体系用于吸收及气体分散等。  \n\n![](images/4d914907b9d3955d7d4049c1fe11d966c7a573af6cf281fc97914b3cf9aed7e4.jpg)  \n图4-1-15 各种涡轮式搅拌器  \n\n轴向流涡轮除产生轴向流外，也产生部分径向流。产生同样的排液量，这种叶轮所需的功率比径向流涡轮要小。它主要用于液-液体系中需要强循环的场合，如均一混合、反应、传热等。  \n\n涡轮式搅拌器的直径 $D$ 与槽径 $T$ 之比通常为 $0,25\\sim0.5$ ，以取0.33居多，如果叶轮端部线速度低时可适当加大。这种搅拌器的叶片数常为3、4、6、8，以6叶最常用。一种使用很广的六叶平直圆盘涡轮各部尺寸推荐比例为 $D:L:B=20:5:4$ 目  \n\n涡轮式搅拌器在搅拌槽中的安装位置，通常取叶轮与槽底的净空距离等于叶轮直径，如为防止槽底有沉淀，叶轮的位置还可适当降低。当槽内液面较高时，可在轴上安装2个或多个叶轮。叶轮间的距离与液体黏度有关。液体黏度大，其间距要小些，但不小于叶轮直径$D$ 。涡轮搅拌器的转速常为 $50\\mathrm{\\sim}300\\mathrm{r/min}$ ，适应的最高黏度为 $30\\mathrm{Pa}\\cdot\\mathbf{s}$ 左右。由于它效能高，用途很广。在涂料行业中使用极普遍。  \n\n![](images/5add0b0ca5976ba93f9fd7a86d3fb1210315707998dfbe9e8b1fde62a9f8cc97.jpg)  \n图4-1-16 三叶后掠式搅拌器  \n\n$\\textcircled{4}$ 三叶后掠式搅拌器又叫三叶后弯（退）式或法武都拉式搅拌器（见图4-1-16)。实际上，它也是涡轮式搅拌器的一个变种。3个后弯叶片向上翘 $10^{\\circ}\\sim15^{\\circ}$ ，后弯角为 $30^{\\circ}$ 或 $50^{\\circ}$ ，其外径 $\\boldsymbol{D}$ 常取槽内径 $T$ 的 $1/2$ 0  \n\n三叶后掠式搅拌器属径流型，转速较高，桨端圆周速度最大可到 $\\bf{15m/s}$ 。适用于中低黏度液体 $(<10\\mathrm{{Pa}\\cdot\\mathbf{s})}$ 。这种搅拌器所产生的液体循环量大，与挡板配合使用，液体的轴向混合显著，能以较小的动力达到很好的搅拌效果。在相同条件下，它的功率消耗比桨式或涡轮式搅拌器小。  \n\n现在，乳液反应釜多采用这种搅拌器。  \n\n$\\textcircled{5}$ 锚式和框式搅拌器图4-1-17和图4-1-18所示为锚式搅拌器和框式搅拌器。它们外形相似，只不过框式搅拌器在中间横竖加了一些桨叶，以加强搅拌槽中心部位的搅动。若将中间横竖增加的桨叶，对称布置成一定的斜度，如斜桨那样，则效果更好。可以把它们看作是桨式搅拌器的变种。  \n\n![](images/60d245c00498fcc05cf723fed784d333c68b81bf621ca688c3afff415d10e153.jpg)  \n图4-1-17 锚式搅拌器  \n\n![](images/eb6729fd3e8bc048eaadd716f4df13374612b2fa9c2ea05b33d12fd4b219751d.jpg)  \n图4-1-18 框式搅拌器  \n\n这两种搅拌器适用于高黏度液体，通常转速较低，常为每分钟几十转。它们当中，框式比锚式更适应高黏度。“锚”和“框”的外缘与搅拌槽的内壁间距甚小，有刮壁效应，可强化传热，有利于防止因物料附壁而造成局部过热或结焦现象。一般取 $\\bar{C}/\\bar{D}=0.\\ \\bar{0}5\\sim0.\\ 08$ n当工艺提出更高要求时，只要搅拌器运转时不碰壁，间距 $c$ 还可以缩小。  \n\n$\\textcircled{6}$ 框板式搅拌器框板式搅拌器结构简单，外形像两扇门(见图4-1-4中的9)。它也是平桨搅拌器的一种变形。  \n\n框板式搅拌器的推荐尺寸为 $D/T=0.41\\sim0.534$ ， $B/T=0.26\\sim0.68$ ， $W/T=0.1\\sim$ 0.129( $D$ 为搅拌桨外径； $T$ 为搅拌槽内径； $B$ 为桨叶高度； $W$ 为桨叶宽度)。这种搅拌桨由于桨叶面积大，一般转速较低，它要借助挡板的作用，来强化轴向的混合。这种桨叶端部边缘较长，桨叶附近的湍动旋涡区较大，有利于分散。  \n\n在我国涂料行业，框板式搅拌器最初应用于引进的醇酸树脂反应釜中(1981年)。后来国产的醇酸树脂及氨基树脂反应釜中也时有选用（大多与换热盘管配合使用)。其混合效果较好，但分散效果不及组合的涡轮式搅拌器。  \n\n![](images/e55fb3b27db38740a9a3964fb1a0b83c43fb0692b27ff19d1ed096914d0bf4b9.jpg)  \n图4-1-19 开孔的框板式搅拌器  \n\n![](images/2ab297754d32588de0d8470595a97b35a9a6f1f62e05b5b59878119dc62423ee.jpg)  \n图4-1-20 网状和梳状打沫器  \n\n为减小运转阻力，改善搅拌效果，也可在框板上开设不同形状、不同数量的孔，如图4-1-19所示。  \n\n②打沫翅为了消除反应釜中液面上可能产生的泡沫，有的反应釜在靠近釜中液面处设置打沫翅（打沫器)，打沫翅主要有网状结构和梳状结构两种，如图4-1-20所示。  \n\n(3）搅拌器的选用和配置要做好搅拌器的选用和配置，首先要了解物料的物理性质、工艺过程的特点及对搅拌的要求。  \n\n不同的工艺过程对反应釜内液体流动状况有不同的要求，如低黏度互溶液体的混合及强化传热，只要求釜内液体有较大的容积循环速率，以达到所需要的调匀度及提高传热系数，而对液体内部的湍流强度及剪切力并无要求。但是，像甘油在植物油中分散这一类非均相系统混合，就要求有较高的湍流强度，以使甘油液滴分散得尽可能小，以增大两相接触面积，有利于化学反应进行。  \n\n![](images/13c35c695ef5188c2b8932b0bdc82419fc69e1c7d6c5dd48219ca32f32f830e4.jpg)  \n图4-1-21根据黏度初选搅拌器1一浆式变种（锚式、框式等）；2一浆式；3一涡轮式；4一推进式、1750 $(\\bar{\\bf{r}}/\\bar{\\bf{m i n}}$ ）或涡轮式；5一推进式、 $1150~\\mathrm{(r/min)}$ 或涡轮式；6一推进式、420 $(\\mathbf{r}/\\mathbf{min})$ 或涡轮式（注： $\\mathrm{1USgal{=}3,7B E L}$  \n\n$\\textcircled{1}$ 搅拌器的选用如上所述，各类搅拌器所形成的液体运动状况不同，按操作特性，可将它们大体上分成两大类。一类是桨叶面积小而转速高的，如推进式、涡轮式、三叶后掠式等属于此类。它们凭借桨叶的高速旋转，获得较高的湍流强度和较大的剪切力，因此又称剪切型搅拌器。另一类是桨叶面积大而转速低的，桨式、锚式、框式等属于此类。它们可以造成一定的总体流动，但液体离开桨叶时的速度并不高，湍流强度和剪切力较小。这一类搅拌器称低剪切型的，较适用于黏度高的液体。  \n\n对于黏度高的液体，如果采用小直径、高转速的推进式或涡轮式搅拌器是不恰当的。因为搅拌器所提供的机械能会因巨大的黏性阻力而很快消耗，不仅湍动程度随着与桨叶距离的增加而急剧下降，而且总体流动的范围也大为缩小。  \n\n就涂料行业而言，液体黏度往往是初步选择搅拌器的依据。此时图4-1-21可供参考。从图中不难看出，涡轮式搅拌器的应用范围极广。  \n\n$\\textcircled{2}$ 搅拌器的配置反应釜可配置一种搅拌器，也可配置多种搅拌器，一般可分为3种不同形式。a.单层单型搅拌器 这是最常见的形式，即选择一种形式的搅拌器单层设置。b.多层单型揽拌器现在反应釜多采用大容积的，因其高度增加，为了提高搅拌效果，可设置 $2\\sim3$ 层搅拌器。c.多层多型搅拌器现在大型反应釜按照反应的需要，配置 $2\\sim3$ 层不同类型的搅拌器，这有多种组合形式，通过试验选择最佳方案，可以使搅拌效果提高很多。尤其在醇酸树脂反应釜中应用较多，下面介绍几种组合形式。  \n\n醇酸树脂生产过程有醇解和酯化两个阶段。除了共同要求搅拌能有效地提高传热效果外，在醇解阶段因是不均相反应，为了充分混合不相容的物料，要求搅拌器有较好的分散特性，使甘油破碎成细滴分散于植物油中，同时起到促进液流湍动、加快反应物扩散、提高反应速度的作用。所以搅拌器速度要快，搅拌强度要较激烈。而酯化阶段为高温均相反应，反应过程中，黏度逐渐增大，要求搅拌在均匀传热的情况下，加速反应物与回流溶剂均匀混合，生成水分及时排出。在此过程还易产生泡沫，一般要求中等强度的搅拌。由于两个阶段对搅拌的要求稍有区别，常采用两种方法予以解决。一是使搅拌器的转速能调节；二是在揽拌器定速的情况下，配置适当的搅拌器，使其基本上能满足工艺要求。  \n\n容积小于 ${\\mathfrak{f}}\\mathbf{m}^{3}$ 的醇酸树脂反应釜可采用单层六叶 $45^{\\circ}$ 折叶涡轮式搅拌器，其直径一般等于或略大于釜径的1/3，桨端圆周速度约为 $\\pm\\mathrm{m}/\\mathrm{s}$ ，转速通常为 $130\\mathrm{r/min}$ 。对于大型的反应釜则有不同的组合形式，例如，内径为 $2400\\mathrm{mm}$ 、筒体高度（不计封头）为 $2500\\mathrm{mm}$ 、全容积为15m的醇酸树脂反应釜的搅拌，一种形式为3层涡轮式搅拌器，下层为直径800mm的六叶直叶开启式涡轮，中、上两层均为直径900mm的四叶折叶开启式涡轮，用30kW电机以变速传动，转速范围为34～136r/min。另有一种形式为2层直径800mm的六叶折叶圆盘涡轮，用22kW电机定速传动，转速为88r/min。实践证明，这两种组合形式效果都较好。单层框板式的搅拌器因其面积大，也有较好搅拌效果。随着搅拌技术的发展，搅拌器的组合将会有更新的创造和发展，以达到更高的效率和更低的能耗。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1103,
+        "chunk": "# 5.反应釜的传动  \n\n按搅拌轴的转速是变速或定速，可将反应釜的传动分为变速传动和定速传动两类。  \n\n(1）变速传动变速传动主要有变频调速、油压马达调速、机械无级调速和带式调速4种，其中以变频调速应用较多，其他3种大多用于进口设备上。较详细的介绍见本章第二节。  \n\n(2）定速传动变速传动由于装置复杂，费用高，大多操作较繁琐，只在少数对搅拌转速有严格要求的反应釜上使用。目前普遍使用的还是定速传动。  \n\n定速传动由电机经减速后实现。电机视生产环境是否易燃易爆采用防爆电机或封闭式电机。减速机主要有摆线针轮减速机、两级齿轮减速机、V带减速机和立式蜗轮减速机。蜗轮减速机又称蜗轮蜗杆减速机，由于有传动效率较低、易发热、结构不紧凑等缺点，现在应用不多。V带减速机结构简单，维修方便，但速比范围小（约3～4.5)，只适用于搅拌轴转速较高（>300r/min）的场合。它和蜗轮减速机还有一个共同的缺点，由于使用V带（即三角胶带)，过载时会产生打滑现象，可能形成静电，所以它们不能用于有严格防爆要求的场合。两级齿轮减速机传动效率较高，使用寿命长，电机与减速机直联或通过联轴器连接，可用于严格要求防爆的场合。  \n\n目前在反应釜上使用最广的是摆线针轮减速机。该机为利用少齿差内啮合行星传动的减速装置。它具有减速比大、传动效率高、运转平稳、体积小等优点。可用于严格要求防爆的场合。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1104,
+        "chunk": "# 6.反应釜的轴封  \n\n轴封为一种动密封装置。它的功用是当反应釜正压操作时，防止釜内的溶剂气体等逸出釜外；同时，也防止釜内负压操作时，空气被抽人釜内而降低了釜内的真空度。因涂料行业的物料大多是易燃易爆和有毒的物料，所以保证轴封严密，对反应釜来说是非常重要的。  \n\n![](images/617afed6a4abb27a19e87750fdc5b44832ba388171a385663d5f95b558d43dc1.jpg)  \n图4-1-22 软填料密封的结构1—压盖；2—双头螺柱；3—螺母；4一垫圈；5—油杯；6—油环；7一软填料；8—本体；  \n\n轴封的形式很多，目前最常用的是软填料密封和机械密封两种形式。  \n\n(1）软填料密封  \n\n9一底环①结构和原理图4-1-22所示为典型的软填料密封结构形式之一。压盖将软填料环（俗称盘根）沿轴向压紧，使其产生径向弹塑性变形，堵塞间隙而密封。  \n\n在软填料密封结构中，可能造成泄漏的渠道有：轴与软填料之间的间隙、软填料与填料箱体内壁之间的间隙及软填料自身的孔隙。为了达到密封的目的，就要压紧软填料，以堵住这3条渠道。这三者中，因为轴要不停地转动，所以要堵住轴与软填料之间的间隙更困难一些。  \n\n软填料在使用--段时间后，逐渐被轴磨损并变硬，软填料中的润滑剂也有损耗。这时就要发生泄漏，需要重新拧紧压盖上的螺母，压紧软填料。但是，软填料压紧的程度要适当。太松固然要泄漏，太紧了则软填料与轴的磨损加剧，不仅无谓地多消耗功率，而且由于软填料的磨损、发热，甚至烧坏，将导致密封更快的失效。  \n\n润滑在软填料密封中是必不可少的。一方面，当压紧软填料时，润滑剂在搅拌轴上形成一层极薄的液膜起到密封作用；另一方面，它又起到润滑作用，减少了软填料与轴摩擦造成的发热，减轻了软填料和轴的磨损及功率的消耗。一般的润滑方法有：选用有目润滑功能的软填料；安装软填料时浸油或涂润滑脂；利用油环注入油脂或其他密封液体。  \n\n$\\textcircled{2}$ 密封材料软填料必须有好的弹性和塑性；能经受釜内介质的浸泡和腐蚀；耐温性能好；耐磨，与轴的摩擦系数小，有自润滑性。常用的软填料是石棉橡胶填料和油浸石棉填料，比较新颖的填料有编织膨胀石墨填料和碳素纤维填料、膨体聚四氟乙烯纤维填料等。碳素纤维填料耐磨，有自润滑性，密封效果好，而且因它耐温 $350^{\\circ}C$ ，可不用冷却水套进行冷却，所以特别适用于高温树脂反应釜。  \n\n$\\textcircled{3}$ 选用注意事项要使软填料密封做到基本不漏，应从下面几方面入手。a.填料箱结构合理，制造、安装精度高，搅拌轴应处于填料箱的轴线上，不偏斜。填料箱体不应焊死在釜盖上。b.轴要光、要圆，运转时摆动量要小，轴的表面最好经表面淬火或喷镀后磨光，也可镀硬铬。c.选用好的软密封填料。d.要经常维护。软填料装人时要一圈一圈的装，并压紧，而且压紧力的大小要适宜，要均匀。最好采用预压成型的填料环。$\\textcircled{4}$ 软填料密封的优缺点软填料密封虽然是比较古老的密封形式，而且一般有易磨损轴、摩擦功率消耗比较大、软填料寿命短、要经常维护及漏损比较大等缺点。但由于它有简单实用、成本低、适用范围广（如可用于腐蚀性介质，工作温度范围大）等优点，至今仍广泛使用。特别是像碳素纤维填料等新颖高档密封填料出现后，在很大程度上克服了软填料密封的缺点，为它带来了新的生机。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1105,
+        "chunk": "# (2）机械密封  \n\n$\\textcircled{1}$ 结构和原理图4-1-23所示为釜用机械密封的结构形式之一。它的密封作用是借助于装在轴上的动环（旋转环）6与装在釜盖上的静环（静止环）13（或10)，两环的端面做相对运动时相互紧贴，防止渗漏。由于它的动密封面不像软填料密封是圆柱面，而是与转轴垂直的端面，所以又称端面密封。图中的弹簧座3用紧定螺钉17固定在轴上，它通过传动螺钉1带动动环6旋转。动环沿轴向可作适量的移动，以适应转轴许可的窜动和振动，并随时补偿端面的磨损。由弹簧的推力和釜内外压差作用在动环上的轴向力（如釜内为真空时，此力与弹簧推力一致；如釜内为正压时，此力与弹簧推力相反)，造成端面适当的压紧力，使这两个与轴线垂直的平直、光洁的端面紧密贴合，同时端面间维持一层极薄的（约为$0.025\\sim0.25\\mu\\mathrm{m})$ ）的液膜，这层液膜起到良好的润滑和密封作用，因而由动环和静环组成的摩擦副能长期工作而泄漏量极小。  \n\n除了端面外，机械密封中还有两个密封点，一个在动环与轴之间，另一个在静环与釜口法兰之间。这两点都是静密封，通常称辅助密封。辅助密封元件通常用O形圈、V形圈或  \n\n![](images/5b01dbf4eafa40264967daf8154c610515b31a8fc69fa2eecbccfcbe4c4b27ca.jpg)  \n图4-1-23 釜用机械密封  \n\n1—传动螺钉；2—螺母；3—弹簧座；4—推环；5—防尘盖；6—动环；7—垫圈；8—螺钉；9—静环压盖； 10,13—静环；11—静环垫；12—静环密封圈；14—润滑盒；15—动环密封圈；16—弹簧；17—紧定螺钉 注：此图左侧为202型结构，右侧为202F型，它们的动、静环材质及静环结构均不同  \n\n波纹管。O形圈常用各种橡胶制造，V形圈常用聚四氟乙烯制造，波纹管有橡胶波纹管、 聚四氟乙烯波纹管和金属波纹管3种。  \n\n釜用机械密封大部分密封介质是气体，故密封端面处于干摩擦状态，磨损较大。同时，气体的渗透性强，容易渗漏。所以必须对密封面进行润滑。一般是将密封端面浸泡在槽内的润滑液中。为了防止润滑液万一渗漏人釜内产生不良后果，此润滑液除了具备润滑性好、不腐蚀零件和沸点较高等条件外，还应能与釜内物料相容。如轴封处温度太高，则还要对槽内润滑液采取冷却措施，如在槽内设冷却蛇管或槽外加冷却水套等。  \n\n单端面密封结构比较简单，但有一些缺点。因密封的介质是气体，当釜内有压力时，润滑液并没有压力，因而端面上的润滑条件无法保证，有发生干摩擦的可能。所以对要求高的场合，以及高压、高真空、高温、强腐蚀、易燃易爆、有毒等情况下，应使用双端面机械密封。  \n\n![](images/ca66277a823fb85949b099cac30e254f10cbedf405fd87e29271250f49177a17.jpg)  \n图4-1-24 双端面密封  \n\n1—光轴；2，4一密封环；3，12—静环；5，14—动环；6一固定环；7，16—轴密封环；8，10—压板；9一密封套：11一垫圈；13—O形环；15—固定环；17—定位螺钉；18—弹簧；19—密封夹套；20—密封板；21一端盖  \n\n图4-1-24所示是一种釜用双端面密封结  \n\n构，密封在充满封液（隔离流体）的夹套中工作，封液的压力要比釜内压力高 $0.05\\sim$ $\\mathrm{0.1MPa}$ ，所以封液有可能漏人釜内，而釜内气体则保证不会外漏。封液在密封面形成液膜，润滑了端面，还可起到冷却和冲洗的作用。由于封液的作用，使双端面机械密封不但做到了釜内物料无泄漏，而且运转可靠，寿命长。封液的压力可由高位平衡罐或气瓶（氮气或二氧化碳）提供，也可采用泵循环加压装置。  \n\n$\\textcircled{2}$ 机械密封材料机械密封的动环和静环，一般用一个硬的材料与一个软的材料配对。如动环常用硬质合金（主要成分为碳化钨)，静环常用浸树脂碳素石墨。浸溃不同的树脂，其性能也有差别。浸酚醛树脂耐酸性好；浸环氧树脂耐碱性好；浸呋喃树脂既耐酸又耐碱，且其耐有机溶剂的性能也较强，所以使用较多。  \n\n辅助密封圈包括动环密封圈和静环密封圈。它们除密封外，还起到部分补偿密封面偏斜和缓冲振动的作用。因此要求密封圈有良好的弹性、小的摩擦系数、耐介质的腐蚀和溶胀、耐老化。辅助密封圈最常用的是橡胶O形圈。普遍使用的是丁腈橡胶，它耐油（汽油、机油)，但耐温不高（约120℃），在苯类溶剂中会溶胀。价格较高的氟橡胶耐温较高（约$200^{\\circ}\\mathrm{C})$ ，耐有机溶剂性能也较好。当橡胶在耐温或耐化学腐蚀方面不能满足要求时，可考虑采用聚四氟乙烯。聚四氟乙烯一般制成V形圈。聚四氟乙烯V形圈对轴的精度要求高，装配时难度较大。  \n\n$\\textcircled{3}$ 釜用机械密封的特点及使用注意事项a.因密封介质为气体，要防止密封端面形成十摩擦。对单端面机械密封，要设置润滑液槽并注人合适的润滑液。对双端面机械密封，要保证封液正常循环或加压。b.因反应釜搅拌轴较长，故要严格控制搅拌轴摆动。为此采取包括优化传动机架结构，提高制造安装精度，精心使用维护，防止搅拌轴弯曲等措施。c.因更换釜用机械密封比较困难，故要考虑拆装方便。可采用夹壳式联轴器（系对开结构)，使搅拌轴与传动轴中间留出足够的空当或在联轴器中间加一短节，这样在拆开夹壳式联轴器或取下联轴器中间的短节后，即可取出或放人机械密封。  \n\n$\\textcircled{4}$ 机械密封的优缺点  \n\n优点：  \n\na.密封性能可靠，泄漏量小；  \nb.摩擦功率消耗小；  \nc.使用寿命长；  \nd.不需要经常调整和维修；  \ne.对轴或轴套造成的磨损很小。  \n缺点：a.结构复杂，装配精度要求高；  \nb.排除故障或更换零部件不方便，停车时间长；  \nc.造价高。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1106,
+        "chunk": "# 7.反应釜的配套设备  \n\n反应釜的配套设备主要有稀释罐和冷凝回流设备（蒸出管或分馏柱、冷凝器和分水器)。一种常见的溶剂法醇酸树脂反应釜与冷凝回流设备的连接如图4-1-25所示。  \n\n从反应釜蒸发出来的溶剂气体和水蒸气，经蒸出管进入冷凝器冷凝并冷却，冷凝液进入分水器，水与溶剂（如二甲苯）分层，溶剂回流到反应釜，水则不断从分水器底部排出。  \n\n为防止蒸出气体走短路，在回流管上设置了液封。显然，分水器要安装得比较高，分水器的液面至反应釜回流液人口处要有足够的位差，以克服反应釜顶部至分水器顶部的压差，并保证有一定的回流速率。  \n\n（1）蒸出管或分馏柱  \n\n$\\textcircled{1}$ 蒸出管根据各品种树脂的不同要求，蒸出管有不同形式。一般使用带夹套的直立（也可倾斜）圆管，管径较大，夹套可按需要通人蒸汽或冷却水，以分别起到保温作用，使气体上升到冷凝器冷凝或使部分气体冷凝流回反应釜。  \n\n溶剂法醇酸树脂反应釜的蒸出管大多采用蒸汽保温的立管（或倾斜)，但要注意蒸汽压力是否够大。如蒸汽压力太低（蒸汽压力为0.3MPa时，对应的饱和蒸汽温度为 $143.4^{\\circ}C)$ _+蒸汽温度可能比蒸出管内的气体温度还低，就起不到保温作用。不如不通蒸汽，只依靠夹套外的保温层保温。  \n\n![](images/c57f8a61cc321b82fdca21a5936c2b1c2d031660cead757ef02daa465789791b.jpg)  \n图4-1-25 溶剂法醇酸树脂反应釜与冷凝回流设备的连接 1—反应釜；2—蒸出管；3—冷凝器；4—分水器； 5—高位槽；6—视镜；7—回流管；8—排水阀  \n\n使用这种蒸出管，沸点低的物料损失较多，容易出现苯酐升华随同气体进入冷凝器导致堵塞列管的情况。同时，由分水器回流人反应釜的二甲苯温度较低，回到反应釜内要吸收较多的热量才能与水共沸蒸发，能量损失大。  \n\n$\\textcircled{2}$ 分馏柱一种改进的形式是把蒸出管改为填充式分馏柱。分馏柱内填充拉西环或鲍尔环，填充高度根据需要而定。分馏柱外有夹套通蒸汽保温。冷凝回流的二甲苯经泵（或计量泵）送入分馏柱顶部淋下，通过填料环与逆流而上的二甲苯-水蒸气接触，在分馏柱内进行传质与传热。减少了回到釜中二甲苯的含水量，提高其温度（约为$110{\\sim}120^{\\circ}C;$ ，而且可使升华的苯酐溶于二甲苯中再返回反应釜而不致进入冷凝器，避免了换热管表面结垢或堵塞。同时防止了反应釜内低沸点等原料的损失。  \n\n图4-1-26所示为国内某厂将蒸出管改为分馏柱的流程。在这个流程里，回流二甲苯进人分馏柱是依靠位差的。如这个位差不足，仍需用回流泵。  \n\n图4-1-27所示为德国一工程公司设计的带分馏柱的醇酸树脂工艺流程。冷凝回流液用回流泵强制循环，并通过流量计计量。  \n\n![](images/29a18e6c8b641e28ffacc0ace4d286f560c4e8a80185a4ebbeab4f265e805c0f.jpg)  \n图4-1-26 蒸出管改为分馏柱流程  \n\n将蒸出管改为分馏柱，使冷凝回流液从分馏柱顶部喷淋回反应釜，有利于共沸液的分离，加快酯化，节约热量，减少低沸物损失，更适宜于沸点较低的酸、醇类的醇酸树脂、聚  \n\n酯以及缩聚型树脂的生产。  \n\n![](images/1521559a74bc9da10e06fa30bf4f0f6fd69ffd43051c8e066986fb8d37f4bda4.jpg)  \n图4-1-27带分馏柱的醇酸树脂工艺流程 1—卸料单元设备；2—称量漏斗；3-送料螺旋；4—反应釜；5,14—搅拌器；6—分馏柱；7—冷凝器； 8—分水器；9—回流泵；10—接收器；11—真空泵；12—导热油泵；13—稀释罐； 15—回流冷凝器；16—产品泵；17—产品过滤器  \n\n③带冷凝器的分馏柱还有一种形式是采用带立式冷凝器的分馏柱，如图4-1-28所示。上部为立式冷凝器，换热管较粗。下部为装填料环的分馏柱。此形式不用回流泵，只是利用自身上部立式冷凝器的冷凝液流到分馏柱内进行传质和传热，减少了低沸点原料的损失，避免了因苯酐升华而堵塞冷凝器。  \n\n(2）冷凝器 冷凝器的作用是将从反应釜蒸发出来的水蒸气和溶剂气体等冷凝下来，同时也可使冷凝液适当冷却。  \n\n![](images/9b9eafe5859910393fc9314a5694dbfbb80ad8d771155f1b51969afa4101ab83.jpg)  \n图4-1-28 带立式冷凝器的分馏柱  \n\n①冷凝器的分类和结构有多种形式换热器可用作冷凝器，如列管式（即管壳式）、螺旋板式、蛇管式、套管式等。最常用的是列管式。  \n\n换热时，通常回流溶剂与水蒸气走管内，冷却水走管间。作为冷凝器，冷却水从下面进入，然后从上面排出。  \n\n壳体上应多开设几个检查清理孔。如冷却水水质不好，冷凝器使用长久后，壳程可能结垢或沉积泥沙，应定期或不定期用水进行反冲洗和清垢。  \n\n树脂生产中所用冷凝器大多是不锈钢冷凝器，即管程与物料接触部分（管束、管板等）  \n\n用不锈钢制造，壳体一般仍用碳钢。  \n\n② 树脂反应釜配套用冷凝器常用的列管式冷凝器，按其安装位置分立式和卧式，对于需要回流的工艺，大多使用倾斜安装的卧式冷凝器。卧式冷凝器的斜度(与水平面夹角)以 $5^{\\circ}\\sim8^{\\circ}$ 居多。  \n\n冷凝器所需的传热面积可依据冷凝物料的数量、冷凝时间及冷却水温度等数据进行计算。本章所列的表4-1-6和表4-1-7也可作参考。作为粗略估算，生产醇酸树脂一般 $\\bf{1m^{3}}$ 的反应釜配备约 $5\\mathrm{m^{2}}$ 冷凝器；生产氨基树脂一般 $\\bf{1m^{3}}$ 反应釜配备约 $\\mathrm{8}\\mathrm{m}^{2}$ 冷凝器。  \n\n一般冷凝器以单程较常用，也可选用面积不等的两程冷凝器，如图4-1-29所示的 $\\mathrm{30m^{2}}$ 冷凝器，第一程换热面积为 $25\\mathrm{m}^{2}$ ，第二程为 $5\\mathrm{m}^{2}$ ，这样不平均分配，适应了冷凝的规律，大部分蒸汽已在第一程冷凝下来，余下的小部分蒸汽，再在第二程进行冷凝。由于延长了冷凝的路程，减少了排空损失，有利于环境保护。  \n\n![](images/469f0139a61c4abaeffab73edfbb87d647e25efb9100b7154332509c33f84f9b.jpg)  \n图4-1-29 冷凝器  \n\n1—平盖；2一前管箱；3—隔板；4一换热管；5—折流板； 6一拉杆；7—支座；8—接管；9—管板；10—后管箱  \n\n这个冷凝器使用薄管板结构，管板厚度为 $12\\mathrm{mm}$ ，比传统的厚管板节约材料 $60\\%$ 以上；同时，使用了带加强筋的平盖，接管在侧面，当需要检查、清理换热管时，只需打开平盖而不必拆除接管，比较方便。还有一个特点，这个冷凝器的壳体上未设置膨胀节，经在醇酸树脂反应釜上长期配套使用证明，它能承受操作中的温差，安全使用。  \n\n(3）分水器也称苯水分离器或油水分离器。它的作用是收集经冷凝器冷凝下来的液体混合物，依靠各自密度的不同进行分层，上部的溶剂（常为二甲苯或丁醇等）经U形回流管返回反应釜，水从分水器底部排放。  \n\n$\\textcircled{1}$ 普通分水器简称分水器（见图4-1-30)，为立式圆筒形容器，顶和底大多用椭圆形封头，也有用锥底的。分水器筒体中部，要有一个圆视镜供照明用，称灯孔。灯孔对面，一般上、下分设两个视镜，上视镜中心宜与回流口低点等高；下视镜能看到水与溶剂的分层面。通常灯孔和视镜孔做得较大，以便供分水器内清洗用。  \n\n分水器下部可增加一个进水口，开始操作时可加水至下视镜中心。  \n\n分水器的容量以略大于釜内反应所能产生的水量为原则。如1000L醇酸树脂反应釜配套的分水器容量宜在 $60L$ 左右。表4-1-6和表4-1-7中所列分水器规格供参考。  \n\n$\\textcircled{2}$ 自动排水分水器（图4-1-31）也称连续分水器，是基于连通器原理设计的。在分水器中，从冷凝器来的冷凝液逐渐分层，溶剂因其密度比水小，所以浮在水面上并从回流管溢流，返回反应釜，下层的水从贮水筒的排水管连续排出。在贮水筒顶部有一根压力平衡管与分水器顶部空间相通，这样可以避免在排水时造成虹吸现象。由于溶剂和水在管道中流动都较慢，排水管的高度H可按流体静压力来计算。但由于密度因温度等因素也会发生变化，安装也会有误差，所以排水管高度应该是可以比较方便地加以调节的。同时要注意下视镜（分界面）不要离连通管太近。也可将连通管从分水器筒体底部管路上接出来，或者干脆不用贮水筒，连通Ⅱ形管（同时接上压力平衡管）直接排水。  \n\n![](images/f081deb4091a7c8bcf8f5f7dd209d7a5535226a978be8b8a56a226865acbec75.jpg)  \n图4-1-30分水器 1—分水器筒体；2—回流管；3—接管； 4—视镜：5一排水阀  \n\n![](images/769f38262583ebcb75bbe2ec62f7997f166fdc7293d1a6a71c486e990ee95bd7.jpg)  \n图4-1-31自动排水分水器1—分水器筒体；2—回流管；3-压力平衡管；4一贮水筒；5—排水管；6—出水槽  \n\n(4）稀释罐稀释罐又称兑稀罐、稀释釜。树脂在稀释罐中用溶剂（一种或多种）予以稀释，使之达到工艺要求的固体分和黏度，然后用泵送到过滤工序进行净化，供制造清漆或色漆用。  \n\n①稀释罐的结构及配套冷凝器稀释罐的结构与反应釜相似，大多是一个立式带搅拌器的容器，常配置一个立式列管式冷凝器，如图4-1-32所示。为生产色泽特别浅的树脂或有其他特殊要求时，稀释罐要用不锈钢制作。要求不高的也可用碳钢制造。  \n\n稀释罐的搅拌，并不需要很激烈。所以一般采用多层桨式搅拌器或折叶涡轮式搅拌器，也可用框式搅拌器。对前两种搅拌器，罐内可加挡板，以加强搅拌效果。  \n\n![](images/08d5c8c5bb602b048e93b39989f0f343a065a1c5b1504a21f7b213ab7278960e.jpg)  \n图4-1-32稀释罐1--罐体；2—搅拌器；3—夹套；4一回流冷凝器  \n\n稀释罐的传热结构，对小容量的稀释罐大多用夹套，容量较大的稀释罐宜采用半管夹套或内部蛇管。在操作时，大多数情况都是通水冷却，以减少溶剂挥发。但有时也用蒸汽加热，目的是提高物料温度，降低其黏度，以满足过滤的要求。无论通水或蒸汽，都要控制好压力，以免发生事故(如带夹套的稀释罐内筒被压)。  \n\n通常在稀释罐的顶部设置回流冷凝器，以回收溶剂，保护环境。回流冷凝器大多为列管式，以立式居多，直接接在稀释罐的出气口上。也有采用卧式倾斜安装的，溶剂冷凝后回流人稀释罐，不凝性气体排至大气中。  \n\n回流冷凝器可以用不锈钢制作，也可用碳钢制作。碳钢耐腐蚀性能差，当使用循环水冷又未采取防腐措施时，碳钢换热管会因锈蚀而穿孔，冷却水可能漏入稀释罐内。所以要经  \n\n常检查。  \n\n② 稀释罐的容量配置由于树脂溶液的固体分一般为50%左右，所以通常推荐稀释罐的容量为反应釜容量的2倍。为给兑稀操作留出一点调整黏度或固体分的余地，稀释罐的容量以大于反应釜容量的2倍、小于反应釜容量的2.5倍为宜。  \n\n稀释罐的搅拌，由于物料黏度大多较低，且不需要很激烈，故所需电机功率比反应釜小，估算时可取 $0.4{\\sim}0.8\\mathrm{kW/m^{3}}$ 中  \n\n稀释罐配套冷凝器的传热面积可以计算或根据现有装置的经验选取。估算时可取 $0.65\\sim$ $1.1\\mathrm{m^{2}/m^{3}}$ ，如采用“反兑稀”（高温树脂加入溶剂中）工艺，可取偏高值。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1107,
+        "chunk": "# 8.反应釜及配套设备的规格  \n\n前已述及，在树脂生产中广泛使用不锈钢反应釜和塘玻璃反应釜。塘玻璃反应釜的夹套一般都是通蒸汽或热水进行加热，近年推出一种电加热塘玻璃反应釜，夹套内装导热油等热载体，用电热棒插人加热。塘玻璃反应釜标准化程度较高，早已定型生产。但不锈钢反应釜尚无统一的标准，有的厂有自己的产品系列，大多数还要按工艺要求设计图纸，专门加工。  \n\n生产不同树脂的反应釜，其配套设备情况不同。即使生产同一品种，基于不同的考虑，所选定的配套规格也不尽相同，所以要根据实际情况，多作分析比较。  \n\n(1）糖玻璃反应釜糖玻璃反应釜按结构有开式（K型）和闭式（F型）之分。开式的釜盖可打开，其公称容积范围一般为 $50\\sim5000\\mathrm{L}$ ，相对较小；闭式反应釜的公称容积范围一般为 $2500{\\sim}12500\\mathrm{L}$ ，容量较大。 $20\\mathrm{m}^{3}$ ， $30\\mathrm{m^{3}}$ 等规格也可定制。  \n\n开式反应釜的结构见图4-1-33。开式反应釜的技术特性见表4-1-3（录自标准HG/T2371—1992)。需要注意的是，有的厂按原化工部部标生产，有的按厂标生产，所以各厂产品仍有差异，包括总体尺寸、开孔数目及大小、开孔接盘是水平或倾斜等方面。  \n\n表4-1-3 塘玻璃开式反应釜技术特性  \n\n\n<html><body><table><tr><td colspan=\"2\">项 目</td><td>1</td><td>2</td><td>3</td><td>4</td><td>5</td><td>6</td><td>7</td><td>8</td><td>9</td><td>10</td><td>11</td><td>12</td><td>13</td><td>14</td></tr><tr><td colspan=\"2\">公称容积/L</td><td>50</td><td>100</td><td>200</td><td>300</td><td>400</td><td>500</td><td>800</td><td></td><td>1000</td><td>15002000</td><td></td><td>2500</td><td>3000 4000</td><td></td><td>5000</td></tr><tr><td colspan=\"2\">夹套换热面积/m²</td><td>0.540.84</td><td></td><td>1.5</td><td>1.9</td><td>2.4</td><td>2.6</td><td>3.7</td><td></td><td>4.5</td><td>5.8</td><td>7.2</td><td>8.2</td><td>9.3</td><td>11.7</td><td>13.4</td></tr><tr><td colspan=\"2\">公称压力/MPa</td><td colspan=\"19\">容器内：0.25、0.6或1.0;夹套内：0.6</td></tr><tr><td colspan=\"2\">介质温度及容器材质</td><td colspan=\"11\">0～200℃时，材质为Q235-A、Q235-B；—20～200C时，材质为20R</td></tr><tr><td colspan=\"2\">搅拌轴公称直径/mm</td><td rowspan=\"2\">40 0.550.75</td><td rowspan=\"2\">50</td><td rowspan=\"2\"></td><td colspan=\"4\">65</td><td colspan=\"5\">80</td><td colspan=\"2\">95</td></tr><tr><td>电动机功率 锚式、框式、桨式搅拌器 叶轮式搅拌器</td><td></td><td>1.1</td><td>1.5</td><td>1.5</td><td>2.2 3.0</td><td>3.0</td><td>3.0 4.0</td><td colspan=\"2\">4.0</td><td colspan=\"2\">5.5 5.5</td></tr><tr><td colspan=\"2\">/kW 电动机类型</td><td></td><td colspan=\"10\">4.0 Y或YB系列（同步转速1500r/min）</td><td></td><td>7.5</td></tr><tr><td colspan=\"2\">搅拌轴公称转速/(r/min)</td><td colspan=\"9\"></td><td></td><td></td><td></td></tr><tr><td colspan=\"2\">轴封允许工作压力/MPa</td><td colspan=\"11\">锚式、框式搅拌器60、80；桨式搅拌器80、125；叶轮式搅拌器125 塘玻璃填料箱或带冷却水夹套塘玻璃填料箱PN≤0.25；单端面机械密封PN≤</td></tr><tr><td colspan=\"2\"></td><td>0.6；双端面机械密封PN≤1.0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td colspan=\"2\">参考质量/kg</td><td>376</td><td>442</td><td>584</td><td>745</td><td>810</td><td>904</td><td>1115</td><td>1785</td><td>1910</td><td>2482</td><td>33963668</td><td>4210</td><td>5274</td></tr></table></body></html>\n\n注：1.参考质量不包括传动装置及塘玻璃层的质量。2.叶轮式搅拌器，即三叶后掠式搅拌器。  \n\n塘玻璃反应釜的搅拌器，目前只有4种形式，即锚式、框式、桨式和叶轮式（三叶后掠式)。近来，采用叶轮式搅拌器较多，同时让一种指状（或叫梳状）挡板与之配合（见图4-1-33中的温度计套管12)，以利于形成上下循环流动。  \n\n![](images/84e99711232ce37f9f389df150773b13f3f7f99eb96216c3c62008794c9c1a14.jpg)  \n图4-1-33 开式糖玻璃反应釜的结构  \n\n1—支脚；2—塘玻璃放料阀；3—排液口；4—夹套；5-搅拌器；6—挂脚；7-人气口； 8一罐体；9—垫片；10—卡子；11—罐盖；12—温度计套管；13—填料箱； 14一摆线减速机；15一电机：传动A一用无支点机架，夹壳联轴器； 传动B一用单支点支架，刚性联轴器  \n\n由于塘玻璃搅拌器大多通过螺纹与传动轴连接，所以严禁倒转，以防脱落而砸坏设备。(2）电加热塘玻璃反应釜由于夹套里要装导热油等热载体，并插入若干只电热棒，所以夹套直径要加大，其余与一般塘玻璃反应釜相同。  \n\n电加热塘玻璃反应釜的技术参数可参考表4-1-4。这种釜宜用于小容量。  \n\n表4-1-4电加热塘玻璃反应釜技术参数  \n\n\n<html><body><table><tr><td>规格/L</td><td>夹套容积/L</td><td>罐内容积/L</td><td>电热功率/kW×支</td><td>工作温度/℃C</td><td>密封形式</td><td>搅拌形式</td><td>搅拌转速/(r/min)</td></tr><tr><td>50</td><td>96</td><td>71</td><td>2X4</td><td>0~200</td><td>填料或机械密封</td><td>锚式</td><td>85,63</td></tr><tr><td>100</td><td>127</td><td>128</td><td>2X6</td><td>0~200</td><td>填料或机械密封</td><td>锚式</td><td>85.63</td></tr><tr><td>300</td><td>218</td><td>369</td><td>4X6</td><td>0~200</td><td>填料或机械密封</td><td>锚式</td><td>85,63</td></tr><tr><td>500</td><td>269</td><td>588</td><td>4X9</td><td>0~200</td><td>填料或机械密封</td><td>框式</td><td>85,63</td></tr><tr><td>1000</td><td>400</td><td>1250</td><td>4X12</td><td>0~200</td><td>填料或机械密封</td><td>框式</td><td>85,63</td></tr><tr><td>1500</td><td>600</td><td>1720</td><td>4X15</td><td>0~200</td><td>填料或机械密封</td><td>框式</td><td>85,63</td></tr><tr><td>2000</td><td>850</td><td>2160</td><td>4X15</td><td>0~200</td><td>填料或机械密封</td><td>框式</td><td>85,63</td></tr><tr><td>3000</td><td>1015</td><td>3380</td><td>5X15</td><td>0~200</td><td>填料或机械密封</td><td>框式</td><td>85,63</td></tr><tr><td>5000</td><td>1400</td><td>5650</td><td>5X18</td><td>0~200</td><td>填料或机械密封</td><td>框式</td><td>85,63</td></tr></table></body></html>  \n\n(3）电加热不锈钢反应釜此处专指在夹套内插人电热棒，通过导热油等热载体进行间接加热的不锈钢反应釜。其技术参数可参考表4-1-5。搅拌器常为锚式或框式，用摆线针轮减速机或蜗轮减速机传动。这种釜宜用于小容量。  \n\n(4）常用树脂反应釜的配套设备规格参照原化工部第三设计院的涂料专用搅拌釜系列及其他资料，汇总编制了醇酸树脂反应装置配套设备规格（表4-1-6）、氨基树脂反应装置配套设备规格（表4-1-7）和丙烯酸树脂反应装置配套设备规格（表4-1-8）等表，供参考。  \n\n表4-1-5电加热不锈钢反应釜技术参数  \n\n\n<html><body><table><tr><td>规格 /L</td><td>实际容 量/L</td><td>电热功率 /kWX支</td><td>内筒直 径/mm</td><td>夹套直径 /mm</td><td>内简高 度/mm</td><td>支座螺孔 中心距/mm</td><td>外形尺寸 /mm</td><td>搅拌功 率/kW</td><td>搅拌转速 /(r/min)</td><td>质量 /kg</td></tr><tr><td>50</td><td>78</td><td>2X4</td><td>400</td><td>600</td><td>350</td><td>754</td><td>824X2015</td><td>1.1</td><td>80</td><td>270</td></tr><tr><td>100</td><td>127</td><td>2X6</td><td>500</td><td>700</td><td>450</td><td>894</td><td>1004X2120</td><td>1.1</td><td>80</td><td>340</td></tr><tr><td>300</td><td>327</td><td>3X6</td><td>700</td><td>900</td><td>650</td><td>1098</td><td>1208×2495</td><td>2.2</td><td>80</td><td>700</td></tr><tr><td>500</td><td>509</td><td>4X9</td><td>900</td><td>1100</td><td>750</td><td>1328</td><td>$1468X2695</td><td>2.2</td><td>80</td><td>930</td></tr><tr><td>1000</td><td>1017</td><td>4X12</td><td>1200</td><td>1400</td><td>900</td><td>1696</td><td>1896×3110</td><td>4.0</td><td>80</td><td>1610</td></tr><tr><td>2000</td><td>2154</td><td>4X15</td><td>1400</td><td>1600</td><td>1300</td><td>1854</td><td>2005X3500</td><td>5.5</td><td>80</td><td>2010</td></tr><tr><td>3000</td><td>3201</td><td>4X15</td><td>1600</td><td>1800</td><td>1500</td><td>2065</td><td>Φ2165X3600</td><td>7.5</td><td>80</td><td>2590</td></tr><tr><td>4000</td><td>4020</td><td>5X15</td><td>1700</td><td>1900</td><td>1600</td><td>2165</td><td>2265X3800</td><td>7.5</td><td>80</td><td>3160</td></tr><tr><td>5000</td><td>5170</td><td>5X18</td><td>1800</td><td>2000</td><td>1700</td><td>2265</td><td>Φ2370X4000</td><td>11.5</td><td>80</td><td>4100</td></tr><tr><td>6000</td><td>6280</td><td>6X18</td><td>1900</td><td>2100</td><td>1900</td><td>2365</td><td>Φ2485X4500</td><td>11.5</td><td>80</td><td>5650</td></tr></table></body></html>  \n\n表4-1-6醇酸树脂反应装置配套设备规格  \n\n\n<html><body><table><tr><td>项目</td><td colspan=\"4\">反应釜</td><td colspan=\"3\">稀释釜</td><td rowspan=\"3\">冷凝器</td><td rowspan=\"3\">分水器</td><td rowspan=\"3\">配套 加热炉</td></tr><tr><td>设计压力/MPa</td><td colspan=\"4\">（釜内)0.05/0.25(夹套、盘管）</td><td colspan=\"3\">（釜内）0.05/0.3（盘管或夹套）</td></tr><tr><td>设计温度/℃</td><td colspan=\"4\">300/300</td><td colspan=\"3\">180</td><td></td><td></td></tr><tr><td>公称容积/L</td><td>尺寸 /PmmXmm</td><td>/L</td><td>/kW</td><td>/m²</td><td>装料容量 搅拌功率 传热面积 公称容积 搅拌功率 传热面积 传热面积 公称容积 /L</td><td>/kW</td><td>/m²</td><td>/m²</td><td>/L</td><td>供热能力 /(MJ/h)</td></tr><tr><td>1000</td><td>1000×1150</td><td>750</td><td>2.2</td><td>3.2</td><td>2000</td><td>2.2</td><td>1.4</td><td>6</td><td>60</td><td>420</td></tr><tr><td>2000</td><td>1300 ×1400</td><td>1500</td><td>2.2~3.7</td><td>5.1</td><td>4000</td><td>3</td><td>2.9</td><td>12</td><td>120</td><td>1050</td></tr><tr><td>3000</td><td>1500×1600</td><td>2300</td><td>3~5.5</td><td>6.9</td><td>6000</td><td>5.5</td><td>4.3</td><td>18</td><td>200</td><td>1050</td></tr><tr><td>4000</td><td>1600×1800</td><td>3000</td><td>4~7.5</td><td>8.3</td><td>8000</td><td>7.5</td><td>5.7</td><td>20</td><td>200</td><td>1680</td></tr><tr><td>5000</td><td>1700×2000</td><td>3700</td><td>4~7.5</td><td>9.8</td><td>10000</td><td>7.5</td><td>7.4</td><td>25</td><td>250</td><td>1680</td></tr><tr><td>6000</td><td>1900×2000</td><td>4500</td><td>5.5~11</td><td>17</td><td>12000</td><td>7.5</td><td>8.5</td><td>30</td><td>300</td><td>2100</td></tr><tr><td>10000</td><td>2200×2400</td><td>7500</td><td>11～15</td><td>31</td><td>20000</td><td>11</td><td>14</td><td>45</td><td>450</td><td>3150</td></tr><tr><td>12000</td><td>2400×2500</td><td>9500</td><td>11～22</td><td>34</td><td>24000</td><td>18.5</td><td>18</td><td>55</td><td>550</td><td>4200</td></tr><tr><td>15000</td><td>2500× 2700</td><td>11000</td><td>18.5~22</td><td>43</td><td>30000</td><td>18.5</td><td>22</td><td>70</td><td>700</td><td>4200</td></tr><tr><td>20000</td><td>2600X3000</td><td>13000</td><td>18.5~30</td><td>56</td><td>40000</td><td>22</td><td>27</td><td>80</td><td>800</td><td>5250</td></tr></table></body></html>\n\n注：稀释釜的容积以略大于反应釜容积的2倍为宜。  \n\n表4-1-7氨基树脂反应装置配套设备规格  \n\n\n<html><body><table><tr><td>项 目</td><td colspan=\"3\">反应釜</td><td rowspan=\"3\">冷凝器</td><td rowspan=\"3\">分水器</td></tr><tr><td>设计压力/MPa</td><td colspan=\"3\">（釜内）－0.1/0.3(夹套、盘管）</td></tr><tr><td>设计温度/C</td><td colspan=\"3\">150/150</td></tr><tr><td>公称容积/L</td><td>装料量/L</td><td>搅拌功率/kW</td><td>传热面积/m²</td><td>传热面积/m²</td><td>公称容积/L</td></tr><tr><td>500</td><td>350</td><td>1.5</td><td>2.3</td><td>4</td><td>40</td></tr><tr><td>1000</td><td>750</td><td>2.2</td><td>3.8</td><td>8</td><td>60</td></tr><tr><td>2000</td><td>1500</td><td>2.2</td><td>5.0</td><td>16</td><td>120</td></tr><tr><td>3000</td><td>2300</td><td>3.0</td><td>6.8</td><td>24</td><td>200</td></tr></table></body></html>  \n\n续表  \n\n<html><body><table><tr><td>项目</td><td colspan=\"3\">反应釜</td><td rowspan=\"2\">冷凝器</td><td rowspan=\"2\">分水器</td></tr><tr><td>设计压力/MPa</td><td colspan=\"3\">（釜内）－0.1/0.3(夹套、盘管）</td></tr><tr><td>设计温度/C</td><td colspan=\"3\">150/150</td><td></td><td></td></tr><tr><td>公称容积/L</td><td>装料量/L</td><td>搅拌功率/kW</td><td>传热面积/m2</td><td>传热面积/m²</td><td>公称容积/L</td></tr><tr><td>4000</td><td>3000</td><td>4.0</td><td>9.3</td><td>32</td><td>200</td></tr><tr><td>5000</td><td>3700</td><td>4.0</td><td>9.3</td><td>40</td><td>250</td></tr><tr><td>6000</td><td>4500</td><td>5.5</td><td>11.7</td><td>48</td><td>300</td></tr><tr><td>8000</td><td>6000</td><td>7.5</td><td>14.7</td><td>64</td><td>350</td></tr><tr><td>10000</td><td>7500</td><td>11</td><td>21</td><td>80</td><td>450</td></tr><tr><td>12000</td><td>9000</td><td>11</td><td>22</td><td>88</td><td>550</td></tr></table></body></html>  \n\n表4-1-8 丙烯酸树脂反应装置配套设备规格  \n\n\n<html><body><table><tr><td rowspan=\"2\">项目</td><td colspan=\"2\" rowspan=\"2\">丙烯酸溶剂型树脂反应釜</td><td colspan=\"4\">丙烯酸乳液型树脂</td></tr><tr><td colspan=\"2\">反应釜</td><td colspan=\"2\">调节釜</td></tr><tr><td>设计压力/MPa</td><td colspan=\"2\">（釜内）-0.1/0.6(夹套、盘管）</td><td colspan=\"2\">（釜内）常压/0.3（夹套）</td><td colspan=\"2\">常压</td></tr><tr><td>设计温度/℃</td><td colspan=\"2\">170/170</td><td colspan=\"2\">150/150</td><td colspan=\"2\"><100</td></tr><tr><td>公称容积/L</td><td>搅拌功率/kW</td><td>传热面积/m²</td><td>搅拌功率/kW</td><td>传热面积/m</td><td>公称容积/L</td><td>搅拌功率/kW</td></tr><tr><td>500</td><td>1.1</td><td>2.5</td><td>1.5</td><td>2.0</td><td>1000</td><td>1.5</td></tr><tr><td>1000</td><td>1.5</td><td>4.1</td><td>1.5</td><td>3.1</td><td>2000</td><td>2.2</td></tr><tr><td>2000</td><td>2.2</td><td>5.8</td><td>2.2</td><td>5.6</td><td>4000</td><td>5.5</td></tr><tr><td>3000</td><td>3</td><td>7.9</td><td>3</td><td>7.4</td><td>6000</td><td>7.5</td></tr><tr><td>4000</td><td>3</td><td>11</td><td>5.5</td><td>8.6</td><td>8000</td><td>7.5</td></tr><tr><td>5000</td><td>4</td><td>11.3</td><td>5.5</td><td>10</td><td>10000</td><td>11</td></tr><tr><td>6000</td><td>5.5</td><td>14</td><td>7.5</td><td>12</td><td>12000</td><td>11</td></tr><tr><td>8000</td><td>7.5</td><td>18</td><td>7.5</td><td>15</td><td>16000</td><td>15</td></tr><tr><td>10000</td><td>7.5</td><td>22</td><td>11</td><td>18</td><td>20000</td><td>18.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1108,
+        "chunk": "# 三、加热设备  \n\n在树脂生产的过程中，温度的控制至关重要。按照工艺要求，使反应在规定的温度下进行，既能保证产品质量，又能缩短工时。同时也要求加热和冷却的速率较快，以减少所占用的时间，提高单机产量。冷却不及时，还会影响产品质量，甚至酿成事故。所以必须合理选用加热方式和设备，并采取相应的冷却措施。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1109,
+        "chunk": "# 1.加热方式的分类及选择  \n\n（1）加热方式的分类加热方式可分为直接加热和间接加热，常用的加热方式见表4-1-9。  \n\n![](images/9048fa2924a35f2a190c69c1163ae2261209a5fa56a1682d2573ff5e29c64ac3.jpg)  \n\n(2）加热方式的选择加热方式的选择，要因地制宜，综合考虑下列问题。  \n\n$\\textcircled{1}$ 生产工艺提出的要求如加热温度、加热速率、是否需要冷却及冷却的速率，要求达到的温度精度、对自控的要求等。  \n\n$\\textcircled{2}$ 生产规模及设备容量的大小近年来导热油（循环）加热很流行，但它也有系统庞大、复杂、附属设备多、耗电量大、占地面积大、占用人员多以及投资费用高等缺点。所以，若生产规模很小或设备容量很小，可能用电加热更经济。  \n\n$\\textcircled{3}$ 当地及现场环境的条件有些地方电力资源充足，用电不紧张，可适当多考虑用一些电加热（要作经济技术对比)。有些工厂场地面积小，无堆煤存灰之处，就不宜选用燃煤热油炉。随着环境保护的要求越来越高，一些城市已开始限制燃煤。有些环境要求防爆，选用的加热方式是否符合要求，还要征得当地消防部门的同意。  \n\n总的来说，在低温树脂的生产中，对温度调节要求不高的可用蒸汽加热，如对反应温度比较敏感、调节范围比较窄、不允许造成局部过热的，则应采用热水或加压热水加热系统。高温树脂生产，可供选择的加热方式较多，要作多方面的分析对比，灵活选择。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1110,
+        "chunk": "# 2.直接火加热  \n\n(1）概述直接火加热即明火加热，是最原始、最古老的加热方法。它利用固体、液体或气体燃料燃烧的火焰或烟道气直接加热釜底及釜壁。由于它简单易行，投资费用低，可达到很高的温度而且升温速率较快，所以至今还有使用。  \n\n(2）3种燃料加热的特点及冷却方法利用固体燃料，用煤的很少见，常用的是焦炭，并用吹风机助燃。一般是釜固定，灶在小车上，小车可在铁轨上移动，此谓“死锅活灶”。另一种是灶在地面上固定，釜在小车上，反应达到终点时立即把小车拉走，此谓“活锅死灶”。无论炉灶是固定的或移动的，劳动强度都很大，环境保护差，温度调节比较困难。  \n\n在直接火加热的几种燃料中，以燃柴油较普遍，燃烧设备有各种燃油喷嘴及燃烧机，燃油喷嘴利用压缩空气或蒸汽雾化、压力雾化、电动转杯式雾化等方法将油雾化，使其能完全燃烧。燃烧机是将燃油喷嘴、风机、油泵等合理地组合于一体，近年比较先进的燃烧机增设了自动点火和熄火保护装置等自控手段，性能更好。  \n\n煤气或天然气加热既清洁又简便，温度控制方便，便于实现自动化。可采用各种燃气烧嘴，也可用不锈钢管钻孔制成环状燃烧器，后者一般由同心圆布置的内外两圈构成，可分别用阀门控制，便于调节火力大小。  \n\n对反应釜降温冷却的方法，一般在炉膛内敷设环形水管，上钻小孔，当需要冷却时，撤离或灭掉火源后向釜壁及釜底喷水。  \n\n(3）直接火加热的缺点及安全注意事项直接火加热的缺点是安全性差，容易发生火灾事故；加热不均匀，易造成局部过热，使产品质量下降，而且容易烧坏釜底。  \n\n发生火灾最常见的原因是釜壁与灶台间有间隙，当出现物料胀锅溢出情况时，易燃物料顺着釜壁流下接触火源而引起燃烧，有时由于炉膛非常热，即使已撤掉火源，也有可能引燃。所以在炉灶上装上反应釜后，要把釜壁与灶台的间隙填死，使安装反应釜的灶台面上即使洒、漏一些物料，也不至于着火燃烧。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1111,
+        "chunk": "# 3.电加热  \n\n(1）工频电感加热采用工频电感加热的反应釜如图4-1-34所示。在铁磁物质制造的反应釜外装有一组或几组感应线圈制成的工频电感加热器，当感应线圈中通过工频交流电$({\\mathrm{50Hz}})$ 时，则在其周围形成交变磁场。在交变磁场作用下，反应釜的铁壳中产生感应电流——涡流。工频电感加热就是利用涡流损耗在铁壳中所产生的热量对釜内物料进行加热。  \n\n由于不锈钢受感应产生的涡流小，所以不锈钢反应釜不能直接用于工频电感加热。涂料生产中的工频电感加热反应釜一般用碳钢和不锈钢的复合钢板制作。  \n\n![](images/148467ca29fa4afa62c6d6a5dce1c679c63e24d3e94257e082bca67b312740df.jpg)  \n图4-1-34 工频电感加热反应釜 $(32\\mathbf{m}^{3}$  \n\n工频电感加热多用于高温反应型的树脂生产。它的优点是取材容易，施工简便，加热比较均匀，控制温度方便，作业环境比较清洁。缺点是功率因数低，约为0.65～0.70，热效率低，耗电量大，运行费用高。近年来，随着其他更节能的加热方式出现，工频电感加热已很少应用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1112,
+        "chunk": "# (2）电阻远红外加热  \n\n1一釜体；2—盘管；3—传动装置；4—搅拌轴；5—打沫器；  \n\n6一电感线圈；7一搅拌桨；  \n\n$\\textcircled{1}$ 结构和原理 里红外线是波长为0.72～1000μm之间的一种电磁波，人们按红外线的波长将其分为近红外线、中红外线和远红外线。通常把波长范围为5.6～1000μm之间的红外线，称为远红外线。  \n\n8一锚式搅拌桨；9—外壳在1000℃高温下长期使用。  \n\n图4-1-35是电阻远红外线加热器的结构。其工作原理是用不锈钢（1Crl8Ni9Ti）电阻带或其他电热材料做电热元件，当电流通过电热元件时，将电能转换成热能，此热能传导给陶瓷碳化硅板（碳化硅板背面，即靠反应釜一侧涂有远红外涂料），激发远红外涂料中的金属氧化物原子，可提高远红外辐射能。此时，碳化硅板既以热传导又以远红外热辐射形式向反应釜传热。所以它也称碳化硅（远红外）辐射加热装置。不锈钢电阻带和碳化硅板外面有隔热性能很好的保温层及绝缘层。目前大多用硅酸铝纤维毡做保温材料，这种被称作耐火纤维的材料可  \n\n$\\textcircled{2}$ 电阻远红外加热的优缺点 电阻远红外加热是20世纪70年代发展起来的一种加热新技术。它的主要优点是功率因数高（约0.97）、热效率高、省电、节能。据介绍，它比工频电感加热可节电25%左右。而且安全、卫生、运行时无噪声。电阻远红外加热反应釜受热均匀，若配用可控硅调功器，能方便地调控温度。  \n\n电阻远红外加热的缺点是一次投资费用高，使用寿命一般不及工频电感加热的长，发生故障的概率比工频电感高，冷却不方便。冷却方法是在釜内设置蛇管通水冷却。此外，对密封风冷式加热器还可往加热器外壳内强制通风，进行冷却。  \n\n$\\textcircled{3}$ 选用注意事项 为保证安全使用并发挥其应有效益，在选用碳化硅辐射加热装置时应主要注意以下事项。  \n\na.即使采用“密封式”结构，也不能满足严格的防爆要求。一个辅助措施是装设可燃气体检测报警器。彻底的办法是让供货厂商设计防爆措施。  \n\n![](images/2dd749f2a1f2e7986d801fa2768af1f6364ff546f38da0c16f38c5745be62ebb.jpg)  \n\n图4-1-35电阻远红外加热器  \n1一釜体；2—防水罩；3，7，13，16—法兰；  \n4，8-加热器外壳；5一碳化硅辐射层；  \n6—隔热绝缘层；9，11，15—电阻带；  \n10—测温热电偶；12，14—电极  \n\nb.应装“过电流”和“漏电”等安全保护装置。  \n\nc.加热器严禁溅水和受潮，否则容易发生事故，可能烧坏电阻带，甚至因短路击穿反应釜釜壁。当用火碱水煮釜清洗时，严防碱水溢出渗入加热器。加热器停用时间较长易吸潮，使用时应先用低电压、后用正常电压烘干，检查电器绝缘性能合格后方可正常工作。  \n\n(3）电热棒加热电热棒是管状电热元件的俗称。它是用金属管做外壳，管中放入合金电阻丝做发热体，在空隙部分紧密填充具有良好绝缘性能和导热性能的结晶氧化镁而组成的一种电加热元件。  \n\n$\\textcircled{1}$ 加热方式的分类及结构电热棒的使用，主要有两种方式。一种方式是直接插入釜内物料中加热。这种方式，热效率当然很高，但由于树脂反应釜内的液体大多是易燃易爆的，故一般不推荐使用。另一种方式是将电热棒插人反应釜夹套中，加热夹套中的热载体，热载体在受热同时给反应釜加热。热载体处于自然对流状态。  \n\n放人夹套中的热载体按工作温度来选择，联苯混合物（道生）虽然热稳定性好，耐温高，使用寿命长，但太易渗漏，还有难闻的气味，所以尽量不用。还是选用适当牌号的导热油较好。一定要注意夹套中的热载体不可加满，要留出一定的空间供受热时膨胀用，也可以设置一个高位膨胀罐，罐上部通大气。  \n\n釜内可设置蛇管，供通水冷却用。  \n\n$\\textcircled{2}$ 电热棒加热的优缺点电热棒加热的优点是简单易行，一次投资费用低，使用温度范围广。  \n\n电热棒间接加热方法的缺点是热载体没有强制循环，电热棒表面的高温易使其局部过热、分解、变质，使用寿命大为缩短；同时电热棒表面也容易结焦，使传热效率降低。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1113,
+        "chunk": "# 4.蒸汽加热  \n\n(1）概述蒸汽加热即饱和水蒸气加热，是低温树脂最常用的加热方法。将蒸汽从上部通入反应釜的夹套或釜内盘管中，然后将冷凝水从夹套或盘管下方通过疏水器排出，这样就可以方便地完成加热操作。由于饱和水蒸气的温度与压力有对应关系，通过压力的调节就能控制加热温度。表4-1-10摘录了部分饱和水蒸气的压力与温度的对应关系。  \n\n表4-1-10 饱和水蒸气压力与温度对照表  \n\n\n<html><body><table><tr><td>表压/MPa</td><td>温度/℃</td><td>表压/MPa</td><td>温度/℃</td></tr><tr><td>0.1</td><td>120.2</td><td>0.6</td><td>164.7</td></tr><tr><td>0.2</td><td>133.3</td><td>0.7</td><td>170.4</td></tr><tr><td>0.3</td><td>143.4</td><td>0.8</td><td>175.1</td></tr><tr><td>0.4</td><td>151.7</td><td>0.9</td><td>179.9</td></tr><tr><td>0.5</td><td>158.7</td><td>1</td><td>183.5</td></tr></table></body></html>  \n\n从表4-1-10中可看出，要加热到 $150^{\\circ}C$ 左右，加上加热时必须的温差，大约要用 $0.6\\sim$ $0.7\\mathrm{MPa}$ 压力的蒸汽才行。如加热温度再提高，由于压力太大，对一般夹套反应釜是不适宜的（如 $220^{\\circ}C$ 对应的蒸汽压力为 $\\mathbf{2.38MPa}$ ， $260\\%$ 为 $4\\cdot79\\mathrm{{MPa}}$ + $300\\%$ 为 $8,85\\mathbf{MPa},$ 。因此，蒸汽加热通常用于反应温度在 $150^{\\circ}C$ 以下的低温树脂的生产。  \n\n(2）操作注意事项 利用蒸汽加热，要注意几个问题  \n\n$\\textcircled{1}$ 排气在开始加热时，要把夹套的空气排尽。一般多在蒸汽入口对面的夹套顶端设置排气旋塞，以排除不凝性气体。  \n\n$\\textcircled{2}$ 放水冷凝水要及时排除。否则部分传热面积被浸泡，将使传热效果变坏。冷凝水要通过疏水器排出，不要使蒸汽从旁路直接逸出，以免浪费能源。  \n\n$\\textcircled{3}$ 勿超压夹套通人蒸汽加热，反应釜本体承受外压，所以蒸汽压力不能超过设备许可的工作压力，特别是当夹套上未装安全阀或来汽管路上未装切实可靠的减压阀时，更要小心谨慎，以免釜体被压或发生其他事故。  \n\n(3）冷却方法只要关掉蒸汽，在冷凝水出口处（疏水器前）通人冷却水，在蒸汽人口处接出冷却水即可。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1114,
+        "chunk": "# 5.热水加热  \n\n（1）热水加热热水加热的优点是加热均匀、缓和，不会产生局部过热现象。缺点是其对流传热系数没有蒸汽的大。加热温度较低，普通热水加热的温度，大约不超过 $90^{\\circ}C$ 。  \n\n(2）加压热水加热加压热水（过热水）加热，其温度视压力的大小可提高很多。如用表压0.7MPa的蒸汽通过一个高效换热器可将水加热到 $150^{\\circ}C$ 左右，加压热水（约0.4MPa）经离心泵密闭循环，向反应釜供热。反应釜可采用半管夹套结构，对温度可进行自动调节，加热均匀，操作方便。加压热水加热可用于低温树脂生产，如丙烯酸树脂和乳液等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1115,
+        "chunk": "# 6.导热油（循环）加热  \n\n为了加热均匀，能精确调控温度并满足安全生产的要求，除去几种电加热方法外，还有普遍使用的间接加热法。间接加热，就是通过热载体来加热。以水为载体的蒸汽加热和热水加热，常用于 $150^{\\circ}C$ 以下。对 $150{\\sim}385^{\\circ}C$ 的范围，常用有机热载体加热。  \n\n有机热载体加热主要有导热油液相加热和联苯混合物气相加热两种方法。联苯混合物由$26.5\\%$ 的联苯与 $73.5\\%$ 的二苯醚组成，俗称道生。由于它极易渗漏，又有一种难以去掉的臭味，且有一定的毒性，加上气相炉危险性大，历史上曾发生过爆炸事故，近年已很少使用。目前广泛使用的是导热油液相加热。  \n\n(1）导热油加热流程导热油液相加热，依靠循环泵进行强制循环。循环泵将导热油注人热油炉，尔后再到用热设备（如反应釜)，此系统称注入式循环系统。若循环泵将热油炉中的导热油抽出，再送人用热设备，则该系统称引出式循环系统。注入式系统可使循环泵在较低温度下运行，用热设备承受的导热油压力亦较低，所以目前国内外导热油加热系统大多采用它。  \n\n由于导热油在加热时体积要膨胀，在冷却时体积要缩小，所以在系统主循环的旁路上，都要安置（高位）膨胀槽，以补偿循环系统中导热油体积的变化。  \n\n图4-1-36为美国孟山都公司提供的液相导热油加热基本流程。该流程的一大特点是膨胀槽的双下降管设计。当系统刚开车需要脱水、脱气时，可将阀门A关闭，阀门B、C全部打开，这样使导热油全部通过膨胀槽，排气速率大大加快，脱水、脱气的时间缩短。日本综研化学株式会社的加热流程，也有与此类似的双下降管设计。  \n\n如除了加热外，还需要利用导热油进行冷却，可采用图4-1-37的流程。此系统中有两套系统：热油系统和冷油系统。当需要冷却时，启用冷油系统。但此时热油炉和热油循环泵都不能停，应先打开阀门 ${\\bf K}_{1}$ ，使热油通过 ${\\bf K}_{1}$ 阀从旁路进行循环。然后倒换用热设备的进出口阀门，关闭 ${\\bf K}_{2}$ ， $\\mathbf{K_{4}}$ ，开启 ${\\bf K}_{3}$ ， ${\\bf K}_{5}$ ，启动冷油循环泵，将冷油贮槽中的冷油送入用热设备，置换热油。对用热设备进行冷却。换热后的油通过冷油冷却器冷却，再进入冷油贮槽，如此循环，直至达到冷却要求。  \n\n有的设计，只利用导热油进行加热，而另外专门用水进行冷却。如用反应釜的夹套或半管夹套加热，釜内蛇管通水冷却。也有用釜内蛇管进行加热，而用反应釜的夹套或半管夹套通水冷却的。这样做的优点是导热油系统流程简化，操作简单；反应釜的夹套或半管夹套因  \n\n![](images/bab7b6d5b3d13135b33220375208be6382f9ab2ef666b28cb191a71dcf9dca2e.jpg)  \n图4-1-36 导热油加热基本流程（美国孟山都公司）  \n\nTIC—温度指示控制器；TI—温度指示；HLA—高液位报警；LLA/S—低液位报警/切断； $\\Delta P$ 一压力差温差应力产生焊缝裂纹的概率下降，设备寿命延长。缺点是加热需要的时间加长。  \n\n![](images/0728676d7ac5a3e1abba80f7492317ab6588c812b79ffb4600ff53edd6c20418.jpg)  \n图4-1-37热油加热装置简要流程（加热和冷却） 1—热油炉；2—膨胀槽；3—用热设备；4—冷油冷却器；5—冷油贮槽； 6—冷油循环泵；7—热油贮槽；8—注油泵；9—过滤器；10一热油循环泵  \n\n近年的加热流程中增加了自动控制系统，如热油炉出口温度和反应釜内温度的自动调节系统，热油炉流量（或压差）自动调节系统等。  \n\n(2）热油炉热油炉是加热导热油的加热炉，是有机热载体加热炉中的液相炉，也称油锅炉。热油炉按所用的燃料不同，大致可分为3类：燃油、燃气热油炉、燃煤热油炉和电加热式热油炉。  \n\n热油炉的规格以供热能力或额定热功率表示。法定计量单位为 $\\mathbf{kJ}/\\mathbf{h}$ （千焦耳/小时）、$\\mathbb{M J}/\\mathbf{h}$ （兆焦耳/小时）、GJ/h（ $10^{9}$ 焦耳/小时）或 $\\mathbf{k}\\ W$ (千瓦)、MW（兆瓦)。国外习惯上用kcal/h（千卡/小时）表示。其间的换算关系为：  \n\n$$\n1\\mathbf{kW}{=}860\\mathbf{kcal/h}{=}3600\\mathbf{kJ/h}\n$$  \n\n$$\n1\\mathbf{kcal/h}{=}4.1868\\mathbf{kJ/h}{=}0.001163\\mathbf{kW}\n$$  \n\n① 燃油、煤气热油炉燃油炉的燃料主要是轻柴油或重油，燃气炉的燃料主要是煤气、天然气或液化石油气。炉子所用燃料不同，反映在燃烧器上有区别，炉子本体结构基本相同。  \n\n图4-1-38为盘管式燃油（气）热油炉结构。该炉系日本综研化学株式会社设计（VCP-N型)，炉为立式圆筒形。盘管有内、外两层，串联。每层盘管有3头，相互并联。燃烧机  \n\n![](images/988f7073a27875171208e1d4ae4c1878b7eea67313816942e0b41b55600ab3b7.jpg)  \n图4-1-38 盘管式燃油（气）热油炉结构  \n\n1一喷燃泵；2—视镜；3一火焰检测器；4—防爆门；   \n5—排气口；6—铭牌；7—人孔；8—提升把；9—炉壁  \n\n保温板；10—炉底保温板；11—工作人员人口；  \n\n12—地脚螺栓；13—空气阻尼调节器；14一鼓风机； 15-燃烧器电机；16一灭火蒸汽人口；17一天棚保温板； 18—安全阀（溢流阀）；19一温度检测口；20一温度计 插人口；21—燃烧器操作箱；22—差压开关；23—排放口； 24—热载体排放阀；25—出口总管；26—热载体出口；  \n\n27—热载体入口；28—人口总管装在炉顶，火焰向下喷。烟气经内、外层盘管间的间隙从上部排气口排入烟肉。炉子中央部位，是主要燃烧区，温度最高，炉管内侧主要接受辐射传热，此区域称辐射室或辐射段。内外层盘管间的间隙内，炉管主要接受对流传热，称对流室或对流段。在热油炉的总热负荷中，辐射段的热负荷约占七成左右。  \n\n该炉热效率较高（≥83%)，安全性能较好。当炉内点不着火或运行中自行灭火时，当热油出口温度到达上限时，或当热油进出口压差下降过大(表示通过炉管的流量下降)时，均能发出警报，并自动停止燃烧器的工作。  \n\n$\\textcircled{2}$ 燃煤热油炉 燃煤热油炉以煤为燃料。它与燃油、燃气炉的区别主要在燃烧系统。燃油、燃气使用各种烧嘴或燃烧机，燃煤则使用各种炉排。为达到环保要求，燃煤炉应配备有效的消烟、除尘设施。大型燃煤炉还配有上煤机和出渣机。  \n\n燃煤热油炉的优点是燃料成本低，但其缺点很多。一是本体及附属设备占地面积大，堆煤和出灰还要占地。二是工人劳动强度大，环境条件差，烟尘排放污染大气。三是自动化程度要比燃油、燃气炉差。四是炉管易被煤灰、烟尘覆盖，要经常清灰。五是当发生临时停电等紧急情况时，炉膛降温慢，易使炉管内导热油过热，影响到导热油及炉管的使用寿命。  \n\n随着对环保的要求日益提高，燃煤热油炉的应用逐渐减少。  \n\n$\\textcircled{3}$ ③电加热式热油炉商品名也称电加热器或油加热器。其结构一般为一细长圆筒，内用电热棒加热，导热油依靠循环泵作强制循环。加热器和循环泵通常装在可移动的铁架上，使用方便，有的产品可配带油冷却器。高位膨胀槽一般由用户自配。  \n\n由于电是二次能源，一般只在热负荷不太大时才选用电加热器。目前，国内生产的电加热器的功率范围约为6～360kW（30～1290MJ/h)，热效率较高，约为0.9～0.95。  \n\n(3）导热油系统的附属设备导热油系统除热油炉外，附属设备还有热油泵、膨胀槽、过滤器、冷却器及贮槽等。  \n\n$\\textcircled{1}$ 热油泵导热油要循环，必须有泵提供动力。导热油循环泵简称为热油泵。  \n\n以前热油泵常选用丫型离心泵。该泵机械密封易泄漏，噪声大，水冷系统较复杂，耗水量大。近年来推广一种RY型风冷式热油泵。该泵结构简单，体积小，采用碳纤维软填料环密封，密封效果好。由于不用水冷却，不但节约了宝贵的水资源，而且避免了冷却水漏入泵内及严寒时冻裂泵体的可能性。该泵系列流量为 $1\\sim500\\mathrm{m^{3}/h}$ ，扬程为 $10\\sim125\\mathrm{m}$ ，电机功率为 $0.37{\\sim}160\\ensuremath{\\mathrm{kW}}$ ，使用温度为一 $-20\\sim350^{\\circ}C$ 9  \n\n屏蔽泵也是比较理想的泵型。其最大优点是无轴封，不存在轴封泄漏问题；其次，因使用石墨轴承，运转时几乎无噪声。它的缺点是价格昂贵，要求进泵的导热油杂质要少，否则易磨坏石墨轴承；适用于热油系统的高温屏蔽泵要用不易结垢的软水进行冷却。此外，屏蔽泵的维护技术要求比较高。  \n\n$\\textcircled{2}$ 膨胀槽膨胀槽或称（高位）膨胀罐，其作用切不可低估。它具有以下功能。  \n\na.膨胀 吸收整个系统中导热油因温度升高所产生的膨胀量（有的可达 $25\\%$ 左右)b.补油 补充系统中因泄漏等原因所造成的损失。  \nc.高位 起补充压头的作用。  \nd.脱水排气在新油加人系统或系统意外进水时进行脱水、排气(低沸物)。  \n$e_{\\cdot}$ 注油向系统补加油时，应从膨胀槽注人，这样有利于降低膨胀槽的油温。  \n膨胀槽安装、使用的注意要点如下。  \n\na.高位安装膨胀槽底应高出系统中所有用热和供热设备导热油最高液面 $1.5\\mathrm{m}$ 以上。  \n\nb.膨胀管宜小膨胀槽下部接膨胀管，其管径一般不大于主管径的一半。管径太小，脱水排气速度慢，耽误时间；管径太大，将导致膨胀槽内油温过高促其氧化，缩短使用寿命。一个可供调节的方法是在膨胀管上设一直径较小的旁路（见图4-1-39)。在不作脱水排气操作时，关掉阀C走旁路（阀D开着)，旁路可不装阀。  \n\n![](images/823c4d0f91335496c0884153474811add7040ae0f1decb0e66beb25187c8e117.jpg)  \n图4-1-39膨胀槽流程（用冷却液封罐隔离） 1—热油循环泵；2一旁路管径约为主路的 $1/3$ ；3—膨胀槽；4—冷却液封罐 HLA—高液位报警；LLA一低液位报警  \n\nc.低位报警膨胀槽应装液面计和最低液位报警器，并设溢流管，溢流管应接贮槽。  \n\nd.油温要低膨胀槽内导热油的温度不应超过 $70^{\\circ}C$ ，如超过，应采取措施防止导热油氧化。一种方法是在膨胀槽液面上通入情性气体（如氮气）保护；另一种方法是设置一个冷却液封罐（见图4-1-39)。这样，与空气接触的只是冷却液封罐内温度较低的很小的液面，几乎不会被氧化，从而起到了保护导热油的作用。  \n\n$\\textcircled{3}$ 过滤器导热油系统使用的过滤器有两种。一种是粗过滤器，目的是滤掉铁锈、焊渣、导热油的结焦物等较大的杂质，一般用筒状不锈钢丝网过滤器，装在循环油泵前，主要为保护油泵。为减小阻力，节约能源，可在操作正常后把滤网取出。  \n\n另一种是细过滤器，目的是滤掉导热油中由于热裂解和氧化而生成的胶质和碳粒等微细杂质。这些杂质会形成结垢，影响传热，可致热油炉炉管局部过热，甚至造成裂解和结焦的恶性循环。这些杂质还会使轴承（屏蔽泵）、轴封、阀杆等机件磨损，产生泄漏，同时使全系统阻力增加。因此，安装并用好细过滤器很有必要。  \n\n细过滤可用粉末冶金微孔过滤器。由于阻力很大，这种过滤器只能装在旁路系统中。  \n\n也有推荐使用玻璃纤维缠绕在多孔金属管上作为滤芯的过滤器  \n\n有的单位在系统停车检修时，利用过滤树脂备用的水平板式过滤机，用硅藻土为助滤剂，将全部导热油进行过滤，效果较好。  \n\n$\\textcircled{4}$ 冷却器加热和冷却兼用的流程，需设置冷却器。目前大多使用管壳式换热器作冷却器，用经冷却塔冷却的工业循环水来冷却导热油。由于循环水中含盐浓度高，又有微生物的作用，碳钢冷却器腐蚀严重，一般使用 $2\\sim3$ 年，换热管就会发生穿孔而漏水。为此，对工业循环水进行化学处理就很有必要，而采用不锈钢材料来制作冷却器的换热管和管板，也是一种比较好的选择。  \n\n螺旋板式冷却器，由于其结构紧凑，占地面积小，传热效率高，也有人采用。为便于清洗，应采用可拆式结构。  \n\n寒冷季节停车时，要防止结冰冻坏冷却器。为此，可采用将水放净或强制流动等措施。  \n\n$\\textcircled{5}$ 贮槽当系统检修或发生意外事故时，需将系统中的导热油放人贮槽中。  \n\n(4）导热油导热油作为热载体应满足下列条件：热稳定性好，抗氧化性能好；沸点或初馏点高，蒸气压低，能在高温下以液相运行，且压力较低；闪点较高，以利于安全生产；毒性低，渗透性小，无刺激性气味；凝固点低，可在寒冷地区使用；对钢材不腐蚀；货源充足，价格合理。  \n\n（5）导热油使用应注意的几个问题  \n\n$\\textcircled{1}$ 导热油的工作温度因为接近炉管内壁那层流体的温度——-膜温，比主流体温度高。所以大多推荐导热油的工作温度比允许最高工作温度低 $20^{\\circ}C$ 以上。  \n\n$\\textcircled{2}$ 导热油的氧化问题导热油的温度越高，氧化速率越快。所以要采取各种方法尽量降低膨胀槽的油温。一定要精心操作，在加热和冷却交替时，严格遵守各阀门的开关顺序，原则是要防止热油系统的导热油流入冷油系统，以稳定膨胀槽液面，使之不剧烈波动，以免热油大量流入膨胀槽，导致油温升高。  \n\n$\\textcircled{3}$ 导热油在炉管内的流速导热油在炉管内应有较高的流速，使之保持湍流状态，以强化传热，防止导热油过热分解，产生积碳。原劳动部《有机热载体炉安全技术监察规程》规定，炉管中导热油的流速，辐射受热面不低于 $\\mathrm{2m/s}$ ，对流受热面不低于 $1.5\\mathrm{m/s}$ 0  \n\n为达到要求的流速，就要有足够的流量通过热油炉。为此要做到以下几点。  \n\n热油系统的流程设计要合理，要安装可以自动调节控制的旁路，当通过热油炉的流量或热油炉进出口压差小于规定值时，能自动开大旁路阀门，加大热油循环量。  \n\n为保证热油循环泵长期连续运行，应配置备用泵。  \n\n要有防止临时停电的措施。最好备有双电源，或备用一台柴油机拖动的循环泵。当无上述条件时，在抓紧停炉降温的同时，将热油炉中的热油放入地下贮槽，让膨胀槽内的冷油自动流下，以保护导热油及炉管。  \n\n$\\textcircled{4}$ 导热油的定期检验按原化工部规定，导热油应每半年取样分析一次，应对化验数据进行分析，找出存在问题及对策。若黏度、残碳、闪点、酸值4项指标中有两项不合格，则导热油应更新或再生。  \n\n（6）导热油系统运行注意事项  \n\n$\\textcircled{1}$ 严格控制热油炉出口油温严禁超温运行，切忌升温过急。一般要求升温速率不大于 $50^{\\circ}C/\\mathrm{h}$ 。热油炉进出口温差推荐为 $20\\sim30^{\\circ}C$ 0  \n\n$\\textcircled{2}$ 注意点火安全对燃油、燃气热油炉，要防止点火时发生爆炸。点火前，应先对炉膛抽风或鼓风，排净可燃气体后方可点火。点火时，要做到“火”等“气”（或油)。  \n\n$\\textcircled{3}$ 勤观察、勤检查操作中应经常观察燃烧火焰和排烟情况，以判断燃烧装置是否完好。对装有视孔的热油炉，要观察炉管有无变色、变形及积灰情况，未装视孔的热油炉，应定期检查炉管。  \n\n$\\textcircled{4}$ 严防导热油系统进水系统如不慎进水，水在高温的油中汽化，将造成系统压力急剧波动（压力表指针乱摆)；循环泵可能产生汽蚀，不能正常工作；膨胀槽排气管冒汽，甚至连油一起冲出。这时只好紧急停炉、降温，找出系统进水原因，予以消除，然后才能重新开车，脱水后才能投人正常运行。  \n\n可能导致导热油系统进水的原因有冷油冷却器被腐蚀进水，用水冷却的循环油泵漏水等。  \n\n$\\textcircled{5}$ 紧急情况停车  \n\na.当突然停电或热油循环泵因故停止运转而不能立即启动备用泵时，应立即停车并降温。  \n\nb.当发现炉管或其他受压元件破裂、泄漏或出现鼓包、变形等缺陷危及安全时，应立即停车。先熄火，并停循环泵，关闭热油炉进出口阀门，同时将炉内导热油放人地下槽。  \n\nc.当系统发生严重泄漏，影响正常工作时，应立即停车。处理方法同b。  \n\n$\\textcircled{6}$ 管路、阀门防止泄漏  \n\na.法兰和阀门都应选用公称压力2.5MPa等级。  \n\nb.法兰垫片采用耐高温和耐油的材料，如金属缠绕石棉垫片或膨胀石墨复合垫片。  \n\nc.阀门填料宜用编织膨胀石墨或碳纤维填料，也可二者组合使用。经常启闭的阀门最好采用金属波纹管阀门，由于导热油与阀杆之间有不锈钢波纹管分隔，可保证阀杆处不泄漏。  \n\n$\\textcircled{7}$ 日常发生故障的原因及处理方法参见HG26173-—1991《热油炉维护检修规程》。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1116,
+        "chunk": "# 四、净化设备",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1117,
+        "chunk": "# 1.概述  \n\n树脂、漆料和清漆中的杂质，除原料及制造过程中带入的机械杂质外，还可能有树脂合成过程中形成的不溶解的胶粒和在贮存过程中析出的不溶解物质。这些杂质如不除掉，将严重影响产品性能。  \n\n从液态涂料半成品或成品中清除固体或胶粒状杂质的液固分离过程，称为净化。  \n\n净化的方法有重力沉降、过滤和离心分离等几种。重力沉降的方法由于耗时长，分离效果差，往往只作为一种辅助方法来使用。离心分离是利用离心力分离流体中悬浮的固体颗粒或液滴的过程。按作用原理，离心分离有离心过滤和离心沉降之分，前者适用于固体含量较高且颗粒较大的悬浮液，在过滤式离心机中进行；后者适用于固体含量较低且颗粒较小的悬浮液，在沉降式离心机中进行。  \n\n最广泛使用的净化方法，还是过滤。树脂、漆料和清漆常用的过滤设备有板框压滤机和箱式压滤机、滤芯过滤器、袋式过滤器、水平板式过滤机和垂直网板式过滤机。  \n\n(1）过滤原理过滤是利用过滤介质从流体中分离固体颗粒的过程。常用滤纸、滤布、金属丝网等多孔物料作为过滤介质，使液体或气体通过，固体颗粒则被截留在过滤介质上。在过滤过程中，被过滤的悬浮液称为滤浆，滤浆中的固体颗粒称为滤渣，被截留在过滤介质上的滤渣称为滤饼，透过滤饼和过滤介质的澄清液称为滤液。  \n\n在过滤开始时，滤液要通过过滤介质，就必须克服过滤介质对流体流动的阻力。此后逐渐形成滤饼，还要加上滤饼的阻力。在大多数情况下，过滤介质并不能完全阻挡滤液中细小微粒的通过。所以在过滤初始，滤液往往略显浑浊。当过滤介质上积有一定厚度的滤饼后，滤液即显澄清。  \n\n单位时间内每单位过滤面积上通过的滤液体积，称为过滤速率。在过滤过程中，保持过滤速率为恒定值的过滤方式称恒速过滤；另一种方式是保持过滤时的压力差为恒定值的恒压过滤。比较合理的过滤方式，是先采用恒速过滤，随着滤饼的不断增厚，过滤速率降低，再逐渐加压，采用恒压过滤。  \n\n(2）表面过滤和深层过滤按过滤机理，可将过滤分为表面过滤和深层过滤，它们在涂料生产中的应用都很广。表面过滤以滤布、滤纸、滤网等为过滤介质，滤渣堆积在过滤介质表面，逐渐形成滤饼。所以也称为滤饼过滤。对于表面过滤，滤饼才是真正有效的过滤介质。  \n\n深层过滤的过滤介质由固体颗粒（助滤剂）堆积成的床层构成，或用短纤维多层绕制成管状滤芯。过滤介质的空隙形成许多曲折、细长的通道，被过滤的颗粒比介质内部的空隙  \n\n![](images/fb742aed9a8bf2e27f98eb0ce1464098e6476babfcd2f1f9d7f8398315fd43ac.jpg)  \n图4-1-40 表面过滤和深层过滤  \n\n小，过滤作用发生在介质的全部空隙体内而不是介质的外表面。悬浮液中细小的颗粒由于热运动和流体的动力作用走向通道的壁面，并借静电和表面力被截留。  \n\n表面过滤和深层过滤的机理可从图4-1-40上形象地体现出来。显然，深层过滤比表面过滤能滤除更多的杂质。另外，表面过滤不适用于软质和纤维状杂质的过滤，而深层过滤几乎适用于各种杂质。  \n\n表面过滤初期压降一般较小，但很快上升，过滤速率也很快下降。而深层过滤则能在相当长的一段时间里维持一定的压降和过滤速率。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1118,
+        "chunk": "# 2.板框压滤机和箱式压滤机  \n\n板框压滤机和箱式压滤机是使用历史悠久且至今仍在使用的液固分离设备。它  \n\n们统称为压滤机。  \n\n(1）板框压滤机板框压滤机（见图4-1-41）主要由止推板、滤框、滤板、主梁、压紧板和压紧装置等零部件组成。滤板和滤框按一定顺序交替排列。不同规格的机组可装滤框约10～60块。滤板和滤框的外廓大多为正方形（见图4-1-42)，滤板上遍布沟渠，其形式有棋盘式、辐射式等多种。  \n\n![](images/04601c53fd26f8c10bf20bc5d1dd295bb0b5d71356ff70fcba751bb4fd91fab6.jpg)  \n\n![](images/aa375bcd62c563bb90cc18071de9717bf21700ed65ed3bbd69461670c8165e26.jpg)  \n图4-1-41 板框压滤机  \n\n<html><body><table><tr><td>项目</td><td>进料口</td><td>出液口</td><td>洗液入口</td><td>洗液出口</td></tr><tr><td>明流不可洗</td><td>A</td><td>E</td><td></td><td></td></tr><tr><td>明流可洗</td><td>A</td><td>E</td><td>D</td><td>E</td></tr><tr><td>暗流不可洗</td><td>A</td><td>B</td><td></td><td></td></tr><tr><td>暗流可洗</td><td>A</td><td>B</td><td>D</td><td>C</td></tr></table></body></html>  \n\n1—止推板；2-滤框；3-滤板；4-主梁；5-压紧板；6-压紧装置板框压滤机按滤液的排出方式分明流式和暗流式两种。图4-1-43是明流式板框压滤机。  \n\n![](images/b7f57c99e7d60096c24e01c2e948c40b7ea2eca3fa048f0c28290a2b58648f14.jpg)  \n图4-1-42滤板和滤框的结构（明流式）  \n\n![](images/05fa4b2fc314b467fa09f54f813aead22086538aa3d4749fcf29fa31d6906454.jpg)  \n图4-1-43 明流式板框压滤机  \n\n![](images/98f4086805b2b46cc323294b47c023da3e355224d0a5544fe38be016d8a44468.jpg)  \n图4-1-44 箱式压滤机  \n\n暗流式是各滤板的滤液通过滤板与滤框下角的一个通道集中后，从止推板出液口流出。明流、暗流各有特点。明流式的优点是“明”，看得清，当某个旋塞流出的滤液浑浊了，说明里面滤布有破损，可立即关掉此旋塞，并不影响整机操作。明流式的缺点是滤液暴露于空气中，易挥发，污染环境，灰尘可能落人。必要时，也可订购明流、暗流两用结构的压滤机。  \n\n板框压滤机又可分为可洗式和不可洗式两种。对滤饼可进行洗涤的结构称为可洗式，对滤饼不能洗涤的结构称为不可洗式。滤饼洗涤的目的在于洗去滤饼中的杂质或洗下滤饼中的物料。过滤颜料，需要用可洗式；过滤树脂、漆料和清漆，常用不可洗式。  \n\n(2）箱式压滤机箱式压滤机又称凹板式压滤机，因为它只有凹的滤板而无滤框。图4-1-44为箱式压滤机。滤布用螺套卡在中心有孔的凹形滤板上。若干滤板组装后，滤板中心的孔就构成了滤浆的进料通道。滤浆再分别进人凹形滤板之间的空间内，滤液穿过滤布，沿滤板上的沟槽，汇集于滤板下方的出口流出。  \n\n箱式压滤机能容纳滤饼的空间较小，所以适用于滤渣含量少，以获得滤液为目的的过滤操作，如树脂、漆料和清漆的过滤。  \n\n(3）压滤机的优缺点优点是结构简单，工作可靠，过滤质量稳定（过滤细度可达$15\\mu\\mathrm{m})$ 15μm)。但由于它存在溶剂挥发大，污染环境，卫生条件差，而且滤布、滤纸损耗大、费用高等致命缺点，所以在涂料生产中的应用日趋减少。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1119,
+        "chunk": "# 3.滤芯过滤器  \n\n滤芯有多种。在涂料行业，最先使用的是纸质滤芯一一纸芯，纸芯原是用于汽车的空气滤清器上的。至今纸芯筒式过滤器仍在使用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1120,
+        "chunk": "# （1）纸芯筒式过滤器  \n\n$\\textcircled{1}$ 结构和原理（图4-1-45） 纸芯筒式过滤器是一个带盖的立式容器，内装若于纸芯。  \n\n![](images/2290dd4578c0c1e781cd8b14db7658b044951b76f7c9f6733be6ae1e24fd6bc5.jpg)  \n图4-1-45 纸芯筒式过滤器  \n\n1—筒体；2—排渣口；3—下封头；   \n4—定位套；5—出料口；6—支脚；7一拉杆螺栓；   \n8一固定板；9—纸芯；10一进料口；11一转臂； 12—吊钩；13—上盖；14—回转螺栓； 15—法兰；16—压紧板；17—弹簧  \n\n纸芯用滤纸像手风琴风箱那样折叠成圆筒状（图4-1-45中的9)，两端粘在钢盖板上（一端有孔），纸芯内用开孔薄钢板圆筒或金属丝网圆筒支撑。常用的纸芯外廓尺寸为70mm×240mm，展开面积约为0.3m，因折叠后的空隙窄小，易被滤渣填满，所以真正起过滤作用的面积比展开面积小。  \n\n使用前将纸芯逐个放在固定板的相应位置上，然后在纸芯封口端的金属盖板上放好弹簧和压紧板，旋紧拉杆螺母。由于纸芯上端是封闭的，下端通过密封垫紧压在定位套上，滤液只能穿过纸芯到下封头出料，滤渣被纸芯截留。过滤时一般用齿轮泵送料。随着过滤的进行，过滤压力逐渐提高，待达到纸芯的许可工作压力（约为0.2MPa）时，停泵换上新的纸芯，再重新过滤。  \n\n$\\textcircled{2}$ 安装方式 纸芯筒式过滤器既可单独使用，也可并联、串联或与其他过滤设备联合使用。也有用金属丝网过滤器或油分离机，作为它的前置粗滤装置。  \n\n有一种安装方式，使用17个纸芯的筒式过滤器，3台为一组。前两台并联，后面集中串联一台。为防止纸芯承受的压力过大，前两台与后面一台中间增设一台齿轮泵。这种方式适合产量较大的产品过滤。前有两台，保证了较大的过滤速度，后面串联一台，使滤液经过两次过滤，比较可靠地保证了过滤的质量。  \n\n$\\textcircled{3}$ 操作注意事项  \n\na.纸芯的质量至关重要。在使用前必须逐个仔细检查，查有无破损，查带折的纸与两端的金属盖板是否粘接牢靠。  \n\nb.使用中要注意调节过滤压力。用齿轮泵送料时一般采用旁路阀调节。应尽量使过滤  \n器在较低压力下工作，以延长纸芯的使用寿命。如过滤的物料黏度太高，可适当提高过滤  \n温度。c.发现细度达不到标准，过滤压力过高或流量明显增大时，应检查、更换纸芯。d.过滤要一次完成，中间不宜中断，过滤结束后要立即将过滤器清洗干净。  \n\n(2）滤芯筒式过滤器当纸芯的强度或耐溶剂性能或过滤质量不能满足工艺要求时，就要寻找更好的滤芯来替换，显然其价格也比纸芯高。目前常见的滤芯有短纤维烧结滤芯、复合纤维滤芯和缠绕滤芯。  \n\n短纤维烧结滤芯外表面大多有十几道环形沟槽，可加大过滤面积。外观像用锯末压制的刚性圆管。国产短纤维烧结滤芯用特定短纤维，加入黏合剂、固化剂和稳定剂，烧结成形。  \n\n这种滤芯机械强度高，受压后滤层内部空隙结构不变。由于滤芯厚度较大，空隙率较高，能实现深层过滤，过滤精度高$10\\mu\\mathrm{m}$ 或更小)。耐腐蚀性能好。  \n\n这种滤芯外径为 $65\\mathrm{mm}$ ，内径约 $27\\mathrm{mm}$ ，基本长度为$250\\mathrm{mm}$ ，加长型有 $500\\mathrm{mm}$ 、 $750\\mathrm{mm}$ 和 $\\mathrm{1000mm~3}$ 种。工作温度为 $0\\sim120^{\\circ}C$ 9  \n\n复合纤维滤芯和缠绕滤芯大多耐温不高（一般不大于$80^{\\circ}C$ )，目前使用较少。  \n\n在选定滤芯后，有两种方案可供选择，  \n\n一种方案是对纸芯筒式过滤器进行适当改动（主要是封住滤芯上口)，用新选定滤芯取代纸芯进行过滤。另一方案是根据工艺要求，选用合适的滤芯过滤器。图4-1-46为一种滤芯筒式过滤器，内装10支滤芯。  \n\n为达到理想的过滤效果，除了要选用高质量的滤芯外，最重要的是要防止侧漏，一定要保证滤芯两端密封良好。  \n\n(3）滤芯管式过滤器将一根长滤芯（或由 $2\\sim3$ 根短的串接）装在管状筒体内，就是滤芯管式过滤器（见图  \n\n![](images/d0c61cc24e1beb93bb6fbcd775555b465211bf08390fbb26cb6dec4a6e7e22ff.jpg)  \n图4-1-46滤芯筒式过滤器1—螺栓；2—上盖；3—滤芯；4—进料口；5—螺母；6—垫圈；7一滤芯中心管；8一可卸花板；9—出料口  \n\n4-1-47）。上盖与筒体用圆螺母锁紧，上盖同时压住滤芯。这种过滤器简单、紧凑，占用空间小。松开圆螺母即可更换滤芯，十分方便。  \n\n使用非纸质滤芯，优点是滤芯强度大，可承受较高压力，不易破损；滤芯刚度好，两端能可靠地压紧；由于是深层过滤，每支滤芯生产能力较大，过滤质量好，可达到满意的细度（可小于 $10\\mu\\mathrm{m}\\dot{}$ )。其主要缺点是滤芯价格高，难以再生而重复使用。为延长滤芯使用寿命，节省开支，常在滤芯过滤器前设置粗过滤器。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1121,
+        "chunk": "# 4.袋式过滤器  \n\n即滤袋式过滤器，国外也称GAF过滤器。  \n\n(1）结构和原理袋式过滤器主要由滤袋、支承滤袋的不锈钢丝加强网篮及过滤容器组成（见图4-1-48)。滤袋借助卡环（不锈钢或塑料制）装在网篮上圈内口。带铰链的平盖为快开结构，开启及更换滤袋都很方便。平盖与进口管之间有1个○形圈，网篮上圈有2个O形圈（上下各一)，压紧平盖时能同时压紧这些〇形圈及滤袋，达到密封的目的。O形圈一般采用耐溶剂的氟橡胶材料。也有用不锈钢板钻孔制成圆筒代替不锈钢丝网篮的，耐压力较高，只是钻孔较费工。  \n\n![](images/651f8bca9e933b7b9986624bcf27fb3beda0885ee034be06bc29c6093c7f1481.jpg)  \n图4-1-47滤芯管式过滤器结构 1,11—螺塞；2—上盖；3—圆螺母；4,5—密封圈； 6—滤芯；7—简体；8—导向杆；9—支承盘；10—简底  \n\n![](images/f650da833a2041dbe7f58ad40946861875e1821b921e1960c39e386666ff061d.jpg)  \n图4-1-48 袋式过滤器  \n\n待过滤液体由泵送人滤袋，杂质被滤袋截留，透过滤袋的滤液从下部流出。  \n\n(2）滤袋对滤袋的要求，首先是过滤性能好，且阻力较小；滤袋要有足够的强度；无论接缝是缝线或热熔结合，都要严密可靠；滤袋袋口裹着卡环，尺寸形状要准确，并有一定弹力。其次，滤袋在过滤时不溶胀，不污染滤液，不允许脱落一丝纤维。最后，价格较低。  \n\n目前涂料行业常用的滤袋主要分两类。  \n\n① 丝网滤袋质地薄，只起表面过滤作用。它主要有尼龙丝网和不锈钢丝网两种。尼龙丝网耐酸碱、耐溶剂，耐温达150℃，过滤精度范围为80～800μm。它主要用作粗过滤；如当两个袋式过滤器申联使用时，可用作初级过滤；它也可用于挂滤袋过滤。不锈钢丝网结实耐用，可清洗再用，因价高且清洗费工费溶剂，很少应用。  \n\n② 无纺布滤袋质地厚，像毛毡。它由高度蓬松性纤维组成，能起表面过滤和深层过滤双重作用，过滤速率较快，能滤除较多杂质。无纺布滤袋的材料常用聚酯或聚丙烯。聚酯耐碱、耐溶剂，耐温达160℃，目前应用较广；聚丙烯耐酸碱，不耐芳香烃类溶剂，耐温约为 $90^{\\circ}C$ 0  \n\n国产滤袋常用规格：过滤面积为0.25m²和0.5m²，滤袋直径均为180mm，长度分别为450mm和850mm。无纺布滤袋的过滤精度范围约为1～200um，涂料过滤常用5μm、$10\\mu\\mathrm{m}$ $15\\mu\\mathrm m$ $25\\mu\\mathrm{m}$ ， $40\\mu\\mathrm m$ 和 $50\\mu\\mathrm{m}$ 等几种。  \n\n(3）操作注意事项  \n\n① 根据需要，双联过滤器既可交替使用，也可并联或改为串联使用。并联为加大滤液流量。串联用于滤渣多、要求高的场合，选用滤袋宜前疏后密，如前用丝网滤袋，后用无纺布滤袋，以期达到既满足过滤细度要求，又延长滤袋更换周期的目的。  \n\n②过滤前应检查滤袋和设备。滤袋规格要符合要求，质量完好，过滤器内部要干净，密封用的几个O形圈不得有缺陷。装滤袋时要注意毛毡状材料的绒面应朝里。装好滤袋，压紧器盖，即可过滤。  \n\n$\\textcircled{3}$ ③要关注过滤压力的变化。刚开泵时，压力约为0.05MPa，随后压力逐渐升高，一般当压力达到 $\\boldsymbol{\\hat{\\mathbf{0}}},4\\mathbf{M}\\mathbf{P}\\mathbf{a}$ 时，即应停机。开盖检查滤袋积渣情况，更换滤袋，继续过滤（脏滤袋清洗后也可再用)。过滤器的压力可通过旁路阀调节。  \n\n$\\textcircled{4}$ 为下次过滤做好准备。过滤器使用后要及时清洗，保持整洁",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1122,
+        "chunk": "# （4）袋式过滤器的优缺点  \n\n① 优点适用范围广，既可过滤树脂、漆料和清漆，也可过滤色漆。可过滤溶剂，也可过滤黏稠物料（黏度可达50Pa·s)。选用不同规格滤袋，过滤精度范围也很大；结构简单紧凑、体积小，可装在小车上流动使用；密闭操作，不污染环境；操作方便；高效，滤袋过滤处理量大，容污量大。  \n\n②缺点滤袋价格较高。虽然清洗后尚可使用，但清洗较麻烦，清洗后易变硬，过滤能力下降，因而过滤费用较大；其次，滤袋的过滤精度随过滤压力的变化有波动，因滤袋是“软”的，当压力较大时，杂质有可能从滤袋的孔中挤过去。所以一般都选用比产品细度稍高档次的滤袋。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1123,
+        "chunk": "# 5.水平板式过滤机  \n\n水平板式过滤机是使用助滤剂的过滤设备，过滤元件为圆盘形，水平安置。按其过滤面积划分型号，常用规格为10m²（还有5m和3m的，使用较少）。  \n\n（1）结构和原理 图4-1-49为水平板式过滤机的结构。它主要由筒体和多层滤板组成。滤板结构如图4-1-50所示。支撑板（过滤盘）上压着多孔板，多孔板上铺滤纸。多层滤板用拉杆螺栓压紧后，再用中心螺栓紧固于筒体中。装好顶盖后，即可进行过滤  \n\n滤浆用泵送人过滤机的筒体内，经支撑板外圆周面上的许多小孔，进入两层滤板之间，滤液穿过滤纸上的助滤层、滤纸和多孔板，沿支撑板上众多球状凸起间的通道，再通过中心罩上的孔洞，流人滤板中心孔道，从筒体底部出料口流出。  \n\n（2）设备配置、流程及操作步骤  \n\n$\\textcircled{1}$ 设备配置 过滤机需配备混合罐和泵  \n（常用齿轮泵）各一台。制造厂将主机、配  \n套设备连同管路、阀门组装在底板上，便于  \n运输及用户使用。除主机是不锈钢材质外，其余设备及管路、阀门系碳钢和铸铁材质。  \n\n![](images/2d2d13fd91a547b50f81c5ce276ab231cc1a636a634190f933baccebcbff84ad.jpg)  \n图4-1-49水平板式过滤机的结构1—简体；2—滤板；3—顶盖；4—旋转吊臂  \n\n![](images/e304b3cba414bde0028603955d631ac5cf953ae3b45d416747eb21d6939d205c.jpg)  \n图4-1-50 滤板结构  \n\n如同时使用多台过滤机，可多备一套滤板作备用。因滤板用久要浸泡在碱水中煮洗，费时。滤纸推荐用 $270g$ 油过滤纸（厚 $0.7\\mathrm{rnm}$ )。硅藻土推荐使用吉林长白等地生产的，牌号为 ZC-101。  \n\n![](images/43dd265e543eb4b0d36312d8df0a934ba3bba3bae18e6616c222906e3a7131bd.jpg)  \n图4-1-51水平板式过滤机工艺流程1—混合罐；2—进料；3—滤浆泵；4—情性压缩气；5—过滤器；6—蒸汽进口；7—冷凝水出口；8—排渣；9—出料；10—取样口  \n\n$\\textcircled{2}$ 流程水平板式过滤机工艺流程见图4-1-51。过滤机从稀释罐来料，一般都是趁热过滤，所以过滤机的夹套大多不需通蒸汽。  \n\n$\\textcircled{3}$ 操作步骤水平板式过滤机利用硅藻土做助滤剂，改善了滤饼特性，达成深层过滤，提高了滤液的质量和过滤速率。所以它的操作也与不用助滤剂的过滤操作不同，其操作步骤如下。  \n\na.助滤剂与滤浆混合及预覆将滤浆用泵送人混合罐，加助滤剂（硅藻土）总量的一半（总量约为滤浆量的1/1000）后搅拌，使滤浆与助滤剂均匀混合。混合后，用泵将混有助滤剂的滤浆送人过滤机并返回混合罐，使之在过滤机与混合罐之间进行循环操作(俗称小循环)，其目的是使助滤剂逐渐预覆在滤纸上。在小循环进行一  \n\n段时间后，不断取样检验细度和透明度，合格后即可开始过滤，滤液不再返回混合罐。“小循环”约需 $15\\mathrm{\\sim}20\\mathrm{min}$ ，泵出口压力约为 $\\boldsymbol{0}.1\\mathrm{{MPa}}$  \n\nb.过滤将总量一半的助滤剂加人稀释罐，使其与滤浆均匀混合后用泵送入过滤机进行过滤。过滤温度应保持在适宜的范围内，如过滤醇酸树脂一般为 $90\\sim100^{\\circ}C$ 0  \n\nc.吹扫和洗涤过滤完毕后，用惰性气体将过滤机和管路中的剩液压回稀释罐。然后在稀释罐中放入适量溶剂，用泵循环清洗全系统，以回收滤饼中夹带的物料。最后再用情性气体将系统中清洗溶剂吹进稀释罐。  \n\nd.卸渣移开顶盖，卸中心螺母，吊出多层滤板，再拆拉杆螺栓，逐板撤掉滤纸和滤饼。然后铺新滤纸，重新组装滤板，拧紧拉杆螺栓，吊回过滤机筒体内，旋紧中心螺母，装好顶盖，以备下次过滤使用。  \n\n(3）操作注意事项$\\textcircled{1}$ 组装滤板要严密、不漏料。  \n\n$\\textcircled{2}$ 过滤压力一般不宜超过 $\\mathsf{0.3M P a}$ 中  \n\n$\\textcircled{3}$ 气体吹扫要注意安全气体吹扫的时间不可过长，滤浆的温度不可过高，过滤机和所有的管路都要可靠接地，以防产生静电。因国内以前用压缩空气吹扫时，曾发生过筒体内爆燃（只是内部滤板局部变形，部分滤饼烧焦，未酿成大伤害)，故现推荐用带压情性气体吹扫。如无条件，也可不用吹扫，采取吊起滤板控干，减少物料损失。  \n\n（4）水平板式过滤机的优缺点  \n\n$\\textcircled{1}$ 优点过滤质量好，滤液清澈透明，细度可小于 $15\\mu\\mathrm{m}$ ；生产能力大。过滤面积为$\\mathrm{10m^{2}}$ 的过滤机每小时可过滤醇酸树脂（ $50\\%$ 固体分） $10t$ 左右；密闭操作，对环境污染小。  \n\n②缺点操作比较麻烦，换一次滤纸要拆装很多螺栓，需要几个人同时操作，劳动强度较大；辅助设备多，要有混合罐（带搅拌)、电动葫芦。吹扫还要有惰性压缩气体。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1124,
+        "chunk": "# 6.垂直网板式过滤机  \n\n垂直网板式过滤机，国外称阿玛（Ama）过滤机，是近年来继水平板式过滤机后在涂料行业普遍推广的过滤设备。  \n\n(1）结构和原理图4-1-52为垂直网板式过滤机。在过滤机筒体内，有数片网板，插装在集液管上。网板由数层不同规格的不锈钢丝网和夹紧它们的圆形（或矩形）管框架铆接而成，丝网的特点是“外密内疏”，内层起支撑作用。网板下端部焊一短管，短管中间的沟槽上嵌装一个橡胶制O形圈，网板下端部插在集液管孔中就靠它密封。  \n\n这种过滤机的一大特色是不用滤布和滤纸。过滤时依靠助滤剂（硅藻土等）在网板上形成的助滤层进行过滤。滤浆用泵送人过滤机筒体内，滤渣被助滤层截留，滤液穿过助滤层和丝网，经集液管流出。可安装气动振动落渣装置和气动排渣阀门，适用于不黏的滤渣。树脂过滤产生的滤渣大多很黏，振动落渣的效果不一定好。  \n\n（2）设备配置、流程及操作要点  \n\n$\\textcircled{1}$ 设备配置 与水平板式过滤机类似，过滤机需配备混合罐和泵（常用齿轮泵、内齿泵）各一台。成套设备包括主机、配套设备、管道、阀门及电气系统，连操作平台及梯子全部组装成一体，便于用户使用。如车间空间较大，也可订购设备，自制较高大的操作台进行安装。  \n\n![](images/1c588f6118bb3379868cfe9a2a55488e710382e53450943697b05d25370003ce.jpg)  \n图4-1-52 垂直网板式过滤机1—网板；2一顶盖及简体；3—振动落渣装置；4一排渣阀门  \n\n因网板使用时间长久后一般要用碱水煮洗，然后冲净晾干，很费工，所以最好有备用件。  \n\n$\\textcircled{2}$ 流程图4-1-53为垂直网板式过滤机流程。从图中可看出，过滤机的流量和压力可通过输液泵的旁路阀来调节。  \n\n![](images/ba2a066060a975ab3dd886f120acff23582d79daee5628facd3905ed15ac784d.jpg)  \n图4-1-53 垂直网板式过滤机流程A一混合罐；B一主过滤器；C一输液泵  \n\n$\\textcircled{3}$ 操作要点垂直网板式过滤机的操作，与水平板式过滤机相似。如有条件，最好能用滤液作小循环，那样得到的助滤层过滤效果更好。预覆助滤剂的加入量约为每平方米过滤面积 $0.\\delta{\\sim}1.2\\mathrm{kg}$ ，助滤层厚度约为 $1.5\\sim3\\mathrm{mm}$ 0  \n\n为了防止过滤压力很快升高，延长过滤周期，也可进行添加助滤剂过滤。一般压力升到$\\mathrm{0.3MPa}$ ，应停止过滤。利用输液泵反转，将过滤机内的残液送回稀释罐，或将残液放入桶中待再过滤。如果有条件也可用压缩气体通入过滤机内压料或吹干滤饼，以减少滤饼夹带的物料。  \n\n清除滤饼比水平板式过滤机方便，开盖即可抽出网板，用木（或牛角）铲刀铲除滤饼。网板可用溶剂清洗或用碱水煮洗。要注意不要损坏O形圈。为减少开盖清渣的次数，有的厂家用溶剂将滤饼冲洗下来，排渣后即可继续过滤。  \n\n（3）操作注意事项$\\textcircled{1}$ 严防助滤层和滤饼脱落。  \n\n$\\textcircled{2}$ 进料前宜预先粗过滤，  \n\n$\\textcircled{3}$ 用好、用活助滤剂助滤剂的品种、规格、用量关系到过滤的质量、速率及费用，在操作中要仔细总结经验，对不同产品作适当调整。一般，滤液细度要求高，要用较细、较多的助滤剂；滤液细度要求低或黏度高，要用较粗、较少的助滤剂。  \n\n$\\textcircled{4}$ 要爱护网板 网板要轻拿轻放。不用钢铲刀刮网板，以免破损。  \n\n（4）型号和规格举例垂直网板式过滤机国内生产厂家较多，结构上大体相同。表4-1-11摘录了NYB型过滤机的部分规格。目前常用 $4\\mathrm m^{2}$ 、 $\\mathrm{7m^{2}}$ 、 $\\bf{10m^{2}}$ 等几种，该系列目前最大规格已达 $90\\mathrm{m}^{2}$  \n\n表4-1-11 垂直网板式过滤机的部分规格  \n\n\n<html><body><table><tr><td rowspan=\"2\">型号</td><td rowspan=\"2\">过滤面积/m²</td><td rowspan=\"2\">滤网片数</td><td colspan=\"2\">处理能力/(t/h)</td><td rowspan=\"2\">过滤罐容积/L</td><td rowspan=\"2\">主机质量/kg</td></tr><tr><td>油脂</td><td>树脂</td></tr><tr><td>NYB -2</td><td>2</td><td>5</td><td>0.4~0.6</td><td>1~2</td><td>120</td><td>300</td></tr><tr><td>NYB -4</td><td>4</td><td></td><td>0.8~1.2</td><td>2~3</td><td>250</td><td>400</td></tr><tr><td>NYB-7</td><td>7</td><td>9</td><td>1.4~2</td><td>4~6</td><td>420</td><td>600</td></tr><tr><td>NYB -10</td><td>10</td><td>10</td><td>2~3</td><td>7~9</td><td>800</td><td>900</td></tr><tr><td>NYB -15</td><td>15</td><td>12</td><td>3~5</td><td>12~14</td><td>1300</td><td>1300</td></tr><tr><td>NYB-20</td><td>20</td><td>12</td><td>4~6</td><td>17~19</td><td>1680</td><td>1700</td></tr><tr><td>NYB -25</td><td>25</td><td>13</td><td>5~7</td><td>22～24</td><td>1900</td><td>2100</td></tr><tr><td>NYB-30</td><td>30</td><td>15</td><td>6~8</td><td>27~29</td><td>2300</td><td>2500</td></tr></table></body></html>\n\n注：1.额定工作压力为 $0.1{\\sim}0.4\\mathrm{MPa}$ ，最大工作压力为 $0.5\\mathrm{MPa}$ 2.工作温度 $\\$150$ 睿  \n\n3.处理能力，油脂类指含 $2\\sqrt{y}=5\\sqrt{y}$ 白土的油类平均过滤量，树脂类指对醇酸树脂过滤细度在 $5\\sim10\\mu\\mathrm{m}$ 时的平均过滤量，因过滤能力与滤浆中杂质含量等多种因素有关，处理能力仅供参考。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1125,
+        "chunk": "# （5）垂直网板式过滤机的优缺点  \n\n$\\textcircled{1}$ 优点不用滤布和滤纸，只用少量助滤剂，辅助材料消耗少，过滤成本低；过滤质量好，滤液清澈透明，细度可小于 $\\mathtt{l i s}\\mu\\mathrm{m}$ ；适应范围广，能过滤各种树脂、漆料、清漆及油料等，而且过滤速率快；操作简便，拆装网板不需要电动葫芦等起重设备，大多一个人即可操作；设备密闭操作，对环境污染小。  \n\n$\\textcircled{2}$ 缺点网板外层席形网的金属丝很细，在操作、清渣过程中容易破损，修复比较困难，更换则成本高；因网板系垂直安装，过滤进行中不能停顿，要一次过滤完毕，否则助滤层和滤饼可能局部落下而造成“短路”，就要重新进行助滤层的预覆；过滤结束时总要剩下部分滤浆，要放人桶中或用泵送回稀释罐，留待下一次过滤。  \n\n![](images/ed8f6d471bac50eb0703285501de441b425e8db1b85a74d4483f75c237a4c790.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1126,
+        "chunk": "# 一、概述  \n\n液态的色漆在涂料中品种最多，产量最大，它通常由漆料、溶剂、颜料（填料）及少量助剂（如催干剂、流平剂、防结皮剂等）组成。从本质上讲，它是固体的颜料和填料在成膜物质溶液（或分散液）中的均匀、稳定的分散体。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1127,
+        "chunk": "# 1.颜料分散过程  \n\n色漆生产的过程就是把颜料固体粒子混入液体漆料中，使之形成一个均匀微细的悬浮分散体。颜料和填料的原始粒子都很细小，其粒径约在0.01～2um之间，比色漆中允许的最大颗粒小许多倍。但是颜料原始粒子在加工和贮运过程中，经常相互黏结成聚集体（二次粒子)，它们可能由几万个甚至几十万个原始粒子组成，其粒径可能增大到100um以上。因此在色漆制造时要将聚集体解除聚集，并稳定而均匀地分散于漆料中。颜料分散过程可分为以下3个阶段。  \n\n① 湿润用漆料置换颜料粒子表面上吸附的气体（如空气）或别的污染物（如水分)。  \n\n②研磨用外力（如撞击力、剪切力）打开和分离颜料的大的聚集体，使之成为符合色漆工艺要求的细小的粒子。虽然称为研磨，但并不是磨碎颜料的原始粒子，而是将聚集体破碎分散于漆料中。  \n\n$\\textcircled{3}$ 稳定使已湿润和分离的颜料细粒分散到大量的液体漆料中去，使每个颜料粒子被漆料长久地分离，形成较长时间的相对稳定的平衡体系，避免这些粒子重新聚集（絮凝）。  \n\n以上这3个阶段是相互联系又难以截然分开的。而且也很难分清在某一设备内只进行某一阶段的作业。  \n\n色漆中颜料分散得越好，色漆的质量性能，如遮盖力、着色力、光泽度等能够明显提高，既能改善色漆和涂层的质量，又可降低昂贵的颜料用量，提高技术经济效果。所以色漆生产过程中如何提高分散效果，研制和采用高效分散设备，以及选用优质颜料和最佳配方成为色漆生产中的重要课题。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1128,
+        "chunk": "# 2.色漆生产过程  \n\n①预分散或称拌合，将颜料在一定设备中先与部分漆料混合，以制得属于颜料色浆半成品的拌合色浆，简称拌合浆。所用设备主要是带有搅拌器的设备。  \n\n②研磨分散简称研磨，是将预分散后的拌合浆，通过各种研磨分散设备进行细分散，得到颜料色浆，达到分散的目的。  \n\n③调漆将研磨得到的颜料色浆，加入余下的漆料及其他助剂、溶剂组分，必要时进行调色，达到色漆质量要求，一般在带有揽拌器的调漆罐中进行。  \n\n$\\textcircled{4}$ 过滤包装通过不同过滤设备除去机械杂质及粗粒，然后包装为成品。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1129,
+        "chunk": "# 3.色漆生产工艺  \n\n色漆的生产工艺一般按所用研磨分散设备来划分，最通行的为砂磨分散工艺、辊磨分散工艺和球磨分散工艺。图4-1-54所示为小批量活动罐式色漆生产工艺流程。  \n\n![](images/58bdc2cef61c58c0b4eac307cdd8f3252e308b526c54ba8ee7e9625cda708817.jpg)  \n图4-1-54 活动罐式色漆生产工艺流程  \n\n从树脂车间用管道送来的漆料从高位罐放入活动漆浆罐，加人颜料、填料（体质颜料）及溶剂，用高速分散机进行拌合和预分散，然后用砂磨机进行研磨分散作业，经多道循环作业至细度合格后进人调漆工序。此谓砂磨分散工艺。辊磨分散工艺与此相仿。原料经高速分散机或其他拌合设备（如搅浆机）拌合和预分散后，将活动漆浆罐推到三辊磨前用电动葫芦吊起或用自动上浆机向三辊磨供料，进行研磨分散作业。经多道循环作业至细度合格后进人调漆工序。至于球磨分散工艺，省掉预分散工序，将原料直接装人球磨机后即进行研磨分散作业，直至细度合格，进入调漆工序。调漆时色浆称重计量，在搅拌下加入经流量计计量的漆料、溶剂及各种助剂，调整颜色和黏度，制成色漆。产品经过滤、灌装（人工或机械）后人库。  \n\n生产规模较大时，则用固定罐生产，液体物料多采用泵送。预分散常在固定罐内进行，固定罐装锯齿圆盘式叶轮进行揽拌或直接用高速分散机进行搅拌。大多采用砂磨分散。同样，调漆在固定调漆罐进行。其容量比活动漆浆罐大。有的调漆罐采用比较先进的重力传感器进行计量。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1130,
+        "chunk": "# 二、预分散设备  \n\n预分散的目的是： $\\textcircled{1}$ 将各种颜料和体质颜料混合均匀； $\\textcircled{2}$ 用漆料取代部分颜料表面所吸附的空气等，使颜料得到部分湿润； $\\textcircled{3}$ 初步打碎大的颜料聚集体。因而这道工序以混合为主，并起部分分散作用。它是研磨分散的配套工序，但色浆预分散的好坏，也直接影响研磨分散的质量和效率。近年开发的各种新型预分散设备，都是以提高分散质量和效率为目的，起到粗分散的作用。过去色漆的研磨分散设备以辊磨机为主，与其配套的是各种类型的搅浆机。近年来，研磨分散设备以砂磨机为主，与其配套的也改用高速分散机，它是目前使用最广的预分散设备。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1131,
+        "chunk": "# 1.高速分散机  \n\n（1）高速分散机的工作原理  \n\n$\\textcircled{1}$ 概述高速分散机的主要工作部件是叶轮，图4-1-55所示为最常用的锯齿圆盘式叶轮。叶轮由高速旋转的分散轴带动。叶轮在搅拌槽中的工作情况如图4-1-56所示。  \n\n![](images/63778169ae595ce82f4741dbcb5016e03f1a5f6d3903b3b042a53ed9b3d3c66c.jpg)  \n图4-1-55 高速分散机的叶轮  \n\n![](images/aa8eab35d7c7911a0495939e9e6fa8b3270fd084ffccd8bb65e003df50456c50.jpg)  \n图4-1-56 高速分散机中叶轮的正确位置和搅拌槽的适宜尺寸  \n\n叶轮的高速旋转使搅拌槽内的漆浆呈现滚动的环流，并产生一个很大的旋涡。位于漆浆顶部表面的颜料粒子，很快呈螺旋状下降到旋涡的底部。在叶轮边缘 $2.5\\sim5\\mathrm{cm}$ 一带，形成一个湍流区。在这个区域内，颜料粒子受到较强的剪切和冲击作用，使其很快分散到漆浆中。在此区域外，形成上、下两个流束，使漆浆得到充分的循环和翻动。若叶轮下方呈现层流状态，不同速度液层之间的相互作用被称为黏度剪切力的作用，能起到很好的分散效果。  \n\n综上所述，高速分散机兼起混合和分散作用。在高速分散机操作的初始阶段，颜料还堆在漆料上面，此时宜采用低速进行混合，防止粉料飞扬，然后再提高转速，增加分散能力。实践证明，叶轮端部的圆周速度必须达到 $20\\mathrm{m}/\\mathrm{s}$ 以上时，才能获得比较满意的分散效果，只是在分散膨胀型漆料时，可降低至 $\\bf{15m/s}$ 。但是叶轮的圆周速度也不可过高，否则会造成漆浆飞溅，使圆盘叶轮过多暴露而导致混入空气，可能破坏叶轮下方已形成的层流状态，使分散效率下降且无谓地增加了功率消耗。一般叶轮的最高圆周速度约为 $25\\mathrm{\\sim}30\\mathrm{m/s}$  \n\n$\\textcircled{2}$ 在叶轮下部产生层流的条件为了使叶轮下部区域达到层流状态，一方面不能过度提高叶轮的圆周速度，另一方面要适当提高漆浆的黏度，并降低叶轮的位置。可利用下式求出层流条件：  \n\n$$\nR e=\\frac{o v h}{\\mu}{\\leqslant}2000\n$$  \n\n式中 $R e$ 一 雷诺数（不大于2000处于层流状态）；$P$ ——漆浆密度， $\\bf{k g/m^{3}}$ $\\pi$ —叶轮圆周速度， $m/{\\mathrm{s}}$ $\\bar{h}$ ——特征尺寸，此处取叶轮距搅拌槽底的距离，m;$\\mu$ —漆浆黏度， $\\mathbf{Pa}\\cdot\\mathbf{s}$ 0  \n\n在已知叶轮圆周速度和漆浆黏度的条件下，可求出叶轮的合理插人深度，或在已知叶轮圆周速度及叶轮插人深度的条件下，求出漆浆的合理黏度以确定应如何配制。  \n\n$\\textcircled{3}$ 叶轮的大小、位置及搅拌槽的适宜尺寸图4-1-56中推荐的尺寸关系说明了搅拌槽直径与叶轮直径的关系及叶轮工作的合理位置。搅浆时可取下限，调漆时可取上限。在实际生产中，可根据漆浆黏度与分散轴转速，适当调整投料高度及叶轮的插人深度。在叶轮高速旋转时，漆浆会形成很深的旋涡，要防止物料从搅拌槽边沿外溢。  \n\n叶轮直径与搅拌槽直径有一个合理的比例，其目的是使物料循环得好。即使具有一样高的圆周速度，一般来说，小叶轮的效果要比大叶轮的效果差。但大叶轮消耗的功率要比小叶轮大很多，因搅拌功率与叶轮直径的五次方及转速的立方成正比。为使循环良好，搅拌槽一般不设挡板，也不应有死角，故以碟形底为好。  \n\n（2）高速分散机的设备结构  \n\n$\\textcircled{1}$ 常用机型的结构 $22\\ensuremath{\\mathrm{kW}}$ 高速分散机是目前广泛使用的机型，图4-1-57为GFJ-22A高速分散机结构，高速分散机主要由机身、传动装置、分散轴和叶轮、液压系统及电气控制箱组成。  \n\n![](images/3e3317ffe7a16ea0d5f94ec4d5e687912c90acdefe0ffd2fbb442f208365851c.jpg)  \n图4-1-57GFJ-22A高速分散机结构  \n\na.机身机身为高速分散机的躯干，它支承传动装置、分散轴和叶轮，它装有液压升降装置和回转装置，使高速分散机的叶轮既能升降，又能围绕机身中心作360°回转。  \n\n·液压升降装置主要由固定的柱塞和可移动的缸体组成。齿轮油泵供应压力油，经单向阀、行程节流阀注人缸体内，推动缸体上升。下降时是靠传动装置和分散轴部分的自重排油而自行下降，下降速率由行程节流阀控制。缸内空气由排气阀排出。  \n\n![](images/1389f6e382765ee8a27553b0ece769d4c35ebd2ad224be3e3780db3d10357cc2.jpg)  \n图4-1-58 液压系统原理 1—油缸柱塞；2—软管；3—截止阀； 4—单向阀（I-25）；5—溢流阀 (P-B25B)；6—齿轮泵（CB-B16）； 7—泵电机（Y90S-4)；8—油箱； 9-电磁滑阀（22D-10B)  \n\n·回转装置缸体与传动箱的连接用滚珠隔开，并可由压环、摩擦片、螺栓和转动手柄锁紧。当转动手柄松开时，通过摇臂转动伞齿轮，带动齿轮副使传动箱回转。  \n\nb.传动装置在传动箱内，主电机上的主动轮，通过两级V带传动，经中间轮，带动从动轮。  \n\nc.分散轴和叶轮分散轴为挠性轴，由从动V带轮带动，由轴承座支承，分散轴下端装叶轮。叶轮大多采用锯齿圆盘式叶轮，常用不锈钢板制。  \n\nd.液压系统 液压系统原理见图4-1-58。  \n\ne.电气控制箱电气控制程序为：主电机运转时，泵电机不能运转；泵电机运转时，主电机不能运转。电器配置可按用户要求配套普通型或防爆型。  \n\n有防爆要求时，装在现场的电机和电器，按防爆等级采用防爆的型号，其余不防爆的器件均需隔离安装。  \n\n$\\textcircled{2}$ 结构改进示例  \n\na.中、小机型一种比较新颖的结构见图4-1-59。与图4-1-57机型比较，有了明显的改进。如取消了中间轮，简化了结构；密封圈改在上面，便于维修，加上升降结构及材质改变，不易泄漏；手摇齿轮处改为导向杆，结构更加稳定。  \n\n![](images/31c2ba91951b92fc8645255ecd0d3de486d7d0776c05fb57ae6eaa67d03c81fd.jpg)  \n图4-1-59中、小机型高速分散机结构改进示意  \n\n1—传动箱；2—主动轮；3—拉紧装置；4—主电机；5--导向套；6—滑动套；7—导向杆；8—柱塞； 9—机身；10-筋板；11—进油口；12—从动轮；13,14—轴承；15—压环；16—大法兰； 17—滚珠护环；18—V带；19—转动手柄；20—托座；21—V形密封圈；22—排气组合； 23—分散轴；24—叶轮；25—叶轮座；26—叶轮压盖；27—压板  \n\nb.大型机（ $40k W$ 及以上）在中、小机型的基础上，将升降的重任交给油缸去完成，如图4-1-60所示。油缸是按国家标准由专业厂制造的，材料上乘，加工精良，质量可靠，  \n\n![](images/049d0bac0697d6d8f1db47908f9cdc9aa9a04e52666a447fcf8e4bacf2799610.jpg)  \n图4-1-60 大型高速分散机结构改进示意  \n\n1—叶轮；2—分散轴；3,5—轴承；4—轴承座；6—-从动轮；7—传动箱；8—V带；9—主动轮；10—拉紧装置；   \n11—主电机；12—导向杆；13—滑动套；14—滑柱；15—油缸；16—大、小齿轮；17—推力轴承；18—机身  \n\n因而基本上不会漏油，这样就从根本上解决了泄漏问题。  \n\nc.大型分散机自动转向安装在操作台或楼板上的大型分散机，经常采用一机配多罐的作业形式，而用人工手动转向，既笨重，又不安全。现在一种自动转向装置已经面世。在换罐时，转动箱上升脱离罐口后，通过电机带动齿轮旋转，使传动箱回转到限定位置，下降后进人另一罐操作。双插杆配置，能达到平稳运转的目的。  \n\nd.一种双层叶轮高速分散机除使用各种不同形状的单层叶轮外，近年张家港市通惠化工机械有限公司推出一种专利产品——双层叶轮（双层齿形强力分散轮，图4-1-61)。据介绍，经用户使用，该叶轮分散用进口钛白粉配制的漆浆，只需 $40\\sim60\\mathrm{min}$ ，细度能达到$17.5\\mu\\mathrm{m}$ 。大大提高了工作效率，降低了能耗。  \n\n![](images/516f2f9492328d816eb2adcb9c15ffa9f14c8d26dff366b133baa9422b521d82.jpg)  \n图4-1-61 双层叶轮  \n\n$\\textcircled{3}$ 高速分散机有关问题讨论  \n\na.安装形式同一机型的高速分散机，有的有两种安装形式，安在地面上的落地式和安在楼板或操作平台上的平台式，如图4-1-62所示。  \n\n![](images/817230a3283e1bd2839bcae7c80b37cb0a84e0865afddf0060b09e6c73995d26.jpg)  \n图4-1-62 高速分散机的两种安装形式  \n\n落地式为基本形式，有的机型只有落地式一种。与落地式高速分散机配套的搅拌槽系移动式容器，统称活动漆浆罐，也有叫漆盆或拉缸的，一般备有很多个。一盆已制备好的漆浆推送到研磨分散工序，又一个空盆进行投料操作，如此循环往复，操作机动灵活，便于清洗、换色，特别适用于多品种、小批量的生产。  \n\n平台式高速分散机要与安在楼板或操作平台上的固定罐配套使用，适用于大批量生产。为更好地发挥设备效能，一台高速分散机可配2～4个固定罐，也可以用2台高速分散机配6个固定罐，依次进行操作。  \n\nb.变速形式高速分散机在工作时，一般在刚加入粉料时需要低速运行，以防粉尘飞扬，待基本混合均匀后，再进行高速分散。所以高速分散机的分散轴起码应具有两档转速，如能实现无级变速，那么操作就更加方便，运转就更平稳了。  \n\n目前，高速分散机常采用下列方法改变速度。  \n\n$\\cdot$ 选用多速电机主电机选用双速或三速电机，可使分散轴获得两档或三档转速，此方法简单可行，因三速电机价高，故以双速电机应用较多。  \n\n·带式调速采用无级变速胶带，实现带式无级变速传动，调速不轻便，一般胶带寿命不长，更换胶带比较麻烦。  \n\n$\\cdot$ 油压马达变速变速方便，变速范围较大，但油压马达要有高压油泵配合，占地面积大，而且油泵的噪声也较大，这种形式多用于进口设备上。  \n\n·采用电磁调速电机可实现无级调速，调速范围广。这种电机结构简单，价格低，但大多不防爆，不能用于需要防爆的场所。  \n\n$\\cdot$ 变频调速通过变频器改变电源频率，从而改变交流异步电机的转速。变频调速用于高速分散机，具有启动电流小、控制平滑、使用方便以及节能等优点，加上近年来装置费用不断降低，其应用日趋普遍。其使用注意事项主要有以下几点。第一，一般变频器不防爆，如工作场所有防爆要求，可将变频器及相关电器安装在配电室内，而将控制面板安装在主机旁。但变频器与主机之间的距离不宜太远。第二，采用变频调速，可选用专用的变频调速三相异步电机或普通电机，前者不防爆，所以涂料行业多使用后者。用普通电机时应注意使用频率范围不可过大，以免电机转速过低或过高，导致发生异常的温升或噪声以及绝缘破坏等情况，一般低频不宜小于 $20{\\sim}25\\mathrm{Hz}$ 。因为在额定频率以下，由于转速下降，电机散热风扇的风量减小，温升必会增加。长期在低速运行，电机就可能烧毁。第三，变频器的使用环境温度应在 $-10{\\sim}40^{\\circ}C$ 之间，故应安装在通风环境较好的不潮湿、无粉尘飞扬的干净场所。虽然它自身带有风扇冷却，但如安装场地狭窄，应另用风扇冷却。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1132,
+        "chunk": "# （3）高速分散机的型号示例  \n\n$\\textcircled{1}$ 型号表示方法由于高速分散机应用广泛，所以制造厂家很多。将比较常见的型号举例加以说明。a.GFJ-22A表示高速分散机，主电机名义功率为 $22\\ensuremath{\\mathrm{kW}}$ ，落地式（字母B代表平台式)。b.FL22表示高速分散机，落地式（字母X代表悬挂式，即平台式)，主电机名义功率为 $22\\ensuremath{\\mathbf{k}}\\ensuremath{\\mathbf{W}}$ oc.GFJ-350表示高速分散机，叶轮直径为 $350\\mathrm{mm}$ 。安装形式到底是落地式或平台式，型号中未表示，需另加文字说明。  \n\n$\\textcircled{2}$ 部分型号及基本参数标注电机名义功率的GFJ高速分散机的主要型号及基本参数见表4-1-12，其中以GFJ-22 型和GFJ-40 型较常用。另外，小型高速分散机尚有GFJ-4、GFJ-3、GFJ-2.2和GFJ-1.5等型号，详见各厂样本。  \n\n（4）高速分散机使用注意事项 先阅读设备说明书，再关注下列注意事项。  \n\n$\\textcircled{1}$ 安全高速旋转的分散轴及边缘尖利的叶轮，对人的安全构成威胁。不准戴手套擦拭运转部位，要严防衣袖、长发等被轴卷住而发生事故，同时要防止包装袋或其他异物掉入设备内。  \n\n表4-1-12GFJ系列高速分散机主要型号及基本参数  \n\n\n<html><body><table><tr><td colspan=\"2\" rowspan=\"2\">基本参数</td><td rowspan=\"2\">GFJ-7A</td><td rowspan=\"2\">GFJ-11A GFJ-11B</td><td rowspan=\"2\">GFJ-22A GFJ-22B</td><td rowspan=\"2\">GFJ-40A GFJ-40B</td><td rowspan=\"2\">GFJ-55B</td><td rowspan=\"2\">GFJ-75B GFJ-90B</td><td rowspan=\"2\">GFJ-110B GFJ-132B</td></tr><tr><td></td></tr><tr><td rowspan=\"2\">主电机功率/kW</td><td rowspan=\"2\">叶轮直径/mm</td><td>7.5 6.5/8</td><td>11 9/11</td><td>22 14/22</td><td>45 30/42</td><td>55 40/45</td><td>75 90</td><td>110 132</td></tr><tr><td>200</td><td>250</td><td>330</td><td>460</td><td>510</td><td>560</td><td>610</td></tr><tr><td rowspan=\"3\">分散 轴转速</td><td rowspan=\"3\">变频 电磁 /(r/min) 双速</td><td>0~2400</td><td>0~2000</td><td>0~1470</td><td>0~1480</td><td>0~1480</td><td>0~1480</td><td>0~1480</td></tr><tr><td>125～1250</td><td>125~1250</td><td>132~1320</td><td>132～1320</td><td>440~1340</td><td>一</td><td>一</td></tr><tr><td>1200/2400</td><td>1000/2000</td><td>730/1470</td><td>740/1480</td><td>740/1480</td><td>一</td><td>一</td></tr><tr><td colspan=\"2\">最大升降行程/mm</td><td>1000</td><td>1000</td><td>1200</td><td>1500</td><td>1800</td><td>2000</td><td>2200</td></tr><tr><td colspan=\"2\">传动箱回转角度/(°)</td><td>360</td><td>360</td><td>360</td><td>360</td><td>360</td><td>360</td><td>360</td></tr><tr><td colspan=\"2\">油泵电机功率/kW</td><td>0.75</td><td>0.75</td><td>1.5</td><td>2.2</td><td>2.2</td><td>3</td><td>4</td></tr><tr><td colspan=\"2\">参考质量/kg</td><td>1000</td><td>1200</td><td>1800</td><td>3000</td><td>3300</td><td>3800</td><td>4500</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 注油油箱内按要求注人润滑油达到油标合理位置，在使用过程中要关注油面高度。同时搞好轴承、齿轮等处的润滑工作。  \n\n$\\textcircled{3}$ 检查叶轮旋转方向要与标示的方向一致。叶轮安装牢固、不松动，外缘齿形应无明显的变形及磨损。用手盘动叶轮应灵活。  \n\n$\\textcircled{4}$ 锁住回转高速分散机在运转时，应锁紧转动手柄，防止传动箱回转，以免发生事故。  \n\n$\\textcircled{5}$ 试车高速分散机安装或大修后，要先经试车，确认正常后再投人生产。试车主要内容如下。  \n\na.试液压升降系统调整溢流阀至规定压力，排除油缸内空气，检查油箱油位，检查各连接部位和密封部位应无渗漏现象。  \n\nb.试传动部分和分散轴启动主电机，无论是三速电机还是双速电机，各档按钮都能正常顺利变换，若是无级变速传动（电磁调速电机、变频或带式无级变速等)，能方便、灵敏地在变速范围内变速，传动部分各处无异常振动、噪声及发热等异常现象，分散轴下端无明显晃动。因分散轴系挠性轴，开车或停车通过第一极限转速（ $\\mathrm{:530\\sim600r/min}$ ）时，分散轴略有振动属于正常现象。  \n\nc.确认主电机和液压泵电机电器连锁可靠为安全起见，这两个电机不能同时启动。  \n\n$\\textcircled{6}$ 严禁开空车无论试车或生产，叶轮必须浸人盛液容器中，才能开车。否则容易甩弯分散轴或发生其他事故。当发现分散轴弯曲或机器的其他异常情况时，均应立即停车处理。对可变速的高速分散机，一般应低速启动和低速停车。  \n\n$\\textcircled{7}$ 对漆浆黏度的要求漆浆的黏度要适中。太稀则分散效果差，太稠使流动性差，也不适合。合适的漆料黏度范围通常为 $0.1\\sim0.4\\mathrm{Pa}\\cdot\\mathrm{~s~}$ ，加人颜料后的漆浆黏度可达 $3\\sim$ $4\\mathrm{{Pa}\\cdot\\ s}$ 。当漆浆比较黏稠时，活动漆盆应固定，以防在操作中发生位移。  \n\n$\\textcircled{8}$ 注意操作过程的温升由于分散机的能量大部分转换为热能，导致漆浆温度升高，黏度降低，这样对分散操作不利。同时，温度升高也加剧了溶剂的挥发。所以要控制温升，尽量合理地缩短开车时间，必要时停车降温，或使用带有夹套可通冷却水的搅拌槽。  \n\n$\\textcircled{9}$ 关注电流操作过程中要经常注意电流的变化，如发现超载运行，应停车检查原因，采取措施后再继续运转。如电流很小，可设法合理地加大负荷，以提高工作效率。  \n\n$\\textcircled{10}$ 搞好卫生停车后及时清洗叶轮、分散轴，搞好设备及环境卫生，最后将分散轴恢  \n\n复至最低位置。  \n\n①爱护设备，及时检查、维护如检查、调整传动V带的松紧程度；主电机、液压泵及电机、轴承等处应无异常的温升、振动及噪声；液压系统应无泄漏。  \n\n(5）高速分散机的优缺点$\\textcircled{1}$ 优点a.结构简单，操作及维护、保养容易。b.应用范围广，既可在配料工序用作预分散，也可在搅稀工序用作调漆，对某些易分散颜料和对细度要求不高的产品，也可直接起分散作用。c.生产效率高。d.换色、清洗方便。$\\textcircled{2}$ 缺点a.分散能力差，不能分散硬的或结实的颜料团粒。b.对黏度太大、流动性差及某些触变性漆浆不适用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1133,
+        "chunk": "# 2.其他预分散设备  \n\n其他预分散（混合）设备还有双轴高速分散机、同心轴高低速分散机、双轴高低速分散机、三轴高低速分散机、多功能搅拌分散釜、稠浆式搅拌机、转桶式搅浆机带锥底罐的双轴高低速分散机以及在线分散机等。  \n\n从适应物料的黏度范围来看，高速分散机和双轴高速分散机适合较低黏度，在线分散机适合低、中黏度，同心轴高低速分散机、多功能搅拌分散釜适合中等黏度，稠浆式搅拌机、双轴高低速分散机适合较高黏度，而三轴高低速分散机和转桶式搅浆机则可适合更高的黏度。总之，上述设备可以胜任涂料生产中各种物料的预分散（混合）作业。  \n\n(1）双轴高速分散机此处所指双轴为等速旋转的两个分散轴，一般以相同转向旋转。每根轴上可装一个叶轮，也可装2个叶轮。图4-1-63所示为GFS-30型双轴高速分散机。该机I型为双轴单叶轮形式，Ⅱ型为双轴双叶轮形式，转速有双速、三速及无级变速3种形式，可选用。  \n\n![](images/d80d083d8b19340a009a27dbb789a275e93e0f4c5990a7334bc45b00b1449be6.jpg)  \n图4-1-63GFS-30型双轴高速分散机  \n\n双轴高速分散机的优点是由于2个轴同时旋转，搅拌槽内液体打漩的现象减轻了，旋涡不太深了，避免了吸人气体，提高了装料系数和分散能力，适用的物料黏度范围较广。  \n\n图4-1-64显示了双轴4个叶轮的交叉布置。在两叶轮的交叉部位，叶轮的运动方向相反，相对的运动速度加大了1倍，产生了很强的剪切作用。4个叶轮彼此外搭，形成3个强剪切区。另外，叶轮圆盘上冲出的月牙孔，还能产生强烈的汽蚀作用。所以这种双轴高速分散机有较强的分散能力。  \n\n![](images/42ba2f5b24bdfbd9d1c4c86a485ec79bf334619f99aa285b89724d3d9a2fa3ce.jpg)  \n图4-1-64 带月牙孔的叶轮交叉布置  \n\n(2）同心轴高低速分散机所谓同心轴，即为同心双轴，中心轴为高速轴，安装叶轮，主要起分散作用。空心轴为低速轴，安装框式搅拌器，主要起混合作用。通过调节两轴的不同转速，这种分散机能适应各种中等黏度物料的预分散。  \n\n一种带固定搅拌罐的同心轴高低速分散机。因所配的揽拌罐容量较大，一般都要在楼板或操作平台上进行加料操作，故也称平台式。  \n\n还有一种与活动漆浆罐配套使用的同心轴高低速分散机（图4-1-65)，机头可通过油压升降。由于框式揽拌器与活动漆浆罐的壁和底的距离较小，可防止物料的粘壁现象。  \n\n(3）双轴高低速分散机双轴高低速分散机也称双轴双速搅拌机，其结构如图4-1-66所示。双轴转速不相同。高速轴位居偏心，其端部装锯齿圆盘式叶轮，叶轮圆周速度约20m/s左右，主要对物料起分散作用。低速轴居中，通常带动一个三叶框式搅拌器（也有称蝶形搅拌器的)，将物料移送至高速轴叶轮区，进行分散。低速轴主要起混合作用，有时俗称搅拌轴，而将高速轴称为分散轴。  \n\n![](images/272b68c73ae439cd2041572928a6c0e8d0258937c47febd655da14deecdaa23c.jpg)  \n图4-1-65 同心轴高低速分散机  \n\n![](images/9c67ee5d3e8ebc65a6497a119e12756af5a8a959e2d0b580575d3e2b2ff39da7.jpg)  \n图4-1-66 双轴高低速分散机  \n\n低速轴带动的框式搅拌器，其外缘与搅拌槽的间隙很小，能起到刮壁作用。  \n\n双轴高低速分散机的高速轴和低速轴通常用两台电机分别传动，它们的速度可以是一个定速，一个可变速，或者两个都可以变速。这种分散机可适用于较高黏度的物料，如铅笔漆、腻子等。有的机型，双轴在做回转运动的同时，通过液压传动兼做上下往复运动，此举扩大了叶轮的作用范围，更有利于搅拌槽内物料的轴向混合。这种机型也称双轴高低速复动式分散机或双轴高低速往复式分散机。  \n\n双轴高低速分散机的型号，如SJ-900型，其中900表示搅拌槽的直径为900mm。SJ-900型使用较早，用量较大。SJ型双轴高低速分散机已形成系列，除SJ-900 外，还有 SJ-600、SJ-1000、SJ-1100 和 SJ-1200 等机型。  \n\n(4）三轴高低速分散机三轴高低速分散机也称三轴搅拌机。图4-1-67是SJ-1100型三 轴高低速分散机。本机由高低速传动及搅拌部件、升降部件、液压站、电控柜和拉缸等组  \n\n成。高速部分由一电机通过V带带动两根高速轴上的2个或4个叶轮，主要起分散作用。  \n低速部分由电机和减速机通过V带带动低速轴上的框式搅拌器，主要起混合作用。  \n\n![](images/f63a807203d991a5c21e744638ab96627206fdb9c997724ccc4e1d372181596a.jpg)  \n图4-1-67三轴高低速分散机（SJ-1100型）  \n\n与双轴高低速分散机相比，此机增加了一根偏置的高速轴及相应的叶轮，这无疑使它能适用于黏度更高的物料。  \n\n（5）多功能搅拌分散釜图4-1-68为FS型多功能搅拌分散釜结构。从结构上来看，它也是一种三轴高低速分散机。居偏心位置的二轴为高速轴，轴上各置两个锯齿圆盘式叶轮，主要起分散作用。居中的低速轴转速较低，带动一个锚式搅拌器，主要起混合作用。为了冷却，该釜常设置水冷夹套（图中未画出）。  \n\n![](images/920c86bdba2d65f943aed75bd9d8acc7240fe96ea2409761db9adda17152d12f.jpg)  \n图4-1-68 FS型多功能搅拌分散釜结构  \n\n![](images/1140ef8598f871d894cae9862a1ccccb2bc3b5901844311942da9b20804fff3c.jpg)  \n图4-1-69 稠浆式搅拌机  \n\n该釜集低速强力搅拌和高速分散多种功能于一体，对中高黏度及触变性物料具有良好的适应性，可用于各种物料的溶解、分散及调和、配色，尤其适合批量乳胶漆的生产。  \n\n![](images/92e475b7804f843bf1f80b2356de59a3cfcbdb93cce397d2caefead1180ac5a3.jpg)  \n图4-1-70 转桶式搅浆机  \n\nFS型多功能搅拌分散釜的公称容积为2～$12\\mathrm{m^{3}}$ ，有7个规格。  \n\n(6）稠浆式搅拌机 也是一种三轴高低速分散机。所不同的是，2个高速轴中的1个改为中速轴，轴上安装了螺旋推进器，可正反双向运转，使物料作轴向上下运动。这种设备适用于黏度较高的稠浆型物料。  \n\n图4-1-69所示为瑞典威斯特灵（WESTER-LINS）公司生产的稠浆式搅拌机。低速轴带动的三叶锚式搅拌器上带有刮刀装置，使容器内不留死角，所有物料都能参与分散。图示设备设有称重传感器。  \n\n国产CJ型稠浆式搅揽拌机的搅拌罐容积为1～5m3，有7个规格。  \n\n(7）转桶式搅浆机也称卧式搅浆机，其外形见图4-1-70。与它配合的漆浆罐放在带大齿轮的齿轮车上，推到搅浆机前与机上的小齿轮啮合后扳下扳把将其锁定。在工作中，漆浆罐是旋转的，由机头带动的一对立式螺旋桨叶与漆浆罐组成了行星式运动，桨叶在自转，漆浆罐在公转。罐边上还装有一把刮刀，起到刮壁的作用，因此这种搅浆机有很好的拌和作用。更换漆浆罐时，通过机械传动装置，可使机头回转拾起。  \n\n这种搅浆机操作方便，能直接往活动漆浆罐投料，漆浆罐和搅拌器清洗方便，特别适合多品种、小批量、产品颜色频繁更换的生产。它能适应高黏度物料，常用来与三辊磨配套使用。  \n\n目前国内生产的B760型搅浆机所用漆浆罐的容量为 $140\\mathrm{L}$ 0  \n\n(8）一种带锥底罐的双轴高低速分散机图4-1-71所示的带锥底罐的双轴高低速分散机是德国耐驰（NETZSCH）公司产品，也称PMD-VC系列混合-搅拌-分散设备。  \n\n$\\textcircled{1}$ 结构和工作原理 在设备运行中，高速旋转的分散叶轮还同时做上下往复运动。当分散叶轮上升至接近液面处，利用声控和功率测量控制原理，自动行程升降装置可保证让其立即向下返回，从而避免了将空气混人物料。慢速传动的框式搅拌器（也称混合臂)，将物料送向偏心布置的分散叶轮，从而达到节能的循环效果。安装在框式搅拌器上的刮板及筒体下部的锥底，可使物料干净地排空。  \n\n混合罐的筒体及锥底外侧焊有螺旋异型管夹套，可通水进行冷却（必要时也可做加热用)。加料可从加料口加人，也可在加料口上附加振动式漏斗加料器  \n\n![](images/dcb41c11a53be7e9116b857b891bc06939f672d868dce0cd91407c59bb965ab9.jpg)  \n图4-1-71 带锥底罐的双轴高低速分散机1一慢速传动装置；2一锥底；3一分散叶轮；4一框式搅拌器；5一螺旋异型管夹套；6一分散轴；7一刮板；8—简体；9—自动行程升降装置；10—电机；11一加料口  \n\n和螺旋输送器加料。  \n\n$\\textcircled{2}$ 设备的特点和优点  \n\na.锥底结构操作弹性大 投料较少也可进行分散作业。  \n\nb.慢速传动装置在底部，上部空间大，便于布置加料装置及操作和维修。  \n\nc.设备内没有死角，分散效果好，可直接用来生产某些乳胶漆，更换产品时设备清洗方便。  \n\n③主要规格及基本参数PMD-VC系列分散设备有8个规格，其有效容积小到50L，大到 $10\\mathrm{m^{3}}$ 。  \n\n(9）在线分散机德国耐驰（NETZSCH）公司近年推出一种新颖的预分散设备—在线分散机（ $\\Psi$ MIX 系列)。  \n\n① 结构和工作原理在线分散机的结构如图4-1-72所示。漆料用输液泵7通过进料管3和喷嘴从4个切线方向进入分散机。分散机的转子在高速旋转，带动漆料加速，并使之沿着分散机的转子与锥形定子间的间隙往外甩。这就相当于一台离心泵，在泵的中心区，即分散机的上方，形成了真空。  \n\n![](images/b0b5296768fc1be7c9ab49c9db06f46c1b7db6f722938e55c02d4fb2465132e6.jpg)  \n图4-1-72 在线分散机  \n\n器；2一打散头；3—进料管；4—颤料从此处进人旋转的液流中被湿润；5—带冷却夹套的锥形定子； 6—安全滑阀；7—输液泵；8—带揽拌器的物料罐；9-转子；10一出口  \n\n颜料从分散机顶部的加料斗经加料器加人，在分散机上方的真空环境下，颜料聚集体中的微气泡膨胀，聚集体破碎。高速旋转的打散头起到进一步打散颜料颗粒的作用。尔后，已散开的颜料细粒被带入已形成的大表面积液流（漆料）中。  \n\n在由锥形定子与转子的间隙形成的狭长的压缩区内，颜料细粒与漆料混合并被湿润。压缩区的压力逐渐升高，至出口处压力最高。这样的压力梯度有利于漆料通过毛细作用，继续深人颜料颗粒内部，使之进一步湿润。  \n\n$\\textcircled{2}$ 操作简介  \n\na.启动将漆料计量后加人物料罐，颜料称重后加入加料斗。启动输液泵和分散机，使液流在物料罐和分散机间不断循环。  \n\nb.加料在分散机上方形成真空后开始加料，根据真空度控制加料速度。出口压力取决于出口管线的阻力，约为 $0.\\ 03\\{\\sim}0.\\ 5\\mathrm{MPa},$ 0  \n\nc.分散和倒罐颜料加料完成后，继续进行分散作业，直至产品质量达到要求。然后通过转换物料罐下方的阀门，将产品排放至产品罐，并对系统进行清洗，以备下一批料的分散。  \n\n$\\textcircled{3}$ 设备特点和适用范围  \n\na.效率高，颜料能在漆料中快速湿润。预分散后的漆料均匀性好。  \n\nb.在真空状态加料，有利于环境保护。  \n\nc.由于定子夹套通水冷却及液流通过原料罐循环，产品温升小。  \n\nd.在线分散机适合于高固体含量组分的分散和难湿润颜料的分散，一般用于大批量、单颜料漆浆的生产。  \n\n$\\textcircled{4}$ 产品型号示例如型号 $\\Psi$ —MIX45，其主要技术参数如下：粉体处理量为 $5m^{3}/\\ensuremath{\\mathrm{h}}$ 悬浮液处理量为 $10{\\sim}15\\mathrm{m}^{3}/\\mathrm{h}$ ；转子功率为 $22\\sim55\\mathrm{kW}$ ；转子转速为 $500{\\sim}2000\\mathrm{r/min}$ ；转子圆周速度为 $10\\mathrm{{\\sim}40m/s}$ ；输液泵功率为 $7.5\\substack{\\sim}11\\mathbf{kW}$ ；进料压力为 $0,03\\sim0,35\\mathrm{MPa}$ ；温升最大为 $5^{\\circ}C$ ；控制系统为PLC（可编程逻辑控制器)；质量为 $2700k g$ 9",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1134,
+        "chunk": "# 三、研磨分散设备",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1135,
+        "chunk": "# 1.概述  \n\n色漆是固体颜料分散在液体漆料中制得的液体物质，所以研磨分散设备无疑是色漆生产的主要设备。色漆研磨与通常固体破碎及机械加工的研磨意义不同，它主要起分散作用，把颜料聚集的大颗粒分离成原始粒子或尽可能小的粒子。可以说研磨是习惯上约定俗成的称呼，所以也有把研磨分散设备直接称分散设备的。  \n\n研磨分散设备类型很多，其基本形式可分为两类。一类带自由运动的研磨介质，另一类不带研磨介质。前者如砂磨机、球磨机，依靠研磨介质（如玻璃珠、钢球、卵石等）在冲击和相互滚动或滑动时产生的冲击力和剪切力进行研磨分散，通常用于流动性较好的中、低黏度漆浆的生产。后者如辊磨，依靠抹研力进行研磨分散，可用于黏度很高甚至成膏状物料的生产。高速分散机也是研磨分散设备，不带研磨介质。它主要用来与砂磨机配合，起预分散作用。除高速分散机外，目前常用的研磨分散设备有砂磨机、三辊磨和球磨机。  \n\n砂磨机于20世纪50年代首先在美国问世。最初是开启式，使用天然沙子作研磨介质，故名砂磨机。后来虽使用玻璃珠等人造研磨介质，有人称之为珠磨机，但习惯上以及一些标准还是称其为砂磨机。20世纪60年代，上海、天津两地涂料企业开始从国外引进开启式砂磨机并自制，1968年，重庆产80L立式开启式砂磨机开始批量生产。由于砂磨机具有生产效率高、能耗低、操作容易、能连续生产等优点，很快在全国涂料行业得到推广。以后又有引进的和国产的立式密闭砂磨机、卧式砂磨机、各式棒销式砂磨机和篮式砂磨机等多种砂磨机，在全国各地的涂料企业中投入生产。各种砂磨机早已取代三辊磨和球磨机，成为涂料生产中最主要的、占垄断地位的研磨分散设备。  \n\n三辊磨是使用历史久远的研磨分散设备，球磨机是最古老的研磨分散设备之一，它们曾经是色漆生产中主要的或重要的研磨分散设备。可是自从各种形式砂磨机推广和普及后，如今它们的应用日渐萎缩。只是由于它们自身仍有一些难以替代的优点，所以尚在少数品种和特殊情况下得以使用。如用三辊磨制造少量调色浆，用球磨机生产毒性大的船舶漆等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1136,
+        "chunk": "# 2.立式开启式砂磨机  \n\n立式开启式砂磨机是砂磨机中应用最早，而且至今仍在广泛使用的砂磨机。  \n\n(1）砂磨机的工作原理立式开启式砂磨机主要由带夹套的筒体、分散轴、分散盘及平衡轮等组成（见图4-1-73）。分散轴上安装若干（如 $8\\sim10$ 个）分散盘，轴下端的平衡轮对分散轴起一定的稳定作用，但也有一些砂磨机不用平衡轮。简体中投入适量的玻璃珠或其他研磨介质。经预分散的漆浆用送料泵从筒体底部输人，送料泵的流量可以调节。一且漆浆送人，立即启动砂磨机，分散轴带动分散盘高速旋转，分散盘外缘的圆周速度达到 $\\mathrm{10m/s}$ 左右（分散轴转速因分散盘大小不同，通常在 $\\mathrm{\\Delta600{\\sim}1500r/\\mathrm{min}}$ 范围内)。靠近分散盘表面的漆浆和玻璃珠受黏度阻力作用随着分散盘运转，抛向砂磨机的筒壁，又返回到中心区。这时形成的湍流总体流型，如图4-1-73所示，可大体描述为双环滚动方式。这种双环滚动产生良好的研磨分散效果，特别是在靠近分散盘表面处，以及分散盘外缘与筒壁之间的区域。漆浆在上升过程中，多次回转于两个分散盘之间作高度湍流运动。颜料粒子在这里受到高速运动玻璃珠的剪切和冲击作用，使颜料分散在漆料中。分散后的漆浆通过筛网从出口溢出，玻璃珠则被筛网截留。  \n\n砂磨机的工作效率高，比球磨机要高出很多倍，究其原因，一是因为研磨介质在砂磨机中获得了高速度（约 $\\mathrm{10m/s)}$ ，所以作用在研磨介质球体上的离心力要比重力大几十倍甚至一百多倍，使球体间相互碰撞、摩擦产生很强的冲击和剪切作用。二是虽然研磨介质球体直径很小（大多为 $\\scriptstyle1\\sim3{\\mathrm{mm}},$ )，但数量却非常之多。所以在筒体单位容积中研磨介质互相碰撞的接触点很多。无数高速运动的小球，都在努力工作，整机的工效自然很高。  \n\n若漆浆经一次分散仍未达到要求的细度，可将流人漆浆罐的漆浆用泵送回砂磨机再作分散，直至合格为止。也可将几台砂磨机串联安装，使漆浆一次通过即可达到需要的细度。这样操作简单，可提高产量和产品质量，使生产更加连续化，适用于大批量生产。串联砂磨的数量，以2台、3台居多，国内最多有达到6台的（此时如其中有1台临时损坏，通过阀门切换将其甩掉，并不影响生产)。漆浆在砂磨机中受到分散盘和玻璃珠等研磨介质的激烈搅拌，必然会引起温度升高，导致溶剂挥发，既浪费物料，又污染了环境，严重时还会影响产品质量，甚至使漆浆胶凝化。所以砂磨机的筒体装有夹套，可通水（或冷冻水）进行冷却，以保持砂磨机筒体内漆浆的温度在许可的范围内。  \n\n![](images/3632e71371d92672de970b3ae714410a79f992d3d93845ba6c7e9757bebc1817.jpg)  \n图4-1-73砂磨机工作原理1一水夹套；2一两分散盘间漆浆的典型流型：3一筛网（顶筛）；4一分散后漆浆出口；5一分散盘；6一漆浆和研磨介质混合物：7一平衡轮；8一底阀；9一经预分散的漆浆人口  \n\n(2）设备结构立式开启式砂磨机整机主要由机身、主电机、传动部件、筒体、分散器、送料系统和电器操纵系统组成。图4-1-74为国内广为使用的SK80-2立式砂磨机的结构。  \n\n$\\textcircled{1}$ 机身是用来安装和固定传动部件和筒体等砂磨机所有的零部件的构件，国产砂磨机早期曾用过整体铸造的铸铁机身，因制造周期长，过于笨重，现已被钢板焊接机身取代。机身一般用地脚螺栓固定。近年也有一些新型砂磨机，注明无需地脚螺栓，只要摆平即可。  \n\n![](images/53e33a635346ddf2ba71f6c6a6fec85571659482075586723e30219ef33863bc.jpg)  \n图4-1-74SK80-2立式砂磨机的结构 1一放料放砂口；2一冷却水进口；3—进料管； 4一无级变速器；5一送料泵；6一调速手轮； 7—操纵按钮板；8—机身；9—分散器； 10—离心离合器；11—主电机；12一传 动部件；13—筛网；14—简体；15—筛 网罩；16—出料嘴；17—出料温度计  \n\n$\\textcircled{2}$ 主电机主电机为驱动砂磨机分散轴的动力源。按使用场所有无防爆要求，常选用封闭型或隔爆型三相异步电动机  \n\n$\\textcircled{3}$ 传动部件传动部件主要包括V带和V带轮、传动轴、轴承座及联轴器等。在立式砂磨机中，由于玻璃珠沉底等原因，启动比较困难，启动电流很大，容易烧坏电机及电器，损坏机件（如断轴），也对车间电网造成冲击。为解决这个问题，有的砂磨机在主电机轴上装上离心离合器或液力耦合器。由于离心离合器在启动时因摩擦而产生的噪声大，摩擦片的磨损也较严重，所以近年逐渐被性能比较先进的液力耦合器所取代。  \n\n液力耦合器是一种动力式液力传动元件，其作用似乎像联轴器，但其功能要超出联轴器很多。如改善了启动性能和过载保护等耦合器特性，都是联轴器所没有的。此外，由于降低了电机的启动电流，缩短了启动时间，可适当降低砂磨机的装机功率，同时也起到了节电的效果。  \n\n$\\textcircled{4}$ 筒体  \n\na.筒体的结构 筒体通常由内筒和夹套焊接而成。砂磨机长期使用后，筒体内壁被磨损，对应各分散盘的位置，磨损成沟槽形状，严重时会磨穿而漏水。内筒损坏可卸下，换上新内筒，焊接后重新使用。近年有一种装配式筒体面世，夹套与内筒不焊接，内筒上下部位依靠2个橡胶○形密封圈与夹套密封，更换内筒比较方便。  \n\nb.底阀筒体底部设有底阀（单向阀）（图4-1-75）。由泵输送的物料打开此阀进入筒体，泵停止送料时，在弹簧和阀芯自重的作用下，阀门关闭，以防止物料和研磨介质倒流。  \n\n![](images/4b8439ebdb7ec9b20bd1b52aefd637a4e6237aaa5f7f2aea2a0044c14dffe1f4.jpg)  \n\n![](images/ec448a1f7845b35e1e16465395ee82be5f8883a7fab130714af9096e35fa05fd.jpg)  \n图4-1-75 底阀  \n图4-1-76 出料筛网  \n\n1—进料接管；2—弹簧；3—阀芯；4—阀座  \n\n1一筛网架；2—筛网片；3—分离圈；4—筛网盖此阀内狭窄处易挂住杂物，以致阻力增加，进料不畅。故要常予清理。  \n\nc.出料筛网（顶筛）简体顶部有出料筛网，也称顶筛。其作用是挡住研磨介质，只让漆浆通过。筛网片常用0.5mm厚的不锈钢板制作，上面密布冲压出来的条状缝隙，缝宽大多为0.5mm。为便于装拆，顶筛都制成两个半圆状，如图4-1-76所示。显然，组成顶筛的筛网架、筛网片、分离圈和筛网盖都是对开，而且是对称的。  \n\nd.筒体的材料筒体内筒的材料主要有碳钢、不锈钢及碳钢加聚氨酯塑料衬里3种，碳钢价廉，使用最普遍；不锈钢内筒适用于水性涂料；聚氨酯塑料有很好的耐磨性、耐腐蚀，可防金属离子沾染物料，在染料行业使用较多，在涂料行业使用时要考虑某些溶剂可能会使其产生溶胀。  \n\n$\\textcircled{5}$ 分散器  \n\na.分散器的组成和结构分散器由分散轴、分散盘、平衡轮和联轴器等零件装配而成，是砂磨机的主要工作部件。图4-1-77是国产砂磨机的一种分散器。分散盘通过圆柱键与分散轴联结，各分散盘被撑套间隔开(图示为带三爪的A型撑套，也可用不带三爪的撑套)。  \n\n![](images/b4e6e2cdf295595786fea46d55684af053a52091b920bb725ef5b5d016562ad2.jpg)  \n图4-1-77 分散器  \n\n1一联轴器；2—分离器；3—调整垫圈；4—垫圈；5—稳流盘；6—撑套； 7—圆柱键；8—A型撑套；9—分散盘；10一分散轴；11—平衡轮  \n\nb.分散盘分散盘是带动研磨介质和物料在砂磨机简体中运动从而完成研磨分散过程的构件，在立式砂磨机中常用的分散盘主要有3种，如图4-1-78所示。图4-1-78中A型是带三爪圆环盘，也称塔形分散盘，3个爪有较强的揽拌作用，适用于黏度较低的物料，因形状复杂，一般需铸造成型。B型是开圆孔平盘。C型是开长槽平盘，它们适用于中、高黏度物料。一般认为开长槽平盘优于开圆孔平盘，目前应用最广。平盘结构简单，便于加工，无论采用硬质材料制作或将制成品经热处理提高硬度，表面均可磨光，增强了耐磨性。还有一种折中的方案，在开长槽平盘下面装带轴孔的三爪撑套，以加强搅拌效果，也较适用于低黏度的物料。  \n\n![](images/52b391546a1393d3049d449b12c4456a3aff5dac2105cfd2063de54a994855c2.jpg)  \n图4-1-78 立式砂磨机常用分散盘  \n\n此外，还有一种宜用于高黏度物料的偏心分散盘（图4-1-79）。也称偏心平盘或偏心环轮型分散盘。它们按顺序装在分散轴上，呈螺旋线排列。3个为一组，一般装9～15个为一套。  \n\n与不偏心的分散盘比较，这种偏心平盘在运转时除剪切力外增加了撞击力，它迎面的一侧都在撞击研磨介质。而且运动和撞击的范围相当大。提高了研磨分散效率。另外，当物料黏度较高时，使用一般的分散盘易形成研磨介质在筒体出口处积聚的现象，而偏心分散盘组合成的螺旋形，能把研磨介质推向筒体人口侧。所以偏心分散盘适用于高黏度物料。  \n\n![](images/5c2f4b9295d9ff1d1c520ed68342524b1874f4f07712236bead3ccbfc0cdf5f4.jpg)  \n图4-1-79 偏心分散盘配置  \n\n由于偏心分散盘对研磨介质冲击较大，因此要求研磨介质应有较高的强度，同时，分散轴的转速也宜适当降低。  \n\n分散盘一般用碳钢、铸铁、合金钢或不锈钢制造。用碳钢和合金钢时，大多施以热处理或化学热处理，以提高其硬度和耐磨性。铸铁最好选用合金耐磨铸铁，硬度较高，而且从表面到内层都很耐磨。不锈钢分散盘大多用于水性漆。还有一种碳钢涂覆聚氨酯塑料分散盘，非常耐磨，而且耐腐蚀，它可以避免因磨损掉下金属粉末而沾污物料。需要注意的是，覆层材料在某些强溶剂中长期浸泡，有可能出现溶胀现象，必要时可先做试验。  \n\n$20\\mathrm{L}$ 以上的立式砂磨机大多装 $8\\sim10$ 个分散盘。有的砂磨机，最上面的 $1\\sim3$ 个分散盘直径比其余的大；还有一些砂磨机，在分散盘上方安装了 $1\\sim2$ 个不开孔的圆盘（图4-1-77中称稳流盘)，原意是为避免或减少研磨介质从砂磨机中进出，因使用效果不佳，现大多不用。  \n\n$\\textcircled{6}$ 送料系统 送料系统由送料泵和变速装置组成。  \n\na.送料泵用于砂磨机送料的泵主要有内齿泵、滚子变量泵、单螺杆泵和气动隔膜泵。内齿泵最常用；滚子变量泵通过调节转子偏心，自身可调节流量，不用配置变速装置；单螺杆泵适用于高黏度物料，目前主要用来为水性涂料送料，因其定子多为橡胶制，长期在溶剂中使用可能要溶胀；气动隔膜泵无泄漏，通过调节气压就可方便地调节流量，目前大多用于密闭式砂磨机，特别适合输送对剪切力敏感的液体。此外，电动隔膜泵和齿轮泵也可使用。  \n\n与砂磨机配套的内齿泵，由于内齿轮的齿形不是渐开线而是圆弧，故常称之为内圆弧齿轮泵。它结构简单紧凑，体积小，便于安装在砂磨机机身侧壁上。它适用范围广且造价低，因而应用十分普遍。图4-1-80显示其工作原理。  \n\n内齿泵的主要零件是互相啮合的一个外转子（内圆弧齿轮）和一个内转子（从动齿轮）及其间的一个月形件，月形件的作用是将吸入腔与排出腔分隔开。此外，组成一台送料泵，还有泵体、泵盖、轴、心轴、轴承、轴封部分以及电机、传动部分等。内齿泵的工作原理：当主动的内圆弧齿轮带动从动齿轮旋转时，在齿轮脱离啮合处形成部分真空而吸人液体，当主动齿轮和从动齿轮转到与月形件接触后，齿槽所形成的封闭容积不再变化，然后齿轮进入啮合，液体受挤压致压力升高而被排出。  \n\n从以上工作原理可知，若泵的旋转方向改变，泵的进口与出口将互换。所以泵的转向一  \n\n![](images/99fd88533a28216bbaa42e38afaa909583c463340c4798b068957bdf50155bc1.jpg)  \n图4-1-80 内齿泵的工作原理  \n\n1—内圆弧齿轮（主动）；2—月形件；3—从动齿轮；4—泵体；5—轴套；6—心轴；7一轴定不能搞错。有的内齿泵，为安全起见，在泵轴的连接处设置了安全剪切销，此销的材质为尼龙-6或硬聚氯乙烯（亦可用毛竹或硬木代替)，当泵内进人异物（如棉纱、钉子等）或其他原因将泵卡死（如长期不用漆浆干涸）时，安全剪切销即被剪断，从而保护了设备。内齿泵的轴封大多为软填料密封，应使用质量好的软填料（如碳纤维填料)，精心维护，以防泄漏。  \n\nb.送料泵的变速装置为了满足生产工艺的需要，送料泵的流量需能随时调节。对于大多数泵来说，调节流量就是调节泵的转速。目前较普遍使用的是机械无级变速装置。其中较常用的有钢球式无级变速器、齿链式无级变速器和带式无级变速器。前两者结构复杂，制造精度高，拆装比较困难，现应用逐渐减少。而带式无级变速器因结构简单，调速方便，无日常维护工作等优点得以推广。此外，由于变频器价格下降，电机变频调速也逐渐被采用。  \n\n$\\textcircled{7}$ 电气控制系统 由电气箱、操作按钮板等组成。  \n\na.控制程序  \n\n·若主电机或泵电机其中之一因过载而断路时，另一电机也自动停车。  \n$\\cdot$ 若泵电机不启动，则主电机不能启动，但可点动。  \n\nb．电器配置  \n\n·主电机、泵电机、按钮、电流表、指示灯可按生产工艺要求选用普通型或防爆型。·电气箱内电器为普通型，可根据现场条件将电器箱安装于车间配电室或其他合适位置，并按电气原理图敷设配线。  \n\n（3）产品的型号示例  \n\n①型号表示方法如目前大量使用的SK80-2A，S代表砂磨机代号，K代表立式开启式（B代表立式密闭式)；80代表简体有效容积（L)；2代表设计序号；A代表改进设计。  \n\n$\\textcircled{2}$ 主要型号及基本参数国内立式开启式砂磨机的生产厂家很多，产品型号、规格繁杂。据已收集的样本统计，砂磨机筒体有效容积，从2L起，最大到500L，其间5L、10L、20L、 $30\\mathrm{L}$ 、 $40\\mathrm{L}$ ， $50\\mathrm{L}$ ， $60L$ ， $80\\mathrm{L}$ 、 $120\\mathbb{L}$ 、160L、300L等规格都有厂家生产。5L以下属实验室设备，以2L较常用，SK2小型砂磨机的电机功率为 $0.55\\mathrm{kW}$ ，主轴转速为 $2800\\mathrm{r/min}$ 分散盘直径为 $72\\mathrm{mm}$ ，分散盘可升降的高度范围为 $\\mathsf{100m m}$ ·  \n\n涂料生产用立式开启式砂磨机的主要型号及基本参数见表4-1-13。其中又以SK80和  \n\nSK40最常用。120L以上的砂磨大多在非涂料行业（如染料行业）使用。此表也适用于立式密闭式砂磨机。  \n\n表4-1-13中所列的生产能力，也是一个笼统的范围，只供参考。因为漆浆的品种不同、颜料性能的差异，对生产能力的影响很大。此外，要求的分散细度越小，生产能力就越低。  \n\n表4-1-13中所列主电机功率，大多为两个数值。一般情况下，当砂磨机带液力耦合器时，选用较小的一挡。如80L立式开启式砂磨机，带液力耦合器时可选用22kW 电机，不带时选用30kW电机。但如遇物料特别黏稠、或密度特别大等情况时，电机功率应按生产工艺要求选用。  \n\n表4-1-13立式开启式砂磨机的主要型号及基本参数  \n\n\n<html><body><table><tr><td>基本参数</td><td>SK10</td><td>SK20</td><td>SK40</td><td>SK60</td><td>SK80</td><td>SK120</td></tr><tr><td>简体有效容积/L</td><td>10</td><td>20</td><td>40</td><td>60</td><td>80</td><td>120</td></tr><tr><td>主电机功率/kW</td><td>5.5,7.5</td><td>11,15</td><td>18.5,22</td><td>22,30</td><td>22,30</td><td>30,37</td></tr><tr><td>泵电机功率/kW</td><td>0.75</td><td>0.75~1.1</td><td>0.75～1.1</td><td>1.1~1.5</td><td>1.1~1.5</td><td>1.5</td></tr><tr><td>泵流量调节范围/（L/min）</td><td>1.5~12</td><td>2~16</td><td colspan=\"4\">3~24</td></tr><tr><td>生产能力/(kg/h)</td><td>20~200</td><td>40~400</td><td>70~700</td><td>100~1000</td><td>120~1200</td><td>150～1500</td></tr><tr><td>分散细度/μm</td><td colspan=\"6\">1<分散细度<20</td></tr><tr><td>物料黏度/Pa·s</td><td colspan=\"6\">SK<2</td></tr><tr><td>分散轴转速/(r/min)</td><td>1440</td><td>1320</td><td>1020</td><td>930</td><td>830</td><td>650</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1137,
+        "chunk": "# （4）立式开启式砂磨机的操作要点  \n\n$\\textcircled{1}$ 运转前的检查事项  \n\na.检查主电机和泵电机的旋转方向是否正确(按机体和泵体上的箭头方向校正)，在调校主电机旋转方向时，必须在未装分散器时进行，因为分散器不允许空车运行。  \n\nb.检查冷却水进出口是否通畅。  \n\nc.主电机V带出厂时为松弛状态，需重新调紧至合适程度。  \n\nd.检查地脚螺栓及各紧固螺栓是否紧固可靠，磨筒是否已固定。  \n\ne.检查送料泵配带的无级变速器的润滑等情况，盘动送料泵看是否能转动。  \n\nf.打开砂磨机底部进料阀门。  \n\ng.检查筒体、管道、阀门是否已清洗干净。  \n\n$\\textcircled{2}$ 运转准备  \n\na.将漆浆用送料泵输人筒体内，约占筒体容积1/3左右。  \n\nb.从筒体顶部加人研磨介质总装填量的一半左右，轻轻点动分散轴（旋转十几转即可)，使漆浆和研磨介质混匀。  \n\nc.加人全部研磨介质，装上筛网盖、分离圈及筛网罩。然后再轻微点动分散轴。研磨介质装填量（按堆积容积计）约占筒体有效容积的 $60\\%\\sim80\\%$ 0  \n\n$\\textcircled{3}$ 试运转a.试运转的目的  \n\n$\\cdot$ 检查机器各部分运转是否正常。  \n$\\cdot$ 清除筒体、管道、阀门、送料泵等处内壁的油污及铁锈等杂物。  \n\nb.试运转的方法和操作程序供试运转的漆浆量约比筒体容积多1倍，时间约半小时。试运转时须注意检查机器的振动、噪声、温升等情况，如有异常，应查出原因予以消除。  \n\n试运转的操作程序是先启动送料泵，并将无级变速器调到最低速，等顶筛可见漆浆液面后停泵。用点动法启动砂磨机，待运转声音正常转入正常开机，即先开泵，后开砂磨机，调整送料泵的转速，以调节进料速度，保持顶筛的正常液面高度（大约在顶筛高度一半左右)。打开冷却水阀门，给砂磨机降温。  \n\n$\\textcircled{4}$ 投料运转  \n\na.投料运转的程序与试运转的程序相同。  \n\nb.如为串联式砂磨，按上述步骤把所有的单机都检查一遍，然后逐台开动，待第一台磨运转正常后即开启第二台磨，依此类推。  \n\nc.砂磨机运转正常后，可以开始检验漆浆细度，根据检测结果，确定研磨分散的道数。  \n\n$\\textcircled{5}$ 换色由于生产条件有限，不可能每种颜色漆浆都有专用的砂磨机，因而换色操作不可避免。一般采取顺序套色操作，其方法是由浅到深。如套色操作不能满足要求，则需进行彻底清洗，一般先用漆料循环冲洗，再用适量的溶剂冲洗。同时要把盛漆浆的容器（漆盆）刷洗干净，以不影响下一产品的色相及质量为准。在实际生产中，对白漆及一些专用品种还是以专磨专用为好。  \n\n$\\textcircled{6}$ 停车  \n\na.研磨分散结束，关送料泵停止加料并关闭进料阀门，停主电机。  \n\nb.关冷却水。冬天停车后，如有可能结冰则应将夹套冷却水放空，以免冻坏设备：用溶剂把顶筛刷洗干净，以免漆浆结皮堵塞筛孔。如发现破损应立即更换。  \n\nd.停车时间较长时，应在停车前往简体内输入适量漆料，以免下次启动困难。长期停车可输人溶剂清洗研磨介质，或将筒体内研磨介质和残余漆浆全部倒出，以防筒体内物料干涸、结块。倒出的研磨介质要用溶剂清洗干净。  \n\n（5）立式开启式砂磨机使用注意事项$\\textcircled{1}$ 在筒体内没有物料和研磨介质时严禁启动。  \n\n$\\textcircled{2}$ 经较长时间停车后开车，应检查顶筛有无干涸结皮，如有此现象，应用溶剂清洗干净，以免开车后漆浆从顶筛上方溢出（冒顶)。砂磨运行时也应常刷洗顶筛，发现破损及时更换。  \n\n$\\textcircled{3}$ 长期停车后开车，应检查分散器是否被漆浆和研磨介质卡住。如盘不动车可用泵输人溶剂予以溶解，然后再启动，不可强行启动，以免损坏设备。  \n\n$\\textcircled{4}$ 用溶剂清洗砂磨机时，分散器只能点动，因为分散盘和研磨介质在溶剂中连续运转磨损很快。  \n\n$\\textcircled{5}$ 研磨介质在装机前，应先过筛和清洗，以清除杂质及小于规格的粒子。砂磨机在使用过程中应经常注意研磨介质的磨损情况，不时予以清洗、过筛、补加或更新。  \n\n$\\textcircled{6}$ 使用液力耦合器时，要选用合适的油并经常关注油量的变化。  \n\n$\\textcircled{7}$ 移动砂磨筒体时，一定要注意安全，防止筒体倒下伤人。  \n\n$\\textcircled{8}$ 无级变速器严禁停车调速  \n\n$\\textcircled{9}$ 严禁设备超负荷运转及带病运转。如发现设备各处有异常的温升、振动及噪声，应立即停车检查并排除故障。  \n\n$\\textcircled{10}$ 爱护设备，及时检查、维护。如检查调整传动V带的松紧程度；做好设备润滑工作；送料泵如有泄漏应及时调整或更换轴封软填料；分散盘严重磨损（外缘厚度小于 $2\\mathrm{mm}^{\\dag}$ ）后应抓紧更换，否则破损分散盘的尖锐边缘会打碎玻璃珠。为缩短停车时间，可准备成套分散器备用。  \n\n（6）立式开启式砂磨机的优缺点  \n\n![](images/eb3ec1e16ba16faf0d4490a7698254c75cb2600683fe8c397b54ca239a2913f5.jpg)  \n图4-1-81SW60-1卧式砂磨机结构1一送料泵（与无级变速器连接）；2一调速手轮；3-主电机；4-支脚；5-电器箱：6一操作按钮板；7-传动部件；8一油位窗；9一电接点温度表；10-主机；11—电接点压力表；12-机身  \n\n$\\textcircled{1}$ 优点立式开启式砂磨机结构简单，制作容易，造价较低。它产能大，运行可靠，且操作、维护、检修也很方便。  \n\n$\\textcircled{2}$ 缺点  \n\na.不适应高黏度和高触变性物料因是在常压下通过筛网出料，处理这两类物料将造成出料困难，会因“糊罗”而导致“冒顶”（即溢料）。开启式砂磨机一般只适用于处理黏度小于$2\\mathrm{{Pa}\\cdot5}$ 的物料。  \n\nb.溶剂挥发比较严重 不仅损失物料，而且不利于环境保护和工人身体健康。c.要勤刷顶筛，比较麻烦顶筛暴露在空气中，漆浆容易结皮，需时常用溶剂洗刷。d.研磨介质可能逸出在操作不当时，研磨介质可能“冒顶”。平时也会有少许研磨介质从顶筛上部进出来。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1138,
+        "chunk": "# 3.卧式砂磨机  \n\n立式砂磨机还有一个难以解决的先天缺陷，就是研磨介质会沉底，以致停车易，启动难。因此也难以使用密度大的研磨介质。而卧式砂磨机，由于其筒体和分散轴系水平放置，就不存在上述缺陷。也因为是卧式，它在结构上只可能是密闭式。  \n\n20世纪70年代国内开始引进卧式砂磨机，20世纪80年代国产机型研制成功，然后逐渐形成系列产品，并得到广泛应用。  \n\n（1）设备结构卧式砂磨机由主机、主电机、传动部件、机身、送料系统和电气控制系统等组成。图4-1-81为60L卧式砂磨机结构。  \n\n①主机主机由筒体、分散轴、分散盘、出料机构、机械密封和轴承座等组成。图4-1-82为60L卧式砂磨机主机结构。  \n\n![](images/9f45b83bbb5f77c16a05e819430095deaa84b179f58fa1bcaaa717da8b395f23.jpg)  \n图4-1-82SW60-1卧式砂磨机主机结构  \n\n1-轴承座；2-注油泵；3-机械密封；4-出料盘；5-出料罩；6-前端盖；7-出料筛圈；8—分散轴；9-撑套；10—分散盘；11—进料管；a-放砂和放漆浆口；b-加料、加砂及压力表口；c—冷却水出口；d—冷却水人口；e—出料口a.简体筒体由不锈钢材料制成，分为内筒和外套。为提高冷却效果，采用了螺旋槽  \n\n冷却结构。内筒很容易从外套中取出，给维修和更换备件提供了方便。  \n\nb.分散轴和分散盘 分散轴上装有数个分散盘。分散盘间用撑套支撑。60L卧式砂磨机采用的是多边形带长槽孔的分散盘，由于多边形和长槽孔同时传递动能以及黏度阻力的作用，使研磨介质球体产生剧烈的摩擦和碰撞，从而达到高效的研磨分散作用。分散盘安装时，制造厂家要求成对组装，如图4-1-83所示（因长槽孔一侧大、另一侧小）。  \n\n![](images/f6522269a24d5697843d03bd9feedd3628acee75bf30ea6e84bbe04ad7baec35.jpg)  \n图4-1-83SW60-1卧式砂磨机分散盘安装示意  \n\nc.出料机构 $60L$ 卧式砂磨机的出料机构，包括出料筛圈和缝隙式动态分离器。  \n\n出料筛圈的外形像一个鼓，故也称鼓形筛圈。在弧形面上沿轴向有很多条很窄的缝，其宽度有 $0.4\\mathrm{mm}$ 和 $0.\\ 6\\mathrm{mm}$ 两种，用户可根据研磨介质直径选用（一般取缝隙宽度不大于研磨介质直径的1/3)。其外形如图4-1-83右端所示。也有用圆筒形筛圈的。  \n\n该筛圈有三大优点：一是出料面积较大；二是用耐磨材料（如硬质合金）制成，硬度很  \n\n![](images/c6715956597e2fb94a0e4ddb129daf7f2880837a1ba80fac2ac902d62d0de274.jpg)  \n图4-1-84SW60-1卧式砂磨机机械密封部分结构  \n\n1一出料盘；2—调整垫；3—外刮刀；   \n4—小弹簧；5一压圈；6—静环；   \n7一静环密封圈；8一动环密封圈；   \n9一动环；10一内刮刀；11一防转销；   \n12—骨架油封；13—传动销；   \n14一油管；15一轴承保护圈（传动圈）  \n\n高，其窄缝用电火花法加工，经久耐用；三是不易被堵塞，因为筛圈快速旋转，且窄缝与旋转方向垂直，研磨介质粒子不易“塞”人此窄缝。  \n\n缝隙式动态分离器由内刮刀和外刮刀组成（见图4-1-84左端），也在出料。  \n\nd.机械密封卧式砂磨机的轴封，常用3种形式。对小容量砂磨机，可用结构比较简单的唇形密封圈密封（一般用2个密封圈)，对大容量砂磨机或腐蚀性强的介质或要求特别高时，首选双端面机械密封。但双端面机械密封结构复杂，成本高；介于上述二者之间，采用经改善端面润滑条件的单端面机械密封，也是一种可行的选择。$60L$ 卧式砂磨机就是这样做的，图4-1-84为其机械密封部分结构图（左端是一个缝隙式动态分离器)。  \n\n按照机械密封的分类方法，这套机械密封应称为外装、外流、旋转、平衡、多弹簧结构的单端面机械密封。与通常的单端面机械密封不同的是，它增加了一个骨架油封作为润滑液的动密封，从而改善了端面的润滑条件。可以用低黏度润滑油、煤油（必要时只好用溶剂）作润滑液。润滑液装在油箱内，借助由分散轴上偏心轮驱动的注油泵（隔膜泵）进行循环。油箱内设置了冷却盘管，可通水进行冷却。  \n\n由于介质压力和润滑液的压力都接近于零，在正常工作时，润滑液因黏度低并有渗透性，所以能克服离心力而渗入密封端面形成液膜。而介质（漆浆）中的溶剂也会渗入到密封端面中去，并有微量通过密封端面泄漏到润滑液中使润滑液改变颜色。因此，可以从润滑液的颜色间接地判断机械密封的泄漏情况。此外，如油箱油面窗液位下降，也表明润滑液泄漏。但润滑液的泄漏往往主要发生在骨架油封上，所以要经过检查分析，找出问题所在。  \n\n为了使密封效果好，寿命长，密封件材料的选用及质量至关重要。动环和静环采用硬质合金材料，两个O形圈及骨架油封选用氟橡胶材质，以防接触溶剂而溶胀。O形圈及骨架油封的质量一定要好，骨架油封的唇口不得有缺陷。  \n\n$\\textcircled{2}$ 主电机和传动部件主电机主要有隔爆型和封闭型两种，研磨分散含有有机溶剂的漆浆，须选用隔爆型。由于卧式砂磨机转速较高，只需用一级带传动就能把电机的转速降到需要的转速。  \n\n$\\textcircled{3}$ 机身机身为钢焊接构件，用来固定和支撑主机、主电机、送料系统及电器箱等部件。  \n\n$\\textcircled{4}$ 送料系统由送料泵和变速装置组成，与立式开启式砂磨机的送料系统基本相同。  \n\n$\\textcircled{5}$ 电气控制系统由电器箱、操作按钮板、电接点压力表和电接点温度表等组成。电接点压力表和电接点温度表分别对进料压力和出料温度进行检测和监控，以保证主机安全运行。主电机和泵电机的控制程序及对电器配置的要求，基本上与立式开启式砂磨机相同。  \n\n（2）产品的型号示例  \n\n$\\textcircled{1}$ 型号表示方法如SW60-1，S代表砂磨机代号，W代表卧式砂磨机，60代表筒体有效容积（L)；1代表设计序号。  \n\n$\\textcircled{2}$ 部分型号及基本参数国内卧式砂磨机的生产厂家很多，产品型号并不统一，规格繁杂。从已收集到的产品样本统计，砂磨机筒体容积从2.5L起，最大到 $250\\mathrm{L}$ ，其间5L、$15\\mathrm{L}$ 、20L、 $25\\mathrm{L}$ 、30L、 $40\\mathrm{L}$ 、45L、50L、60L、70L等规格都有厂家生产。对涂料行业来说，以 $15\\sim60\\mathrm{L}$ 较常用，使用效果也较好。原化学工业部标准《卧式砂磨分散机》（HG5-1618—1986）给出的SW系列砂磨分散机的基本参数见表4-1-14，供参考。  \n\n砂磨机的生产能力与物料性质、细度要求及研磨介质的密度、质量、装填量等因素有关，表中所列只是一个大致的范围。  \n\n$\\textcircled{3}$ 几点说明以生产卧式砂磨机时间较长的重庆地区为例，对一些产品及型号的演变，作几点说明。  \n\na.SW15-2砂磨机SW15-2型是在SW15-1型基础上改进的。首先是将唇式密封圈密封改为机械密封，提高了密封的可靠性和使用寿命；其次将出料方式由缝隙式动态分离器出料改为鼓形筛圈和缝隙式动态分离器共同出料，提高了分离研磨介质的能力。还优化筒体几何尺寸，将筒体长度增加 $25\\%$ ，分散盘由5个增加到6个，提高了设备的研磨分散能力。  \n\n表4-1-14SW系列卧式砂磨机的基本参数  \n\n\n<html><body><table><tr><td>基本参数</td><td>SW5</td><td>SW15</td><td>SW30</td><td>SW45</td><td>SW60</td><td>SW90</td></tr><tr><td>简体有效容积/L</td><td>5</td><td>15</td><td>30</td><td>45</td><td>60</td><td>90</td></tr><tr><td>主电机功率/kW</td><td>11</td><td>18.5</td><td>22</td><td>30</td><td>30</td><td>45</td></tr><tr><td>分散盘直径/mm</td><td>130</td><td>185</td><td>225</td><td>255</td><td>275</td><td>320</td></tr><tr><td>分散轴转速/(r/min)</td><td>1500~2300</td><td>800～1500</td><td>900~1200</td><td>800~1100</td><td>700~1000</td><td>600~800</td></tr><tr><td>泵电机功率/kW</td><td>1.1</td><td>1.1</td><td>1.1</td><td>1.1</td><td>1.5</td><td>1.5</td></tr><tr><td>泵流量调节范围/（L/min）</td><td>2~10</td><td>2~10</td><td>4~20</td><td>4~20</td><td>4~20</td><td>4~20</td></tr><tr><td>冷却水最大消耗量/(t/h)</td><td>1.5</td><td>1.5</td><td>1.5</td><td>2</td><td>2</td><td>2</td></tr><tr><td>生产能力/(kg/h)</td><td>12~120</td><td>30~300</td><td>50~500</td><td>70~700</td><td>100~1000</td><td>120~1200</td></tr><tr><td>物料黏度/Pa·s</td><td colspan=\"6\">≤10</td></tr><tr><td>分散细度/μm</td><td colspan=\"6\">≤20</td></tr></table></body></html>  \n\nb.SW60-1A砂磨机SW60-1A型是SW60-1型基础上改进的。一方面优化了筒体的几何尺寸，简体长度增加了25%，分散盘由7个增加到10个；另一方面将分散轴的转速由70lr/min、908r/min增至740r/min、1100r/min，提高了分散盘的圆周速度。这两项改进，大幅度地提高了设备的研磨分散能力。  \n\nc.WM系列卧式砂磨机（表4-1-15）在保留SW系列的同时，近年又推出WM系列，更适于处理黏度高、要求细度更小的产品。  \n\n表4-1-15WM系列卧式砂磨机技术参数  \n\n\n<html><body><table><tr><td>技术参数</td><td>WM20A</td><td>WM30A</td><td>WM40A</td><td>WM50A</td></tr><tr><td>简体有效容积/L</td><td>20</td><td>30</td><td>40</td><td>50</td></tr><tr><td>主电机功率/kW</td><td colspan=\"2\">22</td><td colspan=\"2\">30</td></tr><tr><td>分散轴转速/(r/min)</td><td>1160,1530</td><td>1000,1300</td><td>890,1160</td><td>800,1100</td></tr><tr><td>分散盘个数</td><td>9</td><td>11</td><td>12</td><td>13</td></tr><tr><td>泵最大供气压力/MPa</td><td colspan=\"4\">0.7</td></tr><tr><td>泵最大空气消耗量/(m/min)</td><td colspan=\"2\">0.3</td><td colspan=\"2\">0.6</td></tr><tr><td>冷却水最大消耗量/(t/h)</td><td colspan=\"2\">1.5</td><td colspan=\"2\">2</td></tr><tr><td>物料黏度/Pa·s</td><td colspan=\"4\">≤10</td></tr><tr><td>进料能力/(L/min)</td><td colspan=\"4\">0~17</td></tr><tr><td>生产能力/(kg/h)</td><td>40~400</td><td>50~600</td><td>0~40 70~700</td><td>100~1000</td></tr></table></body></html>  \n\nWM系列砂磨机采用气动隔膜泵送料；与SW系列相比，它的筒体较细长，同等容量下，用的分散盘较多，转速也略有提高。除表列规格外，近来有的厂家又推出WM5、WM15、WM60、WM90等品种。  \n\n（3）卧式砂磨机使用注意事项  \n\n$\\textcircled{1}$ 参照立式开启式砂磨机使用注意事项中的 $\\textcircled{1}$ ， $\\textcircled{3}$ ， $\\textcircled{4}$ ， $\\textcircled{5}$ 、 $\\textcircled{8}$ 和 $\\textcircled{9}$ 项。  \n\n$\\textcircled{2}$ 严禁开车时向筒体内添加研磨介质。  \n\n$\\textcircled{3}$ 由于安全装置（电接点压力表、电接点温度表）的作用而使设备停止运转时，必须查明原因，排除故障后才能重新开车，同时做好详细记录。  \n\n$\\textcircled{4}$ 要采取措施防止因物料结皮、干涸而使出料筛圈的狭缝堵塞，停车后要往筒体内注入溶剂清洗。如出料筛圈堵塞，要及时拆下清理。  \n\n$\\textcircled{5}$ 爱护设备，及时检查、维护。除参照立式开启式砂磨机部分的内容外，更换分散盘及撑套时要注意顺序位置和旋向，如不全部更换可将新件用在磨损严重处；机械密封润滑液（封液）按设备说明书选用，要特别关注机械密封在运行中有无泄漏。  \n\n（4）卧式砂磨机的优缺点  \n\n$\\textcircled{1}$ 优点  \n\na.与立式砂磨机相比较，容易启动，因而可以用密度大的研磨介质。  \n\nb.研磨介质装量大（装填系数高达 $70\\%\\sim90\\%$ ，研磨分散效率高。  \n\nc.清洗、换色、拆装方便。便于小批量、多品种生产。  \n\nd.卧式砂磨机全是密闭式的，可用于处理高黏度物料和高触变性物料。溶剂挥发少，有利于环境保护。  \n\ne.大多用鼓形筛圈和缝隙式动态分离器一起出料。出料面积较大且不易堵塞。  \n\nf.运转平稳，噪声小。  \n\n$\\check{\\mathbf{g}}$ 、不用地脚螺栓，无需专门的基础，安装、移动都方便。  \n\n$\\textcircled{2}$ 缺点  \n\na.研磨介质，特别是经磨损较小粒的，有向出料端集结的现象，尤其在研磨分散高黏度物料时，此现象更加严重。  \n\nb.由于是卧式，一定要设置可靠的轴封装置（大多用机械密封)，维修较困难且费用高。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1139,
+        "chunk": "# 4.卧式锥形砂磨机  \n\n卧式锥形砂磨机近年来发展较快，故从卧式砂磨机中独立出来专门叙述。与卧式砂磨机比较，它主要是筒体从圆柱形变为圆锥台形，相应的分散盘的外圆直径也呈锥形排列，而它的其他部分结构，与卧式砂磨机相同。  \n\n![](images/7d19d970cfca85abde63ecbe36ab2d627f0dce9a47edd90f0f48d3242f9681b2.jpg)  \n图4-1-85 卧式锥形砂磨机结构  \n\n1一物料人口；2—研磨介质加人口；3—外壳；4—简体；5—分散盘；6—冷却水通道；7—叠片式筛圈；8一机械密封；9—出料口；10一研磨介质放出口  \n\n(1）设备结构及其优点卧式锥形砂磨机的结构如图4-1-85所示。其筒体为圆锥台形，习惯上叫锥形，而且锥形的大头在进料口一侧，出料口在小头一侧。从进口到出口，分散盘的外径也逐渐缩小。  \n\n这种砂磨机在运转时，除了产生如图4-1-73所描绘的双环形滚动的流线外，研磨介质和密度大的粗大粒子因为离心力的作用以及甩向锥面后反弹的关系，有向锥体大头一端运动的倾向，消除了普通卧式砂磨机研磨介质向出料端集结的弊病，研磨介质沿砂磨机筒体轴向分布较均匀，加强了研磨分散的效果，同时也改善了出料装置和轴封的工作环境。  \n\n出料装置为叠片式筛圈[图4-1-86(a)]，其缝隙宽度可以调整。筛圈挡住了研磨介质，分散好的物料从轴中心流出。该机使用四叶状分散盘，其外形如图4-1-86（b）所示。  \n\n砂磨机可通水进行冷却，简体部分螺旋形通道提高了水的流速，强化了冷却效果。大头端盖上也能通水，增加了冷却面积。为防止端盖磨损，在其内侧覆盖了一层可更换的耐磨保护板。该机轴封采用双端面机械密封。  \n\n(2）产品的型号示例如SWZ25-1表示卧式锥形砂磨机，筒体有效容积为25L，1为设计序号。代表卧式锥形砂磨机的代号还有WSZ、ZWS、FM等。  \n\n![](images/412314690cc8508c939fe6f2ae7d359cbbba9f7acfb7853504c69add337feec4.jpg)  \n图4-1-86 出料筛圈和分散盘",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1140,
+        "chunk": "# 5.研磨介质  \n\n砂磨机依靠研磨介质工作，所以只有合理地选用高质量的研磨介质，才能充分发挥砂磨机的研磨分散能力。  \n\n（1）对研磨介质的一般要求选用的研磨介质，应具有适当的密度，粒径大小在合适范围内，外观看上去既光又圆，没有杂质和气孔，化学稳定性好，而最重要的是不易碎裂（在正确使用条件下）和耐磨性好。研磨介质的碎裂和磨损危害很大：因为要经常进行筛选、补充及更换，增加费用，耽误生产；研磨介质碎末不但影响产品细度和质量，而且损坏分散盘、筒体等砂磨机零件及输送泵，使砂磨机的出料和轴封装置不能正常运行。研磨介质的价格要比较低，起码要性能价格比合理。  \n\n(2）研磨介质的主要品种研磨介质的品种很多，天然砂、铬钢珠（密度为 $8\\mathrm{{g}/\\mathrm{{cm}^{3}}}$ 等都可以用作砂磨机的研磨介质，但目前常用的是玻璃珠和陶瓷珠。  \n\n$\\textcircled{1}$ 玻璃珠又分普通玻璃珠、增强玻璃珠（中性玻璃珠）和耐磨玻璃珠（氧化锆玻璃珠）等几种。普通玻璃珠系钠钙玻璃材质，比较便宜。目前应用较广的是增强玻璃珠，系硼硅酸盐玻璃材质，韧性好、耐磨、化学稳定性好，因 $\\mathrm{\\bf{p}H}$ 值为7.2，故又称中性玻璃珠，适合于中、低黏度物料的研磨分散。上述两种玻璃珠的密度为 $\\mathrm{2.45{\\sim}2.5g/\\mathrm{cm}^{3}}$ ，堆积密度约为 $1.5\\mathrm{g/cm^{3}}$ 。  \n\n耐磨玻璃珠（氧化锆玻璃珠）属钠钙锆系玻璃材质，近年研制。它的密度较大，为$\\mathrm{2.7{\\sim}2.8g/\\mathrm{cm}^{3}}$ （堆积密度约为 $1.65{\\sim}1.7\\mathrm{g/cm^{3}})$ ，且硬度、抗压强度及耐磨性均优于上述两种玻璃珠，适合于中、高黏度物料的研磨分散。玻璃珠还有一个共同的优点是其磨损产物是看不见的。  \n\n玻璃珠的规格（直径）范围为 $0.2{\\sim}5\\mathrm{mm}$ 。其间又分多挡，常用规格为 $0.8\\sim1.0\\mathrm{mm}$ $1.0{\\sim}1.5\\mathrm{mm}$ 1 $1.5{\\sim}2.0\\mathrm{mm}$ ， $\\mathrm{2.0{\\sim}2.5m m}$ 和 $2.5{\\sim}3.0{\\mathrm{mm}}$ 等几挡。  \n\n$\\textcircled{2}$ 陶瓷珠 主要有氧化铝陶瓷珠和氧化锆陶瓷珠。  \n\na．氧化铝陶瓷珠因 $\\mathrm{\\bfAl_{2}O_{3}}$ 含量不同，密度也不同，约为 $3.5\\sim3.9\\mathrm{g/cm^{3}}$ ，相应的堆积密度约为 $\\mathrm{2.0{\\sim}2.2g/\\mathrm{cm}^{3}}$ 中  \n\n氧化铝陶瓷珠硬度大，对机件的磨损比较厉害，自身磨耗也较大。目前在砂磨机上应用不多。  \n\nb.氧化锆陶瓷珠氧化锆陶瓷珠内部结构均匀细致，表面光滑，密度高，韧性好，耐冲击，磨耗低。其耐磨性大大优于玻璃珠和氧化铝陶瓷珠。  \n\n常用氧化锆陶瓷珠的化学成分， $Z\\mathrm{rO_{2}}$ 占 $68.5\\%$ ， $\\mathrm{SiO}_{2}$ 占 $31.5\\%$ 。其密度约为 $3.76\\sim$ $4\\mathrm{g/cm^{3}}$ ，堆积密度约为 $\\mathrm{2.3\\sim2.4g/cm^{3}}$ 。一种宜兴产品的规格（直径）有 $0.6\\sim1.0\\mathrm{mm}$ $0.8{\\sim}1.25{\\mathrm{mm}}$ 、 $1.0{\\sim}1.6\\mathrm{mm}$ 和 $1.6{\\sim}2.5\\mathrm{mm}$ 共 $4$ 档。  \n\n进口产品主要来自法国西普（SEPR）公司和以色列瑞米（RAMI）公司，产品资料称寸磨能力达到普通玻璃珠的 $5\\mathord{\\sim}10$ 倍，产品规格档次较多，然而价格昂贵。  \n\n还有一种纯氧化锆珠，俗称锆珠，其特点是密度大，表面光滑，耐磨性好，不易破碎。纯氧化锆珠的理论密度为 $6.09\\mathrm{g/cm^{3}}$ ，实际密度为 $5.9\\mathrm{g}/\\mathrm{cm}^{3}$ ，堆积密度约为 $3.5\\mathrm{g}/\\mathrm{cm}^{3}$ 9由于密度过大，使用较少。  \n\n（3）选择研磨介质的依据  \n\n$\\textcircled{1}$ 研磨介质的密度要根据物料的黏度、密度、固体含量及分散难易程度等因素综合 考虑，选择密度合适的研磨介质。显然，对黏度高、密度大、固体含量高及难分散的漆浆， 要用密度较大的研磨介质。如低黏度漆浆使用高密度研磨介质，无疑会导致过度磨损。  \n\n使用氧化锆陶瓷珠（密度为 $3.7\\delta\\mathrm{g}/\\mathrm{cm}^{3}$ )，法国西普公司对浆料黏度提出要求：一般建议立式砂磨机的浆料黏度不低于 $0.8\\mathrm{Pa}\\cdot\\mathbf{s}$ ，卧式砂磨机的浆料黏度不低于 $0.\\dot{6}\\mathrm{\\Pa\\cdot{\\s}}$ 。玻璃珠的密度一般不超过 $2.5\\mathrm{g}/\\mathrm{cm}^{3}$ ，只适用于中、低黏度的漆浆。  \n\n$\\textcircled{2}$ 研磨介质的粒径根据实验和生产经验，对不易分散或要求分散细度小的漆浆，要选用粒径小的研磨介质；对容易分散或对分散细度要求不高的漆浆，可适当选用粒径较大的研磨介质。粒径较大的长处是机械强度大，不易碎，磨损后仍可继续使用，有利于降低生产成本，提高生产的连续性。  \n\n当然，珠子的直径也不能太小，否则它具有的动能太小，不足以分离颜料聚集体。此外珠子太小，还容易堵塞筛网等出料装置。一般建议最小粒径要大于出口缝隙宽度的2.5倍。  \n\n在串联砂磨机或多筒砂磨机上，研磨介质可采用前粗后细的方案，逐台减小粒径，以求得到既快又好的综合效果。  \n\n目前常用玻璃珠的粒径大多在 $_{1\\sim3\\mathrm{mm}}$ 范围内。  \n\n$\\textcircled{3}$ 研磨介质的装填量砂磨机要装多少研磨介质才合适呢？若装入太少，即装填系数（研磨介质堆积体积与砂磨机筒体有效容积之比）太低，分散效率自然很低。但装得太多，即装填系数超过一定限度时，物料占据的容积减少，研磨介质自身及对机件的磨损加剧，物料温度猛升，主电机负荷加大，连送料泵的压力也升高，这样非但不能提高分散效率，反而无法正常开车。  \n\n研磨介质的装填系数与物料的黏度、分散盘（或棒销）的圆周速度及机器结构等因素有关。一般的经验是物料黏度高，分散盘（或棒销）的圆周速度高，装填系数应稍低，反之则取较高值。  \n\n通常立式开启式砂磨机的装填系数可取 $65\\%\\sim75\\%$ ，特殊情况下可取 $60\\%\\sim80\\%$ ；立式密闭式砂磨机因没有“冒顶”问题，装填系数可取 $80\\%\\sim85\\%$ ；卧式砂磨机启动容易，装填系数可比立式砂磨机大些，一般可取 $80\\%\\sim85\\%$ ，特殊情况下可取 $90\\%$ 量  \n\n确定装填系数后，就可算出研磨介质装填量 $(\\log)$ 。它等于砂磨机筒体有效容积（L)与装填系数及研磨介质堆积密度 $(\\mathrm{g/cm^{3}}$ 或 ${\\bf{k g}}/{\\bf{L}})$ 的乘积。一般来说，只要砂磨机的温升、功率消耗等指标在合适的范围内，适度加大研磨介质装填量，有利于提高砂磨机的生产能力。通过多次生产实践，就能找到相应工艺条件下理想的研磨介质装填量。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1141,
+        "chunk": "# 6.立式密闭式砂磨机  \n\n立式密闭式砂磨机和卧式砂磨机都是在密闭状态下带压操作，能在 $0,05{\\sim}0,3\\mathrm{MPa}$ 压力下强制出料，所以它能适应黏度高的物料和触变性物料。据化工行业标准HG/T2469一1993，立式密闭式砂磨机所处理的物料黏度小于 $\\mathrm{10Pa\\cdot_{s}}$ 8  \n\n根据出料方式不同，可将目前国产的立式密闭式砂磨机分为两种，一种是插入式窗式筛网出料方式，另一种是缝隙式动态分离器出料方式。  \n\n(1）用插人式窗式筛网出料的立式密闭式砂磨机这种砂磨机的代表机型是SB60-1（图4-1-87)，它与开启式砂磨机的主要区别有两处，一是出料的顶筛变成筒体侧面的圆形筛网，称插人式窗式筛网；二是在筒体顶部增设了轴封装置，即密封箱，使筒体可带压操作。  \n\n![](images/247f07e68fb51ba2585361b2074a9c21c5dc400e7d111383e7ecdf785e8c6dbf.jpg)  \n图4-1-87 立式密闭式砂磨机（用插人式窗式筛网出料）  \n\n1—轴承座；2—传动轴；3—弹性联轴器；4—密封箱；5—加砂口；6—视镜；7—温度计；8—出料口； 9—筛网；10—操纵板；11—分散轴；12—隔套；13—分散盘；14—送料泵调速手轮；15—薄膜压力传感器； 16—进料球阀；17—平衡轮；18—钢球无级变速器；19—送料（内齿）泵；20—水表；21—出水管  \n\n$\\textcircled{1}$ 关于出料筛网这种筛网一般面积较小出料阻力大，由于是静态出料，容易堵塞，特别是在分散黑浆和蓝浆时。再一个缺点是由于筛网在侧壁，受研磨介质磨损很厉害。  \n\n$\\textcircled{2}$ 关于密封箱密封箱上部为轴承座，内装2只轴承，以防分散轴摆动。密封箱下部安装一套双端面机械密封。机械密封浸在密封箱内的封液中，封液表面通人空气或情性气体（由空压机或气体钢瓶提供)，使其压力略大于砂磨筒内物料压力。密封箱内还有盘管，可通水冷却。这种砂磨机机械密封的工作条件很恶劣，因为它要密封的液体是带压的漆浆，漆浆内有大量的颜料粒子和破碎的研磨介质碎粒（碎砂)，它们大多很硬，而且是“无孔不人”。它们能钻入运动零件与静止零件之间的各处间隙中，把各种零件磨坏，使机械密封失效。  \n\n由于出料筛网和机械密封都存在难以解决的问题，这种砂磨机已很少应用。  \n\n（2）用缝隙式动态分离器出料的立式密闭式砂磨机  \n\n$\\textcircled{1}$ 概况图4-1-88为此类砂磨机的结构。缝隙式动态分离器设置在简体中心部位的顶端，它由转子和定子组成，与机械密封的动环和静环不同的是转子与定子不接触，而是保持一定的较小的缝隙。图中为平面缝隙，也可以做成锥面缝隙，缝隙的大小可以调节，一般取值为研磨介质直径的1/3左右。由于转子随分散轴同步旋转，所以此缝隙不会堵塞，故称之为动态分离器，其缺点是出料面积较小。还有一种径向缝隙可用来出料，缝隙大小事先设定，不可调节。  \n\n经研磨分散的漆浆，在由送料泵提供的压力作用下，从这个动态的缝隙中“挤”出来，从出口排出。因缝隙较小，流动阻力大，漆浆的压降大，如漆浆出口尺寸较大，又通大气，则位于最上方的轴封装置，基本上不受压。因此，轴封装置除采用机械密封外，还可采取较简单的软填料密封或皮碗密封（也叫唇形密封圈密封）等方式。  \n\n![](images/97c4a0060df3ed97544883789edb5bd5b04f41cd36a58c0559cfd3e32d588a1b.jpg)  \n图4-1-88缝隙式动态分离器出料的 立式密闭式砂磨机示意 1一缝隙式动态分离器；2一机械密封； 3—分散盘；4—底阀  \n\n这种结构的砂磨机，虽然轴封装置的处境有些好转，但对缝隙式动态分离器的要求是很高的，因分离器的缝隙，既要能出料，又要挡住研磨介质，故要求这个缝隙在分散轴转动过程中，应保持间隙一致，否则如果这个间隙时大时小，就会把进入这个间隙内的碎研磨介质研碎。为此，要求分散轴要有很高的运转精度，以及各有关零件要用很硬的耐磨材料制造，并经精密加工、安装等。  \n\n为了加大出料面积，缝隙式动态分离器常与装在分散轴上的出料筛或出料筛圈联合出料。  \n\n$\\textcircled{2}$ 选用注意事项  \n\na.鉴于国产立式密闭式砂磨机起步较晚，成功的经验较少，故在选用时要格外谨慎，除听取制造厂商介绍外，最好能了解现场使用情况。  \n\nb.在选型时，要搞清砂磨机的主要结构，重点是出料结构和轴封结构。使用缝隙式动态分离器出料的砂磨机，其轴封承受的压力小，轴封的结构可简单一些；使用插入式窗式筛网出料的砂磨机，其轴封承受的压力大（一般不超过0.3MPa)，轴封结构要复杂些，大多采用双端面机械密封，外加一些阻挡研磨介质的措施。当砂磨机处理量较大时，只用缝隙式动态分离器，出料面积往往偏小，需附加一些其他的出料措施。  \n\nc.材质的选择主要指砂磨机内筒和分散盘材质的选择。材质的选择要考虑耐磨及不掉色（即在研磨分散浅色漆浆时不影响色泽)。对立式密闭式砂磨机来说，结构的合理与否比材料的耐磨与否更重要。  \n\nd.要选用质量高、耐磨、不易碎的研磨介质。碎的研磨介质会影响出料机构和轴封的正常工作，要经常予以清除或适时更换研磨介质。  \n\ne.无论在选型或使用中，都要关注冷却问题。冷却水要有足够的压力和较低的温度，要采取各种措施（如降低进料黏度、减少研磨介质装填量)，保证漆浆的出口温度不超过工艺许可的温度。对一些高黏度物料，只依靠降低冷却水温度往往不能满足工艺要求，此时需要加大冷却面积，如增加分散轴中心冷却。  \n\nf.在操作中要经常检查轴封有无泄漏，工作是否正常。如为双端面机械密封，要选好合适的封液，保证封液的良好循环或封液液面上必需的压力。  \n\ng.要关注出料结构的工作情况。筛网等的堵塞会导致砂磨机内压力升高，分散轴的异常摆动可能使缝隙式动态分离器研碎研磨介质。出现这些情况要停车，等排除故障后再启动。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1142,
+        "chunk": "# 7.棒销式砂磨机  \n\n棒销式砂磨机因其搅拌部件不是分散盘而是短圆柱状的棒销而得名。因为棒销一般较短因而加大了分散轴直径，相应地缩小了定子（砂磨机筒体）与转子（分散轴或轴套)之间的距离，换言之，即棒销式砂磨机的磨室缝隙宽度要比使用分散盘的砂磨机小很多，因而磨室内的能量密度分布比较均匀，使研磨分散产品能获得较窄的粒度分布，这正好是高档漆产品所必需的性能。同时，磨室内的能量密度也显著提高，研磨分散的效果随之增强。  \n\n（1）棒销式砂磨机的工作原理在棒销式砂磨机的筒体内，高速旋转的转子连同旋转棒销带动物料和研磨介质运动，而筒体及固定棒销是静止的，物料一边伴随研磨介质旋转，一边被送料泵推动向出口流动，在这个过程中，物料受到强烈的撞击和剪切作用而被分散。  \n\n分散作用主要发生在旋转棒销与固定棒销间，在很小的距离内有很大的速度差（旋转棒销外端线速度一般为 $5\\sim8\\mathrm{m}/\\mathrm{s})$ ，这个大的速度梯度产生很大的剪切力，促成了物料分散。从图4-1-89中可看出旋转棒销前进时物料流动流线的变化及产生的许多旋涡。  \n\n另外，在旋转棒销端部与筒体间，也存在速度梯度对物料起分散的作用。  \n\n![](images/d421902a2233d496d78c19282dba303f881acc654e62f0fce812acf98639c895.jpg)  \n图4-1-89 棒销与物 料流动示意 1一旋转棒销；2一固定棒销  \n\n(2）棒销式砂磨机的结构棒销式砂磨机有立式、卧式、卧式锥形等多种形式，现以立式为例说明其基本结构。图4-1-90是棒销式立式密闭砂磨机结构示意，旋转棒销装在圆环上，圆环装在分散轴上。在筒体上装有固定棒销（试验表明，如无固定棒销，分散效能大大降低)。另有一种结构是旋转棒销直接装在转子上，如图4-1-91所示。从图中可看出棒销在各个方位的布置情况。由于棒销在研磨介质中运转，所以要用很硬的耐磨的材料（如硬质合金）制造，并在其磨损后能方便地予以更换。  \n\n![](images/25b06743d7232465affb68224fd9d71f874489c4e3b48d8d752314fd274a1ac4.jpg)  \n图4-1-90 棒销式立式密闭砂磨机  \n\n1-漆浆人口；2—圆环；3—旋转棒销；4—固定棒销；5—简体；6—缝隙式动态分离器；7—漆浆出口  \n\n这种砂磨机结构上的一个特点是除了简体夹套可通水冷却外，其分散轴中心也可通水冷却，这一点对于散热较差的高黏度物料及热敏性物料尤为重要。此外，与普通砂磨机相比，它的有效容积减小，使用的研磨介质也少了，换色、清洗都比较方便。  \n\n![](images/46253783659a8da94c3d763a9db663a6eb85ab3213328a4e067e9f2bcdf9b497.jpg)  \n图4-1-91 棒销布置  \n\n棒销式立式密闭砂磨机的其他结构，与一般立式密闭砂磨机大同小异。出料可用缝隙式动态分离器，或再加上筛圈等装置，以加大出料面积，也可用筛网出料。  \n\n(3）可变容积的棒销式砂磨机 这种砂磨机是在原有立式、卧式或卧式锥形的棒销式砂磨机的基础上，增加了可调筒体容积的结构。  \n\n$\\textcircled{1}$ 立式图4-1-92所示为可变容积的棒销式立式砂磨机。在筒体底部有一个活塞，活塞上镶嵌着一个密封圈作活塞环用，活塞上下移动，随即改变了筒体的容积。活塞上密封圈既不能妨碍活塞移动，又要阻挡物料和研磨介质漏下来，所以对其材质有较高的要求，密封圈在物料中要不被腐蚀、不溶胀。  \n\n![](images/5bc8503bf8fa08946ca385b875dbc7d0d385ac547d8faed79f2e2a304e41f2b1.jpg)  \n图4-1-92 可变容积的棒销式立式砂磨机  \n\n驱动活塞的加压系统一般用液压来控制。与活塞联成一体的是油缸活塞，油缸活塞上镶嵌着耐油的密封圈，液压油带动油缸活塞移动，也就同步带动了活塞移动。  \n\n改变简体容积主要起两个作用：  \n\na.减少磨室内研磨介质装填量，有利于砂磨机启动，这一点对高黏度物料及高密度物料尤为重要；b.改变磨室内研磨介质的装填系数，可适应不同的分散要求。如对于难分散的物料，一般需要较高的研磨介质装填系数。图4-1-92中，活塞不同位置的3个图形，比较形象地显示出可变容积所起的作用。  \n\n②卧式图4-1-93为KWS-25C棒销式卧式砂磨机。该机筒体容积可变，转动手轮可移动活塞，从而改变筒体容积（容积可调范围为20～25L)。该机采用缝隙式动态分离器出料，轴封系双端面机械密封。该机结构上的又一特点是设置了双水内冷系统，除传统的定子（筒体）冷却外，肥大的中空转子也能通水冷却，也制成与定子相似的螺旋槽流道，因而即使在高生产率时，也能使筒体内温升不致太大。  \n\n![](images/559f7d75fd4e1b180525fe36ec3a4a46ca1ec0918b9278a5acdea945e85e241e.jpg)  \n图4-1-93KWS-25C卧式砂磨机结构1—物料人口；2—活塞；3一转子冷却系统；4—定子冷却系统；5—动态分离器；6—机械密封；7—物料出口  \n\n（4）立式双层棒销式砂磨机（见图4-1-94）  \n\n$\\textcircled{1}$ 结构该机的研磨室主要由可调速的内冷却转子、带夹套的定子及动态分离器组成。  \n\n转子为圆柱罩形结构，其外侧排列着很多棒销，定子的外层内侧和内层外侧也排列着很多棒销，转子垂直放置在定子的内、外层之间，形成内、外两个研磨室。在转子上部，设有动态分离器。棒销用高硬度耐磨材料制成，采用螺纹连接予以固定。  \n\n工作时，漆浆由送料泵从中心送人，先后经过内、外两个研磨室的研磨分散，然后从上部通过动态分离器过滤，从出口流出。而研磨介质经转子上的螺旋回流槽，返回内研磨室，形成闭路循环。  \n\n这种砂磨机要用质量高、比较耐磨的研磨介质，粒径范围为 $0.2{\\sim}2\\mathrm{mm}$ 中  \n\n$\\textcircled{2}$ 该机的一些特点  \n\na.磨室缝隙宽度较小，能量密度高，因而研磨分散效率高，能用来加工炭黑等难以分散的颜料和细度要求较高的漆浆。  \n\nb.狭缝型磨室结构耗用的研磨介质少，筒体残留物也少，换色、清洗消耗溶剂少，使用成本低，  \n\nc，定子和转子都能冷却，冷却效果好。  \n\n![](images/75de99ca64cbda6fecc144a9015de3f2a2c509667e8b255e1e43e2a19dada501.jpg)  \n图4-1-94 立式双层棒销式砂磨机  \n\nd.主机采用变频调速，实现软启动，以达到高效、节能的效果。  \n\ne.研磨筒体（定子）采用耐磨的高合金钢，不会污染产品，而且内胆可以更换，附设手动液压系统，便于拆装、清洗。  \n\n③其他机型立式双层棒销式砂磨机除上述转子外侧、定子外层内侧和定子内层外侧共3个面上有棒销的结构外，还有2种结构：一种是转子外侧和内侧、定子外层内侧和定子内层外侧共4个面上都有棒销，这种机型结构复杂，能量密度高，如12L容积的砂磨机配用电机功率达36～45kW；另一种只有转子外侧和定子外层内侧共2个面上有棒销，内研磨室只是2个光面组成的环状窄缝，称简形剪切区。物料和研磨介质先经过外研磨室再到内研磨室，在向上流动（层流）过程中受到剪切力作用，有助于物料的磨光并均匀分散。  \n\n（5）关于型号及选用注意事项  \n\n①型号棒销式砂磨机种类很多，结构复杂，无论引进的或国产的，近年才逐渐多起来。国产机型目前品种不多，型号也不统一。有的制造厂将棒销式并入密闭式砂磨机内，不另给型号，只是在密闭式砂磨机中，注明分散盘式和棒销式两种。  \n\n②棒销式砂磨机选用注意事项棒销式砂磨机结构比较复杂而又独特，磨室内能量密度又高，所以它的磨损及发热都很厉害。除要恪守立式密闭式砂磨机的选用注意事项中的每一项外，更要着重注意下列事项。  \n\na.选用的必要性只有因物料黏度高，要求细度小且有窄的粒度分布等条件，其他砂磨机难以胜任时，才选用棒销式砂磨机。  \n\nb.研磨介质棒销对研磨介质的冲击显然要比分散盘厉害得多，所以一定要选用好的、耐用的、密度较大的研磨介质。  \n\nc.筒体及棒销材质不只是棒销，连筒体的磨损都很严重，所以棒销和筒体都要用高耐磨材料制作。近年又有内衬耐磨陶瓷的筒体问世，不但耐磨，而且无金属离子污染，使研磨产品不变色，更纯净。缺点是造价很高。  \n\nd.冷却结构除夹套冷却外，最好还要有转子中心冷却装置，必要时通冷冻水冷却，还要选用质量好的旋转接头。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1143,
+        "chunk": "# 8.循环卧式砂磨机  \n\n（1）循环卧式砂磨机的结构及流程图4-1-95为LMZ系列大流量循环卧式砂磨机结构及流程。这种砂磨机是德国耐驰（NETZSCH）公司开发的专利产品。该系统由棒销式卧式砂磨机、搅拌槽及循环泵组成。砂磨机在工作时，用泵进行大流量的循环。由于搅拌槽有冷却面积很大的水冷夹套，且槽内又有一个与槽壁间距很小的框式搅拌器在搅动，加上管路的散热，使物料能得到极好的冷却。同时，砂磨机筒体仍有水冷夹套可冷却，必要时，砂磨机的转子还可以通水冷却。  \n\n![](images/f3998c2e2a3021541aaafb001c95a3c5780342d8a7fcf4fc968d94e595ee7318.jpg)  \n图4-1-95 循环卧式砂磨机  \n\n1一搅拌槽；2-物料进口；3-三通阀；4-泵；5-卧式砂磨机；6-物料出口PIS一压力指示开关；TIS一温度指示开关；SIC一转速指示、调节；WQIS一质量积算、指示、联锁；EQIS一能量积算、指示、联锁  \n\n（2）循环卧式砂磨机的特点  \n\n①除砂磨机本身冷却外，采用了外循环冷却措施。所以特别适合研磨分散对温度敏感的产品。  \n\n②它的出料结构采用了受专利保护的转子-缝隙筒分离装置，它位于高速旋转的转子内，过滤面积比一般砂磨机大得多，适用于大流量循环研磨分散工艺。带棒销的转子上，在棒销间开有若干条纵向长槽，研磨介质在离心力的作用下经这些长槽被抛向转子外边而不与缝隙筒接触，所以缝隙筒不易被研磨介质堵塞，也不易磨损，从而大大延长了缝隙简以及砂磨机机械密封的寿命。  \n\n$\\textcircled{3}$ ③可使用较小尺寸的研磨介质，研磨分散效率高，产品细度好。  \n\n④提高砂磨机的流量，缩短了物料颗粒在砂磨机内停留时间，从而使循环运行的工作方式得以实现，这样使产品的粒度分布范围变窄，提高了产品的质量档次，满足了像汽车高级面漆等高档产品的要求。  \n\n③产品能耗参数可以预先输人。操作时能量消耗达到设定值时，产品即已达到了要求的细度，自动停机，操作控制简单，产品质量重复性高。  \n\n③对于一些难分散的颜料，在传统的砂磨机中很难做到充分分散。而在循环卧式砂磨机中，经过多次循环可以将其彻底分散。从而提高了颜料的遮盖力，节约颜料用量。  \n\n(3）循环卧式砂磨机的主要型号及技术参数（见表4-1-16)。  \n\n表4-1-161 LMZ系列循环卧式砂磨机的主要型号及技术参数  \n\n\n<html><body><table><tr><td>型号</td><td>LMZ2</td><td>LMZ4</td><td>LMZ10</td><td>LMZ25</td><td>LMZ60</td><td>LMZ150</td></tr><tr><td>简体容积/L</td><td></td><td>1.6</td><td>4 10</td><td>25</td><td>62</td><td>151</td></tr><tr><td>主电机功率/kW</td><td></td><td>4 13.5~15</td><td>17.5~22</td><td>36~45</td><td>70~90</td><td>160~256</td></tr><tr><td>加工批量/L</td><td>10</td><td>100</td><td>500</td><td>2000</td><td>>2000</td><td>>4000</td></tr><tr><td>转速/(r/min)</td><td>1200~2500</td><td>600~1800</td><td>700~1300</td><td>700～1000</td><td>500～640</td><td></td></tr><tr><td>质量/kg</td><td>280</td><td>600</td><td>1300</td><td>2000</td><td>3500</td><td>6800</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1144,
+        "chunk": "# 9.篮式砂磨机  \n\n篮式砂磨机是一种新型的间歇操作的砂磨机，近年来在国内涂料生产中的应用逐渐增多。由于它的主要工作部件像个圆形篮子，故形象地称之为篮式砂磨机。按篮子在进行分散作业时的运动状态，可将篮式砂磨机分为篮子静止型和篮子旋转型两大类。因为目前国内生产和使用的大多是篮子静止型砂磨机，所以通常说的篮式砂磨机是指静止型的。  \n\n(1）篮子静止型篮式砂磨机  \n\n① 结构和工作原理篮式砂磨机的结构和工作原理如图4-1-96所示。该机主要由主电机、机身、操纵按钮板、传动部件、分散轴、篮子、分散棒、搅拌桨、液压升降系统、温度控制系统及与之配套的带水冷却夹套的活动漆浆罐组成。  \n\n![](images/179a7c66c394196ea6b2880ac5eadf2624bcf25669284e29f9884be33ceff754.jpg)  \n图4-1-96 篮式砂磨机  \n\n1一篮子；2—带水冷却夹套的活动漆浆罐；3—分散轴；4一传动部件；5-温度控制系统；6—主电机；7—操纵按钮板；8一机身；9一液压升降系统；10一分散棒；11一搅拌桨  \n\n篮式砂磨机的外形像高速分散机。用油压升降的机头上固定着一个篮子，工作时篮子浸没在活动漆浆罐的漆浆中。篮子与活动漆浆罐斜底的最小间距必须大于50mm，篮子外侧表面及底面系特制的筛网。筛网用断面为等腰梯形的耐磨金属窄条焊成。间隙呈内小外宽，小处间隙宽约0.5mm。研磨介质装在篮子里，由旋转的分散棒带动运动。常见的分散棒分两层，共8个，相互交叉布置。分散棒要非常耐磨，常用硬质合金或聚四氟乙烯(内有钢芯)制成，后者不及前者耐用，主要用于浅色漆浆。  \n\n工作时，受到离心力的作用，研磨介质和漆浆一起被甩出，研磨介质被筛网截留，在篮内又绕回到中心部位，形成循环。漆浆的流动如图4-1-96中箭头所示。篮子底部有搅拌桨，被分散轴带动旋转，将漆浆向下压向罐底，尔后从外围返回到篮子上部。再次从篮子上部中心环形区吸人，并从底部及侧面排出。漆浆在篮子里受到研磨介质的冲击和摩擦，起到研磨分散作用，直至达到要求的分散细度后，停止作业。  \n\n篮式砂磨机大多采用无级调速，分散轴转速可在设计范围内随意调节。一般都是低速启动，逐渐加速到形成旋涡的良好流动状态。在调整转速的同时，还可以调整篮子位置的高低，以活动漆浆罐罐边漆浆液面基本上成一平面，而不是成波浪形面为好。  \n\n活动漆浆罐的罐体及斜底（以利放净）上有夹套，要确保冷却水通畅，以除去研磨分散作业中产生的热量。该机设置了温度控制系统。当漆浆温度达到事先设定的最高允许温度时，主电机将自动切断电源。  \n\n$\\textcircled{2}$ 产品的型号示例目前，无论是从国外引进或是国产的篮式砂磨机，其主要型号是SS-20（引进）和LS-20（国产)，它们基本上是相同的。  \n\nLS-20表示篮式砂磨机，篮子的有效容积为 $20\\mathbb{L}$ 。它的主要技术参数如下：主电机功率为 $15\\mathrm{kW}$ 或 $22\\mathbf{kW}$ ；调速方式为变频调速或电磁调速电机调速；分散轴转速为 $63\\sim630\\mathrm{r/}$ min；活动漆浆罐最大容积为500L（混浆容量约为 $200\\sim400\\mathrm{L})$ ；机头升降行程为 ${\\mathfrak{g o o m m}}$ 0油泵电机功率为 $0.75\\substack{\\sim}1.1\\mathbf{k}\\mathbf{W}$ ；整机质量约为 $2500\\mathrm{kg}$ 0  \n\n此外，LS-10和LS-40两种型号也已有厂家生产，其主电机功率为11kW和 $30\\mathbf{kW}$ 中  \n\n$\\textcircled{3}$ 篮式砂磨机使用注意事项  \n\na.开车前应对设备、电器、仪表、冷却水及研磨介质等做充分检查和准备。  \n\nb.配制漆浆时，对炭黑等难以分散的颜料，宜用溶剂提前一天预先浸泡，使颜料得以充分湿润，第二天再加漆料和分散剂，用高速分散机进行预分散。  \n\nc.此砂磨机可进行自动定时操作，定时值按工艺要求或经验确定。定时范围为 $1\\sim5\\mathrm{h}$ 口  \n\nd.当篮子没有浸人漆浆里时，不能高速转动分散轴，否则将造成研磨介质破碎以及下部滑动轴承发热和磨损。  \n\ne.每次操作完毕，应将分散轴的转速调到最低后再停车，以保证分散轴在下次操作时能在低速状态下启动。  \n\nf.分散结束后，升高篮子，拉走活动漆浆罐，然后分别用漆料和溶剂清洗篮子和研磨介质。当用溶剂清洗时，分散轴转速不应过高，以免研磨介质磨损。篮子清洗完毕后，宜用干净溶剂浸没篮子，以免篮子内的残余漆浆干涸结皮。  \n\ng.如因超温自动停机时，应先按消除按钮，并相应做好处理后（如适当调高温度计读数或解决冷却水源等)，再重新慢速启动分散轴。  \n\nh.适当提高漆浆的黏度，有利于提高产量。  \n\ni.应经常检查研磨介质的磨损情况，检查的方法是取走篮子上面的两件活动盖，用手插入研磨介质中，如果手上沾了较多的碎珠，说明研磨介质的磨损已有相当程度，就要放出篮子里的研磨介质，重新装上经筛选过的其他研磨介质。放出的研磨介质用溶剂清洗干净，过筛，除去杂质、碎片和小于规格的粒子，留待下次使用。  \n\nj.经检查发现篮子内的研磨介质已经减少，不要简单地往篮子内添加，而应把研磨介质放出，重新加入合乎要求的研磨介质。放出的研磨介质清洗、筛选后留待下次使用。LS-20型篮式砂磨机约装 $15\\sim20\\mathrm{kg}$ 玻璃珠（粒径 $1.5\\sim2\\mathrm{mm}$ ）或 $30\\mathbf{kg}$ 氧化锆陶瓷珠（粒径$0.8{\\sim}1.2\\mathrm{mm};$ 。  \n\n$\\textcircled{4}$ 篮式砂磨机的优缺点a.优点  \n\n$\\cdot$ 利用活动漆浆罐进行配料拌和和研磨分散，无需送料泵和连接管路，特别适用于小批量、多品种的生产。  \n\n$\\cdot$ 工作时转速大多不高，机器运转平稳，噪声小。  \n\n$\\cdot$ 整机的附属设备少，因而检修工作量也小。  \n\n$\\cdot$ 对研磨介质的清洗和更换十分方便。篮子提起后，里面残留的漆浆少，减少了物料损失。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1145,
+        "chunk": "# b.缺点  \n\n$\\cdot$ 间歇生产。  \n$\\cdot$ 由于分散棒和篮子磨损较大，要用耐磨的材料制造，篮子的制造难度较大。  \n\n（2）篮子旋转型篮式砂磨机  \n\n$\\textcircled{1}$ 结构和工作原理 篮子旋转型篮式砂磨机的结构和工作原理如图4-1-97所示。该机结构的特点是采用了特殊的空心轴结构。进行分散作业时，空心轴4带着篮子1旋转，位于篮子内的磨盘2不动。漆浆从上部和下部吸人装有研磨介质的篮子内，受到离心力的作用，漆浆和研磨介质一起被甩出。漆浆通过篮子的缝隙，分上、下两路进行循环。如图4-1-97中箭头所示。篮子由上、下网板及周边网圈组成。总之，篮子上所有的缝隙都不许研磨介质粒子通过。于是，被甩出的研磨介质在周边网圈处碰壁后又绕回到中心部位，形成循环。  \n\n篮子外周边可加装螺带状叶片，加强活动漆浆罐内漆浆的流动，以适应黏度较高的产品。活动漆浆罐上可加密封盖，以减少溶剂挥发。  \n\n$\\textcircled{2}$ 篮子旋转型篮式砂磨机的特点除了也有上述篮子静止型篮式砂磨机的优缺点外，它还有以下特点。  \n\na.清洗更方便，便于换色或换产品产品细度达到要求后，将篮子提升出液面，由于篮子可旋转，可甩净篮子内残留的漆浆。在用漆料或溶剂清洗时，篮子和磨盘以同方向不同的转速旋转，由于没有静止件，所以清洗彻底。篮子表面的杂物在离心力作用下容易被甩出或被洗刷下来。  \n\n![](images/a4dea7b5e7b4fb8462b4010cf2d24d00b9692a049f66458124f9c46cd720764c.jpg)  \n图4-1-97篮子旋转型篮式砂磨机1—篮子；2—磨盘；3—带水冷却夹套的活动漆浆罐；4一空心轴；5—中心轴；6一密封盖  \n\nb.清洗时磨损小由于篮子和磨盘同向旋转，清洗时对研磨介质和机件的磨损都较小。$\\textcircled{3}$ 产品的型号示例目前该机未见国产品种。德国耐驰（NETZSCH）公司TM系列的主要型号为TM2、TM8、TM50和TM80，其主电机功率为 $1.5\\mathrm{kW}$ ， $7.5\\mathrm{kW}$ 、 $37k W$ 和 $75k W$ 0",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1146,
+        "chunk": "# 10.三辊磨  \n\n辊磨因辊简数目不同而分为单辊磨、双辊磨（炼胶机)、三辊磨和五辊磨等几种。  \n\n三辊磨也称三辊机、三辊研磨机、三轴磨等，在辊磨家族中，它是应用最多的一种。  \n\n(1）三辊磨的结构三辊磨的主要部件为安装在机体上的3个辊筒。3个辊筒的排列以水平布置居多。两个辊筒间的距离可根据工艺要求进行调节。一般是中辊在机体上固定，前辊（出料侧）和后辊（加料侧）都可以分别在机体的导轨上前后移动，进行调节。调节的方法可以手动(通过手轮和螺杆)，也可以用液压调节。液压调节的三辊磨结构比较复杂，但调节方便，液压值能显示，减轻了操作的劳动强度。  \n\n除辊筒部件外，组成一台三辊磨还有机体、传动部件、调节部件、加料部件、出料部件、冷却部件、电器仪表及操纵系统等。  \n\n(2）三辊磨的工作原理在三辊磨中，颜料的研磨分散是从往慢辊与中辊之间的空间放人漆浆开始。由于辊筒向内转动，漆浆被拉向加料缝处。由于间隙越来越小，大部分漆浆都不能通过，被迫回到加料沟顶部，然后再一次被向内转动的辊筒带下去，形成在加料沟内不断翻滚，做循环流动，加料沟内这种循环流动，产生相当强的混合和剪切作用。而更强烈的剪切作用发生在通过加料缝的瞬间，因为加料缝的间隙很小（约 $10\\sim50\\mu\\mathrm{m})$ ，且相邻的两辊筒有一个速度差。此时，漆浆中的颜料团粒破裂，被分散到漆料中。通过加料缝的漆浆，小部分黏附在慢辊上，并回到加料沟。大部分黏附在中辊上，进人中辊与快辊之间的刮漆缝。  \n\n在刮漆缝，由于间隙更小，且快辊与中辊的速度差更大，故漆浆受到更为强烈的剪切作用，颜料团粒又一次被分散。通过刮漆缝的漆浆，小部分回到中辊，大部分转向快辊，最后被刮刀刮至刮刀架（出料斗)，流人活动漆盆。若分散细度未达到要求，可再次循环操作，直到合格为止。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1147,
+        "chunk": "# (3）产品的型号示例  \n\n$\\textcircled{1}$ 型号表示方法如目前使用较多的S405型，S代表系列三辊磨，其辊筒直径为 $405\\mathrm{mm}$ 0$\\textcircled{2}$ 部分型号及基本参数目前国内三辊磨生产厂家并不多，部分上海产三辊磨的型号及基本参数见表4-1-17。  \n\n表4-1-17 三辊磨的基本参数  \n\n\n<html><body><table><tr><td>基本参数</td><td>QH3E400</td><td>SM405</td><td>S405</td><td>S260</td><td>S150</td><td>S100</td></tr><tr><td>辊简直径/mm</td><td>400</td><td>405</td><td>405</td><td>260</td><td>150</td><td>100</td></tr><tr><td>辊筒工作面长度/mm</td><td>1300</td><td>810</td><td>810</td><td>675</td><td>300</td><td>250</td></tr><tr><td>快辊转速/(r/min)</td><td>400</td><td>135.5</td><td>116</td><td>155.3</td><td>148</td><td>251</td></tr><tr><td>液压系统压力/MPa</td><td>6.17</td><td>一</td><td>一</td><td>一</td><td></td><td>一</td></tr><tr><td>主电机功率/kW</td><td>55</td><td>15</td><td>15</td><td>7.5</td><td>2.2</td><td>1.1</td></tr><tr><td>质量/kg</td><td>5120</td><td>5200</td><td>5000</td><td>2368</td><td>713</td><td>350</td></tr></table></body></html>  \n\n国内其他厂家的三辊磨产品系列，基本上与此表相似。只是有的厂家，多出一种实验室用小三辊磨，其型号为S65，其技术参数为：辊筒直径 $65\\mathrm{mm}$ ；辊筒工作面长度 $\\mathtt{l23m m}$ ；快辊转速约 $250\\mathrm{r/min}$ ；电机功率 $0.75\\mathrm{kW}$ 。另外，近来又有辊筒直径 $260\\mathrm{mm}$ 和 $\\mathbf{150mm}$ 的全液压三辊磨面世。  \n\n（4）三辊磨的优缺点  \n\n71$\\textcircled{1}$ 优点a.能加工黏度很高的漆浆。b.适宜于对含有难分散颜料的漆浆进行分散。c.换色、清洗方便，特别适合小批量、多品种生产和研制。d.研磨分散质量高，能达到较高的细度，从而充分发挥颜料的着色力、遮盖力等特性，节省颜料用量。$\\textcircled{2}$ 缺点a.生产能力低。b.溶剂挥发大，不但浪费物料，而且污染环境，损害工人健康。c.机器庞大复杂，辊筒表面加工精度高而且需要中高，需要专门机床加工，维修、保  \n\n养技术要求高。  \n\nd.操作技术要求高，手工操作劳动量大，难以实现机械化。e.分散磨蚀性强的颜料时，辊筒表面被严重磨损。f.操作安全性差，容易造成人身或设备事故。所以要严防杂物、工具等落入运转的辊筒间或落人后用手取物，严防辊简夹手，严禁戴手套操作。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1148,
+        "chunk": "# 11．球磨机  \n\n目前涂料生产用的球磨机有卧式球磨机和立式球磨机两种，其中卧式球磨机应用较多。平常不指名说球磨机，就是指卧式球磨机。按操作方式，它们都属于间歇式。  \n\n（1）卧式球磨机  \n\n$\\textcircled{1}$ 设备结构和工作原理球磨机由一个可旋转的水平状圆筒及内装的钢球等研磨介质组成。球磨机在运转时，圆筒中的球受到摩擦力及离心力的作用，提升到一定高度，然后滑落、滚落或泻落而下，球体与球体及球体与筒壁之间，频繁地发生相互撞击和相互摩擦，使颜料团粒受到撞击、挤压和强剪切作用，同时球间漆浆处于高度湍流状态，这样使颜料团粒逐渐分散到漆料中。球磨机运转中球的工作情况如图4-1-98所示。在正常转速下，球的泻落角约为 $45^{\\circ}$ ，对于难分散颜料，可适当提高转速，使泻落角提高到 ${60}^{\\circ}$ 左右。有的球磨机在圆筒内设置了几条防球回滑的挡板（也称提升板）。  \n\n球磨机在运转中，部分机械能变为热能，漆浆温度会有所上升。一般来说，由于温升使漆浆黏度下降有利于分散过程，但也要关注压力升高情况及漆浆对温度升高是否敏感。有的钢壁球磨机设置了冷却夹套，可通水进行冷却。  \n\n涂料生产用的球磨机，主要有两种类型一一钢壁球磨机和钢壁石衬里球磨机，其结构如图4-1-99所示。图中（a）是钢壁球磨机，其圆筒部分用钢板焊制，两侧端盖为铸造的，与圆筒用铆钉或螺栓连接。也有圆筒和端盖全部采用钢板焊接结构。使用经验表明，全部采用焊接结构的球磨机，不仅要保证球磨机的两端轴头有较高的同轴度，而且要保证较高的焊接质量，以免焊缝产生裂纹以致出现漏漆的情况。钢壁球磨机可用钢球作研磨介质，但在运转中噪声极大。如用瓷球或鹅卵石，噪声减小。由于球磨机简体和钢球在运转中都要磨损，显然普通钢壁球磨机不宜用来加工浅色漆浆。但不锈钢壁球磨机并用瓷球例外。图中（b）是钢壁石衬里球磨机，衬里大多用花岗石，一般先加工成弧形板块，再在现场用砌的方法镶拼在圆筒内，两端也砌花岗岩石板。这种球磨机使用瓷球或鹅卵石作研磨介质，运转中噪声较小。可用于生产白色、浅色漆浆以及工艺上不允许掺人金属粉末的产品。  \n\n![](images/37d5d3bddf9de7795f6c509a0dc49ce6e8a02bb7f3dafd4986ec607706ed198f.jpg)  \n图4-1-98 球磨机中球的工作情况  \n\n$\\textcircled{2}$ 影响球磨机分散效率的主要因素  \n\na.球磨机的转速在球磨机中，一般装球至半满（以堆积体积计)，装入漆浆后，漆浆超过球的表面部分，最多约占总容量的 $15\\%$ ，球磨机静止时的状态见图4-1-100(a)。球磨机运转后，其转速对圆简内球的状态有很大的影响。在不同转速下，球的运动状态出现以下3种情况。  \n\n·泻落转速适当时，球不断被提起，不断滑落或滚落，两者均发生在漆浆内。见图4-1-100(b)。  \n\n$\\cdot$ 抛落转速提高到一定程度时，一部分球从漆浆中飞出，在蒸气空间跌落。此时分散  \n\n![](images/7bf9acd5168bcede2c7036e1c44971760d974aa26fa83b73ad0d45370a3dd1b9.jpg)  \n图4-1-99 两种球磨机结构  \n\n1一机体：2—衬里；3—加料孔；4—夹套；5—齿圈；6—减速机； 7一电机；8—栅板；9—出料管及阀门；10—机架  \n\n效果很差，且易造成球和筒壁的破损。见图4-1-100(c)。  \n\n·离心当转速进一步加快，达到某一限度，此时离心力起主导作用，球和漆浆均被甩起，贴附于筒壁上。此时处于相对静止状态，几乎完全没有分散作用。见图4-1-100(d)。  \n\n导致球磨机达到离心状态的转速称临界转速，经理论推导的临界转速n临（r/min）可用下式计算：  \n\n$$\nn_{\\mathbb{H}}=\\frac{42.3}{\\sqrt{D}}\n$$  \n\n式中D—简体内径， $\\mathbf{m}$ 0  \n\n由于计算离心力时是按球极小且紧贴于筒壁上计算的，实际上球磨机内球很多，靠中部  \n\n![](images/ec3e1492604e4419299683bb62129c811b124ba2009678f3105cd892d09c879e.jpg)  \n图4-1-100 球磨机静止和不同转速下的几种状态  \n\n1一空间 $35\\%$ ；2—漆浆装量 $35\\%$ （其中 $20\\%$ 在球的间隙中）；3一装球量 $50\\%$ （以堆积体积计，其中 $20\\%$ 为空隙）  \n\n的球并不贴壁，同时可能存在滑动现象，使球难以与圆筒完全同步旋转，所以实际的临界转速比上式计算的要大些  \n\n在上述3种球的运动状态中，形成泻落是颜料分散所希望的运动形式，而抛落和离心是不希望发生的。  \n\n球磨机是否处于最有效的运动状态，可以从运行中的噪声加以判断。噪声过大，说明球被甩出漆浆之外，球磨机转速过高；噪声偏小，说明球上提不够，球磨机转速过低或漆浆黏度太高；若转速太高，球和漆浆贴附于简壁上，则几乎没有噪声。  \n\n球磨机形成泻落状态的转速，称之为最佳转速，经过长期生产实践，得到一条计算最佳转速的经验式：  \n\n$$\nn_{\\mathrm{\\ell\\pm}}=\\frac{28.8}{\\sqrt{D}}-4.2\\sqrt{D}\n$$  \n\n式中 n佳 球磨机最佳转速， $\\mathbf{r}/\\mathbf{min}$ $D$ 简体内径， $\\mathfrak{m}$ 中  \n\n通过计算，得出球磨机筒体内径从 $300{\\sim}3000\\mathrm{mm}$ 的一组临界转速和最佳转速值，列于表4-1-18，供参考。  \n\n表4-1-18一组球磨机筒体内径与 $n_{\\mathrm{HE}}$ 及 $n_{\\mathrm{E}}$ 值   \n\n\n<html><body><table><tr><td>筒体内径/mm</td><td>临界转速/（r/min)</td><td>最佳转速/(r/min）</td></tr><tr><td>300</td><td>77.2</td><td>50.3</td></tr><tr><td>600</td><td>54.6</td><td>33.9</td></tr><tr><td>900</td><td>44.6</td><td>26.4</td></tr><tr><td>1200</td><td>38.6</td><td>21.7</td></tr><tr><td>1500</td><td>34.5</td><td>18.4</td></tr><tr><td>1800</td><td>31.5</td><td>15.8</td></tr><tr><td>2100</td><td>29.2</td><td>13.8</td></tr><tr><td>2400</td><td>27.3</td><td>12.1</td></tr><tr><td>2700</td><td>25.7</td><td>10.6</td></tr><tr><td>3000</td><td>24.4</td><td>9.4</td></tr></table></body></html>  \n\nb．球的选择 漆浆黏度高时，应选用密度较大的球和尺寸较大的球。  \n\n根据国内的一些厂家的使用经验，一般选用钢球直径约为 $12.5\\sim20\\mathrm{mm}$ ，瓷球直径以$20{\\sim}30\\mathrm{mm}$ 左右为宜，鹅卵石平均尺寸最好在 $35{\\sim}45\\operatorname*{mm}$ 0  \n\n$\\textcircled{3}$ 球磨机型号示例  \n\na.型号表示方法如WQM-500表示卧式球磨机，磨筒容量为 $500L$ 磨筒结构是否有石壁衬里，一般在型号中未表示，需看厂家产品说明书。  \n\nb.部分型号及技术参数  \n\n$\\cdot$ 钢壁球磨机钢壁球磨机可用钢球或瓷球，用户可自选。江阴市双叶机械公司生产的WQM小型卧式球磨机有3L、 $50\\mathrm{L}$ ， $200L$ 和500L等几种规格，其电机功率分别为$0.55\\mathrm{kW}$ 、1.1kW、 $3k W$ 和 $5.5\\mathrm{kW}$ 0  \n\n$\\cdot$ 钢壁石衬里球磨机钢壁内衬花岗岩，石衬里厚度约为 $\\mathbf{100mm}$ 。WQM型钢壁石衬里球磨机目前主要有 $1000\\mathbb{L}$ 、1700L、2000L、 $2500\\mathbb{L}$ 、3000L和 $5000\\mathrm{L}$ 等几种，其电机功率分别为$7.5\\mathrm{kW}$ 、11kW、11kW、 $18.5\\mathrm{kW}$ 1 $22k W$ 和 $37k W$ 。磨球推荐用直径为 $20\\sim30\\mathrm{mm}$ 的瓷球。  \n\n$\\cdot$ 如有特殊要求，可用耐磨陶瓷衬里代替花岗岩衬里。  \n\n$\\textcircled{4}$ 球磨机的优缺点  \n\na.优点  \n\n$\\cdot$ 无需预混作业 可把漆料、颜料等各种原料直接投人球磨机。  \n\n$\\cdot$ 基本上没有挥发损失和污染由于球磨机是完全密闭操作，挥发损失只局限于投料和出料时的损失，对环境的污染小。所以球磨机特别适用于毒性大的漆浆及高挥发分漆浆的分散，例如船舶漆的生产。  \n\n$\\cdot$ 操作简易，运行安全 因而操作过程无需很多关照，节省人力。  \n\n$\\cdot$ 设备结构简单，维修费用低  \n\n$\\cdot$ 适应性强能分散软或硬、粗或细的各种颜料配制的漆浆以及有假稠现象的漆浆。  \n\n$\\cdot$ 在分散过程中可避免金属细末污染产品采用钢壁石衬里球磨机并使用瓷球或鹅卵石，产品不与金属接触，以免金属细末影响产品性能。这个特点使球磨机宜用于制造绝缘漆。  \n\nb.缺点  \n\n$\\cdot$ 工作中噪声太大。  \n$\\cdot$ 设备笨重，占地面积大，消耗动力很大。  \n$\\cdot$ 劳动生产率较低，操作时间长，一般为 $24\\mathrm{h}$ 左右，有的长达 $\\mathfrak{s o h}$ 0  \n\n$\\cdot$ 变换颜色困难，漆浆不易放净。  \n\n$\\cdot$ 不宜加工过于黏稠的漆浆。  \n\n$\\cdot$ 研磨分散细度难以达到 $15\\mu\\mathrm{m}$ ，不宜用于加工高精度漆浆。  \n\n（2）立式球磨机  \n\n$\\textcircled{1}$ 设备结构和工作原理立式球磨机也叫搅拌式球磨机。它与卧式球磨机的区别不仅在“立”与“卧”的外观上，实际上它们在结构和工作原理上也迥然不同，只是在都要用“球”来完成研磨分散作业这一点上是其共同的特点。  \n\n图4-1-101为200L立式球磨机的结构。构成立式球磨机的主要部件是一个带有夹套的立式圆桶（研磨缸）和一个特殊设计的搅拌器。搅拌器一般为棒状，分成数层交叉安装在搅拌轴上。搅拌轴通过快开联轴器由摆线针轮减速机带动旋转，其转速为 $132\\mathrm{r/min}$ 圆桶内装有钢球（直径为 $4\\mathrm{\\sim}10.5\\mathrm{mm}$ ，以用$5\\sim6\\mathrm{mm}$ 居多)，装球容积不超过圆桶容积的$75\\%$ ，漆浆装量以没过球体为宜。在实际工作中，可根据电机负荷大小、漆浆是否可能溢出及分散效率调整装球量。  \n\n![](images/d3d68391f1f7cf14c650e982f3d8d2d6487cd36af240f9dc50637f812f388f0c.jpg)  \n图4-1-101 200L立式球磨机结构  \n\n搅拌器转动后，带动研磨介质运动，研磨介质球体与漆浆产生强烈的剪切和冲击作用，使颜料得以分散。运转中利用进料泵使漆浆在圆桶中循环，可使颜料分散均匀。圆桶底部有筛板，它能让漆浆通过而挡住球体。立式球磨机在工作中发出很大的噪声，发热也较剧烈，所以筒体夹套中要通水进行  \n\n冷却。分散细度合格后，可用进料泵并转换三通阀，将圆桶中的漆浆抽送到料桶。圆桶可通过手动蜗轮翻转机构倾倒，以卸出球体进行清洗或更换。  \n\n在立式球磨机中，球体的运动来源于机械搅拌，其能量远远超过卧式球磨机中同样的球体以泻落状态下落的能量。而且在立式球磨机中不是部分而是所有的球体都处于运动状态进行碰撞和摩擦，因此其分散效率大大超过卧式球磨机。  \n\n$\\textcircled{2}$ 立式球磨机型号示例  \n\na.型号表示方法如LQM200表示立式球磨机，桶体容积为200L。  \n\nb.部分型号及技术参数立式球磨机制造和使用的单位不多，目前产品的主要型号有LQM100、LQM200、LQM300、LQM500，其主电机功率为5.5kW、11kW、18.5kW、22kW。  \n\n现在有的厂家可生产衬聚氨酯塑料或衬陶瓷的立式球磨机，研磨介质使用氧化铝瓷球(直径10～11mm)，这样可避免铁锈污染产品。但磨体加了衬里后，夹套的冷却效果下降。  \n\n$\\textcircled{3}$ 立式球磨机的优缺点  \n\na.优点  \n\n$\\cdot$ 分散效率高于卧式球磨机，仅次于砂磨机。  \n\n·适用范围广。可用来分散各种漆浆，包括那些用难分散颜料配制的漆浆及有假稠现象的漆浆。适应的漆浆黏度范围较宽，约为0.4～2.5Pa·s。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1149,
+        "chunk": "# b.缺点  \n\n$\\cdot$ 噪声太大。  \n\n$\\cdot$ 如使用钢球，不能用于浅色漆浆。  \n$\\cdot$ 换色、清洗不方便。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1150,
+        "chunk": "# 四、调漆设备",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1151,
+        "chunk": "# 1.概述  \n\n调漆也叫调和，是使颜料在漆料中分散以制成色漆的最后一步操作。即将漆浆、漆料、溶剂及各种助剂按配方通过搅拌而配成均匀色漆的操作过程，其目的是达到产品所规定的颜色和黏度，并实现分散体系的稳定化。这一操作在调漆设备中进行。调漆作业有时被俗称为搅稀。  \n\n应当特别指出的是，调漆操作并不是简单的搅拌混合过程，如果操作不当，就会产生颜料再聚集、颜料絮凝、树脂沉淀等所谓“返粗”的弊病。一且发生这种情况，就会使分散作业前功尽弃，除返工重新分散外（实际上往往也很难)，别无他法。因此调漆操作必须谨慎从事，不能轻视马虎。首先，必须重视研磨配方和调漆配方的合理设计。其次，必须注意调漆时操作方法和步骤，应该向处于搅拌状态下的漆浆中缓缓地、小心地加入调漆用漆料，而不应反向地将漆浆加到调漆用的漆料中去。  \n\n调漆设备主要有搅拌装置和容器两部分组成。这两部分成为一个整体就是固定调漆罐，如果两部分分开，一部分是各种形式的搅拌机，另一部分是活动调漆罐或揽拌槽。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1152,
+        "chunk": "# 2.调漆设备的搅拌装置  \n\n目前国内涂料行业的调漆，按其搅拌器形式和转速可分为两大类：一类是利用像高速分散机的锯齿圆盘式叶轮以高速旋转；另一类是采用桨式、涡轮式、锚式或框式等各种搅拌器，按物料黏度和搅拌器结构尺寸，采用中、低转速。前者可直接利用定型的高速分散机，或者用电机直联传动，简单又方便，调漆速度快，但缺点是电机容量大，消耗功率也大；存在漆浆在搅拌中吸人气体产生气泡的弊病，影响产品质量，且对黏度高的物料不适宜；另外由于高速旋转，容易造成操作台振动。后者转速较低，传动平稳，操作平和，功率消耗少，吸入气体很少。为了使同一批次的色漆色泽均一，调漆容器正趋向大型化（大型调漆罐的容量已超过20m3），更以采用速度较低、桨叶直径较大的搅拌器为宜。  \n\n北京化工大学研制的CBY型轴流式搅拌桨，适用于低黏度液体的均相混合，在调漆设备中使用混合效果良好，且功率消耗只有锯齿圆盘式叶轮的 $60\\%$ 左右。还有设备运转平稳，搅拌时液面不产生中心旋涡，因而卷吸空气量很少等优点。图4-1-102所示为CBY型（螺旋）搅拌桨。桨叶由板材成型，叶片的截面形状与飞机机翼相似，叶片沿半径方向按近似等螺距规则变化，叶片的安放角度由叶端的，连续地增大至叶根的0。叶片数目根据需要可在2～6个之间变化。该桨单位功率所产生的循环流量较大。而且桨叶下方液体的轴向速度分布较均匀。经多次试验得出，这种搅拌器的直径与调漆罐直径的比值，一般在0.44左右为佳。通过对3～15m调漆罐实测，轴输人功率平均约为每立方米罐容积需用0.5～$0.9\\mathrm{kW}$ ，罐容积增加，此数值下降。  \n\n在选用或设计调漆用搅拌器时，要注意不要为过分缩短混匀时间而盲目增强搅拌的强烈程度，因为对于大多黏度较低的涂料来说，那样很可能造成讨厌的涂料飞溅现象。  \n\n对高黏度漆浆的调漆，可用锚式、框式搅拌桨，也可以用如图4-1-103所示的MIG式搅拌桨。它属于折叶桨的改型，斜桨的前端改变了倾角，多用多层式。由于 $\\theta_{1}$ 与 $\\theta_{z}$ 方向不同，桨叶根部与端部推动液体的流动方向相反。图中所示的液流为中心部位向下，而四周向上，使槽内液体作连续的循环流动。这种桨的桨径D与槽径T的比值可以在比较大的范围内选取，其值 $D/T{=}0.5{\\sim}0.98$ 。液体黏度大，则 $D/T$ 取大值，同时取较小的层间距。  \n\n![](images/bf37bf5f0192310b3863293c47ee98fed7602752d9b76cf7134f2d0b3e02aec4.jpg)  \n图4-1-102 CBY型螺旋桨  \n\n![](images/c759e8419657d20dd58e26aee1e8f9521dfe54298e2db47933e8486d83395342.jpg)  \n图4-1-104 小型移动式搅拌机  \n\n![](images/dd39d08524669aca98aab9b450e8ba6f5cd7ebffb444e560ad0696991a4365db.jpg)  \n图4-1-103 MIG型搅拌桨  \n\n![](images/d4ddb12548675df98fcbd544060dc36fe35cc900333775af9198c709cb8fdfa1.jpg)  \n图4-1-105 夹持在罐边的电动搅拌器  \n\nMIG式搅拌桨结构简单，制造成本低，搅拌效果好，功率消耗较少。为了适应搅拌槽底部封头形状，也可将它与短的锚式搅拌桨结合使用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1153,
+        "chunk": "# 3.调漆搅拌器的传动配置  \n\n$\\textcircled{1}$ 调漆罐为活动的 传动结构有以下3种情况。  \n\n![](images/d2609b95d2236dfbf9265add3b0bf868e2f2dc9f33fbd2c848a1456cad1c3865.jpg)  \n图4-1-106 电动机直联的高速调漆罐  \n\n1—电机；2—搅拌槽； 3一锯齿圆盘式叶轮；4一出料口 a.利用高速分散机 机头可液压升降。  \n\nb.小型漆罐采用机头可移动的搅拌机（见图4-1-104）产品如YJB型移动式分散机有4kW和2.2kW两种规格，可分别与250L和200L活动漆浆罐配套使用。  \n\nc.用电动搅拌器夹持在漆罐边上进行搅拌 如图4-1-105所示。图中显示了合适的安装位置及安装角度。  \n\n电动搅拌器的产品如佐竹移动式搅拌机，其中510型为电机直联式，520型为齿轮减速方式。它们的特点是使用方便灵活，特别适用于中、小容量的低黏度液体搅拌。此外，还可用风动搅拌器。  \n\n$\\textcircled{2}$ 调漆罐是固定的 传动结构有以下3种情况。a.利用高速分散机 机头可升降和回转。一台高速分散  \n\n机可配合 $2\\sim4$ 个搅拌槽。  \n\nb.电机与传动装置固定安装在顶部这是使用最多的一种传动配置方式。图4-1-106所示为电动机直联的情况，因使用锯齿圆盘式叶轮需要高速，调漆时可采取电机直联。如为其他搅拌形式，需要减速，减速的方法常采用 $V$ 带减速和摆线针轮减速机减速。如TC系列调漆槽，用摆线针轮减速机减速并通过联轴器带动桨式揽拌器运转，其余结构与图4-1-106 相似。TC系列调漆槽的容积为 $0.3{\\sim}10\\mathrm{m}^{3}$ ，有10个规格。  \n\nc.底部传动有正底部（见图4-1-107）和在底部侧面（见图4-1-108）两种方式。  \n\n![](images/33129cba98872f04151c571c4daa7638133a36da84415b7f942da3d187c1ca18.jpg)  \n图4-1-107底部搅拌的调漆罐 1一搅拌槽；2—推进式桨叶； 3一单端面机械密封；4一电机；5—出料口  \n\n![](images/0a45fabc974102449c1fb35328cbf14508bb70c5a8478f3190f2f97eebd2ddc1.jpg)  \n图4-1-108 底部搅拌（侧面）的调漆罐1一搅拌槽；2—搅拌桨；3—主机  \n\n底部传动的优点是：第一，调漆罐上部没有部件，比较宽，便于操作和清洗，这一点对于小容量固定式调漆罐更为重要。第二，不存在润滑油漏人油漆中的可能。第三，结构紧凑，轴短、摆动小。  \n\n底部传动的缺点是增加了轴封装置（大多为机械密封)，多了一个可能泄漏的动密封点，增加了维修工作量。此外，如搅拌槽容量很大，或漆浆黏度很大，底部传动不如顶部传动便于装设多种形式的搅拌器。  \n\n一种底部传动（侧面）的产品称DB型底伸搅拌机，它还有两个优点。一是由于搅拌安在锥底侧面，罐内液体不会产生中心旋涡，搅拌效果好；二是因搅拌在罐底，重组分不会沉底，出料口也不易堵塞。  \n\nDB型底伸搅拌机有 $\\mathrm{1m^{3}}$ 、 $2\\mathrm{m^{3}}$ ， $3\\mathrm{m^{3}}$ 、 $5\\mathrm{m^{3}}$ 四种规格。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1154,
+        "chunk": "# 4.搅拌槽  \n\n调漆罐的罐体，以圆形截面居多，制造比较方便，缺点是在搅拌时罐中液体会随轴一起做圆周运动，影响搅拌效果。通常可在罐体上加挡板，也可以使搅拌器偏心安装（用于中、低速搅拌)，或如图4-1-108那样装在锥底侧壁上。  \n\n方形截面（带较大圆角）的调漆罐不存在液体做圆周运动的病，液体在四角产生涡流，加强了搅拌的效果。  \n\n罐底大多是椭圆形或锥形，以减少死角，利于出料。在出料口带一段接管时，也能形成一点死角，可将接管取消，将凸缘直接焊在罐底上，通过紧贴罐底的放料阀出料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1155,
+        "chunk": "# 五、过滤设备",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1156,
+        "chunk": "# 1.概述  \n\n色漆中的杂质可能来自原料，也可能在制造过程中混人，即使漆料和溶剂都是合格的，但从管道中放出时，可能带有铁锈；在加人粉料拆袋时，可能会混入一些包装材料（如线绳、纸片)；用砂磨机作业时，一些碎的研磨介质（如玻璃珠）已混入漆浆中。冉者整个制造过程不可能是全密闭的，带人尘土和形成漆皮也在所难免。所以色漆在灌装出厂前，一定要过滤，以把住最后的关口，除去各种杂质，保证产品质量。色漆过滤的特点是既要除去杂质，但不能去掉符合细度要求的颜料。这也是它与树脂、漆料和清漆过滤的不同之处。  \n\n色漆过滤的设备和方法主要有罗筛、振动筛、挂滤袋过滤、袋式过滤器和滤芯过滤器。尤以挂滤袋过滤和袋式过滤器的应用最普遍。过滤原理、袋式过滤器和滤芯过滤器已在上一节中叙述，本节再介绍一种兼有滤袋和滤芯二者功能的新型过滤元件。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1157,
+        "chunk": "# 2.罗筛  \n\n罗筛，也称过滤罗，是最原始的过滤器。因它的结构太简单了，说它是工具也恰如其分。  \n\n在一个罗圈上绷上规格（目数）适当的铜丝网或尼龙丝网等，将它置于带支架的漏斗状容器或斜底容器中，容器底部或侧面装灌漆用的鸭嘴阀或专用铜旋塞，这就是一个简单的过滤灌装用罗筛。  \n\n罗面上的丝网，较常用的是黄铜丝编织的，俗称黄铜丝布。规格（目数）按工艺要求选取，大多选 $80\\sim150$ 目。  \n\n丝网规格常以目数来表示。所谓目数，就是指lin（ $:25.4\\mathrm{{mm}}$ ）边长内有多少个孔，表4-1-19列出了部分筛目尺寸对照表，供参考。  \n\n表4-1-19 部分筛目尺寸对照表  \n\n\n<html><body><table><tr><td>规格（目）</td><td>60</td><td>65</td><td>80</td><td>100</td><td>115</td><td>150</td><td>170</td><td>200</td><td>250</td><td>270</td><td>325</td><td>400</td></tr><tr><td>孔径/mm</td><td>0.246</td><td>0.208</td><td>0.175</td><td>0.147</td><td>0.124</td><td>0.104</td><td>0.088</td><td>0.074</td><td>0.061</td><td>0.053</td><td>0.043</td><td>0.038</td></tr></table></body></html>  \n\n罗筛的操作也很简单。进行过滤时，将待滤色漆以适当速度放人罗内，并维持一定的液位，同时用铲刀不时刮动，清理逐渐形成的滤渣，以加快过滤速度。  \n\n罗筛过滤只能用于产量小且对过滤精度要求不高的油漆，现逐渐被挂滤袋过滤所取代。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1158,
+        "chunk": "# 3.振动筛  \n\n使用罗筛过滤时，为了避免滤渣堵住筛孔，要用铲刀经常刮动。振动筛利用筛网的高频振动，有效地克服了这个病。  \n\n(1）结构和工作原理图4-1-109振动筛主要由筛网机构2、机芯振动机构及机座9等部件组成。筛网机构通过3套特制的橡胶弹簧和主支承螺栓与底座连接。机芯振动机构由机芯4、上偏心重锤3和下偏心重锤5组成。上、下偏心重锤的偏心方位可调节。经电机驱动，在上、下偏心重锤产生的离心力作用下，最终使筛网形成高频的水平和垂直两个方向的复合振动（三维振动)，使待过滤物料在筛网上形成轨道旋涡，使过滤能顺利进行。  \n\n对于不同物料的过滤，可选用不同孔径的筛网。同时，可调节偏心重锤的偏心方位，以得到理想的振幅和振型，满足过滤的工艺要求。  \n\n(2）振动筛的优缺点振动筛的优点是：结构简单、紧凑，体积小；一般都不用固定基座，使用时移动方便；过滤效率高，过滤成本低；换色、清洗方便。  \n\n缺点：由于是筛网不带压过滤，筛孔过小时影响过滤速度，所以还不能满足高档色漆的细度要求；工作时有一定程度的噪声；大多系开式过滤，存在溶剂挥发污染环境问题。所以，振动筛宜用于过滤乳胶漆。  \n\n![](images/ef85de57ccb17207c963d4cbccd7f1ac094d6afc251ec97b9c9fa7d23159fadd.jpg)  \n图4-1-109 振动筛  \n\n![](images/300871bf337f180b73ca61687a7f3b80eabbb43f4e43d2955766f7c6c572cb35.jpg)  \n图4-1-110一种兼有滤袋和滤芯功能的新型过滤元件  \n\n1—夹紧机构；2—筛网机构；3—上偏心   \n重锤；4—机芯；5—下偏心重锤；6—橡胶 弹簧；7一橡胶联轴器；8—电机； 9一机座；10—脚轮",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1159,
+        "chunk": "# 4.挂滤袋过滤  \n\n挂滤袋过滤，比罗筛过滤更简单、更方便、更实用，所以几乎到处都在应用。  \n\n把滤袋用铁丝绑或用卡箍卡的办法固定在垂直的放料管上，利用罐内液位的静压，打开放料阀门就可以过滤了。滤渣被截留在滤袋内，滤液用容器盛接。待滤袋内滤渣较多了，可暂停过滤，取下滤袋清除滤渣，将滤袋用溶剂洗净再用，直到不能重复使用时换新滤袋。  \n\n因为是挂滤袋，只利用不大的液体静压力，所以滤袋不能太密，阻力不可过大。目前常用的是尼龙单丝滤袋，标注的过滤细度范围为 $80\\sim800\\mu\\mathrm{m}$ ，可按工艺要求选用。两种常用滤袋的过滤面积为 $0.25\\mathbf{m}^{2}$ 和 $0.5m^{2}$ ，滤袋直径均为 $\\mathbf{180mm}$ ，长度分别为 $450\\mathrm{mm}$ 和$\\bar{8}50\\mathrm{mm}$ 。也可自制或定制更长的滤袋。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1160,
+        "chunk": "# 5.一种兼有滤袋和滤芯功能的新型过滤元件  \n\n(1）结构和工作原理美国HAYWARD过滤系统推出一款新型的过滤元件，它兼有滤袋和滤芯的优点，图4-1-110为其示意。它的核心部分是由两个优质滤材组成的同心圆筒。外圆筒相当于滤袋，内圆筒相当于滤芯。滤浆从二圆筒之间的环形空间上部进人，通过内、外圆筒过滤后，滤液从下部出口流出。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1161,
+        "chunk": "# (2）优点  \n\n$\\textcircled{1}$ 过滤面积大新型过滤元件的过滤面积比同样大小的滤袋多出 $70\\%$ 。因它过滤时流量大，用较小的过滤器即可完成既定的产量，节省了设备投资。  \n\n$\\textcircled{2}$ 容易安装 只要装一个配套的网篮，可在现有的袋式过滤器内安装使用。  \n$\\textcircled{3}$ 更换方便 因滤渣都在内部，清理时不会掉落。这一点优于滤芯。  \n④ 物料损失少新型过滤元件内残留的液体比一般滤袋少，降低了过滤成本。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1162,
+        "chunk": "# 第三节 过程管理  \n\n涂料行业是比较典型的制造业，因此关注于产品的质量特性。随着行业的不断发展进步，其质量管理活动也变得更为科学，已经由单纯的产品质量控制进步为通过对产品生产过程的管理，达到对产品质量的有效控制。因此，科学的管理理念、管理模式的引人成为可行和必然。ISO9000族标准的制定起源于制造业，多年来，随着系列标准的实施，国际标准化组织也在将9000族标准进行多次的修订，使其适用于超出制造行业的各个领域。2000版的ISO9001即提出了包括过程方法在内的八项管理原则。本节将根据涂料行业的特点介绍有关生产和服务过程的控制，以及简要地介绍ISO9001和ISO14000的部分内容。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1163,
+        "chunk": "# 一、ISO9000标准",
+        "category": " Introduction"
+    },
+    {
+        "id": 1164,
+        "chunk": "# 1.ISO9000族标准简介  \n\n随着生产技术的迅速发展，人们深深认识到产品质量的重要性。国际贸易的发展也迫切要求有一个全球认可的质量管理标准，为了适应国际贸易往来与经济合作的需要，国际标准化组织于1979年成立了质量管理和质量保证技术委员会（ISO/TC176），在其努力下于1987年颁布了ISO9000质量管理和质量保证系列标准，从而使世界质量管理和质量活动有了一个基础。ISO9000在世界范围内产生了十分广泛而深刻的影响。  \n\n质量管理的发展至今已经有近100年了，它是伴随着产业革命的兴起而逐渐发展起来的，其发展大体可以分为以下三个阶段。  \n\n（1）质量检验控制（IQC）阶段19世纪末至20世纪30年代，这一阶段工业企业需要靠经验来进行生产和管理，产品质量的控制从生产者自检逐渐过渡到互检，后又发展到设专职检验人员进行产品的质量检查，以加强最终产品的质量检验。英国于1903年把风筝标志用到了符合质量的铁轨上，开启了产品质量认证的历史。  \n\n（2）统计质量控制（SQC）阶段20世纪40年代至60年代初，把数理统计的概念和方法应用到管理中，创造了“控制图”去控制生产过程和预防产品缺陷的质量保证的做法。质量的统计控制法成为质量管理的主要内容。  \n\n（3）全面质量管理（TQC）阶段20世纪60年代至70年代，引进可靠性概念，从产品质量形成的过程去控制产品的质量。这一概念包括：全员性、全过程、全面性、关注顾客、体系方法等。  \n\n1959年由美国发布的MIL-Q-9858A《质量大纲要求》是世界上最早的有关质量保证方面的标准，用于规范国防工业的质量管理和质量保证工作；1971年美国标准化协会（AN-SI）和美国机械工程师协会（ASME）分别发布了一系列有关原子能发电和压力容器生产方面的质量保证标准，其中ANSI/ASQSZ1.15-09《质量体系通用导则》内容全面、严谨，后来成为ISO9004的工作草案；至1979年英国颁布了BS5750的三个质量保证标准，后来的ISO9001、ISO9002、ISO9003三个质量保证标准就是在这些标准的基础上制定出来的。  \n\n随着世界各国经济的迅速发展和日益国际化，对组织的质量管理体系的审核已逐渐形成为国际贸易和国际合作的一种需求，但是由于各国实施的标准不一致，在国际贸易中形成了技术壁垒，给经济的全球化带来了障碍，质量管理和质量保证的国际化成为当时世界各国的迫切需要。同时随着地区化、集团化、全球化经济的发展，市场竞争日趋激烈，顾客对质量的期望越来越高，并且顾客对产品的需求和期望又是不断变化的，如何识别并满足这些需求  \n\n成为组织的新课题  \n\n为了使1987版的ISO9000系列标准更加协调和完善，具有更广泛的适用性，ISO/TC176于1990年决定对标准进行修订，2000年12月15日，ISO/TC176正式发布了2000版的ISO9000族标准。  \n\n2000版ISO9000族标准更加强调了顾客满意及监视和测量的重要性，增强了标准的通用性和广泛的适用性，促进质量管理原则在各类组织中的应用，满足了使用者对标准应更通俗易懂的要求，强调了质量管理体系要求标准和指南标准的一致性。2000版ISO9000族标准对提高组织的运作能力、增强国际贸易、保护顾客利益、提高质量认证的有效性等方面产生了积极而深远的影响。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1165,
+        "chunk": "# 2.ISO9000族标准的构成及基本内容  \n\nISO9000族标准包括4个核心标准，以及相关的用于提高实施质量管理效率的支持性标准和文件，这些标准的标准号和名称见表4-1-20。  \n\n表4-1-209000族标准的构成及其核心标准  \n\n\n<html><body><table><tr><td colspan=\"2\">核心标准</td></tr><tr><td>GB/T 19000—2000 idt ISO 9000:2000</td><td>质量管理体系 基础和术语</td></tr><tr><td>GB/T 19001—2000 idt ISO 9001:2000</td><td>质量管理体系要求</td></tr><tr><td>GB/T 19004—2000 idt ISO 9004:2000</td><td>质量管理体系业绩改进指南</td></tr><tr><td>GB/T 19011—2003 idt ISO 9011:2000</td><td>质量和(或)环境管理体系审核指南</td></tr><tr><td colspan=\"2\">支持性标准和文件</td></tr><tr><td>ISO 10012</td><td>测量控制系统</td></tr><tr><td>ISO/TR 10006</td><td>质量管理项目管理质量指南</td></tr><tr><td>ISO/TR 10007</td><td>质量管理技术状态管理指南</td></tr><tr><td>ISO/TR 10013</td><td>质量管理体系文件指南</td></tr><tr><td>ISO/TR 10014</td><td>质量经济性管理指南</td></tr><tr><td>ISO/TR 10015</td><td>质量管理培训指南</td></tr><tr><td>ISO/TR 10017</td><td></td></tr><tr><td></td><td>统计技术指南</td></tr><tr><td></td><td>质量管理原则</td></tr><tr><td></td><td>选择和使用指南</td></tr><tr><td></td><td>小型企业的应用</td></tr></table></body></html>  \n\nISO9000：2000是对标准所采用术语的定义和介绍。它从质量、管理、组织、过程和产品、特性、合格、文件、检查、审核、测量过程质量保证等10个方面共列出80个有关的术语。  \n\nISO9001：2000是质量管理体系的具体要求。分质量管理体系、管理职责、资源管理、产品实现、测量、分析和改进几大部分，分别对组织、资源、过程、信息等方面的要求（包括文件要求）予以规定。  \n\nISO9004：2000是为组织改进业绩而策划、建立和实施质量管理体系的指南性标准。它与9001是相互协调的一对标准。就质量管理体系、管理职责、资源管理、产品实现、测量、分析和改进、自我评定方法与持续改进的过程等几个部分，提出了组织业绩改进的指导性建议。它超越了9001有关符合性的要求，为追求卓越业绩而扩展了管理的范围。  \n\nISO9011：2000是关于质量和环境管理体系审核的指导原则，它从第三方的视角评价组织实施体系的有效性、符合性。  \n\n2000版ISO9000标准以八项质量管理原则为理论基础，这八项质量管理原则包括：以顾客为关注焦点、领导作用、全员参与、过程方法、管理的系统方法、持续改进、基于事实的决策方法、互利的供方关系。八项质量管理原则是在总结质量管理实践经验的基础上，用高度概括、易于理解的语言所表述的质量管理最基本、最通用的一般规律，是质量管理的理论基础，也是组织的领导者有效地实施质量管理，并进行业绩改进的指导原则。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1166,
+        "chunk": "# 3.ISO9001与其他管理体系标准的相容性  \n\n质量管理体系是在质量方面指挥和控制组织的管理体系，是致力于实现组织的质量方针和质量目标的管理体系，以达到持续的顾客满意。而组织的质量方针和质量目标与其他管理体系的方针和目标是相辅相成、互为补充的。因此，将一个组织的管理体系的各个部分有机地结合或整合成一个整体，形成一体化管理体系，有利于策划、合理配置资源、确定互补的目标并评价组织整体业绩的有效性，这对提高组织的有效性和效率以及资源的综合利用等都是十分有利的。  \n\nISO9001标准使组织能够将自身的质量管理体系与相关的管理体系要求结合或整合，其中规定的质量管理体系要求和其他管理体系要求的内容是相容的。其相容性主要体现在以下方面。  \n\n（1）管理体系的运行模式都是以过程为基础，用“PDCA”循环的方法进行持续改进。(2）都是运用设定目标，系统地识别、评价、控制、监视和测量和管理一个由相互关联的过程组成的体系，并使之能够协调地运行。(3）管理体系标准中要求建立的形成文件的程序（如文件控制、记录控制、内部审核、不合格控制、纠正措施和预防措施等)，在管理要求和方法上都是详细的，因此，依据ISO9001标准的要求制定并保持的形成文件的程序，在其他管理体系中可以共享。(4）ISO9001标准中强调了法律法规的重要性，在环境管理体系和职业健康安全管理体系等标准中同样强调了适用的法律法规的重要性。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1167,
+        "chunk": "# 二、过程管理的理解和应用",
+        "category": " Introduction"
+    },
+    {
+        "id": 1168,
+        "chunk": "# 1.过程的方法和管理的系统方法  \n\n过程是一组将输入转化为输出的相互关联或相互作用的活动。多种过程可以形成过程网络，过程的结果即是产品。通俗意义上可将过程管理视为产品管理的有效手段。过程方法是ISO 9000族标准中的八项质量管理原则之一。  \n\n所谓过程方法，就是组织系统地识别并管理所采用的过程及过程的相互作用。在实际工作中，过程方法包括以下内容。  \n\n(1）识别质量管理体系所需要的过程及其在组织中的应用要识别质量管理体系所需要的过程及其在组织中的应用，包括列出过程、对每一过程规定输人和输出、规定过程的顾客及其要求、规定过程的责任人。  \n\n例如，在涂料生产企业“生产”过程中，输人包括生产配方、计划、物料、产品要求等；输出则包括产品。“生产配方”是上一过程“设计”的输出，而“产品”则是下一过程“销售”的输人。  \n\n（2）确定这些过程的顺序和相互作用这包括列出全流程和过程网络的架构、规定过程的接口、将过程形成文件。  \n\n对于同样的涂料“生产”过程，列出这些过程的顺序和框架结构。例如，采购 $\\rightarrow$ 计划 $\\nrightarrow$ 设计 $\\rightharpoonup$ 生产 $\\rightarrow$ 销售。对诸如设计和生产、生产和销售、甚至设计和销售之间的关联予以确定，可以以文件形式规定过程间的接口，包括职责、权限、信息沟通等。  \n\n(3）确定为确保这些过程的有效运作和控制所需的准则和方法包括规定期望和非期望结果的特性、规定测量、监视和分析的方法、考虑成本、时间、浪费等经济因素、规定数据收集的方法。  \n\n在“生产”过程中，即需要规定有关涂料产品各项性能的标准（参照国标、行标等制订的企标）和相应的检测方法以及记录。  \n\n（4）确保可以获得必要的资源和信息，以支持这些过程的运作和监视包括为每一过程配备资源、建立沟通渠道、提供内外信息、获取反馈、收集数据和保存记忆。  \n\n“生产”过程所需要的资源包括设备、操作工人以及各种生产用料。设备的类别、型号、运行参数、人员的资质以及原料要求都可以在此进行规定。  \n\n(5）监视测量和分析这些过程包括正确测量过程并监视其性能、使用统计技术分析所收集的信息并评价分析结果。  \n\n使用适宜的方法对过程能力、顾客满意等信息进行监视测量。例如设计过程能否满足输人要求，生产过程能否完成计划要求，其达成度、效率如何，需要采集一阶段数据，并运用统计技术做出评价。  \n\n(6）实施必要的措施，以实现这些过程所策划的结果和对这些过程的持续改进包括实施纠正和预防措施、验证纠正和预防措施的实施及有效性。  \n\n对于任何过程中出现的不合格，组织应制定并实施纠正和预防措施，以改进过程。同时在改进实施一定时间后要关注并验证纠正预防措施的有效性。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1169,
+        "chunk": "# 2.管理的系统方法  \n\n针对设定的目标，识别、理解并管理一个由相互关联的过程所组成的体系，有助于提高组织的有效性和效率。  \n\n系统方法的特点： $\\textcircled{1}$ 它围绕某一个设定的方针和目标； $\\textcircled{2}$ 确定实施这一方针和目标的关键活动； $\\textcircled{3}$ 识别由这些活动所构成的过程； $\\textcircled{4}$ 分析这些过程间的相互作用和相互影响的关系； $\\textcircled{5}$ 按某种方式或规律，将这些过程组合成一个系统； $\\textcircled{6}$ 管理由这些过程构筑的系统，使之能协调地运行； $\\textcircled{7}$ 通过测量和评估并保持改进体系。  \n\n在质量管理体系中采用系统方法，即把整个管理体系作为一个大的系统，通过对各个过程的识别、管理达到实现组织的质量目标和质量方针。例如在涂料行业中，很多企业采用了物料计划信息系统管理，即将采购、计划、生产、仓储、销售等多个过程作为一个大的过程，实现系统的统筹管理，以期在这一组过程中达到及时生产、减少库存、降低管理成本的目的。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1170,
+        "chunk": "# 3.二者的关系  \n\n“管理的系统方法”和“过程方法”是十分“亲和”的两个原则。两者研究的对象都与过程相关，他们都以过程为基础，都要求对各个过程之间的相互作用进行识别和管理，都可采用PDCA的循环运行方式，两者都着重于关注顾客的要求，通过识别和管理组织内的过程，以及随后对其开展的持续改进达到增强顾客满意的目标，从而达到促进过程和体系的改进以提高有效性和效率的目的。  \n\n两个原则之间也存在一定的区别：过程方法侧重于研究单个的过程，即过程的输入、输出、活动及所需的资源，以及该过程和其相关过程的关系；过程方法管理的是一组活动及其相关的资源，旨在高效率地达到每个过程的目标。管理的系统方法侧重于研究若干个过程乃至过程网络组成的体系，以及体系运作如何有效地实现组织的目标；通过系统地管理一组过程，旨在达到组织的目标；管理的系统方法是通过优化和协调运作过程，实现组织的整体优化。  \n\n显然，过程方法是管理的系统方法的基础。过程方法和管理的系统方法之间的主要区别见表4-1-21。  \n\n表4-1-21 过程方法和管理的系统方法之间的主要区别  \n\n\n<html><body><table><tr><td>项目</td><td>过程方法</td><td>管理的系统方法</td></tr><tr><td>研究对象</td><td>每个过程及该过程与其他相关过程的关系</td><td>若干过程及至过程网络</td></tr><tr><td>管理对象</td><td>一组活动和相关的资源</td><td>一组过程</td></tr><tr><td>目的</td><td>高效地达到过程的目标</td><td>提高实现组织目标的有效性和效率</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1171,
+        "chunk": "# 三、涂料生产和服务提供的过程管理",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1172,
+        "chunk": "# 1.涂料行业生产过程控制的策划  \n\n生产和服务的提供过程直接影响组织向顾客提供产品或服务的质量，因此生产企业应对如何控制生产和服务提供过程进行策划，对人、机、料、法、环、测等影响生产和服务提供过程质量的所有因素加以控制，使其处于受控条件之下。  \n\n由于不同的产品或服务的类型及生产和服务提供过程的特点不尽相同，其生产和服务提供的受控条件也不尽相同。  \n\n对于涂料行业，按照ISO90017.5.1的要求，受控条件应包括以下几项。  \n\n(1）表述产品特性的信息以作为实施生产和服务提供活动的依据。它可以体现为不同的形式，如涂料产品性能指标说明，包括产品规范、样品、样件、颜色标准、施工条件、设备、包装要求、服务规范等。  \n\n(2）必要时，获得作业指导书并非所有的生产和服务提供过程都需要有相应的作业指导书，但是如果没有作业指导书就可能导致生产或服务提供过程失效或失控的情况下，应向这些活动的操作者提供作业指导书，以便规范和指导生产和服务提供过程的实施。作业指导书的形式可以是多种多样的，如工艺过程卡、操作规范、服务规范、工艺规程以及相应的设备使用指导书等。  \n\n(3）使用适宜的设备在生产和服务提供过程中，使用满足过程能力要求的设备是保障产品质量的重要方面。因此，在生产和服务提供过程中，应使用能够持续稳定地生产合格产品或提供符合要求的服务的设施设备。  \n\n(4）获得和使用监视和测量装置有的生产和服务提供过程需要使用监视和测量设备，应为这些过程配置所需的检测设备，并在这些过程的实施之中使用合适的监视和测量设备。  \n\n(5）实施监视和测量在有些生产和服务提供过程的实施中，需要对这些过程的特性进行监视和测量，以确保这些过程的特性控制在规定或允许的范围内。  \n\n（6）放行、交付和交付后活动的实施按照策划的受控条件对产品放行、交付、交付后的活动实施控制。生产和服务提供过程的控制包括对产品放行（例如产品生产的各工序之间的流转放行）、交付（例如将产品交付给顾客的送货上门）、交付后活动（例如交付后的配套产品的供应、培训、施工指导、维护等售后服务）的控制，在这些活动中，组织应按规定的要求和程序开展活动并实施控制。  \n\n针对以上要求，涂料行业一般应相应地确定以下因素：  \n\n$\\textcircled{1}$ 涂料产品性能指标说明，施工工艺参数，包括环境条件（温度、湿度等)；  \n$\\textcircled{2}$ 提供给生产过程的作业指导书，以及施工过程指导；  \n$\\textcircled{3}$ 确定适宜的生产设备（混合、研磨、调色等设备）以及符合施工要求的涂装设备；  \n$\\textcircled{4}$ 确定符合相应规范要求的检验、试验设备和装置；  \n\n③安排有相应资质的人员、过程，对涂料产品的生产、涂装过程实施相应的检验、指导；  \n③对有交付和交付后活动要求的顾客，应安排适宜的过程，如施工指导、涂装监理。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1173,
+        "chunk": "# 2.生产和服务提供过程的确认  \n\n（1）当生产和服务提供过程的输出不能由后续的监视或测量加以验证时，应对其实施确认。这包括仅在产品使用或服务已交付之后问题才显现的过程。如涂料的调色过程。  \n\n(2）对过程能力进行确认。对在涂料生产、涂装过程中形成的产品问题，进人下一环节或使用后才显露出来的特性，需进行确认。  \n\n(3）充分识别哪些过程需进行确认（在涂料生产企业中，这种过程通常包括合成、研磨、调色等)。  \n\n（4）安排确认活动  \n\n$\\textcircled{1}$ 规定准则 根据过程特点和产品特性，明确规定对过程评审和批准的准则。  \n\n$\\textcircled{2}$ 设备鉴定和人员资格认可评价所用设备的能力（包括安全性、可用性）及维护保养要求和现状；鉴定该过程的操作人员是否具备相应的能力和资格。  \n\n$\\textcircled{3}$ 使用特定的程序和方法确定该过程的操作人员是否具备相应的能力和资格。  \n$\\textcircled{4}$ 记录要求对评审、批准、认可鉴定和工艺参数等要有记录。  \n$\\textcircled{5}$ 再确认按规定的时间间隔或发生问题时，对过程进行再确认。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1174,
+        "chunk": "# 3.标识和可追溯性  \n\n(1）适当时，组织应在产品实现的全过程中使用适宜的方法识别产品组织应针对监视和测量要求识别产品的状态。在有可追溯性要求的场合，组织应控制并记录产品的唯一性标识。用来区分容易混滑的产品的标识通常称为“产品标识”，这种标识是用来标明产品的不同规格型号、不同特点或不同特性的，以达到防止产品在使用中混淆的目的。  \n\n一般地，涂料生产过程中，可标识出原料、半成品、成品及涂装等过程。  \n\n涉及产品的标识又可包括标签、标记、标牌等，包含了产品生产的时间、批次、设备号等内容。  \n\n(2）组织应针对监视和测量要求识别产品的状态产品的监视和测量状态标识的作用是防止不同状态产品在使用中发生混淆，特别是防止误用不合格品。这种标识会根据产品的不同监视和测量状态而发生相应的变化。通常涉及检验状态的标识包括待检、已检、合格、不合格、返工等。  \n\n(3）在有可追溯性要求的场合，组织应控制并记录产品的唯一标识并非所有产品都有实现可追溯性的要求，但不同组织的不同产品由于其要求不同或特殊性，可能会有可追溯性的要求。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1175,
+        "chunk": "# 4.顾客财产  \n\n组织应爱护在组织控制下或组织使用的顾客财产。组织应识别、验证、保护和维护供其使用或构成产品一部分的顾客财产。若顾客财产发生丢失、损坏或发现不适用的情况时，应报告顾客，并保持纪录。  \n\n这里顾客财产是指顾客所拥有的，为满足合同要求向组织提供的产品、设备、财物和信息资料等，包括顾客提供的原料、半成品、包装材料，来自顾客的设备、设施和工具，尤为重要的是顾客知识产权包括提供的规范、标准、样本、产品配方、施工工艺等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1176,
+        "chunk": "# 5.产品防护  \n\n在内部处理和交付到预定的地点期间，组织应针对产品的符合性提供防护，这种防护应包括标识、搬运、包装、贮存和防护。防护也适用于产品的组成部分。  \n\n从原材料的人库保管起，至生产制造中间产品、存放制造产品，乃至最终产品的包装、人库、出库，直到交付到顾客现场，应建立并保持适当的防护标识，包括产品标识、包装标识和运输标识；提供适当的搬运方式和设备，防止在生产、服务提供及交付的搬运时损坏产品；根据产品特点和顾客要求包装产品，重点在于有利于产品搬运、贮存时的防护；原材料、半成品和最终产品的贮存期间，必须提供必要的环境和设施条件，采取有效的管理措施，防止产品损坏变质；对危险材料，组织应采取特殊的保护措施。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1177,
+        "chunk": "# 四、ISO14000简介",
+        "category": " Introduction"
+    },
+    {
+        "id": 1178,
+        "chunk": "# 1.ISO14000系列标准  \n\nISO14000系列标准是国际标准化组织ISO/TC 207负责起草的一系列国际标准。它包括了环境管理体系、环境审核、环境标志、生命周期分析等国际环境管理领域内的许多焦点问题，旨在指导各类组织（企业、公司）取得和表现正确的环境行为。ISO14000系列标准的代号和名称见表4-1-22。  \n\n表4-1-22ISO14000系列标准的代号和名称  \n\n\n<html><body><table><tr><td>名称</td><td>标准号</td><td>名称</td><td>标准号</td></tr><tr><td>环境管理体系（EMS）</td><td>14001~14009</td><td>生命周期评估(LCA)</td><td>14040~14049</td></tr><tr><td>环境审核(EA)</td><td>14010~14019</td><td>术语和定义(T&D)</td><td>14050~14059</td></tr><tr><td>环境标志(EL)</td><td>14020~14029</td><td>产品标准中的环境指标</td><td>14060</td></tr><tr><td>环境行为评价(EPE)</td><td>14030~14039</td><td>备用</td><td>14061~14100</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 1179,
+        "chunk": "# 2.ISO14000系列标准的分类  \n\nISO14000是一个多标准组合系统，它所包含的标准按性质可分为基础标准、基本标准和支持技术类标准三类，按标准的功能划分可以分为评价组织的标准和评价产品的标准两类。详细的分类见表4-1-23。  \n\n表4-1-23ISO14000系列标准的分类  \n\n\n<html><body><table><tr><td>分类方式</td><td>包括的标准大类</td><td>标准内容</td></tr><tr><td rowspan=\"6\">按标准性质分类</td><td>基础标准</td><td>术语标准</td></tr><tr><td>基本标准</td><td>环境管理体系</td></tr><tr><td rowspan=\"3\"></td><td>规范、原理、应用指南</td></tr><tr><td>环境审核</td></tr><tr><td>环境标志</td></tr><tr><td rowspan=\"4\">评价组织</td><td>环境行为评价</td></tr><tr><td>生命周期评估 环境管理体系</td></tr><tr><td>环境行为评价</td></tr><tr><td>环境审核</td></tr><tr><td rowspan=\"2\">按功能分类 评价产品</td><td>生命周期</td></tr><tr><td>环境标志</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1180,
+        "chunk": "# 3.ISO14000系列标准的起源  \n\n欧美一些大公司在20世纪80年代就已开始自发制定公司的环境政策，委托外部的环境咨询公司来调查他们的环境绩效，并对外公布调查结果（这可以认为是环境审核的前身）。以此证明他们优良的环境管理和引为自豪的环境绩效。它们的做法得到了公众对公司的理解，并赢得广泛认可，公司也相应地获得经济与环境效益。为了推行这种做法，到1990年末，欧洲制定了两个有关计划，为公司提供环境管理的方法，使其不必为证明信誉而各自采取单独行动。第一计划为BS7750，由英国标准所制定；第二个计划是欧盟的环境管理系统，称为生态管理和审核法案（Eco-Management and Audit Scheme，EMAS)，其大部分内容来源于BS7750。很多公司试用这些标准后，取得了较好的环境效益和经济效益。这两个标准在欧洲得到较好的推广和实施。  \n\n同时，世界上其他国家也开始按照BS7750和EMAS的条款，并参照本国的法规和标准，建立环境管理体系。另外一项具有基础性意义的行动则是1987年ISO颁发的世界上第一套管理系列标准——-ISO9000质量管理与质量保证取得了成功。许多国家和地区对ISO9000系列标准极为重视，积极建立企业质量管理体系并获得第三方认证，以此作为开展国际贸易进人国际市场的优势条件之一。ISO9000的成功经验证明，国际标准中设立管理系列标准的可行性和巨大进步意义。因此，ISO在成功制定ISO 9000系列标准的基础上，开始着手制定标准序号为14000的系列环境管理标准。因此可以说欧洲发达国家积极推行的BS7750、EMAS以及ISO9000的成功经验是ISO14000系列标准的基础。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1181,
+        "chunk": "# 4.几项环境管理标准简介及其作用  \n\n(1）ISO14001《环境管理体系规范及使用指南》ISO14001是ISO14000系列标准中的主体标准。它规定了组织建立、实施并保持的环境管理体系的基本模式和17项基本要求。该体系适用于任何类型和规模的组织，并适用于各种地理、文化和社会条件。这样一个体系可供组织建立一套机制用来确定环境方针和目标等，通过环境管理体系的持续改进实现组织环境绩效的持续改进。本标准的总目的是支持环境保护和污染预防，协调它们与社会需求和经济需求的关系。  \n\n环境管理体系（EMS）是整个组织管理体系中的一部分，用来制定和实施其环境方针，并管理其环境因素，包括为制定、实施、实现、评审和保持环境方针所需的组织机构、计划活动、职责、惯例、程序、过程和资源。  \n\nISO14001：1996《环境管理体系规范及使用指南》是国际标准化组织于1996年正式颁布的可用于认证目的的国际标准，是ISO14000系列标准的核心，它要求组织通过建立环境管理体系来达到支持环境保护、预防污染和持续改进的目标，并可通过取得第三方认证机构认证的形式，向外界证明其环境管理体系的符合性和环境管理水平。  \n\n由于ISO14001环境管理体系的实施可以为企业带来节能降耗、增强竞争力、赢得市场和政府、公众信任等诸多好处，所以自发布之日起即得到了广大企业的积极响应，被视为进人国际市场的“绿色通行证”。同时，由于ISO14001的推广和普及在宏观上可以起到协调经济发展与环境保护的关系、提高全民环保意识、促进节约和推动技术进步等作用，因此也受到了各国政府和民众越来越多的关注。为了更加清晰和明确ISO14001标准的要求，ISO对该标准进行了修订，并于2004年11月15日颁布了新版标准ISO14001：2004《环境管理体系要求及使用指南》。  \n\nISO14001标准是在当今人类社会面临严重的环境问题（如温室效应、臭氧层破坏、生物多样性的破坏、生态环境恶化、海洋污染等）的背景下产生的，是工业发达国家环境管理经验的结晶，其基本思想是引导组织按照PDCA的模式建立环境管理的自我约束机制，从最高领导到每个职工都以主动、自觉的精神处理好自身发展与环境保护的关系，不断改善环境绩效，进行有效的污染预防，最终实现组织的良性发展。该标准适用于任何类型与规模的组织，并适用于各种地理、文化和社会环境。  \n\n(2）ISO14004《环境管理体系原则、体系和支持技术通用指南》本标准简述了环境管理体系的五项原则，为建立和实施环境管理体系，加强环境管理体系与其管理体系的协调提供可操作的建议和指导。它同时也向组织提供了如何有效地改进或保持的建议，使组织通过资源配置、职责分配以及对操作惯例、程序和过程的不断评价（评审或审核）来有序而一致地处理环境事务，从而确保组织确定并实现其环境目标，达到持续满足国家或国际要求的能力。  \n\n(3）ISO14010《环境审核指南通用原则》环境审核与质量体系审核一样，是验证和帮助改进环境绩效的一项重要手段。ISO14010标准给出了环境审核定义及有关术语，并阐述了环境审核通用原则，旨在向组织、审核员和委托方提供各种环境审核的一般原理。  \n\n(4）ISO14011《环境审核指南审核程序环境管理体系审核》本标准提供了进行环境管理体系审核的程序，包括审核目的、启动审核直至审核结束一系列步骤要求，以判定环境管理体系是否符合环境管理体系审核准则。本标准适用于实施环境管理体系的一切类型和规模的组织。  \n\n(5）ISO14012《环境审核指南环境审核员资格要求》本标准提供了关于环境审核员的资格要求，它对内部审核员和外部审核员同样适用。  \n\n(6）ISO14040《生命周期评价原则和框架》这一标准于1997年6月1日正式颁布，是ISO14000系列标准中的工具性标准。  \n\n标准将一个产品完整的环境生命周期评价工作分为四个基本阶段：目的与范围的确定、清单分析（即分析产品从原材料获取到最终废置整个生命过程各个阶段中的环境投人与产出及其影响的清单)、影响评价（根据清单分析的结果，分析产品各生命阶段对环境的影响，或比较类似产品对环境的影响）、结果释义（将得到的结果与所确定的目的进行比较，确定潜在的改进方向)。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1182,
+        "chunk": "# 5.ISO14001标准的运行模式及主要内容  \n\n环境管理体系模式不是一个封闭的过程，而是一个周而复始、螺旋上升的循环过程，体系按照这一模式运行，在不断循环的过程中实现持续改进。体系的运行过程分五大部分，是体系的五个一级要素，各个部分又分若干条款，称为二级要素。见表4-1-24。  \n\n表4-1-24IS014001标准体系的运行过程  \n\n\n<html><body><table><tr><td>一级要素</td><td>二级要素</td><td>一级要素</td><td>二级要素</td></tr><tr><td>环境方针</td><td>环境方针</td><td rowspan=\"3\"></td><td></td></tr><tr><td>规划(策划)</td><td>环境因素 法律和其他要求 目标和指标</td><td>文件控制 实施和运行 运行控制</td></tr><tr><td></td><td>环境管理方案 组织结构和责任</td><td>应急准备和反映 检测和测量</td></tr><tr><td>实施和运行</td><td>培训、意识和能力 信息交流</td><td>检查和纠正措施</td><td>不一致纠正和预防措施 记录</td></tr><tr><td></td><td>环境管理体系文件</td><td>管理评审</td><td>环境管理体系审核 管理评审</td></tr></table></body></html>  \n\n(1）第一部分环境方针表达了组织在环境管理上的总体原则和意向，是环境管理体系运行的主导，其他要素所进行的活动都是直接或间接地为实现环境方针服务的。它所解决的问题是：为什么要做，目的是什么。  \n\n(2）第二部分环境策划环境策划是组织对其环境管理活动的规划工作。包括确定组织的活动、产品或服务中所包含的环境因素；确定组织所应遵守的法律、法规要求和其他要求；根据环境方针制定环境目标和指标规定有关职能和层次的职责，以及实现目标和指标的方法和时间表。它所解决的问题是：要做什么。  \n\n(3）第三部分实施运行这是将上面策划工作付诸实行并进而予以实现的过程，包括规定环境管理所需的组织结构和职责，相应的权限和资源；对员工进行有关环境的教育与培训，环境意识和有关能力的培养；建立环境管理中所需的内、外部信息交流机制，有效地进行信息交流；制定环境管理体系运行中所需制定的各种文件；对文件的管理，包括文件的标识、保管、修订、审批、撤销、保密等方面的活动；对组织运行中涉及环境因素，尤其是重要环境因素的运行活动的控制；确定组织活动可能发生的事故，制定应急措施，并在紧急情况发生时及时作出响应。它所解决的问题是：怎么做。  \n\n(4）第四部分检查和纠正措施在实施环境管理体系的过程中，要经常地对体系的运行情况和环境表现进行检查，以确定体系是否得到正确有效的实施。其环境方针、目标和指标的要求是否得到满足，如发现不符合，应考虑采取适当的纠正措施。它所解决的问题是：所做的是否正确。  \n\n(5）第五部分管理评审是组织的最高管理者对环境管理体系的适宜性、充分性和有效性的评价，包括对体系的改进。它所解决的问题是：是否在做对的工作。  \n\n经过五个部分的运行，体系完成了一个循环过程，通过修正，又进人下一个更高层次的循环。整个体系并不是一系列功能模块的搭接，而是相互联系的一个整体，充分体现了全局观念、协作观念、动态适应观念。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1183,
+        "chunk": "# 6.一个组织实施环境管理体系将要达到的效果  \n\n当组织建立了环境管理体系之后，通过管理活动程序、建立规范化文件和记录等措施可以协调不同的职能部门之间的关系，并可以达到下列目的：  \n\n$\\textcircled{1}$ 建立良好的环境方针和环境管理基础；$\\textcircled{2}$ 有利于找出并控制重大的环境因素和影响；$\\textcircled{3}$ 有利于识别有关的环境法规要求与现行状况的差距；$\\textcircled{4}$ 减少由于污染事故或违反法律法规所造成的环境影响；$\\textcircled{5}$ 建立组织内污染防止优先序列，并为实现污染预防目标而努力；$\\textcircled{6}$ 可以提高监测环境的能力和评价该体系的效率，包括促进体系的改进和调整，以适应新的和不断变化的情况和要求；$\\textcircled{7}$ 由于改善环境从而带来许多重要的商业、环境机会。总之，环境管理体系将有助于组织系统化地处理环境问题，并将环境保护和企业经营结合起来，使之成为企业日常运行和经营策略的一个部分。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1184,
+        "chunk": "# 7.企业申请ISO14000认证需要的基本条件  \n\n企业要申请认证，应找已通过中国环境管理体系认证机构认可委员会认可的认证机构进行申请，可以要求该机构出示“认可证书”。  \n\n企业建立的环境管理体系要申请认证，必须满足以下两个基本条件：  \n\n$\\textcircled{1}$ 遵守中国的环境法律、法规、标准和总量控制的要求；  \n\n$\\textcircled{2}$ 体系试运行满3个月。  \n\n这里的环境法律、法规、标准和总量控制的要求包括国家和地方的要求。  \n\n对于涂料行业，还要根据其产品的特点，在运行体系实施认证工作中注意以下几个问题。  \n\n(1）解析生产工艺，充分识别环境因素涂料种类繁多，不同种类的涂料，因生产所用的原料、辅料不同，生产工艺不同，涉及的环境因素也不相同。组织应对环境因素进行充分的识别，应自查是否遗漏了重要环境因素，是否满足ISO14001标准的要求。充分识别物料的迁移、变化的规律。例如，投料过程中的加料口可能导致有毒有害溶剂、粉尘等的挥发泄漏，应作为环境因素进行识别。  \n\n(2）关注有害材料替代使用状况在很多涂料生产企业中，可能大量使用苯、醛、酮、醚类溶剂；在固体原料中含有汞、铬、镉、砷、铅、锡等重金属和有毒物质。这些有毒有害化学品的使用，以及跑、冒、滴、漏、意外遗洒、在产品中的含量等，都是重要环境因素。  \n\n是否充分识别这些环境因素，是否对其采取了有效的控制措施，产品中的有害物质是否达到国家标准，特别是是否制订了替代这些材料的方案，其实施状况及效果如何，关系到能否从源头减少污染，是持续改进环境行为和绩效的关键问题。  \n\n(3）重视安全隐患目前，许多涂料企业规模小，技术装备落后，人员素质不高，安全隐患较多，这是申请环境管理体系认证所需关注的重要问题。企业是否针对所有可能发生的紧急情况制订了切实可行、有效的应急预案，关系到一些潜在的紧急情况下的环境因素是否得到识别。例如，某高空装卸料有没有防护栏，以防止操作时物料因为不小心掉落，造成环境污染；溶剂储存区有无消防设施和防火标识，这些都应该进行识别并制订应急预案。  \n\n(4）详细评估节能降耗效果在涂料生产中，要使用大量原料、辅料，电能、热能的消耗也相当多，并且生产过程手工操作多，跑、冒、滴、漏和计量不准确等问题多有发生。对此，企业应详细评估物料配方和能量消耗是否合理，有无节约潜力，现场管理有无漏洞，计量器具配备是否合理、齐全，环境目标、指标和运行控制程序是否覆盖受审核方的全部活动，以及产品和服务中所涉及的节能降耗的全部内容。这对企业而言，提高了环境绩效，同时，在认证审核中，节能降耗也是作为判断EMS有效性的重点之一，故应予以重视。  \n\n(5）评价对法律法规符合性遵守法律法规是组织在环境方针中明确做出的承诺，无违法超标行为是通过EMS审核的最低要求。对组织环境法律法规的符合性的评价，其范围不但包括通用的法律法规，还要涵盖有关涂料产品的国家标准、行业标准等其他要求。特别是民用涂料产品，是否达到相关标准规定的指标，既是事关人身健康的大问题，也是评价组织与法律法规符合性的核心内容。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1185,
+        "chunk": "# 参考文献  \n\n[1] 涂料工艺编委会编，涂料工艺（上、下册）．第3版．北京：化学工业出版社，1997.  \n[2] 段质美等．涂料工业，1982，（1）：6-10.  \n[3] 倪玉德主编：涂料制造技术，北京：化学工业出版社，2003.  \n[4] 朱桂莞，孙建．涂料设备，1992，（总16）：13-17（内部刊物）.  \n[5] 潘元奇：涂料与应用，1987，（4）：26-36（内部刊物）.  \n[6] 陈敏恒，丛德滋，方图南编．化工原理，北京：化学工业出版社，1985.  \n[7] 王仁辅，傅振英主编．动量传变过程，徐州：中国矿业大学出版社，1992.  \n[8] 丁绪淮，周理编著，液体搅拌，北京：化学工业出版社，1983.  \n[9] 王凯，冯连芳著．混合设备设计，北京：机械工业出版社，2000.  \n[10］化工设备设计全书编辑委员会，化工设备设计全书·搅拌设备，北京：化学工业出版社，2003.」盈根，化，，/；1-0.  \n[12]林猛流等．化工设备设计，1986，（1)：54-59.  \n[13]林猛流等．涂料设备，1990，（总11)：57-72（内部刊物）.  \n[14]阿 陈志平，章序文，林云华等编著，搅拌与混合设备设计选用手册．北京：化学工业出版社，2004.  \n[15] 胡国桢，石流，阎家宾主编，化工密封技术，北京；化学工业出版社，1990.  \n[16] 李继和，蔡纪宁，林学海编，机械密封技术，北京：化学工业出版社，1988.  \n[17］潘元奇．涂料设备，1992，（总16)：43-51（内部刊物).  \n［18］李幼样．化工设备设计，1988，（4)；42-44.  \n［19］王泳厚主编．涂料工人必读，武汉：湖北科学技术出版社，1986.  \n[20] 李国起，景继厚等．涂料工业，1990，（5)：21-23.  \n[21］陈育民，张强，高增祥．涂料设备，1993，（总18)：33-34（内部刊物).  \n[22]裘桃梅．涂料设备，1993，（总18)：36-40（内部刊物).  \n[23] 沈锦周．涂料工业，1992，（5)：42-46.  \n[24] 马庆麟主编．涂料工业手册．北京：化学工业出版社，2001.  \n[25］朱九龄，程大壮．涂料设备，1993，（总18)：49-53（内部刊物).  \n［26］［苏］戈尔洛夫斯基，科祖林著．涂料工厂设备．第3版．周本励，冯明霞译．北京：化学工业出版社，1987.  \n[27］劳动部．有机热载体炉安全技术及有关条款说明．北京：劳动部锅炉压力容器安全杂志社，1993.  \n[28］化学工业部．有机载热体加热炉安全技术规程．1993（内部资料).  \n[29］黄森炎．涂料设备，1989，（总8)：35-38（内部刊物）.  \n[30］美国孟山都（MONSANTO）公司．液相导热油系统设计指南（内部资料).  \n[31］王起明，李宏斌．涂料设备，1993，（总17)：21-22（内部刊物).  \n[32］潘元奇．涂料工业，1992，（6)：21-24.  \n[33］潘元奇．化工之友，1991，（3)：21-22.  \n[34]化学工业部设备维护检修规程编委会，化工部设备维护检修规程：第七分册·化工部分．北京：化学工业出版社，1992.  \n[35］潘元奇．涂料工业，1994，（3)：16-21.  \n[36］潘元奇．涂料与应用，1984，（1)：71-78（内部刊物).  \n［37］方图南，潘元奇．化工设备与防腐蚀，2001，（3)：2-7.  \n[38］牟富君．涂料设备，1992，（总15)：62-68（内部刊物).  \n［39］孔繁臣，吕厚连．涂料设备，1991，（总13)：23-29（内部刊物).  \n［40］沈浩主编．制漆配色调制工．北京：化学工业出版社，2006.  \n［41]［美］巴顿TC著．涂料流动和颜料分散．郭隽奎，王长卓译．北京：化学工业出版社，1988.  \n[42]吴金胜，李淑娴编译．涂料设备，1987，（总4)：1-14（内部刊物).  \n［43]潘元奇，涂料与应用，1988，（1)：4-14（内部刊物).  \n[44］沈锦周．涂料工业，1992，(6)：47-51.  \n［45］潘元奇．涂料与应用，1992，（3)：1-6.  \n[46］北京红狮涂料公司．涂料设备，1991，（总14)：27-31（内部刊物).  \n[47］王永琪，廖红，王晶，涂料设备，1995，（总20)：9-13（内部刊物).  \n［48］阁太涛译．涂料设备，1988，（总6)：127-128（内部刊物).  \n[49］刘恩林．涂料工业，1979，（4)：34-41.  \n[50］北京化工大学混合工程教研室（吴德均执笔)．涂料设备，1994，（总19)：25-29（内部刊物).  \n[51]程文龙，周荫朴，吴德均．涂料设备，1995，（总20)：14-16（内部刊物).  \n[52]牟富君．涂料设备，1993，（总17）：11-13（内部刊物).  \n[53]质量管理体系基础和术语．ISO $9000$ ：2005.北京：中国标准出版社，2005.  \n［54］质量管理体系要求．ISO9001：2008．北京：中国标准出版社，2008.  \n[55］环境管理体系要求及使用指南．ISO14001：2004．北京：中国标准出版社，2004.  \n[56]张德平，张跃平编著，ISO14001：2004环境管理体系审核要点与审核中常见不符合．北京：中国标准出版社，2006.",
+        "category": " References"
+    },
+    {
+        "id": 1186,
+        "chunk": "# 涂料工厂设计",
+        "category": " Introduction"
+    },
+    {
+        "id": 1187,
+        "chunk": "# 第一节 绪论  \n\n工厂设计是一项技术与经济相结合的综合性设计工作。工厂设计通常包括设计前期工作、初步设计和详细施工设计3个阶段。  \n\n（1）设计前期工作包括商务计划，项目建议书，可行性研究，厂址选择和投资计划。投资计划由建设项目的项目组织编制，其目的是根据可行性研究报告和厂址选择报告，对建设项目的主要问题，即产品方案、建设规模、建设地区和地点、专业化协作范围、投资限额、资金来源、要求达到的技术水平和经济效益等作出决策。  \n\n(2）初步设计根据批准的投资计划进行编制。初步设计包括：确定主要原材料、燃料、水、动力的来源和用量；规定工艺过程、物料储运（见物料搬运）、环境保护等设计的主要原则；明确设备、建筑物和公用系统的构成和要求；进行工厂布置，设计全厂和车间的平面布置图；提出生产组织、管理信息系统和生活福利设施的方案；计算主要设备材料的数量、各项技术经济指标和工程概算。批准后的初步设计是建设投资的拨款、成套设备订购和施工图设计的依据。  \n\n(3）施工图的设计绘制各种建筑物的建筑结构详图、设备和管线的安装详图、各项室外工程的施工详图，编制全部设备材料明细表和施工预算。  \n\n工厂设计需要考虑多方面的问题，应运用系统工程并以发展的观点考虑以下的原则：从实际情况出发，按不同的要求选择合理的方案。采用科学技术研究的新成果，包括先进工艺、高效设备和机械化、自动化手段以及计算机辅助管理等方法。采用的技术和装备应与原料、技术、劳动力等资源条件相适应。讲究投资的经济效益和建设的社会效果。在各个设计阶段对不同的设计方案应进行技术经济分析和效果评价。技术经济分析选用多项相互联系的技术经济指标，一般是采用投资回收期和投资收益率等作为重要指标。资金支付与收益年份并不相同，因此应根据贴现利率将资金折算为同一年份的现值，使经济比较建立在可比的基础上。  \n\n本章节主要介绍工厂选址和工厂设施设计，其他相关的内容只做简单介绍。考虑到粉末涂料和液体涂料的完全不同，而液体涂料工厂设计的要求比粉末涂料的设计相对复杂，因此本章的工厂设施设计以液体涂料为例。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1188,
+        "chunk": "# 第二节 商务计划、项目建议和工厂选址  \n\n商务计划是任何一个新投资的基础。在任何投资决策之前，一份可靠完整的商务计划是  \n\n不可缺少的。  \n\n(1）市场综述主要对整个宏观经济的现状和将来进行描述，着重于经济的总需求和总供给（产出)、商业周期、整体价格（通货膨胀）水平和整体就业（失业）水平等。  \n\n(2）行业、行业预测及市场分析仔细研究相关领域的微观经济的发展，着重于客户、公司和行业之间的对于特定商品和服务的供需现状和发展。  \n\n(3）市场细分及客户结构着重于目标市场的产业结构，市场总量分析，市场前景分析，客户结构分析。  \n\n（4）竞争对手 包括直接竞争对手和替代品供应商。  \n\n(5）项目公司内部分析对公司现状、发展历史、股东结构、管理团队、经营业绩、发展规划进行分析，一般定义为“SWOT”分析，即成功关键因素分析。  \n\n(6）营销策略目标份额、行业地位、市场定位、定价、分销、产品及产量预测、新产品研究等。  \n\n（7）组织计划所有权的形式，合作者或主要股权所有人的身份，负责人的权利，管理层成员的背景，组织成员的角色和责任。  \n\n在商务计划通过管理层讨论并认为可行后，项目进行下一阶段—向公司决策层提交项目建议书。  \n\n项目建议是在商务计划的基础上，进行初步的投资建议。除总结商务计划的主要内容外，主要介绍项目目标、建议和投资分析。  \n\n（1）商务计划书中的主要内容。  \n\n(2）生产现状分析现有工厂位置、生产条件、生产技术、产品技术、客户需求、供应链现状。(3）项目可选方案建议主要从优势、劣势、成本和时间出发，分析解决生产现状的不同方案，并确定最佳建议方案。(4）最佳方案设计场地规模、生产规模、工厂布置、主要设备、技术基础、物流计划。(5）项目组织结构基本的组织架构及人选，包括筹划指导委员会、项目所有者、项目经理、项目工程师等。(6）项目进度设计和投资预算根据所选择的方案，对项目进度进行编制，并定制总投资报表。(7）财务计划销售预测、收入预测、投入产出、投资回报预测、现金流预测、敏感性分析及投资预算。  \n\n将项目建议提交给公司决策层后，如认可该项目的可行性，则进行工厂选址和工厂设计。  \n\n工厂选址由项目组承担。项目组会形成一个选址委员会，它一般由项目组的商务负责人、技术负责人、其他有经验的专家、外部专家及律师组成。工厂选址是对不同城市、地区进行宏观和微观的评价，确定评价因素，对不同的地址，根据所要考虑的因素进行评价，从而确定理想的工厂位置。  \n\n厂址选择要认真贯彻国家的建设方针，服从城市建设规划，注意节约用地和环境保护，处理好生产与生活、近期与远期等各方面的关系。  \n\n涂料工厂厂址选择一般有以下几个基本要求：厂址应靠近原料、燃料供应地区及产品销售地区，使产品的生产和物流费用最低；应具备方便而经济的运输条件；应具备充分的水、电、汽供应条件；其附近应具有一定的公用事业基础，以便利用其生活福利设施；其地形应满足总图布置的要求；自然条件有利于“三废”的治理与综合利用。  \n\n对于影响工厂选址的因素，可根据它们与成本的关系进行分类。与成本有直接关系的因素，称为成本因素，可以用货币单位来表示各可行位置的实际成本值。与成本无直接关系，但能间接影响产品成本和未来企业发展的因素，称为非成本因素，常见的几种成本和非成本因素见表4-2-1。  \n\n表4-2-1 常见的几种成本和非成本因素  \n\n\n<html><body><table><tr><td>成本因素</td><td>非成本因素</td><td>成本因素</td><td>非成本因素</td></tr><tr><td>运输成本</td><td>社区情况</td><td>土地成本和建筑成本</td><td>文化习俗</td></tr><tr><td>原料供应</td><td>气候和地理环境</td><td>税率、保险和利率</td><td>当地政府政策</td></tr><tr><td>水力、动力和能源的供应量和成本</td><td>环境保护</td><td>财务供应：资本及贷款的机会</td><td>扩展机会</td></tr><tr><td>劳动力成本</td><td>政治稳定因素</td><td>各类服务和保养费用</td><td>当地竞争者</td></tr></table></body></html>  \n\n按照设施选址的程序，在确定了设施选址所要考虑的决定因素之后，还需要对各个位置进行初步筛选，排除不可行的方案，提出几个预选地址，接下来要确定采用何种评价方法。目前，方法有许多。基本可以分两类，一是同时考虑成本和非成本因素的综合方法；另一是只考虑成本因素的评价方法。具体评价方法可参考相关文献。  \n\n![](images/1f5fa7cdbe489c7ba054f60c1b9b173c85218b30fdf13d619fa6934fb1f319db.jpg)  \n\n可行性研究是在项目建议书的基础上编制的。可行性研究的主要任务为如何有效地进行工程项目的建设提供依据。可行性研究是项目建议书的细化，主要包括以下15部分。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1189,
+        "chunk": "# 1.总论  \n\n概述工程项目的依据、研究范围、目的和要求。简要说明工程项目的主要研究过程、论据和结论性意见，以及存在问题。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1190,
+        "chunk": "# 2.建设规模和产品方案  \n\n根据商务计划书中的市场计划，对计划销售的产品进行销量预测，并根据销售量预测、计划原材料的用量。有了销售量和原材料的用量，则可以预计建设规模。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1191,
+        "chunk": "# 3.工艺生产技术方案  \n\n涂料生产的工艺流程简短而繁多，具有较大的灵活性和通用性。涂料生产工艺是生产设施设计的基础。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1192,
+        "chunk": "# 4.产品质量标准  \n\n企业可执行的质量标准有国家标准、国际标准和企业标准。但是，任何一个产品必须符合国家相关标准。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1193,
+        "chunk": "# 5.主要生产设备选择及标准  \n\n涂料生产主要设备有分散机、砂磨机、调色机、贮罐、泵等。分散机和调色机一般为非标设备，通常是通过设备制造商根据主要产品性能、介质性质和产能进行设计和制造的。定型设备则由工艺设计人员提供参数来采购。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1194,
+        "chunk": "# 6.物料贮存消耗及来源  \n\n（1）物料消耗 根据商务计划书中产品销量预测、计划原辅材料的单耗和年消耗量。  \n\n(2）物料贮存涂料需要贮存的物料主要有原辅材料、包装材料和成品。原材料中有固体原料和液体原料（粉末涂料除外)。其中还有一些属于危险化学品，必须根据材料的危险性质分别进行贮存。为此，在厂区内应设立固体危险品仓库、固体非危险品仓库、液体危险品罐区和液体危险品堆场。固体物料仓库按贮存物料的危险性质进行分区；危险化学品贮存区与其他区域用实体墙隔开，液体危险品罐区用于贮存各种液体危险化学品，四周设置防火堤，不同品种间设置隔堤，防火防爆设计要符合有关安全规范的要求。液体原料用槽车运来，用原料泵将槽车内的物料打人贮罐。使用时用原料泵将贮存在罐中的物料送到生产装置。贮罐放空管道上均设阻火器，以消除火灾隐患。卸车时采用密闭系统；在罐顶设有气相平衡管，卸车时与槽车的气相平衡管相连。可以防止火灾隐患，减少挥发性物料的损失。  \n\n(3）库存管理涂料生产所需原料数量大，种类繁多，成品更是成千上万种。库存管理建议采用货架贮存，条形码读取模式，从而减少手工操作的失误。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1195,
+        "chunk": "# (4）工厂物流布置原则  \n\n$\\textcircled{1}$ 规划原则要在建厂之初做好物料搬运的规划和设计，与工厂布置设计结合进行，在内容上密切协调，适应组织结构的合理化和管理的方便，使有密切关系或性质相近的作业单位布置在一个区域并就近布置，甚至合并在同一个建筑物内。  \n\n$\\textcircled{2}$ 系统原则要在生产系统的整个物流系统分析的基础上进行物料搬运的规划和设计，达到全系统的协调与平衡。  \n\n$\\textcircled{3}$ 简化原则尽可能简化搬运作业，减少运输环节，避免迁回、交叉的搬运路线，缩减搬运距离和次数，利用新技术消除搬运的必要性，符合工艺过程的要求。尽量使生产对象流动顺畅，避免工序间的往返交错，使设备投资最小，生产周期最短。  \n\n$\\textcircled{4}$ 节约原则采取立体空间运输和贮存，节约场地；采用重力来移动物料以节约劳动力、能量和设备投资；改善物流路线状态以节约搬运费用。  \n\n$\\textcircled{5}$ 柔性原则能机动地改换搬运物料、搬运途径和时间，使之适应产品需求的变化、工艺和设备的更新及扩大生产能力的需要。  \n\n$\\textcircled{6}$ 安全原则要确保安全搬运和环境保护，为职工提供方便、安全、舒适的作业环境，使之合乎生理、心理的要求，为提高生产效率和保证员工身心健康创造条件。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1196,
+        "chunk": "# 7.动力消耗及来源  \n\n为减少基础设施的投人和能源供应的保证，工厂的选址一般在工业园内。因此，生产用水、用汽和用电均可直接从园区供水管网、蒸汽管网和供电网接入。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1197,
+        "chunk": "# 8.运输  \n\n根据工厂实际情况，原辅材料、包装材料和产品的运输主要依托社会运力，采用汽车运输和船舶运输。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1198,
+        "chunk": "# 9.项目厂址与建设条件  \n\n（1）项目厂址项目选址要综合考察投资环境和投资政策，仔细研究地理位置和基础配套设施，以及相关的市场和资源，根据所选择的评估方法来决定项目的厂址。所选的厂址应该周围环境较好，交通便利，大型运输车辆进出方便，水、电和蒸汽供应充足，公用设施配套齐全。  \n\n化工企业厂址必须考虑当地风向因素，一般应位于城镇、工厂居住区全年最小频率风向的上风方向。厂区具体定位应与当地现有和规划的交通线路、车站、港口进行便捷合理的联结。厂前区尽量临靠公路干道，铁路、索道和码头应在厂后、侧部位，避免不同方式的交通线路平面交叉。集中建设的工厂居住区不宜分散在铁路或公路干道两侧，邻近居住区的线路应保持有关规范所规定的距离。  \n\n(2）建设条件主要介绍厂址所在地的自然条件、地理条件、地质条件和人文条件。应考虑所在地区的自然环境，危险有害因素主要包括雷击、雨雪、台风、洪水、高温、冰冻、地震等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1199,
+        "chunk": "# 10．工厂布置  \n\n工厂总平面布置原则为：以生产工艺流程合理，物流顺畅便捷，功能分区明确为基本原则，并满足地区总体规划、绿化、卫生、防火、防震等要求，尽量做到节约用地、降低能耗、节省投资。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1200,
+        "chunk": "# 11.组织机构及人员培训  \n\n(1）企业体制 根据投资方的意愿和有效管理原则来制定组织架构，责任分工。  \n\n(2）劳动定员和人员培训对从事本项目产品生产操作及质量检验的人员要进行专业技术培训，使其具有本项目产品生产的基础理论知识和实际操作技能。在培训的基础上进行基本理论和实际操作的考核，符合要求者持证上岗。主要培训方式为：组织安全教育、工艺流程、操作规程的业务学习。上岗前需要足够的培训，并要组织考核，择优上岗。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1201,
+        "chunk": "# 12.项目进度及实施方案  \n\n(1）项目进度项目建设期一般分为两部分，其中可研报告、厂址选择、公司建立、购买土地、选择承包商等前期工作为一部分，工程设计、土建施工、设备招标采购、设备管道安装调试、试车投产等为另一部分。  \n\n(2）实施方案  \n\n$\\textcircled{1}$ 实施条件准备：施工场地、交通运输、施工用电、施工用水等。  \n\n$\\textcircled{2}$ 实施阶段：包括前期工作，如公司建立、购买土地、建设方案、资金落实、技术落实、设备的供货商技术、信誉等各方面工作；设计阶段方案和施工阶段方案。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1202,
+        "chunk": "# (3）管理措施  \n\n$\\textcircled{1}$ 建立一个强有力的指挥系统，对设计、采购、施工实行统一指挥和协调，调动各协作单位和部门的积极性。  \n\n$\\textcircled{2}$ 设计、施工、建设单位都要建立保证体系、进度控制体系和投资控制体系，切实搞好本项工程的三大控制。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1203,
+        "chunk": "# 13.总投资估算和投资计划  \n\n(1）投资估算项目总投资由固定资产投资总额和运作流动资金组成。  \n\n固定资产投资总额包括设备购置费、建筑工程费、安装工程费、土地使用权费、工程设计费、建设单位管理费、工程监理费等。  \n\n运作流动资金是为工厂建成后正常运作所需的资金，根据企业流动资金周转情况和产品的生产特点而计算。  \n\n(2）投资计划根据项目的实际情况，计算项目建设期，固定资产投资于建设期全部投入。流动资金根据各年生产负荷的安排，逐年进行投入。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1204,
+        "chunk": "# 14.财务预测和评价  \n\n财务预测是根据产品销售计划、定价、成本而核算的。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1205,
+        "chunk": "# 15.风险分析及主要对策  \n\n风险分析要根据经营市场的风险、市场竞争对手的风险、产品价格的风险、管理风险及其他风险进行综合考虑。针对以上风险和影响，项目单位应积极采取相应措施，将风险和影响因素降低到最低程度。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1206,
+        "chunk": "# 第四节 工厂基础设计和配套设施设计  \n\n工厂总体设计应参照并符合国家及当地建筑用地的要求，可参照相关规范与法规：  \n\n《企业总平面设计规范》GB50187—1993  \n《厂矿道路设计规范》GBJ22—1987  \n《石油化工企业设计防火规范》GB50160—1992  \n《建筑设计防火规范》GBJ16—1987（2001年版）  \n《工业企业设计卫生标准》GBZ1-2002",
+        "category": " References"
+    },
+    {
+        "id": 1207,
+        "chunk": "# 一、总图总平面布置  \n\n总平面布置是所有工艺及内部物流的基础，而它又是工艺设计和物流设计的结果。  \n\n涂料生产是一个物理混合过程，其物料的内部运输量是设计量的4～5倍。如原材料到厂后卸货贮存在原料区，生产前要备料到备料区，生产时要把备好的原料运到生产设备的位置，生产包装后转运到仓库贮存，发货时要把货物从仓库中取出，拆分，打托，装上卡车。因此，其工厂内部的物流高效是非常重要的。同时，涂料使用的原料一般在300～500种左右，而成品则在800～1500种甚至更多。所以，其中仓库的科学性设计是一个非常重要的课题。  \n\n按项目购置的建设用地面积，根据场地大小，生产装置区及原料贮存区集中布置于工程用地的中部和靠近出口的位置，主要分为：非危险品原料仓库、危险品原料库、生产车间、危险品罐区及非危险品罐区，非危险品成品仓库、危险品成品库。  \n\n消防水泵房、消防水池、变配电所、空压站及冷冻站布置在厂区公用工程区。行政办公区，包含办公楼及停车场等必要设施，布置紧靠主干道的进口和上风口位置，以减少生产废气对办公环境的影响，而且，方便对外联络，不干扰生产。  \n\n工厂布置的原则是满足工艺要求，保证场地排水短捷、顺畅。  \n\n图4-2-1为一典型的涂料工厂布置简图。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1208,
+        "chunk": "# 二、公用及辅助工程",
+        "category": " Introduction"
+    },
+    {
+        "id": 1209,
+        "chunk": "# 1.给、排水及蒸汽  \n\n给、排水及蒸汽的设计依据有：  \n\n《建筑给排水设计规范》（GB50015—2003）《室外给水设计规范》（GBJ13—1997）《室外排水设计规范》（GBJ14—1997）《生活饮用水卫生标准》（GB5479—1989）  \n\n![](images/828d3002d7ca3dc60b865b1e368b2032227e6b7ebb8f0fdd4f3401f6a16b96df.jpg)  \n图4-2-1 典型涂料工厂的布置简图  \n\n《工业循环水处理设计规范》（GB50050—1995）  \n《洁净厂房设计规范》（GB50073—2001）  \n《建筑设计防火规范》（GBJ16一2001）  \n《自动喷水灭火系统设计规范》（GB50084一2001）  \n《建筑灭火器配置设计规范》（GBJ140—1997）  \n《蒸汽供热系统凝结水回收及蒸汽疏水阀技术管理要求》（GB/T12712—1991)  \n\n工厂用水分为生产用水和生活用水两部分，根据生产所需的冷却水量、消防水量和产品用水量来计算。而生活用水量则与员工数量有关。一般来说，装置用水来自园区的自来水供水管网。自来水水质应符合生活饮用水标准。采用的管径由设计人员进行设计。  \n\n排水分为三个系统：雨水/净下水系统、生活污水系统和工业污水系统。净下水系统接人园区净下水排水管网。工业污水采用专用的污水收集系统收集起来，定期用专车送去合同单位委托处理（具有环保废物处置资质)；或设计污水处理装置，处理达标后归入雨水系统。生活污水系统则与市政的污水系统相连。",
+        "category": " References"
+    },
+    {
+        "id": 1210,
+        "chunk": "# 2.供电  \n\n供电设计依据主要参考如下：  \n\n《供配电系统设计规范》（GB50052—1995）  \n《低压配电设计规范》（GB50054—1995）  \n《通用用电设备配电设计规范》（GB50055一1993）  \n《电力装置的继电保护和自动装置设计规范》（GB50062—1992）  \n《工业企业照明设计标准》（GBJ50034一1993）  \n《医药工业洁净厂房设计规范》  \n《火灾自动报警系统设计规范》（GB50116—1998）  \n《建筑设计防火规范》（GBJ16—2001）  \n《爆炸和火灾危险环境电力装置设计规范》（GB50058—1992）  \n《建筑物防雷设计规范》（GB50057—2000）  \n《电力工程电缆设计规范》（GB50217一1994）  \n《民用建筑电气设计规范》（JGJ/T16—1992）  \n《评价企业合理用电技术导则》（GB/T3485—1998）  \n\n（1）动力电源根据所有设备的负荷由专业设计人员计算出总安装容量、动力安装容量、照明安装容量、视在功率和电容补偿功率。一般来说，消防泵房用电、应急照明及火灾报警系统均为消防用电设备，属一级用电负荷。生产性用电设备均为三级负荷。一级负荷需要双电源供电。因此，设计全厂配备一台柴油发电机组，作为一级负荷的备用电源。而三级负荷的电源则从市政电网接线后经电缆引入变电所。  \n\n一级负荷供电的建筑，当采用自备发电设备作备用电源时，自备发电设备应设置自动和手动启动装置，且自动启动方式应能在30s内供电。  \n\n消防应急照明灯具和灯光疏散指示标志的备用电源的连续供电时间不应少于 $30\\mathrm{min}$ 消防用电设备应采用专用的供电回路，当生产、生活用电被切断时，应仍能保证消防用电。其配电设备应有明显标志。消防控制室、消防水泵房、防烟与排烟风机房的消防用电设备及消防电梯等的供电，应在其配电线路的最末一级配电箱处设置自动切换装置。沿疏散走道设置的灯光疏散指示标志，应设置在疏散走道及其转角处距地面高度 $1.0\\mathrm{m}$ 以下的墙面上，且灯光疏散指示标志间距不应大于 $20.0\\mathrm{m}$ ；对于袋形走道，不应大于$10.0\\mathrm{m}$ ；在走道转角区，不应大于 $1.0\\mathrm{m}$ ，其指示标志应符合现行国家标准《消防安全标志》GB13495的有关规定。  \n\n(2）电力安全设计原则  \n\n$\\textcircled{1}$ 电气线路应避开可能受到机械损伤、振动、腐蚀以及可能受热的地方。  \n\n$\\textcircled{2}$ 正常不带电，而事故时可能带电的配电装置及电气设备外露可导电部分，均应按《工业与民用电力装置的接地设计设施》（GBJ66—1984）要求设计可靠接地装置，车间接地要等电位接地。  \n\n$\\textcircled{3}$ 各装置防静电设计应符合《化工企业静电接地设计规程》（HG/T20675—1990）的规定。各装置防静电设计应根据生产工艺要求、作业环境特点和物料的性质采取相应的防静电措施。  \n\n$\\textcircled{4}$ 低压配电室的配电设备布局应符合 $\\yen103,456$ 及以下变电所设计规范》（GB50053）、《供配电系统设计规范》（GB50052）、《低压配电设计规范》（GB50054）的规定。  \n\n$\\textcircled{5}$ 各装置、设备、设施及建筑物，应根据国家标准和规定确定防雷等级，设计可靠的防雷保护装置，防止雷电对人身、设备以及建筑物的危害和破坏。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1211,
+        "chunk": "# 三、建筑结构形式  \n\n土建工程方案设计的主要依据有：  \n\n《建筑结构可靠度设计统一标准》（GB50068一2001）《建筑结构荷载规范》（GB50009一2001）《建筑地基基础设计规范》（GB50007—2002）《混凝土结构设计规范》（GB50010—2002）  \n\n《砌体结构设计规范》（GB50003一2001）《洁净厂房设计规范》（GB50073一2001）《外墙外保温工程技术规程》（JG」144一2004）《建筑照明设计标准》（GB50034一2004）《建筑采光设计标准》（GB/T50033—2001）  \n\n生产车间及危险品仓库的生产类别为甲类，具有防爆、防腐要求。根据生产特点，生产车间采用钢筋混凝土柱，楼层全开式框架结构，部分封闭房间和楼梯间与生产区的隔墙为钢筋砖填充防爆墙。  \n\n危险品仓库采用钢筋混凝土柱，彩钢板轻型屋面，由于危险品仓库内贮存物品的火灾危险为甲类，因此屋盖系统采用轻质屋盖，作为泄压面积。围护墙体设置足够面积的侧窗，以满足防爆泄压要求。散发较空气重的可燃气体、可燃蒸气的甲类厂房以及有粉尘、纤维爆炸危险的乙类厂房，有防爆要求的混凝土地、楼面做成不发火花水泥砂浆地坪，采用绝缘材料作整体面层时，应采取防静电措施。  \n\n根据《建筑抗震设计规范》（GB50011一2001）要求，本建设项目抗震措施应符合本地区抗震设防烈度的要求，抗震设防烈度设为7度，框架部分抗震等级设为四级，并制定具体的防震救灾预案。  \n\n厂房内不宜设置地沟，必须设置时，其盖板应严密，地沟应采取防止可燃气体、可燃蒸气及粉尘、纤维在地沟积聚的有效措施，且与相邻厂房连通处应采用防火材料密封。  \n\n门窗优先选用塑钢门窗，内外装修应做到与周围环境协调统一，充分利用地方材料和不同的装饰材料以满足工艺要求。  \n\n主要土建构成包括需要建设涂料工艺生产厂房、制冷站、变配电所、空压站和污水收集系统、原材料及成品仓库、液体罐区、半露天堆放场以及配套的办公生活设施等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1212,
+        "chunk": "# 1.厂房（仓库）的耐火等级  \n\n可分为一、二、三、四级。其构件的燃烧性能和耐火极限除另有规定者外，不应低于表4-2-2和表4-2-3的规定。  \n\n表4-2-2厂房（仓库）建筑构件的燃烧性能和耐火极限 单位：h  \n\n\n<html><body><table><tr><td>名称</td><td colspan=\"4\">耐火等级</td></tr><tr><td>构件</td><td>一级</td><td>二级</td><td>三级</td><td>四级</td></tr><tr><td>防火墙</td><td>不燃烧体 3.00</td><td>不燃烧体 3.00</td><td>不燃烧体 3.00</td><td>不燃烧体 3.00</td></tr><tr><td>承重墙</td><td>不燃烧体 3.00</td><td>不燃烧体 2.50</td><td>不燃烧体 2.00</td><td>难燃烧体 0.50</td></tr><tr><td>楼梯间和电梯井的墙 墙</td><td>不燃烧体 2.00</td><td>不燃烧体 2.00</td><td>不燃烧体 1.50</td><td>难燃烧体 0.50</td></tr><tr><td>疏散走道两侧的隔墙</td><td>不燃烧体 1.00</td><td>不燃烧体 1.00</td><td>不燃烧体 0.50</td><td>难燃烧体 0.25</td></tr><tr><td>非承重外墙</td><td>不燃烧体 0.75</td><td>不燃烧体 0.50</td><td>难燃烧体 0.50</td><td>难燃烧体 0.25</td></tr><tr><td>房间隔墙</td><td>不燃烧体 0.75</td><td>不燃烧体 0.50</td><td>难燃烧体 0.50</td><td>难燃烧体 0.25</td></tr></table></body></html>  \n\n<html><body><table><tr><td>名称</td><td colspan=\"4\">耐火等级</td></tr><tr><td>构件</td><td>一级</td><td>二级</td><td>三级</td><td>四级</td></tr><tr><td>柱</td><td>不燃烧体 3.00</td><td>不燃烧体 2.50</td><td>不燃烧体 2.00</td><td>难燃烧体 0.50</td></tr><tr><td>楽</td><td>不燃烧体 2.00</td><td>不燃烧体 1.50</td><td>不燃烧体 1.00</td><td>难燃烧体 0.50</td></tr><tr><td>楼板</td><td>不燃烧体 1.50</td><td>不燃烧体 1.00</td><td>不燃烧体 0.75</td><td>难燃烧体 0.50</td></tr><tr><td>屋顶承重构件</td><td>不.烧体</td><td>不热烧体</td><td>难0烧体</td><td>燃烧体</td></tr><tr><td>疏散楼梯</td><td>不燃烧体 1.50</td><td>不燃烧体 1.00</td><td>不燃烧体 0.75</td><td>燃烧体</td></tr><tr><td>吊顶（包括吊顶格栅）</td><td>不燃烧体 0.25</td><td>难燃烧体 0.25</td><td>难燃烧体 0.15</td><td>燃烧体</td></tr></table></body></html>\n\n$\\textcircled{1}$ 二级耐火等级建筑的吊顶采用不燃烧体时，其耐火极限不限。  \n\n表4-2-3厂房的耐火等级、层数和防火分区的最大允许建筑面积  \n\n\n<html><body><table><tr><td rowspan=\"2\">生产类别</td><td rowspan=\"2\">厂房的 耐火等级</td><td rowspan=\"2\">最多允许层数</td><td colspan=\"4\">每个防火分区的最大允许建筑面积/m</td></tr><tr><td>单层厂房</td><td>多层厂房</td><td>高层厂房</td><td>地下、半地下厂房，厂房的</td></tr><tr><td>甲</td><td>一级 二级</td><td>除生产必须采用多层 者外，宜采用单层</td><td>4000 3000</td><td>3000 2000</td><td></td><td>一</td></tr><tr><td>乙</td><td>一级 二级</td><td>不限 6</td><td>5000 4000</td><td>4000 3000</td><td>2000 1500</td><td></td></tr><tr><td rowspan=\"3\">丙</td><td>一级</td><td>不限</td><td>不限</td><td>6000</td><td>3000</td><td>500</td></tr><tr><td>二级</td><td>不限</td><td>8000</td><td>4000</td><td>2000</td><td>500</td></tr><tr><td>三级</td><td>2</td><td>3000</td><td>2000</td><td></td><td></td></tr><tr><td rowspan=\"3\">丁</td><td>一、二级</td><td>不限</td><td>不限</td><td>不限</td><td>4000</td><td>1000</td></tr><tr><td>三级</td><td>3</td><td>4000</td><td>2000</td><td></td><td></td></tr><tr><td>四级</td><td>1</td><td>1000</td><td>1</td><td></td><td></td></tr><tr><td rowspan=\"3\"></td><td>一、二级</td><td>不限</td><td>不限</td><td>不限</td><td>6000</td><td>1000</td></tr><tr><td>三级</td><td>3</td><td>5000</td><td>3000</td><td></td><td></td></tr><tr><td>四级</td><td>1</td><td>1500</td><td></td><td></td><td></td></tr></table></body></html>\n\n$\\textcircled{1}$ 防火分区之间应采用防火墙分隔。除甲类厂房外的一、二级耐火等级单层厂房，当其防火分区的建筑面积大于本表规定，且设置防火墙确有困难时，可采用防火卷帘或防火分隔水幕分隔。采用防火卷帘时应符合有关规范的规定；采用防火分隔水幕时，应符合现行国家标准《自动喷水灭火系统设计规范》 $G B50084$ 的有关规定。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1213,
+        "chunk": "# 2.建筑物间距  \n\n严格按照国家及地方的有关标准和规范进行设计，表4-2-4和表4-2-5为建筑防火规范中的基本间距。  \n\n续表  \n表4-2-4甲类仓库之间及其与其他建筑、明火或散发火花地点、铁路等的防火间距 单位：m  \n\n\n<html><body><table><tr><td rowspan=\"3\">名称</td><td colspan=\"4\">甲类仓库及其储量/t</td></tr><tr><td colspan=\"2\">甲类贮存物品第3、4项</td><td colspan=\"2\">甲类贮存物品第1、2、5、6项</td></tr><tr><td>≤5</td><td>>5</td><td colspan=\"2\">≤10 >10</td></tr><tr><td>重要公共建筑</td><td colspan=\"4\">50.0</td></tr><tr><td>甲类仓库</td><td colspan=\"4\"></td></tr><tr><td>民用建筑、明火或散发火花地点</td><td>30.0</td><td>40.0</td><td>20.0 25.0</td><td>30.0</td></tr></table></body></html>  \n\n续表  \n\n<html><body><table><tr><td colspan=\"2\"></td><td colspan=\"4\">甲类仓库及其储量/t</td></tr><tr><td colspan=\"2\" rowspan=\"2\">名 称</td><td colspan=\"2\">甲类贮存物品第3、4项</td><td colspan=\"2\">甲类贮存物品第1、2、5、6项</td></tr><tr><td>≤5</td><td>>5</td><td>≤10</td><td>>10</td></tr><tr><td rowspan=\"3\">其他建筑</td><td>一、二级耐火等级</td><td>15.0</td><td>20.0</td><td>12.0</td><td>15.0</td></tr><tr><td>三级耐火等级</td><td>20.0</td><td>25.0</td><td>15.0</td><td>20.0</td></tr><tr><td>四级耐火等级</td><td>25.0</td><td>30.0</td><td>20.0</td><td>25.0</td></tr><tr><td colspan=\"2\">电力系统电压为35～500kV且每台变压器 容量在10MW以上的室外变、配电站 工业企业的变压器总油量大于5t的室外降</td><td>30.0</td><td>40.0</td><td>25.0</td><td>30.0</td></tr><tr><td colspan=\"2\">压变电站 厂外道路路边</td><td colspan=\"4\">20.0</td></tr><tr><td rowspan=\"2\">厂内道路路边</td><td>主要</td><td colspan=\"4\">10.0</td></tr><tr><td>次要</td><td colspan=\"4\">5.0</td></tr></table></body></html>  \n\n表4-2-5厂房之间及其与乙、丙、丁、戊类仓库、民用建筑等之间的防火间距 单位：m  \n\n\n<html><body><table><tr><td colspan=\"4\" rowspan=\"3\">名 称 甲类房</td><td colspan=\"4\">单层、多层丙、丁、</td><td rowspan=\"3\">商层房 （仓库）</td><td colspan=\"3\">民用建筑</td></tr><tr><td rowspan=\"2\">单层多层 房(仓库)</td><td colspan=\"3\">戊类厂房（仓库）</td><td colspan=\"3\">耐火等级</td></tr><tr><td>、二级</td><td colspan=\"3\">三级 四级</td><td>、二级</td><td>三级</td><td>四级</td></tr><tr><td colspan=\"3\">甲类厂房</td><td>12.0</td><td>12.0</td><td>12.0</td><td>14.0</td><td>16.0</td><td>13.0</td><td>25.0</td><td></td><td></td></tr><tr><td colspan=\"3\">单层、多层乙类厂房</td><td>12.0</td><td>10.0</td><td>10.0</td><td>12.0</td><td>14.0</td><td>13.0</td><td>25.0</td><td></td><td></td></tr><tr><td rowspan=\"3\">单层、多层丙、 丁类厂房</td><td>一、二级</td><td>12.0</td><td>10.0</td><td>10.0</td><td>12.0</td><td>14.0</td><td>13.0</td><td>10.0</td><td>12.0</td><td></td><td>14.0</td></tr><tr><td>三级 耐</td><td>14.0</td><td>12.0</td><td>12.0</td><td>14.0</td><td>16.0</td><td></td><td>15.0</td><td>12.0</td><td>14.0</td><td>16.0</td></tr><tr><td>火 四级</td><td>16.0</td><td>14.0</td><td>14.0</td><td>16.0</td><td></td><td>18.0</td><td>17.0</td><td>14.0</td><td>16.0</td><td>18.0</td></tr><tr><td rowspan=\"3\">单层、多层戊 类厂房</td><td>等 一、二级</td><td>12.0</td><td>10.0</td><td>10.0</td><td>12.0</td><td>14.0</td><td></td><td>13.0</td><td>6.0</td><td>7.0</td><td>9.0</td></tr><tr><td>级 三级</td><td>14.0</td><td>12.0</td><td>12.0</td><td>14.0</td><td>16.0</td><td></td><td>15.0</td><td>7.0</td><td>8.0</td><td>10.0</td></tr><tr><td>四级</td><td>16.0</td><td>14.0</td><td>14.0</td><td>16.0</td><td>18.0</td><td>17.0</td><td></td><td>9.0</td><td>10.0</td><td>12.0</td></tr><tr><td rowspan=\"3\">室外变、配电站 变压器总油量/t</td><td>≥5,≤10</td><td rowspan=\"3\">25.0</td><td rowspan=\"3\"></td><td>12.0</td><td></td><td>15.0</td><td>20.0</td><td>12.0</td><td>15.0</td><td>20.0</td><td>25.0</td></tr><tr><td>>10,≤50</td><td>25.0</td><td>15.0</td><td>20.0</td><td>25.0</td><td>15.0</td><td>20.0</td><td>25.0</td><td>30.0</td></tr><tr><td>>50</td><td>20.0</td><td>25.0</td><td></td><td>30.0</td><td>20.0</td><td>25.0</td><td>30.0</td><td>35.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1214,
+        "chunk": "# 3.厂房的安全疏散  \n\n厂房应设置两个以上的安全出口，厂房内最远工作地点离出口的距离、楼梯走道及门的宽度应符合相应的规定。  \n\n$\\textcircled{1}$ 厂房的安全出口应分散布置。每个防火分区、一个防火分区的每个楼层，其相邻2个安全出口最近边缘之间的水平距离不应小于 $5.0\\mathrm{m}$ 0  \n\n$\\textcircled{2}$ 厂房的每个防火分区、一个防火分区内的每个楼层，其安全出口的数量应经计算确 定，且不应少于2个。  \n\n$\\textcircled{3}$ 地下、半地下厂房或厂房的地下室、半地下室，当有多个防火分区相邻布置，并采用防火墙分隔时，每个防火分区可利用防火墙上通向相邻防火分区的甲级防火门作为第二安全出口，但每个防火分区必须至少有1个直通室外的安全出口。  \n\n④厂房内任一点到最近安全出口的距离不应大于表4-2-6的规定。  \n\n表4-2-6厂房内任一点到最近安全出口的距离 单位：m  \n\n\n<html><body><table><tr><td>生产类别</td><td>耐火等级</td><td>单层厂房</td><td>多层厂房</td><td>高层厂房</td><td>地下、半地下厂房或厂房的地下室、半地下室</td></tr><tr><td>甲</td><td>一、二级</td><td>30.0</td><td>25.0</td><td>一</td><td>一</td></tr><tr><td>乙</td><td>一、二级</td><td>75.0</td><td>50.0</td><td>30.0</td><td>一</td></tr><tr><td>丙</td><td>一、二级</td><td>80.0</td><td>60.0</td><td>40.0</td><td>30.0</td></tr><tr><td>丁</td><td>三级 一、二级 三级</td><td>60.0 不限 60.0</td><td>40.0 不限 50.0</td><td>一 50.0 一</td><td>45.0 一</td></tr><tr><td></td><td>四级 一、二级 三级 四级</td><td>50.0 不限 100.0 60.0</td><td>一 不限 75.0 一</td><td>一 75.0 一</td><td>60.0 一 一</td></tr></table></body></html>  \n\n③厂房内的疏散楼梯、走道、门的各自总净宽度应根据疏散人数，按规定经计算确定。但疏散楼梯的最小净宽度不宜小于1.1m，疏散走道的最小净宽度不宜小于1.4m，门的最小净宽度不宜小于0.9m。当每层人数不相等时，疏散楼梯的总净宽度应分层计算，下层楼梯总净宽度应按该层或该层以上人数最多的一层计算。首层外门的总净宽度应按该层或该层以上人数最多的一层计算，且该门的最小净宽度不应小于 $1.2\\mathbf{m}$  \n\n仓库的安全出口应分散布置。每个防火分区、一个防火分区的每个楼层，其相邻2个安全出口最近边缘之间的水平距离不应小于 $5.0\\mathrm{m}$  \n\n③每座仓库的安全出口不应少于2个，当一座仓库的占地面积小于等于300m时，可设置1个安全出口。仓库内每个防火分区通向疏散走道、楼梯或室外的出口不宜少于2个，当防火分区的建筑面积小于等于100m时，可设置1个。通向疏散走道或楼梯的门应为乙级防火门。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1215,
+        "chunk": "# 4.防雷  \n\n建筑物的防雷分类及防雷措施，应按现行国家标准《建筑物防雷设计规范》的有关规定执行。防雷接地装置的电阻要求，应按现行国家标准《石油库设计规范》、《建筑物防雷设计规范》的有关规定执行。  \n\n工艺装置内露天布置的塔、容器等，当顶板厚度等于或大于 $4\\mathrm{mm}$ 时，可不设避雷针保护，但必须设防雷接地。可燃液体贮罐的温度、液位等测量装置，应采用铠装电缆或钢管配线，电缆外皮或配线钢管与罐体应作电气连接。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1216,
+        "chunk": "# 5.静电接地  \n\n对爆炸、火灾危险场所内可能产生静电危险的设备和管道、装卸的管道、汽车罐车均应采取静电接地措施。每组专设的静电接地体的接地电阻值，宜小于 $100\\Omega$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1217,
+        "chunk": "# 四、消防  \n\n消防设计的主要依据为：  \n\n《中华人民共和国消防法》《建筑设计防火规范》（GBJ16—2001）《建筑灭火器配置设计规范》（GBJ140一1997）《建筑防雷设计规范》（GB50057—1994）  \n\n《火灾自动报警系统设计规范》（GBJ116—1988）《爆炸和火灾危险环境电力装置设计规范》（GB50058—1992）",
+        "category": " References"
+    },
+    {
+        "id": 1218,
+        "chunk": "# 1.消防措施综述  \n\n根据中华人民共和国国家标准《建筑设计防火规范》（GBJ16—2001）和《石油化工企业设计防火规范》（GB50160—1992）的生产厂房火灾危险性分类（见表4-2-7)，工艺生产装置生产厂房、液体罐区及泵房和危险品仓库的火灾危险性为甲类，有较大的火灾危险性；其墙、柱、梁、楼板屋顶承重构件、疏散楼梯等应分别达到相应的耐火极限；按照生产厂房的耐火等级标准，这些装置建构筑物的耐火等级为二级。其他建构筑物火灾危险等级为戊级，耐火等级二级。  \n\n表4-2-7 贮存物品的火灾危险性分类  \n\n\n<html><body><table><tr><td>仓库类别</td><td>项别</td><td>贮存物品的火灾危险性特征</td></tr><tr><td rowspan=\"5\">甲</td><td>1</td><td>闪点小于28℃的液体</td></tr><tr><td>2</td><td>爆炸下限小于10%的气体，以及受到水或空气中水蒸气的作用，能产生爆炸下限小于10%气体的固 体物质</td></tr><tr><td>3</td><td>常温下能自行分解或在空气中氧化能导致迅速自燃或爆炸的物质</td></tr><tr><td>4</td><td>常温下受到水或空气中水蒸气的作用，能产生可燃气体并引起燃烧或爆炸的物质</td></tr><tr><td>5 6</td><td>遇酸、受热、撞击、摩擦以及遇有机物或硫黄等易燃的无机物，极易引起燃烧或爆炸的强氧化剂</td></tr><tr><td rowspan=\"2\">乙</td><td>１ 2 3 4</td><td>受撞击、摩擦或与氧化剂、有机物接触时能引起燃烧或爆炸的物质 闪点大于等于28℃，但小于60℃的液体 爆炸下限大于等于10%的气体 不属于甲类的氧化剂</td></tr><tr><td>5 6 1</td><td>不属于甲类的化学易燃危险固体 助燃气体 常温下与空气接触能缓慢氧化，积热不散引起自燃的物品</td></tr><tr><td>丙 丁</td><td>2</td><td>闪点大于等于60℃的液体 可燃固体</td></tr><tr><td>戊</td><td></td><td>难燃烧物品</td></tr><tr><td></td><td></td><td>不燃烧物品</td></tr></table></body></html>  \n\n根据项目的具体情况，应严格采取如下消防安全措施，保证装置生产安全：  \n\n$\\textcircled{1}$ 严格按照国家及地方的有关标准和规范进行设计。$\\textcircled{2}$ 总图布置中充分考虑防火间距，消防通道畅通。$\\textcircled{3}$ 工艺装置设计中充分考虑工艺过程及设备的设置和选型，消除火灾隐患。$\\textcircled{4}$ 建筑设计遵循建筑防火规定，厂区道路、供水条件及建构筑物耐火等级等均要符合消防规范的要求。承重部分采用防火结构，有利于防火。建筑物均设有符合要求的出人口、楼梯和通道，有利于安全疏散。  \n\n对职工尤其是操作工人应继续进行系统的防火教育，加强其安全意识。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1219,
+        "chunk": "# 2.消防设施  \n\n工厂应根据物品贮存量、建筑物大小、物品化学性质配置足够的消防设施。  \n\n(1）水消防系统在整个厂区范围内设置水消防系统。该系统由消防水池、消防水泵、消防给水管网、室外消火栓组成。消防给水管网布置在厂区道路旁，形成环网状。消防给水采用临时高压制，火灾时由设置在消防水泵房的消防水泵加压供水。水源来自工厂生活水供水管网和消防水池。工厂、仓库、堆场、贮罐（区）和民用建筑的室外消防用水量，按同一时间内的火灾次数和一次灭火用水量确定（见表4-2-8)：室外消防水量 $30\\mathrm{L}/\\mathrm{s}$ ，供水压力  \n\n为 $\\tilde{\\mathbb{O}}_{*}\\hat{\\mathfrak{G}}\\mathbf{M}\\mathbf{Pa}$ 0  \n\n\n<html><body><table><tr><td rowspan=\"2\">耐火 等级</td><td colspan=\"2\" rowspan=\"2\">建筑物类别</td><td colspan=\"6\">：建筑物体积V/m3</td></tr><tr><td>V≤1500</td><td>1500<V≤3000</td><td>3000<V≤5000</td><td></td><td>5000<V≤2000020000<V≤50000V>50000</td><td></td></tr><tr><td rowspan=\"6\">二级</td><td rowspan=\"2\">厂房</td><td>甲、乙类 丙类</td><td>10</td><td>15</td><td>20</td><td>25</td><td>30</td><td>35</td></tr><tr><td></td><td>10</td><td>15</td><td>20</td><td>25</td><td>30</td><td>40</td></tr><tr><td rowspan=\"2\"></td><td>丁、戊类</td><td>10</td><td>10</td><td>10</td><td>15</td><td>15</td><td>20</td></tr><tr><td>甲、乙类</td><td>15</td><td>15</td><td>25</td><td>25</td><td>一</td><td>一</td></tr><tr><td rowspan=\"2\">仓库</td><td>丙类</td><td>15</td><td>15</td><td>25</td><td>25</td><td>35</td><td>45</td></tr><tr><td>丁、戊类</td><td>10</td><td>10</td><td>10</td><td>15</td><td>15</td><td>20</td></tr><tr><td colspan=\"2\">民用建筑</td><td></td><td>10</td><td>15</td><td>15</td><td>20</td><td>25</td><td>30</td></tr><tr><td rowspan=\"3\">三级</td><td>厂房(仓库)</td><td>乙、丙类 丁、戊类</td><td>15</td><td>20</td><td>30</td><td>40</td><td>45</td><td>一</td></tr><tr><td></td><td></td><td>10</td><td>10</td><td>15</td><td>20</td><td>25</td><td>35</td></tr><tr><td colspan=\"2\">民用建筑</td><td>10</td><td>15</td><td>20</td><td>25</td><td>30</td><td>一</td></tr><tr><td rowspan=\"2\">四级</td><td>丁、戊类厂房(仓库)</td><td></td><td>10</td><td>15</td><td>20</td><td>25</td><td>一</td><td>一</td></tr><tr><td>民用建筑</td><td></td><td>10</td><td>15</td><td>20</td><td>25</td><td></td><td></td></tr></table></body></html>  \n\n在生产车间、危险品仓库、半露天堆场、非危险品仓及办公楼等建筑物内设室内自动水喷淋系统及消防竖管（参见表4-2-9)。  \n\n表4-2-9 室内消火栓用水量  \n\n\n<html><body><table><tr><td rowspan=\"2\">建筑物名称</td><td rowspan=\"2\">高度h/m、层数、体积V/m 或座位数n/个</td><td rowspan=\"2\"></td><td rowspan=\"2\">消火栓用水量/(L/s)</td><td rowspan=\"2\">同时使用水枪</td><td rowspan=\"2\">每根竖管最小 流量/(L/s)</td></tr><tr><td>数量/支</td></tr><tr><td rowspan=\"3\">厂房</td><td>h≤24</td><td>V≤10000 V>10000</td><td>5</td><td>2</td><td>5</td></tr><tr><td></td><td></td><td>10</td><td>2</td><td>10</td></tr><tr><td colspan=\"2\">24<h≤50 h>50</td><td>25 30</td><td>5 6</td><td>15 15</td></tr><tr><td rowspan=\"3\">仓库</td><td>h≤24</td><td>V≤5000</td><td>5</td><td></td><td>5</td></tr><tr><td></td><td>V>5000</td><td>10</td><td>2</td><td>10</td></tr><tr><td colspan=\"2\">24<h≤50 h>50</td><td>30</td><td>6</td><td>15</td></tr><tr><td rowspan=\"2\">科研楼、试验楼</td><td colspan=\"2\">h≤24，V≤10000</td><td>40</td><td>8</td><td>15</td></tr><tr><td colspan=\"2\">h≤24,V>10000</td><td>10 15</td><td>2</td><td>10</td></tr></table></body></html>  \n\n(2）泡沫消防系统在甲乙级厂房仓库危险品罐区设固定自动泡沫消防系统。该系统由消防水池、泡沫消防泵、泡沫比例混合装置、泡沫消防管网、泡沫栓、泡沫产生器、报警阀、泡沫喷淋等组成。固定泡沫系统流量 $8.8L/s$ 。供水压力为 $0.85\\mathrm{{MPa}}$ 。同时，按规定在相应位置配备移动式灭火器，在建筑物四周布置室外消防栓  \n\n设置固定式泡沫灭火系统的贮罐区，在其防火堤外设置用于扑救液体流散火灾的辅助泡沫枪，其数量及其泡沫混合液连续供给时间，不应小于表4-2-10 的规定。每支辅助泡沫枪的泡沫混合液流量不应小于 $240\\mathrm{L}/\\operatorname*{min}$  \n\n表4-2-8工厂、仓库和民用建筑一次灭火的室外消火栓用水量 单位： $L/s$   \n表4-2-10 泡沫枪数和连续供给时间  \n\n\n<html><body><table><tr><td>贮罐直径/m</td><td>配备泡沫枪数/支</td><td>连续供给时间/min</td><td>贮罐直径/m</td><td>配备泡沫枪数/支</td><td>连续供给时间/min</td></tr><tr><td>≤10</td><td>１</td><td>10</td><td>>30且≤40</td><td>2</td><td>30</td></tr><tr><td>>10且≤20</td><td>1</td><td>20</td><td>>40</td><td>3</td><td>30</td></tr><tr><td>>20且≤30</td><td>2</td><td>20</td><td></td><td></td><td></td></tr></table></body></html>  \n\n(3）其他灭火设备及消防设施生产厂房、仓库、办公楼等内部根据面积和危险等级配备一定数量移动式灭火器。灭火器品种、规格和数量按照《建筑灭火器配置设计规范》的要求进行配置。可采用磷酸铵盐干粉灭火器和二氧化碳灭火器，以及推车式灭火器。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1220,
+        "chunk": "# 3.消防安全措施  \n\n根据工厂的具体情况，应采取如下消防安全措施，保证装置生产安全。  \n\n$\\textcircled{1}$ 总图布置中充分考虑防火间距，消防通道畅通。  \n\n$\\textcircled{2}$ 工艺装置区、液化烃贮罐区应设环形消防车道。可燃液体的贮罐区、装卸区及化学危险品仓库区应设环形消防车道。  \n\n$\\textcircled{3}$ 工艺装置设计中充分考虑工艺过程及设备的设置和选型，消除火灾隐患。沿地面或低支架敷设的管道，不应环绕工艺装置或罐组四周布置。距散发比空气重的可燃气体设备$30\\mathrm{m}$ 以内的管沟、电缆沟、电缆隧道，应采取防止可燃气体窜人和积聚的措施。  \n\n$\\textcircled{4}$ 工艺设备（以下简称设备）、管道和构件的材料，应符合下列规定：设备本体（不含衬里）及其基础，管道（不含衬里）及其支、吊架和基础，应采用非燃烧材料，但油罐底板垫层可采用沥青砂。  \n\n设备和管道应根据其内部物料的火灾危险性和操作条件，设置相应的仪表、报警信号、自动联锁保护系统或紧急停车措施。  \n\n$\\textcircled{5}$ 设备、可燃液体罐，建筑物平面布置的防火间距、防火等级应符合《建筑设计防火规范》的要求。  \n\n$\\textcircled{6}$ 罐组内相邻可燃液体地上贮罐的防火间距，不应小于表4-2-11的规定。  \n\n表4-2-11甲、乙、丙类液体贮罐之间的防火间距 单位：m  \n\n\n<html><body><table><tr><td rowspan=\"2\" colspan=\"3\">类别</td><td colspan=\"5\">贮罐形式</td></tr><tr><td></td><td>固定顶罐</td><td></td><td>浮顶</td><td>卧式 贮罐</td></tr><tr><td rowspan=\"3\">甲、乙类液体</td><td rowspan=\"3\">单罐容量 V/m</td><td>V≤1000</td><td>地上式 0.75D</td><td>半地下式</td><td>地下式</td><td>贮罐</td><td rowspan=\"3\">不小于0.8m</td></tr><tr><td>V>1000</td><td>0.6D</td><td>0.5D</td><td>0.4D</td><td>0.4D</td></tr><tr><td>不论容量大小</td><td>0.4D</td><td>不限</td><td>不限</td><td></td></tr></table></body></html>\n\n注：1.表中 $D$ 为相邻较大罐的直径，单罐容积大于 $\\mathrm{1000m^{3}}$ 的贮罐取直径或高度的较大值。2.贮存不同类别液体的或不同型式的相邻贮罐的防火间距，应采用本表规定的较大值。3.高架罐的防火间距，不应小于 $0.6\\mathrm{m}$ 4.现有浅盘式内浮顶罐的防火间距同固定顶罐。  \n\n$\\textcircled{7}$ 对职工尤其是操作工人应继续进行系统的防火教育，定期检修消防设备及器材；对消防人员进行培训，人员持证上岗，加强其安全意识。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1221,
+        "chunk": "# 4.火灾报警系统  \n\n设计时应设置火灾探测器、手动火灾报警按钮、声光报警器、区域报警显示器、水流指示器、防火卷帘门设二总线制编码模块，消防信号接人消防控制室内的火灾报警控制器。火灾自动报警系统由专用消防供电回路供电，并配备直流备用电源，并与地方消防网络系统连接，实现自动模式；同时设广播系统以便疏散。  \n\n车间内设置消火栓信号系统，事故时启动消防水泵。  \n\n空调送回风风道应设有联动防火阀，一旦防火阀动作，必须切断送、回风风机电源。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1222,
+        "chunk": "# 五、环境保护",
+        "category": " Conclusions"
+    },
+    {
+        "id": 1223,
+        "chunk": "# 1.概述  \n\n根据《中华人民共和国环境保护法》等有关法规，在项目实施过程中对生产过程中排出的污染物应采取必要的措施，使之达到国家规定的标准。项目设计时，应按照清除污染、保护环境、综合利用、化害为利的原则进行设计，三废治理工程与主体工程项目同时设计、施工，同时建成投产，使生产中产生的“三废”达到国家规定标准后排放。废气排放标准为《工业“三废”排放试行标准》（GBJ4)；废水排放标准为《污水综合排放标准》（GB8978)。  \n\n设计的主要标准依据如下：  \n\n《中华人民共和国环境保护法》  \n\n《建设项目环境保护管理条例》国务院（1998）253号  \n《建设项目环境保护设计规定》（1987）国环字第002号  \n《污水综合排放标准》（GB8978—1996）  \n《工业企业厂界噪声标准》（GB12348—1990)  \n《环境空气质量标准》（GB3095一1996）  \n《大气污染物综合排放标准》（GB16297一1996）",
+        "category": " Introduction"
+    },
+    {
+        "id": 1224,
+        "chunk": "# 2.主要污染源及污染物  \n\n涂料生产过程中排放的污染物主要为有机挥发物、废水和噪声。工艺过程中产生的废水主要是设备清洗水。废水含有有机物质和无机悬浮物质，需要进行专门的处理。工艺过程中产生的有机挥发物主要是由于溶剂挥发所致。有机挥发物会污染大气，需要进行收集和活性炭处理。主要生产设备如风机、压缩机、输送泵、灌装机等生产过程中会产生一定的噪声，对环境造成一定的污染。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1225,
+        "chunk": "# 3.废水治理  \n\n生产污水排放应采用暗管或覆土厚度不小于 $200\\mathrm{mm}$ 的暗沟。设施内部若必须采用明沟排水时，应分段设置。生活污水在化粪池进行初步处理后用做绿化补充水，也可排人工业园区污水收集系统。生产中使用的清净的冷却水循环可做绿化补充水使用。  \n\n生产中的设备清洗水，及含可燃液体的污水及被可燃液体严重污染的雨水，应排入生产污水管道，送至污水处理场处理。污水处理场（站）的处理能力，应考虑开停工、检修、事故等工况。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1226,
+        "chunk": "# 4.废渣（液）污染物控制措施  \n\n(1）严格控制新鲜水用量。新建厂新鲜水的单耗，达到国内同行业先进水平。(2）优先选用不产生或少产生废水的工艺及设备。生产用水，多次利用、循环使用及回用，以减少废水的排放量。(3）原料、燃料、产品的露天堆场和装卸站台及码头，应有防止雨水冲刷物料而造成污染的措施。(4）自采样、溢流、事故及管道低点排出的物料（如油品、溶剂、化学药剂等)，应进人收集系统或其他收集设施，不得就地排放和排人排水系统。(5）贮存化学药剂、废渣（液）的容器，应有排尽、收集措施，不得将上述物料排人排水系统。  \n\n(6）凡易受污染场所（如塔区、泵区、换热器区、化工原料罐区及浮顶油罐顶、原油及化工原料装卸台等）的初期雨水和地面冲洗水，应排人相应的排水系统，经处理合格后排放。  \n\n（7）不同的废渣（液）宜单独贮存。两种或两种以上废渣（液）混合贮存时，应符合下列要求：  \n\n$\\textcircled{1}$ 不产生新的有害有毒物质；$\\textcircled{2}$ 不发生有害的化学反应；$\\textcircled{3}$ 有利于堆放贮存、综合利用或处理。(8）设备检修及开停工时，排出的废渣（液)，必须设置收集设施，以便进一步处理。（9）有毒害、易扬尘的废渣（液）装卸和输送时，应采取密闭或增湿等措施。(10）可燃废渣（液）在焚烧过程中产生的有害气体，必须经净化处理；焚烧后的残渣应妥善处置，其他有危害的废渣，送有资质的专业危废处理公司处理。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1227,
+        "chunk": "# 5.噪声污染的防治  \n\n涂料生产噪声污染主要来源于各种机械设备。根据目前的技术条件，在多数情况下还难于采用从噪声源入手降低噪声，以达到环境标准的措施。只能在噪声传播途中采取控制措施，如消声、隔声、减振等。  \n\n工艺装置、加热护和锅炉等的蒸汽或压力气体的放空，应选用适用于该种气体特性的放空消声器，并考虑排气口噪声扩散的指向性。  \n\n当低噪声空冷器不能满足环境噪声标准时，应设置吸声或隔声屏等降低其噪声的影响。  \n\n对离厂界较近的高噪声源（如锅炉、加热炉、空压站等)，除应采取必要的综合治理设施外，还可利用绿化带或卫生防护距离减弱噪声对环境的影响。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1228,
+        "chunk": "# 6.废气、粉尘污染防治  \n\n（1）凡连续散发有毒有害气体、粉尘、恶臭等物质的生产过程，应设计成密闭的生产系统。当需外排时，还应设置除尘、吸收等净化设施。  \n\n(2）对含有易挥发物质的原料、成品、中间产品等贮存设施，应有防止挥发物逸出的措施，如采用浮顶罐、油气回收等。  \n\n（3）污染大气的放空尾气，应回收利用或妥善处理。  \n\n（4）易挥发的原料、产品，应密闭装卸或浸没装卸。  \n\n(5）排气筒（管）的设计高度，应根据环境影响报告书（表）的要求确定。  \n\n(6）排放有毒有害气体的排气筒（管)，必须设置采样口，采样口的设计，应按《石油化工企业排气筒（管）采样口设计规范》（SH3056）执行。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1229,
+        "chunk": "# 7.绿化  \n\n绿化可以清洁空气，补充氧气，改善工厂小气候，减少有害气体的危害。因此，可利用车间周围、道路两旁空地进行绿化。选择适应当地生长条件的乔木、灌木及草皮进行栽种。厂区绿化设计指标，应以厂区绿化用地系数表示：位于一般地区的企业，不应小于 $12\\%$ 中有些工业区要求达到 $35\\%$ 0  \n\n为在达标的基础上进一步减少噪声、废气等的影响，全厂应重视绿化工作，具体如下：  \n\n(1）厂区建设应重视绿化工作，并从整体上与厂貌协调，注意绿化布局的层次、风格；(2）厂区内的绿化覆盖率达到设计要求，充分考虑植被的多样性，可采用“乔、灌、花、草”相结合的多层次复合绿化系统，合理分配高大与低矮植物的布设；  \n\n(3）厂内应充分利用建设用地区域内空地、道路两旁进行绿化，同时在车间四周建设一定的绿化隔离带，达到降噪和吸尘作用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1230,
+        "chunk": "# 六、职业安全卫生  \n\n职业女主卫生议计低循如1：《中华人民共和国劳动法》（中华人民共和国主席令第28号，1995年1月1日施行)《中华人民共和国安全生产法》（2002年11月1日实施)《建设项目（工程）职业安全卫生监督规定》［中华人民共和国劳动部（1996）3号令]《建筑防雷设计规范》（GB50057—2001)《生产过程安全卫生总则》（GBJ2801—1991)《工业企业设计卫生标准》（GBZ1一2002)《工业企业噪声控制设计规范》（GBJ87—1985)《电器设备安全设计导则》（GB4064—1983)《中华人民共和国消防法》（中华人民共和国主席令第4号，1998年9月1日施行)《中华人民共和国职业病防治法》（中华人民共和国主席令第60号，2002年5月1日  \n施行)《使用有毒物品作业场所劳动保护条例》（2002年5月19日国务院发布）《危险化学品安全管理条例》（中华人民共和国国务院令344号，2002年3月15日  \n施行)《国务院关于加强防尘防毒工作的决定》（国发［1984］97号）《中华人民共和国监控化学品管理条例》（国务院令第190号)《特种设备安全监察条例》国务院令第373号，2003年6月1日施行)《建设项目（工程）劳动安全卫生监察规定》（原劳动部令第3号，1997年1月1日  \n施行）《爆炸危险场所安全规定》（原劳动部［1995］56号）《工作场所安全使用化学品规定》（原劳动部发［1996］423号)《中华人民共和国爆炸危险场所电气安全规程》（劳人护[1987］36号)《职业健康监护管理办法》（卫生部令第23号）《职业病诊断与鉴定管理办法》（卫生部，2002年5月1日施行)《劳动防护用品监督管理规定》（国家安监总局令第1号，2005年9月1日施行)《危险化学品建设项目安全许可实施办法》（国家安监总局令第8号，2006年10月1日  \n施行)《危险化学品事故应急救援预案（单位版）编制指南》（安监管危化字［2004］43号)《特种设备质量监督与安全监察规定》（国家质量技术监督局令第13号，2000.10.1)《特种设备作业人员监督管理办法》（国家质检总局令第70号，2005.7.1)《作业场所安全使用化学品公约》(第170号国际公约)",
+        "category": " References"
+    },
+    {
+        "id": 1231,
+        "chunk": "# 1.危害因素分析  \n\n(1）装置特点涂料装置工艺过程属于物理过程，没有高温高压操作工况。但是生产原材料品种繁多，性质复杂，有易燃易爆危险化学品，还有对人体有一定毒害性的物品，产品中的溶剂也有一定的燃烧危险。因此，防火防爆和防毒是设计、施工和生产应该注意的重点。  \n\n另外，在工厂操作中也会产生机械伤害，电气伤害和噪声危害也有发生的可能。因此，这些一般性伤害的预防也需要予以重视。  \n\n（2）生产过程主要不安全因素分析  \n\n① 燃烧和爆炸危险由于工艺过程中使用易燃易爆物品，部分属于甲B类易燃易爆危险物质。在这些危险品比较集中的工艺生产装置、液体罐区和危险品仓库，燃烧、爆炸是始终存在的潜在危险。  \n\n$\\textcircled{2}$ 转动设备伤害装置大量使用一些转动设备，如各种搅拌机、离心机、输送泵、风机、压缩机等。这些转动机械在运行和检修的时候，有对人体造成伤害的可能。  \n\n$\\textcircled{3}$ 机械性伤害地面暗井、坑、沟、设备平台、楼梯等有造成人体滑倒、坠落等事故的可能。  \n\n$\\textcircled{4}$ 噪声各种机械在运转时都会发出一定的噪声，对人体产生声危害。主要危害表现 为头晕、恶心、失眠、心悸、听力减退、神经衰弱等症状。  \n\n$\\textcircled{5}$ 热辐射和烫伤某些操作岗位的操作温度比较高。这会对操作人员造成热辐射、烫伤的危险。  \n\n$\\textcircled{6}$ 电气伤害电气设备的漏电、接地不良等可能造成人身伤害和设备破坏。  \n\n$\\textcircled{7}$ 毒害性多种物料对人体均有一定的毒害性，某些物品燃烧时会产生有毒气体一氧化碳等。所以如果不加强防范，或者在某种事故状态下，有发生中毒的危险。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1232,
+        "chunk": "# 2.生产工艺及生产设备安全对策措施  \n\n（1）生产工艺安全对策措施  \n\n$\\textcircled{1}$ 生产工艺安全设计必须符合人-机工程原则，以便最大限度地降低操作者的劳动强度以及精神紧张状态；  \n\n$\\textcircled{2}$ 应防止工作人员直接接触具有危险有害因素的设备、设施、生产原材料及产品；  \n\n$\\textcircled{3}$ 工艺过程中一直存在着有毒物质，应在生产过程中采取有效措施避免有毒物质泄漏，厂房内设通风设备，使有毒蒸气浓度不超过国家卫生标准；  \n\n$\\textcircled{4}$ 对高温管道和设备均进行保温和人身防护，对一些高温设备及管道，进行保温、隔热，以防灼伤人体，采取保温措施后的表面温度不大于 $40C$ 中  \n\n$\\textcircled{5}$ 在使用二甲苯等危险物品时，应严格执行操作规程，确保安全生产。在车间内易接触有机物及其蒸气等有毒物质的位置，应设置安全喷淋洗眼器，当发生意外伤害事故时，通过快速喷淋、冲洗，把伤害程度减到最低；  \n\n$\\textcircled{6}$ 对生产线，主机采用计算机控制，配有电气连锁、电气保护、自动报警、自动停车并设有各种安全装置，意外事故状态时，对设备及人身进行保护；  \n\n$\\textcircled{7}$ 工厂采用的生产设备和机械化装置（包括自动化装置）必须互相匹配、协调，在生产过程中应有机地融为一体，不得构成危险或不安全因素；  \n\n$\\textcircled{8}$ 工厂必须在危险区内为操作者选择、提供并强制使用安全装置。安全装置包括安全保护装置（如各种防护罩、防护隔栏等）与安全控制装置（如双手控制装置、光控式保护装置等）两大类；  \n\n$\\textcircled{9}$ 事故停车开关必须安装在操作人员能够迅速触及的地方，以保证安全操作；  \n\n$\\textcircled{10}$ 机械设备应装配可靠的光电保护装置，定期检查、及时更换；  \n\n$\\textcircled{17}$ 车间各区域（空间）、部门和设备，凡可能危及人身安全时应按有关规定，于醒目处设标志牌；  \n\n$\\textcircled{12}$ 操作工人应经常注意设备的工作状态，发现异常声音和振动，必须及时停机检查；  \n\n③工厂必须设置安全检查机构，安全检查机构由专职安全检查人员和兼职安全检查人员组成；  \n\n$\\textcircled{14}$ 对建筑物应在设计中采取隔声、吸声措施，噪声高的设备旁悬挂吸声板，操作人员佩戴防声耳塞减少噪声影响；  \n\n$\\textcircled{15}$ 根据作业场所特点，正确选择I、Ⅱ、Ⅲ类手持电动工具，确保安全可靠，并根据要求严格执行安全操作规程；  \n\n$\\textcircled{15}$ 安装在设备周围的配管、阀门、仪表等要留有充分的空间，以免互相碰撞，并且稳妥地固定；  \n\n$\\textcircled{17}$ 在生产过程中应加强对各类设备的日常检查和维修保养，生产装置所配备的各种压力表、温度计、安全阀、报警器等仪表必须齐全，并按规定定期进行检验、检测或校验；  \n\n$\\textcircled{18}$ 生产装置漆色应明确安全色制度，对有毒有害场所要有安全标志；  \n\n$\\textcircled{19}$ 定期对各种加工设备进行检查检修；  \n\n$\\textcircled{20}$ 设备检修过程中检修人员必须在人员监护下进行检修作业。  \n\n（2）生产设备安全对策措施  \n\n$\\textcircled{1}$ 转动设备的高速转动部分如电机部分应采用加罩防护或隐蔽防护，同时对裸露的转动部件需采取适当的保护措施。这些措施包括：在不同的危险部位设立防护栏杆，或对危险区域采用涂色、警示线等办法，以防止操作工接近危险部位，设备平台及楼梯均设置护栏。  \n\n$\\textcircled{2}$ 对有振动及噪声产生的设备应采用减振垫、减振器及隔声操作室以减缓振动及噪声危害的程度。其中，有强烈振动的高噪声设备，不宜布置在楼板上或钢制平台上；对分散布置的高噪声设备，宜采用隔声罩；对集中布置的高噪声设备，宜采用隔声间，对难以采用隔声罩或隔声间的某些高噪声设备，宜在声源附近或受声处设置隔声屏障；对不需要人员始终在设备旁操作的高噪声车间和站房，如空压站等设计隔声值班室或控制室。  \n\n$\\textcircled{3}$ 定期检查设备的防护措施是否有效，对设备进行清洗。  \n\n$\\textcircled{4}$ 空压机等噪声高的设备、机组，要单独放在室内，基础要采取减振措施，气流出口配备消声器，管道采用软连接，控制室采用双层隔声玻璃窗和隔声门。  \n\n$\\textcircled{5}$ 制定叉车的安全对策措施。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1233,
+        "chunk": "# 3.电气设备系统的安全对策措施  \n\n$\\textcircled{1}$ 事故照明灯具布置在可能引起事故的设备、材料、物品的周围和主要通道、危险地段、出人口等处，事故照明的照度不应低于工作照明度的 $10\\%$ 鼎  \n\n$\\textcircled{2}$ 在爆炸及火灾危险场所维护检查电气设备时，严禁解除保护、联锁和信号装置；故障停电后未查清原因前禁止强行送电；严禁带电对接电线（明火对接）和使用能产生冲击火花的工、器具。  \n\n$\\textcircled{3}$ 采取“电缆进出口用网格围住，防止小动物进人；配电间应有防雨、雪进人的措施，并有通风排湿措施；土建设计必须符合配电所设计规范，电缆沟应有排水措施”等措施以防止“高、低压跳闸事故”。  \n\n$\\textcircled{4}$ 采取“严禁长时间超负荷运行；定期检查维护电气设备等，在事故前清除各类隐患；严格遵守变压器运行规程，定期检查，确保各项保护齐全有效”等措施以防止“变压器着火、爆炸”。  \n\n$\\textcircled{5}$ 采取“变压器设置围栏并挂警示牌；杜绝违章作业；立即检查，清除漏电点；检修或更换故障设备；加强职工教育，提高职工安全意识和自我保护意识，杜绝违章作业”等措施以防止“变压器、开关柜等触电事故”。  \n\n③采取“严格遵守操作规程；检修时加强自我保护意识，集中思想，消除马虎、不在乎的麻痹思想”等措施以防止“开关柜电弧灼伤事故”。  \n\n?采取“认真对设计进行审查工作；规范电气施工，严格把好采购质量关，杜绝假冒、伪劣产品；电气设备、电缆、导线附近不得堆放易燃物；防止易燃、易爆物质泄漏，并设置报警装置”等措施以防止“电缆、导线着火事故”。  \n\n$\\textcircled{8}$ 采取“规范电气施工，并加强验收工作；加强巡回检查，及时发现井检修、更换；保持环境干燥、清洁，加强通风；严禁违章，特别要严禁非专业人员进行电气作业；定期检查和更新设备；加强职工教育，建立健全规章制度，提高职工安全意识”等措施以防止“电缆、导线等裸露、漏电事故”。  \n\n$\\textcircled{9}$ 采取“加强对操作工人的教育，增强其工作责任心，增加其安全知识；加强对管理人员的安全教育，增强其法制观念，增加其安全知识”等措施以防止“人体误接触带电设备触电事故”。  \n\n$\\textcircled{10}$ 采取“各装置、设备、设施及建筑物，应根据国家标准和规定确定防雷等级，设计可靠的防雷保护装置，防止雷电对人身、设备以及建筑物的危害和破坏”等措施以防止“雷电引发的电气事故”。  \n\n$\\textcircled{11}$ 采取“降低液体物料在管道中的流速；采取静电跨接、直接接地、间接接地等手段，把设备、管道等与大地作可靠的电气连接”等措施以防止“静电引发的电气事故”。  \n\n$\\textcircled{12}$ 对操作人员应做岗前安全技术培训，提高安全技术防护水平，严格执行规章制度，落实安全生产责任制；加强职工技术培训、安全培训；努力提高职工技术素质、安全意识和自我保护意识。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1234,
+        "chunk": "# 4.职业性危害方面的对策措施  \n\n(1）防毒本工程项目中涉及二甲苯等有毒物质，在生产中要针对这些物质提出如下安全对策措施：  \n\n$\\textcircled{1}$ 防止物料外泄是生产、贮存、运输过程中十分重要的步骤，泄漏事故可能会引起连续的严重事故（如毒物作用及火灾爆炸)。设备失效及人为失误是泄漏事故的主要原因，因此，选择合适的设备，加强设计、管理及全体职工的职责是降低泄漏事故发生的关键因素。  \n\n$\\textcircled{2}$ 加强操作工人防护措施，从事有毒有害介质作业的工人上岗时应穿戴工作服、安全帽、防护眼镜和合适材料的手套，车间常备救护用具及药品。  \n\n$\\textcircled{3}$ 接触有毒有害物质的作业人员必须进行就业前的体检和定期的健康检查，开展安全员“健康监护”。  \n\n(2）防噪声尽可能选用低噪声的压缩机、风机等机械设备，当实际运行中出现噪声危害时，应采取隔离噪声源、设置消声器、减振等措施减轻噪声危害。工人在作业中接触高于85dB（A）噪声源时，应使用耳塞或耳罩，安排适当工间休息；长期在高噪声设备周围工作的人员应定期进行听力检查。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1235,
+        "chunk": "# 5.消防安全对策措施  \n\n$\\textcircled{1}$ 在消防设计中要严格执行规范规定，充分尊重消防监督部门的意见，吸收国内外先进经验，把好设计关，消防系统必须通过当地消防部门的验收认可。  \n\n$\\textcircled{2}$ 消防系统的布置、设计要合理，留有足够的消防通道，保证消防、急救车辆到达该区域畅通无阻。同时人流、物流不交叉，道路宽度应符合有关规范要求。  \n\n$\\textcircled{3}$ 生产装置区、贮罐区、仓库除应设置固定式、半固定式灭火设施外，还应按规定设置小型灭火器材。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1236,
+        "chunk": "# 一、设备设计应遵循的主要法规和标准、规范  \n\n《钢制管壳式换热器》（GB151)  \n《钢制焊接常压容器》（JB/T4735）  \n《机械搅拌设备》（HG/T20569）  \n《塑料设备》（HG20640)  \n《钢制压力容器》（GB150）  \n《化工管道设计规范》（HGJ8）  \n《设备及管道保温设计导则》（GB8175）  \n《设备及管道保温设计通则》（GB1790）  \n《化工设备，管道外防腐设计规定》（GBJ34）  \n《原油长输管道工艺及输油站设计规范》（SJY13）  \n《石油化工企业设备与管道涂料防腐设计与施工规范》（SHJ22）  \n《钢制管道及储罐防腐蚀工程设计规范》（SY』7）  \n《石油化工企业蒸汽伴管及夹套设计规范》（SHJ40）  \n《石油化工企业管道柔性设计规范》（SHJ41）  \n《石油化工企业管道布置设计通则》（SHJ.12)  \n《化工厂管架设计规定》（HGJ22）  \n《石油化工剧毒，易燃，可燃介质管道施工及验收规范》（SHJ501)  \n《压力容器安全技术监督规则》［劳锅字（1990）8号］  \n《锅炉压力容器安全监察暂行条例》［国发（1982）22号］  \n《锅炉压力容器安全监察暂行条例实施细则》［劳人锅（1982）6号]  \n《常用立式储罐抗震鉴定标准及条文说明》（SHJ26）  \n《钢制化工容器材料选用规定》（HG】15）  \n《钢制化工容器设计基础规定》（HGJ14）  \n《钢制化工容器强度计算规定》（HGJ16）  \n《钢制化工容器结构设计规定》（HGJ17），  \n《钢制低温压力容器技术规定》（HGJ19）  \n《立式圆筒形钢制焊接储罐设计规范及条文说明》（CD130A2）  \n《生产设备安全卫生设施总则》（GB5083）",
+        "category": " References"
+    },
+    {
+        "id": 1237,
+        "chunk": "# 二、树脂合成工艺  \n\n树脂合成基本组成部分有：反应釜，加热及冷却系统，加压及真空系统，蒸馏系统，包装系统，操作控制系统及辅助设备（如备料釜、贮料釜、氮封系统、压缩空气、计量系统、分离釜、稀释罐、过滤器及废气、废水收集处理系统等)。一般来说，树脂合成工艺流程及技术要求（合成参数）由树脂研发部门提供，设计人员（一般为专业的化工设计院）会根据具体要求来设计工艺流程图，根据投资预算和产量预估来设计设备布置、设备结构、设备材质、管线安装、介质选择、控制方案等。  \n\n在过去很长一段时间内，非常多的涂料工厂包括了树脂合成技术。随着专业化和企业并购的加速，大部分的涂料巨头放弃了树脂合成技术，从而专注于涂料的技术开发、生产、应用领域及客户开发。故而本节就不加以详尽描述。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1238,
+        "chunk": "# 三、涂料生产工艺  \n\n纯粹涂料生产的工艺流程简短而繁多，具有较大的灵活性。一般根据涂料的品种，规模，配方而设定具体的流程方案。流程方案和投资的大小也有关系，从手工工厂到全自动化的工厂，工艺流程差异很大。  \n\n涂料生产线主要包括：原料贮罐，输送系统，研磨分散设备，调漆罐，调色系统，包装系统，操作控制系统及辅助设备（加热，降温，通风，除尘等)。一般来说，生产工艺流程及技术要求（合成参数）由研发部门和工艺工程师提供，设计人员（一般为专业的化工设计院）会根据具体要求来设计工艺流程图，根据投资预算和产量预估来设计设备布置，设备结构设备材质，管线安装，介质选择，控制方案等。表4-2-12为主要设备表。  \n\n表4-2-12 主要设备表  \n\n\n<html><body><table><tr><td>带刮边器的无极变速PLC控制高速分散机（防爆和非防爆）</td><td>半自动重量包装机</td></tr><tr><td>三轴无极变速PLC控制分散机（防爆和非防爆）</td><td>半自动体积包装机</td></tr><tr><td>一机多缸的无极变速PLC控制高速分散机（防爆和非防爆）</td><td>包装平台</td></tr><tr><td>移动式无极变速PLC控制高速分散机（防爆和非防爆）</td><td>全自动包装机</td></tr><tr><td>砂磨机</td><td>手动包装机</td></tr><tr><td>带无极变速PLC控制的搅拌机的不同大小的基料贮罐（防爆和非防爆）</td><td>稀释剂包装机（防爆）</td></tr><tr><td>不同大小的生产稀释剂，组分B等混合机及罐（防爆）</td><td>带气动泵的过滤装置</td></tr><tr><td>带无极变速搅拌机的不同大小的调漆罐（防爆和非防爆）</td><td>抽风和冷却系统</td></tr><tr><td>带无极变速搅拌机的不同大小的调色罐（防爆和非防爆）</td><td>除尘器（防爆和非防爆）</td></tr><tr><td>移动式无极变速PLC控制混合机（防爆和非防爆）</td><td>全自动泡沫喷淋系统、水喷淋系统</td></tr><tr><td>不同大小的不锈钢移动缸</td><td>温感、烟感紧急报警系统</td></tr><tr><td>无极变速的PLC控制的不同型号的齿轮泵</td><td>200kg桶操作器</td></tr><tr><td>各种气动PLC控制阀门</td><td>用于大包装物品的起重气动葫芦（防爆和非防爆）</td></tr><tr><td>助剂添加系统</td><td>液压式提升机</td></tr><tr><td>氨水添加设备</td><td>电动叉车及充电器</td></tr><tr><td>电子托盘器</td><td>工具及移动贮罐清洗用的设备</td></tr><tr><td>不同型号的防爆电子秤</td><td>低压清洗器</td></tr><tr><td>带电子秤的称重器</td><td>高压清洗机</td></tr><tr><td>带电子秤的桶操作器（防爆）</td><td>液体泄漏清洗设备</td></tr><tr><td>PLC控制电子地磅（防爆和非防爆）</td><td>移动缸清洗设备</td></tr><tr><td>PLC控制的不同直径和流速的LC计</td><td>真空吸尘器</td></tr><tr><td>PLC控制的不同直径和流速的质量流量计</td><td>紧急淋浴</td></tr><tr><td>PLC控制的低液位控制及报警装置</td><td>洗眼器</td></tr><tr><td>PLC 控制的高液位控制及报警装置</td><td>垃圾压缩机</td></tr><tr><td>关桶器</td><td>手推车</td></tr><tr><td>细度计</td><td>移动灭火器</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1239,
+        "chunk": "# 四、涂料生产主要设备  \n\n涂料的生产工艺过程中所用的主要设备为研磨分散设备，其对颜料在涂料中的分散状态、最佳颜料性能（着色力、遮盖力、耐候性等）的利用，以及由此而导致的漆液和涂膜的性能，起着非常重要的作用。因此，和精心设计色漆配方一样，选择先进、高效率的分散研磨设备，是保证生产高质量的涂料产品不可忽视的重要环节。  \n\n设备选择和生产工艺与品种相关。有些颜料是很容易被破坏的（如云母、珠光颜料、铝粉、氧化亚铜)，而有些是一定要在非常强的剪切力下经研磨才可以达到最佳性能的（如有机色粉)。涂料的品种繁多，对生产设备的要求也有很大差异。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1240,
+        "chunk": "# 1.捏和机  \n\n在涂料腻子生产时，如各种建筑用的腻子、浮雕漆、石头漆等不同用途的高固含量，高黏度，高触变，对细度要求不高的产品，捏合机是一种不错的选择。捏合机的种类繁多，锥形、卧式、V形、旋转等，技术成熟，用途广泛。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1241,
+        "chunk": "# 2.球磨机/三辊研磨机  \n\n球磨机有卧式球磨机和立式球磨机，属间歇式操作球磨机，可参见图4-1-99和图4-1-101。  \n\n三辊研磨机适用于加工高黏度的料浆和难于分散的颜料。但开式的操作，使工作环境恶劣，操作安全性差及分散的物料损失大，结构复杂，调试困难，生产效率低，在现代的涂料行业中基本不再使用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1242,
+        "chunk": "# 3.砂磨机  \n\n砂磨机是目前涂料工业上应用最广的研磨设备之一，可连续生产，加工产品的质量重复性好、控制简单、操作容易，适应于高细度要求的面漆和大部分色浆制作。但对于特别的颜料，如对温度敏感的颜料、珠光颜料、片状颜料，则不是很合适，而且，料浆黏度高时加工困难，换色时清洗困难、残留多。砂磨机的设计和品种繁多，选择时要根据物料的黏度，颜料的性质，产量的需求来确定合适的型号和研磨介质。砂磨机可参阅图4-1-74。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1243,
+        "chunk": "# 4.篮式砂磨机  \n\n篮式砂磨机是开发较新的产品，集研磨和分散为一体的新型砂磨机。利用循环研磨技术，其原理类似高循环大流量卧式研磨机，适合研磨固含量较高、黏度大、难研磨的涂料和产品；带有强制的冷却装置，适合温度敏感型的颜料。高效分散研磨，具有启动平稳、连续生产效率高、换色方便、清洗容易、操作简单等优点。篮式砂磨机可参阅图4-1-96。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1244,
+        "chunk": "# 5.高速分散机  \n\n高速分散机是最常用的涂料生产设备，也是涂料用研磨分散设备中结构最简单的一种，其工作原理是：电动机的转动经过无级变速后，带动主轴以一定的速度转动，主轴下端装有分散叶轮，叶轮的高速旋转对物料产生混合和分散作用，适合超细颜料的研磨分散，结构简单，操作维护保养容易，使用灵活，预混合分散及调漆皆可使用，清洗方便，生产效率高，产能大，污染小。随着新型高速分散机设备（如双轴双叶轮高速分散机、三轴高速分散机、不同品种的分散盘、不同旋转方式等）的出现，其应用范围日趋扩大。但对于生产高细度要求的涂料和有机色浆，主要用于预分散。高速分散机可参阅图4-1-57。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1245,
+        "chunk": "# 6.涂料成套设备  \n\n涂料成套设备是设备生产商为客户提供的一体化的研磨涂料自动化成套设备，设备能独立完成真空进料、分散、研磨细化、冷却、调漆、过滤、自动灌装等全过程，一般为自动化控制真空进料，电子计量，在线检测，生产过程自动化控制PLC人机界面，配方由CPU自动存储。生产商可以根据客户的产品品种、产量需求来设计不同功能的成套设备。  \n\n在线混合分散设备是涂料设备领域的最新设计，基于的原理是：把干颜料粒子混合、分散，确保颜料粒子在真空下接触液体前充分碾碎。真空可以使颜料粒子和基料混合充分，而且，解决了粉尘和溶剂挥发的问题，同时，这种新技术可以大大降低生产时间，减少空间占有，容易清洗，产量可大可小，可以连续生产，也可以间断生产。该设备使润湿更充分，分散更彻底，可节省90%的能源，减少温度升高，降低操作风险，应用广泛，容易清洗。  \n\n在线混合分散设备可参见图4-1-72。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1246,
+        "chunk": "# 参考文献  \n\n[1]企业总平面设计规范．GB50187—1993.  \n[2］厂矿道路设计规范．GBJ22—1987.  \n[3］石油化工企业设计防火规范．GB50160—1992.  \n[4］建筑设计防火规范．GBJ16—1987（2001).  \n[5] 工业企业设计卫生标准．GBZ1—2002.  \n[6]建筑给排水设计规范．GB50015—2003.  \n[7] 室外给水设计规范，GBJ13—1986（1997）.  \n[8]室外排水设计规范．GBJ14—1987（1997）.  \n[9]生活饮用水卫生标准，GB5479—1989.  \n[10] 工业循环水处理设计规范．GB50050—1995.  \n[11] 洁净厂房设计规范：GB50073—2001.  \n[12] 自动喷水灭火系统设计规范：GB50084—2001.  \n[13] 建筑灭火器配置设计规范．GBJ140—1990（1997）.  \n[14] 蒸汽供热系统凝结水回收及蒸汽疏水阀技术管理要求．GB/T12712—1991.  \n[15] 供配电系统设计规范.GB50052—1995.  \n[16] 低压配电设计规范：GB50054—1995.  \n[17］通用用电设备配电设计规范．GB50055—1993.  \n[18] 电力装置的继电保护和自动装置设计规范.GB50062一1992.  \n[19] 工业企业照明设计标准.GB50034—1993.  \n[20] 医药工业洁净厂房设计规范.  \n[21]火灾自动报警系统设计规范．GB50116—1998.  \n[22] 爆炸和火灾危险环境电力装置设计规范，GB50058—1992.  \n[23]建筑物防雷设计规范．GB50057—1994（2000).  \n［24]电力工程电缆设计规范．GB50217—1994.  \n[25]民用建筑电气设计规范．JGJ/T16—1992.  \n[26]评价企业合理用电技术导则．GB/T3485—1998.  \n[27]采暖通风与空气调节设计规范，GBJ19—1987.  \n[28]石油化工采暖通风与空气调节设计规范．SH3004—1999.  \n[29］建筑专业提供的建筑平、立、剖面图.  \n[30]空调通风系统运行管理规范．GB50365—2005.  \n[31]采暖通风与空气调节设计规范，GB50019—2003.  \n[32]通风与空调工程施工质量验收规范，GB50243—2002.[33] 民用建筑热工设计规范.GB50176—1993.  \n[34] 评价企业合理用热技术导则.GB/T3486—1993.  \n[35] 建筑结构可靠度设计统一标准.GB50068一2001.  \n[36] 建筑结构荷载规范.GB50009-2001.  \n[37] 建筑地基基础设计规范.GB50007—2002.  \n[38] 混凝土结构设计规范：GB50010—2002.  \n[39] 砌体结构设计规范：GB50003—2001.",
+        "category": " References"
+    },
+    {
+        "id": 1247,
+        "chunk": "# 涂料性能测试",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1248,
+        "chunk": "# 一、涂料性能  \n\n涂料虽属于精细化工产品，但按组成，它是由不同的化工产品组成的混合物，而不是化合物，更不是纯化工产品。液态涂料中的清漆，大多数是不同化工产品的溶液，少数是分散体；色漆则都是固体化工产品（颜料、填料）在溶液或分散液中的分散体。粉末涂料是化工产品的固-固分散体。由涂料形成的涂膜则是以具有黏弹性的无定形高聚物为主体组成的固态混合物。  \n\n涂料作为装饰保护材料使用，它属于高聚物材料，但涂料本身是半成品，所形成的涂膜才是高聚物材料；而涂膜又与塑料、橡胶、纤维等高聚物材料不同，不能独立存在，必须黏附在其他被涂物件上才能成为材料。所以涂料和涂膜既具有一般聚合物材料的通性，又有与一般聚合物材料不同的特性。最主要的是涂膜必须适应被涂物件材质性能的要求，与底材结合成为一体。  \n\n涂料是为被涂物件服务的材料，应用于被涂物件表面。由于被涂物件是多种多样的，使用条件千变万化，因而涂料与涂膜必须具备被涂物件所要求的性能，也就是以被涂物件的要求作为确定涂料和涂膜性能的依据。  \n\n因此涂料的性能表示的是它的使用价值，而且是综合性的、广泛的和长时间的使用价值。  \n\n涂料的性能虽然是以涂料和涂膜的基本物理和化学性质为依据，但并不是全面的表示，通常提到的涂料的性能只表现了涂料和涂膜的基本性质中的某一部分。  \n\n涂料的性能包括涂料产品本身和涂膜的性能。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1249,
+        "chunk": "# 1.涂料产品本身的性能  \n\n涂料产品本身的性能一般包括以下两个方面：  \n\n$\\textcircled{1}$ ① 涂料在未使用前应具备的性能，或称涂料原始状态的性能，所表示的是涂料作为商品在贮存过程中的各方面性能和质量情况；  \n\n$\\textcircled{2}$ ② 涂料使用时应具备的性能，或称涂料施工性能，所表示的是涂料的使用方式、使用条件，形成涂膜所要求的条件，以及在形成涂膜过程中涂料的表现等方面情况。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1250,
+        "chunk": "# 2.涂膜的性能  \n\n涂膜的性能即涂膜应具备的性能，也是涂料最主要的性能。涂料产品本身的性能只是为了得到需要的涂膜，而涂膜性能才能表现涂料是否满足了被涂物件的使用要求，亦即涂膜性能表现涂料的装饰、保护和其他作用。涂膜性能包括范围很广，因被涂物件要求而异，主要有装饰方面、与被涂物件附着方面、机械强度方面、抵抗外来介质和大自然侵蚀以及自身老化破坏等各种性能。  \n\n经过多年的实践，对涂料的性能分别给以适当的名称，例如涂料物理状态方面的有密度、黏度等，涂膜光学性质方面的有光泽、颜色，机械性质方面的有硬度、柔韧性等，用来表示某一方面的涂料性能。随着涂料品种的发展，表示涂料性能的具体项目逐渐增加，现代的涂料性能的内容逐步接近涂料的实际性质。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1251,
+        "chunk": "# 二、涂料产品的技术指标与标准  \n\n涂料的性能是多方面的，为了评价涂料具有什么样的性能，以及性能的高低，多年来创造和制定了许多试验方法，从不同的角度和方面对涂料性能进行考查，并尽量用数值来表示。这些表示值就成为代表涂料某一方面性能的指示数值，通称涂料产品的技术指标，但它只是用某一检测方法所得的指标，若用另外的检测方法可能得到另外的数值。综合多方面性能检测的结果，可以对涂料的性能有比较完整的认识，既有利于使用，又有利于提高性能。原则上讲，对涂料性能的认识越全面，才越能发挥它的作用，因此在研制涂料新品种时要从更多的方面、用更多的考查方法和更长的时间来认识它的性能，才能得到完美的结果。但在涂料产品投入生产以后，为了保证产品质量的一致性，常常将涂料性能中主要部分的内容定为技术指标，作为考查的对象。因此应该注意到产品技术指标只是部分地表现了涂料的性能。这就使技术指标与涂料真正性能之间存在着差别。  \n\n用主要的涂料产品技术指标所规定的数值综合起来以表示涂料的性能，就构成涂料产品的标准。作为标准来说，它具有统一性、科学性、广泛性、约束性和可行性。产品标准以技术指标为主要内容，技术指标又以指定的检测方法的测定结果来表示。一个涂料产品研制和生产出来，就要制定产品标准，作为评定本产品的依据。  \n\n现在，国际上标准化管理工作日益深入，世界主要国家都制定了本国涂料产品标准。我国制定有涂料产品的国家标准、行业标准。生产涂料企业为了组织生产也制定相应的企业标准。  \n\n涂料产品标准中，除了说明产品的组成、特性、适用范围及用途以外，主要内容是列出产品的技术要求。列入标准中的技术要求是有选择的，遵循三项基本原则：  \n\n(1）目的性原则应根据产品用途和制定产品标准的目的，有针对性地选择必要的技术内容，以保证产品的质量和适用性，实现品种控制。  \n\n(2）最大自由度原则在规定产品标准的技术内容时，原则上只应规定性能要求，要使实现这些性能要求的手段有最大的选用范围。  \n\n(3）可证实性原则原则上，产品标准中规定的技术要求只应规定能用试验方法等加以验证的要求。  \n\n技术要求包括的项目应充分考虑其使用要求及其基本特性和安全因素等，尽可能定量表示，一般由下列4项指标构成。  \n\n(1）通用指标通用指标是指对表明各种涂料产品性能均属必要的指标项目，如表示涂料的原漆状态的指标，如颜色、外观、黏度、细度、密度、固体含量、干燥时间等。  \n\n(2）专用指标指为表现本涂料产品的特有性能必须定人的指标，以表示与其他品种的区分。也可根据用户使用要求模拟产品特性定出专用指标。  \n\n(3）施工技术要求为了确保本产品在施工过程中得到满意的工程质量，须对产品的施工性能规定的技术要求，如使用量、涂刷性、施工涂层的重涂性、防流挂性等。  \n\n(4）安全、卫生、环保技术要求由于目前涂料产品大多属易燃、易爆，并可能具有毒性及污染的物质，在产品标准中要对安全、卫生、环保方面的技术指标有明确规定，都应符合国家法规要求，特别是对国家有关规定的有毒物质如镉、铅、铬、汞、苯等的含量范围应该定有具体指标，同时应符合环保法规的规定。今后这项要求将越来越重要。我国在2001年制定了涂料有害物质限量强制性国家标准，即GB18581—2001《室内装饰装修材料溶剂型木器涂料中有害物质限量》和GB18582—2001《室内装饰装修材料内墙涂料中有害物质限量》。并且随着涂料制造水平的提高，有害物质进一步降低，因此在2006年修订了GB18582。具体指标如表4-3-1、表4-3-2。  \n\n表4-3-1GB18581—2001对人体有害物质容许限值的要求   \n\n\n<html><body><table><tr><td rowspan=\"2\">项 目</td><td colspan=\"3\">限量值</td></tr><tr><td>硝基漆类</td><td>聚氨酯漆类</td><td>醇酸漆类</td></tr><tr><td>挥发性有机化合物(VOC)/(g/L)</td><td>750</td><td>光泽(60°)≥80,600 光泽(60°)<80,700</td><td>550</td></tr><tr><td>苯/%</td><td colspan=\"3\">0.5</td></tr><tr><td>甲苯和二甲苯总和/%</td><td>45</td><td>40</td><td>10</td></tr><tr><td>游离甲苯二异氰酸酯（TDI)/% ≤</td><td></td><td>0.7</td><td></td></tr><tr><td rowspan=\"4\">重金属（限色漆）/（mg/kg）</td><td>可溶性铅</td><td colspan=\"2\">90</td></tr><tr><td>可溶性 ≤</td><td colspan=\"2\">75</td></tr><tr><td>可溶性铬</td><td>60</td><td></td></tr><tr><td>可溶性汞</td><td colspan=\"2\">60</td></tr></table></body></html>\n\n$\\textcircled{1}$ 按产品规定的配比和稀释比例混合后测定。如稀释剂的使用量为某一范围时，应按照推荐的最大稀释量稀释后进行测定。  \n\n$\\textcircled{2}$ 如产品规定了稀释比例或产品由双组分或多组分组成时，应分别测定稀释剂和各组分中的含量，再按产品规定的配比计算混合后涂料中的总量。如稀释剂的使用量为某一范围时，应按照推荐的最大稀释量进行计算。  \n\n$\\textcircled{3}$ 如聚氨酯漆类规定了稀释比例或由双组分组成时，应先测定固化剂（含甲苯二异氰酸酯预聚物）中的含量，再按产品规定的配比计算混合后涂料中的含量。如稀释剂的使用量为某一范围时，应按照推荐的最小稀释量进行计算。  \n\n表4-3-2GB18582—2007对人体有害物质容许限值的要求   \n\n\n<html><body><table><tr><td colspan=\"2\">项目</td><td colspan=\"2\">限量值</td></tr><tr><td colspan=\"2\"></td><td>水性墙面涂料</td><td>水性墙面腻子</td></tr><tr><td colspan=\"2\">挥发性有机化合物(VOC)</td><td>120(g/L)</td><td>15(g/kg)</td></tr><tr><td colspan=\"2\">游离甲醛/(mg/kg) ≤</td><td colspan=\"2\">100</td></tr><tr><td colspan=\"2\">苯、甲苯、乙苯和二甲苯总和/(mg/kg) ≤</td><td colspan=\"2\">300</td></tr><tr><td rowspan=\"4\">重金属/(mg/kg）</td><td>可溶性铅 ≤</td><td colspan=\"2\">90</td></tr><tr><td>可溶性镉 ≤</td><td colspan=\"2\">75</td></tr><tr><td>可溶性铬 ≤</td><td colspan=\"2\">60</td></tr><tr><td>可溶性汞 ≤</td><td colspan=\"2\">60</td></tr></table></body></html>\n\n$\\textcircled{1}$ 涂料产品所有项目不考虑稀释配比。$\\textcircled{2}$ 膏状腻子所有项目均不考虑稀释配比；粉状腻子除可溶性重金属项目直接测定粉体外，其余三项是指按产品规定的配比将粉体与水或胶黏剂等其他液体混合后测定的。如配比为某一范围时，水应按照最小稀释量混合后测定，胶黏剂等其他液体应按照最大稀释量混合后测定。  \n\n在标准中要根据这些技术要求选定和标明适当的试验方法。选定技术要求时除了遵照上述的原则外，还要注意以下4个方面。  \n\n① 技术要求列为标准的内容，作为生产和使用双方验收产品的依据，所定的项目必须能真实反映本产品特性，对于必要的项目必须列入，而不必要的项目就不宜列人，项目的选择必须符合实际。  \n\n② 技术指标的高低也应符合实际，技术指标的数值应是产品在正常情况下的最低保证数值。过分降低其数值等于降低产品性能水平，而盲目提高并不等于提高产品质量，反而会造成不必要的浪费。  \n\n③制定技术指标时必须对多批次产品进行准确的测定，积累相当数量的数据。用少量的数据来制定标准是不切实际的。  \n\n④ 标准有一定的严肃性，不宜轻率变动。但随着产品的改进和使用条件的变化，技术要求也要适当修订。通常可先由供需双方协议指标，在经过一定时间的验证后，再正式制定或修订。  \n\n在产品标准中，从产品实用要求考虑，施工参考条件也是重要的。它的主要内容应该包括以下几项。  \n\n（1）适用涂装方式。  \n\n（2）底面漆配套选择。  \n\n(3）涂料的调配（制）多组分涂料混配比例和程序、熟化时间、使用有效时间；稀释剂使用品种、稀释比率；其他助剂使用品种、比率；搅拌、过筛及保存方法等。  \n\n(4）施工工艺要求环境条件；基材表面处理方法及达到的要求；施工黏度；标准涂装量；标准涂膜厚度；涂装间隔时间（每遍干燥时间)；腻子使用品种及规定厚度；磨光方法；涂装遍（道或次）数要求；干燥条件；使用前需养护时间；注意事项以及其他特殊要求。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1252,
+        "chunk": "# 三、涂料检测的目的与特点  \n\n如前所述，表示涂料产品性能的技术要求指标是通过试验方法来确定的，因此用规定的试验方法来评价涂料产品性能的涂料检测工作就成为涂料生产和使用过程中的重要环节。  \n\n涂料检测的目的归纳起来有以下3个方面。  \n\n① 通过有限的试验，对所研制的涂料产品进行考查，为选定产品的配方设计、工艺条件提供数据，指导试验工作，从而编制产品技术规格和标准。  \n\n$\\textcircled{2}$ 通过各个项目的检查，达到控制产品质量的目的。对涂料生产单位用以保证正常生产和出厂产品批次质量一致；使用单位通过检测验收产品，以保证施工的正常进行。  \n\n$\\textcircled{3}$ 通过检测试验得出的数据，开展基础理论的研究，找出组分与性能之间的关系，从而发现原有产品存在的问题及改进的方向。并且可以为新的科研课题和新产品的开发提供数据。  \n\n因此，涂料检测可以说是开展涂料科学研究、实现涂料产品开发、保证生产和使用的正常的必要步骤和手段。  \n\n涂料检测是标准化工作的一项重要内容，它与标准化工作相互依赖、相互促进。涂料检测又是推行全面质量管理的一个重要环节，不论是涂料生产还是涂料施工都需要推行全面质量管理，以适应社会发展的需要，在当前强调建立质量保证体系的前提下，涂料检测更具有重要的意义。  \n\n涂料检测的特点可以归纳为以下6个方面。  \n\n$\\textcircled{1}$ 如前所述，涂料的性能是通过施工后的涂膜来体现的，因此涂料检测的重点是对涂膜性能的检测，对于涂料产品本身状态的检测也是必要的，但主要是考察产品质量的一致性。因而在涂料的成膜过程和成膜后性能的检测是对涂料产品品种质量评判的基础，是考核涂料质量的主要内容。这方面的检测方法发展得最多最快。  \n\n② 涂膜性能的检测为了尽量模仿实际条件，大多是在相应的底材上进行检测，因此试验底材的选择对试验结果有一定的关系，更重要的是试验涂膜在底材上的制备工艺和质量对测试结果有显著的影响。  \n\n$\\textcircled{3}$ 涂料性能的检测，单纯依靠化学组成分析不能完全判定其质量状况，而是看它是否符合所要求的材料性能，故较多地是以物理检查为主。此外，在物理性能检查中，一个检测方法测得的结果往往是几个性能的综合，例如，测柔韧性常用的弯曲试验，所反映的不单纯是柔韧性，还涉及涂膜的硬度、附着力和延伸性。  \n\n$\\textcircled{4}$ 涂料产品繁多，要求不同，为了表达其性能，经过多年的实践，发展了多种检测方法，同一检测项目有各种方法，它们从不同角度进行检测，所得结果往往有差异，因此在涂料检测时应针对产品性能，在多种试验方法中选择最合适的方法。  \n\n$\\textcircled{5}$ 检测方法虽然经过多年发展，尽量用量值表示，但还有些检测项目是通过与标准状况比较，或者用变化程度如“无变化”、“轻微变化”等表示，在评定结果时干扰因素较多。还有，检测方法还没有全部仪器化，有些靠目测观察，易造成主观上的误差，增加了检测结果评定的难度。所以有些检验项目规定同时采用3块或更多块样板进行测试，以多数结果作为最后判定。  \n\n$\\textcircled{6}$ 涂料产品通过检测，最后结果的评定对于同类产品的可比性较大，对于不同组成的产品可比性较小。由于检测项目是多方面的，对涂料性能的最后判断必须用各项指标来综合平衡，单独某项指标的比较，不能说明该产品性能的优劣。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1253,
+        "chunk": "# 四、涂料检测的发展与标准化  \n\n广义的涂料检测包括为了涂料基础理论研究、生产过程控制、产品性能质量控制和施工过程质量管理等方面而进行的各项检测工作，通常则指对涂料产品性能检查和质量控制方面，即按产品规定的技术要求进行检测。  \n\n产品的技术要求包括涂料本身性能和涂膜性能两方面，因而检测的内容也就以这两方面来分类。按照每一项技术指标的要求而定出相应的检测方法，这些检测的方法有的以技术指标的名称命名，如密度、硬度等，有的则以所采用的试验方法来命名，如弯曲试验、压痕试验等。  \n\n涂料的检测项目随着涂料产品的发展而发展，传统涂料品种简单，检测项目较少、方法简单，基本是手摸眼看。涂料生产的发展，促使检测项目增多，检测方法科学化，由定性到定量，由手工测试到仪器分析。现在运用现代科学技术的方法得到快速发展。  \n\n$\\textcircled{1}$ 应用仪器分析和测试成为检测方法的主流，更多的利用电子技术实现数字显示、微机控制等，测试精密度和准确度提高。  \n\n$\\textcircled{2}$ 经过多年的发展，一个检测项目发展了多种检测方法，分别使用不同的检验仪器，虽然有些方法和仪器被淘汰，但仍有较多方法因其所具特色而保留下来，因而形成了检测方法和仪器的多样化。  \n\n$\\textcircled{3}$ 新的检验方法和仪器的不断出现，推动了检测技术的发展。从涂料生产到施工都加强了对检测技术的重视，但是一个新型方法或仪器的采用，需要经过较长时间的考验，才能确立和定型。  \n\n由于多年的发展，世界各国分别选用不同的涂料检测方法和仪器，制定了各国独自的检验方法标准，并颁布执行。如美国ASTM标准、德国DIN标准、日本JIS标准中都制定了多项涂料检测方法标准。国际标准化组织ISO也制定了许多检测方法，向各国推荐实施，以求国际的标准化。我国陆续制定和多次修订了涂料检测方法的国家标准、行业标准，并颁布实施。其中大多数标准等同、等效或参照ISO标准。现在随着产品的发展，如有关粉末涂料、电泳涂料以及特种涂料的检验方法也陆续制定。本章将重点介绍通用的涂料产品的检测方法，以我国国家标准规定的方法为主。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1254,
+        "chunk": "# 第二节 涂料产品检测  \n\n涂料产品检测的内容包括两方面，即涂料原始状态的检测和涂料使用性能的检测。涂料原始状态的检测目的是说明涂料在产成后装入容器和在容器贮存后的质量状态，考查其是否符合预定要求。可以说原始状态的质量情况对以后涂料使用产生影响，是涂膜质量好坏的基础。它包括3个方面，一方面是涂料的物理性状的检查，如密度、黏度、清漆的透明度和颜色以及色漆的细度等；一方面是涂料在容器中经受时间、温度等变化可能发生的状态改变情况的考查，如在容器中状态、贮存稳定性、水性漆冻融稳定性等；第三方面是涂料组成的分析，现在环保法规对涂料所含组分的管理越来越严格，对污染环境、危害健康的挥发性气体和有毒物质的含量都有严格规定，特别是对用于食品包装、儿童玩具等的涂料控制最严。因此工业管理和使用部门要对涂料中有关组分进行检测，此外为了验证涂料的品种，也要进行一些必要的组分分析。从涂料施工和经济效益角度考虑，控制涂料中成膜组分的含量最为重要。所以涂料组分的分析项目随着时代的进展逐步增加。除了最通用和必须控制的不挥发分含量以外，还有灰分、不皂化物、溶剂不溶物、酸值等一般通性的检测。此外，属于组分含量的检测项目有苯酐含量、脂肪酸含量、氯含量、氧含量，有毒物质如砷、铅、铬、铜、酚、硝基化合物的定量和定性分析，还有各种可挥发物质的分析检测。这些项目的检测方法通常多用化学分析和仪器分析。在本节中主要介绍前两方面和第三方面中通用的不挥发分含量的检测，对于其他组分的分析在另节中介绍。  \n\n涂料使用性能的检测主要是为了涂料施工的需要。从涂料的研制开始，就应该考虑涂料的施工条件、施工方法，从而确定所研制的涂料的最佳应用条件。为了使用者的方便，保证所生产的产品的质量，也要对其施工性能进行检测。研制过程中所试验的有关施工性能的项目一般要在较广泛的范围进行条件试验。如在不同施工方法时的最佳施工黏度，不同施工黏度能得到涂膜的厚度等，这是研究工作的需要。在为了产品控制时，则只对规定的主要施工性能项目进行检测。在本节中叙述的是控制产品质量的必要的施工性能检测项目。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1255,
+        "chunk": "# 一、涂料产品的取样  \n\n涂料产品的取样用于检测涂料产品本身以及所制成的涂膜。取样是为了得到适当数量的品质一致的测试样品，要求对所测试的产品具有足够的代表性。取样工作是检测工作的第一步，非常重要，取样的正确与否直接影响检测结果的准确性。对于涂料产品的取样，目前我国参照国际标准ISO155制定了国家标准GB/T3186—2006《涂料产品的取样》，标准中规定了以下三项主要内容。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1256,
+        "chunk": "# 1.产品类型  \n\n根据现有的涂料品种分为五个类型。  \n\nA型：单一均匀液相的流体，如清漆和稀释剂。B型：2个液相组成的流体，如乳液。C型：1个或2个液相与1个或多个固相一起组成的流体，如色漆和乳胶漆。D型：黏稠状，由1个或多个固相带有少量液相所组成，如腻子、厚浆涂料和用油或清漆调制的颜料色浆，也包括黏稠的树脂状物质。E型：粉末状，如粉末涂料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1257,
+        "chunk": "# 2.取样数目  \n\n按随机取样法，对同一生产厂生产的相同包装的产品进行取样，取样数应不低于  \n\n$$\ns{=}\\sqrt{\\frac{n}{2}}\n$$  \n\n式中—取样数； 71- 一交货产品的桶数。  \n\n为方便起见，建议按表4-3-3所列数字进行取样。  \n\n表4-3-3 产品取样规则  \n\n\n<html><body><table><tr><td>交货产品的桶数</td><td>取样数</td><td>交货产品的桶数</td><td>取样数</td></tr><tr><td>1~2</td><td>全部</td><td>26~100</td><td>5</td></tr><tr><td>3~8</td><td>2</td><td>101～500</td><td>8</td></tr><tr><td>9~25</td><td>3</td><td>501~1000</td><td>13</td></tr></table></body></html>  \n\n其后类推， $s{=}\\sqrt{\\frac{n}{2}}$ 。若交付批是由不同生产批的容器组成的，那么应对每个生产批的容器取样。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1258,
+        "chunk": "# 3.取样器械  \n\n为了保证取样器械不受产品侵蚀，而且容易清洗，采用不锈钢、黄铜或玻璃制品，并应有光滑表面，无尖锐的内角或凹槽等。实用取样器如图4-3-1～图4-3-3所示。  \n\n![](images/6ff7f9bdad1e58414a8d4b3c3f295e7e65056c906c45a5e5da79fdc0988332a9.jpg)  \n图4-3-1 取样瓶  \n\n![](images/aa9410acd2d2000c6d8e3612a16031eb58538bbd13ec905f910907f73e73b808.jpg)  \n图4-3-2 取样管  \n\n![](images/6c81e01df106e6d18e6903c0abbd93aab68ef03ee72e75f29aa52effe3d7bcc8.jpg)  \n图4-3-3 取样器  \n\n在涂料产品取样时还应注意以下几点：  \n\n$\\textcircled{1}$ 取样时所用的工具、器皿等均应仔细清洗干净，金属容器内不允许有残留的酸、碱性物质；  \n\n$\\textcircled{2}$ 所取的样品数量除足以提供规定的全部试验项目检验之用外，还应有足够的数量做贮存试验以及在日后需要时可对某些性能做重复试验之用；  \n\n$\\textcircled{3}$ 样品一般应放于清洁干燥、密闭性好的金属小罐或磨口玻璃瓶内贴上标签，注明生  \n\n产批次及取样日期等有关细节，并贮存在温度没有较大变动的场所。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1259,
+        "chunk": "# 二、涂料原始状态的检测",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1260,
+        "chunk": "# 1.清漆和清油的透明度  \n\n清漆和清油都是胶体溶液，其透明程度或浑浊程度都是由于光线照射在分散相微粒上产生散射光而引起的。在生产过程中，各种物料的纯净程度不够、机械杂质的混人、物料的局部过热、树脂的互溶性差、溶剂对树脂的溶解性低、催干剂的析出以及水分的渗人等都会影响产品的透明度。外观浑浊而不透明的产品将影响成膜后的光泽和颜色，以及使附着力和对化学介质的抵抗力下降。  \n\n测定方法一般是按GB/T1721—2008《清漆、清油及稀释剂外观和透明度测定法》进行的。将试样装于容量为25mL的比色管内，调整到温度25℃±1℃，于暗箱的透射光下与一系列不同浑浊程度的标准液比较，选出与试样最接近的某级标准溶液，分别以透明、微浑、浑浊三个等级来表示，即标准GB/T1721—2008中的1、2、3级。  \n\n目前逐步趋向于采用光电式浊度计来进行测定，以消除由于产品色相深浅不同而对目测结果的干扰，并提高测试的准确度。此类仪器的测量光路如图4-3-4所示。  \n\n图中A为反射罩，S为灯源钨丝，它位于被测溶液试管T的底部中央处，钨丝发射的光直接以一定的立体角通过可转换的滤光片F投射到试管T的底部，由于光在试管中受溶液中杂质或悬浊物的影响，而产生散射光，再经反射罩A反射，投射在硫化镉光敏电阻上而被接收。  \n\n![](images/f62e51caa9cdeaa3d9cbad5618c63412d699f6ed706715189658e83de3a6e746.jpg)  \n图4-3-4 浊度测量光路示意图  \n\n根据浊度定义，浊度是指扩散光系数与总的透光系数之比，可以下式表示。  \n\n$$\nD{=}\\frac{\\tau_{\\mathrm{k}}}{\\tau}\\times100\\%\n$$  \n\n式中 $D^{\\prime}$ —浊度值， $\\%$ 电——总的透光系数；——扩散光系数。  \n\n选用适当的磨砂有机玻璃棒校正标准浊度，定为100，用蒸馏水校零。当仪器校正后，即可直接测得被测溶液的浊度值。  \n\n例如：F01-1酚醛清漆的透明度，当采用红色滤光片测定，达1级透明时，测得数值即为零；若2级微浑时则数值在10～11之间，这样就可用数字来表示清漆的浑浊程度。  \n\n仪器设计有几片可替换的滤光片（白、红、绿、蓝)，旨在减小由于被测溶液带色所产生对光的吸收作用而影响正常的浊度测量值。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1261,
+        "chunk": "# 2.清漆和清油的颜色  \n\n清漆和清油等透明液体涂料由于对光的吸收而产生不同的颜色，通常要求其颜色越浅越好。检测颜色的方法是将这些涂料产品与一系列标准色阶的溶液或玻璃，在天然散射光或规定的人工光源的透射光下比较，确定其颜色的深浅程度。  \n\n依据所选用标准的不同，有以下几类检测方法。  \n\n(1）铁钻比色法我国国家标准GB/T1722—1992《清漆、清油及稀释剂颜色测定法》规定，以目视法将试样与一系列标有色阶标号的铁钻标准色阶溶液进行比较，选出与试样颜色深浅相同或最近似的标准色阶溶液，其色阶号即代表试样的颜色。铁钻比色计标准色阶溶液由不同比例的三氯化铁和氯化钴的盐酸溶液配成，共分18个色阶，最浅的为1号，最深的18号。测试时将试样装人试管中，在23℃士2℃下于人造日光比色箱或暗箱的透射光下进行测定。  \n\n(2）铂钻比色法我国等效采用ISO6271—1981《透明液体———以铂-钻等级评定颜色》制定了GB/T9282—1988《透明液体以铂-钻等级评定颜色》的国家标准，规定用铂-钻单位来评定颜色的方法。铂钻单位是1L溶液中含 $\\mathrm{{1mg}}$ 铂（以氯铂酸盐离子形式存在）及 $2\\mathrm{mg}$ 氯化钻（Ⅱ）六水合物的溶液颜色，配制的标准溶液按所含铂钴单位从 $0\\sim500$ 分为25级。测定时将试样倒人比色管中至刻度线处，盖上盖子放入比色计中，目视观察与标准比色溶液进行比较，达到最接近的某个铂钻标准比色溶液，颜色即以其铂钴单位值表示。  \n\n(3）加氏颜色等级法（Gardner colour scale）中国等效采用ISO4630—1981标准制定了GB/T9281—1988《色漆和清漆用漆基加氏颜色等级评定透明液体的颜色》的国家标准，适用于清漆及树脂溶液，测定结果用加氏颜色号表示。标准色阶由18块标准颜色玻璃或18个标准色阶溶液组成。标准颜色玻璃的宽度不小于 $\\mathtt{l i m m}$ ，每个色阶均以色度坐标与光透射率来确定。标准色阶溶液是将配置好的有色溶液装于无色玻璃试管内，氯铂酸钾溶液用作浅色标准（ $1\\sim8$ 号)，氯化铁与氯化钴的盐酸溶液用作深色标准（ $(9\\sim18$ 号)。测试方法是在规定的CIE光源C照明下，以 $30{\\sim}50\\mathrm{cm}$ 之间的视距进行观察、比较，与试样颜色最接近的标准号数，即为试样的颜色结果。一般常用的是标准色阶溶液。  \n\n(4）罗维朋（Lovibond）比色法在我国国家标准GB/T1722—1992中还规定了用罗维朋比色计目视比色测定颜色的方法。将试样置于罗维朋比色计中的样品池中，用具有罗维朋色度标单位值的红、黄、蓝三原色滤色片与试样进行目视匹配，当匹配色与试样颜色一致时，以三滤色片的色度标单位值表示试样的颜色。  \n\n此外还有碘液比色法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1262,
+        "chunk": "# 3.密度  \n\n密度的定义为：在规定的温度下，物体的单位体积的质量，常用单位为 $\\mathrm{{g/cm^{3}}}$ 或$\\mathbf{g}/\\mathrm{m}\\mathbf{L}$ 9  \n\n测定涂料产品密度的目的，主要是控制产品包装容器中固定容积的质量；在检测产品遮盖力时也有意义，以便了解在施工时单位容积能涂覆的面积等。  \n\n目前密度测定按国家标准 $\\mathrm{GB/T\\6750-2007}$ 《色漆和清漆密度的测定比重瓶法》进行。该标准中指定使用比重瓶（质量/体积杯）法，作为在规定的温度下测定液体色漆、清漆及有关产品密度的标准方法。比重瓶有两种，一种是容量为 $20\\sim100\\mathrm{mI}.$ 的玻璃比重瓶；另一种是容量为 $37\\mathrm{mL}$ 的金属比重杯，如图4-3-5所示。  \n\n测定时首先用蒸馏水校准比重瓶的体积，然后称量产品及比重瓶的质量，密度按下式计算：  \n\n![](images/0840d814adaecffa5f22d4d48542e9fa3daf6c6098ebb43a745f23d1909a261d.jpg)  \n图4-3-5 金属比重杯  \n\n$$\n\\rho_{t}={\\frac{m_{2}-m_{0}}{V}}\n$$  \n\n式中 $m_{0}$ ——空比重瓶的质量，g；$m_{2}$ 比重瓶和产品的质量， $g_{\\frac{3}{4}}$ $V$ 在试验温度下比重瓶的体积，mL；t—试验温度（ $23^{\\circ}C$ 或其他商定的温度）， $q_{C}$ 0  \n\n在工厂成品检验中，较多的是使用金属比重杯，因操作方便、易清洗，但测试时要防止试样在比重杯中产生气泡，同时要立即快速地称量，以减少质量损失。  \n\n对于需较精确测定密度的涂料及油料，则可采用威氏比重天平（Westphalbalance），但操作较繁杂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1263,
+        "chunk": "# 4.细度  \n\n色漆中使用的颜料和体质颜料，应该是以微小的颗粒均匀地分散在漆料之中，当涂成十几到几十微米厚的薄膜时，涂膜表面应平整光滑，不能有颜料等颗粒状物体显现出来。为了表达涂料中颜料等的分散程度，制定了细度这个检测项目。除了用于检查色漆以外，现在对清漆有时也进行细度检测，以检查其中是否含有微小的机械杂质。细度也称研磨细度。  \n\n细度的检测是将涂料铺展为厚度不同的薄膜，观察在何种厚度下显现出颜料的粒子，即称之为该涂料的细度，所用的测试仪器通称为细度计，检测结果以微米表示。实际测得的数值是该涂料中最大的固体颗粒的大小尺寸，表示的是其粗粒子存在的程度。应该指出，这些粗粒子并不是单个的颜料或体质颜料粒子的大小，而是色漆在生产过程中颜料研磨分散后存在的凝聚团的大小。单个颜料或体质颜料的颗粒一般为零点几微米，一旦聚集起来就可以大到几十微米甚至上百微米，色漆在研磨过程中只能将大的颜料凝聚团分散成小的颜料凝聚团，目前最精密的研磨过程也不能将凝聚团分散成单个粒子，而只是将凝聚团分散到粒径小至 $10\\mu\\mathrm m$ 左右而已。  \n\n研磨细度是色漆重要的内在质量之一，对成膜质量，漆膜的光泽、耐久性，涂料的贮存稳定性等均有很大的影响。颗粒细、分散程度好的色漆，其颜料能较好地被润湿，颗粒间未被漆料充满的空间少，这样制得的漆膜颜色均匀、表面平整、光泽好，且漆在贮存过程中颜料不易发生沉淀、结块等现象，提高了贮存稳定性。  \n\n当然，细度也不是越细越好，要求过细不但延长了研磨工时，占用了研磨设备，同时也会影响漆膜的附着力，必须根据品种和用途来区别对待。一般来说，底漆和面漆要求的细度是不一样的，我国目前底漆细度要求不大于 $50\\mu\\mathrm{m}$ 或 $60\\mu\\mathrm{m}$ ，醇酸、氨基等装饰性面漆细度不大于 $20\\mu\\mathrm{m}$ ，有个别品种要求达到 $15\\mu\\mathrm{m}$ 以下。  \n\n研磨细度的测定目前世界各国基本都采用刮板细度计，测试原理完全相同，仅在刮板的大小、材质及读数的单位方面有所差别。刮板细度计是一块带有从0到若干微米深的楔形沟槽的磨光平板，槽边有刻度线标明该处槽沟的深度；另有一刮刀，两刃均磨光。使用时，将试样滴人沟槽的最深部位，然后用刮刀垂直接触平板，以适宜的速度把漆拉过槽的整个长度，立即用 $30^{\\circ}$ 的角度对光观察沟槽中颗粒均匀显露的位置，即为该试样的细度。此法操作简便，清洗容易，测试速度快，适于现场生产控制使用，但需注意试样的稀稠度应符合产品标准的规定，以免测试时产生误差。  \n\n刮板细度计目前趋向于采用双槽式，以便被测试样与标准样品可同时进行比较试验，或在一次试验中，可同时获得被测试样两个平行的测试数据。在读数判定方面，某些标准推荐用线条法来判定色漆的细度，与粒子密集程度法相比，线条法细度值大约为粒子密集法的一半，可适用于对细度要求不高的底漆、船底漆以及由于特殊需要加入粒子较粗的毒料、防滑成分的防污漆和防滑漆等。  \n\n通用的细度计的规格各国不同，我国国家标准GB/T1724—1979（1989）《涂料细度测定法》规定的细度计有3种规格： $0\\sim150\\mu\\mathrm{m}$ ， $0\\sim100\\mu\\mathrm{m}$ 和 $0\\sim50\\mu\\mathrm{m}$ 。我国等效采用ISO标准的GB6753.1—2007《色漆、清漆和印刷油墨研磨细度的测定》则分为 $100\\mu\\mathrm{m}$ $50\\mu\\mathrm{m}$ 、 $25\\mu\\mathrm{m}$ 和 $15\\mu\\mathrm{m}$ 等 $4$ 种规格。美国ASTMD1210（1979）规定为沟槽长度 $100\\mu\\mathrm{m}$ ，分  \n\n![](images/25f9aa54ae319737e5597457592a00c18f1dc15d3c91e4ed2e65365a063796ed.jpg)  \n图4-3-6 研磨细度换算图  \n\n级用海格曼级、mil和涂料工艺联合会FSPT规格表示。日本JIS标准则为 $100\\mu\\mathrm{m}$ 。美国的海格曼级、mil、FSPT级与 $\\mu\\mathrm{m}$ 的换算关系如图4-3-6所示。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1264,
+        "chunk": "# 5.黏度  \n\n黏度是流体的主要物理特性。流体在外力作用下流动和变形，黏度是表示流体流变特性的一个项目，它是对流体具有的抗拒流动的内部阻力的量度，所以也称为内摩擦力系数。它以对流体施加的外力与产生流动速度梯度的比值表示。外力有剪切力和拉伸力，通常将剪切力与剪切速度梯度的比值称为剪切黏度，通称动力黏度，国际单位为帕·秒（ $(\\mathrm{{Pa}}\\cdot\\mathrm{{s})}$ [习用单位为 $\\mathbf{P}$ (泊)、 $\\mathrm{cP}$ (厘泊)， $1\\mathrm{{Pa}\\cdot\\ s=10\\mathrm{{P}}}$ ， $\\mathrm{1mPa\\cdot{s}=}$ $\\mathrm{1cP]}$ 。动力黏度与密度的比值称为运动黏度，其国际单位是平方米每秒 $(\\mathbf{m}^{2}/\\mathbf{s})$ [习用单位是st（斯）、cSt（厘斯)， $\\scriptstyle1{\\mathrm{cSt}}=1{\\mathrm{mm}}^{2}/{\\mathrm{s}}]$  \n\n流体有牛顿型和非牛顿型流体之分，牛顿型流体是流体在一定温度下，在很宽的剪切速率范围内，黏度值保持不变。非牛顿型流体则剪切应力不与速率成正比，它的黏度值随切变应力的变化而改变。随着切变应力的增加，黏度值降低的流体称为假塑性流动；切变应力增加，黏度值也随之增加的称为膨胀性流动；如果在流体流动发生以前必须施加一定的切变应力才能流动，低于这个屈服值，流体只能变形的称为塑性流动。对于非牛顿型流动的黏度通常称为表观黏度，以与牛顿型流体的黏度区别。表观黏度是这个黏度值仅与一个剪切速率相关，一种流体在不同的剪切速率下，可以表现出不同的表观黏度值。  \n\n液体涂料中除了溶剂型清漆和低黏度的色漆属于牛顿型流动以外，绝大多数的色漆属于非牛顿型中的假塑性流动或塑性流动，因此它们的黏度值实际是它们的表观黏度。  \n\n对于厚浆状的涂料如腻子等，习惯上称其黏度为稠度（consistency），表示的也是其流动性。  \n\n涂料某些品种具有的触变性，也是一种流变性质，即这些品种受到外力时黏度降低，而静止后很快恢复原来黏稠度的性质，这种性质有利于涂料的施工。  \n\n液体涂料，特别是含有密度大的颜料的色漆，为了在容器中能够长期贮存，通常保持较高的黏度值，通称涂料的原始黏度。在施工时，需要用稀释剂调整至较低的黏度，以适合不同施工方法的需要。这时的黏度通称施工黏度。涂料的原始黏度因品种而异。如一般清漆在 $150{\\sim}300\\mathrm{mm}^{2}/s$ ，一般磁漆在 $200{\\sim}300\\mathrm{mm}^{2}/\\mathrm{s}$ ，硝基漆比醇酸漆更稠，有个别厚浆型品种能高达数万厘斯。施工黏度刷涂较高，约在 $250\\mathrm{mm}^{2}/\\mathrm{s}$ 左右，空气喷涂时的施工黏度通常要求 $50\\mathrm{mm}^{2}/\\mathrm{s}$ 左右，无空气喷涂、淋涂或浸涂等要求施工黏度各异。如前所述，涂料的原始黏度和施工黏度随温度升降而变化其数值，因此只能在同一温度条件下测定。  \n\n(1）液体涂料黏度的测定方法液体涂料的黏度检测方法有多种，分别适用于不同的品种。这些检测方法主要采用间接比较测定的方法。对透明清漆和低黏度色漆的黏度检测以流出法为主，对透明清漆的检测还有气泡法和落球法。对高黏度色漆则通过测定不同剪切速率下应力的方法来测定黏度，采用这种方法还可测定其他的相应流变特性。  \n\n$\\textcircled{1}$ 流出法通过测定液体涂料在一定容积的容器内流出的时间来表示此涂料的黏度，这是比较常用的方法，依据使用的仪器可分为毛细管法和流量杯法。  \n\n毛细管法测定涂料黏度是最古老的方法，也是一种经典的方法。  \n\n毛细管黏度计的基本结构如图4-3-7所示。它适用于测定清澈透明的液体。毛细管黏度计有多种型号，如奥斯特瓦尔德黏度计（Ostwaldviscome-ter）、赛波特黏度计（Sayboltviscometer）、坎农-芬斯克黏度计（Cannon-Fenske viscometer）、乌氏（乌布洛德）黏度计（Ubbelohdeviscometer）等。各种黏度计又按毛细管内径尺寸不同规格，分别适用于不同范围黏度的测量。由于毛细管黏度计易损坏，而且操作清洗均较麻烦，不适合用于工业生产，现主要用于其他黏度计的校正。  \n\n流量杯法实质上是毛细管黏度计的工业化应用。从结构上来说是将毛细管黏度计计时的起止线之间的容积放大，并把细长的毛细管部分改为粗短的小孔。由于容积大，流出孔粗短，因此操作、清洗均较方便，且可以适用于不透明的色漆，故现在应用比较广泛。流量杯黏度计所测定的黏度为运动黏度，通常以一定量的试样从黏度杯流出的时间来表示，以秒（s）作为单位。这种黏度计适用于低黏度的清漆和色漆，而不适用于测定非牛顿型流体的涂料如高稠度、高颜料分涂料。流量杯黏度计由于流出孔直径大、长度短，因而流动的稳定性较差；再加上流动过程中雷诺数较大，因此它不能代替毛细管黏度计用于科学研究方面。  \n\n![](images/1110c3951b75f6ef412e1230a67a17bf651f441f0e49d6c8674b98b28077d956.jpg)  \n图4-3-7 毛细管黏度计示意图  \n\n世界各国使用的流量杯黏度计各有不同名称，都按流出孔径大小划分为不同型号。各种黏度杯的形状大致相同，但结构尺寸略有差别。我国通用涂-1黏度计和涂-4黏度计（GB/T1723一1993），同时等效采用ISO流量杯（ $\\mathrm{:GB/T\\6753.4-1998})$ ；美国规定采用的是福特(Ford）杯［ASTMD1200—1994（1999)]；德国采用的是DIN黏度杯（DIN53211—1987)。它们都按孔径大小分为不同的型号，如ISO杯有 ${\\mathfrak{3}}^{\\sharp}$ ， $4^{\\sharp}$ 和 ${\\mathfrak{G}}^{\\sharp}$ 三种，福特杯有 $2^{\\sharp}$ ，$3^{\\#}$ 和 $4^{\\sharp}$ 三种，DIN杯有 $2^{\\sharp}$ 、 ${\\mathfrak{3}}^{\\#}$ 1 $4^{\\sharp}$ ， ${\\hat{6}}^{\\sharp}$ 和 $8^{\\sharp}$ 五种。每种型号的黏度杯都有其最佳的测量范围，我国涂-1黏度计适用于测定流出时间大于20s的涂料，涂-4黏度计适宜测定流出时间在 $20\\sim100s$ 的涂料，ISO及福特杯则规定为 $30\\sim90{\\mathrm{s}}$ ，若低于或高于流出时间范围，则所测得的数据准确度就差。用流出时间可换算成运动黏度，但各种黏度杯换算的公式不同。同样孔径大小的黏度杯因其结构尺寸不同，同样流出时间换算得到的运动黏度值不同，也就是同一运动黏度值的样品在不同型号黏度杯的流出时间有很大差别。我国涂 $^{-4}$ 黏度计接近福特 $47$ 杯，但与ISO $4^{\\sharp}$ 杯差别很大。如测得流出时间65s，用涂 $-4$ 黏度计时的运动黏度换算值为 $250\\mathrm{mm}^{2}/\\mathrm{s}$ ，福特$\\sharp^{\\sharp}$ 杯则为 $232\\mathrm{mm}^{2}/\\mathrm{s}$ ，两者比较接近，而ISO $\\sharp^{\\sharp}$ 杯则为$85\\mathrm{mm^{2}/s}$ 。运动黏度为 $300\\mathrm{mm^{2}/s}$ 的涂料样品，用涂-4黏度计测得的流出时间为 $80{\\_}$ ，用福特 $4^{\\#}$ 杯为82s，用DIN$4^{\\sharp}$ 杯为67s，而用ISO $4^{\\sharp}$ 杯则超过100s，结果不准，必须换用 $\\mathrm{ISO~}\\hat{6}^{\\sharp}$ 杯（孔径为 $\\mathrm{{\\acute{6}m m}}.$ )，测得的流出时间为  \n\n![](images/990404b55b89704951fa9a2916669ef9db6c9ce6b1e3183b99d09037a0ada564.jpg)  \n图4-3-8涂-4杯黏度计  \n\n$445$ 。因此在选用流量杯测定黏度时，需要根据样品黏度情况选择合适型号的黏度计，对测得的流出时间最好在规定范围的中间，并且注明使用何种型号的黏度计所测。这在制定涂料产品技术指标时就应予以注意，选择恰当的黏度测定方法。图4-3-8和图4-3-9分别列出涂-4 黏度计和ISO流量杯的尺寸。福特杯的规格参见ASTMD1200—1994(1999)。涂-4黏度计的最佳测定范围为流出时间20～100s，适宜测定运动黏度60～$360\\mathrm{mm^{2}/s}$ 的涂料。  \n\n下列公式可将用涂-4黏度计测得的试样的流出时间s换算成运动黏度值 $\\mathrm{mm}^{2}/s$ 中  \n\n![](images/cc02dee1b89380f58319c7b68a2cedf58e5622012137651d6c30455c226479dc.jpg)  \n图4-3-9 ISO2431流量杯  \n\n<html><body><table><tr><td>型号</td><td>3#杯</td><td>4#杯</td><td>6#杯</td></tr><tr><td>A</td><td>63.0</td><td>62.7</td><td>62.1</td></tr><tr><td>B</td><td>3.00</td><td>4.00</td><td>6.00</td></tr><tr><td>C</td><td>5.0</td><td>6.0</td><td>8.0</td></tr></table></body></html>  \n\n$t<23s$ 时 $t=0,154\\nu+11$ $23\\leq t<150s$ 时 $t=0,223v+6,0$ 式中t——流出时间，s;——运动黏度， $\\mathrm{mm}^{2}/\\mathrm{s}$ 目  \n\n另外有一种适用于施工现场的流出型黏度计，称为察恩黏度计（Zahncup)，如图4-3-10所示。它是一种圆柱形、球形底，并配有较长提手的轻便黏度杯。其容积约为 $\\bf{44c m^{3}}$ ，按底部所开小孔的尺寸分为5个型号，合成一套。各个型号的孔的半径为：  \n\n<html><body><table><tr><td>1#</td><td>1.00mm</td><td>4#</td><td>2.13mm</td></tr><tr><td>2#</td><td>1.37mm</td><td>5#</td><td>2.64mm</td></tr><tr><td>3#</td><td>1.88mm</td><td></td><td></td></tr></table></body></html>  \n\n最佳的测量范围都是在流出时间 $30\\sim905$ ，各个型号分别测量不同黏度的产品，测定的范围为 $\\mathbf{30}{\\sim}2000\\mathbf{mm}^{2}/s,$ 。此种黏度计的特点是简易、操作方便、适合现场使用。  \n\n![](images/e961554bc4c82d31aad924fe738e4b31773fe845a4f268b69ead6304ebe31d45.jpg)  \n图4-3-10察恩黏度计  \n\n$\\textcircled{2}$ 落球法落球法利用固体物质在液体中流动的速度快慢来测定液体的黏度，所用仪器称为落球黏度计，适用于测定黏度较高的透明液体涂料，如硝酸纤维素清漆及漆料，多用于生产控制。  \n\n最简单的落球黏度计是由一根精确尺寸的玻璃管，内装满被测液体，用一钢质（或铝质、玻璃）小球沿管中心自由落下，取自由降落过程中的一段距离，测定其时间，以s表示。垂直式落球黏度计测得的秒数可以用斯托克斯（Stokes）公式近似换算成动力黏度 $\\eta\\ (\\mathrm{Pa}\\cdot\\{\\mathfrak{s}\\})$ 。  \n\n$$\n\\eta{=}\\frac{1}{18}\\times\\frac{d^{2}}{v}(\\rho_{\\mathrm{s}}{-}\\rho_{\\mathrm{f}})_{E}\n$$  \n\n式中 $d$ —钢球直径， $\\mathrm{cm}$ $\\ v$ 钢球下降速度， $\\mathrm{cm/s}$ $\\rho_{s}$ 钢球的密度， $\\mathbf{g}/\\mathrm{cm}^{3}$ 0$p_{f}$ 试样的密度， $\\mathrm{{g/cm^{3}}}$ $\\bar{\\pmb{g}}$ 一重力加速度， $980c m/s^{2}$ 0  \n\n我国国家标准GB/T1723—1993《涂料黏度测定法》规定了落球黏度计的规格和测试方法。  \n\n偏心式落球黏度计是落球黏度计的改进产品，即赫伯勒（Hoppler）黏度计。其特点是管子倾斜成一定的角度，使小球沿管壁稳定下滑，可避免小球在垂直降落过程中因偏离垂线而引起的测量误差；另外小球沿管壁下滑时，在管壁上能映出银灰点，故也可以测定不透明液体的黏度。  \n\n$\\textcircled{3}$ 气泡法利用空气气泡在液体中的流动速度来测定涂料产品的黏度，所测黏度也是运动黏度，它只适用于透明清漆。工业上常用的是加氏（GardnerHoldt）气泡黏度计，在一套同一规格的玻璃管内封人不同黏度的标准液，进行编号，将待测试样装人同样规格的管内，在相同温度下，和标准管一起翻转过来，比较管中气泡移动的速度，就可求出试样黏度，以与最近似的标准管的编号表示其黏度，通称加氏标准管号黏度，由A5起到Z10，现有41个档次。也可不与标准管比较，而是测定气泡上升的时间，用秒数作为黏度的单位。编号、秒等这些条件黏度可以换算成标准的运动黏度或动力黏度，见表4-3-4。加氏标准管内径为 $10\\mathrm{mm}\\pm0.5\\mathrm{mm}$ ，总长 $113\\mathrm{mm}\\pm0.5\\mathrm{mm}$ ，在距管底 $100\\mathrm{mm}\\pm1\\mathrm{mm}$ 及 $108\\mathrm{{mm}\\pm1\\mathrm{{mm}}}$ 处，各划一道线，即液体装至 $\\mathtt{l o o m m}\\pm\\mathtt{l m m}$ 刻度处，管塞盖至 $\\mathtt{l o g m m}$ 士 $\\mathbf{lmm}$ 刻度处，气泡长度为 $\\mathtt{8m m\\pm1m m}$  \n\n表4-3-4 加氏气泡黏度计（ $25^{\\circ}C$ 测定）  \n\n\n<html><body><table><tr><td>系列</td><td>管号</td><td>气泡上升时间/s</td><td>运动黏度/（mm²/s）</td><td>系列</td><td>管号</td><td>气泡上升时间/s</td><td>运动黏度/（mm²/s）</td></tr><tr><td>低黏度系</td><td>A-5 A-4 A-3 A-2</td><td></td><td>0.5 6.2 14 22</td><td></td><td>U V W X Y</td><td>9.2 13.0 15.7 18.9</td><td></td><td>630 880 1070</td></tr><tr><td></td><td>A-1 A</td><td></td><td>32 50</td><td></td><td></td><td></td><td></td><td>1300</td></tr><tr><td></td><td></td><td>B</td><td></td><td>65</td><td>高黏度系</td><td>Z</td><td>25.8 33.3</td><td>1800</td></tr><tr><td></td><td>C</td><td></td><td></td><td>85</td><td></td><td></td><td></td><td>2300</td></tr><tr><td></td><td>D</td><td>1.46</td><td>100</td><td></td><td>Z-1</td><td></td><td>38.6</td><td>2700</td></tr><tr><td></td><td>E</td><td>1.83 2.05</td><td></td><td>125 140</td><td>Z-2</td><td></td><td>49.85</td><td>3620</td></tr><tr><td></td><td>F</td><td></td><td></td><td></td><td></td><td>Z-3</td><td></td><td></td></tr><tr><td></td><td>G</td><td>2.42</td><td></td><td>165</td><td></td><td></td><td>67.90</td><td>4630</td></tr><tr><td></td><td>H</td><td>2.93</td><td>200</td><td></td><td>Z-4</td><td></td><td>91.0</td><td>6200</td></tr><tr><td>清漆系</td><td>I</td><td>3.30</td><td>225</td><td></td><td>Z-5</td><td></td><td>144.50</td><td>9850</td></tr><tr><td></td><td>』</td><td>3.67</td><td></td><td>250</td><td>Z-6</td><td></td><td>217.10</td><td>14800</td></tr><tr><td></td><td>K</td><td>4.03</td><td>280</td><td>橡胶系</td><td>Z-7</td><td></td><td></td><td>38800</td></tr><tr><td></td><td>L</td><td>4.40</td><td>300</td><td></td><td>Z-8</td><td></td><td></td><td></td></tr><tr><td></td><td>M</td><td>4.7</td><td>320</td><td></td><td></td><td></td><td></td><td>59000</td></tr><tr><td></td><td>N</td><td>5.0</td><td>340</td><td></td><td>Z-9</td><td></td><td></td><td>85500</td></tr><tr><td></td><td>0</td><td>5.4</td><td>370</td><td></td><td>Z-10</td><td></td><td></td><td>106600</td></tr><tr><td></td><td>P</td><td>5.8</td><td>400</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>Q</td><td>6.4</td><td>440</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>R</td><td>6.9</td><td>470</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>S</td><td>7.3</td><td>500</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>T</td><td>8.1</td><td>550</td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n此外美国ASTMD1545--1998规定的检测黏度方法，原理与加氏管法相同，只是管的规格与计算单位与加氏管法不同。ASTM管的内径为 $10.65\\mathrm{mm}\\pm0.25\\mathrm{mm}$ ，总长为 $114\\mathrm{mm}$ $\\pm1\\mathrm{mm}$ ，划3条线，刻划线距离（从管底外部量起)，第一道在 $27\\mathrm{mm}\\pm0.5\\mathrm{mm}$ 处，第二道在 $100\\mathrm{mm}\\pm0.5\\mathrm{mm}$ 处，第三道在 $108\\mathrm{mm}\\pm0.5\\mathrm{mm}$ 处（必须保证第一道与第二道线间距离为 $73\\mathrm{mm}\\pm0.5\\mathrm{mm})$ 。该法测定气泡在第一道线与第二道线之间的移动时间。黏度标准管共分36个，低黏度从 $0.22\\mathrm{mm}^{2}/\\mathrm{s}$ 到 $8.0\\mathrm{mm}^{2}/\\mathrm{s}$ 分15个档次，中黏度由 $\\mathrm{10mm^{2}/s}$ 到 $200\\mathrm{mm}^{2}/s$ 分14个档次，高黏度从 $250\\mathrm{mm}^{2}/s$ 到 $1000\\mathrm{mm^{2}/s}$ 分7个档次。这两种气泡黏度计的比较见图4-3-11。  \n\n![](images/26ea1264e552b8f5e27f3643b4e8fdb7bf14b43716aeaa993e488cd58dfe7918.jpg)  \n图4-3-11加氏管字母黏度与ASTM管号的比较换算图（ASTM管号也是气泡上升时间，限于在 $2.65\\mathrm{cm}^{2}/\\mathrm{s}$ 以上）  \n\n$\\textcircled{4}$ 设定剪切速率测定法高黏度的色漆具有非牛顿型流动性质，它们在不同的剪切应力作用下产生不同的剪切速率，因而它们的黏度不是一个定值，用上面三种方法都不能测出它们的比较实际的黏度值。要测定它们的黏度，需要在设定的剪切应力和设定的剪切速率下测定，改变其剪切应力或其剪切速率，则得到另一个黏度数值，如果在固定的剪切应力下，改变剪切速率，则可以得到这个涂料的表观黏度曲线，可以说明它的流变性。这种测定黏度的方法就是使涂料试样产生流动（通常是回转流动）测定使其达到固定速率时需要的应力，而换算成黏度单位。这种测定仪器称为旋转黏度计。  \n\n最初的旋转黏度计的构造为两个同心圆筒，内筒可以转动（图4-3-12)。用重锤的质量使内筒转动，测试的指标是在规定的时间内，转动一定的距离（ $\\bf{l m}^{\\prime}$ ）所需要的重锤质量；或固定重锤质量，测定转动一定的距离所需要的时间。以后进行了改进，用电机带动，调节转速，使内筒在给定的较低转速（如 $\\bar{6}{\\sim}120\\mathbf{r}/\\operatorname*{min}$ 左右）下转动，以使液体的流动条件符合简单运动。测定内简转动对外筒造成的力矩，就可换算成动力黏度的数值。  \n\n![](images/d5cbeca4039a179c2fd7e7bf25ea08612b51f8762989eecb088dde1f57c163b1.jpg)  \n图4-3-12各种旋转黏度计的图形示意1一同心圆筒式；2一桨式；3一转盘式；4一锥板式  \n\n![](images/7f8b86e4571181c44cd842a7ebde64f85ce07293b7188b8839e00ea4aae3c34a.jpg)  \n图4-3-13 同心圆筒旋转黏度计  \n\n![](images/5b9a5714eded17e565f371125a87c29f15911f8f59fe97f494510c109994a40e.jpg)  \n图4-3-14 桨式旋转黏度计  \n\n现代的旋转黏度计有很多形式，如图4-3-13～图4-3-16所示。各种类型的旋转黏度计都能自动显示数值和调节。  \n\n各种类型的旋转黏度计分别适用于测试不同的涂料产品。一般色漆的质量控制，通常选用转盘式的，它的精确度已能满足要求。可测得几个转速下的黏度，由此可得出流动曲线，可以测定触变性。对于乳胶漆类大多使用桨式，如斯托默黏度计（Stormer viscometer）。对于特别黏稠的涂料，通常采用锥板式旋转黏度计。  \n\n我国国家标准GB/T9269—2009《建筑涂料黏度的测定斯托默黏度计法》规定了用斯托默黏度计测定涂料黏度的方法，适用于测定非牛顿型建筑涂料，测试结果以克雷布斯单位（Krebs unit， $k_{11,}^{2}$ ）表示。这种单位的换算按仪器附有的换算表换算。  \n\n我国国家标准 $\\mathrm{GB/T\\9751-2008}$ 《涂料在高剪切速率下黏度的测定》等效采用了ISO标准，所用仪器为锥板式或圆筒形黏度计和浸没式黏度计（即转子和定子均浸没于试料中的黏度计)，检测涂料在5000～20000s-的剪切速率下的动力黏度，以Pa·s表示。  \n\n转盘式旋转黏度计的测定方法在美国ASTMD2196—1999中有详细的规定，测定结果以 $\\operatorname{m}\\operatorname{Pa}\\cdot\\mathfrak{s}$ 表示。表4-3-5为旋转黏度计的类型及应用。  \n\n![](images/8f98fceaab93d42696873314adf78674d9a63ef73788d40a1ed685b47eeefac1.jpg)  \n图4-3-15 转盘式旋转黏度计  \n\n![](images/2524d3f79a7eb1fbaaf8b0bc34bf92bb1b8ab6f385c9809453af2c875d85be07.jpg)  \n图4-3-16 锥板式旋转黏度计  \n\n表4-3-5 旋转黏度计的类型及应用  \n\n\n<html><body><table><tr><td colspan=\"2\">类 型</td><td>工业用黏度计举例</td><td>应用</td></tr><tr><td rowspan=\"2\">同心圆简</td><td>内筒旋转</td><td>中国成都NXS-11型 瑞士 Epprecht Rheomat</td><td rowspan=\"2\">适用于测定油类和涂料的动力黏度及流 变性质，测定的黏度范围较大</td></tr><tr><td>外简旋转</td><td>中国上海NDJ-2型 美国 Stormer</td></tr><tr><td colspan=\"2\">桨式</td><td>中国天津QNZ型 美国Stormer</td><td>用于一般的黏度和稠度的测定</td></tr><tr><td colspan=\"2\">转盘式</td><td>中国上海NDJ-1型 日本 BL、BM、BH 美国 Borrkfield</td><td>可测定动力黏度及流动曲线，以中等黏 度最为合适</td></tr><tr><td colspan=\"2\">锥板式</td><td>德国Rotovisco 英国ICI 中国兰州NZB-1型</td><td>用于测定较黏稠的涂料、油墨和其他物 料的流变性质</td></tr></table></body></html>  \n\n(2）厚漆、腻子稠度的测定厚漆、腻子及其他厚浆型涂料通过测定其稠度来反映其流动性能。稠度的测定方法见我国国家标准GB/T1749—1979（1989）《厚漆、腻子稠度测定法》中的规定，取定量体积的试样，在固定压力下经过一定时间后，以试样流展扩散的直径表示，单位为 $\\mathrm{cm}$  \n\n(3）涂料触变性的测定如前所述，涂料受外力例如进行搅拌或摇动时，黏度降低，但在停止搅拌静置一段时间后，黏度又上升，这种性质即为触变性。不同品种涂料的触变性不同。使用旋转黏度计可以测定触变性的有无和大小。首先从低速开始，逐渐增大转速（即剪切速率)，间隔固定的时间，改变一次转速，这样可以得到图4-3-17中的ABC线；再把转速按同样的间隔时间以逐步递减的方式再测定一次，得到图中的CA线，如果得到一个环状曲线，则说明涂料具有触变性，环的面积表示触变性的大小。  \n\n![](images/c610386b51bf7a301a889f1cdac5272cff5b21e6c1d9fdb8d7cbcb758549c8b1.jpg)  \n图4-3-17 触变性曲线",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1265,
+        "chunk": "# 6.不挥发分含量  \n\n不挥发分或称固体分指的是涂料组分中经过施工后留下成为涂膜的部分，它的含量高低对形成的涂膜的质量和涂料使用价值有直接关系。现在为了保护环境，减少挥发有机物对大气的污染，国际上提倡生产高固体分涂料。测定不挥发分含量应该属于涂料组成的分析项目，通常把它列为对涂料状态的检测项目。测定不挥发分最常用的方法是加热烘焙以除去蒸发成分。各国标准略有不同，基本原理都是一样的。将涂料在一定温度下加热烘焙，干燥后剩余物质量与试样质量比较，以百分数表示。我国国家标准GB/T1725—2007《色漆、清漆和塑料不挥发物含量的测定》规定的检测方法是用玻璃培养皿和玻璃表面皿，在鼓风恒温烘箱中测定。等效采用国际标准ISO1515—1973《色漆和清漆挥发物和不挥发物的测定》的国家标准GB/T6751—1986中，规定可用玻璃、马口铁或铝质的直径约 $75\\mathrm{mm}$ 的平底圆盘，也可在鼓风恒温烘箱中进行。温度规定为 $105^{\\circ}\\mathsf{C}\\pm2^{\\circ}\\mathsf{C}$ ，烘焙 $\\mathrm{3h}$ 。GB/T1725—2007标准中规定了对不同品种涂料的取样数量、烘焙温度，烘焙时间为 $30\\mathrm{{min}}$ 。如产品标准对烘焙温度与时间有规定时，则按产品标准规定进行。  \n\n目前还流行一种快速测定法，即将试样置于 $10\\mathrm{cm}\\times15\\mathrm{cm}$ 的铝箔（或锡箔）上，立即折叠称量，然后打开放人恒温烘箱。此法中试验量大为减少（约取样 $0,2\\sim0,5\\mathrm{g})$ ，涂层厚度减薄，因此焙烘时间也大大缩短。  \n\n在国家标准GB/T9272—2007《色漆和清漆通过测量干涂层密度测定涂料的不挥发物体积分数》中测定液体涂料在规定的温度和时间固化或干燥后所留下的干膜的体积，以百分数表示，测得的结果可用来计算涂料按一定干涂膜厚度要求施涂时所能涂装的面积大小。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1266,
+        "chunk": "# 7.容器中状态和贮存稳定性  \n\n涂料产品从制成至使用往往需要一段时间，有长有短。理想的涂料产品在容器中贮存应不发生质量变化，在打开容器进行施工时应与产品刚生产时相同。但由于涂料品种不同、生产控制水平不同或贮存保管不善等原因，往往在容器中产品的物理性状发生变化，严重的可能影响使用，特别是氧化干燥型涂料最易发生变化。所以一般涂料有保质期限的规定。在生产方面应该尽量延长产品保质期限，在使用时首先应该检查涂料产品在原装容器中贮存的时间是否过期，及其原装状态。在购进一批涂料产品时，为了保证使用时不发生问题，应该抽样检测产品在容器中的状态，并进行在特定条件下贮存的试验，以检查其质量的变化，即贮存稳定性的检查。贮存稳定性也应作为涂料设计生产过程中的一个必要的性能控制项目。  \n\n容器中状态的检查通常在涂料取样过程中进行。在取样时应先检查容器是否完整，标志的生产日期与取样检查日期的间隔时间应明确记录清楚，检查封口是否完整严密，做好记录以后再打开封盖。对液体涂料要检查的项目有：结皮情况、分层现象、色漆有无液体上浮或颜料上浮现象，用木条或金属棍或玻璃棒插人容器检查有无沉淀结块，沉淀是否容易搅起，经过搅拌是否均匀，颜色是否上下一致等。对检查情况要做好记录。在检查完容器中状态后，再搅匀取出代表性样品。日本JIS规格所列检测方法可供参考。  \n\n贮存稳定性是指涂料产品在正常的包装状态和贮存条件下，经过一定的贮存期限后，产品的物理或化学性能所能达到原规定的使用要求的程度，或者说是涂料产品抵抗在规定条件下进行存放后可能发生的性能变化的程度。对贮存稳定性的检测，我国制定了国家标准GB/T6753.3—1986《涂料贮存稳定性试验方法》。依据此标准，测定的条件分为自然环境贮存和在 $50^{\\circ}C\\pm2^{\\circ}C$ 加速条件下贮存两种。将待试样品取3份分别装人容积为0.4L的标准的压盖式金属漆罐中，1罐原始试样在贮存前检查，2罐进行贮存性试验。检查的项目为：  \n\n$\\textcircled{1}$ 结皮、腐蚀和腐败味的检查，分为0、2、4、6、8和10共6个等级评定；  \n\n$\\textcircled{2}$ 沉降程度的检查，也按以上6级评定；  \n$\\textcircled{3}$ 涂膜颗粒、胶块及刷痕的检查，也按以上6级评定；  \n$\\textcircled{4}$ 黏度变化的检查，比较贮存后与原始黏度，依其比值百分数也按6级评定。  \n\n最后综合以“通过”或“不通过”为结论性评定，或按产品要求评定。  \n\n根据产品品种的要求，对不同品种也有不同的贮存稳定性的检测方法，如美国ASTMD1309一1993（2004）规定的马路画线漆贮存期间沉降性的检测方法。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1267,
+        "chunk": "# 8.结皮性  \n\n氧化干燥型清漆和色漆在贮存中的结皮倾向是一个长期存在的问题。它也是贮存稳定性检测内容的一个项目，但有时把它单列出来，专门进行检测。涂料产品结皮不但会改变涂料组分比例，影响成膜性能，还会引起涂料的其他各种病，造成施工质量的下降，因此必须努力避免和防止，至少应控制结皮的形成速度和结皮的性质。目前对涂料中加入防结皮剂，或使产品具有一定的触变性，均是减少和防止结皮所采取的一些措施。  \n\n结皮性测定主要有两个方面：一个是测定涂料在密闭桶内结皮生成的可能性，一个是测定在开桶后的使用过程中结皮形成的速度。对于某些涂料来说，在开桶的情况下，结皮现象不可能完全避免，但如何使结皮生成的速度及其性质能控制在可容许的范围内，以尽量减少损失，则是涂料生产者应注意的问题。  \n\n(1）密闭试验推荐用带有螺旋顶盖的玻璃瓶，装人容积2/3的试样，旋紧顶盖，倒放暗处，可定期检查或直到结皮生成为止。  \n\n（2）敬罐试验试样装人漆罐深度的一半，盖并时常观察，直到结皮为止。以上两项试验时最好用一已知结皮性质的样品同时存放作对比，以便在不同阶段比较这两者的结皮情况。  \n\n日本JIS规格K5400中列有结皮性试验方法，可供参考。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1268,
+        "chunk": "# 9.冻融稳定性  \n\n主要适用于以合成乳胶或合成树脂乳液为漆基的水性漆，在经受冷冻继之融化后，其稠度、抗絮凝或结块、起斑等方面无有害性变化，而能保持其原有性能，称为具有冻融稳定性。  \n\n我国国家标准 $\\mathrm{GB/T\\9268-1988}$ 《乳胶漆耐冻融性的测定》规定了检测冻融稳定性的方法。主要是将试验样品在温度一 $18^{\\circ}C\\pm2^{\\circ}C$ 条件下冷冻 $17\\mathrm{h}$ ，然后在 $23^{\\circ}C\\pm2^{\\circ}C$ 放置，分别在6h和 $48\\mathrm{h}$ 后进行检验，与在 $23^{\\circ}C\\pm2^{\\circ}C$ 温度下存放的对比样品对比： $\\textcircled{1}$ 测定黏度（用斯托默黏度计)； $\\textcircled{2}$ 观察评定容器中试验样品的沉淀、胶结、聚结、结块等状况，以“无变化”、“轻微”和“严重”表示； $\\textcircled{3}$ 将对比样品和试验样品刷在同一块规定的试板上，在至少干燥 $24\\mathrm{h}$ 后，目视观察并记录两者干漆膜的遮盖力、光泽、凝聚、斑点和颜色的变化情况。美国ASTMD2243—1995（2003）规定为在- $-9.4^{\\circ}\\mathbb{C}\\pm2.8^{\\circ}\\mathbb{C}$ 冷冻7天后测定。  \n\n也有的乳胶漆产品规定检测方法采用多次冻融循环。如有些外墙涂料的检测采用$-5^{\\circ}C\\pm1^{\\circ}C$ ， $\\mathrm{16h}$ ，然后在 $23^{\\circ}C\\pm2^{\\circ}C$ 条件下8h为一循环。共进行3次循环，然后判断结果。从实践来看，抗冻融试验破坏的明显与否不仅仅取决于温度负得多低、时间多长，更取决于冷冻和融化反复次数的多少，即合理的循环周期。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1269,
+        "chunk": "# 10.稀释剂的性状检测  \n\n稀释剂是涂料中一类重要的辅助材料。它的性能和质量直接影响到用来稀释的涂料产品和涂膜的性能。对稀释剂性能也必须在使用前检测，其主要检测项目有下面7个。  \n\n（1）透明度。  \n\n(2）颜色（这两个项目的检测方法已在前面叙述)。  \n\n(3）挥发性检测挥发性能，用与乙醚挥发时间进行比较，以其比值表示。检测方法按行业标准HG/T3860—2006《稀释剂、防潮剂挥发性测定法》执行。  \n\n(4）胶凝数胶凝数表示的是稀释剂稀释硝化棉（或过氯乙烯树脂）溶液的能力，逐渐滴人与稀释剂配制的溶液不相混溶的有机溶剂，直至树脂析出，溶液变浑浊，以耗用的滴入溶剂的体积（mL）表示，其数值越高，表示稀释剂的稀释力越强。  \n\n(5）白化性白化性表示稀释剂加人被稀释产品中造成漆膜发白及失光的现象的可能性，稀释剂要求无白化性为合格。  \n\n(6）水分测定稀释剂中是否含有水分，有定性和定量的检测方法。  \n\n(7）闪点稀释剂的闪点测定可依照GB/T5208—1985《涂料闪点测定法快速平衡 法》进行。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1270,
+        "chunk": "# 三、涂料施工性能的检测  \n\n涂料的施工性能至关重要，它直接影响到涂膜的质量。过去由于大多采用手工施工，对涂料施工性能要求不多，也不严格。随着现代化大生产流水线施工的发展，对涂料施工性能的要求项目逐渐增多，规定逐渐严格。例如现代电泳漆的施工性能就是一个典型例子。涂料施工性能从将涂料施工到被涂物件开始，至形成涂膜为止，其中包括施工性（刷涂性、喷涂性或刮涂性）、双组分涂料的混合性能、活化时间和使用有效时间、使用量和标准涂装量、湿膜和干膜厚度、流平性和流挂性、最低成膜温度、干燥时间、遮盖性能等。电泳漆、粉末涂料则各有其特定的旋工性能。对涂料施工性能的检测是对涂料能否符合被涂物件需要的一个重要方面。它的检测结果在一定程度上说明这种涂料产品最佳的施工条件。施工性能检测方法虽然尽量模仿实际施工情况，但由于方法的可行性和结果的重现性的要求，是在特定的条件下进行检测的，因而与实际施工时的情况还是有出人，这是需要注意的。另外有一些项目只能得到比较性结果，而不能数值化。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1271,
+        "chunk": "# 1.使用量  \n\n使用量是指涂料在正常施工情况下，在单位面积上制成一定厚度的涂膜所需的漆量，以$\\mathbf{g}/\\mathbf{m^{2}}$ 表示。  \n\n使用量的测定，可作为设计施工单位估算涂料用料计划的参考。它与涂料中着色颜料的多少无关，但受产品的密度影响较大。涂料使用量与实际消耗量不同。测定的方法有刷涂法和喷涂法，喷涂法所测得的数值，不包括喷涂时飞溅和损失的漆，因此，它比实际消耗量为低。测定时涂漆厚度因产品而异，同时还由于测定者手法不同造成涂刷厚度产生差异，故所测使用量数值只是一个参考数值，与现场施工时单位面积的实际消耗量有差别。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1272,
+        "chunk": "# 2.施工性  \n\n施工性用来检测涂料产品施工的难易程度。液体涂料施工性良好，即指涂料用刷、喷或刮涂等方法施工到被涂物件表面上时，不但容易施工，而且所得到的涂膜很快流平，没有流挂、起皱、缩边、渗色或咬底等现象。依据施工方法，施工性分别称为刷涂性、喷涂性或刮涂性（对腻子的施工）等。施工性的考查用实际施工结果给予定性的结论，在评定时存在着主观因素，所以最好用与标准样品比较得出结果。我国国家标准GB/T6753.6—1986《涂料产品的大面积刷涂试验》规定的方法主要用于评价在严格规定的底材上大面积施涂色漆、清漆及有关产品的刷涂性和流动性，除了考察平面外，还观察在有凸出部位和锐角部位致使涂料收缩的倾向，可以获得更完整的结果。所用试板面积较大，钢板的尺寸不小于 $\\ln x$ $1\\mathrm{m}\\times0.00123\\mathrm{m}$ ，木板尺寸不小于 $1\\mathrm{m}\\times0.9\\mathrm{m}\\times0.006\\mathrm{m}$ ，水泥板尺寸不小于 $\\operatorname{lm}\\times0,\\operatorname{g}_{\\operatorname{m}}\\times$ $0.005\\mathrm{m}$ 。对刷子尺寸和刷涂工艺有具体规定。评价内容包括与标准样品比较的施工性能的差异和涂膜刷痕消失、流挂、收缩等规定的缺欠的现象。日本JISK5400中对施工性检测规定的试验板尺寸为500mm×200mm，根据产品规定分别检验刷涂、喷涂或刮涂性能，并且按涂一道和涂二道进行检查，用文字表示检查结果。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1273,
+        "chunk": "# 3.流平性  \n\n流平性是涂料施工性能中一个重要项目，从涂料施工性中单独分出，专列为一个检测项目。流平性是指涂料在施工后，其涂膜由不规则、不平整的表面流展成平坦而光滑表面的能力。涂膜的流平是重力、表面张力和剪切力的综合效果，因此流平的前提是涂料是否能润湿工件表面，即是否具有较好的流动性，这就与涂料的组成、性能和施工方式等有关。另外涂料中若加入硅油、醋丁纤维素等助剂，也可直接改善涂膜的流平性。  \n\n在国家标准GB/T1750—1979（1989）《涂料流平性测定法》中规定流平性的测定方法，分为刷涂法和喷涂法两种，以刷纹消失和形成平滑漆膜所需时间来评定，以分钟表示。刷涂法的测定方法是将试样按GB/T1727—1992《漆膜一般制备法》中规定，将试样调至施工黏度，涂刷在马口铁板上，使之平滑均匀，然后在涂膜中部用刷子纵向抹一刷痕，观察多少时间刷痕消失，涂膜又恢复成平滑表面，合格与否由产品标准规定，一般流平性良好的涂膜在 $10\\mathrm{min}$ 之内就可以流平。喷涂法则观察涂漆表面达到均匀、光滑、无皱（无橘皮或鹅皮）状态的时间，同样以产品标准规定评定是否合格。美国ASTMD2801—1994检测涂料流平性方法规定，使用有几个不同深度间隙的流平性试验刮刀，将涂料刮成几对不同厚度的平行的条形涂层，观察完全和部分流到一起的条形涂层数，与标准图形对照，用 $0\\sim10$ 级表示，10级表示完全流平，0级则表示流平性最差。此方法适用于白及浅色漆。ASTMD4062—1999（2003）规定了使用Leneta levelingtestblade 检测水性和非水性浅色建筑涂料的流平性的方法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1274,
+        "chunk": "# 4.流挂性  \n\n液体涂料涂刷在垂直表面上，受重力的影响，在湿膜未干燥以前，部分湿膜的表面容易有向下流坠，形成上部变薄、下部变厚，严重的形成球形、波纹形状的现象，这种现象说明这种涂料易流挂，或其抗流挂性不好，是涂料应该避免的性能。它的起因主要是涂料的流动特性不适宜，或者是涂层过厚超过涂料可能达到的限度，或是涂装环境和施工条件不合适。涂料的流挂速度与涂料黏度成反比，与涂层厚度的二次方成正比。涂膜的流挂性不合标准规定，干后就难得到平整、厚薄均匀的涂膜，影响装饰外观，还要影响各项保护性能。所以对涂料的流挂性也需要检测。一般的测定方法是在试板上涂上一定厚度的涂膜，将试板垂直立放，观察湿膜的流坠现象，进行记录，检查是否符合产品标准规定。我国国家标准GB/T9264—1988《色漆流挂性的测定》检验方法，采用流挂试验仪对色漆的流挂性进行测定，以垂直放置、不流到下一个厚度条膜的涂膜厚度为不流挂的读数。厚度数值越大，说明涂料越不容易产生流挂现象。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1275,
+        "chunk": "# 5.干燥时间  \n\n液体涂料涂于物件表面从流体层变为固体涂膜的物理或化学变化过程通称涂膜的干燥。于燥过程依据涂膜物理性状主要是黏度的变化过程可分为不同阶段，习惯上分为表面干燥、实际干燥和完全干燥三个阶段，美国ASTMD1640—2003把干燥过程分成八个阶段。对于干燥的时间，施工部门的要求是越短越好，以免涂饰工件沾上雨露尘土，并可大大缩短施工周期；而对涂料制造来说，因受使用材料的限制，往往均要求一定的于燥时间，才能保证成膜后的质量。由于涂料的完全于燥所需时间较长，故一般只测定表面干燥（表干）和实际干燥（实干）两项。  \n\n(1）表面干燥时间测定常用的方法有吹棉球法、指触法［GB/T1728—1979（1989）]和小玻璃球法（GB/T6753.2—1986）。吹棉球法是在漆膜表面上放一脱脂棉球，用嘴沿水平方向轻吹棉球，如能吹走而膜面不留有棉丝，即认为表面干燥。指触法是以手指轻触漆膜表面，如感到有些发黏，但无漆粘在手指上，即认为表面干燥或称指触干。小玻璃球法是将约 $0.5\\mathrm{g}$ 的直径为 $125\\sim250\\mu\\mathrm{m}$ 的小玻璃球于 $50\\sim150\\mathrm{mm}$ 的高度倒在漆膜表面，当漆膜上的小玻璃球能用刷子轻轻刷离，而不损伤漆膜表面时，即认为达到表面干燥，记录其时间。按产品规定判断是否合格。  \n\n（2）实际干燥时间测定常用的有压滤纸法、压棉球法、刀片法和厚层十燥法。我国国家标准GB/T1728—1979（1989）有详细规定。在ISO9117：1990标准中有用对涂层施加负载以测定完全干燥程度的方法。压滤纸法是在漆膜上用干燥试验器（如图4-3-18所示）压上一片定性滤纸，经30s后移去试验器，将样板翻转而滤纸能自由落下，即认为实际干燥。同样，压棉球法采用30s后移去试验器和脱脂棉球，若漆膜上无棉球痕迹及失光现象，即认为实际干燥。刀片法使用保险刀片，适用于厚涂层和腻子膜。厚层干燥法主要用于绝缘漆。漆膜干燥时间受周围环境的温度、湿度、通风、光照等因素影响，故测定时必须具备一定的环境和设备，在恒温恒湿室中进行。  \n\n![](images/efcdc4e44299fde0750af6a5e48a3f783e4dfc47ddad745a3f99fd52e7cd04b5.jpg)  \n图4-3-18 干燥试验器  \n\n![](images/ea76596383b460258258da9b680d10315c855efcf9667dc5f124b4a5ad71c86e.jpg)  \n图4-3-19 齿轮型干燥测定仪  \n\n由于涂料的干燥和涂膜的形成是一个进行得很缓慢的和连续的过程，因此为了能观察到干燥过程中的整个变化，可以采用自动于燥时间测定器。一种是利用电机通过减速箱带动齿轮，以 $30\\mathrm{mm/h}$ 的缓慢速度在漆膜上直线走动，全程共24h，随着漆膜的逐渐十燥，齿轮痕迹也逐步由深至浅，直至全部消失（图4-3-19)。另一种是利用电机带动盛有细砂的漏斗，在涂有漆膜的样板上缓慢移动，砂子就不断地掉落在漆膜上形成直线状的砂粒痕迹，以测定干燥的不同阶段所需要的时间（图4-3-20)。较先进的有利用针尖缓慢地在漆膜上画出半径 $5\\mathrm{cm}$ 的圆，画一圈需 $24\\mathbf{h}$ ，这样就可在较小的试板面积上观察漆膜随时间而变化的干燥程度（图4-3-21)。  \n\n![](images/251e0bf8cb3ba66a80528378efa9a2441ed64312f6957f0527edf4543b3cdf91.jpg)  \n图4-3-20 落砂型于燥测定仪  \n\n![](images/5892110a9e5a63b5d5104846e23e094aaa67a166de6899b7ac8ff57f40b80582.jpg)  \n图4-3-21 画圈型干燥测定仪",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1276,
+        "chunk": "# 6.涂膜厚度  \n\n在涂料检验过程中，漆膜厚度是一项很重要的控制指标。涂料某些物理性能的测定及耐久性等一些专用性能的试验，均需要把涂料制成试板，在一定的膜厚下进行比较；在施工应用中，由于涂装的漆膜厚薄不匀或厚度未达到规定要求，均将对涂层性能产生很大的影响。因此如何正确测定漆膜厚度是质量检验中重要的一环，必须给予应有的重视。  \n\n目前，测定漆膜厚度有各种方法和仪器，选用时应考虑测定漆膜的场合（实验室或现场)、底材（金属、木材、玻璃)、表面状况（平整、粗糙、平面、曲面）和漆膜状态（湿、干）等因素，这样才能合理使用检测仪器和提高测试的精确度。  \n\n我国等效采用ISO2808：2007制定了GB/T13452.2《色漆和清漆漆膜厚度的测定》。其中于膜厚度的测定方法，列为方法 $1{\\sim}5$ ，湿膜厚度的测定方法列为方法6。见表4-3-6。  \n\n表4-3-6 干膜厚度的测定方法  \n\n\n<html><body><table><tr><td>编号及说明</td><td>应用</td><td>注</td></tr><tr><td>方法1： 以干膜质量对应于干膜厚度的干膜 厚度测量方法</td><td>适用于漆膜过软，不能用仪器测量 的漆膜。例如气干漆处于固化早期的|之间的平均漆膜厚度 试板</td><td>测量精确性差，但可用于核定规定限度 测试中漆膜无损</td></tr><tr><td>方法2： 以千分尺法测量干膜厚度</td><td>试板或实质上平整的涂漆面</td><td>漆膜必须硬到足以经受住与千分尺卡头 紧密接触时而无压痕 精确度为±2μm 测试中漆膜受损</td></tr><tr><td>方法3： 以指示表法测量干膜厚度</td><td>同方法2</td><td>漆膜必须足够硬，以耐受放下仪器压脚 时无压痕 精确度为士2μm 测试中漆膜受损</td></tr><tr><td>方法4： 以显微镜法测量干膜厚度</td><td>A法：漆膜厚度测量精确度为士2um 或更精确 B法：漆膜厚度测量精确度为1μm</td><td>切下试板或涂漆物体的一部分，并使之 埋在树脂中。此法推荐作为仲裁方法及用 于多变外形底材如喷丸金属上的漆膜测量 使用专用的显微镜观察测量从底材上取 下的一小部分漆膜纵断面的厚度</td></tr><tr><td>方法5： 非破坏性仪器测量法</td><td>适用于磁性金属底材</td><td>仪器运转根据： ①磁通量原理 ②涡流原理</td></tr><tr><td>β射线反向散射法</td><td>适用于非磁性金属底材 主要用于移动中漆膜，如卷涂涂料 漆膜的连续测定</td><td>③磁引力脱离原理 仪器运转根据涡流原理 使用具有放射性源的高度专门化仪器。 为使测量准确，漆膜必须均匀</td></tr><tr><td>方法6： 湿膜厚度的测量</td><td>A.轮规：适用于实验室试板或新涂 漆表面的湿膜厚度测量 B.梳规：适用于现场涂膜操作时的 湿膜厚度测量</td><td>测量精确性差，但能估计膜干时的大致 厚度 测量值可粗略指明湿膜厚度 注：两种情况都应以方法5校核干膜 厚度</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1277,
+        "chunk": "# （1）湿膜厚度的测定  \n\n湿膜的测量必须在漆膜制备后立即进行，以免由于挥发性溶剂的蒸发而使漆膜发生收缩现象。GB/T13452.2—1992的方法6中规定使用轮规和梳规测定的方法。在美国ASTMD1212—1991（2001）中规定用轮规和用Pfund湿膜计测定的方法。  \n\n$\\textcircled{1}$ 轮规基本上是由3个圆盘组成的一个整体，外侧两个圆盘同样大小，中间圆盘是偏心的，且半径较短，以使3个圆盘在某一半径处相切（即处在同一平面上)，这样该处的间隙为零。在相反的半径方向上，间隔即为最大。在圆盘外侧有刻度，以指示不同间隙的读数。测试时（见图4-3-22）须注意仪器必须垂直于被测表面，不能左右晃动，否则将得不出正确的结果；另外仪器在表面上的滚动，若是由零开始，则由于湿膜的被挤压而把漆推向前，得出的厚度读数将大于实际湿膜厚度，使结果产生一定的误差。  \n\n$\\textcircled{2}$ 梳规一种可放在口袋里随身携带的金属板或塑料片，形状为正方形或矩形，如图4-3-23所示。在其4边都切有带不同读数的齿，每一边的两端都处在同一水平面上，而中间各齿则距水平面有依次递升的不同间隙。使用时将垂直接触于试验表面，这样将有一部分齿被漆膜所沾湿。湿膜厚度为在沾湿的最后一齿与下一个未被沾湿的齿之间的读数。梳规是一种价格低廉的简便测量仪器，特别适用于在施工现场使用。  \n\n![](images/8eda9c518aa76b897d1d4f103a15f738ebf8159bb5a35eeddd8c9a95a3fc96d8.jpg)  \n图4-3-22 轮规  \n\n![](images/656d6dc888047b234f7a7ddadd9046349360db649315169103103cdace8795cb.jpg)  \n图4-3-23 梳规  \n\n$\\textcircled{3}$ Pfund湿膜计仪器系一个凸面透镜L（曲率半径为 $250\\mathrm{mm}$ ）和2个金属圆管 $\\mathbf{T}_{1}$ 和$\\mathrm{T_{2}}$ 组成，见图4-3-24。使用时用手缓慢地将管 $\\mathrm{\\DeltaT_{1}}$ 往下压，以使装在底部的透镜 $\\texttt{L}$ 通过湿膜触及底板表面，量取涂料在透镜上沾附部分的直径，按下式计算，即可得出湿膜厚度 $h$ ，以 $\\mu\\mathrm{m}$ 表示。  \n\n$$\nh{=}\\frac{D^{2}\\times1000}{16r}{=}0.25D^{2}\n$$  \n\n式中 $D$ 沾附部分直径， $\\mathrm{mm}$ 透镜的曲率半径， $250\\mathrm{mm}$ 0需指出的是，涂膜在镜面上由于表面张力的缘故，因而所测得的湿膜厚度与实际的湿膜厚度稍有差别，公式是在假设这两者完全相等的情况下成立的。为使结果更可靠起见，尚需引人修正系数，详见美国ASTMD1212—1991（2001)。  \n\n![](images/86794aa86c4f45c557a286d71e1b92f641d3cfcd5d5d226247f8deb9aae7f23e.jpg)  \n图4-3-24Pfund 湿膜计  \n\n以上3种湿膜厚度计从实际应用来看，以轮规较为理想，既能在实验室使用，也能在现场进行测定，使用简便，读数准确。Pfund湿膜计虽然也较为精确，但操作和计算较烦琐。梳规成本低廉，携带方便，但误差较大，只能用于施工现场对湿膜厚度作粗略测定。  \n\n(2）干膜厚度的测定在实际工作中大量遇到的是干膜厚度的测量，目前已有不少种方法和仪器，但每一种方法都有一定的局限性，能适用于所有类型样品的环境的则仅仅是少数。依工作原理来分，基本上分为两大类：磁性法和机械法。  \n\n$\\textcircled{1}$ 磁性法根据被测底材不同，又可分为磁性测厚仪和非磁性测厚仪。磁性测厚仪主要是利用电磁场磁阻的原理来测量钢铁底板上涂层的厚度；非磁性测厚仪则用涡流测厚原理来测量诸如铝板、铜板等不导磁底板上涂层的厚度。需注意的是，某些涂料品种由于含有铁红、铝粉等，将对测试结果有一定的影响。磁性法目前已成为干膜厚度测定的主要方法。国际和国内都有磁性和非磁性测厚仪的生产，同时不断进行改进，创出多种形式和牌号，如对施工现场干膜厚度的测量，已发展有永久磁体来代替电磁场，使结构简单，便于携带，但精确度稍差。又如将电源改为干电池或充电电池，同样能使结构紧凑，便于携带，且仍能保持较高的精确度。现在的测厚仪主要是数字显示式，直接读出数据，并发展成适合多种形状表面测厚的多用式仪器。  \n\n常用的磁性测厚仪和非磁性测厚仪的型号和规格可参见表4-3-7。  \n\n表4-3-7 常用测厚仪型号和规格  \n\n\n<html><body><table><tr><td>品种</td><td>型号</td><td>量程/m</td><td>测量精度/%</td><td>生产厂</td></tr><tr><td rowspan=\"5\">磁性测厚仪</td><td>QUC-200</td><td>0~200</td><td>士3</td><td>中国天津市建筑仪器试验机公司</td></tr><tr><td>MCH-1</td><td>0～2000</td><td>士3</td><td>中国山东济宁超声电子仪器厂</td></tr><tr><td>SDHC</td><td>0～3000</td><td>≤±5</td><td>中国广东江门市化工仪表厂</td></tr><tr><td>Mikrotest-F</td><td>0～1000</td><td>5</td><td>德国E.P.K公司</td></tr><tr><td>Elcometer-F1</td><td>0~1250</td><td>士3</td><td>英国埃高(Elcometer)公司</td></tr><tr><td rowspan=\"4\">非磁性测厚仪</td><td>MINISCOPE200</td><td>0～1000</td><td>±3</td><td>中国沈阳仪器仪表工艺研究所</td></tr><tr><td>7503</td><td>0~300</td><td>±3</td><td>中国厦门第二电子仪器厂</td></tr><tr><td>Positector6000N2</td><td>0~1500</td><td>士3</td><td>美国狄夫高（Defelsko）公司</td></tr><tr><td>Coatest 1000N</td><td>0～1000</td><td>士3</td><td>英国COATEST公司</td></tr></table></body></html>\n\n注：上列各厂家均同时有磁性和非磁性两种测厚仪生产。  \n\n$\\textcircled{2}$ 机械法使用杠杆千分尺或千分表测定涂膜厚度的方法使用较久，优点是使用时不受底材性质的限制和漆膜中导电或导磁颜料的影响，仪器本身精度可读到 $\\pm2\\mu\\mathrm{m}$ 。但只能对较小面积的样板进行测试，为了消除误差，必须多次测量，手续烦琐，不如磁性法测厚仪简便。  \n\n![](images/f225ff623b9083d632703634da3125096a1945bc6961568d9606af68dcafdfa5.jpg)  \n图4-3-25 显微镜测厚法 1—面漆；2—底漆；3—底材  \n\n测定漆膜厚度的显微镜法，已被推荐为漆膜厚度测定的仲裁方法。其测试原理如图4-3-25所示。该法是用一定角度的切割刀具将涂层作一 $\\mathbf{V}$ 形缺口直至底材，然后用带有标尺的显微镜测定 $\\alpha^{\\prime}$ 和 $\\theta^{\\prime}$ 的宽度。标尺的分度已通过校准系数换算成相应的微米数，因此可从显微镜中直接读出漆膜的实际厚度 $(a,b)$ 。此法的最大优点是除能测定总漆膜厚度外，尚能测定多层漆系统的每层漆的漆膜厚度，同时可以在任何底材上进行，其不足之处是将使漆膜遭受局部破坏。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1278,
+        "chunk": "# 7.遮盖力  \n\n色漆均匀地涂刷在物体表面，由于涂膜对光的吸收、反射和散射而使底材颜色不再呈现出来的能力，称为色漆的遮盖力。遮盖力的高低由涂料的组成决定。同样质量的色漆产品，遮盖力高的在相同的施工条件下就可比遮盖力低的涂装更多的面积。  \n\n目前色漆遮盖力的测定方法有下面三种。  \n\n（1）单位面积质量法测定遮盖单位面积所需的最小用漆量，用 $\\mathbf{g}/\\mathbf{m}^{2}$ 表示遮盖力。通常采用黑白格玻璃板，也可用标准的黑白格纸。我国国家标准GB/T1726—1989《涂料遮盖力测定法》规定了使用黑白格板，有刷涂法和喷涂法两种测定方法。  \n\n(2）最小漆膜厚度法利用遮盖住底面所需的最小湿膜厚度以测定色漆的遮盖力，所得结果以 $\\mu\\mathrm{m}$ 表示。测定仪系用一块黑白间半的光学玻璃平板，其边上标有毫米刻度，在其上盖有一块在一端有一定高度的透明玻璃顶板，从而形成一个楔形空间，测定时在底板上倒上少量样品，来回移动顶板，一直到通过顶板及漆层看不到底板E的黑白分界线为止，记下从分界线至顶板前端的读数，由于楔形空间的角度是已知的，就可求出最小湿膜厚度，或者通过仪器所附的换算表换算出单位面积用漆量。此法用漆量少，测试速度快，但仍为目测，存在测试结果准确性问题。  \n\n(3）反射率对比法为了克服目测终点的困难，ISO及各国标准均推荐采用反射率仪对遮盖力进行比较准确的评定。但这种方法主要适用于白色和浅色漆，系把试样以不同厚度涂布于透明聚酯膜上，干燥之后置于黑、白玻璃板上，用反射率仪测定其反射率，从而得出对比率CR。  \n\n$$\nC R=\\frac{R_{\\mathrm{B}}}{R_{\\mathrm{W}}}\n$$  \n\n式中 $R_{\\mathrm{{B}}}$ ——黑板上的反射率；  \n\nRw—白板上的反射率。  \n\n当对比率等于0.98时，即认为全部遮盖，根据漆膜厚度就可得出遮盖力。此法终点判断比较准确，能克服上述两方法的不足，但操作较复杂些。我国已等效采用ISO标准，制定了GB/T13452.3—1992《色漆和清漆遮盖力的测定第一部分：适用白色和浅色漆的Kubelka-Munk法》，等效采用ISO6504/1—1983（1989）标准，所测得的遮盖力系指对比率必须是0.98时的涂布率，适用于三刺激值中 $\\mathbf{Y}$ 大于70的色漆漆膜，不适用于荧光和金属漆。还可测得不同涂布率 $(\\mathbf{m}^{2}/\\mathbf{L})$ 时的对比率，即其相应的遮盖率。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1279,
+        "chunk": "# 8.多组分涂料的混合性与使用寿命  \n\n多组分涂料的混合性和使用寿命是它特有的重要施工性能。多组分涂料组分之间的混合性不好，得不到良好的涂膜。组分混合后最好很快混合均匀，不需要很长的熟化时间；混合好的涂料要有较长的使用寿命，即在较长的时间内涂料性能不发生变化，如变稠、胶化等，而保证所得涂膜质量一致。涂料的使用寿命长对施工有利，当然它的长短是由涂料组成决定的。多组分涂料的混合性和使用寿命列为它的技术指标，通常是它的必测项目。测试方法比较简单。  \n\n(1）混合性通常检测方法是按产品规定的比例在容器中混合，用玻璃棒进行搅拌，如果很容易地混成均匀液体，则认为混合性“合格”。  \n\n(2）使用寿命将组分在一定容量的容器中按比例混合后，按照产品规定的使用寿命条件放置，达到规定的最低时间后，检查其搅拌难易程度、黏度变化和凝胶情况，并且涂制样板放置一定时间（如 $24\\mathbf{h}$ 或 $48\\mathrm{h}$ ）后与标准样板对比检查漆膜外观有无变化或缺陷（如孔穴、流坠、颗粒等）产生。如果不发生异常现象，则认为“合格”。为了准确判断多组分涂料的可使用时间，可以对混合后的多组分涂料按一定时间间隔检测其黏度，观察其黏度变化情况。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1280,
+        "chunk": "# 第三节 涂膜性能检测  \n\n涂膜性能检测是涂料检测中最重要的部分。涂膜的检测结果基本反映了产品的质量水平和它的功能水平。涂膜性能检测的内容主要包括4个方面： $\\textcircled{1}$ 基本物理性能的检测，其中有表观及光学性质、机械性能和应用性能（如重涂性、打磨性等）； $\\textcircled{2}$ 耐物理变化性能的检测，如对光、热、声、电等的抵抗能力的检测； $\\textcircled{3}$ 耐化学性能的检测，主要是检查涂膜对各种化学品的抵抗性能和防腐蚀（锈蚀）性能； $\\textcircled{4}$ 耐久性能的检测。这些检测项目主要是对涂在底材上的涂膜进行的。有个别产品需要对其游离膜进行一些项目的检测。  \n\n经过多年的研究开发，涂膜性能检测的方法中每一项性能几乎都有不同的方法，各有优缺点，分别从不同角度说明其性能。也有时用不同方法会得出不同的结论。同时近年来对一种方法也开发出多种不同类型的仪器，其精确性也有不同。因而对涂膜性能检测的方法和仪器要根据产品的性能需要而加以选定，以便正确反映产品的真实状况。此外检测的目的不同，也需要选择合适的检测项目和方法：为了控制产品质量，一般是选用通用的标准的检测方法；为了开发品种，研究产品结构与性质的关系，就需要广泛地检测，以实现预期的要求。现在世界各国都制定了许多涂膜检测方法的标准，并且在不断地发展。  \n\n涂膜的检测，通常是在标准状态下进行的，虽然尽力模仿施工时的条件，结果还是有差异的，可能涂膜性能检测结果很好，而在实际施工时反而不好，这就要深入研究找出原因，采用更为准确或更接近实际条件的检测方法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1281,
+        "chunk": "# 一、均匀涂膜的制备  \n\n要使涂膜检测的结果准确可靠，就需要制备符合要求的标准涂膜。按照产品标准的规定，在指定的底材上制备具有指定厚度的均匀的涂膜，是涂膜检测的基础。制得的涂膜要能真实地反映涂膜的本质，即使有缺陷也要反映出来，但又不能由于外部的原因，如制备的环境，而使涂膜本质有所改变。  \n\n要制得均匀的涂膜样板，要注意底板的选择与处理、制备方法与条件两个方面。底板的材质根据产品标准选定，表面处理要达到要求。制备涂膜时，涂料黏度、制备方法、环境温度和湿度、干燥条件和时间等，都要严格遵守规定的要求。  \n\n各国对涂膜制备均制定有标准方法，我国国家标准GB/T1727—1992《漆膜一般制备法》规定了制备一般涂膜的材料、底板的表面处理、制板方法、涂膜的干燥和状态调节、恒温恒湿条件以及涂膜厚度等。制板方法列出刷涂法、喷涂法、浸涂法、刮涂法、均匀漆膜制备法和浇注法。其中漆膜制备器（刮涂器和线棒涂布器）是常用的制备仪器  \n\n![](images/6f2a0a25df96e9eba2ef20ef95d324f4fc9259fd50e47ae687f698e39c141815.jpg)  \n图4-3-26 刮涂器 （漆膜涂布器)  \n\n刮涂器法所采用的仪器叫刮涂器（doctorblade）或叫漆膜涂布器，如图4-3-26所示。操作时，将试样倒在底板上，用刮涂器把样品展平。由于刮涂器刀片与平面具有一定的间隙，因此就可得到一定厚度的湿膜。根据试验需要，可以调节刀片与平面的间隙以便制得各种厚度的漆膜。一般来说，刮涂的湿膜厚度只是刮刀与底板之间缝隙间距的一半，而刮涂法的成功与否则取决于底板的平整度以及刮刀的质量，否则会产生波纹的涂膜或其他不规则的现象。  \n\n后又发展了线棒式刮涂器，这种仪器有两种形式。一种是金属棒，在它上面紧紧地缠着金属线，涂料通过金属线所形成的空间流涂在样板上，金属线越粗，则空间越大，其漆膜也越厚。这种刮涂器特别适用于有挠曲性的底材，如纸或薄的金属板。另一种形式是一根尼龙棒，直接在棒上车削成螺丝纹，对浅色漆可以用黑色棒，对深色漆可以用白色棒，这种相对照的颜色有助于对刮涂器的清洗。  \n\n为了使刮涂器的操作平稳、均匀，以消除人为的操作误差，现在发展成由电机带动方式的自动漆膜涂布器，以使刮涂的漆膜更为均匀一致。图4-3-27所示的即为其中的一种，参见ASTMD 823—1995。  \n\n有时为了试验研究和检测某些涂膜性能的需要，应用不附在底材上的自由膜。自由膜的制备方法过去用锡汞齐法，在镀锡钢板表面用喷涂法或浸涂法涂装，固化以后，将涂漆钢板的一端放人盛有汞的广口瓶中，汞渗人钢板涂层下和锡发生锡汞齐反应，最后涂膜从钢板上可完全脱落下来。采用这种方法对操作人员身体有损害，在一些国家已禁止使用。现在多数可从涂有脱模剂的玻璃板上制得，也有用脱膜纸制备的。涂层可用线棒涂布器涂布，可以得到厚薄均匀的自由涂膜  \n\n![](images/b9be152a3ac68d157ebe32dd409babf1662456ea5bb2506fc7fc3b180ef71ba1.jpg)  \n图4-3-27 自动漆膜涂布器",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1282,
+        "chunk": "# 二、涂膜的表观及光学性能的检测",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1283,
+        "chunk": "# 1.涂膜的外观  \n\n对用于检测涂料施工性制备的涂膜样板，使其干燥后，或用制得的均匀涂膜的样板，检测涂膜的表面状态，通常在日光下肉眼观察，可以检查出涂膜有无缺陷，如刷痕、颗粒、起泡、起皱、缩孔等。一般是与标准样板对比。由于制备样板通常在室内标准状况下进行，操作又比较仔细，所得结果比较标准，但与实际施工条件的涂膜的外观是有差距的。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1284,
+        "chunk": "# 2.光泽  \n\n光线照射在平滑表面上，一部分反射，一部分透入物体内部产生折射。光反射的规律是入射角等于反射角。反射光的光强与入射光光强的比值称为反射率。光投射到平整表面上的反射称为镜面反射。涂膜的光泽就是涂膜表面将照射在其上的光线向一定方向反射出去的能力，也称镜面光泽度。反射的光量越大，则其光泽越高。光泽是漆膜性能检验中的一个重要项目，光泽的测定基本上采用两大类仪器，即光电光泽计和投影光泽计，目前以前者为主。  \n\n![](images/2b8cdf1e543ae6288894b0bb288daa1352dcb0e8131e34f41d3d4868c8789fc1.jpg)  \n图4-3-28 光泽测定原理简图  \n\n（1）光电光泽计光电光泽计是目前测定光泽的主要仪器，虽然有多种规格型号，但其测试原理基本相同，如图4-3-28所示。  \n\n光源S所发射的光线经透镜 $\\mathbb{L}_{1}$ 变成平行光线以一定的角度 $\\alpha$ ，如 $45^{\\circ}$ 投射到被测表面T上，由T以同样的角度反射的光线经透镜 $\\mathbf{L}_{2}$ 聚集到光电池 $\\bar{\\mathbf{F}}$ 上，产生的光电流借助于检流计就可得出光泽的读数。  \n\n光电池F所接受的光通量大小取决于样板的反射能力。若人射角为 $45^{\\circ}$ ，涂膜的光泽值为由试验样板上反射出来的光通量和由折射率为1.567的黑色玻璃板上反射出来的光通量的比值，以百分数表示。  \n\n$$\nG_{s}(\\%)=\\frac{\\phi_{s}}{\\phi_{0}}\\times100\\%\n$$  \n\n式中 $G_{\\mathrm{s}}$ ———以百分数表示的光泽值；  \n\n$\\phi_{\\mathrm{s}}$ 样板反射出来的光通量， $9\\%$  \n\n$\\phi_{0}$ ——一折射率为1.567的黑色抛光玻璃板反射出来的光通量，其值为 $100\\%$ 中  \n\n由此可见，只要使被测样板与标准板进行比较即可测得光泽值，仪器本身所带的黑色玻璃为二级标准板，其光泽值应由原始标准板来标定。  \n\n漆膜表面反射光的强弱，不但取决于漆膜表面的平整和粗糙程度，还取决于漆膜表面对投射光的反射量和透过量的多少。在同一个漆膜表面上，以不同入射角投射的光，会出现不同的反光强度。因此在测量漆膜光泽时，必须先固定光的入射角度。日本标准JIS Z8741—1997中规定不同入射角度所应用的范围如表4-3-8所示。  \n\n美国标准ASTMD523—1989（1999）中的规定：  \n\n\n<html><body><table><tr><td>人射角度</td><td>85°</td><td>75°</td><td>60°</td><td>45°</td><td>20°</td></tr><tr><td>适用品种</td><td>涂膜</td><td>纸面及其他</td><td>塑料、涂膜</td><td>塑料</td><td>塑料、涂膜</td></tr><tr><td>适用范围</td><td>60°测定小于 10%的表面</td><td></td><td></td><td></td><td>60°测定大于70%的表面</td></tr></table></body></html>  \n\n<html><body><table><tr><td>入射角度</td><td>85°</td><td>60°</td><td>20°</td></tr><tr><td>适用范围</td><td>低光泽漆膜</td><td>-般光泽漆膜</td><td>高光泽漆膜</td></tr></table></body></html>  \n\n因此涂膜的光泽可分类如下（以 $60^{\\circ}$ 光泽计测量）：  \n\n\n<html><body><table><tr><td>高光泽</td><td>70%或70%以上</td><td>蛋壳光至平光</td><td>6%~2%</td></tr><tr><td>半光或中等光泽</td><td>70%~30%</td><td>平光</td><td>2%和2%以下</td></tr><tr><td>蛋壳光</td><td>30%~6%</td><td></td><td></td></tr></table></body></html>  \n\n属于 $70\\%$ 以上的高光泽漆膜则应使用 $20^{\\circ}$ 的光电光泽计测定；相反，对于低于 $30\\%$ 的低光泽漆膜，则以采用 $85^{\\circ}$ 的光电光泽计更为理想。因此目前光电光泽计主要是多角光泽计$o^{o}$ ， $20^{\\circ}$ ? $45^{\\circ}$ ? ${\\hat{6}}{\\hat{0}}^{\\circ}$ ， $75^{\\circ}$ ， $85^{\\circ}.$ ）和变角光泽计（ $20^{\\circ}\\sim85^{\\circ}$ 之间均可测定)，一台仪器能有多种用途，从而增大了测试的范围。  \n\n目前国内常用的光电光泽计的型号和规格可参见表4-3-9。  \n\n表4-3-8 不同入射角的应用范围  \n表4-3-9 常用光电光泽计型号和规格  \n\n\n<html><body><table><tr><td>型号</td><td>特征</td><td>角度</td><td>精密度 光泽单位</td><td>生产厂</td></tr><tr><td>KGZ-1A</td><td>台式、普及型、数显</td><td>20°、60°、85°</td><td>1</td><td>中国天津科器高新技术公司</td></tr><tr><td>GZ-2</td><td>台式、普及型</td><td>45°</td><td>±1</td><td>中国广西梧州市化工仪器厂</td></tr><tr><td>WGG(B)-1</td><td>台式、普及型、数显</td><td>20°、45°、75°</td><td>±1</td><td>中国泉州市伟达计量仪器厂</td></tr><tr><td>HGG</td><td>袖珍型、数显</td><td>20°、60°、85°</td><td>±1</td><td>中国上海海港实业总公司技术开发中心</td></tr><tr><td>4520</td><td>袖珍型、数显</td><td>20°、60°、85°</td><td>±1</td><td>德国BYK-Gardner公司</td></tr><tr><td>NOVO-GLOSS</td><td>袖珍型、数显</td><td>各种角度</td><td>±0.5</td><td>英国PHOPIONT公司</td></tr><tr><td>UGV-5D</td><td>台式、数显</td><td>20°～85°(可变角度)</td><td>±1</td><td>日本Suga 试验机株式会社</td></tr></table></body></html>  \n\n(2）投影光泽计光电光泽计虽有一定的科学性，但若漆膜有擦痕、波纹或橘皮等病，就会产生漫反射，使反射光不易集中在光电池接收器上，另外漆膜颜色的不同也会产生与人们视觉不一致的光泽度。为此长期以来仍保留并进一步发展了投影光泽计，一种是将漆膜光泽与一套已知光泽的标准板来比较，找出与被测样板反光量相等的标准板，用标准板的标号来表示被测样板的光泽度，如过去最早使用的底特律光泽计。另一种是在漆膜的表面上反射各种印刷图案或数字，用反射影像的清晰度与标准光泽板反射的同样影像的清晰度来比较，以评定光泽，如亨特尔（Hunter）光泽计，见图4-3-29。这些仪器制作简单，光源固定，可不受漆膜颜色和自然光线等条件的影响，但由于都是目测评定，且都需要定期更换标准光泽板，因此使其在使用方面有一定的局限性。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1285,
+        "chunk": "# 3.鲜映性  \n\n鲜映性是指涂膜表面反映影像（或投影）的清晰程度，以DOI值表示（distinctnessofimage)。它能表征与涂膜装饰性相关的一些性能（如光泽、平滑度、丰满度等）的综合指标，测定内容实际上也是涂膜的散射和漫反射的综合效应。它可用来对飞机、汽车、精密仪器、家用电器，特别是高级轿车车身等的涂膜的装饰性进行等级评定。  \n\n鲜映性测定仪的关键装置是一系列标准的鲜映性数码板，以数码表示等级，分为0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1.0、1.2、1.5、2.0共13个等级，称为DOI值。每个DOI值旁印有几个数字，随着DOI值升高，印的数字越来越小，用肉眼越不容易辨认。观察被测表面并读取可清晰地看到的DOI值旁的数字，即为相应的鲜映性。  \n\n![](images/2081cb139ffd07acfdf26ca87a63f1546be81d33cad93bec29e3af342335f43a.jpg)  \n图4-3-29 亨特尔光泽计  \n\n该仪器国外产品有“PGD4鲜映仪”，见图4-3-30，国内有天津市材料试验机厂与长春汽车材料研究所生产的“QYG型涂膜鲜映性仪”。目前我国国家标准GB/T13492—1992《各色汽车面漆》中I型面漆的技术要求中已规定有鲜映性指标，属于出厂检验项目，要求必须达到 $0.6\\sim0.8$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1286,
+        "chunk": "# 4.雾影  \n\n![](images/f07e89f0b262ec4f49375e6bce4f22cc7ecef6e6109ca0856b2be3abf8fefd21.jpg)  \n图4-3-30 雾影光泽仪  \n\n雾影系高光泽漆膜由于光线照射而产生的漫反射现象。雾影只有在高光泽条件下产生，且光泽必须在 $90\\%$ 以上（用 $20^{\\circ}$ 法测定)。  \n\n前面所述的鲜映性测定仪，是测量散射和漫反射的综合效应，且以散射为主，而目前人们倾向于把这两个因素分开，以解决雾影的测定问题。现在出现的雾影光泽仪实际上是一台双光束光泽仪，其中参比光束可以消除温度对光泽以及颜色对雾影值的影响。仪器的主接收器接受漆膜的光泽，而副接收器则接受反射光泽周围的雾影。  \n\n雾影值最高可达1000，但评价涂料时，雾影值在250以下就足够了，故仪器测试范围为 $0\\sim250$ 。涂料厂生产的产品，其雾影值应定在20以下，否则漆膜雾影很大，将严重影响高光泽漆膜的外观，尤其浅色漆影响更为显著。  \n\n目前国内汽车涂料生产厂及用户使用的雾影光泽仪主要是德国BYKGardner公司生产的台式雾影光泽仪，编号为4600，液晶显示，精度为 $\\leq1$ 光泽单位，见图4-3-30。最新的发展是微型雾影光泽仪，编号为4630，仪器精度相同，但体积大大缩小，系袖珍便携式，仪器仅重 $600\\mathbf{g}$ 0",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1287,
+        "chunk": "# 5.颜色  \n\n颜色是一种视觉，所谓视觉就是不同波长的光刺激人的眼睛之后，在大脑中所引起的反映。涂膜的颜色是当光照到涂膜上时，经过吸收、反射、折射等作用后，从其表面反射或透射出来，进人我们眼睛的颜色。决定涂膜颜色的是照射光源、涂膜本身性质和人眼。  \n\n测定漆膜颜色的一般方法是按GB9761--1988《色漆和清漆的目视比色》的规定，将试样与标准样同时制板，在相同的条件施工、干燥后，在天然散射光线下目测检查，如试样与标准样颜色无显著区别，即认为符合技术容差范围。也可以将试样制板后，与标准色卡进行比较，或在比色箱CIE标准光源D65的人造日光照射下比较，以适合用户的需要。  \n\n虽然一般用肉眼可以区分漆膜颜色的差别，但由于受到色彩记忆能力和自然条件等因素的限制，不可避免会有人为误差的产生，因此我国国家标准GB11186.1.2.3—1989《漆膜颜色的测量方法》规定用光谱光度计、滤光光谱光度计和三刺激值色度计测定涂膜颜色方法，即用通称的光电色差仪来对颜色进行定量测定，以把人们对颜色的感觉用数字表达出来。国际上最为通用的颜色测定系统是国际照度委员会所颁布的C、I、E坐标系统，即测定三元刺激值x、y、2。由于所有的颜色都可以由红、绿和蓝光来合成，三元刺激值的原理是依据人的眼神经对红、绿、蓝3个颜色所引起的刺激量的不同来计算的。因此在色差仪中，在固定的光源下，以红滤色片测得的反射率为x值，以绿滤色片测得的反射率为y值，以蓝滤色片测得的反射率为z值，然后通过公式计算，即可得出色差。色差的单位为NBS（nationalbureau of standardsunit），原由美国国家标准局制定，一个NBS单位表示一般目光能辨别的极微小颜色间的差别，该单位的数值与人的感觉的关系如下所示：  \n\n<html><body><table><tr><td>NBS单位</td><td>相应于人的色差感觉</td><td>NBS单位</td><td>相应于人的色差感觉</td></tr><tr><td>0~0.5</td><td>极轻微（trace)</td><td>3.0~6.0</td><td>严重（appreciable)</td></tr><tr><td>0.5~1.5</td><td>轻微（slight）</td><td>6.0～12.0</td><td>强烈（much）</td></tr><tr><td>1.5~3.0</td><td>明显（noticable）</td><td>12.0以上</td><td>极强烈（verymuch)</td></tr></table></body></html>  \n\n在没有光电测色仪的场合，或为了快速评定漆膜颜色的变化，也可采用国际标准化组织机构研究并推荐的《染色牢度褪色样卡》即5级灰色标准样卡。我国纺织工业部早有发行，是5对灰色标样，分成5个等级，分别代表原样与试后样的相对变化程度。其原理是基于灰色在色光方面变化较少，故在光线的吸收和反射上较为稳定，这样肉眼就比较容易区分。涂料样板经试验后，与标准板一起与灰色样卡比较以观察变色程度所属灰色样卡的等级。具体评定如表4-3-10所示。  \n\n表4-3-10 灰色样卡的色差等级  \n\n\n<html><body><table><tr><td>等级</td><td>变色程度</td><td>变色状况（试板与标准板的颜色比较）</td><td>色差(NBS单位)</td></tr><tr><td>0</td><td>无变化</td><td>相同</td><td>0</td></tr><tr><td>1</td><td>轻微变色</td><td>稍有差异</td><td>1.5</td></tr><tr><td>2</td><td>明显变色</td><td>较大差异</td><td>3.0</td></tr><tr><td>3</td><td>严重变色</td><td>很大差异</td><td>6.0</td></tr><tr><td>4</td><td>完全变色</td><td>完全不同</td><td>12.0</td></tr></table></body></html>  \n\n此样卡可按国家标准GB250《染色牢度褪色样卡》技术规定复制，其色差采用分光光度计测定，按阿特姆斯（Adams）色值公式计算。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1288,
+        "chunk": "# 6.白度  \n\n白度是指在某种程度上白色涂膜接近于理想白色的颜色属性。白色漆膜的白度不仅表现了颜色的特征，同时也反映了所使用的白色颜料的优劣。白度越高，则遮盖力也越强，其他性能也相应地得到提高。  \n\n在涂料检验中，漆膜的白度一般用目测即可进行评定，但往往因白色漆膜的色相不同而造成人们视觉的差异，不能对真正的白色作出客观的评价，故目前已普遍采用仪器测定。按颜色测定原理，要完全确定一个白色，需要3个参数，在这一点上，白色与其他颜色没有什么区别，但在实际应用中，只需测定绿光反射率 $G$ 和蓝光反射率 $B$ ，即可得出白度和白度指数值。  \n\n蓝光白度（W） 直接测量试样对蓝光的反射能力， $\\scriptstyle{W=B}$ 白度指数 (WI) 定义为蓝光与绿光的反射率差。  \n\n$$\nW I{=}4B{-}3G\n$$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1289,
+        "chunk": "# 7.明度  \n\n明度是物体反射光的量度。从不同颜色比较，白色涂膜反射光的能力最强。明度高的白色或彩色涂膜表示它反射了大部分投射在涂膜上的光。有些国家规定对白色涂膜的明度进行测定，作为检验白色涂料光学性能优劣的判断。日本JIS规格K-5400采用 $45^{\\circ}$ ? $0^{\\circ}$ 扩散反射率以测定白色涂膜的明度。即用入射角为45°、反射角为0°的扩散反射仪测定，通过用标准白色样块校正的仪器，测出其反射率数值，数值越高，明度越大。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1290,
+        "chunk": "# 三、涂膜力学性能的检测  \n\n涂膜作为保护性材料，它必须具备一定的强度，所以它的力学性能是很重要的性能。前面已经提到，涂膜属于黏弹性固体，它的物理性质有一定的特殊性；涂膜的各项性能多是根据实际需要而定名的，所以涂膜的力学性能虽然也用与其他材料同样的名称，但其含义有所不同，并且表示其性能常常冠以“耐”或“抗”来命名。涂膜的力学性能间的关联性很强，每个性能的检测有多种方法，分别从不同的角度来表示其性能的情况，在选用时要根据产品情况和施工需要来确定。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1291,
+        "chunk": "# 1.硬度  \n\n是表示漆膜机械强度的重要性能之一，其物理意义可理解为漆膜表面对作用其上的另一个硬度较大的物体所表现的阻力。这个阻力可以通过一定质量的负荷，作用在比较小的接触面积上，测定漆膜抵抗包括由于碰撞、压陷或者擦划等造成的变形的能力而表现出来。  \n\n涂膜的硬度测定方法很多，目前常用的有3类方法，即摆杆阻尼硬度法、划痕硬度法和压痕硬度法。3种方法表达涂膜的不同类型的阻力，各代表不同的应力应变关系。  \n\n(1）摆杆阻尼硬度法通过摆杆横杆下面嵌人的两个钢球接触涂膜样板，在摆杆以一定周期摆动时，摆杆的固定质量对涂膜压迫，而使涂膜产生抗力，根据摆的摇摆规定振幅所需要的时间判定涂膜的硬度，摆动衰减时间长的涂膜硬度高。这种检测方法或称摆杆阻尼试验。所用仪器称为摆杆阻尼试验仪，通用的有科尼格（Konig）摆（简称K摆）和珀萨兹（Persoz）摆（简称P摆）两种形式。现在这两种形式的摆杆硬度试验仪已被我国国家标准GB/T1730—2007《漆膜硬度的测定摆杆阻尼试验》采用。两种摆的结构、质量、尺寸、摆动周期及摆幅不同。摆杆与涂层间的相互作用还取决于涂层具有的复杂的弹性和黏弹性。这两种摆的测定结果之间不能建立起通用的换算关系。在产品检测时通常只规定使用其中一种摆杆仪器。摆杆阻尼试验的结果与测试时的环境有关，应在控制温、湿度条件，无气流影响的情况下进行。此外，涂膜厚度及底材材质也对阻尼时间有影响。摆杆试验仪的测定结果以秒计，K摆在抛光平板玻璃板上的标准时间为 $250{\\bf s}\\pm10{\\bf s}$ ，P摆为 $420s$ 。现在的两种试验仪都附有光电控制的计数装置，自动记录阻尼时间。  \n\n我国国家标准GB/T1730—2007《漆膜硬度的测定摆杆阻尼试验》中还规定可用双摆杆阻尼试验仪检测硬度的方法。  \n\n用摆杆阻尼试验仪测定涂层时，摆动衰减的主要原因是因为涂层对机械能的吸收，摆动衰减时间和损失模量成反比，模量损失用来表示吸收机械能的能力。因为从动力学性质测定的论述中，在玻璃态区域和橡胶态区域的损失模量都比较低，可以推测在这两个区域内摆动衰减时间长，实际上摆杆试验测定软的橡胶涂层其衰减时间变长证明这一情况。因而有人认为摆杆试验是涂层损失模量的检测而不是涂膜硬度的检测。  \n\n美国ASTMD2134—1993所规定的斯韦德硬度计（Swardrocker）也是采用与摆杆阻尼试验仪相同的原理，以两个相距 $25\\mathrm{mm}$ 的扁平金属环相连与涂膜样板接触，沿环的边缘固定重物。测定时仪器在涂膜上以近似于圆的形式摆动。用在固定量的衰减期内所需的摆动次数的2倍值表示涂膜的硬度。用在抛光的平板玻璃上摆动50次作为校正标准，即玻璃的硬度值为100，涂膜的硬度值小于100，以数值的高低表示涂膜硬度的高低。斯韦德硬度计的摆动衰减是由于滚动摩擦和机械损失能引起的。从实际应用来看，这种硬度计观察比较方便，相对误差较小，测试速度较快，但灵敏度较差。它适于较软的涂膜的测定。  \n\n摆杆阻尼试验方法测试的优点是对涂膜不破坏。  \n\n(2）划痕硬度法采用在漆膜表面用硬物划出痕迹或划伤涂膜的方法以测定涂膜硬度。常用的有铅笔硬度法和划针测定法。  \n\n铅笔硬度法有手工操作和仪器试验两种方法，是采用已知硬度的铅笔测定涂膜硬度，以涂膜不被型伤的铅笔硬度(手工操作)，或型伤涂膜的下一级硬度的铅笔硬度(仪器试验)作为涂膜的硬度。铅笔应采用规定的生产厂制造的符合标准的高级绘图铅笔，按规定削出笔芯。各国采用的铅笔硬度分级不同。我国国家标准GB/T6739—2006《涂膜硬度铅笔测定法》中规定使用的铅笔由6H到6B共13级，6H最硬，6B最软。作为仲裁试验要用仪器试验方法，通用仪器型号有QHQ型铅笔法划痕硬度仪。  \n\n划针测定法系用仪器的针尖划伤涂膜，用涂膜抗划针划透性来代表涂膜硬度。以在规定负荷下是否被划针划透，或划针划透涂层所需最小负荷来表示。现在使用的仪器有自动型和手动型两种，自动型可以依靠导电性从电工仪表中直接显示结果，我国国家标准GB/T9279—2007《色漆和清漆划痕试验》规定用自动型仪器作为仲裁试验的仪器，所得结果比较准确。  \n\n划痕法测定硬度时，涂膜不仅受压力的作用，而且受剪力的作用，对涂膜的附着力也有所体现，因此它所测定的涂膜硬度特征是与摆杆阻尼试验法有所不同的。  \n\n(3）压痕硬度法采用一定质量的压头对涂膜压人，从压痕的长度或面积来测定涂膜的硬度。有不同型号的压痕硬度试验仪器。我国国家标准GB/T9275—1988《色漆和清漆巴克霍尔兹压痕试验》规定使用巴克霍尔兹（Buchholz）压痕试验仪测试涂膜硬度的方法。测得的压痕长度表现了涂层对仪器的压痕器压入的抵抗能力，其结果以抗压痕性表示，计算公式为：  \n\n$$\nH{=}100/L\n$$  \n\n式中H——抗压痕性；$L$ 压痕长度， $\\mathbf{mm}$ 0  \n\n美国ASTMD1474—1998则规定可使用Knoop压头和Pfund压头两种压痕试验仪。前者如 Tukon 硬度计，后者如 Pfund 硬度计。Knoop 压头为金刚石角锥，Pfund 压头为透明无色石英半球状体。用Knoop压头的检验结果称为Knoop硬度值，简称KHN，按以下公式计算得出：  \n\n$$\nK H N={\\frac{L}{l^{2}c_{\\mathrm{p}}}}\n$$  \n\n式中 $L$ —压头上负荷质量， $\\mathbf{kg}$ $l$ —压痕长度， $\\mathbf{mm}$ Cp——压头常数，7.028×10-2 口  \n\n用Pfund压头的检验结果称为Pfund硬度值，简称PHN，其计算公式为：  \n\n$$\nP H N{=}\\frac{L}{A}{=}\\frac{4L}{n d^{2}}{=}1.27\\left(\\frac{L}{d^{2}}\\right)\n$$  \n\n式中 $L$ ——负荷质量，规定为 $1,0\\mathrm{kg}$ $A$ —-压痕面积， $\\mathrm{mm}$ $d^{2}$ —一平均压痕直径， $\\mathbf{mm}$ 章  \n\n公式简化为PHN=1.27/d²  \n\n压痕硬度在硬膜比较明显，一般结果与涂膜厚度有关，对同一涂料来说，薄膜的压痕硬度值要高于厚膜。从实际测量看，白色及彩色漆的压痕长度易于判断。压痕试验对有弹性的如橡胶涂层结果不准确。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1292,
+        "chunk": "# 2.耐冲击性  \n\n或称冲击强度，系指涂于底材上的涂膜在经受高速率的重力作用下发生快速变形而不出现开裂或从金属底材上脱落的能力，它表现了被试验漆膜的柔韧性和对底材的附着力。需注意的是，所谓耐冲击性实际是一个冲击负荷造成的快速变形，应与漆膜经受静态负荷下冲击的性能区分开。静态负荷下的变形受到塑性和时间等因素的影响，而在冲击负荷的情况下就不存在这个问题。所以ISO6272一2002改称落锤试验。  \n\n耐冲击性所用仪器为冲击试验仪，以一定质量的重锤落在涂膜样板上，使涂膜经受伸长变形而不引起破坏的最大高度，用重锤质量与高度的乘积表示涂膜的耐冲击性，通常用N·cm（kgf·cm）表示。美国习惯用in·lb表示。冲击检测可分为正冲和反冲，即涂膜面向上为正冲，涂膜面向下为反冲，对大多数涂料来说，反冲比正冲要严格。涂膜的厚度以及底材的厚度和表面处理情况都会影响冲击强度的结果，因而需要标准化。  \n\n现在各国通用的冲击试验仪形状基本相同，但重锤质量、冲头尺寸和滑筒高度有不同规格。我国国家标准GB1732—1993《漆膜耐冲击测定法》规定重锤质量 $1000\\mathbf{g}\\pm\\mathbf{1}\\mathbf{g}$ ，冲头进入凹槽的深度为 $2\\mathrm{mm}\\pm0.1\\mathrm{mm}$ ，滑筒刻度等于 $50\\mathrm{cm}\\pm0.1\\mathrm{cm}$ ，分度为 $1\\mathrm{cm}$ 。因为所用重锤质量是固定的，所以其检测结果以不引起涂膜破坏的最大高度（cm）表示。现在有可变式冲击试验器，滑筒刻度增至 $120\\mathrm{cm}$ ，甚至更高，重锤及冲头有多种规格，可按不同标准更换测试，新的国家标准GB/T20624.1—2006《色漆和清漆快速变形（耐冲击性）试验第1部分：落锤试验（大面积冲头）》和GB/T20624.2—2006《色漆和清漆快速变形（耐冲击性）试验第2部分：落锤试验（小面积冲头)》就是如此。  \n\n此外对于管状涂漆样品可采用图4-3-31所示的摆锤式撞击器。仪器有可摆动的两臂，涂漆后的管状试件均固定在两臂上，使两臂以一定的力量彼此撞击，观察漆膜的破坏情况。  \n\n美国ASTMG14—1988（1996）规定采用的落锤试验仪，铁砧底座改为相应的夹紧装置，可以在重锤的作用下，便涂漆管子的表面上产生一个点冲击，然后用电测的方法检查涂层由于冲击而产生的裂痕。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1293,
+        "chunk": "# 3.柔韧性  \n\n当涂于底材上的漆膜受到外力作用而弯曲时，所表现的弹性、塑性和附着力等的综合性能称为柔韧性。涂膜的柔韧性由涂料的组成所决定。它与检测时涂层变形的时间和速度有关。耐冲击性和后成型性也是柔韧性的一种反映。柔韧性的测定主要通过涂膜与底材共同受力弯曲，检查其破裂伸长情况，其中也包括了涂膜与底材的界面作用。  \n\n目前涂层柔韧性的测定主要有以下3种仪器。  \n\n(1）轴棒测定器 国家标准GB/T1731—1993《漆膜柔韧性测定法》规定使用轴棒测定器（见图4-3-32）。它是由粗细不同的7个钢制的轴棒所组成的，固定于底座上，底座可用螺丝钉固定在试验台边上。每个轴棒长度均为 $35\\mathrm{mm}$ ，曲率半径分别为0.5mm、1mm、1.5mm、2mm、2.5mm、5mm和7.5mm。测试时将涂漆的马口铁板在不同直径的轴棒上弯曲，以其弯曲后不引起漆膜破坏的最小轴棒的直径 $:\\mathrm{mm}.$ 来表示。  \n\n![](images/15a6d149c6b45080f62140bded98fc6f4426454dd4c0974e5bcaa2b582d324c1.jpg)  \n图4-3-31 摆锤式撞击器  \n\n![](images/202d81ec4dd89228a6af995667f185f38091a79d5fe91bfa81a4172d122493d6.jpg)  \n图4-3-32 柔韧性测定器  \n\n漆膜在不同直径的轴棒上弯曲时，轴棒直径与漆膜相对伸长率的关系如表4-3-11所示。  \n\n表4-3-11轴棒直径与漆膜相对伸长率的关系  \n\n\n<html><body><table><tr><td>轴棒直径/mm</td><td>1</td><td>2</td><td>3</td><td>4</td><td>5</td><td>10</td><td>15</td></tr><tr><td>漆膜内表面的伸长率/%</td><td>20.00</td><td>11.1</td><td>7.69</td><td>5.88</td><td>4.76</td><td>2.44</td><td>1.64</td></tr><tr><td>漆膜外表面的伸长率/%</td><td>23.20</td><td>12.9</td><td>8.92</td><td>6.82</td><td>5.52</td><td>2.83</td><td>1.90</td></tr></table></body></html>  \n\n以上伸长率是在马口铁板厚度为0.25mm、漆膜厚度为0.02mm的条件下计算所得的。其计算公式如下：  \n\n$$\n\\varepsilon_{1}=\\frac{h_{2}/2}{r+h_{2}/2}\\times100\\%\n$$  \n\n$$\n\\varepsilon_{2}=\\frac{h_{1}+h_{2}/2}{r+h_{2}/2}\\times100\\%\n$$  \n\n式中 $\\varepsilon_{1}$ 1 漆膜内表面的伸长率， $\\%$ $E_{2}$ 漆膜外表面的伸长率， $0\\%$ $h_{1}$ 漆膜厚度， $\\mathrm{mm}$ 2$h_{2}$ 底板厚度， $\\mathrm{mm}$ i轴棒半径，mm。  \n\n从式中可看出：在其他条件相同时，若增加漆膜厚度（或底板厚度），则漆膜相对伸长率也将随之增大。  \n\n（2）圆柱轴弯曲试验仪国家标准GB/T6742—2007《漆膜弯曲试验（圆柱轴）》中规定使用圆柱轴弯曲试验仪（见图4-3-33）。它适用于0.3mm厚度以下的试板，轴的直径分别为2mm、3mm、4mm、5mm、6mm、8mm、10mm、12mm、16mm、20mm、25mm和32mm。测试时，插人试板，并使涂漆面朝外，平稳地合上仪器，使试板在轴上弯曲180°，然后观察漆膜是否开裂或被剥离。此法优点是可以采用整板试验，且手掌不接触漆膜，消除了人体对试板温度升高的影响。  \n\n![](images/d210a4636e7bf311a99b9232fa19416e8eaf825a0432ac4d20948f3985fd22a3.jpg)  \n图4-3-33圆柱轴弯曲试验仪1-轴；2一相当于轴高的挡条  \n\n![](images/4fdb7760768878efb7c0290204d86169cb649372896a9a43aabee8e3038a8d04.jpg)  \n图4-3-34 锥形挠曲测试仪  \n\n(3）锥形挠曲测验仪国家标准GB/T11185—1989《漆膜弯曲试验（锥形轴）》中规定使用锥形挠曲测试仪（如图4-3-34所示），它的中心轴是个圆锥体，长 $203\\mathrm{mm}$ ，直径从最大$38\\mathrm{mm}$ 延伸至最小 $3.2\\mathrm{mm}$ 。把试验样板插人固定后，转动上部手柄，使试板紧贴圆锥体表面挠曲，观察引起漆膜破坏的最小直径（ $:\\mathrm{mm}.$ ）即代表该漆膜的柔韧性。这种仪器的特点也是可以采用整板试验，且避免了用一套常规轴棒结果的不连续性。在漆膜厚度已知的情况下，同样可以求得漆膜百分伸长率。  \n\n此外，腻子的柔韧性的测定另有一项标准方法，使用柔韧性测定仪测定，具体方法参阅GB/T1748—1979（1989）《腻子膜柔韧性测定法》。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1294,
+        "chunk": "# 4.杯突试验  \n\n杯突试验（也叫顶杯试验或压陷试验）所使用的仪器系头部有一球形冲头，恒速地推向涂漆试板背部，以观察正面漆膜是否开裂或从底材上剥离。漆膜破坏时冲头压人的最小深度即为杯突指数［也称为艾利克逊（Erichsen）数]，以 $\\mathrm{mm}$ 表示，它与耐冲击性所表现的性能不同。杯突试验的主要结构见图4-3-35。  \n\n最初，杯突试验主要用来测定金属板材的强度和变形性能。若冲压出现裂纹，其压入深度即为该金属板材的强度。试验金属底材上的漆膜，实际上就是在底材伸长的情况下，测定它的强度、弹性及其对金属的附着力。这在卷涂工业和制罐工业中需进行后成型的那些涂料，如卷钢涂料、罐头漆等是必不可少的测试项目。  \n\n按GB/T9753—2007《色漆和清漆 杯突试验》的规定，测试涂漆样板时，仪器的球形冲头直径为 $20\\mathrm{mm}$ ，且试板应是平整、无变形、厚度不小于 $0.3\\mathrm{mm}$ 及不大于 $1.25\\mathrm{mm}$ 的磨光钢板。而在实际测定中，若采用厚度小于 $0.3\\mathrm{mm}$ 的马口铁板，当冲压深度达 $\\mathrm{{8mm}}$ 时，漆膜虽未破坏或脱落，但底材马口铁板已经裂开，从而导致试验失败。  \n\n![](images/7faff8ec32123f23abc17c33cf3458475dc1d7e9db7cbbacd5f352d8462abf93.jpg)  \n图4-3-35 杯突试验机 1—冲模；2—试板夹紧器； 3—冲头；4—试板  \n\n由于漆膜的强度、弹性、附着力等性能均与大气温度、湿度、底材处理和漆膜厚度等因素有关，因此杯突试验也应在标准条件下进行。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1295,
+        "chunk": "# 5.T型弯曲试验  \n\n和杯突试验相同，T型弯曲试验也属于对涂膜的后成型性试验，用来衡量涂膜在成型加工中不开裂和没有损坏的能力，特别是卷板涂料和罐头漆的性能检测的重要项目。T型弯曲是将涂膜面向外将样板对弯 ${180}^{\\circ}$ ，如果无破损，可计为零T或0T。零T表示在弯曲内没有金属的厚度，如果发现开裂，再加人一个金属板板厚的弯曲，如果这次没有开裂，弯曲计做1T，依次可得到2T、3T等。可用手工方法检测，美国ASTMD3281—1984规定可用冲击楔形弯曲仪（impact-type wedge bend apparatus）检测，使用-个力加速弯曲并通过落体冲击试验和黏胶带试验，可以对涂膜附着变形的情况有比较完整和准确的认识，便于判断涂膜性能。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1296,
+        "chunk": "# 6.附着力  \n\n系指漆膜与被涂物件表面通过物理和化学力的作用结合在一起的坚牢程度。根据吸着学说，这种附着强度的产生是由于涂膜中聚合物的极性基团（如羟基或羧基）与被涂物表面的极性基相互结合所致，因此凡是减少这种极性结合的各种因素均将导致漆膜附着力的降低。  \n\n如：被涂物表面有污染、水分；涂膜本身有较大的收缩应力；聚合物在固化过程中相互交联而消耗了极性基的数量等。  \n\n要真正测得漆膜与被涂漆物件的附着力是比较困难的，目前还没有一个十全十美的方法，只能以间接的手段来测定，往往测得的附着力数值还包括了一些其他方面的综合性能。前面介绍的划痕硬度、耐冲击性、柔韧性等试验方法也可以间接地表现出漆膜的附着力。目前测定漆膜附着力一般采用以下两类方法。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1297,
+        "chunk": "# (1）综合测定法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1298,
+        "chunk": "# 0 1 1 1 2 m 4 一 5大于4级的严 重脱落  \n\n①十字划格法最早采用保险刀片在漆膜上切6道平行的切痕（长约10～20mm，切痕间的距离为1mm），应该切穿漆膜的整个深度；然后再切同样的切痕6道，与前者垂直，形成许多小方格，过后用手指轻轻触摸，漆膜不应从片格中脱落，而仍与底板牢固结合者为合格。此法比较简单，不需特殊的仪器设备，适合在施工现场中应用，但保险刀片较软，对于漆膜较厚或硬度较高的并不适用，为此又发展了单刀或多刀的手工切割刀具和机械切割仪器。划格结果形成的图形如图4-3-36所示。此为按国家标准GB/T9286—1998《色漆和清漆漆膜的划格试验》的结果分级法。目前涂层的附着力一般均较好，单纯使用划格法不能区分出优劣，这时就必须使用胶带法相配合，以得到满意的结果。胶带一般是25mm宽的半透明胶带，背材为聚酯薄膜或醋酸纤维，将胶带贴在整个划格上，然后以最小角度撕下，结果可根据漆膜表面被脱落面积的比例来求得。美国ASTMD3359—2002中的B法中规定的分级方法与我国国家标准相反，其5级最好，0级最差；而德国DIN53151标准则与我国国家标准一致。  \n\n②交叉切痕法原理基本相同，但用多样交叉的切痕以形成各种大小不同的面积来观察附着力，如图4-3-37所示。此法某些国家已把  \n\n![](images/7646538e651e846c96acc35772558cba54d50c7df35395869fd0891eaea5b55c.jpg)  \n图4-3-36 划格法测 定附着力 0—最好；5—最差  \n\n它列人了标准。  \n\n![](images/b8f1227f8e4596703bb642857bd3a808b1597379e0290927a2e27e6eb8f407a7.jpg)  \n图4-3-37 交叉切痕法  \n图4-3-38 划圈法附着力测定仪  \n\n$\\textcircled{3}$ ③划圈法按国家标准GB/T1720—1989中规定采用附着力测定仪，如图4-3-38所示。针尖在漆膜上划出一定长度、依次重叠的圆滚线图形，使漆膜分成面积大小不同的7个部位，见图4-3-39。凡第一部位内漆膜完好者，则附着力最好，为1级；第二部位完好者，则为2级；依此类推，7级的附着力最差。  \n\n目前划圈法附着力测定仪新的改进是采用一个硬度很大的可长期使用的耐磨针头来代替唱针，以减少每次测试时需换针头的麻烦。另外在测定仪的底座下还安有几节电池及一个蜂鸣器，当针尖在刺透漆膜真正达到底板时，蜂鸣器就给予响声，然后就可进行测试，这样可避免因漆膜厚度不匀或针尖有时并未真正接触底板而造成的试验误差。  \n\n$\\textcircled{4}$ 划痕法此法为美国ASTMD2197—1998（2004）所采用，有两种方法。甲法用平衡杆刮痕附着力测定仪（balanced-beam adhesiontester）测定，刮针用直径 $1.\\delta\\mathrm{mm}$ 的镀铬钢丝弯成外圈半径为 $3.25\\mathrm{mm}$ （0.128in）的U形环圈。检测时，样板平行移动，环形圈接触涂膜，从仪器的平衡盘上加减负荷质量以测出能划开漆膜最小荷重，结果以负荷质量（kg）表示。乙法用微型刀附着力试验仪（microknife adhesiontester）测定，仪器上装有尖棱的直径为$0.1\\mathrm{{mm}\\pm0.005\\mathrm{{mm}}}$ 的金刚石刀头，检测时在样板上刻划出平行的沟槽，同时改变负荷质量测量。附着力越好的涂膜，沟槽的间距越近。用使涂膜破坏时沟漕间的距离，与负荷质量的关系值作为微型刀附着力值，来表示测定结果。其计算公式如下所示：  \n\n![](images/af959bb8075bc5c3ac0fc7d80f115ec8e86a7343ba8ca0ab71233c85d52d419e.jpg)  \n图4-3-39 划圈法附着力的分级  \n\n$$\nA{=}\\frac{10d_{\\mathrm{a}}}{\\frac{L_{\\mathrm{a}}}{\\sqrt{L_{\\mathrm{a}}}}}{=}\\frac{d_{\\mathrm{a}}}{c}\n$$  \n\n式中 $A$ 微型刀附着力值，$d_{\\mathrm{a}}$ 1 涂膜破坏时沟槽距离， $\\mu\\mathrm{m}$ $L_{\\mathrm{a}}$ -—负荷质量， $\\bf\\delta g$ 费  \n\n$$\nc{=}\\frac{\\sqrt{L_{\\mathrm{a}}}}{10}\n$$  \n\n需指出的是，用综合测定法测出的附着力不是单纯的附着力，它还含有漆膜的变形和破坏时的抵抗力等。  \n\n(2）剥落试验法这种方法比综合测定法前进了一步，它主要是测定把漆膜从底板上脱落所需之功，或在垂直方向把漆膜从底板上拉开一定的面积所需之力。目前应用较多的可举以下两种为例。  \n\n$\\textcircled{1}$ 扭开法系采用扭断附着力测定仪，如图4-3-40所示。用适当的胶黏剂将一个不锈钢的圆柱形测头与待测样板的漆面黏合，再把仪器本体套在测头上，徐徐用力将仪器扭转90°，测定漆膜被扭开时所需的扭矩，可直接从表盘上得出读数，这样就可计算出不锈钢测头底面的扭断应力，该数值即相当于被试漆膜的扭断附着力。  \n\n$$\nf_{\\bar{\\mathrm{s}}}=\\frac{T r}{I_{\\bar{\\mathrm{p}}}}\n$$  \n\n式中 $f_{s}$ 一 扭断应力， $\\mathbf{P\\bar{a}}$ $\\tau$ 扭矩， $\\mathbf{N}\\cdot\\mathbf{\\taum}$ $r$ 测头底面半径， $\\mathrm{cm}$ $I_{\\mathfrak{p}}$ 扭断面有效惯量， $\\mathrm{cm^{4}}$ d  \n\n$$\nI_{\\mathrm{p}}{=}\\frac{\\pi}{32}(D_{\\mathrm{o}}^{4}{-}D_{\\mathrm{i}}^{4})\n$$  \n\n式中 $D_{\\circ}$ 筒的外径， $c m$ $D_{\\bar{\\mathsf{i}}}$ 简的内径， $\\mathrm{cm}$ 0  \n\n由于 $r/I_{\\mathrm{p}}$ 均为仪器的常数，因此只需将扭矩测出，乘上一定的常数即可。  \n\n使用此法测定附着力，不论在平面、垂直面或倾斜面上均能进行，且可以不受实验室或施工现场的限制，但由于其测试过程较繁杂，为了使胶黏剂固化完全，一般需等6h后才能进行测定，故不如划格法、划圈法等快速简便。  \n\n$\\textcircled{2}$ 拉开法在规定的速度下，在试样的黏结面上施加垂直的均匀拉力，以测定涂层间或涂层与底材拉开时单位面积上所需的力。试验可采用一般的拉力试验机，试件为两个金属试柱的对接件（见图4-3-40）或组合件。胶黏剂可用氰基丙烯酸酯、双组分无溶剂环氧化物以及过氧化物催化的聚酯胶黏剂。在湿度较高的试验条件下，胶黏剂的固化时间要尽可能短，最好使用双组分快干环氧胶黏剂。测定时拉力机夹具以不超过1MPa/s的速度进行拉伸，直至破坏，考核其附着力和破坏形式。涂层的附着力按下式计算：  \n\n![](images/8b08827e8da6b35c6779d5f9ef9d5864d0dcce4d9bdfa0ac3b95668c2b66b7b3.jpg)  \n图4-3-40对接试件1一胶黏剂：2-涂层  \n\n式中-—涂层的附着力， $\\mathbf{MPa}$ F- 破坏力，N；A- 试柱横截面积， $\\mathbf{m}^{2}$ 9  \n\nGB/T5210—2006《色漆和清漆拉开法附着力试验》规定破坏形式有9种：A—底材内聚破坏；A/B—第一道涂层与底材间的附着破坏；B—第一道涂层的内聚破坏；B/C-—第一道涂层与第二道涂层间的附着破坏；n复合涂层的第n道涂层的内聚破坏；n/m—复合涂层的第n道涂层与第m道涂层间的附着破坏；/Y—最后一道涂层与胶黏剂间的附着破坏；Y——胶黏剂的内聚破坏；Y/Z——胶黏剂与试柱间的胶结破坏。规定试验结果用附着力数值与破坏类型表示，对每种破坏类型，估计破坏面积的百分数，精确至10%。如果涂料体系在平均3MPa的拉力下破坏，检查表明第一道涂层的内聚破坏面积大约为20%，第一道涂层与第二道涂层间的附着面积大约为80%，这样拉开法试验的结果可表示为：3MPa（2.5\\~2.9MPa），20%B，80%B/C。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1299,
+        "chunk": "# 7.耐磨性  \n\n其定义为涂层对摩擦机械作用的抵抗能力，它是那些在使用过程中经常受到机械磨损的漆膜的重要特性之一。耐磨性实际上是漆膜的硬度、附着力和内聚力综合效应的体现，与底材种类、表面处理、漆膜在干燥过程中的温度和湿度有关。在其他条件相同的情况下，涂层耐磨性优于金属材料，因为有黏弹性效应，能把能量缓冲、吸收和释放掉。目前一般是采用砂粒或砂轮等磨料来测定漆膜的耐磨程度，常用的有以下几种。  \n\n（1）落砂法落砂法是最简单的一种方法，仪器见图4-3-41。即让一定大小的砂粒，从规定的高度落到试验样板上，称取将漆膜破坏所需要的砂量，其结果以磨耗系数V/T来表示。其中V为砂的体积（L）；T为涂层厚度 $(\\mu\\mathrm{m})_{\\circ}$  \n\n落砂法中漆膜除受砂粒的磨损外，还受砂粒的冲击作用，因此对砂粒的要求比较严格。此法虽较古老，但美国ASTM仍作为正式测试标准保留至今。  \n\n（2）喷射法喷射法主要是以模拟实际情况为主，如汽车底盘的喷丸试验，以及航空发动机的高温砂蚀试验等。喷射的磨料可以是石英砂、铁丸、铝丸等，在一定的距离，以固定的喷嘴口径，通过压缩空气或二氧化碳气体将磨料喷打在涂层上，以开始露出金属底材为测试终点。有时采用 $150^{\\circ}C$ 的热压缩空气将预热过的石英砂喷出，进行高温砂蚀试验。美国ASTMD658—1991规定使用磨耗检测仪，磨料粒径为 $75\\sim90\\mu\\mathrm{m}$ 之间，通过磨耗每单位厚度所需磨料的质量来表示其耐磨性。  \n\n![](images/dfc6451220647e0605fe356d2e6e1ae7c2806097f537ee2d9817eb8925f1f9f6.jpg)  \n图4-3-41 落砂试验器  \n\n(3）橡胶砂轮法 橡胶砂轮法目前国际上通常采用Taber磨耗试验器来进行，见图4-3-42。仪器有两个橡胶砂轮，一个从中心向外磨损样板，另一个则从外向中心磨损样板，在轮上还可根据试验要求施加各种负荷，被试样板则固定在轮下旋转的圆盘上，  \n\n![](images/b5229b119ce6a2a106bf39b3d306881bf59205fa1fc9174cc861468e25aa3389.jpg)  \n图4-3-42Taber磨耗试验器  \n\n试验可以干磨也可以湿磨，其结果以漆膜正好被磨透所需的磨转次数或经一定的磨转次数后漆膜的失重来表示。  \n\n国家标准GB/T1768—2006《色漆和清漆耐磨性的测定旋转橡胶砂轮法》规定采用磨耗试验仪，经一定的磨转次数后，以漆膜的失重来表示其耐磨性。因失重法可不受漆膜厚度的影响，同样的负荷和转数，失重越小则耐磨性越好，此法对主要受重荷摩擦的路标漆、地板漆等最为适用，并发现与实际的现场磨耗结果有良好的关系。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1300,
+        "chunk": "# 8.抗石击性  \n\n又称石凿试验，是因汽车工业的特殊需要而在近年开发的一项涂膜检测项目，专用于检测汽车涂膜。它模仿汽车行驶过程中砂石冲击汽车涂层的情况，说明涂膜抵抗砂石高速冲击的能力。这项检测实际上是冲击、摩擦和附着力的综合性检验项目。它与用喷射法检测涂膜的耐磨性的方法相似，但又不相同，主要差别是喷射的砂石粒径大，喷射时的压力高，结果判定方法不同。例如最常用的检测方法是把直径为4～5mm的钢砂用压缩空气吹动喷打在被测样板上，每次喷钢砂500g，在10s±1s内以2MPa的压力冲向样板，重复2次，然后贴上腔带纸拉掉松动的涂膜，随即将涂膜破坏情况与一系列标准图片比较，取其近似的标准编号，即为该涂膜的抗石击性的结果，0级最好，10级最差。有专用的试验仪器，如日本（Suga）试验机株式会社的KSS-1型、德国BYK-Gardner公司的ESP-10型。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1301,
+        "chunk": "# 9.磨光性  \n\n系指漆膜或腻子层，经用砂纸或浮石等研磨材料干磨或湿磨后，产生平滑无光表面的难易程度。这是漆膜的一项实用性能，对施工质量和效率产生影响，特别是对底漆和腻子，它是一项重要的性能指标。  \n\n根据产品要求，研磨材料可以选用各种规格的浮石、砂纸或砂布，可以是干磨或蘸水湿磨，以打磨漆膜过程的难易程度和经打磨后涂膜的表面状态（如发热、变软等）来评定。过去通用手工打磨，简易方便，但操作不当易产生误差。GB/T1770—1979（1989）《底漆、腻子膜打磨性测定法》中规定用DM-1型打磨性测定仪的机械打磨测定方法，试板装于仪器吸盘正中，磨头装上规定型号的水砂纸，仪器可自动进行规定次数的打磨，保证了相同的负荷和均匀的打磨速度，所得结果比较准确。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1302,
+        "chunk": "# 10.重涂性  \n\n系指在涂膜表面用同一涂料进行再次涂覆的难易程度和效果，也是涂膜实用性能之一。因为在涂料施工时经常是多道涂饰，膜间的附着好坏影响到涂层质量。重涂性试验是在干燥  \n\n后的涂膜上按规定进行打磨后，再按规定方法涂上同一种涂料，其厚度按产品规定要求，在涂饰过程中检查涂覆的难易程度，涂饰后的涂膜对光目测其涂膜状况，再按规定时间干燥后检查涂膜状况有无缺陷发生，必要时检测其附着力。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1303,
+        "chunk": "# 11.面漆配套性  \n\n通常系底漆的测定项目，其意义与重涂性类似，只是为两种不同涂料之间的涂饰难易程度和两种不同涂膜的膜间附着情况的测定。测定方法也与重涂性相同。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1304,
+        "chunk": "# 12.耐码垛性  \n\n系指单层涂膜或复合涂膜体系在规定条件下充分干燥后，在两个涂漆表面或一个涂漆表面与另一种物质表面在受压的条件下接触放置时涂膜的耐损坏能力，或称耐叠置性、堆积耐压性。因为涂漆后的被涂物件经常是多个码放在一起，涂膜承受相当大的压力，涂膜不能因而发生粘连或破损，这是实际使用过程中对涂膜性能的要求，因此对涂层耐码垛性的检查也成为当前对涂膜实用性能的重要检测项目。  \n\n耐码垛性的检测尽量模仿涂漆物件被互相堆起来的条件。GB/T9280—1998《色漆和清漆耐码垛性试验》规定使用的仪器由一个底座和一个能自由滑动的压柱组成。按照规定准备好涂漆样板，测试时将样板以90°士2°角互相交叠，试板表面紧密接触，放于仪器底座上，将规定码放在压柱上，然后将所有质量慢慢地放置在两试板的接触面上，完全覆盖试板所接触的正方形，保持至规定时间。检查在接触面涂层有无损伤，例如可见的印痕、样板粘连或涂膜脱落等，以此评定其耐码垛性，如果需要，可计算出涂膜表面所受压力：  \n\n$$\nP{=}\\frac{m_{1}{+}m_{2}}{l^{2}}g{\\times}10^{3}\n$$  \n\n式中 $P$ —压力(压强)；$m_{1}$ 压柱的质量；$m z$ 码的质量；$l$ -试板宽度；$\\boldsymbol{\\mathbf{\\mathit{g}}}$ 一重力加速度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1305,
+        "chunk": "# 13.耐洗刷性  \n\n系测定涂层在使用期间经反复洗刷除去污染物时的相对抗磨蚀性。对于建筑涂料，特别是内用墙壁漆，在靠近门户、窗口等部位，常常易被弄脏，就需经常擦洗，因此耐洗刷性就  \n\n![](images/a2bd480a28cf8330cb047d260fc4dc48382f8c805a79c6886efcd55054cbc587.jpg)  \n图4-3-43 耐洗刷性试验器  \n\n成为这些漆类的一项很重要的考核指标。  \n\n我国国家标准GB/T9266—1988《建筑涂料涂层耐洗刷性》规定测试时使用洗刷试验机，如图4-3-43所示。试板用夹子固定后，使用鬃刷以每分钟固定的往复频率在漆膜表面上来回摩擦，同时不断滴加洗涤剂，试验连续进行直到漆膜露底为止，或按产品标准规定的次数进行。对于外墙漆国内一般都采用0.5%皂液，1000次为合格指标；内墙漆则根据不同品种从几十次到几百次不等。洗刷机可采用1个试验头，也可以采用2个试验头，以便同时对两种试板进行耐洗刷性能的比较。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1306,
+        "chunk": "# 四、涂膜耐物理变化性能的检测  \n\n涂膜在使用过程中除了受外力作用外，受光、热、电的作用也会使涂膜的强度、外观等发生变化。根据产品要求，检测涂膜对这些因素的抵抗能力。常见的检测项目和方法列举如下。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1307,
+        "chunk": "# 1.耐光性  \n\n指涂膜受光线照射后保持其原来光学性能如颜色、光泽等的能力，其中又分为保光性、保色性和耐黄变性。涂膜在日光照射下起变化，但需时较长，通常对涂膜的耐光性检测采用人造光源，以加速涂膜的变化，缩短检测时间。  \n\n(1）保光性指涂膜在经受光线照射下能保持其原来光泽的能力。通行的检测方法是将被测涂膜样板遮盖住一部分，在日光或人造光源下照射一定时间后，用光电光泽计测定未照射和被照射部分的光泽，以其比值表示保光性的结果。  \n\n(2）保色性指涂膜经受光线照射下保持其原来颜色的能力。通常检测方法也是比较被照射涂膜与未照射涂膜在颜色上的差别，用肉眼或色差仪测定。在日本JIS标准中规定使用400W高压汞灯的旋转褪色试验仪检查，光线照射时温度上升，需采用通风和调温。  \n\n(3）耐黄变性含有油脂的涂料的涂膜在使用过程中经常会产生黄变，甚至有的白漆标准板在阴暗处存放过程中就会逐步地产生黄变现象。原因大都是涂料所含油类干燥过程和继续氧化时生成的分解物质带有黄色，在浅色漆上比较容易觉察。为了预先防止和判断黄变的产生，就必须对此项目进行检验。  \n\n首先是将试样涂于磨砂玻璃板上，经干燥静置后放人装有饱和硫酸钾溶液的干燥器内，经一定时间后取出，测出涂膜颜色的三刺激值 $x,y,z$ ，然后按下式计算泛黄程度值 $(D)$ 0  \n\n$$\nD{=}(1.28x{-}1.06z)/y\n$$  \n\n也可在干燥器底部放入浓度为 $2\\%\\sim5\\%$ 的氨水，使漆膜在氨水所产生的蒸气中经历一定时间，然后取出检查，目测或测定泛黄程度值。试验时最好同时有一个已知耐黄变性的涂层试板一起进行，以作参照。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1308,
+        "chunk": "# 2.耐热性、耐寒性及耐温变性  \n\n这三项试验是检测涂膜抵抗环境温度的能力的项目，分别适用于不同涂料产品。  \n\n(1）耐热性指漆膜对高温的抵抗能力。由于许多涂漆产品被使用在温度较高的场合，因此耐热性的判定是这些产品上的涂膜的重要技术指标之一。若涂层不耐热，就会产生起泡、变色、开裂、脱落等现象，使漆膜起不到应有的保护作用。  \n\n涂膜的耐热性与涂料的组成，即所选用的树脂和颜料有关，也与被涂物底材及表面处理有关。  \n\n测定耐热性的方法国内外基本相同，都是采用鼓风恒温烘箱或高温炉，在达到产品标准规定的温度和时间后，对漆膜表面状况进行检查，或者在耐热试验后进行其他性能测试，如冲击、弯曲、浸水、盐雾试验等，以其测试数据表示。  \n\n(2）耐寒性指涂膜对低温的抵抗能力。特别是用于检测水性建筑涂料，在寒冷的气温环境下，涂膜能否保持其原有力学性能，不发生开裂等破坏现象。通常的检测方法是将涂膜样板按照产品标准规定放人低温箱中，例如在一 $40^{\\circ}C$ 或一 $60^{\\circ}C$ 保持一定时间，取出观察涂膜变化情况。  \n\n（3）耐温变性指涂膜经受高温和低温急速变化情况下，抵抗被破坏的能力。这个检测项目与单独的耐热、耐寒判断结果不同，是检测涂膜在骤冷骤热情况下涂膜机械强度的变化而引起的开裂、起泡、脱皮等破坏现象。通常检测方法是在高温如60℃保持一定时间后，再在低温如一20℃放置一定时间，如此经过若干次循环，最后观察涂膜变化情况。具体的温度、放置时间和循环次数应根据产品标准规定进行。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1309,
+        "chunk": "# 3.电绝缘性  \n\n一般涂膜都具有一定的电绝缘性，但对绝缘漆其电绝缘性是重要的性能项目，需要进行专门的检测。电绝缘性的检测内容包括涂膜的体积电阻、电气强度、介电常数以及耐电弧性等，有专门的检测方法和检测仪器。我国现有的绝缘漆性能测试的方法有以下标准：  \n\n$\\textcircled{1}$ HG/T3355—2006《绝缘漆膜制备法》   \n$\\textcircled{2}$ HG/T3356—2006《绝缘漆膜吸水率测定法》   \n$\\textcircled{3}$ HG/T3357—2006《绝缘漆膜耐油性测定法》   \n$\\textcircled{4}$ HG/T3330—1980（1985）《绝缘漆膜击穿强度测定法》   \n$\\textcircled{5}$ HG/T3331—1978（1985）《绝缘漆膜表面电阻及体积电阻系数测定法》   \n$\\textcircled{6}$ HG/T3332—1980（1985）《绝缘漆耐电弧性测定法》",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1310,
+        "chunk": "# 五、涂膜耐化学及耐腐蚀性能的检测  \n\n涂膜在大气环境下要受到空气中水分及其他各种化学成分的侵蚀；被涂物件的使用条件也可能使涂膜接触各种化学物品。涂在物件上的涂膜具有保护被涂物件不受腐蚀的作用，如防止金属生锈、木材腐蚀等，因而涂膜的耐化学及耐腐蚀性成为涂膜发挥保护作用的一类重要性能。对涂膜的耐化学和耐腐蚀要求是多种多样的，涂膜要按照不同的需要来满足。涂膜的耐化学和耐腐蚀性主要由涂料的结构组成决定，但施工的配套、施工条件和质量也对涂膜的这方面性能产生影响。在设计和研制涂料时，要根据使用要求选用适当的方法对其耐化学和耐腐蚀性能进行检测，尽量模仿实用条件和可能遇到的情况。但由于实验条件与实际的差别，性能的检测结果通常是在规定条件下得到的数据，更多的是比较定性的结论，与千变万化的实际应用情况很难达到完全吻合。现在正在不断改进这方面的检测方法，以求适应要求。  \n\n涂膜的耐化学及耐腐蚀性能的检测通常包括3个方面：  \n\n$\\textcircled{1}$ 对接触化学介质而引起的破坏的抵抗性能的检测，如耐水性、耐盐水性、耐石油制品性、耐化学品性等；$\\textcircled{2}$ 对大气环境中物质破坏的抵抗性能的检测，如耐潮湿性、耐污染性、耐化工气体性、耐霉菌性等；$\\textcircled{3}$ 对防止介质引起底材发生腐蚀的能力的检测，总的是耐腐蚀性和耐锈蚀性的检测，通常以湿热试验、盐雾试验和水汽透过试验来表示其能力。  \n\n在进行耐化学及耐腐蚀性能检测时，所得数据多是比较值，有的按其破坏程度分级，有的按产品标准规定的时间判断是否合格。各国的标准不尽相同。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1311,
+        "chunk": "# 1.耐水性  \n\n涂料在实际应用过程中往往与潮湿的空气或水分直接接触，随着漆膜的膨胀与透水，就会发生起泡、变色、脱落、附着力下降等各种破坏现象，直接影响到涂料的使用寿命，因此对某些涂料产品必须进行耐水性能检测。漆膜的耐水性好坏与树脂中所含的极性基团、颜料中的水溶盐、涂膜中的各种添加剂等因素有关，也受被涂物的表面处理及涂膜的干燥条件等因素影响。  \n\n目前常用的耐水性测定方法大致有以下几种：常温浸水法、浸沸水法、加速耐水法。  \n\n（1）常温浸水法常温浸水法是一种最普遍采用的方法，适用于醇酸、氨基漆等绝大多数品种。国家标准GB/T1733—1993规定将涂漆样板的2/3面积放入温度为 $(23\\pm2)^{\\circ}C$ 的蒸馏水中，待达到产品标准规定的浸泡时间后取出，目测评定是否有起泡、失光、变色等现象，也可用仪器测定漆膜失光率、附着力的下降程度。该法简便易行，但所用的水质对漆膜耐水性有很大的影响。  \n\n(2）浸沸水法浸沸水法适用于经常与盛有热水、热汤等器皿接触的物件的涂膜。测定时，将涂漆样板的2/3面积浸挂在沸腾的蒸馏水中，待达到产品标准规定的时间后取出，以目测检查起泡、生锈、失光、变色等破坏现象。此法中沸水应始终保持沸腾状态，试验时为保持同一液面，也需用正在沸腾的水进行补充。  \n\n(3）加速耐水法常温浸水法虽然简便易行，但对某些涂料测试时需时较长，影响产品的周转。为了缩短周期，加快试验进程，GB/T5209—1985《色漆和清漆耐水性测定浸水法》中规定采用（ $40\\pm1)^{\\circ}C$ 的流动水法，对水质作了规定。试验槽如图4-3-44所示，用循环泵或通人干燥、无油的压缩空气，以保持水的流动，水的电导率规定不大于 $2\\mu\\mathrm{S}/\\mathrm{m}$ 0  \n\n通过试验发现，按 $(40\\pm1)^{\\circ}C$ 的流动水所做的试验，与 $(25\\pm1)^{\\circ}C$ 常温浸水法作比较，白色氨基漆达到同样破坏的等级，其加速倍率约为6～9倍，这样原来需3天时间的试验，现在当天就能得出结果，大大提高了测试效率。  \n\n![](images/104b4ffc621e68aae7c468847c792ae0569c05c717a2c74b2fa44d0c31666861.jpg)  \n图4-3-44 耐水试验槽",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1312,
+        "chunk": "# 2.耐盐水性  \n\n涂膜在盐水中不仅受到水的浸泡而发生溶胀，同时受到溶液中氯离子的渗透而引起强烈腐蚀，因此漆膜除了可能出现耐水性中的起泡、变色等现象外，还会产生许多锈点和锈蚀等破坏。所以可用耐盐水性试验判断涂膜防护性能。  \n\n目前盐水一般都采用3%（质量分数）的氯化钠溶液，测试时，将试板2/3面积浸人，按产品标准规定的时间浸泡后取出并检查。这种常温浸盐水法国内外基本相同，仅试验温度有所差别。另外国家标准GB/T1763—1979（1989）中规定，也可采用加温耐盐水法，试验温度为 $(40\\pm1)^{\\circ}C$ ，采用一套恒温设备控制。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1313,
+        "chunk": "# 3.耐石油制品性  \n\n现代工业产品，如交通工具、机床、工程机械和工业装备等，经常会接触到各种石油制品，如汽油、润滑油、变压器油等。这些物件的涂膜必须具有对这些石油制品侵蚀作用的抵抗能力。不同产品规定了对不同石油制品的耐性标准，其中最普遍的是耐汽油性。  \n\n耐汽油性的检测是测定涂膜对汽油的抵抗能力，即在规定的条件下进行试验，观察涂膜有无变色、失光、发白、起泡、软化、脱落等现象，以及恢复原状态的难易程度。其他耐润滑油性、耐变压器油性的测试方法基本相同。  \n\n对于用于贮存石油制品的容器的涂膜，除了检测涂膜的耐石油制品性以外，还要进行涂膜对石油制品的品质影响的检验，一般在涂料产品标准中规定其检验方法。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1314,
+        "chunk": "# 4.耐化学品性  \n\n涂膜可能接触到的各种化学品有以下两类。  \n\n① 工业化学品酸、碱、盐和有机溶剂等属于工业化学品。酸、碱、盐等化学品对金属被涂物件能直接发生“干蚀”而使金属腐蚀，因此涂膜对这些工业化学品侵蚀的抵抗性能是非常重要的。我国习惯上把防止由于酸、碱、盐等工业介质的腐蚀称为防腐，把防止天然介质（水、海水、大气及土壤等）的腐蚀称为防锈，以示区别，但总称为防腐蚀。通过涂膜对这些工业介质的抵抗性能的测定，可以判断涂膜防腐蚀性能。有机溶剂对涂膜有一定的侵蚀作用，涂膜的耐溶剂性好坏能表示出涂膜所具有的机械强度，所以也是一个重要检测项目。  \n\n② 家用化学品属于这类的品种很多，依据国际上的习惯，包括水、洗涤剂或肥皂液、酱油、醋、油脂、酒类、饮料（如咖啡、茶)、果汁、调味品（如芥末、番茄酱)、化妆品（如口红）、墨水和油墨、润滑油脂、药品（如碘酒）以及其他。涂膜接触到这些物品，如果被沾污留有痕迹，或受到侵蚀，都将影响装饰和保护作用。现在的家用电器、家具等都特别重视对这些化学品的抵抗性能的检测。  \n\n下面介绍几种有代表性的检测方法。  \n\n（1）耐酸性和耐碱性一般涂膜的耐酸性和耐碱性检测方法基本相同，国家标准GB/T9274-1988《色漆和清漆耐液体介质的测定》中规定，除了使用钢棒和铝棒外，也可使用冷轧钢板等，浸泡法测试温度定为 $(23\\pm2)^{\\circ}C$ 9  \n\n对于建筑涂料的耐碱性试验，在国家标准 $\\mathrm{GB/T}~9265{-}1988~\\Updownarrow$ 建筑涂料涂层耐碱性的测定》中另有规定。用涂于石棉水泥板上的涂膜浸人饱和氢氧化钙溶液中，检查其结果。  \n\n(2）耐溶剂性除了产品有规定以外，通常都按国家标准GB/T9274-—1988《色漆和清漆耐液体介质的测定》中的浸泡法进行，按产品标准规定的时间在 $(23\\pm2)^{\\circ}C$ 浸泡。  \n\n近年来国际上推荐一种甲乙酮来回擦拭法，既能测出涂膜耐有机溶剂能力的强弱，更能判断涂膜的机械强度，对交联型涂料可以考察其交联密度的大致情况。通用的方法是使用一个中空的管状容器，带有一个毡制的尖端，在涂膜上每秒擦拭一个来回，通过时间计算出来回擦拭的次数，计算擦掉一定厚度的涂层后露出底材所需来回擦拭的次数，例如进行200或300次来回擦拭，涂膜仍不露底，可表示其结果为 $^{200+}$ 或 $300+$ 0  \n\n(3）耐家用化学品性又称污染试验（stainresistancetest）。通常采用国家标准GB/T9274—1988《色漆和清漆耐液体介质的测定》中的点滴法进行检验。又分覆盖法和散开法。将测试液体滴在制好的试验样板涂膜表面，每滴约 $0.1\\mathrm{ml}$ ，覆盖法在液滴上覆以表面Ⅲ，开法则不加覆盖。在 $(23\\pm2)^{\\circ}C$ 下，在规定的时间内，样板应不受干扰。达到产品标准规定时间后，如果是水溶液则用水清洗，如果是非水溶液，则用对涂膜无损害的溶剂彻底冲洗，并立即检查涂膜变化情况。一般是根据变化情况划分等级标准，有的国家分为11级，10级最好，0级最差。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1315,
+        "chunk": "# 5.耐湿性  \n\n指涂膜受潮湿环境作用的抵抗能力，通常是对涂膜样板在高湿度条件下进行检测。我国等效采用ISO6270—1980标准制定了GB/T13893—1992《色漆和清漆耐湿性的测定连续冷凝法》，规定了检测涂膜在连续冷凝的高湿度环境中的耐湿性的方法，用于测定多孔性底材（如木材、水泥石棉板）和非多孔性底材（如金属）上的涂层的耐湿性能。标准规定采用耐湿性测定仪，样板放于仪器的顶盖位置，仪器的水浴温度控制在 $(40\\pm2)^{\\circ}C$ ，保持试验样板下方 $25\\mathrm{mm}$ 空间的气温为！ $37\\pm2)^{\\circ}C$ ，涂层表面连续处于冷凝状态，按规定的时间进行试验。试验结束时取下样板，立即检查其表面破坏情况，按GB/T1740--2007《样板评级方法或协议》评价其耐湿性。  \n\n此外，也有在常温下的检测方法，如日本JISK5661—1983《建筑用防火涂料标准》中规定有耐湿性检验项目，其方法为将涂漆样板在不受雨露侵蚀与日光直射、通风良好的环境下，垂直放置7天后，在温度（20士3)℃、湿度约90%的容器中垂直放置72h后，取出检查涂膜状况。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1316,
+        "chunk": "# 6.耐污染性  \n\n涂膜在使用过程中，经常暴露和接触到各种环境的大气介质，当涂层本身固化不彻底或漆膜不够平整光滑时，涂膜表面就会不同程度地沾上煤灰、油斑、尘埃、动物的排泄物等各种外来污物，影响了漆膜的外观、颜色和光泽。特别是白色和浅色的外墙建筑涂料，涂膜沾污后影响整个建筑物甚至城市的美观。因此对抗污染（沾污）性的控制和检测是很重要的项目。  \n\n对于暴露在大气中的试板，可使用色差仪测定漆膜暴露前后的反射值，其差值就可以认为是由于沾染污物的结果，一般以污物堆集指数来衡量。  \n\n污物堆集指数=L $=\\frac{L_{\\mathrm{B}}}{L_{\\mathrm{A}}}\\times100\\times100\\%$ 式中 $L_{\\mathrm{A}}$ ——漆膜未暴露前的反射值， $\\%$ $L_{\\mathrm{B}}$ 漆膜经暴露一定时间后的反射值， $g_{\\frac{\\pi}{2}}$  \n\n对于建筑涂料，尤其是白色和浅色的外墙漆抗沾污的检测，目前一般采用有一定规格的粉煤灰与自来水，配成 $1:1$ 的粉煤灰水，均匀涂刷在漆膜表面，按一定的循环周期进行，然后测定漆膜反射系数的下降率，对于白色漆膜，则为白度值的下降率，可按下式计算：  \n\n$$\nC_{n}=\\frac{A-B}{A}\\times100\\%\n$$  \n\n式中 $C_{n}$ 经 $\\varkappa$ 次污染后的白度值下降率， $g_{\\phi}$  \n\n$A$ -- 漆膜原始白度值， $9\\%$ $B$ 漆膜经 $\\scriptstyle{\\bar{n}}$ 次污染后的白度值， $\\frac{6}{70}$ $n$ 根据涂料品种不同，在 $5\\mathord{\\sim}15$ 次之间选取。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1317,
+        "chunk": "# 7.耐化工气体性  \n\n随着工业的发展，许多城镇都处于工业大气的环境中，空气中含有大量的工业废气和酸雾等化工气体，尤其在化工厂及其邻近地区所使用的设备、构件、管道、建筑物等，危害更为严重，为此在这些地区所使用的涂料不仅要具有一定的耐候性，更需要有较好的抵抗这些化工气体腐蚀性的能力。除了在现场挂片或实地涂装进行考核外，为了能快速得出试验结果，在实验室一般采用 ${\\bf S}{\\bf O}_{2}$ 或 $\\mathrm{\\mathbf{NH_{3}}}$ 对漆膜进行耐化工气体的腐蚀试验。这也是涂膜耐腐蚀试验的一个项目。  \n\n试验可在一气密箱中进行， $\\mathrm{{SO}_{2}}$ 可由气体钢瓶或气体发生设备供给，并配有合适的调节及测量装置。当试验涂层不超过 $40\\mu\\mathrm{m}$ 时，一般推荐用0.2L ${\\mathrm{SO}}_{2}$ 。由于干燥的 $\\mathrm{SO_{2}}$ 腐蚀性不大，因此试验必须在一定的温度和湿度下进行。  \n\n另外，每次试验周期通入的 $\\mathrm{SO}_{2}$ 是同一体积，所以在箱内试板的总面积是一个重要条件，因为不同类型的漆膜吸收 $\\mathrm{SO_{2}}$ 的速率和程度是不同的，因此试验条件会受到箱内试板类型的影响。  \n\n为了使试验更接近实际情况，也可把 ${\\mathrm{SO}}_{2}$ （或 $\\mathrm{\\DeltaNH_{3}}$ ）试验与人工加速老化试验结合起来，以模拟化工厂的室外环境条件，使测试结果与实际应用更为一致。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1318,
+        "chunk": "# 8.抗霉菌性  \n\n一般适于霉菌生长的温度是 $15\\sim35^{\\circ}C$ ，最适宜的温度是 $25\\sim30^{\\circ}C$ ，当温度低于 $0^{\\circ}C$ 或高于40℃时，霉菌实际上不生长。适于霉菌生长的相对湿度是80%以上，超过95%时生长最为旺盛，低于75%时霉菌不生长，但并不死亡，所以最适宜于霉菌生长的气候条件是温度 $30^{\\circ}C$ 与相对湿度 $95\\%\\sim100\\%$ 9  \n\n霉菌对涂料的破坏作用首先是霉菌在漆膜上的生长引起漆膜表面的斑点、起泡；同时由于霉菌在新陈代谢过程中所产生的有机酸，能引起漆膜表面颜料的溶解及漆基的水解，从而透人底层，导致漆膜破坏并失去其保护作用。因此对使用在我国南方及出口湿热带地区的涂料品种必须进行防霉试验。  \n\n在试验中所需选择的菌种随不同地区、不同季节的气候条件变化而有所不同；各个国家和地区的霉菌试验方法标准中规定使用的菌种也不一样。根据我国具体情况及试验要求，认为以下几种菌种是具有代表性的，可供选择的有：黑曲霉、黄曲霉、土曲霉、焦曲霉、萨氏曲霉、杂色曲霉、土生曲霉、产黄青霉、球毛壳霉、木霉、宛氏拟青霉、蜡叶芽枝霉等。  \n\n各种霉菌在生长过程中除了必要的温度、湿度外，还需供给一定的碳源、氯源及其他微量元素。在实验室内可以配制各种培养基以满足霉菌培育所需要的养分。培养基分为两种：全部用一定纯度的化学药品配制而成的培养基称为合成培养基，如蔡氏培养基、无碳培养基等；含有天然物的培养基称为天然培养基，如马铃薯培养基、麦芽汁培养基等。  \n\n防霉试验方法一般有悬挂法和培养Ⅲ法，对于大件成品的漆膜表面还可采用局部法。悬挂法要求有专门的霉菌试验箱，箱内悬挂样品处的有效空间应恒定地保持温度 $28\\sim$ $30^{\\circ}C$ 、相对湿度 $95\\%\\sim100\\%$ 的范围，样品表面不允许有大量凝露。培养皿法则可采用一般烘箱或低温烘箱，保持温度 $28\\sim30^{\\circ}C$ ，相对湿度则由培养Ⅲ内的培养基来保持，可不用控制。  \n\n从实际试验效果来看，悬挂法霉菌生长速度慢，需时较长，不太好观察，规定的28天时间还有延长的趋势，但其能适合零部件或整机的防霉试验。培养皿法霉菌生长速度快，好检查，规定为21天，实际上14天基本上就能定级，但其试验时需把样品制成$\\mathrm{15mm\\times40mm}$ 的小片试样才能进行，且试验条件较为严酷，长霉等级一般比悬挂法要快$2\\sim3$ 级。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1319,
+        "chunk": "# 9.耐腐蚀性  \n\n涂膜抵抗外来介质作用防止被涂底材发生腐蚀是涂膜一项重要的保护性能。腐蚀包括外来天然介质引起的锈蚀和工业介质引起的腐蚀，天然介质引起的锈蚀是普遍存在的，工业介质引起的腐蚀条件更为苛刻。而且这些引起腐蚀的条件千变万化，各种被涂物件所处环境不同，这就造成了对涂膜的耐腐蚀性评价的困难。在设计生产涂料产品时，耐腐蚀性是最复杂的课题之一。  \n\n评价涂膜的耐腐蚀性最实际的方法是实物试验，即将涂料涂在被涂物件上，在实际的条件下使用，长时期观察其发生腐蚀的情况，以判断这种涂料是否耐腐蚀，是否适合使用要求，这需要较长的时间，很难实现。退一步的做法是挂板模拟试验，即将涂料制成样板，在尽量与实际一致的环境条件下试验，用样板代替实物，例如船底涂料在海水中的实海测试、海港浮筏挂板试验等，这种方法试验周期还是太长。如日本JIS标准规定试验防锈性时间长达2年。现在更多地采用实验室模拟加速测试方法，这些方法包括盐雾试验、湿热试验、水汽透过性试验等，虽然可在实验室内进行，缩短实验周期，但只能得相对的有局限性的结果，有人指出目前常用的方法还不能算是完美、准确的方法，它们只对相同类型的涂料产品具有可比性，而不能用于不同体系涂料的评价，此外试验的结果往往和实际情况有差距。因此用这些试验方法作为控制质量虽是可行的，但同时还需儿种试验同时进行，以综合结果评定耐腐蚀性的好坏。现在国际上正在不断研究更为准确的模拟试验方法。  \n\n（1）盐雾试验 盐雾试验是目前普遍用来检验涂膜耐腐蚀性的方法。  \n\n大气中的盐雾是由悬浮的氯化物的微小液滴所组成的弥散系统，它是由于海水的浪花和海浪击岸时泼洒成的微小水滴经气流输送过程所形成的。一般在沿海或近海地区的大气中都充满着盐雾。由于盐雾中的氯化物，如氯化钠、氯化镁具有在很低相对湿度下吸潮的性能以及氯离子具有很大的腐蚀性，因此盐雾对于在沿海或近海地区的金属材料及其保护层具有强烈的腐蚀作用。  \n\n目前各国盐雾试验标准中所采用的盐水配方大体上可分为两类：一类是纯的氯化钠盐水；一类是所谓的人造海水。它们的 $\\mathbf{pH}$ 值都控制在 $6.5\\sim7.2$ 的范围内，一般称为中性盐雾试验。纯的氯化钠盐水，有采用 $3\\%$ ? $5\\%$ 和 $20\\%$ 的。由于浓度过大有使试验箱内相对湿度下降，造成样板表面有盐结晶析出，降低腐蚀强度，以及喷嘴经常易堵的毛病，故一般现在均采用 $3\\%\\sim5\\%$ 之间。  \n\n人造海水配方如下：  \n\n$N a C l$ $\\mathbf{Mg}\\mathbf{Cl}_{2}$  \n\n1g/L  \n\n其目的是使溶液的成分更接近于天然海水，以模拟真实海洋大气的腐蚀条件。从试验结果来看，其腐蚀速度不如纯氯化钠盐水的快。  \n\n为了提高盐雾试验的效果，目前发展了醋酸盐雾试验，即用醋酸将纯氯化钠盐水的$\\mathfrak{p H}$ 调整至酸性（ $\\mathsf{\\Pi}_{\\mathsf{P}}\\mathrm{H}$ 在 $3.1{\\sim}3.3$ 之间)。更进一步的发展是氯化铜改性的醋酸盐雾试验，即除了用醋酸调节成酸性外，再加人适量的 $\\mathrm{CuCl_{2}\\cdot2H_{2}O}$ 。这两种方法的目的就是试图克服以往盐雾试验存在的可靠性和重现性问题，并大大加速腐蚀的速度。参见ASTMG43—1975(1980)。  \n\n温度与腐蚀速率有着密切的关系。温度高时腐蚀加快，但可靠性和重现性下降。目前大多数国家标准中规定的是 $35\\mathrm{^\\circC}$ 和 $40^{\\circ}C$ 两种。  \n\n![](images/aebb549d9f2fd7491ec2c5a4fb69aa4ac9d1ebdfd4ab26c91c79d31c7d07f145.jpg)  \n图4-3-45 盐雾试验箱  \n\n喷雾周期根据不同要求可采用连续喷雾或间歇喷雾（如每小时内，喷雾 $15\\mathrm{min}$ ，停喷$45\\mathrm{min})$ ，但以连续喷雾的破坏速度为快。  \n\n目前，我国国家标准GB/T1771—2007《色漆和清漆耐中性盐雾性能的测定》系等效采用国际标准ISO7253—1984，试验中盐水浓度为！ $(50\\pm10)\\mathrm{g/L}$ ， $\\mathrm{\\pH}$ 值为 $6.5\\sim7.2$ ，温度 $(35\\pm2)^{\\circ}C$ ，连续喷雾。此试验条件与美国ASTMB117—2003标准完全相同。  \n\n盐雾试验设备（见图4-3-45）目前采用较多的是喷嘴式的，即使一定压力的空气通过试验箱内的喷嘴，把盐水喷成雾状而沉降在试验样板上。喷嘴可以是玻璃制的，也可以是塑料或其他合金钢制的。采用喷嘴式盐雾箱试验时需注意以下事项。  \n\n$\\textcircled{1}$ 试验过程中，必须经常检查喷嘴是否堵塞，以保证喷雾的正常进行。  \n\n②所用的压缩空气必须经空气过滤器除油和空气饱和器加热饱和。  \n\n③喷雾压力应严格控制，使在规定值上下很窄的范围内波动，以免影响试验的重现性。④ 需要进行相互比较的同一批样板应尽量在同一次试验里进行。样板涂漆表面与盐雾沉降方向成30°角放置。在每次检查后，应交换样板的放置位置，以消除设备内喷雾量及温度的不均匀所引起的误差。  \n\n标准中规定被测试涂膜样板必须在封边后测试，观察涂膜状况有无变色、起泡、生锈和脱落现象，按其轻重程度、起泡大小和面积、锈点大小来分级。有的标准中还规定在测试前对涂膜斜十字切割露底，放人盐雾箱中测试，其结果以在切痕周边锈蚀蔓延的距离和附看力损失的距离来评定。  \n\n美国ASTMD2933—1986提出一个循环试验法，即样板在盐雾箱中放置4h后，不冲洗或干燥立即将样板放人温度 $37.8^{\\circ}C$ 、相对湿度 $100\\%$ 的湿热试验箱中 $\\mathrm{18h}$ ，然后不干燥直接放入温度为 $(-23\\pm2)^{\\circ}C$ 的冷冻箱中 $\\mathrm{2h}$ ，此为1次循环，重复试验至产品规定的要求，一般为 $5\\sim35$ 次循环。据称35次循环试验的结果比在美国佛罗里达内陆曝晒2年的条件还要苛刻，但不及在佛罗里达海滩曝晒18个月那样严重。  \n\n(2）湿热试验湿热试验也是检测涂膜耐腐蚀性的一种方法，一般与盐雾试验同时进行。  \n\n饱和水蒸气对漆膜的破坏作用主要基于以下两点。  \n\n$\\textcircled{1}$ 水对漆膜有渗透作用，透过漆膜的一层或多层，在漆膜与漆膜之间积聚，产生了最初的起泡；随后深人一步发展，最后到达漆膜与底板之间产生最后的起泡，同时水分与金属底板接触，产生电化学腐蚀作用。  \n\n$\\textcircled{2}$ 漆膜本身也可以吸收一部分水分，使漆膜发生膨胀，降低了漆膜和底板的附着力， 从而产生起泡现象。  \n\n一般在相对湿度较低的情况下，漆膜附着力的变化是不明显的，但随着相对湿度增加到$90\\%$ ，甚至更高，附着力的丧失就会变得很快，除了个别漆膜外，大多数漆膜在干燥后附着力均不能恢复。  \n\n在相同的相对湿度下，温度越高，绝对湿度越大，周围空间水蒸气压力增加，水汽向漆膜内扩散就越显著，加快了受潮速度。同时温度越高，高分子链的热运动越厉害，分子间的作用力减弱，加速形成了分子间的空隙，有利于水分的进人。  \n\n在相同的绝对湿度下，温度越低，则相对湿度就越高，水分向漆膜内部渗透的趋向就越大。另一方面，相对湿度高时，水分凝结的趋势增加，在涂料表面凝结的水分增多，因而涂料受潮的速度也就加大了。  \n\n根据上述一些理由，目前推荐的湿热试验周期有许多种：高温高湿短周期、温湿度交变的试验周期和恒温恒湿的试验周期等。如表4-3-12所列。  \n\n表4-3-12 湿热试验周期举例  \n\n\n<html><body><table><tr><td>高温高湿短周期</td><td>温度（55±2）℃，相对湿度94%～98%，16h 温度35℃以下，相对湿度94%～100%，8h 24h为一周期，连续试验7d</td></tr><tr><td>温湿度交变试验周期</td><td>加热：温度25～40℃，相对湿度95%～98%，0.5h 受潮：温度（40士2）℃，相对湿度95%～98%，16h 降温：温度40～25℃，相对湿度不小于90%，2.5h</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>温湿度交变试验周期</td><td>冷却：温度（25±2）℃，相对湿度95%～100%，不少于5h 24h为一周期，连续试验21d</td></tr><tr><td>恒温恒湿试验周期</td><td>温度（47±1)℃，相对湿度96%±2% 24h为一周期，连续试验到样板破坏为止</td></tr></table></body></html>  \n\n从实际试验情况来看，过高的温度，虽然周期短、破坏快，但在某些情况下会因变化太快而不能很好地区别样板的优、劣，甚至会歪曲试验的真相。温湿度交变的试验周期，由于有低温高湿阶段，使水汽在漆膜表面上凝露，有利于水分渗透到漆膜内部，从而加速了对漆膜的破坏，但从目前试验的趋向来看，在湿热试验中不要产生过多凝露的倾向。因为凝露太多，在漆膜上形成一层水膜，易造成漆膜中的可溶物质过多地被溶解出来，与实际湿热情况不符。  \n\n我国国家标准GB/T1740—2007《漆膜耐湿热测定法》规定用恒温恒湿试验周期方法。  \n\n目前，耐湿热试验一般均在调温调湿箱内进行。由于湿热试验中最主要的影响因素是温度和湿度，因此在每次试验中需特别注意对这两个因素的控制，以免影响试验结果。另外在试验时垂直悬挂的样板之间应保持一定的距离，以不相互重叠碰撞为准（ $2\\cdots4\\mathrm{cm})$ 。样板在各周期检查时还应互换位置，以尽可能地减少因设备内温、湿度的不均匀所造成的试验误差。试验用水也应注意采用蒸馏水或离子交换树脂净化水。  \n\n对于样板的评定主要观察涂膜有无起泡、生锈和脱落，按其损坏程度进行评级。  \n\n(3）水汽透过性试验前面已经提到，水通过涂膜渗透达到底材，因而引起腐蚀。因此对涂膜进行水汽透过性检测，可以判断涂膜耐腐蚀程度。这项试验用游离涂膜来进行，所以检验手续比较繁杂。它是用渗透性试验杯测定，将游离涂膜夹在试验杯中，在膜两面施加不同的恒定的相对湿度，在一定的时间内，计算出透过规定的表面积试膜的水蒸气质量，以$\\mathbf{g}/(\\mathbf{m^{2}}\\cdot\\mathrm{d})$ 表示水汽透过率，数值低表示透过水汽少，可以作为各种涂料耐腐蚀程度的一种表示方法。这个方法一般用于涂料产品的研究。  \n\n(4）钢铁表面丝状腐蚀试验钢铁表面发生细丝状腐蚀（丝状锈蚀）可使表面涂层呈现疏松线状隆起现象，通称丝状腐蚀（filiform sorrosion)，它常是由一个或几个腐蚀生长点辐射而成的。试验和评价色漆或清漆涂层在有微量盐分和规定的相对湿度下，由于划痕引起钢铁表面上产生丝状腐蚀情况，也是对耐腐蚀性的一种检测方法。我国等效采用ISO4623—1984，制定了 $\\mathrm{GB/T13452.4-1992}$ 《色漆和清漆钢铁表面上的丝状腐蚀试验》。检测方法中规定，在被试样板上刻划两条相互垂直、间距（及离样板边缘）不小于 $20\\mathrm{mm}$ 的各长$\\mathrm{50mm}$ 的划痕，在划痕上能清晰看到金属表面。将样板浸人 $\\mathbb{1}\\mathbb{g}/\\mathbb{L}$ 的氯化钠溶液 $30\\sim60{\\mathrm{s}}$ (浸泡法)，或者放于符合GB/T1771—2007规定的中性盐雾中达到协议规定时间（盐水喷雾法)，然后放人温度 $(40\\pm2)^{\\circ}C$ 、相对湿度 $80\\%\\pm5\\%$ 的试验箱中，按规定时间进行检验，根据划痕扩展开的丝状腐蚀程度和数量来进行评价。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1320,
+        "chunk": "# 六、涂膜耐久性能的检测  \n\n涂料的质量除了取决于各项物理性能指标的检验外，更重要的是其使用寿命，即涂料本身对大气的耐久性。这种耐久性的表现代表了该涂料的真正实用价值，是该涂料各种技术性能指标的综合表现，因此，进行涂料的耐候性试验是很必要的。提高涂料的耐候性，是改进涂料质量的关键。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1321,
+        "chunk": "# 1．大气老化试验  \n\n涂料在使用过程中受到各种不同因素的作用，使涂层的物理化学和力学性能引起不可逆的变化，并最终导致涂层的破坏，这种现象一般称为涂膜的老化。  \n\n涂料的大气老化试验是指在各种气候类型区域里研究大气各种因素如日光、风、雪、雨、露、温度、湿度、氧气、化工气体等对涂层所起的老化破坏作用，通过试板的外观检查以鉴定其耐久性。也可在曝晒过程中进行漆膜的物理力学性能及游离漆膜的性能测试，但做得并不多。  \n\n根据大气种类可分为乡村大气、工业大气和海洋性大气；根据地区又可分为温带、寒带、干热带、湿热带等类型；而根据曝露方法又可分为朝南 $45^{\\circ}$ 、当地纬度、垂直角度及水平曝露等方式。  \n\n(1）气候、季节、曝晒角度的影响我国面积广大，气候类型复杂，从北到南、由东到西气候条件很不一样，往往同一个配方的品种，在不同地区使用性能差异很大，因此为了全面考核某一个品种的耐久性，就有必要在各个气候类型区域内同时进行曝晒试验。  \n\n通过一系列样品的曝晒可得出不同气候地区对试板破坏的严酷程度。以同样的醇酸品种，如白、红、绿、黑四种颜色，采用同样的施工工艺，同时在天津、上海、武汉、重庆、广州、海南等地进行曝晒，可发现气候条件以重庆、广州、海南等地最为严酷，样板破坏严重；武汉、上海居中，天津破坏最慢；而在重庆、广州、海南等地中，又以海南最快，样板破坏最为厉害。  \n\n样品的耐久性除与气候地区有关外，曝晒季节对其影响也很大。由于季节不同，样品所经历的气候条件不同，漆膜的破坏程度也不同。  \n\n对于自干类型的涂料，在春季曝晒时，由于漆膜尚未完全坚实，就受到温差的急剧变化而引起漆膜变形；接着在夏季又遭受到强烈的紫外线照射或大量的雨水侵袭而进一步造成破坏。在秋季曝晒时，由于气温较平稳，紫外线强度也日趋下降，致使新涂的漆膜能有一段继续坚硬的过程，从而经得起来年的大气破坏作用。  \n\n实际试验也证实了这点，即春季晒板破坏最快，秋季晒板破坏最慢。其顺序是：春 $\\nrightarrow$ 夏 $\\rightarrow$ 冬 $\\rightarrow$ 秋。因此，从涂料的角度来看，试验在春季，施工在秋季是有其一定道理的。  \n\n需指出的是，我国南方地处温热带或亚湿热带的一些地区，虽然炎热，但温差变化较小，气候随季节不同的变化不太显著，故曝晒季节对漆膜耐久性的影响不如我国其他地区大。  \n\n另外，曝晒角度对涂料的耐久性影响也是需要加以考虑的。因为在大气老化中，光是一个很重要的因素，因此应该尽量设法以最合适的角度来最大限度地利用太阳能。  \n\n经试验发现，在短期曝晒过程中及为了加速样品的破坏，每年的上半年可采用春、夏季最热角度（即 $\\phi-25^{\\circ}$ ，其中 $\\phi$ 为当地纬度)；下半年则可调节成秋、冬季最热角度（0.893$\\phi+24^{\\circ})$ ，这样易于快速地获得天然曝晒试验的结果。对于需要连续曝晒几年或因条件所限而不考虑来回调整角度的，则采取当地纬度最为适宜，以使样品比其他角度能受到更多的和更长时间的光照。  \n\n(2）曝晒场的设立曝晒场应建立在平坦、空旷的地方，周围无高大障碍物，使样板能充分受到各种大气因素的作用。若作为一般的大气曝晒试验，即乡村大气，则应尽量避免各种工业有害气体的影响。  \n\n曝晒场应有明亮的工作室、贮存室，并应具有必需的气象观测设备，各种漆膜检查的仪器及洗手池、上下水、照明电等各种设施。  \n\n气象资料的观测视曝晒场环境、规模和人力而定，若在邻近有气象台（站）者，可直接  \n\n采用气象台（站）的数据。  \n\n曝晒架可用钢材或木材制成，并用耐候性较好的涂料涂装，其结构应力求简便、牢固，能调节曝晒角度者更好。  \n\n(3）样板检查方法我国国家标准GB/T9276—1996《涂层自然气候暴露试验方法》中规定了以年和月为样板检查的计时单位，规定在曝晒的第一至第三个月内，每隔15天检查一次；从第四个月起，每月检查一次；一年以后每3个月检查一次。由于涂料品种的不同以及曝晒地区破坏速度的不同，检查周期可根据情况适当变更。  \n\n规定的检查项目包括失光、变色、粉化、裂纹、起泡、斑点、生锈、泛金、沾污、长霉和脱落等。  \n\n检查主要是目测法，比较简便，能具体判断涂装的实用性能和耐老化程度的差别，但易产生个人的主观误差。其中漆膜的光泽和颜色，可用仪器测定，以数值来反映漆膜耐久性的变化。  \n\n对于色漆粉化程度可按GB/T14826—1993《色漆涂层粉化程度的测定方法及评定》的规定，或者采用粉化测定仪，或者采用手工测定，对照标准评定等级。具体评级方法在国家标准GB/T1766—1995《色漆和清漆涂层老化的评级方法》中有规定。  \n\n此外，近年来利用仪器分析日渐增多，如对漆膜表面进行复型，在电子显微镜下就可观察到漆膜表面微细结构的改变，从而在较短的时间内就可预测天然曝晒的最终结果。也可在曝晒样板上切下游离漆膜进行红外分析，以判断曝晒的不同阶段漆膜老化所达到的程度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1322,
+        "chunk": "# 2.人工加速老化试验  \n\n人工加速老化试验是基于大量的天然曝露试验的结果，从中找出规律，找出气候因素与漆膜破坏之间的关系，以便在实验室内人为地创造出模拟这些气候因素的条件并给予一定的加速性，以克服天然曝露试验需时过长的不足。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1323,
+        "chunk": "# （1）试验中的有关因素  \n\n$\\textcircled{1}$ 光源从国内外已有的试验情况来看，光源是漆膜老化中的一个很重要的因素。太阳光谱一般可分为3个区域：紫外线区、可见光区和红外线区。经测定，晴天太阳当头时（指赤道的中午)，海平面的太阳能分布如下：  \n\n紫外线 \\*\\*\\* $290{\\sim}400\\mathrm{nm})$ 占 $4\\%$ 可见光 $(400{\\sim}700\\mathrm{nm})$ 占 $43\\%$ 红外线 $(700-2500\\mathrm{nm})$ 占 $53\\%$  \n\n虽然紫外线能量仅占太阳总能量的 $4\\%$ ，但许多材料却正是在紫外线区域内遭受破坏的。如硝基纤维素主要是在 $310\\mathrm{nm}$ 波长光的辐射下分解；不饱和聚酯与苯乙烯的共聚物在波长为 $325\\mathrm{nm}$ 时很快变黄；聚丙烯、聚氨基甲酸酯等在 $330\\sim370\\mathrm{nm}$ 时出现老化。  \n\n$\\textcircled{2}$ 温度由于光的作用总是伴随着温度的上升，因此温度升高也是促使漆膜老化的一个重要因素。漆膜的热老化，主要是由于交联过程及聚合物分子链的破坏：交联的结果，产生了立体结构，使漆膜变硬、变脆、失去弹性；而分子链破坏的结果使大分子链断裂，减少了分子长度及分子量，形成了游离基团，表现为发软、发黏。  \n\n在人工加速老化试验中，一定的温度配合周期性的降雨，造成频繁的交变温度，其影响比单纯的热老化更为重要，因为这样使涂层和底板发生不断的膨胀和收缩，就可导致涂层中形成很大的内应力。在大多数情况下，漆膜组成的体系中含有成分和结构不同的物质：底漆、腻子、色漆、磁漆或清漆，因此在受温度交变作用时，由于在各层中的应力有所不同，再加上具有一定波长的强烈光照，很容易造成漆膜的开裂  \n\n③湿度在大气中曝露，漆膜实际上是长时间保持在潮湿状态下，尤其在湿热带地区更是如此。低湿度的紫外线照射虽然也能使漆膜产生失光、粉化，但作用较慢，并且很少出现龟裂；而在高湿度下，紫外线照射就成为一个更有效的破坏因素，使上述破坏作用大大增强。其原因主要是水分的吸收引起了漆膜的溶胀，体积变化，或使漆膜中水溶性物质溶解出来，当受光线照射时，就易使漆膜结构破坏或加快了光化学变化的作用。当然湿度的影响应考虑到温度、水分以及光照等各因素互相促进的总体影响。  \n\n④氧气漆膜中的聚合物仅仅由于日光而解离的情况非常少，由于日光和氧气的相互作用，即所谓的日光氧化而促进老化是值得注意的。被太阳能所活化的氧会引起漆膜表面的氧化作用，结果增加了漆膜的孔隙并形成了漆膜的失光。已证实在人工加速老化试验循环中，增加氧处理具有重要的意义，尤其是在较高压力的氧气处理中，显著地增加了由于裂缝和龟裂所引起的破坏现象。  \n\n（2）人工加速老化设备为了模仿自然界中各种气候因素，以便在实验室内创造出所谓人工气候，并且能达到加速试验的目的，可采用人工老化机（图4-3-46）。其构造大致可分为上、中、下3个部分。上部主要是老化机的主配电盘，装有各种控制仪表及开关。中部为样品进行老化的实验室。下部为传动机构、鼓风机及发湿箱等。  \n\n![](images/5fd782e7358fc8b885cfaeb21347a685a39a0479f75d1f298c3b12cf39ebef71.jpg)  \n图4-3-46人工老化机  \n\n人工老化机根据所采用的光源可分为荧光紫外线型、阳光炭弧型、氙灯型、高压水银灯以及组合光源等类型。荧光紫外线型试验箱由耐腐蚀金属材料制成，包含8支紫外灯，盛水盘，试验样品架和温度、时间控制系统及指示器。荧光紫外灯的波长分为：UV-A波长范围为315\\~400nm，UV-B波长范围为280\\~315nm，UV-C波长范围为<280nm。涂料人工加速老化使用最多是UV-A和UV-B。  \n\n高压水银灯是一种水银蒸气的弧光放电灯，有直形和U形的。与紫外线炭弧灯相同，也主要产生紫外线能量。但高压水银灯发出的光谱是线状光谱，是不连续的，能量集中在几条特征谱线附近，除了具有300～380nm的波段外，其小于290nm的短波成分也较多，因此使它对漆膜的破坏有着与炭弧灯不同的影响。  \n\n阳光炭弧型则利用炭棒内含有的金属元素不同，使发出的光谱除了包括紫外线区域278～400nm的以外，可见光部分领域也很大，红外线部分则很少，这样就使灯源的光谱能量与太阳的光谱能量分布较为接近，比单纯的发射紫外波段的炭弧灯和高压水银灯提高了一步。  \n\n近期推广采用的氙灯，是一种内充高纯度氙气的弧光放电灯，它由一根透明石英玻璃管制成，两端各封接有一金属电极。氙灯比上述几种光源先进之处是：首先其光谱能量分布更为接近太阳光，这样试验的模拟性就可大为提高；另外氙灯的辐射强度也比较均匀，当灯电流在相当范围内变化时，其光谱分布的特性仍然不变。当然氙灯也含有少量天然光中所没有的300nm以下的短波成分及发热量较大的红外部分，因此为了避免影响试验结果，也必须对光进行过滤以及需用冷水对灯管进行冷却。  \n\n人工老化机的各种类型列于表4-3-13。  \n\n表4-3-13人工老化机的各种类型  \n\n\n<html><body><table><tr><td>类型</td><td>特征</td><td>工业上用的型号举例</td></tr><tr><td>荧光紫外灯</td><td>紫外波段，连续光源，模拟性和加速性并重</td><td>美国Q-PANELUV-SPRAY型</td></tr><tr><td>高压水银灯</td><td>紫外波段，线状光谱，加速性好</td><td>德国ERICHSEN249型 前苏联AHHCT-2-4-2型</td></tr><tr><td>阳光炭弧灯</td><td>连续光谱，既有紫外波段又有可见光部分，模拟性 和加速性并重</td><td>中国LH-2型 美国XW-R型 日本WEL-SUN-DC型</td></tr><tr><td>氙（气）灯</td><td>光谱能量分布比较接近太阳光，模拟性好，但加速 性较慢</td><td>中国6XW-2型 美国Q-SUN型 美国ATLASCA-5000型 日本WEL-6XS-DC型</td></tr></table></body></html>\n\n$\\textcircled{1}$ 采用的炭棒可连续点燃 $5.5\\mathrm{h}$ $\\textcircled{2}$ 系氙灯与炭棒两用型老化机。  \n\n通过某些品种的加速老化试验，我们可以得出这些设备对试验效果的基本概念：采用荧光紫外型老化机，其UVA-340紫外灯光源能很好地模拟太阳光谱中短波紫外线（<365nm）部分，理论上这种方法的测试结果和户外自然老化的相关性较好，实际检测结果与天然曝晒试验的结果基本相同。其差异主要集中在无法模拟户外自然曝晒中样板产生的锈蚀。需要注意的是，如果测试循环仅采用紫外曝晒，人工加速老化试验和户外自然曝晒有较大差异，为了提高二者的相关性，必须在人工老化的测试循环中加入冷凝循环。此外需要指出的是，相比UVB-313灯管而言，UVA-340灯管不会产生非正常的黄变。  \n\n阳光型老化机从实际试验情况来看，在加速倍率上并不比紫外线炭弧型的快多少，在破坏现象上也基本一致，但在某些破坏特征方面，尤以漆膜在老化过程中的颜色变化，与天然曝晒的色相变化颇为一致，显示了比紫外线炭弧型及高压水银灯型的老化机优越。  \n\n氙灯与高压水银灯一样，也是灯管型，使用操作较简便，并且氙灯与天然的模拟性很好，对于褪色试验特别合适，不足之处是加速倍率不够理想。为了既能解决模拟性，又能提高加速性，国内外有推荐采用组合光源的，即把上述各种灯源中的两种，以适当的配合同时装置在老化机中，以解决模拟与加速的矛盾。但直至目前，还未见到有广泛的推广和应用。  \n\n（3）人工加速老化试验的发展如前面所述，大气曝晒虽然符合天然气候条件，但试验周期太长；人工加速老化虽然提高了曝晒速率，但模拟性还存在着一定问题。克服上述问题的有效办法是近年来发展起来的大气加速老化试验，即利用天然太阳光来加速，使在与天然气候条件比较一致的情况下加速漆膜老化。  \n\n大气加速老化机的主要结构是利用一个整  \n\n![](images/038f200506346e384aa8e1c616b4000f603c22c2a7bfa95eeba6fd910f8004ba.jpg)  \n图4-3-47大气加速老化机1一光电探头；2-鼓风机；3一喷水嘴；4一旋转轴；5-反射镜；6一减速箱；7-电磁阀；8一电子自动控制器  \n\n天跟着太阳旋转的框架，见图4-3-47。架上有10块150mm×1500mm的铝板反射镜，每面镜子都将太阳光线反射集中到一条150mm×1500mm的样品架上。这些反射镜是经过电抛光的光亮铝片，能反射85%左右的可见光和70%～80%的紫外线。在样品架上面还装有鼓风管，以使样品表面温度与朝南 $45^{\\circ}$ 角曝晒的情况相近。样品架下面设有喷水管，定时对样品喷射蒸馏水以进一步加快老化速度。经试验证明：在这样的试验机上曝晒的涂料样品，其破坏速度比朝南 $45^{\\circ}$ 角曝晒的样品快 $\\hat{6}\\sim\\mathbb{1}2$ 倍，故初步看来，这种利用天然曝晒条件采取一定的措施使其强化以达到使漆膜加速破坏的方法是合理的。因为首先它利用的是天然太阳光，可避免在老化机中人工光源与天然光的差别；另外它模拟性好，破坏现象真实，这样与朝南45°角曝晒的相互关系就较为确切，因此从技术角度来看这是一个很好的发展方向。目前存在的问题是由于大气加速老化装置在自然条件下进行试验，因此受气候条件的影响就比较大，尤其在南方湿热带地区，经常下雨、天阴，日照时间短，这样就影响了它的正常使用，故一般在气候比较干燥的区域或阳光照射较强烈的高原地带使用更为合适。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1324,
+        "chunk": "# 第四节 涂料和涂膜的组成分析  \n\n对涂料产品进行组成分析的作用有以下四点：  \n\n$\\textcircled{1}$ ①验证产品的组成是否与原设计配方保持数量的一致性；  \n$\\textcircled{2}$ 通过组成分析以控制产品的某些物化指标；  \n$\\textcircled{3}$ 检查涂料产品中某些特定物质的存在及其含量；  \n$\\textcircled{4}$ 判断未知产品的类型及其结构。  \n\n涂料组成分析的内容通常有下面两方面，一是根据涂料产品的技术要求进行的专门项目的分析检测，如不挥发分含量、灰分、水分，某些产品所含代表性组分的存在和含量，如醇酸树脂漆中的苯酐含量和某些特定物质（如重金属）的存在和含量等。通过这些项目的检测，或作定性分析或作定量鉴定，可以确认这些物质的存在或含量是否符合产品标准中的规定，以评定产品是合格还是不合格。二是对涂料产品进行全部组成的分析，包括定性鉴定和定量测定，通称涂料产品的剖析。在产品检测中通常很少进行全面分析，主要用于对未知产品或对产品进行科学研究方面。  \n\n涂膜组成分析主要用于对涂料产品的科学研究。进行分析的作用有：  \n\n① 研究涂料产品中的组分在成膜过程中的变化情况，如通过化学交联的涂料在成膜前后的变化，以及其交联程度等的分析；  \n\n$\\textcircled{2}$ 研究涂膜组分对产品性能的影响；  \n$\\textcircled{3}$ ， 研究未知涂膜的结构状况，判断其性能概况。  \n\n对涂膜分析可以是分析某项组成，也可以进行全面定性或定量分析，按需要而定。通常涂膜分析的重点是涂膜中高聚物的组成和结构特性方面。  \n\n除了涂料组成分析中的某些项目外，涂料和涂膜在分析时首先要进行组分的分离，然后再进行定性或定量分析。分离操作步骤有简有繁，根据检测内容而定。定性或定量分析方法有化学分析和仪器分析两种。过去主要靠化学分析方法，现在则广泛采用现代化的仪器分析技术，如电子显微镜、红外光谱、X射线衍射、气相色谱和凝胶色谱等。运用这些分析技术可以解决使用一般检测仪器和化学分析所不能分析或鉴定的问题。它们的共同特点是试验需用样品数量少，测试范围广，速度快，分析精度高。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1325,
+        "chunk": "# 一、涂料和涂膜的组分分离  \n\n涂料组分分析的第一个步骤是对样品进行分离操作。根据不同的检测目的，采取不同的分离步骤。液体涂料最常用的分离方法是用溶剂溶解后采用离心分离法，将液体涂料分为溶剂可溶物和溶剂不溶物，然后再分别提取。根据涂料产品的类型选用不同的溶剂。依据国家标准GB/T9760—1988中的规定，适用于溶剂稀释型色漆的溶剂有甲苯-乙醇（4：1）（适用于自干型色漆)、二甲苯-正丁醇（9：1）（适用于烘干型色漆)、甲苯（适用于氯化橡胶型色漆)、丁酮（适用于硝基漆)；适用于水分散型色漆的溶剂有丙酮、1，1,1-三氯乙烷和四氯呋喃；适用于聚氯乙烯塑性溶胶和有机溶胶以及非水分散型涂料的有四氢呋喃、环已酮和环戊酮。  \n\n色漆的具体分离操作是将涂料样品放人离心管中，加人适当数量的溶剂，在离心机中进行分离，直到完全分离成一层清澈的液体和一个不溶解的颗粒（颜料）饼为止。反复进行3次，最后再用丙酮（聚氯乙烯塑性溶胶类型除外）稀释后，进行离心分离一次，则样品分为溶剂可溶物和溶剂不溶物两部分。溶剂不溶物在 $105^{\\circ}\\mathrm{C}\\pm2^{\\circ}\\mathrm{C}$ 下烘至恒重。也可以先将样品进行离心分离，吸取上层清液以作漆基分析，再用溶剂萃取。  \n\n对于水性乳胶涂料也可采取制膜法，对漆基用溶剂萃取，然后与溶剂不溶物分离，将制得的涂膜放在马弗炉中，在一定温度 $(475^{\\circ}C\\pm25^{\\circ}C$ ）下灰化后分离出颜料。  \n\n涂膜的组分分离可按溶剂萃取法进行，溶剂要适当选择。  \n\n如果主要是分析液体涂料的溶剂组分的组成，则可采用直接蒸馏法蒸出溶剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1326,
+        "chunk": "# 二、涂料组分的单项分析  \n\n现在，涂料产品标准中规定的较普遍的组分分析检测项目是不挥发分含量的检测，其检测方法已在涂料性能检测中叙述。与之相对应的挥发分含量可通过计算得出。除此以外，在产品标准中常见的技术指标项目还有：水分、灰分、酸值和闪点；有些醇酸树脂漆标准中列有苯酐含量；有些涂料产品对所含重金属含量有规定。下面简述这些单项检测的方法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1327,
+        "chunk": "# 1.水分  \n\n对溶剂型涂料可按GB/T1746—1979（1989）《涂料水分测定法》中规定的蒸馏法，用水分测定器测定，蒸馏至接收器中水的体积不再增加为止，以试样中所含水量的百分数表示结果。  \n\n此外，还可用卡尔-费休法进行水分的测定，如ASTMD4017—1990所规定的。  \n\n用气相色谱法可测定水性涂料的水分含量，如ASTMD3792—1991所规定的。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1328,
+        "chunk": "# 2.灰分  \n\n涂料中的灰分是涂料经灼烧灰化后的剩余物含量，可作为涂料中所含无机颜（填）料量的概略表示数值。试样放于坩埚中，在马弗炉中焙烧至恒重，结果以百分数表示。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1329,
+        "chunk": "# 3.酸值  \n\n对有些涂料品种有时要测定其中游离酸含量，以中和 $1\\mathrm{g}$ 试样所需氢氧化钾质量（mg)表示酸值。依据涂料品种不同分别采取稀释法、溶剂抽出法、水抽出法、水-溶液分层法和离心沉淀法提取试样，进行测定，以 $\\mathrm{\\mgKOH/g}$ 表示。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1330,
+        "chunk": "# 4.闪点  \n\n溶剂型涂料通常要测定闪点，作为安全使用的技术数据。实际检测的是所含可挥发的混合溶剂的闪点。检测涂料闪点的方法通常是用GB/T5208—1985《涂料闪点测定法快速平衡法》。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1331,
+        "chunk": "# 5.醇酸漆中苯酐含量  \n\n可用化学分析法测定。称取一定量的样品，如果是色漆要先进行溶剂提取，然后离心分  \n\n离得到溶剂可溶物，与氢氧化钙进行化学反应，滴定所生成的苯二甲酸钙含量，计算出其苯酐含量。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1332,
+        "chunk": "# 6.涂料中重金属含量  \n\n根据环保法规的规定，限制涂料产品中的重金属含量，甚至不允许重金属存在。这些重金属包括铅、锑、钡、镉、铬、汞、铜、铁、铝、钛等。对这些重金属含量的检测有两种方法，一种是在涂料中含量的检测，另一种是这些涂料中的重金属相当于胃酸所溶解的酸“可溶性”金属含量。  \n\n涂料中重金属含量的检测有化学分析法和仪器分析法两种。如日本JIS规格中有测定涂料溶剂不溶物中铅（包括二氧化铅、四氧化三铅)、铬、铁、铜、铝含量的化学分析方法。仪器分析法则通用原子吸收光谱法。  \n\n对涂料中酸“可溶性”金属的检测，依据国家标准GB/T9760—1988《色漆和清漆液体或粉末状色漆中酸萃取物的制备》的规定，首先用溶剂稀释液体涂料，离心分离成溶剂可溶物和溶剂不溶物两部分，然后用相当于胃酸的 $0.07\\mathrm{mol/L}$ 的稀盐酸对溶剂不溶物进行萃取，将离心得到的溶剂可溶物蒸发至干，残渣经干燥灰化后，用硝酸萃取，得到的以上两种萃取液，分别按照GB/T9758—1988《色漆和清漆“可溶性”金属含量测定》和GB/T13402.1一1992的方法，用火焰原子吸收光谱法测定铅、锑、镉、铬（色漆的液体部分中）的含量；用火焰原子发射光谱法测定钡的含量；用分光光度法测定6价铬（色漆的颜料部分中）的含量；再用无焰原子吸收光谱法测定汞的含量。此外钡的含量也可用极谱法测定。  \n\n原子吸收光谱法系根据原子吸收固定波长的光谱，原子浓度不同，则吸光值不同的原理，通过光谱仪标定出某个金属的标准溶液浓度与相应吸光值曲线，用试样溶液在固定光谱下测出的吸光值计算出其含量。原子吸收光谱法有火焰（乙炔/空气燃烧的火焰）和无焰（冷蒸气）之分。  \n\n原子发射光谱法是测量某一金属原子在火焰中于固定的波长处所发出的辐射的强度，得出该金属的质量，采用火焰原子发射光谱仪测定。  \n\n分光光度法是用分光光度计测量在固定波长处的吸光值，然后计算出所含金属量。  \n\n极谱法是通过测定电解极谱池中溶液在极谱仪中显现的波峰高度，计算出金属的含量。  \n\n对涂膜中重金属含量的分析，则先将涂膜在 $475^{\\circ}C\\pm25^{\\circ}C$ 干烧灰化，然后根据所测重金属种类采用相应的试剂萃取，可用化学分析或仪器分析方法测定。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1333,
+        "chunk": "# 三、涂料和涂膜的全面分析  \n\n涂料的全面分析即对涂料中所含的漆基（包括成膜物质、增韧剂等有机物质)、颜料和溶剂3类组分进行定性和定量鉴定。涂膜则不包括溶剂。现在一般以仪器分析为主。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1334,
+        "chunk": "# 1.漆基的剖析  \n\n对漆基分析常用的方法是红外吸收光谱法和气相色谱法。用凝胶色谱法可测定漆基中高聚物的结构。此外还可用核磁共振法。  \n\n(1）红外吸收光谱法用红外吸收光谱法可根据红外谱图中所呈现的特征基团（如氨基、羧基、双键及取代位置等）来分析推断漆基所属的类型，同时也可以用于涂料生产工艺过程、成膜机理及老化过程等方面的研究。  \n\n红外波长范围为 $1\\sim300\\mu\\mathrm{m}$ ，一般红外波长为 $2,5\\sim25\\mu\\mathrm{m}$ （波数为 $4000{\\sim}400\\mathrm{cm}^{-1}$ )。目前红外光谱已成为涂料分析研究中重要的测试方法之一，借助于它可以解决物质的定性和定量问题，以及判别有关分子的结构一—基团的分析和各种化合物的鉴别。  \n\n红外光谱所用的仪器为红外分光光度计，如图4-3-48所示。其简单原理是从光源射出的红外线，分成基准光束和试样光束，由扇形旋转镜把它们先后引人单色器内。试样吸收了红外线时，这两种光束就产生了光的强度差，可由热电偶来测得，作为交流信号被放大后，再通过一系列调整装置，就能自动地记录下该试样的红外吸收谱图。  \n\n![](images/022b05de4c5aaebb2319138aa508fca35145a60ff7d0bdce3f7e38e6671c1071.jpg)  \n图4-3-48红外分光光度计工作原理简图  \n\n1—光楔；2—扇形旋转镜；3—单色器；4—热电偶；5—放大器；6—调整装置；7—记录器  \n\n测定红外光谱时，试样可以是气态、液态或固态。气体样品可用气体吸收池。液体样品可夹于两片氯化钠薄片中间作定性检查，也可放于特制的液体吸收池中。固体样品则采用压片法，即把样品与溴化钾粉末均匀混合压成薄片。  \n\n测试所得的红外谱图，横轴表示波数（ $\\mathrm{cm}^{-1}$ ）或波长 $(\\mu\\mathbf{m})$ ，纵轴表示透射百分率或光密度。鉴定未知性质的样品时，一般是与已知样品的标准谱图作比较，根据在一定波数处的吸收峰就可以定性，根据透射百分率的多少就可作定量的估算。  \n\n但需指出的是：红外吸收光谱法的灵敏度一般较低，对于谱线吸收度相对较低的组分，以及其主要谱线由于与主要组分的谱线相重叠而受到干扰时，有时虽含量并不低，却未能从漆基的红外谱图中检出，此时就需辅以其他分析方法以对组分进行分离，然后再用红外吸收光谱法加以鉴定。  \n\n(2）气相色谱法气相色谱对高聚物的分析大多采用“热解法”。即将固态的高聚物在热解器中加热到数百摄氏度或更高的温度，高聚物的大分子则因受热而分解（即大分子链断裂)，对断裂以后的小分子进行色谱测定，从而可推算出高聚物原来的结构。如芳族胺固化的环氧树脂的热解色谱分析。  \n\n气相色谱法是1952年出现的一种分离、定性和定量三步同时进行的一种新型的物理测试方法，近20年来发展迅速。由于它具有分离效能高、分析速度快、样品用量少等特点，因而已在有关的科学研究和工业生产中得到广泛的应用。  \n\n气相色谱法主要是依靠物质在两个不同相之间的不同分布而使不同组分得以分离的，这两个相之一称为流动相，另一相称为固定相，其间的分布作用主要为吸附和分溶两种形式。若流动相是气体（一般为 $\\mathrm{N}_{2},\\ \\mathrm{H}_{2}$ 、He、Ar等，称为载气)，固定相是固体吸附剂，叫气固吸附色谱。若固定相是附着于情性担体（一般为硅藻土型）上的低蒸气压的有机“溶剂”，称为固定液，叫气液分配色谱。  \n\n气相色谱仪测试的简化流程如图4-3-49所示。  \n\n样品首先打人汽化室，瞬间被汽化成气体，被载气带人色谱柱进行分离，分离后各组分先后进入鉴定器，产生的信号经放大后，在记录器上自动记录下来。  \n\n![](images/054e30c8e8dfa65ebc0423721f5a2924d22f6bb0c88f064736552891b3f8f312.jpg)  \n图4-3-49 气相色谱仪流程简图  \n\n1—载气瓶；2—流速计；3—汽化室；4—色谱柱；5—鉴定器；6—放大器；7—记录器  \n\n由气相色谱法所获得的色谱图，并不能使我们直接了解被分离组分的成分，对未知成分的定性，需要用已知纯物质的色谱图进行对照，这就是气相色谱法的缺点之一。然而，近年来气相色谱-红外光谱、气相色谱-质谱联合技术的发展，在很大程度上已弥补了这一缺陷。目前气相色谱在涂料中可进行溶剂、油、树脂、增塑剂、聚合物（热解后）和乳化剂等的分离和鉴别。  \n\n通常可将气相色谱法与红外光谱法结合起来进行漆基分析。  \n\n(3）凝胶色谱法凝胶色谱法是1964年后出现的一种快速测定高聚物分子量分布的方法，20世纪70年代继仪器化后又采用高效凝胶填料达到了高速与高效化，因而被誉为在分子量测定技术上的重要突破。  \n\n凝胶色谱是一种用溶剂作流动相，多孔填料或凝胶作分离介质的柱色谱。当多分散的高分子溶液注人柱内后，溶液流经多孔凝胶或填料，此时高聚物按尺寸大小分开。由于样品中尺寸最大的分子比多孔凝胶中所有孔穴都大，不能进人孔内，只能在填料间隙中流动而最先被淋出柱外。试样中尺寸再小一些的分子，能扩散进入填料中那些比较大的孔穴中，随着淋洗过程又重新扩散出来，因而被推迟一些时间淋出柱外。试样中分子尺寸最小的，由于可以出人所有的孔，结果被滞缓于最后流出，由此实现了按分子量大小的分离。  \n\n凝胶色谱法可作为测定分子量及其分布的快速、有效的手段，它可以分离的分子量范围很广，从小分子到分子量 $10^{5}$ 以上的高分子，并被广泛应用于高聚物体系的基础研究中，如聚合反应历程的研究、聚合条件的控制等。另外凝胶色谱法对含有分子量差别比较大的混合物和低聚物的分离是非常有效的，对于一般有机化合物的混合物也可以用它来作首选分离，以判明混合物的复合程度，以便进一步选用其他方法作更细致的分离。因此它无论在高分子化合物还是在小分子化合物中都有独特的用途。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1335,
+        "chunk": "# 2.颜料的剖析  \n\n颜料，特别是无机颜料，主要的分析手段是X射线衍射法。它可以对液体涂料样品不经分离直接进行颜料的定性和定量分析。若与样品的固体分测定结合，漆基和溶剂的各自含量也可一并求得。  \n\nX射线衍射法在多组分混合颜料鉴定中也有一个灵敏度和谱线干扰问题，此时应辅以X荧光等元素分析法，或应用富集和分离手段分别检出。  \n\n有机颜料采用X射线衍射法时比无机颜料的灵敏度低，不易检出，应先利用重力差异将有机颜料分出，然后用红外光谱法鉴定。  \n\nX射线是电磁波的一种，是本质上与寻常光线完全相同的电磁辐射，只不过其波长极小（仅为 $10^{-8}\\mathrm{cm})$ 。在衍射方面应用的X射线，其波长约为 $(0,5{\\sim}2.5)\\times10^{-8}\\mathrm{cm}$ 。 $\\mathbf{\\boldsymbol{x}}$ 射线衍射是研究物质结构的一种先进分析技术，这种技术是在1912年发现了晶体能衍射 $\\mathbf{X}$ 射线，并由其衍射的方式能揭示出晶体内部的结构而开始的，现已发展成为化学研究中重要的物理测试工具之一。  \n\n晶体学的研究表明，晶体具有有规则的内部排列，相邻原子间的间距和X射线波长具有相同的数量级，均为 $10^{-8}\\mathrm{cm}$ 左右，因此可以利用晶体作为产生 $X$ 射线衍射的光栅，使人射的X射线经过某种晶体后发生衍射。其衍射角 $\\theta$ 、晶体晶面间距 $d$ 和人射 $X$ 射线的波长遵循布喇格定律，即  \n\n$$\n2d\\sin\\theta=n\\lambda\n$$  \n\n式中 $n$ 衍射级数； $d$ 晶体晶面间距， $\\mathbf{nm}$ r $\\theta$ 衍射角，（°）； A- 人射的X射线的波长， $\\mathbf{nm}$ 0  \n\n根据这个公式，若已知X射线的波长及入射角时，就可计算出在结晶格子间的两面间距离，从而判断结晶的构造。  \n\n由于自然界中结晶物质都具有自己的特征衍射谱图（包括谱线位置和强度)，因此可以通过晶体物质的X射线衍射谱图的记录和分析，反映出该物质的化学组成及其存在状态，即物相。  \n\nX射线衍射仪的构造可分为3个部分。  \n\n(1）X射线发生器产生稳定的负高压给X射线管，使X射线管内的热电子在高压电场作用下，撞击阳极金属靶产生特征X射线。  \n\n(2）测角器主要是使X射线束以某一个入射角射到样品上，并用对X射线高度灵敏的计数管接收衍射的X射线，把其变成电脉冲信号。  \n\n(3）记录器把由计数管传送来的信号经过电子放大，记录在图纸上形成X射线衍射图。  \n\n依据X射线衍射图可以剖析涂料中的颜料和体质颜料的组成，也可对无机颜料或有机颜料的类型进行分析，在颜料工业中是研究工艺的一项重要分析方法。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1336,
+        "chunk": "# 3.溶剂的剖析  \n\n对从涂料样品中蒸馏得到的溶剂，可用红外吸收光谱法直接进行定性。混合溶剂的各个组分的定量测定可用气相色谱法。用气相色谱与质谱联机测定方法可得到更精确的结果。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1337,
+        "chunk": "# 四、涂膜结构电子显微镜检查  \n\n对涂膜的内部和表面微观结构可以用电子显微镜进行检查。  \n\n电子显微镜从20世纪30年代开始至今，已在分析方面得到广泛应用。  \n\n一般所用的光学显微镜其放大能力最多 $1000{\\sim}1500$ 倍，继续放大，则分辨不清。主要是由于光学显微镜是用可见光作为光源的，分辨能力受到可见光波长的限制。分辨能力的大小主要取决于波长，波长越短，则分辨本领越高。电子显微镜是利用在真空中高速运动的电子流作为光源，其波长约为可见光的 $10^{-5}$ ，并且电子的波长又可随加速电压的不同而改变，加速电压越高，波长越短，因此电子显微镜具有分辨能力高、放大倍数大的特点，已成为探讨微观世界的有力工具。  \n\n![](images/292d581174aceaa74bfaf80adc19d2e620e894a0b5b8ca02f39bcc11dcf4fa88.jpg)  \n图4-3-50工作原理比较简图1一电子枪；2一磁场聚光镜；3-磁场物镜；4一磁场投影镜；5一荧光屏或感光片；6一聚光镜；7—物镜；8-投影镜；9一观察屏  \n\n电子显微镜工作原理及与光学显微镜的比较如图4-3-50所示。  \n\n电子显微镜电子的来源是热离子阴极。射出的电子经过加速先由磁场聚光镜使之平行，然后打到试样上，由于试样各部分的厚度和密度不同，因此透过的电子密度也就不同。透过试样的电子流经过磁场物镜放大成中间影像在磁场投影镜的物面上，冉由磁场投影镜将中间影像放大而投射于荧光屏或感光片上，我们就可借荧光屏见到试样被放大后的最后影像。  \n\n涂膜用电子显微镜检查包括以下两项。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1338,
+        "chunk": "# 1.漆膜表面的检查  \n\n一般采用复型法。可对漆膜的表面结构进行分析，对天然和人工老化不同时期的漆膜变化状况及表面缺陷可进行观察。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1339,
+        "chunk": "# 2.漆膜内部的检查  \n\n可采用超薄切片法、超薄涂膜法以及对某些漆样用腐蚀复型法以对漆膜内部结构进行分析。可以观察到颜料粒子在漆膜内部的分布和分散状态，底、面漆之间的相互结合情况等。  \n\n此外，电子显微镜还可用于颜料检测，可测定各种颜料粒子的大小和形状，对于较规则的颜料粒子可计算出其平均大小和比表面积；对一些不规则的颜料则可给出最小到最大的范围；对一些后处理颜料、包核颜料，可进行表面状况及包覆情况的分析。  \n\n另外，电子显微镜也可对一些高聚物溶液的结构和结晶性质以及聚合物体系中的相互扩散作用进行观察和分析。  \n\n以上介绍了几种在涂料中常用的仪器分析方法。除此以外还有：能快速提供关于热稳定性结果的“热天平”；能提供热分解时所发生的热函变化结果的“差热分析”；可测定基团上氢的位置的“核磁共振”以及可以求出某物质的分子量的“质谱”等分析方法。应该指出：每一种分析技术都有它的局限性和不完整性，在许多情况下，仅使用一种测试方法对于所要分析解决的问题往往得到的结果是不完全或不够充分的。因此有必要将两种或两种以上的方法结合起来，如将色谱与质谱、红外光谱结合起来，就能够完满地解决未知物的分析。对于涂料生产和科研工作者来说，如何正确理解、使用和组合这些先进测试技术是很重要的。对于有关的分析技术可参考相应的专业书籍，特别是高聚物科学技术书籍。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1340,
+        "chunk": "# 参考文献  \n\n[1] 涂料与颜料标准汇编：涂料产品建筑涂料卷，北京：中国标准出版社，2007.[2] 涂料与颜料标准汇编：涂料产品 专用涂料卷．北京：中国标准出版社，2007，[3] 涂料与颜料标准汇编：涂料产品通用涂料卷，北京：中国标准出版社，2007.[4]涂料与颜料标准汇编：涂料试验方法涂膜性能卷，北京：中国标准出版社，2007.  \n\n[5]涂料与颜料标准汇编：涂料试验方法液体和施工性能卷，北京：中国标准出版社，2007.  \n[6] 涂料与颜料标准汇编：涂料试验方法通用卷，北京：中国标准出版社，2007.  \n[7] 涂料与颜料标准汇编：颜料产品和试验方法涂膜性能卷，北京：中国标准出版社，2007.  \n[8] Annual Book of ASTM Standards: Part 27. 2006.  \n[9] 日本规格协会．JIS涂料．1987.  \n[10] ZenoW．威克斯等著．有机涂料科学与技术．经良等译．北京：化学工业出版社，2002.  \n[11] 虞莹莹主编．涂料工业用检验方法与仪器大全，北京：化学工业出版社，2007.  \n\n第五篇",
+        "category": " References"
+    },
+    {
+        "id": 1341,
+        "chunk": "# 第一章",
+        "category": " Introduction"
+    },
+    {
+        "id": 1342,
+        "chunk": "# 涂料涂装一体化的概念  \n\n前边的章节对不同类型的涂料做了非常详细的描述。无论是哪一种涂料，在某种意义上说都还只是一种半成品，它们或者是含有大量溶剂的液状物，或者是尚未发生交联反应的分离组分。这些半成品只有通过适当的工艺过程涂布在被涂物表面后，经历溶剂挥发、漆基交联等过程，形成网状涂膜后才能真正发挥涂料的保护、装饰、特殊功能等作用。这个把涂料变成涂膜的过程就是涂装。涂层质量的好坏不仅与涂料本身的质量相关，而且很大程度上取决于涂装的质量水平。  \n\n长期以来我国的涂料领域存在着涂料和涂装分离、重涂料开发轻涂装研究的问题。新中国成立以来，我国的涂料行业由于有天津灯塔、上海开林等几大涂料集团的支撑，涂料研发人员具有相当的理论知识水平，但是涂装技术的研究一直不是很系统，往往是游离于涂料行业之外，一般在造船、汽车制造等行业的大厂有涂装公司，但也只是停留在使用技能的研究阶段，而涂料制造商一般也很少进行涂料施工方面的研究。改革开放以来，随着国际知名企业进入我国，在汽车、集装箱、船舶、卷钢等领域也将涂料涂装一体化的先进概念带入我国。所谓涂料涂装一体化的概念，就是涂料商不仅仅负责涂料的研发和生产销售，同时还负责为客户设计涂料涂装配套方案，设计涂装施工工艺，甚至派工程师在涂装现场指导施工。按照现代的管理理念，这些涂料实体产品以外的服务和活动是整体产品的一部分，因此在跨国涂料公司，为客户进行的涂装设计、现场管理和指导等工作都是免费的，或者说是包含在整体产品价格之内的。近年来在家装行业更出现了内墙乳胶漆免费涂装的产品销售方式，事实上实现了以涂膜代替涂料作为产品销售的革命。  \n\n本章为涂料行业的从业人员简要介绍一些涂料专业技术知识以外的涂料涂装一体化知识，主要侧重于涂装设计。具体的专业知识，如表面处理方法和涂装方法等，将在后续章节介绍。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1343,
+        "chunk": "# 第一节 涂装配套设计  \n\n在涂料涂装一体化体系中，涂装配套设计是涂料使用之前必须要做的首要工作，它往往  \n\n是被涂物设计规范的一部分。由于专业分工的要求，涂料研究人员往往需要为客户提供涂装配套设计工作。这里所说的涂装配套（coating system），通常主要包括涂料品种、底材处理和涂装工艺三个部分。  \n\n对于汽车、集装箱、船舶等大量工业化生产的产品，其行业内一般都有现成的与涂装配套相关的标准。对涂料公司的涂装设计人员来说，需要面对的往往是一些具体的项目，如各类工业项目的涂装配套设计，钢结构防腐涂装配套的设计等。  \n\n涂装配套设计时往往要关注涂膜的使用环境、涂膜使用寿命、涂料的特性、涂装方法选择、底材处理方法等，另外还要考虑经济和安全条件的限制。涂装设计师要考虑的各种因素可以参考图5-1-1。  \n\n![](images/2fec9870f97b48572b67f30baea2a6c68b787e4ac5d2474f2f0e263b1a62c986.jpg)  \n图5-1-1 涂装设计的参考因素",
+        "category": " Introduction"
+    },
+    {
+        "id": 1344,
+        "chunk": "# 一、涂膜使用环境分析  \n\n在设计涂装配套前，必须要详细了解被涂物本身的特性、所处的环境和接触的介质等。例如钢结构一般会暴露在不同的大气环境中，可能包括室内环境、一般的户外环境、严重腐蚀的环境等。汽车通常会在户外使用，既要考虑阳光曝晒、雨水侵蚀、砂石冲击等对漆膜的防护性能的破坏，又要考虑这些因素对漆膜的颜色、光泽等装饰性因素的影响。而飞机除了考虑耐候性、耐磨性、硬度、柔韧性等，温度的大幅度变化也是涂装配套设计的最主要环境因素。在充分了解了这些可能对被涂物造成腐蚀或破坏以及可能导致涂膜早期劣化的因素后，方可设计出符合被涂物使用要求的涂装配套。目前，很多行业都对其被涂物所处的环境作了分类总结并形成了标准。例如，ISO12944就对钢结构所处的腐蚀环境系统进行了详细的分类。一般情况下，导致钢结构产生腐蚀的环境因素主要有大气、水和土壤等。ISO12944-2定义了大气腐蚀环境的级别以及钢结构在水下和埋地时腐蚀环境的分类（表5-1-1和表5-1-2）关于ISO12944的详细介绍见第三篇第三章第三节。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1345,
+        "chunk": "# 二、经济性分析  \n\n和设计任何产品一样，涂装配套的设计也是各方面因素的平衡。通常，设计质量好的涂装配套和设计价格低廉的涂装配套都不是很难的事，但是设计一个既好又便宜的涂装配套就需要平衡各种因素。一般来说，满足最基本的保护功能是设计涂装配套时要考虑的首要因素，在这个前提的基础上，才可以考虑如何降低成本。涂装配套的成本包括很多方面，设计时既要考虑涂料自身的成本，同时也要考虑底材处理、涂装方法甚至工期等各方面的成本。  \n\n例如，对于在工厂内的大批量生产，采用喷射底材处理、标准的涂层组合以及无空气喷涂的施工方法可能是最经济的，但是如果是同样的被涂物在没有动力源的野外进行涂装，采用简单的打磨处理，用对底材处理要求较低的带锈涂料和刷涂方法可能反而是比较经济的。  \n\n表5-1-1IS012944规定的大气环境腐蚀级别  \n\n\n<html><body><table><tr><td rowspan=\"3\">腐蚀 类型</td><td colspan=\"4\">单位面积上腐蚀产生的质量损失</td><td colspan=\"2\">温性气候下的典型环境</td></tr><tr><td colspan=\"2\">低碳钢</td><td colspan=\"2\">锌</td><td rowspan=\"2\">外部</td><td rowspan=\"2\">内部</td></tr><tr><td>质量 损失 /(g/m²)</td><td>厚度 损失 /μm</td><td>质量 损失 /（g/m²）</td><td>厚度 损失 /μm</td></tr><tr><td>C1 很低</td><td>≤10</td><td>≤1.3</td><td>≤0.7</td><td>≤0.1</td><td></td><td>有供热装置的建筑物内部， 空气洁净，如商场、学校、宾 馆等</td></tr><tr><td>C2 低</td><td>10~200</td><td>1.3~25</td><td>0.7~5</td><td>0.1~0.7</td><td>大气污染程度较低的农 村、田园地区</td><td>无供热装置的建筑物内部， 可能产生结露，如库房、体育 馆等</td></tr><tr><td>C3 中</td><td>200~400</td><td>25~50</td><td>5~15</td><td>0.7~2.1</td><td>城市和工业大气环境， 中等二氧化硫污染，低盐 度沿海地区</td><td>高湿度和有污染空气的生 产场所，如食品加工厂、洗衣 场、酿酒厂、奶品厂等</td></tr><tr><td>C4 高</td><td>400～650</td><td>50~80</td><td>15~30</td><td>2.1~4.2</td><td>高盐度的工业区和沿海 地区</td><td>化工厂、游泳池、造船厂和 沿海航行的船舶等</td></tr><tr><td>C5-I 很高 (工业)</td><td>650～1500</td><td>80~200</td><td>30~60</td><td>4.2~8.4</td><td>高盐度和恶劣大气环境 的工业区域</td><td>长期处于高湿度高污染环 境的建筑物等</td></tr><tr><td>C5-M 很高 (海洋)</td><td>650～1500</td><td>80~200</td><td>30～60</td><td>4.2~8.4</td><td>高盐度环境的沿海设施 和海上平台</td><td>长期处于高湿度高污染环 境的建筑物等</td></tr></table></body></html>  \n\n表5-1-2ISO12944规定的水和埋地环境腐蚀级别  \n水和土壤的腐蚀分类  \n\n\n<html><body><table><tr><td>分类</td><td>环境</td><td>环境和结构实例</td></tr><tr><td>Im1</td><td>淡水</td><td rowspan=\"2\">河流上安装的结构，如水力发电站</td></tr><tr><td>Im2</td><td>海水、盐水</td><td>港口、海边的结构，如闸门、防波堤；海上的平台结构</td></tr><tr><td>Im3</td><td>土壤</td><td>埋地贮罐、钢桩和管道</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1346,
+        "chunk": "# 三、表面处理的类型和方法的选择  \n\n底材的表面处理对涂膜性能的发挥至关重要，因此在涂装设计时必须选定适当的表面处理方法。后续章节将详细介绍各种底材的表面处理方法。在用涂料被覆的材料中，使用最多的底材是钢材，如汽车、船舶等都会使用各种规格的钢材。钢材的表面处理方式有酸洗、磷化等化学处理法和喷射、打磨等物理方法，还有火焰处理、高压水处理等其他方法，各种处理方法都有各自的特点和使用对象，很难说哪一种表面处理方法是最好的。在设计涂装配套时要针对被涂物的种类、使用环境及使用的涂料品种等因素综合考虑，选择合适的处理方法。如船舶集装箱等采用比较厚的钢板，通常采用喷砂和抛丸处理，而对于汽车上的薄板部件，则要使用磷化等方法进行处理。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1347,
+        "chunk": "# 四、涂料的选择  \n\n涂料是涂装配套的主体，可以说是涂装配套中最主要的部分，根据不同的使用环境，涂料可以分为防腐涂料、装饰涂料和功能涂料等，但是这种分类不是绝对的，有些涂装配套系统往往兼具防腐和装饰的功能。  \n\n为了发挥防腐和装饰等功能，涂装配套系统往往由多道涂膜组合在一起，形成一个整体体系，这也就是所谓的“配套系统”的意义所在。各道涂层在整个体系中发挥着不同的作用，一般的涂层系统往往包括底漆、腻子、中间漆、面漆等。另外还有一些特殊涂料如粉末涂料等，在施工中只采用单层涂装。选择各涂层的涂料时应该参考以下原则。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1348,
+        "chunk": "# 1.底漆  \n\n底漆是整个涂层的基础，它的主要作用是为整个涂层提供防腐性和对底材的附着力。底漆的涂装质量对涂装系统的防腐效果和使用寿命至关重要。选择底漆时应考虑以下因素。  \n\n$\\textcircled{1}$ 底漆应对底材和下一道涂料都要有良好的附着力。通常采用基料中含有羟基、羧基等极性基团的醇酸、环氧类涂料作为底漆。$\\textcircled{2}$ 防腐底漆应具有良好的屏蔽性。对屏蔽性要求较高的涂层体系，在设计底漆时要选用含有片状颜料的涂料，这是因为片状颜料能切断涂层中的毛细孔，延长腐蚀介质的通过路径，从而屏蔽水、氧和离子等腐蚀因子透过。$\\textcircled{3}$ 底漆中应含较多的颜料、填料，以增加表面粗糙度，增加与中间漆或面漆的层间密合；同时降低底漆的收缩率，减少因为溶剂挥发及树脂交联固化反应产生体积收缩而使涂膜附着力降低。$\\textcircled{4}$ 底漆对底材表面应有良好的润湿性。在混凝土及木材等非金属底材上要选择能对底材表面透入较深、以利于涂层对底材锚固的底漆。$\\textcircled{5}$ 对于特殊底材（如铝、锌等）应选用含有缓蚀颜料和附着力增强剂的功能性底漆。$\\textcircled{6}$ 对于严酷的腐蚀环境往往要使用富含锌、铝等活泼金属粉末的牺牲阳极底漆，以加强防腐功能并阻止因外力破坏损伤涂膜后腐蚀的进一步扩散。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1349,
+        "chunk": "# 2.腻子  \n\n有些被涂物即使涂过底漆以后，其表面也有可能因为加工的原因留有裂缝、孔隙和凹凸等造成的不平整，需要先用腻子找平。腻子可以看成是PVC值很高的涂料，具有很好的厚涂性，但是由于成膜物较少，有弹性差、易开裂、防护性能差等缺点，往往会降低整个涂层配套系统的性能，因此如果加工条件允许的话，应尽量通过提高被涂物的原始外观并配合选用合适的中间漆来提高涂层的装饰性，尽量避免使用腻子。选择腻子时要考虑以下因素。  \n\n$\\textcircled{1}$ 腻子要与底漆相容，并对底漆和下一道涂层均有良好的附着力。  \n\n$\\textcircled{2}$ 对于要一次涂装比较厚的腻子，应有较高的固体分，否则腻子干燥后会因为体积收缩过大造成塌陷。$\\textcircled{3}$ 腻子的收缩率等指标要尽量和相关涂层接近，以避免产生收缩过度和开裂等弊病。$\\textcircled{4}$ 腻子要便于施工和打磨，一般腻子的硬度不能高于底漆的硬度，否则打磨时会过度伤害底漆。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1350,
+        "chunk": "# 3.中间漆  \n\n中间漆对底漆和面漆起着承上启下的作用，它的主要作用是提高涂膜的厚度和平整度，从而强化整个涂装配套体系的防腐和装饰性能。选择中间漆时要考虑如下原则。  \n\n$\\textcircled{1}$ 中间漆应对底漆和面漆都有良好的附着力。有些底漆表面往往不能直接覆涂面漆，如锌粉漆表面直接涂装含有醇酸树脂的面漆会因酸性成膜物和锌粉反应生成皂类而造成早期剥落，此时一定要设计一层对底漆和面漆都有较好附着力的环氧类中间漆将底漆和面漆隔离开。  \n\n②中间漆应采用厚涂型涂料，以增加涂层的总体厚度，提高整个涂层的防腐性能。涂层的防腐性能有时依赖于整个涂层系统的总体膜厚，有些功能性底漆无法涂得太厚，而面漆的成本又相对较高，所以合理使用中间漆，既可以保证整体膜厚又可以减少面漆的用量，降低配套成本。  \n\n$\\textcircled{3}$ 有些特殊功能可以通过中间漆来实现，如桥梁构件在工厂制造好以后有时候需要半年以上才能到现场安装完毕并涂装面漆，对于这类涂装间隔要求较长的涂装配套应采用没有涂装间隔要求的环氧云母氧化铁中间漆，来避免涂装面漆前大量的中间漆涂层的拉毛和清理工作。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1351,
+        "chunk": "# 4.面漆  \n\n面漆的主要作用是装饰，有的还兼具一些防腐保护功能。由于面漆的成本较高，通常设计的膜厚较低。设计面漆时应考虑以下原则。  \n\n$\\textcircled{1}$ 面漆应具有较好的耐候性，如抗失光、抗粉化、变色程度小等。不同品种的面漆的耐候性主要与所采用的树脂中的化学键的键能高低有关，在耐候性要求高的场合，应该选用氟碳、有机硅和聚氨酯等类型的面漆。另外有些面漆还可以通过添加铝粉、云母氧化铁等阻隔阳光的颜料，来延长涂膜的使用寿命。  \n\n$\\textcircled{2}$ 面漆还需要具备一定的防护作用，如在化工污染较为严重的区域，要求面漆能抵抗一定程度的酸碱腐蚀。对在沿海地区使用的涂装系统，还需要面漆能抵御海洋环境特有的严酷腐蚀条件并有较好的抗离子渗透能力。  \n\n$\\textcircled{3}$ 面漆应具有较好的装饰性，并可通过其色彩、光泽、图纹等的变换来快速改进环境的装饰效果。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1352,
+        "chunk": "# 五、涂膜期待使用寿命分析  \n\n在选择涂料时，涂膜的使用年限是非常重要的参考因素，由于被涂物建造条件的限制，有的可以随时进行涂膜维护，有的则永远不可能进行维护，因此对涂膜系统的使用年限要求是不同的。ISO12944标准中将钢结构的涂膜使用寿命分为L、M、H（低、中、高）三个级别，分别为5年、10年和15年，但是要注意，这里所说的涂膜使用寿命只是一个技术参数，是设计涂装配套和对涂膜进行维修和换涂的依据，而往往并非涂膜的担保使用年限。对于不同的使用年限，在选定涂料时不仅要考虑涂料的品种，还要考虑其膜厚以及不同种涂料的搭配。因此，常常会出现同一个建筑物的不同部位采用不同的涂膜系统的情况，例如海上钻井平台，其甲板平台和生活区部位由于维修方便可以使用相对比较廉价而涂膜使用寿命不是很长的涂层组合，在飞溅区和水下部位，由于防腐要求苛刻且维修困难，就要使用涂膜寿命年限较长的重防腐涂层组合，而对于钢管桩等无法维护的埋地部位，则往往采用永久或半永久的涂层组合，很多时候还需要同时采用涂料以外的其他防腐措施，见表5-1-3。  \n\n表5-1-3海上钻井平台不同部位的涂膜组合  \n\n\n<html><body><table><tr><td>部位</td><td>期待使用年限/年</td><td>涂膜组合/μm</td></tr><tr><td>甲板和居住区</td><td>2~5</td><td>环氧漆 50 丙烯酸面漆 40</td></tr><tr><td>飞溅区</td><td>10</td><td>耐磨环氧漆 300 聚氨酯面漆 60</td></tr><tr><td>海底埋地区</td><td>15以上</td><td>焦油环氧漆 450</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1353,
+        "chunk": "# 六、涂装配套的选定  \n\n在充分分析了被涂物的使用环境、期待使用寿命以及被涂物的使用特点和成本因素后，方可以决定使用哪种涂装配套。针对不同的设计要求，可以有多种涂装配套可供选择，当然这些配套往往会各自在某些方面有些侧重，有的防腐效果相对好一些，有的装饰效果好一些，有的则成本低一些。设计配套时要满足使用方的要求，当然也常常体现设计者的风格。  \n\n现在对于大多数的被涂物和使用条件，相关的标准或设计手册中都有对应的涂装配套方案，进行设计时可以在参考这些方案的基础上，再结合项目的具体情况，制定出更加合理的配套方案。  \n\n表5-1-4是ISO12944中推荐的可以用于C4腐蚀环境的、使用各种涂料品种的涂装配套。C4腐蚀环境是指高盐度的工业区和沿海地区以及诸如化工厂、游泳池、造船厂和沿海航行的船舶等所处的腐蚀环境，这是一种比较苛刻的腐蚀环境。从表5-1-4中可以看出，对应这种配套的底材处理都要求达到 $\\mathbf{S}\\mathbf{a}2\\frac{\\mathbb{1}}{\\mathbb{2}}$ 级，不推荐St等底材处理方式。  \n\n表5-1-4ISO12944推荐用于C4腐蚀环境的各种涂装配套  \n\n\n<html><body><table><tr><td rowspan=\"2\">配套 编号</td><td colspan=\"2\">表面处理 等级</td><td colspan=\"4\">底漆</td><td colspan=\"3\">面漆(包括中间漆）</td><td colspan=\"2\">涂装系统</td><td colspan=\"3\">期待寿命 ISO 12944-1</td></tr><tr><td>St 2</td><td>2 Sa2</td><td rowspan=\"9\">所用树脂</td><td rowspan=\"9\"></td><td>种类</td><td>膜厚</td><td></td><td>树脂</td><td>道数</td><td>膜厚</td><td>总膜</td><td>L</td><td>M</td><td>H</td></tr><tr><td></td><td></td><td rowspan=\"7\"></td><td>道数</td><td>80</td><td>醇酸</td><td>2~3</td><td>120</td><td>道遵邀 3~5</td><td>200</td><td></td><td></td><td></td></tr><tr><td>S4,01</td><td>X X</td><td></td><td>1~2 1~2</td><td>80</td><td>2</td><td></td><td>3~4</td><td>240</td><td></td><td></td><td></td></tr><tr><td>S4,02</td><td>X</td><td>醇酸</td><td>1~2</td><td>80</td><td rowspan=\"2\">沥青</td><td>2~3</td><td>160 200</td><td>3~5</td><td>280</td><td></td><td></td><td></td></tr><tr><td>S4,03</td><td></td><td></td><td></td><td rowspan=\"2\">丙烯酸， 氯化橡胶，</td><td>2~3</td><td>120</td><td>3~5</td><td>200</td><td></td><td></td><td></td></tr><tr><td>S4,04</td><td>X</td><td>1~2</td><td>80</td><td rowspan=\"2\">聚氯乙烯</td><td></td><td></td><td>240</td><td></td><td></td><td></td></tr><tr><td>S4,05</td><td>X</td><td>1~2</td><td>80</td><td>2~3</td><td>160</td><td>3~5 3~4 240</td><td></td><td></td><td></td></tr><tr><td>S4,06</td><td></td><td>X 丙烯酸， X</td><td>1~2</td><td>80 80</td><td>沥青</td><td>2 2~3</td><td>160 200</td><td>3~5</td><td></td><td></td><td></td></tr><tr><td>S4,07</td><td></td><td rowspan=\"7\">X X</td><td>氯化橡胶， 聚氯乙烯</td><td rowspan=\"7\">Misc</td><td>1~2 1~2</td><td>80 80</td><td rowspan=\"7\"></td><td>2~3</td><td></td><td>280 200</td><td></td><td></td><td rowspan=\"2\"></td></tr><tr><td>S4,08</td><td></td><td></td><td></td><td>丙烯酸，</td><td>120 160</td><td>3~5 3~5</td><td>240</td><td></td></tr><tr><td>S4,09</td><td></td><td></td><td>1~2</td><td>氯化橡胶， 160</td><td>2~3</td><td></td><td>2 200</td><td></td><td></td><td></td></tr><tr><td>S4,10</td><td>X</td><td></td><td>1</td><td>聚氯乙烯 160</td><td>1</td><td>40</td><td>2</td><td></td><td></td><td></td></tr><tr><td>S4.11</td><td>X</td><td></td><td>1</td><td></td><td>1</td><td>120</td><td>280</td><td></td><td></td><td></td></tr><tr><td>S4,12</td><td>X X</td><td></td><td>1~2 80</td><td>环氧，聚</td><td>2~3 120</td><td>3~5</td><td>200</td><td></td><td></td><td></td></tr><tr><td>S4,13</td><td></td><td>环氧</td><td>1~2</td><td>80 氨酯</td><td>2~3</td><td>160</td><td>3~5 3~5</td><td>240 280</td><td></td><td></td></tr><tr><td>S4,14</td><td></td><td rowspan=\"9\">X</td><td rowspan=\"9\">环氧，聚 氨酯</td><td rowspan=\"9\"></td><td>1~2</td><td>80 80</td><td rowspan=\"4\">丙烯酸，</td><td>2~3</td><td>200 240</td><td>4~6</td><td>320</td><td></td><td rowspan=\"2\"></td></tr><tr><td>S4,15</td><td>X</td><td>1~2</td><td></td><td>3~4 1~2</td><td>120</td><td></td><td></td><td></td></tr><tr><td>S4,16</td><td>X</td><td>1</td><td>40</td><td>氯化橡胶，</td><td></td><td>2~3 3~4</td><td>160 200</td><td></td><td></td></tr><tr><td>S4,17 S4,18</td><td>X X</td><td>1 1</td><td>40 40</td><td>2~3 2~3</td><td>160 200</td><td>3~4</td><td>240</td><td></td><td></td></tr><tr><td>S4,19</td><td>X</td><td></td><td></td><td rowspan=\"5\"></td><td>环氧，聚</td><td>120</td><td>2~3</td><td>160</td><td></td><td></td></tr><tr><td>S4,20</td><td></td><td>1 1</td><td>40 40</td><td>1~2 2~3</td><td>160</td><td>3~4 200</td><td></td><td></td><td></td></tr><tr><td>S4,21</td><td>X</td><td>1</td><td>40</td><td>2~3</td><td>200</td><td>3~4</td><td>240</td><td></td><td></td></tr><tr><td>S4,22</td><td>X X</td><td>1</td><td>氨酯 40</td><td>2~3</td><td>240</td><td>3~4 280</td><td></td><td></td><td></td></tr><tr><td>S4,23</td><td></td><td>Zn(R)</td><td>1</td><td></td><td>3~4</td><td>280</td><td>4~5 320</td><td></td><td></td></tr><tr><td>S4,24</td><td>X X</td><td rowspan=\"9\">ESI</td><td rowspan=\"9\"></td><td rowspan=\"9\"></td><td>１</td><td>80</td><td rowspan=\"3\">丙烯酸， 环氧，聚</td><td></td><td></td><td>1 80</td><td></td><td></td><td></td></tr><tr><td>S4,25</td><td>X</td><td>1</td><td>80</td><td>1~2</td><td>80</td><td>2~3</td><td>160</td><td></td><td></td></tr><tr><td>S4,26</td><td></td><td>1</td><td>氯化橡胶， 聚氯乙烯</td><td>2~3</td><td>120</td><td>3~4 200</td><td></td><td></td><td></td></tr><tr><td>S4,27</td><td>X</td><td>１</td><td>80</td><td>2~3</td><td>160</td><td>3~4</td><td>240</td><td></td><td></td></tr><tr><td>S4,28</td><td>X</td><td>1</td><td>80</td><td>1~2</td><td>80</td><td>2~3</td><td>160</td><td></td><td></td></tr><tr><td>S4,29</td><td>X</td><td>1</td><td>80</td><td>2~3</td><td>120</td><td>3~4</td><td>200</td><td></td><td></td></tr><tr><td>S4,30</td><td>X</td><td>１</td><td>80</td><td>2~3</td><td>160</td><td>3~4</td><td>240</td><td></td><td></td></tr><tr><td>S4,31</td><td>X</td><td>1 1</td><td>80 氨酯 80</td><td>2~3 3--4</td><td>200 200</td><td>3~4</td><td>280</td></table></body></html>\n\n注：阴影部分表示该配套推荐用于此防腐类型。  \n\n对于相同的H级（15年）的涂膜使用寿命，可以在表5-1-4中查到S4，03/S4，07/S4，11/S4，18/S4，21/S4，22等多个配套，如 S4，22便可以细化成表5-1-5的形式，这个配套适用于对防腐和装饰要求都比较高的场合。当然也可以细化成表5-1-6的形式，它适用于只要求防腐性而不要求装饰性的场合，如钢箱梁等的内表面。  \n\n表5-1-5 细化的S4，23配套  \n\n\n<html><body><table><tr><td>项目名称</td><td colspan=\"3\">C4环境下钢结构防腐涂装配套</td></tr><tr><td>使用条件</td><td colspan=\"3\">高盐度的工业区和沿海地区以及化工厂、游泳池、造船厂和沿海航行的船舶等腐蚀环境</td></tr><tr><td>涂膜使用寿命/年</td><td colspan=\"3\">15</td></tr><tr><td>底材处理方式 涂料类型</td><td>涂膜厚度/μm</td><td>Sa2 道数/道</td><td>每层膜厚/μm</td></tr><tr><td>环氧富锌底漆</td><td>40</td><td>1</td><td>40</td></tr><tr><td>厚涂环氧漆</td><td>90</td><td>2</td><td>180</td></tr><tr><td>聚氨酯面漆</td><td>60</td><td>1</td><td>60</td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td>总膜厚</td><td></td><td></td><td>280</td></tr></table></body></html>  \n\n表5-1-6细化的S4，22配套（用于没有装饰性要求的场合）  \n\n\n<html><body><table><tr><td>项目名称</td><td colspan=\"3\">C4环境下钢结构防腐涂装配套</td></tr><tr><td>使用条件</td><td colspan=\"3\">高盐度的工业区和沿海地区以及化工厂、游泳池、造船厂和沿海航行的船舶等腐蚀环境</td></tr><tr><td>涂膜使用寿命/年 底材处理方式</td><td colspan=\"3\">15</td></tr><tr><td>涂料类型</td><td>涂膜厚度/μm</td><td>Sa2 道数/道</td><td>每层膜厚/μm</td></tr><tr><td>环氧富锌底漆 厚涂环氧漆</td><td>40 120</td><td>1 2</td><td>40</td></tr><tr><td>总膜厚</td><td></td><td></td><td>240 280</td></tr></table></body></html>  \n\n![](images/f2430226b2cfe4537d238a879e2a24d13dcb1184f0528f8827f8a794583bc236.jpg)  \n\n施工工艺是涂料供应商向涂料使用单位提供的或者是两者共同制定的施工指南，是在涂装配套基础之上对施工过程的要求和注意事项的详细描述，对充分发挥涂料和整个涂层系统的性能、保证涂料的正确使用具有重要的意义。涂装工艺通常包括以下部分。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1354,
+        "chunk": "# 一、表面处理要求及注意事项  \n\n表面处理的方式通常在涂装配套中已经有明确的要求和描述，在涂装工艺指导书中，除了要规定涂装配套中要求的底材处理的等级以外，通常还会根据需要规定一些更详细的技术指标，如底材处理的粗糙度、磨料的尺寸、洗液的pH、磷化膜的重量等，以及底材处理作业时对环境条件的温湿度要求等。  \n\n很多情况下处理后的底材在涂装之前还要经过焊接等加工工序，往往会对已经处理过的底材造成破坏，因此施工工艺中还需对焊道等加工部位规定二次底材处理的方法和控制指标。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1355,
+        "chunk": "# 二、涂装方法的选择  \n\n选择什么样的涂装方法是首先要明确的。涂装工艺中一般要规定整体的涂装方法和局部  \n\n的涂装方法，例如船舶的大部分部位要求使用无空气喷涂，预涂和一些复杂的、难以涂装的部位则允许采用刷涂和辊涂等方法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1356,
+        "chunk": "# 三、涂料的准备  \n\n在施工工艺中应明确涂料的配比、开罐容器中状态的确认、混合揽拌方法、稀释比例等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1357,
+        "chunk": "# 四、涂装过程的要求  \n\n涂装过程中首先必须要明确对环境条件的要求，在对金属底材上喷涂通用涂料时，一般规定环境温度应该高于露点温度 $3^{\\circ}C$ 以上，环境湿度应低于 $80\\%$ 。对于在室内涂装的，应规定施工时的温度、湿度、照明、通风等控制参数；对于在室外涂装的，还应该规定风速、灰尘等的控制指标。同时要明确禁止进行涂装作业的天气条件，如下雨、风速过大、湿度过高，温度过高或过低等。  \n\n一般还要对涂装过程中的其他注意事项加以说明，如涂装间隔的管理、涂料混合使用期的控制、涂装流水线的速度、强制干燥的条件等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1358,
+        "chunk": "# 五、涂膜检验  \n\n涂装完成后，涂膜的检查和验收是一项非常重要的工作，它是判断整个涂装工作是否符合要求以及可否进人下一道工序的依据。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1359,
+        "chunk": "# 1.涂膜厚度检验  \n\n涂膜厚度是涂膜检验中最重要的工作，在涂装工艺中要规定涂膜厚度的检验方法和使用的仪器。通常要求在涂装施工过程中应经常检测湿膜厚度，虽然湿膜厚度不是判断漆膜合格的依据，但它是控制干膜厚度的重要方法。待涂层干燥后，应再次检测干膜厚度，以保证膜厚符合规定要求。目前金属底材的干膜厚度检测主要采用电磁式测厚仪，非金属底材可以采用千分尺等测厚仪。对于多道涂层的配套，由于通常都不会在涂层完全干燥后涂装下一道涂层，因此一般不单独检测各涂层的膜厚，而是在完工后检测全部涂层的总厚度。当有特殊要求时，可以用特殊的检测设备分别检测完工后各层涂膜的厚度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1360,
+        "chunk": "# 2.涂层厚度是否合格的判定标准  \n\n涂装工艺中必须规定涂膜厚度是否合格的判定标准。物件本身的构造、涂喷工作的管理情况、涂装操作人员的素质等都可能造成涂层厚薄不均，因此，如果要百分之百地保证全部涂层都超过规定厚度，不但会大大增加涂料的用量，实际上也难以实现，通常按干燥涂层厚度测定值的分布状态来判断整个涂层是否合乎标准。例如：某些行业接受双90原则，即所有测定点的膜厚值不得低于规定厚度的 $90\\%$ 。达到规定厚度的测量点数目应超过测量点总数的 $90\\%$ 0",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1361,
+        "chunk": "# 3.涂膜质量检验  \n\n涂膜质量的检验主要是判别漆膜是否有严重影响涂膜使用功能的漆病。涂装工艺中一般要规定哪些漆病是不允许的，并规定出现这些漆病的处理原则。例如，对于汽车漆膜来说，表面轻微的橘皮也是不允许的，必须要修补或返工，但是这种漆病对集装箱和船舶的涂膜来说则往往是无足轻重的。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1362,
+        "chunk": "# 六、安全注意事项  \n\n涂料的施工过程存在各种安全隐患，溶剂型涂料都是易燃易爆的，有的涂装工作是高空作业，涂料本身对人的身体也会产生伤害，因此要求在涂料施工工艺中必须根据所使用涂料和施工方法的特点明确安全注意事项。这些安全注意事项通常要包括对脚手架的要求、防火要求、安全卫生要求以及意外事故的应急处理措施等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1363,
+        "chunk": "# 七、涂装工艺指导书举例  \n\n下面举一个一般钢结构的涂装施工工艺指导书的例子，可以作为涂装工艺设计的参考。一般通用钢结构涂装工艺指导书",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1364,
+        "chunk": "# 1.结构处理  \n\n在进行表面处理前，应对钢材表面缺陷进行处理，包括：  \n\n$\\textcircled{1}$ 钢材边沿的飞边毛刺和瓦斯切割面应打磨光顺；  \n$\\textcircled{2}$ 去除飞溅、焊渣等；  \n$\\textcircled{3}$ 凹坑、夹层等钢材表面缺陷要用砂轮或电焊补平的方法进行修整；  \n$\\textcircled{4}$ 焊缝接头、咬边、凸出处要打磨光顺；  \n$\\textcircled{5}$ 彻底清除钢材表面的酸、碱、盐和油脂等污染物。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1365,
+        "chunk": "# 2.脚手架  \n\n脚手架应搭设在坚固、满足安全要求的基础之上，并应便于进行表面处理、涂料施工、检查验收等工作。脚手架层间距离以 $1,8\\sim2.0\\mathrm{m}$ 为宜；脚手架与被涂物不应有触碰处，且边缘与被涂物间的距离最好大于 $10\\mathrm{{cm}}$ ；脚手架应选择不受喷射处理影响、不易积聚磨料和灰尘等杂质，易于清洁、质轻易搬运的材料；脚手架端须安装胶套，以免拆除时碰坏涂膜；脚手架管两端应封堵，以免积留磨料和灰尘。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1366,
+        "chunk": "# 3.表面处理  \n\n主要部件或主要设备表面除锈等级必须达到ISO $\\mathrm{Sa}2\\frac{1}{2}$ 级。辅助部件或设备表面除锈等级必须达到ISOSa2级或ISOSt3级。  \n\n喷射除锈标准ISO $\\mathrm{Sa2}$ 级的要求如下：在不放大的情况下进行观察，表面应无可见油脂和油垢，并且几乎没有氧化皮、铁锈、涂料涂层和异物。任何残留物都应该是牢固附着的。  \n\n喷射除锈标准ISO $\\mathbf{Sa}2\\frac{1}{2}$ 的要求如下：达到近乎白色金属的清洁度，在不放大的情况下进行观察，表面应无可见油脂和油垢，并无氧化皮、铁锈、涂料涂层和异物。任何残留的痕迹应仅为点状或条状的轻微色斑。  \n\nISOSt3级的要求如下：非常彻底的手工和动力工具清理，在不放大的情况下进行观察，表面应无可见的油脂和污垢，并且没有附着的氧化皮、铁锈、涂料涂层和异物。表面应具有金属底材的光泽。  \n\n表面处理时的要求如下。  \n\n$\\textcircled{1}$ 使用的磨料应经过盐分、干燥和油污等测试，并且符合要求。$\\textcircled{2}$ 压缩空气应经过油水分离器去除水分和油污。$\\textcircled{3}$ 喷射处理后钢板表面的粗糙度范围应在 $30\\mathrm{\\sim}80\\mu\\mathrm{m}$ $\\textcircled{4}$ 喷射及检验期间，环境空气相对湿度应低于 $50\\%$  \n\n$\\textcircled{5}$ 喷涂前应用真空吸尘器吸净被喷射物和灰尘，特别是被涂表面和脚手板上不应有残留的灰尘。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1367,
+        "chunk": "# 4.预涂  \n\n涂装每一道涂料前都应对全部焊缝及不易喷涂的区域进行预涂。  \n\n5.施工  \n\n$\\textcircled{1}$ 涂装方式采用高压无气喷涂，并使用产品说明书中规定的喷嘴。  \n$\\textcircled{2}$ 漆膜表面应平整、光洁，不应有流挂、针孔等涂膜缺陷。  \n$\\textcircled{3}$ 喷涂时，环境相对湿度应低于 $80\\%$ ，钢板温度应高于露点 $3^{\\circ}C$ 中$\\textcircled{4}$ 在喷涂作业期间，底材温度应控制在 $50^{\\circ}C$ 以下。  \n$\\textcircled{5}$ 涂装作业时应严格遵守产品说明书规定的涂装间隔。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1368,
+        "chunk": "# 6.检验及验收  \n\n最终涂膜厚度检验应在涂料干燥后进行，干膜厚度的测定应保证至少每 $5\\mathbf{m}^{2}$ 测一点，焊缝周围 $\\mathbf{100mm}$ 范围内不测量。  \n\n所测量的干膜厚度值不得低于规定膜厚的 $90\\%$ ，未达到规定膜厚的点数不能超过总测量点数的 $10\\%$ 。对低于规定膜厚的测量点附近区域应进行修补，以达到规定膜厚。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1369,
+        "chunk": "# 7.涂膜修补  \n\n被破坏但没有露出底材的涂膜可采用动力工具打磨处理，打磨边缘应有坡度，打磨后补涂相应的涂料。  \n\n被破坏且已经露出底材的涂膜，当其面积小于 $0.\\ 02\\mathrm{m}^{2}$ 时可以采用动力工具打磨，打磨边缘应有坡度，打磨后补涂相应的涂料。当漆膜损坏面积大于 $0.02\\mathrm{m}^{2}$ 时，应对缺陷部位进行喷射处理，破坏区域的边缘应用动力工具打磨出坡度，并按涂装配套补涂相应的涂料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1370,
+        "chunk": "# 8.安全措施  \n\n在涂料施工中的任何操作均应遵守以下安全措施。  \n\n$\\textcircled{1}$ 施工现场应保证良好的通风。  \n$\\textcircled{2}$ 涂料含有可燃物质，施工时要远离火源并禁止在邻近地区吸烟。  \n$\\textcircled{3}$ 应避免涂料接触皮肤和眼睛。  \n$\\textcircled{4}$ 如果涂料接触到皮肤，应用温水以及适当的清洗剂清洗。  \n$\\textcircled{5}$ 如果皮肤接触到眼睛，应用大量水冲洗并迅速就医。  \n$\\textcircled{6}$ 遵守施工现场的一切健康安全管理规定。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1371,
+        "chunk": "# 第三节产品说明书的编制  \n\n产品说明书又称为“产品使用手册（operatingmanual)”，是厂商为销售其产品而编写的一种销售手册，主要是用来指导客户如何正确使用所购产品，以免因使用不当或保管不当而造成不良后果。产品说明书在英语中通常有三种不同的说法，即：instruction，direction，description，可以看出产品说明书在使用中所发挥的介绍、指导、描述作用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1372,
+        "chunk": "# 一、产品说明书的基本要求  \n\n$\\textcircled{1}$ 产品说明书应明确给出产品用途和适用范围，并根据产品的特点和需要给出主要组  \n\n成、性能、形式、规格、使用、操作、维修、保养和贮存等方法，以及保护涂装者和产品的安全措施。  \n\n$\\textcircled{2}$ 产品说明书应规定必要的保护环境和节约能源方面的内容，必要时应配备相应的MSDS等安全操作说明。  \n\n$\\textcircled{3}$ 产品说明书应对涂料所具有的易燃、易爆、有毒、有腐蚀性等性质提出注意事项、防护措施和发生意外时的紧急处理办法等内容。  \n\n$\\textcircled{4}$ 当产品组成、性能等改动时，使用说明书的有关内容必须按规定程序及时作相应修改。  \n\n$\\textcircled{5}$ 涂料属于有安全限制要求和有有效期限的产品，说明书应提供产品的贮存期等数据。  \n\n$\\textcircled{6}$ 产品说明书的内容应与涂料制造商印发的有关同种产品的资料或宣传品如广告或产品包装上的内容一致。  \n\n$\\textcircled{7}$ 当需要时，应在产品包装或说明书封面显著位置注明：“使用产品前，请阅读产品使用说明书”。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1373,
+        "chunk": "# 二、产品说明书的具体内容  \n\n一般来说，涂料的产品说明书要对产品进行描述，让使用者对涂料有初步的认识，同时还应该提供适当的施工使用指导。产品说明书一般分为五个部分：产品说明、物理参数、施工说明、安全措施和其他部分。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1374,
+        "chunk": "# 1.说明部分  \n\n产品说明书的说明部分应包括产品类型、组成、基本特性和使用范围等。这一部分的目的是使使用者能基本了解产品的使用特点和范围，并能针对不同的施工条件、防腐要求来选择适当的产品。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1375,
+        "chunk": "# 2.物理参数  \n\n产品说明书中通常应包含如下的物理参数  \n\n(1）固体分涂料产品的固体分有体积固体分和质量固体分两种表示方法，质量固体分一般是按照GB1725定义并测定的，可以理解为产品中含有效成膜物的多少。体积固体分在GB9272中被称为“不挥发分容量”，在ISO3233或ASTMD2697等方法中被称为体积固体分（SVR)。该参数可以用来帮助使用者进行干、湿膜厚度的换算。  \n\n(2）理论涂覆率理论涂覆率可以根据相关的实验方法（如ASTM）在实验室中测得，它对现场施工具有重要的指导意义。参考理论涂覆率可以大概得出每个产品的使用量，使用户初步了解产品的使用成本。理论涂覆率不适用于多孔的材料，如木材、混凝土等。实际涂覆率受到施工条件、工人技术、施工表面的形状、施工物的质地、涂膜厚度和工作时的环境条件等很多因素的影响，这一点需要时应该在说明书中告知客户。  \n\n(3）闪点涂料挥发出的气体与空气混合后漂浮在涂料的表面，在适当的温度下一接触明火就会产生微弱的闪光，但并不燃烧。这个瞬间闪火时的最低温度就是闪点。闪点的测定有开口杯和闭口杯两种测定方法，一般涂料产品的闪点采用闭口杯法测定，国标的测定方法是GB6753.5《涂料及相关产品闪点测定法闭口杯平衡法》。双组分产品的闪点除非特别说明，均为混合后的闪点。闪点是涂料产品的基本安全信息，为了防止在贮存、运输和使用时发生火灾，这个数据必须要提供给涂料使用者。  \n\n(4）贮存期限贮存期限是指涂料在正常的贮存条件下，产品在密封良好的容器中保持良好质量状态的时间。涂料的贮存期限通常限于一年以内，对于易于沉淀的富锌漆及其树脂一直存在缓慢反应的涂料，贮存期一般定为六个月。说明书中的贮存期限通常是指存放在  \n\n$20^{\\circ}C$ 或以下的环境，温度升高有可能会缩短贮存期限",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1376,
+        "chunk": "# 3.施工说明  \n\n产品说明书应给出一些对现场施工具有指导作用的数据，这些数据包括产品的干燥时间、涂装间隔、混合使用期等。  \n\n（1）产品干燥时间干燥时间对于控制现场后续的搬运、安装等工作具有指导意义。一般干燥时间包括指触干和完全固化等。指触干是指用手指轻轻压涂膜表面而不留下印痕或不觉得粘手时的干燥状态。完全固化时间是对双组分涂料而言，固化时间的测定通常以环境温度为20℃时为基准。在固化过程中，温度升高会加速固化反应的进行，反之温度降低会减缓固化过程，对绝大多说的双组分涂料产品而言，往往都有施工温度的范围要求，如果低于最低施工温度，则固化反应基本停止，涂膜无法达到干燥，这一点也应该在说明书中有所反映。  \n\n(2）混合使用期混合使用期即双组分涂料产品混合后可以使用的期限。双组分涂料混合后，固化反应就开始进行，当达到一定阶段后涂料的物理性能会产生很大变化，影响施工及涂装效果，此时可判定为超过混合使用期。超过混合使用期的涂料不能再使用。  \n\n(3）涂装间隔涂装间隔是指从一道涂膜涂装完毕到开始进行下一道涂装时所需要间隔的时间。涂装间隔一般与温度、膜厚及涂膜暴露的环境等有关。有些涂料的层间附着力在很大程度上受到涂装间隔的影响，如果涂装间隔已经超过说明书规定的最大涂装间隔，则必须对漆膜表面进行适当的处理。某些特种涂料没有最大涂装间隔，但是涂装底漆后工件的存放条件必须达到一定标准，不能长期裸露放置。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1377,
+        "chunk": "# 4.安全措施  \n\n产品说明书应为如何处理和使用涂料提供安全措施，以及在贮存、运输和施工时的预防措施和紧急事故处理方法等。这些措施应当遵守国家和当地的各项安全要求和条例。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1378,
+        "chunk": "# 5.其他部分  \n\n说明书还应对推荐使用的施工方法，如喷涂、刷涂等；所要求的施工参数，如喷涂的压力、枪嘴尺寸、涂料的稀释比例等；以及对被涂物进行表面处理的方法等进行适当的描述。  \n\n（1）混合比例多组分产品应向客户提供主剂和固化剂的混合使用比例，现在多组分涂料一般按照混合比例成套销售，方便客户按照配比将两组分混合在一个容器中熟化后使用。当不能一次全部混合使用时，混合比例数据可保证配漆比例正确。  \n\n(2）稀释剂和加量施工中必须要保证涂料有适当的黏度，可加人少量稀释剂以便达到理想黏度。施工方法不同，对涂料的稀释比例要求也不同。说明书中应规定使用稀释剂的种类以及推荐的各种施工方法对应的稀释比例。  \n\n(3）表面处理表面处理指的是涂装前被涂物表面必须达到的清洁程度。一般产品说明书中提出的清洁标准参照国际通用的标准或国家标准，是指使用涂料产品必须要达到的底材处理等级。  \n\n（4）施工条件涂料施工质量对成膜效果以及长期防腐性能等至关重要。在室外施工时，恶劣的天气条件如雨、雪、大风等，以及温度过高或过低、湿度过大、被涂表面有结露等现象时都会对涂装效果产生非常大的影响，因此必要时在说明书中应该明确施工条件。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1379,
+        "chunk": "# 第四节化学品安全技术说明书的编写  \n\n涂料作为一种化学产品，在生产、贮存运输和使用过程中应严格遵守特定的原则和规程。涂料按其形态分为水性涂料、溶剂型涂料、粉末涂料、无溶剂涂料等，其中以溶剂型涂料的危险性最大，根据其所含溶剂的种类、含量、采用颜料、填料的差异及树脂、助剂等的特点，对其生产和使用有不同的安全要求。本节讨论的化学品安全技术说明书是指涂料产品，尤其是溶剂型涂料应提供的、作为安全指导性的技术文件，主要从材料安全数据表的作用意义、生产销售企业及使用企业的责任出发说明化学品安全技术说明书（MSDS）的重要性，同时对其在编写过程中的相关国际国内的法规、必要包含的内容等做简单说明。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1380,
+        "chunk": "# 一、MSDS的意义  \n\n化学品安全技术说明书（MSDS）为化学物质及其制品提供了有关安全、健康和环境保护方面的各种信息，并能提供有关化学品的基本知识、防护措施和应急行动等方面的资料。它是化学品生产供应企业向用户提供包括运输、操作处置、贮存和应急行动等基本危害信息的工具。在一些国家，MSDS也称作物质安全技术说明书（SDS)，在ISO11014中即采用SDS术语。  \n\nMSDS 的英文全程是Material SafetyData Sheet———国际上称作化学品安全说明书（亦叫“物质安全资料表”，化学品安全信息卡，或者材料安全数据表)，它是传递化学品危害信息的重要文件，化学品生产商和贸易商用它来向用户阐明化学品的理化特性（如 $\\mathtt{p H}$ 、闪点、易燃度、反应活性等）以及对使用者的健康可能产生的危害（如致癌、致畸等)。它是一份关于危险化学品的燃、爆性能，毒性和环境危害，以及安全使用、泄漏应急救护处置、主要理化参数、法律法规等方面信息的综合性文件。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1381,
+        "chunk": "# 二、对于MSDS的编制要求  \n\n各国对MSDS的所包含的内容要求大体相同，以下是一些国际标准组织要求在MSDS中必须包含的内容。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1382,
+        "chunk": "# 1.符合美国OSHA要求的MSDS应具备的内容  \n\n第一项：制造商和联系方法。  \n第二项：危险化学品组分。  \n第三项：理化特性。  \n第四项：燃烧与爆炸数据。  \n第五项：反应活性数据。  \n第六项：健康危害数据。  \n第七项：安全操作和使用方法。  \n第八项：防护方法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1383,
+        "chunk": "# 2.符合加拿大WHMIS要求的MSDS应具备的内容  \n\n第一项：产品名称和制造商信息。  \n第二项：危险化学品组分。  \n第三项：物理特性。  \n第四项：消防或燃爆数据。  \n第五项：反应活性数据。  \n第六项：毒理学特性。  \n第七项：预防措施。  \n第八项：急救方法。  \n\n第九项：MSDS的编制依据。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1384,
+        "chunk": "# 3.我国对MSDS的编写规定  \n\n作为对生产企业的强制要求和使用单位的安全保障，MSDS越来越多地被工业防腐等领域所重视。我国对于MSDS的编制也有严格的规定，我国使用的标准是GB16483—2000，为使我国化学品安全技术说明书编写格式和内容尽可能与国际标准一致，以尽快适应国际贸易、技术和经济交流的需要，该标准等效采用ISO11014-1：1994《化学品安全技术说明书》。  \n\nGB16483—2000规定，化学品安全技术说明书应包括以下16部分内容。  \n\n(1）化学品及企业标识主要应标明化学品名称、生产企业名称、地址、邮编、电话、应急电话、传真等信息。  \n\n(2）成分/组成信息标明该化学品是纯化学品还是混合物。对于纯化学品，应给出其化学品名称或商品名和通用名。对于混合物，应给出危害性组分的浓度或浓度范围。  \n\n无论是纯化学品还是混合物，如果其中包含有害性组分，则应给出化学文摘索引登记号(CAS号）。  \n\n（3）危险性概述简要概述本化学品最重要的危害和效应，主要包括：危险类别、侵入途径、健康危害、环境危害、燃爆危险等信息。  \n\n(4）急救措施指作业人员受到意外伤害时所需采取的现场自救或互救的简要处理方法，包括眼睛接触、皮肤接触、吸人、食人的急救措施等。  \n\n(5）消防措施主要表示化学品的物理和化学特殊危险性、合适的灭火介质、不合适的灭火介质以及消防人员个体防护等方面的信息，包括：危险特性、灭火介质和方法以及灭火注意事项等。  \n\n(6）泄漏应急处理指化学品泄漏后现场可采用的简单有效的应急措施、注意事项和消除方法，包括应急行动、应急人员防护、环保措施、消除方法等内容。  \n\n(7）操作处置与贮存主要是指化学品操作处置和安全贮存方面的信息资料，包括操作处置作业中的安全注意事项、安全贮存条件和注意事项。  \n\n(8）接触控制/个体防护指在生产、操作、处置、搬运和使用化学品的作业过程中，为保护作业人员免受化学品危害而采取的防护方法和手段。包括最高容许浓度、工程控制、呼吸系统防护、眼眼防护、身体防护、手防护、其他防护要求。  \n\n(9）理化特性主要描述化学品的外观及理化性质等方面的信息，包括外观与性状、$\\mathbf{pH}$ 、沸点、熔点、相对密度、相对蒸气密度、饱和蒸气压、燃烧热、临界温度、临界压力、辛醇/水分配系数、闪点、引燃温度、爆炸极限、溶解性、主要用途和其他一些特殊理化性质。  \n\n(10）稳定性和反应性主要叙述化学品的稳定性和反应活性方面的信息，包括：稳定性、禁配物、应避免接触的条件、聚合危害、分解产物。  \n\n(11）毒理学资料提供化学品的毒理学信息，包括不同接触方式的急性毒性（ $\\mathrm{LD}_{50}$ $L C_{50})$ 、刺激性、致敏性、亚急性和慢性毒性，致突变性、致畸性、致癌性等。  \n\n(12）生态学资料主要陈述化学品的环境生态效应、行为和转归，包括生物效应（如$\\mathrm{LD_{50},\\ L C_{50})}$ 、生物降解性、生物富集、环境迁移及其他有害的环境影响等。  \n\n(13）废弃处置废弃处置是指对被化学品污染的包装和无使用价值的化学品的安全处理方法，包括废弃处置方法和注意事项。  \n\n(14）运输信息主要是指国内、国际化学品包装、运输的要求及运输规定的分类和编号，包括危险货物编号、包装类别、包装标志、包装方法、UN编号及运输注意事项等。  \n\n（15）法规信息主要是化学品管理方面的法律条款和标准。  \n\n(16）其他信息主要提供其他对安全有重要意义的信息，包括参考文献、填表时间、填表部门、数据审核单位等。  \n\n该标准规定，安全技术说明书的16大项内容在编写时不能随意删除或合并，其顺序不可随意变更。该标准还附有详细的标准编写指南，对每一项所包含内容进行了详细规定。  \n\n安全技术说明书的正文应采用简捷、明了、通俗易懂的规范汉字表述。数字资料要准确可靠，系统全面。  \n\n从化学品的制作之日算起，安全技术说明书的内容每五年应更新一次，若发现新的危害性，在有关信息发布后的半年内，生产企业必须对安全技术说明书的内容进行修订。  \n\n安全技术说明书应采用“一品种一卡片”的方式编写，同类物、同系物的技术说明书不能互相替代；混合物要填写有害性组分及其含量范围，所填数据应是可靠和有依据的。一种化学品具有一种以上的危害性时，要综合表述其主、次危害性以及急救、防护措施。  \n\n安全技术说明书由化学品的生产供应企业编印，在交付商品时提供给用户，作为对用户的一种服务随商品在市场上流通。化学品的用户在接收使用化学品时，要认真阅读技术说明书，了解和掌握化学品的危险性，并根据使用的情形制订安全操作规程，选用合适的防护器具，培训作业人员。  \n\n安全技术说明书的数值和资料要准确可靠，选用的参考资料要有权威性，必要时应咨询省级以上职业安全卫生专门机构。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1385,
+        "chunk": "# 三、MSDS的使用  \n\nMSDS是对于化学品使用的重要补充材料。在化学品发展过程中，伴随它给人们生活带来的极大改善，其固有的危险性也给人类的生存带来极大的威胁，引起全世界的高度重视，建立和完善法律法规，提供详细的信息，就是对化学品从生产到使用的各个环节可能产生的危害预防和防护问题作出规定，为保护人的健康、安全、环境等提供依据和保障。对于涂料行业来说，由于涂料中化学成分复杂，在其生产和使用中存在各种危险因素，包括毒性、燃烧、爆炸等，涂料生产企业有责任将产品潜在的危害和相应急救措施告知使用者。  \n\n涂料的组成不同，对人体的危害性也不同。在涂料生产和施工过程中，经过呼吸道吸入引起中毒的有：树脂中可挥发有毒单体、溶剂蒸气、粉尘；经皮肤或黏膜接触引起中毒的有：涂料的原料、成品、涂料漆雾等。这些化学物质以较小的剂量即可引起机体的功能或器官损害，严重的能危及生命。涂料生产商通过MSDS 提供了较为详细的信息，可以使处于生产和使用涂料状态的人员有针对性地采取措施，如佩戴护目镜、穿着安全的工作服和工作鞋、必要时佩戴面具等，在特殊状态如包装破损、泄漏时能够采取的紧急防范处理措施等。  \n\n另外由于涂料生产和施工中往往使用大量中闪点的有机溶剂，因此燃烧性是涂料的又一个危险性能，需要通过MSDS中给出的闪点等信息，使有关人员了解涂料的燃烧性，减少涂料生产和使用过程中火灾发生的概率。  \n\n涂料生产企业和使用者应该高度重视MSDS的使用，在生产和使用过程中，首先要主动取得MSDS，并由安全环保专业人员组织相关作业人员学习如何正确选择和使用个人防护用品、怎样防止和处理贮存及运输中发生泄漏或燃爆事故、如何防止环境污染以及掌握急救的措施和消防方法等，以达到在第一时间将危害和损失减到最小。其次还要按MSDS的建议和信息，落实各项预防事故的相应措施和设置，例如发放相适应的个人劳动保护用品；置备净水洗眼器或冲淋器；危险化学品的贮存应按说明书规定分类隔放；仓库应配备相应的消防器材等。随着国家在加强各项安全条例及法规的贯彻实施和全民安全意识教育，必将加快  \n\nMSDS的认识推广和普及，从而提高使用涂料等化学品安全管理能力，有效预防和减少事故，改善健康、提高安全和环保水平。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1386,
+        "chunk": "# 参考文献  \n\n[1] 鹤田清治，寺内淑晃，安原清，鎏装の，东京：技术书院，1999.  \n[2] 关西涂料株式会社，桥梁涂装，大阪：关西涂料株式会社，2005.  \n[3] ISO 12944:1998.  \n[4] 日本涂料工业协会：重防腐涂料与涂装，东京：日本涂料工业协会，1995.12.  \n[5] 庞启财，防腐蚀涂料涂装和质量控制．北京：化学工业出版社，2003.  \n[6] GB9969-1.1998.工业产品使用说明书.  \n[7] 赵敏主编．涂料毒性与安全实用手册，北京：化学工业出版社，2004.  \n[8] GB16483—2000.化学品安全技术说明书.",
+        "category": " References"
+    },
+    {
+        "id": 1387,
+        "chunk": "# 底材表面处理标准和检测方法  \n\n通常把为了涂装涂料而对被涂物件表面进行的一切准备工作称为被涂物的表面处理，或称底材处理。在表面处理之前，被涂物的表面状态往往达不到涂装涂料的标准，如钢铁在加工、贮运过程中会被氧化，或者粘有灰尘油脂等异物；混凝土的表面化学性质常会不够稳定，而木材的表面则过于粗糙或者过于平滑。总之底材的初始状态在大多数情况下不宜直接进行涂装，需要做适当的表面处理。在涂料行业中应用最多的底材是钢铁，如钢结构、船舶、集装箱、汽车等，其次是混凝土、轻金属，另外还有木材、塑料等其他非金属材料。本章将重点介绍钢材的表面处理方法和相关标准，对其他底材的处理也做一些简单说明。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1388,
+        "chunk": "# 第一节 钢材表面的物理处理方法  \n\n钢材的表面处理包括物理处理和化学处理两种方式，将在本节和第二节分别予以介绍。这两种方法的目的都是清洁底材表面，并使底材表面的状况发生改变，从而增强对涂膜的结合力，提高涂膜的防腐保护和装饰效果。  \n\n钢材表面的物理处理方法是指通过使用手工器具、动力工具或机械设备来清洁并整理钢材的表面，以达到清除表面杂质、产生一定的粗糙度并使钢材整体表面趋于平整的效果。有的物理处理方法如抛丸和喷砂等还可释放底材因加工产生的内部应力。  \n\n钢材在加工和贮存过程中，其表面会附着很多杂质和污染物，它们包括表面的油污、氧化物、旧漆膜和其他固体附着物，这些物质往往会影响涂膜的附着力、干燥速率、光泽和涂膜外观等，有时还会造成缩孔、起泡、点蚀甚至脱落等涂膜病。物理处理方法的主要目的就是清除这些物质。  \n\n钢铁表面的物理处理方法主要包括手工工具清理、动力工具清理和喷射处理等，前者主要靠人工操作，后者采用电和压缩空气等作为动力，并使用各种机械设备。手工工具清理适合污物附着不牢固、处理量相对较小、没有动力条件的作业场合，处理的效果往往差一些。动力工具处理的效率较高，适合较大批量的处理工作。而喷射处理往往适合工业化生产。在选择底材处理方式时，还要考虑总费用的限制和环保的要求等因素。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1389,
+        "chunk": "# 一、手工工具清理  \n\n手工工具清理是一种原始的除锈方式，其方法是用简单的工具敲松和铲除底材表面厚的和疏松的锈蚀物。用这种方法可以除去附着不牢的氧化皮、松散的旧涂膜和其他杂物。但是对于附着力牢固的氧化皮、铁锈等则往往无能为力。手工清理所用的工具有锤子、铲刀、钢丝刷、砂布砂纸等，手工工具清理的所有工作都要靠人工完成，劳动强度大，操作环境恶劣，效率低，除锈质量也较差。手动工具的优点是便于携带且不需动力源，缺点是表面粗糙度小且处理效果不好。现在手工除锈主要是作为辅助手段，如用于小面积的除锈或者机械设备难以完成的除锈作业。还可以用在喷射除锈前对厚锈和松散起泡的旧涂膜先进行手工铲除，以节省喷射的成本。  \n\n手工工具清理常用的清理工具有榔头、铲刀、刮刀、锉刀、钢丝刷、砂布、砂纸等（图5-2-1)。榔头一般用于敲松和除去局部较厚的锈层和旧漆膜；锉刀用于除去牢固附着在底材表面的硬质凸起物，如焊瘤等；刮刀用于除去缝隙中的铁锈和腻子等；铲刀用于铲除油污、附着不牢的异物和旧漆膜。钢丝刷可用于清除较薄的疏松锈层、旧涂膜等；砂布砂纸一般用于清除较轻的锈和旧涂膜。  \n\n![](images/710c1d6965fcaa8da95ce2174b742cf626e8f6d9cc407845ebff2a797e784031.jpg)  \n图5-2-1 手动工具  \n\n手动工具清理操作开始时，首先要检查表面的状况，如是否有厚锈层和油类、油脂或其他污物；然后用铲刀除去较厚的油污和附着不牢的异物、铁锈；再用溶剂清洗或擦拭去残留的油污；有锈层存在时要用榔头敲松厚锈层，并用刮刀或铲刀除去；用锉刀除去毛刺、焊渣和各种突出物；用砂纸打磨平面和突出部位的铁锈，用钢丝刷清理缝隙和麻坑内的铁锈；用铲刀除去翘起和附着不牢的旧漆膜，用砂纸磨去粉化的旧漆膜，尚未失效的韧性漆膜可以保留；最后要用压缩空气吹去浮尘，或用抹布清洁表面，并尽快涂装底漆。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1390,
+        "chunk": "# 二、动力工具清理  \n\n动力工具清理与手工清理的工具相似，但这些工具要使用诸如电或压缩空气等动力源，清理效率大大提高，可以达到手工工具的4～6倍。动力工具可以除去所有松散的附着异物，如氧化皮、铁锈、旧涂膜等，但是不能除去附着牢固的异物，也主要用于修理场合。这种方法设备噪声很大，粉尘多且与操作者直接接触，对人员的伤害和环境的污染较严重，现在已经很少大规模使用。  \n\n动力工具包括砂轮机、动力钢丝刷、气铲、风动打锈锤、针束除锈器等（图5-2-2)，可分别用于不同的部位。下面介绍一下常用动力工具的用途。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1391,
+        "chunk": "# 1．砂轮机  \n\n砂轮机主要用于清除铸件的毛刺，清理焊缝，打磨厚锈层，它的除锈工件是砂轮盘，分为直柄和端型等。工作原理是依靠砂轮的高速旋转来磨削和敲击底材表面，达到清除杂  \n\n![](images/460e49c4dd498137027e9b55aedffb9b5003f77bf9dc9f19656ebcaba5c8253a.jpg)  \n图5-2-2 各种动力清理工具  \n\n质和平整底材表面的效果",
+        "category": " Introduction"
+    },
+    {
+        "id": 1392,
+        "chunk": "# 2.动力钢丝刷  \n\n钢丝刷使用灵活方便，用电或压缩空气作为动力，主要依靠钢丝相对于底材相对运动时产生的摩擦和剪切力除去钢材表面的异物。适用于除锈、除旧涂膜，清理焊缝，去毛刺、飞边等，还可以去除凹陷处的污物。但用它不能除去氧化皮、焊接飞溅物等附着牢固的异物。根据不同的用途，刷面有轮形、杯形、伞形等形状。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1393,
+        "chunk": "# 3.风动打锈锤  \n\n风动打锈锤又称敲铲枪，主要是依靠压缩空气驱动锤头作往复运动，撞击金属表面铁锈，从而使其脱落除去，是一种比较灵活的除锈工具，适用于比较狭小的区域。其主体由锤体、手柄、旋塞构成，垂头有多种形状，棱角形锤头适用于平面除锈，尖型锤头则适于边角、凹坑和浅缝处除锈。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1394,
+        "chunk": "# 4.针束除锈器  \n\n针束除锈器也是由电或压缩空气驱动，依靠针束的旋转和往复运动冲击底材，达到清理效果，常被用于焊缝、螺母、孔洞等狭小区域。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1395,
+        "chunk": "# 三、喷射处理  \n\n喷射处理是依靠动力赋予喷射介质一定的能量，并使喷射介质冲击被处理底材的表面，通过冲击、磨削等作用清除掉其表面的杂质，并产生一定的粗糙度的方法。喷射的动力通常有离心力、高压气体、高压液体等，具体的清理方法有喷砂处理、抛丸处理和高压水处理等。需要提出的是，对于喷射处理方法的叫法有多种，例如抛丸处理也可以被称为抛砂处理，因为这种抛射处理方法使用的介质（即磨料）不只限于钢丸，有时也使用砂粒等，同样喷砂处理有时也会因为使用钢丸作为磨料而被称为喷丸处理，高压水处理也会因在水中夹带有磨料而称为湿喷砂处理。为了便于读者理解，在这里把各种方法简单地分为抛丸清理、喷  \n\n砂清理和高压水喷射处理",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1396,
+        "chunk": "# 1.抛丸清理  \n\n抛丸是指通过抛丸设备高速旋转的叶轮把钢丸、砂粒和钢丝断等磨料以很高的速度和一定的角度抛射到工作表面上，让丸料冲击工作表面，产生冲击和磨削作用达到清除钢材表面异物、消除应力和产生粗糙度的作用。  \n\n抛丸机通常由叶轮、定向套、分丸轮、叶片等组成（图5-2-3)。工作时电动机带动叶轮以2500r/min左右的转速高速旋转，钢丸等磨料靠重力进入分丸轮，并同叶轮一起旋转产生离心力，在从定向套飞出的过程中被加速，最后以60～80m/s的速度飞出，抛射到被处理的底材表面。  \n\n![](images/fd9251dc92ab9eb03aab3c1bc224d1e4f0a830403bf537b554a4043ce6995012.jpg)  \n图5-2-3抛丸清理的原理1—叶轮；2—分丸轮；3—叶片；4一钢丸运动轨迹  \n\n抛丸机操作时通过控制和选择丸料的颗粒大小、形状以及调整和设定机器的行走速度，控制丸料的抛射流量，可以得到不同的抛射强度，从而获得不同的表面处理效果。  \n\n现代的抛丸清理一般都是流水线作业，包括抛丸机、输送装置、通风除尘装置、喷漆装置和加热装置等。集装箱钢板表面处理流水线的工艺如图5-2-4所示。  \n\n![](images/aed40181ec096351c9294c7269d9aa61c5b9f87de0e642541d115d7eb52eabca.jpg)  \n图5-2-4 集装箱钢板表面处理流水线  \n\n(1）钢板输送整个流水线上钢板的输送是由辊道来完成的，辊道由电机通过调速系统带动，速度一般为10m/min左右。  \n\n(2）抛丸除锈集装箱钢板厚度一般不超过6mm，钢板表面状态较好，杂质以氧化皮和铁锈居多，通常采用4～16抛头抛丸机。一般要求粗糙度达到25～50um，因此单独使用钢丸作为磨料很难达到这种要求，需要加入棱角砂和钢丝切段等磨料。  \n\n(3）气流清理气流清理主要用来清除碎磨料和粉尘，通过通风除尘系统实现磨料的循环和钢材表面净化的目的，有的流水线采用45°角倾斜放置钢板的方式，可以使废磨料和粉尘在重力和气流的双重作用下轻易离开底材表面。  \n\n(4）车间底漆涂装车间底漆的涂装膜厚为10μm左右，主要采用喷涂的方式，在边缘处自动控制开枪关枪时间，一般是双面同时涂装。近来也出现了辊涂车间底漆的方式，涂料和稀释剂耗量比喷涂法少。  \n\n（5）涂层于燥由于生产节奏快，要采用强制干燥的方式，一般为 $80^{\\circ}C$ 烘十 $1\\sim2\\mathrm{min}$ 中通常配有通风装置，以利于溶剂尽快挥发。烘干之后要配备吹风装置，使涂膜温度尽快降低至室温。  \n\n(6）钢板堆码堆码之前要观察钢板有无漏底，尤其是要通过反光镜观察钢板背面状况，发现漏底时一般通过刷涂的方法及时修补。堆码时要求将钢板排列整齐，以利叉车运送方便。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1397,
+        "chunk": "# 2.喷砂处理  \n\n喷砂处理是最常用的一种表面处理方法，被广泛用于钢结构、贮罐等涂装前的底材处理、现场组装后的二次底材处理以及小面积修补涂料时的底材处理等。它具有较好的处理效果和经济性，是各种物理处理方法中性价比最高的一种，喷砂处理的缺点是过程中容易产生粉尘，会对环境造成污染并对工人身体健康造成损害。  \n\n(1）喷砂处理的工作原理喷砂处理是一种以压缩空气为动力的清理方法，其原理是：  \n\n![](images/e14085a8c2252a48eebee85a8aecade2081e0f195ef1a49f56843bb45b8d2187.jpg)  \n图5-2-5喷砂原理1一贮砂罐；2一喷枪接口；3一混合室：4一压缩空气进口  \n\n磨料被高压空气推人或吸入管道，并在管道内被气流不断加速，形成磨料流从喷枪喷出，磨料流以极高的速度冲击底材表面，依靠冲击和磨削等作用除去金属底材表面的铁锈、氧化皮等污物，并在表面形成一定的粗糙度。  \n\n喷砂处理按照磨料进人系统的方式分为吸入式和压出式两种，其原理如图5-2-5所示。  \n\n(2）喷砂系统的组成喷砂处理系统由压力装置、吸人装置、喷砂装置、回收装置、通风除尘装置等部分组成（图5-2-6)。其工作原理如下：压力装置产生的压缩空气进人贮砂罐，推动罐内的磨料经导管进人喷枪，从喷嘴射向工作表面。喷出的磨料经筛网落入磨料坑，经回输砂装置送回贮砂罐再重复使用。磨料室内的含尘气体和磨料回收装置中的粉尘通过风机吸进除尘设备除尘，  \n\n然后排向大气。  \n\n(3）喷砂处理的分类喷砂处理是一种比较方便的底材处理方法，其应用也有很多种类，包括开放式喷砂、密闭式喷砂和自动循环式喷砂等。  \n\n$\\textcircled{1}$ 开放式喷砂开放式喷砂处理方式被广泛应用于贮罐、桥梁等大型工件的现场底材处理，采用开式作业，对场地条件要求低，底材处理质量好，费用也比较低。但是由于噪声大、磨料回收率低，对环境的污染较大。·  \n\n开放式喷砂系统主要包括空压机、高压罐、管路、喷枪和磨料回收装置。  \n\n$\\textcircled{2}$ 密闭式喷砂密闭式喷砂系统将喷砂操作部分密闭起来，有效地减少了污染。密闭的喷砂室设有除尘和磨料回收系统。小型的密闭喷砂室适于处理小的工件，效率不高；大型密闭喷砂室很多是自动的，可以用于连续化生产或处理如船舶分段等大型工件。进入喷砂室工作的人员需要配备独立呼吸系统和防护服装。  \n\n$\\textcircled{3}$ 自动循环式喷砂自动循环式喷砂系统在开放式喷砂系统的基础上进行了改进，采用了特殊的喷嘴，这种喷嘴配有一个带有毛刷的密闭材料外套，外套和真空除尘系统相连。工作时外套紧贴工件表面，磨料流对工件喷射后产生的粉尘和废磨料能被真空系统及时抽到  \n\n![](images/8f402c5acf9ee8a924caf7d1e6f09ba47fc542123622469563093e81b5c8e296.jpg)  \n图5-2-6 喷砂系统  \n\nA一空气压缩机；B—压缩空气贮罐；C—贮砂罐；D—喷枪；E-喷室；F—除尘分离器；G—排风机；H—集尘器；I—螺旋输砂装置；J—吊斗输砂装置  \n\n分离筛选装置，经分离和过滤后可以送回系统重复使用，从而避免了粉尘等有害物的扩散，减少了环境污染。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1398,
+        "chunk": "# 3.水喷射处理  \n\n水喷射处理是一种相对较新的技术，它利用高压水的冲击力，对底材表面附着物产生冲击、水楔、疲劳和气蚀等作用，使其脱落而除去。水喷射处理有两个显著的优点，第一，它喷射的介质主要是水，能抑制粉尘的释放，有利于环保，因此使用范围比其他喷射方法要广；第二，它不仅可以除去氧化皮、铁锈和旧涂层等杂质，还可以溶解并冲掉可溶性盐类，这是干法喷射无法做到的。但这种方法不能在底材的表面产生粗糙度，而且有可能使邻近的完好涂膜产生开裂。由于水的存在，清理后的钢材在涂装之前往往会产生锈蚀，因此有时需要在水里加人缓蚀剂。  \n\n(1）水喷射处理系统的组成水喷射处理系统通常由高压水泵、高压管路、控制装置和喷枪等组成，先进的水喷射系统往往还配有水循环装置，利用真空原理将喷射后产生的废水和杂质回收起来，进行过滤分离后，水可以重复使用。  \n\n(2）水喷射处理的分类按照通行的标准，水喷射处理可分为低压水清理、高压水清理、高压水喷射和超高压水喷射四类。  \n\n$\\textcircled{1}$ ①低压水清理（LPWC）压力小于34MPa，通常用于除去疏松的氧化皮或沉积物的表面水清洗。  \n\n$\\textcircled{2}$ ②高压水清理（HPWC）压力为34～70MPa，用于除去旧的锈皮和疏松漆膜，使用“鼓风式喷射”枪嘴喷出水流，每分钟流量大约为60L。  \n\n$\\textcircled{3}$ 高压水喷射（HPWJ) 压力为 $70{\\sim}170\\mathrm{MPa}$ 0  \n\n$\\textcircled{4}$ ④ 超高压水喷射（UHPJC）压力大于170MPa，用于完全除去所有锈蚀和氧化皮，并且可除去所有的残存旧涂膜。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1399,
+        "chunk": "# 四、钢铁表面处理的相关标准  \n\n对于涂料公司的涂装管理工程师而言，如何评价处理后的金属表面是否达到了可以涂装涂料的标准要求是保证漆膜发挥性能的关键，其意义往往要比了解表面处理过程本身重要得多。为了正确地评价表面处理的质量，许多国家都制定了表面处理质量评定标准。其中比较权威的是：国际标准化组织（ISO）、美国钢结构涂装协会（SSPC)、日本造船研究协会(JSRA)、美国防腐工程师联合会（NACE）等制定的相应底材处理标准。中国也等效采用ISO8501-1：1988标准的有关部分，制定了关于钢铁除锈的国家标准GB8923—1988《涂装前钢材表面锈蚀等级和除锈等级》。下面对一些常用的标准和它们之间的相互关系作简单介绍。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1400,
+        "chunk": "# 1.ISO标准  \n\n一般来讲，影响涂层性能的因素主要包括底材上存在的铁锈和氧化皮、表面的污染物、旧漆膜、灰尘、离子以及底材处理后的表面粗糙度等。ISO标准针对这些情况，制定了相应的ISO8501、ISO8502及ISO8503等一系列标准来对金属表面的状况做出评价，ISO8501是对钢板除锈质量的评价标准，ISO8502是对表面处理后的钢材的一些检测方法，ISO8503则是关于喷射清理后钢材表面粗糙度的评定标准。各标准的名称见表5-2-1。  \n\n表5-2-1 相关ISO标准的名称  \n\n\n<html><body><table><tr><td colspan=\"2\">ISO标准号</td><td>标准名称</td></tr><tr><td rowspan=\"2\">ISO 8501</td><td>ISO 8501-1</td><td>钢材在涂装涂料及相关产品前的预处理，表面清洁度的目视评定</td></tr><tr><td>ISO 8501-2</td><td>用于评定原先涂过涂料的钢材进行局部除锈的标准</td></tr><tr><td rowspan=\"9\">ISO 8502</td><td>ISO 8502-1</td><td>喷射处理过的钢材表面进行可溶性铁盐的检测方法</td></tr><tr><td>ISO 8502-2</td><td>经除锈过的钢材表面氯化物的检测方法</td></tr><tr><td>ISO 8502-3</td><td>涂装前表面灰尘沾污程度标准</td></tr><tr><td>ISO 8502-4</td><td>涂装前钢材表面结露可能性的评定</td></tr><tr><td>ISO 8502-5</td><td>涂装前钢材表面氯化物测定法，氯离子检测法</td></tr><tr><td>ISO 8502-6</td><td>表面可溶性杂质取样及测定方法，BRESLE方法</td></tr><tr><td>ISO 8502-7</td><td>涂装前表面可溶性杂质分析，氯离子现场分析法</td></tr><tr><td>ISO 8502-8</td><td>涂装前表面可溶性杂质分析，硫酸盐现场分析法</td></tr><tr><td>ISO 8502-9</td><td>可溶性盐电导率的现场检测法</td></tr><tr><td rowspan=\"3\"></td><td>ISO 8502-10</td><td>可溶性盐的滴定法现场检测法</td></tr><tr><td>ISO 8503-1</td><td>表面粗糙度比较样块的技术要求和定义</td></tr><tr><td>ISO 8503-2</td><td>喷射清理后钢材表面粗糙度分级-—比较样块法</td></tr><tr><td rowspan=\"2\">ISO 8503</td><td>ISO 8503-3</td><td>ISO基准样块的校验和表面粗糙度的测定方法 显微镜调焦法</td></tr><tr><td>ISO 8503-4</td><td>ISO 基准样块的校验和表面粗糙度的测定方法 触针法</td></tr></table></body></html>  \n\n(1）锈蚀和预处理等级的评价ISO8501-1是目视评定锈蚀等级和预处理等级的依据，这个标准主要包括锈蚀等级、预处理等级、目视评定步骤等几个部分和28张典型样板的照片。在实际工作中通常是结合标准的描述和对照样板的照片来判断底材的等级和是否达到了预处理的标准要求。需要说明的是，在本书中转载的这些照片只是为了用来向读者介绍和说明相关的标准，不能用做判断底材处理的等级依据。如果读者需要，可以向有关方购买相应的标准。  \n\n$\\textcircled{1}$ 金属表面的锈蚀等级ISO8501-1将未涂装过的金属表面按氧化皮覆盖情况和锈蚀程度分为A、B、C、D四个等级（图5-2-7)，对各等级的原始状态描述如下。  \n\nA：钢材表面大面积覆盖附着氧化皮，但几乎没有铁锈。  \n\n![](images/9be845354a629419ec671f7cf89a63284fdbd5eaf907a80a58772efea927edf4.jpg)  \n图5-2-7金属表面锈蚀等级评定照片  \n\nB：钢材表面已开始锈蚀，且氧化皮已开始剥落。C：钢材表面的氧化皮已因锈蚀而产生剥落或者可以刮除，但在正常视力观察下仅可见少量点蚀。D：氧化皮已因锈蚀而剥落，在正常视力观察下，已可见到普遍发生点蚀的钢材表面。②喷射清理预处理（Sa）以喷射方式进行的表面预处理，以字母“Sa”表示。ISO8501-1将喷射处理分为 Sal、Sa2、Sa2和 Sa3四个等级，并给出了各个等级金属底材表面的喷射处理的文字描述和照片。  \n\n$\\mathbf{Sa}2\\frac{\\mathbb{1}}{\\mathbb{2}}$ 被称作“非常彻底的喷射处理”级别，是最常用的底材处理等级，绝大多数的钢材涂装配套都要求底材处理达到这个等级。这个级别在ISO8501-1中是这样定义的：“在不放大的情况下进行观察时，表面应无可见的油脂和污垢，并且没有氧化皮、铁锈、涂料涂层和异物。任何残留的痕迹应仅是点状或条纹状的轻微色斑”，ISO 8501-1中针对A、B、C、D四种表面状态的钢材处理后达到Sa2的照片如图5-2-8所示。  \n\nSa3是比Sa2一更严格的处理级别，称作“使钢材表面更洁净的喷射处理”，通常应用在一些特殊场合的涂装配套的底材处理，如化学品舱和化学品贮罐等。它要求处理到金属表面没有杂质的状态。Sa3级在ISO8501-1中的描述为：“在不放大情况下进行观察时，表面应无可见的油脂和污垢，并且没有氧化皮、铁锈、涂料涂层和异物。该表面应具有均匀的金属光泽”（图5-2-9）。  \n\n③手工和动力工具清理预处理（St）ISO8501-1将动力工具处理分为St2和St3两个级别。St3是涂装涂料时常用的处理级别；对于一些渗透性好的油性涂料和对底材处理要求不高的带锈型涂料，底材的处理等级要求可以定为St2，以节约施工成本。St2的文字描述为：在不放大情况下进行观察时，表面应无可见的油脂和污垢，并且几乎没有附着不牢的氧化皮、铁锈、涂料涂层和异物（图5-2-10)。St3的描述与St2基本相同，但“表面处理要彻底得多，表面应具有金属底材的光泽”（图5-2-11)。  \n\n$\\textcircled{4}$ 火焰清理预处理（FI）火焰处理主要用于清除底材表面的油污等，常用于不锈钢表面的处理。用火焰清理方式进行的表面处理以字母“FT”表示。其状态被描述为：“在不放  \n\n![](images/b0ddd5926040e5c54f8eeac4fc9656320d8731a0d85c5cc7a478130fd0db1842.jpg)  \n图5-2-8 金属底材Sa2 级表面处理参考图片  \n\n![](images/eb7ff0976183e084e4b15330b95e349960ae14207b6aff077a29e688fee44ddb.jpg)  \n\n图5-210BC $_{\\mathrm{~\\tiny~D~}}$ 级金属底材St2级表面处理参考图片大情况下进行观察时，表面应无氧化皮、铁锈、涂料涂层和异物，任何残留物仅应显示为表面褪色”。  \n\n![](images/5242399a53b4536cdddd5dc2b4ba971c3ec17942d36a83d56589e050cc7578f1.jpg)  \n图5-2-11B、C、D级金属底材St3级表面处理参考图片  \n\n(2）钢材表面粗糙度金属表面经过喷射清理后，就会获得一定的表面粗糙度或表面轮廓。表面粗糙度的存在会使金属表面的面积明显增加，有利于涂料和底材之间的附着。当然并不是粗糙度越大越好，因为在实际涂装时涂料必须要能够覆盖住这些粗糙度的波峰，如果粗糙度和涂膜的厚度差距过小，容易造成波峰处的膜厚变薄，影响保护效果，另外过大的粗糙度会由于涂料对底材的浸润不良造成涂膜防腐性和附着性的降低。  \n\n$\\textcircled{1}$ 表面粗糙度的定义表面粗糙度有三种常用的表示方法，即 $R_{\\mathrm{a}}$ ， $R_{\\mathrm{y}}$ 和 $R_{z}$ 。 $R_{\\mathrm{{a}}}$ 表示波峰、波谷到虚构的中心线的平均距离； $R_{\\bar{z}}$ 表示波峰到波谷的平均值，即在中心线上下各取5个点，将这些点至中心线的距离标记为 $y_{1}\\sim$ y10， $R_{z}{=}(y_{1}+y_{2}+y_{3}+y_{4}+\\cdots+y_{10})/5;$ $R_{\\mathrm{y}}$ 为波峰到波谷的最大值，也称作 $R_{\\mathrm{max}}$ ，应用触针法可以测定 $R_{y}$ 。对于喷射处理的表面粗糙度，通常用 $R_{z}$ 来描述，一般叫做喷砂粗糙度，$R_{\\mathrm{z}}=(4{\\sim}6)R_{\\mathrm{a}}$ ，通常取最大系数6。各种表面粗糙度表示方法示意如图5-2-12所示。  \n\n$\\textcircled{2}$ 表面粗糙度的测定方法ISO8503规定了三种粗糙度的评价方法，即比较样块法、显微调焦法和触针法。ISO8503-1把表面粗糙度样板分为钢砂（样板G）和钢丸（样板S）喷射处理两种。每一种表面粗糙度样板分为4块$(\\mathrm{~I~}{\\sim}\\mathbb{V})$ ，这四块样板可以分为细、中、粗三级，标准板的分级描述见表5-2-2。在实际工作中用这些样块作为对比标准，通过视觉和触觉来对比判断底材的处理程度。  \n\n![](images/6eb735f0b83fbb9d9c5257fc31226db04977b2dc9fe74e643cd6e044e306e07b.jpg)  \n图5-2-12 各种表面粗糙度表示方法示意  \n\nISO8503-3规定了显微调焦法测定给定区域的表面粗糙度 $R_{\\mathbf{y}}$ 的方法。这种方法利用显微镜调焦的原理，将处理过的底材样块或复制物放在规定的显微镜下观察，记录能用显微镜刚刚能清楚观察到波峰时的调焦距离 $r_{1}$ 和刚刚能清楚观察到波谷时的调焦距离 $r_{2},r_{1}$ 和 $r_{2}$ 的差值即为波峰到波谷间的距离 $h_{y}$ 。该标准要求检测20个值，取其算数平均值 $h_{\\mathbf{y}}$ 作为检测结果，这里的 $h_{y}$ 值可以认为是 $R_{\\mathrm{y}}$ 值。  \n\n现在一般采用触针式的电子粗糙度仪来检测粗糙度，它可以直接读出以微米表示的粗糙度值 $R_{y}$ 。ISO8503-4规定了用触针法测定给定区域的平均表面粗糙度 $R_{\\mathbf{y5}}$ 的方法，这种方法通过用触计式粗糙度仪检测 $12.5\\mathrm{mm}$ 评价长度上的连续五个点的 $R_{y}$ 值（同时规定每个 $R_{\\mathrm{y}}$ 值的取样长度为 $\\mathrm{5mm}$ )，再取这五个检测值的算术平均值即得到这个评价区域的 $R_{\\mathbf{y}5}$  \n\n表5-2-2ISO粗糙度标准板的描述  \n\n\n<html><body><table><tr><td>处理方法</td><td>等级</td><td colspan=\"2\">表面粗糙度</td><td></td></tr><tr><td rowspan=\"3\">钢砂处理表面</td><td>细fine G</td><td>表面轮廊等于样板I～Ⅱ，但不包括Ⅱ</td><td>Ry23～49μm，典型值为25～45μm</td><td rowspan=\"3\"></td></tr><tr><td>中medium G</td><td>表面轮廊等于样板Ⅱ～Ⅲ，但不包括Ⅲ</td><td>R,50～84μm，典型值为55~80μm</td></tr><tr><td>粗coarse G</td><td>表面轮廊等于样板Ⅲ～IV，但不包括IV</td><td>R,85～130μm，典型值为85～129μm</td></tr><tr><td rowspan=\"3\">钢丸处理表面</td><td>细fine S</td><td>表面轮廊等于样板I～Ⅱ，但不包括Ⅱ</td><td>R,23～34μm，典型值为25～30μm</td><td></td></tr><tr><td>中medium S</td><td>表面轮廓等于样板～Ⅲ，但不包括Ⅲ</td><td></td><td>Ry35～59μm，典型值为40～55μm</td></tr><tr><td>粗coarse S</td><td>表面轮廊等于样板Ⅲ～IV，但不包括IV</td><td>R,60～84um，典型值为65～80μm</td><td></td></tr></table></body></html>  \n\n(3）灰尘清洁度钢材表面的灰尘对涂料与钢材表面的附着力有很大的影响。涂料对于灰尘的附着力是相当好的，但灰尘在钢材上却几乎没有任何的附着力。而且灰尘的存在很容易使涂层浸水后产生起泡。ISO8502-3规定了钢材表面灰尘清洁度的检查标准，检查方法是把胶带摩擦压在钢材表面，然后取起放在白色的背景上，灰尘的多少和粒度就会清晰地表现出来，再把它与标准对比判断就可以得出灰尘清洁度和灰尘粒径等级。灰尘清洁度分为$1\\sim5$ 五个级别，灰尘粒径分为 $0\\sim5$ 级六个级别。标准中提供了灰尘清洁度级别的对比图片，灰尘粒径的各级别描述如下。  \n\n$\\textcircled{1}0$ 级 10倍放大镜下不可见微粒。  \n$\\textcircled{2}1$ 级 10倍放大镜下可见而肉眼不可见（颗粒直径小于 $50\\mu\\mathrm{m}\\dot{}$ 。  \n$\\textcircled{3}2$ 级 正常或矫正视力下刚刚可见（颗粒直径为 $50\\mathrm{\\sim}100\\mu\\mathrm{m}).$ 。  \n$\\textcircled{4}3$ 级 正常或矫正视力下明显可见（直径小于 $0.5\\mathrm{mm}$ ）的颗粒。  \n$\\textcircled{5}$ 4级 直径为 $0.5{\\sim}2.5\\operatorname*{min}$ 的颗粒。  \n$\\textcircled{6}5$ 级 直径大于 $2.5\\mathrm{mm}$ 的颗粒。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1401,
+        "chunk": "# 2.SSPC的底材处理标准  \n\n大四钢细阀仍云（JI）有」一去底处理，包旧刑消优、明力上共处理、喷射处理和火焰处理等，共分11个等级。  \n\n(1）SP1溶剂处理，用溶剂或其蒸汽、乳化液、碱或水蒸气完全除去油脂、蜡、灰尘及其他污物，适用低湿度的室外环境。(2）SP2手动工具处理，使用手动工具如钢丝刷、铲刀、锤、砂纸等，通过削、磨、刷等方法去除松散的锈迹、氧化皮和旧漆膜等，以达到指定等级。(3）SP3机械工具处理，使用机械工具如风铲、除鳞机、砂轮等，通过削、磨、刷等方法去除松散的锈迹、氧化皮和旧漆膜等，以达到指定等级。(4）SP4火焰除锈处理，用乙炔焰烧除油污，脱除锈蚀及松动的氧化皮，再接着用钢丝刷或喷射除锈，趁热涂装。(5）SP5喷砂出白级处理，通过干式或湿式喷砂、抛丸的方法除去所有可见的锈迹、氧化皮、漆皮等。(6）SP6商业级喷砂处理，喷砂处理至被处理面积的2/3的部分没有可见的残迹。(7）SP7扫砂除锈处理，喷砂除去所有附着不牢固的氧化皮、锈迹和漆皮，露出大多数有锈斑点的钢材表面。(8)SP8浸酸除锈法，通过酸液和电解质的浸洗除去所有锈迹和氧化皮。(9）SP9暴露后喷射，钢材先通过暴露的方法除去氧化皮后再进行喷射除锈。（10）SP10喷砂近白处理，喷砂处理至接近SP5标准表面，至少 $95\\%$ 的被处理表面没有可见的残渣。  \n\n(11）SP11动力工具清理至裸露金属，SSPC-VIS1将处理前的钢材分为A、B、C、D、G五个级别，其中的前四个级别和ISO标准类似，G 级用来描述表面覆盖有漆膜的钢材的状态，它又分为G1、G2、G3三个等级，G1表面有大量小的点蚀，G2表面有中等程度锈蚀凹坑，G3表面有严重的锈蚀凹坑。SSPC-VIS1给出了这三个等级的底材不同处理方法和处理等级的典型照片（图5-2-13）。  \n\n![](images/2d7d1879acad1217bef782f3b3333ae0711a6cd060f36d23efe4c80a0057faba.jpg)  \n图：5-2-13SSPC-VIS1处理前的钢材状态图片",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1402,
+        "chunk": "# 3.NACE标准  \n\n美国腐蚀工程师协会（NACE）制定的底材处理标准可以分为NACENo.1、NACENo.2、NACE No.3、NACE No.4、NACE No.5、NACE No.6、NACE No.8，共七个级别。1994年10月，NACE和SSPC联合制定了磨料喷砂清理标准，共有以下四个部分。  \n\nNACE No.1/SSPC SP-5 金属喷砂出 NACE No.3/SSPC SP-6 商业级喷砂白处理 处理NACENo.2/SSPCSP-10金属喷砂近 NACE No.4/SSPC SP-7 扫砂级喷砂似出白处理 处理而后又共同制定了其他的底材处理标准，即NACE No.5/SSPC SP-12 水喷射处理 NACE No.8/SSPC SP-14 工业级喷砂标准 清理标准NACE No. 6/SSPC SP-13 混凝土表面处理标准",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1403,
+        "chunk": "# 4.不同表面处理的标准级别对应  \n\n虽然各种底材处理标准的内容不同，但是它们之间有着一些对应关系，现将各国除锈标准的对应关系列于表5-2-3中，供参考。  \n\n表5-2-3 各国除锈标准的对应关系  \n\n\n<html><body><table><tr><td colspan=\"8\">标准名称</td><td rowspan=\"3\">表面处法</td><td rowspan=\"3\">(处理内容法)</td><td rowspan=\"3\">除率</td></tr><tr><td>美国</td><td>瑞典</td><td>中国</td><td>英国</td><td>德国</td><td>国际</td><td>美国</td><td></td></tr><tr><td>SSPC</td><td>SIS</td><td>GB</td><td>BS</td><td>DIN</td><td>ISO</td><td>NACE</td><td>SPSS</td></tr><tr><td>SP-5</td><td colspan=\"2\">A,B.C,D</td><td>1级</td><td>Sa3</td><td>Sa3</td><td>No.1</td><td>喷 Sd3</td><td>喷丸</td><td>白清除露出</td><td>99</td></tr><tr><td>SP-10</td><td colspan=\"2\">AD</td><td>2级</td><td>Sa2</td><td>Sa2</td><td>No.2</td><td>Sd2,Sh2</td><td>喷丸</td><td>白喷除接近</td><td>95</td></tr><tr><td>SP-6</td><td colspan=\"2\">B,c,D</td><td>3级</td><td>Sa2</td><td>Sa2</td><td>No.3</td><td>Sdl,Sh1</td><td>喷</td><td>喷砂清除</td><td>67</td></tr><tr><td>SP-7</td><td colspan=\"2\">BSc,D</td><td></td><td>Sa1</td><td>Sal</td><td>No.4</td><td>Ss</td><td>喷</td><td>喷砂清除</td><td></td></tr><tr><td>SP-3</td><td colspan=\"2\">St3 B,C,D</td><td>一</td><td>St3</td><td>St3</td><td>一</td><td>Pt3</td><td>动力工具除锈</td><td></td><td></td></tr><tr><td>SP-2</td><td colspan=\"2\">BSt,D</td><td></td><td>St2</td><td>St2</td><td></td><td>Pt2</td><td>手工除锈</td><td></td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1404,
+        "chunk": "# ISO、SSPC和NACE三个标准之间也存在一定的对应关系，见表5-2-4。  \n\n表5-2-4表面处理标准对应表  \n\n\n<html><body><table><tr><td>SSPC</td><td>ISO</td><td>NACE</td><td>SSPC</td><td>ISO</td><td>NACE</td></tr><tr><td>SP1</td><td></td><td></td><td>SP8</td><td></td><td></td></tr><tr><td>SP2 SP3</td><td></td><td></td><td>SP9 SP10</td><td></td><td>No.2</td></tr><tr><td>SP4</td><td></td><td></td><td>SP11</td><td></td><td></td></tr><tr><td>SP5</td><td>Sa3</td><td>No.1</td><td>SP12</td><td></td><td>No.5</td></tr><tr><td>SP6</td><td>Sa2</td><td>No.3</td><td>SP13</td><td></td><td>No.6</td></tr><tr><td>SP7</td><td>Sal</td><td>No.4</td><td>SP14</td><td></td><td>No.8</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1405,
+        "chunk": "# 5.几种物理处理方法的对比  \n\n各种底材处理方法都有其特点，有的除锈质量较好，有的施工比较方便，有的则费用较低，所以在设计表面处理时应该综合考虑各种因素，确定比较适合的方法。表5-2-5列出了几种物理处理方法的优缺点，供参考。  \n\n表5-2-5几种物理处理方法对比  \n\n\n<html><body><table><tr><td>除锈方法</td><td>除锈 质量</td><td>表面粗 糙度</td><td>对漆膜保护 性能的影响</td><td>必要的施 工场地</td><td>现场施 工的适用</td><td>粉尘 问题</td><td>钢板厚 度限制</td><td>除锈费用</td></tr><tr><td>喷射处理</td><td></td><td></td><td></td><td>X</td><td></td><td>X</td><td>X</td><td>X</td></tr><tr><td>动力工具处理</td><td>##</td><td>X</td><td></td><td></td><td>#</td><td></td><td></td><td></td></tr><tr><td>手工工具处理</td><td>X</td><td>X</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>水喷射处理</td><td></td><td>X</td><td>△</td><td></td><td></td><td></td><td>X</td><td>X</td></tr></table></body></html>\n\n注： $\\boxed{1}$ 代表最佳；○代表良好； $\\Delta$ 代表勉强适用； $x$ 代表不适合，差，费用大，缺点多。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1406,
+        "chunk": "# 第二节 钢材表面的化学处理  \n\n实验表明，钢铁表面不经涂前处理的试件两年后涂层有 $60\\%$ 被锈蚀，而经过精细涂前处理的试件只发现个别锈点。因为钢铁表面的锈迹不但会影响涂料涂层与钢铁表面的粘接，还会对钢铁表面产生继续锈蚀，以致使涂层遭到严重破坏。  \n\n通常在金属零件表面往往附有氧化皮、油脂、灰尘等污垢物，如果在涂装前不把这些异物去除，将影响涂膜固化或造成涂膜龟裂、剥落，尤其是残留的氧化皮还会在涂膜下继续生长而失去涂装的意义。因此，涂装前处理的目的就是除去金属表面附着的各种污垢物，以提高金属与涂膜的附着力，从而保护金属不受腐蚀破坏。  \n\n人们通常把金属涂装前需要进行的脱脂、除锈、磷化这三道工序通称为“前处理”。前处理方法一般分为两大类，即机械的涂装前处理和化学的涂装前处理。  \n\n机械的涂装前处理方法在第一节中已有介绍，它包括采用键刀、刮刀、钢丝刷等工具以人工的操作方法或采用喷砂、喷丸、抛丸等的机械方法，除去金属表面的污垢物。前者不能把金属表面的氧化皮、污垢等异物彻底清除，但操作简便。而后者可以将其去除并可获得洁净且有一定粗糙度的表面，从而可增加涂料的附着力，并且效率高，但对于外形比较复杂或薄板成型的工件则不大适用。  \n\n化学的涂装前处理包括脱脂、酸洗和磷化等。  \n\n（1）脱脂由于防锈或加工的需要，在金属表面往往涂有防锈油、压延油、切削油等油性物质，灰尘极易附着其上。涂装前要把这些污垢物去掉，常用碱性脱脂剂、有机溶剂、乳化液脱脂剂或溶剂蒸气进行清洗，这是酸洗、磷化工序前所必须的。  \n\n(2）酸洗金属表面覆盖的氧化皮或锈蚀物会使涂膜的附着力、耐腐蚀性显著降低。为此要采用各种酸液将其去掉，这就是酸洗。为了防止过酸洗或氢脆，需要添加缓蚀剂。  \n\n(3）磷化（氧化）金属表面与磷化液反应，可使其表面生成一层稳定、难溶的无机化合物，这种化合物可提高涂膜的附着力和耐腐蚀性。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1407,
+        "chunk": "# 一、除油脂  \n\n除油脂的目的在于清除掉工件表面的油脂、油污，包括机械法、化学法两类。机械法主要有手工擦刷、喷砂抛丸、火焰灼烧等。化学法有溶剂清洗、酸性清洗剂清洗、强碱液清洗、低碱性清洗剂清洗等。以下主要介绍化学法除油脂工艺。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1408,
+        "chunk": "# 1.溶剂清洗  \n\n溶剂法除油脂一般采用非易燃的卤代烃蒸气法或乳化法。最常见的是采用三氯乙烷、三氯乙烯、全氯乙烯蒸气来去除油脂。蒸气脱脂速度快，效率高，脱脂干净彻底，对各类油及脂的去除效果都非常好。在氯代烃中加人一定的乳化液，不管是浸泡还是喷淋效果都很好。由于氯代卤都有一定的毒性，汽化温度也较高，再者由于新型水基低碱性清洗剂的出现，溶剂蒸气和乳液除油脂方法现在已经很少使用了。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1409,
+        "chunk": "# 2.酸性清洗剂清洗  \n\n酸性清洗剂除油脂是一种应用非常广泛的方法。它利用表面活性剂的乳化、润湿、渗透原理，并借助于酸腐蚀金属产生氢气的机械剥离作用，达到除油脂的目的。酸性清洗剂可在低温和中温下使用。低温一般只能除掉液态油，中温就可除掉油和脂，一般只适合于浸泡处理方式。酸性清洗剂主要由表面活性剂（如OP类非离子型活性剂、阴离子磺酸钠型）、普通无机酸、缓蚀剂三大部分组成。由于它兼备有除锈与除油脂双重功能，人们习惯称之为“二合—”处理液。常见的酸性清洗剂配方及工艺参数见表5-2-6。  \n\n表5-2-6 常见酸性清洗剂配方和工艺  \n\n\n<html><body><table><tr><td>工艺</td><td>低温型</td><td>中温型</td><td>磷酸酸基型</td></tr><tr><td>工业盐酸（31%）/%</td><td>20~50</td><td>0</td><td>0</td></tr><tr><td>工业硫酸（98%）/%</td><td>0~15</td><td>15~30</td><td>0</td></tr><tr><td>工业磷酸（85%）/%</td><td>0</td><td>0</td><td>10~40</td></tr><tr><td>表面活性剂（OP类，磺酸类）/%</td><td>0.4～1. 0</td><td>0. 4~1.0</td><td>0.4~1.0</td></tr><tr><td>缓蚀剂</td><td>适量</td><td>适量</td><td>适量</td></tr><tr><td>使用温度/℃</td><td>常量～45</td><td>50~80</td><td>常温～80</td></tr><tr><td>处理时间/min</td><td>适当</td><td>5~10</td><td>适当</td></tr></table></body></html>  \n\n盐酸、硫酸基的清洗剂应用最为广泛，其成本低，效率也较高。但酸洗残留的 $C1^{-}$ P$\\mathrm{5O_{\\sharp}^{2-}}$ 对工件的后腐蚀危害很大。磷酸基本没有腐蚀物残留的隐患，但磷酸成本较高，清洗效率低些。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1410,
+        "chunk": "# 3.强碱液清洗  \n\n强碱液除油脂是一种传统的有效方法。它是利用强碱对植物油的皂化反应，形成溶于水的皂化物来达到除油脂的目的。纯粹的强碱液只能皂化除掉植物油脂而不能除掉矿物油脂。因此人们通过在强碱液中加入表面活性剂，一般是磺酸类阴离子活性剂，利用表面活性剂的乳化作用达到除矿物油的目的。强碱液除油脂的使用温度都较高，通常 ${>}80^{\\circ}C$ 。常用强碱液  \n\n清洗配方与工艺如下。  \n\n\n<html><body><table><tr><td>氢氧化钠/%</td><td>5~10</td><td>处理温度/℃</td><td>>80</td></tr><tr><td>硅酸钠/%</td><td>2~8</td><td>处理时间/min</td><td>5~20</td></tr><tr><td>磷酸钠（或碳酸钠）/%</td><td>1~10</td><td>处理方式</td><td>浸泡、喷淋均可</td></tr><tr><td>表面活性剂（磺酸类）/%</td><td>2~5</td><td></td><td></td></tr></table></body></html>  \n\n强碱液除油脂需要较高温度，能耗大，对设备腐蚀性也大，并且材料成本并不算低，因此这种方法的应用正逐步减少。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1411,
+        "chunk": "# 4.低碱性清洗液清洗  \n\n低碱性清洗液是当前应用最为广泛的一类除油脂剂。它的碱性低，一般 $\\mathsf{p H}$ 为 ${\\mathfrak{g}}\\sim{\\mathrm{12}}$ 对设备腐蚀较小，对工件表面状态破坏小，可在低温和中温下使用，除油脂效率较高。特别在喷淋方式使用时，除油脂效果特别好。低碱性清洗剂主要由无机低碱性助剂、表面活性剂、消泡剂等组成。无机型助剂主要是硅酸钠、三聚磷酸钠、磷酸钠、碳酸钠等。其作用是提供一定的碱度，有分散悬浮作用。可防止脱下来的油脂重新吸附在工件表面。表面活性剂主要采用非离子型与阴离子型，一般是聚氯乙烯OP类和磺酸盐型，它在除油脂过程中起主要的作用。在有特殊要求时还需要加入一些其他添加物，如喷淋时需要加人消泡剂，有时还加人表面调整剂，起到脱脂、表调双重功能。低碱性清洗剂已有很多商业化产品，如PA30-IM、PA30-SM、FC-C4328、Pyroclean442等。  \n\n一般常用的低碱性清洗液配方和工艺见表5-2-7。  \n\n表5-2-7 常用低碱性清洗液配方和工艺  \n\n\n<html><body><table><tr><td>类型</td><td>浸泡型</td><td>喷淋型</td><td>类型</td><td>浸泡型</td><td>喷淋型</td></tr><tr><td>三聚磷酸钠/（g/L）</td><td>4~10</td><td>4~10</td><td>表面调整剂/(g/L)</td><td>0~3</td><td>0~3</td></tr><tr><td>硅酸钠/(g/L)</td><td>0~10</td><td>0~10</td><td>游离碱度/点</td><td>5~20</td><td>5~15</td></tr><tr><td>碳酸钠/(g/L)</td><td>4~10</td><td>4~10</td><td>处理温度/C</td><td>常温～80</td><td>40～70</td></tr><tr><td>消泡剂/(g/L)</td><td></td><td>0.5~3.0</td><td>处理时间/min</td><td>5~20</td><td>1.5~3. 0</td></tr></table></body></html>  \n\n浸泡型清洗剂主要应注意的是表面活性剂的浊点问题，当处理温度高于浊点时，表面活性剂析出上浮，使之失去脱脂能力，一般加人阴离子型活性剂即可解决。喷淋型清洗剂应加人足够的消泡剂，在喷淋时不产生泡沫尤为重要。  \n\n铝件、锌件清洗时，必须考虑到它们在碱性条件下的腐蚀问题，一般宜用接近中性的清洗剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1412,
+        "chunk": "# 二、酸洗  \n\n用酸洗除锈、除氧化皮的方法是工业领域应用最为广泛的方法。利用酸对氧化物溶解以及腐蚀产生氢气的机械剥离作用达到除锈和除氧化皮的目的。酸洗中使用最为常见的是盐酸、硫酸、磷酸。硝酸由于在酸洗时产生有毒的二氧化氮气体，一般很少应用。盐酸酸洗适合在低温下使用，不宜超过 $45^{\\circ}C$ ，使用浓度 $10\\%\\sim45\\%$ ，还应加人适量的酸雾抑制剂为宜。硫酸在低温下的酸洗速率很慢，宜在中温使用，温度 $50\\sim80^{\\circ}C$ ，使用浓度 $10\\%\\sim25\\%$ 。磷酸酸洗的优点是不会产生腐蚀性残留物（盐酸、硫酸酸洗后或多或少会有 $\\mathbf{Cl^{-}}$ ， $\\mathrm{5O_{4}^{2-}}$ 残留)，比较安全，但磷酸的缺点是成本较高，酸洗速率较慢，一般使用浓度 $10\\%\\sim40\\%$ ，处理温度可常温至 $80^{\\circ}C$ 。在酸洗工艺中，采用混合酸也是非常有效的方法，如盐酸-硫酸混合酸、磷酸-柠檬酸混合酸。  \n\n在酸洗除锈除氧化皮槽液中，必须加入适量的缓蚀剂。缓蚀剂的种类很多，选用也比较容易，它的作用是抑制金属腐蚀和防止“氢脆”。但酸洗“氢脆”敏感的工件时，缓蚀剂的选择应特别小心，因为某些缓蚀剂抑制两个氢原子变为氢分子的反应，即2[H]—→Hz↑，使金属表面氢原子的浓度提高，增强了“氢脆”倾向。因此必须查阅有关腐蚀数据手册，或做“氢脆”试验，避免选用危险的缓蚀剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1413,
+        "chunk": "# 三、磷化处理  \n\n磷化处理工艺应用于工业已有近百年的历史，磷化工艺过程是一种化学与电化学反应形成磷酸盐化学转化膜的过程，这层不溶的化学转化膜通常是由金属与稀磷酸或酸性磷酸盐溶液反应形成的。磷化处理过程所形成的磷酸盐转化膜称之为磷化膜。磷化的目的主要是给基体金属提供保护，在一定程度上防止金属被腐蚀；或用于涂漆前打底，提高漆膜层的附着力与防腐蚀能力。在金属冷加工工艺中也通常使用磷化膜起减摩润滑使用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1414,
+        "chunk": "# 1.磷化的分类  \n\n磷化的分类方法很多，但一般是按磷化成膜体系、磷化膜厚度、磷化使用温度、促进剂类型进行分类。  \n\n（1）按磷化成膜体系主要分为：锌系、锌钙系、锌锰系、锰系、铁系、非晶相铁系六大类。  \n\n(2）按磷化膜厚度（磷化膜重）分，可分为次轻量级、轻量级、次重量级、重量级四种。其中次轻量级膜重仅 $0.1{\\sim}1.0{\\bf g}/\\mathrm{m}^{2}$ ，一般是非晶相铁系磷化膜，仅用于漆前打底，特别是变形大工件的涂漆前打底效果很好。轻量级膜重 $\\mathrm{1.1{\\sim}4.5g/m^{2}}$ ，广泛应用于漆前打底，在防腐蚀和冷加工行业应用较少。次重量级磷化膜重 $4.6\\sim7.5{\\mathrm{g}}/{\\mathrm{m}}^{2}$ ，由于膜重较大，膜较厚（一般 $>3\\mu\\mathrm{m};$ ，较少作为漆前打底（仅作为基本不变形的钢铁件漆前打底)，可用于防腐蚀及冷加工减摩润滑。重量级膜重大于 $7.5\\mathrm{g/m^{2}}$ ，不作为漆前打底用，广泛用于防腐蚀及冷加工。  \n\n(3）按处理温度可分为常温、低温、中温、高温四类。常温磷化就是不加温磷化。低温磷化一般处理温度 $30{\\sim}45^{\\circ}C$ ，中温磷化一般 $60\\sim70^{\\circ}C$ ，高温磷化一般 $>80^{\\circ}C$ ，温度划分法本身并不严格。  \n\n(4）按促进剂类型分类，由于磷化促进剂主要只有几种，按促进剂的类型分类有利于槽液的了解。根据促进剂类型大体可决定磷化处理温度，如 $\\mathrm{NO}_{3}^{-}$ 促进剂主要就是中温磷化。促进剂主要分为：硝酸盐型、亚硝酸盐型、氯酸盐型、有机氮化物型、钼酸盐型等主要类型。每一个促进剂类型又可与其他促进剂配套使用，有不少的分支系列。硝酸盐型包括： $\\mathrm{NO}_{3}^{-}$ 型， $\\mathrm{NO_{3}^{-}/N O_{2}^{-}}$ （自生型)。氯酸盐型包括： $\\mathrm{ClO_{3}^{-}}$ ， $\\mathrm{ClO_{3}^{-}/\\ N O_{3}^{-}}$ ， $\\mathrm{ClO_{3}^{-}/\\ N O_{2}^{-}}$ 。亚硝酸盐包括：硝基胍 $\\mathrm{R{-NO_{2}^{-}/\\ C l O_{3}^{-}}}$ 。钼酸盐型包括： $\\mathrm{MoO_{4}^{-}}$ ， $\\mathrm{MoO_{4}^{-}/\\ C l O_{3}^{-}}$ ， $\\mathrm{MoO_{4}^{-}/N O_{3}^{-}}$ 。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1415,
+        "chunk": "# 2.防锈磷化处理工艺  \n\n磷化工艺的早期应用是防锈，钢铁件经磷化处理形成一层磷化膜，起到防锈作用。经过磷化防锈处理的工件防锈期可达几个月甚至几年（对涂漆工件而言)，广泛用于工序间、运输、包装贮存及使用过程中的防锈，防锈磷化主要有铁系磷化、锌系磷化、锰系磷化三大品种。  \n\n铁系磷化的主体槽液成分是磷酸亚铁溶液，不含氧化类促进剂，并且有高游离酸度。这种铁系磷化处理温度高于 $95^{\\circ}C$ ，处理时间长达 $30\\mathrm{min}$ 以上，磷化膜重大于 $\\mathrm{10g/m^{2}}$ ，并且有除锈和磷化双重功能。这种高温铁系磷化由于磷化速率太慢，现在应用很少。锰系磷化用作防锈磷化具有最佳性能，磷化膜微观结构呈颗粒密堆集状，是应用最为广泛的防锈磷化。加与不加促进剂均可，如果加人硝酸盐或硝基胍促进剂可加快磷化成膜速率。通常处理温度  \n\n80～100℃，处理时间10～20min，膜重在7.5g/m²以上。锌系磷化也是广泛应用的一种防锈磷化，通常采用硝酸盐作为促进剂，处理温度80～90℃，处理时间10～15min，磷化膜重大于 $7.5{\\mathrm{g}}/{\\mathrm{m}}^{2}$ ，磷化膜微观结构一般是针片紧密堆集型。  \n\n防锈磷化—般工艺流程为：除油除锈→水清洗→表面调整活化→磷化→水清洗→铬酸盐处理 $\\mathbf{-}\\mathbf{\\delta}$ 烘干 $\\nrightarrow$ 涂油脂或染色处理。  \n\n通过强碱强酸处理过的工件会导致磷化膜粗化现象，应采用表面调整。表面调整的目的是促使磷化形成晶粒细致、密实的磷化膜，以及提高磷化速率。表面调整剂主要有两种：一种是酸性表调剂，如草酸；另一种是胶体钛。两者的应用都非常普及，前者还兼备有除轻锈（工件运行过程中形成的“水锈”及“风锈”）的作用。在磷化前处理工艺中，是否选用表面调整工序和选用哪一种表调剂都是由工艺与磷化膜的要求来决定的。一般原则是：涂漆前打底磷化、快速低温磷化需要表面调整。如果工件在进人磷化槽时，已经二次生锈，最好采用酸性表调，但酸性表面调整只适合于 ${\\geq}50^{\\circ}C$ 的中温磷化。一般中温锌钙系磷化不表面调整也行，锌系磷化可采用草酸、胶体钛表面调整。锰系磷化可采用不溶性磷酸锰悬浮液活化。铁系磷化一般不需要调整活化处理。磷化后的工件经铬酸盐封闭可大幅度提高防锈性，如再经过涂油或染色处理可将防锈性提高几位甚至几十倍。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1416,
+        "chunk": "# 3.减摩磷化处理工艺  \n\n对于发动机活塞环、齿轮、制冷压缩机一类工件，它不仅承受一次载荷，而且还有运动摩擦，要求工件能减摩、耐磨。锰系磷化膜具有较高的硬度和热稳定性，能耐磨损，磷化膜具有较好的减摩润滑作用。因此，广泛应用于活塞环、轴承支座、压缩机等零部件。这类耐磨减摩磷化处理温度 $70\\sim100^{\\circ}C$ ，处理时间 $10{\\sim}20\\mathrm{min}$ ，磷化膜重大于 $7.5\\mathrm{g}/\\mathrm{m}^{2}$ 0  \n\n在冷加工行业，如接管、拉丝、挤压、深拉延等工序，要求磷化膜提供减摩润滑性能，一般采用锌系磷化：一是锌系磷化膜皂化后形成润滑性很好的硬脂酸锌层；二是锌系磷化操作温度比较低，可在 $40^{\\circ}C$ ， $60^{\\circ}C$ 或 $90^{\\circ}C$ 条件下进行磷化处理，磷化时间 $4\\mathrm{\\sim}10\\mathrm{min}$ ，有时甚至几十秒钟即可，磷化膜重量要求 $\\mathrm{\\geq3g/m^{2}}$ 便可。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1417,
+        "chunk": "# 4.漆前磷化处理工艺  \n\n涂装底漆前的磷化处理，将提高漆膜与基体金属的附着力，提高整个涂层系统的耐腐蚀能力；提供工序间保护以免形成二次生锈。因此漆前磷化的首要问题是磷化膜必须与底漆有优良的配套性，而磷化膜本身的防锈性是次要的，磷化膜细致密实、膜薄。当磷化膜粗厚时，会对漆膜的综合性能产生负效应。磷化体系与工艺的选定主要由：工件材质、油锈程度、几何形状；磷化与涂漆的时间间隔；底漆品种和施工方式以及相关场地设备条件决定。一般来说，低碳钢较高碳钢容易进行磷化处理，磷化成膜性能好些。对于有锈（氧化皮）工件必须经过酸洗工序，而酸洗后的工件将给磷化带来很多麻烦，如工序间生锈泛黄、残留酸液的清除、磷化膜出现粗化等。酸洗后的工件在进行锌系、锌锰系磷化前一般要进行表面调整处理。在间歇式的生产场合，由于受条件限制，磷化工件必须存放一段时间后才能涂漆，因此要求磷化膜本身具有较好的防锈性。如果存放期在10天以上，一般应采用中温磷化，如中温锌系、中温锌锰系、中温锌钙系等，磷化膜的厚度最好应在 $\\mathrm{2.0{\\sim}4.5g/m^{2}}$ 之间。磷化后的工件应立即烘干，不宜自然晾干，以免在夹缝、焊接处形成锈蚀。如果存放期只有$3\\sim5$ 天，可用低温锌系、轻铁系磷化，烘干效果会好于自然晾干。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1418,
+        "chunk": "# 四、铬酸盐处理  \n\n铬酸盐处理是使金属表面转化成以铬酸盐为主要组成的膜的一种工艺方法，实现这种转  \n\n化所用的介质一般是以铬酸、碱金属的铬酸盐或重铬酸盐为基本成分的溶液。大多数工业上常用的金属或金属镀层，都可以使其表面转化成铬酸盐膜。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1419,
+        "chunk": "# 1.铬酸盐处理的目的  \n\n钢铁材料表面经过铬酸盐化学转化处理后可显著提高其抗蚀能力，同时该转化膜对涂层有良好的附着力，加之成本低廉，因而在汽车、机械、家用电器、建筑材料等领域得到了厂泛应用。铬酸盐处理除具有适用性广的特点外，还具有工艺方法简便、处理所需时间较短以及所得转化膜在防护性能上比磷酸盐膜还要好等多方面的优点。金属进行铬酸盐处理的目的是：  \n\n$\\textcircled{1}$ 提高金属或金属镀层的耐腐蚀性能；  \n$\\textcircled{2}$ 提高金属同漆层或其他有机涂料的黏附能力；  \n$\\textcircled{3}$ 避免金属表面污染；  \n$\\textcircled{4}$ 获得带色的装饰外观。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1420,
+        "chunk": "# 2.铬化膜的形成  \n\n通常，金属在含有能起活化作用的添加物的铬酸盐溶液中，形成铬酸盐转化膜的过程大致分为如下向个步骤：  \n\n$\\textcircled{1}$ 金属表面被氧化，并以离子形式进入溶液，同时有氢在表面上析出；  \n$\\textcircled{2}$ 所析出的氢，促使一定数量的六价铬还原成三价铬；  \n$\\textcircled{3}$ 金属溶液界面区 $\\mathbf{pH}$ 的升高，三价铬以氢氧化铬胶体形式沉淀；  \n$\\textcircled{4}$ 氢氧化铬胶体自溶液中吸附和结合一定数量的六价铬，构成具有某种组成的转化膜。  \n\n各种金属在铬酸盐溶液中，形成铬酸盐膜的转化过程虽然大致相同，但涉及过程的细节，特别是中间产物的形态，则因受转化的金属而异。即使是同一种金属也因不同的研究条件而有着不完全的反应机理。一般来说，铬酸盐膜层可分为两种类型，即黄色与绿色的铬酸盐膜层。由于两者色相的组成不同，在处理液中的反应机理也不同。虽然铬酸盐可在镉、铁、铜、镁、锡、银等金属表面上析出，但主要是用于铝材及锌材表面的成膜。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1421,
+        "chunk": "# 3.铬化膜的性质  \n\n一般来说，铬酸盐转化膜的主要组分是六价铬与三价铬的化合物及基底金属铬酸盐，至于各组分的比例以及是否含有其他别的化合物，这将取决于成膜条件。对于钢铁表面所形成的铬酸盐膜而言，根据不同研究者的观察，其组成与结构也不完全一样。在含有氟化物及其他添加剂的铬酸溶液中，膜的组成除三价铬和铁的含水氧化物外，还含有六价铬的复合物。  \n\n各种金属上的铬酸盐膜，大都具有某种色泽特征，其深浅受处理金属的种类、成膜工艺条件和后处理的方法等多种因素而定。膜厚一般在 $0.3{\\sim}30\\mathrm{mg/dm^{2}}$ 之间。铬酸盐膜的最大优点是电阻率十分低，特别适合在电气和电子工业中应用。铬酸盐转化膜的孔隙率通常是比较低的。薄的铬酸盐膜对色料具有较好的吸收能力，容易进行着色。铬酸盐膜对靠空气干燥的漆料如硝基漆橡胶和其他黏结剂都有较好的黏附能力。此外，铬酸盐膜对金属有缓蚀作用，一旦腐蚀，介质透过漆膜，钝化膜进行自我修复，仍可延缓底层锈蚀出现，使漆膜保持完好。铬酸盐膜同基底金属结合力通常是十分良好的，当经受压缩或成型加工时，具有足够的韧性，但耐磨性非常差，其硬度在很大程度上取决于成膜条件。薄的铬酸盐膜对焊接无明显影响，而厚的铬酸盐膜层对焊接带来困难。  \n\n铬酸盐膜的防护特征：经过铬酸盐处理的金属，其耐蚀性与金属本身以及成膜工艺条件不同而不同，但总在一定程度上有所提高。其防护作用通常认为：一是膜的致密性保证与腐蚀介质隔开；二是六价铬起到缓蚀作用。在各种介质中的耐蚀性是不一样的，铬酸盐膜对基底金属在各种介质中的耐蚀性影响，要视基底金属的种类、成膜的工艺条件和坏境条件等诸多因素而定。因此，在这方面的许多试验数据，只有在符合特定试验条件下才有参考价值。加热对铬酸盐膜防护性能有重要的影响，铬酸盐膜在超过某一特定温度下加热时，其防护作用将要下降，这是由于膜的组成和结构在加热时产生了变化。因此，在使用时要特别注意。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1422,
+        "chunk": "# 五、金属表面化学处理的检测标准  \n\n（1）除油效果的检测除油效果的好坏，可用多种方法判断，最常用且较简便的方法是水膜中断法，即工件经过彻底水洗后，观察水是否能在表面完全润湿。如果除油彻底，水洗后表面应能形成连续的水膜，否则除油不彻底。此外，还有荧光染料法、喷雾器法、放射性同位素法等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1423,
+        "chunk": "# （2）磷化膜质量评定方法  \n\n$\\textcircled{1}$ 外观目测法目测法是用肉眼观察磷化膜的表面颜色、结晶粗细、膜层的连续性及缺陷。好的磷化膜，外观均匀、完整、细密，无金属亮点，无白灰。锌系磷化膜为灰色膜，铁系磷化膜为彩虹色膜。  \n\n$\\textcircled{2}$ 厚度（或重量法）测定磷化膜厚度测定可直接采用磁性测厚仪，使用方便、快速，但是薄膜磷化厚度在 $3\\mu\\mathrm{m}$ 以下，测厚仪精度有限，有时误差较大。采用重量法测定较为准确，对钢板上的磷化膜测定方法是将磷化板浸泡在 $75\\mathrm{{^\\circC}}$ 、浓度为 $5\\%$ 的铬酸溶液中 $10{\\sim}15\\operatorname*{min}$ 以除去磷化膜，然后根据除去膜层前后的重量差求得膜重，单位一般以 ${\\bf\\dot{g}/\\mathbf{\\dot{m}}^{2}\\mathbf{\\dot{\\omega}}^{p}}$ 表示。  \n\n(3）腐蚀性测定 最简便的方法称点滴法，点滴测试液的组成如下。  \n\n硫酸铜 $\\mathrm{CuSO_{4}\\cdot5H_{2}O/(g/L)}$ 41 0.1mol/L盐酸 $\\mathrm{HCl}/(\\mathrm{mL}/\\mathrm{L})$  \n\n氯化钠 $\\mathrm{NaCl/f(g/L)}$  \n\n35  \n\n用脱脂棉蘸冰醋酸或汽油去除磷化膜表面的油污，然后滴一滴测试溶液在其表面上，当试液的天蓝色变成土红色的为终点，记录所需时间（min)。  \n\n对于薄膜磷化，应将磷化与其后序的涂层复合起来进行盐雾试验、耐湿热试验。  \n\n（4）脱脂剂总碱度及游离碱度的测定  \n\n$\\textcircled{1}$ 试剂及仪器酚酞指示剂，甲基橙指示剂， $0.1\\mathrm{mol/L}$ 的HCI；滴定管、移液管、 $250\\mathrm{mL}$ 的锥形瓶。  \n\n$\\textcircled{2}$ 操作步骤用移液管吸取 $10\\mathrm{mL}$ 脱脂工作液于锥形瓶中，加人 $10\\mathrm{mL}$ 的蒸馏水。滴人三滴酚酰指示剂，用 $0.1\\mathrm{mol/L}$ 的HCI滴至颜色由粉红色至无色为终点，设所消耗的HCl的体积（ $\\mathrm{mL}$ ）为游离酸度的点数；滴人三滴甲基橙指示剂、上述HCI继续滴定至溶液颜色由橙色变为红色为终点，所用HCl的体积（ $:\\mathrm{mL}$ ）即为总碱度点数。  \n\n（5）表调剂含量的比色法测定  \n\n$\\textcircled{1}$ 试剂及仪器 $98\\%\\mathrm{~H_{2}S O_{4}~}$ ， $\\mathrm{{H}}_{2}\\mathrm{{O}}_{2}$ ；比色管 $50\\mathrm{mL}$ 规格，移液管。  \n\n$\\textcircled{2}$ 操作步骤准确配制质量分数为 $0.1\\%$ 的表调剂水溶液，取 $25\\mathrm{mL}$ 置于 $50\\mathrm{mL}$ 的比色管中，加人浓度为 $98\\%$ 的 $\\mathrm{H_{2}S O_{4}\\ 5m L}$ 摇匀，再加 $\\mathrm{H_{2}O_{2}\\ 5m L}$ ，摇匀即显出黄色，则为质量分数 $0.1\\%$ 的表调剂标准溶液颜色。按上述方法分别配制质量分数为 $0.15\\%$ ， $0.3\\%$ 的标准溶液看其颜色。  \n\n取工作液 $25\\mathrm{mL}$ ，按上述方法加 $\\mathrm{HzSO_{4}}$ 和 $\\mathrm{H}_{2}\\mathrm{O}_{2}$ 制出工作液的颜色。将工作液颜色与标准颜色进行目视比色，以确定工作液的浓度范围。  \n\n另外，在生产线上使用表调剂时，也有用 $\\mathsf{p H}$ 、碱度来控制槽液浓度的，具体采用哪一种方法，可与供应商来讨论确定。  \n\n(6）总酸度（TA）的测定取处理液10mL，用酚作指示剂，以0.1mol/L的标准氢氧化钠溶液滴定溶液变粉红时（pH8.5时）所耗用的NaOH标准溶液的体积（mL）称为总酸度，用“点”来表示。例如，有的磷化总酸控制范围为 $18\\sim24$ 点。  \n\n(7）游离酸度的测定取处理液10mL，用溴酚蓝作指示剂，以0.1mol/L的NaOH标准溶液滴定至溶液变蓝时为终点，所耗用 $\\mathrm{\\DeltaNaOH}$ 的体积（ $\\operatorname{\\mathrm{(mL)}}$ ）为游离酸度的“点”数。  \n\n以上滴定属中和滴法，通常根据指示剂颜色变化来判断滴定终点，因此难免因操作者不同而产生某些误差，如要求结果更为精确时可采用以下方法：  \n\n$\\textcircled{1}$ 用 $\\mathbf{\\pH}$ 为3.8的溴酚蓝标准液比色来确定终点；  \n\n$\\textcircled{2}$ 用 $\\mathbf{\\pH}$ 为3.8作终点的 $\\mathbf{pH}$ 滴定法。  \n\n上述中和滴定法也可用申基橙作指示剂。  \n\n（8）促进剂的点数用发酵管装满槽液，把空气排出，加 $2{\\sim}3{\\mathrm{g}}$ 固体氨基苯磺酸，放置数秒钟后，从发酵管刻上读出发气量的体积（mL)，即是促进剂的点数。  \n\n![](images/6b49325faaa32fa386df46ac1a8f7739b0e0bc0f47b5a24b554100c19a02b96c.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1424,
+        "chunk": "# 一、锌及锌合金的表面预处理  \n\n锌及锌合金在正常的条件下不易被腐蚀，但若有酸、碱或电解盐的存在下则会很快被腐蚀，所以在锌及锌合金表面涂装保护是必要的。因为锌及锌合金表面平滑，涂膜不易附着，而经过表面处理可使工件表面粗糙，形成能防止与涂料反应的保护膜，可使涂膜与工件表面结合牢固。目前常用的表面处理方法有以下几种。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1425,
+        "chunk": "# 1.表面脱脂  \n\n锌及锌合金的被涂物和其他金属制品一样，在加工和贮运过程中会沾上油污，在涂装前表面预处理（如磷化处理）必须先进行脱脂清洗，不然会影响涂膜的附着力，容易起泡脱落。其脱脂方法和操作基本上与黑色金属相同，只不过锌及锌合金不能像黑色金属那样能耐强碱的侵蚀，所以不能采用强碱配制的清洗剂清洗，一般宜采用有机溶剂脱脂法、表面活性剂脱脂法，或由碳酸钠、磷酸钠和硅酸钠等配制的弱碱性清洗剂脱脂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1426,
+        "chunk": "# 2.磷化处理  \n\n磷化处理是利用磷酸或含磷酸盐的溶液对工件进行处理，使其基底金属表面生成一层不溶性磷酸盐膜的过程。例如锌及锌合金与磷化溶液反应时，就在其表面生成一种不溶性的$\\mathrm{{Zn}_{3}(P O_{4})_{2}\\cdot4H_{2}O}$ 膜，从而起到了保护作用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1427,
+        "chunk": "# 3.铬酸盐处理  \n\n将锌及锌合金在含铬的酸性溶液中处理1min左右的无机铬酸盐膜。膜层的结构可表示为 $\\mathrm{XZnCrO_{4}\\bullet3Z n(O H)_{2}\\bullet3Z n X}$ （X是某种阴离子，如硫酸根离子)。  \n\n根据实际使用的不同处理液配方，膜层可呈无色、黄色或橄榄绿色，膜层厚度及耐腐蚀性能也依次增加。采用稀酸或稀碱对有色膜进行脱色处理，可获得无色膜层。  \n\n无色膜层的耐腐蚀性能有限，主要用于工件存放和处理过程中暂时性保护。这种处理通常是在电镀锌和热浸镀锌完成后立即进行。  \n\n黄色膜具有良好的耐腐蚀性能，也可作为一般涂装和粉末涂装的良好基底。橄榄绿色膜  \n\n则专门用作耐腐蚀保护层。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1428,
+        "chunk": "# 二、铝及铝合金的表面预处理  \n\n铝是一种比较活泼的金属，但纯铝在常温下或干燥空气中则比较稳定。这是因为铝在空气中与氧发生作用，在铝表面生成一层薄而致密的氧化膜，其厚度为 $0.01\\sim0.015\\mu\\mathrm{m}$ ，能起到保护作用。在铝中加人 $\\mathbf{M}_{\\mathbf{E}}$ ， $c_{u}$ 、Zn等元素制成铝合金后，虽然机械强度提高了，但耐腐蚀性下降了。这就需要根据使用环境的要求，经过一定的表面处理，再涂装所需的涂料加以保护。  \n\n铝及铝合金表面光滑，涂膜附着不牢，经过化学转化膜处理后，可以提高基体与涂膜间的结合力。  \n\n铝及铝合金在进行化学转化膜处理之前，也要进行清洗，去掉油污和杂物，其清洗方法与锌及锌合金的表面脱脂方法相同。下面将铝及铝合金的涂装前表面预处理方法介绍如下。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1429,
+        "chunk": "# 1.化学氧化膜法（碱性溶液氧化法）  \n\n将铝及铝合金置于含碳酸钠、铬酸盐等碱性溶液中，在高温下处理 $5\\sim20\\mathrm{min}$ ，使表面生成一层氧化膜。氧化后的工件要进行钝化处理，其目的是使氧化膜稳定，并中和残留在工件表面的碱性溶液，可进一步提高耐腐蚀能力。钝化溶液为含铬酐 $20\\mathrm{g/L}$ 的水溶液，处理时间为 $5\\sim15{\\bf s}$ ，冲洗干净后，再放到 $50^{\\circ}C$ 的烘箱中烘干，烘干后即可涂装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1430,
+        "chunk": "# 2.磷酸铬酸盐膜 （绿膜铬酸盐法）  \n\n这种处理液的主要成分是磷酸、铬酸，内含有作为腐蚀剂的氟化物或其复合盐，溶液的$\\mathbf{pH}$ 为 $1.5{\\sim}3.0$ 品  \n\n与磷酸盐不同，被还原的氢氧化铬与磷酸反应，生成难溶性的磷酸铬（三价铬）析出。  \n化学反应如下。  \n\n$\\textcircled{1}$ 氢氟酸引起铝腐蚀的化学反应。  \n\n阳极：  \n\n$$\n\\begin{array}{r l}{2\\mathrm{Al}+6\\mathrm{HF}\\longrightarrow2\\mathrm{AlF}_{3}+3\\mathrm{H}_{2}\\uparrow}&{{}}\\\\ {2\\mathrm{Al}\\longrightarrow2\\mathrm{Al}^{3+}+3\\mathrm{H}_{2}\\uparrow}&{{}}\\\\ {6\\mathrm{H}^{+}+6\\mathrm{e}^{-}\\longrightarrow3\\mathrm{H}_{2}\\uparrow}&{{}}\\end{array}\n$$  \n\n阴极：  \n\n铝的表面附近的溶液因 $\\mathbf{H^{+}}$ 减少而使 $\\mathbf{pH}$ 上升。  \n\n$\\textcircled{2}\\mathrm{\\textrm{HCrz}}\\mathrm{\\mathrm{O}}_{7}^{-}$ 离解，在阴极上 $\\mathbf{Cr^{\\tilde{6}+}}$ 的化学反应。  \n\n$$\n3\\mathrm{H}_{2}+\\mathrm{HCr}_{2}\\mathrm{O}_{7}^{-}\\longrightarrow2\\mathrm{Cr}(\\mathrm{OH})_{3}+\\mathrm{OH}^{-}\n$$  \n\n$\\textcircled{3}$ 在某一 $\\mathbf{pH}$ 下，由于三价铬和磷酸化学反应，析出磷酸铬。  \n\n$$\n\\begin{array}{r l}{2\\mathrm{Cr}(\\bar{\\mathrm{OH}})_{3}+2\\mathrm{H}_{3}\\mathrm{PO}_{4}\\longrightarrow2\\mathrm{Cr}\\mathrm{PO}_{4}\\downarrow+6\\mathrm{H}_{2}\\bar{\\mathrm{O}}}&{}\\\\ {2\\mathrm{Al}^{3+}+2\\mathrm{H}_{3}\\mathrm{PO}_{4}\\longrightarrow2\\mathrm{Al}\\mathrm{PO}_{4}\\downarrow+6\\mathrm{H}^{+}}&{}\\end{array}\n$$  \n\n$\\textcircled{4}$ 铝氧化物析出的化学反应。  \n\n$$\n2\\mathrm{Al^{3+}}+6\\mathrm{OH^{-}}\\longrightarrow2\\mathrm{Al(OH)_{3}}\\longrightarrow\\mathrm{Al_{2}O_{3}}+2\\mathrm{H_{2}O}\n$$  \n\n所生成的膜为非晶质，其组成为 $\\mathrm{Al_{2}O_{3}\\bullet2C r P O_{4}\\bullet8H_{2}O_{4}}$ 中  \n\n薄的处理膜（小于 $\\mathrm{1g/m^{2}}$ ）适用于涂膜底层。厚的处理膜则具有良好的耐蚀能力，并适于装饰性应用。虽然新鲜的处理液可以形成色泽鲜艳的绿膜，但随着槽液中 $\\mathbf{Al^{3+}}$ 含量的增加，其色泽会逐渐变淡。为了防止色泽的变化，必须控制槽液中 $\\mathbf{Al^{3+}}$ 含量。为此，可添加碱金属氟盐，使 $\\mathbf{Al^{3+}}$ 作为配位氟化物沉淀析出。铝合金典型的铬酸、磷酸盐处理工艺规程见表5-2-8。  \n\n表5-2-8铝合金典型的铬酸、磷酸盐处理工艺规程  \n\n\n<html><body><table><tr><td>溶液组成及工艺</td><td>配方1</td><td>配方2</td></tr><tr><td>铬酐/(g/L)</td><td>12</td><td>7</td></tr><tr><td>磷酸(纯)/(g/L)</td><td>67</td><td>58</td></tr><tr><td>氟化钠/(g/L)</td><td>4~5</td><td>3~5</td></tr><tr><td>温度/C</td><td>50</td><td>25</td></tr><tr><td rowspan=\"2\">时间/min</td><td>2(浸渍法）</td><td>10(浸渍法)</td></tr><tr><td>0.5(喷射法)</td><td>3～5(喷射法)</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1431,
+        "chunk": "# 3.铬酸盐膜（黄膜铬酸盐法)  \n\n处理液的主要成分为铬酸，内含有作为浸湿剂的氟化物及其盐，溶液的 $\\mathbf{\\pH}$ 为 $1.8\\sim3.0,$ 另外，也有在处理液中加人钨化物、硒、铁氰化钾等成膜促进剂的。这种膜生成的化学反应如下。  \n\n$\\textcircled{1}$ 氢氟酸引起铝腐蚀的化学反应。  \n\n$$\n2\\mathrm{Al+6HF}\\longrightarrow2\\mathrm{AlF_{3}+3H_{2}}\\uparrow\n$$  \n\n在阳极：  \n\n$$\n\\mathrm{2Al\\longrightarrow2Al^{3+}+6e^{-}}\n$$  \n\n在阴极： $6\\mathrm{H^{+}+6e^{-}\\longrightarrow3H_{2}}\\uparrow$  \n\n在铝工件表面附近的溶液中，由于 $\\mathrm{H^{+}}$ 的减少，溶液的 $\\mathrm{\\pH}$ 上升。  \n\n$\\textcircled{2}\\mathrm{HCr}_{2}\\mathrm{O}_{7}^{-}$ 离解，在阴极上 $\\mathbb{C}\\mathbb{r}^{6+}$ 还原为 $\\mathbf{Cr^{3+}}$ 的化学反应。  \n\n$\\textcircled{3}$ 在某一 $\\tt p H$ 下，析出6价铬和3价铬的氢氧化物化学反应。  \n$2\\mathrm{Cr(OH)_{3}}+\\mathrm{CrO_{4}^{2-}}+2\\mathrm{H^{+}}\\longrightarrow\\mathrm{Cr(OH)_{3}}\\cdot\\mathrm{Cr(OH)}\\cdot\\mathrm{CrO_{4}}+2\\mathrm{H_{2}O}\\longrightarrow\\mathrm{Cr(OH)_{2}}\\cdot\\mathrm{HCrO_{4}}+2\\mathrm{H}$ 20$\\textcircled{4}$ 铝氧化物析出的化学反应。  \n\n$$\n2\\mathrm{Al^{3+}}+6\\mathrm{OH^{-}}\\longrightarrow2\\mathrm{Al(OH)_{3}}\\not\\\\\\\\\\substack{\\not\\downarrow}\\longrightarrow\\mathrm{Al_{2}O_{3}}\\not\\downarrow+3\\mathrm{H_{2}O}\n$$  \n\n所生成的膜是非晶质的，其组成如下。  \n\n非促进型液 $\\mathrm{(Cr^{5+},\\ F^{-}}$ 、无机酸）时为 $\\mathrm{Cr(OH)_{2}\\bullet H C r O_{4}\\bullet A l(O H)_{3}\\bullet2H_{2}O_{4}}$  \n\n促进型液 $(\\overrightarrow{\\mathbf{C}}^{\\hat{\\mathbf{\\alpha}}+}\\cdot\\overrightarrow{\\mathbf{F}}^{-}$ 、铁氰酸盐）时为 $\\mathrm{CrFe(CN)_{6}\\bullet6C r(O H)_{3}\\bullet H_{2}C r O_{4}\\bullet4A l(O H)_{3}}$ ” ${\\mathfrak{S}}{\\mathrm{H}}_{2}{\\bigcirc}_{\\circ}$  \n\n铝合金涂装底层的铬酸盐处理工艺规程如下。  \n\n<html><body><table><tr><td>铬酸/（g/L)</td><td>3.5~4</td><td>pH 1.5</td></tr><tr><td>重铬酸钠/（g/L)</td><td>3.0～3.5</td><td>温度/C 30</td></tr><tr><td>氟化钠/（g/L)</td><td>0.8</td><td>时间/min 3</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1432,
+        "chunk": "# 4.电化学氧化法  \n\n铝及铝合金的电化学氧化法，即阳极氧化法，一般简称为阳极化法，是将铝合金工件装挂在电解槽中的阳极上，阴极是不溶性的铝板，当接通电流后，由于电极的电化学反应，使铝工件表面生成氧化膜。  \n\n阳极化的特点在于氧化成膜的过程中同时发生两个过程：一是工件表面三氧化二铝氧化膜的生成过程；二是在氧化膜生成的同时，伴随着氧化膜溶解的过程。只有当膜的生成速率大于膜的溶解速率时，才可获得所需要的氧化膜，其成膜机理如下。  \n\n在阳极化时，槽液中的水首先被电解，化学反应：$\\mathrm{H}_{2}\\mathrm{O}{\\rightleftharpoons}\\mathrm{H}^{+}+\\mathrm{OH}^{-}$  \n\n在阳极上生成化学活泼性很强的初生态氧：  \n\n$$\n2\\mathrm{OH^{-}\\frac{\\#H\\#K\\#K\\#}{\\hbar}}\\mathrm{~H}_{2}\\mathrm{O}+2\\mathrm{e}^{-}+[\\mathrm{O}]\n$$  \n\n由于氧原子本身很活泼，便与铝工件表面发生化学反应，生成三氧化二铝膜层：  \n\n在膜形成的同时，又伴随着膜的溶解过程。阳极氧化法所用的电解液主要有硫酸、铬酸和草酸溶液三种。当电解液为硫酸时，其化学反应为：  \n\n实际上铝及铝合金经阳极化法处理后得到的膜分为两层：内层由AlO3组成；外层由$\\mathrm{{Al}_{2}\\mathrm{{O}_{3}\\cdot\\mathrm{{H}_{2}\\mathrm{{O}}}}}$ 由组成。  \n\n![](images/bea22e1f453f303c299833f92c4ea6311434f0bff5dddf63f91854b0c75f9cf3.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1433,
+        "chunk": "# 一、清除表面油污和其他脏物  \n\n可用洗涤剂擦洗基层，或用溶剂清洗第一遍，再用洗涤剂擦洗，或用质量分数为 $5\\%$ ～$10\\%$ 的火碱水清洗，然后用清水洗净。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1434,
+        "chunk": "# 二、清除水泥浮浆、泛碱物及其他松散物质  \n\n可用钢丝刷刷除或用毛刷清除，对泛碱、析盐的基层可用3%的草酸溶液清洗，然后用清水洗净。对泛碱严重或水泥浮浆多的部位可用质量分数为5%～10%的盐酸溶液刷洗，但酸液等在表面存留的时间不宜超过5min，必须用清水彻底清净。泛碱和析盐清洗后应注意观察数日，如再出现析盐和泛碱，应重复进行清洗，并推迟刷涂涂料，直至泛碱物消失为止。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1435,
+        "chunk": "# 三、清除表面光滑的方法  \n\n混凝土表面过于光滑，不利于涂料的渗透和附着，须进行清除。清除的方法可用酸蚀、喷砂、钢丝刷刷毛或自然风化，或在表面涂一层3%的氯化锌和2%的磷酸的混合液，或涂一层4%的聚乙烯醇溶液，或20%的乳液均可增加基层和涂层的附着力。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1436,
+        "chunk": "# 四、混凝土表面气孔及缝隙的处理  \n\n混凝土表面的气孔宜挑破并填平，否则空气回拱破跑出，毁坏涂层。手工和机械打磨对清除气孔比较费工，且效果也不理想。一般需采用喷砂处理。混凝土表面的孔隙及挑破的气孔要填平。室外和潮湿环境要用水泥或有机黏结剂的腻子填充。室内干燥环境可使用普通的石膏或聚合物腻子。对粉化或多孔隙表面，为黏附住松散物质和封闭住表面，可先涂刷一层耐碱的渗透性底漆，如稀释的乳胶漆。为减少收缩沉陷，腻子中体质颜料的比例可稍大于黏结剂。  \n\n![](images/1a34b193d2bae6c12afbd4a9d3daf688eebc027a88f2d432f4ee56ac31b1eba2.jpg)  \n\n塑料及橡胶表面预处理的目的是提高涂层与塑料及橡胶表面结合力。处理的内容有以下几个方面：①去除表面污物；②使极性低的塑料及橡胶表面极性化；③表面粗化；①消除塑料及橡胶制品成型时的残余应力。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1437,
+        "chunk": "# 一、塑料及橡胶表面处理的方法",
+        "category": " Introduction"
+    },
+    {
+        "id": 1438,
+        "chunk": "# 1.去除表面污物  \n\n(1）溶剂清洗对与涂层附着良好的塑料，如ABS、聚苯乙烯、有机玻璃等热塑性耐有机溶剂差的塑料，可简单用肥皂水、去污粉等擦洗；对耐溶剂性好的塑料，如聚烯烃和热固性塑料，可用三氯乙烷、三氯乙烯等含氯溶剂和甲苯等芳香族溶剂进行蒸气清洗1～3min即可。各种塑料的结晶性、耐热性和耐溶剂性见表5-2-9。  \n\n表5-2-9 各种塑料结晶性、耐热性、耐溶剂性  \n\n\n<html><body><table><tr><td rowspan=\"2\">类别</td><td rowspan=\"2\">品名</td><td rowspan=\"2\">结晶性</td><td rowspan=\"2\">若变形温度 (4. 6x10°Pa)</td><td rowspan=\"2\">连续耐 热性/C</td><td colspan=\"7\">耐溶剂性</td></tr><tr><td>脂类族</td><td>芳族</td><td>氯化烃</td><td>醇类</td><td>翻类</td><td>脂类</td><td>醚类</td></tr><tr><td rowspan=\"7\">热塑性</td><td>聚乙烯</td><td>高</td><td>60～82</td><td>50</td><td></td><td></td><td>X</td><td>√</td><td>√</td><td>√</td><td>V</td></tr><tr><td>聚丙烯</td><td>高</td><td>90~110</td><td>105</td><td>√</td><td></td><td>X</td><td></td><td>V</td><td>V</td><td>V</td></tr><tr><td>聚苯乙烯</td><td>低</td><td>6997</td><td>50</td><td>V</td><td>X</td><td>X</td><td></td><td>X</td><td>X</td><td>X</td></tr><tr><td>ABS</td><td>低</td><td>88～113</td><td>60</td><td></td><td>△</td><td>X</td><td></td><td>X</td><td>X</td><td>X</td></tr><tr><td>聚氯乙烯</td><td>中</td><td>82</td><td>55</td><td></td><td>X</td><td>X</td><td></td><td>X</td><td>X</td><td></td></tr><tr><td>聚碳酸酯</td><td>低</td><td>145~148</td><td>110</td><td>V</td><td>X</td><td>X</td><td>√</td><td>X</td><td>X</td><td>V</td></tr><tr><td>聚甲醛</td><td>高</td><td>124</td><td></td><td>V</td><td>V</td><td></td><td>√</td><td>√</td><td>V</td><td></td></tr><tr><td rowspan=\"3\">热固性</td><td>尼龙-6</td><td>高</td><td>86</td><td>60~95</td><td>V</td><td></td><td>X</td><td>√</td><td></td><td>√</td><td></td></tr><tr><td>环氧树脂</td><td>低</td><td></td><td></td><td>V</td><td></td><td></td><td>√</td><td>V</td><td></td><td></td></tr><tr><td>酚醛树脂</td><td>低</td><td></td><td></td><td>V</td><td>√</td><td></td><td></td><td>V</td><td>√</td><td>√</td></tr><tr><td></td><td>三聚氰胺树脂</td><td>低</td><td>100</td><td></td><td></td><td>√</td><td></td><td>√</td><td>√</td><td></td><td>√</td></tr></table></body></html>\n\n注： $v^{i}$ 代表耐溶剂性好；代表一般； $x$ 代表耐溶剂性差。  \n\n(2）等离子流处理等离子流中有红外线、紫外线、离子、自由基等。由于其高能反应性可与塑料及橡胶表面起各种反应，使表面污物除去，并生成双键和其他官能团。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1439,
+        "chunk": "# 2.极性化  \n\n对聚乙烯、聚丙烯等结晶性高的非极性塑料，可用强酸强氧化物组合的酸性液处理，令其表面氧化而导入基、羧基等官能团，以提高对漆膜的附着力。此法同时使塑料表面形成粗糙面，提高附着力。通常酸液配方是：重铬酸钾 $4.5\\%$ ；水 $8.0\\%$ ；浓硫酸 $87.5\\%$ 。先将前两者配成溶液，然后缓缓加入浓硫酸混合均匀即可，或按表5-2-10配置。  \n\n表5-2-10 极性化酸液处理  \n\n\n<html><body><table><tr><td>铬酸钾/质量份</td><td>浓硫酸/质量份</td><td>水/质量份</td><td>温度/℃</td><td>时间/min</td></tr><tr><td>75</td><td>1500</td><td>120</td><td>70~75</td><td>5~10</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1440,
+        "chunk": "# 3.表面粗化  \n\n非极性塑料表面粗化可按表5-2-10酸液处理，对坚硬光滑的热固性塑料可用喷砂处理；质软的硬质聚氯乙烯的处理方法可根据增韧剂的品种、含量及用途而定。一般可在三氯乙烯溶液中浸渍几秒钟，去除表面游离的增韧剂，然后轻擦干燥。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1441,
+        "chunk": "# 4.消除内应力  \n\n内应力不除，漆膜易生细纹。其原因是塑料表面因溶剂渗透、内聚力下降，导致应力释放。消除内应力方法是将塑料在热变形温度以下进行一定时间退火即可。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1442,
+        "chunk": "# 二、塑料及橡胶表面处理的检测方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1443,
+        "chunk": "# 1.甲酰胺溶液实验方法  \n\n用缠于棒上棉球，蘸取甲酰胺和乙二醇乙醚（乙基溶纤剂）的混合液，在被处理过的薄膜上涂布约6.5cm（直径约2.9cm)，若此薄膜上的液膜保持2s以上不破时，再用表面张力高的混合液试验；若薄膜在2s内破裂成小液滴时，则再用张力低的混合液实验，从而获得适当的表面张力值。  \n\n张力值大，说明薄膜与油墨、涂料、黏合剂的亲和性良好。对塑料表面印刷来说，表面张力应为（38～40）mN/m，对涂饰来说，则应为（48～54)mN/m。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1444,
+        "chunk": "# 2.乙醇溶液实验方法  \n\n将经过火焰处理的塑料表面，浸入清洁的冷水或3质量份乙醇和1质量份水组成的溶液中，若水膜能保持30s，则认为处理合适。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1445,
+        "chunk": "# 3.染料溶液实验方法  \n\n用染料（如纯色淀蓝）的硝基乙烷溶液（4g/L）涂刷，若润湿的表面不形成液滴，则为合格。  \n\n![](images/282fc5952b9018c70409d4a4d0812774c4ac58f4a6c66cb249edd1c5b5bf14f2.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1446,
+        "chunk": "# 一、木材的种类及特征  \n\n木材种类繁多，主要有天然实木木材和复合型材料。  \n\n天然实木依生长的环境不同所产生的材质就不同，即使同一棵树木也无法得到完全相同材质，所以木材会有不同的变化、不同的特性，这就是木材的天然特性。  \n\n树种不同，木材结构差别就很大，按树种分类大致分为针叶树和阔叶树两大类。根据孔眼的不同，阔叶树可分为环孔材、散孔材、半环孔材等。  \n\n最常见的复合材料有三合板、五合板、密度板、刨花板等。因各种复合材料板的组合结构不同，可克服木材的胀缩、翘曲、开裂等缺点，具有一定的优越性。  \n\n木材剖面依据锯切方向不同，可分为横切面、径切面与弦切面。在木材横切面上，其中心部分为髓心，周围一圈圈同心圆状的轮环，即年轮。在每一圈靠里面（即树心）的部分为春材（早材)，是春夏季长成的，材质松软，颜色浅淡；在年轮靠外边部分称为秋材（晚材)，是夏秋季节长成的，材质硬而质密、颜色深。  \n\n这种由年轮形成的木材颜色深浅变化和材质疏密在径切面与弦切面上更为明显。由年轮、木射线、节子、导管、与不同锯切方向等因素构成了木材花纹，在径切面呈平行条纹状，在弦切面上呈山峰状，形成木材特有的美观质感。  \n\n由于木材结构复杂多变，在选材、组合上要十分巧妙才可制成美观的制品，否则给木制品的着色、涂装带来困难，出现着色不匀、下陷等病。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1447,
+        "chunk": "# 二、木材涂装前处理的意义  \n\n木材涂装前处理的主要意义在于为最终的木制品表面涂装涂料提供一个平整光滑、颜色均匀、木纹清晰的表面。天然木材由于其本身的生长特性、贮存条件和加工处理成型方式的  \n\n不同往往会存在一些缺陷，如实木中的木节疤、开裂、腐朽、发霉、虫眼，胶合板中的离缝、渗胶、切削刀痕、进料机压痕等。如果在涂装前不能处理好这些缺陷，势必会成为整个涂装过程的隐患，会影响涂装的整体效果。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1448,
+        "chunk": "# 三、木材涂装前处理的方法  \n\n木材的性质和构造随树种而有所不同。当涂装木材表面时应注意木材的硬度、纹理、空隙度、水分、颜色以及是否含有树脂、单宁酸等物质。木材的表面处理常有以下几种工序及方法。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1449,
+        "chunk": "# 1．木材的干燥  \n\n新木材通常都含有很多水分，并且在贮存过程中还会从潮湿的空气中继续吸收水分，所以在施工之前，要将木材存放在通风良好的地方自然晾干或进入烘房内用低温烘干。木材经于燥处理时，应控制含水量在 $8\\%\\sim12\\%$ ，这样才能防止涂层发生开裂、起泡、回黏等病。木材的干燥方法有人工干燥、自然干燥和简易人工十燥等方法。  \n\n(1）人工于燥将木材密封在蒸汽干燥室内，使木材干燥，干燥的程度最高可使木材含水量仅达 $3\\%$ ，但经过高温蒸发后的木质发脆，失去韧性，容易受到损坏而不利于雕刻。  \n\n(2）自然干燥将木材（板材、方才或圆木）分类放置于通风处，搁置或码垛，垛底离地60cm左右，中间留有空隙，使空气流通，带走水分，木材逐渐干燥。自然干燥一般要经过数月或数年，才能达到一定的干燥要求。  \n\n(3）简易人工干燥一是将原木按类别堆放在烘房内，通过锅炉供热的方式强制烘干木材内的水分，控制水分含量在 $8\\%\\sim12\\%$ ；二是将原木用水煮或浸泡，在水中去除木材中的树脂成分，然后放在空气中晾干或烘干，该法干燥时间会缩短，但浸水的木材易变色，有损木质。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1450,
+        "chunk": "# 2.清除木脂  \n\n针叶树材如各种松材和云杉等都有树脂，在节缝处树脂更多。松脂含松香和松节油，木材含松脂会降低涂层的附着力，影响涂层的干燥和颜色的均匀性。如树脂从木材内部向表面渗出，还会使涂层发黏、损坏。因此，涂装前应将树脂去除。清除树脂可用下列方法。  \n\n$\\textcircled{1}$ 将松脂富集部位挖掉，再补上同样大小的木材，但应保持纤维方向一致。$\\textcircled{2}$ 用有机溶剂解除去松脂，同时刷 $1{\\sim}2$ 道虫胶漆作为阻挡层，以防松脂从木材内部渗出。常用有机溶剂有乙醇、松节油、汽油、甲苯及丙酮等。$\\textcircled{3}$ 用碱液清洗。可用 $5\\%\\sim8\\%$ 的碳酸钠水溶液或 $4\\%\\sim5\\%$ 的苛性钠水溶液清洗，使松脂皂化，再用热水洗，待表面干燥后，刷 $1\\sim2$ 道虫胶漆。$\\textcircled{4}$ 用碱液-丙酮混合溶液清洗。用碱液 $\\bar{80}\\bar{\\bf g}$ （浓度为 $5\\%\\sim6\\%$ 的碳酸钠）和丙酮水溶液$200\\mathbf{g}$ （丙酮 $50\\mathrm{g}$ 加水 $150\\mathbf{g}^{\\cdot}$ ）混合均匀，涂抹在松脂处，然后用水洗干净，待十燥后刷 $1{\\sim}2$ 道虫胶漆。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1451,
+        "chunk": "# 3.防霉  \n\n为了避免木材长时间受潮而出现霉菌，可在未涂装前先薄涂一层防霉剂。例如，用乙基磷酸汞或氯化酚、对甲苯氨基磺酰的溶液来处理，待干透以后再行涂装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1452,
+        "chunk": "# 4.漂白  \n\n木材含有天然色素，有时这种色素可作为装饰，需要保留，可以省去漂白工序。但是木材的固有颜色，特别是深色往往会影响着色色调的鲜明性，因此需要漂白。漂白的目的是：  \n\n使心材与边材颜色一致；使木材的本色变得更白或使被污染的木材颜色变淡；对于要求明亮着色加工的制品，漂白可以提高着色的效果；可获得与木材固有颜色无关的任意颜色的涂层。  \n\n木材用漂白剂的配方和使用方法可见表5-2-11。  \n\n表5-2-11 木材用漂白剂配方和使用方法  \n\n\n<html><body><table><tr><td>序号</td><td>组成</td><td>使用方法</td></tr><tr><td>1</td><td>双氧水（30%)100份 水50～100份 氨水(25%)100份</td><td>混合溶液充分搅拌均匀后，刷涂在欲漂白的部位，放置一天。溶液 氧化作用可使木材中的色素分解，褪掉颜色</td></tr><tr><td>2</td><td>I液：次氯酸钠50g 水1000mL</td><td>先将I液中的次氯酸钠溶于70C左右的水中，再涂刷在需漂白的 部位。再用Ⅱ液涂刷以中和木材中的残氯。再用水洗净</td></tr><tr><td>3</td><td>Ⅱ液：亚硫酸钠1%～5% 硫黄</td><td>此法适用于小型产品。将产品置于密封容器内，在容器内燃烧硫 黄，利用所产生的二氧化硫气体进行漂白</td></tr><tr><td>4</td><td>I液：碳酸钠180g/L Ⅱ液：双氧水20%</td><td>先用I液涂刷在需漂白的部位，放置5min，再用ⅡI液涂刷，放置数 小时，用水洗净</td></tr><tr><td>5</td><td>I液：草酸5%～10% Ⅱ液：硫酸钠5%</td><td>先用I液涂刷在需漂白的部位，放置10～20min，再用Ⅱ液涂刷， 进行中和，然后用水洗净</td></tr><tr><td>6</td><td>I液：氢氧化钠50g/L Ⅱ液：冰醋酸20% Ⅲ液：盐酸1%</td><td>先用I液涂刷在需漂白的部位，放置5min，再用Ⅱ液或Ⅲ液进行 中和，然后用水洗净</td></tr><tr><td>7</td><td>I液：碳酸钠20g/L 水（50~60℃)1000mL Ⅱ液：双氧水（35%）80mL 水20mL</td><td>I液、Ⅱ液可单独使用，或I液与Ⅱ液混合使用（等量混合） 将溶液涂刷在需漂白的部位，使其浸透，放置数分钟到数十分钟， 再用湿布抹净</td></tr></table></body></html>  \n\n漂白剂一般都有腐蚀性，盛漂白剂的容器应用玻璃、陶瓷、塑料等材料制造。毛刷应用合成纤维（如尼龙）制造。漂白剂对皮肤、衣服也有腐蚀作用，漂白剂的蒸气也能使眉毛和头发变色。人体应避免直接接触漂白剂，同时还要防止漂白剂分解失效。双氧水等受日光照射或温度升高时，容易分解，降低甚至丧失漂白能力。因此，应保存在阴凉处。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1453,
+        "chunk": "# 5.木材的砂光  \n\n木材经过各种机械加工处理后，其表面往往高低不平，需要处理成适合涂装的平滑平面，要采用填充、砂光和其他手段来对木材调整。  \n\n砂光程序无论采用人工或机械作业，都要根据不同的产品结构、木质的软硬以及实木和薄片来选用适当的砂纸型号。目前在家具行业中大多数使用的是 $240^{\\#}\\sim400^{\\#}$ 砂纸来处理木制品表面的平整度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1454,
+        "chunk": "# 6.虫孔、死结、斑痕、裂缝等的修补  \n\n对于木材表面一些细小的缺陷如裂缝、虫眼、钉眼等可用腻子嵌补，常用的腻子有水性腻子、硝基腻子、聚氨酯腻子、不饱和聚酯腻子等。木材表面的木节、腐朽等大的缺陷可采用挖补的处理工艺，用手工挖补或钻孔填补圆木块。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1455,
+        "chunk": "# 7.素材调整  \n\n由于木材天然生成，本身颜色不一致，易造成产品涂装后色相的差异，故在涂装前一般要选择各种染料或高透明颜料对木材颜色进行调整，以保证木材颜色的均一性。着色材料的施工方法及优缺点见表5-2-12。  \n\n表5-2-12着色材料的施工方法及优缺点  \n\n\n<html><body><table><tr><td>项 目</td><td>染料</td><td>颜料</td></tr><tr><td>主要组分</td><td>金属络合物</td><td>经特殊处理的颜料</td></tr><tr><td>溶剂体系</td><td>各种有机溶剂/去离子水</td><td>有机溶剂/去离子水</td></tr><tr><td>耐候性</td><td>较差，容易褪色</td><td>优异，不褪色</td></tr><tr><td>着色后清晰度</td><td>透明性优</td><td>透明性较好</td></tr><tr><td>施工方法</td><td>喷涂/浸涂</td><td>喷涂或擦拭</td></tr><tr><td>性能特点</td><td>相溶性好，颜色鲜艳</td><td>颜色立体层次感优</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1456,
+        "chunk": "# 8.特殊处理  \n\n一般特殊工艺（如仿古涂装工艺）在涂装前白坯还会做一些特殊处理，常采用螺母、螺栓、螺丝、钉子、雕刻刀、锂刀等工具仿制出年代久远而形成的各种破坏效果。常用方法有以下几点。  \n\n$\\textcircled{1}$ 碰撞伤采用螺母、螺栓、螺丝等工具敲打而成。  \n$\\textcircled{2}$ 裂痕采用雕刻刀在木材顶端顺着木材纹理方向仿制出开裂效果。  \n$\\textcircled{3}$ 虫孔取钉子在木材上不规则地、有深浅地敲打出钉眼。  \n$\\textcircled{4}$ 磨损用雕刻刀在木制品边缘和边角处锉损，然后用 $240^{\\sharp}$ 圆盘砂磨损、倒边。  \n当木材处理完成以上工序后，才可进行涂装工序，以得到更佳的涂装效果。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1457,
+        "chunk": "# 9.木材涂装前处理对涂装效果的影响  \n\n经表面处理后的半制品白坏进入到涂装工序时，即使工艺设计非常合理，木工技术和涂装技术再好，如果不注重底材处理，也会直接影响到整个制品的品质和商品价值。各处理工序对涂装效果的影响列于表5-2-13。  \n\n表5-2-13 各处理工序对涂装效果的影响  \n\n\n<html><body><table><tr><td>序号</td><td>工序</td><td>不合格项目</td><td>对涂装效果的影响</td></tr><tr><td>1</td><td>木材的干燥</td><td>木材含水率过高</td><td>①涂膜容易发生气泡，产生针孔和暗泡 ②涂膜干燥缓慢 ③涂装时易产生白化现象 ④时间长涂膜易产生龟裂、剥落、失光及附着不良等现象 ③容易滋生霉菌</td></tr><tr><td>2</td><td>清除木脂</td><td>木材脂清除不彻底</td><td>①上层喷涂硝基漆时造成不干现象 ②喷涂聚氨酯漆时易产生干燥不良及板面发花现象 ③木材制品在冷热交替的环境中长期放置易产生颜色变化，如产生</td></tr><tr><td rowspan=\"2\">3</td><td rowspan=\"2\">漂白</td><td>由于漂白剂选用不当造 成漂白效果差异</td><td>黑斑等现象 涂装清漆后造成颜色差异</td></tr><tr><td>漂白剂水洗不干净</td><td>上层涂装含TDI类型的聚氨酯漆时，易造成漆膜在短时间内产生黄 变、发脆现象</td></tr><tr><td>4</td><td>木材砂光</td><td>砂光不良</td><td>①影响涂膜平坦效果 ②可能增加涂料用量 ③影响着色效果 ④会产生严重的砂痕，破坏木纹的天然纹理</td></tr><tr><td>5</td><td>素材调整</td><td>木材表面颜色不一致</td><td>造成木材制品批次间颜色差异</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1458,
+        "chunk": "# 参考文献  \n\n[1］叶杨祥，潘肇基主编：涂装技术实用手册．北京：机械工业出版社，2005.  \n\n[2] 涂料工艺编委会编，涂料工艺：下册．北京：化学工业出版社，1997.  \n[3] 曹京宜等，涂装表面预处理技术与应用，北京：化学工业出版社，2004.  \n[4] 周良．喷丸（砂）、喷涂技术及装备．北京：化学工业出版社，2008.  \n[5] NACE．检察员培训教材课程：教师手册．NACE国际，2007.  \n[6] 孙兰新，宋文章，王善勤等．涂装工艺与设备，北京：中国轻工业出版社，2001.[7] 杨世芳，木器涂料涂装技术问答．北京：化学工业出版社，2008.  \n[8] 李芳，苏立荣，沈春林等，建筑涂装工程问答实录，北京：机械工业出版社，2008.[9] ISO8501-1.钢材在涂装油漆及相关产品前的预处理表面清洁度的目视评定.[10] ISO8501-2.用于评定原先涂过涂料的钢材进行局部除锈的标准.  \n[11] ISO8502-1.喷射处理过的钢材表面进行可溶性铁盐的检测方法，  \n[12] ISO8502-2.经除锈过的钢材表面氯化物的检测方法.  \n[13] ISO8502-3.涂装前表面灰尘沾污程度标准  \n[14] ISO8502-4.涂装前钢材表面结露可能性的评定.  \n[15] ISO8502-5.涂装前钢材表面氯化物测定法，氯离子检测法.  \n[16] ISO8502-6，表面可溶性杂质取样及测定方法，BRESLE方法.  \n[17] ISO8502-7，涂装前表面可溶性杂质分析，氯离子现场分析法.  \n[18] ISO8502-8.涂装前表面可溶性杂质分析，硫酸盐现场分析法，  \n[19] ISO8502-9.可溶性盐导电率的现场检测法.  \n[20] ISO8502-10，可溶性盐的滴定法现场检测法.  \n[21] ISO8503-1.表面粗糙度比较样块的技术要求和定义.  \n[22] ISO8503-2.喷射清理后钢材表面粗糙度分级——比较样块法、  \n[23] ISO 8503-3.ISO基准样块的校验和表面粗糙度的测定方法———显微镜调焦法.[24] ISO8503-4.ISO基准样块的校验和表面粗糙度的测定方法——触针法，",
+        "category": " References"
+    },
+    {
+        "id": 1459,
+        "chunk": "# 第三章",
+        "category": " Introduction"
+    },
+    {
+        "id": 1460,
+        "chunk": "# 涂料施工方法  \n\n涂料施工是发挥涂料性能的关键，对涂膜性能有重要的影响。随着时代的发展，施工方法发生了日新月异的变化，涂料施工过程更加机械化、自动化和连续化。选用合适的涂布方法可以提高涂料利用率和施工效率，并且能够保证涂膜质量，发挥涂料的作用，同时可以改善施工的劳动条件和强度。  \n\n涂布方法分为手工工具涂装、机械设备涂装和电力涂装三类。手工工具涂装是古老传统的涂漆方法，目前还在应用，主要有刷涂、辊刷涂、刮涂、丝网涂等方法。机械设备涂装是目前应用最广的一种方法，最主要的是喷枪喷涂法，包括空气喷涂、无空气喷涂和热喷涂，除此之外还有浸涂、淋涂、辊涂、抽涂等。电力涂装是近几年发展最快的方法，现在已从机械化逐步发展到自动化、连续化和专业化，有的方法已与前处理和干燥前后工序连接起来，形成专业的涂装工程流水线。这类方法包括静电粉末涂装、电沉积涂装和自沉积涂装等。这三类涂布方法有其各自的特点，手工工具涂装效率低，但方便灵活，目前仍被用于大规模涂装前的预涂和小批量的涂装等，而机械设备和电力涂装的效率高，涂装效果也好，但是往往对复杂结构的被涂物无能为力，而且设备投资成本很高，适于大规模的涂装。在实际工作中一般依据被涂物的形状、涂布的目的、对涂层质量的要求和涂料的特性来选择适当的涂装方法。  \n\n刷涂法（brush coating）是借助漆刷与被涂物表面的直接接触，使涂料均匀地润湿涂布在被涂物表面而形成涂膜的涂布方法。刷涂是使用最古老、最简单的涂装方法，适用于涂装任何形状的被涂物，经过长期的应用，形成了一套传统的工艺操作技术。因此，即使涂装技术发展日新月异的今天，刷涂仍然是普遍采用的方法之一。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1461,
+        "chunk": "# 一、刷涂的特点  \n\n刷涂的优点是操作简便，节省涂料，所需的工具简单，适用的范围广，不受涂装场所和环境条件的限制，适用于刷涂各种材质、各种形状的被涂物。刷涂法的适应性很强，除了表干过快的涂料以外，几乎所有的涂料均可以采用刷涂进行施工。刷涂时涂料借助漆刷与被涂物直接接触的机械作用，能很好地润湿到被涂物的表面，并渗人被涂物表面的细孔，因而可以增加涂膜的附着力。刷涂的缺点是生产效率低，劳动强度大，不适用于流水线施工；装饰性能差，质量不稳定，容易产生刷痕，需要熟练的操作工人才能弥补装饰性差的缺点。而且，干燥速率过快的硝基漆和过氯乙烯漆等也不适于刷涂施工。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1462,
+        "chunk": "# 二、漆刷的类型  \n\n漆刷的种类很多，形状各异。按照刷毛的质地可以分为硬毛刷和软毛刷，硬毛刷多为猪繁或马制作，也有用人的头发制作的；软毛刷一般为羊毛制作，也有用狸毛、毛和狼毛制作的，但价格较高，很少使用；目前还有用尼龙或聚酯等合成材料代替天然毛制作的，综合品质好。天然繁毛刷通常适用于溶剂型涂料的涂装，但不适于水性涂料的涂装；羊毛刷用于刷水性漆，既适用于涂刷墙面漆也适用于涂刷木器漆；合成材料刷多用于刷水性漆。按照漆刷的形状可以分为：扁形刷、圆形刷、板刷、歪柄刷、排笔刷等，如图5-3-1所示。  \n\n![](images/95428dd4d7e5953222139c3dd3110f493309f4a28e67b06c5d88f67c885d37e3.jpg)  \n图5-3-1 漆刷的种类",
+        "category": " Introduction"
+    },
+    {
+        "id": 1463,
+        "chunk": "# 三、刷涂基本操作方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1464,
+        "chunk": "# 1.准备  \n\n在刷涂前要做好认真的准备。首先要准备一个干净的容器，将涂料搅拌均匀，用稀释剂调整好涂料的黏度，去除涂料表面的颗粒；站在被涂物的前面，摆正姿势。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1465,
+        "chunk": "# 2.执刷  \n\n刷涂时要紧握手柄的中心，拇指在前，食指和中指在后并抵住木柄，手握漆刷要牢固，不能使漆刷任意松动，如图5-3-2所示。在刷涂过程中，刷柄应始终与被涂物表面处于垂直状态，以使长度约一半的刷毛顺一个方向贴附在被涂物表面较好，漆刷运行时用力要适度，运行速度要均衡。  \n\n刷涂前先将漆刷放人涂料至刷毛的1/3～2/3处，使漆刷蘸上涂料，刷柄不要接触容器内壁，蘸漆后应以刷尖轻触罐壁数次，以使漆刷含漆饱满而又不会淌下。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1466,
+        "chunk": "# 3.刷涂方法  \n\n刷涂的方法有两种，分别是三阶段法和棒涂法。三阶段法最常用，适用于大多数涂料的刷涂，棒涂法适用于刷涂快干涂料。现分别介绍如下。  \n\n![](images/de32a2c3705ded504d4e2d6423bf79d83aa21ecb67d18942cb34c81427bed43e.jpg)  \n图5-3-2 执刷方法  \n\n（1）三阶段法 所谓三阶段法，是指涂布、抹平、修整三个刷涂步骤，如图5-3-3所示。  \n\n涂布是将刷毛黏附的涂料涂布在漆刷所触及范围内的被涂物表面，漆刷的运行轨迹可根据所用涂料在被涂物表面的流平情况，保留一定的间隔；抹平是将已经涂布在被涂物表面的涂料展开抹平，将漆刷前后触及的、所有保留的间隔面均涂布上涂料，不能露底，一般垂直于涂布方向；修整是按照一定方向涂刷均匀，消除刷痕与膜厚不均匀的情况。  \n\n![](images/5914ae5c6b59459c4c7f8b379b301afcad61a5a1d98dc3901ba3264f43b82868.jpg)  \n图5-3-3 刷涂步骤  \n\n（2）棒涂法棒涂法适用于刷涂快干型涂料，它将涂布、抹平、修整三个步骤合为一个，如图5-3-4所示。棒涂法每次刷涂的宽度比较窄，不能反复刷涂，必须在将涂料涂布在被涂物表面的同时，尽可能快地将涂料抹平，修整好涂膜，漆刷宜采用平行轨迹，并重叠漆刷的1/3的宽度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1467,
+        "chunk": "# 4.刷涂的操作技巧  \n\n刷涂操作的基本原则是先里后外、先左后右、先上后下、先难后易、先线角后平面，要一面一面地顺序刷涂，以免遗漏。  \n\n![](images/74ff9b865a503982ca36df2c65fd3c76d5e39aa3c9014fb29ea9eb1a6475e264.jpg)  \n图5-3-4 棒涂法  \n\n刷涂时关键的控制指标是黏度。涂料黏度的高低影响漆刷的蘸漆量、刷涂涂膜的厚度、涂膜的流平和立面的流挂等，刷涂前要仔细反复试涂，以达到良好的刷涂效果。  \n\n刷涂时漆刷蘸涂料、涂布、抹平、修整等几个步骤应该是连贯的，不能有停顿，熟练的操作者可以将涂布、抹平、修整三个步骤连续地完成，形成良好的涂膜。  \n\n在进行涂布和抹平操作时，漆刷要始终垂直于被涂物表面，并用力使刷毛大部分贴附在被涂物表面；在修整时，用力要小，漆刷应向刷涂运行的方向倾斜，用刷毛的前端轻轻地刷涂修整，以便达到满意的修整效果；涂布、抹平、修整三个步骤应该纵横交替进行，但对于被涂物的垂直面，最后的修整方向应该是沿着垂直方向进行竖刷；木质的被涂物最后的修整步骤应该与木纹走向一致；刷涂每次黏附的涂料量最好保持一致，每次黏附的涂料刷涂面积也要保持一致。刷涂要均匀，厚度要适当，过薄易漏底，过厚则易起皱或流挂。  \n\n刷涂面积较大的被涂物时，通常先从左上角开始刷涂，每蘸一次涂料，按照涂布、抹平、修整三个步骤完成一定的刷涂面积后，再蘸涂料刷涂下一块面积。对于面积较大、形状复杂的被涂物，死角等不易刷涂部位最好应先进行预涂；仰面刷涂时，漆刷每次黏附的涂料要少一点，刷涂用力也不要太重，速度也不要太快，以免涂料掉落。  \n\n刷涂施工后，漆刷要及时清洗干净，晾干保存，以备下次使用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1468,
+        "chunk": "# 第二节 刮涂法  \n\n刮涂（knifecoating）是利用刮具，将腻子或黏稠涂料涂布在被涂物表面的涂布方法。刮涂是涂装施工中常用的方法，主要用于刮涂腻子，也可以用于刮涂厚浆型涂料。通常用于  \n\n修饰凹凸不平的表面，修整被涂物的造型缺陷。刮涂的施工方法简单，不需要很多投资，适用于要求厚涂层和平的表面，不适于薄涂层。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1469,
+        "chunk": "# 一、刮涂用具  \n\n刮涂为手工操作，所用的工具有刮刀、腻子盘、配套的打磨工具、砂布和水砂纸等。刮涂的主要工具是刮刀，根据刮刀的材质可以分为：钢制刮刀、牛角刮刀、塑料刮刀、橡胶刮刀、木质刮刀等。一般根据涂刮表面的大小和形状来选择刮刀，刮涂表面大要选用大刮刀，反之要用小刮刀。刮涂平面时要用刚性较好的钢片、牛角或塑料刮刀，刮涂棱边和圆角要用柔性的橡胶刮刀。  \n\n腻子盘有调腻盘和托腻盘两种。调腻盘用于调整腻子的稠度，托腻盘用来盛装调整好的腻子，通常由钢板或木板制作，在专门的商店都可以买到。  \n\n一般用砂纸或纱布打磨腻子层。粗磨用150～220砂纸，用于初步打磨；细磨用220#～600#砂纸，将腻子打磨平整。垫板通常是粘有薄泡沫层的木质或钢制平板，打磨前将砂布或砂纸卡在垫板的一面，然后对腻子层进行打磨，达到磨高不磨低的目的。小的垫板可以直接用纱布将其裹紧，大的垫板设有固定纱布的机构，用于固定砂布或砂纸。打磨垫板如图5-3-5所示。  \n\n![](images/fd7ff2fe36024c56ecbe66bc60d300c1733ffa5ddaa647c290cce8c0a06a7754.jpg)  \n图5-3-5打磨垫板  \n\n![](images/4301c14d0ef50d0db3140414bc9cfa7489e4c3451d043771346fd6c2546e51c2.jpg)  \n图5-3-6 气动打磨机  \n\n打磨机可以按照动力驱动方式分为气动打磨机和电动打磨机两种，气动打磨机的应用比较普遍。气动打磨机如图 5-3-6所示。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1470,
+        "chunk": "# 二、刮涂的基本技法  \n\n刮涂可以分为局部刮涂和全面刮涂。局部刮涂又叫嵌刮，用于填补局部的凹陷，嵌刮施工要求腻子要松散、稠厚些，以使腻子层结实、平整。全面刮涂又称为满批，是指在被涂物表面上全面进行填补，满批施工要求腻子要略稀些，以利于刮批，满批腻子可以节省涂料，获得较好的涂饰效果。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1471,
+        "chunk": "# 1．嵌刮技法  \n\n嵌刮腻子的刮刀刃口要平直，嵌填时要紧握刮刀，向手心方向倾斜一定的角度，均匀用力，将腻子刮填嵌人凹陷内，然后再用刮刀先压后刮，将四周的腻子刮涂干净。一次刮涂不能太厚，避免造成干燥不良。为了防止腻子干燥收缩形成凹陷，要多次复嵌，嵌补的腻子应比被涂物面略高，需多道刮涂时，应该在前道腻子层干燥后，稍经打磨再刮涂下一道。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1472,
+        "chunk": "# 2.满批技法  \n\n满批多为修补凹凸不平的较大平面或装饰要求较高的产品。头道腻子刮涂时要多蘸腻子，先平面后棱角，以高处为准，就高不就低，刮刀要向前倾斜一定的角度，均匀用力，从上到下或从左到右一次刮下，来回刮1～2次即可，避免多次刮涂起卷。头道腻子稍厚，二道、三道腻子要稀一些，头道腻子主要考虑与底材的结合，要刮实；二道腻子要刮平，允许有少量的针孔，但不允许有气泡；三道腻子要刮光，为打磨创造有利的条件。  \n\n打磨是刮涂必需的后处理工序。一般先用粗砂纸打磨平整，再用细砂纸打磨光滑。为了提高效率，可以采用打磨机打磨，打磨机适宜打磨平面，形状复杂的表面效果不佳，容易产生过磨的现象。所以打磨机打磨到一定程度后，仍需要手工打磨。  \n\n![](images/dfc8df77e86180fdbbd83005f69ee4b1e85c09cdf41736e3b81587d79e4d4712.jpg)  \n\n辊刷涂法（rollercoating）是指用辊刷黏附涂料，借助辊刷的滚动将涂料转移到被涂物的表面，形成涂膜的涂装方法。辊刷涂适用于宽和平的表面，涂装效率高，是刷涂效率的两倍，但对“切人型”的角落或边缘的涂装比较困难。通常用于船舶、桥梁、各种大型机械设备和建筑涂装等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1473,
+        "chunk": "# 一、辊刷涂法的特点  \n\n$\\textcircled{1}$ 施工效率高于刷涂，是手工施工中最快的方法。$\\textcircled{2}$ 涂料的浪费少，对环境的污染小。$\\textcircled{3}$ 适用于大面积平面的涂装，对结构复杂和凹凸不平的表面不适用。$\\textcircled{4}$ 涂膜的装饰性一般，容易留下滚痕。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1474,
+        "chunk": "# 二、辊刷的构造  \n\n辊刷由两部分组成，即刷辊和支承机构，如图5-3-7所示。  \n刷辊由辊芯、连接层和含漆层组成，如图5-3-8所示。  \n\n辊芯连接支承机构，能够滚动；连接层连接辊芯和含漆层；含漆层黏附在刷辊的外表面，是辊刷的关键部件。  \n\n含漆层分为纤维含漆层和发泡含漆层。纤维含漆层用天然纤维或合成纤维制成，天然纤维主要采用羊毛，合成纤维有尼龙、聚酯、聚丙烯等。含漆层的种类、覆盖层的厚度和密度  \n\n![](images/2c215686b15ca9bdb5acf2063ec3bcdf398b499342b39bb6706daed7426f579e.jpg)  \n图5-3-7 辊刷的构造 1—手柄；2—支架； 3—支承座；4一简芯  \n\n决定了辊刷涂膜的质量和外观，通常要根据施工的要求进行选择。按照纤维的长度又有长毛、中毛和短毛之分。长毛含漆层的毛长为 $18\\mathrm{\\sim}30\\mathrm{mm}$ ，用于粗糙表面涂装；中毛含漆层毛长为 $10\\sim$ $17\\mathrm{mm}$ ，属于通用型；短毛含漆层的毛长为 $2\\mathrm{\\sim}9\\mathrm{{fmm}}$ ，用于装饰性要求高的表面涂装。  \n\n![](images/b8adb5808697dcdf63633be4d20028fbc9501b0422c26eb784b91c64b9062403.jpg)  \n图5-3-8 刷辊的构造 1—辊芯；2—连接层；3—含漆层  \n\n支承机构由支承刷辊的机构和手柄两部分组成，用以支持刷辊进行辊涂施工。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1475,
+        "chunk": "# 三、辊刷的种类  \n\n按照辊刷的形状可以分为标准型和特殊型。根据涂料的取得方式分为普通型辊刷和压送式辊刷。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1476,
+        "chunk": "# 1.标准型辊刷  \n\n标准型辊刷的刷辊呈圆筒形，按照辊刷的内径可以分为通用型、大型和小型，通用型辊刷内径为38mm，辊幅为100～220mm，适用于一般的平面或曲面；小型辊刷的内径为16～25mm，一般用于被涂物的内角和拐角的涂装；大型辊刷的内径为50～58mm，适用于大面积的辊涂。  \n\n![](images/deb85d8dd9d8d822410f7125166e3b4edbd5dae26b58fbfcaabae1d132513493.jpg)  \n图5-3-9 压送式辊刷1—辊刷；2—压送装置  \n\n特殊型辊刷的刷辊不呈标准的圆筒形，可以设计成引擎形、锥形、棱角形、半圆形等，以满足形状复杂的被涂物的涂装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1477,
+        "chunk": "# 2.特殊型辊刷",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1478,
+        "chunk": "# 3.压送式辊刷  \n\n压送式辊刷是用压送泵或蓄压器向刷辊供给涂料，涂料经压送泵增压后由输送管道输出，再经支承杆与辊芯的内腔输送到含漆层，利用辊刷进行辊涂施工。其构造如图5-3-9所示。  \n\n由于可以自动供给涂料，而且涂料的输出量可以调整，  \n\n以阿！压送式辊刷能够进行连续涂装，涂膜的厚度均匀，适用于大面积被涂物的涂装；但压送式辊刷比较重，劳动强度大，而且在涂装过程中要经常转移输送管路，不适宜小面积的涂装。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1479,
+        "chunk": "# 四、辊刷涂操作要领  \n\n刷涂施工前首先应该根据被涂物的形状和涂料的特性选择合适的刷辊，可供选择的参数 有刷辊形状、刷毛的长短、刷辊的大小、柄的长短等。  \n\n施工时要正确地手持辊刷，食指在前，拇指和中指在后握住刷柄，用力自然。在辊刷涂料盘内注人涂料，注人的涂料量以能够没入辊刷外径的一半为宜，辊刷在盘内滚动粘上涂料，并反复滚动使含漆层均匀地黏附涂料，并去除气泡或杂质。  \n\n辊涂包括辊布、辊平、修饰三个步骤，如图3-5-10所示。辊布是用刷辊将涂料涂布在被涂物表面上，通常按照W形轨迹运行，滚动轨迹纵横交错，相互重叠，使涂膜厚度均匀。在辊刷压附被涂物的表面初期，用力要轻，避免涂料的过度飞溅或涂膜偏厚；随后逐渐加大压附用力，使刷辊黏附的涂料均匀地黏附在被涂物的表面。辊平是用刷辊轻轻地将辊布的涂料辊刷均匀。修饰是用刷辊沿一定的方向辊饰，尽量消除辊痕，达到修饰美观的目的。对于装饰性要求较高的涂层，要严格按照三个步骤进行施工，同时要选择短毛的刷滚；对于涂膜外观要求不高的涂层，也可将辊平和修饰合为一步进行。  \n\n辊刷使用后，应刮除黏附的涂料，用相应的稀释剂清洗干净，晾干后妥善保存。  \n\n![](images/eac1c7069b296a6a730b3ae82ac119bd2e1d2d15cbcb1c855893f9ea94c0da29.jpg)  \n图5-3-10 辊筒刷涂操作步骤  \n\n丝网法涂装（silk screenprinting）常用于文具、产品包装和路牌、标志等的涂装。其方法是在尼龙网上涂感光胶液，再用图案感光膜紧贴丝网曝光、冲洗，并除去未感光部分的胶膜。丝网干后再刷一层硬化剂以保护胶膜。将制好的丝网平放于被涂物表面，操作时将已刻印好的丝网平放在预涂刷的表面，用硬橡胶刮板来回刮涂一到二次，使涂料渗透到下面，就可在被涂物表面获得相应的图案和文字。  \n\n这种方法具有如下特点。  \n\n$\\textcircled{1}$ 适应性广丝网印刷幅面可大可小。  \n$\\textcircled{2}$ 墨色厚实在所有印刷工艺中，丝网印刷墨层最厚，饱和度高，专色印刷效果更佳。  \n$\\textcircled{3}$ 成本低丝网印刷制版容易，印刷工艺简单。  \n$\\textcircled{4}$ 生产效率低丝网印刷速度慢，不适合联机生产。  \n$\\textcircled{5}$ 图像精度低丝网印刷分辨率不能做得很高，不能印制复杂的图案。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1480,
+        "chunk": "# 第五节 喷涂法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1481,
+        "chunk": "# 一、空气喷涂法  \n\n空气喷涂法（airspraying）是最简单、最基本的喷涂方法，也是目前广泛使用的一种涂装方法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1482,
+        "chunk": "# 1.原理  \n\n空气喷涂法的原理是利用气压在 ${\\hat{0}}.2{\\sim}0.5\\mathbf{M}\\mathbf{Pa}$ 之间的压缩空气气流从喷枪的中心孔喷出，在喷嘴前端形成负压区，容器中的涂料被吸入负压区并从喷嘴喷出，迅速进人压缩空气流，使液-气相急骤扩散，涂料被微粒化，涂料呈漆雾状飞向并附着在被涂物表面，形成连续的涂膜，其原理如图5-3-11所示。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1483,
+        "chunk": "# 2.特点  \n\n空气喷涂具有如下的特点。  \n\n（1）适应性强空气喷涂可以几乎不受涂料品种和被涂物形状的限制，可用于各种涂装作业场所，只要有气源即可使用，是目前被广泛采用的涂装方法之一。  \n\n（2）漆膜外观质量好 空气喷涂所获得的漆膜平整光滑，可达到较好的装饰性。  \n\n（3）涂料雾化充分 不易产生针孔、气泡等病。  \n\n（4）涂装效率高 空气喷涂效率比刷涂快 $8\\sim$ 10倍，每小时可涂装 $150{\\sim}200\\mathrm{m}^{2}$ 9  \n\n![](images/2f627d417664b7ad4362a9628ad1969e2ba20df7dbb6f453253532d3f66c7d07.jpg)  \n图5-3-11空气喷涂原理 1—涂料罐；2一空气流； 3-涂料雾化区；4一负压区  \n\n(5）涂料损失率大空气喷涂漆雾易飞散，污染环境，涂料损失大，利用率一般只有$50\\%$ 左右。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1484,
+        "chunk": "# 3.喷枪的种类  \n\n喷枪是空气喷涂的关键部件。喷枪依据其涂料的雾化方式可分为外混式和内混式两大类，两者都是借助压缩空气的急骤膨胀和扩散作用使涂料雾化，并形成喷雾图形，但由于雾化方式不同，其用途也不相同，目前使用最广的是外混式。外混式和内混式喷枪的结构与特点见表5-3-1。  \n\n表5-3-1外混式和内混式喷枪的结构与特点  \n\n\n<html><body><table><tr><td>分类</td><td>构造</td><td>特 点</td></tr><tr><td>外混式</td><td>1-空气帽；2-涂料喷嘴；3-针阀</td><td>1.涂料与空气在空气帽的外侧混合 2.适宜低黏度的涂料，雾化效果好</td></tr><tr><td>内混式</td><td>1-空气帽；2-涂料喷嘴：3-针阀</td><td>1.涂料与空气在空气帽内侧混合 2.适宜高黏度、厚膜型涂料的涂装</td></tr></table></body></html>  \n\n按照涂料供给方式不同，喷枪可分为吸上式、重力式和压送式三种，如图5-3-12所示。  \n\n![](images/a0ac3055a9ad7a1031effe70a382430914a8f2e74a7f2cc7cd5ca9d12e24d21f.jpg)  \n图5-3-12 喷枪的种类  \n\n（1）吸上式喷枪涂料罐位于喷枪的下部，压缩空气从空气帽的中心孔喷出，在涂料喷嘴的前端形成负压，将涂料从涂料罐内吸出并雾化。吸上式喷枪的涂料喷出量受涂料黏度和密度的影响较大，不适用于密度大且易沉降的涂料。吸上式喷枪应用最普遍，适用于非连续性喷涂。  \n\n（2）重力式喷枪涂料罐位于喷枪的上部，涂料靠自身的重力与涂料喷嘴前端形成负压的共同作用从涂料喷嘴喷出，与空气混合并雾化。重力式喷枪适用于涂料用量少且换色频繁  \n\n的喷涂作业。  \n\n(3）压送式喷枪压送式喷枪是从专门的涂料增压罐供给涂 料，增压后的涂料从涂料喷嘴喷出，与空气混合并雾化。压送式喷 枪适用于涂料用量多且需连续的喷涂作业。  \n\n(4）新型空气喷枪（HVLP/LVLP/LVMP）  \n\n$\\textcircled{1}$ HVLP（高流量低压力）喷枪是在普通空气喷枪的基础上配以特殊的文丘里喷嘴得到的新型喷枪，如图5-3-13所示。  \n\n![](images/8140dd8b9f6e8dbab9e5cd87b6c08bb442791bcdc68cdac90eb6d4f5759fb182.jpg)  \n图5-3-13 HVLP喷枪  \n\nHVLP喷枪使用较大容积的空气，在较低的压力下雾化涂料，通过减少在喷嘴处的雾化空气压力，降低涂料喷速，减少被雾化涂料粒子的反弹和过喷，从而节省涂料消耗。这种喷枪的涂料利用率高，比普通的空气喷涂节省涂料20%～70%，涂装质量好，使用方便、可靠。  \n\n②LVLP（低流量低压力）喷枪的雾化压力小，空气消耗量低，可以喷涂高黏度涂料缺点是涂料喷出量少，喷涂效率低。  \n\n③LVMP（低流量中压力）喷枪的喷涂速度和雾化效率均优于HVLP和LVLP，涂料的利用率达到70%左右，是目前较好的一种空气喷涂技术。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1485,
+        "chunk": "# 4.喷枪的结构  \n\n空气喷枪分为枪头、调节机构和枪体三部分，具体构造如图5-3-14所示。  \n\n![](images/ee9317fa95291ca30c71b8778c48c7976089147008de69cbb5e6b65e210a92fc.jpg)  \n图5-3-14 喷枪整体构造  \n\n1一空气帽；2一涂料喷嘴；3—针阀；4一喷雾图形   \n调节旋钮；5一涂料喷出量调节旋钮；6一空气阀； 7—压缩空气管接头；8一空气量调节旋钮； 9—枪体；10—扳机：11一涂料管接头  \n\n(1）枪头枪头由空气帽、针阀和喷嘴三部分组成，它的作用是可以将涂料雾化，喷涂至被涂物表面，进一步形成连续的涂膜。  \n\n(2）调节机构 调节机构是指调节涂料喷出量、压缩空气流量和喷雾图形的装置。  \n\n(3）枪体枪体上装有扳机和各种防止涂料和空气渗漏的密封件，并制成便于手握的形状。扳机用于控制涂料和压缩空气通道的开启和关闭。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1486,
+        "chunk": "# 5.喷涂方法  \n\n（1）喷枪的调节 喷涂作业之前，必须调整喷枪，以达到适宜的喷涂条件。要根据被涂物的形状、涂料特性、预期的质量要求等，对喷枪的空气压力、涂料喷出量和喷雾图形进行调节，达到最适宜的喷涂条件。  \n\n喷涂时应该根据喷涂涂料的特性和被涂物的表面状况，调节好喷枪的空气压力。空气压力高漆雾粒子细，但漆雾飞散多，涂料损失大。为了减少涂料损失，在满足喷涂效率的前提下，应尽量采用小的空气压力；但过低的空气压力会使漆雾粒子变大，漆膜表面变粗，还容易产生橘皮等缺陷。  \n\n喷雾图形一般呈椭圆形，长边的大小称为幅宽。幅宽应该根据被涂物的形状进行调整，幅宽过小影响喷涂效率，幅宽过大漆雾分散多，涂料损失大。喷涂前要根据喷枪的特性和被涂物形状调整好喷雾图形。椭圆形喷雾图形一般呈中间厚两边薄的状态，喷涂时要注意每一枪要和上一枪的图形有一定的搭接，确保涂膜的厚度均匀。涂料喷出量受到空气量的影响，  \n\n![](images/8b21643dbce7569826b04a1c2d3c16c0ad3b7061eeeb7a51dd4c6d92c30b9997.jpg)  \n图5-3-15 喷涂距离的影响  \n\n增加空气量可以增加涂料喷出量  \n\n(2）喷涂施工要点 要获得良好的喷涂效果，必须控制好喷涂距离、喷枪运行速度、喷雾图形的搭接等施工参数。  \n\n喷涂距离是指喷枪的前端与被涂物之间的距离，在整个喷涂过程中喷涂距离必须保持均匀一致。喷涂距离影响涂膜厚度和涂装效率，在同等条件下，距离近漆膜厚、涂装效率高；距离远涂膜薄、涂装效率低。喷涂距离过近，单位面积形成的漆膜过厚，易产生流挂；喷涂距离过远，漆雾粒子在大气中运行时间长，稀释剂挥发多，涂料飞散多，涂料损失大。喷涂过程中喷枪要保持水平，如果喷枪倾斜，则喷雾图形的上部和下部的漆膜厚度也会产生差异，造成上部过厚，下部过薄的弊病，如图5-3-15所示。  \n\n保持喷枪与被涂物表面的垂直也是确保涂膜厚度均匀一致的重要因素，喷涂时要始终保持喷枪与被涂物表面垂直，从而使喷涂距离恒定。如果喷枪呈圆弧形运行，则喷涂距离在不断地变化，所获得的漆膜中部与两端不同，造成中间厚、两端薄的病，如图5-3-16所示。  \n\n![](images/af1a080e54ff0cb8e44702b0b847f3b1dfae9eaa540f51d11a9bf3bdb7c85f7d.jpg)  \n图5-3-16 喷枪运行不当对喷涂距离的影响  \n\n喷涂作业时，喷枪运行速度要适当，并保持恒定。喷枪的运行速度一般控制在30～60cm/s，运行速度过慢，形成的涂膜厚，易产生流挂；反之，运行速度过快，形成的漆膜薄，易产生漏底。喷枪运行速度受涂料喷出量和漆雾图形幅宽的制约，喷涂时喷雾图形之间的部分重叠图形称为搭接。由于喷雾图形中部漆膜较厚，边沿较薄，喷涂时前后喷雾图形必须相互搭接，才能使漆膜均匀一致。  \n\n(3）涂料黏度的调节涂料的黏度影响涂料喷出量，黏度高，涂料喷出量小；反之，黏度低，涂料喷出量大。涂料黏度对雾化效果有影响，进而影响涂膜的平整度。因此喷涂时应重视涂料黏度的调整，喷涂前应进行必要的稀释，将喷涂黏度调整到合适的范围。  \n\n(4）压缩空气的要求空气喷涂使用的压缩空气必须经过过滤，除去油和水分，以免混人涂料中影响涂膜质量。为了获得所需的空气压力，要配置调压阀，而且要安装在易于看见和调整的地方，便于检查和调节。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1487,
+        "chunk": "# 6.喷枪的选择和维护  \n\n枪体的大小、重量、涂料供给方式、喷嘴口径和空气使用量是喷枪的主要参数，也是喷枪选用的主要依据，在实际操作时应该根据喷涂作业条件综合考虑这些要素，选择合适的喷枪。  \n\n(1）喷枪的选择原则一般情况下，大型被涂物和大批量连续喷涂作业，可选用大型喷  \n\n枪；小型或凹凸不平的被涂物，可选用小型喷枪，但是小喷枪的涂料喷出量小，喷涂效率低。为减轻操作者的劳动强度，在可能的情况下应尽量选用小型喷枪。  \n\n涂料的颜色更换频繁，涂料用量少、小批量的涂装作业，适宜选用涂料罐容量为1L以下的重力式喷枪；有更换颜色的要求，涂料用量稍大，并须进行侧面喷涂的喷涂作业，宜选用涂料罐容量为1L的吸上式喷枪；颜色比较单一，涂料用量大的连续喷涂作业，可选用压送式喷枪。  \n\n通常依据涂料喷出量选择喷嘴的孔径。喷嘴孔径越大，涂料喷出量越大。黏度高的涂料喷出量小，应选用涂料喷嘴口径较大的喷枪。压送式喷枪的喷出量随压送涂料压力的提高而增加，因此，可选用喷嘴较小的喷枪。  \n\n(2）喷枪的维护和保养使用后的喷枪应该立即进行维护和保养，保持喷枪的良好状态，便于今后的使用。喷枪维护和保养时应注意以下几点。  \n\n① 喷枪使用后，应先将剩余的涂料倒出，用清洗溶剂将涂料罐清洗干净，然后再向涂料罐中加人清洗溶剂，像喷漆一样喷出清洗溶剂，以清洗涂料通道。要坚持“少量多次”的原则，彻底将喷枪清洗干净。  \n\n② 要将空气帽、涂料喷嘴和枪体彻底刷洗干净，是否干净的标准是不能看出上次喷涂的涂料是哪种颜色的涂料。当发现堵塞时，应用硬度不高的针状物疏通，避免损伤涂料喷嘴和空气帽。  \n\n③ 暂停喷涂时，为了防止干结的涂料堵塞涂料和空气通道，应立即将枪头浸人溶剂中；喷枪长期不用，应将喷枪彻底清洗干净后涂上防锈油，以防止锈蚀。  \n\n④要经常检查枪体的针阀、空气阀的密封垫，发现渗漏，及时更换。  \n\n③要定期拆卸和组装喷枪，组装后应检查各活动部件，保证各种接口处无空气和涂料的渗漏，扣动扳机开始应只有空气喷出，继续扣紧才应喷出涂料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1488,
+        "chunk": "# 二、无空气喷涂法  \n\n高压无气喷涂（airless spraying）是通过给涂料施加高压，使涂料喷出时雾化成极细小微粒，雾化的涂料喷射到被涂物的表面，形成连续涂膜的涂装方法。无气喷涂的推广使用增加了涂料的利用率，减少了对大气的污染、提高了涂装作业效率。随着时代的进步，无气喷涂工艺与设备有了明显的改进和发展，满足了各种涂装作业的需要，已经在船舶、集装箱、桥梁、钢结构件、建筑及各种机械行业得到了广  \n\n泛应用，是目前应用最广泛的涂装方法之一，",
+        "category": " Introduction"
+    },
+    {
+        "id": 1489,
+        "chunk": "# 1.原理  \n\n无气喷涂的原理如图5-3-17所示。加压设备对涂料施加高压，使其以“薄片”形式从喷嘴口喷出，当涂料离开涂料喷嘴的瞬间，便以高达$100\\mathrm{m}/\\mathrm{s}$ 的速度与空气发生激烈的高速冲撞，使涂料破碎成微粒，在涂料粒子的速度未衰减前，涂料粒子继续向前与空气不断地多次冲撞，涂料粒子不断地被粉碎，使涂料雾化，并黏附在被涂物表面，形成连续的漆膜。  \n\n![](images/96debfb1002d952fb1c63c8206ba6f4fcd692fd652c5e82ebb4fd5876b5a7e02.jpg)  \n图5-3-17 无气喷涂的原理",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1490,
+        "chunk": "# 2.特点  \n\n(1）漆雾的飞散少 由于不使用空气雾化，无空气喷涂漆雾飞散少，而且涂料的喷涂黏度较  \n\n1一涂料罐；2一涂料输送管路；3一高压过滤器；   \n4一空气进口；5—油水分离器；6—高压泵；7-喷枪  \n\n高，施工固体分高，稀释剂加量减少，减轻了对环境的污染；涂装效率高，节约涂料。  \n\n(2）涂料的喷出量多涂料的喷出量多，涂装效率高，无气喷涂的涂装效率是刷涂的10倍以上，是空气喷涂的3倍以上，可达到 $400{\\sim}1000\\mathrm{m}^{2}/\\mathrm{h}$ 。可获得较厚的漆膜，减少喷涂道数。  \n\n(3）可以喷涂高黏度涂料既可以喷涂黏度较低的普通涂料，也可以喷涂高黏度涂料。  \n\n（4）容易实现自动化 设备简单，容易实施喷漆工艺的自动化和无人涂装。  \n\n(5）装饰性一般涂料雾化粒子较粗，雾化液滴一般为70～150um，比空气喷涂的雾化粒子20～50um大三倍，因此涂膜的装饰性一般。  \n\n(6）调节喷出量和喷雾图形复杂无气喷枪没有涂料喷出量和漆雾图形幅宽的调节机构，只有通过更换喷嘴才能满足调节的要求，操作比较麻烦。与空气喷涂喷雾扇形的羽状边缘不同，无气喷涂的喷雾扇形的边缘尖锐，产生所谓的鱼尾喷涂，使用旧的枪嘴在扇形的边缘容易产生漆的弊病。  \n\n(7）需要高压管路涂料喷涂过程中需要高压，因此需要耐高压的涂料输送管道。高压涂料喷出速度高达100m/s，涂料射流可以穿透皮肤，需要注意安全。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1491,
+        "chunk": "# 3.无气喷涂设备  \n\n![](images/806c2117db16e6adbf08f4104a2b69d8f1b0efcea9598dac67355a8f631c0a7b.jpg)  \n图5-3-18 无气喷涂设备的构造  \n\n1—动力源；2—高压泵；3—涂料进口； 4一蓄压过滤器；5—涂料输送管道；6—喷枪  \n\n无气喷涂设备由动力源、喷枪、高压泵和蓄压过滤器等组成，如图5-3-18所示。  \n\n(1）动力源根据涂料被加压的方式，无气喷涂的动力源有压缩空气、油压和电动三种类型。目前大部分采用压缩空气作为动力源，这种方法操作简便、安全，应用最广泛。  \n\n(2）喷枪无气喷枪由枪体、涂料喷嘴、过滤网、顶针、扳机、密封垫、连接部件等组成。枪体要轻巧，喷涂时操作方便，扳机启闭灵活，与高压管连接处转动灵活，密封良好。由于涂料通道要承受高压，要求具有优异的耐高压密封性，不泄漏高压涂料。常用的无空气喷枪有手持式喷枪、长杆式喷枪和自动喷枪等。  \n\n无气喷枪最关键的部件是涂料喷嘴，喷嘴的几何形状、孔径大小与加工精度等决定了涂料的雾化效果、喷出量、喷雾图形的形状和幅宽等施工参数。由于要经受高压涂料的强烈摩擦，喷嘴要耐磨损，一般采用耐磨材料制作，如硬制合金等。常用的无空气喷嘴有标准型枪嘴、自清洁枪嘴、圆形喷嘴和可调喷嘴等几种。  \n\n标准型喷嘴（图5-3-19）的开口呈橄榄形，喷雾图形呈椭圆形。喷雾图形的幅宽为150～600mm，涂料喷出量一般为0.2～5L/min，可以满足各种喷涂需要。这种喷嘴被堵塞时处理比较麻烦，目前应用越来越少。  \n\n自清型喷嘴是将标准型喷嘴做在了换向机构之上，当喷嘴被堵塞时，将整个机构旋转180°，就可以使喷嘴转变方向，从而将堵塞物轻而易举地冲掉。目前以圆柱自清型喷嘴（图5-3-20）最为常用。  \n\n另外还有适用于如管道内壁等狭窄部位喷涂的圆形喷嘴和带有可以调节涂料喷出量及喷雾图形宽度的可调节型枪嘴，满足各种被涂物的涂装要求。  \n\n![](images/b6c2d9bbd97ffd1dc595bec95b1716f87406b2558ccb70cc53697bfa94908cf7.jpg)  \n图5-3-19 标准型喷嘴1—喷嘴；2—橄榄形开口  \n\n（3）高压泵高压泵是无空气喷涂的心脏，它把动力源的能量转换给涂料，赋予涂料非常高的飞行速度，它的工作状态是决定涂装效果的关键。  \n\n$\\textcircled{1}$ 工作原理高压泵按照工作原理分为复动式和单动式两种。复动式的柱塞向上或向下运动时都能输出涂料，涂料的压力波动小，零部件磨损小，使用寿命长，目前被广泛使用。  \n\n![](images/31213a1d59ba7527b9e48fec07352f8e72db6918ebd2df201563b16e5e67b9bd.jpg)  \n图5-3-20 自清洁喷嘴1—喷嘴：2—喷嘴开口；3一换向反冲阀  \n\n其加压原理是，泵的上部气压P驱动加压活塞，使其推动泵下部的柱塞，给涂料施加压力，加压活塞的面积A与柱塞面积a之比越大，所产生的涂料压力越高。复动式高压泵工作原理和加压原理如图5-3-21和图5-3-22所示。  \n\n![](images/ba876dbc2c2499a11c152652cd1c09912ceb252d95598475d9f1c740354eba91.jpg)  \n图5-3-21 复动式高压泵工作原理  \n\n涂料压力 $(\\phi)=$ 活塞面积 ${\\frac{A}{a}}x$ 空气压力 $(P)$ 柱塞面积  \n\n单动型高压泵结构简单，但零部件使用寿命短，应用不多。  \n\n$\\textcircled{2}$ 分类根据动力源的不同，无气喷涂用的高压泵分为气动、油压和电动三种。气动高压泵应用最为广泛，这种高压泵以压缩空气为动力，压力一般为0.4～0.6MPa，可以通过减压阀调节进口压缩空气压力，从而控制涂料的压力。其构造示意如图5-3-23所示。  \n\n![](images/820311fd01357c2f8ada3ae12e043277cc2952978b1863329b1884a9278e0bad.jpg)  \n图5-3-22 复动型高压泵加压原理  \n\n![](images/611038b43eb65f7fcbca7cb9f31d8a90655fe5171a58faabab5523b53b7f18a0.jpg)  \n图5-3-23气动高压泵构造示意图1一汽缸；2-高压涂料出口：3一吸漆阀；4一出漆阀；5一柱塞；6一活塞：7-压缩空气人口  \n\n按照高压泵的设计原理，涂料压力可达到压缩空气压力的几十倍。涂料压力与压缩空气输人压力的比值称为泵压比，等于柱塞的面积与加压活塞面积的比值。喷涂作业时，涂料的喷出压力不一定符合出厂注明的压力，准确的涂料喷出压力应该根据高压泵的特性曲线确定。另外，如果涂料输送管道较长，还要考虑管道压降的影响。气动高压泵优点是使用安全，设备结构简单，操作容易掌握；缺点是动力消耗大，噪声严重。  \n\n液压高压泵以油压作为动力，借助减压阀控制油压，从而调整涂料的喷出压力，准确地喷出压力也要根据高压泵的特性曲线确定。油压高压泵的优点是动力利用率高，噪声比气动高压泵低；使用也很安全，维护不困难，成本低；缺点是需要专用的油压源，油压源所用的油有可能混人涂料中，产生涂膜病。  \n\n电动高压泵以交流电源驱动，喷出压力可达25MPa。涂料喷出量影响涂料喷出压力，准确的涂料喷出压力也需根据泵的特性曲线确定。电动高压泵的优点是移动方便，只要有电源即可，作业适应性强，成本低，噪声小。  \n\n(4）蓄压过滤器蓄压过滤器由蓄压器桶体、过滤网、过滤网架、放泄阀、出漆阀组  \n成。其作用是稳定涂料压力，过滤涂料中的杂质，避免喷嘴堵塞。(5）输送管道输送管道要求耐高压和涂料溶剂的侵蚀，避免渗漏，耐压强度达到  \n$\\mathsf{25M P a}$ ，甚至要求达到35MPa，同时输送管道要能消除静电，避免静电的积聚而发生火灾。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1492,
+        "chunk": "# 4.喷涂工艺  \n\n(1）涂料喷嘴的选择涂料喷出量和喷雾图形的幅宽是涂料喷嘴口径选择的依据。涂料喷嘴说明书中标注的涂料喷出量是在特定的喷涂条件（黏度、密度、涂料压力）下测试的数据，称为标准喷出量，枪嘴选择时应当根据涂料的实际喷涂情况来确定。喷雾图形幅宽和涂料喷出量不像空气喷涂那样容易调节，只能通过更换喷嘴来进行。标准的喷雾图形幅宽是喷涂距离在 $\\mathbf{300mm}$ 喷涂时喷雾图形的幅宽。各厂商都有一系列规格的喷嘴，供施工者选择。  \n\n中国船舶工业总公司直属四川长江机械厂的标准系列喷嘴共有C、B、W、Z四种系列型号，共三百多种。  \n\n$\\textcircled{1}$ C型喷嘴雾化较好，均匀细腻，喷涂后涂料较光滑、美观。适用于对涂膜要求较高的场合。  \n\n$\\textcircled{2}$ B型喷嘴雾化较C型稍差些，适用于对涂膜外观要求不太严格的场合。  \n\n$\\textcircled{3}$ W型喷嘴 适用于喷涂水性涂料。  \n\n$\\textcircled{4}Z$ 型喷嘴 适用于喷涂富锌涂料。  \n\n型号由五位阿拉伯数字组成，前三个数字表示每分钟的流量（喷嘴压力为 $\\mathrm{10MPa}$ ，介质为乳化液)，后两个数字表示喷雾幅宽。如02035表示每分钟流量为2L，喷雾幅宽为$35c m$ 。美国固瑞克（GRACO）公司是著名的涂装设备供应商。该公司的标准型喷嘴为163系列，共有123个型号。其型号为163三位数字后为一短横线，然后再连一个三位数，第一位数表示距喷嘴12in（ $\\mathrm{.1in=2.54cm}$ ，下同）距离时的喷雾幅宽的 $1/2\\mathrm{in}$ ，后两位表示喷嘴孔径的1000倍。如163-415型表示：标准喷嘴，喷雾幅宽 $4\\times2=8\\mathrm{in}\\left(203\\mathrm{mm}\\right)$ ，孔径为0.015in $(0,38\\mathrm{mm})$ 。286系列为回转自清洁型喷嘴，后面数字概念不变，现被广泛采用。  \n\n相对来说，长江机械厂的枪嘴采用了国际单位，表示方法比较容易理解和识别。  \n\n（2）涂料密度和压力对喷出量的影响涂料的实际喷涂量受涂料密度和压力的影响，一般要根据涂料密度和压力进行修正。如果实际喷涂所用涂料的密度比标准密度大，则实际涂料喷出量小于标准喷出量；反之则实际喷出量大于标准喷出量。  \n\n涂料压力是重要的喷涂工艺参数。喷涂压力增大可以使涂料的喷出量增加，但是涂料压力要控制适当，不适当地依靠提高喷涂压力来增加涂料喷出量是不经济的。涂料输送管道内的压力损失以及喷枪与高压泵所处的高度差都会影响最终的喷涂压力，从而影响涂料的喷出量和喷涂效率。  \n\n(3）喷涂要领喷涂距离通常为30～50cm。距离太大会造成涂膜表面粗糙，涂料的损失也大，对于某些快干涂料，还会产生干喷雾现象，即涂料的雾化粒子未到达被涂物表面时，已成为干燥的粉末状态。距离太小既会造成操作困难又容易发生涂膜过厚并引起流挂和橘皮等弊病。  \n\n喷枪与被涂物表面应该始终保持垂直，喷枪左右上下移动时，应注意与被涂物表面等距，避免做弧形或曲线移动，以保持涂装膜厚均匀。  \n\n喷枪移动的速度要适当。根据膜厚的要求确定喷枪的移动速度，膜厚要求高，移动速度稍慢；反之，膜厚要求低，移动速度稍快。喷涂时要经常用湿膜计控制湿膜厚度，做到即符合要求又不超厚造成浪费。  \n\n另外，喷涂工作通常要遵循先上后下、先难后易的原则进行。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1493,
+        "chunk": "# 5.无气喷涂设备的选用和维护  \n\n(1）无气喷涂设备的选用无气喷涂设备有很多型号，应根据所用涂料的特性、被涂物的形状与生产批量、施工场所具备的条件等选择适当的型号。涂料的黏度是首先考虑的选择因素。高黏度涂料，难于雾化的涂料必须选用泵压比高的型号。被涂物的形状和生产批量是设备型号选择的第二因素。被涂物形状小或批量小，一般选用涂料喷出量较小的型号；被涂物面积大或批量大，如船舶、桥梁、集装箱涂装连续生产线等，选用涂料喷涂量较大的型号。施工场所具备的条件也是选择的因素之一。如果有压缩空气，可选用气动无气喷涂设备，如果作业场所没有压缩空气，而有电源，可选用电动无气喷涂设备。设备型号选择时，以上三要素要综合衡量，既要满足涂装的实际需求，又能达到合理经济的目的。  \n\n(2）无气喷涂设备的保养为了保证无气喷涂设备的正常使用，延长设备的使用寿命，使用过程中要及时保养和维护。使用的压缩空气要定期排除水分和杂质；施工压力要低于设备的上限；使用后设备要清洗干净；应经常检查设备运转情况，发现故障，及时排除。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1494,
+        "chunk": "# 6.新型无气喷涂设备  \n\n近十几年来，涂料新品种的研发突飞猛进，新的涂料品种不断出现，促进了涂装设备的发展。为适应新型涂料涂装的需要和改善无气喷涂设备的某些性能，不断有新型的专用无气喷涂设备推向市场。  \n\n（1）双组分无气喷涂设备双组分涂料如胺固化环氧树脂涂料、异氰酸酯固化聚氨酯涂料等由于具有优异的综合性能，得到越来越广泛的应用。但这类涂料的两组分混合后必须在规定的时间内用完，如一次调配过多，容易产生浪费，而且超过使用期限的涂料如果处理不当，很有可能会固化在喷漆泵和管道中，造成巨大的浪费。为解决这个问题，双组分无气喷涂设备将涂料两组分的混合和喷涂同步进行，巧妙地克服了上述缺点，特别适用于喷涂双组分涂料。其原理如图5-3-24所示。  \n\n按照涂料的混合方式，这类双组分喷涂机可分为内混式和外混式两大类，其中以内混式应用比较广泛，在此主要介绍这种方式。内混式双组分无气喷涂设备是将涂料按照两组分的质量比换算成体积比，经过双组分泵将主剂和固化剂压送至混合器内进行混合，然后由喷枪喷出。设备构造如图5-3-25所示。  \n\n涂料的混合是在混合器内进行的。混合器由导管组成，内部装有一定数量的液流分割器，具有分割、变向和转移涂料的作用。导管内的分割器呈螺旋状，即能将贴近管壁流动沿着扭曲面向导管的中心部位转移，又能将导管中心部位的液流向管壁转移，如此反复不停地转移导管内液流的位置，从而使主剂与固化剂充分的混合。为了确保喷涂质量，必须保证双组分涂料的正确配比。在涂装作业前，按照双组分涂料所要求的质量比和两组分的密度，计算出两组分的体积比并设定好，涂装过程中禁止随意调整；为了避免涂料固化在混合器内，堵塞导管，喷涂作业长时间停机时，应关闭涂料控制阀，启动清洗程序，将混合器清洗干净。喷涂作业结束后，应将设备内的涂料全部清除，并用清洗溶剂清洗干净。  \n\n![](images/fbdad2337d2c6374a8ae2223ddabb8543fd69c7b00d35bbe590ce549fc7858c8.jpg)  \n图5-3-24双组分无气喷涂原理1一涂料罐（主剂、固化剂）；2一涂料泵；3一分配漆缸；4一加热器；5-清洗泵；6一混合器；7一回流循环系统  \n\n![](images/b2b70a03dddd5b82b4a44cfb0c21907916e162a132506d774c3d6d16303947c0.jpg)  \n图5-3-25双组分喷涂设备构造图 1—主剂罐；2—固化剂罐；3一高压泵； 4—涂料输送管道；5—喷枪  \n\n(2）富锌涂料无气喷涂设备富锌涂料具有优异的防腐蚀性能，在海洋与工业环境等严酷腐蚀性的重防腐领域被广泛应用。但这种涂料密度大，沉降速度快，易结块，容易堵塞喷涂系统，且锌粉含量高，容易损坏高压泵的压送机构，普通设备无法喷涂，需要采用专门的喷涂设备。  \n\n富锌涂料专用无气喷涂设备是根据富锌涂料的特点进行设计的，如图5-3-26所示。  \n\n![](images/d530ff75089a7fa7980fae9042ab504ad522dfc6229f0f3b9e4067b7880861a0.jpg)  \n图5-3-26富锌涂料专用喷涂机 1一进漆口；2—循环管路；3—高压泵； 4—涂料管路；5—喷枪  \n\n![](images/3f3d4d2b26ff80c33c3b91edc9f7b88951db2bbb268d1d22baeace1fb114c1bd.jpg)  \n图5-3-27热喷涂的基本原理 1一涂料罐；2—高压泵；3—加热器； 4一过滤器；5一热喷枪；6—旋转阀  \n\n为了满足富锌涂料喷涂的要求，高压泵的进口压力比较大，一般不小于0.4MPa，加压活塞与连杆的运动速率也较缓慢；为了提高耐磨性，材质采用特殊的耐磨材料制造；为了解决喷涂过程中涂料的沉淀问题，配备有专门的搅拌装置，新型设备配备了涂料自循环系统；涂料喷出量大，压缩空气进气管与涂料输送管的口径也比通常的大；高压泵的加压活塞系统和高压柱塞系统为分体式，清洗、保养和更换易损件容易。  \n\n(3）加热无气喷涂设备当涂料的温度升高时，由于黏性液体内部摩擦减少，其黏度会随着下降。加热喷涂设备的功能是确保涂料雾化所需的适宜黏度，并使其保持恒定不变，发挥这种功能的是涂料加热器。热喷涂是在普通喷涂的基础上预先将涂料加热再喷涂的施工方法，基本原理如图5-3-27所示。加热喷涂有如下特点：  \n\n$\\textcircled{1}$ 可以节省溶剂 $30\\%$ 左右，有机溶剂挥发量少，有利于减轻对环境的污染；$\\textcircled{2}$ 涂料的固体分增高，可以提高喷涂一道的漆膜厚度，可缩短涂装作业周期；$\\textcircled{3}$ 喷涂黏度稳定，不会受季节气候的变化的影响，能确保漆膜厚度均匀一致；$\\textcircled{4}$ 温度的下降发生在离开喷枪口和到达工件之间，导致涂料黏度显著增加，减少了高固体涂料发生流挂的可能性；  \n\n$\\textcircled{5}$ 改善了涂料的流平性，能提高漆膜的丰满度和光泽。  \n\n通常的加热喷涂设备是无空气喷涂喷枪配以涂料加热器，其中加热器是热喷涂技术的关键设备。涂料加热器的加热方式有热水加热、蒸汽加热、电加热等。由于电加热方式升温快，温度容易控制，所以被广泛采用。但使用加热喷涂方法时必须注意涂料对热喷涂的适应性：有些涂料如聚氨酯涂料、水分散热固型涂料，在加热条件下会影响其化学稳定性，不适宜采用热喷涂。  \n\n一般热喷涂采用的加热温度为 $38\\sim65^{\\circ}C$ ，因为各种涂料的温度黏性特性不一样，预先应测定温度黏度特性曲线，有助于准确选择加热温度。  \n\n涂料加热器必须安装防爆装置。经常检查温度控制机构的可靠性，以防温度过高引起事故。  \n\n（4）超临界液体喷涂设备超临界液体喷涂是利用在超临界状态下，二氧化碳呈现类似于烃类的溶解作用，而二氧化碳不算VOC，这样可以减少VOC的排放。二氧化碳的超临界条件是临界温度为 $31.3^{\\circ}\\mathrm{C}$ ，临界压力为 $\\boldsymbol{\\mathcal{I}}.4\\mathrm{MPa}$ 。要进行超临界喷涂必须控制温度和压力，同时必须使用双面进料喷涂，一面进料用低溶剂型涂料；另一面使用超临界二氧化碳。当涂料离开枪口时，二氧化碳迅速汽化而打碎了已经雾化的液滴，使之粒径减小，因而形成较窄粒径分布。此液滴的大小与空气喷枪所获得的液滴大小类似，而比无空气喷枪喷涂的液滴要小得多，所以装饰性较好。同时二氧化碳的挥发在液滴到达表面前已经完成，因此所涂装的涂膜黏度较高，不容易产生流挂，同时提高了涂覆效率，减少了过喷和废物处理问题。美国联碳公司已经使用超临界涂装技术进行木器家具的涂装，涂装质量优于传统的空气辅助无气喷涂，可以减少VOC排放 $57\\%\\sim57\\%$ ，同时可以减少操作费用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1495,
+        "chunk": "# 三、高压辅气喷涂法  \n\n空气喷涂涂料损耗大，而高压无气喷涂质量不理想。高压辅气喷涂（air asstant spraying）设备集中了无气喷涂和空气喷涂的特点，降低了高压无气喷涂的涂料压力（5MPa以下)，减少了喷涂射流的速度，借助少量压缩空气，帮助改善雾化效果。这种涂装方法雾化效果好，涂料利用率高，漆膜装饰性好，适用于金属制品、电器制品、车辆、高档家具和工艺品的涂装。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1496,
+        "chunk": "# 1.原理  \n\n当涂料在低压条件下被压送并从涂料喷嘴喷出时，借助从空气帽喷出的雾化空气流，促进漆雾细化，使涂料呈漆雾状飞向并附着在被涂物表面，涂料雾粒迅速集聚成连续的漆膜。  \n\n![](images/0c5144f0cc7092a9b71898dfd7de85ec8b56995122e02d802827e0b0626a5a9e.jpg)  \n图5-3-28 辅气喷涂原理图  \n\n1一涂料罐；2—涂料管道；3—高压过滤器： 4—压缩空气；5—油水分离器；6一高压泵； 7一辅气喷枪  \n\n其原理如图5-3-28所示。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1497,
+        "chunk": "# 2.特点  \n\n（1）喷涂的压力低高压辅气喷涂涂料压力仅为$\\mathrm{4\\sim6MPa}$ ，远低于无气喷涂涂料压力（ $\\mathrm{:10MPa},$ ，从而延长了高压泵和喷枪的使用寿命，降低了涂料输送管道的耐压强度要求；同时因为压力低，减少了柱塞泵往复运动产生的噪声污染。  \n\n（2）雾化效果好 高压辅气喷涂漆雾粒子细，粒子可达 $70\\mu\\mathrm m$ ，提高了漆膜的装饰性。  \n\n(3）漆雾图形可调节解决了无气喷涂喷雾图形无法调节的问题，可以根据被涂物的形状任意调整喷雾图形的幅宽，操作方便。  \n\n（4）涂装效率高 高压辅气喷涂的涂装效率可达$75\\%$ ，漆雾飞散少，涂装效率高。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1498,
+        "chunk": "# 3.高压辅气喷涂设备  \n\n高压辅气喷涂设备是在高压无气喷涂设备的基础上增加了空气输送管，用以辅助雾化涂料，所以能够喷涂黏度较高的涂料，喷涂效率高，并能获得较厚的涂膜。设备构造如图5-3-29所示。  \n\n![](images/e99d7019104c48322f06a3a1df03de5afffd05717276027e6fea0463d4d88680.jpg)  \n图5-3-29 高压辅气喷涂机1—高压辅气喷枪；2一涂料输送管；3一空气输送管；4一进漆口；5一高压泵  \n\n![](images/ba59b7bad466c924eece1f6fc452319617bb4d3a77e795dc4f33f0a0808fed7a.jpg)  \n图5-3-30 高压辅气喷枪  \n\n1一喷雾图形调节装置；2一空气管接头；   \n3—涂料管接头；4—空气帽；5一涂料喷嘴  \n\n高压辅气喷涂设备所用的喷枪与无气喷涂喷枪的枪嘴类似，只是在原来的基础上增设了空气帽和漆雾图形调节装置，如图5-3-30所示。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1499,
+        "chunk": "# 四、静电喷涂法  \n\n静电涂装（electrostatic spraying）具有涂料利用率高、对大气的污染少、涂装作业效率高等优点。随着时代的发展，静电涂装设备有了明显的改进和发展，满足了各种涂装作业的需要，已经在汽车、农用机器、家用电器、日用五金、钢制家具、电动工具及玩具等工业  \n\n领域得到了广泛应用，是目前应用广泛的涂装方法之一",
+        "category": " Introduction"
+    },
+    {
+        "id": 1500,
+        "chunk": "# 1.原理  \n\n静电喷涂是利用高压静电场使带负电的涂料微粒沿着电场相反的方向定向运动，并使涂料微粒吸附在带正电工件表面的一种喷涂方法。工作时静电喷涂的喷枪接负极，工件接正极并接地，在高压电源的高电压作用下，喷枪的端部与工件之间就形成一个静电场，使空气产生强烈的电晕放电。涂料经喷嘴雾化后喷出，被雾化的涂料微粒通过枪口极针的边缘时因接触而带电，当经过电晕放电所产生的气体电离区时，将再一次增加其表面电荷密度。这些带负电荷的涂料微粒在静电场作用下，向异极性的工件表面运动，并被沉积在工件表面上形成均匀的涂膜，其原理如图5-3-31所示。  \n\n![](images/f69852672d350e9e0b0afdbd105bfbffd230298f227340d5c68419cf213cad86.jpg)  \n图5-3-31静电涂装原理示意图 1一交流电源；2—高压电源；3—涂料管；4—空气管；5—高压电缆； 6一静电喷枪；7一电力线；8一被涂工件",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1501,
+        "chunk": "# 2.特点  \n\n(1）涂料利用率高采用静电涂装，涂料粒子受电场作用力被吸附在工件表面，显著减少了飞散和反弹，使涂料利用率大幅度提高，涂料利用率比空气喷涂提高1～2倍。  \n\n(2）涂装效率高静电喷涂易于自动化流水作业，生产效率比空气喷涂提高1～2倍，提高了劳动生产率。(3）涂膜质量好带电涂料粒子受电场的作用产生环抱效应，获得的涂膜均匀、平整、光滑、丰满，光泽高，装饰性好。(4）改善涂装条件静电涂装可以在静电喷涂室内进行，使涂装环境大为改善。(5）火灾的危险性大静电喷涂设备复杂，喷具是特制的，工作状态有几万伏高压，具有较大的火灾风险，需要严格执行操作规程。(6）涂料的电阻要低静电涂装对涂料的电性能有一定要求，一般要求涂料的电阻小于$100\\mathbf{M}\\Omega$ ，同时易受环境温湿度的影响。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1502,
+        "chunk": "# 3.影响静电涂装的因素  \n\n(1）电压电压是影响涂装效率的重要因素，喷涂效率一般随着电压的升高迅速增加。采用高电压，涂覆效率高，但容易发生高压击穿导致火灾的危险。一般电压范围控制在$90\\mathbf{kV}$ 左右。  \n\n(2）涂料的黏度涂料的黏度愈高，雾化性能愈差。但黏度高时，涂料的兑稀率低，施工固体分高，涂膜丰满、光泽高。静电喷涂用涂料施工黏度要比普通喷涂略低，以利于雾化的涂料微粒沿着电力线方向环抱沉积，一般控制在 $15\\sim20\\mathrm{s}$ (涂4杯)。  \n\n(3）涂料的电性能介电常数是衡量涂料电性能最主要的参数。涂料的电性能直接影响静电雾化性能及静电效果，阻抗值过高带电困难，静电效果差；过小则易漏电，危害喷枪且不利于安全。普通涂料极性很低，电阻往往大于 ${100}\\mathbf{M}\\Omega$ ，为了使涂料能适应静电涂装，必须用介电常数较高的溶剂或专用导静电助剂来调整涂料的阻抗，使之在 $0.05\\sim$ 50MΩ之间。  \n\n(4）喷涂距离根据计算，每1cm间隔空气能承载10kV电场作用，低于此极限就会极间击穿，产生火灾的危险。喷涂距离越近，喷涂效率越高；反之，距离越远，喷涂效率越低。通常喷涂距离为 $30{\\sim}35\\mathrm{cm}$ ：  \n\n(5）旋杯的转速旋杯的转速越快，涂料的雾化粒子愈细，涂装效率愈高；但涂料粒子的运动速度过快，不利于带上电荷，从而导致已雾化的粒子中颜料含量的差异，造成涂膜不均匀。  \n\n(6）喷枪的布置旋杯式静电喷枪，在工件上形成的涂膜为中空形厚度不均的涂膜。因此要根据被涂工件的具体情况，配置多支喷枪，从而获得均匀的涂膜。  \n\n(7）旋杯的口径旋杯的半径愈大，则涂料粒子愈细，一般要根据涂装的实际情况，选择合适的旋杯口径。  \n\n(8）喷涂量喷涂量愈小愈有利于涂料粒子的微粒化，但喷涂量小，涂装效率低。因此要根据涂装质量和喷涂效率的要求，来确定涂料的喷涂量。  \n\n另外，工件的悬挂方法、极针的配置、涂料的表面张力和涂料的输送方式等也对静电涂装的效果有一定影响。上述这些因素不是相互孤立的，必须综合考虑才能获得满意的涂装效果。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1503,
+        "chunk": "# 4.静电喷涂装置  \n\n(1）静电涂装设备的类型静电喷涂装置分为手动涂装用和自动涂装用。手动涂装用一般均是手提式，分为空气雾化方式、无空气雾化方式、电气雾化方式三种；自动涂装用分为固定式和移动式，固定式分为空气雾化方式、电气雾化方式两种。移动式分为空气雾化方式、无空气雾化方式、电气雾化方式三种。下面主要介绍常用的静电喷涂装置。  \n\n![](images/9b583dd148fe8290326b26d1a4e19ff677c632b15ca309752a732aaccd66dca5.jpg)  \n图5-3-32手提式空气雾化静电喷涂设备 1一高电压发生器；2—AC电源；3—压缩空气输人口； 4一空气管；5—高压电缆；6—静电喷枪；7一涂料输送管； 8-涂料泵；9一涂料贮罐  \n\n$\\textcircled{1}$ 手提式空气雾化静电喷涂设备空气雾化静电喷涂的雾化方式为压缩空气，在喷枪口高压电极作用使雾化涂料带电，雾化微粒沿着电力线的方向吸附沉积在被涂工件表面，形成涂膜。空气雾化静电喷枪的结构轻巧，适应性灵活，特别适于作用场地狭小和外形复杂的被涂工件，被广泛用于机械、农机行业。手提式空气雾化静电涂装设备由高压电源、供漆系统和静电喷枪组成，如图5-3-32所示。  \n\n$\\textcircled{2}$ 低压无气静电喷涂设备 低压静电喷涂结合了无气喷涂技术和静电喷涂技术的优点。涂料被高压柱塞泵压缩，通过喷枪口瞬时失压雾化，并在高电位电极放电而带上电荷，在电场的作用下，被吸附于工件表面。这种设备与空气静电喷涂设  \n\n备比，雾化涂料微粒的动力足，能够喷涂黏度较高的涂料，喷涂量较大，涂装效率高，如图5-3-33所示。  \n\n![](images/6fe13863b8d3a80193be01988c637c84f4398dbf977fa837a21e0da82bd96b9f.jpg)  \n图5-3-33无气静电喷涂设备 1—高压电源；2—电缆；3—高压泵；4—静电喷枪；5—涂料罐；6—涂料输送管道  \n\n![](images/f30a964bd40573e4a2b1a770001783316967b9047139412db30defbc377a9c5d.jpg)  \n图5-3-34旋杯式静电喷涂设备示意图1一支柱：2—电动机；3一高压整流装置；4一转杯；;一涂料量调节装置；6—涂料贮槽；7—运输带；8一被涂物  \n\n$\\textcircled{3}$ 旋杯式静电喷涂设备旋杯式静电喷涂是目前国内外应用广泛的静电喷涂设备之一。由高压电源、静电喷枪、供漆系统和运输系统组成，如图5-3-34所示。高压施加于喷杯，涂料经过喷杯时被雾化带电，沿着电力线方向吸附并沉积在被涂工件上形成涂膜。  \n\n$\\textcircled{4}$ 旋盘式静电喷涂设备旋盘式静电喷涂设备又称为Ω形静电喷涂设备，是目前被广泛采用的一种静电涂装设备，适用于机电行业、汽车行业、自行车、仪器仪表、家用电器以及各种零部件的表面装饰等。该设备由 $\\Omega$ 形喷漆室、旋盘式静电喷枪、高压电源、供漆装置和电控装置组成，如图5-3-35所示。  \n\n(2）高压电源静电涂装的高压一般通过静电发生器提供，要求静电发生器安全、稳定可靠，使用寿命长，输出电压高而电流低，并带安全保护装置。高压静电发生器有晶体管和电子管两种。均有足够的输出功率，并装有击穿保护装置，当产生放电时能自动切断高压，保证人身安全。  \n\n![](images/ed1ce20382db4c838940627e49694f21fd9791d4accaedfe947ebb292363e576.jpg)  \n图5-3-35旋盘式静电涂装设备示意图1—Q形喷漆室；2—供漆系统；3一高压电源；4一电控系统：5一旋盘式静电喷枪；6一悬挂运输系统；7一被涂工件  \n\n随着科技的发展，目前已经能将高压发生器集成固化并安装于枪体本身之中。这种设计有两个优点：不用高压加载，提高了操作的安全性；普通导线比高压电缆轻便，减轻了手提式喷枪的重量，增加了操作的灵活性，降低了工人的劳动强度，提高了涂装质量。美国GRACO公司更推出了一种新型的内置式静电喷枪（PROXS4AA系列)，无需外接电源，利用压缩空气带动枪内的涡轮机发生静电，安全性极高。这种喷枪在接地良好的情况下，即使喷枪带电极针与工件短路，因释放能量极少，仅产生电弧光而不产生电火花，不会有着火的危险，如图5-3-36所示。  \n\n![](images/8a5abce3bed65c7aa3323c60ea2cfdc4c6731c85d6749e7ed7c96972ed2d6ff4.jpg)  \n图5-3-36内置式静电喷枪 1一主空气管；2一墙；3—空气管；4一涂料管；5—静电喷枪  \n\n(3）供漆装置供漆装置是涂料的输送装置，要求连续、稳定。目前常用的有自流式供漆装置、压力罐式供漆装置、压力供漆站三种形式，用户可以根据具体的要求进行选择.  \n\n(4）喷漆室静电喷漆室一般由室体、通风装置、安全装置等组成。室体是静电喷漆室的关键，依据室体的形式可以分为开式、死端式、通过式和Ω形静电喷涂室等。根据工件大小、形状及生产批量来确定室体的形式，批量大的一般采用通过式和Ω形静电喷漆室。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1504,
+        "chunk": "# 五、气雾罐喷涂法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1505,
+        "chunk": "# 1.概述  \n\n气雾罐喷涂法（aerosolspraying）是在气雾罐（既是涂料容器又是增压器）中灌人涂料和液化气体，掀压按钮时，利用液化气体的压力进行自压喷涂的涂装方法。气雾罐喷涂示意图如图5-3-37所示。  \n\n常用的气体发射剂有三氯氟甲烷或二氯二氟甲烷等。这种喷涂方法适用于家庭用小物品和交通车辆车体的修补等，不适应于大面积的、连续生产的被涂物。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1506,
+        "chunk": "# 2.特点  \n\n$\\textcircled{1}$ ①操作灵活简便：施工场地要求通风、无尘即可，无需气源、电源等硬件设施。  \n\n$\\textcircled{2}$ 喷涂的压力较低，要求涂料的黏度较低  \n\n$\\textcircled{3}$ 适用范围广：广泛应用于各种金属、表面处理过的木材、玻璃、ABS塑料等多种底材的涂装。  \n\n$\\textcircled{4}$ 漆膜装饰性好，漆膜较平整。  \n\n$\\textcircled{5}$ 漆雾 $E$ 扬，污染空气，涂料利用率仅为$30\\%\\sim50\\%$ ，浪费较大。  \n\n$\\textcircled{6}$ 涂装效率一般，只用于小规模施工",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1507,
+        "chunk": "# 3.施工注意事项  \n\n$\\textcircled{1}$ 涂装前要彻底去除需喷漆部位的油污、水渍和灰尘。$\\textcircled{2}$ 用原子灰填平凹陷的部位并磨平。$\\textcircled{3}$ 喷漆前必须上下左右摇动罐子约 $2\\mathrm{min}$ ，使涂料充分混合均匀。$\\textcircled{4}$ 在距被喷物表面 $20\\sim30\\mathrm{cm}$ 处，用食指压下喷头来回匀速喷涂。$\\textcircled{5}$ 未用完的气雾罐在存放时，应先将漆罐倒置压下喷头 $2\\sim35$ ，以清理干净喷嘴内的余漆，以防堵塞。  \n\n![](images/9493c8de54e709438c92a5521163954e8e431c31d86273915a6fabb639db78df.jpg)  \n图5-3-37气雾罐喷涂示意图1一搅拌球；2一气雾罐罐体；3一阀门；4一喷嘴按钮；5一阻塞孔；6一立管  \n\n$\\textcircled{6}$ 对不明材质表面最好先小面积试喷， $10\\mathrm{{min}}$ 后无不良反应再使用。$\\textcircled{7}$ 应在阴凉于燥、无灰尘、空气流通的环境下施工；不要在雨天或严寒环境下施工。$\\textcircled{8}$ 气雾罐为易燃品，要存放在低于 $40^{\\circ}C$ 的地方，远离明火，严禁曝晒、刺破或烧气雾罐。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1508,
+        "chunk": "# 六、喷涂方法性能比较  \n\n不同的喷涂方法各有其优缺点，实际工作中要根据涂装场地的实际情况、涂装质量的要求、工件的形状和涂装是否为连续生产等因素综合考虑决定。各种喷涂方法性能比较见表5-3-2。  \n\n表5-3-2 各种喷涂方法的性能比较  \n\n\n<html><body><table><tr><td>项 目</td><td>空气喷涂</td><td>高压无气喷涂</td><td>高压辅气喷涂</td><td>静电喷涂</td><td>气雾罐喷涂</td></tr><tr><td>喷涂质量</td><td>O</td><td>△</td><td>△</td><td></td><td>O</td></tr><tr><td>污染程度</td><td>X</td><td>△</td><td>a</td><td></td><td>X</td></tr><tr><td>工作效率</td><td>△</td><td></td><td>△</td><td></td><td>X</td></tr><tr><td>准备时间</td><td>O</td><td>△</td><td>△</td><td>△</td><td></td></tr><tr><td>工件形状影响</td><td>X</td><td>△</td><td>X</td><td>X</td><td>X</td></tr><tr><td>安全性</td><td></td><td></td><td></td><td>X</td><td></td></tr><tr><td>一次膜厚/μm</td><td>30</td><td>40以上 40~80</td><td>40</td><td>30</td><td>20</td></tr><tr><td>涂料利用率/%</td><td>30~60</td><td>无</td><td>50~80</td><td>70~90</td><td>30~60</td></tr><tr><td>对涂料电阻要求 压缩空气消耗量</td><td>无 大</td><td>小</td><td>无 小</td><td>有 大</td><td>无 无</td></tr></table></body></html>\n\n注： $\\bigoplus$ 代表优秀； $0$ 代表良好； $\\Delta$ 代表一般； $x$ 代表较差。  \n\n浸涂（dippingcoating）是传统的涂装方法之一，这种方法设备简单，操作灵活，适用于形状简单、无凹坑、不兜漆的流线型工件，而带有深槽、盲孔等能积蓄涂料，且余漆不易去除的被涂物不适宜采用浸涂方法。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1509,
+        "chunk": "# 一、原理  \n\n浸涂法的原理很简单，如图5-3-38所示，将被涂物全部浸没在涂料中，经短时间浸泡后，再将工件从涂料中取出，被涂物表面就会黏附涂料形成涂膜，再将多余的漆液滴尽并流回漆槽。  \n\n![](images/bc5f69640607095148924c1a1ea10f90271010cdbccf92101046922fc3655752.jpg)  \n图5-3-38 浸涂原理图1—浸涂槽；2—被涂物；3一起吊设备",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1510,
+        "chunk": "# 二、特点  \n\n$\\textcircled{1}$ ①设备简单，操作简便，小批量可用手工浸涂法，大批量可用机械浸涂，进行流水线生产，比较容易实现涂装自动化，生产效率高。  \n\n$\\textcircled{2}$ ②涂料损失少，利用率高，对环境的污染小。  \n\n$\\textcircled{3}$ ③涂层的装饰性一般，比不上喷涂、刷涂，涂装表面容易上薄下厚，易产生流挂。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1511,
+        "chunk": "# 三、浸涂设备  \n\n浸涂的方法很多，过去用手工浸涂法，现在大多采用批量浸涂法，批量涂漆有传动浸涂法、回转浸涂法、离心浸涂  \n\n法、真空浸涂法和浸涂-流涂法等。传动浸涂操作简单，生产效率高，应用比较广泛，在此主要对传动浸涂的方法和设备进行介绍。传动浸涂设备通常包括浸涂槽、去余漆装置、搅拌装置、加热冷却装置、通风、防火装置，此外还需要配置输送悬挂装置和贮漆槽。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1512,
+        "chunk": "# 1.浸涂槽  \n\n浸涂槽是浸涂所需要的最主要设备，根据浸涂的作业方式可以分为：船形浸涂槽和矩形浸涂槽，分别适于通过式浸涂法和间隙式浸涂法。槽体的形状和尺寸根据被涂物的形状和尺寸决定。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1513,
+        "chunk": "# 2.去余漆装置  \n\n去余漆的方式有自然滴落去余漆和静电去余漆两种。通常采用的是自然滴落去余漆法，设备简单。静电去余漆装置去余漆的效率高，但设备复杂，有一定的危险性。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1514,
+        "chunk": "# 3.搅拌装置  \n\n为防止浸涂槽内的涂料沉淀结块，保证涂料的均一，浸涂施工必须配置搅拌装置。常用的搅拌装置有泵循环搅拌装置和机械搅拌装置。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1515,
+        "chunk": "# 4.加热、冷却装置  \n\n浸涂施工必须配置加热和冷却装置，必要时对涂料进行加热或降温，以保证涂料的黏度在规定的范围内，从而保证施工正常进行。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1516,
+        "chunk": "# 5.通风、防火装置  \n\n浸涂为开作业，施工过程中溶剂在不断挥发，为确保作业环境的安全，减少对操作工人的危害，浸涂设备必须配置通风和防火装置。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1517,
+        "chunk": "# 四、浸涂工艺",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1518,
+        "chunk": "# 1.浸涂对涂料的要求  \n\n浸涂涂料一次投入量大，同时要长期反复使用，所以要求涂料使用期长，沉降速度慢，涂装过程中能保持浸涂槽内的涂料组分均一，因此涂料的选择必须得当。烘烤型涂料和水性涂料适宜采用浸涂方法。快干型涂料、双组分固化涂料和颜填料密度大的涂料不适宜采用浸涂方法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1519,
+        "chunk": "# 2.主要工艺条件  \n\n浸涂最合适的涂装膜厚是30μm，膜厚的控制可以通过黏度进行调节。涂料黏度越大，膜厚越厚；反之，黏度越小，膜厚越薄。浸涂时应该根据具体的涂装要求确定合适的涂料黏度，并进行严格的控制。  \n\n涂料的黏度和温度密切相关，黏度随温度的升高而降低，因此浸涂槽内的温度必须严格控制，使其保持稳定。  \n\n被涂物出槽的速率要适宜。出槽速率过快将造成浸涂槽内涂料剧烈运动，从而产生气泡，影响浸涂的质量。反之，如果出槽速率慢，而溶剂挥发速率快，则在垂直平面的漆膜厚度不均，一般出槽速率控制在 $10\\mathrm{{cm}/\\mathrm{{min}}}$ 左右。  \n\n在施工过程中需进行适当的搅拌，保持浸涂槽内涂料的均匀，防止涂料沉淀。  \n\n施工过程中要加强通风，保持操作环境空气的流通，从而减少有机溶剂对操作工人的危害。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1520,
+        "chunk": "# 第七节 帘幕淋涂法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1521,
+        "chunk": "# 一、原理  \n\n淋涂是将涂料喷淋或流淌过工件的表面形成连续漆膜的涂装方法。对小批量物件采用手工操作，向被涂工件上浇漆，俗称浇漆法。发展为自动流水线生产后，则称幕涂法（curtaincoating）。它是浸涂方法的改进，增加了一些装置，适用于大批量流水线生产方式，是一种比较经济和高效的涂装方法。自动帘幕淋涂法的原理是将涂料贮存于高位槽中，当工件通过传送带自帘幕中穿过时，涂料从槽下喷嘴细缝中呈幕帘状不断淋在被涂工件上，形成均匀的涂膜，多余的涂料流回容器，通过泵送到高位槽循环使用，如图5-3-39所示。该方法适于钢铁板材、胶合板和塑料板等平板状或带状材料的涂装，易于大批量自动流水线生产。  \n\n![](images/832c5bc303825d16807cb99eba327528ce49962d3a7fd7021118af2a9956cfd5.jpg)  \n图5-3-39帘幕淋涂原理图1—涂料人口；2—涂料贮槽；3—喷嘴；4—涂料流：5—被涂物；6—滴漆槽：7-循环泵",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1522,
+        "chunk": "# 二、幕涂法的特点  \n\n$\\textcircled{1}$ 幕涂法涂料用量少，利用率高。漆液不是分散为雾状喷出，而是以液流的形式滴落，同时仅在循  \n\n环过程中有部分溶剂的挥发，余漆可以通过收集系统进行回收，减少了涂料的损失。  \n\n$\\textcircled{2}$ 由于幕涂法采用流水线生产，适用于自动化大批量生产，被涂工件通过快速输送机构输送，涂覆速率快，涂装效率高。  \n\n③可以通过控制帘幕的厚度、流量和被涂工件的输送速率等工艺参数控制涂装过程，连续生产过程中可以控制膜厚较厚而且均匀稳定。  \n\n$\\textcircled{4}$ 幕涂法的工艺参数容易控制，设备清洗方便，操作也比较方便。  \n\n③幕涂法的适用面较窄，仅适用于平面的涂装，不适于垂直面或立体工件的涂装。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1523,
+        "chunk": "# 三、幕涂设备组成  \n\n根据帘幕淋涂设备涂装宽度不同，有多种型号的设备可供选用，可以根据被涂物的情况选择具体的型号。帘幕淋涂机由涂料槽、涂料循环系统、帘幕头和输送机构组成，如图5-3-40所示。  \n\n![](images/d4c11ea0f8d37f1be96c8201eee1ff811abc4831150170ec47cf4d567aed917f.jpg)  \n图5-3-40 通过式幕帘淋涂设备  \n\n1一涂料槽；2-涂料泵；3-压送管路；4-过滤器；5-输送量调节阀；6一高位压力调节槽；7一涂料帘幕流出狭缝；8-回流管；9-被涂物输送机；10-涂料收集器：11-输送回流管",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1524,
+        "chunk": "# 1.涂料槽  \n\n涂料槽是盛涂料的容器。为了保证涂料黏度的稳定，涂料槽可以做成带夹层的容器，夹层内可以通热水或冷水，以保持涂料的温度恒定。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1525,
+        "chunk": "# 2.涂料循环系统  \n\n涂料循环系统由涂料泵、压缩管路、过滤器、输送量调节阀、收集器和回流管组成。涂料循环系统的作用是向帘幕头输送涂料和收集返回的涂料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1526,
+        "chunk": "# 3.帘幕头  \n\n帘幕头是涂料帘幕形成的关键设备，是涂料的流出部件，由高位压力涂料槽、帘幕流出狭缝、狭缝调节装置和防风板组成。涂料帘幕流出狭缝位于高位压力调节槽的底部，可以通  \n\n过调节装置调节狭缝的宽度，从而达到控制涂覆膜厚的目的。  \n\n输送机构的作用是输送被涂物，保证涂装连续进行，输送机构由输送带、变速电动机和速度调节装置组成，速度调节应该能够无级调速，以满足连续涂装的要求，调速范围一般为$50\\mathrm{\\sim}150\\mathrm{m/min}$ 司  \n\n为预防火灾事故，确保帘幕淋涂作业安全，淋涂应该在专门的淋涂室内进行，并配备可靠的通风装置和自动灭火装置。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1527,
+        "chunk": "# 四、幕涂工艺  \n\n狭缝宽度、涂料黏度、涂料压力和被涂物的输送速率是影响帘幕涂装质量的重要参数，要根据实际情况进行调节，才能获得理想的涂层。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1528,
+        "chunk": "# 1.狭缝宽度  \n\n在涂料黏度和压力一定的情况下，狭缝越宽，涂料的涂布量越多；狭缝越窄，涂料的涂布量越少，如果狭缝过窄，涂料流出量过少，会使涂料帘幕断开，不能形成连续的涂膜。一般涂料选用的狭缝宽度为 $0.5\\sim0.8\\mathrm{mm}$ 0",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1529,
+        "chunk": "# 2.涂料黏度  \n\n要根据涂料品种、被涂物材质和需要的膜厚调整涂料的黏度，帘幕涂装涂料的黏度范围一般为 $15\\mathrm{\\sim}120\\mathrm{s}$ (涂-4杯)。温度对黏度的影响很大，一般要求淋漆室的温度要保持 $20\\sim$ $30^{\\circ}C$ ，必要时可通热水或冷水进行加热或冷却。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1530,
+        "chunk": "# 3.涂料压力  \n\n增加涂料压力，涂料滴落的速率加快，涂布量增加，涂装膜厚也增加；反之，降低涂料压力，涂料滴落的速率减慢，涂布量也减少，涂装膜厚降低，通常选用的压力范围为 $0.01{\\sim}0.02\\mathrm{MPa}$ 0",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1531,
+        "chunk": "# 4.被涂物的输送速率  \n\n输送带的速率决定被涂物输送速率，输送速率越快，涂装效率越高，涂布量越小，涂装 膜厚降低；相反，输送速率越慢，涂装效率越低，涂布量越大，涂装膜厚增加。一般被涂物 输送速率为 $70{\\sim}100\\mathrm{m/min}$ 0  \n\n![](images/8a30a63506975032b8b09dd3835621ed5219f5d16445feadf2f28297af969ff2.jpg)  \n\n细长的待涂工件沿水平的方向一个个被抽走涂漆的涂装方法叫抽涂法。被涂物通过抽涂机进行涂装，适用于铅笔杆、伞把、钓鱼竿及金属导线等被涂物，容易实现连续化自动涂装。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1532,
+        "chunk": "# 一、原理  \n\n抽涂法（pullcoating）的操作原理是工件通过内装涂料的漆槽下部的三通形抽涂孔，工件出口处有一个橡胶垫圈制成的将具，其直径稍大于工件，通过此持具可将多余的涂料清除掉，从而得到厚薄均匀的涂膜，如图5-3-41所示。  \n\n![](images/aa84c6d26891dc65cc583e29c1bc0da0d88b8dec883e5ef31557c638271418a4.jpg)  \n图5-3-41抽涂法示意图1一被涂物；2一弹性具；3—贮漆槽；4一顶出机构；5一排漆口  \n\n抽涂装置可以分为多次授挤型和一次授挤型，授挤用的橡胶板或橡胶套筒是抽涂装置的关键，简单工件要抽涂2～3次，铅笔、漆包线等要反复抽涂10次以上。漆膜厚度与孔洞的直径和被涂物的传输速率有关，通常传输速率为$0.5\\mathrm{m/s}$ 0",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1533,
+        "chunk": "# 二、特点  \n\n$\\textcircled{1}$ ①抽涂能使涂漆、干燥形成流水线，从而实现连续化涂装，效率高，适用于大批量生产。  \n\n$\\textcircled{2}$ 抽涂要求涂料的黏度小，固体分要高。  \n③工件必须定型，需要为圆柱状，适用于线状和棒状的被涂物。  \n\n辊涂（rollingmachine coating）是首先利用转辊蘸取涂料，然后借助转辊在转动过程中与被涂物接触，将涂料涂覆在被涂物的表面，形成连续涂膜的涂装方法。辊涂适用于平面状和带状被涂物的涂装，广泛应用于金属板、胶合板、布或纸的涂装，特别适用于金属卷材涂装。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1534,
+        "chunk": "# 一、原理  \n\n辊涂法的原理是转辊在涂料槽中转动，黏附一定的涂料，在转辊表面形成一定厚度的湿膜，然后借助转辊在转动过程中与被涂物接触，将涂料涂覆在被涂物的表面，形成连续的涂膜，如图5-3-42所示。辊涂特别适用于烘烤型涂料，要求涂料具有良好的流平性，润湿性和附着力，最好能够在短时间内烘烤固化成膜。辊涂容易实现连续化生产作业，涂装速率快，生产效率高。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1535,
+        "chunk": "# 二、辊涂机的构造",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1536,
+        "chunk": "# 1.构造  \n\n![](images/2793ce5b25c2b77968f534830f71b2a8f0a1e79d56d509d1c2792c256c40786f.jpg)  \n图5-3-42 辊涂原理图1—涂料贮槽；2—被涂物  \n\n辊涂机由涂料盘、取料辊和涂覆辊组成，如图  \n\n5-3-43所示。涂料盘用于存放调制好的涂料；取料辊的作用是从涂料盘中蘸取涂料，并将涂料转移给涂覆辊；涂覆辊将涂料涂覆在被涂物的表面，从而获得连续的涂膜。每个转辊均设有调节装置，可以调节转辊之间的间隙和压力，以便获得所需要的膜厚。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1537,
+        "chunk": "# 2.驱动方式  \n\n转辊的驱动方式分为集体驱动和单辊驱动。集体驱动由一台电动机驱动，工艺参数不易改变，目前应用较少。单辊驱动是每个转辊均配置专用的电动机，转动方向和转速均可调整，工艺参数容易改变，目前应用广泛。  \n\n![](images/7c3adfde6e7c242245c07c5ff8a7435356b45741eca77c9dc40b450ebba63ab7.jpg)  \n图5-3-43 辊涂机的构造  \n\n1--取料辊；2—涂覆辊；3—调节辊；4一被涂钢板（可下降）；5—涂料盘",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1538,
+        "chunk": "# 三、辊涂机的种类  \n\n根据涂覆辊和被涂物的转动方向的异同，辊涂机可以分为同向辊涂机和逆向辊涂机，如图5-3-44所示。同向辊涂机涂覆辊的转动方向和被涂物的移动方向相同，适用于低黏度涂料，通常用于薄膜型涂料，涂装膜厚一般在 $10\\cdots$ $20\\mu\\mathrm{m}$ 。逆向辊涂机涂覆辊的转动方向和被涂物的移动方向相反，适用于高黏度涂料，黏度可达120s（涂-4杯）一般用于厚膜型涂料，涂装膜厚一般在 $50\\sim500\\mu\\mathrm{m}$ 司",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1539,
+        "chunk": "# 四、辊涂工艺  \n\n辊涂机转辊的材质、组合、转动方向、转辊之间的间隙和周速比、涂料供给方式是影响辊涂质量的重要因素，要根据具体的辊涂要求选择合适的参数。  \n\n![](images/ced96eff0427991c43b2d24f07263f2f3b918fe0c1c8d0dd3feb36589ff0a58d.jpg)  \n图5-3-44 辊涂机的种类  \n\n一供料辊；2—涂覆辊；3—支持辊；4—工件；5—刮板",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1540,
+        "chunk": "# 1.膜厚的控制  \n\n一般取料辊和涂覆辊之间的间隙越大，辊涂的膜厚越厚，还可以通过调整周速比控制辊涂的涂装膜厚。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1541,
+        "chunk": "# 2.供料方式的选择  \n\n辊涂机的供料方式有底部供料和顶部供料两种方式。底部供料是取料辊从下面蘸取涂料，黏度适用范围窄，使用受到一定的限制。顶部供料是取料辊从上部取料，涂料容易润湿和黏附，适用范围较宽，应用比较普遍。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1542,
+        "chunk": "# 3.涂覆辊的选择  \n\n涂覆辊一般为橡胶辊，当被涂物为挠曲性的材质，如纸、布、塑料薄膜等采用钢制涂覆  \n\n辊。在涂覆过程中要保持涂覆辊的清洁，防止灰尘和异物的黏附，避免损伤涂覆辊，从而影响涂膜外观。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1543,
+        "chunk": "# 4.周速比的调节  \n\n涂覆辊与支持辊转速的比值叫周速比。为了使涂覆辊上的涂料涂覆到被涂物表面，并获得满意的涂覆效果，必须选择适当的周速比。逆向辊涂时，周速比要稍大于1；同向辊涂时，周速比要稍小于1，可以获得比较好的涂覆效果。  \n\n![](images/04c6e5649c2fcb360206c1cf42415b660a4f989d4dc8319df5ed5c5af3995b29.jpg)  \n\n电泳涂装（electro-coating）是利用外加电场使悬浮于电泳液中的颜料和树脂等微粒定向迁移并沉积于工件表面的涂装方法。电泳涂装技术的出现是涂装技术上革命性的飞跃，具有无可比拟的高效、低污染等突出优点，目前在汽车、建材、五金、家电等行业得到了广泛的应用。电泳涂装法包括阳极电泳和阴极电泳，阴极电泳泳透力高，耐蚀性好，目前被广泛采用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1544,
+        "chunk": "# 一、原理  \n\n电泳涂装是把工件和对应的电极放人水溶性涂料中，接上电源后，依靠电场所产生的物理化学作用，使涂料的树脂、颜料、填料在以被涂物为电极的表面均匀地析出沉积，形成不溶于水的涂膜的涂装方法。电泳涂装是一个极其复杂的电化学反应过程，包括电泳（elec-trophoresis）、电解（electrolysis）、电沉积（electrodeposition）和电渗（electroosmosis）四个过程。其原理和电极反应见表5-3-3。  \n\n表5-3-3 电泳涂装的原理  \n\n\n<html><body><table><tr><td>分类</td><td>阳极电泳</td><td>阴极电泳</td></tr><tr><td>基本原理</td><td>H+ OH 中 中和剂：KOH有机胺类 H2</td><td>OH H H R—NH+ O</td></tr><tr><td>pH变化</td><td>pH降低析出</td><td rowspan=\"2\">中和剂：有机酸 pH升高析出</td></tr><tr><td rowspan=\"2\">阳极： 2HO—→4H++4e-+O↑ （水溶性） 电极反应 Me-→Me\"++ne- 阴极： 2HO+2e-→2OH-+H↑</td></tr><tr><td>阳极： R—COO+H+—→COOH-R (不溶性) (水溶性） R—COO-+Me+—→(R—COO)Me (析出） 阴极：</td><td>2HO+2e-—→2OH-+H↑ R—NH++OH-—→R—N+HO (不溶性，析出)</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 1545,
+        "chunk": "# 二、特点  \n\n电泳涂装采用了电沉积工艺，具有以下特点：  \n\n$\\textcircled{1}$ 采用水溶性涂料，以水为分散介质，节省了大量有机溶剂，大大降低了大气污染和对环境的危害，避免了产生火灾的危险；  \n\n$\\textcircled{2}$ 电泳涂装效率高，涂料损失少，涂料的利用率可达 $95\\%$ 以上；$\\textcircled{3}$ 涂膜厚度均一，边缘覆盖性好，能满足形状复杂工件涂装的要求；$\\textcircled{4}$ 涂膜的力学性能优异，同时具有良好的附着力和耐冲击性能；$\\textcircled{5}$ 设备复杂，自动化流水线的投资费用高，耗电量大，涂装的管理复杂，施工控制严格，并需要进行废水的处理；$\\textcircled{6}$ 电泳槽的容积大，更换颜色比较麻烦。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1546,
+        "chunk": "# 三、工艺过程  \n\n在涂装前要对工件进行表面预处理，目前常用的电泳涂装工艺流程如下：工件 $\\cdot+$ 预脱脂 $\\blacktriangleleft$ 脱脂 $\\twoheadrightarrow$ 水洗 $\\nrightarrow$ 热水洗 $\\rightarrow$ 表面调整 $\\cdots$ 磷化 $\\cdot^{-}$ 水洗 $-\\mathbf{\\delta}$ 去离子水洗 $\\twoheadrightarrow$ 热风烘干 $\\twoheadrightarrow$ 电泳沉积 $\\nrightarrow$ 超滤循环水洗 $\\nrightarrow$ 烘烤成膜 $\\blacktriangleright$ 冷却 $\\nrightarrow$ 涂装面漆。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1547,
+        "chunk": "# 四、主要工艺参数  \n\n为了保证涂装的质量，必须对电泳液进行严格的科学管理，要定期对电泳液固体分、颜基比、 $\\mathtt{p H}$ 、电导率和电泳涂层厚度等进行测定，在测定数据的基础上调整电泳涂装的各项参数。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1548,
+        "chunk": "# 1.电泳电压  \n\n电压对漆膜的影响很大，电压越高，漆膜越厚。提高电压，对于难涂装部位可提高涂装能力，缩短施工时间，但电泳电压超过涂层的击穿电压，涂层即会被击穿，造成涂膜病，因此要确定最佳的电泳电压。电泳涂装采用的是定电压法，电压的选择一般由涂料的种类和施工的要求确定。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1549,
+        "chunk": "# 2.电泳时间  \n\n漆膜厚度随着电泳时间的延长而增加，但当漆膜达到一定的厚度时，继续延长时间，也不能增加厚度，反而增加副反应；反之，电泳时间过短，涂膜过薄。电泳时间应该根据所用的电压确定，在保证涂层质量的前提下，时间越短越好。一般电压下电泳时间为 $1\\sim3\\mathrm{min}$ ·大型工件 $3\\mathrm{\\sim}4\\mathrm{min}$ ，如果被涂物形状复杂，可以适当提高电压、延长电泳时间。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1550,
+        "chunk": "# 3.电泳温度  \n\n随着电泳液温度的升高，电泳沉积的速率加快，成膜速率快。但温度过高会导致涂层粗糙、橘皮，还容易引起涂料变质，因此必须控制电泳温度，一般控制在 $15\\sim30^{\\circ}C$ 0",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1551,
+        "chunk": "# 4.涂料固体分  \n\n采用低固体分的电泳液，工件带出的电泳液损失少，电渗性好，水洗时用水量少，废水处理容易。固体分过低，涂层过薄，会使涂层外观劣化，易产生针孔，电泳液不易维护；固体分过高，涂层易产生粗糙、橘皮等病。一般阳极电泳液的固体分控制在 $10\\%\\sim15\\%$ 阴极电泳液的固体分控制在 $18\\%\\sim20\\%$ 。  \n\n另外，影响电泳涂装的参数还有涂料的 $\\tt p H$ 、涂料电阻、极间距离等参数，要根据具体涂装要求选择合适的工艺参数。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1552,
+        "chunk": "# 五、电泳涂装设备  \n\n电泳涂装设备是由电泳槽、搅拌装置、涂料过滤装置、温度调节装置、涂料补给装置、直流电源装置、水洗装置、超滤装置、烘烤装置和备用罐等组成。电泳涂装设备可以分为连续通过式和间歇垂直升降式两大类。连续式适用于大批量涂装生产，在工业上应用较广；间歇式适用于小批量涂装作业。连续通过式电泳涂装设备如图5-3-45所示。  \n\n![](images/8f6dc39823fb81c4e5906afea03eb44e400f14ee88a2f17ca8fb66d9fbea9b43.jpg)  \n图5-3-45 电泳涂装设备示意图  \n\n1一主槽；2—直流电源；3—水洗喷嘴；4—输送链；5—工件；6—温度调整器；7—过滤器；   \n8—循环泵；9—涂料补给装置；10—前处理装置；11—检知装置；12—干燥炉；13—送风口",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1553,
+        "chunk": "# 1.电泳槽  \n\n电泳槽分为船形槽和矩形槽两种形式，前者适用于连续通过式电泳涂装生产线，后者适用于间歇垂直升降式涂装生产线。槽体的大小和形状要根据工件的大小、形状和施工工艺确定，在保证一定的极间距离条件下，应尽量设计的小些。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1554,
+        "chunk": "# 2.搅拌系统  \n\n循环搅拌系统可以使施工过程中的漆液保持均匀一致，一般采用循环泵，当循环泵开动时，槽内漆液均匀翻动，漆液一般每小时循环 $4\\sim6$ 次。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1555,
+        "chunk": "# 3.电极装置  \n\n电极装置由极板、隔膜罩及辅助电极组成。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1556,
+        "chunk": "# 4.温度调节系统  \n\n温度调节系统是为了使漆液保持一定的温度，一般电泳涂装的温度在 $20\\sim30^{\\circ}C$ 0",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1557,
+        "chunk": "# 5.超滤设备  \n\n电泳超滤（ultrafiltration）系统的主要作用有：  \n\n$\\textcircled{1}$ 维持槽液体系稳定，提高漆膜质量；  \n$\\textcircled{2}$ ， 回收电泳涂料，提高涂料的利用率，降低电泳后清洗纯水的用量；  \n$\\textcircled{3}$ 减少涂装废水的产生，从而减少去离子水的用量。  \n(1）超滤原理超滤原理是一种膜分离过程，超滤是利用一种压力活性膜在外界推动力  \n\n（压力）作用下截留水中胶体、颗粒和分子量相对较高的物质，而让水和小的溶质颗粒透过膜的分离过程。也就是说，当水通过超滤膜后，可将水中含有的大部分高分子量物质除去，同时还可去除大量的有机物等。  \n\n(2）超滤装置的结构超滤装置由预滤器、超滤器、循环泵和超滤液贮存输送装置组成，其中超滤器是整个超滤系统的关键。  \n\n透过率和截留率是超滤器的重要参数。透过率是指单位面积超滤膜在一定时间内所能通过液体的量，单位为 $^{*6}\\mathrm{L}/(\\mathrm{m^{2}\\cdot h})^{*}$ 。透过率主要受漆液压力的影响，压力愈高，透过率愈高，在相同的条件下，透过率愈高，表明超滤性能愈好。截留率是指超滤膜阻止漆液中高分子成膜物质通过的能力，截留率愈高、超滤透过液水质愈好。  \n\n另外，电泳涂装设备还包括涂料补给装置、通风系统、供电装置、水洗装置等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1558,
+        "chunk": "# 第十一节 自沉积涂漆法  \n\n自沉积涂装（chemical-phoretic coating）利用化学能将成膜物覆盖在铁制品表面形成涂层。钢铁表面只需除锈后即可涂装，不必进行磷化处理。20世纪80年代，美国、加拿大、法国、日本等国已用于汽车零部件涂装，20世纪80年代中期，我国已将自泳涂料用于汽车车身及货箱涂装，与国际先进水平差距不大。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1559,
+        "chunk": "# 一、原理  \n\n自沉积涂装的成膜机理是通过工件的电化学反应，使乳液破乳而沉积在工件的表面，形成湿膜，再经高温烘烤固化成膜。化学反应机理如下。溶解反应：Fe(工件） $\\mathrm{\\Omega}^{\\prime}+2\\mathrm{HF}\\longrightarrow\\mathrm{Fe}^{2+}+\\mathrm{H}_{2}\\uparrow+2\\mathrm{F}^{-}$ Fe(工件 $)+2\\mathrm{FeF_{3}}\\longrightarrow3\\mathrm{Fe}^{2+}+6\\mathrm{F}^{-}$ 成膜后的氧化反应： $2\\mathrm{Fe}^{2+}+\\mathrm{H}_{2}\\mathrm{O}_{2}+2\\mathrm{HF}\\longrightarrow2\\mathrm{Fe}^{3+}+2\\mathrm{H}_{2}\\mathrm{O}+\\frac{1}{2}\\mathrm{O}_{2}\\uparrow+2\\mathrm{F}^{-}$ 随着 $\\mathrm{Fe^{3+}}$ 浓度不断升高，逐渐破乳、自沉积形成湿膜，经过烘烤固化成自泳涂层。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1560,
+        "chunk": "# 二、特点  \n\n(1）低污染、高安全性由于自泳涂料以水为分散介质，不含任何有机溶剂，无有机溶剂的排放。  \n\n(2）低成本、高性能自泳涂装工艺简单，设备投资少；自泳涂层具有良好的耐蚀性，优良的力学性能。  \n\n(3）低能耗、高泳透力自泳涂装不需施加电场，靠乳胶溶液经一系列化学作用沉积于金属表面，烘烤温度低，同等规模的生产线可节能 $30\\%$ 以上；自泳涂装对于形状复杂的工件，均能获得厚度均匀的涂层，不存在电泳涂装中泳透力的限制。  \n\n（4）配套性能优异 用作底漆与常规的面漆有很好的配套性。  \n\n(5）颜色单一、限用于底漆限于其沉积机理，自泳涂装只能用于钢铁零件，颜色仅局限于黑色，色调较单一，故一般用于底漆涂装。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1561,
+        "chunk": "# 三、自泳涂装工艺  \n\n自泳涂装主要工艺流程如下：  \n\n![](images/75f50c51e9f8cb36e6d09c2bd5f6dd96da42a2821b6fb81b8a7d563074ce073e.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1562,
+        "chunk": "# 四、影响因素  \n\n影响自泳涂装的工艺参数有固体分、 $\\mathfrak{p H}$ 、 $\\mathrm{Fe^{3+}}$ 含量、氧化还原电位、沉积温度、时间和烘烤温度等，要根据实际情况进行调节，以获得预期的涂装效果。  \n\n![](images/ff3d0d50679fe35755c7b62a567aee7fdb7cbd818d5916a08741c02fcc44d783.jpg)  \n\n粉末涂装是指粉末涂料涂布到经过表面处理的清洁的被涂物上、经过烘烤熔融并形成光滑涂膜的工艺过程。粉末涂料是一种低污染、省能源的环保型涂料，但涂装过程中存在粉末爆炸的危险。  \n\n粉末涂装的成膜机理不同于液体涂料，是一种干燥的涂装工艺，必须采用特殊的涂装方法，常用的粉末涂装方法有静电喷涂法、流化床涂装法（普通流化床和静电流化床）和火焰涂装法，另外还有粉末电泳涂装法、等离子喷涂法、无空气热喷涂法等，在此重点介绍前三种涂装方法。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1563,
+        "chunk": "# 一、静电涂装法  \n\n粉末静电喷涂法（electrostatic powder coating）是粉末涂料施工中应用最多的涂装方法。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1564,
+        "chunk": "# 1.原理  \n\n静电喷涂是利用静电粉末喷枪喷出的粉末涂料在分散的同时被产生电晕放电，从而带上负电荷，在静电力和压缩空气的作用下，粉末被均匀地吸附在工件上，经加热粉末熔融固化成均匀、连续、平整、光滑的涂膜，原理如图5-3-46所示。带负电的涂料粉末在空气流的作用下，受静电场静电引力的作用定向地飞向接地带正电的工件上，由于电荷之间的作用而使涂料牢牢地吸附在工件上。一般只需几分钟便可使涂层达到50～150um，之后由于静电排斥，粉末就不再吸附到工件上，因此容易得到均匀的膜厚。喷涂后的工件在固化炉中加热，使涂层流平，形成均匀的涂层。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1565,
+        "chunk": "# 2.工艺流程  \n\n粉末静电喷涂工艺流程包括工件预处理、静电喷涂、烘烤固化等主要过程，另外包括空气净化、粉末回收等辅助过程。  \n\n![](images/d5057ced56cc0ad88b59e4edf3785cecb5897aa6646a21042c99bcd80c45ad2a.jpg)  \n\n图5-3-46粉末静电喷涂的原理 1—接地装置；2—工件；3一粉末静电喷枪； 4一输粉管；5—供粉器；6—压缩空气；7—振动器； 8—高频高压静电发生器；9一高压电缆  \n\n![](images/d81261ab9556c3848d707dcb4608cf54ddfbedae7201b50a44102482a1db1dee.jpg)  \n图5-3-47 手提式静电喷粉枪  \n\n1—喷杯；2—喷头；3—套筒；4—送粉管；5—扳机；   \n6一枪身；7—枪柄；8—高压电缆；9—低压导电线",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1566,
+        "chunk": "# 3.静电喷涂设备  \n\n静电喷涂的主要设备包括静电喷粉枪、高压静电发生器、供粉器、喷粉柜、粉末回收装置和烘烤炉等。  \n\n（1）静电喷粉枪静电喷粉枪是静电喷涂的关键设备，应具有理想的带电和扩散结构，以产生良好的电晕放电，使喷出粉末带上负电荷，喷出的粉末均匀。静电喷枪有手提式和固定式两种。固定式喷枪可以与自动升降的机械和机械手配套使用，一般用于生产线；手提式喷枪使用方便，灵活性大，结构如图5-3-47所示。  \n\n(2）高压静电发生器高压静电发生器的作用是提供喷涂用的高压，要求安全、稳定可靠，使用寿命长，输出电压高而电流低，并带安全保护装置。一般采用 ${\\bf30}\\sim\\delta0{\\bf\\ k V}$ ，电流值低于 $200\\mathrm{mA}$  \n\n(3）供粉器供粉器是静电喷枪取得高效率、高质量的关键，要求粉末涂料的供给连续、均匀。按结构供粉器有三类：压力式、抽吸式和机械式供粉器等，目前抽吸式应用最多。  \n\n(4）喷粉柜喷粉柜要求经济、耐久、实用，喷粉柜的大小取决于被涂物的大小、传送速率和喷枪的数量。  \n\n(5）粉末回收设备粉末静电涂装必须配备回收设备，直接关系到粉末涂料利用率和环境保护。回收设备的种类有旋风、布袋、旋风和布袋的组合等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1567,
+        "chunk": "# 4.影响粉末静电喷涂的因素  \n\n在粉末静电喷涂工艺中，影响涂膜性能的因素有粉末粒径、电导率、供粉压力和数量、喷涂压力、喷涂距离等，要根据具体的施工要求进行选择和调整。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1568,
+        "chunk": "# 二、流化床涂装法  \n\n流化床涂装法（fluidized-bedcoating）是一种简单的浸涂工艺，既适用于热塑性粉末涂料，也适用于热固性粉末涂料，主要用于绝缘和防腐蚀涂层，在家用电器和生活用品的表面保护和装饰中应用广泛。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1569,
+        "chunk": "# 1.原理  \n\n流化床涂装法原理与浸涂法类似，净化的压缩空气通人气室，经均压后通过微孔透气隔板进入流化槽中，槽中的粉末涂料在压缩空气的揽动下悬浮，形成平稳悬浮、沸腾状态的粉末-空气混合物，接触到预热后的工件立即黏附、熔融在工件表面，将工件取出加热烘烤形成一层连续均匀的涂层。硫化槽中粉末空气混合物像沸腾的液体一样，其悬浮的流动行为和流体相似，因此叫流化床涂装法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1570,
+        "chunk": "# 2.工艺流程  \n\n工艺流程如下：  \n\n![](images/3fa8e4d039090dbe4602a519670d04017c2595090aac7d411579e4be52ecdf10.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1571,
+        "chunk": "# 3.流化床的结构  \n\n流化床涂装法的关键设备是流化床。流化床由气室、微孔透气隔板和流化槽组成。结构 如图5-3-48所示。  \n\n(1）气室气室的作用是将压缩空气进行分散，通过均压板降压后成为均匀上升的  \n\n气流。  \n\n(2）微孔透气隔板微孔透气隔板是流化床的关键设备，主要作用是保证粉末涂料在流化床中达到均匀、良好的悬浮状态。要求孔径均匀一致、透气率高、机械强度好。  \n\n(3）流化槽流化槽是涂覆施工的场所，粉末涂料在流化槽中形成流动沸腾状态。流化槽可以根据工件的形状和大小，可以是圆形的，也可以是方形的。  \n\n![](images/675659864b0b23aa2878f2beff772d1c426863b4a2023c03db1bce5b7e98b9fa.jpg)  \n图5-3-48流化床工艺示意图1—压缩空气人口；2一气室；3一透气隔板；4一流动化粉末涂料；5—流化槽；6—预热工件；7一工件不断融附涂料  \n\n![](images/3b21aef7bbf17b8e0c22510dfa2472959a975b90fbd664bffd88f7663589d72a.jpg)  \n图5-3-49静电流化床涂装原理 1一被涂物；2—接地；3—高电压极；4一空气； 5一透气隔板；6—粉体浮动层；7—粉体流动层",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1572,
+        "chunk": "# 4.影响因素  \n\n影响粉末涂装的主要因素有粉末涂料的特性、气压和供气量、预热温度、工件浸入方向等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1573,
+        "chunk": "# 三、静电流化床涂装法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1574,
+        "chunk": "# 1.原理  \n\n静电流化床涂装法（electrostatic fluidized-bed coating）是在普通流化床床身的粉末中放置一个负高压电极，该电极产生电晕放电，可使得粉末微粒带电，这些带电的粉末就会被设有接地电压的待涂工件所吸附而形成涂膜，原理如图5-3-49所示。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1575,
+        "chunk": "# 2.工艺流程  \n\n工艺流程如下：  \n\n![](images/852721c9ef553fc64375ca209f287ed4b90692f6bb28c70c9f62dc75afcde0d1.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1576,
+        "chunk": "# 3.静电流化床设备  \n\n静电流化床设备由涂覆室、高压静电发生器、电动和气动控制柜、回收系统和固化炉组成。静电流化床的设备与普通流化床类似，只是在普通流化床的基础上增加了一个电晕电极和高压静电发生器。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1577,
+        "chunk": "# 4.影响要素  \n\n影响粉末涂装的主要因素有粉末状态、高压电极的位置、电场强度、粉末状态、流化床气压、回收气流等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1578,
+        "chunk": "# 四、火焰喷涂法  \n\n粉末涂料火焰喷涂法（flamecoating）亦称热熔射喷涂法或熔融喷涂法。主要用于金属表面涂装聚乙烯、尼龙、氯化聚醚、含氟树脂等热塑性粉末涂料，适宜于防腐蚀涂层、耐磨涂层和一般装饰性涂层。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1579,
+        "chunk": "# 1.原理  \n\n用压缩空气将粉末涂料从火焰喷枪中心吹出，高速通过喷嘴外围喷出的火焰区域，使涂料成为熔融状态喷射黏附到已经预热的工件上，涂膜颗粒相互融合形成光滑的涂膜。火焰燃烧的燃料一般采用乙炔和氧的混合气体，输送粉末和冷却保护气体采用脱水除油的压缩空气或氮气，原理如图5-3-50所示。  \n\n![](images/5a054cbadcf3877b752e7f45758b74e5615588b202f6c1f82e6c7be03a7ebbe0.jpg)  \n图5-3-50粉末涂料熔射法原理1一粉末；2—可燃气体（乙炔-氧）；3一冷却气体；4—喷嘴；5—火焰；6—涂膜；7—工件",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1580,
+        "chunk": "# 2.工艺流程  \n\n火焰喷涂法的流程如下：  \n\n![](images/60d8be6e91a0ad554ca6bfd5f45fa12ca91e02bfbcef625d7b890555be12ab39.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1581,
+        "chunk": "# 3.火焰喷涂设备  \n\n火焰喷涂法主要设备由燃气瓶、氧气瓶、流量控制装置和喷枪组成，其中最主要的设备是喷枪，如图5-3-51所示。粉末从枪嘴中心的铜管喷出，氧气和乙炔混合气从枪嘴外围的气体喷出管喷出形成火焰，粉末通过火焰熔融而附着到工件上，进而固化成膜。  \n\n![](images/a94a3b8063ec97ccdd5d11aa0e66f95f0477db29f1ccc9723f8b687612a95425.jpg)  \n图5-3-51火焰喷涂设备1—乙炔气体；2一氧气；3一气体流量计；4一压缩空气；5—空气控制器；6—粉末管；7一喷枪",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1582,
+        "chunk": "# 4.主要工艺参数  \n\n火焰喷涂法工件一般要预热，工件预热温度一般为 $180\\sim200^{\\circ}C$ 。可燃气体管上必须装有回火防止器，喷粉时不能关闭冷却气体。冷却空气的量、火焰温度、粉末通过火焰的时间和距离等均会影响涂装效果。  \n\n一般火焰喷涂法施工中的主要技术参数如下：  \n\n$\\textcircled{1}$ 粉末喷出量 $30\\sim60\\mathrm{g/min}$ $\\textcircled{2}$ 氧气压力 $0.2{\\sim}0.5{\\bf{M P a}}$ 。 $\\textcircled{3}$ 乙炔气体压力 $0.05\\mathrm{MPa}$ $\\textcircled{4}$ 压缩空气压力 $0.1{\\sim}0.5\\ensuremath{\\mathrm{MPa}}$ $\\textcircled{5}$ 喷射面积 $10{\\sim}15\\mathrm{m}^{2}/\\mathrm{h}$ $\\textcircled{6}$ 涂覆效率 $70\\%$ 0  \n\n![](images/50874fdc0d109e5e720a2b6f0c36782a5158ed1bb2e538fba4c8b037d09371c6.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1583,
+        "chunk": "# 一、概述  \n\n随着我国经济的发展，通过技术引进和与国外的技术交流，我国的涂装技术有了突飞猛进的进步，自动化涂装与手工涂装相比具有明显的优势，它涂装效率高，可以满足多品种、小批量、多尺寸、多色彩涂装产品的要求，已经逐步取代手工涂装而成为涂装的重要方式，广泛应用于各种涂装领域。  \n\n自动涂装系统适于大批量生产，实现了流水化连续作业，提高了生产效率，提高了质量的稳定性，改善了涂膜外观，并且大大降低涂装人员的劳动强度。自动化涂装系统还减少了涂料的浪费，提高涂料的利用率，同时自动涂装系统产生的漆雾少，减少能量消耗，实现了室内涂装，有利于改善工作环境，保护操作人员的安全和健康，有利于环境质量的改善。  \n\n随着时代的发展，自动化涂装设备实现了立体自动跟踪和换色，可以生产出各种式样和色彩的产品。  \n\n自动化涂装系统由被涂物形状识别系统、控制系统、喷涂系统等组成。涂装过程中要控制喷具的运动轨迹，同时还必须控制涂料的雾化质量、雾幅大小、黏度和流量等技术参数。所有的参数控制可以通过计算机控制系统完成，根据控制系统的复杂程度可以分为往复涂装机和涂装机器人。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1584,
+        "chunk": "# 二、往复涂装机  \n\n往复式涂装机的控制系统相对简单，可以携带自动喷枪，在输送装置的配合下，完成对工件表面的涂装。往复式涂装系统的组成如图5-3-52所示。  \n\n根据喷涂的运动轨迹，往复涂装机可以分为水平、垂直和门式等形式。  \n\n![](images/e20e7a13907af1e4b7d5ae4e0d3085f3f7f395c61f63a6b91d658802920e8ef8.jpg)  \n图5-3-52往复式涂装系统的组成1—主控系统；2一辅助控制系统；3—传送带控制系统；4—脉冲发生器；5一被涂物；6一喷枪；7—传送带；8—喷涂室",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1585,
+        "chunk": "# 1.水平往复式涂装机  \n\n水平式往复涂装机最为常用，通过喷枪前后运动和被涂物的水平运动，实现对被涂物的快速涂装，特别适于平面被涂物的涂装，如钢板、木板等。水平式往复涂装机如图5-3-53所示。  \n\n![](images/918eb976a5bae33e0c14cd0b1cdbbfdfbe627aab64d12a3bc7a9a9fa134970d4.jpg)  \n图5-3-53水平往复涂装机示意图1—上喷枪；2—下喷枪；3—工件识别装置；4—被涂物",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1586,
+        "chunk": "# 2.侧喷机  \n\n侧喷机喷头一般有三个自由度，即上下往复、前后运动和垂直平面的运动。这三种参数的调节可以保证喷涂在行程内任意点与工件保持同等距离和喷涂轴线垂直工件表面，得到良好的喷涂距离和角度，保证最佳的喷涂方向和质量。侧喷机如图5-3-54所示。  \n\n![](images/9485f03bdf59f056da46d1f927c3945879559c0faf90e53bf1becd3a90a82229.jpg)  \n图5-3-54侧喷机1—机座；2—喷枪；3—工件识别装置；4一往复升降装置  \n\n![](images/60194a405db5d699115b045147a4eef76c019dba366d7ee15b08c8bc075ce8c1.jpg)  \n图5-3-55门式喷涂机示意图1—侧喷枪（上下移动）；2一顶喷枪（左右移动）；3一门式喷涂机移动方向（前后运动）",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1587,
+        "chunk": "# 3.门式喷涂机  \n\n门式喷涂机结合了水平喷涂机和侧喷机特点，通过门式喷枪的上下往复和左右运动以及喷涂机的水平运动，可以实现被涂物的三维涂装，常见的门式喷涂机示意图如图5-3-55所示。  \n\n近期，出现了新型的固定门式喷涂机，即喷涂机是固定的，多把喷枪分布在固定门式结构上，通过被涂物的水平运动，实现被涂物的三维涂装，这种技术革新，减少了喷枪的运动，从而减少了振动，提高的涂装的速率和质量，代表着门式喷涂机的未来发展的方向，如图5-3-56所示。  \n\n![](images/87f0eb0cedfefe5f310f3c8e3ec30812c4793e208f314f423097002aa4cc0c23.jpg)  \n图5-3-56固定门式喷涂机1一固定多个喷枪（顶部和两侧）2-被涂物运动轨道；3一被涂物  \n\n![](images/a3886a23f2ddef5c83a8847d1c91887115fd3bc623658ed2792e58a1944a28fa.jpg)  \n图5-3-57涂装机器人的组成  \n\n1一油压系统；2一机器人控制系统；3一传送带控制系统；4一脉冲发生器；5—被涂物；6—喷涂装置；7—传送带；8—涂装室；9一操作控制台",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1588,
+        "chunk": "# 三、涂装机器人  \n\n涂装机器人结构较普通的往复涂装机复杂，能进行复杂轨迹的喷涂，可以对工件内、外表面根据预设的程序进行逐一涂装。涂装机器人能很好地替代工人进行喷涂，特别是在汽车内腔喷涂中得到较大范围地使用。涂装机器人的组成如图5-3-57所示。常见的涂装机器人示意如图5-3-58所示。  \n\n![](images/1b4eb218c8e60396b83bc241d6c8e5e30372977ab5ac9ad7fe4ea42c6978baa4.jpg)  \n图5-3-58 涂装机器人  \n\n1一涂装机器人；2-车身；3-喷枪；4-供漆系统涂装机器人具有如下的特点。  \n\n① 涂装机器人动作灵活，能喷涂空间的任意位置和方向。目前，先进的机器人可以模仿人的动作，一般具有五六个自由度以上，可以满足多品种、小批量、多色彩和各种形状被涂物的涂装要求。表5-3-4为某型号涂装机器人的参数。  \n\n表5-3-4某型号涂装机器人的参数  \n\n\n<html><body><table><tr><td rowspan=\"7\">动作自由度</td><td>序号</td><td>项目</td><td>5轴</td><td>6轴</td></tr><tr><td>1</td><td>腕的左右旋转 腕的上下移动</td><td>130°,3820mm</td><td>130°,3820mm</td></tr><tr><td>2 3</td><td>腕的前后</td><td>2250mm 100°,1300mm</td><td>2250mm 100°,1300mm</td></tr><tr><td>4</td><td>手的上下摆动</td><td>240° 240°</td><td></td></tr><tr><td>5</td><td>手的左右摆动</td><td></td><td></td></tr><tr><td>6</td><td>手的回转</td><td>240°</td><td></td></tr><tr><td>7 8</td><td>手的摆动 一 回转</td><td>90°ON-OFF</td><td>240°</td></tr><tr><td colspan=\"3\">可搬重量/kg</td><td>240°</td><td></td></tr><tr><td colspan=\"3\">最大速率/(m/s)</td><td>2</td><td></td></tr><tr><td colspan=\"3\"></td><td>5</td><td></td></tr><tr><td colspan=\"3\">操作精度/mm</td><td colspan=\"2\">±2</td></tr><tr><td colspan=\"3\">重量/kg</td><td colspan=\"2\"></td></tr><tr><td colspan=\"3\">防爆构造</td><td colspan=\"2\">450 2G4</td></tr></table></body></html>  \n\n$\\textcircled{2}$ 涂装机器人的作业环境一般均是易燃易爆的，需要配备可靠的防爆措施。常见的涂装机器人有油压式和电动式，防爆措施有一定差异，但防爆方式必须通过有关部门的认定。  \n\n$\\textcircled{3}$ 机器人涂装系统适用于全自动涂装生产线，劳动生产率高，同时节省涂料，涂料的利用率高。  \n\n$\\textcircled{4}$ 设备结构紧凑，节省占地面积，降低了运行费用。  \n\n$\\textcircled{5}$ 涂装机器人结构复杂，必须配备故障诊断系统，及时排除故障，保证涂装的顺利进行。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1589,
+        "chunk": "# 参考文献  \n\n[1］叶杨祥，潘肇基主编．涂装技术实用手册，北京：机械工业出版社，2005.  \n[2] 涂料工艺编委会编．涂料工艺：下，北京：化学工业出版社，1997.  \n[3］汪国平编著，船舶涂料与涂装技术，北京：化学工业出版社，2006.  \n[4] 李敏风编著：集装箱涂料与涂装技术，北京：化学工业出版社，2002.  \n[5] 张学敏编著．涂装工艺学．北京：化学工业出版社，2002.  \n[6] 王健，刘会成，刘新主编．防腐蚀涂料与涂装工．北京：化学工业出版社，2006.  \n[7]长谷川谦三著：料塗装技术．东京：日本理工出版会，2007.  \n[8] 鹤田清治，寺内淑晃，安原清著，装の，东京：技术书院，2000.  \n[9] 西村利明，柳田昭雄编．v涂料读本（涂装编），东京：关西涂料株式会社，1998.  \n[10］W．威克斯，N．琼斯，S．柏巴斯著．有机涂料科学和技术．经良等译．北京：化学工业出版社，2002.  \n[11］徐秉凯等主编．国内外涂料使用手册．南京：江苏科学技术出版社，2005.  \n[12] 曾敏生著．影响涂料利用率因素及改进措施．涂料工业，2005，（5）.  \n[13］冯立明，牛玉超，张殿平等主编．涂装工艺与设备，北京：化学工业出版社，2004.",
+        "category": " References"
+    },
+    {
+        "id": 1590,
+        "chunk": "# 涂装现场管理和技术服务  \n\n绝大多数涂料在出厂的时候都是以液体混合物的形式存在的，只有经过良好的施工过程，到达被涂物表面并经过良好的干燥过程形成涂膜后，才能获得应有的涂膜性能。由此可知，良好的涂装管理和涂料生产厂家专业的施工指导能够在涂料转化成涂膜这一过程中起到非常重要的作用。本章将以油性防腐涂料的施工为例，重点介绍涂料施工过程中的现场管理和涂料厂家技术服务人员的工作要点。  \n\n![](images/dce362f52877e701f2f35414c47042155e278f236bfbf1a8957394ccd99cfcc9.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 1591,
+        "chunk": "# 一、涂料的贮存  \n\n涂料一般都是由成膜物质、颜料、助剂和溶剂四部分组成的混合物，在贮存过程中各个组分会发生不同的物理、化学变化。特别是在温度、湿度等条件有较大改变的环境中，这些物理或化学变化的速率会加大，有时会导致涂料的提前失效。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1592,
+        "chunk": "# 1.涂料的贮存  \n\n涂料的贮存场所应为保持凉爽、干燥且通风良好的室内环境，贮存温度应符合产品说明书的规定，在贮存过程中应避免以下几种情况。  \n\n(1）温度过高温度上升会导致涂料中各个组分的反应活性提高，涂料中的成膜物质与颜料、成膜物质与助剂、颜料与助剂之间会因为温度的升高而发生化学反应，这些化学反应会造成涂料的黏度升高，产生胶化、絮凝等涂料病态，最终可能会使涂料提前失效。在没有化学反应的前提下，当温度升高时涂料本身的黏度会下降，黏度降低会造成整个体系的防沉降性能下降，颜料与成膜物质之间的稳定体系被破坏，导致涂料在包装桶内发生沉淀、结块等问题。因此要维持涂料的正常性能，规定最高的贮存温度是必需的。另外，由于大多数涂料产品是易燃、易爆品，过高的温度也会加大燃烧和爆炸的危险。所以，一般规定涂料贮存时的最高温度不应超过 $40^{\\circ}C$ 卷  \n\n(2）温度过低涂料的贮存温度过低时往往会使涂料体系的黏度上升，一些助剂在温度过低的情况下也有可能失效。对于以水为主要溶剂体系的涂料，当温度下降到冰点以下时，溶剂会冻结，影响涂料的稳定性，反复冻融以后可能会发生破乳等病态，所以一般要规定涂料可贮存的最低温度，为了保证涂料的正常使用，通常规定涂料贮存时的最低温度不应低于 $5^{\\circ}C$ 。  \n\n(3）露天摆放当涂料在露天摆放时，涂料的包装物直接暴露在室外，遭受雨、雪、日光等介质的侵袭，包装物有可能会提前失效，出现泄漏、破损、生锈等问题，影响涂料的品质甚至会使涂料提前失效。露天下的阳光曝晒还会使包装桶内产生高温，造成溶剂挥发和包装桶变形，成为火灾和爆炸的隐患，因此一般规定涂料禁止露天摆放，对于在施工现场需要临时露天摆放的涂料，在不同的季节要做好相应的保温和降温措施，如冬季要用保温材料苦盖，夏季要注意洒水降温。  \n\n(4）空气相对湿度过高涂料贮存环境的相对湿度过高时，会使金属制的包装物被腐蚀生锈，特别是当包装桶的密封部位边缘发生锈蚀时，由于锈蚀而发生的体积膨胀能使密封失效，从而发生泄漏。失去包装物屏蔽的涂料由于直接暴露在环境中会加速提前失效。过高的环境湿度还会使对水敏感的涂料由于包装密闭不严等原因而提前实效。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1593,
+        "chunk": "# 2.涂料的保质期  \n\n涂料的保质期通常是指涂料产品在正常的贮存条件下能够正常施工，并且在施工后能够保证涂膜正常性能的贮存期限。一般来说，大部分涂料产品在其说明书中规定的保质期是12个月，易沉淀和在贮存过程中存在缓慢化学反应的涂料保质期一般规定为6个月。使用厂家对大多数涂料都可以参照这一标准执行。但是有些涂料产品在生产之后的一段时间内其内部发生这样或者那样的物理化学变化而导致贮存时间缩短，而使用厂家对此没有提前了解的话就容易造成损失。如大多数的无机硅酸锌涂料的液体组分生产出来以后，其内部仍然在发生着缓慢的水解反应，在常温下的贮存期一般为6个月，但是在高温高湿的条件下这一反应可能会加速，造成不到六个月后就有可能影响到涂料的品质。  \n\n当然并不是涂料到了保质期就不能使用了，有些涂料产品在包装完好的情况下能够在更长的时间内正常使用。但是超过使用期后能否正常使用需要专业人士来进行判定，在涂料的使用过程中应尽量遵守涂料生产企业保质期的规定，避免在使用过程中出现不必要的麻烦。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1594,
+        "chunk": "# 二、涂料的现场管理  \n\n涂料从贮存的场所运抵施工现场后，需要对涂料产品进行评估，以确定产品的数量能否满足要求和贮存后的涂料质量是否有变化。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1595,
+        "chunk": "# 1.产品数量的确认  \n\n$\\textcircled{1}$ 预先评估计算被涂物的面积，从而确定将要涂装的面积。② 根据涂装面积和涂料产品说明书中给出的理论涂布率（单位涂料能够涂装的面积或  \n单位面积所需的涂料量）计算出理论涂料用量。$\\textcircled{3}$ 根据被涂物的形状、大小、涂膜厚度、环境情况、涂装方式、工人熟练程度等条件  \n推断出每个使用单位上涂料的损耗率。$\\textcircled{4}$ 根据涂料的理论用量和损耗率，计算出涂装所需的实际涂料量。  \n\n通常有如下的公式：  \n\n涂料实际量 $\\b=$ 理论涂料用量 $\\times(1+$ 损耗率）  \n\n$\\textcircled{5}$ 按照计算出的涂料实际需要量，结合现场情况计算出所需相关产品（如溶剂等）的数量。$\\textcircled{6}$ 按照涂料实际需要量，领出所需涂料及相关产品，并运抵现场。$\\textcircled{7}$ 现场清点涂料数量，要特别注意，多组分涂料的每个组分一定要按套相互对应，绝对不能出现有一个组分缺少或多出的情况。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1596,
+        "chunk": "# 2.现场产品质量的确认  \n\n$\\textcircled{1}$ 确认产品包装完好，没有因运输过程导致的洒、漏及包装桶严重变形等情况。  \n\n②产品标签完好，没有因污染而无法辨认的标签，也没有因粘贴不牢而缺少的标签。  \n\n$\\textcircled{3}$ ③确认产品包装名称与所需的产品相符，并且没有超过保质期。  \n\n④ 打开包装后，观察涂料的容器中状态，产品应无结块、成胶、起皮、严重沉淀等病态，且容易搅拌，搅拌后无颜色不均、返粗等病态。如是透明涂料产品，除了应避免上述问题以外，产品在搅拌前后应始终保持澄清、透明。  \n\n③将涂料各组分混合均匀后观察，有无返粗、增稠等现象，确认涂料能否正常施工。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1597,
+        "chunk": "# 第二节 涂装环境管理  \n\n涂料在施工过程中始终受到周围环境的影响，而且工人的操作也与周围环境密切相关，因此，除了涂料品质和设备因素外，涂装环境是影响涂装质量的最大客观因素之一。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1598,
+        "chunk": "# 一、照明的管理  \n\n涂料施工的现场既有各种不同的涂料桶、喷涂设备，又有各种输送管道，有时还有脚手架等，往往比较杂乱，因此必须要保证一定的照明条件。只有这样才能保证工人准确识别涂料产品，便于涂装作业，也有利于涂装后的检查工作，特别是对保证作业安全，减少工伤也是非常必要的。  \n\n我国在GB50034《2004建筑照明设计标准》中规定了工厂中各种环境所需要照明的标准，该标准要求表面处理车间、涂装施工车间等的照度要达到75～150lx。  \n\n此外，需要提出的是，用于涂料颜色检验的照明条件要依据GB/T3181—2008《漆膜颜色标准》中的规定，“采用具有与CIE标准照明体D65光谱能量分布相近似的、人工光源照明的比色箱，其比色位置的照度应在1000～4000lx”。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1599,
+        "chunk": "# 二、通风的管理",
+        "category": " Introduction"
+    },
+    {
+        "id": 1600,
+        "chunk": "# 1.室内施工时涂装环境的通风  \n\n正规的涂装工作一般都是在相对隔离的涂装车间内进行的，涂装车间由于周围环境相对独立。其内部空气流通一般都不畅通，因此要设置必要的通风设施。通风的作用有三个方面：保证操作者人身安全、避免发生火灾事故、确保涂料施工质量。  \n\n(1）保证操作者人身安全在涂料的施工过程中，周围环境空气中弥漫着大量的溶剂蒸气，在通风条件不良的情况下，这些蒸气会降低环境中氧的含量。溶剂蒸气会经过呼吸系统和皮肤接触进入人体，造成神经系统和内脏器官的损伤。因此要加强通风以保证施工环境中空气的相对新鲜和洁净，避免给操作者带来人身伤害。  \n\n(2）避免发生火灾事故在涂料施工过程中，整个施工环境中存在大量的可燃气体、可燃液体蒸气和可燃粉尘，这些物质与空气混合并达到一定浓度时，遇火源就会燃烧或爆炸。这个遇火源能够发生燃烧或爆炸的浓度范围，称为爆炸极限。加强通风的重要作用就是尽量稀释可燃气体、可燃液体蒸气或可燃粉尘在空气中的浓度，将其控制在爆炸极限以外，减小爆炸的可能。  \n\n(3）确保涂料施工质量在涂料的施工过程中，涂料中的溶剂会不断挥发到空气中，当空气中的溶剂蒸气浓度较高时，残存在涂料中的溶剂的挥发速率就会降低，在涂料表面形成溶剂膜，影响涂料的成膜过程。加强通风能够加速涂料中溶剂的挥发，促进涂料形成均匀稳定的涂膜。当空气的相对湿度较高时，涂料表面的温度会因溶剂的挥发而迅速降低，造成空气中的水分在涂料表面凝结，在涂料表面形成水膜与涂膜的界面，造成涂膜病，甚至影响涂料正常成膜。在通风不畅的环境里，漆雾悬浮在空气中缓慢降落，如果在降落的时候涂膜已经表干，落下的漆雾会在涂膜表面形成细小的粉尘颗粒，影响涂膜表面状态。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1601,
+        "chunk": "# 2.室外施工时风速的管理  \n\n当整个涂装工作在室外进行时，通风条件基本可以得到保证，但是这时需要注意的是风力过大对涂装质量的影响。  \n\n（1）风力过大对表面清洁度的影响当环境风力较大时，周围空气中的悬浮灰尘量会大大增加，特别是在一些污染严重的地方，悬浮颗粒的数量会更多，这就会使底材上或者是每道漆涂装后的涂膜表面附着大量的灰尘颗粒。在下道漆涂装时，这些黏附在底材上和涂层间的不明成分颗粒不但会影响涂膜的表面状态，而且还会对涂料的层间附着力以及涂膜的长期防腐性能产生较大的影响。  \n\n(2）风力过大对涂料损耗的影响使用喷涂等涂装方式进行施工时，涂装工具不直接与被涂物表面接触，喷出的涂料雾化粒子要经过一段空间距离后才能到达被涂物表面。当风力较大时，一部分涂料的雾化粒子会被风吹散至空气中，这样到达被涂物表面的涂料量就会减少。随着环境风力加大，涂料的损耗量会不断加大，通常要求在涂装施工时风速要小于四级$(5,5{\\sim}7,9\\mathrm{m}/s)$ 这样才能够尽可能地减少风对损耗的影响。  \n\n(3）风力过大对涂装质量的影响使用喷涂等方式进行涂装时，风力过大会导致雾化的涂料粒子在空气中飘散过程中其中的溶剂快速闪干（flashoff)。闪干后的涂料粒子落到被涂物表面会造成涂膜附着力下降；落到周围涂膜上会影响周围涂膜的表面状态，并会影响下道漆的附着力。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1602,
+        "chunk": "# 三、温度的管理  \n\n不同品种涂料的干燥方式往往不同，有的涂料干燥过程是物理方式，有的则是化学方式。这两种干燥的过程都需要能量的参与。除了少数涂料（如紫外固化涂料等）的固化过程与环境温度关系不大以外，大多数涂料的固化速率都与环境温度密切相关。涂料施工过程中，温度的管理主要是指环境温度、底材温度、涂料温度、露点温度等的控制。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1603,
+        "chunk": "# 1.环境温度  \n\n主要是指涂料施工时周围空气的温度，也是自干型涂料施工后干燥过程中周围空气的温度。要保证涂料在施工时的良好效果，其周围环境的温度就应当保持在较适宜的区间。室温环境 $(23^{\\circ}C\\pm2^{\\circ}C)$ ）对于大多数涂料来说都是比较适宜的施工温度，除了需要强制干燥的涂料，室温环境也是比较适宜的干燥环境。大多数涂料都有较宽的干燥温度范围，但不同涂料品种的干燥的温度区间也是不同的。涂料厂商的说明书中都会列出干燥的温度区间，使用者可以依此选择施工和干燥时的环境温度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1604,
+        "chunk": "# 2.底材温度  \n\n底材温度是指在进行涂装时底材的表面温度。这一温度在室内条件下与环境温度是基本一致的，但是在室外施工时由于底材的热容不同以及阳光照射的原因，底材温度往往与环境温度不一致。阳光直射的部位一般会比环境温度要高，通常早上钢材的表面温度会低于环境温度，傍晚表面温度会高于环境温度。底材的表面温度管理通常有三方面的应用，一个是用于与露点温度比较，来判断施工时表面结露的可能性；另一个是控制底材的表面温度，避免因底材温度过高造成涂料中的溶剂挥发速率过快导致漆病；第三个是用于与涂料温度进行比较，避免因两者温差过大产生漆病。另外，当底材温度低于冰点时，在夜间环境下底材表面往往会结冰或结霜，而且很难用肉眼发现，如果这时施工往往会带来意想不到的问题，要特别注意。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1605,
+        "chunk": "# 3.涂料温度  \n\n涂料温度是指施工时的涂料温度。涂料的临时贮存与调制往往在调漆间进行，与涂装车间不在一起，当调漆间的温度与涂装车间的温度差异较大时，会因为两个温度的差异导致漆病的发生。涂料的温度对施工有较大的影响，特别是对于一些不能通过调整稀释剂比例调整黏度的涂料产品，温度的调整就显得更为重要，如无溶剂环氧涂料、聚脲涂料等都需要靠调整涂料的温度来调整黏度以避免漆病和减少施工难度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1606,
+        "chunk": "# 四、相对湿度的管理  \n\n湿度是湿空气中所含的水蒸气的质量与绝对干空气的质量之比。这个概念通常只用于理论的计算中，在实际的应用中通常使用的是相对湿度的概念，即在一定的总压下，湿空气中水蒸气分压与同温度下水的饱和蒸气压之比的百分数，称为相对湿度百分数，简称相对湿度(结露)。  \n\n![](images/d440d201d6c24e0168fc0248d2f76845edb7280d1b4e6d232ec909ae3c645e37.jpg)  \n(a）于湿温度计  \n\n![](images/f4b10f7facaa22a064549acbe655d1dfb47db83fc8cce8d75f07d7acfe937bc8.jpg)  \n图5-4-1 干-湿温度计和露点盘",
+        "category": " Introduction"
+    },
+    {
+        "id": 1607,
+        "chunk": "# 1.相对湿度的测量  \n\n在了解相对湿度的测量之前，先了解以下几个概念。  \n\n(1）干球温度用普通温度计测得的湿空气温度为其真实温度。为了避免与湿球温度相混淆，称这样测得的温度为干球温度，简称温度。  \n\n(2）湿球温度用水保持湿润的纱布包裹温度计的感温部分（水银球或酒精球)，这种温度计为湿球温度计。若将湿球温度计置于一定温度和湿度的湿空气流中，达到平衡或稳定时的温度称为该空气的湿球温度。  \n\n(3）露点露点是指将不饱和的空气等湿度冷却至饱和状态，此时的温度称为该空气的露点。当空气的温度下降到露点时，底材表面就会开始结露。露点温度通常与空气的相对湿度和环境温度等相关。  \n\n了解了上述的几个概念后就可以比较容易地理解相对湿度的测量。首先，用一种简单的工具“干-湿温度计”[图5-4-1(a)］测量出空气中的干球温度和湿球温度，然后，可以利用湿空气的温度-湿度图（t-H图）查出相关的数据。在施工现场，为了方便起见，可以利用一种简便的工具—露点盘［图5-4-1(b)］来查出相对湿度和露点温度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1608,
+        "chunk": "# 2.相对湿度的控制  \n\n讨论相对湿度对涂装的影响，实际上是考察结露对室外涂装的影响，室内条件下一般很少出现结露的情况。ISO8502-4中规定：除非有其他因素认可，当使用涂料时，底材表面温度应该至少高于露点3℃。通常在涂装规格书中会同时给出相对湿度的限值（小于85%）和表面温度与露点的差值（通常为3℃）要求，因此施工过程中有必要对两个要求同时进行测量和控制。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1609,
+        "chunk": "# 3.相对湿度的调整  \n\n空气的相对湿度和结露的可能性不是一成不变的，它是受多种条件影响的，如周围的热源、阳光对底材表面的照射、周围空气的流动、底材表面吸潮性污染介质的影响等。上面提到的“钢板表面温度至少高于露点3℃”是在通常情况下的约束条件，也是一般执行规则。它能够保证在一般条件下尽量避免由于钢板结露对涂装带来的影响。当空气相对湿度达到或超过 $85\\%$ ，而涂装工作必须进行时，需要采取特殊的措施，才能减少结露对涂装的影响。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1610,
+        "chunk": "# 五、空气污染影响的控制  \n\n在涂装过程中，周围环境的洁净与否会始终影响着整个涂装过程。总体而言，在厂房内施工时周围环境相对洁净，涂装过程受到的影响较小。而在户外施工时就要充分考虑到环境空气污染对涂装质量的影响，尽量避免在不洁净的空气中进行施工，或采取必要的手段减少空气污染带来的影响。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1611,
+        "chunk": "# 1.空气灰尘污染  \n\n空气中的固体粉尘颗粒的体积和密集程度会影响到涂料施工的效果。在遍布灰尘的空气中施工时，灰尘会附着在被涂物的表面，当灰尘的密集度达到一定值时，会影响到涂膜的性能。很多国际标准中都对底材表面的灰尘污染情况有具体描述，如ISO8502-3中将钢材表面的灰尘分为6级（表5-4-1)，并描述了灰尘粒子的状态和可参考的颗粒直径范围。ISO8502-3还提供了用胶带测量表面灰尘的方法。  \n\n表5-4-1 灰尘粒子大小分级  \n\n\n<html><body><table><tr><td>级别</td><td>颗粒的描述</td><td>颗粒参考直径/μm</td></tr><tr><td>0</td><td>灰尘粒子在10倍放大条件下不可见</td><td></td></tr><tr><td>1</td><td>灰尘粒子在10倍放大条件下刚刚可见，但是在正常视力条件下不可见</td><td><50μm</td></tr><tr><td>2</td><td>灰尘粒子在正常视力条件下刚刚可见</td><td>50~100μm</td></tr><tr><td>3</td><td>灰尘粒子在正常视力条件下能清楚地看见</td><td>≤0.5mm</td></tr><tr><td>4</td><td>灰尘粒子直径在0.5～2.5mm</td><td>0.5～2.5mm</td></tr><tr><td>5</td><td>灰尘粒子直径大于2.5mm</td><td>>2.5mm</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 1612,
+        "chunk": "# 2.盐分污染  \n\n盐分通常是指氯化钠、氯化镁等，这些物质易吸水，它们能够形成盐雾粒子随空气漂浮，特别是在沿海地区浓度比较高。这些盐雾粒子附着在底材表面时极易造成初期腐蚀，经过表面处理的钢铁表面迅速变黑等现象就是由于盐分造成腐蚀引起的。涂料涂覆在有盐分的底材后，经过一段时间盐分就会与水在底材与涂膜之间形成电解液，造成底材的提前腐蚀，并可能引起涂膜起泡等缺陷。这种因盐分污染使底材被腐蚀而造成的涂膜失效在金属、混凝土等材质上表现的尤为突出。ISO8502-6提供了测量表面盐分的方法，在一些标准中也提供了盐分的具体控制指标，如在《所有类型船舶专用海水压载水舱和散货船双舷侧处所保护涂层性能标准》中提供的要求是盐分 $\\leqslant50\\mathrm{mg/m^{2}}$ （以氯化钠计，电导率测定依据ISO8502-9）。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1613,
+        "chunk": "# 3.化学介质污染  \n\n对于大多数工业结构材料来说，最能加速其腐蚀过程的化学物质有二氧化硫、硫化氢、氨等。其中特别严重的是二氧化硫的污染。二氧化硫在不同的大气环境中的含量差别很大，在城市和工业区可达 $0.1{\\sim}100\\mathrm{mg/m^{3}}$ 。通常化学介质的污染又和空气的相对湿度密切相关的。当相对湿度低于临界湿度（约为70%）时，金属表面没有水膜，受到的仅仅是由于化学作用引起的腐蚀，既使长期暴露，腐蚀也是比较小的。而当湿度高于临界湿度时，底材表面凝结的水膜会溶解空气中的化学物质而形成电解液，此时便发生了严重的电化学腐蚀，腐蚀速率会突然增加。如果在这种情况下涂装，往往会导致涂膜的提前失效。因此，进行表面处理后的金属材料应及时进行涂装，以免被空气中的腐蚀性化学介质污染。  \n\n综上所述，在整个涂装过程中涂装环境对涂料施工的质量有很大影响。在涂料施工时，要充分重视周围环境的变化，并做好必要的准备，尽量减小环境因素对涂装效果的影响。  \n\n![](images/85e18edc634b32944f3667f8923325ce6acfab33b6889f4f2d1208574ea580d2.jpg)  \n\n涂料在不同的阶段会有不同的缺陷产生，其产生原因、缺陷的形态和处理方法等也各不相同，在这里把它分为三类：涂料的缺陷、涂膜老化缺陷和涂装缺陷。  \n\n涂料缺陷是指涂料本身在生产和贮存过程中受涂料配方、生产工艺、包装工艺和贮存条件等因素的影响而形成的涂料本身的病态。这种缺陷有些是可以通过调整涂装施工条件解决的，如易流挂、黏度过高、沉淀等；有些缺陷如成胶、颜色不准、返粗等则是不能通过调整涂装施工条件来解决的。  \n\n涂膜老化缺陷是指涂膜在使用过程中，受到外界影响发生自然老化而产生的病态，这通常都是由涂料本身的性能决定的。  \n\n涂装缺陷是指在涂料施工和涂料成膜过程中受施工条件和环境因素的影响而形成的影响涂膜性能、涂膜外观等指标的病态。这些缺陷通常都可以通过调整施工参数和控制环境条件等方法来改善涂膜的形成过程并达到充分发挥涂膜作用的效果。本节重点介绍此类涂装缺陷的产生和解决方法。  \n\n涂装缺陷的种类很多，大致分为以下几种：露底、起泡、剥落、开裂、长霉、发白、失光、浮色、凹穴、针孔、皱纹、流挂、气泡、污染、褪色、污点、斑点、橘皮、杂物、渗色、凸斑、擦伤、打伤、撞伤、色斑、色光、泛金、起霜、晶纹、漏涂等。在实际涂装过程各种用途的涂料产生涂装缺陷的原因和改进措施可以参考相应章节中的内容。  \n\n![](images/f587bcd0c3bde929e6d9025f2cdd10f84f7b3ba18ab69df343863107eff23ad4.jpg)  \n\n涂料在施工后，要进行涂膜的整体检验，以确定涂膜的涂装效果是否符合设计的要求，以及是否满足今后涂膜使用环境的要求。涂膜验收的主要手段是对施工后的涂膜进行整体检测。由于现场的条件有限，往往只能通过有限的检测项目来确定涂装效果。随着技术水平的不断进步，越来越多的便携式检测仪器不断出现，使得能够在现场检测的项目越来越多，也使现场的涂膜检验更加科学和重要。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1614,
+        "chunk": "# 一、涂膜表面状态的验收  \n\n装饰作用是涂料重要的基本作用，涂料在施工后要达到一定的表面效果才能够体现出装饰效果。良好的表面状态除了能够起到装饰效果外，还能加强涂膜的整体保护作用。另外，涂膜的很多特殊效果，如不粘涂层、防污涂层、防结露涂层等，都需要通过良好的表面状态才能体现出来。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1615,
+        "chunk": "# 1.颜色的检查，  \n\n涂料的面漆都是按照标准色卡进行调制，涂料出厂时颜色与标准色卡是一致的。在贮存过程中涂料中的颜料颗粒往往会发生自聚现象，造成施工后的涂膜颜色与标准色卡有偏差。这种偏差可以用色差来定量表示，GB/T3181—2008《漆膜颜色标准》将色差定义为以定量表示的色知觉差异，通常以 $\\Delta E$ 表示。按照GB/T1766—2008《色漆和清漆涂层老化的评级方法》的规定，色差值 $\\le1.5$ 时目测可认为无变色。通常在现场可以使用便携式的色差计进行测量。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1616,
+        "chunk": "# 2.表面光泽的检查  \n\n涂料的光泽度是在配方的设计阶段就已经确定了的。但施工工艺的变化，可能会导致涂膜表面光泽偏离规定值，如涂膜表面过于粗糙、没有配套底漆、涂层厚度不足等都会影响光泽值。在现场可以使用便携式的光泽计进行现场光泽检查，以确定涂膜的光泽是否能够满足要求。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1617,
+        "chunk": "# 3.涂膜表面状态的检查  \n\n对涂膜表面状态的检查通常采用目视比较的方法，在判定标准上与每个检查员的自身水平和经验有关，这一项通常没有具体的标准，大多数的标准也是以“平整、无异常”作为基本评语。在进行表面状态的检查时要关注以下几个方面：在不考虑底材变形的情况下涂膜是否能自然地形成一个整体平面而没有可见的凹坑、凸起等机械变形；涂膜是否表面光滑、平整，肉眼观察没有漆雾、漆渣等异物，且手感较好；涂膜表面是否有皱纹、缩孔、针孔等各种施工缺陷，边角部位漆膜包覆是否良好；涂膜颜色是否均匀、光泽是否正常，在自然光线下是否有异常现象。对于橘纹漆、真石涂料、防滑涂料等具有特殊效果的涂料，其表面状态可不按照上述的标准评价，但应与其所具有的功能相一致。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1618,
+        "chunk": "# 二、涂膜厚度的验收  \n\n涂膜厚度是涂膜能否达到预定防腐性能和装饰效果的关键因素，因此涂膜厚度的检测是一项非常重要和必须要实施的检测工作。通过涂膜厚度的检测能够判断涂料施工的水平和质量，保证涂料施工顺利进行。由于涂料干燥后测得的涂膜厚度不能随意更改，必须通过增加道数或者打磨的方法进行涂膜厚度的增减，所以通常在施工过程中要经常对涂料湿膜厚度进行测量并作为涂料干燥膜厚的参考，以便在施工过程中随时调整涂膜厚度。由于各家涂料商供应的产品有差异，同一干膜厚度所对应的湿膜厚度并不完全一致，因此最终涂膜厚度的指标还是以实际测得的于燥涂膜的厚度为标准。  \n\n涂料的干膜厚度与湿膜厚度可按照下面的公式进行换算。  \n\n式中 D干膜厚度 -干燥涂膜的厚度；  \n\nD湿膜厚度 涂料的湿膜厚度；SVR- 涂料的体积固体含量。  \n\n通常该公式只能近似换算干燥涂膜的厚度，实际要以仪器测量值为准。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1619,
+        "chunk": "# 1.测定涂膜厚度的方法  \n\n测定干燥涂膜厚度的方法有很多种，比较常用的有切开法、电磁法、涡流法、超声波法等。切开法是以固定角度的刀头将涂膜切开，然后通过带有刻度的显微镜观察表面，读出涂膜的厚度，此种方法的优点是可以测量多种底材、观察多道涂膜的厚度，缺点是需要切开涂膜，会造成涂膜损伤。电磁法是利用直流电感生的磁场，测量磁性底材上非磁性涂膜的厚度。直流电透过涂膜并在底材上发生电磁感应，涂膜越厚电磁感应力越弱，反之电磁感应力越强，两者呈线性关系。首先测量基体的感应强度，再将电信号测量数据转换为干膜厚度读数在仪表盘或屏幕上显示出来。该方法的优点是可数字显示、读数准确，测量方便且不破坏底材；缺点是仅适用于磁性底材，易受周围磁场和磁性金属的影响。涡流法是利用涡电流测量原理测量导电基体上的非导电涂层干膜厚度的仪器，借助于通入探测器的交流电在基体内感生涡流。再将涡流测量值转换为干膜厚度值，优点是可测量非磁性金属底材、读数准确；缺点是易受周围电场的影响。超声波法是利用超声波脉冲反射的原理进行测量，优点是适用金属和非金属底材、可测量多道涂膜厚度；缺点是对于薄膜涂层和粗糙底材精度稍差。国内外许多仪器生产商都能够提供相关的检测设备，如Elcometer等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1620,
+        "chunk": "# 2.涂膜厚度的验收  \n\n通常在涂料施工的技术标准中会专门写到对干燥涂膜的厚度要求，涂膜厚度的验收通常规定有两个指标：①最低膜厚指标；②达到膜厚的点占总测量点的比例。如90-90原则是指测试的干膜厚度的数值不能低于规定膜厚的 $90\\%$ ，且满足规定膜厚的测量点的数量不得少于总测量点数量的 $90\\%$ 。依此类推还有85-85原则，80-80原则等，当然有些技术要求会将规定膜厚定义为平均膜厚或者定义为最低膜厚。因此所有的验收标准需要在施工前进行确认，以免在施工后产生歧义。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1621,
+        "chunk": "# 三、涂膜物理性能的验收  \n\n受条件和检测仪器的限制，在涂装现场可以进行物理性能测量的项目不是很多，在这里只选择几种常见的物理性能指标进行介绍。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1622,
+        "chunk": "# 1．附着力  \n\n附着力是指涂膜与被涂物之间通过物理和化学作用结合在一起的强度。在现场检测附着力的目的主要是用来确定涂膜今后的耐久性的指标。使用的主要方法多为拉拔法，依据的标准为GB/T5210—2006《色漆和清漆拉开法附着力试验》。具体的操作步骤是将试样粘接在涂膜表面，在规定的速度下，在试样的胶结面上施加垂直、均匀的拉力，以测定涂层与底材间附着破坏时所需的力，以 $\\mathrm{^{46}k g f/c m^{2}\\Sigma^{9}}$ 表示 $(1\\mathbf{kg}\\mathbf{f}/\\mathbf{cm}^{2}=0.098\\mathbf{MPa})$ 。在现场有时也用划格法作为附着力的参考，GB/T9286—1998《色漆和清漆漆膜的划格试验》规定了在以直角网格图形切割涂层穿透至底材时来评定涂层从底材上脱离的抗性的一种试验方法。由于此方法测得的性能除了取决于该涂料对上道涂层或底材的附着力外，还取决于一些其他各种因素，因此一般不能将这个方法作为正式的附着力测定方法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1623,
+        "chunk": "# 2.硬度  \n\n可以理解为漆膜表面对作用其上的另一个硬度较大的物体所表现的阻力。在涂装现场可以依照GB6739—2006《色漆和清漆铅笔法测定漆膜硬度》中的B法来测量涂膜的铅笔硬度，以检验涂膜的硬度是否达到要求。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1624,
+        "chunk": "# 3.干燥状况  \n\n干燥状况是指涂料施工后涂膜从流动的液体状态向稳定的固体状态转变的过程中所呈现出来的不同的状况。在实际工作中经常需要对涂装后涂膜的干燥状况进行检察，以确定下一步需要进行的覆涂、浸水、堆码、机械加工等作业的工作进度。在现场可以按照GB/T1728—1979（1989）《漆膜、腻子膜于燥时间测定法》中的指触法测量涂膜表面干燥时间，按照GB/T1728—1979（1989）中的压棉球法、刀片法等测量实际干燥时间。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1625,
+        "chunk": "# 第五节 涂料施工的技术服务  \n\n涂料在出厂的时候不具有涂膜的性能，当液体涂料干燥并形成完整的涂膜后，才具有应有的性能。通常，涂料的成膜过程与液体涂料本身的性能息息相关，而涂料的施工人员对液体涂料的性能没有足够的了解，所以涂料的使用过程需要在生产厂家的专业人员指导下进行，这就是人们所说的对涂料的技术服务。几乎所有的国际涂料公司都有专业的技术服务人员，国内的涂料公司也在逐步向这一目标努力，可以说涂料的技术服务是一个公司必不可少的工作内容。  \n\n技术服务工作对于涂料公司来说，既是技术工作的延伸，也是销售工作的组成部分，对于保证产品质量、提升企业形象和拉近与客户的关系至关重要。以下主要从技术方面讲述涂料施工的技术服务工作。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1626,
+        "chunk": "# 一、涂料施工技术服务的目的  \n\n涂料公司现场施工技术服务是涂料产品的增值服务内容之一，它的主要目的是观察、监督施工的全过程并向客户提供专业指导，使涂料达到最好的使用效果。除此之外，还具有如下目的。  \n\n$\\textcircled{1}$ 减少因表面处理、涂料施工不当造成的涂膜性能降低和客户投诉。$\\textcircled{2}$ 完成本公司对客户承担的技术指导义务。同时通过技术服务保持同客户的密切关系。$\\textcircled{3}$ 通过现场观察更确切地了解本公司产品的实际使用情况，为产品的不断改进和新产品研发提供信息。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1627,
+        "chunk": "# 二、技术服务人员的主要工作内容  \n\n技术服务人员在施工现场主要从事以下工作。  \n\n$\\textcircled{1}$ 指导施工人员现场操作，保证公司产品合理使用。$\\textcircled{2}$ 查验发到现场的货物，控制现场涂料消耗、统计现场涂料耗量和库存，记录各项数据，并完成施工报告。$\\textcircled{3}$ 与公司保持联系，及时反馈客户对公司产品的意见和要求，保证供货的及时性及信息的畅通。$\\textcircled{4}$ 向客户解释产品性能，保证客户能正确理解产品的施工要求，并具体解决因现场施工引起的投诉等问题。  \n\n当然，现场技术服务人员的工作不止这些，由于技术服务人员处在施工现场的第一线，往往能够了解最新的市场和产品使用信息，所以还要做好信息的收集整理等工作，为公司的营销策划和产品升级换代提供数据支持。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1628,
+        "chunk": "# 三、技术服务人员的工作方法  \n\n技术服务人员的主要工作方法首先是观察，并将观察到的情况整理成文字及图片报告，最后依据观察得出的结论指导自己的行动。  \n\n(1）观察技术服务人员要深入到施工现场各个方面进行观察，对于发现的一切可疑之处要进行初步分析并做好记录，记录可以采用多种形式，如文字、草图、照片或者录像等。  \n\n(2）整理报告将观察的情况和分析的结果用报告的形式记录下来并存档，注意报告的  \n\n记录要领。  \n\n$\\textcircled{1}$ 各类报告应当尽可能地使用正式报告书形式。  \n\n②各类报告在某阶段工作完成之后立即着手完成，以防止因记忆不全而遗漏。  \n\n$\\textcircled{3}$ 报告书应尽快送交公司的主管部门并等待指示进行下一步工作。  \n\n④报告中如需图片帮助说明问题，应有相应的文字说明。  \n\n$\\textcircled{5}$ 报告应及时提供涂料施工中出现的问题$\\textcircled{6}$ 报告应如实填写，报告中的个人意见也应如实阐述。  \n\n(3）行动依据现场分析的结果或者公司主管部门的指示进行下一步工作。技术服务人员依据合同规定，有权利执行以下的行动。  \n\n$\\textcircled{1}$ 指导施工人员改进不符合标准的施工。  \n\n$\\textcircled{2}$ 如果采取上述措施仍然无法改观，应向客户（业主）如实报告并提出标准施工要求等具体意见。  \n\n$\\textcircled{3}$ 如按要求施工后仍达不到产品说明书和涂装规范规定的标准，技术服务人员有权利召开业主、施工单位、涂料公司、监理等各方的代表会议。在此会议上，技术服务人员应如实报告施工时的实际情况，并且应当策略地强调非标准施工对涂料性能的影响和后果，并应由各方讨论制定切实可行的补救措施以便有效地执行合约。会议记录应由参加集体会议的各方代表签字。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1629,
+        "chunk": "# 四、施工前的准备工作  \n\n和做所有工作一样，每名技术服务人员应当在奔赴现场开始技术服务工作之前，需要一些必要的准备工作，这些工作的大部分往往都是是重复性的，经验丰富的技术服务人员会把准备工作列人日常工作之中。但是涂料的施工从来也没有出现过完全相同的情况和条件，即使在同一工厂，使用同样的涂料产品，也会因为季节更替、涂料批次、工人调整、设备更换等原因使得施工的条件发生变化。因此，每个项目的准备工作往往又有其各自的特点，为了避免或减少工作中可能会出现的各种差错，技术服务人员必须在施工前把有关的情况尽可能多地了解清楚，施工前的准备工作主要包括以下几个方面。  \n\n（1）首先确认必须要带到现场的物品，最好做成清单的形式，一方面便于每次出发前都能够快速了解这些物品是否已经准备到位；另一方面也有利于工作返回时清点这些物品，防止丢失。通常包括如下的确认工作。  \n\n$\\textcircled{1}$ 检查施工工具、检验工具及检测仪器是否齐全且工作正常。  \n\n$\\textcircled{2}$ 带好本公司的产品说明书。  \n\n$\\textcircled{3}$ 带好有关的书面报告单、笔记本电脑及相关电子文件。  \n\n$\\textcircled{4}$ 确认与施工有关的人员联系资料（姓名、职务、电话）。  \n\n$\\textcircled{5}$ 查阅并准备好曾经施工过的相似项目的施工报告。  \n\n$\\textcircled{6}$ 与此次施工有关的参考资料。  \n\n(2）在施工前技术服务人员要将整个施工过程做一遍预想，并对可能出现的问题和现场的情况作出预案，以便能在发生问题时更好地处理紧急事件。因此技术服务人员还需要了解以下内容。  \n\n$\\textcircled{1}$ 项目的时间进度安排。  \n\n$\\textcircled{2}$ 项目所处现场的气候条件。  \n\n$\\textcircled{3}$ 表面处理情况。  \n\n$\\textcircled{4}$ 涂料的准备情况。  \n\n$\\textcircled{5}$ 施工检查区域和需要跟踪的测试点。  \n\n在大多数情况下，通过这样的自我检查就可以发现一些问题，技术服务人员应该尽量在到达现场前掌握这些问题并准备好相关资料，做好充分的准备。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1630,
+        "chunk": "# 五、现场技术服务工作的展开  \n\n涂料公司的技术服务人员应该始终把技术服务看做是完善本公司产品的重要环节，并让客户相信，技术服务工作是旨在帮助他们以最经济的方法达到施工的最佳效果。技术服务人员在现场必须要努力争取得到现场相关部门的支持，取得所需的相关资料，熟悉自己的工作环境，并制定好工作计划。技术服务人员应当清醒地认识到这样一个事实，即在自已有限的职责范围内，应努力在整个施工过程中对涂装工作进行必要的干预和指正，而不能等工作完成后再进行检查。其中道理不难明白，一项工作一旦完成，施工设备和人员都已经从现场撤出，再要求施工方返工是非常困难的。  \n\n在现场的工作应该按照以下步骤进行。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1631,
+        "chunk": "# 1.组织召开施工前的工作准备会议  \n\n在和现场相关人员进行充分讨论的基础上确定相关事项，制订工作计划，并尽量按照计划展开工作。工作计划应该包括如下内容。  \n\n$\\textcircled{1}$ 表面处理前的检查要点。  \n$\\textcircled{2}$ 表面处理时的检查要点。  \n$\\textcircled{3}$ 涂料施工前的检查要点。  \n$\\textcircled{4}$ 涂料施工时的检查要点。  \n$\\textcircled{5}$ 涂料施工后的检查要点。  \n$\\textcircled{6}$ 技术服务人员在现场的工作权限。  \n$\\textcircled{7}$ 技术服务人员的报告程序。  \n$\\textcircled{8}$ 现场会议召开的频率和时间安排。  \n$\\textcircled{9}$ 施工与说明书要求有偏差时应采取的措施。  \n$\\textcircled{10}$ 检查方法和标准。  \n$\\textcircled{11}$ 检查地点和时间。  \n$\\textcircled{12}$ 验收步骤。  \n\n技术服务人员要及时以会议纪要的形式将讨论后的工作计划通知现场各方，指导实际工作，同时要将该计划上报给自己公司的主管部门备案，以利于后续工作的开展。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1632,
+        "chunk": "# 2.现场工作的展开  \n\n到达现场后要对现场的生产设备、工艺状况、施工人员素质等进行调查，对整体生产能力进行评价，同时找出可能出现问题的关键环节。对于发现的问题要及时与施工单位进行交流沟通，以便在开工之前就能使施工条件得到改善。开工前应与业主、施工方、监理等相关单位召开产前会，确定生产工艺、质量控制标准、各方的接口环节等各方面的内容。  \n\n技术服务人员每大要提前到达施工现场，与施工单位协调当日工作安排。对现场的施工环境进行检查，确认能否满足涂料施工要求，并根据环境情况与施工单位交流施工建议。即使是在厂房内施工也要对涂装环境进行评价，避免因环境问题带来的涂膜缺陷，甚至影响长期质量。  \n\n技术服务人员的日常工作主要包括以下内容。  \n\n① 检查表面处理情况，对于表面处理的质量进行评价，确认能否进行后续施工，对于不符合质量要求的工件要求返工。  \n\n$\\textcircled{2}$ 核对涂料品种和产品名称，检查施工设备，对整体生产状况进行评价，并记录发现的问题，向施工单位提出改进要求。  \n\n$\\textcircled{3}$ 检查涂料的施工过程，若发现施工过程的缺陷，要及时与施工单位协调，对施工过程进行调整，满足涂料产品质量要求。  \n\n$\\textcircled{4}$ 若发现有涂膜缺陷，应积极想出解决办法，并指导施工人员进行修补，同时要分析涂膜缺陷产生的原因，指导施工人员调整施工设备，改进施工方法，避免涂膜缺陷再次发生。  \n\n$\\textcircled{5}$ 完整记录整个施工过程并制作施工报告，提供给客户并发送给自己公司存档。  \n\n$\\textcircled{6}$ 对于施工过程中不能满足质量要求而因种种原因又不得不施工的项目要做好完整记录，向业主方、施工方、监理方和本公司进行反馈，并将报告存档，作为今后发生质量问题时的证据。  \n\n$\\textcircled{7}$ 在施工过程中为了保证质量稳定，技术服务人员需要不定期地组织业主、施工方、监理等相关单位进行施工情况的讨论，提出不符合质量要求的项目，以督促各方改进。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1633,
+        "chunk": "# 六、技术服务的记录与报告  \n\n报告是一种信息的传播形式，它往往出自某一事件的观察者，并能使关心这一事件的人在不到现场的情况下，即能对该事物做出详细的了解和正确的评判。  \n\n技术服务人员完成技术服务报告的目的是维护本公司的利益，为公司提供产品追溯的依据，同时也为了对客户负责，为客户提供技术档案。除此之外制作一份良好的施工报告还能够达到以下效果。  \n\n$\\textcircled{1}$ 建立产品参考资料及施工档案，以备追溯。  \n$\\textcircled{2}$ 了解不同表面处理、施工条件以及不同涂料系列的有机联系。  \n$\\textcircled{3}$ 增进与客户的良好关系。  \n$\\textcircled{4}$ 避免不公正的投诉以及为此而付出的代价。  \n$\\textcircled{5}$ 为将来分析涂膜的长期性能提供依据。  \n\n报告按其内容通常可分为原始记录、非正式报告和正式报告三种。原始记录又包括文字记录和图像记录等。凡与所作的涂装施工有关系的各种活动都应做好原始文字记录，如交谈、会议要点、现场检查结果以及所有以后需要写人报告的相关内容。图像资料在许多场合常常能比文字更形象、更直接地说明问题。所以，在有可能的情况下要多用图像资料来充实报告。但每一份图像资料都应该是为了说明某一个问题、解释某一件事或坚持某一论点服务的，要避免那些毫无价值或参考价值很少的图像资料。在现场拍摄每照一张图片后，都应立即记录其内容提要，以免时间长了出现混淆。  \n\n每个涂料公司通常会根据其涂料施工的特点制定一整套的报告格式供技术服务人员使用，称这些报告为正式报告。技术服务人员可以根据项目的具体情况挑选对应的报告。以下列举几种报告格式（表5-4-2和表5-4-3)，供大家参考。  \n\n与正式报告相对应，当使用预先设计的报告模式不能充分表达自已对现场情况的描述时，技术服务人员就必须创造一种格式的报告来满足实际需要。把这种报告形式称作不定式报告或非正式报告。这种报告通常因项目和情况的不同其内容也不尽相同。需要技术服务人员具有较强的随机应变的能力。  \n\n表5-4-2XXXX×项目技术服务日报表（例  \n\n\n<html><body><table><tr><td>项目名称</td><td></td><td>业主名称</td><td></td></tr><tr><td>监理单位</td><td></td><td>承包商</td><td></td></tr><tr><td>施工结构名称</td><td></td><td>施工单位</td><td></td></tr><tr><td colspan=\"4\">环境状况</td></tr><tr><td>天气状况</td><td></td><td>环境温度</td><td></td></tr><tr><td>相对湿度</td><td></td><td>风力</td><td></td></tr><tr><td>露点温度</td><td></td><td>底材温度</td><td></td></tr><tr><td colspan=\"4\">现场表面处理</td></tr><tr><td>钢材原始状态</td><td></td><td>表面处理方式</td><td></td></tr><tr><td>喷砂级别</td><td></td><td colspan=\"2\">打磨级别</td></tr><tr><td>其他处理级别</td><td></td><td colspan=\"2\">结构处理情况（飞溅锐边等）</td></tr><tr><td>磨料种类</td><td></td><td colspan=\"2\">磨料状况</td></tr><tr><td>表面粗糙度</td><td></td><td>表面清洁度</td><td></td></tr><tr><td>表面处理综合判定</td><td colspan=\"3\"></td></tr><tr><td colspan=\"4\"></td></tr><tr><td>涂装检查</td><td></td><td>涂装部位</td><td></td></tr><tr><td>涂装方式 喷漆泵型号</td><td></td><td>泵压缩比</td><td></td></tr><tr><td>进口压力</td><td></td><td>喷嘴型号</td><td></td></tr><tr><td>涂料名称</td><td></td><td>产品批号(主剂/固化剂)</td><td></td></tr><tr><td>稀释比例</td><td></td><td>干燥状况</td><td></td></tr></table></body></html>  \n\n涂装厚度测量简图  \n\n\n<html><body><table><tr><td>被涂装部位简图</td><td colspan=\"5\">膜厚/μm</td></tr><tr><td rowspan=\"7\"></td><td>1</td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td>2</td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td>3</td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td>4</td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n涂料用量  \n\n\n<html><body><table><tr><td>涂装面积</td><td></td><td>涂料用量</td><td></td></tr><tr><td colspan=\"4\">总结</td></tr></table></body></html>\n\n涂装效果总体评价：  \n\n表5-4-3×XX××项目附着力检查报告（例）  \n\n\n<html><body><table><tr><td>项目名称</td><td></td></tr><tr><td>测试标准/方法</td><td></td></tr><tr><td>测试仪器型号</td><td></td></tr><tr><td>使用胶或胶带名称/型号</td><td></td></tr><tr><td>测试部位</td><td></td></tr><tr><td>施工日期</td><td></td></tr><tr><td>测试日期</td><td></td></tr><tr><td>测试地点</td><td></td></tr><tr><td>天气状况(环境温度、相对湿度等)</td><td></td></tr><tr><td colspan=\"2\">涂层配套系统名称</td></tr><tr><td>1</td><td></td></tr><tr><td>2</td><td></td></tr><tr><td>3</td><td></td></tr><tr><td>4</td><td></td></tr><tr><td>5</td><td></td></tr><tr><td>6</td><td></td></tr></table></body></html>\n\n测试部位简图  \n\n<html><body><table><tr><td>测试部位</td><td>测试结果（胶带法要有胶带存档）</td></tr><tr><td>１</td><td></td></tr><tr><td></td><td></td></tr><tr><td></td><td></td></tr><tr><td>4</td><td></td></tr><tr><td>5</td><td></td></tr><tr><td></td><td></td></tr><tr><td></td><td></td></tr><tr><td>8</td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>业主代表</td><td></td></tr><tr><td>监理代表</td><td></td></tr><tr><td>施工单位代表</td><td></td></tr><tr><td>涂料公司代表</td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1634,
+        "chunk": "# 参考文献  \n\n[1］王健，刘会成，刘新主编，防腐蚀涂料与涂装工．北京：化学工业出版社，2006.  \n\n[2]鹤田清治，寺内淑晃，安原清，鎏装の，东京：技术书院，2000.  \n[3]日本关西涂料株式会社．桥梁涂装．大阪：关西涂料株式会社，2005.  \n[4]ISO129441998.  \n[5]日本涂料工业协会．重防腐涂料与涂装．东京：日本工业协会．1995.  \n[6]庞启财．防腐蚀涂料涂装和质量控制．北京：化学工业出版社，2003.  \n[7］GB9969.1—1998．工业产品使用说明书．2008.  \n[8] 杨世芳主编，木器涂料涂装技术问答．北京：化学工业出版社，2008.  \n[9]李芳，苏立荣，沈春林等编，建筑涂装工程问答实录．北京：机械工业出版社，2008.  \n[10] 叶杨祥，潘肇基主编，涂装技术实用手册，北京：机械工业出版社，2005.  \n[11] 长谷川谦三著，料塗装技術．东京：日本理工出版会，2007.  \n[12] 曹京宜等，涂装表面预处理技术与应用，北京：化学工业出版社，2004.  \n[13] 周良，喷丸（砂）、喷涂技术及装备．北京；化学工业出版社，2008.  \n［14]NACE．检察员培训教材课程：教师手册．NACE国际，2007.  \n[15] 孙兰新，宋文章，王善勤等．涂装工艺与设备，北京：中国轻工业出版社，2001.  \n［16]涂料工艺编委会编．涂料工艺：下册，北京：化学工业出版社，1997.  \n［17］汪国平编著．船舶涂料与涂装技术．北京：化学工业出版社，2006.  \n[18] 李敏风编著，集装箱涂料与涂装技术，北京：化学工业出版社，2002.  \n［19］张学敏编著，涂装工艺学．北京：化学工业出版社，2002.  \n[20] 西村利明，柳田昭雄编集，涂料读本，《涂装编》，东京：关西涂料株式会社，1998.  \n[21] W．威克斯，N．琼斯，S．柏巴斯．有机涂料科学和技术．经俘良等译．北京：化学工业出版社，2002.  \n[22］徐秉凯等主编．国内外涂料使用手册．南京：江苏科学技术出版社，2005.  \n[23] 曾敏生．影响涂料利用率因素及改进措施．涂料工业，2005，（5）.  \n[24］冯立明，牛玉超，张殿平等编．涂装工艺与设备．北京：化学工业出版社，2007.  \n[25]GB50034—2004.建筑照明设计标准.  \n[26］天津大学化工原理教研室编．化工原理．天津：天津科学技术出版社，1987.  \n[27］魏宝明主编．金属腐蚀理论及应用．北京：化学工业出版社，2004.  \n[28]ISO 8502-3 1992.  \n[29]ISO 8502-4 1993.  \n[30]ISO 8502-9 1998.  \n[31］GB/T3181—-2008.漆膜颜色标准.  \n[32］GB/T1766—2008．色漆和清漆涂层老化的评级方法.  \n[33] GB/T5210—2006．色漆和清漆拉开法附着力试验.  \n[34]GB/T9286—1998．色漆和清漆漆膜的划格试验.  \n[35] GB/T6739—2006．色漆和清漆铅笔法测定漆膜硬度.  \n［36］GB/T1728—1979（1989)．漆膜、腻子膜干燥时间测定法.",
+        "category": " References"
+    },
+    {
+        "id": 1635,
+        "chunk": "# 涂装施工安全、卫生和污染治理",
+        "category": " Introduction"
+    },
+    {
+        "id": 1636,
+        "chunk": "# 第一节 概述  \n\n涂料涂装，尤其是溶剂型涂料的涂装是一个危险的过程，其主要的危险在于施工者可能会接触到那些对人体健康造成危害的物质。喷涂作业时的危害可能来自于：火灾与爆炸、喷涂设备、搬运作业、噪声、有限空间作业等。因此，使用涂料及有关化学品的人员应查询产品安全标签、安全技术说明书和涂装作业可能导致危及安全与健康的相关资料，接受相关安全技术培训。在作业过程中应始终严格遵守安全生产、工业卫生的规章制度，及时报告可能造成危害和无法处理的情况。  \n\n本章旨在帮助建立安全的工作方法和环境，主要内容包括：危险因素及防护措施、一般安全措施一—个人防护用品（PPE）、使用涂料时的安全工作指导和环境、环境保护和污染预防。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1637,
+        "chunk": "# 第二节 涂装施工的危险因素及防护措施",
+        "category": " Introduction"
+    },
+    {
+        "id": 1638,
+        "chunk": "# 一、涂装施工的危险因素  \n\n涂料不论是在处理、使用还是在涂装过程中都伴随着各种危险有害因素。涂料中可能含有有害物质，因此被归类为危险品。在使用过程中，如不慎吸人、接触或误食，都可能会造成伤害和疾病。这些有害物质包括稀释剂、除油剂、脱漆剂及表面处理活动所产生的粉尘。  \n\n涂装作业过程主要的危险是火灾和爆炸，其次是所使用的设备、电气、带压力的涂料、沉重的涂料容器和噪声所带来的危险。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1639,
+        "chunk": "# 1.有害物质  \n\n与涂料施工相关的有害物质包括涂料、稀释剂、设备清洁剂、除油剂、脱漆剂和用于表面处理的产品。接触这些有害物质可能会导致如下短期和/或长期的健康影响。 精A5  \n\n（1）短期影响包括刺激性皮炎；皮肤和眼睛灼伤；呕吐；鼻子、喉咙和肺部刺激；头痛、头晕、疲劳。（2）长期影响包括过敏性皮炎；职业性哮喘；生殖系统损害；肾和肝损害；“涂料工综合征”，由于长期接触溶剂而导致的中枢神经系统损害；癌症。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1640,
+        "chunk": "# 2.有害物质侵入人体的方式  \n\n(1）吸人和食人喷涂作业活动增加了接触有害物质的机会，使用者更容易接触到有害蒸气、粉尘（干喷)、喷雾（浮质）以及清洁过程中用到的溶剂（干净的和污染的）。  \n\n有害物质（粉尘和喷雾）通常通过呼吸道和消化道进人人体。接触有害物质后可能会造成急、慢性健康危害。急性危害可能表现为呼吸道感染、呼吸短促、头晕、胸闷、恶心、头痛；慢性危害可能表现为肺部功能减退、呼吸系统疾病、哮喘、肺气肿症状、中枢神经系统损害，有的还可以或可能导致癌症。  \n\n聚脲弹性体材料（SPUA）材料本身不含VOC，不污染环境、不损害人体健康，但是，由于其快速的凝胶和高压操作的特性，会造成施工现场漆雾弥漫，凝胶的颗粒物四处飘散。如果人体吸入这些固体颗粒会有损身体健康；如果凝胶颗粒飘落到周边有用物体上（如仪器设备、办公家具、灯具标识等)，会沾污器具，难以清除。因此要求：施工人员必须穿戴连体防护服装、佩戴面具和呼吸器；对有清洁性要求的物体表面进行遮盖防护。  \n\n（2）直接接触喷涂活动、触碰涂料或未干的喷漆表面也可能使皮肤或眼睛直接接触到有害物质。对眼睛的影响可表现为剧烈的烧灼感，皮肤接触涂料和溶剂可能导致急性的刺激性皮炎，慢性过敏性皮炎或皮肤出现脱脂（天然油脂的流失）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1641,
+        "chunk": "# 3.火灾与爆炸  \n\n大部分的喷涂作业时会释放出溶剂蒸气，因此喷涂中易燃物质（如溶剂）的使用增加了火灾与爆炸的危险，涂料喷雾在作业空间内迅速扩散时可能遇上许多潜在的着火源，火源有如下几种。  \n\n(1）明火（火焰、火星、灼热）涂装作业场所内部或外部带入的烟火，焊接火花，烘干设备过热表面，灯具破裂时的明火，加热的钢板，照明灯具的灼热表面，设备、工件、管道、散热器、电器等过高温度的表面。  \n\n(2）静电放电静电喷枪与工件间距离过近，使用、贮存、输送有机溶剂的设备、容器、管道静电积累或容器、管道破裂，倾倒有机溶剂等，接地不好的设备释放静电所产生的电火花和电弧。  \n\n(3）摩擦冲击工件、钢铁工具、容器相互碰撞，带钉鞋或鞋底夹有外露金属件与地坪撞击等，能产生火花的设备，如打磨砂轮（机)。  \n\n（4）电器火花电路开启与切断、断路、过载、线路电位差引起的熔融金属，保险丝熔断，外露灼热丝等，手提电池供电设备（如相机、手电、手机等)。  \n\n(5）化学能自燃（如亚麻籽油、漆垢、沾染涂料的纤维堆积蓄热)，物质混合剧烈放热反应（如聚酯漆与引发剂)，加热涂料时添加有机溶剂，铝粉受潮产生氢气放热自燃，在“罐”内待处理的双组分涂料；雷电、日光聚集等。  \n\n有限空间及通风不良的场所，易燃气体及粉尘积聚达到爆炸极限时，遇到着火源会在瞬间产生燃烧爆炸。  \n\n溶剂闪点是火险的一个指标。闪点定义是：挥发性可燃物质上方的蒸气，在空气中接触火焰时燃烧的最低温度。闪点越低，火险越大。表5-5-1列出了涂料中常用溶剂的闪点。配制的涂料的闪点一般与使用溶剂的闪点相当。然而许多涂料含有混合溶剂，溶剂的闪点不能作为涂料闪点的精确衡量标准。  \n\n表5-5-1 溶剂闪点  \n\n\n<html><body><table><tr><td rowspan=\"2\">溶剂</td><td>闪点(封闭杯法)</td><td rowspan=\"2\">溶剂</td><td>闪点(封闭杯法)</td></tr><tr><td>/C</td><td>/C</td></tr><tr><td>乙酸戊酯</td><td>29</td><td>异丙醇</td><td>12</td></tr><tr><td>乙酸丁酯 正丁醇</td><td>29 35</td><td>甲基正丁酮 甲基溶纤剂（乙二醇单甲醚）</td><td>23 42</td></tr><tr><td>丁基卡必醇（二乙二醇单丁醚）</td><td>101</td><td>乙酸化甲基溶纤剂（乙酸化乙二醇单甲醚）</td><td>49</td></tr><tr><td>丁基溶纤剂（乙二醇单丁醚）</td><td>60</td><td>丁酮</td><td>-1</td></tr><tr><td>卡必醇（二乙二醇单乙醚）</td><td></td><td>甲基异丁酮</td><td></td></tr><tr><td></td><td>96</td><td></td><td>16</td></tr><tr><td>溶纤剂（乙二醇单乙醚）</td><td>42</td><td>溶剂油（稀释剂）</td><td>43</td></tr><tr><td>乙酸化溶纤剂（乙酸化乙二醇单乙醚）</td><td>51</td><td>SOLVATONE溶剂M</td><td>26</td></tr><tr><td>环乙酮</td><td>44</td><td>干式清洗溶剂（Ⅱ型）</td><td>59</td></tr><tr><td>双丙酮醇</td><td>47</td><td>苯乙烯</td><td>32</td></tr><tr><td>乙醇</td><td>13</td><td>甲苯</td><td>4</td></tr><tr><td>超高闪点石脑油</td><td>43</td><td>松节油</td><td>35</td></tr><tr><td>乙酸异丁酯</td><td>18</td><td>VM&P石脑油</td><td>-7</td></tr><tr><td>异丁醇</td><td>28</td><td>二甲苯</td><td>17</td></tr><tr><td>异佛尔酮</td><td>82</td><td></td><td></td></tr></table></body></html>\n\n注：上述溶剂中有些已被定为有毒/危险品，其使用应符合各项防护措施。其中有些具有生殖危害——影响到人类繁衍过程。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1642,
+        "chunk": "# 4.喷涂穿透伤害  \n\n涂料喷雾穿透伤害来源于无气喷涂过程中的巨大压力。涂料穿透进入身体的后果极为严重，涂料中溶剂会溶解脂肪组织和肌肉表皮神经，不适当的处理会导致坏疽和截肢。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1643,
+        "chunk": "# 【高压油穿透事故案例】  \n\n某工人在一次液压系统测试中食指指尖被穿透。初诊医生认为这是小伤，清洁包扎后就让病人走了。15h后，该病人返回医院看了急诊，由于油已经渗透到腕骨周围通道，他不得不接受了一个大的清创手术。尽管接受了各种治疗，其伤口一直未愈合，最终导致食指坏死，最后只得截肢。  \n\n为了尽可能减少可能出现的组织功能退化、坏疽及最终的截肢，所有穿透伤害必须立即接受外科手术治疗。外科医生须了解高压涂料喷枪伤害事故及处置的信息。  \n\n由于高压喷漆作业，区域内存在危险量的易燃和可燃性蒸气、漆雾、粉尘或积聚可燃性残存物。为避免伤害，强烈建议使用无气喷涂设备喷涂涂料时应严格遵循以下规则：  \n\n$\\textcircled{1}$ 喷漆区域内不应设置与喷漆无关的电气设备。在进行静电喷漆作业时，严禁在静电喷漆区中使用携带式灯具和其他移动式用电设备；  \n\n$\\textcircled{2}$ 喷漆室应安装可燃气体浓度和火灾报警装置（防爆型)，该装置应与自动停止供料、切断电源装置、自动灭火装置等相连锁；  \n\n$\\textcircled{3}$ 当设备处于加压状态时，不准将喷枪嘴对着别人及自身，不得用手指触摸喷嘴，或窥视枪口，也不要让枪嘴靠近身体的任何部位；  \n\n$\\textcircled{4}$ 所有喷涂作业人员都应采用定岗、定职、定责进行管理，接受安全作业、设备操作维修、个人防护、意外情况处理、防火灭火、涂料贮存与管理及使用等方面的技术培训，未经培训不得上岗；  \n\n$\\textcircled{5}$ 由于静电的潜在危险，喷涂区域内所有设备体外露导电部分及装置外可导电部分均应可靠接地；  \n\n$\\textcircled{6}$ 喷涂操作开始前，必须确保空气软管安全可靠，应检查其断裂、泄漏、划破、膨胀和活接头的损坏情况，如存在上述任何一项情况，都要立即更换，严禁用胶带粘贴胶管；  \n\n?当把喷枪传递给他人或停止使用时必须把安全门销住；  \n③多支喷枪同时作业时，必须拉开间距（5m左右)，并按同一方向进行喷涂；  \n③在喷涂作业中如果需要暂停作业或设备不用时，应关闭电源开关，喷枪应卸压；  \n①停止喷漆时，应先关闭输漆开关，然后关闭高压电流等其他开关。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1644,
+        "chunk": "# 5.人工搬运  \n\n很多被喷涂的物件形状复杂。这使得喷涂工缩紧、扭曲、弯曲或者将喷枪高举过头部作业，将导致身体过度疲劳，从而引起潜在的人工搬运伤害。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1645,
+        "chunk": "# 6.噪声  \n\n噪声对作业者的身体会造成很多不利影响，在工作中噪声造成的不利影响包括：使人们交流困难、难以集中精力、疲劳、不舒服、紧张、生产效率降低。涂料喷涂设备的工作噪声常常很大，这有可能导致耳聋。除喷涂设备产生的噪声外，周边其他操作产生的噪声，如喷砂、打磨、电焊、切割等均对身体有很大影响。  \n\n涂漆施工过程所用的风机、水泵、电机等各个噪声源部件及其风管、水管等应采取消声和隔振措施，使操作位置的噪声符合当地法规的规定。无气喷涂泵须装配消声器。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1646,
+        "chunk": "# 7.电  \n\n涂料喷涂会涉及电气设备（如照明、静电喷涂设备），接地不好或保养不善都可能会导致触电。任何喷涂操作都可能产生静电电荷，包括稀释和清洁。静电电荷有点燃易燃物质的可能。  \n\n电气装置和设备在涂料喷涂区、涂料搅拌区和贮藏区都是危险的。在这些区域使用的电气设备应是特别设计的，应防火防爆并符合当地法规的要求。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1647,
+        "chunk": "# 二、防护措施",
+        "category": " Introduction"
+    },
+    {
+        "id": 1648,
+        "chunk": "# 1.防火  \n\n火源可定义为能点燃易燃易爆气体或空气浮质的某种能量来源。火源常存在于涂料喷涂活动附近，应配备适当的消防器具。  \n\n在任何喷涂操作开始之前，须做好现场控制以消除火源，确保正确的接地，鉴别潜在的电路短路等以防止火灾和爆炸。  \n\n喷涂作业应在喷涂作业场或在划定的区域内进行，该区域为禁火区，严禁各种火花溅入以及进行明火作业。  \n\n喷涂作业场所的出入口至少应有两个；人口处及其他禁止明火的场所都应有禁止烟火的安全标志。区域内所有的电气设备、照明设施应符合国家有关爆炸危险场所电气安全的规定，实现电气整体防爆。  \n\n区域应按涂漆范围和用漆量设置足够数量的消防器材，并定期检查，保持有效状态。  \n\n进人作业区的人员，不得携带打火机、火柴等火种或任何可能引起火花的电气设备，也不得从事有可能引起机械火花和电火花的各种作业。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1649,
+        "chunk": "# 2.涂装作业安全管理  \n\n(1）搅拌、倾倒和稀释涂料的搅拌、倾倒和稀释必须在通风良好的环境下进行，操作者应穿戴适当的防护设备，如有溢流和飞溅点，应立即清洁；将可燃或易燃涂料从一个金属容器倒入另一个金属容器前，应将两个金属容器有效地连接和接地。若工艺条件许可，可向喷漆的涂料中加人适量的抗静电添加剂。  \n\n正在处理的任何物料（涂料、稀释剂、清洁剂、除油剂等）若飞溅到身体的任何部位，须立即用肥皂和水清洗皮肤。不得使用涂料稀料和清洁剂，因其会被皮肤吸收。被污染的衣物须尽早更换。  \n\n“空”桶内残留有涂料和溶剂蒸气，也是危险的。在根据当地法规进行处理之前，须将空桶运送到安全的地方并让其“干燥”。任何双组分材料须分开处理，以避免发生放热反应。  \n\n(2）涂料的贮存涂料及相关辅料的存贮应按有关部门的规定执行，须遵循以下指导。  \n\n$\\textcircled{1}$ 易燃材料须存贮于密封紧固、标签清晰的容器中。  \n\n$\\textcircled{2}$ 产品在贮存时应保持通风、干燥，防止日光直接照射；必须严禁烟火，隔绝火源，远离热源，操作过程中严禁火花产生，并应设置完善的消防设备；贮存场所应设置防雷击装置。  \n\n$\\textcircled{3}$ 工作结束后，应将剩余的涂料及辅料倒入密闭容器中放回原处贮存。  \n\n$\\textcircled{4}$ 大型溶剂（稀释剂）容器在液体运输过程中须接地。  \n\n$\\textcircled{5}$ 涂料不应贮存于喷涂区域。涂漆作业场所允许存放一定量的涂料及辅料，但不应超过一个班次的用量。  \n\n(3）设备的检查维护与检修所有设备应经常检查维护以保持良好的工作状态。  \n\n$\\textcircled{1}$ 喷漆设备只准喷漆人员操作，其他人不得擅自乱动。  \n\na.喷枪的喷嘴应保持畅通，其扣动扳机和安全阀性能应可靠，不准使用部件失效的喷枪；  \n\nb.连接喷枪的液流软管必须要保证导电性能良好，要保证喷枪通过软管连接接地；  \n\nc.喷漆操作时，不准使软管扭结，禁止用软管拖拉设备，软管的金属接头应采用包扎措施，以避免软管拖动时与钢板摩擦产生火花。  \n\n$\\textcircled{2}$ 应根据作业环境、设备状态、生产负荷、机械磨损等实际情况，明确规定检查、检修周期及其项目。压缩空气驱动型无空气喷涂装置的进气端应设置限压安全装置，并配置超压安全报警装置和接地装置。  \n\n（4）清洁和废物的处理吸湿材料如纸张、锯屑等会增加火灾和爆炸的危险，因而不能用于吸附滴落或过度喷涂的涂料。沾有涂料或溶剂的棉纱、抹布等清洁用材料不应乱抛，应放人带盖的金属箱（桶）内并进行“标识”，当班清除和进行妥善处理，如可行在处理前应用水使其潮湿。所有废弃材料的处理应遵循当地的法规。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1650,
+        "chunk": "# (5）喷涂作业  \n\n$\\textcircled{1}$ 喷涂作业人员必须经过安全技术培训，未经培训不准上岗。喷漆作业前必须对所有的喷漆设备及工具进行全面检查，确认无问题时方可工作。  \n\n$\\textcircled{2}$ 作业中，企业安全技术部门应设专人定时测定密闭空间内空气中氧含量和可燃气体浓度，氧含量应在 $18\\%$ 以上，可燃气体浓度应低于爆炸下限的 $10\\%$ 。在有限空间，例如船舶的舱内进行喷漆作业时，至少配备两人以上共同操作，若作业场所过于狭小，仅能容纳单人操作时，另外一人应负责监护。  \n\n$\\textcircled{3}$ 为确保喷漆工能持续地呼吸到洁净空气，在室内喷涂时，通风装置应始终处于工作状态，被喷涂物应总是处于喷漆工与排风出口之间。无气喷漆的高压射流和渗漏会导致严重伤害事故，因此任何情况下，不应将承压的无空气喷涂装置的喷嘴对准人体、电源、热源，亦不应以手掌试压，以确保其不暴露于危险物质中或免受穿透伤害。  \n\n④ 作业完毕后，必须及时将喷枪撤出舱外，并继续进行通风，直至漆膜完全固化；并对工作场所进行及时清理，将剩余的涂料和溶剂及时送回仓库，不准随便乱放。  \n\n(6）个人卫生应提供洗手设施和其他便利。休息室应避免与喷涂过程有关的危险及潜在污染物的侵害。食物和饮料不得带人喷涂区、存贮区或搅拌区。  \n\n(7）应急程序应急程序用于出现泄漏、溅洒、危险物质非受控排放等紧急情况的处置方法，该程序应包括现场清理、废弃处置、人员防护及当地法规的要求。所有相关人员都应充分了解本地应急程序的规定。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1651,
+        "chunk": "# 3.有限空间涂装作业  \n\n(1）作业前准备作业人员必须持有有限空间作业许可证，检测（或验证）有限空间及有害物质浓度后才能进入有限空间。有限空间必须牢固，防止侧翻、滚动及坠落。在容器制造时，因工艺要求有限空间必须转动时，应限制最高转速。  \n\n必须将有限空间内液体、固体沉积物及时清除处理，或采用其他适当介质进行清洗、置换，且保持足够的通风量，将危险有害的气体排出有限空间，同时降温，直至达到安全作业环境。  \n\n(2）可燃气体检测为防止爆炸事故，对有限空间的喷漆作业及作业完后，必须对可燃气体进行检测，空间内的实测值应符合当地法规的要求。未经检测的舱（室)，严禁从事任何喷涂工作。  \n\n测爆仪器必须是经国家级机构认可的仪器，国外进口的仪器，必须有产品合格证书及使用说明书，并按证书校验合格的才能使用。  \n\n测爆人员必须经过专门的测爆安全技术训练，掌握测爆理论，熟练使用测爆仪器。  \n\n舱（室）分段涂漆完毕，待涂料表面固化后，才能提出测爆申请。  \n\n应按规定选择测点。测试结束后，应在测爆申请单上签署意见，内容包括作业范围、时间、注意事项，若不符合下道工序作业条件，应予以禁止。  \n\n(3）作业安全与卫生有限空间作业人员必须经过专业安全技术教育培训。作业前应公布作业方案，对作业内容、危害等进行教育，培训还应包括有关职业安全法规、标准以及紧急情况下的个人避险常识、室息、中毒及其他伤害的急救知识等内容。  \n\n在有限空间进行涂装作业时，场外必须有人监护，遇有紧急情况，应立即发出呼救信号；在仅有顶部出人口的有限空间内进行涂装作业的人员，除佩戴个人防护用品外，还必须腰系救生索，以便在必要时由外部监护人员拉出有限空间。  \n\n在有限空间进行涂装作业时，不论是否存在可燃性气体或粉尘，都应严禁携带能产生烟气、明火、电火花的器具或火种进入有限空间。涂装作业完毕后，必须将剩余的涂料、溶剂等物全部清理出有限空间，并存放到指定的安全地点。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1652,
+        "chunk": "# 三、安全技术教育培训  \n\n涂装作业人员应按当地法规的规定进行安全技术培训，必要时应获得其上岗证书后持证上岗。涂装作业操作人员安全技术培训应包括以下内容。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1653,
+        "chunk": "# 1.涂装作业安全技术规程  \n\n旧的工作习惯很难在短时间内发生改变，养成良好的工作习惯需要深人、全面、长期的培训，并在日常工作中应明确正确的工作程序，接受监督和管理。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1654,
+        "chunk": "# 2.过程中危险有害因素  \n\n这部分内容是指工艺过程危险有害因素，安全防护措施，故障情况下应急措施；接触的有害因素对人体健康影响，个人防护知识，中毒急救措施；使用的涂料及有关化学品危险特性，防止火灾措施，灭火器材使用方法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1655,
+        "chunk": "# 3.着装与装备  \n\n施工人员需要接受连体工作衣和装备的性能、使用及保养方面的培训。并掌握袖口和手套、长裤和靴子的搭接，头罩的使用和皮肤防护霜的使用方法。  \n\n在对涂装作业人员进行安全技术培训时，应向其提供所用化学品特性和有害成分说明；化学品标识和标签包含的资料；危险化学品的安全技术说明书。未经专业安全技术培训并取得安全资格的人员不得从事涂装工程、涂装作业管理、操作、维护和检修工作。出现以下情况时，应对其进行安全技术再培训：①新的或修订的涂装安全国家标准；②进行涂装技术改进； $\\textcircled{3}$ 改变涂装工艺； $\\textcircled{4}$ 增加新的涂装设备。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1656,
+        "chunk": "# 4.个人安全  \n\n安全施工的相关指导和培训都是针对个人的，其效果也取决于个人的执行情况，其根本目的是确保施工人员得到良好的防护。  \n\n![](images/d3aeea5ed2fce452329caecc0407c629d387f66de31978551c68f398900f31c7.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 1657,
+        "chunk": "# 一、个人劳动保护用品  \n\n个人劳动保护用品（PPE）是指作业人员在生产过程中为免遭或减轻事故伤害和职业危害而随身穿（佩）戴的用品。PPE的使用作为危险保护程序仅仅限于其他控制程序不能实行的工种和工作场所。同一作业要求护品具有多种防护功能时，该PPE应具有复合性防护功能。  \n\n在涂料喷涂时应始将终穿戴适当的PPE作为附加的控制程序。PPE必须是经过国家及地方有关部门认可的、符合国家标准的产品，务必安全卫生、质量可靠。个人劳保用品的基本要求：  \n\n$\\textcircled{1}$ 选择恰当并适合于任务和人员；  \n$\\textcircled{2}$ 容易获得；  \n$\\textcircled{3}$ 清洁；  \n$\\textcircled{4}$ 使用后能正确贮藏或处理。  \n\n企业应根据安全生产和防止职业危害的需要、作业人员接触的主要危险特性或特殊劳动条件的作业类别，发给涂装作业人员适宜的劳动保护用品，并应遵守下列规定：  \n\n$\\textcircled{1}$ ①有机溶剂作业场所应提供防静电服和防静电鞋；  \n$\\textcircled{2}$ ②酸碱作业场所应提供防酸（碱）服和耐酸（碱）鞋；  \n③有限空间涂装作业场所提供供应空气的呼吸保护器。  \n\n各种防护用具应该专人保管，使用前必须按照产品使用说明认真检查，不符合标准的防护用具一律不准使用。涂装作业使用的劳动保护用品禁止穿着离开工厂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1658,
+        "chunk": "# 二、个人劳动保护用品须具备的特征",
+        "category": " Introduction"
+    },
+    {
+        "id": 1659,
+        "chunk": "# 1.基本着装  \n\n牢固的长袖棉质连体服适合大多数工种，不推荐使用易燃且可能产生静电的尼龙和聚丙  \n\n烯纤维类连体服。污染严重的连体服须立即更换。参与在短期内可能遭受严重污染的项目时，可考虑穿戴带头罩的一次性连体服。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1660,
+        "chunk": "# 2.手套  \n\n手套是用来保护手或手的一部分使其免受伤害的个体防护用品，也可以扩展到覆盖前臂的部分。合适的手套能防止皮肤直接接触溶剂等有害物质。也能帮助减少割伤和擦伤等有形损伤。在涂料喷涂时，丁睛手套能提供最好的防溶剂性能。需要更多信息时可咨询手套制造商。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1661,
+        "chunk": "# 3.工作鞋  \n\n所用的工作鞋和靴子须有钢头。任何情况下不允许穿露脚趾的便鞋。在涂料施工时，推荐使用能卸载静电、带有防滑鞋底和皮质鞋面的鞋。穿用防静电鞋、导电鞋不应同时穿绝缘的毛料厚袜及绝缘的鞋垫。使用防静电鞋的场所应是防静电地面，使用导电鞋的场所应是导电地面。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1662,
+        "chunk": "# 4.呼吸防护  \n\n在没有防护的情况下，任何人都不应暴露在能够或可能危害健康的空气环境中。  \n\n(1）呼吸防护用品的选择任何可能接触喷雾和蒸气的人必须佩戴呼吸保护装置，除了应根据有害环境选择正确的呼吸防护用品外，不同的作业状况也会影响呼吸防护用品的选择。  \n\n空气污染物同时刺激眼睛或皮肤，或可经皮肤吸收，或对皮肤有腐蚀性，应选择全面罩，并采取防护措施保护其他裸露皮肤；选择的呼吸防护用品应与其他个人防护用品相兼容。  \n\n若选择供气式呼吸防护用品，应注意作业地点与气源之间的距离、空气导管对现场其他作业人员的妨碍、供气管路被损坏或被切断等问题，并采取可能的预防措施。  \n\n若现场存在高温、低温或高湿，或存在有机溶剂及其他腐蚀性物质，应选择耐高温、耐低温或耐腐蚀的呼吸防护用品，或选择能调节温度、湿度的供气式呼吸防护用品。  \n\n若作业强度较大，或作业时间较长，应选择呼吸负荷较低的呼吸防护用品，如供气式或送风过滤式呼吸防护用品。  \n\n应评价作业环境，确定作业人员是否将承受物理因素（如高温）的不良影响，选择能够减轻这种不良影响、佩戴舒适的呼吸防护用品，如选择有降温功能的供气式呼吸防护用品。  \n\n任何呼吸防护用品的防护功能都是有限的，应让使用者了解所使用的呼吸防护用品的局限性。使用任何一种呼吸防护用品都应仔细阅读产品使用说明，并严格按要求使用。所有使用者都应接受呼吸防护服务器使用方法的培训。  \n\n(2）呼吸防护用品的使用使用前应检查呼吸防护用品的完整性、过滤元件的适用性、电池电量、气瓶贮气量等，消除不符合有关规定的现象后才允许使用。  \n\n进人有害环境前及在有害环境内作业的整个过程都应佩戴呼吸防护用品。当使用中感到异味、咳嗽、刺激、恶心等不适症状时，应立即离开有害环境，并应检查呼吸防护用品，确定并排除故障后方可重新进入有害环境；若无故障存在，应更换有效的过滤元件。若呼吸防护用品同时使用数个过滤元件，如双过滤盒，应同时更换。  \n\n除通用部件外，在未得到呼吸防护用品生产者认可的前提下，不应将不同品牌的呼吸防护用品部件拼装或组合使用。  \n\n(3）呼吸防护用品的维护应按照呼吸防护用品使用说明书中有关内容和要求，由受过培训的人员实施检查和维护，对使用说明书未包括的内容，应向制造商或经销商咨询。应按国家有关规定，在具有相应压力容器检测资格的机构定期检测空气瓶或氧气瓶。  \n\n滤芯应根据制造商的推荐和/或当地法规相关要求进行更换。滤芯式呼吸器不能用于氧气缺乏环境（当空气中的氧气含量低于 $20\\%$ )。不允许使用者自行重新装填过滤式呼吸防护用品滤毒罐或滤毒盒内的吸附过滤材料，也不允许采取任何方法自行延长已经失效的过滤元件的使用寿命。  \n\n个人专用的呼吸防护用品应定期清洗和消毒，非个人专用的每次使用后都应清洗和消毒。不允许清洗过滤元件。对可更换过滤元件的过滤式呼吸防护用品，清洗前应将过滤元件取下。呼吸防护用品应保存在清洁、干燥、无油污、无阳光直射和无腐蚀性气体的地方。若呼吸防护用品不经常使用，建议将呼吸防护用品放人密封袋内贮存，贮存时应避免面罩变形。  \n\n所有紧急情况和救援使用的呼吸防护用品应保持待用状态，并置于适宜贮存、便于管理、取用方便的地方，不得随意变更存放地点。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1663,
+        "chunk": "# 5.眼面防护用品  \n\n所有喷涂操作必须保护眼睛。应佩戴安全的护目装备，比如安全眼镜、护目镜、面罩等以免溅到液体。眼面防护用品应当符合相应的标准。镜片或面材须能抵抗所用的溶剂。当涂料混合或倾倒操作会造成飞溅的风险时，就应佩戴整个面部的防护。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1664,
+        "chunk": "# 6.听力防护用品  \n\n因为听力的损失是不可恢复的，当暴露于噪声中时，应对听力进行保护。生产车间和作业场所的工作地点的噪声标准应符合当地的法规要求，未达到标准的必须发放听力防护用品。通常当作业环境噪声超过85dB时就应使用适当的听力防护用品，如耳塞或耳罩。所使用的护耳器须适合周边声音的频率。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1665,
+        "chunk": "# 7．身体防护  \n\n应穿着覆盖身体、手臂和腿部的工作服，皮肤不应暴露。隔离性护肤霜可有助于保护难于遮盖的皮肤，例如面部和颈部，但是一旦已接触有害物质，则不应再使用。护肤用品在使用条件下应具有无毒、无菌、无刺激等安全性能，应正确选择隔离性护肤霜，凡士林因能使溶剂渗透，导致暴露，涂装作业不应选择凡士林等矿脂型护肤品。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1666,
+        "chunk": "# 三、个人劳动保护用品的维护和报废规定  \n\n（1）个人劳动保护用品维护内容应包括： $\\textcircled{1}$ 定期清洁与消毒。 $\\textcircled{2}$ 用品的干燥。 $\\textcircled{3}$ 缺陷与损坏的检查。 $\\textcircled{4}$ 老化和坏损部件的修理与更换。 $\\textcircled{5}$ 不使用时的贮存。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1667,
+        "chunk": "# (2）报废规定  \n\n企业内的安全技术部门每年应定期或不定期检查涂装作业劳动保护用品，需要技术鉴定的送国家授权的劳动保护用品检验站检验。  \n\n不符合下列条件之一的，应立即予以报废，报废后的劳动保护用品禁止作为劳动保护用品使用。  \n\n$\\textcircled{1}$ 不符合国家标准或专业标准。  \n\n$\\textcircled{2}$ 未达到上级劳动保护监察机构根据有关标准和规程所规定的功能指标。$\\textcircled{3}$ 在使用或保管贮存期内遭到损坏或超过有效使用期，经检验未达到原规定的有效防",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1668,
+        "chunk": "# 护功能最低指标。  \n\n![](images/d95d9a9fc497758ae934ea5f52d7299c9c5833d100d360245f9cce6ace9abbf5.jpg)  \n\n涂料可能对皮肤和呼吸系统造成长期的及终生的疾病。涂料的使用都应明确并严格遵守当地健康、安全和环保的相关法规，在涂装施工前应要求涂料供应商提供涂料产品的安全健康说明书。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1669,
+        "chunk": "# 一、健康危害  \n\n喷涂过程中产生的雾状的湿涂料小颗粒称为漆雾，溶剂挥发十燥后的漆雾又被称为漆雾粉尘。含异氰酸酯的蒸气、漆雾和喷尘会刺激呼吸道及眼睛，可能会引起皮肤的过敏反应，并诱发或加重哮喘或皮炎。  \n\n职业性皮肤过敏是人体对某种物质的过敏性反应，这种反应常常难区别于一般的刺激反应。过敏反应可能在一次或多次接触某种物质之后的一段时间后才会出现症状。若某人对某种物质过敏，那么即使接触到的数量极少也会引起过敏性反应。  \n\n例如，异氰酸酯可能会引起呼吸道过敏，有时也被称作“职业性哮喘”。早期已有案例证明这也可能造成非常严重和致命的后果。过敏的早期症状可以表现为流泪、流涕，继续发展会导致气喘、胸闷、咳嗽或窒息。  \n\n目前，异氰酸酯固化涂料的喷涂施工的接触性是最高的，接触异氰酸酯的危险在喷涂施工中比在刷涂或辊涂施工中要多得多。根据英国健康与安全协会的统计，它是英国职业哮喘病的最主要的原因之一。如包装和控制不当，异氰酸酯的漆雾和蒸气可能扩散到作业区域外，给他人的健康带来危害。相对于湿涂料，干燥的漆雾粉尘的危险则要小得多。通过佩戴适当的个人劳保用品和保持良好的卫生习惯可以把潜在的危害减少到可接受的程度。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1670,
+        "chunk": "# 二、有工作危险的人员  \n\n显然越靠近涂料作业的人，接触到涂料和漆雾尘埃的可能性越大。但是每一个在漆雾尘埃可及范围内的人均会有危险，他们包括：  \n\n$\\textcircled{1}$ 喷漆者和高空车驾驶员；$\\textcircled{2}$ 涂料混合和搅拌及喷漆泵的操作人员；$\\textcircled{3}$ 其他在涂料飞溅区工作的人员，如装配工、搬运工、监工、操作工及涂料技术服务人员；$\\textcircled{4}$ 其他可能接触干喷的人员，如脚手架拆卸工、拆除螺旋桨遮盖膜的操作员、船坞及清洁人员等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1671,
+        "chunk": "# 三、防护措施  \n\n最佳的预防措施是尽可能远离涂料施工区域，尽可能减少人员接触涂料、喷雾和干喷的机会。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1672,
+        "chunk": "# 1.在喷漆过程中  \n\n当喷涂施工开始时，在作业现场区域内只能有喷漆人员和高空行车驾驶员；看泵人、监  \n\n工和技术服务代表应站在喷涂区外或者站在喷涂施工的上风向，其他人员应远离施工区域。应尽可能在喷漆区域前设置“禁人区”标志，任何进入“禁人区”的人员均必须穿戴适当的防护用品，特别要进行呼吸保护。  \n\n应避免在大风天气喷涂涂料。在密闭区域喷涂时，必须确保有完善的安全作业程序。如使用异氰酸酯固化涂料、防污漆等除应遵循常规喷涂的规定外，还应遵守其相关具体规定。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1673,
+        "chunk": "# 2.在喷漆结束后  \n\n在喷涂结束后，应清除干喷漆雾，防止其随风扩散；落到脚手架、保护遮蔽等物件上的干喷应及时冲洗掉或扫掉，废弃物应根据当地法规进行合法处置。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1674,
+        "chunk": "# 3.贮存和管理  \n\n涂料通常含有溶剂。溶剂蒸气重于空气，会沿着地面扩散，与空气形成爆炸混合物。因此贮存、生产和施工区域应通风，以避免空气中易燃或易爆蒸气浓度高于所允许的接触最高值。  \n\n产品应贮存于干燥，通风良好，远离热源和阳光直射的地方。贮存在混凝土地面或其他不可渗透的地面上，最好带有能容纳溢出物的层面。  \n\n产品堆码不能高于三层托板。包装容器要盖紧。开启过的容器必须再仔细密封，并保持竖放，以防泄漏。未经批准不得进人贮存区域。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1675,
+        "chunk": "# 四、工作服与装备  \n\n涂料喷涂施工只能在合适的、具备有效排气通风装置的室内使用，以避免喷雾逸出工作区域。当在有限的空间进行喷涂作业时，即使空气流通时也必须佩戴供气的呼吸保护装置。除非特别说明，关于PPE的信息适用于所有施工方式。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1676,
+        "chunk": "# 1．工作服  \n\n所有施工人员（喷漆工、高架车操作工、看泵人、管理人员、技术服务人员）都应穿着以下工作服：  \n\n$\\textcircled{1}$ 长袖长裤腿连体服或一次性的带兜帽的连体工作衣 (穿在棉质连体工作衣外)；  \n$\\textcircled{2}$ 长筒手套；  \n$\\textcircled{3}$ 长筒靴，能保护脚踝和小腿下部。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1677,
+        "chunk": "# 2.呼吸防护  \n\n当喷涂过程中有接触涂料喷雾、蒸气的危险时，喷漆工和其助手必须佩戴适当的呼吸器，如有需要应提供通风设备进行排风。该设备应能保护穿着者避免吸入颗粒。应选用经过核准的呼吸器。在有限空间使用该产品时必须佩戴供气呼吸器，即使在开放的空间，喷漆的时候也应该佩戴供气呼吸器。当在开放且通风良好的区域用刷子和辊筒操作产品时可以用过滤面具代替供气呼吸器。如果供气呼吸器不适用，应佩戴合适的、带筒形滤芯的呼吸器。  \n\n呼吸防护设备不能存放于可能会遭受污染的环境。应经常检查呼吸防护设备和滤芯，以保证呼吸装置的状态。  \n\n喷漆手及其助手和操作工应佩戴防溶剂的呼吸保护器。这包括保护整个脸部皮肤。施工组的其他人员应佩戴防溶剂和微小颗粒的半遮面呼吸器。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1678,
+        "chunk": "# 3.眼睛防护  \n\n施工者在喷涂和搅拌过程中，应佩戴全遮面式保护装备。  \n\n每个在现场工作的人员都必须使用眼面保护用具。如安全眼镜、护目镜、防护面罩等以免溅到液体。护目装备应当符合相应的标准。当混合或倾倒操作会造成飞溅的风险时，就应佩戴整个面部的防护。作为一个好的工作惯例，建议设立固定的冲洗眼睛的装置。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1679,
+        "chunk": "# 4.皮肤防护  \n\n因涂料会造成过敏性和潜在危害，应使用PPE尽可能地保护皮肤。  \n\n在混合涂料和施工时，应当戴好由适当材料制成的手套。应穿看遮盖身体、手臂和腿部的工作服，皮肤不应暴露。隔离性护肤霜可有助于保护难于遮盖的皮肤，例如面部和颈部，但是一且已接触，则不应再使用。不应使用诸如凡士林等矿脂型护肤品。接触产品后应清洗全身。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1680,
+        "chunk": "# 5.高温天气  \n\n在炎热天气下，紧贴皮肤的连体服很快会被汗水浸湿。此时，工作服外涂料污渍中的化学物质会渗透连体服，接触并刺激皮肤。为避免此种情况，推荐穿着内外两件连体服；或是能提供足够防护且不会被涂料和汗水浸透的单层连体服。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1681,
+        "chunk": "# 6.着装习惯  \n\n为避免涂料与人体直接接触，任何时候都应正常穿戴个人劳保用品。  \n\n连体服必须充分伸展，完全覆盖全身，不可卷起袖子裤腿，以避免皮肤接触涂料。头罩应紧贴脸部；里层棉质连体服的衣袖口、裤腿可分别塞入手套和长筒靴内；可弃式（一次性）连体工作衣应遮盖住手套和工作靴，袖口和手套之间不应有空隙使皮肤暴露。可使用胶带密封袖口和手套的连接处。手套应有长袖筒。  \n\n连体服应有自粘搭扣，或有松紧的袖口，以确保袖口盖住腕处，在连体服和手套之间无皮肤暴露。也可使用同样的方法确保靴子和裤脚之间连接紧密无间隙。应穿着带铁头并至少半遮小腿的靴子。不能穿低帮鞋和便鞋。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1682,
+        "chunk": "# 7.换装和清洁习惯  \n\n一次性连体工作衣在每次使用后应及时更换，至少应每天更换。丢弃的连体服应正确处理。  \n\n在涂料施工后，应更换并清洗棉质连体服。如有涂料渗透到连体服内层，应立即更换。如手套内层有溶剂渗入或内层已被污染，应立即更换，亦可考虑在内部加戴一双棉/线手套。安全帽内的吸汗带应经常清洗，应用清洁剂和水清除帽子上的污染物和干喷污染物。  \n\n在每个班次之后，应使用清洁剂和水清洗全遮面和半遮面面具的内外侧，并存放于专用的地点。半遮面面具应每日更换，或如果有气味应更频繁地更换。在前一班结束后下一班开始前，应更换滤芯。施工含异氰酸酯涂料时，应确保使用正确的滤芯式呼吸器。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1683,
+        "chunk": "# 8.注意个人卫生  \n\n在如厕前，抽烟、吃喝前应脱掉外层连体服，认真地洗手。  \n\n人体皮肤大多比手部皮肤细腻娇嫩，它们若接触到刺激性物质会令人感到不适，此种情况应尽量避免。  \n\n接触到涂料或漆雾的施工人员，在工作结束后应洗澡。不能直接换上生活装或穿着工作服回家。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1684,
+        "chunk": "# 五、急救措施",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1685,
+        "chunk": "# 1.一般处理  \n\n如有任何疑问或症状，应立即去医院治疗。不得给失去知觉的人通过口腔喂食任何  \n\n东西。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1686,
+        "chunk": "# 2.皮肤接触  \n\n目前对于皮肤刺激和过敏尚没有特效解毒药。一旦接触到有害物质，应立即脱去沾污的衣物，用肥皂水或认可的皮肤清洁剂轻柔并彻底地清洗所有充血的部位，然后涂抹上消炎药膏。勿用溶剂或稀释剂进行清洗。  \n\n受创部位会在几天内康复。如皮肤状况有恶化的迹象，应立即就医。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1687,
+        "chunk": "# 3.眼睛接触  \n\n如涂料或漆雾进入眼睛，应拨开眼脸用清水或生理盐水冲洗至少 $10\\mathrm{min}$ 以上，若仍感不适，应立即就医。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1688,
+        "chunk": "# 4.吸入  \n\n将病人移至空气新鲜处，使其保持安静并保暖。如呼吸不正常或停止，应进行人工呼吸。如失去知觉，应使其保持安全姿势并立即找医生治疗。不可喂食任何东西。发现任何呼吸系统症状应立即就医。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1689,
+        "chunk": "# 5.吞入  \n\n如不慎吞人涂料或稀释剂等，应立即找医生治疗，不要紧张，不要试图呕吐。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 1690,
+        "chunk": "# 六、泄漏应急处理  \n\n发生涂料或稀释剂泄漏时，应移除火源，禁止开灯和开启或关闭不防爆的电器。如果在有限空间内发生大量溢漏，应疏散该区域的人群，再次进入之前应确保溶剂蒸气量低于它的爆炸下限。同时还要保持通风，避免吸人溶剂蒸气。  \n\n使用不易燃材料来容纳和吸收泄漏物，例如沙子，泥土或者蛭石。将其置人一个合适的盖子较松的容器中以避免气体膨胀(如异氰酸酯会与湿气反应释放出二氧化碳)。  \n\n受污染区域须立即用去污剂进行清理。在残余物中加人合适的去污剂，放置在非密封容器中若干天直至反应不再持续后方可将闭紧的容器按照当地的废物处理法规进行处置。  \n\n严禁让泄漏物料进入排水沟和任何其他水道。如果有任何土地和水受到污染请告知当地的环境保护部门。  \n\n![](images/81c138d4c1b382a0d41a37809c9543316f16924de416d5aa94b6870045a04a27.jpg)  \n\n进行表面处理并使用液体涂料施工时，大部分所使用的材料都含有对健康有害或有毒的物质，所使用的方法和设备也可能会对工人的健康和安全构成危险。大部分液体涂料都存在爆炸危险，而此类操作产生的污染可能对环境造成不利影响。  \n\n世界上的大部分国家都制定了相关法规标准、管理职业安全、工人安全和环境保护的相关事务。除了现有的法律之外，行业及公司一般也都制定了相应的标准和规定对这些方面进行管理。  \n\n涂料施工方和涂料供应商有责任采取防范措施来保护员工健康，避免事故发生，保护环境免受污染。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1691,
+        "chunk": "# 一、健康安全  \n\n在防腐涂装作业过程中的职业健康安全危害主要出现在以下几个方面。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1692,
+        "chunk": "# 1.粉尘  \n\n涂装作业的各个工作步骤中都会产生粉尘，有时还会产生大量的粉尘。这些粉尘都是潜在的刺激物，在喷砂作业中（尤其涉及防污漆）产生的粉尘是有毒粉尘。  \n\n生产性粉尘会危害到操作者的眼睛、黏膜（呼吸道）和肺，轻的会引起流泪或者咳嗽，高浓度的刺激性粉尘可能会造成急、慢性中毒。  \n\n通过空气传播的有毒粉尘主要来自于对涂装表面的打磨、喷砂清洁及液体涂料的喷涂作业，这些粉尘可能含有重金属（如锡、铅、镉)、致癌物质（如焦油、沥青、铬）等有毒物质。有毒物质可能通过呼吸道、消化道及皮肤侵入人体，有的可能刺激上呼吸道黏膜，有的会引起过敏反应或皮炎，有的会造成急性中毒（如在过度接触锡和锌时）或慢性中毒（如在长期接触焦油、沥青、锡时)，有的可以或可能致癌、致畸、致突变等。值得注意的是，空气传播有毒粉尘颗粒可以随风传播相当长的距离，此距离内的影响也应纳入防护的考虑。  \n\n一般防护措施通常是在工作场所安装带废气过滤的通风装置，施工者穿戴必要的个人防护用品，如隔离工作服、手套、过滤面罩、护目镜或防护霜等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1693,
+        "chunk": "# 2.烟尘和蒸气  \n\n钢材的焊接和热处理会产生烟尘，尤其是喷涂了预涂底漆或者完整的涂层系统的钢材。烟尘来自于焊接电极及涂料的燃烧。显然，这些烟尘同样会造成职业性健康伤害，必须加以防范。对于原来喷涂过涂层的钢材来说，可以通过打磨或喷砂去除全部涂层系统来使这一问题得到缓解。  \n\n焊接和燃烧工作区域内应采取良好的全面通风措施，排出工作现场的烟尘。必要时，焊接工人必须佩戴个人过滤面罩，甚至应为每个工人提供独立供气系统。  \n\n蒸气的产生主要由于含溶剂涂料的使用，喷涂以及干燥/固化过程中都有溶剂的蒸发。大部分溶剂都含有有毒物质，接触这些物质可能对工人造成急性和慢性影响。溶剂蒸气通过呼吸道及皮肤侵入人体，可能对下列器官具有毒性和破坏性：①大脑和神经；②眼睛；③呼吸系统； $\\textcircled{4}$ 皮肤； $\\textcircled{5}$ 循环系统（肝肾）； $\\textcircled{6}$ 生殖系统。  \n\n急性中毒症状主要和溶剂的毒性有关，开始可能是头晕乏力(或者耳鸣)，严重的最终会失去知觉。慢性中毒症状可以表现为：注意力无法集中、丧失协调能力、丧失记忆，往往还会伴随着过度兴奋和具有攻击性。换句话说就是大脑和神经受到了损害。有报道证明，溶剂中毒还会造成肝肾的损伤。  \n\n世界卫生组织（WHO)、国际癌症研究机构（IARC）还指出了涂料工人所面临的职业风险。在“部分有机溶剂、树脂单体和相关化合物、颜料以及涂料生产和涂装的职业暴露对人体致癌风险评估专论”一文中，IARC做出了一系列阐述，其中就指出了“涂料工人的职业暴露可能引发癌症，具有致癌性”。值得注意的是IARC在这里并没有指明某种特定的化学物质或者某类化学物质是致癌的，而是得出“涂料工的工作是致癌性的”这个总体结论。  \n\nIARC的专论中的其他相关资料说明涂料工人可能患上职业性刺激性和职业过敏性接触性皮炎(皮肤问题)、慢性支气管炎和哮喘（肺部问题)，并对神经系统产生不利影响（溶剂神经毒性)。IARC推断说有迹象表明此类工作可能还会对肝、肾、血液和造血器官产生不利影响。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1694,
+        "chunk": "# 3.坠落和摔倒  \n\n在防腐涂装作业过程中，施工伤害除了接触有害因素外，相关部分与坠落和摔倒有关，如从梯子、脚手架或者起重机上坠落，踩在未干的涂料、尘土上滑倒，或者被管子和电线绊倒的现象。  \n\n一般来说，这类危险只要正确架设脚手架就可以有效减少。不少国家都针对脚手架的架设与安装制定了一些规定和法规，但在许多情况下尚未充分涉及防腐行业的特殊需求。随着该产业内高压水喷射应用的不断增加，脚手架的安装和架设过程中将必须考虑到这种技术的特殊要求。  \n\n消除滑倒和绊倒危险的最佳方式是对作业现场进行有效的管理，达到良好的整理和清洁。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1695,
+        "chunk": "# 4.爆炸和火灾  \n\n在实际应用中，应该知道液体涂料中使用的所有溶剂都存在爆炸和火灾危险。为了达到快干涂料的要求，绝大部分所使用的溶剂都具有高挥发性。这意味着溶剂的浓度将迅速达到可能发生爆炸和火灾的水平。  \n\n对于爆炸来说，有限空间及通风不良的场所内易燃气体浓度及粉尘浓度达到爆炸极限时，遇到着火源就会瞬间燃烧爆炸。  \n\n火灾或爆炸的发生必须具备氧气、可燃物质和着火源三个条件。防火防爆的主要工作就是消除着火源。因此不得在可能含有稀释剂或涂料产生的溶剂烟气的区域进行像焊接或者燃烧这样的高温作业；涂料施工区域内的电气设备和装置必须是防爆型的；可能或者已知会产生静电的设备（比如无气喷涂设备等）必须正确接地；像热风机这样的加热器不得放在可能达到一定的溶剂蒸气浓度的区域，也不能用含有溶剂蒸气的空气作为此类设备的进气。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1696,
+        "chunk": "# 二、环境保护措施  \n\n由于防腐涂装作业中会使用到大量的有毒有害物质，同时涂装过程中还会对环境造成危害。目前预防性的环保工作主要集中在以下四个领域： $\\textcircled{1}$ 粉尘控制； $\\textcircled{2}$ 溶剂控制； $\\textcircled{3}$ 噪声控制； $\\textcircled{4}$ 废物处置。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1697,
+        "chunk": "# 1．粉尘控制  \n\n如上所述，防腐涂装作业活动将产生大量粉尘，并且这些粉尘可能通过空气传播到离实际工作场地很远的地方。这些含有有害物质的喷涂涂料粉尘可能积聚在停放车辆上，落在地面上，渗透到土壤中污染水源。  \n\n喷漆前钢材或混凝土表面的喷砂处理可能从基材表面本身或者基材表面的现有涂层上产生大量的有害灰尘，因此也可能会对环境造成不利影响。  \n\n许多地方已经限制在室外进行维修喷涂和喷砂处理工作，如美国已经制定了法规强制要求将废物作为有毒材料进行收集和处理。虽然这些规定增加了维修的成本，但涂料行业已经开发出了无需喷砂处理的替代涂料品种。降低成本的另一种有效方法是喷砂材料的循环利用，这不仅可以更有效地利用喷砂介质，同时还可以减少废物的产生。  \n\n还有一些国家或地区采用替代性的喷砂方法，如高压水喷射等，用于应对维修工作中的粉尘危害，同时减少废弃材料的产生。  \n\n人们对喷砂清洁方法以及用过的喷砂材料相关危害的认识的不断提高，促使人们不断努力来寻找替代性的清洁方法和新型涂料。  \n\n实现尘埃控制的措施包括遮盖工作区域、过滤来自建筑物和工棚的排气、不要露天弃置尘埃致其随风飘散等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1698,
+        "chunk": "# 2.溶剂控制  \n\n在过去的几十年间，尤其是在美国和欧洲的涂料生产商和消费者们都受到了来自政府立法机构的越来越大的压力，被要求减少甚至是去除产品和各种生产工艺中的挥发性有机物(VOC).  \n\n环境问题引起了人们对涂料中挥发性有机物的特别关注，这是因为挥发性有机物会与NO（氮氧化物）结合形成对流层中的臭氧。而臭氧将不利于植物的生长，极端情况下还会损伤植物的叶子。  \n\n大部分有机溶剂都能形成臭氧，但它们的反应可能性和速率各不相同。烃的反应速率比醇快，从而导致了工厂区域所形成的烟雾数量的增加。氯化烃不会形成对流层中的臭氧，但它们可以破坏大气最上部保护地球的臭氧层。因此它们不能作为烃和醇等溶剂在环境上可以接受的代替品。  \n\n显然重新调整溶剂混合物的配方是无法解决臭氧问题的。减少对流层中臭氧的形成唯一有效的解决办法就是通过增加水性涂料和无溶剂涂料的使用，来减少溶剂散发。  \n\n人们最关心的还是空气污染问题。全世界的涂料年销售量约为1500万吨，而大部分涂料中有50%是由有机溶剂构成的，涂料当然会引起人们对溶剂散发的关注。由于溶剂现在被认为是主要的空气污染源之一，因此涂料的生产商和用户们就不得不遵守各地的排放法规。  \n\n涂料中的VOC含量和由于溶剂的大量排放所导致的潜在风险无疑是全球的涂料产业最关心的问题。",
+        "category": " Introduction"
+    },
+    {
+        "id": 1699,
+        "chunk": "# 3.噪声控制  \n\n和有毒化学物质一样，噪声同样可能对进行防腐涂装作业的工人造成威胁。除了听力受损这样明显的健康风险之外，噪声音量过高还可能造成其他危险，如工人可能无法听到附近的同事发出的警告。因此必须对暴露于噪声的情况进行监测，当噪声超过安全水平时，必须采取措施对工人进行保护。  \n\n大多数场地的两个主要噪声源包括：  \n\n$\\textcircled{1}$ 场地产生的或者与工艺相关的永久噪声源，如蒸汽通风口和空压机等；$\\textcircled{2}$ 承包商造成的暂时性或间歇性噪声源，如供气式喷砂面罩、喷砂以及电动工具清洁等。  \n\n企业必须了解所有场地产生的或者与工艺相关的永久噪声源，并在现场平面图上绘出这些“必须进行听力保护”的区域。即使此类管制区域不要求承包商对永久性噪声级进行监测，承包商也必须考虑这些区域产生的噪声对员工所经受的最终总噪声水平的影响。  \n\n承包商造成的暂时性噪声源可以通过对噪声水平的取样或区域监测知道。承包商有责任保护其雇员、其他职业人员以及该地区来自其他行业的人员免受噪声源的影响。综上所述，必须测量并了解总体的噪声环境—一现有的工艺水平和维护操作。  \n\n进行维修涂料的工人要连续受到原本很安静的工厂场地内喷砂产生的高噪声水平的困扰，其作业在“必须进行听力保护”的区域内，他们应当受到和船东的雇工同等的关注。  \n\n承包商造成的噪声可以通过简单的书面程序加以管理，其内容包括工程控制、取样、教育以及个人防护等。  \n\n噪声控制必须首先考虑工程控制，这是因为源头控制是噪声问题的首选解决方案。最好只能允许噪声水平较低的（小于85dB）空压机和其他设备进人现场。承包商带人现场的所有机器，如果运行时高于这一水平或者无法保持安静，则必须首先在全速运转的情况下进行噪声水平检测。随后噪声水平高于85dB的机器应当设置围栏，并按照下述步骤设置警示标志。当工人在未被工厂所有者宜布成为必须进行听力保护的区域内，开始使用喷砂设备、电动工具或者其他能够产生高噪声（不低于85dB）的设备时，应对噪声水平进行检查。工作开始时，应在噪声源处测取声音水平读数。然后将分贝计从噪声源处逐渐移开，直至读数降至85dB以下为止。而围栏就应设在该点处，并用标识说明“越过此点为高噪声水平——必须进行听力保护”。应当通过工人用领口的计量仪对喷砂头盔内本班次的噪声读数进行计量，并对来自喷砂头盔、供气设备、空压机以及其他产生噪声的设备的供货商提供的噪声水平数据进行整理；还应该用声量计进行抽查，以确认早先的数据。美国国家职业安全与健康协会建议头盔内的噪声水平应小于80dB。  \n\n此外，工厂厂主在向合同工介绍场地时，要强调指出场地内必须进行听力保护的区域的所在位置。其他可能产生高噪声的间歇性噪声源（如蒸汽释放阀等）也应当加以明确，并纳入承包商为员工进行的危险评估和介绍计划。  \n\n如果噪声被强调为一种危害的话，那么就必须配备听力防护措施，并对其使用进行监督。  \n\n综上所述，由于承包商所雇用的操作工人的非连续性特点，作为未来基准的对维修合同工人的听力检测、定期检测，往往不能达到真正目的。尽管如此，承包商可能还是希望在新工作开始前对所有的工人进行基本检测，用于确定听力受损水平。这些数据可以用于将处于危险状态的工人安排到噪声程度较低的区域，从而避免以后有关的纠纷。  \n\n在防腐工作中所使用的大部分机器都会产生噪声，这是不可避免的，但可以采取某些措施来降低噪声的水平。  \n\n通过采用听力保护措施，可以很好地保护工人免受噪声的危害，但身处工作场地环境中的人们实际情况却不是这样，这些必须予以考虑。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1700,
+        "chunk": "# 4.废物处置  \n\n在最普遍的定义中，危险废弃物是指那些若处理不当，可能对人体健康或环境造成真正威胁或危害的所有废弃物。一般来说，如果一种材料表现出了在现有法律中列为危险废弃物特征的任何特性，那么就会被认为是危险废弃物。  \n\n在大部分国家，对于会产生如喷砂清洁残渣、废料、涂料残渣等废物的设备，其运营者必须遵守此类废物处置的法规措施。运营者，不论规模大小，都必须了解并遵守此类法律法规，并对废物进行合法处置。建议设备运营商与有关主管部门联系，获取该方面的最新资料，因为这是一个不断发展的领域。  \n\n设备运营商有责任确定适用于其操作的国家、地区和当地的法规，并确定如何让设备运行符合法规的要求。  \n\n大部分来自涂料操作的废弃物材料由于具有可燃性，都被证明属于危险废弃物。这一特征被定义为闪点低于 $60^{\\circ}C$ 的液体，或者可能由于摩擦引发火灾的废弃物，它们在被点燃时，会剧烈燃烧，造成危害。涂料、稀释剂以及清洁剂中使用的大部分溶剂的闪点都在 $60^{\\circ}C$ 以下。  \n\n导致某些残留物和涂料废弃物被归于危险废弃物的另一个特点是毒性。具有此特性的材料被定义为可能向地下水渗透含有特殊有害成分的有害浓缩液的废物。这些被人们所关注的成分主要有基于铅、铬和镉的颜料和添加剂，以及在处理、施工和涂层去除过程中所产生的各种有机物。  \n\nSPUA材料属于难降解的高分子材料，其废弃物通常采用掩埋处理，不会对环境造成污染；或者对其进行粉碎造粒，用作其他产品的耐磨填充材料。就目前的技术状态而言，还没有对其进行分解、回收等无害化处理的工艺装置；建议用户不宜采用烧的方式进行处理，否则会产生大量有害物质污染环境、损害人体健康。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 1701,
+        "chunk": "# 5.与涂装安全、防护相关的国家标准和行业标准  \n\nGB6514—1995《涂装作业安全规程 涂漆工艺安全及其通风净化》   \nGB7691—2003《涂装作业安全规程 安全管理通则》   \nGB7692—1999《涂装作业安全规程涂漆前处理工艺安全及其通风净化》   \nGB/T11651—1989《劳动防护用品选用规则》   \nGB12367—2006《涂装作业安全规程静电喷漆工艺安全》   \nGB/T12624—2006《劳动防护手套通用技术条件》   \nGB/T12903—1991《个人防护用品术语》   \nGB12942—2006《涂装作业安全规程有限空间作业安全技术要求》   \nGB/T13641—2006《劳动护肤剂通用技术条件》   \nGB/T14441—1993《涂装作业安全规程术语》   \nGB14444—2006《涂装作业安全规程喷漆室安全技术规定》   \nGB/T18664—2002《呼吸防护用品的选择、使用与维护》   \nCB3381—1991《船舶涂装作业安全规程》   \nHG/T2458—1993《涂料产品检验运输和贮存通则》",
+        "category": " References"
+    },
+    {
+        "id": 1702,
+        "chunk": "# 参考文献  \n\n[1] GB6514—1995．涂装作业安全规程 涂漆工艺安全及其通风净化[2] GB7691—2003．涂装作业安全规程安全管理通则.  \n[3] GB7692—1999.涂装作业安全规程涂漆前处理工艺安全及其通风净化.  \n[4] GB/T11651—1989.劳动防护用品选用规则.  \n[5] GB12367—2006．涂装作业安全规程静电喷漆工艺安全.  \n[6] GB/T12624—2006.劳动防护手套通用技术条件.  \n[7] GB/T12903—1991.个人防护用品术语.  \n[8] GB12942—2006，涂装作业安全规程有限空间作业安全技术要求.  \n[9] GB/T13641—2006.劳动护肤剂通用技术条件.  \n[10] GB/T14441—1993.涂装作业安全规程术语.  \n[11] GB14444一2006.涂装作业安全规程喷漆室安全技术规定.  \n[12] GB/T18664—2002.呼吸防护用品的选择、使用与维护.  \n[13] CB3381—1991.船舶涂装作业安全规程.  \n[14] HG/T2458—1993.涂料产品检验运输和贮存通则.  \n［General Information]  \n书名 $\\c=$ 涂料工艺（第4版）下册  \n作者 $\\mathbf{\\bar{\\rho}}=\\mathbf{\\rho}$ 刘登良主编  \n页数 $\\mathbf{\\tau}=\\mathbf{\\tau}$ 1800  \n出版社=化学工业出版社  \n出版日期 $\\c=$ 2010  \nSS号 $\\c=$ 12473664  \nDX号=  \nURLhttp:llbookl．duiu．comlbookDetail．jsp?d  \nNumbr=&d=204018350E153ABB9B73FEBC82B56715  \n封面  \n书名  \n版权  \n前言  \n目录  \n第三篇涂料各论  \n第三章 重防腐涂料  \n第一节 金属腐蚀与防护简论&李荣俊‧李兴仁金属腐蚀的定义金属腐蚀的危害性三、金属腐蚀的分类四、金属在自然环境中的腐蚀  \n第二节 重防腐涂料简述&李荣俊孙凌云、 重防腐涂料的特点常用重防腐涂料简述  \n第三节 重防腐涂料涂装&李荣俊‧黄安‧李华刚1、 重防腐涂装设计原则“全寿命经济分析法”设计思想简介三、 防腐涂层配套体系的设计四、 重防腐涂装施工工艺要点  \n第四节 混凝土结构的腐蚀与防护&林绍基李荣俊1、 混凝土结构腐蚀的严重性一、 钢筋混凝土结构的腐蚀机理三、钢筋混凝土腐蚀环境分析四、混凝土结构腐蚀防护措施五、混凝土防护涂层配套体系六、混凝土结构防护涂装的特殊性和施工工艺要点  \n第五节典型重防腐涂料与涂装一、桥梁防腐涂料与涂装&孙凌云李兴仁石油化工防腐蚀涂料& 刘新  \n三、建筑钢结构防腐蚀涂料& 刘新  \n四、港口机械与设备钢结构防护涂装&马赫‧李荣俊‧刘新五、电力系统用防腐涂料&黄安李桂宁 宋志荣史春晖六、地坪涂料&周子七、耐温防腐涂料& 唐峰王健八、机车涂料&孟庆昂九、工程机械涂料& 刘新易海瑞  \n参考文献  \n第四章海洋涂料  \n第一节‧船舶涂料一、 船舶涂料概况&王健车间底漆&王健袁林森三、船底防锈漆&金晓鸿四、船底防污漆&任卫东 王健五、船壳／甲板漆&唐海英六、各种舱室漆&金晓鸿朱红七、船舶漆的涂装& 龚骏‧朱洪　王健  \n第二节集装箱涂料&刘会成1、 集装箱涂料简介集装箱涂料的配套方案和集装箱涂料三、集装箱生产线及对涂料性能的要求和影响四、常见的涂膜病及解决方法五、集装箱涂料、涂装的发展趋势  \n第三节海洋工程重防腐涂料&刘新　杜阳、海洋油气资源开发及海洋工程简史",
+        "category": " References"
+    },
+    {
+        "id": 1703,
+        "chunk": "# 二、海洋工程结构物分类",
+        "category": " Introduction"
+    },
+    {
+        "id": 1704,
+        "chunk": "# 三、海洋的腐蚀环境  \n\n五、海洋工程防腐涂料六、海洋工程防腐蚀涂料性能要求七、海洋工程防腐涂料系统八、海洋工程涂装质量要求  \n参考文献  \n第五章预涂卷材涂料&王利群  \n第一节　预涂卷材概述  \n第二节　预涂卷材生产工艺  \n第三节 底材的预处理、 脱脂二、 表面调整处理三、 化学转化处理四、环保型处理液  \n第四节 预涂卷材涂料概述预涂卷材涂料的特点和性能要习预涂卷材涂料的组成三、 预涂卷材涂料性能的影响因素四、预涂卷材涂料的性能检验标准五、预涂卷材涂料的性能检验方法  \n第五节 预涂卷材用底漆1、 预涂卷材底漆概述预涂卷材底漆的组成三、环氧类底漆四、聚酯类底漆五、高性能卷材底漆六、水性底漆  \n第六节 预涂卷材用面漆、 预涂卷材用面漆概述一 聚酯类面漆三、 聚乙烯类面漆四、 丙烯酸类面漆五、耐久型面漆  \n第七节 预涂卷材用背面漆1、 背漆概述环氧背漆三、 聚酯背漆  \n第八节 卷铝涂料卷铝及铝塑复合板生产工艺三、 卷铝涂料  \n第九节 卷材涂料新进展1、 家电用卷材涂料汽车用卷材涂料三、 食品罐用卷材涂料四、隔热卷材涂料五、纳米材料的应用六、特殊功能性彩板用卷材涂料七、环保卷材涂料八、结论  \n参考文献  \n第六章塑料涂料&李少香  \n第一节‧塑料底材的特征一、塑料的组成与分类",
+        "category": " References"
+    },
+    {
+        "id": 1705,
+        "chunk": "# 二、塑料的特性",
+        "category": " Introduction"
+    },
+    {
+        "id": 1706,
+        "chunk": "# 三、常用塑料性能简介  \n\n第二节 塑料涂料的附着力、 塑料制品的表面张力及液体在聚合物表面润湿和铺展的基本条件、 溶解度参数  \n\n三、提高漆膜附着的途径  \n第三节塑料底材的表面处理塑料的常规处理方法表面应力的消除三、表面处理的评价方法  \n第四节 塑料用涂料的分类塑料用涂料选择基本原则主要塑料底材用涂料  \n第五节 塑料涂料的涂装1、 塑料涂料涂装施工方法塑料制品表面处理三、涂膜干燥类型四、塑胶漆涂膜的性能测试五、最新塑胶涂装方法六、塑胶漆膜缺陷及分析  \n参考文献  \n第七章木用涂料  \n第一节‧木用涂料沿革& 叶汉慈  \n第二节木材与木质材料的特性及涂装前的基本要求&吴智慧叶汉慈、木材的特性、木质材料的特性三、木制品应为涂装提供的条件  \n第三节木用涂料的品种及分类&叶汉慈张纯名、 木用涂料的品种木用涂料产品分类  \n第四节木用涂料产品基础配方及原理&王庆生谢晓芳曾光明赖华一、腻子二、封闭底漆三、底漆四、面漆五、固化剂六、稀释剂七、蓝、白水八、着色材料  \n第五节木用涂料产品的涂装应用&叶汉慈张纯名、现场调配、涂料产品底面漆配套原理三、木用涂装常用涂装工艺  \n第六节 木用涂装常见问题的现象、原因及处理&叶汉慈张纯名涂料涂装前常见漆病的预防及处理涂料涂装过程中常见漆病的预防及处理三、涂料涂装之后常见漆病的预防及处理四、木用涂料涂装管理与涂装难题  \n第七节 木用涂料主要性能指标及检验&刘红一、木用涂料需要控制的指标、有关木用涂料性能的国家标准和行业标准三、木质家具标准中对涂膜性能的要求四、通用检验方法五、特殊指标和特殊检测方法六、木用涂料生产、施工、成膜后的有害物质标准及测试方法",
+        "category": " Introduction"
+    },
+    {
+        "id": 1707,
+        "chunk": "# 第八节 木用涂料与涂装的发展&叶汉慈  \n\n家具的发展  \n1 底材应用  \n三四五 木用涂料的发展木用涂装的发展综述  \n参考文献  \n第八章 粉末涂料&史英骥  \n第一节 热塑性粉末涂料一、乙烯基尖木涂科二、聚烯烃粉末涂料三、尼龙粉末涂料四、热塑性聚酯粉末涂料  \n第二节热固性粉末涂料、纯环氧型粉末涂料  \n二、环氧／聚酯混合型粉末涂料  \n三、纯聚酯型粉末涂料  \n四、丙烯酸型粉末涂料  \n五、其他类型粉末涂料及辐射固化的粉末涂料  \n第三节‧热固性粉末涂料的生产技术1、 粉末涂料的配方及原材料二、粉末涂料的生产工艺三、粉末涂料生产及产品质量控制  \n第四节‧热固性粉末涂料的涂装工艺一、表面处理二、粉末涂料的涂装三、展望  \n参考文献  \n第九章航空航天涂料&孟军锋马宏冯俊忠  \n第一节　飞机蒙皮涂料、 飞机蒙皮涂料的现状及趋势飞机蒙皮涂料的作用三、飞机蒙皮涂料的组成四、飞机蒙皮涂料施工五、飞机蒙皮涂料展望  \n第二节消融隔热涂料1、 、概述二、消融材料三、消融隔热涂层的作用机理四、消融隔热涂料的配方设计原则五、消融隔热涂层的组成  \n第三节隔热保温涂料二、概述热控涂料三、耐高温隔热保温涂料四、小结  \n参考文献  \n第十章机床涂料与涂装& 谢劲  \n第一节概述  \n一、涂装的作用  \n二、机床涂装作业特点  \n第二节机床涂装用涂料二、机床涂装用涂料选用原则二、机床涂装常用涂料  \n第三节 机床涂装工艺",
+        "category": " References"
+    },
+    {
+        "id": 1708,
+        "chunk": "# 一、机床零、部件涂装工艺  \n\n二、机床钣金件涂装工艺三、成品机床涂装工艺四、机床一次涂装工艺五、美术漆及其涂装工艺  \n\n六、机床涂装中常见的漆膜病及防止方法  \n第四节 机床色彩格调机床色彩格调选择原则机床色彩配置原则一 世界各地对色彩的爱好与禁忌  \n第五节 机床涂层质量的检验涂层外观质量检验涂层耐温热试验三、 涂层耐工作介质试验  \n参考文献  \n第十一章 防火涂料&王华进  \n第一节 防火涂料概述  \n第二节 防火涂料的分类  \n第三节 防火涂料的防火机理  \n第四节 防火涂料的组成",
+        "category": " Introduction"
+    },
+    {
+        "id": 1709,
+        "chunk": "# 一、基体树脂  \n\n二、 阻燃剂第五节 防火涂料的配方设计一、钢结构防火涂料的配方设计第六节 防火涂料的发展参考文献第十二章 道路交通标线涂料&杜玲玲第一节 标线涂料的特殊性能要求第二节 我国现有标线涂料的主要品种第三节 标线涂料的组分、配方和生产",
+        "category": " References"
+    },
+    {
+        "id": 1710,
+        "chunk": "# 一、热熔标线涂料  \n\n二、溶剂标线涂料  \n\n三、水性标线涂料  \n\n四、双组分标线涂料  \n\n五、路面防滑涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 1711,
+        "chunk": "# 第四节 标线涂料的标准和检测  \n\n? 标线涂料的标准二 标线涂料特定的检测项目三四 按普通涂料常规检测的检测项目标线涂料的实用性能考核  \n第五节 标线施工材料的合理选用一 各种标线涂料的性能和优缺点对比二 标线使用性能室内模拟试验结果m 标线涂料的合理选用四、 标线用玻璃珠的正确选择和使用  \n第六节 标线涂料的施工标线施工的特点市售标线涂料的选择依据m 标线的分类四、 标线质量的基本要求五、 标线划设的工序六 各种标线涂料的施工设备、施工参数和注意事项  \n第七节 标线施工质量的控制一、标线施工质量的要求",
+        "category": " Introduction"
+    },
+    {
+        "id": 1712,
+        "chunk": "# 二、热熔标线涂层缺陷形态、产生原因和防止措施  \n\n三、 溶剂、水性和双组分标线涂层缺陷形态、产生原因和防止措施第八节 标线涂料的技术进展1 新开发的标线涂料1 国外有关标线涂料的技术标准三 中国、日本、英国、美国热熔反光标线涂料标准的对比四、 欧洲标准ZTVM02手册对反光标线材料的最低要求五、 标线涂料的发展趋势  \n\n参考文献  \n第四篇 涂料制造过程控制  \n第一章 涂料生产设备  \n第一节 树脂、漆料和清漆生产设备&潘元奇概述反应装置加热设备四、 净化设备  \n第二节 色漆生产设备&潘元奇概述预分散设备研磨分散设备四、 调漆设备五、 过滤设备",
+        "category": " Introduction"
+    },
+    {
+        "id": 1713,
+        "chunk": "# 第三节 过程管理&陈苹  \n\n-、ISO 9000标准  \n\n二、过程管理的理解和应用",
+        "category": " Introduction"
+    },
+    {
+        "id": 1714,
+        "chunk": "# 三、涂料生产和服务提供的过程管理  \n\n四、IS○ 14000简介",
+        "category": " Introduction"
+    },
+    {
+        "id": 1715,
+        "chunk": "# 参考文献  \n\n第二章 涂料工厂设计&戴蓉晖  \n第一节 绪论  \n第二节 商务计划、项目建议和工厂选址  \n第三节 可行性研究  \n第四节 工厂基础设计和配套设施设计  \n\n总图总平面布置S  \n\n一、设备设计应遵循的主要法规和标准、规范",
+        "category": " References"
+    },
+    {
+        "id": 1716,
+        "chunk": "# 二、树脂合成工艺",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1717,
+        "chunk": "# 三、涂料生产工艺",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1718,
+        "chunk": "# 四、涂料生产主要设备  \n\n参考文献  \n第三章 涂料性能测试&钱叶苗  \n第一节 概论涂料性能涂料产品的技术指标与标准三 涂料检测的目的与特点四、 涂料检测的发展与标准化  \n\n第二节 涂料产品检测涂料产品的取样涂料原始状态的检测涂料施工性能的检测",
+        "category": " References"
+    },
+    {
+        "id": 1719,
+        "chunk": "# 第三节 涂膜性能检测  \n\n均匀涂膜的制备一 涂膜的表观及光学性能的检测三 涂膜力学性能的检测四、 涂膜耐物理变化性能的检测五、 涂膜耐化学及耐腐蚀性能的检测六、 涂膜耐久性能的检测  \n第四节 涂料和涂膜的组成分析涂料和涂膜的组分分离涂料组分的单项分析三、 涂料和涂膜的全面分析四、涂膜结构电子显微镜检查  \n参考文献  \n第五篇 涂装过程控制  \n第一章 涂料涂装一体化的概念  \n第一节 涂装配套设计&刘会成涂膜使用环境分析经济性分析三、 表面处理的类型和方法的选择四、 涂料的选择五、 涂膜期待使用寿命分析六、 涂装配套的选定",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1720,
+        "chunk": "# 第二节 涂装工艺的制定&刘会成  \n\n表面处理要求及注意事项一三四五六七 涂装方法的选择 涂装过程的要求涂膜检验安全注意事项涂装工艺指导书举例第三节 产品说明书的编制&赵琪慧、产品说明书的基本要求二、产品说明书的具体内容  \n\n第四节 化学品安全技术说明书的编写&赵琪慧  \n\n一、MS D S 的意义二、对于MS DS 的编制要求三、MS D S 的使用  \n\n参考文献第二章 底材表面处理标准和检测方法第一节 钢材表面的物理处理方法&刘会成",
+        "category": " References"
+    },
+    {
+        "id": 1721,
+        "chunk": "# 一、手工工具清理  \n\n二、动力工具清理",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1722,
+        "chunk": "# 三、喷射处理  \n\n四、钢铁表面处理的相关标准  \n\n第二节 钢材表面的化学处理&林安 方达经除油脂酸洗二 磷化处理四 铬酸盐处理五、 金属表面化学处理的检测标准  \n第三节 其他金属的表面处理锌及锌合金的表面预处理铝及铝合金的表面预处理  \n第四节 混凝土的表面处理&林安一、清除表面油污和其他脏物二、 清除水泥浮浆、泛三、 清除表面光滑的方氵四、混凝土表面气孔及  \n第五节 塑料及橡胶表面处1， 塑料及橡胶表面处塑料及橡胶表面处  \n第六节‧木材的表面处理&氵一、 木材的种类及特征二、 木材涂装前处理的三、木材涂装前处理的;  \n参考文献  \n第三章涂料施工方法&李  \n第一节 刷涂法一、 刷涂的特点1、 漆刷的类型三、 刷涂基本操作方法  \n第二节 刮涂法1、 刮涂用具二、 刮涂的基本技法  \n第三节辊刷涂法1、 辊刷涂法的特点二、 辊刷的构造三、辊刷的种类四、辊刷涂操作要领  \n第四节 丝网法  \n第五节 喷涂法1、 空气喷涂法二、 无空气喷涂法三、 高压辅气喷涂法四、静电喷涂法五、 气雾罐喷涂法六、喷涂方法性能比较  \n第六节 浸涂法特点浸涂设备四、 浸涂工艺  \n第七节 帘幕淋涂法幕涂法的特点幕涂设备组成四、 幕涂工艺  \n第八节 抽涂法三、 原特  \n第九节 辊涂法一、 原理二、 辊涂机的构造三、 辊涂机的种类四、 辊涂工艺  \n第十节 电泳涂装法一、 原理特 工艺过程四、 主要工艺参数",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1723,
+        "chunk": "# 五、电泳涂装设备第十一节　自沉积涂漆法  \n\n原理二 特点一三 自泳涂装工艺四、 影响因素  \n\n第十二节 粉末涂装方法静电涂装法流化床涂装法三 静电流化床涂装法四、火焰喷涂法  \n第十三节 自动涂装系统一、概述二、往复涂装机三、涂装机器人  \n参考文献  \n第四章 涂装现场管理和技术服务&史春晖  \n第一节 涂料的贮存和现场物料管理",
+        "category": " References"
+    },
+    {
+        "id": 1724,
+        "chunk": "# 一、涂料的贮存",
+        "category": " Introduction"
+    },
+    {
+        "id": 1725,
+        "chunk": "# 二、涂料的现场管理",
+        "category": " Introduction"
+    },
+    {
+        "id": 1726,
+        "chunk": "# 第二节 涂装环境管理",
+        "category": " Introduction"
+    },
+    {
+        "id": 1727,
+        "chunk": "# 、照明的管理",
+        "category": " Introduction"
+    },
+    {
+        "id": 1728,
+        "chunk": "# 二、通风的管理  \n\n三 温度的管理四、 相对湿度的管理五、 空气污染影响的控制  \n第三节 涂装缺陷及现场处置  \n第四节 涂装验收涂膜表面状态的验收涂膜厚度的验收涂膜物理性能的验收  \n第五节 涂料施工的技术服务涂料施工技术服务的目的技术服务人员的主要工作内容三 技术服务人员的工作方法.四、 施工前的准备工作五六 现场技术服务工作的展开技术服务的记录与报告",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 1729,
+        "chunk": "# 参考文献  \n\n第五章 涂装施工安全、卫生和污染治理&祝家洵　钱捷　任卫东　王健  \n第一节 概述  \n第二节 涂装施工的危险因素及防护措施一、 涂装施工的危险因素二、 防护措施三、 安全技术教育培训  \n第三节 一般安全措施——个人劳动保护用品个人劳动保护用品个人劳动保护用品须具备的特征三 个人劳动保护用品的维护和报废规定  \n第四节 涂料的安全施下指导  \n\n一、健康危害  \n一 有工作危险的人员  \n三、防护措施 三  \n四、 工作服与装备  \n五、急救措施  \n六、泄漏应急处理  \n第五节 健康和环保措施健康安全环境保护措施  \n参考文献",
+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,77 @@
+[
+    {
+        "id": 1,
+        "chunk": "# 海洋环境智能防腐涂层：结构设计与响应机制  \n\n孙迎翔1，2，柯燕飞2，吴杨敏\\*2，赵长春\\*3，赵文杰2（1. 宁波大学材料科学与化学工程学院，宁波315211；2. 中国科学院宁波材料技术与工程研究所海洋关键材料重点实验室，宁波315201；3. 北京航空航天大学宁波创新研究院，宁波315800）  \n\n摘　要：为满足海洋环境下的长周期腐蚀防护的需求，当前研究重点主要集中在高性能智能响应腐蚀防护涂层，以及设计和开发出具有早期损伤预警与自修复功能的复合涂层。系统概述了国内外海洋苛刻环境下智能防腐涂层材料的最新研究进展，主要包括自修复防腐涂层和自预警防腐涂层，并介绍了关键因素对腐蚀防护性能的影响。未来，水下自修复、多通道缺陷响应、原位海洋验证实验和工业化应用是发展高性能海洋环境智能防腐涂层的重要趋势。  \n\n关键词：海洋环境；腐蚀防护；自修复；自预警；智能响应  \n\n中图分类号：TQ635. 1 文献标志码：A 文章编号：0253-4312（2024）09-0077-08  \ndoi：10. 12020/j. issn. 0253-4312. 2024-177",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# Intelligent Anti-corrosion Coating for Marine Environments： Structural Design and Response Mechanism  \n\nSUN Yingxiang1，2，KE Yanfei2，WU Yangmin2，ZHAO Changchun3，ZHAO Wenjie2 （1. School of Materials Science and Chemical Engineering，Ningbo University，Ningbo   315211，China； 2. Key Laboratory of Advanced Marine Materials，Ningbo Institute of Materials Technology and Engineering， Chinese Academy of Sciences，Ningbo   315201，China；3. Ningbo Institute of Technology， Beihang University，Ningbo   315800，China）  \n\nAbstract：To meet the requirements for long-term corrosion protection in marine environments，current research mainly focuses on high-performance intelligent response corrosion protection coatings，and the design and development of composite coatings with early damage self-warning and self-healing functions. In this paper，the latest research progress on intelligent anti-corrosion coating materials in harsh marine environments were reviewed， mainly including self-healing corrosion protection coating and self-warning corrosion protection coating，and the key factors affecting corrosion protection performance were also introduced. In the future，underwater self-healing，multi-channel defect response，in-situ marine validation experiments and industrial applications will be the important trends for the development of high-performance intelligent anti-corrosion coatings for marine environments.  \n\nKey words：marine environment；corrosion protection；self-healing；self-warning； intelligent response  \n\n早在2017 年，中国工程院侯保荣院士就指出，我国每年因腐蚀造成的经济损失高达2. 1 万亿元人民币，约占当年国民生产总值的 $3.34\\%^{[1]}$ 。因此，针对苛刻海洋环境中的关键和共性腐蚀问题，发展高性能长寿命腐蚀防护技术，减少因腐蚀而引起的安全和经济损失等问题，提升海工装备等金属构件的运行稳定性和可靠性，具有重要的意义。  \n\n当前，海洋环境中腐蚀防护策略主要包括电化学保护、缓蚀剂保护和有机涂层保护等。涂覆有机涂层因其简单的操作、良好的稳定性和优异的力学性能等优势，是当前应用最广泛的一种防腐方法。传统有机涂层在涂覆、成膜、固化和服役过程中不可避免地会产生微缺陷，从而导致涂层快速失效。尤其是在海洋环境中，随着服役时间的延长，损伤区域会急剧向外扩展，引发严重的界面腐蚀乃至涂层剥离失效。因此，在发生损伤时立即精准地定位缺陷和腐蚀区域，同时对损伤区域进行高效及时的修复，从而降低生产、维护成本，开发环境智能响应型防腐涂层，大幅度延长海工设施等金属装备在海洋环境中的长效稳定服役具有重要意义。  \n\n因此，本文在介绍环境智能响应型防腐涂层概念的基础上，分类总结了国内外海洋苛刻环境下自修复、自预警等涂层的最新研究进展，讨论了关键因素对其腐蚀防护性能的影响，最后阐述了目前环境智能响应型防腐涂层面临的机遇和挑战，并展望了其发展方向与趋势。",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# 智能响应涂层  \n\n当前，智能响应型防腐涂层根据功能可分为：自修复防腐涂层和自预警防腐涂层。",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1. 1 自修复涂层",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 1. 1. 1 外援型自修复防腐涂层  \n\n外援型自修复防腐涂层主要是指在聚合物基质中引入功能性填料来赋予涂层一定的自修复性能。这些功能性填料主要包括缓蚀剂、修复剂等，通常负载在填料表面或者容器内部，并通过外界刺激响应释放，发生修复行为。早在2001年，White等[2]首次将含有修复剂的微胶囊引入到涂层内部，当涂层发生损伤时，微胶囊囊壁破裂会释放出内部的修复剂，实现涂层的自修复，修复效率最高可达 $75\\%$ ，从而延长涂层的服役周期。此后，自修复防腐涂层领域的报道日渐增多。  \n\n苯并三氮唑（BTA）是一类非常经典的缓蚀剂，广泛应用于金属的腐蚀防护领域[3]。Liu 等[4]将环糊精（CD）引入到还原氧化石墨烯（ ${\\bf\\Gamma}_{\\mathrm{rGO}})$ ）表面制备了石墨烯基纳米容器 $\\left(\\mathrm{rGO-CD}\\right)$ ），并将BTA 缓蚀剂负载在容器内部（rGO-CD-BTA）以赋予环氧涂层优异的自修复能力。相比于 $\\mathrm{pH}{=}4$ 和 7 的服役环境， $\\mathrm{rGO-CD-}$ BTA 在 $\\mathrm{\\pH=}10$ 时拥有最大的曲线斜率（0. 278），表明复合涂层具有优异的基于 $\\mathrm{\\pH}$ 刺激响应性；微区电化学（LEIS）测试结果表明，由于BTA 的刺激响应释放，复合涂层（rGO-CD-BTA/EP）划痕附近的电化学反应会受到很大的抑制，腐蚀面积和反应程度随时间的延长不断减少，说明其具有优异的刺激响应自修复性能。Ouyang 等[5]对介孔二氧化硅（MSN）表面进行硅烷改性，负载2-巯基苯并噻唑（MBT），并结合层状双金属氢氧化物（LDH），得到基于 $\\mathrm{\\pH}$ 响应释放的MSN-MBT@LDHs 纳 米 填 料 。 结 果 表 明 ，MSN-MBT@LDHs 在酸性条件下（ $\\mathrm{\\pH}=2$ ），MBT 会大量释放，从而修复涂层缺陷。  \n\n北京科技大学张达威教授团队基于氮化钛（TiN）纳米颗粒的光热响应特性制备了一种具有双重作用的自修复防腐涂层[6]。他们设计了一种TiN $@$ 介孔二氧化硅 $\\mathrm{(mSiO_{2}}$ ）核壳纳米容器，负载BTA 分子$\\left(\\mathrm{TiN-BTA@mSiO}_{2}\\right.$ ），并添加到可自修复的环氧涂层中。在近红外（NIR）照射下，TiN 的光热效应不仅可以促进BTA 分子从纳米容器中释放到涂层缺陷处，还可以促发受损环氧树脂的自修复，实现基于光热驱动的双重自修复效果（图 1）。He 等[7] 将8-羟基喹啉（8-HQ）和二氧化钛（ $\\left(\\operatorname{TiO}_{2}\\right.$ ）一起封装在聚乙烯亚胺（PEI）上，构筑新型聚电解质纳米结构涂层。由于 $\\mathrm{TiO}_{2}$ 的光效应，在波长为 $260\\mathrm{nm}$ 的紫外光照射下，8-HQ 能够有效刺激释放，及时抑制金属基底的腐蚀行为并形成新的钝化层，从而实现涂层的自修复效应。  \n\n![](images/79ae222d424c5fe759a31139abe75dde5d8fe36960bc0a4cdd09511d2bd4fea3.jpg)  \n图 1　TiN-BTA $\\mathrm{\\@mSiO}_{2}$ 环氧复合涂层光热触发自修复机制 Fig. 1　The schematic diagram of photothermal-triggered selfhealing performance of epoxy resin based on TiN$\\mathrm{BTA}@\\mathrm{mSiO}_{2}$ nanoparticles  \n\nLDH 是一类常见的层状离子黏土矿物，具有优异的离子容纳能力，可在一定条件下进行离子交换[8]。目前，基于其特殊的离子交换能力，LDH 已被广泛应用于智能腐蚀防护领域。Li 等[9]利用噻吩衍生物缓蚀剂修饰 $\\mathrm{MgAl-LDH}$ 。结果表明，腐蚀性离子能够通过阴离子交换触发噻吩衍生物缓蚀剂的释放，从而实现优异的自修复效果。  \n\n外援型自修复智能防腐涂层适用于大缺陷的修复，在海洋腐蚀防护领域表现出优异的防护效果。然而，也存在一些制约其发展的问题。外援型自修复涂层由于内部的修复剂无法得到及时的补充，其修复效率会随着服役时间的延长而逐渐减弱甚至消失。此外，在工业应用中，无论是将修复剂直接添加进涂层内部，还是封装在纳米填料上，都必须确保其化学和物理稳定性，这也直接决定了涂层的自修复性能。未来应重点关注提升外援型自修复防腐涂层的修复性能、多次修复以及环境适应性等方面。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 1. 1. 2 本征型自修复防腐涂层  \n\n本征型自修复防腐涂层是指聚合物基质或者填料之间特殊的化学键或者官能团在光、热或者磁等外部条件刺激下发生断裂、重组，从而实现自修复。2002 年，Chen 等[10]利用马来酰亚胺和呋喃单体之间的Diels-Alder 环加成反应，开发了一种在加热条件下可实现自愈合的涂层。自此，开启了本征型自修  \n\n复涂层的研究热潮[11-13]。  \n\nLiu等[14]利用环糊精修饰GO作为主体分子，并在环氧链段上接枝金刚烷，以此为客体分子，开发了一种基于主客体相互作用的本征型自修复防腐涂层。基于环糊精与金刚烷之间的非共价键相互作用，复合涂层表现出优异的水下自修复能力（ $\\cdot24\\mathrm{h}$ 完成自修复）。这主要归因于当涂层出现裂纹缺陷时，聚合物基质中的金刚烷、环糊精、聚合物链段分子间能发生相互作用，并在断裂处实现分子重构，进而实现损伤修复。  \n\n受天然珍珠层和贻贝启发，Zhu 等[15]利用侧链具有四重氢键的“T”型扩链剂对聚氨酯（PU）预聚体进行修饰，并利用多巴胺（DA）修饰GO（PDG），在PU 与GO 连接处引入高密度非共价氢键作用，从而增强涂层的自修复性能和力学强度。为验证复合涂层的室温（ $25^{\\circ}\\mathrm{C}$ ）自修复性，将该涂层剪成两半，在 $25\\ \\mathrm{^\\circC}$ 环境下接触1 h，表现出良好的力学稳定性，其修复效率高达 $90.7\\%$ 。SEM 照片显示， $\\mathrm{PU-PDG-}0.5\\%$ 涂层由于多重氢键的相互作用，在室温接触1 h 后，基本完全修复涂层受损区域。涂层引入人工缺陷后，在初始阶段，缺陷处与完整处的阻抗值有明显的差异，但是在水中浸泡 $2\\mathrm{h}$ 后，缺陷处与完整处的阻抗值基本一样。在浸泡 $24\\mathrm{h}$ 后，缺陷处与完整处仍表现出相近的阻抗值，说明复合涂层修复行为稳定可靠。Li等[16]通过喷涂方法制备了具有超快自修复性的PU 涂层。在室温、空气条件下，PU涂层在不需要任何外界条件的帮助下，依靠自身氢键的运动可引起涂层本身微结构的断裂和重构，使得涂层在 $30\\mathrm{min}$ 内划痕完全修复，表现出优异的自修复性能。  \n\n陕西科技大学佟立波教授课题组受丝素蛋白启发，制备了主被动一体化自修复 $\\mathrm{Ti}_{3}\\mathrm{C}_{2}\\mathrm{T}_{x}/\\mathrm{PU}$ 复合涂层[17]。复合涂层表现出优异的室温自修复能力，修复率高达 $140\\%$ 。这主要归因于在制备涂层过程中，将二硫键和能够形成氢键的扩链剂添加到PU 分子链段中，赋予涂层优异的自由基转移和氢键动态重组的性能，从而实现高效自修复腐蚀防护。此外，复合涂层也表现出优异的长效腐蚀防护能力，在经过 $3.5\\%\\mathrm{NaCl}$ 溶液浸泡 14 d，其低频阻抗值高达$10^{8}\\Omega\\cdot\\mathrm{cm}^{2}$ ，相比纯PU 提升1 个数量级。这主要归因于 $\\mathrm{Ti}_{3}\\mathrm{C}_{2}\\mathrm{T}_{\\boldsymbol{x}}$ 能够发挥片层结构优势，延长了腐蚀介质的扩散路径；氨基酸也能在涂层受损后迅速吸附在金属基底形成保护膜。  \n\n基于化学键动态可逆反应思路，河北工业大学潘明旺教授团队设计开发了一种基于PU 的长效自修复复合涂层[18]。首先利用3-氨丙基三乙氧基硅烷修饰正丙醇锆（TPOZ）以此来增强与水性聚氨酯（WPU）之间的相容性，并基于缩合水解反应生成动态可逆键，从而赋予复合涂层优异的自修复能力。接着将氨基修饰的TPOZ（ $\\mathrm{A-Zr}\\mathrm{O}_{2}$ ）引入到甘氨酰胺修饰的 WPU 中 $(\\mathrm{WPUG}_{x})$ ），得到具有优异自修复特性 的 聚 氨 酯 复 合 涂 层 $\\mathrm{(WPUG\\it/A\\mathrm{-}Z r O_{2}}$ ）。 由 于$\\mathrm{A-Zr}0_{2}$ 的硬相作用和氢键网络的软相作用，赋予涂层优异的自修复能力和力学性能，其自修复效率高达 $92.58\\%$ ，在高效腐蚀防护领域显示出良好的应用前景。  \n\n吉林大学孙俊奇教授团队基于超分子作用力概念，将醛基和氨基以物质的量比 $1\\colon1$ 的方式将苯-1，3，5-三甲醛（BTC）和双氨基封端聚二甲基硅氧烷 $\\left(\\mathrm{NH}_{2}\\mathrm{-PDMS-NH}_{2}\\right)$ ）添加到含有二氧化硅的四氢呋喃溶液中，最后喷涂在基底上得到具有自修复特性的复合涂层[19]。由于 $\\mathrm{NH}_{2}{\\mathrm{-PDMS-NH}_{2}}$ 具有氨基特性，能与BTC 发生席夫碱反应，生成具有高键能和动态共价键特性的亚胺键，因此赋予涂层良好的自修复特性，尤其是低温自修复特性，为基底提供了良好的防护。  \n\nDiels-Alder 是一种典型的热响应可逆反应[20]。Barner-Kowollik 课题组利用 retro-Diels-Alder 反应设计了一种基于氰基二硫酯和环戊二烯的快速自修复涂层体系[21-22]。其中，Diels-Alder 反应可在 $120\\ \\mathrm{^\\circC}$ 下在 $5\\mathrm{min}$ 内完成动态键/化学键的断裂与重组。此外，在涂层内部添加一定的增塑剂也有助于实现较为温和的自修复过程。Postiglione 等[23]向含有三官能和双官能呋喃和双马来酰亚胺的聚合物树脂中加入 $10\\%$ 的甲苯醇增塑剂，在 $120\\ \\mathrm{^{\\circ}C}$ 加热 $5\\mathrm{min}$ ，可实现 $100~{\\upmu\\mathrm{m}}$ 划痕的完全修复，体现了优异的热致驱动自修复性能。  \n\n本征型自修复防腐涂层通常需要将损伤区域完全接触，才能发生有效的修复行为。因此，通常会引入柔性链段来保证聚合物基质的可移动性，但这会牺牲涂层的力学性能。此外，在海洋苛刻环境中，光、热和磁等触发条件难以实现。因此，设计制备环境高适应性本征型自修复腐蚀防护涂层以实现在海洋环境中的实际应用具有重要研究意义和应用价值。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 1. 2 自预警涂层",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 1. 2. 1 自预警涂层概述  \n\n自预警涂层主要是指当涂层发生损伤后能够以某种信号及时传递出来的智能防护涂层[24]。在腐蚀初期对涂层进行有效的定位及预警，能大幅提升涂层的维护效率和服役年限，可有效避免因涂层失效而造成的重大事故。因此，设计和开发具有自预警性能的智能防腐涂层具有重要的实际应用价值。",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 1. 2. 2 自预警涂层在腐蚀防护中的应用  \n\n目前，在涂层中引入含有显色剂成分的填料或接枝变色基团实现涂层损伤预警是一个主流策略。Li 等[25]将2’-7’-二氯荧光素包覆在微胶囊内制备自预警涂层。当涂层发生机械破损时，破裂的微胶囊会释放荧光素，荧光素与聚合物基质反应，会引起从浅黄色到亮红色的急剧颜色变化。  \n\nLiu 等[26]将菲咯啉（Phen）作为 Q235 碳钢腐蚀响应的指示剂，并将其封装进MSN 纳米容器内部，制备腐蚀自预警智能防护涂层。在环氧涂层表面引入人工缺陷，并浸泡在 $3.5\\%\\mathrm{NaCl}$ 溶液中，短短 $5\\mathrm{min}$ 内，就可以通过显著的橙红色迅速预警出由涂层损坏引起的电化学腐蚀。经过 $120\\mathrm{min}$ 后，缺陷处的红色愈发明显，表明了其优异的自预警性能。Cheng 等[27]将1，10-菲咯啉−5-氨基负载在聚多巴胺修饰的GO 纳米片上，并与热响应自修复特性的聚合物结合在一起。结果表明，基于GO 和聚多巴胺的光热特性，复合涂层在近红外辐射下表现出快速的裂纹闭合行为。此外，Phen-Fe 复合物表现出清晰的荧光淬灭以报告早期腐蚀现象。  \n\n北京科技大学马菱薇教授等在MSN 上负载单宁酸（TA-MSNs）以此作为功能填料赋予环氧涂层自修复和自预警性能[28]。当涂层发生破损缺陷时，TA 分子能够从涂层中释放出来，与 $\\mathrm{Fe}^{3+}$ 发生络合反应，生成一种蓝黑色的保护膜，既可以预警早期腐蚀行为，又能在一定程度上抑制腐蚀反应，从而延长金属的服役周期。在环氧涂层中加入 $5\\%$ TA-MSNs 时，其低频阻抗值比纯环氧涂层的高2个数量级，腐蚀防护能力优异。  \n\n聚苯胺（PANI）是一类具有明显钝化和光热效应的材料，可以赋予涂层智能效应[29-30]。当前，有学者在PANI 本征自修复特性的基础上，在其表面接枝荧光探针，从而使得聚合物涂层兼具修复和自预警性能。基于此，江南大学罗静教授课题组在PANI 微球中封装8-HQ 并引入到聚合物树脂中，成功制备了自预警自修复一体化智能防护涂层[31]。采用光聚合和界 面 苯 胺 聚 合 相 结 合 的 方 式 成 功 制 备 了  \n\n8-HQ@PANI 微球，并系统考察了该微球对聚合物涂层早期预警及修复的影响行为。在涂层表面引入人工划痕并放置在中性盐雾箱中，经过 $48\\mathrm{~h~}$ 的浸泡，纯涂层没有出现任何变化，而复合涂层出现明显的蓝色荧光，且随着浸泡时间的延长，荧光效应愈发明显。这主要是因为当涂层发生破损时，8-HQ 会从8-HQ@PANI 微球中释放出来并与 $\\mathrm{Al}^{3+}$ 发生螯合反应，产生荧光自预警。此外，PANI能够在近红外光照下引起树脂分子链段的重构，同时产生致密的保护膜，实现涂层的自修复。类似的，该课题组将8-HQ负载在三羟甲基丙烷三丙烯酸酯微球上，发现8-HQ既可以修复涂层破损区域，又能对腐蚀进行早期预警[32]。  \n\n碳量子点（CQDs）是一类具有显著荧光性能的零维碳纳米材料，在涂层预警等领域中表现出极大的应用潜力[33-34]。Lü 等[35]利用表面含有丰富极性官能团的 CQDs 修饰石墨相氮化碳纳米片（ $\\mathrm{(g-C_{3}N_{4}}$ ，CNNs），并制备了兼具主/被动自修复和早期预警一体化的复合防腐涂层。基于CQDs 对金属基底的吸附特性，使涂层由被动防护转为主动防腐。此外，CQDs 具有出色的荧光特性，能够精准监测涂层中的微裂纹，实现早期预警（图2）。  \n\n![](images/b0df80a1cee0e78fe31dd706e32748267e303bbac8ae2b8c673c12835ffe46d2.jpg)  \n图2　利用CQDs的荧光特性精准监测涂层中的微裂纹  \n\nFig. 2　Accurate monitoring of microcracks in coatings using the fluorescence characteristics of CQDs  \n\n发展自修复-自预警功能一体化复合防腐涂层正成为一个重要趋势。Li 等[36]利用聚多巴胺修饰六方氮化硼（PN），以此来连接金属有机框架（ $\\mathrm{\\Deltazn-MOF-}$ 74），构建基于 $\\mathrm{PN-Zn-MOF-}74$ 纳米容器的智能防腐涂层。在涂层服役过程中， $\\mathrm{Fe}^{3+}$ 和 $Z\\mathrm{n}^{2+}$ 之间的阳离子交换行为可消除 $\\mathrm{Zn-MOF-}74$ 的荧光特性，并在受损区域重新形成弱荧光化合物，实现涂层的早期预警。此外， $\\mathrm{Fe}^{3+}$ 和 $\\mathrm{H^{+}}$ 会逐渐在受损区域释放，与纳米容器中封装的 $Z\\mathrm{n}^{2+}$ 和聚多巴胺迅速交换并反应，形成致密的保护膜，实现涂层的主动防护。  \n\n目前，自预警智能防腐涂层已逐渐成为智能涂层发展的一个重要方向。保持高精度、高灵敏度和高海洋环境适应性是目前预警方向的研究热点。此外，还应该进一步降低自预警智能防腐涂层的制备成本和提高预警性能的普适性，发展预警-修复一体化海洋环境高性能防腐涂层。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 1. 3 智能响应涂层的驱动要素  \n\n环境智能响应型涂层在发挥自修复、自预警智能响应防护功能时通常需要外界条件一定的刺激，主要包括pH、磁场、力等因素。这些因素对复合涂层  \n\n的防腐性能有重要的影响。",
+        "category": " Introduction"
+    },
+    {
+        "id": 11,
+        "chunk": "# 1. 3. 1 pH  \n\n目前，大多数自修复涂层要依靠 $\\mathrm{\\pH}$ 的变化驱动涂层内部腐蚀防护反应的发生， $\\mathrm{\\pH}$ 对涂层的防腐能力有重要影响[37-38]。Huang 等[39]利用 $\\mathrm{rGO}/$ 介孔二氧化硅与 $\\mathrm{\\pH}$ 响应性的 $N,N-$ 甲基丙烯酸二甲氨基乙酯（PDMAEMA）进行三明治结构设计，并负载BTA 分子，以此来增强环氧复合涂层的防腐能力。结果表明，PDMAEMA 作为 $\\mathrm{\\pH}$ 驱动的阀门，可有效调控 $\\mathrm{\\pH}$ 从而控制BTA 的释放，实现了复合涂层基于pH 变化的智能自修复腐蚀防护。此外，在NIR 光照下， $\\mathrm{rGO}$ 显著的光热效应不仅可以提高涂层表面温度实现复合涂层的自修复，还可以促进BTA 的释放以抑制腐蚀活性，从而实现涂层的长效腐蚀防护。Mirmohseni等[40]利用水包油微乳液成功制备了负载缓蚀剂的二氧化硅胶囊，并设置pH 开关，成功实现了MBT 的智能释放，从而赋予复合涂层优异的自修复性能。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 1. 3. 2 磁场  \n\n磁场也是影响复合涂层防腐性能的一个重要因素[41]。Ma 等[42]通过水热法成功制备了 $\\mathrm{rGO}$ 负载四氧化三铁纳米颗粒 $\\left(\\mathrm{rGO-Fe}_{3}\\mathrm{O}_{4}\\right)$ ），并将其均匀分散在硅油中制备 $\\mathrm{rG0{-}F e_{3}O_{4}/O i l}$ 基于磁场驱动的自修复涂层。在磁场的驱动下， $\\mathrm{rG0-Fe}_{3}\\mathrm{O}_{4}/\\mathrm{Oil}$ 能定向覆盖损伤区域，实现局部腐蚀区域的智能修复。Ding 等[43]利用 $\\mathrm{Fe}_{3}\\mathrm{O}_{4}$ 对石墨烯纳米片进行改性，并将其分散在环氧树脂中，在均匀磁场和超声波条件下固化，进而在树脂内部形成定向排列的石墨烯纳米片。对于富锌涂层而言，与非磁性层相比，定向排列磁性石墨烯的存在改善了物理屏蔽和阴极保护性能。这种改进是由于平行排列降低了有效的电子传输并提高了锌颗粒的活性，从而赋予复合涂层优异的防护能力。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 1. 3. 3 力  \n\n涂层在实际服役过程中，通常是受到机械外力压迫而造成缺陷、损伤。因此，开发基于力致响应智能防腐涂层是一种有效策略。螺吡喃因其良好的力致响应特性，被广泛应用于智能防护涂层。Davis等[44]利用螺吡喃修饰聚（丙烯酸甲酯）得到了一种基于力致响应变色的聚合物材料，拉伸结果表明，在外力作用下，聚合物拉伸处会逐渐转变为红色，且随着拉伸程度的增加颜色逐渐变深，实现了对机械外力的自预警。Song 等[45]在聚氨酯主链中引入双羟基螺吡喃，合成了一种力致诱导变色的自预警/自修复涂层。结果表明，在外力作用下，随着拉伸程度的增加，螺吡喃中螺环C—O 键的断裂能够有效转化为颜色的变化，使涂层实现从黄色到淡蓝色乃至深紫色的转变。此外，由于氢键的相互作用，该聚氨酯涂层表现出优异的自修复行为，其修复效率高达 $98.3\\%$ 。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 2 结　语  \n\n目前，智能响应型防腐复合涂层仍处于实验室初步探索阶段，距离工业化应用还有很长的距离。  \n\n（1）当前自修复防腐涂层适用于微小的缺陷，很难实现大面积破损区域的修复。针对外援型自修复涂层，要重点关注缓蚀剂的负载效率、容器与树脂之间的界面相容性。对于本征型自修复涂层而言，要注意涂层本身力学性能与修复效率的平衡。此外，智能防腐复合涂层的水下自修复性能也应该重点关注和研究。  \n\n（）腐蚀预警在智能响应型防护涂层领域的研究相对较少，主要是通过显色反应来判断涂层的受损情况，对于其损伤程度难以定量化，且灵敏度较低，不具备普适性。此外，发展多通道缺陷响应模式，实现缺陷腐蚀实时监测，建立涂层缺陷-腐蚀-预警之间的构效关系，是智能腐蚀防护涂层发展的一个重要方向。  \n\n（3）原位海洋环境验证实验是智能响应型防腐涂层发展的重要趋势。它能及时监测各种腐蚀参数的变化，提供更详细、真实的统计数据，以便更精确地评估其防腐能力和环境适应性，这有助于进一步提高和优化智能防腐涂层材料的开发和应用。  \n\n（）海洋苛刻环境下智能防腐涂层的工业化应用仍存在大量技术瓶颈，制备工艺复杂、施工环境恶劣、成本高等。此外，复合涂层的耐久性和稳定性也需要进一步提高。因此，在海洋环境如跨海大桥、海上风电等涂覆智能防腐涂料还有大量工作待深入探索和研究。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 15,
+        "chunk": "# 参考文献  \n\n[ 1 ] HOU B，LI X，MA X，et al. The cost of corrosion in China[J]. npj Materials Degradation，2017，1（1）：4.   \n[ 2 ] WHITE S，SOTTOS N，GEUBELLE P，et al. Autonomic healing of polymer composites[J]. Nature，2001，409： 794-797.   \n[ 3 ] WANG J， ZHAO J， TABISH M， et al. Intelligent anticorrosion coating based on mesostructured $\\mathrm{BTA@mCeO_{2}/}$ $\\mathrm{g-C_{3}N_{4}}$ nanocomposites for inhibiting the filiform corrosion of $\\mathrm{Zn{-}M g{-}A l}$ coated steel[J]. Corrosion Science，2023，221： 111331.   \n[ 4 ] LIU C，ZHAO H，HOU P，et al. Efficient Graphene/cyclodextrinbased nanocontainer：synthesis and host-guest inclusion for self-healing anticorrosion application[J]. ACS Applied Materials & Interfaces，2018，10（42）：36229-36239.   \n[ 5 ] OUYANG Y，LI L X，XIE Z H，et al. A self-healing coating based on facile pH-responsive nanocontainers for corrosion protection of magnesium alloy[J]. 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Autonomous indication of mechanical damage in polymeric coatings[J]. Advanced Materials，2016，28（11）：2189-2194.   \n[26] LIU C，JIN Z，CHENG L，et al. Synthesis of nanosensors for autonomous warning of damage and self-repairing in polymeric coatings[J]. Nanoscale，2020，12（5）：3194- 3204.   \n[27] CHENG L，LIU C，ZHAO H，et al. Photothermal-triggered shape memory coatings with active repairing and corrosion sensing properties[J]. Journal of Materials Chemistry A， 2021，9（39）：22509-22521.   \n[28] 马菱薇，杨雪婷，郑凯宁，等. 基于单宁酸负载的自预警- 自修复双重功能防腐涂层[J]. 材料开发与应用，2024，39（2）： 95-105. MA L W，YANG X T，ZHENG K N，et al. Self-reporting and self-healing dual functional anticorrosive coating based on tannic acid additives[J]. Development and Application of Materials，2024，39（2）：95-105.   \n[29] 张青青，陈亚鑫，刘仁，等. 基于聚苯胺微胶囊的双重自 修复防腐涂层[J]. 高分子学报，2023，54（5）：720-730. ZHANG Q Q，CHEN Y X，LIU R，et al. Dual-action selfhealing anticorrosive coating based on polyaniline microcapsules[J]. Acta Polymerica Sinica，2023，54（5）： 720-730.   \n[30] 王波，许胤杰，王海波. 基于改性氧化石墨烯/聚苯胺增 强水性聚氨酯防腐涂层的制备及性能研究[J]. 涂料工 业，2024，54（4）：54-61. WANG B，XU Y J，WANG H B. Preparation and performance of modified graphene oxide/polyanilinereinforced waterborne polyurethane anticorrosive coating[J]. Paint & Coatings Industry，2024，54（4）：54-61.   \n[31] ZHANG Q，LI W，LIU X，et al. Polyaniline microspheres with corrosion inhibition，corrosion sensing，and photothermal self-healing properties toward intelligent coating[J]. ACS Applied Materials & Interfaces，2023，16（1）：1461-1473.   \n[32] LI W，TAO J，CHEN Y，et al. Porous microspheres with corrosion sensing and active protecting abilities towards intelligent self-reporting and anti-corrosion coating[J]. Progress in Organic Coatings，2023，178：107468.   \n[33] 史燕妮，李敏，陈师，等. 碳量子点及其性能研究进展[J]. 高分子通报，2016，1：39-46. SHI Y N，LI M，CHEN S，et al. Progress on the carbon quantum dots and their properties[J]. Polymer Bulletin， 2016，1：39-46.   \n[34] RAHIMI M，MAHANI M，HASSANI Z. Carbon quantum dots fluorescence quenching for potassium optode construction[J]. Luminescence，2019，34（4）：402-406.   \n[35] LÜ Y，ZHAO W，QIANG Y，et al. Constructing the interface of g-C3N4/epoxy composites using carbon quantum dots to achieve self-repairing，early corrosion monitoring and superior anticorrosion performance[J]. Corrosion Science， 2023，225：111601.   \n[36] LI X，GONG B，JIN Y，et al. Intelligent water-borne coatings with self-reporting， self-healing， and robust barrier performance for the active corrosion protection of Q235 steels[J]. Progress in Organic Coatings，2024，189： 108366.   \n[37] LIU T，ZHANG D，MA L，et al. Smart protective coatings with self-sensing and active corrosion protection dual functionality from pH-sensitive calcium carbonate microcontainers[J]. Corrosion Science，2022，200：110254.   \n[38] CI X，ZHAO W，GAO W. Achieving high loading inhibitor carriers with pH-response for active corrosion protection using attapulgite[J]. Materials Today Nano，2022，19： 100228.   \n[39] HUANG Y，WANG P，TAN W，et al. Photothermal and pH dual-responsive self-healing coating for smart corrosion protection[J]. Journal of Materials Science & Technology， 2022，107：34-42.   \n[40] MIRMOHSENI A，AKBARI M，NAJJAR R，et al. Selfhealing waterborne polyurethane coating by pH-dependent triggered-release mechanism[J]. Journal of Applied Polymer Science，2018，136（8）：47082.   \n[41] LI X，LU P，FU X，et al. Magnetically controlled interface weaving of dual-layer heterogeneous coatings with active and passive anti-corrosion protection[J]. Progress in Organic Coatings，2024，186：108064.   \n[42] MA A，WEI J，WU Y，et al. A novel directional repairing rGO-Fe O /Oil coating with magnetic driving for metal protection and self-healing[J]. Chemical Engineering Journal，2021，421：129597.   \n[43] DING R，CHEN S，ZHOU N，et al. The diffusion-dynamical and electrochemical effect mechanism of oriented magnetic graphene on zinc-rich coatings and the electrodynamics and quantum mechanics mechanism of electron conduction in graphene zinc-rich coatings[J]. Journal of Alloys and Compounds，2019，784：756-768.   \n[44] DAVIS DA，HAMILTON A，YANG J，et al. Force-induced activation of covalent bonds in mechanoresponsive polymeric materials[J]. Nature，2009，459（7243）：68-72.   \n[45] SONG X，SONG Y，CUI X，et al. Intrinsic healable mechanochromic materials via incorporation of spiropyran mechanophore into polymer main chain[J]. Polymer，2022， 250：124878.  \n\n收稿日期 2024-08-05（修改稿）",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# A Universal Strategy for Growing a Tenacious Hydrogel Coating from a Sticky Initiation Layer  \n\nRongnian Xu, Yunlei Zhang, Shuanhong Ma,\\* Zhengfeng Ma, Bo Yu, Meirong Cai, and Feng Zhou\\*  \n\nControllably coating the surfaces of substrates/medical devices with hydrogels exhibits great application potential, but lacks universal techniques. Herein, a new method, namely ultraviolet-triggered surface catalytically initiated radical polymerization (UV-SCIRP) from a sticky initiation layer (SIL) (SIL@UV-SCIRP), is proposed for growing hydrogel coatings. The method involves three key steps: 1) depositing a sticky polydopamine/ $\\mathsf{\\Pi}_{\\mathsf{F e}^{3+}}$ coating on the surface of the substrates-SIL, 2) reducing $\\mathsf{F e}^{3+}$ ions to $\\mathsf{F e}^{2+}$ ions as active catalysts by UV illumination with the assistance of citric acid, and 3) conducting SCIRP in a monomer solution at room temperature for growing hydrogel coatings. In this manner, practically any substrate’s surface (natural or artificial materials) can be modified by hydrogel coatings with controllable thickness and diverse compositions. The hydrogel coatings exhibit good interface bonding with the substrates and enable easy changes in their wett­ability and lubrication performances. Importantly, this novel method facilitates the smooth growth of uniform hydrogel lubrication coatings on the surface of a range of medical devices with complex geometries. Finally, as a proof-of-concept, the slippery balls coated with hydrogel exhibited smooth movement within the catheter and esophagus. Hence, this method can prove to be a pioneering universal modification tool, especially in surface/interface science and engineering.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1. Introduction  \n\nDue to good biocompatibility, stimulus responsiveness, and biochemical properties analogous to those of natural tissues, hydrogels, which are essentially water-containing hydrophilic polymers with 3D cross-linked network structures, have evoked a keen research interest in a wide range of areas, including tissue engineering,[1] actuation,[2] and biomedicine.[3] Over the past few decades, hydrogels with the latest and most comprehensive functionalities have been synthesized through various strategies.[4] Nevertheless, a myriad of efforts and attention have been devoted to the ontological design of hydrogels. Meanwhile, the controlled modification of hydrogels as functional coatings on the surfaces of substrates has emerged as both a promising and challenging topic,[5] particularly in the field of electronic and medical devices. In connection therewith, a number of transformative developments have been achieved pertaining to the strategies of coating substrates with hydrogels, including surface bridge method,[6] surface initiation method,[7] hydrogel painting method,[8] and surface catalytically initiated radical polymerization (SCIRP) method.[9,10]  \n\nConsidering the surface bridge method, it first requires to graft coupling molecules with specific functional groups, while the thickness of the hydrogel coating depends upon the amount of monomer solution dropped on the surface, thereby resulting in poor thickness controllability. The hydrogel painting method is based on the silane grafting of the polymer layer before undergoing the curing process. Suo et  al. formulated a family of hydrogel paints in the form of photoinitiatorgrafted polymer chains.[11] Furthermore, a concept of renatured hydrogel painting was proposed to decorate uniform hydrogel coatings on tangible surfaces.[12] The SCIRP method entails the iron catalyst to be doped into the substrates beforehand, while the inherent properties of the substrates would suffer some change.[9] The surface photo/thermal-initiation method proposed by Zhao et  al. is currently a trending research topic that enables the modification of hydrogel coatings on the surfaces of a wide range of medical devices and soft robots.[13,14] Nonetheless, such initiation method is based on long-term $(30{-}90~\\mathrm{\\min})$ UV irradiation or heating along with an accumulated thermal effect, which may induce cross-linking polymerization or viscosity increasement of the entire monomer solution that stays away from the reaction interface; in particular, it is only functional for polymer substrates that can swell in organic solvents containing benzophenone. Analogous to Zhao’s strategy, Gong et al. developed a universal method for decorating hydrogel coatings onto the surface of diverse substrates in two steps: first, forming a thin, physically bound primer layer containing radical initiators, then conducting photo-induced polymerization after applying presolution to the treated surface.[15] Hence, a more general strategy for controllably growing hydrogels on the surface of diverse solid materials regardless of material geometry and category under mild reaction conditions has remained a key challenge in this field. This work revolves around the objective of devising a wider-ranging and universal strategy to modify various substrates with desirable hydrogel layers.  \n\nMussel-inspired polydopamine (PDA) has emerged as a widely popular and preferred functional molecule for coating diverse substrates, including metals, metal oxides, polymers, and ceramics, which can be attributed to its conducive features, such as mild reaction conditions and easy one-step processing.[16] In particular, the profusely available functional catechol groups in PDA provide effective anchoring sites for transition metal ions to form polymer–metal ion complexes,[17] such as PDA- $\\mathrm{Fe}^{3+}$ . Based on two typical scientific mechanisms, $\\mathrm{Fe}^{2+}$ is capable of catalytically decomposing persulfate to generate free radicals that induce monomer polymerization at low temperatures[18] and $\\mathrm{Fe}^{3+}$ ions can be reduced to $\\mathrm{Fe}^{2+}$ ions when facilitated by citrate acid under the illumination of UV light,[19] an innovative method called ultraviolet-triggered surface catalytically initiated radical polymerization (UV-SCIRP) from a sticky initiation layer (SIL) (SIL $@$ UV-SCIRP) is proposed to grow hydrogel coatings universally on various substrate surfaces, which can efficiently compete with the abovementioned methods.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2. Results and Discussion  \n\nDepositing the PDA adhesive coating on the surface of the substrates is a key step in this method. Commonly, the PDA coating contains adhesive catechol groups and reactive sites, helping it bond with substrates through numerous molecular interactions.[20] Citric acid (CA) is a compound with three carboxyl groups. The pH level of the mixed solution of $\\mathrm{FeCl}_{3}{\\cdot}6\\mathrm{H}_{2}\\mathrm{O}$ and CA is 4.0, and only one carboxyl group of CA experienced deprotonation in this circumstance, so the deprotonated carboxyl will coordinate with $\\mathrm{Fe}^{3+}$ ions to form an $\\mathrm{Fe}^{3+}.$ –CA complex. Then, the substrate deposited with PDA can partly coordinate with $\\mathrm{Fe}^{3+}$ ions (competitively associated with citric acid) to form a $\\mathrm{PDA}/\\mathrm{CA}{-}\\mathrm{Fe}^{3+}$ composite layer (Figure 1a). The conceptual mechanism of the method is shown in Figure  1b. The $\\mathrm{Fe}^{3+}$ ions within $\\mathrm{PDA}/\\mathrm{CA}{-}\\mathrm{Fe}^{3+}$ can then be reduced to $\\mathrm{Fe}^{2+}$ ions using UV illumination with the assistance of CA,[19,21] generating an active sticky catalyst initiation layer (SIL). Subsequently, the solid–liquid interface redox reaction is performed between $\\mathrm{Fe}^{2+}$ and $\\mathrm{S}_{2}\\mathrm{O}_{8}{}^{2-}$ ions in monomer solution to generate radical anion ${\\mathrm{SO}}_{4}^{-}{\\cdot}$ , along with the dramatic reduction of the decomposition activation energy,[18,22] to initiate monomer polymerization at room temperature. Intuitively, the poly(acrylic acid)–poly(acrylamide) (PAA-PAM) hydrogel coating can be successfully grown on the surface of the Ti substrate by the SIL $@$ UV-SCIRP method, according to the fluorescence optical photograph (Figure 1c).  \n\nThe detailed preparation process of the proposed SIL@UVSCIRP method is demonstrated in Figure  1d. Specifically, the substrates are immersed first into the trimethylaminomethane (Tris) solution to deposit the adhesive PDA coating and were subsequently subjected to the treatment in aqueous solution containing $\\mathrm{FeCl}_{3}{\\cdot}6\\mathrm{H}_{2}\\mathrm{O}$ and CA for $^3\\mathrm{~h~}$ to form a PDA/ ${\\mathrm{CA-Fe}}^{3+}$ composite layer (Figure  1d-i), in which $\\mathrm{Fe}^{3+}$ forms a competitive cross-linking coordination with PDA and CA. Next, the PDA/CA– $\\mathrm{\\cdot}\\mathrm{Fe}^{3+}$ -decorated substrates are irradiated by UV light to reduce $\\mathrm{Fe}^{3+}$ to $\\mathrm{Fe}^{2+}$ , which acts as an active surface catalyst (Figure  1d-ii). The $\\mathrm{Fe}^{2+}$ catalyst-loaded substrates are then immersed into the monomer solution to perform interface-dominated radical polymerization for in situ growth of hydrogel coatings on the surfaces of substrates at room temperature (Figure  1d-iii,iv). Among them, it is anticipated that the grown hydrogel network combines preferentially with a sticky initiation layer (SIL) by noncovalent interactions, such as ion coordination $(\\mathrm{COO^{-}{-}F e^{3+}{-}C O O^{-}})$ and hydrogen bonding $(\\mathrm{COOH-N-H})$ . At the same time, the radical anion $\\mathrm{SO}_{4}{}^{-\\cdot}$ may extract reactive hydrogen from the amine group $\\left(\\mathrm{-NH-}\\right)$ of PDA, resulting in the generation of an RN• radical to realize covalent coupling with the hydrogel network (Figure S1, Supporting Information).[23] The hydrogel coating is denoted as $\\mathrm{H}_{\\mathrm{m}}$ (H represents the hydrogel, and m represents the composition of the hydrogel). The exceptional advantages of the current method can be outlined as follows: the modification appears suitable for most of the surfaces, the entire polymerization process is conducted at room temperature, the monomer solution needs not be degassed, the coating process can be completed within a few minutes, the thickness of the hydrogel coating is highly controllable, and the monomer solution reacted upon is reusable up to several times (Figure 1e).  \n\nThe substrates of hydrophilic titanium $(\\mathrm{Ti})$ and hydrophobic polyethylene (PE) were employed to investigate the growth kinetics of the $\\mathrm{H_{PAA-PAM}}$ coating under numerous conditions. The thickness of the $\\mathrm{H_{PAA-PAM}}$ coating on the surfaces of Ti and PE substrates is highly dependent on the PDA deposition time and the coating growth time. As shown in Figure 2a, the thickness of the $\\mathrm{H_{PAA-PAM}}$ coating on $\\mathrm{\\DeltaTi}$ gradually increases from 76.4 to $385.1\\upmu\\mathrm{m}$ , while it progresses from 65.5 to $285.1\\upmu\\mathrm{m}$ on PE, along with extending the PDA deposition time from 12 to $72\\mathrm{~h~}$ . The most likely scenario is that a longer deposition time enables an ever-increasing number of PDA molecules on the substrate, facilitating coordination with a greater number of $\\mathrm{Fe}^{3+}$ ions to produce a high number of $\\mathrm{Fe}^{2+}$ catalysts after UV irradiation. Figure  2b demonstrates that extending the growth time from $30~\\mathrm{s}$ to 10 min in the monomer solution also tends to induce an evident increase in the thickness of the HPAA-PAM coating on Ti (from 48.1  to $303.5~{\\upmu\\mathrm{m}}_{,}^{}$ and PE (from 48.1  to $278.1~{\\upmu\\mathrm{m}})$ substrates. The inserted cross-sectional micro­scopy images (Figure  2a,b) intuitively demonstrate the growth process of the $\\mathrm{H}_{\\mathrm{PAA-PAM}}$ coating (colored layers). Meanwhile, the chemical component of the grown $\\mathrm{H}_{\\mathrm{PAA-PAM}}$ coating can be confirmed using Fourier transform infrared spectroscopy (Figure  S2, Supporting Information). Taking the Ti substrate as an example, the peaks at 3335  and $3186~\\mathrm{cm}^{-1}$ are assigned to the acylamino group $(\\mathrm{NH}_{2}\\mathrm{-}\\mathrm{C=}\\mathrm{O-}$ ), while 2930  and $1651~\\mathrm{cm}^{-1}$ are the characteristic peaks of alkyl $(\\mathrm{-CH}_{3},\\mathrm{-CH}_{2}\\mathrm{-})$ and carbonyl $(-\\mathrm{COOH})$ groups, signifying the successful modification of the $\\mathrm{H_{PAA-PAM}}$ coating. Significantly, the $\\mathrm{SIL}@$ UV-SCIRP method is suitable for a series of monomers, and hydrogel coatings with diverse components can be successfully modified on the Ti substrates, including poly(vinyl alcohol)– poly(2-hydroxyethyl methacrylate), poly(ethylene glycol) methyl ether methacrylate–poly(acrylic acid), PAA-PAM, poly(ethylene glycol) methyl ether methacrylate–poly(acrylic acid)–poly(2- hydroxyethyl methacrylate)), poly(vinyl alcohol)–poly(acrylic acid)–poly(acrylamide), and poly(2-hydroxyethyl methacrylate)– sodium alginate–calcium chloride (Figure  2c). However, even more importantly, we found that the monomer solution is reusable up to several times for growing the hydrogel coating on the PDA/CA–Fe3+-decorated substrate, which can be regarded as a great improvement compared to UV-initiated technology.[13] As illustrated in Figure S3a, Supporting Information, the growth thickness of the $\\mathrm{H_{PAA-PAM}}$ coating on the Ti substrate amounts to ${\\approx}150~\\ensuremath{\\upmu\\mathrm{m}}$ every time. Finally, the bottom monomer solution polymerized due to the accumulative diffusion of the generated $\\mathrm{Fe}^{2+}$ ion catalyst at the interface, while the top phase remained unpolymerized after growing ${\\approx}15$ times (Figure S3b, Supporting Information).  \n\n![](images/ed80c78c27956f11ddc34630f67571dad70c7f0c4870cc713add936936198d82.jpg)  \nFigure 1.  Mechanism of SIL@UV-SCIRP method. a) Schematic diagram showing anchoring of the adhesive PDA/CA–Fe3+ coating on the substrate surface through certain interactions. b) The interface polymerization mechanism involved in the SIL $@$ UV-SCIRP method to form a uniform hydrogel coating on the substrate surface. c) Fluorescence optical photograph of Ti substrate half-grown with $H_{P A A-P A M}$ coating containing rhodamine 6G. The universal substrates demonstrated in the paper are Ti, alumina (Al), gold (Au), polyethylene (PE), polyurethane (PU), poly(tetrafluoroethylene) (PTFE), poly(ethylene terephthalate) (PET), polypropylene (PP), nylon, polyimide (PI), Si, glass, ceramic, pine, and hair surfaces. d) Schematic diagram illustrating the detailed preparation process of the SIL $@$ UV-SCIRP method. (i) Formation of PDA/CA– ${\\cdot}\\mathsf{F e}^{3+}$ coating layer on the substrate surface; (ii) in situ generation of $\\mathsf{F e}^{2+}$ ions catalyst with UV irradiation with the assistance of CA; (iii) immersing the catalyst-loaded substrate into the monomer solution for achieving interface radical polymerization; (iv) formation of uniform hydrogel coating (orange network) on the substrate surface. e) Exceptional benefits of the current SIL $@$ UV-SCIRP method for growing hydrogel coatings.  \n\nOwing to the assembly advantage of PDA coatings on diverse substrates,[16] hydrogel coatings can be successfully grown on nearly all substrates (natural or artificial), including metals, polymers, inorganics, and organisms, by the SIL $@$ UV-SCIRP method. As shown in Figure 2d, the thickness of the HPAA-PAM coating on Ti, alumina (Al), gold (Au), PE, polyurethane (PU), poly(tetrafluoroethylene) (PTFE), poly(ethylene terephthalate) (PET), polypropylene (PP), nylon, polyimide (PI), Si, glass, ceramic, pine, and hair surfaces was found to be $\\approx151.9$ , 150.6, 181.9, 122.9, 128.7, 108.4, 145.1, 150.0, 146.8, 142.9, 150.3, 143.2, 155.5, 135.3, and $43.0~{\\upmu\\mathrm{m}}$ , respectively (deposition time: $24\\mathrm{~h~}$ , growth time: $2\\ \\mathrm{min}$ ). The presence of the $\\mathrm{H}_{\\mathrm{PAA-PAM}}$ coating enables an easy change of the wettability of the substrates. The contact angles for bare Ti, Al, Au, PE, PU, PTFE, PET, PP, nylon, PI, Si, and glass substrates are ${\\approx}51.7{^{\\circ}}$ , $89.4^{\\circ}$ , $54.1^{\\circ}$ , $99.0^{\\circ}$ , $105.4^{\\circ}$ , $103.5^{\\circ}$ , $55.9^{\\circ}$ , $86.4^{\\circ}$ , $51.5^{\\circ}$ , $64.1^{\\circ}$ , $82.5^{\\circ}$ , $19.9^{\\circ}$ , and $82.8^{\\circ}$ (Figure S4, Supporting Information), respectively. As a comparison, all of them suffer a reduction and fall below $15^{\\circ}$ after being modified by the $\\mathrm{H}_{\\mathrm{PAA-PAM}}$ coating. Intuitively, uniform coating on substrates with diverse geometric shapes/sizes can be observed and verified clearly through fluorescence imaging after dyeing the $\\mathrm{H}_{\\mathrm{PAA-PAM}}$ coating with rhodamine 6G on the outer surface of bone/pine/hair (Figure 2e).  \n\n![](images/0410d5d0e3ad1ffb7f61f492cf4f3b9f6e4299b20a96c902c6f4ab0888a75452.jpg)  \nFigure 2.  Controllable modification of hydrogel coating on various substrates by the SIL $@$ UV-SCIRP method. a,b) The thickness change of the $\\mathsf{H}_{\\mathsf{P A A-P A M}}$ coating on the Ti/PE substrate surface with PDA deposition time and polymerization growth time (the inserted pictures are the crosssectional optical microscopy images of Ti/PE substrates and hydrogel coating layer). c) The thickness of hydrogel coating with different components on the Ti substrate (deposition time: 24 h). d) The thickness of the $H_{P A A-P A M}$ coating and contact angle of various substrates with the $H_{P A A-P A M}$ coating (deposition time: $24\\ h$ , growth time: 2  min). e) Optical images (left) of various substrates and fluorescence images (right) of various substrates (e1: bone, $\\boldsymbol{\\mathrm{e}}_{2}$ : pine.) after modifying the HPAA-PAM coating with rhodamine 6G $(\\mathsf{I}\\mathsf{m g}\\mathsf{m}\\mathsf{L}^{-1})$ , and $\\left(\\mathsf{e}_{3}\\right)$ optical (left) and fluorescence microscopy images (right) of hair after growing the $H_{P A A\\cdot P A M}$ coating with rhodamine 6G $(1\\mathrm{mg}\\mathrm{m}\\mathrm{L}^{-1}.$ ) (deposition time: $24\\mathsf{h}$ , growth time: $2\\mathsf{m i n}$ ).  \n\nThe interface combination force between the substrate and the hydrogel coating was analyzed by administering a $90^{\\circ}$ peeling test with PET as stiff backing (Figure 3a). Figure  3b portrays three typical snapshots from the peeling test process, where the partial HPAA-PAM coating still remains on the Ti substrate after testing (yellow dotted box), signifying a strong bonding force between the grown hydrogel and the Ti substrate. More intuitively, the PE substrate decorated with hydrogel coating after the $90^{\\circ}$ peeling test was dyed with rhodamine B $(1\\ \\mathrm{mg\\mL^{-1}})$ to obtain the corresponding fluorescence images. As shown in Figure S5, Supporting Information, there is apparent residual on the PE substrate surface. By and large, the peeling force per unit width of the HPAA-PAM coating for the Ti substrate is found to be ${\\approx}70\\ \\mathrm{~N~m^{-1}}$ , while it is approximately $35~\\mathrm{N~m^{-1}}$ for the PE substrate (Figure 3c). Attributable to the presence of the adhesive PDA layer, the bonding strength of the HPAA-PAM coating is considerably better than that of the previously reported method.[9] Nevertheless, due to the weak mechanical strength of the classic PAA-PAM hydrogel network (elastic modulus $\\approx~39~\\mathrm{\\kPa})$  \n\n![](images/c2c8c763c2beaad45abde62651990da9619fe08a8dc8f96f0ad0f4d9adff876f.jpg)  \nFigure 3.  a) Schematic illustration of the $90^{\\circ}$ peeling test for analyzing the interface combination strength between the substrate and the hydrogel coating, and stiff backing (PET) is introduced to prevent elongation of the HPAA-PAM coating along the peeling direction. b) Snapshots of the $90^{\\circ}$ peeling test on Ti substrate with the $H_{P A A-P A M}$ coating and residual hydrogel (yellow dotted box). The scale bar is 2 cm. c) The $90^{\\circ}$ peeling force per width versus displacement curve of the $\\mathsf{H}_{\\mathsf{P A A-P A M}}$ coating on $\\bar{\\mathsf{T i}}$ and PE substrates. d) Cross-sectional SEM morphology exhibiting the interface between $\\bar{\\mathsf{T i}}$ substrate and $H_{P A A\\cdot P A M}$ coating, and e) corresponding chemical component analysis obtained by EDS mapping, carbon (C, red), oxygen (O, yellow), nitrogen (N, turquoise), and titanium (Ti, blue). f) The friction coefficient curves of Ti and PE substrates before/after growing the $\\mathsf{H}_{\\mathsf{P A A-P A M}}$ coating. g) The friction coefficients of various substrates before and after growing the $\\mathsf{H}_{\\mathsf{P A A-P A M}}$ coating. h) The variation in friction coefficient of Ti substrate upon circularly growing HPAA-PAM coating by SIL $@$ UV-SCIRP method. In all cases, the PDA deposition time is $24\\mathsf{h}$ , and the polymerization growth time is $2\\min$ .  \n\n(Figure S6, Supporting Information) and slim thickness of the hydrogel coating, no valuable network dissipation is achieved to obtain higher interface strength. However, due to the universality of the SIL $@$ UV-SCIRP method for different kinds of monomer solutions, it would still be suitable for obtaining tough hydrogel coatings.  \n\nThe good combination between the hydrogel coating and substrates is attributable to the possible formation of a covalent couple between the SIL and hydrogel coating.[23] Subsequently, the cross-sectional scanning electron microscopy morphology (Figure  3d) and energy dispersive spectroscopy mapping (Figure 3e) further validate the good combination of the HPAA-PAM coating and the Ti/PE substrates (Figure S7, Supporting Information). The resulting HPAA-PAM coating effectuates an evident reduction in the surface friction force of the substrates, which could be characterized by the friction coefficients measured from a ball-on-disk reciprocating tribometer with water as a lubricant. The friction coefficients decrease significantly from 1.287  to 0.075 $_{(\\approx17}$ -fold) for the Ti substrate and 1.822  to 0.040 $(\\approx43$ -fold) for the PE substrate over the entire 300  cycles (Figure  3f). Moreover, to prove the durability and lifetime of the $\\mathrm{H_{PAA-PAM}}$ coating, the reciprocating tests were extended up to 7200  cycles (Figure S8, Supporting Information). The friction coefficient of the PE substrate with the $\\mathrm{H_{PAA-PAM}}$ coating was stable at 0.032  during the entire 7200 cycles, demonstrating the good robustness of the hydrogel coating. Figure $3\\mathrm{g}$ demonstrates that all the bare substrates, including Ti, Al, Au, PE, and nylon, exhibit high friction coefficients in water $(>1.25)$ , while their surfaces reveal a very low friction coefficient $_{(<0.08)}$ after growing the HPAA-PAM coating, clearly highlighting the versatility of the lubrication enhancement brought by the SIL $@$ UV-SCIRP method. More importantly, the proposed method can be used to achieve constant lubrication modification for the substrates continuously, and even more so, without damaging the inherent surface feature of the substrate itself (Figure 3h).  \n\nThe patterned coating of hydrogels with controllable shape and size is also feasible through our SIL $@$ UV-SCIRP method, assisted by the UV grayscale exposure technique.[24] Not only regular patterns such as round (left) and grid (right) of the $\\mathrm{H}_{\\mathrm{PAA-PAM}}$ coatings can be easily constructed (Figure 4a), but also sophisticated patterns such as butterfly can be successfully generated on the substrate surface (Figure  4b). Intriguingly, the temperature-responsive HPNIPAM-PAA coating pattern was constructed on the Ti substrate satisfactorily to accomplish the challenge of the “Sichuan opera face” (Figure  4c). In a $20~^{\\circ}\\mathrm{C}$ water bath, the “face” looks blurry due to the network swelling of the hydrogel coating, while it becomes clear and white in a $40~^{\\circ}\\mathrm{C}$ water bath. Furthermore, controllable hydrogel coating could be performed on porous hydrophobic substrates to prepare functional membrane materials. As shown in Figure  4d, the porous PE substrate with nine channels tends to be hydrophobic in air, and water drops tend to suspend on its surface, while it changes to be hydrophilic after growing the $\\mathrm{H_{PAA-PAM}}$ coating to allow the water to easily drop down from the channels. Such an evident wettability transition can also be realized from a hydrophobic state to a hydrophilic state for the PTFE filter membrane after growing the $\\mathrm{H_{PAA-PAM}}$ coating (Figure 4e), inferring its potential applicability in the field of liquid separation. Furthermore, the SIL $@$ UV-SCIRP method is highly conducive to developing hydrogel-based composite materials. As shown in Figure  4f, the hydrogel fiber composite material can be prepared easily by growing the HPAA-PAM coating in situ on nonwoven fabrics and comes with a significant enhancement in tensile strength (from ${\\approx}2.65$ to $8.80~\\mathrm{\\MPa}$ ) as well as elastic modulus (from 4.58  to 19.13  MPa) (Figure S9a,b, Supporting Information).  \n\n![](images/d20be7dabdd6e2fca5f89abf6620a4e6b93e4aa021281d4c2104bca1c773ac26.jpg)  \nFigure 4.  The patterned coating of hydrogels on a flat substrate and uniform coating of hydrogels on structured substrates. a) Fluorescence images of the substrate after growing regular patterned $H_{P A A-P A M}$ coating with rhodamine 6G $(\\bar{1}\\mathsf{m g}\\mathsf{m}\\mathsf{L}^{-\\bar{1}})$ round (left), and grid (right). b) Schematic illustration of the butterfly model (left) and (right) fluorescence photograph of the Ti substrate after growing the patterned $H_{P A A\\cdot P A M}$ coating with rhodamine 6G $(\\mathsf{l}\\mathsf{m}\\mathsf{g}\\mathsf{m}\\mathsf{L}^{-\\mathsf{l}})$ . c) The dynamic color change of the intricate HPNIPAM-PAA coating patter te to realize the art of a “Sichuan opera face” in a 20 and $40~^{\\circ}\\mathsf{C}$ water bath. d) Photographs showing the transition from the hydrophobic (left) to hydrophilic (right) state of the PE substrate with nine channels before/after growing the $H_{P A A-P A M}$ coating. e) Optical and fluoresce es of the PTFE filter ne before/after growing the HPAA-PAM coating with rhodamine 6G $(7~\\mathrm{mg}~\\mathrm{mL^{-1}})$ . f) Preparation of fiber-reinforced PAA-PAM composite hydrogel materials by applying the SIL $@$ UV-SCIRP method. In all cases, the PDA deposition time is $24\\ h$ , and the polymerization growth time is $30~\\mathsf{s}$ .  \n\nAlthough the modification of hydrogel coating on medical device surfaces is deemed as an effective approach to change their inherent lubrication property,[13] it is highly demanding to simultaneously fulfill two key requirements of applicability for substrates with different components and precisely controllable thickness of the coating. The $\\mathrm{SIL}@$ UV-SCIRP method enables the growth of $\\mathrm{H_{PAA-PAM}}$ coating with a controllable thickness on diverse medical devices possessing various shapes and sizes, including hollow throat (a), suction head (b), biliary stent (c), drainage tube (d), polyvinyl chloride (PVC) catheter (e), stomach tube (f), latex catheter (g), and titanium alloy bulb of artificial hip joint (h) (Figure 5, left). Noticeably, the uniformity of the $\\mathrm{H_{PAA-PAM}}$ coating can be observed under fluorescence imaging after being dyed with rhodamine 6G (Figure  5a–h, right). Meanwhile, the cross-sectional fluorescence microscopy images of the modified PVC catheter (Figure S10a, Supporting Information) and latex catheter (Figure S10b, Supporting Information) show that the thickness of the $\\mathrm{H}_{\\mathrm{PAA-PAM}}$ coating is 84.6 and $53.0\\upmu\\mathrm{m}.$ , respectively. Additionally, water was used as a lubricant to analyze the lubrication performance of the two kinds of hydrogel-modified catheters. The average friction coefficients of the bare PVC catheter (Figure 5i) and latex catheter (Figure 5j) without hydrogel coating is 3.504 and 1.879, respectively. In contrast, the average friction coefficients of the PVC catheter and latex catheter decrease to ${\\approx}0.0437$ and $0.0467$ after modifying the $\\mathrm{H}_{\\mathrm{PAA-PAM}}$ coating, validating their remarkable lubrication capability. Predictably, our SIL $@$ UV-SCIRP method provides the capability to modify the hydrophilic hydrogel coating on the surfaces of various medical devices to reduce the interface friction force during the process of implantation/intervention.  \n\nFinally, to validate the potential applicability of the SIL $@$ UV-SCIRP method in implanted/interventional processes under a 3D cavity tissue environment, hydrogel-coated spherical solids with slippery surface features were employed to conduct the demonstration experiments. As shown in Figure 6a and Movie S1, Supporting Information, the alumina ball (diameter: $2.5~\\mathrm{\\mm})$ with lubricated HPAA-PAM coating can smoothly migrate along the water flow within the cavity of the “S” PVC catheter tube under the $50~\\mathrm{rpm}$ flow rate (Figure S11, Supporting Information). In contrast, the bare alumina ball without hydrogel coating gets stuck in the corner due to the high friction force at the contact interface. Correspondingly, Figure 6b clearly illustrates the motion path curves of the bare alumina ball and lubricated alumina ball. The bare alumina ball can migrate for only ${\\approx}4.5~\\mathrm{cm}$ during the first $4\\mathrm{~s~}$ , but then it remains stagnant for the following $4{-}10\\mathrm{~s~}$ . Conversely, the alumina ball with the $\\mathrm{H}_{\\mathrm{PAA-PAM}}$ coating can move easily along the $\\ensuremath{^\\circ}\\mathrm{S}^{\\prime\\prime}$ track for ${\\approx}27$ cm within 10 s (Figure 6b). To quantitatively examine the effect of lubrication on the movement of balls, the interface friction forces between the balls and the inner surface of the channels were measured by pulling the constrained balls from one end of the catheter tube to the other end. As shown in Figure 6c, the friction force between the bare alumina ball and the channel could reach to $0.2~\\mathrm{N}$ , while it is only ${\\approx}0.03\\ \\mathrm{N}$ after decorating with the $\\mathrm{H_{PAA-PAM}}$ coating. To simulate the shearing process more meticulously in implanted/interventional scenes, natural cattle esophagus, regarded as a typical tissue transportation scenario,[25] and a large steel ball (diameter: $5~\\mathrm{cm}$ was employed to inspect the friction force at the interface (Figure S12, Supporting Information). A schematic illustration of the cattle esophagus and real optical images of the sample are shown in Figure  6d. The friction force between the bare steel ball and the internal surface of the cattle esophagus is found to be ${\\approx}6\\ \\mathrm{N}$ , while it is only ${\\approx}1\\mathrm{\\DeltaN}$ for the modified ball (Figure 6e). These results mentioned above are a strong inference for the potential applicability of the SIL $@$ UV-SCIRP method for the lubrication modification of biomedical equipment.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# 3. Conclusion  \n\nAn innovative modification method called SIL@UV-SCIRP is proposed to grow hydrogel coatings with good interface combination for universal substrate surfaces, including metals, polymers, inorganics, and organisms. Compared to the reported techniques, the remarkable benefits of the current method are obvious: it can theoretically be applied on any substrate, the reaction is performed mildly at room temperature, the monomer solution need not be degassed, the coating can be completed effectively within a few minutes, the thickness of the hydrogel layer is highly controllable either through the PDA deposition time or via the monomer polymerization time, and the reacted monomer solution is reusable up to several times. The hydrogel coatings exhibit decent interface combination strength with substrates and is highly feasible for varying the inherent wetting and lubrication performances of the relevant substrate surfaces. Numerous regular and intricate patterned hydrogel coatings can be generated readily by fixed-site reduction of $\\mathrm{Fe}^{2+}$ catalysts with the assistance of the UV grayscale exposure technique. Significantly, this method is a universal tool to modify hydrogel coatings on the outer surface of diverse medical devices, such as hollow throat, suction head, biliary stent, drainage tube, PVC catheter, stomach tube, latex catheter, and titanium alloy bulb of an artificial hip joint. Finally, to prove the potential applicability of this method in implanted/interventional processes, lubricated spherical solids with hydrogel coatings were employed to simulate the directional migration behavior of specific devices within 3D constrained channels. Both alumina and steel balls with hydrophilic hydrogel lubrication coatings exhibit a smooth movement ability within the channel of the artificial PVC catheter tube or even natural cattle esophagus. We believe that this innovative method could become a universal modification tool in surface/interface science and engineering.  \n\n![](images/fc9d65a56816b23d782da393414a10c1695c03f3b75804b22122b9f188bb02cc.jpg)  \nFigure 5.  Growing hydrogel coatings on the surface of various medical devices. Optical photos of medical devices (left) and corresponding fluorescence photos after partly coating $H_{P A A\\cdot P A M}$ with rhodamine 6G $(\\mathsf{I}\\mathsf{m g}\\mathsf{m}\\mathsf{L}^{-1})$ (PDA deposition time: $24\\mathsf{h}$ , polymerization growth time: 30 s). a) Hollow throat; b) Suction head; c) biliary stent; d) drainage tube; e) PVC catheter; f) stomach tube; g) latex catheter; h) titanium alloy bulb of artificial hip joint. The scale bar is $2c m$ . The friction coefficient curves of bare catheters and catheters modified with $\\mathsf{H}_{\\mathsf{P A A-P A M}}$ coating (load: $0.2~\\mathsf{N}$ , sliding frequency: $1H z$ , lubricant: $H_{2}O)$ : i) PVC catheter, j) latex catheter.  \n\n![](images/4a9ce161245df7921f9e75fd50d8fef480a15dc1114502ae9d6923689ea859e4.jpg)  \nFigure 6.  Schematic illustrations of the conceptual demonstration for the potential application of hydrogel coatings. a) Snapshots of demonstrating the movement state of the controlled alumina ball (above) and modified-alumina ball with $H_{P A A-P A M}$ coating (below) within the ${}^{u}{\\sf S}^{\\prime\\prime}$ PVC catheter tube under a 50-rpm flow rate (PDA deposition ti $24\\mathsf{h}$ rowth time: $30~\\mathsf{s}$ , diameter of alumina ball: $2.5~\\mathsf{m m}$ ). b) The migration path curves of the controlled alumina ball (above) ball with $\\mathsf{H}_{\\mathsf{P A A-P A M}}$ coating (below) within the channel of the PVC catheter tube. c) The friction force versus displaceme a ball and the urfac e of the PVC catheter tube under a tensile speed of $5\\min\\min^{-1}$ . d) Schematic illustration of the it eal photos. e) The friction fo place curves between the steel ball and the inner surface of natura ttl before/after growing $\\mathsf{H}_{\\mathsf{P A A-P A M}}$ coating (tensile speed: $50\\min\\operatorname*{min}{}$ ; PDA deposition time: $24\\mathsf{h}$ , polymerization growth time: $30~\\mathsf{s}$ , diameter of steel ball: $5c m$ ).",
+        "category": " Conclusions"
+    },
+    {
+        "id": 5,
+        "chunk": "# Supporting Information  \n\nSupporting Information is available from the Wiley Online Library or from the author.",
+        "category": " References"
+    },
+    {
+        "id": 6,
+        "chunk": "# Acknowledgements  \n\nThe authors are grateful for financial support from National Natural Science Foundation of China (22032006, 52075522, and 22072169), Key Research Program of the Chinese Academy of Sciences (XDPB24), Outstanding Youth Fund of Gansu Province (21JR7RA095), Key Research Project of Shandong Provincial Natural Science Foundation (ZR2021ZD27), and the Youth Innovation Promotion Association of the Chinese Academy of Sciences (2019411).",
+        "category": " Acknowledgements"
+    },
+    {
+        "id": 7,
+        "chunk": "# Conflict of Interest  \n\nThe authors declare no conflict of interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 8,
+        "chunk": "# Author Contributions  \n\nR.X. and Y.Z. contributed equally to this work. S.M. and F.Z. conceived the idea and supervised the entire research. R.X. and Y.Z. performed the experiments and completed the whole characterizations. R.X. and S.M. drafted the manuscript. F.Z. revised and finalized the manuscript. All the authors discussed the results and provided technical suggestions.",
+        "category": " Author Contributions"
+    },
+    {
+        "id": 9,
+        "chunk": "# Data Availability Statement  \n\nResearch data are not shared.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 10,
+        "chunk": "# Keywords  \n\nhydrogel coatings, polymerization, sticky initiation layers, surface modifications  \n\nReceived: November 3, 2021   \nRevised: January 4, 2022   \nPublished online: February 5, 2022  \n\n[5]\t J. Liu, S. Qu, Z. Suo, W. Yang, Natl. Sci. Rev. 2021, 8, nwaa254.   \n[6]\t a) W.  Li, X.  Liu, Z.  Deng, Y.  Chen, Q.  Yu, W.  Tang, T. L.  Sun, Y. S.  Zhang, K.  Yue, Adv. Mater. 2019, 31, 1904732; b) H.  Yuk, T. Zhang, S. Lin, G. A. Parada, X. Zhao, Nat. Mater. 2016, 15, 190.   \n[7]\t a) M. H.  Schneider, Y.  Tran, P.  Tabeling, Langmuir 2011, 27, 1232; b) H. Yuk, T. Zhang, G. A. Parada, X. Liu, X. Zhao, Nat. Commun. 2016, 7, 12028.   \n[8]\t a) X.  Yao, J.  Liu, C.  Yang, X.  Yang, J.  Wei, Y.  Xia, X.  Gong, Z.  Suo, Adv. Mater. 2019, 31, 1903062; b) Q.  Liu, G.  Nian, C.  Yang, S.  Qu, Z.  Suo, Nat. Commun. 2018, 9, 846; c) X.  Yang, C.  Yang, J.  Liu, X. Yao, Z. Suo, Sci. China: Technol. Sci. 2020, 63, 1314.   \n[9]\t S. Ma, C. Yan, M. Cai, J. Yang, X. Wang, F. Zhou, W. Liu, Adv. Mater. 2018, 30, 1803371.   \n[10]\t S. W. Song, S. Lee, J. K. Choe, N. H. Kim, J. Kang, A. C. Lee, Y. Choi, A.  Choi, Y.  Jeong, W.  Lee, J. Y.  Kim, S.  Kwon, J.  Kim, Sci. Adv. 2021, 7, eabf3804.   \n[11]\t T.  Yin, S. R.  Lavoie, S.  Qu, Z.  Suo, Cell Rep. Phys. Sci. 2021, 2, 100463.   \n[12]\t Z.  Yang, Y.  He, S.  Liao, Y.  Ma, X.  Tao, Y.  Wang, Sci. Adv. 2021, 7, eabf9117.   \n[13]\t Y.  Yu, H.  Yuk, G. A.  Parada, Y.  Wu, X.  Liu, C. S.  Nabzdyk, K. Youcef-Toumi, J. Zang, X. Zhao, Adv. Mater. 2019, 31, 1807101.   \n[14]\t a) G. A. Parada, H. Yuk, X. Liu, A. J. Hsieh, X. Zhao, Adv. Healthcare Mater. 2017, 6, 1700520; b) Y.  Kim, G. A.  Parada, S.  Liu, X.  Zhao, Sci. Rob. 2019, 4, eaax7329; c) G. Parada, Y. Yu, W. Riley, S. Lojovich, D.  Tshikudi, Q.  Ling, Y.  Zhang, J.  Wang, L.  Ling, Y.  Yang, S.  Nadkarni, C.  Nabzdyk, X.  Zhao, Adv. Healthcare Mater. 2020, 9, 2001116.   \n[15]\t R.  Takahashi, K.  Shimano, H.  Okazaki, T.  Kurokawa, T.  Nakajima, T. Nonoyama, D. R. King, J. P. Gong, Adv. Mater. Interfaces 2018, 5, 1801018.   \n[16]\t H.  Lee, S. M.  Dellatore, W. M.  Miller, P. B.  Messersmith, Science 2007, 318, 426.   \n[17]\t J. Yang, M. A. C. Stuart, M. Kamperman, Chem. Soc. Rev. 2014, 43, 8271.   \n[18]\t D. A. House, Chem. Rev. 1962, 62, 185.   \n[19]\t Y. Gao, K. Wu, Z. Suo, Adv. Mater. 2019, 31, 1806948.   \n[20]\t H. A.  Lee, Y.  Ma, F.  Zhou, S.  Hong, H.  Lee, Acc. Chem. Res. 2019, 52, 704.   \n[21]\t J. L.  Frahn, Aust. J. Chem. 1958, 11, 399; b) F.  Peng, G.  Li, X.  Liu, S. Wu, Z. Tong, J. Am. Chem. Soc. 2008, 130, 16166.   \n[22]\t a) I.  Epold, N.  Dulova, J. Environ. Chem. Eng. 2015, 3, 1207; b) J. W. L. Fordham, H. L. Williams, J. Am. Chem. Soc. 1951, 73, 4855.   \n[23]\t a) Y.  Wang, J.  Yang, K.  Qiu, Acta Polym. Sin. 1994, 1, 188; b) D. L. Hall-Edgefield, T. Shi, K. Nguyen, A. Sidorenko, ACS Appl. Mater. Interfaces 2014, 6, 22026; c) W. Sheng, B. Li, X. Wang, B. Dai, B. Yu, X. Jia, F. Zhou, Chem. Sci. 2015, 6, 2068.   \n[24]\t X. Kuang, J. Wu, K. Chen, Z. Zhao, Z. Ding, F. Hu, D. Fang, H. J. Qi, Sci. Adv. 2019, 5, eaav5790.   \n[25]\t A. Oezcelik, S. R. DeMeester, Thorac. Surg. Clin. 2011, 21, 289.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,47 @@
+[
+    {
+        "id": 1,
+        "chunk": "# ADVANCED MATERIALS  \n\nSupporting Information  \n\nfor Adv. Mater., DOI: 10.1002/adma.202108889  \n\nA Universal Strategy for Growing a Tenacious Hydrogel Coating from a Sticky Initiation Layer  \n\nRongnian Xu, Yunlei Zhang, Shuanhong Ma,\\* Zhengfeng Ma, Bo Yu, Meirong Cai, and Feng Zhou\\*",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# Supporting Information",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# A Universal Strategy for Growing a Tenacious Hydrogel Coating from a Sticky Initiation Layer (SIL)  \n\nRongnian $X u^{\\#}$ , Yunlei Zhang#, Shuanhong Ma\\*, Zhengfeng Ma, Bo Yu, Meirong Cai, and Feng Zhou\\*  \n\nDr. R. Xu, Y. Zhang, Dr. S. Ma, Z. Ma, Prof. B. Yu, Prof. M. Cai, Prof. F. Zhou   \nState Key Laboratory of Solid Lubrication   \nLanzhou Institute of Chemical Physics   \nChinese Academy of Sciences   \nLanzhou 730000, China   \nE-mail: mashuanhong@licp.cas.cn; zhouf@licp.cas.cn   \nDr. R. Xu, Y. Zhang   \nCollege of Materials Science and Opto-Electronic Technology, University of Chinese   \nAcademy of Sciences,   \nBeijing 100049, China   \nDr. R. Xu   \nCollege of Chemistry and Chemical Engineering, Northwest Normal University,   \nLanzhou 730070, China   \nDr. S. Ma, Dr. Z. Ma   \nShandong Laboratory of Yantai Advanced Materials and Green Manufacture   \nYantai, 264006, China   \nDr. S. Ma, Dr. Z. Ma   \nYantai Zhongke Research Institute of Advanced Materials and Green Chemical Engineering   \nYantai, 264006, China",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "#Dr. R. Xu and Y. Zhang contribute equally to this work. Keywords: surface modification, polymerization, hydrogel coatings, sticky initiation layer",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# Experimental Section  \n\nMaterials: Dopamine hydrochloride (DOPA, $98\\%$ , J&K Chemical Ltd.), trimethylaminomethane (Tris, $299.9\\%$ (titration), crystalline, ABCONE), citric acid monohydrate (AR, Chengdu Kelong Chemical Reagent Co. Ltd.), sodium hydroxide (NaOH, $296.0\\%$ , Tianjin li an Long Bohua Pharmaceutical Chemistry Reagent Co. Ltd.), Acrylamide (AM, $99\\%$ , J&K Chemicall Ltd.), Acrylic acid (AA, $599\\%$ , TCI Co. Ltd.), N, $\\mathbf{N^{\\prime}}$ - Methylenebis (acrylamide) (MBAA, $99\\%$ , Sigma–Aldrich), ammonium persulfate (APS, $298\\%$ , Chengdu Kelong Chemical Reagent Co. Ltd.), iron (III) chloride hexadydrate $\\mathrm{(FeCl_{3}.6H_{2}O}$ , AR, Tianjin Kemio Chemical Reagent Co. Ltd.), poly(vinyl alcohol) (PVA, $99.9\\%$ , Shanghai City Sinopharm Chemical Reagent Co. Ltd.), poly(ethylene glycol) methyl ether methacrylate (OEGMA, mean molecular weight: 475, 100 ppm MeHQ, 200 ppm BHT, MACKLIN), 2-hydroxyethyl methacrylate (HEMA, $99\\%$ , J&K Chemical Ltd), sodium alginate (SA, Xilong Chemical Co. Ltd.), calcium chloride $(\\mathbf{CaCl}_{2},\\mathbf{\\mu{\\geq}}96\\%$ , Tianjin Fengyue Chemical Co. Ltd.), rhodamine 6G ( $98.5\\%$ , J&K Chemical Ltd), and rhodamine B $(98.5\\%$ , Energy Chemical Ltd).  \n\nCharacterizations: An Olympus optical microscope was used to obtain cross-sectional images of the sample and the thickness of the hydrogel coating. The static contact angles were measured by a DSA-100 optical contact angle meter (Krüss Company, Germany) at ambient temperature $(25~^{\\circ}\\mathrm{C})$ with a droplet of ${5\\upmu\\mathrm{L}}$ of deionized water in air. The final contact angle value was averaged by measuring three different positions on the sample. The cross-sectional morphology was characterized by SEM (PhenomPro X, Netherlands). The $90^{\\circ}$ peeling test was performed on an electrical universal material testing machine with a $500\\mathrm{N}$ load cell (EZTest, SHIMADZU) under a tensile speed of $10\\ \\mathrm{mm/min}$ . The tensile measurement was also performed on an electrical universal material testing machine with a $500\\mathrm{N}$ load cell (EZ-Test, SHIMADZU) under a tensile speed of $100\\mathrm{mm/min}$ . The elastic modulus was calculated from the slope during $5\\%$ strain ratio of the stress-strain curve. The chemical composition of the samples was characterized by a PerkinElmer transform infrared spectrometer (PerkinElmer, USA) with attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR).  \n\nPDA deposition on versatile substrates: First, the versatile substrates were washed completely with alcohol and deionized water under ultrasound followed by drying under ${\\bf N}_{2}$ flow and activated with oxygen plasma for $2~\\mathrm{min}$ ; then, they were immersed in an aqueous solution of dopamine ( $2~\\mathrm{mg/mL}$ , in $10~\\mathrm{mM}$ Tris buffer, $\\mathrm{pH}~8.5\\$ under stirring for a certain time; finally, the samples were rinsed with deionized water and alcohol to remove unreacted chemicals and dried with ${\\bf N}_{2}$ .  \n\nThe production of the $F e^{2+}$ catalyst: First, 5.91 g CA and $5.09\\ \\mathrm{\\g\\FeCl_{3}{\\cdot}6H_{2}O}$ were dissolved in $150~\\mathrm{mL}$ deionized water, and 1 mol/L NaOH solution was added to the above solution until the $\\mathrm{pH}$ reached 4.0; then the substrate deposited with the PDA coating was immersed into the mixed solution for $3\\mathrm{~h~}$ ; finally, the substrates were exposed to UV light ( $365\\mathrm{nm}$ , $15\\mathrm{mW/cm}^{2}$ ) for 2 min to produce $\\mathrm{Fe}^{2+}$ in situ.  \n\nPreparation of HPAA-PAM coating on versatile substrates: The substrates after UV irradiation were immersed into the PAA-PAM monomer solution ( $4.26\\ \\mathrm{g}$ AM, $\\ensuremath{1.08\\mathrm{~g}}$ AA, $_{0.02\\mathrm{~g~}}$ APS and $0.05\\mathrm{~g~}$ MBAA, 30 mL $\\mathrm{H}_{2}\\mathrm{O}$ ) to perform SCIRP for a certain time to grow a uniform hydrogel coating. Furthermore, substrates/devices with growed hydrogel coatings after removal from the monomer solution will be allowed to naturally age for $5\\ \\mathrm{min}$ at room temperature. Meanwhile, the reserved $\\mathrm{Fe}^{2+}$ catalyst and $S_{2}{\\mathrm{O}}_{8}{}^{2-}$ initiator within the network of the formed hydrogel coating initiated further radical polymerization of monomers until most of them were completely consumed. In addition, the substrates with the HPAA-PAM coating after aging were rinsed with deionized water five times to further remove unreacted monomers.  \n\nPreparation of HPNIPAM-PAA coating on Ti substrate: The substrates after UV irradiation were immersed into the monomer solution $(6.78\\ \\mathrm{g}$ NIPAM, 0.864 g AA, $0.02{\\mathrm{~g~}}$ APS and 0.05 $\\mathbf{g}$ MBAA, 40 mL $\\mathrm{H}_{2}\\mathrm{O}$ ) to perform SCIRP for $25~\\mathrm{min}$ .  Furthermore, the Ti substrate with growed PNIPAM-PAA hydrogel coating after removing from the monomer solution was allowed for natural aging of $5\\mathrm{min}$ at room temperature. Finally, the substrates with the HPAAPAM coating after aging were rinsed with deionized water five times to further remove unreacted monomers.  \n\nPreparation of HPVA-PHEMA coating on Ti substrate: First, $6.5\\ \\mathrm{g}$ HEMA, 0.01 g MBAA, 0.02 g APS and $0.1\\ \\mathrm{g}$ AA were dissolved in 50 mL $\\mathrm{H}_{2}\\mathrm{O}$ (solution A), $20\\ \\mathrm{g}$ PVA was dissolved in 100 mL $\\mathrm{H}_{2}\\mathrm{O}$ and heated to $100~^{\\mathrm{{o}}}\\mathrm{{C}}$ until complete dissolution (solution B); then, solution A was mixed with solution B at a volume ratio of 1.5:1; finally, the substrates after UV irradiation were immersed in the above mixed monomer solution to perform SCIRP for 25 min and put into the freeze-dryer to experience freezing $\\left(-40~^{\\mathrm{{o}}}\\mathrm{{C})}$ and thawing $(20~^{\\circ}\\mathrm{C})$ for 3 cycles. After encountering the cyclic freezing-thawing process, the Ti substrate with the HPVAPHEMA coating was rinsed with deionized water five times to remove unreacted monomers.  \n\nPreparation of HPOEGMA-PAA coating on Ti substrate: The substrates after UV irradiation were immersed into the POEGMA-PAA monomer solution ( $\\ensuremath{\\mathrm{\\:6.5~g}}$ OEGMA, 1.08 g AA, 0.01 g MBAA, $_{0.02\\mathrm{~g~}}$ APS, 40 mL $\\mathrm{H}_{2}\\mathrm{O}$ ) to perform SCIRP for $25\\ \\mathrm{min}$ . Furthermore, the Ti substrate with growed POEGMA-PAA hydrogel coating after removing from the monomer solution was allowed to naturally age for 5 min at room temperature. Finally, the Ti substrate with the HPOEGMA-PAA coating after aging was rinsed with deionized water five times to further remove unreacted monomers.  \n\nPreparation of HPOEGMA-PAA-PHEMA coating on Ti substrate: The substrates after UV irradiation were immersed into the POEGMA-PAA monomer solution $3.75\\ \\mathrm{g}$ OEGMA, 3.25 g HEMA, $\\boldsymbol{1.08\\mathrm{g}}$ AA, $_{\\mathrm{0.01~g}}$ MBAA, $0.02{\\mathrm{~g~}}$ APS, 20 mL $\\mathrm{H}_{2}\\mathrm{O}$ ) to perform SCIRP for $25\\mathrm{min}$ . Furthermore, the Ti substrate with growed POEGMA-PAA-PHEMA hydrogel coating after removal from the monomer solution was allowed to naturally age for $5\\ \\mathrm{min}$ at room temperature. Finally, the Ti substrates with the HPOEGMA-PAA-PHEMA coating after aging were rinsed with deionized water five times to further remove unreacted monomers.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# WILEY-VCH  \n\nPreparation of HPVA-PAA-PAM coating on Ti substrate: First, $4.26\\ \\mathrm{g}$ AM, $\\ensuremath{1.08\\mathrm{~g}}$ AA, $\\mathbf{0.02\\g}$ APS and $0.05\\mathrm{~g~}$ MBAA were dissolved in 30 mL $\\mathrm{H}_{2}\\mathrm{O}$ (solution C), $20\\ \\mathrm{g}$ PVA was dissolved in $100~\\mathrm{{mL}}$ $\\mathrm{H}_{2}\\mathrm{O}$ and heated to $100^{\\circ}\\mathrm{C}$ until complete dissolution (solution B); then, solution C was mixed with solution B at a volume ratio of 1:1; finally, the substrates after UV irradiation were immersed in the above mixed monomer solution to perform SCIRP for 2 min and put into the freeze-dryer to experience freezing $\\left(-40~^{\\mathrm{{o}}}\\mathrm{{C})}$ and thawing $(20~^{\\circ}\\mathrm{C})$ for 3 cycles. After encountering the cyclic freezing-thawing process, the Ti substrate with the HPVA-PAA-PAM coating was rinsed with deionized water five times to remove unreacted monomers.  \n\nPreparation of HPHEMA-SA-Ca coating on Ti substrate: First, $6.5\\mathrm{~g~}$ HEMA, 0.01 g MBAA, $0.02{\\mathrm{~g~}}$ APS and $_{\\textrm{1g}}$ SA were dissolved in 50 mL $_\\mathrm{H_{2}O}$ and stirred until complete dissolution; then, the substrates after UV irradiation were immersed into the above monomer solution to perform SCIRP for $2~\\mathrm{min}$ ; finally, the Ti substrate with HPHEMA-SA coating was immersed into CaCl2 solution $(2\\%)$ for $2\\mathrm{h}$ .  \n\nPreparation of patterned hydrogel coating on Ti substrate: First, $5.91\\ \\mathrm{g}$ CA and $5.09\\mathrm{~g~}$ FeCl3· $6\\mathrm{H}_{2}\\mathrm{O}$ were dissolved in $150~\\mathrm{mL}$ deionized water, and 1 mol/L NaOH solution was added to the above solution until the pH reached 4.0. Then, the substrate deposited with the PDA coating was immersed into the above mixed solution for $3\\mathrm{~h~}$ . Subsequently, the treated substrate was placed under the programmable UV light source of a 3D printer for $5~\\mathrm{min}$ to reduce $\\mathrm{Fe}^{3+}$ . Next, the substrate after irradiation with UV light was immersed in monomer solution A to grow a patterned hydrogel coating for a certain time. Correspondingly, the Ti substrate with a growed patterned PAA-PAM hydrogel coating after removal from the monomer solution was allowed to naturally age for $5~\\mathrm{min}$ at room temperature. Finally, the sample after aging was rinsed with deionized water five times to further remove unreacted monomers.  \n\nPreparation of hydrogel coating on the outer surface of various medical devices: First, the medical devices were washed with alcohol and deionized water under ultrasound conditions,",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# WILEY-VCH  \n\nwhich were followed by drying with ${\\bf N}_{2}$ flow and activating with oxygen plasma for $2~\\mathrm{min}$ . Subsequently, the treated medical devices were immersed in an aqueous solution of dopamine ( $2~\\mathrm{mg/mL}$ , in $10~\\mathrm{mM}$ Tris buffer, $\\mathrm{pH}8.5\\rangle$ ) under stirring for $24\\mathrm{~h~}$ to decorate the PDA layer. Next, the PDA-decorated medical devices were rinsed with deionized water and alcohol to remove unreacted chemicals. Then, $5.91\\ \\mathrm{g}\\ \\mathrm{CA}$ and $5.09\\ \\mathrm{g\\FeCl_{3}}{\\cdot}6\\mathrm{H}_{2}\\mathrm{O}$ were dissolved in 150 mL deionized water, and 1 mol/L NaOH solution was added to the above solution until the pH reached 4.0. The PDA-decorated medical devices were immersed in the above mixed solution for $3\\mathrm{{h}}$ . Hereafter, they were exposed to UV light ( $365\\mathrm{nm}$ , $15\\mathrm{mW}/\\mathrm{cm}^{2}$ ) for $2\\mathrm{min}$ to produce $\\mathrm{Fe}^{2+}$ in situ and then immersed in solution A to grow hydrogel coatings for a certain time. Correspondingly, the medical devices with growed PAA-PAM hydrogel coating after removal from the monomer solution were allowed to naturally age for $5~\\mathrm{{min}}$ at room temperature. Finally, the medical devices after aging were rinsed with deionized water five times to further remove unreacted monomers.  \n\nThe demonstrative experiment of alumina ball in PVC catheter: First, the PVC catheter within alumina ball inside was connected with the tube of peristaltic pump and fixed on the desk; then, the alumina ball was swept by the 50-rpm flow rate along the “S” track of PVC catheter.  \n\nFriction force test of alumina ball in PVC catheter: First, the alumina ball was glued to one end of wire, while the other end of wire was stuck into the upper clamp of universal material testing. Meanwhile, the alumina ball was inserted into the PVC catheter with deionized water as lubricant. The force curve was obtained with the dynamic movement of the upper clamp under a constant tensile speed of $5\\mathrm{{mm}/\\mathrm{{min}}}$ .  \n\nFriction force test of steel ball in cattle esophagus: First, the steel ball was glued to one end of the wire rod, while the other end of the wire rod was stuck into the upper clamp of universal material testing. Meanwhile, the steel ball was inserted into the cattle esophagus, while the cattle esophagus was fixed in the bottom tray. The force curve of the steel ball in the cattle esophagus was obtained with the movement of the upper clamp under a constant tensile speed of $50\\mathrm{{mm}/\\mathrm{{min}}}$ .  \n\nFriction Test: The friction test was performed on a conventional ball-on-disk reciprocating tribometer (CSM, Switzerland) under $0.2\\mathrm{~N~}$ and $1\\ \\mathrm{Hz}$ for 300 s in a water bath using elastomeric poly(dimethylsiloxane) (PDMS) hemispheres with a diameter of $6~\\mathrm{mm}$ as pins. The PDMS pins were made by putting the mixture of PDMS and curing agents (mass ratio $\\scriptstyle\\mathbf{\\alpha}=10:1$ ) into a polystyrene 96-well cell culture plate mode under incubation in a $60~^{\\mathrm{{o}}}\\mathrm{{C}}$ oven for $^{4\\mathrm{~h~}}$ . Each sample was measured three times at different positions to obtain the final average value.  \n\nWet mechanical modulus test of the HPAA-PAM coating: The modulus of the HPAA-PAM coating was measured by employing a micronanoindentation on a Bioindenter UNHT3 Bio (Anton Paar). The radius of the indenter (rubby ball) was $0.5\\mathrm{mm}$ , and the normal load was $200~\\upmu\\mathrm{N}$ in the test.  \n\n$$\n\\begin{array}{r l}&{\\mathsf{F e}^{2+}{+}\\mathsf{S}_{2}\\mathsf{O}_{8}{^{2-}}\\longrightarrow\\mathsf{F e}^{3+}{+}\\mathsf{S O}_{4}{^{2-}}\\le\\mathsf{S O}_{4}{^{-}}}\\\\ &{\\mathsf{S O}_{4}{^{-}}*\\mathsf{H}_{2}\\varpi\\longrightarrow\\mathsf{H O}\\bullet\\mathsf{H S O}_{4}}\\\\ &{\\mathsf{H O}\\bullet\\mathsf{H N H}\\longrightarrow\\mathsf{R N}\\bullet\\mathsf{H}_{2}\\mathsf{O}}\\\\ &{\\mathsf{R N}\\bullet\\mathsf{M}\\longrightarrow\\mathsf{R N M}\\bullet}\\end{array}\n$$  \n\n![](images/eb05cfcba48d5330c833b979c386ceadf56600c87c656de7486602645ca19435.jpg)  \nFigure S1. Mechanism for radical generation on the PDA backbone along with covalent coupling between PDA and the hydrogel network (RNH represents PDA, M represents monomer).   \nFigure S2. Component characterization after performing SIL $@$ UV-SCIRP. FT-IR spectra curves of titanium (Ti) and polyethylene (PE) substrates with HPAA-PAM coating.  \n\n![](images/b4c4ce5680b43035156dbaca79d3d5be9da3b7c982c5e56e7ada593edde5a479.jpg)  \nFigure S3. The reusable monomer solution for SIL $@$ UV-SCIRP. (a) Thickness of the HPAAPAM coating on the Ti substrate after growing in the same monomer solution for different times (deposition time: $24\\mathrm{~h~}$ , growth time: $2\\ \\mathrm{min}.$ ). (b) Optical images of fluorescent monomer solution after growing HPAA-PAM coating for different times.  \n\n![](images/5e775b57ec1b77a55ab06b7500a1f36efa00a24dd04ca68616d613338a464d3b.jpg)  \nFigure S4. Wettability characterization. The contact angles of various bare substrates before growing hydrogel coating.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# WILEY-VCH  \n\n![](images/5636f38e6160729a94634c69f4a5afb21746550da8452034fc09b634e01646b0.jpg)  \nFigure S5. Fluorescence images of the PE substrate with hydrogel coating containing rhodamine B $\\mathrm{(1~mg/mL)}$ .  \n\n![](images/e7b563de450d0f1630674077006d7f6b6fe8cf533669d82d844ec64831a11749.jpg)  \nFigure S6. The Modulus of the HPAA-PAM coating measured by micro-nanoindentation.  \n\n![](images/d89ec408f52473a2dd6592aa1a4cf474f6f264f5b4eb30ac05d678a9c1693c7e.jpg)  \nFigure S7. Morphology characterization after performing SIL $@$ UV-SCIRP. (a) Crosssectional morphology of PE substrate convalently bonded with HPAA-PAM coating and (b) corresponding EDS mapping of carbon (C, red), oxygen (O, purple) and nitrogen (N, green).  \n\n![](images/e8c7c19fcb3345285a69a60cf3ad0403613d4d7a67bde65493d8089bf7664497.jpg)  \nFigure S8. The friction curve of the HPAA-PAM coating on PE substrate for 7200 sliding cycles.  \n\n![](images/0cbefa46201ce788f4ea975884bd76957084a094d13926aab0c5b75aacd1b72a.jpg)  \nFigure S9. Mechanical properties of the fiber-enhanced composite hydrogels prepared by the SIL $@$ UV-SCIRP method. (a) The stress-strain curves of pure fiber and fiber-hydrogel composite, and (b) the corresponding elastic modulus.  \n\n![](images/18d06c2584cec7793b80da847d993b8e22e8c03b817f85be99b1ce4deca09b47.jpg)  \nFigure S10. Surface lubrication modification of SIL $@$ UV-SCIRP. The cross-sectional fluorescence microscopic images of catheters modified with HPAA-PAM lubrication coating stained with rhodamine 6G. (a) PVC catheter and (b) Latex catheter.  \n\n![](images/3438540e9bf65a0509956f70a32d04c6c4f8734dc4a44dc8ba92c9a853429afb.jpg)  \nFigure S11. Demonstration of lubrication-assisted movement of hydrogel-decorated balls within confined channels. Schematic illustration of the movement of alumina ball and alumina ball modified with HPAA-PAM coating within the channel of an “S-shaped” PVC catheter under a $50\\mathrm{rpm}$ flow rate.  \n\n![](images/41360523ade5481aaac93af4c9bd8a189814f3fe24cc5707d4a7e4c43e5ea476.jpg)  \nFigure S12. The lift test method for capturing the friction force signal of steel ball in cattle esophagus.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# Supporting Movies  \n\nSupplementary Movie 1: The moving process of a controlled alumina ball (left) and modified-alumina ball with HPAA-PAM coating (right) along the water flow within the “S” PVC catheter tube under a 50-rpm flow rate.",
+        "category": " Results and discussion"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Multifunctional Nano-Conductive Hydrogels With High Mechanical Strength, Toughness and Fatigue Resistance as Self-Powered Wearable Sensors and Deep Learning-Assisted Recognition System  \n\nYanqing Wang, Picheng Chen, Yu Ding, Penghao Zhu, Yuetao Liu, Chuanxing Wang, and Chuanhui Gao\\*  \n\nHigh mechanical strength, toughness, and fatigue resistance are essential to improve the reliability of conductive hydrogels for self-powered sensing. However, achieving mutually exclusive properties simultaneously remains challenging. Hence, a novel directed interlocking strategy based on topological network structure and mechanical training is proposed to construct tough hydrogels by optimizing the network structure and modulating the orientation of molecular chains. Combining $Z n^{2+}$ crosslinked cellulose nanofibers (CNFs) and a polyacrylamide-poly(vinyl alcohol) double-network, the unique interlocked-network structure exhibits an enhanced toughening effect due to hydrogen bonding and metal-ligand interactions. The aligned nanocrystalline domains achieved by training further contribute to an increase in the toughness and fatigue thresholds. This innovative approach synergistically enhances the mechanical properties of the nano-conductive hydrogel, achieving a maximum tensile strength of 4.98 MPa and a toughness of 48 MJ $\\mathbf{m}^{-3}$ . Notably, the CNFs template with anchored polyaniline, when oriented through mechanical training, forms a unique directional conductive pathway, which significantly enhances the power output performance. Besides, a motion recognition system based on a self-powered sensing device is designed with the assistance of deep learning techniques to accurately identify human motion behaviors. This work showcases a potentially transformative flexible electronic material for self-powered sensing systems and intelligent recognition systems.",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1. Introduction  \n\nIn recent years, the integrated sensing system comprising a friction nanogenerator (TENG), a supercapacitor (SC), and flexible sensors has increasingly attracted the attention of researchers.[1] The development of this device addresses the issues of excessive dependence on external power sources and the inability to satisfy the demand for lightweight portability.[1b, 2] TENG effectively converts mechanical energy into electrical energy, and when coupled with the energy storage capabilities of SC, smart sensing devices can continuously access green and stable power sources.[3] However, although traditional inorganic semiconductor materials can be used as substrates to meet the requirements of power supply output and sensitivity of the aforementioned units, their lack of mechanical flexibility, poor fatigue resistance, environmental tolerance and biocompatibility seriously hinder the application of wearable electronic devices.[4] In this context, hydrogel materials assume a pivotal role, due to the low cost, facile preparation and biocompatibility.  \n\nTheoretically, the mechanical strength, fatigue resistance and conductivity of hydrogels are closely related to the durability and power output of self-powered systems.[5] Unfortunately, current conductive hydrogels are unable to meet the demands of various scenarios due to the above performance partly shortcomings. Many effective mechanisms have been developed to enhance the mechanical properties of hydrogels, including hierarchically structured networks, nanofiller composite, hydrophobically bonded and metal coordination hydrogels. For instance, Gong’s team[6] pioneered a dual network (DN) hydrogel mechanism. The hydrogel typically comprises a strongly crosslinked rigid network and a weakly crosslinked flexible network. Superior applications of DN hydrogels have been demonstrated in numerous fields over the years. Building on this, in response to the permanent damage to the hydrogel from notch cracking and improving fatigue resistance, Suo’s team[7] synthesised a highly stretchable and ductile hydrogel containing two different types of crosslinks. The unique design allows the covalently crosslinked network to be crack-bridged and the ionic interaction crosslinked network to re-heal after damage, thereby further expanding the potential application scenarios of the hydrogel. Jiang’s team[8] proposed a simple strategy for preparing hydrogels with high strength, toughness and ion conductivity. The anisotropic structure constructed by directional freezing combined with the metal coordination effect and salting-out effect could achieve the densification of the network structure, thereby greatly improving the mechanical properties. The high strength and tough hydrogels were also assembled with sensors to realize intelligent applications. The incorporation of nanofibers can simultaneously enhance fatigue resistance and fracture toughness by modifying the structural orientation. Sun et al.[9] introduced rod-shaped cellulose nanocrystals into a conventional polyacrylamide hydrogel network via a straightforward method. The polymer network is capable of switching the orientation during cyclic loading, thereby transmitting stresses to impede crack extension. In order to counteract the effects of low strength and poor fatigue resistance, Zhao et al.[10] obtained a hydrogel that resembles a muscle-oriented arrangement through the implementation of mechanical training. The cyclic freeze-thawed PVAbased hydrogel was observed to achieve a muscle fibre structure in a mechanical training environment, effectively increasing the mechanical strength and fatigue resistance of the material. However, it was discovered that hydrogels comprising solely of PVA, which possess a single network structure, lack an effective constraining structure to impede the movement of the PVA chain segments. This renders it challenging to maintain the microcrystalline orientation imparted by mechanical training, and furthermore, the lifting effect is difficult to sustain.[11] In light of the aforementioned studies, the development of triple network hydrogels has received a lot of attention from researchers in recent years.[12] This type of hydrogel could withstand greater external forces and exhibit enhanced flexibility, meeting the needs of more application scenarios due to its unique topology and dissipation mechanism.  \n\nIonic conductive hydrogels that facilitate ionic conduction are of significant interest to researchers due to the advantages they offer, including good conductivity and cost-effectiveness. Hong et al.[13] developed a class of hydrogel electrolytes with exceptional conductivity by immersing chemically crosslinked polymer films in a sodium perchlorate solution. In the application of hybrid capacitors, the advantages of hydrogel electrolytes enabled the attainment of high multiplicative capacity, ultra-high specific capacity with long cycling capability, and other beneficial properties. Chen et al.[14] introduced NaCl into doublenetwork hydrogels to develop a hydrogel electrolyte with both outstanding toughness and electrical conductivity. As an ideal candidate for flexible electronic devices, the fabricated hydrogel electrolyte was applied in the field of flexible sensing. Furthermore, the device maintained good electrical conductivity even at low temperatures. Despite the impressive tensile toughness of ion-conductive hydrogels, the challenge of balancing electrical conductivity and mechanical integrity has remained a significant concern in the field.[10] Furthermore, issues such as low ionic conductivity continue to impact the performance of electronic devices. In contrast, the incorporation of conductive fillers, such as metal nanoparticles, carbon nanotubes,[15] MXene,[16] and polypyrrole[17] into electronic conductive hydrogels significantly enhances the electrical conductivity and contributes to the overall strength. Cai et al.[18] prepared a high-performance hydrogel material from polyvinyl alcohol, lignin and silver nanoparticles (AgNPs), which can confer a high electrical conductivity of $1\\mathrm{S}\\mathrm{m}^{-1}$ while enhancing the mechanical properties ( $_{\\mathrm{13.3\\MPa}}$ stress and toughness of 78.1 MJ $\\mathbf{m}^{-3}$ ) of the material. Similarly, Zhu’s team[19] used silver nanowires (AgNWs) as conductive fillers in combination with polyamide nanofibres and polyvinyl alcohol to design a heterogeneous structure that gives the hydrogel an ultra-high apparent conductivity, based on which the hydrogel also exhibits good shielding properties against electromagnetic interference. The in-plane configuration of the fibre structure, in conjunction with robust hydrogen bonding, facilitated the attainment of a tensile strength of $5.5\\ \\mathrm{MPa}$ and a fracture energy of 5.7 kJ $\\mathbf{m}^{-2}$ for the hybrid hydrogels. An organohydrogel-based ionic diode with dual response to humidity and pressure is presented by Yin et al.[20] The introduction of MXene as the conducting phase improves the overall rectification ratio of the material, while the diode exhibits excellent power density with output current under pressure. This study demonstrates the potential of hydrogels in the field of energy harvesting and sustainable energy development. However, under large mechanical stretching and compression, conductive fillers are prone to leakage or uneven distribution, which lowers the percolation threshold.[21] Therefore, how to ensure a better integration between the conductive filler and the gel matrix is still a contemporary concern. Furthermore, the water within the conductive hydrogel matrix is prone to freezing or evaporation in response to extreme environmental conditions, coupled with the lack of effective healing properties, which significantly restricts the potential applications of the material. Consequently, the development of highly conductive and durable multifunctional hydrogel-based electronic devices continues to present significant challenges.  \n\nHerein, we present a study on the high mechanical strength, toughness and fatigue-resistant multifunctional conductive hydrogels for constructing self-powered sensing devices and deep learning-assisted recognition systems. A unique triple interlocking network composed of polyvinyl alcohol (PVA), polyacrylamide (PAAm), and $\\mathrm{CNFs}{\\cdot}\\mathrm{Zn}^{2+}$ ensures structural stability, while the oriented alignment of the molecular chains, aided by mechanical training, significantly improves strength $(4.98\\:\\mathrm{MPa})$ and toughness $(48{\\mathrm{~M}}{\\mathrm{J}}{\\mathrm{~m}}^{-3},$ ). This process of nanocrystalline domain formation and reorientation endowed the conductive hydrogels with crack extension insensitivity, thus improving the fatigue resistance. The configuration of the interlocking network structure guarantees the continuous improvement effect of the mechanical training orientation structure. The proposed oriented interlocking strategy overcomes the limitations of conventional conductive hydrogels, which typically cannot achieve strength, toughness and fatigue resistance simultaneously. Furthermore, template structures were introduced into the system to overcome unwanted interactions between the gel matrix and the conductive filler. The polyaniline (PANI) anchored to CNFs forms a unique conductive pathway by constructing conductive fibres during training, with post-orientation conductivity reaching $12~\\mathrm{S~m}^{-1}$ , ensuring robust output performance in self-powered devices. Besides, to expand the application scenarios of the conductive hydrogel, we introduce self-healing property, antifreezing and moisturising property. This ensures that the prepared hydrogel remains functional over extended periods. The conductive gel has been successfully applied to self-powered sensing systems and a deep-learning-assisted motion recognition system has been developed, demonstrating reliable practical application value.  \n\n![](images/fdc3709744bdf1fce23e9a7d543436e07bf3681d27da2c222b3363af9dfbbd7e.jpg)  \nScheme 1. The schematic preparation of the all-round $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ hydrogel and the self-powered application system.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2. Results and Discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2.1. Design Principle and Synthesis of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}\\mathsf{-}\\mathsf{Z}\\mathsf{n}^{2+}$ Hydrogel  \n\nFrom advancements in human-computer interaction to applications in medical sensing, electronic skin, and environmental monitoring, various crucial technologies depend on the collection and transmission of signals by electronic sensing devices. However, ensuring the transmission of stable signals places higher demands on the reliability of the device body. In this study, a novel strategy of simple toughening enhancement is employed to improve the durability and stability of conductive hydrogels. These hydrogels were then assembled into a comprehensive self-powered system for applications in smart sensing and deep learning-assisted recognition, as depicted in Scheme 1. The third network composed of CNFs- $Z\\mathrm{n}^{2+}$ was introduced onto the traditional PVA-PAAm dual network hydrogel. This network could fracture before the covalent bonding network under external forces, owing to the synergistic effect of hydrogen bonding and metal-ligand bonding. It enhanced the strength and toughness of the material by effectively dissipating mechanical energy. Building upon this foundation, the mechanical training strategy was introduced into the interlocked-network system to simulate the anisotropic structure and alignment of tendons, further improving the toughness and fatigue resistance of the material. The alignment of PVA molecular chains resulted in the directional arrangement of the added nanocrystalline domains, which effectively dissipated the stress transfer between molecular chains.  \n\nFurthermore, under mechanical training, the aligned molecular chains exerted a clamping effect on the cracks, thereby increasing the required fracture energy compared to that of amorphous polymer chains. This enhancement significantly improved the fatigue resistance of the material. The interlocking structure ensures that the orientation gain achieved through mechanical training is maintained over time. Additionally, to guarantee the durability and environmental resilience of the assembled selfpowered sensing devices, the materials were endowed with selfrepairing properties and anti-freezing ability. This extension further broadens the application scenarios of hydrogels. For the purposes of clarity, we denote the borax-crosslinked PVA network with PAAm network constituting a dual-network hydrogel as $\\mathrm{PVA_{B}}$ -PAAm, the PVA Borax/AAm/CNF-PANI hydrogel as $\\mathrm{P_{\\mathrm{{B}}}A C_{\\mathrm{{A}}}}$ hydrogel, and the hydrogel impregnated with $\\mathsf{Z n}(\\mathsf{B F}_{4})_{2}$ ions as $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogel (Subscript $\\mathrm{{}^{\\prime\\prime}\\mathrm{{B}^{\\prime\\prime}}}$ represents Borax, while the subscript “A” represents PANI).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2.2. Network Structure Analysis of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}{\\mathsf{-}}\\mathsf{Z}\\mathsf{n}^{2+}$ Hydrogel  \n\nA series of characterizations were conducted to investigate the network structure and composition of the $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogels. Figure 1(a) illustrated a schematic representation of the self-assembly process of CNFs and PANI. The advanced template technology enabled a more uniform distribution of conductive fillers, thereby facilitating precise control of the microscale structure. Figure 1(b) illustrated that the CNFs-PANI suspension, when placed independently for 3 days, could still be stable. The formation of the template structure can be observed by TEM. The average diameter of the pristine CNFs was approximately $30\\mathrm{nm}$ . TEM images of templated cellulose nanofibers, prepared by in situ polymerization of ANI on the surface of CNFs, revealed a significant thickening of the nanofiber structure. It is possible that these irregular protrusions may have originated from ANI polymerization, indicating that the synthesis of CNFs-PANI was accomplished successfully. To elucidate the nature of the highly binding mode between CNFs and PANI, a molecular simulation of the self-assembly process was conducted using molecular electrostatic potential, as shown in Figure 1(c). The presence of a lone pair of electrons in ANI and the orbitals it occupied could be conjugated to the benzene ring, since the electron cloud could be dispersed to the benzene ring, thus the density of the electron cloud around the N atom was reduced. The hydroxyl and carboxyl groups present on the molecular chain of the CNFs could restrict the nucleation position of the ANI intermediates by electrostatic attraction.[22] This allowed the conductive filler PANI to carry out the self-assembling process on the surface of the CNFs molecules, forming a tightly bound structure. The compositional structure of CNFs-PANI was further characterized by FT-IR tests, as shown in Figure S1 (Supporting Information). For CNFs, the peak observed at $3390~\\mathrm{cm}^{-1}$ corresponded to the $-\\mathrm{OH}$ stretching vibration, whereas the peak at a wavelength of $1722~\\mathrm{cm}^{-1}$ denoted the oxidized carboxylate functional group.[23] For PANI, the absorption peaks observed at 1587 and $1411\\mathrm{cm}^{-1}$ correspond to the $-\\mathrm{NH}$ stretching vibration and the $C^{-\\mathsf{C}}$ stretching vibration of the quinone and benzene rings on PANI, respectively.[24] Compared the reactants, the principal peaks associated with both quinone and benzene rings on the CNFs-PANI complexes exhibited a gradual shift toward lower frequencies ( $1570\\mathrm{cm}^{-1}$ and $1390~\\mathrm{cm}^{-1}.$ ), thereby confirming the occurrence of robust interactions between PANI and CNFs, which ultimately led to the formation of a tightly anchored template structure.[25]  \n\nThe interlocking structure of $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogels with a triple topological network was next investigated. Figure 1(d) illustrated the FT-IR spectra of the various components of the CNFsPANI, $\\mathrm{PVA_{B}}$ -PAAm, $\\mathrm{P_{B}A C_{A}}$ and $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogels. The incorporation of CNFs had led to the formation of hydrogen bindings structure within the system, resulting in the gradual shift of the $-\\mathrm{C}=0$ peaks to lower wave numbers. Furthermore, the absorption peak at $1725~\\mathrm{cm}^{-1}$ corresponded to the metal-ligand bond formed by $\\scriptstyle{\\mathrm{Zn}}^{2+}$ .[26] Notably, the sharp peaks were observed at $1458~\\mathrm{cm^{-1}}$ , $1453~\\mathrm{cm}^{-1}$ and $1425~\\mathrm{cm^{-1}}$ , which were due to the borate bindings configuration within the system.[24,25] Further insights into the interlocking structure of the $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogel was gleaned through XPS tests. As shown in Figure 1(e), the presence of C, N, O and $Z\\mathrm{n}$ elements in the $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogel were evident from the test spectra. To verify the formation of metal-ligand bonds, we focus here on the analysis of the element Zn. The binding energy of $\\mathrm{Zn^{2+}}$ in the prepared $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogel exhibited a gradual shift toward higher binding energy, indicating the formation of robust $Z\\mathrm{n-O}$ polar bonds between - COOH and ${\\mathrm{Zn}}^{2+}$ on CNFs (Figure 1(f)).[1c,27] This observation, in conjunction with the FT-IR analyses, provided compelling evidence for the formation of metal-ligand bonds. Furthermore, the mapping of the Zn element indicated a uniform distribution, which was conducive to the stability of the structure and provided support for the preparation of high-strength and hightoughness hydrogels. Additionally, the surface morphology of different component hydrogels was analyzed. In comparison to the $\\mathrm{PVA}_{\\mathrm{B}}$ -PAAM hydrogels with $5\\upmu\\mathrm{m}$ average pore size (Figure 1g), the $\\mathrm{P_{B}A C_{A}}$ hydrogel exhibited a denser structure (Figure 1h), which possessed an average pore size of around $3\\upmu\\mathrm{m}$ . This was attributed to the fact that the CNFs chains were combined with the double-network hydrogel in the form of semi-intercalation and the abundant -COOH and $-\\mathrm{OH}$ on the chains form dense hydrogen bindings with the components in the system. The introduction of $\\scriptstyle{\\mathrm{Zn}}^{2+}$ as a cross-linking point and its interspersion with the CNFs resulted in the formation of the third network, which constituted a unique topology structure with the doublenetwork hydrogel (Figure 1i). This process led to the formation of a dense net-like structure in $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogels.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.3. Mechanical Properties of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}{\\mathsf{-}}\\mathsf{Z}\\mathsf{n}^{2+}$ Hydrogels Based on Directional Interlocking Strategy  \n\nThe mechanical properties of hydrogel materials, including stress at break (strength), elongation at break (toughness) and fatigue threshold, are interrelated but conflicting. An increase in elastic modulus and strength leads to a decrease in material deformability.[28] Furthermore, the existing robust conductive hydrogel materials remain susceptible to fatigue fracture following prolonged mechanical cyclic loading, which greatly limits the application of hydrogel materials.[29] To address these challenges, a topologically interlocked hydrogel with a triple network structure was first designed. As illustrated in Figure 2(a), the tensile curves of both the $\\mathrm{PVA_{B}}$ -PAAM dual network hydrogel and the $\\mathrm{P_{B}A C_{A}}$ semi-interpenetrating network hydrogel demonstrated good elastic behavior. As the content of CNFs increased, the tensile stress and fracture strain of the $\\mathrm{P_{\\mathrm{{B}}}A C_{\\mathrm{{A}}}}$ hydrogels both increased simultaneously. At a CNFs content of $4\\mathrm{wt\\%}$ , the maximum stress reached $0.67\\mathrm{MPa}$ , which was approximately 27 times the mechanical strength of the $\\mathrm{PVA_{B}}$ -PAAM hydrogel. Furthermore, as illustrated in Figure $2(\\mathsf{b})$ and Figure S2 (Supporting  \n\n![](images/9aaaa9c8fae9030c55d5f68191a55c60d2d0ae9223142bdb4121fa1c65f45eb7.jpg)  \nFigure 1. Structural characterization of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ hydrogel. a) Schematic diagram of the templated CNFs-PANI assembly. b) The images of CNFs, ANI and CNFs-PANI; TEM images of CNFs and CNFs-PANI. c) Molecular electrostatic potential of CNFs and ANI. d) The FT-IR spectrum of CNFsPANI, $P V A_{\\mathsf{B}}$ -PAAm, $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}$ and $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.Z\\mathsf{n}^{2+}$ hydrogel. e) XPS spectrum of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ hydrogel. f) XPS spectra of Zn in hydrogels. SEM images of g) $P V A_{B}$ -PAAm, h) $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}$ and i) $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ hydrogel. Scale bar: 1 cm.  \n\n![](images/7bdb637c4066eb99657ecea2554e084d87d8974170714733333708e19208d2a6.jpg)  \nFigure 2. Mechanical properties of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.Z\\mathsf{n}^{2+}$ hydrogels. a) Stress-strain curves and b) toughness of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}$ hydrogels with different CNFs ratios. c) Stress-strain curves and d) toughness of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ hydrogels with different $Z n^{2+}$ ratios. Rheological testing of hydrogels at different e) strains and $\\mathsf{f})$ frequencies g) Interactions between the components in the $P V A_{B}$ -PAAm hydrogel and h) the corresponding distribution plots. i) Interactions between the components in the $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}$ hydrogel and j) the corresponding distribution plots. k) Interactions between the components in the $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}{-}Z\\mathsf{n}^{2+}$ hydrogel and l) the corresponding distribution plots.  \n\nInformation), the $\\mathrm{P_{B}A C_{A}}$ hydrogels also demonstrated satisfactory toughness $(3.6~\\mathrm{MJ~m}^{-3}$ ) and Young’s modulus $(0.28\\ \\mathrm{MPa})$ , expanding the scope of applications for wearable sensors. These high mechanical properties are attributed to the formation of an effective hydrogen bonding system between the CNFs and the $\\mathrm{PVA_{B}}$ -PAAM network, which enhanced the interactions between the molecular chains. However, the addition of an excess of CNFs $(5~\\mathrm{wt}\\%)$ resulted in the formation of agglomerates due to the own large aspect ratio and entanglement between molecular chains.[30] This led to an uneven stress distribution in the hydrogels. Furthermore, the excess CNFs led to hydrogen bonding between CNFs-CNFs and a reduction in the CNFs-PVA or CNFsPAAm interactions, thereby resulted in a reduction in mechanical strength. Consequently, the $\\mathrm{P_{B}A C_{A}}$ hydrogels with a content of $4\\mathrm{wt\\%}$ CNFs were selected for the subsequent investigation.  \n\nThe $\\mathrm{P_{B}A C_{A}}$ hydrogels were subsequently immersed in a $\\mathsf{Z n}(\\mathsf{B F}_{4})_{2}$ solution to enhance the metal cross-linking system, aiming to construct a triple-network interlocking structure. As illustrated in Figure 2(c), the composite hydrogel, further cross-linked by $Z\\mathrm{n}^{2+}$ , demonstrated remarkable tensile strength $(2.52\\ \\mathrm{MPa})$ and strain at break $(1520.4\\%)$ , which were 3.8 and 1.3 times higher than those of the $\\mathrm{P_{B}A C_{A}}$ hydrogels, respectively. Furthermore, the incorporation of the interlocking structure had resulted in an unexpected increase in pressure resistance (Figure S3, Supporting Information). Concomitantly, the toughness and Young’s modulus of the $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogels exhibited varying degrees of enhancement, as illustrated in Figure $2(\\mathrm{d})$ and Figure S4 (Supporting Information). CNFs, in a semi-interpenetrating form, constructed the network structure and achieved a mechanical interlock with the $\\mathrm{PVA_{B}}$ -PAAM hydrogel under the action of $Z\\mathrm{n}^{2+}$ , significantly enhancing the mechanical strength of the material.  \n\nTo further investigate the enhancement mechanism of the interlocking network, dynamic rheological tests were performed on various hydrogel combinations. Figure 2(e) exhibited the test curves of $\\mathsf{P}_{\\mathrm{B}}\\mathsf{A C}_{\\mathrm{A}}$ and $\\mathrm{P_{B}A C_{A}{-}Z n^{2+}}$ hydrogels at constant frequency in relation to dynamic strain. In the linear viscoelastic region, both hydrogels demonstrated pronounced elastic behavior, with the energy storage modulus $(\\mathbf{G}^{\\prime})$ consistently exceeding the loss modulus $\\big(\\mathrm{G}^{\\prime\\prime}\\big)$ . Upon application of a specific strain, the $\\mathbf{G}^{\\prime\\prime}$ of both $\\mathrm{P_{B}A C_{A}}$ and $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogels initially demonstrated an enhancement, followed by a decline. This pattern was notably reversed for $\\mathbf{G}^{\\prime\\prime}$ . The critical strains at the crossing points in the test curves indicated that the transition from the gel state to the viscous flow state occurred due to the collapse of the polymer network structure.[31] Notably, the critical strain of the $\\mathrm{P_{B}A C_{A}}$ hydrogel was $23\\%$ , while that of the $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogel was $210\\%$ . The test results confirmed that the triple network interlocking structure constructed by $Z\\mathrm{n}^{2+}$ enhanced the stability of the hydrogels. Furthermore, the frequency scans of the two hydrogels at constant strain were tested. As illustrated in Figure $2(\\mathrm{f})$ , both the $\\mathsf{P}_{\\mathtt{B}}\\mathtt{A C}_{\\mathtt{A}}$ and $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogels exhibited elastic solid-state behavior. However, the $G^{\\prime}$ of the $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogels were significantly higher than that of the $\\mathrm{P_{B}A C_{A}}$ hydrogels. This was attributed to the introduction of $Z\\mathrm{n}^{2+}$ , which optimized the interlocking topological network. The sacrificial bonds present therein dissipate mechanical interactions, thereby enhancing the mechanical strength of the material. Subsequently, it was observed that the mechanical properties of $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogels exhibited a decreasing trend when the ${\\mathrm{Zn}}^{2+}$ concentration reached $4~\\mathrm{mol~L^{-1}}$ . This decrease was attributed to the excess $\\mathrm{Zn^{2+}}$ remaining uninvolved in the cross-linking behavior and being free within the network, thereby weakening the interactions between the molecular chains.  \n\nFurther insight into the relationship between the microscopic interlocking structure and macroscopic mechanical behavior was gained through simulations. The use of IRI plots (Figure $2(\\mathrm{g,i,k})]$ and ELF function topography (Figure $2(\\mathrm{h,j,l})$ ) to represent the interaction forms allowed the gradual increase in the pink areas (intermolecular interactions) to be observed with the incorporation of CNFs and $Z\\mathrm{n}^{2+}$ . This indicated that the intermolecular interactions were enhanced after the construction of the triple interlocking network structure, with higher values also observed in the corresponding equivalent surface-enclosed regions.  \n\nTo further enhance the mechanical strength and fatigue resistance of conductive hydrogels with interlocking structures, a mechanical training approach was introduced to achieve oriented nanofiber alignment structures in muscle-like hydrogels. Figure 3(a) schematically depicted the training strategy for skeletal muscle-like hydrogels. Initially, the tensile limit strain for mechanical training was determined by the energy loss of cyclic stretching at different strains,[32] as shown in Figure S5 (Supporting Information). Upon relaxation of the first cyclic stretching, the directionally arranged fiber structures in the network typically revert to the initial disordered distribution state. As the number of training cycles increased, the plastic deformation phenomena accumulated in the $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogels network, causing the hydrogel samples gradually elongated in the tensile direction and maintain the oriented arrangement. The cyclic tensile tests at $200\\%$ , $400\\%$ , $60\\%$ , $80\\%$ , and $100\\%$ strains revealed that the $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogel exhibited notable hysteresis phenomena, with the lowest residual strain values of the $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogels occurring when subjected to strains between 0 and $400\\%$ . However, as the cyclic strains exceeded $400\\%$ the residual tensile strain values of the hydrogel gradually increased, indicating that the interlocking network structure began showing signs of rupture. To maintain the optimal training effect, $400\\%$ tensile strain was chosen as the mechanical training condition. Subsequently, the mechanical properties of the $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogels were examined under varying training periods, with the tensile stress and fracture strain of the $\\mathrm{P_{B}A C_{A}}$ $Z\\mathrm{n}^{2+}$ hydrogels exhibiting varying degrees of enhancement under the accelerated mechanical training environment. The hydrogel splines were named $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn^{\\vec{2}+}}{\\cdot}\\mathrm{X}$ , where ${\\boldsymbol{\\mathrm{X}}}=1$ min, 3 min, 5 min. As illustrated in Figure ${3(b,c)}$ , following a training period of 3 minutes, the tensile strength of the $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}{-3}$ hydrogel reached $4.98~\\mathrm{MPa}$ , while the strain at break reached $2100\\%$ , representing a doubling of the stress and a 1.5-fold increase in the strain compared to that of the $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogels, which was a highly unusual occurrence in the literature on high-strength hydrogels. The strength and toughness of the $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}{-5}$ hydrogel $(48\\mathrm{~M})\\mathrm{~m}^{-3},$ ) were found to be stable when trained to 5 minutes (Figure S6, Supporting Information), because of the oriented alignment of the molecular chain segments in the interlocking network. It was noteworthy that the mechanically trained $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogels exhibited anisotropic behavior. As illustrated in Figure 3(d), the mechanical strength of the $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogel in the vertical direction (2 MPa) was comparable to that of the untrained hydrogel, but considerably lower than that of the hydrogel parallel to the training direction. This was attributed to the fact that the original hydrogen bonding and nanocrystalline domains between the molecular chain segments perpendicular to the stretching direction remain unchanged, while the effect of transverse shrinkage was minimized.[10]  \n\n![](images/e2bbddbc70a87637abf9515580afae0aa467fe9708658d16a297b35ff55bc6e9.jpg)  \nFigure 3. Mechanical properties of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.Z\\mathsf{n}^{2+}$ hydrogels under mechanical training. a) Schematic diagram of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ hydrogel mechanical training. b) $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}{-}Z\\mathsf{n}^{2+}$ hydrogels possess extraordinarily large tensile strains. c) Stress–strain graphs of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}{-}Z\\mathsf{n}^{2+}$ hydrogels at different training times. d) Stress-strain plots of mechanically trained hydrogels in parallel and perpendicular directions. e) SAXS patterns of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ hydrogels before and after mechanical training. f) FT-IR curves changes before and after $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A}\\dot{\\mathsf{C}}_{\\mathsf{A}}.\\dot{Z}\\mathsf{n}^{2+}$ hydrogel training. g) Tear patterns of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ hydrogel cracks in different stretch directions. h) Stress–strain diagrams of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}{-}Z\\mathsf{n}^{2+}$ hydrogel crack extension in different directions. i) Fracture energy and crack extension strain of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ hydrogels in different training directions.  \n\nThe exceptional mechanical properties of training $\\mathrm{P_{B}A C_{A}}$ $Z\\mathrm{n}^{2+}$ hydrogels were elucidated through several tests. First, SAXS analysis was employed to study the nanocrystal arrangement of the training hydrogel (Figure 3e). It can be observed that the original randomly oriented nanocrystalline domains in the $\\mathrm{P_{B}A C_{A}}.$ $Z\\mathrm{n}^{2+}$ hydrogel were reoriented after training. This resulted in the reconfiguration of the hydrogen bonding system and interlocking structure between the PVA chain segments and the CNFs chain segments, which impeded the movement of the chain segments. The simultaneous enhancement of the strength and toughness of the $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogel was achieved. Furthermore, the SEM analysis revealed that the original pore-like structure transitioned to a seam-like state along the training direction, leading to a reduction in the original spacing between chain segments. Additionally, the network structure exhibited a denser configuration following the oriented arrangement (Figure S7, Supporting Information). The changes in the cross-linked network of $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogels before and after training were further analyzed by FT-IR testing. The original interlocking structure was reoriented and rearranged following training, while the PVA chains rich in $-\\mathrm{OH}$ and CNFs chains underwent a similar rearrangement. PVA chains were observed to slip with the CNFs chains, thereby re-forming a denser hydrogen bonding system. This resulted in a shift of the FT-IR peaks of the trained $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogels towards lower wavelengths (Figure 3f). Crystallinity of materials often indispensably influences the mechanical properties. To demonstrate the change in crystallinity of the PVA chain segments and nanofibers before and after training, validation analyses were also performed by XRD and DSC tests. As illustrated in Figure S8 (Supporting Information), the chain segments within the interlocking network became aligned in a tightly ordered configuration following the slip. Formation of nanocrystalline domains among the PVA molecular chains and nanofibers led to an oriented arrangement, resulting in significantly enhanced intensity of the crystalline peaks in the trained $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogel relative to the initial state. This evidence suggested that the mechanical training process has the potential to significantly improve the crystallinity of the hydrogel. The same conclusion can be drawn from the DSC test in Figure S9 (Supporting Information). Calculations led to the conclusion that trained hydrogels could achieve a crystallinity of $30\\%$ . The increase in crystallinity could be attributed to the rearrangement of disordered molecular chains following mechanical training, accompanied by a gradual increase in the number of nanocrystalline domains between the resulting oriented structures. The designed triple interlocking network possessed an adequate energy dissipation structure, and mechanical training provided external support for directional arrangement of interlocking chain segments and crystalline domains in the $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogel. Unique design also lays the foundation for the construction of the directional conductive pathway in the following.  \n\nTo verify the uniqueness of CNFs-based triple-network interlocking hydrogels during mechanical training, SA-based triplenetwork hydrogels were prepared and mechanically trained using the same method. As illustrated in Figure S10 (Supporting Information), the tensile strength of SA-based hydrogels could reach $0.5~\\mathrm{MPa}$ , and the mechanical properties of the hydrogels did not exhibit significant alterations following multiple mechanical trainings. SA, as a semi-rigid biobased filler, could form interactions with the dual-network hydrogels and thus enhance the mechanical properties. However, it did not contribute to the increase in crystallinity during the mechanical training process. Significantly, the formation of hydrogen bonds between CNFs molecules and van der Waals interactions between neighboring glucose units, which promoted the parallel stacking of cellulose chains.[33] This resulted in an increase in the number of crystalline domains and a tendency towards oriented rows.[34] This, in conjunction with the synergistic effect of the crystalline domains formed between the PVA chain segments, led to an improvement in the mechanical strength of the $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogels.  \n\nThe resistance to crack extension determines the resistance of the hydrogel, thus the ability of trained $\\mathrm{P_{B}A C_{A}{-}Z n^{2+}}$ hydrogels to resist crack extension was analyzed. As illustrated in Figure $3(\\mathrm{g})$ , the mechanically trained $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogel demonstrated high-strength mechanical properties, with the directionally arranged molecular chain segments distributed perpendicularly to the crack notch. When subjected to external force, the notched sample formed a bridging at the crack tip, enabling the aligned nanocrystalline domains to effectively transfer and dissipate the resulting stress concentration. As the notch further expanded, the oriented molecular chain segments required more energy to fracture.[35] Consequently, the fatigue threshold was considerably higher than that of the general hydrogel. When the cracks were aligned with the training direction, the notch was gradually enlarged with the application of external force, accompanied by an increase in the molecular chain gap. This resulted in the destruction of the original molecular chain arrangement and a reduction in the fatigue threshold. To provide further evidence that the $\\mathrm{P_{B}A C_{A}{-}Z n^{2+}}$ hydrogel exhibited good fatigue resistance, the results of the fatigue threshold test were presented in Figure S11 (Supporting Information). The fatigue threshold of the trained $\\mathrm{P_{B}A C_{A}{-}Z n^{2+}}$ hydrogel was found to be up to $1320\\:\\mathrm{J}/\\mathrm{m}^{2}$ . It is notable that many stretchable and flexible materials still fracture when left in working conditions for extended periods of time, which is in stark contrast to the prepared hydrogels. This renders training $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogels a high-performance, durable, low-cost alternative to flexible materials for use in situations such as flexible substrates and artificial muscles. Figure $3(\\mathrm{h})$ illustrated the notched ultimate strain test of the training hydrogel, conducted to assess the sensitivity of the $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogel to crack resistance. The results demonstrated that the crack extension strains along parallel and perpendicular to the training direction can reach $840\\%$ and $274\\%$ , respectively. Consequently, the incorporation of high mechanical strength and good crack resistance enabled the fracture energy of the $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogel to reach 208.6 KJ $\\mathrm{m}^{-2}$ (parallel direction) and $30~\\mathrm{KJ/m^{2}}$ (perpendicular direction), respectively, thereby demonstrating the good fatigue resistance (Figure 3i).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.4. Self-Healing Properties of $\\tt P_{B}A C_{A}.Z n^{2+}$ Hydrogels  \n\nIt is anticipated that $\\mathrm{P_{B}A C_{A}{-}Z n^{2+}}$ hydrogels will demonstrate rapid and efficient self-healing properties due to the multiple reversible interactions introduced into the 3D crosslinked network. Figure $4(\\mathsf{a})$ schematically depicted the working mechanism of hydrogen bonds, borate bonds and metal coordination bonds within the $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogels when subjected to mechanical damage. As illustrated in Figure 4(b) and Figure S12a (Supporting Information), the fractured hydrogels demonstrated rapid self-healing properties after re-docking, reaching a self-healing efficiency of $95.1\\%$ within $^{4\\mathrm{h}}$ . Furthermore, the stress could be healed to more than $90\\%$ of the initial hydrogel strength, due to the synergistic repair effect among multiple reversible interactions. Strikingly, the trained hydrogels also exhibited the impressive self-healing properties, as shown in Figure 4(c,d) and Figure S12(b) (Supporting Information). This may be attributed to the re-slippage of molecular chain segments in the original interlocking network after training, leading to the breakage and reorganization of old dynamic bonds while maintaining the reparable properties. It was noteworthy that the self-healing efficiency $(92.9\\%)$ of the $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogels exhibited a minor decline following the mechanical training. This could be attributed to the fact that the crystallinity of the hydrogels increased after mechanical training, resulting in a hard-phase region that impeded the movement of molecular chains and, consequently, hindered the self-healing behavior.[36] To further characterize the self-healing property, the prepared conductive nano-hydrogels were connected to a circuit to test the ability to light up a light bulb (Figure 4e). The conductive hydrogel, undamaged, could be connected to the circuit and the light bulb will illuminate as normal. However, if the material was cut off, the circuit became disconnected and the light bulb will extinguish immediately. Interestingly, the healed hydrogel then restored the original brightness of the bulb when connected to the circuit. Furthermore, the healed conductive hydrogel could still be stretched freely. As illustrated in Figure 4(f), the conductive hydrogel demonstrated an above- $95\\%$ resistance recovery rate following multiple cyclic selfhealing, thereby demonstrating outstanding self-healing properties. As expected, the healed hydrogel samples maintained the ability to produce a clear electrical signal under $100\\%$ tensile strain, exhibiting a high degree of similarity to the initial electrical signal (Figure S13, Supporting Information). As a demonstration, the self-healing properties were subjected to microscopic analysis via rheological testing, as illustrated in Figure $4(\\mathrm{g)}$ . For a period of $100\\mathrm{{s}}$ , when subjected to low shear strain, the conductive hydrogel’s complete interlocking network ensured that the energy storage modulus was consistently greater than the loss modulus. However, the original network structure was destroyed when the shear strain increased, resulting in a significant decrease in both the energy storage modulus and the loss modulus. Upon transitioning to the subsequent cycle, the numerous reversible bonds within the system complete the reconstruction, thereby restoring the original network properties of the gel and exhibiting rapid self-healing capabilities. It is encouraging to note that our work exhibits outstanding performance among the reported high-strength hydrogels, thereby demonstrating the durability and stability of the $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogels (Figure 4(h) and Table S3, Supporting Information).  \n\n![](images/b760df9eb558564aef821e984a481bfdbbf60e8c9ce1fcd8b2179cb4bb3ba5b2.jpg)  \nFigure 4. Characterization of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ hydrogel self-healing properties. a) Schematic representation of self-healing system based on multiple dynamically bonded hydrogels. b) Self-healing efficiency of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.Z\\mathsf{n}^{2+}$ hydrogels at different times. c) Self-healing mechanism of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}{-}Z\\mathsf{n}^{2+}$ hydrogel after mechanical training. d) Self-healing efficiency of training hydrogels at different times. e) Self-healing properties of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ hydrogels in electrical circuits and macroscopic fracture repair. f) Stability of resistance values before and after self-healing. g) Rheological properties of $\\mathsf{P}_{\\mathsf{B}}^{\\mathsf{^{\\prime}}}\\mathsf{A C}_{\\mathsf{A}}{-}Z\\mathsf{n}^{2+}$ hydrogels before and self-healing. h) Comparison of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}{-}Z\\mathsf{n}^{2+}$ hydrogel in terms of toughness, stress, strain, self-healing and fatigue resistance with existing literature.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.5. Anti-Freezing Properties of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}{\\mathsf{-}}\\mathsf{Z}\\mathsf{n}^{2+}$ Hydrogels  \n\nAt sub-zero temperatures, the ordered ice lattice is formed by disordered hydrogen bonding between water molecules, which leads to icing of conventional conductive hydrogels and reduces the durability of the material.[37] The strong electronegativity of the fluorine atom enables the introduced $\\mathsf{Z n}(\\mathsf{B F}_{4})_{2}$ salt to break the original hydrogen bindings between the ice crystals, conferring the antifreeze property to the $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogel. Figure 5(a) illustrated the antifreeze property of the conductive hydrogels. The hydrogel with $\\mathsf{Z n}(\\mathsf{B F}_{4})_{2}$ could be bent arbitrarily, whereas the control $\\mathrm{P_{B}A C_{A}}$ samples were covered ice crystals all over the surface and lost the original mechanical flexibility. To gain further insight into the environmental tolerance of the $\\mathrm{P_{B}A C_{A}{-}Z n^{2+}}$ hydrogels, the freezing point was determined by differential scanning calorimetry (DSC). Typically, the melting of ice crystals resulted in a pronounced heat absorption peak, indicative of the freezing point. The test results demonstrated that the $\\mathrm{P_{B}A C_{A}{-}Z n^{2+}}$ hydrogel exhibited good lowtemperature tolerance (Figure 5b). When the salt solution concentration reached $4~\\mathrm{mol~L^{-1}}$ , no heat absorption peak was observed in the test results, which was attributed to the low free water content in the hydrogel, thereby demonstrating enhanced low-temperature tolerance. A further Raman test was employed to explore the variation rule of hydrogen bonding in the conducting hydrogel (Figure S14, Supporting Information). The broad peaks appearing at $3100{-}3700~\\mathrm{cm^{-1}}$ in the test spectra represent $-\\mathrm{OH}$ in water molecules. To elucidate the different kinds of hydrogen bonding, the broad peaks were further analyzed as shown in Figure 5(c). It is observed that the concentration of $\\mathrm{\\Gamma_{O-H\\mathrm{...F}}}$ type water molecules increased with the $\\mathsf{Z n}(\\mathsf{B F}_{4})_{2}$ concentration. This indicated that the introduction of $\\mathrm{BF_{4}}^{2-}$ disrupted the original hydrogen-bonding system between ice crystal molecules and lowered the freezing point of the $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogel (Figure 5(d)). Furthermore, the conductivity of the hydrogel was evaluated at low temperatures (Figure 5(e)). The results of the tests demonstrated that the $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogel exhibited exceptional conductivity at a temperature of $-20{}^{\\circ}\\mathrm{C}$ In contrast, the control $\\mathrm{P_{B}A C_{A}}$ hydrogel failed to illuminate the bulb in the circuit due to the formation of ice, thereby posing challenges in low-temperature environments and reducing its practical applicability.  \n\nThe solvation effect of $\\mathsf{Z n}(\\mathsf{B F}_{4})_{2}$ ions imparted good moisturizing properties to the $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogel.[38] As illustrated in Figure $5(\\mathrm{f})$ , the control $\\mathrm{P_{B}A C_{A}}$ hydrogel exhibited a tendency to desiccate within $24\\mathrm{~h~}$ , accompanied by a significant loss of moisture. In contrast, the $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogel demonstrated remarkable stability, maintaining its original state with minimal moisture dissipation. The moisturizing properties of the hydrogels were also evaluated over a seven-day period, as shown in Figure ${}5(\\mathrm{g})$ . It can be observed that the $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogel retained more than $80\\%$ of its original moisture content. This was attributed to the dynamic equilibrium between the hydrogel and its surrounding environment, occurring at similar vapor pressures without moisture loss. In contrast, the control hydrogel exhibited higher vapor pressures than the environment, leading to a gradual loss of moisture and functionality.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.6. Trained $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}{\\mathsf{-}}\\mathsf{Z}\\mathsf{n}^{2+}$ Hydrogels Application to Triboelectric Nanogenerator  \n\nDue to its outstanding flexibility, mechanical strength, and conductivity, the trained $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogel was utilized as a flexible electrode for triboelectric nanogenerator (TENG) and applied to self-powered systems. Figure 6(a) depicted a singleelectrode mode triboelectric nanogenerator (S-TENG) comprised of a trained $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogel as the electrode and Ecoflex silicone rubber as the negative friction layer. The S-TENG operates based on the friction electric effect, generating voltage during the contact-detachment state.[1a,39] Initially, when the polyurethane film contacted the negative friction layer, an equal and opposite charge was generated at the S-TENG interface (i). The potential between the polyurethane film and the Ecoflex silicone rubber layer was almost zero in this state. Once the polyurethane film was separated from the S-TENG, the positive charge in the $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogel, serving as an electrode, moved to the upper layer to balance the negative charge on the Ecoflex silicone rubber layer (ii). This resulted in the generation of transient currents as charges flow to ground along the external circuit until all electrostatic charges were shielded. Subsequently, the electron flow ceases as the two friction layers gradually move away and reach a state of complete separation (iii). Upon the re-approach of the polyurethane film to the S-TENG, the electrons flow back to the $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogel electrode along the external circuit (iv), and the S-TENG system generated alternating current during the continuous contact and separation process.[16] To gain a more intuitive understanding of the S-TENG’s working mechanism, a simulation was conducted using Comsol Multiphysics software to analyze the change in electric potential during constant contact and separation. As illustrated in Figure 6(b), when the silicone rubber and polyurethane film were in a state of continuous contact and separation, a notable change occurs in the potential difference between the two friction layers, resulting in the generation of alternating current through the flow of electrons in the external circuit. It has been reported that the change in hydrogel conductivity had a significant impact on the output performance of TENG. It is noteworthy that the oriented alignment of the anchored polyaniline CNFs nanofibers upon receiving mechanical training resulted in the formation of unique conductive channels, which significantly enhanced the conductivity of the hydrogel. This, in turn, further enhanced the output performance of the S-TENG, as demonstrated by the specific analyses in the next section.  \n\n![](images/bb766c666e3cf90c89290edf3ec0deae71c9bd69b7e671dcdcb2cba5dc0113e4.jpg)  \nFigure 5. Anti-freezing and moisturizing properties of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ hydrogels. a) Images of the control and $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ hydrogel at low temperature. b) DSC plots of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}^{-}\\mathsf{Z n}^{2+}$ hydrogels with different $Z n^{2+}$ concentrations. c) Control and $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.Z\\mathsf{n}^{2+}$ hydrogel lamp experiments at low temperatures. d) $0\\mathrm{-}\\mathsf{H}$ stretching vibrational Raman spectra after peak splitting. e) Peak intensity of the d) plot response. f) Comparative images of moisturizing properties of control and $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ hydrogel. g) Moisturizing properties of control and $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ hydrogel left in air for 7 days. Scale bar: 1 cm.  \n\n![](images/d45b70fc994ab0c09107895ab23a1455145494606f30c4e6199191dfbcf7b450.jpg)  \nFigure 6. $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.Z\\mathsf{n}^{2+}$ hydrogels applications for triboelectric nanogenerators. a) The working principle of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}{-}Z\\mathsf{n}^{2+}$ hydrogels TENG. b) Electric potential distribution simulation. The output performance of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}{-}Z\\mathsf{n}^{2+}$ hydrogel TENG composed of different polyaniline contents, including c) $V_{\\mathrm{oc}},$ d) $\\varrho_{\\mathrm{sc}}$ and e) $I_{\\mathsf{s c}}$ . f ) $V_{\\mathrm{oc}}$ , g) $I_{\\mathsf{s c}}$ and $\\boldsymbol{\\mathsf{h}}$ ) $\\varrho_{\\mathrm{sc}}$ of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.Z\\mathsf{n}^{2+}$ hydrogels TENG at different frequencies. i) $V_{\\mathrm{oc}}$ , $I_{\\mathsf{s c}}$ and $\\varrho_{\\mathrm{sc}}$ of $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ hydrogels TENG as a function of different load resistances. j) Output stability characterization.  \n\nFigure $6(\\mathrm{c})$ depicted the electrical output performance of $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogel-assembled S-TENG with varying polyaniline contents at a fixed frequency. Encouragingly, the open-circuit voltage $\\left(V_{o c}\\right)$ output value of the S-TENG increased linearly with increasing PANI loading, reaching a peak value of up to $100.02{\\mathrm{V}}.$ However, when the PANI content reached $9\\mathrm{wt\\%}$ , the $V_{o c}$ of the STENG exhibited a significant decrease, similar to that observed in the short-circuit current $(I_{s c})$ and short-circuit quantity $(Q_{s c})$ . This phenomenon was primarily attributed to the inability of CNFs nanofibers to accommodate an excessive amount of PANI. The electron transport capability of $\\mathrm{P_{B}A C_{A}{-}Z n^{2+}}$ hydrogel was impeded by the conductive fillers dispersed in the network agglomerates, which directly increased the resistance of the conductive hydrogels. Notably, the S-TENG exhibited an $I_{s c}$ and $Q_{s c}$ of $2.53\\upmu\\mathrm{A}$ and $31.39~\\mathrm{nC}$ , respectively, when the PANI content was $7\\mathrm{wt}\\%$ (Figure 6(d,e)). In addition to the inherent output performance, output performance of S-TENG was also tested at $0.5{\\cdot}2\\ \\mathrm{Hz}$ frequencies. Indeed, the $V_{o c}$ , $I_{s c}$ and $Q_{s c}$ all demonstrated stable states (Figure 6(f–h)), which resulted from training the $\\mathrm{P_{B}A C_{A}}.$ $Z\\mathrm{n}^{2+}$ hydrogel-oriented interlocking structure with high stability and reliability. Similarly, the output performance of S-TENG was influenced by the load resistance. As the external load resistance increased, the open-circuit voltage $(V_{o c})$ increases from an initial value of $3.5\\mathrm{~V~}$ to $85~\\mathrm{V}.$ In accordance with Ohm’s law, the current density was known to decrease in the opposite direction.[40] Notably, when the load resistance reached $1.5\\times10^{8}\\Omega$ , the STENG achieved a maximum power density of $8.5~\\upmu\\mathrm{W}~\\mathrm{cm}^{-2}$ , as shown in Figure $6(\\mathrm{i})$ . The stability of S-TENG was of great importance, given the high electrical output performance previously mentioned. S-TENG can maintain a stable output over 3000 operating cycles (Figure 6(j)), while the healed electrode was still able to achieve the initial output performance (Figure S15, Supporting Information). As anticipated, the robust mechanical and electrical conductivity of the hydrogel were instrumental in conferring the S-TENG system with remarkable output performance, fatigue resistance and damage resistance, thereby ensuring the device’s prolonged operational stability.  \n\nInterestingly, the output performance of S-TENG was also tested as a self-powered tactile sensing system. Figure S16a (Supporting Information) illustrated a schematic of the sensor’s ability to recognize that S-TENG can output electrical signals with varying peaks and shapes in response to pressure. Initially, a simple letter “a” was written, resulting in a clear and repetitive electrical signal, as shown in Figure S16b (Supporting Information). More encouragingly, the multiple-letter phrases “OK” and “TENG” also conveyed the electrical signals completely and clearly, demonstrating S-TENG’s high stability and sensitivity (Figure S16c,d, Supporting Information). The sensing system was expected to be utilized for self-powered writing recognition and information encryption applications.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.7. $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}{\\mathsf{-}}\\mathsf{Z}\\mathsf{n}^{2+}$ Hydrogel Self-Powered System  \n\nDue to its favorable electrochemical stability, anchoring of polyaniline with CNFs as a template can result in the formation of conductive fibers. In contrast to the liquid metal-based conductive pathways developed by Wang et al.,[35] these fibers exhibited a directional arrangement facilitated by mechanical training, thus constructing a unique conductive pathway. This was illustrated in Figure 7(a). Initially, the formation of the conductive pathway was confirmed by changes in conductivity, demonstrating the anisotropy of $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogel’s conductivity as shown in Figure 7(b). The conductivity of hydrogel parallel to the training direction notably increased from $6\\mathrm{~S~m~}^{-1}$ to $12\\mathrm{~S~m~}^{-1}$ initially, while that perpendicular to the training direction significantly decreased to $2~\\mathrm{S~m^{-1}}$ . This phenomenon could be attributed to the directional alignment of the conducting fibers. Following mechanical training, the polyaniline anchored to the CNFs formed conductive channels parallel to the training direction, significantly enhancing the conductivity. However, in the perpendicular direction, mechanical training compressed and obstructed the transport channels, thereby reducing the conductivity. The constructed conductive pathway facilitates the stable and efficient transmission of electrical signals in practical applications, thus markedly enhancing the output performance of S-TENG.  \n\nDue to its mechanical stability and high electrical conductivity, the trained hydrogel was utilized as a strain sensor to monitor human life activities (Figure 7(c)). To ascertain the potential of hydrogels as sensors, the sensing sensitivity was validated utilizing the GF factor. Figure $7(\\mathrm{d})$ depicted the linear relationship between the rate of change of resistance and strain, and the GF factor was maintained at 9.98 when the maximum strain reached $200\\%$ . It was evident that the stable structure and unique conductive channels support the ultra-high sensitivity behavior of the $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogel. Critically, the constructed sensor can be securely attached to the human wrist to monitor the minute pulse signal, thereby greatly expanding the hydrogel’s application scope (Figure 7(e)). Subsequently, the performance of the supercapacitor (SC) with the $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogel as the solid-state electrolyte was evaluated (Figure $7(\\mathrm{f})$ ). Galvanostatic charge/discharge curves at $0.5~\\mathrm{mA}~\\mathrm{cm}^{-2}{\\cdot}5~\\mathrm{mA}~\\mathrm{cm}^{-2}$ current densities were demonstrated in Figure $7(\\mathrm{g})$ . The approximate triangular test curves clearly demonstrated the reversible charge/discharge performance of the supercapacitor. The corresponding CV curves of the SC were shown in Figure $7(\\mathrm{h})$ . It can be observed that the peak current of the $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogelbased SC gradually increases under different sweep speeds. Notably, the CV curves exhibited pseudo-rectangular shapes, thereby corroborating the reversibility of the supercapacitor.[41] The antifreeze property of the SC demonstrated good tolerance at low temperatures (Figure S17, Supporting Information). Finally, the ability of the $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogel-based S-TENG and SC to convert mechanical energy into electrical energy, store electrical energy, and drive electronic devices was verified (Figure 7(i,j)). In particular, the $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogel-based SC can store the electrical energy generated by the S-TENG. When the circuit is connected, the SC was in a charging state. When the switch was disconnected, the SC formed a closed circuit with the light bulb of the external load, thereby successfully lighting it up. Similarly, the external load can be substituted with a strain sensor attached to the human epidermis to form a self-powered sensing system.  \n\n![](images/699156a627fe1a7d952f4b9867bc0460224911da78c79f7ca1df2f3c8474e147.jpg)  \nFigure 7. Self-powered output performance system. a) The directionally arranged CNFs form conductive pathways. b) Conductivity in parallel and perpendicular directions. c) $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ hydrogels were assembled as strain sensors to monitor human life activities. d) GF values of the hydrogel sensor. e) Hydrogel sensors could monitor pulse signals. f) $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ hydrogels were assembled as supercapacitors. g) GCD curves of supercapacitor at current densities of $0.5{-}5\\mathsf{m A c m}^{-2}$ . h) CV curves of supercapacitor with different sweep rates. i) $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}{-}Z\\mathsf{n}^{2+}$ hydrogels TENG Circuit diagram. j) The self-powered system lights the bulbs.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 2.8. Deep-Learning-Assisted Wearable Recognition System  \n\nWearable recognition systems based on deep learning have garnered the interest of numerous researchers in personalized and intelligent human-computer interaction applications.[42] Illustrated in Figure 8(a), an interactive system was constructed for recognizing complex human movement behavior utilizing deep learning model-assisted $\\mathrm{P_{B}A C_{A}}{\\cdot}\\mathrm{Zn}^{2+}$ hydrogel sensors. Specifically, as volunteer moved, the sensors affixed to the skin could transmit electrical signals to the algorithmic model for training and testing. With successive training iterations, the training loss diminished gradually, while testing accuracy improved incrementally, thereby achieving the objective of signal recognition. To showcase the performance of the designed preprocessing recognition system and the hybrid lightweight algorithm, the volunteers were tested for electrical signal recognition under different motion patterns (Figure 8(b)). Initially, the acquired electrical signal data were utilized for training the deep learning model, which comprised a convolutional neural network (CNN) and a gate recurrent unit (GRU). In this instance, the convolutional neural network was responsible for collecting and extracting the distinguishing features of the delivered signals, while the gate recurrent unit was responsible for the subsequent data capture dependencies, as illustrated in Figure 8(c,d). Although the electrical signals delivered during different movement patterns exhibited high similarity, they could still be distinguished by peak intensity and utilized as the foundation for constructing the classification system. Throughout the testing process, prediction parameters were determined by the electrical signals transmitted over a 5-second period and the model could provide the relevant eigenvalues for each recognition prediction. As illustrated in Figure 8(e), the recognition accuracy of the proposed model gradually reached saturation following several training sessions. The convergence of the system was close to 1, indicating that the system was approaching a stable state. Figure ${}^{8(\\mathrm{f)}}$ illustrated the confusion matrix between the true value and the predicted value during the recognition of motion signals. Its average prediction accuracy could reach $96.5\\%$ , indicating the system’s capability to accurately recognize motion signals, thereby providing a reference for the practical application of intelligent sensing in the future.  \n\n![](images/89efa9b324605419741cfcd88994757dc47bc577e7070be125369e1049dbb7ea.jpg)  \nFigure 8. Deep-learning-assisted recognition system. a) Wearable identification system with self-powered sensors. b) Electrical signal transmission in different gaits. c) Schematic diagram of the identification prediction system. d) Signal classification process demonstration. e) Identify the resultant confusion matrix. f) Recognition result accuracy.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3. Conclusion  \n\nIn conclusion, we propose a directional interlocking strategy based on topological networks and mechanical training. The prepared $\\mathrm{P_{B}A C_{A}{\\cdot}Z n^{2+}}$ hydrogels demonstrate impressive mechanical strength, toughness and fatigue resistance. Notably, the opened directional conductive pathway significantly enhances the conductivity of the hydrogel and thus the output performance of the self-powered device. Under the influence of multiple reversible effects, the mechanically damaged hydrogel material can quickly and efficiently repair itself. Furthermore, the strong interaction between fluorine atoms and water molecules provides the conductive hydrogel with anti-freezing properties. Finally, the developed self-powered system has demonstrated practical applications, opening a range of potential applications for stable and durable multifunctional hydrogel materials.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 13,
+        "chunk": "# 4. Experimental Section  \n\nMaterials: Oxidized cellulose nanofiber suspension (CNFs) was synthesized within the laboratory. Polyvinyl alcohol (PVA, $99\\%$ hydrolyzed, $M_{\\mathrm{w}}=85000{-}124000)$ , acrylamide (AAm, $99\\%$ ), aniline (ANI, $\\geq99\\%$ ), sodium tetraborate decahydrate (Borax, $99.5\\%\\AA)$ , zinc tetrafluoroborate $(Z\\mathsf{n}(\\mathsf{B F}_{4})_{2}$ , CP), potassium persulfate (KPS, $99.5\\%$ ) and $\\mathsf{N},\\mathsf{N}^{\\prime}$ methylenebisacrylamide (MBAA, $98\\%$ ) were purchased from Aladdin Chemical Reagent Co. Sodium hypochlorite (NaClO, CP), sodium bromide (NaBr, $\\geq98.0\\%$ ) were purchased from Sinopharm Chemical Reagent Co., Ltd. 2,2,6,6-tetramethylpiperidinyl-1-oxide (TEMPO, $98\\%$ ) was purchased from Macklin Biochemical Co., Ltd.  \n\nSynthesis of Oxidized Cellulose Nanofiber (CNFs): Briefly, a $50~\\mathrm{mL}$ sample of the $1\\%$ dissociated fiber slurry was weighed in a flask. Subsequently, NaBr $(0.05\\ \\mathrm{g})$ and TEMPO $(0.015\\ \\mathrm{g})$ reagent were added to the solution and mixed until homogeneous. Then, add 3 mL NaClO solution to the mixed solution and stir evenly. Besides, $0.1\\mathrm{~M~HCl}$ solution need to be added to adjust the pH of the system. During this process, add $0.1~\\mathsf{M}$ NaOH solution to maintain $\\mathsf{p H}$ and place the mixed solution in an ice bath environment for oxidation. The reaction time was $\\rceil5\\mathrm{~h~}$ . After the reaction was completed, the mixed solution was filtered and washed with water several times to obtain the final product CNFs.  \n\nSynthesis of CNFs-Templated PANI: First, the suspension of CNFs $(\\mathsf{70g})$ , ANI $(0.5~\\mathrm{mL})$ , and phytic acid $(7.5~\\mathsf{m L})$ were prepared by adding the components to deionized water and stirring in an ice bath until a homogeneous mixture was achieved. The desired amount of KPS (0.01 g) was then added to the above mixture and placed in an ice bath environment, where it was stirred for $12\\mathrm{~h~}$ . Finally, the resulting mixture was placed in a dialysis bag and dialyzed for two days to remove unreacted monomers and adjusted to neutrality to obtain CNFs templated PANI, abbreviated as CNFs-PANI.  \n\nSynthesis of $P_{B}A C_{A}.Z n^{2+}$ Hydrogels: Briefly, a certain quantity of PVA, AAm, Borax and the synthesized CNFs-PANI were placed in a three-necked flask and thoroughly mixed. Subsequently, KPS and MBAA were added to the mixture and stirred until a homogeneous solution was obtained. The polymerization solution was injected into a specific mold and placed at $65~^{\\circ}C$ to initiate polymerization. After five hours, a PVA $_{\\mathsf{B o r a x}}/\\mathsf{A A m/C N F}.$ PANI hydrogel, abbreviated as $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}$ hydrogel, was obtained (Subscript “B” represents Borax, while the subscript “A” represents PANI). The prepared hydrogel was immersed in the $Z\\mathsf{n}(\\mathsf{B F}_{4})_{2}$ solution for $6\\mathfrak{h}$ , and the final product was obtained and noted as $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ hydrogel. For comparison, the dual network hydrogels composed of PVA (crosslinked by borax) and PAAm were abbreviated as $P V A_{\\mathsf{B}}$ -PAAm. The specific reagent dosages were presented in Table S1 and S2 of the supporting information.  \n\nAssembly of $P_{B}A C_{A}.Z n^{2+}$ Hydrogel Sensor: Conductive tape was attached to both ends of the $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}{-}Z\\mathsf{n}^{2+}$ hydrogel samples and connected with wires. The assembled sensors were then placed on different parts of the volunteer’s body for the purpose of electrical signal testing.  \n\nConstruction and Characterization of $P_{B}A C_{A}.Z n^{2+}$ Hydrogel Supercapacitor: The supercapacitor was composed of two electrodes with $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.$ $Z n^{2+}$ hydrogel electrolyte sandwiched between carbon cloth to form an integrated component. Cyclic voltammetry (CV) curves and galvanostatic charge/discharge (GCD) curves of supercapacitors were obtained using an electrochemical workstation (CHI 660E).  \n\nFabrication and Characterization of $P_{B}A\\bar{C}_{A}.Z n^{2+}$ Hydrogel TENG: The prepared $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.Z\\mathsf{n}^{2+}$ hydrogel was sandwiched between two layers of Ecoflex film to form a single-electrode TENG system. A linear motor (LinMot E1100) was employed to provide mechanical force. The triboelectric outputs of charge, current voltage and of the $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ -TENG were recorded using a Keithley 6514 electrometer. COMSOL Multiphysics was utilized to simulate the potential distribution during the $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}{-}Z\\mathsf{n}^{2+}$ - TENG simulation.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 14,
+        "chunk": "# Supporting Information  \n\nSupporting Information is available from the Wiley Online Library or from the author.",
+        "category": " References"
+    },
+    {
+        "id": 15,
+        "chunk": "# Acknowledgements  \n\nSupported by the Taishan Industrial Experts Program, National Natural Science Foundation of China (51872150) and “QingChuang Science and Technology Plan” Project of Colleges and Universities in Shandong Province (2020KJC005).",
+        "category": " References"
+    },
+    {
+        "id": 16,
+        "chunk": "# Conflict of Interest  \n\nThe authors declare no conflict of interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 17,
+        "chunk": "# Data Availability Statement  \n\nThe data that support the findings of this study are available in the supplementary material of this article.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# Keywords  \n\nconductive hydrogel, deep learning, mechanical strength, self-powered sensing, toughness  \n\nReceived: May 27, 2024   \nRevised: August 21, 2024   \nPublished online: September 20, 2024  \n\n[1] a) L. Lamanna, G. Pace, I. K. Ilic, P. Cataldi, F. Viola, M. Friuli, V. Galli, C. Demitri, M. Caironi, Nano Energy 2023, 108, 108168; b) Z. Qin, G. Zhao, Y. Zhang, Z. Gu, Y. Tang, J. T. Aladejana, J. Ren, Y. Jiang, Z. Guo, X. Peng, X. Zhang, B. B. Xu, T. Chen, Small 2023, 19, 2303038; c) C. Lu, X. Wang, Y. Shen, S. Xu, C. Huang, C. Wang, H. Xie, J. Wang, Q. Yong, F. Chu, Adv. Funct. Mater. 2023, 34, 2311502.   \n[2] a) Y. Wang, P. Chen, X. Zhou, Y. Liu, N. Wang, C. Gao, ACS Appl. Mater. Interfaces 2022, 14, 47100; b) Y. Wang, B. Pang, R. Wang, Y. Gao, Y. Liu, C. Gao, Composites, Part A 2022, 160, 107039.   \n[3] a) J. Dong, S. Huang, J. Luo, J. Zhao, F. R. Fan, Z.-Q. Tian, Nano Energy 2022, 95, 106971; b) T. Li, H. Qi, X. Dong, G. Li, W. Zhai, Adv. Mater. 2024, 36, 2304145.   \n[4] Y. Li, Z. Tian, X. Z. Gao, H. Y. Zhao, X. Li, Z. L. Wang, Z. Z. Yu, D. Yang, Adv. Funct. Mater. 2023, 33, 2308845.   \n[5] a) J. Yue, C. Li, X. Ji, Y. Tao, J. Lu, Y. Cheng, J. Du, H. Wang, Chem. Eng. J. 2023, 466, 143358; b) L. Zhang, S. Wang, Z. Wang, Z. Liu, X. Xu, H. Liu, D. Wang, Z. Tian, ACS Nano 2023, 17, 13948.   \n[6] J. P. Gong, Y. Katsuyama, T. Kurokawa, Y. Osada, Adv. Mater. 2003, 15, 1155.   \n[7] J. Y. Sun, X. Zhao, W. R. Illeperuma, O. Chaudhuri, K. H. Oh, D. J. Mooney, J. J. Vlassak, Z. Suo, Nature 2012, 489, 133.   \n[8] L. Zhang, K. Wang, S. Weng, X. Jiang, Chem. Eng. J. 2023, 463, 142414.   \n[9] D. Sun, Y. Gao, Y. Zhou, M. Yang, J. Hu, T. Lu, T. Wang, ACS Appl. Mater. Interfaces 2022, 14, 49389.   \n[10] S. Lin, J. Liu, X. Liu, X. Zhao, Proc. Natl. Acad. Sci. USA 2019, 116, 10244.   \n[11] C. Zhang, S. Shen, C. Wu, L. Wang, S. Lei, Z. Wang, Chem. Eng. J. 2023, 465, 142882.   \n[12] N. Li, Y. Han, F. Yu, W. Wang, Q. Liu, X. Qian, Z. 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Mckinley, X. Zhao, Sci. Adv. 2019, 5, eaau8528.; b) M. Hua, S. Wu, Y. Ma, Y. Zhao, Z. Chen, I. Frenkel, J. Strzalka, H. Zhou, X. Zhu, X. He, Nature 2021, 590, 594.   \n[29] a) C. Xiang, Z. Wang, C. Yang, X. Yao, Y. Wang, Z. Suo, Mater. Today 2020, 34, 7; b) W. Zhang, J. Hu, J. Tang, Z. Wang, J. Wang, T. Lu, Z. Suo, ACS Macro Lett. 2019, 8, 17.   \n[30] Y. Cheng, J. Zang, X. Zhao, H. Wang, Y. Hu, Carbohydr. Polym. 2022, 277, 118872.   \n[31] Y. Wang, P. Li, S. Cao, Y. Liu, C. Gao, Nanoscale 2023, 15, 18667.   \n[32] M. Yan, J. Cai, Z. Fang, H. Wang, X. Qiu, W. Liu, ACS Sustainable Chem. Eng. 2022, 10, 12993.   \n[33] Z. Chen, Y. Hu, G. Shi, H. Zhuo, M. A. Ali, E. Jamróz, H. Zhang, L. Zhong, X. Peng, Adv. Funct. Mater. 2023, 33, 2214245.   \n[34] W. Kong, C. Wang, C. Jia, Y. Kuang, G. Pastel, C. Chen, G. Chen, S. He, H. Huang, J. Zhang, S. Wang, L. Hu, Adv. Mater. 2018, 30, 1801934.   \n[35] X. Wang, S. Zheng, J. Xiong, Z. Liu, Q. Li, W. Li, F. Yan, Adv. Mater. 2024.   \n[36] a) Y. Wang, M. Zhu, C. Hao, R. Dai, M. Huang, H. Liu, S. He, W. Liu, Eur. Polym. J. 2022, 167, 111060; b) C. Xing, H. Wu, R. Du, Q. Zhang, X. Jia, Polym. Chem. 2021, 12, 4778.   \n[37] a) Y. Shi, R. Wang, S. Bi, M. Yang, L. Liu, Z. Niu, Adv. Funct. Mater. 2023, 33, 2214546; b) D. Bao, Z. Wen, J. Shi, L. Xie, H. Jiang, J. Jiang, Y. Yang, W. Liao, X. Sun, J. Mater. Chem. A 2020, 8, 13787.   \n[38] a) L. Zhao, B. Wang, Z. Mao, X. Sui, X. Feng, Chem. Eng. J. 2022, 433, 133500; b) Z. Xu, F. Zhou, H. Yan, G. Gao, H. Li, R. Li, T. Chen, Nano Energy 2021, 90.   \n[39] a) Y. Feng, J. Yu, D. Sun, C. Dang, W. Ren, C. Shao, R. Sun, Nano Energy 2022, 98, 107284; b) W. Akram, Q. Chen, G. Xia, J. Fang, Nano Energy 2023, 106, 108043.   \n[40] M. B. Durukan, M. O. Cicek, D. Doganay, M. C. Gorur, S. Çınar, H. E. Unalan, Adv. Funct. Mater. 2021, 32, 2106066.   \n[41] a) Y. Zou, C. Chen, Y. Sun, S. Gan, L. Dong, J. Zhao, J. Rong, Chem. Eng. J. 2021, 418, 128616; b) Y. Liu, H. Li, X. Wang, T. Lv, K. Dong, Z. Chen, Y. Yang, S. Cao, T. Chen, J. Mater. Chem. A 2021, 9, 12051.   \n[42] a) K. Li, D. Zhang, H. Zhang, D. Wang, Z. Xu, H. Cai, H. Xia, ACS Appl. Mater. Interfaces 2023, 15, 32993; b) R. Mao, D. Zhang, Z. Wang, H. Zhang, D. Wang, M. Tang, L. Zhou, H. Cai, H. Xia, Nano Energy 2023, 111, 108418.",
+        "category": " References"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/╔┘╤∙▒╛SI.json b/task2/task2-chunks/╔┘╤∙▒╛SI.json
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+[
+    {
+        "id": 1,
+        "chunk": "# nature computational science",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# Harnessing large language models for datascarce learning of polymer properties  \n\nIn the format provided by the authors and unedited  \n\nSupplementary Algorithm 1 The key steps of the two-phase training strategy.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 3,
+        "chunk": "# 1: LLM encoder pretraining:  \n\n2: Use a large dataset of unlabeled SMILES representations of polymers to pretrain an LLM encoder M˜ encode.   \n3: Phase-1 supervised pretraining:   \n4: Use physics-based hypothetical polymer generation methods, such as group contribution (GC), to generate a large dataset of physically meaningful synthetic polymer structures $\\{X_{i}\\}_{i=1}^{S_{G C}}$ with the correlation of fundamental thermophysical properties;   \n5: Build a physics-based model $\\boldsymbol{\\mathcal{M}}_{\\mathrm{p}h y s i c s}$ of the real-world physical process, by leveraging on the fundamental properties calculated from physically meaningful synthetic polymers;   \n6: Construct a physically meaningful synthetic dataset $\\mathcal{D}_{G C}:=\\{(X_{i},\\mathcal{M}_{\\mathrm{p}h y s i c s}(X_{i}))\\}_{i=1}^{S_{G C}}$ ;   \n7: Apply supervised pretraining to the LLM decoder/predictor using the synthetic dataset $\\mathit{\\Delta}\\mathcal{D}_{\\mathit{G C}}$ , to obtain an LLM decoder $\\dot{\\mathcal{M}}_{\\mathrm{decode}}$ with physically consistent initial state;   \n8: Phase-2 finetuning:   \n9: Collect a (usually small) set of high-fidelity measurements from experiments, denoted as $\\mathcal{D}_{H F}\\mathrel{\\mathop:}=$ $\\{({X}_{i}^{H F},{Y}_{i}^{H F})\\}_{i=1}^{S_{H F}}$ ;   \n10: Split the high-fidelity experimental dataset $\\mathcal{D}_{H F}$ as a training set $\\mathcal{D}_{H F}^{\\mathrm{t}r a i n}$ and a test set $\\mathcal{D}_{H F}^{\\mathrm{t}e s t}$ , and finetune the phase-1 LLM $\\tilde{\\mathcal{M}}_{\\mathrm{decode}}$ using $\\mathcal{D}_{H F}^{\\mathrm{t}r a i n}$ ;   \n11: Obtain the final physics-guided LLM, and report the prediction accuracy on the test dataset $\\mathcal{D}_{H F}^{\\mathrm{t}e s t}$ .",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/╕┤╨╘╦о─¤╜║═┐┴╧ Sci. Adv.json b/task2/task2-chunks/╕┤╨╘╦о─¤╜║═┐┴╧ Sci. Adv.json
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+[
+    {
+        "id": 1,
+        "chunk": "# M A T E R I A L S S C I E N C E",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Renatured hydrogel painting",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 3,
+        "chunk": "# Zhaoxiang Yang, Yonglin $\\boldsymbol{\\mathsf{H e}}^{*}$ , Shenglong Liao, Yingchao Ma, Xinglei Tao, Yapei Wang\\*  \n\nHydrogel coatings pave an avenue for improving the lubricity, biocompatibility, and flexibility of solid surfaces. From the viewpoint of practical applications, this work establishes a scalable method to firmly adhere hydrogel layers to diverse solid surfaces. The strategy, termed as renatured hydrogel painting (RHP), refers to adhering dehydrated xerogel to a surface with appropriate glues, followed by the formation of a hydrogel layer after rehydration of the xerogel. With the benefits of simplicity and generality, this strategy can be readily applied to different hydrogel systems, no matter what the substrate is. Hydrogel adhesion is demonstrated by its tolerance against mechanical impact with hydrodynamic shearing at $14\\ m/s$ . This method affords powerful supplements to renew the surface chemistry and physical properties of solid substrates. In addition, we show that the RHP technique can be applied to living tissue, with potential for clinical applications such as the protection of bone tissue.  \n\nCopyright $\\circledcirc$ 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# INTRODUCTION  \n\nSurface coatings are regarded as a key window to couple solid-state materials with external media. In the case of closely contacting with external media, the surface coatings are expected to exhibit adequate stability and durability against friction, corrosion, or other chemical and physical disturbances (1–3). Particularly for the sake of biomedical equipment and implantable devices, surface coatings can be hardly popularized without reasonable lubricity and biocompatibility besides the consideration of other surface properties (4–9). For example, the surgery of partial hip replacement is an important treatment for femur head necrosis and some degenerative osteoarthrosis (10), in which artificial femur head is an essential substitute to the diseased one so as to restore the joint movement. However, the occurrence of rigorous friction between the artificial femur head and the original acetabulum generally gives rise to acetabular chondrocyte damage and inflammation. This disadvantage clinically weakens the tolerance against intense movements and also shortens the service life of the artificial joints (11–13). Coating the artificial femur head with a protective layer that satisfies the demands on good biocompatibility, lubricity, and appropriate flexibility has been recognized as a critical step in the success of partial hip replacement. Biocompatible and lubricated coatings are also essentially needed in many other medical items and marine objects, such as medical catheters (14) and ship hulls (15) where extraordinary lubricity may be beneficial to the prohibition of biofilms so as to obtain antibacterial or antifouling surfaces (16).  \n\nHydrogels are rising as an innovative branch of soft materials with excellent lubrication (17, 18), biocompatibility (19, 20), and flexibility (21,  22) owing to their high water content. The diverse formulation and tunable porosity render the great possibilities to serve hydrogels as smart surface coatings with the ability of selfhealing (23), transporting nutrients, accommodating cell proliferation (24, 25), and delivering cargos (26, 27). Although there have been tremendous progresses in pinning hydrogels on different substrates, which accordingly demonstrates the great potentials in clinical and marine applications (28–32), there remains a need for a more versatile method to firmly and scalably coat hydrogels on various solid substrates regardless of surface topology and material category. In hindsight, the ideally versatile hydrogel painting meets several challenges: (i) The painting method should exhibit excellent compatibility to numerous substrates with the use of various hydrogel formulations, and it should also minimize the dependence on the surface topology. (ii) The adhesion force between the hydrogel and the surface should be able to resist physical and chemical disturbances, particularly including the mechanical friction, the expansion and contraction in the process of hydrogel swelling and dehydration, and the erosion led by acid or alkali media. The hydrogel coatings would have longer lifetime and better durability if they can be self-healable. (iii) Intending for practical applications, the hydrogel painting ideally is a time-saving and inexpensive fabrication process, avoiding lengthy laboratory work and the use of aggressive solvents or energy costs.  \n\nThroughout the history of hydrogel painting, it is challenging to propose a hydrogel painting strategy that satisfies all those aspects as stated above at the same time. Water and oxygen loaded in the hydrogels are two main obstacles that hinder the substantial adhesion of hydrogels on solid substrates (29,  33–36). Specifically, the activity of hydrophilic moieties within the hydrogel is significantly weakened by the water-induced hydration effect (37–39), so strong bonding of hydrogel with solid surface is rarely facilitated in the case of direct hydrogel painting. The existence of oxygen can inhibit the free radical–based reactions, which is a fatal drawback for anchoring hydrogels on vinyl-functionalized surfaces via free radical polymerization (14). In this work, we innovatively proposed a concept of renatured hydrogel painting (RHP), referring to a two-step technology of sticking hydrogel layers on solid surfaces. Concretely, dehydrated xerogel particles were first stuck on solid surfaces with the help of special adhesive. Then, the xerogel particles were rehydrated in an aqueous medium, which led to the formation of a uniform hydrogel coating layer on the objective surface. The RHP method successfully enabled to coat hydrogels on large-area surfaces of metal, Teflon, ceramic, glass, wood, polyurethane (PU), polydimethylsiloxane (PDMS), and polyvinyl chloride (PVC) with the painting area readily up to $2.0\\mathrm{m}^{\\hat{2}}$ . Different hydrogels could be firmly bonded on those surfaces, and the hydrogel layers did not lose their mechanical performance after compression with normal pressure up to $50\\mathrm{\\kPa}$ . As a reference, the pressure of an adult applied on the ground is about $17.5\\ \\mathrm{kPa}$ . In addition to mechanical compression in the vertical direction, the hydrogel coating layers could also endure the shearing force led by flowing water in lateral direction, with a water jet rate of $14~\\mathrm{m/s}$ , which is close to the speed of a cargo ship in an ocean.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# RESULTS",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# Preparation and characterization of RHPs on solid surfaces  \n\nAs schematically illustrated in Fig.  1A and fig. S1, the RHP technique involves two steps. First, an uncured fluidic adhesive is spread or sprayed on the surface of a specific substrate, followed by an immediate coverage of xerogel particles. The adhesive acts as a linker, bonding the xerogel particles with the underneath substrate. Second, a hydrogel layer comes into being after the xerogel particles are renatured in the presence of water. The preferred choice of adhesive relies on the substrate material. Taking glass as an exemplified substrate material, a classical adhesive is epoxy that is reactive with material consisting of polar groups. Both scanning electron microscopy (SEM) and confocal microscopy illustrate the stepwise preparation of a hydrogel painting consisting of polyacrylamide-alginate double network on a PU surface (see Fig.  1,  B  and  C). Typically, uncured epoxy resin was diluted by acetone to facilitate spreading or spraying operations (figs. S2 and S3). After the evaporation of acetone, xerogel microparticles made of a polyacrylamide-alginate- $\\cdot\\mathrm{Ca}^{2+}$ double-network hydrogel were paved on the epoxy layer. It is supposed that the epoxy may cure together with the xerogel particles, and the “key-lock” structures along with the possible reactivity at appropriate temperature between the epoxy and xerogel particles may account for the stability of hydrogel layers against the rehydration process and mechanical operations in the following studies (see fig. S4). According to resolution of surface structures in Fig. 1B (ii and iii), the xerogel particles appear to be reshaped, from irregular spheres to tangled fibers, after rehydration in an aqueous environment (see fig. S5). This phenomenon of hydrogel reshaping is defined as a so-called renaturation process, accompanied by the diffusion and reorganization of polymer chains to form a new hydrogel network. The confocal microscopy image clearly demonstrates the formation of a hydrogel layer on the cured epoxy layer and the close combination between the two layers (Fig. 1C). It is noteworthy that the epoxy constituents are also interspersed in the hydrogel layer, which should also contribute to fastening the hydrogel coatings against water swelling and mechanical disturbance (40, 41).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# Lubricity of RHP  \n\nInvestigations are made for the lubricity of RHPs made of three kinds of xerogel particles with the same composition yet different sizes, including small particles (SP; 30 to $40\\upmu\\mathrm{m}$ ), medium particles (MP; 60 to $80\\upmu\\mathrm{m}\\cdot$ ), and large particles (LP; 100 to $150~{\\upmu\\mathrm{m}}$ ). As shown in Fig. 2A and figs. S6 and S7, both SEM and optical observations confirm that flatter hydrogel painting is obtained with the use of smaller xerogel particles. As assessed by the profilometer (Fig. 2B), the arithmetical mean deviations of the surface profile $\\left(R_{\\mathrm{a}}\\right)$ , as the representative index of surface roughness, of the SP-RHP, MP-RHP, and LP-RHP are 4.90, 8.94, and $55.22\\upmu\\mathrm{m}$ , respectively, fully agreeing  \n\n![](images/90fbeeb3e00025b6fdca6bfd17409a36e13038b4f9d137c69670ed85ac7eb134.jpg)  \nFig. 1. Preparation and characterization of RHP. (A) Schematic illustration of the RHP technique. (B) SEM images of the adhesive layer (i, epoxy resin), the xerogel microparticle layer before rehydration (ii), and the rehydrated hydrogel layer after lyophilization (iii). (C) Confocal microscope images of the layered structure of RHP. The entire thickness is about $20\\upmu\\mathrm{m}$ . The adhesive and hydrogel layers are colorized with green and red fluorescence dyes, respectively.  \n\nYang et al., Sci. Adv. 2021; 7 : eabf9117     2 June 2021 with the fact that the RHP made of smaller xerogel particles has smaller surface roughness. It should be noted that the $R_{\\mathrm{a}}$ of three RHPs are all smaller than the size of their corresponding xerogel particles, further confirming the occurrence of renaturation in the rehydration process. It is assumed that the polymer chains within the smaller xerogel particles are easier to be relaxed from the particle interior once they are hydrated so as to reach a higher degree of chain interpenetration between neighbor particles.  \n\n![](images/02760b6549b7827cb84b3622fe71ce3c2ebdfd0326cb6d361b86c7d2b463fbcd.jpg)  \nFig. 2. Lubricity assessment of RHP. (A) SEM images of RHPs made of small xerogel particles (SP), medium xerogel particles (MP) and large xerogel particles (LP). (B) Surface roughness of the hydrogel coatings made of SP, MP, and LP. (C) Schematic diagram of the friction coefficient measurement by rheometer. (D) The friction coefficients under different pressures of RHPs made of SP, MP and LP. (E) Repeated friction coefficient test of the SP-RHP under low pressure and high pressure, alternatively. (F) Friction coefficients of PU, glass, and RHP under different pressures. Photo credit: (insets in 2A) Zhaoxiang Yang and Yonglin He, Renmin University of China.  \n\nAn overwhelming majority of hydrogel coatings have remarkable lubricity in terms of the hydration layer on their surfaces. With respect to this intriguing event, the friction coefficients of the RHP made of xerogel particles with different sizes were evaluated by a rheometer under different pressures (Fig.  2C). Notably, a smaller xerogel particle corresponds to a hydrogel surface with lower friction coefficient, which accords with the higher flatness and lower surface roughness of SP-RHP relative to MP- and LP-RHPs (Fig. 2D). Therefore, the SP-RHP was chosen as the superior choice in the following experiments, unless otherwise indicated. It should also be noted that all three RHPs exhibit lower friction coefficients under higher pressure, which is not consistent with the behaviors of other hydrogel coatings (28) but similar to the shear-thinning perform­ ance of typical polymer solutions. It is supposed that the hydrogel chains of RHP resulting from xerogel particles are more unfettered than that of monolithic hydrogels, which should be the critical determinant for explaining the renaturation of SP-RHP. In this regard, higher shearing pressure may promote the orientation or unentanglement of polymer chains within RHPs so as to decrease the friction resistance. The reliable friction coefficient against cycles of rheological test between low pressure $(12.7\\mathrm{kPa})$ and high pressure $(50.8\\mathrm{kPa})$ confirms the excellent stability and repeatability of the lubricity, which has been recognized as an important factor for ensuring longer lifetime of surface coatings (Fig.  2E). It is worth noting that the pressure of $50.8\\mathrm{~kPa}$ is almost three times higher than the pressure on feet of an adult. To further verify the benefit of hydrogel for improving lubricity, we comprehensively compared the RHP with smooth PU and glass surfaces. As summarized in Fig.  2F, the friction coefficient of RHP is two and one orders of magnitude lower than that of PU and glass, respectively. Besides, contrary to RHP, both PU and glass surfaces suffer higher friction coefficient under higher shearing pressure.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# Robustness of RHP  \n\nFollowing the same procedure for preparing RHP on glass, RHP was prepared on a metal slice that was subjected to a water jet to assess the robustness of hydrogel coatings. As shown in Fig. 3A, the RHP was impinged by a water jet with a water flowing rate of 13 to $14~\\mathrm{m/s}$ . This flowing rate is equivalent to 25 to 27 knots/hour. As a reference, the average speed of cargo ships moving in water is about 15 to 20 knots/hour. After such a rigorous impingement, negligible damages were found throughout the whole RHP surface (Fig. 3A and movie S1). If the RHP was impregnated by silicone oil and then soaked in deionized water, then the exuviation of an “oil skin” was observed away from the RHP surface, indicating the wonderful preservation of integrity and oleophobicity of the RHP (figs. S8 and S9).  \n\nThe durability of lubricity, as stated above, is also a character to demonstrate the robustness of RHPs. After being stored in acidic $\\mathrm{(pH}=3\\dot{)}$ ) or alkaline $\\mathrm{\\langlepH=11}$ ) solution for 24 hours, the friction coefficient of RHP at $\\mathrm{pH}3$ remains almost unchanged, while the friction coefficient of RHP at $\\mathrm{pH}11$ decreases gradually (fig. S10). It is assumed that the alkaline condition can cause the hydrolysis of polyacrylamide (PAM) (42), involving a nucleophilic addition reaction of hydroxide to the amide carbonyl and a subsequent elimination of the amide ion $\\left(-\\mathrm{NH}_{2}\\right)$ to yield a carboxyl group (fig. S11A). The generation of carboxyl group increases the electrostatic repulsion between PAM chains, thus enabling surface polymer chains to be looser and more compliant. Meanwhile, the introduction of carboxyl groups also increases the surface hydrophilicity (fig. S11B), which is beneficial for improving lubrication. The friction coefficients of MP-RHP and LP-RHP decrease gradually, yet the friction coefficient of SP-RHP remains almost unchanged after being stored in deionized water for 6 weeks (see Fig. 3B). Incidentally, the xerogel particles, as a form of light and dry powder, are extremely suitable for storage and carriage. These unique features are favorable in moving forward with the commercialization of RHP technique, not to mention insusceptible to mildew (see fig. S12).  \n\nThe volume change in the dehydration-renaturation process is another important factor to influence the RHP adhesion on solid surfaces. In principle, the hydrogel has a higher degree of deformation than the underneath substrate in response to humidity change (43, 44). This is a negative finding in the case of hydrogel coatings on nonswelling substrates. Yet, the results of both surface topography and friction coefficient indicate that RHPs are extremely stable against the dehydration-renaturation treatment (Fig.  3C and fig. S13). It is assumed that the adhesive interpenetrates among or into the xerogel particles, which may account for the stability of the coating in the hydration and dehydration process. In addition, the RHP also exhibits antiscratching performance. As illustrated in Fig. 3D, the RHP can fully restore to its original surface topography in 36 hours after it receives an incision by a knife. Such a self-healing capability is attributed to the refilling of hydrogel in the scratched area where the capillary effect may facilitate the extension and migration polymer chains in aqueous condition.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# Versatility of RHP  \n\nThe RHP technique is applicable to many substrates and diverse hydrogel formulas in Fig. 4. As exemplified in Fig. 4A and movie S2, RHP was also successfully fabricated on a Teflon substrate with the help of a cyanoacrylate adhesive. In contrast to the uncoated Teflon surface and the surface coated with cured adhesive that have water contact angles of $112^{\\circ}$ and $83^{\\circ}$ , respectively, the RHP-coated surface is much more hydrophilic with a water contact angle of $11^{\\circ}$ . This notable wettability difference was clearly specified by a patterned RHP on a Teflon film (see fig. S14 and movie S2). After getting splashed with an aqueous solution containing Rhodamine B, an “RUC” red pattern where RHP was coated was quickly distinguished from the surrounded Teflon matrix.  \n\nOther substrates like ceramics and wood could be also coated with RHPs, by which the surfaces were endowed with antifouling and lubricant performance. As shown in Fig. 4B and movie S3, the right side of a porcelain bowl was coated with RHP, while the left  \n\n![](images/70ec54f8587c5de43d3896b8707de013fe6a4f669a21ac0583500d5785876f4b.jpg)  \nFig. 3. Robustness assessment of RHP. (A) Impingement test of RHP on a metal slice against a water jet (flow rate is about 13 to $14\\mathsf{m}/\\mathsf{s}$ ). (B) The friction coefficient and optical images of RHPs soaked in phosphate-buffered saline solution over time. (C) Friction coefficient and SEM images of a typical RHP that receives a dehydrationrenaturation treatment. (D) SEM images of a scratch on the RHP surface after 0, 6, and 36 hours in deionized water. Photo credit: (A and B) Zhaoxiang Yang and Yonglin He, Renmin University of China.  \n\nYang et al., Sci. Adv. 2021; 7 : eabf9117     2 June 2021 side was unmodified. When the oil contaminates the inner surface of the bowl, oil attached on the side with RHP could be easily cleared by deionized water, while the unmodified surface was fully stained with oil. Another example is a wooden board, which shows better lubricity after being coated with RHP. To vividly present the improved lubricity by RHP, we placed a wooden chess piece on two wooden boards with or without RHP at a specific tilting angle. The chess piece could easily slide off the RHP-modified surface at a tilting angle of $15^{\\circ}$ . In contrast, the wooden chess piece did not move at all on the unmodified wooden board even with a tilting angle of $45^{\\circ}$ (see Fig. 4C and movie S4).  \n\n![](images/9b2a0d0ab54bf0cd07535e1f694f8d5f8cf4b28b235b556ec10980af5d4604d4.jpg)  \nFig. 4. Versatility of RHP. (A) The wettability change of Teflon surfaces before and after RHP modification, corresponding to contact angle (CA) changing from $112^{\\circ}$ to $11^{\\circ}$ . (B) Modification of a porcelain bowl with a layer of RHP, leading to antifouling properties. Peanut oil could be removed by deionized water from the RHP surface (right), while oil stains on the unmodified surface remain (left). (C) The modification of wood boards with RHP by which surface lubricity is reinforced. The chess piece can easily slide off the RHP surface at a tilting angle of $15^{\\circ}$ . However, the chess piece stays on the unmodified surface even at a tilting angle of $45^{\\circ}$ . (D) Modification of PDMS with RHP that is labeled with Rhodamine B. During the course of tensile stretching with strain ranging from 0 to $100\\%$ , RHP is deformed synchronously with PDMS substrate, while the hydrogel film in the control group slips relative to the deformed substrate. Photo credit: (A, B, C, and D) Zhaoxiang Yang and Yonglin He, Renmin University of China.  \n\nThe RHP technique can be also extended to elastic substrates. Taking PDMS as an example, a silicone adhesive was used to firmly anchor RHP on PDMS surface. As a control, a hydrogel film was directly polymerized on PDMS surface without using adhesive. As shown in Fig. 4D, the RHP would be elongated together with PDMS when a tensile stretching was applied on two ends of the PDMS substrate, while the hydrogel film in a control group slipped instead of elongated with stretched PDMS. Water-soluble fluorescent dyes can be efficiently loaded in the RHP layer, which acts as a prober to help the direct monitoring of hydrogel elongation in this study. Meanwhile, loading cargos in RHP offers inspirations for drug delivery to the sites of interest if RHP technique can be applied on elastic catheters. Fluorescence photographs obviously confirm that the RHP exhibits no relative displacement with the PDMS substrate under the tensile strain ranging from 0 to $100\\%$ (fig. S15 and movie S5), which is indicative of the strong combination between PDMS and RHP. In addition, the surface wettability of RHP as represented by contact angle does not change after the tensile stretching operation (see fig. S16). Besides the studies of changing substrate materials, some other hydrogel formulas can be also formulated into RHPs (see fig. S17), confirming the generality and diversity of the RHP technology.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# Application of RHP in partial hip replacement  \n\nAs emphasized in Introduction, the lubricity between the artificial femur head and the original acetabulum is significantly important for the prognosis of the partial hip replacement. Among numerous attempts to reduce the friction in the hip joint, serum has been exploited as a popularly clinical lubricant, yet it is inevitably faced with the problems of rapid degradation and leakage from the joint (11, 13). Because of its unique characters of excellent lubricity and robustness, RHP may be ideally suited for playing a better role as lubricant in the repaired joints. A model surgery was presented in Fig. 5A, in which the RHP technique was applied to the hip joints of an adult domestic pig. The hip joint typically consists of two parts, including the acetabulum (A) and femur head (FH) (Fig. 5A, i). In the clinical surgery of partial hip replacement surgery, the necrotic femur head is generally replaced with an artificial femur head, and the healthy acetabulum is left unchanged. Two artificial femur heads were prepared by three-dimensional (3D) printing, according to the profiles of the natural femur heads that were reconstructed by a 3D scanner (fig. S18). As illustrated in Fig. 5A (ii) and movie S6, the artificial left femur head was coated with RHP, and the right one was unmodified as a reference sample. Keeping two acetabula (A-Left and A-Right) fixed, the friction test was done by rotating the artificial femur heads against the acetabulum under a given pressure in normal direction. Setting the pressure and rotation speed as the same, the cartilage on the left acetabulum was fully preserved after continuous rotation for $35\\mathrm{min}$ , while notable damage was observed in the cartilage on the right acetabulum (Fig. 5B). Magnetic resonance imaging (MRI) was used to specifically identify the damage of the left and right acetabular. On the basis of the cross-sectional imaging of cartilages in a horizontal plane, unlike the serious loss of cartilage (white shadow) on the right acetabulum, the cartilage on the left acetabulum remains almost unchanged after the friction tests (Fig. 5C and movie S7). The distinct protection of the acetabular cartilage from abrasion suggests that RHP may become a promising choice in the efforts to lubricate joints. Referring to the high cell viability of MCF-7, it is confirmed that the cytotoxicity of cured epoxy resin is negligible (fig. S19). Through the choice of biocompatible hydrogels, RHPs present great potential in applications with medical purposes.  \n\n![](images/c285408d81c8eb3a4db54e1ba2409363f260b136ab0e628eef5b39304bd72b4d.jpg)  \nFig. 5. Application of RHP in partial hip replacement surgery. (A) Schematic illustration of friction tests within hip joints, in which A, FH, A-Left, and A-Right are short for acetabulum, femur head, left acetabulum, and right acetabulum, respectively. (B) Photographs of the artificial femur head and acetabulum, and the profile of cartilages at different stages of the friction treatment. (C) Cross section MRI for the left and right acetabular cartilage (white shadow). Photo credit: (B) Zhaoxiang Yang and Yonglin He, Renmin University of China.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# Large-area preparation of RHP  \n\nRHP is a time-saving and inexpensive fabrication process, which avoids the use of aggressive solvents. It also does not rely on free radical–based polymerization and special treatment of substrate surfaces. In practice, both steps of adhesive coating and xerogel particle coating can be accomplished by means of spraying method. This technological innovation affords great convenience to prepare hydrogel coatings on a large-area substrate. As shown in Fig.  6A and movie S8, we demonstrated the possibility of preparing a hydrogel film on a 1 m–by–2 m PVC square by spraying epoxy adhesive, xerogel particles, and water in sequence. The success of RHP formation throughout the whole PVC sheet was convinced by the pronounced surface hydrophilicity. As a control, untreated PVC surface could not be wetted by the water loaded with red dyes (see Fig. 6B and fig. S20).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# DISCUSSION  \n\nIn summary, we developed a simple yet effective method, named renatured hydrogel painting (RHP), to prepare robust hydrogel coatings on various solid substrates. This hydrogel painting method involves the coating of adhesive and xerogel particles, followed by rehydration of xerogel into hydrogel. In addition to laboratory fabrication in small scale, each step can be readily scaled up with the combination of traditional spraying-based painting method. The adequate linkage by the cured adhesive enables the hydrogel coatings to accommodate arbitrary mechanical operations and volume changes in the dehydration-rehydration process. The excellent lubricity and notable robustness would attract interests in surface modification of both living and nonliving objects by means of RHP method. As far as we know, this is the first strategy for making hydrogel coatings that owns so many merits at the same time, including generality, high durability, acid and alkali resistance, self-healing capability, convenience, low cost, no aggressive solvent, no surface pretreatment, and scalable fabrication. Besides the samples as investigated in this work, this method is readily applicable to a wide range of adhesives, hydrogel formulas, and substrate materials. Their reasonable combination could possibly produce special substrates where particular hydrogel coatings are needed.  \n\n![](images/ba99a10822b90fd59830d2f149123a00c7a5ac6328ad806c600b86f0372bb22e.jpg)  \nFig. 6. RHP on a large-area PVC sheet (1 m by $2m.$ ). (A) Demonstration of the stepwise preparation of RHP with a combination spraying methodology. (B) Photographs of untreated (left) and RHP-modified (right) PVC sheets, respectively. Photo credit: (A and B) Yingchao Ma and Yonglin He, Renmin University of China.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# MATERIALS AND METHODS Materials  \n\nEpoxy adhesive (Ergo 7300), auxiliary product for cyanoacrylate adhesives (Ergo 5180), and one-component instant cyanoacrylate adhesives (Ergo 5400) were purchased from Ergo (Switzerland) as linkers. The solvent of acetone $\\mathrm{(C_{3}H_{6}O)}$ was purchased from Beijing Chemical Works (Beijing, China). Sodium alginate (SA) was purchased from Lyntech (Beijing, China), which was extracted from brown algae according to the product introduction. Acrylamide (AM), gelatin (type B) was purchased from Aladdin Bio-Chem (Shanghai, China). $N,$ , $N^{\\prime}$ -methylenebisacrylamide $(97\\%)$ (MBAM) was obtained from Alfa Aesar. Calcium chloride $(\\mathrm{CaCl}_{2})$ was provided by Beijing Chemical Reagent Company (Beijing, China). N, N, $N^{\\prime}$ , $N^{\\prime}$ - tetramethyl-ethylenediamine (TEMED) was supplied by J&K Scientific (Beijing, China). Silicone adhesive (DOW CORNING 3140 RTV) was purchased from Dow Silicones Corporation.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 14,
+        "chunk": "# Preparation and viscosity testing of linker solution  \n\nThe epoxy resin components A and B were added to acetone with a ratio of 1:1, and they were fully stirred to form a uniform solution. The linker solution was freshly prepared just before use, but the component A or B solution could be stored separately for the long term. The viscosity of epoxy resin solution was measured by a rheometer (MCR 302, Anton Paar). The shear rate varied from ${{10}^{-1}}$ to ${{10}^{3}}{{\\ s}^{-1}}$ . A steel parallel rotor with a diameter of $20~\\mathrm{mm}$ was used. The gap was kept at $50\\upmu\\mathrm{m}$ , and the temperature was fixed at $25^{\\circ}\\mathrm{C}$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# Preparation of RHP  \n\nPAM-alginate- ${\\mathrm{Ca}}^{2+}$ hydrogel was prepared by curing a precursor solution [20 weight $\\%$ (wt $\\%$ ) AM, 0.05 wt $\\%$ MBAM, 2 wt $\\%$ SA,  \n\n0.05 wt $\\%$ $(\\mathrm{NH}_{4})_{2}\\mathrm{S}_{2}\\mathrm{O}_{8}$ , 0.34 wt $\\%$ $\\mathrm{CaSO}_{4}{\\cdot}2\\mathrm{H}_{2}\\mathrm{O}$ , 0.1 wt $\\%$ TEMED] for 12 hours at room temperature. The double-network xerogel was made by vacuum freeze-drying and then triturated into multisize xerogel microparticles by ball milling. Using ethanol as the solution, the multisize xerogel microparticles were filtered by size. After the evaporation of the ethanol, SP (30 to $40\\upmu\\mathrm{m}$ ), MP (60 to $80\\upmu\\mathrm{m}$ ), and LP (100 to $150\\upmu\\mathrm{m}\\dot{}.$ ) were obtained. The substrates were first cleaned with deionized water and ethanol followed by drying under room temperature. The linker solution was coated on the surface of dry substrates. Then, the xerogel powder was sprayed on the intermediate layer prepolymer. After the polymerization of the linker, a uniform hydrogel coating was obtained, and then it was immersed in deionized water for 24 hours.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 16,
+        "chunk": "# Confocal microscope images  \n\nThe PAM-Alginate hydrogel labeled with Rhodamine B was prepared by curing a pregel solution, containing 20  wt $\\%$ AM, 0.05  wt $\\%$ MBAM, 2  wt $\\%$ SA, 0.05  wt $\\%$ $\\mathrm{(NH_{4})_{2}S_{2}O_{8}}$ , 0.34  wt $\\%$ $\\mathrm{CaSO}_{4}{\\cdot}2\\mathrm{H}_{2}\\mathrm{O}$ , 0.1 wt $\\%$ TEMED, and Rhodamine B $(10^{-5}\\mathrm{g}/\\mathrm{ml})$ , for 12 hours at room temperature. The xerogel containing Rhodamine B was punched into xerogel microparticles by ball milling. $\\operatorname{sp}_{s}$ with size approximately at $30~{\\upmu\\mathrm{m}}$ were screened out via rational filtration. The glass substrates were cleaned with deionized water and ethanol followed by drying under room temperature. Then, a linker solution containing epoxy resin prepolymer $\\left(1.0~\\mathrm{g/ml}\\right)$ and petroleum fluorescent tracing dye $(10^{-5}\\dot{\\mathrm{g/ml}})$ in acetone was coated on the surface of cleaned glass slide. Afterward, the xerogel powder was sprayed on the adhesive layer after its precuring for $15\\ \\mathrm{min}$ at $75^{\\circ}\\mathrm{C}$ . The sandwich-like sample was further placed in an oven with a temperature of $75^{\\circ}\\mathrm{C}$ for another 3 hours and then immersed in Rhodamine B solution $(10^{-5}\\mathrm{g}/\\mathrm{ml})$ for 24 hours to allow the rehydration of xerogel particles.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 17,
+        "chunk": "# Friction coefficient measurements  \n\nFriction coefficients of all samples were measured by a rotational rheometer (MCR 302, Anton Paar). Each sample (under water) was loaded on the rheometer, and a set of normal pressures (6.35 to $50.8\\ \\mathrm{kPa})$ was applied to the sample with a shear rate of $0.5\\ {\\mathfrak{s}}^{-1}$ .  \n\nFrom a rotational shearing test, the friction coefficient $\\left(\\upmu_{\\mathrm{k}}\\right)$ is measured as  \n\n$$\n\\upmu_{\\mathrm{k}}=\\uptau/P\n$$  \n\nwhere $\\boldsymbol{\\uptau}$ is the shear stress and $P$ is the pressure applied to the surface.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# Antiscratching test of RHP  \n\nThe RHPs on a PU film were scratched by a knife in the water. The 0-hour samples were taken out immediately after scratched, and the remaining samples were taken out after 6 and 36 hours in water, respectively.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 19,
+        "chunk": "# Water jet impingement test of RHP  \n\nFirst, the RHP coated on metal panel was put into the silicone oil to be fully impregnated, and the oil skin in the hydrogel coating was gradually removed when it was put into the deionized water, which proves the completeness and continuity of the hydrogel coating. Then, the RHP coated on metal panel was used for the water jet impingement test. Briefly, a high-pressure water gun was used to impact the RHP coated on metal panel. Last, the panel that had withstood an impact was subjected to the oil skin delamination experiment to verify the completeness of the hydrogel coating.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 20,
+        "chunk": "# Friction experiment between the artificial bone and the acetabulum in vitro  \n\nThe left and right hip joints were taken from the same domestic pig. The 3D structures of left femur head and right femur head were obtained by 3D scanner (OKIO 5M, TEN YOUN). Then, a pair of femoral heads were reconstructed through 3D printing (Form 2, Formlab). A milling machine (Sieg Super X3, SIEGIND) was used for the friction experiments in vitro. First, the acetabulum was fixed on the worktable of the milling machine, and the artificial femur heads were fixed on the milling head. The same compression length of spring made the hip joint sustains the same normal force in each experiment. Then, the artificial femoral heads rubbed the acetabulum at rotational speed $300~\\mathrm{rpm}$ , and deionized water was continuously added to the hip joints to keep wetting. Last, MRI (Philips Achieva $3.0\\mathrm{T}$ TX) was used to detect the damage degree of the left and right acetabular cartilages.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 21,
+        "chunk": "# Fabrication process of RHP on PVC  \n\nSpraying the epoxy solution on the PVC substrate took about $5\\mathrm{{min}}$ . The epoxy resin was allowed to be precured for $30~\\mathrm{min}$ at room temperature. Then, the xerogel powders were sprayed on the surface of partially cured epoxy resin, which took about $15\\mathrm{min}$ . After further curing of the epoxy resin for 3 hours at room temperature, the RHP coating was immediately formed once the xerogel layer was rinsed by water.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 22,
+        "chunk": "# SUPPLEMENTARY MATERIALS  \n\nSupplementary material for this article is available at http://advances.sciencemag.org/cgi content/full/7/23/eabf9117/DC1",
+        "category": " References"
+    },
+    {
+        "id": 23,
+        "chunk": "# REFERENCES AND NOTES  \n\n1.\t H. Lee, S. M. Dellatore, W. M. Miller, P. B. Messersmith, Mussel-inspired surface chemistry for multifunctional coatings. Science 318, 426–430 (2007).   \n2.\t Z. Suo, W. Yang, Functional hydrogel coatings. Natl. Sci. Rev. 8, nwaa254 (2021).   \n3.\t T. Zhao, G. Wang, D. Hao, L. Chen, K. Liu, M. Liu, Macroscopic layered organogel–hydrogel hybrids with controllable wetting and swelling performance. Adv. Funct. Mater. 28, 1800793 (2018). 4.\t A. J. T. Teo, A. Mishra, I. Park, Y.-J. Kim, W.-T. Park, Y.-J. Yoon, Polymeric biomaterials for medical implants and devices. ACS Biomater Sci. Eng. 2, 454–472 (2016).   \n5.\t S. I. Park, D. S. Brenner, G. Shin, C. D. Morgan, B. A. Copits, H. U. Chung, M. Y. Pullen, K. N. Noh, S. Davidson, S. J. Oh, J. Yoon, K.-I. Jang, V. K. Samineni, M. Norman, J. G. Grajales-Reyes, S. K. Vogt, S. S. Sundaram, K. M. Wilson, J. S. Ha, R. Xu, T. Pan, T.-I. Kim, Y. Huang, M. C. Montana, J. P. Golden, M. R. Bruchas, R. W. Gereau, J. A. Rogers, Soft, stretchable, fully implantable miniaturized optoelectronic systems for wireless optogenetics. Nat. Biotechnol. 33, 1280–1286 (2015).   \n6.\t J. W. Jeong, J. G. McCall, G. Shin, Y. Zhang, R. Al-Hasani, M. Kim, S. Li, J. Y. Sim, K.-I. Jang, Y. Shi, D. Y. Hong, Y. Liu, G. P. Schmitz, L. Xia, Z. He, P. Gamble, W. Z. Ray, Y. Huang, M. R. Bruchas, J. A. Rogers, Wireless optofluidic systems for programmable in vivo pharmacology and optogenetics. Cell 162, 662–674 (2015). 7.\t X. Tao, S. Liao, S. Wang, D. Wu, Y. Wang, Body compatible thermometer based on green electrolytes. 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Eng. 5, 6311–6318 (2019).   \n22.\t V. Nele, J. P. Wojciechowski, J. P. K. Armstrong, M. M. Stevens, Tailoring gelation mechanisms for advanced hydrogel applications. Adv. Funct. Mater. 30, 2002759 (2020).   \n23.\t A. Sinclair, M. B. O’Kelly, T. Bai, H.-C. Hung, P. Jain, S. Jiang, Self-healing zwitterionic microgels as a versatile platform for malleable cell constructs and injectable therapies. Adv. Mater. 30, 1803087 (2018).   \n24.\t G. Chen, Y. Yu, X. Wu, G. Wang, J. Ren, Y. Zhao, Bioinspired multifunctional hybrid hydrogel promotes wound healing. Adv. Funct. Mater. 28, 1801386 (2018).   \n25.\t J. S. Miller, K. R. Stevens, M. T. Yang, B. M. Baker, D.-H. T. Nguyen, D. M. Cohen, E. Toro, A. A. Chen, P. A. Galie, X. Yu, R. Chaturvedi, S. N. Bhatia, C. S. Chen, Rapid casting of patterned vascular networks for perfusable engineered three-dimensional tissues. Nat. Mater. 11, 768–774 (2012).   \n26.\t Y. Wen, Y. Liu, H. Zhang, M. Zou, D. Yan, D. Chen, Y. Zhao, A responsive porous hydrogel particle-based delivery system for oncotherapy. Nanoscale 11, 2687–2693 (2019).   \n27.\t Z. W. K. Low, Y. Luo, K. Zhang, Q. Lin, C. Owh, X. Chen, X. J. Loh, Tough hydrogel module towards an implantable remote and controlled release device. Biomater. Sci. 8, 960–972 (2020).   \n28. Y. Yu, H. Yuk, G. A. Parada, Y. Wu, X. Liu, C. S. Nabzdyk, K. Youcef-Toumi, J. Zang, X. Zhao, Multifunctional “hydrogel skins” on diverse polymers with arbitrary shapes. Adv. Mater. 31, 1807101 (2019).   \n29.\t X. Yao, J. Liu, C. Yang, X. Yang, J. Wei, Y. Xia, X. Gong, Z. Suo, Hydrogel paint. Adv. Mater. 31, 1903062 (2019).   \n30.\t R. Takahashi, K. Shimano, H. Okazaki, T. Kurokawa, T. Nakajima, T. Nonoyama, D. R. King, J. P. Gong, Tough particle-based double network hydrogels for functional solid surface coatings. Adv. Mater. Interfaces 5, 1801018 (2018).   \n31.\t W. Li, X. Liu, Z. Deng, Y. Chen, Q. Yu, W. Tang, T. L. Sun, Y. S. Zhang, K. Yue, Tough bonding, on-demand debonding, and facile rebonding between hydrogels and diverse metal surfaces. Adv. Mater. 31, 1904732 (2019).   \n32.\t S. Pan, F. Zhang, P. Cai, M. Wang, K. He, Y. Luo, Z. Li, G. Chen, S. Ji, Z. Liu, X. J. Loh, X. Chen, Mechanically interlocked hydrogel–elastomer hybrids for on-skin electronics. Adv. Funct. Mater. 30, 1909540 (2020).   \n33.\t J. Y. Chung, M. K. Chaudhury, Soft and hard adhesion. J. Adhes. 81, 1119–1145 (2005).   \n34.\t H. Lee, B. P. Lee, P. B. Messersmith, A reversible wet/dry adhesive inspired by mussels and geckos. Nature 448, 338–341 (2007).   \n35.\t H. Fan, J. Wang, Z. Tao, J. Huang, P. Rao, T. Kurokawa, J. P. Gong, Adjacent cationic– aromatic sequences yield strong electrostatic adhesion of hydrogels in seawater. Nat. Commun. 10, 5127 (2019).   \n36.\t H. Yuk, C. E. Varela, C. S. Nabzdyk, X. Mao, R. F. Padera, E. T. Roche, X. Zhao, Dry double-sided tape for adhesion of wet tissues and devices. Nature 575, 169–174 (2019).   \n37.\t Q. Zhao, D. W. Lee, B. K. Ahn, S. Seo, Y. Kaufman, J. N. Israelachvili, J. H. Waite, Underwater contact adhesion and microarchitecture in polyelectrolyte complexes actuated by solvent exchange. Nat. Mater. 15, 407–412 (2016).   \n38.\t S. Singla, G. Amarpuri, N. Dhopatkar, T. A. Blackledge, A. Dhinojwala, Hygroscopic compounds in spider aggregate glue remove interfacial water to maintain adhesion in humid conditions. Nat. Commun. 9, 1890 (2018).   \n39.\t J. Li, A. D. Celiz, J. Yang, Q. Yang, I. Wamala, W. Whyte, B. R. Seo, N. V. Vasilyev, J. J. Vlassak, Z. Suo, D. J. Mooney, Tough adhesives for diverse wet surfaces. Science 357, 378–381 (2017).   \n40.\t Z. Zhang, Z. Chen, Y. Wang, J. Chi, Y. Wang, Y. Zhao, Bioinspired bilayer structural color hydrogel actuator with multienvironment responsiveness and survivability. Small Methods 3, 1900519 (2019).   \n41.\t J. Yang, R. Bai, B. Chen, Z. Suo, Hydrogel adhesion: A supramolecular synergy of chemistry, topology, and mechanics. Adv. Funct. Mater. 30, 1901693 (2020).   \n42.\t M. J. Caulfield, G. G. Qiao, D. H. Solomon, Some aspects of the properties and degradation of polyacrylamides. Biophys. J. 102, 3067–3084 (2002).   \n43.\t K. Saha, J. Kim, E. Irwin, J. Yoon, F. Momin, V. Trujillo, D. V. Schaffer, K. E. Healy, R. C. Hayward, Surface creasing instability of soft polyacrylamide cell culture substrates. Biophys. J. 99, L94–L96 (2010).   \n44.\t M. K. Kang, R. Huang, Swell-induced surface instability of confined hydrogel layers on substrates. J. Mech. Phys. Solids 58, 1582–1598 (2010).  \n\nAcknowledgments: We are grateful to Y. Qiao and B. Hu from Institute of Microbiology, Chinese Academy of Sciences for help on the profilometer test and S. Lyu for help in MRI. X. Lian is acknowledged for help on contact angle measurement. Funding: This work was financially supported by the National Natural Science Foundation of China (22005336, 21825503, and 21674127). Author contributions: All authors discussed the results and revised the manuscript. Z.Y. led the project design and all the experiments under the supervision of Y.W. and Y.H. Y.H. assisted all the experiments in this project. S.L. assisted the fabrication of the artificial femur heads and the data analysis. Y.M. and X.T. helped with the large-area coating of RHP on PVC film. Competing interests: Y.W., Y.H., and Z.Y. are coinventors on a patent application for the use of RHP, filed by Renmin University of China (no. 201911335876.0, 23 December 2019). The remaining authors declare no competing interests. Data and materials availability: All data needed to evaluate the conclusions in the paper are present in the paper and/or the Supplementary Materials. Additional data related to this paper may be requested from the authors.  \n\nSubmitted 27 November 2020   \nAccepted 15 April 2021   \nPublished 2 June 2021   \n10.1126/sciadv.abf9117  \n\nCitation: Z. Yang, Y. He, S. Liao, Y. Ma, X. Tao, Y. Wang, Renatured hydrogel painting. Sci. Adv. 7, eabf9117 (2021).",
+        "category": " References"
+    },
+    {
+        "id": 24,
+        "chunk": "# ScienceAdvances  \n\nRenatured hydrogel painting Zhaoxiang Yang, Yonglin He, Shenglong Liao, Yingchao Ma, Xinglei Tao and Yapei Wang  \n\nSci Adv 7 (23), eabf9117. DOI: 10.1126/sciadv.abf9117  \n\nARTICLE TOOLS  \n\nSUPPLEMENTARY MATERIALS  \n\nREFERENCES  \n\nThis article cites 44 articles, 3 of which you can access for free http://advances.sciencemag.org/content/7/23/eabf9117#BIBL  \n\nPERMISSIONS  \n\nUse of this article is subject to the Terms of Service",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# High-Throughput Synthesis, Analysis, and Optimization of Injectable Hydrogels for Protein Delivery  \n\nFei Xu, Brandon Corbett, Sydney Bell, Chiyan Zhang, Monika Budi Hartono, Zohreh Jomeh Farsangi, John MacGregor, and Todd Hoare\\*  \n\nDepartment of Chemical Engineering, McMaster University, 1280 Main Street West, Hamilton, Ontario L8S 4L8, Canada  \n\nSupporting Information  \n\nABSTRACT: The development of in situ-gelling hydrogels that can enable prolonged protein release is increasingly important due to the emergence of a growing number of protein-based therapeutics. Herein, we describe a highthroughput strategy to fabricate, characterize, and subsequently optimize hydrazone-cross-linked in situ-gelling hydrogels for protein delivery. Hydrogels are fabricated using an automated high-throughput robot to mix a variety of thermoresponsive, nonthermoresponsive, charged, neutral, naturally sourced, and synthetic polymers functionalized with hydrazide or aldehyde groups, generating in situ-gelling  \n\n![](images/7d5a8c05811fcd80dcef1be125fd00361741e156eed7fba9d1dfe6ff3ee4660f.jpg)  \n\nhydrogels with well-defined compositions within a 96-well plate. High-throughput characterization strategies are subsequently developed to enable on-plate analysis of hydrogel swelling, mechanics, degradation, transparency, and protein (ovalbumin) release kinetics that yield results consistent with those collected using traditional bulk hydrogel analysis techniques. Dynamic regression and latent variable modeling are then applied to fit performance statistics to the collected data set; subsequently, numerical optimization is used to identify mixtures of precursor polymers that exhibit targeted combinations of minimal burst release, maximum total protein release, minimum release rate, and maximum transparency (the latter of particular relevance for ophthalmic protein delivery applications). Given the rapid throughput of the protocols developed (i.e., 126 hydrogels can be synthesized and screened in quadruplicate within hours), this approach offers particular promise for accelerating the identification of injectable hydrogel compositions relevant for both protein delivery as well as other biomedical applications for which clearly predefined materials properties are required.",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# INTRODUCTION  \n\nIn situ gelling hydrogels that can spontaneously gel in the body via physical1−3 and chemical reactions4,5 have attracted significant interest in the context of drug delivery and, more specifically, protein delivery. The internal gel porosity, typically on the same few nm length scale of most proteins, can be engineered by manipulating the cross-linker density6 and the structure of the gel building blocks7,8 to either irreversibly entrap the protein9,10 or control protein release at a rate proportional to the relative sizes of the protein and the pore network created.11 Furthermore, by introducing affinity groups into the hydrogel that can interact with proteins (e.g., charged moieties or hydrophobic domains), the affinity of the protein for the gel phase can be engineered to further tune release kinetics.12,13 If the in situ chemistry creates a degradable crosslink, further control over protein release kinetics can be achieved based on not only diffusion/affinity but also the rate of bulk matrix degradation.14−16 Leveraging these advantages, in situ-gelling hydrogels have been demonstrated to enable, for example, sustained release of vascular endothelium growth factor (VEGF) or bevacizumab for eye diseases.17,18  \n\nIn designing hydrogels specifically for protein delivery applications, the choice of the constituent polymer is particularly critical. The majority of effort has focused on one of two classes of polymers: (1) naturally occurring polymers that can be degraded via various oxidative or enzymatic pathways in vivo and have established records of biocompatibility (e.g., alginate, chitosan, dextran, hyaluronic acid, and various soluble cellulose derivatives),19,20 but can offer significant batch-to-batch variability and limited options for chemical functionalization, or (2) smart materials that can undergo physical changes in swelling upon the exposure of different environmental stimuli such as temperature, $\\mathrm{\\tt{pH}},$ or ionic strength. Temperature-responsive smart materials such as poly(N-isopropylacrylamide) (PNIPAM)21,22 or poly(ethylene oxide)/poly(propylene oxide) block copolymers (Pluronics23) have attracted particular interest given their potential to both facilitate in situ gelation upon heating from room temperature to physiological temperature as well as deswell in the body to entrap a protein cargo and thus prolong its release. Poly(oligo ethylene glycol methacrylate) (POEGMA) has more recently been explored as an alternative thermoresponsive polymer that exhibits similar properties to PNIPAM but avoids many of the regulatory issues that have limited the translation of PNIPAMbased materials to the clinic.4,24−27 In addition, the lower critical solution temperature (LCST) of POEGMA-based polymers can be tuned from 22 to ${\\tt>}90{\\ ^{\\circ}C}$ by changing the number of ethylene oxide (EO) repeat units in the side chain of the polymer.26−28 However, the successful translation of smart polymers requires solving key challenges around degradation29,30 and avoiding the convective burst release of the protein payload that is often observed as the gel deswells at physiological temperature.31,32  \n\nBased on these inherent limitations of both natural and synthetic polymer-based conventional hydrogels for protein delivery, coupled with the multiple potential variables (e.g., hydrogel cross-link density, degradability, porosity, chemical affinity) that must be optimized for each specific protein to be delivered, the development of hydrogel-based protein delivery vehicles remains a challenging and largely trial-and-error process for each protein type and dose targeted. Given the sharply increasing number of protein-based therapeutics now transitioning into the clinic,33 developing a rapid method to design a controlled delivery vehicle most suitable to deliver a given protein at the required dose over the required time is increasingly important.  \n\nIn our previous work, we have extensively explored the use of hydrazide-aldehyde chemistry for creating functional in situgelling hydrogels based on PNIPAM,21 POEGMA,24 charged POEGMA derivatives,12,34 and natural polymers like carboxymethyl cellulose and dextran.35,36 Hydrazone chemistry is attractive, given its combination of rapid gelation (between seconds to minutes following mixing via coextrusion through a double barrel syringe) and hydrolytic degradability (tunable between weeks to months at neutral $\\mathrm{\\pH}$ ).12,24,31 In addition, by mixing different hydrazide and aldehyde precursor polymers with different properties (for example, natural degradable polymers, thermoresponsive polymers,30 and thermoresponsive polymers with different phase transition temperatures31), we have demonstrated the potential to precisely tune hydrogel properties by simple additive mixing, including the potential to prolong the release of model proteins through the formation of phase-separated domains within hydrogels.31 This mixingbased approach is attractive in that multiple hydrogels with significantly different properties can be fabricated by mixing a smaller set of precursor polymers in different ratios, reducing the required synthetic burden for hydrogel optimization. However, if a specific set of properties is desired, even this mixing approach becomes a slow trial-and-error process, particularly if the precursor polymers phase separate or interact in some way that makes the overall properties of the resulting hydrogel nonadditive (and thus less predictable) based on the precursor polymer content.  \n\nGiven the clear potential of precursor polymer mixing to generate hydrogels with targeted properties, applying highthroughput fabrication techniques to produce such hydrogels via automated mixing protocols offers a potential solution to this challenge. High-throughput screening techniques have been widely used in the field of drug or cell-based assays;37,38 however, few reports have discussed the use of highthroughput robotics to fabricate and optimize hydrogels. This gap is likely due to the technical challenges inherent in both repeatedly fabricating gels in high throughput, as well as subsequently characterizing the properties of the resulting hydrogel arrays with sufficient speed that synthesizing hydrogels in high-throughput would be practically beneficial. However, if these challenges can be overcome, the high amount of data that can be generated quickly using highthroughput approaches is ideal for not only screening potential hydrogel compositions for particular end-uses but also for applying statistical optimization techniques that can fit multivariate mathematical models to the high-throughput data and (following model inversion) subsequently predict formulations that would offer better performance in terms of achieving a specific set of property targets. We have previously demonstrated the potential of latent variable methods to assist in designing multiresponsive polymers based on historical data;39 by using high-throughput data collection to rapidly collect this historical data, we expect that we can significantly accelerate the identification of hydrogel compositions suitable for protein delivery.  \n\nHerein, we report high-throughput techniques to both fabricate and characterize hydrogel arrays based on the programmable mixing of 13 different precursor polymers (12 functionalized with hydrazide groups and 2 functionalized with aldehyde groups). In particular, precursor polymers with various charges (anionic, cationic, neutral), degradabilities (i.e., naturally sourced vs synthetic), and thermoresponsiveness (using both PNIPAM and POEGMA functional copolymers with various LCST values) were mixed in various ratios to fabricate 126 different hydrogels using a high-content robotics system in $<25~\\mathrm{\\min}$ . Subsequently, high-throughput test methods were developed and validated to probe the physical and pharmacokinetic properties of such hydrogels. Fitting a multivariate model to this high-throughput data set was demonstrated to enable a priori prediction of key hydrogel properties relevant to protein delivery; subsequent model inversion enabled the prediction of hydrogel recipes leading to improved protein release kinetics customized to the priorities of each drug release case.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# EXPERIMENTAL SECTION  \n\nMaterials. Oligo(ethylene glycol) methyl ether methacrylate $(\\mathrm{OEGMA}_{475},$ $M_{\\mathrm{n}}~=~475~\\mathrm{g/mol})$ and di(ethylene glycol) methyl ether methacrylate $(\\mathbf{M}(\\mathrm{EO})_{2}\\mathbf{MA})$ were purchased from SigmaAldrich and were purified using an aluminum oxide (Sigma-Aldrich, type CG-20) column to remove the methyl ether hydroquinone (MEHQ) and butylated hydroxytoluene (BHT) inhibitors. N-(2,2- Dimethoxyethyl) methacrylamide (DMEMAm) was synthesized following our previous protocol.25 Dextran $\\left(M_{\\mathrm{r}}\\ =\\ 40000\\ \\mathrm{g/mol}\\right)$ chitosan (low molecular weight), sodium carboxymethyl cellulose (CMC, $M_{\\mathrm{w}}=90000\\mathrm{g/mol}$ , $\\mathrm{DS}\\ =\\ 0.9\\ \\cdot$ ), $N,N_{\\astrosun}$ -dimethylaminoethyl methacrylate (DMAEMA), $N$ -isopropylacrylamide (NIPAM, $99\\%$ ), acrylic acid (AA, $99\\%$ ), thioglycolic acid (TGA, $98\\%$ ), $N\\mathrm{.}$ - hydroxysuccinimide (NHS, $97\\%$ ), monochloroacetic acid (MACC), and $N,N.$ -dimethylformamide (DMF, $99\\%$ ) were purchased from Sigma-Aldrich and used as received. Adipic acid dihydrazide (ADH, Alfa Aesar, $98\\%$ ), $N^{\\prime}$ -ethyl-N-(3-(dimethylamino)propyl)-carbodiimide (EDC, Carbosynth, Compton $\\mathrm{CA},$ commercial grade), 2,2- azobisisobutyric acid dimethyl ester (AIBMe, Wako Chemicals, $98.5\\%$ ), and dioxane (Caledon Laboratories, $99\\%$ ) were used as received. Sodium hydroxide (NaOH) and hydrogen chloride (HCl) were purchased from LabChem Inc. and used as received. NIH 3T3 mouse fibroblast cells were purchased from ATCC (Cedarlane Laboratories, Burlington, ON, Canada). Dulbecco’s Modified Eagle’s Medium (DMEM, Life Technologies), fetal bovine serum (FBS, ThermoFisher), penicillin-streptomycin (PS, ThermoFisher), PrestoBlue cell viability reagent (ThermoFisher), a Bradford reagent kit (Sigma-Aldrich), and albumin from chicken egg white (ovalbumin, Sigma-Aldrich) were used as received. Milli- $\\mathrm{\\DeltaQ}$ grade distilled deionized water (DIW) and $10~\\mathrm{mM}$ PBS was used for experiments.  \n\nTable 1. Synthetic Recipes for POEGMA Polymer Precursors   \n\n\n<html><body><table><tr><td></td><td>OEGMA475 (mmol)</td><td>M(EO)MA (mmol)</td><td>AA (mmol)</td><td>DMEMAm (mmol)</td><td>TGA (mmol)</td><td>AIBMe (mmol)</td><td>DMAEMA (mmol)</td></tr><tr><td>POH30</td><td>0.0</td><td>21.3</td><td>9.0</td><td></td><td>0.1</td><td>0.16</td><td></td></tr><tr><td>PO10H30</td><td>1.8</td><td>18.0</td><td>8.5</td><td></td><td>0.1</td><td>0.16</td><td rowspan=\"6\">3.5</td></tr><tr><td>PO50H30</td><td>4.2</td><td>4.2</td><td>3.6</td><td></td><td>0.1</td><td>0.16</td></tr><tr><td>PO100H30</td><td>8.4</td><td>0.0</td><td>3.6</td><td></td><td>0.02</td><td>0.16</td></tr><tr><td>PO100H30C20</td><td>8.4</td><td>0.0</td><td>5.1</td><td></td><td>0.02</td><td>0.16</td></tr><tr><td>PO100H30A20</td><td>8.4</td><td>0.0</td><td>8.6</td><td></td><td>0.02</td><td>0.16</td></tr><tr><td>PO10A30</td><td>1.8</td><td>18.0</td><td></td><td>7.5</td><td>0.1</td><td>0.22</td></tr><tr><td>PO100A30</td><td>8.4</td><td>0.0</td><td></td><td>3.5</td><td>0.02</td><td>0.22</td></tr></table></body></html>  \n\nSynthesis and Characterization of Polymer Precursors. Chemical Characterization. $^{1}\\mathrm{H}$ NMR was performed using a Bruker ${600~\\mathrm{MHz}}$ spectrometer using deuterated chloroform as the solvent. The carboxylic acid content of relevant polymer precursors was determined by base-into-acid titration (ManTech Associates) using $100\\ \\mathrm{mM\\NaOH}$ as the base. The lower critical solution temperatures (LCST) of the polymer precursors were determined from a $10~\\mathrm{mg/}$ mL polymer solution in $10\\ \\mathrm{mM}$ PBS using a Variant Cary Bio 100 UV−vis spectrophotometer ramped over a temperature range of $20-$ $80~^{\\circ}\\mathrm{C}$ at a rate of $0.5~\\mathrm{{}^{\\circ}C/m i n}$ . The molecular weight of polymer precursors was determined using gel permeation chromatography (GPC). Samples soluble in water were analyzed using a system consisting of a Waters 515 HPLC pump, a Waters 717 plus Autosampler and three columns (Waters Ultrahydrogel-120, $-250,$ $-500$ ; $7.8\\times300\\ \\mathrm{mm}$ ; $6~\\mu\\mathrm{m}$ particles), with a continuous phase consisting of $0.5\\mathrm{~M~}$ sodium nitrate and $25\\ \\mathrm{mM}\\ 2$ -(cyclohexylamino) ethanesulfonic acid maintained at $\\mathrm{pH}10.0$ at $30~^{\\circ}\\mathrm{C}$ . Samples soluble in DMF were analyzed using a Polymer Laboratories PL-50 GPC system consisting of three Phenomenex PhenogelTM columns ( $300\\times$ $4.6\\ \\mathrm{mm}$ , ${\\mathfrak{s}}\\mu\\mathrm{{m}};$ pore size: 100, 500, 104 Å), with the continuous phase consisting of DMF containing $50\\ \\mathrm{\\mM}$ LiBr maintained at room temperature. All samples for GPC were filtered using a $0.2\\ \\mu\\mathrm{m}$ filter. Hydrazide-Functionalized POEGMA. The synthetic recipes and resulting chemical properties of POEGMA hydrazide precursor polymers produced are shown in Table 1. All hydrazide functionalized POEGMA polymers were synthesized following recipes previously reported.40 In brief, diethylene glycol methacrylate $(\\mathbf{M}(\\mathrm{EO})_{2}\\mathbf{MA},$ , $n=$ 2), oligo ethylene glycol methacrylate $\\mathrm{'OEGMA_{475}},$ $n=8,9$ ), acrylic acid (AA), 2,2-azobisisobutryic acid dimethyl ester (AIBMe), thioglycolic acid (TGA), and $20~\\mathrm{mL}$ of dioxane were added in a 50 mL Schlenk three-neck flask and purged with nitrogen for $30\\ \\mathrm{min}$ before being placed into a $75~^{\\circ}\\mathrm{C}$ oil bath. The polymerization was completed in $^{4\\mathrm{h}}$ under magnetic stirring to obtain poly(OEGMA-coAA) copolymer, followed by rotary evaporation to remove extra dioxane. Subsequently, poly(OEGMA-co-AA) was redissolved in 100 mL of DIW, and the acrylic acid residues were functionalized with hydrazide groups via carbodiimide chemistry using a 5-fold excess of adipic acid dihydrazide and an 2.5-fold excess of EDC $\\mathrm{(pH=4.75)}$ . The resulting POEGMA precursor polymers are labeled as $\\mathrm{PO}_{\\boldsymbol{x}}\\mathrm{H}_{\\boldsymbol{y}},$ where $x$ represents the mole percentage of $\\mathrm{OEGMA_{475}}$ relative to the sum of the $\\mathrm{OEGMA_{475}}$ (long chain, high transition temperature) and $\\mathbf{M}(\\mathrm{EO})_{2}\\mathbf{MA}$ (short chain, low transition temperature) OEGMA monomers added and $y$ is the overall mol $\\%$ of monomer residues bearing hydrazide groups. By changing the ratio of $\\mathrm{OEGMA_{475}/}$ $\\begin{array}{r}{\\mathbf{M}(\\mathrm{EO})_{2}\\mathbf{M}\\mathbf{A},}\\end{array}$ the LCST of POEGMA precursors can be adjusted from low $\\mathrm{(PO_{0}H_{30}}$ and $\\mathrm{PO}_{10}\\mathrm{H}_{30}\\big)$ to medium $\\mathrm{(PO}_{50}\\mathrm{H}_{30}\\mathrm{)}$ to high $\\mathrm{(PO}_{100}\\mathrm{H}_{30}\\right)$ .28,31 The hydrazide content was determined by the difference in the titrated $-\\mathrm{COOH}$ content of the polymers before and after ADH functionalization. Charged POEGMA precursors $\\mathrm{PO}_{100}\\mathrm{H}_{30}$ -cationic and $\\mathrm{PO}_{100}\\mathrm{H}_{30^{-}}$ anionic were synthesized using the same protocols but adding $20~\\mathrm{mol}$ $\\%$ of $N,N$ -dimethylaminoethyl methacrylate (cationic) or $2\\Bar{0}\\mathrm{~mol~}\\%$ extra acrylic acid (anionic), respectively (Table 1).12,34 All precursors were dialyzed for purification ( $^{6+}$ hours for 6 cycles using dialysis tubing with molecular weight cutoff (MWCO) of $3.5~\\mathrm{\\kDa})$ , lyophilized, and stored in a 15 wt $\\%$ solution of $10\\ \\mathrm{mM}\\ \\mathrm{PBS}$ at 4 $^{\\circ}\\mathrm{C}$ . Polymers were characterized as described above, with the additional step of base-into-acid conductometric titration (as previously described) to determine the net cationic and anionic charge content.  \n\nHydrazide-Functionalized PNIPAM (PNIPAM-Hzd). PNIPAM-Hzd precursor was synthesized following previous work.21,41 In brief, 4.00 $\\mathsf{g}$ $\\textsl{g}(0.035\\ \\mathrm{mol})$ of NIPAM, $\\boldsymbol{1.00\\mathrm{~g}}$ $\\mathrm{\\bar{\\langle}0.014~m o l\\rangle}$ of acrylic acid, $87\\ \\mu\\mathrm{L}$ $\\left(1.25\\mathrm{\\mmol}\\right)$ of TGA and $55.5~\\mathrm{\\mg}$ $\\mathrm{(0.24~mmol)}$ of AIBMe were dissolved in $20~\\mathrm{mL}$ of ethanol and polymerized for overnight at $56^{\\circ}\\mathrm{C}$ under nitrogen. The solution was then lyophilized, redissolved in DIW, and functionalized with hydrazide groups using ADH/EDC chemistry as described for the POEGMA precursors. The resulting PNIPAM-Hzd polymer was then dialyzed $^{\\circ+}$ hours for 6 cycles, $\\mathrm{MWCO}~=~3.5~\\mathrm{\\kDa};$ ) and lyophilized for storage. The hydrazide content was determined by the difference in the titrated $-\\mathrm{COOH}$ contents of the polymers before and after ADH functionalization.  \n\nHydrazide-Functionalized Dextran (Dextran-Hzd). Hydrazidefunctionalized dextran was prepared following previous work.42−44 A total of $\\textsf{S g}$ ( $\\left(0.13\\mathrm{\\mmol}\\right)^{\\cdot}$ ) of dextran from Leuconostoc spp (SigmaAldrich, $M_{\\mathrm{r}}\\sim40000)$ was dissolved in $42~\\mathrm{mL}$ of a $3~\\mathrm{M}$ solution of ${\\mathrm{NaOH}}_{;}$ , after which $7.29\\ \\mathrm{g}$ $\\mathrm{77~mmol)}$ of chloroacetic acid was added and stirred at room temperature until dissolution. Subsequently, the solution was heated at $70~^{\\circ}\\mathrm{C}$ for $90~\\mathrm{{min}}$ , cooled back to room temperature, and neutralized to $\\mathrm{pH}~7.0$ by adding acetic acid. The product was precipitated with methanol and collected through vacuum filtration to acquire a raw product that was stirred in acetone overnight to fully precipitate. Subsequently, the resulting product was washed with acetone and dried in an oven at $60~^{\\circ}\\mathrm{C}$ . The resulting carboxymethylated dextran was then functionalized with hydrazide groups by adding 2.5-fold excess EDC and 5-fold excess ADH in water $\\left(\\mathsf{p H4.75}\\right)$ . The final product was obtained by dialysis ( $^{6+}$ hours for 6 cycles, $\\mathrm{MWCO}\\ =\\ 12\\ \\mathrm{kDa}$ ) and lyophilized for storage. The hydrazide content was determined by the difference in the titrated −COOH content between the carboxymethylated dextrans before and after ADH functionalization.  \n\nHydrazide-Functionalized Chitosan (Chitosan-Hzd). ChitosanHzd was prepared following previously reported protocols.45,46 A total of $_{\\textrm{1g}}$ of chitosan was slowly added to a solution of sodium hydroxide (NaOH, $43.75~\\mathrm{\\mmol}$ dissolved in $2{\\mathrm{~mL~}}$ of Milli-Q DIW) under magnetic stirring to swell (but not dissolve) the chitosan powder, followed by the addition of $8{\\mathrm{~mL~}}$ of 2-propanol. The mixture was stirred for $^{\\textrm{1h,}}$ after which $1.75\\mathrm{g}\\left(0.02\\mathrm{mol}\\right)$ of monochloroacetic acid predissolved in $2\\mathrm{mL}$ of isopropanol was added. After $^{4\\mathrm{h},}$ the reaction was stopped by adding $50~\\mathrm{\\mL}$ of $70\\%$ ethanol. The resulting carboxymethylated chitosan was then purified by dialysis ( $^{6+}$ hours for 6 cycles, $\\mathrm{MWCO}=12\\ \\mathrm{kDa}$ ) and functionalized with hydrazide groups using the same EDC/ADH chemistry outlined for dextran. The final product was dialyzed and lyophilized for storage. The hydrazide content was determined by the difference in the titrated −COOH content between the carboxymethylated chitosan before and after ADH functionalization.  \n\nHydrazide-Functionalized Sodium Carboxymethyl Cellulose (CMC-Hzd). Synthesis of CMC-Hzd was reported in previous work.44 A total of $1.0\\mathrm{~g~}$ of CMC $\\left(0.01\\mathrm{\\mmol}\\right)^{\\cdot}$ ) and $_{3\\mathrm{~g~}}$ ( $\\cdot0.02\\ \\mathrm{mol},$ )  \n\nTable 2. Chemical Characterization of Polymer Precursors   \n\n\n<html><body><table><tr><td>category</td><td>polymers</td><td> functional group</td><td>functionality mol %</td><td>M, 10° g mol-1</td><td> PDI</td><td>charge</td><td>LCST °C</td><td>concn mg/mL</td></tr><tr><td>group T</td><td>POH30</td><td>NHNH</td><td>30.5a</td><td>16.5b</td><td>2.95</td><td>neutral</td><td>36.6</td><td>150</td></tr><tr><td rowspan=\"12\">group C</td><td>PO10H30</td><td>NHNH</td><td>31.9a</td><td>19.8h</td><td>2.18</td><td>neutral</td><td>52.6</td><td>150</td></tr><tr><td>PO50H30</td><td>NHNH</td><td>29.6a</td><td>31.1b</td><td>1.76</td><td>neutral</td><td>>80</td><td>150</td></tr><tr><td>PO100H30</td><td>NHNH</td><td>29.5a</td><td>29.7℃</td><td>2.82</td><td>neutral</td><td>>80</td><td>150</td></tr><tr><td>PNIPAM-Hzd</td><td>NHNH</td><td>26.5a</td><td>25.3b</td><td>1.43</td><td>neutral</td><td>32.0</td><td>60</td></tr><tr><td>CMC40-Hzd</td><td>NHNH</td><td>23.3a</td><td>90d</td><td>N/A</td><td>neutral</td><td>>80</td><td>40</td></tr><tr><td>PO10A30</td><td>CHO</td><td>31.6d</td><td>17.4b</td><td>2.24</td><td>neutral</td><td>44.5</td><td>150</td></tr><tr><td>PO100H30</td><td>NHNH</td><td>29.5a</td><td>29.7℃</td><td>2.82</td><td>neutral</td><td>>80</td><td>150</td></tr><tr><td>PO100H30C20</td><td>NHNH</td><td>33.3a</td><td>31.2</td><td>3.75</td><td>cationic</td><td>>80</td><td>150</td></tr><tr><td>PO100H30A20</td><td>NHNH</td><td>27.8a</td><td>29.8</td><td>2.82</td><td>anionic</td><td>>80</td><td>150</td></tr><tr><td>CMC20-Hzd</td><td>NHNH</td><td>23.3a</td><td>90℃</td><td>N/A</td><td>neutral</td><td>>80</td><td>20</td></tr><tr><td>dextran-Hzd</td><td>NHNH</td><td>25.7a</td><td>40°</td><td>N/A</td><td>neutral</td><td>>80</td><td>15</td></tr><tr><td>chitosan-Hzd</td><td>NHNH</td><td>26.7a</td><td>lowe</td><td>N/A</td><td>cationic</td><td>>80</td><td>20</td></tr><tr><td>PO100A30</td><td>CHO</td><td>28.2d</td><td>24.1℃</td><td>3.25</td><td>neutral</td><td>>80</td><td>150</td></tr></table></body></html>\n\naDetermined by base-into-acid titration. bDetermined by DMF GPC. cDetermined by aqueous GPC. dDetermined by $\\mathrm{^{1}H}$ NMR. eInformation provided by supplier. $\\mathrm{LCST}=$ lower critical solution temperature  \n\nof ADH were dissolved in $200~\\mathrm{mL}$ of DIW. Following this, premade solutions of $\\boldsymbol{0.07\\mathrm{g}}$ $\\mathrm{0.6~mmol})$ of NHS (suspended in $4~\\mathrm{mL}$ of a 1:1 $\\mathrm{DMSO/H_{2}O}$ solution) and $_{0.3\\mathrm{~g~}}$ ( $1.6\\ \\mathrm{mmol})$ of EDC (dissolved in 1 mL of a 1:1 $\\mathrm{DMSO/H_{2}O}$ solution) were added to the flask sequentially. The $\\mathrm{\\pH}$ of CMC solution was adjusted to $\\mathsf{p H}6.8$ using $\\mathrm{\\DeltaNaOH}$ and HCl solutions until no longer changed $({\\sim}4\\ \\mathrm{h})$ . The resulting hydrazide-functionalized polymer was dialyzed dialysis $^{'}6+$ hours for 6 cycles, $\\mathrm{MWCO}=12\\mathrm{\\kDa}$ ) and lyophilized for storage. The hydrazide content was determined by the difference in the titrated −COOH content before and after ADH functionalization. Two different concentrations of CMC-Hzd $\\mathrm{\\CMC_{40}–H z d}$ and $\\mathrm{CMC}_{20^{-}}$ Hzd) were used, with the subscript in each case corresponding to 40 and $20~\\mathrm{mg/mL}$ .  \n\nAldehyde-Functionalized POEGMA Polymer Precursors. Aldehyde-functionalized POEGMA precursors were synthesized as previously described.4,25 Briefly, diethylene glycol methacrylate $\\mathbf{\\left(M(EO)}_{2}\\mathbf{MA}$ , $\\begin{array}{l c l}{n}&{=}&{2,}\\end{array}$ ), oligo ethylene glycol methacrylate $(\\mathrm{OEGMA}_{475},$ $\\begin{array}{r l r}{n}&{{}=}&{8,9}\\end{array}$ ), $N\\mathrm{.}$ -(2,2-dimethoxyethyl) methacrylamide (DMEMAm), AIBMe initiator, and TGA chain transfer agent were dissolved in $20~\\mathrm{mL}$ of dioxane and reacted for $^\\textrm{\\scriptsize4h}$ at $75~^{\\circ}\\mathrm{C}$ under nitrogen. The resulting poly(OEGMA-co-DMEMAm) polymer precursors $(\\sim4\\textrm{g})$ were subsequently dissolved in $75~\\mathrm{mL}$ of DIW, followed by adding $25~\\mathrm{\\mL}$ of $1.0\\mathrm{~M~HCl}$ and reacted at room temperature for $24\\mathrm{~h~}$ to convert the acetal groups in the DMEMAm residues to aldehyde groups to form $\\mathrm{PO}_{x}\\mathrm{A}_{y},$ where $x$ represents the $\\mathrm{OEGMA}_{475}/\\mathrm{M}(\\mathrm{EO})_{2}\\mathrm{\\bar{M}A}$ ratio (as with the hydrazide polymers) and y represents the overall mole fraction of monomers bearing an aldehyde group (Table 1). The resulting precursors were dialyzed $^{\\prime}6+$ hours for 6 cycles, using dialysis tubing with MWCO of $3.5\\mathrm{\\kDa}$ ), lyophilized, and stored in $15\\%$ solutions in $10~\\mathrm{mM}$ PBS at $4~^{\\circ}\\mathrm{C}$ . The aldehyde content of the polymers was determined by $^{1}\\mathrm{H}$ NMR comparing the aldehyde proton $(\\delta\\sim9)$ with the methoxy proton ( $\\overset{\\cdot}{\\delta}$ $\\sim3.5)$ .  \n\nHydrogel Preparation. Hydrogels were prepared using an automated material screening high-throughput robotics system (Tecan Evo 200). Polymer precursor solutions were first loaded in a 24 well-plate ( $2\\ \\mathrm{\\mL}$ /well for each precursor polymer). Subsequently, 8 available robotic arms were used to aspirate preprogrammed volumes of each hydrazide precursor polymer into different wells of a 96 well-plate (Greiner, VWR) using a factorial design strategy, in which each possible equal volume combination of the six hydrazide precursor polymers within each series (Table 2) was pipetted sequentially into each well (Figure 1; see Tables S1 and S2 for detailed recipes of polymers dispensed into each well). The pipetting parameters were optimized for different ranges of liquid types; for example, the aspiration speed used for low-viscosity POEGMA polymer precursors was $800\\ \\mu\\mathrm{L}/s,$ while an aspiration speed of $100\\ \\mu\\mathrm{L}/\\mathrm{s}$ was used for the relatively viscous chitosan precursor. After dispensing all the hydrazide precursor polymers, the plate was automatically moved to a shaker platform and mixed at 1700 rpm for $10\\mathrm{~s~}$ to promote mixing of all added hydrazide components. The plate was then moved back to the pipetting platform, and the relevant aldehyde precursor polymer was added column by column to each well, with the plate moved back to the shaker for $\\textit{\\textbf{5s}}$ after each column of aldehyde polymer was added. To avoid bubbles and promote mixing when adding the aldehyde polymer precursors, (1) $70~\\mu\\mathrm{L}$ of POA was aspirated, but only $60~\\mu\\mathrm{L}$ was dispensed in each well (ensuring no air is injected), and (2) the pipet tips were fully immersed in the hydrazide polymer solutions.  \n\n![](images/792dc3edb8820f1227bb376027473c61f9b949a4eb21e3db155c6692902519dc.jpg)  \nFigure 1. Schematic of compositions of hydrazide polymer precursors in a 96-well plate.  \n\nHigh-Throughput Hydrogel Characterization. Hydrogel Swelling. A total of $120~\\mu\\mathrm{L}$ of $10\\ \\mathrm{mM}$ PBS was added to each well containing a hydrogel and incubated for $^{48\\mathrm{~h~}}$ at $22\\ ^{\\circ}\\mathrm{C},$ a time confirmed to achieve equilibrium swelling in previous experiments12,24 and a temperature below the LCST values of each polymer precursor. The “find contact” function of a Mach-1 micromechanical tester fitted with a $1\\ \\mathrm{mm}$ diameter rounded tip indenter (Biomomentum, Laval, Canada) was used to track the change in the height of the hydrogel in each well before and after swelling according to the height of hydrogel in each well, as per eq 1.  \n\n![](images/dc61bd84090466a463f44a15ecc25a5c0af6570eb4f59fe64cc3e5edb939f738.jpg)  \nFigure 2. Model form for partial least-squares analysis of high-throughput hydrogel data.  \n\n$$\n{\\mathrm{normalizedvolume}}={\\frac{V_{\\mathrm{final}}}{V_{\\mathrm{initial}}}}={\\frac{A\\times H_{\\mathrm{gel}}}{120~{\\upmu\\mathrm{L}}}}\n$$  \n\nHere, $V_{\\mathrm{final}}$ and $V_{\\mathrm{initial}}$ are the volumes of gel before $\\left(t=0\\mathrm{h}\\right)$ and after swelling $t=48\\ \\mathrm{h},$ , respectively, $A$ is the cross-sectional area of each well in 96 well-plate $(0.{\\bar{3}}4\\thinspace\\mathrm{cm}^{2})$ , and $H_{\\mathrm{gel}}$ is the height of gel measured by Mach-1 tester (i.e., the height of the gel at the test time point subtracted by the premeasured height of the empty well). Error bars represent the standard deviation of four independent measurements $\\left(n=4\\right)$ .  \n\nHydrogel Mechanics. The compressive modulus of the hydrogels was measured inside the 96-well plates using a $1~\\mathrm{mm}$ diameter rounded tip indenter and the Mach-1 micromechanical tester with a multiwell plate attachment. The modulus was measured by finding the contact in each well and performing a $10\\%$ compression, with the modulus corresponding to the slope of the resulting stress versus strain curve. Error bars represent the standard deviation of four independent measurements $\\left(n=4\\right)$ .  \n\nHydrogel Degradation. Hydrogel degradation was determined by tracking the change in the compressive modulus of the hydrogels in acid-accelerated conditions to allow for comparisons between the degradation rates of different hydrogels under practical-to-measure timeframes. Following an equilibrium swelling step ( $\\ln\\mathrm{\\Delta}$ of PBS/ well, $22\\ ^{\\circ}\\mathrm{C},$ after $^{72\\mathrm{~h~}}$ ), the PBS was removed and a compressive modulus measurement was done in each well using the Mach-1 micromechanical tester as described above. Subsequently, $100\\ \\mathrm{mM}$ HCl ( $120~\\mu\\mathrm{L}$ per well, $22\\ ^{\\circ}\\mathrm{C})$ was added to each well, and the compressive modulus measurement was repeated at predetermined time intervals until complete gel degradation (considered to be the point at which the modulus of the residual hydrogel was below the detection threshold of the find contact measurement). Error bars represent the standard deviation of four independent measurements $\\overset{\\mathcal{-}}{\\left(n\\right.}=4\\overset{\\mathcal{-}}{\\left)}$ .  \n\nTransparency. The transmittance of each hydrogel was determined using a VICTOR 3 multilabel microplate reader operating at a wavelength of $595~\\mathrm{{\\nm}}$ . The transmittance was scanned over a temperature range of 25 to $40\\ ^{\\circ}\\mathrm{C},$ using an equilibration time of 10 min at each fixed temperature measurement. Error bars represent the standard deviation of four independent measurements $\\left(n=4\\right)$ .  \n\nDrug Release Kinetics. Hydrogels were prepared as described above using the high-throughput robotics system but also dissolving $25~\\mathrm{mg/mL}$ ovalbumin in the POA component (i.e., the component added consistently to each well), resulting in a total of $1.5~\\mathrm{mg}$ protein encapsulated in each gel. For drug release experiment, hydrogels were first fabricated inside a 96-well MultiScreen-Mesh filter plate and then submerged in a 96-well receiver with $10\\ \\mathrm{mM}$ PBS (EMD Millipore, see Supporting Information, Figure S1). A total of $100\\mu\\mathrm{L}$ of PBS was added on the top of each hydrogel, while $250\\mu\\mathrm{L}$ of PBS was added in the bottom (i.e., in the receiving chamber) of each insert, after which the samples were incubated at $37~^{\\circ}\\mathrm{C}$ over a one-month period. At predetermined intervals, $20~\\mu\\mathrm{L}$ of medium was taken from the reserved plate for each sample and assayed for protein concentration using a Bradford assay, with the concentration calculated based on a calibration of standard ovalbumin concentrations $\\displaystyle{{'R}^{2}=0.99},$ ). Error bars represent the standard deviation of four independent measurements $\\left(n=4\\right)$ . All volumes of PBS was replaced with fresh PBS after measurement every time.  \n\nDynamic and Latent Variable Modeling and Analysis. Dynamic Modeling of Drug Release Kinetics. Data from the drug release kinetics measurements were first modeled using dynamic regression modeling to convert the kinetic curves into fitting parameters that could be incorporated into the multivariate statistical model. The release kinetics profiles were fit to a modified first-order (i.e., diffusion-governed) model (eq 2):  \n\n$$\n\\hat{y}(t)=y_{f}+(y_{0}-y_{f})e^{-t/\\tau}\n$$  \n\nwhere $\\hat{y}(t)$ represents the predicted protein concentration at time $t,$ and $y_{0},y_{\\beta}$ and $\\tau$ are modeling parameters representing the initial drug concentration, final drug concentration (at infinite time), and first order rate constant (reflecting the release rate), respectively. Note that the $y_{0}$ term was included to compensate for burst release early in the release process, while the $y_{f}$ term was incorporated to compensate for potential protein entrapment inside the gels, particularly relevant for temperature-responsive hydrogels that significantly dehydrate over time. Parameters that minimized the sum of squared error between the experimental and predicted data were fit by explicitly finding the zero of the gradient of the quadratic cost function for each given kinetic profile using Matlab’s fsolve function. Model fits were evaluated both qualitatively (by visual inspection) and quantitatively (using the squared prediction error statistic).  \n\nIngredient Modeling. To assess the impact of different hydrogel chemistries (i.e., mixtures of predefined precursor polymers) on hydrogel performance, a multivariate modeling technique developed by Muteki and MacGregor47 was used. The basis of this method is to combine raw ingredient properties (here, the different precursor polymer compositions) with ratios using linear mixing rules to calculate “pseudo” mixture properties. These mixture properties can then be used in the input space of a regressive (typically latent variable) model to predict product performance. Here, for each hydrogel fabricated, the concentration (wt $\\%$ ), molecular weight, and degree of functionalization $\\mathrm{(mmol/g)}$ of each precursor polymer used to form the mixed hydrogels were used to calculate the pseudo mixture values of each of those properties based on linear mixture rules (i.e., by weighting the properties of each ingredient by the weight percentage of that ingredient used in the formulation). The resulting pseudo mixture properties were subsequently used in a partial least-squares regression to relate the mixture formulations to the performance parameters of the resulting hydrogels, as per the model form shown in Figure 2. The model was fit using the NIPALS algorithm and Aspen Technology’s ProMV software package. To ensure a good model fit, only experiments with a “good” dynamic model fits (as assessed by the sum of squared error) were used in the training data of the model. This approach would not be statistically appropriate if the objective of this analysis was to establish confidence in model coefficients for gaining mechanistic insight; however, given that the objective of the modeling in this case was instead to advise a direction for further experimentation toward achieving better hydrogel properties, limiting the input data to only the highest quality samples available is justifiable. This choice is particularly justifiable in this work in light of the relatively high noise associated with the moderate-to-high uncertainties observed with many (but not all) of the high-throughput characterization techniques developed, uncertainties that complicate explicit interpretation of the trends from each data set analyzed unless a data filtering approach was used.  \n\nOptimization. To make informed decisions about what formulations would achieve target hydrogel performance characteristics based on predefined criteria, the identified partial least-squares (PLS) model was inverted to allow for the prediction of polymer mixtures (bounded by what range of concentrations is physically possible given the rheological properties of each mixture component) that would achieve hydrogel compositions with targeted properties. Optimization was performed by solving the following quadratic programming problem using Matlab (eqs 3−8):  \n\n$$\n\\underset{r,z}{\\mathrm{min}}(\\hat{y}-y_{t})^{T}P_{y}(\\hat{y}-y_{t})+\\left(\\frac{t}{s_{a}}\\right)^{T}P_{H T}{}^{2}\\Bigg(\\frac{t}{s_{a}}\\Bigg)+(x-P t)^{T}P_{S P E_{x}}{}(x-P t)\n$$  \n\n$$\n{\\begin{array}{r l}&{s\\cdot t\\cdot\\sum r_{i}=1.0}\\\\ &{r_{i}\\in[0.1]\\ \\forall\\ i}\\\\ &{x=[r^{T}X_{p}r^{T}]^{T}}\\\\ &{{\\widehat{\\boldsymbol{y}}}=Q t}\\\\ &{t=x^{T}W^{*}}\\end{array}}\n$$  \n\ncontrolling protein release kinetics from hydrogels. Table 2 shows the chemical properties of each of the precursor polymers.  \n\nwhere $\\hat{\\pmb{y}}$ represents the predicted product qualities (here, the drug release kinetic parameters and transparency); $y_{t}$ represents the target properties; $P_{y},P_{H T^{2}},$ and $P_{S P E_{x}}$ are symmetric penalty matrices that can be adjusted to weight the relative importance of meeting the target hydrogel performance, minimizing extrapolation within the latent variable space, and minimizing extrapolation away from the latent space respectively; $\\boldsymbol{\\mathrm{\\ell}}_{Q}$ is the PLS coefficient matrix relating outcomes to the vector of latent space scores $\\mathbf{\\Delta}_{t,\\tiny{\\begin{array}{r l}\\end{array}}}$ and $W^{*}$ is the matrix of PLS coefficients relating inputs $\\pmb{x}$ to scores; the interested reader is referred to reference 64 for more complete details on the meaning of these scores.47 The input, $\\mathbf{\\delta}_{\\pmb{x},}$ is comprised of the ratios of the pseudo mixture properties $\\left(r^{T}X_{p}\\right)$ and the precursor polymer ratios used to form hydrogels in each well $(r)$ . The first two constraints (eqs 4 and 5) enforce that the sum of the ratios should be 1 and all ingredient ratios must be between 0 and 1. The second term in eq 2 prevents extrapolation of the model within the latent space beyond the statistical limits of the high throughput input data, while the third term of the objective function enforces a soft constraint on the squared prediction error (SPE) of the input space; the latter is essential in this case to reflect the covariance structure of the inputs since not all of the polymer recipe variables modeled are completely independent (e.g., wt $\\%$ polymer is confounded by the significant higher viscosities and thus lower concentrations of CMC-Hzd and Chitosan-Hzd that can be used to prepare hydrogels).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# RESULTS AND DISCUSSION  \n\nSynthesis of Hydrogel Precursors. Six hydrazidefunctionalized hydrogel precursor polymers were synthesized for each series of materials studied (i.e., thermoresponsive vs nonthermoresponsive and charged vs neutral). This number was chosen given that all possible combinations of each of the six precursor polymers could be prepared on a single 96-well plate (63 total hydrogels/series), enabling comprehensive high-throughput characterization of hydrogel swelling, degradation, transparency, and drug release kinetics all in a single synthetic and analysis step. The two series of polymers were selected based on the integral role of hydrogel porosity (regulated by thermoresponsiveness) and protein−hydrogel interactions (regulated by both hydrophobicity and charge) on  \n\nAll synthetic polymers (POEGMA, PNIPAM) were synthesized via free radical copolymerization using a chain transfer agent to limit the molecular weight of polymers. The measured number-average molecular weight $\\bar{(\\boldsymbol{M_{\\mathrm{n}}})}$ of both hydrazide and aldehyde-functionalized POEGMA or PNIPAM polymers was measured to lie between 16 and $22\\times10^{3}\\mathrm{g/mol},$ below the $\\ensuremath{M_{\\mathrm{n}}}\\sim40\\times10^{3}\\mathrm{g/mol}$ associated with in vivo renal clearance (Table 2).30,48 The degree of hydrazide or aldehyde functionalization between the different POEGMA precursor polymers was also designed to be similar (Table 2), such that the degree of cross-linking is likely to be comparable between different mixed combinations. The lower critical solution temperatures (LCSTs) of the $\\mathrm{PO}_{x}$ POEGMA-based hydrazidefunctionalized precursor polymers varied between ${\\sim}37\\ ^{\\circ}\\mathrm{C}$ for $\\mathrm{PO}_{0}\\mathrm{H}_{30}$ to ${>}80{}^{\\circ}\\mathrm{C}$ for $\\mathrm{PO}_{50}\\mathrm{H}_{30}$ and $\\mathrm{PO}_{100}\\mathrm{H}_{30},$ consistent with our previous reports.31,48 Note that the resulting volume phase transition temperatures (VPTTs) of the single-component hydrogels were significantly lower than the precursor polymer LCST values due to the consumption of the more polar hydrazide groups upon hydrazone bond formation, resulting in hydrogel VPTT values ranging from ${\\sim}26\\ ^{\\circ}\\mathrm{C}$ for ${\\mathrm{PO}}_{0}$ (collapsed at $37\\ ^{\\circ}\\mathrm{C}\\$ ), ${\\sim}32{\\mathrm{-}}33^{\\circ}\\mathrm{C}$ for $\\mathrm{PO}_{10}$ (slightly collapsed at $37{}^{\\circ}\\mathrm{C}\\mathrm{)}$ ), ${>}80{}^{\\circ}\\mathrm{C}$ for $\\mathrm{PO}_{50}$ (swollen at $37\\ {}^{\\circ}{\\bf C}{\\bf\\dot{\\Psi}},$ ), and ${>}80{}^{\\circ}\\bar{\\mathrm{C}}$ for $\\mathrm{PO}_{100}$ (swollen at $37\\ ^{\\circ}\\mathrm{C}$ ).31,48 As such, the thermoresponsive POEGMA precursor polymers selected for screening span the full range of the phase transition temperatures relevant to physiological protein release. CMC-Hzd was included in the thermoresponsive series as a nonthermoresponsive carbohydrate component for comparison with the high transition temperature $\\mathrm{PO}_{50}$ and $\\mathrm{PO}_{100}$ components to assess how using a temperature-independent, but more highly viscous, precursor component would affect the protein release properties. Note that $595\\%$ of the −COOH groups on all of the PNIPAM, POEGMA, and CMC precursor polymers were converted to hydrazide groups as per conductometric titration, such that all precursor polymers in this first series have similar (essentially neutral) net charges.  \n\nCharge was introduced into the precursor polymers by (1) copolymerizing the cationic comonomer DMAEMA (cationic, $\\mathrm{P}\\bar{\\mathrm{O}}_{100}\\mathrm{\\dot{H}}_{30}\\mathrm{C}_{20}\\big)$ or the anionic comonomer AA (anionic, $\\mathrm{PO}_{100}\\mathrm{H}_{30}\\mathrm{A}_{20}\\right)$ to form $20\\mathrm{~\\mol~\\}\\%$ functional monomer POEGMA-based synthetic copolymers or (2) selecting natively cationic (chitosan) or anionic (carboxymethyl cellulose) naturally sourced polymers. As such, different cationic, anionic, and amphoteric hydrogels with different charge contents can be prepared by mixing different combinations of cationic, anionic, and neutral $\\mathrm{PO}_{100}$ -based hydrazide precursors together with the nonthermoresponsive neutral aldehyde polymer $\\mathrm{PO}_{100}\\mathrm{A}_{30}$ .  \n\nThe concentrations of each polymer used were selected based on (1) the viscosity of the precursor polymers (ensuring that robotic pipetting is feasible), (2) the concentration at which the single component hydrazide and aldehyde gelling pair gels within $2{-}30\\ \\operatorname*{min}$ (ensuring that mixing is possible prior to gelation), and (3) published recipes of single component hydrazide and aldehyde gelling pairs that have been demonstrated to yield mechanically robust hydrogels with relevant biomedical properties.21,34,36,40,43,44,48 As such, while the mass concentrations and functional group densities of polymer in each combination gel do not match, the resulting hydrogels all have similar gelation times and compressive moduli on the same order of magnitude (tens of $\\mathbf{kPa}_{,}$ , see Supporting Information, Figure S2). In addition, the latent variable statistical model applied to the resulting data takes these different concentrations into account in the optimization protocol while also allowing them to vary in the optimization step in order to achieve target hydrogel properties.  \n\n![](images/1ed06146615f17810ecec16f090020ca49a5261d621b01238cf1841b0d6c183c.jpg)  \nFigure 3. Schematic of the high-throughput robotic fabrication approach and the structures of the hydrazide and aldehyde-functionalized polymer precursors used for hydrogel preparation.  \n\nCytotoxicity measurements using the Presto Blue assay in conjunction with NIH 3T3 mouse fibroblast cells indicated that high cell viability was maintained after $24\\mathrm{~h~}$ of incubation with each hydrogel precursor up to concentrations of at least 2 $\\mathrm{mg/mL},$ , a relatively high concentration for in vitro cytotoxicity screening (Supporting Information, Figure S3). As such, coupled with the degradability of the hydrogel networks (enabled by the presence of the naturally sourced polymers and the hydrolytically labile hydrazone cross-links), both sets of combinatorial hydrogels tested have potential for in vivo use.  \n\nPreparation of Multicomponent Hydrogels Using High-Throughput Robotics. Multicomponent hydrogels were prepared using a Tecan Evo 200 robot to mix preformed solutions of hydrogel precursor solutions in $10\\mathrm{\\mM}$ PBS at preprogrammed ratios, as shown visually in Figure 1. Two categories of materials were separately assayed: thermoresponsive versus nonthermoresponsive hydrogels (group T) and charged versus neutral hydrogels (group C; Figure 3). Each possible combination of the six hydrazide precursor polymers in each set was pipetted by the robot into separate wells of a 96-well plate according to combinatorial theory (eq 9).  \n\n$$\nC_{6}^{1}+C_{6}^{2}+C_{6}^{3}+C_{6}^{4}+C_{6}^{5}+C_{6}^{6}=63\n$$  \n\nFor example, $C_{6}^{2}$ refers to each possible combination of two premixed hydrazide polymers were cross-linked with one aldehyde polymer (15 combinations total). A total of $60~\\mu\\mathrm{L}$ of hydrazide precursor polymer was dispensed into each well for each combination tested, corresponding to $30~\\mu\\mathrm{L}$ of each of two precursor polymers dispensed, $20~\\mu\\mathrm{L}$ of each of three precursor polymers dispensed, and so on; this design approach facilitates the creation of each of the mixed hydrogel combinations listed above without changing the total gel volume. The result of this protocol was that 126 different hydrogels could be fabricated in quadruplicate in ${\\sim}25~\\mathrm{min}$ .  \n\nPhysiochemical Properties of Combinatorial Hydrogels. To address the key challenge of high-throughput materials screening (i.e., the characterization of the properties of the fabricated materials), we developed a series of analytical techniques for assessing the typically reported properties of hydrogels (mechanics, swelling, degradation, and transparency) relevant for biomedical applications that could be performed reliably at reasonably high speeds ( $^{\\cdot}<2\\mathrm{~h~}$ per plate of 63 hydrogels) without requiring removal of the hydrogels from the wells. Mechanics, swelling, and degradation measurements were all performed using a Mach-1 micromechanical tester fitted with a multiwell plate adapter that allows the instrument to individually address each well of a 96-well plate.  \n\nSwelling. Hydrogel swelling was measured by comparing the point at which the microindenter contacted the hydrogel interface (i.e., normal force $>0.005\\mathrm{~N~}$ ) before and after a $^{48\\mathrm{~h~}}$ swelling period in $10\\mathrm{mM}\\mathrm{PBS}$ at $22{}^{\\circ}\\mathrm{C};$ the room temperature test condition was chosen to minimize the effect of the phase transition of thermoresponsive hydrogels on the measured swelling results. Figure 4 shows the swelling responses of single-component hydrogels in each series, while Supporting Information, Figures S4 (thermoresponsive series) and S5 (charged series) show the results for each combinatorial hydrogel fabricated. As anticipated, the thermoresponsive $\\mathrm{PO}_{0}\\mathrm{H}_{30}$ and PNIPAM-Hzd single component hydrogels deswelled over the test period, yielding equilibrium swelling ratios of $0.91\\pm0.09$ $\\left(\\mathrm{PO}_{0}\\mathrm{H}_{30}\\right)$ and $0.82\\pm0.11$ (PNIPAMHzd), respectively. While the absolute swelling ratios are lower for the constrained (in-plate) and unconstrained (free disk) swelling measurements, the swelling data in Figure 4 correlates well $\\ ^{\\prime}R^{2}\\ =\\ 0.84)$ with the unconstrained swelling measurements performed using the conventional disk method (Supporting Information, Figure S6), confirming the predictive ability of the multiwell plate assay for measuring hydrogel swelling. Similarly, mixing $\\mathrm{PO}_{0}\\mathrm{H}_{30}$ or PNIPAM-Hzd with any of $\\mathrm{PO}_{10}\\mathrm{H}_{30},$ $\\mathrm{PO}_{50}\\mathrm{H}_{30},$ $\\mathrm{PO}_{100}\\mathrm{H}_{30},$ or $\\mathrm{CMC}_{40}–\\mathrm{Hzd}$ resulted in hydrogels with significantly suppressed swelling over the $^{48\\mathrm{~h~}}$ incubation period for each binary or ternary combinations tested (Supporting Information, Figure S4A,B). The binary combination of $\\mathrm{PO}_{0}\\mathrm{H}_{30}$ and $\\mathrm{CMC}_{40}–\\mathrm{Hzd}$ (T2−12) exhibited a particularly noteworthy deswelling ratio of $0.70\\pm0.06,$ despite the fact that the $\\mathrm{CMC}_{40}$ -Hzd single component gels swell over the same time period (Figure 4A); similarly, the ternary combination of $\\mathrm{PO_{10}H_{30}}+\\mathrm{PO_{100}H_{30}}+$ PNIPAM-Hzd (T3−3)  \n\n![](images/e21795184306104a50d10fde1f9de8048516737340b0b9e6e5313df86c8f3b63.jpg)  \nFigure 4. Volume-based swelling ratios of (A) thermoresponsive vs nonthermoresponsive (T series) single-component hydrogels and (B) charged vs neutral (C series) single-component hydrogels before (blue) and after (red) swelling for $^{48\\mathrm{~h~}}$ in $10~\\mathrm{mM}$ PBS at room temperature $22\\ {}^{\\circ}\\mathrm{C};$ ; $n=$ 4). See Supporting Information, Figures S4 and S5, for the corresponding results for the combinatorial hydrogels.  \n\n![](images/1cdcf4ddd04615c1a9dc18899b14d0ea501fbe10d0c89a06b7613f39b66ac511.jpg)  \nFigure 5. Compressive modulus ( $\\dot{\\boldsymbol{t}}=0$ h data points) and degradation kinetics (tracked by changes in the measured compressive modulus over time of exposure to $0.1\\mathrm{~M~}$ HCl at $22\\ ^{\\circ}\\mathrm{C}$ ) for (A) thermoresponsive vs nonthermoresponsive $\\mathrm{\\bar{T}}$ series) single-component hydrogels and (B) charged vs neutral (C series) single-component hydrogels $\\left(n=4\\right)$ ; (C) Comparison of the compressive modulus of hydrogels in the $\\mathrm{\\DeltaT}$ series before and after acid degradation over $72\\ \\mathrm{h};$ (D) Comparison of the compressive modulus of hydrogels in the C series before and after acid degradation over $24\\mathrm{~h~}$ . See Supporting Information, Figures S7 and S8, for the corresponding results for the combinatorial hydrogels.  \n\nexhibited a swelling ratio of $0.70\\pm0.07_{.}$ , despite the presence of just one precursor polymer (PNIPAM-Hzd) that deswelled as a single component gel (Figure 4A). In contrast, each fivecomponent hydrogel in which $\\mathrm{PO}_{0}\\mathrm{H}_{30}$ and PNIPAM-Hzd represented two of the five components (i.e., comprise $40\\%$ of the total volume and ${>}50\\%$ of the total polymer mass, Supporting Information, Figure S4D) exhibited substantial swelling, with the minimum swelling ratio among the four such hydrogels tested being $1.1\\pm\\:0.3$ and the others reaching as high as $1.6\\pm0.4$ . As such, combinations of precursor polymers result in nonadditive swelling properties, suggesting the potential utility of this mixing approach to generate new and optimized protein release kinetics. We hypothesize that these observed nonadditive effects on hydrogel properties to probable phase separation within these combination gels, creating segregated mass distributions between pro-swelling and antiswelling precursor polymer domains.  \n\nSwelling ratios for the charged hydrogel series also showed nonlinear effects, although the general trends were much more consistent. Comparing Figure 4A and 4B, the swelling ratios in Figure 4B were typically higher, consistent with the higher hydrophilicity of the cross-linking polymer $\\mathrm{PO}_{100}\\mathrm{A}_{30}$ compared to $\\mathrm{PO}_{10}\\mathrm{A}_{30}\\big)$ , as well as the charged nature of many of the hydrazide precursor polymers that can drive Donnan equilibrium-related swelling at the physiological test $\\mathrm{\\tt{pH}}$ . Combinations of two, five, or six precursor polymers (Supporting Information, Figure $S5\\mathrm{A,D}$ ) all resulted in hydrogels with generally similar swelling ratios to the single component hydrogels; in contrast, combinations of three or four precursor polymers (Supporting Information, Figure S5B,C) resulted in hydrogels with significantly higher swelling ratios. The amphoteric hydrogel combinations of $\\mathrm{PO}_{100}\\mathrm{H}_{30}\\mathrm{A}_{20}$ $^+$ dextran-Hzd $^+$ chitosan-Hzd (C3−19) and $\\mathrm{PO}_{100}\\mathrm{H}_{30}\\mathrm{A}_{20}+$ CMC-Hzd $^+$ dextran-Hzd $^+$ chitosan-Hzd (C4−15) exhibited particularly notable swelling ratios of $1.9\\pm0.4$ and $2.2\\pm0.1$ , respectively, suggesting a benefit to creating mixed charge hydrogels to promote high swelling. In this context, combinatorial mixing can again enable access to a broader potential range of hydrogel swelling responses than possible with the single-component hydrogels.  \n\nMechanics. A simple $10\\%$ compression protocol from the point of contact was used in combination with the high throughput accessory of the Mach-1 micromechanical tester to measure the compressive modulus at $22~^{\\circ}\\mathrm{C}$ both before and after the incubation of the hydrogels in $10~\\mathrm{mM}$ PBS at room temperature $\\left(22^{\\circ}\\mathrm{C}\\right)$ for $^{72\\mathrm{h},}$ with the time chosen to ensure all gels reach equilibrium swelling before measurement. The compressive modulus of single-component POEGMA hydrogels after swelling decreased from $\\mathrm{PO}_{0}\\mathrm{H}_{30}$ $(59\\pm34\\mathrm{\\kPa})$ to $\\mathrm{PO}_{100}\\mathrm{H}_{30}$ ( $\\langle33\\pm5\\mathrm{\\kPa}\\rangle$ (Figure 5A, time $t=0\\mathrm{~h~}$ ), a trend consistent with previous observations on bulk gels as the proportion of the long-chain $\\mathrm{OEGMA}_{475}$ monomer is reduced.48 Furthermore, charged hydrogels prepared with POEGMA-based precursor polymers exhibited substantially higher moduli than those prepared based on the higher molecular weight naturally sourced precursors (Figure 5B, time $t=0\\mathrm{h}$ ), again consistent with previous reports.34 As such, the high-throughput mechanics assay yields modulus trends mirroring those achieved with the conventional technique.  \n\nMixing different precursor polymers again demonstrates nonlinear effects (Supporting Information, Figures S7 and S8), although the relatively large error bars observed particularly with some of the higher-modulus mixtures limit the scope of conclusions that can be drawn. For example, among the binary thermoresponsive combinations (Figure S7A), the combination of $\\mathrm{PO}_{0}\\mathrm{H}_{30}+\\mathrm{PO}_{50}\\mathrm{H}_{30}$ (T2−10, in which one component is thermoresponsive and the other is not at physiological temperature) exhibited a compressive modulus of $89\\pm21\\mathrm{{kPa}}_{;}$ equivalent to a $\\mathrm{PO}_{0}\\mathrm{H}_{30}$ single-component gel and somewhat higher than a $\\mathrm{PO}_{50}\\mathrm{H}_{30}$ single-component gel $\\left(p\\ <\\ 0.1\\right)$ ; in contrast, the combination of $\\mathrm{PO}_{0}\\mathrm{H}_{30}+\\mathrm{PO}_{10}\\mathrm{H}_{30}$ $(\\mathrm{T}2-2,$ in which both components are thermoresponsive but to different degrees at physiological temperature) resulted in a hydrogel with a much lower compressive modulus of $15~\\pm~7~\\mathrm{{kPa}},$ , substantially weaker than either single-component gel $(p\\ <$ 0.01 for both comparisons). We hypothesize this difference is again related to differences in phase separation, with the double thermoresponsive binary gel $(\\mathrm{T}2-2)$ more likely to generate bulk phase-segregated domains and the single thermoresponsive binary gel (T2−10) more likely to form a continuous nonresponsive phase with collapsed thermoresponsive domains that may mechanically reinforce the hydrogel. Such differences are suppressed as more components are added to the gels and, thus, the probability of some form of macroscopic phase separation is increased, with all five- and six-component hydrogels exhibiting similar moduli within experimental error. Similar general trends are observed with the charged precursor data (Supporting Information, Figure S8). Binary and ternary combinations (Figures S7A and S8B) exhibited substantially higher variability in modulus values than the five and six-component mixtures (Figure S8D), with amphoteric hydrogels such as $\\mathrm{PO_{100}H_{30}~+~\\mathrm{PO_{100}H_{30}C_{20}~+~}}$ $\\mathrm{PO}_{100}\\mathrm{H}_{30}\\mathrm{A}_{20}$ (C3−1), exhibiting particularly high moduli, consistent with the demonstrated high capacity of amphoteric hydrogels for retaining water in the presence of salt (i.e., PBS) and facilitating dual ionic/covalent cross-linking at physiological $\\mathrm{\\ttpH}$ .34  \n\nDegradation. Degradation kinetics were assessed by tracking the decrease in the compressive modulus of the hydrogels over time upon exposure to acidic degradation conditions $\\langle0.1\\mathrm{M}\\mathrm{HCl},\\bar{2}2^{\\circ}\\mathrm{C}\\rangle$ ; note that this acidic condition was chosen to accelerate the degradation of the hydrazone bond to enable comparisons between the degradation potential of various hydrogel compositions on a shorter time scale. Upon exposure to 0.1 M HCl, the compressive modulus of most hydrogels decreased to ${\\sim}50\\%$ or less of the initial modulus very quickly (comparing $t=0$ and $^{2\\mathrm{~h~}}$ in Figure 5A and B), with the modulus of most of the single-component charged series hydrogels decreasing to nearly zero after $24\\ensuremath{\\mathrm{~h~}}$ of incubation consistent with visually observed gel degradation at this time point (Figure 5D). In contrast, thermoresponsive hydrogels based on POEGMA or, in particular, PNIPAM (which deswells the most relative to its preparation state at room temperature, Figure 4A) retained at least ${\\sim}20{\\mathrm{-}}50\\%$ of their initial modulus after $24\\mathrm{h}$ and persisted for at least $^{72\\mathrm{{h}}}$ in the presence of 0.1 M HCl (Figure 5C). This notably slower degradation of the thermoresponsive hydrogels and, in particular, the PNIPAM-Hzd hydrogel, is consistent with previous observations,21,30 as well as theory, in that introducing charge promotes swelling (Figure 4B) and thus faster hydrolytic degradation (Figure 5B), while introducing thermoresponsive components suppresses swelling (Figure 4A) and thus also degradation (Figure 5A). On this basis, the suitability of the high-throughput measurement protocol used for probing degradation rates is confirmed.  \n\n![](images/de9100ab067225051bf0e240275ed006acc10ec3f55798e0509c9ad6b7ac958f.jpg)  \nFigure 6. Transmittance of (A) thermoresponsive vs nonthermoresponsive (T series) single-component hydrogels and (B) charged vs neutral (C series) single-component hydrogels as a function of temperature ${\\mathit{\\check{n}}}=4{\\mathit{\\check{\\Psi}}},$ ). See Supporting Information, Figures S9−S16, for the corresponding results for the combinatorial hydrogels.  \n\nNonadditive effects are again observed in the degradation performance of the combinatorial hydrogels, particularly in the thermoresponsive binary and ternary mixture hydrogels (Supporting Information, Figures S7A,B). Of particular note, $\\mathrm{PO}_{0}\\mathrm{H}_{30}+$ PNIPAM-Hzd (T2−11) and $\\mathrm{PO}_{10}\\mathrm{H}_{30}+\\mathrm{PO}_{0}\\mathrm{H}_{30}+$ PNIPAM-Hzd $\\left(\\mathrm{T}3-6\\right)$ , both of which contain mixtures of only thermoresponsive polymers, exhibited no significant change in their compressive modulus after $^{72\\mathrm{~h~}}$ of acid degradation $\\left(p>$ 0.1 for both pairwise comparisons between the modulus measurements at the 0 and $^{72\\mathrm{~h~}}$ time points); this represents a substantially slower degradation rate than any of the single component thermoresponsive hydrogels (Figure 5A). Combining the nonthermoresponsive but more viscous CMC-Hzd with $\\mathrm{PO}_{0}\\mathrm{H}_{30}$ and PNIPAM-Hzd (T3−19) similarly suppresses degradation over the $^{72\\mathrm{~h~}}$ test period, consistent with the slower diffusion of water expected into this hydrogel. While the mixture modulus results are less dramatically different within the charged series, more neutral binary and ternary combinations (e.g., $\\mathrm{PO}_{100}\\mathrm{H}_{30}$ + Dextran − C2−4 or $\\mathrm{\\Delta}\\mathrm{\\supset_{100}H_{30}}+\\mathrm{PO_{100}H_{30}}\\mathrm{-cat}+\\mathrm{Dextran}-\\mathrm{C}3-\\mathrm{\\B{:}}$ ) show somewhat reduced degradation rates, consistent with the lower observed swelling in those hydrogels (Figure 4B).  \n\nTransparency. Transparency measurements give insight into the homogeneity of the gels, allowing us to correlate, at least in part, the nonlinear changes in swelling, mechanics, and degradation noted in the previous sections to potential phase separation within these materials. Optical transparency is also an important parameter in some applications of injectable hydrogels (e.g., ophthalmic delivery) that are particular targets for protein-based therapies.49 Transmittance as a function of temperature was measured by ramping the temperature of a microplate reader from 25 to $40~^{\\circ}\\mathrm{C}$ and tracking the resulting transmittance at ${595}\\ \\mathrm{nm}$ , far outside the window in which any of the components of any of the combinatorial hydrogels would absorb due to chemical bonding; as such, the transmittance measurement corresponds to the light scattered by each hydrogel and, by extension, the number and size of phase-separated domains present in each hydrogel sample. As expected, low VPTT hydrogels such as $\\mathrm{PO}_{0}\\mathrm{H}_{30}$ and PNIPAMHzd showed low transmittance $48\\%$ for $\\mathrm{PO}_{0}\\mathrm{H}_{30}$ and $45\\%$ for PNIPAM-Hzd) even at $25~^{\\circ}\\mathrm{C}_{\\mathrm{\\ell}}$ , consistent with the deswelling response observed for both these hydrogels at room temperature (Figures 4A and 6A); further decreased transmittance values were observed as the temperature was increased to 40 $^{\\circ}\\mathrm{C}$ ( $29\\%$ for $\\mathrm{PO}_{0}\\mathrm{H}_{30},$ $30\\%$ for PNIPAM-Hzd, Figure 6A). In contrast, only a slight reduction in transmittance was observed for the $\\mathrm{PO}_{10}\\mathrm{H}_{30}$ single-component hydrogel (consistent with the reported ${\\sim}33\\ ^{\\circ}\\mathrm{C}$ onset transition temperature of this hydrogel48), and no change in transmittance was observed for higher transition temperature or nonthermoresponsive singlecomponent gels over the full temperature range probed (Figure 6A). None of the charged gels exhibited a thermal phase transition (Figure 6B), with all gels showing transmittance values of ${\\sim}95\\%$ , as expected within the probed temperature range.  \n\nUpon mixing different components, a substantially broader range of transmittances was achieved, with the thermoresponsive (T series) hydrogels showing transmittances spanning from ${\\sim}20\\%$ (or less) to $595\\%$ (Supporting Information, Figures S8, S10, S12, and S14). For example, the ${\\mathrm{T}}3{-}3$ hydrogel noted to have a particularly large deswelling response $\\left(\\mathrm{PO_{10}H_{30}}+\\mathrm{PO_{100}H_{30}}+\\right.$ PNIPAM-Hzd, Figure 4A) also exhibited a particularly low transmittance ( $\\cdot<20\\%$ over the full temperature range), consistent with phase separation among the different transition temperature thermoresponsive components of this hydrogel. While the inclusion of CMC-Hzd preserved high deswelling, it also significantly increased the transmittance of the resulting hydrogels; the T2−12 hydrogel $\\left(\\mathrm{PO}_{0}\\mathrm{H}_{30}+\\mathrm{CMC}\\mathrm{-}\\mathrm{Hzd}\\right)$ that exhibited similar deswelling to the $_{\\mathrm{T}3-3}$ hydrogel maintained a transmittance of ${\\sim}50\\%$ at $25~^{\\circ}\\mathrm{C}$ . The PNIPAM-Hzd component particularly appears to play a key role in creating hydrogels with lower transmittances; for example, in the five-component thermoresponsive combinatorial gels (Figure S3D), the one hydrogel prepared without the PNIPAM-Hzd component $(\\mathrm{T}5-2)$ still maintained $>60\\%$ transmittance, while all formulations containing PNIPAM-Hzd had transmittances $<40\\%$ .  \n\nInterestingly, some charged (C series) hydrogels yielded transmittances as low as $\\sim60\\%$ (Supporting Information, Figures S9, S11, S13, and S14), despite the fact that each single-component hydrogel was highly transparent (Figure 6B). In particular, binary mixtures of different carbohydrates (e.g., $\\mathrm{CMC}_{20}–\\mathrm{Hzd}+$ chitosan-Hzd − C2−14 or $\\mathrm{CMC}_{20}–\\mathrm{Hzd}+$ dextran-Hzd − C2−15) exhibited significantly lower transmittances than achieved by mixing different POEGMA precursor polymers, a result consistent with the different base chemistries and higher viscosities of the carbohydrate starting materials that could result in more thermodynamic phase separation and less effective mixing during hydrogel fabrication. In addition, higher-order mixtures, including chitosan-Hzd (e.g., C4−10, C4−12, C4−15, or any of the five-component gels aside from $C5{-}1$ , which excludes chitosan-Hzd), all exhibit lower transmittances than other combinations, potentially attributable to the reduced solubility of the carboxymethylated chitosan at physiological pH following the consumption of a portion of those carboxyl groups during the hydrazide functionalization process. As such, minimizing the use of PNIPAM-Hzd and chitosan-Hzd results in hydrogels with enhanced transparency without changing the swelling response.  \n\n![](images/ee12a5a46f6833ef4a8cdfc92d6647971511bb3f3690e32346b2a9acfb860c1f.jpg)  \nFigure 7. Cumulative ovalbumin release kinetics from (A) thermoresponsive vs nonthermoresponsive (T series) single component hydrogels and (B) charged vs neutral (C series) single component hydrogels in $10~\\mathrm{mM}$ PBS at $37^{\\circ}\\mathrm{C}$ $\\left(n=4\\right)$ ). See Supporting Information, Figures S9−S15, for the corresponding results for the combinatorial hydrogels.  \n\nDrug Release Kinetics. To assess the kinetics of protein release from the combinatorial hydrogels, ovalbumin was dissolved in the aldehyde precursor solution used to prepare the high-throughput hydrogels, resulting in a uniform loading of $1.5\\mathrm{\\mg}$ ovalbumin/well. Ovalbumin $\\left(M_{\\mathrm{w}}\\:=\\:45\\:\\mathrm{\\kDa}\\right)$ was chosen as our model protein based on its reported role as an effective analogue of ranibizuman $(M_{\\mathrm{w}}=46~\\mathrm{kDa})$ ), a key antiVEGF antibody for treatment of eye disease such as age-related macular degeneration (AMD).50 By using a multiwell filter plate with individual well collectors, the cumulative protein release from each sample can be individually tracked over a one month release period. Figure 7 shows the cumulative ovalbumin release profiles (measured via the Bradford assay) for each single-component gel. Thermoresponsive hydrogels showed higher $\\%$ drug release than nonthermoresponsive hydrogels (Figure 7A), with the PNIPAM-Hzd gels that deswell the most exhibiting the maximum total drug release $(89\\%)$ and the highest day one burst release $(70\\%)$ , consistent with convective transport of the protein out of the gel as the thermal collapse occurs. Nonthermoresponsive gels such as $\\mathrm{CMC}_{40}–\\mathrm{Hzd}$ and $\\mathrm{PO}_{100}\\mathrm{H}_{30}$ exhibited substantially lower burst releases ( ${\\sim}32\\%$ day one release) but also significant retention of protein, with only ${\\sim}44\\%$ overall release achieved after one month. In comparison, the intermediate transition temperature $\\mathrm{PO}_{50}\\mathrm{H}_{30}$ single component hydrogel exhibited comparable burst release to the nonthermoresponsive gels ( ${\\sim}42\\%$ day one release) but significantly higher total release over the test period $\\left({>}60\\%\\right)$ , suggesting that moderate thermoresponsiveness may be beneficial for achieving prolonged protein release. The charged single component hydrogels (Figure 7B) showed significantly less burst release (between ${\\sim}10\\%$ to $28\\%$ after 1 day compared to ${\\sim}28\\%$ for the neutral $\\mathrm{PO}_{100}\\mathrm{H}_{30}$ control) but also significantly higher protein retention, particularly for the carbohydrate-based hydrogels, which retained between 58 and $68\\%$ of their cargo, even after one month (at least in the absence of oxidative degradation that is known to primarily degrade carbohydrate precursor polymers in vivo). This general result is consistent with the increased affinity of the charged gels for proteins,51,52 a result further demonstrated by the longer time frame of controlled release observed in the charged gels (up to 6−7 days) relative to the thermoresponsive gels (up to 2−3 days) despite the significantly higher water contents and, thus, lower diffusion resistances of the charged hydrogels (Figure 4B).  \n\nThe combinatorial hydrogels again show interesting results in terms of manipulating the burst release, total duration of significant protein release, and the entrapped protein fraction of each hydrogel (Supporting Information, Figures S9−S15). While the charged combinations all trended similarly (i.e., samples with less burst release also released less protein, Figures S10, S12, and S14), the thermoresponsive hydrogels showed some independence among these variables. For example, the $\\mathrm{PO_{10}H_{30}\\ +\\ P O_{100}H_{30}\\ +\\ P O_{0}H_{30}}$ hydrogel containing a mixture of POEGMA-based polymers with different phase transition temperatures $\\left(\\mathrm{T}3\\mathrm{-}1\\right)$ exhibited a high burst release of ${\\sim}60\\%$ and a high cumulative release of ${>}90\\%$ , but effectively sustained ovalbumin release effectively over ${\\sim}10$ days, while the ${\\mathrm{T}}3{-}3$ gel in which the $\\mathrm{PO}_{0}\\mathrm{H}_{30}$ component is replaced with PNIPAM-Hzd exhibited similar burst and total ovalbumin release, but a substantially shorter release time of ${\\sim}3$ days. The binary combinations exhibiting the highest degree of deswelling (T2−2 and T2−10, Figure S4A) also exhibited the fastest and highest total ovalbumin release consistent with higher convective water transport from these gels, while binary hydrogels formed by combining CMCHzd with an intermediate transition temperature POEGMA precursor (i.e., $\\mathrm{PO}_{10}\\mathrm{H}_{30}\\ -\\ \\mathrm{T}2{-}5$ or $\\mathrm{PO}_{50}\\mathrm{H}_{30}\\ -\\ \\mathrm{T}2\\mathrm{-}14)$ exhibited the lowest total release. These results suggest that mixing different precursor polymers may be an effective approach for tuning protein release from hydrogels. Note that hydrazone chemistry has previously been shown to maintain good protein activity, suggesting its relevance for designing in situ-gelling protein delivery vehicles.  \n\nLatent Variable Analysis and Optimization. Given the large amount of data generated by the high-throughput fabrication and characterization approaches developed, latent variable methods are ideally suited to fit the high-throughput data to a mathematical model and subsequently invert the model to identify optimal mixtures of precursor polymers that will provide desirable properties. While the thermoresponsive and charged polymer series were fabricated separately based on the experimental limitations of the high-throughput robotics system, a single latent variable model was built that combines data from both series by assigning a value of zero to any precursor polymer not included in a given hydrogel. For quantifying drug release kinetics, the kinetic curves in Figure 7 and Supporting Information, Figures S9−S15, were fit to the model $\\hat{\\boldsymbol{y}}^{}(t)=\\dot{\\boldsymbol{y}}_{f}+(\\boldsymbol{y}_{0}-\\boldsymbol{y}_{f})e^{-t/\\tau},$ in which $y_{0}$ approximated the burst release of protein from each gel, $y_{f}$ compensated for potential entrapment of protein within the gel, and $\\tau$ was the time constant related to the rate of protein release. A representative model fit is shown in Supporting Information,  \n\n![](images/b91f35348a2a86b69a48370bad5da97df10d2e318de9865b0c719036ebc1cca9.jpg)  \nFigure 8. Coefficient plots relating the key output variables to the recipe variables (i.e., the type of polymer used, concentration of polymer used, degree of polymer functionalization, and polymer molecular weight) for (A) $y_{0},$ (B) $y_{\\beta}$ (C) $\\tau,$ and (D) hydrogel transparency.  \n\nFigure S16, while Supporting Information, Figure S17 shows the root mean squared error for all drug release kinetic points evaluated. Overall, the modified first-order model can accurately fit the release profiles measured, with an average root mean squared error of only $1.7\\%$ drug released. As such, the model parameters extracted from these fits can reliably describe the overall drug release kinetics achieved with most of the 126 hydrogels analyzed via three fitted parameters that can be incorporated directly into predictive models.  \n\nA global model was first attempted to be built that included all the parameters measured via high-throughput (i.e., swelling ratio, compressive modulus, degradation rate constant, transparency, and drug release kinetics). However, only the transparency $(R^{2}\\ =\\ 61.2\\%$ , $Q^{2}\\ =\\ 58.1\\%$ ) and drug release kinetics ${\\left(R^{2}=[y_{0};85.0\\%,y_{f};61.2\\%,\\tau;59.1\\%],\\right.}$ , $Q^{2}=\\bar{[{y_{0}};{83.5\\%}},$ yf: $58.1\\%,\\ \\tau\\colon55.9\\%]\\big)$ , where $R^{2}$ represents the percentage of overall variance explained and $Q^{2}$ represents the percentage of variance explained during cross-validation, could be fit with reasonable predictive confidence. The obvious nonlinear effects outlined in the discussion for the swelling, degradation, and mechanics measurements, coupled with the relatively large uncertainty inherent in some of the raw compressive modulus measurements, likely account for these relatively poor fits. As such, an alternative model was built that included all the gels tested from both series but only transparency and the drug release parameters as $y$ -variables, resulting in a 12 component PLS model which explained $67\\%$ of the variance in the output space (Supporting Information, Figure S18). The observed versus predicted plots for each of the drug release kinetic parameters (Supporting Information, Figures S19−S21) and the transparency measurements (Supporting Information, Figure S22) confirm the utility of the model for predicting hydrogel transparency and drug release kinetics.  \n\nCorrespondingly, the coefficient plots associated with the model fit, summarized in Figure 8, as well as the loading biplot (Supporting Information, Figure S23) reflect many of the key qualitative trends identified in the experimental data analysis. In the coefficient plots in Figure 8, positive coefficients indicate that the variable in question is positively correlated with the hydrogel property considered in each panel, while negative coefficients indicate a negative correlation; the larger the absolute magnitude of the coefficient and the smaller the error bar (particularly if the error range does not cross zero), the larger the effect of that particular variable on a given hydrogel property. CMC suppresses drug burst, while PNIPAM-Hzd and other thermoresponsive POEGMA polymers ( $\\mathrm{\\DeltaPO_{0}H_{30}}$ and $\\mathrm{PO}_{10}\\mathrm{H}_{30}\\big)$ promote drug burst $(y_{0},$ Figure 8A) as well as more complete release of the protein from the gel $\\left(y_{\\hat{f}}\\right.$ Figure 8B). The incorporation of charged POEGMA precursor polymers and chitosan both result in larger $\\tau$ values (i.e., slower release) due to electrostatic interactions with the protein cargo (Figures 7B and 8C), while hydrogels prepared with the more hydrophilic $\\mathrm{PO}_{100}\\mathrm{H}_{30}$ precursor polymer result in lower $\\tau$ values (i.e., faster release) due to their high swelling (Figures 4A and 8C). The thermoresponsive PNIPAM-Hzd and $\\mathrm{PO}_{0}\\mathrm{H}_{30}$ precursor polymers negatively contribute to transparency, while the $\\mathrm{PO}_{100}$ precursor polymers enhance transparency (Figure 8D). Note that none of the pseudo variables representing weightings of different polymer compositions (i.e., molecular weight, polymer concentration, and $\\mathrm{{mmol}/\\mathrm{{g}}}$ functionalization) show obvious trends, given that these variables are highly correlated with the physicochemical properties of the polymers; for example, hydrogels prepared with Chitosan-Hzd or CMC-Hzd will inherently have lower weighted polymer concentrations and degrees of functionalization based on their higher viscosities and lower numbers of derivatizable functional groups. However, the match between the model predictions of the effects of each polymer component and both qualitative observations and theory clearly suggest the potential of the model for the prediction of key gel properties.  \n\nTable 3. Model-Predicted Optimal Recipes for Each Optimization Criteriona   \n\n\n<html><body><table><tr><td rowspan=\"2\">polymer precursors</td><td colspan=\"4\">M1-</td><td colspan=\"4\">M2-</td><td colspan=\"4\"> M3-</td></tr><tr><td>1</td><td>2</td><td>3</td><td>4</td><td>1</td><td>2</td><td>3</td><td>4</td><td>1</td><td>2</td><td>3</td><td>4</td></tr><tr><td>POH30</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>PO10H30</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>1</td><td></td><td></td><td></td></tr><tr><td>PO50H30</td><td>31</td><td>50</td><td>14</td><td>7</td><td>15</td><td>30</td><td></td><td>50</td><td></td><td></td><td></td><td></td></tr><tr><td>PO100H30</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>7</td><td></td><td></td><td></td></tr><tr><td>PNIPAM-Hzd</td><td></td><td></td><td></td><td></td><td>35</td><td>20</td><td>50</td><td></td><td></td><td></td><td></td><td>18</td></tr><tr><td>CMC40-Hzd</td><td>19</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> PO100H30C20</td><td></td><td></td><td>36</td><td>43</td><td></td><td></td><td></td><td></td><td>14</td><td>21</td><td>39</td><td>20</td></tr><tr><td>PO100H30A20</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>10</td><td>13</td><td>10</td><td>12</td></tr><tr><td>CMC20-Hzd</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>10</td><td>13</td><td>1</td><td></td></tr><tr><td>dextran-Hzd</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>8</td><td>3</td><td></td><td></td></tr><tr><td>chitosan-Hzd</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>PO10A30</td><td></td><td></td><td></td><td></td><td></td><td></td><td>39</td><td>7</td><td></td><td></td><td></td><td>4</td></tr><tr><td>PO100A30</td><td>50</td><td>50</td><td>50</td><td>50</td><td>50</td><td>50</td><td>11</td><td>43</td><td>50</td><td>50</td><td>50</td><td>46</td></tr></table></body></html>\n\nNumbers correspond to $\\mu\\mathrm{L}$ of each precursor component solution defined in Table 2 that were added to each well.  \n\n![](images/d3c32505ad09509fecb5353444427c9c080bcf17083f018391dc16f6cacd8b31.jpg)  \nFigure 9. Properties of optimized hydrogel formulations: $(\\mathbf{A},\\mathbf{B})$ minimize burst $\\left(y_{0}\\right)$ , maximize total protein release $\\left(y_{f}\\right)$ , maximize transparency (M1) optimization: (A) Cumulative ovalbumin release kinetics as a function of time ( $10\\ \\mathrm{mM}$ PBS, $37\\ ^{\\circ}\\mathrm{C})$ ); (B) transmittance measured at a wavelength of $595\\mathrm{nm}$ as a function of temperature. (C, D) Minimize burst $\\left(y_{0}\\right)_{\\cdot}$ , minimize release rate (maximize $\\tau$ ), and maximize total release $\\left(y_{\\mathscr{f}}\\right)$ M2) optimization: (C) cumulative ovalbumin release kinetics as a function of time ( $10\\ \\mathrm{mM}$ PBS, $37\\ ^{\\circ}\\mathrm{C})$ ); (D) transmittance measured at a wavelength of ${\\mathfrak{s o s}}_{\\mathrm{nm}}$ as a function of temperature. (E, F) Minimize burst $\\left(y_{0}\\right)$ , minimize release rate (maximize $\\tau$ ), maximize total release $\\left(y_{f}\\right)$ , and maximize transparency (M3) optimization: (E) cumulative ovalbumin release kinetics as a function of time ( $10\\mathrm{\\mM}$ PBS, $37~^{\\circ}\\mathrm{C}$ ); (F) transmittance measured at a wavelength of $595\\ \\mathrm{nm}$ as a function of temperature. Error bars represent the standard deviation of four replicate measurements $\\left(n=4\\right)$ ).  \n\nThe model was next inverted to optimize the hydrogel compositions for protein delivery based on one of three criteria, each of which are relevant to different protein delivery applications: (M1) minimize burst $\\left(y_{0}\\right)$ , maximize total protein release $(y_{f})$ , maximize transparency (ideal for ophthalmic drug delivery in which minimizing the burst release is more important than maximizing the overall release period); (M2) minimize burst $\\left(y_{0}\\right)$ , minimize release rate (maximize $\\tau$ ), maximize total release $(y_{f})$ (ideal for other drug release applications in which transparency is not important); and (M3) minimize burst $\\left(y_{0}\\right)$ , minimize release rate (maximize $\\tau$ ), maximize total release $\\left(y_{f}\\right)$ , and maximize transparency (ideal for ophthalmic drug delivery applications in which slower release is as important as minimal burst). Each maximization/ minimization objective was equally weighted, although different weightings could be incorporated if desired to emphasize the importance of one or more parameters versus others. Four improved compositions $\\left(\\mathrm{A-D}\\right)^{-}$ were subsequently predicted for each optimization case, allowing any of the 12 hydrazide precursor polymers or 2 aldehyde precursor polymers available to be mixed at any mass ratio to create a new hydrogel. Table 3 shows the optimized recipes selected, while Supporting Information, Figure S23, shows the loading biplot displaying the initial high-throughput data in reduced two-dimensional space together with the relative locations of the new recipes identified by the model.  \n\nOf note, the use of $\\mathrm{PO}_{50}\\mathrm{H}_{30}$ is suggested by multiple optimized recipes for criteria M1 and M2, consistent with the qualitative observations around the potential utility of this precursor polymer for prolonging release while avoiding convective burst. $\\mathrm{PO}_{100}\\mathrm{A}_{30}$ was recommended as the aldehyde polymer for most formulations, although combinations of the dual thermoresponsive $\\mathrm{PO}_{10}\\mathrm{A}_{30}/$ PNIPAM-Hzd precursor polymers were recommended for the M2 optimization in which transparency was not a targeted property. M3 also recommends the use of amphoteric hydrogels in each predicted optimized recipe, consistent with the model objectives to achieve both transparency and longer release periods (i.e., larger $\\tau$ values). Neither chitosan-Hzd nor $\\mathrm{PO}_{0}\\mathrm{H}_{30}$ is recommended for any formulation, likely based on the issues around transparency with chitosan-containing hydrogels (Figure 6) and the lower internal phase separation and thus potential for protein partitioning observed with $\\mathrm{PO}_{0}\\mathrm{H}_{30}$ relative to PNIPAM-Hzd (which otherwise exhibits similar properties).  \n\nThe predicted optimized recipes were then fabricated and characterized for protein release kinetics and transmittance using the same high-throughput analysis techniques, the results of which are shown in Figure 9. Substantial improvements in hydrogel properties are achieved based on the optimization trials. For optimization M1, much higher transparencies are observed ( $597\\%$ in cases in which maximum transparency is a specific target) without suppressing the total release ( ${>}80\\%$ for $\\mathbf{M}1{-}2$ and $>70\\%$ for all other tests conducted) or promoting substantial burst release; this represents a combination of properties not achieved with any of the initial high-throughput screened recipes. For optimization M2, low burst release and high total release are similarly observed, although no obvious improvement was achieved with release duration despite it being a target parameter of the optimization; of note, one formulation had low transparency consistent with transparency not being a target parameter in this optimization. For optimization M3, low burst release, high transparency, and prolonged release periods ${\\bf>}10$ days) are all achieved with higher total release amounts than observed for any of the initial high-throughput samples with even comparable release durations, again showing the benefits of this optimization approach for designing functional hydrogels.  \n\nFurther improvements in gel properties may be achievable upon additional iterations as the results from the first cycle of optimization are added back into the model, enabling the model to become more informed over a broader sample space. While the volume of high-throughput data provided herein as training data is not necessarily required for pursuing such a model-based optimization strategy, the rapid nature of data collection using the high-throughput protocols developed (i.e., successful synthesis of quadruplicate samples of 126 hydrogels within $<25~\\mathrm{\\min}$ and subsequent characterization of those hydrogels in $<30~\\mathrm{min}$ per plate for swelling, $<2\\mathrm{~h~}$ per plate for mechanics/degradation, and $<2~\\mathrm{\\min}$ per plate for transparency), coupled with the facile mixing-based synthetic protocol for preparing hydrazone cross-linked hydrogels that is ideally suited for automated liquid handling systems, make this combination of high-throughput synthesis and statistical modeling both practical and effective. To our knowledge, the approaches described herein for injectable hydrogel fabrication and characterization allow by far the fastest screening of gel properties reported to date. Such high-speed analysis is beneficial to identify functional hydrogel compositions for applications such as drug delivery in which the interplay between different hydrogel properties make explicit prediction of effective compositions challenging.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# CONCLUSIONS  \n\nWe demonstrate the potential of automated high-throughput synthesis and characterization strategies to prepare and screen in situ-gelling hydrogel compositions for targeted applications. In particular, we demonstrate how mixtures of charged and thermoresponsive precursor polymers can reduce burst release, maximize total release, and slow the overall release kinetics of a model protein (here, ovalbumin). Hydrogel compositions optimization is significantly aided by latent variable statistical modeling strategies that provide predictive potential to identify new compositions with improved target properties based on previously collected data. The combination of a highthroughput strategy to rapidly collect large amounts of data (particularly enabled by the development of the suite of highthroughput hydrogel characterization protocols developed and optimized in this paper, the major bottleneck of most materials high-throughput screening applications) with a “big data” latent variable statistical approach that can quantitatively interpret this data thus represents a promising approach to rapidly identifying new injectable hydrogels for protein delivery and/or other applications in which suites of required target properties can be precisely defined (and, thus, optimized for) at the start of the development process.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 6,
+        "chunk": "# ASSOCIATED CONTENT",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# $\\otimes$ Supporting Information  \n\nThe Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.biomac.9b01132.  \n\nTables describing all hydrogel compositions fabricated, schematics of the high-throughput drug release apparatus, high throughput data associated with all combinatorial hydrogel mechanics, swelling, degradation, transparency, and ovalbumin release kinetics, cytocomptability tests on the precursor polymers, sample model fits and squared error plots associated with the fits to the drug release kinetics data, goodness of fit data for the latent variable model constructed, observed versus actual plots for hydrogel transparency and drug release parameters, and a loading biplot showing the relative positions of the hydrogels tested in latent variable space are provided (PDF)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# AUTHOR INFORMATION  \n\nCorresponding Author   \n$^{*}\\mathrm{E}$ -mail: hoaretr@mcmaster.ca.   \nORCID $\\circledcirc$   \nTodd Hoare: 0000-0002-5698-8463   \nNotes   \nThe authors declare no competing financial interest.",
+        "category": " Abstract"
+    },
+    {
+        "id": 9,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nFunding from the Natural Sciences and Engineering Research Council of Canada (Strategic Project Grant # STPGP447372- 13) is gratefully acknowledged. Funding of Corbett’s postdoctoral fellowship by ProSensus Inc. and Mitacs (Accelerate Grant #IT08155) is also acknowledged. ProMV software for performing the latent variable analysis was provided free of charge by ProSensus Inc.",
+        "category": " Acknowledgments"
+    },
+    {
+        "id": 10,
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Injectable, Mixed Natural-Synthetic Polymer Hydrogels with Modular Properties. Biomacromolecules 2012, 13 (2), 369−378.   \n(31) Bakaic, E.; Smeets, N. M. B.; Dorrington, H.; Hoare, T. Offthe-Shelf” Thermoresponsive Hydrogel Design: Tuning Hydrogel Properties by Mixing Precursor Polymers with Different LowerCritical Solution Temperatures. RSC Adv. 2015, 5 (42), 33364− 33376.   \n(32) Ward, M. A.; Georgiou, T. K. Thermoresponsive Polymers for Biomedical Applications. Polymers 2011, 3 (3), 1215−1242.   \n(33) Caló, E.; Khutoryanskiy, V. V. Biomedical Applications of Hydrogels: A Review of Patents and Commercial Products. Eur. Polym. J. 2015, 65, 252−267.   \n(34) Bakaic, E.; Smeets, N. M. B.; Barrigar, O.; Alsop, R.; Rheinstädter, M. C.; Hoare, T. PH-Ionizable in Situ Gelling Poly(Oligo Ethylene Glycol Methacrylate)-Based Hydrogels: The Role of Internal Network Structures in Controlling Macroscopic Properties. Macromolecules 2017, 50 (19), 7687−7698.   \n(35) Campbell, S. B.; Patenaude, M.; Hoare, T. Injectable Superparamagnets: Highly Elastic and Degradable Poly(N-Isopropylacrylamide)−Superparamagnetic Iron Oxide Nanoparticle (SPION) Composite Hydrogels. Biomacromolecules 2013, 14 (3), 644−653. (36) Sivakumaran, D.; Maitland, D.; Hoare, T. Injectable MicrogelHydrogel Composites for Prolonged Small-Molecule Drug Delivery. Biomacromolecules 2011, 12 (11), 4112−4120.   \n(37) Fernandes, T. G.; Diogo, M. M.; Clark, D. S.; Dordick, J. S.; Cabral, J. M. S. High-Throughput Cellular Microarray Platforms: Applications in Drug Discovery, Toxicology and Stem Cell Research. Trends Biotechnol. 2009, 27 (6), 342−349.   \n(38) Xu, F.; Wu, J.; Wang, S.; Durmus, N. G.; Gurkan, U. A.; Demirci, U. Microengineering Methods for Cell-Based Microarrays and High-Throughput Drug-Screening Applications. Biofabrication 2011, 3 (3), 34101.   \n(39) Tzoc Torres, J. M. G.; Nichols, E.; MacGregor, J. F.; Hoare, T. Designing Multi-Responsive Polymers Using Latent Variable Methods. Polymer 2014, 55 (2), 505−516.   \n(40) Bakaic, E.; Smeets, N. M. B.; Dorrington, H.; Hoare, T. Offthe-Shelf” Thermoresponsive Hydrogel Design: Tuning Hydrogel Properties by Mixing Precursor Polymers with Different LowerCritical Solution Temperatures. RSC Adv. 2015, 5 (42), 33364− 33376.   \n(41) Campbell, S.; Maitland, D.; Hoare, T. Enhanced Pulsatile Drug Release from Injectable Magnetic Hydrogels with Embedded Thermosensitive Microgels. ACS Macro Lett. 2015, 4 (3), 312−316. (42) Mateen, R.; Hoare, T. Carboxymethyl and Hydrazide Functionalized $\\beta$ -Cyclodextrin Derivatives: A Systematic Investigation of Complexation Behaviours with the Model Hydrophobic Drug Dexamethasone. Int. J. Pharm. 2014, 472 (1), 315−326.   \n(43) Mateen, R.; Hoare, T. Injectable, in Situ Gelling, CyclodextrinDextran Hydrogels for the Partitioning-Driven Release of Hydrophobic Drugs. J. Mater. Chem. B 2014, 2 (32), 5157−5167.   \n(44) Yang, X.; Bakaic, E.; Hoare, T.; Cranston, E. D. Injectable Polysaccharide Hydrogels Reinforced with Cellulose Nanocrystals: Morphology, Rheology, Degradation, and Cytotoxicity. Biomacromolecules 2013, 14 (12), 4447−4455.   \n(45) Anitha, A.; Maya, S.; Deepa, N.; Chennazhi, K. P.; Nair, S. V.; Tamura, H.; Jayakumar, R. Efficient Water Soluble O-Carboxymethyl Chitosan Nanocarrier for the Delivery of Curcumin to Cancer Cells. Carbohydr. Polym. 2011, 83 (2), 452−461. (46) Fei Liu, X.; Lin Guan, Y.; Zhi Yang, D.; Li, Z.; De Yao, K. Antibacterial Action of Chitosan and Carboxymethylated Chitosan. J. Appl. Polym. Sci. 2001, 79 (7), 1324−1335.   \n(47) Muteki, K.; MacGregor, J. F.; Ueda, T. Rapid Development of New Polymer Blends: The Optimal Selection of Materials and Blend Ratios. Ind. Eng. Chem. Res. 2006, 45 (13), 4653−4660.   \n(48) Smeets, N. M. B.; Bakaic, E.; Patenaude, M.; Hoare, T. Injectable Poly(Oligoethylene Glycol Methacrylate)-Based Hydrogels with Tunable Phase Transition Behaviours: Physicochemical and Biological Responses. Acta Biomater. 2014, 10 (10), 4143−4155. (49) Ng, E. W. M.; Shima, D. T.; Calias, P.; Cunningham, E. T., Jr.; Guyer, D. R.; Adamis, A. P. Pegaptanib, a Targeted Anti-VEGF Aptamer for Ocular Vascular Disease. Nat. Rev. Drug Discovery 2006, 5, 123−132.   \n(50) Osswald, C. R.; Kang-Mieler, J. J. Controlled and Extended Release of a Model Protein from a Microsphere-Hydrogel Drug Delivery System. Ann. Biomed. Eng. 2015, 43 (11), 2609−2617. (51) Schmaljohann, D. Thermo- and PH-Responsive Polymers in Drug Delivery. Adv. Drug Delivery Rev. 2006, 58 (15), 1655−1670. (52) Mura, S.; Nicolas, J.; Couvreur, P. Stimuli-Responsive Nanocarriers for Drug Delivery. Nat. Mater. 2013, 12, 991−1003.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Polymer Coating Materials and Their Fouling Release Activity: A Cheminformatics Approach to Predict Properties  \n\nBakhtiyor Rasulev,\\*,†,§ Farukh Jabeen,† Shane Stafslien,‡ Bret J. Chisholm,§ James Bahr,‡ Martin Ossowski,† and Philip Boudjouk\\*,†,∥  \n\n†Center for Computationally Assisted Science and Technology, North Dakota State University, Fargo, North Dakota, United States ‡Research and Creative Activities, North Dakota State University, Fargo, North Dakota, United States §Department of Coatings and Polymeric Materials, North Dakota State University, Fargo, North Dakota, United States ∥Department of Chemistry and Biochemistry, North Dakota State University, Fargo, North Dakota, United States  \n\n\\*S Supporting Information  \n\n![](images/12ba40b8957b366f98beda47316eccc70eb8f29b40ef8fa6b3dfc6166b7cd6e4.jpg)  \n\nABSTRACT: A novel cheminformatics-based approach has been employed to investigate a set of polymer coating materials designed to mitigate the accumulation of marine biofouling on surfaces immersed in the sea. Specifically, a set of 27 nontoxic, amphiphilic polysiloxane-based polymer coatings was synthesized using a combinatorial, high-throughput approach and characterized for fouling-release (FR) activity toward a number of relevant marine fouling organisms, including bacteria, microalgae, and adult barnacles. In order to model these complex systems adequately, a new computational technique was used in which all investigated polymer-based coating materials were considered as mixture systems comprising several compositional variables at a range of concentrations. By applying a combination of methodologies for mixture systems and a quantitative structure−activity relationship approach (QSAR), seven unique QSAR models were developed that were able to successfully predict the desired FR properties. Furthermore, the developed models identified several significant descriptors responsible for FR activity of investigated polymer-based coating materials, with correlation coefficients ranging from ${r_{\\mathrm{test}}}^{2}=0.{\\dot{63}}$ to 0.94. The computational models derived from this study may serve as a powerful set of tools to predict optimal combinations of source components to produce amphiphilic polysiloxane-based coating systems with effective, broad-spectrum FR properties.  \n\nKEYWORDS: polymer coating materials, QSAR, mixture, polysiloxane, antifouling, fouling-release",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# INTRODUCTION  \n\nCoating materials are widely used in industry and medicine. In this regard, polymer-based coating materials have innumerable applications because they are versatile, cost-effective, and can be tailored to a variety of specifications.1−4 The science of polymer synthesis allows for excellent control over the properties of a bulk polymer system. However, control over surface properties is a major challenge in modern polymer science. It is particularly formidable to predict the surface property of complex polymer materials when the initial mixture of polymer components changes.5,6  \n\nMarine biofouling affects all submerged surfaces causing detrimental effects on shipping and leisure vessels, heat exchangers, oceanographic sensors, and aquaculture systems.  \n\nBiofouling of ship hulls is an ongoing issue that has major economic and environmental impact. Biofouling increases hydrodynamic drag that translates to dramatic reductions in fuel efficiency.7,8 In this regard, early antifouling (AF) strategies involved embedding metal and/or organometallic-based biocides into the polymer matrix of an AF paint. For example, in the 1960s, organotin-based AF coatings were developed and found to be highly effective.9 However, the broad-spectrum activity of the organotin group, primarily tributyltin (TBT), resulted in adverse effects on nontargeted organisms10 and was found to be unacceptably persistent in the marine environment.11 As a result, the International Maritime Organization Convention on the Control of Harmful AF Systems banned the use of TBT in marine coatings after 2008. Due to this ban, new AF coatings have been primarily based on copper-containing biocides.12 Although the toxic effects of copper to nontarget organisms are not as severe as those of tin, the use of copper still represents a serious environmental concern.  \n\nAs a nontoxic alternative to AF coatings, fouling-release (FR) coatings were developed and commercialized. Unlike AF coatings, FR coatings do not contain biocides and combat ship hull fouling by minimizing the adhesion strength between the attached organism and the coating surface so that the fouling can be removed through hydrodynamic shearing. Some relationships between the type of surface (hydrophobic or hydrophilic) and fouling adhesion was discussed by Krishnan et al.13−16, where the authors indicated that different marine organisms have different adhesion properties to hydrophobic and hydrophilic surfaces. For example, the authors showed that while Navicula cells released more easily from hydrophilic surfaces, Ulva sporelings showed higher removal from hydrophobic surfaces. Ideally, the adhesion strength between the attached fouling organisms and coating surface is low enough to enable release of the majority of the attached fouling when the vessel is underway. Thus, commercially available FR coatings are generally based on polysiloxanes17 It is generally accepted that the relatively good FR performance of polysiloxane-based coatings is a result of both the low surface energy of polysiloxanes and their low moduli.18,19 As a result, it has been of interest to investigate the modification of polysiloxanes with hydrophilic moieties to reduce biofouling. For example, polydimethylsiloxane (PDMS) elastomers were surface modified with PEOs using platinum-catalyzed hydrosilylation, and modified surfaces provided a $90\\%$ reduction of fibrinogen adsorption compared to the unmodified PDMS control.20  \n\nPolysiloxane-based amphiphilic polymer coating materials have been recently investigated for the fouling release (FR) activity by other researchers.21,22 In previous work22 these materials were synthesized using combinatorial analysis and investigated for the best components’ composition to obtain a polymer coating with desired properties. However, combinatorial analysis enables synthesis of a limited number of polymer coating materials and does not directly specify the main structural factors that are responsible for imparting optimal release of biofouling from coating surfaces. In this case, computational methods, such as quantitative structure− activity/property relationships (QSAR/QSPR), can be helpful in elucidating these key attributes and generate ideas for further improvement of these coating systems.  \n\nQSAR analysis is based on the premise that the structure of a molecule is the principal determinant of its physicochemical, toxicological, and biomedicinal properties.2 3−26 Presently, QSAR is widely applied to the development of rationales to enhance desirable properties by tuning the structure within the congeneric series of compounds, including polymers. This popular approach utilizes statistical methods to determine a correlation among structural features of compounds and the studied property(s). Most QSAR/QSPR models tend to follow a similar strategy.27 This includes the following: (1) data set selection, (2) molecular structure generation, (3) geometry optimization of molecular structures using appropriate procedures, (4) various descriptors generation, (5) variable selection and/or data reduction methods, (6) model generation, (7) and validation and predictability evaluation of the developed models.28,29  \n\nTo date, there are only a few publications related to QSARs of polymers, since polymers are inherently complicated macromolecular systems, possessing large molecular sizes, conformationally labile structures, nonsystematic cross-linking, etc.30−32 For example, attempts have been made to develop special descriptors that encode polymer structures.31 As the next step, several efforts were made to build QSAR models for various properties of polymers.30,32 For this purpose, researchers often use the information based on monomer structure.30,32 Yu et al.32 developed two artificial neural network (ANN) models to predict reactivity parameters ln $\\boldsymbol{Q}$ and e of acrylate monomers, applying data from density functional theory (DFT) calculations at the $\\mathrm{B}3\\mathrm{LYP}/6{\\cdot}31\\mathrm{G}(\\mathrm{d},\\mathrm{p})$ level. The authors found that the resonance and polar effects of acrylate monomers can be reflected by quantum-chemical descriptors such as Mulliken and atomic polar tensor (APT) charges, the total dipole moment $\\left(\\mu_{\\mathrm{T}}\\right)$ , the lowest unoccupied molecular orbital energy $\\left(E_{\\mathrm{LUMO}}\\right)$ , and the total energy $\\bar{(}E_{\\mathrm{T}})$ . In other work, authors developed a QSPR model for refractive indices of 234 structurally diverse polymers.30 The reported model involved a single molecular descriptor and a conformationindependent approach, in which the most appropriate polymer structures were investigated by considering $_{1-5}$ monomeric repeating units. Another study, which is very close to the current study attempting to investigate and predict surface adhesion property of a library of 496 polymers, was published by Winkler and coauthors.33 The authors used a data set provided by Yang et al.34 and applied a QSAR approach to build neural network predictive models. The authors generated satisfactory models with ${r_{\\mathrm{test}}}^{2}=0.63$ ; however, no detailed information on the data set and which polymer structures were used for descriptor generation (linear or cross-linked) were provided in this paper, which makes it difficult to reproduce the results and investigate further applications. In this regard, systematic and reproducible investigations of a number of data sets is still needed for these kinds of systems, to more adequately address new challenges in this field.  \n\nFor polymer coating systems, the situation is even more complicated, since these materials often comprise highly crosslinked polymers, combining several different monomers in the polymeric system. As a result of this complexity, the classical QSAR approaches are not readily applicable for polymer coating systems, and no publications on this topic are presently known. Molecular modeling approaches to deal with polymer coatings, computational investigations, and rational design have been unsuccessful because of the highly complicated structures of the systems which prevent direct modeling.  \n\nAs mentioned above, the prediction of surface properties for complex polymer coating systems when the initial mixture of polymer substrates changes is an exceedingly difficult and challenging task. However, we recently reported preliminary studies with application of a novel mixture-QSAR approach for polymer coatings.35,36 In this paper, an attempt to develop a first QSAR-based model(s) is reported which provides a possible avenue in which to computationally predict FR properties of the coatings investigated. Described herein is a computational methodology applied to amphiphilic polysiloxane coatings and structure−activity modeling results obtained for several marine organisms, including bacteria, microalgae, and adult barnacles.  \n\nTable 1. List of Polymer Coatings, Concentration of Components, and Observed FR Activities (End Point Values)   \n\n\n<html><body><table><tr><td>samplesc</td><td>CF3- PDMS</td><td> PDMS</td><td>silica disp.a</td><td> BA</td><td>TMS- PEG</td><td>MeTAcSi</td><td>cat. h soln.b</td><td>c. lyt retention</td><td>c. lyt c. lyt retraction removal</td><td>h. pac retention</td><td>h. pac removal</td><td>a. amph attachmnt</td><td>a. amph adhesion</td></tr><tr><td>OPEG/ 11.0CF3</td><td>2.06</td><td>21.76</td><td>12.57</td><td>19.8</td><td>0</td><td>3.06</td><td>3.75 1.99</td><td>99.8</td><td>46.1</td><td>0.52</td><td>5.2</td><td>0</td><td>0.18</td></tr><tr><td>OPEG/ 13.75CF3</td><td>2.58</td><td>21.1</td><td>12.58</td><td>19.81 0</td><td></td><td>3.06 3.76</td><td>2.30</td><td>99.9</td><td>55.0</td><td>0.65</td><td>20.9</td><td>0</td><td>0.16</td></tr><tr><td>OPEG/ 16.5CF3</td><td>3.09</td><td>20.42</td><td>12.57</td><td>19.81 0</td><td></td><td>3.06 3.75</td><td>2.10</td><td>100.0</td><td>40.6</td><td>0.46</td><td>0.0</td><td>0</td><td>0.16</td></tr><tr><td>OPEG/ 19.25CF3</td><td>3.59</td><td>19.65</td><td>12.51 19.7</td><td>０</td><td></td><td>3.04 3.73</td><td>2.33</td><td>99.8</td><td>40.3</td><td>0.59</td><td>23.3</td><td></td><td>0.18</td></tr><tr><td>OPEG/ 22.0CF3</td><td>4.11</td><td>19.04</td><td>12.55</td><td>19.77 0</td><td></td><td>3.05 3.75</td><td>2.18</td><td>99.0</td><td>37.9</td><td>0.64</td><td>30.8</td><td>0</td><td>0.15</td></tr><tr><td>OPEG/ 24.75CF3</td><td>4.63</td><td>18.4 12.57</td><td>19.8</td><td>0</td><td></td><td>3.06 3.75</td><td>1.85</td><td>88.9</td><td>41.6</td><td>0.56</td><td>15.3</td><td>0</td><td>0.13</td></tr><tr><td>OPEG/ 27.5CF3</td><td>6.31</td><td>21.74 15.42</td><td>24.29</td><td>0</td><td></td><td>3.75 4.6</td><td>1.95</td><td>97.9</td><td>45.7</td><td>0.51</td><td>9.2</td><td>1</td><td>0.15</td></tr><tr><td>OPEG/ 30.25CF3</td><td>6.99</td><td>21.06 15.52</td><td></td><td>24.45 0</td><td></td><td>3.78 4.63</td><td>1.99</td><td>93.0</td><td>50.9</td><td>0.62</td><td>52.4</td><td>3</td><td>0.15</td></tr><tr><td>OPEG/ 0CF3</td><td>0</td><td>24.43 12.56</td><td></td><td>19.78 0</td><td></td><td>3.06 3.75</td><td>1.87</td><td>100.0</td><td>35.1</td><td>0.63</td><td>6.6</td><td>１</td><td>0.23</td></tr><tr><td>6PEG/ 11.0CF3</td><td>1.93</td><td>20.38 11.78</td><td></td><td>20.56</td><td>1.83</td><td>2.87 3.76</td><td>0.83</td><td>5.4</td><td>85.6</td><td>0.43</td><td>16.1</td><td>２</td><td>0.13</td></tr><tr><td>6PEG/ 13.75CF3</td><td>2.41</td><td>19.75 11.77</td><td>20.55</td><td></td><td>1.82</td><td>2.86 3.76</td><td>0.72</td><td>1.9</td><td>93.1</td><td>0.30</td><td>0.0</td><td>1</td><td>0.10</td></tr><tr><td>6PEG/ 16.5CF3</td><td>2.9</td><td>19.14 11.79</td><td>20.58</td><td></td><td>1.83</td><td>2.87 3.76</td><td>0.72</td><td>4.2</td><td>95.8</td><td>0.34</td><td>33.1</td><td>２</td><td>0.11</td></tr><tr><td>6PEG/ 19.25CF3</td><td>3.31</td><td>18.14 11.55</td><td>20.17</td><td></td><td>1.79</td><td>2.81 3.69</td><td>0.67</td><td>13.5</td><td>96.3</td><td>0.26</td><td>15.8</td><td>3</td><td>0.13</td></tr><tr><td>6PEG/ 22.0CF3</td><td>3.88</td><td>17.95 11.83</td><td>20.66</td><td></td><td>1.83</td><td>2.88 3.78</td><td>0.33</td><td>0.1</td><td>97.1</td><td>0.23</td><td>41.5</td><td>3</td><td>0.08</td></tr><tr><td>6PEG/ 24.75CF3</td><td>4.34</td><td>17.25 11.78</td><td>20.57</td><td></td><td>1.83</td><td>2.87 3.76</td><td>0.35</td><td>0.8</td><td>93.6</td><td>0.20</td><td>29.4</td><td>2</td><td>0.07</td></tr><tr><td>6PEG/</td><td>5.92</td><td>20.38 14.45</td><td></td><td>25.23</td><td>2.24</td><td>3.52 4.62</td><td>0.28</td><td>0.5</td><td>93.9</td><td>0.17</td><td>84.8</td><td>５</td><td>0.10</td></tr><tr><td>27.5CF3 6PEG/</td><td>6.55</td><td>19.74 14.55</td><td>25.4</td><td></td><td>2.26</td><td>3.54 4.65</td><td>0.46</td><td>2.4</td><td>95.8</td><td>0.22</td><td>49.6</td><td>６</td><td>0.08</td></tr><tr><td>30.25CF3 6PEG/</td><td>0</td><td>22.95 11.8</td><td>20.6</td><td></td><td>1.83</td><td>2.87 3.77</td><td>2.14</td><td>100.0</td><td>36.6</td><td>0.52</td><td>26.1</td><td>０</td><td>0.13</td></tr><tr><td>0CF3 8PEG/</td><td>1.89</td><td>19.93</td><td>11.51</td><td>20.75</td><td>2.38</td><td>2.8 3.76</td><td>0.90</td><td>9.4</td><td>94.8</td><td>0.32</td><td>0.0</td><td></td><td>0.11</td></tr><tr><td>11.0CF3 8PEG/</td><td>2.36</td><td>19.3 11.51</td><td></td><td>20.75</td><td>2.38</td><td>2.8 3.76</td><td>0.41</td><td>1.7</td><td>96.0</td><td>0.33</td><td>27.3</td><td>3</td><td>0.08</td></tr><tr><td>13.75CF3 8PEG/</td><td>2.83</td><td>18.72</td><td>11.53 20.78</td><td></td><td>2.38</td><td>2.81 3.76</td><td>0.39</td><td>0.6</td><td>96.7</td><td>0.24</td><td>16.3</td><td>3</td><td>0.09</td></tr><tr><td>16.5CF3 8PEG/</td><td>3.3</td><td>18.1 11.52</td><td>20.78</td><td></td><td>2.38</td><td>2.8 3.76</td><td>0.60</td><td>3.2</td><td>95.9</td><td>0.39</td><td>52.5</td><td>3</td><td>0.08</td></tr><tr><td>19.25CF3 8PEG/</td><td>3.77</td><td>17.47 11.52</td><td>20.77</td><td></td><td>2.38</td><td>2.8 3.76</td><td>0.73</td><td>20.0</td><td>94.7</td><td>0.05</td><td>59.9</td><td>7</td><td>0.09</td></tr><tr><td>22.0CF3 8PEG/</td><td>4.25</td><td>16.86</td><td>20.77</td><td></td><td></td><td>2.8 3.76</td><td>1.04</td><td>9.6</td><td>92.3</td><td>0.21</td><td>63.9</td><td>8</td><td>0.17</td></tr><tr><td>24.75CF3 8PEG/</td><td>5.8</td><td>11.52 19.96 14.15</td><td>25.52</td><td></td><td>2.38 2.93</td><td>3.44 4.62</td><td>0.85</td><td>8.2</td><td>97.3</td><td>0.10</td><td></td><td></td><td>0.08</td></tr><tr><td>27.5CF3 8PEG/</td><td>6.42</td><td>19.34</td><td>25.7</td><td></td><td>2.95</td><td>3.47 4.65</td><td>0.65</td><td>13.1</td><td>99.6</td><td>0.03</td><td>98.4 100.0</td><td>7</td><td>0.05</td></tr><tr><td>30.25CF3 8PEG/ 0CF3</td><td>0 22.39</td><td>14.26 11.51</td><td>20.75</td><td>2.38</td><td>2.8</td><td>3.76</td><td>1.99</td><td>92.7</td><td>30.9</td><td>0.32</td><td>0.0</td><td>５ 1</td><td>0.15</td></tr></table></body></html>\n\naSilica was dispersed in BA (butyl acetate) at a 20:80 silica/BA wt./wt. ratio (silica disp.)22 bTBAF (tetrabutylammonium fluoride) was diluted with MIBK (4-methyl-2-pentanone) to produce a $50~\\mathrm{mM}$ solution (cat. soln.). cCoating compositions were encoded as follows: xPEG/yCF3 where $x$ is the TMS-PEG content expressed as a weight percentage relative to the total weight of PDMS, $\\mathrm{CF}_{3}–\\mathrm{PDMS},$ , silica, TMS-PEG, and MeTAcSi, and $y$ is the content of $\\mathrm{CF}_{3}$ -PDMS expressed as a weight percentage relative to total weight of $\\mathrm{CF}_{3}$ -PDMS and PDMS.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# MATERIALS AND METHODS  \n\nPolymer Coating Materials. A set of 27 polymer coatings was produced using a combinatorial approach and characterized for activity toward a number of relevant marine fouling organisms, including bacteria, microalgae, and adult barnacles22 (Table 1). The details on coating preparation and fouling-release experiments were described previously.22 An automated water-jet method was used to evaluate the adhesion of two marine bacteria in a rapid manner, Cellulophaga lytica and Halomonas pacif ica, and a microalgae diatom, Navicula incerta, to coatings prepared in multiwell plates using methods that have been previously described in detail.12 In addition, the coatings were evaluated for their ability to prevent or minimize the adhesion strength of barnacles (Amphibalanus Amphitrite) using a rapid laboratory reattachment assay that has been previously described in detail.22 All components of the polymer coatings were identified structurally and characterized computationally.21,22  \n\n![](images/d68d0cbcbbcb8df8a8f147edd433fafdc9f33784703c239e9f491bc2f9973e33.jpg)  \nFigure 1. A representation of a highly cross-linked polymer coating (represented as a mustard colored material within a blue box) derived from multiple reactive components.  \n\nTable 2. A List of the Components Used to Produce the Polysiloxane-Based Fouling-Release Coatings Investigated   \n\n\n<html><body><table><tr><td>Component</td><td>Molecular Structure</td></tr><tr><td>CF3-PDMS</td><td>HC OH CH2 HC</td></tr><tr><td></td><td>HC CH3 H3C CH HC CH3 0 H3C 0 CH3 HC H3C CH3</td></tr><tr><td></td><td>CH3 HC O 0</td></tr><tr><td></td><td>CH3 HO- Si- OH CH3</td></tr><tr><td>TMS-PEG</td><td>H3C H CH</td></tr></table></body></html>  \n\nIn order to model these complex systems, all coatings investigated were considered as mixture systems, having components in various initial concentrations (Figure 1). The main components involved in the study are listed in Table 2. A set of parameters/descriptors was generated that encoded each component of the system.  \n\nDescriptors Generation. To relate components’ structure changes to FR properties for each initial component of the polymer coating, a set of properties/descriptors was computationally generated that encoded the chemical structure. The structures were built and prepared for further use by Chemaxon software.37 Dragon 6 software38 was used to generate a set of descriptors. This software provides more than 4500 various descriptors corresponding to 0D, 1D, 2D, and 3D indexes. The descriptors are comprised of 20 different classes constitutional, topological, walk and path counts, connectivity indices, information indices, 2D autocorrelations, edge adjacency indices, Burden eigenvalues, topological charge indices, eigenvalue based indices, randic molecular profiles, geometrical descriptors, RDF descriptors, 3D-MoRSE descriptors, WHIM descriptors, GETAWAY descriptors, functional groups, atom-centered fragments, charge descriptors, and molecular property descriptors.38,39 Constant and near to constant descriptors were eliminated. After filtering out constant and close to constant descriptors, about 1200 descriptors in total were generated per each main component of the polymer coating.  \n\nMixture Descriptors. Due to the complexity of polymer coatings, a new approach to describe the polymer coating system was applied. For this work, the following methodology was utilized. Each polymer coating was considered as a mixture system, where components were in various concentrations, and descriptors for each polymer coating were calculated based on structures and concentrations of each component (so-called mixture descriptors) in the coating. Figure 1 represents the overall idea and complexity of the polymer coating.  \n\nTo implement this approach, the following equations were applied:  \n\n$$\nD_{\\operatorname*{mix}}=f\\big(C_{1}\\times D_{n},~C_{2}\\times D_{n},~C_{3}\\times D_{n},~C_{4}\\times D_{n}...C_{n}\\times D_{n}\\big)\n$$  \n\nwhere $D_{\\mathrm{mix}}$ is a mixture descriptor, $C_{n}$ is the concentration of an individual component in the mixture, and $D_{n}$ is a descriptor of individual component  \n\n$$\nA_{\\mathrm{mix}}=f(P_{1},P_{2},P_{3},P_{4},\\ldots P_{n})\n$$  \n\nwhere $A_{\\mathrm{mix}}$ is the activity of the mixture system, $P$ is the component property, $P=(C_{n}\\times D_{\\operatorname*{mix}_{-}n})$  \n\n$$\nA_{\\mathrm{mix}}=(C_{1}\\times D_{\\mathrm{mix1}})+(C_{2}\\times D_{\\mathrm{mix2}})...+(C_{n}\\times D_{\\mathrm{mix3}})\n$$  \n\nwhere $C$ is the coefficient, $D_{\\operatorname*{mix}_{-}n}$ is the mixture descriptor, and $A_{\\mathrm{mix}}$ is the activity of the mixture system  \n\nThe first equation, eq 1, shows how the mixture descriptors were obtained, by including the same type of descriptor $\\left(D_{n}\\right)$ from each component to describe the mixture system. Equation 2 represents the activity of the mixture system that depends on properties of the components in this system. The next equation, eq 3, represents the summary of eq 1 and eq 2, which can be considered as an overall MLR-based QSAR equation, covering the presence of mixture descriptors and coefficients in the model. The overall scheme of the applied approach is represented in Figure 2.  \n\n![](images/9213bd913002163d5f7c7e1b43c68428a2f5383c148749a751ac25f2a27fcc71.jpg)  \nFigure 2. Scheme of applied mixture−QSAR approach to polymer coatings, where Comp 1···Comp 5 are components of the polymer coating, $C_{1}...C_{5}$ are concentrations of components, and $D_{n}$ are descriptors’ values for the components.  \n\nQSAR Modeling. After the calculation of all mixture descriptors, the next step was QSAR modeling. For that, the set of 27 coatings was divided into training (21 coatings) and test sets (6 coatings), $75\\%$ training set and $25\\%$ test set.  \n\nOverall, QSAR is a mathematical relationship between a biological activity of a molecular system and its geometric, chemical, or physical characteristics. QSAR attempts to find a consistent relationship between biological activity and molecular properties, so that these “rules” can be used to evaluate the activity of new chemical systems. Once a valid QSAR has been determined, it should be possible to predict the physical property or biological activity of related compounds or drug candidates before they are put through expensive and time-consuming biological testing. In some cases, only computed values need to be known to make an assessment.  \n\nIn the current study, the correlation between activity and structural properties was developed by using the variable selection Genetic Algorithm (GA) and Multiple Linear Regression Analysis (MLRA) methods. Thus, preliminary model selection was performed by means of the GA-MLRA40−43 technique as implemented in the QSARINS $2.2^{44,45}$ program. It is worth noting that genetic algorithms have been applied in recent studies as a powerful tool to address many problems in QSAR studies.40−43 The method is based on the mechanism of natural evolution, where the higher descriptor weights are more preserved in the mathematic evolution process and finally in the model, while the lower weight descriptor is eliminated. In this study, the GA variable selection technique was used to reduce the number of descriptors that is applied for the final model and GA variable selection started with a population of 500 random models and 2000 iterations to evolution with the mutation probability specified at $40\\%$ . The MLRA technique was used to develop final QSAR models, since it is transparent, easy to interpret, and ideal to obtain reproducible results.  \n\nSeveral QSAR models were developed (one model per each end point), followed by statistical analysis with evaluation by squared correlation coefficient $r^{2}$ root-mean-square error RMSE, Fisher coefficient $F,$ and noncollinearity of descriptors in the model. A final set of QSARs was generated by using the GA-MLR approach and tested by applying the “leave-one-out” technique (the process of removing a molecule from the set, then creating and validating the model against the individual molecules, which was performed for the entire training set), $q^{2}$ .  \n\nThus, we utilized the following equations to calculate correlation coefficient, $r^{2}$ (eq 4), and the root-mean-square error of calibration (training) ${\\mathrm{RMSE}}_{\\mathrm{C}},$ as the measures of goodness-of-fit for each developed model (eq 5):  \n\n$$\nR^{2}=1-\\frac{\\sum_{i=1}^{n}\\big(y_{i}^{\\mathrm{obs}}-y_{i}^{\\mathrm{pred}}\\big)^{2}}{\\sum_{i=1}^{n}\\big(y_{i}^{\\mathrm{obs}}-\\tilde{y}^{\\mathrm{obs}}\\big)^{2}}\n$$  \n\n$$\n\\mathrm{RMSE}_{\\mathrm{C}}=\\sqrt{\\frac{\\sum_{i=1}^{n}{\\binom{\\mathrm{obs}}{i}}^{\\mathrm{pred}})^{2}}{n}}\n$$  \n\nTo verify stability of the models (sensitivity to the composition of the training set), in each case, we calculated the cross-validated coefficient $\\overline{{q_{\\mathrm{LOO}}}}^{2}$ (leave-one-out method) and root-mean-square error of cross-validation $\\mathrm{RMSE}_{\\mathrm{CV}}$ . Both statistics were calculated according to eq 6 and eq 7:  \n\n$$\n{Q_{\\mathrm{LOO}}^{2}=1-\\frac{\\sum_{i=1}^{n}\\big(y_{i}^{\\mathrm{obs}}-y_{i}^{\\mathrm{predcv}}\\big)^{2}}{\\sum_{j=1}^{n}\\big(y_{j}^{\\mathrm{obs}}-\\tilde{y}^{\\mathrm{obs}}\\big)^{2}}}\n$$  \n\n$$\n\\mathrm{RMSE}_{\\mathrm{CV}}=\\sqrt{\\frac{\\sum_{i=1}^{n}\\big(y_{i}^{\\mathrm{obs}}-y_{i}^{\\mathrm{predcv}}\\big)^{2}}{n}}\n$$  \n\nFollowing the recommendations by Gramatica and Chirico and by $\\mathrm{Lin},^{46,47}$ we calculated the Concordance Correlation Coefficient (CCC) as a more restrictive parameter for expressing external predictivity of each model in comparing to the commonly used external (test set) validation coefficient ${q_{\\mathrm{Ext}}}^{2}$ (eq 8) and root-meansquare error of prediction $\\mathrm{(RMSE_{P};}$ eq 9). In this work, we applied all three of these statistics.  \n\n$$\nQ_{\\mathrm{EXT}}^{2}=1-\\sum_{j=1}^{k}{(y_{j}^{\\mathrm{obs}}-y_{j}^{\\mathrm{pred}})^{2}}/\\sum_{j=1}^{k}{(y_{j}^{\\mathrm{obs}}-\\hat{y}^{\\mathrm{obs}})^{2}}\n$$  \n\n$$\n\\mathrm{RMSE}_{\\mathrm{p}}=\\sqrt{\\frac{\\sum_{i=1}^{k}{(y_{j}^{\\mathrm{obs}}-y_{j}^{\\mathrm{pred}})^{2}}}{k}}\n$$  \n\nwhere $y_{j}^{\\mathrm{{obs}}}$ is experimental (observed) value of the property for the ith/jth compound; $y_{j}^{\\mathrm{pred}}$ is the predicted value for the ith/jth compound; $\\tilde{y}$ and $\\hat{y}$ are the mean experimental value of the property in the training and validation set, respectively; $n$ and $k$ are the number of compounds in the training and validation set, respectively.  \n\nAdditionally, the chemical applicability domain (AD) for the models obtained was calculated by the leverage approach to verify predictive reliability.29,48 To visualize the applicability domain of the QSPR models, the Williams plot was used. Thus, the Williams plot of standardized cross-validated residuals (RES) versus leverage (Hat diagonal) values (HAT) clearly depicts both the response outliers (Y outliers) and structurally influential compounds ( $X$ outliers) in a model.  \n\n![](images/47f9c0444e69e64a2ce7b1f8b7c5ece420729e796e37d2e82f683d20e3465309.jpg)  \nFigure 3. Scheme of the overall steps for polymer coating modeling and design.  \n\nTable 3. List of Developed Models for Seven Investigated End Points (Regression and Classification Models)   \n\n\n<html><body><table><tr><td colspan=\"2\">regression models</td><td colspan=\"7\"></td></tr><tr><td>model/end point</td><td>descriptors</td><td>R² (training)</td><td> RMSE (training)</td><td>Q² (training)</td><td>F-test</td><td>R² (test)</td><td>RMSE (test)</td><td> R² (y-scrambling)</td></tr><tr><td>Model 1 C.lyt Retention</td><td>Mor18v</td><td>0.72</td><td>0.38</td><td>0.66</td><td>48.98</td><td>0.63</td><td>0.46</td><td>0.11 ± 0.40</td></tr><tr><td>Model 2 C.lyt. Retraction</td><td>Mor09m</td><td>0.81</td><td>19.31</td><td>0.77</td><td>82.01</td><td>0.75</td><td>24.08</td><td>0.14 ± 0.42</td></tr><tr><td>Model 3 C.lyt Removal</td><td>Mor09m</td><td>0.85</td><td>10.07</td><td>0.82</td><td>110.67</td><td>0.94</td><td>9.16</td><td>0.13 ± 0.44</td></tr><tr><td>Model 4 H.pac Retention</td><td>SPAM, DLS_04</td><td>0.86</td><td>0.07</td><td>0.80</td><td>53.21</td><td>0.79</td><td>0.08</td><td>0.01 ± 0.52</td></tr><tr><td>Model 5 H.pac Removal</td><td>VR2_RG</td><td>0.76</td><td>14.84</td><td>0.71</td><td>61.78</td><td>0.67</td><td>24.35</td><td>0.06 ± 0.54</td></tr><tr><td>Model 6 A.amph Attachment</td><td>AVS_B(p)</td><td>0.63</td><td>1.54</td><td>0.54</td><td>31.85</td><td>0.91</td><td>0.76</td><td>0.04 ± 0.46</td></tr><tr><td>Model 7 A.amph Adhesion</td><td>Mor09p</td><td>0.84</td><td>0.02</td><td>0.78</td><td>91.69</td><td>0.85</td><td>0.01</td><td>0.07 ± 0.55</td></tr><tr><td>classification models</td><td>accuracy (training)</td><td>error rate (training)</td><td>sensitivity (training)</td><td>specificity (training)</td><td>accuracy (test)</td><td>error rate</td><td>sensitivity (test)</td><td>specificity (test)</td></tr><tr><td>Model 1 C.lyt Retention</td><td>Mor18v 1.00</td><td>0.00</td><td>1.00</td><td>1.00</td><td>0.83</td><td>0.16</td><td>0.75</td><td>1.00</td></tr><tr><td>Model 2 C.lyt. Retraction</td><td>Mor09m 1.00</td><td>0.00</td><td>1.00</td><td>1.00</td><td>1.00</td><td>0.00</td><td>1.00</td><td>1.00</td></tr><tr><td>Model 3 C.lyt Removal</td><td>Mor09m 1.00</td><td>0.00</td><td>1.00</td><td>1.00</td><td>1.00</td><td>0.00</td><td>1.00</td><td>1.00</td></tr></table></body></html>  \n\nAll initial descriptors were normalized before calculation of mixture descriptors. The normalization of descriptors was carried out using Matlab.49  \n\nDecision Trees Method. The classification analysis was established by the Decision Trees method50 using Matlab.49 The quality of all developed models was determined using eqs 10, 13, and 14:  \n\n$$\n\\mathrm{Classification\\accuracy}={\\frac{\\mathrm{TP}+\\mathrm{TN}}{\\mathrm{TP}+\\mathrm{TN}+\\mathrm{FP}+\\mathrm{FN}}}\\times100\n$$  \n\nwhere TP is the number of true positive classifications (toxic substance), FN is the number of false positive classifications, TN is the number of true negative classifications (nontoxic substance), and FP is the number of false negative classifications.  \n\n$$\n{\\mathrm{Error~rate}}={\\frac{{\\mathrm{FP}}+{\\mathrm{FN}}}{{\\mathrm{TP}}+{\\mathrm{TN}}+{\\mathrm{FP}}+{\\mathrm{FN}}}}\\times100 \n$$  \n\n$$\n\\mathrm{Sensitivity=\\frac{TP}{\\ T P\\ +\\ F N}\\times100}\n$$  \n\n$$\n\\mathrm{Specificity}=\\frac{\\mathrm{TN}}{\\mathrm{TN}+\\mathrm{FP}}\\times100\\\n$$  \n\n$$\n\\mathrm{y=\\frac{sensitivity+specificity}{2}\\times100}\n$$  \n\nVisualization. All visualization plots and figures were obtained using QSARINS 2.2,43,44 Chemaxon Suite,37 and MS Office PowerPoint applications.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# RESULTS AND DISCUSSION  \n\nThe overall scheme of the study can be represented by Figure 3, where experimental data set and QSAR modeling are shown as Task 1 and Task 2 (only Cheminformatics), in order to find the desired properties, shown in Task 3.  \n\nTable 2 lists the components and their structures used to produce the polymer coatings studied in this research, while in Table 1 can be found the list of components and concentrations of the components.  \n\nAfter all preliminary steps (structure preparation, descriptors generation, and mixture descriptors calculation), the QSAR modeling was applied and a set of predictive models for various end points developed based on 27 polymer coatings with fouling-release properties.  \n\nThe list of models and associated descriptors with each model is provided in Table 3 (the additional statistical data are given in Table S3).  \n\nThus, Model 1 (eq 15) that predicts the marine bacteria Cellulophaga lytica biofilm retention index for the set of polymer coating materials is represented below:  \n\nTable 4. List of Models and Corresponding Descriptors Selected for Each Model   \n\n\n<html><body><table><tr><td>model/end point</td><td>descriptor</td><td> definition and scope</td><td> descriptor type</td></tr><tr><td>Modell C.lyt Retention</td><td>Mor18v</td><td> signal 18/weighted by van der Waals volume</td><td>3D-MoRSE descriptors38</td></tr><tr><td>Model2 C.lyt. Retraction</td><td>Mor09m</td><td> signal 09/weighted by mass</td><td>3D-MoRSE descriptors38</td></tr><tr><td>Model 3 C.lyt Removal</td><td>Mor09m</td><td> signal 09/weighted by mass</td><td>3D-MoRSE descriptors38</td></tr><tr><td>Model 4 H.pac Retention</td><td></td><td> SPAM DLS_04 average span R modified drug-like score from Chen et al. (7 rules)</td><td>shape indices,38 basic indices38</td></tr><tr><td>Model 5 H.pac Removal</td><td>VR2_RG</td><td>normalized Randic-like eigenvector-based index from reciprocal squared geometrical3D-matrix based38 matrix</td><td></td></tr><tr><td>Model 6 A.amph Attachment</td><td>AVS_B(p)</td><td>average vertex sum from Burden matrix weighted by polarizability</td><td>2D-matrix based38</td></tr><tr><td>Model 7 A.amph Adhesion</td><td>Mor09p</td><td> signal 09/weighted by polarizability</td><td> 3D-MoRSE descriptors38</td></tr></table></body></html>  \n\n![](images/b1880fd0342f19b80e0d2c9513c54595b81ec71525fe6f4de666d187686b7f82.jpg)  \nFigure 4. Plots for C.lytica biofilm retention model 1: (a) obs vs pred correlation, (b) Williams plot, where yellow dots $\\mathbf{\\tau}=\\mathbf{\\tau}$ training set, blue dots $\\mathbf{\\tau}=\\mathbf{\\tau}$ test set; (c) $y$ -scrambling results, where blue and dark blue dots are $r^{\\hat{2}}$ and $q^{2}$ of original model, other dots, yellow and red, are simulated $r^{2}$ and $q^{2}$ values.  \n\n$$\n\\mathrm{Amix}(\\mathrm{C.lyt\\_ret})=2.01\\left(\\pm0.85\\right)\\mathrm{Mor18v}-0.39\\left(\\pm0.29\\right)\n$$  \n\n$$\n(n=27,r_{\\mathrm{train}}^{2}=0.72,q_{\\mathrm{loo}}^{2}=0.66,r_{\\mathrm{test}}^{2}=0.63,\\mathrm{H}\n$$  \n\n$$\n\\mathrm{E}_{\\mathrm{tr}}=0.384,F=48.985)\n$$  \n\nwhere Mor18v is 3D-MoRSE descriptor signal 18/weighted by van der Waals volume.38  \n\nAs can be seen from model 1, the C. lytica biofilm retention index depends here on signal 18/weighted by van der Waals volume, the 3D-MoRSE descriptor of main components.38 It is important to note that coatings possessing good antifouling (AF)/FR properties should ideally exhibit a low amount of biofilm retention. Therefore, the identification of all features (descriptors) of the coating components that are positively associated with a reduction in C. lytica biofilm retention is desirable. In model 1 (eq 15), Mor18v, is weighted by van der Waals volume, which means the specific van der Waals volume size of the polymer coating’s structure plays a significant role in the retention of C. lytica biofilm. Thus, the positive contribution of this descriptor suggests that the amount of C. lytica biofilm retention increases with increasing van der Waals volume of the polymeric system, and consequently, to adequately mitigate biofilm retention, the Mor18v descriptor needs to have low values.  \n\nTable 4 provides a list of models utilized and the corresponding descriptors selected for each model (1−7). Figures $^{4-9}$ provide plots generated using models $^{1-7,}$ respectively. Each figure contains a plot of (a) the correlation between observed and predicted values, (b) Williams plot (AD plot), and (c) Y-scrambling validation results for the investigated end point. The plot of observed vs predicted values shows the predictive ability of the model by representing the location of the points on the correlation line. The Williams plot reflects the applicability domain of the model and ability of the model to successfully predict the values for a similar set of coatings. Y-scrambling is a validation technique, which shows the unique character of the model developed, i.e., a good model has higher $R^{2}$ $(Q^{2})$ values and better separation from all other simulated (unrealistic) ones.  \n\nFigure 4 displays plots produced using model 1 for the prediction of the C. lytica biofilm retention index. As can be seen, the correlation is quite good, where $r^{2}=0.82,$ , Figure 4a. In Figure 4b, the AD plot is shown, which confirms that all points are located within $3\\sigma$ of the error limit and, therefore, reaffirms that all coating compositions are within an applicability domain. The third plot in Figure $\\scriptstyle4c$ is from the $y.$ -scrambling experiment, which validates the model developed. Thus, all other generated $y$ -scrambling models have lower $r^{2}$ values and higher errors, which confirms the model developed is robust and is not a chance of correlation.  \n\nHowever, it can be seen that experimental data for C. lytica biofilm retention are clustered into two main groups (Figure 4a). In this case, the use of regression methods for model development is not recommended. Therefore, Model 1 was recalculated using classification methods, where biofilm retention data were converted to binary format $-0$ and 1, where 0 indicates no significant effect and 1 indicates a significant effect. The converted data for C. lytica biofilm retention, retraction, and removal FR properties are shown in SI Table S1. The classification model for C. lytica biofilm retention shows excellent correlation for the training set with an accuracy of $100\\%$ and slightly lower accuracy for the test set,  \n\n![](images/e5bb2e5c76fdfe3f53b3352d508225c71f08fa8aff30e5c838d4aff27215bfec.jpg)  \nFigure 5. Decision trees for classification DT models 1−3 based on one-rule criteria. Classification DT models represented for (a) C. lytica biofilm retention, (b) C. lytica biofilm retraction, (c) C. lytica biofilm removal. For each DT model, the mixture descriptor name and the rule value for the normalized value of the descriptor are shown.  \n\n![](images/563d206e21d9a1fd8efa4098b7c46525a9998111f5c791773c4d786cdaaaa095.jpg)  \nFigure 6. Plots for $H.$ pacif ica biofilm retention model 4: (a) obs vs pred correlation, (b) Williams plot, where yellow dots $\\mathbf{\\sigma}=\\mathbf{\\sigma}$ training set, blue dots $\\mathbf{\\tau}=\\mathbf{\\tau}$ test set; (c) $y.$ -scrambling results, where blue and dark blue dots are the $r^{2}$ and $q^{2}$ of the original model, other dots, yellow and red, are simulated $r^{2}$ and $q^{2}$ values.  \n\n$83\\%$ (Table 3, classification models, Model 1). In addition, Figure 5a shows the classification decision tree model based on the one-descriptor rule, where the value of mixture descriptor Mor18v determines a low and high C. lytica biofilm retention level, providing a great accuracy in prediction.  \n\nFor the C. lytica biofilm retraction model also was developed a regression model, Model 2, and is represented in Figure S1. However, taking into account clustered data, for this property a classification model is developed as well, which gives much better accuracy in comparing to a regression one, Figure S1a and Table 3 (classification models, Model 2).  \n\nThus, a low value of biofilm retraction index indicates good FR properties of the coating. The C. lytica biofilm retraction model (2) consists of one descriptor, $M o r09m^{38}$ (Table 4). The $M o r09m$ descriptor is weighted by the mass of polymer fragment (component) and has a negative sign. In this case, a larger value for this descriptor is associated with a lower C. lytica biofilm retraction index, thus an improved FR property for this bacterium.  \n\nThe classification model for C. lytica biofilm retraction shows excellent correlation for both the training set and for the test set with an accuracy of $100\\%$ (Table 3, classification models, Model 2). In addition, Figure 5b shows the classification decision tree model based on a one-descriptor rule, where the value of mixture descriptor $M o r09m$ determines a low and high C. lytica biofilm retraction level, providing a high degree of predictive accuracy.  \n\nA similar case was observed for Model 3, which represents the model for the C. lytica biofilm removal index, where both regression and classification models were developed. The regression model has almost the same predictive power with only one descriptor, as for Model 2 (Table 3, Figure S2, Figure 5). For this end point, a high removal index is associated with good FR properties. Model 3 has only one descriptor, similarly to the previous model, $M o r09m$ (Table 4), which is the 3DMoRSE descriptor weighted by mass,38 where a higher value for this descriptor corresponds with an increase in the C. lytica biofilm removal index. This very well corresponds to required values of the same descriptor for model 2. Interestingly, the classification model for C. lytica biofilm removal shows excellent accuracy for both the training set and test set, with an accuracy of $100\\%$ (Table 3, classification models, Model 2), and a decision tree model based on one descriptor rule (Figure 5c). In the classification model, the value of mixture descriptor $M o r09m$ perfectly predicts a C. lytica biofilm removal index, where if $M o r09m$ is larger than 0.63, then the C. lytica biofilm removal index is large and vice versa (Figure 5c, Table 3, classification models).  \n\nAt the same time, regression-based Model 3 shows a less accurate prediction, $85\\%$ ${{\\'}_{r}}^{2}\\ =\\ 0.85)$ and has one outlier, coating $\\#27$ (Figure S2a). The AD plot is good (Figure S2b) and $y$ -scrambling (Figure S2c) has a good split between original model and simulated ones.  \n\nModel 4 shows the biofilm retention index prediction for a different marine bacterium, Halomonas pacif ica (Table 3, Figure  \n\n![](images/22ac4d839e306255d6c1902f6ed29cfede5eefbfe568d48a2d657c17c6f666dd.jpg)  \nFigure 7. Plots for $H_{\\sun}$ . pacif ica biofilm removal model 5: (a) obs vs pred correlation, (b) Williams plot, where yellow dots $\\mathbf{\\tau}=\\mathbf{\\tau}$ training set, blue dots $\\mathbf{\\sigma}=\\mathbf{\\sigma}$ test set; (c) $y$ -scrambling results, where blue and dark blue dots are the $r^{2}$ and $q^{2}$ of the original model; other dots, yellow and red, are simulated $r^{2}$ and $q^{2}$ values.  \n\n![](images/df8764691c594507b10e1dd75c6c30a91d43a5e4005b967bbe6339ce5bcdcd35.jpg)  \nFigure 8. Plots for A. amphitrite reattachment model 6: (a) obs vs pred correlation, (b) Williams plot, where yellow dots $\\mathbf{\\tau}=\\mathbf{\\tau}$ training set, blue dots $\\mathbf{\\Sigma}=\\mathbf{\\Sigma}$ test set; (c) $y$ -scrambling results, where blue and dark blue dots are the $r^{2}$ and $q^{2}$ of the original model; other dots, yellow and red, are simulated $r^{2}$ and $q^{2}$ values.  \n\n6). Thus, model 4 has only two descriptors, SPAM and DLS_04 (Table 4). The SPAM descriptor is responsible for the shape38 of structural fragments in the polymer composition. The DLS_04 descriptor is related to drug-like score indices, similar to drug-like filters implemented by Chen et al.51 This index takes into account a set of properties, including the number of H-bond donors, H-bond acceptors, molecular weight, lipophilicity, number of $\\mathsf{C}(\\mathsf{c p}^{3})$ atoms, ratio of hydrogen atoms to nonhalogen heavy atoms, and unsaturation index. Lower values of the DLS_04 index assumes that the chemical is not good for drug-like purposes (i.e., has properties not suitable for interaction with biological systems) and is in accordance with the aim of this study, since a good (low) biofilm retention index suggests a poor interaction with biomass (i.e., mitigates adhesive bonding). Thus, an increase in the value of SPAM descriptor corresponds with a decrease in the H. pacifica biofilm retention index, while the value of the DLS_04 descriptor should be kept low to maintain a good low biofilm retention index level. As can be seen in Figure 6a, this model has no outliers and possesses a good correlation coefficient, $r^{2}=$ 0.86. The AD plot shows all points within $3\\sigma$ of the error limit (Figure $6\\ensuremath{\\mathrm{b}}$ ). The $y$ -scrambling plot on Figure 6c confirms that all other simulated $y$ -scrambling models have much lower $r^{2}$ values than the original model.  \n\nModel 5 represents the prediction for the $H.$ . pacif ica biofilm removal index (Table 3 and Figure 7). Model 5 has only one descriptor, VR2_RG (Table 4), which is based on the geometric topology of the components’ structure.38 To achieve good FR properties, the biofilm removal index should be maintained as high as possible, while the value of the VR2_RG descriptor needs to be high as well. As can be seen Figure 7a, model 5 has no outliers, and the correlation coefficient is satisfactory, $r^{2}=0.76$ . The prediction points related to coatings in the AD plot are within $3\\sigma$ of the error limit (Figure 7b). Moreover, the $y$ -scrambling plot in Figure 7c shows wellseparated values of $r^{2}$ and $\\overset{\\cdot}{q}^{2}$ for the original model from all other simulated y-scrambling models, which confirms the robustness of the developed model.  \n\nThe last two models, models 6 and 7, predict end points for the barnacle species, Amphibalanus amphitrite. Thus, model 6 represents the reattachment index (i.e., the percentage of barnacles that could not attach) prediction for A. Amphitrite, while model 7 represents the adhesion index (i.e., shear force adhesion strength of attached barnacles $\\left(\\mathrm{MPa}\\right)$ ). Model 6 has only one descriptor, $A V S\\_B(p)$ (Table 4), which is a geometrical descriptor weighted by polarizability.21 For good FR properties, the reattachment index needs to be higher, close to 1. On the basis of model 6, the higher the value of the  \n\n![](images/ac0d43b58357eb822bb85dfad6017ea10d0f517981e62d4e352c1fc9eb8a40f6.jpg)  \nFigure 9. Plots for A. amphitrite adhesion model 7: (a) obs vs pred correlation, (b) Williams plot, where yellow dots $\\mathbf{\\tau}=\\mathbf{\\tau}$ training set, blue dots $\\mathbf{\\tau}=\\mathbf{\\tau}$ test set; (c) y-scrambling results, where blue and dark blue dots are the $r^{2}$ and $q^{2}$ of the original model; other dots, yellow and red, are simulated $r^{2}$ and $q^{2}$ values.  \n\n$A V S\\_B(p)$ descriptor, the better the A. amphitrite reattachment index. According to this model, the polarizability index of the coating’s components should be as large as possible. As can be seen in Figure 8a, this model has no outliers, and the correlation coefficient is satisfactory for the training set, $r^{2}={}$ 0.63, while for the validation set, this model shows a very good prediction, $r^{2}=0.91$ . The AD plot shows all points within $3\\sigma$ of the error limit (Figure 8b). Furthermore, the $y$ -scrambling plot in Figure 8c shows much higher $r^{2}$ $\\left(q^{2}\\right)$ values for the original model in comparison to all other simulated $y$ -scrambling models, which confirms the robustness of the model.  \n\nModel 7 represents the adhesion index for the same barnacle species, A. amphitrite (Table 3, Figure 9). Thus, model 7 consists of one descriptor, $M o r09p$ (Table 4), and it represents signal 09, weighted by polarizability, a 3D-MoRSE descriptor.21 For good FR properties, the values of the adhesion index should be low. Then, according to model 7, since the regression coefficient of the $\\mathbf{Mor09}\\mathrm{p}$ descriptor has a negative sign, then this descriptor has to possess a larger value in order to have an adhesion index at a low level. This model has only one outlier (#24) and possesses a good correlation coefficient after its removal, $r^{2}=0.84$ . The validation set’s prediction coefficient is high, $r^{2}~=~0.85$ . The AD plot shows that all the coatings’ prediction points are within $3\\sigma$ of the error limit (outlier $\\#24$ is not shown; Figure 9b). In addition, the $y.$ -scrambling plot confirms that the original model is robust and all other generated $y$ -scrambling models have significantly lower $r^{2}$ values (Figure 9c).  \n\nEach of the above model eqs 1−7 underwent a randomization process, where up to 300 simulations per model were carried out, but none of the identified simulated models showed any chance correlation ( $y$ -randomization). In addition, all models were validated by external test sets and have shown statistical robustness with ${r_{\\mathrm{test}}}^{2}$ within the range $0.63\\substack{-0.94}$ (Table 3). All descriptors that appeared in developed models had no cross-correlation higher than 0.6. This, again, confirms that the developed QSAR models based on the new approach are able to provide a good prediction performance for further rational design of polymer coatings with improved FR properties.  \n\nImportantly, since each applied descriptor is mixture based, it takes into account not only the change in concentration of a particular component but the overall pattern of components mixture, i.e., relative fraction to each other. Even if only one component’s concentration changes, the information on other components’ relative concentration to each other at this step is still taken into account. In this way, the mixture-based descriptor keeps the overall concentration pattern-related information to make predictions. As an example, a significant influence on FR properties, including on C. lytica retention, retraction, and removal indexes plays a concentration of $\\mathrm{CF}_{3}-$ PDMS, where the absence of this component significantly changes the FR property (Table S2, highlighted items). The influence of each component’s concentration was also discussed in our original experimental study,22 while the current study is mainly focused on the overall methodology-related idea test for polymer coating properties prediction, taking into account a combination of factors, structural and concentration-based.  \n\nOn the basis of the findings discussed above, the following structural and physicochemical criteria of the components must be considered when designing coatings with optimal FR properties. In this regard, two polarizability indices showed significant contribution to the C. lytica biofilm retention index and A. Amphitrite attachment index, where in both cases components need to have a high polarizability. Two other activities, C.lyt. biofilm retention and C.lyt. biofilm retraction, showed a strong correlation with the descriptor that weighted by mass of the fragments, which suggests that structural fragments of the components need to have higher mass, while keeping a lower value of van der Waals volume, according to model 1 (C.lyt. retention). Thus, in this study, several descriptors responsible for the size, mass, and volume of the components are shown to be important for obtaining the desired FR properties. Specifically, high values of SPAM (shape and size of polymer fragments), $M o r09m$ (mass of the polymer fragments), and VR2_RG (geometric topology size) resulted in improved FR properties, while values of Mor18v (van der Waals volume) and drug-like score (DLS_04) need to be low. Furthermore, the A. amphitrite adhesion index possesses very specific properties, and it requires certain values of few peculiar physicochemical properties, different from other end points, such as high polarizability of the components’ structures. One more specific index that should be taken into account is DLS_04, which is responsible for drug-like properties. In our case, the value of this index should be lower to diminish the interaction with biomass (i.e., adhesive bonding).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# CONCLUSIONS  \n\nIn this work, a comprehensive structure−activity analysis for a series of polymer coating materials was performed with the application of a novel cheminformatics-based mixture-QSAR approach. A set of 27 polymer coating materials with fouling release activity was investigated. To describe the properties of the investigated polymer coatings, a set of 1200 structural mixture-based descriptors was generated. The experimental and computational data were combined to find the best predictive models, and for this purpose a GA-MLR-based analysis was applied. As a result, seven mixture-QSAR models were developed for various organisms, including bacteria, algae, and barnacles, applying multiple-linear regression methods as well as classification methods. For models 1−3, the classification models showed a better accuracy in prediction. Several structural and physicochemical criteria of the coating components were found to be important for obtaining good, broad-spectrum FR properties. The selected structural and physicochemical criteria include polarizability of the components, several descriptors that are responsible for the size, mass and volume of the components, shape index, and specific druglike index to describe interaction with biomass, based on the components’ structures. The correlation coefficients for the predicted external sets of the models range from $r^{2}=0.63$ to 0.94. All predictions were tested on an external validation set to confirm the models’ performances. The contributions of certain structural properties to the investigated activities were analyzed and discussed. On the basis of developed models, it is now possible to predict an optimal combination of source components to develop a polymer coating material with the desired FR properties. In summary, our results clearly indicate that the developed QSAR models based on a mixture approach are able to provide a good prediction performance for polymer coating materials. This will allow rational design of materials with improved FR properties. The methodology can be applied to predict other properties of polymer coating materials, by developing a mixture-based cheminformatics model for properties of interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 6,
+        "chunk": "# ASSOCIATED CONTENT",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# $\\otimes$ Supporting Information  \n\nThe Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.6b12766.  \n\nTables S1 and S2 and S3 and Figures S1 and S2 (PDF)",
+        "category": " References"
+    },
+    {
+        "id": 8,
+        "chunk": "# AUTHOR INFORMATION  \n\nCorresponding Authors $^{*}\\mathrm{E}$ -mail: bakhtiyor.rasulev@ndsu.edu. \\*E-mail: philip.boudjouk@ndsu.edu. ORCID Bakhtiyor Rasulev: 0000-0002-7845-4884",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# Author Contributions  \n\nThe manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.  \n\nNotes The authors declare no competing financial interest.",
+        "category": " References"
+    },
+    {
+        "id": 10,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nComputer access and financial and administrative support from the North Dakota State University Center for Computationally  \n\nAssisted Science and Technology and the Department of Energy through Grant No. DE-SC0001717 and Office of Naval Research awards N00014-11-1-0032 and N00014-12-1-0641 are gratefully acknowledged.  \n\nREFERENCES (1) Hezinger, A.; Teßmar, J.; Göpferich, A. Polymer Coating of Quantum Dots − A Powerful Tool toward Diagnostics and Sensorics. Eur. J. Pharm. Biopharm. 2008, 68 (1), 138−152. (2) Ju, H.; McCloskey, B. D.; Sagle, A. C.; Wu, Y.-H.; Kusuma, V. A.; Freeman, B. D. Crosslinked Poly (ethylene oxide) Fouling Resistant Coating Materials for Oil/Water Separation. J. Membr. Sci. 2008, 307 (2), 260−267. (3) Licari, J. J. Coating Materials for Electronic Applications: Polymers, Processing, Reliability, Testing; William Andrew, 2003. (4) Stuart, M. A. C.; Huck, W. 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G.; Davies, M. C.; Alexander, M. R.; Winkler, D. A. Modelling Human Embryoid Body Cell Adhesion to a Combinatorial Library of Polymer Surfaces. J. Mater. Chem. 2012, 22 (39), 20902−20906. (34) Yang, J.; Mei, Y.; Hook, A. L.; Taylor, M.; Urquhart, A. J.; Bogatyrev, S. R.; Langer, R.; Anderson, D. G.; Davies, M. C.; Alexander, M. R. Polymer Surface Functionalities that Control Human Embryoid Body Cell Adhesion Revealed by High Throughput Surface Characterization of Combinatorial Material Microarrays. Biomaterials 2010, 31 (34), 8827−8838.   \n(35) Rasulev, B.; Jabeen, F.; Stafslien, S.; Chisholm, B. J.; Bahr, J.; Ossowski, M.; Boudjouk, P. In Predictive Model for Polymer Coating Materials and their Antifouling Activity: Application of Mixture-QSAR Approach, 250th American Chemical Society National Meeting & Exposition, Boston, MA, 2015; pp COMP-218.   \n(36) Jabeen, F.; Rasulev, B.; Ossowski, M.; Chisholm, B. J.; Stafslien, S.; Boudjouk, P. In QSPR/QSAR Studies of Antifouling/Fouling-Release Surface Coatings Containing Quaternary Ammonium Salts, 250th American Chemical Society National Meeting & Exposition, Boston, MA 2015; pp CINF-169.   \n(37) Chemaxon Marvin, 2014; http://www.chemaxon.com.   \n(38) Todeschini, R.; Consonni, V. Handbook of Molecular Descriptors; Wiley-VCH: Weinheim, 2008. (39) Todeschini, R.; Consonni, V.; Mauri, A.; Pavan, M. DRAGON - Software for the Calculation of Molecular Descriptors, Version 6 for Windows; Talete SRL: Milan, Italy, 2014.   \n(40) Ahmed, L.; Rasulev, B.; Turabekova, M.; Leszczynska, D.; Leszczynski, J. Receptor- and Ligand-Based Study of Fullerene Analogues: Comprehensive Computational Approach Including Quantum-Chemical, QSAR and Molecular Docking Simulations. Org. Biomol. Chem. 2013, 11 (35), 5798−5808.   \n(41) Devillers, J. Genetic Algorithms in Molecular Modeling; Academic Press: London, 1996.   \n(42) Rasulev, B.; Saidkhodzhaev, A.; Nazrullaev, S.; Akhmedkhodzhaeva, K.; Khushbaktova, Z.; Leszczynski, J. Molecular Modelling and QSAR Analysis of the Estrogenic Activity of Terpenoids Isolated from Ferula Plants. SAR QSAR Environ. Res. 2007, 18 (7−8), 663−673.   \n(43) Sizochenko, N.; Leszczynski, J. Review of Current and Emerging Approaches for Quantitative Nanostructure-Activity Relationship Modeling: The Case of Inorganic Nanoparticles. J. Nanotox Nanomed 2016, 1 (1), 1−16.   \n(44) Gramatica, P.; Cassani, S.; Chirico, N. QSARINS-chem: Insubria Datasets and New QSAR/QSPR Models for Environmental Pollutants in QSARINS. J. Comput. Chem. 2014, 35 (13), 1036−1044. (45) Gramatica, P.; Chirico, N.; Papa, E.; Cassani, S.; Kovarich, S. QSARINS: A New Software for the Development, Analysis, and Validation of QSAR MLR models. J. Comput. Chem. 2013, 34 (24), 2121−2132.   \n(46) Chirico, N.; Gramatica, P. Real External Predictivity of QSAR Models: How To Evaluate It? Comparison of Different Validation Criteria and Proposal of Using the Concordance Correlation Coefficient. J. Chem. Inf. Model. 2011, 51 (9), 2320−2335.   \n(47) Lin, L. I. K. Assay Validation Using the Concordance Correlation-Coefficient. Biometrics 1992, 48 (2), 599−604.   \n(48) Gramatica, P.; Giani, E.; Papa, E. Statistical External Validation and Consensus Modeling: A QSPR Case Study for Koc Prediction. J. Mol. Graphics Modell. 2007, 25 (6), 755−766.   \n(49) MathWorks, I. MATLAB and Statistics Toolbox Release; The MathWorks: Natick, MA, 2012.   \n(50) Myles, A. J.; Feudale, R. N.; Liu, Y.; Woody, N. A.; Brown, S. D. An Introduction to Decision Tree Modeling. J. Chemom. 2004, 18, 275−285.   \n(51) Chen, G.; Zheng, S.; Luo, X.; Shen, J.; Zhu, W.; Liu, H.; Gui, C.; Zhang, J.; Zheng, M.; Puah, C. M.; Chen, K.; Jiang, H. Focused Combinatorial Library Design Based on Structural Diversity, Druglikeness and Binding Affinity Score. J. Comb. Chem. 2005, 7 (3), 398− 406.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,112 @@
+[
+    {
+        "id": 1,
+        "chunk": "文章编号：  1008-9357(2024)02-0157-14  \n\nDOI:    10.14133/j.cnki.1008-9357.20231230001",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# 高分子材料基因组研究进展  \n\n应斐儿1，  高    梁2，  林嘉平2，  杜    磊2（华东理工大学 1. 科技信息研究所; 2. 材料科学与工程学院, 上海市先进聚合物材料重点实验室,上海 200237）  \n\n摘    要：  改变传统专家系统分析的方法，运用信息学中的科学计量方法，即基于信息学的第四研究范式，客观、全面地分析了高分子材料基因组领域的现状和发展趋势。研究表明，该领域已经进入了“快速发展期”，形成了一些稳定产出的学术团队。目前的研究热点主要集中于机器学习策略在高分子材料中的应用，并且在光电材料、高分子电介质材料、高分子纳米复合材料、高性能复合材料和高分子生物材料上取得了一定的进展。最后，结合目前的研究进展探讨了高分子材料基因组未来的发展方向。  \n\n关键词：  高分子材料基因组；科学计量；研究现状；高分子材料；机器学习中图分类号：  O63 文献标志码：  A",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# Research Progress of Polymer Material Genomes  \n\nYING Feier1, GAO Liang2, LIN Jiaping2, DU Lei2 （1. Institute of Science and Technology Information；2. Shanghai Key Laboratory of Advanced Polymeric Materials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China）  \n\nAbstract:  Polymer material genomes approach can effectively shorten the research and development cycle of new materials and reduce the research and development cost by building infrastructure such as high-throughput calculation, high-throughput experiment and materials big data. As the volume of publications in this field increases, new methods are needed to review and analyze trends in the field of knowledge. Based on the fourth research paradigm of informatics, this review changes the traditional  expert  system  analysis  method  and  uses  scientometrics  to  review  the  research  progress  in  the  field  of  polymer material  genomes.  From  the  five  dimensions  of  publication  trend,  journal  distribution,  research  country  distribution,  highyield authors and academic teams, and co-citation network, this review objectively and comprehensively analyzes the research distribution and status in this field. The field of polymer material genomes has entered a “period of rapid development” and has  formed  some  academic  teams  with  stable  outputs.  At  present,  the  hot  topics  of  research  are  mainly  focused  on  the application of machine learning strategies in polymer materials, and certain progress has been made in photoelectric materials, polymer  dielectric  materials,  polymer  nanocomposites,  high-performance  composites  and  polymer  biomaterials.  Finally, combining with the current research progress, it is proposed to promote the construction of polymer material database, and further develop the polymer material genome method with wider properties and accurate prediction.  \n\nKey words: polymer material genomes；   scientometrics；   research status；   polymer material；   machine learning  \n\n新材料作为当今高新科技和高端制造业发展的基石，对国民经济、国防及其他高新技术产业起重要的支撑作用。传统的材料研发依靠“试错法”，按照“提出假设-实验验证”的模式开展材料研究，研发周期长、成本高，无法满足高性能新材料的研发需求。为加速新材料产业的发展，2011 年提出的“材料基因组计划”(Materials Genome Initiative，MGI) 是指：通过建设材料高通量计算、高通量实验和材料大数据等基础设施，有效缩短新材料的研发周期、降低研发成本[1]。  \n\n“材料基因”一词最早由美国宾夕法尼亚州立大学刘梓葵教授提出，灵感来源于人类基因组计划及相图计算方法的成功应用[2]。2008 年，集成计算材料工程 (Integrated Computational Materials Engineering，ICME) 学科，旨在将计算材料学科的工具集成为一个系统，以加速材料的研发过程[3]。MGI 将 ICME 的理念扩展到整个材料科学、技术与工程链条[4]，变革传统“试错法”的材料研究模式，通过“理性设计-高通量实验-大数据技术”新型材料研发模式显著提高新材料的研发效率。在捕捉到 MGI 释放的重要信息后，欧洲[5]、日本[6, 7]迅速启动类似计划，我国学者在广泛调研后，于 2011 年 12 月召开了以“材料科学系统工程”为主题的香山科学会议，研讨我国如何规划、开展实施自己的材料基因工程计划。2015 年，科技部启动了“材料基因工程关键技术与支撑平台”重点专项，支持开展材料基因工程基础理论、关键技术与装备、验证性示范应用的研究。  \n\n材料科学研究先后历经了 4 种科学范式：第一范式 (经验科学) 以实验试错法为核心，基于研究者在过去实验中所积累的经验开展研究工作；第二范式 (理论科学) 进入了理论模型产生知识的阶段，通过归纳过去的经验发现科学定律；第三范式 (计算科学) 利用计算机模拟原子或者分子的微观状态，密度泛函理论 (DFT)、分子动力学等计算模拟方法在这个时期得到大量应用；第四范式 (数据驱动科学) 从实验和模拟产生的大量数据出发，对未知的数据进行推断和预测[8]。材料基因工程以第四范式为核心，将理论计算、数据库技术、人工智能和实验有机结合，显著提高新材料的研发速度，降低研发成本。高分子材料具备质量轻、耐腐蚀、可加工、可穿戴、电绝缘、成本低等优异特性，通过对重复单元结构、链结构、结晶度、形貌结构的调节，所表现出的多种功能在生物、医学和工程等领域应用广泛。因其复杂的化学和形态参数空间，科研人员往往需要大量专业领域知识的储备、化学经验和直觉，才能建立并探索合理的化学空间，这制约了高分子材料的快速研发。基于材料基因组思想，高分子材料的理性设计和实验验证由三部分组成：(1) 将可能影响材料性能的因素定义为“基因”，通过“基因”编辑或组合获得一系列“虚拟材料”；(2) 建立基于实验数据或模拟数据的性能预测模型，实现对“虚拟材料”的高通量筛选；(3) 合成筛选出的“虚拟材料”，通过性能表征验证筛选结果的可靠性[9]。  \n\n目前，高分子材料基因组领域已经取得了一些成果，国内外学者已从多角度对高分子材料基因组的研究进展进行梳理。Audus 等[10] 认为阻碍高分子信息学广泛应用的障碍是缺乏相关数据库，高分子领域文献中存在大量有价值的科学数据，可以通过自动化数据挖掘及数据库建立加以利用，而数据库建立反过来又可以通过数据驱动助力新材料的设计。Chen 等[11] 回顾了简单线性回归方法和深度学习方法等机器学习方法的特点，介绍了在各个领域使用机器学习辅助材料设计的 9 个典型案例。总结了公开可用的材料数据库、有机分子的特征表示、特征生成的开源工具、分子生成的方法以及材料性质预测的机器学习模型。Sattari 等[12]认为通过材料数据发现隐藏知识、设计具有特定性能的高分子材料已经发展成重要的材料信息学方法，聚焦高分子材料的表征和逆向设计策略，介绍了用于高分子材料逆向设计的高通量虚拟筛选、全局优化和生成模型三种主流数据驱动算法。李云琦等[13] 综述了高分子材料的合成与自组装、机械热性质、光电声磁性质、分离性质和加工性质等方面大数据研究的一些典型进展，强调了多尺度结构信息的数字化和数据缺失是高分子材料大数据研究明显滞后于金属、无机非金属和小分子材料的主要原因。Gong 等[14] 从结构描述符、材料数据库和分子结构标识符三个方面介绍机器学习在高分子材料基因组中的应用，整理了近几年高分子材料基因组领域常用的机器学习算法，根据研究进展梳理了当前领域中的难题与挑战。Du 等[9] 总结了实现高通量性能预测 (表征) 的四种方法，并指出在当前技术条件下，基于数据挖掘寻找代理量的方法和基于机器学习创建预测模型的方法是最具可行性的方法，从这两方面梳理了近年来高分子材料基因组的进展，对高分子材料基因组的发展方向进行了展望。Hou 等[15] 介绍了国内外学者利用计算材料学辅助开发高性能弹性体、光学高分子、能源高分子、导热高分子和生物医用高分子等材料的研究成果，从计算模拟方法、实验等方面提  \n\n出了材料基因组计划未来面临的挑战。  \n\n现有高分子材料基因组领域的研究综述多以专家的定性分析和主观综述为主，在文献梳理的客观性方面略显不足，缺乏文献的可视化分析。随着高分子材料基因组领域发文量的增加，需要新的方法来审查和分析知识领域的趋势。本文采用科学计量学的研究方法，对高分子材料基因组领域研究文献进行系统梳理，探索该研究领域的研究现状，挖掘研究热点，为促进国内相关理论研究与实践发展提供参考。",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1 数据来源与分析方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 1.1 数据来源  \n\nWeb of Science（WoS）核心数据库被认为是具有完整参考文献的文摘型数据库[16]，是科学计量学分析最首选的数据库之一。为保证数据完整性及代表性，以 WoS 核心合集收录的文献数据作为检索源，通过对高分子材料基因组概念的解析，以领域名称“material\\* informat\\*”、“material\\* genome”、“polymer\\* informat\\*”、“polymer\\* genome”和领域研究方法“high-throughput calculation\\*” 、“high-throughput computing”、“high-throughput  experiment\\* ” 、 “high-throughput  characterization ” 、 “high-throughput  screening ” 、 “machinelearning”、“deep learning”、“artificial intelligence”、“active learning”、“active and reinforcement learning”、“AI ” 、 “Bayesian  optimization ” 、 “multi-task  learning ” 、 “transfer  learning ” 、 “Variational  Autoencoder\\* ” 、“reinforcement  learning ” 、 “generative  adversarial  network ” 、 “neural  network\\* ” 、 “polymer\\*  database ” 、“Gaussian process\\*” 等关键词构建数据集，文献类型为“article”或“review”，检索时间截至 2023 年 6 月 30 日。对检索得到的数据集进行进一步筛选，去除重复文献、著录不完整文献以及不符合研究领域的文献，最终获得 718 篇文献。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 1.2 分析步骤  \n\n文献计量分析是一种通过数学、统计等方式对出版物进行广泛分析的研究方法[17]，当应用于科学领域时，又被称为科学计量法，是科技情报领域的重要研究方法之一。知识图谱法则是将某研究领域的科学知识进行可视化从而展示某研究领域的知识基础、研究热点、演化趋势的一种分析方法[18]。本文将收集筛选得到的文献以全记录与引用的参考文献的方式导出纯文本文件，采用科学计量法和知识图谱软件 CiteSpace(版本：6.2.R2) 对高分子材料基因组领域相关文献数据进行可视化分析，由发文趋势、期刊分布、研究国家分布、高产作者与学术团队和共被引聚类5 个维度探究高分子材料基因组领域的研究分布和现状。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2    高分子材料基因组研究分布",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.1 发文趋势  \n\n文献的年度发文数量（图 1（a））及累计发文曲线（图 1（b））能反映学者对研究领域关注的变化。从总体趋势看，高分子材料基因组领域的文献发表数量呈上升趋势，按照增长趋势可以将高分子材料基因组的研究分为两个时期，即“起步探索期”和“快速发展期”。 $1999{\\sim}2017$ 年为“起步探索期”，该阶段文献发表数量相对较少，文献增长速度缓慢，虽已提出“材料基因组”这一概念，但由于材料基因组方法在材料学科领域应用的不成熟和高分子材料结构的复杂性，只有部分学者对高分子材料基因组方法有初步探索。2018 年至今为“快速发展期”，高分子材料基因组领域文献发表数量呈指数增长趋势，2019 年该领域文献发表数量首次突破 50 篇，增长率达到 $120\\%$ ，研究内容更广泛深入，利用机器学习方法进行高分子材料性质预测和设计在这一阶段得到充分发展。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.2 期刊分布  \n\n文献发表的期刊分布可展现研究所涉及的学科类型及不同学科对该选题的关注程度。高分子材料基因组领域中，718 篇文献共涉及 302 种期刊，表 1 为文献在载文数量排名前 10 的期刊和高分子学报 (ActaPolymerica Sinica) 中的分布情况，引入期刊引证报告（JCR）的期刊分区和期刊影响因子（JIF）评价期刊的影响力。文献在期刊中的分布呈现以下特征：(1) 按照 JCR 中对期刊所属类别的划分，该领域研究方向涉及高分子科学、材料科学、化学、物理、纳米科学与纳米技术、复合材料等多学科，学科分布多样。(2) 在发文数量排名前 10 的期刊中，Polymers 为一本国际开放获取的高分子科学期刊，是该领域发文数量较多的期刊，占文献总数的 $5.15\\%$ 。此外，Macromolecules 和 Polymer 均为高分子领域具有一定影响力的期刊，关注高分子学科各方面原创性、基础性和有影响力的研究，这些高影响因子期刊说明高分子材料基因组作为高分子领域的前沿方法已经获得了广泛关注。  \n\n![](images/dc65c4f3832d7914b142382d6455b0e45563910d585756e7b72919fc2e952728.jpg)  \n图 1    高分子材料基因组领域 (a) 年度发文数量和 (b) 累计发文数量曲线  \nFig. 1    (a) Number of annual publications and (b) cumulative number of publications in the field of polymer material genomes  \n\n表 1    高分子材料基因组领域文献在期刊中的分布情况  \nTable 1    Distribution of literature in the field of polymer material genomes in journals   \n\n\n<html><body><table><tr><td> Rank</td><td>Journal title</td><td>Record count</td><td>Percentage/%</td><td>JCR</td><td>JIF(2022)</td></tr><tr><td>1</td><td>Polymers</td><td>37</td><td>5.15</td><td>Q1</td><td>5</td></tr><tr><td>２</td><td>Computational Materials Science</td><td>26</td><td>3.62</td><td>Q2</td><td>3.3</td></tr><tr><td>3</td><td>ACS Applied Materials & Interfaces</td><td>20</td><td>2.78</td><td>Q1</td><td>9.5</td></tr><tr><td>4</td><td>Journal of Chemical Physics</td><td>17</td><td>2.36</td><td>Q1</td><td>4.4</td></tr><tr><td></td><td>Macromolecules</td><td>15</td><td>2.09</td><td>Q1</td><td>5.5</td></tr><tr><td>６</td><td> Journal of Applied Polymer Science</td><td>14</td><td>1.95</td><td>Q2</td><td>3</td></tr><tr><td>７</td><td>Composite Structures</td><td>13</td><td>1.81</td><td>Q1</td><td>6.3</td></tr><tr><td>8</td><td>Polymer</td><td>13</td><td>1.81</td><td>Q1</td><td>4.6</td></tr><tr><td>9</td><td>NPJ Computational Materials</td><td>12</td><td>1.67</td><td>Q1</td><td>9.7</td></tr><tr><td>10</td><td>Composites Science and Technology</td><td>11</td><td>1.53</td><td>Q1</td><td>9.1</td></tr><tr><td>11</td><td>Acta Polymerica Sinica</td><td>５</td><td>0.70</td><td>Q3</td><td>1.9</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.3 国家分布  \n\n选取累计文献发表数量前十的国家/地区作为样本，引入文献被引频次 (Citation) 和合作网络中的中介中心性 (Centrality) 这两个指标分析各国在高分子材料基因组研究领域的学术产出能力 (表 2)。文献被引频次可以反映国家/地区发文的影响力，中介中心性则代表该国家/地区在合作网络中的关键程度 (一般认为网络中中介中心性大于 0.1 的节点是关键节点)。在文献总量和文献被引频次上可以看出美国作为材料基因组计划概念的提出者在该领域深耕已久，文献数量和文献影响力处于世界前列，同时在合作网络中也占据重要位置。我国虽然在材料基因工程领域起步稍晚，但在科技部“材料基因工程关键技术与支撑平台”重点专项、国家自然科学基金等相关项目的支持下，自2019 年起发文数量攀升，目前也具备较强的科研产出能力。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 2.4    高产作者及学术团队  \n\n高产作者即特定研究领域的领军人物，其突出成果代表了该领域的研究水平和方向。在高分子材料基因组领域中，署名作者共 2 465 位。根据普莱斯定律，在同一主题中，半数的论文为一群高生产能力作者所撰，这一作者集合的数量约等于全部作者总数的平方根，即 $N=0.749\\sqrt{n_{\\mathrm{max}}}$ 。其中 $n_{\\mathrm{max}}$ 为最高产作者发表的论文数量， $N$ 为核心作者的产量阈值。由公式计算可得高分子材料基因组核心作者的最低发文阈值为 4 篇，共有73 位作者满足条件，将其界定为高分子材料基因组候选高产作者。  \n\n表 2    高分子材料基因组领域文献在国家/地区中的分布情况  \nTable 2    Distribution of literature in the field of polymer material genomes among countries/regions   \n\n\n<html><body><table><tr><td>Rank</td><td>Country/Region</td><td>Record count</td><td>Citation</td><td>Centrality</td></tr><tr><td>1</td><td>USA</td><td>219</td><td>5826</td><td>0.49</td></tr><tr><td>２</td><td>China</td><td>177</td><td>3182</td><td>0.39</td></tr><tr><td>3</td><td>Japan</td><td>53</td><td>922</td><td>0.13</td></tr><tr><td>4</td><td> India</td><td>41</td><td>451</td><td>0.13</td></tr><tr><td>4</td><td> Iran</td><td>41</td><td>664</td><td>0.17</td></tr><tr><td>6</td><td>Germany</td><td>37</td><td>2767</td><td>0.15</td></tr><tr><td>７</td><td>United Kingdom</td><td>33</td><td>810</td><td>0.06</td></tr><tr><td>８</td><td>South Korea</td><td>28</td><td>316</td><td>0.05</td></tr><tr><td>9</td><td>Canada</td><td>21</td><td>270</td><td>0.09</td></tr><tr><td>10</td><td>Turkiye</td><td>20</td><td>212</td><td>0.09</td></tr></table></body></html>  \n\n进入 20 世纪，科学研究的最基本组织已从个体为主转向学术团队为主，科学合作已成为科学研究的主要形式。为进一步挖掘具有一定学术影响力的研究团队，将每篇文献中标注的所有作者都定义为该篇文献的作者，借助 CiteSpace 可视化分析软件进行作者合著网络的分析，设置显示发文数量在 4 篇以上的作者，生成作者合著图谱，快速分析该研究领域的主要研究人员和团队合作关系。图 2 所示为高分子材料基因组研究领域已形成的一些主要学术研究团队。  \n\n![](images/32c9c74676579678640eba4fe52c965e0cc51fa36315b4d199cf93b8175cef4d.jpg)  \n图 2    高分子材料基因组领域的合著者网络图谱（图谱节点代表作者，节点越大，作者发表的文章越多；节点之间的线条表示作 者之间的合作关系） Fig. 2    Co-occurring authors network in the field of polymer material genomes (The node represents the author, and the larger the node, the more the author has published; The lines between nodes represent cooperative relationships between authors)  \n\n佐治亚理工学院 Ramprasad 团队是合著网络中发表文献数量最多的学术研究团队，该团队旨在开发和应用计算和机器学习工具，以加速高分子电介质材料的发现。Ramprasad 课题组[19] 提出了一种合理的五步设计策略，可有效筛选和识别用于电容储存应用的先进高分子介电材料。为了更快获取高分子的带隙和介电常数，他们还基于 DFT 计算生成的数据构建机器学习模型加速高分子电介质设计，通过机器学习得以了解不同结构片段的特性，并准确预测高分子电介质的带隙和介电常数[20]。此外，Ramprasad 等收集了通过计算(带隙、介电常数、折射率和活化能) 和实验 (玻璃化转变温度、溶解度参数和密度) 获得的高分子数据集，开发了一种从原子结构到拓扑结构特征的指纹方案，通过将指纹 (或特征) 映射到属性来训练机器学习模型，并将这些模型整合到一个名为 Polymer Genome(www.polymergenome.org) 的在线平台中[21]。  \n\n本课题组针对耐高温树脂的设计建立高分子材料基因组方法，从“基因-结构-性能”构效关系出发，根据性能需求，设计、选取不同结构的“基因”，产生候选结构，进行性能预测和高通量筛选，显著提高高分子材料的设计效率。运用该方法，我们设计了系列先进复合材料基体树脂，如具有高热分解温度和低固化放热焓的含硅芳炔树脂(PSA)[22]、兼具高耐热性和高韧性的聚酰亚胺树脂(PI)[23]、高耐热性且易加工的热固性PI 树脂[24]等。本课题组作为国内首家开展高分子材料基因组研究的学术团队，目前已经建立国内首个高分子材料基因组研发平台 AI plus Polymers (https://polymergenome.ecust.edu.cn)[25]。该平台包含树脂结构性能数据库和基团间化学反应数据库，在此基础上，创建了面向高分子 10 余种性能的机器学习预测模型，使平台具备数据检索、性能预测、配方优化等多项功能。借助 AI plus Polymers，我们设计研制了兼具优异韧性和耐高温性的新型聚硅炔酰亚胺(PSI) 树脂，其力学性能与聚酰亚胺相当，加工和耐热性能均优于聚酰亚胺[26]。  \n\n在合著网络中，还有许多学术团队对高分子材料基因组领域的研究做出了贡献，如：Diaz 课题组通过数据库挖掘高分子材料的定量结构-性能关系 (QSPR) 模型，从而预测高分子材料的力学性能[27, 28]、折射率[29] 等其他性能；Li 和 Tao[30] 针对高分子玻璃化转变温度，比较了不同机器学习模型在该体系下取得的结果；Brison课题组[31-33]构建了面向高分子纳米复合材料分析与设计的材料基因组方法，并搭建了 NanoMine 平台管理和存储高分子纳米复合材料的各种实验数据；Saeki 课题组[34, 35] 通过机器学习模型筛选设计了有机太阳能电池共轭高分子结构；Patra 课题组[36, 37] 利用机器学习算法加快了软物质材料的设计。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3    高分子材料基因组研究现状  \n\n为挖掘高分子材料基因组领域目前的研究现状和研究热点，对 2011 年以来发表的文献绘制共被引聚类图谱，并归纳出该领域进入“快速发展期”后的 7 个研究主题 (图 3)。表 3 中按照核心论文 (Core paper) 数列出了 7 个主题所代表的研究关键词 (Research keywords) 和参考文献平均年份 (Mean year)。通过对聚类信息的关键词、施引文献和被引文献的解读，发现目前的研究热点主要集中于机器学习方法在高分子材料中的应用（主题#1）。基于“理性设计-高通量实验-大数据技术”材料研发模式，高分子材料基因组方法在新型高分子材料的研究设计中也已经形成了一定规模的研究，主题#2、#3、#4、#5、#6、#7 体现了高分子材料基因组方法在高分子光电材料、高分子电介质材料、高性能高分子纳米复合材料、高性能高分子复合材料基体树脂、高分子生物材料这几种材料设计中的应用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3.1    机器学习在高分子材料基因组的应用  \n\n表 3 的主题#1 体现了机器学习方法在高分子材料基因组中的应用。从历史数据中挖掘潜在规律，对未知数据进行分类或预测，是高分子材料基因组研究方法的重要组成部分，诸多学者也在该方向对高分子材料基因组展开了研究综述[11, 14, 38, 39]。基于机器学习方法的高分子材料设计和性能预测的一般工作流程包括 3个主要步骤：用一组描述符或特征在数据集中表示材料，在描述符和目标属性之间建立映射模型，作出材料预测并对其真实性能进行验证。  \n\n在构建既能机器易读又能准确描述物质结构信息的分子结构描述符时，Lin 等[40] 在SMILES[41] 的基础上提出了一种专为高分子设计的分子结构表达系统 BigSMILES，将重复单元由大括号括起来以表示高分子片段，以键合描述符表述不同重复单元间的连接形式，该系统的机器可读性和广泛适用性很好。随着深度学习的发展，除了将分子结构转化为线性文本符号外，还可以将其通过图神经网络 (GNN) 转化为独特的输出向量来表示[42]。Aldeghi 等[43] 开发了分子集成的图形表示和相关的 wD-MPNN 架构捕捉高分子材料的关键特征，如链结构、单体化学计量数和聚合度，与现有方法相比其准确性更高。在对多个目标同时优化时，Gurnani 等[44]构建了多任务高分子 GNN 架构 (polyGNN)，从高分子重复单元中学习重要特征，该方法预计可以实现高分子信息学领域更复杂、更大规模的筛选。  \n\n将机器学习方法集成到高分子系统研究的多尺度分子模拟方法中，特别是在粗粒化模拟的背景下，存在  \n\n![](images/b152f2093e0b23743cb40963975d502211063d55dd578a9b84b31e35a2536aa5.jpg)  \n图 3 $2011{\\sim}2023$ 年高分子材料基因组文献共被引图谱（共被引网络共包含 607 个节点，1 387 条边，聚类模块值 $\\varrho$ 为 0.838 7(大于 0.5)，聚类平均轮廓值 $s$ 为 0.901 8(大于 0.7)，聚类结构显著）  \n\nFig. 3    References co-citation network with corresponding topic related to studies on polymer material genomes (2011—2023) (The co-cited network contains 607 nodes and 1 387 edges, the clustering module value $\\boldsymbol{\\mathcal{Q}}$ is 0.838 7(greater than 0.5), the clustering average contour value $S$ is 0.901 8(greater than 0.7), and the clustering structure is significant)  \n\n表 3    高分子材料基因组领域研究主题关键词  \nTable 3    Research topic keywords in the field of polymer material genomes   \n\n\n<html><body><table><tr><td>Topic ID</td><td>Research keywords</td><td>Core paper</td><td>Mean year</td></tr><tr><td>#1</td><td>Benchmarking machine learning model; Automated copolymer synthesis; f-19 mri agent; Learning-guided discovery; Polymer informatics</td><td>69</td><td>2019</td></tr><tr><td>#2</td><td>Polymer genome; Efficient multiscale optoelectronic prediction; Polymer science; Organic solar cell; Targeted sequence design</td><td>47</td><td>2018</td></tr><tr><td>#3</td><td>Machine learning strategies; Structure-property relationship; Polymer sequence design; all-organic polymer dielectrics; Recent progress</td><td>25</td><td>2018</td></tr><tr><td>#4</td><td>Centric nanocomposites design; Extreme condition; Using syntax-directed variational Autoencoder; Polymer nanocomposite data; Curation frameworks access</td><td>15</td><td>2018</td></tr><tr><td>#5</td><td>Polymer genome approach; New method; Learning enhanced material; Silicon-containing Arylacetylene resin; Learning-assisted design</td><td>7</td><td>2019</td></tr><tr><td>#6</td><td>Learning-enabled design; Self-assembled monolayer; Protein resistance; Antifouling Polymer brushe; Future biomaterials discovery</td><td>7</td><td>2018</td></tr><tr><td>#7</td><td>Synthesis; Heat-resistant silicon-containing arylacetylene resin; Design; Silicon-containing Fluorenylacetylene resin; High thermal stability</td><td>4</td><td>2018</td></tr></table></body></html>  \n\n巨大的开发潜力。Wang 等[45] 提出了将粗粒化分子动力学 (MD) 与机器学习结合来设计固态高分子电解质的策略。他们先将高分子的化学结构 (全原子模型) 转化为粗粒化模型，再通过粗粒化 MD 模拟计算当前模拟体系中 Li 离子传导率；接着，通过贝叶斯优化找出 Li 离子传导率更优的粗粒化模型，循环迭代，最终获得性能最佳的粗粒化模拟体系及其对应的粗粒化参数。虽然能将全原子模型转化为粗粒化模型，但是目前该技术仍难以利用已知的粗粒化参数反向推导出对应的全原子模型，无法直接获得高 Li 离子电导率的固态高分子电介质材料，但这种策略下获得的最佳粗粒化参数仍然能间接为固态高分子电介质材料的结构设计和合成提供参考和借鉴。  \n\n利用预训练模型来完成另一项任务的迁移学习，已经成为越来越流行的机器学习框架。在处理有限训练集的情况下，需要迁移学习来获得特征和相关属性的预训练模型，与小数据集机器学习模型相比，可以在预测精度上有更突出的表现。例如，针对导热系数 ( ) 实验数据集有限的问题， ${\\sf W}{\\sf u}$ 等[46] 首先寻找与导热性相关的代理性能作为替代设计目标，通过贝叶斯设计生成虚拟化学结构库，为获得可靠的预测模型提供了足够的数据。在此基础上，使用迁移学习技术开发了λ的神经网络模型，在以玻璃化转变温度和熔化温度为目标产生的虚拟库上筛选候选材料，并进行实验室合成和热物理性能的实验表征。迁移模型的平均绝对误差(MAE) 达到 $0.0204\\mathrm{W}/(\\mathrm{m}\\cdot\\mathrm{K}).$ ，与直接使用实验数据进行模型训练相比，MAE 降低了 $40\\%$ 左右，大大提高了预测准确性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.2    高分子材料基因组在设计光电材料中的应用  \n\n表 3 的主题#2 体现了高分子材料基因组在高分子光电材料的设计以及性能预测中的作用。共轭高分子具有优异的光电性质和可加工性，被广泛用于有机光伏 (OPV) 器件的制备。有机光伏器件通常由 p 型高分子 (或分子) 和 $\\mathbf{\\eta}_{\\mathrm{~n~}}$ 型富勒烯 (或非富勒烯) 分子组成，尽管材料信息学在数据科学方面取得了快速进展，但OPV 材料的数据驱动分子设计仍然具有挑战性。Saeki 课题组[34] 从文献中手工收集了大约1 000 个实验参数，包括能量转化效率 (PCE)、分子量和电子特性，利用人工神经网络 (ANN) 和随机森林 (RF) 对高分子-富勒烯有机光伏应用的共轭分子进行筛选。由于 ANN 模型通常需要数百万个数据条目来构建一个准确模型，实验中 RF 模型显示出更高的准确性，因此，Saeki 等最后通过 RF 模型、专家经验和时间分辨微波电导率（TRMC）分析相结合提出了一种设计高分子 (主链和侧链) 的替代方法。随后，Saeki 课题组[35] 还利用基于实验数据集的 RF 模型对由供体和受体单元组合产生的 200 932 种共轭高分子进行了虚拟筛选，证明了机器学习方法可以利用相对较少的实验数据点和筛选大量的分子结构来开发OPV。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3.3    高分子材料基因组在设计电介质材料中的应用  \n\n表 3 的主题#3 体现了高分子材料基因组在设计电介质材料中的应用。相较陶瓷等无机材料，高分子材料具有成本低、化学稳定性强、柔韧性好等特点，已成为广泛使用的商用电介质材料。然而，高分子材料的介电常数较小，存在改进空间。  \n\nRamprasad 课题组[19] 提出了一种合理的分层建模设计策略，可有效筛选和识别用于电容储存应用的先进高分子电介质。该设计策略分为 5 个步骤：(1) 将高分子电介质材料中常见的 7 种化学结构作为“基因”，以4 个片段构建线性高分子链的重复单元，通过组合进行化学空间探索；(2) 利用 DFT、密度泛函微扰理论（DFPT）和等效介质理论计算候选结构的带隙和介电常数，筛选获得复合条件的“基因”组合；(3) 由向下选择的重复单元组成高分子的三维结构/形态预测；(4) 再次利用 DFT、DFPT 和等效介质理论计算三维结构的性能； (5) 候选高分子的合成和表征。通过逐步模拟搜索策略，获得了 3 种最有应用价值的“基因”组合。为了加速材料设计，Ramprasad 课题组[47] 从通过第一性原理计算生成的数据中提取规律，构建了通过输入高分子结构来预测带隙和介电常数的机器学习模型。引入遗传算法，他们生成了 300 个随机结构的初始种群，结合了杂交、精英保留和突变，产生“后代”结构。每一代适应度得分最高的高分子结构被列入最佳方案列表，最终，这个列表将包含最接近目标性能的高分子结构。  \n\n对于超高功率密度和高温下工作的应用场景，例如运输系统、航空航天、钻井和天然气勘探中的电气化，对能够耐受巨大电场和高温的高分子电介质材料的需求也在不断增加。Ramprasad 课题组[48] 提出了一种耐极端温度高能量密度的高分子电介质的设计：(1) 进行全面的温度相关击穿实验以获得高质量的击穿强度$(E_{\\mathrm{bd}})$ ；(2) 选择铝电极的带隙、电子注入势垒和内聚能密度 3 种性质来筛选高 $E_{\\mathrm{bd}}$ 的高分子，玻璃化转变温度和介电常数作为热稳定性和介电极化的代理量；(3) 使用先前开发的机器学习模型预测 13 000 种全有机高分子的 5 个代理量性质[21, 49] ，筛选出 9 种满足性能要求和合成可及性的代表性高分子，为合理设计耐极端温度高能量密度的高分子电介质提供了途径。  \n\n纯高分子的介电常数往往较低，可以通过添加无机填料来改善性能。填料的尺寸和介电性会对高分子基复合材料的介电击穿性能产生影响，基于聚酰亚胺 (PI) 和聚偏氟乙烯 (PVDF) 两种代表性高分子，Yue 等[50]考虑了影响高分子基复合材料击穿强度的 3 个最重要变量 (填料介电常数、填料尺寸和填料含量)，对 504 组数据进行了高通量随机击穿模拟，并将模拟结果作为机器学习数据集，获得高分子基复合材料击穿强度预测。结合经典的介电常数预测公式，对高分子基复合材料的储能密度进行了预测，并通过介电常数和击穿强度实验验证了预测准确性。这项工作为电容储能应用中高能量密度高分子基复合材料的设计和制造提供了参考。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 3.4    高分子材料基因组在设计高分子纳米复合材料中的应用  \n\n表 3 的主题#4 体现了高分子材料基因组在设计高分子纳米复合材料中的应用。高分子纳米复合材料被定义为含有纳米颗粒的有机基体材料，实验表明，通过在基体中加入少量填料，高分子纳米复合材料的介电性能、力学性能和光学性能都比其基体体系有显著提高[51]。  \n\n定制纳米复合材料以满足特定应用需求仍然是一项具有挑战性的任务，因为纳米复合材料的组成 (即高分子、纳米颗粒和表面改性剂的选择) 和微观结构 (即颗粒的分散和几何排列) 的设计空间巨大，纳米颗粒周围区域的界面特性建模给设计过程带来了额外的复杂性，并且需要昂贵的计算模拟。因此，以前设计高分子纳米复合材料的尝试都集中在寻找固定成分组合的最佳微观结构上。Iyer 等[52] 提出了一个以数据为中心的设计框架，通过混合变量贝叶斯优化同时确定最佳成分和微观结构。该框架将实验数据与最先进的相间建模、微观结构表征和重建以及机器学习技术相结合。潜在变量高斯过程量化了由定性和定量材料设计变量组成的混合变量设计空间中缺乏数据的不确定性。电绝缘纳米复合材料的设计是一个多准则优化问题，其目标是最大化介质击穿强度，同时最小化介电常数和介电损耗，在数十次迭代中识别帕累托前沿（Paretofrontier），表明介电性能之间的权衡，说明以数据为中心的设计有效地将实验数据与贝叶斯优化模拟相结合，是工程材料系统设计的有效方法。  \n\n相较机器学习模型，深度学习往往具有更好的特征学习能力。Wang 等[51] 提出了一种基于数据驱动和深度学习的方法来建模聚合物纳米复合材料的结构-性能关系的模型。首先，分析 NanoMin 存档的实验数据，采用微观结构重建方法和有限元分析相结合的方法生成了一组模拟数据，探索得到有关界面相、体积分数和分散度之间的相互作用关系。其次，使用深度学习方法建立定量的结构-属性关系，提出了一种多任务卷积神经网络，使用有限元模拟生成大小为 11 000 的计算数据集，利用微观结构图像预测聚合物纳米复合材料的力学性能。结果表明，所提出的深度学习模型对玻璃模量 (glassy modulus) 的预测精度提高了 $45.2\\%$ ，橡胶模量(rubbery modulus) 提高了 $34.2\\%$ ，tan $\\delta$ 的预测精度提高了 $19.7\\%$ 。此外，通过修改深度学习模型的输入，Wang等还证明了提出的深度学习方法是一种无特征工程、高精度、可泛化和可解释的模型。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 3.5    高分子材料基因组在设计高性能复合材料基体树脂中的应用  \n\n表 3 的主题#5 和主题#7 均体现了高分子材料基因组在设计高性能树脂中的应用。航空航天和电子信息等领域的发展对耐热高分子的需求日益增加，耐热高分子及其复合材料的研究引起了人们的广泛关注[53, 54]。含硅芳炔树脂（PSA）是一种无机-有机杂化高分子，固化后PSA 形成高度交联的网络，表现出优异的耐热性能，作为高性能高分子复合材料的基体具有很大的潜力[55-57]。然而，材料的不同性能之间往往存在相互制约的关系，树脂耐热性的提高往往伴随着可加工性的下降[58, 59]。Zhu 等[22] 开发了一种材料基因组方法，提出了一种基于不同属性关键特征的两步筛选策略：(1) 用树脂中最弱键的解离能 (BDE) 代理热分解性能，以 $\\mathrm{Si}{-}\\mathrm{CH}_{3}$ 中硅碳键的 BDE 为阈值，通过 DFT 计算筛选出 BDE 大于阈值的候选 PSA 结构；(2) 用分子连接指数法计算的零切黏度和以 DFT 计算得到的能带间隙代理加工性能，以零切黏度小于 $0.5\\mathrm{Pa\\cdots}$ (树脂传递模塑工艺对黏度的要求) 且能带间隙最小为标准，筛选出最佳结构并将其命名为 PSNP。除了理论计算和模拟之外，机器学习是对巨大的化学空间进行有效预测的更有效方法。Zhang 等[60] 建立了用于评估 PSA 加工性能和耐热性能的机器学习模型：(1) 将二炔单体和二氯硅烷单体分别定义为 A 和 B“基因”，将这些“基因”组合成 368 种候选树脂；(2) 定义氮气气氛下的热失重 $5\\%$ 时的温度 $T_{\\mathrm{d}5}$ ）表示树脂的耐热性能，室温下的 $\\lg\\eta(\\eta$ 为黏度）表示加工性能，从数据库中获取数据并使用多层感知器 (MLP) 算法训练预测模型。利用 MLP 模型分别预测了 368 种候选树脂的 $\\lg\\eta$ 和 $T_{\\mathrm{d}5}$ 的加工性能和耐热性能，加权获得 10 种最佳“虚拟材料”；(3) 制备并表征了一种含有 2,7-二乙基萘和二氯甲基乙烯硅烷的易于合成的优选树脂 (PSNP-MV)。实验和理论模拟结果表明，该树脂具有较好的低黏度加工性能和良好的耐高温性能，验证了材料基因组方法的筛选结果。  \n\n环氧树脂是应用广泛的树脂基体之一。航空航天领域中的复合材料，如薄膜太阳帆等大型空间结构的展开支撑系统，需满足轻质量、高可靠性、高刚度、大形变的需求。然而，强度、模量、韧性等多种力学性能相互制约，很难用传统试错法获得兼具以上性能的环氧树脂。Hu 等[61] 提出了一种机器学习辅助材料基因组方法快速设计具有优异力学性能 (高拉伸模量、高拉伸强度和高韧性) 的新型环氧热固性材料：(1) 利用图卷积神经网络结合分子描述符与分子图表示方法捕获环氧结构的基因特征，基于 Flory 经典凝胶理论开发了可描述聚合物交联特性的交联密度描述符，建立了环氧树脂拉伸强度、拉伸模量、断裂伸长率、玻璃化转变温度的机器学习模型；(2) 定义合成环氧树脂的两种反应物环氧化物和胺为“基因”，通过各种排列组合，形成了24 万种候选的环氧树脂结构；(3) 通过机器学习性能预估模型，对海量虚拟结构进行了高通量预测和筛选，得到了 10 余种兼具高模、高强、高韧特性的新型环氧树脂结构。实验验证表明，在保持高模、高强的同时，新型环氧树脂断裂伸长率可达 $6.7\\%$ ，有效解决了环氧树脂的脆性难题。  \n\n氰酸酯树脂因其优异的尺寸稳定性及与碳纤维增强材料良好的界面相容性，可用作航空航天结构复合材料的基体树脂。 $\\mathrm{\\DeltaXu}$ 等[62] 提出了一种材料设计策略，以发现具有低吸湿性、低线性热膨胀系数和高拉伸模量的氰酸酯树脂：(1) 将氰酸酯基团的对碳、间碳和正碳分别设为#1、#2 和#3，将与其相连的基团分别称为#A、#B 和#C“基因”；(2) 从化学数据库和文献中收集数据，通过拆分化学结构产生了 256 个# A“基因”、17 个#B“基因”和 46 个#C“基因”，通过基因组合和结构清洗，获得了 573 591 个候选聚合物空间；(3) 利用图学习算法对化学结构进行数字化表示以便计算机读取，经高斯过程回归方法分别构建吸湿率、热膨胀系数和拉伸模量的性能预测模型，获得了结构与性能关系的高精度映射。通过机器学习模型，筛选了一系列具有低吸湿性、低线性热膨胀系数和高拉伸模量的“虚拟结构”，并通过计算机模拟和实验验证了其具有较强的综合性能。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# 3.6    高分子材料基因组在设计生物材料中的应用  \n\n表 3 的主题#6 体现了高分子材料基因组在设计生物材料中的应用。“生物材料”一词指的是与生命系统密切接触的一种用途极其广泛的材料[63]，相较其他功能高分子材料，设计并制备具有特定功能的新型生物高分子材料是新材料开发中的难点。  \n\n防污材料在一定程度上抵抗蛋白质、细胞、细菌和生物体的有害吸附，Liu 等[64] 构建了一个预测聚合物蛋白质吸附量的模型，以发现新型防污聚合物刷。他们从文献收集了 14 个两性离子、14 个亲水性聚合物刷的单体结构和 94 个蛋白质吸附数据点；基于描述符建立了人工神经网络模型 (ANN)，发现现有聚合物刷的潜在防污性能以及聚合物刷结构-防污性能之间的关系；在 ANN 模型的基础上，使用因子分析法，将描述符转化为官能团，建立了基于官能团的支持向量回归 (SVR) 模型，用以设计新型防污聚合物刷。基于 ANN 和 SVR模型，Liu 等筛选了三种重新利用的聚合物刷和三种新设计的聚合物刷，它们都对未稀释的人类血清和血浆中的蛋白质吸附具有优异的表面抗性，实验验证结果与模型的预测值高度一致，证明该机器学习模型可用于新型高分子防污刷的确定、再利用和设计。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 4    结论与展望",
+        "category": " Conclusions"
+    },
+    {
+        "id": 20,
+        "chunk": "# 4.1    结　论  \n\n本文以 WoS 核心合集中高分子材料基因组领域的科技文献为研究对象，借助科学计量学和可视化知识图谱方法分析领域文献的分布现状和研究热点，具有一定参考价值及借鉴意义。  \n\n从研究分布来看，通过科学计量和作者合著网络可以发现：(1) 高分子材料基因组的研究文献已呈现指数增长模式，进入了快速发展期；(2) 高分子科学、材料科学、化学、物理、纳米科学与纳米技术、复合材料等多学科对该选题的关注程度高，高分子材料基因组作为高分子材料科学中的前沿方法获得了广泛关注；(3) 美国作为最先启动材料基因组计划的国家处于发文数量和国际影响力的顶峰，我国在高分子材料基因组领域中也存在较强的学术产出能力；(4) 国内外高分子材料基因组领域均存在成果显著且稳定的学术团队，构成了此领域的核心研究力量，但合著网络密度低，存在研究主体相互之间合作不紧密的现象。  \n\n从研究现状来看，通过共被引聚类和对聚类关键词、施引文献、被引文献的解读归纳了目前持续活跃的6 个研究热点。目前的研究热点仍然集中在机器学习策略在高分子材料的应用上，特征或描述符的选择、机器学习结合多尺度分子模拟方法、小数据集机器学习成了目前的研究热点。从具体研究的材料类型来看，大部分研究内容集中在光电材料、电介质材料、高分子纳米复合材料、高性能复合材料和高分子生物材料上，这与领域核心学术团队的产出也有很大关系。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 21,
+        "chunk": "# 4.2    展　望  \n\n（1）推动高分子材料数据库的建设：机器学习模型的数据点数量和质量可以决定模型的性能。收集高分子材料数据点的方法共有 4 种，即从现有数据库中收集数据、从文献中收集数据、从计算模拟或理论模型中收集数据以及从实验中收集数据。目前，高分子材料可用的数据点仍然主要集中在线性聚合物上，对于一些新的聚合物甚至没有任何可用的数据库，这要求推动高分子材料数据库的建设，构建高分子数据分享平台，文献发表的过程中要求作者提供研究相关的数据集。虽然关于高分子的研究论文数量在不断增加，累积的数据已经相当丰富，但采用手动的方式摘录文献数据非常耗时费力，自然语言处理技术可以帮助科研人员从文献文本中提取材料组成、参数性能等信息，以便数据收集和帮助科研人员更好地理解和利用大规模材料科学文本数据。基于计算模拟获得数据相对容易，大量的材料属性目前已可以较为可靠地计算出来，但计算低成本、模拟高精度的第一性原理计算仍然十分有限。基于实验的材料数据库必须按照一定标准进行组织，值得注意的是，科研人员往往总是倾向报道正面的研究结果，而在高分子材料基因组方法中，负面的实验数据也同样重要，因此要鼓励科研人员同时分享正面和负面的实验数据。此外，高通量实验方法作为材料基因组的一部分在高分子领域还没有很多应用，通过高通量实验一次性获得批量的样品数据，不仅可以从中筛选出符合性能要求的新型材料，还可以为高分子材料基因数据库提供大量可靠的实验数据结果，该方法是一条极具潜力的筛选途径。  \n\n（2）进一步发展包含性能更广且预测精确的高分子材料基因组方法：高分子材料基因组方法有效提高了新型高分子的设计和性能预测效率，根据共被引分析可知目前的高分子材料基因组领域研究内容集中，往往针对特定类型的高分子材料。这一方面是因为数据集限制，另一方面也是因为高分子材料具有复杂的多层次结构，在高分子材料基因组方法的选取上，需要依据不同的体系选择不同的描述符，能够适用于所有体系的方法不存在，因此建立预测精度高、普适性强、性能预测更广泛的高分子材料基因组大模型是所面临的主要问题。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 22,
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ITOH M, IWATA K, ISHIKAWA J I, SUKAWA H, KIMURA H, OKITA K. Various silicon-containing polymers with Si(H)-C identto C units [J]. Journal of Polymer Science Part A:Polymer Chemistry，2001，39（15）：2658-2669.  \n[56] BREFORT J L, CORRIU R J P, GERBIER P, GUERIN C, HENNER B J L, JEAN A, KUHLMANN T, GARNIER F, YASSAR A.New  poly[(silylene)diacetylenes]  and  poly[(germylene)diacetylenes]:  Synthesis  and  conductive  properties  [J].  Organometallics，1992，11（7）：2500-2506.  \n[57] LIAW D J, WANG K L, HUANG Y C, LEE K R, LAI J Y, HA C S. Advanced polyimide materials: Syntheses, physical propertiesand applications [J]. Progress in Polymer Science，2012，37（7）：907-974.  \n[58] KELLER T M, DOMINGUEZ D D. High temperature resorcinol-based phthalonitrile polymer [J]. Polymer，2005，46（13）：4614-4618.  \n[59] ZHANG  S,  DU  S,  WANG  L,  LIN  J,  DU  L,  XU  X,  GAO  L.  Design  of  silicon-containing  arylacetylene  resins  aided  by  machinelearning enhanced materials genome approach [J]. Chemical Engineering Journal，2022，448：137643.  \n[60] HU  Y,  ZHAO  W,  WANG  L,  LIN  J,  DU  L.  Machine-learning-assisted  design  of  highly  tough  thermosetting  polymers  [J].  ACSApplied Materials & Interfaces，2022，14（49）：55004-55016.  \n[61] XU X, ZHAO W, HU Y, WANG L, LIN J, QI H, DU L. Discovery of thermosetting polymers with low hygroscopicity, low thermalexpansivity, and high modulus by machine learning [J]. Journal of Materials Chemistry A，2023，11（24）：12918-12927.  \n[62] KERNER J, DOGAN A, RECUM H V. Machine learning and big data provide crucial insight for future biomaterials discovery andresearch [J]. Acta Biomaterialia，2021，130：54-65.  \n[63] LIU  Y,  ZHANG  D,  TANG  Y,  ZHANG  Y,  GONG  X,  XIE  S,  ZHENG  J.  Machine  learning-enabled  repurposing  and  design  ofantifouling polymer brushes [J]. Chemical Engineering Journal，2021，420：129872.  \n[64] YAN C, LI G. The rise of machine learning in polymer discovery [J]. Advanced Intelligent Systems，2023，5（4）：2200243.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "PAPER • OPEN ACCESS",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# You may also like",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# Solidification process analysis and parameter optimization of powder coating by electrostatic spraying  \n\nTo cite this article: Ran Yan etal2023 J.Phys.:Conf.Ser.2539 012092  \n\n- The characteristics of particle charging and deposition during powder coating processes with coarse powder Xiangbo Meng, Hui Zhang and Jingxu (Jesse) Zhu  \n\n- Study on the characterization technology of hiding power of powder coating Bing Xue, Ran Yan, Can Wang et al.  \n\n- Line balancing synchronization in powder coating workstation: A metal industry case study   \nF. H. Ho, M. Al-Haqeem Chee S. Abu and Y. L. Woo  \n\nView the article online for updates and enhancements.",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# UNITED THROUGH SCIENCE & TECHNOLOGY",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# Science + Technology + YOU!",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 248th ECS Meeting Chicago, IL October12-16,2025 Hilton Chicago  \n\nSUBMIT ABSTRACTS by March28,2025",
+        "category": " Abstract"
+    },
+    {
+        "id": 7,
+        "chunk": "# Solidification process analysis and parameter optimization of powder coating by electrostatic spraying  \n\nRanYana, Bing Xuea\\*, Yongyong Yuea  \n\na Jiangsu XCMG Construction Machinery Research Institute Co. Ltd., Xu Zhou, Jiangsu, China  \n\n\\*Corresponding author’s e-mail: xueb@xcmg.com  \n\nABSTRACT: Aiming at formulating reasonable curing process parameters of powder coating, solving the problems of over-drying of thin plate and impervious drying of the thick plate during combined drying of workpieces with different thicknesses, analyzing the optimal curing temperature range of powder coating by differential scanning calorimetry (DSC), and designing a three-factor and four-level DOE test scheme within the optimal curing temperature range to test the curing time of powder coating are necessary. Using Minitab analysis software, the significance of the influence of various factors on the powder curing time is verified and the powder coating curing process model is built on this basis. The results show that the furnace temperature and workpiece thickness have significant effects on the shortest and longest curing time of powder coating. And there is no obvious interaction between furnace temperature and heating rate. The curing process model based on this can effectively solve the drying problem of composite plates with different thicknesses and reduce energy consumption.",
+        "category": " Abstract"
+    },
+    {
+        "id": 8,
+        "chunk": "# 1. INTRODUCTION  \n\nAs solvent-free solid powder environmentally friendly coating, powder coating has been widely used in various fields for its excellent coating performance, and powder electrostatic spraying has become one of the main surface treatment methods [1-3]. Different from solvent-based coatings, the curing of powder coatings needs to be carried out in the molten state and requires high-temperature curing. Generally, it needs to be at the substrate temperature of $180~^{\\circ}\\mathrm{C}$ for more than 15 minutes or at the substrate temperature of $200^{\\circ}\\mathrm{C}$ for more than 10 minutes to obtain a good curing effect. Moreover, the organic compounds in the powder coating formula are easy to be oxidized due to the influence of too high temperature or too long baking time, resulting in yellowing oxide and over-drying, which affects the consistency of coating quality [4,5]. And due to the economic and efficient characteristics of powder coating, the coating products gradually expand to thick plates and structural parts, but the heating rate of plates with different thicknesses and the maximum temperature of steel plates are different. If the same baking and curing conditions are adopted, it is easy to cause problems such as impermeability of thick plates and over-drying of thin plates, resulting in serious quality hidden dangers [6,7]. In the field of construction machinery, the workpiece structure is complex, and there are a large number of thin and thick plate composite structures [8], to ensure the complete curing and crosslinking reaction. It is necessary to set the appropriate curing temperature and curing process beat, and select reasonable thickness differences between thin and thick plate combinations, to avoid the decline of product paint film appearance quality caused by the problems of thick plate dryness and thin plate over-drying during the curing process of the powder paint film.  \n\nIn this paper, the non-isothermal curing reaction of powder coatings is analyzed by differential scanning calorimetry (DSC), and many curing process data of the production line are collected. A three-factor and four-level DOE test is designed to test the curing time in the laboratory, and Minitab analysis software is used to analyze the factors. The residual, main effect analysis and general linear fitting analysis are carried out on the test results of the shortest curing time, that is, the time just reaching the complete curing state, and the longest curing time, that is, the critical time of over-drying state. The influence degree of each factor on the curing time is determined, and the curing process model is constructed to guide the determination of the powder curing process of composite board.",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2. EXPERIMENTAL",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.1 Materials and instruments  \n\nDSC 6000 differential scanning calorimeter; FCD-3000 oven; BYK color difference meter; Acetone, analytically pure; Polyester thermosetting powder coating, commercially available; Steel plate (150 $\\mathrm{mm}\\times70\\mathrm{mm}\\times2\\mathrm{mm}$ ).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 2.2 Experimental process",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# 2.2.1 The sample preparation  \n\nCommercial polyester thermosetting powder coating was sprayed on $150\\ \\mathrm{mm}\\times70\\ \\mathrm{mm}\\times0.2{\\sim}0.3\\ \\mathrm{mm}$ tinplate with film thickness between $60~{\\upmu\\mathrm{m}}{-}80~{\\upmu\\mathrm{m}}$ . Different oven temperatures were set and corresponding heating rates were controlled for curing.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# 2.2.2 Determination of the shortest curing time and the longest curing time  \n\nStart timing after the furnace temperature rises to the set temperature, take out the cured paint film every 5min. Wipe the cured paint film with non-woven fabric dipped in acetone solution, and the non-woven fabric has no sticky color, that is, it is completely cured, and the record that the curing time at this time is the shortest curing time. Taking the standard color board as the standard, the color difference of the cured paint film is tested by the BYK color difference instrument. The color difference $\\leq1.5$ is considered as the critical point of the over-drying of the paint film, and the curing time when the color difference of the paint film is more than 1.5 is recorded as the longest curing time.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 14,
+        "chunk": "# 2.2.3 Testing and Characterization  \n\nDifferential scanning calorimetry (DSC) was used to measure the optimum curing temperature range of industrial polyester thermosetting powder coating under programmed temperature control. The temperature rise rate was $10\\ {^{\\circ}\\mathrm{C/min}}$ and the temperature rise range was $20^{\\circ}\\mathrm{C}{-}300^{\\circ}\\mathrm{C}$ .  \n\nWithin the optimum curing temperature range of powder coating, based on the thickness of commonly used workpieces in the field of construction machinery and the current situation of coating production lines of various companies, the full factor test is designed by DOE. The furnace temperature, heating rate, and steel plate thickness are set as independent variables, and the shortest curing time and the longest curing time are set as dependent variables. The test scheme is shown in Table 1.  \n\nTable 1. Test design factor coding level.   \n\n\n<html><body><table><tr><td>Factor</td><td>Encoding</td><td>Number of levels</td><td colspan=\"3\">The level of value</td></tr><tr><td>Furnace temperature /°C</td><td>A</td><td>3</td><td>180 200</td><td>220</td><td>/</td></tr><tr><td>Temperature rate/ (C·min-1)</td><td>B</td><td>3</td><td>8</td><td>15 20</td><td>/</td></tr><tr><td>Height of workpiece /mm</td><td>C</td><td>4</td><td>5</td><td>15 30</td><td>90</td></tr></table></body></html>\n\nThe shortest curing time and longest curing time of commercial powder coatings were tested by acetone solution and BYK colorimeter. Residual analysis, main effect analysis, and general linear  \n\nfitting analysis were carried out on the shortest and longest curing time by Minitab, to analyze the influence of furnace temperature, heating rate, and workpiece thickness on curing time. Table 2 shows the full factorial experimental design and experimental results generated by Minitab software.  \n\nTable 2. Experimental design and results of over-drying powder coatings   \n\n\n<html><body><table><tr><td>StdOrder</td><td>Run Order</td><td>A</td><td>B</td><td>C</td><td>Minimum constant temperature</td><td>Maximum constant temperature</td></tr><tr><td>3</td><td>1</td><td>180</td><td>8</td><td>30</td><td>curing time /min 16</td><td>curing time /min 180</td></tr><tr><td>29</td><td>2</td><td>220</td><td>15</td><td>5</td><td>5</td><td>35</td></tr><tr><td>10</td><td>3</td><td>180</td><td>20</td><td>15</td><td>13</td><td>130</td></tr><tr><td>20</td><td>4</td><td>200</td><td>15</td><td>90</td><td>30</td><td>250</td></tr><tr><td>16</td><td>5</td><td>200</td><td>8</td><td>90</td><td>35</td><td>260</td></tr><tr><td>31</td><td>6</td><td>220</td><td>15</td><td>30</td><td>12</td><td>110</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>......</td><td>·.....</td><td></td><td></td><td>.....</td><td>....</td><td>.....</td></tr><tr><td>25</td><td>30</td><td>220</td><td>8</td><td>5</td><td>4</td><td>30</td></tr><tr><td>24</td><td>31</td><td>200</td><td>20</td><td>90</td><td>25</td><td>245</td></tr><tr><td>23</td><td>32</td><td>200</td><td>20</td><td>30</td><td>18</td><td>50</td></tr><tr><td>12</td><td>33</td><td>180</td><td>20</td><td>90</td><td>50</td><td>390</td></tr><tr><td>27</td><td>34</td><td>220</td><td>8</td><td>30</td><td>13</td><td>105</td></tr><tr><td>17</td><td>35</td><td>200</td><td>15</td><td>5</td><td>8</td><td>70</td></tr><tr><td>36</td><td>36</td><td>220</td><td>20</td><td>90</td><td>19</td><td>185</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3. RESULTS AND DISCUSSION",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 3.1 DSC curve analysis  \n\nFigure 1 shows the DSC curve of polyester thermosetting powder coating during curing at $20{}^{\\circ}\\mathrm{C}-300{}^{\\circ}\\mathrm{C}$ (the heating rate is $10\\ \\mathrm{^{\\circ}C}\\ /\\ \\mathrm{min})$ . There is an obvious endothermic transition at $62.7~^{\\circ}\\mathrm{C}$ , where the temperature is the melting point of the powder coating. When the temperature further increases, the curve begins to show an exothermic transition near $133~^{\\circ}\\mathrm{C}_{\\mathrm{\\i}}$ indicating that the powder begins to cure at this temperature; as the temperature continues to rise, it can be seen that the exothermic reaction rate gradually increases, and the maximum exothermic rate is between $180~^{\\circ}\\mathrm{C}$ and $220~^{\\circ}\\mathrm{C}$ , which is also the fastest curing temperature of powder coating. By analyzing the DSC curve of polyester thermosetting powder coatings, it can be concluded that the curing temperature range of powder coatings is $133^{\\circ}\\mathrm{C}\\sim230^{\\circ}\\mathrm{C}.$ , and the best curing temperature range is $180\\sim220^{\\circ}\\mathrm{C}$ .  \n\n![](images/9c3eebe32057fbd8c420d6a7eb5b6ae9fb0fecd35e2ae7dc5bd027c50a9801d8.jpg)  \nFigure 1. Non-isothermal DSC curve of polyester thermosetting powder",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 3.2 DOE full factorial test data analysis  \n\nThe residual plot can be used to determine the stability and abnormality of the test data. In the DOE full-factor test, Minitab software is used to carry out residual analysis on the shortest curing time and the longest curing time. As shown in the residual diagram in Figure 2, the test data of curing time obey the normal distribution, the residual fluctuates randomly up and down the horizontal axis, and there are no obvious laws and trends such as rising and falling, indicating that the test data is stable and reliable, and no abnormal values are found, which can perform effective general linear fitting analysis and main effects analysis.  \n\n![](images/3d2eb42961d896152025f34f5c74dbb523615059dd225c860daafb5b21b62bd6.jpg)  \nFigure 2. Residual diagram of furnace temperature, heating rate, and workpiece thickness on constant temperature curing time.  \n\nTo explore the influence of each group of key parameters on the curing time, the main effect analysis was carried out on the test results. As shown in Figure 3, in the main effect diagram of each influencing factor, the slope and range of furnace temperature and workpiece thickness to the shortest curing time and longest curing time are larger, on the contrary, the slope of heating rate to curing time is smaller and close to 0, that is, the furnace temperature and the thickness of the workpiece are the main factors affecting the curing of the powder coating, and the heating rate has the least effect on the curing time, which can be ignored.  \n\nGeneral linear model fitting is primarily used to determine whether the association between the dependent variable and each independent variable is statistically significant. Statistically, the P value is a significant level, representing the significant degree of association between the dependent and independent variables. When the $\\mathrm{\\bfP}$ value is less than 0.05, it indicates that there is a significant linear correlation between the data of the two groups of fitted independent variables and dependent variables. When the $\\mathrm{~\\bf~P~}$ value is greater than or equal to 0.05, it means that there is no significant linear relationship between the two groups of independent variables being fitted and the data of the dependent variable, that is, the independent variable has a low degree of influence on the dependent variable. R-sq, also known as the goodness of fit, is an important parameter to measure whether the linear fitting model obtained from the linear fitting analysis is good or not. It is the ratio of the sum of squares of regression to the sum of squares of total deviation. The closer the value is to $100\\%$ , the better the linear fitting model obtained.  \n\n![](images/207df74e02fec67d2307c0a018995c5df8a8c47a340e59e11749c291ac8681d0.jpg)  \nFigure 3. Main effect diagram of furnace temperature, heating rate, and workpiece thickness.  \n\nTo further determine the influence degree of each influence factor on the curing time of powder coating, a general linear fitting was carried out on the results of the DOE full-factor test. Among them, furnace temperature, heating rate, and workpiece thickness are independent variables, and the shortest curing time and the longest curing time are dependent variables. The results generated by Minitab software were shown in Table 3. It can be seen from the fitting results that the R-sq of the linear model is $99.24\\%$ and $99.86\\%$ respectively, indicating that the linear model is in good agreement with the test data and the fitting results are reliable. As results in the two groups, the $\\mathrm{~\\bf~P~}$ values of heating rate, furnace temperature \\* heating rate, and heating rate \\* workpiece thickness are more than 0.05, and the P values of furnace temperature, workpiece thickness, and furnace temperature \\* workpiece thickness are less than 0.05. It shows that there is a significant linear correlation between furnace temperature, workpiece thickness, and curing time, and there is no significant linear correlation between heating rate and curing time. Therefore, in the following research, the influence of heating rate on curing time is small, and there is no significant linear correlation, which can be ignored.  \n\nTable 3. General linear model analysis of minimum curing time and maximum curing time.   \n\n\n<html><body><table><tr><td rowspan=\"2\">Source</td><td colspan=\"2\">Minimum curing time</td><td colspan=\"2\">Maximum curing time</td></tr><tr><td>P-Value</td><td>R-sp</td><td>P-Value</td><td>R-sp</td></tr><tr><td>Furnace temperature /°C</td><td>0.000</td><td></td><td>0.000</td><td></td></tr><tr><td>Temperature rate /°C·min-l</td><td>0.002</td><td></td><td>0.023</td><td></td></tr><tr><td>Workpiece thickness /mm</td><td>0.000</td><td></td><td>0.000</td><td></td></tr><tr><td>Furnace temperature /°C*Temperature rate /C·min-1</td><td>0.488</td><td>99.24%</td><td>0.853</td><td>99.86%</td></tr><tr><td>Furnace temperature /°C* Workpiece thickness /mm</td><td>0.000</td><td></td><td>0.000</td><td></td></tr><tr><td>Workpiece thickness /mm Temperature rate /°C·min-1*</td><td>0.203</td><td></td><td>0.374</td><td></td></tr></table></body></html>  \n\nThrough the above residual analysis, main effect analysis, and general linear model analysis, it can be concluded that the most significant factors affecting the curing time of powder coating are furnace temperature and workpiece thickness, and the heating rate has little influence on curing time. Therefore, the influence of furnace temperature and workpiece thickness on the curing time of powder coating is mainly considered in the following studies. The following will take furnace temperatures of $220^{\\circ}\\mathrm{C}$ , $200^{\\circ}\\mathrm{C}$ , and $180^{\\circ}\\mathrm{C}$ as examples to explore the influence of different workpiece thicknesses on the curing time of powder coatings under fixed furnace temperatures, and design the curing process model of powder coatings.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# 3.3 Design of curing process model for powder coatings  \n\nTo meet the production requirements, workpieces of different thicknesses need to be combined and enter the curing chamber at the same time. Therefore, a reasonable combined thickness difference of steel plate needs to be set to prevent the coating from not fully curing on the thick plate or over-drying on the thin plate due to the unreasonable setting of combined thickness difference. The basic principle of setting combined thickness difference is: the shortest curing time of a thick plate is less than the longest curing time of a thin plate. After obtaining the shortest and longest curing time of steel surfaces with different thicknesses, the curing process design model is drawn to guide the optimal design of drying time of steel plate combination with different thicknesses and reduce the drying energy consumption in the coating process.  \n\nUnder the condition of $220^{\\circ}\\mathrm{C}$ furnace temperature, the minimum curing time and maximum curing time of steel plate with characteristic thickness are measured and the curing process model diagram is designed based on the corresponding relationship between plate thickness and curing time. As shown in Figure 4 (a), the t1 curve is the shortest curing time curve of steel plates with different thicknesses, the $\\mathbf{t}_{2}$ curve is the longest curing time curve of steel plates with different thicknesses, the steel plate thickness $\\mathtt{h}_{0}$ can be combined with the thinnest steel plate thickness $\\mathbf{h}_{2}$ , and the energy consumption is the lowest, that is when the thick plate $\\mathtt{h}_{0}$ and the thin plate $\\mathbf{h}_{3}$ are cured at the same time, the thin plate will be over dried or the thick plate will not dry thoroughly, so it cannot be combined. Therefore, under the fixed furnace temperature, the maximum temperature $\\mathrm{T}_{1}$ is measured corresponding to the thinnest workpiece, the maximum temperature $\\mathrm{T}_{2}$ is measured corresponding to the thickest workpiece of the production line, the maximum curing time $\\mathbf{t}_{2}$ is measured corresponding to the powder coating under $\\mathrm{T}_{1}$ with BYK color difference instrument, and the minimum curing time $\\mathbf{t}_{1}$ is measured corresponding to the powder coating under $\\mathrm{T}_{2}$ with acetone wiping method. If $\\mathbf{t}_{1}<\\mathbf{t}_{2}$ , the two thicknesses can be combined for drying, if $\\mathbf{t}_{1}>\\mathbf{t}_{2}$ , the two thicknesses cannot be combined for drying. A comparative analysis of curing process models at $220^{\\circ}\\mathrm{C}$ , $200^{\\circ}\\mathrm{C}$ , and $180^{\\circ}\\mathrm{C}$ oven temperatures is carried out based on the designed curing process model. As shown in Figure 4(b), as the oven temperature decreases, the powder coating curing window moves to the right and widens, and the minimum curing time changes little with the furnace temperature slope, that is, the minimum curing time of powder coatings is mainly affected by its curing performance; the longest curing time changes with the furnace temperature and the slope changes greatly and the right shift is greater, that is, the longest curing time of powder coatings is greatly affected by the temperature of the oven and the thickness of the plate.  \n\n![](images/37a71b146e51de52af58eed0e443dbd4a94d7ba71f6ea76a9d792e25f8a29495.jpg)  \nFigure $4.220^{\\circ}\\mathrm{C}$ curing process model diagram (a) and $220^{\\circ}\\mathrm{C}$ , $200^{\\circ}\\mathrm{C}$ , $180^{\\circ}\\mathrm{C}$ process model comparison diagram (b).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 4. CONCLUSION  \n\nThe best curing temperature range of powder coating was tested by DSC, and the DOE all-factor test design was carried out within the best curing temperature range. Furnace temperature, heating rate, and workpiece thickness were set as independent variables, and the shortest curing time and longest curing time of powder coating were determined by the acetone wipe method and color difference method. Using Minitab software to carry out residual analysis, main effect analysis, and general linear fitting analysis on the determination results of curing time, it can be concluded that furnace temperature and workpiece thickness were the most influential factors on the curing time of powder coating, while heating rate had little influence on curing time. On this basis, the curing process model of powder coating is designed, which can effectively guide the selection of curing furnace temperature and curing beat of powder coating in the production line, and guide the selection of thickness difference during combined curing of workpieces with different thickness, to avoid problems such as over-drying of thin plate and impervious drying of thick plate, minimize energy consumption, improve production efficiency, and save cost.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 20,
+        "chunk": "# ACKNOWLEDGEMENT  \n\nThis paper is the periodical result of the Natural Science Foundation Project—Youth Fund Project (BK20180176 Construction and Mechanism of Corrosion Self-repairing Functional Coatings Based on Graphene-based Corrosion Inhibitors Nano-compartments).",
+        "category": " References"
+    },
+    {
+        "id": 21,
+        "chunk": "# REFERENCES  \n\n[1] Wang, W. X., Wang Y.Y., Han Y.Y., Liu Z.L., and Wang C. X., Analysis of curing kinetics of polyester /TGIC powder coatings, Paint & Coatings Industry, 49, 41-46 (2019).   \n[2] Zhao, C.N., Liu, C.M., and Qi, X.A., Study on new powder Coating system for steel structural parts of construction Machinery, Paint & Coatings Industry, 51, 64-68 (2021).   \n[3] Mao, Y.D., Pan, G., Liu, Y. Q., W, T. Z., Qin, M. Y., Wang, X. R., and Wu J. S., Study on curing parameters of infrared curing powder coatings by gas catalytic combustion, Modern Paint & Finishing, 24, 11-14 (2021).   \n[4] Zhang, H., Yan, B. W., Yang, S., Huang, J.B., Liu, W. and Shao, Y. Y., Research status and development of functional powder coatings, Chemical Industry and Engineering, 37, 1-18 (2020).   \n[5] Ou, Y. J.Q., Chen, J. H. and Chen, W. G., Study on powder coatings for construction machinery, Coating and Protection, 2, 9-15 (2020).   \n[6] Gan, L., Sun, Z. J., Gu, Y. Z., Li, M. and Zhang, Z. G., Study on curing reaction of epoxy resin by temperature and isothermal non-model kinetics, Acta Polymeric Clinical, 8, 1016-1022(2010).   \n[7] Lin, Y. J. Test, and analysis of coating properties under different curing processes of powder spraying, World Nonferrous Metals, 3, 192-194(2018).   \n[8] Liu, H., Hu, C. L. and Liu, B. X., Analysis on Curing Process of Static Spraying Powder Coating on Aluminium Alloy Profile, Paint & Coatings Industry, 44, 64-67(2014).",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Direct steering of de novo molecular generation with descriptor conditional recurrent neural networks  \n\nPanagiotis-Christos Kotsias $\\textcircled{10}1$ , Josep Arús-Pous1,2, Hongming Chen1,3, Ola Engkvist $\\textcircled{1}$ 1, Christian Tyrchan4 and Esben Jannik Bjerrum   1 ✉  \n\nDeep learning has acquired considerable momentum over the past couple of years in the domain of de novo drug design. Here, we propose a simple approach to the task of focused molecular generation for drug design purposes by constructing a conditional recurrent neural network (cRNN). We aggregate selected molecular descriptors and transform them into the initial memory state of the network before starting the generation of alphanumeric strings that describe molecules. We thus tackle the inverse design problem directly, as the cRNNs may generate molecules near the specified conditions. Moreover, we exemplify a novel way of assessing the focus of the conditional output of such a model using negative log-likelihood plots. The output is more focused than traditional unbiased RNNs, yet less focused than autoencoders, thus representing a novel method with intermediate output specificity between well-established methods. Conceptually, our architecture shows promise for the generalized problem of steering of sequential data generation with recurrent neural networks.  \n\nhe disruptive impact deep generative models have delivered over the past couple of years has found applications in various aspects of content creation. Neural networks have proven potent in generating news headlines1, synthesizing music2 or poems3 and drawing realistic paintings4. In the life sciences, they have driven innovation in tasks such as bioactivity and synthesis prediction5, segmentation of biological images6 and de novo design of molecules7. In the latter domain, in particular, deep learning serves as a prominent stakeholder by offering the capability to direct the generative process towards chemical regions of interest8–10. A challenging task deep networks are trying to address is inverse molecular design11—the generation of molecular structures that meet desired conditions, such as specific physicochemical properties or properties predicted by quantitative structure–activity relationship (QSAR) models.  \n\nThe ‘simplified molecular-input line-entry system’ (SMILES)12 is a popular choice13 to represent molecules when using recurrent neural networks (RNNs). The alphanumeric nature of SMILES strings makes them compatible with state-of-the-art natural language-processing algorithms, such as RNNs, performing sequence modelling and generation. In particular, RNNs are a widely accepted approach to the task of sequence modelling because of their ability to memorize previously predicted characters of a partially finished SMILES string and incorporate them into their inference while building up the complete sequence14.  \n\nUnbiased RNN generative models trained on a relatively small number of SMILES strings have been shown to be able to cover a much larger chemical space15. Moreover, augmentation of a dataset using SMILES with randomized atom order has demonstrated state-of-the-art performance with respect to the uniformity and completeness of the coverage of chemical regions, compared to simply using their canonical variants16. After learning the general rules of the chemical space, for example atom type, bond type and size of molecules, the prior network can be further specialized using smaller datasets in a transfer learning fashion17 or using reinforcement learning18–20.  \n\nMore complicated architectures, such as autoencoders21, which include two jointly trained neural networks responsible for converting the input to and back from a latent representation, have been extensively benchmarked22,23. The quality of the latent space of an autoencoder was also proven to benefit from the usage of randomized SMILES strings24–26. Moreover, the latent space representation of a molecule can be used in optimizing QSAR endpoints using generative adversarial networks $(\\mathrm{GANs})^{27}$ , Bayesian optimization21 or particle swarm optimization28. The combination of a heteroencoder25, trained on pairs of randomized SMILES strings of the same molecule, with a $\\mathrm{GAN^{29}}$ has further demonstrated automatic navigation towards properties of interest.  \n\nAlternatively, learning to precondition structure generation eliminates the need for optimization loops. One approach demonstrated this capability by concatenating SMILES strings with the properties of interest as input to a variational autoencoder30. Molecular graphs31 have also been used in pairs along with the desired change in properties as conditions on which to train a variational autoencoder. Latent representations that are generated by a GAN architecture may also be exploited as input conditions for decoding neural networks29.  \n\nIn this work, we demonstrate that molecule-side information, such as molecular descriptors, can be incorporated into the RNN-based generative process. We construct conditional recurrent neural networks (cRNNs) by setting the internal states of long short-term memory cells $\\mathrm{(LSTMs^{32}}$ ) after some input conditions.  \n\n![](images/e7fd0234b8e0f23f3a727d2fce27582be499fa8231f6a8c613bf792c3da18c7c.jpg)  \nFig. 1 | cRNN models based on different conditions. a, The physchem-based (PCB) model accepts six scalar properties: the Wildman–Crippen partition coefficient (logP), topological polar surface area (TPSA), molecular weight (MW), drug-likeness (QED), number of hydrogen-bond acceptors (HBA) and donors (HBD) as calculated by the RDKit Python library, concatenated with the probabilistic bioactivity prediction of the QSAR model. b, The fingerprint-based (FPB) model accepts a 2,048 bit Morgan fingerprint vector calculated by RDKit. Both models are trained on randomized SMILES strings as targets. c, Model inference is biased by the conditional seed and triggered by the starting character ‘^’. Inference stops when $'8^{\\prime}$ is generated.  \n\nThe architecture is related to, but conceptually simpler than, a conditional autoencoder, as we only utilize an RNN-based decoder part. The generation is conditioned with properties calculated directly from the molecular structure or QSAR models, so the encoder part is no longer needed. The conditional seed successfully steers the focus of the RNN towards a particular subset of the chemical domain, such as bioactive compounds, with respect to a specific protein target. Our approach complements existing state-of-the-art conditional generative models such as conditional variational autoencoders, reinforcement learning and so on, and may be used for populating of specialized molecular libraries. We also demonstrate a novel way of assessing the focus of a probabilistic sequence generator using negative log-likelihood (NLL) plots. Owing to the nature of the problem for which our method is showcased, it may also be generalized to other applications where conditioning of sequential data is needed, such as natural language generation or time-series forecasting.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Results and discussion  \n\nResulting datasets. The filtering process described in the Methods resulted in the sizes of datasets shown in Table 1. The QSAR support vector classification model with parameters $C=5.53$ and $\\gamma=0.022$ was selected as the one with the highest F1-score (0.92) towards the DRD2 validation set. This model was used to label all compounds in the ChEMBL dataset, leading to $2.3\\%$ of the ChEMBL compounds being classified with a probability greater than $50\\%$ of being active against the DRD2 receptor (Table 1). As shown in Extended Data Fig. 1, the property distributions of the two datasets largely follow each other, except that the QED score of the DRD2 dataset is shifted towards higher values because those molecules are expected to be a priori drug-like.  \n\nNLL distributions of datasets. The NLL of sampling molecules from the ChEMBL25 dataset and from the known active compounds of the DRD2 dataset was calculated for all different models.  \n\nTable 1 | Size and percentage of active compounds per dataset   \n\n\n<html><body><table><tr><td>Dataset</td><td>Total samples</td><td>Active %</td></tr><tr><td>DRD2_TRAIN</td><td>71,512</td><td>6.7a</td></tr><tr><td>DRD2_VALID</td><td>17,800</td><td>6.3a</td></tr><tr><td>DRD2_TEST</td><td>17,817</td><td>6.4a</td></tr><tr><td>ChEMBL25_TRAIN</td><td>1,347,173</td><td>2.3b</td></tr><tr><td>ChEMBL25_TEST</td><td>149,679</td><td>2.3b</td></tr></table></body></html>\n\naKnown active compounds. bPredicted active compounds $(P\\ge0.5)$ by the QSAR model.  \n\nIn total, 1,000 molecules were randomly selected from each of the ChEMBL25 train and ChEMBL25 test datasets and the active compounds of the DRD2 train and DRD2 test datasets. After performing 10,000 randomization operations per molecule, all unique random strings per molecule were collected. Then, by using equation (5), the NLL of sampling a molecule was approximated as the cumulative likelihood over all its uniquely derived random representations, given each model.  \n\nFigure 2 shows all different NLL distributions using the smoothened estimate of the density function of the underlying histograms. As showcased in Supplementary section ‘Likelihood of sampling of canonical SMILES’, selecting the canonical form to calculate the NLL plots of Fig. 2 is not expected to alter the quantitative conclusions that can be drawn from them.  \n\nThe FPB model results in the sharpest distribution of NLL values with the lowest mean and variance compared to the other three models with respect to all datasets. Similarly, the PCB model shows the second lowest NLL mean value per dataset. The arrangement of the plots is as expected, because the amount of chemical information in the 2,048 bits of a Morgan fingerprint exceeds the information that is contained within the seven scalar descriptors used in the PCB model, especially from a structural point of view. The graphs of the conditional models show a slight shift towards higher values for the DRD2 datasets due to the uncertainty that is inherent to unseen data. Nevertheless, both conditional models have a lower mean NLL—and thus a higher probability— of sampling a SMILES string representation corresponding to the molecule from which the conditions originated, compared to the prior network both before and after being trained with transfer learning. The transfer learning model curve exchanges its relative position with the prior model curve between the two datasets because the focus of the model trained with transfer learning has been shifted away from the majority of molecules in ChEMBL and thus it is more difficult to sample their respective SMILES strings.  \n\n![](images/6c1302ba969c9fd52398025127badcbf86de162097820c2b658fa31933e1f5b9.jpg)  \nFig. 2 | NLL of sampling known molecules. a–d, The NLL values of 1,000 molecules randomly drawn from each of four datasets (ChEMBL25_TRAIN (a), ChEMBL25_TEST (b), DRD2_TRAIN_ACTIVES (c) and DRD2_TEST_ACTIVES (d)) were calculated using the PCB, FPB, transfer learning (TL) and prior models. For each molecule, 10,000 randomizations were performed, and its NLL was approximated as the cumulative NLL of sampling all unique random strings obtained for that molecule out of the 10,000 randomization attempts. The plots show the estimate of the density of the underlying NLL histograms using the kdeplot function of the seaborn Python library with a bandwidth value of 3.0. The mean and standard deviation of the sampled data distributions are annotated. The ChEMBL25 sets consist of both predicted active and inactive compounds, whereas only the known actives were selected from the DRD2 sets for this test. The graphs are truncated at a maximum NLL value of 70.  \n\nIdeally, all models should be able to sample the intended chemical space uniformly and this would be expressed by zero variance of the NLL distribution, which should approximate a Dirac distribution. Under such ideal conditions, it would be possible to estimate the size of the output space by simply inverting the (constant) probability of sampling any molecule; for example, a probability of 0.01 would mean that, in total, 100 molecules could be sampled. As an example, a sharp NLL distribution around a value of 10 would imply a uniform probability distribution at a value of $4.54\\times10^{-5}$ or an equiprobable output space of 22,000 unique molecules. Similarly, NLL values of 20 and 30 would point to output domains of ${\\sim}10^{8}$ and $10^{13}$ molecules, respectively. Even though the distributions of Fig. 2 are far from Dirac distributions, a comparison of the distributions may serve as a qualitative insight into the relative change in the order of magnitude of their output space.  \n\nAdditionally, the position of the distributions can be interpreted in two ways. First, the closer to zero the NLL distribution moves, the more deterministic the output of the model gets. This can be due to either limited generalizability of the model or a more detailed description of the target, such as in the case of a conditional network. Second, differences in NLL distributions between train and test sets can be a sign of overfitting or mode collapse15. This seems to be the case with the transfer learning model, which exhibits a distribution with a lower mean NLL towards the active compounds in the DRD2 train dataset compared to the unseen active ones in the DRD2 test set. In contrast, the NLL distributions of sampling all four datasets with either of the conditional networks, regardless of the dataset, are on par, which makes overfitting a less likely cause. Here, the similar distributions, regardless of the dataset, demonstrate that the conditional models can generate valid SMILES that correspond to both active and inactive compounds with equal ease, given that the states are set accordingly.  \n\nSampling of active molecules. The structures shown in Fig. 3 were suggested by the two conditional networks using known active compounds from the DRD2 test set as conditional seeds, which were selected randomly (shown in the centre). The SMILES strings corresponding to the exemplified molecules in the dashed circle were generated by the FPB model, whereas those outside it were generated by the PCB model. A batch of 256 SMILES strings was sampled per model per  seed, and all molecules displayed were filtered to have a QED score greater than 0.8 and were predicted to be active by the QSAR model with a probability greater than 0.8, given that both seeds met those values. Of all 256 generated SMILES strings in each batch sampled by the FPB model, ${\\sim}5\\%$ referred to unique molecules that jointly satisfy these challenging constraints, because of high repeatability in the output (discussed in the next section). Similarly, ${\\sim}5\\%$ and $22\\%$ of the PCB-generated SMILES strings corresponded to unique molecules that meet the specifications of the first and second seed, respectively. The rest of the unique molecules corresponding to valid generated SMILES strings for those two given seeds are shown in Supplementary Figs. 4–11.  \n\n![](images/74e0b502d13ca5dd6204fa1dea6199c70e9e61cdc0691963acec33329d161c9f.jpg)  \nFig. 3 | Unique structures corresponding to generated SMILES strings from two different known active seeds. The seeds were randomly selected from the DRD2 test set and are shown in the centre. The selected FPB (within the dashed circle) and PCB (outside the dashed circle) generations shown have QED values of ${\\ge}0.8$ and a predicted active probability of ${\\ge}0.8$ . The FPB-generated molecules mostly maintain the seeding scaffold whereas the PCB-generated ones change scaffolds. A quantitative investigation of more structures is reported in Table 2 and the rest of the unique generated molecules for those two given seeds are shown in Supplementary Figs. 4–11.  \n\nThe FPB-based generations demonstrate almost identical structure to the seed, at least at a scaffold level. On the other hand, the PCB-generated molecules have clearly different scaffolds from the seed, which can be attributed to the fact that the selected physicochemical descriptors do not encode structural information directly.  \n\nThe correlation between the seed and the output of the models was further investigated by calculating the Tanimoto similarity of multiple batches of generated SMILES strings. For that purpose, 100 seeds were randomly selected from the unseen active compounds of the DRD2 test set and, for each one, 256 SMILES strings were generated in a batch by each of the conditional models, yielding a total of 25,600 SMILES strings. For each batch, the pairwise Tanimoto similarities were calculated between the Murcko scaffolds of the associated seed and of all unique molecules behind the generated SMILES strings. Given that fingerprints are not a complete molecular representation, they may be decoded to different molecules than the ones from which they originated, yet frequently with the same scaffold. To account for fingerprints that are not naturally decoded to the exact seeding molecule, the similarity of scaffolds is shown because it enjoys higher values even when scaffold decoration is slightly different. By doing this, we emphasize even more the fact that the FPB model maintains the structural characteristics of the input whereas the output of the PCB is structurally dissimilar to the molecule (and the scaffold of the molecule) from which the seeding conditions originated. The exact reconstructability of the two models on a molecular level is reported in Table 2.  \n\nThe resulting Tanimoto similarity histograms are plotted in Extended Data Fig. 2a, while histograms of the predicted probability  \n\nTable 2 | Comparison of cRNN and transfer learning models with respect to custom metrics and the MOSES suite   \n\n\n<html><body><table><tr><td rowspan=\"2\">Metrics</td><td rowspan=\"2\"></td><td colspan=\"3\">Models</td></tr><tr><td>PCB</td><td>FPB</td><td>TL</td></tr><tr><td>MOSES</td><td></td><td></td><td></td><td></td></tr><tr><td>Valid</td><td>→</td><td>0.881</td><td>0.951</td><td>0.968</td></tr><tr><td>Unique@1k</td><td>→</td><td>0.996</td><td>0.276</td><td>1.000</td></tr><tr><td>Unique@10k</td><td>→</td><td>0.996</td><td>0.304</td><td>0.996</td></tr><tr><td>FCD</td><td>↓</td><td>7.981</td><td>5.590</td><td>8.438</td></tr><tr><td>SNN</td><td>→</td><td>0.341</td><td>0.774</td><td>0.375</td></tr><tr><td>Frag</td><td>→</td><td>0.920</td><td>0.966</td><td>0.938</td></tr><tr><td>Scaf</td><td>→</td><td>0.094</td><td>0.491</td><td>0.193</td></tr><tr><td>IntDiv</td><td>→</td><td>0.845</td><td>0.834</td><td>0.846</td></tr><tr><td>Custom</td><td></td><td></td><td></td><td></td></tr><tr><td>Noveltya</td><td>→</td><td>0.878</td><td>0.299</td><td>0.953</td></tr><tr><td>Predicted active fractionb</td><td>→</td><td>0.536</td><td>0.194</td><td>0.474</td></tr><tr><td>Reconstructabilityc</td><td>－</td><td>≤0.001</td><td>0.630</td><td></td></tr></table></body></html>  \n\nThe DRD2 test set was used as a reference set for the MOSES framework and the seed conditions were drawn from it to be used by the PCB and the FPB cRNN models. Upwards-pointing arrows show that higher scores are considered better. Downwards-pointing arrows show that lower scores are considered better. Numbers in bold show the best score for that metric. Molecules with a predicted probability greater than 0.5 by the QSAR model were considered active. Uniqueness, novelty, predicted active fraction and reconstructability were assessed on a molecular level using the underlying canonical SMILES behind all generated strings. aCalculated with respect to the molecules behind the generated SMILES strings and the merged active molecules of the DRD2_TRAIN and ChEMBL25_TRAIN datasets only. bFraction of 25,600 generated SMILES strings that are valid and refer to unique and predicted active molecules. cCalculated based on the most frequently sampled SMILES string out of 256 strings per conditional seed.  \n\nof them being active towards DRD2 are plotted in Extended Data Fig. 2b. The PCB-generated scaffolds tend to be dissimilar to their seeds, in contrast to the FPB-generated ones, the similarity of which to the seeding scaffold follows a bimodal distribution that is shifted to the right, showing that similar or identical scaffolds are generated. However, in both cases, the distribution of active probabilities is comparable (Extended Data Fig. 2b), proving that both models can generate SMILES strings that refer to predicted active compounds given the appropriate conditions. Evaluation of the performance of the QSAR model on all ‘unseen’ known active molecules of the DRD2 test set shows that it misclassifies $10\\%$ of all cases as inactive (with a predicted active probability less than 0.5), whereas in $4\\%$ of all cases it mis-assigns a probability of being active in the range of 0.0–0.1. This implies that the inherent imperfections in the QSAR model may be responsible for the respective mode collapse observed in Extended Data Fig. 2b. The reason why the peak around an active probability of 0 of the FPB curve is higher than for PCB is because the FPB model offers a substantially lower number of unique molecules behind its generated SMILES strings and, thus, misclassification errors are enhanced when normalizing the plots with the histogram density instead of bin count.  \n\nThis supports the previous observation that the PCB model can generate different scaffolds from the same seed. Additionally, it identifies the sampling domain of each model. The main advantage of using fingerprints is that structural restrictions are directly encoded, a fact that is of use when scaffolds that are similar or identical to the seed need to be generated. On the other hand, using physicochemical properties as conditions offers a more versatile sampling, so this model could thus be applicable to explorations outside of a known scaffold, yet within the boundaries of the desired property setpoints.  \n\nBenchmarking. To quantitatively assess the performance of the proposed cRNN architecture against the selected baseline as well as other published work in the field, it was run through relevant and compatible metrics from the two main benchmarking suites in the field of de novo molecular generation: MOSES22 and GuacaMol23.  \n\nMOSES benchmark. The two cRNN models, along with the baseline trained with transfer learning, were tested with respect to the metrics provided by the MOSES framework22. For that purpose, 25,600 SMILES were additionally sampled by the model trained with transfer learning, similar to the sampling done for the other models as described in the previous sections. The metrics were calculated with respect to the active compounds of the DRD2 test set that was used as a reference dataset.  \n\nThe PCB model performs the worst with respect to most metrics, except for the predicted active fraction and uniqueness of underlying canonical SMILES among 10,000 sampled SMILES strings. However, the metrics need to be interpreted carefully. The seed conditions used for the generation were extracted from active compounds of the DRD2 test set, which were not included in the training set of both conditional models. The active class is heavily under-represented in the datasets on which they were trained (only $2.3\\%$ of predicted actives in ChEMBL; Table 1) and thus the set of conditional seeds corresponds to a demanding task, which becomes even harder for the PCB model to fulfil because much less information is included in the physicochemical descriptors than in the fingerprints. On the contrary, the transfer learning model was trained directly on known actives and it is independent of any input during generation, while trying to replicate what has been seen during training. Lacking input conditions offers an implicit advantage over the conditional models in terms of valid generated SMILES strings, because specific input combinations may cause a consistent drop in generated validity. However, within a sample of 10,000 generated SMILES strings, the PCB and the transfer learning models are on par regarding uniqueness of the underlying canonical SMILES behind their sampled strings. This metric is a performance indicator, yet it does not fully expose the differences between the models, simply because the output space is too large to generate enough strings with duplicate canonical forms within only 10,000 sampled SMILES strings. On the other hand, the FPB model has low uniqueness, but this is expected as the more deterministic nature and the lower number of possible SMILES to sample from a single fingerprint naturally leads to duplicated outputs and penalized uniqueness.  \n\nThe Fréchet ChemNet distance33 (FCD) underlines the chemical distance between the reference and the generated distributions. As such, it is heavily in favour of the conditional models, because the seeds drawn from the test set purposely force the generated distributions towards it and consequently towards lower FCD values. Moreover, because the DRD2 train and test sets had been clustered and the fact that the transfer learning model was further trained on one of them explains the deviation from the other with respect to the FCD metric. Internal diversity also exhibits expected behaviour for a similar reason; the seeds narrow the output down compared to an ideally random sampler in the DRD2 active domain, such as the transfer learning model.  \n\nAmong all 25,600 SMILES generations, a higher novelty of underlying canonical SMILES was achieved by the transfer learning model. This was due to the lower validity and uniqueness of the conditional models because the upper novelty boundary is defined by the product of validity and uniqueness. For the PCB model that boundary is $\\sim0.881\\times0.996=0.877.$ which is reached as seen in Table 2. This is an indicator that the PCB model, even though it suffers from lower validity compared to the transfer learning model, does not copy the training dataset. Similarly, the upper novelty boundary for the FPB is around $0.951\\times0.304=0.289$ , which was slightly exceeded because uniqueness $@10\\mathbf{k}$ calculated by MOSES is probably lower than the complete uniqueness of all 25,600 generated SMILES strings. For the transfer learning model, the upper boundary $0.968\\times0.996=0.964$ was almost reached as well. As observed, even though the absolute number of novel compounds was higher for the transfer learning model, none of the models replicated the training datasets.  \n\nIt is noteworthy that a higher fraction of predicted active molecules on the basis of the underlying unique canonical SMILES strings was sampled by the PCB model, whereas the least of them were generated by the FPB model. The FPB model was punished because of its high reconstructability, which negatively affects its uniqueness score.  \n\nMore specifically, the molecular reconstructability of the input descriptors was assessed by trying to retrieve the molecule that was represented by them at each batch. By identifying the most frequently sampled canonical SMILES string in batches of 256 generated strings given a single conditional seed, almost $65\\%$ of the FPB-generated batches primarily consisted of strings with the same canonical form as the molecule behind the seeding fingerprint. Those were considered successful reconstructions. Further experimentation with a deeper FPB model with four decoding layers and 512 LSTM units each made it possible to increase the reconstructability to $72\\%$ . Fingerprints are commonly thought of as being non-invertible (Table $1^{9}$ ) due to information loss in the embedding and hashing operations. However, as Morgan fingerprints can be understood as graph convolutional embeddings34, they are in fact partly invertible when considered in the scope of the training set. Nonetheless, reconstructions were very scarce when using the physicochemical descriptors in the PCB model, because 256 sampled SMILES strings were not enough to identify a specific molecule in the diverse chemical space behind a set of given input conditions.  \n\nTo investigate whether novelty of the conditional models is influenced by the training or seeding dataset, 100 new conditions were drawn from each one of the training and test subsets of ChEMBL. Then, the novelty of the unique canonical forms behind all valid SMILES strings out of 256 generated strings (one batch) per set of conditions was assessed with respect to both datasets. The results are shown in Extended Data Fig. 3. As hypothesized, both models may use the conditions stemming from unseen molecules and generate strings that describe structures that are not present in either dataset. For any of the models, the difference between datasets is insignificant, reflecting a consistent generation of SMILES strings that point to novel molecules, regardless of the origin of the seeding conditions.  \n\n<html><body><table><tr><td colspan=\"7\">Table3|Comparison of the cRNN models with the generative models benchmarked in the GuacaMol suite</td></tr><tr><td> Benchmark</td><td>Best of dataset</td><td>SMILES LSTM</td><td>SMILES GA</td><td>Graph GA</td><td>Graph MCTS</td><td>cRNN (ours)</td></tr><tr><td>Celecoxib red.</td><td>0.505</td><td>1.000</td><td>0.607</td><td>1.000</td><td>0.378</td><td>1.000a</td></tr><tr><td>Troglitazone red.</td><td>0.419</td><td>1.000</td><td>0.558</td><td>1.000</td><td>0.312</td><td>1.000a</td></tr><tr><td>Thiothixene red.</td><td>0.456</td><td>1.000</td><td>0.495</td><td>1.000</td><td>0.308</td><td>1.000a</td></tr><tr><td>logP (-1.0)</td><td>1.000</td><td>1.000</td><td>1.000</td><td>1.000</td><td>0.980</td><td>1.000b</td></tr><tr><td>logP (8.0)</td><td>1.000</td><td>1.000</td><td>1.000</td><td>1.000</td><td>0.979</td><td>1.000b</td></tr><tr><td>TPSA (150.0)</td><td>1.000</td><td>1.000</td><td>1.000</td><td>1.000</td><td>1.000</td><td>1.000b</td></tr><tr><td>CNS MPO</td><td>1.000</td><td>1.000</td><td>1.000</td><td>1.000</td><td>1.000</td><td>1.000b</td></tr><tr><td>QED</td><td>0.948</td><td>0.948</td><td>0.948</td><td>0.948</td><td>0.944</td><td>0.948b</td></tr></table></body></html>\n\nThe cRNN architecture (rightmost) achieves a maximum score in all relevant test cases. Best scores per metric are highlighted in bold. GA, genetic algorithm; MCTS, Monte Carlo tree search. aConsidering the FPB cRNN. bConsidering the PCB cRNN.  \n\nGuacaMol benchmark. To compare the cRNN architecture against more generative models other than the chosen baseline, we chose to test it on all applicable goal-directed tasks defined in the GuacaMol23 scoring suite considering the selected input descriptors for the PCB and FPB models.  \n\nFor the FPB model, the tasks corresponding to rediscovery of celecoxib, troglitazone and thiothixene were employed. Rediscovery is defined as a maximization of the similarity score (1.0) between the calculated ECFC4 fingerprints of the generated structures and the target molecule. It is important to underline that, even though the FPB model has been trained on Morgan fingerprints, rediscovery is awarded a score of 1.0, regardless of the fingerprint representation, if the correct structure is generated. Moreover, the models tested with GuacaMol used prior knowledge, where applicable, in the form of 100–300 known highest-scoring molecules from the ChEMBL dataset as initial points for the optimization. They were also exposed to the target of interest via the scoring function in a feedback loop. To account for the benefit of steering the output using the feedback loop and to ensure a fair comparison, the FPB cRNN was preconditioned with the Morgan fingerprint of the target. According to GuacaMol, a maximum of approximately 10,000 generations (SMILES or graphs) took place using each model, and an early stop was allowed if the maximum score was achieved. Similarly, the FPB model was asked to generate 39 batches of 256 SMILES strings using the same conditional seed, for each of the three targets. It is noteworthy that it rediscovered all three targets even from the very first batch of 256 generated SMILES strings.  \n\nRegarding property satisfaction benchmarks, the ones that were applicable to the input descriptors with which the PCB cRNN was trained were the two logP targets and the TPSA, QED and the central nervous system multi-parameter optimization (CNS MPO) tasks. Similarly, the 100 top-scoring molecules from the ChEMBL25 test dataset were selected as conditional seeds for the PCB model to generate a single batch of 256 SMILES strings from. It is noteworthy that all molecules in ChEMBL and all virtual compounds generated by the models of the GuacaMol suite could not exceed a QED score of 0.948; this was also observed with the results of our method. Additionally, no molecule with a QED score higher than this value is reported in ref. 35, meaning that there might be an inherent natural upper bound of QED around 0.948, regardless of its definition. Given that high QED scores are scarce, only 54 known molecules in the ChEMBL25 test dataset had a value of ${\\sim}0.948$ , thus fewer seeds were used. All the results are summarized in Table 3.  \n\nOverall, the results demonstrate that the cRNN architecture performs on par with the best scoring literature algorithms featured in the GuacaMol benchmarking suite, achieving a maximum score for all eight given tasks.  \n\nControl of generated properties. The primary advantage of the PCB model is the ability to generate SMILES strings of molecules that follow the desirable properties. This was tested by using 10 conditional seeds derived from randomly selected active compounds from the DRD2 test set whose QED scores are all greater than 0.5. For each conditional seed, a batch of 256 SMILES were generated and the physicochemical properties defined in the input conditions were calculated for all valid SMILES using RDKit. As shown in Fig. 4, most of the properties of the generated valid SMILES exhibit only a small deviation from the defined conditional setpoint, with the QED property having relatively large variance around the reference level.  \n\nAll 10 property combinations that were used as a reference for this experiment were drawn from known active molecules from the DRD2 test set to challenge the PCB model with truly rare combinations, because the active molecules of the DRD2 test set have been excluded from ChEMBL and were also clustered to be dissimilar from the training and validation sets of the QSAR model. The DRD2 activity setpoint for this experiment, instead of being set to active for all 10 seeding conditions due to prior knowledge, was set according to the QSAR model’s prediction for each of the 10 known active seeds because the generated SMILES strings would be evaluated by the QSAR model anyway. Due to the QSAR model’s imperfection, two of the known active seeds (5 and 8) were falsely predicted as inactive, and the setpoint for those two was set as inactive. Therefore, the upper limit of the percentage of predicted active SMILES strings is expected to be $80\\%$ . After evaluating the probability of all generated SMILES strings that corresponded to valid molecules, ${\\sim}40\\%$ of them were predicted as active with a probability not less than 0.5.  \n\nTo further investigate the capability of a cRNN to control the properties of the molecules corresponding to its generated SMILES strings, more experiments were conducted where single properties were varied in both directions while keeping the rest of them fixed. A molecule from within the first and third quartiles with respect to all properties of the DRD2 test dataset was selected from which to obtain the initial conditions. Then, for each of the descriptors apart from the active probability, five values were tried out in a stepwise ascending fashion, spanning the value range between the first and third quartiles of each property, while keeping the rest of the conditions at the initial level. The tested conditions correspond to arbitrary property setpoints, unlike the ones shown in Fig. 4. The reference (red line) and generated (blue dots) properties of all valid SMILES strings are shown in Extended Data Fig. 4. Each column of cells per plot corresponds to the tuning of a single property while keeping the other five conditions fixed at the initial values. Overall, logP, TPSA, molecular weight and HBD setpoints were adequately matched in the generated molecular properties, followed by HBA, which seems to be unstable for low values of logP and high values of MW. The QED formula contains the weighted $\\mathsf{s u m}^{35}$ of all the other five properties; consequently, the requested conditions along with the QED setpoint may render it impossible for that equation to be satisfied. Therefore, the QED property was hard to keep at the reference value as shown by the large spread around the target value (Extended Data Fig. 4).  \n\n![](images/d37ece0158341a7e555782281c7f7629b52de13aa9aa3978caa87a8c85a247c5.jpg)  \nFig. 4 | Property satisfaction with the PCB model. Reference properties (red) are plotted against the properties of generated valid SMILES (blue) for 10 random conditional seeds from the DRD2 test set. The properties considered are the logP, TPSA, MW, QED, HBA and HBD. The numbers in parentheses denote the number of unique valid molecules out of a batch of 256 generated SMILES strings. The patterns of all generated properties follow the reference. The QED constraint is the hardest to satisfy.  \n\nThis is particularly evident in the region around low values of MW or requested high values of QED for the given seed. In the first case, logP and QED decreased under the influence of the value of MW, which was controlled by the cRNN. From the short length of the step, it is observed that this batch of SMILES suffered from high invalidity and, as far as the valid examples are concerned, their logP and QED values were much lower than the setpoint. Similarly, requested high values of QED, given the values of the other five properties, were impossible to achieve, which affected the values of all properties and eventually led to none of their setpoints being respected, as annotated with the arrow markings in Extended Data Fig. 4.  \n\nThese are the cases for which input combinations were ill-defined and resulted in either unattractive or invalid structures, something that has also been observed in the latent space vectors of autoencoders27. In the cRNN context, such combinations may refer to under-represented regions in the training dataset due either to a lack of relevant samples in the source or conflicts between the requested descriptor ranges. The conditions are entangled because they depend on each other, as observed from the behaviour of the QED score. In most cases, the user is probably interested in tuning only one of the properties rather than restraining many of them; nonetheless, all property conditions ought to be set at reasonable values to avoid the entanglement problem. More sophisticated sampling approaches, such as the LatentGAN architecture29, could potentially address the entanglement problem. In particular, the generator component of LatentGAN may be used to autonomously propose a valid combination of input properties that lead to active generations towards bioactivity targets.  \n\nExclusivity of sampling. Sampling the cRNN model with the seed conditions derived from a query structure should theoretically make it more likely to generate structures similar to the seed (Fig. 2) and less likely to sample dissimilar molecules. To investigate this hypothesis, 100,000 molecules were randomly selected from the ChEMBL test set and clustered using the DBSCAN algorithm36, based on the Euclidean distance of their five scaled physicochemical properties (logP, TPSA, MW, HBA and HBD). A value of the maximum neighbour distance, $\\varepsilon=0.1$ and 10 minimum samples for associating core points were selected as parameters of the DBSCAN algorithm.  \n\nNext, two clusters of molecules (with sizes of 53 and 57, respectively) were manually selected to keep the variance of their descriptors within a range as narrow as possible, with preferably small overlap. The distributions of logP, TPSA and MW of the selected clusters are shown in Fig. 5a–c. All the molecules of the first cluster resulted in an HBA count of four and an HBD count of zero, while all molecules of the second cluster resulted in counts of four and one, respectively. The selected clusters show minimal or no overlapping with respect to logP, TPSA and HBD count, whereas they share the same count of HBA and similar values of MW. The values of QED and predicted probability of being active were not considered during clustering.  \n\n![](images/d10983da9336a2a5e45cffd0b623d13b174980013665efaae4d6847a11332123.jpg)  \nFig. 5 | Exclusivity of sampling. a–c, Distribution of logP (a), TPSA (b) and MW (c) of each cluster. d, Distribution of calculated NLL of sampling each cluster using the two cluster centres as seeds, interchangeably. All distribution curves were fit using the kdeplot method of the seaborn Python library and default settings. A total of 10,000 randomization operations were performed on each molecule and all resulting unique randomized strings per molecule were considered when calculating the NLL using equation (5). It is shown that using a relevant seed makes it more probable to sample SMILES strings that correspond to chemically neighbouring molecules than molecules from another cluster.  \n\nA total of 10,000 randomization attempts were performed on each molecule and all resulting unique randomized strings per molecule were considered when calculating the NLL using equation (5). The seed conditions were selected as the coordinates of the geometric centre of each cluster. The conditional NLL of sampling the molecules of each cluster under different seeds was calculated according to equation (5) (Fig. 5d). The cross-conditional NLL was calculated for each cluster by swapping the conditional seeds of both clusters. Theoretically, the generation of molecules from these two clusters during conditional sampling should be mutually exclusive using their own cluster centre as seed. In other words, using each cluster centre as the seed should give a higher probability to sample molecules within the relevant cluster.  \n\nThis hypothesis is supported by Fig. 5d. When the conditional vector is derived from the seed of cluster 1, it is more likely to sample SMILES from the same molecular cluster (dark blue curve) than the ones from the second cluster (light red curve, Fig. 5d). The same applies when conditioning the generation with the molecules of the second cluster (dark red and light blue curves, Fig. 5d). Even though there is an overlap between the self-conditional and cross-conditional NLL curves, in both cases the former ones describe lower NLL values, thus showing that relevant molecules are more likely to be sampled. Overall, both clusters are comparably probable to be sampled when their own seeds are used as conditions (dark blue and dark red curves, Fig. 5d). Finally, by comparing the self-conditional NLL curves of Fig. 5d to the curves of Fig. 2, it is observed that the NLL curves of Fig. 5d are all shifted towards higher NLL values. This is expected though, because the conditions considered for each molecule were not derived from its own properties but instead from the mean properties of the cluster.  \n\nOn the use of NLL for conditional model assessment. Given the size of the chemical subspace that generative models represent, sampling 1,000 or 10,000 molecules, as the main benchmarking suites22,23 propose, may not sufficiently exemplify a model’s capacity. For uniformly trained models16 with a potential target space of zillions of equiprobable molecular strings, the expectation of rediscovering a particular molecule of interest from a left-out testing dataset as a proof of concept may be unrealistic. One may argue that the ability of a model (or the lack of it) to find a specific molecule in a finite number of attempts is indicative of the probability of distinguishing it from all other molecules and, thus, of the model’s focus on that target. However, in such an experimental set-up, we can either reject a model’s inability or fail to reject it, because accepting this hypothesis would require a significantly larger number of attempts.  \n\nIn this work, we have attempted to gain insight into different aspects of the proposed cRNN architecture using distributions of CNLL values, as described by equation (1). In Fig. 2a,b, we employ the CNLL values to assess the training quality of the cRNN models, effectively bridging the gap between unbiased and conditional models. Instead of attempting to rediscover some known active molecules from the DRD2 training and testing datasets, we prove that they would be almost as easy to sample as molecules from ChEMBL using the cRNN models as shown in Fig. 2c,d. By retrospectively calculating the NLL values for all SMILES sequences in the complete DRD2 datasets, we demonstrate the correct focus of the output of the model in a transparent fashion while exhaustively using all the available ground truth.  \n\nConsequently, we see two main benefits. First, evaluation of the output is independent of any custom scoring (QSAR) model that induces additional noise to the results, which otherwise reflect the multiplicative performance of the generative and QSAR models. This also deals with potential mode-collapsing problems of the QSAR model when applied on unseen or novel data by eliminating them from the evaluation process. Second, the CNLL formula will yield an interpretable score for any arbitrary sequence, regardless of the size of the output space of a model. By using a meaningful threshold, this score would directly reflect the model’s ability to reach the sequence of interest.  \n\nMoreover, by exchanging conditional seeds between clusters as shown in Fig. 5d, the cross-conditional NLL values can indicate the exclusivity of the focus of a model. In the field of de novo design, this could be translated to probabilistic avoidance of structural alerts, such as toxic substructures, and could serve as a meaningful test case during benchmarking of different models.  \n\nThe definition of the CNLL as proposed in equation (1) allows for the evaluation of the probability of generating a sequence given a fixed set of descriptors. As evinced by the experiments in this work, the more information that is induced into the network by the choice of descriptors, the more deterministic its output becomes. Through this operationalization, one may appreciate the stochasticity in the learnt decision process of an RNN. Thus, the combination of manually selecting the input features to train on, along with post-processing of the results using CNLL plots, could be an alternative approach to assess the collective feature importance between discrete sets of inputs of an RNN for sequence generation—a field that is under research for black box models37,38.  \n\nAll in all, we believe that such an analysis based on NLL statistics is essential for a fair comparison between models and can be adopted by all probabilistic sequence generators, regardless of domain. Yet, to extend existing benchmarks to the proposed novel direction, except for predicting a sequence, all relevant models should be modified to deliver the joint probability of sampling that sequence, or its equivalent NLL.  \n\nApplications to drug discovery and beyond. Among the core contributions of this manuscript lies the controlled specificity of the output space of the proposed cRNN architecture. The FPB cRNN, as seen from Fig. 2, has the least stochastic output of all the models, a behaviour that is close to what would be expected from autoencoding networks. The PCB NLL values for all datasets lie between the NLL values of the FPB and the unbiased models. This is significant, because it implies that the PCB model has a more diverse output space than the FPB (or similar autoencoding networks) while maintaining its focus on the property setpoints, as shown in Fig. 4 and Extended Data Fig. 4. This offers an incomparable advantage over the baseline model trained with transfer learning, because the baseline does not provide any degrees of freedom to the user to shape the output after it has been trained on a dataset. This means that the PCB model is able to find multiple near solutions to the multi-objective optimization problem at hand, whereas most current work in the literature focuses on optimization of just a single property at a time, that is, maximization of logP.  \n\nMoreover, we have shown that a cRNN can learn either physicochemical or structural characteristics, depending on the set of descriptors that are chosen by the user to expose the network to during training. Here, the selected properties consist of five physicochemical properties, a well-defined weighted average of them (QED) and a data-driven scoring function (QSAR model) based on public data. This diverse selection showcases the method in a transparent and reproducible way, while at the same time underlining the versatility of the algorithm for drug design purposes. Therefore, the cRNN architecture provides a way of addressing the inverse QSAR problem directly as the PCB cRNN is able to generate molecular structures with desired properties.  \n\nOn the contrary, other available methods suggest the use of optimization algorithms21,28 or reinforcement learning18 to close the loop and steer one or more initial candidate molecules towards the aspired region of the chemical domain in an iterative process. Such optimization approaches require looping over a cost or desirability function, whereas in our case a batch of 256 potentially interesting SMILES strings with properties close to predefined target values can be directly generated with a single forward pass of the trained cRNN. The main advantage of the proposed algorithm over this family of methods is that the inference time of a cRNN is not affected by the arbitrary complexity of the input, because it is exposed to it during training and its weights are adjusted to a specific task. It exhibits quasi-constant inference time, because the implication of sampling a sequence of unknown length on runtime performance is a common denominator for both types of algorithm. In contrast, optimization algorithms that are applied on universally pre-trained models require ad hoc exploration of the chemical space during runtime. This characteristic allows for interactive applications to be built, where a constant feedback cycle permits smooth experimentation, such as allowing the user to dynamically select the target properties and visualize the results within a laboratory set-up.  \n\nNevertheless, a combination of the two distinct approaches could potentially yield even greater benefits. The pre-trained cRNN could complement a reinforcement learning $\\mathrm{loop}^{18}$ by proposing abundant meaningful starting points that would speed up or enhance its convergence in a lead-optimization fashion. Other optimization techniques, such as particle swarm28 or Bayesian optimization21, could be used to finetune the conditional seed on top of a cRNN instead of a simple decoder, which in the case of the PCB model would be chemically interpretable, whereas the FBP model could suggest a series of similar compounds based on the optimized seed.  \n\nMost importantly, however, our proposed method addresses the general inverse design problem, where a recommender system proposes solutions on a multidimensional manifold that conform to desired specifications. One may extrapolate from our case study to a more generalized approach to the task of customizing the specificity of—and not just the context of—sequential data generation. Such examples could be natural language generation, where the focus of the context is set according to keywords, or autoregression of time-series, where the initial conditions could be set via the cRNN states. Last, but not least, based on the authors’ prior experience in the field, maintaining the levels of several process (state) variables at a specified reference using just a single output, regardless of the mode collapse that appears around extreme setpoints as shown in Extended Data Fig. 4, could be exploited in the context of decoupled control of a nonlinear dynamical system. It would be stimulating to see a comparison of cRNNs against existing solutions based on artificial neural networks39. In the same context, the cross-conditional NLL could also reveal the probabilistic distance of the output from undesirable states, such as structural resonance or singular configurations of robotic arms.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 3,
+        "chunk": "# Conclusions  \n\nIn this work, the effect of introducing molecular descriptors as inputs to an existing SMILES generator architecture based on RNNs has been investigated. Primarily, it has been shown that known molecules are more likely to be rediscovered when sampling using the descriptor conditions that represent them as inputs to a cRNN, compared to a prior unbiased model that is simply trained on the complete molecular dataset. Our approach also demonstrated the capacity of generating novel compounds that were predicted active against the DRD2 receptor, which were also chemically closer to known active compounds than the ones generated by a baseline model trained with transfer learning. Additionally, a larger fraction of predicted actives was generated by the cRNN than the baseline model. After evaluating our model against literature benchmarks, the cRNN architecture was proven at least as good as the top-scoring models of a benchmarking suite, achieving the maximum score in eight relevant goal-directed tasks. Using molecular fingerprints as conditions focuses the molecular generation even more than physicochemical properties, by acting as structural restrictions that impose a scaffold on the output that is similar, if not identical, to the reference. This also demonstrated the capability of the proposed architecture to function as a fingerprint inverter, by being able to resample the original molecule even up to $72\\%$ of the time by using a more complex network. On the other hand, physicochemical properties are more versatile and lead to molecules with more diverse structures and different scaffolds than the molecule from which the conditions were derived. The cRNN architecture tackles the inverse QSAR problem by directly shaping the properties of the generated molecules while avoiding online optimization loops. Nonetheless, even though we have been able to optimize the conditions independently of each other, not all input combinations led to valid structures due to the conditions being correlated. As an example, this was observed when conditioning with a high QED setpoint while keeping the other conditions, which are constituents of the QED score calculation, fixed. Most notably, the cRNN has thus been demonstrated as a potentially useful architecture with an arbitrarily intermediate output space between unbiased character-based RNNs and fully steered autoencoders with a 1:1 relation between latent space vectors and molecules. Additionally, our experiments exemplify a novel way of assessing the focus of the conditional output of a model using NLL plots. Due to the nature of the problem this approach targets, it is expected that the proposed architecture can also be of importance in applications in sequential content creation other than drug design.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 4,
+        "chunk": "# Methods  \n\nDatasets. The datasets used in this work originate from two publicly available sources: ChEMBL40 and ExCAPE-DB41. Data from ChEMBL were used to train the generative neural network, while data regarding the dopamine receptor D2 (DRD2) target from ExCAPE-DB were used to train a QSAR model using a support vector classifier to estimate the likelihood of a generated compound being potent towards DRD2.  \n\nChEMBL. The neural network was trained with a subset of ChEMBL version 25. Initially, the complete dataset was standardized with the MolVS Python module42 using the super parent setting, which standardizes fragment, charge, isotope, stereochemistry and tautomeric states. Molecules were filtered to only contain the atoms [H, C, N, O, F, S, Cl, Br] and for a total of fewer than 50 heavy atoms. Next, the known active molecules found in the DRD2 dataset (see section ‘ExCAPE-DB’)  \n\nwere removed from the dataset. The dataset was split into training and test subsets in a 9:1 ratio. During training, $10\\%$ of the training subset was used as a fixed validation set.  \n\nExCAPE-DB. All data regarding the DRD2 entry in ExCAPE-DB were downloaded43 and preprocessed as follows. First, duplicate compounds as well as SMILES strings12 that were not sanitizable by RDKit $\\mathrm{v}2018.09.1^{44}$ were removed from the DRD2 dataset. In total 7,129 compounds had a pXC50 value greater than five and were selected as known actives along with 100,000 random DRD2 measured-inactive compounds from ExCAPE-DB. Stereochemical information was removed by converting all molecules to non-isomeric SMILES strings. The dataset was further reduced to exclude SMILES strings that were longer than the ones in ChEMBL or contained characters not found in ChEMBL. This led to removing strings with iodine and phosphorus. All active molecules were clustered based on the pairwise Tanimoto distance of their Morgan fingerprints with a radius of two using the implementation of the Butina algorithm45 found in RDKit. The maximum distance threshold for the algorithm to associate neighbours was fixed to 0.4, with a value above this dictating different clusters. All clusters were sorted based on their size and were assigned to the train, validation and test subsets iteratively using a ‘4-1-1’ scheme; that is, for every four clusters assigned to the train set, one cluster was assigned to the validation set and one to the test set in order of decreasing cluster size.  \n\nThe curated datasets used to train all models are available from https://github. com/pcko1/Deep-Drug-Coder/tree/master/datasets.  \n\nSMILES strings randomization and vectorization. During training, the atom order of all molecules was randomized using RDKit. After converting them back to SMILES, every constituting character was one-hot encoded. Every SMILES string was thus represented by a two-dimensional (2D) array with dimensions corresponding to the length of the vocabulary and the maximum canonical SMILES length found in ChEMBL, with an offset of five extra characters to account for randomized SMILES that were longer than their canonical representation. The delimiting characters ‘^’ and $\\cdot\\varsigma^{,}$ were inserted in the beginning and end of each one-hot-encoded string, respectively. Resulting arrays that corresponded to shorter SMILES strings were padded with the end character $^{\\bullet}\\mathfrak{S}^{:}$ The considered vocabulary consisted of 35 tokens that included all common unique alphanumeric characters found in ChEMBL and DRD2 datasets after filtering, the delimiters $\\cdot_{\\wedge^{\\prime}}$ and $\\cdot\\varsigma_{;}^{*}$ and the token ‘?’ to account for one-hot encoding of unknown characters.  \n\nThe randomization and vectorization of all SMILES strings was performed dynamically using a modified version of the molvecgen Python package46 during training.  \n\nDRD2 QSAR model. A probabilistic support vector machine classification model was used for bioactivity prediction. The standard implementation of a support vector machine (SVM) from the scikit-learn $\\mathrm{v}0.20.3^{47}$ Python package was used, with the radial basis function as a kernel function. The model was trained to discriminate active compounds from inactive ones based on their 2,048-bit-radius 2 Morgan fingerprint representations. Because a poor choice of the regularization parameter, $C_{:}$ and kernel coefficient, $\\gamma,$ may have a detrimental effect on the performance of an SVM, these were optimized with a randomized search in which 50 different values per parameter were drawn from two exponential distributions with replacement. The choice of fingerprint type and radius was based on published work48,49 and was not optimized further.  \n\nRecurrent neural network. The neural network resembles the decoder architecture described in ref. 25. It was implemented in Keras $\\mathbf{v}2.2.4^{50}$ with a TensorFlowGPU v1.12.0 backend51 and is schematically shown in Fig. 1. The network accepts a vector of molecular descriptors as inputs to a set of six Dense feedforward layers of 256 units each, using the $\\mathrm{ReLU}^{52}$ activation function. The output of each individual Dense layer is used to set either the cell state or the hidden state of each of the recurrent layers of the network. There are, in total, three unidirectional recurrent layers in the network, each consisting of 256 LSTM32 neurons. The output of the final LSTM layer is fed to a feedforward layer with 35 units, which is the length of the character space, using softmax activation. Batch normalization was applied to the outputs of all LSTMs and all but the last Dense layers. Keras CUDA-enabled CuDNNLSTM units were used in the recurrent layers.  \n\nThe model was trained for 100 epochs with randomized SMILES strings following the ‘teacher’s forcing’ method53, using the ground truth at each step as prior knowledge instead of the character previously predicted by the network. A batch size of 128 sequences was used along with the Adam optimizer with default parameters54 and an initial learning rate of $10^{-3}$ . A custom learning rate schedule was used, where the learning rate was kept constant for the first 50 epochs and then decayed exponentially at each epoch, down to a value of $10^{-6}$ at the final epoch.  \n\nA copy of the trained model was modified for the purpose of predicting single characters to jointly form SMILES strings. While maintaining the trained connection weights, the shape of the output of the last feedforward layer was set to a 1D vector expressing the probability of sampling each of the known characters at every step. Also, the LSTM layers were set to stateful mode. During inference, a single character per iteration is sampled out of this vector of probabilities using multinomial sampling. After setting the initial states according to the descriptors of interest, the biased generation is triggered by feeding the start- character $\\cdot_{\\wedge^{\\prime}}$ to the network and ends when the end character $\\cdot\\varsigma^{,}$ is sampled.  \n\nTwo different cRNN models were constructed and trained following this procedure, each based on different input descriptors. The first physchem-based (PCB) model is shown schematically in Fig. 1a. The model uses the Wildman– Crippen partition coefficient55 (logP), topological polar surface area (TPSA), molecular weight (MW), number of hydrogen bond acceptors (HBA), number of hydrogen-bond donors (HBD) and the drug-likeness score35 (QED) calculated using their RDKit implementations as well as the soft label predicted by the QSAR support vector classification (SVC) model described above. The calculated values were scaled individually to achieve a distribution with zero mean and unit variance, and they were concatenated into a single input vector.  \n\nThe second fingerprint-based (FPB, Fig. 1b) model was trained solely on Morgan fingerprints of radius 2 and 2,048 bits, which are similar to extended connectivity fingerprints (ECFPs). The training and inference schemes of the cRNN models are described in Fig. 1a–c, respectively.  \n\nModel training and inferencing was performed on an NVIDIA Tesla V100 GPU on a 64 bit CentOS v7.5 server with 128 GB of RAM. The training process of the PCB and FPB models utilized 5 and 25 GB of RAM, respectively.  \n\nTransfer learning model. The baseline model consists of the same neural network architecture as described above with the notable difference that the initial states, instead of being set based on known descriptors, are instead being reset to zero in the beginning of the generation of each string. This approach is similar to the prior network described in ref. 18 with the difference that each character is treated independently rather than within multi-character tokens. The network was likewise trained with teacher’s forcing, learning the character set and the grammar of the SMILES strings found in ChEMBL. The selected RNN dimensions were identical to the ones in the case of the cRNN.  \n\nNext, the prior model was further trained exclusively with the known actives of the DRD2 train dataset for an additional 200 epochs, following a transfer learning strategy56. The initial learning rate was set to $10^{-4.5}$ and was decayed exponentially to $10^{-6}$ by the end of the training.  \n\nLikelihood of sequences and molecules. The likelihood of sampling a given SMILES string was estimated using NLL as previously described15, with a modification that incorporates the knowledge that is induced into the initial states of the generation in the case of a conditional model. The conditional NLL (CNLL) is defined as  \n\n$$\n\\mathrm{CNLL}(S|c)=-\\left[\\ln{P(X_{1}=T_{1}|c)}+\\sum_{i=2}^{N}\\ln{P(X_{i}=T_{i}|X_{i-1}=T_{i-1},\\ldots,X_{1}=T_{1},c)}\\right]\n$$  \n\nwhere $T_{i}$ are the characters in the known SMILES sequence S, $X_{i}$ are the predicted model outputs, $N$ is the length of sequence $s$ , and $\\boldsymbol{c}$ refers to the seeding conditions. The sign of the log-likelihood is made negative to reflect that higher values correspond to more improbable sequences.  \n\nThe true probability of sampling a molecule $M$ is given by the cumulative probability over all its $U$ unique random representations $S_{j}{\\mathrm{:}}$  \n\n$$\nP(M|c)=\\sum_{j=1}^{U}P\\big(S_{j}|c\\big)=\\sum_{j=1}^{U}\\mathrm{e}^{-\\mathrm{CNLL}\\big(S_{j}|c\\big)}\n$$  \n\nThus, the CNLL of a molecule is given by the negative of the natural logarithm of equation (2):  \n\n$$\n\\mathrm{CNLL}(M|c)=-\\mathrm{ln}\\sum_{j=1}^{U}\\mathrm{e}^{-\\mathrm{CNLL}\\left(S_{j}|c\\right)}\n$$  \n\nBecause the true number of all unique representations of a molecule is a priori unknown, the likelihood of a molecule can be approximated by a smaller number of unique representations $u$ such that  \n\n$$\n\\mathrm{CNLL}(M|c)=\\operatorname*{lim}_{u\\to U}\\left(-\\ln\\sum_{j=1}^{u}\\mathrm{e}^{-\\mathrm{CNLL}\\left(S_{j}|c\\right)}\\right)\n$$  \n\nwhere  \n\n$$\n\\mathrm{CNLL}(M|c,u)\\overset{\\Delta}{=}-\\ln\\sum_{j=1}^{u}\\mathrm{e}^{-\\mathrm{CNLL}\\left(S_{j}|c\\right)}\n$$  \n\nis the approximation of the true molecular likelihood given input conditions $c$ and a set of $u$ unique random string representations $S_{j}$ . Finally, from equations (2) and (4) we can derive that  \n\n$$\n\\begin{array}{r l}&{P(M|c)\\geq P(M|c,u)\\geq P\\big(S_{j}|c\\big)\\iff-\\ln(P(M|c))\\leq-\\ln(P(M|c,u))\\leq-\\ln\\big(P\\big(S_{j}|c\\big)\\big)}\\\\ &{\\iff\\mathrm{CNLI}(M|c)\\leq\\mathrm{CNLI}(M|c,u)\\leq\\mathrm{CNLI}\\big(S_{j}|c\\big)}\\end{array}\n$$  \n\nThis means that the molecular NLL cannot be higher than the NLL of any individual random sequence corresponding to the given molecule.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# Data availability  \n\nThe curated datasets used to train all models are available at https://github.com/ pcko1/Deep-Drug-Coder/tree/master/datasets.",
+        "category": " References"
+    },
+    {
+        "id": 6,
+        "chunk": "# Code availability  \n\nThe Python code and the trained neural networks used in this work are available under MIT licence57 in the Deep Drug Coder (DDC) GitHub repository https://github.com/pcko1/Deep-Drug-Coder and https://doi.org/10.5281/ zenodo.3739063, which also includes an optional encoding network to constitute a molecular heteroencoder.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# Received: 20 November 2019; Accepted: 14 April 2020; Published online: 18 May 2020",
+        "category": " References"
+    },
+    {
+        "id": 8,
+        "chunk": "# References  \n\n1.\t Lopyrev, K. Generating news headlines with recurrent neural networks. Preprint at https://arxiv.org/pdf/1512.01712.pdf (2015).   \n2.\t Briot, J.-P., Hadjeres, G. & Pachet, F.-D. Deep Learning Techniques for Music Generation (Springer, 2020).   \n3.\t Wang, Z. et al. Chinese poetry generation with planning based neural network. In Proceedings of 26th International Conference of Computing and Linguistics 1051–1060 (COLING 2016 Organizing Committee, 2016).   \n4.\t Elgammal, A., Liu, B., Elhoseiny, M. & Mazzone, M. CAN: Creative adversarial networks, generating ‘art’ by learning about styles and deviating from style norms. Preprint at https://arxiv.org/abs/1706.07068 (2017).   \n5.\t Segler, M. H. S., Preuss, M. & Waller, M. P. Planning chemical syntheses with deep neural networks and symbolic AI. Nature 555, 604–610 (2018).   \n6.\t Ronneberger, O., Fischer, P. & Brox, T. U-Net: convolutional networks for biomedical image segmentation. 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SMILES, a chemical language and information system. 1: Introduction to methodology and encoding rules. J. Chem. Inf. Comput. Sci.   \n28, 31–36 (1988).   \n13.\tSchwalbe-Koda, D. & Gómez-Bombarelli, R. Generative models for automatic chemical design. Preprint at https://arxiv.org/pdf/1907.01632.pdf (2019).   \n14.\tLipton, Z. C., Berkowitz, J. & Elkan, C. A critical review of recurrent neural networks for sequence learning. Preprint at https://arxiv.org/pdf/1506.00019. pdf (2015).   \n15.\tArús-Pous, J. et al. Exploring the GDB-13 chemical space using deep generative models. J. Cheminform. 11, 20 (2019).   \n16.\tArús-Pous, J. et al. Randomized SMILES strings improve the quality of molecular generative models. J. Cheminform. 11, 71 (2019).   \n17.\tSegler, M. H. S., Kogej, T., Tyrchan, C. & Waller, M. P. Generating focused molecule libraries for drug discovery with recurrent neural networks. ACS Cent. 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Model. 59,   \n1096–1108 (2019).   \n24.\tBjerrum, E. J. SMILES enumeration as data augmentation for neural network modeling of molecules. Preprint at https://arxiv.org/pdf/1703.07076.pdf (2017).   \n25.\tBjerrum, E. J. & Sattarov, B. Improving chemical autoencoder latent space and molecular de novo generation diversity with heteroencoders. Biomolecules 8, 131 (2018).   \n26.\tWinter, R., Montanari, F., Noé, F. & Clevert, D. A. Learning continuous and data-driven molecular descriptors by translating equivalent chemical representations. Chem. Sci. 10, 1692–1701 (2019).   \n27.\tBlaschke, T., Olivecrona, M., Engkvist, O., Bajorath, J. & Chen, H. Application of generative autoencoder in de novo molecular design. Mol. Inform. 37, 1–11 (2018).   \n28.\tWinter, R. et al. Efficient multi-objective molecular optimization in a continuous latent space. Chem. Sci 10, 8016–8024 (2019).   \n29.\tPrykhodko, O. et al. A de novo molecular generation method using latent vector based generative adversarial network. J. Cheminform 11, 74 (2019).   \n30.\tLim, J., Ryu, S., Kim, J. W. & Kim, W. Y. Molecular generative model based on conditional variational autoencoder for de novo molecular design. J. Cheminform. 10, 31 (2018).   \n31.\tJin, W., Barzilay, R. & Jaakkola, T. S. Multi-resolution autoregressive graph-to-graph translation for molecules. Preprint at https://chemrxiv.org/ articles/Multi-Resolution_Autoregressive_Graph-to-Graph_Translation_for_ Molecules/8266745/1 (2019).   \n32.\tHochreiter, S. & Schmidhuber, J. Long short-term memory. Neural Comput. 9, 1–32 (1997).   \n33.\tPreuer, K., Renz, P., Unterthiner, T., Hochreiter, S. & Klambauer, G. Fréchet ChemNet distance: a metric for generative models for molecules in drug discovery. J. Chem. Inf. Model. 58, 1736–1741 (2018).   \n34.\tDuvenaud, D. K. et al. Convolutional networks on graphs for learning molecular fingerprints. In Advances in Neural Information Processing Systems Vol. 28 (eds Cortes, C., Lawrence, N. D., Lee, D. D., Sugiyama, M. & Garnett, R.) 2224–2232 (Curran Associates, 2015).   \n35.\tBickerton, G. R., Paolini, G. V., Besnard, J., Muresan, S. & Hopkins, A. L. Quantifying the chemical beauty of drugs. Nat. Chem. 4, 90–98 (2012).   \n36.\tEster, M., Kriegel, H., Xu, X. & Miinchen, D. A density-based algorithm for discovering clusters in large spatial databases with noise. In Proceedings of the Second International Conference on Knowledge, Discovery and Data Mining 226–231 (AAAI Press, 1996).   \n37.\tŠkrlj, B., Džeroski, S., Lavrač, N. & Petkovič, M. Feature importance estimation with self-attention networks. Preprint at https://arxiv.org/ pdf/2002.04464.pdf (2020).   \n38.\tOlden, J. D., Joy, M. K. & Death, R. G. An accurate comparison of methods for quantifying variable importance in artificial neural networks using simulated data. Ecol. Model. 178, 389–397 (2004).   \n39.\tHung, L. & Chung, H. Decoupled control using neural network-based sliding-mode controller for nonlinear systems. Expert Syst. Appl. 32, 1168–1182 (2007).   \n40.\tGaulton, A. et al. The ChEMBL database in 2017. Nucleic Acids Res. 45, D945–D954 (2017).   \n41.\tSun, J. et al. ExCAPE-DB: an integrated large scale dataset facilitating big data analysis in chemogenomics. J. Cheminform. 9, 41 (2017).   \n42.\tSwain, M. MolVS: Molecule Validation and Standardization v0.1.1 (2019); https://molvs.readthedocs.io/en/latest/   \n43.\tSun, J. et al. ExCAPEDB (2019); https://solr.ideaconsult.net/search/excape/   \n44.\tLandrum, G. et al. RDKit: Open-Source Cheminformatics Software (2019); https://www.rdkit.org/   \n45.\tButina, D. Unsupervised data base clustering based on daylight’s fingerprint and Tanimoto similarity: a fast and automated way to cluster small and large data sets. J. Chem. Inf. Comput. Sci. 39, 747–750 (1999).   \n46.\tBjerrum, E. J. Molvecgen: Molecular Vectorization and Batch Generation (2019); https://github.com/EBjerrum/molvecgen   \n47.\tPedregosa, F. et al. Scikit-learn: machine learning in Python. J. Mach. Learn. Res. 12, 2825–2830 (2011).   \n48.\tO’Boyle, N. M. & Sayle, R. A. Comparing structural fingerprints using a literature-based similarity benchmark. J. Cheminform. 8, 36 (2016).   \n49.\tProbst, D. & Reymond, J. L. A probabilistic molecular fingerprint for big data settings. J. Cheminform. 10, 66 (2018).   \n50.\tChollet, F. Keras (2019); https://keras.io/   \n51.\tAbadi, M. et al. TensorFlow: large-scale machine learning on heterogeneous distributed systems. Preprint at https://arxiv.org/pdf/1603.04467.pdf (2016).   \n52.\tArora, R., Basu, A., Mianjy, P. & Mukherjee, A. Understanding deep neural networks with rectified linear units. Preprint at https://arxiv.org/pdf/ 1611.01491.pdf (2016).   \n53.\tWilliams, R. J. & Zipser, D. A learning algorithm for continually running fully recurrent neural networks. Neural Comput. 1, 270–280 (2008).   \n54.\tKingma, D. P. & Ba, J. Adam: a method for stochastic optimization. In 3rd International Conference for Learning Representations, (ICLR) 2015, San Diego, CA, USA, May 7-9, 2015, Conference Track Proceedings (eds Bengio, Y. & LeCun, Y.) (2015).   \n55.\tWildman, S. A. & Crippen, G. M. Prediction of physicochemical parameters by atomic contributions. J. Chem. Inf. Comput. Sci. 39, 868–873 (1999).   \n56.\tTan, C. et al. A survey on deep transfer learning. In Artificial Neural Networks and Machine Learning — ICANN 2018 (eds Krurková, V., Manolopoulos, Y., Hammer, B., Iliadis, L. & Maglogiannis, I.) 270–279 (Springer, 2018).   \n57.\tMIT Licence; https://opensource.org/licenses/MIT",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# Acknowledgements  \n\nWe thank the entire MolecularAI team at AstraZeneca for their invaluable input and the fruitful discussions held during development of the present work. J.A.-P. is supported financially by the European Union’s Horizon 2020 research and innovation programme under a Marie Skłodowska-Curie grant (agreement no. 676434, ‘Big Data in Chemistry’, ‘BIGCHEM’; http://bigchem.eu).",
+        "category": " References"
+    },
+    {
+        "id": 10,
+        "chunk": "# Author contributions  \n\nP.-C.K. and E.J.B. planned the project and jointly performed analysis of the results. P.-C.K. developed the necessary code. E.J.B. supervised the overall project. J.A.-P. assisted with the preprocessing of the datasets. J.A.-P., H.C., O.E. and C.T. provided valuable  \n\nfeedback on the methods used, the experimental set-up and the results at every stage.   \nP.-C.K. wrote the manuscript and all authors reviewed it.",
+        "category": " Abstract/Introduction/Materials and methods/Results and discussion/Conclusions/References \n\nText segment classification: Author contributions is not part of the primary research sections and typically provides information about the contribution of authors to the study; it is commonly found in papers right before the acknowledgment or after the conclusion. However, since this section does not correspond to any of the specified categories, it does not fit nicely into the standard sections of a research paper provided.\n\nGiven that additional clarification might point towards the context, it may belong to a section categorized as 'Acknowledgments' or a similar section not listed.\n\nHowever, if forced to choose from the provided categories, we could interpret it as an appendix to the results of the discussion since it outlines contributions related to the project outcomes. \n\nThus, here is the closest fit:\n\nCategory: Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# Competing interests  \n\nThe authors declare no competing interests.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 12,
+        "chunk": "# Additional information  \n\nExtended data is available for this paper at https://doi.org/10.1038/s42256-020-0174-5.  \n\nSupplementary information is available for this paper at https://doi.org/10.1038/ s42256-020-0174-5.  \n\nCorrespondence and requests for materials should be addressed to E.J.B.  \n\nReprints and permissions information is available at www.nature.com/reprints.  \n\nPublisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.  \n\n$\\circledcirc$ The Author(s), under exclusive licence to Springer Nature Limited 2020",
+        "category": " References"
+    },
+    {
+        "id": 13,
+        "chunk": "# Articles",
+        "category": " References"
+    },
+    {
+        "id": 14,
+        "chunk": "# Nature Machine Intelligence  \n\n![](images/36cfc006b213525f07a0d47fa3b60fa6006a7164ef662bad9fbd3d9c391a844e.jpg)  \nExtended Data Fig. 1 | Distribution of physicochemical properties of datasets. a, Wildman-Crippen coefficient (logP), b, topological polar surface area (TPSA), c, molecular weight (MW), d, drug-likeness score (QED), e, number of hydrogen bond acceptors (HBA) and f, hydrogen bond donors (HBD) with respect to the complete CHEMBL25 and DRD2 datasets before splitting. Subfigures a-d show the continuous histogram density as estimated by the kdeplot method of the seaborn Python library using default parameters.  \n\n![](images/6d888e805118956c96b967c888968aeaaa3650d60cc1b4dedce6d26560d49ffc.jpg)  \nExtended Data Fig. 2 | Tanimoto similarity and predicted activity of generated structures. a, Distribution of pairwise Tanimoto similarity of uniquely generated Murcko scaffolds to the seeding Murcko scaffold. The physchem-based (PCB) model generates SMILES that correspond to new scaffolds whereas the fingerprint-based (FPB) model generates scaffolds that are more similar or even identical to the seeding scaffold. b, Predicted active probability of all unique structures behind all generated SMILES strings per model. Both models generate SMILES that are predicted to be active with similar probability distributions.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# Articles  \n\n![](images/c7ab0d9a56a893edc1076b43ac476bd59714c05ae243cb8e554156aaaf7b7fc2.jpg)  \nNature Machine Intelligence   \nExtended Data Fig. 3 | Novelty of uniquely generated underlying molecules with respect to different datasets. Novelty is assessed with respect to the train and test ChEMBL datasets using the physchem-based (PCB) and fingerprint-based (FPB) models. The first element of every pair on the $\\mathsf{x}$ -axis corresponds to the dataset the conditions were drawn from. The second element represents the dataset with respect to which novelty was calculated. For any model the difference between datasets is insignificant, reflecting a consistent generation of novel compounds regardless of the seeding conditions. The numbers correspond to the fraction of valid unique novel molecules out of 25,600 generated SMILES strings.  \n\n![](images/4140e9abde6c4945b1af034731fecd7a889551f6d944ec4db6a7e837fda4aad5.jpg)  \nExtended Data Fig. 4 | Optimization of properties individually in every direction with the physchem-based model. The pattern of the molecular properties of the generated valid SMILES (blue dots) seems to follow the set conditions (red lines). The length of a step represents the number of valid SMILES for that setpoint out of 256 sampled SMILES strings. Low molecular weight or high QED setpoints lead to unstable generation of valid SMILES for the given condition. QED displays the largest deviations from the seed conditions and is the hardest property to control as the formula contains a weighted sum of the other five properties. The area annotated by arrows refers to an input combination with a high QED target that caused the output to collapse with respect to the rate of valid SMILES and the fulfillment of the specified conditions. The exact percentage of unique molecules stemming from all valid SMILES sampled at each step is shown in Supplementary Fig. 12.",
+        "category": " Results and discussion"
+    }
+]
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+    {
+        "id": 1,
+        "chunk": "# 基于机器学习的隐身涂料设计方法与研究进展  \n\n刘 旭1，刘永豪2，齐建涛\\*2（1. 海军航空大学青岛校区，山东青岛264000；2. 中国石油大学（华东），山东青岛266580）  \n\n摘　要：隐身涂料通过对雷达波、红外辐射、可见光及激光信号特性的调控，广泛应用于军事装备与先进技术领域。然而，隐身涂料的设计涉及多种材料和复杂加工参数的耗时实验。为了克服这些限制，数据驱动的涂料设计方法受到广泛关注。文章综述了基于机器学习的隐身涂料设计的最新进展。概括了隐身涂料的主要类型，包括吸波涂料、电磁屏蔽涂料、红外隐身涂料和复合隐身涂料，探讨了传统设计方法面临的挑战。介绍了数据驱动的隐身涂料设计，展示了数据预处理与特征提取策略如何优化模型输入，强调了高质量数据库、模型可解释性与多目标优化的重要性。此外，总结了机器学习在隐身涂料性能预测、材料筛选、结构设计及逆向优化等方面的研究案例。最后，探讨了各领域数据驱动下功能涂料的最新研究，为隐身涂料的智能设计提供参考。  \n\n关键词：隐身涂料；机器学习；数据驱动；设计方法  \n\n中图分类号：TQ637. 7 文献标志码：A 文章编号：0253-4312（2025）03-0013-06  \ndoi：10. 12020/j. issn. 0253-4312. 2024-319",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# Research Progress and Design Methods of Stealth Coatings Based on Machine Learning  \n\nLIU Xu1，LIU Yonghao2，QI Jiantao2（1. Naval Aviation University Qingdao Campus，Qingdao，Shandong   264000，China；2. China University ofPetroleum（East China），Qingdao，Shandong   266580，China）  \n\nAbstract：Stealth coatings，by regulating radar waves，infrared radiation，visible light，and laser signals，were widely applied in military equipment and advanced technological fields. However，the design of stealth coatings involved time-consuming experiments due to the complexity of material selection and processing parameters. To address these limitations，datadriven coatings design methods had attracted increasing attention. This review highlighted recent advances in stealth coatings design based on machine learning. It summarized the main types of stealth coatings，including radar-absorbing，electromagnetic shielding，infrared stealth，and composite stealth coatings，while discussing the challenges of traditional design methods. The review introduced data-driven stealth coatings design approaches，demonstrating how data preprocessing and feature extraction strategied optimize model inputs. It underscored the significance of high-quality databases，model interpretability，and multi-objective optimization. Additionally，research cases were presented where machine learning had been applied in performance prediction，material screening，structural design，and inversed optimization of stealth coatings. Finally，recent data-driven research advancements in functional coatings across various fields were explored，providing valuable insights into the intelligent design of future stealth coatings.  \n\nKey words：stealth coatings；machine learning；data-driven；design methods  \n\n隐身涂料作为隐身技术的重要组成部分，通过对电磁波、红外辐射等能量形式的吸收、反射与屏蔽，广泛应用于航空航天、舰船和地面装备等领域，在提升航空器材隐身性能方面具有关键作用[1]。在现代战场上，高技术探测手段中雷达探测约占 $60\\%$ ，红外探测约占$30\\%^{\\left[2\\right]}$ 。随着军事装备的快速发展，隐身涂料的类型逐渐多样化，隐身涂层在战机涂层系统中所占比例已超过 $50\\%$ ，飞机的隐身性能已成为衡量武器装备先进性的重要指标[3]。通过减少雷达波段的电磁反射，隐身涂料能够显著降低被探测的可能性，从而提升飞机在复杂应用场景和动态威胁环境中的生存能力[4]。  \n\n隐身涂料研究正从单一功能优化向多功能集成与智能化方向快速推进。然而，隐身涂料的开发涉及复杂的材料选择、多变量性能优化和环境适应性设计[5]，这对传统的实验与仿真方法提出了极大挑战。这种复杂性导致开发周期长、成本高，难以满足现代武器装备的快速迭代需求。在这一背景下，机器学习技术为隐身涂料研究带来了革命性变革。机器学习通过挖掘材料属性与性能之间的复杂关联，构建高效预测模型，突破了传统方法的局限性[6]。相比传统实验与仿真，机器学习可快速解析高维非线性关系，实现性能预测与逆向设计闭环优化，从而降低研发成本并缩短开发周期。尤其是在跨学科融合的背景下，机器学习与材料科学、电磁学等领域的结合[7]，使得隐身涂料研究从“经验驱动”向“数据驱动”转型，加速了多功能、高性能涂料的开发。  \n\n本文介绍了不同类型隐身涂料及其在传统研发方式中面临的挑战，分析了数据驱动在隐身涂料设计中的关键环节，系统梳理了机器学习在隐身涂料研究中的应用，旨在为隐身涂料的设计提供参考与实践指导。",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# 1 隐身涂料的介绍  \n\n隐身涂料根据目标波段电磁波衰减或屏蔽的机理分为吸波涂料、电磁屏蔽涂料、红外隐身涂料、复合隐身涂料等。吸波涂料通过吸收不同频段的电磁波，抑制信号的反射和散射，从而减少环境中的电磁干扰[8]。其性能取决于吸波材料的种类及结构设计，常见材料包括铁氧体、碳基材料和导电聚合物等[9]。通过优化材料组成和涂层厚度，进一步提升吸波性能，以满足特定的应用需求[10]。电磁屏蔽涂料通过反射、吸收以及耗散电磁能量，以此减少电磁干扰对设备正常运行的威胁[11]。近年来，纳米材料的加入为电磁屏蔽涂料注入了新活力，显著提升了其屏蔽效能与机械性能。红外隐身涂料用于降低目标在红外成像设备中的可探测性，常用材料包括碳基材料、金属氧化物、陶瓷材料以及铝粉、青铜粉等金属材料，这些材料通过在不同温度范围内调控辐射特性实现红外隐身。复合隐身涂料结合吸波、电磁屏蔽和红外隐身等功能，通过材料的协同作用实现多频段隐身效果[12]。  \n\n随着探测技术的多样化，单一波段隐身涂料难以应对复杂的实战需求，发展具备多频谱兼容性能的隐身涂料已成为重要方向。传统材料开发方法以试错法和经验为主[13]，尽管这种方法在已知材料的测试中有效，但其效率低、成本高，过于依赖研究人员的专业素养，难以在多组分和复杂体系中发现新材料[14]。因此，机器学习的融入将成为推动新型隐身涂料研发的重要力量。",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2 数据驱动的隐身涂料设计  \n\n为应对隐身涂料传统研发方式面临的挑战，数据驱动的设计方法是将设计流程从传统的“试错法”转变为依赖大规模数据和算法模型的闭环优化。图1展示了数据驱动的隐身涂料设计流程，涵盖数据库建立、模型构建、样本推荐和实验验证等关键步骤。",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2. 1 数据的获取与组织  \n\n数据库在隐身涂料的智能设计中扮演着至关重要的角色。隐身涂料的性能受材料成分、结构设计和环境条件的多重影响，其性能优化需要整合多维度、多来源的数据[15]。数据来源是隐身涂料数据库构建的基础，其主要包括文献资料、实验数据和数值模拟数据等，数据库的质量和数量直接决定了模型的预测精度和泛化能力[16-17]。在隐身涂料的研究中，实验获取数据成本高、周期长，且许多特殊性能的测试需要昂贵的设备和复杂的实验条件。文献资料提供了现成的、经过科学验证的公开数据来源，能够减少实验工作量，补充数据集的不足。实验数据是数据库的重要组成部分，涵盖隐身涂料在吸波性能、电磁屏蔽性能以及环境适应性等方面的测试结果。数值模拟数据是实验数据的重要补充，在数据获取成本较高或实验条件受限的情况下，通过有限元分析、时域有限差分等仿真工具生成的电磁参数数据，可显著扩展数据库的覆盖范围[18]。  \n\n![](images/4663b7f4e6b417a11beb8e093feaf507c1fac975c3dd00c6fa0b42cbf494e03f.jpg)  \n图1　数据驱动的隐身涂料设计流程  \nFig. 1　Data-driven design process of stealth coatings",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2. 2 数据处理与特征优化策略  \n\n在基于机器学习的隐身涂料设计中，电磁参数、层厚配置、填料比例以及测量条件等多维度因素数据存在噪声、缺失与异常值[19]。为确保模型预测的准确性，需要对隐身涂料的数据进行处理。通过滤波和降噪技术提高电磁响应数据的信噪比，采用插值填补缺失值，利用归一化与标准化手段消除跨越多个数量级的隐身特性指标的量纲差异，并借助异常检测剔除偏离值，为后续的模型训练与设计优化提供可靠的输入基础。  \n\n在此基础上，对高维冗余特征进行精炼与优化能显著提升模型设计能力和效率。特征提取应着重发掘与隐身性能设计相关的关键参数，将多维数据简化为能表征设计目标的核心变量[20]。通过特征选择和降维方法去除冗余信息，提高模型的泛化能力和计算效率。同时，多模态特征融合可以整合电磁特性、材料组成与结构参数，以全面描绘隐身涂料的设计空间，从而在机器学习模型的帮助下更高效地搜索与优化满足隐身需求的材料和涂层结构组合。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 3 机器学习在隐身涂料设计中的应用",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 3. 1 性能预测  \n\n吸波涂料的性能评估主要依赖于其吸波效率，并会受到材料的电磁参数和几何特性等因素影响[21]。机器学习模型可根据输入参数精准预测材料在不同频率下的吸波表现。Sidi Salah 等[22]利用多层感知器神经网络优化了聚碳酸酯/多壁碳纳米管复合材料的吸波性能。结果表明，当CNT 含量为 $5\\%$ 时，该复合材料在微波频段表现出最佳吸波性能。此外，基于人工神经网络的模型成功预测了宽带吸波材料的反射频谱，不仅降低了对全波仿真的依赖，还提升了预测效率和准确性[23]。通过收集大规模实验和仿真数据，可以实现特定频率段的屏蔽效能预测模型构建。韩玲艳[24]利用遗传算法优化了涂层的电磁参数与厚度，使其在特定频段内显著降低了雷达散射截面。  \n\n涂层材料的环境适应性是其实际应用中的重要性能指标，尤其是在高温、高湿和腐蚀等极端环境中的性能稳定性[25]。虽然目前针对隐身涂料环境适应性的机器学习研究案例较少，但在其他材料领域，已有成功案例可供借鉴。Kuang 等[26]基于机器学习模型对低合金钢在大气条件下的腐蚀速率进行了预测，模型整合了环境参数和材料特性，通过XGBoost等算法显著提高了预测精度和模型的泛化能力，展现了机器学习在处理复杂环境因素与材料性能之间非线性关系的潜力。类似的方法可以被引入隐身涂料的环境适应性预测中，通过构建涂料特性与外界环境条件之间的映射关系，快速评估其在极端环境下的性能变化。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 3. 2 材料筛选与设计  \n\n机器学习是隐身涂料开发中材料筛选与设计的重要应用方向。通过建立材料属性与目标性能的映射关系，快速甄选出满足特定隐身性能要求的材料组合。仲陆祎等[27]利用随机森林回归和支持向量回归模型，构建了羰基铁/四氧化三铁复合吸波材料的磁导率预测模型。通过两步高通量筛选，选出3个性能优异的虚拟材料样本，其中实验验证的样本预测误差仅为 $3.14\\%$ 和 $-6.56\\%$ 。该研究揭示了工艺参数与材料性能的内在关系，为运用机器学习优化设计隐身涂料提供了新思路。  \n\n在材料设计方面，机器学习通过回归模型或生成模型实现性能驱动的逆向设计。Liu 等[28]提出了一种结合 Maxwell-Garnett 模型、机器学习和电磁仿真的数据驱动框架，用于优化材料的吸波性能。通过构建目标导向的设计策略，利用机器学习算法评估吸波材料的关键设计参数。通过模型的高效迭代优化，研究筛选出最优的材料设计方案，实现了从正向预测到逆向设计的功能转变。优化后的材料在$1.76\\mathrm{mm}$ 厚度下实现了 $8.2\\:\\mathrm{GHz}$ 的宽吸收带宽，覆盖X波段和 $\\mathrm{Ku}$ 波段，展现了多目标性能优化的优越性。  \n\n隐身涂料的开发往往需要在吸波性能、电磁屏蔽能力和耐候性等多个指标之间找到平衡。机器学习结合进化算法为解决此类问题提供了高效手段。Green 等[29]利用数据驱动框架优化了聚（3，4-乙撑二氧噻吩）（PEDOT)的微波吸收性能，通过非线性插值技术显著提升了宽带吸收能力。实验验证表明，当PEDOT 含量为 $30.0\\%$ 时，材料在 $3.4\\mathrm{mm}$ 厚度下实现了−54. 0 dB 的吸收峰值，吸收带宽也得到显著提升。该研究为隐身涂料的多目标性能优化提供了新的技术路径。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3. 3 逆向设计与生成策略  \n\n逆向设计与生成策略为新型隐身涂料开发和性能优化提供了创新性方法。通过构建逆向设计模型，可根据目标性能需求生成满足要求的材料结构和成分，实现从“数据驱动”向“性能驱动”的转变。图2展示了机器学习在隐身涂料设计中的双向功能，从材料参数预测性能到根据性能需求逆向生成材料参数，体现了机器学习技术在隐身涂料设计中的潜力与灵活性。  \n\n![](images/062eb790eced6edfdfcca06ffd898e120840eeae3489d127a95953a0d9d7babf.jpg)  \n图2　基于机器学习的隐身涂料正向预测和逆向设计示意图 Fig. 2　Schematic diagram of forward prediction and inverse design of stealth coatings based on machine learning  \n\n逆向设计推动了隐身涂料研究从传统的性能预测向主动优化的转型。Che 等[30]提出了一种基于支持向量回归和逆向投影算法的高通量设计框架，改善了羰基铁/四氧化三铁复合吸波涂料的微波吸收性能。优化后的材料展现出反射损耗最低值−45. 3 dB，吸收带宽提升了 $360\\%$ 。与此同时，蔡长旭[31]通过卷积神经网络和增量学习算法，将逆向设计成功应用于多层吸波材料和蜂窝吸波材料的优化开发，表明了逆向设计方法能够有效应对多目标性能需求。  \n\n隐身涂料设计通常需要兼顾多项性能要求，而传统设计方法在高维设计空间中难以找到全局最优解。机器学习结合生成模型与进化算法，为多目标优化提供了高效工具。郭昱辉[32]利用深度学习与粒子群算法结合，优化了低反射率雷达超材料的幅度与相位调控。此外，生成对抗网络和深度神经网络为隐身涂料的逆向设计带来了更大灵活性。Wang等[33]通过深度学习与严格耦合波分析法的结合，在近红外激光波长处达到0. 88 的高吸收率。田宇泽[34]基于深度神经网络预测吸波体的电磁特性，并结合生成对抗网络实现了吸波体结构的按需设计。  \n\n综上所述，现阶段机器学习在隐身涂料中的应用特点相较于传统方法，主要体现在从多角度大幅提升隐身涂料设计的效率，尚无研究证实可以直接通过数据驱动的方式实现新型隐身涂料的创新设计。现有文献大多聚焦于隐身材料的性能优化与结构设计，针对基于机器学习的涂覆型隐身材料设计的研究仍较匮乏。然而，这些研究所采用的技术框架与数据驱动方法，对于隐身涂料的性能预测、材料筛选以及逆向设计等方面仍具有重要的参考与借鉴价值。随着人工智能的日益发展与多学科交叉的不断加强，机器学习有望在隐身涂料的设计上实现“高效”到“创新”的突破。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 4 结　语  \n\n机器学习技术已应用于航空工业中的热障/环境障涂层、海洋工业中的防腐/防污涂料以及能源产业中的光催化涂层等各行业功能性涂料的设计，成功研发出超硬高熵陶瓷涂层、激光熔覆镍基自熔融合金涂层和水声聚氨酯涂层等功能性涂层。尽管数据驱动的设计方法在隐身涂料的研发中极具潜力，当前的研究依然面临数据共享与标准化的不足、实验数据可重复性与误差传播问题、模型可解释性较低以及多目标优化难度高等挑战。  \n\n未来，隐身涂料研究应加快构建高质量、可复用的开放式数据库与标准化数据处理流程，提高模型在跨尺度、跨领域数据环境下的泛化能力，为多源异构数据的高效管理与调用奠定基础。同时，通过整合材料科学、电磁学与人工智能等多学科优势，发展具备物理机理解读能力的可解释性模型，将已有基础学科理论纳入解释过程，构建一种“数据驱动 $^+$ 机理解释”的混合模型框架，为隐身涂料的优化设计提供保障。进一步还可以关注可持续性与环境影响评估，将功能性与绿色环保理念融入数据驱动的材料设计框架中，确保隐身涂层在实际使用中具备长寿命、低能耗和环境友好特性。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 12,
+        "chunk": "# 参考文献  \n\n[ 1 ] 于思珂，鲍艳，高璐，等. 多功能红外隐身材料的设计及应用[J]. 化学进展，2024，36（9）：1349-1362.YU S K，BAO Y，GAO L，et al. Design and application ofmultifunctional infrared stealth materials[J]. Advances inChemistry，2024，36（9）：1349-1362.  \n[ 2 ] 徐国跃，钱淇，方罡，等. 多频段隐身材料的研究现状与进展[J]. 航空科学技术，2022，33（1）：1-9.XU G Y，QIAN Q，FANG G，et al. Research status andprogress of multi-spectrum stealth materials[J]. AeronauticalScience & Technology，2022，33（1）：1-9.  \n[ 3 ] 陈易诚，涂建勇，李鑫，等. 雷达/红外兼容隐身材料设计原理及研究进展[J/OL]. 材料导报，2024：1-17（2024-05-07）[2024-12-16]. http：//kns. cnki. net/kcms/detail/50. 1078.TB. 20240507. 1107. 004. html.CHEN Y C，TU J Y，LI X，et al. Design principles andresearch progress of radar/infrared compatible stealthmaterials[J/OL]. Materials Herald，2024：1-17（2024-05-07）[2024-12-16]. http：//kns. cnki. net/kcms/detail/50. 1078.TB. 20240507. 1107. 004. html.  \n[ 4 ] JIN L，ZHAO Y，CHEN C，et al. Application，development，and challenges of stealth materials/structures in next-generation aviation equipment[J]. Applied Surface ScienceAdvances，2024，19：100575.  \n[ 5 ] 江文杰. 红外隐身涂料的制备及其在帐篷织物上的应用[D].上海：东华大学，2016.JIANG W J. Preparation of infrared stealth coating and itsapplication on tent fabric[D]. Shanghai：Donghua University，2016.  \n[ 6 ] 沙伟华，田永丰，施颖波，等. 浅谈人工智能在化学涂料领域的应用[J]. 现代涂料与涂装，2023，26（10）：39-42.SHA W H，TIAN Y F，SHI Y B，et al. An overview of theapplication of artificial intelligence in the field of chemicalcoatings[J]. Modern Coatings and Painting，2023，26（10）：科学的研究进展[J]. 吉林师范大学学报（自然科学版），2023，44（1）：21-33.ZHAO R，SHI J C，LIU F N，et al. Research progress ofartificial neural network accelerated computational materialsscience[J]. Journal of Jilin Normal University（Natural ScienceEdition），2023，44（1）：21-33.  \n[ 8 ] 王小兵，沈显灿，杨鸯群，等. 隐身纳米吸波材料的研究进展[J]. 当代化工研究，2024（11）：24-26.WANG X B，SHEN X C，YANG Y Y，et al. 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ACS Nano，2018，12（6）：6326-6334.  \n[19] NADELL C C，HUANG B，MALOF J M，et al. Deeplearning for accelerated all-dielectric metasurface design[J].Optics Express，2019，27（20）：27523-27535.  \n[20] 刘阳. 基于深度学习的超材料电磁仿真技术研究[D]. 武汉：华中师范大学，2019.LIU Y. Research on electromagnetic simulation technologyof metamaterials based on deep learning[D]. Wuhan：CentralChina Normal University，2019.  \n[21] 尉涞，吴楠，邢素丽，等. 层合结构复合材料电磁结构铺层优化设计[J/OL]. 国防科技大学学报，2024：1-8（2024-12-06）[2025-01-06]. http：//kns. cnki. net/kcms/detail/43.1067. T. 20241206. 1056. 002. html.WEI L，WU N，XING S L，et al. Optimized design ofelectromagnetic structural lay-ups for laminated structuralcomposites[J/OL]. Journal of National University of DefenseTechnology，2024：1-8（2024-12-06）[2025-01-06]. http：//kns. cnki. net/kcms/detail/43. 1067. T. 20241206. 1056.002. html.  \n[22] SIDI SALAH L，CHOUAI M，DANLEE Y，et al. Simulationand optimization of electromagnetic absorption of polycarbonate/CNT composites using machine learning[J]. Micromachines，2020，11（8）：778.  \n[23] 杨晓璐. 基于机器学习和优化算法的宽带超材料吸波器研究[D]. 南京：东南大学，2022.YANG X L. Research on broadband metamaterial absorberbased on machine learning and optimisation algorithm[D].Nanjing：Southeast University，2022.  \n[24] 韩玲艳. 基于机器学习的吸波材料优化设计方法[D]. 上海：华东师范大学，2020.HAN L Y. Optimal design method for wave-absorbingmaterials based on machine learning[D]. Shanghai：EastChina Normal University，2020.  \n[25] 孙迎翔，柯燕飞，吴杨敏，等. 海洋环境智能防腐涂层：结构设计与响应机制[J]. 涂料工业，2024，54（9）：77-84.SUN Y X，KE Y F，WU Y M，et al. Intelligent anti-corrosion coating for marine environments：structural designand response mechanism[J]. Paint & Coatings Industry，2024，54（9）：77-84.  \n[26] KUANG J，LONG Z. Prediction model for corrosion rate oflow-alloy steels under atmospheric conditions usingmachine learning algorithms[J]. International Journal ofMinerals，Metallurgy and Materials，2024，31 （2） ：337-350.  \n[27] 仲陆祎，权斌，车仁超，等. 基于机器学习的羰基铁/四氧化三铁复合吸波材料的优化设计[J]. 中国材料进展，2024，43（7）：652-657.ZHONG L Y，QUAN B，CHE R C，et al. Optimal design ofcarbonyl iron/triiron tetraoxide composite wave-absorbingmaterials based on machine learning[J]. Progress ofMaterials in China，2024，43（7）：652-657.  \n[28] LIU Y，HUANG X，YAN X，et al. Performance optimizationengineering of multicomponent absorbing materials basedon machine learning[J]. ACS Applied Materials &Interfaces，2023，15（22）：27056-27064.  \n[29] GREEN M，THI VAN TRAN A，CHEN X. Realizingmaximum microwave absorption of poly（3， $^{4-}$ ethylened-ioxythiophene）with a data-driven method[J]. ACS AppliedElectronic Materials，2020，2（9）：2937-2944.  \n[30] CHE R，WU Z，QUAN B，et al. Machine learning-directedfast and high-throughput acquisition of high-efficiencymicrowave absorbents from infinite design space[J].Advanced Functional Materials，2023，33（50）：2303108.  \n[31] 蔡长旭. 基于机器学习的吸波材料优化研究[D]. 成都：电子科技大学，2023.CAI C X. Optimisation study of wave-absorbing materialsbased on machine learning[D]. Chengdu：University ofElectronic Science and Technology，2023.  \n[32] 郭昱辉 . 机器学习的电磁损耗与相位对消超材料设计[D]. 武汉：华中科技大学，2023.GUO Y H. Design of electromagnetic loss and phasecancellation metamaterials based on machine learning[D].Wuhan：Huazhong University of Science and Technology，2023.  \n[33] WANG L，DONG J，ZHANG W，et al. Deep learningassisted optimization of metasurface for multi-band compatibleinfrared stealth and radiative thermal management[J].Nanomaterials，2023，13（6）：1030.  \n[34] 田宇泽. 机器学习的电磁超材料逆向设计方法研究[D].武汉：华中师范大学，2021.TIAN Y Z. Research on reverse design method ofelectromagnetic metamaterials based on machine learning[D].Wuhan：Huazhong Normal University，2021.  \n\n收稿日期 2025-02-06（修改稿）",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Soft Materials and Devices Enabling Sensorimotor Functions in Soft Robots  \n\nPublished as part of Chemical Reviews special issue “Soft Robotics”. Jiangtao Su, Ke He, Yanzhen Li, Jiaqi Tu, and Xiaodong Chen\\*",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# Cite This: https://doi.org/10.1021/acs.chemrev.4c00906",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# ACCESS  \n\nMetrics & More  \n\nArticle Recommendations  \n\nABSTRACT: Sensorimotor functions, the seamless integration of sensing, decision-making, and actuation, are fundamental for robots to interact with their environments. Inspired by biological systems, the incorporation of soft materials and devices into robotics holds significant promise for enhancing these functions. However, current robotics systems often lack the autonomy and intelligence observed in nature due to limited sensorimotor integration, particularly in flexible sensing and actuation. As the field progresses toward soft, flexible, and stretchable materials, developing such materials and devices becomes increasingly critical for advanced robotics. Despite rapid advancements individually in soft materials and flexible devices, their combined applications to enable sensorimotor capabilities in robots are emerging. This review addresses this emerging field by providing a comprehensive overview of soft materials and devices that enable sensorimotor functions in robots. We delve into the latest development in soft sensing technologies, actuation mechanism, structural designs, and fabrication techniques. Additionally, we explore strategies for sensorimotor control, the integration of artificial intelligence (AI), and practical application across various domains such as healthcare, augmented and virtual reality, and exploration. By drawing parallels with biological systems, this review aims to guide future research and development in soft robots, ultimately enhancing the autonomy and adaptability of robots in unstructured environments.",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# CONTENTS  \n\n1. Introduction   \n2. Sensing Technologies and Materials 2.1. Pressure Sensors 2.1.1. Piezoresistive 2.1.2. Capacitive 2.1.3. Piezoelectric 2.1.4. Triboelectric 2.1.5. Other (Magnetic and Optical) 2.2. Strain Sensors 2.2.1. Resistive 2.2.2. Capacitive 2.2.3. Piezoelectric and Triboelectric 2.2.4. Other 2.3. Temperature Sensors 2.3.1. Resistive type 2.3.2. Thermistor 2.3.3. Thermocouple 2.3.4. Other 2.4. Optical Sensors 2.4.1. Mechanism and Materials 2.4.2. Integrated Photonic Systems 2.5. Chemical Sensors 2.5.1. Carbon Materials  \n\n![](images/96138d327b80c177be4806e4a206e06195e8ba9391691ea63e850fa1e44ba272.jpg)  \n\n2.5.2. Transition Metal Dichalcogenides   \n(TMDs) Z   \n2.5.3. Metal−Organic Frameworks (MOFs) Z   \n2.5.4. Metal Oxides and Composites Z   \n2.5.5. Other Materials Z   \n2.6. Acoustic Sensors AB   \n2.6.1. Ultrasound Waves AB   \n2.6.2. Audible Waves AD   \n2.7. Electromagnetic Sensors AE   \n2.7.1. Magnetoreception AE   \n2.7.2. Electroreception AE   \n2.8. Multimodal Integration AG   \n2.8.1. Normal and Shear Force AG   \n2.8.2. Other Integrated Multimodal Sensing   \nTechnologies AI   \n2.9. Future Development AJ   \n3. Actuation Modalities and Materials AL  \n\n3.1. Fluidic Actuators 3.1.1. Hydraulic 3.1.2. Pneumatic 3.2. Electroactive Actuators 3.2.1. Dielectric Elastomer Actuators 3.2.2. Hydraulically Amplified Electrostatic Actuators 3.2.3. Piezoelectric Actuators 3.2.4. Electrochemical Actuators 3.3. Magnetic Actuators 3.3.1. Solid-state Magnetic Robots 3.3.2. Liquid-State Magnetic Robots 3.3.3. Magnetic Robot Swarm 3.4. Optical Actuators 3.4.1. Liquid-Crystal Polymers 3.4.2. Hydrogels 3.4.3. Shape-Memory Polymers 3.4.4. Light-Responsive Liquids 3.5. Thermal Actuators 3.5.1. Liquid-Crystal Elastomers 3.5.2. Shape-Memory Materials 3.6. Chemical Actuators 3.6.1. Organic Vapors and Solvents 3.6.2. Humidity-Related Reactions 3.6.3. Enzymes 3.6.4. pH 3.7. Other Actuation Modalities 3.7.1. Acoustic 3.7.2. Biohybrid 3.7.3. Humidity 3.7.4. Energy Storage 3.7.5. Phase Change 3.7.6. Combustion 3.8. Future Development   \n4. Structure and Mechanics 4.1. Buckling Structures 4.2. Kirigami and Origami 4.3. Fibers and Fabrics 4.4. Other Structures   \n5. Fabrication Techniques 5.1. Templating 5.1.1. Molding 5.1.2. Lithography 5.1.3. Coating 5.1.4. Printing 5.2. Laser-Assisted Fabrication 5.2.1. Cutting 5.2.2. Engraving 5.2.3. Surface Modification 5.3. 3D Printing 5.3.1. Principles of 3D Printing 5.3.2. Printing Soft Electronic Devices 5.3.3. Printing Soft Actuators 5.3.4. Printing Soft Robots with Sensing Abilities 5.4. Transfer Printing 5.4.1. Mechanically Guided 5.4.2. Stimuli-Triggered 5.4.3. Other Transfer Printings Methods 5.4.4. 3D Curvy Electronics via Transfer Printing 5.5. Assembly 5.5.1. Materials Level  \n\n5.5.2. Electronic Device Level 5.5.3. Robotic System Level 6. Sensorimotor Control 6.1. Sensorimotor Control Frameworks 6.2. Control of Soft Robots 6.2.1. Model-Based Control 6.2.2. Data-Driven Control 6.2.3. Hierarchical/Hybrid Control 6.3. Emerging Approaches 6.3.1. Embodied Intelligence 6.3.2. Morphological Computation 6.3.3. Mechanical Computing 7. Artificial Intelligence (AI) in Soft Robots with Sensorimotor Functions 7.1. Machine Learning Framework 7.2. AI for Flexible Electronic Sensing Devices 7.3. AI for Soft Robotic Systems 8. Applications 8.1. Exploration 8.1.1. Aerial 8.1.2. Terrestrial 8.1.3. Aquatic 8.1.4. Cross-Media 8.2. Healthcare 8.2.1. Exoskeletons 8.2.2. Prosthetics 8.2.3. Artificial Organs 8.2.4. Drug Delivery 8.2.5. Catheters 8.2.6. Surgical Tools 8.3. Extended Reality (XR: AR/VR/MR) 8.3.1. Haptic Feedback Devices 8.3.2. XR Applications and Human−Machine Interaction 8.4. Manipulation 8.4.1. Object Handling 8.4.2. Object Recognition 9. Considerations for Future Development 9.1. Materials Discovery 9.2. Biomimicking 9.3. Energy 9.4. Manufacturing 9.5. Artificial Intelligence 9.6. Sustainability 10. Concluding Remarks Author Information Corresponding Author Authors Author Contributions Notes Biographies Acknowledgments References",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 1. INTRODUCTION  \n\nSensorimotor processes in biological species constitute an integrated system of sensory input and motor output essential for interaction with the environment.1−6 Sensory receptors, specialized for detecting various stimuli, such as light, sound, or touch, transmit this information to corresponding sensory cortexes in the central nervous system (CNS).7−16 The CNS processes these sensory inputs to generate appropriate motor responses, thereby establishing a continuous cycle of sensing, decision-making, and action that coordinates all the sensory organs, brain, and muscles for a specific task (Figure 1a). This intricate system facilitates both simple reflex actions and complex, coordinated behaviors, such as locomotion, flight, and predation in animals (Figure 1b).17−22 These adaptive, adept, agile, autonomous, and dexterous sensorimotor activities are a masterpiece for the seamless coordination of sensory receptors, controllers, and muscles or actuators. The integration of sensorimotor functions is vital for survival and daily activities, enabling organisms to respond adeptly to environmental changes, adapt through experience, and acquire new skills via feedback and practice.23,24 By contrast, the adaptability, agility, dexterity, and intelligence of conventional  \n\n![](images/03bb2ddc4714b6105a4ea267286f295ad3683cb33f9fb23277bd324d3f9d0c81.jpg)  \nFigure 1. Sensorimotor systems in human beings, animals, and soft robot. (a) Schematic illustration of human sensorimotor system. This system is mainly composed of sensory system (vision, touch, hearing, smell, and taste), muscular system (a variety of muscles spread throughout the whole body), and peripheral nervous system, and central nervous system (five sensory cortexes corresponding to the sensory system and one motor cortex). These systems coordinate synergically for a specific task. (b) Examples of sensorimotor actions in animals, such as elephant trunk for eating, octopus (escaping from dangers), hawk (patrolling for prey), star-nosed mole (exploring surroundings), gecko (preying), and bee (flying). These adaptive, adept, agile, autonomous, and dexterous sensorimotor activities are a masterpiece for the seamless coordination of sensory receptors, controllers, and muscles or actuators. Reproduced with permission from ref 37. Copyright 2020 Elsevier. Reproduced with permission from ref 38. Copyright 2024 American Association for the Advancement of Science. Reproduced with permission from ref 39. Copyright 2023 Springer Nature. Reproduced with permission from ref 40. Copyright 2001 Springer Nature. Reproduced with permission from ref 41. Copyright 2023 Deutsche Gesellschaft für Herpetologie and Terrarienkunde (DGHT). Reproduced with permission from ref 42. Copyright 2024 Taylor & Francis. (c) A simplified architecture for sensory motor control system. In this system, physical and chemical stimuli from the environments are first transduced to electrical signals by sensory receptors (sensors), followed by transmission and processing of the data in central nervous system (controller). After multimodal date fusion and high-level computation and interpretation, movement commands are sent out from motor cortex in the central nervous system, and corresponding actions or muscle movements are made to accomplish a specific task. Sensory inputs and motor outputs are made continuously, so that a cycle of closed-loop sensory-motor coordination for daily activities is established. (d) Drawing analogy from biological species, similar sensorimotor control process can also be built in robots. Here we term this as sensorimotor robot, in which a wide spectrum of sensors, actuators, and controllers that mimic their counterparts in biological species are required.  \n\n![](images/efd3856dcfa216bcd080177e132adf0164f6196bd44f47a5ddb5128e169610c0.jpg)  \nFigure 2. An overview of the development of soft sensors and actuators in last 70 years and their convergence. Silk screen plastic pressure arrays. Reproduced with permission from ref 44. Copyright 1954 Elsevier. Flexible piezo-resistive sensor. Reproduced with permission from ref 45. Copyright 1988 SPIE. Soft tribo-sensor. Reproduced with permission from ref 46. Copyright 1999 SAGE Publications. OFET pressure sensor matrix. Reproduced with permission from ref 47. Copyright 2004 United States National Academy of Sciences. Wearable glucose sensor. Reproduced with permission from ref 48. Copyright 2006 Elsevier. Stretchable silicon circuits. Reproduced with permission from ref 49. Copyright 2008 American Association for the Advancement of Science. Electronic eyes. Reproduced with permission from ref 50. Copyright 2008 Springer Nature. Nonvolatile memory transistors. Reproduced with permission from ref 51. Copyright 2009 American Association for the Advancement of Science. Skin-like pressure and strain sensors. Reproduced with permission from ref 52. Copyright 2011 Springer Nature. Epidermal electronics.  \n\nReproduced with permission from ref 53. Copyright 2011 American Association for the Advancement of Science. Imperceptible electronics. Reproduced with permission from ref 64. Copyright 2013 Springer Nature. Integrated sweat sensor. Reproduced with permission from ref 65. Copyright 2016 Springer Nature. Intrinsically stretchable transistor. Reproduced with permission from ref 66. Copyright 2018 Springer Nature. Tactile glove. Reproduced with permission from ref 67. Copyright 2019 Springer Nature. Ultrasensitive strain gauges. Reproduced with permission from ref 68. Copyright 2020 Springer Nature. Acoustic fabrics. Reproduced with permission from ref 69. Copyright 2022 Springer Nature. Artificial eyes in harsh environment. Reproduced with permission from ref 70. Copyright 2023 American Association for the Advancement of Science. Bioresorbable ultrasound sensor. Reproduced with permission from ref 71. Copyright 2024 American Association for the Advancement of Science. Wearable exoskeleton. Reproduced with permission from ref 83. Copyright 1957 Cyberneticzoo. Pneumatic manipulator. Reproduced with permission from ref 117. Copyright 2021 American Association for the Advancement of Science. Soft pneumatic elephant trunk. Reproduced with permission from ref 84. Copyright 1984 Cyberneticzoo. Mechanochemical actuators. Reproduced with permission from ref 85. Copyright 1987 Taylor $\\&$ Francis. Shape memory alloy actuator. Reproduced with permission from ref 86. Copyright 1989 Taylor & Francis. Piezoelectric actuators. Reproduced with permission from ref 87. Copyright 1993 Cambridge University Press. Conjugated polymer microactuators. Reproduced with permission from ref 88. Copyright 2000 American Association for the Advancement of Science. Muscular films actuators. Reproduced with permission from ref 89. Copyright 2007 American Association for the Advancement of Science. Liquid-crystal network actuators. Reproduced with permission from ref 90. Copyright 2009 Springer Nature. Multigait soft robot. Reproduced with permission from ref 91. Copyright 2011 United States National Academy of Sciences. Octopus-inspired soft robot. Reproduced with permission from ref 92. Copyright 2012 Taylor & Francis. Soft robot powered by explosion. Reproduced with permission from ref 93. Copyright 2013 Wiley. Entirely soft autonomous robots. Reproduced with permission from ref 110. Copyright 2016 Springer Nature. Magnetic-driven soft robot. Reproduced with permission from ref 111. Copyright 2018 Springer Nature. Ultragentle manipulator. Reproduced with permission from ref 112. Copyright 2019 American Association for the Advancement of Science. Deep sea soft robot. Reproduced with permission from ref 113. Copyright 2021 Springer Nature. Surgical robots. Reproduced with permission from ref 114. Copyright 2023 American Association for the Advancement of Science. Magnetic continuum robot. Reproduced with permission from ref 115. Copyright 2024 American Association for the Advancement of Science. Soft prosthetic hand by optical waveguides. Reproduced with permission from ref 118. Copyright 2016 American Association for the Advancement of Science. Robot with stretchable electroluminescent skin. Reproduced with permission from ref 119. Copyright 2016 American Association for the Advancement of Science. Strain sensing actuator. Reproduced with permission from ref 120. Copyright 2016 Wiley. Optoelectronic sensory foams with proprioception. Reproduced with permission from ref 121. Copyright 2018 American Association for the Advancement of Science. Soft somatosensitive actuators. Reproduced with permission from ref 122. Copyright 2018 Wiley. OmniSkins. Reproduced with permission from ref 123. Copyright 2018 American Association for the Advancement of Science. Actuators with embedded flex sensors. Reproduced with permission from ref 124. Copyright 2018 Elsevier. Wirelessly activated fully soft robots by e-skin. Reproduced with permission from ref 125. Copyright 2018 American Association for the Advancement of Science. Resistive sensors on soft robot. Reproduced with permission from ref 126. Copyright 2019 Frontiers. E-skin on soft robotic hand. Reproduced with permission from ref 127. Copyright 2019 Wiley. Earthworm-inspired soft robot with perceptive skin. Reproduced with permission from ref 128. Copyright 2019 IOP Publishing. Heterogeneous sensing in a multifunctional soft sensor. Reproduced with permission from ref 129. Copyright 2020 American Association for the Advancement of Science. TENG sensors on soft robot. Reproduced with permission from ref 130. Copyright 2020 Springer Nature. Actuators embedded with paper electronics. Reproduced with permission from ref 131. Copyright 2020 Wiley. Integration of sensing and shape-deforming capabilities for a bioinspired soft robot. Reproduced with permission from ref 132. Copyright 2021 Elsevier. Multifunctional e-skin on soft gripper. Reproduced with permission from ref 133. Copyright 2021 American Association for the Advancement of Science. Origami actuators with on-board sensing. Reproduced with permission from ref 134. Copyright 2021 Wiley. Proprioceptive soft robot module. Reproduced with permission from ref 135. Copyright 2022 MDPI. Proprioception and exteroception in soft robot. Reproduced with permission from ref 136. Copyright 2023 Wiley. Octopus-inspired sensorized soft arm. Reproduced with permission from ref 137. Copyright 2023 American Association for the Advancement of Science. Soft fluidic robots with sensing capabilities. Reproduced with permission from ref 138. Copyright 2024 Springer Nature.  \n\nrobot pale when compared with that of biological species, due to a lack of multimodal, long-term, and synergistic sensorimotor process with continuous sensory input, motor output and learning. Nevertheless, this foundational concept in biology can be mirrored in the design of soft robotic systems, where environmental signals are detected by sensors, analyzed by a central processing unit (CPU), and followed by precise actuation (Figure 1c).25−36  \n\nHerein, we term this kind of intelligent machine as sensorimotor robots (Figure 1d). Thus, sensorimotor robots are engineered systems designed to emulate the sensorimotor processes found in biological organisms. These robots integrate sensory data acquisition with closed-loop motor control to interact dynamically, effectively, and continuously with their environment. Key components and functionalities of sensorimotor robots include: a) Sensors: The robot is equipped with various sensors with corresponding data acquisition and communication platforms to detect environmental stimuli and their own posture (exteroception and proprioception). These can include cameras (vision), microphones (sound), gas sensors (smell), touch sensors, gyroscopes (balance), and more. These sensors serve as bridges connecting the physical and digital worlds, providing quantitative and digitalized inputs for the robotic system. b) Processing units or controllers: The robot’s central processing unit (CPU) or artificial intelligence (AI) system processes the sensory data and makes decisions about the appropriate actions to take. While the former involves interpreting the sensory inputs to understand the environment and context, the latter one refers to algorithms and other approaches for path planning, obstacle avoidance, object recognition, and more. c) Actuators: The robot uses actuators, such as motors and servos, to execute the planned actions. These actuators are responsible for precise movements and manipulations required for the robot to perform its tasks. A wide range of soft actuation mechanisms, including fluidicdriven actuators, dielectric elastomer actuators, and stimuliresponsive smart materials, hold promise for the actuation of sensorimotor robots. By emulating the sensing−decision− action loop observed in biological entities, we aim to develop a robust sensorimotor framework for soft robots, enhancing their capability to interact with and adapt to their surroundings in a manner analogous to living organisms.  \n\nIn this framework, sensing and actuation are two of the most critical foundations for soft robotics and Figure 2 listed the development of representative work about soft sensors and actuators and their intersections in the past 70 years. Sensing involves the detection of various environmental stimuli through specialized sensors, which can be traced back to thousands of years ago.43 Conventional sensors and devices for such detection are hard, rigid, and brittle, such as the ancient setup for earthquake detection and modern computer platform based on silicon chips, which is not compatible with soft systems. Owning to the breakthroughs made in soft materials, conductive polymers, nanomaterials, mechanics, and fabrication techniques, a variety of soft sensors are created, ranging from different types of pressure, chemical, optical sensors to memory devices and integrated flexible sensing devices.44−63 Recently, with the technological maturity, more and more attention about flexible devices has been paid to higher density and performance, harsh working conditions, multimodal sensing capabilities, sustainability, etc.64−82 On the other side, the research on soft actuators was stemmed from the implementation of wearable exoskeletons for the disabled.83 After that, interests about soft robots were increasing and various actuation mechanisms (e.g., pneumatic, chemical, piezoelectric, etc.) and smart materials (e.g., shape-memory materials, polymers, liquid-crystal materials, etc.) are proposed and discovered, achieving controllable movement of soft matter.84−103 However, compared with the soft creatures in nature, such robots can only achieve simple movement modes and have limited functionalities, which restricts their potentials as soft machines.104−109 Thus, in the past ten years, tremendous efforts in both materials and manufacturing techniques have been made to creating more advanced soft machines, enabling a number of unimaginable functionalities, such as autonomy, reconfigurability, working in extreme conditions, etc.110−115  \n\n![](images/bbcecc79fd65daae5214dd80474d6577855f251bc8174efc961488c87cd4ce31.jpg)  \nFigure 3. An overview of sensorimotor materials for soft robots. The organization starts from materials and structures for sensors and actuators for soft robots, which are two fundamental physical foundation. Followed by discussion of manufacture techniques (such as templating, laser fabrication, 3D printing, transfer printing, etc.) and sensorimotor control (such as sensorimotor framework, control strategies, etc.), artificial intelligence used in soft electronics and robots are introduced. The synergistic work of these aspects from materials, structures, and manufacture to sensorimotor control and AI enables a variety of applications, such as exploration, healthcare, AR/VR, human−machine interaction, manipulation, and recognition. Reproduced with permission from ref 151. Copyright 2023 Springer Nature. Reproduced with permission from ref 152. Copyright 2018 Oxford University Press. Reproduced with permission from ref 153. Copyright 2022 Wiley. Reproduced with permission from ref 154. Copyright 2022 Wiley. Reproduced with permission from ref 155. Copyright 2014 Springer Nature. Reproduced with permission from ref 156. Copyright 2006 Springer Nature. Reproduced with permission from ref 157. Copyright 2024 Springer Nature. Reproduced with permission from ref 158. Copyright 2023 Springer Nature. Reproduced with permission from ref 159. Copyright 2019 Springer Nature. Reproduced with permission from ref 160. Copyright 2022 Springer Nature. Reproduced with permission from ref 163. Copyright 2023 Springer Nature. Reproduced with permission from ref 161. Copyright 2022 Springer Nature. Reproduced with permission from ref 164. Copyright 2023 American Association for the Advancement of Science. Reproduced with permission from ref 162. Copyright 2020 American Association for the Advancement of Science.  \n\nUndoubtably, while soft machines are promising in applications ranging from prosthetic hands and exoskeletons to AR/VR and exploration due to their intrinsic softness and compliance, soft electronic devices are paving the way for their long-term development toward full autonomy and intelligenc e.116 However, most of reported soft robots can only move and respond passively, lacking the function of sensing internal and external information. This absence of sensory input could not make up a complete sensorimotor system and makes the soft machine impotent working in changing and unstructured environments.  \n\nIn contrast, by integrating advanced sensing and actuation capabilities, soft robots can navigate and manipulate their environments in perceptive and active ways, due to the coordination of sensory inputs and motor outputs, mimicking the sophisticated sensorimotor loop of human beings.139,140 This is a critical step for the transition of soft robots from structure to function and further to intelligence. Nevertheless, compared with the vast number of works about soft sensors and actuators, the investigation to their intersection has a shorter history and there are limited number of representative works that achieved the integration of sensors on soft machines for stimuli and position detection, object recognition, and manipulation.118−138,141 As the advancements of science and technology, research on this sensorimotor intersection is sure to rise and it is worth to review the developments in sensorimotor of soft machines to shed light on its future. Although there are a number of papers have reviewed the progress in soft robots and flexible sensors, they are limited either in lacking of a comprehensive framework of sensorimotor (e.g., sensors, actuators, controls, etc.) or the completeness and depth of sensory and actuation system (e.g., materials, structures, manufacturing, etc.).142−150 Aiming to address these limitations and build a groundwork for the continued sensorimotor work on soft machines, here we provided a holistic review on the sensorimotor materials for soft robots.  \n\n![](images/976d59f620b25088c30d84c9b3fd76e82e48a301c0f73db17d185028ee420f9a.jpg)  \nFigure 4. Chemicals of commonly used substrate materials and functional materials in flexible sensing devices and a summary of Young’s modulus and conductivity of these materials. Values were extracted from refs 183−200.  \n\nIn this review, we extrapolated an exhaustive story about sensorimotor materials for soft machines from different perspectives that are indispensable for this interdisciplinary field, ranging from sensing/actuation materials, structures, and mechanics to manufacturing techniques, sensorimotor control, artificial intelligence, and applications (Figure 3).151−164 First of all, while sensing and actuation are two of the most important foundations involved in the architecture of sensorimotor, starting from materials aspects, we made a complete review with regards to various types of flexible sensors and soft actuators in terms of their working principles, materials composition, and device performance and advancements.  \n\nWith equal significance, structures and mechanics provide another design dimension and guideline for flexible electronic devices and soft machines. We systematically reviewed the commonly used structures (such as buckling structure, kirigami, origami, fibers, fabrics, etc.) involved in electronic devices and soft robots. Then, five mostly employed fabrication techniques in soft electronics and actuators (templating, laser assisted fabrication, 3D printing, transferring printing and assembly) are discussed in terms of their working principles and corresponding fabrication examples. Drawing the analogy from sensorimotor loop or sensorimotor control from biology, we next built a comprehensive framework of sensorimotor control for soft robots that links sensing−decision−action in a closed-loop network and explored the strategies for soft robotic control. Afterward, AI involved in flexible sensing devices and soft robotic system is discussed. Followed by this, examples about the application of soft robots in a variety of scenarios are offered, ranging from exploration and AR/VR to healthcare and manipulation. Last but not least, insights with regards to the future development of soft machines are provided, aiming at shedding light on the long-standing issues and challenges faced by soft robotic research and human beings.  \n\n![](images/a7e9ae452cda034b9a3367e81cd1d58ecba90dd3a11bd908b5ad27ba455cfb9f.jpg)  \nFigure 5. Various mechanisms of pressure sensors. $\\left(\\mathsf{a{-}d}\\right)$ Piezoresistive pressure sensors based on geometrical effect (a), disconnection mechanism (b), crack propagation (c), and tunnelling effect (d). Reproduced with permission from ref 201. Copyright 2009 Wiley. Reproduced with permission from ref 202. Copyright 2014 Wiley. Reproduced with permission from ref 203. Copyright 2014 Springer Nature. Reproduced with permission from ref 204. Copyright 2020 Springer Nature. $\\left(\\mathrm{e-g}\\right)$ capacitive pressure sensors based on electrodes distance change (e), relative electrode areas change (f), and dielectric change $(\\mathbf{g})$ . Reproduced with permission from ref 205. Copyright 2016 Wiley. Reproduced with permission from ref 206. Copyright 2020 American Chemical Society. Reproduced with permission from ref 207. Copyright 2021 Wiley. $(\\mathrm{h-k})$ Triboelectric pressure sensors based on vertical contact mode $\\mathrm{(h)}$ , single electrode mode (i), sliding mode (j), and freestanding mode (k). Reproduced with permission from ref 208. Copyright 2012 American Chemical Society. Reproduced with permission from ref 209. Copyright 2014 American Chemical Society. Reproduced with permission from ref 210. Copyright 2014 Wiley. Reproduced with permission from ref 211. Copyright 2014 Wiley. $\\left(\\operatorname{l-n}\\right)$ Other mechanisms for pressure sensors, including piezoelectric pressure sensors (l), optical-based pressure sensors $\\mathrm{(m)}$ , and magnetic pressure sensors $\\mathbf{\\rho}(\\mathbf{n})$ . Reproduced with permission from ref 212. Copyright 2015 Springer Nature. Reproduced with permission from ref 118. Copyright 2016 American Association for the Advancement of Science. Reproduced with permission from ref 213. Copyright 2024 MDPI, Basel, Switzerland.",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2. SENSING TECHNOLOGIES AND MATERIALS  \n\nSensing technologies have revolutionized the way we interact with the world, playing a crucial role in a wide range of applications, from healthcare monitoring and environmental sensing to industrial automation and wearable electronic s.165−172 Flexible sensors demonstrate significant advantages over conventional rigid sensors in terms of adaptability, comfort, and integration with dynamic and irregular surfaces.173,174 The effectiveness and versatility of these technologies are deeply rooted in the materials and mechanisms that underpin their functionality. The rapid development of nanomaterials, composites, carbon-based materials, conductive polymers, organic semiconductors, liquid metal, and ionic elastomers has spurred the emergence of a wide array of flexible devices and platforms.175−182 These materials offer exceptional electrical properties and mechanical flexibility, enabling the creation of devices that can bend and stretch without losing functionality.  \n\nAs sensing technologies continue to evolve, ongoing research and development of new materials will undoubtedly lead to even more innovative and impactful applications. This section provides a brief overview of the various sensing technologies and materials. In terms of materials, we categorize them into substrate materials and functional materials and Figure 4 listed the chemical structures of most widely used materials as well as their Young’s modulus and conductivity, which are two key indicators for the mechanical and electrical properties of soft electronic devices. While soft materials play indispensable roles in the sensing and actuation of soft robots, the definition of softness is very diverse. To be more specific, softness in materials is a key characteristic defined by their ability to deform under applied forces, and it is typically quantified by properties such as Young’s modulus, shear modulus, compressive modulus, indentation hardness, strainto-failure and others. Young’s modulus, which represents the ratio of stress to strain in the elastic region, is particularly important in assessing the stiffness of a material, with lower values indicating greater softness, as these materials deform more easily under the same stress. Thus, Young’s modulus is considered as one crucial indicator of the softness of materials employed in flexible sensors and soft actuators. It can be shown from Figure 4, the lower the Young’s modulus, the softer the materials are. Similarly, materials with lower shear modulus and compressive modulus are also considered softer, as they exhibit greater deformation when subjected to shear or compressive forces. Softness can also be assessed through methods such as indentation hardness, where the depth of the indentation made by a probe under a specified load is measured, with softer materials showing deeper impressions. Strain-to-failure, which measures the extent of deformation before a material breaks, is another important metric, with softer materials typically exhibiting larger strains before rupture. Additionally, Poisson’s ratio, which quantifies the lateral strain relative to axial strain when a material is stretched or compressed, tends to be higher in softer materials, indicating that they deform more easily in multiple directions. In soft robotics, these properties are crucial as they directly influence the material’s performance in dynamic environments. Soft materials, particularly those with low Young’s modulus and high strain-to-failure, are selected to provide flexibility, compliance, and adaptability, enabling soft robots to interact safely with delicate objects or human skin. Such materials are essential for applications that require high degrees of flexibility and safe human−robot interaction, as well as for creating soft actuators and grippers that can manipulate objects gently without causing damage.  \n\nBeginning with mechanical sensors, including pressure sensors and strain sensors, different mechanisms are reviewed. These mechanisms include piezoresistive, capacitive, piezoelectric, and triboelectric, along with other methods such as magnetic and optical sensing. Each technology offers unique advantages and challenges, making them suitable for different applications and environments. Following this, temperature sensing technologies are examined, with a focus on resistive sensors, thermistors, and thermocouples. These sensors are essential for many applications, from industrial control to medical diagnostics. Photonic sensing is then discussed, primarily focusing on the interaction of light with materials to detect environmental changes, offering high sensitivity and specificity. Chemical sensing technologies are presented next, with a focus on materials such as carbon-based materials, transition metal dichalcogenides (TMDs), metal−organic frameworks (MOFs), metal oxides, and their composites. These materials are crucial for detecting chemical substances in fields like environmental monitoring, healthcare, and safety. Acoustic sensing technologies, covering both ultrasound and audible waves, are also important for applications ranging from medical imaging to structural health monitoring. Electromagnetic sensing, including magnetic and electric sensors, detect changes in electromagnetic fields and are crucial for applications in communications, navigation, and security. Finally, this section explores multimodal integration in sensing technologies, focusing on the integration of normal and shear forces and other advanced multimodal sensing technologies. This integration enhances the functionality and performance of sensors, enabling them to provide more comprehensive and accurate data.",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.1. Pressure Sensors  \n\nIndeed, tactile sensors utilize various mechanisms to detect and respond to external stimuli. Among the most common are resistance, capacitance, triboelectricity, and others, each employing unique materials and structural designs. We systematically summarized the working mechanisms of these sensors in Figure 5.  \n\nResistance-based tactile sensors utilize various mechanisms to detect and respond to pressure or force. One common method involves the geometric changes of conductive materials or polymers, where the resistance changes with deformation (Figure 5a).201 Another mechanism is based on the disconnection mechanism, where the conductive path within the materials is disrupted or reconnected under external stimuli, such as pressure. This connection typically occurs between electrodes and piezoresistive materials (Figure 5b).202 Additionally, some sensors operate on the principle of crack propagation, where external force generates cracks in a conductive layer, leading to an increase in resistance. Upon release of the force, the conductive path reconnects, resulting in the recovery of resistance (Figure 5c).203 Another mechanism is based on the tunneling effect, which relies on specific material properties to detect changes in resistance (Figure 5d).204  \n\nCapacitance-based sensors, on the other hand, measure changes in capacitance. Based on the calculation equation of capacitance, there are three main factors that influence the capacitance change, including the relative area between electrodes, the dielectric constant of the dielectric material, and the distance between electrodes. One design involves monitoring changes in the distance between the electrodes (Figure 5e).205 When the dielectric material is deformable, external stimuli cause changes in the distance between electrodes, resulting in a change in capacitance. Another approach is to detect changes in the relative electrode area (Figure 5f).206 External stimuli induce displacement of the electrodes, altering the relative area between them and thus affecting capacitance. Additionally, capacitance-based sensors can utilize different dielectric materials, each with its own response to external force or deformation (Figure 5g).207 When subjected to force, these materials exhibit varying changes in their effective dielectric constant, leading to fluctuations in capacitance.  \n\nTriboelectric sensors operate on the principle of the triboelectric effect, which generates electrical charge when two materials come into contact and then separate. This effect has been harnessed in various contact modes, including vertical contact mode (Figure 5h),208 single electrode mode (Figure 5i),209 sliding mode (Figure 5j),210 and freestanding mode (Figure 5k).211 In each mode, mechanical stimuli cause contact and separation between materials, leading to the generation of electrical signals that can be detected and measured. Triboelectric sensors have found applications in touch and pressure sensing, where they excel in converting mechanical stimuli into electrical signals for further processing and analysis.  \n\nIn addition to resistance, capacitance, and triboelectric mechanisms, other approaches have been explored for tactile sensing. Piezoelectric sensors utilize specific materials to generate electric charges in response to mechanical stress, leveraging the asymmetric arrangement of atoms or molecules in their crystal structure (Figure 5l).212 Optical-based sensors measure changes in light intensity or wavelength caused by deformation, offering advantages in terms of precision and stability (Figure $\\mathrm{5m}\\mathrm{\\overline{{\\Omega}}}$ ).118 Magnetic tactile sensors, on the other hand, employ magnetic fields to detect and measure tactile interactions or pressure, often integrating magnetized materials or magnetic field sensors into a substrate (Figure 5n).213 Each mechanism has its own set of advantages and is suitable for different applications based on factors like sensitivity, response time, and environmental conditions.  \n\n![](images/3906082246275d2e3e8c6e4efc9c6c4bddeb25da073c6707ed2fb94df40c93b9.jpg)  \nFigure 6. Different kinds of materials for piezoresistive pressure sensors. $(\\mathsf{a}\\mathrm{-}\\mathsf{d})$ Piezoresistive pressure sensor based on metal materials, such as liquid metal (a), AuNWs (b), CuNWs (c), and conductive yarn (d). Reproduced with permission from ref 214. Copyright 2019 Wiley. Reproduced with permission from ref 215. Copyright 2014 Springer Nature. Reproduced with permission from ref 216. Copyright 2022 Elsevier. Reproduced with permission from ref 217. Copyright 2022 ACM. (e−h) Resistance change based on carbon materials, such as graphene (e), SWCNT (f), CNT/CB $\\mathbf{\\eta}(\\mathbf{g})$ , and Velostat (h). Reproduced with permission from ref 218. Copyright 2015 Springer Nature. Reproduced with permission from ref 219. Copyright 2023 Elsevier. Reproduced with permission from ref 220. Copyright 2023 Elsevier. Reproduced with permission from ref 125. Copyright 2018 American Association for the Advancement of Science. (i−l) Resistance change based on polymers, for example, PAAM/PVA hydrogel (i), ACC/PAA/alginate hydrogel (j), PDA@CNT/PAM hydrogel (k), and PEDOT:PSS (l). Reproduced with permission from ref 221. Copyright 2023 Elsevier. Reproduced with permission from ref 222. Copyright 2017 Wiley. Reproduced with permission from ref 223. Copyright 2023 Elsevier. Reproduced with permission from ref 224. Copyright 2019 American Association for the Advancement of Science.  \n\n2.1.1. Piezoresistive. In recent years, piezoresistive sensors have witnessed significant advancements across diverse material platforms, notably encompassing metal-based, carbonbased, and polymer-based materials. Each material type brings distinct properties and functionalities to the table, unlocking novel capabilities for a wide range of applications. Metal-based materials have emerged as promising candidates for the fabrication of sensitive and robust resistive pressure sensors, offering significant advancements in healthcare monitoring and wearable devices. Liquid metal is one candidate material, which is famous by its high mobility and conductivity. A 3D-printed rigid microbump-integrated liquid metal-based soft pressure sensor (3D-BLiPS) combines multimaterial fused deposition modeling to achieve a one-step, direct process fabrication (Figure 6a).214 This sensor demonstrates exceptional sensitivity enhanced by a microbump array and excellent robustness to multidirectional stretching, temperature changes, and water immersion. Other common metals, like Au and $\\mathrm{Cu}$ , were applied with novel structures, such as nanowires. A flexible pressure sensor based on ultrathin Au nanowires embedded in tissue paper enables real-time monitoring of blood pulses and detection of small vibration forces (Figure 6b).215 Cu nanowires have also been integrated with cotton fibers to fabricate superhydrophobic piezoresistive pressure sensors, suitable for flexible electronics applications even in humid environments (Figure 6c).216 Moreover, a conductive yarn based on stainless steel was used to detect pressure and integrated into soft pneumatic actuators, presenting a costeffective and robust solution for designing sensing-integrated actuators in assistive wearables and robotics (Figure 6d).217  \n\nCarbon-based materials address the need for high sensitivity and wide pressure range detection in electronic skin and tactile sensing systems, including graphene, carbon nanotube (CNT), and carbon black (CB). For example, laser-scribed graphene (LSG) was utilized to fabricate a flexible and ultrasensitive pressure sensor with a foam-like structure (Figure 6e).218 Other structures, like micropyramidal structure inspired by human skin, have also been explored (Figure 6f).219 It can identify the hardness values of different objects, enabling precise detection of external information in human−machine interaction scenarios. In addition, a washable piezoresistive pressure sensor using porous CNT/CB sponge offers a practical solution for wearable devices (Figure 6g).220 This sensor exhibits excellent compression cycle stability, making it suitable for human motion monitoring and foot membrane inflammation prevention. Moreover, a skin-like driving system enables the compact and reversible assembly of fully soft robots, addressing the compliance gap in existing models (Figure 6h).125 By integrating electronic skins with wireless interskin communication, this system enables untethered, reversible assembly of driving capability, paving the way for highly compact soft robotic designs with minimized inherent hardness and universal robotic actuation.  \n\n![](images/d0640c014e02d15ca82e43fc0470ae25a816953f15ce74d9a4b1b469b2b78eba.jpg)  \nFigure 7. Various structures applied in capacitive pressure sensors. $\\left(\\mathsf{a}-\\mathsf{c}\\right)$ Porous structures with different materials, including GNPs/WMCNTs/ SR/PS (a), PDMS (b) and nanocomposite (c). Reproduced with permission from ref 225. Copyright 2019 American Chemical Society. Reproduced with permission from ref 226. Copyright 2016 Wiley. Reproduced with permission from ref 227. Copyright 2021 Wiley. $\\left(\\mathrm{d-f}\\right)$ Pyramid or dome structures with different materials, such as PVDF (d), polyurethane (e), and parylene (f). Reproduced with permission from ref 228. Copyright 2016 Wiley. Reproduced with permission from ref 229. Copyright 2020 Wiley. Reproduced with permission from ref 230. Copyright 2018 Wiley. $\\mathrm{(g-i)}$ Pillar or cone structures with different materials, like PDMS/CIP (g), PDMS/NOA (h), and P(VDF-TrFE) (i). Reproduced with permission from ref 231. Copyright 2020 Elsevier. Reproduced with permission from ref 232. Copyright 2022 American Association for the Advancement of Science. Reproduced with permission from ref 233. Copyright 2019 Wiley. (j−l) Hybrid or hierarchical structures with various materials, including PU (j), PDMS (k), and CNT/PDMS (l). Reproduced with permission from ref 234. Copyright 2018 American Association for the Advancement of Science. Reproduced with permission from ref 235. Copyright 2019 American Chemical Society. Reproduced with permission from ref 236. Copyright 2021 Wiley.  \n\nPolymer-based materials have emerged as promising candidates for flexible and biocompatible pressure sensors, especially hydrogels. These materials offer versatility and compatibility with various applications in healthcare monitoring, artificial intelligence, and wearable devices. For instance, polyacrylamide (PAAm)/poly(vinyl alcohol) (PVA) hydrogels were decorated with pyramid microarrays to detect pressure with high sensitivity and low detection limit (Figure 6i).221 Furthermore, bioinspired mineral hydrogels have constituted the mechanically adaptable ionic skin sensors capable of sensing subtle pressure changes, such as a gentle finger touch or human motion (Figure 6j).222 Another potential benefit comes from hydrogels is self-healing property, such as polyacrylamide (PAM) nanocomposite hydrogels (Figure 6k).223 Moreover, a scalable communication architecture known as the asynchronously coded electronic skin (ACES) has been introduced to enable the asynchronous readout of thousands of tactile sensors through a single conductor (Figure 6l).224 This architecture enables rapid tactile perception and sensor arrays that are dynamically reconfigurable, facilitating applications in artificial intelligence-enhanced autonomous robots and prosthetics.  \n\n2.1.2. Capacitive. Capacitive tactile sensors are known for their fast response and wide dynamic detection range, but they often suffer from interference and noise. In the basic parallel plate model, three main factors determine capacitance: the dielectric constant of the materials, the relative area of the electrodes, and the distance between electrodes. Therefore, the design principles of capacitive tactile sensors revolve around materials and structural design. the current status of capacitive tactile sensors is discussed in the following part, from the perspective of structural design.  \n\nVarious structural designs have been explored by researchers to enhance the performance of capacitive tactile sensors, especially improving sensitivity and response time (Figure 7). One common type of structures is the porous structure, which undergoes significant deformation under external stimuli (Figure $\\mathrm{7a-\\bar{c},}$ .225−227 For instance, a conductive porous nanocomposite fabricated with carbon nanotubes (CNTs)- doped Ecoflex (Figure 7c), exhibiting $86\\%$ porosity, demonstrated enhance sensitivity (i.e., more than $400\\%$ ) over wide ranges.227 Another prevalent type is the pyramid or dome structure, which concentrates external stress specific locations to amplify the output signal (Figure 7d−f).228−230 An example includes a conductive array integrated with single-walled carbon nanotubes (SWCNTs) and microstructural poly(dimethylsiloxane) (PDMS) (Figure 7f), serving as the electrode of capacitance, contributing to high sensitivity and a linear response.230  \n\n![](images/be1536d6bcbf84e5ad11b3c07a88d8ce38e316e63d23574ebaa7fa6380656047.jpg)  \nFigure 8. Different functional materials for piezoelectric pressure sensors. $\\left(\\mathsf{a}-\\mathsf{c}\\right)$ Inorganic piezoelectric materials, including ZnO $(\\mathsf{a},\\mathsf{b})$ and $\\mathrm{BaTiO}_{3}$ (c). Reproduced with permission from ref 239. Copyright 2014 American Chemical Society. Reproduced with permission from ref 240. Copyright 2016 The Royal Society of Chemistry. Reproduced with permission from ref 241. Copyright 2014 American Chemical Society. (d−f) Organic piezoelectric materials, such as $\\beta$ -Gly/CS film (d), PEDOT ${\\ @\\mathrm{PVDF}}$ fabric (e), and PVDF MNFs (f). Reproduced with permission from ref 242. Copyright 2020 American Chemical Society. Reproduced with permission from ref 243. Copyright 2017 Springer Nature. Reproduced with permission from ref 244. Copyright 2017 IOP Publishing. $\\mathrm{(g-i)}$ Piezoelectric composite materials for pressure sensors, including ppy-PDMS $(\\mathbf{g})$ , BTO/P(VDF-TrFE) nanofibers (h), and PDMS/plastics . Reproduced with permission from ref 245. Copyright 2018 Elsevier. Reproduced with permission from ref 246. Copyright 2019 American Chemical Society. Reproduced with permission from ref 247. Copyright 2012 Wiley.  \n\nSimilarly, pillar or cone structure, with larger height-tobottom ratios compared to pyramid or dome structures, have been explored (Figure $\\mathrm{7g-i)}$ .231−233 For instance, inspired by the interlocked microbridges between the epidermis and dermis, a highly sensitive capacitive tactile sensor with interlocked asymmetric nanocones (Figure 7i) demonstrated rapid response time and high sensitivity due to the highly localized stress at the contact apexes.233 Additionally, hybrid or hierarchical structures, combining different microstructures, offer advantages in accommodating diverse tactile sensing requirements (Figure 7j−l).234−236 For example, a biomimetic tactile sensor, combining with pyramid structure and natureinspired phyllotaxis spirals (Figure 7j), resulted in increased sensitivity and excellent stability.234  \n\n2.1.3. Piezoelectric. Piezoelectric pressure sensors operate based on the piezoelectric effect, which generates an electric charge in response to mechanical stress on specific materials like quartz crystals or ceramics. When pressure is applied, it deforms the material’s crystalline structure, redistributing internal electric charges and creating a voltage difference across the material.237,238 This voltage is proportional to the applied pressure, enabling precise measurement. These sensors typically consist of a piezoelectric material sandwiched between two electrodes that collect the generated charges. Recent advancements in materials science have led to the development of novel piezoelectric materials with enhanced sensitivity, flexibility, and biocompatibility. The following overview discusses inorganic, organic, and composite materials for piezoelectric pressure sensors, highlighting their unique properties and applications.  \n\nAs for inorganic materials, zinc oxide $(\\mathsf{Z n O})$ and polyvinylidene fluoride (PVDF) are the main candidates. Nanowires (NWs) and nanorods structures have been investigated to enhance the performance of piezoelectricity. A $\\mathrm{{}}Z\\mathrm{{nO}}$ NWs-based touch pad offers a simple yet effective solution for user interfaces (Figure 8a).239 The touch-induced electric charges are converted into voltage outputs, enabling user input for various applications such as programming and gaming. Another flexible self-powered tactile sensor array based on $\\mathrm{{znO}}$ nanorods (Figure 8b).240 Besides ${\\mathrm{{ZnO}}}.$ , PVDF and its composites are promising. A composite thin film, comprising hemispherically aggregated $\\mathrm{\\bfBaTiO}_{3}$ nanoparticles (NPs) and poly(vinylidene fluoride-co-hexafluoropropene)  \n\n![](images/de16e79bde027a152f46cca985cfeda401c0a50482b85725b316906829740a5a.jpg)  \nFigure 9. Various electrode materials for triboelectric pressure sensors. $\\left(\\mathsf{a}-\\mathsf{c}\\right)$ Metal electrode materials including AgNWs $(\\mathfrak{a},\\mathfrak{c})$ and $\\mathtt{C u}$ (b). Reproduced with permission from ref 250. Copyright 2020 Wiley. Reproduced with permission from ref 251. Copyright 2016 Wiley. Reproduced with permission from ref 252. Copyright 2020 American Association for the Advancement of Science. (d−f) Semiconductor electrode materials for triboelectric pressure sensors, including CNTs (d), MWCNTs (e), and graphene (f). Reproduced with permission from ref 253. Copyright 2021 Wiley. Reproduced with permission from ref 254. Copyright 2018 Wiley. Reproduced with permission from ref 255. Copyright 2016 Elsevier. $\\mathrm{(g-i)}$ Gel electrode materials for triboelectric pressure sensors, including PVA/PA hydrogel $(\\mathbf{g})$ , MPP-hydrogel (h), and PAMPS ionogel (i). Reproduced with permission from ref 256. Copyright 2022 Elsevier. Reproduced with permission from ref 257. Copyright 2022 Wiley. Reproduced with permission from ref 258. Copyright 2019 Elsevier. (j−l) Hybrid electrode materials for triboelectric pressure sensors, including Ag/PVA nanofibers (j), rGO@AgNWs (k), and PTFE/PS/PET/PA66 (l). Reproduced with permission from ref 259. Copyright 2018 Wiley. Reproduced with permission from ref 260. Copyright 2020 Elsevier. Reproduced with permission from ref 261. Copyright 2022 American Association for the Advancement of Science.  \n\nP(VDF-HFP), was utilized to develop high-performance flexible nanogenerators (Figure 8c).241 By employing a solvent evaporation method, the formation of hemispherical BTOP(VDF-HFP) clusters significantly enhances piezoelectric power generation, making them suitable for large-scale fabrication of high-performance flexible nanogenerators.  \n\nOrganic piezoelectric materials usually exhibit intrinsic flexibility and compatibility. For example, biodegradable glycine−chitosan piezoelectric films are fabricated through the self-assembly of glycine molecules, exhibiting a sensitivity comparable to nondegradable commercial piezoelectric materials (Figure 8d).242 Another self-powered and wearable electronic skin was designed by weaving polyvinylidene fluoride (PVDF) electrospun yarns of nanofibers coated with PEDOT (Figure 8e).243 For mass production, the printed circuit board technology can be combined (Figure 8f).244  \n\nEncapsulation enables electrical superposition by connecting PVDF micro/nano fibers collectively and effectively in serial/ parallel patterns, achieving high current and voltage output.  \n\nOther materials are also promising, including 3D polypyrrole (PPy) network composite with PDMS and $\\mathrm{BaTiO}_{3}$ nanoparticles (Figure 8g),245 barium titanate (BTO)/P(VDFTrFE) composite nanofibers (Figure 8h),246 and $\\mathbf{BaTiO}_{3}$ nanoparticles with graphitic carbons (Figure 8i).247 By dispersing nanoparticles or combining with other nanomaterials in a polymer matrix can enhance the piezoelectric outputs and power generation.  \n\n2.1.4. Triboelectric. Triboelectric pressure sensors leverage the triboelectric effect, where electric charge is generated by material contact and separation.248,249 Under pressure, deformation modifies contact area and pressure distribution, causing charge redistribution and signal generation. By employing materials with distinct triboelectric properties, like electron affinities or work functions, these sensors produce charges upon contact and separation. The ensuing signal accurately mirrors the applied pressure, facilitating precise sensing. Ongoing research delves into diverse electrode materials, including metals, semiconductors, gels, and hybrids, aiming to enhance sensor performance, flexibility, and functionality.  \n\n![](images/3eb2128f2e96579aae9e0733431ff4002ce302bc4f59cdef744da5e7f6cff6ba.jpg)  \nFigure 10. Magnetic $(\\mathsf{a}-\\mathsf{d})$ and optical (e−f) pressure sensors. (a) Magnetic tactile sensor with bionic hair array. Reproduced with permission from ref 266. Copyright 2024 Wiley. (b) Soft magnetic skin for deformation sensing. Reproduced with permission from ref 267. Copyright 2019 Wiley. (c) Tactile sensor based on magnetic fields. Reproduced with permission from ref 268. Copyright 2019 Springer Nature. (d) Soft magnetic skin for tactile sensing. Reproduced with permission from ref 269. Copyright 2021 American Association for the Advancement of Science. (e) An optical-based 3-axis pressure sensor. Reproduced with permission from ref 270. Copyright 2023 American Association for the Advancement of Science. (f) Optical tactile sensor for haptic perception. Reproduced with permission from ref 271. Copyright 2023 Wiley.  \n\nMetal electrode-based TENGs have attracted attention for their robustness and versatility. Bioinspired surface microstructures and polytetrafluoroethylene (PTFE) tinny burrs have enhanced the sensitivity of TENGs to pressure stimuli, enabling applications in robotic tactile sensing and object recognition (Figure 9a).250 Similarly, hemispheres-arraystructured TENGs offer durability in harsh environments and can function as active self-powered sensor arrays for detecting pressure distribution (Figure 9b).251 Not only microstructure, but also nanofibers can be applied. The breathable and biodegradable e-skin, based on silver nanowires and biocompatible polymers, demonstrates real-time monitoring of physiological signals and joint movements, showcasing the potential for healthcare applications (Figure 9c).252  \n\nSemiconductor electrodes are additional choices. Textile triboelectric sensors, leveraging lightweight and mechanically durable materials, offer high-fidelity pulse waveform monitoring validated against traditional blood pressure cuffs (Figure 9d).253 Moreover, paper-based TENGs with multiwalled carbon nanotubes coated air-laid paper electrodes provide washability, breathability, and mechanical stability, making them suitable for integration into wearable devices (Figure 9e).254 The conformal integration of TENGs on human skin enables self-powered touch sensors, facilitating assistive communication systems for individuals with mobility impairments (Figure 9f).255  \n\nGel electrodes offer unique opportunities for human− machine interaction in medical applications, like hydrogels and inongels. Stretchable hydrogel-based TENGs provide selfpowered sensing capabilities, allowing for the transmission of distress calls through finger bending in diagnostic scenario (Figure 9g).256 Another triple-network conductive hydrogel electrodes enhance TENG performance by improving conductivity and electrical output while maintaining mechanical robustness and elasticity, laying the foundation for advanced medical diagnostic tools (Figure 9h).257 In addition, tactile sensors with ionogel electrodes offer high sensitivity for monitoring various human activities (Figure 9i).258  \n\nHybrid electrodes combine the advantages of different materials to achieve highly stretchable and fast rapid response. Ag-nanofiber electrode-based triboelectric sensors enable rapid tactile mapping and detection of various objects, expanding their applications in touchpad technology and interactive interfaces (Figure 9j).259 Multilayered thermoplastic polyurethane (TPU) with silver nanowires (AgNWs) and reduced graphene oxide (rGO) bring about high stretchability (Figure 9k).260 Moreover, smart fingers integrating triboelectric sensing and machine learning enable accurate identification of material type and roughness, offering possibilities for intelligent manipulators and prosthetic devices (Figure 9l).261 The diverse electrode materials explored in triboelectric pressure sensors highlight their potential to revolutionize wearable electronics, human−machine interactions, and medical diagnostics. These advancements underscore the critical role of electrode materials in shaping sensor performance and functionality, paving the way for innovative solutions in tactile sensing and electronic skin technologies.  \n\n2.1.5. Other (Magnetic and Optical). There are many other types of pressure sensors or tactile sensors including magnetic and optical sensors.262−265 Magnetic-based pressure sensors have emerged as a promising avenue in the field of tactile sensing, offering significant potential for applications in robotics, healthcare, and object recognition. Magnetic-based pressure sensors operate on the principle of detecting changes in magnetic fields induced by mechanical pressure. These sensors typically consist of a magnet and a magnetic field sensor, such as a Hall-effect sensor, offering several advantages such as high sensitivity and versatility.  \n\nTable 1. Summary of Flexible Pressure Sensors: Mechanisms, Main Materials, and Performance   \n\n\n<html><body><table><tr><td>Sensing mechanism</td><td> Sensing materials</td><td> Structures</td><td>Sensitivity (kPa-1)'</td><td>Pressure range (kPa)</td><td>Response/recovery time (ms)</td><td>The limit of detection (Pa)</td><td>Cycling stability</td><td> Ref</td></tr><tr><td rowspan=\"9\">Piezoresistive</td><td>Liquid metal</td><td>Microbump</td><td>0.158</td><td>0-50</td><td>77</td><td><16</td><td>10,000</td><td>214</td></tr><tr><td>AuNWs</td><td>Fiber</td><td>>1.14</td><td>0-50</td><td><17</td><td>13</td><td>>50,000</td><td>215</td></tr><tr><td>CuNWs/cotton</td><td>Fiber</td><td>0.15</td><td>1.3-20</td><td>400/300</td><td>N/A</td><td>500</td><td>216</td></tr><tr><td>Graphene</td><td>Foam-like</td><td>0.96</td><td>0-113</td><td>72/0.4</td><td>N/A</td><td>100</td><td>218</td></tr><tr><td>CNT/CB</td><td>Sponge</td><td>164 (0-2.1 kPa)</td><td>0-20</td><td>420/330</td><td>11</td><td>8,000</td><td>220</td></tr><tr><td>PAAm/PVA hydrogel</td><td> Pyramid</td><td>2.27</td><td>0-5</td><td>180/170</td><td>9</td><td>1,000</td><td>221</td></tr><tr><td>P(VDF-TrFe)/ rGO</td><td>Nanofiber</td><td>15.6</td><td>0-55</td><td><5</td><td>1.2</td><td>100,000</td><td>275</td></tr><tr><td>PVDF/PEDOT</td><td>Nanofiber</td><td>18.376 (~100 Pa)</td><td>0.002-10</td><td>15</td><td>2</td><td>7,500</td><td>243</td></tr><tr><td>GNPs/ WMCNTs/SR/ PU</td><td>Porous</td><td>0.062</td><td>0-4.5</td><td>~45</td><td>~3</td><td>2,000</td><td>225</td></tr><tr><td></td><td>PDMS</td><td>Porous</td><td>0.63</td><td>>90</td><td>40</td><td>2.42</td><td>10,000</td><td>226</td></tr><tr><td></td><td>Ecoflex/CNT</td><td>Porous</td><td>3.13 (0-1 kPa)</td><td>0-50</td><td>94</td><td>0.07</td><td>5,000</td><td>227</td></tr><tr><td></td><td>PDMS/SWNT</td><td> Pyramid</td><td>0.7</td><td>0-25</td><td>50</td><td>N/A</td><td>10,000</td><td>230</td></tr><tr><td></td><td>PDMS</td><td> Pillar</td><td>0.301 (0-2 kPa)</td><td>0-200</td><td>~200/~200</td><td>1.2</td><td>5,000</td><td>231</td></tr><tr><td></td><td>PDMS</td><td>Slant hierarchical microstructure</td><td>36000 (0.1-1.2 kPa)</td><td>0-300</td><td>40/70</td><td>0.015</td><td>5,000</td><td>232</td></tr><tr><td></td><td>P(VDF-TrFE)</td><td>Interlocked nanocones</td><td>6.583 (0-0.1 kPa)</td><td>0-1</td><td>48/36</td><td>~3</td><td>10,000</td><td>233</td></tr><tr><td></td><td>PDMS</td><td> Porous pyramid</td><td>44.5 (0-0.1 kPa)</td><td>0-35</td><td>50/100</td><td>0.14</td><td>5,000</td><td>235</td></tr><tr><td rowspan=\"4\">Piezoelectric</td><td>PDMS/CNT</td><td>Gradient microdome</td><td>0.065</td><td>0-1700</td><td><100</td><td>N/A</td><td>7,000</td><td>236</td></tr><tr><td>PAN-C/BTO</td><td>Nanofiber</td><td>1.44 V/N</td><td>0.15-25 N</td><td>N/A</td><td>N/A</td><td>60,000</td><td>276</td></tr><tr><td>P(VDF-TrFE)</td><td>Film</td><td>~0.025V (0-20 kPa)</td><td>0-70</td><td>N/A</td><td><800</td><td>400</td><td>277</td></tr><tr><td>Glycine-chitosan</td><td>Film</td><td>~2.82mV</td><td>5-60</td><td><100</td><td>N/A</td><td>9,000</td><td>242</td></tr><tr><td rowspan=\"5\">Triboelectric</td><td>PDA@BTO/ PVDF</td><td>Film</td><td>~0.775 V/N</td><td>0-250 N</td><td>61</td><td>N/A</td><td>1,000</td><td>278</td></tr><tr><td>PTFE/AgNWs</td><td> Pillar</td><td>127.22 mV</td><td>5-50</td><td>N/A</td><td>N/A</td><td>5,000</td><td>250</td></tr><tr><td>PLGA/AgNWs/ PVA</td><td>Hierarchical porous structure</td><td>0.011</td><td>0-40</td><td>N/A</td><td>N/A</td><td>50,000</td><td>252</td></tr><tr><td>PDMS/PAMPS ionogel</td><td>Triangular stripes</td><td>1.76 V/N</td><td>0.1-1 N</td><td>260 (2 Hz)</td><td>N/A</td><td>6,000</td><td>258</td></tr><tr><td>TPU/AgNWs/ rGO</td><td>Multilayer</td><td>78.4</td><td>0-5</td><td>1.4</td><td>N/A</td><td>10,000</td><td>260</td></tr><tr><td rowspan=\"3\">Optical</td><td>NdFeB/Ecoflex</td><td>Cilia array</td><td>6.63 μT/mN</td><td>0-19.5 mN</td><td>73/81</td><td>N/A</td><td>3,000</td><td>266</td></tr><tr><td>NdFeB/PDMS AuNPs/PDMS</td><td>Film </td><td>0.01</td><td>0-120</td><td>~15</td><td>N/A</td><td>30,000</td><td>269 271</td></tr><tr><td></td><td>Fiber</td><td>3.05 dB/N</td><td>0-4.5 N</td><td>23/27</td><td>2.5 mN</td><td>3000</td><td></td></tr></table></body></html>  \n\nOne example is inspired by the bionics of hairs on human skin. magnetic cilia arrays embedded with magnetic particles were utilized to fabricate magnetic sensor arrays (Figure 10a).266 They can detect both magnitude and direction of external forces with resolutions as low as $0.2~\\mathrm{\\mN}$ , and distinguish between different objects based on their magnetic properties. Another magnetic-based tactile skin, utilizing silicone elastomer loaded with magnetic microparticles, is capable of estimating force and localizing contact over large areas with minimal wiring complexity (Figure 10b).267 Moreover, integration of magnetic microelectromechanical systems (MEMS) into electronic skins has enabled bifunctional tactile and touchless perception (Figure 10c).268 they can transduce both mechanical pressure and magnetic field stimuli simultaneously, enabling real-time distinction between tactile and touchless interactions. Distinguish between normal and shear forces have also been achieved by magnetic sensors (Figure 10d).269 These sensors utilize sinusoidally magnetized flexible films and Hall sensors to accurately measure both normal and shear forces, achieving super-resolved accuracy enhanced by deep learning algorithms, offering new possibilities for adaptive grasping and dexterous manipulation. Optical sensors are known for their accuracy and precision.272−274 Thin-film and flexible multipoint 3-axis pressure sensors have been developed using optical methods, enabling high-accuracy sensing of pressure distribution over large areas (Figure 10e).270 By integrating porous rubber as a pressure-sensitive optical modulator, these sensors achieve high sensitivity without sacrificing flexibility or thickness. Furthermore, flexible optical tactile sensors based on soft and plasmonic optical fibers have been introduced, offering sensitive and instantaneous sensing of contact force with low hysteresis and tunable sensitivity (Figure 10f).271 These sensors transduce mechanical stimuli into interpretable light signals, enabling real-time monitoring of pressure and precise perception of object properties.  \n\nTable 2. Summary of Performance Results of Recently Reported Stretchable Strain Sensors with Different Types   \n\n\n<html><body><table><tr><td>Type</td><td> Materials</td><td>Sensing range</td><td>Gauge factor</td><td>Cyclic ability</td><td>Response time</td><td>Relaxation time</td><td>Hysteresis</td><td> Ref</td></tr><tr><td>Resistive</td><td>MWCNT/natural latex</td><td>200%</td><td>Negative</td><td>2000</td><td>NA</td><td>NA</td><td>NA</td><td>279</td></tr><tr><td>Resistive</td><td>AgNPs/PDMS</td><td>0.65%</td><td>1400 (0-0.46%) 18000 (0.46-0.65%)</td><td>>7000</td><td>258 ms</td><td>247 ms</td><td>NA</td><td>279</td></tr><tr><td>Resistive</td><td>PVA/CA/AgNPs</td><td>596%</td><td>1.6</td><td>200</td><td>90 ms</td><td>240 ms</td><td>0.54% (Residual</td><td>280</td></tr><tr><td>Resistive</td><td>PEDOT:PSS/PVA hydrogel</td><td>300%</td><td>4.07</td><td>2000</td><td>NA</td><td>NA</td><td>strain) <1.5%</td><td>281</td></tr><tr><td>Resistive</td><td>Ionogels</td><td>1000%</td><td>0.83 (0-200%) 1.38 (200-400%)</td><td>300</td><td>200 ms</td><td>300 ms</td><td>0.25%</td><td>282</td></tr><tr><td>Resistive</td><td>Au/carbon black/PDMS</td><td></td><td>1.85 (400-600%) 2420</td><td></td><td></td><td></td><td></td><td>283</td></tr><tr><td>Resistive</td><td>FeO4/carbon black/silicone</td><td>45% 180%</td><td>3.24 (0-120%)</td><td>>12000 9000</td><td>17.5 ms 78 ms</td><td>22.5 ms 65 ms</td><td>NA NA</td><td>284</td></tr><tr><td></td><td>rubber</td><td></td><td>21.985 (120-180%)</td><td></td><td></td><td></td><td></td><td>285</td></tr><tr><td>Capacitive Capacitive</td><td>FPCB electrode/silicone MXene/PVA hydrogel</td><td>30%</td><td>0.52</td><td>1000</td><td>NA</td><td>NA</td><td>3.37%</td><td>286</td></tr><tr><td>Piezoelectric</td><td>PVDF nanoyarn</td><td>200% <10%</td><td>0.4 3.95 V kPa-1</td><td>10000</td><td>190 ms</td><td>160 ms</td><td>NA</td><td>287</td></tr><tr><td>Piezoelectric</td><td>ZnO vertically aligned</td><td>0-420 Torr</td><td>3.15 × 10-² kPa-1</td><td>20000 NA</td><td>50 ms 100 ms</td><td>NA 100 ms</td><td>NA NA</td><td>288</td></tr><tr><td></td><td>nanowire/graphene</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Triboelectric Triboelectric</td><td>Polypropylene yarn PTFE fibers/nylon fibers</td><td>30% 80%</td><td>45.47 V (20-30%) Output 0.5 V (under 1%</td><td>40000 >20000</td><td><100 ms 70 ms </td><td><100 ms 71 ms</td><td>NA NA</td><td>289 290</td></tr><tr><td></td><td></td><td></td><td>stretch strain)</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Light Light</td><td>Graphene/PDMS Plasmonic gold NPs/PDMS</td><td>150% 100%</td><td>NA NA</td><td>200 6000</td><td>NA 12 ms </td><td>NA NA</td><td>NA NA</td><td>291 292</td></tr></table></body></html>  \n\nIn short conclusion, various types of pressure sensors also contribute significantly to the field of tactile sensing, providing distinctive capabilities and applications in robotics, healthcare, and human−machine interaction (Table 1). Ongoing research and development endeavors continue to drive innovation in tactile sensing technology, offering promising prospects for further advancements and integration into various practical applications.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.2. Strain Sensors  \n\nStrain sensors are devices that detect deformation or strain in a material and convert this mechanical deformation into an electrical signal. This deformation can be caused by tension, compression, or shear forces. Within the realm of flexible and stretchable strain sensors, three primary classifications emerge: (i) resistive-type, (ii) capacitive-type sensors, and (iii) piezoelectric and triboelectric sensors. Table 2 summarizes the performance of strain sensors developed recently.  \n\nPiezoresistive strain sensors rely on the piezoresistive effect, where the electrical resistance of a material changes when it is deformed. Capacitive strain sensors detect strain by measuring changes in capacitance. When the sensor deforms, the distance between the plates of a capacitor or the dielectric properties of the material changes, leading to a change in capacitance. The third type of strain sensors may utilize the piezoelectric or triboelectric effect, where certain materials generate an electric charge in response to mechanical stress. In addition to the primary types mentioned above, there are several other kinds of strain sensors, including optical fiber strain sensors, which use changes in light properties to detect strain, and resistive foil strain gauges, which are among the most traditional and widely used strain measurement devices. Strain sensors based on magnetic mechanisms also show great potential in emerging applications. These sensors are indispensable tools in modern engineering and technology, providing critical data for robotics.  \n\n2.2.1. Resistive. Resistive strain sensors can be categorized into three types based on their functional materials: carbon nanomaterial-based resistive strain sensors, metal-based resistive strain sensors, and those utilizing other materials. These sensors typically consist of electrically conductive sensing films integrated with flexible substrates. When composite structures undergo deformation, microstructural changes within the sensing films lead to variations in electrical resistance corresponding to the applied strain. Upon strain release, the sensing films revert to their initial configurations, restoring the electrical resistance of the sensors.293 Representative resistive strain sensors are discussed below.  \n\nCNTs are commonly used as conductive materials in resistive strain sensors. A transparent stretchable strain sensor based on single-walled carbon nanotubes (SWCNTs) is reported by Wang et al. (Figure 11a).294 The SWCNT layer was transferred to a PDMS film for a highly transparent stretchable strain sensor with a uniform patterned sensing layer. Yamada et al. presented a category of wearable and stretchable devices constructed using thin films composed of aligned SWCNTs, as shown in Figure $116^{295}$ These SWCNTs film devices, designed for characterizing strain sensors, were fabricated on a dog-bone-shaped substrate composed of PDMS, enabling strain measurements of up to $280\\%$ . In another research, graphene is also used as functional materials (Figure 11c).204 A conductive nanonetwork composed of graphene nanoribbons (GNRs) was established on the surfaces of electrospun TPU fibrous membranes, enabling precise sensing of human motion. This achievement was validated through training sessions with elite dragon boat paddlers.  \n\nIn terms of metal-based resistive strain sensors, Bai et al. fabricated epidermal fabric strain sensors with Au coated TPU fibers, as shown in Figure 11d.296 The effects of prestretch direction and plating strain on sensor response are examined. Additionally, the response of the sensor, including its measuring range and sensitivity, can be controlled during the fabrication process. Another resistive strain sensor was reported to fabricated using core−shell Ag@Au structures with PU (Figure 11e).297 The nanomesh-design of a strain sensor is capable of direct printing onto hands. It imitates human cutaneous receptors by converting electrical resistance change caused by gentle skin stretches into proprioceptive sensations. Besides, Liquid metals (gallium−indium alloy) are commonly used as an intrinsic resistive strain sensor, such as patterned Ga−In strain sensor on gloves (Figure 11f)298 and Ga−In tattoo (Figure 11g).299  \n\n![](images/d116b71af4300a35b09c2b9608654131b191c3b7ce0d67e39c3f1d953cdb8b5b.jpg)  \nFigure 11. Resistance-type flexible strain sensor for soft robotics, classified by the types of active materials. Strain sensors based on carbon nanomaterials, including (a, b) SWCNTs and (c) Graphene. Reproduced with permission from ref 294. Copyright 2020 Springer Nature. Reproduced with permission from ref 295. Copyright 2011 Springer Nature. Reproduced with permission from ref 204. Copyright 2020 Springer Nature. Strain sensors based on metal materials, including (d) Au, (e) Ag and Au, and $\\left(\\mathrm{f{-}g}\\right)$ liquid metal. Reproduced with permission from ref 296. Copyright 2023 Wiley. Reproduced with permission from ref 297. Copyright 2023 Springer Nature. Reproduced with permission from ref 298. Copyright 2020 Wiley. Reproduced with permission from ref 299. Copyright 2021 American Association for the Advancement of Science. Resistive-type strain sensors based on other materials including $\\left(\\mathrm{h-j}\\right)$ conductive polymer, $(\\mathrm{j,k}$ and $^{1,\\mathrm{{m}}}.$ ) composite, and (n) MXene. Reproduced with permission from ref 300. Copyright 2022 Wiley. Reproduced with permission from ref 281. Copyright 2022 Wiley. Reproduced with permission from ref 301. Copyright 2017 Wiley. Reproduced with permission from ref 302. Copyright 2020 American Association for the Advancement of Science. Reproduced with permission from ref 303. Copyright 2017 Wiley. Reproduced with permission from ref 304. Copyright 2021 Wiley. Reproduced with permission from ref 305. Copyright 2023 Wiley.  \n\nOther functional materials including hydrogels, composites, and nanomaterials are widely used in resistive strain sensors. Taking the benefit of hydrogels’ tissue-like softness, Yao et al. introduced a novel phenylboronic acid-ionic liquid (PBA-IL) monomer (Figure 11h)300 The incorporation of multiple crosslinking networks, including dynamic covalent bonds (boronic ester bonds), physical interactions (hydrogen bonds and electrostatic interactions), and chain entanglement allows the as-prepared PAM/PBA-IL/CNF hydrogel to achieve a favorable balance between high performance and multifunctionality. Minimize response hysteresis of strain is challenging, especially when using polymer as substrates. To solve this, Shen et al. presented a PEDOT:PSS-PVA hydrogel strain sensor. Owing to the microphase semiseparated network, the hydrogel strain sensor shows large sensing range $\\left({>}300\\%\\right)$ and ultralow hysteresis (Figure 11i)281 Another hydrogel-based strain sensor, achieve long-lasting moisture and extreme temperature tolerance (Figure 11l).303 Different application scenarios require the strain sensors to attain different properties. To ensure the hydrogel-based strain sensor showed no expansion under water, Ren et al. reported an antiswellable, and ionic conductive hydrogel (DN-FT-HCl) for resistive strain sensors, as shown in Figure $\\scriptstyle11{\\mathrm{m}}$ .304 The increased hydrogen bonding facilitated by the flexible poly(hydroxyethyl methacrylate) chains confers resistance to deformation in the hydrogel. In addition, conducting polymer composite as resistive strain sensor are also reported (Figure 11j)301 This composite comprises three key components: polyaniline (PANI), poly(acrylic acid) (PAA), and phytic acid (PA). The cross-links between polymers form a robust and flexible material which make the composite an ideal material for electronic skins. CB/PDMS composite was proposed to fabricated all-soft robotic textiles with sensing abilities (Figure $11\\mathbf{k})^{302}$ Moreover, nanomaterials other than carbon nanomaterials are also ideal candidates for strain sensor, among which MXene stands out with its high conductivity. Zhao et al. introduced a MXene nanoflake-based hydrogel, as shown in Figure $11\\mathrm{n}^{305}$ Due to the properties of MXene nanoflakes, including hydrophilicity, abundant surface functional groups, and high specific surface area, alongside hydrogen bonding and electrostatic interactions among the components, hydrogels demonstrate exceptional mechanical properties, conductivity, and water retention.  \n\n![](images/18066db2e3e14e69fb7549e44db429e397338f3f729bfa99bff33ead154f9733.jpg)  \nFigure 12. Capacitive-type flexible strain sensor for soft robotics, classified by the types of active materials: Carbon-based capacitive strain sensors, for example (a) CNT and (b) rGO. Reproduced with permission from ref 306. Copyright 2022 Wiley. Reproduced with permission from ref 307. Copyright 2022 American Chemical Society. Metal-based capacitive strain sensors, for example $^{\\mathrm{(c,d)}}$ liquid metal and (e) AgNWs. Reproduced with permission from ref 308. Copyright 2022 Wiley. Reproduced with permission from ref 309. Copyright 2023 Springer Nature. Reproduced with permission from ref 310. Copyright 2023 Wiley. Polymer-based capacitive strain sensors using gels. (f) Hydro/Organo-Gels. (g) Organogel/ Hydrogel. Reproduced with permission from ref 311. Copyright 2021 Wiley. Reproduced with permission from ref 312. Copyright 2023 American Chemical Society.  \n\n2.2.2. Capacitive. Other than resistive flexible strain sensor, capacitive ones utilize a highly compliant dielectric layer positioned between two stretchable electrodes. Tensile strain brings the electrodes into closer proximity, leading to a rise in capacitance.  \n\nFor highly sensitive and stretchable strain sensors, high linearity and low hysteresis are especially challenging. Focusing on improving the dynamic properties of strain sensor, Hu et al. reported a superstretchable and highly sensitive capacitive strain sensor, composed of two strips of wrinkled carbon nanotube-based electrodes separated by a dielectric tape (Figure 12a).306 The sensor was manufactured by transferring carbon nanotube film electrodes, formed through spraycoating, onto both sides of prestretched VHB elastomer, thereby significantly reducing costs. Through the integration of nanomaterials and a wrinkled film structure, this device achieves a gauge factor of 2.07 at $300\\%$ strain, demonstrating excellent linearity and negligible hysteresis. In the meanwhile, ultrasensitivity is also required in some scenarios. In another work by Jiang et al., an exceptionally stretchable and selfhealing hydrogel conductor was developed through a strategy employing both hard and soft dynamic networks (Figure 12b).307 This approach involved the integration of conductive silver nanowire assemblies with wrinkled reduced graphene oxide (RGO) nanosheets within an $\\mathrm{\\Ag{-}}S$ coordinationassisted polyacrylamide hydrogel network. The resulting hydrogel exhibited outstanding performance compared to previously reported stretchable conductors, demonstrating a remarkable elongation of $3250\\%$ .  \n\n![](images/c8882916a73384a110168c83f01da1967143bbf88287dc3d2f6f6fa23207802a.jpg)  \nFigure 13. Flexible strain sensors with other mechanisms. Piezoelectricity-based strain sensors: (a) inorganic tensile strain sensors, (b) strain sensor with hybrid working mechanism, (c) Kirigami strain sensor. Reproduced with permission from ref 316. Copyright 2022 Springer Nature. Reproduced with permission from ref 315. Copyright 2022 Elsevier. Reproduced with permission from ref 314. Copyright 2022 Springer Nature. Triboelectricity-based strain sensors: (d) fiber-shaped strain sensors, (e) triboelectricity-based sensors for gesture detection, (f) triboelectric sensors for lip motion. Reproduced with permission from ref 290. Copyright 2022 American Chemical Society. Reproduced with permission from ref 317. Copyright 2020 Springer Nature. Reproduced with permission from ref 318. Copyright 2023 Springer Nature. Light-based strain sensors, including (g) optical waveguides and $\\mathrm{(h)}$ optical fibers. (i) Magnetic-based strain sensors. Reproduced with permission from ref 118. Copyright 2016 American Association for the Advancement of Science. Reproduced with permission from ref 319. Copyright 2018 Wiley. Reproduced with permission from ref 320. Copyright 2022 American Chemical Society.  \n\nDickey et al. presented a LM-interdigitated capacitive strain sensor (LMICSS) comprising a polydimethylsiloxane (PDMS) microfluidic network filled with LM, depicted in Figure 12c.308  \n\nAs anticipated, capacitance diminished as strain increases. The sensor exhibits high stretchability $(100\\%)$ with a gauge factor of $-0.3$ and excellent durability. Moreover, it demonstrated minimal hysteresis $(<1\\%)$ and is free from crosstalk between strain and normal stress sensing, attributable to its coplanar electrode microchannel configuration. In another work, Fu et al. introduced a $\\mathrm{Ga-In}$ wrapped with thin oxide layer aiming at overcoming the trade-off between soft self-healing properties and high fracture toughness, thus enabling the transformation of soft and weak materials into ones that are both soft and tough while possessing self-healing capabilities (Figure 12d).309 This distinctive approach, inspired by the structure of vascular smooth muscle, was achieved through a hierarchical design involving the integration of core−shell structured spindle Galinstan microdroplets into a soft self-healing polyurea matrix via molecularly interfacial metal-coordinated assembly. The resulting composite exhibited remarkable enhancements in crack-resistant strain and fracture toughness. AgNWs are reported to be used as functional materials in another capacitive strain sensor design. To solve the interference problem, Pan et al. presented a highly antijamming capacitive flexible pressure sensor utilizing a polyvinylidene fluoride (PVDF) $(\\varpi\\mathrm{AgNW}s@\\mathrm{TiO}_{2}$ film as the dielectric layer. The PVDF film incorporates $\\mathsf{A g N W s}@\\mathrm{TiO}_{2}$ with a core−shell structure. This incorporation not only boosts the initial capacitance but also aligns the dielectric constant, dielectric loss, and breakdown strength of the dielectric layer, as shown in Figure 12e.310  \n\nCapacitive-type strain sensors utilizing hydrogel ionic conductors have experienced rapid advancement owing to their resilient structure, drift-free sensing capability, heightened sensitivity, and precision. The electro-mechanical stability of conventional hydrogel conductors, typically susceptible to significant deformation and harsh mechanical forces, continues to pose a challenge. To obtain robust capacitive strain sensor, Mo et al. introduced a dynamically supertough capacitive-type strain sensor based on energy-dissipative dual-cross-linked hydrogel conductors and an organogel dielectric with high adhesive strength (Figure 12f).311 Leveraging the mechanical benefits of the hydrogel and organogel materials, the strain sensor demonstrated exceptional stretchability and a superior linear sensitivity with a gauge factor of approximately $0.8\\%$ at $100\\%$ strain. Furthermore, the sensor exhibited remarkable stability against severe mechanical stresses, enduring even when subjected to extreme scenarios such as being run over by a car on 20 occasions. Utilizing the observed phenomenon of minimal volume change during solvent replacement in the transition from organogels to hydrogels, Zhou et al. designed distinct types of capacitive and resistive strain sensors through various organogel/hydrogel hybrids featuring intricate patterns.312 By relying on the solvent replacement area for pattern formation, we could conveniently fabricate flexible electronic sensors based on organogel/hydrogel hybrids, featuring complex topological structures and functionalities.  \n\n2.2.3. Piezoelectric and Triboelectric. Piezoelectric and triboelectric devices also show their great potential in flexible strain sensors, for effective harvesting of instant mechanical energy to create self-powered systems .313 Bending sensing is a highlight topic in soft robotics and human−machine interaction (HMI), where accuracy of detection of angle change is important. Kim et al. developed a high-performance kirigami piezoelectric strain sensor, evaluating its sensing performance through finite element analysis and optimizing the kirigami patterns (Figure 13c).314 The electromechanical properties of sensors featuring four distinct kirigami patterns analyzed. The piezoelectric strain sensor showed voltage measurement circuit that improved measurement accuracy by amplifying the output voltage 86.5 times. Hybrid systems were developed through both piezoelectric and triboelectric mechanisms to meet the needs of some scenarios. For example, Wang et al. introduced an autonomous wake-up wireless sensing approach utilizing a hybrid generator in wearable bending (Figure 13b).315 Unlike continuous data recording and transmission, the TENG signal triggered the recording of PENG voltage amplitude, serving as angle sensing data for wireless transmission. This concise and precise sensing method with autonomous wake-up is anticipated to mitigate computational load and power consumption in wireless sensing, offering greater potential for wearable wireless monitoring and human−computer interaction. With the rapid development of material science and nanotechnology, a new sensing mechanism based on traditional piezoelectric mechanism was developed, which was called piezotronics effect. The piezotronic effect harnesses the piezoelectric potential generated in materials with piezoelectric properties to act as a “gate” voltage, thereby regulating the charge carrier transport properties to fabricate novel devices. By leveraging the coupling between piezoelectricity and the transport properties of semiconductors, piezotronic sensors utilize strain-induced piezoelectric polarization charges and the resulting piezoelectric potentials at interfaces to linearly adjust the interface barrier height and exponentially control carrier transport. An optimized piezotronic tunneling strain sensor is developed using the $\\mathrm{Ag/HfO_{2}/n\\mathrm{-}Z n O}$ structure (Figure 13a).316 Piezotronic modification effects on interface tunneling transport are observed to occur in two distinct stages: ultralow strain $\\left(<0.01\\%\\right)$ and relatively high strain $\\left(0.01{-}0.10\\%\\right)$ . These stages correspond to the predominant influence of piezotronic regulation on barrier width and barrier height, respectively.  \n\nIn a wearable sign-to-speech translation system, a triboelectric sensing array was integrated on a glove for real-time gesture attraction (Figure 13e).317 A coiled structural configuration ensured that the yarn-based stretchable sensing unit maintains adequate electrical conductivity even when subjected to extreme stretching, thereby ensuring the exceptional durability of the sensing units. The system achieved a recognition rate of $98.63\\%$ and completes recognition in less than 1 s. Structural engineering is important in triboelectric device design. A helical fiber strain sensor (HFSS) was developed by incorporating a helical structure onto a stretchable substrate fiber (Figure 13d).290 Unlike other stretchable fiber strain TENGs, HFSSs fully leverage their helical design. Even with minor stretching, alterations in the contact state between the two triboelectric layers (PTFE and nylon) generate a significant electrical signal. In another application, Lu et al. introduced a novel lip-language decoding system (LLDS) designed to capture mouth muscle movements using flexible, low-cost, self-powered sensors and to recognize signals through a deep learning classifier (Figure 13f).318 These self-powered sensors were strategically positioned at the junction of mouth muscles and were fabricated using flexible polymer films to enhance skin sensation in the mouth region. To address challenges related to signal diversity and limited sample size, they employ a dilated recurrent neural network model based on prototype learning. The system achieved a testing accuracy of $94.5\\%$ .  \n\n2.2.4. Other. In addition to the aforementioned mechanisms, strain sensors based on light and magnetism are emerging and provide instructive ideas for strain sensor designs. Zhao et al. introduced the utilization of stretchable optical waveguides for strain sensing in a prosthetic hand (Figure 13g).118 These photonic strain sensors, characterized by ease of fabrication, chemical inertness, and minimal hysteresis, exhibited high precision in their output signals. To showcase their potential, they were employed as curvature, elongation, and force sensors integrated within a fiberreinforced soft prosthetic hand. This optoelectronically innervated prosthetic hand was utilized to conduct a range of active sensation experiments inspired by the functionalities of a natural hand. As the soft optical systems exhibited notable versatility, particularly in scenarios involving extensive and repetitive deformations necessitating dynamically responsive materials. A study demonstrated the efficacy of stretchable step-index optical fibers, showcasing their ability to withstand strains of up to $300\\%$ reversibly while effectively guiding light (Figure 13h).319 Employing a continuous and scalable meltflow process, the fibers were fabricated by coextruding two thermoplastic elastomers, thus establishing their core-high index and cladding-low index structure. Deformation of these fibers through stretching, bending, and indentation elicits detectable, predictable, reversible, and wavelength-dependent alterations in light transmission. In existing devices, the presence of wires and power supplies poses inconveniences and potential hazards. Magnetic-based systems have emerged as promising alternatives for wireless and passive sensing; however, their widespread adoption in biomechanical monitoring has been hindered by disparities in mechanical properties, limited biocompatibility, and inadequate sensitivity. Addressing these challenges, researchers have developed a wireless and passive flexible magnetic-based strain sensor using a gelatin methacrylate/ $\\mathrm{\\mathrm{Fe}}_{3}\\mathrm{O}_{4}$ magnetic hydrogel (Figure 13i).320 This sensor boasted ultrasoft mechanical characteristics, robust magnetic properties, and sustained stability in saline environments, enabling the monitoring of strains as low as $50~\\mu\\mathrm{m}$ Additionally, a sensing model had been devised to determine the optimal detection site and establish the relationship between relative magnetic permeability and sensor sensitivity.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.3. Temperature Sensors  \n\nTemperature sensing technology has advanced significantly in recent years, offering diverse solutions across different domains, from healthcare to robotics. In this review, we categorize temperature sensors into four types: resistive temperature sensors, thermistors, thermocouples, and other emerging technologies. Each type offers unique advantages and applications, contributing to the broad spectrum of temperature sensing capabilities.  \n\n![](images/072b2d639fe67ac5fd89a0fb31927f9dd5e9337c8deaf8a38335dce5f103c717.jpg)  \nFigure 14. Temperature sensors with various mechanisms, including resistive temperature sensors $\\left(\\mathsf{a}-\\mathsf{f}\\right)$ , thermistor $^{(\\mathrm{g,h)}}$ , thermocouple (i,j), and others $\\mathbf{\\Phi}(\\mathrm{k},\\mathrm{l})$ . (a) Soft electronic arrays for sensing and actuation. Reproduced with permission from ref 321. Copyright 2020 Springer Nature. (b) Multifunctional integumentary membranes for spatiotemporal cardiac measurements and stimulation. Reproduced with permission from ref 322. Copyright 2014 Springer Nature. (c) PEDOT:PSS-based temperature sensor for health monitoring. Reproduced with permission from ref 323. Copyright 2020 Springer Nature. (d) Wearable temperature sensor based on graphene nanowalls. Reproduced with permission from ref 324. Copyright 2015 The Royal Society of Chemistry. (e) Stretchable and conformable networks for multifunctional sensing. Reproduced with permission from ref 325. Copyright 2018 Springer Nature. (f) Skin temperature detection based on transparent and flexible fingerprint sensor array. Reproduced with permission from ref 326. Copyright 2018 Springer Nature. (g) Hydrogel-based ionic skin for a soft robotic gripper. Reproduced with permission from ref 327. Copyright 2020 The Royal Society of Chemistry. (h) Wireless soft sensors for continuous temperature measurement. Reproduced with permission from ref 328. Copyright 2021 Springer Nature. (i) Flexible temperature sensor for functional microfingers. Reproduced with permission from ref 329. Copyright 2019 Springer Nature. (j) Stretchable thermoelectric fabric for wearable temperature sensors. Reproduced with permission from ref 330. Copyright 2018 The Royal Society of Chemistry. (k) Stretchable temperature sensors based on hydrogel films. Reproduced with permission from ref 331. Copyright 2021 American Chemical Society. (l) Stretchable silicon nanoribbon electronics for skin prosthesis. Reproduced with permission from ref 332. Copyright 2014 Springer Nature.  \n\n![](images/bc14009182b4fb786bf59d139ed998e41b0fc8461a32727a542f457a466e3706.jpg)  \nFigure 15. Primary working principles of PDs. (a) Photodiodes. (b) Photoresistors. (c) Phototransistors. Reproduced with permission from ref 335. Copyright 2024 American Chemical Society. Inorganic PDs, including (d) 0D nanomaterials, (e) 1D nanomaterials for artificial retina, (f) 2D nanomaterials. Organic PDs: (g) organic RGB RDs, (h) optoelectronic synapse, and (i) synaptic transistors. Reproduced with permission from ref 339. Copyright 2020 Wiley. Reproduced with permission from ref 340. Copyright 2020 Springer Nature. Reproduced with permission from ref 341. Copyright 2023 Springer Nature. Reproduced with permission from ref 342. Copyright 2021 Wiley. Reproduced with permission from ref 343. Copyright 2023 Springer Nature. Reproduced with permission from ref 344. Copyright 2022 Springer Nature. Structural integrated photonic sensor systems with (j,k) origami designs, (l) kirigami design. $\\scriptstyle{\\left({\\mathrm{m},\\mathrm{n}}\\right)}$ island-bridge design, (o) pop-up design, and (p) Fiddler crab eye mimicking artificial vision system. (q) Aquatic-vision-inspired camera. Reproduced with permission from ref 345. Copyright 2017 Springer Nature. Reproduced with permission from ref 346. Copyright 2019 Wiley. Reproduced with permission from ref 347. Copyright 2021 Springer Nature. Reproduced with permission from ref 348. Copyright 2019 Springer Nature. Reproduced with permission from ref 349. Copyright 2013 Springer Nature. Reproduced with permission from ref 350. Copyright 2018 Springer Nature. Reproduced with permission from ref 351. Copyright 2022 Springer Nature. Reproduced with permission from ref 352. Copyright 2020 Springer Nature.  \n\n2.3.1. Resistive type. Resistive temperature sensors have garnered significant attention due to their simplicity, versatility, and reliability in various applications. These sensors operate based on the principle that the material resistance changes with temperature. Some of them focus on healthcare applications. For minimally invasive cardiac surgery, the soft multilayer electronic arrays were integrated into endocardial balloon catheters (Figure 14a).321 These arrays enable high-density spatiotemporal sensing and actuation, facilitating precise mapping of temperature, pressure, and electrophysiological parameters during surgical procedures. For physiological mapping and stimulation, 3D elastic membranes shaped to match the epicardium of the heart offer deformable arrays of multifunctional sensors and components, providing comprehensive coverage of the heart’s surface (Figure 14b).322 Furthermore, advancements in printed flexible temperature sensors, such as those based on cross-linked PEDOT:PSS, offer enhanced stability and sensitivity, making them suitable for real-time healthcare monitoring in wearable applications (Figure 14c).323 Graphene nanowalls-based wearable temperature sensors exhibit high sensitivity, fast response/recovery speed, and long-term stability, positioning them as valuable tools for personalized healthcare systems (Figure 14d).324 Other temperature sensors pay attention to the robotics or devices. Inspired by human skin, highly stretchable sensor matrix networks enable multifunctional sensing, including temperature detection (Figure 14e).325 Also, lastly, transparent and flexible fingerprint sensor arrays offer multiplexed detection of tactile pressure and finger skin temperature, integrating seamlessly into mobile smart devices (Figure 14f).326  \n\n2.3.2. Thermistor. Thermistors, temperature sensors renowned for their sensitivity to temperature fluctuations, have witnessed recent advancements aimed at overcoming challenges posed by extreme environmental conditions and facilitating continuous temperature monitoring at vital interfaces. For instance, temperature sensors based on zwitterionic PIL hydrogels exhibit remarkable superstretchability, self-healing capabilities, and high conductivity, ensuring stable sensing across a broad temperature range (Figure $\\mathrm{14g)}$ .327 Moreover, soft, skin-mountable sensor systems have emerged to enable uninterrupted monitoring of pressure and temperature at crucial skin interfaces, showcasing feasibility and functionality in hospital settings. These systems hold promise for enhancing patient care and may find diverse applications in healthcare (Figure 14h).328  \n\n2.3.3. Thermocouple. Thermocouples, composed of two dissimilar metal wires fused together, generate a voltage proportional to the temperature variance between the two junctions. Recent advancements in thermocouples have spurred innovations in flexible microactuator-integrated temperature sensors, featuring functional microfingers with temperature sensing capabilities. These sensors exhibit reliability amidst actuation effects and offer potential for applications necessitating flexible and precise temperature measurements (Figure 14i).329 Moreover, textile-based selfpowered temperature sensors, crafted using commercial thermoelectric inks, present linear temperature-sensing capabilities, and high durability. These sensors are well-suited for human−machine interfaces and health monitoring applications (Figure 14j).330  \n\n2.3.4. Other. In addition to the aforementioned advancements, emerging technologies are reshaping the landscape of temperature sensing, offering novel solutions with enhanced capabilities and versatility. One such innovation is the development of stretchable transparent temperature sensors, which employ a novel thin-film sandwich structure (Figure 14k).331 These sensors represent a significant breakthrough as they allow for comfortable attachment to human skin while enabling reliable monitoring of diverse environmental conditions. By relying on changes in capacitance rather than conventional methods, these sensors offer improved accuracy and responsiveness, making them ideal for applications requiring precise temperature measurements in wearable electronics, healthcare, and environmental monitoring.  \n\nMoreover, the integration of smart prosthetic skins equipped with ultrathin, single crystalline silicon nanoribbon sensors marks another notable advancement in temperature sensing technology (Figure 14l).332 These sensors provide highly localized mechanical and thermal perception, mimicking the sensitivity of human skin. As a result, they offer new possibilities for prosthetic and sensory interface technologies, enhancing the functionality and user experience of prosthetic limbs and wearable devices.  \n\nIn conclusion, the evolution of temperature sensing technology is driven by continuous advancements in materials, fabrication techniques, and integration methods.333 From flexible and wearable sensors to sophisticated prosthetic skins, temperature sensors are becoming increasingly sophisticated and versatile, enabling a wide range of applications across various industries.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.4. Optical Sensors  \n\nA photodetector functions as a sensor, detecting light and converting photons into an electrical signal. These devices are ubiquitous in daily life, employed in optical telecommunications, imaging, and biomedical sensing.334 In recent years, flexible photodetector systems have been investigated in robotic applications, such as e-eyes, and flexible cameras.335−337  \n\n2.4.1. Mechanism and Materials. Photodetectors (PDs) convert incident light into electrical signals, primarily utilizing either the photoconductive or photovoltaic effect. The photoconductive effect occurs when absorbed photons generate additional free carriers, reducing semiconductor resistance. Under low light conditions, minimal dark currents flow between the source and drain. However, with light absorption, photon energy exceeding the bandgap creates electron−hole pairs, enhancing photocurrent and reducing device resistance. The photogating effect, a variation of the photoconductive process, arises from trapped photogenerated carriers on defects or surfaces.338  \n\nPDs are categorized into three structures: photodiodes, photoresistors, and phototransistors (pTrs). Photodiodes, commonly employed in flexible and stretchable PDs due to their photovoltaic effect, comprise two-terminal electrodes and an active photoresponsive layer (Figure 15a). Typically, vertically stacked, these photodiodes utilize transparent metal top electrodes, such as ITO, enabling incident light penetration to the active layer, generating electron−hole pairs. This vertical design facilitates rapid response times owing to the short distance between photocarriers and electrodes. In contrast, photoresistors (Figure 15b) feature a simpler configuration with source and drain electrodes and an active layer forming two Ohmic contacts. Operating on the photoconductive effect, they exhibit a wide dynamic range despite extended response times. pTrs, a hybrid of transistors and photodiodes, possess three terminals: source, drain, and gate electrodes, along with an active layer (Figure 15c). Structurally resembling conventional TFTs, pTrs employ photoconductive material in lieu of a semiconducting layer. Under illumination, pTrs, akin to photodiodes, generate electron−hole pairs, and a gate voltage modulates induced photocurrents to amplify output signals, achieving higher sensitivity compared to photodiodes.  \n\nFlexible PDs can be classified through functional materials: inorganic materials and organic materials. Inorganic materialbased PDs exhibit excellent optoelectronic performance, characterized by high carrier mobility facilitated by advanced fabrication techniques. Nonetheless, the inherent bulkiness, brittleness, and rigidity of inorganic semiconducting materials pose challenges for integrating them into flexible or stretchable optoelectronic devices. Addressing this limitation, nanoscale size reduction is employed to enhance the device’s flexibility while preserving the high-performance attributes of inorganic materials. 0D nanomaterial-based PDs exhibit distinct optical, electrical, and mechanical features influenced by the size and shape of semiconducting nanoparticles (NPs) and quantum dots (QDs). Shen et al. demonstrated a straightforward onepot synthesis of all-inorganic $\\mathrm{Cs}\\mathrm{Pb}{\\mathrm{Br}}_{3}$ quantum dots (QDs) under ambient conditions (Figure 15d).339 Particularly, the CsBr/KBr assisted strategy enhances the electrical and optical properties of the QDs. The resulting arrays display significant folding endurance, electrical stability, and uniform performance. Optoelectronic devices leveraging 1D nanomaterials exploit their optical and electrical properties. The advantageous physical attributes, such as a large surface area-to-volume ratio and wire-like geometry, make them conducive to developing high-quality PDs, extending photocarrier lifetimes, reducing transit times, and enhancing mechanical flexibility. Gu et al. presented the development of an artificial visual system employing a spherical biomimetic electrochemical eye (EC-EYE) featuring a hemispherical retina composed of a densely packed perovskite nanowire array fabricated via vaporphase deposition. The device design closely mimics the structural characteristics of the human eye, offering the potential for achieving high-resolution imaging by individually addressing nanowires electrically (Figure 15e).340 Recently, 2D materials have emerged as functional layers in flexible photodetectors, leveraging their exceptional optoelectronic characteristics and high mechanical flexibility. arrays can directly perceive different types of motion at sensory terminals, emulating the nonspiking graded neurons of insect vision systems. The charge dynamics of the shallow trapping centers in $\\mathbf{MoS}_{2}$ phototransistors mimic the characteristics of graded neurons, showing an information transmission rate of 1200 bit $\\ensuremath{\\mathbf{s}}^{-1}$ and effectively encoding temporal light information. Chen et al. introduced phototransistor arrays capable of directly perceiving various types of motion at sensory terminals, emulating the nonspiking graded neurons found in insect vision systems. The charge dynamics of shallow trapping centers in $\\mathbf{MoS}_{2}$ phototransistors mimic the characteristics of graded neurons, exhibiting an information transmission rate of 1200 bits per second and effectively encoding temporal light information (Figure 15f).341 Organic semiconductors have attracted significant attention for flexible and stretchable PDs owing to their distinctive physical, optical, and electrical properties. These include intrinsic flexibility and stretchability, a broad response range, low fabrication cost, lightweight construction, and high compatibility with other electronic components. Moreover, the tunable characteristics of organic semiconductors through chemical design offer additional advantages for the development of customized devices, as the smart artificial retina exhibited in Figure 15g−i.342−344  \n\n2.4.2. Integrated Photonic Systems. Sensing is vital for the survival of most animals, necessitating the processing of vast amounts of external information from visual, auditory, and tactile stimuli. Visual data, in particular, constitutes a substantial portion of this information, driving the development of artificial vision systems. The camera, comprising multiple lenses and a planar image sensor, constitutes a fundamental component of these systems. Recent advancements in electronics and mechanics enable modern machines and robots to perform diverse tasks using various sensing systems, including vision. Consequently, artificial vision systems have become integral visual components of machines and robots.  \n\nStructural engineering offers a convenient approach to enhance the flexibility and stretchability of devices. By cutting, folding, or employing both techniques, a 2D membrane device can be converted into a 3D structure while preserving its optical and electrical properties. Various structural engineering techniques, including kirigami, origami, interconnection designs, and pop-up structures, have been introduced for the fabrication of flexible and stretchable PDs. Origami structures can directly achieve hemispherical electronic eye systems (Figure 15j).345 The folding mechanism is applied to both concave and convex curvilinear arrays of photodetectors, incorporating single-crystalline silicon nanomembranes. Another research presented a photodetector array with a 3D configuration utilizing $\\mathsf{a}{\\mathsf{-}}\\mathsf{G a}_{2}\\mathsf{O}_{3}$ films on a PET substrate (Figure 15k).346 The photodetector cells reveal excellent electrical stability under large bending angle and after thousands of bending cycles. Kirigami design is based on cutting techniques other than folding prepatterned membranes. Rao et al. presented curved and shape-adaptive imagers utilizing ultrathin Si optoelectronic pixel arrays featuring a stretchable kirigami pixel design. Before stretching, the imager achieves a pixel fill factor of $78\\%$ and maintains its optoelectronic performance even when subjected to biaxial stretching of up to $30\\%$ (Figure 15l).347 In addition, islandbridge designs provide the mechanical flexibility of the device by supporting external strains during the deformation process. Sim et al. described a manufacturing technique known as conformal additive stamp (CAS) printing and demonstrate its capability to consistently produce devices with three-dimensional shapes (Figure $15\\mathrm{m}$ ). A digital camera was presented to mimic hemispherical apposition compound eyes found in biology. The high-density PDs were connected through islandbright design which shows low stress concentration in simulation results (Figure 15n). The pop-up structure has been employed in the fabrication of flexible and stretchable PDs by regulating the adhesion between material interfaces and alleviating mechanical strain through delaminated regions. The device membrane was then transferred onto the prestrained elastomeric surface (Figure 15o).350 Larger angles image detection is challenging. Cameras, inspired by the human eye, provide narrow fields of view of less than $100^{\\circ}$ . To solve this, Kim et al. presented a bioinspired camera that leverages the distinctive optical benefits of aquatic vision. This is achieved through the integration of a monocentric lens and a hemispherical silicon nanorod photodiode array. The nanorod photodiode array features a textured and passivated structure, enhancing its light sensitivity and enabling improved imaging performance, particularly under vignetting conditions (Figure 15q).351 Another design of integrated photonic systems focused on panoramic imaging. Microlens arrays featuring a flat surface and a graded refractive index profile are incorporated onto flexible comb-shaped silicon PD arrays, which are affixed to a 3D spherical structure. The combined device demonstrates an exceptionally broad field of view, encompassing nearly the entire 3D space (Figure 15p).352  \n\n![](images/c4d24acaba3834c9ac4ccefda03e1834c06e58686ef922365507edcd58c04185.jpg)  \nFigure 16. Chemical sensors. (a) A gas sensor based on carbon nanotubes. (b) An electrolyte-gated graphene field-effect transistor to detect bactericidal activity. (c) $\\mathbf{MoS}_{2}$ -based field-effect transistor for NO gas detection. (d) Two-dimensional tin disulfide $\\left(\\mathsf{S n S}_{2}\\right)$ flakes-based $\\mathrm{NO}_{2}$ gas sensor. (e) $\\mathrm{Cu}_{3}\\big(\\mathrm{HHTP}\\big)_{2}$ -based FET device for gas sensing. (f,g) Metallophthalocyanine-based MOF utilized for gas sensing. $\\mathbf{\\eta}(\\mathbf{h})$ Gas sensors by integrating nanostructured metal oxides with MOF materials. (i−l) Illustration of metal oxides and their composites used for gas sensors. $\\left({\\mathrm{m-p}}\\right)$ Illustration of other materials used for gas sensors including black phosphorus, MXene, conducting polymers and quantum dots. (a) Reproduced with permission from ref 353. Copyright 2021 The Author(s). Published by the Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported License. (b) Reproduced with permission from ref 354. Copyright 2010 American Chemical Society. (c) Reproduced with permission from ref 355. Copyright 2012 Wiley. (d) Reproduced with permission from ref 360. Copyright 2015 American Chemical Society. (e) Reproduced with permission from ref 356. Copyright 2018 Wiley. (f) Reproduced with permission from ref 357. Copyright 2018 American Chemical Society. (g) Reproduced with permission from ref 358. Copyright 2022 Wiley. (h) Reproduced with permission from ref 359. Copyright 2016 Wiley. (i) Reproduced with permission from ref 361. Copyright 2024 Springer Nature. (j) Reproduced with permission from ref 362. Copyright 2014 The Royal Society of Chemistry. (k) Reproduced with permission from ref 363. Copyright 2024, The Authors, Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). (l) Reproduced with permission from ref 364. Copyright 2014 American Chemical Society. (m) Reproduced with permission from ref 365. Copyright 2015 American Chemical Society. (n) Reproduced with permission from ref 366. Copyright 2017 American Chemical Society. (o) Reproduced with permission from ref 367. Copyright 2003 Springer Nature. (p) Reproduced with permission from ref 368. Copyright 2014 Wiley.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 2.5. Chemical Sensors  \n\nChemical sensor is another cornerstone of modern soft robotic systems, facilitating their ability to perceive and interact with the surrounding environment intelligently. As soft robotics continues to advance, the integration of chemical sensors offers unprecedented opportunities for enhanced functionality and adaptability. These sensors are meticulously designed to detect and quantify specific chemical compounds or changes in the environment, providing crucial information for decisionmaking and autonomous operation. Whether deployed in medical devices for real-time diagnostics, environmental monitoring systems for pollution detection, or industrial robots for quality control, chemical sensors enable soft robots to navigate complex and dynamic environments with precision and efficacy. Harnessing the synergy between chemical sensing and soft robotics holds immense potential to revolutionize various domains, driving innovation and addressing pressing societal challenges.  \n\n2.5.1. Carbon Materials. Carbon-based materials such as carbon nanotubes and graphene have been widely utilized in the fabrication of chemical sensors due to their exceptional properties. With their large surface area, excellent electrical conductivity, and chemical stability, these materials offer an ideal platform for detecting and quantifying various analytes in the environment. Additionally, their high sensitivity and selectivity make them well-suited for detecting even trace amounts of target molecules. Moreover, the inherent flexibility and tunability of carbon-based materials enable the development of flexible and wearable chemical sensors, perfectly aligned with the requirements of soft robotic applications. Sangaletti’s group investigated the efficacy of a sensor array based on functionalized carbon nanotubes (CNTs) for breath analysis, particularly in breathomics applications (Figure 16a). The study involved fabricating a sensor array comprising CNTbased sensors and assessing their ability to detect specific biomarkers in breath samples. Various gases and volatiles, such as $\\mathrm{NH}_{3},\\mathrm{NO}_{2},\\mathrm{H}_{2}\\mathrm{S},$ and benzene, were tested to evaluate the sensor array2’s s2ensitivity and selectivity.353 Loh’s group developed a bioelectronic platform leveraging a graphenelipid bilayer interface (Figure 16b). Through an electrolytegated graphene field-effect transistor, they scrutinized the electrical interaction between graphene and charged lipid membranes.354  \n\n2.5.2. Transition Metal Dichalcogenides (TMDs). The emergence of two-dimensional (2D) transition metal dichalcogenides (TMDs) has emerged as a promising avenue for the fabrication of gas sensors. Zhang’s group fabricated single- and multilayer $\\mathbf{MoS}_{2}$ films using the mechanical exfoliation method. They then used these films to fabricate field-effect transistor (FET) devices (Figure 16c). The FET devices were used to detect the adsorption of NO gas.355 Ou’s group developed a gas sensor utilizing two-dimensional tin disulfide $(\\mathrm{{SnS}}_{2})$ flakes for selective and reversible nitrogen dioxide $\\left(\\mathrm{NO}_{2}\\right)$ gas detection (Figure 16d). This sensor exhibits high sensitivity and superior selectivity to $\\mathrm{NO}_{2},$ particularly at temperatures below $160~^{\\circ}\\mathrm{C}$ .  \n\n2.5.3. Metal−Organic Frameworks (MOFs). Metal− organic framework (MOF) materials have garnered significant attention in the field of chemical sensors due to their unique properties and tunability. These porous materials consist of metal ions or clusters coordinated with organic ligands, resulting in a highly porous and crystalline structure. MOFs offer a large surface area, diverse pore sizes, and adjustable chemical properties, making them ideal candidates for various sensing applications. Rubio-Giménez et al. investigated the chemiresistive response of ultrathin films composed of conductive MOFs (Figure 16e). They synthesized highly oriented semiconductive $\\mathrm{Cu}_{3}\\big(\\mathrm{HHTP}\\big)_{2}$ films using a bottomup approach and integrated them into field-effect transistor (FET)-type devices. Their study aimed to elucidate the underlying mechanisms behind the chemiresistive response observed in these devices. Combining experimental data with computational modeling, the authors proposed that changes in the electrical conductivity of the Cu-CAT-1 films are governed by the coordination of guest molecules with the open metal sites in the 2D MOF layer.356 Mirica’s group has made significant strides in the development of modular metal− organic frameworks (MOFs) utilizing metallophthalocyaninebased building blocks (Figure $16\\mathrm{f,g},$ ). These MOFs boast outstanding conductivity, low-dimensionality, high surface area, and a precisely ordered arrangement of active sites at the nanoscale. Leveraging these properties, the group has incorporated these MOFs into chemiresistive gas sensing devices, achieving excellent sensitivity and impressively low detection limits for gases like $\\mathrm{NH}_{3},$ $\\operatorname{H}_{2}S,$ and NO.357,358 Xu’s group proposed an approach to enhance the performance of chemiresistor gas sensors by integrating nanostructured metal oxides (MOXs) with MOFs into a core−sheath nanowire structure (Figure 16h). In their study, a hydrophobic and catalytic Zeolitic Imidazolate Framework-CoZn (ZIF-CoZn) thin film was coated onto $\\mathrm{znO}$ nanowires, forming a core− sheath nanowire array. This $\\mathrm{ZnO}@\\mathrm{ZIF-CoZn}$ nanowire array exhibited markedly improved sensing capabilities for acetone detection under humid conditions. It demonstrated enhanced selectivity, superior response and recovery behavior, and reduced operating temperatures compared to sensors based solely on $\\mathrm{znO}$ nanowire arrays.359  \n\n2.5.4. Metal Oxides and Composites. Fan’s group developed a highly sensitive and selective gas sensor based on biomimetic olfactory chip (BOC) technology. The fabrication process involved depositing a $\\mathrm{PdO}/\\mathrm{SnO}_{2}$ sensing film on a custom MEMS substrate using atomic layer deposition (ALD), creating a gradient film composition using sputtering, and fabricating electrodes, an insulating layer, and a heater on the substrate (Figure 16i).361 Wang’s group reported the synthesis of plate-like $\\mathtt{p-n}$ heterogeneous ${\\mathrm{NiO}}/{\\mathrm{WO}}_{3}$ nanocomposites by annealing $\\mathrm{\\Ni(OH)}_{2}$ and $\\mathrm{H}_{2}\\mathrm{WO}_{4}$ in air (Figure 16j). These nanocomposites were investigated for their gas-sensing behavior toward various toxic gases, including $\\mathrm{H}_{2}S,$ $\\mathrm{CH}_{4},$ NO, $\\mathrm{NO}_{2},$ ${\\mathrm{~\\thinspaceSO}}_{2},$ and CO.362 Liu’s group developed a hierarchical nanoheterostructure comprising HFIP-grafted $\\alpha$ - ${\\mathrm{Fe}}_{2}{\\mathrm{O}}_{3}@$ multiwall carbon nanotubes (MWCNTs) to create high-performance chemiresistive sensors for nerve agents (Figure $\\mathbf{l}6\\mathbf{k}\\overline{{\\mathbf{\\Omega}}}$ ). The synthesis process involved directly growing $\\scriptstyle\\alpha-\\mathrm{Fe}_{2}\\mathrm{O}_{3}$ nanorods onto MWCNT backbones, followed by functionalization with hexafluoroisopropanol (HFIP). These composites were utilized for detecting dimethyl methylphosphonate (DMMP), a sarin simulant gas. Results demonstrated that the HFIP- ${\\cdot\\alpha{\\cdot}\\mathrm{Fe}_{2}\\mathrm{O}_{3}}@\\mathrm{MWCNT}$ hybrids exhibited exceptional DMMP-sensing capabilities, including low operating temperature, high response, short response/recovery time, and low detection limit.363 Kim’s group reported on the development of highly sensitive and selective gas sensors for detecting $\\mathrm{H}_{2}S$ and acetone in humid environments.364 These sensors employ $\\mathrm{SnO}_{2}$ nanofibers combined with reduced graphene oxide (RGO) nanosheets to form composite sensing layers (Figure 16l). The proportion of RGO in these layers is finetuned to modify the sensors’ properties. The sensors were evaluated for their responsiveness to $\\mathrm{H}_{2}S$ and acetone at various temperatures, revealing that certain RGO concentrations yield the strongest response to each gas. They demonstrate rapid response and recovery times, and high specificity for $\\mathrm{H}_{2}S$ and acetone.  \n\n2.5.5. Other Materials. Zhou’s group explored the chemical sensing capabilities of multilayer black phosphorus (BP) field-effect transistors (FETs) for detecting nitrogen dioxide $\\left(\\mathrm{NO}_{2}\\right)$ (Figure $16\\mathrm{m}\\dot{}$ ). They tested the BP FETs by exposing them to various concentrations of $\\mathrm{NO}_{2}$ and tracking the changes in conductance. These devices demonstrated a significant increase in conductance upon exposure to $\\mathrm{NO}_{2},$ showing exceptional sensitivity with detection limits as low as 5 parts per billion (ppb).365 In addition, MXene is also used for  \n\n![](images/1451d0ef74beb00be2f72bd22767bfe6e2584bc2aa482e7da0f401ad1f98ee95.jpg)  \nFigure 17. Flexible ultrasound devices with single units $\\left({\\mathsf{a}}{-}{\\mathsf{d}}\\right)$ or array devices (d−k). (a) Schematic of single-unit-based ultrasound device. (b) Ultrasonic autopositioning for soft robotic perception system. Reproduced with permission from ref 370. Copyright 2023 American Chemical Society. (c) Miniaturized electromechanical devices for deep tissue characterization. Reproduced with permission from ref 371. Copyright 2021 Springer Nature. (d) Mechano-acoustic sensing of physiological process and body motions. Reproduced with permission from ref 372. Copyright 2020 Springer Nature. (e) Schematic of array-based ultrasound device. (f) Stretchable ultrasonic phased arrays for continuous monitoring of deeptissue hemodynamics. Reproduced with permission from ref 373. Copyright 2021 Springer Nature. (g) Bioadhesive ultrasound for long-term  \n\ncontinuous imaging of diverse organs. Reproduced with permission from ref 374. Copyright 2022 American Association for the Advancement of Science. (h) Stretchable ultrasonic transducer arrays for imaging on complex surfaces. Reproduced with permission from ref 375. Copyright 2018 American Association for the Advancement of Science. (i) A conformal ultrasonic device for monitoring central blood pressure waveform. Reproduced with permission from ref 376. Copyright 2018 Springer Nature. (j) A wearable cardiac ultrasound imager. Reproduced with permission from ref 377. Copyright 2023 Springer Nature. $(\\bar{\\mathbf{k}})$ A conformal phased-array ultrasound patch for bladder volume monitoring. Reproduced with permission from ref 378. Copyright 2024 Springer Nature.  \n\ngas sensor fabrication. Kim’s group has developed wearable gas sensors using $\\mathrm{Ti}_{3}\\mathrm{C}_{2}\\mathrm{T}_{\\boldsymbol{x}}$ nanosheets, a type of two-dimensional material derived from $\\mathrm{Ti}_{3}\\mathrm{AlC}_{2}$ (Figure 16n). These nanosheets are integrated onto flexible polyimide platforms, creating sensors that can operate at room temperature. The sensors’ performance was evaluated against various gases including ethanol, methanol, acetone, and ammonia. The results demonstrated a p-type sensing behavior, with the highest sensitivity to ammonia and the least to acetone, where the detection limit for acetone was theoretically established at about 9.27 ppm compounds, underscoring the diagnostic potential of this technology.366 Janata et al. explored the application of conducting polymers in electronics, particularly in the construction of devices and as selective layers in chemical sensors. The study emphasizes the conductivity and work function of conducting polymers and investigates how these properties are influenced by interactions with ambient gases (Figure 16o). This interaction is critical for understanding the functionality of conducting polymers in various environmental conditions. Additionally, the authors describe various electronic devices that can be fabricated using conducting polymers, including chemiresistors, field-effect transistors (FETs), capacitors, and diodes.367 Tang’s group conducted research on the sensing mechanism of $\\mathrm{NO}_{2}$ gas using lead sulfide colloidal quantum dots (PbS CQDs) (Figure $16\\mathrm{p})$ . They synthesized these quantum dots and used them to develop a high-performance, paper-based flexible $\\mathrm{NO}_{2}$ gas sensor. The study explored various treatments to enhance the sensing characteristics of the devices. It was found that $\\mathrm{NO}_{2}$ interacts with the surface of the PbS CQDs, leading to p-type doping and a decrease in resistance. These sensors not only operate effectively at room temperature but also demonstrate high sensitivity and rapid response to $\\mathrm{NO}_{2}$ exposure. Additionally, the flexibility and durability of the paper-based sensors highlight their potential for practical applications in environmental monitoring and safety.368",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 2.6. Acoustic Sensors  \n\nAcoustic devices encompass a diverse array of technologies that harnessing sound waves to fulfill a multitude of functions, spanning from communication and sensing to medical imaging and industrial testing.369 Acoustic waves are mechanical vibrations that propagate through mediums like air, water, or solid materials, characterized by frequencies, wavelengths, and amplitudes. These waves can be broadly classified into three main types based on their frequencies: audible waves $20\\mathrm{Hz}$ to $20,000~\\mathrm{Hz},$ , ultrasound waves $\\left(>20,000~\\mathrm{Hz}\\right)$ , and infrasonic waves $\\left(<20~\\mathrm{Hz}\\right)$ . Given their crucial applications in fields like healthcare and imaging, our focus here will primarily center on ultrasound and audible ranges.  \n\nThe audible range pertains to frequencies detectable by the human ear, where sound waves manifest as various pitches. Lower frequencies correspond to deeper tones, like those of a bass drum, while higher frequencies produce sharper sounds, like to a whistle. In contrast, ultrasound waves possess shorter wavelengths and higher frequencies than audible sound waves, enabling them to penetrate materials and generate detailed images of internal structures. Ultrasound technology finds extensive use not only in medical imaging, including prenatal ultrasounds for monitoring fetal development, but also in industrial applications, such as nondestructive material testing. Thereby, acoustic devices serve as indispensable tools across a spectrum of fields, facilitating communication, sensing, imaging, and measurement across frequencies ranging from the audible realm to ultrasound frequencies. Their adaptability and efficacy underscore their pivotal role in modern technology and everyday life.  \n\n2.6.1. Ultrasound Waves. Ultrasound devices have revolutionized various fields, including medical imaging, longterm healthcare monitoring, and intelligent robotics. This is because ultrasound waves have the ability to penetrate not only materials but also the human body without harmful effects, allowing them to provide detailed information about internal organs. Based on the number of transducers, these devices can be categorized into two types: single-unit-based ultrasound devices and array-based ultrasound devices.  \n\nSingle-unit ultrasound devices typically consist of a single transducer element that emits and receives ultrasound waves (Figure 17a). Based on the information obtained from these waves, useful data can be analyzed and extracted. These devices are simple and compact, making them suitable for portable applications and point-of-care diagnostics. In robotic systems, ultrasonic sensors have been integrated with flexible triboelectric sensors to achieve not only remote object positioning but also multimodal cognitive intelligence. Such advancements are pivotal in expanding the capabilities of soft robotic systems, paving the way for industrial automation and healthcare (Figure 17b).370 For the diagnosis of human body conditions, miniaturized electromagnetic devices have been designed to measure the Young’s modulus of skin and soft tissue, offering a novel approach to accurately locating lesions associated with skin conditions like psoriasis. This facilitates early intervention and personalized treatment strategies (Figure 17c).371 Moreover, these devices enable monitoring of various physiological processes for healthcare and rehabilitation. For instance, skin-mounted soft electronics incorporating triaxial accelerometers enable continuous measurement of mechano-acoustic signals, including heart rate, respiration, and subtle body movements (Figure 17d).372  \n\nOn the other hand, array-based ultrasound devices consist of multiple transducer elements arranged in a linear or twodimensional array (Figure 17e). By controlling the timing and amplitude of each transducer element, array-based devices can produce focused ultrasound beams and perform advanced imaging techniques such as beamforming and synthetic aperture imaging. This allows for improved image quality, spatial resolution, and visualization of complex structures in three dimensions. For example, a skin-conformal ultrasonic phased array capable of monitoring hemodynamic signals from deep tissues, empowering individuals to track their cardiovascular health in real-time and facilitating early intervention in case of abnormalities (Figure 17f).373 Similarly, a bioadhesive ultrasound device for continuous imaging of internal organs over extended periods. The ability, providing uninterrupted imaging of diverse internal structures, holds immense potential for diagnosing and monitoring many medical conditions, from gastrointestinal disorders to cardiac abnormalities (Figure 17g).374  \n\n![](images/af15116f8668d6a2038d333bb81939b7ddcc31df297232896966558b86916159.jpg)  \nFigure 18. Flexible acoustic devices with different mechanisms. (a) Transparent and conductive nanomembranes for skin-attachable loudspeakers and microphones. Reproduced with permission from ref 379. Copyright 2018 American Association for the Advancement of Science. (b) An acoustic interface for wearable human−machine interaction. Reproduced with permission from ref 380. Copyright 2021 Wiley. (c) Acoustic smart skin for human−machine interface. Reproduced with permission from ref 381. Copyright 2022 American Association for the Advancement of Science. (d) An ultrathin conformable vibration-responsive electronic skin for vocal recognition. Reproduced with permission from ref 382. Copyright 2019 Springer Nature. (e) An ultrasensitive artificial mechanotransducer skin. Reproduced with permission from ref 383. Copyright 2017 Wiley. (f) Acoustic fabrics via single fiber. Reproduced with permission from ref 384. Copyright 2022 Springer Nature. (g) Fully flexible electromagnetic vibration sensor with origami magnetic membranes. Reproduced with permission from ref 385. Copyright 2020 Wiley. (h) An ultrasensitive MXene-based intelligent artificial eardrum. Reproduced with permission from ref 386. Copyright 2022 American Association for the Advancement of Science.  \n\nThe development of a stretchable ultrasound probe marks another milestone in ultrasound technology (Figure 17h).375 This innovative probe can conform to nonplanar complex surfaces, enabling high-resolution imaging through anatomically challenging regions. Such advancements are invaluable in fields like structural engineering, where detecting defects in intricate geometries is paramount. Furthermore, wearable ultrasonic devices, designed for continuous monitoring of central blood pressure waveforms (Figure 17i), continuous cardiac function assessment (Figure 17j) and volumetric organ monitoring (Figure 17k), represent significant strides toward personalized healthcare.376−378 By leveraging advancements in materials science and signal processing algorithms, these devices offer unparalleled accuracy and reliability, empowering individuals to monitor their health proactively.  \n\n![](images/0cd539d4c03ed7e6298973a6b13e39d54f9db4d831a625dd715d3866a4f5fea0.jpg)  \nFigure 19. Flexible magnetoreception and Electroreception sensing systems for soft robotics. (a) Flying migrating birds. Credits: Jiangtao Su (b) Pigeons’ organ for navigation. Reproduced with permission from ref 387. Copyright 2003 Wiley. (c) The mechanism of navigation organ. Reproduced with permission from ref 388. Copyright 2012 American Association for the Advancement of Science. Flexible magnetoreception based on different mechanisms: (d) Hall effect-based flexible tactile sensors. Reproduced with permission from ref 389. Copyright 2021 Springer Nature. (e) Magneto-piezoresistance based touchless Sensing Interface. Reproduced with permission from ref 390. Copyright 2021 American Chemical Society. (f) GMR based e-skins. Reproduced with permission from ref 391. Copyright 2020 American Association for the Advancement of Science. (g) AMR-based flexible magnetic sensors. Reproduced with permission from ref 392. Copyright 2016 Wiley. (h) Electrosensory systems in sharks. Reproduced with permission from ref 393. Copyright 2022 American Association for the Advancement of Science. Electroreception systems based on different mechanisms: (i) Electrostatics based electroreceptors for precontact somatosensation. Reproduced with permission from ref 393. Copyright 2022 American Association for the Advancement of Science. (j) Flexible capacitive sensor for wireless perception. Reproduced with permission from ref 394. Copyright 2021 IEEE. (k) Flexible capacitive sensor sheet for proximity detection. Reproduced with permission from ref 395. Copyright 2021 Wiley.  \n\nIn summary, recent advancements in ultrasound technology have propelled the field toward unprecedented heights. Whether in the form of single-unit devices or array-based systems, these innovations hold the potential to revolutionize diverse industries and improve the quality of life for millions worldwide.  \n\n2.6.2. Audible Waves. Acoustic devices for audible waves play a crucial role in various applications, from human machine interaction to healthcare monitoring. This part explores recent developments in acoustic sensors across different mechanisms, including triboelectric, capacitive, piezoelectric, magnetic, and resistive sensors, highlighting their unique capabilities and potential applications.  \n\nTriboelectric sensors harness the principle of triboelectricity, where contact electrification occurs due to the contact and separation of materials. For example, the development of ultrathin and transparent hybrid nanomembrane, embedding with silver nanowire arrays within a polymer matrix (Figure 18a), enables the creation of skin-attachable loudspeakers and microphones, facilitating voice recognition and human− machine interaction.379 Another example is the waterproof  \n\nAcoustic Sensor designed to serve as a wearable translation interface for human−machine interaction, covering almost the entire human audible range from 0.1 to $20\\mathrm{kHz}$ . It functions as a high-fidelity auditory platform suitable for various applications, including music recording and speech recognition (Figure 18b).380 Furthermore, dual-mode human−machine interfaces have also been explored, such as frequency-selective acoustic and haptic sensors with hierarchical structures showing high sensitivity and noise-independent voice recognition (Figure 18c).381  \n\nCapacitive sensors utilize changes in capacitance to detect acoustic signals, typically by measuring the distance change between electrodes. For example, ultrathin, conformable vibration-responsive electronic skins have been developed capable of detecting skin acceleration correlated with voice pressure (Figure 18d).382 These sensors exhibit outstanding sensitivity and skin conformity, making them suitable for voice recognition applications such as security authentication and remote-control systems. Additionally, capacitive sensors with waterproof capability have been developed, serving as wearable translation interfaces for human−machine interaction (Figure 18e).383 These sensors enable users to interact with devices in various environments without concern for water damage, expanding their potential applications in both consumer electronics and industrial settings.  \n\nPiezoelectric sensors convert mechanical stress into electrical signals, offering high sensitivity and frequency response. Fabrics integrated with piezoelectric fibers have been developed, functioning as sensitive audible microphones while retaining fabric qualities such as washability and draping (Figure 18f).384 These fabrics enable applications ranging from precise acoustic impulse direction measurement to cardiac sound auscultation, opening up new possibilities for smart clothing. Magnetic sensors detect mechanical motion through changes in magnetic fields. For example, the development of fully flexible electromechanical system sensors for wearable monitoring of mechanical displacement (Figure $18\\mathrm{g}$ ).385 These sensors offer broad frequency responses and high sensitivities, enabling applications in biophysical sensing, motion detection, and voice recognition. Resistive sensors, such as those based on two-dimensional MXene materials, mimic the function of human eardrums for voice detection and recognition (Figure 18h).386 MXene-based artificial eardrums exhibit extremely high sensitivity and low detection limits, enabling accurate voice classification through machine learning algorithms. These sensors hold promise for wearable acoustical healthcare devices.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 2.7. Electromagnetic Sensors  \n\nElectromagnetic sensing is crucial in robotics due to its ability to gather information about the surrounding environment using electromagnetic waves. These waves encompass various frequencies, such as radio waves, microwaves, and infrared radiation, allowing robots to perceive their surroundings in diverse conditions and across different distances. By detecting electromagnetic signals reflected off objects or emitted by them, robots can accurately sense distances, identify obstacles, and navigate through complex environments. Overall, electromagnetic sensing plays a pivotal role in robotics by providing vital sensory input, enhancing robot perception, and facilitating intelligent decision-making processes, ultimately contributing to their autonomy and effectiveness in a wide range of applications. Here, we focused on the magnetoreception and electroreception systems.  \n\n2.7.1. Magnetoreception. Migrating birds are capable navigators, relying on a combination of sensory cues and innate abilities to orient themselves and navigate across varying distances (Figure 19a). They can use the Earth’s magnetic field for orientation, adjusting their flight paths accordingly. Fleissner et al. examined the subcellular organization of afferent trigeminal terminals in the upper beak of the homing pigeon, Columba livia (Figure 19b).387 These terminals are approximately $5~\\mu\\mathrm{{m}}$ in diameter and contain superparamagnetic magnetite (SPM) crystals. The surroundings of one SPM cluster are the subcellular structure of a putative pigeon-type magnetoreceptor. The current model of avian magnetoreception proposes the existence of two magnetic sensory structures: one located in the eye, which provides a magnetic reference direction, and another situated in the upper beak to gauge magnetic-field intensity, serving as input for the navigational map. Neurons within the pigeon brain encode information regarding Earth’s magnetic field to facilitate orientation and navigation (Figure 19c).388  \n\nInspired from navigable birds, robotics with the magnetosensing ability shows great potential to obtain an inherently touchless detection, opening up a broad spectrum of interaction scenarios.396 Magnetoreceptors’s mechanisms can be roughly classified into four types: Hall effects, magnetopiezoresistance, giant magnetoresistive (GMR) and anisotropic magnetoresistive (AMR).397 Kaidarova et al. reported a type of laser-scribed graphene Hall sensors with linear response to magnetic fields. They also exhibit a low constant noise voltage floor for a bias current of $100\\mu\\mathrm{A}$ at room temperature, which is comparable with state-of-the-art low-noise Hall sensors (Figure 19d).389 In another work, Zhang et al. proposed a new touchless sensing device based on the magneto-piezoresistive effect (Figure 19e).390 By having a hierarchical magnetoelastomer coated with a 3D piezoresistive network for touchless tactile perception, the attractive magnetic force induced by the approaching magnetic material initially acts on the ferromagnetic substrate and then transmits to the coated piezoresistive layer, leading to a change in resistance. GMR is a quantum mechanical magnetoresistance effect seen in multilayers made of alternating ferromagnetic and nonmagnetic conducting layers. Kondo et al. reported the development and low-voltage operation of an imperceptible organic electronic system comprising solely p-type organic thin-film transistors (OTFTs), capable of integrating all components required for the operation of an active magnetosensory matrix (MSM) system (Figure 19f).391 Unlike GMR, the AMR effect is a phenomenon that the resistance of anisotropic magnetic materials changes with the angle between the magnetization and the current direction. A self-biased AMR magnetic field sensors was proposed, which exhibit a sensitivity limit of approximately $150~\\mathrm{nT}$ at $3\\:\\mathrm{Hz}$ when fabricated on PR-buffered flexible PET foils (Figure $19\\mathrm{g}$ ).392 These sensors also demonstrate a sensitivity of $42~\\Bar{\\mathrm{T}}^{-1}$ , similar to that of AMR sensors on rigid oxidized silicon substrates. Furthermore, the AMR sensors on flexible substrates exhibit excellent deformation stability, with no degradation in electrical output observed even at bending radii as small as $5~\\mathrm{mm}$ .  \n\n2.7.2. Electroreception. Interestingly, certain organisms in nature, such as sharks inhabiting the dark sea, utilize an electroreception strategy for remote perception. Sharks possess the ability to detect minute electric field gradients in the ambient environment through a multitude of electroreceptors dispersed across their head. Electric signals are captured by dermal pores and conveyed to the shark’s electrosensory cells.  \n\n![](images/4a2452f74101f9bdeb7ac8de193f831495bde912890ed90cbe05a3405c05c9c4.jpg)  \nFigure 20. Flexible sensors for normal and shear force detection based on $\\left(\\mathsf{a}-\\mathsf{f}\\right)$ piezoresistive, (i−l) capacitive, and $\\left({\\mathrm{m-p}}\\right)$ magnetic mechanism. (a) Photograph of the mechanoreceptor-inspired soft sensing device with multimodal tactile information detection abilities. Reproduced with permission from ref 400. Copyright 2022 Wiley. (b) Flexible sensor that can detect the direction of external force based on self-adjusting CNT arrays. Reproduced with permission from ref 401. Copyright 2018 IOP Publishing. (c) Schematic illustration of the structure of tenon and mortiseinspired six-dimension force sensor. Reproduced with permission from ref 402. Copyright 2022 Elsevier. (d) Top: Schematic illustration of the flexible sensor with opposite resistance responding that can detect normal and tangential forces. Bottom: photograph of the flexible force sensor. Reproduced with permission from ref 403. Copyright 2018 Wiley. (e) Schematic illustration of the skin-inspired multimodal mechanoreceptor that can detect normal and shear forces, and hardness, texture, and tackiness of objects. Reproduced with permission from ref 404. Copyright 2024 Wiley. (f) Photograph of the three-dimensional piezoresistive structures with multimodal sensing abilities. Reproduced with permission from ref 405. Copyright 2019 American Association for the Advancement of Science. (g) Structure of the three-axial flexible capacitive force sensor. Reproduced with permission from ref 406. Copyright 2011 IOP Publishing. (h) Flexible three-axial capacitive tactile sensor with multilayered dielectric structures. Reproduced with permission from ref 407. Copyright 2017 Springer Nature. (i) Photograph of the highly sensitive flexible three-axial force sensor. Reproduced with permission from ref 408. Copyright 2014 Wiley. (j) Schematic illustration of the pyramid-plug structureinspired tactile sensor for measurement of pressure, shear force, and torsion. Reproduced with permission from ref 409. Copyright 2018 Wiley. (k) Photograph of the polymer-based capacitive sensor array that can measure normal and shear forces. Reproduced with permission from ref 410. Copyright 2010 MDPI. (l) Hierarchically patterned e-skin that can detect the direction of forces and its integration on a robotic hand. Reproduced with permission from ref 234. Copyright 2018 American Association for the Advancement of Science. $\\mathrm{(m)}$ Structure of the three-axial Hall effectbased tactile sensor. Reproduced with permission from ref 411. Copyright 2016 MDPI. (n) Photograph of the split-type magnetic tactile sensors. Reproduced with permission from ref 412. Copyright 2023 Wiley. (o) Soft magnetic e-skin with high tactile sensing resolution and force decoupling capabilities. Reproduced with permission from ref 269. Copyright 2021 American Association for the Advancement of Science. (p) Schematic illustration of the multimodal magnetoelastic e-skin that can work underwater. Reproduced with permission from ref 413. Copyright 2024 American Association for the Advancement of Science.  \n\nSubsequently, electrically gated ion channels are activated, facilitating the movement of ions across the cell membrane (as shown in Figure 19h).393 Based on electrostatic induction effect, an artificial electroreceptor was designed for detecting approaching targets. (Figure 19i).393 This receptor can encode environmental precontact information into a sequence of voltage pulses, serving as distinctive interfaces for precontact interactions with humans. Flexible capacitive sensors are also used for electroreception in distant-response scenarios. Qin et al. introduced a flexible dual-mode capacitive sensor for interactive and wireless sensing of a proximity contact interface (Figure 19j).394 The sensors were fabricated via large-scale screen printing and rapid laser engraving techniques. Incorporating a microcone structure on a dielectric film, the dual-mode sensors achieved a detection distance of up to 20 cm in proximity mode, with an expanded operating range of $200\\mathrm{kPa}$ , a low detection limit of $10.2\\mathrm{Pa},$ , and a rapid response time of $90~\\mathrm{{ms}}$ . In a flexible trimodal sensing systems, proximity sensing sensor sheet relies on self-capacitance measurement (Figure 19k).395 An electrode layer functions as a sensing electrode, emitting electric field (E-field) lines in multiple directions when positively charged. As a conductor (e.g., a hand) approaches, whether grounded or capacitively coupled to virtual ground, E-field lines partially converge toward its surface, resulting in increased capacitance between the sensing electrode and ground.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 2.8. Multimodal Integration  \n\nThe aforementioned sections have discussed sensing technologies primarily designed to detect singular stimuli. However, simultaneous detection of multiple stimuli is crucial for obtaining a comprehensive understanding of the surrounding environment.398 For instance, in robotic systems, acquiring both pressure and temperature information is essential for successfully handling a cup of hot water and determining its temperature. This cannot be accomplished with sensors utilizing a single sensing modality. This section focuses on introducing multimodal sensing technologies integrated into soft robots, which represent a pivotal step toward enabling real-world applications of robotics in various domains.  \n\n2.8.1. Normal and Shear Force. To date, there has been relatively fewer reports on flexible sensors capable of measuring both normal and shear forces compared to sensors solely designed for normal force detection. This discrepancy arises from the inherent complexity involved in their design, fabrication, integration, and data acquisition.399 Nonetheless, the necessity of measuring both normal and shear forces is undeniable in robotic applications, particularly for tasks involving dexterous manipulation, slip detection, and advanced manufacturing processes. Designing sensors for such multifaceted measurements typically relies on employing appropriate structural and geometric configurations. In our overview, we categorize these sensors based on three primary working mechanisms: resistive, capacitive, and magnetic.  \n\nBy mimicking the working principles of mechanoreceptors in human skin, Gao et al. reported a simple, thin, soft, intelligent tactile sensor that can detect normal and shear forces, which is composed of an asymmetrically arrangement of strain sensing unit array, as shown in Figure 20a.400 The sensitivity for such force detection can be reached to $0.11~\\mathrm{~kPa}^{-1}$ , $2.5~\\ \\mathrm{N}^{-1}$ , respectively.  \n\nLee et al. also presented a highly sensitive force sensor leveraging self-adjusting carbon nanotube (CNT) arrays (Figure 20b).401 These arrays are grown directly on silicon microstructures using a space-confined growth technique, facilitating effortless self-adjustment upon contact and the microstructures with integrated CNTs are embedded in polydimethylsiloxane structures to further enhance the flexibility and softness. The sensing principle for this device relies on detecting variations in contact resistance between opposing CNT arrays when force from different direction is applied. Inspired by tenon-and-mortise in traditional Chinese ancient architecture, Hu et al. designed a flexible sixdimensional force sensor with interlocking structures (Figure 20c), providing a new strategy for the design of multidimensional force sensors.402 As shown in Figure 20d, another versatile tactile sensor capable of detecting both normal and tangential forces was reported by Mu et al.403 This flexible and stretchable e-skin features a two-layered structure comprising carbon nanotubes (CNTs) and graphene oxide (GO) integrated into a 3D conductive network anchored on a thin porous polydimethylsiloxane (PDMS) layer. Inspired by the structure of skin on fingertips and the active sensing strategies of biological species, Su et al. reported an artificial 3D mechanoreceptor (SENS) capable of detecting multiple mechanical stimuli, such as normal and shear force, as shown in Figure 20e.404 Additionally, a tensor-based nonlinear theoretical model was developed to characterize the threedimensional deformation (including tensile, compressive, and shear deformation) of the SENS, offering valuable insights for designing and optimizing its multimodal sensing properties with high accuracy. Furthermore, this work introduced a comprehensive functional framework establishing a link between sensing and action within the closed-loop sensorimotor control of robots engaged in dynamic haptic exploration. This framework enables the robotic system integrated with SENS to autonomously detect attributes such as hardness, surface texture, and tackiness. By employment of three-dimensional structure in the design, Won et al. presented a microelectromechanical sensor with monocrystalline silicon nanomembranes as piezoresistive elements (Figure 20f).405 This design facilitates independent and concurrent measurements of various mechanical stimuli, including normal force, shear force, bending, and temperature. Moreover, the fabrication and assembly procedures enable scalable manufacturing of interconnected arrays of these sensors, facilitating spatiotemporal mapping capabilities.  \n\nApart from resistive sensors, sensors based on capacitive principles can also be designed for spatial force measurement. Lee et al. reported real-time measurement of diverse contact forces applied to a novel flexible capacitive three-axis tactile sensor array (Figure $20\\mathrm{g}$ ), which is constructed using polydimethylsiloxane (PDMS).406 To dissect contact forces into their normal and shear components, each unit sensor is equipped with four capacitors, strategically separated by walltype spacers to enhance mechanical response time. Unlike traditional dielectric layers comprising a single material, Huang et al. incorporated a multilayered dielectric consisting of both air gaps and polydimethylsiloxane for a flexible three-axial force sensor (Figure 20h).407 The structural changes in the multilayered dielectric under external forces result in variations in dielectric constant $(\\varepsilon)$ , leading to capacitance alterations. Measurement outcomes demonstrate a detectable force range of approximately $_{0-10\\mathrm{~N~}}$ for all three axes.  \n\nAlternatively, by leveraging conductive fabrics, Viry et al. introduced a compact, three-dimensional flexible capacitive three-axial force sensor (shown in Figure 20i), demonstrating superior performance through innovative dielectric multilayer structuring and material combinations.408 The sensor exhibits exceptional compliance, robustness, and stability during handling, along with remarkable sensitivity (less than $10~\\mathrm{mg}$ and $8\\mu\\mathrm{m}$ minimal detectable weight and displacement, respectively) and a wide detection range (measured up to $190\\ensuremath{\\mathrm{~\\kPa~}}$ , estimated up to $400~\\mathrm{kPa},$ . Choi et al. further developed a pyramid-patterned ionic gel inspired by neural mechanoreceptors and engraved electrodes, as shown in Figure 20j.409 Leveraging the pyramid-plug structure, the sensor’s deformation mechanism varies depending on the type of external mechanical loading applied. Notably, the sensor exhibits high sensitivities of $1.93~\\mathrm{kPa}^{-1}$ , $29.88\\ \\mathrm{\\dot{N}^{-1}}$ , and 3.39 $\\mathrm{(N~cm)^{-1}}$ for pressure, shear force, and torsion. Furthermore, the sensor offers versatility by functioning through either capacitive or piezoresistive transduction methods. While the examples introduced above mainly focus on single three-axial force sensor units, it is worth noting that sensor arrays based on similar capacitive mechanisms can also be developed, as shown in Figure $20\\mathrm{k}^{410}$ and Figure 20l.234 Cheng et al. introduced a polymer-based capacitive sensing array capable of measuring both normal and shear forces, achieved through micromachining techniques and flexible printed circuit board (FPCB) technologies. Each shear sensing element comprises four capacitive sensing cells arranged in a $2\\times2$ array, with each cell featuring two sensing electrodes and a common floating electrode, which could simplify the capacitive structures, and enhance manufacturability. Boutry et al. presented a biomimetic soft e-skin enabled by a threedimensional structure mimicking the interlocked dermisepidermis interface in human skin. The e-skin features pyramid microstructures arranged along nature-inspired phyllotaxis spirals to enhance the performance, and comprises a capacitor array capable of real-time measurement and discrimination of both normal and tangential forces. The e-skin demonstrates its utility by providing sensing feedback for controlling a robot arm across various tasks, showcasing its potential applications in robotics with tactile feedback.  \n\n![](images/b53569a6346dfaed593487918b5782db399e529e9e2228cc1dd2287dae0cb705.jpg)  \nFigure 21. Flexible sensors integrated with multimodal sensing capabilities. (a) Ion-based e-skin with strain-temperature decoupling capabilities. Reproduced with permission from ref 416. Copyright 2020 American Association for the Advancement of Science. (b) Tactile-olfactory sensing array inspired by star nose. Reproduced with permission from ref 417. Copyright 2022 Springer Nature. (c) Wireless platform that can detect vascular pressure, flow rate and temperature. Reproduced with permission from ref 418. Copyright 2023 Springer Nature. (d) Photograph of soft gripper integrated with multimodal sensors that can measure proximity and temperature. Reproduced with permission from ref 419. Copyright 2022 Springer Nature. (e) Structure of the artificial sensory neuron with visual-haptic fusion. Reproduced with permission from ref 420. Copyright 2020 Springer Nature. (f) Photograph of multifunctional flexible sensing skin integrated on a curved surface. Reproduced with permission from ref 421. Copyright 2021 Elsevier. (g) Soft robotic manipulator integrated with self-powered sensors for pressure, strain, and temperature perception. Reproduced with permission from ref 422. Copyright 2021 Wiley. (h) Schematic structure of the ferroelectric skin inspired by fingertip skin that can detect temperature, static and dynamic pressure. Reproduced with permission from ref 423. Copyright 2015 American Association for the Advancement of Science. (i) Schematic illustration of the nonvon Neumann architecture for multiple signal processing. Reproduced with permission from ref 424. Copyright 2022 American Association for the Advancement of Science.  \n\nTactile sensors utilizing magnetic mechanisms offer an alternative solution for three-axial force sensing. Typically, these sensors incorporate small magnets embedded in a polymer matrix or magnetic composites, beneath which resides a Hall sensor for measuring magnetic information (Figure $20\\mathrm{m},$ ).411 When subjected to external forces, the deformation of elastomeric materials occurs, leading to variations in magnetic flux densities within the materials. This change can be accurately detected by the Hall sensor. As shown in Figure $20\\mathbf{n}_{\\cdot}$ , Dai et al. reported a split-type magnetic soft tactile sensor inspired by the layered structures found in tactile sensory organs like human skin and fish lateral lines.412 By employing a centripetal magnetization arrangement and theoretical decoupling model, the sensor achieves wireless 3D force sensing with high accuracy $(1.33\\%)$ . Its 3D force decoupling capability enables perception akin to human skin in multiple dimensions without requiring complex calibration. Yan et al. also introduced a soft tactile sensor with self-decoupling and super-resolution capabilities (Figure 20o), achieved by designing a sinusoidally magnetized flexible film (∼0.5 mm thick).269 The sensor accurately measures normal and shear forces (in one dimension) with a single unit, achieving a 60-fold superresolved accuracy through deep learning. While the devices mentioned above typically operate in ambient environments, their future applications may extend beyond these settings. Particularly, the demand for flexible devices functioning in extreme conditions is increasing for applications such as outer space and deep-sea exploration. By using giant magnetoelasticity in soft polymer systems, Zhou et al. reported a multimodal underwater robotic skin (Figure $20\\mathrm{p}$ ),413 which provide a solution for intelligent machines in extreme environment. Besides the above-mentioned mechanism, there are also 3-axis flexible sensors based on other approach, such as optical and piezoelectric.414,415  \n\n2.8.2. Other Integrated Multimodal Sensing Technologies. Multimodal sensing refers to the integration of multiple sensing capabilities within a single flexible or stretchable platform. Such capabilities are enabled by employing different types of sensors for various kinds of physical, chemical, or biological information detection. For example, a flexible artificial multimodal ionic receptor capable of distinguishing between thermal and mechanical stimuli was introduced by You et al.416 They found that two variables: charge relaxation time and the normalized capacitance in this device can serve as a strain-insensitive intrinsic measure of absolute temperature, and temperature-insensitive extrinsic measure of strain, respectively. This artificial receptor can concurrently detect temperature and strain by assessing these variables at only two measurement frequencies without signal interference, providing real-time information on force direction and strain profiles during various tactile motions such as shear, pinch, spread, and torsion (Figure 21a). Inspired by the natural sense-fusion mechanism observed in the star-nosed mole, Liu et al. developed a tactile-olfactory sensing array inspired by the natural sense-fusion mechanism observed in the star-nosed mole, as shown in Figure 21b.417 Without relying on visual input, this array enables real-time capture of local topography, stiffness, and odor from a variety of objects and can achieve an accuracy of $96.9\\%$ for classification of 11 typical objects. This tactile-olfactory bionic sensing system demonstrated remarkable resilience to environmental interference, underscoring its potential for robust object recognition in difficult environments where conventional methods may falter.  \n\nRecently, Kwon et al. presented the design features and operational characteristics of an integrated wireless multimodal sensor, which was specifically engineered for implantation within the heart or a blood vessel. This sensor enables simultaneous real-time measurements of pressure, flow rate, and temperature (Figure 21c).418 Moreover, there are also examples of flexible multimodal sensors integrated on soft robots, morphing aircraft, and other objects. Ham et al. introduced a versatile multimodal sensor network for proximity and temperature detection (Figure 21d).419 This sensor network was seamlessly integrated into a flexible and stretchable soft robotic hand for food applications and interacting with a warm baby doll for medical purposes. Apart from pressure, temperature, and olfaction, vision also plays a crucial role in the perception of biological species. Wan et al. developed a bimodal artificial sensory neuron to replicate sensory fusion processes in human beings.420 Optical and pressure information were collected by the neuron first, followed by transmitting into postsynaptic currents, as shown in Figure 21e. Such fusion of visual and tactile signals was conformed to enhance the recognition capability by simulating a multitransparency pattern recognition task. Xiong et al. further demonstrated advancements of aircrafts enabled by multifunctional e-skin that have capabilities to accurately measure surface pressure, temperature, wall shear stress, and flutter, as well as detect sudden impacts and predict separation and stall occurrences (Figure 21f).421 As illustrated in Figure $21\\mathrm{g},$ Sun et al. also demonstrated that soft robotic grippers integrated with self-power multifunctional sensor can automatically recognize 28 objects with an accuracy of 97.143%.422 In this system, pressure information was acquired from triboelectric nanogenerators, and temperature information was from pyroelectric temperature sensors. It is interesting to note that human skins are not only sensitive to static pressure, but also to dynamic pressure such as vibrations with different frequencies. On the one hand, this is attribute to the four types of mechanoreceptors embedded in the skin, in which two of them are slow adapting receptors and another two are fasting adapting receptors. On the other, the distinctive fingerprint patterns and intricately interlocked epidermal−dermal microridges serve a crucial function in amplifying and transmitting tactile signals to diverse mechanoreceptors, facilitating the spatiotemporal perception of both static and dynamic tactile stimuli. Drawing inspiration from this structure, Park et al. proposed fingerprint-like patterns and interlocked microstructures within ferroelectric films, as shown in Figure 21h, which enable superior piezoelectric, pyroelectric, and piezoresistive sensing of both static and dynamic mechanothermal signals.423 This artificial skin exhibits the capability to detect and differentiate between multiple spatiotemporal tactile stimuli, including static and dynamic pressure, vibration, and temperature, with remarkable sensitivity. Besides the aforementioned examples of multimodal sensing, there are still many other designs, enabling technologies, and combinations of sensing modalities. This will be remained as a research frontier for both scientists and engineers. Once the number and type of sensor increase, data acquisition and processing would become problematic. To solve this issue, Ho et al. introduced an artificial synaptic multiplexing unit capable of facilitating a parallel multi-input control system (Figure 21i).424 This innovative multi-input control system can simultaneously handle input and feedback signals, representing a significant advancement for industries reliant on processing large volumes of streaming data.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 2.9. Future Development  \n\nIn short conclusion, this section delves into the various mechanisms, materials, and applications of these sensing technologies to provide a thorough understanding of the current state and future potential of sensor systems. This knowledge is essential for researchers, engineers, and practitioners seeking to develop and deploy advanced sensing solutions in an increasingly interconnected and data-driven world. However, there are endless frontiers for the exploration of soft sensors in the next few decades, as exemplified by recent work on flexible sensors.425−427 Here, we summarized the three main aspects for the future development of soft sensors and also provided our opinions for corresponding issues: mechanism selection, metrics optimization, and system integration (Figure 22).  \n\nSelecting an appropriate sensing mechanism requires a comprehensive understanding of the strengths and limitations of each option. The selection process should align with the specific requirements and performance objectives of the intended application. For example, resistive sensors are valued for their low cost and simplicity, making them suitable for integration (Figure 22a). However, they exhibit limitations such as hysteresis, which compromises accuracy during cyclic measurements, susceptibility to drift over time, and sensitivity to temperature fluctuations, restricting their reliability in dynamic environments. Capacitive sensors, characterized by high sensitivity due to their ability to convert external stimuli into structural deformations, are ideal for high-precision applications like touchscreens and tactile sensors (Figure 22b). Their minimal power consumption enhances suitability for energy-sensitive systems. Nevertheless, fabrication challenges, susceptibility to environmental and crosstalk interference, and the need for shielding or calibration remain significant considerations. Piezoelectric sensors excel in dynamic stimuli detection and self-powering capabilities, making them indispensable for applications such as vibration monitoring and energy harvesting (Figure 22c). However, the fragility of piezoelectric materials and the complexity of their fabrication processes can elevate costs. Other mechanisms, including optical and magnetic sensors, present unique advantages. Optical sensors offer exceptional precision and stability for applications like biomedical devices and environmental monitoring (Figure 22d), albeit at the expense of high costs and complexity. Magnetic sensors, prized for their versatility and noncontact operation, face challenges in signal processing and mitigating interference (Figure 22e).  \n\nAfter mechanism selection, optimizing device performance metrics is crucial for ensuring reliable and precise functionality. Sensitivity can be enhanced through advanced sensor architectures, incorporating hierarchical or nanostructured materials to amplify responses to external stimuli (Figure 22f). Stability, essential for long-term performance, can be improved with robust encapsulation and durable interface connections to mitigate environmental degradation (Figure $22\\mathbf{g})$ . Selectivity, the ability to target specific stimuli while avoiding interference, can be achieved using tailored response designs and advanced algorithms, including machine learning, to enhance precision (Figure 22h). Flexibility is critical for applications like wearable electronics and soft robotics, often achieved through the use of soft materials and innovative structural designs (Figure 22i). Dynamic applications, such as real-time monitoring, benefit from rapid response times, optimized through nanomaterial reinforcement and signalefficient designs (Figure 22j). Extending detection range involves advanced materials and hierarchical structures, enabling broader applicability (Figure 22k). Linearity, ensuring proportional input−output relationships, requires hybrid structures and computational approaches to minimize distortion (Figure 22l). Addressing hysteresis, which reflects discrepancies in cyclic loading and unloading, involves reducing interfacial friction and controlling elastic deformation (Figure $22\\mathrm{m}\\mathrm{,}$ ). Achieving these optimizations demands a multidisciplinary approach encompassing materials science, mechanical engineering, and machine learning.  \n\nAfter decades of development, research on soft sensors focuses has increasingly shifted toward system integration, aiming to create devices that can be seamlessly deployed in real-world applications with reliability and convenience. To achieve this, comprehensive efforts are required to address critical aspects to make soft sensors into deployable systems, targeting multimodal sensing, high-density and large-area detection, efficient data acquisition, robust signal transmission, and sustainable power solutions.  \n\nMultimodality allows sensors to detect diverse stimuli and perform sensor fusion for enriched data output. However, challenges such as mode interference, compatibility, and decoupling must be addressed to ensure robust performance (Figure 22n). High-density and large-area sensing is vital for robotics and interactive interfaces, requiring considerations of miniaturization and scalability (Figure 22o). In data acquisition and processing, balancing sampling rates with real-time analysis can be achieved through data compression and edge computing (Figure 22p). Wireless signal transmission is increasingly reliant on bandwidth optimization and interference reduction (Figure 22q). Flexible power solutions, such as advanced batteries and energy harvesting, enable long-term operation with reduced reliance on external sources (Figure 22r). These integrated efforts collectively drive the translation of soft sensors from fundamental research prototypes to practical technologies, paving the way for their deployment in real-world applications.  \n\nIn short summary, as we already discussed a variety of working mechanism for soft sensors above, their advantages and disadvantages should be kept in mind for better and more efficient device design (Figure $22\\mathsf{a}\\mathrm{-}\\mathsf{e}$ ). For example, when the device is designed for detection of high-frequency stimuli, like the fast-adapting receptors in the skin, sensors based on a piezoelectric mechanism are preferred due to its inherent merits. After mechanism selection, the metrics of the device can be optimized, such as sensitivity, stability, selectivity, flexibility, response time, detection range, linearity, and hysteresis (Figure $22\\mathrm{f-m}$ ). Overall, the optimization of device metrics relies several key approaches: materials, structure engineering, fabrication, computational design, machine learning, etc.432−437 After decades of development, research on soft sensors focuses more and more on system integration, aiming to fabricate devices that can be immediately put to real world applications reliably and conveniently. For such integration, continuous efforts should be put on multimodality, high-density and large-area, data acquisition and processing, signal transmission, and power source, and more details can be found in Figure 22n−r.418,428−431  \n\n![](images/d0e42cdc75ac27cca28741d715936ef98bf4dcad346499ce0b9e3832a1fb09b4.jpg)  \nFigure 22. A summary for the future development of soft sensors in terms of mechanism selection, metrics optimization, and system integration. Advantages and disadvantages of the soft sensors based on five most common working mechanisms, including (a) resistive, (b) capacitive, (c) piezoelectric, (d) optical, and (e) magnetic. Definition and key strategies for optimization of the metrics of soft sensors, including (f) sensitivity, $(\\mathbf{g})$ stability, (h) selectivity, (i) flexibility, (j) response time, (k) detection range, (l) linearity, and $\\mathrm{(m)}$ hysteresis. Key points in the system integration level for soft sensors in terms of $\\mathbf{\\eta}(\\mathbf{n})$ multimodality, (o) high-density and large-area, (p) data acquisition and processing, (q) signal transmission, (r) power source. Reproduced with permission from ref 428. Copyright 2024 American Association for the Advancement of Science. Reproduced with permission from ref 429. Copyright 2024 Springer Nature. Reproduced with permission from ref 430. Copyright 2022 American Association for the Advancement of Science. Reproduced with permission from ref 418. Copyright 2023 Springer Nature. Reproduced with permission from ref 431. Copyright 2023 Springer Nature.  \n\n![](images/e664689b9ab32a49dbb5d4f37e402afd894219d88d204ddebf0ff95b01840c88.jpg)  \nFigure 23. Actuation mechanisms for different actuation modalities in soft robotics. (a) Fluidic actuation. (b) Magnetic actuation. (c) Chemical actuation. $(\\mathrm{d-g})$ Electroactive actuation: Dielectric elastomer actuators, hydraulically amplified actuators, and electrochemical actuators and piezoelectric actuators. $\\mathrm{(h,i)}$ Optical and thermal actuation: shape-memory actuators and liquid-crystal polymer actuators. $(\\mathrm{j-l})$ Other actuation modalities: Acoustically driven, biohybrid, and phase change actuators.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 3. ACTUATION MODALITIES AND MATERIALS  \n\nActuators are indispensable components of sensorimotor systems in the burgeoning field of soft robotics. Functioning analogously to motors, these actuators distinguish themselves from their traditional counterparts through their intrinsic flexibility and complianc e.108,117,438−442 Traditional machinery employs actuators and motors that are typically rigid, offering precision but sacrificing adaptability. In contrast, the innovative realm of soft robotics has pioneered the use of a vast array of materials engineered to perform various actuation modalities (Figure 23).443,444  \n\nFluidic actuation encompasses both pneumatic and hydraulic systems, which operate by building up positive pressure through gases and liquids, respectively.445,446 Magnetic actuation leverages the response of ferromagnetic or ferrimagnetic materials embedded within the actuators to applied magnetic fields.447,448 A significant class of actuation, electroactive actuations, includes dielectric elastomer actuators (DEAs), hydraulically amplified dielectric elastomer actuators (HADEAs), piezoelectric actuators, and electrochemical actuators. DEAs utilize extremely high electric fields (kilovolts) to deform elastomeric materials sandwiched between compliant electrodes, while in HADEAs, the elastomers are replaced with liquid dielectrics.449,450 Electrochemical actuators, operated at lower voltages, feature ionic polymer−metal composites (IPMCs) that utilize ion migration under electric fields.451,452 Additionally, the piezoelectric effect is employed in creating actuators for microrobotic applications.453,454 Chemical actuations include responsive systems that utilize bimorph or gradient structures responding to the absorption/ desorption of water/solvents or changes in $\\mathsf{p H}$ , typically resulting from the swelling/deswelling of responsive materials.455,456 Enzyme-mediated actuations represent an intriguing category where chemical reactions drive actuation.457,458 Furthermore, optical and thermal actuation modalities, such as light-responsive liquid-crystal elastomer (LCE) and liquidcrystal polymer (LCP) actuators, as well as typical thermalresponsive actuators like shape-memory alloys (SMAs) and polymers, play significant roles.459−462 The field also explores novel actuations including acoustically driven, biohybrid, and phase change actuators.463−465  \n\n![](images/124cd9076e71d825e93d47a3943ba8ec5ed72978d6841803c8c59fb7420314d2.jpg)  \nFigure 24. Summary of static and dynamic performance characteristics of actuators: (a) Illustration of the relationship between maximum stroke and maximum force output. (b) Graph of force density versus actuation speed. (c) Graph showing the correlation between power density and work density. (d) Graph showing the relationship between power density and actuation efficiency. Reproduced with permission from ref 467. Copyright 2021 The Author(s). Published by PNAS. This open access article is distributed under Creative Commons Attribution-NonCommercialNoDerivatives License 4.0 (CC BY-NC-ND). (e) Diagram showing the relationship between output force, strain, response speed, and driven voltage for four main types of electroactive actuators: electrochemical, piezoelectric, HASEL, and DEA actuators. Reproduced with permission from ref 550. Copyright 2020 Wiley. Reproduced with permission from ref 454. Copyright 2019 Springer Nature. Reproduced with permission from ref 479. Copyright 2018 American Association for the Advancement of Science. Reproduced with permission from ref 449. Copyright 2019 American Association for the Advancement of Science.  \n\n![](images/82ba59a9f725cdbf89272e93f6072fde514e4a2b6e915a65d0019a2cbf0e1e4a.jpg)  \nFigure 25. Fluidic actuations for soft robotics. (a) Illustration of a robotic spider of a soft robotic spider constructed from laminated multilayers utilizing lithography and laser micromachining techniques. (b) Time-lapse images of an untethered soft robotic fish powered by soft electronic pump performing swimming motion underwater. (c) Images of an untethered soft gripper that can swiftly seize a falling ping-pong ball. (d) Image of a third-generation of pleated pneumatic artificial muscle (PPAM) device. (e) Image of an electronics-free autonomous gripper fabricated using desktop fused filament fabrication (FFF) three-dimensional printing. (f) Image of an electronics-free pneumatic soft-legged quadruped robot. (g) Walking pneumatic-driven soft robot with embedded hysteretic valves. (h) Commercialized collaborative robots from Festo Pte. Ltd. (a) Reproduced with permission from ref 468. Copyright 2018 Wiley. (b) Reproduced with permission from ref 469. Copyright 2021, The Authors, published by Springer Nature. Reproduced under the terms of the Creative Commons Attribution 4.0 International License. (c) Reproduced with permission from ref 470. Copyright 2023, The Authors, published by Springer Nature. Reproduced under the terms of the Creative Commons Attribution 4.0 International License. (d) Reproduced with permission from ref 471. Copyright 2012, Taylor & Fransis. (e) Reproduced with permission from ref 164. Copyright 2023 American Association for the Advancement of Science. (f) Reproduced with permission from ref 473. Copyright 2021 American Association for the Advancement of Science. (g) Reproduced with permission from ref 474. Copyright 2022 Elsevier. (h) Reproduced with permission from ref 472. Copyright 2020 Elsevier.  \n\nEach modality leverages unique physical principles and material properties to fulfill specific functional requirements in soft robotic systems.444,466 Pneumatic and hydraulic actuators, widely used for their high actuation force and speed, large actuation stroke, and work density (Figure $24\\mathsf{a}-\\mathsf{d},$ ), are often coupled with a pumping control system, which limits their untethered applications. Electrically based actuators integrate well with electronic sensing and control systems, showing promise for AI-driven robotic systems of the future. DEA actuators display the highest actuation strain, speed, and power density, though they are limited by high operating voltages (>kilovolts). Efforts are underway to develop low-voltage DEAs. In contrast, IPMC actuators can be operated at voltages of as low as $_{1-3\\mathrm{V}}$ . But they display the lowest actuation strain and power density, making them only suitable for applications requiring minimal actuation. Magnetic, optical, and thermal actuators are all well-suited for untethered robot applications; magnetic actuation, for instance, provides high force and speed but requires sophisticated machinery to manipulate the magnetic field. LCE actuators outperform IPMCs in actuation strain and power density but exhibit even slower response speeds. As for thermal actuators, SMAs possess the highest work and power densities. However, typical SMA actuators have limited applications in soft robotics due to the rigid components. Novel shape-memory polymer actuators made from elastomers show potential for broader use in soft robotics. Nevertheless, one performance of actuators may be affected by another. For example, the actuation performance of electroactive actuators is indeed highly dependent on the driving voltages, and there is often a trade-off between the performance indicators, such as output force, strain, and respond speed, as shown in Figure 24e. Thus, such trade-off effects should be considered when designing actuators for a specific application.  \n\nThis section provides an in-depth exploration of various actuation modalities commonly employed in soft robotics. It delves into the scientific principles underpinning each type of actuation, detailing the mechanisms that drive their functionality and the materials essential for their construction. Furthermore, a comprehensive comparison of these modalities is presented, assessing their respective advantages and disadvantages with respect to actuation performance, efficiency, and control complexity, offering practical guidance on selecting and implementing these actuators in soft robotics applications.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 3.1. Fluidic Actuators  \n\nFluidic actuators operate primarily through the application of pressure, typically positive pressure, to achieve deformation. They are capable of generating significantly high actuation forces and speeds, making them a popular choice across various applications. As a result, numerous commercial products, such as pneumatic grippers, have become widely utilized within the industry. Despite their widespread adoption and utility, one major limitation is their dependency on relatively large-sized external rigid pumps, which can hinder their integration into untethered soft robotics where compactness and flexibility are crucial. To resolve such an issue, innovative designed have been made to achieve soft pumping systems. In the forthcoming sections, we will provide a detailed exploration of both hydraulic and pneumatic actuators, including operational mechanisms, typical applications, and the specific challenges they face.  \n\n3.1.1. Hydraulic. Hydraulic actuators function by injecting fluid into specifically engineered chambers, where pressure accumulation enables diverse movements, such as bending and twisting. These movements are integral for various tasks including object manipulation, emulation of biological mechanisms, and implementing locomotion. Ranzani et al. introduced the microfluidic origami reconfigurable pneumatic/ hydraulic (MORPH) actuation system.468 Through the utilization of lithography and laser micromachining, they produced soft laminated multilayers featuring embedded microfluidic channels arranged in complex, arbitrary structures. The multilayer soft lithography process enables the conversion of 2D laminates into 3D devices. Illustrated in Figure 25a, a MORPH system composed of 12 layers of laminates was assembled to replicate the movements of a peacock spider, boasting 9 independently controllable degrees of freedom (DoFs) and 5 structural DoFs.  \n\nAs mentioned earlier, conventional fluidic actuators often rely on bulky rigid pumping systems, posing a challenge. To address this issue, drawing inspiration from spider hydraulic systems, Zou’s group devised a soft electronic pumping system utilizing an electrohydrodynamic (EHD) mechanism, offering superior actuation performance coupled with self-healing capability.469 The operational principle of these soft electronic pumps hinges on the application of a strong nonuniform electric field between positive and grounding electrodes. During this process, electrons near the positive electrodes overcome potential barriers and dissociate from neutral liquid molecules, transforming into free electrons. These electrons are then absorbed into the positive electrodes, leaving behind positively charged ions. Driven by Coulomb forces, these ions migrate toward the grounding electrodes, dragging neutral liquid molecules with them through a hole, generating a robust jet. Upon reaching the grounding electrodes, the ions recombine with electrons on the electrode surfaces, restoring neutral liquid molecules. This continuous flow persists through the migration of electrons and ions under the electric field, ceasing only when the field is removed. The self-healing mechanism involves a functional liquid composed of dibutyl sebacate and tung oil solution, where tung oil’s solidification properties, triggered by exposure to air, facilitate automatic repair of damages in soft robots. Figure 25b illustrates an untethered soft robotic fish, propelled by the soft electronic pump, demonstrating swimming motion underwater. By incorporating soft EHD pumps, actuators, healing electrofluids, and E-skins, they have developed soft fluidic robots distinguished by their rapid actuation and advanced selfprotection capabilities.470 Utilizing this technology, Figure 25c demonstrates an untethered soft gripper that can swiftly seize a falling ping-pong ball, dropped from a height at a speed of 65 $\\mathrm{cm}/\\mathrm{s},$ controlled manually through a smartphone app.  \n\n3.1.2. Pneumatic. Since Joseph L. McKibben pioneered the first basic soft fluidic robot, known as the McKibben artificial muscle, in the 1950s, extensive research has been dedicated to refining the design, actuation, sensing, control, and applications of such robots.471 Pneumatic artificial muscles (PAM) find widespread use in walking robots and rehabilitation devices, with various forms commercialized by companies.472 These muscles, including the well-known McKibben muscle, typically consist of a rubber inner tube expanding when inflated, with tension transferred by a braided sleeving, albeit with drawbacks like dry friction and rubber tube deformation. To address these issues, the pleated pneumatic artificial muscle (PPAM) was developed, featuring a mathematical model ensuring accurate performance prediction.471 The PPAM’s innovative design allows operation at low pressures, ranging from 20 mbar to 4 bar gauge pressure, with contractions exceeding $40\\%$ . A third generation of PPAM, presented by Villegas et al., simplifies manufacturing and improves durability, leveraging fused deposition modeling (FDM) rapid prototyping for complex and lightweight end closures (Figure 25d).471 Unlike previous generations, continuous high-tensile fibers are now integrated into toothed end closures and folded membranes, streamlining production and reducing weight.  \n\nPneumatic actuators are manufactured through molding and assembly processes, which often involve numerous manual steps and limit complexity. Additionally, integrating complex control components, such as electronic pumps and microcontrollers, is necessary to achieve even basic functions. Desktop fused filament fabrication (FFF) three-dimensional printing offers a more accessible alternative with reduced manual labor and the ability to produce intricate structures. However, FFF-printed soft robots commonly exhibit high effective stiffness and numerous leaks due to material and process constraints, restricting their utility. Zhai et al. introduced a design approach for 3D printing monolithic, airtight, high-performance soft pneumatic robots using a commercially available desktop FFF printer.164 Key design principles include printing structures with a single continuous toolpath, known as an Eulerian path, to ensure airtightness, and creating thin-walled structures with low stiffness, comparable to silicone-molded parts, when combined with the first principle. Following this design methodology, a  \n\n![](images/b80d6260e93f2c26318a3b377006117fb7e9b3bcf7b7a193ab79a01bd8821c8b.jpg)  \nFigure 26. Electroactive soft actuators. (a) Photograph of the soft dynamic DEA valves. (b) Photograph of a transparent loudspeaker. (c) Photograph of the untethered insect robot based on low-voltage DEA. (d) Photograph of the pipeline inspection robots driven by DEA. (e) A soft gripper based on two modified stacks of donut-shaped HASEL actuators for handle delicate objects. (f) Photograph of EBM arrays with of six pouches. $\\mathbf{\\eta}(\\mathbf{g})$ Photograph of the ${\\boldsymbol{\\mathfrak{s}}}\\times{\\boldsymbol{\\mathfrak{s}}}$ array of HAXELs actuators. (h) Photograph of a five-pouch HALVE actuator equipped with chrome/gold electrodes, lifting its $_{13-\\mathrm{g}}$ power supply. (i) Optical image of the 3D microscale mechanical frameworks with piezoelectric thin-film actuators. (j) Photograph of the untethered insect-sized flapping-wing MAV. (k) Photograph of the configuration of the insect-scale fast moving soft robot. (l) Photograph of the BFFSPR robot climbing a $12^{\\circ}$ slope. $\\mathrm{(m)}$ Schematic representation of the actuation mechanism in the Graphdiyne-Based Electrochemical Actuator. (n) Demonstration of the MXene-based electrochemical acuators in a kinetic art. (o) Photographs of the $\\mathbf{MoS}_{2}$ -based actuator lifting an object at $0.3\\mathrm{V}$ . (p) Photographs of the nickel nanowire-forest-based actuator deforming. (a) Reproduced with permission from ref 476. Copyright 2021 National Academy of Sciences. (b) Reproduced with permission from ref 477. Copyright 2013 American Association for the Advancement of Science. (c) Reproduced with permission from ref 449. Copyright 2019 American Association for the Advancement of Science. (d) Reproduced with permission from ref 478. Copyright 2022 American Association for the Advancement of Science. (e) Reproduced with permission from ref 479. Copyright 2018 American Association for the Advancement of Science. (f) Reproduced with permission from ref 481. Copyright 2021 American Association for the Advancement of Science. $(\\mathbf{g})$ Reproduced with permission from ref 480. Copyright 2020 Wiley. (h) Reproduced with permission from ref 482. Copyright 2024, The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC). (i) Reproduced with permission from ref 483. Copyright 2018, The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC). (j) Reproduced with permission from ref  \n\n454. Copyright 2019 Springer Nature. (k) Reproduced with permission from ref 484. Copyright 2019 American Association for the Advancement of Science. (l) Reproduced with permission from ref 485. Copyright 2023 Wiley. (m) Reproduced with permission from ref 486. Copyright 2018, The Authors, published by Springer Nature. Reproduced under the terms of the Creative Commons Attribution 4.0 International License. (n) Reproduced with permission from ref 487. Copyright 2019 American Association for the Advancement of Science. (o) Reproduced with permission from ref 488. Copyright 2017 Springer Nature. (p) Reproduced with permission from ref 489. Copyright 2016 Wiley.  \n\ncustomized electronics-free pneumatically driven autonomous gripper was fabricated (Figure 25e). Traditionally, the control of such pneumatic robots has relied on electromechanical components like valves and pumps, which tend to be bulky and costly. Tolley’s group introduced a novel method for governing the movements of soft-legged robots using basic pneumatic circuits, completely devoid of electronic elements.473 This method orchestrates locomotion patterns through ring oscillators composed of soft valves, generating oscillatory signals akin to biological central pattern generator neural circuits. Pneumatic logic components respond to sensor inputs, directing the actions of these oscillators. They illustrate this method by designing pneumatic control circuits capable of generating walking patterns for a soft-legged quadruped with three degrees of freedom per leg, and seamlessly switching between gaits to regulate the direction of movement (Figure 25f). There are also other interesting pneumatic-driven soft robots, such as the walking soft robot with embedded hysteretic valves and elephant trunk-inspired soft robotic arm (Figure 25g,h).472,474",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# 3.2. Electroactive Actuators  \n\nElectrically responsive actuators are particularly well-suited for integration with electronic sensing and control systems, making them foundational components in the development of sophisticated, AI-driven robotic systems.475 Their inherent compatibility with electronic technologies allows for seamless communication and synchronization between sensors, actuators, and controllers. This integration facilitates precise, realtime adjustments to actuator behavior based on continuous sensory feedback, which is crucial for adaptive and intelligent robotic functioning.  \n\n3.2.1. Dielectric Elastomer Actuators. Dielectric elastomer actuators (DEAs) are highly valued in soft robotics due to their exceptional energy density, efficiency, flexibility, and lightweight design. These attributes make them ideal for overcoming limitations in traditional fluid-driven soft robots, which often suffer from rigid and limiting control systems. To enhance adaptability and mobility, various forms of soft valves for fluidic actuators have been developed, notably those driven electrically. A significant breakthrough was achieved by the Wood group, who developed an electrically powered soft valve for hydraulic actuators equipped with mesoscale channels (Figure 26a).476 This innovation utilizes a new class of ultrahigh-power density dynamic DEAs, which are capable of operating at frequencies of ${500}\\mathrm{Hz}$ or higher. These advanced actuators generate a blocked force that is $300\\%$ greater than that of previously used dynamic DEAs. Moreover, they achieve a loaded power density of $290\\mathrm{\\W\\bulletkg^{-1}}$ under operating conditions, marking a substantial enhancement in both performance and efficiency for applications in soft robotics. Suo’s group achieved a notable breakthrough with the development of a transparent loudspeaker that can produce sound over the entire audible spectrum, ranging from $20\\ \\mathrm{Hz}$ to  \n\n$20~\\mathrm{kHz}$ (Figure $26\\mathsf{b}$ ).477 They crafted this innovative device using $1\\ \\mathrm{mm}$ thick VHB 4910 tape (3M) as the dielectric layer and a $100\\mathrm{-}\\mu\\mathrm{m}$ thick polyacrylamide hydrogel containing NaCl as the electrolyte. The loudspeaker’s effectiveness was demonstrated through a spectrogram of the recorded sound, which successfully replicated the main signal of the original test sound across the entire range of audible frequencies. Shea’s group has enhanced the capabilities of dielectric elastomer actuators (DEAs), which are typically known for kilohertz operation and high power density but require several kilovolts to achieve full strain.449 The mass of these kilovolt power supplies has traditionally limited the speed and performance of DEA-driven robots. In their recent work, they introduced DEAnsect: an autonomous, insect-sized ( $40\\ \\mathrm{mm}$ long), fast 1 $\\cdot30\\mathrm{\\mm/s}$ tethered, $12\\mathrm{mm}/s$ untethered), and ultralight $\\left(1\\ \\mathrm{g}\\right)$ legged soft robot (Figure 26c). Equipped with integrated sensors, power units, battery, and control electronics, DEAnsect is powered by three low-voltage stacked DEAs (LVSDEAs), each operating a leg at $450\\mathrm{~V~}$ and over $600~\\mathrm{Hz}$ . Despite its minimal weight, with a $190\\mathrm{-mg}$ body and $780~\\mathrm{mg}$ of onboard electronics. In addition, Tao et al. developed a pipeline inspection robot designed to navigate pipes with subcentimeter diameters and various curvatures The robot utilizes high-power DEAs for its elongation units and smart composite microstructure (SCM)-based, high-efficiency transmissions for its anchoring units (Figure 26d).478 Through meticulous modeling and analysis of the robot’s dynamic characteristics, as well as precise tuning of the activation voltages’ frequencies and phases, this pipeline robot can achieve rapid motion in various directions, surpassing 1 body length per second in subcentimeter-sized pipes.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "#  \n\n3.2.2. Hydraulically Amplified Electrostatic Actuators. Dielectric elastomer actuators (DEAs) are known for their high actuation strain and efficiency, yet they are prone to failures such as dielectric breakdown and electrical aging due to the high electric fields required for operation. In response to these limitations, Keplinger’s group has introduced a pioneering class of high-performance, muscle-mimetic soft transducers named hydraulically amplified self-healing electrostatic (HASEL) actuators.479 These actuators employ an electrohydraulic mechanism to activate all-soft matter hydraulic architectures, blending the advantages of soft fluidic actuators with the muscle-like performance and self-sensing capabilities of DEAs. Unlike conventional soft fluidic actuators that experience inefficiencies due to fluid transport through channel systems, HASEL actuators create hydraulic pressure locally via electrostatic forces acting on liquid dielectrics integrated within the soft structure. This novel application of liquid dielectrics not only boosts efficiency but also facilitates self-healing, enabling the actuators to instantly regain functionality after experiencing multiple dielectric breakdowns. Figure 26e demonstrates a soft gripper crafted from two modified stacks of donut-shaped HASEL actuators. This gripper is specifically designed to handle delicate objects, such as a raspberry. Fontana’s group developed an electrostatic actuator called the circular electrostatic bellow muscle (EBM), made from thin films, liquid dielectrics, and rigid polymeric stiffeners. This unit is designed for out-of-plane contraction, is easy to manufacture, and can be configured into arrays or stacks. EBMs function as contractile artificial muscles, pumps for fluid-driven soft robots, or energy harvesters. With diameters ranging from 20 to $40\\ \\mathrm{mm}$ , these EBMs can exert forces up to $\\bar{6}\\mathrm{~N~}$ , lift over a hundred times their weight, and achieve contractions over $40\\%$ with strain rates surpassing $120\\%$ per second and a bandwidth above 10 Hz. By arranging six in-series EBM pouches in a $1\\times6$ layout (Figure 26f), strokes of up to $43\\%$ of the muscle’s initial length were achieved. Shea’s group has addressed a long-standing challenge in soft actuators\u0001creating thin devices that combine high force and large displacement\u0001through the development of a new type of actuator known as the hydraulically amplified taxel (HAXEL). This innovative design features a fluid-filled cavity enclosed by a nonstretchable polymer shell with an elastic central top, allowing significant expansion when activated. The use of materials with high breakdown voltage enhances energy efficiency, while the thin, flexible design makes HAXEL arrays ideal for immersive virtual reality applications, such as tactile gloves, bracelets, and customizable body patches (Figure 26g).480  \n\nTo lower the operating voltages, Katzschmann’s group developed the hydraulically amplified low-voltage electrostatic (HALVE) actuator, achieving an average power density of 50.5 ${\\mathrm{W/kg}}$ and a peak strain rate of $971\\%$ per second at $1100~\\mathrm{V}_{;}$ , comparable to mammalian skeletal muscle.482 This actuator is safe to touch, waterproof, and self-clearing, making it suitable for robotics and wearables. It uses a three-part design: a strong polymer outer shell, an electrode, and a high-energy density dielectric layer of P(VDF-TrFE-CTFE), enhancing electrostatic performance while lowering voltage requirements. The central cavity filled with dielectric oil amplifies the hydraulic effect. Using the Peano-HASEL actuator geometry, the device operates below 1300 V. When voltage is applied, Coulomb forces attract the electrodes, displacing the dielectric oil and deforming the actuator into a cylindrical shape that performs mechanical work. This modular structure enhances the actuator’s efficiency and application versatility (Figure 26h).  \n\n3.2.3. Piezoelectric Actuators. Recent advances have heightened interest in the development of subgram vehicles, prized for their high maneuverability\u0001thanks to favorable torque and inertia scaling\u0001and their ability to perform tasks such as environmental monitoring and navigation in confined spaces. As micro aerial vehicles (MAVs) become smaller, traditional actuation mechanisms and bearings encounter significant challenges. These include reduced efficiency of electromagnetic motors and heightened frictional losses due to unfavorable scaling laws. Consequently, piezoelectric actuators, whose power density scales inversely with their length, are favored in microscale applications. Their ability to perform oscillatory operations is particularly well-suited to the flapping motions required by MAVs. Ning et al. have furthered the capabilities of mechanically active 3D MEMS by developing complex 3D mesoscale architectures that incorporate integrated piezoelectric actuators under independent electrical control (Figure 26i).483 This allows for the dynamic excitation of selected vibrational modes. Innovative transfer printing techniques facilitate the integration of ultrathin piezoelectric films and ductile metals onto polymer layers, which are lithographically patterned into 2D geometries. Controlled mechanical buckling processes then convert these 2D multifunctional material structures into precisely defined 3D architectures. These structures are versatile enough to be deployed onto both flat and curved surfaces, accommodating a variety of substrate types. Wood’s group successfully achieved sustained untethered flight with an insect-sized flapping-wing MAV (Figure 26j).454 They tackled the integration challenges of onboard electronics within a constrained payload capacity and achieved a lift-to-weight ratio surpassing that of typical biological counterparts. The vehicle features four wings powered by two alumina-reinforced piezoelectric actuators, enhancing its aerodynamic efficiency. This integrated system weighs just $259~\\mathrm{\\mg}$ and operates on a mere 110−120 milliwatts of power. To optimize efficiency, the authors finetuned the drive signals, reducing both power consumption and the mass and complexity of the drive electronics. The design improvements included a new actuator made from micromachined alumina and thorough benchtop tests to confirm the wing kinematics and system frequency response. Ultimately, the vehicle demonstrated successful untethered flight powered by solar cells, marking significant advancements in the performance and efficiency of flapping-wing MAVs driven by piezoelectric actuators. Lin’s group has developed a fast and ultrarobust insect-scale soft robot, inspired by the dynamics of animal locomotion.484 This robot can travel at speeds of up to 20 body lengths per second, endure the weight of an adult stepping on it, carry loads six times its own weight, and efficiently climb slopes (Figure 26k). The enhancements in its design include optimized geometric parameters and the addition of a back leg, which significantly increased its speed. Yin’s group has developed a soft robot named the Bio-Mimic, Fast-Moving, and Flippable Soft Piezoelectric Robot (BFFSPR), inspired by the rapid and agile gait of cheetahs.485 This robot employs a double spiral structure coupled with a piezoelectric actuator to facilitate high-speed movement and exceptional agility, making it highly adaptable to complex environments (Figure 26l).  \n\n3.2.4. Electrochemical Actuators. Electrochemical or ionic polymer−metal composite (IPMC) actuators are a type of soft actuator that leverage ionic movement within a polymer matrix under an electric field to create motion. These actuators are known for their low voltage operation, flexibility, and the ability to produce large bending or twisting motions, which make them highly suitable for soft robotics. In soft robotics, IPMC actuators are particularly valued for their biomimetic properties, allowing them to mimic the gentle yet complex movements of biological organisms. This capability makes them ideal for applications where delicate interaction with the environment is necessary, such as in medical devices for minimally invasive surgeries or wearable technology that interacts directly with the human body. Their inherent softness and compliance also enable the design of robots that can safely operate in unstructured and dynamic environments, further expanding the scope of robotic applications to areas that require a high degree of adaptability and safety.  \n\nNovel materials have been used for the fabrication of electrochemical actuators. Chen’ group developed a highperformance electrochemical actuator based on graphdiyne.486 The actuator exhibited an unprecedented electro-mechanical transduction efficiency of up to $6.03\\%$ and maintained excellent performance over 100,000 cycles. The researchers identified the alkene−alkyne complex transition within the  \n\n![](images/cd90b36d29dd8e09dd52dae4bbad02448ae5f54026be7b21bcca2776d5b45fe5.jpg)  \nFigure 27. Soft robot actuated by magnetism. (a) 3D-printed ferromagnetic actuator featuring a hexapedal structure, which wraps around and transports an oblong pharmaceutical pill using rolling-based locomotion. (b) Images of the multimodal small-scaled robot climbed a water meniscus, landed on a solid platform, jumped over an obstacle, and walked away. (c) Photograph of the multilayer soft robot for on-demand multitargeted adhesion. (d) Image of the scaled robot inspired by the overlapping design of the pangolin is shown on the right. (e) Images showing the folding of the MaSoChain and disassembly. (f) Images showing the swimming motion of the jellyfish-like robot visualized by fluorescein dye. (g) Photograph of the miniature magnetic gripper lifting a PDMS cube. (h) Photographs illustrating the strain engineering process used to create helical structures for incorporating magnetic composites. (i) Optical images of ferrofluid droplets navigating through a circularly curved channel, a sharp turn, and a gap. (j) Illustration and video snapshots depict the deformation, cargo delivery, and splitting of a liquid metal magnetic soft robot (LMMSR). (k) Microscopic images showing hematite colloidal particles forming liquid, chain, vortex, and ribbon swarming patterns under magnetic fields. (l) Image of the microdisks forming a pattern with 5-fold symmetry. (m) Images showing the rheotaxis of the acousto-manetic microswarm rolling along the capillary wall under a combined acoustic and magnetic field. (a) Reproduced with permission from ref 111. Copyright 2018 Springer Nature. (b) Reproduced with permission from ref 490. Copyright 2018 Springer Nature. (c) Reproduced with permission from ref 109. Copyright 2024, The Authors, published by Springer Nature. (d) Reproduced under the terms of the Creative Commons Attribution 4.0 International License. Reproduced with permission from ref 491. Copyright 2023, The Authors, published by Springer Nature. Reproduced under the terms of the Creative Commons Attribution 4.0 International License. (e) Reproduced with permission from ref 492. Copyright 2023, The Authors, published by Springer Nature. Reproduced under the terms of the Creative Commons Attribution 4.0 International License. (f) Reproduced with permission from ref 493. Copyright 2019, The Authors, published by Springer Nature. Reproduced under the terms of the Creative Commons Attribution 4.0 International License. (g) Reproduced with permission from ref 494. Copyright 2018 Wiley. (h) Reproduced with permission from ref 495. Copyright 2023 Wiley. (i) Reproduced with permission from ref 496. Copyright 2022, The Authors, published by Springer Nature. Reproduced under the terms of the Creative Commons Attribution 4.0 International License. (j) Reproduced with permission  \n\nfrom ref 497. Copyright 2023, The Authors, published by Springer Nature. Reproduced under the terms of the Creative Commons Attribution 4.0 International License. (k) Reproduced with permission from ref 498. Copyright 2019 American Association for the Advancement of Science. (l) Reproduced with permission from ref 499. Copyright 2022, The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC). $\\mathbf{\\tau}(\\mathbf{m})$ Reproduced with permission from ref 500. Copyright 2021 Springer Nature.  \n\ngraphdiyne structure as the key mechanism behind the enhanced performance, which was verified using in situ sum frequency generation spectroscopy (Figure $26\\mathrm{m}\\dot{}$ ). In addition to graphdiyne, MXene has also been utilized in significant advancements within soft robotics.487 Oh’s group developed MXene artificial muscles that showcase ultrafast response times of under one second, exceptional bending strains up to $1.37\\%$ , and durable cyclic stability for up to 18,000 cycles (Figure $26\\mathbf{n}\\mathrm{\\dot{\\Omega}}$ ). These muscles maintain high structural reliability across various frequencies and voltages without delamination, thanks to the use of a $\\mathrm{Ti}_{3}\\mathrm{C}_{2}\\mathrm{T}_{\\it x}$ electrode ionically cross-linked with poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate). Demonstrating their versatility, practical applications of these MXene-based actuators include an origami-inspired wearable brooch and kinetic art pieces, highlighting their potential for innovative robotic devices. Acerce utilized two-dimensional metallic molybdenum disulfide $(\\mathbf{MoS}_{2})$ to achieve a low operating voltage of just $0.3\\mathrm{~V~}$ while developing a robust electrochemical actuator.488 This actuator, constructed from chemically exfoliated $\\mathbf{MoS}_{2}$ nanosheets on thin plastic substrates, demonstrated the ability to generate significant mechanical forces. It could lift masses more than 150 times heavier than the electrode itself over several millimeters for hundreds of cycles (Figure 26o). The films produced mechanical stresses around $17\\ \\mathrm{MPa}$ \u0001on par with ceramic piezoelectric actuators\u0001and sustained strains up to $0.6\\%$ , functioning effectively at frequencies up to $1\\ \\mathrm{Hz}$ . This high performance is credited to the excellent electrical conductivity of the metallic 1T phase of $\\mathrm{MoS}_{2},$ the significant elastic modulus of the restacked $\\mathbf{MoS}_{2}$ layers, and rapid proton diffusion through the nanosheets. These advancements herald the potential for new electrochemical actuators designed for high-strain and high-frequency uses. Cheng et al. developed a high-performance electrochemical actuator using a unique three-dimensional anodic aluminum oxide (AAO) template filled with nickel nanowires.489 These nanowires are organized into a dual-level “nanowire-forest” structure that enhances ion transport and actuation strain due to their high surface-area-tovolume ratio and mechanical stability. The system demonstrates a rapid and reversible actuation mechanism, capable of significant mechanical displacement observable by the naked eye, with potential applications in robotics and microelectromechanical systems (Figure 26p).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# 3.3. Magnetic Actuators  \n\nMagnetic actuators leverage the force generated by magnetic fields to drive movement and are increasingly used in the field of soft robotics due to their unique advantages. These actuators provide wireless actuation, allowing for greater flexibility and adaptability in designing robots that can operate in intricate or harsh environments without the need for physical connections. In soft robotics, magnetic actuators are especially valued for their ability to produce precise, controlled movements through noncontact means, making them ideal for applications requiring gentle and complex manipulations, such as in biomedical devices or when handling delicate materials. Furthermore, their capacity for rapid response and reversibility enhances the functionality of soft robotic systems, enabling them to perform tasks with higher efficiency and adaptability, ranging from targeted drug delivery within the human body to intricate object manipulation in unstructured settings.  \n\n3.3.1. Solid-state Magnetic Robots. While solid-state magnetic actuators have been extensively explored, Zhao’s group has made significant advancements by developing a method for 3D printing soft materials with programmed ferromagnetic domains.111 Utilizing a composite ink composed of magnetizable microparticles and fumed silica nanoparticles embedded in a silicone rubber matrix, they applied a magnetic field during the printing process to induce patterned magnetic polarity in the printed filaments. This innovative approach enabled the programming of complex 3D shapes capable of undergoing rapid transformations under magnetic actuation. The resulting structures demonstrated high actuation speed and power density, surpassing those of existing 3D-printed active materials. The team expanded this technique to create high-aspect-ratio multilayered and auxetic structures with negative Poisson’s ratios. They showcased various functionalities such as reconfigurable soft electronics, mechanical metamaterials, and soft robots that can crawl, roll, catch objects, and transport pharmaceutical doses (Figure 27a). Sitti’s group has developed a versatile soft robot capable of multiple locomotion modes including walking, rolling, and undulating swimming (Figure 27b).490 This robot has demonstrated its ability to navigate through a synthetic stomach phantom, move within ex vivo chicken tissue under ultrasound guidance, and grip, transport, and selectively release cargo. Yu’s group developed a magnetic multilayer soft robot for targeted adhesion in the stomach. They fabricated the robot using a magnetic film, an adhesive film, and different layers assembled through laser cutting and plasma treatment (Figure 27c).109 Sitti’s group has advanced the development of untethered miniature robots capable of on-demand heating for biomedical applications, inspired by the unique structure of pangolins (Figure 27d). These bilayered soft robots demonstrated multiple functionalities, including selective cargo release, in situ demagnetization, hyperthermia treatment, and bleeding control, optimized for efficient Joule heating. The robots have shown promise for medical applications such as stopping bleeding and administering hyperthermia therapy. Furthermore, the team developed a wireless magnetic soft millirobot equipped for thermal adhesive bonding, cargo release, and targeted drug delivery. This robot was thoroughly evaluated for its heating performance, mechanical properties, and deformation capabilities.491  \n\nNelson’s group has developed magnetic soft-robotic chains (MaSoChains), a novel magnetic soft-robotic chains capable of self-folding into programmable shapes.492 These chains are made from alternating soft and rigid segments, assembled with NdFeB magnets, allowing them to transform into various functional structures such as grippers and tethered capsule endoscopes (Figure 27e). Additionally, the integration of flexible printed circuit boards (PCBs) within the MaSoChains has expanded their functionality by incorporating electronic components. This study introduces an innovative approach to designing self-folding soft-robotic chains with reconfigurable shapes and functionalities, showing great potential for applications in minimally invasive surgeries. Sitti’s group also developed a soft millirobot inspired by the ephyra, a juvenile stage of jellyfish, capable of manipulating fluidic flow to perform various functions and tasks. This robot can be actuated using magnetic fields, biological muscle cells, or shape-memory alloys to achieve diverse swimming modes (Figure 27f). The team also explored the robot’s ability to retain objects, uncovering two mechanisms that could lead to object escape.493 Visel’s group has designed and fabricated miniature soft electromagnetic actuators (EMAs) using silicone polymer, liquid metal alloy (EGaIn), and magnetic powder.494 These actuators incorporate 3D helical coil conductors as electromagnetic inductors and find use in applications like soft vibrotactile actuators (SVAs) and miniature soft electromagnetic grippers (SEMGs) (Figure $27\\mathbf{g})$ . This work addressed challenges in creating highperformance EMAs and introduces new methods for designing and fabricating soft composite structures. Anikeeva’s group has developed 3D magnetic soft robots using fiber-based actuators and magnetic elastomer composites, controlled by unidirectional magnetic fields.495 They crafted helical structures from thermally drawn elastomeric fibers embedded with a magnetic composite (Figure 27h). By adjusting strain and magnetization treatments, they created worm-like crawlers and bipedal walkers capable of moving in magnetic fields orthogonal to their plane of motion. The robots demonstrated functionalities such as cargo carrying, and multiple robots could be simultaneously controlled\u0001even in opposing directions\u0001 with a single stationary electromagnet.  \n\n3.3.2. Liquid-State Magnetic Robots. Magnetic liquidbased actuators and robots represent another significant category in the field. Zhang’s group conducted experiments with hydrocarbon oil-based ferrofluids to understand the dynamics and behavior of ferrofluid droplets across various terrains. Using both positive and negative casting techniques, along with 3D printing technology, they crafted liquid cilia arrays to interact with the droplets. The team developed magnetic actuation systems to precisely control these droplets and applied mathematical equations to model their behavior (Figure 27i).496 They also delved into the wetting dynamics of ferrofluid droplets on different substrates, demonstrating multiple motion modes. Furthermore, the research explored the applications of ferrofluid droplets as liquid capsules, liquid cilia, and liquid skin in the creation of miniature soft machines, highlighting their potential in biomedical applications. Ma’s group developed a magnetic liquid metal composite by integrating iron oxide magnetic nanoparticles into eutectic gallium indium liquid metal through a reactive wetting mechanism.497 To enhance wettability between the magnetic nanoparticles and the liquid metal, a silver intermediate layer was introduced. The resulting composite displayed excellent suspension stability and magnetism. Utilizing this composite, the researchers crafted a miniature soft robot that demonstrated controlled deformation and locomotion under an external magnetic field (Figure 27j). The composite’s biocompatibility was confirmed as nontoxic to normal cells, and it exhibited remarkable stability in the stomach’s acidic environment. Additionally, the remote magnetic manipulation of the soft robot was successfully demonstrated using an imaging system. This study not only advances the development of magnetic liquid metal composites for biomedical applications in miniature soft robots but also suggests a new composite preparation strategy that could enhance the wetting conditions between liquid metal and various inorganic nonmetallic materials.  \n\n3.3.3. Magnetic Robot Swarm. Magnetic robot swarms represent a cutting-edge innovation in the field of microrobotics, harnessing the principles of magnetism to control and manipulate small-scale robotic systems collectively. These swarms are composed of tiny individual robots, each embedded with magnetic materials, allowing them to respond dynamically to magnetic fields. This response enables the coordinated control of large groups of robots, facilitating complex, synchronized movements that mimic natural swarms found in biological systems. Xie et al. have developed a system of magnetic microrobots capable of forming various collective formations\u0001liquid, chain, vortex, and ribbon\u0001in response to programmed alternating magnetic fields (Figure 27k). They explored how these microrobots can navigate narrow channels, handle substantial loads, and perform synchronized manipulations. The team characterized the physical mechanisms driving the dynamics of these microrobotic swarms and created a computational model to simulate the observed phenomena accurately. The study demonstrated the swarms’ ability to precisely follow planned paths, navigate through constricted spaces, and conduct collective tasks, showcasing the versatility and control of reconfigurable microrobot swarms for a range of practical applications.4 Sitti’s group conducted a comprehensive study on the interrelationships among information, structure, and interactions within a system of microdisks (Figure 27l). Utilizing a combination of experimental observations, numerical simulations, and theoretical calculations, they gained insights into these crucial connections. They revealed direct links between information, structures, and interactions, highlighting the influence of neighbor distances in pattern formation.499 Nelson’s group has made significant advances in the manipulation and control of microparticles using acoustic and magnetic fields. They developed an acoustofluidic device capable of manipulating particles with ultrasound and engineered an experimental setup to control microparticles using both acoustic and magnetic fields simultaneously.500 Their research demonstrated that magnetic forces can overcome thermal fluctuations in stabilizing particle swarms, particularly for particles with radii of $3\\mu\\mathrm{m}$ . The team observed that a swarm of microparticles could migrate upstream when subjected to combined acoustic and magnetic fields. Moreover, they successfully designed and characterized self-assembled microswarms capable of upstream motility under these conditions. These microswarms exhibited a rolling-type motion along the walls of a microchannel when exposed to external flow and could move upstream against flow velocities up to $1.2\\ \\mathrm{mm}/\\mathrm{s},$ , driven by acoustically induced reaction forces (Figure $27\\mathrm{m}\\mathrm{\\dot{\\Omega}}$ ). The researchers suggest that these bioinspired micro/nanorobotic systems hold promising potential for applications in targeted therapeutics, noninvasive surgery, and precise drug delivery to challenging locations.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# 3.4. Optical Actuators  \n\nOptical responsive actuators leverage light to induce motion in materials, offering innovative applications in the field of soft robotics. These actuators operate on mechanisms such as photomechanical effects, photochemical reactions, and photothermal changes, which allow materials like azobenzene polymers and liquid-crystal elastomers to expand, contract, or bend in response to specific light wavelengths. Their capacity for precise, remote, and wireless control makes them ideal for scenarios where electrical wiring or complex mechanical setups are impractical. As such, optical responsive actuators are gaining traction in areas such as biomedical devices, adaptive structures, and interactive consumer electronics, where their ability to alter physical properties on-demand can significantly enhance functionality and user interaction.  \n\n![](images/029bfec62414e15e68e2f5b447d54dc83912906554852345a810d02ee338c662.jpg)  \nFigure 28. Light-driven liquid-crystal polymer materials actuators. (a) Schematics illustrating the isomeric transformation of azobenzene and the light-driven actuation of liquid-crystal film (LDLCF) (b) Illustration of robot locomotion using a traveling-wave feature, with images showing the displacement of the microrobot as it responds to traveling light patterns of different wavelengths. (c) Schematic of artery wall structure showing the tunica media with alternating muscle and elastic layers for deformation and robustness. Adjacent images show light-induced motion of a silicone oil slug in a TMA, taken through an optical filter to block wavelengths below $530~\\mathrm{nm}$ . (d) Chemical composition of the LC monomer mixture and photographs depicting the rolling motion of a kirigami robot activated by light irradiation. (e) Schematics showing an opto-chemo-mechanical feedback loop modulates the transiently activated region, crucial for complex micropost motion. (f) Schematic diagrams illustrating the mechanism behind artificial goosebump generation in the microactuation system. (a) Reproduced with permission from ref 501. Copyright 2015, The Authors, published by Springer Nature. Reproduced under the terms of the Creative Commons Attribution 4.0 International License. (b) Reproduced with permission from ref 502. Copyright 2016 Springer Nature. (c) Reproduced with permission from ref 503. Copyright 2016 Springer Nature. (d) Reproduced with permission from ref 504. Copyright 2019 Wiley. (e) Reproduced with permission from ref 505. Copyright 2022 Springer Nature. (f) Reproduced with permission from ref 506. Copyright 2024, The Authors, published by Springer Nature. Reproduced under the terms of the Creative Commons Attribution 4.0 International License.  \n\n![](images/5c683dcee9a2b0ade5b5a482bcfcc90f03aaf81d0bea445231379eddbe0c686f.jpg)  \nFigure 29. Optical-driven soft actuators based on hydrogels, shape-memory polymers, and light responsive liquids. (a) Schematic illustration showing the expansion and contraction of the $[\\mathrm{c}2]\\mathrm{AzoCD}_{2}$ hydrogel in response to photoirradiation. (b) Schematics of the photoexpansion actuation and photographs of the bending performance. (c) Schematics of the supramolecular photoresponsive hydrogel and photograph of the twisted hydrogel. (d) Schematic depicting the design of light-induced bidirectional contraction−expansion. (e) Illustration of the chemical structure photopolymerizable photo switching monomer and the light-responsive walking of the hydrogel hybrid under rotating magnetic fields. (f) Illustration of the photoisomerization of dithienylethene (DTE) and the gel−sol transition process. (g) Shape-memory polymer ribbon exhibiting spiral shape recovery to its original form under UV illumination. (h) Images showing the shape-memory performance of the hyperbranched coumarate polyesters-based polymer film responding to UV light. (i) Photographs capturing the light-driven motion of an olive oil droplet on a silica plate (j) Illustration of the manipulation of droplets in three dimensions. (a) Reproduced with permission from ref 507. Copyright 2016 Springer Nature. (b) Reproduced with permission from ref 508. Copyright 2020 American Chemical Society. (c) Reproduced with permission from ref 509. Copyright 2020 Wiley. (d) Reproduced with permission from ref 510. Copyright 2024, The Authors, published by Springer Nature. Reproduced under the terms of the Creative Commons Attribution 4.0 International License. (e) Reproduced with permission from ref 511. Copyright 2020 American Association for the Advancement of Science. (f) Reproduced with permission from ref 512. Copyright 2020 Wiley. (g) Reproduced with permission from ref 513. Copyright 2005 Springer Nature. (h) Reproduced with permission from ref 514. Copyright 2013 Wiley. (i) Reproduced with permission from ref 515. Copyright 2000 American Association for the Advancement of Science. (j) Reproduced with permission from ref 516. Copyright 2018 Wiley.  \n\n3.4.1. Liquid-Crystal Polymers. Liquid-crystal polymer (LCP) materials based optical actuators represent a sophisticated blend of material science and light-responsive technology, providing a dynamic foundation for advancements in soft robotics and beyond. These actuators utilize the unique properties of LCPs\u0001such as their molecular alignment and anisotropy\u0001to respond to light, particularly in the ultraviolet and visible spectra. When light is applied, LCPs can undergo rapid changes in shape, alignment, or both, driven by the material’s tendency to order or disorder its molecular structure in response to photonic stimuli. Huang et al. developed a miniaturized swimming soft robot capable of complex movement, uniquely powered and controlled by remote light signals, thus eliminating the need for onboard electronics or batteries. The design features a head, a flexible flagellum, and a gripper. The flagellum, made from a flexible polymer, is actuated by a light-driven liquid-crystal film (LDLCF) embedded with azobenzene chromophores. Exposure to UV light causes the LDLCF to bend, swinging the flagellum to propel the robot forward, while exposure to visible light allows it to recover its original shape (Figure 28a). The gripper, constructed from LDLCF and polyethylene terephthalate (PET), opens and closes in response to light, enabling it to grasp and release objects. Controlled by alternating flashes of UV and white light, this innovative approach allows the robot to swim and transport loads effectively.501 Fischer’s group used structured light to control the shape changes and locomotion of microrobots made of photoactive liquid-crystal elastomers (Figure 28b). They fabricated cylindrical and disc-shaped microrobots and demonstrated that they can be driven by structured monochromatic light to perform biomimetic motions. The microrobots were able to generate travelingwave motions to self-propel without external forces or torques. The researchers also showed that the microrobots can exhibit versatile locomotion behaviors on demand, including translational motion and rotation, by controlling the light patterns. The use of structured light fields allowed for precise control over the local actuation dynamics within the microrobots, enabling high-level control over their macroscopic behavior.502 Lv et al. conducted a detailed study on the development of linear liquid-crystal polymer (LLCP) fibers and films. They explored the behavior of tubular microactuators (TMAs) crafted from LLCP films, assessing their mechanical robustness and capability for light-induced motion (Figure 28c). Demonstrations included the use of photoinduced asymmetric deformation of TMAs to manipulate fluid slugs, enabling the mixing of multiphase liquids, combining liquids, propelling liquids uphill, and capturing and conveying microspheres.503  \n\nCheng et al. have innovatively applied kirigami-based techniques combined with liquid-crystal polymer networks (LCNs) to craft complex 3D robotic structures activated by light.504 They manipulated the LCN films through external stress fields such as stretching, twisting, and bending to initiate out-of-plane deformations. By engraving kirigami patterns onto these films and then detaching them from the substrate, the team achieved 2D-to-3D shape morphing (Figure 28d). This approach was exemplified in the creation of a kirigami-based rolling robot equipped with light-actuated petals, which demonstrated the ability to perform multigait rolling movements, navigate predesigned 2D trajectories, and climb slopes. This study underscores the potential of kirigami as a versatile technique for developing complex, flexible 3D structures with light-activated robotic functionalities. Aizenberg’s group has advanced the use of liquid-crystalline elastomers (LCEs) to create microstructures that demonstrate self-regulated actuation under various conditions (Figure 28e).505 They utilized finite element simulations and developed a discrete model to study the collective behavior of microstructure arrays. The research showed that LCE microstructures could perform stroke-like motions under intense illumination, with the trajectories of these motions influenced by factors like illumination intensity, director tilt, size, temperature, and irradiation patterns. Further exploration revealed that microstructures with complex geometries and multiple joints could achieve programmable deformations and intricate motion patterns. Sitti’s group has developed a microactuation system utilizing light-responsive liquid-crystal elastomers (LCEs) as artificial skin, coupled with 3D-printed passive polymer microstructures.506 This innovative system is activated through exposure to a programmable femtosecond laser, which precisely generates localized artificial goosebumps (Figure 28f). This capability enables controlled manipulation of light reflection, disassembly of self-assembled microstructures held together by capillary forces, and has potential applications in information storage. The fabrication of this system involves a two-step thiol-Michael reaction that incorporates mobile liquid-crystal molecules, enhancing the responsiveness of the LCE skin. The system has been further applied to create micromirrors and selectively open and close mushroom-like microstructures, demonstrating its versatility.  \n\n3.4.2. Hydrogels. Hydrogel actuators are emerging as a transformative technology in the field of soft robotics, leveraging the unique properties of hydrogels\u0001water-swollen polymeric networks capable of undergoing significant volume change in response to various stimuli. These actuators harness the inherent softness, flexibility, and high-water content of hydrogels, making them ideal for mimicking the natural movements of living tissues, thus offering biocompatibility and inherent safety for interactions with humans. The primary appeal of hydrogel actuators lies in their ability to respond to a range of environmental cues such as temperature, pH, light, and electric or magnetic fields. This responsiveness can induce rapid and reversible changes in the hydrogel’s shape, volume, and mechanical properties, driving the actuation needed for movement and function in soft robotic systems. For instance, temperature-responsive hydrogels can expand or contract substantially with slight changes in temperature, enabling actuation that can mimic muscle contractions.  \n\nHarada’s group has innovated in the development of photoresponsive molecular actuators by utilizing rotaxanebased compounds, specifically [c2]daisy chains.507 These actuators were synthesized through the cross-linking of a cyclodextrin (CD) derivative and TetraPEG via amide bond formation. The resulting $[\\mathrm{c}2]\\mathrm{AzoCD}_{2}$ hydrogel and xerogel demonstrated remarkably fast response times to ultraviolet irradiation, with the xerogel responding 10,800 times faster than its hydrogel counterpart (Figure 29a). Notably, the [c2]AzoCD2 xerogel also exhibited pseudoreversible deformation under dry conditions. Stupp’s group has developed innovative cross-linked hydrogel networks by synthesizing polymerizable sulfonated spiropyran molecules (Figure 29b). Unlike typical photoresponsive materials that contract, these hydrogels exhibit a unique expansion upon exposure to visible light. This photoexpansion effect can be finely adjusted by altering the solution’s $\\mathrm{\\ttpH}$ or the composition of the polymeric backbone. Furthermore, the researchers engineered artificial muscles demonstrating negative phototaxis\u0001bending away from the light source.508 The bending angle and the kinetics of these artificial muscles can be tailored through strategic selection of spiropyran molecules and polymeric networks. However, light-driven hydrogel actuators face significant hurdles, notably sluggish responsiveness and subpar mechanical characteristics. A novel approach has emerged to tackle these challenges. Connal’s group pioneers a novel supramolecular design strategy, harnessing a benzylimine-functionalized anthracene group. This innovation not only shifts the absorption spectrum into the visible range but also bolsters the supramolecular network via π−π interactions (Figure 29c).509  \n\nMoreover, the integration of acid−ether hydrogen bonds serves to dissipate energy during mechanical stress, while preserving the hydrogel’s hydrophilicity. The resultant doublecross-linked supramolecular hydrogel, synthesized with ease, boasts a unique combination of superior strength, rapid selfrepair, and swift shape transformation under visible light stimuli, whether in wet or dry conditions. Prior endeavors predominantly focused on either intricately designing heterogeneously structured hydrogels or intricately manipulating external stimuli. However, achieving self-regulated reversal shape deformation in homogeneous hydrogels under a constant stimulus posed a considerable challenge. Guo and colleagues introduce a molecularly designed homogeneous hydrogel containing two spiropyrans that demonstrate selfregulated transient deformation reversal under constant illumination.510 They further developed hydrogel film actuators capable of intricate temporary bidirectional shape transformations and self-regulated reversal rolling under illumination. (Figure 29d). Li et al. engineered hydrogel− metal hybrid materials capable of swift and customizable locomotion when exposed to light and magnetic fields.511 The hydrogels exhibit shape changes in response to both light and magnetic fields. When exposed to light, dehydration caused by the isomerization of a photoswitching molecule leads to the shrinkage of the hydrogels, resulting in mechanical deformation and bending. In the presence of a magnetic field, ferromagnetic nanowires embedded within the hydrogel experience magnetic torques and tend to align with the field, inducing macroscopic deformation. The hydrogels are sensitive to spatial gradients in hydrophobicity triggered by light exposure and the alignment of nanowires induced by the magnetic field, enabling programmable shape changes and locomotion (Figure 29e). These hydrogels exhibited versatile mobility, including walking, steering, climbing, and cargo delivery, all orchestrated by an external magnetic field and light. Zhang’s group introduced a photoresponsive hydrogel− nanopipette hybrid system for single-cell operations, enabling precise drug delivery with minimal cell damage.512 Unlike previous methods, this system operates without high electric potential or organic solvents, preserving cell integrity. Leveraging the hydrogel’s photoresponsive properties, it achieves potential-free, noninvasive drug injection, ensuring high cell viability. The system also allows for dose-controllable drug delivery, demonstrated with reduced lethal doses of doxorubicin across cell lines. The gel−sol transition triggered by visible light drives drug injection without external stimuli (Figure 29f). Real-time control over dosage is achieved through light stimulation. This breakthrough offers a promising tool for single-cell studies and theranostics.  \n\n3.4.3. Shape-Memory Polymers. Shape-memory polymer actuators represent a cutting-edge technology in the field of soft robotics. These advanced materials possess the remarkable ability to change shape in response to external stimuli, such as temperature, light, or electrical fields, and subsequently revert to their original shape upon the removal of the stimulus. This unique property makes shape-memory polymer actuators ideal for a wide range of applications in soft robotics, including gripping, locomotion, and morphing structures. By harnessing the inherent flexibility and adaptability of shape-memory polymers, researchers are paving the way for the development of highly versatile and intelligent robotic systems capable of performing complex tasks with precision and efficiency.  \n\nLendlein et al. pioneered the light-induced shape-memory polymers, revolutionizing the field with their ability to be deformed and fixed into temporary shapes through UV light illumination (Figure $29\\mathrm{g}$ .513 These polymers exhibit the capability to revert to their original shape when exposed to UV light of a different wavelength. This study involved synthesizing two types of photoresponsive. Additionally, the researchers conducted tests on a specific grafted polymer, investigating the influence of UV irradiation on the temperature of the polymer film during the experiments. Kaneko’s group synthesized hyperbranched coumarate polyesters through a polycondensation method, resulting in polymers with elastomeric properties, excellent solubility, and shape-memory characteristics.514 Furthermore, the researchers explored the photodeformation capabilities of these polymers, showcasing their potential for intricate shape-memory effects (Figure 29h).  \n\n3.4.4. Light-Responsive Liquids. Light-responsive liquid actuators represent a dynamic and promising frontier in soft robotics. These innovative materials harness the power of light to trigger shape changes and actuation, offering unique advantages such as rapid response times, precise control, and adaptability.  \n\nIchimura et al. present an intriguing study on manipulating the macroscopic motion of liquids on solid surfaces through photoirradiation of a photoisomerizable monolayer. By introducing a calix[4]resorcinarene derivative onto a substrate surface, they demonstrate how asymmetrical photoirradiation induces a gradient in surface free energy, resulting in directional motion of liquid droplets (Figure 29i). The direction and velocity of this motion are controllable by adjusting the direction and intensity gradient of light.515 In addition, Officer’s group has demonstrated a breakthrough in fluidic manipulation by showcasing the ability to precisely move droplets in three dimensions using light (Figure 29j). This feat was achieved through the incorporation of a photoactive material, spiropyran (SP), into the droplets, enabling their movement in any direction within water using simple light sources. The motion of the droplets was driven by a light-induced change in interfacial tension, known as Marangoni flow. Moreover, the researchers illustrated the versatility of this technology by combining a photoactive droplet with another carrying a “cargo,” then moving the resulting larger droplet to a designated “reactor” droplet where the cargo undergoes a chemical reaction.516",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# 3.5. Thermal Actuators  \n\nThermal actuators serve as fundamental components in the rapidly evolving field of soft robotics, offering unique capabilities for precise and adaptable motion. These actuators harness the principles of thermal expansion or contraction to induce mechanical deformation, enabling a wide range of dynamic movements. By leveraging thermal energy as a driving force, researchers are exploring innovative avenues for the development of soft robotic systems capable of performing complex tasks with dexterity and efficiency.  \n\n3.5.1. Liquid-Crystal Elastomers. Liquid-crystal elastomers (LCEs) represent a fascinating class of materials with immense potential in the realm of soft robotics. These unique materials combine the properties of both liquid crystals and elastomers, offering a remarkable combination of responsiveness, flexibility, and tunability. LCEs undergo reversible shape changes in response to external stimuli such as temperature, light, or mechanical stress, making them ideal candidates for  \n\n![](images/625a4f5b2290eb44128aa33e447ef169cc8a2a29d246503cc0b7df98d7775170.jpg)  \nFigure 30. Thermal-driven actuators based on liquid-crystal elastomers. (a) Illustration depicting the actuation mechanism of the LCE fiber and photographs showcasing the length of LCE microfiber in polydomain, monodomain, and isotropic states. (b) Illustration demonstrating the shapemorphing transition from 1D to 2D of cubic voxels. (c) Schematic of the chemical structure of the main-chain LCE capable of surface alignment, accompanied by photographs illustrating mechanical multistability. (d) Photographs illustrating the restoration of deformed dynamic 3D structures. (e) Photograph showing the multimodal dielectric actuations. (f) Illustration of contrast in stability of isotropization temperature $\\left(\\mathrm{{T_{i}}}\\right)$ achieved through annealing between LC vitrimer networks and other polymer networks and thermal actuation of an aligned xLCE between $160~^{\\circ}\\mathrm{C}$ (isotropic phase) and $140~^{\\circ}\\mathrm{C}$ (liquid-crystal phase) after 200 rapid heating−cooling cycles on a hot plate. (g) LCE shells actuators with negative order parameter. (a) Reproduced with permission from ref 517. Copyright 2021 American Association for the Advancement of Science. (b) Reproduced with permission from ref 518. Copyright 2021, The Authors, published by Springer Nature. Reproduced under the terms of the Creative Commons Attribution 4.0 International License. (c) Reproduced with permission from ref 519. Copyright 2015 American Association for  \n\nthe Advancement of Science. (d) Reproduced with permission from ref 520. Copyright 2016 American Chemical Society. (e) Reproduced with permission from ref 521. Copyright 2024 Wiley. (f) Reproduced with permission from ref 522. Copyright 2023, The Authors, published by Springer Nature. Reproduced under the terms of the Creative Commons Attribution 4.0 International License. (g) Reproduced with permission from ref 523. Copyright 2019, The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).  \n\nactuation and control in soft robotic systems. Their ability to undergo large deformations while maintaining structural integrity opens up new possibilities for designing soft robots capable of intricate movements and shape-shifting behaviors. As researchers continue to explore the diverse capabilities of LCEs and develop novel fabrication techniques, these materials hold promise for revolutionizing the field of soft robotics by enabling the creation of highly adaptive and versatile robotic systems.  \n\nCai’s group has devised an innovative approach for fabricating thin LCE microfibers through electrospinning, unlocking a myriad of possibilities in soft robotics and microfluidics (Figure 30a). These LCE microfibers exhibit impressive actuation capabilities, boasting large strains, rapid response speeds, and high-power densities. Leveraging these unique properties, the group successfully engineered microtweezers, microrobots, and a light-powered microfluidic pump, showcasing the versatility of electrospun LCE microfiber actuators. Notably, the electrospinning technique enables mass production of LCE microfibers with small diameters, resulting in enhanced thermal actuation speeds compared to previous methods.517 In another work, Sitti’s group has pioneered a novel method for fabricating liquid-crystal elastomers (LCEs) with intricate three-dimensional (3D) geometries and customizable director fields.518 Leveraging a two-photon polymerization process, they engineered individual LCE voxels with programmable director fields, allowing precise control over their shape and orientation. These voxels were skillfully assembled to create 1D, 2D, and 3D structures with unprecedented director fields, enabling shape-morphing behaviors previously unattainable (Figure 30b). They showcased the potential for programmable shape transformations in LCE devices, shedding light on their promising applications in diverse fields. White’s group has developed an innovative method for crafting soft, ordered LCEs, capable of programmable shape change and actuation (Figure 30c).519 Their approach involves precisely directing the molecular order, referred to as the director, within small volume elements called voxels. Through this control over the voxel director, they have achieved mastery over the material’s mechanical response. Demonstrating their versatility, these materials exhibit controlled bending and stretching in response to thermal or chemical stimuli. The programmable mechanical behavior of these LCEs holds significant promise for applications ranging from monolithic multifunctional devices to reconfigurable substrates for flexible devices in aerospace, medicine, and consumer goods industries.  \n\nJi’s group has introduced a novel material termed carbon nanotube dispersed liquid-crystalline vitrimers, unlocking the potential for crafting dynamic three-dimensional (3D) structures.520 These structures exhibit reversible shape changes and boast easy modification, repair, and assembly facilitated by light activation (Figure 30d). Remarkably, this material enables the fabrication of intricate 3D structures sans the need for screws, glues, or molds. Demonstrating its versatility, the researchers showcased the creation of complex structures with diverse alignment modes. Furthermore, the material’s photowelding capability permits the joining of different parts without adhesives, while its capacity for healing microcracks and functioning at extremely low temperatures further enhances its utility. Jin’s group has introduced a liquid-crystal dielectric elastomer (LC-DE) capable of dynamically altering its dielectric actuation modes in response to temperature fluctuations. Fabricated using liquid-crystal organo-gels, the LC-DE undergoes reversible shape changes with varying temperatures. Notably, the temporary and permanent shapes of the LC-DE possess distinct bending stiffness, resulting in different dielectric actuation modes under an electric field. The temporary shape can be programmed or reprogrammed through force-directed solvent evaporation, while the permanent shape can be reconfigured through bond exchangeenabled stress relaxation. This innovative material exhibits multimodal dielectric actuation behaviors upon temperature change, with the potential for further diversification through shape programming (Figure 30e). Additionally, the LC-DE demonstrates reduced driving electric field requirements and bidirectional actuation manners, attributed to the space charge mechanism. Ji’s group conducted a study into the impact of annealing on the structure and properties of a thermotropic LCE (Figure 30f). Their research revealed that annealing induces changes in the actuation temperature of the LCE. Through a series of experiments, they measured the actuation temperature and utilized differential scanning calorimetry (DSC) to analyze the thermal behavior of the LCE. The study demonstrated that annealing fully cross-linked LCEs with dynamic covalent bonds enables adjustment of the isotropization temperature $(T_{\\mathrm{i}})$ , consequently affecting the actuation temperature. Remarkably, the changes in $T_{\\mathrm{i}}$ were reversible and stable, offering the capability to tune actuation temperatures without altering the material’s chemical composition. Lagerwall’s group has delved into the realm of LCE shell actuators with a negative order parameter through a combination of experiments and simulations. Employing a microfluidic and osmotic stretching approach, they successfully engineered LCE shells exhibiting a negative order parameter. Furthermore, the researchers explored the thermal response of these LCE shells, showcasing various actuation modes (Figure $30{\\bf g})$ ). This study unveils a novel class of LCE actuators with unique characteristics and sheds light on the behavior of liquidcrystal elastomers.523  \n\n3.5.2. Shape-Memory Materials. A shape-memory polymer (SMP) possess the remarkable ability to undergo substantial deformations in response to external stimuli, such as temperature, light, or moisture, and subsequently revert to their original shape upon stimulus removal.524,525 This unique capability enables SMP actuators to execute complex and precise movements, making them ideal candidates for a wide array of applications in soft robotics. By harnessing the inherent flexibility and adaptability of SMPs, researchers are forging new pathways in the development of intelligent and responsive robotic systems capable of performing intricate tasks with agility and efficiency.  \n\n![](images/9f522ccee7c918a7a2caef9bf247154602eb1eb8253b2c54ee178f046bc71a28.jpg)  \nFigure 31. Thermal-driven actuators based on shape-memory materials. (a) Schematic illustrating the temperature-dependent structures of the double-crystalline SMPs. (b) Illustration of the two-way reversible shape-memory behavior. (c) Photographs illustrating the shape-recovery behaviors of encapsulated composites without onset delay. (d) Optical image depicting a soft electrically actuated quadruped (SEAQ) walking on a rocky surface. (e) Illustration of the object grabbing performance facilitated by the parallel-processable synaptic array (PPSA). (f) Sequential images capturing Tribot in its distance-jump gait, from initial to landing positions. $(\\mathrm{g,h,i})$ Shape-memory ceramic, hydrogel, and hybrid-based actuators. (a) Reproduced with permission from ref 526. Copyright 2021 Elsevier. (b) Reproduced with permission from ref 527. Copyright 2014 American Chemical Society. (c) Reproduced with permission from ref 528. Copyright 2023 Springer Nature. (d) Reproduced with permission from ref 461. Copyright 2018 American Association for the Advancement of Science. (e) Reproduced with permission from ref 529. Copyright 2023, The Authors, published by Springer Nature. Reproduced under the terms of the Creative Commons Attribution 4.0 International License. (f) Reproduced with permission from ref 530. Copyright 2019 Springer Nature. (g) Reproduced with permission from ref 531. Copyright 2013 American Association for the Advancement of Science. (h) Reproduced with permission from ref 532. Copyright 1995 Springer Nature. (i) Reproduced with permission from ref 533. Copyright 2012 Elsevier.  \n\nPan’s group conducted a comprehensive study on doublecrystalline supramolecular polymers (SMPs) comprising oligomeric polycaprolactone (PCL) end-functionalized with self-complementary quadruple hydrogen bonding 2-ureido-4- pyrimidinone (UPy) units. Notably, the study unveiled the dual shape-memory effects of the UPy-terminated PCLs (U  \n\nPCLs), showcasing their potential for diverse applications (Figure 31a).526 Sheiko’s group has pioneered a novel strategy for facilitating reversible shape transformation in semicrystalline shape-memory materials.527 This innovative approach integrates three distinct shape-memory behaviors: conventional one-way shape memory, two-way reversible shape memory, and one-way reversible shape memory. The key to achieving shape reversibility lies in the partial melting of a crystalline scaffold, which leaves behind a latent template for recrystallization and ensures the memory of a temporary shape.  \n\n![](images/827172cd47314bad49b675027847cf6f4eebbedfac90bff8bd322bffcc7c3587.jpg)  \nFigure 32. Chemically driven actuators. (a) Schematic of the actuation mechanism of the porous membrane actuator and photographs of reversible actuation of star-shaped “flower” responding to humidity changes. (b) Schematic showing the configuration and actuation mechanism of the multifunctional soft actuator. (c) Schematic depicting the synthesis of carbon nitride polymer (CNP) composed of heptazine as a repeating unit and illustration showcasing the actuating motions of a CNP film triggered by changes in humidity. (d) Schematic illustration depicting the structure of MXene-Based soft actuator and the mechanism for moisture-driven actuating, humidity energy harvesting, self-powered humidity sensing, and real-time motion tracking. (e) Illustration depicting the mechanism of switchable and reversible biocatalyzed bending of a bilayer hybrid asymmetric hydrogel system. The lower row shows the reversible pH-stimulated bending of the bilayer glucose oxidase/urease-functionalized asymmetric hybrid system responding to glucose or urea. (f) Schematic showing the actuation mechanism of the glucose-powered polymer actuator and photographs showing the actuation performance. $(\\mathbf{g})$ Schematic depicting the actuation process of the urease-containing gel, showcasing the pH-responsive behavior and time-lapse photographs illustrating the dynamic actuation performance of the gel over time. (a) Reproduced with permission from ref 534. Copyright 2014, The Authors, published by Springer Nature. Reproduced under the terms of the Creative Commons Attribution 4.0 International License. (b) Reproduced with permission from ref 535. Copyright 2022 American Chemical Society. (c) Reproduced with permission from ref 536. Copyright 2016 Springer Nature. (d) Reproduced with permission from ref 537. Copyright 2021 American Chemical Society. (e) Reproduced with permission from ref 458. Copyright 2016 American Chemical Society. (f) Reproduced with permission from ref 457. Copyright 2019 Wiley. (g) Reproduced with permission from ref 538. Copyright 2023 Wiley.  \n\nThrough experimentation with various shapes, the authors demonstrated the efficacy of this strategy and elucidated the role of polymer crystallites in shaping memory behavior (Figure 31b).  \n\nNi et al. developed a shape-memory hydrogel utilizing phase separation as the underlying mechanism.528 This hydrogel, formulated from an aqueous photocurable resin, demonstrated remarkable versatility and programmability. By adjusting the programming time and monomer concentration, they could precisely control the degree of phase separation and the onset delay of shape recovery (Figure 31c). The team showcased the hydrogel’s versatility by fabricating a range of devices with customizable shape recovery properties. Other than shapememory polymers, shape-memory alloys have also been widely used in soft robotics. Majidi’s group has developed untethered soft robots capable of dynamic locomotion at speeds comparable to biological organisms.461 This achievement is realized through the utilization of compliant lightweight actuators featuring a shape-memory alloy (SMA). These SMA-based compliant actuators can seamlessly transition between a compliant unactuated state and a stiff actuated state, enabling rapid motions and generating substantial forces akin to natural muscle. The soft robots were validated in two distinct testbeds: a soft electrically actuated quadruped (SEAQ) and a multigait caterpillar-inspired robot. The SEAQ demonstrated versatile locomotion capabilities, including walking on various surfaces, climbing over obstacles, and achieving a maximum speed of 0.56 body lengths per second (blps) (Figure 31d). Cho’s group has developed a fully parallel-processable control system for robotic fingers by integrating a synaptic array with a robotic hand.529 The synaptic array, composed of ion-gel-based synaptic transistors connected to an ion gel dielectric, enables parallel signal processing and multiactuation control. Meanwhile, the robotic hand comprises three fingers crafted from NiTi shape-memory alloy fiber embedded in a 3D-printed body. The researchers demonstrated that the synaptic control system facilitates coordinated finger movement with reduced control complexity, leveraging the benefits of parallel multiplexing and analog logic. Furthermore, they showcased the system’s capability to execute complex actuations, including grasping objects with curvature and intricate designs (Figure 31e). Paik’s group designed a compact robot inspired by trap-jaw ants, capable of executing five distinct locomotion modes: vertical jumping, horizontal jumping, somersault jumping, walking, and crawling.530 This versatile locomotion mechanism is designed with minimal components and assembly steps, offering tunable power requirements (Figure 31f). In addition, shape-memory ceramic, shape-memory hydrogels, and shape-memory hybrid materials are also used to fabricate actuators (Figure 31g,h,i).531−533",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# 3.6. Chemical Actuators  \n\nChemical actuators represent a unique class of materials utilized in soft robotics, offering distinct advantages in responsiveness, adaptability, and energy efficiency. These actuators harness chemical reactions to induce mechanical motion, enabling precise control and manipulation of soft robotic systems. By leveraging the inherent properties of responsive materials in response to specific environmental stimuli such as $\\mathrm{\\ttpH}_{\\mathrm{\\tt3}}$ , temperature, light, or solvent composition. This brief intro highlights the pivotal role of chemical actuators in soft robotics, paving the way for innovative applications in fields ranging from biomedical devices to adaptive structures and beyond.  \n\n3.6.1. Organic Vapors and Solvents. Yuan’s group has introduced a groundbreaking porous polymer actuator that exhibits exceptional responsiveness to acetone vapor, surpassing previous state-of-the-art actuators by an order of magnitude in speed (Figure 32a). This novel actuator stands out for its multiresponsiveness to various organic vapors, both in dry and wet conditions, distinguishing it from conventional gel actuation systems that lose effectiveness when dried out.534 Notably, the actuator is straightforward to manufacture and can endure rigorous processing and pressing treatments. Furthermore, the researchers showcased the transferability of the actuator’s responsiveness to other objects through surface coating. This performance is attributed to the actuator’s unique combination of porous morphology, gradient structure, and the interaction between solvent molecules and the actuator material. Wang’s group has fabricated a multifunctional soft actuator driven by liquid, vapor, and light, leveraging a PDMS/ CNTs-PDMS-PVDF sandwich structure film.535 This innovative actuator demonstrated rapid and robust responses to various organic solvents, vapor, and light stimuli. Its fast response speeds and ability to mimic diverse motion behaviors make it promising for applications in energy-saving soft grippers, fast-speed soft crawlers, and jellyfish-like soft swimmers (Figure 32b). Additionally, the group developed another sandwich actuator driven by multiple external stimuli, including liquids, vapor, and solar light, utilizing aligned carbon nanotubes. This ultrafast-responsive actuator supports programmable motions and holds potential applications in healthcare, bioengineering, chip technology, and mobile sensors, showcasing its versatility and broad utility across various fields.  \n\n3.6.2. Humidity-Related Reactions. Aida’s group has made significant strides in developing an autonomous film actuator responsive to ambient humidity fluctuations. Crafted from a $\\pi$ -stacked carbon nitride polymer, this film boasts a tough, ultralightweight, and highly anisotropic layered structure (Figure 32c). Remarkably, the actuation of the film is rapid and durable, capable of over 10,000 repeated cycles without degradation.536 The researchers further showcase the film’s ability to unidirectionally walk when shielded from water adsorption. Its actuation is primarily driven by the adsorption and desorption of minute water amounts triggered by ambient humidity shifts. Additionally, the film can be activated by either heating or light irradiation.  \n\nQiu’s group has developed a moisture-responsive actuator using MXene materials, exploring its properties and applications in generating electricity from ambient humidity. The core of their work lies in a soft actuator, composed of MXene, cellulose, and polystyrene sulfonic acid (PSSA), capable of humidity-driven actuation, energy harvesting, selfpowered sensing, and real-time motion tracking (Figure 32d).537 By capturing the chemical potential of humidity, the actuator generates mechanical power through asymmetric expansion and electricity via directional proton diffusion, offering high power density and open-circuit voltage.  \n\n3.6.3. Enzymes. Willner’s group has introduced asymmetric two-layer hybrid DNA-based hydrogels capable of reversible shape transitions.458 These hydrogels feature layerselective switchable stimuli-responsive elements, dictating their stiffness. Trigger-induced stress in one layer induces bending of the hydrogel structure, which can be restored to its original linear bilayer form upon stress removal. The stiffness of the DNA hydrogel layers can be controlled by various triggers, including thermal, pH, $\\mathrm{K^{+}}$ ion/crown ether, chemical, or biocatalytic stimuli (Figure 32e). Jager’s group has introduced a self-powered artificial muscle fueled by glucose and oxygen .457 This innovative actuator integrates glucose oxidase and laccase enzymes, which catalytically convert glucose and oxygen into electrical power. The generated electrical energy drives movement in the actuator, facilitated by the electroactive polymer polypyrrole, resulting in bending motions (Figure 32f). The integrated bioelectrode pair exhibits a maximum open-circuit voltage of $0.70~\\pm~0.04~\\mathrm{~V~}$ and a maximum power density of $0.27\\mu\\mathrm{W}\\ \\mathrm{cm}^{-2}$ . Through full integration of the enzymes, the artificial muscle operates autonomously, capable of reversible bending in both directions solely powered by glucose and oxygen. This advancement holds promise for applications in soft robotics, implantable medical devices, and environmental monitoring.  \n\n![](images/f11eed6c4acbbdff362dc8f30a1a52d5431d1680fffee8cafabecf6320da17ca.jpg)  \nFigure 33. Soft robots by other actuation modalities. (a) Diagram depicting the ultrasound-driven actuator. When subjected to sweeping frequency ultrasound excitation, the artificial muscle undergoes multimode deformation over time, as illustrated at time points $\\mathrm{T}_{1},\\mathrm{T}_{2},$ and $\\mathrm{T}_{3}$ . (b) Optical images depicting the downward motion of microrobots within 3D channels inclined at different angles. (c) Photographs demonstrating the precise modulation of the Venus flytrap’s response time, enabling the phytoactuator mounted on a manipulator to capture a moving object. (d) Photographs displaying muscular bending responses of the worm under different laser intensities. (e) Images showing the pillar couple bends when wet and straightens when dry (top). (f) Bioinspired design of the autonomous seed carrier with self-drilling capability. $(\\mathbf{g})$ Image depicting the engineered jumper alongside time-lapse frames capturing the acceleration phase of the jumper’s motion. (h) Structural depiction and operational principle of the phase-change-based soft composite material, alongside an illustration demonstrating the expansion process using a single ethanol bubble. (i) Schematic illustrating the mechanism of combustion and time-lapse images showcasing the actuation process. (a) Reproduced with permission from ref 540. Copyright bioRxiv 2024, under a CC-BY-NC-ND 4.0 International license. (b) Reproduced with permission from ref 541. Copyright 2023, The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC). (c) Reproduced with permission from ref 464. Copyright 2021 Springer Nature. (d) Reproduced with permission from ref 543. Copyright 2021 American Association for the Advancement of Science. (e) Reproduced with permission from ref 544. Copyright 2022 Springer Nature. (f) Reproduced with permission from ref 545. Copyright 2023 Springer Nature. $\\mathbf{\\eta}(\\mathbf{g})$ Reproduced with permission from ref 546. Copyright 2022 Springer Nature. (h) Reproduced with permission from ref 547. Copyright 2017, The Authors, published by Springer Nature. Reproduced under the terms of the Creative Commons Attribution 4.0 International License. (i) Reproduced with permission from ref 548. Copyright 2023 American Association for the Advancement of Science.  \n\n3.6.4. pH. Walther’s group presented a method to achieve autonomous control in soft robotic actuators by integrating autonomous chemical controllers with pH-responsive hydrogels.538 Leveraging a one-component transient pH-flip mechanism based on activated carboxylic acids, which undergo spontaneous $\\mathrm{\\tt{pH}}$ -dependent decarboxylation in solution, they demonstrate precise control over $\\mathrm{\\ttpH}$ drop and transient state duration by injecting varying quantities of the activated acid into a buffer solution (Figure $32\\mathrm{g}$ . By coupling this pH-flip with hydrogels, they enable autonomous motion, leveraging the hydrogels’ swelling and deswelling responses to $\\mathsf{p H}$ changes for actuation. Their approach finds applications in interlocking puzzle pieces and grasping objects with small orifices. Furthermore, they explore incorporating chemomechanical feedback by coupling the pH-flip with the urea/ urease enzymatic reaction, facilitating additional control over actuation.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# 3.7. Other Actuation Modalities  \n\nIn addition to the aforementioned actuation modalities for soft actuators, there are other types such as acoustic, biohybrid, and combustion. Moreover, combining multiple actuation modalities within a single soft robot is not uncommon.539 There are still many innovative actuation modalities yet to be discovered and exploited.  \n\n3.7.1. Acoustic. Ahmed’s group has introduced a new class of soft artificial muscles that leverage acoustically activated microbubble arrays to achieve precise and programmable actuation (Figure 33a). These acoustic artificial muscles are characterized by their dynamic programmability, large force intensity, rapid responsiveness, wireless controllability, all while being exceptionally compact and lightweight. Their findings demonstrate that the use of resonant microbubbles allows for the amplification of acoustic energy, enabling a weak sound source to produce substantial actuation in the artificial muscle. They have successfully engineered a broad array of preprogrammed movements and applications for the artificial muscle, which are directed by the unique configuration of the microbubbles and the ultrasound excitation parameters, such as voltage and frequency. They showcased the strength and durability of these muscles by incorporating the variable-sized microbubble arrays into devices such as a soft gripper, a biomimetic stingray robot, a shape transformer, and a robotic skin.540 In another study, they developed an acoustically driven helical microrobot that emulates the spiral motion of natural microswimmers (Figure 33b). Fabricated using 3D printing, these microrobots were meticulously examined through computer simulations to ascertain the forces and torques acting upon them. Through manipulation with a single sound source, the microrobots showcased bidirectional movement, with the ability to adjust motion by modulating the acoustic frequency.541  \n\n3.7.2. Biohybrid. Biohybrid robots are another interesting and promising type of robots.542 Chen’s group developed an electrical phytoactuator by pairing a Venus flytrap as the actuating component with conformable electrodes for modulation.464 They engineered plant-conformable electrodes and adhesive hydrogels to interact with the plant without impeding its movement or physiology. This phytoactuator could be wirelessly controlled via smartphone and integrated into diverse platforms. The study showcased its capability to grasp thin wires and capture moving objects, boasting a rapid response time of approximately 1.3 s and low power consumption (Figure 33c). Additionally, the research delved into the design, fabrication, and characterization of the system’s components, outlining potential applications and future avenues of exploration. Liu’s group provided a method to regulate the locomotion of a live Caenorhabditis elegans worm, culminating in the creation of a controllable living soft microrobot named “RoboWorm” via optogenetic excitation and visual feedback. The RoboWorm successfully emulated natural worm locomotion patterns and adeptly maneuvered through obstacles (Figure 33d). The study also entailed the development of dynamic and kinematic models to elucidate the worm’s crawling mechanism and the implementation of closed-loop motion control.543  \n\n3.7.3. Humidity. Zhang et al. conducted extensive experiments and analyses to explore the hygroscopic motion of pine cones and develop biomimetic actuators based on this mechanism.544 They investigated the microstructure of vascular bundles (VBs) within the pine cones and analyzed their role in hygroscopic deformation. Building on these findings, they 3D printed artificial actuators mimicking the pine cone structure and demonstrated their mechanical properties and shape transformations. The study revealed that pine cones undergo ultraslow deformation primarily due to the unique spring/square microtube heterostructure of the VBs. Inspired by this mechanism, the researchers developed soft actuators capable of controlled, imperceptibly slow motion (Figure 33e). These actuators have potential applications in camouflage and reconnaissance due to their low motion velocity compared to other humidity-driven actuators. Yao et al. devised and manufactured autonomous self-drilling seed carriers utilizing wood veneer as the primary material. Drawing inspiration from the hygroscopic behavior of natural grass seeds, the carriers featured a three-tailed configuration and a hygromorphic coiling body (Figure 33f). Tailoring the design for diverse terrains and payloads, including embedding symbiotic species and delivering beneficial nematodes, the seed carriers exhibited promising applications in agriculture, reforestation, and environmental conservation. Additionally, the study elucidated design principles for transforming wood veneer into stiff and biodegradable hygromorphic actuators with substantial bending curvatures.545  \n\n3.7.4. Energy Storage. Hawkes et al. presented a comparative model examining the energetics of biological and engineered jumpers.546 They evaluated specific-energy production limits and utilization in both biological and engineered jumpers, analyzing components like motor, spring, linkage, and payload. The findings revealed that while biological jumpers are constrained by the work capacity of linear muscles, engineered jumpers can surpass this limit by employing work multiplication. Leveraging these insights, the researched devised an engineered jumper featuring a highspecific-energy hybrid spring-linkage, achieving remarkable jump heights exceeding $30\\mathrm{~m~}$ (Figure $33\\mathbf{g}$ ).  \n\n3.7.5. Phase Change. Lipson’s group pioneered a selfcontained soft composite material featuring a silicone elastomer matrix infused with ethanol distributed in microbubbles (Figure 33h). This innovative material boasted impressive mechanical properties, including high strain and stress capabilities coupled with low density. It offered versatility in manufacturing methods, allowing for casting or 3D printing, and found utility as an actuator in diverse robotic applications. Demonstrating remarkable expansion−contraction abilities, it showcased the capacity to lift weights exceeding its own. Notably, it provided high strain levels even when powered by low-voltage sources, rendering it ideal for untethered applications.547  \n\n![](images/d9bc3f11c2b581a2624dfd3062e14b6f536e1591d7576588b971d3c72570f844.jpg)  \nFigure 34. A summary of future development of soft actuators. (a) Key points for the significance and future development for several performance indicators of soft actuators, including elastic modulus, actuation strain, work density, power density and strain rate. (b) Comparison of human skeletal muscles with multiple actuators as artificial muscles in terms of the above-mentioned performance indicators. The data was extracted from refs 108, 444, 461, 471, 549−554.  \n\n3.7.6. Combustion. Shepherd’s team has pioneered the development of potent soft combustion actuators tailored for insect-scale robots (Figure 33i).548 By leveraging high-energy density chemical fuels, they significantly enhanced the performance of microactuators compared to existing technologies. Demonstrating their innovation, they engineered a $325{\\cdot}\\mathrm{mg}$ soft combustion microactuator capable of remarkable displacements of $140\\%$ , operating frequencies exceeding 100 $\\mathbf{Hz},$ and generating forces surpassing $9.5\\ \\mathrm{N}$ . These advancements were further integrated into an insect-scale quadrupedal robot, showcasing diverse gait patterns, precise directional control, and a payload capacity 22 times its body weight. This robotic platform adeptly navigated uneven terrain and overcame obstacles with ease.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 25,
+        "chunk": "# 3.8. Future Development  \n\nSoft actuators, designed to emulate the flexibility and functionality of natural muscle, have become pivotal in advancing applications where interaction with humans or sensitive environments is necessary. These actuators offer significant advantages over traditional rigid actuators by providing greater compliance and safety. Among the types explored are pneumatic actuators, known for their high specific power, which can reach up to $20,000~\\mathrm{W/kg};$ shape-memory alloys, which offer distinct responses under thermal activation; dielectric elastomer actuators, which can achieve substantial actuation strains up to $1000\\%$ ; and ionic polymer−metal composites, valued for their low voltage operations. By comparing these with human skeletal muscles, which typically operate within a specific power range of 50 to $280~\\mathrm{W/kg}$ and an actuation strain of $30{-}40\\%$ , it becomes clear how each soft actuator can be optimized for specific tasks in robotics, medical devices, and more (Figure 34).  \n\n![](images/4b16eabd279940f6e4bfbbcc79a30a905a7e4216dd142cddd49d3b717e7ddc47.jpg)  \nFigure 35. Soft sensing and actuation structures based on buckling. Soft structures in sensing devices, including (a) wavy, (b) crumpling, (c) serpentine, (d) arc-shaped, (e) fractal design, (f) noncoplanar serpentines, (g) 2D spiral, (h) 3D helical, and (i) hierarchical buckling. Reproduced with permission from ref 593. Copyright 2006 Springer Nature. Reproduced with permission from ref 597. Copyright 2013 Springer Nature. Reproduced with permission from ref 53. Copyright 2011 American Association for the Advancement of Science. Reproduced with permission from ref 601. Copyright 2009 Wiley. Reproduced with permission from ref 603. Copyright 2014 Springer Nature. Reproduced with permission from ref 604. Copyright 2008 United States National Academy of Sciences. Reproduced with permission from ref 605. Copyright 2015 IOP publishing. Reproduced with permission from ref 606. Copyright 2017 Springer Nature. Reproduced with permission from ref 607. Copyright 2017 Elsevier. Soft structures in soft robots, including (j) wavy ring, (k) caterpillar structure, (l) spiral shape, $(\\mathtt{m},\\mathtt{n})$ tortuous structures, $(\\circ,\\mathsf{p},\\mathsf{q})$ helical structures. Reproduced with permission from ref 608. Copyright 2023 Wiley. Reproduced with permission from ref 609. Copyright 2023 American Association for the Advancement of Science. Reproduced with permission from ref 610. Copyright 2023 Wiley. Reproduced with permission from ref 611. Copyright 2022 United States National Academy of Sciences. Reproduced with permission from ref 612. Copyright 2021 Springer Nature. Reproduced with permission from ref 613. Copyright 2021 Springer Nature. Reproduced with permission from ref 614. Copyright 2023 American Association for the Advancement of Science. Reproduced with permission from ref 615. Copyright 2014 American Chemical Society.  \n\nWhile these artificial muscles often surpass human muscles in specific power and strain capabilities, they also face challenges such as fatigue, the need for external power sources, and sensitivity to environmental conditions, factors where natural muscles generally maintain robust performance. This examination not only delves into the technical specifications of each actuator type but also highlights their transformative potential in the burgeoning field of soft robotics, along with a realistic assessment of their advantages and drawbacks compared to human musculature.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 26,
+        "chunk": "# 4. STRUCTURE AND MECHANICS  \n\nThe rapid advancements of flexible electronic devices and soft robot have witnessed the transformation from hard and rigid materials-based dyestveicmes. $60,61,96,11\\bar{7},555-5\\bar{6}3$ m t  s fwt oarnthd nleoxtiibnlge that the performance of such flexible systems is comparable or even superior than that of conventional rigid devices. For example, the flexibility and biocompatibility of soft neural device could make more precise neural recording possi$\\mathbf{\\Delta}\\mathbf{b}\\mathbf{le},^{564,565}$ and the intrinsic softness of soft robot can increase the safety between the human−robot interaction.566−568 This materials-based paradigm shift opens new windows for boundless applications in prosthetics ,569 brain−machine interface,570,571 metaverse,572 and so on.97,573 However, the employment of soft materials in soft electronics and robots may also suffer a certain number of limitations that could impeded the further real-world applications, such as limited stretchability and hysteresis in soft electronics, low actuation speed and output forces for soft machines, etc.117,574−576 To overcome these challenges, structural materials would provide an excellent solution to the issues.577−580 Assisted by mechanically guided design and analysis, the structural devices could exhibit unprecedent mechanical performances that are hard to achieve by their soft counterparts, achieving ultralow hysteresis and hyperstretchability for electronic devices and fast response time and other elegant performances.581−584 In this section, four types of structures for soft electronics and robots are summarized and discussed: buckling structures, kirigami and origami, fibers and fabrics, and other structures.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 27,
+        "chunk": "# 4.1. Buckling Structures  \n\nBuckling structures refer to the design or arrangement within the device that allows it to undergo controlled collapsing, crumpling, curving, wrapping, or other behaviors with response to mechanical stress.585−590 This controlled buckling can be utilized to enhance the device’s mechanical properties, such as flexibility, stretchability, or conformability .183,591,592 Moreover, this structure is not uncommon both in electronic devices and soft robotic systems.  \n\nIn flexible electronic devices, common buckling structures include wavy, crumpling, serpentine, arc-shaped, fractal design, noncoplanar serpentines, 2D spiral, 3D helical, and hierarchical buckling, as shown in Figure 35a-i. According to mechanics of materials, the rigidity can be greatly reduced by decreasing the thickness of materials, which becomes a widely used approach to fabricate wavy structure for stretchable electronics. By utilizing this approach, precisely engineered wavy semiconductor nanoribbons (GaAs and Si) were successfully prepared by Sun et al.593 This structure can effectively enhance the stretchability of brittle and rigid materials. Moreover, the layout of wavy structure can be precisely controlled by selectively bonding of ribbon thin film and the substrate, on which a number of interesting working are based.594,595 Crumpling is another structural strategy to control the properties of materials, such as graphene.596 Based on this, Zang et al. reported an reversibly controlled approach for the crumpling and unfolding of graphene sheets.597 Serpentine interconnects refer to a specific type of pathway designed to accommodate mechanical strain and deformation. Generally speaking, there are two curved sections (arc) and three linear sections (arm) involved in such serpentine pathway and its mechanical performance is dependent on the parameters of each section, such as the radius and width of arc, and the length of the arm.598−600 In an integrated epidermal electronic system, such serpentine structure is employed for the mechanical performance of the system.53 Like the wavy structure created by selective bonding, the arc-shaped interconnections undergo compression-induced buckling, transitioning from a flat arrangement. As shown in Figure 35d, 2D silicon-based circuits can be engineered to adapt to a wide range of curvilinear surfaces by the employment of structured silicon layouts with polymer/metal interconnects.601  \n\nIn this way, curvilinear electronic devices on arbitrary surface can be well fabricated. Fractal design is a design principle where the same pattern repeats at different scales within a specific structure.602 These designs often exhibit self-similarity, meaning that they look similar at any level of magnification. This principle could provide a powerful design source for both stretchable interconnects and functional layers to achieve large stretchability as well as seamless hard−soft materials integration (Figure 35e).603  \n\nDifferent from the aforementioned serpentine structures, Kim et al. reported the concepts and exploration of noncoplanar structures that could accomplish even high stretchability and accommodate almost every mechanical deformation to high levels of strain (Figure 35f).604 Other structures have also been widely used in electronic devices, such as 2D spiral and 3D helical structure, as shown in Figure 35g, h.605,606 The origin of which can be found in nature and daily objects such as nautilus shells and springs. While the former structures are fabricated by wrapping a circle around a fixed point, the latter one takes the advantage of less physical coupling with the substrate to suppress strain concentrations during the deformation. Besides, Huang et al. reported a new type of self-similar piezoelectric nano/microfibers with hyper stretchability by regulating the manufacture parameters in the electrohydrodynamical printing process, providing insights into the digital manufacturing of stretchable devices (Figure 35i).607  \n\nAs for soft robots, a variety of buckling structures have also been widely used in this field. For example, Zhao et al. reported a self-sustained snapping autonomous soft robot that can be driven either by light or thermal (Figure 35j).608 With wavy ring-like structure, such robot is made of liquid-crystal elastomer and takes the advantage the symmetry of the shape to control the movement pattern of the robot. Specifically, such robots with symmetric shape tend to have self-dancing motion, and those with unsymmetric shapes may exhibit directional crawling behavior due to the friction difference. In another work, a caterpillar-inspired crawling robot with multiple movement modes is developed by Wu et al., as shown in Figure 35k.609 Enabled by joule heating, bidirectional locomotion can also be achieved for this robot due to the friction competition of the front and rear part with the ground. However, due to the intrinsic properties of soft materials, soft robots often suffer from limited agilities. Such limitations can be overcome by structural engineering of the physical body of soft robots. In Figure 35l, a spiral robot made of piezoelectric composites is demonstrated, with an impressive forward locomotion speed of 76 body length per second.6 Apart from locomotion, the ability of grasping is another essentially vital skills for soft robots. Although a number of pneumatic driven soft grippers for grasping tasks have been discussed previously, the requirement of perception and feedback control makes dexterous manipulation and handling much more complicated and challenging. Alternatively, Becker et al. introduced a novel grasping strategy by active entanglement, which circumvent the employment of motion planning and feedback (Figure $35\\mathrm{m}{\\ddot{}}$ ).611 Benefitted from such grasping strategy, a wide range of objects with different size, weight, and shape can be conformably grasped without any sensing and feedback control. Generally speaking, the morphing pattern of soft grippers is closely related with its physical information, such as size, Young’s modulus, and geometry. To make soft robots work effectively as designed, complicated prototyping processes are needed, ranging from modeling to optimization and fabrication. What makes it even worse is that conventional fabrication techniques may limited in terms of scalability, robustness, and design flexibility. To solve this, Jones et al. developed an all-in-one approach to fabricate programmable soft pneumatic actuators by harnessing the interfacial flows in uncured soft materials, as shown in Figure $35\\mathrm{n}$ .612 This novel approach would accelerate the development of soft machines with more complicated structures and provide more functions in soft robot that are attributed to the geometric and material properties. Helical structure is another widely studied designs for soft machines. In two separate works, Hu et al. reported helical-artificial fibrous muscle structured soft actuators with multiple degrees of freedom, with one exhibiting a myriad of oscillating modalities, and another adaptive omnidirectional reorientation abilities, as shown in Figure 35o,p.613,614 On the other hand, helical designs can also be used for propelling robots. Schamel et al. demonstrated the effective control of propulsion of microrobots in complex viscoelastic media, which is promising for future biomedical applications (Figure 35q).615",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 28,
+        "chunk": "# 4.2. Kirigami and Origami  \n\nOriginating form artistic work, Kirigami and origami have a much longer history than soft electronic devices and robotic systems. In their design, a range of techniques are utilized to engineer 2D sheets, such as papers and plastic films, into various 3D structures with special functionalities. Such interesting structures has also provided endless inspiration sources for the development of both flexible sensing devices and soft robotics.616−618 For example, kirigami and origami is not only an approach to design and fabrication of devices with unprecedented flexibility and stretchability, but also provides additional space for the functionality of these device in terms of morphing abilities, signal processing, logic computation, and so on.619,620 This could be an important aspect for next generation flexible systems with intelligence.621  \n\n![](images/8ec72b85f08db1a2107e4ed421bef3d8eedb4e283a592d0308f6ce593431668f.jpg)  \nFigure 36. Kirigami and origami structures for sensing devices and actuation. (a) Engineering of elasticity in nanocomposites by kirigami strategy. Reproduced with permission from ref 622. Copyright 2015 Springer Nature. (b) Schematic illustration of snakeskin-inspired kirigami metamaterials for conformal electronic armor. Reproduced with permission from ref 623. Copyright 2022 Wiley. (c) Photograph of the graphene kirigami. Reproduced with permission from ref 624. Copyright 2015 Springer Nature. (d) Photograph of the supercapacitor with customizable stretchability enabled by kirigami. Reproduced with permission from ref 625. Copyright 2018 Wiley. (e) Crawling soft actuator enabled by kirigami skin. Reproduced with permission from ref 626. Copyright 2018 American Association for the Advancement of Science. (f) Kirigami soft grippers. Reproduced with permission from ref 627. Copyright 2021 American Association for the Advancement of Science. (g) Programmable shapemorphing kirigami sheets. Reproduced with permission from ref 628. Copyright 2022 Springer Nature. (h) Programmable shapes by kirigami tessellations. Reproduced with permission from ref 629. Copyright 2019 Springer Nature. (i) Hemispherical electronic eye enabled by origami silicon. Reproduced with permission from ref 630. Copyright 2017 Springer Nature. (j) Origami mechanologic. Reproduced with permission from ref 631. Copyright 2018 United States National Academy of Sciences. (k) Origami paper photodetector arrays. Reproduced with permission from ref 632. Copyright 2017 American Chemical Society. (l) Miura-origami-inspired power generator. Reproduced with permission from ref 633. Copyright 2020 Springer Nature. (m) Shape morphing structures by origami. Reproduced with permission from ref 634. Copyright 2023 Springer Nature. (n) Paper robots integrated based on origami. Reproduced with permission from ref 635. Copyright 2023 Springer Nature. (o) Stretchable origami robotic arm with omnidirectional bending and twisting. Reproduced with permission from ref 636. Copyright 2021 United States National Academy of Sciences. (p) Robotic metamorphosis by origami exoskeletons. Reproduced with permission from ref 637. Copyright 2017 American Association for the Advancement of Science.  \n\nElasticity in rigid composite is usually hard to predict due to the stochastic emergence and distribution of strain-concentrating defects. Kirigami could provide a solution to this situation by preventing unpredictable local failure, and the maximum strain can also be increased from $4\\%$ to $370\\%$ , as shown in Figure 36a.622 This predictable behavior of elasticity in nanocomposites and stretchability pave way for the development of stretchable electronic and optoelectronic devices and other applications. From another aspect, Jiang et al. reported a snakeskin-inspired kirigami structure that can be used for adaptive conformal electronics (Figure 36b).623 This structure not only has similar functions as conventional e-skins, but more fascinatingly, could protect itself from external damages. Aside from this, kirigami can also be applied to other materials and dimensions. In their work, Blees et al. demonstrated the kirigami of graphene with tunable and robust mechanical performances in microscale (Figure 36c).624 More fundamentally, they found that the Föppl-von Kármán number in the materials, an indicator of the ratio between inplane stiffness and out-of-plane bending stiffness, is a crucial parameter for kirigami. Materials with higher Föppl-von Kármán number tend to be easier bend and crumple. These insights into graphene kirigami successfully establishes the connection between graphene sheets and microscale resilient systems. Other electronic parts, such as capacitors, can also be empower by the employment of kirigami. Lv et al. developed an editable, stretchable supercapacitors based on mechanically strengthened ultralong $\\mathrm{MnO}_{2}$ nanowire composites, as shown in Figure 36d.625 Move further, such kirigami-based supercapacitors were integrated with strain sensor into a system, and maintained stable sensing capabilities under large deformation, indicating the numerous possibilities of kirigami structures in different kinds of electronic devices.  \n\nApart from electronic part, kirigami structures can also find their major roles in soft actuators by providing various types of actuation mechanisms. By harnessing kirigami structures around an extending soft actuator, the crawling abilities of such actuators can be effectively enhanced, as shown in Figure 36e.626 The kirigami structures involved in this crawling robot were induced by the transformation of flat surface to snakeskin-like 3D textured surface. This transformation can further result in the friction force between the surface and the ground and then makes impact on the locomotion. Kirigami can also be used for soft grippers to handling objects that are challenging for conventional grippers. In one work, Yang and co-workers reported a soft gripper using kirigami shells, as shown in Figure $36\\mathrm{f.}^{627}$ Followed by finite element analysis, theoretical modeling, and experiment, the kirigami gripper is proven to grasp delicate and slippery objects. Moreover, such technique to fabricate robotic grippers can be miniaturized, modularized, and remotely actuated, which will promote the development of novel grippers for robotic applications. In another work, Hong et al. also demonstrated a soft gripper based on shape-morphing kirigami sheet (Figure $36\\mathrm{g}$ ).628 The principle behind was based on controlling the curvature of cut boundaries, which was inspired by the Gauss-Bonnet theorem. This programmable, universal, and nondestructive gripper moves further and can grasp even more delicate objects, such as raw egg yolk and human hair. Owning to their merits ranging from rich and compact morphing shape to special materials properties, kirigami tessellations could also be promising for robotics. However, the design of such structures has long been hindered by challenges from geometric and topological constraints. Choi et al. provided a theoretical framework of designing kirigami tessellation structures that can conform to any target shapes and also fabricated corresponding models to validate their inverse design approach (Figure 36h).629  \n\nDifferent from kirigami that cuts papers in a variety of techniques, origami employs folding approaches to engineer the structure and mechanical properties of sheets, which has also been widely reported in soft electronic devices and robotic systems. The first example of origami on soft electronic device is hemispherical electronic eye systems. It is widely known that design and integration of silicon optoelectronic device in hemispherical shape with high resolution is formidable. Based on convex isogonal polyhedral concepts, Zhang et al. successfully fabricated such device on a semispherical surface by shaping the raw silicon-based device into truncated icosahedron and then folding then into hemispherical surfaces (Figure 36i).630 Conventional, the decision process for soft robot is achieved by central processing in the sense-decideaction loop. However, central processing unit is typically rigid and hard, with is incompatible with the soft body of robots. By utilizing an origami waterbomb as a mechanical storage device, Treml and co-workers demonstrated programmable mechanical computation that is embedded into the body of soft robots, as illustrated in Figure 36j.631 Except for electronics device on curved surface, origami can be also beneficial for stretchable devices. Lin et al. reported an origami-based photodetector arrays that can withstand more than $1000\\%$ of strain, as well as bending and twisting without any performance degradation (Figure 36k).632 Benefit from the folded Miura structure, the orientation of the photodetector arrays and be adjusted to maximize the light harvesting efficiency. Tao et al. reported another kind of energy harvester (triboelectric nanogenerator) based on origami structure, as shown in Figure 36l.633 All these electronic devices represent the unique properties that origami can bring.  \n\nFor soft machines, origami engineering has also enabled a series of intelligent robots. However, current strategies for either kirigami or origami are restricted by permanent deformation, requirement of prepatterning, and cannot change their shape once designed. To address these limitations, Meeussen et al. proposed a multistable shape-morphing strategies that allows the erase of shapes and structures, as shown in Figure $36\\mathrm{m}.^{634}$ This strategy does not only make reprogrammable and robust actuation possible, but also can be applied to other undulation patterns and dimensions from miniature to architectural scales. In Figure ${36}\\mathrm{n},$ , Yan and coworkers reported an autonomous origami-based robot by integrating sensing, computation, and actuation into a comprehensive structure.635 Specifically, this autonomy in soft robots were achieved by combining flexible bistable mechanisms, acting as the information processing unit, with conductive thermal materials, acting as the actuation unit. Origami robot fabricated based on this functional integration can successfully capture preys and avoid obstacles, shedding light on the future development of fully soft intelligent machines. It should be noted that origami module can also work along with other actuation modules for soft robots with more diverse movement patterns and functionalities. Drawn inspiration from octopus arms, Wu et al. demonstrated an origami-based robotic arm with multimodal deformation capabilities, such as stretching, folding, bending, and twisting, which is controlled by magnetic module, as illustrated in Figure 36o.636 Starting from investigation the magnetic actuation patterns of deploying, folding, and bending of single unit Kresling, units of this patterns exhibit sophisticated movement with higher degree of freedom, mimicking the essential functions of octopus arms. Metamorphosis is another interesting topic for soft robot. By utilizing self-folding origami exoskeletons as the metamorphosis base of robot, Miyashita et al. introduced an approach for soft robot that can change their capabilities according to needs (Figure 36p).637 The origami metamorphosis can be activated by magnetic, heat, and water. Each stimulus controls a specific movement of the robot, which is promising for soft machines working in changing environment.  \n\n![](images/5c91a8098a7ce08c768201b0303afd36987d2143d26ad5da8fceb95815004eb7.jpg)  \nFigure 37. Fibers and fabrics for soft sensing and actuation materials. (a) Ultrasensitive textile pressure sensor. Reproduced with permission from ref 653. Copyright 2015 Wiley. (b) Fabric-based optical communications by diode fibers. Reproduced with permission from ref 654. Copyright 2018 Springer Nature. (c) Optoelectronic devices by semiconductor fiber. Reproduced with permission from ref 655. Copyright 2024 Springer Nature. (d) Chipless textile electronics by body-coupled fiber. Reproduced with permission from ref 656. Copyright 2024 Springer Nature. (e) Large-area display textiles. Reproduced with permission from ref 657. Copyright 2021 Springer Nature. (f) Rechargeable solid-state zinc-ion fiber battery. Reproduced with permission from ref 658. Copyright 2021 American Association for the Advancement of Science. (g) Metamaterial textiles for wireless body sensor networks. Reproduced with permission from ref 659. Copyright 2019 Springer Nature. (h) Tactile textiles for human−environment interaction. Reproduced with permission from ref 660. Copyright 2021 Springer Nature. (i) Electric actuated CNT artificial muscles. Reproduced with permission from ref 661. Copyright 2014 American Chemical Society. (j) Fiber pumps for wearable fluidic systems. Reproduced with permission from ref 662. Copyright 2023 American Association for the Advancement of Science. (k) Photoresponsive molecular motors. Reproduced with permission from ref 663. Copyright 2018 Springer Nature. (l) Thermal-driven fiber muscles. Reproduced with permission from ref 664. Copyright 2014 American Association for the Advancement of Science. (m) Helical fiber actuators driven by solvents and vapors. Reproduced with permission from ref 665. Copyright 2015 Springer Nature. (n) Magnetic-driven continuum fiber robots. Reproduced with permission from ref 666. Copyright 2019 American Association for the Advancement of Science. (o) Pneumatic soft robot by fabrics. Reproduced with permission from ref 667. Copyright 2023 Wiley. (p) Encoded soft textile robots. Reproduced with permission from ref 668. Copyright 2024 American Association for the Advancement of Science.  \n\n![](images/ec484482b84890c753a163da3dca81c56b9f75ab694bd40d5e77786e0e35cfb7.jpg)  \nFigure 38. Other structures for soft electronics and soft robots. (a) Mechanical integrated circuit materials. Reproduced with permission from ref 669. Copyright 2022 Springer Nature. (b) Mechanical metamaterial with stable memory. Reproduced with permission from ref 670. Copyright 2021 Springer Nature. (c) Meta-mechanotronic materials for self-powered computation. Reproduced with permission from ref 671. Copyright 2023 Elsevier. (d) Architected materials with neural learning abilities. Reproduced with permission from ref 672. Copyright 2022 American Association for the Advancement of Science. (e) Physically intelligent materials for on-board control. Reproduced with permission from ref 673. Copyright 2023 American Association for the Advancement of Science. (f) Mechanical metamaterials for counting and sequential information processing. Reproduced with permission from ref 674. Copyright 2023 American Physical Society. (g) Elastically instable materials for soft robot with high-speed and high-force. Reproduced with permission from ref 675. Copyright 2020 American Association for the Advancement of Science. (h) Dome-patterned metamaterial sheets for soft gripper. Reproduced with permission from ref 676. Copyright 2020 Wiley. (i) Buckling elastomeric materials for the actuation of soft machines. Reproduced with permission from ref 677. Copyright 2015 Wiley. (j) Self-folding materials for robots. Reproduced with permission from ref 678. Copyright 2014 American Association for the Advancement of Science. (k) Self-growing robot navigation in unstructured environments. Reproduced with permission from ref 679. Copyright 2024 American Association for the Advancement of Science. (l) Pneumatic shape-morphing elastomers. Reproduced with permission from ref 680. Copyright 2019 Springer Nature.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 29,
+        "chunk": "# 4.3. Fibers and Fabrics  \n\nFibers and fabrics, stemming from nature and refined by human ingenuity, have intertwined themselves throughout the entirety of human civilization’s narrative.638−640 From the earliest threads spun by ancient cultures to the sophisticated textiles of modern times, fibers have been integral to human life, serving as the building blocks of clothing, shelter, and countless other essentials. Through innovation and craftsmanship, humans have transformed raw fibers into intricate fabrics, weaving together stories of culture, technology, and progress. This ancient artistry continues to shape our world today in an increasing pace, as fibers and fabrics not only serve for conventional applications, such as clothing, furnishing, and industry, but also are integrated with electronic components and other functions for more possibilities.174,639,641 In recent years, there has been a growing interest in developing novel smart responsive functions for fibers and fabrics to enable seamless integration of actuators, sensors, power sources, and other components.642−645 While the marriage between fibers and fabrics and electronics holds promise for a range of applications, including wearable electronics, smart clothing, perception augmentation, health monitoring, and biomedical application, the convergence of textile technology and soft robotics opens up new possibilities for creating intelligent and adaptive systems that enhance human−machine interactions and contribute to various fields, from healthcare to remote operation and beyond.646−652 The following session will discuss the latest representative advancements made in fibers and fabrics for soft electronic devices and robotic applications.  \n\nA variety of sensors based on different working mechanism have been exhaustively discussed in Section 2, and a majority of these sensors are in the form of soft film. However, it should be noted that sensors should not be restricted within this form. Fiber sensors are also possible, as the fiber-based ultrasensitive pressure sensor in Figure 37a and photodetector in Figure 37b.653,654 Figure 37c shows the wearable electronic device enabled by semiconductor fiber.655 Nevertheless, rigid silicon components are usually needed in conventional fiber electronic systems for energy supply, computation, and communication, which greatly limits the development of textile electronics. To address this, Yang et al. introduced a chipless body-coupled energy interaction mechanism using a singular fiber, eliminating the necessity for additional chips or batteries on textile surfaces (Figure 37d).656 In another work, by interlacing conductive weft and luminescent warp fibers, Shi et al. created $\\mu\\mathrm{m}$ -scale electroluminescent units at the intersections of the weft and warp, and demonstrated an integrated textile system comprising a display, keyboard, and power supply can function as a communication tool (Figure 37e).657 To solve the power supply issue of electronic textiles, Xiao et al. presented a rechargeable solid-state fiber battery, which can work for more than $500\\mathrm{~h~}$ and its capacity can maintain $98\\%$ after over 1000 charging and recharging cycles (Figure 37f).658 Except these examples, fibers can also be used for metamaterials for wireless transmission and large-area tactile sensor arrays, as shown in Figure 37g,h.659,660  \n\nActuators can either be in a single fiber form or woven textile form and driven by stimuli including electric, light, thermal, solvent, magnetic, pneumatic, etc. Figure 37i shows an electricdriven artificial yarn muscle utilizing a spinnable carbon nanotube (CNT) sheet with impressive performance metrics for torsional and tensile actuation.661 Figure 37j is another electric-driven textile-based actuator integrated with a fiber pump.662 Chen et al. illustrated the macroscopic contractile motion resembling muscle behavior in a supramolecular system primarily composed of water (Figure 37k).663 This system arises from the hierarchical self-assembly of a photoresponsive amphiphilic molecular motor and exhibits significant motion amplitudes, rapid response times, precise shape control. To lower the cost of artificial muscles and improve their performances such as hysteresis, efficiency, cycle life, Haines et al. demonstrated the feasibility of converting inexpensive, high-strength polymer fibers commonly used in fishing lines and sewing threads into efficient tensile and torsional muscles through a simple twist-insertion process, as shown in Figure 37l.664 By employing a hierarchical and helical assembly process of aligned carbon nanotubes, Chen and coworkers demonstrated the creation of actuating fibers responsive to solvent and vapor stimuli (Figure 37m).665 The nanoscale gaps between individual nanotubes and micrometer-scale gaps among the primary fibers contribute to the swift response and substantial actuation stroke and the compact coil structure enables the reversibility of rotation. Figure $37{\\mathrm{n}}$ exhibits ferromagnetic soft continuum robots in a fiber form possessing omnidirectional steering and navigation capabilities driven by magnetic, which can be used for minimally invasive robotic surgery for inaccessible lesions.666 The integration of fibers and textiles with pneumatic actuators may open avenues to wearable robotics, programmable textile soft robotics and many other possibilities. Sanchez et al. investigated the influence of knit structure and yarn material properties on textile mechanics, followed by developing 3D knit soft actuators capable of extension, contraction, and bending (Figure 37o).667 It is worth noting that the properties of the textile can be customized by knit architectures and yarn materials, resulting in the on-demand manufacturing of textilebased soft robots with personalized performance. In another work, Guo et al. introduced a methodology to streamline the construction of 3D soft textile robots through 2D sewing process, as shown in Figure $37\\mathrm{p.}^{668}$ In this technique, the actuation performance of the soft robot can be programmed and guided by its textile shells, which will expedite the development and iteration of soft robots with tailored performance for safe human−robot interactions, wearable devices, and healthcare applications.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 30,
+        "chunk": "# 4.4. Other Structures  \n\nBesides the aforementioned three major types of structures for electronic devices and soft robots, buckling structures, kirigami and origami, and fibers and fabrics, there are many other types of structures that exhibit unique properties for specific applications. Compared with the previous three types of structures, the last type of structures is less matured and investigated, which is worth of being explored. If employed properly, these structures will undoubtably bring the soft sensing and actuation system into a completely new level.  \n\nRecent, scientists have integrated sensing and actuating functionalities into soft matter and thus such intelligent materials can respond properly to environmental stimuli. Nevertheless, information processing in such systems has been constrained by unconventional methods with limited scalability. Helou and co-workers introduced a new type of integrated circuits materials across various scales and physical environments (Figure 38a).669 These materials are able to execute sophisticated arithmetic, number comparison, and binary data decoding into visual representations. This research establishes a connection between Boolean mathematics and kinematically reconfigurable electrical circuits, facilitating all combinational logic operations in soft, conductive mechanical materials. Chen et al. reported a design framework for a tileable mechanical metamaterial with stable memory at the unit-cell level (Figure 38b).670 It employs physical binary elements analogous to digital bits, allowing for independent and reversible switching between two stable states using magnetic actuation. Each state corresponds to a distinct mechanical response, enabling reversible cycling until reprogramming. Encoding binary instructions onto the array yields varied mechanical properties, such as stiffness and strength spanning an order of magnitude. This approach promises advanced forms of mechanical metamaterials with stable memory and on-demand reprogrammability. By integrating mechanical metamaterials, digital electronics, and triboelectric nano energy harvesting technologies into a platform, Zhang et al. demonstrated the use of digital unit cells as building blocks for synthesizing mechanical configurations, performing binary/ ternary computations, and realizing digital logic gates, as shown in Figure 38c.671 The ability to autonomously learn and maintaining this learning ability among changing circumstances is universal to living species, however, challenging to materials. In Figure 38d, Lee and co-workers introduced a new category of engineered materials that mimic the learning process of artificial neural networks (ANNs) by adjusting the stiffness of their constituent beams, laying the groundwork for the development of artificial-intelligent materials capable of learning behaviors and properties.672 Autonomous sensing and control aim to circumvent the use of bulky and intricate electronic sensors, microcontrollers, and actuators, which gains increasing attention from both scientists and engineers. To achieve this goal, He et al. presented an electronics-free, onboard-controlling method for soft robots, where the composition and structure of their bodies encompass sensing, control, and actuation feedback loops, as illustrated in Figure 38e.673 In their designs, several types of materials that are responsive to external stimuli (light, heat, solvents) are used as the control module of the robot, which provides an new idea for autonomous soft robots operating in uncertain or dynamic environments. Interestingly, Kwakernaak et al. demonstrated irreversible metamaterials capable of counting mechanical stimuli and storing the outcome (Figure 38f).674 Such metamaterials sheds light on the transient memories of complex media and paves the way for advancements in smart sensing, soft robotics, and mechanical information processing. The involvement of other types of structures in soft robotic system is also common. By exploiting mechanical instability of materials, Tang et al. demonstrated a spine-inspired soft machines capable of rapid movement, as shown in Figure $38\\mathrm{g.}^{675}$ Different from conventional soft robots that prioritize stability, this universal design principle harnesses tunable snapthrough bistability to unlock the full potential of soft robots to rapidly store and release energy within milliseconds. Furthermore, arrays of bistable have also been employed in the work of Faber and co-workers.676 In their work, soft sheets with array of patterned, reconfigurable bistable domes are integrated on 3D printed soft robotic grippers (Figure 38h).  \n\n![](images/bcae841eb9f0995c4ec1f1280a69ef0ffb2567a5e1d130efe6f938fd2d0f548d.jpg)  \nFigure 39. Fabrication techniques of soft electronic devices and robots by templating. (a) Simplified fabrication process of soft robot by casting. Reproduced with permission from ref 690. Copyright 2013 The American Society of Mechanical Engineers. (b) Schematic illustration of injection molding. Reproduced with permission from ref 154. Copyright 2022 Wiley. (c) Microscopic robots by photolithography. Reproduced with permission from ref 691. Copyright 2022 American Association for the Advancement of Science. (d) Simplified schematic illustration of soft lithography. Reproduced with permission from ref 692. Copyright 2007 Springer Nature. (e) Soft magnetic robot by agglutinate magnetic spray coating. Reproduced with permission from ref 693. Copyright 2020 American Association for the Advancement of Science. (f) Part of functional layer of the insect-scale soft robot fabricated by e-beam coating. Reproduced with permission from ref 694. Copyright 2021 American Association for the Advancement of Science. (g) Schematic illustration of working mechanism of stencil printing. Reproduced with permission from ref 695. Copyright 2017 American Chemical Society. (h) Schematic illustration of working mechanism of screen printing. Reproduced with permission from ref 696. Copyright 2017 Springer Nature.  \n\nStoring and processing spatially distributed mechanical signals could be achieved through this structure. Due to its fast response time, mechanical instability can be also used for soft grippers. In Figure 38i, Yang et al. demonstrated a novel actuation mechanism based on the collapse of a set of elastomeric beams.677 To be more specific, when negative pneumatic pressure is applied, the elastic beam elements within these actuators experience a reversible, cooperative collapse, resulting in the generation of rotational motion, and finally the gripper also can open and close according to this rotational motion. The use of origami in soft robot has been discussed in the previous section. Different from conventional ones, Felton and co-workers further enrich the role of origami in intelligent soft machines by utilization of shape-memory composites as the hinges of soft robots.678 As the hinge is stimuli-responsive, the robot could autonomously transform into a fully functional and intricate machine from a flat paper, exhibiting the same folded patterns derived from computational origami, as shown in Figure 38j. This marriage between metamaterials with intelligent matter holds the potential for machines with autonomous behaviors. Another solution for autonomous navigating and exploring soft robots can lie in the self-growing. However, the capability to grow and maneuver effectively in unstructured scenarios is still in the developmental stages. In Figure 38k, Dottore et al. presented an autonomous growing robot inspired by climbing plants’ adaptive strategies.679 Mimicking the apical shoot, it senses and coordinates growth using additive manufacturing and a sensorized tip. Growth direction is guided by stimuli like gravity and light, enabling navigation and adaptation to the environment. The robot can twine around vertical supports for stress relief and anchorage, adjusting material printing for varied needs. These features offer potential for applications in exploring, monitoring, and constructing complex infrastructures autonomously. Siéfert with co-workers got inspirations from biological morphogenesis and reported a novel approach for elastomer plates to change their shapes under applied pressure (Figure 38l).680 It should be noted that precisely controlled airway networks enable arbitrary changes of three-dimensional shapes in this work.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 31,
+        "chunk": "# 5. FABRICATION TECHNIQUES  \n\nThis section will navigate into the realm of fabrication. The fabrication of tools represents a fundamental aspect of human behavior and culture, distinguishing us from other animals and serving as a hallmark of our species’ evolutionary success. Through tool fabrication, humans have transformed their relationship with the natural world and reshaped the course of history. Undoubtably, fabrication also plays an indispensable role in soft robotics.681−683 It is the foundation to the development and deployment of hardware (physical body) of soft robots and sensors and it is also crucial for the further development and application of intelligent soft machines.575,684,685 The revolution in the fabrication techniques marks the radical advancements in soft robots and the way they interact with human beings, as revolution in manufacturing could not only bring mass production to meet the increasing needs of general public, but also bring unexpected materialssotf uscotcuierteys.-6f8u6n−c6t8i8onGsefnoreramlloy espuenaekxipneg,cttehderaeppalriecatmiaonysctyepneasr osf fabrication forms for soft robot and sensors. Herein, we select the most representative paradigms to further discussion: templating, laser assisted fabrication, 3D printing, transfer printing, and assembly. These five different fabrication modes may work either independently or together for electronic devices or soft machines.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 32,
+        "chunk": "# 5.1. Templating  \n\nTemplating is often used for fabricating soft robot actuators, grippers, and sensors with well-defined shapes and geometries. It allows for precise control over the final structure and enables batch fabrication of identical components.683 The templates involved in the fabrication process can be made from various materials, such as rigid substrates or sacrificial materials that are later removed.551 While the range of materials and resolution can be wide for templating, each templating technique has its own working parameters,689 here’re the details for the prevalent templating techniques.  \n\n5.1.1. Molding. Molding in soft robotics involves using molds to shape elastomeric materials into desired structures or components. Here we classify molding techniques into two categories according to their difference in fabrication procedure: casting and injection molding. Casting uses a mold with specific cavity to produce solid objects by pouring a liquid material into the cavity, as illustrated in Figure 39a.690 Before casting, a mold of the desired object is prepared either by 3D printing, machining, or other techniques from various materials such as wood, metal, or plastic. It represents the shape and features of the final soft robot component and thus its resolution limit is determined by that of molds. To prevent the casting material from sticking to the mold, a release agent is often applied to the mold surface to ensure easy removal of the cast part. Then, the elastomeric casting material, typically a two-part liquid silicone rubber is mixed and poured into the mold cavity followed by removal of air bubbles. Once the mixed elastomeric materials solidify, the mold is opened, and the cast part is removed. Casting offers several advantages for fabricating soft robot components, including the ability to produce complex shapes, customization of material properties, and scalability for mass production. Similarly, injection molding is another common manufacturing process used to produce large quantities of identical parts with high precision, as illustrated in Figure 39b.154 The elastomeric material is heated until it becomes molten and then injected into a mold cavity under high pressure. Overall, injection molding offers advantages in terms of precision, complexity, material selection, postprocessing requirements, efficiency, and scalability, making it a preferred choice for many manufacturing applications, especially in industries such as automotive, electronics, medical devices, and consumer products.  \n\n5.1.2. Lithography. Lithography is essential in the fabrication of microelectronics, where it is used to define the intricate patterns of transistors, interconnects, and other components on semiconductor wafers.697−699 It is also employed in the production of MEMS devices, sensors, optical components, and photonic devices. Lithography relies on the principle of selectively transferring a pattern from a mask or template onto a substrate coated with a photosensitive material, known as a photoresist. The mask contains the desired pattern, which is usually created by electron beam lithography. There are a number of steps involved in this technique, such as coating, exposure, development, and etching. It should be noted that the resolution of lithography, or the smallest feature size that can be reliably patterned, depends on factors such as the wavelength of the light source, the numerical aperture of the optics, and the characteristics of the resist material. Advances in lithography technology have enabled the production of increasingly smaller features, pushing the limits of nanoscale fabrication. Benefitted from the advancements of photolithography, Reynolds et al. demonstrated a type of microscopic robots with integrated control and information systems by photolithography.691 As shown in Figure $39\\mathrm{c},$ , these autonomous robots, sized between 100 and $250\\ \\mu\\mathrm{m}$ , exhibit responsiveness to optical commands with speeds exceeding $10~\\mu\\mathrm{m}$ per second (the inset is a structure of the functional microrobot during the photolithography process). This work is interesting and insightful, laying the groundwork for widespread use in performing intricate tasks, adapting to surroundings, and external communication.  \n\nSoft lithography is a versatile and widely used molding technique in soft robotics, in which a set of techniques were used in microfabrication to create patterns and structures on surfaces, as illustrated in Figure 39d.692 Unlike traditional lithography methods that involve hard materials like silicon, soft lithography uses elastomeric materials such as polydimethylsiloxane (PDMS) as molds or stamps.700 These stamps are typically created by casting from master templates made through conventional lithography or other methods. Once cured, the PDMS replica is peeled off the master mold, resulting in a negative impression of the mold’s features. This negative mold can then be used to create multiple copies of the soft robot component. There are a number of examples that employ soft lithography to fabricate soft robot components with precise features and complex geometries, such as pneumatic actuators, microfluidic channels, and sensor arrays.701−703  \n\n5.1.3. Coating. Coating refers to the process of applying a thin layer of material onto a substrate or template surface. This coating serves various purposes depending on the specific application. In soft robots, coating can be utilized to apply thin functional layers onto flexible components, enhancing their properties or adding functionalities in a controlled manner. According to the formation process of the coated film, coating can be classified into many categories, such as blade coating, spinning coating, spray coating, dip coating, e-beam coating, etc. Blade coating is a method for applying a uniform layer of liquid or viscous material onto a substrate. A blade spreads the material over the substrate’s surface and excess material is removed as the blade passes, ensuring an even layer.704 Spin coating utilizes centrifugal force to spread the liquid outward and then forms a uniform layer. In this process, a small volume of the liquid is dispensed onto the substrate’s center, which is then rapidly spun. Control over spin speed and duration determines film thickness .705 The aforementioned two coating approaches are mainly for applying thin films on a flat or 2D surface. Nonetheless, there may be cases where fabricating of thin film functional layer in arbitrary and 3D complex surfaces, in which blade and spin coating could not satisfy and spray and dip coating can provide more space. In spray coating, liquid coating materials are atomized into small droplets in the form of fine mist or aerosol using a spray gun or nozzle first, and then are propelled onto the substrate surface by compressed air or other means, as shown in Figure 39e.693 This technique offers several advantages, including uniform coverage over complex shapes or irregular surfaces, high throughput, and the ability to coat large areas quickly. As for dip coating, the substrate is dipped into the solution at a controlled rate, allowing the material to adhere to its surface. Upon withdrawal, excess material drips off, leaving behind a uniform coating layer. Dip coating also offers advantages in terms of simplicity, and the ability to coat complex shapes.706 For more precise control the thickness and composition of the films, e-beam coating, also known as electron beam evaporation, can be employed with a wide selection range of materials, including metals, semiconductors, and dielectrics.707 In this process, a high-energy electron beam is directed at a solid material, causing atoms or molecules to be ejected and form a vapor. This vaporized material then condenses onto the substrate surface, forming a thin film that can be precisely controlled in nanoscale. As shown in Figure 39f, Liang et al. demonstrated an agile insect-scale soft robots with trajectory control.694 This robot was driven by piezoelectric thin film and the thin layers in its body was fabricated by e-beam coating, indicating the power of this coating technique.  \n\n5.1.4. Printing. In the realm of templating, we classify printing into stencil printing and screen printing. Both stencil printing and screen-printing offer advantages such as high resolution, scalability, and compatibility with a wide range of materials for fabrication of patterns, making them valuable techniques in the fabrication of electronic devices and soft robotics components. Nevertheless, they bear some differences. As illustrated in Figure ${39}\\mathrm{g},$ a thin sheet of material with a designed pattern is placed over the surface to be printed in stencil printing, and the stencil can be employed with various materials, such as paper, plastic, or metal.695 Ink is then applied over the stencil, followed by pushing the ink through the openings onto the surface below using a roller, brush, blade, or spray gun, until the desired image or pattern is printed on the substrate. In contrast, screen printing involves the transfer of ink through a mesh screen onto a substrate, such as paper, fabric, metal, or plastic. The process begins with the preparation of a screen mesh, typically made of porous fabric stretched tightly over a frame, and the desired stencil is created on the screen by blocking out areas where ink should not pass through. Once the screen is prepared, ink is applied to the top of the screen, and a squeegee is used to evenly distribute the ink across the screen’s surface, forcing it through the open areas of the screen and onto the substrate below (Figure 39h).696 This process allows for the creation of intricate patterns. Depending on the complexity of the design, multiple layers of patterns may be applied, with each pattern requiring a separate screen and printing pass. In short summary, both screen printing and stencil printing facilitate the transfer of designs onto surfaces. Screen printing stands out for its versatility and high resolution, making it ideal for printed electronics, especially multilayered, multimaterials devices. On the other hand, stencil printing provides simplicity and fast customization.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 33,
+        "chunk": "# 5.2. Laser-Assisted Fabrication  \n\nSince the debut of the laser in the 1960s, its unique properties, including coherence, monochromaticity, and high energy density, have revolutionized manufacturing.708 In fabrication, lasers serve multiple roles, including precise material removal, heat generation for welding, and surface modification for marking and engravin g.709−713 Laser beams are directed by computer-controlled systems, allowing for intricate designs and high levels of automation. The importance of laser-assisted fabrication lies in its ability to achieve exceptional precision, speed, and versatility across various materials, including metals, plastics, ceramics, and composites. In soft sensing devices and robotics, for examples, laser ablation and laser direct writing techniques allow for the creation of fine features and complex circuitry on flexible substrates, enabling the production of bendable, stretchable, and lightweight electronic devices.714−716 Laser cutting and laser micromachining enable the precise shaping of soft materials like elastomers and hydrogels, facilitating the creation of soft actuators and sensors. Moreover, laser-based additive manufacturing methods, such as selective laser sintering or stereolithography, allow for the fabrication of complex structures layer by layer, offering unprecedented design freedom and functionality.717 Herein, we summarize three major roles of laser in the fabrication of soft robots and sensing devices for the relevant scope of this review: cutting, engraving, and modification.  \n\n![](images/dddda887553a8e2c273e1eb99e667363f66924f04c84302e5cf9ca2458f84332.jpg)  \nFigure 40. Laser-assisted fabrication of soft electronic devices and soft robots. (a) Laser cutting enabled 3D electronics. Reproduced with permission from ref 718. Copyright 2022 American Chemical Society. (b) Multimaterial pneumatic soft actuators through laser cutting. Reproduced with permission from ref 719. Copyright 2021 Wiley. (c) Laser-engraved wearable sensor for physiological signals detection. Reproduced with permission from ref 720. Copyright 2020 Springer Nature. (d) Stretchable pumps enabled by laser engraving. Reproduced with permission from ref 721. Copyright 2019 Springer Nature. (e) Flexible temperature sensor via laser reduced graphene oxide. Reproduced with permission from ref 722. Copyright 2022 Elsevier. (f) UV laser patterning of elastomeric sheets for soft robots. Reproduced with permission from ref 723. Copyright 2021 American Association for the Advancement of Science.  \n\n5.2.1. Cutting. Laser cutting utilizes a high-powered laser beam to precisely cut through materials, which can range from metals, plastics, and wood to glass, ceramics, and composites. The laser beam is focused onto the surface of the material, causing it to melt, burn, or vaporize along the desired cutting path. Laser cutting is an indispensable process in the manufacturing of electronic devices, serving crucial roles across multiple stages of their production. As shown in Figure 40a, it is employed in the fabrication of Printed Circuit Boards (PCBs),718 where it precisely cuts substrates and drills microvias, as well as in the dicing and singulating of semiconductor wafers and components. In the realm of flexible electronics, lasers shape substrates and also create conductive traces, enabling the production of flexible devices and wearable sensors. For soft robotics, laser cutting is employed to create intricate patterns and structures in materials such as silicone, rubber, and hydrogels, enabling the production of soft actuators and grippers, as demonstrated in Figure 40b.719 Attribute from laser cutting, 2D patterns with arbitrary shapes and sizes can be fabricated rapidly, these patterns could not only immediately serves as the working substrates or functional layers of the devices, but also can act as the enabling media for kirigami, origami, and other structures.  \n\n5.2.2. Engraving. While laser cutting is primarily used for cutting through materials to create shapes and parts, laser engraving, on the other hand, involves using a laser beam to remove material from the surface of an object to create a shallow depression or etched design. In this process, instead of cutting all the way through the material, the laser beam removes only a thin layer from the surface, leaving behind a permanent mark or design. For electronic devices, laser has been widely used as an efficient tool to convert organic materials to porous graphene structures. It is worth noting that the underlying mechanism for such conversion is the carbonization and graphitization of the engraved materials by laser, whose parameter should be carefully selected for products with a specific performance. Over the years, laserinduced graphene was successfully prepared from a wide range of materials, such as woods, paper, commercial polyimide, etc.710 For example, Lin et al. presented a facile and scalable method for producing porous graphene by using a $\\mathrm{CO}_{2}$ infrared laser on commercially available polymer films.724 The laser irradiation converts $\\mathsf{s p}^{3}$ -carbon atoms to $\\mathsf{s p}^{2}$ -carbon atoms, resulting in laser-induced graphene (LIG) with high electrical conductivity. Moreover, the graphene can also be patterned into interdigitated electrodes for energy storage device applications. Apart from fabrication of single type of electronic elements, laser engraving technology can also be used to manufacture multimodal wearable devices. In another example, Yang and co-workers reported a fully laser-engraved sensor capable of simultaneously sampling sweat, sensing chemicals, and monitoring vital signs, as shown in Figure 40c.720 This multimodal device enables continuous detection of temperature, respiration rate, and low levels of uric acid and tyrosine, which indicates the possibility of such technology in scalable manufacturing of multimodal functional devices for real world applications. Besides, laser engraving technology can also be used for soft actuation or robotic system. As shown in Figure 40d, Cacucciolo et al. demonstrated a stretchable pump for soft machines.721 This stretchable pump was composed several layers of soft materials, and the electrodes in both top and bottom layers are fabricated by laser engraving.  \n\n5.2.3. Surface Modification. Laser modification encompasses a variety of techniques used to alter material properties  \n\n![](images/be4a1ea45513b7361385d6e8fd25b8c46b0d3a3ba16a7a782b0ef73cae0dc175.jpg)  \nFigure 41. Fabrication techniques of soft electronic devices and robots based on 3D printing. Schematic illustration the working principles of commonly used 3D printing technologies, including (a) IJP, (b) DIW, (c) FDM, (d) DLP, (e) SLA, (f) TPP. (g) Printing of three-dimensional stretchable electronics. Reproduced with permission from ref 743. Copyright 2023 Springer Nature. (h) 3D printing of tissue adhesive. Reproduced with permission from ref 744. Copyright 2024 Springer Nature. (i) 3D printing of soft hydrogel electronics. Reproduced with permission from ref 745. Copyright 2022 Springer Nature. (j) 3D printing of silica aerogels. Reproduced with permission from ref 746. Copyright 2020 Springer Nature. (k) Multimaterial printing of filaments with subvoxel control enabled by nozzle rotation. Reproduced with permission from ref 747. Copyright 2023 Springer Nature. (l) 3D-printed entirely soft, autonomous robots. Reproduced with permission from ref 110. Copyright 2016 Springer Nature. (m) 3D-printed soft robot powered by combustion. Reproduced with permission from ref 748. Copyright 2015 American Association for the Advancement of Science. (n) 3D-printed biomimetic artificial muscles. Reproduced with permission from ref 749. Copyright 2022 American Association for the Advancement of Science. (o) 3D-printed Untethered soft robotic matter with passive control of shape morphing and propulsion. Reproduced with permission from ref 750. Copyright 2019 American Association for the Advancement of Science. (p) 3D-printed omnidirectional and exteroceptive soft actuators. Reproduced with permission from ref 751. Copyright 2022 American Association for the Advancement of Science. (q) Embedded 3D printing for soft somatosensitive actuators. Reproduced with permission from ref 752. Copyright 2018  \n\nWiley. (r) Proprioceptive three-dimensional architected robotic metamaterials by printing. Reproduced with permission from ref 753. Copyright 2022 American Association for the Advancement of Science. (s) Flexible electroluminescent soft robots by 3D printing. Reproduced with permission from ref 754. Copyright 2022 Springer Nature. (t) 3D-printed sensorized soft actuators. Reproduced with permission from ref 755. Copyright 2022 American Association for the Advancement of Science. (u) Soft robotic devices by vision-controlled jetting. Reproduced with permission from ref 756. Copyright 2023 Springer Nature.  \n\nthrough the application of laser energy. This can include surface modification processes like laser annealing, alloying, and texturing, as well as methods for introducing dopants or additive manufacturing techniques such as selective laser melting.725,726 These processes can be used to improve the surface hardness, wear resistance, or corrosion resistance of materials, as well as to modify their electrical, optical, or mechanical properties. Laser modification finds applications in diverse fields such as surface engineering, microfabrication, additive manufacturing, and semiconductor device processing, offering versatile solutions for tailored material properties and advanced manufacturing processes, like the achievements made by other modification techniques.727,728 In a work, Chen and co-workers reported a strategy to fabricate a rapid-response flexible temperature sensor with proximity sensing capability using laser-reduced graphene oxide (Figure 40e).722 In their experiments, UV laser was utilized to reduce GO for the sensor and it was found that the combined effects of GO concentration and laser scan line spacing can influence sensor sensitivity. Zhang et al. introduced a method for programmable and reprocessable multifunctional soft robots, enabled by designing and incorporating features and functions into elastomeric surfaces, as illustrated in Figure 40f.723 Specifically, the surfaces of elastomeric sheet can be modified by selective laser scanning. Upon modification, the elastomers’ functionalities can be controlled by infusing with particle solution and solvent retreatment. These processes find applications in smart soft robot and healthcare, offering tailored material properties and advanced actuation capabilities.  \n\nIn addition to laser cutting, engraving, and modification, various other laser-based fabrication techniques also play pivotal roles across industries, such as welding, sintering, marking, and so on. Together, these techniques expand the capabilities of laser-based fabrication, catering to diverse manufacturing needs across electronics manufacturing, soft robotics and beyond. Looking ahead, the prospects for laserbased fabrication are promising, with ongoing research pushing the boundaries of what is possible in terms of device functionalities and manufacturing capabilities. However, it is essential to acknowledge the limitations, such as complexity, scalability, cost, energy consumption, and material compatibility, which may pose challenges in certain applications. Nevertheless, with continued innovation and advancements in laser technology, the future holds exciting possibilities for the integration of laser-based fabrication techniques into diverse fields, driving forward the development of next-generation devices and technologies.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 34,
+        "chunk": "# 5.3. 3D Printing  \n\n3D printing, also known as additive manufacturing, is a process of creating three-dimensional objects by adding material layer by layer according to a digital design. Unlike traditional subtractive manufacturing methods, where material is removed from a solid block, 3D printing builds sophisticated structures and objects from the ground up, offering greater design  \n\n5.3.1. Principles of 3D Printing. According to the working principles, 3D printing technology can be classified as inkjet printing (IJP), direct ink writing (DIW), fused deposition modeling (FDM), digital light processing (DLP), stereolithography (SLA), two-photon polymerization (TPP), selective laser sintering (SLS), etc., and Figure 41a−f illustrates the working principles and process of six types of 3D printing technologies that are widely used.  \n\nInkjet printing (IJP) is a digital printing technology that utilizes small droplets of ink to create designed patterns on various substrates.737 The process involves ejecting ink droplets from a printhead (nozzle) onto the substrate in a controlled manner, driven by thermal or piezoelectric approach. In thermal inkjet printing, a tiny resistor heats up and vaporizes a small volume of ink, causing it to form a droplet that is ejected onto the substrate. In piezoelectric inkjet printing, electrically charged piezoelectric crystals change shape when exposed to an electric field, causing pressure changes that eject ink droplets from the printhead onto the substrate. Unlike traditional 3D printing methods, which rely on solid filaments or powders, direct ink writing (DIW) enables the deposition of soft, viscoelastic materials such as hydrogels, polymers, or colloidal suspensions by extruding ink or paste-like materials through a nozzle or syringe onto a substrate in a layer-by-layer fashion.738 In fused deposition modeling (FDM), thermoplastic filament is melted and extruded through a heated nozzle, which moves along a predetermined path.739 As the extruded material is deposited onto a build platform, it quickly solidifies, forming a solid layer. The build platform then moves down incrementally, and the process is repeated layer by layer until the entire object is complete. Digital light processing (DLP) uses a digital light projector to selectively cure liquid resin into a solid object.740 In DLP printers, a light source, typically a high-intensity UV lamp or LED, projects an image of each layer of the object onto a vat of liquid photopolymer resin. The image is projected onto the resin surface through a digital micromirror device, which contains millions of tiny mirrors that can tilt to either reflect light toward the resin or away from it. By selectively activating the mirrors according to the digital design, the desired pattern of light is projected onto the resin, causing it to polymerize and solidify where the light strikes. After each layer is cured, the build platform moves incrementally, and the process is repeated layer by layer until the entire object is formed. In stereolithography (SLA) printing, a liquid photopolymer resin is selectively cured, or solidified, layer by layer using a UV laser.741 The process begins with a vat of liquid resin, and a UV laser is directed onto the surface of the resin, tracing the shape of the object to be printed based on a digital 3D model. When the UV laser hits the liquid resin, it causes a chemical reaction that polymerizes the resin, transforming it from a liquid to a solid. Once a layer is cured, the build platform moves down slightly, and the process is repeated to create the next layer. Two-photon polymerization (TPP) is an advanced additive manufacturing technique used to create high-resolution three-dimensional structures at the micro- and nanoscale.742 Unlike traditional 3D printing methods that solidify materials layer by layer, TPP utilizes a focused laser beam to induce polymerization within a photosensitive resin. The process involves focusing ultrashort laser pulses (typically in the femtosecond range) at a specific point within the resin volume. When two photons of light are absorbed simultaneously by a photosensitive molecule, they combine their energy to induce a chemical reaction, causing the resin to solidify only at the focal point of the laser beam. By precisely controlling the movement of the laser beam relative to the resin, complex three-dimensional structures with submicron resolution can be fabricated.  \n\n5.3.2. Printing Soft Electronic Devices. 3D printing of soft electronic devices involves the fabrication of flexible and stretchable electronic components using additive manufacturing techniques.757−760 This process enables the integration of electronic functionalities into soft and deformable materials, such as elastomers or hydrogels, to create devices that can conform to complex shapes, bend, stretch, and even withstand deformation.761 The merits of 3D printing of soft electronic devices lie in its customization, complex geometries, material flexibility, integration of functionalities, etc. Recently, there has been a vast number of works on this field.  \n\nAlthough 3D printing has the potential to fabricate intricate and versatile soft electronic devices, printing solid-state elastic conductors with complex three-dimensional shapes poses a challenge due to the rheological properties of conventional inks, which typically allow only for layer-by-layer deposition. To address this issue, Lee et al. demonstrated the printing of elastic conductors in all directions enabled by an emulsion system, which is composed of a conductive elastomer composite, immiscible solvent, and emulsifying solvent (Figure 41g).743 By this approach, the direct writing of freestanding, filamentary, and out-of-plane three-dimensional shapes is possible with a minimum feature size of less than $100\\ \\mu\\mathrm{{m}}$ and a stretchability of over $150\\%$ . In another work, Wu and coworkers introduced a novel 3D printable tissue adhesive produced via direct-ink-writing technology, as shown in Figure 41h.744 This adhesive allows for the fabrication of flexible, stretchable, biocompatible bioadhesive patches and devices with customizable architectures, opening up new avenues for tailored designs to suit specific applications. Electronics fabricated from hydrogels bear intrinsic resemblances to biological tissue and hold significant promise for biomedical applications, and such devices should feature customizable three-dimensional circuits. However, the production of sophisticated three-dimensional circuits embedded within a hydrogel matrix poses challenges using current materials and manufacturing techniques. In Figure 41i, by employing a curable hydrogel-based supporting matrix and a stretchable silver-hydrogel ink, Hui et al. presented a novel approach for three-dimensional printing of hydrogel electronics.745 Owning to the yield stress fluid behavior of the matrix, it is possible for the precise placement of silver-hydrogel ink circuits and electronic components within. This approach enables the creation of electronic devices such as strain sensors, inductors, and biological electrodes, showcasing its versatility and potential for various applications. Printed electronics in extreme conditions, such as high temperature, is also of significance, with thermal insulation being one of the most predominant markets. Zhao et al. addressed the challenges in printing of silica aerogels with a direct ink writing method using a slurry of silica aerogel powder and a diluted silica nanoparticle suspension, leveraging shear-thinning behavior to enable easy flow during printing while maintaining shape postprinting, as exhibited in Figure 41j.746 The deployment of multimaterial 3D printing with precise subfeatures control could provide design space for generating multifunctional architected structures. Larson and co-workers presented a rotational multimaterial 3D printing platform that enables subvoxel control over the local orientation of azimuthally heterogeneous architected filaments (Figure 41k).747 By continuously rotating a multimaterial nozzle with a controlled ratio of angular-to-translational velocity, helical filaments with programmable helix angle, layer thickness, and interfacial area between multiple materials within a cylindrical voxel are successfully fabricated. This method further extends the capability of 3D printing technology for generating multifunctional architected matter inspired by biological motifs.  \n\n5.3.3. Printing Soft Actuators. Roboticists are exploring the creation of biologically inspired robots featuring soft or partially soft bodies, which hold promise for increased durability, adaptability, and safety in human interactions compared to traditional rigid robots. However, significant hurdles in the design and production of soft robots persist, including intricate fabrication processes and the integration of soft and rigid elements. 3D printing technology offers unique advantages in the production of soft actuators, allowing for the precise control of geometry, internal structure, and material composition. $732,762{\\-}{-}764\\$ This enables the creation of complex, customized actuators with tailored mechanical properties and functionalities with response to external stimuli such as heat, electricity, or light.765,766  \n\nDespite the progress made on soft robots, most of them still rely on tethering to rigid robotic control systems and power sources, which may limit their potentials in unstructured environments and other conditions. To fully unleash their potential, Wehner and co-workers introduced an entirely soft, autonomous robots using 3D printing technology, as shown in Figure 41l.110 In this work, not only the body, but the rest parts of soft robot, such as control and actuation module, are composed entirely of soft materials. For example, the control is achieved by microfluidic logic that autonomously regulates fluid flow, thus controlling the catalytic decomposition of an onboard monopropellant fuel supply. Gas generated from the fuel decomposition inflates fluidic networks downstream of the reaction sites, resulting in actuation, which facilitates the programmable integration of multiple materials and functions within autonomous robots. In another work, a combustionpowered robot with a body that transitions from a rigid core to a soft exterior was fabricated using multimaterial 3D printing by Bartlett et al., as shown in Figure $41\\mathrm m$ .748 This contrasting stiffness contributes to the seamless integration between the rigid driving components and the soft body, thereby enhancing the untethered jumping performance of the robot. To replicate the versatility and elegance of movements observed in complex muscle arrangements, Pascali et al. introduced a novel class of pneumatic actuators that are designed to contract and extend according to a mathematical model (Figure 41n).749 They can be implemented at various dimensional scales and with diverse materials and mechanical capabilities, such as a pneumatic artificial hand that can be fully three-dimensionally printed in a single step, enabling the emulation of lifelike movements.  \n\n![](images/fb550f87ea7feaf2b34a97fbba35ac9c77b24febcad88193beedebd73f2db520.jpg)  \nFigure 42. Various transfer printing technologies for soft electronic devices and robots. Schematic illustration of working principles of three different mechanically guided transfer printing technologies, including (a) kinetically controlled, (b) reversible adhesion, and (c) shear-enhanced. Reproduced with permission from ref 156. Copyright 2006 Springer Nature. Reproduced with permission from ref 776. Copyright 2010 United States National Academy of Sciences. Reproduced with permission from ref 777. Copyright 2011 American Institute of Physics. Schematic illustration of working principles of three different stimuli-triggered transfer printing technologies, including (d) laser-driven, (e) thermal controlled, and (f) magnetic controlled. Reproduced with permission from ref 778. Copyright 2023 American Association for the Advancement of Science. Reproduced with permission from ref 779. Copyright 2021 Wiley. Reproduced with permission from ref 780. Copyright 2019 Elsevier. Schematic illustration of other working principles for transfer printing, including (g) hydroprinting, (h) UV tape-assisted, (i) capillary forceassisted. Reproduced with permission from ref 781. Copyright 2017 Wiley. Reproduced with permission from ref 782. Copyright 2024 Springer Nature. Reproduced with permission from ref 783. Copyright 2017 American Chemical Society. (j) Large-area, conformable tattoo-like electrodes on human body. Reproduced with permission from ref 784. Copyright 2020 American Association for the Advancement of Science. (k) Wrap-like transfer printing for three-dimensional curvy electronics. Reproduced with permission from ref 785. Copyright 2023American Association for the Advancement of Science. (l) Conformable flexible sheets on spherical surfaces by transfer printing. Reproduced with permission from ref 786. Copyright 2023American Association for the Advancement of Science.  \n\nBesides the above 3D printing examples for soft actuators, this technology can also be used for printing of intelligent soft materials for robots that are capable of undergoing repeated shape-morphing and self-propulsion in reaction to external cues. In Figure 41o, Kotikian and co-workers utilized 3D printing to produce soft robotic materials comprising bilayers of liquid-crystal elastomers with orthogonal director alignment and varying nematic-to-isotropic transition temperatures.750 By modifying their chemistry and printed structure, the actuation behavior of the robot can be tailored, capable of assuming taskspecific configurations as needed. As economy and technology advance, incorporating sustainability principles into the development of novel fabrication methods is imperative. For this, Heiden et al. introduced a 3D printing process to fabricate fully biodegradable pneumatic actuators demonstrate omnidirectional movement with fast response times (Figure 41p).751 Additionally, they can be reprinted multiple times or disposed of without hazard at the end of their lifespan, potentially paving the way for a sustainable future in soft robotics.  \n\n5.3.4. Printing Soft Robots with Sensing Abilities. Moving further, sensing is essential for soft robotics as it enables these flexible and versatile systems to perceive, understand, and interact with their surroundings, and 3D printing of soft robots with sensing abilities is undoubtably one of the most promising ways to unlock the potential applications of this. In Figure 41q, Truby et al. employed embedded 3D printing technology to fabricate soft somatosensitive actuators.752 Multiple conductive features incorporated into a soft robotic gripper can provide proprioceptive and haptic feedback through embedded curvature, inflation, and contact sensors. This work facilitates the integration of complex sensing mechanisms into soft actuating systems, representing a crucial step toward achieving closed-loop feedback control in soft robots, machines, and haptic devices. In another work, Cui et al. introduced a design and manufacturing approach to produce a novel category of proprioception robotic metamaterials with self-sensing and feedback control, which could not only have multimodal locomotion abilities, but also can actively sense and execute movements (Figure 41r).753  \n\nPrinting of soft robot with sensing abilities can also be achieved by other principles. For example, 3D printable inks with ion-conducting, electroluminescent, and insulating dielectric properties are developed by Zhang et al., and this ink enables effortless and customizable 3D printing of flexible electroluminescent devices and soft robotics (Figure 41s).754  \n\nBy integrating the printed electroluminescent devices with a soft quadrupedal robot and sensing units, an artificial camouflage that can adapt to the environment by displaying matching colors is demonstrated, establishing an effective framework for next-generation soft camouflages. In another work, Truby et al. proposed a novel approach to sensorize architected materials via fluidic innervation.755 As illustrated in Figure 41t, networks of empty, air-filled channels are directly embedded within the actuator, the deformation information on the materials can be obtained by monitoring pressure changes within these channels. By 3D printing of sensorized structures from a single material, this strategy streamlines the design of sensorized materials by integrating structural, sensing, and actuation capabilities solely through geometric control, with applications ranging from wearables and smart structures to robotics. Although 3D printing examples of soft sensing robot keep increasing, the task of automatically and rapidly fabricating functional systems with diverse elastic properties, resolutions, and integrated actuation and sensing channels remains a significant hurdle. Buchner et al. propose a novel inkjet deposition process enables the creation of complex systems and robots, as shown in Figure 41u.756 The printing geometry was captured in this process to eliminate the need for mechanical planarizers, enabling the printing of a wider range of materials and elastic moduli. This approach offers an automated, scalable, and high-throughput process for producing sophisticated structures, functional devices, and robotic systems with enhanced performances.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 35,
+        "chunk": "# 5.4. Transfer Printing  \n\nThe increasing popularity of flexible and soft functional devices has driven the integration of components and functions on a platform seamlessly. Such components with high performance are usually fabricated on conventional substrates such as silicon wafer and should be transferred to the target substrate for the integration of flexible functional device. Transfer printing technology serves as a crucial technique for integrating diverse cdoevmicpeos antds sinoftt sopbaottisa.l7l6y o7r7g3 nIti edn, fumnpcatsisoens  erleacntgre iocf methods and techniques to reorganize materials, patterns, or functional components from one substrate to another. Such methodological approaches provide a versatile platform technology and adaptable means of fabricating high-performance, heterogeneously integrated functional systems at a costeffective scale.711,774,775 The key to the successful transfer printing is the proper control of energy release across different interfaces and there are several types of controlling strategies, such as mechanically guided, stimuli-triggered, and others.  \n\n5.4.1. Mechanically Guided. Mechanically guided transfer printing leverages the adhesion strength between the donor and receiver interface to achieve controllable adhesion and release of the components by regulate the interfacial mechanics. Meitl et al. reported a universal technique for transferring of different components based on a kinetically controlled approach by using an elastomeric stamp (Figure  \n\n42a).156 Specifically, they found the adhesion strength is dependent on the separation speed between two object and they can successfully control the transfer process by properly control the speed. This technique is not only facile and easy, but also applicable to different types of materials and sizes and shapes. In Figure 42b, Kim et al. provided another solution via pressure induced switching of adhesion strength between rigid objects and elastomeric surfaces to deterministically transfer of components.776 This adhesion strength can be reversibly switched by over 3 orders of magnitude. Besides, Carlson and co-workers introduced a shear-enhanced transfer printing technology for deterministic materials assembly, as illustrated in Figure 42c.777 They found the adhesion behavior could be effectively regulated by directional shear strain. Through analytical and finite element modeling, along with practical printing demonstrations, they uncovered the fundamental mechanics behind this process and showcase its potential for material assembly.  \n\n5.4.2. Stimuli-Triggered. Another commonly used transfer printing technique is stimuli-triggered transfer printing. In this technique, the adhesion strength between the transferred objects and the stamps can be controlled by external stimuli, such as laser, heat, vacuum, etc. By carefully engineering the properties of the materials involved, such as their adhesion strength, responsiveness to stimuli, and surface characteristics, transfer printing can be initiated or halted on demand. Chen and co-workers introduced a laser projection proximity transfer technique, in which the distance between the chip and stamp and their contact area can be regulated by hierarchical gasneedles stamp, as shown in Figure 42d.778 Combining exceptional adhesion switchability $_{\\sim1000}$ times) and high transfer accuracy $(\\sim4\\ \\mu\\mathrm{m})$ , this technique exhibits remarkable capabilities for deterministic microarray assembly, exemplified by its application in programmable microtransfer printing of MicroLED microchips for flexible displays. In addition, Luo et al. introduced a thermally controlled tunable adhesive capable of both eliminating interfacial adhesion during printing and enhancing it for pick-up, enabled by thermal-controlled suction and thrust, which not only facilitates reliable and damage-free transfer printing, but offer insights into the design and operation of the thermally controlled tunable adhesive (Figure 42e).779 In another work, Linghu et al. developed a magnetcontrolled transfer printing method and also constructed an analytical mechanics model to further elucidate the corresponding underlying mechanism, as illustrated in Figure 42f.780  \n\n5.4.3. Other Transfer Printings Methods. Apart from the previously mentioned mechanically guided and stimulitriggered transfer printing technologies, a range of alternative approaches are being employed for material transfer. These include hydroprinting, UV tape-assisted transfer printing, and capillary force-assisted transfer printing Figure $\\hat{4}2g\\mathrm{-i}$ 781−783 Each of these techniques is tailored for specific transfer scenarios. For instance, hydroprinting offers distinct advantages for transferring patterns onto 3D structures or curved surfaces, while UV tape-assisted transfer printing and capillary force-assisted transfer printing excel in transferring 2D materials with high fidelity, thereby expanding the possibilities for diverse performance and functionality.  \n\n5.4.4. 3D Curvy Electronics via Transfer Printing. The prevalence of 3D curved surfaces in both natural and industrial environments has catalyzed the emergence of 3D curved electronics, which can unleash many possibilities including conformable bioelectronics, antennas, bioinspired electronic eyes, metasurface engineering, and soft robotics.787−790 However, different from planar electronics, design and fabrication soft electronic devices that can be conformable to any 3D surface is challenging to both scientists and engineers. Transfer printing could be one of the most promising and effective way to fabricate electronics in a 3D manner. 791 For examples, Wang et al. presented a transfer process inspired by Cartan curves to creating large-area, soft, breathable, and conformable electrodes that can cover extensive areas such as the entire chest, forearm, or neck of human beings (Figure 42j).784 Chen et al. introduced an automated wrap-like transfer printing prototype, which is suitable for fabricating 3D curvy electronics. In this method, prefabricated planar circuits are seamlessly integrated onto the target surface, ensuring complete coverage, with the aid of a petal-like stamp under a gentle and uniform pressure field (Figure 42k).785 In Figure 42l, Liu and co-workers employed a blend of experimental, analytical, and numerical methodologies to thoroughly examine the conformability of circular sheets on spherical surfaces.786 By scrutinizing the buckling behavior of thin films on curved surfaces, a scaling law that accurately forecasts the conformability of flexible sheets on spheres is proposed in their work, providing insights for the future development of conformable electronics.  \n\n![](images/6d1cb0ea882029a96c5b7d57698e30b0182554e628530ca1a371ebce72c4d3b5.jpg)  \nFigure 43. Fabrication by assembly of components at different level scales: $(\\mathsf{a}\\mathrm{-}\\mathsf{d})$ materials level, $\\left(\\mathrm{e-h}\\right)$ electronic device level, (i−l) robotic system level. (a) Plasmonic welding of silver nanowire junctions. Reproduced with permission from ref 796. Copyright 2012 Springer Nature. (b) Direct bonding of gold electrodes onto ultrathin polymer films. Reproduced with permission from ref 797. Copyright 2021 American Association for the Advancement of Science. (c) Autonomous alignment and healing in multilayer polymers. Reproduced with permission from ref 798. Copyright 2023 American Association for the Advancement of Science. (d) Biphasic, nanodispersed interface for connection and encapsulation of soft-rigid electronic devices. Reproduced with permission from ref 799. Copyright 2023 Springer Nature. (e) Assembly of 3D electronics. Reproduced with permission from ref 800. Copyright 2018 Springer Nature. (f) Deterministically assembly of 3D curved mesosurfaces using microlattice designs. Reproduced with permission from ref 801. Copyright 2023 American Association for the Advancement of Science. (g) Highdensity bimodal sensor arrays by assembly. Reproduced with permission from ref 802. Copyright 2022 Wiley. (h) Monolithically integrated, lowvoltage, soft e-skin with capabilities of multimodal perception, neuromorphic pulse-train signal generation, and closed-loop actuation. Reproduced with permission from ref 803. Copyright 2023 American Association for the Advancement of Science. (i) Assembly of submillimeter-scale multimaterial terrestrial robots. Reproduced with permission from ref 804. Copyright 2022 American Association for the Advancement of Science. (j) Robotic system that can change its physical shape and compliance by collective assembly. Reproduced with permission from ref 805. Copyright 2024 American Association for the Advancement of Science. (k) Photograph of a robotic structural system that assembles individual block into a whole programmable structure. Reproduced with permission from ref 806. Copyright 2024 American Association for the Advancement of Science. (l) 3D miniature magnetic soft machines via multimaterial heterogeneous assembly. Reproduced with permission from ref 807. Copyright 2021 American Association for the Advancement of Science.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 36,
+        "chunk": "# 5.5. Assembly  \n\nAssembly typically involves the process of combining multiple parts or layers to create a new structure or device with innovative functionalities and form factors.792 This process often entails combining materials like polymers, metals, and semiconductors to form flexible substrates, circuits, sensors, and displays.595,789,793,794 For instance, in flexible sensors or wearable electronics, assembly involves integrating sensing elements, electronic components, and flexible substrates into a single device that can conform to the contours of the human body or other flexible surfaces.795 Here, according to the degree and complexity level of integration, we divide assembly into three categories: assembly on materials level, electronic device level, and robotic system level.  \n\n5.5.1. Materials Level. Starting from materials, assembly in this level involves the integration of two or more materials to form a single functional part, utilizing techniques such as welding, bonding, self-healing, and other principles. Garnett et al. presented a novel method called light-induced plasmonic nanowelding, which facilitates the assembly of metallic nanowires into large interconnected networks (Figure 43a).796 In this technique, light concentrate on the small gaps at nanowire junctions that need to be joined, ensuring physical connections between wires without causing damage to substrates. Takakuwa and co-workers introduced water vapor plasma-assisted bonding approach to facilitate the direct bonding of gold electrodes onto ultrathin polymer films in room temperature and atmospheric pressure (Figure 43b).797 In this process, the plasma can generate hydroxyl groups that aid in the bonding process between two gold surfaces, resulting in the formation of a robust and enduring interface. Cooper et al. also employed healing multilayered and functional polymers to assembly two materials together.798 As shown in Figure 43c, two distinct dynamic polymers with incompatible backbones yet sharing identical dynamic bonds can autonomously realign during this healing process. Jiang et al. created a biphasic, nanodispersed interface capable of seamlessly connecting soft, rigid, and encapsulation modules for durable and highly flexible devices (Figure 43d).799 This plug-and-play interface may streamline and expedite the development of stretchable devices for on-skin and other applications.  \n\n5.5.2. Electronic Device Level. In contrast to materiallevel assembly, electronic device-level assembly emphasizes the comprehensive functionalities of flexible electronic devices by integrating diverse materials, functional components, and other electronic devices to create a platform ready for immediate use. For example, Huang et al. presented a framework for the development of 3D integrated stretchable electronics with higher integration density on stretchable substrates and new functionalities compared with their conventional counterparts (Figure 43e).800 This approach involves constructing threedimensional devices layer by layer, employing transfer printing to place predesigned stretchable circuits onto elastomers and creating vertical interconnect accesses using laser ablation and controlled soldering, which is an exemplar implementation of assembly at electronic device level. Cheng et al. devised a mechanically guided assembly of programmable 3D curved mesosurfaces from 2D films, with demonstration for a conformable electronic device for cardiac and cell scaffold (Figure 43f).801 In another work, Cui et al. introduced an assembly approach for integrating 112 bimodal sensors into a thin, conformal, and stretchable tactile glove for body features extraction with an accuracy of $98\\%$ enabling the digitalization of tactile information, as shown in Figure $43\\mathrm{g.}^{802}$ By materials and structure design, Wang et al. demonstrated an e-skin that incorporates organic semiconductor transistors with capabilities including multimodal perception, neuromorphic pulsetrain signal generation, and closed-loop actuation (Figure  \n\n43h).803 This assembled electronic device bears merits like low subthreshold swing, low operation voltage, low power consumption, and moderate-scale circuit integration complexity.  \n\n5.5.3. Robotic System Level. At the robotic system level, assembly entails a more complex integration process compared to material or electronic device levels. This is because it involves not only materials properties, functions, and electronic devices, but also actuators, sensorimotor controllers, communication elements, and various other components. Moreover, several factors outside of aforementioned points must be carefully considered at this level, including systematic reliability, compatibility, robustness, etc. Han and co-workers demonstrated terrestrial robots with intricate, 3D geometries and multimodal movement capabilities enabled by heterogeneous material assembly (Figure 43i).804 Looking from another perspective, assembly should not be restricted from individual components or elements, and one robotic system could also assemble with another system to form a larger collective system. In response, Saintyves et al. reported a robotic system capable of altering both their physical shape and compliance to accommodate environmental constraints (Figure 43j).805 This system comprises gear-like units, each housing a single actuator, enabling units to self-assemble into larger granular aggregates. Gregg et al. also devised a robotic structural system that assembles individual block into a whole programmable structure, facilitating robust collective automated assembly and reconfiguration of large functional structures using robots (Figure 43k).806 In addition, Zhang et al. proposed a bottom-up assembly-based approach to 3D microfabrication of wireless magnetic soft machines at both the milli- and submillimeter scales (Figure 43l).807 This assembly method allows for the fabrication of structures with arbitrary multimaterial compositions, 3D geometries, and programmable magnetization profiles biomedical engineering applications.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 37,
+        "chunk": "# 6. SENSORIMOTOR CONTROL  \n\nSensorimotor control involves the coordination of sensory perception (as discussed in Section 2) with motor commands, or actuation (as discussed in Section 3) to enable a robot to perceive its environment and act accordingly. It is the process by which a robot uses its sensors (such as vision, touch, temperature, or proximity sensors) to gather data continuously about its surroundings and then adjusts its movements or behaviors based on this information.808−810 This control paradigm allows soft robots to interact with and navigate through their environment in a dynamic and adaptive manner. For example, a robot equipped with sensorimotor control can avoid obstacles, respond to stimuli in real-time, or manipulate objects with precision by constantly adjusting its actions based on real-time sensory feedback. Nowadays, researchers and engineers employ various techniques, including feedback control loops, machine learning algorithms, and sensory fusion strategies, to develop sophisticated sensorimotor control systems for soft robotics. This sensorimotor control architecture forms the cornerstone of next-generation soft robotic systems, offering unprecedented levels of autonomy, adaptability, and efficiency in diverse operational contexts.811",
+        "category": " Introduction"
+    },
+    {
+        "id": 38,
+        "chunk": "# 6.1. Sensorimotor Control Frameworks  \n\nIn essence, sensorimotor control mimics the way humans and animals interact with the world around them, where sensory input guides motor actions, enabling robots to perform tasks effectively and autonomously.152,812 Figure 44a illustrates the system architecture of a sensorimotor control framework and corresponding components involved.813 In the middle part of this classical sensorimotor control architecture, mechanical system (musculoskeletal system) represents the actuator, and sensory system (sensory receptors) the sensor. When soft robots interact with the environment or perform tasks, various information are collected by the sensors and then sent to controller (central nervous system) for further processing.814 Based on this information, different actuation commands are sent to the mechanical system in real time, and soft robots can respond to stimuli correspondingly. This cycle of task− sensor−controller−actuator enable the establishment of a closed-loop feedback for exteroception. It is worth to mention the internal state of the musculoskeletal system can also be reflected by sensory receptors. This internal physical stimulation is the proprioception of such system, providing the robot with awareness of its own body position, orientation, and movement, further contributing to its ability to execute tasks accurately and efficiently. Overall, the synergistic work between proprioception and exteroception serve as the foundation for enabling soft robots to interact with their environment, perform tasks, and exhibit adaptive behavior, akin to the sensory-motor capabilities observed in biological organisms.  \n\n![](images/0b2a2f2c8c0f748ca3485984b874123001597c5194a159c09f8dc9bd24d920a5.jpg)  \nFigure 44. Sensorimotor control frameworks for biological species and soft robots. (a) System architecture of a sensorimotor control framework and the main components involved in. Reproduced with permission from ref 813. Copyright 2007 American Association for the Advancement of Science. (b) Sensorimotor pathway in controlling locomotion for a cockroach, which represents a general model for sensorimotor control. Reproduced with permission from ref 815. Copyright 2000 American Association for the Advancement of Science. (c) Schematic of the neuromechanical system of locomotion in a hierarchical organization for vertebrates. Reproduced with permission from ref 816. Copyright 2023 The Company of Biologists. (d) Flow diagram of motor control principles with examples of robots. Reproduced with permission from ref 817. Copyright 2023 American Association for the Advancement of Science.  \n\nTable 3. Comparison of Modal-Based and Data-Driven Control of Soft Robot   \n\n\n<html><body><table><tr><td colspan=\"2\"> Approach</td><td> Principles</td><td>Advantages Assumes entire body bends with aSimplifes the mathematical modeling</td><td>Disadvantages Limited accuracy for large</td><td>Applicability Uniform bending situations where the complexity of variable curvature is not</td></tr><tr><td rowspan=\"10\">Model- based</td><td>Constant curvature (CC)</td><td>constant curvature</td><td> and control of bending segments</td><td>deformations or nonuniform curvature</td><td>necessary</td></tr><tr><td>Variable curvature (VC)</td><td>length of the segment</td><td>Allows curvature to vary along the More accurate representation of deformations, especially for complex</td><td>More complex to model and control, higher computational cost</td><td>Complex soft robotic structures where curvature varies along the length of the segment</td></tr><tr><td>Piecewise constant</td><td>Assumes segments bend with</td><td>bending Simplifies control and kinematic</td><td> May not capture complex</td><td>Continuum robots and soft robotic arms where smooth bending motions are</td></tr><tr><td>curvature (PCC) Piecewise constant</td><td>constant curvature Assumes constant strain within</td><td>modeling Simplifies computational efforts, suitable</td><td>deformations</td><td>required May notcapturehighstraingradientsStructuralanalysis,stres,and straincalculations where the deformation is linear</td></tr><tr><td>strain (PCS) Cosserat rod</td><td>each finite element Extends beam theory to include</td><td>for less complex strain variations Detailed description of deformations</td><td>accurately Complex to implement</td><td>and predictable within each segment Used in scenarios where the bending and twisting of flexible structures are critical</td></tr><tr><td>theory Hyperelastic</td><td>shear deformations Constitutive models for stress-</td><td>Captures nonlinear elastic behavior</td><td>Requires material-specific parameters</td><td>such as tentacles and manipulators in soft robotics. Modeling soft materials with nonlinear stress-strain relationships, like silicone in</td></tr><tr><td> material models</td><td>strain relationship of soft materials Mesh of finite elements for</td><td> accurately</td><td></td><td>soft robotics</td></tr><tr><td>Finite element method (FEM)</td><td>detailed deformations Based on experimental data or</td><td>Highly accurate, models complex interactions</td><td>Computationally intensive</td><td>Comprehensive simulations of stress, strain, and deformation in complex structure:</td></tr><tr><td>Black-box models</td><td>simulations Based on physical principles of</td><td>Adaptability, scalability, more computationally efficient</td><td>Lack of transparency, interpretability, and generalization</td><td>Efficient in handling complex and nonlinear relationships in various contexts.</td></tr><tr><td>White-box models</td><td>materials</td><td>Clear understanding of underlying physical principles and mechanisms</td><td>Labor-intensive and computationally expensive</td><td> Suitable for scenarios where detailed understanding of system mechanics is critical</td></tr><tr><td>Data-</td><td>Gray-box models</td><td>Based on physical principles and empirical results</td><td>Offers a blend of transparency and empirical flexibility</td><td>Requires significant computational resources and validation efforts</td><td>Versatile for scenarios where a blend of theory and data-driven insights is beneficial</td></tr><tr><td>driven</td><td></td><td> Supervised learning Based on labeled data learning</td><td>Structured learning and good interpretability</td><td>Requires large amounts of labeled data for training and limited adaptability</td><td>Can train models to classify specific motions or states based on labeled training data, enabling precise control and interaction</td></tr><tr><td></td><td>Reinforcement learning</td><td>Based on data learning</td><td>Adaptive, continuous learning, and versatility</td><td>Requires significant computational resources and time</td><td>Can enable soft robots to adapt their grasp strategy based on feedback from sensors andthesuccess ofpreviousattempts,improvinggrasping efficiencyandreliability</td></tr></table></body></html>  \n\nTo make this sensing-action loop more intuitive and clearer, sensorimotor pathway in controlling the locomotion of a cockroach is provided in Figure 44b.815 The interaction between the central nervous system (CNS) and the musculoskeletal system orchestrates the motor actions of an animal. The CNS generates motor commands that prompt the musculoskeletal system to act upon the external environment. Concurrently, the external environment is sensed through various modalities, and this sensory information is relayed back to the CNS for processing. Sensory feedback can be broadly categorized into guidance and equilibrium cues from diverse modalities, represented together as light blue, and rapid phasic feedback from mechanosensors, depicted in dark blue. The CNS integrates this sensory feedback and adjusts the motor commands accordingly, facilitating adaptive responses. Simultaneously, viscoelastic mechanical preflexes, depicted in red, swiftly counteract perturbations, contributing to the animal’s stability and agility in dynamic environments. This intricate interplay between sensory feedback, motor commands, and mechanical preflexes enables animals to navigate and interact effectively with their surroundings.  \n\nLooking from the point of view of neuromechanics, sensorimotor control in vertebrates is more complexed and exhibits a hierarchical organizing structure, as shown in Figure 44c.816 In such hierarchical organization, central pattern generators (CPGs) serve as the foundation, generating rhythmic commands that act as feedforward signals for coordinating basic tasks and movements. Descending commands from higher brain centers then activate and modulate these CPGs, allowing for task selection and refinement of motor patterns based on contextual demands and goals. Additionally, reflex pathways contribute by providing rapid and stabilizing responses to external perturbations, ensuring stability and adaptability during motor execution. This hierarchical framework illustrates how different levels of neural control collaborate to orchestrate complex behaviors, with CPGs providing fundamental rhythms, descending commands refining motor output, and reflexes ensuring robustness in the face of environmental challenges.  \n\nAdvancements in understanding the interneuronal networks and cellular mechanisms involved in sensorimotor control have revealed the multifaceted integration of sensory feedback. It is now evident that sensory information is processed at multiple levels within the nervous system. First, sensory feedback operates through distinct reflex pathways, enabling rapid and automatic responses to immediate stimuli. Additionally, sensory signals modulate CPGs, influencing rhythmic motor patterns and coordination, such as walking or swimming. Moreover, these inputs converge with longer-latency feedback loops, integrating information to regulate higher-order functions such as navigation, task selection, and other adaptive and goal-directed behaviors. This hierarchical integration of sensory feedback underscores the complexity and sophistication of sensorimotor control mechanisms, highlighting the intricate interplay between neural circuits and sensory inputs in orchestrating motor actions and behaviors.  \n\nThe principles of motor control elucidated through studies on biological systems have not only advanced our understanding of fundamental science but have also been instrumental in shaping the development of robotic systems. By studying how animals control their movements, researchers have gained valuable insights into the underlying neural mechanisms, sensory processing, and biomechanical principles involved in motor control. These insights have, in turn, inspired the design and optimization of robotic control algorithms, sensor technologies, and mechanical architectures, as depicted in Figure 44d.817 For example, rhythmic bursts of activity generated by CPGs can facilitate coordinated movements of robots, as the four-legged walking robots marked by teal. Additionally, motor circuits receive feedback from mechanosensory and proprioceptive receptors in the body and limbs, enabling reflex-based control (robots marked by red). Moreover, robot marked by red and teal employes CPG dynamics adjusted by mechanosensory feedback to enhance locomotion robustness and efficiency in uncertain environments.  \n\nOverall, the translation of core motor control principles from biological systems to robotics not only advances our scientific understanding but also drives innovation in engineering, leading to the development of more capable, adaptive, and efficient robotic systems with a wide range of applications across industries.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 39,
+        "chunk": "# 6.2. Control of Soft Robots  \n\nThe control of soft robots presents unique challenges due to their compliant and deformable nature.818−821 Unlike traditional rigid robots, soft robots often lack precise and predictable kinematics, making traditional control methods less applicable. However, several approaches have been developed to address these challenges and effectively control soft robots. A comparison between the control approaches used in soft robots is made in Table 3.  \n\n6.2.1. Model-Based Control. Model-based control of soft robots involves using mathematical models that accurately describe the behavior of the robot’s deformable structure and actuators.822−824 Unlike rigid-body models commonly used in traditional robotics, these models incorporate the complex mechanics of soft materials, accounting for their nonlinear elasticity, compliance, and deformation characteristics. By developing appropriate models tailored to the unique characteristics of soft materials, such as finite element method (FEM) model,825 piecewise constant strain (PCS) model,826 and piecewise constant curvature (PCC) model,827 the relationship between actuator inputs and resulting deformations can be accurately predicted and thus the full potential of soft robotics can be entirely unlocked.  \n\nDrawing inspirations from humans performing interactive tasks, Jiang et al. proposed a hierarchical control system for soft arms, which is composed of three levels: a low-level controller for motion control of the arm tip, a high-level controller for behavior control based on the low-level controller’s outputs, and a top-level planner for task selection (Figure 45a).828  \n\n![](images/26b4b549c10e075f7b390afa8639322b16aa6c59570db48f0e051b80caef4aa2.jpg)  \nFigure 45. Control of soft robot, including model-based control, data-driven control, and hybrid control. (a) Soft manipulators by hierarchical control. Reproduced with permission from ref 828. Copyright 2021 SAGE Publications. (b) Soft manipulator for dynamic tasks. Reproduced with permission from ref 829. Copyright 2023 Wiley. (c) Octopus-inspired sensorized soft arm. Reproduced with permission from ref 137. Copyright 2023 American Association for the Advancement of Science. (d) Photograph and schematic illustrations of the soft robotic flatworm during locomotion. (e) Control framework of the soft robotic flatworm. Reproduced with permission from ref 832. Copyright 2023 Wiley. (f) Architecture of control hierarchy inspired by octopus. (g) Schematic illustration of the working process of the hierarchical control. (h) Architecture of neural network energy shaping control. Reproduced with permission from ref 835. Copyright 2023 Wiley.  \n\nSpecifically, two control models are employed to achieve motion control of the soft arm during interactions with the environment: simplified Jacobian model and Q-learning-based control model. Benefit from such models, the soft arms can perform interaction tasks akin to humans, without the need for sensory inputs or additional environment models. In order to make soft robot move faster and manipulate more efficiently, Fischer et al. introduced a dynamic model by incorporating additional elements such as variable stiffness and actuation behavior in soft robotic manipulators for their dynamic control, as shown in Figure 45b.829 In another work, Xie and co-workers reported an octopus-inspired soft robotic arm integrated with sensorized skin that are capable of reaching, sensing, grasping, and interacting with the environments (Figure 45c).137 The effective movement and interaction of this soft arm is based on a bending-elongation propagation model, offering insights into the development of soft electronic devices and actuators and their integration.  \n\n![](images/bbb7c1c129c70369f378d71a102f67c285548856dc39c943347b147e274e0a44.jpg)  \nFigure 46. Other emerging approaches for the control of soft robot. (a) Embodied intelligence. Reproduced with permission from ref 846. Copyright 2015 American Association for the Advancement of Science. (b) Morphological computation. Reproduced with permission from ref 847. Copyright 2017 Taylor & Francis. (c) Mechanical computing. Reproduced with permission from ref 848. Copyright 2021 Springer Nature. (d) Energy-efficient gait with minimal control by avian-inspired leg clutching. Reproduced with permission from ref 849. Copyright 2022 American Association for the Advancement of Science. (e) Swarm of sterically interacting robots by morphological computation. Reproduced with permission from ref 850. Copyright 2023 American Association for the Advancement of Science. (f) Digital pneumatic logic for soft robotic control. Reproduced with permission from ref 851. Copyright 2024 American Association for the Advancement of Science.  \n\nModel-based control offers several advantages for soft robots, including the ability to predict and optimize performance, design controllers tailored to specific tasks, and analyze the effects of different design parameters. However, accurate modeling of the complex mechanics of soft materials remains a significant challenge, requiring careful consideration of nonlinearities, material properties, and environmental factors.  \n\n6.2.2. Data-Driven Control. Data-driven control of soft robots involves leveraging experimental or real-world data to develop control strategies without relying heavily on analytical models.830,831 Unlike model-based control, which requires accurate mathematical descriptions of the robot’s dynamics, data-driven control focuses on learning control policies directly from data collected during robot operation. For example, Ju et al. reported a reinforcement learning-based control framework tailored for soft robots with high degrees of freedom, as shown in Figure 45d.832 This framework is designed to enable the execution of global tasks by coordinating the actions of multiple segments equipped with independently controllable embedded actuators. The control policies are formulated leveraging localized proprioceptive self-sensing capabilities, allowing for effective feedback control within each segment (Figure 45e). As demonstration, soft physical robots are developed and deployed in various tasks as expected, thereby validating the effectiveness and applicability of such a datadriven-based control framework in enabling multifunctional, high degrees of freedom soft robots to perform complex tasks.  \n\nData-driven control offers several advantages for soft robots, including the ability to adapt to complex and uncertain environments, learn from experience, and handle nonlinear and time-varying dynamics without requiring explicit models.833,834 However, data-driven approaches may require large amounts of training data and careful consideration of issues such as overfitting and generalization. Additionally, interpretability and robustness can be challenges with complex machine learning models. Despite these challenges, data-driven control presents a promising approach for advancing the capabilities of soft robots in real-world applications.  \n\n6.2.3. Hierarchical/Hybrid Control. The octopus exhibits a neural architecture that contrasts sharply with the predominantly centralized brain structure found in vertebrates.836,837 Instead of a centralized brain, two-thirds of the octopus’s neural tissue is distributed throughout its arms, primarily responsible for low-level sensorimotor tasks and coordination of whole-arm movements (Figure 45f). In contrast, the central nervous system comprises the remaining third of the neural tissue that is responsible for higher-level functions such as learning and decision-making, integrating signals from the entire body. This hierarchical organization enables the octopus to exhibit complex behaviors and adaptability, showcasing the efficiency and versatility of decentralized control systems in biological organisms. Inspired by this hierarchical structure, Shih and co-workers introduced a hierarchical control/hybrid control framework for the purpose of coordination of multiple soft arms, consisting of three hierarchical levels: high-level decision-making, low-level motor activation, and local reflexive behaviors via sensory feedback.835 As shown in Figure $45\\mathrm{g},$ while central level works for decision making, such as reaching for food or crawling, muscle activations translate incoming commands into suitable deformations at the arm level through a rapid energy-shaping method aimed at reducing energy consumption. Figure 45h describes the architecture of neural network energy shaping control. It should be noted that model-free reinforcement learning in this work is mainly for high-level decision-making and model-based energy shaping for arm-level motor execution. Also, there’re also some proposed hierarchical sensorimotor control frameworks for human-in-the-loop robotic hands.810",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 40,
+        "chunk": "# 6.3. Emerging Approaches  \n\nIn addition to traditional control strategies for soft robots, such as model-based, data-driven, and hybrid control, emerging techniques like embodied intelligence, morphological computation, and mechanical computing offer significant advantages.25,838−842 Compared to conventional methods, these unconventional approaches have the merits ranging from enhancing energy efficiency, adaptability, and simplifying control by utilizing the robot’s physical interactions with its environment to reduces computational load and improves taskspecific performance and to offer inherent parallelism, greater durability, and seamless integration with soft materials. These unconventional approaches capitalize on the physical properties of soft robots, resulting in more efficient, adaptable, and robust control systems.  \n\n6.3.1. Embodied Intelligence. Embodied intelligence means that intelligence is not solely confined to the brain or central processing unit of an agent but is distributed throughout its entire body or structure. In other words, the physical design and material properties of the soft robot contribute significantly to its ability to perceive, interact with, and adapt to its environment.843  \n\nIn soft robotics, the physical embodiment of the robot, typically made from compliant and deformable materials, plays a crucial role in its intelligence. By designing the robot’s body to have properties such as compliance, variable stiffness, and dexterity, it can better navigate complex and dynamic environments. Rather than relying solely on complex algorithms or centralized control systems, soft robots leverage their physical structure to perform tasks efficiently and adaptively. For example, a soft robotic gripper with compliant fingers can conform to the shape of objects it grasps, allowing for more reliable and versatile manipulation.844 Similarly, a soft-bodied robot with variable stiffness can adjust its rigidity to navigate different terrain or interact safely with humans.845 In essence, embodied intelligence in soft robotics emphasizes the integration of sensing, computation, and action within the robot’s physical form, enabling it to exhibit intelligent behavior without the need for extensive programming or external control.  \n\nFigure 46a provides a possible architecture of embodied intelligence, with the abilities to seamlessly integrate sensing, computation, and actuation throughout the continuous structure.846 Sensors embedded within the material can detect changes or stimuli across its entire surface, while computing elements process this information locally. Actuators embedded within or connected to the material can then respond to these signals, allowing for distributed and coordinated motion or behavior. This continuous coupling between sensors and actuators at different locations enables soft robots to adapt and interact with their environment in a more fluid and versatile manner.  \n\n6.3.2. Morphological Computation. While embodied intelligence provides the overarching framework that encompasses the interaction between the robot and its environment, morphological computation is a specific mechanism through which this interaction occurs, emphasizing the role of the robot’s physical morphology in achieving intelligent behavior.852 In another words, embodied intelligence broadly involves the idea that intelligence emerges from the interaction between an agent (such as a robot) and its environment, with the agent’s body playing a central role in this interaction.850 This includes not only the physical structure of the robot but also its sensory and motor capabilities. Whereas, morphological computation specifically focuses on how the physical morphology of the robot, including its shape, material properties, and mechanical design, can contribute to computational processes. It emphasizes the idea that the robot’s body itself can perform computations or assist in problem-solving tasks, reducing the reliance on centralized control or complex algorithms. Thus, embodied intelligence encompasses the broader framework within which morphological computation operates. Eder and co-workers introduced a morphological computation-based control approach for a highly complex pneumatically driven robotic arm composed of multiple modular segments (Figure 46b).847 By harnessing the dynamics of the robot as a computational resource, the control task is simplified to a straightforward linear regression process, thereby streamlining the control process and enhancing computational efficiency. This work underscores the potential of morphological computation in revolutionizing control strategies for soft robotics, offering a promising pathway toward achieving robust and efficient control in complex robotic systems.  \n\n![](images/0c279a2d878d622879bb35cc7c99c8a1ff37030e630cfc67ebcc098d31a4995b.jpg)  \nFigure 47. (a) Venn diagram of machine learning algorithms learning concepts and classes with model sketch maps. (b) Diagram showing the convergence of AI with soft robots as Soft Robot Agent AI. (c) An overview of the implementation of Soft Robot Agent AI.  \n\n6.3.3. Mechanical Computing. While electronic computing offered advantages in miniaturization and integration, recent developments have spurred a reevaluation of mechanical mechanisms in conjunction with materials science and robotics. This interdisciplinary approach opens avenues for novel computing systems that interact with and adapt to their environment, augmenting traditional electronic computing. Yasuda and co-workers gave their insights into the mechanical computing as a new paradigm for soft robotics, and also provided an architecture for such unconventional computing (Figure 46c).848 By leveraging adaptable materials and structures as a distributed information processing network, mechanical computing systems introduce a paradigm where information processing becomes akin to a material property, alongside traditional attributes like strength and stiffness. The acknowledgment of information processing as a material property heralds a transformative shift in computing systems, necessitating a multidisciplinary approach to address the ensuing challenges, including materials science, information theory, computer science, additive manufacturing, and robotics. The framework they provided would serve as a catalyst for innovation, inspiring researchers to explore new avenues in material-driven computation and finally paving the way for groundbreaking advancements in sensorimotor control of soft robotics.  \n\nOverall, we’ve delved into three key concepts within the field of soft robotics: embodied intelligence, morphological computation, and mechanical computing. Not independent of each other, each of these concepts offers unique insights into the design and operation of robotic systems, highlighting the importance of the physical embodiment, material properties, and interaction with the environment in achieving intelligent behavior. By integrating these principles, researchers can develop innovative approaches to robotics and control, as the three examples shown in Figure 46d−f, that push the boundaries of traditional methodologies and pave the way for new technological advancements.849−851 It can be envisioned that the weights of these emerging approaches in the control of soft robotic systems will be poised to grow.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 41,
+        "chunk": "# 7. ARTIFICIAL INTELLIGENCE (AI) IN SOFT ROBOTS WITH SENSORIMOTOR FUNCTIONS  \n\nArtificial intelligence (AI), machine learning (ML), and deep learning (DL) play crucial roles in robotics.853,854 Robots utilize these technologies to perceive and interact with their environment, make decisions, and execute complex tasks.855 Sensing and actuation components are vital for robots to interpret various signals and perform actions such as grasping and manipulation. As a result, a variety of ML and DL techniques are employed in these tasks. The integration of ML, and DL into robotics holds great potential, empowering robots to enhance their intelligence, autonomy, and effectiveness across various applications.856  \n\nWith equal significance, the integration of AI with electronic sensing devices exemplifies humanity’s drive for innovation and efficiency, significantly enhancing sensor capabilities and transforming our interaction with the world.857 AI-enabled sensors are reshaping industries such as healthcare diagnostics and industrial automation by improving data analysis and predictive capabilities. These devices capture diverse inputs\u0001 like strain, pressure, and temperature\u0001using AI for advanced pattern recognition and predictive analysis, yielding diverse outputs from gesture recognition to material property calculations.  \n\nThe convergence of AI and soft robotics marks a new era of innovation, overcoming previous limitations and equipping soft robots with cognitive abilities for perception, learning, and intelligent decision-making. This synergy has the potential to revolutionize industries such as healthcare, manufacturing, and exploration by enabling soft robots to navigate uncertainties, adapt to dynamic environments, and perform tasks with precision. AI also enhances control in soft robotics through machine learning and neural networks, allowing adaptive and responsive strategies for diverse environments. Overall, the integration of AI in soft robotics fosters unprecedented advancements, transforming how robots perceive, interact with, and adapt to their surroundings, thereby pushing the boundaries of robotic systems.",
+        "category": " Introduction"
+    },
+    {
+        "id": 42,
+        "chunk": "# 7.1. Machine Learning Framework  \n\nIn the era of the Fourth Industrial Revolution (Industry 4.0), vast amounts of data, including IoT data, cybersecurity data, mobile data, business data, social media data, and health data, are generated. The intelligent analysis of this data and the development of smart, automated applications hinge on the knowledge of AI, particularly, ML.858 This field synthesizes concepts from various disciplines, including artificial intelligence, probability and statistics, computer science, information theory, psychology, control theory, and philosophy.859 Within the realm of machine learning, various techniques such as classification analysis, regression, data clustering, feature engineering, dimensionality reduction, association rule learning, and reinforcement learning are utilized to effectively construct data-driven systems.  \n\nML models and Artificial neural networks (including DL) used in robotics are shown in Figure 47a. Machine learning includes basic machine learning methods and artificial neural networks (which can be further classified into shallow neural networks and deep neural networks). Traditional ML algorithms contain SVM (support vector machine), decision tree, kNN (k-nearest neighbor) and Adaboost. Random forest (RF) learning model with multiple decision trees uses “parallel ensembling” which fits several decision tree classifiers in parallel on different data set subsamples and uses majority voting or averages for the outcome or final result. In sensorrelated research, supervised learning methods such as kNN, SVM, and supervised deep learning models are predominantly utilized. These algorithms are primarily employed for classification tasks, enabling the differentiation of various objects upon contact. Unlike the random forest that uses parallel ensembling, Adaboost uses “sequential ensembling”. It creates a powerful classifier by combining many poorly performing classifiers to obtain a good classifier of high accuracy. In DL algorithms, CNNs (convolutional neural networks), RNNs (recurrent neural networks), MLPs (multilayer perceptions), autoencoder, and transformer. CNNs are commonly utilized for image recognition tasks due to their ability to effectively capture spatial patterns. In addition, CNNs are employed for sensors with two-dimensional array data types, such as e-skin. These networks are used for tasks such as object contact classification. RNNs excel in sequential data processing tasks such as speech recognition and natural language processing. Therefore, algorithms, such as RNN and long short-term memory (LSTM), adept at handling timeseries data are frequently used for time-series classification and execution tasks.860 MLPs are versatile neural networks used for various tasks including classification and regression. These algorithms are sensitive to feature scaling and offer various tunable hyperparameters, such as the number of hidden layers, neurons, and iterations, which can lead to computationally expensive models. Autoencoders are unsupervised learning models utilized for feature learning and data compression tasks. Transformers, known for their attention mechanism, have revolutionized natural language processing tasks, particularly in machine translation and text generation.  \n\nDifferent machine learning algorithms serve distinct purposes in soft robotics applications. For electronic sensing devices, CNNs excel at processing spatial data from distributed sensor networks and visual feedback, while MLPs are versatile for sensor calibration and multisensor fusion. RNNs demonstrate superior performance in temporal sequence prediction and continuous motion control due to their memory capabilities. The transformer architecture enables complex sequence-to-sequence tasks and simultaneous processing of multiple sensor inputs. Autoencoders are particularly valuable for dimensionality reduction and denoising of highdimensional sensor data. Supporting algorithms like SVMs and decision trees provide efficient solutions for classification tasks and interpretable control decisions. The integration of multiple algorithms often yields the most robust solution: CNNs handle perception tasks, RNNs manage temporal predictions, while lighter architectures like MLPs or decision trees enable realtime control. The selection of specific algorithms depends on the application requirements, such as computational resources, response time, and the complexity of the sensing or control task. In terms of soft robotic control, various machine learning approaches offer unique advantages. Reinforcement learning (RL) has demonstrated remarkable capabilities in learning complex control policies for soft robots through trial-and-error interactions with the environment. Deep RL algorithms can handle the high-dimensional state spaces typical in soft robotics, learning to map sensory inputs directly to actuation commands while adapting to material nonlinearities and environmental uncertainties. Model-based RL approaches are particularly valuable as they can learn dynamic models of the soft robot’s behavior, enabling more efficient policy learning and better generalization to new tasks. For trajectory optimization, RNNs and LSTMs excel at learning continuous motion patterns and predicting deformation behaviors, while MLPs can efficiently map desired states to actuation inputs. Hybrid approaches that combine multiple algorithms have been found to be most effective, as they can leverage the strengths of each algorithm to provide a comprehensive solution for soft robotic tasks.  \n\nAs shown in Figure 47b, the convergence of artificial intelligence (AI) and soft robotics represents a transformative shift in the capabilities of robotic systems, driven by the integration of advanced “brains” and adaptive “bodies”. This integration follows a progression through six levels of development: structural, mechanism, movement, perceptual, cognitive, and fully autonomous. At the structural level, the focus lies on designing and optimizing soft robotic bodies, leveraging flexible materials and novel fabrication techniques to mimic biological forms. As the system evolves to the mechanism level, AI is employed to refine actuation and mechanical operations, ensuring seamless interaction between the robot’s components. The movement level emphasizes coordinated and adaptive motion, where AI algorithms enable tasks like locomotion and manipulation, bridging the gap between mechanical design and environmental interaction. The integration deepens at the perceptual level, where AI facilitates advanced sensing capabilities, allowing robots to interpret tactile, visual, and environmental inputs with greater precision. This stage enhances the robot’s responsiveness to external stimuli, enabling effective interaction with dynamic surroundings. Progressing to the cognitive level, AI drives learning, decision-making, and reasoning processes, empowering robots to undertake complex tasks such as navigation, problem-solving, and collaborative operations. Finally, at the fully autonomous level, robots achieve independence, performing intricate tasks with minimal or no human supervision in unstructured and dynamic environments. This continuum reflects a decreasing reliance on human oversight and an increasing capacity for robotic self-regulation, marked by the progressive enhancement of both physical and cognitive functionalities. The integration of AI in this framework not only transforms soft robotics but also unlocks new opportunities for autonomous systems in healthcare, manufacturing, and exploration. As robots evolve into entities with stronger “brains” and perceptive “bodies,” the synergy between AI and soft robotics continues to shape the future of intelligent, adaptable machines.  \n\nIn this review, we define such soft intelligent machines as Soft Robot Agent AI. This represents a sophisticated integration of agent-based artificial intelligence with soft robotic systems, combining cognitive intelligence with physical adaptability to enable autonomous and intelligent behavior in complex environments. In this framework, the AI agent functions as a decision-making entity that perceives its environment, processes sensory data, and executes actions to achieve predefined goals. The inherent flexibility and compliance of soft robotic structures enhance this capability, allowing these systems to perform intricate tasks in dynamic and unstructured conditions. The synergy between AI and soft robotics facilitates a seamless interaction between sensing, actuation, and control, enabling robots to autonomously navigate, manipulate, and interact with their surroundings. By leveraging advanced machine learning techniques, such as reinforcement learning and neural networks, Soft Robot Agent AI systems can continuously adapt and optimize their performance based on real-time feedback. The implementation of Soft Robot Agent AI (Figure 47c) involves the integration of artificial intelligence with soft robotic systems, creating an intelligent agent capable of perceiving, learning, and acting autonomously in complex environments. This process begins by embedding multimodal sensory inputs, such as visual, tactile, auditory, and environmental data, into the robot, enabling it to perceive its surroundings in real-time. These inputs are processed through AI algorithms that allow the agent to recognize and interpret stimuli, adapt to changing conditions, and make informed decisions based on its environment. A critical aspect of this implementation is the use of a closed-loop feedback system for continuous learning, where sensory inputs are continuously fed into the AI, allowing it to adjust its actions and improve performance over time. The integration of learning models allows the system to adapt and optimize its decision-making processes through experience. Furthermore, memory systems help the robot store and retrieve knowledge, enabling it to reason and make informed decisions based on past experiences.  \n\nBy grounding the agent in both physical and virtual environments, Soft Robot Agent AI can interact with the world in a more robust, context-aware manner. The interaction between perception, cognition, and action enables the robot to respond dynamically and intelligently to environmental changes, while ensuring accuracy and relevancy in decisionmaking. This multilayered, adaptive system enhances the robot’s versatility, making it suitable for diverse applications such as healthcare, human−robot collaboration, and industrial automation.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 43,
+        "chunk": "# 7.2. AI for Flexible Electronic Sensing Devices  \n\nIn an era marked by the relentless advancement of technology, the marriage of AI with electronic sensing devices stands as a testament to humanity’s quest for innovation and efficienc y.861−865 This amalgamation not only empowers electronic sensors with enhanced capabilities but also revolutionizes the way we perceive and interact with the world around us.866 From the intricacies of healthcare diagnostics to the complexities of industrial automation, AI-infused soft sensing devices are reshaping industries, augmenting human capabilities, and unlocking new realms of possibilit y.862,863,867,868 In this exploration, we delve into the realm of AI-enabled electronic sensing devices, unraveling their transformative potential, applications, and the profound impact they wield on our daily lives and the future of technology.  \n\n![](images/d8cfa29dfb7f16557743045b4ff2cacdcdbb76daf92ff7fed37475b8dee0b1ee.jpg)  \nFigure 48. Artificial intelligence for flexible electronic sensing devices. (a) Working flow of electronic sensing devices with AI for signal processing. (b) RF for gas classification. Reproduced with permission from ref 870. Copyright 2022 American Association for the Advancement of Science. (c) kNN for decoding of facial expressions. Reproduced with permission from ref 871. Copyright 2020 Springer Nature. (d) SVM for sign-to-speech translation. Reproduced with permission from ref 872. Copyright 2020 Springer Nature. (e) CNN for learning human grasping and object recognition. Reproduced with permission from ref 67. Copyright 2019 Springer Nature. (f) AdaBoost for monitoring blood pressure. Reproduced with permission from ref 873. Copyright 2022 Springer Nature. (g) GlovePose for hand movement capturing. Reproduced with permission from ref 877. Copyright 2024 Springer Nature.  \n\nThe fusion of AI with electronic sensing devices has been regarded as an indispensable approach in the intricate tapestry of modern flexible sensing landscapes. Their true potential lies not merely in data collection, but in the transformative power of AI-driven analysis and more, serving as the catalyst for unlocking the latent insights buried within the deluge of sensory data.869 As the illustrated working flow of AI in electronic devices in Figure 48a, for example, these devices are first designed to capture a myriad of inputs ranging from strain and pressure to temperature and chemical composition. Harnessing the capabilities of AI, these electronic sensing devices transcend mere observation, delving into the realms of pattern recognition and predictive analysis. The outputs generated by this symbiotic relationship between sensor and AI are as diverse as the inputs they process. From the recognition of gestures and textures to the calculation of Young’s Modulus and thermal conductivity, this powerful tool can enhance our understanding of the physical world in unprecedented ways.  \n\nThe applications enabled by the marriage of sensory input and AI-driven analysis span a vast spectrum of fields. Capman et al. introduced graphene-based variable capacitor arrays, containing functionalized sensors with different chemical receptors (Figure 48b).870 Powered by random forest classification (RF), gas classification with an accuracy of $98\\%$ can be achieved, which is comparable with analytes. This finding highlights the critical role of analysis methods, particularly machine learning, in noisy environments. In another work, Sun and co-workers employed kNN to decode of facial movements via real-time detection and classification of skin-deformation signatures by conformable piezoelectric thin films, holding promise for nonverbal communication technology and neuromuscular condition monitoring (Figure 48c).871 In addition to facial expression, hand gestures can also be recognized and translated to language assisted by AI. As shown in Figure 48d, Zhou and co-workers demonstrated a wearable sign-to-speech translation system, consisting of yarn-based stretchable sensor arrays and a wireless printed circuit board.872 Features extracted from transmitted data act as inputs for the trained multiclass SVM classifier, which can enhance the accuracy and resilience of the wearable sign-tospeech translation system. Also aiming at hand, Sundaram et al. demonstrated a wearable glove integrated with 548 tactile sensors to learn the signatures of the human grasp, as shown in Figure 48e.67 The integration of a scalable tactile glove with a deep CNN to identify objects, estimate their weight, and analyze tactile patterns during grasping is intriguing. The largescale data set collected from interactions with various objects, together with machine learning techniques could provide valuable insights into human grasping dynamics.  \n\n![](images/6af96b1e13847ea106d84133656181849055bfc5256a1e7fdffbdf601f060508.jpg)  \nFigure 49. Artificial intelligence for soft robotic systems. (a) Working flow of perception robotic systems with inputs of information such as vision, tactile, hearing, and magnetic. Followed by signal processing with AI, a variety of applications can be the enabled as the output of this system. Examples including (b) RNN for soft robotic proprioception. Reproduced with permission from ref 882. Copyright 2019 American Association for the Advancement of Science. (c) CNN for bending perception. Reproduced with permission from ref 883. Copyright 2021 Cambridge University Press. (d) kNN for robotic physicochemical sensing Reproduced with permission from ref 884. Copyright 2022 American Association for the Advancement of Science. (e) CELM for dynamic handling. Reproduced with permission from ref 885. Copyright 2015 Taylor & Francis. (f) Reinforcement learning for robotic adaptation. Reproduced with ref 886. Copyright 2022 Wiley. (g) Transformer for morphological reconstruction. Reproduced with permission from ref 158. Copyright 2023 Springer Nature.  \n\nDespite the aforementioned commonly used machine learning techniques, some special approaches are also adopted in the deployment of flexible sensing devices. For example, a different machine learning models with adaptive boosting (AdaBoost) was employed to continuously monitor arterial blood pressure (BP) by Kireev and co-workers (Figure 48f).873  \n\nAdaBoost, as a boosting algorithm, iteratively trains weak learners (in this case, decision trees) to focus on the data points that are difficult to predict, ultimately improving the overall model’s performance.874−876 In this context, AdaBoost is effectively utilized to correlate the extracted features with control BP values. The iterative nature of AdaBoost allows it to select the most informative features and build a strong ensemble model from multiple weak learners. By iteratively adjusting the weights of misclassified data points, AdaBoost ensures that subsequent weak learners focus more on the difficult-to-predict instances, thereby improving the overall predictive accuracy. In another work, Tashakori et al. reported an accurate and dynamic approach for tracking the movement of fingers by a smart glove integrated with sensor yarns and machine learning, as demonstrated in Figure $48\\mathrm{g.}^{877}$ The high dynamic range of the sensor yarns, capable of responding to strains ranging from $0.005\\%$ to $155\\%$ , coupled with stability during extensive use and washing cycles, ensures reliable and durable performance. The use of multistage machine learning techniques (GlovePose) enables accurate estimation of joint angles that rivals that of costly motion-capture cameras, without the limitations of occlusion or field-of-view constraints. This AI-enabled innovative technology has the potential to revolutionize how hand movements are tracked and utilized in various applications, paving the way for more intuitive and immersive human−computer interactions, advanced robotics, and personalized tele-health solutions.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 44,
+        "chunk": "# 7.3. AI for Soft Robotic Systems  \n\nIn the realm of robotics, the convergence of AI with soft robotics heralds a new era of innovation and possibility.136,878−880 By leveraging the capabilities of AI, soft robots transcend the limitations of their predecessors, offering solutions to complex challenges while endowing soft robots with cognitive abilities and enabling perception, learning, and intelligent decision-making.881 This amalgamation of AI and soft robotics stands poised to revolutionize industries ranging from healthcare and manufacturing to exploration and beyond. In this discourse, we embark on an exploration of the symbiotic relationship between AI and soft robotics, delving into how AI-driven intelligence empowers soft robots to navigate uncertainty, adapt to dynamic environments, and perform tasks with precision and efficiency. From advanced control algorithms to machine learning and neural networks, we unravel the transformative potential of AI in shaping the future of soft robotics, pushing the boundaries of what is achievable in robotic systems.  \n\nIn the integrated workflow of AI within a soft robotic system, sensory inputs (such as vision, tactile, hearing, etc.) are first processed to perceive and map the environment, enabling accurate localization and object detection, as the example illustrated in Figure 49a. AI algorithms then make decisions based on this information, determining optimal control strategies for the robot’s actions, which can include navigation, manipulation, recognition, action planning, shape adaptation and so on. Through continuous learning and adaptation, the system refines its behaviors over time, leveraging feedback to improve performance and adapt to changing conditions. In scenarios involving human interaction, AI facilitates seamless communication and collaboration, ensuring safe and effective engagement. This iterative process enables soft robots to autonomously perceive, learn, adapt, and interact with their surroundings intelligently, opening up diverse applications across industries.  \n\nPerception serves as a foundational pillar within the realm of intelligent autonomous systems, essential for facilitating closedloop control and the accurate representation of the surrounding environment. Within the context of traditional rigid robotics, the attainment of robust perception has been facilitated by the deployment of highly specialized sensors meticulously arranged to capture both proprioceptive and exteroceptive information with high fidelity. However, the emergence of soft robotics with inherent modeling complexity and nonlinear challenges in soft materials introduces a paradigm shift, presenting a new hurdle to the development of soft robotics. This complexity introduces ambiguity in the design, integration of soft sensors, and modeling, fabrication, and control of soft robotics, further amplifying the intricacies of perception within the realm of soft robotics. To address this issue, Thuruthel et al. proposed a solution for modeling unknown soft actuated systems.882 Specifically, a redundant and unstructured sensor within a soft actuator alongside a vision-based motion capture system for ground truth are employed in this system, as shown in Figure 49b. Demonstrating real-time kinematic modeling of soft continuum actuators while effectively handling sensor nonlinearities and drift, this innovative approach facilitates the development of force and deformation models as well as the integration of action and perception in robotic systems. Also utilizing visual information, Zhang and co-workers introduced another perceptive soft robotic finger, which comprises a colored soft inner chamber, an outer structure, and an endoscope camera (Figure 49c).883 The bending perception of the soft finger relies on the images that are prepossessed by deep learning techniques, and CNN is trained to discern the bending states of the finger.  \n\nWhile most reported robotic sensing technologies have mainly emphasized monitoring physical parameters such as pressure, strain and temperature, the incorporation of other sensing modalities with multimodal perception abilities is comparatively less. For example, robots integrated with chemical sensors for autonomous dry-phase analyte detection could be of significance in agriculture, security, environmental protection, and public health, which presents a particularly daunting challenge that remains largely unexplored. In accordance with this, Yu et al. demonstrated an AI-powered multimodal robotic sensing system that can not only detect electrophysiology signals and tactile information, but a wide range of hazardous materials including nitroaromatic explosives, pesticides, nerve agents, and infectious pathogens (Figure 49d).884 In their work, a multimodal large-area eskin was fabricated by inkjet printing of custom-developed nanomaterial inks, which could significantly advance robotic capabilities by enabling them to detect and react to stimuli in their surroundings, thereby enhancing their autonomy and decision-making prowess.  \n\nApart from sensing in soft robotics, AI also plays a significant role in the precise control of them, a task critical for their effective operation in diverse and dynamic environments. Through the application of AI techniques like machine learning and neural networks, soft robots can achieve adaptive and responsive control strategies autonomously, enhancing efficiency and robustness in completing tasks. Figure 49e demonstrates a bionic handling assistant empower by constrained extreme learning machine (CELM) for dynamic handling of objects and interaction.885 This approach not only demonstrates the seamless integration of specific operation modes and varying levels of control for soft continuum robots, but more importantly, serves as a blueprint for control design across similar platforms. Behrens et al. presented another control scheme for smart helical magnetic hydrogel microrobot by leveraging the soft actor-critic reinforcement learning algorithm to derive a control policy, as illustrated in Figure 49f.886 The control policies involved in this work are learned by the reinforcement learning agent from both state vector input and raw images, with the behavior of the agent recapitulating that of rationally designed physical modelbased controllers microrobots. This application of deep reinforcement learning in the control of microrobots holds endless promise for significantly enhancing the boundaries of future microrobot generations. By leveraging transformer, soft robots can efficiently process complex sensory inputs, such as tactile and visual data, enabling them to better understand their environment and make informed decisions in real-time. Based on transformers, Hu and co-workers introduced an intelligent stretchable capacitive e-skin for soft robots with high proprioceptive geometry resolution (3900), achieving their morphological reconstruction with high fidelity, as shown in Figure 49g.158 The deformation of soft robot can be measured by capacitive sensors that are integrated throughout its body, followed by translating these deformation information into high-density point clouds representing the complete geometry using a deep architecture based on transformers. Benefitting from this approach, issues regarding with high density proprioceptive geometry resolution on soft robots can be addressed, holding promise for the unprecedent advancements a in soft robotics, including precise closed-loop control, digital twin modeling, etc.  \n\n![](images/fff3b08126ff2d0e66fa03aafc7aa57d0d3ad0c76c5b1144bb1992b31e57f591.jpg)  \nFigure 50. Application of soft robot for exploration. (a) Wind-dispersed wireless sensing devices, inspired by plant seed dispersal mechanisms. (b) Photograph of the 3D microfliers inspired by seeds. (c) Exploded view of our origami microflier displaying its key components and Outdoor drop tests. (d) Illustration depicting drone flight showcasing avian-inspired wing and tail morphing abilities. (e) Image showing the burrowing soft robot for subterranean navigation. (f) Image depicting the robophysical model inspired by Caenorhabditis elegans navigating a pile of rocks. (g) Image depicting the bioinspired mouse robot navigating a maze, showcasing lateral flexion enabled by its compliant spine. (h) Imaging depicting the core components of the Exobiology Extant Life Surveyor (EELS) robot. (i) Illustration depicting the design of the soft robot and its field test in the South China Sea. (j) Illustration of the design of the soft robotic fish (Sofi) and underwater exploration. (k) Illustration of the lionfish-inspired robot with multifunctional zinc iodide redox flow batteries for power. (l) Image of the custom soft manipulators in operation within the deep-sea environment. $\\mathrm{(m)}$ A turtle-inspired terrestrial−aquatic robot. (n) A terrestrial−aerial hybrid robot. (o) An aerial−aquatic hybrid robot inspired by the remora fish. (a) Reproduced with permission from ref 902. Copyright 2022 Springer Nature. (b) Reproduced with permission from ref 905. Copyright 20221 Springer Nature. (c) Reproduced with permission from ref 903. Copyright 2023 American Association for the Advancement of Science. (d) Reproduced with permission from ref 904. Copyright 2020 American Association for the Advancement of Science. (e) Reproduced with permission from ref 906. Copyright 2021 American Association for the Advancement of Science. (f) Reproduced with permission from ref 907. Copyright 2023 American Association for the Advancement of Science. (g) Reproduced with permission from ref 908. Copyright 2023 American Association for the Advancement of Science. (h) Reproduced with permission from ref 909. Copyright 2024 American Association for the Advancement of Science. (i) Reproduced with permission from ref 910. Copyright 2021 Springer Nature. (j) Reproduced with permission from ref 911. Copyright 2018 American Association for the Advancement of Science. (k) Reproduced with permission from ref 159. Copyright 2019 Springer Nature. (l) Reproduced with permission from ref 912. Copyright 2018 The Authors. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. (m) Reproduced with permission from ref 913. Copyright 2022 Springer Nature. (n) Reproduced with permission from ref 914. Copyright 2023 Cambridge University Press. (o) Reproduced with permission from ref 915. Copyright 2022 American Association for the Advancement of Science.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 45,
+        "chunk": "# 8. APPLICATIONS  \n\nSoft robotics has emerged as a transformative field with vast application scopes across various industries. From exploration in challenging terrains to revolutionizing healthcare, from enhancing immersive experiences in XR/AR/VR to enabling delicate object manipulation, soft robotics offers unprecedented versatility and adaptability.887−896 In exploration, soft robots navigate through rugged landscapes and confined spaces with agility and resilience, advancing missions in space, deep sea, and disaster zones. In healthcare, they facilitate minimally invasive surgeries, prosthetics, and assistive devices with gentle interaction and high dexterity, enhancing patient care and rehabilitation. Moreover, soft robotics enhances XR/AR/VR experiences by providing realistic haptic feedback and intuitive interactions, elevating immersive simulations and training programs. Furthermore, in object manipulation, soft robots excel in delicate tasks, such as handling fragile items or gripping irregularly shaped objects, offering precision and flexibility in industrial and manufacturing processes.897 Overall, the application scopes of soft robotics are diverse and expanding, offering innovative solutions to complex challenges across industries.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 46,
+        "chunk": "# 8.1. Exploration  \n\nSoft robotic exploration encompasses a dynamic field where flexible and adaptable robots are deployed across diverse environments, including aerial, terrestrial, and aquatic domains.893,898−901 T hese robots, characterized by their compliant and deformable structures, offer unique advantages such as enhanced maneuverability, resilience to environmental obstacles, and the ability to traverse challenging terrains. In aerial exploration, soft robots navigate through the skies with agility, accessing remote or hazardous locations where traditional rigid-bodied robots struggle to operate. Terrestrial exploration involves the deployment of soft robots on land, enabling them to traverse rugged landscapes, negotiate obstacles, and interact safely with the environment. In aquatic exploration, soft robots excel in navigating underwater environments, offering precise control and maneuverability while minimizing disturbances to delicate ecosystems. Overall, soft robotic exploration presents a versatile and promising approach to uncovering new frontiers and gaining insights into various natural and man-made environments.  \n\n8.1.1. Aerial. Gollakota’s group pioneered the development and testing of wind-dispersed battery-free wireless sensing devices. Drawing inspiration from plant seed dispersal mechanisms, they engineered millimeter-scale devices weighing a mere $30~\\mathrm{mg}$ . Powered by lightweight solar cells and featuring a backscatter communication link, these innovative devices represent a leap forward in autonomous sensing technology. Leveraging dandelion-inspired structures for wide-area dispersal and upright landing, they demonstrated remarkable capabilities, traveling distances of $50-100\\mathrm{~m~}$ in gentle to moderate breezes (Figure 50a).902 Similarly, Roger’s group has also developed wind-dispersed, battery-free wireless devices inspired by seeds (Figure 50b). Through mechanically guided assembly techniques, they’ve created miniature 3D fliers for diverse applications in environmental monitoring and surveillance. These fliers, spanning various scales, incorporate active electronic and colorimetric payloads. Their innovative approach combines bioinspired design principles with analytical, computational, and experimental studies of aerodynamics, paving the way for a wide range of practical applications. Gollakota et al. engineered solar-powered origami microfliers capable of altering their shape midair to control dispersal distance. Employing bistable leaf-out origami structures and a low-power actuator, these microfliers integrated a range of components, including a microcontroller, Bluetooth radio, and sensors for environmental data collection. Demonstrating impressive capabilities, they traveled up to 98 m in a gentle breeze, transmitting data wirelessly over $60\\mathrm{~m~}$ (Figure 50c).903 Floriano developed LisHawk, a drone featuring morphing wings and tails inspired by avian flight (Figure 50d).904 Through wind tunnel experiments, morphology optimization, and flight tests, they assessed its performance, noting enhanced maneuverability and agility in both standard and aggressive flight.  \n\n8.1.2. Terrestrial. For terrestrial exploration, Naclerio et al. investigated subterranean locomotion, devising a soft burrowing robot.906 Testing three hypotheses regarding interaction forces in granular media, they validated them through experiments. The robot successfully burrowed through sand in different paths, horizontally and vertically (Figure 50e). Goldman’s group studied limbless locomotion using both biological and robophysical models, focusing on the nematode Caenorhabditis elegans. They developed a snake-like robot model to emulate its movement, aiming to explore the role of mechanical intelligence in navigating complex environments (Figure 50f). Comparing C. elegans’ locomotion kinematics to the robophysical model, they discovered that mechanical intelligence simplifies control and enables effective navigation in diverse terrains.907 Bing et al. introduced NeRmo, a bioinspired robotic mouse equipped with a flexible spine mirroring the musculoskeletal structure of actual mice.908 This innovative design enhances NeRmo’s locomotive capabilities, enhancing static stability, walking speed, and maneuverability (Figure 50g). Vaquero et al. reported the snake-like robot called Exobiology Extant Life Surveyor (EELS) tailored for exploration on Enceladus, Saturn’s icy moon (Figure 50h).909 They discussed mobility strategies, task planning modules, and shared insights from both laboratory and field testing phases, outlining limitations and lessons learned along the way.  \n\n![](images/03468513c5ea81ae51b06fa663d3fc5b2786a65bee4d3416f3305790c4fb0fb0.jpg)  \nFigure 51. Application of soft robot for healthcare. (a) Photographs displaying the components of the exosuit. (b) Photographs showing the textile pneumatic muscle prototypes for upper limb active suit applications. (c) Photograph showing the exoskeleton system based on sample efficient active learning. (d) Illustration of the passive exosuit with body-powered variable impedance. (e) Photograph showing the components of the 3Dprinted soft robotic hand with multiarticulating capabilities. (f) Photograph of a transradial amputee demonstrating the soft robot hand controlled by both myoelectric signals and tactile feedback. (g) An illustration depicting the third thumb mounted on the side of the palm, augmenting neural body representation. (h) Photograph of an individual wearing the neuromusculoskeletal prosthesis to perform daily tasks. (i) In vivo demonstration of the soft robotic sleeve providing cardiac assist in a porcine model of acute heart failure. (j) Illustration of the robotic right ventricle (RRV) recording invasive hemodynamics in vivo. (k) Illustration depicting the tester wearing the laser-induced graphene (LIG) artificial throat. (l) Illustration of the magnetic soft robotic bladder (MRB) assisted urination. (a) Reproduced with permission from ref 920. Copyright 2019 American Association for the Advancement of Science. (b) Reproduced with permission from ref 921. Copyright 2018 Taylor & Francis. (c) Reproduced with permission from ref 922. Copyright 2023 American Association for the Advancement of Science. (d) Reproduced with permission from ref 923. Copyright 2021 American Association for the Advancement of Science. (e) Reproduced with permission from ref 924. Copyright 2020 The Authors. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. (f) Reproduced with permission from ref 925. Copyright 2023 Springer Nature. (g) Reproduced with permission from ref 926. Copyright 2021 American Association for the Advancement of Science. (h) Reproduced with permission from ref 927. Copyright 2023 American Association for the Advancement of Science. (i) Reproduced with permission from ref 928. Copyright 2017 American Association for the Advancement of Science. (j) Reproduced with permission from ref 929. Copyright 2023, The Authors, published by Springer Nature. Reproduced under the terms of the Creative Commons Attribution 4.0 International License. (k) Reproduced with permission from ref 930. Copyright 2017, The Authors, published by Springer Nature. Reproduced under the terms of the Creative Commons Attribution 4.0 International License. (l) Reproduced with permission from ref 931. Copyright 2022, The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).  \n\n8.1.3. Aquatic. For aquatic exploration, Li et al. conducted field tests in the Mariana Trench and the South China Sea to evaluate the performance of a self-powered soft robot designed for deep-sea exploration (Figure 50i). Utilizing high-voltage square-wave a.c. voltages for actuation, the robot demonstrated sustained flapping motion for $45\\mathrm{min}$ powered by a lithium-ion battery. To safeguard electronics from pressure, they were integrated into a silicone matrix and distributed to mitigate shear stress. Experimental and theoretical analyses confirmed the pressure resilience of both electronic components and soft actuators, showcasing the promise of lightweight, soft devices for extreme deep-sea exploration.910 Katzschmann et al. introduced SoFi, an untethered soft-bodied robotic fish, designed for aquatic exploration.911 Controlled remotely by a human diver through an acoustic communication modem, SoFi navigates three-dimensionally, capturing underwater footage and studying aquatic life (Figure 50j). It boasts autonomous depth control via dive planes and a compact buoyancy control unit, alongside an underwater remote control system facilitated by a miniaturized acoustic communication module. Shepherd’s group pioneered a robotic system driven by a liquid-infused battery, inspired by the energy storage concept of redox flow batteries (Figure 50k).159 Utilizing zinc iodide and distilled water, the battery cells were constructed with RFB components, offering a high energy density akin to circulatory systems. This integrated design merges hydraulic force transmission, actuation, and energy storage, resulting in a system energy density of $53\\mathrm{~J~g^{-1}}$ . Demonstrating remarkable endurance, the robot achieves prolonged underwater swimming at a speed of 1.56 body lengths per minute, showcasing the efficacy of this innovative approach through underwater demonstrations. Vogt et al. developed custom soft robotic manipulators for deep-sea exploration and interaction with marine organisms.912 Tested at depths of up to $2224\\mathrm{m}$ using a remotely operated vehicle (ROV) in the Phoenix Islands Protected Area, they enabled the study of various soft-bodied and fragile marine life forms. Instant feedback from ROV pilots and biologists allowed for swift redesign and fabrication of manipulators at sea, including the addition of features like “fingernails” for improved grasping (Figure 50l).  \n\n8.1.4. Cross-Media. Kramer-Bottiglio’s group addressed the challenge of designing mobile robots capable of traversing multiple environments effectively. Traditional approaches, such as biomimetic design or adding unique propulsive mechanisms, often result in either suboptimal performance or energyinefficient designs. To overcome these limitations, the researchers implemented “adaptive morphogenesis,” a design strategy inspired by terrestrial and aquatic turtles. This strategy involves integrating rigid components and soft materials to enable the robot to adapt its morphology and behaviors for specialized locomotion across terrestrial, aquatic, and transitional zones. The resulting robot demonstrates improved efficiency through the interplay of gait, limb shape, and environmental medium, highlighting the efficacy of adaptive morphogenesis for enhancing multienvironmental locomotion in robots (Figure $50\\mathrm{m}\\overline{{}},$ ).913 Zhang et al. introduced the autonomous quadrotor tilting hybrid robot (AQT-HR), a terrestrial−aerial hybrid robot integrating flying and driving functionalities. The robot employs a quadrotor for flight and a tilting mechanism for ground locomotion, facilitating autonomous mode switching (Figure 50n).914 Wen’s group developed an innovative aerial-aquatic hitchhiking robot capable of flying, swimming, and adhering to surfaces in both air and water, inspired by the adhesive method of the remora fish (Figure 50o).915 Its hitchhiking capability enables resting on stationary surfaces or attaching to moving hosts, prolonging operational time and expanding monitoring range.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 47,
+        "chunk": "# 8.2. Healthcare  \n\nSoft robotics has emerged as a transformative field, offering innovative solutions across various domains, including exoskeleton, prosthetics and artificial organs.891,916−918 In the realm of exoskeleton prosthetics, soft robotics introduces novel approaches that prioritize comfort, flexibility, and natural movement, mirroring the characteristics of human muscles and tendons. These advancements aim to enhance mobility and quality of life for individuals with mobility impairments by providing lightweight, adaptable, and intuitive prosthetic devices. 919  \n\n8.2.1. Exoskeletons. Kim’s group has developed a lightweight and portable exosuit designed to assist with hip extension during both walking and running.920 This innovative exosuit automatically adjusts its actuation profiles based on the wearer’s estimated potential energy fluctuations, seamlessly transitioning between walking and running modes. Moreover, the exosuit exhibited versatility by effectively reducing metabolic rates across different running speeds and even uphill walking scenarios (Figure 51a). Belforte et al. developed textile pneumatic muscle prototypes intended for integration into active suits for upper limb rehabilitation (Figure 51b).921 These prototypes, constructed from natural latex and fabric tubes, underwent rigorous pressure−length and pressure−force measurements. Rouse’s group introduced an innovative active learning approach to fine-tune the control parameters of ankle exoskeletons based on user preferences (Figure 51c).922 Their method employed a neural network model coupled with an evolutionary algorithm to rank suggestions for parameter adjustments efficiently. Through simulations and experiments involving human participants, the algorithm demonstrated an impressive average accuracy of $88\\%$ in optimizing control parameters. Cho’s group developed a body-powered variable impedance exosuit designed to optimize lifting posture and reduce the risk of injury during object handling tasks (Figure 51d). The suit utilizes artificial biarticular tendons positioned strategically behind the wearer’s back, hip, and knee joints to create a force field that promotes squatting while hindering stooping. Moreover, metabolic rate decreased during squatting, and compression force on the lumbosacral joint was reduced, indicating enhanced biomechanical efficiency and reduced strain. The immediate motor adaptation observed suggests the potential of the exosuit as an assistive device for training individuals in safer lifting practices.923  \n\n8.2.2. Prosthetics. Mohammadi designed X-Limb, a soft robotic prosthetic hand, which underwent comprehensive evaluation covering mechanical, morphological, kinodynamic, functional, and durability aspects.924 X-Limb emerges as a lightweight, durable, and functional prosthetic hand meeting essential mechanical and kinodynamic requisites while offering practical usability (Figure 51e). Capable of executing various grasp types, X-Limb caters to individuals with upper limb loss, offering versatility and adaptability. Notably, open-source files enable customization and cost-effective fabrication. Utilizing 3D printing technology, X-Limb integrates membraneenclosed flexure joints, synergy-based thumb motion, and a cable-driven actuation system. Zhao’s group engineered a soft neuroprosthetic hand tailored for individuals with transradial amputations (Figure 51f). Boasting six degrees of freedom, this innovation is orchestrated via myoelectric signals from four EMG sensors, coupled with five elastomeric capacitive sensors on the fingertips, delivering tactile feedback. Leveraging 3D printing and cost-effective materials, fabrication encompasses assembly, yielding a meticulously crafted device. Comparative analysis against a conventional rigid neuroprosthetic hand revealed the soft counterpart’s remarkable advantages in speed and dexterity. Moreover, the study delves into the analytical model and finite-element simulations, dissecting pneumatic response dynamics and bending angles of flexible joints within the hand.925 Interestingly, Makin’s group initiated a study examining the impact of hand augmentation using an additional robotic thumb on body representation (Figure  \n\n![](images/6b573b3fa68529519fca562e3f691a62c03a30f0325f27bd6f29aba4715d0516.jpg)  \nFigure 52. Application of soft robot for healthcare. (a) SEM images showcasing the binding between the Janus platelet micromotors (JPL-motor, green) and E. coli (red). (b) Images illustrating how the FSDSR utilizes soft robotic actuations to control drug delivery. (c) In vivo tracking and navigation of a microswarm in the femoral vein of the rat guided by laser speckle contrast imaging (LSCI). (d) Illustration depicting the design of the autonomous robotic catheter (e) In vivo navigation of dexterous helical magnetic robot. (f) Robotic embolization in a rabbit blood vessel in vivo using Magnetic soft microfiberbots. $(\\mathbf{g})$ photographs showing the in vivo acute recording of somatosensory evoked potentials (SSEPs) using an electrocorticography system with a soft robotic actuator. (h) Photographs demonstrating the water-induced shape-adaptive implantation of a circular WRAP electrode on the surface of a rat heart. (i) In vivo experimentation showcasing the use of magnetoelectric nonlinear metamaterial (MNM) for neural stimulation. (a) Reproduced with permission from ref 932. Copyright 2020 American Association for the Advancement of Science. (b) Reproduced with permission from ref 933. Copyright 2023 American Association for the Advancement of Science. (c) Reproduced with permission from ref 934. Copyright 2024 American Association for the Advancement of Science. (d) Reproduced with permission from ref 935. Copyright 2019 American Association for the Advancement of Science. (e) Reproduced with permission from ref 940. Copyright 2024 American Association for the Advancement of Science. (f) Reproduced with permission from ref 936. Copyright 2024 American Association for the Advancement of Science. (g) Reproduced with permission from ref 937. Copyright 2023 American Association for the Advancement of Science. (h) Reproduced with permission from ref 938. Copyright 2023 Springer Nature. (i) Reproduced with permission from ref 939. Copyright 2024 Springer Nature.  \n\n51g). Through a longitudinal experimental setup involving 36 healthy volunteers, randomly assigned to augmentation or control groups, the study assessed various parameters such as wear time, pressure sensor data, task performance, numerical cognition, hand kinematics, embodiment questionnaires, and neuroimaging scans. The findings revealed significant alterations in body representation, including enhanced hand motor control, finger coordination, and a sense of embodiment toward the extra thumb. This research highlights how motor augmentation can induce brain plasticity and reshape body perception.926 Ortiz-Catalan et al. detailed the clinical implementation of a transradial neuromusculoskeletal prosthesis, involving titanium implants in the radius and ulna bones, electromuscular constructs, and electrodes in muscles and nerves (Figure 51h). Assessment revealed enhanced prosthetic function, reduced postamputation pain, and improved quality of life. The study underscores the stability of the neuromusculoskeletal interface, sensory feedback via direct neural stimulation, and prosthesis control and signal quality, aiming to elevate the functionality and well-being of individuals with upper limb amputations.927  \n\n8.2.3. Artificial Organs. Roche et al. developed a soft robotic sleeve for cardiac ventricular assist, designed to mimic natural heart motion with linear contractile elements.928 Customizable for patient-specific needs, the sleeve serves as a bridge to transplant for heart failure patients. In vitro and ex vivo experiments optimized the design, followed by testing in pig cadavers and live pigs with acute heart failure (Figure 51i). Results showed increased ejection output and reestablished cardiac output, with the device conforming to the heart surface, synchronizing with native motion, and displacing physiological fluid volumes. Inflammation was mitigated at the device-tissue interface using hydrogel, highlighting the potential of soft robotics in supporting heart function. In addition, Singh et al. presented the development and validation of the robotic right ventricle (RRV), a hybrid soft robotic platform designed to emulate the physiological and mechanical characteristics of the right ventricle (RV) of the heart (Figure 51j). This innovative system integrates a chemically treated endocardial scaffold with a soft robotic synthetic myocardium, effectively replicating RV biomechanics and hemodynamics. Through in vivo studies with porcine models, the RRV demonstrated promise for applications in tricuspid valve repair and replacement.929 Tao’s group introduced an innovative artificial throat leveraging laser-induced graphene (LIG) technology, capable of both sound generation and detection. Fabricated through a singlestep laser writing process on a polyimide film, the LIG throat exhibited a broad frequency range ( $100~\\mathrm{Hz}$ to $40\\ \\mathrm{kHz}$ ) for sound generation, with adjustable sound pressure levels by varying LIG thickness. Moreover, it effectively detected diverse throat vibrations like coughs, hums, and screams, converting them into controllable sounds, while showcasing voice recognition capabilities (Figure 51k). With promising potential in aiding individuals with disabilities, voice control systems, and wearable electronics, the LIG artificial throat marks a significant advancement in human−machine interaction technology.930 Zang’s group developed and validated an implantable magnetic soft robotic bladder (MRB) for assisting urination in individuals with underactive bladders (UABs) (Figure 51l). By applying mechanical compression to the UAB using magnetic fields, the MRB enables on-demand contraction of the detrusor muscle. Testing in a porcine model demonstrated successful urination with increased pressure and fast urine flow, indicating the potential of MRB technology as a promising therapeutic strategy for UABs in humans, with improved efficacy and fewer adverse effects compared to existing methods.931  \n\n8.2.4. Drug Delivery. Soft robotics and actuators have emerged as promising tools for drug delivery applications. Tang et al. introduced Janus platelet micromotors (JPLmotors) by modifying natural platelet cells with asymmetrically immobilized urease enzymes (Figure 52a). This modification enables enhanced chemophoretic motion of the platelets through the decomposition of urea in biofluids. Importantly, this modification preserves the platelets’ inherent biofunctionalities, including their ability to effectively target cancer cells and bacteria. The JPL-motors demonstrate efficient propulsion in the presence of urea fuel, resulting in improved binding efficiency with biological targets. Furthermore, when loaded with model anticancer or antibiotic drugs, they exhibit enhanced therapeutic efficacy.932 Duffy’s group introduced the fibrosensing dynamic soft reservoir (FSDSR), an implantable soft robotic drug delivery device capable of monitoring the foreign body response and adjusting its actuation regimen to counter the effects of fibrotic capsule formation.933 The FSDSR incorporates a FibroSensing membrane to detect changes in electrical impedance, enabling real-time monitoring of fibrotic capsule formation. In vitro tests using Matrigel and myofibroblast proliferation, as well as in vivo experiments in a rodent model, demonstrated the FSDSR’s ability to modulate the foreign body response, enhance drug release, and show potential for closed-loop drug delivery (Figure 52b). Zhang’s group presented a method for real-time tracking and navigation of a magnetic microswarm within biological vascular systems using laser speckle contrast imaging (LSCI) (Figure 52c). The study involved developing a magnetic microswarm system utilizing $\\mathrm{Fe}_{3}\\mathrm{O}_{4}@\\mathrm{PDA}@\\mathrm{Au}$ nanoparticles, controlled by a rotating magnetic field. Experiments were conducted across various environments, including flat surfaces, artificial blood vessel phantoms, ex vivo human placenta, and in vivo rat femoral vein. The research showcased LSCI’s capability to visualize and track the microswarm in realtime, highlighting its potential for biomedical applications like targeted drug delivery in complex environments.934  \n\n8.2.5. Catheters. Dupont’s group investigated the potential of autonomous catheter navigation for intracardiac procedures using a robotic catheter and haptic vision sensor.935 They designed and built the robotic catheter and sensor, developed control algorithms, and optimized the catheter design (Figure 52d). In vivo experiments on animals tested the system’s navigation and task performance, such as leak closure and occluder deployment. Results indicated comparable or improved performance compared to hand-held or teleoperated methods, showcasing the promise of autonomous robotic systems in intracardiac procedures. Introducing a helical magnetic continuum robot $\\operatorname{\\Pi}({\\mathrm{mCR}})$ for remote magnetic navigation in the vasculature, Nelson’s group presents an innovative approach (Figure 52e). Actuated by an electromagnetic navigation system (eMNS), the $\\mathbf{\\Pi}_{\\mathrm{mCR}}$ comprises a torquable backbone, a magnetic tip, and an advancer unit. Through experiments in vitro and in vivo, the efficacy of the helical locomotion principle was assessed, demonstrating successful navigation through blood vessels with minimal damage to the vessel wall.115 Zang and colleagues conducted a comprehensive study on magnetic soft microfiberbots for endovascular intervention (Figure 52f). The fabrication process involves blending ferromagnetic particles with a soft elastomeric matrix to form magnetic microfibers of varying diameters, which are then shaped into helical structures. In vitro and ex vivo experiments showcased the microfiberbots’ deployment, steerability, and embolization capability. Further evaluations included assessments of biocompatibility and functionality. The findings underscore the promising clinical application of these microfiberbots for robotic embolization in submillimeter regions.936  \n\n8.2.6. Surgical Tools. Lacour’s group developed a soft, deployable electrocorticography (ECoG) device for recording brain activity.937 This device features a flexible array of microelectrodes that can be implanted on the brain’s surface (Figure ${\\mathfrak{s}}2{\\mathfrak{g}},\\quad$ ). A significant innovation is its deployable design, facilitating insertion through a small burr hole and subsequent expansion to cover a larger brain area. In vitro and in vivo experiments confirmed its ability to record high-quality neural signals over several weeks. Chen’s group developed a novel wrap electrode array (WRAP-electrode array) for neural interfacing applications.938 The fabrication process involved preparing WRAP films using PEG, PEO, and $\\alpha$ -CD, followed by depositing Au patterns on the WRAP film. Mechanical properties, structure, and water responsiveness of the WRAP films were characterized. The WRAP-electrode array was evaluated for electrical and electrochemical properties, in vitro and in vivo biocompatibility, and functionality in nerve stimulation and electrophysiological signal recording (Figure 52h). The research demonstrates the potential of WRAP films as versatile and biocompatible materials for soft and conformal electrode applications in neural and cardiac systems. Robinson’s group developed and characterized self-rectifying magnetoelectric metamaterials for remote neural stimulation and motor function restoration.939 They engineered a composite material, termed self-rectifying magnetoelectric nonlinear metamaterial (MNM), by incorporating a nanoscale rectifying electron transport (RET) layer into an existing magnetoelectric (ME) laminate. The study demonstrated that MNM could wirelessly stimulate peripheral nerves in anesthetized rats, restoring sensory reflex and signal propagation in a severed nerve with latencies of less than 5 ms (Figure 52i). Additionally, the research included fabrication and characterization of magnetostrictive-electrostrictive (ME) composites and magnetostrictive-nanomagnetic (MNM) composites, along with in vivo experiments assessing the biocompatibility of MNM composites and their ability to stimulate the sciatic peripheral nerve in rats.  \n\n![](images/a33d41d76743c8897fae840fa8a7116b3f3eccc033c38935163d8adcb6c582cf.jpg)  \nFigure 53. Application of soft robot for sensory feedback. (a) Untethered pneumatic glove for multimode haptic feedback. Reproduced with permission from ref 942. Copyright 2023 Wiley. (b) Cutaneous tactile force feedback. Reproduced with permission from ref 943. Copyright 2014 ACM. (c) Wearable haptic display. Reproduced with permission from ref 944. Copyright 2007 ACM. (d) Wearable haptics with electrostatic actuators. Reproduced with permission from ref 480. Copyright 2020 Wiley. (e) Wireless self-sensing and haptic-reproducing electronic skin. Reproduced with permission from ref 945. Copyright 2022 American Association for the Advancement of Science. (f) Untethered feel-through haptics with elastomer actuators. Reproduced with permission from ref 946. Copyright 2020 Wiley. (g) Stretchable skin-like thermal device. Reproduced with permission from ref 947. Copyright 2020 Wiley. (h) Stretchable and transparent metal nanowire heater. Reproduced with permission from ref 948. Copyright 2015 Wiley. (i) Soft robotic glove for rehabilitation. Reproduced with permission from ref 949. Copyright 2014 Elsevier. (j) Haptic glove using tendon-driven soft robotic mechanism. Reproduced with permission from ref 950. Copyright 2020 Baik, Park, and Park. (k) A kinesthetic haptic device for index finger. Reproduced with permission from ref 951. Copyright 2022 Springer Nature. (l) Haptic glove integrating with actuators on top of the hand and fingers. Reproduced with permission from ref 952. Copyright 2022 Wiley.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 48,
+        "chunk": "# 8.3. Extended Reality (XR: AR/VR/MR)  \n\nIn the realm of soft robotics, particularly in the domain of sensory feedback, recent developments are poised to revolutionize human−computer interaction (HCI) by providing users with not only tactile sensations but also kinesthetic information. Spanning from virtual reality (VR) environments to augmented reality (AR) settings, these breakthroughs represent a critical advancement in merging robotics, HCI, and immersive technologies, heralding a future where tactile interactions seamlessly bridge the digital and physical worlds.941 Soft robotics has emerged as a groundbreaking field with vast potential to reshape human−machine interaction (HMI) within extended reality (XR) environments. By leveraging advancements in materials science, sensor technology, and human−computer interfaces, these innovations are paving the way for a more interconnected and interactive future in virtual and augmented realities.  \n\n![](images/0693dadb95f98e17a45fdd455273f7f5f8694684e9584cc70cc560f50c142d43.jpg)  \nFigure 54. Application of soft robots for XR and human−machine interaction. (a) Active mechanical haptics with high-fidelity perceptions. Reproduced with permission from ref 954. Copyright 2023 Springer Nature. (b) Super-resolution wearable electrotactile rendering system. Reproduced with permission from ref 955. Copyright 2020 American Association for the Advancement of Science. (c) Soft and wireless olfactory interface. Reproduced with permission from ref 956. Copyright 2023 Springer Nature. (d) Skin-integrated wireless haptic interfaces. Reproduced with permission from ref 957. Copyright 2019 Springer Nature. (e) A portable force feedback origami robot. Reproduced with permission from ref 958. Copyright 2019 Springer Nature. (f) A wireless haptic interface for programmable patterns of touch. Reproduced with permission from ref 959. Copyright 2022 Springer Nature. (g) Electronic skin as wireless human−machine interfaces. Reproduced with permission from ref 960. Copyright 2022 American Association for the Advancement of Science. (h) Human−robot facial coexpression. Reproduced with permission from ref 961. Copyright 2024 American Association for the Advancement of Science. (i) Touchless interactive teaching of soft robots. Reproduced with permission from ref 962. Copyright 2022 Springer Nature.  \n\n8.3.1. Haptic Feedback Devices. There have been notable advancements in soft robots designed to provide sensory feedback, encompassing both cutaneous and kinesthetic domains. These devices are poised to revolutionize human−computer interaction (HCI) by offering users tactile sensations and kinesthetic information. The latest innovations in cutaneous feedback devices span a spectrum of modalities, including normal indentation, lateral stretching, vibration, and thermal feedback.  \n\nThe development of the HaptGlove represents a significant breakthrough in normal indentation feedback devices for virtual reality (VR) environments. This untethered and lightweight pneumatic glove integrates haptic feedback modules and fiber sensors to provide users with immersive tactile experiences (Figure 53a).942 Users can interact with virtual objects with remarkable accuracy and dexterity, thanks to the variable stiffness force feedback and fingertip force and vibration feedback provided by the HaptGlove. Furthermore, research on modulating cutaneous force in teleoperation systems offers promising insights into enhancing haptic rendering while preserving system stability (Figure 53b).943 Moving on to lateral stretching, wearable haptic displays offer new avenues for enhancing tactile interactions in VR environments. By focusing on finger deformation and utilizing soft actuators, these devices provide users with realistic sensations of weight and inertia (Figure 53c).944 The integration of flexible hydraulically amplified electrostatic actuators in haptic sleeves demonstrates the potential for generating rich vibrotactile feedback across a wide frequency range, further enhancing the user’s sensory experience in VR and AR environments (Figure 53d).480  \n\nIn the realm of vibration feedback devices, wireless selfsensing e-skin and feel-through haptic gloves demonstrate the potential of vibration feedback devices in facilitating remote touch communication and enhancing task performance in VR and augmented reality (AR) environments (Figure 53e and Figure 53f).945,946 These innovations enable bidirectional touch interactions between users and provide rich vibrotactile feedback. The integration of extremely thin actuators in e-skin devices allows for dynamic mechanical stimulus on the skin, paving the way for realistic tactile sensations in virtual environments. Transitioning to thermal feedback, skin-like thermo-haptic devices and highly stretchable transparent heaters represent significant advancements in thermal feedback technology for VR applications (Figure 53g).947 By dynamically adjusting temperature based on user interactions, these devices enhance immersion and realism. The skin-like thermohaptic device offers both cold and hot sensation feedback, providing users with unique thermal sensations for a more immersive VR experience. Similarly, highly stretchable transparent heaters offer versatile applications in wearable electronics, including personal thermal management and healthcare purposes (Figure 53h).948  \n\nIn addition to cutaneous feedback devices, significant progress has been made in the development of kinesthetic feedback devices, particularly in the context of hand rehabilitation and VR interaction (Figure 53i).949 Soft robotic gloves and tendon-driven haptic gloves offer precise functional grasping support and realistic tactile feedback, enhancing user freedom and independence in VR environments. The portable, assistive soft robotic glove is designed to augment hand rehabilitation for individuals with grasp pathologies, providing specific bending, twisting, and extending trajectories to support the range of motion of individual fingers. On the other hand, the tendon-driven haptic glove utilizes a perception-based force distribution strategy to provide haptic feedback to users’ fingers in VR environments, enhancing the perceived realism and acuity of contact force (Figure 53j).950 Except for another two eamples for kinesthetic feedback device (Figure $53\\mathrm{k},\\mathrm{l}),{}^{951,952}$ relevant wearable devices are numerous, opening the window for next gereration of intelligent wearables for Metaverse.  \n\nSignificant progress has been achieved in the evolution of soft robots designed to provide sensory feedback, encompassing both cutaneous and kinesthetic domains. These advancements hold the potential to revolutionize HCI by providing users with tactile sensations and kinesthetic information. From normal indentation to lateral stretching, vibration, and thermal feedback, recent innovations in cutaneous feedback devices have broadened the range of tactile experiences available. This collective progress represents a crucial advancement in the convergence of robotics, HCI, and immersive technologies, paving the way for a future where tactile interactions seamlessly blend the digital and physical realms.  \n\n8.3.2. XR Applications and Human−Machine Interaction. In recent years, soft robotics has emerged as a transformative field with vast potential to revolutionize human−machine interaction (HMI) within extended reality (XR) environments. Soft robots, characterized by their flexibility, adaptability, and ability to mimic biological systems, offer unique advantages in creating immersive experiences and delivering realistic tactile feedback in virtual and augmented reality settings.953  \n\nSoft robotics technology has made significant strides in replicating authentic tactile sensations within virtual environments, thereby enhancing user immersion and engagement. Innovations such as haptic devices with stiffness feedback enable users to actively experience touching objects with varying degrees of hardness or softness, contributing to the creation of more realistic XR experiences (Figure 54a).954 By simulating the sense of touch, these devices bridge the gap between physical and virtual worlds, allowing users to interact with virtual objects in a more intuitive and lifelike manner. Touch feedback systems represent another promising area of soft robotics research, offering high spatial resolution and rapid refresh rates for rendering tactile stimuli in XR environments. Wearable electrotactile rendering devices, for example, provide users with the ability to perceive textures and shapes in virtual objects with unprecedented fidelity (Figure 54b).955 These systems find applications in diverse fields such as braille displays, virtual reality shopping, and digital experiences, expanding the scope of XR technology into new domains and industries.  \n\nOlfaction feedback, often overlooked in traditional VR or XR systems, plays a crucial role in enhancing immersion and emotional engagement within XR environments. Skin-interfaced olfactory feedback systems leverage arrays of flexible and miniaturized odor generators to deliver programmable scentbased stimuli (Figure 54c).956 These systems find applications in entertainment, education, healthcare, and beyond, offering new avenues for sensory exploration and interaction in virtual spaces.  \n\nThe integration of soft robotics with social media platforms introduces novel interactions for interactive communication and personal engagement within XR environments. Wireless platforms capable of delivering programmable mechanical vibrations enable seamless communication via the skin, facilitating social interactions, prosthetic control, and gaming experiences (Figure 54d).957 By leveraging the sense of touch as a communication channel, these systems enhance user engagement and foster meaningful connections in virtual communities. Soft robotics has also made significant contributions to gaming interfaces, with foldable origami robots offering portable solutions for haptic exploration and interaction. These robots enable users to engage with virtual environments in new and exciting ways, enhancing player immersion and interaction in gaming environment (Figure 54e).958 By providing tactile feedback and intuitive control mechanisms, these systems offer immersive gaming experiences that blur the lines between physical and virtual realities.  \n\nWireless haptic interfaces have emerged as powerful tools for conveying spatial information and enhancing navigation in XR environments. These interfaces provide intuitive feedback for navigation instructions, musical translation, and sensory replacement feedback for robotic prosthetics, offering new opportunities for immersive experiences in medicine, sports, and gaming (Figure 54f).959 By leveraging the sense of touch as a means of spatial communication, these systems enable users to navigate virtual environments with greater precision and efficiency. Closed-loop human−machine interfaces based on skin-integrated electronics have transformed human−robot interaction in XR settings. These interfaces enable wireless motion capture and haptic feedback, paving the way for noncontact collection of biosamples, nursing infectious disease patients, and immersive teleoperation in healthcare application (Figure $\\displaystyle{\\langle4\\mathrm{g}\\rangle}$ .960 By integrating visual and haptic feedback, these systems provide users with a seamless and intuitive interface for interacting with robots in XR environments, enabling a wide range of applications in healthcare, entertainment, and beyond.  \n\n![](images/cc7c02ac5c9befa0fc0ed6b9c73bf37ff5fc347c114b131cf4d79e8a49c2d0b5.jpg)  \nFigure 55. Application of soft robot for handling, manipulation, and recognition. (a) Demonstration of the soft gripper of embedded pneumatic networks (PneuNets) within elastomers. (b) Photographs showing the demonstration of the high adaption feature of the gripper based on layer jamming. (c) Demonstration of a soft gripper based on tensile jamming. (d) Demonstration of a soft gripper based on the jamming of granular material. (e) Demonstration of a multifinger soft gripper with gecko-inspired adhesives. (f) Demonstration of the robot hand integrated with quadruple tactile sensors for garbage sorting. (g) Demonstartion of a soft prosthetic hand equipped with stretchable optical waveguides as sensors for detecting shape and texture. (h) Demonstration of an iontronic skin-based soft robotic hand for object recognition. (a) Reproduced with permission from ref 963. Copyright 2011 Wiley. (b) Reproduced with permission from ref 964. Copyright 2022 American Society of Mechanical Engineering. (c) Reproduced with permission from ref 965. Copyright 2021, The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC). (d) Reproduced with permission from ref 966. Copyright 2010 National Academy of Sciences. (e) Reproduced with permission from ref 967. Copyright 2021 American Association for the Advancement of Science. (f) Reproduced with permission from ref 162. Copyright 2020 American Association for the Advancement of Science. (g) Reproduced with permission from ref 118. Copyright 2016 American Association for the Advancement of Science. (h) Reproduced with permission from ref 968. Copyright 2023, The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BYNC).  \n\nAdvancements in humanoid robotics have enabled robots to mimic human facial expressions in real-time, enhancing nonverbal communication and interaction within XR environments. By training robots to anticipate and coexpress facial expressions simultaneously with humans, researchers have overcome barriers to natural and genuine interaction, fostering greater social connection and empathy between humans and machines (Figure 54h).961 By enhancing the expressiveness of humanoid robots, these systems enable more engaging and intuitive interactions in XR settings, fostering greater social connection and empathy between humans and machines. Flexible sensory interfaces offer intuitive and user-friendly approaches to teaching soft robots complex movements and tasks within XR environments. Bimodal smart skin technology, for example, enables humans to teach soft robots movements via bare hand−eye coordination, empowering users to teach robots specific tasks such as completing mazes, taking throat swabs, and grasping objects (Figure 54i).962 By providing intuitive and nonprogrammable teaching methods, these interfaces democratize the use of soft robots in various applications, enabling broader adoption and utilization across diverse domains.  \n\nIn conclusion, the integration of soft robots with XR systems holds immense promise for revolutionizing human−machine interaction across diverse domains. By leveraging the latest advancements in materials science, sensor technology, and human−computer interfaces, researchers continue to push the boundaries of XR and HMI, paving the way for a more connected and interactive future. As soft robotics technology continues to evolve, it is poised to play a central role in shaping the XR experiences of tomorrow, offering new avenues for creativity, exploration, and collaboration in VR and AR.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 49,
+        "chunk": "# 8.4. Manipulation  \n\nSoft robotics has emerged as a transformative field, offering innovative solutions for object manipulation and recognition. Unlike traditional rigid robots, soft robots are constructed from flexible and deformable materials, allowing them to adapt to complex environments and interact with objects more naturally. These robots are inspired by biological systems, enabling them to perform delicate tasks with dexterity and precision.  \n\nSoft robotic systems utilize advanced sensing technologies, such as computer vision and tactile sensors, to recognize and manipulate objects with varying shapes, sizes, and properties. By integrating soft actuators and sensors, these robots can grasp, lift, and manipulate objects with greater flexibility and sensitivity.  \n\n8.4.1. Object Handling. Whitesides’s group proposed the utilization of soft materials, particularly elastomers, in crafting fully soft robots.963 Traditional rigid robots face challenges in delicately handling fragile objects and traversing unpredictable terrains. In response, soft robots offer promising solutions. The concept of soft robots encompasses machines fashioned from soft materials or those comprising multiple hard-robotic actuators operating synergistically to exhibit soft-robot-like properties. Whitesides’s group emphasizes soft elastomeric materials, highlighting their benefits, such as continuous deformation and expansive ranges of motion dictated by material properties (Figure 55a). Their approach involves designing and fabricating soft robots through embedded pneumatic networks (PneuNets) within elastomers. These networks function akin to balloons, inflating to enact movement. By employing pneumatic systems for energy supply and employing diverse materials for control, they pave the way for innovative soft robotics application.  \n\nSu’s group introduces a soft robotic gripper employing layer jamming technology, offering a unique blend of high payload capacity and adaptability.964 This gripper, crafted through 3D printing with two materials, integrates jamming layers to bolster its payload capacity. Actuation occurs through inflating the internal air chamber, enabling significant bending angles. Notably, for heavy payloads, the gripper employs negative air pressure on the jamming layers, effectively locking it in the desired shape. Remarkably adaptable, it can securely grasp w80 objects ranging from 6 to $10\\mathrm{~kg},$ rivaling rigid-body grippers in performance (Figure 55b). Kramer-Bottiglio’s group reported a design termed “tensile jamming fibers,” capable of swiftly adjusting their tensile stiffness while preserving low bending stiffness (Figure 55c). These fibers find application in two key domains: modular variable trajectory actuators and shapechanging membranes. The study showcases the fibers’ prowess, presenting mechanical testing outcomes and manufacturing intricacies. The overarching aim is to realize reconfigurable soft robotics and shape-changing systems leveraging the unique attributes of tensile jamming fibers.965 Brown et al. devised a versatile gripper utilizing the principle of granular jamming.966 Instead of traditional fingers, a single mass of granular material conforms to the shape of an object upon contact, facilitated by vacuum-induced contraction and hardening (Figure 55d). Through experiments, the researchers showcased the gripper’s efficacy in grasping various objects, ranging from spheres to cubes. They also elucidated the underlying gripping mechanisms, including friction and suction, and developed a model linking these mechanisms to the jammed material’s strength. The study underscores the gripper’s potential for reliably handling objects of diverse shapes, particularly in scenarios requiring rapid and informed manipulation. Ruotolo’s group introduced a robotic hand design named farmHand, incorporating gecko-inspired adhesives for grasping and manipulation tasks (Figure 55e). The hand features compliant finger pads with angled ribs for enhanced contact and load sharing. A control strategy aligns phalange orientations to surface normals, reducing pressure inconsistencies. Testing validated load sharing and manipulation capabilities, showcasing versatility in various tasks.967  \n\n8.4.2. Object Recognition. Zhu’s group introduced a robot hand equipped with quadruple tactile sensors, enhancing object recognition during grasping .162 These sensors feature a multilayer microstructure inspired by skin, enabling perception of thermal conductivity, contact pressure, and object/environment temperature simultaneously. Through fusion with machine learning, the hand can accurately identify diverse objects based on shape, size, and material (Figure 55f). The researchers demonstrated its efficacy in garbage sorting, achieving a remarkable $94\\%$ classification accuracy across seven types of garbage. Shepherd’s group introduced a soft prosthetic hand featuring stretchable optical waveguides serving as sensors for strain, curvature, elongation, and force detection.118 These waveguides are crafted via a four-step soft lithography procedure, comprising a core material with a high refractive index and a cladding material with a low refractive index. With exceptional compliance and stretchability, these waveguides function effectively as sensors for diverse deformations. Integrated into the fingers of the prosthetic hand, they facilitate active sensation experiments, including shape and softness detection (Figure 55g). Guo’s group devised a highly sensitive and mechanically robust iontronic skin for robotics, embedding isolated microstructured ionic gels (IMIGs) within an elastomeric matrix.968 This design ensured heightened sensitivity, minimal response to shear stress, and swift response-recovery rates. The skin exhibited resilience under severe mechanical conditions, enabling realtime pressure mapping and object recognition (Figure 55h).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 50,
+        "chunk": "# 9. CONSIDERATIONS FOR FUTURE DEVELOPMENT  \n\nUndoubtably, numerous advancements have been made in the field of soft robots in terms of sensing, actuation, control, and applications. These advancements have not only changed the research paradigm but also the way human beings interact with the world. However, as we look toward the future development of sensorimotor materials and soft robots, several key considerations should be taken into account.117,559 As summarized in Figure 56, we categorize these considerations into materials discovery, biomimicking, energy, manufacturing, artificial intelligence, and sustainability.  \n\n![](images/7ee8c950166f017b02286685a82a821a405b57f4e7d498100c74a4438d7b848d.jpg)  \nFigure 56. Summary of future development considerations of soft intelligent machines.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 51,
+        "chunk": "# 9.1. Materials Discovery  \n\nThe discovery of new materials will undoubtfully drive the development of soft robotics and flexible electronics, offering significant advantages in terms of functionality, efficiency, and adaptability.969,970 For example, the debut of stimuli responsive smart materials (LCEs, magnetic fluids, shape-memory polymers, etc.) opens new avenues for the development of untethered soft robots,971,972 and the introduction of conductive polymers addresses the dilemma between mechanical flexibility and electrical conductivity of materials,973 enabling the integration of electronic devices in an unprecedented way. Despite numerous breakthroughs in materials science, such as graphene, conductive polymers, 2D materials, hydrogels, and ion gels, the search of novel materials with better performances and functionalities is endless and there’s plenty of space within this discovery. For example, biohybrid materials that combines synthetic materials with biological components (like cells or proteins) allows for the creation of living, responsive systems for applications in medical robotics and tissue engineering.974−978 On the other hand, metamaterials, engineered with properties not found in natural materials, are also revolutionizing electronics and robotics. Such materials could not only enable the miniaturization of high-performance antennas and improve electromagnetic wave manipulation in electronics, but also can empower soft robots with unconventional functionalities ranging from actuation and computation to signal processin g.979,980 Another interesting point is edible robotic food that can serve as functional components, such as health monitoring and drug delivery, which could open a new avenue for robotics, healthcare, and the environment.981 As research progresses, these new materials enable the development of more advanced and durable systems that can operate in a variety of environments and applications, from medical devices to wearable technology and beyond. Their unique properties allow for the creation of robots and electronics that are lighter, more energy-efficient, and capable of performing complex tasks, ultimately expanding the potential applications of these technologies.",
+        "category": " Introduction"
+    },
+    {
+        "id": 52,
+        "chunk": "# 9.2. Biomimicking  \n\nBiomimicking, or biomimicry, leverages nature’s evolved solutions to create innovative and efficient technologies across various fields. By emulating natural designs and processes honed over millions of years, biomimicking leads to advancements in both flexible electronic devices and soft robots.982−984 For example, octopus-inspired soft robots offer superior adaptability and delicate interaction capabilities,137,985 while gecko-inspired adhesives enhance wearable electronic devices’ comfort and effectiveness. 6 Such biomimicking approach also fosters eco-friendly and energy-efficient solutions, such as selfcleaning surfaces for efficient photovoltaics and chameleoninspired color-changing materials for flexible displays.987,988 Moreover, biomimicking also drives medical advancements, improving prosthetics’ designs and functionalities. Despite these advancements, current technologies have achieved biomimicry at a relatively low level, which only exhibits limited functionality, lacking the intricacy of multiple functionalities and subsystems as well as their coordination in an efficient and reliable way. By contrast, biological species exhibit complex, integrated sensorimotor systems that enable highly responsive, adaptive, and efficient interactions with their environment. Thus, future research should delve deeper into these mechanisms, studying the intricate neural networks, sensory feedback loops, and adaptive learning processes that animals use. Taking the research of e-skin as an example, rather than focusing only on the detection of pressure, it is crucial to achieve other functions possessed by real skin. Real skin not only senses pressure but also has the ability to detect temperature, differentiate between normal and shear forces, and respond to both static and dynamic stimuli.989,990 Moreover, it has self-healing properties that enable it to repair damage and maintain functionality over time.991 As for the conventional signal processing approaches involved in e-skin, while the data acquisition is based on sequential measurement of time division multiple access at each measurement cycle, the information processing mainly utilizes analytical or data-driven approaches.992,993 Unavoidably, a number of challenges are involved in such approaches, ranging from complex switching circuits and readout latency to signal interference and power consumption.994 On the contrary, biological species employs event-driven spike generation solution that allows parallel data processing without the readout delay, which can greatly reduce the power consumption to process volumes of sensing dat a.995,996 Therefore, such signal processing techniques as well as neuromorphic computing in biological species should be further deployed in the development of intelligent soft machines. $430,997,998$ Moving further to sensorimotor control, it has been found that hierarchical control strategies are widely used in animals for the intricate movement of muscles.4,999 These strategies involve multiple layers of control, from highlevel planning and coordination to low-level execution of precise movements, allowing animals to perform complex tasks efficiently and adaptively. By studying these natural hierarchical control systems, we can develop novel and powerful control technologies for soft robots.1000−1007 In a word, we can develop more advanced, autonomous, and intelligent materials, robots, and systems by closely replicating these sophisticated mechanisms in biological systems.",
+        "category": " Introduction"
+    },
+    {
+        "id": 53,
+        "chunk": "# 9.3. Energy  \n\nThe significance of energy in soft robots and electronic devices cannot be overstated. As these technologies continue to advance, it poses significant challenges for the development of next-generation power sources.1008−1010 These challenges include balancing size, weight, flexibility and other physical properties with power functions. As smaller devices and robots face considerable payload restrictions and energy requirements, careful consideration of the size and weight of energy sources during the design phase is crucial.1011 The compactness and lightweight nature of these devices necessitate efficient energy storage solutions that do not compromise their operational capabilities. Balancing energy density with size, weight, and structures constraints is essential to ensure that these devices can perform effectively without frequent recharging or added bulk.1012 Additionally, the development of soft, flexible, and stretchable batteries could greatly contribute to the advancement of all soft electronic devices and systems.1013 Incorporating such energy storage solutions allows for greater design freedom, enabling the creation of more ergonomic, compact and user-friendly devices that can seamlessly integrate with the human body or adapt to dynamic environments. Apart from these examples, there are many other application scenarios that require the next-generation energy sources. While maintaining efficient energy storage and management in compact and flexible forms is difficult, advancements in materials, nanotechnology, and energy harvesting from ambient environment offer promising solutions.1014−1017",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 54,
+        "chunk": "# 9.4. Manufacturing  \n\nThe goal of advanced manufacturing in the future is to create highly adaptable, efficient, and high-performing systems that outperform their predecessor and meet diverse application needs. The birth of such systems will be driven by innovations and technological breakthroughs such as 4D printing, multimaterial printing, seamless integration technology, nanomanufacturing, digital twins, AI, and sustainable practices. Different from 3D printing, 4D printing will create dynamic, responsive structures that adapt to environmental stimuli, while multimaterial and hybrid manufacturing will seamlessly combine diverse materials for enhanced functionality.1018−1020 Nanomanufacturing will enable precise nanoscale features and utilize nanomaterials to boost performance. Digital twins and simulations will optimize design and maintenance, reducing development time and costs.1021 AI integration will enhance automation, precision, and efficiency in manufacturing processes. Sustainable manufacturing will focus on biocompatible, eco-friendly materials and energy-efficient processes, reducing environmental impact. By adopting and coordinating these cutting-edge techniques, the future of these fields promises improved solutions, greater sustainability, and innovative applications across diverse industries.",
+        "category": " Introduction"
+    },
+    {
+        "id": 55,
+        "chunk": "# 9.5. Artificial Intelligence  \n\nIt can be envisioned that AI will be indispensable in soft robotics in near future, playing a crucial role in various aspects from design optimization and manufacturing process management to signal processing, analysis, decision-making and control. AI-driven algorithms will optimize the design of soft robots, ensuring their efficiency, performance, and adaptability to specific tasks and environments. In manufacturing, AI will manage processes, reducing waste, enhancing quality control, and improving efficiency through predictive maintenance and real-time monitoring.1022 More interestingly, AI will be part of soft robots itself, acting as the minds and enabling them to process and analyze sensory data, making informed decisions and adjustments for control in real-time .1023 With the assist from AI, the autonomy, functionality, and intelligence of soft robots can be enhanced in an unprecedented level.1024 On the other hand, the integration of large models (such as generative pretrained transformer, GPT) into soft robotics holds significant potential for enhancing human−robot interaction, programming and control, problem-solving and optimization, training and learning, and assistive application s.1025−1031 These AI models excel in natural language processing, enabling users to interact with soft robots using spoken or written language, simplifying programming tasks, and facilitating more intuitive communication. However, challenges such as ensuring robustness, accuracy, safety, and addressing ethical considerations need to be addressed to ensure responsible deployment and adoption.",
+        "category": " Introduction"
+    },
+    {
+        "id": 56,
+        "chunk": "# 9.6. Sustainability  \n\nAiming at mitigating environmental impacts, promoting resource conservation, and fostering long-term viability in the field of technology, sustainability entails a comprehensive approach focusing on materials innovation, green manufacturing, energy efficiency, circular design principles, regulatory compliance, and public engagement.1032 To be more specific, this includes the adoption of biodegradable and recyclable materials, implementation of sustainable manufacturing practices, improvement of energy efficiency through energy harvesting and storage, and design for disassembly and upgradability to extend lifespans and reduce wastes from both electronic devices and soft robots.751,1033−1037 Lifecycle assessments and adherence to environmental regulations will be paramount, along with efforts to increase public awareness and education about sustainable practices. By prioritizing sustainability throughout the product lifecycle, manufacturers can create more environmentally friendly and socially responsible technologies, contributing to a greener and more sustainable future. Ultimately, the significance of advancing sustainability in soft robots and flexible electronic devices extends beyond technological innovation to encompass broader societal and environmental benefits, contributing to a more sustainable future for generations to come.",
+        "category": " Introduction"
+    },
+    {
+        "id": 57,
+        "chunk": "# 10. CONCLUDING REMARKS  \n\nThe intersection between flexible sensing devices and soft robots is an emerging field poised for the continuing development of soft intelligent machines and their real-world applications for exploration, healthcare, entertainment, and industry by providing enhanced adaptability, safer interactions, and the ability to function in unstructured environments. Despite numerous advancements being made in soft materials and actuators, multifunctional flexible sensors, advanced control systems, and energy-efficient power supplies over the years, the marriage between soft electronic device and robot is just in its early stage and corresponding challenges do exist. These include devising the output performance of soft sensors and actuators according to needs, ensuring the durability and reliability of flexible components under repetitive stress and harsh conditions, achieving seamless integration between soft materials and electronic devices, improving the robustness of the sensorimotor control system, and developing scalable and cost-effective manufacturing processes.  \n\nTraditionally, sensors and actuators in soft robotics have been developed and optimized independently, which can result in suboptimal performance, energy inefficiencies, and a lack of seamless interaction between components. By adopting a codesign approach, the sensor and actuator systems are developed concurrently from systematic design perspective, with the design of each component informed by the requirements and constraints of the other. This integrated approach enables more efficient, adaptive, and responsive systems, where the actuation can be directly informed by sensory feedback, and the sensor can be optimized to capture the most relevant physical parameters that enhance actuator performance. Co-optimization takes this integration a step further, focusing on the simultaneous optimization of both components to maximize system performance. By considering the sensor and actuator as a unified system, co-optimization ensures that the functionalities of each component complement each other, leading to improved energy efficiency, faster response times, and more precise control. For example, soft actuators can be designed to deform in a way that generates specific sensory feedback, allowing for continuous, real-time adjustments to the system’s behavior. Similarly, sensors can be optimized to detect parameters that are crucial for actuator control, such as strain, pressure, and temperature, enabling the actuation system to adapt dynamically to environmental conditions and internal changes.  \n\nSuch codesign and co-optimization of soft sensors and actuators are also crucial for developing adaptive soft robotic systems with sensorimotor functions. By optimizing relevant components in tandem, closed-loop, energy-efficient, adaptive, and intelligent systems can be created, where real-time sensor feedback informs and adjusts actuator behavior in unstructured environments. This is particularly valuable in complex tasks such as manipulation, where precise coordination between the sensor and actuator is necessary for tasks such as object grasping or delicate assembly. The integration of these elements not only enhances the functionality of soft robots but also contributes to their robustness, adaptability and autonomy in real-world applications. Moreover, advances in materials science play a pivotal role in the codesign and cooptimization process. The development of materials that simultaneously enable both sensing and actuation functions is key to simplifying the design and reducing the weight and complexity of soft robotic systems. Materials such as piezoelectric polymers, electroactive elastomers, or multifunctional composites can serve both as sensors and actuators, offering significant advantages in terms of compactness, efficiency, and system integration. The selection of such materials allows for the development of highly integrated systems that reduce the need for external wiring and support structures, thereby enhancing the system’s flexibility and scalability. In a word, the codesign and co-optimization of soft sensors and actuators represent an essential direction for future research in soft robotics. This integrated approach has the potential to significantly enhance the intelligence, adaptability, and efficiency of soft robots, paving the way for their application in complex and dynamic environments such as healthcare, human−robot interaction, and autonomous systems. Future work should focus on refining computational models and control strategies that facilitate the optimization of sensor-actuator systems, as well as exploring new materials that support multifunctionality. Ultimately, the integration of sensing and actuation in a cohesive, optimized system will be key to unlocking the full potential of soft robots.  \n\nThe ultimate goal of soft robotic research is to develop robots that possess intelligence comparable to or even beyond that of humans, enabling them to naturally interact with their environment, learn from experiences, and autonomously perform complex tasks. Achieving this vision, undoubtedly, requires a multidisciplinary approach that draws upon the expertise of biologists, neuroscientists, materials scientists, roboticists, and engineers. Each discipline contributes valuable insights and techniques, such as biological inspiration for sensorimotor integration, advances in materials for flexible actuation, and breakthroughs in AI for autonomous decisionmaking. The convergence of these fields will facilitate the creation of highly efficient and adaptable sensorimotor systems, which can respond intelligently to dynamic environments and complex scenarios. The future of soft robots holds immense promise, and with continued collaboration, innovation, and dedication, we are on the cusp of realizing a new era of autonomy, intelligence, and sustainability.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 58,
+        "chunk": "# AUTHOR INFORMATION",
+        "category": " References"
+    },
+    {
+        "id": 59,
+        "chunk": "# Corresponding Author  \n\nXiaodong Chen − Innovative Centre for Flexible Devices (iFLEX), Max Planck−NTU Joint Lab for Artificial Senses, School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore; $\\circledcirc$ orcid.org/0000-0002-3312-1664; Email: chenxd $@$ ntu.edu.sg",
+        "category": " References"
+    },
+    {
+        "id": 60,
+        "chunk": "# Authors  \n\nJiangtao Su − Innovative Centre for Flexible Devices (iFLEX), Max Planck−NTU Joint Lab for Artificial Senses, School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore Ke He − Innovative Centre for Flexible Devices (iFLEX), Max Planck−NTU Joint Lab for Artificial Senses, School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore Yanzhen Li − Innovative Centre for Flexible Devices (iFLEX), Max Planck−NTU Joint Lab for Artificial Senses, School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore Jiaqi Tu − Innovative Centre for Flexible Devices (iFLEX), Max Planck−NTU Joint Lab for Artificial Senses, School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore",
+        "category": " References"
+    },
+    {
+        "id": 61,
+        "chunk": "# Author Contributions  \n\nX.C. and J.S. conceived the topic and proposed the structure of this review. J.S., K.H., Y.L., and J.T. carried out data curation and analysis, produced the figures, and prepared the manuscript in consultation with X.C. CRediT: Jiangtao Su conceptualization, data curation, formal analysis, visualization, writing - original draft, writing - review & editing; Ke He conceptualization, formal analysis, visualization, writing - original draft; Yanzhen Li conceptualization, data curation, writing - original draft; Jiaqi Tu data curation, formal analysis, writing - original draft; Xiaodong Chen conceptualization, formal analysis, investigation, project administration, resources, supervision, visualization, writing - original draft, writing - review $\\&$ editing.",
+        "category": " Abstract"
+    },
+    {
+        "id": 62,
+        "chunk": "# Notes  \n\nThe authors declare no competing financial interest.",
+        "category": " References"
+    },
+    {
+        "id": 63,
+        "chunk": "# Biographies  \n\nJiangtao Su is a Ph.D. candidate at the School of Materials Science and Engineering, Nanyang Technological University in Singapore, and he is also an academic visiting guest at The Institute of Robotics and Intelligent Systems, Department of Mechanical & Process Engineering, ETH Zurich in Switzerland. His research focuses on flexible devices, robotics, metamaterials and advanced manufacturing. Ke He is a dedicated research fellow at the School of Materials Science and Engineering, Nanyang Technological University in Singapore. He received his Ph.D. degree in Physical Chemistry from Jilin University in 2014. His research interests primarily revolve around bioinspired materials and devices, with a specific focus on biomimicking, soft robotics, and wearable healthcare applications.  \n\nYanzhen Li is pursuing his Ph.D. in the School of Materials Science and Engineering at Nanyang Technological University, Singapore. He received his B.Sc. in Materials Science of Physics from Nanjing University in 2020. His research focuses on mechanical sensors and other flexible electronic devices.  \n\nTu Jiaqi is currently pursuing his Ph.D. at the School of Materials Science and Engineering, Nanyang Technological University in Singapore. He received his Bachelor’s degree in Materials Science and Engineering from Zhejiang University. His research interests lie in the development and application of flexible tactile sensors, with a particular focus on enhancing sensor performance and reliability for various applications, including wearable technology and healthcare monitoring.  \n\nXiaodong Chen is a Distinguished University Professor at Nanyang Technological University, Singapore (NTU), holding appointments as Professor of Materials Science and Engineering, and Professor (by courtesy) of Chemistry and Medicine. A leading expert in the areas of flexible materials and devices, nanobio interface, and nanoelectronics, he currently serves as Editor-in-Chief of ACS Nano. He is a Fellow of Singapore National Academy of Science, a Fellow of the Academy of Engineering Singapore, and a member of the German National Academy of Sciences Leopoldina. His contributions to science and engineering have been recognized with numerous prestigious awards and honors, including Singapore President’s Science Award, Singapore NRF Investigatorship, Friedrich Wilhelm Bessel Research Award, the Dan Maydan Prize in Nanoscience and Nanotechnology, and the Kabiller Young Investigator Award.",
+        "category": " References"
+    },
+    {
+        "id": 64,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nFinancial support was provided by the Agency for Science, Technology and Research (A\\*STAR) under its AME Programmatic Funding Scheme (Project #A18A1b0045), the National Research Foundation, Singapore (NRF) under NRF’s Medium Sized Centre: Singapore Hybrid-Integrated NextGeneration $\\mu$ -Electronics (SHINE) Centre funding programme and the Smart Grippers for Soft Robotics (SGSR) Programme under the National Research Foundation, Prime Minister’s Office, Singapore under its Campus of Research Excellence and Technological Enterprise (CREATE) programme.",
+        "category": " References"
+    },
+    {
+        "id": 65,
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+        "chunk": "# Views & Comments",
+        "category": " References"
+    },
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+        "chunk": "# Generative AI for Materials Discovery: Design Without Understanding  \n\nJianjun Hu a, Qin Li b, Nihang Fu a  \n\na Department of Computer Science and Engineering, University of South Carolina, Columbia, SC 29208, USA b College of Big Data Statistics, Guizhou University of Finance and Economics, Guiyang 550025, China",
+        "category": " Abstract"
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+    {
+        "id": 3,
+        "chunk": "# 1. Design as building-block assembling  \n\nIn the 21st century, society is facing several fundamental challenges, including global climate change, the energy crisis, and public health crises such as cancers and coronavirus disease 2019 (COVID-19). Their solutions share a certain commonality: They all involve the discovery of novel atomic structures such as materials, molecules, proteins, and drugs. Designing such functional atomic structures is challenging due to the astonishing complexity of their inter-atomic interactions, sophisticated physical/chemical/geometric constraints and patterns in the formation of stable structures, and the relation between structures and their functions.  \n\nLike most engineering design activities, the mainstream paradigm of materials design is currently the rational design approach, which emphasizes a causal understanding of the structure– function relationship and depends on heuristic expert knowledge and explicit design rules. The typical ‘‘tinkeringº design process starts with topology design with a limited number of prototypes and ends with parametric design. However, the traditional materials design paradigm is encountering increasing challenges in designing extraordinary functional materials that can effectively meet our needs: It usually leads to sub-optimal solutions in the huge chemical design space due to the limited search capability; it cannot handle the huge amount of implicit knowledge and constraints well and cannot exploit such rules for efficient design space exploration; it requires too many explicit design rules; and it presents difficulties in the design of highly constrained structures such as periodic inorganic crystals.  \n\nHere, we argue for a transformative shift from rational materials design to a data-driven deep generative materials design paradigm, in which known materials data are fed to deep generative models in order to enable the models to learn explicit and implicit knowledge of atomic structures and then exploit the models for efficient structure generation. This shift is inspired by two major, recent achievements in artificial intelligence (AI). The first of these is that the data-driven deep learning algorithm AlphaFold2 shows that deep learning models can solve the ‘‘finding-a-needle-inthe-haystackº issue inherent in the protein structure prediction problem by exploiting the learned implicit rules and constraints from known protein structures for efficient sampling in the protein structure space. The second achievement is that deep-learningbased artificial-intelligence-generated content (AIGC) technologies have been accelerating in generating authentic images, videos, texts, music, and human voices. Despite the apparent differences between digital artifacts and atomic structures, it can be seen in Table 1 that designing images and texts shares many characteristics with the task of designing proteins, materials, and molecules, in which building blocks of different levels are assembled together to form specific stable or meaningful structures that satisfy diverse grammatical, physical, chemical, or geometric constraints.  \n\nCompared with earlier generative design systems [1] that explicitly define the building blocks and generative rules or grammars, the deep generative design paradigm employs deep neural networks to learn the physical or chemical rules for assembling synthesizable and stable structures. Deep generative material design thus offers a new methodology and a philosophy that views materials in terms of dynamic processes and their outcomes and in which neural networks can be used to learn not only static interatomic interactions but also self-assembly and self-organization dynamic processes. Just as nature came to use the physical apparatus of DNA as the information carrier of synthesis rules for protein synthesis and biochemistry through evolution, deep neural networks can also be exploited similarly to achieve nature’s way of materials design via learning the designing rules from known materials or computational simulations. Just as a female frog can give birth to a frog without knowing how a frog is grown from a zygote through a developmental process, deep generative design can follow a similar design-without-understanding process for creative design.  \n\nTable 1 A comparison of designing images and texts with designing proteins, materials, and molecules.   \n\n\n<html><body><table><tr><td>Domain</td><td>Building block</td><td>Structures</td></tr><tr><td>Image/video</td><td>Pixel → patches/strips</td><td>Objects/shapes</td></tr><tr><td>Language</td><td>Characters → words → sentences → paragraphs</td><td>Text</td></tr><tr><td>Proteins</td><td>Amino acids（AAs)→ AA sequence</td><td>Three-dimensional</td></tr><tr><td>Materials</td><td>→ secondary structures Atoms → bonds → polyhedrons</td><td>protein structures Crystal structures</td></tr><tr><td>Molecules</td><td></td><td></td></tr><tr><td></td><td>Atoms → bonds → groups</td><td>Organic molecules</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2. Generative artificial intelligence for design  \n\nGenerative AI started in the 1950s with Claude Shannon’s Markov chains for language generation; it then evolved to Hopfield networks and Boltzmann machines for image and music generation in the 1980s and on to probabilistic graphical models such as hidden Markov models and the Gaussian mixture models in the 1990s. However, it was not until the emergence of generative adversarial networks (GANs) [2] in 2014 that generative AI could really create authentic images, videos, texts, and audio. Trained with a large number of existing data samples, modern deep neural network models can generate strikingly real digital artifacts that are now widely used in the AIGC community by chat generative pre-trained transformer (ChatGPT) or other software. These models can learn the delicate and sophisticated patterns, rhythms, styles, geometrical constraints, and/or interdependencies among building blocks from known samples through their networks and then exploit this implicit knowledge for the effective and efficient generation of new content.  \n\nDeep generative models have been increasingly applied to the generative design of DNAs and proteins (sequences and structures), molecules (composition and conformations) [3], materials (composition and structures), and engineering design [4]. Although the tokens or building blocks differ, most of these works share a set of common generative model architectures, as shown in Fig. 1.  \n\nThe variational autoencoder (VAE) model is composed of an encoder that maximally compresses the raw input information $x$ into a lower-dimension latent space $z$ so that the decoder can reconstruct the input as $x^{\\prime}$ with a minimal amount of reconstruction error; the latent space is regularized by minimizing the Kullback–Leibler divergence between the returned latent distribution and a standard Gaussian distribution. The GAN model consists of two components: a generator and a discriminator. The generator learns to create new samples that mimic the distribution of the training data, while the discriminator learns to distinguish between real and fake samples. The two components are trained together in a process called adversarial training, where the generator attempts to create increasingly realistic materials and the discriminator becomes better at distinguishing between real and fake samples. Compared with the VAE model, which has literal reconstruction loss, GAN models are capable of capturing the semantic information of the training sample distribution and generating diverse new generations.  \n\nThe diffusion model works by destroying training data through the successive addition of Gaussian noise and then learning to recover the data by reversing this noising process using a denoising neural network. After training, the model can generate data by simply passing randomly sampled noise through the learned denoising process. One of the key advantages of the diffusion model is that it can generate highly realistic and diverse images without the need for complex adversarial training. It can also generate images with controllable attributes by conditioning the diffusion process on additional inputs, such as class labels or semantic embeddings. Another major category of generative models is autoregressive network models such as generative pre-trained transformer (GPT), which are a type of language model used for text generation that generates text by predicting the next word in a sequence based on the previous words in the sequence. This model is trained on a large corpus of text and learns the probability distribution of each word, given its previous words. These models can also be used for image generation in a pixel-by-pixel way.  \n\n![](images/5a28e9973af56ad7d8f87de10c10da2c1e01d9581d864c6c9af07cf5c0d12ca2.jpg)  \nFig. 1. Deep generative neural network models. $x$ is the training sample; $x^{\\prime}$ is the generated sample; $z$ represents a latent vector; $\\pmb{x}_{i}$ represents latent vectors $(i=1,2,...,n)$ VAE: variational autoencoder.  \n\nGenerative flow network (GFlowNet) models [5] are probabilistic models that construct objects by iteratively sampling a probability distribution over possible building blocks and adding the next. They build objects at a frequency proportional to the reward. GFlowNet models are trained to mirror the reward function learned by the surrogate model; the generative model can then be used to generate many structures using the GFlowNet, which are then prioritized using the surrogate model. This makes GFlowNet good for sampling intelligently in a large chemical design space.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 3. Generative AI for materials discovery  \n\nIn traditional materials design, researchers rely on trial and error to test new materials, which can be a time-consuming and expensive process. Generative materials design aims to speed up this process by learning and exploiting chemical/geometric/physical constraints for the efficient generation of new materials that meet specific criteria, such as synthesizability, stability, conductivity, or optical properties. These materials can then be synthesized and tested in the lab, potentially leading to new discoveries. Fig. 2 shows representative generative models for materials design.",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 3.1. Generative design of material compositions  \n\nThe goal of material composition design is to discover compositions that can be synthesized into stable crystal structures. These hypothetical compositions can be used to guide experimental synthesis or be fed to crystal-structure-prediction algorithms, if available, to obtain their stable structures. Material compositions can also be fed to composition-based machine learning models of material properties such as elastic constants or band gaps for composition screening. However, material composition generation is non-trivial due to three major challenges:  \n\n(1) This is a ‘‘finding-a-needle-in-the-haystackº problem [6]. The space for three-element materials exceeds $10^{9}$ combinations, and the four-element space exceeds $10^{12}$ combinations; moreover, a majority of these combinations do not even satisfy basic chemical rulesÐonly $6.7\\text{\\textperthousand}$ and $7.8\\text{\\textperthousand}$ satisfy the constraints of charge neutrality and electronegativity balance for four- and five-element compositions, respectively, assuming the number of atoms for each element is $\\leq8$ .  \n\n(2) The relationship between a given composition and its synthesizability and capability to form stable structures is complex due to the many sophisticated chemical and geometric constraints. (3) Without the structure information, it is difficult to evaluate the quality of generated candidates, such as the synthesizability or structural stability, in order to screen promising candidates.  \n\nOne of the earliest generative design studies utilized real vectors to encode the numbers of atoms for elements in a composition [7] using both conditional VAE and conditional GAN models. However, the models tended to generate mostly chemically invalid compositions, which could not be easily screened using the basic chemical rules of charge neutrality and electronegativity balance due to their real-valued atom number representation. Realizing the importance of the discrete encoding of the number of atoms of elements, we proposed the MatGAN material composition generator [8], which is based on a GAN generative deep learning model and a one-hot binary matrix representation of material compositions. This encoding scheme greatly facilitates the convolution neural networks of the GAN to learn the sophisticated chemical rules or patterns within the known materials in the Inorganic Crystal Structure Database (ICSD) and Materials Project database. It was found that the percentage of chemically valid (i.e., charge-neutral and electronegativity-balanced) samples out of all generated compositions by MatGAN reached $84.5\\%$ when the GAN model was trained with the samples in the ICSD, even though no such chemical rules are explicitly enforced in our GAN model. This indicates MatGAN’s capability to learn implicit chemical composition rules, which allows it to exploit learned implicit constraints in generating promising compositions that are more likely to form stable and synthesizable compounds.  \n\nA material composition such as $\\mathrm{SrTiO}_{3}$ can be naturally represented as a sequence of element symbols, such as Sr Ti O O O;  \n\n![](images/f0c1321256f90b51ffbf4f9964c97c88de18ebbab352238dbb3d0db59709b186.jpg)  \nFig. 2. Representative frameworks for deep generative materials design. RoBERTa: robustly optimized bidirectional encoder representation from transformers (BERT) approach; BLMM: blank language models for materials; CDVAE: crystal diffusion variational autoencoder; GNN: graph neural network.  \n\nthis inspired us to build composition generators using modern generative language models such as GPT and bidirectional encoder representation from transformers (BERT). These models have achieved huge success in the generation of texts, molecules, and protein sequences. In Ref. [9], we developed and benchmarked seven modern language models (including GPT, GPT-2, GPT-Neo, GPT-J, blank language models for materials (BLMM), bidirectional and autoregressive transformers (BART), and robustly optimized BERT approach (RoBERTa)) as MTransformer algorithms for composition generation. Six different datasets with/without noncharge-neutral or balanced electronegativity samples from the ICSD, Open Quantum Materials Database (OQMD), and Materials Project database were used to train these models. We found that the causal language model (e.g., GPT)-based material transformers could generate chemically valid material compositions of which as high as $97.54\\%$ were charge-neutral and $91.40\\%$ were electronegativity-balanced, exhibiting an enrichment more than six times higher than a baseline pseudo-random sampling algorithm. This finding demonstrates the capability of language models to capture the implicit chemical rules and constraints for the formation of chemically valid materials compositions. To further improve the interpretability of the learned language model, we applied a blank-filling probabilistic language model to the material composition generation problem [10]. Our crystal transformer algorithm demonstrated the highest generation performance in terms of the percentages of charge neutrality and electronegativity. It also allows the designers to tinker with a given material composition in order to explore the design space based on its learned materials chemistry, which is useful for materials doping.  \n\nOne of the key decisions in material composition generative design is how to evaluate the generation performance, especially when the structure information is unavailable. While charge neutrality, electronegativity balance, and predicted formation energy can be used as the first level of performance measures, such models can also be evaluated using novelty, uniqueness, and recovery rate, among which the latter is especially useful: If a generator can rediscover most of the leave-out compositions that have been synthesized before, it is a strong indication of its generation power.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 3.2. Generative design of crystal structures  \n\nThe de novo generation of novel synthesizable and stable crystal materials is a challenging task due to the highly sophisticated relationships from the composition to stable structures. Unlike organic molecules and other structures, crystal materials tend to have periodic structures with high symmetry, which leads to a highly constrained multimodal design space. The significantly higher diversity of the element types $(>85)$ and the complex inter-atomic interactions exacerbate the problem.  \n\nThe field of data-driven crystal structure generative design has recently been emerging rapidly based on a series of deep generative models with a variety of crystal encodings. iMatGen, which is short for image-based materials generator, is one of the earliest algorithms for crystal structure generation. This VAE-based model was trained with structures of the $\\mathsf{V}_{x}\\mathsf{O}_{y}$ family and was able to discover 40 relatively stable structures with $E_{\\mathrm{hull}}<80$ meV per atom $\\cdot E_{\\mathrm{hull}}$ : the energy above hull; $1\\ \\mathrm{meV}=1.602\\times10^{-22}\\mathrm{J}$ ). Kim et al. [11] demonstrated that a GAN-based generative model using point clouds as inputs could be used to generate stable $\\scriptstyle\\mathbf{Mg-Mn-O}$ ternary compounds. Using a voxelized crystal representation of iMatGen, Court et al. [12] trained a conditional deep-featureconsistent VAE for the generation of new crystals that went beyond a specific chemical system. However, their model needed a U-Net segmentation network to map the predicted electron density into atomic sites, which hindered its performance.  \n\nTo exploit the symmetry of crystals, we developed CubicGAN [13], a GAN-based generative model for generic cubic crystal structure generation. Our model was used to generate 506 new-prototype stable hypothetical materials, such as $\\mathrm{Li}_{6}\\mathrm{N}_{6}\\mathrm{Cl}$ and ${\\mathsf{C a C O}}_{6}.$ as verified by phonon dispersion density functional theory (DFT) calculations. We further showed that, by incorporating additional symmetry principles and physics-based constraints into the generative models, the generation performance could be significantly improved, as shown by our physics guided crystal generative model (PGCGM) algorithm [14], which can generate the crystal structures of more than 30 space groups. Another major progress in generative crystal material design is the crystal diffusion variational autoencoder (CDVAE) [15], which trains a decoder that can generate materials in a diffusion process. The neural-networkbased diffusion model makes it possible to move atomic coordinates toward a lower energy state with appropriate atom types to satisfy bonding preferences between neighbors. It also models interactions across periodic boundaries and respects permutation, translation, rotation, and periodic invariances, which can further improve its performance. This model has been used to discover thousands of hypothetical two-dimensional (2D) materials; however, its capability in three-dimensional (3D) material generation (especially high-symmetry materials) needs further improvement [14], which has been partially achieved in the newest model, MatterGen [16].  \n\nWhile our review of generative materials design has focused on inorganic materials, the same principles and models have also been widely applied to the generative design of proteins [17], organic materials [3,18], and architected materials, for which both language models and diffusion models are intensively used for forward and inverse design [19].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 4. Challenges and opportunities  \n\nGenerative material design is still in an emerging stage, and there are many significant challenges and related opportunities that must be addressed, ranging from algorithm models to training datasets or design objectives.  \n\nChallenge 1: Controlled generative design with multiobjective functions and complex physicochemical or geometric constraints. This challenge is compounded by the fact that the simulation codes for most performances are not even differentiable, which makes it difficult to incorporate those performance objectives into the loss function to guide the model training and generation.  \n\nChallenge 2: Mixing large language models (LLMs) with generative models for generative materials design. While deep language models have been combined with generative models for protein [20] and simplified molecular-input line-entry system (SMILES)-based molecule design [18], it is challenging to apply this to crystal material design due to the high symmetry constraints and the difficulty of finding stable and synthesizable crystal structures.  \n\nChallenge 3: Fast validation models for screening final candidate materials. Many material design constraints (explicit or implicit) cannot be incorporated into a generative model and can only be validated over generated samples. However, filtering criteria such as synthesizability, mechanical stability, and thermodynamic stability are all very difficult to compute. The consideration of manufacturability makes it even worse. The question of how to improve the hit rate of generating physically and chemically feasible materials and train fast and accurate evaluation models is a key unsolved problem.  \n\nChallenge 4: Creative generative design. The objective of design is to find novel materials with exceptional properties while current generative models are trained to generate samples similar to the training sets. Another obstacle is that neural networks are good at interpolation but not at extrapolation, which makes the performance prediction of out-of-distribution samples difficult and misleads generation models to generate invalid designs.  \n\nChallenge 5: Generative design with limited datasets. Due to the high costs of experiments or DFT calculations, most current materials datasets are small in terms of macro material properties such as thermal conductivity and piezoelectricity. However, there are a large number of unlabeled material structures. Opportunities exist here to exploit advanced machine learning techniques such as pretraining and physics-informed neural networks to address these issues. There is also promise in exploring surrogate models trained with mixed fidelity datasets and studying out-of-distribution machine learning models with high generalization performance for novel samples.  \n\nWith the emergence of more advanced deep generative AI techniques, as demonstrated by OpenAI’s Sora for text-to-video generation, generative design research for materials and structures will undergo a transformative revolution in the coming years, which can greatly assist in addressing the global challenges of climate change, energy, and human health.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# References  \n\n[1] McCormack J, Dorin A, Innocent T. Generative design: a paradigm for design research. In: Redmond J, Durling D, de Bono A, editors. Proceedings of Futureground, Design Research Society International Conference; 2004 Nov 17–21; Melbourne, VIC, Australia. Clayton: Monash University Publishing; 2004.   \n[2] Goodfellow I, Pouget-Abadie J, Mirza M, Xu B, Warde-Farley D, Ozair S, et al. Generative adversarial networks. Commun ACM 2020;63(11):139–44.   \n[3] Bilodeau C, Jin W, Jaakkola T, Barzilay R, Jensen KF. Generative models for molecular discovery: recent advances and challenges. Wiley Interdiscip Rev Comput Mol Sci 2022;12(5):e1608.   \n[4] Regenwetter L, Nobari AH, Ahmed F. Deep generative models in engineering design: a review. J Mech Des 2022;144(7):071704.   \n[5] Bengio E, Jain M, Korablyov M, Precup D, Bengio Y. Flow network based generative models for non-iterative diverse candidate generation. In: Ranzato M, Beygelzimer A, Dauphin Y, Liang PS, Wortman Vaughan J, editors. Advances in neural information processing systems 34. Red Hook: Curran Associates, Inc.; 2021. p. 27381–94. [6] Davies DW, Butler KT, Jackson AJ, Morris A, Frost JM, Skelton JM, et al. Computational screening of all stoichiometric inorganic materials. Chem 2016;1(4):617–27. [7] Sawada Y, Morikawa K, Fujii M. Study of deep generative models for inorganic chemical compositions. 2019. arXiv:1910.11499. [8] Dan Y, Zhao Y, Li X, Li S, Hu M, Hu J. Generative adversarial networks (GAN) based efficient sampling of chemical composition space for inverse design of inorganic materials. npj Comput Mater 2020;6(1):84. [9] Fu N, Wei L, Song Y, Li Q, Xin R, Omee SS, et al. Material transformers: deep learning language models for generative materials design. Mach Learn Sci Technol 2023;4(1):015001.   \n[10] Wei L, Li $\\scriptstyle{\\mathsf{Q}},$ Song Y, Stefanov S, Siriwardane EMD, Chen F, et al. Crystal transformer: self-learning neural language model for generative and tinkering design of materials. 2022. arXiv:2204.11953.   \n[11] Kim S, Noh J, Gu GH, Aspuru-Guzik A, Jung Y. Generative adversarial networks for crystal structure prediction. ACS Cent Sci 2020;6(8):1412–20.   \n[12] Court CJ, Yildirim B, Jain A, Cole JM. 3-D inorganic crystal structure generation and property prediction via representation learning. J Chem Inf Model 2020;60 (10):4518–35.   \n[13] Zhao Y, Al-Fahdi M, Hu M, Siriwardane EMD, Song Y, Nasiri A, et al. Highthroughput discovery of novel cubic crystal materials using deep generative neural networks. Adv Sci 2021;8(20):2100566.   \n[14] Zhao Y, Siriwardane EMD, Wu Z, Fu N, Al-Fahdi M, Hu M, et al. Physics guided deep learning for generative design of crystal materials with symmetry constraints. npj Comput Mater 2023;9(1):38.   \n[15] Xie T, Fu X, Ganea OE, Barzilay R, Jaakkola T. Crystal diffusion variational autoencoder for periodic material generation. 2021. arXiv:2110.06197.   \n[16] Zeni C, Pinsler R, Zügner D, Fowler A, Horton M, Fu X, et al. MatterGen: a generative model for inorganic materials design. 2023. arXiv:2312. 03687.   \n[17] Buehler MJ. Generative pretrained autoregressive transformer graph neural network applied to the analysis and discovery of novel proteins. J Appl Phys 2023;134(8):084902.   \n[18] Luu RK, Wysokowski M, Buehler MJ. Generative discovery of de novo chemical designs using diffusion modeling and transformer deep neural networks with application to deep eutectic solvents. Appl Phys Lett 2023;122(23):234103.   \n[19] Lew AJ, Buehler MJ. Single-shot forward and inverse hierarchical architected materials design for nonlinear mechanical properties using an attention– diffusion model. Mater Today 2023;64:10–20.   \n[20] Ni B, Kaplan DL, Buehler MJ. ForceGen: end-to-end de novo protein generation based on nonlinear mechanical unfolding responses using a language diffusion model. Sci Adv 2024;10(6):eadl4000.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# A Solvent Regulated Hydrogen Bond Crosslinking Strategy to Prepare Robust Hydrogel Paint for Oil/Water Separation  \n\nZhongxiang Bai, Kun Jia,\\* Chenchen Liu, Lingling Wang, Guo Lin, Yumin Huang, Shuning Liu, and Xiaobo Liu\\*  \n\nHydrogel modified porous matrix with the super-wetting surface (i.e., superhydrophilic/underwater super-oleophobic) is ideal for oil/water separation. However, the deterioration in mechanical strength and separation efficiency during the swelling process and complicated synthesis procedure limits its industrial application. In this study, a strategy of using ethanol to dynamically regulate the hydrogen bond crosslinking between polyvinyl alcohol (PVA) and tannic acid (TA) is proposed to prepare a “hydrogel paint”, which can be simply applied on the porous substrate surface by different one-step operations (dipping, brushing, spraying, etc.) without additional cross-linking. The underline mechanism is attributed to the re-establishment of intermolecular hydrogen bond mediated cross-linking between PVA and TA during ethanol evaporation. Consequently, the resultant hydrogel coating exhibits ultra-high strength $(>10M P a)$ ), swelling volume stability, and excellent oil-water separation efficiency $(>99\\%)$ . This study will provide new insights into the scalable fabrication of hydrogel-coated porous materials for oil/water separation in industrial scenarios.",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1. Introduction  \n\nThe oil/water mixture deriving from industrial wastewater discharge and offshore crude oil leakage have brought great challenges to environmental protection, human health and biological survival.[1] Thus, the technologies or materials that can effectively separate oil from water are of great importance in terms of sustainable development. In recent years, functionalized membrane materials with special wettability are considered to be a more effective water treatment technology due to its high separation efficiency and low energy consumption.[2] Particularly, the super-hydrophilic/super-oleophobic (SHL/SOB) materials exhibit obvious advantages in resisting oil contamination compared to super-hydrophobic (SHB) materials, but their application is still hindered because oil with low surface tension tends to diffuse on most of solid surfaces.[3] Thus, the materials showing super-hydrophilic/underwater super-oleophobic (SHL/UWSOB) properties after water pre-wetting have been considered as superior candidate for oil-water separation.  \n\nBiomimetic strategies play important roles in design of advanced functional materials for separation applications. For instance, the underwater oil-repellent surface of marine organisms has brought a new way to develop the research of SHL/ UWSOB materials.[4] In 2009, Liu et  al. found that the micro-/nanostructures on the surface of fish scales displayed a unique underwater super-oleophobicity.[5] Inspired by fish scales, various surface functionalization methods, such as chemical corrosion,[6] electrodeposition,[7] heat treatment,[8] etc., have been employed to fabricate SHL/UWSOB materials. However, these methods are usually energyintensive, and the manufacturing process is only suitable for laboratory environments, presenting challenges in real-life industrial applications. Later, Jiang’s group reported a micro-structured hydrogel coating on the surface of stainless-steel mesh (SSM), which opened a new way for the preparation of SHL/UWSOB materials.[9] It is worth noting that the hydrogel coating of porous substrates is more complicated than that of non-porous substrates, because the hydrogel coating on porous substrates also has the risk/defects of blocking the pore structure and reducing flux. In addition, the hydrogel coating applied to oil-water separation should exhibit good swelling stability, as water swelling usually results to deterioration of surface wetting and mechanical properties.[10]  \n\nDipping, spraying, brushing or shear coating is regarded as efficient technique to fabricate uniform coatings on large areas.[11] For hydrogel coatings on grid or porous substrates, the complete coating process normally involves the sol-gel transition. The conventional methods to prepare polymer hydrogels often involve monomers polymerization and macromolecular crosslinking,[12] which inevitably leads to the abrupt increase in viscosity of pre-gel solutions caused by rapid reaction kinetics. Therefore, it is difficult to apply a common paint coating method to a hydrogel coating. To avoid this problem, the current commonly used strategy is to form gel coating through a two-step method.[13] The first step is to dissolve the existing polymer and decorate it on the surface of the porous substrate; the second step is to form a 3D crosslinked networks on the surface of the substrate by means of solution immersion assisted cross-linking, repeated freeze-thaw, irradiation crosslinking and other methods.[12,14] Polyvinyl alcohol (PVA), as the largest by production scale existing polymer, has attracted extensive interest for hydrogel coatings due to its low cost, nontoxic, and intrinsic hydrophilicity. For instance, Jiang et  al.[13c] used glutaraldehyde as a cross-linking agent to enable crosslinking of PVA on filter paper through a simple aldehyde condensation reaction to prepare a hydrogel-coating for oil/water separation. Liu et al.[15] prepared PVA coated SSM for oil/water separation in complex environment through repeated freezethaw assisted method. Although these PVA hydrogel coatings prepared by physical or chemical methods have achieved success, there are still challenges in practical applications in terms of the cross-linking control, the cost of scalable preparation, as well as the hydrogel coating strength.  \n\nHerein, we proposed an ethanol/water solvent system to regulate the hydrogen bond cross-linking between PVA and TA, and prepared a “hydrogel paint” by a one-pot method. Ethanol in the solvent system temporarily hinders the cross-linking of PVA and TA to form a uniform hydrogel paint, which can be coated on the surface of the metal mesh (SSM) by the common paint application method. Interestingly, when ethanol in the hydrogel paint on the surface of the SSM gradually evaporates, the hydrogen bond cross-linking between PVA and TA is reestablished. The obtained hydrogel coating layer possesses stable swelling volume, ultra-high strength and stable repellency to various types of oil, and the gel-coated SSM displays a gravity-driven high separation efficiency and a long-term cyclic stability.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2. Results and Discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2.1. Hydrogel Paint Preparation and Formation Mechanism  \n\nPoly(vinyl alcohol) (PVA) has been intensively used in the fabrication of hydrogels,[16] and the appropriate crosslinking agents are generally introduced to manipulate the crosslinking kinetics as well as density so as to obtain anti-swelling hydrogels. However, there are contradictions in the conventional hydrogels preparation protocols: weak interactions are preferred to ensure the fluidity of the hydrogel paint during the co-dissolution of PVA and crosslinking agent, while the strong interactions are acclaimed to ensure the high strength and stability of the hydrogel during the crosslinking process. For example, it was recently found that a small amount of plant-derived polyphenol TA could be co-dissolved with PVA without formation of hydrogels;[17] however, when a large amount of TA and PVA were co-dissolved, gelatinous precipitates were generated due to the strong hydrogen bonding (Figure  1a).[18] Inspired by the principle of using non-derived solvents to destroy the intra or intermolecular hydrogen bond to dissolve cellulose,[19] if the PVA/ TA solvent system is added molecules with stronger hydrogen bond with PVA or TA to isolate the intermolecular hydrogen bond between PVA and TA, the resultant mixture solution would exhibit uniform fluidity and good processability for mesh substrate coating. More importantly, when the molecules used to isolate can be removed, the strong hydrogen bond between  \n\nPVA and TA will be reformed, enabling the in-situ preparation of hydrogel coatings on the mesh surface.  \n\nFor this reason, we chose ethanol to replace part of water to weaken the strong hydrogen bond cross-linking between TA and PVA, and obtained a stable and homogeneous hydrogel paint. The hydrogel paint can be applied to the surface of the porous SSM through one-step method (dipping, spraying, brushing or shearing) similar to that used for common paint (Figure  1b). As shown in Scheme  1, after the ethanol in the coating was removed, the hydrogen bond between PVA and TA is re-established to form a 3D network structure. Ethanol can be removed by volatilization or solvent diffusion. Since the volatilization method is simpler and the resulting coating is more uniform (Figure S1 in the Supporting Information), the subsequent experiment uses the volatilization method to prepare the PVA-TA hydrogel coating. The effect of the volume ratio of ethanol in the solvent on the hydrogel paint (Table S1 and Figures S2 and S3, Supporting Information) was studied, and it was found that the volume ratio of ethanol had an effect on the uniformity of the hydrogel paint, which in turn affected the gel coating rate and water flux of the SSM. For comprehensive performance, a water/ethanol volume ratio of 5:5 is finally selected as the optimized solvent system of PVA/TA. The effect of TA content (Table S2 and Figure S4, Supporting Information) and PVA/TA concentration (Table S3 and Figure S5, Supporting Information) in the hydrogel paint on coating performance is also discussed in detail. In addition, in order to increase the surface roughness of the coating and the stability of the PVA-TA gel, an appropriate amount of nano-sized $\\mathrm{SiO}_{2}$ was added.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2.2. Characterization of Hydrogel Coatings  \n\nFourier transform infrared (FTIR) spectroscopy was used to identify the hydrogen bond cross-linking between TA and PVA molecules (Figure  2a). Compared to PVA, the hydrogel containing TA appeared new absorption peaks at 1714 and $1612\\mathrm{cm}^{-1}$ , which were assigned to the stretching vibration of the $\\scriptstyle{\\mathrm{C=O}}$ and $\\scriptstyle{\\mathrm{C=C}}$ and the peak at $750~\\mathrm{cm}^{-1}$ was attributed to the stretching vibration of C-H on the aromatic ring, the bending deformation of C-OH and benzene ring torsion.[20] The broad and strong absorption bands at 3250 and $3365~\\mathrm{cm}^{-1}$ are attributed to the symmetrical stretching vibration of hydroxyl groups $(\\boldsymbol{\\mathrm{v}}_{\\mathrm{O-H}})$ of PVA and TA,[16a] while the $\\boldsymbol{\\mathbf{v}}_{\\mathrm{O-H}}$ peaks of the PVA−TA and PVATA- $\\mathrm{SiO}_{2}$ shifted to a lower wavenumber of 3232 and $3234~\\mathrm{cm}^{-1}$ , respectively. Simultaneously, the PVA showed typical $\\mathsf{v}_{\\mathrm{C-OH}}$ at $1087\\mathrm{cm}^{-1}$ ,[21] which shifted to a lower wavenumber of $1030~\\mathrm{cm}^{-1}$ after being treated with TA. It is well-known that the formation of intra- or intermolecular hydrogen bond reduces the force constants of the chemical bonds, leading to the red shifting of their vibrational frequencies.[17,22] Therefore, the chemical shift of $\\boldsymbol{\\mathrm{v}}_{\\mathrm{O-H}}$ and $\\mathsf{\\Pi}\\mathsf{v}_{\\mathrm{C.OH}}$ implies that hydrogen bond cross-linking is formed between PVA-TA.[23] In addition, the FTIR spectra of PVA-TA and PVA-TA $\\boldsymbol{\\mathcal{Q}}\\boldsymbol{\\mathrm{SiO}}_{2}$ hydrogels did not show new peaks produced by chemical reactions, indicating that the cross-linking system was exclusively enabled by physical effects.  \n\nWe then used X-ray diffraction (XRD) to characterize the structure of the PVA, TA, PVA-TA and PVA-TA $@\\mathrm{SiO}_{2}$ . As shown in Figure 2b, the XRD pattern of PVA shows three typical peaks at $2\\theta=19.6^{\\circ}$ , $2\\theta=22.9^{\\circ}$ , and $2\\theta=40.8^{\\circ}$ , corresponding to the (101), (200), and (102) planes of PVA crystallites.[17,24] Due to the amorphous nature of TA, there are no sharp crystalline peaks in the XRD pattern of TA, instead of a blunt peak at $2\\theta=25.9^{\\circ}$ . The introduction of TA causes a significant reduction in the typical crystallization peak of PVA, which is due to the fact that the strong hydrogen bond between PVA and TA inhibits the crystallization of PVA chains, and this result is consistent with previous reports.[17–18]  \n\n![](images/03c151e4ce4b930740e4f49b457bf870097ad89f614831a793980d512a9257fc.jpg)  \nFigure 1.  a) Photograph of PVA and TA dissolved in $H_{2}O$ and $\\mathsf{H}_{2}\\mathsf{O}/\\mathsf{C}_{2}\\mathsf{H}_{5}\\mathsf{O}\\mathsf{H}$ mixed solvent. b) Schematic fabrication of hydrogel coated SSM by different techniques.  \n\n![](images/8bff83bfc9f44e23768912d6bd2aa054301adcbd1fe27c6b73c04f7cbc9b4a86.jpg)  \nScheme 1.  Schematic illustration of reconstruction of hydrogen bond of PVA and TA when the ethanol is evaporated.  \n\n![](images/bf7eb8ba8286845cdc7cf692115f39766ddbf684003d1f08525cc50ced3e7ec5.jpg)  \nFigure 2.  a) ATR-FTIR spectra and b) X-ray diffraction (XRD) patterns of PVA, TA, PVA-TA and PVA-TA $@\\mathsf{S i O}_{2}$ . c) TGA, and d) DTG curves of PVA, PVA-TA, and PVA-TA $\\textcircled{\\sc1}$ hydrogels.  \n\nIn addition, the thermal gravimetric analysis (TGA) was conducted for PVA, PVA-TA, and PVA-TA $@\\mathrm{SiO}_{2}$ (Figure 2c,d). The first weight loss platform appearing at $80{-}150^{\\circ}\\mathrm{C}$ was due to the evaporation of bound water in hydrogels. The second weight loss plateau period was detected between 200 and $500~^{\\circ}\\mathrm{C}$ , and the initial weight loss temperatures of PVA-TA and PVA-TA $\\ @\\operatorname{SiO}_{2}$ were slightly lower than PVA. This phenomenon may be due to the fact that TA destroys the crystallization of PVA.[25] Interestingly, in the range of $220{-}350^{\\circ}\\mathrm{C}$ , the thermal degradation rate of PVA and TA alone was higher than that of PVA-TA and PVA-TA $@$ $\\mathrm{SiO}_{2}$ (Figure  2d and Figure S6: Supporting Information), and the weight-loss rates of PVA, PVA-TA, and PVA-TA $\\ @\\operatorname{SiO}_{2}$ were $92\\%$ , $79\\%$ , and $76\\%$ , respectively.  \n\nAlthough many previous works have reported high strength hydrogels, maintaining mechanical strength for a long time in oil/water separation environments is still challenging because the heterogeneous swelling of hydrogels likely results in low polymer chain density and small friction between polymer chains.[10,26] Given that hydrogen bond crosslinking is an effective method to restrain swelling,[27] we have characterized the swelling properties and corresponding mechanical properties of PVA-TA and PVA-TA $\\ @\\operatorname{SiO}_{2}$ under different conditions. As shown in Figure  3a, the equilibrium swelling ratio (ESR) of PVA-TA and PVA-TA $@\\mathrm{SiO}_{2}$ in highly acidic and saline environments was much lower than that of common hydrogels, only $6\\mathrm{-}18\\%$ , and the ESR of PVA-TA $@\\mathrm{SiO}_{2}$ was greater than that of PVA-TA. However, in a highly alkaline environment, the ESR of the hydrogel increased drastically, and PVA-TA $\\ @\\operatorname{SiO}_{2}$ was more stable than PVA-TA. It could also be observed from Figure $3\\mathrm{g}$ that the swelling volumes of PVA-TA and $\\mathrm{PVA\\mathrm{\\cdotTA@SiO_{2}}}$ increased under the highly alkaline environment, while the volume basically did not change under the acidic and saline environment. In addition, we observed that the transparency of the gels decreased after being immersed in pure water, strong acid and high-salt solutions, possibly due to the separation of the hydrophobic phase caused by hydrogen bond.[28] In a highly alkaline environment, the gel cross-linking network was no longer dense, and the hydrophobic phase separation was declined, which leaded to an increase in gel transparency.[29] Twenty-five phenolic hydroxyl groups in the TA molecule, which are protonated under acidic conditions, are excellent hydrogen donors and recipients for binding with hydroxyl groups of PVA.[30] As the pH value increases, the ionization of TA increases, resulting in a decrease in the density of the hydrogen bond cross-linking network of the hydrogel and an increase in water absorption. Since the hydrogen bond is sensitive to $\\mathsf{p H}$ variations, we prepared a series of solutions with a $\\mathrm{\\pH}$ range of 2–12, and then soaked the PVA-TA and $\\mathrm{PVA-TA@SiO}_{2}$ hydrogel samples in these solutions for $24\\mathrm{~h~}$ . As shown in Figure 3b, the ESR of PVA-TA and PVA-TA $@\\mathrm{SiO}_{2}$ stabilized at around $11\\%$ and $18\\%$ , respectively, in the range of $\\mathrm{pH}=2\\mathrm{-}8$ . At $\\mathrm{pH}=10\\$ , the ESR of the gels showed an apparent upward trend. When $\\mathrm{pH}=12\\$ , the water absorption rate of the hydrogel increased sharply, and the ESR of PVA-TA and PVA-TA $@\\mathrm{SiO}_{2}$ became 9.7 times and 3.1 times than that of the neutral environment, respectively. The PVA-TA and PVA-TA $@\\mathrm{SiO}_{2}$ hydrogels exhibit a pH-dependent swelling behavior as a consequence of the ionization of the functional groups in the phenolic structures.[25,31] Correspondingly, we tested the mechanical strength of the hydrogel after reaching swelling equilibrium under different environments. Figure 3c,d showed that the PVA-TA $@\\mathrm{SiO}_{2}$ hydrogel in the pure water swelling equilibrium demonstrated excellent mechanical properties with a tensile strength of $11.8\\mathrm{~MPa}$ , and a breaking strain of $487\\%$ , which is much higher than the currently reported supramolecular polymer hydrogel. [27b,32] As shown in Figure S7 (Supporting Information), the PVA-TA $@\\mathrm{SiO}_{2}$ hydrogel strip with a thickness of ${\\approx}0.3~\\mathrm{mm}$ , width $\\mathrm{\\Delta\\sf{}\\approx10\\ m m}$ was capable of withstanding a weight of $2.5~\\mathrm{kg}$ without any damage. More interestingly, although the PVA-TA $@\\mathrm{SiO}_{2}$ showed a yielding during stretching, no necking phenomenon as that of common high strength hydrogels was observed (Figure S8, Supporting Information), suggesting that hydrogen bond cross-links undergo gradual separation rather than sudden cumulative damage, which implies that the gel could bear greater loads, thereby avoiding catastrophic failure as a coating.[28] Under high acid and salt conditions, the tensile strength of $\\mathrm{PVA–TA@SiO_{2}}$ increased to 15.7 and $12.5\\ \\mathrm{MPa}$ (Figure  3e), respectively, but after swelling and equilibrium in $1\\ \\mathrm{M}\\ \\mathrm{NaOH}$ , the tensile strength decreased sharply to $0.2~\\mathrm{MPa}$ .  \n\n![](images/bb7f1260f4804e20269a5d7244b58c8113948fd73c8385191cb6416b7d6e92ac.jpg)  \nFigure 3.  Swelling and mechanical properties of PVA-TA and PVA- ${\\mathsf{T A@S i O}}_{2}$ hydrogels: The equilibrium swelling rate of hydrogels in a) extreme environments and at b) $\\mathsf{p H}=2-12$ . Photograph of PVA-TA $\\textcircled{a}{\\mathsf{S i O}}_{2}$ in c) tensile test and d) stress–strain curve under extreme environment. The tensile strength of hydrogels in e) extreme environments and f) at ${\\mathsf{p H}}=2{-}12$ g) Photograph of hydrogel swelling under extreme conditions.  \n\n![](images/d63c0f6883845e8c9bec93e83f4611b068123a0eb741e3ec3aa9a1848799c143.jpg)  \nScheme 2.  The preparation of PVA-TA $@\\mathsf{S i O}_{2}$ decorated SSM by dip coating method and its oil/water separation mechanism  \n\nAs the $\\mathrm{\\ttpH}$ value of the swelling environment increased from 2 to 12, the tensile strength of $\\mathrm{PVA-TA@SiO}_{2}$ hydrogel decreased from 14.0 to $7.2~\\mathrm{MPa}$ (Figure  3f), which is still an outstanding strength for hydrogel materials. In addition, the breaking energy (Figure S9, Supporting Information) of PVA-TA and PVA-TA $@\\mathrm{SiO}_{2}$ in different environments was also similar to the change trend of tensile strength. In the whole test conditions, the tensile strength of PVA-TA $\\ @\\operatorname{SiO}_{2}$ was better than that of PVA-TA, especially in the high alkaline environment $\\mathrm{(pH=}$ 12), which was mainly due to the presence of $\\mathrm{SiO}_{2}$ providing more hydrogen bond crosslinking points.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.3. Micro-Morphology and Wettability of Hydrogel-Coated Metal Mesh  \n\nThe surface chemical composition and microstructure are the two key factors affecting the surface wettability of materials.[33] Herein, we successfully deposited PVA-TA and PVA-TA $@\\mathrm{SiO}_{2}$ hydrogels on SSM substrate through a simple dip-coating process. As shown in Scheme  2, the ultrasonic-washed SSM was placed in the solution of PVA-TA or $\\mathrm{PVA-TA@SiO}_{2}$ at $60~^{\\circ}\\mathrm{C}$ for 2 min, followed by ethanol evaporation in the air to form a hydrogel coating. The surface morphology of the pristine SSM and the hydrogel coated SSM were characterized by scanning electron microscope (SEM). As illustrated in Figure 4, the pristine SSM has a smooth surface structure with an average pore size about $50\\upmu\\mathrm{m}$ . After being decorated with PVA-TA hydrogel, a smooth and dense hydrogel layer was built on the surface of $\\mathrm{{\\ss{M}}}$ , and the coating thickness was about $1.9~{\\upmu\\mathrm{m}}$ . In sharp contrast, the SSM decorated with $\\mathrm{PVA-TA@SiO_{2}}$ hydrogel has a rough surface with nanostructures, and the coating thickness was about $2.1\\upmu\\mathrm{m}$ . EDX analysis also proved that the hydrogel covered the steel wires uniformly and almost no hydrogel existed in the pores of the SSM, which ensures free passage of water through the prepared coated $\\mathrm{{{SSM}}}$ .  \n\nThe wettability and oil-adhesion properties of SSM decorated with PVA-TA and PVA-TA $\\ @\\operatorname{SiO}_{2}$ hydrogels were characterized. As shown in Figure 5a, after modification of PVA-TA hydrogel, the water contact angle of SSM in the air decreased from $114.7^{\\circ}\\pm3.2^{\\circ}$ to $55.5^{\\circ}\\pm2.7^{\\circ}$ . Generally, chemical composition and surface roughness are essential factors of super-wettability surface.[34] Even though tannic acid and polyvinyl alcohol molecules are both hydrophilic, since the surface of the gel coating is smooth, the water droplets are not completely spread on the surface. In contrast, M/PVA-TA exhibited super-oleophobic properties underwater, with an oil contact angle (OCA) of $152.3^{\\circ}\\pm2.6^{\\circ}$ and a sliding angle of $7.0^{\\circ}$ (Figure S10a, Supporting Information). When $\\mathrm{SiO}_{2}$ was doped in the PVA-TA hydrogel, $\\mathrm{M}/\\mathrm{PVA}{\\cdot}\\mathrm{TA}@\\mathrm{SiO}_{2}$ exhibited super-hydrophilic properties in the air $(\\mathbb{W}\\mathbb{C}\\mathbb{A}=0^{\\circ}$ ) and super-oleophobic underwater (OCA $=156.3^{\\circ}\\pm1.1^{\\circ}.$ ), and the sliding angle was $3.0^{\\circ}$ (Figure S10b, Supporting Information). According to the surface wettability theory of Cassie-Baxter,[35] the underwater superoleophobicity is achieved in oil/water/solid three-phase system by introducing the repulsive liquid phase into the micro-structured surface. In water, the 3D network hydrogel coatings on the surface of SSM absorb water to its equilibrium state. The rough nanostructure of the PVA-TA $@\\mathrm{SiO}_{2}$ hydrogel surface captures more water, and when oil droplets contact the surface, an oil/water/solid composite interface is formed, which is beneficial to prevent oil in contact with the $\\mathrm{{\\sfSSM}}$ and form an underwater superoleophobic surface. We tested the underwater wettability of various oils and organic solvents (including xylene, cetane, hexane, soybean oil and pump oil) to M/PVA-TA $@\\mathrm{SiO}_{2}$ , and the OCAs were all greater than $150^{\\circ}$ (Figure  5b). Considering that oily wastewater is usually in a variety of complex environments, the underwater oil contact angle of M/PVA-TA (Figure 5c) and $\\mathrm{M}/\\mathrm{PVA}{\\cdot}\\mathrm{TA}\\ @\\mathrm{SiO}_{2}$ (Figure  5d) at $\\mathrm{pH}=2\\mathrm{-}12$ was tested. Both M/PVA-TA and $\\mathrm{M}/\\mathrm{PVA}{\\cdot}\\mathrm{TA}\\ @\\mathrm{SiO}_{2}$ had contact angles greater than $150^{\\circ}$ within the $\\mathrm{\\pH}$ range of 2–12. In comparison, $\\mathrm{M}/\\mathrm{PVA}{\\cdot}\\mathrm{TA}\\ @\\mathrm{SiO}_{2}$ is more oil-repellent, and with the increase of $\\mathrm{\\pH}$ value, the underwater oil contact angle has a tendency to increase, which is due to the increase of water content of gel coating.  \n\n![](images/64335f496b7b0082b05f024dde7c990743223fd1f82e30a8e36ca60ae6629ade.jpg)  \nFigure 4.  SEM images of hydrogels decorated SSM and EDX image of $M/P V A-T A@S i O_{2}$ .  \n\n![](images/8bfbd9df4a219bddd0739ced431e1a6b8e92e76d3a754a4363e5aa716e42e0c7.jpg)  \nFigure 5.  a) The water contact angles and underwater oil contact angles of original SSM, M/PVA-TA and $M/P V A\\mathrm{-}\\mathsf{T A}@\\mathsf{S i O}_{2}$ . b) Underwater oil contac angles of the M/PVA-TA $\\textcircled{\\sc1}$ for the various oils. c) The oil contact angles of M/PVA-TA in a $\\mathsf{p H}=2-12$ water environment. d) The oil contact angle of $\\mathsf{M}/\\mathsf{P V}\\mathsf{A}\\mathsf{-T A@S i O}_{2}$ in a $\\mathsf{p H}=2–12$ water environment.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.4. Oil/Water Separation of Hydrogel-Coated SSM  \n\nIn the process of oil-water mixture separation, membrane materials usually suffer from serious oil fouling and pore-blocking, which reduces its separation efficiency and service life. Figure 6a demonstrated the process of oil droplet (chloroform) preloading and adhering to $\\mathrm{{\\sfSSM}}$ underwater. When the oil droplet was loaded on the unmodified SSM, the oil droplet was in full contact with the surface after being pressed in $60~\\mathrm{s}$ After the pressure was removed, the oil droplet was found to adhere to the SSM, indicating poor oil-resistance adhesion performance. However, compared with the pristine SSM, the oil droplets were easily detached from the $\\mathrm{M}/\\mathrm{PVA}{\\cdot}\\mathrm{TA}@\\mathrm{SiO}_{2}$ surface, and there were no oil droplets remaining on the surface. Furthermore, the pre-wetted pristine mesh and the PVA-TA $@\\mathrm{SiO}_{2}$ coated mesh were immersed in hexane to make the surface adhere to oil, and then transferred to deionized water (Figure 6b and Movie S1, Supporting Information). It could be observed that large amount of oil stayed on the pristine SSM surface, while the oil completely slipped off on the PVA-TA $\\ @\\operatorname{SiO}_{2}$ modified SSM, indicating the excellent self-cleaning ability of the gelcoated SSM. Similarly, in Movie S2 (Supporting Information), we found that chloroform adheres to the pristine $\\mathrm{{\\calS}}\\mathrm{{\\calS}}\\mathrm{{\\calM}}$ underwater, but it could easily slip off the surface of the PVA-TA $@$ $\\mathrm{SiO}_{2}$ decorated SSM. These results consistently implied that the PVA-TA $\\ @\\operatorname{SiO}_{2}$ hydrogel coating could effectively prevent the network structure of SSM from being contaminated or blocked by oil during the oil/water separation process, which ensures its potential re-usability.  \n\nTo test the oil/water separation capability of the hydrogelcoated mesh, the mixture of oil (xylene, cetane, hexane, soybean oil, and pump oil) and water was continuously injected into the device shown in Figure  7a. During the entire separation process, no external force was applied, and water rapidly permeated through the PVA-TA ${\\mathcal{Q}}\\mathrm{SiO}_{2}$ coated mesh, while the oil was retained in the upper separating funnel (Movie S3, Supporting Information). After the separation process, nearly no visible oil in the permeated water. As a result, the separation efficiency of different oil products by infrared spectrometer was determined to be above $99\\%$ (Figure 7b). Besides, to demonstrate the robust anti-fouling performance and durability of the $\\mathrm{M}/\\mathrm{PVA}{\\cdot}\\mathrm{TA}\\ @\\mathrm{SiO}_{2}$ , 30 cycles of separation experiments of hexane/water mixture were carried out. As shown in Figure 7c, the PVA-TA $@\\mathrm{SiO}_{2}$ coated SSM remained at a high-level after 30 cycles of separation. Specifically, the flux was greater than $6\\times10^{4}\\mathrm{~L~m}^{-2}\\mathrm{~h}^{-1}$ , and the separation efficiency remained above $99\\%$ . The OCAs of $\\mathrm{M}/\\mathrm{PVA}{\\cdot}\\mathrm{TA}@\\mathrm{SiO}_{2}$ were tested after separation in different cycles (Figure 7d). It was found that the OCAs on the surface of the PVA-TA $\\ @\\operatorname{SiO}_{2}$ coated SSM slightly increased and decreased, and it was still in a super-oleophobic state $(153^{\\circ}-157^{\\circ})$ , which further demonstrated the stability of its underwater super-oleophobic performance. Besides, $\\mathrm{M}/\\mathrm{PVA}{\\cdot}\\mathrm{TA}\\ @\\mathrm{SiO}_{2}$ exhibits better flux and separation efficiency than PVA-TA (Figure S11, Supporting Information), which is consistent with the previous results of wettability characterization. We also measured the intrusion pressure of oil flowing through the coated SSM to characterize the maximum height of oil that the PVA-TA $@\\mathrm{SiO}_{2}$ coated SSM can support. As shown in Figure S12 (Supporting Information), the height measured with hexane as the sample oil was about $16.40~\\mathrm{cm}$ , and the penetration pressure of the oil is $1.06~\\mathrm{kPa}$ . In addition, the separation efficiency and intrusion pressure of $\\mathrm{{{SSM}}}$ with different pore sizes modified by hydrogel coating were also characterized in detail (Figure S13, Supporting Information).  \n\n![](images/a7acd18ebb4d4a7475f408657dba4dcf1e5f49d2154f5eca9b548784232b5efe.jpg)  \nFigure 6.  a) Images show that the adhesion behavior of oil droplets (chloroform) on the surfaces of the pristine SSM and the PVA-TA $\\textcircled{\\sc1}$ coated SSM. b) The underwater self-cleaning ability of the PVA-TA $@\\mathsf{S i O}_{2}$ coated SSM and pristine mesh.  \n\nTo further study the separation performance of PVA-TA $@\\mathrm{SiO}_{2}$ coated $\\mathrm{{\\ss{M}}}$ in different environments, we measured its separation flux and efficiency under artificial seawater and different acid-base conditions. As shown in Figure  7e, $\\mathrm{M}/\\mathrm{PVA}{\\cdot}\\mathrm{TA}\\ @\\mathrm{SiO}_{2}$ had higher stability under artificial seawater and $\\mathrm{pH}=2\\mathrm{-}10$ . At $\\mathrm{pH}=12\\$ , the gel network on the surface was destroyed, but the oxidation of TA may form a hydrophilic layer on the surface of the mesh, which still had a separation function when wetted by water. However, it was found in the separation experiment that the TA oxide layer did not possess the water retention function of the gel layer. After the moisture on the grid surface evaporates in a short time, the oil droplets will pass through the filter. Finally, we also demonstrated the potential of PVA-TA $@\\mathrm{SiO}_{2}$ hydrogel coating for separating oilin-water emulsions. Compared with the oil/water mixture, the oil-in-water emulsion contains emulsified oil droplets ranging from hundreds of nanometers to dozens of micrometer, and due to the presence of surfactants on the oil/water interface, the emulsion is extremely stable and difficult to separate by using $\\mathrm{{{SSM}}}$ . Therefore, a polytetrafluoroethylene (PTFE) membrane with a pore size of $1.0\\upmu\\mathrm{m}$ was selected as the porous substrate to apply PVA-TA $@\\mathrm{SiO}_{2}$ paint. As shown in Figures S14 and S15 (Supporting Information), PTFE/PVA-TA $@\\mathrm{SiO}_{2}$ exhibits excellent underwater super-oleophobic properties, with OCAs of $157.8^{\\circ}$ and sliding angle of $2.0^{\\circ}$ . In the emulsion separation experiment, it showed a separation efficiency ${>}99.5\\%$ and stable antifouling performance, demonstrating the effectiveness of the PVA-TA $@\\mathrm{SiO}_{2}$ coating for the separation emulsion  \n\n![](images/d54ebc5d1521d561d92ae0af1a539baf1eb75c87a57cf886bd5f3ace0493fa12.jpg)  \nFigure 7.  a) Typical oil-water separation experiment process. b) Flux and separation efficiency of $M/P V A\\cdot T A@{\\mathsf{S i O}}_{2}$ for the various oil/water mixtures c) Flux and separation efficiency of M/PVA-TA $\\textcircled{\\sc1}$ for 30 cycles test of hexane/water mixture. d) The underwater oil contact angles of M/PVA-TA $@$ $\\mathsf{S i O}_{2}$ during the cyclic separation experiment. e) Flux and separation efficiency of M/PVA-TA $@\\mathsf{S i O}_{2}$ for the various environments.  \n\nBesides, the mechanical stability of the PVA-TA $@\\mathrm{SiO}_{2}$ coating in the dry and wet state was studied through sand abrasion and water shock experiments. After rubbed by rolling sand grains $(200{-}600~\\upmu\\mathrm{m})$ from the height of 20 to $100\\ \\mathrm{cm}$ (FigureS16b,c:SupportingInformation),theOCAs(FigureS16d, Supporting Information) of the coating grid decreased slightly as the impact height increased, and the underwater super-oleophobic state was always maintained. This is due to the excellent mechanical properties of the gel in the dry state (Figure S16a, Supporting Information). Similarly, after a $20{-}100~\\mathrm{cm}$ water impact test, the OCAs (Figure S16e, Supporting Information) of PVA-TA $\\ @\\operatorname{SiO}_{2}$ coated SSM remained stable, which was attributed to the ultra-high strength of the hydrogel coating and the strong adhesion strength $(757.9\\mathrm{kPa})$ to the stainless steel substrate (Figure S17, Supporting Information). Meanwhile, this work also exhibited advantages in terms of hydrogel strength and separation efficiency compared with previously reported (Table S4, Supporting Information). In general, the hydrogel coated mesh exhibits stability and durability under complex conditions, and has practical application potential in the field of oil-water separation.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 3. Conclusions  \n\nIn conclusion, we reported a simple but effective strategy that exploring ethanol to dynamically modulate the hydrogen bond between PVA and TA in water to prepare a uniform hydrogel coating on SSM surface. When the ethanol evaporates, the initially inhibited hydrogen bond cross-link between PVA and TA is re-formed, which leads to the in situ generation of super-hydrophilic/underwater super-oleophobic PVA-TA $@$ $\\mathrm{SiO}_{2}$ hydrogel coated mesh for robust oil/water separation. The hydrogen bond cross-linked hydrogel composed of PVA, TA and $\\mathrm{SiO}_{2}$ nanoparticles has an ultra-high tensile strength $({>}10\\ \\mathrm{MPa})$ to ensure the stability of the coating under longterm operation. Meanwhile, the gel also shows low expansibility, good adhesion to $\\mathrm{{\\sfSSM}}$ and stable super-wettability in practical application environments. Based on the excellent water retention and stability of the PVA-TA $@\\mathrm{SiO}_{2}$ gel coating, the as-prepared mesh can selectively separate water from the oil/water mixture quickly (flux exceeds $6\\times10^{4}\\mathrm{~L~m^{-2}~h^{-1}})$ , with high separation efficiency $(>99\\%)$ and resistance to oil fouling and they are easy to recycle. We believe that this work has broad application prospects in the fields of underwater petroleum transportation, oil spill accident treatment and domestic sewage purification, and provides important insights into the field of interface wetting modification of hydrogel coatings, and promotes the transformation of hydrogel coating materials from laboratory models to practical applications.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 9,
+        "chunk": "# 4. Experimental Section  \n\nMaterials: All chemicals were obtained from suppliers without additional purification. Polyvinyl Alcohol (PVA-1799, ${\\approx}99\\%$ hydrolyzed) was purchased from Aladdin. Tannic acid (TA, $M\\mathrm{w}=7707\\textrm{g}\\mathsf{m o l}^{-1})$ was obtained from Tianjin Hengxing Chemical Reagent Co. Ltd. Nanoscale $\\mathsf{T i O}_{2}$ $(30\\ n m)$ was purchased from Macklin. The stainless-steel mesh (SSM, 300 mesh) was got from Hebei Anshun Xing Hardware Technology Co., Ltd. The stainless steel sheet (section: $75\\:\\mathrm{mm}\\times0.2\\:\\mathrm{mm};$ was purchased from Hongdu Metal Co., Ltd. Soybean oil and pump oil were purchased from the local market. The polytetrafluoroethylene (PTFE, ${\\mathrm{~1~}}\\upmu\\mathsf{m})$ membrane was purchased from Yibo Filter Equipment Factory. All other chemicals were analytical grade and commercially available from Chron chemicals (Chengdu, China). Deionized water was used throughout the experiment.  \n\nPreparation of PVA-TA and PVA- ${\\cdot\\ T A@S i O_{2}}$ Hydrogels Coated Mesh: PVA $(3.0~\\ g)$ and TA $(3.0~\\mathrm{g})$ were dissolved in $94.0~\\mathrm{g}$ mixed solvent (deionized water/ ethanol $=1\\colon1\\ \\mathsf{v}/\\mathsf{v})$ with stirring at ${\\approx}90^{\\circ}\\mathsf C$ for $6\\mathfrak{h}$ to obtain PVA-TA hydrogel paint. The preparation process of PVA- $\\mathsf{T A@S i O}_{2}$ hydrogel paint was similar to that of PVA-TA. Before adding PVA and TA, $0.6\\ g\\ S_{1}\\mathrm{O}_{2}$ was added to water/ethanol solvent under ultra-sonication for $30\\mathrm{\\min}$ . The quality of PVA, TA and water/ethanol solvent was equal to that of PVA-TA paint. Unless otherwise specified, the concentration of $\\mathsf{S i O}_{2}$ , PVA and TA in the pre-gel was as described above. The SSM (the average pore diameter of $\\approx50~{\\upmu\\mathrm{m}}$ ) was immersed in the above pre-gel solution for $2\\min$ . Then the SSM was taken out from the pre-gel and dried at room temperature to get the hydrogel-coated mesh. The SSM decorated with PVA-TA and PVA-TA $\\@{\\sf S i O}_{2}$ were denoted as M/PVA-TA and M/PVA-TA $\\textcircled{0}$ ${\\mathsf{S i O}}_{2},$ , respectively.  \n\nInstruments and Characterization: The chemical structures were characterized by Fourier transform infrared (FT-IR) (PerkinElmer, Inc., Waltham, MA) at a resolution of $4c m^{-1}$ in the range of $4000{-}500~{\\mathsf{c m}}^{-1}$ Thermogravimetric analysis (TGA) was conducted on TA $Q50$ under an air atmosphere at a heating rate of $20^{\\circ}\\mathsf{C}\\mathsf{m i n}^{-1}$ from 50 to $700^{\\circ}\\mathsf C$ X-ray diffraction (XRD, XPERT PRO, Netherlands) was applied to characterize the crystallization performance of hydrogels, and the scan angle was $5^{\\circ}$ to $50^{\\circ}$ . An electronic universal testing machine (Instron 5567) was used to test the mechanical properties of hydrogel samples (length $50\\mathsf{m m}$ , width $\\mathsf{10}\\mathsf{m m}$ , thickness $0.3\\mathsf{m m}^{\\mathrm{~.~}}$ ) with a stretching speed of $50\\mathsf{m m}$ $\\mathsf{m i n}^{-1}$ . SEM images of the hydrogel coated mesh were obtained using a field emission scanning electron microscope (FESEM, JMS-6490 LV) at $20\\ \\mathsf{k V}.$ Contact angles were measured on DSA 30 machine at ambient temperature.  \n\nThe equilibrium swelling ratio (ESR) of hydrogels in different environments is defined as:  \n\n$$\nE S R=\\frac{\\mathbb{W}_{\\mathrm{s}}-\\mathbb{W}_{\\mathrm{d}}}{\\mathbb{W}_{\\mathrm{d}}}\\times100\\%\n$$  \n\nwhere ${\\sf W}_{\\sf d}$ and ${\\sf W}_{\\sf s}$ are the weight of the hydrogels before and after swelling, respectively.  \n\nOil/Water Separation Experiments: The hydrogel-coated SSM was used to separate the oil/ water mixture $(30\\mathrm{\\mL},\\mathbb{1};2,\\up v/\\up v)$ . The flux of the SSM  \n\nis determined by calculating the filtration time of oil/water mixture and the formula is as follows:  \n\n$$\nF I u x=\\frac{V}{A\\times\\Delta T}\n$$  \n\nWhere $V$ (L), A $(\\mathsf{m}^{2})$ , and $\\Delta T$ (h) are the volume of the filtering water, membrane contacting area, and time used, respectively.  \n\nThe oil concentration before and after separation was determined by an infrared spectrometer oil content analyzer (OIL460, China). The separation efficiency $(R\\%)$ is calculated by the following formula:  \n\n$$\nR^{\\circ}\\rho=\\left(1-\\frac{C_{a}}{C_{b}}\\right)\\times100\\%\n$$  \n\nwhere $C_{a}$ and $C_{\\flat}$ are the oil concentrations after and before separation, respectively.  \n\nThe oil intrusion pressure is determined by the maximum height $(h_{\\mathsf{m a x}})$ of oil that the SSM can support and calculated as follows:  \n\n$$\nP_{o i l}=\\rho g h_{\\operatorname*{max}}\n$$  \n\nwhere $\\rho$ is the density of oil, $g$ is the gravitational acceleration.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# Supporting Information  \n\nSupporting Information is available from the Wiley Online Library or from the author.",
+        "category": " References"
+    },
+    {
+        "id": 11,
+        "chunk": "# Acknowledgements  \n\nThis work was supported by National Natural Science Foundation of China (52173068, 51773028, 52073039), the Fundamental Research Funds for the Central Universities (ZYGX2019J026), Sichuan Science and Technology Program (2020YFG0100, 2019YJ0197, 2019YFG0056, 2021YFH0023) and International Science and Technology Cooperation Project from Chengdu municipal government (2019-GH02-00037-HZ).",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# Conflict of Interest  \n\nThe authors declare no conflict of interest.",
+        "category": " References"
+    },
+    {
+        "id": 13,
+        "chunk": "# Data Availability Statement  \n\nResearch data are not shared.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# Keywords  \n\nhydrogel paint, oil/water separation, polyvinyl alcohol, tannic acid, ultrahigh strength hydrogels  \n\nReceived: May 18, 2021 Revised: August 13, 2021 Published online:  \n\n[1]\t a) C.  Zhou, D.  Huang, P.  Xu, G.  Zeng, J.  Huang, T.  Shi, C.  Lai, C.  Zhang, M.  Cheng, Y.  Lu, A.  Duan, W.  Xiong, M.  Zhou, Chem. Eng. J. 2019, 370, 1077; b) X. Dong, S. Gao, J. Huang, S. Li, T. Zhu,  \n\nY. Cheng, Y. Zhao, Z. Chen, Y. Lai, J. Mater. Chem. A 2019, 7, 2122; c) Y. Xie, Y. Gu, J. Meng, X. Yan, Y. Chen, X. Guo, W. Lang, J. Hazard. Mater. 2020, 398, 122862. [2]\t R. K. Gupta, G. J. Dunderdale, M. W. England, A. Hozumi, J. Mater. Chem. A 2017, 5, 16025.   \n[3]\t a) X.  Lin, J.  Heo, M.  Choi, J.  Hong, J. Membr. Sci. 2019, 580, 248; b) Y. Wang, X. Gong, J. Mater. Chem. A 2017, 5, 3759.   \n[4]\t a) Y. Si, Z. Dong, L. Jiang, ACS Cent. 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J. 2020, 395, 125123.   \n[12]\t L. Xu, S. Gao, Q. Guo, C. Wang, Y. Qiao, D. Qiu, Adv. Mater. 2020, 32, 2004579.   \n[13]\t a) L.  Dai, B.  Wang, X.  An, L.  Zhang, A.  Khan, Y.  Ni, Carbohydr. Polym. 2017, 169, 9; b) Y.  Li, H.  Zhang, C.  Ma, H.  Yin, L.  Gong, Y.  Duh, R.  Feng, Carbohydr. Polym. 2019, 226, 115279; c) J.  Fan, Y. Song, S. Wang, J. Meng, G. Yang, X. Guo, L. Feng, L. Jiang, Adv. Funct. Mater. 2015, 25, 5368; d) Y.  Liu, L.  Wang, H.  Lu, Z.  Huang, ACS Appl. Mater. Interfaces 2020, 2, 4770.   \n[14]\t M. A. Darabi, A. Khosrozadeh, Y. Wang, N. Ashammakhi, H. Alem, A.  Erdem, Q.  Chang, K.  Xu, Y.  Liu, G.  Luo, A.  Khademhosseini, M. Xing, Adv. Sci. 2020, 7, 1902740.   \n[15]\t Y.  Liu, J.  Yin, Y.  Fu, P.  Zhao, Y.  Zhang, B.  He, P.  He, Chem. Eng. J. 2020, 382, 122925.   \n[16]\t a) H.  Liu, H.  Yu, X.  Yuan, W.  Ding, Y.  Li, J.  Wang, Chem. Eng. J. 2019, 374, 1394; b) S. L.  Pedersen, T. H.  Huynh, P.  Pöschko, A. S.  Fruergaard, M. T.  Jarlstad Olesen, Y.  Chen, H.  Birkedal, G.  Subbiahdoss, E.  Reimhult, J.  Thøgersen, A. N.  Zelikin, ACS Nano 2020, 14, 9145; c) Y.  Li, S.  Li, J.  Sun, Adv. Mater. 2021, 33, 2007371.   \n[17]\t Y. Chen, L. Peng, T. Liu, Y. Wang, S. Shi, H. Wang, ACS Appl. Mater. Interfaces 2016, 8, 27199.   \n[18]\t W.  Niu, Y.  Zhu, R.  Wang, Z.  Lu, X.  Liu, J.  Sun, ACS Appl. Mater. Interfaces 2020, 12, 30805.   \n[19]\t a) J. Cai, L. Zhang, J. Zhou, H. Li, H. Chen, H. Jin, Macromol. Rapid Commun. 2004, 25, 1558; b) J.  Cai, L.  Zhang, Macromol. Biosci. 2005, 5, 539.   \n[20]\t a) F.  Weber, A.  Barrantes, H.  Tiainen, Langmuir 2019, 35, 3327; b) M. Arshad, A. Beg, Z. A. Siddiqui, Angew. Makromol. Chem. 1969, 7, 67.   \n[21]\t S. M. Pawde, K. Deshmukh, J. Appl. Polym. Sci. 2008, 109, 3431.   \n[22]\t Y. Chen, C. Jiao, Y. Zhao, J. Zhang, H. Wang, ACS Omega 2018, 3, 11788.   \n[23]\t F.  Lin, Z.  Wang, J.  Chen, B.  Lu, L.  Tang, X.  Chen, C.  Lin, B.  Huang, H. Zeng, Y. Chen, J. Mater. Chem. 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+        "category": " References"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/╙╛╛╡╖└╬э╥й╦о╕─╔╞╩ф╚ы-20191028.json b/task2/task2-chunks/╙╛╛╡╖└╬э╥й╦о╕─╔╞╩ф╚ы-20191028.json
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index 0000000..d0dc1cc
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+++ b/task2/task2-chunks/╙╛╛╡╖└╬э╥й╦о╕─╔╞╩ф╚ы-20191028.json
@@ -0,0 +1,27 @@
+[
+    {
+        "id": 1,
+        "chunk": "# 泳镜防雾药水改善输入",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1 产品与功能描述：  \n\n1.1 产品描述：需求方为专业泳镜产品生产商，主要产品为国际高端品牌游泳眼镜；  \n1.2 产品材质：游泳眼镜的镜片均为PC（聚碳酸酯）通过注塑机注塑而成；  \n1.3 应用场景：业余或比赛用泳池、户外淡水、户外海水等区域；需要对高湿、高温环境具备一定的耐受性；  \n1.4 功能描述：除了其他泳镜产品必须具备的安全、防护功能外，在使用者佩戴后还应该具备较强的防雾性能，需要保证使用者在佩戴的整个过程中镜片的内表面没有雾气，不会影响使用者在水下或水上的视线；同时，对于防雾涂层使用的化学产品，必须符合各主要经济体的安全性要求，所有使用的原材料、配料必须是对人体安全、没有短暂或长期的潜在性安全或健康风险的材料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2 主要性能指标  \n\n2.1 防雾性能测试方法及允收标准：  \n\n<html><body><table><tr><td>编号</td><td>检验项目</td><td>检验方法</td><td>检验标准</td><td>AQL</td></tr><tr><td>1</td><td>防雾持久性/ 功能测试 （泡氯水+未 晾干+60度水 蒸汽30秒）</td><td>1.将防雾好的镜片放在浓度为100ppm 氯水中浸泡1小时； 2．浸泡过程中每10分钟检查一下镜片 3.1小时后将镜片取出，将未晾干的镜 片内表面（防雾面）放在60度水面上方 5CM 处保持30秒 4.移开镜片观察防雾层的变化 5.若不合格，则结束测试；若OK，则 将镜片内表面继续放在60度水面上方</td><td>1.泡氯水检查应无化学成 分形成在镜片上； 2．蒸汽测试检查应无起 皮，无雾气，无结露。</td><td>每个班次每 个产品在首 检时取一次 样,取样2 付 0收1退</td></tr></table></body></html>  \n\n<html><body><table><tr><td></td><td rowspan=\"2\">5CM处保持15分钟 6．移开镜片观察防雾层的变化</td><td rowspan=\"2\"></td></tr><tr><td>1．将防雾好的镜片放在浓度为100ppm</td></tr><tr><td>防雾持久性/ 功能测试</td><td>氯水中浸泡1小时； 2.浸泡过程中每10分钟检查一下镜片 3.1小时后将镜片取出，将晾干的镜片 内表面（防雾面）放在60度水面上方 5CM处保持30秒</td><td>无起皮， 无雾气，无结露。 每个班次每</td></tr><tr><td>2 （泡氯水+晾 干+60度水蒸 汽30秒)</td><td>4.移开镜片观察防雾层的变化； 5.若不合格，则结束测试；若OK，则 将镜片内表面继续放在60度水面上方 5CM处保持15分钟；</td><td>个产品在首 检时取一次 样,取样 2付 0收1退</td></tr><tr><td>防雾功能测试 3 （冰箱测试）</td><td>6.移开镜片观察防雾层的变化。 1.将镜片放在温度为5℃，湿度为 60±5）%的环境中30分钟，然后取出 镜片在室温下检查镜片防雾层变化。</td><td>无雾气，无结露</td></tr></table></body></html>  \n\n<html><body><table><tr><td rowspan=\"2\">4</td><td>防雾层老化测 试</td><td>将防雾好的镜片放入温度为40℃，湿度 为80%的试验箱内，放置时间为48小 时，每隔24小时检查一次。</td><td>1.48小时后防雾层无物理 变化，如起皱，脱落，结 晶等； 2.48小时后镜片防雾层无</td><td rowspan=\"2\"></td></tr><tr><td>5 晾化测试</td><td>1.将防雾好的镜片在常温长湿下放置6个 月</td><td>永久雾状 1.每周观察镜片有无物理 变化如：起皱，脱落等； 2.记录每隔一周的检查结 果</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2.2 安全符合性要求：  \n\n2.2.1 防雾涂层所使用的所有原材料、辅材均不得具有对人体造成现实或潜在的、短期或长期的安全或健康损害的风险；  \n2.2.2 应符合世界主要经济体的相关产品的安全性标准或有害物质限定，如欧盟的ROHS、REACH 等；",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 3 改善需求：  \n\n3.1 缩短烘干或固化时间，目标 $\\leqslant60$ 秒；  \n3.2 降低固化使用的能耗，取消高温高能的固化方式；  \n3.3 药水使用简便，即取即用，无需复杂、繁琐的使用前准备、勾兑程序；无需严苛的存储条件，常温常湿条件下可以保存；  \n3.4 无需复杂、繁琐的后处理程序，如水洗等；涂完即用；  \n3.5 提升防雾功能持久性：3.5.1 首次使用前，保质期 1 年或以上；3.5.2 多次使用后，防雾性能保证在 2 个月或 15 次以上；  \n3.6 镜片未附着的药水可以重复使用，允许添加或再次勾兑；  \n3.7 提升经济性：单副镜片（2 片）使用的药水成本≤RMB 0.15",
+        "category": " Results and discussion"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/╚э╨╘║═╥║╠м╖╓╫╙▓─┴╧╡─╗·╞ў╤з╧░.json b/task2/task2-chunks/╚э╨╘║═╥║╠м╖╓╫╙▓─┴╧╡─╗·╞ў╤з╧░.json
new file mode 100644
index 0000000..9ce2464
--- /dev/null
+++ b/task2/task2-chunks/╚э╨╘║═╥║╠м╖╓╫╙▓─┴╧╡─╗·╞ў╤з╧░.json
@@ -0,0 +1,102 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Machine learning for soft and liquid molecular materials  \n\nTetiana Orlova, $\\textcircled{1}$ a Anastasiia Piven, $\\textcircled{1}$ a Darina Darmoroz, $\\textcircled{1}$ a Timur Aliev, $\\textcircled{1}$ Tamer Mahmoud Tamer Abdel Razik, $\\textcircled{1}$ a Anton Boitsev, $\\textcircled{1}$ b Natalia Grafeeva $\\textcircled{1}$ and Ekaterina Skorb \\*a  \n\nReceived 27th November 2022   \nAccepted 15th February 2023  \n\nDOI: 10.1039/d2dd00132b rsc.li/digitaldiscovery  \n\nThis review discusses three types of soft matter and liquid molecular materials, namely hydrogels, liquid crystals and gas bubbles in liquids, which are explored with an emergent machine learning approach. We summarize specific examples of the use of machine learning technique to study the structure and properties of soft matter at the molecular, microscopic and macroscopic levels. The approaches of artificial intelligence have greatly improved the prediction of material properties, stimulated the progress in modeling methodologies capable of revealing physical phenomena, and opened up new perspectives in the design and use of soft material devices. For this reason we also provide guidance on machine learning methods and recommendations on best practices for data understanding.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1 Machine learning methods: general introduction  \n\nAlthough ML technology appeared in the middle of the previous century, real opportunities for the practical application of the developed algorithms appeared only when the computing power of personal computers changed signicantly. This is due to the fact that most of the algorithms developed require a considerable amount of computing resources. Today, ML algorithms are widely used for the tasks of recognizing the plots of drawings, faces, the tonality of texts, annotating texts, checking grammar, spelling, and many other tasks as well. Therefore, spheres of human activity where the road to ML approaches is open are developing at an unprecedented pace and many researchers in various branches of science question themselves how to apply ML methods in their own “sandbox”.  \n\nThe eld of so and liquid molecular materials can also be such a playground (Fig. 1). In this article, we consider the main categories of ML problems and algorithms and their applicability in the eld. Among the tasks to be solved by ML methods, several categories are particularly in demand. Let us briey introduce them to you.  \n\nThe purpose of dimensionality reduction1 is as follows. A large number of data features are reduced to fewer for future data visualization or application of other ML algorithms in real time. The anomaly detection2 is also a very important eld. Atypical objects (which are found in any industry) are separated from the usual (standard) ones based on various statistical characteristics of the entire sample or other ML algorithms. The regression3 is the task of predicting the possible characteristics of new objects based on a sample of existing objects with a set of features, while the classication4 is the task of assigning objects to predened groups based on a set of features (there can be 2 or more classes). Finally, the clustering5 is the task of dividing the analyzed objects into an unknown number of groups based on a set of features, highlighting the structure in the data.  \n\nThe tasks mentioned above are solved by various methods, but perhaps the most well-known in this eld are the following.  \n\n![](images/de1b0271cea832fea24b1eefaf3b32daf5fb512feee29dc355a0e64022f3ed92.jpg)  \nFig. 1 (a) Soft and liquid molecular systems considered in this review. (b) Scopus analysis of the number of published papers, when the search query is associated with the title, keywords and abstract, and the results are limited to articles and conference papers.  \n\nThe Principal component method6 (PCA) is basically an orthogonal transformation that allows to translate observations of interrelated variables into a set of principal components or linearly uncorrelated values. PCA is used to provide visualization of the source data, as well as to minimize them and facilitate the learning process itself.  \n\nThe Nearest neighbor method7 (k-NN) is a very popular classication method, sometimes used in regression problems. This is one of the most intuitive approaches to classication. The essence of the method is as follows: new objects are added to objects already divided into classes according to the principle of “the nearest neighbor”. Hence, the new object falls into the class that is closer to it by attributes. The distance (proximity) between neighbors is determined by various metrics.  \n\nDecision trees8 are a method that implements decision– making based on the use of a tree graph. Such a tree is formed from the minimum possible number of questions with an unambiguous answer (either “yes” or “no”) based on existing labeled data. Aer entering the sequence of answers, the user comes to the right choice. As a rule, the method is used in classication tasks.  \n\nThe Support Vector Machine9 (SVM) is an algorithm that is actively used to solve classication problems. The main idea of the algorithm is iterative partitioning of $N\\cdot$ -dimensional objects by hyperplane of dimension $\\left(N-1\\right)$ .  \n\nClustering algorithms5 deal with the distribution of analyzed objects into clusters, in which similar elements should appear. Various algorithms based on probability, density, dimension reduction, etc. are used for clustering.  \n\nNeural networks10 are an apparatus based on a mathematical model of the interaction of neurons in the human brain. To apply the model, the network is pre-trained on the basis of existing “marked up” data. Currently, the neural networks approach is one of the most popular branches of machine learning. Unlike classical ML algorithms, their advantage is that complex and important work on the formation of features before applying the algorithm (feature extraction) is alienated from the researcher and le to the algorithm.  \n\nIn the next section of the article, we focus on the machine learning methods already applied in liquid molecular materials tasks and to what extent this application is justied.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2 Machine learning for hydrogels",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2.1 Introduction in hydrogels  \n\nDue to their unique features like swelling and deswelling and stimuli-responsiveness, polymer hydrogels have attracted much attention as outstanding – so and wet – materials (e.g., temperature, $\\mathsf{p H}$ , ionic strength, or chemical reactions).11 On the other hand, traditional single-network hydrogels are too so and fragile, with low fracture energies to maintain their strong resistance to crack propagation.12 Hydrogel as a material can be classied according to different criteria. The preparation method is one of the earliest hydrogels that can be divided according to enveloped polymer sources into hydrogel, semisynthetic, and synthetic hydrogels. Most natural-based hydrogels are biodegradable, whereas the synthetic-based ones can be nondegradable and have a long life (or be undegradable). Hydrogels can be classied as anionic, non-anionic, or neutral according to the ionic charges on the polymer and fragments. Classify hydrogels using homopolymers, copolymers, or interpenetrated polymers. The amphoteric change of hydrogel charges with different environmental conditions could give the hydrogel intelligent properties.13  \n\nRecently, there has been increased interest in hydrogel because of its unique properties that enable it to spread in several applications. Additionally, numerous books and articles on hydrogel materials have been published over the past few decades and offer more comprehensive and varied perspectives. There has been a fast growth of novel hydrogel materials and correlated research between 2000 and 2021, which has not been reviewed frequently. Fig. 1b shows a recent number of publications, including hydrogel and machine learning.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2.2 Models for functional hydrogel  \n\nRegardless of the materials class or performance criteria, hydrogel science research aims to build process–structure– property–performance correlations.14 These relationships between a material's manufacturing process, its micro-or nanoscale structure, and its properties and performance in a given application frequently involve complex cause and effect interactions, requiring a sizeable parametric space and a variety of synthetic characterization and theoretical techniques. Materials scientists have already identied three interacting paradigms to generate those types of relationships: theory, experiment, and simulations. While tests directly measure and quantify material performance, the theory provides a mathematical framework for understanding and predicting correlations. The most recent of the three paradigms, computational simulations, uses theory to do granular hydrogel simulations of experiments to provide more insight into difficult or impossible phenomena to detect experimentally. If an experiment doesn't support a theoretical relationship, it isn't complete, and simulation approaches are oen better at describing what happened in the experiment.14  \n\nThe signicantly increased ability of materials scientists to collect, share, and analyze large volumes of data in recent decades has led to what many are calling the fourth paradigm of materials science, also known as data-driven materials discovery or materials informatics (MI).15,16  \n\nMI is a discipline in which correlation relationships can be suggested or validated by examining massive data sets of materials using statistical techniques, many of which use machine learning. An informatics strategy uses these enormous data sets to alter more standard correlation relationship development methods. For example, a more traditional technique might utilize a theoretical model based on our understanding of chemistry and physics to predict a material's attributes based on its structure and composition. Experimental measurements of the structures and expected properties can then be used to validate or alter the theoretical model. Instead, an informatics method develops a model using data from the inputs (structure) and the measured responses (properties).  \n\nThis model can then predict responses to similar or only slightly different inputs, and cross-validation can test and improve its ability to do this.  \n\nA wide range of technological applications are enabled by functional hydrogels, which are made up of crosslinked 3D macromolecules and molecular building blocks that selforganize into complex structures as a result of their adjustable connections. Inverse approaches allow designers to navigate their intrinsically high-dimensional design areas in order to generate materials with specic qualities. While a number of physically driven inverse techniques have been effectively applied in some circumstances, their application to directing experimental materials discovery has been conned to a few proof-of-concept investigations thus far.17 We highlight recent improvements in inverse methods for hydrogel design that address two issues: (1) methodological limits that prevent such approaches from satisfying design requirements and (2) computing challenges that limit the pore size and network structure that may be addressed. Methods to identify order parameters that characterize complicated structural motifs, as well as approaches to effectively compute macroscopic features from the underlying structure, have proven to be particularly effective. We also talk about promising ways to improve the accuracy and computational efficiency of models that are relevant to experiments, such as nding materials that work in more than one thermodynamic state, making protocols for externally directed assembly that are easy to use in experiments, and coming up with other ways to improve the accuracy and computational efficiency of models that are relevant to experiments.  \n\nDrug delivery systems,18 wound dressing membranes,19 cell culture,20 tissue engineering21 and other critical applications have all beneted from tailored hydrogels. The use-inspired behaviors of these materials are caused by the physicochemical properties of their constituent components and their internal spatial organization (i.e., structure). Synthetic polymers, polysaccharides, and proteins can serve as powerful material building blocks for hydrogel formation because their mutual interactions, which help determine the system's favored equilibrium state, can be systematically varied through, for example, their size, shape, charge, composition/sequence, and surface functionalization.  \n\nThis opens up many design possibilities. It is a big job to determine which building components may consistently selfassemble a material with a given structure or desired macroscopic features. Innovative approaches to the search for new self-assembling materials are routinely used. In such approaches, an initial set of material building blocks is synthesized, and strategies are developed to make self-assembly easier in an experiment or a computer simulation. The structure and qualities of the nal material are next investigated. These processes are repeated (typically numerous times) to hunt for materials with superior attributes using other building blocks or protocols. Instead of framing this process as an inverse problem, framing it as a methodology and amenable to meeting stated design objectives can be advantageous. For example, a gure of merit (FOM) can be set up based on the desired structure or macroscopic property, and constrained optimization methods can move through the multidimensional design space and determine which building blocks, interactions, or protocols are best for making material.  \n\nKalasin and his coworkers developed The Remote Articial Intelligence-Assisted Epidermal Wearable Sensing for Environmental Heat-Stress Sweat Creatinine Monitoring based on Satellite-Based Sensor. His group develop coated nylon with poly(vinyl alcohol) (PVA)- $\\mathrm{Cu}^{2+}$ -poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) and cuprous oxide nanoparticles. The system was equipped with heart rate monitoring and a satellite communication device to locate wearers, and incorporates machine learning to predict the levels of environmental heat stress. Electrochemical impedance spectroscopy (EIS) was used to investigate different charge-transfer resistances of PVA and PEDOT:PSS with cuprous and cuprite ions induced by single-chain and ionic cross-linking.22  \n\nTo improve the performance of ultrasound-mediated chemical sensing using titanium dioxide $\\left(\\mathrm{TiO}_{2}\\right)$ nanoparticlesembedded hydrogel, Islam and his colleagues used machine learning. A new wireless pH sensing technology has been developed using ultrasound transmission through titanium dioxide $\\left(\\mathrm{TiO}_{2}\\right)$ nanoparticle-embedded hydrogels. An ultrasonic transmitter/receiver pair and a $\\mathrm{TiO}_{2}$ -embedded hydrogel implanted under the skin make up the sensing system (or any other body area that requires pH monitoring). Filling hydrogel with $\\mathrm{TiO}_{2}$ nanoparticles improves ultrasonic wave backscattering, obviating the need for complex readout devices like ultrasound imaging. The physical behavior of ultrasonic waves changes as they ow through the hydrogel, depending on the thickness of the hydrogel. The ultrasonic receiver, located on the other side of the body, captures the changed ultrasonic wave caused by the hydrogel. Ultrasound activities were used to investigate the volumetric transition of hydrogel wirelessly. The delivered ultrasonic signals are gathered with feature extraction for machine learning applications in mind. This approach uses ultrasonic waves to measure pH information with low reection and noise effects. Despite having many scopes, no machine learning-enabled direct pH measurement systems have been published previously. The measurement errors of today's stateof-the-art pH sensors (with analyte) are within 0.1 to $0.01~\\mathrm{pH}$ . So, this research aims to nd ways to use machine learning to make the error rate even lower.23  \n\nFor 3D printed bioink, Lee and his colleagues use a machine learning-based design technique. They used a model system using naturally produced biomaterials to build a machine learning-based method for designing a 3D-printable bioink. First, they showed that, compared to native collagen, atelocollagen (AC) had better physical qualities for printing (NC). NC gel had highly crosslinked and temperature-responsive irreversible behavior, resulting in brittleness and high yield stress. In contrast, AC gel had weakly elastic and temperatureresponsive reversible activity, generating a so cream-like structure with low yield stress. Then, using machine learning, they identied a universal relationship between the mechanical parameters of ink and printability: a high elastic modulus increases shape delity, and extrusion is possible below the threshold yield stress. Based on this relationship, they were able to use multiple regression analysis to make a lot of different formulations of bio-inks made from natural materials with great shape delity. Finally, using a framework of high form delity bioink, a 3D model of a cell-laden hydrogel was created, revealing that the cells are incredibly viable and proliferative in the 3D structures.24  \n\nLiu and his colleagues created a system based on photography and machine learning, which they used to hydrogel pressure distribution sensors. The team proposed and built a hydrogel pressure distribution sensor that can monitor pressure distribution across the entire hydrogel component. This is performed via a technique called electrical impedance tomography (EIT), which involves putting electrodes just around the hydrogel (EIT) (Fig. 2). Meanwhile, $\\mathrm{PAAm/PAA{\\cdot}F e^{3+}}$ doublenetwork hydrogels were developed as hydrogel pressuresensitive substrates, and mechanical and electrical tests conrmed their suitability as sensitive elements for hydrogel pressure distribution sensors. A machine learning method based on the hydrogel pressure distribution sensor was also used to create a pressure distribution reconstruction model. Finally, the hydrogel pressure distribution sensor was used to test the viability of the EIT strategy-based hydrogel pressure distribution sensor by applying forces of known position and magnitude. The real sensor data was then reassembled and compared to the applied force.25  \n\nLi and his co-authors use chemical characteristics to examine the design of self-assembly dipeptide hydrogels and machine learning (Fig. 3). They built a peptide-like chemical library for screening chemicals that can produce hydrogels based on a Ugi four-component reaction. A rheometer and transmission electron microscopy (TEM) evaluated selected hydrogels, which were then grown with an adherent cell line. The machine learning method was designed to recognize these chemical properties and forecast whether a chemical structure may form a hydrogel at neutral pH without any divalent or trivalent metal ions. In addition, the molecular structure and gelation property connection was summarized.26  \n\nThe researchers examined several polysaccharide hydrogels to nd functional properties that could predict antibiotic accumulation in Gram-negative bacteria. A model composed of starch hydrogel was evaluated in the Gram-negative model bacterium $E$ . coli and shown to be exceptionally capable of discriminating high from low-accumulating antibiotics. The rapid penetration of porin-dependent antibiotics in the starch gel matches Gram-negative specic porin-mediated absorption. However, ndings on nalidixic acid permeation and structurepermeability connections suggest that this approach can also discover high-accumulating medicines with good porinindependent outer membrane penetration. Whether manually pipetted or printed, model preparation is simple, reproducible, cost-effective, and risk-free. Membrane-permeation tests can be done automatically and give accurate results in as little as 10 minutes. This makes them great for high-throughput screening of compounds with different physical and chemical properties.  \n\n![](images/e0d50ff21a373ea21359ee93be5e8b879d265b4a4dba1f8146d53e64f750b5fe.jpg)  \nFig. 2 (a) Hydrogel pressure distribution sensor consisting of two parts, an electrode array board where the hydrogel can be placed, and a driver board, tested with a force gauge. (b) Predicted maps of plantar pressure distribution during the simulated walking process, starting with heel under pressure, then with whole foot under pressure, next with main force on the forefoot, and finally with big toe under pressure while the foot is lifted. (c) The maximum predicted impedance value of the compressed area (MPICA) shows a linear correlation with the actual pressure applied to the sensor. All figures are adapted with permission from ref. 25.  \n\n![](images/a783a177eb39ec10d50c45b34506f75e4d84166949b8e91618535fe043a64fa8.jpg)  \nFig. 3 (a) A typical method of peptide-based hydrogel preparation and the question of hydrogel formation as a binary classification problem. (b) The precision–recall (PR) and receiver operating characteristic (ROC) curves obtained for the random forest and gradient boosting models of hydrogel formation. All figures reprinted with permission from ref. 26.  \n\nModern machine learning approaches to in vitro data offer evidence of the inuence of previously revealed molecular characteristics in bacteria. Based on in vitro permeation data, it was determined that a small set of seven features was all that was needed to build a reliable machine learning model that predicted well. In testing the ability of different medicines to pass through cells in a lab, the rst evidence of bacterial accumulation of aminoglycosides and sulfonamides, which are essential antibiotics for treating Gram-negative infections, was found. By optimizing the composition of the alginate formulation or using biological hydrogels, the experiment could be changed to study the permeability of biolms, exopolysaccharides, or mucus on a larger scale.27",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.3 Machine learning approaches  \n\nEnergy sources that integrate with a person have certain requirements: extensibility, soness and exibility. The triboelectric nanogenerator (TENG) developed by Fan et al.28 based on catechol-chitosan-diatom hydrogel allows these requirements to be taken into account. Based on the data obtained from the TENG based on the tremor of the hands of a sick and a healthy person, the KNN and SVM models were trained, of which the linear SVM showed an accuracy of $100\\%$ . Hydrogelbased TENG data show that hydrogels and articial intelligence can be combined into smart electronics, which over time will help track the condition of athletes, as well as patients with certain diseases in real time29 (Fig. 4a).  \n\nHydrogels are being used in conjunction with machine learning for biological stem cell research. A group of scientists from Rutgers University created a system to analyze the high content of the true three-dimensional organization of SC-35 cells with machine learning approaches to classify the resulting cell states when cells are cultured in three-dimensional scaffolds. This system makes it possible to study cells without destroying them, since PCR, ow cytometry and immunoassays are time consuming and require cells to be extracted from the system (differentiation, apoptosis, transformation). Decision tree models for three types of cells were trained in the WEKA soware package.30 Each of the models showed an accuracy above $70\\%$ with an average error of no more than 0.4 (ref. 31) (Fig. 4b).  \n\nIn an article by a research group from the ITMO University's ISC Infochemistry Scientic Center, hydrogels were used to collect a database using cyclic voltammetry. The obtained data was used to create a random forest model in the WEKA soware package.30 Four different hydrogels were used with different combinations of encephalitis antibody and antigen. The accuracy of the model was $93\\%^{32}$ (Fig. 4c).  \n\nHierarchical machine learning with small datasets has made it possible to create a pipeline that allows to analyze and predict the parameters required for the 3D printing method of so hydrogel molds – freeform reversible embedding of suspended hydrogel (FRESH).33 During the study, 48 seals were analyzed. They were analyzed based on a statistical comparison of CAD les and, obtained from them, real samples. LASSO regression with the parametrization of the middle layer to the upper one showed good values of the coefficient of determination $R^{2}={}$ 0.643 34 (Fig. 5a).  \n\nHydrogels are used in supramolecular chemistry to study and analyze the process of release of supramolecular assemblies. The support vector machine was used to predict the binding energies of supramolecular assemblies with various molecules. Supervised learning was applied to create classi- cation and regression models. In the training dataset, the data obtained by the DFT method were used, such as: geometry from optimized orientation, eigenvalues condensed to atoms, all electrons, condensed to atoms, geometry accompanying electronic data, electrostatic properties, electric eld gradient, gradient eigenvalues. Also in the dataset, environmental data was used, such as: temperature, buffer and salt concentration and pH. In the course of the study, it was possible to train models that showed their effectiveness by correctly predicting the binding energy of cucurbit[7]uril with promising drugs against low-grade gliomas in children: the RAF type II inhibitor TAK-580 (ref. 35) and the MEK inhibitor selumetinib.36 The models predicted that RAF would have a high binding energy and MEK would have a low binding energy, which was conrmed experimentally. RAF and MEK were incorporated into a hydrogel based on cucurbit[7]uril with the same release kinetics of both guest structures for the needs local drug delivery37 (Fig. 5b).  \n\n![](images/fc26b20ec9daa9b894c054046aa8b936b7635f12697ec7957bc0b9a628f5294f.jpg)  \nFig. 4 (a) Catechol-chitosan-diatom hydrogel as triboelectric nanogenerators for collecting energy from human movements to monitor the health of a person with Parkinson's disease using machine learning methods. Reprinted with permission from ref. 29. (b) Predictive cell-state classification model based on computed quantitative 3D nuclear metrics for splicing factor SC-35. Reprinted with permission from ref. 31. (c) Using the random forest algorithm to determine the presence of encephalitis antigen in an electrochemical system. Reprinted with permission from ref. 32.  \n\n![](images/fe52fcacd729d903fae99d09e4636497ede1c047390945080f7f5c988d3109a9.jpg)  \nFig. 5 (a) Hierarchical machine learning to predict the best parameters for 3D printing of elements from alginate hydrogel. Reprinted with permission from ref. 34. (b) Use of support vector machine for binding energy prediction in supramolecular chemistry with hydrogel depot release. Reprinted from ref. 37 with permission from the Royal Society of Chemistry. (c) The use of hydrogels based on collagen, fibrils and hyaluronic acid for the development of 3D biofilms using machine learning methods. Reprinted with permission from ref. 38.  \n\nHydrogels based on collagen, bril and hyaluronic acid are considered for 3D printable bioinks. The correlation between rheological properties and printability was analyzed using the relative least general generalization algorithm. The input parameters were the concentrations of three initial components of the hydrogel. Two outputs were obtained. The rst output is the rheological parameters, and the second output were printing results such as shape delity. Combining it with multiple regression analysis, Lee with co-authors showed operating window maps to determine printability of natural hydrogels38 (Fig. 5c).  \n\nResearch is also using machine learning to automate the hydrogel manufacturing process. Hydrogels in which bacteria were introduced were used as an experiment. Differential dynamic microscopy was used to determine the gelation rate. For the selection of parameters, Bayesian methods of machine learning were used. A machine learning pipeline was obtained, which independently selected parameters for gelation, and aer the experiment, estimated the speed and selected more efficient parameters.39",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 3 Machine learning for liquid crystals",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 3.1 Prediction of liquid crystal phases based on molecularlevel description  \n\nFor all known liquid crystal (LC) phases, thermotropic, lyotropic and metallotropic, the mesophase formation depends on the molecular architecture of a substance, which includes chemical structure, topology, polarity and polarizability.40 The phase transition to the LC state is driven by macroscopic physical parameters such as temperature, concentration, pressure, and the ratio of organic and inorganic components for metallotropic LCs.40 Despite the general understanding about the chemical structures typical of mesogenic compounds, it remains difficult to predict the formation of an LC state for a particular chemical substance. Thus, early attempts to use a machine learning approach for liquid crystals were focused on predicting the mesogenic properties of mono-component materials.  \n\nVarious classication algorithms, such as multi-linear regression analysis and neural networks, were tested aiming to predict liquid-crystalline property from molecular structures of individual chemical compounds encoded by different sets of numerical descriptors along with the clearing temperatures.41–44 Despite the large number of compounds used for to train neural networks by Kr¨anz with co-authors,41 the clearing temperatures were predicted by the best with a standard deviation of $13^{\\circ}$ , which is a rather high error, especially in the case of LC materials with a clearing temperature close to room temperature. Improvements in neural network model descriptors have reduced the RMS error to just a few degrees42 along with successful encoding of clearing temperature trends into homologous trends.43 A comparison of three classes of machine learning algorithms such as eager learners, lazy learners, and neural networks has shown that no heuristic is better than another on the set of all possible problems.44 All classication algorithms represented good methods for predicting the liquidcrystalline property, but their efficiency depended on a specic problem.  \n\nThe quantitative structure–property relationship (QSPR) methodology, combined with a specic type of feed-forward articial neural network, has been applied to predict the liquid crystallinity and phase transition temperature of bentcore molecules.48 (Fig. 6a) The authors turned to nonlinear QSPR models and for the rst time used a group method of data handling type neural network, testing several machine learning models with different sets of molecular structure descriptors. The developed neural network models demonstrate an improvement in determining the clearing temperatures compared to the results obtained in a previous study.49 using the multivariate adaptive regression splines technique. Key structural features that affect the transition temperature of vering bent-core aromatic compounds have also been identied.  \n\nRecently, a general methodology was presented by Chen and coworkers50 to identify appropriate machine learning algorithms and molecular descriptors for predicting a wide variety of liquid crystal behavior of organic compounds based on QSPR. Almost a dozen machine learning algorithms were compared using a dataset from the LiqCryst 5.2 database51 with 3786 entries, of which 2780 compounds exhibit liquid crystal behavior. The most accurate for predicting the liquid-crystalline behavior was the random forest algorithm, while the molecular descriptor took into account the mesogen and wings of the chemical structure. Other advantages of the classier included no pre-processing, quick training, simplicity and versatility for different descriptor inputs. This extensive study can serve as the basis for constructing a multipurpose QSPR model for each type of mesogenic molecule, including the prediction of desired LC properties for unknown or not yet synthesized compounds.  \n\nAer a number of the above-mentioned studies predicting the properties of monodisperse molecular systems, a similar attempt was made for polydisperse systems.45 (Fig. 6b) A dissipative particle dynamics simulation method, developed specically for so matter and complex liquids,52 was used to analyse self-assemble structures and phase transitions in the binary LC system. The order parameter and the phase transition temperature were predicted using several different machine learning algorithms, among which the random forest method showed the highest predictive ability. This study is an important step forward since many of technologically signicant liquid crystals are multi-component mixtures, for instance, the widely popular thermotropic nematic LC E7 (Merck).53  \n\n![](images/6ccc88312645027fd17de241875084fabf6db5e8bd215a5a33a9514f46c8971b.jpg)  \nFig. 6 (a) Phase transition temperature prediction for binary LC systems using machine learning methods (random forest, linear regression, ridge regression, elastic network regression, and support vector regression). Reprinted with permission from ref. 45. (b) Analysis of phase transitions in liquid crystal 12BBAA (4-bromobenzylidene- $4^{\\prime}$ -dodecyloxyaniline) using the $\\mathsf{k}$ -means cluster analysis of infrared spectra. Reprinted with permission from ref. 46. (c) Che and the twenty nsaturated and ten saturated fatty acids studied, where blue arrows indicate the locatio perimentally revealed (left) and predicted (right) phase diagrams for mono saturated y acids for samples. The mesophase type is indicated as the inv $\\begin{array}{r}{(\\mathsf{Q}_{||}^{\\mathsf{D}})_{+}}\\end{array}$ primitive cubic $(\\dot{\\bigcirc}_{||}^{\\mathsf{P}})$ , inverse hexagonal $(H_{1\\vert})$ , microemulsion $(\\mathsf{L}_{2})$ , micellar cubic $(\\mathsf{I}_{2})$ , lamellar crystal $(\\mathsf{L}_{c})_{.}$ , and a combination of $L_{\\alpha}+L_{2}+L_{3}$ phases. Reprinted with permission from ref. 47.  \n\nLipid-based lyotropic LCs are of considerable interest as potential delivery systems for drugs and in vivo imaging contrast agents. Therefore, Le and Tran extended machine learning to predict the complex phase behavior of monoolein and phytantriol based lyotropic LC nanomaterials.54 Robust models were developed for seven different mesophases considering the effects of two types of lipids, 20 unsaturated fatty acids, 10 saturated fatty acids, a range of fatty acid/lipid ratios, and temperature. The phase behavior prediction was obtained with high accuracy using a Bayesian regularized articial neural network. In addition, the developed models were able to interpolate data for the same fatty acids at temperatures that have not yet been tested, as well as extrapolate data for new lipid nanomaterials, thus elucidating rules that will be useful for the future development of advanced lipid systems for therapeutic delivery. It is worth noting that earlier Le with co-authors reported on the same Bayesian regularized neural network capable of predicting with high accuracy the complex nonstationary behaviour of amphiphilic nanostructured mesophases over time and under the inuence of various crystallization screens.47  \n\nMore than 50 new LC phases have been discovered during extensive studies of bent-shaped molecules over the last 20 years.55 Among them, one of the most fascinating is the twistbend nematic phase, when the director follows an oblique helicoid at a constant oblique angle to the helix axis. Recently,56 it was demonstrated that a machine learning protocol can describe the helical trajectories of hard curved spherocylinders57 that form the twist-bend phase in dynamic Monte Carlo simulations. The pitch and radius of the trajectories of diffusing hard particles are determined by the pitch and conical angle of twist-bend nematic phase, thereby relating the structural and dynamic properties of this complexly ordered LC. Such studies are important not only for fundamental science, but also for the industry of LC-based devices, for instance, optoelectronic elements with switching times that are determined by the diffusion rate.  \n\nThe machine learning-based analysis of molecular descriptors or molecular dynamics data is not the solely way to predict complex phase behaviour. For example, the cluster analysis method was applied to the temperature-dependent infrared spectra of a mesogenic chemical compound 12BBAA (4-bromobenzylidene-40-dodecyloxyaniline)46 (Fig. 6c). Changes in the FT-IR spectra are associated with the alkyloxy chain melting phenomena. Thus, phase transitions from an isotropic liquid to smectic A, crystalline smectic B, and a crystalline phase were successfully predicted from spectroscopy data on the characteristics of vibrational bands.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 3.2 Prediction of liquid crystal characteristics from macroscopic data  \n\nOptical microscopy was the rst early method to demonstrate that LCs represent a new state of matter.58 Observations of the optical textures of liquid crystals can provide a lot of information about the macroscopic structure of LC phases.59 There are many experimental methods for studying the structure and physical properties of LCs, but oen routine inspection by polarized optical microscopy is sufficient to draw conclusions about the ordering and symmetry of the LC phase. Obviously, it is a tempting idea to predict the parameters of a LC phase only from textures images.  \n\nThe group led by Ribeiro showed that machine learning methods are able to capture many fundamental characteristics of liquid crystals in an equilibrium state directly from optical images of LC textures.60,62,63 Convolutional neural networks (CNNs) and k-nearest neighbors algorithm trained on simulated optical images of nematics and cholesterics have successfully predicted the LC phase (nematic or isotropic), the order parameter, and the pitch of the cholesteric helix.60,62 (Fig. 7a) Furthermore, these algorithms demonstrated ability to predict the temperature of the nematic phase, the phase transition and its order, and the chiral dopant concentrations from experimentally obtained optical microscopy images(Fig. 7b). Newly,63 it has been shown that ordinary networks of only 24 nodes encode enough optical information that, when combined with a simple machine learning method, is enough to identify and classify mesophase transitions with high accuracy, determine concentrations of chiral molecular dopants, and predict sample temperature.  \n\nAnother useful technique is to apply machine learning technique for estimating the macroscopic parameters of physical models describing complex LC states. This has been demonstrated for active nematic hydrodynamics.61,64 Neural networks predicted multiple hydrodynamic parameters using only movies of the director eld (Fig. 7c) and forecasted the chaotic dynamics of these systems including point defect nucleation, splitting and annihilation.  \n\nAn approach of analyzing spatiotemporal variations in the parameters of nonequilibrium systems, combined with machine learning methods, could explain the nucleation and behavior of dynamic supramolecular patterns in chiral nematics.65 As the authors suggested, the continuous rotation of chiral patterns in a photoactive LC under constant illumination with a focused ligh beam is sustained by the reaction-diffusion process of embedded light-driven chiral molecular motors coupled to the long-range director eld due by molecular diffusion. Despite this hypothesis and the analysis of the rotation period on the size of chiral pattern, the rotation equation depending on the physicochemical parameters of the system has not been explicitly obtained. Machine learning methods could reveal hidden connections between the macroscopic organization of the director eld and molecular photoisomerization along with diffusion, but this task remains to be explored.  \n\n![](images/7a5427d2edcf669eacf05576ed34afda19852e38581cd751cf1bfa482ad688bd.jpg)  \nFig. 7 (a) Prediction of the pitch length from numerically simulated optical images of the cholesteric LC phase with convolutional neural networks. Reprinted with permission from ref. 60. (b) Prediction of the sample temperature from experimental micro-photographs of E7 nematic LC textures. The network architecture is modified by including additional convolutional layers before each max-polling layer for high prediction accuracy. Reprinted with permission from ref. 60. (c) Extracting hydrodynamic parameters from a libraty of simulated LC director fields using a supervised neural network, and demonstrating the capabilities of a neural network as surrogate model of time evolution. Reprinted with permission from ref. 61.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3.3 Reading indicators of liquid crystal sensors  \n\nOne of the basic features of liquid crystals is their extreme sensitivity to external physical and chemical stimuli, ranging from temperature and mechanical deformations to ultraviolet radiation and chemical agents.66 External stimuli affect the orientational LC structure, which leads to the transformation and amplication of a physical, chemical, or biological event into an easily detectable optical signal due to the LC optical anisotropy.67 The two main implementations of LC sensors involve measuring the light transmission intensity by a LCbased sample placed between a pair of polarizers, or the position of the selective reection band in the case of chiral LCs with a cholesteric pitch comparable to the wavelengths of visible light.  \n\nSince all LCs are highly sensitive materials, the problem of analyzing sensor readings becomes especially important for chemical and biosensors, when precise agent detection at minimum concentration is crucial. Machine learning has great potential for ltering a useful optical signal caused by a change in the LC orientation structure under the action of a measured stimulus from random uctuations in the director eld or the inuence of side physicochemical factors.68 In other words, it is necessary to accurately and quickly solve the problem of pattern recognition and classication, for which machine learning was originally developed.69  \n\nIn response to the global COVID-19 pandemic, Xu with coworkers developed a SARS-CoV-2 point-of-care detection kit based on the response of LC lms to femtomolar concentrations of single-stranded ribonucleic acid (ssRNA).70 For this purpose, the LC layer was decorated with a cationic surfactant and a complementary probe of 15-mer single-stranded deoxyribonucleic acid (ssDNA). The minimum concentration of SARSCoV-2 RNA led to the ordering transition, causing changes in the optical response. Then micrographs were captured by a support vector machine for statistical classication into two categories, positive or negative. Furthermore, in order to obtain a reliable reading of test results for non-expert users, a smartphone application has been developed based on SVM(Fig. 8a).  \n\nRoque with co-authors applied CNNs and support vector machines to recognize more than 10 different volatile organic compounds (VOCs) using LC sensors.71,72 (Fig. 8b) In various multicompartment gel lms containing nematic or smectic droplets, variations in optical textures were registered due to orientational transitions of LC molecules in the presence of VOC vapors. Functional and structural differences in the selected VOCs were small. Depending on the LC material, VOC, and droplet diameter, the prediction accuracy ranged from moderate $50\\mathrm{-}60\\%$ to near $100\\%$ . The change in optical texture also depended on the concentration of VOCs, for example, the mean absolute error in determining the concentration of acetone was below $0.25\\%$ .  \n\n![](images/260ae9bd73c378548d35e75fdaba7abcb7a1005849d50fff51fa4eee8633d511.jpg)  \nFig. 8 (a) SARS-CoV-2 point-of-care detector kit for smartphone app with a reliable readout of the test result by machine learning based algorithm when adsorption of SARS-CoV-2 RNA at the water-LC interface results in an optical response of the LC film. Reprinted with permission from ref. 70. (b) Textural changes of nematic LC-based hybrid gels and corresponding signals during VOC vapor exposure and subsequent recovery along with a collective accuracy prediction plot for 12 VOCs. Reprinted with permission from ref. 72.  \n\nThe research group led by Abbott and Zavala has made signicant contributions to the eld of machine learning methods for LC sensors.73–75 They developed LC-based sensors that exhibited optical responses to ${\\bf N}_{2}$ -water $30\\%$ relative humidity) and ${\\bf N}_{2}{\\bf-D M M P}$ (10 ppm) gaseous environments.73,74 AlexNet, the CNN used in their rst study,73 showed a classied accuracy of $99\\%$ based on grayscale micrographs. However, such a high level of accuracy required the use of a large number of features, so the more compact VGG16-CNN using color micrographs was tested and demonstrated a perfect classication accuracy while the number of features was reduced to less than 100.74  \n\nThe most original study by the group led by Abbott and Zavala is aimed at identifying bacterial agents and quantifying the concentration of bacterial endotoxins.75 Instead of taking optical microphotographs, the authors for the rst time used ow cytometry with measuring the intensity of side-scattered and forward-scattered light by LC droplets. The ratio of these intensities depended on the droplet orientational structure, the specic changes in which the authors attributed with the molecular structure of the lipid A domain of bacterial endotoxins. Endonet-CNN predicted endotoxin sources directly by the ratio of scattered light intensities and estimated endotoxin concentrations over a wide range of eight orders of magnitude from $1~{\\upmu\\mathrm{g}}~\\mathrm{mL}^{-1}$ to $0.01\\ \\mathrm{pg}\\ \\mathrm{mL}^{-1}$ .",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3.4 Quality assessment of liquid crystal displays  \n\nThe at panel display is perhaps the most well-known LC-based device. We deal with LC displays (LCDs) in our daily life in laptops, smart watches, mobile phones, instrumental panels, and so on. A typical LC display has a multi-layer arrangement that consists of a uniformly oriented thin layer of LC molecules placed between glass substrates with ITO electrodes, which in turn are sandwiched between a pair of 90-degree crossed polarizers. Depending on whether the display is reective or transmissive, a reector or backlight is mounted behind the second polarizer. The electric eld applied to the electrodes leads to the reorientation of the LC molecules and change in the intensity of the transmitted polarized light, thus switching the display pixels between the ON and OFF states.76  \n\nImage formation is affected by each layer of the LCD. ITO electrode defects result in permanent bright dots or black pixels on the screen. The brightness of the backlight affects the sharpness and contrast of the image. Therefore, it is important for manufacturers to evaluate the quality of LCDs directly at the factories in automatic mode without inspection by human eyes and at high speed. Clearly, machine learning could serve as a highly efficient method for solving this task.  \n\nThe early attempts to apply various ML algorithms to assess the quality of LCDs were made more than 10 years ago aiming to detect and classify defects of TFT-LCD arrays.77–80 Both assessments are crucial for LCD manufacturing, as identifying the type of defect allows the necessary corrective actions to be taken for its elimination and prevent future failures. In an early study,77 different types of defects were determined with an accuracy of about $86\\%$ to almost $93\\%$ using various ML algorithms such as a support vector machine-based classier and a backpropagation neural network. The data of the analyzed samples were obtained from a real manufacture process. Later, it was shown that modied support vector data descriptions78,79 provide a high defect detection rate of $90\\mathrm{-}96\\%$ and capable of defect detection on an LCD image within $60\\mathrm{ms}$ .78 A method that combines K-means clustering with a backpropagation neural network machine learning algorithm outperforms others in the specic task of predicting the heights of thin lm transistorliquid crystal display photo-spacers.80  \n\nML methods, primarily neural networks, have also been tested to control the local backlight dimming, which is important for less loss of image detail, higher contrast ratio, and low power consumption of LCDs.81–83 A comparative study of local backlight dimming prediction accuracy applied to the subjective evaluation of video quality, impacted by ambient light exposure and peak white (maximum display brightness), revealed that Elastic Net algorithm performed best compared to partial least squares regression and support vector regression.81 The CNN-based algorithm made it possible to control the backlight intensity along with reducing the loss of detail while achieving a high contrast ratio by taking into account the diffusion property of light and leakage property of liquid crystal.82 However, this ML method required statistical information of pixel values in each local block. The local dimming algorithm based on the U-net convolutional network enabled the compensation of pixel data transferred to a panel directly from an input image, without any information about dimming levels of the backlight unit sub-blocks.83  \n\nMachine learning can be successfully used to predict the quality of a whole product through each process data.84 Usually, the overall assessment of product quality in industry is carried out by a sampling method that is not comprehensive and has no timeliness. The random support vector machine method, which combines the support vector machine and random forest, showed the mean square error 0.6 percent lower than that of random forest, despite the fact that the random forest is considered the best traditional machine learning algorithm. A comprehensive three-stage data science framework has also been developed, consisting of variable selection, metrology prediction, and process control.85 At each stage, different ML methods were used to identify the key factors, for instance, the decision tree, stepwise regression, and random forest. The proposed data science framework, applied to an empirical study of a leading TFT-LCD manufacturer, allowed to determine the variables affecting yield, predict the photo spacer thickness with higher performance than the company's method, and proposed the process control in the color lter manufacturing process. All this helps to reduce the cost for process monitoring and quality in TFT-LCD manufacturing.  \n\nSpecic tasks, such as dead pixels and mura detection during manufacturing process were also adequately addressed by ML.86,87 Typically, such defects are detected by an operator, which is not always performed reliable and increases the cost of production. The support vector machine algorithm proved to be the most effective in detecting dead pixels with an accuracy of about $92\\%$ compared to random forest.86 In contrast, mura (a variation in local brightness with no distinct contour on a uniform LCD surface) was predicted using the random forest algorithm with a detection rate above $99\\%$ and a processing time of $27~\\mathrm{ms}$ per image, which is a competitive result for industrial systems.87",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 4 Machine learning for bubbles",
+        "category": " Introduction"
+    },
+    {
+        "id": 13,
+        "chunk": "# 4.1 Cavitation bubbles' analysis  \n\nThe cavitation process that occurs in liquid ows is an important characteristic of the system. The constant movement of bubbles complicates their analysis, for example, the identi- cation of bubbles, determining the shape, size and quantity. Machine learning methods are successfully used to simplify bubble analysis.  \n\nParameters such as bubble size and shape statistics generally determine bubbly ow. Using the analysis of cavitation bubbles and machine learning methods, it is possible to predict the structure of the ow. A similar method is demonstrated in a number of articles. Using graph les as inputs, Gao et al. classied samples by ow structure via convolutional neural networks.88 Two convolutional neural networks were used to classify 6 ow structures and void fraction (Fig. 9a). The accuracy was more than $92\\%$ , the root mean square error was 0.0038 for the ow structure forecast.  \n\nNot only graph les can be used as machine learning inputs. Bubble images are a common inputs to cavitation bubbles analysis. Even images of micro-size bubbles can be processed successfully. CNNs can be also used for microbubble analysis. Qaddoori et al. performed a similar approach to determine the size of microbubbles using pre-processed images.89 The images were preliminary converted into HSV format and then processed with CNN (Fig. 9b). According to this approach, the microbubble size was determined both by the number of pixels and luminosity intensity. The method showed $100\\%$ accuracy in microbubble size determination. Bubble' image analysis via CNNs also enables identication of the ow patterns.90,91  \n\nHigh-speed cameras are widely used to capture cavitation bubbles, but the resulting images are oen of a low quality. Machine learning can also be used to improve defects of input images. Poletaev et al. used deep learning, specically CNN, to build a model capable of detecting and tracing overlapping, blurry, and non-spherical cavitation bubbles, and demonstrated its further analysis.92 Various models and training parameters were performed, and the proposed approach was found to be effective, as the accuracy was about $97\\%$ on the test dataset. CNNs showed high efficiency in a wide range of studies with defective images, as well as deep neural networks.93,94 CNNs were also applied to reconstruct the bubble pattern and its further identication.95 He et al. further developed the approach and used pulse-coupled neural networks (PCNN) for bubble segmentation.96 The proposed scheme turned to be effective also for image enhancement (Fig. 9c). The segmentation accuracy was about $90\\%$ .  \n\nDeep learning and convolutional neural networks can be successfully replaced with classical machine learning methods such as decision trees, support vector machines, linear regression, etc. Srivastava et al. demonstrated an approach to determine the size of bubbles depending on environment change. Cavitation bubble data was extracted from images using ImageJ scripts. Various regression models were used based om multilayer perceptron, decision tree, support vector machine. Performed models showed the same high efficiency as articial neural network (ANN).97 Classic ML methods were successfully applied to determine the size of bubbles in real column reactors.98,99  \n\n![](images/853092db821931a632c5fd3872820bf0ee4d3cb1cae9af0e6f359eb0696a0d96.jpg)  \nFig. 9 (a) Convolutional neural network architecture with two inputs for stream structure classification and void fraction measurement. Reprinted with permission from ref. 88. (b) Bubble analysis based on image pre-processing and convolution neural network. Reprinted with permission from ref. 89. (c) Image processing algorithm based on PCNN. Reprinted with permission from ref. 96. (d) Classification of alcohol concentration based on cavitation bubble images and CNN. Reprinted with permission from ref. 103.  \n\nThe discussed approaches require a relatively large dataset of input images. To solve the small dataset problem, Fu and Liu used generative adversarial networks to create a BubGAN model.100 The performed model can generate image les that can later be used to create other models for cavitation bubble analysis. The algorithm showed high efficiency and image detection. The root mean square error (RMSE) was about $2-3\\%$ . This method is effective when it is necessary to create the intended applications of cavitation bubbles in the decit of the liquid in which they were formed. This approach is proposed for both statistical machine learning methods, and is also applied to identify bubbles with high efficiency.29  \n\nGenerative adversarial network (GAN) was also used for dataset enhancement and bubble image synthesis, while models for bubble segmentation were developed.101 The combination of image synthesis and the U-Net model provided more accurate bubble segmentation in comparison with previous models.  \n\nCavitation bubbles can interact with each other, which complicates the analysis of bubbles ow analysis and image defects. Bubbles' interaction is hardly described by 2D images.  \n\nShao et al. performed a 3D reconstruction via CNN with U-net architecture.102 The result was a model that can be used to create a 3D graph with the distribution of bubbles.  \n\nCavitation bubbles can transform not only via interactions with each other, but also by bubble growth, decomposition, or collapse. Bubble's shape transformation depends on the liquid content and can be used for quantitative content analysis of a liquid probe. CNN coupled with the transfer learning method allowed to classify samples by uid content using a series of bubble images in dynamics (Fig. 9d).103 Pretrained CNNs with frozen layers can be successfully used for efficient model training without requiring a large dataset.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 4.2 Modelling of processes in bubbly ows  \n\nMachine learning can be combined with classic approaches to model bubbly ows and simulate complex liquid systems. Several complex liquid systems require the integration of machine learning methods into the previously performed simulation approach. The combination of precise numeric methods and neural networks is then turned into an advanced simulation model. Mosavi et al. performed this approach to create a model for predicting macroscopic parameters such as gas velocity in a multiphase reactor.104 The combination of adaptive-network-based fuzzy inference system (ANFIS) and computational uid dynamics (CFD) provided $R=0.99$ and a signicant reduction in simulation time. The same approach was successfully performed for a column reactor with three input parameters for ANFIS (Fig. 10a). ANFIS is widely used for hydrodynamics simulation in a wide range of real reactors.105–109  \n\nThe bubble size prediction discussed earlier can also be combined with physics, mathematics, and machine learning to get a simulation model. Jung et al. performed an efficient model that can accurately predict the size of cavitation bubbles on test data and in real systems.110 The approach was to create a pipeline with a multilayer perceptron (MLP) model capable of simulating the size of cavitation bubbles for various parameters (Fig. 10b). A low error of no more than $5\\%$ was obtained.  \n\n![](images/d421511fb3869252d59e65184b932dc59bc225827d9011a2f6c20e3fb5b63932.jpg)  \nFig. 10 (a) ANFIS structure scheme. Reprinted with permission from ref. 105. (b) Bubble size prediction based on a multi-layer artificial neural network. Reprinted with permission from ref. 110. (c) Workflow of applying ANN-Lee model for simulation of bubble condensation. Reprinted with permission from ref. 118. (d) Marginal and pairwise joint distribution of constitutive relation parameters. Reprinted with permission from ref. 119. (e) Using the YOLO net to predict the anomalous shape of cavitation bubbles. Reprinted with permission from ref. 120.  \n\nSimilar pipelines were applied to identify the ow regime.111 Two-phase ow data was measured and extracted using Ultrasound Doppler Velocimetry (UDV). The obtained data was analyzed using three classication algorithms such as decision tree, K nearest neighbor, and support vector machine. All three algorithms showed classication accuracy above $90\\%$ in real time. For comparison, CNN and LSTM were used to identify the ow regime with an accuracy of about $94\\%$ . The effectiveness of the proposed approach was also showed by another research groups.112 Classic machine learning methods are also relevant for predicting the characteristics of the ow regime, the behavior of a single bubble in a ow, and its deformation.113–117  \n\nIntegration of machine learning methods increases the efficiency of simulation models that are hardly performed for bubbles' transformation processes. Then, the bubble condensation simulation, which was previously performed using only the Lee model, was successfully implemented using articial neural networks.118 The back propagation articial neural network was used to obtain an empirical coefficient for the Lee model (Fig. 10c). The database consisted of four numerical inputs such as Prandtl and Reynolds numbers. The predicted empirical coefficient was in a good agreement with literature data, as well as modeling via the coupled ANN-Lee model.  \n\nA similar advanced approach with the integration of machine learning to clarify inputs and outputs was applied to ow simulation. Liu et al. used machine learning techniques to reduce the computational costs for multiphase computational uid dynamics (MCFD) simulation of bubbly ow.119 Principal component analysis was performed to decrease the subspace of each MCFD simulation output, and then a feedforward neural network was used for surrogate modelling to predict MCFD results. A Gaussian process was used to obtain the model form uncertainty and parameters distribution (Fig. 10d).  \n\n![](images/7b20c497a9b75a789b902b36372fbda8e163759bf3e0be47a3ea0374fd73741f.jpg)  \nFig. 11 Envisioned development of a machine learning approach for further deep analysis of complex soft and liquid material systems.  \n\nCombining machine learning methods with only numerical methods is also an efficient approach, especially for real systems such as reactor with complex ows. Wang et al. discussed the applicability of CNNs combined with improved three-frame difference (ITFD) method for recognizing and tracking bubbles in a plate heat exchanger (PHE).120 The bubble size accuracy determination was $94\\%$ (Fig. 10e).  \n\nML can also be applied for dynamic processes modelling without any support with classical simulation methods. This approach was performed to predict the migration of cavitation bubbles.121 The research demonstrated that instead of traditional experimental and numerical methods, a two-branch model of a deep neural network with the embedding of a Kelvin impulse can be used. The demonstrated method showed high efficiency.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 5 Conclusions  \n\nThe rst attempts to apply ML methods for understanding the so matter structure and properties have been made since the $90~\\mathrm{s}$ , but the rapid growth of research in this area has occurred in the last few years. This happened due to the active development of machine learning and articial intelligence approaches for many branches of science and is reected both in the number of original research articles (Fig. 1) and in the appearance of the rst reviews.122–124  \n\nThe correct and appropriate use of ML techniques for so and liquid molecular materials allows discovering their new properties at all scales, from molecular to macroscopic, based on the analysis of experimental or simulated homogeneous data sets, and demonstrate the promise of so materials devices for complex technological applications. Our review provides many examples supporting this conclusion.  \n\nHowever, several remarks should be made to all the analyzed studies (Fig. 11). Generally, even recent studies do not consider multimodal data obtained by various methods. Also, most of the research papers do not offer open access to either the data or the source code of the used machine learning model. The importance of this practice has already been emphasized in chemistry125 and should be recognized by researchers in the eld of so materials. An open data policy will enable in-depth studies using various big data analysis algorithms when considering existing scientic problems in so matter from different points of view. Consideration of complex data sets involves the introduction of universal descriptors that could link together the various properties of the analyzed system at several levels of the hierarchy. This will most likely require the creation of new, integrated approaches for multivariate analysis of the systems under study, that will be based on several ML methods. Validation of the created complex ML approaches, interpretation of the obtained ML data, their reliability and validity remain critical issues. The implementation of these steps in the development of machine learning technique will ensure the formation of a universal approach to the analysis and prediction of the behavior of systems and materials with a complex architecture. It will also pave the path to new interdisciplinary areas of research and bring scientic results that are difficult to imagine at the current level of applying ML and articial intelligence methods for so and liquid molecular materials.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 16,
+        "chunk": "# Data availability  \n\nData sharing not applicable to this article as no datasets were generated or analysed during the current study.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# Author contributions  \n\nT. O.: investigation; validation; writing – review editing; A. P.: investigation; writing – original dra; D. D.: investigation; writing – original dra; T. A.: data curation; investigation; writing – original dra; T. M. T. A. R.: investigation; writing – original dra; A. B.: investigation; writing – original dra; N. G.: writing – original dra; E. S.: conceptualization; supervision; validation.",
+        "category": " Abstract"
+    },
+    {
+        "id": 18,
+        "chunk": "# Conflicts of interest  \n\nThere are no conicts to declare.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 19,
+        "chunk": "# Acknowledgements  \n\nThe RSF grant no 21-13-00403 supports research related to hydrogel and machine learning approach. The RSF grant no 22- 13-00185 supports research related to liquid crystals and machine learning approach. The goszadanie no. FSER-2021- 0013 supports research related to bubble dynamics and machine learning approach. We thank the ITMO Fellowship and Professorship Program for the infrastructural support.",
+        "category": " References"
+    },
+    {
+        "id": 20,
+        "chunk": "# References  \n\n1 L. van der Maaten, E. Postma and J. van den Herik, J. Mach. Learn. Res., 2009, 10, 66–71.   \n2 V. Chandola, A. Banerjee and V. Kumar, ACM Comput. Surv., 2009, 41, 1–58.   \n3 D. A. Freedman, Statistical Models: Theory and Practice, Cambridge University Press, 1st edn, 2009.   \n4 R. A. Fisher, Ann. Eugen., 1936, 7, 179–188.   \n5 B. Everitt, Cluster analysis, Wiley, Chichester, West Sussex, U.K, 1st edn, 2011.   \n6 I. T. Jolliffe and J. Cadima, Philos. Trans. R. Soc., A, 2016, 374, 20150202.   \n7 K. Beyer, Database Theory—ICDT’99, 1999, 217–235.   \n8 J. R. Quinlan, Int. J. Man-Mach. Stud., 1987, 27, 221–234.   \n9 C. Cortes and V. Vapnik, Mach. Learn., 1995, 20, 273–297.   \n10 J. J. Hopeld, Proc. Natl. Acad. Sci. U. S. A., 1982, 79, 2554– 2558.   \n11 J. Shang and P. Theato, So Matter, 2018, 14, 8401–8407.   \n12 H. Lei, L. Dong, Y. Li, J. Zhang, H. Chen, J. Wu, Y. Zhang, Q. Fan, B. Xue, M. Qin, B. Chen, Y. Cao and W. Wang, Nat. 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+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,32 @@
+[
+    {
+        "id": 1,
+        "chunk": "# 人工智能+新材料研发：迈向 “预测性设计”和“精准创制”  \n\n![](images/9323803c5f149f5a3ffa88e5d74d68950a36237c3e4e56234c7f2901f5961b45.jpg)  \n\n郭子芳  \n中国石化北京化工研究院  \n副院长",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# AI阅评  \n\n人工智能技术能更加精准地实现材料设计、性能预测和工艺优化，为研发决策提供科学、可靠的依据，加速新材料的研发与应用，为化工材料领域的创新发展注入强劲动力。  \n\n本文对AI技术在化工材料研发中的多维应用进行了系统性梳理，重点聚焦于高通量分子筛选、反应路径优化、工艺参数智能调控等核心技术场景。针对模型可解释性这一瓶颈，文章创新性地提出“混合增强智能”解决方案，将物理机理模型与深度学习网络有机融合。这些研究成果对石油化工行业数字化转型具有重要实践价值。  \n\n![](images/1af5b1409254e162a6f79f7d10295058c40d3598a75ee9226b5c3798e3171fae.jpg)  \n\n2024年诺贝尔化学奖与物理学奖花落人工智能（AI）相关研究项目，这一标志性事件不仅彰显了AI技术的成熟度，更预示着它正以革新之势重塑科学研究的固有范式。在化工与材料研发领域，众多企业敏锐捕捉到这一技术变革的浪潮，纷纷投身其中，或自主探索，或携手科技企业，借助AI技术赋能科研开发，力求推动行业从传统模式向“预测性设计”和“精准创制”的智能化方向大步迈进。",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 人工智能技术在化工材料研发领域的应用  \n\n当下，AI技术在化工材料研发领域已展现出巨大的应用潜力，不少企业已收获显著成果。  \n\n巴斯夫引入高性能超级计算机Quriosity，将AI融入分子与化合物模拟计算流程。这一举措大幅提升了计算效率，能够快速筛选聚合物结构，加速新型分子和化合物的开发进程。曾经需要耗时一年的计算任务，如今仅需短短数天即可完成，而且还能挖掘出传统方法难以察觉的潜在关联性，为研发工作开辟新思路。  \n\n陶氏化学与微软达成合作，将AzureAI和机器学习技术深度整合到聚氨酯等材料研发中。其构建的AI模型宛如智能大脑，能够在短短几秒内对数百万种配方组合进行分析筛选，并给出极具针对性的优化建议。原本需要4～6个月才能完成的实验室探索工作，现在仅需30秒就能完成，效率提升约20万倍，大大缩短了新材料差异化解决方案的上市时间，使企业在市场竞争中抢占先机。  \n\n万华化学借助AI技术在催化剂筛选环节实现了重大突破。面对14000多种备选方案，AI算法迅速筛选出156种具有潜力的选项，随后进一步优化至4种，精准推荐分子合成实验，极大缩短了研发周期，让科研效率得到质的飞跃。  \n\n宁德时代则另辟蹊径，将材料机理、大数据分析与AI算法有机结合，加速电解液、正极、包覆等电池材料的开发。通过这种创新模式，不仅研发周期缩短了 $30\\%$ ，研发成本也降低了$30\\%$ ，在提升产品性能的同时，有效提升了企业的经济效益。  \n\n晶泰科技利用量子物理模拟、AI算法与云计算技术搭建智能化药物研发平台，在药物研发领域大放异彩。在项目初期，该平台可生成百万量级的虚拟分子，并快速筛选出关键候选分子。在与辉瑞合作研发新冠口服药PAXLOVID时，AI预测算法结合实验验证，仅用6周就成功确定优势药物晶型，而传统方法则需要数月以上的时间，充分展示了AI技术在药物研发领域的高效性。  \n\n从这些案例不难看出，AI技术与多学科知识的深度融合，能够在海量方案中快速筛选出可行选项，并进一步优化，显著缩短实验和研发周期，提高研发效率。同时，它还能更加精准地实现材料设计、性能预测和工艺优化，为研发决策天津石化南港中心实验室运用人工智能技术，实现机器人替代人工完成液体样品的分样、加标，提高色谱检测的自动化、高效化、规范化水平。 董波/摄  \n\n![](images/67a4a9476099c7fd2708dd644a04ee7237941c521d6aaa2b4a9b1e698e6c4e15.jpg)  \n\n提供科学、可靠的依据，加速新材料的发现与应用，为化工材料领域的创新发展注入强劲动力。",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 人工智能技术在化工材料研发领域面临的挑战  \n\n尽管A I 技术在化工材料研发领域前景广阔，但在实际应用过程中，仍面临着诸多严峻挑战。",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# （一）在数据层面，主要面临数据稀缺、异构化、质量缺陷等困境  \n\n目前，大量有价值的有效数据分散存储于企业内部，且多以非结构化形式存在，这使得数据的流通与整合困难重重。尤其是在新型材料研发方面，由于缺乏历史数据作为支撑，AI技术面临着严重的“冷启动”难题。此外，单纯依靠实验获取数据不仅耗时费力，成本也极高，严重制约了数据的广泛收集与应用。  \n\n在新材料设计过程中，需要融合多种不同类型的数据，如分子结构（简化分子线性输入规范（SMILES））、光谱数据（红外、拉曼）以及工艺参数（温度、压力）等。同时，还需实现从微观数据到宏观性能的跨尺度数据关联，这对数据处理技术与整合方法提出了极高的要求。然而，不同机构在材料成分标注（如质量分数与摩尔分数混用）、实验条件记录等方面缺乏统一规范，导致数据融合与模型训练效率低下。  \n\n实验过程中不可避免地会产生各种误差，如设备测量误差、批次误差等，这些误差严重影响了数据的准确性。此外，不同实验室对于同一现象的定义往往存在较大差异，导致数据标注的一致性难以保障，数据的可靠性与可用性大打折扣。数据质量还体现在数据的不均衡性上，在化工材料研发数据中，某些性能优良或特殊的材料数据占比极少，这使得模型在训练时难以充分学习少数类数据，从而影响对稀有但重要材料特性的预测和分析。  \n\n（二）在算法和模型层面，面临模型可解释性矛盾、多尺度建模时空鸿沟、小样本学习瓶颈等挑战  \n\n深度神经网络在材料性能预测方面虽然能够达到较高的准确率，但其内部物化机制的解释度却很低，形成了典型的“黑箱模型困境”。究其原因，现有AI模型大多以数据驱动为主，缺乏对质量守恒、热力学定律等基础物理规律的有效嵌入，导致预测结果可能与科学常识相悖。因此，如何在保证模型复杂度的同时，提高其物理可解释性，成为亟待解决的关键难题。  \n\n材料研发需要跨越从飞秒级分子动力学到年尺度老化实验的12个数量级的时间维度，同时关联量子计算与反应器级的空间特征。尽管目前有一些模型框架尝试通过多尺度理论建模来缩小这一鸿沟，但在实际应用中仍受到计算资源与算法效率的双重制约。  \n\n在新材料研发场景中，可用数据量往往非常有限，通常小于100个样本数量，这使得传统模型的泛化误差较大。对于未经验证的体系，零样本探索的预测失效率更高。虽然迁移学习等技术为解决这一问题提供了一些思路，但数据噪声与领域差异仍然显著影响着模型的迁移效果。  \n\n（三）在人才层面，跨学科知识融合不足、人才培养体系不完善、人才吸引力和留存问题皆不容忽视  \n\n化工材料研发涉及化学、物理等多学科知识，而AI技术则需要计算机科学、数学、统计学等领域的专业知识。这两种知识体系之间存在较大差异，导致既懂化工材料又精通AI技术的复合型人才极度稀缺。此外，AI算法专家与化工材料领域专家之间存在明显的知识壁垒，双方沟通协作困难，也阻碍了算法模型与化工材料研发的深度融合。  \n\n当前，许多从事AI技术的人才缺乏化工材料研发的实际项目经验，对研发流程、需求和痛点了解不够深入。同时，化工材料AI研发领域的实践平台和项目刚刚开始，人才在实践中积累经验、提升能力还不够，这也在一定程度上制约了AI技术在该领域的应用与发展。  \n\nA I 领域高端人才竞争异常激烈，与互联网、金融等热门行业相比，化工材料行业因研发环境相对艰苦、待遇水平不高等因素，在吸引和留住人才方面面临较大压力，人才流失现象也较为严重。",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 利用AI技术加速化工材料研发的思考建议  \n\n加速A I 技术在化工材料研发中的落地应用，可以从数据、算法和模型、人才三个关键层  \n\n面着手应对挑战。  \n\n（一）在数据层面，加强数据整合与共享，建立和完善数据标准化，提升数据质量，挖掘数据实现增值  \n\n应建立企业内部统一的数据管理平台，将各业务部门、子公司分散的数据资源进行有效整合，打破数据孤岛，实现数据的集中存储与共享，让数据在企业内部自由流通。同时，积极与外部科研机构、高校开展合作，建立数据共享机制，广泛获取更多维度的外部数据，丰富数据来源，为AI模型训练提供充足的数据支持。  \n\n制定涵盖材料成分标注、实验条件记录等方面的统一数据标准和规范，确保不同来源的数据具有一致性和可比性，便于后续的数据融合与模型训练，提升数据的可用性和价值。  \n\n构建全面的数据质量评估体系，对数据的准确性、完整性、一致性等进行严格评估与监控。加强数据清洗和预处理工作，去除数据中的噪声和错误数据。同时，优化实验设计和操作流程，从源头上减少误差，保障数据质量。  \n\n充分利用数据挖掘技术，从海量的历史数据中挖掘潜在的规律和知识，为新材料研发提供有价值的参考。通过数据分析预测新的市场需求和研发方向，为企业的战略决策提供有力支撑，实现数据的价值最大化。  \n\n（二）在算法和模型层面，增强模型可解释性，多尺度优化建模，突破小样本学习技术  \n\n研发将物理规律、化学原理等有效嵌入其中的AI模型，使模型的预测结果具有科学依据且可解释。同时，加强对模型的验证与评估，确保其可靠性和准确性，为研发决策提供可靠的支持。  \n\n开展多尺度建模技术研究，建立从微观到宏观的跨尺度模型，实现不同尺度数据的融合与分析。通过优化模型的算法和计算方法，提高模型的计算效率和精度，降低误差累积，提升模型在化工材料研发中的实用性和可靠性。  \n\n积极探索适合小样本数据的学习方法，如迁移学习、元学习等，提高模型在小样本数据下的泛化能力和预测性能。加强数据增强技术研究，通过数据增强方法扩充小样本数据集，提升模型的训练效果，有效解决小样本数据带来的挑战。  \n\n（三）在人才层面，建设高效的人才培养体系，跨学科融合培养，着力吸引和留住人才  \n\n建立跨学科的人才培养体系，加强化工材料专业与计算机科学、数学、统计学等专业的交叉融合，培养既懂化工材料又精通AI的复合型人才。鼓励员工积极参与跨学科的学习和培训，提升员工的综合素质和跨学科能力，为企业的AI技术应用提供坚实的人才保障。  \n\n加强高校与企业的合作，建立实习基地和实践平台，为高校学生提供更多接触实际项目的机会，培养学生的实践能力和创新意识。同时，加强企业内部人才培养，通过内部培训、项目实践等方式，提升员工的AI技术水平和应用能力。  \n\n制定具有竞争力的人才政策，提高化工材料行业对人才的吸引力。为人才提供良好的工作环境和广阔的发展空间，给予他们具有挑战性的项目任务，激发人才的创新活力。加强企业文化建设，增强人才的归属感和忠诚度，留住优秀人才，打造一支稳定、高素质的人才队伍。  \n\n只有积极应对挑战并采取切实有效的措施，加速AI技术在化工材料研发中的落地应用，提升企业的创新能力与核心竞争力，企业才能在激烈的市场竞争中脱颖而出，引领化工材料研发行业的创新发展。",
+        "category": " Introduction"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Design of functional and sustainable polymers assisted by artificial intelligence  \n\nHuan Tran    1,2, Rishi Gurnani2, Chiho ${\\ K}\\ i\\mathbf{m}^{1,2}$ , Ghanshyam Pilania3, Ha-Kyung Kwon4, Ryan P. Lively5   \n& Rampi Ramprasad    1,2",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# Abstract  \n\nArtificial intelligence (AI)-based methods continue to make inroads into accelerated materials design and development. Here, we review AI-enabled advances made in the subfield of polymer informatics, with a particular focus on the design of application-specific practical polymeric materials. We consider exemplar design attempts within a few critical and emerging application spaces, including materials designs for storing, producing and conserving energy, and those that can prepare us for a sustainable economy powered by recyclable and/or biodegradable polymers. AI-powered workflows help to efficiently search the staggeringly large chemical and configurational space of materials, using modern machine-learning (ML) algorithms to solve ‘forward’ and ‘inverse’ materials design problems. A theme explored throughout this Review is a practical informatics-based design protocol that involves creating a set of application-specific target property criteria, building ML model predictors for those relevant target properties, enumerating or generating a tangible population of viable polymers, and selecting candidates that meet design recommendations. The protocol is demonstrated for several energyand sustainability-related applications. Finally, we offer our outlook on the lingering obstacles that must be overcome to achieve widespread adoption of informatics-driven protocols in industrial-scale materials development.",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# Review article",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# Introduction  \n\nPolymeric materials have an ancient history, but the foundations of modern polymer science can be traced back to work by Hermann Staudinger in the 1920s. His groundbreaking idea1 was that highmolecular-weight materials, such as rubber, cellulose and proteins, consist of lengthy chains formed by repeating molecular-size units linked by covalent bonds2,3. This fundamental concept of modern polymer science played a crucial role in numerous remarkable discoveries and advancements (Fig. 1a), including the creation of innovative polymers such as polypropylene, neoprene, nylon, Teflon and Kevlar. These polymers, from daily packaging materials to high-tech device components, have permeated every aspect of our world4–13. The ability to control essential parameters such as chemical structure, processing conditions and additives has enabled the development of synthetic polymers with diverse properties, ranging from rigidity to elasticity, a broad range of electrical conductivity, and permeability and selectivity to specific gases. This versatility stems from factors such as the structural diversity of organic materials, the exceptional synthetic ingenuity of chemists, and the vast chemical space that polymers occupy. Staudinger’s seminal work, honoured with a Nobel Prize in 1953, laid the foundation for successive Nobel Prizes in this field.  \n\nAlthough many noteworthy polymeric materials have been discovered, developed and commercially deployed over the past century, the transition from concept to deployment has required years to decades even in the most successful instances (Fig. 1b). Several factors have contributed to this prolonged timeline. First, key concepts originate from the intuition and experience of a select few expert scientists and engineers. Pursuing these original ideas, either using physical experimentation or computer simulations, demands specialized skills, funds, resources and time; methodically exploring the vast chemical and/or processing space is non-trivial even within a restricted class of materials. The new material must satisfy various success metrics, encompassing properties, performance, cost, safety and supply chain considerations. And finally, attaining a satisfactory end point in a timely manner, ahead of the competition, necessitates prioritizing options such as the fastest or most cost-effective synthetic pathways. These considerations lead to substantial trial-and-error activities, missed opportunities and a sizeable reliance on serendipity.  \n\nIt is tempting to imagine a future in which materials intuition, experience, and the vast repository of data and knowledge can be encoded and embedded in a powerful artificial intelligence (AI) expert system. This could not only safeguard against the loss (or neglect) of valuable assets, be they data or knowledge, but also hold the promise of continuous improvement, rapid and reliable property predictions, informed decision-making and democratization — making expertise readily accessible to anyone at any time. This philosophy has catalysed the emergence of several materials informatics ecosystems, summarized in Table 1, around the globe in the past decade or ${\\mathsf{s o}}^{14}$ . Fuelled in part by the Materials Genome Initiative, these ecosystems serve to complement, augment and elevate the impact of empirical or computation-based materials research. Various indicators suggest that this vision is gaining traction in industry15,16, driven by the perception and expectation that such AI-based knowledge systems can substantially reduce both the number and timelines of iterative cycles preceding the deployment of new materials.  \n\nThis Review centres on polymer informatics17–22, specifically delving into AI-driven polymer designs tailored for various applications. The roots of polymer informatics can be traced back decades, initially emerging as ‘group contribution’ methods23. These methods used numerical representations of polymers based on their molecular fragments, mapped onto properties through linear regression for rapid predictions. Today’s polymer informatics ecosystems have evolved considerably. First, contemporary polymer property datasets are larger, more reliable and cover many more properties than the group contribution methods. Second, recent numerical representation (or fingerprinting) schemes24–27 are much more comprehensive, in some cases24,25 incorporating thousands of descriptors across multiple length scales, ranging from the atomic to block to chain levels. They are also scalable (to handle search spaces of over a billion candidates), leveraging modern transformer-based28,29, graph-based30–32 and chemical language models33. Finally, machine-learning (ML) algorithms that map polymer fingerprints to properties (leading to predictive models) can handle extensive datasets, are generalizable and interpretable, and accommodate data from diverse sources and fidelity levels24,25,34.  \n\nThese rapid and reliable property prediction models are critical for materials informatics. However, materials design requires more than prediction; it must involve the ability to ‘invert’ the prediction process and recommend materials that align with target properties or performances35–37. Over the past decade, various inverse methods, including high-throughput screening38,39, Monte Carlo schemes40, recommender systems41, Bayesian optimization42,43, particle swarm optimization44–46, evolutionary or genetic algorithms47,48, syntax-directed variational autoencoders49,50 and graph-to-graph translation30, have proven effective at proposing candidate materials, particularly for polymers. However, a key challenge is ensuring that these materials are synthetically feasible. To tackle this, an emerging approach, which we call ‘virtual forward synthesis’ (VFS), could leverage millions of commercially available or easy-to-synthesize monomers and insert them in several hundreds of known polymerization reaction templates to digitally generate any number of synthetically accessible polymers51–53.  \n\nA robust strategy for use-inspired, application-driven, synthetically accessible polymer design involves several steps (Box 1). It begins with defining a set of screening criteria based on desired property values. A vast search space is then defined, potentially involving a large library of polymers produced through VFS or similar methods. In parallel, predictive ML models for these key properties are developed using sufficiently large and diverse datasets of measured or computed values54. The models predict key properties for polymers in the search space, and those meeting desired values are selected as potential candidates. The design loop is ‘closed’ by testing the recommended candidates via physical experiments. Success is declared if the candidates meet the required property or performance criteria. If not, the design loop cycle repeats.  \n\nIn this Review, we highlight several polymer design endeavours undertaken in the past few years that have benefited from applying AI or informatics methodologies. These case studies span polymer dielectrics for energy storage7,55,56, fuel-cell membranes and ionomers57, solid polymer electrolytes for batteries58–61, gas10,62 and liquid mixture63–66 separation membranes, biodegradable polymers67 and depolymerizable polymers68–71. We then examine challenges and opportunities on the horizon, touching on complex scenarios involving composites, formulations and cross-linked polymers; the autonomous extraction of property data from the exponentially increasing literature using natural language processing techniques; and the use of computational–experimental information fusion and multifidelity methods to produce and leverage data covering ever-greater chemical spaces. Ultimately, transitioning from successful laboratory-scale synthesis to commercialization is the definitive validation of the real-world value of polymer informatics.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# Review article  \n\nb Typical deployment progress of some notable polymers  \n\n![](images/6dce0c297bbdee2474c6e4b4c73565cf78491da0e86867c39db76abad74aa3ea.jpg)  \na Selected milestones of polymer science   \nFig. 1 | Polymer innovations over the past two centuries. a, Selected chronological milestones in polymer science. b, Traditional transition from concept to deployment of some notable polymeric materials. LDPE, low-density polyethylene; PVC, poly(vinyl chloride).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# Application-specific design of polymers Dielectric polymers for electrostatic energy storage  \n\nThe escalating global demands for electric power and energy storage present profound challenges, one of the foremost being the design of materials for use in electrostatic capacitor devices that can withstand extreme electric fields and temperatures7,72–79. The selection of suitable dielectric materials, temperatures and electric fields for such applications is bound by the limitations imposed by electrical breakdown. Beyond a critical field intensity, accelerating electron cascades within an insulator lead to electrical discharge and system failure. This behaviour is exacerbated at elevated temperatures and is inherently governed by the material’s chemical composition and morphology80.  \n\nPolymeric dielectric materials, owing to their graceful failure modes, are the materials of choice for capacitive energy storage across transportation, aerospace, energy and defence sectors. In comparison to more extensively discussed energy-storage devices such as batteries, fuel cells and supercapacitors, electrostatic capacitors present unparalleled power density7,55,72–76 (Fig. 2a). This positions electrostatic capacitors as particularly advantageous for a wide array of applications, including hybrid and all-electric systems, pulsed power systems, wind pitch control, aircraft launchers and space exploration7,72–76.  \n\nCurrent high-power capacitors use biaxially oriented polypropylene (BOPP) as the dielectric, a material that has been used for over three decades. Its long-term presence is due to its high electrical breakdown strength of over $700\\mathsf{M V}\\mathsf{m}^{-1}$ at room temperature, low cost for mass production, and considerable investment from the academic community, industry and supply chain. BOPP, along with similar commercial polyolefins, also exhibits low dielectric loss and a substantial electronic bandgap, attributed, in part, to the absence of $\\pi$ -stacking moieties. Despite these features, these materials have a low dielectric constant, resulting in a diminished electrostatic energy density — a critical ‘figure of merit’ for this application. At room temperature, BOPP registers a baseline energy density of 5 J $\\mathsf{c m}^{-3}$ , which rapidly degrades with increasing temperature.  \n\nRational materials design approaches to surpass BOPP in electro­ static energy storage have proven successful55,56,81–83, driven by the establishment of clear property-based screening criteria and the integration of computational methodologies that primarily use density",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# Review article  \n\nTable 1 | Notable polymer informatics ecosystems   \n\n\n<html><body><table><tr><td colspan=\"2\"></td><td colspan=\"2\">Location</td></tr><tr><td> Name</td><td>Category</td><td>Short description ~32k homopolymers, copolymers, polymer blends and </td><td></td></tr><tr><td>Polylnfo</td><td>Database</td><td>composites, ~5ook experimental data points</td><td>https://polymer.nims.go.jp</td></tr><tr><td> PI1M</td><td>Database, open</td><td>~1M polymers generated from generative models trained https://github.com/RUlMINMA1996/PI1M on ~12k actual polymers</td><td></td></tr><tr><td>CHEMnetBASE</td><td> Database, open</td><td>Polymers and properties</td><td>https://poly.chemnetbase.com</td></tr><tr><td>polyVERSE</td><td>Database, open</td><td>~200M generated polymers, ~1Ok properties computed for synthesized polymers</td><td>https://github.com/Ramprasad-Group/ 33,54,80,271 polyVERSE</td></tr><tr><td></td><td> Polymer Scholar Database, open</td><td>~300k polymer property records extracted from literature</td><td>https://polymerscholar.org</td></tr><tr><td>OMG</td><td>Database, open</td><td>Open Macromolecular Genome,~12M linear homopolymers created by commercially available monomers and 17 canonical polymerizations</td><td>https://zenodo.org/records/7556992</td></tr><tr><td>HTPMD</td><td>Database, open</td><td>6,286 high-throughput MD trajectories of amorphous polymer electrolytes and analysis tools</td><td>https://www.htpmd.matr.io, https://github.com/TRl-AMDD/htp_md</td></tr><tr><td>PPPdb CRIPT</td><td>Database, predictor</td><td>Polymer Property Database and Predictor for polymer properties and phase diagrams</td><td>https://pppdb.uchicago.edu</td></tr><tr><td></td><td> Enabling capability</td><td>Community Resource for Innovation in Polymer Technology, graph data model for scalable, efficient and complex polymer data structure</td><td> https://criptapp.org</td></tr><tr><td>SMILES</td><td>Enabling capability</td><td>Line notation, capable of representing the atomic connectivity of polymers</td><td></td></tr><tr><td>CurlySMILES</td><td> Enabling capability</td><td>Line notation and tools, handling stereogenicity, electron delocalization charges, extramolecular interactions and so on</td><td>https://www.axeleratio.com/csm/py/code/</td></tr><tr><td>BigSMILES</td><td>Enabling capability</td><td>Line notation and tools, handling the stochastic nature of polymers</td><td>https://olsenlabmit.github.io/BigSMILES</td></tr><tr><td>G-BigSMILES</td><td>Enabling capability</td><td>Generative BigSMILES, line notation and tools, generating realistic polymer ensembles</td><td>https://github.com/lnnocentBug/ bigSMILESgen</td></tr><tr><td>polyDAT</td><td>Enabling capability</td><td>Generic schema, handling chemical information, synthetical pathways and processing procedures Multigraph neural network, processing polymer repeat</td><td>https://olsenlabmit.github.io/BigSMILES</td></tr><tr><td></td><td>software</td><td>units as graphs to map onto properties, developing predictive models</td><td>https://github.com/Ramprasad-Group/</td></tr><tr><td>polyBERT MaterialsBERT</td><td>Enabling capability, software Enabling capability,</td><td>Chemical fingerprinting capability, processing polymer chemical structure to learn and predict properties Large language model, fine-tuned PubMedBERT on</td><td>https://github.com/Ramprasad-Group/ polyBERT https://huggingface.co/pranav-s/</td></tr><tr><td></td><td>software</td><td>2.4M materials science abstracts, used to extract data available in Polymer Scholar</td><td>MaterialsBERT</td></tr><tr><td>RadonPy</td><td> Software, open</td><td>Open Python library, automating polymer property calculations using MD simulations</td><td> https://github.com/RadonPy/RadonPy</td></tr><tr><td>Polymer Genome</td><td>Predictor</td><td>Informatics platform, offering 3 dozen polymer property https://www.polymergenome.org predictors</td><td></td></tr><tr><td>PolymRize</td><td>Enabling capability, predictor, commercial</td><td>Commercial platform to train models, predict property, and screen for target polymers and formulations</td><td>https://polymrize.matmerize.com</td></tr></table></body></html>\n\nMD, molecular dynamics; NA, not available.  \n\nfunctional theory $\\left(\\mathsf{D F T}\\right)^{84,85}$ , in conjunction with physical experiments. Early efforts to define screening criteria emphasized the simultaneous attainment of a large electronic bandgap and a high dielectric constant as crucial to achieving high energy density55,56. However, the screening strategy has since been rethought in light of the inverse relationship between these two properties, particularly pronounced in polymers where dielectric response is dominated by electronic polarization.  \n\nTo elucidate this inverse correlation between bandgap and dielectric constant, high-throughput DFT computations55 were conducted for hundreds of hypothetical polymers constructed from common building blocks found in known polymers55,56 (Fig. 2b). The pragmatic choice to focus on polymers with a moderate bandgap $(>4\\mathrm{eV})$ and a moderate dielectric constant $(>3)$ , rather than much higher values of both properties, resulted in the discovery of numerous polymers — including a polythiourea, a polyurea and a polyimide (inset, Fig. 2b) — with energy densities exceeding 9 J $\\mathsf{c m}^{-3}$ , twice that of BOPP, or better.  \n\nEnhancing the energy density of capacitors at elevated temperatures remains a challenge, whose solution is crucial for not only",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# Review article  \n\nsubstantial space and weight savings but also enabling high-temperature operations. Commercial materials such as BOPP rapidly decline in performance and energy density as temperatures rise (Fig. 2c). To discover high-energy-density polymers capable of withstanding temperatures up to $200^{\\circ}\\mathrm{C}$ , an additional critical criterion is needed to complement those based on bandgap and dielectric constant. This third screening criterion emphasizes that the glass transition temperature must surpass a specified threshold $-200^{\\circ}\\mathsf{C}$ in this case — for stable operation at elevated temperatures. Thus, the new screening criteria to design polymers with high energy density, tolerant to large electric field and temperature, are based on the simultaneous maximization of bandgap, dielectric constant and glass transition temperature.  \n\nFollowing the strategy outlined in Box 1, the most reliable available data (measured or generated using DFT) for these three properties have been used to build robust ML models and create new polymers with substantial energy density, stable across a broad temperature range up to $200^{\\circ}\\mathrm{C}$ (refs. 7,55,56,80). Using VFS, over 50,000 candidate polymers were virtually generated, starting from suitable commercially available monomers and the ring-opening metathesis polymerization (ROMP) template. Bandgap, dielectric constant and glass transition temperature of the polymers were predicted, and those satisfying the screening criteria specified in Fig. 2c, about 30 polymers, were presented to synthetic chemists. Five of these were chosen, and four were successfully synthesized and characterized experimentally. All four polymers substantially surpassed BOPP, but one of them, a previously unknown polynorbornene dielectric named PONB-2Me5Cl, was a clear outlier with extraordinary energy density over a broad range of temperatures80. At $200^{\\circ}\\mathrm{C}$ , PONB-2Me5Cl has an unprecedented energy density of $8.3\\mathsf{J}\\mathsf{c m}^{-3}$ , over an order of magnitude higher than any commercial alternative80. The reason for the superior performance of PONB-2Me5Cl is that it simultaneously displays high bandgap, high dielectric constant and high glass transition temperature owing to,",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# Box 1 | An AI-based, use-inspired and application-driven strategy for polymer design  \n\nApplication-driven strategies for polymer design share certain key steps.",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# Define screening criteria  \n\nFirst, a set of screening criteria specified in terms of property values desired for the application must be defined.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# Define the search space  \n\nNext, a protocol to create a candidate list of polymers must be developed. Although numerous enumerative and generative approaches have been used, the greatest barrier has been to produce materials designs that are genuinely synthetically accessible, cost-effective and safe. A powerful approach proposed recently is ‘virtual forward synthesis’, or VFS, which starts with commercially available monomer molecules and creates polymers using known polymerization reaction templates. Polymers generated using VFS have a naturally high probability of synthetic success.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# Machine-learning model development  \n\nIn parallel, reliable machine learning (ML) models are developed to predict the relevant properties rapidly and accurately. ML models are needed because determination or estimation of most properties of new-to-the-world polymers using traditional options is too slow (for example, physical experiments), impractical (for example, simulations based on density functional theory) or semiquantitative at best (for example, classical simulations via molecular dynamics simulations). Developing these ML models requires a sufficiently large and diverse initial training dataset, produced using prior physical experiments or computational methods. The polymer property datasets are then converted to machine-readable numerical form (or ‘fingerprinted’), followed by ‘learning’ the mapping between polymers and properties using suitable ML algorithms.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# Candidate selection and recommendation  \n\nFinally, properties of relevance may be predicted using the ML models developed previously for the generated list of polymers, and those that meet the screening criteria are selected and recommended for physical experimentation and validation. The fresh data thus obtained from physical experiments, whether meeting the required criteria or not, may be used to restart the design cycle, which may progress in an iterative manner (also referred to as ‘active learning’) until the design goals are reached.  \n\n![](images/991d67c75b24a3672bb7c802b771f7cae2686ea0796078db84b0f464fde267ba.jpg)  \nAn AI-based application-specific polymer design strategy   \nAI, artificial intelligence.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# Review article  \n\n![](images/224423a0f96c9232ad2cc8f91983de77b66fc8c55605e493569bf811d5f8c479.jpg)  \n\n![](images/4f8bd9204b5ce216a4367b5849a880b39209970bcbe7c1a6e83fad0cd7d1ef66.jpg)  \nc Designed high-temperature polymer dielectrics  \n\n<html><body><table><tr><td>Property</td><td>Desired value</td></tr><tr><td>Dielectric constant</td><td>>3</td></tr><tr><td>Bandgap</td><td>>3eV</td></tr><tr><td>Glass transition temperature</td><td>>150℃</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 15,
+        "chunk": "# PNB and PONB polymers  \n\n![](images/b4eaeeac017c4d1d60f05bcdd430f6b559fb524c66c7b66384afb5fabfb14958.jpg)  \nFig. 2 | Dielectric polymers for energy storage. a, Ragone plot of various classes of energy-storage systems, including electrostatic capacitors. b, The inverse relationship between dielectric constant and bandgap, which defines the screening for optimal candidates. Three candidates, labelled 1, 2 and 3, were selected, synthesized and validated. c, PONB-2Me5Cl, a newly discovered and tested polymer for energy storage at high temperature, aided by a rethought set of screening criteria (inset table) to address high-temperature behaviours. Four candidate polymers in this class were synthesized and tested; all of them  \n\nrespectively, the lack of conjugation along the backbone, the rotatable polar group in the pendant side chain, and the stiff backbone combined with a bulky side chain. Such a combination of features and properties is rare (and possibly non-existent) in polymers synthesized thus far, highlighting how AI algorithms can aid in extending discoveries beyond conventional human imagination.  \n\nLooking ahead, there are additional opportunities to explore. Whereas the work discussed above revolved around a specific organic polymerization template (namely ROMP), there are hundreds of other templates available51–53, some even incorporating metal atoms in the backbone that can substantially increase dielectric constant86,87. Each template may be coupled with available (in orders of billions) and new-to-the-world (countably infinite) monomers, which could lead to numerous hypothetical, but synthesizable, polymers that are even better than the known and discovered candidates. However, practical considerations, such as monomer cost, complexities and scalability of polymerization processes, toxicity concerns, the role of were high performing, with PONB-2Me5Cl displaying the best performance, substantially higher than regular polymers like biaxially oriented polypropylene (BOPP), polyether ether ketone (PEEK), polyetherimide (PEI), polyfluoroethylene (PFE) and polyimine (PI), by up to one order of magnitude, especially at high temperatures. DFT, density functional theory; PNB, polynorbornene; PONB, polyoxanorbornene. Panel b reprinted from ref. 56, Springer Nature Limited. Panel c reprinted from ref. 80, Springer Nature Limited.  \n\npolymer–electrode interfaces88,89, and aspects related to recyclability and sustainability, impose limitations.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# Polymers for fuel-cell applications  \n\nFuel cells are devices that generate electricity directly from the chemical energy of reactants, namely a fuel (such as hydrogen) and an oxidant (such as oxygen)90. A typical fuel cell consists of a fuel electrode (anode), an oxidant electrode (cathode) and an electrolyte filled in between (Fig. 3a). The electrolyte is a material that allows the charge carriers (such as protons) to transport efficiently while blocking carriers of opposite charge (such as electrons) and the gas reactants from penetrating and diffusing. The catalyst layers, where the oxidation and reduction reactions occur, are typically created by binding nanoparticles of electrocatalysts (such as platinum) to a support with a polymeric ionomer solution. The electrolyte and the catalyst layers of both electrodes accommodate all the essential chemical reactions and charge transports. Starting from early concepts in the 1840s, fuel cells have",
+        "category": " Introduction"
+    },
+    {
+        "id": 17,
+        "chunk": "# Review article  \n\nnow been used in transportation, consumer electronics, residential power supply and more91–94. Compared with capacitors, fuel cells are generally higher in energy density but lower in power density (Fig. 2a).  \n\nNafion, a perfluorosulfonic acid (PSFA) polymer (chemical structure in Fig. 3a), is the currently dominant proton exchange membrane (PEM) — that is, the proton-conducting electrolyte — and ionomer of both electrodes in modern fuel cells8,91–94. Given the conflicting requirements for PEM and ionomers57 (Fig. 3b), this choice is not always optimal. For example, the low permeability of Nafion to $\\mathbf{O}_{2}$ (refs. 95,96) is good for a PEM but not for a cathode ionomer97–99. In addition, the required proton conductivity of Nafion can only be obtained when it is submerged in water or when its humidity is nearly $100\\%$ , a challenging working condition to maintain. Moreover, the relatively low glass transition temperature $(T_{\\mathrm{g}}{\\approx}120^{\\circ}\\mathrm{C})$ of Nafion limits its working temperatures. Finally, Nafion is expensive. These factors, among others, drive the search for Nafion alternatives100–106, specifically fluorine-free materials105. The main approaches used thus far are empirical, focusing on controlling certain key features of Nafion, such as the sulfonic $(-\\mathsf{S O}_{3})$ group105, and exploring its related chemistries97,100, with limited successes.  \n\nIn fuel-cell design, ML approaches have been used mostly for device modelling100,107–109. In a rare work57 using an ML strategy to discover new polymers for fuel-cell applications, a list of screening criteria were established in terms of important properties of PEM and ionomers (Fig. 3b). Suitable datasets were curated, and ML models needed for the properties were developed (some are available in Polymer Genome). The most important model was trained concurrently on two datasets of proton conductivity and water uptake, enabling it to predict these correlated properties simultaneously. This model is an example of the multitask learning technique, used to fuse multiple data channels as elaborated in the ‘Computational–experimental data fusion and multifidelity learning’ section. In this design problem, the VFS approach was applied in a restricted manner by considering about 60,000 homopolymers and copolymers that were experimentally synthesized and reported. More than 60 polymers were identified as possible candidates for PEM, cathode ionomer and anode ionomer (examples are shown in Fig. 3c).  \n\n![](images/788e322eb0260b50e26543b5b7e9587d8a5acc8fea3613bcf464dffbc63be83e.jpg)  \na Fuel cell concept and applications  \n\nFuture work could address some critical gaps in this initial attempt towards designing polymers for fuel-cell applications. First, owing to the historical emphasis on PSFA membranes, the curated data are dominated by polymers with sulfonic $(-\\mathsf{S O}_{3})$ groups, crucial for water retention in PSFA (although other groups may lead to similar functionality)57. Thus, a criterion of ‘having the sulfonic group’ may be used to narrow down the candidate pool. Second, this work was limited in the search space definition, containing only previously reported polymers (albeit for any applications, not just for fuel cells), further restricting the number of discoveries. Going forward, when the training data contain other polymer classes and when the full power of VFS is exploited to cover the vast space of synthesizable polymers51,52, numerous highly qualified candidates for fuel-cell PEM and ionomers can be expected. Development may also be needed to address  \n\nb Key properties required for fuel-cell applications   \n\n\n<html><body><table><tr><td rowspan=\"2\">Key properties</td><td colspan=\"3\">Desired values</td></tr><tr><td>PEM</td><td>Cathode ionomer</td><td>Anode ionomer</td></tr><tr><td>Proton conductivity (S cm-1)</td><td>High</td><td>High</td><td>High</td></tr><tr><td>Opermeability (barrer)</td><td><18</td><td>>18</td><td>NA</td></tr><tr><td>Hpermeability (barrer)</td><td><37</td><td>NA</td><td>>37</td></tr><tr><td>Bandgap (eV)</td><td>>4</td><td>NA</td><td>NA</td></tr><tr><td>Glass transition temperature (°C)</td><td>>123</td><td>>123</td><td>>123</td></tr><tr><td>Thermal decomposition temperature (°C)</td><td>>373</td><td>>373</td><td>>373</td></tr><tr><td>Young's modulus (MPa)</td><td>>156</td><td>>156</td><td>>156</td></tr><tr><td>Having -SO group?</td><td>Yes</td><td>Yes</td><td>Yes</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# c Some candidate polymers for PEM  \n\n![](images/c4ce4aa270188dbaf799f0ad70bb04691aaa494d9f8b195f05c5ec70d13bf632.jpg)  \nFig. 3 | Polymers for fuel cells. a, A schematic illustration of a fuel cell, which uses Nafion for a proton exchange membrane (PEM) and ionomers. b, Screening criteria suggested for a PEM, cathode ionomer and anode ionomer. c, Some polymers discovered for PEM.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# Review article  \n\nconcerns such as the toxicity and sustainability of the candidates, and the scalability of their synthetic routes. As next-generation fuel cells that involve anions rather than protons are being considered110,111, the current approach will need to expand further to meet the requirements of anion exchange membrane designs.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# Polymers for Li-ion battery electrolytes  \n\nLithium-ion batteries are currently used in almost all kinds of electrically powered devices, from portable electronics to hybrid cars, electric cars and aeroplanes, and their adoption is set to surge as global electrification progresses. Serious efforts to develop Li-ion batteries commenced in the 1960s, then accelerated owing to the oil crisis of the early 1970s112. The main advantages of Li-ion batteries are high densities of energy and power, robustness and long life cycle. In the Ragone plot (Fig. 2a), Li-ion batteries are intermediate to capacitors and fuel cells. A Li-ion battery cell (Fig. 4a) has an anode (the reductant) and a cathode (the oxidant), where Li ions are deposited and released, and an electrolyte, through which Li ions are transported. A separator is needed to prevent physical contact between the electrodes while allowing Li ions to shuttle through113. Optimizing the current materials and discovering new ones for anodes114,115, cathodes116–119 and, especially, electrolytes58–61,119, have been important foci of the field120–122.  \n\n![](images/ab2fa0be915800b8d99cd5795e6ee82576cc2faf99274501cfbe945340828a73.jpg)  \na Lithium-ion battery concept (discharging status)  \n\n![](images/6ea0d1f31f573a0944f77d244f33457ffaf5ee2c80e2ee41d979f40c32860321.jpg)  \nb AI-assisted discoveries of polymers for electrolytes  \n\n![](images/16626644e8bc6b087e4e0e7c2d03814b8e9f14e6310c9a620aa5a11aeece1c3c.jpg)  \nc A chemistry-informed neural network   \nFig. 4 | Polymers for Li-ion batteries. a, A schematic structure of a Li-ion battery. b, Some artificial intelligence (AI)-assisted discoveries of solid polymer electrolytes (SPEs) compared to previously studied SPEs, and their ionic conductivity relationship with the glass transition temperature. c, ChemArr, a physics-informed neural network, enforcing the Arrhenius formula in the predictions of Li-ion conductivity. d, Predicted Li-ion conductivity as a function  \n\n![](images/c1538ea91e33c4d420b285bebba30abc0bf7a1f44ccb0c92398aae46b54d1bda.jpg)  \nd Arrhenius plot of ionic conductivity   \nof temperature, which agrees well with the Arrhenius formula. e, Some polymers discovered for Li-ion battery electrolytes using machine learning strategies. MAE, mean absolute error; PEO, poly(ethylene oxide). Panel b reprinted with permission from ref. 146, American Chemical Society. Panels c and d reprinted from ref. 143, CC BY 4.0.  \n\ne Discovered polymer electrolytes   \n\n\n<html><body><table><tr><td>Polymer 2D structure</td><td>lonic conductivity (mS cm-1)</td></tr><tr><td></td><td>2.041 ± 0.384</td></tr><tr><td>n</td><td>1.605 ± 0.054</td></tr><tr><td></td><td>1.517 ± 0.101</td></tr><tr><td></td><td>1.515 ± 0.199</td></tr><tr><td></td><td>1.501 ± 0.124</td></tr><tr><td>N</td><td>1.491 ± 0.176</td></tr><tr><td></td><td>1.481 ± 0.262</td></tr><tr><td></td><td>1.473 ± 0.140</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 21,
+        "chunk": "# Review article  \n\nThe search for new electrolyte materials is motivated by safety concerns and the flammability of current liquid electrolytes, such as solutions of lithium hexafluorophosphate and some flammable organic liquids. Such materials are believed to lead to spontaneous explosions and fires in some Li-ion battery units123, as in more than 20 documented fires in Tesla models since their introduction124 and a Boeing 787 Dreamliner aeroplane125. As a potential alternative, solid polymer electrolytes (SPEs) that are light, cheap and, most importantly, safe have been examined, including those based on poly(ethylene oxide) (PEO)126–129, polyacetals130,131, polyethylene carbonates132, polyesters133, polyacrylonitrile (PAN)134, poly(vinyl alcohol) (PVA)135, poly(methyl methacrylate) (PMMA)136, and polymer blends such as PEO/PAN137 and PVA/PMMA138. However, these SPEs still have major disadvantages for use in Li-ion batteries, one of which is their low Li-ion conductivity $(\\lesssim10^{-5}\\mathsf{S c m}^{-1})$ at practical operating temperatures (the target conductivities are ${\\gtrsim}10^{-4}\\mathsf{S c m}^{-1})$ .  \n\nAlthough a number of SPE candidates have been explored, they represent only a tiny fraction of the polymer space, which comprises tens of thousands of already known and synthesized polymers25,57, or millions of commercially available or easy-to-synthesize monomers that can be polymerized via hundreds of known polymerization reaction templates. There is a good explanation for this: putting physical experimentation aside, physics-based computational methods are not ready to evaluate SPE candidates. Classical molecular dynamics (MD) simulation, the most practical computational method to estimate Li-ion conductivity today in polymers128,129,139,140, is, at best, semiquantitative, and requires extreme care and specialized skills. Good candidates for potential SPEs are likely to be somewhere in the vast untapped polymer space, awaiting discovery and deployment.  \n\nML approaches have made some progress42,139,141–144, especially in accelerating the MD-based evaluations of SPEs and decision-making procedures. Bayesian optimization has been used to drive coarsegrained MD explorations of the polymer space. One endeavour142 identified polymer blends with optimized Li-ion conductivity and mechanical strengths; another42, by generating a big volume of data, uncovered the relationships between the Li-ion conductivity and relevant atomic-level features such as molecule size and non-bonding interaction strengths. Based on an interesting idea to ‘accelerate’ the MD simulations, a ML capability was developed139 to perform early predictions of the equilibrium Li-ion transport properties of a polymer from its chemo-structural descriptors and information obtained within the first 0.5 ns of the MD trajectory. This scheme could reduce the MD simulation times by $90\\%$ , substantially accelerating explorations for SPEs139. In recognition of the importance of high-fidelity data in the field, a cloud-based platform was established145 to share raw data from 6,286 MD trajectories of amorphous polymer electrolytes and standard post-processing and analysis tools.  \n\nThe impact of ML approaches extends beyond the acceleration of MD simulations. By constructing a database of SPEs, a transfer-learned graph neural network was trained and used146 to search over 9,600 combinations of polymers, dopants, salts and other parameters, leading to the discovery of eight polyphenylene sulfides, which were then validated experimentally (six of them are shown in Fig. 4b). ChemArr is a physics-informed neural network in which the Arrhenius equation, which governs the temperature dependence of the Li-ion conductivity, is explicitly encoded143 (Fig. 4c). The model was trained on a dataset of 7,133 experimental Li-ion conductivity data points curated for 247 unique polymers, and its power to predict Li-ion conductivity was demonstrated on two unseen new polymers, named $\\mathsf{\\Sigma}_{-}\\mathsf{C O D C}_{4}\\mathsf{C F}_{3}\\mathsf{S A}$ (Fig. 4d) and $\\mathsf{P_{-}C_{10}P A_{-}M C}$ . Attempts to design new SPEs were further extended to involve a quantum annealer, inverting the developed regression model to identify the ‘ideal features’ of the desired SPEs147. Existing databases were then searched, uncovering a trithiocarbonatebased polymer resembling the ideal SPE. This polymer was synthesized and shown to offer a conductivity of $10^{-6}{\\mathsf{S c m}}^{-1}$ and thermal stabilities above $80^{\\circ}\\mathsf{C}$ . Efforts in the past 2–3 years have leveraged the development of generative models (Generative Pre-trained Transformer (GPT)-based and diffusion-based) to conditionally and continually design new homopolymers with high predicted Li-ion conductivities148,149. Using this approach, 19 polymer repeat units were found149 to display computed ionic conductivities (via MD simulations) surpassing that of PEO (Fig. 4e).  \n\nAlthough Li-ion conductivity is the most important property of a SPE for Li-ion batteries, SPEs should also have a large electrochemical stability window, which controls the open-circuit voltage and ultimately the cycle life of the batteries, and should be mechanically strong, thermally stable and durable for safety reasons. The critical gaps to address arethe develpment of necessarily bigger, more diverse, high-quality databases, and training powerful predictive models of the desired properties. The quantitative screening criteria for SPEs, like those in Fig. 2c and Fig. 3b, as well as for the novelty and validity of the candidates148 should be established. Then, the vast space of synthetically accessible polymers can be screened to identify superior SPE candidates. Regardless of the specific approaches adopted, care must be taken to safeguard the likelihood of finding viable and scalable synthetic routes of the SPE candidates.",
+        "category": " Introduction"
+    },
+    {
+        "id": 22,
+        "chunk": "# Membranes for gas separation  \n\nUsing synthetic polymer-based membranes to separate gas mixtures10,62,150–157 — for example, removing ${\\mathsf{C O}}_{2}$ from natural gas or removing $\\mathbf{O}_{2}$ from air — is favoured over competing technologies owing to the suitable combinations of energy efficiency, cost and size in these membranes158. Compared with distillation, which conventionally requires a massive amount of heat, membranes can, in principle, separate gas mixtures in the presence of just a pressure gradient (Fig. 5a). An important performance measure of a gas separation membrane is the selectivity, which, for binary mixtures, is defined as $\\alpha_{\\mathrm{ij}}\\equiv\\mathbb{P}_{i}/\\mathbb{P}_{j},$ where $\\mathbb{P}_{i}$ and $\\mathbb{P}_{j}$ are the permeabilities of i, the more permeable gas, and $j$ , the less permeable gas. Although many other technological factors influence the success or failure of a particular membrane, an ideal membrane material will have high selectivity and high permeability to the wanted gas. This combination simplifies the membrane engineering process and reduces the operating and capital costs.  \n\nThe selectivity and permeability depend heavily on the size of ‘free volume elements’ (FVEs) — the small, often-ephemeral gaps between polymer chains — and the frequency at which these gaps appear and disappear owing to thermal fluctuations in the polymer chains. The selectivity is maximal when the FVEs have a uniform size, preferably positioned between the kinetic diameters of the desired and undesired gases159,160. Therefore, an ideal FVE size distribution should be tight and appropriately centred (inset, Fig. 5a). The permeability is high when FVEs with appropriate size for gas diffusion are created at a rapid frequency. Typically, materials that exhibit high frequencies of FVE creation often have a broad distribution of FVE sizes, giving rise to the well-known trade-off between permselectivity and permeability157,159 (see Fig. 5b for an example).  \n\nThe most obvious consequence of the trade-off is the presence of a performance upper bound, pointed out in 1991 (refs. 157,159).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# Review article  \n\n![](images/13d546b40be4b97fde57a561598f535e364ca503456c3d7675260b9aa4a3ac9a.jpg)  \na Gas atom transport in polymer membranes   \nb Robeson plot for gas separation membranes   \nseparation membrane, working in the presence of a pressure difference between ingress and egress, and three pore-size distributions that are ideal, normal and poor for the selectivity. b, Robeson plot for $\\mathrm{CO}_{2}/\\mathrm{CH}_{4}$ selectivity, given with respect to the ${\\mathsf{C O}}_{2}$ permeability, showing the trade-off between permeability and   \nclassic membrane polymers discovered over the years. c, Chemical structures of some known and machine-learning (ML)-derived polymers. For ML-derived polymers, data were generated either by molecular dynamics (MD) simulation or experiments.  \n\nResiding below this bound are the known polymers of that time, including Matrimid, a polyimide membrane that is still commercially used today161,162. Since then, a handful of new polymers have been discovered that surpass the 1991 bound, establishing two new bounds dated in 2008 and 2019 (refs. 147,160). One of the earliest discoveries that pushes the 1991 bound was PIM-1, or Polymer of Intrinsic Microporosity 1, which possesses a new repeat unit chemistry147. Specifically, PIM-1 and other PIMs feature a site of contortion (that is, a spiro centre) in every repeat",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# Review article  \n\nunit that ‘kinks’ the polymer chain at extreme angles. This feature alone is often insufficient to make a polymer a ‘PIM’; another salient design motif is the incorporation of the spiro centre into a ladder polymer. The combination of these features, unseen in previous polymers, results in the record-breaking permeability of PIM-1. In summary, new chemistries can substantially improve performance, continuously pushing the existing bounds upwards, although this process might have a conceptual upper limit153.  \n\nAlthough permeability and selectivity may be estimated using MD simulations, this method is not quantitative enough to discover new and improved gas separation membranes. Works in the past 6–7 years have shifted towards ML approaches, training predictive models on past data to estimate the gas permeability from the chemical structure25,154,155,163–165. In 2022, six ML models for the permeabilities of He, $\\mathsf{H}_{2},\\mathsf{O}_{2},\\mathsf{N}_{2},\\mathsf{C O}_{2}$ and $\\mathrm{CH}_{4}$ were developed and used155 to screen more than 9 million hypothetical polymers, identifying thousands predicted to be ultrapermeable to $\\mathbf{O}_{2}$ and $\\mathbf{CO}_{2}$ . Eight candidates, named P-DNN-C1 through P-DNN-C4, P-DNN-D1, P-DNN-D2, P-RF-C and P-RF-D (Fig. 5c), were validated using MD simulations. In another effort, six models for the permeability of the six gases mentioned above were developed and used154 for 11,325 polymers from the National Institute for Materials Science (NIMS) database, predicting hundreds lying above the upper bounds for the $\\mathbf{O}_{2}/\\Nu_{2}$ and $\\mathrm{CO_{2}/C H_{4}}$ separations. Two of them, namely poly[(1,3-dioxoisoindoline2,5-diyl)sulfonyl(1,3-dioxoisoindoline-5,2-diyl)-1,4-phenyleneoxy1,4-phenylene] and poly[(1,3-dioxoisoindoline-2,5-diyl)sulfo­nyl­(1,3- dioxoisoindoline-5,2-diyl)-1,4-phenylenemethylene-1,4-phenylene] (labelled as P432092 and P432095 in the NIMS database), were synthesized and tested for $\\mathrm{CO}_{2}/\\mathrm{CH}_{4}$ separation (Fig. 5c). Targeting $\\mathbf{CO}_{2}$ separation from N2 for carbon capture, three models, including one for PCO2 were developed and used to identify hundreds of high- $\\mathbf{\\bar{P}}_{\\mathbf{C}0_{2}}$ polymers163 Three of them, labelled as Giro-1, Giro-2 and Giro-3 (Fig. 5c), display high $\\mathbb{P}_{\\mathbf{C}0_{2}},$ as estimated by MD simulations.  \n\nThese exemplary works highlight the role of ML approaches in designing membranes for gas separation. Yet critical challenges remain. One persistent challenge, common to all application domains, is ensuring that the recommended polymers are synthetically feasible and scalable. As an illustration, only two of the ML-derived polymers shown in Fig. 5c have been synthesized; the remaining candidates are difficult to make. Constructing a vast space of synthetically accessible polymers using VFS could be a solution, provided VFS includes reaction templates and chemistries with ladder features and spiro centres.  \n\nA second challenge, also relevant to all applications, is that the models need to train on data spanning large enough chemical spaces. To alleviate this challenge, MD-simulated data (although low in fidelity) for $\\mathbb{P}_{i}$ (ref. 166) and related or correlated properties may be generated to augment available measured data. For example, the solubility $\\mathbb{S}_{i}$ and diffusivity $D_{i}$ of a gas in a polymer i are related to the permeability by $\\mathbb{P}_{i}=D_{i}\\times\\mathbb{S}_{i}$ . Furthermore, the fractional free volume (FFV) of polymers, as discussed above, is strongly correlated to their permeability167. Data (measured and/or simulated) from any of two or more of these four properties $(\\mathbb{P}_{i},D_{i},\\mathbb{S}_{i})$ , FFV), may be leveraged in a multitask ML architecture to learn all properties simultaneously, improving the accuracy and the robustness of the $\\mathbb{P}_{i}$ predictors.  \n\nFinally, ‘ageing’ (or degradation) problems that pervade gas separations applications should be addressed. Over time, $\\mathbb{P}_{i}$ can decrease owing to altered or degraded distribution of FVEs, and this behaviour should be managed appropriately. Membranes for gas separation should be mechanically, thermally and chemically stable over $5+$ years for viable real-world applications. Testing these long time frames in an experimental laboratory is typically infeasible; development of algorithms to predict ageing of a given polymer would accelerate development in this field. Beyond membrane performance and ageing, incorporating additional properties in the screening criteria relevant for scale-up such as tensile modulus, glass transition temperature and thermal decomposition temperature would be impactful.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 25,
+        "chunk": "# Membranes for organic liquid mixture separations  \n\nPolymer-membrane-based separations of non-aqueous or organic– water liquid mixtures solve a different class of problems relative to gas separations. Membrane-based separations of liquid mixtures, driven by pressure rather than heat, are energy and economically efficient63–66. This method is important to the chemical and pharmaceutical industries, where separation processes, such as in the recovery of organic solvents, could account for up to $40\\mathrm{-}70\\%$ of the capital and operating cost63. Technically, membranes can be used to separate organic compounds with similar boiling points65 or that are temperature sensitive168; these types of separations are challenging or expensive to carry out with incumbent technologies, such as vacuum distillation. Important liquid mixture separations accessible to membranes include water purification, solvent recovery, solute concentration, diluent separation, iterative synthesis of oligomers, homogeneous catalyst recovery, natural product extraction, membrane reactors and solute fractionation, among many others63–65,169. Membranes that can separate the liquid phase of small molecules, such as ethanol and iso-octane, typically operate in a solution-diffusion regime, like gas separations.  \n\nOne difficulty for this class of membrane-based separations is estimating how well the membrane will perform when challenged with a new complex mixture. The efficiency of a separation depends on several factors, including the characteristics of the liquid mixture to be separated (such as the number of distinct solute and solvent types, concentration, size, polarity and so forth of each solute and solvent), the choice of the membranes, the operating conditions (such as pressure) and the time-dependent performance fluctuations (that is, the ageing). In the design problem of membranes for separation of organic liquid mixtures specifically, this high dimensionality of the search space makes it a daunting task for traditional physics-based models alone.  \n\nTo handle complex mixtures, ML models based on neural networks, random forest models and support vector machines were established to predict important liquid mixture transport properties such as the permeance and rejection of mixtures containing a solvent and a solute169. Nonlinear regression techniques, whose parameters are determined by a combination of genetic programming and global deterministic optimization, were used to predict the permeance of pure solvents and solvent mixtures through membranes170, and the solute rejection in liquid mixtures containing multiple solvents and/or solutes171. Building on this work, some ML models were developed172 that can predict the solute rejection using the molecular structure of the solute as input. Unlike previous counterparts that can handle a few fixed solutes, these models can be generalized to any solute.  \n\nEach of the above works are suitable for mixtures containing solutes of a particular size $(100-2,000\\ g\\ m\\mathrm{ol^{-1})}$ and often much smaller solvents that permeate via a pore-flow style mechanism. However, these models are unsuitable for mixtures of small molecules, or complex mixtures (for example, crude oil containing thousands of components), with near equal concentrations, in which there is no clear solvent or solute. Moreover, not all membranes operate with a pore-flow transport modality; indeed, many effective membranes",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 26,
+        "chunk": "# Review article  \n\n![](images/d81b192271aa0fbd6b23696a1151a339ded0b942520a8a6f0f918339645b32d1.jpg)  \na Multiscale approach integrating machine learning and transport modelling",
+        "category": " Introduction"
+    },
+    {
+        "id": 27,
+        "chunk": "# b Polymers used to test the multiscale predictive model  \n\n![](images/f8e93603353f34f27649c396d0ddccfabbc406d8d7643df524aec8ad041d95a4.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 28,
+        "chunk": "# Review article  \n\nFig. 6 | Polymers for the separation of complex liquid mixtures. a, Multiscale data-driven transport modelling framework informed by physics and/or chemistry. b, Five polymer membranes used to validate the framework. c, Test results from four selected membranes on 9-component or 12-component hydrocarbon mixtures, showing close correspondence between predicted and operate in the solution-diffusion regime. To extend the range of possible mixtures and operation regimes, a multiscale approach integrating a multicomponent mass transport scheme with a physics-informed ML approach was developed173 (Fig. 6a). First, a neural network was used to predict the diffusivity and sorption uptake of each individual mixture component for a given membrane. Then, these predictions were fed into a Maxwell–Stefan solution-diffusion transport model174, from which each component’s flux was predicted. Importantly, this approach generalizes to the separation of arbitrary mixtures and linear membranes. Physical experiments then validated the framework’s ability to predict the permeation outcomes of complex liquid mixtures through membranes. Five polymers, two of them (Torlon and Matrimid) commercially available and the others (DUCKY-9, DUCKY-10 and SBAD-1) recently lab-synthesized66,175 (Fig. 6b), and mixtures of either 9 or 12 liquid components (Fig. 6c) or real crude oils with thousands of liquid components (Fig. 6d), were tested. This multitiered approach could predict the separation of complex mixtures to within $6\\%$ of the measured values173 (Fig. 6c,d).  \n\nAlthough the ability to build robust ML models that can handle multicomponent industrial-scale complex liquid mixtures has been demonstrated, their potential can be expanded by continually training the models on emerging new data for other complex mixtures. Furthermore, the true opportunity is to leverage these models to suggest new polymer membranes and optimal operating conditions for industrially important liquid mixtures. This gap may be addressed with the adoption of generative methods, like the VFS approach, to generate a diverse pool of candidates, forecast permeation performance for complex liquid mixtures and subsequently identify those meeting predefined criteria.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 29,
+        "chunk": "# Conducting conjugated polymers  \n\nThe development of conducting polymers176–180 marks a milestone in the history of polymers. In the early 1970s, polyacetylene was synthesized, exhibiting semiconducting behaviour ascribed to the delocalized $\\pi$ -electrons arising from its conjugated structure179. Treating polyacetylene with Lewis acids or bases was revealed to substantially enhance its conductivity, sometimes by up to 13 orders of magnitude180, and turning it into a conductor. Because this process involves the removal or addition of electrons to the polymer chains, it is termed ‘doping’ in analogy to the doping procedures adopted in silicon technology. Doping is important to controlling the conductivity of conducting polymers, allowing them to find applications in organic light-emitting diodes181,182, organic field-effect transistors183,184, organic solar cells185,186, biomedicine187–190 and beyond.  \n\nUsing a curated set of 389 experimental data points covering 226 polymers and 65 dopants, with conductivities spanning 16 orders of magnitude, a data-driven approach was able to accelerate the identification of suitable candidates for conducting polymers191. Classification and regression models to predict conductivity were developed191 from handcrafted chemical fingerprinting schemes. The classification model categorized the conductivity as low, medium or high, while the regression model provided numerical predictions. The models were measured results. d, Test results from two selected membranes on real crude oils with thousands of liquid components, showing close correspondence between predicted and measured results. ML, machine learning. Panels c and d reprinted from ref. 173, CC BY 4.0.  \n\nused to screen over 800,000 polymer–dopant combinations, recommending 500 candidates for experimentation. Guidelines highlighting the critical features for conductivity were also compiled to aid future design efforts.  \n\nBeyond electronics, a vast amount of data have been published on a wide array of doped polymers in organic photovoltaics192, including their open-circuit voltage, power conversion efficiency and other relevant parameters. Such data must be collected and curated (preferably aided by the natural language processing techniques discussed below) before they are ready for informatics, and these efforts are ongoing.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 30,
+        "chunk": "# Polymers for a sustainable world  \n\nWe now turn to the global issue of plastic pollution12,193. An enormous volume of plastics is produced every year, but their high chemical and thermal stability makes them extremely difficult to recycle194–197. According to a recent report by Greenpeace, only $5\\%$ of about 51 million tonnes of plastic created in the United States alone in 2021 was recycled198, leaving the remaining for landfill at their end of life. Multiple approaches are expected to address this critical problem199–201. Technical solutions, such as developing and recycling polymers, are particularly useful and active202–204. Among the many classes of recyclable polymers (Fig. 7a), we address those that are biologically and chemically recyclable.  \n\nBiodegradable polymers. In biological recycling, biodegradable polymers are transformed into natural by-products such as water and $\\mathbf{CO}_{2}$ through the actions of enzymes from microorganisms such as bacteria (Fig. 7b). Several biodegradable polymer classes, including those derived from chitosan, alginate, collagen, gelatin, cellulose, hyaluronate, silk, fibrinogen and starch, have been actively considered205 to replace petroleum-based plastics. Applications for these polymers are targeted in numerous fields, including biomedicine206, the food industry207,208, packaging209, water purification210,211, electronics212, the automotive industry213, sustainable aviation fuel214, cosmetic products215, fabrics, paint additives, printing and adhesives, to name just a few.  \n\nNaturally, the most important property of biodegradable polymers is their biodegradability — that is, the ability of the materials to be decomposed by enzymes. Perhaps because the biodegradation processes are highly complex and sensitive to extrinsic (such as processing) and environmental conditions, quantifying and documenting the biodegradability in a consistent manner are non-trivial216. Commonly used measures of biodegradability are highly diverse, including weight loss217, total organic carbon formed218, tensile strength, carbonyl index and molecular weight change219, and a yes/no categorical variable220 during biodegradability testing. The lack of a robust and consistent definition of biodegradability makes it challenging to create good databases for this important property. Initial steps have been taken to predict the biodegradability of polyesters using ML methods220. Clearly, to design degradable polymers for specific applications in the future, it will be necessary to predict the biodegradability of polymers",
+        "category": " Introduction"
+    },
+    {
+        "id": 31,
+        "chunk": "# Review article",
+        "category": " Introduction"
+    },
+    {
+        "id": 32,
+        "chunk": "# b Biorecycling: life cycle of biodegradable polymers  \n\n![](images/8d18581e27a94276b6c94b0e85c90017e0adacf33f380ab476678b68749214d5.jpg)  \na Recyclable polymers  \n\nRaw materials rich   \nin starches that replace   \npetroleum products   \nin bioplastics  \n\nHarvested plant materials to proceed to extract the starches  \n\nChemical compounds refined in biorefineries to fit the manufacturers’ specifications  \n\n![](images/81a5fb76999ecd4eb42b70fbc40ff747ab77ef06d000024f7625a04bf2cdd660.jpg)  \n\nOrganic waste to be composted and returned to the earth as mulch  \n\nDisposed bioplastic products in an organic waste collection bin  \n\nProducts manufactured using granules of the compounds  \n\n![](images/c8f1541b40a4d06ed66b318a4da64d2c37b9dc2f96b1f540890fc52a8e844767.jpg)  \nc Pipeline to design new PHA-based bioplastic candidates  \n\n![](images/73de797f41b41c423b86ac8a1ec7e0e8af0fa78f637154c4dc5d411d1c79e680.jpg)  \nd Ring-opening enthalpy $(\\Delta H_{_{R O P}}$ ) measured and computed for cycloalkanes  \n\n![](images/225e074f16146f07393bf53453c09ee576d64c315ddb4e0bc084121a104682fe.jpg)  \ne Polybenzothiocane, a recyclable polymer   \nFig. 7 | Polymers for a sustainable world. a, Regular recycling methods of recyclable polymers. b, The life cycle of biodegradable polymers in biorecycling. c, An artificial intelligence-assisted scheme to design biodegradable polymers. d, Measured and computed ring-opening enthalpy of cycloalkanes, showing  \n\nin a quantitative manner meeting different measures of biodegradability. This will require the development of high-quality datasets that include not only the chemical structure and biodegradability of the polymers but also other important information such as the biodegradation time profile, relevant environmental conditions, processing history, morphology and sample geometry.  \n\nPutting the quantitative predictions of biodegradability aside, and focusing only on the design of polymer chemistries amenable for biodegradation, the search space is narrowed simply to materials close correspondence between the two approaches. e, Polybenzothiocane, a chemically recyclable polymer developed in a synergy between computational, machine learning and experimental approaches. PHA, polyhydroxyalkanoate. Panel d adapted with permission from ref. 68, American Chemical Society.  \n\noccupying a known biodegradable chemical class that also display application-specific property values. Polyhydroxyalkanoates (PHAs) have emerged as a promising class of biodegradable polymers whose tremendous chemical diversity is directly accessible via biosynthesis by microalgae and bacteria. PHAs are known to be produced by about 300 species of bacteria that thrive in wastewater effluent and can be cultivated year-round, making them synthetically sustainable221,222. A vast diversity of polymer compositions is possible from the over 150 PHA monomers available, and configurational",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 33,
+        "chunk": "# Review article  \n\n(random, alternate, block copolymer, blend and so on) and morphological (percentage crystallinity, molecular weight, dispersity and so on) degrees of freedom allow for additional tunability. However, the design rules mapping the chemistry and structure of these biopolymers onto their properties remain largely unexplored. Although DFT computations and classical MD simulations have been used for this purpose223–225, predictive ML models are more reliable and scalable. In one work67, PHA-based plastics were targeted as replacements for seven common petroleum-based consumer plastics. With this goal, multitask deep neural networks were trained on a multiproperty polymer dataset consisting of nearly 23,000 experimental data points of 13 different properties and validated on a diverse set of 15,344 homo­ polymers and 7,512 copolymers. Nearly 1.4 million PHA-based polymers were screened using these models, identifying two biodegradable replacements for each commodity petroleum-based plastic (Fig. 7c). Although future experimental efforts are required to validate the predictions, this work demonstrates the potential of informatics-based tools in addressing the needs of biodegradable polymer design.  \n\nApart from the technical feasibility, it is challenging to make biopolymer production and recycling economically viable and sustainable, despite the ever-growing demand, policy-driven push, and concomitant trends in market growth for environment-friendly plastics. The cost-competitiveness and scalability of the synthetic routes for usable biopolymers, and the polymer waste recycling processes, are of prime consideration. Whereas the production cost of traditional polymers is around US\\$1,000–1,500 per metric tonne, that of commonly used biopolymers can vary from 4 to 10 times more226,227, owing in large part to expensive carbon substrates, the highly sterile conditions required in batch reactors during fermentation, and the laborious and time-intensive downstream processes needed to extract and purify the synthesized biopolymers228. Genetically engineering microorganisms with designer metabolic pathways that improve accumulation of biopolymer granules constitutes a future avenue worth exploring.  \n\nChemically recyclable polymers. In chemical recycling, polymers reversibly depolymerize into monomers. Ring-opening polymers, created by opening cyclic monomers and polymerizing them, are particularly suitable because the ring-opening (that is, polymerization) and ring-closing (that is, depolymerization) reactions are easy to manipulate (Fig. 7d). On depolymerization, the monomer feedstocks can be repolymerized to create new materials with original purity and performances. The polymerization and depolymerization processes may be tuned by controllable parameters such as the monomer ring size, catalysts, temperature, solvents and other triggers199,200,229,230. Research efforts in designing chemically recyclable ring-opening polymers for sustainability are timely69,70.  \n\nOne of the most important controllable parameters in such chemical recycling processes is ring-opening enthalpy, $\\Delta H_{\\mathrm{ROP}}$ , defined as the difference between the energy of the polymer and that of the ring monomers. Ring-opening polymers that are depolymerizable should have slightly negative $\\Delta H_{\\mathrm{ROP}},$ falling roughly between $-20\\ k\\mathrm{l}\\mathsf{m o l}^{-1}$ and $-10\\left\\mathrm{kJ\\mol^{-1}}$ . Although $\\Delta H_{\\mathrm{ROP}}$ can be measured experimentally, computational approaches can be much faster. This aspect is crucial for the selection of suitable monomers and eventually for the design of new depolymerizable polymers. The critical gap here is that although $\\Delta H_{\\mathrm{ROP}}$ can be roughly computed in a simple and intuitive way, doing so with a satisfactory level of accuracy is non-trivial. Challenges in computing $\\Delta H_{\\mathrm{ROP}}$ are diverse, including creating suitable atomic-scale polymer models, selecting the right level of theory, appropriately sampling the polymer configurational space and, finally, reaching an ambitious level of the ‘chemical accuracy’, that is, about 5 kJ mol−1 or lower, expected of ab initio calculations231.  \n\nA computational method has been developed68 to quickly and accurately calculate $\\Delta H_{\\mathrm{ROP}}$ for arbitrary polymers. Central to this scheme is a procedure designed to extensively sample the configuration space and compute the energies of the samples using DFT. Then, $\\Delta H_{\\mathrm{ROP}}$ obtained for polymer models of different sizes is extrapolated to the limit of the polymer at infinite size. Although this method is robust and accurate, as demonstrated by the experimental and computed ring-opening enthalpies of the cycloalkane series (Fig. 7d), it is computationally demanding. To accelerate the accurate estimation of $\\Delta H_{\\mathrm{ROP}}$ a predictive ML model has been trained71 on both experimental and computed data. This model provides $\\Delta H_{\\mathrm{ROP}}$ predictions with an averaged error of about $8\\mathrm{kJ}\\mathsf{m o l}^{-1}$ , close to the desired chemical accuracy $(-5\\mathsf{k})\\mathsf{m o l}^{-1})^{231}$ .  \n\nThese computational and ML approaches, developed synergistically with experimental efforts, have contributed to new ring monomers that have been successfully polymerized. Synergistic computations and experiments69 investigated a series of depolymerizable thiolactones created by systematically changing the pattern of methyl substitution and incorporation of sulfur heteroatoms. Chemically recyclable polythioethers (Fig. 7e) have also been synthesized from readily accessible benzothiocane monomers70.  \n\nFuture designs of chemically recyclable polymers will benefit from further advances in ML models. For instance, the ML approach to predict $\\Delta H_{\\mathrm{ROP}}$ can be improved considerably by growing and diversifying both the computational and experimental $\\Delta H_{\\mathrm{ROP}}$ datasets. VFS may be used to generate hypothetical polymers via reaction templates amenable to depolymerization. Reliable models will also need to be developed to rapidly predict other relevant properties, beyond $\\Delta H_{\\mathrm{ROP}},$ for the large number of generated polymers. Attributes of interest include thermal, mechanical, gas/solvent solubility, gas/solvent transport and thermodynamic properties, depending on the application area of interest. As with the other applications discussed above, successful materials design is an exercise in multiobjective property optimization. Beyond properties, successful and scaled-up development of chemically recyclable polymers involves synthetic considerations, such as the entropy of (de)polymerization, kinetics, solvent effects and catalyst selection199.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 34,
+        "chunk": "# Critical next steps Polymer composites and formulations  \n\nIn the real world, polymer composites or formulations are much more common than homogeneous neat polymers. They come in various forms, involving a base polymer matrix and additives such as reinforcing and flame-retardant materials, rheology modifiers and processing conditions. The polymer matrix is the primary continuous phase in these materials. The dispersed phase, containing the additives embedded in a discontinuous manner, and the processing protocols modulate the properties, overall appeal and utility of the polymer composites232,233.  \n\nThe versatility of polymer composites, allowing for desirable properties to be customized on demand, has led to their widespread applications234–239. For electric vehicles, composites with suitable impact resistance, corrosion resistance, durability, and flame resistance and fire containment are used in battery enclosures. In hydrogen fuel-cell vehicles, mechanically robust composites are used to construct pressure vessels for hydrogen storage, while advancements in",
+        "category": " Introduction"
+    },
+    {
+        "id": 35,
+        "chunk": "# Review article  \n\npolymer composites for fuel-cell membranes and ionomers are still sought after101–103.  \n\nThe performance of a composite is intricately linked to factors such as the chemistry and topology of the base polymer (which may also be a copolymer or polymer blend), additives and processing conditions. Although informatics protocols can handle these variations, adequate data pertaining to these variations must be captured. Progress has been made to handle copolymers and blends within informatics schemes, including representations240, and efforts are emerging to handle more complex composites with a variety of additives.  \n\nTraditional approaches to optimize composites, primarily involving physical manufacturing and testing, are arduous and time consuming238. ML approaches are much more efficient, either accelerating composite simulations241 or training on experimental data to predict mechanical properties, such as fracture behaviour, ductility and density242. In a recent effort, a polymer composite database was curated based on technical datasheets from major manufacturers (Tran, H. et al., unpublished work). Using handcrafted features for the polymers, fillers and processing parameters, ML models for tensile modulus and stress at break were developed (Tran, H. et al., unpublished work). A sizeable opportunity exists for developing similar models for a large spectrum of composite properties — including mechanical, thermal, flammability and transport properties — using similar approaches, a logical evolution of the AI-based protocol depicted in Box 1.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 36,
+        "chunk": "# Autonomous data extraction from literature using language models  \n\nThe annual growth rate of materials science papers is about $6\\%$ . Owing to the non-machine-readable nature of the content, the expanding literature makes it difficult to extract valuable quantitative and qualitative information about material properties, manually discern trends and locate materials with desirable properties. Furthermore, data corresponding to negative (or undesired) results are unlikely to be reported, skewing the balance of literature data. These factors impede progress in materials informatics, where property predictor training relies on labour-intensive data curation from literature.  \n\nNatural language processing (NLP) techniques, such as named entity recognition (NER), relation extraction, co-referencing and named entity normalization, are vital for extracting information243,244. Transformer-based models like Bidirectional Encoder Representations from Transformers (BERT)192,245 and ChatGPT, trained on extensive unlabelled text, are predominant in self-supervised learning for contextual embeddings and information understanding. NER and relation extraction commonly use a BERT-based architecture, with labelled inputs (words and phrases indicated as material, property, characterization method and so on) feeding into task-specific ML models. Adapting these methods to new domains necessitates ontology-based labelling of new datasets. Tools like ChemDataExtractor246, ChemSpot247 and ChemicalTagger248 specialize in NER for material entities, but these prior NLP efforts have focused predominantly on inorganic materials249,250 and organic molecules251,252, neglecting polymers.  \n\nExtracting information about polymers is challenging because their naming conventions vary, and these names (which in many cases do not reflect the chemical content of the polymer) cannot be directly converted to simplified molecular-input line-entry system (SMILES) strings that represent the atomic connectivity of polymers in line notation. Efforts in the past 2–3 years have taken important steps to address these polymer-specific issues192,243,244,251,253. Of note is a pipeline for extracting material property data from a large body of polymer literature, derived from a corpus of over 2.4 million materials science articles published in the past two decades192. A NER model was trained on annotated versions of the polymer text using MaterialsBERT, a language model based on PubMedBERT254. Using this pipeline, over 1.1 million polymer property records were extracted from the full text of the corpus. The extracted data are available at Polymer Scholar (Table 1).  \n\nMoving forward, such data and knowledge extraction endeavours must progress beyond individual sections of text, encompassing tables, figures and data dispersed throughout the full article. Each of these elements presents unique challenges. Extracting information from the full text is already intricate as relevant data may be dispersed across paragraphs, necessitating substantial advancements in relation extraction methods. Leveraging large language models such as GPT and LlaMa with tailored prompt engineering offers a promising avenue. Recognizing polymer chemical structure images and transforming them into polymer SMILES strings255 will also be important and may benefit from advances in molecular image recognition and SMILES conversion25,255. The ultimate aspiration and imperative are to establish an autonomous pipeline commencing from published literature and patents, culminating in the extracted material property information.",
+        "category": " Introduction"
+    },
+    {
+        "id": 37,
+        "chunk": "# Computational–experimental data fusion and multifidelity learning  \n\nIn polymer informatics, an important yet underexplored opportunity lies in harnessing simulation data to construct predictive ML models. Intriguingly, the initial publicly accessible models in Polymer Genome were trained on data generated using DFT. However, challenges in producing DFT-based data for essential properties such as glass transition temperature, gas permeabilities and ionic conductivities prompted a shift towards using measured data for the model development. This approach has reached its limits, given the reliance on databases and handbooks with limited content, the struggle to capture the expanding literature data (notwithstanding the advent of NLP approaches) and the inherent limitations of physical experiments in sampling the vast chemical space.  \n\nTraditionally, the prevailing wisdom cautioned against relying solely on computer simulation data owing to certain perceived concerns. Although DFT computations are accurate, they are computationally expensive, impractical for realistic length scales and timescales, and cannot access properties of practical importance using current computational resources. Classical force fields or potentials can circumvent these challenges, but their reliability and quantitative nature are often questionable. A gap exists not only between available computational options but also between computational and experimental avenues.  \n\nEnter multifidelity or multitask learning (MTL) approaches, poised to bridge this gap. Considering two data channels, one reliable but sparse (for example, physical measurements) and the other less trustworthy but correlated to the former (for example, classical simulations of related properties), MTL approaches leverage both channels, learning correlations and predicting at the higher fidelity level while generalizing at the lower fidelity but more diverse level. Numerous success stories in this domain already exist34,256–258.  \n\nThe past decade witnessed the proliferation of DFT-based materials databases, such as Materials Project259, aflowlib260, OQMD261 and NOMAD262,263, but exclusively for inorganic materials. Computational data for polymers54,264 are limited, but we expect them to grow considerably. Extant datasets are summarized in Table 1. The anticipation for the next decade is a swift emergence of polymer databases covering DFT",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 38,
+        "chunk": "# Review article  \n\nand classical force-field-based data for a myriad of polymer properties, in addition to data from physical experiments; polyVERSE (briefly described in Table 1) is an initial step to alleviate this burden. Widespread availability of such databases enables computational dataset(s) to be fused with measurement datasets, to cover chemical spaces at previously unimaginable scales. MTL approaches that exploit an amalgamation of computational and experimentally measured data are expected to give rise to a new breed of predictive models.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 39,
+        "chunk": "# Physics-enforced deep learning  \n\nAlthough data-driven approaches have substantially advanced materials discovery, the extensive reservoir of knowledge, experience, intuition, heuristics, phenomenological understanding and established relationships — collectively termed ‘known physics’ — within the domains of materials and chemistry cannot be disregarded. Integrating or imposing such known principles into ML models enhances their predictive power and ensures adherence to physical laws, leading to improved generalizability of predictions and accurate representation of physical phenomena. Furthermore, integration of known physics can address the inherent data scarcity issues prevalent in materials research.  \n\nIllustrative instances of incorporating known physics into ML models are discussed in the ‘Membranes for gas separation’ section, in which the gas permeability is elucidated as the product of gas solubility and diffusivity, and in the ‘Membranes for organic liquid mixture separations’ section, in which the organic molecule diffusivity through a polymer is conditioned on the molecular volume. The established Arrhenius relationship between ionic conductivity and temperature has also been leveraged to generate reliable predictions of lithium-ion conductivity in polymers143, despite limited coverage in the conductivity dataset of polymer and lithium salt chemical spaces.  \n\nIn practice, established equations are embedded within the loss function of neural network architectures, penalizing predictions that deviate from these principles. Physics-enforced neural networks represent a promising avenue to mitigate data scarcity, enhance generalizability and produce inherently interpretable predictive models265–268.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 40,
+        "chunk": "# Outlook  \n\nThrough compelling use cases, we have explored the transformative impact of AI methods and informatics on accelerating polymer discovery across diverse applications, including energy-storage materials, separation membranes and sustainable materials. Several challenges must be addressed. To continuously improve intelligence, relevant high-fidelity and low-fidelity data must be captured or generated in a consistent, systematic and (re)usable manner; NLP and image analytics methods, alongside physics-driven and ML-accelerated computer simulation techniques, will be key to accumulating such data. To maximize impact, it is imperative to foster technologically relevant use cases beyond academic laboratories.  \n\nAs AI-based materials intelligence ecosystems mature and evolve, they will enhance the capabilities of human researchers, driving efficiencies, accelerating discoveries and enhancing productivity. 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+        "category": " Results and discussion"
+    },
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+        "id": 45,
+        "chunk": "# Acknowledgements  \n\nThe authors acknowledge support from several grants from the Office of Naval Research, the National Science Foundation and Toyota Research Institute, and a grant from the Department of Energy via the Center for Understanding and Controlling Accelerated and Gradual Evolution of Materials for Energy (UNCAGE-ME), an Energy Frontier Research Center under award no. DE-SC0012577.",
+        "category": " References"
+    },
+    {
+        "id": 46,
+        "chunk": "# Author contributions  \n\nR.R. conceived and outlined the general manuscript. H.T. and R.R. wrote the initial manuscript with contributions from R.G., C.K., G.P., H.-K.K. and R.P.L. All authors edited the manuscript and figures and approved the final version for submission.",
+        "category": " References"
+    },
+    {
+        "id": 47,
+        "chunk": "# Competing interests  \n\nThe authors declare no competing interests.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 48,
+        "chunk": "# Additional information  \n\nPeer review information Nature Reviews Materials thanks the anonymous reviewers for their contribution to the peer review of this work.  \n\nPublisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.  \n\nSpringer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author selfarchiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.  \n\n$\\circledcirc$ Springer Nature Limited 2024",
+        "category": " References"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/╚╦╣д╓╟─▄╕и╓·╨┬╗п╤з╞╖╔ш╝╞╩╙╜╟.json b/task2/task2-chunks/╚╦╣д╓╟─▄╕и╓·╨┬╗п╤з╞╖╔ш╝╞╩╙╜╟.json
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@@ -0,0 +1,12 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Artificial intelligence-assisted design of new chemical materials: a perspective  \n\nFeng QIAN $^*$ , Wenli DU, Weimin ZHONG, Yang TANG & Jingyi LU  \n\nKey Laboratory of Smart Manufacturing in Energy Chemical Process, Ministry of Education, East China University of Science and Technology, Shanghai 200237, China  \n\nReceived 17 October 2023/Accepted 17 November 2023/Published online 19 July 2024  \n\nNew chemical materials are a fresh category of substances created through chemical reactions or by refining existing materials through secondary processes. By using creative methods, advanced technologies, innovative techniques, and state-of-the-art equipment, these materials (e.g., high-end polyolefin, nano materials) [1] are carefully designed and developed to showcase outstanding performance and unique capabilities beyond what traditional chemical materials can offer [2]. They possess characteristics such as light weight, impressive functionalities, strong performance, and high technological value. These materials serve as the building blocks of advanced foundational materials, hold significant strategic importance, and represent the forefront of cutting-edge innovations in materials science. Nevertheless, the progress in researching and developing new chemical materials frequently falls behind, resulting in a delay in meeting the demands of various applications [3]. It is crucial to establish a novel design paradigm for new chemical materials and even other fields that can bring about a transformation in the methods of researching and producing new materials for practical usage [4, 5].  \n\nUp to now, materials science research has undergone four paradigms: empirical, theoretical, computational, and data-driven, as illustrated in Figure 1(a) [6]. The first paradigm (empirical science) relies on trial-and-error experiments drawing from researchers’ accumulated experience, while suffering from low efficiency and resource-intensive processes. The second paradigm (theoretical science) involves creating scientific laws and theories based on past experiences, providing a theoretical basis to improve trial-anderror methods, however, it may oversimplify complex material systems. The third paradigm (computational science) uses computer simulations of atomic or molecular interactions, to understand macroscopic properties, but requires significant computational resources. The fourth paradigm (data-driven science) entails intelligent analysis of extensive data using algorithms to reveal hidden connections between data points. At present, the primary method for developing new chemical materials continues to be empirical or theoretical trial-and-error approaches, demanding ongoing experimentation and repetitive trials to navigate vast chemical structures [3].  \n\nIn sharp contrast, the fourth paradigm, anchored in data-driven methods and synergized with the earlier three paradigms, revolves prominently around the fusion of theoretical calculations, database technologies, and, most notably, artificial intelligence (AI), all in tandem with traditional experiments. AI empowers the analysis of the vast data, uncovering complex patterns and relationships that might elude human perception alone, and it has been widely applied in various fields (e.g., autonomous vehicles, industrial manufacturing) [7–9]. The ultimate objective of applying AI is twofold: to expedite the pace of new material discovery and to significantly trim the expenditures entailed in research endeavors. By enabling AI in the entire life cycle of new chemical material design, the transformation of the research and development paradigm for new materials is achieved through optimal structural design for product performance; the functionality and performance of new material products are enhanced through building a regulatory mechanism for consistent product quality and the maximization of the high-end value chain in the industrial ecosystem is ensured through developing comprehensive quality-benefit optimization decision solutions [10]. AI-assisted design propels the metamorphosis of new chemical materials, realizing intelligent digitization in design, elevating it to a high-end and high-value paradigm, and achieving green and low-carbon transformation. This endeavor inherently aligns with the concepts of digital transformation, the digital economy, and the industrial metaverse [11].  \n\nIn addition, human knowledge and other social elements are now integral throughout the entire life cycle of the AIassisted design for new chemical materials [12]. These factors have become crucial and can even play a decisive role at every stage of real-world process industries. The interactions between cyber-physical-social system (CPSS) and these societal factors are illustrated in Figure 1(a), and we also demonstrate a simple development cycle for new chemical materials with AI in CPSS.  \n\nCPSSs [13–15] will carry out parallel execution and selfsynchronization, and influence the physical, information, cognitive, and social domains. Technically, CPSSs can excavate the inner principles of technology from the micro level and form the overall structure of designing new chemical materials from the macro level. Leveraging human knowledge [16] across design, production, and management, alongside knowledge-based automation technology, holds the promise of driving smart manufacturing and informed decision-making.  \n\n![](images/731e511e73a1337956470d69290981908a91347fbdf98ea7813e10dff8ba5088.jpg)  \nFigure 1 (Color online) (a) Four paradigms for material design and overview of AI-assisted material design with cyber-physicalsocial system (left). To accelerate the process of developing new chemical materials, it is urgent to apply AI-based technology in data-driven science to realize intelligent design in the entire cycle of material design. Here, we show a simple demonstration for new chemical material with an AI-assisted design framework (right). (b) Main process of designing new chemical materials, including the phases of design, manufacturing, and usage. Human knowledge is fully utilized to accelerate the entire process.  \n\nIn this study, we design an entire circle for designing new chemical materials in CPSS, shown in Figure 1(b), including the phase of design, manufacture, and usage. For design, high-throughout techniques provide a large amount of cyber data to learn potential structure-activity relationships assisted with AI techniques, e.g., machine learning, deep learning, and reinforcement learning. Then, all suboptimal candidates are filtered out for physical production, and according to product performance and human guidance, the model is further optimized to search for better process parameters when engineering amplification. For manufacturing, human supervision is integrated with quality cyber characterization and detection to ensure safety, stability, and quality consistency for physical devices to adjust corresponding process parameters. For usage, with production iteration, new products will generate positive economic effects and boost the development of various fields, including electronics, medical, and the environment. To understand the thought patterns related to the proposed CPSS framework for designing new chemical materials, we conclude the following challenging research topics for the near future.  \n\n(1) Visualization and digitization: Designing cuttingedge simulations enables precise 3D modeling of molecular structures, allowing researchers to visualize intricate details. Applying virtual reality and metaverse technologies offers immersive experiences, aiding in the comprehension of complex molecular arrangements in materials. Efficient visualization and digitization-driven approach facilitate tailored materials design with enhanced accuracy and efficiency, forming a core pillar of the multidisciplinary process.  \n\n(2) Industrial intelligence: To build reliable industrial intelligence, sophisticated AI-based algorithms, multi-source data acquisition mechanism, few-shot learning, domainspecific large models fine-tuned by existing models or trained from scratch (e.g., polyBERT [16], ChatGPT [17]) should be developed for accurate property predictions and dynamic processes optimization. Assurance mechanisms should also be considered for real-time adjustments to ensure reliability and safety. This intelligent integration of information and physical processes enhances efficiency and innovation.  \n\n(3) Privacy protection: The concern for data privacy is quite common in the age of AI; thus blockchain and federated learning technologies can be further considered to create secure, decentralized data sharing mechanisms for collaborative research. This ensures that researchers collectively harness the power of data without compromising sensitive information, fostering trust and cooperation.  \n\n(4) Industrial software: To enhance the universality of the technology, integrated industrial software should be developed, realizing the functions discussed above. In addition, the journey from small-scale platforms or software to pilot testing and eventually scaling up to an enterprise level is a critical application transformation process to be considered.  \n\nIn this study, a vision for designing new chemical materials towards a CPSS future is presented by fully incorporating human intelligence into existing traditional cyber and physical manufacturing systems. In the pursuit of future AIassisted new chemical material design under full life circle, metaverse takes on a significant role. Imagine a collaborative virtual environment where researchers, engineers, and AI agents coexist seamlessly. This digital realm allows for real-time interactions, data sharing, and joint exploration of novel structures of new materials. Furthermore, blockchain technologies should be considered to protect the data privacy for fair distribution of credit and resources among collaborators. In addition, the visualization of material design is essential, and this capability enhances interdisciplinary communication and accelerates the convergence of diverse perspectives toward optimal material outcomes. To realize industrial intelligence, industrial large-scale models and multi-modal intelligence should be further researched, in the form of industrial software in the final. We hope that this perspective will help shape the thinking of the next generation of AI-assisted design pattern for new chemical materials.  \n\nAcknowledgements This work was supported by National Natural Science Foundation of China (Grant Nos. 61988101, 62394345), Shanghai Committee of Science and Technology, China (Grant No. 22DZ1101500), Fundamental Research Funds for the Central Universities (Grant No. 222202417006), and  \n\nShanghai AI Lab.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# References  \n\n1 Kumar S, Wang Z, Zhang W, et al. Optically active nanomaterials and its biosensing applications—a review. Biosensors, 2023, 13: 85 2 Zheng Z P, Huang Y J, Wu F, et al. Multidimensional modulation of light fields via a combination of two-dimensional materials and meta-structures. Sci China Inf Sci, 2023, 66: 160403   \n3 Cheetham A K, Seshadri R, Wudl F. Chemical synthesis and materials discovery. Nat Synth, 2022, 1: 514–520 4 Law K L, Narayan R. Reducing environmental plastic pollution by designing polymer materials for managed end-oflife. Nat Rev Mater, 2022, 7: 104–116 5 Wang C, Liang J, Kim J T, et al. Prospects of halide-based all-solid-state batteries: From material design to practical application. Sci Adv, 2022, 8: eadc9516 6 Agrawal A, Choudhary A. Perspective: materials informatics and big data: Realization of the “fourth paradigm” of science in materials science. APL Mater, 2016, 4: 053208 7 Zhu G X, Lyu Z H, Jiao X, et al. Pushing AI to wireless network edge: an overview on integrated sensing, communication, and computation towards 6G. Sci China Inf Sci, 2023, 66: 130301 8 Zhang B, Zhu J, Su H. Toward the third generation artificial intelligence. Sci China Inf Sci, 2023, 66: 121101 9 Zhang Y, Carballo A, Yang H, et al. Perception and sensing for autonomous vehicles under adverse weather conditions: a survey. ISPRS J Photogrammetry Remote Sens, 2023, 196: 146–177   \n10 Wang H, Fu T, Du Y, et al. Scientific discovery in the age of artificial intelligence. Nature, 2023, 620: 47–60   \n11 Qian F. The future of smart process manufacturing. Engineering, 2023, 22: 20–22   \n12 Qian F, Tang Y, Yu X. The future of process industry: a cyber-physical-social system perspective. IEEE Trans Cybern, 2024, 54: 3878–3889   \n13 Liu L, Zhao X D, Wang B H, et al. Event-triggered state estimation for cyber-physical systems with partially observed injection attacks. Sci China Inf Sci, 2023, 66: 169202   \n14 Sun Q, Chen J C, Shi Y. Event-triggered robust MPC of nonlinear cyber-physical systems against DoS attacks. Sci China Inf Sci, 2022, 65: 110202   \n15 Wang X, Cheng X, Lu J, et al. Metaverses-based parallel oil fields in CPSS: a framework and methodology. IEEE Trans Syst Man Cybern Syst, 2023, 53: 2138–2147   \n16 Kuenneth C, Ramprasad R. polyBERT: a chemical language model to enable fully machine-driven ultrafast polymer informatics. Nat Commun, 2023, 14: 4099   \n17 Fu N, Wei L, Song Y, et al. Material transformers: deep learning language models for generative materials design. Mach Learn-Sci Technol, 2023, 4: 015001",
+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,12 @@
+[
+    {
+        "id": 1,
+        "chunk": "Editorial",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# AI in Chemical Engineering: A New Chapter of Innovation  \n\nQilong Ren a,b  \n\na Key Laboratory of Biomass Chemical Engineering of the Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China b Institute of Zhejiang University–Quzhou, Quzhou 324000, China  \n\n![](images/5f05cf41f968025af9620bed16bb2901a9eb4b368fb4066e1177a54b5cde6e6b.jpg)  \n\nThe integration of artificial intelligence (AI) into chemical engineering marks a transformative era, redefining traditional methodologies with AI-driven approaches. AI has emerged as a powerful ally in tackling complex problems once considered insurmountable. As chemical engineering grapples with increasingly complex systems and stringent sustainability targets, AI sets the stage for a new generation of solutions.  \n\nAI applications in chemical engineering rely on three primary mechanisms: data-driven modeling, knowledge-based systems, and hybrid approaches that combine both. Often, data-driven models dominate, leveraging machine learning algorithms to extract patterns and insights from large datasets. In contrast, knowledge-based systems incorporate domain expertise and first-principles understanding to guide AI decision-making. Some applications require a synergistic combination of both approaches, necessitating the careful integration of data-driven and knowledge-based methodologies. To address these challenges and explore innovative solutions, experts worldwide have been invited to contribute articles on this topic.  \n\nMesoscience, a field pioneered by Jinghai Li and others, seeks to bridge the macroscopic and microscopic scales by focusing on mesoscale problems at various system levels. It addresses the common challenges in different disciplinary fields by analyzing the competition between dominant mechanisms within complex systems. Integrating mesoscience with AI has proven to be a promising approach to modeling complex systems effectively. The research group led by Li Guo has proposed and demonstrated the use of mesoscience-guided deep learning (MGDL) for modeling complex chemical systems. By integrating physical principles and mesoscopic insights into deep learning architectures, they have significantly improved model accuracy and interpretability. Their work demonstrates AI’s potential to bridge the gap between empirical data and theoretical understanding, enhancing the predictive capabilities of models in multiphase systems.  \n\nIn chemical engineering and materials science, accurately predicting pure component properties is foundational to designing and optimizing chemical processes and developing novel materials. Historically, these properties have been estimated using empirical methods such as group contribution approaches, which rely on the additive contributions of molecular fragments to predict properties such as boiling points, vapor pressures, and solubilities. However, these methods can suffer from limitations in accuracy, especially with complex molecules for which the interactions between functional groups are non-additive. Focusing on estimating pure component properties, Xi Chen and coworkers have developed an enhanced machine learning framework that leverages group contribution methods and Gaussian processes. By mapping discrete molecular structures into a continuous domain, their model improves the representation of complex molecular interactions, leading to more accurate predictions of physicochemical properties.  \n\nIn the pursuit of sustainable chemistry and engineering, the development of novel solvents plays a critical role in advancing green processes and reducing environmental impact. Among the most promising innovations in this field are deep eutectic solvents (DESs). However, the rational design of DESs has been impeded by the lack of predictive models capable of accurately identifying suitable combinations of components and predicting the resulting properties of the solvent mixture. Qing Shao and his team address the challenge of discovering new DESs by employing machine learning models that identify unique hydrogen bond features. Their work has led to the development of 30 models using various algorithms, significantly advancing the rational design of non-ionic designer solvents.  \n\nPorous media are integral to many environmental and energy systems, where accurately predicting reactive transport is crucial. Traditional modeling approaches struggle with the complexity of such environments, often failing to adequately represent the heterogeneous nature of porous materials. The group led by Cheng Lian and Honglai Liu introduces Porous-DeepONet, an AI model that solves parametric reactive transport equations in porous media. By incorporating convolutional neural networks, they enhance the model’s ability to capture the intricate features of porous media, enabling accurate predictions of reactive transport phenomena.  \n\nModeling dynamic chemical processes is essential in optimizing operations and ensuring safety. Traditional models often rely on first-principles equations, which can be complex and computationally expensive. The advent of machine learning—particularly deep learning techniques—has introduced more efficient and accurate ways to model these processes. Weifeng Shen’s group has developed the light attention–convolution–gate recurrent unit (LACG) architecture for chemical process modeling. This architecture, which combines convolutional and recurrent neural networks with a light attention mechanism, demonstrates superior performance in modeling dynamic chemical processes.  \n\nDiscovering and developing new materials has traditionally relied heavily on rational design approaches, which involve a meticulous understanding of material properties and their underlying atomic structures. However, the inherent limitations of this method, which include its time-consuming nature and the difficulty of exploring vast chemical spaces, have spurred a shift toward more agile and efficient techniques. In this context, Jianjun Hu and coworkers explore the use of generative AI for materials discovery. By moving beyond traditional rational design approaches, they advocate for a data-driven strategy that can rapidly identify novel materials with exceptional properties. A review article from Xinyan Liu’s group highlights the role of machine learning in accelerating the discovery of heterogeneous catalysts. The review underscores the potential of AI in predicting surface reactivity with lower computational costs, offering a roadmap for the rational design of catalysts.  \n\nAs AI continues to permeate various sectors of chemical engineering, the demand for transparent and accountable AI systems grows. AI models are increasingly employed for process optimization, materials discovery, and predictive maintenance. However, the complexity of these models often leads to a ‘‘black box” effect, in which the decision-making processes remain opaque to users. A review from Jesse Zhu’s group focuses on the concept of transparency in AI applications within chemical engineering. By emphasizing the importance of causality, explainability, and informativeness, the researchers advocate for responsible AI utilization. Their review showcases state-of-the-art applications that combine physical principles with AI, promoting a hybrid modeling approach that enhances the reliability and interpretability of AI models in chemical engineering.  \n\nWhile the potential of AI in chemical engineering is immense, several challenges remain, including the scarcity of high-quality data, the need for robust validation metrics, and the integration of AI with existing engineering practices. Moreover, ensuring the interpretability and transparency of AI models is imperative for building trust and facilitating the widespread adoption of such models in industry.  \n\nDespite these challenges, the future of AI in chemical engineering is promising, with ongoing advancements in AI techniques and increasing collaborations between academia and industry. The integration of AI into chemical engineering is set to redefine how we approach complex problems in our field. From enhanced materials discovery to process optimization, AI is poised to deliver significant advancements. We anticipate the development of more sophisticated AI models that can handle multimodal data, integrate domain knowledge, and provide real-time process optimization. The emergence of AI-driven design platforms and digital twins will greatly facilitate predictive maintenance, process optimization, and sustainable chemical production. Let us embrace this exciting journey as we harness the power of AI to drive innovation and excellence in chemical engineering.",
+        "category": " Introduction"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# 人工智能在血液疾病诊疗中的应用研究进展  \n\n张礼潜1, 安倬玉1, 崔丽娟2, 李文倩3, 张晓辉1\\*  \n\n1. 北京大学人民医院, 北京大学血液病研究所, 国家血液系统疾病临床医学研究中心, 血液肿瘤细胞和基因治疗北京市重点实验室, 北京  \n100044  \n2. 宁夏医科大学总医院血液科, 银川 750003  \n3. 青海省人民医院血液风湿科, 西宁 810007  \n\\* 联系人, E-mail: zhangxh@bjmu.edu.cn  \n\n2024-11-05 收稿, 2025-02-09 修回, 2025-02-10 接受国家重点研发计划(2023YFC2507803)、国家自然科学基金(82230004, 82430006)、首都卫生发展科研专项(2022-1-4082)资助摘要 血液疾病指原发于造血系统或主要累及血液和造血器官的疾病, 主要包括良性血液疾病和恶性血液疾病两种类型, 不仅对患者的生活质量和生命安全造成负面影响, 也给家庭和社会带来了沉重的负担. 随着计算机与机器学习等相关技术的快速发展, 人工智能已被广泛应用于医学领域和临床研究. 在血液疾病诊疗方面, 基于随机森林、决策树、支持向量机和线性回归等机器学习算法构建的人工智能模型展现出了卓越的工作效能, 在合理利用既有数据、图像识别和组学分析等任务中取得了优于传统方法的表现. 本文综述了人工智能应用于血液疾病预测、诊断、预后评估与治疗指导领域的研究进展, 总结了人工智能技术在该领域的突出成果与局限性, 以期为推动机器学习技术进一步应用于血液疾病诊疗提供参考.  \n\n关键词 血液疾病, 人工智能, 机器学习, 临床诊疗  \n\n血液疾病是指原发于造血系统或影响造血系统伴发血液异常改变的疾病. 常见的血液疾病包括贫血、免疫性血小板减少症等良性血液疾病和包括白血病(leukemia)、淋巴瘤与多发性骨髓瘤(multiple myeloma,MM)等在内的恶性血液疾病[1], 不同血液疾病的患病率与预后情况不尽相同[2]. 流行病学调查显示, 仅在2022年, 我国新增血液系统肿瘤患者逾21万人, 直接因血液系统肿瘤死亡的人数也超过8000人[3]. 近年来, 非霍奇金淋巴瘤和MM等恶性疾病的发病率更是持续升高, 给患者造成了沉重的疾病负担[4]. 提高血液疾病的诊治水平是当前临床医学领域的重要命题之一.  \n\n人工智能(artificial intelligence, AI)是计算机科学的一门分支学科, 被定义为研究、开发用于模拟、延伸和扩展人的智能行为的理论、方法及技术等的一门综合性科学. 在过去十余年间, 人工智能技术得益于计算能力的增长和算法的迭代进步而蓬勃发展, 其与医学领域之间的联系也随之日趋紧密[5]. 绝大多数应用于医学研究领域的人工智能技术均属于机器学习(ma-chine learning, ML)范畴, 这使得二者的概念在医学领域常常发生混淆[6,7]. 机器学习被定义为计算机通过算法自主获取源数据中的核心信息并寻找最有效的途径来实现既定目标的过程[8], 包括监督学习、半监督学习、无监督学习等类型[9]. 在当前的血液疾病研究领域, 人工智能与机器学习技术已被广泛应用于多种疾病的预测、诊断、预后评估之中[6], 在数据处理、图像处理、遗传学数据分析和策略优化等任务中均取得了卓越表现.",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1 血液疾病临床诊疗视角下的人工智能  \n\n人工智能的概念最早由John McCarthy等提出, 并由Alan Turing进一步完善[7]. 人工智能技术可以被理解为一项经由模拟人类认知功能而使机器能够获得与人类相似的感知力、洞察力, 并做出相应判断和决策的技术[10]. 作为人工智能的一个子领域, 机器学习被定义为一种能够使机器实现从既有数据中自动学习并执行预测或决策任务的算法, 而非直接编程以完成目标[7,11]. 机器学习技术在处理复杂或非线性数据等方面具有突出优势, 这为其被应用于具有复杂数据集的临床医学科研领域提供了可能. 鉴于机器学习技术的广泛应用, 在有关血液疾病诊疗的临床语境下, 在血液疾病诊疗中, 人工智能与机器学习的概念常被交替使用[6,12]. 需要注意的是, 尽管机器学习是应用于临床领域的主要人工智能类型, 大语言模型和大数据分析等人工智能分支领域在血液疾病诊疗中的巨大应用潜力也不容忽视[13]. 大语言模型以对自然语言的概率分布进行建模为目标, 研究者们对其在智能问诊、辅助诊断、治疗决策等临床诊疗领域中的应用前景进行了广泛的探索. 尽管当前鲜有研究将大语言模型应用于血液疾病领域, 但Kumari等人[14]的工作也揭示了大语言模型在处理复杂血液疾病案例相关信息中的良好前景.大数据分析技术立足于对大规模数据集的分析与处理,已被充分应用于数据整合、数据标准化与数据分析等临床研究场景. 在血液疾病诊疗领域, 大数据分析技术为研究者们实现对多中心、多组学数据的有效整合与分析提供了有效工具[15]. 基于大数据分析技术, Me-deiros等人[16]通过整合全国范围内的信息对老年AML患者的预后情况进行了分析, Warnat-Herresthal等人[17]则依托于多组学数据构建了准确的急性粒细胞白血病(acute myeloid leukemia, AML)预测模型. 需要注意的是, 机器学习、大语言模型与大数据分析等人工智能技术在应用语境下并非孤立存在, 往往被联合使用以完成既定目标. 例如, 大语言模型的建模过程可能涉及机器学习的监督学习或无监督学习方法, 而经大数据分析技术整合后的数据也可以经由机器学习方法进一步完成临床预测模型的构建.  \n\n在血液疾病诊疗领域, 对机器学习的分类主要以学习方法的不同为导向. 常见的机器学习类型包括监督学习、半监督学习、无监督学习和强化学习等[9,12],不同的机器学习类型依托于不同类型的算法以实现,表1对常见的机器学习类型与算法进行了总结. 深度学习是另一种受到广泛关注的机器学习类型, 其与传统机器学习在结构模式上存在不同, 具体表现为对数据的特征与结构模式的学习建立在多层神经网络结构的基础上. 深度学习在学习数据中的深层次特征和非线性关系方面有着突出优势, 在高维数据处理、图像识别与分析等任务中取得了良好表现[5].  \n\n应用于血液疾病诊疗场景中的机器学习工作流程包括数据收集和预处理、算法选择与建模、模型训练、模型评估与优化以及临床应用几项内容[7,18]. 数据收集是机器学习技术应用于优化血液疾病诊疗方法的前提; 研究者可能选用的算法模型与所研究的血液疾病问题共同决定了一项研究中对数据预处理的要求,既包括以恰当的方法处理原始数据中的缺失或异常数据, 也包含特征选择——即识别并选择对解决目标问题贡献较大的变量; 对算法的选择与以此为基础的模型构建直接决定了机器学习技术实现既定目标的路径;在完成建模后, 数据集往往被分为训练集和测试集, 由训练集得到的模型随后在测试集中接受验证和评估,并根据评估结果被加以校准; 此外, 经由上述过程构建出的人工智能模型还需要经过对模型的诠释、评估不确定性以及开放访问途径等步骤, 从而最终应用于血液疾病诊疗工作[7,12].  \n\n表 1 机器学习分类、代表算法及应用场景 Table 1 Classification, representative algorithms, and application scenarios of machine learning   \n\n\n<html><body><table><tr><td>分类</td><td>主要功能</td><td>代表算法</td><td>应用场景</td></tr><tr><td rowspan=\"3\">监督学习</td><td rowspan=\"3\">训练模型根据输入数据特征预测输出标 签，常用于解决分类与回归问题</td><td>随机森林</td><td>可用于解决分类问题和回归问题、处理大规模数据 集等</td></tr><tr><td>决策树</td><td>可用于解决分类问题和回归问题等</td></tr><tr><td>支持向量机</td><td>可用于解决二分类问题、小样本问题和回归问题等</td></tr><tr><td rowspan=\"2\">半监督学习</td><td rowspan=\"2\">使用包含已标记和未标记数据的数据集进 行模型训练，常用于文本分类、图像识别 等领域</td><td>自训练</td><td>可用于图像识别、异常检测等 可用于解决分类问题和回归问题、图像识别和</td></tr><tr><td>半监督支持向量机</td><td>异常检测等</td></tr><tr><td>非监督学习</td><td>训练模型探索数据的内在结构和模式，常 用于解决聚类、降维、异常检测问题</td><td>K-均值聚类 谱聚类</td><td>可用于图像处理、生信分析等 可用于图像处理、文本挖掘、生信分析等</td></tr><tr><td rowspan=\"2\">强化学习</td><td rowspan=\"2\">在与环境的交互中进行模型训练，常用于 机器人控制等交互领域</td><td>Deep Q-Network</td><td>可用于图像处理等</td></tr><tr><td>Deep Deterministic Policy Gradient</td><td>可用于策略优化等</td></tr></table></body></html>  \n\n基于上述工作流程, 应用于血液疾病诊疗领域的人工智能和机器学习技术在对血液疾病的预测、诊断、风险分层和预后评估等方向都取得了出色表现.在不同的具体任务类型中, 人工智能也展现出了优于传统方法的效能: 依托于深度学习和大数据分析等技术, 人工智能方法能够更加合理和充分地利用现有的血液疾病相关数据, 为研究者和临床医生提供更多的指导信息; 人工智能所具有的快速、准确识别图像信息能力和良好的特征提取能力等特点为满足血液疾病临床研究中病理图像处理的需求开辟了新路径; 在组学数据分析方面, 人工智能卓越的数据整合能力也为高效处理高维多组学数据、提高聚类精度和降低计算成本提供了可能[19]. 图1对人工智能技术应用于血液疾病诊疗的基本范式进行了概括.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2 人工智能在血液疾病预测中的应用  \n\n预测特定人群中血液疾病发生的可能性可以为血液疾病尤其是恶性血液疾病的早期诊断与提供支持,从而帮助临床医生及早干预并改善患者的预后结局.在血液疾病预测领域, 人工智能已被成功应用于评估部分疾病与并发症的发生风险. 在白血病复发预测的研究中, Pan等人[20]应用随机森林(random forest, RF)、决策树(decision tree, DT)、支持向量机(support vectormachine, SVM)和线性回归(linear regression)4种分类算法构建了急性淋巴细胞白血病(acute lymphocytic leu-kemia, ALL)的复发预测模型, 而Hauser等人[21]则应用其他机器学习算法探索了基于全血细胞计数对慢性粒细胞白血病(chronic myeloid leukemia, CML)进行预测的可能性, 二者所得到的模型分别表现出了高达0.92和0.90的优异曲线下面积(area under the curve, AUC). 一些研究者对造血干细胞移植(hematopoietic stem celltransplantation, HSCT)后的白血病复发预测模型进行了深入研究, Fuse等人[22]应用交替决策树(alternatingdecision tree, ADTree)算法建立起了移植后一年内的急性白血病复发预测模型, 该模型被认为具有良好的通用性与可解释性; Zhang等人[23]则将自动图像分析检测技术应用于预测AML患者的HSCT后复发, 该团队利用深度学习方法对39例AML患者的骨髓细胞涂片进行了图像处理, 进而使用特征选择算法基于骨髓细胞的形状和纹理特征形成了预测模型的顶部特征, 最终应用RF等算法构建了能够有效预测AML患者移植后复发的模型.  \n\n关于人工智能技术应用于其他血液肿瘤预测的研究也取得了一些进展. Goswami等人[24]采用由谱聚类和快速节俭树算法组成的堆叠机器模型对MM患者自体HSCT后36个月的复发进行了预测, 并提出了一个可应用于指导临床诊疗实践的分期方案. Radhachandran等人[25]利用机器学习技术建立了优化的极限梯度提升(xtreme gradient boosting, XGB)模型以实现诊断前预测骨髓异常增生综合征(myelodysplastic syndrome), 该模型高达0.87的AUC显著优于传统算法. 也有研究者关注到了HSCT术后并发症预测领域的相对空白. Arai等人[26]应用ADTree算法在HSCT治疗后患者人群中建构了基于机器学习的急性移植物抗宿主病(acute graftversus-host disease, aGVHD)预测模型, 并在验证队列中确认了所得到模型的可靠性; 有赖于机器学习方法,能够有效预测HSCT后静脉血栓栓塞和aGVHD发生及患者生存率的临床预测模型得以成为现实[27,28]; Fan等人[29]完成的用于预测HSCT后应用抗胸腺细胞球蛋白预防GVHD人群EB病毒(Epstein-Barr virus)再感染的综合机器学习模型也是这一研究方向上的成功案例.Musiał等人[30]则将机器学习算法与肾小管损伤标志物相结合, 提出了新的儿童HSCT后急性肾损伤预测模型,拓展了移植后急性肾损伤的预测路径.  \n\n人工智能技术同样被成功应用于对良性血液疾病的预测. Jardim等人[31]探索了人工智能用于预测A型血友病患者发生凝血因子抑制物生成这一并发症的可能性, 尽管所得模型仍有待进一步验证, 但也体现了研究者所采用的基于网络的机器学习算法的潜力. Saputra等人[32]应用人工智能技术以解决不同贫血类型难以快速区分的难题, 构建起了基于极限学习机(extremelearning machine)算法的贫血预测与分类模型; Gardu-no-Rapp等人[33]使用深度学习技术方法构建了多种神经网络模型, 经对比得到了能够对缺铁性贫血进行早期预测的门控循; 环单元模型; Schipper等人[34]则利用血常规参数分别构建了AUC高达0.88和0.84的XGB与逻辑回归模型, 提供了有效预测和区分地中海贫血与缺铁性贫血的方法.  \n\n![](images/d0ee9642d87c781a67018338f53b95674c6d89adb2ac7c55dd2421d1749ba933.jpg)  \n图 1 人工智能赋能血液疾病诊疗 Figure 1 Diagnostic and therapeutic models for hematologic diseases empowered by artificial intelligence",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# 3 人工智能在血液疾病诊断中的应用  \n\n对血液疾病的准确诊断是疾病诊疗过程中的重要环节, 是实现血液疾病早期治疗的重要前提, 不仅有利于改善患者预后, 还可以减轻家庭与社会的疾病负担.人工智能赋能的新诊断方法已在各项临床试验中取得了良好反馈, 在白血病领域更是取得了突出的进展. 不同研究者基于不同的临床检测项目数据利用人工智能技术构建了白血病诊断工具. Alcazer等人[35]依托于多中心数据库, 将包括血常规、血生化和凝血指标在内的共计19项常见临床实验室检测指标纳入模型中, 建立起了能够对ALL和AML等急性白血病亚型进行准确诊断的急性白血病人工智能预测模型. Haider等人[36]回顾性纳入了1577例血液肿瘤患者的血常规数据, 采用径向基函数网络(radial basis function network)架构对数据集中的不同血液恶性肿瘤进行分类诊断建模,得到了AUC高达0.905的、能够有效区分和诊断包括慢性淋巴细胞白血病(chronic lymphocytic leukemia,  \n\nCLL)在内的多种白血病亚型及其他恶性血液疾病的机器学习诊断模型. EI Alaoui等人[37]基于全血细胞计数比较了RF、XGB和DT算法所得到的模型性能, 发现基于DT算法构建的模型对诊断ALL有高达 $91.4\\%$ 的准确率.  \n\n得益于人工智能在图像识别与信息提取方面的突出优势, 人工智能技术被广泛应用于基于血涂片或其他病理图像的白血病诊断领域. Mohammed及其团队[38]提出了一种能够根据血涂片图像将白细胞分类为CLL或正常细胞的系统, 该系统源自由SVM算法、k-最邻近( $\\mathbf{k}$ -nearest neighbors, KNN)算法和DT算法组成的融合模型. 该团队还将该系统的诊断效能与流式细胞术进行了对比并确认了二者的一致性. Steinbuss等人[39]也基于淋巴结组织病理学图像数据开展了应用深度学习技术构建CLL等疾病诊断模型的研究. 在病理图像之外, 人工智能技术同样被成功应用于依托流式细胞术或遗传学特征开展的白血病诊断之中. 既往综述对结合了聚类技术和机器学习的计算机驱动流式细胞术分析方法进行了总结, 指出了其有助于提高恶性血液疾病的诊断准确率[40]. 借助人工智能技术, 研究者们对患者的遗传学特征与白血病诊断之间的有机关联进行了发掘, 其中Warnat-Herresthal等人[17]的研究具有突出代表性. 该团队使用来自105个不同研究的12029例样本的基因组学和转录组学数据开展大规模研究,应用数据驱动的高维统计方法构建了基于机器学习与深度学习技术的AML诊断模型, 该模型在准确性高的同时兼具良好的可扩展性和低边际成本.  \n\n人工智能技术在其他血液疾病诊断中的应用也取得了长足的进展. Gutierrez-Rodrigues等人[41]使用25项在患者初诊时所记录的临床或实验室变量开发了获得或遗传性骨髓衰竭(bone marrow failure)的诊断模型, 从新视角出发强调了初始评估对于骨髓衰竭诊断的重要意义. Ramzan等人[42]将兼具注意力模块和空间注意力的综合机器学习模型创新性地应用于贫血诊断中, 所构建的AlexNet多重空间注意力模型具有高达 $99.58\\%$ 的诊断准确率. RF、SVM和KNN等机器学习算法均被应用于MM诊断领域, 并展现出了出色的诊断效能. 在HSCT后并发症领域, Sharifi等人[43]采用无监督方法对HSCT后肺部并发症的鉴别诊断进行了研究; Shao等人[44]则在检测microRNA的基础上应用RF算法建立起了能够高效诊断HSCT后感染性发热的人工智能模型,该模型表现出了超过 $90\\%$ 的诊断准确率.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# 4 人工智能在血液疾病预后评估与治疗指导中的应用  \n\n血液疾病尤其是血液恶性疾病的预后存在很大异质性, 及时且准确的危险分层与预后评估可以为临床干预提供有效指导, 帮助医生平衡治疗获益与可能的副反应或风险, 降低不良预后结局的发生可能. Chen等人[45]引入无监督聚类步骤以提供CLL人群的离散危险分层, 为更好地解释应用于血液疾病预后评估中的机器学习模型提供了可行的方法. Agius等人[46]采用恰当的预处理方式消减了数据集中缺失变量的影响, 并通过整合28种机器学习算法开发出了慢性淋巴细胞白血病(chronic lymphocytic leukemia, CLL)治疗-感染模型(CLL-TIM), 该模型在内部测试队列与独立的外部队列得到了验证, 并展现出优于现有CLL预后评估金标准的良好评估效能. Qin等人[47]着眼于AML发病机制中涉及的异常程序性细胞死亡机制, 开发了将遗传学数据与AML患者的临床预后及药物治疗反应相关联的机器学习模型. 在儿童白血病方面, 来自国内外的八项临床研究也揭示了RF和LASSO(least absolute shrinkageand selection operator)等机器学习算法应用在儿童急性白血病预后结局评估领域的良好前景[48].  \n\n以机器学习方法为代表的人工智能同样被广泛应用于评估白血病以外的血液疾病的预后情况. Farswan等人[49]结合常见的实验室检查参数构建了优于传统分期的MM改良分期系统, 其他研究团队也分别基于不同的遗传学数据使用机器学习模型实现了对MM患者的总生存期的准确预测和评估. 借助神经网络分析, 研究者们也构建起了患者的遗传信息和淋巴瘤等血液系统肿瘤的预后之间的联系[50]. Zhang及其团队[51]将机器学习技术应用于原发性免疫性血小板减少症(primary im-mune thrombocytopenia, ITP)患者的危重出血事件分析中, 并将基于多中心回顾性数据开发出的RF算法模型在国内的39个中心进行前瞻性验证, 提出了能够快速且准确识别ITP患者出血风险概况以提供临床决策指导的人工智能方法. 近期的一项研究也揭示了应用机器学习方法通过特定的凝血因子蛋白序列预测女性A型血友病患者预后的可能性[52].  \n\n人工智能技术在血液疾病预后评估中的应用也被拓展到多种治疗措施或方案的治疗反应预测领域, 智能模型对于疗效的准确评估在临床决策中意义重大.HSCT的预后评估是学者们关注的重点, 包括RF、随机生存森林(random survival forest)和SVM等算法均被成功应用于HSCT后患者的预后分析之中. 依托人工智能方法, Tislevoll等人[53]使用多维细胞计数技术对AML患者的生存结局进行了有效评估, 以Lee等人[54]为代表的多个团队则分别对血液肿瘤患者的基因表达情况与药物治疗反应间存在的联系进行了探索. Xu等人[55]也在ITP人群中利用机器学习算法建立了AUC高达高达0.964的疗效预测评分系统, 可用于指导ITP患者的个体化治疗. Rodríguez-Belenguer等人[56]于近期发表的工作聚焦于血液肿瘤患者接种新型冠状病毒疫苗后可能的低应答或无应答情况, 应用机器学习方法得到了准确且解释性良好的预后模型, 其相对新颖的研究方向具有借鉴意义.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 5 血液疾病诊疗中人工智能的局限性  \n\n尽管在应用层面已经取得了许多成果, 但血液疾病诊疗领域中的人工智能仍存在着一定的局限性. 首先, 人工智能系统的准确性高度依赖于原始数据集的质量, 这对原始数据集的完整性和可靠性提出了要求,而临床研究所得到的复杂或存在缺失的数据集可能对基于此进行的人工智能应用研究造成不利影响. 尽管如此, 借助在特征识别等领域相较传统方法有明显优势的机器学习方法, 人工智能技术不仅可能克服复杂的原始数据集限制, 还可能展现出优于既往统计方法的模型效能. 过小的样本量也可能损害机器学习模型的性能[13], 为机器学习与大数据分析技术在罕见病诊治或其他基于小规模数据库的研究中的应用造成了一定制约. 这对研究者们在技术层面提出了更高的要求,能否根据待解决的临床问题选取恰当的人工智能工具与算法类型, 可能直接决定了人工智能否成功应用于受到数据限制的血液疾病治疗场景中. 需要指出的是,尽管部分研究采用了多中心临床数据[35,52], 但大多数有关人工智能的血液疾病研究都是在来自单中心的数据基础上完成的, 这也削弱了所得到模型的外部适用性. 在预测模型拟合以外, 以大语言模型为代表的交互性人工智能技术还面临着输出幻觉、泛化等问题, 这些问题有赖于完善模型建构方法或优化评估指标等手  \n\n段加以解决[14].  \n\n其次, 来自伦理方面的挑战也是人工智能技术在应用于血液疾病的临床诊疗时必须面对的问题. 包括大语言模型和大数据分析在内的人工智能技术对医患关系的潜在影响、患者隐私泄露的风险、社会偏见在决策过程中被放大的可能性以及人工智能被用于牟取不当利益的风险等问题均需要经过审慎的伦理考量加以解决[57,58].  \n\n此外, 对人工智能模型的合理解释也是决定其临床应用价值的重要因素. 人机交互是人工智能技术走向应用的一项重要内容, 而许多模型对医生而言仍是黑箱状态, 这对人工智能系统应用于临床实践中产生了阻碍, 博弈论等方法乃至大语言模型技术的应用有望解决这一问题[59,60]. 人工智能工具所带来的人机交互需求也给临床医生提出了进一步的要求, 在掌握有关人工智能系统的基本知识基础上, 结合现有的临床指南、共识与自身经验依然是作出临床决策的关键.在对人工智能模型的评估方面, 传统的统计学评价指标如特异度和灵敏度可能存在局限性, 仍需要引入如精确度(真阳性数除以真阳性和假阳性数之和)等更加有效的评估指标以准确判定人工智能工具的效能[7].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 6 讨论与展望  \n\n人工智能技术的蓬勃发展推动了其在医学领域的应用日趋成熟, 并在血液疾病这一专科领域体现出推动传统诊疗范式发生转变的巨大潜能. 本文基于有关血液疾病诊疗的应用视角对人工智能进行了阐释,并回顾了人工智能在预测、诊断、危险分层和预后评估等血液疾病诊疗领域所取得的应用性进展, 强调了以机器学习为代表的人工智能技术在图像识别和高维数据处理等方面表现出的卓越性能, 也对大语言模型、大数据分析技术等人工智能技术的应用现状进行了总结. 尽管仍面临着原始数据的制约、伦理争论与人机交互障碍等挑战, 但人工智能已经展现出了良好的发展前景, 有望进一步应用于临床实践之中, 在实现科技赋能优化现有临床诊疗范式的同时改善患者预后结局.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
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Artificial intelligence in hematology: current challenges and opportunities. Curr Hematol Malig Rep, 2020, 15: 203–210   \n7 Radakovich N, Nagy M, Nazha A. Machine learning in haematological malignancies. Lancet Haematology, 2020, 7: e541–e550   \n8 Deo R C. Machine learning in medicine. Circulation, 2015, 132: 1920–1930 9 Yang J F, Qiao P R, Li Y, et al. A review of Machine-learning classification and algorithms (in Chinese). Stat Decis, 2019, 35: 36‒40 [杨剑锋, 乔佩 蕊, 李永梅, 等. 机器学习分类问题及算法研究综述. 统计与决策, 2019, 35: 36‒40]   \n10 An Z Y, Zhang X H. Embracing the age of artificial intelligence: paradigm shifts, opportunities, and challenges in the treatment of acute graftversus-host disease after allogeneic hematopoietic stem cell transplantation. Sci China Life Sci, 2024, 67: 1302–1304   \n11 Beam A L, Kohane I S. Big data and machine learning in health care. JAMA, 2018, 319: 1317–1318   \n12 Shouval R, Fein J A, Savani B, et al. Machine learning and artificial intelligence in haematology. 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Prediction of inhibitor development in previously untreated and minimally treated children with severe and moderately severe hemophilia A using a machine-learning network. J Thrombosis Haemostasis, 2024, 22: 2426–2437   \n32 Saputra D C E, Sunat K, Ratnaningsih T. A new artificial intelligence approach using extreme learning machine as the potentially effective model to predict and analyze the diagnosis of anemia. Healthcare, 2023, 11: 697   \n33 Garduno-Rapp N E, Ng Y S, Weon J L, et al. Early identification of patients at risk for iron-deficiency anemia using deep learning techniques. Am J Clin Pathol, 2024, 162: 243–251   \n34 Schipper A, Rutten M, van Gammeren A, et al. Machine learning-based prediction of hemoglobinopathies using complete blood count data. Clin Chem, 2024, 70: 1064–1075   \n35 Alcazer V, Le Meur G, Roccon M, et al. Evaluation of a machine-learning model based on laboratory parameters for the prediction of acute leukaemia subtypes: a multicentre model development and validation study in France. Lancet Digital Health, 2024, 6: e323–e333   \n36 Haider R Z, Ujjan I U, Khan N A, et al. Beyond the in-practice cbc: the research CBC parameters-driven machine learning predictive modeling for early differentiation among leukemias. Diagnostics, 2022, 12: 138   \n37 El Alaoui Y, Padmanabhan R, Elomri A, et al. An artificial intelligence-based diagnostic system for acute lymphoblastic leukemia detection. Stud Health Technol Inform, 2023, 305: 265‒268   \n38 Mohammed E A, Mohamed M M A, Naugler C, et al. Toward leveraging big value from data: chronic lymphocytic leukemia cell classification. Netw Model Anal Health Inform Bioinforma, 2017, 6: 6   \n39 Steinbuss G, Kriegsmann M, Zgorzelski C, et al. Deep learning for the classification of non-hodgkin lymphoma on histopathological images. Cancers, 2021, 13: 2419   \n40 Duetz C, Bachas C, Westers T M, et al. Computational analysis of flow cytometry data in hematological malignancies: Future clinical practice? Curr Opin Oncol, 2020, 32: 162–169   \n41 Gutierrez-Rodrigues F, Munger E, Ma X, et al. Differential diagnosis of bone marrow failure syndromes guided by machine learning. Blood, 2022, doi: 10.1182/blood.2022017518   \n42 Ramzan M, Sheng J, Saeed M U, et al. Revolutionizing anemia detection: integrative machine learning models and advanced attention mechanisms. Vis Comput Ind Biomed Art, 2024, 7: 18   \n43 Sharifi H, Lai Y K, Guo H, et al. Machine learning algorithms to differentiate among pulmonary complications after hematopoietic cell transplant. Chest, 2020, 158: 1090–1103   \n44 Shao W, Wang Y, Liu L, et al. Combining serum microRNAs and machine learning algorithms for diagnosing infectious fever after HSCT. Ann Hematol, 2024, 103: 2089–2102   \n45 Chen D, Goyal G, Go R S, et al. Improved interpretability of machine learning model using unsupervised clustering: predicting time to first treatment in chronic lymphocytic leukemia. JCO Clin Cancer Inf, 2019, 3: 1–11   \n46 Agius R, Brieghel C, Andersen M A, et al. Machine learning can identify newly diagnosed patients with CLL at high risk of infection. Nat Commun, 2020, 11: 363   \n47 Qin Y, Pu X, Hu D, et al. Machine learning-based biomarker screening for acute myeloid leukemia prognosis and therapy from diverse cell-death patterns. Sci Rep, 2024, 14: 17874   \n48 Gurumurthy G, Gurumurthy J, Gurumurthy S. Machine learning in paediatric haematological malignancies: A systematic review of prognosis, toxicity and treatment response models. Pediatr Res, 2024, doi: 10.1038/s41390-024-03494-9   \n49 Farswan A, Gupta A, Gupta R, et al. AI-supported modified risk staging for multiple myeloma cancer useful in real-world scenario. Transl Oncol, 2021, 14: 101157   \n50 Yuan J, Zhang Y, Wang X. Application of machine learning in the management of lymphoma: current practice and future prospects. Dig Health, 2024, 10: 20552076241247963   \n51 An Z Y, Wu Y J, Hou Y, et al. A life-threatening bleeding prediction model for immune thrombocytopenia based on personalized machine learning: a nationwide prospective cohort study. Sci Bull, 2023, 68: 2106–2114   \n52 Rawal A, Kidchob C, Ou J, et al. Application of machine learning approaches for predicting hemophilia A severity. J Thrombosis Haemostasis, 2024, 22: 1909–1918   \n53 Tislevoll B S, Hellesøy M, Fagerholt O H E, et al. Early response evaluation by single cell signaling profiling in acute myeloid leukemia. Nat Commun, 2023, 14: 115   \n54 Lee S I, Celik S, Logsdon B A, et al. A machine learning approach to integrate big data for precision medicine in acute myeloid leukemia. Nat Commun, 2018, 9: 42   \n55 Xu M, Liu J, Huang L, et al. A novel scoring model for predicting efficacy and guiding individualised treatment in immune thrombocytopaenia. Br J Haematol, 2024, 205: 1108–1120   \n56 Rodríguez-Belenguer P, Piñana J L, Sánchez-Montañés M, et al. A machine learning approach to identify groups of patients with hematological malignant disorders. Comput Methods Programs Biomed, 2024, 246: 108011   \n57 Challen R, Denny J, Pitt M, et al. Artificial intelligence, bias and clinical safety. BMJ Qual Saf, 2019, 28: 231–237   \n58 Walter W, Pohlkamp C, Meggendorfer M, et al. Artificial intelligence in hematological diagnostics: Game changer or gadget? Blood Rev, 2023, 58: 101019   \n59 Chan K Y Y, Zhang C, Wong Y T S, et al. R4 RGS proteins suppress engraftment of human hematopoietic stem/progenitor cells by modulating SDF-1/CXCR4 signaling. Blood Adv, 2021, 5: 4380–4392   \n60 Yang G, Ye Q, Xia J. Unbox the black-box for the medical explainable AI via multi-modal and multi-centre data fusion: a mini-review, two showcases and beyond. Inf Fusion, 2022, 77: 29–52  \n\n![](images/5cefa2d6dfa9d5f8aed01cb44e09b619e2a8d95fe99e84f9c1fa144eb672a293.jpg)  \n\nSummary for “人工智能在血液疾病诊疗中的应用研究进展”",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# Research progress of artificial intelligence in the clinical diagnosis and treatment of hematological diseases  \n\nLiqian Zhang1, Zhuoyu An1, Lijuan Cui2, Wenqian Li3 & Xiaohui Zhang1  \n\n1 Peking University People’s Hospital, Peking University Institute of Hematology, National Clinical Research Center for Hematologic Disease, Beijing   \nKey Laboratory of Cell and Gene Therapy for Hematologic Malignancies, Beijing 100044, China   \n2 Department of Hematology, General Hospital of Ningxia Medical University, Yinchuan 750003, China   \n3 Department of Hematology and Rheumatology, Qinghai Provincial People’s Hospital, Xining 810007, China   \n\\* Corresponding author, E-mail: zhangxh@bjmu.edu.cn  \n\nHematological diseases, characterized by bleeding, fever, and abnormal blood components, are disorders originating from or affecting the blood and the hematopoietic system. Common examples of hematological diseases include benign diseases such as anemia and malignant diseases such as leukemia, lymphoma, and multiple myeloma. The prognosis of these disorders varies and poses a significant disease burden. Improving the diagnosis and treatment of hematological diseases is a key focus in clinical medicine. Artificial intelligence (AI) is a branch of computer science that aims to simulate, study, and extend theories, methods, technologies, and applications of human intelligence. With the rapid development of relevant technologies, AI is increasingly utilized in clinical medicine. In the clinical research field, AI technology primarily involves machine learning (ML), where computers independently extract core information from data through algorithms to achieve established goals. ML encompasses supervised learning, semi-supervised learning, unsupervised learning, and reinforcement learning, all of which are implemented through various algorithms, including random forests, decision trees, support vector machines, neural networks, and Progress. The process of ML in clinical practice includes data collection, preprocessing, algorithm selection, model building, model training, evaluation, optimization, and clinical application. In current research, AI and ML have been widely utilized for prediction, diagnosis, prognosis evaluation, and treatment guidance across a variety of blood diseases, demonstrating exceptional effectiveness in tasks, such as image recognition, omics data mining, and others. For instance, some relapse prediction models for leukemia have been successfully established through different ML algorithms. Researchers have efficiently predicted other benign and malignant hematologic disorders by using AI methods. In the realm of blood disease diagnosis, accurate diagnoses of leukemia have been achieved through the use of AI algorithms with various clinical data, including laboratory test results, blood smears, and genetic information. Additionally, ML prediction models for bone marrow failure, anemia, and other blood disorders have demonstrated excellent performance. Clinical studies focusing on various leukemia subtypes have also shown the value of ML models based on random forests, decision trees, and additional algorithms in guiding treatment decisions. Furthermore, Farswan et al., Zhang et al., and other teams have applied AI to accurately assess the prognosis of other hematological disorders such as multiple myeloma and primary immune thrombocytopenia. AI tools have also demonstrated impressive performance in predicting treatment responses in patients with various blood diseases. Despite challenges such as limitations in original data, ethical debates, and barriers to human-computer interaction, the aforementioned research results have sufficiently demonstrated AI’s potential for development. It is anticipated that AI could be applied in clinical practice, leading to significant improvements in patient prognosis while optimizing the current clinical diagnosis and treatment paradigm for blood diseases.  \n\nblood diseases, artificial intelligence, machine learning, clinical diagnosis and treatment",
+        "category": " Introduction"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# AI energized hydrogel design, optimization and application in biomedicine  \n\nZuhao Li a,b,c,1, Peiran $\\mathbf{Song^{\\mathrm{b,c,1}}}$ , Guangfeng Li b,c,1, Yafei Han b,c, Xiaoxiang Ren b,c,\\*\\*\\*, Long Bai b,c,\\*\\*, Jiacan Su a,b,c,\\*  \n\na Department of Orthopedics, Xinhua Hospital Affiliated to Shanghai Jiao Tong University School of Medicine, Shanghai, 200092, China b Organoid Research Center, Institute of Translational Medicine, Shanghai University, Shanghai, 200444, China c National Center for Translational Medicine (Shanghai) SHU Branch, Shanghai University, Shanghai, 200444, China",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# A R T I C L E  I N F O",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# A B S T R A C T  \n\nKeywords:   \nArtificial intelligence   \nHydrogel   \nDesign   \nOptimization   \nBiomedicine application  \n\nTraditional hydrogel design and optimization methods usually rely on repeated experiments, which is timeconsuming and expensive, resulting in a slow-moving of advanced hydrogel development. With the rapid development of artificial intelligence (AI) technology and increasing material data, AI-energized design and optimization of hydrogels for biomedical applications has emerged as a revolutionary breakthrough in materials science. This review begins by outlining the history of AI and the potential advantages of using AI in the design and optimization of hydrogels, such as prediction and optimization of properties, multi-attribute optimization, high-throughput screening, automated material discovery, optimizing experimental design, and etc. Then, we focus on the various applications of hydrogels supported by AI technology in biomedicine, including drug de­ livery, bio-inks for advanced manufacturing, tissue repair, and biosensors, so as to provide a clear and comprehensive understanding of researchers in this field. Finally, we discuss the future directions and prospects, and provide a new perspective for the research and development of novel hydrogel materials for biomedical applications.",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1. Introduction  \n\nWith the tremendous progress made in materials synthesis technol­ ogy, biomaterials have become the foundation for numerous emerging pharmaceutical and medical applications. They are also a critical issue of research in addressing biomedical needs [1–4]. Particularly, hydro­ gels are a type of three-dimensional (3D) network structure primarily composed of water and network polymers. These materials exhibit high water content and have similarities to natural tissues [5,6]. Hydrogels have been greatly developed and optimized in recent decades due to a variety of fascinating physical and chemical properties, including biocompatibility, high water absorption, degradability, injectable properties, adjustable mechanical properties, and intelligent environ­ mental responsiveness. As a result, they have found broad applications in drug delivery system, wound dressing, contact lens, bone tissue en­ gineering, soft robotics, biosensors and etc [7–9]. However, the devel­ opment of hydrogels is hampered by various challenges such as complicated artificial design process, time-consuming post-­ optimization, and long application cycles [10]. Addressing these prob­ lems requires a comprehensive understanding and application of interdisciplinary techniques, combined with advanced experimental techniques and computational simulation methods.  \n\nArtificial intelligence (AI) is a discipline that focuses on enabling computers to think, judge, and make decisions like humans. AI systems can undergo training using extensive datasets to make predictions, categorize objects, and carry out various intricate tasks. This field en­ compasses sub-fields such as machine learning (ML), natural language processing, images recognition, and algorithms and models that find wide applications across various industries [11,12]. ML, as an advanced and innovative field stemming from the advancements in AI, is a multidisciplinary domain that integrates control theory, computer sci­ ence, determinism, mathematics, philosophy, and various other disci­ plines. Its intersection with these diverse fields makes it a dynamic and all-encompassing area of study [13,14]. ML involves the study, simulation, and implementation of human learning activities using computers. This interdisciplinary field focuses on developing algorithms and models that enable computers to learn from data and improve their performance over time [15]. The use of AI techniques, for example, high-throughput experimentation and the expansion of results to the database of Food and Drug Administration (FDA)-approved excipients, have greatly enhanced the progress of biomaterial design and produc­ tion [16]. Incorporating ML techniques has further expedited biomate­ rial synthesis by shifting it towards a data-driven paradigm, leveraging descriptive-predictive-prescriptive methods and large-scale data anal­ ysis to optimize the search for the most effective biomaterials [17]. Specifically, the application of AI in the design and preparation of hydrogels offers numerous potential advantages. For instance, AI tech­ nology allows for the prediction and optimization of hydrogel compo­ sition and properties. Models can be built to automatically adjust parameters during hydrogel preparation process to achieve the best preparation outcomes [18,19]. Additionally, AI also has the potential to significantly impact the application of hydrogels. In the biomedical field, for example, hydrogels are often used for tissue engineering, drug delivery systems, and wound dressings. AI’s image processing and recognition capabilities can automatically analyze and diagnose a pa­ tient’s wound or lesion area, subsequently guiding the selection of suitable hydrogel materials and preparation methods. Furthermore, AI can be employed to monitor hydrogel performance and application environment. By utilizing sensor networks and data acquisition systems, real-time monitoring of parameters such as temperature, humidity, and pH value can be achieved. Combined with AI algorithms, any deviations from normal conditions can be promptly identified, enabling appro­ priate actions to ensure hydrogel performance and stability [20–23].  \n\nOverall, the application of AI in hydrogels encompasses various as­ pects, including material design and preparation process optimization, material characterization analysis, high-throughput screening, and performance monitoring and control. These applications facilitate the improvement the function and application effectiveness of hydrogels, thereby promoting advancements in hydrogel technology. Although AI has begun to applied to the design and optimization of hydrogels and their biomedical applications, as far as we know, there is currently no comprehensive review that summarizes the integration of AI and hydrogels. In this review, the evolution of AI and its benefits in the context of hydrogels are briefly outlined, along with its application scenarios. Subsequently, we provide a comprehensive description of the state-of-the-art progress in the field of AI-energized hydrogel design and optimization, and its applications in biomedicine. Finally, we will pre­ sent a discussion of the prospects and limitations of AI-Energized hydrogels. Through comprehensive research and analysis of relevant literature, our goal is to offer a clear and deep understanding for researchers and pave the way for future study in this field.  \n\n![](images/e739cfb18c45e87bf1bcb51b4bc5c71458be275c798e3619edc60f56da3761a9.jpg)  \nFig. 1. (A) The development history of hydrogels. (B) Hydrogels for various tissue engineering applications, such as repair the tissues of bone, cartilage, oral, meniscus, muscle, skin, cardiac, cornea, neural, vascular, hepatic, gastric, and so on. (C) Problems and challenges in the design, optimization and biomedical ap­ plications of hydrogels.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2. Overview of hydrogels and its development dilemma  \n\nSince the pioneering work of Wichterle et al. in utilizing hydrated hydroxymethyl methacrylate (HEMA) network in contact lenses in the 1960s, various functional hydrogels have sparked significant research interest in the application of tissue engineering and biomedicine (Fig. 1A) [24,25]. Due to the presence of hydrophilic components within the polymer backbone, hydrogels have the ability to retain a significant amount of water and exhibit physicochemical properties resembling those of liquid water. This unique property allows hydrogels to display a solid-like rheological behavior on a macroscopic scale. This fascinating characteristic of hydrogels opens up the possibility of mimicking various features of the ECM found in tissues [26]. Furthermore, the gelation of hydrogels can be achieved through different methods such as physical cross-linking, dynamic cross-linking, and chemical cross-linking [27]. These techniques offer opportunities for engineering the gelation pro­ cess to meet specific needs. Additionally, advanced chemical approaches have been developed to precisely manipulate the shape, structure, and architecture of hydrogels. Through these methods, hydrogels can be tailored with desirable functionalities including adjustable properties, excellent biocompatibility, controllable degradability, and mechanical compatibility with biological tissues. This unique characteristic makes them similar to biological tissues, enabling interactions with living cells and surrounding environments [28]. As a result, they have found broad applications in drug delivery system, wound dressing, contact lens, bone tissue engineering, biosensors and etc (Fig. 1B) [6,29–34]. Details of current preparation, performance and application of typical hydrogels are listed in Table 1 [35–42].  \n\nIn tissue engineering, hydrogels provide a supportive framework for the growth and regeneration of cells. Their biocompatibility and ability to mimic the natural ECM make them ideal scaffolds for tissue regen­ eration. By encapsulating cells within hydrogel matrices, scientists have successfully created artificial tissues and organs, leading to advance­ ments in regenerative medicine [43,44]. Beyond tissue engineering, hydrogels have also found applications in drug delivery systems. The porous structure of hydrogels allows for controlled release of drugs, ensuring their gradual release over an extended period. This controlled drug delivery minimizes side effects and enhances therapeutic efficacy. Furthermore, hydrogels can be tailored to respond to specific stimuli, such as temperature, pH, or enzymatic activity, enabling targeted drug delivery and precise treatment [45–47]. Moreover, hydrogels have been explored for biosensing and diagnostic purposes. By incorporating spe­ cific molecules or nanoparticles into the hydrogel network, researchers have developed sensors capable of detecting various analytes, including glucose, proteins, and DNA. These hydrogel-based biosensors offer a sensitive and selective detection platform for disease diagnosis and monitoring [48,49].  \n\nHowever, the development of hydrogels, as well as biomaterials in general, has been hampered by challenges such as complicated artificial design process, time-consuming post-optimization, and prolonged pre­ clinical testing cycles. These challenges include material screening, control of the preparation process, time and cost constraints, complex testing, characterization, optimization and prediction [10,50]. The design and preparation of hydrogels with specific properties often involve time-consuming trial and error processes to optimize the formulation (Fig. 1C). Overcoming these bottlenecks, finding effective optimization methods and predictive models to enhance hydrogel per­ formance and preparation efficiency remain major challenges [51]. Addressing these problems requires the comprehensive application of materials science, chemical engineering, and other relevant fields of knowledge, combined with advanced experimental techniques and computational simulation methods. Predictably, with the continuous progress made in interdisciplinary, these bottlenecks are expected to be gradually overcome.",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 3. Overview of AI and its prospects in hydrogels  \n\nAI, originating in computer science, involves the development of machines with the ability to simulate human intelligence. These intel­ ligent systems are programmed to think and learn in a manner similar to humans. They are designed to carry out tasks that traditionally neces­ sitate human intelligence, including language translation, speech recognition, problem-solving, and decision-making [52]. The AI systems use algorithms and data to analyze and interpret information, make predictions, and take actions based on their analysis. AI technology is widely applicable and is used across a broad spectrum of industries, including medical care, finance, industrial manufacturing, trans­ portation, and many other domains. Its versatile applications have made it an essential tool in modern society [53]. The origins of AI can be dated back to the 1950s [54], a time when John McCarthy first introduced the term \"AI\" in 1956 during a conference at Dartmouth College [55]. Over the past few decades, AI has gone through multiple stages and signifi­ cant milestones. Here are some important developments in its history:  \n\nTable 1 Details of preparation, performance and application of typical hydrogels.   \n\n\n<html><body><table><tr><td>Hydrogels</td><td>Preparation</td><td>Performance</td><td>Application</td><td>Refs</td></tr><tr><td>Polyacrylamide (PAAm)</td><td>Free radical polymerization of acrylamide monomers in the presence of a crosslinker, such as MBA.</td><td>High water absorption capacity and tunable mechanical strength, depending on the crosslinking density.</td><td>Tissuee engineering, drug delivery, wound dressings, and etc. due to their biocompatibility and ability to swell in biological fluids.</td><td>[35]</td></tr><tr><td>Polyvinyl Alcohol (PVA)</td><td>Crosslinking PVA chains with a crosslinking agent, such as glutaraldehyde or borate ions.</td><td>Excellent biocompatibility, high water content, and good mechanical properties.</td><td>Contact lenses, wound dressing materials, and as scafolds for tissue engineering due to their biocompatibility and optical clarity.</td><td>[36,37]</td></tr><tr><td>Polyethylene Glycol (PEG)</td><td>Physical or chemical crosslinking of PEG chains with crosslinking agents or through</td><td>Excellent tunability of mechanical properties and degradation rates.</td><td>3D cell culture platforms, injectable materials for tissue engineering, and drug delivery systems.</td><td>[38,39]</td></tr><tr><td>Sodium Alginate</td><td>photopolymerization. Ionotropic gelation of sodium alginate with divalent cations, such as calcium ions.</td><td>High water absorption capacity and can form a gel under mild conditions</td><td>Pharmaceutical industry for drug delivery, food industry for encapsulation of bioactive compounds.</td><td>[40-42]</td></tr></table></body></html>  \n\nSymbolic Period (1956–1974): During this period, the focus was mainly on using logical symbols and rules to represent knowledge and reasoning. Many symbol-based expert systems emerged during this time.  \n\nConnectionist Period (1980s): Connectionism emphasized simu­ lating the connections and learning processes between neurons in the human brain through network structures. This period witnessed the rise of research on neural networks and deep learning.  \n\nKnowledge-based Period (1980–1995): The knowledge-based period focused on constructing systems with a large amount of domain-specific knowledge. Expert systems and rule-based reasoning became mainstream.  \n\nStatistical Learning Period (1995-present): With the improvement in computational power and the widespread application of big data, statistical learning methods, for instance, support vector machines, random forests, and deep learning have become the primary approaches. This period is also known as the “era of machine learning”.  \n\nReinforcement Learning Period (2006-present): Reinforcement learning is a method that allows intelligent agents to learn through trial and error and feedback. This approach has found extensive applications in fields such as gaming and robot control.  \n\nRecent milestones, such as AlphaGo [56], AlphaFold [57], and ChatGPT [58], have permeated various industries and achieved signif­ icant breakthroughs, and its potential for applications has an extremely vast space limited only by our imagination. In the future, AI will continue to develop rapidly, bringing more convenience and innovation to our lives and work.  \n\nML, as a subset of AI, which has emerged as the most advanced technology stemming from the progress of AI, forms the fundamental basis for the majority of AI applications in the present era. ML encom­ passes three primary strategies: supervised learning, unsupervised learning, and reinforcement learning (Fig. 2A) [59,60]. There are several common ML models, such as random forests (RF), support vector machines (SVM), logistic regression, neural networks, recurrent neural networks (RNNs), convolutional neural networks (CNNs), graph neural networks (GNNs), and transformers, offer the tools and methodologies that enable AI systems to accomplish complex tasks that were once considered unattainable (Fig. 2B). As described in our previous review, each different strategy and ML model has its own strengths and fields of application that can be used to solve different problems [59].  \n\nAI technology offers numerous advantages in the design and opti­ mization of hydrogels. For materials property prediction and design, AI is used to process extensive volumes of data and train models to predict the physical and chemical properties of different hydrogel materials. This helps researchers in designing customized hydrogel materials to meet specific application requirements. For optimization, through ML algorithms, AI can analyze the relationships between the composition, structure, and properties of hydrogels, providing optimization recom­ mendations. It assists researchers in quickly screening the best material combinations to enhance the performance and stability of hydrogels. AIenergized hydrogel products have various potential application sce­ narios in biomedical field, including wound healing, tissue engineering, advanced manufacturing, drug delivery, and biosensors. AI can assist in designing and manufacturing these hydrogel materials, improving the efficiency and safety of the products. In summary, the application of AI in hydrogel design and optimization accelerates the material develop­ ment process, enhances material properties, and promotes the use of hydrogels in various fields.  \n\n![](images/42a7b06e850be7a87929dc272f073f82b78d4c17261dc7ea1faee44d46c860cd.jpg)  \nFig. 2. (A) The main types of ML, including supervised learning, unsupervised learning, and reinforcement learning. (B) Several common ML models offer the tools and methodologies for AI systems.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 4. Advantages of AI in hydrogel engineering  \n\nOwing to various fascinating physical and chemical properties, hydrogels have widely applied in drug delivery system, wound dressing, contact lens, tissue engineering, and etc [32,61–66]. However, the developmental workflow of hydrogels, as well as biomaterials in gen­ eral, has remained slow-moving due to some bottlenecks in the design and optimization of hydrogels. With the rapid development of AI tech­ nology, there are many potential advantages in the design and optimi­ zation of materials, such as prediction and optimization of properties, multi-attribute optimization, high-throughput screening, automated material discovery, optimizing experimental design, and etc. Herein, we describe some potentially important advantages of AI in hydrogel design and optimization in hopes of providing ideas for the preparation of advanced hydrogels.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 4.1. Detecting the properties of hydrogels  \n\nInvestigating each hydrogel formulation in practice is both a costly and time-consuming endeavor. In some cases, some formulations aren’t feasible due to their material properties, and inspecting them wastes valuable resources. Computational prediction naturally plays a critical role in the optimization of hydrogel formulations [60]. For the past few years, AI has obtained significant attention in the area of material characterization analysis. Deep learning, in particular, is highly effective in addressing complex nonlinear mapping [67,68].  \n\nThe potential applications of flexible hydrogels as pressure distri­ bution sensors are indeed promising. Whereas the existing hydrogel pressure distribution sensors employ an array-type structure with intricate wiring and exhibit exceedingly low resolution, significantly impeding the flexibility of the hydrogels and constraining its potential development and applications [69,70]. To address these limitations, Liu et al. developed a pressure distribution reconstruction model according to the hydrogel pressure distribution sensors using a ML method. To enhance the accuracy of plantar pressure distribution reconstruction, a substantial quantity of plantar pressure distribution data collected from clinical sources can be fed into the network for secondary learning [71]. The authors utilize the ML method due to its capacity to conduct tar­ geted optimization and secondary learning, which are important ad­ vantages compared to the traditional electrical impedance tomography method. A comprehensive understanding of the rheological properties of polymeric materials can be harnessed to design a diverse range of injectable hydrogels, including those used as bio-inks for 3D printing. Furthermore, advanced techniques have utilized AI-energized methods to detect the viscosity of polymeric materials [72]. In a recent study, an inductive logic programming-based method was employed to assess the correlation between the rheological behaviors and printability of  \n\n![](images/bc0f371c85787bc7a22826b42780923219df036ae74167ba1cabf859576a9c3b.jpg)  \nFig. 3. (A) Illustration of bio-inks development according to mathematical strategies to predict tissue engineering issues. (B) Schematic diagram for developing 3D printable naturally derived bio-inks. (C) Scheme illustrating the preparation of the cell-laden 3D biomimetic structure composed by low viscosity hydrogel $(1\\%$ collagen) as cell vehicles and high viscosity hydrogel bio-inks as frameworks. Adapted with permission [73]. Copyright $\\circledcirc$ 2020, IOP Publishing Ltd.  \n\nFDA-approved natural polymers (Fig. 3) [73]. This powerful program­ ming tool, along with other ML strategies, is categorized under the subset of AI, where advanced computational models are capable of processing massive amounts of data to recognize patterns [74]. How­ ever, as the field of AI continues to evolve, it becomes increasingly important to conduct new studies focused on predicting the rheological behaviors of prepared hydrogels. For detecting the properties of pre­ pared hydrogels, AI can construct a complex composition-process-structure-property model to analyze the mechani­ cal properties, water absorption properties, viscosity, stability, con­ ductivity, degradability, and other inherent characteristics of prepared hydrogels. Consequently, efficient characterization analysis energized by AI offers a convenient procedure for the design and optimization of hydrogels.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 4.2. Predicting and optimizing the properties of hydrogels  \n\nHigh-throughput characterization of the relations between compo­ sition, process, structure, and property is essential in facilitating the discovery of molecules and materials, as well as the formation of manufacturing paradigms. For predicting and optimizing the properties of hydrogels, AI can analyze the complex composition-process-structureproperty model to predict various properties like mechanical strength, water absorption, stability, and etc., thus providing guidance for hydrogel design and optimization. For example, a comprehensive un­ derstanding of the rheological properties of polymeric materials can be leveraged to fabricate injectable hydrogels suitable for 3D printing. ML can accurately predict the rheological properties of hydrogels and optimize their formulations (Fig. 4A). Recently, a robust supervised ML model successfully predicted the viscosity of polymer composites con­ taining nanoparticles [75]. By utilizing automatic sensing and physical guidance of $\\mathbf{ML}$ , the rheological properties of hydrogels can be rapidly and autonomously characterized with high-throughput (Fig. 4B). Spe­ cifically, this innovative high-throughput method accurately charac­ terized the rheological properties of hydrogels in 96-well plates, achieving a remarkable rate of $24~{\\mathfrak{s}}/$ sample, which is 70 times faster than the current state-of-the-art [76]. Ultimately, this high-throughput performance prediction strategy paves the way for optimal design of hydrogels.  \n\nIn addition to monitoring the rheological properties of hydrogels, AIenergized high-throughput screening can also predict and optimize various properties of hydrogels. A statistical and AI method based on principal component analysis can be employed to evaluate the adsorp­ tion efficiency of hydrogels by applying varying parameters, achieving a rapid and efficient evaluation of the composite hydrogels’ properties [77].  \n\nThe influence of critical parameters such as raw materials concen­ trations size and zeta potential of nanoparticles, and pH value of solu­ tions on the stiffness, gelation time, and adhesion behavior can be comprehensively investigated by an ANNs model, thus predicting the properties of hydrogels [78–80]. Furthermore, AI-energized high-­ throughput screening significantly reduces raw material consumption.  \n\n![](images/fd794d790f393f5c6a6ebd5521b0b2e69a4f2f5429f8792ca16fe7ad5605b78d.jpg)  \nFig. 4. (A) Diagram of optimizing hydrogel formulations by using ML. Rheological information of hydrogels must be first collected through experiments or obtained from literature. Then, the collected information is fed into ML-based algorithms. Robust algorithms can predict the properties of different components and help optimize the formulation of hydrogels. (B) Illustration of a method for rapidly and autonomously characterizing the rheological properties of hydrogels by highthroughput through automated sensing and physically guided supervised ML. Adapted with permission [76]. Copyright $\\circledcirc$ 2022, Elsevier Ltd. (C) The impact of innovative autonomous sensors and data-driven HTC strategies on achievable screening throughput compared to conventional characterization methods. Adapted with permission [76]. Copyright $\\circledcirc$ 2022, Elsevier Ltd.  \n\nSeifermann et al. reported a high-throughput tactics according to miniaturized experiments and ML to optimize the photostability prop­ erties of materials. Within 13 experiments, the authors successfully optimized the material properties of approximately 13,440 possible hydrogels, using a total of only $0.65~\\mathrm{mL}$ of the original solution and about $170\\mathrm{mg}$ , that is, $836~\\ensuremath{\\upmu\\mathrm{mol}}$ monomer and crosslinker [81].  \n\nOverall, utilizing AI technology to predict and optimize the proper­ ties of prepared hydrogels significantly decreases the time and expenses associated with individual experiments. The AI-energized highthroughput screening strategy has demonstrated notable efficiency and practicality compared to traditional methods for predicting and opti­ mizing properties of hydrogels. It is anticipated to emerge as a novel tool for quality control and assurance in emerging sectors.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 4.3. Materials discovery of hydrogels  \n\nAI-energized materials discovery is a cutting-edge field that com­ bines AI algorithms and computational methods to expedite the process of identifying and designing novel materials with specific properties [82]. Thanks to advancements in materials science, there is a substantial amount of data available from experimental and simulation studies, which forms the basis for employing ML techniques in materials research and development [83,84]. AI algorithms can be applied in various ways within materials discovery. By analyzing and predicting the behavior of materials using the available data, AI can assist re­ searchers in conducting more efficient and targeted experimentation [85–87]. Say concretely, this entails analyzing existing databases, sci­ entific literature, and experimental results to uncover patterns and re­ lationships between the composition, structure, and properties of materials (Fig. 5) [17,88,89]. Quantitative structure properties re­ lationships provide the unique property to correlate microscale molec­ ular descriptors to larger macroscale material properties [90,91]. Such knowledge can then guide the search for novel materials with desired characteristics.  \n\n![](images/85466a796cb1735deb1feb5398e5ca852eb33dc627a1bd069781c7e02172a2f8.jpg)  \nFig. 5. (A) Overview of the AI-energized materials discovery. Adapted from CC-BY open access publications [88]. Copyright $\\circledcirc$ 2016, Elsevier Ltd. (B) An illustration of material discovery, using titanium alloy as an example. (i) Properties prediction processes, such as filtering of martensite start (Ms) temperature and combining maps. (ii) Constraining the prediction in βLow-assisted alloy development for low-modulus and low- $\\cdot\\{\\beta$ stabilizer $\\upbeta$ -titanium alloys. Adapted with permission [89]. Copyright $\\circledcirc$ 2020, Elsevier Ltd.  \n\nThe development of materials data science has spurred initiatives such as the Materials Genome Initiative (MGI) in the United States, which aims to accelerate research cycles and reduce costs through highthroughput computing, data-driven methods, and big data technologies [92]. ML, which falls within the realm of AI and data science, plays a crucial role in the MGI. ML entails constructing computers that enhance their performance autonomously by leveraging past experiences. It is a rapidly growing interdisciplinary field dominated by computer science and statistics, and is essential to AI and data science [93–95]. The advancement in ML has been propelled by the emergence of innovative learning algorithms and theoretical frameworks, as well as the increasing availability of online data and low-cost computation. ML methods are extensively used across various domains, including science, technology, and commerce, facilitating evidence-based decision-making in areas, for example, medical care, manufacturing, education, finance, law enforcement, and marketing [96].  \n\nHybrid materials have been the subject of research for several de­ cades; however, the complete understanding of their formation remains elusive, and the evolution of novel compounds largely depends on exploratory and trial-and-error synthesis [97–99]. Recently, simulationand data-driven methods have emerged as an alternative to the tradi­ tional method of experimental trial-and-error. ML models, in particular, have shown promise in predicting the conditions necessary for the for­ mation of new hybrid materials. In fact, these models have out­ performed traditional human strategies and have been successful in predicting the formation conditions with a certain level of accuracy, achieving an 89 percent success rate [100]. The integration of high-throughput synthesis and evaluation means enables the elucidation of the structure-property relationship using a large volume of empirical data, facilitating the identification of potential target candidates for synthetic efforts [101,102].  \n\nIn summary, AI-energized materials discovery leverages AI algo­ rithms and computational methods to accelerate the identification and design of new materials. The wealth of data available and ML techniques help researchers analyze and predict material behavior, facilitating more efficient experimentation and guiding the search for desired ma­ terial properties. However, there is still much work to be done regarding the AI strategy in predicting materials design for hydrogels in biomed­ icine. There are several methods available that can provide insights for guiding the discovery or design of next-generation materials. Simulation-based predictions can assist in identifying potential target candidates for synthetic endeavors by analyzing their physical proper­ ties. Integrated high-throughput synthesis and evaluation means allows for the determination of structure-property relationships from large experimental datasets. Additionally, clustering based on similar out­ comes can provide valuable insights. These AI-driven approaches can greatly facilitate the discovery and design of next-generation materials in the field of hydrogel biomedicine [103].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 5. Applications of AI-energized hydrogel design in biomedicine  \n\nAi-energized design and optimization can obtain advanced hydro­ gels, making them play a broader role in biomedical applications, for instance, drug delivery systems, bio-inks for advanced manufacturing, tissue repair, biosensors, and etc. Herein, we focus on the various ap­ plications of hydrogels supported by AI technology in biomedicine, so as to provide a clear and comprehensive understanding of researchers in this field.",
+        "category": " Introduction"
+    },
+    {
+        "id": 12,
+        "chunk": "# 5.1. Drug delivery systems  \n\nHydrogels hold great promise as drug delivery systems, thanks to their excellent biocompatibility and similar properties to natural tissues [104–106]. However, the development workflow for hydrogel-based drug delivery systems relies heavily on trial and error, leading to sig­ nificant requirements in terms of time and material resources. AI has the potential to mitigate this challenge by leveraging insights gained from collected data, enabling a more focused and predictive experimental method [107]. The applicability of AI in the workflow of hydrogels as drug delivery systems has been demonstrated through the establishment of predictive models, optimization of algorithms, and image processing and recognition. AI can be effectively utilized to predict hydrogel for­ mation, optimize hydrogel performances, and ultimately to tune the drug release profiles (Fig. 6A) [108].  \n\nFirstly, AI technology is utilized to construct models for predicting the release behavior of drugs incorporated in hydrogels, considering the permeability, diffusion rate, dissociation rate, as well as the structure and properties of hydrogels. By analyzing a significant amount of experimental data, these models can provide insights into the release rate and duration of drugs in hydrogels, thus supporting the design of sustained-release drug systems [109,110]. Secondly, AI can enhance the performance and efficacy of drug sustained-release systems by opti­ mizing algorithms. Through AI algorithms, the optimal drug loading, hydrogel composition ratio, preparation conditions, and other parame­ ters can be determined to achieve prolonged or precisely controlled release rates. The optimization algorithm based on AI strategy can un­ dergo multiple simulations and employ genetic algorithms to identify the optimal strategy for sustaining drug release [111,112]. Additionally, AI can facilitate the monitoring and control of drug slow-release systems through image processing and recognition technology [113,114]. For instance, by incorporating nanoparticles or markers to the surface or inside of the hydrogels, AI’s image recognition capabilities enable real-time monitoring of the drug release profiles. This real-time data analysis allows for a deeper understanding of drug release, leading to more accurate adjustments of system parameters for better control of the drug release profiles [108,115].  \n\nAccurately predicting the formation of hydrogels is essential in the development of efficient drug delivery systems. To address this issue, Li et al. employed a combinatorial chemistry approach to construct a diverse library of ${>}2000$ peptides for the analysis of their self-assembly behavior [116]. In this study, the authors utilized AI to establish cor­ relations between quantitative structure-property relationships, chemi­ cal properties, and self-assembly behaviors. Through this approach, the study identified prominent structural features successfully that signifi­ cantly contribute to the formation of hydrogels.  \n\nAfter being successfully formed, the hydrogel system must have properties that are specifically designed for its intended purpose. These properties include the ability to respond to temperature changes for injectable delivery and interact with biological systems, such as a new mucoadhesive thermos-gelling hydrogel for sublingual enhancement [112] and orotransmucosal vaccine-delivery platforms [117]. For instance, Rio et al. utilized AI as an instrument to investigate in­ teractions between polymers in order to develop thermosensitive hydrogels that are appropriate for delivering proteins to the rectum in cases of inflammatory bowel disease. Enemas containing Pluronic F68,  \n\n![](images/6a0a33a7ee57e1e082ff562cd6fd84e80b187eefc99721cafed1a85bc17ce422.jpg)  \nFig. 6. (A) AI strategies, such as RF, ANNs, and SVM, have been applied at multiple steps, including (1) forecasting hydrogel formation according to previous ingredients, (2) improving 3D printing performance, (3) adjusting injectable properties, (4) optimizing supporting functions, (5) optimizing and forecasting drug release curves, and (6) upgrading clinical effects, to enhance the preparation of hydrogel drug delivery systems. Adapted with permission [108]. Copyright $\\circledcirc$ 2022, Elsevier Ltd. (B) Synthesis, analysis and optimization of specific injectable hydrogels for delivering proteins by the high-throughput strategies. Adapted with permission [119]. Copyright $\\circledcirc$ 2019 American Chemical Society.  \n\nPluronic F127, and Methocel K4M were developed and analyzed for delivering proteins to the rectum. The researchers utilized a commer­ cially available hybrid AI tool platform that integrated artificial neural networks (ANNs), fuzzy logic technologies (FormRules version 4.03), with the polymer concentrations as input variables to establish corre­ lations with the ultimate characteristics of the hydrogels [118]. Through this AI-energized strategy, it is possible to determine the role of each polymer component in the hydrogel formulation on the features of the obtained hydrogel, for instance, F127 affects the injectability and mucosal adhesion.  \n\nAchieving sustained and dose-specific release profiles is clinically significant for drug delivery systems and requires predicting and opti­ mizing parameters, including minimizing uncontrol release and maxi­ mizing cumulative release [120,121]. But the compatibility of data-hungry ML techniques is limited by the time- and resource-intensive nature of drug release tests. To address this issue, a research pointed fabricating various hydrazine-crosslinked in situ formed hydrogels (126 in quadruplicate) using combinatorial methods. The initial characterization was completed within hours, followed by parallelized release experiments conducted in a 96-well plate format (Fig. 6B). The release curves were subsequently fitted to an amendatory first-order equation in order to determine the parameters associated with burst release, cumulative protein release, as well as release rate. The authors developed a partial least-squares model to explain $60\\text{\\textperthousand}$ of the variance and forecast optimal polymer combinations for protein delivery applications [119]. In addition, Castro et al. developed a literature-mined dataset to estimate the critical parameters in regard to the formulation pipeline and dissolution characteristics in vitro [107].  \n\nApart from these, it is also worth considering other relevant strategies used to the release systems. For instance, in a drug release research of injectable formulations, shapely additive explanation dependence plots were employed to evaluate characteristic importance and the in­ teractions among the features. The resulting model achieved precise predictions of release using a small amount of training data consisting of 102 formulations. This achievement was further validated through an external dataset of 79 unseen release profiles, obtained from literature mining (Fig. 7) [122]. The authors pointed out that ML algorithms have the capability to predict experimental drug release from the advanced drug delivery systems. The use of these trained models can provide valuable insights for designing new long-acting injectables.  \n\nLong-acting injectable formulations are regarded as a strategy with great potential for treating chronic diseases due to their ability to enhance therapeutic efficacy, patient compliance, and safety. Moreover, previous studies have demonstrated the potential of utilizing AI algo­ rithms to forecast release profiles from advanced drug delivery systems. These predictive models can effectively inform the development of novel long-acting injectable formulations. Employing this data-driven strategy promises to save time and economic budgets related to drug formulation development.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 5.2. Bio-inks for advanced manufacturing  \n\nSince the early 1980s, 3D printing technology has been in a booming phase, encompassing various techniques such as from fused-filament fabrication for complex plastic structures to the development of nextgeneration bioprinting technology (Fig. 8A) [123]. Hydrogels, as bio-inks to incorporate living cells and/or bioactive substances to form biomaterial solutions for printing 3D structured functional scaffolds in a layer-by-layer way. This technology is expected to play an important role in areas such as regenerative medicine, tissue repair and organ transplantation. The mechanical forces utilized in extrusion bioprinting can be categorized into three classes: pneumatic, piston, and screw-driven (Fig. 8B) [124]. Leveraging its intrinsic customizability and rapid fabricating capabilities, 3D bio-printing has the potential to facilitate the large-scale production of personalized artificial or bionic organs, as well as smart wearables [125,126]. Despite this potential, the development of 3D bio-printed multifunctional products is still at a preliminary stage. One significant challenge is formulating inks, typi­ cally hydrogels, that maintain functionality after printing and are compatible with other inks to fabricate complex multifunctional archi­ tectures [127]. Another obstacle arises from the fact that traditional printing platforms are chiefly ex situ printing [128]. The fabricate-then-transfer process has several drawbacks, including dis­ crepancies between the printed and target surfaces, damage to delicate materials like hydrogels during manual handling, which can impact post-transfer fidelity, the risk of contamination during transportation and manual transplantation, and constraints in minimally invasive surgery [129–131]. A potential workaround is to employ AI-powered, minimally invasive 3D-printing methods to directly manufacture on target surfaces.  \n\n![](images/1b0872ada371ee73708f572766a59179215d329044d1bd6326f3fa694744857f.jpg)  \nFig. 7. (A) Selected administration routes of long-acting injectables formulations approved by FDA. (B) Typical trial-and-error loop conventionally used in the development of classical long-acting injectables formulation. (C) Training and analyzing ML models to enhance the developing of new long-acting injectables systems, termed “Data-driven long-acting injectables formulation development”. Adapted with permission [122]. This is an open access article distributed under the terms of the Creative Commons CC BY license.  \n\nAI-powered printing utilizes past experiences to make predictions about future states, enabling quick adaptation to dynamic and changing targets [133]. In the realm of printing procedures, AI plays a prominent role at three levels: open-loop AI, closed-loop AI, and predictive AI (Fig. 8C). Detailed descriptions of the specific characteristics and ad­ vantages of these three AI-energized 3D printing strategies can be found in a previous review [132]. Herein, our focus is primarily on exploring the printability and advancements of these AI-energized hydrogels development and fabrication as bio-inks.  \n\nIn the realm of bio-inks design for 3D printing, the primary role of AI is to predict and optimize hydrogel properties, enable high-throughput screening, and facilitate new material discovery. Kim et al. utilized a ML based model system developed by MATLAB software to design a 3Dprintable hydrogel ink composed of functionalized alginate and DNA (DNA@FSA inks) (Fig. 9). The printability scores of the datasets were predicted by adjusting the independent input variables, including printing temperature $27^{\\circ}\\mathrm{C}$ and $37^{\\circ}\\mathrm{C})$ , nozzle size (0.2 and $0.4~\\mathrm{{mm}}\\dot{}$ , pneumatic pressure (20 and $60\\mathrm{kPa}$ ), FSA concentration (from 1.2 to 3.8 $\\mathbf{w}/\\mathbf{v}\\%$ at intervals of $0.2\\mathrm{w}/\\mathrm{v}\\%)$ ), and gel concentration (1, 2, 2.5, 3, and $4\\ \\mathrm{w}/\\mathrm{v}\\%)$ . The results revealed that the highest printability grade was obtained with FSA concentrations of 2.6 and $2.8~\\mathrm{w}/\\mathrm{v}\\%$ . Consequently, according to the ML approach, $3~\\mathrm{w/v\\%}$ FSA was used to optimize and stabilize the printing process [134]. The 3D-printed wound dressing was designed to achieve optimal porosity, allowing for effective absorption of exudate and blood at the wound site. Additionally, the mechanical properties of the dressing can be adjusted to ensure good shape fidelity and ease of printing during the 3D printing process. As a result, this innovative DNA-induced biomineralization strategy resulted in a func­ tional platform with great potential for clinical applications in both acute and chronic wound repair.  \n\nEnhancing the quality of 3D printed bio-scaffolds extends beyond the accuracy and spatial control of material deposition. Preserving the functionality of the ink, particularly cell viability, throughout the printing process is crucial for achieving optimal print quality [135]. Given the distinct advantages of AI in material discovery and screening, and high-throughput prediction and optimization of material properties, it is anticipated that AI-energized bio-inks preparation will overcome the current technological barriers and pave the way for advancements in  \n\n![](images/8508cb8c960cc0efd3b28e1813f6e823381b9ed5da2b6c8c1aea87273844a288.jpg)  \nFig. 8. (A) The 3D bioprinting process includes pre-bioprinting, bioprinting, and post-bioprinting. (B) Constructs printed from bio-inks and applications and schematic of pneumatic-, piston-, and screw-driven printing. Adapted with permission [124]. Copyright $\\circledcirc$ 2023 The Authors. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. (C) AI can be involved in various stages of 3D bio-printing in different ways, including AI-energized fabrication and data-driven fabrication. The illustration indicates the bio-printing procedure for different levels AI involvement in fabrication, such as 3D printing without AI, open-loop AI printing, closed-loop AI printing and predictive AI printing. Adapted with permission [132]. Copyright $\\circledcirc$ 2020, Springer Nature Limited.  \n\n3D printing technology.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 5.3. Tissue repair  \n\nIn recent years, a variety of tissue engineering strategies have been used to repair damaged tissues in the body, and great progress has been made [136–139]. Hydrogels are commonly applied materials in repairing tissues, such as bone and skin tissues, and AI strategies can achieve more efficient and precise preparation [140]. AI can be utilized in various aspects of hydrogel composition screening, material prepa­ ration, and performance optimization. Through the analysis of extensive medical data and experiential knowledge, AI can assist in rapidly selecting appropriate material combinations and predict their perfor­ mance through simulation and calculation. Additionally, AI can also employ ML algorithms to optimize the preparation process of hydrogels, thereby improving production efficiency and quality control [141,142]. For example, by using the image processing and recognition capabilities of AI, it is possible to automatically analyze and diagnose the wounds or lesion areas of patients, and then select appropriate hydrogel materials and preparation methods (Fig. 10A). AI-based algorithms can be employed to evaluate changes in wound characteristics, guiding the design and preparation of hydrogels, as well as estimating the efficacy of therapy and predicting healing outcomes (Fig. 10B) [143]. The multi­ functional hydrogel wound dressing offers a comprehensive approach to wound care, combining precise treatment, real-time monitoring, and personalized management for intelligent wound monitoring. This innovative solution not only accelerates the healing process but also effectively reduces the risk of bacterial infections. It represents a sig­ nificant advancement in the field of intelligent wound management and sets a new standard for future developments in this area.  \n\nThe application forms of hydrogels as wound dressings are various, among which hydrogels as bio-inks are used to prepare personalized dressings by 3D printing, which represents an advanced preparation method [144–146]. However, optimizing the printing parameters typi­ cally depends on previous knowledge and a significant number of laborious verification experiments [147]. To resolve the problem, a high-throughput printing-condition-screening system with the assis­ tance of AI (AI-HTPCSS) was proposed by Chen et al., using extrusion bio-printing as the demonstration (Fig. 11A). Specifically, for the proof of concept, the phase diagram of alginate-gelatin ink for gel printing could be obtained based on AI-HTPCSS. (Fig. 11B and C). Based on the optimized conditions, 3D grid-like hydrogel scaffolds with different structures can be printed. The scaffolds exhibited good consistency with the digital models and possessed excellent mechanical and biological features (Fig. 11D). Finally, systematic in vitro and in vivo evaluations demonstrated that scaffolds printed under optimized conditions can apparently accelerate the diabetic wounds healing (Fig. 11E) [148]. The AI-HTPCSS proposed in this work demonstrated a universal platform for rapid screening of optimal printing conditions for given combinations of bio-printers and bio-ink materials, showing promise for potential ap­ plications in tissue engineering and regenerative medicine.  \n\n![](images/8457649d45ba76d7b235e2dc869a23f3735b72ae391f25cdf3b4e0972a3047fd.jpg)  \nFig. 9. (A) Illustration of developing bioinspired 3D-printed hydrogels by DNA-induced biomineralization. (B) ML modeling applying Gaussian process regression to predict the printability score of the prepared hydrogel bio-inks. (C) Various scores based on variable nozzle size, temperature, pneumatic pressure, and FSA con­ centration. Adapted with permission [134]. This is an open access article distributed under the terms of the Creative Commons CC BY license.  \n\n![](images/41c17367e3f6652b741379c82e6ce78be50ba1f46136a3036bc0dca7b67b49e9.jpg)  \nFig. 10. (A) Description of the wound recognition. Personalized 3D printed hydrogel wound dressings can match the shape and size of the wound by recognizing wound characteristics. (B) Flow chart of intelligent wound monitoring with multifunctional hydrogel dressings, including (i) wound recognition, (ii) real-time status supervising and (iii) customized wound management. Adapted with permission [143]. Copyright $\\circledcirc$ 2022, Elsevier Ltd.  \n\n![](images/7704ce715453aa76d1e5a2a855a676e7af35744a6e9e7c43cc1f8f85103cb281.jpg)  \nFig. 11. Illustration of the AI-HTPCSS for fast screening of the optimized extrusion bio-printing conditions of a given bio-printer and bio-ink combination. (A) Overview of the AI-HTPCSS. (B) The morphologies of extrusion patterns under different bio-printing parameters, such as droplets, lines of droplets, or lines. (C) Graphical representing the line uniformities of extruded patterns under different bio-printing parameters. (D) Optimized bio-printing conditions are sued to prepare multi-layer 3D mesh-like hydrogel scaffolds with different structures. (E) The application of the optimal printed hydrogel dressings for accelerating the healing of diabetic wounds. Adapted with permission [148]. Copyright $\\circledcirc$ 2022, Wiley-VCH GmbH.  \n\nHowever, it should be noted that at the current level of technological development, hydrogels prepared using AI are still in the research and development stage. Before practical application, extensive clinical trials and approval processes are required to ensure their safety and effectiveness.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 5.4. Biosensors  \n\nHydrogels, as a kind of materials for preparing electronic skin and wearable devices as biosensors, have numerous advantages. For instance, hydrogels exhibit good flexibility and elasticity, allowing it to have better contact and adherence to human skin, thus increasing comfort when worn [149,150]. Hydrogels also possess excellent water absorption properties, which can help maintain the moisturization and stability of the skin. Additionally, hydrogels exhibit good conductivity, which can provide stable signal transmission and response [151–153]. As a potential candidate material for biosensors, the requirements for various properties of hydrogels are extremely demanding. However, relying on traditional material screening methods and optimization strategies greatly limits the design and preparation of advanced hydrogels, as the addition of more and more components during the material preparation process is required to enhance and regulate their mechanical, biomedical, electrical, and self-healing properties [154–156]. Because of its unique advantages in component screening, characterization analysis and performance optimization of hydrogels, AI is extremely important in the preparation of advanced electronic skin and wearable devices.  \n\nFor instance, high-throughput screening enables efficient and sys­ tematic exploration of the effects of multiple components on poly­ sulfobetaine hydrogel properties, thus providing a valuable database for diverse applications. Through high-throughput screening, the authors obtained optimized polysulfobetaine hydrogels and demonstrated that this electronic skin processing exceptionally mechanical properties and self-healing capabilities at ambient conditions (Fig. 12) [157]. This work not only extends the high-throughput synthetic methodology to the field of hydrogel electronics but also opens up new avenues for healable flexible electronic devices through advancements in material develop­ ment and device design.  \n\nBy combining AI technology, electronic skin can achieve more intelligent functions. For example, by sensing environmental changes and physiological parameters of the human body, biosensors can monitor health conditions in real time and provide personalized health advice [158,159]. In addition, electronic skin can also communicate wirelessly with other devices or systems, enabling more convenient in­ formation exchange and control operations [160]. Through integration with ML module and proper training, the hydrogel-based platform achieved high accuracy in recognizing human handwriting movements, ranging from individual letters to words, phrases, and short sentences. This hydrogel-based ionic skin combines superior mechanical properties with self-evolving sensing capabilities, unleashing its potential as an intelligent human-device interface and promoting the application of AI in customized electronic devices [161].  \n\nIt should be noted that further research and experimental validation are necessary for the development of this technology to ensure the sta­ bility, safety, and reliability of electronic skin. Moreover, considerations regarding personal privacy and data protection need to be taken into account during its application.  \n\n![](images/7ec453d8b751304c5179f16fd93cf2d6ca3902cfbc3970cd2832b128ddb6518b.jpg)  \nFig. 12. (A) Overview of high-throughput multi-channel feeder. (B) Schematic diagram of material synthesis reactions. (C) The device structure of the hydrogelbased capacitive sensor and its response to applied pressure before cutting and after self-healing are analyzed. Adapted with permission [157]. Copyright $\\circledcirc$ 2021, Wiley-VCH GmbH.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 6. Summary and perspectives  \n\nHydrogels are materials with a high-water content that exhibit unique properties, making them suitable for various applications [162]. However, the developmental workflow of hydrogels, which is largely based on trial and error and requires significant amounts of time and material resources, alike has remained slow-moving due to some bot­ tlenecks in the design, optimization and application of hydrogels. AI has made significant advances in various fields, including the design and optimization of hydrogels for biomedical applications. AI can help alleviate this burden by obtaining insights from generated data to ach­ ieve more targeted and predictive experimental methods. AI-energized hydrogel design involves using ML algorithms to analyze large data­ sets and identify optimal combinations of polymers, cross-linking agents, and other additives to create hydrogels with specific proper­ ties. By leveraging AI, researchers can accelerate the process of designing and optimizing hydrogels with desired characteristics, such as mechanical strength, porosity, biocompatibility, and drug release pro­ files. Energized by AI, hydrogels have shown advanced applications in tissue engineering, including drug delivery, bio-inks for advanced manufacturing, tissue repair, and biosensors.  \n\n![](images/a85d63a49ac65c21434fc23f61b315b48698b1346ffde0a87141e67579bd737a.jpg)  \nFig. 13. The current development trends and potential applications of AIenergized design and optimization of hydrogels in biomedicine.  \n\nBesides these already developed biomedical applications, AIenergized hydrogel design and optimization also has potential applica­ tions in a number of other fields (Fig. 13). For example, the utilization of ML-based methods shows promise for both soft robot proprioception and object recognition when resistive or capacitive readings are accessible [163,164]. The combination of recently developed physics engines and deep learning is utilized to optimize soft robots [165]. These gradient-based optimization methods have the potential to be more computationally efficient. In addition, through simulation of virtual robots using data-driven models, it becomes possible to concurrently optimize various objectives, including geometry, controller models, and physical system properties for system identification [166]. Using ML to assist in sensing and control holds great potential as it can expand the capabilities of intelligent robotics systems. In addition, AI-energized hydrogels also are expected to play an important role in personalized medicine with a focus on cancer therapy and immunovaccines. On the one hand, AI using ML algorithms to recognize and predict the pattern of various factors in the tumor microenvironment, including analyzing the gene expression pattern, protein level and cell type of tumor tissue, as well as predicting the tumor’s response to different treatments. On the other hand, through the acquisition of these data, AI-energized design and optimization of hydrogels can better mimic and build 3D tumor microenvironments, and is expected to provide equal or even better practicality than animal models or other preclinical models.  \n\nOne area where AI has been particularly useful is in predicting the behavior of hydrogels in complex biological environments [167]. Traditional methods for hydrogel design and optimization often rely on trial-and-error approaches, which can be time-consuming and costly. AI algorithms can analyze existing experimental data to identify patterns and correlations between hydrogel composition and performance. This information can then be used to predict the behavior of new hydrogel formulations and guide the design process. Furthermore, AI can also aid in the discovery of novel hydrogel materials by performing virtual screening of large databases, simulating molecular interactions, and predicting the properties of potential candidate molecules. This can help researchers identify promising candidates for further experimental testing, potentially saving time and resources. In addition to design and discovery, AI can also assist in optimizing the manufacturing process of hydrogels. By analyzing process parameters and experimental data, AI algorithms can help identify optimal conditions for hydrogel synthesis, resulting in improved reproducibility and scalability. In summary, AI offers valuable tools and techniques for the design and optimization of hydrogels. By leveraging ML, optimization algorithms, and generative models, AI can accelerate the development of advanced hydrogel ma­ terials with applications in various fields.  \n\nDespite this potential, the development of AI-energized multifunc­ tional hydrogel products is still at a preliminary stage. The utilization of AI generally necessitates a larger volume of data for training, validation, and testing purposes. For example, in the development of hydrogel drug delivery system, in addition to effectively modulating the input pa­ rameters, it is crucial to have sufficiently informative output hydrogel release. The availability of abundant experimental data covering both the input parameters and output release would facilitate the develop­ ment of enhanced predictive insights into the relationships. Therefore, there is a need to establish a centralized and standardized system for collating hydrogel drug release results, enabling effortless crosscomparisons between studies [168–170]. One potential avenue is the implementation of a standardized release and testing protocol that re­ searchers can adopt in their investigations. Such a protocol would enable the normalization of initial parameters and variables across different research groups, facilitating more efficient comparisons. Moreover, standardization could be extended to data annotation and processing methods, ensuring the generation of a comprehensive hyperparametric dataset [171].  \n\nIt is important to note that while AI-energized hydrogel design shows great promise, it is still an emerging field. Further research and devel­ opment are needed to fully harness the potential of AI in designing hydrogels for biomedical applications. As technology continues to advance, we can expect AI to play an increasingly crucial role in accelerating the development of innovative hydrogel-based therapies.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 17,
+        "chunk": "# CRediT authorship contribution statement  \n\nZuhao Li: Writing – original draft, Software, Investigation, Data curation, Conceptualization. Peiran Song: Resources, Methodology, Investigation, Formal analysis. Guangfeng Li: Visualization, Validation, Resources, Conceptualization. Yafei Han: Validation, Software, Meth­ odology. Xiaoxiang Ren: Writing – review & editing, Supervision. Long Bai: Writing – review & editing, Supervision, Methodology. Jiacan Su: Writing – review & editing, Supervision, Project administration.",
+        "category": " References"
+    },
+    {
+        "id": 18,
+        "chunk": "# Declaration of competing interest  \n\nThe authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 19,
+        "chunk": "# Data availability  \n\nData will be made available on request.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# Acknowledgements  \n\nThis work was financially supported by National Natural Science Foundation of China (82230071, 82172098), Integrated Project of Major Research Plan of National Natural Science Foundation of China (92249303), Shanghai Committee of Science and Technology (23141900600, Laboratory Animal Research Project), Shanghai Clinical Research Plan of SHDC2023CRT01, Young Elite Scientist Sponsorship Program by China Association for Science and Technology (YESS20230049).",
+        "category": " References"
+    },
+    {
+        "id": 21,
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+        "id": 1,
+        "chunk": "# AI-guided few-shot inverse design of HDPmimicking polymers against drug-resistant bacteria  \n\nReceived: 26 September 2023  \n\nAccepted: 11 July 2024  \n\nPublished online: 26 July 2024  \n\nCheck for updates  \n\nTianyu Wu1,7, Min Zhou $\\textcircled{1}2,7$ , Jingcheng Zou 3, Qi Chen3, Feng Qian1, Jürgen Kurths 4,5,6, Runhui Liu 2,3 & Yang Tang 1  \n\nHost defense peptide (HDP)-mimicking polymers are promising therapeutic alternatives to antibiotics and have large-scale untapped potential. Artificial intelligence (AI) exhibits promising performance on large-scale chemicalcontent design, however, existing AI methods face difficulties on scarcity data in each family of HDP-mimicking polymers $(<10^{2})$ , much smaller than public polymer datasets $(>10^{5})$ , and multi-constraints on properties and structures when exploring high-dimensional polymer space. Herein, we develop a universal AI-guided few-shot inverse design framework by designing multi-modal representations to enrich polymer information for predictions and creating a graph grammar distillation for chemical space restriction to improve the efficiency of multi-constrained polymer generation with reinforcement learning. Exampled with HDP-mimicking $\\beta$ -amino acid polymers, we successfully simulate predictions of over $10^{5}$ polymers and identify 83 optimal polymers. Furthermore, we synthesize an optimal polymer $\\mathsf{D M}_{0.8}i\\mathsf{P e n}_{0.2}$ and find that this polymer exhibits broad-spectrum and potent antibacterial activity against multiple clinically isolated antibiotic-resistant pathogens, validating the effectiveness of AI-guided design strategy.  \n\nAs the global risk of antimicrobial resistance continues to escalate, it is urgent to develop alternative strategies to combat antibiotic-resistant bacteria1–4. One of the pressing clinical needs is the discovery of promising broad-spectrum antibacterial agents against both Grampositive and Gram-negative bacteria, especially against antibioticresistant pathogens5,6. Host defense peptides (HDPs) have garnered considerable attention owing to the advantages of broad-spectrum antibacterial property and low susceptibility to antimicrobial resistance7,8. However, the application of HDPs is hindered by their easy enzymatic degradation and expensiveness9,10. HDP-mimicking polymers have been designed to address the shortcomings of natural HDPs and have emerged as promising antimicrobial alternatives11–15. Furthermore, the discovery of HDP-mimicking antibacterial polymers is limited to conventional designing and optimization strategy, which is semiempirical and inefficient. Artificial intelligence (AI) enables rapid design and optimization of various chemical-contents16–21, and it is expected to substantially accelerate the discovery of promising HDPmimicking polymers22–25.  \n\nNevertheless, two orthogonal challenges inhibit the practical usage of AI for polymers design, specifically in polymer prediction and polymer generation. For polymer prediction, the available few-shot data of peptide-mimicking polymers $10^{2}$ or even fewer) in each family is much smaller than data of polymers from public datasets $(10^{5}–10^{6}$ or even more)26–28. This scarcity of data leads to a serious issue for causing overfitting of the predictive model when method transfer, resulting in a decline in performance of the predictive models. For polymer generation, polymer space is constructed by numerous variables of polymers in structures, composition, chain length etc., presenting challenges for AI to efficiently and accurately explore for reasonable polymers with multiple desirable property constraints, of which some may even be inversely related, in the vast high-dimensional polymer space29. This challenge implies that the existing AI methods focus more on optimizing polymers with tailored sequence or composition, since these polymers can be coarse-grained simulated or enumerated30, than exploring for novel chemical structures for subunits31–33. Consequently, there is an urgent need to develop an efficient AI method which is capable of predicting and generating novel polymer structures with multi-constraints using few-shot polymer data.  \n\nTo address those two challenges above, herein we develop an endto-end AI-guided few-shot inverse design framework to realize an effective exploration of novel polymers under the condition of fewshot data and multiple constraints in high-dimensional polymer space. To enhance the performance of predictive model for polymers, we construct multi-modal polymer representations to enrich the multiscale polymeric information for few-shot polymer data. This increases the alignment between predictive models and actual polymer systems compared to one single representation34,35. To accurately explore for novel polymer structures within desired properties, we develop a grammar knowledge distillation, which distills a graph grammar fragment set according to the existed few-shot polymer data and recombines these grammar as distilled molecules set to restrict the highdimensional polymer space. These process contributes to improve the efficiency of AI exploration under multi-constraints and ensure the chemical rationality and availability of polymer structures. HDPmimicking $\\beta$ -amino acid polymers have attracted significant attention and demonstrated enormous potential for various applications due to striking structural similarity to natural peptides, superior biocompatibility and high resistance to protease hydrolysis13,36–38. By implementing our AI design framework, using only 86 HDP-mimicking $\\beta$ -amino acid polymers as a model39–43, we successfully simulate predictions of over $10^{5}$ polymers and indeed identify 83 candidates exhibiting broad-spectrum activity against antibiotic-resistant bacteria. In addition, we synthesize an optimal polymer DM0.8iPen0.2 and find that this polymer demonstrates broad-spectrum and potent antibacterial activity against drug-resistant clinically isolated pathogens, which validates the effectiveness and reliability of our AI design method. Furthermore, our framework is a completely data-driven method and it can be universally transferred to various few-shot polymer design tasks. With constructing proper predictive model and generative model, the usage can be further expanded. In one word, AI-guided polymer design accelerates the discovery of potent antimicrobial agents against antibiotic-resistant bacteria and offers a promising strategy to combat antibiotic resistance.  \n\ninfluenced by varying the side chain hydrophobicity (side chain carbon atom number and its atomic spatial arrangement) and the ratio of hydrophobic component/positively charged component. The antibacterial activity data including the minimum inhibitory concentration (MIC) values of polymers against Gram-positive bacterial Staphylococcus aureus (S. aureus) and Gram-positive bacterial Escherichia coli (E. coli), as well as hemolytic toxicity data was collected with the minimum concentration to cause $10\\%$ hemolysis $\\mathrm{(HC_{10})}$ values (Supplementary Data 1). Due to the characteristics of abundant structures of $\\beta$ -amino acid polymers, we conducted a refined classification according to the different position of side chain substituents and cyclic/non-cyclic substitution pattern and defined 11 scaffolds to accurately characterize the polymer structure one-on-one (Fig. 1a, Supplementary Fig. 2, Supplementary Table 1 and Supplementary Data 2). Secondly, we transformed the polymer structure into multimodal polymer representations to capture comprehensive multi-scale polymer information for training the predictive model so as to enhance the model performance (Fig. 1b). Then, we developed a graph grammar distillation method to pre-train the generative model for generating $\\beta$ -amino acid polymers structures which tend to rationality and availability based on the chemical principle (Fig. 1c). Specifically, the chemical structure of collected $\\beta$ -amino acids polymer aforementioned and homologous natural $\\alpha$ -amino acids were resolved into a variety of molecular graph grammar fragments, which were subsequently recombined to form new molecules (Supplementary Data 3). The process of resolution-recombination was iterated and these recombined mass molecules were used for pre-training the generative model (Supplementary Data 4 and Supplementary Data 5), allowing for the generation of a more focused polymer chemical space. Our graph grammar distillation method could not only contribute to restrict the vast and high-dimensional chemical space of polymers but also generate more reasonable novel polymer structures for practical usage. Finally, we combined these two pre-trained models in reinforcement learning (RL) to form a polymer inverse design framework. The predictive and the generative model were respectively regarded as the environment and the agent to construct a RL pattern. The generative model generated a set of novel polymers and the predictive models provided the corresponding rewards after the evaluation of their bioactivity and structures. Through these rewards, the parameters of the generative model were updated to search for new polymer structures in next RL episode. With such iteration of generative and predictive model, a set of candidate polymers were finally discovered according to the predefined bioactivity values.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Construction and evaluation of the multi-modal polymer representations",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 3,
+        "chunk": "# Results",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# Framework overview  \n\nTo overcome the limitation associated with the limited information available from few-shot polymers, we employed the multi-modal polymer representations to extract comprehensive multi-scale polymer information. First, we constructed a text-sequence polymer representation using BigSMILES44 and we further introduced a definition to incorporate information about the proportion of cationic and hydrophobic subunits in the polymer chain, so as to extract the globallevel polymer information.  \n\nThe main procedure of our polymer inverse design framework was illustrated in Fig. 1. First, we collected a set of existing data comprising chemical structures and their bioactivity activity of HDP-mimicking $\\beta$ - amino acid polymers. The chemical structure of the totally 86 polymers was composed of a positively charged subunit (dimethyl (DM), monomethyl (MM)) and a hydrophobic subunit (cyclopentyl (CP), cyclohexyl (CH), etc.) in different proportions with the total chain length of 20 (Fig. 1a and Supplementary Fig. 1). Previous studies indicated that the biological activity of $\\beta$ -amino acid polymers was mainly  \n\nSecondly, we constructed a polymer graph representation by concreting the linking rules of bonding descriptors in BigSMILES syntax, which demonstrated the connection relationships between the subunits in polymer, as new nodes and edges in polymer graph to extract local-level polymer information (see Methods). Finally, we utilized the descriptors from the Mordred calculator45 to describe the characteristics and properties of cationic and hydrophobic subunits. To ensure as much information as possible are embedded in descriptors, we employed a machine learning-based descriptor downselection process46, filtering out 40 optimal descriptors with strong correlation to target activity from the original 3654 descriptors (see Methods). In all subunits are achiral. b We conduct a multi-modal polymer representation method, including text sequence, graph with additional polymer settings and descriptors embedded with 2D- and 3D-properties of subunits to expand for multiscale polymer information to realize few-shot polymer prediction. c We develop a graph grammar distillation method in which we utilize $\\beta$ -amino acids and natural $\\alpha$ - amino acids to learn the split graph grammar fragments. These fragments are reconstructed as distilled molecule dataset to pre-train the generative model to restrict the huge chemical space for exploration.  \n\n![](images/3a9a280a341ad654f3e2283565cca790d07df27e42a3f7f93d17998a25f6ae8a.jpg)  \nFig. 1 | Framework overview. a By collecting 86 data comprising chemical structures and their bioactivity of $\\ddot{\\boldsymbol{\\beta}}$ -amino acid polymers, we develop an AI-guided fewshot inverse design framework to find promising polymers with broad-spectrum antibacterial efficacy and low cytotoxicity. In addition, we conduct a refined classification according to the different position of side chain substituents and cyclic or non-cyclic substitution pattern, which defines a scaffold set for the following polymer generation. x and y are defined as the percentages of a positively charged subunit and a hydrophobic subunit in $\\beta$ -amino acid polymers, respectively. ${}^{\\mathfrak{n}}\\mathbb{R}_{1},\\mathbb{R}_{2},$ ${\\bf R}_{3},{\\bf R}_{4}^{\\prime\\prime}$ means that more than one substitution point should be decorated. Note that  \n\naddition, we conducted the data augmentation on three multi-modal polymer representations by introducing permutation invariance47, which allowed for significant reductions in prediction errors for multicomponent systems (see Methods).  \n\nIn this manuscript, we randomly selected $80\\%$ of collected 86 polymers as the training set $D_{t r a i n\\_o r i}$ and the rest of $20\\%$ of data were set as the unseen testing set $D_{t e s t}$ . Thus, all models were trained and evaluated in same data situation. We first evaluated the performance of applying descriptor downselection and data augmentation that were two important operations of influencing the input representations. We defined an augmented training data $D_{t r a i n\\_a u g},$ which contained original training data $D_{t r a i n\\_o r i}$ along with additional data by tuning all possible polymer sequences of cationic and hydrophobic subunits in all representations. In this stage, we constructed 4 classic machine learning based regression models, including Gradient Boosting Decision Tree (GBDT)48, Random Forest $(\\mathsf{R F})^{46}$ , Extreme Gradient Boosting $(\\mathsf{X G B})^{49}$ and Adaptive Boosting (Adaboost)50 for bioactivity prediction. The model performance was characterized by calculating the mean R-squared coefficient (R2). We applied a 15-fold cross validation on $D_{t r a i n\\_o r i}$ and $D_{t r a i n\\_a u g}$ to evaluate the performance of different models with fixed descriptors (Fig. 2a–l and Supplementary Fig. 9).  \n\nGenerally speaking, GBDT models performed best than other methods on each task (Fig. $2\\mathsf{a}\\mathsf{-c}$ for GBDT, Fig. 2d–f for RF, Fig. 2g–i for XGB, Fig. 2j–l for Adaboost). The results showed that the mean R2 values of GBDT for $D_{t r a i n\\_o r i}$ increased gradually to the 0.626, 0.640 and 0.795 on predicting the values of MICS.aureus, $\\mathbf{MIC}_{E.c o l i}$ and $\\mathsf{H C}_{10}$ of polymers with applying descriptors downselection, showing that more related information was selected step by step (Fig. $2\\mathsf{a-c},$ blue boxes). After applying data augmentation, the mean R2 values showed a more obvious increase to 0.739, 0.681 and 0.831 for $D_{t r a i n\\_a u g}$ compared to using $D_{t r a i n\\_o r i},$ indicating the increased prediction accuracy (Fig. 2a–2c, red boxes). Via a final evaluation with GBDT on $D_{t e s t},$ the mean R2 values reached 0.672, 0.537 and 0.834 for ${\\sf M I C}_{S}$ .aureus, $\\mathsf{M I C}_{E.c o l i}$ and $\\mathsf{H C}_{10},$ regarding as a machine learning baseline in this manuscript. Results for all machine learning models on $D_{t e s t}$ were demonstrated in Fig. $2\\mathsf{m}\\mathrm{-}\\mathsf{o}$ .  \n\nMoreover, we further studied the performance of all the predictive network by combing three modals of text sequence of polymer, polymer graph and descriptors with applying descriptor downselection and data augmentation discussed before. In addition, we added GBDT, RF, XGB and Adaboost as basic benchmark models and we also introduced the most commonly used polymer representation of Morgan fingerprints51,52 for comparison. All models were trained on $D_{t r a i n\\_a u g}$ and evaluated on $D_{t e s t}$ for performance comparison, and R2 was again used as the metric. We designed different deep neural network structures for each single representation and an integrated framework for multi-modal representations (see Methods). With final evaluation on $D_{t e s t},$ it was obviously found that GBDT again demonstrated the best in all machine learning based models with mean R2 values of 0.672, 0.537 and 0.834 for MICS.aureus, $\\mathsf{M I C}_{E.c o l i}$ and $\\mathsf{H C}_{10}$ (Fig. $2\\mathsf{m}\\mathrm{-}\\mathsf{o},$ ). The “Descriptor_Opt” demonstrated the best in all single representation with mean R2 values of 0.606, 0.415 and 0.852, whereas the mean R2 values of Morgan was 0.606, 0.415 and 0.852. In addition, the combination of three modals “Seq+Graph $^+$ Descriptor_Opt” showed the highest mean R2 values at 0.697, 0.556 and 0.900, indicating that our constructed multi-modal polymer representations obviously improved the accuracy and stability of the predictive model for few-shot polymers (More results concluded in Supplementary Fig. 13 and Supplementary Tables 3, 4).  \n\nWe further compared in detail about the bioactivity of all polymers between the predictive values and the real measured ones (Fig. 3a). We divided the data according to the positively charged subunit and hydrophobic subunit so as to more rigorously embody the differences of the compositions (Supplementary Fig. 1). Note that log transformation was performed to all the estimated results. The final R2 scores of our model reached 0.91, 0.88 and 0.91 on MICS.aureus, $\\mathsf{M I C}_{E.c o l i}$ and $\\mathsf{H C}_{10}$ for DM series polymers, and 0.92, 0.84 and 0.96 on MM series polymers. It was obviously found from the radar plot that the predicted values highly fit real measured values, indicating that our predictive model was capable of making credible predictions of the bioactivity of $\\beta$ -amino acid polymers.  \n\nMoreover, considering the variegation of antibacterial polymers and the rarity of partial types of polymers, we evaluated the transferability of our proposed method in order to broaden its applicability. We collected additional data on $\\alpha$ amino acid polymers53, polymethacrylates54–57, polymethacrylamides58 and other categories59–61 to evaluate the transferability of our model (Supplementary Data 6). Note that we use the metric of mean absolute error (MAE) to show direct difference of the transferability performance of our model in different categories of antibacterial polymers. According to the evaluated results, for $\\alpha$ -amino acid polymers, the MAE was only 0.51 and 0.79 for $\\mathsf{M I C}_{S.a u r e u s}$ and ${\\sf M I C}_{E.c o l i},$ which was close to the MAE of $\\ddot{\\beta}$ -amino acid polymers (0.17 and 0.40 for $\\mathsf{M I C}_{S.a u r e u s}$ and $\\mathsf{M I C}_{E.c o l i},$ Fig. 3b–e). This fact suggested promising prospects for transferring our method to other categories of antibacterial polymers that possess similar structural characteristics to $\\beta$ amino acid polymers. For polymethacrylates, the MAE reached 1.24 and 1.95 (nearly six times than $\\beta$ -amino acid polymers) for $\\mathsf{M I C}_{S.a u r e u s}$ and ${\\sf M I C}_{E.c o l i},$ respectively (Fig. 3f–i). For polymethacrylamides, the MAE reached 2.33 and 3.75 (nearly ten times than $\\beta$ -amino acid polymers) for $\\mathsf{M I C}_{S.a u r e u s}$ and $\\mathsf{M I C}_{E.c o l i},$ respectively (Fig. $3\\mathbf{j}\\mathbf{-}\\mathbf{m})$ . These results showed that our model encountered challenges when predicting the properties of other polymers for example polymethacrylates and polymethacrylamides due to substantial dissimilarities with $\\beta$ -amino acid polymers. In summary, our model demonstrated promising transferability to $\\alpha$ -amino acid polymers which had highly similarity with our trained data of $\\beta$ -amino acid polymers, while our model were not suggested to be directly transferred to other categories before we further improved the performance of the model (All results shown in Supplementary Figs. 14–22).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# Performance evaluation of graph grammar distillation  \n\nWe evaluated the performance of the generative model produced from the pre-training of graph grammar distillation using ChEMBL62 as a control, which was a commonly used dataset to pre-train a generative model and included abundant and diverse chemical structures. We conducted a fine-tuning process with reinforcement learning (RL) for 450 iterations on these two pre-trained generative models to generate polymer subunits with desired chemical structures in multiple given constraints of carbon atoms number and elemental composition in the side chain structure (Task 1 in Method). The generated subunits were scored as reward feedback (details of the rewards see Methods). The subunit that met the given constraints would get a positive reward, and the subunit that did not met the constraints would get a negative reward.  \n\nThe results showed that in the last several iterations in RL training, the average total rewards of polymers on the values of MICS.aureus and carbon atom constraints for graph grammar distillation pre-trained generative model got a positive value, indicating that the generated subunits met the design requirements (Fig. 4a). In contrast, the corresponding average total rewards in the ChEMBL pre-trained generative model obtained the negative values (Fig. 4a), indicating that many generated subunits were hard to meet the design requirements, especially for carbon atom constraint (Fig. 4b, c). More comparative results between the model pre-trained by ChEMBL and graph grammar distillation were shown in Supplementary Figs. 25–27. We further evaluated the performance of the graph grammar distillation pretrained generative model in multi constraints of all three bioactivities, polymer carbon atom number and carbon ring number (Task 2 in Methods, Supplementary Figs. 28, 29). These results exhibited that graph grammar distillation successfully restricted the highdimensional chemical space and the generative model pre-trained by refer to the most extreme, nonoutlier data points, with minima on the left and maxima on the right. $\\mathbf{m}\\mathbf{-}\\mathbf{0}$ Property prediction results of unseen test set $D_{t e s t}$ with deep neural network on $\\mathsf{M I C}_{S.a u r e u s},$ $\\mathsf{M I C}_{E.c o l i}$ and $\\mathsf{H C}_{10}$ with different polymer representation combination $(n=10)$ ). The borders of the boxes indicate the first quartile (left) and the third quartile (right) of the results. The line in the box indicates the median. The whiskers refer to the most extreme, nonoutlier data points, with minima on the left and maxima on the right. “Seq” is the abbreviation of “Sequence” (Source data are provided as a Source Data file).  \n\n![](images/93a8b473639ff9068fc7e860aa2bfed1ea5ca8e90909552d901c8f7e7b84b2d2.jpg)  \nGradient Boosting Decision Tree (GBDT, a–c), Random Forest (RF, d–f), Extreme Gradient Boosting (XGB, $\\mathbf{g-i})$ , Adaptive Boosting (Adaboost, j–l) for applying descriptors downselection and data augmentation on predicting the values of the minimum inhibitory concentration (MIC) for S. aureus $(\\mathbf{MIC}_{S.a u r e u s})$ and E. coli $(\\mathsf{M I C}_{E.c o l i})$ and the value of the minimum concentration to cause $10\\%$ hemolysis $\\mathrm{(HC_{10})}$ with the metric of R-squared coefficient (R2). Descriptor_Init to Descriptor_Opt are different sets of descriptors (from the initial set to the optimized set) when downselection. Red boxes are results for augmented data and the bules for original data. The borders of the boxes indicate the first quartile (left) and the third  \n\nit possessed the strong capabilities for an efficient customized generation of polymer subunits.  \n\nTo verify the structural diversity of generated polymers by our generative model under multiple constraint conditions, we generated the $\\beta$ -amino acid polymer library consisting of 2114 types of hydrophobic subunits for every cationic subunit and visualized all hydrophobic subunits with Topological Data Analysis Mapper $({\\mathrm{TMAP}})^{63}$ . These hydrophobic subunits covered the possible side chain structures, encompassing various substitution forms, equally distributed as the defined scaffolds, including the representative six styles of $\\beta$ -amino acid polymers (Fig. 4d). This indicated that our graph grammar distillation based generative model was able to generate various of $\\beta$ -amino acid polymers with abundant cationic and hydrophobic subunits for the discovery of novel antibacterial candidates.  \n\n![](images/ce0213bcf6061402fdf1e2715b8a6f1d8803b669a905f94415c9b1f723aab9c5.jpg)  \nFig. 3 | Results of the predictive model. a Comparison between predicted values and real measured values for $\\beta$ -amino acid polymers. Results show a desirable accuracy, with the metric of R-squared coefficient (R2) reaching 0.91, 0.88 and 0.91 on the values of the minimum inhibitory concentration for S. aureus $(\\mathsf{M I C}_{S.a u r e u s})$ , E. coli $(\\mathsf{M I C}_{E.c o l i})$ and the value of the minimum concentration to cause $10\\%$ hemolysis $\\mathrm{(HC_{10})}$ on polymers with dimethyl (DM) subunit, and 0.92, 0.84 and 0.96 on polymers with monomethyl (MM) subunit. Text abbreviations (HE, OC, etc.) mean   \ndifferent hydrophobic subunits. All values are transformed values by natural logarithm. b–m Comparison between predicted values and real measured values for $\\alpha\\cdot$ amino acid polymers (b), polymethacrylates (f) and polymethacrylamides (j). Predicted values on MICS.aureus (c, g, k) and $\\mathtt{M I C}_{E.c o l i}$ (d, h, l) in various proportion are recorded with natural logarithmic transformation (log). We also visualize mean absolute error (MAE) of the predictions for each polymer $(\\mathbf{e},\\mathbf{i},\\mathbf{m})$ to show the difference when model transferring (Source data are provided as a Source Data file).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# Visualized analysis of AI-predicted structure and activity of $\\pmb{\\beta}$ -amino acid polymers  \n\nWe made overall predictions on three bioactivities of the generated cationic-hydrophobic $\\beta$ -amino acid polymers with the aforementioned 2114 types of hydrophobic subunits. The ratio of cationic to hydrophobic subunit was limited to 0.1 to 0.9 (9 samples). Thus, the bioactivity data of 19,026 polymers could be generated for each cationic subunit. Taking the DM/MM as a representative cationic subunit, we visualized three predicted distributions of the bioactivities of MICS.aureus, $\\mathsf{M I C}_{E.c o l i}$ and $\\mathsf{H C}_{10}$ and we further categorized the polymers according to the different ranges of carbon numbers in hydrophobic subunits (Fig. 4e–j). According to the prediction, for polymers with DM subunit, concretely $85.0\\%$ , $92.2\\%$ and $92.8\\%$ of polymers in each range (5-6, 7-8 and 10-11) reached the MIC values $<25\\upmu\\mathrm{g}\\mathsf{m}\\mathsf{L}^{-1}$ against S. aureus (Fig. 4e) and $44.1\\%$ , $36.5\\%$ and $28.6\\%$ against E. coli (Fig. 4f). Whereas, for polymers with MM subunit, less polymers possessed high activity against S. aureus and $E.$ . coli with MIC value $<25\\upmu\\mathrm{g}\\mathrm{m}\\mathrm{L}^{-1}$ and $7.2\\%$ , $29.7\\%$ and $21.7\\%$ polymers in each range reached the value against S. aureus (Fig. 4h) and $7.5\\%$ , $2.1\\%$ and $0.0\\%$ against $E.$ coli (Fig. 4i). These results indicated that the polymers with DM subunit showed greater opportunities to explore the promising broad-spectrum antibacterial polymers. Moreover, for the given threshold of $\\mathsf{H C}_{10}$ value $>50\\upmu\\mathrm{g}\\ \\mathsf{m}^{-1}$ , no matter what the cationic subunit was DM or MM, the ratios of the generated polymers in 19,026 samples gradually decreased with an increasing carbon number (Fig. $\\mathbf{4g},\\mathbf{j})$ . The aforementioned findings guided us to select an appropriate range of carbon numbers $(<11)$ for better polymer activity in the following design.  \n\n![](images/b5c762fd1d672b5f9e204d21522ac57a74736ff8e180e2ce71a28a27e1f1d89d.jpg)  \nFig. 4 | Results of the generative model and visualized analysis. a–c Average reward curves show opposite model performance when fine-tuning model pretrained by graph grammar distillation (red) and ChEMBL dataset (blue) with reinforcement learning. Total reward consists of the constraints about the values of the minimum inhibitory concentration for S. aureus $(\\mathsf{M I C}_{S.a u r e u s})$ and number of carbon numbers (less than 11). A higher reward means that the model generates more desired structures as expected. d Overview of the Topological Data Analysis Mapper (TMAP) for 2114 generated hydrophobic subunits colored by the corresponding scaffolds. Subunits with the same scaffolds are generally clustered  \n\ntogether. Note that all subunits are achiral. Cluster A–E include the representative six styles of $\\beta$ -amino acid polymers which are mostly appeared in our data. e–j Property prediction distributions on three bioactivities, including the values of the minimum inhibitory concentration for S. aureus $(\\mathsf{M I C}_{S.a u r e u s})$ , E. coli $(\\mathbf{MIC}_{E.c o l i})$ and the value of the minimum concentration to cause $10\\%$ hemolysis $\\mathrm{(HC_{10})}$ , for the generated $19,026\\beta$ -amino acid polymers with fixed dimethyl (DM, $\\mathbf{e}{\\boldsymbol{-}}\\mathbf{g})$ or monomethyl $(\\mathsf{M M},\\hslash-\\mathbf{j})$ positively charged subunits. Ratios of polymers in different carbon range which reach the threshold of specific bioactivity are calculated (Source data are provided as a Source Data file).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# Visualized analysis of AI-predicted antibacterial selection index (SI) of $\\pmb{\\beta}$ -amino acid polymers  \n\nWe further made overall predictions on antibacterial SI of the generated $\\beta$ -amino acid polymers as one of the important parameters to evaluate selectivity and safety of the antibacterial agents64. Herein, we focused on exploring the optimal antibacterial $\\beta$ -amino acid polymer with a high SI value by finding the suitable hydrophobic subunit using DM as cationic subunit. We used a uniform manifold approximation and projection $(\\mathsf{U M A P})^{65}$ to project all $\\beta$ -amino acid polymers with DM subunit onto a 2D embedding chemical space (Fig. 5). We collected the SI values of all generated 19,026 polymers by calculating ${\\mathsf{H C}}_{10}/{\\mathsf{M I C}}$ against S. aureus and E. coli, respectively, and we conducted the classification and visualized analysis on these data according to the range of SI. Finally, we filtered out 9 broad-spectrum antibacterial candidates with both high activities and SI values including 4 different structures of hydrophobic subunits. It was worth noting that most suboptimal polymers (greed, gray and yellow points) were clustered near the candidates (red star), which inspired us to make a detailed exploration for the hidden candidates in the near space of the optimal polymer points.  \n\nDiscovery of broad-spectrum antibacterial candidate polymers We run our framework to discover broad-spectrum antibacterial polymers with desirable bioactivities $(\\mathsf{M I C}_{S.a u r e u s}<25\\upmu\\mathrm{g}\\quad\\mathsf{m L}^{-1},$ $\\mathsf{M I C}_{E.c o l i}<25\\upmu\\mathrm{g\\mL^{-1}}$ and $\\mathsf{H C}_{10}>100\\upmu\\mathrm{g\\mL^{-1}},$ . We conducted a systematical exploration for candidate polymers by using different $\\beta$ - amino acid polymer scaffolds (Supplementary Figs. 30–50), and finally found 83 novel broad-spectrum antibacterial candidates by limiting the carbon number of hydrophobic subunit to less than 11 (Supplementary Tables 6–20). Displaying the scaffold of $\\beta^{3}$ -amino acid as a hydrophobic subunit example model (Task 3 in Methods), we collected 640 $\\beta$ -amino acid polymers using DM as the cationic subunit and various substituted $\\beta^{3}$ -amino acids in the RL fine-tuning process (Fig. 6a). We made a prediction on the values of MICS.aureus, $\\mathsf{M I C}_{E.c o l i}$ and $\\mathsf{H C}_{10}$ with the predictive model, and projected all values in a 3Dspace with the three properties as coordinates (Fig. 6b). From these results, we finally filtered out 5 candidate polymers in this polymer generated $\\beta^{3}$ -amino acid polymers with fixed DM subunit. Blue plots describe the distribution of each generated polymer coordinated with ( $\\mathsf{H C}_{10},\\mathsf{M I C}_{S.a u r e u s}$ and $\\mathsf{M I C}_{E.c o l i})$ according to the predicted value. Orange plots are the projection on $(\\mathsf{H C}_{10},\\mathsf{M I C}_{S.a u r e u s})$ space, green plots are the projection on $(\\mathrm{HC}_{10},\\mathrm{MIC}_{E.c o l i})$ space, while purple plots are the projection on $(\\mathsf{M I C}_{S.a u r e u s},$ $\\mathsf{M I C}_{E.c o l i})$ space. Red stars are polymers reaching three desired properties of $\\mathsf{M I C}_{S.a u r e u s}<25$ $\\mathsf{M I C}_{E.c o l i}<25$ and $\\mathsf{H C}_{10}>\\mathsf{100}$ , simultaneously.  \n\n![](images/8412a2384b70a4524df5e9b8589d674b22321980eeffef9ae21b330fe6322ec5.jpg)  \nFig. 5 | Chemical space visualization with Uniform manifold approximation and projection (UMAP) colored by the selected index (SI) values of generated polymers. We construct a chemical space with the generated polymers bearing dimethyl (DM) as positively charged subunit. Each polymer is colored according to the values of the SI for S. aureus $(\\mathsf{S l}_{S.a u r e u s})$ and $E.$ . coli $(\\mathsf{S l}_{E.c o l i})$ by the predictied values of the minimum inhibitory concentration for S. aureus $(\\mathbf{MIC}_{S.a u r e u s})$ , E. coli   \n$(\\mathsf{M I C}_{E.c o l i})$ and the value of the minimum concentration to cause $10\\%$ hemolysis $\\mathrm{(HC_{10})}$ . Polymers with desirable SI values $(\\mathsf{S l}_{S.a u r e u s}>10\\$ and $\\mathsf{S l}_{E.c o l i}>10)$ are displayed with red stars. Moreover, it can be clearly found that most suboptimal polymers with $\\mathsf{S l}_{S.a u r e u s}{>}5$ or $\\mathsf{S l}_{E.c o l i}{>}5$ (green, yellow and gray points) are clustered together nearby the red star points, meaning that more potential structures exist around them (Source data are provided as a Source Data file).  \n\n![](images/30f7205e3013af95b12114708950575cd547f83fbb54b4e846f174b6bd6d2636.jpg)  \nFig. 6 | Discovery of broad-spectrum antibacterial polymers bearing $\\pmb{\\beta}^{3}.$ - amino acid. a Various $\\beta^{3}$ -amino acid generated in the discovery process with fixed dimethyl (DM) subunit. Note that all subunits are achiral. $\\mathbf{x}$ and y are defined as the percentages of a positively charged subunit and a hydrophobic subunit in $\\beta$ -amino acid polymers, respectively. b 3D-projection of the bioactivities on the values of the minimum inhibitory concentration for S. aureus $(\\mathsf{M I C}_{S.a u r e u s})$ , E. coli $(\\mathrm{MIC}_{E.c o l i})$ and the value of minimum concentration to cause $10\\%$ hemolysis $\\mathrm{(HC_{10})}$ for the   \nHC10 means the value of the minimum concentration to cause $10\\%$ hemolysis, while $\\mathsf{M l C}_{S.a u r e u s}$ and $\\mathsf{M l C}_{E.c o l i}$ mean the values of the the minimum inhibitory concentration for S. aureus and E. coli.  \n\n<html><body><table><tr><td colspan=\"6\">Table 1| Display of the final filtered out candidate polymers with predicted properties </td></tr><tr><td>Structure</td><td>Polymer Candidate 1</td><td>x:y</td><td>HC1o(μg mL-1)</td><td>MICs.aureus (μg mL-1)</td><td>MICE.coli(μg mL-1)</td></tr><tr><td>NH NH</td><td></td><td>9:1</td><td>119.6</td><td>8.31</td><td>24.9</td></tr><tr><td>HgN NH NH</td><td>-20 Candidate 2</td><td>7:3</td><td>134.6</td><td>15.5</td><td>14.6</td></tr><tr><td>HgN</td><td>-20</td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>Candidate 3</td><td>8:2</td><td>137.7</td><td>13.9</td><td>15.2</td></tr><tr><td>NH</td><td>Candidate 4</td><td>9:1</td><td>214.8</td><td>12.7</td><td>20.0</td></tr><tr><td>H3N</td><td>Candidate 5</td><td>8:2</td><td>156.9</td><td>10.2</td><td>24.1</td></tr></table></body></html>  \n\nscaffolds which meet ideal properties (MICS.aureus $<25$ , $\\mathsf{M I C}_{E.c o l i}<25$ and $\\mathsf{H C}_{10}>\\mathsf{100})$ (Table 1). In addition, we expanded our model on poly $\\overset{\\cdot}{\\alpha}$ -amino acid) and polypeptoid scaffolds to explore further potential application of our method (Supplementary Figs. 51–55). All experimental settings were same, and we also screened out several broad-spectrum antibacterial candidate polymers.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# Synthesis and broad-spectrum antibacterial validation of AIpredicted $\\pmb{\\beta}$ -amino acid polymers  \n\nIn order to verify the accuracy and reliability of the AI system for predicting antibacterial activity and hemolytic toxicity of HDPmimicking $\\beta$ -amino acid polymers, we selected the $\\beta$ -amino acid polymers $\\mathsf{D M}_{x}i\\mathsf{P e n}_{y}$ from the numerous candidate polymers. Firstly, the DM monomer and iPen monomer were copolymerized and subsequently deprotected to obtain the $\\beta$ -amino acid polymers with different ratios of positive charge and hydrophobicity (Fig. $7\\mathsf{a})^{66}$ . Gel permeation chromatography (GPC) characterization of the $N$ -Bocprotected polymers showed a narrow distribution of molecular weight $(D=1.09\\ –1.15)$ and controllable molecular weight as well as chain length $\\mathrm{(DP=}20\\mathrm{-}23)$ (Fig. 7b and Table 2). Proton nuclear magnetic resonance (1H NMR) of $N$ -Boc-deprotected polymers implied a continuous increase in the proportion of hydrophobic subunit (Fig. 7c).  \n\nThen, we tested the hemolytic toxicity against human red blood cells (hRBCs) and cytotoxicity of this polymer libraries using Human umbilical vein endothelial cell line (HUVEC) and the African green monkey kidney fibroblasts (COS7) cells as representative mammalian cells, and found that the hemolytic and cytotoxic activities increased (values decreased) along with the increasing ratio of the iPen component, with the minimum concentration to cause $50\\%$ hemolysis $\\mathrm{(HC_{50})}$ values dropping from $200\\upmu\\up g\\ \\mathrm{mL}^{-1}$ to $12.5\\upmu\\mathrm{g}\\ \\mathsf{m L}^{-1}$ and the minimum concentration to cause $50\\%$ inhibition $(\\mathrm{IC}_{50})$ values dropping from $200\\upmu\\mathrm{g}\\mathrm{mL}^{-1}$ to $75\\upmu\\mathrm{g}\\mathrm{m}\\mathrm{L}^{-1}$ . When the hydrophobicity ratio reached $30\\%$ , the hemolysis of the polymers was significant (Fig. 7d–f). In addition, we also tested the antibacterial activity of these polymers against multiple drug-resistant Gram positive and Gram negative bacteria including three strains of methicillin-resistant S. aureus (MRSA), clinically isolated multidrug-resistant strains S. aureus R03 and two strains of vancomycin resistant enterococcus (VRE), and two strains of multidrug-resistant Escherichia coli. All these polymers displayed strong and broad-spectrum antibacterial activities with MIC in the range of $6.25{\\mathrm{-}}50\\upmu\\mathrm{g}\\mathsf{m L}^{-1}$ . When the hydrophobicity ratio was in the range of $20\\%$ , the polymers showed potent activities against all bacterial strains with MIC in the range of $6.25{-}12.5\\upmu\\mathrm{g}\\mathrm{mL}^{-1}$ (Table 3). Combining the experimental data of hemolysis, cytotoxicity and antibacterial activities, $\\mathsf{D M}_{0.8}i\\mathsf{P e n}_{0.2}$ as the optimal antibacterial candidate exhibited broad-spectrum and potent antibacterial activity, which was consistent to our results predicted by AI system. Our AI system made accuracy predictions on antibacterial activity, and also found out the cationic/hydrophobic subunit ratio with low toxicity. Furthermore, $\\mathsf{D M}_{0.8}i\\mathsf{P e n}_{0.2}$ showed desirable antibacterial selectivity with SI values against mammalian cells of hRBC, HUVEC and COS7 at 12–32 (Fig. $7\\bf{g}\\mathrm{-i)}$ , and antibacterial SI values bigger than 10 indicated that the candidate has selective antibacterial activity and potential application11,67,68, proving the discovery of promising antimicrobial alternatives. It was worth noting that $\\mathsf{D M}_{0.8}i\\mathsf{P e n}_{0.2}$ possessed a unique structure characterized by different hydrophobic subunits in comparison to previously reported antimicrobial $\\beta$ -amino acid polymers. Importantly, our prediction showed that $\\mathsf{D M}_{0.8}i\\mathsf{P e n}_{0.2}$ had lower cytotoxicity and improved antimicrobial selectivity compared to amphiphilic polymers reported earlier, which utilized DM as the cationic subunit and hydrophobic subunits with lower carbon numbers, such as DM:CHx, DM:βCP, $\\mathsf{D M}!\\beta\\mathsf{C H}^{42}$ .  \n\n![](images/c2ee88fc455fb63741bc604cb75ac980bd6640c72cfb6e5f1f52b918662be098.jpg)  \nFig. 7 | Experimental validation. a Synthesis of host defense peptides-mimicking $\\beta$ -amino acid polymers $\\mathsf{D M}_{x}i\\mathsf{P e n}_{y}(\\mathbf{x}+\\mathbf{y}=\\mathbf{1},\\mathbf{y}=0\\mathbf{-}0.5)$ , R represents the side chain from one of the starting monomers of DM and iPen. b Gel permeation chromatography (GPC) traces of $N$ -Boc-protected $\\mathsf{D M}_{x}i\\mathsf{P e n}_{\\mathrm{y}}$ . c Proton nuclear magnetic resonance (1H NMR) characterization of N-Boc-deprotected DMxiPeny. $\\mathsf{H}_{1},\\mathsf{H}_{2}$ and ${\\sf H}_{3}$ represent the characteristic peaks from iPen component within polymers. d Hemolysis of polymers against human red blood cells (hRBCs). ${\\mathsf{H C}}_{50}$ means the   \nminimum concentration to cause $50\\%$ hemolysis. e Cytotoxicity of polymers against Human umbilical vein endothelial cell line (HUVEC) cells. $\\mathrm{IC}_{50}$ means the minimum concentration to cause $50\\%$ inhibition. f Cytotoxicity of polymers against African green monkey kidney fibroblasts (COS7) cells. $\\mathbf{g}$ –i Selectivity index (SI) of the optimal polymer $\\mathsf{D M}_{0.8}i\\mathsf{P e n}_{0.2}$ calculated from ${\\mathsf{H C}}_{50}/{\\mathsf{M I C}}$ against hRBCs, $\\mathrm{IC}_{50}/$ MIC against HUVEC cells and COS7 cells. MIC means the minimum inhibitory concentration.  \n\nTable 2 | Gel permeation chromatography (GPC) characterization of N-Boc protected $\\mathsf{D M}_{x}i\\mathsf{P e n}_{y}$   \n\n\n<html><body><table><tr><td>x:y Mn(g mol-1)</td><td>DP D</td></tr><tr><td>10:0 5100</td><td>22 1.12</td></tr><tr><td>9:1 4900</td><td>22 1.13</td></tr><tr><td>8:2 5020</td><td>23 1.15</td></tr><tr><td>7:3 4500</td><td>22 1.13</td></tr><tr><td>6:4 4400</td><td>23 1.12</td></tr><tr><td>5:5 3600</td><td>20 1.09</td></tr></table></body></html>\n\n$M_{n}$ means the obtained number average molecular weight, D means dispersity index, $D P$ means degree of polymerization.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# Antimicrobial mechanism study of $\\pmb{\\beta}$ -amino acid polymer $\\mathbf{(DM_{0.8}}i\\mathbf{Pen_{0.2}}\\mathbf{)_{20}}$  \n\nWe investigated the antimicrobial mechanisms of the optimal polymer $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ against drug-resistant positive and drug-resistant negative bacteria. For the representative gram-positive bacteria of S. aureus, we conducted cytoplasmic membrane depolarization assay using DiSC3(5) dye as the bacterial membrane potential probe and cytoplasmic membrane permeability assay using propidium iodide (PI) dye as nucleic acid staining reagent to evaluate the interaction between $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ and bacterial membrane. It was found that $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ displayed a significant depolarization effect on S. aureus comparable to Triton X-100 (TX-100) and a strong membrane permeabilization effect (Fig. 8a, b). Scanning Electron Microscope (SEM) characterization demonstrated that the cell membrane of $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ treated S. aureus have obvious damage compared to untreated and normal S. aureus (Fig. 8c). In addition, we conducted the time-laps fluorescent confocal imaging to observe a dynamic sterilization process using the green fluorescent dyelabeled $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ . After treating S. aureus with dye-labeled $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ at $1\\times\\mathsf{M B C}$ (minimum bactericidal concentration), it was observed that $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ with green fluorescence and PI with red fluorescence entered into the bacteria cytoplasm almost simultaneously at about 30s, which echoed the strong membrane permeabilization effect (Fig. 8d). The above experiments all implied an antimicrobial mechanism by which $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ killing drugresistant S. aureus by strong interaction with bacteria membrane. For the representative gram-negative bacteria of $E.$ coli, we found that $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ have strong outer membrane perturbation ability via outer membrane permeabilization test (Fig. 8e). Continuous studies indicated that $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ displayed a strong depolarization and permeabilization effect against $E.$ . coli, which was consistent with experimental results of wrinkles appearing on the membrane surface of $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ treated $E.$ coli in SEM characterization (Fig. 8f, g, Supplementary Fig. 56). Moreover, the confocal imaging of dynamic sterilization process demonstrated that $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ with green fluorescence was gradually enriched on the membrane surface and then PI with red fluorescence started to entered into the bacteria cytoplasm (Fig. 8h). All those experimental results indicated that $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ killed drug-resistant $E.$ . coli via antibacterial mechanism of membrane damage.  \n\nTable 3 | Minimum inhibitory concentration (MIC) values of library DMxiPeny(x:y) against clinically isolated drug-resistant bacterial   \n\n\n<html><body><table><tr><td rowspan=\"2\"> Strain</td><td colspan=\"6\">MIC(μg mL-1)</td></tr><tr><td>10:0</td><td>9:1</td><td>8:2</td><td>7:3</td><td>6:4</td><td>5:5</td></tr><tr><td>Staphylococcus aureusUsA300</td><td>25</td><td>12.5</td><td>12.5</td><td>12.5</td><td>12.5</td><td>12.5</td></tr><tr><td>Staphylococcus aureus MU50</td><td>25</td><td>12.5</td><td>12.5</td><td>12.5</td><td>12.5</td><td>25</td></tr><tr><td>Staphylococcus aureus Newman</td><td>50</td><td>25</td><td>12.5</td><td>12.5</td><td>12.5</td><td>50</td></tr><tr><td>Staphylococcus aureus R02</td><td>25</td><td>12.5</td><td>12.5</td><td>12.5</td><td>12.5</td><td>25</td></tr><tr><td>Staphylococcus aureus R03</td><td>25</td><td>25</td><td>12.5</td><td>12.5</td><td>12.5</td><td>25</td></tr><tr><td>Vancomycin resistantenterococcus-1</td><td>12.5</td><td>6.25</td><td>6.25</td><td>6.25</td><td>6.25</td><td>12.5</td></tr><tr><td>Vancomycin resistant enterococcus-2</td><td>12.5</td><td>6.25</td><td>6.25</td><td>6.25</td><td>6.25</td><td>12.5</td></tr><tr><td>Escherichia coli JM109</td><td>25</td><td>12.5</td><td>12.5</td><td>12.5</td><td>12.5</td><td>25</td></tr><tr><td>Escherichia coli R19</td><td>50</td><td>25</td><td>12.5</td><td>12.5</td><td>12.5</td><td>25</td></tr><tr><td>Pseudomonas aeruginosa R09</td><td>12.5</td><td>6.25</td><td>6.25</td><td>6.25</td><td>6.25</td><td>25</td></tr><tr><td>Pseudomonas aeruginosa R10</td><td>12.5</td><td>12.5</td><td>6.25</td><td>6.25</td><td>6.25</td><td>25</td></tr></table></body></html>\n\nValues in bold indicate the performance of $\\mathsf{D M}_{0.8}i\\mathsf{P e n}_{0.2}$ which is chosen as the optimal antibacterial candidate.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# Discussion  \n\nArtificial intelligence (AI) has already made significant contributions to the entire life-cycle of drug design. However, there is currently a lack of efficient AI methods specifically tailored for designing host defense peptide-mimicking polymers, mainly due to the scarcity number of available polymers in each family and multi-constraints when exploring the vast high-dimensional polymer space. In this study, we have developed an end-to-end AI-guided inverse design framework to realize effective exploration of novel host defense peptide-mimicking polymers under the conditions of 86 few-shot polymer data.  \n\nBy applying multi-modal polymer representations, we extract multi-scale polymer information to improve the accuracy of the predictive model for few-shot data setting. All quantitative results prove a high reliability and stability of the predictive model, which can be further applied for the design process. Moreover, we distill the knowledge of our $\\beta$ -amino acids data and the natural $\\alpha$ -amino acids data, helping to construct a more concentrated chemical space for exploration. Thus, the generative model is able to efficiently generate polymers with high chemical rationality and synthetic feasibility under multiple constraints on desired bioactivities, toxicity and structures. Through iterative prediction and generation in reinforcement learning, we generate more than $10^{5}$ novel cationic-hydrophobic $\\beta$ -amino acid polymers, and we finally find 83 optimal polymers with the desired properties.  \n\nWe also synthesize one of the predicted candidates, $\\mathsf{D M}_{0.8}i\\mathsf{P e n}_{0.2},$ and verify the bioactivities. This polymer displays broad-spectrum and potent antibacterial activity and desirable antibacterial selectivity, indicating the effectiveness and feasibility of our AI strategy. Furthermore, our proposed data-driven AI strategy exhibits robust adaptability and holds great potential for application in various other domains beyond just a few-shot polymer or molecular systems. Through the utilization of our AI framework, we open up fresh opportunities to tackle the pressing challenge of efficiently identifying promising antibacterial polymers to counteract the growing threat of antibiotic resistance. In future studies, it worth exploring the AI-guided antimicrobial polymer design on more backbone types of polymers and more factors, such as various polymer descriptors, to more effectively find antimicrobial polymer candidates belonging to diverse species.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# Methods",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# Data preprocessing  \n\nWe made same data preprocessing to all the antibacterial activity data including MIC values as well as $\\mathsf{H C}_{10}$ values. If the end point of bacterial growth had not been arrived during the experiment, the values was estimated to be the current available value. (e.g., for the experimental estimated value $\\mathsf{H C}_{10}>400\\upmu\\mathrm{g}\\mathsf{m L}^{-1}.$ , it was seen as $400\\upmu\\mathrm{g}\\mathsf{m}\\mathsf{L}^{-1})$ . Note that natural logarithm transformation was performed to all the estimated results due to the regular values so that all the results were transformed as integers labels for corresponding properties (e.g., $\"12.5\"$ was recorded as $^{\\prime\\prime}{}_{3}\\mathrm{^{\\prime\\prime}}$ , $^{\\prime\\prime}400^{\\prime\\prime}$ was recorded as $\"8\"$ ). All models were trained to predict the natural logarithm of all properties.  \n\n![](images/cb204003a128ee47111217d4f81a43c391d6dd5105c0a2baca6d62bb0d578ecd.jpg)  \nFig. 8 | Antimicrobial mechanism study. a Cytoplasmic membrane depolarization of $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ against S. aureus USA300. TX-100 means Triton X-100. MIC means the minimum inhibitory concentration. b Cytoplasmic membrane permeability of $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ against S. aureus USA300. c Scanning Electron Microscope (SEM) characterization on S. aureus USA300 with and without $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ treatment at $1\\times\\mathsf{M B C}$ . The SEM sample was prepared once, and at least 50 fungal cells were observed individually in the sample, showing results similar to the representative SEM images shown in the figure. MBC means minimum bactericidal concentration. d Time-laps confocal fluorescence imaging on the   \ninteraction between S. aureus USA300 and fluorescent dye-labeled $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ at $\\mathbf{1}\\times\\mathbf{MBC},$ in the presence of propidium iodide (PI). e Outer membrane permeability of $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ against $E.$ coli R19. f Cytoplasmic membrane depolarization of $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ against E. coli R19. g SEM characterization on E. coli R19 with and without $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ treatment at $1\\times\\mathsf{M B C}$ . The SEM sample was prepared once, and at least 50 fungal cells were observed individually in the sample, showing results similar to the representative SEM images shown in the figure. h Time-laps confocal fluorescence imaging on the interaction between E. coli R19 and fluorescent dye-labeled $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ at $1\\times\\mathsf{M B C}$ , in the presence of PI.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# Polymer data augmentation  \n\nAn important property for cationic-hydrophobic $\\beta$ -amino acid polymers, or more specifically for multi-component polymers is that the machine learning or deep learning model used should follow the permutation invariance of the polymer input, i.e. the results of the model should not be influenced by the order of the components, and it could be formulated as,  \n\n$$\n\\left\\{\\begin{array}{l l}{H{=}M_{1}[(p_{1},r_{1}),(p_{2},r_{2})]{=}M_{1}[(p_{2},r_{2}),(p_{1},r_{1})],}\\\\ {S{=}M_{2}[(p_{1},r_{1}),(p_{2},r_{2})]{=}M_{2}[(p_{2},r_{2}),(p_{1},r_{1})],}\\\\ {E{=}M_{3}[(p_{1},r_{1}),(p_{2},r_{2})]{=}M_{3}[(p_{2},r_{2}),(p_{1},r_{1})],}\\end{array}\\right.\n$$  \n\nwhere $M_{1},M_{2},M_{3}$ were different map functions from the polymer input to corresponding properties, $H,S,E$ were the value of MICS.aureus, $\\mathsf{M I C}_{E.c o l i}$ and $\\mathsf{H C}_{10}$ , respectively, $p,r$ were the polymer unit and its composition information. In the previous work47, it had been proved that by considering the permutation invariance, the model accuracy can be improved. In this way, we reasonably introduced this property as a method for data augmentation, aiming at improving the accuracy of the predictive model. Detailed, we adjusted the order of the input cationic and hydrophobic subunits and the feature orders in all representations were also changed with the same property label, so as to avoid the influence of the input order.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# Multi-modal random polymer representation  \n\nTranslating polymers into machine readable vectors was one important problem with ongoing concerns for polymer informatics69. Different from micromolecules with deterministic topology connections of atoms and bonds, it was hard to completely represent random polymers with unregular sequence by general representation methods for micromolecules (e.g., SMILES or graphs) due to the intrinsically stochastic nature of polymers44. Generally considering, the property of a polymer was mainly decided by 1) structures of subunits and 2) subunit sequence connection, while for random polymers, the subunit ratio should be taken into consideration instead of sequence connection. In our work, we proposed a multi-modal polymer representation method from the following three perspectives:  \n\nMolecular descriptors. Molecular descriptors are mathematical representation of chemicals which are generally used to build predictive models. We used an open-sourced Mordred calculator45, which included 1826 two- and three-dimensional descriptors. For cationichydrophobic polymers, descriptors of both the cationic and hydrophobic subunits were calculated and stacked together, totally dimensioned 3654 for candidate descriptor vector with adding composition information $r_{1},r_{2}$ of two subunits. Then we applied a two-stage descriptor downselection strategy with a stage of statistical downselection and a stage of machine learning based downselection46. In the first stage, constant or almost constant descriptors were dropped from the initial set (Init., 3654 descriptors), and descriptors with variance larger than $10\\%$ of the mean value across the initial set were filtered out as validate set (Var., 1014 descriptors). Next, we evaluated Spearman rank correlations of each descriptor pair, and descriptors with correlation higher than 0.9 as well as correlation with the target property (MICS.aureus, $\\mathsf{M I C}_{E.c o l i}$ and ${\\mathsf{H C}}_{10},$ ) lower than 0.05 were filtered out as correlation set (Cor., 182, 171, 174 descriptors for ${\\sf M I C}_{S}$ .aureus, $\\mathsf{M I C}_{E.c o l i}$ and $\\mathsf{H C}_{10}$ , respectively). In the second stage, a recursive feature elimination (RFE) method70 was introduced on the Cor. descriptors set based on a random forest (RF) model. With RF regression, each descriptor was eliminated recursively according to the importance rankings until the last descriptor. Then, a 15-fold cross-validation was adopted with repeated stratified subsampling descriptors. The principle of choosing the optimized descriptor set was to choose a descriptor which has the lowest mean RMSE. In this way, descriptors with most important information related on the target property were selected. In our work, we chose 40 descriptors as the optimized molecular descriptors (Opt., 40 descriptors for MICS.aureus, $\\mathsf{M I C}_{E.c o l i}$ and ${\\mathsf{H C}}_{10},$ respectively) for part of the input of the predictive model (Results of selected descriptors are shown in Supplementary Figs. 3–8, and supplied predictive results are shown in Supplementary Fig. 9).  \n\nMolecular representations. Molecular representations are another popular ways to encode molecules. In recent polymer informatics, BigSMILES is a recently developed structurally-based line notation to reflect the stochastic nature of polymer molecules44. Compared with molecular descriptors, hidden chemical information could be learned from molecular representations via a data-driven pattern. According to the syntax of BigSMILES, we developed two kinds of other rules to completely define cationic-hydrophobic $\\beta$ -amino acid polymers, and also these rules are universal for other random polymers.  \n\nSequence representation. Traditional SMILES strings generally consisted of various atom tokens (e.g., $^{\\prime\\prime}\\mathrm{C}^{\\prime\\prime},\\ ^{\\prime\\prime}\\mathrm{O}^{\\prime\\prime},\\ ^{\\prime\\prime}[\\mathrm{NH}3+]^{\\prime\\prime})$ , bond tokens (e.g., $\\tilde{\\mathbf{\\Gamma}}^{\\prime\\prime}=\\tilde{\\mathbf{\\Gamma}}^{\\prime\\prime},\\tilde{\\mathbf{\\Gamma}}^{\\prime\\prime}\\mathcal{H}^{\\prime\\prime})$ and branching tokens (e.g., $^{\\prime\\prime}(\\not{O}^{\\prime\\prime},{}^{\\prime\\prime}1,2^{\\prime\\prime})$ to encode molecules. In BigSMILES sequence, the stochastic object and the bonding descriptors were two new joined elements compared with basic SMILES grammar. We further introduced several additional definition so as the composition information of each repeated subunit in the stochastic object could be expressed, which was not included in BigSMILES. Take $\\mathsf{D M}_{0.6}\\mathsf{B U}_{0.4}$ as an example, it could be written as: $\\{[>]N C(C)(C)C(C[N H3+])C=O.[+r n=60],$ $N C(C C C)C C=O[<].[+r n=40]\\}$ , where $\\prime\\prime[\\mathrm{+rn}=60]^{\\prime\\prime}$ showed that the DM subunit has the ratio of $60\\%$ . $\">\"$ and $\"<\"$ were two conjugate types of boding descriptors showing how repeat units were linked. For simplicity, we omitted exterior strings (since they are all same for our cationic-hydrophobic $\\beta$ -amino acid polymers) and we used the simplification style. Other cationichydrophobic polymers were defined like such. After collecting all characters involved, the one-hot encoding of the BigSMILES strings could be generated as the input. All the sequences are written manually and it is hard to be applied to large-scale datasets for further performance comparison, since there is still not mature toolkit for polymers.  \n\nGraph representation. Similarly, we construct graph representation for random polymers according to the BigSMILES syntax, shown in Supplementary Fig. 10. In BigSMILES syntax, bond descriptors are introduced to specify where and how repeat units can be joined with another repeat unit. Bonding descriptors are placed on atoms of a repeat unit that could form direct bonds with another repeat unit. In BigSMILES, there are two types of bonding descriptors: one is the $\"\\$1$ descriptor, or AA-type descriptor, which means it can only be connected with the same descriptors; the other is the $\"<\"$ and $\">\"$ descriptors, or AB-type descriptor, which means one descriptor should be connected with the conjugate descriptor. These rules are translated into our tasks to represent a cationic-hydrophobic amphiphilic $\\beta$ - amino acid polymer.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# Predictive network  \n\nWe testified the property prediction performance using various of representations and we set Morgan fingerprints, which was widely used in polymer property prediction35, as baseline. In this study, we mainly used the following combinations according to three proposed multi-modal representations with properly designed network structures for specific tasks71,72: 1) Descriptor vector (from Descriptor_Init to  \n\nDescriptor_Opt), 2) Sequence vector, 3) Graph vector, 4) Sequence vector and Descriptor vector (Seq+Descriptor_Opt), 5) Graph vector and Descriptor vector (Graph $^+$ Descriptor_Opt), 6) Sequence vector, graph vector and Descriptor vector (Seq+Graph+Descriptor_Opt). Noted that we used the optimized descriptors for fusing since they had reached better model performance.  \n\nNetwork architectures. For situation 1), we transformed the descriptor feature $F_{f}$ by subtracting the means and dividing by the standard deviations as normalization process and we simply trained a Fullyconnected Feed-forward Neural Network (FFN) for prediction. The dimensionality of the input feature $F_{j}$ is $[B,N_{D}]$ and the dimensionality of the input layer of FNN is $[N_{D},D_{f}]$ , where $B$ is the number of batch size, $N_{D}$ is the number of descriptors used and $D_{f}$ is the dimensionality of the hidden layers in FNN. For 2), we used the bidirectional Gate Recurrent Unit $(\\mathbf{G}\\mathbf{R}\\mathbf{U})^{73,74}$ to extract the hidden information embedded in Sequence vector, and can be formulated as,  \n\n$$\n\\left\\{\\begin{array}{l l}{\\overrightarrow{h_{k}}=\\overrightarrow{\\mathbf{GRU}}(t_{k},\\overrightarrow{h_{k-1}}),}\\\\ {\\overleftarrow{h_{k}}=\\overleftarrow{\\mathbf{GRU}}(t_{k},\\overbrace{h_{k-1}}^{\\left.}),}\\end{array}\\right.\n$$  \n\nwhere $t_{k}$ was the token embedding, and $\\overrightarrow{h_{k}},\\overleftarrow{h_{k}}$ were bidirectional hidden states for the $k_{t h}$ token of a string embedded by GRU, and the current hidden state $h_{k}$ was obtained as,  \n\n$$\nh_{k}=({\\overrightarrow{h_{k}}},{\\overleftarrow{h_{k}}}).\n$$  \n\nFinally, we used $F_{s}$ to denote the contextual representation of a sequence string with length $n$ as,  \n\n$$\nF_{s}=(h_{0},h_{1},\\cdots,h_{n}).\n$$  \n\nThe dimensionality of the input sequence vector is $[B,n]$ and the dimensionality of the sequence embedding is $[n,D_{s}]_{i}$ , where $B$ is the number of batch size, $n$ is the number of each input sequence and $D_{s}$ is the dimensionality of the hidden layers in GRU. The final dimensionality of the sequence feature $F_{s}$ is $[B,D_{s}]$ .  \n\nFor 3), we apply a Bidirectional Message Communication $\\mathbf{GNN}^{75}$ , which makes full use of the node message for more effective message interactions to extract the local information embedded in the graph. The network structures can be seen in Supplementary Fig. S11 and the pseudocode of the model were concluded in Supplementary Information as Algorithm 1.  \n\nSpecifically, the input of the algorithm is each polymer graph $G\\mathrm{=}(\\gamma,\\mathcal{E})$ and all of its atom attributes $x_{\\upsilon}(\\forall\\upsilon\\in\\mathcal{V})$ and bond attributes $x_{e_{v w}}(\\forall e_{v w}\\in\\mathcal{E})$ . The initial node feature $h_{\\nu}^{0}$ is simply the atom attributes, while the initial edge feature $h_{e_{v w}}^{0}$ is the bond attributes. Then, according to the network depth $T,$ a $T$ steps message aggregation and update procedure is applied. In each step t, each node message vector $m_{\\upsilon}^{t+1}$ is aggregated according to its incoming edges and each edge message vector $m_{e_{v w}^{t+1}}$ is aggregated according to its neighbor nodes, shown as,  \n\n$$\n\\begin{array}{r}{\\left\\{\\begin{array}{l l}{m_{\\upsilon}^{t+1}=\\mathbf{MAX}(h_{e_{u v}}^{t})\\odot\\mathbf{SUM}(h_{e_{u v}}^{t}),u\\in\\mathcal{N}(\\upsilon),}\\\\ {m_{e_{v w}}^{t+1}=\\mathbf{MEAN}(h_{\\upsilon}^{t},h_{w}^{t}),}\\end{array}\\right.}\\end{array}\n$$  \n\nwhere MAX, SUM, MEAN are the corresponding aggregating strategy, $\\odot$ is an element-wise multiplication operator. Then the obtained message vectors of node and edge $m_{\\nu}^{t+1},m_{e_{v w}}^{t+1}$ are concatenated with the corresponding current hidden states to be sent to the communicate function which use an addition operator as communicative kernel to calculate the communicative vector $p_{v}^{t+1},p_{e_{v w}}^{t+1}$ . Then the hidden state of the node and edge are updated with skip  \n\nconnection as,  \n\n$$\n\\begin{array}{r}{\\left\\{\\begin{array}{l l}{\\boldsymbol{h}_{\\nu}^{t+1}=\\boldsymbol{U}_{\\nu}^{t}(\\boldsymbol{p}_{\\nu}^{t+1},\\boldsymbol{h}_{\\nu}^{0})=\\mathbf{ReL}\\mathbf{U}(\\boldsymbol{h}_{\\nu}^{0}+\\mathbf{W}_{\\mathbf{v}}\\cdot\\boldsymbol{p}_{\\nu}^{t+1}),}\\\\ {\\boldsymbol{h}_{e_{v w}}^{t+1}=\\boldsymbol{U}_{e}^{t}(\\boldsymbol{p}_{e_{v w}}^{t+1},\\boldsymbol{h}_{e_{v w}}^{0})=\\mathbf{ReL}\\mathbf{U}(\\boldsymbol{h}_{e_{v w}}^{0}+\\mathbf{W}_{\\mathbf{e}}\\cdot\\boldsymbol{p}_{e_{v w}}^{t+1}),}\\end{array}\\right.}\\end{array}\n$$  \n\nwhere ReLU is the rectified linear unit and ${\\bf W_{v}},{\\bf W_{e}}$ are learned matrices. After $T$ step iteration, a GRU based readout function is applied to the final node representation $h_{\\nu}^{T}$ to get the graph-level representation $F_{g}$ as,  \n\n$$\nF_{g}=\\sum_{\\nu\\in\\mathcal{V}}\\mathbf{GR}\\mathbf{U}(h_{\\nu}^{T}).\n$$  \n\nThe dimensionality of the input atom vector and bond vector in graph are $[B,N_{v},F_{v}]$ and $[B,N_{e},F_{e}],$ and the dimensionality of the atom embedding and bond embedding in Bidirectional Message Communication GNN are $[F_{\\nu},D_{g}]$ and $[F_{e},D_{g}],$ where $B$ is the number of batch size, $N_{v},N_{e}$ are the atom number and bond number in each input molecular graph, $\\boldsymbol{F}_{\\nu}$ and $F_{e}$ are the number of attributes for each atom and bond and $D_{g}$ is the dimensionality of the hidden layers in GNN. The final dimensionality of the graph feature $F_{g}$ is $[B,D_{g}]$ . For 1)-3), the network structures can be seen in Supplementary Fig. 11.  \n\nSince 4), 5) and 6) involved multiple polymer vectors, we developed a multi-modal polymer representation method with adjustable network blocks for specific representations. A core motivation was how to learn more abundant chemical information from limited data points and how to find connections and differences between information in diverse representations. From feature descriptors, various basic chemical or calculated information could be gained. In contrast, from sequence or graph representations, distributions of atoms and bonds on spatial and numerical were explicitly displayed, while more implicit information, which might not be calculated through a specific equation, was generally learned with the help of datadriven deep learning. Since the available data are very limited, to learn better polymer feature for few-shot prediction, we tempted to merge various representations which is one of the main contributions of our work.  \n\nThe main structure included several customized representation learning blocks to extract implicit information from various representations (descriptors, sequence and graph here), and this process could be formulated as,  \n\n$$\nF_{j}=\\mathbf{Combine}(F_{f},F_{s},F_{g}),\n$$  \n\nwhere Combine was the function to assemble different representations with adding and stacking, and $F_{j}$ was the joint feature by stacking all the vector features with the dimensionality of $[B,D_{j}],D_{j}=D+N_{D}$ $(D=D_{f}=D_{s}=D_{g})$ . According to the different input representations in 4), 5) and 6), different blocks are inserted as shown in Supplementary Fig. 12.  \n\nThen a Transformer-based feature combination block was built with the input of $F_{j}.$ The Transformer had been proved as a powerful model on various fields through its power on extracting comprehensive information. To find connections between the learned implicit information from Sequence and Graph representation and the explicit information embedded in descriptors, we further used descriptors $F_{f}$ as the attention bias in the self-attention mechanism, and this process could be formulated as:  \n\n$$\nQ=F_{j}W_{Q},K=F_{j}W_{K},V=F_{j}W_{V},\n$$  \n\n$$\n\\mathbf{Attention}(F_{j}){=}\\mathbf{softmax}(Q K^{\\top}/\\sqrt{d_{K}}+F_{f})V,\n$$  \n\nwhere $W_{Q},W_{K},W_{V}$ were the corresponding projecting matrices of $Q$ (query), $K$ (keys), $\\boldsymbol{V}$ (values), $d_{K}$ was the dimension of keys, Attention was the self-attention mechanism in Transformer and softmax was the softmax function. With the calculation of the Transformer block and feedforward network (FNN) block, we got the final predictions of the properties with the dimensionality of $^{[B,1]}$ ,  \n\n$$\nP=\\mathbf{F}\\mathbf{N}\\mathbf{N}(\\mathbf{Transformer}(F_{j},F_{f})).\n$$  \n\nPredictive model training settings. We randomly split the training data $D_{t r a i n\\_a u g}$ into 8:1:1 train/valid/test ratios and we applied bayesian optimization to find the optimal hyper-parameters. Then we used the optimized parameters to retrain the model for 10 independent runs with different random seeds. Specifically, a dynamic changed learning rate was used with the Adam optimizer with mean squared error (MSE) loss to train the model. We set an initial learning rate as $10^{-4}$ and it would be doubled as a max learning rate in 5 warm up training epochs, and finally the learning would return the $10^{-4}$ as a final value. The training epoch and the batch size were set as 100 and 16 respectively. In each epoch, if the validation MSE reduced, the model would be saved. The parameters of each block of GNN, GRU, Transformer and FNN were all recorded in Supplementary Table 2. In addition, since the operation of random data splitting would cause uneven distribution of training data, we applied the ensembling technique, which is a common technique in machine learning. Multiple independently trained models with different random seeds were combined to produce an averaging predictions so as to prevent overfitting on partial results. After training, the unseen testing data $D_{t e s t}$ was used to evaluate the performance of the model, using the R-squared coefficient (R2, higher R2 means better performance of the model) and root-mean-squared error (RMSE, lower RMSE means better performance of the model) as metrics. The implementation of the model relies on Pytorch and RDKit package.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 16,
+        "chunk": "# Scaffold-decorator generative network  \n\nTake the hydrophobic subunit “BU” as an example, its SMILES string was “NC(CCCC)C $\\scriptstyle\\mathbf{C}=\\mathbf{O}^{\\prime\\prime}$ , which could also be seen as that a side chain “[\\*] CCCC” was decorated to the scaffold $^{\\prime\\prime}{\\sf N C}([^{*}]){\\sf C C}=0^{\\prime\\prime}$ , where “[\\*]” was the special attachment token for substitution. For scaffold with more than one substitution, a symbol $\"|\"$ was introduced to differentiate decorations76. Therefore, the core problem of polymer design could be transformed as finding the optimized decoration for the specific scaffold to formulate subunits for polymer with desirable properties. We summarized the whole designing procedure in two stages. Firstly, we pre-trained a GRU-based molecular scaffold-decorator with the ability of generating valid subunits. Secondly, a reinforcement learning finetuning stage was adopted to explore the chemical space for optimal polymers. When fine-tuning, each reasonable molecule would be recorded for the convenience of final analysis and evaluation.  \n\nNetwork architectures. The implementation of scaffold-decorator network was totally an encoder-decoder architecture with attention mechanism. The encoder was a bidirectional RNN sequenced with an embedding layer and three layers of bidirectional GRU cells of 256 dimensions. Then the hidden states were sent to the decoder, which was a single direction RNN sequenced with an embedding layer, three layers of GRU cells of 256 dimensions. Finally, an global attention layer as adopted to sum up the output of the encoder and the decoder, and a liner layer was connected to calculate the probability of each possible token $x_{i}.$ . The model was trained to maximize the Negative LogLikehood (NLL) loss written as:  \n\nwhere $P(x_{i}|\\boldsymbol x_{<i})$ was the probability when sampling the $i_{t h}$ token of decoration sequence S with given the previous tokens and the input scaffold.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 17,
+        "chunk": "# Graph grammar distillation  \n\nA direct idea was that the subunits for which we would like to explore had similar structures thus these structures must distributed closely in the huge chemical space (Supplementary Fig. 24). Generally, our $\\beta$ - amino acids have similar structures with natural $\\alpha$ -amino acids. However, if we pre-training our model with large-scale public data, those rules for constructing complex structures or undesirable chemical elements (e.g., Br,Cl) may also be embedded in the model. Thus, it takes a long time for further RL fine-tuning to adjust the parameters to avoid generating those subunits. Thereby, we first collected all cationic and hydrophobic $\\beta$ -amino acids in our data and several natural $\\alpha$ - amino acids structures (Supplementary Fig. 23). Then, we used a hyper-graph based data-efficient graph grammar learning method $(\\mathrm{DEG})^{77}$ to collect various graph grammar rules from the given amino acids. Thus, various grammar rules were learned automatically from the training data, and specific rules could be learned according to the given data if needed. By doing so, we extracted grammar knowledge and we recombined these grammar to construct a distilled set of molecules. Then, we similarly used the RECAP rules to slice molecules, gaining 0.3 million pairs of scaffold-decoration data. We took these data to pre-train a generative model with the same structures above and constructed a more-focused chemical space embedded in the model for further exploration, so as to accelerate the search efficiency under multi constraints for RL agent.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# Reinforcement learning  \n\nTo further guide our generative model pre-trained by graph grammar distillation toward relevant areas in chemical space according to customized requirements, we adopted REINVENT $2.0^{78}$ . It is a recently developed reinforcement learning method for de novo drug design, for fine-tuning to carry out a constellation of specific tasks of design. By fine-tuning, various user-defined requirements could be satisfied to generate molecules of interest. In our cases, we realized the following requirements: 1) polymer generation under various scaffold subunit structures (e.g., $\\scriptstyle\"\\mathsf{N C}([^{*}])\\mathsf{C C}=0^{\\prime\\prime}$ , $\\scriptstyle\\mathbf{\\\"}\\mathbf{NCC}(\\mathbf{C=O})\\mathbf{1}[\\mathbf{\\\"}]\\mathbf{C}1^{\\prime}$ , $^{\\prime\\prime}{\\sf N C I}[^{*}]{\\sf C1C}{=}0^{\\prime\\prime})$ , 2) polymer generation under multi-objective constraints (e.g., carbon numbers, ring number and $\\mathsf{M I C}_{S.a u r e u s}/\\mathsf{M I C}_{E.c o l i}/\\mathsf{H C}_{10}$ thresholds).  \n\nThe main roles in REINVENT 2.0 included a prior model $M_{\\mathrm{Prior}},$ an agent model $M_{\\mathrm{Agent}}$ and a score modulating block. The prior model was the pre-trained scaffold-decorator generative model introduced above, while the agent model shared the identical network structures and the initialization parameters of the agent model as completely the same as the prior model. The score modulating block could be regarded as the environment which fed back rewards according to the targeted scoring functions.  \n\nThen we introduced the reinforcement learning cycle. First, the agent model $M_{\\mathrm{agent}}$ sampled batch of SMILES decorations for a specific scaffold, and the decorated polymer were scored according to the scoring function $S_{\\mathrm{score}}$ (introduced in Eq. (15)). Among each course of sampling molecules, the agent chose the next possible token, seen as the action $A_{\\mathrm{action}}$ , according to the current token sequence, regarded as the state $S_{\\mathrm{state}}$ in the RL framework. Thus, the agent learned a conditional probability $p(A|S)$ to generate the desired molecules when the episodes go on. To train the agent model, we used the NLL, similar to Eq. (12), to represent the agent likelihood of the generated decoration sequence S as $\\mathsf{N L L}(\\mathsf{S})_{\\mathsf{A g e n t}}.$ . Then S would be given to the prior model $M_{\\mathrm{Prior}}$ to calculate the augmented likelihood with the score $S_{\\mathrm{score}}(\\pmb{\\mathsf{S}})$ . Ultimately, the loss of the agent could be calculated as:  \n\n$$\n\\mathsf{N L L}(\\pmb{\\mathsf{S}})=-\\sum_{i=1}^{n}\\log P(x_{i}|\\boldsymbol{x}_{<i},\\mathsf{s c a f f o l d}),\n$$  \n\n$$\n\\mathsf{N L L}(\\pmb{\\mathsf{S}})_{\\mathrm{Augmented}}=\\mathsf{N L L}(\\pmb{\\mathsf{S}})_{\\mathrm{Prior}}-\\sigma S_{\\mathrm{score}}(\\pmb{\\mathsf{S}}),\n$$  \n\n$$\n\\begin{array}{r}{\\mathbf{loss}=[\\mathbf{NLL}(\\pmb{\\mathsf{S}})_{\\mathrm{Augmented}}-\\mathbf{NLL}(\\pmb{\\mathsf{S}})_{\\mathrm{Agent}}]^{2},}\\end{array}\n$$  \n\nwhere $\\sigma$ was the scalar value to scale up the output of the score function. During the training process, we collected all valid generated molecules for data analysis, and molecules with desired properties would be further filtered out for experimental validation.  \n\nGenerative model training settings. For the graph grammar distillation pre-training process, the training epoch, batch size and the learning rate were set as 450, 256 and $10^{-3}$ respectively. The dimensionality of hidden layers of GRU was set as 256. For the reinforcement learning fine-tuning process, the training epoch, batch size and the learning rate were set as 450, 30 and $10^{-9}$ respectively. Also, we use the negative log likelihood (NLL) loss to train the model and the implementation of the model relies on Pytorch and RDKit package. All hyperparameters are concluded in Supplementary Table 5.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 19,
+        "chunk": "# Score and metric  \n\nIn this study, we aimed to find more potential cationic and hydrophobic subunit combinations with specific composition rations, which satisfied the desired properties: $\\mathsf{M I C}_{S.a u r e u s}<25$ , $\\mathsf{M I C}_{E.c o l i}>25$ and $\\mathsf{H C}_{10}>100$ . Moreover, we designed several penalty rules or customized constraints to accelerate the learning process with narrowing down the scope of exploration. The final score function $S_{\\mathrm{score}}(\\pmb{\\mathsf{S}})$ , which could also be seen as the reward in RL, was written as:  \n\n$$\nS_{\\mathrm{score}}(\\mathbf{S}){=}S_{\\mathrm{property}}(\\mathbf{S}){+}S_{\\mathrm{penalty}}(\\mathbf{S}){+}S_{\\mathrm{constrain}}(\\mathbf{S}),\n$$  \n\nwhere Sproperty, Spenalty, $S_{\\mathrm{c}}$ onstrain were three different parts of target activities, penalty of irrationality and customlized constraints for scoring.  \n\nProperty score. We used the previously trained predictive network to calculate the value of MICS.aureus, $\\mathsf{M I C}_{E.c o l i}$ and $\\mathsf{H C}_{10}$ respectively. For all the calculated values, we applied score transformations (sigmoid for $\\mathsf{H C}_{10}$ and reverse sigmoid for $\\mathsf{M I C}_{S.a u r e u s}$ and $\\mathsf{M I C}_{E.c o l i})$ so that each component returned a value between [0,1] (the higher the better). This operation helped to avoid one-sided impacts of single-properties and adjust the influence of multi-parameter objectives, and the property scoring function could be written as:  \n\n$$\nS_{\\mathrm{property}}(\\pmb{\\mathsf{S}})=a*\\mathsf{M I C}_{S.a u r e u s}(\\pmb{\\mathsf{S}})+b*\\mathsf{M I C}_{E.c o l i}(\\pmb{\\mathsf{S}})+c*\\mathsf{H C}_{10}(\\pmb{\\mathsf{S}}),\n$$  \n\nwhere a, $^{b}$ and $c$ were adjustable weights showing that which the agent should put more focus on. They were decided by customized design demands. In this work, we focused more on the antimicrobial activity and hence, we set a larger value for $a=b=2$ than $c=1$ .  \n\nPenalty score. To improve the rationality and correctness of the generated molecules, we designed several structural penalties as the penalty scoring function,  \n\n$$\nS_{\\mathrm{penalty}}({\\bf S})=\\left\\{\\begin{array}{l}{{-{\\cal S},\\mathrm{\\when\\molecule\\is\\invalid},}}\\\\ {{-3,\\mathrm{\\when\\unexpected\\elements\\exist}.}}\\end{array}\\right.\n$$  \n\nConstrain score. To further constrain the structures of the generated molecules, we also designed several constraints which can be used alternatively,  \n\n$$\nS_{\\mathrm{constrain}}(\\mathbb{S})=\\left\\{{\\begin{array}{r l}{C/2,\\quad}&{C_{\\mathrm{number}}\\leq X,}\\\\ {-2,}&{C_{\\mathrm{number}}>X,}\\end{array}}+\\left\\{{\\begin{array}{r l r l}{-3,\\quad}&{R>Y,}\\\\ {0,\\quad}&{R\\leq Y,}\\end{array}}\\right.\n$$  \n\nwhere $C_{\\mathrm{number}}$ was the carbon number of the final decorated molecule, $R$ was the ring number and $\\chi$ , Y were adjustable constants to decide how many carbon atoms or how many circles should be generated. As discussed before, to prove the rationality of the generated polymers, we set $\\scriptstyle{X=11}$ and $\\scriptstyle{\\gamma=1}$ in our exploration settings to prove the toxicity without chemical structural rationality.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 20,
+        "chunk": "# Evaluation settings  \n\nTo exactly find new candidate polymers with desired properties, we set three situations to evaluate the performance of the generative model pre-trained by graph grammar distillation. It is worth noting that in all situations, we fixed the cationic monomer as DM and MM structures and focused on designing new hydrophobic monomers. This helped to improve the synthetic possibility for final validation. Even new cationic monomers were not taken into consideration. It was still a challenging problem since there still existed multiconstraints (structures, properties etc.) and should be taken into consideration to adjust hydrophobic subunits. Details are outlined below: Task 1: Cationic: DM/MM, hydrophobic: any scaffold, reward design:  \n\n$$\nS_{\\mathrm{score}}(\\mathbf{S})=2*\\mathsf{M I C}_{S.a u r e u s}(\\mathbf{S})+S_{\\mathrm{penalty}}(\\mathbf{S}).\n$$  \n\nTask 2: Cationic: DM/MM, hydrophobic: any scaffold, reward design:  \n\n$$\n\\begin{array}{r l}&{S_{\\mathrm{score}}(\\pmb{\\mathsf{S}})=2*\\mathsf{M I C}_{S.a u r e u s}(\\pmb{\\mathsf{S}})+2*\\mathsf{M I C}_{E.c o l i}(\\pmb{\\mathsf{S}})}\\\\ &{\\qquad+1*\\mathsf{H C}_{10}(\\pmb{\\mathsf{S}})+S_{\\mathrm{penalty}}(\\pmb{\\mathsf{S}})+S_{\\mathrm{constrain}}(\\pmb{\\mathsf{S}}),}\\end{array}\n$$  \n\nwhere $\\scriptstyle{\\chi=11}$ , $\\scriptstyle{\\gamma=1}.$ Task 3: Cationic: DM, hydrophobic: $\\mathsf{N C}([^{*}])\\mathsf{C}\\mathsf{C}(=0)$ , reward design:  \n\n$$\n\\begin{array}{r l}&{S_{\\mathrm{score}}(\\pmb{S})=1*\\mathsf{M I C}_{\\pmb{S}.a u r e u s}(\\pmb{S})+1*\\mathsf{M I C}_{E.c o l i}(\\pmb{S})+3*\\mathsf{H C}_{10}(\\pmb{S})}\\\\ &{\\qquad+S_{\\mathrm{penalty}}(\\pmb{S})+S_{\\mathrm{constrain}}(\\pmb{S}),}\\end{array}\n$$  \n\nwhere $\\scriptstyle{X=11}$ , $\\scriptstyle{\\gamma=1}.$  \n\nTask 1 was designed to evaluate the performance of the model pre-trained by graph grammar distillation and the model pre-trained by ChEMBL. Task 2 referred to analysis the distributions of the generated polymers with evaluations by the predictive model, aiming at further find the desirable area with more possible optimal candidates under multiple-constrains. Following the results in Task 2, we made further qualifications on a specific scaffold structure, aiming exploring more candidate polymer with specific scaffold for real-work synthesis, as Task 3. Note that we defined a high weight for $\\mathsf{H C}_{10}$ which was mainly due to the fact that for polymers with a fixed DM subunit, most polymers showed undesirable property on $\\mathsf{H C}_{10}$ and we gave more weights on it.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 21,
+        "chunk": "# Materials  \n\nAll chemical reagents and solvents were used without further purification. Anhydrous dichloromethane (DCM) and anhydrous Tetrahydrofuran (THF) were purchased from Sigma-Aldrich. Ethyl acetate (EtOAc) and other solvents were purchased from Shanghai Titan Technology Co., Ltd. Synthesized chemicals were purified using a SepaBean machine equipped with Sepaflash columns produced by Santai Technologies Inc in China. The water used in these experiments was obtained from a Millipore water purification system with a resistivity of 18.2 MΩ.cm. 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) was purchased from MACKLIN regent, Shanghai. Dulbecco’s modified Eagle medium (DMEM) were purchased from Hyclone (USA).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 22,
+        "chunk": "# Cell lines  \n\nHuman umbilical vein endothelial cell line (HUVEC) and the African green monkey kidney fibroblasts (COS7) cells were obtained from the Cell Bank of the Chinese Academy of Sciences (Shanghai, China).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 23,
+        "chunk": "# Measurements  \n\nNuclear magnetic resonance (NMR) spectra were collected on a Bruker spectrometer at $400\\mathsf{M H z}$ using $\\mathsf{C D C l}_{3}$ as the solvent and ${600}\\ensuremath{\\mathsf{M H z}}$ using ${\\bf D}_{2}{\\bf O}$ as the solvent. The corresponding chemical shifts were referenced to residual protons in the deuterated NMR solvents. High resolution electrospray ionization time-of-flight mass spectrometry (HRESI-MS) was collected on a Waters XEVO G2 TOF mass spectrometer. Gel permeation chromatography (GPC) was performed on a Waters GPC instrument equipped with a refractive index detector (Waters 2414) using dimethylformamide (DMF), supplemented with 0.01 M LiBr, as the mobile phase at a flow rate of $1\\mathrm{mL}\\mathrm{min}^{-1}$ at $50^{\\circ}\\mathrm{C}.$ . The GPC were equipped by a Tosoh TSKgel Alpha2500 column (particle size $7\\upmu\\mathrm{m})$ and a Tosoh TSKgel Alpha-3000 column (particle size $7\\upmu\\mathrm{m})$ ) linked in series. Relative numberaverage molecular weight $(M_{n})$ , degree of polymerization (DP) and dispersity index (D) were calculated from a calibration curve using polymethylmethacrylate (PMMA) as standards. Before GPC characterization, all samples were filtered through $0.22\\upmu\\mathrm{m}$ polytetrafluoroethylene (PTFE) filters. Optical density (OD) value and fluorescence value were recorded on a multifunction microplate reader (SpectraMax M2).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 24,
+        "chunk": "# Synthesis of $\\pmb{\\beta}$ -lactams  \n\n$(\\pm)$ -3-tert-Butyloxycarbonylaminomethyl-4,4-dimethyl azetidin-2-one (3, $\\beta$ -lactam DM, Supplementary Fig. 57) was synthesized by following previously reported procedure43. Briefly, 3,3-Dimethylallyl bromide $(15.0\\mathrm{g},0.1\\mathrm{mol})$ and potassium phthalimide $(20.4\\mathrm{g},0.11\\mathrm{mol})$ ) potassium phthalimide was mixed in $300\\mathrm{mL}$ DMF. The reaction mixture was stirred vigorously at room temperature for $16\\mathsf{h}$ and then poured into $\\mathbf{800mL}$ ice water with vigorous stirring to result precipitate. The precipitate was collected by filtration and washing with ethanol to give the crude product. After removing the solvent under vacuum, the intermediate compound 1 (Supplementary Fig. 57) was directly used without purification $(20.0\\mathbf{g},93.0\\%)$ . $\\mathsf{\\Pi}^{1}\\mathsf{H}$ NMR $(400\\mathsf{M H z}$ , $\\mathsf{C D C l}_{3},$ , Supplementary Fig. 58): δ 7.90-7.78 (m, 2H), 7.72-7.66 (m, 2H), 5.27 (dt, $\\mathsf{J}=7.2,1.2\\mathsf{H z},$ 1H), 4.5 (d, ${\\bf J}=7.2{\\sf H z}$ , 2H), 1.83 (s, 3H), 1.70 (s, 3H). HRESIMS (Supplementary Fig. 59): $\\boldsymbol{\\mathsf{m}}/z$ calculated for $\\mathrm{C_{13}H_{14}N O_{2}}$ $[\\mathsf{M}+\\mathsf{H}]^{+}$ : 216.1025; Found: 216.1024.  \n\nTo a solution of the intermediate compound 1 $(20.0\\mathbf{g}.$ $0.093\\mathrm{mol};$ in dichloromethane $(50\\mathrm{mL})$ was added chlorosulfonyl isocyanate $(10.4\\mathrm{mL}$ , 0.11 mol) under $\\mathsf{N}_{2}$ atmosphere. The reaction mixture was stirred for $30\\mathrm{min}$ at $0^{\\circ}\\mathrm{C}$ and then warmed up to room temperature for $72\\mathrm{{h}}$ . Then the reaction mixture was poured into a suspension of ${\\bf N a}_{2}{\\bf S O}_{3}$ $(41.6\\mathrm{g},\\ 0.33\\mathrm{mol})$ and ${\\sf N a}_{2}{\\sf H P O}_{4}$ $(46.9\\mathrm{g},0.33\\mathrm{mol})$ in water $(800\\mathrm{mL})$ ) and was stirred for $^{12\\mathrm{h}}$ . The aqueous phase was extracted with dichloromethane $(3\\times500\\mathrm{mL})$ ). The organic phase was combined and then dried over anhydrous magnesium sulfate and concentrated under vacuum to give the crude product. The crude product was purified by recrystallization from ethyl acetate and hexane to afford maleimide-protected DM (compound 2, Supplementary Fig. 57) as white solid $(14.6\\mathbf{g},$ $60.8\\%$ ). ${}^{1}\\mathsf{H}$ NMR ${\\bf\\langle400M H z}$ , $\\mathsf{C D C l}_{3}$ , Supplementary Fig. 60): $\\delta7.89$ - 7.81 (m, 2H), 7.77-7.67 $(\\mathsf{m},2\\mathsf{H})$ , 6.00 (br, 1H), 4.09 (dd, $\\mathsf{J}=8.0$ , 14.0 Hz, 1H), 3.91 (dd, $\\mathsf{J}=8.0$ , $14.0\\mathsf{H z}$ , 1H), 3.41 (t, $\\mathsf{\\Pi},\\mathsf{J}=8.0\\mathsf{H z}$ , 1H), 1.47 (s, 3H), 1.45 (s, 3H). HRESI-MS (Supplementary Fig. 61): $\\mathsf{m}/z$ calculated for $\\mathbf{C_{14}H_{15}N_{2}O_{3}}$ $[\\mathsf{M}+\\mathsf{H}]^{+}$ : 259.1083; Found: 259.1084.  \n\nTo a solution of above compound 2 $\\left(14.6\\mathrm{g},\\ 56.5\\mathsf{m m o l}\\right)$ in methanol $(200\\mathrm{mL})$ was added a solution of hydrazin hydrate $80\\%$ solution in water, $14~\\mathrm{mL}$ ). The reaction mixture was stirred at $70^{\\circ}\\mathrm{C}$ for $12\\mathsf{h}$ to result precipitate. After removing the precipitate by filtration, the filtrate was coevaporated with toluene $(3\\times200~\\mathrm{mL})$ for removing the residual hydrazine hydrate. The residue, di-tertbutyl dicarbonate $(\\mathsf{B o c}_{2}0$ , $24.6{\\bf g}$ $113.0\\mathrm{{mmol}}\\mathrm{{}}$ ) and triethylamine $(15.3\\mathrm{mL}$ , 113.0 mmol) were mixed in $500\\mathrm{mL}$ methanol. The reaction mixture was refluxed for $6\\mathfrak{h}$ . After filtration, the solvent was concentrated under vacuum to give the residue. The residue was dissolved in dichloromethane $(200\\mathrm{mL})$ and then washed sequentially with hydrochloric acid solution (1 N), sodium hydroxide solution (1 N) and brine $(200\\mathrm{mL})$ ). The organic phase was dried over anhydrous magnesium sulfate and then concentrated under vacuum to give the crude product, which was directly purified by column chromatography to obtain $\\beta$ -Lactam DM (compound 3, Supplementary Fig. 57) as white solid $(9.7\\mathrm{g},75.2\\%)$ . $\\mathsf{\\Pi}^{\\mathrm{1}}\\mathsf{H}$ NMR $(400\\mathsf{M H z}$ , $\\mathsf{C D C l}_{3}$ , Supplementary Fig. 62): δ 5.9 (s, 1H), 4.9 (s, 1H), 3.66-3.56 (m, 1H), 3.28 $(\\mathbf{t},\\mathbf{J}=10.2\\mathsf{H z}$ , 1H), 2.97 $(\\mathbf{t},\\mathbf{J}=7.8\\mathsf{H z}$ , 1H), 1.45 (s, 3H), 1.43 (s, 9H), 1.37 (s, 3H). $^{13}{\\mathsf{C}}$ NMR ( ${\\bf100M H z}$ , $\\mathsf{C D C l}_{3}$ , Supplementary Fig. 63): $\\delta$ 169.01, 155.79, 79.58, 58.24, 54.80, 37.07, 28.62, 28.37, 22.86. HRESI-MS (Supplementary Fig. 64): $\\mathsf{m}/z$ calculated for $\\mathrm{C_{11}H_{20}N_{2}N a O_{3}}$ $[M+\\mathsf{N a}]^{+}$ : 251.1372; Found: 251.1371.  \n\n4-(2-methylpropyl)azetidin-2-one (compound 4, $\\beta$ -lactam iPen, Supplementary Fig. 57) was synthesized according to the method reported in previous literature66. Briefly, to a solution of 5-Methyl-1- hexene $(3.5\\mathrm{g},\\ 35.6\\mathrm{mmol}$ , 1.0 equiv.) in dichloromethane $(\\boldsymbol{10}\\:\\mathrm{mL})$ , chlorosulfonyl isocyanate (3.3 mL, 37.4 mmol, 1.05 equiv.) was added at $0^{\\circ}\\mathbf{C}$ under $\\mathsf{N}_{2}$ atmosphere. The reaction mixture was stirred for 3 days at room temperature then monitored by thin layer chromatography (TLC). The reaction was quenched via carefully transferring into the buffer $(200\\mathrm{mL})$ consisting of anhydrous sodium sulfite $(13.5\\mathrm{g},$ 106.8 mmol, 3.0 equiv.) and disodium hydrogen phosphate $(15.2\\mathrm{g},$ 106.8 mmol, 3.0 equiv.), the mixture was stirred for overnight and extracted with dichloromethane $(3\\times100~\\mathrm{mL})$ , then the organic layer was combined and dried over anhydrous $\\mathsf{M g S O_{4}}$ . After removing the solvent under vacuum, the crude product was purified by silica gel column chromatography to afford $\\beta$ -lactam iPen (compound 4) as colorless oil ( $2.1\\mathrm{g},$ , $41.7\\%$ yield). $\\mathsf{\\Pi}^{\\mathsf{I}}\\mathsf{H}$ NMR ( $400\\mathsf{M H z}$ , $\\mathsf{C D C l}_{3},$ Supplementary Fig. 65): $\\delta6.06$ (s, 1H), 3.60-3.54 (m, 1H), 3.04 (ddd, $\\mathsf{J}=14.8$ , 4.8, 2 Hz, 1H), 3.04 (dq, $\\mathsf{J}=14.8$ , $1.2\\mathsf{H z}$ , 1H), 1.69-1.49 (m, 3H), 1.26-1.10 (m, 2H), 0.89 (d, ${\\mathsf{J}}=6.8{\\mathsf{H z}}$ , 6H). $^{13}{\\bf C}$ NMR $(100\\mathsf{M H z}$ , $\\mathsf{C D C l}_{3}$ , Supplementary Fig. 66): δ 168.87, 48.22, 43.09, 35.07, 33.14, 27.70, 22.34. HRESI-MS (Supplementary Fig. 67): $\\boldsymbol{\\mathsf{m}}/z$ calculated for $\\mathbf{C_{8}H_{15}N N a O}$ [M $+\\mathsf{N a}]^{+}{:164.1051}$ ; Found 164.1053.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 25,
+        "chunk": "# Synthesis of $\\pmb{\\beta}$ -amino acid polymers  \n\nAll polymerizations of $\\beta$ -lactams were carried in nitrogen-regulated glove box at room temperature. Initiator (tBuBzCl), $\\beta$ -lactams (DM and iPen) and the base catalyst LiHMDS were dissolved in dry THF to a concentration of $0.2\\ensuremath{\\mathsf{M}}$ respectively. The positive charge and hydrophobic composition of $\\beta$ -amino acid polymers was controlled by the initial feed ratio of tBuBzCl: DM: iPen. Briefly, 2 mL $\\beta$ -lactams with different volume ratios of DM: iPen were mixed, after adding $100\\upmu\\upiota$ tBuBzCl solution in THF and $300{\\upmu\\mathrm{L}}$ LiHMDS in THF into the mixture sequentially, the reaction mixture was stirred for $^{12\\mathrm{h}}$ . When the polymerization reaction was completed, the reaction mixture was poured into cold petroleum ether (PE, $45\\mathrm{mL},$ ) to precipitate out the crude product as a white solid, followed by centrifugation (2810 g) to remove the solvent. The crude product was dissolved in $2\\mathrm{mL}$ THF followed by pouring cold petroleum ether $(45\\mathrm{mL})$ to precipitate out the crude product. The $N$ -Boc protected polymers were purified by dissolution-precipitation process using THF/PE $(2\\mathrm{mL}/45\\mathrm{mL})$ three times and vacuum drying for overnight to give a white solid. The number-average molecular weight $(M_{n})$ and polydispersity index (D) were characterized by GPC using N, N-dimethylformamide (DMF) as the mobile phase.  \n\nN-Boc protected polymers were dissolved in trifluoroacetic acid (2 mL). Then the mixture was under shaking for $2\\mathfrak{h}$ at room temperature. After removing the solvent under a nitrogen flow, the residue was dissolved in methanol $\\left(1\\mathrm{mL}\\right)$ , followed by addition of cold MTBE $(45\\mathrm{mL})$ to precipitate out the crude polymers. The crude polymers were purified by three times of dissolution-precipitation process using methanol/MTBE $(1\\mathrm{mL}/45\\mathrm{mL})$ and vacuum drying for overnight. The purified polymers were dissolved in Milli-Q water and lyophilized to obtain a white powder in the form of TFA salt $(>80.0\\%$ yield), which was further characterized by $\\mathsf{\\Pi}^{\\mathrm{1}}\\mathsf{H}$ NMR and used for antibacterial assay.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 26,
+        "chunk": "# Minimum inhibitory concentration (MIC) assay  \n\n11 strains of gram positive and negative bacteria were respectively cultured in Luria-Bertani (LB) medium for $^{9\\mathfrak{h}}$ at $37^{\\circ}\\mathrm{C}$ under shaking at 200 rpm. After centrifugation at $4000~\\mathrm{rpm}$ for $5\\mathrm{{min}}$ , the bacteria in the culture medium were collected and re-suspended in MuellerHinton (MH) medium to $2\\times10^{5}\\mathrm{CFU\\mL^{-1}}$ as the working suspension. The deprotected polymer $\\mathsf{D M}_{x}i\\mathsf{P e n}_{y}$ libraries were respectively diluted to concentrations ranging from $3.13\\upmu\\mathrm{g}\\mathrm{mL}^{-1}$ to $400\\upmu\\mathrm{g}\\mathsf{m}\\mathsf{L}^{-1}$ by a twofold gradient dilution in a 96-well plate. After mixing equal volumes of bacterial cells suspension $(50\\upmu\\mathrm{L})$ and DMxiPeny solution $(50\\upmu\\mathrm{L})$ in each well, the 96-well plates were incubated at $37^{\\circ}\\mathrm{C}$ for $^{9\\mathfrak{h}}$ to collect OD values on a SpectraMax ${\\mathfrak{B}}_{\\mathbf{M}2}$ plate reader. MH medium was used as the blank; bacteria in MH medium was used as positive control. The percentage of bacterial cells survival was calculated from the equation below:  \n\n$$\n\\mathrm{Cell\\growth{\\left(\\%\\right)}}=\\frac{\\mathrm{OD_{600}^{p o l y m e r}}-\\mathrm{OD_{600}^{b l a n k}}}{\\mathrm{OD_{600}^{c o n t r o l}}-\\mathrm{OD_{600}^{b l a n k}}}\\times100.\n$$  \n\nThe MIC value was defined as the lowest concentration of an antimicrobial agent to completely inhibit microbial growth. Measurements were performed in duplicates, and the experiments were repeated at least twice.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 27,
+        "chunk": "# Hemolysis assay  \n\nFresh human blood was washed with Tris-buffered saline (TBS, $\\mathsf{p H}=$ 7.2) for three times and the collected human red blood cells (hRBCs) were diluted to $5\\%$ (v/v) with TBS to obtain working suspension. $\\mathsf{D M}_{x}i\\mathsf{P e n}_{y}$ solution were diluted to concentrations ranging from 3.13 to $400\\upmu\\mathrm{g}\\ \\mathsf{m}^{-1}$ by a two-fold gradient dilution in a 96-well plate. After mixing an equal volume of hRBCs suspension and $\\mathsf{D M}_{x}i\\mathsf{P e n}_{y}$ solution, 96-well plates were incubated at $37^{\\circ}\\mathrm{C}$ for 1 h. TBS was used as the blank, the mixture of Triton X-100 $0.1\\%$ in TBS) and hRBCs was used as the positive control. After centrifugation, ${\\ }^{80}\\upmu\\upiota$ of the supernatant in each well was transferred to another 96-well plate and the optical density (OD) value was collected at $405\\ \\mathrm{nm}$ . The percentage of hemolysis was calculated from  \n\n$$\n\\mathsf{h e m o l y s i s}\\left(\\%\\right)=\\frac{\\mathbf{OD}_{405}^{\\mathrm{polymer}}-\\mathbf{OD}_{405}^{\\mathsf{b l a n k}}}{\\mathbf{OD}_{405}^{\\mathrm{control}}-\\mathbf{OD}_{405}^{\\mathsf{b l a n k}}}\\times100.\n$$  \n\nThe ${\\mathsf{H C}}_{50}$ was defined as the concentration of a compound to cause $50\\%$ hemolysis. Measurements were performed in triplicate. The experiments were repeated three times independently.  \n\nAll sourced blood for hemolysis assays were donated by the Shanghai RuiJin Rehabilitation Hospital before the blood is disposed as scheduled and no recruitment information was supplied to the researchers of this project as per the agreement with University of East China University of Science and Technology Human Ethics Approval, therefore recruitment information are unknown.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 28,
+        "chunk": "# Cytotoxicity assay  \n\nThe cytotoxicity of $\\beta$ -amino acid polymers was studied using MTT assay. Specifically, COS-7 and HUVEC cells were respectively incubated in Dulbecco’s Modified Eagle’s Medium (DMEM) containing FBS $(10\\%)$  \n\nand penicillin/streptomycin $(1\\%)$ at $37^{\\circ}\\mathrm{C}$ in a humidified atmosphere containing $5^{\\circ}\\mathbf{C}\\mathbf{C}0_{2}$ . Cells were seeded in a 96 well plates at 5000 cells in $100\\upmu\\mathrm{L}$ DMEM medium for each well and the plates were incubated at $37^{\\circ}\\mathrm{C}$ in a humidified atmosphere containing $5\\%\\mathrm{CO}_{2}$ for $24\\mathsf{h}$ . Different concentrations of $\\mathsf{D M}_{x}i\\mathsf{P e n}_{y}$ solution ranging from $400\\upmu\\mathrm{g}\\mathsf{m}\\mathsf{L}^{-1}$ to $3.13\\upmu\\mathrm{g}\\mathrm{\\mL}^{-1}$ were prepared and added to HUVEC and COS-7 cells, respectively. The plates were incubated for another 48 hours. An aliquot of $10\\upmu\\mathrm{L}$ MTT solution $(5\\mathrm{{mg}\\mathrm{{mL^{-1})}}}$ in phosphate buffered saline (PBS) was added in each well and the plate was incubated for $4\\mathfrak{h}$ . After removing the supernatant, $150\\upmu\\upiota$ DMSO was added in each well and then the plate was shaken for 15 min before measuring the absorbance at $570\\ensuremath{\\mathrm{nm}}$ on a microplate reader. The untreated cells were used as positive control, DMEM solution was used as blank. The percentage of cell viability was calculated from  \n\n$$\n\\mathrm{Cell\\viability}(\\%)=\\frac{\\mathsf{A}_{570}^{\\mathrm{polymer}}-\\mathsf{A}_{570}^{\\mathsf{b l a n k}}}{\\mathsf{A}_{570}^{\\mathrm{control}}-\\mathsf{A}_{570}^{\\mathsf{b l a n k}}}\\times100.\n$$  \n\nThe $\\mathsf{I C}_{50}$ was defined as the minimum concentration to cause $50\\%$ inhibition. All experiments were carried out with three replicates. Each experiment was repeated at least twice.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 29,
+        "chunk": "# Synthesis of dye-labeled $(\\mathbf{D}\\mathbf{M_{0.8}}i\\mathbf{Pen_{0.2}})_{20}$  \n\nThe dye-labeled $\\beta$ -amino acid polymer $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ was synthesized according to the protocol in our previous study79. Briefly, the initiator Dye-NHS ester, co-initiator LiHMDS, DM monomer and iPen monomer were dissolved in dried tetrahydrofuran (THF) to the solution with a final concentration of $0.2\\mathsf{M}$ inside a glove box. DM $(1.6\\mathrm{mL})$ , iPen $(0.4\\mathrm{mL})$ and Dye-NHS ester $\\mathbf{\\Gamma}(0.1\\mathsf{m L})$ were mixed and stirred. Subsequently, LiHMDS $(0.3\\mathrm{mL})$ was quickly added into the mixture. The reaction mixture was stirred for $6\\mathfrak{h}$ at room temperature and then quenched with 5 drops of MeOH. After removing the solvent under $\\mathsf{N}_{2}$ flow, the residue was dissolved in THF (1 mL) and transferred to a centrifuge tube, followed by slowly addition of cold PE $(45\\mathrm{mL})$ into the mixture to precipitate out a yellow product. The N-Boc protected polymer was further purified via three times of dissolution-precipitation process using the solvent of THF/PE $\\mathrm{(1mL/}$ $45\\mathrm{mL}$ then vacuum dried and characterized by GPC using DMF containing $10\\mathrm{\\mM}$ LiBr as mobile phase. This polymer was dissolved in $2\\mathrm{mL}$ TFA and stirred at room temperature for $2\\mathfrak{h}$ to remove the Boc protection. After removing the TFA under $\\mathsf{N}_{2}$ flow, the residue was dissolved in MeOH (1 mL), followed by slow addition of cold methyl tert-butyl ether (MTBE, $45\\mathrm{mL}$ ) to precipitate out a yellow product. The N-Boc deprotected polymer was further purified via three times of dissolution-precipitation process using the solvent of MeOH/MTBE $(1\\mathrm{mL}/45\\mathrm{mL})$ ) then vacuum dried and dissolved in MilliQ water. Subsequently, the solution was subjected to lyophilization to give a final dye-labeled polymer $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ , which was used for confocal imaging.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 30,
+        "chunk": "# Time-lapse fluorescent confocal imaging assay  \n\nThe confocal imaging assay for drug-resistant S. aureus and drugresistant $E$ . coli was conducted according to the protocol in our previous study80. Briefly, the dye-labeled $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ ( $(4\\times\\mathsf{M B C}$ , green fluorescence) and propidium iodide ( $40\\mathsf{m M}$ , red fluorescence) were mixed in equal volumes to prepare a working solution. In addition, the bacteria were cultured in LB medium at $37^{\\circ}\\mathrm{C}$ for $6\\mathsf{h}$ to obtain the bacterial suspension, the bacterial suspension was washed by PBS buffer and then diluted in MH medium to achieve a working suspension with a cell density of $\\mathbf{1}\\times\\mathbf{10^{7}}\\mathbf{CFU\\SigmamL^{-1}}$ . $10\\upmu\\mathrm{L}$ of the bacterial suspension was dropped into a glass-bottomed cell culture dish for $10\\mathrm{{min}}$ to allow the bacteria to attach to the bottom. Subsequently, $10\\upmu\\mathrm{L}$ of working solution was added to the bacterial drop. The confocal images were captured at the various time points for three channels: bright field, $488\\mathsf{n m}$ (green fluorescence) and $562\\mathsf{n m}$ (red fluorescence), respectively. These images were used to record the bactericidal process.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 31,
+        "chunk": "# Outer membrane permeabilization assay  \n\nThe outer membrane permeabilization assay for drug-resistant E. coli was conducted according to the protocol in our previous study43. Briefly, the bacteria were cultured in LB medium at $37^{\\circ}\\mathrm{C}$ for $6\\mathsf{h}$ to obtain the bacterial suspension, the bacterial suspension was washed by PBS buffer and then diluted in HEPES medium ( $\\boldsymbol{5}\\boldsymbol{\\mathrm{mM}}$ HEPES, $20\\mathsf{m}\\mathsf{M}$ glucose, $\\mathsf{p H}=7.4$ ) to achieve a working suspension with a cell density of $3\\times10^{8}\\thinspace\\mathrm{CFUmL^{-1}}$ , followed by addition of 1-N-phenyl-naphthylamine (NPN) dye at a final concentration of $10\\upmu\\mathrm{M}$ . ${\\mathfrak{s o}}\\upmu\\upiota$ of working suspension containing NPN was added to each well of a 384-well plate. The fluorescence changes (excitation $\\lambda=350\\mathrm{nm}$ , emission $\\lambda{=}420\\mathrm{nm},$ ) were recorded on a SpectraMax ${\\bf\\tau}^{\\otimes}{\\bf M}2$ plate reader (Molecular Devics, USA). Once the fluorescence intensity remained stable, $10\\upmu\\mathrm{L}$ of $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ was added to the bacterial solution, and the fluorescence intensity was recorded continuously.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 32,
+        "chunk": "# Cytoplasmic membrane depolarization assay  \n\nThe cytoplasmic membrane depolarization for drug-resistant S. aureus and drug-resistant $\\boldsymbol{{\\cal E}}$ . coli was conducted according to the protocol in our previous study43. The drug-resistant bacteria were cultured in LB medium at $37^{\\circ}\\mathrm{C}$ for $6\\mathfrak{h}$ , and then the bacterial suspension was diluted in HEPES medium ( $\\mathsf{\\Pi}_{5\\mathsf{m M}}$ HEPES, $20\\mathrm{mM}$ glucose, $\\mathsf{p H}=7.4\\AA,$ ) to achieve a working suspension with a cell density of $\\mathbf{1}\\times\\mathbf{10^{7}}{\\mathrm{~CFU~mL^{-1}}}$ , followed by addition of 3, $3^{\\prime}$ -dipropylthiadicarbocyanine iodide (diSC3(5)) dye at a final concentration of $0.8\\upmu\\mathrm{M}$ . The bacterial suspension was incubated for 1 h, followed by the addition of KCl to a final concentration of $0.1\\ensuremath{\\mathsf{M}}$ to balance the cytoplasmic and external ${\\sf K}^{+}$ concentration. ${\\mathfrak{s o}}\\upmu\\upiota$ of bacterial suspension containing diSC3(5) was added to each well of a 384-well plate. The fluorescence changes (excitation $\\lambda=622{\\mathrm{nm}}$ , emission $\\lambda=673\\mathrm{nm}$ ) were recorded on a SpectraMax ${\\bf\\tau}^{\\otimes}{\\bf M}2$ plate reader (Molecular Devics, USA). Once the fluorescence intensity remained stable, $10\\upmu\\mathrm{L}$ of $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ and $0.1\\%$ Triton $\\mathbf{\\times}\\mathbf{-}100$ as the positive control was separately added to the bacterial solution and the fluorescence intensity was recorded continuously.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 33,
+        "chunk": "# Cytoplasmic membrane permeabilization assay  \n\nThe cytoplasmic membrane permeabilization assay for drug-resistant S. aureus and drug-resistant $E.$ coli was conducted according to the protocol in our previous study43. The drug-resistant bacteria were cultured in LB medium at $37^{\\circ}\\mathbf{C}$ for $^{6\\mathfrak{h}}$ , and then the bacterial suspension was diluted in HEPES medium (5 mM HEPES, $5\\mathsf{m M}$ glucose, $\\mathsf{p H}=7.4$ ) to achieve a working suspension with a cell density of $1\\times10^{8}$ $\\mathrm{CFU}\\mathrm{m}\\mathrm{L}^{-1}.$ , followed by addition of propidium iodide (PI) dye at a final concentration of $10\\upmu\\mathrm{M}$ . $150\\upmu\\upiota$ of bacterial suspension containing PI was added to each well of a corning 96-well plate. The fluorescence changes (excitation $\\lambda=535\\mathrm{{nm}}$ , emission $\\lambda{=}617\\mathsf{n m},$ ) were recorded on a SpectraMax $\\mathbf{\\phi}^{\\ast}(\\mathfrak{s})\\mathbf{M}2$ plate reader (Molecular Devics, USA). Once the fluorescence intensity remained stable, $10\\upmu\\mathrm{L}$ of $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ was added to the bacterial solution and the fluorescence intensity was recorded continuously.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 34,
+        "chunk": "# SEM characterization of bacteria morphology  \n\nThe SEM characterization for drug-resistant S. aureus and drugresistant $E.$ coli was conducted according to the protocol in our previous study79. Briefly, the drug-resistant bacteria were cultured in LB medium at $37^{\\circ}\\mathrm{C}$ for $^{9\\mathfrak{h}}$ , and then the bacterial suspension was diluted in LB medium to achieve a working suspension with a cell density of $\\mathbf{1}\\times\\mathbf{10}^{7}~\\mathrm{CFU~mL^{-1}}.$ , followed by addition of $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ at a final concentration of $1\\times\\mathsf{M B C}$ . The bacterial suspension was incubated at $37^{\\circ}\\mathrm{C}$ for $30\\mathrm{min}$ . An untreated bacteria suspension was used as the control. $(\\mathrm{DM}_{0.8}i\\mathrm{Pen}_{0.2})_{20}$ treated and untreated bacteria were collected by centrifugation at $1700\\times g$ for $5\\mathrm{{min}}$ . They were washed with phosphate buffer saline (PBS) once and then fixed with $4\\%$ glutaraldehyde in phosphate buffer (PB) at $25^{\\circ}\\mathrm{C}$ overnight. The bacteria were further washed with PBS and dehydrated with gradient ethanol (EtOH) solutions (30, 50, 70, 80, 90, 95, and then $100\\%$ ethanol). The samples were dried in air and then used for Field Emission Scanning Electron Microscopy (FESEM) characterization.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 35,
+        "chunk": "# Reporting summary  \n\nFurther information on research design is available in the Nature Portfolio Reporting Summary linked to this article.",
+        "category": " Abstract"
+    },
+    {
+        "id": 36,
+        "chunk": "# Data availability  \n\nAll collected raw data of $\\beta$ -amino acid polymers, $\\alpha$ -amino acid polymers, polymethacrylates, polymethacrylamides and other categories are available on GitHub: https://github.com/TianyuWu813/polymer_ prediction. All raw data to train the generative model are available on https://github.com/TianyuWu813/polymer_generation. The source data for all figures and tables in the manuscript and in the Supplementary Information are provided with this paper. Source data are provided with this paper.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 37,
+        "chunk": "# Code availability  \n\nCodes supporting this study are available on GitHub and Zenodo: https://github.com/TianyuWu813/polymer_prediction for polymer property prediction81 and https://github.com/TianyuWu813/polymer_ generation for polymer generation82.",
+        "category": " References"
+    },
+    {
+        "id": 38,
+        "chunk": "# References  \n\n1. Ghosh, C., Sarkar, P., Issa, R. & Haldar, J. Alternatives to conventional antibiotics in the era of antimicrobial resistance. Trends Microbiol. 27, 323–338 (2019).   \n2. Kwon, J.H., Powderly, W.G. The post-antibiotic era is here (American Association for the Advancement of Science, 2021).   \n3. Schrader, S. M. et al. Multiform antimicrobial resistance from a metabolic mutation. Sci. Adv. 7, 2037 (2021).   \n4. Thompson, T. The staggering death toll of drug-resistant bacteria. Nature, https://doi.org/10.1038/d41586-022-00228- $\\cdot\\mathsf{x}$ (2022).   \n5. Zhong, W. et al. Designer broad-spectrum polyimidazolium antibiotics. Proc. Natl Acad. Sci. USA 117, 31376–31385 (2020).   \n6. Mitcheltree, M. J. et al. A synthetic antibiotic class overcoming bacterial multidrug resistance. Nature 599, 507–512 (2021).   \n7. Hancock, R. E. & Sahl, H.-G. Antimicrobial and host-defense peptides as new anti-infective therapeutic strategies. Nat. 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+        "category": " References"
+    },
+    {
+        "id": 39,
+        "chunk": "# Acknowledgements  \n\nThis research was supported by National Natural Science Foundation of China (Basic Science Center Program: No. 61988101), National Natural Science Foundation of China (No. T2325010, No. 22075078, No.62233005 and No. 62293502), National Key Research and Development Program of China (2022YFC2303100), German Research Foundation DFG (Project No.411803875), Fundamental Research Funds for the Central Universities (222202417006), Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism (Shanghai Municipal Education Commission), and the Programme of Introducing Talents of Discipline to Universities (the 111 Project) under Grant B17017 and Shanghai AI Lab. We also thank the Research Center of Analysis and Test of East China University of Science and Technology for the help with the characterization. The authors also thank the support of the Analysis and Testing Center of School of Chemical Engineering, East China university of Science and Technology. Thanks for the staff members of the Integrated Laser Microscopy System at the National Facility for Protein Science in Shanghai (NFPS), Zhangjiang Lab, China, for providing technical support and assistance in data collection and analysis. Please refer to Journal-level guidance for any specific requirements.",
+        "category": " Acknowledgements"
+    },
+    {
+        "id": 40,
+        "chunk": "# Author contributions  \n\nY.T. and R.L. directed the whole project and conceived the idea. T.W. and M.Z. designed the experiments and wrote the manuscript together. T.W. constructed the polymer inverse design framework. M.Z. contributed to the polymer synthesis,antibacterial mechanism study and the data analysis. F.Q and J.K contributed to result discussion. J.Z. conducted the antibacterial assay. Q.C. conducted the cytotoxic assay. All authors proofread the manuscript.",
+        "category": " Abstract"
+    },
+    {
+        "id": 41,
+        "chunk": "# Competing interests  \n\nThe authors declare no competing interests.  \n\nAdditional information   \nSupplementary information The online version contains supplementary material available at   \nhttps://doi.org/10.1038/s41467-024-50533-4.  \n\nCorrespondence and requests for materials should be addressed to Runhui Liu or Yang Tang.  \n\nPeer review information Nature Communications thanks the anonymous, reviewer(s) for their contribution to the peer review of this work. A peer review file is available.  \n\nReprints and permissions information is available at http://www.nature.com/reprints  \n\nPublisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 42,
+        "chunk": "# Article  \n\nOpen Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/ licenses/by/4.0/.  \n\n$\\circledcirc$ The Author(s) 2024",
+        "category": " References"
+    }
+]
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+    {
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+        "chunk": "分  类  号：R318.08  \n研究生学号：2020741014  \n\n单位代码：10183密    级：公开",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# 吉 林 大 学博士学位论文  \n\n局部递送雷帕霉素通过调控骨质疏松微环境促进 3D 打印微   \n孔假体界面骨整合的机制研究   \nStudy on the mechanism of local rapamycin delivery to   \npromote the osseointegration of 3D printed microporous   \nprosthetic interface by regulating the osteoporotic   \nmicroenvironment  \n\n作者姓名：李祖浩专    业：外科学研究方向：骨组织工程指导教师：王金成 教授培养单位：白求恩第二临床医学院  \n\n2023 年 5 月  \n\n局部递送雷帕霉素通过调控骨质疏松微环境促进 3D 打印微   \n孔假体界面骨整合的机制研究   \nStudy on the mechanism of local rapamycin delivery to   \npromote the osseointegration of 3D printed microporous   \nprosthetic interface by regulating the osteoporotic   \nmicroenvironment  \n\n作者姓名：李祖浩专业名称：外科学指导教师：王金成 教授学位类别：医学博士  \n\n论文答辩日期： 2023 年  5 月 26 日授予学位日期： 年    月    日  \n\n答辩委员会组成：  \n\n姓名 职称 工作单位  \n主席 李春义 教授 吉林农业大学  \n委员 丁建勋 研究员 中国科学院长春应用化学研究所刘钦毅 教授 吉林大学黄岚峰 副教授 吉林大学赵昕 副教授 吉林大学",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# 中文摘要",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# 局部递送雷帕霉素通过调控骨质疏松微环境促进 3D 打印微孔假体",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 界面骨整合的机制研究  \n\n骨整合指假体植入后假体界面与宿主骨组织之间形成的牢固连接，优良的骨整合是实现假体植入后长期稳定、延长假体使用寿命的关键因素。然而，临床上接受关节置换手术的患者多数为老年患者，常伴有骨质疏松，在假体植入后由于局部骨质不良、骨再生能力不佳，造成骨整合效果不理想，从而导致术后假体松动、移位和假体周围骨折等并发症高发。为提升骨整合效率，通过新兴的 3D 打印技术制备的个性化假体，在宏观上与植入位置的骨缺损高度匹配，在微观上可控的微孔结构提供初始稳定性、降低弹性模量、诱导骨长入与骨整合。然而，临床上广泛使用的3D 打印钛合金假体仍具有一定的生物惰性，在骨质疏松状态下的骨整合效率还有待进一步提高。目前有研究表明，骨质疏松状态下的骨再生和骨整合能力不足，可能是部分由于骨质疏松源性骨髓间充质干细胞（Osteoporosisderived bone marrow mesechymal stem cell, OP-BMSCs）低下的自噬能力导致细胞活性和增殖能力下降，成骨分化不足，趋向于成脂分化而造成。因此，在利于骨长入的3D 打印微孔假体界面负载激活 OP-BMSCs 自噬活性的药物，是恢复 OP-BMSCs 细胞活性和功能、促进假体界面骨整合的潜在策略。  \n\n针对上述问题，本研究拟设计自噬激活剂——雷帕霉素的两种递送策略来加强3D 打印假体界面的骨整合效果，具体方法如下：  \n\n（1）研究体系一：经皮超声介导雷帕霉素递送通过激活自噬和调控成骨微环境促进骨质疏松状态下假体界面骨整合：$\\textcircled{1}$ ． $\\mathrm{Ti_{6}A l_{4}V}$ 粉末为原料，利用 3D 打印电子束熔融技术成功制备了孔径为 800$\\upmu\\mathrm{m}$ ，孔隙率约为 $70\\%$ 的钛合金微孔假体，并对获得支架的表面形貌和力学性能进行分析。$\\textcircled{2}$ ．通过双侧卵巢切除术法制备骨质疏松兔子模型，提取和培养 BMSCs，使用流式细胞学对 BMSCs 典型的细胞表面抗原表达特点（CD45、CD90、CD105）进行分析以及成骨、成软骨和成脂三向分化能力进行鉴定。  \n\n$\\textcircled{3}$ ．首先通过体外检测超声介导雷帕霉素递送药物浓度与作用时间的关系，使用FITC-雷帕霉素体内递送，通过对皮肤、肌肉和骨的组织学观察确定在超声电导仪的频率为 $30\\mathrm{kHz}$ ，强度为 $45\\mathrm{W}/\\mathrm{cm}^{2}$ ，时间为 $10\\mathrm{min}$ 时超声介导雷帕霉素递送的安全性和有效性；随后通过 Western Blot 检测细胞中自噬关键蛋白 mTOR、LC3Ⅱ/Ⅰ和 P62 的表达水平，Ad-mCherry-GFP-LC3B 双荧光腺病毒感染细胞以及透射电子显微镜观察细胞内自噬泡形成情况，综合评估超声递送雷帕霉素对 OP-BMSCs 自噬水平的影响。  \n$\\textcircled{4}$ ．探究超声介导雷帕霉素递送对 OP-BMSCs 的功能调节，主要包括 CCK-8 法检测细胞增殖，Calcein-AM/PI 细胞活死染色分析细胞活性，鬼笔环肽染色观察细胞骨架，细胞划痕实验和 Transwell 实验检查细胞迁移能力，茜素红染色、RT-qPCR 和免疫荧光染色探究细胞成骨分化情况，油红 O 染色分析细胞成脂肪分化能力。  \n$\\textcircled{5}$ ．植入 3D 打印微孔假体至兔左侧股骨远端外侧髁，观察超声介导雷帕霉素递送促进骨质疏松状态下假体界面骨整合，主要包括 Micro-CT、硬组织切片和力学测试评估界面骨整合与周围骨质情况，界面周围骨质 mTOR、LC3Ⅱ/Ⅰ和P62的蛋白水平检测评估自噬变化，界面周围骨质 RT-qPCR 和免疫荧光染色观察成骨相关标记物的表达。  \n（2）研究体系二：功能化水凝胶介导的雷帕霉素局部递送通过激活自噬和调控成骨微环境促进骨质疏松状态下假体界面骨整合  \n$\\textcircled{1}$ ．通过交联 N-羧乙基壳聚糖（CEC)、纳米银线（AgNW）、聚乙烯醇（PVA）、琼脂糖和甘油合成 CEC-PVA-AgNW 水凝胶，并表征水凝胶的流变学特征、力学性质、微观形貌、降解、生物相容性等理化性质。  \n$\\textcircled{2}$ ．制备3D 打印微孔假体，并将负载雷帕霉素的水凝胶与微孔假体复合构建 3D打印生物活性界面；评估 3D 打印生物活性界面的药物释放曲线以及对金黄色葡萄球菌（S. aureus）和耐甲氧西林金黄色葡萄球菌（MRSA）的抗菌性能。$\\textcircled{3}$ ．通过 Western Blot 检测细胞中自噬关键蛋白 mTOR、LC3Ⅱ/Ⅰ和 P62 的表达水平以及 Ad-mCherry-GFP-LC3B 双荧光腺病毒感染细胞，评估 3D 打印生物活性界面对OP-BMSCs 自噬的影响。  \n$\\textcircled{4}$ ．探究3D 打印生物活性界面对 OP-BMSCs 的功能调节，主要包括 CCK-8 法检测细胞增殖，Calcein-AM/PI 细胞活死染色分析细胞活性，鬼笔环肽染色观察细胞骨架，茜素红染色和 RT-qPCR 探究细胞成骨分化情况，油红 O 染色分析细胞成脂肪分化能力。  \n$\\textcircled{5}$ ．将3D 打印生物活性假体界面植入兔左侧股骨远端外侧髁，观察其在骨质疏松状态下的骨整合情况，主要包括 Micro-CT 评估骨长入，硬组织切片评估骨整合效果，力学测试评估界面骨整合与周围骨质情况，界面周围骨质 mTOR、LC3Ⅱ/Ⅰ和P62 的蛋白水平检测评估自噬变化，界面周围骨质 RT-qPCR 和免疫荧光染色观察成骨相关标记物的表达。  \n$\\textcircled{6}$ ．3D 打印生物活性界面植入含有 S. aureus 和 MRSA 的股骨远端骨缺损中，评估在感染状态下假体界面的骨整合，包括血液学检查评估全身感染状态，影像学、硬切片组织学和力学测试评估假体界面骨整合效果。  \n\n通过这两个体系研究发现，无论是经皮超声介导雷帕霉素递送还是功能化水凝胶介导的雷帕霉素局部递送，都可以通过激活 OP-BMSCs 自噬活性来提高细胞活性和成骨分化能力，同时抑制成脂分化，从而促进3D 打印微孔假体界面在骨质疏松状态下的骨整合。此外，功能化水凝胶中由于AgNW 的引入赋予了 3D打印生物活性界面独特的抗菌性能，可以有效的预防假体周围感染。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 关键词：  \n\n骨质疏松，3D 打印，水凝胶，骨整合，自噬",
+        "category": " Abstract"
+    },
+    {
+        "id": 7,
+        "chunk": "# Abstract",
+        "category": " Abstract"
+    },
+    {
+        "id": 8,
+        "chunk": "# Study on the mechanism of local rapamycin delivery to promote the osseointegration of 3D printed microporous prosthetic interface by regulating the osteoporotic microenvironment  \n\nOsteointegration refers to the firm connection between the prosthesis interface and the host bone tissue after the prosthesis is implanted. Excellent osteointegration is the key factor to achieve long-term stability and prolong the service life of the prosthesis. However, most of the patients receiving joint replacement surgery in clinic are elderly patients, often accompanied by osteoporosis. After the prosthesis is implanted, the osteointegration is not ideal due to local bone recession and poor bone regeneration ability, which leads to a high incidence of complications such as prosthesis loosening, displacement and periprosthetic fractures. In order to improve the osteointegration, the personalized prosthesis prepared by the emerging 3D printing technology is highly matched with the bone defect at the implantation site in the macro, and the micro controllable microporous structure provides initial stability, reduces the elastic modulus, and induces bone ingrowth and bone integration. However, 3D printed titanium alloy prosthesis, which is widely used in clinical practice, still has a certain degree of biological inertia, and the osteointegration efficiency under osteoporosis still needs to be improved. At present, some studies have shown that the insufficient ability of bone regeneration and osteointegration in osteoporosis may be partly due to the low autophagy level of osteoporotic derived bone marrow mesenchymal stem cells (OPBMSCs), which leads to low cell viability and proliferation, insufficient osteogenic differentiation and preferable adipogenic differentiation. Therefore, loading drugs that activate the autophagic activity of OP-BMSCs at the 3D printed microporous prosthesis interface which is conducive to bone growth is a potential strategy to restore the activity and function of OP-BMSCs and promote osseointegration. In view of the above problems, this study intends to design two delivery strategies of autophagy activator (rapamycin) to enhance the osseointegration of 3D printed prosthesis interface. The specific strategies are as follows:  \n\n(1) Research system I: Percutaneous ultrasound mediated rapamycin delivery promotes osseointegration at the prosthesis interface under osteoporosis by activating autophagy and regulating the osteogenic microenvironment.  \n\n$\\textcircled{1}$ .Using Ti6Al4V powder as raw material, we have successfully prepared 3D printed titanium alloy microporous prosthesis with the pore diameter was about $800~{\\upmu\\mathrm{m}}$ and porosity was about $70\\%$ . And then, the surface morphology and mechanical properties of the obtained scaffold were analyzed.  \n\n$\\textcircled{2}$ . The osteoporotic rabbit model was prepared by bilateral ovariectomy, and then BMSCs were extracted and cultured, and the typical cell surface antigen expression (CD45, CD90, CD105) of BMSCs were identified by flow cytometry, and the triadic differentiation ability of osteogenesis, chondrogenesis and adipogenesis was analyzed. $\\textcircled{3}$ . First, the relationship between the concentration of rapamycin by ultrasound mediated delivery and the action time was detected in vitro, and FITC-rapamycin was used for delivery in vivo, and the skin, muscle and bone tissues were observed. Thus, the safety and efficient parameters of ultrasound conductance instrument to deliver rapamycin were determined, namely the frequency was $30~\\mathrm{kHz}$ , the intensity was $45\\mathrm{W}/\\mathrm{cm}^{2}$ , and the time was 10 minutes. Then Western Blot was applied to evaluate the expression of the key autophagic proteins (mTOR, LC3 Ⅱ/Ⅰ and P62), Ad-mCherryGFP-LC3B double fluorescent adenovirus infection cells, and transmission electron microscopy for observing the formation of autophagic vesicles in cells, thus comprehensively evaluating the impact of ultrasound mediated rapamycin delivery on the autophagic level of OP-BMSCs.  \n\n$\\textcircled{4}$ . Studies on the cell functions of OP-BMSCs regulated by ultrasound mediated rapamycin delivery, mainly including CCK-8 assay to test cell proliferation, Calcein AM/PI staining to analyze cell activity, phalloidin staining to observe the cytoskeleton, cell scratch test and Transwell test to check the cell migration ability, alizarin red staining, RT-qPCR and immunofluorescence staining to explore the osteoblastic differentiation of OP-BMSCs, and Oil Red O staining to detect the adipogenic differentiation of OP-BMSCs.  \n\n$\\textcircled{5}$ The 3D printed microporous prosthesis was implanted into the lateral condyle of the left distal femur of rabbits. A series of tests were used to observe the ultrasound mediated rapamycin delivery promoting osseointegration of the prosthesis interface in osteoporosis, mainly including Micro-CT, hard tissue slice, and mechanical test evaluated the osseointegration at the interface and the surrounding bone condition; VI  \n\ndetection of protein level of mTOR, LC3 II/I and P62  in the bone tissue assessed autophagic changes around the interface; the expression of osteogenic markers was observed by RT-qPCR and immunofluorescence staining in the bone around the interface.  \n\n(2) Research system II: Functional hydrogel mediated local delivery of rapamycin promotes osseointegration at the prosthesis interface under osteoporosis by activating autophagy and regulating the osteogenic microenvironment.   \n$\\textcircled{1}$ . CEC-PVA-AgNW hydrogels were synthesized by cross-linking N-carboxyethyl chitosan (CEC), silver nanowires (AgNW), polyvinyl alcohol (PVA), agarose and glycerin, and then the characteristics of rheological festures, mechanical properties, microscopic morphology, degradation, biocompatibility, and other physical and chemical properties of the hydrogels were detected.   \n$\\textcircled{2}$ . 3D printed microporous prosthesis was prepared, and the 3D printed bioactive interface was constructed by compositing the rapamycin loaded hydrogel with microporous prosthesis. The drug release curve of 3D printed bioactive interface and the antibacterial performance against S. aureus and MRSA were evaluated.   \n$\\textcircled{3}$ . The expression levels of key proteins of autophagy (mTOR, LC3 Ⅱ/Ⅰ and P62) were evaluated by Western Blot, and Ad mCherry GFP-LC3B double fluorescent adenovirus infection cells were used to evaluate the regulation of 3D printed bioactive interface on autophagy of OP-BMSCs.   \n$\\textcircled{4}$ . Studies on the cell functions of OP-BMSCs regulated by 3D printed bioactive interface, mainly including CCK-8 assay to test cell proliferation, Calcein AM/PI staining to analyze cell activity, phalloidin staining to observe the cytoskeleton, alizarin red staining and RT-qPCR to explore the osteoblastic differentiation of OP-BMSCs, and Oil Red O staining to detect the adipogenic differentiation of OP-BMSCs. $\\textcircled{5}$ . The 3D printed bioactive prosthesis interface was implanted into the lateral condyle of the left distal femur of rabbits. A series of tests were used to observe the 3D printed bioactive prosthesis interface promoting osseointegration in osteoporosis, mainly including Micro-CT, hard tissue slice, and mechanical test evaluated the osseointegration at the interface and the surrounding bone condition; detection of protein level of mTOR, LC3 II/I and P62 in the bone tissue assessed autophagic changes around the interface; the expression of osteogenic markers was observed by RT-qPCR and immunofluorescence staining in the bone around the interface.  \n\n$\\textcircled{6}$ . 3D printed bioactive interface was implanted into the distal femoral bone defects infected with S. aureus and MRSA, to evaluate the bone integration of the prosthesis interface under infection, including hematological examination to evaluate the status of systemic infection, and imaging, hard section histology and mechanical testing to evaluate the bone integration effect of the prosthesis interface.  \n\nThrough the studies of these two systems, it was found that both percutaneous ultrasound mediated rapamycin delivery and functional hydrogel mediated local delivery of rapamycin could improve the cell activity and osteogenic differentiation capacities of OP-BMSCs while inhibiting adipogenic differentiation by activating the autophagic activity, thereby promoting the bone integration of 3D printed microporous prosthesis interface in osteoporosis. In addition, the introduction of AgNW into functional hydrogel endows 3D printed bioactive interface with unique antibacterial performance, which can effectively prevent infection around the prosthesis.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# Keywords:  \n\nOsteoporosis, 3D printing, Hydrogel, Osteointegration, Autophagy",
+        "category": " Abstract"
+    },
+    {
+        "id": 10,
+        "chunk": "# 目  录  \n\n第 1 章 绪论.  \n1.1 骨质疏松性骨整合微环境  \n1.1.1 骨整合的生理过程 . .1  \n1.1.2 骨质疏松性骨微环境. 3  \n1.2 骨质疏松性骨整合的假体设计 .12  \n1.2.1 假体主体材料 . ...12  \n1.2.2 3D 打印微孔假体 ...14  \n1.2.3 假体表面涂层与改性 . ..17  \n1.2.4 局部递送活性物质 . ...19  \n1.3 局部活性物质递送策略. .22  \n1.3.1 体内局部递送系统 . .22  \n1.3.2 体外经皮递送系统 . .25  \n1.4 选题目的与主要研究内容 . .27  \n第 2 章 经皮超声介导雷帕霉素递送通过激活自噬和调控成骨微环境  \n促进骨质疏松状态下假体界面骨整合 . .29  \n2.1 3D 打印微孔假体界面的制备与表征.. ..30  \n2.1.1 实验仪器与材料 . ..30  \n2.1.2 实验方法 . ..30  \n2.1.3 实验结果 . ..31  \n2.1.4 讨论 . ...32  \n2.1.5 小结 ..33  \n2.2 骨质疏松家兔模型建立及 BMSCs 提取、培养和鉴定 .. ..33  \n2.2.1 实验仪器与材料 . ...33  \n2.2.2 实验方法 ..35  \n2.2.3 实验结果 ..37  \n2.2.4 讨论 .. ...40  \n2.2.5 小结 ..40  \n2.3 超声介导雷帕霉素递送激活 OP-BMSCs 自噬 . ..41  \n2.3.1 实验仪器与材料 . ...41  \n2.3.2 实验方法 . ..42  \n2.3.3 实验结果 ...45  \n2.3.4 讨论 .. ..47  \n2.3.5 小结 ..49  \n2.4 超声介导雷帕霉素递送调节 OP-BMSCs 功能 .49  \n2.4.1 实验仪器与材料 .49  \n2.4.2 实验方法 . ...51  \n2.4.3 结果 . ....55  \n2.4.4 讨论 ... ...59  \n2.4.5 小结 .60  \n2.5 超声介导雷帕霉素递送促进骨质疏松状态下假体界面骨整合 61  \n2.5.1 实验仪器与材料 ..61  \n2.5.2 实验方法 ..62  \n2.5.3 结果 . ...67  \n2.5.4 讨论 . .72  \n2.5.5 小结 . ...76  \n2.6 本章总结 76  \n第 3 章 功能化水凝胶介导的雷帕霉素局部递送通过激活自噬和调控  \n成骨微环境促进骨质疏松状态下假体界面骨整合 . 77  \n3.1 水凝胶的制备与表征 .. ..78  \n3.1.1 实验仪器与材料 . ...78  \n3.1.2 实验方法 ..79  \n3.1.3 结果 .. ...81  \n3.1.4 讨论 . ..84  \n3.1.5 小结 . ....85  \n3.2 3D 打印生物活性界面制备、表征与抗菌性分析 . .....85  \n3.2.1 实验仪器与材料 .... ....85  \n3.2.2 实验方法 ..87  \n3.2.3 结果 .. ...88  \n3.2.4 讨论 . ....90  \n3.2.5 小结 ..91  \n3.3 3D 打印生物活性界面激活 OP-BMSCs 自噬 . ...91  \n3.3.1 实验仪器与材料 ..91  \n3.3.2 实验方法 . ...92  \n3.3.3 实验结果 ....93  \n3.3.4 讨论 ... ....94  \n3.3.5 小结 ..95  \n3.4 3D 打印生物活性界面调节 OP-BMSCs 功能 . ...95  \n3.4.1 实验仪器与材料 ...95  \n3.4.2 实验方法 ..97  \n3.4.3 结果 . ...99  \n3.4.4 讨论 . .101  \n3.4.5 小结 . .102  \n\n3.5 3D 打印生物活性界面促进骨质疏松状态下假体界面骨整合 . 103  \n\n3.5.1 实验仪器与材料. .103  \n3.5.2 实验方法 . .104  \n3.5.3 结果 .105  \n3.5.4 讨论 . 111  \n3.5.5 小结 .113  \n3.6 3D 打印生物活性界面促进感染状态下假体界面骨整合 .113  \n3.6.1 实验仪器与材料 .113  \n3.6.2 实验方法 .114  \n3.6.3 结果 . 115  \n3.6.4 讨论 . .117  \n3.7 本章总结. 118  \n第4 章 全文结论与展望 .121  \n4.1 全文结论. .121  \n4.2 本论文关键创新点. .121  \n4.3 研究展望 .122  \n参考文献 . 123",
+        "category": " Introduction"
+    },
+    {
+        "id": 11,
+        "chunk": "# 英文缩略词表  \n\n<html><body><table><tr><td>英文缩写</td><td>英文全称</td><td>中文全称</td></tr><tr><td>MSCs</td><td>Mesenchymal stem cells</td><td>间充质干细胞</td></tr><tr><td></td><td>OP-BMSCs Osteoporosis derived-bone marrow 骨质疏松状态下的骨髓间</td><td></td></tr><tr><td></td><td>mesenchymal stem cells</td><td>质干细胞</td></tr><tr><td>mTOR</td><td> Mechanistic Target of Rapamycin</td><td>机械性雷帕霉素的靶标</td></tr><tr><td>ROS</td><td>Reactive oxygen species</td><td>活性氧</td></tr><tr><td>BMP-2</td><td>Bone morphogenetic protein-2</td><td>骨形态发生蛋白-2</td></tr><tr><td>TGF-β PDGF-BB</td><td>Transforming growth factor-β</td><td>转化生长因子-β</td></tr><tr><td>TNF-α</td><td>Platelet-derived growth factor BB</td><td>血小板衍生生长因子BB</td></tr><tr><td>IL-1</td><td>Tumor necrosis factor-α</td><td>肿瘤坏死因子-α</td></tr><tr><td>SLS</td><td>Interleukin-1</td><td>白介素-1</td></tr><tr><td>SLM</td><td>Selective laser sintering</td><td>选区激光烧结</td></tr><tr><td></td><td>Selective laser melting</td><td>选区激光熔融</td></tr><tr><td>EBM p-OGP</td><td>Electron beam melting, Phosphorylated　osteogenic　growth 磷酸化成骨生长肽</td><td>电子束熔融</td></tr><tr><td></td><td> peptide</td><td></td></tr><tr><td>VEGF</td><td>Vascular endothelial growth factor</td><td>血管内皮细胞生长因子</td></tr><tr><td>OPG</td><td>Osteoprotegerin</td><td>骨保护素</td></tr><tr><td>PTH</td><td>1-34 human parathyroid hormone</td><td>1-34人甲状旁腺激素</td></tr><tr><td>OVX</td><td>Ovariectomy</td><td>卵巢切除术</td></tr><tr><td>ELISA</td><td>Enzyme-linked immunosorbent assay</td><td>酶联免疫吸附试验</td></tr><tr><td>BMD</td><td>Bone mineral density</td><td>骨密度</td></tr><tr><td>MAR</td><td>Mineral apposition rate</td><td>矿物质沉积率</td></tr><tr><td>MS/BS</td><td>Mineralizing surface per bone surface 矿化表面/骨表面</td><td></td></tr><tr><td>BFR/BS</td><td>Bone formation rate per bone surface</td><td>骨形成率/骨表面</td></tr><tr><td>CEC</td><td>N-carboxyethyl chitosan</td><td>N-羧乙基壳聚糖</td></tr><tr><td>AgNW</td><td>Silver Nanowires</td><td>纳米银线</td></tr><tr><td>PVA</td><td>Polyvinyl alcohol</td><td>聚乙烯醇</td></tr></table></body></html>",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# 第 1 章 绪论",
+        "category": " Introduction"
+    },
+    {
+        "id": 13,
+        "chunk": "# 1.1 骨质疏松性骨整合微环境  \n\n随着人口老龄化的进展，骨关节炎的患病率逐年增加，且与骨质疏松的发病率成正相关。根据全球疾病负担显示膝关节和髋关节骨关节炎的全球年龄标准化发病率分别为 $3.8\\%$ 和 $0.85\\%$ [1]。从具体数字来说，目前全球已有超过 3 亿骨关节炎患者，而我国的骨关节炎流行病例居全球首位，40 岁以上原发性骨关节炎患者总体患病率高达 $46.3\\%^{[2]}$ 。全关节置换术已成为降低疼痛和恢复关节功能的有效解决方案。然而，假体植入后的无菌性松动、移位，假体周围骨折以及感染等导致的失败以及在这些情况下所需的翻修手术仍然是一个重大的临床挑战。  \n\n假体植入后的长期稳定性是骨关节外科手术成功的关键之一。骨整合是骨与内植物之间的功能结构连接，被认为是非骨水泥假体固定和整合的关键过程[3]。骨整合是宿主骨与植入物界面之间由新生骨组织牢固连接，假体与骨位置关系稳定，不发生相对微动、位移。骨整合受多种因素的影响，主要包括植入物的性能和受体疾病状态等。随着人口老龄化的加深，接受关节置换的患者合并骨质疏松症的病例已成为常规，这一比例可达 $31\\%$ ，甚至更高 [4, 5]。骨质疏松症患者在假体植入后骨整合能力不足，假体无菌性松动、移位和假体周围骨折等并发症高是困扰关节外科的难题 [6]。因此，深入理解骨整合的机制、阐明骨质疏松骨整合受限的原因、设计利于骨质疏松患者骨整合的假体是关节外科亟需解决的重点问题之一。",
+        "category": " Introduction"
+    },
+    {
+        "id": 14,
+        "chunk": "# 1.1.1 骨整合的生理过程  \n\n骨整合是指宿主骨和人工植入物表面之间形成有序化的结构连接和功能联系，是影响内植物植入后假体寿命的关键性事件。假体植入后界面骨整合过程与骨损伤后的愈合过程具有一定的相似性，它们都涉及骨质破坏、免疫细胞募集、血管新生、骨基质沉积、骨化等阶段，但它们最大的区别在于连接结构的不同：骨愈合是骨与骨之间的连接，而骨整合是骨与异种假体界面材料的连接。骨整合是一个涉及一系列级联响应的动态过程，包括一系列的细胞和细胞外生物事件，其中植入物表面的特性起着重要作用。如图 1.1 所示，骨整合的过程可以根据假体界面周围发生的生物反应大致分为 5 个阶段 [7]。  \n\n（ⅰ）外伤、截骨导致的骨损伤、以及异体植入物置入体内后会迅速在局部产生炎症反应，导致各种蛋白质的释放，如生长因子和细胞因子，同时红细胞、血小板与植入物表面接触，启动外源性凝血过程，在植入物表面形成凝血块 [7, 8]。几分钟后，这些凝血块中释放的蛋白质和脂质将被植入物表面吸附，作为细胞迁移和增殖的信号 [9]。蛋白质的具体类型和粘附牢固度在很大程度上取决于植入物表面的特征，如形貌特征、粗糙度和亲水性等。随后，血小板促进纤维蛋白基质的形成，这些纤维蛋白基质是细胞迁移和附着的“桥梁”[10-12]。  \n\n（ⅱ）在假体植入后 2-3 天，巨噬细胞和中性粒细胞通过“桥梁”附着在植入物界面上，清除病原体和坏死组织，分解凝血块，为随后形成的新生血管腾出空间 [13, 14]。在第4 天之后 ，在植入物和宿主骨之间的间隙发生血管生成事件，非分化骨髓间充质干细胞（Mesenchymal stem cells, MSCs）聚集在血管结构周围。在一系列生长因子和细胞因子的影响下，MSCs 分化为成骨细胞，可产生细胞外基质并形成未成熟的编织骨 [15, 16]。然而，此时的 MSCs 也可以分化为成纤维细胞，这可能会刺激植入物表面形成纤维膜，并阻碍骨长入过程 [17, 18]。而 MSCs的这种不定向分化主要受假体表面性质和周围细胞通讯的影响 [19, 20]。  \n\n（ⅲ）在假体植入 1–2 周后编织骨形成持续发生。由于 MSCs 的运动由纤维蛋白桥引导，因此根据 MSCs 的粘附方式可分为两种类型的成骨作用，即接触成骨和距离成骨。接触成骨作用是指直接在植入物表面开始的成骨。另一方面，距离成骨作用出现在植入物周围的骨骼或组织，可以通过纤维蛋白桥迁移到植入物表面[21, 22]。Choi 等人证明，两种成骨过程相互作用，假体植入后的周围骨组织经历的远距离成骨可以传递诱导接触成骨的信号 [23]。  \n\n（ⅳ）在假体植入 2 周之后 ，骨-内植物间隙被新生的编织骨填充，骨整合的后续过程是骨沉积和重塑。在这一过程中，破骨细胞重新吸收新形成的骨，以消除微裂纹，优化板层骨的表面。破骨细胞建立了一个封闭区，并创建了各种微米级和纳米级包含生化信息的微观形貌，引导成骨细胞找到需要新骨形成的位置[24, 25]。  \n\n（ⅴ）破骨细胞和成骨细胞协调合作，将脆弱的临时编织骨逐渐转变为平行的纤维骨，然后转变为板层骨，这种动态过程持续存在达 1 年或更长时间。  \n\n假体植入后影响骨整合的因素是多方面的，这些因素通常可被分为两个方面：即骨-种植体界面周围的环境因素和种植体本身的设计。环境因素包括载荷条件、宿主骨特性、界面距离、局部血供、局部成骨细胞和破骨细胞浓度以及全身疾病（骨质疏松、糖尿病、类风湿性关节炎和吸烟等）[26-28]。另一方面，假体的性质，包括材料成分、表面涂层、拓扑结构、宏观和微观结构、粗糙度、孔径和孔隙率等因素也会极大地影响骨整合的效果 [29-31]。根据不同疾病状态的患者，设计优化的假体，对于促进假体界面骨整合，提高假体植入成功率和使用寿命是至关重要的。  \n\n![](images/fc8e7df10b948cd8414dc308e6252e69d00496b7b57e8032b317ff608e81ec9f.jpg)  \n\n图 1.1 植入物假体界面骨整合过程示意图。（ⅰ）血凝块和纤维蛋白基质的形成；（ⅱ）血管生成和编织骨形成；（ⅲ）距离成骨和接触成骨；（ⅳ）新生的编织骨骼填补了缺口，并进行了骨骼重塑；（ⅴ）编织骨骼转化为板层骨骼。Dc，分解的血凝块；M， 巨噬细胞；MSC，间充质干细胞；N，中性粒细胞；O， 骨细胞；Ob，成骨细胞；Oc，破骨细胞 [7]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 1.1.2 骨质疏松性骨微环境  \n\n骨质疏松是以全身骨量减少，骨组织的微观结构改变，易引起脆性骨折为特征的一种渐进性、全身性疾病 [32]。随着人口老龄化的进展，我国 40 岁以上人群中骨质疏松的患病率高达 $19.74\\%$ 至 $24.62\\%$ ，尤其是绝经后妇女和老年人具有更高的患病率，这与需要接受关节置换的骨关节炎的患者群有着极大的年龄重合[33, 34]。先前有研究显示，接受关节置换的患者中，高达 $50\\%$ 的患者合并有骨质疏松症，其中女性患者占 $53.4\\%$ ，男性患者占 $7\\%$ [35]。正常状态下，由成骨细胞介导的骨形成和破骨细胞导致的骨质吸收共同维持体内的骨代谢处于动态平衡状态。然而，当破骨细胞主导的骨吸收活性增强，而没有相应提高的骨形成活性，则会导致骨密度下降，甚至骨质疏松。绝经后妇女体内的雌激素水平因卵巢功能逐渐衰竭而下降，雌激素缺乏通过影响 T 淋巴细胞、B 淋巴细胞、单核细胞和一系列细胞因子水平，增加骨转换和导致骨代谢失衡。除了雌激素缺乏，骨质疏松状态下糖皮质激素含量增高、维生素 D 和活性因子水平低下也是造成包括自噬改变、氧化应激以及慢性炎症等特定病理性骨微环境的重要因素（如图 1.2）[36]。此外，表观遗传变化，如非编码 RNA 和 DNA 甲基化的变化，也可以减少成骨基因的表达 [37]。在骨质疏松状态下，成骨细胞介导的骨形成作用下降、破骨细胞主导的骨吸收活性过度活跃，造成体内成骨-破骨平衡失紊，造成骨质下降、骨量丢失和损伤后骨修复缓慢或不足。骨质疏松的这种骨微环境导致假体植入后内植物与宿主骨结合不牢固，较差的骨整合易导致假体无菌性松动、移位和假体周围骨折等术后并发症 [38-40]。研究表明，细胞功能极其依赖于周围的微环境（细胞外基质、体液成分等），相反，未能保持微环境的稳定性很可能导致细胞/组织的异常变化 [41]。因此，充分了解骨质疏松的疾病机理和假体界面周围局部的骨微环境，对于新型假体的设计和促进界面骨整合具有指导性意义。  \n\n![](images/7c0e56d542ef47029bf0b25167458a77e7e55dd44442da12dbfab0149dc993a3.jpg)  \n图 1.2 骨质疏松局部病理性骨微环境特征 [36]。",
+        "category": " Introduction"
+    },
+    {
+        "id": 16,
+        "chunk": "# 1.1.2.1 自噬及其改变  \n\n自噬是指具有双层膜结构包裹部分胞质和细胞内需降解的细胞器、蛋白质等成分所形成自噬小体，并随后可与溶酶体融合形成自噬溶酶体，将其所包裹的内容物进行有序降解，以实现细胞本身的代谢需求和更新相应细胞器的过程 [42]。自噬是一种细胞内固有的自我防御和应激调控机制，通过自噬和溶酶体功能清除、消化和降解受损的细胞器、变性的蛋白以及核酸等，从而实现对细胞内物质的循环利用，并为衰老细胞修复和重塑提供必要的原料。自噬具有多种多样的生理功能，比如耐受饥饿、清除胞内异常折叠的蛋白以及受损的细胞器、促进细胞分化和机体发育、延长寿命、清除病原微生物等。自噬调节缺陷在许多疾病中起着核心作用，包括退行性病变、癌症、感染和代谢性疾病 [43]。  \n\n根据细胞内底物运送到溶酶体腔的方式，如图 1.3A 所示，哺乳动物的自噬分为的 3 种类型，即 $\\textcircled{1}$ 巨自噬（macro-autophagy）：胞质中的一些膜性结构通过扩展、包绕待降解物而形成自噬小体，随后与溶酶体融合形成自噬溶酶体并降解其包绕的内容物； $\\textcircled{2}$ 微自噬（micro-autophagy）：溶酶体的膜向内内陷直接包裹细胞内容物并在溶酶体内降解； $\\textcircled{3}$ 分 子 伴 侣 介 导 自 噬 （ chaper-one-mediatedautophagy）：细胞质内的蛋白结合到分子伴侣后被转运到溶酶体腔中，随后被溶酶体酶消化。平时所说的自噬通常指巨自噬。细胞受到自噬相关信号诱导后，在胞浆内可形成小的类似“脂质体样”的膜结构，然后不断扩张呈扁平状，似一个由2 层脂双层组成的碗，可在电镜下观察到，被称之为Phagophore，是自噬发生关键性铁证之一。随后，Phagophore 不断延伸，将胞浆中各种各样的成分揽入“碗”中，然后“收口”，成为密闭、球形的autophagosome，即“自噬体”。通过电镜观察到自噬体的形成是自噬发生的关键性铁证之二。通常，自噬体有两个关键特征：一是双层膜，二是内部含有胞浆成分。自噬体形成后，可与细胞内吞的吞噬泡、吞饮泡和内体融合（这种情况不是必然要发生的）。随后自噬体通过与溶酶体融合后形成autolysosome，在这过程中自噬体的内膜被溶酶体酶降解，使得这两者原有的内容物融合为一体，自噬体中所封装的“货物”也随之被降解，这些降解产物包括氨基酸、脂肪酸等被运输到胞浆中以供细胞重新再利用，而剩余的残渣则被排出至胞外或滞留于胞浆中（如图1.3B）[44]。  \n\n![](images/947765bf2fd703efb6e1da61cc9b4fa7d0ee1d731ab6ab421352d603e0ab009c.jpg)  \n图1.3 （A）哺乳动物中三种类型细胞自噬示意图;（B）巨自噬的过程 [44]。  \n\n与年龄相关的自噬抑制或效率降低可能会导致老年人骨质丢失和骨质疏松。在骨质疏松状态下的骨髓间充质干细胞（ Osteoporosis derived-bone marrowmesenchymal stem cells, OP-BMSCs）自噬水平低下，可能是骨损伤后成骨能力不足的重要原因 [45]。Liu 等人确定自噬受体 Optineurin（OPTN）是决定 BMSCs 细胞命运的关键分子，其在老龄小鼠中的表达降低，老龄小鼠和 optn-/-小鼠出现骨质疏松性骨质流失，BMSCs 老化加剧，成骨减少，脂肪生成增加 [46]。此外，与衰老相关性骨质疏松的一个重要风险因素是维生素 D 不足。维生素 D3 可提高细胞质钙水平，CaMKKβ-AMPK 信号通路被激活，从而抑制 mTORC1 的活性，促进自噬 [47]。糖皮质激素水平升高是导致衰老的另一个因素，过量的糖皮质激素可诱导 BMSCs 凋亡，然而通过诱导自噬，糖皮质激素诱导的 BMSCs 凋亡可以被阻止 [36]。据报道，骨质疏松大鼠模型中成骨细胞的自噬水平也降低 [48]。成骨细胞特异性缺失FIP200（哺乳动物自噬的关键成分）的小鼠，由于成骨细胞终末分化缺陷和骨生成减少而发生骨质减少 [49]。Onal 等人在6 月龄的小鼠中有条件地敲除了骨细胞的自噬基因 Atg7，除了破骨细胞和成骨细胞数量下降、骨生成率下降和氧化应激增加外，他们还发现了骨量下降 [50]。这些变化也是衰老小鼠的特征，此外，自噬可以抑制氧化应激介导的成骨细胞凋亡 [51]。综上可知，骨质疏松局部骨微环境中低下的自噬水平是造成骨再生受限，假体界面骨整合不足的一个重要原因。  \n\n自噬可以通过多种信号途径进行调节，其中一个关键分子是机械性雷帕霉素的靶标（Mechanistic Target Of Rapamycin, mTOR），它可以感知细胞内外的各种信号变化，并调节自噬水平以响应外部环境的刺激。其中，mTOR 抑制剂——雷帕霉素作为经典的自噬诱导剂，可在上游激活隔离膜的形成，也称为 Phagophore，从而启动下游的自噬活动（如图 1.4）[43]。绝经后骨质疏松哺乳动物 BMSCs 的自噬水平降低，然而，雷帕霉素抑制关键靶点 mTOR 可以恢复自噬水平，增强OP-BMSCs 的增殖和成骨分化潜能，并改善体内的骨微结构 [45]。雷帕霉素作为经典的自噬诱导剂，可以激活细胞的自噬活性 [52, 53]。既往研究显示通过雷帕霉素来激活自噬，可部分改善骨质疏松状态下的成骨不良，增加骨量 [54, 55]。这些结果表明，自噬调节 BMSCs 的再生功能并控制骨质疏松症的发展，通过雷帕霉素激活自噬可能为增强骨质疏松症的骨整合提供有效的治疗策略。  \n\n![](images/e36d91860e9cd235ce19fec1556a98451f24ebd51a1e31a77b10dcd92c6b5c34.jpg)  \n图1.4 自噬核心机制的示意图模型 [43]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 1.1.2.2 氧化应激  \n\n与健康人群相比，骨质疏松症患者表现出更高的氧化应激水平。具体来说，在骨质疏松状态下，雌激素缺乏会上调活性氧（Reactive oxygen species, ROS）水平，如 $\\ensuremath{\\mathbf{O}}_{2}^{-}$ , $\\mathrm{H}_{2}\\mathrm{O}_{2}$ ，OH-，导致ROS 在骨髓微环境中快速积累。而骨髓微环境通过为骨相关细胞提供生化、物理和机械信号，是骨形成的主要场所 [56-58]。局部微环境中 ROS 水平的升高会抑制MSCs 的分化，严重阻碍植入物的早期骨整合，从而增加二次手术的风险。此外，氧化剂中间产物的过度积累将对机体的免疫和骨骼系统产生不利影响，加剧骨质流失并阻碍植入物的骨整合[59]。  \n\n此外，ROS 堆积也可影响局部免疫微环境。骨免疫调节已被广泛认为是骨再生的一个重要组成部分，因为它可以有效调节骨免疫环境，促进骨组织再生 [60,61]。研究表明，ROS 在炎症反应期间同时作为信号分子和效应分子发挥作用，导致免疫细胞向植入部位募集，从而干扰骨整合，并对周围组织造成损伤和纤维化[62, 63]。此外，由于巨噬细胞具有被刺激发育为破骨细胞的能力，与骨免疫调节密切相关，以及 M1/M2 极化的异质性，巨噬细胞吸引了大量关注 [64]。在成骨方面，M2 巨噬细胞可以显著刺激 MSCs/前体成骨细胞分化为成熟的成骨细胞并增强骨矿化，这部分归因于 M2 巨噬细胞分泌抗炎因子（如 IL-4、IL-10 等）和生长因子（如 BMP-2、TGF- $\\cdot\\upbeta$ 等）[65, 66]。在血管生成方面，M2 巨噬细胞分泌的因子，尤其是血小板衍生生长因子 BB（Platelet-derived growth factor BB, PDGF-BB），可以有效促进新血管的形成，从而加速骨修复过程 [67]。此外，在预防骨溶解方面，M2 巨噬细胞产生的细胞因子（如 IL-4 和 IL-13）不仅可以抑制破骨细胞前体的分化，还可以抑制成熟破骨细胞的活性，从而抑制骨吸收 [68]。因此，M2 巨噬细胞在促进成骨/血管生成和抑制骨溶解方面发挥着关键作用，这对于改善骨质疏松症患者的骨骼健康具有重要的理论和实践意义。然而，在骨质疏松状态下，ROS 堆积导致的氧化应激微环境中，巨噬细胞向 M2 极化受阻，转而更多的向M1 极化 [68]。M1 型巨噬细胞主要分泌促炎因子，具有很强的杀死微生物特性，在炎症早期承担着重要作用，但是过度的炎症持续也容易引起组织破坏。巨噬细胞过度的 M1 极化，导致 M1/M2 细胞类群比例失调，持续分泌肿瘤坏死因子- $\\mathbf{\\sigma}\\cdot\\mathbf{a}$ （Tumor necrosis factor- $\\mathbf{\\nabla}\\cdot\\mathbf{a}$ , TNF- $\\mathbf{\\nabla}\\cdot\\mathbf{a}$ ）、白介素-1（Interleukin-1, IL-1）和白介素-6（Interleukin-6, IL-6）等促炎因子 [69]。这种免疫失调的微环境导致骨髓内形成一个慢性、低度炎症的衰老状态，显著影响了骨质疏松状态下细胞成骨分化和骨形成 [70]。基于此，Chen 等人采用电化学阳极氧化方法进行表面改性， 开发了负载超低剂量银纳米粒子的 $\\mathrm{TiO}_{2}$ 纳米管（Ag@TiO2-NTs）作为抗氧化剂，通过清除活性氧，可以有效诱导巨噬细胞极化为 M2 表型，从而为调节骨免疫调节活性提供良好的微环境，并且通过抑制 PI3K/Akt、抑制下游效应器GLUT1 和激活自噬 [71]。  \n\n有研究表明，抑制 ROS 的过度积累可以显著增加成骨相关标志物的表达，增加骨量 [72, 73]。因此，针对内源性 ROS 堆积的负调控策略有望成为促进钛种植体界面的骨长入和骨整合的可行途径。表面抗氧化涂层制备被认为是赋予钛植入物优异抗氧化性能的最有前景的方法之一。先前的研究表明，在氧化应激条件下，钛植入物上的阳极氧化纳米材料具有优越的抗氧化能力，比未经处理的钛假体更有利于成骨 [74]。近年来，大量功能性聚合物涂层（例如丝素蛋白、原花青素等）被用于开发抗氧化钛植入物 [75, 76]。如图1.5 所示，为解决骨质疏松症下 ROS 的过度积累干扰钛植入物的生物活性及其早期骨整合，Shen 等人通过微弧氧化制备了一系列掺锶钛植入物。通过增加过氧化氢酶/超氧化物歧化酶活性和降低ROS 水平，高掺锶样品（ $\\mathrm{Sr}75\\%$ 和 $\\mathrm{{sr}100\\%}$ ）在诱导 MC3T3-E1 细胞成骨分化和  \n\nRAW264.7 细胞 M2 表型极化方面优于 $S r25\\%$ ，从而增强早期骨整合。此外，体外细胞共培养和体内研究的结果也表明，高掺锶样品（尤其是 $S_{\\mathrm{{r}100\\%}}$ ）在氧化应激微环境下对骨免疫调节具有积极作用。最终，对比结果表明高比例掺锶的微弧氧化涂层更有利于骨质疏松患者的骨再生与假体界面骨整合 [77]。  \n\n![](images/b0be32281f1ec4d8944eae7051ee2ac7c2ee977d0a2666cf4a4a577b1c540dd1.jpg)  \n\n图1.5 氧化应激条件下高掺锶钛假体促进早期骨整合的示意图。首先，释放的 ${\\mathrm{Sr}}^{2+}$ 通过增强过氧化氢酶和超氧化物歧化酶的活性，消除了成骨细胞过多的内源性ROS，赋予了优越的成骨诱导和抗氧化特性；其次， $\\mathrm{Sr}^{2+}$ 通过抑制氧化应激和炎症水平来调节巨噬细胞的形态和过氧化氢酶/超氧化物歧化酶活性，从而促进巨噬细胞向 M2 极化；最后，M2 巨噬细胞大量表达成骨相关细胞因子，如 TGF-β1、BMP-2，可有效改善成骨 [77]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# 1.1.2.3 慢性炎症  \n\n各种年龄相关疾病，包括骨质疏松和脆性骨折，较高的发病率常与慢性炎症相关 [78]。各种促炎信号作用于 MSCs 和破骨细胞前体，加速破骨细胞介导的骨吸收 [79]。老年人较高的血清炎症标记物水平预测了与年龄相关的骨丢失和骨吸收增加 [80]。免疫系统在老年骨质疏松症发病中的作用主要是由于受到雌激素缺乏和继发性甲状旁腺功能亢进的影响。绝经后妇女显著的雌激素缺乏除了直接影10  \n\n响骨细胞外，还间接导致慢性、低度炎症表型，即细胞因子表达改变和免疫细胞形态改变 [70]。根据研究，雌激素缺乏导致促炎细胞因子大量增加，包括 IL-1、IL-6、TNF- $\\mathbf{\\sigma}\\cdot\\mathbf{a}$ 、巨噬细胞集落刺激因子和前列腺素 E2 [81-83]。这些细胞因子大多数直接或间接作用于成骨细胞和破骨细胞，促进单核细胞向成熟破骨细胞分化，并调节破骨细胞功能。TNF- $\\mathbf{\\sigma}\\cdot\\mathbf{a}$ 可增加成骨细胞凋亡和 RANKL 的表达，这间接导致破骨细胞分化和活性的增加，并抑制破骨细胞凋亡，从而导致绝经后骨质疏松症患者的骨量丢失 [84]。Zha 等人发现，绝经后骨质疏松患者的 TNF- $\\mathbf{\\sigma}\\cdot\\mathbf{a}$ 水平高于非绝经女性，通过体外刺激 ${\\mathrm{NF}}{\\mathrm{-}}{\\mathrm{\\kappa}}\\mathrm{B}$ 和 PI3K/Akt 途径，TNF- $\\mathbf{\\sigma}\\cdot\\mathbf{a}$ 可协同增强 RANKL诱导的破骨细胞形成 [85]。  \n\n为解决骨质疏松症局部微环境中炎症因子过高这一问题，Li 等人设计了一种由纳米羟基磷灰石、白藜芦醇和壳聚糖构成的复合微球，通过局部缓释白藜芦醇以创造有利的局部微环境，从而改善成骨（如图 1.6）。具体来说，该微球具有抗炎活性，表现为在 RAW 264.7 细胞中促炎细胞因子 TNF- $\\mathbf{\\nabla}\\cdot\\mathbf{a}$ 、 $\\mathrm{IL}\\mathrm{-}1\\upbeta$ 和一氧化氮合成酶的表达呈白藜芦醇剂量依赖性降低。此外，复合微球有利于 BMSCs 在其表面粘附和增殖，并通过上调 Runx-2、ALP、Col-1 和 OCN 的表达和大量矿化而增强其成骨分化的能力。当植入骨质疏松大鼠股骨髁缺损处时，增强的软骨内成和骨再生表明，该复合微球更有利于受损的骨折愈合，可作为骨质疏松性骨缺损或骨折治疗的多功能填料 [86]。此外，Wang 等人通过微弧氧化和电化学沉积技术在钛种植体表面制备掺锶纳米结构，然后通过逐层自组装技术添加嵌入丝素蛋白基汉黄芩素纳米粒子的多层涂层。研究发现，该功能化植入物可以持续释放汉黄芩素和 $\\mathrm{Sr}^{2+}$ 超过 7 天和 21 天，可以显著抑制种植体周围炎性因子的表达，并有效促进假体界面的新骨形成，为开发促进骨质疏松性骨整合用途的功能性钛合金材料提供了一种简单有效的方法 [87]。  \n\n![](images/36e78133f8b283dadccb55985f328bf65badf1dc3f2e15b31ba072b90b9b0c81.jpg)  \n图1.6 （A）通过纳米羟基磷灰石（n-HA）、白藜芦醇（Res）和壳聚糖（CS）制备复合微球的示意图；（B）复合微球抑制促炎细胞因子 TNF- $\\mathbf{\\nabla}\\cdot\\mathbf{a}$ 和 IL-1β 的表达，呈白藜芦醇剂量依赖性；（C）Masson 三色染色观察复合微球对骨质疏松骨缺损的修复情况 [86]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 1.2 骨质疏松性骨整合的假体设计  \n\n研究表明，骨整合过程受多种因素的影响，这些因素通常可分为两个方面：即骨-种植体界面周围的环境因素和种植体本身的设计。自从认识到假体界面骨整合的重要性以来，骨科医生和材料学家已经制定了许多策略来加快骨整合的发生，实现更快、更牢固的生物学固定。在骨质疏松状态下，目前大量的研究聚焦于探索假体的材料成分、制备方式、表面结构和活性物质递送等策略来促进界面骨整合的效果，从而减少术后假体并发症。",
+        "category": " Introduction"
+    },
+    {
+        "id": 20,
+        "chunk": "# 1.2.1 假体主体材料  \n\n假体的主体材料决定这内植物的力学性能和生物相容性，极大地影响着宿主细胞在假体界面的粘附和分化，是控制骨-假体界面骨整合的重要因素。金属材料，如钛及其合金、坦、钴铬合金等，由于其合适的生物力学特性，在骨科假体中占据主要位置。",
+        "category": " Introduction"
+    },
+    {
+        "id": 21,
+        "chunk": "# 1.2.1.1 钛及其合金  \n\n钛及其合金由于其优异的机械性能，如高强度、耐腐蚀性、低弹性模量和自然界丰富的来源，是目前临床上用于制备内植物最常用商业材料 [88, 89]。纯钛表面形成稳定的氧化层是纯钛假体生物相容性和增强耐腐蚀能力的原因。然而，这使得钛很难蚀刻、塑性 [90]。目前，钛合金由于具有更高的孔结构和更好的塑性而被引入市场，其中 $\\mathrm{Ti_{6}A l_{4}V(6\\%}$ 铝； $4\\%$ 钒）在所有钛合金中占据最重要的位置。铝可以提高合金的强度，同时降低其密度，而钒可以防止铝腐蚀，钛合金内植物已广泛用于骨外科、牙科和血管外科的医疗领域 [91]。传统钛合金植入物采用模具铸造或减法技术制造，如机械加工、多点成形和数控加工，因此很难在真实骨组织中模拟皮质骨和松质骨的结构 [92]。随着 3D 打印技术的出现，这些问题可能会得到解决。自 2015 年以来，3D 打印医疗设备在患者直接治疗中的使用大幅增加。最常见的是外科，尤其是骨科（ $36\\%$ ）和骨科肿瘤（ $(32\\%)$ ），其次是颌面外科（ $6\\%$ ）、神经外科（ $4\\%$ ）和整形外科（ $1\\%$ ）[93, 94]。",
+        "category": " Introduction"
+    },
+    {
+        "id": 22,
+        "chunk": "# 1.2.1.2 坦金属  \n\n钽金属是一种高度惰性和耐腐蚀的材料，具有极高的熔点（ $3017^{\\circ}\\mathrm{C})$ ）。与钛不同的是，钽具有很高的导热性和导电性，并且已被证明比钛更具生物相容性。钽金属表面的氧化反应有助于成骨细胞的粘附、增殖和分化，并且比常用的$\\mathrm{Ti_{6}A l_{4}V}$ 更好 [95, 96]。因此，钽金属因其快速和长期固定性而成为翻修髋关节置换术中髋臼重建的重要组成部分 [97, 98]。此外，钽也可以制成多孔植入物。由于其高体积孔隙率，钽被称为小梁金属。多孔钽的弹性模量与软骨下骨的弹性模量相似，有助于减少应力遮挡和减少骨溶解。同时，高摩擦系数使多孔坦比传统的无骨水泥假体具有更好的初始稳定性 [99, 100]。因此，坦金属制备的假体在骨质疏松状态下具有较好的骨诱导性，可获得满意的骨整合效果[101-104]。然而，多孔钽结构太薄，难以制造准确的内部形貌。此外，钽金属在自然界储存量少，提纯和制造成本高，阻碍了其广泛应用 [105]。将坦金属以粉末形式生产，并以涂层的方式在加载到其他植入物的表面，也显示出令人满意骨整合的效果 [106-108]。",
+        "category": " Introduction"
+    },
+    {
+        "id": 23,
+        "chunk": "# 1.2.1.3 钴铬合金  \n\n钴铬（CoCr）合金因其高耐磨性和耐腐蚀性，常用于金属对金属的全髋关节置换假体。它还被发现兼具材料韧性、屈服强度、延展性和硬度方面的极好特性。钴提高了合金的强度，而铬提高耐腐蚀性。然而，添加超过 $30\\%$ 的铬会使该合金难以铸造，并导致脆性相变 [109]。因此，用于制造金对金植入物的 CoCr 合金通常含有约 $64\\%C0$ 、约 $28\\%C\\mathrm{r}$ 以及少量其他金属（如钼、铝、镍、锰、铁和镧）[110, 111]。 $\\mathbf{CoCr}$ 合金本身的特性再加上高抛光降低表面粗糙度的技术，使得假体在磨合期后的磨损率比传统假体低 40 倍，容积磨损率降低 200 倍。此外，髋臼部分直径设计较大，使得股骨头与髋臼之间的磨损程度大大减小，极大的延长了假体使用寿命，并取得良好的患者满意度 [112, 113]。然而，CoCr 合金的骨整合能力和生物相容性通常被认为低于钛合金 [114]。另一个与CoCr 合金相关的问题是，生物材料的降解将产生大量纳米颗粒，这可能导致过敏反应和细胞毒性 [115]。据报道， CoCr 合金植入物患者的血液中Co/Cr 浓度通常会升高 [116]。但降解的颗粒物与并发症之间的生物学相关性尚未得到彻底评估，也有学者认为患者血液和组织中的Co/Cr 浓度过低，不会增加系统性疾病的风险 [117]。",
+        "category": " Introduction"
+    },
+    {
+        "id": 24,
+        "chunk": "# 1.2.2 3D 打印微孔假体  \n\n3D 打印技术是快速成型的一种，也被称为增材制造，是一种以数字模型文件为基础，使用粉末状塑料或者金属等可粘合材料作为原料，根据预设好的空间结构进行逐层打印制造物件的一种新型技术。目前，用于钛合金材料的主流 3D打印方法包括选区激光烧结（Selective laser sintering, SLS）、选区激光熔融（Selective laser melting, SLM）、电子束熔融（Electron beam melting, EBM）等 [118-120]。简要来说，3D 打印骨科假体的制备过程为首先利用软件设计或影像学 CT扫描获得预打印物体的结构外形，建立 3D 模型，然后将模型导入生成 STL 文件格式，而后将该格式文件导入 3D 打印机进行分层切片，打印出实物并对其进行后处理包括抛光和灭菌等，最后得到与预设计相符的个体化假体，并用于骨科植入（如图 1.7） [121]。  \n\n![](images/2eb9e431c5280da0cbec35b6b0428bfdb7b6bd16baa423dd1044dc5e44082e6d.jpg)  \n图1.7 3D 打印骨科假体制备过程示意图及本课题组打印获得的成品假体 [121]。  \n\n与传统假体相比，个体化设计的 3D 打印假体可以制造成微孔结构，该设计不仅具有与松质骨类似的弹性模量，可以避免应力遮挡及骨吸收，而且能够增加假体与周围骨质间的接触面积，增强界面的初始稳定性，强制性地限制界面微移动 [122, 123]。通过 3D 打印方法制备的骨科内植物具有可控的三维立体微孔结构，可维持成骨细胞形态的同时并促进其粘附、增殖及生物活性，促进成骨相关胶原（如I 型胶原和V 型胶原）的分泌，以达到诱导骨质向内生长和获得假体界面骨整合的目的 [124-126]。因此，中国食品药品监督管理局自 2015 年起，已批准具有微孔结构界面的3D 打印金属垫块、髋臼杯和椎间融合器等植入体进行临床应用。既往临床研究已证实，使用具有微孔结构修饰的 3D 打印假体在关节置换术后的可以诱导新生骨质长入假体微孔内部，有效恢复组织的结构稳定性，加强假体-骨界面良好的骨整合，显著降低术后假体翻修率 [97, 127-130]。其中，微孔结构是决定3D 打印假体骨整合效果的决定性因素，但目前对于最合适的微孔参数（包括孔径、孔隙率、微孔形状等）尚未有定论 [122]。  \n\n假体微孔尺寸影响细胞和组织在支架表面的粘附方式，及假体内部组织的物质交换。当孔径过小时（如 $<300~\\upmu\\mathrm{m}$ ）材料的表面张力较大，且桁架间距小于细胞移行跨越的距离限制，导致细胞跨越微孔沿支架表面生长，在支架表面形成薄层组织。这种新生薄层组织阻碍了新生骨组织向微孔内部的长入，将会影响骨整合的质量和强度。同时，组织薄层覆盖了支架表面微孔，阻断了支架内部新生组织的营养供应，不利于支架微孔内骨长入和新骨生成 [131]。相反，当孔径大于细胞移行跨越的距离时，细胞及组织会粘附于桁架内并向孔隙内部生长，进而实现骨长入。但孔径过大（ $(\\geq1000~\\upmu\\mathrm{m})$ ），假体与自体骨虽然能发生组织学层面的骨整合，但由于接触面积受限，导致骨整合界面总体力学结合强度不足，不能实现支架的长期稳定固定。如图 1.8 所示，近期的一项研究将 $700~{\\upmu\\mathrm{m}}$ 孔径的支架孔隙率分别设计为 $40\\%$ 、 $70\\%$ 和 $90\\%$ ；而孔隙率为 $70\\%$ 的支架孔径分别为 400、700和 $900~{\\upmu\\mathrm{m}}$ ，以论证孔隙大小和孔隙率协同促进体外成骨活性和体内新骨形成的最佳参数。就该研究中的孔径而言，用于提高成骨能力的最佳孔径为 $700\\upmu\\mathrm{m}(\\up p70)$ ，孔径过小或过大都可能或多或少地阻碍细胞行为和骨再生，即使孔径（300-900$\\upmu\\mathrm{m}$ ）和孔隙度（ $70\\%$ ）都在推荐值范围内；此外，在恒定孔径下（ $700\\upmu\\mathrm{m})$ ，与孔隙率为 $40\\%$ （ $\\mathtt{p40}$ ）相比，孔隙率较高的 $70\\%$ （p70）和 $90\\%$ （ $\\mathsf{p}90$ ）更有利于骨形成和骨整合[132]。  \n\n![](images/af2d836a0dff71256257c9591cf9f44d084e4b9d09049f49f549c7ade47e1f77.jpg)  \n图1.8 不同孔径、孔隙率支架的制备及其对骨形成和骨整合的影响 [132]。  \n\n除了孔径和孔隙率，在假体制备过程中通过调整走线方式，即可获得不同形态的孔隙结构。其中，三角形、正方形和正六边形是最常见的三种微孔形态。由于假体桁架间不同的排布方式，会影响细胞在假体界面上的迁移行为 [133]。研究表明桁架间夹角越小（如三角形微孔），细胞在微孔中可以有更多的粘附面积，提升细胞粘附效率，并可以接受更多的物理刺激实现成骨分化；在桁架间夹角较大（如六边形微孔）的假体中，细胞在微孔中粘附效率则相对较低 [134]。另外，有学者利用 Micro-CT 技术扫描人松质骨骨小梁结构，重建出具有天然骨小梁分布特点的3D 模型并打印出高度仿生化的微孔假体。假体中的仿生骨小梁微孔结构构建了利于BMSCs 增殖、分化的细胞微环境，并可以通过调整仿生骨小梁微孔的密度模拟自体骨骨小梁排列特征，以获得生物力学与自体骨高度相似的 3D打印钛合金微孔假体 [135]。  \n\n尽管3D 打印微孔假体的应用在一定程度上可以促进骨质疏松状态下的界面骨整合，降低假体松动和下沉的可能，但临床上使用的钛合金材料的生物惰性，以及金属微孔表面光滑等物理特征不利于 BMSCs 粘附和增殖，不利于负载可调节骨质疏松性骨微环境的活性药物，不能充分调动内源性 OP-BMSCs 的成骨作用。因此，骨质疏松状态下的假体界面周围骨质再生以及骨整合的改善仍是亟须解决的问题。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 25,
+        "chunk": "# 1.2.3 假体表面涂层与改性  \n\n大量研究证明，假体表面的特性会影响周围微环境，这对骨整合来说非常重要 [27, 136, 137]。为了提高表面粗糙度、物理模拟宿主骨结构和提高植入物的生物相容性，假体表面改性技术经历了不断的发展和演变。根据表面特征，这些改性技术可分为三类：即物理改性、化学改性和生物改性（表 1.1）。这些技术可以单独使用，也可以组合使用，每种方法都有其特定的优点和局限性，必须根据植入材料、应用情况和制造程序选择合适的方法。  \n\n表1.1 改性技术分类与特定  \n\n\n<html><body><table><tr><td>种类 技术</td><td></td><td>特点</td></tr><tr><td>物理</td><td>喷砂</td><td>简单、低成本；促进骨细胞和细菌附着</td></tr><tr><td>技术</td><td>增材制造</td><td>创建复杂的3D结构；过程简单；节约材料</td></tr><tr><td></td><td>等离子喷涂</td><td>热技术；经济和安全</td></tr><tr><td></td><td>物理气相沉积</td><td>真空沉积；利用各种无机材料和一些有机材料；强</td></tr><tr><td></td><td></td><td>附着力</td></tr></table></body></html>  \n\n续表：  \n\n\n<html><body><table><tr><td>种类</td><td>技术</td><td>特点</td></tr><tr><td rowspan=\"4\">化学</td><td>机械加工</td><td>增加粗糙度的简单方法；速度慢，效率低</td></tr><tr><td>激光处理</td><td>实现复杂和精确的形貌；快速而清洁</td></tr><tr><td>阳极氧化</td><td>加速电化学过程；提高耐蚀性；创建纳米特征</td></tr><tr><td>溶胶-凝胶</td><td>低温技术；药物输送</td></tr><tr><td rowspan=\"3\"></td><td>化学气相沉积</td><td>生成精细的固体薄膜；构建均质和分层结构</td></tr><tr><td>酸蚀</td><td>制造粗糙度；取决于酸浓度、温度和时间</td></tr><tr><td>碱处理</td><td>均匀延伸；不损坏机械性能</td></tr><tr><td>生物</td><td>细胞</td><td>MSCs和胚胎干细胞等</td></tr><tr><td>技术</td><td>蛋白</td><td>直接促进成骨细胞的附着、增殖和分化</td></tr></table></body></html>  \n\n目前，钛金属是应用最广泛的骨科植入物材料，其有着生物相容性好、耐腐蚀佳、强度与天然骨接近等优势。钛合金表面会自发形成一层 $5{\\mathrm{-}}10{\\mathrm{nm}}$ 厚的 $\\mathrm{TiO}_{2}$ 氧化层 [138]。虽然有一些实验证明钛合金在体液中游离 $\\mathrm{Ti}^{4+}$ ，并吸附体液中羟基以促进 $\\mathrm{Ca}^{2+}$ 在植入物表面沉积，但这种氧化还原反应极其微弱，钛合金通常还是被认为是一种生物惰性材料，在植入体内后与机体间的交互反应较弱 [139, 140]。喷砂是一种典型的物理表面改性技术，它通过压缩空气的加压喷射将磨料颗粒（即砂、氧化铝、二氧化硅、羟基磷灰石、二氧化钛）压在植入物表面上 [141]。羟基磷灰石是组成人体骨骼的最主要无机成分，具有理想的骨诱导生物活性 [142]。目前，已有多种品牌型号的羟基磷灰石涂层的钛合金骨科假体上市并广泛投入临床使用 [143, 144]。针对骨质疏松状态下 ROS 堆积和 OP-BMSCs 成骨能力不足的微环境，Chen 等人通过羟基磷灰石涂层和生物分子移植在钛表面构建了一个 ROS 反应系统。将多孔羟基磷灰石和磷酸化成骨生长肽（Phosphorylated osteogenicgrowth peptide, p-OGP）引入钛表面，协同提高 OP-BMSCs 的成骨分化。ROS 在骨质疏松微环境中触发 DNA 适配体 Apt 19S 的释放，因其与 MSCs 膜上的碱性磷酸酶具有高度亲和力，可引导 OP-BMSCs 迁移至假体植入部位。一旦 OP-BMSCs 到达种植体界面，p-OGP 促进成骨相关蛋白表达，羟基磷灰石降解释放钙和磷离子，并整合到骨组织中，以促进骨基质的矿化（如图 1.9）[145]。  \n\n![](images/cc1ad4e8d4fba359f805ceb321852a1936d7139f736caff4256ec151e89a8c7f.jpg)  \n图 1.9 羟基磷灰石涂层和生物分子移植在钛表面构建了 ROS 响应的功能性钛种植体，促进骨质疏松症局部骨重建 [145]。  \n\n另外，植入物的表面的微观形态对骨整合效果也具有明显的影响。关节假体柄根据其表面形态可以分为光滑面、粗糙面、珊瑚面、微丝面、微孔面等类型 [146,147]。经长期临床观察验证，光滑面的植入物不易与自体骨间形成高强度骨整合，从而易导致假体下沉、松动等植入术后并发症的发生。经表面处理后的植入物，其表面粗糙度增加，提高了亲水性和表面积，可以促进细胞在植入物表面的粘附效率，为骨整合中新骨生长提供了更多的结合面积，利于形成高强度的骨-植入物连接界面 [148, 149]。此外，钽、镁、锶等金属已被证实具有较好的骨诱导功能，也可作为钛合金假体的表面涂层而促进骨整合 [150]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 26,
+        "chunk": "# 1.2.4 局部递送活性物质  \n\n除了针对假体的材料、制备方式和表面改性这些策略来增加假体界面的活性，局部递送活性物质调节骨质疏松微环境是另一个重要的手段来加强假体界面骨整合。与间接成骨刺激方法（物理和化学表面改性）相反，包括细胞封装和生物活性因子或药物负载在内的局部活性物质递送技术，可直接促进成骨相关细胞的附着、增殖和分化。各种细胞和活性因子被负载到多孔植入物表面或内部：如MSCs、胚胎干细胞、血管内皮生长因子（Vascular endothelial growth factor, VEGF）、骨 形 态 发 生 蛋 白 -2 （ Bone morphogenetic protein-2, BMP-2 ） 和 骨 保 护 素（Osteoprotegerin, OPG）等，并在骨质疏松状态下获得满意的假体界面骨整合效果 [151-157]。为了抑制骨质疏松症局部过度的骨吸收并促进假体界面骨整合，我们先前的研究构建了一种 3D 打印多孔钛合金/泊洛沙姆407 水凝胶系统，以装载经典的抗骨质疏松药物——唑来膦酸。这种复合假体具有良好的生物相容性，随着水凝胶的降解，能够持续释放低浓度的唑来膦酸，抑制破骨细胞的分化的同时促进OP-BMSCs 增殖和成骨分化，从而促进骨质疏松状态下的假体界面骨整合（图1.10）[154]。  \n\n![](images/66060e454b761ed7cf75f0e677cbe8c13618fcd839ff182d7a7e29235e4f127c.jpg)  \n图1.10（A）负载唑来膦酸的 3D 打印多孔钛合金/泊洛沙姆407 水凝胶系统以促进骨质疏松假体界面骨整合示意图；（B）3D 打印多孔钛合金及其负载水凝胶后的外观及微观图像；（C）Micro-CT 三维重建观察假体界面骨长入与骨整合 [154]。  \n\n近年来，除了使用骨吸收抑制剂外，合成代谢药物在抗骨质疏松方面的开发也引起了研究者们更多的关注。特立帕肽，也称为 1-34 人甲状旁腺激素（1-34human parathyroid hormone, PTH），是目前美国食品和药物管理局（FDA）批准用于治疗骨质疏松症的唯一合成代谢药物 [158]。通过将特立帕肽封装在泊洛沙姆407 水凝胶中，构建可注射局部药物缓释系统可上调 Runx-2、Col-1、骨钙素（OCN）和骨桥蛋白（OPN）的表达，有利于 BMSCs 的增殖、迁移和成骨分化，促进骨质疏松性骨缺损的愈合 [159]。然而，这种局部活性物质递送的策略对假体界面骨整合的效果因种子细胞的种类、密度、分化潜能以及活性物质和药物的选择及其释放策略而异。之前的一项研究显示，PTH 具有同时激活成骨细胞和破骨细胞的独特能力，并且局部持续释放 PTH 显示对破骨细胞比成骨细胞的激活程度更高，从而导致净骨吸收 [160]。随着对特立帕肽不同释放节律的更详细研究，有报导表明，负载还原氧化石墨烯壳聚糖水凝胶通过光热触发的特立帕肽仿生脉冲释放比持续药物递送对骨质疏松性骨再生的效果更为满意 [161]。值得探索的是，有人提出脉冲式释放的 PTH 在促进骨再生方面也存在一些缺陷，例如小鼠颅骨骨缺损修复的结果表明，PTH 脉冲组仍有许多材料残留 [162]。其原因可能是虽然脉冲释放大大增强了成骨细胞的活性，但对破骨细胞的激活作用太弱，因此植入缺损处的材料降解速度与骨形成速度不匹配，从而导致缺损处的骨修复不够彻底 [163]。因此，Kuang 等人提出了一种刺激响应的双模式系统（连续 $+$ 脉冲模式）来精确控制局部PTH 释放。具体而言，通过聚合物聚 N-丙烯酰甘氨酸-丙烯酰胺共聚物（PNAm）和吲哚青绿（ICG）的自组装，合成了近红外光调制的热敏聚合物微球。微球与 PTH 络合后，再与水凝胶混合，注入骨缺损部位。在双模式释放系统下 PTH 以低浓度持续释放，在近红外光照射下脉冲释放 PTH。结果表明，这种 PTH 的双模式释放平台可以同时协同增强成骨细胞和破骨细胞的活性，并在骨质疏松性骨缺损中获得比连续给药和单独脉冲释放更好的修复结果（图 1.11）。此外，生物活性物质如何递送到靶部位并维持活性发挥高效作用，也是获得良好骨整合效果至关重要的因素[164]。  \n\n![](images/f0196c301acadca86d790288b16d0b2945f6b593c308e1493abb2d6bb37e8f3c.jpg)  \n图 1.11（A）近红外光响应负载 PTH 的 PNAm/ICG 微球的制备示意图；（B）可注射的PTH 双模式释放策略修复骨质疏松大鼠骨缺损；（C）通过Micro-CT 对缺损部位进行三维重建，以评估 12 周骨质疏松大鼠的骨再生；（D）不同药物释放模式下成骨细胞和破骨细胞的活性调节示意图 [164]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 27,
+        "chunk": "# 1.3 局部活性物质递送策略  \n\n局部活性物质递送体系能实现对治疗剂的负载和可控释放，提高病灶部位药物的富集量和利用率，降低全身用药的剂量及毒副作用，是近年来生物组织工程领域的研究热点。根据局部活性物质递送策略的不同，可分为植入式的体内递送系统和经皮式的体外递送系统。",
+        "category": " Introduction"
+    },
+    {
+        "id": 28,
+        "chunk": "# 1.3.1 体内局部递送系统  \n\n局部递送系统通常包括网络结构和颗粒结构，其中，网络结构系统包括支架、水凝胶和纳米纤维，而常见的颗粒结构系统包括纳米乳液 、胶束、固体脂质纳米粒（SLN）、纳米结构脂质载体（NLC）、脂质体和聚合物纳米胶囊等（图 1.12）[165]。其中，水凝胶由于具有三维多孔网络结构和良好的生物相容性，已被广泛开发为外泌体、生长因子、药物等的持续局部递送载体，成为骨组织工程支架的极佳候选者，为探索和理解细胞生态微环境提供了一个良好的体内外活性因子的负载模型。水凝胶特有的多孔网络结构为负载药物提供足够的空间，同时可通过降解控制释放药物，其可控的药物释放动力学潜在地解决传统药物治疗中的弥散性和突释问题。而面对众多的生物材料，了解不同活性物质（药物、生长因子、外泌体）负载与控释的通用策略，更有目的性地去选择合适的凝胶基材，对于获得满意的骨再生和骨整合效果具有重要的意义。  \n\n![](images/3ddb466b1efaf484a50c2dd145a3356a1540d92c6ead5564f008a74ab12ae1da.jpg)  \n图1.12 常见局部体内药物递送系统 [165]。  \n\n水凝胶作为药物递送体系的性能取决于凝胶的物理和化学性质以及治疗剂的装载机制。如图 1.13 所示，水凝胶负载活性物质的方式包含三种主要方法：物理包埋/混合、静电吸附、共价锚定，每种方法都有其特定的优缺点，应在考虑所用水凝胶网络以及药物性质后进行选择 [166]。水凝胶负载活性物质后，可在生理条件下实现缓释药物的效果，其控释方式包含被动扩散（一般借助水凝胶内外的渗透压差）、主动释放（如凝胶网络的瓦解等）[167]。此外，相关负载与控释领域的水凝胶设计常涉及不同类型的外界刺激（如 pH、温度、活性酶和炎症介质浓度等），以凸显药物递送型水凝胶构建的创新性，即在外界刺激下，实现原位药物可控的智能化递送。在相关研究中，水凝胶扮演骨架的角色，并在此骨架中引入刺激响应性的链段设计，或引入偶联药物/活性因子的中间桥梁，进而锚定药物。其本质是利用凝胶骨架上可共价反应的活性官能团（如- $\\scriptstyle\\cdot C=C-$ 、-COOH、-NH2等）或通过静电作用、疏水缔合非共价键作用等，来实现药物的有效负载。比如，丙烯酰化-聚乙二醇-琥珀酰亚胺酯（AC-PEG-NHS）是一种双功能 PEG 交联剂，属于异官能团双取代聚乙二醇衍生物，其一端修饰有丙烯酸酯基团，另一端修饰有NHS 基团。其中，丙烯酸酯可参与双键修饰类聚合物光固化凝胶体系的构成，而 NHS 可与蛋白或药物分子上的氨基（ $\\left.-\\mathrm{NH}_{2}\\right.$ ）反应形成稳定酰胺键，因此可实现目标蛋白或药物与双键修饰高分子的桥联作用，延缓缓释周期，避免药物的突释。基于该原理的材料体系已被广泛应用于药物负载、蛋白锚定等生物医学领域。  \n\n![](images/980ab05242919b92af6ff5a827442d3432b5a86ef76d2babcb6f910b8a1fb099.jpg)  \n图1.13 水凝胶负载药物的不同策略及其特点 [166]。  \n\n此外，生长因子一般是指对机体生长、发育具有广泛而特定的调节作用一些活性蛋白类或者多肽类物质。若涉及单一生长因子的控释或生长因子协同治疗对组织的修复等方向，药物负载与控释的方式同样适用于生长因子，即通过物理共混、化学键合、静电作用（可根据蛋白的等电点来设计，利用静电作用）等方式负载于光固化凝胶载体中。而对于细胞和外泌体的负载与控释，一般选择简单的物理共混，以最大程度减少细胞和外泌体的功能活性损失。我们先前的研究使用通过原位交联 N-羧乙基壳聚糖、己二酸二酰肼与透明质酸醛，制备了可注射和自愈合的超分子多糖水凝胶，用于递送 BMP-2 和BMSCs 并与3D 打印微孔钛合金支架复合构建生物活性假体。如图1.14 所示，这种 3D 打印生物活性假体界面能够极大的促进骨质疏松状态下的内植物骨整合 [154]。  \n\n![](images/3b168705dbdad73c444b06f156f7589e8d83dfabe31949c0d5d66225df5bb911.jpg)  \n图1.14 （A）负载 BMP-2 和BMSCs 的超分子水凝胶与 3D 打印微孔钛合金支架复合构建生物活性假体。（B）3D 打印生物活性界面促进骨质疏松状态下假体界面骨整合 [154]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 29,
+        "chunk": "# 1.3.2 体外经皮递送系统  \n\n除了体内植入式的局部递送系统，体外经皮药物递送包括化学增强剂、离子导入/电穿孔、超声、喷射注射和微针系统等，已被广泛研究并逐渐应用于临床（图 1.15）[168]。其中，经皮超声介导的局部药物递送因其精准可控、安全无创的特性而备受关注。早在 1950 年，Fellinger 和 Schmidt 首次报道用氢化可的松软膏结合超声导入成功治疗手部指关节多关节炎，随后研究者发现超声波可以辅助增强药物、蛋白质、DNA/RNA 和其他一些化合物在细胞和组织的吸收，在此研究基础上，创建了无创的超声介导的药物递送理论 [169]。经皮超声导药仪器的原理主要是通过可控的电信号经过放大作用后到达压电晶体，在换能器的尖端转换为经皮药物递送所需要的超声波。高能量的超声波集中在皮肤上时，通过热效应、空泡化效应和声流效应三种主要机制对组织和细胞产生影响 [170]。通过这些作用可使皮肤、组织膜形成或\\和扩大已形成孔道，使其通透性增加，增强药物的渗透作用。此外，这些效应还可使药物粒子获得向特定方向运动的动能，即沿着声波传播的方向做定向运动，从而实现药物靶向运输，并使局部组织和细胞内药物浓度达到预定的浓度。超声透皮给药法是一种安全有效的给药策略，可部分替代传统的注射给药，特别是对生物大分子药物，可以实现给药的最优化 [171, 172]。  \n\n![](images/94fcd9cfb7c2fd00d5562bf464e4e807201327431a0ecc25cb2f2e81d41517e5.jpg)  \n图1.15 常见不同机制经皮给药的代表性策略，包括化学促进剂促进、电动促进、机械力触发和微针辅助给药系统 [168]。  \n\n超声波作用频率、强度和时间是决定上述几个效应、及其对皮肤损伤的关键参数。组织的声波吸收系数随着超声频率的增加而增加；此外，空泡化效应也由超声波频率决定，空泡直径与超声波频率呈反比，且空泡尺寸越大，其稳定性越差 [170]。在固定频率超声下，组织温度升高幅度与超声强度和作用时间直接相关[173]。在应用过程中，超声波强度也应受到限制，以避免潜在的皮肤损伤。总的来说，经皮超声介导药物递送中使用的超声条件主要集中在频率为 $0.02\\mathrm{-}16\\mathrm{MHz}$ ，强度为 $0.008{-}50\\mathrm{W/cm}^{2}$ 之间变化 [174]。与被动给药相比，超声介导的递送特征性药物转运增强约可提高 10 倍 [175]。低频超声（ ${<}100\\mathrm{kHz}$ ）对药物经皮递送的效率明显大于高频超声（ ${>}700\\mathrm{kHz}$ ）[170]。例如，低频超声波对于皮肤通透性的改善作用明显强于高频超声波，如 $20~\\mathrm{kHz}$ 的低频超声介导的经皮给药效果大约为1 MHz 高频超声波作用的 3 倍 [176]。Merino 等人报道的另一个例子表明，与低频超声（ $20~\\mathrm{kHz}$ ）相比，使用高频超声（ $10~\\mathrm{MHz}$ ）没有引起药物递送效率增强[177]。近些年，随着科技的不断进步，低频超声波经皮给药的研究得到了广泛的开展 [178, 179]。相较于临床常用的静脉穿刺给药方式，低频超声介导的药物输送具有无痛、无创、感染风险低、病人满意度高、对血管刺激小的优点。目前随着低频超声给药技术的不断成熟，在临床上，已经开发出了相关的操作仪器，且在众  \n\n多的临床科室投入使用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 30,
+        "chunk": "# 1.4 选题目的与主要研究内容  \n\n目前，临床上接受关节置换手术的患者多数为老年患者，常伴有骨质疏松，在假体植入后由于局部骨质不良、骨再生能力不佳，造成骨整合效果不理想，从而导致术后假体松动、移位和假体周围骨折等并发症高发。骨整合的发生很大程度依赖骨-假体界面的生物活性和附近参与骨再生细胞的功能。经上综述可知，骨质疏松状态下的骨再生和骨整合能力受限，可能是部分由于 OP-BMSCs 低下的自噬能力导致细胞活性和增殖能力低下，成骨分化不足，趋向于成脂分化而造成。因而，在利于骨长入的 3D 打印微孔假体界面负载可激活 OP-BMSCs 自噬活性的药物，是恢复 OP-BMSCs 细胞活性和功能，促进假体界面骨整合的潜在策略。经皮超声介导的药物递送具有精准可控、安全无创的特点，且可根据实际情况方便地进行药物种类或者剂量的调整，是一个局部给药的优选策略。考虑到通过特制的超声电导仪频繁的经皮给药，可能导致患者依从性差，且增加了经济和时间负担，所以本研究还构建了一种“3D 打印金属微孔/水凝胶的生物活性界面”作为一站式植入物，在体内进行长期、稳定的雷帕霉素缓释，是另一种可供选择的策略。因此，本研究拟通过构建经皮超声介导雷帕霉素递送和功能化水凝胶介导的雷帕霉素局部递送两种策略，上调 OP-BMSCs 的自噬水平，以恢复下降的细胞活性（包括细胞活力、增殖、迁移和成骨）和抑制成脂分化，从而促进 3D打印微孔假体界面在骨质疏松状态下的骨整合。",
+        "category": " Introduction"
+    },
+    {
+        "id": 31,
+        "chunk": "# 第 2 章  经皮超声介导雷帕霉素递送通过激活自噬和调控成骨微环境促进骨质疏松状态下假体界面骨整合  \n\n骨质疏松症患者骨髓中的 OP-BMSCs 具有受损的细胞功能和低下的成骨活性，导致假体植入后骨整合不足，增加了关节置换术后灾难性并发症的发生的风险。OP-BMSCs 低下的自噬活性是导致细胞功能低下和骨整合不良的重要因素，而低下的细胞自噬活性可以通过经典的自噬激活剂——雷帕霉素激活。因此，在骨质疏松环境下，通过局部递送雷帕霉素激活 OP-BMSCs 自噬以促进 3D 打印假体界面的骨整合具有重要意义。经皮超声介导药物递送作为一种无创的药物递送方式而备受关注。在本研究体系中，我们将雷帕霉素作为模型药物，通过经皮超声介导递送来上调 OP-BMSCs 的自噬水平，以恢复下降的细胞活性（包括细胞活力、增殖、迁移和成骨）和抑制成脂分化，从而改善假体界面骨整合（如图 2.1）。  \n\n![](images/058ecb3be349ddb43be485bf4fdc1a6473b3b99aa053f2989740aa205d3d6138.jpg)  \n图 2.1 经皮超声介导雷帕霉素递送激活自噬和调控成骨微环境促进骨质疏松状态下微孔界面骨整合。",
+        "category": " Introduction"
+    },
+    {
+        "id": 32,
+        "chunk": "# 2.1 3D 打印微孔假体界面的制备与表征",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 33,
+        "chunk": "# 2.1.1 实验仪器与材料  \n\n2.1.1.1 实验仪器   \n\n\n<html><body><table><tr><td>仪器</td><td>品牌</td></tr><tr><td>EBM机</td><td>瑞典 Arcam 公司</td></tr><tr><td>超声波清洗机</td><td>上海比朗仪器制造有限公司</td></tr><tr><td>Micro-CT</td><td>德国Bruker 公司</td></tr><tr><td>扫描电子显微镜</td><td>日本JEOL公司</td></tr><tr><td>高压灭菌锅</td><td>上海昕仪仪器仪表有限公司</td></tr><tr><td>干燥箱</td><td>上海昕仪仪器仪表有限公司</td></tr><tr><td>万能力学测试机</td><td>上海长肯试验设备有限公司</td></tr><tr><td>电子天平</td><td>上海花潮电器有限公司</td></tr></table></body></html>  \n\n2.1.1.2 主要试剂  \n\n\n<html><body><table><tr><td>试剂</td><td>品牌</td></tr><tr><td>Ti6Al4V粉末</td><td>北京爱康医疗</td></tr><tr><td>无水乙醇</td><td>山东利尔康医疗科技有限公司</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 34,
+        "chunk": "# 2.1.2 实验方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 35,
+        "chunk": "# 2.1.2.1 3D 打印钛合金微孔支架的制备  \n\n以 $\\mathrm{Ti}_{6}\\mathrm{Al}_{4}\\mathrm{V}$ 粉末为原料，通过 EBM 技术打印仿生钛合金微孔假体：直径为 10$\\mathrm{mm}$ ，高度 $3.5~\\mathrm{mm}$ 的平板状支架用于细胞实验和理化性能测试；直径为 $6~\\mathrm{mm}$ ，高度 $10\\mathrm{mm}$ 的柱状支架用于动物实验。具体步骤如下：  \n\n1) 使用 CAD 软件准备微孔支架的 STL 文件模型。支架形状设计为上述的平板状和圆柱状，孔径为 $800~{\\upmu\\mathrm{m}}$ ，孔隙率为 $70\\%$ ；  \n\n2) 使用 Cura 软件对将 STL 文件模型进行切片处理，设置层间叠加角度为$90^{\\circ}$ ，并输出为G-code 文件；  \n\n3) 将 G-code 文件导入 EBM 系统，成型仓中填充 $\\mathrm{Ti}_{6}\\mathrm{Al}_{4}\\mathrm{V}$ 粉末，粒径为 10-$50~{\\upmu\\mathrm{m}}$ ，在真空、 $700\\mathrm{~\\textdegree~}$ 条件下，投射直径为 $100~{\\upmu\\mathrm{m}}$ 电子束流，以 $10000\\ \\mathrm{mm/s}$ 速度进行逐层熔融成型；4) 不同形状的微孔支架打印完成后，在无水乙醇和去离子水中清洗，超声震荡，每次处理 $15\\mathrm{min}$ ，以去除支架孔隙内残余 $\\mathrm{Ti}_{6}\\mathrm{Al}_{4}\\mathrm{V}$ 粉末；5) 对获得的支架进行高压蒸汽灭菌消毒（ $\\langle121^{\\circ}\\mathrm{C},30\\mathrm{min}\\rangle$ ，无菌条件保存供后续实验使用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 36,
+        "chunk": "# 2.1.2.2 3D 打印钛合金微孔支架的表征  \n\n1) 使用 Micro-CT 扫描（电压： $102\\mathrm{kV}$ ，电流： $100\\mathrm{mA}$ ）对3D 打印微孔支架的结构进行观察，并分析孔隙率。  \n2) 对微孔支架进行喷金处理后，使用扫描电子显微镜，在 $3\\mathrm{kV}$ 的加速电压下，对3D 打印微孔支架表面形态进行观察，并分析孔径大小。  \n3) 使用万能力学测试机对支架的力学性能进行表征。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 37,
+        "chunk": "# 2.1.2.3 数据统计分析  \n\n每组实验均重复 3 次或 3 次以上，计数结果以均数 $\\cdot\\pm$ 标准差的形式表现，两组数据间的比较用独立 t 检验，两组以上数据用 one way ANOVA 伴随 Student-Newman-Keuls post-hoc 检验校正，当 $p{<}0.05$ 表示组间差异有统计学意义。统计学分析使用SPSS 软件。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 38,
+        "chunk": "# 2.1.3 实验结果  \n\n如图 2.2A 所示，通过 3D 打印技术，我们成功制备了平板状和圆柱状的两种形状的钛合金微孔支架。平板状支架，直径为 $10~\\mathrm{mm}$ ，高为 $3.5~\\mathrm{mm}$ ，横向桁架数为12，纵向桁架数为 4；圆柱状支架直径为 $6\\mathrm{mm}$ ，高为 $10\\mathrm{mm}$ ，横向桁架数为 7，纵向桁架数为 12。两种形状支架的层间桁架均是以 $90^{\\circ}$ 直角交角连接，支架微孔的形状为正方形，表面微孔分布均匀，可见孔间良好的互通结构。  \n\n通过对支架进行 Micro-CT 扫描并定量分析可知微孔支架的孔隙率为$69.2{\\pm}0.9\\%$ 。使用扫描电子显微镜对微孔支架的表面形貌行观察，如图2.2B 所示，微孔的平均直径为 $796.0{\\pm}1.9\\upmu\\mathrm{m}$ ，微孔形态及分布较为均匀，桁架排列规则，桁架之间交角为 $90^{\\circ}$ ，微孔连续性良好。在高倍视野下，可见支架的桁架上分布着较多直径为 $10{-}50~\\upmu\\mathrm{m}$ 的未熔解的 $\\mathrm{Ti_{6}A l_{4}V}$ 粉末。随后，使用万能力学测试机对微孔支架的力学性能进行检测，抗压强度测量期间的荷载-位移曲线转换为应力-应变曲线，并根据曲线计算显示抗压强度为 $48.0{\\pm}2.1\\mathrm{MPa}$ ，而微孔支架的弹性模量为 $1.63{\\pm}0.2\\mathrm{GPa}.$ 。  \n\n![](images/3a4f0a94e8f097d8dfd753a797a83ebb42e7c951638f01df97740ec0b7368e06.jpg)  \n图2.2（A）平板状和圆柱状 3D 打印钛合金微孔支架外观；（B）扫描电镜观察支 架微观结构的图像。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 39,
+        "chunk": "# 2.1.4 讨论  \n\n假体的骨整合能力通常取决于其组成材料的骨传导性，这进一步与假体的孔隙率、孔径分布程度有关。数十年来，骨科医生及生物材料研究者试图寻找出最利于骨长入与整合的假体表面微孔的孔径尺寸。Polo-Corrales 等人研究发现，100$\\upmu\\mathrm{m}$ 的孔径是实现骨-假体界面整合的最低孔隙尺寸指标，低于这一孔径可能会对孔隙中的血管长入及骨形成存在阻碍作用 [131]。 $100{-}500~{\\upmu\\mathrm{m}}$ 的孔径可能有利于成骨细胞的粘附、增殖和分化 [121, 180]。本课题组前期对已发表的骨科微孔植入物的孔径尺寸进行了综述总结，并论证得出假体表面微孔尺寸在 ${500-800\\upmu\\mathrm{m}}$ 时，植入物界面具有最佳的诱导骨长入和骨整合效果 [122]。对于骨组织工程微孔支架，孔隙率也是影响微孔结构植入物生物学功能的关键指标。人体松质骨的孔隙率通常为 $75\\mathrm{-}90\\%$ 。微孔支架的孔隙率在 $50\\%$ 以上，尤其是在 $60\\text{\\textperthousand}$ 的范围内，在结构和机械性能上与人体小梁骨相似 [181]。  \n\n随着 3D 打印技术的兴起及优化，使得个体化、精准制造的微孔假体更易实现。与传统的减材制造方法相比，通过 3D 打印增材制造技术生产的微孔支架的孔径尺寸、形态和孔隙率等参数更易控制，且微孔间互通性良好 [182, 183]。因此，我们通过3D 打印技术制备获得了本研究使用的微孔钛合金支架。就力学性能而言，皮质骨的抗压强度和弹性模量分别为 100−250MPa 和7−20GPa，松质骨的相应值分别为 $11{-}24~\\mathrm{MPa}$ 和 $1.5{-}11.2\\ \\mathrm{GPa}\\ ^{[184]}$ 。本研究中使用的3D 打印微孔假体抗压强度为 $48.0{\\pm}2.1\\ \\mathrm{MPa}$ ，弹性模量为 $1.63{\\pm}0.2\\ \\mathrm{GPa}$ ， 具有较好的力学仿生性能，可以作为负重区域的植入材料，起到支撑作用。同时，与钛及其合金相比，3D 打印微孔钛合金假体的抗压强度和弹性模量明显降低，这可以在一定程度上避免假体植入后的应力屏蔽和骨溶解 [185]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 40,
+        "chunk": "# 2.1.5 小结  \n\n我们通过 3D 打印技术获得的微孔钛合金支架，孔隙率和孔径分别约为$69.2{\\pm}0.9\\%$ 和 $796.0{\\pm}1.9~{\\upmu\\mathrm{m}}$ ，与预设的参数相符。这种具有高孔隙率和仿生力学性能的微孔支架预期可以扩大的界面表面积、增加表面粗糙度、改善植入物的初始稳定性、诱导骨向内生长，从而减少假体植入后的微动并促进界面骨整合。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 41,
+        "chunk": "# 2.2 骨质疏松家兔模型建立及 BMSCs 提取、培养和鉴定",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 42,
+        "chunk": "# 2.2.1 实验仪器与材料  \n\n2.2.1.1 实验仪器   \n\n\n<html><body><table><tr><td>仪器名称</td><td>厂家</td></tr><tr><td>超净操作台</td><td>美国Airtech公司</td></tr><tr><td>细胞培养箱</td><td>美国 Thermo 公司</td></tr><tr><td>恒温水浴锅</td><td>上海昕仪仪器仪表有限公司</td></tr><tr><td>台式低速离心机</td><td>上海秋佐科学仪器有限公司</td></tr><tr><td>超速离心机</td><td>美国 Thermo 公司</td></tr><tr><td>光学显微镜</td><td>日本 Olympus 公司</td></tr><tr><td>荧光倒置显微镜</td><td>日本Olympus 公司</td></tr><tr><td>共聚焦显微镜</td><td>日本Olympus 公司</td></tr><tr><td>冰箱</td><td>青岛海尔生物医疗股份有限公司</td></tr><tr><td>超低温冰箱</td><td>青岛海尔生物医疗股份有限公司</td></tr><tr><td>高压灭菌锅</td><td>上海昕仪仪器仪表有限公司</td></tr><tr><td>干燥箱</td><td>上海昕仪仪器仪表有限公司</td></tr></table></body></html>  \n\n续表：  \n\n\n<html><body><table><tr><td>外科手术器械</td><td>杭州青牛医疗器械有限公司</td></tr><tr><td>移液器</td><td>德国Eppendorf 公司</td></tr><tr><td>细胞计数板</td><td>上海求精生化试剂仪器有限公司</td></tr><tr><td>细胞培养皿</td><td>美国Corning公司</td></tr><tr><td>超声波清洗机</td><td>上海比朗仪器制造有限公司</td></tr><tr><td>离心管</td><td>美国Corning公司</td></tr><tr><td>液氮容器</td><td>成都金凤液氮容器有限公司</td></tr><tr><td>电子天平</td><td>上海花潮电器有限公司</td></tr><tr><td>Micro-CT</td><td>德国Bruker 公司</td></tr><tr><td>酶标仪</td><td>美国 Thermo 公司</td></tr><tr><td>流式细胞仪</td><td>美国Thermo 公司</td></tr></table></body></html>  \n\n2.2.1.2 主要试剂  \n\n\n<html><body><table><tr><td>试剂名称</td><td>厂家</td></tr><tr><td>L-DMEM培养基</td><td>美国Gibco公司</td></tr><tr><td>青链霉素</td><td>美国Gibco 公司</td></tr><tr><td>胎牛血清</td><td>美国Gibco公司</td></tr><tr><td>0.25%胰蛋白酶</td><td>美国Gibco公司</td></tr><tr><td>BMSCs成骨诱导培养基</td><td>美国Hyclone 公司</td></tr><tr><td>BMSCs成软骨诱导培养基</td><td>美国Hyclone 公司</td></tr><tr><td>BMSCs成脂诱导培养基</td><td>美国Hyclone公司</td></tr><tr><td>多聚甲醛</td><td>上海Aladdin 生化科技有限公司</td></tr><tr><td>PBS缓冲液</td><td>北京索莱宝科技有限公司</td></tr><tr><td>鼠抗兔CD90抗体</td><td>北京博奥森生物技术有限公司</td></tr><tr><td>鼠抗兔CD105抗体</td><td>北京博奥森生物技术有限公司</td></tr><tr><td>鼠抗兔CD45抗体</td><td>北京博奥森生物技术有限公司</td></tr><tr><td>羊抗鼠二抗</td><td>北京博奥森生物技术有限公司</td></tr><tr><td>无水乙醇</td><td>山东利尔康医疗科技有限公司</td></tr></table></body></html>  \n\n续表：  \n\n\n<html><body><table><tr><td>75%医用酒精</td><td>山东利尔康医疗科技有限公司</td></tr><tr><td>碘伏毒液</td><td>山东利尔康医疗科技有限公司</td></tr><tr><td>兽用青霉素</td><td>华北制药集团有限责任公司</td></tr><tr><td>戊巴比妥钠</td><td>北京索莱宝科技有限公司</td></tr><tr><td>兔雌激素ELISA试剂盒</td><td>上海恒远生物科技有限公司</td></tr><tr><td>碱性磷酸酶试剂盒</td><td>上海碧云天生物科技有限公司</td></tr><tr><td>甲苯胺蓝染色液</td><td>北京索莱宝科技有限公司</td></tr><tr><td>油红O染色液</td><td>北京索莱宝科技有限公司</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 43,
+        "chunk": "# 2.2.1.3 实验动物  \n\n新西兰大耳白兔：由吉林大学基础医学院实验动物中心提供。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 44,
+        "chunk": "# 2.2.2 实验方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 45,
+        "chunk": "# 2.2.2.1 骨质疏松动物模型制备  \n\n1）雌性5 月龄新西兰大耳白兔，体重约 $2.5\\mathrm{kg}$ ，共106 只，适应性饲养 1 周后通过双侧卵巢切除术（Ovariectomy, OVX）制备骨质疏松模型。具体来说，术前12 小时禁食水，通过耳缘静脉注射 $3\\%$ 戊巴比妥钠（ $(50\\mathrm{mg/kg})$ ）进行全身麻醉，充分麻醉后腹部术区常规备皮，仰卧位固定于手术台，消毒、铺单。取下腹部正中切口，约 $2{-}3~\\mathrm{cm}$ 长，子宫位于膀胱的背侧，呈明显的粉红色。如果一开始未找到子宫，可轻轻牵拉将盲肠或膀胱拨至一旁以暴露子宫。辨认出子宫后，用手指或镊子轻轻抓住子宫并将其提拉出腹腔，沿子宫角追踪输卵管，卵巢位于输卵管头侧。轻轻提拉卵巢蒂以获得较好的视野观察组织，用小的蚊式止血钳穿过卵巢蒂进行钳夹。然后用 4-0 可吸收线在卵巢下方结扎。结扎后完整切除卵巢，并检查确认血管无出血后将组织放回腹腔。同理，结扎并切除另一侧卵巢。观察无明显出血后关闭腹腔。假手术组（Sham）为寻找到卵巢后不做结扎和切除处理即放回腹腔，缝合腹部切口。术后动物在笼内自由活动，术后连续 3 天肌肉注射青霉素（ $1.5\\mathrm{mg/kg})$ ），切口碘伏消毒以防止感染。其中 OVX 组数量为 89 只，Sham数量为 17 只。术后 10 个月，OVX 组与 Sham 组各取 5 只，收集血液和骨组织样本验证骨质疏松疏松模型建立。  \n\n2）术后 10 个月，收集全血样本 $5\\mathrm{ml}$ ，室温放置 2 小时后于 $1000\\ \\mathrm{g}$ 离心 20min，取上清，按照酶联免疫吸附试验（Enzyme-linked immunosorbent assay, ELISA）试剂盒说明书进行检测，加入终止液后，于 $15\\mathrm{min}$ 内使用酶标仪在 $450\\mathrm{nm}$ 波长处测定各孔的OD 值，并绘制标准曲线计算个样本雌激素浓度。  \n\n3）术后 10 个月，使用过量麻醉法处死实验动物，收集股骨样本。采用 Micro-CT 对股骨远端进行扫描，并通过骨形态计量学分析骨密度（Bone mineral density,BMD）和骨体积分数（BV/TV）确认骨质疏松状态。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 46,
+        "chunk": "# 2.2.2.2 BMSCs 分离和培养  \n\n将兔子安乐处死后，在严格无菌操作下分离四肢长骨，无菌提取新鲜骨髓血，采用梯度离心法，即在 $4^{\\circ}\\mathrm{C}$ 下 $1200\\mathrm{rmp}$ 离心 $10\\mathrm{min}$ ，获取 BMSCs。含 $20\\%$ 胎牛血清、 $1\\%$ 青-链霉素的低糖 DMEM 作为完全细胞培养基。将获得的细胞置于培养皿中，并加入 $10\\mathrm{ml}$ 完全培养基，在 $37^{\\circ}\\mathrm{C}$ 、 $5\\%C O_{2}$ 环境的培养箱中进行细胞培养。24 小时后进行半换液，之后每三天进行细胞换液，待细胞融合度超过 $80\\%$ 后，进行消化传代。其中，骨质疏松来源的 BMSCs 标记为OP-BMSCs，健康来源的 BMSCs 标记为 H-BMSCs。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 47,
+        "chunk": "# 2.2.2.3 BMSCs 细胞表面抗原鉴定  \n\n$0.25\\%$ 胰蛋白酶 $2~\\mathrm{ml}$ 加入培养皿中对 BMSCs 进行消化， $2~\\mathrm{min}$ 后加入等量低糖DMEM 培养基，离心（ $1000\\mathrm{rmp}$ ，5 min）后弃上清并用PBS 重悬细胞，调整细胞浓度为 $1{\\times}10^{6}/\\mathrm{ml}$ 。吸取细胞悬液 $1~\\mathrm{ml}$ 于离心管中， $50\\%$ 乙醇透化处理 30min，离心（ $1500\\mathrm{rmp}$ ， $10\\mathrm{min}\\dot{.}$ ）后制备单细胞悬液 $100\\upmu\\mathrm{l}$ ，加入一抗抗体（CD45、CD90、CD105），常温孵育 $30~\\mathrm{min}$ ，离心去上清液，加入 FITC 标记的二抗避光孵育 $30\\mathrm{min}$ ， $4^{\\circ}\\mathrm{C}$ ，PBS 洗涤离心去上清液，加入 PBS 重悬细胞，将流式管中的样品上机进行测试。其中设置两个对照组：包括空白对照组为不加一抗、不加二抗；阴性对照组不加一抗、只加二抗。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 48,
+        "chunk": "# 2.2.2.4 BMSCs 成骨诱导及鉴定  \n\n1）将 BMSCs 以 $1\\times10^{4}/$ 孔的密度接种至 24 孔板中，待细胞贴壁后换液，使用成骨诱导培养基进行随后的诱导培养，每 3 天进行换液，成骨诱导培养 14 天；  \n\n2）BCIP/NBT 染色液工作液配制：ALP 显色缓冲液 $3\\mathrm{ml+BCIP}$ 液 $10\\upmu\\mathrm{l}{+}\\mathrm{NBT}$ 液 $20\\upmu\\mathrm{l}$ ；  \n\n3） $10\\%$ 多聚甲醛固定细胞 $10~\\mathrm{min}$ ，弃去固定液，PBS 洗涤，每孔中加入配置好的染色液工作液 $300\\upmu\\mathrm{l}$ ，室温避光孵育 $30\\mathrm{min}$ 后去离子水洗涤终止染色，镜下观察拍照。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 49,
+        "chunk": "# 2.2.2.5 BMSCs 成软骨诱导及鉴定  \n\n1）将 BMSCs 以 $1\\times10^{4}/$ 孔的密度接种至 24 孔板中，待细胞贴壁后更换软骨诱导培养基进行培养，每 3 天进行换液，成软骨诱导培养 14 天；  \n\n2）用 $10\\%$ 多聚甲醛固定细胞 1h，弃去固定液，自来水冲 $15\\mathrm{min}$ ，蒸馏水洗1 次，每孔中加入甲苯胺蓝染色液 $400\\upmu\\mathrm{l}$ ，室温下浸染 $15\\mathrm{min}$ ， $95\\%$ 酒精洗去多余染液 ，滤纸吸干，光镜下观察。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 50,
+        "chunk": "# 2.2.2.6 BMSCs 成脂诱导及鉴定  \n\n1）将 BMSCs 以 $1\\times10^{4}/$ 孔的密度接种至 24 孔板中，待细胞贴壁后换液，使用成脂诱导培养基A 液进行培养，3 天后换用成脂诱导培养基B 液进行培养 $24\\mathrm{h}$ 。  \n\nA、B 培养基交替使用培养至第 21 天；  \n\n2） $10\\%$ 多聚甲醛固定细胞 $10\\mathrm{min}$ ，弃去固定液，PBS 洗涤，加入油红 O 染色液 $400~\\upmu\\mathrm{l}$ 孵育 $30~\\mathrm{min}$ ，移除油红 O 染液，并用 PBS 洗涤 2 次，光镜下观察。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 51,
+        "chunk": "# 2.2.2.7 数据统计分析  \n\n同章节 2.1.2.3。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 52,
+        "chunk": "# 2.2.3 实验结果",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 53,
+        "chunk": "# 2.2.3.1 骨质疏松动物模型制备  \n\n如图 2.3A 所示，雌性新西兰大耳白兔在双侧卵巢切除 10 个月后，血清雌激素水平为 $11.8{\\pm}3.2\\mathrm{pg/ml}$ ，相较于假手术组（ $(42.3{\\pm}6.2\\mathrm{pg/ml})$ ）明显降低。Micro-CT扫描后对股骨远端骨质进行三维重建，如图 2.3B，OVX 组可见骨量减少、骨组织的微观结构退化，具体表现为骨皮质变薄，骨小梁数量减少。进一步骨形态计量学分析显示相较于假手术组，OVX 模型组的骨体积分数（如图 2.3C）和骨密度（如图2.3D）显著降低。综上，可确认在双侧卵巢切除术后 10 个月，骨质疏松动物模型成功建立。  \n\n![](images/b4b642d986ecb066c0f4809eb379beea3b8e0f44e5c342cda1925efa1c5ffe4c.jpg)  \n图2.3（A）血清雌激素水平；（B）Micro-CT 三维重建图；（C）骨体积分数定量分析；（D）骨密度定量分析（ $\\because p<0.01$ ; ${***p}<0.001\\rangle$ ）。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 54,
+        "chunk": "# 2.2.3.2 BMSCs 生长和形态学特点  \n\n分离获得的 BMSCs 起初呈现为透明球形，24 小时后可见细胞贴壁呈短梭形，48 小时后可见明显条索状排列的梭形细胞。如图 2.4 所示，培养 5 天后 H-BMSCs 融合度达到 $80\\%$ 以上，细胞排列较为致密、规则，而 OP-BMSCs 融合度稍低于 H-BMSCs。  \n\n![](images/44d5109889b3d7f6e9bce896c7a46a9815804947eb6aa5f6cfe99186a56c3a5f.jpg)  \n图2.4 骨质疏松来源的 BMSCs 与健康来源的 BMSCs 的形态学特征。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 55,
+        "chunk": "# 2.2.3.3 BMSCs 表面抗原鉴定  \n\n通过流式细胞术对分离获得的 H-BMSCs 和 OP-BMSCs 的表面抗原进行检测。结果显示获得的细胞均表现为 CD90 呈阳性表达，CD34 和 CD45 呈阴性表  \n\n达，两组细胞均符合 BMSCs 典型的细胞表面抗原表达特点（图 2.5）。  \n\n![](images/207c7f5d017923800cca98f61a95027ace0df158f17c42eef7aedb25bcf58119.jpg)  \n图2.5 （A）流式细胞术鉴定H-BMSCs 表型抗原；（B）流式细胞术鉴定OP-BMSCs表型抗原。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 56,
+        "chunk": "# 2.2.3.4 BMSCs 三向分化鉴定  \n\n如图 2.6 所示，获得的 H-BMSCs 与 OP-BMSCs 经过成骨诱导分化 14 天后，碱性磷酸酶染色可见胞质中出现深染的黑褐色团块，显示细胞经成骨诱导后往成骨方向分化；甲苯胺蓝染色显示胞质被染为紫红色，表明 BMSCs 经成软骨诱导培养后可向成软骨方向分化；油红 O 染色可见细胞中出现红色脂滴且有融合迹象，证明BMSCs 经成脂诱导分化后可向成脂肪方向分化。且相较于 H-BMSCs，OP-BMSCs 在碱性磷酸酶染色和甲苯胺蓝染色中细胞阳性着色较浅，而油红 O染色阳性脂滴形成更多。  \n\n![](images/44580f05195489d8fab37deb03201fa98ac5b3cd02e325f13b5324d99d552b98.jpg)  \n图2.6 碱性磷酸酶染色、甲苯胺蓝染色和油红 O 染色分别验证H-BMSCs 和OP-BMSCs 的成骨、成软骨和成脂三向分化能力。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 57,
+        "chunk": "# 2.2.4 讨论  \n\n骨质疏松症是主要由于骨量降低、骨的微观结构破坏和脆性增加，导致患者容易出现骨折的一种全身性、代谢性骨病。其中，绝经后骨质疏松一般发生在女性绝经后 5-10 年，这是由于女性绝经后雌激素在体内水平急剧下降，引起骨含量减少和钙成分吸收障碍，致骨代谢出现异常而出现骨质疏松表现 [186, 187]。双侧卵巢切除术是制备骨质疏松动物模型的经典方法 [188-190]。在本研究中，双侧卵巢切除术后 10 个月，可见白兔血清雌激素水平明显下降，骨密度和骨量显著低下，证明成功地建立了骨质疏松动物模型。  \n\nBMSCs 是一类具有自我更新和多向分化潜能的种子细胞，可分化为成骨细胞、软骨细胞、脂肪细胞、成纤维细胞和神经相关细胞等。BMSCs 广泛存在于骨髓腔中，对骨损伤后的修复起至关重要的作用 [191, 192]。骨质疏松患者骨折或者关节置换术后骨再生和骨整合能力不足，可能是部分由于 BMSCs 低下的自噬能力导致成骨分化不足，趋向于成脂分化而造成 [193, 194]。因此，我们使用收集健康白兔与骨质疏松白兔骨髓血中中的 BMSCs 进行分离、培养，用于后续细胞学研究。BMSCs 的提取过程严格遵循无菌原则。由于骨髓血中存在大量的红细胞和脂肪颗粒，如使用传统的贴壁法，细胞在培养皿上贴附效率不高，且考虑到骨质疏松模型制备周期较长、来源不易，我们采用密度梯度离心法保证 BMSCs 的提取效率，此方法能将骨髓血中的各成分高效地分离 [195]。随后，我们通过对获得的细胞形态观察、细胞表面标志物鉴定和多向诱导分化来确定获得的细胞确为BMSCs。此外，在多向诱导分化实验中可见相较于 H-BMSCs，OP-BMSCs 在碱性磷酸酶染色中细胞阳性着色较浅，而油红 O 染色阳性脂滴更多且融合，反应OP-BMSCs 成骨分化能力减弱而趋向于成脂分化，与既往文献结论相同 [45, 196]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 58,
+        "chunk": "# 2.2.5 小结  \n\n本章节通过双侧卵巢切除法，在手术 10 个月后对血清雌激素水平测定和Micro-CT 定量分析骨量验证成功制备了骨质疏松动物模型。随后，使用密度梯度离心法获取种子细胞并培养、扩增，并通过对细胞的形态观察、表面标志物鉴定和多向诱导分化来确定获得的细胞确为 BMSCs。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 59,
+        "chunk": "# 2.3 超声介导雷帕霉素递送激活 OP-BMSCs 自噬",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 60,
+        "chunk": "# 2.3.1 实验仪器与材料  \n\n2.3.1.1 实验仪器   \n\n\n<html><body><table><tr><td>仪器名称</td><td>厂家</td></tr><tr><td>超声电导仪</td><td>北京诺亚同舟医疗技术有限公司</td></tr><tr><td>细胞培养箱</td><td>美国Thermo 公司</td></tr><tr><td>超净操作台</td><td>美国Airtech公司</td></tr><tr><td>蛋白电泳及转膜仪</td><td>中国 Tanon 公司</td></tr><tr><td>Clinx Science Instruments</td><td>上海勤翔科学仪器有限公司</td></tr><tr><td>高效液相色谱-串联质谱仪</td><td>美国 Thermo 公司</td></tr><tr><td>透射电子显微镜</td><td>日本JEOL公司</td></tr></table></body></html>\n\n其他仪器同 2.2.1.1。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 61,
+        "chunk": "# 2.3.1.2 主要试剂  \n\n<html><body><table><tr><td>试剂名称</td><td>厂家</td></tr><tr><td>Triton-X 100</td><td>美国Invitrogen 公司</td></tr><tr><td>蛋白裂解液</td><td>北京全式金生物技术有限公司</td></tr><tr><td>蛋白酶抑制剂</td><td>北京全式金生物技术有限公司</td></tr><tr><td>5x蛋白上样缓冲液</td><td>北京鼎国昌盛生物技术有限公司</td></tr><tr><td>BCA蛋白浓度测定试剂盒</td><td>上海碧云天生物技术有限公司,</td></tr><tr><td>Protein leader</td><td>美国 Thermo 公司</td></tr><tr><td>PVDF膜</td><td>美国Millipore公司</td></tr><tr><td>SDS-PAGE凝胶配制试剂盒</td><td>北京鼎国昌盛生物技术有限公司</td></tr><tr><td>脱脂奶粉</td><td>北京鼎国昌盛生物技术有限公司</td></tr><tr><td>山羊血清</td><td>上海源叶生物科技有限公司</td></tr><tr><td>目的蛋白一抗</td><td>北京博奥森生物技术有限公司</td></tr><tr><td>标记二抗</td><td>北京博奥森生物技术有限公司</td></tr><tr><td>Ad-McHery-GFP/LC3B</td><td>上海碧云天生物技术有限公司</td></tr></table></body></html>  \n\n续表：  \n\n\n<html><body><table><tr><td>雷帕霉素</td><td>美国Sigma-Aldrich 公司</td></tr><tr><td>FITC-雷帕霉素</td><td>西安齐岳生物科技有限公司</td></tr><tr><td>戊二醛</td><td>美国 Sigma-Aldrich 公司</td></tr><tr><td>酸</td><td>上海Aladdin生化科技有限公司</td></tr><tr><td>丙酮</td><td>上海Aladdin生化科技有限公司</td></tr></table></body></html>\n\n其他试剂同 2.2.1.2。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 62,
+        "chunk": "# 2.3.1.3 溶液配制  \n\n1）电泳缓冲液（1L）  \n\nSDS 1.0 g 甘氨酸 14.4 g Tris 3.0 g  \n\n2）电转缓冲液（1L）  \n\n甲醛 200 ml甘氨酸 14.4 gTris 3.0 g  \n\n3）TBST 溶液（ $500\\mathrm{ml}\\cdot$ ）  \n\nNaCl 4.09 g Tris 0.605 g Tween 20 0.5 ml  \n\n4）Western Blot 封闭液： $5\\%$ 脱脂奶粉  \n\n称取 1g 脱脂奶粉加到 $20~\\mathrm{ml}$ TBST 溶液中，于摇床上摇匀。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 63,
+        "chunk": "# 2.3.1.4 实验动物  \n\n新西兰大耳白兔：由吉林大学基础医学院实验动物中心提供。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 64,
+        "chunk": "# 2.3.2 实验方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 65,
+        "chunk": "# 2.3.2.1 经皮超声介导雷帕霉素递送效率检测  \n\n1）体外超声导药效率分析：取 $9.14~\\upmu\\mathrm{g}$ 雷帕霉素充分溶解于 $10~\\mathrm{ml}$ 低糖DMEM 中，配置出浓度为 $1000~\\mathrm{{nM}}$ 雷帕霉素溶液。将明胶海绵裁剪为直径为 1cm 的圆片状，并将 $200~\\upmu\\mathrm{l}$ 雷帕霉素溶液添加到明胶海绵块中。将明胶海绵与超声发射探头紧密贴合，然后用新鲜兔皮外层包裹明胶海绵与探头，兔皮内层朝向含有 $2~\\mathrm{ml}$ 溶液的孔板。设置超声电导仪的频率为 $30~\\mathrm{kHz}$ ，强度为 $45\\ \\mathrm{W/cm}^{2}$ ，每隔 $2\\mathrm{min}$ 收集孔板中的液体，并用新鲜溶液等量替换，导药结束后用高效液相色谱-串联质谱仪检测各时间点孔板中雷帕霉素的浓度。  \n\n2）体内超声导药效率分析：将 3D 打印微孔钛合金支架植入兔左侧股骨远端外侧髁（具体手术操作步骤见 2.5.2.1 章节）。同上，配制浓度为 $1000~\\mathrm{{nM}}$ 的FITC-雷帕霉素。然后将浸有 $200~\\upmu\\mathrm{l}$ 药液的明胶海绵稳定放置在左侧股骨远端外侧髁皮肤与超声发射器头之间进行药物递送，设置超声电导仪的频率为 $30\\mathrm{kHz}$ ，强度为 $45\\mathrm{W/cm}^{2}$ ，时间为 $10\\mathrm{min}$ 。作为对照，Con 组未接受超声导药处理，UI组只接受不含雷帕霉素的超声处理。导药结束后，过量麻醉法处死动物，收集左膝外侧髁软组织及股骨进行切片，在荧光显微镜下观察 FITC-雷帕霉素在组织内的分布情况。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 66,
+        "chunk": "# 2.3.2.2 各组细胞的 mTOR、LC3Ⅱ/Ⅰ和 P62 的蛋白水平检测  \n\n通过 Western Blot 检测细胞中 mTOR、LC3Ⅱ/Ⅰ和 P62 的蛋白表达水平，评估细胞的自噬水平，具体步骤如下：  \n\n1）H-BMSCs 和 OP-BMSCs 以 $1\\times10^{4}/$ 每孔种植在 12 孔板中，H-BMSCs 不接受任何处理（Health 组），OP-BMSCs 不接受任何处理（OP 组），OP-BMSCs接受不含雷帕霉素的超声处理（OP-UI 组），OP-BMSCs 接受含雷帕霉素的超声导药处理（OP-UIRa 组）。超声电导仪工作参数：频率为 $30\\mathrm{kHz}$ ，强度为 $45\\mathrm{W}/\\mathrm{cm}^{2}$ ，时间为 $10\\mathrm{min}/$ 每天。  \n\n2）将接受不同处理 3 天后的细胞用PBS 轻轻冲洗两遍，加入 $1\\mathrm{mlPBS}$ ，将培养板置于冰上，用细胞刮刀刮取贴壁细胞，并将液体转移至 $1.5~\\mathrm{ml}$ EP 管中，离心（ $\\cdot5\\mathrm{min}$ ， $3000\\mathrm{rpm}\\rrangle$ ），弃上清收集细胞沉淀。加入 $160\\upmu\\mathrm{l}$ 含蛋白酶抑制剂的蛋白裂解液，吹打沉淀后振荡涡旋器振荡 15s，静置 $10\\mathrm{min}$ ，重复上述步骤 3 次，离心（10min， $12000\\mathrm{rpm}\\therefore$ ），收集上清。 $160\\upmu\\mathrm{l}$ 上清液中加入 $40\\upmu\\updownarrow5\\times$ 蛋白上样缓冲液， $100^{\\circ}\\mathrm{C}$ 水浴加热 $5\\mathrm{min}$ ，置于冰上冷却，保存于- $-20^{\\circ}\\mathrm{C}$ 备用。  \n\n3）BCA 法测定总蛋白浓度：取 $2~\\upmu\\upmu$ 蛋白样品，并加入 $18~\\upmu\\upmu$ 双蒸水稀释。根据 BCA 试剂盒说明书，将 A、B 溶液以 1：50 的比例混合均匀，每孔 $200~\\upmu\\mathrm{l}$ 混合液；在 96 孔板中加入 $200~\\upmu\\mathrm{l}$ 混合液，以及 $20~\\upmu\\mathrm{l}$ 蛋白标准品和待测蛋白样品，低速振荡 $30\\mathrm{s}$ ， $37^{\\circ}\\mathrm{C}$ 孵育 $30\\mathrm{min}$ ，用酶标仪在 $594\\mathrm{nm}$ 测定吸光光度值并记录结果。根据上述结果绘制标准曲线并计算相应待测样品的蛋白浓度。  \n\n4）Western Blot 检测：根据目的蛋白分子量大小配制 $10\\%$ 的 SDS 凝胶，每个样品上样量为 $15~{\\upmu\\mathrm{g}}$ 总蛋白，根据蛋白浓度计算后使用 $1\\times$ 蛋白上样缓冲液补齐体系使上样体积一致。 $80\\mathrm{V}$ 恒压电泳 $30\\mathrm{min}$ 左右至蛋白跑至分离胶，再以 $120\\mathrm{V}$ 恒压继续电泳至目的蛋白分离。使用湿性电转法将凝胶上的蛋白转至甲醛激活的PVDF 膜上，恒流法电转（电流 $200~\\mathrm{{mA}}$ ，电压不低于 80V）。取出电转结束的PVDF 膜， $5\\%$ 的脱脂奶粉室温下于摇床上封闭 1 h，TBST 洗膜3 次，每次 5 min，加入一抗工作液 $4^{\\circ}\\mathrm{C}$ 孵育过夜（一抗稀释浓度分别为： $\\upbeta$ -actin 1:1000，mTOR 1：200、LC3Ⅱ 1:100、LC3Ⅰ 1:100 和 P62 1:200）。第二天 TBST 洗膜 3 次，每次$10\\mathrm{min}$ ，加入 HRP 标记的相应二抗工作液（稀释浓度均为：1：500），于摇床上室温孵育 $45~\\mathrm{min}$ 。TBST 洗膜 3 次，每次 $5~\\mathrm{min}$ ，加入 ECL 显影液利用 ClinxScience Instruments 曝光，保存图片，并使用 Image J 软件计算各条带灰度值，以$\\upbeta$ -actin 为内参计算各组蛋白的表达量。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 67,
+        "chunk": "# 2.3.2.3 Ad-mCherry-GFP-LC3B 双荧光腺病毒感染细胞  \n\n1）为了分析不同条件下的自噬通量，将 H-BMSCs 和 OP-BMSCs 以 $1\\times10^{4}/$ 每孔种植在在6 孔培养板上，并在达到 $50\\%-60\\%$ 的融合时进行感染；2）用 PBS 洗涤三次后，用浓度为 10 摩尔的表达 mCherry-GFP-LC3B 融合蛋白的腺病毒（Ad-McHery-GFP/LC3B）感染细胞。 $24\\mathrm{h}$ 后， $4\\%$ 多聚甲醛固定，PBS 洗涤 3 遍，通过荧光显微镜观察 mCherry 和 GFP 的表达来显示自噬体和自噬溶酶体的变化",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 68,
+        "chunk": "# 2.3.2.4 透射电子显微镜观察细胞内自噬表达  \n\n1）同 2.3.2.2 步骤 1）处理各组细胞3 天后，收集细胞；  \n\n2) $2.5\\%$ 戊二醛 $4^{\\circ}\\mathrm{C}$ 固定 2-4h；  \n\n3) 等渗： $1{\\times}\\mathrm{PBS}$ 液置换 $4^{\\circ}\\mathrm{C}$ 过夜；  \n\n4) $1\\%$ 锇酸 $4^{\\circ}\\mathrm{C}$ 固定2h： $1\\%$ 锇酸的配制：去离子水进行配制 $2\\%$ 锇酸工作液静置3 天充分溶解，再用 $1{\\times}\\mathrm{PBS}$ 稀释到浓度为 $1\\%$ 锇酸染液（ $(2\\%$ 的锇酸为原液）；  \n\n5) $1{\\times}\\mathrm{PBS}$ 漂洗， $5\\operatorname*{min}^{\\times3}$ 次；  \n\n6) 酒精和丙酮脱水： $50\\%$ 酒精（ $20\\ \\mathrm{min}\\times1$ 次） $\\rightarrow70\\%$ 酒精（ $20\\ \\mathrm{min}{\\times}1$ 次）$\\rightarrow90\\%$ 酒精（ $20\\mathrm{min}{\\times}1$ 次） $\\rightarrow100\\%$ 酒精（ $20\\ \\mathrm{min}{\\times}1$ 次） $\\rightarrow100\\%$ 丙酮（ $30\\ \\mathrm{min}\\times2$ 次)；  \n7). 包埋剂浸透（烤灯复温， $37^{\\circ}\\mathrm{C}$ 浸透）：环氧树脂：丙酮 $|=1{:}1$ （ $60\\mathrm{{min}\\times1}$ 次）$\\rightarrow$ 环氧树脂：丙酮 $=2{:}1$ （ $60\\mathrm{min}\\mathrm{\\times}1$ 次） $\\rightarrow$ 环氧树脂：丙酮 $|=3{:}1$ （ $60\\mathrm{min}{\\times}1$ 次）；  \n8) 纯包埋剂包埋： $40^{\\circ}\\mathrm{C}/2\\mathrm{h}{\\rightarrow}65^{\\circ}\\mathrm{C}/3\\mathrm{h}{\\rightarrow}80^{\\circ}\\mathrm{C}/15\\mathrm{h}$ ；  \n9) 半薄切片定位： 制备半薄切片，甲苯胺蓝染色，进行目标位置；  \n10) 超薄切片制备： $70\\mathrm{nm}$ 超薄切片；  \n11) 染色： $1\\%$ 乙酸铀酰染色 $10\\mathrm{min}$ 后，去离子水洗 $10\\mathrm{min}$ ； $1\\%$ 柠檬酸铅染$10\\mathrm{min}$ ，去离子水洗 $10\\mathrm{min}$ ；  \n12) 透射电镜拍照。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 69,
+        "chunk": "# 2.3.2.5 数据统计分析  \n\n同章节 2.1.2.3。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 70,
+        "chunk": "# 2.3.3 实验结果",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 71,
+        "chunk": "# 2.3.3.1 经皮超声介导雷帕霉素递送效率  \n\n为明确超声导药能够顺利通过皮肤进入靶部位，首先构建模拟体外超声导药体系（图 2.7A）。如图 2.7B 显示，超声电导仪工作 $10~\\mathrm{min}$ 后，培养基中雷帕霉素的浓度为 $98.33\\pm3.09\\mathrm{nM}$ ，几乎将明胶海绵中的雷帕霉素完全透皮释放。随后，我们使用 FITC 标记的雷帕霉素对植入微孔支架后的兔模型进行超声导药（图2.7C）。如图 2.7D 显示，在 UIRa 组中可以观察到皮肤、肌肉组织以及微孔支架孔隙中布满绿色荧光标记的雷帕霉素，表明本实验中使用的经皮超声导药的策略能够成功地将雷帕霉素递送至靶部位。  \n\n![](images/3925108ef166de05760d8d1e6679b0a0e7706edbc6a060f0c3d9a5cc48a19905.jpg)  \n图 2.7（A）体外超声介导雷帕霉素递送模式图；（B）体外雷帕霉素浓度与超声电导时间的关系；（C）体内超声介导雷帕霉素递送模式图；（D）体内皮肤、肌肉及植入骨组织的微孔支架孔隙中 FITC-雷帕霉素的荧光分布。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 72,
+        "chunk": "# 2.3.3.2 自噬关键蛋白 mTOR、LC3Ⅱ/Ⅰ和 P62 的表达水平  \n\n为了确认自噬相关蛋白在超声电导雷帕霉素后的变化，我们利用 WesternBlot 技术检测了经过不同处理后的细胞中这些的蛋白表达水平（图 2.8A）。如图2.8B 定量分析显示，与 H-BMSCs 相比，OP 和 OP-UI 中的 mTOR 和 P62 表达水平增高，LC3Ⅱ/Ⅰ比值下降，表明 OP-BMSCs 的自噬受到抑制，而单纯使用不含雷帕霉素的超声电导作用并不会逆转这种趋势。而通过递送 mTOR 抑制剂雷帕霉素可以使OP-BMSCs 的中的mTOR 蛋白表达受到抑制，从而提高 LC3Ⅱ/Ⅰ比值和减少P62 表达，激活细胞自噬。  \n\n![](images/01aaa586a4d9a36e28e793f2badfdf4d67d485ea630b3b5538b79d3cf438543b.jpg)  \n图 2.8（A）Western Blot 显影条带及相应分子量， $\\upbeta$ -actin 为内参分子；（B）各组蛋白条带灰度值统计结果（ $^{\\cdot}\\ast_{p}<0.05$ ; $**_{p}<0.01)$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 73,
+        "chunk": "# 2.3.3.3 Ad-mCherry-GFP-LC3B 双荧光腺病毒感染细胞观察自噬通量变化  \n\n如图 2.9A 所示，Ad-mCherry-GFP-LC3B 感染细胞后，mCherry 和 GFP 荧光融合形成的黄色斑点表明自噬体（白色箭头），其未与溶酶体融合。绿色荧光蛋白可以在酸性环境中降解，因此红色斑点代表与溶酶体融合的自噬体（红色箭头）。在健康组中观察到一定量的黄点和红点，显示 H-BMSCs 中自噬正常活性水平。然而，OP 和OP-UI 组中的红点较少，表明自噬通量减少。相反，在 OP-UIRa 组中，红色斑点（与黄色斑点相比）增加，表明自噬通量被激活。  \n\n此外，透射电镜观察显示，与 OP 和 OP-UI 组相比，Health 组和 OP-UIRa 组的自噬泡数量增加（图 2.9B）。这些结果证实，相比于 H-BMSCs，OP-BMSCs 自噬活性降低，而超声介导的雷帕霉素递送可使OP-BMSCs 受损的自噬活性上调，并接近至健康状态。  \n\n![](images/f5552c327482f591c6f1a0872a615245b243ff15e4261683eb87dbdd3c77b562.jpg)  \n图 2.9（A）Ad-mCherry-GFP-LC3B 双荧光腺病毒感染细胞，白色箭头表示自噬体，红色箭头表示自噬溶酶体；（B）透射电镜观察细胞内自噬泡形成。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 74,
+        "chunk": "# 2.3.4 讨论  \n\n本实验所采用的超声电导仪（NAVA-01CSSY）由北京诺亚同舟医疗技术有限公司提供，该经皮超声导药系统是一种以一定参数范围的超声波为主要动力，能够实现向靶部位无创经皮递送药物的专用医学设备，利用超低频超声波的聚焦辐射压产生足够的冲击力，使机械能转化为强大而可控的动能，将递送的药物透过皮肤靶向进入体内治疗部位，达到提高局部组织和细胞内药物浓度的效果。其具体机制可分为人工生物通道的建立和强力定向驱动。其中人工生物通道的建立机制包括：1）、电致孔技术：是采用一种特定的瞬时电脉冲，改变组织膜和细胞膜脂质颗粒的排列，使之有序化，形成药物通透的水性孔道。密集的孔道在一定范围内形成药物进入体内的高通透区。2）、超声空化技术：利用超声波的空化作用，可使皮肤细胞膜、组织膜形成和扩大已形成的生物孔道，大孔径可达 $250\\mathrm{nm}$ ，孔道可维持时间长达两小时。此外，强力定向驱动的机制包括：1）、超声波对流转运作用与辐射压作用使药物粒子和分子获得定向转运的动能，沿声波传播方向运动。2）、现代离子导入在电场作用下，离子型药物活化，按电趋向性定向泳动。3）、病变组织药物浸润，促进药物自细胞外向细胞内转运 [197-200]。因此，在设置超声电导仪参数频率为 $30\\mathrm{kHz}$ ，强度为 $45\\mathrm{W}/\\mathrm{cm}^{2}$ ，可以很好的将负载的药物经皮分散到溶液中；在该参数下通过 $10~\\mathrm{min}$ 体内超声电导，可以很好的将雷帕霉素递送至皮下软组织及植入股骨髁内的微孔支架内部，这种成功经皮递送雷帕霉素到靶部位为后续的研究提供了理论基础。  \n\nBMSCs 具有自我更新和多向分化的潜能，在假体植入后的骨再生和骨整合中发挥关键作用 [201-203]。基线水平的自噬活性可以维持干细胞的干性和分化能力。然而，自噬的失衡导致细胞衰老、数量减少和功能受损 [204-206]。在骨质疏松状态下，OP-BMSCs 的自噬水平低下，可能是骨损伤后成骨能力不足的重要原因[45]。自噬可以通过多种信号途径进行调节，其中一个关键分子是雷帕霉素的靶标（Target of Rapamycin, TOR），它可以感知细胞内外的各种信号变化，并调节自噬水平以响应外部环境的刺激。先前的研究表明，mTOR 是哺乳动物 TOR 的同系物，可以调节细胞周期、生长和增殖 [207]。绝经后骨质疏松哺乳动物 BMSCs的自噬水平降低，然而，雷帕霉素抑制关键靶点 mTOR 可以恢复自噬水平，增强OP-BMSCs 的增殖和成骨分化潜能，并改善体内的骨微观结构 [45]。雷帕霉素作为经典的自噬诱导剂，可激活细胞的自噬活性 [52, 53]。既往研究显示通过雷帕霉素激活细胞自噬，可以部分改善骨质疏松状态下的成骨不良，增加骨量 [54, 55]。这些结果表明，自噬调节 BMSCs 的再生功能并控制骨质疏松症的发展，而通过雷帕霉素激活自噬可能为增强骨质疏松状态下的假体界面骨整合提供有效的治疗策略。  \n\n在自噬形成时，胞浆型 LC3（即LC3-I）会被酶解掉一小段多肽，从而形成  \n\n（自噬体）膜型（即 LC3-II），在此过程中，LC3-II 比例增加代表自噬启动；而可通过自噬来降解得 P62 可反映自噬发生的强度。在自噬过程中，LC3 II 升高的同时伴随 P62 水平下降，则可证明自噬流通畅；若 LC3II 升高的同时伴随 P62也升高，则意味着自噬起始阶段正常，但下游不通畅，吞噬体和溶酶体不能顺利地融合 [208]。除此之外，通过 Ad-mCherry-GFP-LC3B 双荧光腺病毒感染细胞检测观察自噬通量情况，由于 GFP 在酸性环境中可被降解，红绿荧光合并后出现的黄色斑点即表示未与溶酶体融合的自噬体，结合后显示的红色斑点代表可将绿色荧光淬灭的自噬溶酶体。如自噬通常、吞噬体和溶酶体能正常融合，则显示未红色荧光多于黄色荧光；若自噬下游受阻，导致吞噬体和溶酶体不能正常进行融合，则主要显示为黄色荧光。我们通过一系列检测证明 OP-BMSCs 低下的自噬水平可以通过雷帕霉素的递送而得到纠正，且几乎可以恢复到正常状态下的水平。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 75,
+        "chunk": "# 2.3.5 小结  \n\n本实验所采用的超声电导仪可以成功地将雷帕霉素递送至靶部位，并通过Western Blot 法检测自噬通路关键蛋白、Ad-mCherry-GFP-LC3B 双荧光腺病毒感染和透射电镜观察自噬体，证明这种策略可以激活细胞自噬，纠正OP-BMSCs 低下的自噬水平，甚至恢复到正常状态下的水平。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 76,
+        "chunk": "# 2.4 超声介导雷帕霉素递送调节 OP-BMSCs 功能",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 77,
+        "chunk": "# 2.4.1 实验仪器与材料",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 78,
+        "chunk": "# 2.4.1.1 实验仪器  \n\n<html><body><table><tr><td>仪器名称</td><td>厂家</td></tr><tr><td>超声电导仪</td><td>北京诺亚同舟医疗技术有限公司</td></tr><tr><td>超净操作台</td><td>美国Airtech公司</td></tr><tr><td>细胞培养箱</td><td>美国 Thermo 公司</td></tr><tr><td>光学显微镜</td><td>日本Olympus 公司</td></tr><tr><td>荧光倒置显微镜</td><td>日本Olympus 公司</td></tr><tr><td>Transwell 孔板</td><td>美国Corning 公司</td></tr></table></body></html>  \n\n续表：  \n\n\n<html><body><table><tr><td>PCR板 瑞士Roche 公司</td></tr><tr><td>LightCycler 480 瑞士Roche 公司</td></tr><tr><td>分光光度计 NanoDrop 2000 美国Thermo 公司</td></tr></table></body></html>  \n\n其他仪器同 2.2.1.1。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 79,
+        "chunk": "# 2.4.1.2 主要试剂  \n\n<html><body><table><tr><td>试剂名称</td><td>厂家</td></tr><tr><td>雷帕霉素</td><td>美国 Sigma-Aldrich 公司</td></tr><tr><td>CCK-8试剂盒</td><td>上海贝博生物科技有限公司</td></tr><tr><td>Calcein-AM/PI染色试剂盒</td><td>上海贝博生物科技有限公司</td></tr><tr><td>甲醇</td><td>上海Aladdin生化科技有限公司</td></tr><tr><td>多聚甲醛</td><td>上海Aladdin生化科技有限公司</td></tr><tr><td>Phalloidin-鬼笔环肽染色试剂盒</td><td>北京索莱宝科技有限公司</td></tr><tr><td>油红〇染色液</td><td>北京索莱宝科技有限公司</td></tr><tr><td>总 RNA提取试剂盒</td><td>上海Promega 生物产品有限公司</td></tr><tr><td>RNA逆转录试剂盒</td><td>日本 Takara 公司</td></tr><tr><td>SYBR Green Master mix</td><td>瑞士Roche 公司</td></tr><tr><td>qPCR引物</td><td>上海生工生物有限公司</td></tr><tr><td>RT-qPCR 试剂盒</td><td>北京全式金生物技术有限公司</td></tr><tr><td>茜素红染液</td><td>北京索莱宝科技有限公司</td></tr><tr><td>氯化十六烷基吡啶</td><td>美国 Sigma-Aldrich 公司</td></tr><tr><td>Runx-2 单克隆抗体</td><td>美国Abcam公司</td></tr><tr><td>ALP 单克隆抗体</td><td>美国Abcamy公司</td></tr><tr><td>OCN单克隆抗体</td><td>美国Abcam公司</td></tr><tr><td>OPN单克隆抗体</td><td>美国Abcam公司</td></tr><tr><td>山羊抗兔Cy3荧光二抗</td><td>北京博奥森生物技术有限公司</td></tr><tr><td>山羊抗小鼠 AlexaFluor?488 荧光二抗</td><td>美国 Thermo 公司</td></tr><tr><td>DAPI</td><td>北京索莱宝生物科技有限公司</td></tr><tr><td>含 DAPI 抗淬灭封片剂</td><td>美国Vector 公司</td></tr></table></body></html>  \n\n其他试剂同 2.2.1.2。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 80,
+        "chunk": "# 2.4.1.3 溶液配制",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 81,
+        "chunk": "# 1）免疫荧光封闭液  \n\n在 $20~\\mathrm{ml}$ PBS 中加入 $0.2\\mathrm{g}\\mathrm{BSA}$ ，置于水平摇床室温摇 $20\\mathrm{{min}}$ ，再加入 $200{\\mathrm{ul}}$ 山羊血清封闭液并混匀， $4^{\\circ}\\mathrm{C}$ 保存。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 82,
+        "chunk": "# 2.4.2 实验方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 83,
+        "chunk": "# 2.4.2.1 CCK-8 法测试细胞增殖情况  \n\n将细胞以 $1\\times10^{4}/$ 孔的密度种植在 12 孔板中，待细胞贴壁后，给与超声介导的雷帕霉素递送处理，具体操作同章节 2.3.2.2 步骤 1）。在第 1，4 和 7 天时使用CCK-8 试剂盒检测细胞增殖情况，具体操作如下：  \n\n1）在预定检测时间点，更换培养基后加入 $10\\%$ 体积的CCK-8 反应液；2）将 12 孔板放入 $37^{\\circ}\\mathrm{C}$ 、 $5\\%\\mathrm{CO}_{2}$ 的孵箱中避光孵育 $2\\mathrm{h}$ ；3）取出 12 孔板，在每个样品中吸取 $100~\\upmu\\mathrm{l}$ 的液体转移到96 孔板；4）转移结束后，迅速将 96 孔板放置在酶标仪内检测各组 OD 值，检测波长为 $450\\mathrm{nm}$ ；5）收集所得数据，进行统计分析。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 84,
+        "chunk": "# 2.4.2.2 Calcein-AM/PI 细胞活死染色  \n\n将细胞以 $1\\times10^{4}/$ 孔的密度种植在 12 孔板中，待细胞贴壁后，给与超声介导的雷帕霉素递送处理，具体操作同章节 2.3.2.2 步骤 1）。在第3 天时使用 Calcein-AM/PI 试剂盒检测细胞活死情况，具体操作如下：  \n1）配制染色工作液：Calcein-AM 工作液： $0.5\\operatorname{ml}\\mathrm{C}+10\\operatorname{ul}\\mathrm{A}+4.5\\operatorname{ml}$ 无菌去离子水。PI 工作液： $0.5\\mathrm{ml}\\mathrm{C}+5\\mathrm{ul}\\mathrm{B}+4.5\\mathrm{ml}$ 无菌去离子水；  \n2）细胞固定：吸取培养基， $4\\%$ 多聚甲醛溶液固定 $10~\\mathrm{min}$ ，PBS 清洗 3 次；  \n3）每孔加入 $0.5{\\mathrm{ml}}$ Calcein-AM 工作液避光孵育 $15\\mathrm{min}$ ，随后避光环境下加入PI 工作液 $0.5{\\mathrm{ml}}$ 继续避光孵育 $5\\mathrm{min}$ ；  \n4）迅速转移到暗室中，荧光显微镜下观察并拍照；  \n5）收集所得图片，Image J 分析细胞存活率。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 85,
+        "chunk": "# 2.4.2.3 Phalloidin-鬼笔环肽染色  \n\n将细胞以 $1\\times10^{4}/$ 孔的密度种植在 12 孔板中，待细胞贴壁后，给与超声介导的雷帕霉素递送处理，具体操作同章节 2.3.2.2 步骤 1）。在第 3 天时使用Phalloidin-鬼笔环肽试剂盒染色观察细胞形态，具体操作如下：  \n\n1）去除培养液，将细胞用 PBS 清洗3 次， $4\\%$ 多聚甲醛在室温下固定 $10\\mathrm{min}$ ；  \n2）去除固定液，PBS 清洗细胞3 次；  \n3）室温下， $0.5\\%$ 的 triton X-100 对细胞进行透化处理 $5\\mathrm{min}$ ，再次用PBS 清洗细胞3 次；  \n4）吸取 $400~\\upmu\\mathrm{l}$ 配置好的 Phalloidin-鬼笔环肽工作液加入孔板中，室温避光孵育 $30\\mathrm{min}$ ，PBS 清洗 3 次；  \n5）吸取 $400~\\upmu\\mathrm{l}$ 的DAPI 溶液（浓度 $100~\\mathrm{{nM}}$ ）对细胞核复染 $2~\\mathrm{min}$ ；  \n\n6）在荧光显微镜下进行观察并拍照，Image J 分析细胞荧光强度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 86,
+        "chunk": "# 2.4.2.4 细胞划痕实验  \n\n将细胞以 $1\\times10^{4}/$ 孔的密度种植在 24 孔板中，待细胞融合到 $85\\%$ 以上后，用$200\\upmu\\mathrm{l}$ 枪头在孔板中央画一条直线，PBS 冲洗数次，去除漂浮细胞。随后给与超声介导的雷帕霉素递送处理，具体操作同章节 2.3.2.2 步骤 1）。在第 $0\\mathrm{{h}}$ 和 $24\\mathrm{~h~}$ 时使用Calcein-AM/PI 试剂盒染色，具体操作如章节 2.4.2.2。根据图像计算细胞迁移率。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 87,
+        "chunk": "# 2.4.2.5 Transwell 细胞迁移实验  \n\n将细胞以 $1\\times10^{4}/$ 孔的密度种植在 Transwell 小室中，给与超声介导的雷帕霉素递送处理，具体操作同章节 2.3.2.2 步骤 1）。在 $24\\mathrm{~h~}$ 后取出 Transwell 小室，弃培养液，无钙 PBS 清洗 2 次，甲醇固定 $30~\\mathrm{min}$ ，适当风干小室； $0.1\\%$ 结晶紫染色 $20\\mathrm{min}$ ，用棉签轻轻擦去上层未迁移细胞，显微镜下随机观察 5 个视野，计数。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 88,
+        "chunk": "# 2.4.2.6 茜素红染色  \n\n将细胞以 $1\\times10^{4}/$ 孔的密度种植在 12 孔板中，待细胞贴壁后，更换成骨诱导培养基，给与超声介导的雷帕霉素递送处理，具体操作同章节 2.3.2.2 步骤 1）。  \n\n在成骨诱导后的第 7 天和第14 天进行茜素红染色，具体步骤如下：  \n\n1）去除培养基， $4\\%$ 多聚甲醛固定 $15\\mathrm{min}$ 后去除固定液，PBS 清洗3 次；2）将 PBS 完全吸净后，加入 $2\\%$ 茜素红 S 染色液 $0.5~\\mathrm{ml}$ ，染色 $15~\\mathrm{min}$ ，去除染色液，PBS 洗涤 3 次；3）然后将染色好的细胞样品拍照，并放置在显微镜下进行观察；4）为半定量分析钙结节，孔板中加入氯化十六烷基吡啶 $\\mathrm{~1~ml}$ ，并将孔板置于摇床上摇晃过夜，充分溶解沉积的钙结节。吸取孔中上清液转移到 96 孔板中，使用酶标仪在 $570\\mathrm{nm}$ 波长处检测样品吸光度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 89,
+        "chunk": "# 2.4.2.7 RT-qPCR  \n\n将细胞以 $1\\times10^{4}/$ 孔的密度种植在 12 孔板中，待细胞贴壁后换液，使用成骨诱导培养基，给与超声介导的雷帕霉素递送处理，具体操作同章节 2.3.2.2 步骤1）。在成骨诱导 7 天和 14 天后进行 PCR 检测分析细胞中 Runx-2、ALP、OCN和OPN 的基因表达情况，具体步骤如下：  \n\n1）总 RNA 的提取：去除培养基，PBS 轻轻冲洗细胞2 遍，用胰酶消化至细胞变圆但未浮起时去除胰酶，加入 $1~\\mathrm{ml}$ PBS 吹打、重悬细胞，收集细胞转移到$1.5\\mathrm{ml}$ 无核酸酶 EP 管中，离心（ ${3000}\\mathrm{rpm}$ ，5 min）弃 PBS。根据 Promega 总 RNA提取试剂盒的说明书，加入 $300\\upmu\\mathrm{l}$ 裂解液并反复吹打细胞沉淀 5 次左右，至肉眼无可见细胞沉淀，室温裂解 $15\\mathrm{min}$ 后加入中和液 $300\\upmu\\mathrm{l}$ ，吹打3 次混匀，室温放置 $5~\\mathrm{min}$ 。为提高RNA 获得率，可于 $70^{\\circ}\\mathrm{C}$ 环境下加热 $3~\\mathrm{min}$ 后离心（ $12000~\\mathrm{g}$ ，5 min）；  \n\n2）总 RNA 浓度测量：用 NanoDrop 2000 分光光度计检验各组 RNA 样品的浓度和纯度。若 A260/A280 比值处于 1.9-2.1 之间时认为 RNA 样品为无蛋白质污染，可用于后续实验，所有 RNA 样品- $.80^{\\circ}\\mathrm{C}$ 保存待用；  \n\n3）逆转录合成 cDNA：参考Takara 逆转录试剂盒的使用说明，每个 RNA 样品以 $500~\\mathrm{ng}$ 的总质量进行逆转录，加入无核酸酶水和其它预混试剂至总体系为$20~\\upmu\\mathrm{l}$ ，加入 $0.2~\\mathrm{ml}$ 无核酸酶 EP 管，置于 PCR 热循环仪进行逆转录反应，反应条件为： $37^{\\circ}\\mathrm{C}$ ， $15\\mathrm{min}$ ； $85^{\\circ}\\mathrm{C}$ ，5 s； $4^{\\circ}\\mathrm{C}$ ，降温，获得的逆转录产物- $\\cdot20^{\\circ}\\mathrm{C}$ 保存待用；  \n\n4）RT-qPCR: 配制 qPCR 反应体系 $20\\upmu\\mathrm{l}$ ，包括 SYBR Green Mastermix $10\\upmu\\mathrm{l}$ ，  \n\n$10\\ \\mathrm{\\textmumol{/L}}$ 上下游混合物 $1~\\upmu\\mathrm{l}$ ， $\\mathrm{\\ddH}_{2}\\mathrm{O}~8~\\upmu\\mathrm{l}$ 和 $\\mathrm{cDNA}1\\upmu\\mathrm{l}{\\mathrm{~}}_{}$ 。将上述反应体系转移入PCR 专用96 孔板中，每个样品每种引物设置 3 个复孔，每个样品设置2 个空白对照孔（将cDNA 更换为 $\\mathrm{\\dd{d}H_{2}O}\\rangle$ ），封膜，离心（ $2500\\mathrm{rpm}$ ，3 min）。将 PCR板放置入罗氏LightCycler480 仪器进行实时荧光定量反应。反应条件如下：第一步， $95^{\\circ}\\mathrm{C}$ ， $10\\mathrm{min}$ （聚合酶激活）；第二步， $95^{\\circ}\\mathrm{C}$ ，15 s（DNA 变性）， $60^{\\circ}\\mathrm{C}$ ，1min（DNA 退火与延伸），循环 40 次此步骤；第三步，添加溶解曲线， $95^{\\circ}\\mathrm{C}{-}15$ s， $60^{\\circ}\\mathrm{C}{-}30~\\mathrm{s}$ ， $95^{\\circ}\\mathrm{C}{-}15\\ \\mathrm{s}$ ；第四步，冷却至 $37^{\\circ}\\mathrm{C}$ 。收集结果并在 LightCycler 480软件进行数据分析，只有当每个样品的溶解曲线显示为单峰且在峰值出现前平坦的Ct 值可纳入至后续的计算。采用 $2^{-\\Delta\\Delta\\mathrm{Ct}}$ 计算方法，各引物信息见表 2.1，以 ${\\mathfrak{\\beta}}.$ -actin 为内参。  \n\n表2.1 各基因引物信息  \n\n\n<html><body><table><tr><td>Gene subtype</td><td>Oligonucleotide Primers (5'-3\")</td></tr><tr><td>ALP</td><td>F: 5'-ATC GGA CCC TGC CTT ACC-3'</td></tr><tr><td>Runx-2</td><td>R: 5'-CTC TTG GGC TTG CTG TCG-3' F: 5'-ACTACCAGCCACCGAGACCA-3'</td></tr><tr><td>OCN</td><td>R: 5'ACTGCTTGCAGCCTTAAATGACTCT-3' F: 5'-AGCCACCGAGACACCATGAGA-3'</td></tr><tr><td>OPN</td><td>R: 5'-AGCCACCGAGACACCATGAGA-3'</td></tr><tr><td></td><td>F: 5'-GCTAAACCCTGACCCATCT-3' R: 5'-CGTCGGATTCATTGGAGT-3'</td></tr><tr><td>GAPDH</td><td>F: 5'- GTATGATTCCACCCACGGCA-3'</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 90,
+        "chunk": "# 2.4.2.8 免疫荧光染色  \n\n将细胞以 $1\\times10^{4}/$ 孔的密度种植在 12 孔板中，待细胞贴壁后，更换成骨诱导培养基，给与超声介导的雷帕霉素递送处理，具体操作同章节 2.3.2.2 步骤 1）。在成骨诱导 14 天后进行免疫荧光染色分析细胞中 Runx-2、ALP、OCN 和 OPN的蛋白表达情况，具体步骤如下：  \n\n1）细胞固定和穿孔：弃去培养基，PBS 轻轻冲洗2 遍，每孔中加入 $4\\%$ 多聚甲醛 $\\mathrm{1ml}$ 于室温下固定 $15\\mathrm{min}$ ，去除固定液后 PBS 洗3 次，每孔加入 $0.5\\%$ Triton$\\mathrm{X}{-}100\\ 1\\ \\mathrm{ml}$ ，室温透化 $15\\mathrm{min}$ ，PBS 洗 3 次；  \n\n2）封闭：样品置于湿盒中，加入封闭液封闭 $30\\mathrm{min}$ ， $37^{\\circ}\\mathrm{C}$ ；  \n\n3）一抗孵育：吸干封闭液，加入 $1\\%$ BSA 制备的一抗混合液（Runx-2 抗体1：50、ALP 抗体 1：50、OCN 抗体 1：100、OPN 抗体 1：100），置于湿盒内，$4^{\\circ}\\mathrm{C}$ 孵育过夜；  \n\n4）二抗孵育：吸去一抗，PBS 洗片 3 次，加入 Alexa Fluor $\\textsuperscript{\\textregistered}$ 488 和 Cy3 荧光二抗（ $1\\%\\mathrm{BSA}$ 按 1：600 稀释），置于湿盒内， $37^{\\circ}\\mathrm{C}$ 避光孵育 $45\\mathrm{min}$ ；  \n\n5）细胞核染色及观察：PBS 清洗3 次，避光加入 DAPI（1：600）孵育 $5\\mathrm{min}$ ，PBS 清洗3 次，利用抗淬灭封片剂封片；  \n\n6）荧光显微镜下观察并拍照，并用 Image J 定量分析荧光强度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 91,
+        "chunk": "# 2.4.2.9 油红 O 染色  \n\n将细胞以 $1{\\times}10^{4}/$ 孔的密度种植在 12 孔板中，待细胞贴壁后换液，使用成脂诱导培养基，给与超声介导的雷帕霉素递送处理，具体操作同章节 2.3.2.2 步骤1）。具体步骤如下：  \n\n1）待细胞贴壁后更换成脂诱导培养基 A 液进行培养，3 天后换用成脂诱导培养基B 液进行培养 $24\\mathrm{h}$ ，如此A、B 培养基交替使用培养至第 21 天；2） $10\\%$ 多聚甲醛固定细胞 $10\\mathrm{min}$ ，弃去固定液，PBS 洗涤，加入油红 O 染色液 $400~\\upmu\\mathrm{l}$ 孵育 $30~\\mathrm{min}$ ，移除油红 O 染液，并用 PBS 洗涤 2 次，光镜下观察；3）使用甲醇洗脱染色 $30\\mathrm{min}$ ，并使用酶标仪在 $510\\mathrm{nm}$ 处测量吸光度进行定量。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 92,
+        "chunk": "# 2.4.2.10 数据统计分析  \n\n同章节 2.1.2.3。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 93,
+        "chunk": "# 2.4.3 结果",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 94,
+        "chunk": "# 2.4.3.1 细胞增殖与活性  \n\n为了探究超声介导雷帕霉素递送对 OP-BMSCs 的调节作用，我们首先使用CCK-8 法检测不同培养环境中的细胞增殖情况。图 2.10A 所示，在培养第 4 和第 7 天时，OP 组和 OP-UI 组中的 OP-BMSCs 增殖速率显著慢于 Health 组的 H-BMSCs（ $\\mathsf{p}{\\mathrm{<}}0.01$ ），而超声介导雷帕霉素递送可以显著改善 OP-BMSCs 的增殖能力（ $\\cdot\\mathrm{p}{<}0.05)$ ）。随后，Calcein-AM/PI 染色对活死细胞的标记如图2.10B 所示，与Health 组和 OP-UIRa 组相比，OP 和 OP-UI 组中观察到更多红染的死细胞，定量分析显示在健康组、OP 组、OP-UI 组和 OPUIRa 组的细胞存活率分别为$96.04{\\pm}1.74\\%$ 、 $84.89{\\pm}3.76\\%$ 、 $85.99{\\scriptstyle\\pm2.80\\%}$ 和 $92.17{\\scriptstyle\\pm2.84\\%}$ （图 2.10C）。Phalloidin-鬼笔环肽显示与 OP 或 OP-UI 组相比，OP-UIRa 组中的 OP-BMSCs 显示出更好的铺展状态和更多的板足延伸，细胞骨架沿长轴排列并具有更强的荧光强度（图2.10D、E）。  \n\n![](images/89d39461933e21dcbd6dbf665366c2f150bb5d1021c190f3b49764652cdafa6c.jpg)  \n图 2.10（A）CCK-8 法测定细胞增殖情况；（B）Calcein-AM/PI 染色标记活死细胞；（C）细胞存活率计算；(D) Phalloidin-鬼笔环肽染色图像；(E) Phalloidin-鬼笔环肽染色荧光强度定量分析（ $^{*}p<0.05$ ; $**_{p}<0.01\\$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 95,
+        "chunk": "# 2.4.3.2 细胞迁移能力  \n\n为研究超声介导雷帕霉素递送对 OP-BMSCs 迁移能力的影响，我们采用了划痕实验与 Transwell 细胞迁移实验进行验证。如图 2.11A 细胞划痕实验所示，制造划痕 $24\\mathrm{h}$ 后，Health 组和OP-UIRa 组的细胞趋向于向划痕中间聚集，而 OP组和 OP-UI 组的细胞表现出迁移较慢，图像中仍有较为明显的划痕。此外，transwell 分析显示，Health 组和 OP-UIRa 组迁移透过孔室底部的细胞数明显高于 OP 组和 OP-UIRa 组（ $\\scriptstyle\\cdot\\mathtt{p}^{<0.05)}$ ）（图 2.11B、C）。  \n\n![](images/bf5393bf4fa4855438cabecfe4ea0b49b53ddb8b873cf7316758dbd891d80611.jpg)  \n图 2.11（A）细胞划痕实验图像；（B）Transwell 细胞迁移实验；(C) 定量分析Transwell 实验细胞迁移数量（ $^{\\cdot}\\ast_{p}<0.05)$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 96,
+        "chunk": "# 2.4.3.3 细胞成骨分化  \n\n为研究超声介导雷帕霉素递送对 OP-BMSCs 成骨分化能力的影响，我们对细胞中沉积的钙结节进行了茜素红染色，对成骨分化标志物 ALP、Runx-2、OCN和OPN 进行PCR 检测和免疫荧光分析。  \n\n首先，我们对各实验组进行茜素红染色，直观地评估骨基质的矿化水平，如图 2.12A 所示，在第 7 天时各组钙沉积均较少，但是 Health 组和 OP-UIRa 组还是优于 OP 组和 OP-UI 组，这种差异在第 14 天时更明显。通过氯化十六烷基吡啶洗脱被茜素红着色的钙结节，通过半定量分析显示进一步验证了超声介导雷帕霉素递送可以促进 OP-BMSCs 的矿化（图2.12B）。随后，我们通过 PCR 实验探究各组细胞中成骨相关基因的表达水平。如图 2.12C、D，早期成骨标志物 ALP和Runx-2在Health组和OP-UIRa组中的表达显著高于OP组和OP-UI组（ $\\cdot\\mathbf{p}{<}0.05)$ ）。此外，晚期成骨标志物 OCN 和OPN 的表达情况也具有相似趋势（图 2.12E、F）。相较于 Health 组，OP-UIRa 组只有在第 7 天时的 OCN 和第 14 天时的 OPN 表达水平有所下降（ $(\\mathtt{p}{<}0.05)$ ），其余基因和时间点均无统计学差异，表明超声介导雷帕霉素递送几乎可以使 OP-BMSCs 中成骨基因的表达水平恢复至 H-BMSCs 能力。  \n\n![](images/348cbda262329d262121cc423a563b73ba48603fdb0d2525f2bb830523cc0bd3.jpg)  \n图2.12（A）茜素红染色图像；（B）茜素红染色半定量分析；(C-F) PCR 检测成骨相关基因 ALP、Runx-2、OCN 和 OPN 的表达（ $^{*}p<0.05$ ; $**_{p}<0.01$ ; $\\ast\\ast\\ast_{p}<$ 0.001）。  \n\n为了进一步验证成骨相关标志物在细胞中的表达情况，我们对细胞中的ALP、Runx-2、OCN 和 OPN 蛋白表达情况进行免疫荧光染色（图 2.13A）。如图 2.13B所示，通过对荧光强度的定量分析可知这些成骨相关蛋白在Health 组和OP-UIRa组中的表达显著高于 OP 组和OP-UI 组。  \n\n![](images/d94cafd885b07e57b0894a73d8d2a1a209b84b371b0090dd4afd028a0cf16ba0.jpg)  \n图2.13（A）细胞中成骨相关蛋白 ALP、Runx-2、OCN 和OPN 的免疫荧光染色；（B）定量分析免疫荧光染色图像的荧光强度（ ${}^{:*}p<0.05$ ; $^{**}p<0.01$ ; $^{***}p<0.001.$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 97,
+        "chunk": "# 2.4.3.4 细胞成脂分化  \n\n油红 O 染色被用于观察细胞成脂分化的趋势（图 2.14A）。如图 2.14B 定量分析所示，OP 和 OP-UI 组的脂滴数量增加，显著高于 Health 组和 OP-UIRa 组（ $_{\\cdot\\mathrm{{p}<0.001}}$ ），表明超声介导的雷帕霉素递送较大程度地抑制 OP-BMSCs 成脂分化，虽然不能完全达到与 H-BMSCs 相同的程度。  \n\n![](images/1e543dd90da40b264eb6cefd7bdca47d7a3e33fabf475722a63535605098755d.jpg)  \n图2.14 （A）油红 O 染色图像；（B）油红O 染色定量分析（ $^{*}p<0.05$ ; $^{**}p<0.01$ ;\\* $^{**}p<0.001\\rangle$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 98,
+        "chunk": "# 2.4.4 讨论  \n\n在骨质疏松症和年龄相关的骨丢失中，骨髓中 BMSCs 不仅数量减少，而且其增殖、活性和迁移能力也受到抑制，而成脂分化潜能增加。细胞活力的降低延缓了骨损伤部位干细胞的募集和成骨分化，从而导致骨修复受损 [209]。这些现象被证明与 OP-BMSCs 的低下的自噬水平有关 [210, 211]。在 2.3 章节中我们成功地使用超声介导雷帕霉素递送激活了 OP-BMSCs 的自噬活性，在这里，我们主要观察OP-BMSCs 的自噬被激活后各种细胞功能的恢复情况。  \n\n首先，随着培养时间的延长，各组中的细胞数量显著增加。然而，与 H-BMSCs相比，OP 组和 OP-UI 组中的 OP-BMSCs 的增殖受到抑制（ $\\cdot\\mathtt{p}^{<0.01)}$ ），但这种抑制可以通过雷帕霉素递送来实现部分逆转，该观察结果与先前的研究一致 [212]。活细胞被 Calcein-AM 的绿色荧光标记，PI 则可以特异性透过死细胞的细胞膜，并嵌入 DNA 双螺旋结构使死细胞被红色荧光标记 [213]。Calcein-AM/PI 对细胞进行活死染色也证明通过雷帕霉素递送可以恢复 OP-BMSCs 的存活率。F-肌动蛋白丝在BMSCs 的早期成熟中具有重要作用，通过靶向增殖和分化来调节细胞功能 [214]。本章节中中，细胞 F-肌动蛋白用 phaloidin-鬼笔环肽染色以检测细胞骨架。超声介导的雷帕霉素递送处理的 OP-BMSCs 显示出更好的铺展性和更多的板足延伸。F-肌动蛋白丝和细胞骨架的荧光强度增强有利于 BMSCs 的细胞活性和早期成骨分化 [215]。因此，超声介导的雷帕霉素递送可能具有显著增强 OP-BMSCs 的F-肌动蛋白和细胞骨架重组的作用，从而潜在地改善 OP-BMSCs 的迁移和成骨分化。随后，细胞划痕实验和 transwell 检测证实超声介导的雷帕霉素递送可显著改善OP-BMSCs 的迁移能力。  \n\n除了增殖和迁移外，BMSCs 的成骨分化是骨再生的关键过程。由于过度的骨吸收和有限的骨形成能力，骨质疏松症导致骨量下降并限制损伤后的骨再生。BMSCs 被认为是损伤后参与骨修复的成骨细胞的主要来源。然而，骨质疏松微环境中的BMSCs 数量不足，部分丧失了自我更新和分化能力。先前的研究显示骨质疏松症中的骨丢失不仅是由于成骨活性降低和破骨细胞活化增加的失衡，而且与骨髓腔中的高脂肪有关 [216]。由于雌激素缺乏的环境，OP-BMSCs 具有潜在分化为脂肪细胞而不是成骨细胞的趋势，会导致骨丢失和脂肪积聚 [217, 218]。因此，调节OP-BMSCs 成骨-成脂分化的平衡是促进骨质疏松症患者假体界面骨再生和骨整合的潜在策略。在本章节，我们通过茜素红染色、RT-qPCR、免疫荧光和油红O 染色等一列研究证明超声介导的雷帕霉素递送可以调节OP-BMSCs 成骨-成脂分化平衡，即诱导 OP-BMSCs 成骨分化而抑制成脂分化。  \n\n绝经后骨质疏松症中 BMSCs 的退行性改变与骨破坏有关，这些退行性变化包括细胞增殖能力受损、分化不平衡和衰老加剧 [219, 220]。我们的结果表明，与 H-BMSCs 相比，OP-BMSCs 的增殖、存活、迁移和成骨分化能力降低，而成脂肪分化能力提高，这些结果与之前的研究结果一致 [45, 196]。将OP 组和OP-UI 组相比可见，单独对 OP-BMSCs 进行超声处理（不负载雷帕霉素）并不影响细胞功能，而超声介导的雷帕霉素递送有效地改善了 OP-BMSCs 的细胞增殖、活力、迁移和成骨-成脂分化平衡。因此，我们推测超声介导的雷帕霉素递送可以有效逆转 OP-BMSCs 的退行性状态，这为骨质疏松症患者假体植入后增强界面骨整合的提供了替代策略。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 99,
+        "chunk": "# 2.4.5 小结  \n\n相较于 H-BMSCs，OP-BMSCs 的增殖、存活、迁移和成骨分化能力降低，而成脂肪分化能力提高。OP-BMSCs 这些受损的细胞功能可以通过雷帕霉素递送来激活 OP-BMSCs 的自噬活性而完全或者部分恢复，从而为增强骨质疏松症患60  \n\n者假体植入后界面骨整合提供了替代策略。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 100,
+        "chunk": "# 2.5 超声介导雷帕霉素递送促进骨质疏松状态下假体界面骨整合",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 101,
+        "chunk": "# 2.5.1 实验仪器与材料  \n\n2.5.1.1 实验仪器   \n\n\n<html><body><table><tr><td>仪器名称</td><td>厂家</td></tr><tr><td>超声电导仪</td><td>北京诺亚同舟医疗技术有限公司</td></tr><tr><td>外科手术器械</td><td>杭州青牛医疗器械有限公司</td></tr><tr><td>Micro-CT</td><td>比利时 Bruker 公司</td></tr><tr><td>硬组织切片机</td><td>德国Leica公司</td></tr><tr><td>冰冻切片机</td><td>德国Leica公司</td></tr><tr><td>万能力学测试机</td><td>日本Shimadzu公司</td></tr></table></body></html>\n\n其他仪器同 2.2.1.1。  \n\n2.5.1.2 主要试剂  \n\n\n<html><body><table><tr><td>试剂名称</td><td>厂家</td></tr><tr><td>雷帕霉素</td><td>美国Sigma-Aldrich 公司</td></tr><tr><td>碘伏毒液</td><td>山东利尔康医疗科技有限公司</td></tr><tr><td>兽用青霉素</td><td>华北制药集团有限责任公司</td></tr><tr><td>戊巴比妥钠</td><td>北京索莱宝科技有限公司</td></tr><tr><td>苏木精和伊红（H&E）染料</td><td>美国 Thermo 公司</td></tr><tr><td>Van Gieson 染料</td><td>美国 Thermo 公司</td></tr><tr><td>钙黄绿素</td><td>上海源叶生物科技有限公司</td></tr><tr><td>多聚甲醛</td><td>上海Aladdin生化科技有限公司</td></tr><tr><td>小鼠抗Runx-2抗体</td><td>美国Abcam公司</td></tr><tr><td>兔抗 ALP抗体</td><td>美国Abcamy公司</td></tr><tr><td>小鼠抗OCN抗体</td><td>美国Abcam公司</td></tr><tr><td>兔抗OPN抗体</td><td>美国Abcam公司</td></tr></table></body></html>  \n\n续表：  \n\n\n<html><body><table><tr><td>山羊抗兔Cy3荧光二抗</td><td>北京博奥森生物技术有限公司</td></tr><tr><td>山羊抗小鼠AlexaFluor?488 荧光二抗</td><td>美国Thermo 公司</td></tr><tr><td>DAPI</td><td>北京索莱宝生物科技有限公司</td></tr><tr><td>含DAPI抗淬灭封片剂</td><td>美国Vector公司</td></tr></table></body></html>\n\n其他试剂同 2.3.1.2 及 2.4.1.2。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 102,
+        "chunk": "# 2.5.1.3 实验动物  \n\n新西兰大耳白兔：由吉林大学基础医学院实验动物中心提供。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 103,
+        "chunk": "# 2.5.2 实验方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 104,
+        "chunk": "# 2.5.2.1 骨质疏松兔股骨远端假体植入和组织获取  \n\n通过双侧卵巢切除术法制备骨质疏松兔模型，详细造模过程见章节 2.2.2.1。卵巢切除术后 10 个月骨质疏松模型建立，植入 3D 打印微孔假体至兔左侧股骨远端外侧髁。假体植入手术具体操作步骤为：术前 12h 禁食水， $3\\%$ 戊巴比妥钠（ $\\mathrm{\\50mg/kg}^{\\mathrm{'}}$ ）耳缘静脉注射，麻醉后，右侧卧位，暴露左侧膝关节。术区常规备皮、消毒、铺单。沿髌骨沟外侧入路切开皮肤，逐层分离软组织，暴露股骨远端外侧髁。使用定制的手钻于股骨外上髁处制备深度为 $10\\mathrm{mm}$ ，直径为 $5\\mathrm{mm}$ 的圆柱形骨缺损，然后植入与之匹配的 3D 打印微孔支架，随后逐层缝合软组织、闭合皮肤。术后兔子在笼内自由运动，连续 3 天肌肉注射青霉素（ $1.5\\mathrm{mg/kg}\\cdot$ ）以防止感染，伤口碘伏消毒至愈合。  \n\n动物实验共分为 4 个组，每组12 只。10 个月前未进行卵巢切除的假手术组中的非骨质疏松兔子作为健康对照组（Health 组），并在假体植入后不接收额外治疗处理。骨质疏松兔子假体界面植入后，左侧股骨远端外侧髁分别接受无额外治疗、不含雷帕霉素的单独超声治疗和超声介导的雷帕霉素递送，分别简称为 OP组、OP-UI 组和 OP-UIRa 组。OP-UIRa 组即为将 $200\\upmu\\mathrm{l}$ 雷帕霉素溶液（ $\\mathrm{{(1000nM)}}$ ）加入明胶海绵中，然后将明胶海绵紧密贴合在超声发射器和左股骨远端外侧髁的皮肤之间，用于药物递送。OP-UI 组的明胶海绵中为生理盐水浸湿，不含雷帕霉素。在假体植入后 1 周开始超声治疗，每周 2 次。设置超声电导仪的频率为 30$\\mathrm{kHz}$ ，强度为 $45\\mathrm{W/cm}^{2}$ ，时间为 $10\\mathrm{min}$ 。  \n\n所有动物在处死前第 14 天和第4 天肌肉注射钙黄绿素（ $({8\\mathrm{mg/kg}})$ ），以检测骨形成过程中的矿物质沉积率（Mineral apposition rate，MAR），矿化表面/骨表面（Mineralizing surface per bone surface, MS/BS ）和 骨形 成率 / 骨表 面（ Boneformation rate per bone surface, BFR/BS）。术后第 12 周，过量麻醉法处死实验动物，收集左侧股骨样本，并将其固定在 $4\\%$ 多聚甲醛中或储存在- $.80^{\\circ}\\mathrm{C}$ 下进行进一步研究。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 105,
+        "chunk": "# 2.5.2.2 H&E 染色  \n\n收集左侧股骨远端皮肤和内脏，进行 H&E 染色以评估超声介导雷帕霉素递送的安全性。具体步骤如下：  \n\n1）取材：使用 $4\\%$ 多聚甲醛将收集的新鲜组织固定 $48\\mathrm{h}$ ，随后使用手术刀在通风橱内将组织修理平整，将修切好的组织进行标记并置于脱水盒内；  \n\n2）脱水：将脱水盒置于吊篮中，在脱水机内依次使用不同浓度的酒精进行梯度脱水，即 $75\\%$ 酒精脱水 $4h{-}85\\%$ 酒精脱水 $2h{-}90\\%$ 酒精脱水 $2h{-}95\\%$ 酒精脱水 $\\mathsf{1h}.$ -无水乙醇I 脱水 $30\\mathrm{min}.$ -无水乙醇II 脱水 $30\\mathrm{min}.$ -醇苯 $5{\\mathrm{-}}10\\operatorname*{min}.$ -二甲苯 I 5-10 min-二甲苯 $\\mathrm{II}5{-}10\\mathrm{min}.$ -蜡 $\\mathrm{~I~}1\\mathrm{~h~}$ -蜡 $\\mathrm{~II~}1\\mathrm{~h}.$ -蜡 III $^{\\textrm{1h}}$ ；  \n\n3）包埋：将浸好蜡的组织块置于包埋机中进行包埋，先将充分融化的蜡放入包埋框中，在蜡凝固前将组织从脱水盒中取出，并按照包埋面的要求放入包埋框中并进行标记，随后在- $-20^{\\circ}$ 的冻台中进行冷却，蜡凝固后将蜡块从包埋框中取出并修整蜡块至理想界面；  \n\n4）切片：将修整好的蜡块固定在石蜡切片机上进行组织切片，片厚约 ${5\\upmu\\mathrm{m}}$ ，将切片漂浮于摊片机 $40^{\\circ}\\mathrm{C}$ 温水中使组织片展平，随后用载玻片轻柔的将组织捞起，置于 $60^{\\circ}\\mathrm{C}$ 烘箱内烤片，至烤干水烤化蜡后取出切片，常温保存备用；  \n\n5）石蜡切片脱蜡至水：将切片依次放入二甲苯Ⅰ $20\\mathrm{min}.$ 二甲苯Ⅱ $20\\mathrm{min\\mathrm{.}}$ 无水乙醇Ⅰ $10\\mathrm{min}.$ -无水乙醇Ⅱ $10\\mathrm{min}{\\cdot}95\\%$ 酒精 $5\\mathrm{min}{\\cdot}90\\%$ 酒精 $5\\mathrm{min}{-}80\\%$ 酒精$5\\mathrm{min}{-}70\\%$ 酒精 $5\\mathrm{min}$ -蒸馏水洗；  \n\n6）苏木素染细胞核：使用Harris 苏木素将切片染 $3{-}8\\operatorname*{min}$ ，自来水冲洗， $1\\%$ 盐酸酒精分化数秒，自来水冲洗， $0.6\\%$ 氨水返蓝，用流水进行冲洗；  \n\n7）伊红染细胞质：使用伊红染液将切片染色 $1{-}3~\\mathrm{min}$ ；  \n\n8）脱水封片：依次将切片放入 $95\\%$ 酒精 $15\\mathrm{min}{\\cdot}95\\%$ 酒精 II 5 min-无水乙醇  \n\nⅠ 5 min -无水乙醇Ⅱ 5 min -二甲苯Ⅰ 5 min -二甲苯Ⅱ 5 min 中脱水透明，将切片从二甲苯中拿出来稍晾干，用中性树胶进行封片；  \n\n9）使用显微镜观察，并进行图像采集分析。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 106,
+        "chunk": "# 2.5.2.3 Micro-CT 评估骨长入  \n\n使用Micro-CT 对收集的股骨远端组织进行扫描，工作参数设置为电压： $90\\mathrm{V}$ ，电流： $114~\\upmu\\mathrm{A}$ ，扫描分辨率： $18~{\\upmu\\mathrm{m}}$ ，并选用 $\\mathrm{\\Al/Cu}$ 滤片以避免金属伪影。具体观察指标如下：  \n\n1）获取 X 线正位片以观察假体有无松动、移位的情况；  \n2）假体界面骨长入情况分析：使用 NRecon 软件选取支架所在区域为感兴趣区域进行三维重建，并定量分析骨体积百分比（BV/TV）、骨小梁厚度（Tb. Th）、骨小梁数目（Tb. N）和骨小梁分离度（Tb. Sp）；  \n3）假体周围骨质情况分析：选取股骨远端 2 cm 区域（包含假体）为感兴趣区域，分析界面周围骨形态学参数，包括骨体积百分比（BV/TV）、骨小梁厚度（Tb. Th）、骨小梁数目（Tb. N）和骨小梁分离度（Tb. Sp）；另外选取假体近端及近处1 cm 区域为感兴趣区域分析皮质骨厚度（Ct.Th）和皮质骨面积（Ct.Ar）。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 107,
+        "chunk": "# 2.5.2.4 硬组织切片评估骨整合效果  \n\n收集股骨远端样本，制备未脱钙硬组织切片，Van-Gieson 染色观察再生骨组织与假体微孔界面整合情况，具体步骤如下：  \n\n（1）股骨远端样本放入 $10\\%$ 甲醛溶液中浸泡 $48\\mathrm{h}$ ， $70\\%$ 酒精处理 $2\\mathrm{h}$ ， $95\\%$ 酒精处理 $20\\mathrm{h}$ ， $100\\%$ 酒精处理 $2\\mathrm{h}$ ，随后在减压下干燥 $6\\mathrm{{h}}$ ;（2）通过上述操作凝固蛋白、防腐、脱水、干燥等处理后，将组织置于装有聚甲基丙烯酸甲酯单体的玻璃管中，在低真空下浸渗 $30~\\mathrm{min}$ 至无气泡冒出，随后在 $27^{\\circ}\\mathrm{C}$ 水浴中固化。为避免聚甲基丙烯酸甲酯单体在固化时发生炸裂，应特别注意固化时保持温度均匀;（3）使用硬组织切片机制备约 $200\\upmu\\mathrm{m}$ 的组织切片，用速干胶将切片粘于树脂片上，用磨片机将树脂片上的组织切片磨至约 $50~{\\upmu\\mathrm{m}}$ 厚，抛光；（4）将切片依次放入浓度为 $10\\%$ 、 $80\\%$ 、 $95\\%$ 的酒精内脱水各 $1\\mathrm{min}$ ，取出后用蒸馏水洗涤；  \n\n（5）有机溶剂脱去有机树脂，Weigert 氏苏木素染液染 $20\\mathrm{min}$ ，并流水冲洗$10\\mathrm{min}$ ，使用 Van-Gieson 染液染色 $5\\mathrm{min}$ ；  \n\n（6）依次用浓度 $80\\%$ 、 $90\\%$ 的酒精脱水后，用自来水冲洗 $30\\mathrm{min}$ ；  \n\n（7）放入二甲苯中两次，其浓度为 $10\\%$ ，透明后置于载玻片上用加拿大胶封固。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 108,
+        "chunk": "# 2.5.2.5 力学测试评估界面骨整合与周围骨质情况  \n\n1）支架推出实验评估假体-骨界面的整合强度。具体步骤如下：股骨远端内侧进行打磨，从内侧髁暴露支架内部圆面，用牙托粉将股骨内侧髁固定于操作台上，使支架纵轴与台面方向垂直；万能力学试验机上端固定直径为 $6\\mathrm{mm}$ 的硬质挤压点，并与固定支架上端纵向对齐；以 $0.1~\\mathrm{mm/s}$ 速度对股骨远端外侧髁的支架圆面进行挤压推出，每 0.5s 记录挤压点处受力情况，直至支架完全脱出，记录全称挤压点受力最大值。  \n\n2）三点弯曲实验评估周围骨质强度。具体步骤如下：将股骨远端样本放在跨距为 $30~\\mathrm{mm}$ 的马鞍形支具上，其中金属假体植入部位位于正中间位置；使用万能力学试验机对马鞍形支具的中间位置骨干处施加压力，压力加载速度为 2$\\mathrm{{mm/min}}$ ，试验以股骨样本断裂为结束点。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 109,
+        "chunk": "# 2.5.2.6 界面周围骨质中 mTOR、LC3Ⅱ/Ⅰ和 P62 的蛋白水平检测  \n\n在力学测试推出支架后，收集假体界面周围骨质，通过 Western Blot 检测骨质中 mTOR、LC3Ⅱ/Ⅰ和 P62 的蛋白表达水平，以评估假体界面周围的自噬情况。具体步骤如下：  \n\n1）骨组织总蛋白提取：将收集的骨组织置于研钵中加入 1 ml PBS，在液氮上研磨匀浆至肉眼无可见固体组织，收集液体，离心（ $2000~\\mathrm{rpm}$ ，5min），去上清。称取 $100\\mathrm{mg}$ 粉碎的骨组织，放置到离心管柱中，加入 $80\\mathrm{mg}$ 蛋白研磨粉覆盖组织样品，加入 ${100}\\mathrm{ul}$ 含蛋白酶抑制剂的蛋白裂解液。立刻用塑料研磨棒按住组织扭转研磨 $3\\mathrm{min}$ ，将剩余的 ${100}\\mathrm{ul}$ 裂解液加入，继续研磨 $1\\mathrm{min}$ 。离心（12000rpm，1min），取上清即为总蛋白，并将其转移到一个新管。管底的白色沉淀是穿过柱子的蛋白研磨粉，弃掉即可。取 $160\\upmu\\mathrm{l}$ 上清液中加入 $40\\upmu\\updownarrow5\\times$ 蛋白上样缓冲液， $100^{\\circ}\\mathrm{C}$ 水浴加热 $5\\mathrm{min}$ ，置于冰上冷却，保存于- $-20^{\\circ}\\mathrm{C}$ 备用 ；  \n\n2）随后BCA法测定总蛋白浓度和Western Blot检测的操作步骤同章节2.3.2.2中的3）和 4）。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 110,
+        "chunk": "# 2.5.2.7 界面周围骨质中成骨相关基因检测  \n\n在力学测试推出支架后，收集假体界面周围骨质，通过 RT-qPCR 法检测骨质中成骨相关基因 ALP、Runx-2、OCN 和 OPN 的表达水平。具体步骤如下：  \n\n1）骨组织总RNA 提取：将收集的骨组织至于研钵中加入 $1\\mathrm{ml}\\mathrm{PBS}$ ，在液氮上研磨匀浆至肉眼无可见固体组织，收集液体，离心（ $2000~\\mathrm{rpm}$ ，5min），去上清。根据Promega 总RNA 提取试剂盒的说明书，具体步骤同章节2.4.2.7。  \n\n2）其与步骤同章节 2.4.2.7。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 111,
+        "chunk": "# 2.5.2.8 界面周围骨质中成骨相关蛋白免疫荧光染色  \n\n在力学测试推出支架后，收集股骨远端样本，通过疫荧光染色检测骨质中成骨相关蛋白ALP、Runx-2、OCN 和OPN 的表达水平。具体步骤如下：  \n\n1）股骨远端样本放入 $10\\%$ 多聚甲醛溶液中浸泡 $48\\mathrm{h}$ ，PBS 清洗 3 次，每次$20\\mathrm{min}$ ，用蒸馏水洗清洗 3 次，每次 $20\\mathrm{min}$ ；  \n\n2）骨组织样本组织转移至 20-30 倍体积的 $10\\%$ EDTA 脱钙液中，每周换液1 次直至终点，脱钙总时间约为 2 个月，待脱钙完成后，用蒸馏水冲洗数次；  \n\n3）常规脱水、包埋、切片和石蜡切片脱蜡至水同章节 2.5.2.2 中步骤 2）、3）、4）和5）；  \n\n4）抗原修复：将组织切片放入装满 EDTA 抗原修复缓冲液（ $\\mathfrak{p H}9.0\\dot{!}$ ）的修复盒中，置于微波炉内行抗原修复。中火至沸后断电间隔 $10~\\mathrm{min}$ 中低火至沸，操作过程中避免缓冲液过度蒸发造成干片。自然冷却后将组织切片放入 PBS（pH7.4）中，在脱色摇床上晃动洗涤 3 次，每次 $5\\mathrm{min}$ ；  \n\n5）穿孔及封闭：取切片室温晾干，PBS 洗片3 次， $0.5\\%$ Triton X-100 室温通透 $15\\mathrm{min}$ ，PBS 洗片3 次，加入封闭液于 $37^{\\circ}\\mathrm{C}$ 封闭 $30\\mathrm{min}$ ；  \n\n6）加一抗：吸干封闭液，加入 $1\\%\\mathrm{BSA}$ 稀释的一抗（小鼠抗 Runx-2 抗体1：50 稀释和兔抗 ALP 抗体 1:100 稀释，小鼠抗 OCN 抗体 1：50 稀释和兔抗 OPN抗体1：100 稀释），置于湿盒内， $4^{\\circ}\\mathrm{C}$ 下孵育过夜，操作过程中在湿盒内加入少量水，避免抗体蒸发；  \n\n7）加二抗：切片置于 PBS 中在脱色摇床上晃动洗涤 3 次，每次 $5~\\mathrm{min}$ ，将切片稍甩干，随后在圈内滴加山羊抗兔 Cy3 荧光二抗或山羊抗小鼠Alexa Fluor $\\textsuperscript{\\textregistered}$ 488 荧光二抗（利用 $1\\%\\mathrm{BSA}$ 按1：600 稀释），置于湿盒内， $37^{\\circ}\\mathrm{C}$ 避光孵育 $1\\mathrm{h}$ ；  \n\n8）DAPI 染色复染细胞核：玻片置于PBS（ $\\mathsf{p H}7.4\\AA\\AA\\AA$ ）中在脱色摇床上晃动洗涤 3 次，每次 $5~\\mathrm{min}$ ，将切片稍甩干，随后在圈内滴加 DAPI 染液，避光室温孵育 $10\\mathrm{min}$ ；  \n\n9）封片：将切片放入 PBS（ $\\mathrm{pH}7.4\\AA\\AA$ ）中，在脱色摇床上晃动洗涤 3 次，每次$5\\mathrm{min}$ ，将切片稍甩干，随后用抗荧光淬灭封片剂进行封片；  \n\n10）镜下观察拍照：切片置于荧光显微镜下观察，并拍摄图像、分析。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 112,
+        "chunk": "# 2.5.2.9 数据统计分析  \n\n同章节 2.1.2.3。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 113,
+        "chunk": "# 2.5.3 结果",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 114,
+        "chunk": "# 2.5.3.1 超声介导雷帕霉素递送体内安全性分析  \n\n为了探究超声介导雷帕霉素递送对局部皮肤以及内脏的安全性，我们收集探头接触的左膝外侧髁皮肤及主要脏器进行 H&E 染色。与植入支架后不接受额外治疗的 OP 组相比，每周 2 次接受超声介导的雷帕霉素递送的 OP-UIRa 组中的皮肤组织形态未见明显改变（图 2.15A），表明体内研究使用的超声电导仪参数（即频率： $30\\mathrm{kHz}$ ，强度： $45\\mathrm{W}/\\mathrm{cm}^{2}$ ，时间： $10\\mathrm{min}$ ）对接触皮肤无损害，可以作为常规导药功率使用。随后，为了探究递送进入体内的雷帕霉素是否对脏器产生影响，我们收集了主要脏器，包括心、肝、脾、肺和肾进行 H&E 染色。如图2.15B 显示，结果显示OP-UIRa 组主要脏器的组织形态学结构与 OP 组相比无显著差异，均保持正常的形态。  \n\n![](images/47046900d9b8c368156727e09524e25204e4c067899cf277f4ddf6aedcc9b36a.jpg)  \n图 2.15（A）左膝外侧髁皮肤 H&E 染色；（B）主要脏器，包括心、肝、脾、肺  \n\n和肾H&E 染色。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 115,
+        "chunk": "# 2.5.3.2 影像学评估假体界面骨整合效果  \n\n左侧股骨远端正位 X 线片显示，3D 打印钛合金微孔假体与股骨长轴垂直，未发生明显松动、移位（图 2.16A）。随后，通过 Micro-CT 检测假体界面的表面和微孔内部的骨形成。如图 2.16B 典型的3D 重建图像显示与OP 和 OP-UI 组相比，OP-UIRa 组中具有更多的骨组织（黄色）在假体表面和孔隙中，甚至达到了与 Health 组相似的骨量。进一步的定量分析表明，Health、OP、OP-UI 和 OP-UIRa 组的 BV/TV 值分别为 $20.5{\\pm}2.7\\%$ ， $12.4{\\pm}2.5\\%$ ， $13.2{\\pm}2.0\\%$ 和 $17.6{\\pm}2.4\\%$ 。与OP 组和 OP-UI 组相比，OP-UIRa 组在植入后 12 周时表现出明显增加的骨体积分数（BV/TV， $\\mathsf{p}{<}0.05)$ ）、骨小梁厚度（Tb.Th， $\\mathsf{p}{<}0.05$ ）和骨小梁数量（Tb.N，$\\mathsf{p}{<}0.01$ ），并减少了界面新骨的骨小梁分离度（Tb.Sp， $\\mathsf{p}{<}0.05$ ）（图 2.16 C-F）。此外，这些结果显示 OP-UIRa 组和 Health 组之间的骨形态计量学参数并无显著差异，表明通过经皮超声介导的雷帕霉素递送可以有效促进骨质疏松状态下的微孔假体表面的骨形成与长入，甚至可达到健康状态下的再生骨量水平。  \n\n![](images/24607f7a1f45f5c934489fa58adadefd06a2ba2ac70a9cb235761a564ea3ed61.jpg)  \n图 2.16（A）左股骨远端 X 线正位片；（B）Micro-CT 3D 重建图像白色为支架，黄色为骨组织；（C-F）Micro-CT 结果定量分析 BV/TV，Tb.Th，Tb.N 和 Tb.Sp 参数（ $^{*}p<0.05$ ; $^{**}p<0.01$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 116,
+        "chunk": "# 2.5.3.3 组织学评估假体界面骨形成与整合效果  \n\n为了观察周围骨组织与假体界面的骨形成与整合效率，我们制备了不脱钙的硬组织切片，并在荧光显微镜下直接观察钙黄绿素双标染色（图2.17A）。动态组织形态计量分析结果表明，与 OP 和OP-UI 组相比，OP-UIRa 组加速了骨缺损区域的新骨形成，如 MAR，MS/BS，BFR/BS 显著增加；但是，相较于Health 组，OP-UIRa 组 MAR 和 BFR/BS 值仍具有差异（ $\\scriptstyle\\cdot\\mathtt{p}<0.05\\ \\lambda$ ）（图 2.17B-D）。随后将硬组织切片进行 Van Gieson 染色观察骨整合情况。如图 2.17E 所示，OP 组和 OP-UI 组的再生骨量有限，再生骨和假体界面之间存在明显的间隙；而在 OP-UIRa和Health 组中，可见再生骨组织与假体表面微孔结构形成明显的结合，并长入内部孔隙中；而相较于 OP-UIRa 组，Health 组中再生的骨组织更能长入到深达微孔支架的中心位置。这些结果表明，经皮超声介导的雷帕霉素递送可以显著促进3D 打印微孔界面在骨质疏松状态下的骨形成和骨整合，从而减少假体植入后松动和移位等术后并发症的发生。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 117,
+        "chunk": "# 2.5.3.4 力学评估假体界面骨整合效果  \n\n为了进一步验证假体界面和宿主骨之间的骨整合强度，我们进行了生物力学测试来记录支架推出时的峰值力。Health 组、OP 组、OP-UI 组和 OP-UIRa 组的支架推出力峰值分别为 $558.5{\\pm}52.2\\mathrm{N}$ ， $227.5{\\pm}31.4\\mathrm{N}$ ， $277.0{\\scriptstyle\\pm53.0\\mathrm{N}}$ 和 $490.2{\\pm}31.4\\$ N（图2.17F）。力学测试结果与影像学和组织学评估结果基本一致，即新骨生成量和骨小梁长入深度与假体界面骨整合强度成正比。  \n\n![](images/a41b02f5b30a92f1fd1059ce9863586851e9bfab993292f915f1b8c817ff6a41.jpg)  \n图2.17（A）不脱钙的硬组织切片观察钙黄绿素荧光双标；（B-D）通过钙黄绿素荧光双标对 MAR、MS/BS 和 BFR/BS 进行定量统计；（E）Van Gieson 染色观察假体界面骨长入与整合（黑色区域表示微孔假体，红色区域表示骨组织）；（F）植入12 周后通过生物力学支架推出测试评估骨整合强度（ $^{*}p<0.05$ ; $^{**}p<0.01$ ;  \n\n\\*\\* $^{*}p<0.001)$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 118,
+        "chunk": "# 2.5.3.5 假体界面周围骨量与骨质情况分析  \n\n通过 Micro-CT 和生物力学测试检测假体界面周围的骨量与骨质情况，以评估关节置换术后假体周围骨折的发生率。股骨远端代表性横断面图表明，与 OP和 OP-UI 组相比，Health 组和 OP-UIRa 组的假体远端具有更致密的小梁骨结构和假体近端具有更厚的皮质骨厚度（图 2.18A）。如图 2.18B 所示，选取股骨远端$2\\mathrm{cm}$ 区域（包含假体）为感兴趣区域，分析界面周围骨形态学参数表明，Health、OP、OP-UI 和 OP-UIRa 组的 BV/TV 值分别为 $36.81{\\scriptstyle\\pm4.92\\%}$ 、 $22.73{\\scriptstyle\\pm3.69\\%}$ 、$21.85{\\scriptstyle\\pm2.02\\%}$ 和 $28.83{\\scriptstyle\\pm4.42\\%}$ 。此外，骨小梁分析结果与 BV/TV 一致，即相比于OP 和 OP-UI 组，Health 组和 OP-UIRa 组中，假体界面周围松质骨的 Tb.Th 和Tb.N 显著增加，Tb.Sp 显著降低。另外选取假体近端水平及近处 1 cm 区域为感兴趣区域分析皮质骨厚度（Ct.Th）和皮质骨面积（Ct.Ar）。如图2.18C 所示，OP-UIRa 组的 Ct.Th 和 Ct.Ar 参数明显优于 OP 和 OP-UI 组（ $\\scriptstyle(\\mathtt{p}<0.05)$ ），与 Health 组并无显著差异。  \n\n随后，三点弯曲实验被用于进一步验证假体周围骨质的抗折强度（图2.18D）。在OP-UIRa 的远端股骨中观察到明显更大的最大失效载荷，其约为 OP 组和OP-UI 组的1.29 倍和1.28 倍。这些结果提供了坚实的证据证明超声介导的雷帕霉素递送可显著改善假体界面周围骨量和骨质，并有望减少在骨质疏松模型中假体植入后假体周围骨折的发生率。  \n\n![](images/7d6a594f72a5a24233c6ca0388079d2b23c7a8091db13a76a3677a556a68c894.jpg)  \n图2.18（A）Micro-CT 观察假体界面远端和近端的骨量和骨质情况；（B）股骨远端 $2\\ \\mathrm{cm}$ 区域（包含假体）的骨形态学参数分析，包括 BV/TV、Tb.Th、Tb.N 和Tb.Sp；（C）假体近端水平及近处1 cm 区域皮质骨参数分析，包括Ct.Th 和Ct.Ar；（D）生物力学三点弯曲实验分析该节段骨的抗折强度（ $^{*}p<0.05$ ; $**_{p}<0.01\\dot{,}$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 119,
+        "chunk": "# 2.5.3.6 超声介导雷帕霉素递送激活假体界面周围自噬  \n\n为了研究超声介导的雷帕霉素递送增强骨质疏松状态下骨整合的体内机制，我们收集了假体界面表面和孔隙中的骨组织，通过 Western Blot 检测自噬通路关键蛋白以评估局部骨组织中的自噬水平（图 2.19A）。结果表明，超声介导的雷帕霉素递送显著抑制假体周围 mTOR 表达，激活 LC3 II/I，并清除累积的 P62 蛋白，从而上调骨质疏松状态下假体界面周围的自噬活性（图 2.19B）。  \n\n![](images/0cfd3eac70101e6afd4c3a2739b7ea5cbcc4af74cd048d31b121d3eac50087b0.jpg)  \n图 2.19（A）Western Blot 显影条带及相应分子量， $\\upbeta$ -actin 为内参分子；（B）各组蛋白条带灰度值统计结果（ $^{*}p<0.05$ ; $**_{p}<0.01\\dot{.}$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 120,
+        "chunk": "# 2.5.3.7 超声介导雷帕霉素递送促进假体界面周围成骨标志物表达  \n\n将假体界面表面、孔隙中以及假体周围的骨组织进行检测以分析局部微环境中的成骨情况。如图 2.20A 所示，RT-qPCR 分析显示与 OP 组和 OP-UI 组相比，OP-UIRa 组成骨相关基因 Runx-2、ALP、OCN 和 OPN 的表达水平显著提高；此外，OP-UIRa 组的 Runx-2 和 OCN 水平低于 Health 组（ $(\\mathfrak{p}{<}0.05)$ ），但 ALP 和 OPN表达与 Health 组相似。  \n\n随后，在假体界面被推出后，对骨组织脱钙并进行免疫荧光染色以评估周围骨组织中成骨相关蛋白的表达（图 2.20B）。定量分析荧光强度显示，相较于 OP组和 OP-UI 组，超声介导雷帕霉素递送显著增加了 Runx-2、ALP、OCN 和 OPN在假体界面周围的表达；此外，OP-UIRa 组的 ALP 和 Runx-2 表达低于 Health 组（ $\\cdot\\mathrm{p}{<}0.05)$ ），但 OPN 和 OCN 水平与 Health 组相似（图 2.20C）。这些结果显示超声介导雷帕霉素递送能够显著促进骨质疏松状态下植入的假体界面及周围骨组织中成骨标志物的表达。  \n\n![](images/43c6b598c183cd3d1dcd7898a75ed36537c276a78775f631caea9b9682f149cb.jpg)  \n图 2.20（A）RT-qPCR 分析成骨相关基因 Runx-2、ALP、OCN 和 OPN 在假体界面周围骨组织中的表达情况；（B）假体界面周围骨组织的 Runx-2、ALP、OCN和OPN 免疫荧光染色；（C）定量分析成骨相关蛋白的荧光强度（ $^{\\cdot}\\ast_{p}<0.05$ ; $\\ast\\ast_{p}$ $\\mathrm{~<0.01~}\\AA$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 121,
+        "chunk": "# 2.5.4 讨论  \n\n随着人口老龄化的加剧，越来越多的接受关节置换术患者伴随患有骨质疏松症。一项回顾性研究发现，接受了髋关节置换手术人群中， $50\\%$ 的患者患有骨质疏松症，其中女性 $53.4\\%$ 和男性 $7\\%$ [35]。由于骨质疏松微环境中过度的骨丢失和低下的成骨能力，使得骨再生能力受限以及假体界面的骨整合不足，从而增加了术后并发症发生，如假体移位和松动以及假体周围骨折等 [221, 222]。因此，提高骨质疏松患者假体界面的骨整合效率具有极大的临床意义。考虑到骨质疏松状态下低下的骨再生与骨整合能力部分归因于 OP-BMSCs 低下的自噬水平所致，使用经典的自噬激活剂——雷帕霉素来促进假体界面骨整合是一个值得考虑的策略。但是，雷帕霉素的全身副作用，如免疫抑制，可能会限制其全身应用来促进骨质疏松症中假体骨整合 [223, 224]。因此，寻找一种有效的局部给药方法，调节 OP-BMSCs 的自噬水平以获得优化的骨整合效果，是一种潜在的替代方法。  \n\n本研究拟通过局部递送自噬激活剂——雷帕霉素以激活 OP-BMSCs 低下的自噬水平，从而促进 3D 打印假体界面的骨整合。与口服和注射的传统给药方法相比，治疗性超声递送药物的转运效率可极大地提高，因此，局部超声递送药物可以减少药物使用剂量，从而避免对全身器官的毒性和损伤，此外优势还包括消除首过代谢，以剂量控制的方式实现个体化给药，无创模式避免了避免穿刺给药潜在的感染风险和引起的疼痛 [225]。此外，这种局部药物递送方式还可以在治疗过程中根据复查结果随时调整药物使用剂量，达到个体化的标准。在超声递送药物的应用中，超声的频率范围参数可以在 0.02 和16MHz 之间的变化；强度参数可以在 0.008 和 $50\\mathrm{W}/\\mathrm{cm}^{2}$ 之间变化。其中，超声波强度是一个主要限制因素，过大的强度可能会造成潜在的皮肤损伤。为了研究透皮超声对局部皮肤的影响以及雷帕霉素对器官的毒性，对皮肤以及主要内脏（心、肝、脾、肺和肾）进行了 H&E染色。结果证明在本研究中我们使用的超声电导仪参数（即频率： $30\\mathrm{kHz}$ ，强度：$45\\mathrm{W/cm}^{2}$ ，时间： $10\\mathrm{min}$ ）不会对局部皮肤产生损伤；而每次 $200\\upmu\\mathrm{l}$ 雷帕霉素溶液（ $1000\\mathrm{nM}\\rangle$ ）、一周 2 次的递药频次也不会对对器官造成毒性和损伤。这些结果表明，本研究中使用的超声介导的雷帕霉素递送策略具有良好的生物安全性，为体内应用促进假体界面骨整合提供了理论基础。  \n\n我们在骨质疏松动物模型体内验证超声介导的雷帕霉素递送策略的骨整合效果。首先，在股骨外侧髁缺损模型中，我们使用特定的钻头制备略小于圆柱形假体尺寸的骨缺损（缺损深度： $10\\mathrm{mm}$ ，直径： $5\\mathrm{mm}$ ；假体长度： $10\\mathrm{mm}$ ，直径：$6\\mathrm{mm}.$ ），以模拟临床的压配式假体植入，以增加了植入初期假体的稳定性，避免假体微动和利于界面骨整合的发生。除了假体界面初始稳定性不足，另一种造成假体松动的常见原因是假体磨损后脱落的金属或高分子颗粒引起的炎症反应。散落在假体周围的颗粒被机体免疫系统识别并视为为异物，趋化巨噬细胞吞噬颗粒，随后启动一系列炎症及联反应，引起假体周围软组织坏死和骨溶解，阻碍骨整合的发生 [226, 227]。在 2.1.3 章节中，我们发现制备的 3D 打印钛合金微孔假体表面有大量未熔融的Ti6Al4V 粉末，这些颗粒可能发生脱落引起无菌性炎症，从而影响骨整合的潜在风险。在此，我们通过股骨远端 X 线正位片未见骨溶解征象，且假体均在位，无明显松动，基本可排除假体表面钛合金颗粒脱落引起的不良后果。随着工程技术的发展，3D 打印作为一种高精度、个体化定制式的骨科假体制造方法而被广泛应用 [228]。3D 打印技术，又被称为增材制造或者快速成型技术，通过在电脑上设计三维实体模型文件，然后逐层堆积的方式来制备具有复杂结构的个性化植入物 [229]。相比于传统的植入物制备手段，3D 打印技术能够快速制造出孔隙形状、孔隙率、孔径大小和宏观形状等参数精确可控的个体化假体 [230,231]。我们制备的孔径、孔隙率及机械性能与宿主骨相似的仿生微孔钛合金支架，具有足够的强度来提供力学支撑，并且与传统钛合金假体相比，有效的减少假体的弹性模量以避免与骨之间的应力屏蔽作用；并且互通的孔隙结构增加了假体表面积，增强了界面与周围组织的结合力与初始稳定性，同时也能够诱导周围骨组织长入微孔内部。在 X 线正位片结果中显示各组假体均在位，无明显松动、移位，以及 Micro-CT 和组织学切片表明各组微孔界面或多或少均有骨组织长入，显示3D 打印微孔假体界面确能提供适当的初始稳定性和诱导骨长入。但是，在骨质疏松状态下，不给与特殊处理的 OP 组和 OP-UI 组骨长入以及力学结合强度明显不足，是否能提供长期可靠的稳定性仍有待商榷。经过章节 2.3 和章节 2.4研究，我们进一步验证 OP-BMSCs 自噬水平下降导致的细胞功能衰退是骨质疏松状态下成骨能力不足的重要原因，因此，我们拟通过经皮超声介导雷帕霉素递送来激活自噬，调节成骨微环境，来进一步促进骨质疏松状态下的假体界面骨整合。  \n\n通过评估假体界面的骨整合强度，可以预测假体移位、松动发生的概率。影像学和组织学手段可以直观地观察到假体界面周围新生骨组织的长入情况。通过Micro-CT 和硬组织切片显示经皮超声介导雷帕霉素递送可以显著促进骨质疏松状态下的微孔假体表面的骨形成与长入，甚至可接近健康状态下的再生骨量水平。但假体植入最终诉求是获得植入的长期稳定性，因此，生物力学测试在评估骨整合效果中是不可或缺的。假体的力学推出测试进一步证明经皮超声介导雷帕霉素递送可以显著提高宿主骨-假体界面的结合力，表明具有优越的骨整合效果。这些结果表明，经皮超声介导的雷帕霉素递送可以显著促进 3D 打印微孔界面在骨质疏松状态下的骨形成和骨整合，从而减少假体植入后松动和移位等术后并发症的发生。  \n\n此外，除了假体松动和移位，假体周围骨折也是假体植入后一个重要的术后并发症，通常与关节置换术后假体周围的骨量和骨质情况有关 [232, 233]。通过Micro-CT 评估假体界面周围的松质骨和皮质骨的骨量和骨质，以及生物力学测试分析假体周围骨组织的抗折强度，可以预测假体周围骨折发生的概率。在本研究中，Micro-CT 结果显示经皮超声介导的雷帕霉素递送可以改善整个股骨远端的骨微观结构，增加局部的骨量，以及增加假体近端皮质骨的厚度和面积；同时，三点弯曲实验显示经皮超声介导的雷帕霉素递送可以显著提高假体周围骨组织的抗折强度。这些结果表明，经皮超声介导的雷帕霉素递送可以显著改善 3D 打印微孔界面周围的骨量和骨质情况，增加骨组织的抗折强度，从而减少假体植入术后假体周围骨折等并发症的发生。  \n\n既往研究已经证明，雷帕霉素可以通过抑制雷帕霉素敏感的 mTOR 靶点和激活BMP/Smad 信号，诱导干细胞向成骨细胞分化 [234]。此外，Qi 等人和 Ma 等人证明系统应用雷帕霉素可以通过增加骨密度、骨体积百分比、骨小梁数目和骨小梁厚度，有效减轻骨质疏松模型的骨丢失 [45, 196]。因此，在本研究中，为了探究经皮超声将雷帕霉素递送到微孔假体植入区域后，对局部自噬情况和成骨微环境的调控，我们进行了一系列的验证。通过对假体界面骨组织中的自噬关键蛋白分析显示，经皮超声将雷帕霉素递送可以显著抑制mTOR 蛋白的表达，（自噬体）膜型蛋白 LC3-II 比例升高，自噬降解蛋白 P62 降低，表明局部微环境中自噬启动，且保持通畅，可有效清除代谢废物。最后，从基因和蛋白层面进一步显示成骨相关标志物Runx-2、ALP、OCN 和OPN 表达上调，表明经皮超声将雷帕霉素递送改善了界面周围的成骨微环境，促进细胞成骨分化、诱导骨形成与长入，从而获得稳定的界面骨整合和改善的周围骨微观结构，为减少假体置换术后松动、移位和假体周围骨折等并发症的发生提供基础。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 122,
+        "chunk": "# 2.5.5 小结  \n\n在假体植入后使用经皮超声介导的雷帕霉素递送策略具有良好的生物安全性，可以有效的激活假体界面周围微环境中的自噬活性，改善成骨微环境，从而获得良好的界面骨整合，并改善周围骨量和骨质情况，有效的减少假体置换术后松动、移位和假体周围骨折等并发症的发生。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 123,
+        "chunk": "# 2.6 本章总结  \n\n在本章研究中，我们设计了一种局部超声介的导雷帕霉素递送策略，以激活OP-BMSCs 的退化的自噬水平，从而恢复其下降的细胞活性，包括增殖、存活、迁移、形态和成骨分化能力，同时抑制 OP-BMSCs 潜在的成脂分化能力。更重要的是，在骨质疏松症动物模型体内假体植入术后使用超声介导的雷帕霉素递送可以显著提高的3D 打印钛合金假体界面的骨整合及假面周围的骨量和骨质，减少假体置换术后松动、移位和假体周围骨折等并发症的发生。总的来说，本研究证实了超声介导的雷帕霉素递送这种个性化的策略通过调节 OP-BMSCs 自噬来促进骨质疏松状态下的假体界面骨整合机制，为提高骨质疏松等特殊骨质不良人群人工假体的研发提供新的思路。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 124,
+        "chunk": "# 第 3 章  功能化水凝胶介导的雷帕霉素局部递送通过激活自噬和调控成骨微环境促进骨质疏松状态下假体界面骨整合  \n\n骨质疏松患者在关节置换术后更易发生假体松动、移位和假体周围骨折等严重并发症，其主要原因可能与 OP-BMSCs 自噬能力低下导致的增殖受限、成骨活性缺陷和成脂分化增加有关。个体化 3D 打印假体表面的微孔结构可以增强界面初始稳定性的同时促进骨长入，但受限于钛合金假体界面的生物惰性、微孔的孔隙较大及表面光滑等物理特征，不利于 BMSCs 粘附和增殖，难以负载可激活OP-BMSCs 自噬能力的成分，不利于 OP-BMSCs 增殖和成骨分化，无法达到高效骨整合的作用。自噬激活剂——雷帕霉素可以上调 OP-BMSCs 自噬水平，促进其增殖和成骨分化，从而加速骨质疏松状态下的骨再生。  \n\n本论文在第二章部分设计了一种经皮超声介导的雷帕霉素递送策略，可以有效的激活 OP-BMSCs 自噬活性，改善成骨微环境，成功地促进了假体界面骨整合。但是，通过特制的超声电导仪频繁的经皮给药，可能导致患者依从性差，且增加了经济和时间负担。因此，本章节我们试图构建一种“3D 打印金属微孔/水凝胶的生物活性界面”作为一站式植入物，以壳聚糖（CEC）、聚乙烯醇（PVA），纳米银线（AgNW）和硼砂制备的多功能水凝胶（CEC-PVA-AgNW）作为药物递送系统缓释雷帕霉素上调 OP-BMSCs 的自噬水平，并利于其在金属微孔表面的粘附、增殖，激发其成骨分化潜能，促进假体界面的骨整合。此外，除了假体界面的骨整合不良导致的松动、移位和假体周围骨折等严重并发症，假体周围感染也是导致植入手术失败不可忽视的因素。通过掺杂纳米银线赋予功能化水凝胶高效的抗菌性能，可以有效减少假体周围感染的发生率，进一步优化生物活性界面植入后的成功率（图 3.1）。  \n\n![](images/3b522aa2550c4ae3068ab9d01b857a0e323058ea56b559b8a148381964450f19.jpg)  \n图 3.1 功能化水凝胶介导的雷帕霉素局部递送通过激活自噬和调控成骨微环境促进骨质疏松状态下假体界面骨整合，同时抑制细菌引起的假体周围感染。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 125,
+        "chunk": "# 3.1 水凝胶的制备与表征",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 126,
+        "chunk": "# 3.1.1 实验仪器与材料",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 127,
+        "chunk": "# 3.1.1.1 实验仪器  \n\n<html><body><table><tr><td>仪器名称</td><td>厂家</td></tr><tr><td>DF-101S集热式恒温加热磁力搅拌器</td><td>上海秋佐科学仪器有限公司</td></tr><tr><td>LC-OES-60高速精密增力搅拌机</td><td>上海力辰邦西仪器科技有限公司</td></tr><tr><td>恒温水浴锅</td><td>上海昕仪仪器仪表有限公司</td></tr><tr><td>MilliQ 纯水仪</td><td>美国MILLIPORE公司</td></tr><tr><td>冻干机</td><td>苏州安泰空气技术有限公司</td></tr><tr><td>高压灭菌锅</td><td>上海昕仪仪器仪表有限公司</td></tr></table></body></html>  \n\n第 3 章  功能化水凝胶介导的雷帕霉素局部递送通过激活自噬和调控成骨微环境促进骨质疏松状态下假体界面骨整合  \n3.1.1.2 主要试剂  \n\n\n<html><body><table><tr><td colspan=\"2\">续表：</td></tr><tr><td>干燥箱</td><td>上海昕仪仪器仪表有限公司</td></tr><tr><td>移液器</td><td>德国Eppendorf 公司</td></tr><tr><td>电子天平</td><td>上海花潮电器有限公司</td></tr><tr><td>扫描电子显微镜</td><td>日本JEOL公司</td></tr><tr><td>流变仪</td><td>美国 TA Instruments-Waters LLC 公司</td></tr></table></body></html>  \n\n<html><body><table><tr><td>试剂名称</td><td>厂家</td></tr><tr><td>壳聚糖</td><td>上海Aladdin生化科技有限公司</td></tr><tr><td>丙烯酸</td><td>广州西陇化工有限公司</td></tr><tr><td>氯化氢</td><td>北京化工厂有限责任公司</td></tr><tr><td>氢氧化钠</td><td>北京化工厂有限责任公司</td></tr><tr><td>乙醇</td><td>北京化工厂有限责任公司</td></tr><tr><td>乙二醇</td><td>北京化工厂有限责任公司</td></tr><tr><td>氯化铜</td><td>天津永盛精细化工有限公司</td></tr><tr><td>硝酸银</td><td>国药集团化学试剂上海有限公司</td></tr><tr><td>聚乙烯醇（PVA)</td><td>美国 Sigma-Aldrich 公司</td></tr><tr><td>聚乙烯基吡咯烷酮（PVPON)</td><td>美国 Sigma-Aldrich 公司</td></tr><tr><td>PBS缓冲液</td><td>北京索莱宝科技有限公司</td></tr><tr><td>叠氮化钠</td><td>上海Aladdin生化科技有限公司</td></tr><tr><td>琼脂糖</td><td>上海Aladdin生化科技有限公司</td></tr><tr><td>甘油</td><td>上海Aladdin生化科技有限公司</td></tr><tr><td>硼砂</td><td>北京化工厂有限责任公司</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 128,
+        "chunk": "# 3.1.2 实验方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 129,
+        "chunk": "# 3.1.2.1 水凝胶的制备  \n\n1）N-羧乙基壳聚糖（ $N.$ -carboxyethyl chitosan, CEC）制备：将壳聚糖（ $2\\mathrm{g}$ ， $12.4\\mathrm{mmol})$ ）与丙烯酸（ $2.9\\mathrm{mL}$ , 42.6 mmol）溶解于 $100\\mathrm{mL}$ 去离子水中，并在 $50^{\\circ}\\mathrm{C}$ 的水浴中磁力搅拌72h。随后，滴加 NaOH 溶液调节体系pH 值至10–12。将上述所得溶液置于去离子水中透析（MWCO 14000）3 天，将产品冷冻干，获得 CEC 粉末备用；  \n\n2）纳米银线（Silver Nanowires, AgNW）制备：  \n\n在磁力搅拌下（ $260\\mathrm{rpm}$ ）将无水乙二醇（ ${5}\\mathrm{ml}$ ）加热至 $151.5^{\\circ}\\mathrm{C}1\\$ 小时。向体系中加入 含 $\\mathrm{CuCl}_{2}$ 的乙二醇溶液（ $(4\\mathrm{mmol}\\mathrm{L}^{-1},0.9\\mathrm{ml})$ ）。继续搅拌 $15\\mathrm{min}$ ，然后加入溶于乙二醇中的聚乙烯基吡咯烷酮（PVPON）溶液（ $(0.1\\mathrm{g},2.5\\mathrm{ml})$ ），然后注射溶有 $\\mathrm{AgNO_{3}}$ 的乙二醇溶液（ $(0.05\\mathrm{g},2.5~\\mathrm{ml})$ ），继续搅拌 $30~\\mathrm{min}$ ，待反应结束体系冷却至室温后， $2000\\mathrm{rpm}$ ， $5\\mathrm{min}$ 乙醇离心洗涤多次，获得 AgNW 待用；  \n\n3）CEC-PVA-AgNW 水凝胶合成：  \n\n将 $0.5\\mathrm{g}$ 聚乙烯醇（Polyvinyl alcohol, PVA），CEC（ $\\left(0.025\\mathrm{g}\\right)$ ），琼脂糖（0.025g）和甘油（ $0.2~\\mathrm{ml}$ ）溶解在 $10~\\mathrm{ml}$ 去离子水中，将该混合物在 $90^{\\circ}\\mathrm{C}$ 磁搅拌下油浴 $2\\mathrm{h}$ ，然后向上述溶液中加入 $\\mathrm{AgNW}\\left(0.2\\mathrm{mg}\\mathrm{ml}^{-1}\\right)$ ），并继续搅拌 $15\\mathrm{min}$ 。最后，将 $10\\mathrm{mlNa_{2}B_{4}O_{7}}$ 溶液（ $\\boldsymbol{0.04\\mathrm{mol}\\mathrm{L}^{-1}}$ ）加入上述混合物中，通过搅拌约 $10\\mathrm{min}$ 即可获得 CEC-PVA-AgNW 水凝胶。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 130,
+        "chunk": "# 3.1.2.2 水凝胶的流变性能测试  \n\n夹具使用直径为 $10~\\mathrm{mm}$ 的圆形平行板，间隙设置为 $1000~{\\upmu\\mathrm{m}}$ 。在测试过程中，用盖子将水凝胶盖住避免水分蒸发致水凝胶干燥而影响测试结果。在时间扫描模式下，设置流变仪的频率为 $10\\mathrm{rad/s}$ ，应变为 $0.1\\%$ ，温度为 $25^{\\circ}\\mathrm{C}$ ；在应变扫描模式下，设置流变仪的频率为 $10\\mathrm{rad/s}$ ，应变在 $10{-}500\\%$ 范围内，温度为 $25^{\\circ}\\mathrm{C}$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 131,
+        "chunk": "# 3.1.2.3 水凝胶的微观结构表征  \n\n将获得的 CEC-PVA-AgNW 水凝胶冻干、脱模，在样本表面进行喷金处理后在扫描电子显微镜下进行观察水凝胶表面微观结构。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 132,
+        "chunk": "# 3.1.2.4 水凝胶的自愈合与导电性  \n\n将两块完整的水凝胶用剪刀物理剪切成两半，将不同部分的水凝胶结合在一起，观察来自不同水凝胶的两个半部分的结合情况。除了机械自修复性能外，CEC-PVA-AgNW 水凝胶的导电性能自动修复情况通过连接发光二极管进行检测。  \n\n即将CEC-PVA-AgNW 水凝胶连接到具有发光二极管作为指示器的电路中，并通过电源点亮发光二极管。当水凝胶物理切割成两半时，二极管熄灭。随后，将分离的两半放在一起，观察发光二极管是否可以再次点亮。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 133,
+        "chunk": "# 3.1.2.5 水凝胶的体外降解实验  \n\n通过记录水凝胶干态质量的变化来评估其体外降解率。首先，将 $100~\\mathrm{{mg}}$ 冻干水凝胶放入体外生理模拟液中（ $37^{\\mathrm{{\\circ}}}\\mathrm{C}$ ，PBS 缓冲液）。并在溶液中加入 $0.02\\mathrm{wt\\%}$ 叠氮化钠，用于抑制细菌生长。在预先设定的时间点收集PBS 中残存的水凝胶，冻干后计算质量损失。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 134,
+        "chunk": "# 3.1.2.6 数据统计分析  \n\n同章节 2.1.2.3。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 135,
+        "chunk": "# 3.1.3 结果",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 136,
+        "chunk": "# 3.1.3.1 CEC-PVA-AgNW 水凝胶合成  \n\n如图 3.2A 所示，我们成功制备了纳米结构的银线。为了赋予材料药物递送和骨再生性能，我们首先选择生物相容性聚合物制备具有多网络结构的水凝胶。简而言之，将 $\\mathrm{Na}_{2}\\mathrm{B}_{4}\\mathrm{O}_{7}$ 溶液添加到 PVA、CEC、琼脂糖、甘油和 AgNW 的混合溶液中，均匀搅拌后即可获得透明的导电超分子水凝胶（图 3.2B）。 通过扫描电子显微镜可观察水凝胶为互联多孔结构（图 3.2C）。如图3.2D 所示，水凝胶的骨架网络主要由 CEC-琼脂糖、CEC-PVA 和琼脂糖-PVA 之间的强氢键组成。由于PVA-硼砂-PVA 和 PVA-甘油-PVA 的动态反应，也形成了可逆网络。PVA 和 AgNW之间的静态氢键网络，可使导电 AgNW 均匀分散在水凝胶中。此外，在体外模拟液PBS 中，水凝胶可在 36-48 天内缓慢降解（图 3.3）。  \n\n![](images/2672aedfc85271061a160e9dbeb49483921f6cf9b171f1a8f457e1792b8d7683.jpg)  \n图 3.2（A）通过扫面电子显微镜观察 AgNW 的微观结构；（B）CEC-PVA-AgNW水凝胶合成外相；（C）通过扫面电子显微镜CEC-PVA-AgNW 水凝胶的微观结构；（D）CEC-PVA-AgNW 水凝胶成胶机理图示。  \n\n![](images/8ddf30a5c1cb5353b4c27cecbcfd2a6f314036939236dde5077ba7084a5ed0c3.jpg)  \n图 3.3 CEC-PVA-AgNW 水凝胶的降解曲线。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 137,
+        "chunk": "# 3.1.3.2 CEC-PVA-AgNW 水凝胶多功能特性  \n\n首先，通过宏观实验观察水凝胶的自修复性能。如图 3.4A 所示，两块水凝胶分别用不同的颜色染色，然后用剪刀物理切割成两半后再将不同部分结合在一起，来自不同水凝胶的两个半部分可以在 5 min 后愈合。为了观察水凝胶的导电性，以及机械自修复之后的导电情况，我们将 CEC-PVA-AgNW 水凝胶连接到具有发光二极管作为指示器的电路中，并通过电源点亮二极管。当水凝胶物理切割成两半时，二极管熄灭。随后，将分离的两半放在一起，由于氢键在室温下可逆地结合和解离，二极管可以再次点亮（图 3.4B）。为了进一步定量证明水凝胶的自愈合特性，进行了流变学分析。如图 3.4C 所示，CEC-PVA-AgNW 水凝胶的储能模量（G’）和损耗模量（G’’）在低应变下保持恒定值，而随着应变的增强，它们可以在 $400\\%$ 的应变下相交。该交界点就是破坏水凝胶正常网络结构所需的临界值。根据 G’和 G’’随剪切应变的演变，我们将剪切应变在 $500\\%$ 和 $10\\%$ 之间交替变化，如图 3.4D 所示，水凝胶交替表现出高应变时的液体和低应变时的固体行为，机械性能几乎完全恢复到模量的原始值。  \n\n![](images/3f9c0f015b06fc45a492e818b0f0612746847336fc7c84efd0e2908d8e497e00.jpg)  \n图 3.4（A）将水凝胶切成两块后在环境条件下的自愈合图像；（B）自愈合水凝胶连接到二极管电路中恢复电导性的宏观照片；（C）PVA-NCECS-AG/AG NWs水凝胶在固定角频率（ $\\mathrm{\\Delta\\cdot10\\rad/s)}$ ）下的应变相关振荡剪切流变学；（d）使用交替的低（ $(10\\%)$ ）至高（ $50\\%$ ）剪切应变测量水凝胶的自愈合性能。每个应变间隔保持为100s，固定频率保持为 $10{\\mathrm{~rad/s}}.$ 。  \n\n随后，我们检测了水凝胶的透明性。如图 3.5A 所示，显示了具有不同浓度AgNW 的水凝胶在 $400{-}700~\\mathrm{nm}$ 波长范围内的光透射率。水凝胶的透明度可以通过改变 $\\operatorname{AgNW}$ 的浓度来改变。当 $\\operatorname{AgNW}$ 含量从 0 增加到 $0.2\\mathrm{mg/mL}$ 时，水凝胶在 $660\\mathrm{nm}$ 波长下的每毫米厚度的平均透射率从 $93\\%$ 降低到 $74\\%$ 。此外，当水凝胶覆盖在纸板上时，纸板上的“SKLJLU”文字清晰可见，表明其较高的透明度高（图3.5B）。此外，水凝胶的在不同环境中的智能响应性被进一步探究。如图 3-5C 所示，通过提高温度（ $90^{\\circ}\\mathrm{C}$ ）或超声刺激（ $20\\mathrm{min}.$ ）可破坏水凝胶网络结构。除了外加的物理刺激外，降低 pH（0.1M）或添加竞争性含二醇分子（如果糖、葡萄糖、多巴胺和维生素 B6）也可能快速触发水凝胶结构的破坏。这种刺激响应性能主要归因于 $\\mathrm{\\DeltaNa}_{2}\\mathrm{B}_{4}\\mathrm{O}_{7}$ 和PVA 之间形成可逆性质的硼酸盐（图 3.5D）。  \n\n![](images/fec0118895c56a7c236ea1284ba1611afc8bec4c1f0c456a4991bf2bb82fdc15.jpg)  \n图 3.5（A） 含不同浓度 AgNW（0, 0.05, 0.10, 0.15, $0.20~\\mathrm{mg/mL}$ ）的水凝胶的宏观透光图像；（B）含不同浓度 AgNW 的水凝胶在空气中的透光光谱；（C）由不同刺激（如加热、超声、果糖、葡萄糖、多巴胺、维生素 B6 和 HCl）触发的水凝胶的凝胶-溶胶相变；（D）水凝胶对不同刺激的多重响应机制示意图。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 138,
+        "chunk": "# 3.1.4 讨论  \n\n在本章节中，我们通过将 $\\mathrm{Na}_{2}\\mathrm{B}_{4}\\mathrm{O}_{7}$ 溶液添加到PVA、CEC、琼脂糖、甘油和AgNW 的混合溶液中，获得了具有溶胀稳定、有序降解、自愈合、导电、透明和智能响应的多功能超分子水凝胶。该水凝胶的骨架网络主要由 CEC-琼脂糖、CEC-PVA 和琼脂糖-PVA 之间的强氢键（氢键 I）组成 [235]。这些强氢键允许水凝胶立即形成，并赋予超分子水凝胶稳定的机械性能。由于 PVA-硼砂-PVA 和PVA-甘油-PVA（氢键 II）的动态反应，也形成了可逆网络 [236]。此外，PVA 和AgNW 之间的静态氢键网络（氢键 III），可使导电 AgNW 均匀分散在水凝胶中。制备的水凝胶具有互联的多孔结构，可以保证营养和氧气运输，使细胞迁移和增殖，从而增强新组织的形成。众多氢键的形成，赋予了水凝胶较为致密的多孔结构，赋予了水凝胶潜在的药物递送能力 [237, 238]；而AgNW 的引入可能给水凝胶带来有力的抗菌性能 [239, 240]。对于骨生成，水凝胶的有序降解为骨向内长入多孔界面提供了空间。水凝胶在体外模拟液体 PBS 中可在36-48 天内缓慢降解。先前的研究报道，生物活性水凝胶植入后约 2-4 周发生血管生成和骨形成，本研究中获得的水凝胶的有序降解速率有利于为骨再生提供空间 [241]。  \n\n由于 PVA-硼砂 PVA 和 PVA-甘油-PVA 之间的动态氢键，赋予 CEC-PVA-AgNW 水凝胶优异的自修复性能，并可使重新愈合的水凝胶可以长时间保持结构的稳定性。除了机械自修复性能外，CEC-PVA-AgNW 水凝胶的导电性能可以自动修复。通过在系统中加入金属颗粒制备导电材料引起了研究人员的广泛关注，并在生物医学中具有潜在应用 [242-244]。在过去的几十年中，智能软材料因为其宏观结构和物理性能在响应特定刺激时表现出显著的变化，引起了越来越多的关注[245, 246]。通过上述水凝胶中的可逆键的存在，赋予了水凝胶作为刺激响应宏观结构的前景。这种刺激响应性能主要归因于 $\\mathrm{Na}_{2}\\mathrm{B}_{4}\\mathrm{O}_{7}$ 和 PVA 之间形成可逆性质的硼酸盐。更具体地说，基于硼酸盐的反应的平衡可以通过加热、超声波、降低 pH值和引入含二醇的分子来调节。自由分子中的二醇基团比 PVA 聚合物更具反应性，因此可作为PVA 的竞争对手与 $\\mathrm{Na}_{2}\\mathrm{B}_{4}\\mathrm{O}_{7}$ 反应 [247]。因此，超分子水凝胶在含有二醇基团的分子（如果糖、葡萄糖、多巴胺和维生素 B6）存在下解离和溶解。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 139,
+        "chunk": "# 3.1.5 小结  \n\n我们通过将 $\\mathrm{Na}_{2}\\mathrm{B}_{4}\\mathrm{O}_{7}$ 溶液添加到 PVA、CEC、琼脂糖、甘油和 AgNW 的混合溶液中，成功制备了超分子水凝胶。获得的 CEC-PVA-AgNW 水凝胶具有稳定的有序降解性、自愈合能力、导电性、透明性、智能响应性，以及潜在的药物递送和抗菌性能。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 140,
+        "chunk": "# 3.2 3D 打印生物活性界面制备、表征与抗菌性分析",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 141,
+        "chunk": "# 3.2.1 实验仪器与材料",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 142,
+        "chunk": "# 3.2.1.1 实验仪器  \n\n<html><body><table><tr><td>仪器 品牌</td></tr><tr><td>EBM机 瑞典 Arcam 公司</td></tr><tr><td>超净操作台 美国Airtech公司</td></tr></table></body></html>  \n\n3.2.1.2 主要试剂  \n\n\n<html><body><table><tr><td>细胞培养箱</td><td>美国Thermo 公司</td></tr><tr><td>超声波清洗机</td><td>上海比朗仪器制造有限公司</td></tr><tr><td>Micro-CT</td><td>德国 Bruker 公司</td></tr><tr><td>冻干机</td><td>苏州安泰空气技术有限公司</td></tr><tr><td>扫描电子显微镜</td><td>日本JEOL公司</td></tr><tr><td>高效液相色谱-串联质谱仪</td><td>美国 Thermo 公司</td></tr><tr><td>细菌培养试管</td><td>泰州市方格医疗器械有限公司</td></tr><tr><td>恒温震荡箱</td><td>上海一恒科学仪器有限公司</td></tr><tr><td>荧光倒置显微镜</td><td>日本Olympus 公司</td></tr><tr><td>酶标仪</td><td>美国Thermo 公司</td></tr><tr><td>高压灭菌锅</td><td>上海昕仪仪器仪表有限公司</td></tr><tr><td>冰箱</td><td>青岛海尔生物医疗股份有限公司</td></tr><tr><td>超低温冰箱</td><td>青岛海尔生物医疗股份有限公司</td></tr><tr><td>干燥箱</td><td>上海昕仪仪器仪表有限公司</td></tr><tr><td>万能力学测试机</td><td>上海长肯试验设备有限公司</td></tr><tr><td>电子天平</td><td>上海花潮电器有限公司</td></tr></table></body></html>  \n\n<html><body><table><tr><td>试剂名称</td><td>厂家</td></tr><tr><td>Ti6A14V粉末</td><td>北京爱康医疗</td></tr><tr><td>雷帕霉素</td><td>美国 Sigma-Aldrich 公司</td></tr><tr><td>金黄色葡萄球菌（S.aureus）</td><td>ATCC</td></tr><tr><td>耐甲氧西林金黄色葡萄球菌（MRSA)</td><td>ATCC</td></tr><tr><td>LB培养基</td><td>北京索莱宝科技有限公司</td></tr><tr><td>活/死细菌染色试剂盒</td><td>上海翌圣生物科技股份有限公司</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 143,
+        "chunk": "# 3.2.2 实验方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 144,
+        "chunk": "# 3.2.2.1 3D 打印微孔假体的制备与表征  \n\n同章节 2.1。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 145,
+        "chunk": "# 3.2.2.2 3D 打印生物活性界面的制备  \n\n在凝胶溶液混合前，将 $10\\mathrm{mlNa}_{2}\\mathrm{B}_{4}\\mathrm{O}_{7}$ 溶液（ $0.04\\mathrm{mol}\\mathrm{L}^{-1}$ ）溶液中预先加入放有3D 打印微孔假体的模具中，再往模具中加入含有雷帕霉素（ $54.85~\\mathrm{mg}$ ）的PVA（ $(0.5\\mathrm{g})$ ）、CEC（ $\\left(0.025\\mathrm{g}\\right)$ ）、琼脂糖（ $(0.025\\mathrm{g})$ ）、甘油（ $0.2{\\mathrm{ml}}$ ）和 AgNW（ $0.2\\mathrm{mg}$ $\\mathrm{ml}^{-1}$ ）混合溶液，搅拌 $15\\mathrm{min}$ ，使溶胶充分混合并浸入微孔内部并成胶，最终获得雷帕霉素终浓度为 $3~{\\upmu\\mathrm{M}}$ 的3D 打印生物活性界面。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 146,
+        "chunk": "# 3.2.2.3 3D 打印生物活性界面微观结构观察  \n\n将获得的 3D 打印生物活性假体界面冻干、脱模，在样本表面进行喷金处理后在扫描电子显微镜下进行观察假体界面的微观结构。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 147,
+        "chunk": "# 3.2.2.4 雷帕霉素药物释放分析  \n\n将负载雷帕霉素的生物活性界面置于在 $37^{\\circ}\\mathrm{C}$ ，含 $2~\\mathrm{ml}$ PBS 的玻璃瓶中，设置5 个平行瓶。在预定时间点，抽取 $2~\\mathrm{ml}$ PBS 并储存在- $80^{\\circ}\\mathrm{C}$ 冰箱中，再加入 2ml 新鲜 PBS。用高效液相色谱法（HPLC，检测波长为 $278~\\mathrm{nm}$ ）分析 PBS 中雷帕霉素的释放水平，其参数设定如下，流动相 A：三乙胺缓冲液/已腈/四氢呋喃$\\scriptstyle=96/3/1$ ，流动相 B：三乙胺缓冲液/已腈/四氢呋喃 $=70/29/1$ ，流速为 $1.0\\ \\mathrm{ml/min}$ ，检测波长为 $278~\\mathrm{nm}$ ，先行梯度洗脱。通过标准曲线计算样本浓度及药物累计释放量。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 148,
+        "chunk": "# 3.2.2.5 细菌活死染色实验  \n\n取 $1~\\mathrm{ml}$ 初始菌液加入细菌培养试管，再加入 LB 液体培养基 $5~\\mathrm{ml}$ ，将试管放入恒温震荡箱中，设置温度为 $37^{\\circ}\\mathrm{C}$ ，转速为 $100\\mathrm{r/min}$ 。培养 $20\\mathrm{h}$ 后收集试管中培养液 $100\\upmu\\mathrm{l}$ ，进行细菌活死染色，具体步骤如下：  \n\n1）将1 体积的 DMAO 和2 体积的EthD-Ⅲ在离心管中充分混合均匀，加入8 体积的 $0.85\\%\\mathrm{NaCl}$ 得到 $100\\times$ 染色工作液；  \n\n2） $100\\upmu\\mathrm{l}$ 菌液中加入 $1\\upmu\\mathrm{l}$ 的 $100\\times$ 染色工作液，混合均匀，室温下避光孵育$15\\mathrm{min}$ ;  \n\n3）取 $10~\\upmu\\mathrm{l}$ 染色后的菌液滴加在载玻片上，并盖上盖玻片；  \n4）荧光显微镜下观察细菌活死情况。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 149,
+        "chunk": "# 3.2.2.6 细菌增殖抑制实验  \n\n取 $1~\\mathrm{ml}$ 初始菌液加入细菌培养试管，再加入 LB 液体培养基 $5~\\mathrm{ml}$ ，将试管放入恒温震荡箱中，设置温度为 $37^{\\circ}\\mathrm{C}$ ，转速为 $100\\mathrm{r/min}$ 。分别在培养 0、2、4、12、20、40、60 和 $80\\mathrm{h}$ 后收集试管中培养液 $100\\upmu\\mathrm{l}$ 并转移到96 孔板中，使用酶标仪在 $600\\mathrm{nm}$ 波长测量菌液的吸光度。LB 液体培养基作为空白对照（NC）组，并绘制细菌生长曲线。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 150,
+        "chunk": "# 3.2.2.7 数据统计分析  \n\n同章节 2.1.2.3。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 151,
+        "chunk": "# 3.2.3 结果",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 152,
+        "chunk": "# 3.2.3.1 3D 打印生物活性界面构建与表征  \n\n通过前述方法，我们获得了同章节 2.1.3 同样参数的 3D 打印平板状和圆柱状的两种形状的钛合金微孔支架，即孔隙率为 $69.2{\\pm}0.9\\%$ ，孔径为 $796.0{\\pm}1.9\\upmu\\mathrm{m}$ ，抗压强度为 $48.0{\\pm}2.1\\mathrm{MPa}$ ，弹性模量为 $1.63{\\scriptstyle\\pm0.2\\mathrm{GP}}$ 。按照如图3.6A 所示制备3D打印生物活性界面，即将3D 打印微孔支架预先置于含有 $\\mathrm{Na}_{2}\\mathrm{B}_{4}\\mathrm{O}_{7}$ 溶液的模具中，再往模具中加入含有将雷帕霉素的 PVA、CEC、琼脂糖、甘油和 AgNW 混合溶液，搅拌 $15\\mathrm{min}$ ，即可获得雷帕霉素终浓度为 $3\\upmu\\mathrm{M}$ 的3D 打印生物活性界面（图3.6B）。如图3.6C 所示，在扫面电镜下可观察到微孔支架内部完全填充多孔互通结构的水凝胶网络，这表明复合生物活性假体界面的成功构建。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 153,
+        "chunk": "# 3.2.3.2 3D 打印生物活性界面的药物释放曲线  \n\n作为一种药物递送系统，药物的持续稳定释放对于生物应用至关重要。如图3.6D 所示，我们记录了48 天内雷帕霉素在3D 打印生物活性界面中的释放曲线。前三天，雷帕霉素的累计释放量为 $18.77{\\scriptstyle\\pm2.13\\%}$ ，而随后的释放曲线逐渐稳定，  \n\n表明药物释放稳定且持续至第 36 天的释放量为 $78.16{\\pm}1.88\\%$ ，并在第 48 天总共释放 $80.13{\\pm}1.91\\%$ 封装药量。  \n\n![](images/acf1668a164d754f529a54d81c11fcab4b37765bdf2378877aa359c0e8ba3435.jpg)  \n图 3.6（A）3D 打印钛合金微孔支架与负载雷帕霉素的 CEC-PVA-AgNW 水凝胶构建的3D 打印生物活性界面的模式图；（B）平板状和圆柱状3D 打印生物活性界面外观；（C）通过扫描电子显微镜观察 3D 打印生物活性界面微观结构；（D）雷帕霉素在3D 打印生物活性界面中的药物释放曲线。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 154,
+        "chunk": "# 3.2.3.3 3D 打印生物活性界面的抗菌性  \n\n在培养 $20\\mathrm{~h~}$ 后，活死染色图像显示在 NC 组和 pTi 组中培养的大多数 S.aureus 和MRSA 细菌保持存活，表明纯多孔钛合金微孔支架没有抗菌性能。而在水凝胶和负载雷帕霉素的水凝胶填充的多孔钛合金微孔支架中（即 $\\mathsf{p T i}\\ @\\mathsf{G e l}$ 组和 pTi-Rap $@\\mathrm{Gel}$ 组）中培养的细菌几乎死亡（图 3.7A、B）。定量分析显示，在NC 组、pTi 组、 $\\mathtt{p T i}\\ @\\mathtt{G e l}$ 组和 pTi-Rap $@\\mathrm{Gel}$ 组中，S. aureus 的存活率分别为$95.36{\\pm}1.72\\%$ 、 $93.90{\\scriptstyle\\pm1.98\\%}$ 、 $14.50{\\pm}2.23\\%$ 和 $12.61{\\scriptstyle\\pm4.42\\%}$ （图 3.7C）；而 MRSA 的存活率为 $94.54{\\scriptstyle\\pm2.18\\%}$ 、 $93.98{\\pm}1.25\\%$ 、 $20.14{\\scriptstyle\\pm4.08\\%}$ 和 $19.02{\\pm}2.72\\%$ （图 3.7D）。此外，通过吸光度评估菌细增殖曲线表明，与 NC 组和pTi 组相比， $\\mathsf{p T i}\\ @\\mathsf{G e l}$ 组和 pTi-Rap@Gel 组在 80 小时内对 S. aureus（图 3.7E）和 MRSA（图 3.7F）细菌增殖具有较强的抑制作用。  \n\n![](images/50c76d05908548f66f8dbcb9057695fb8216be9129ff394f7f0af51b868e9094.jpg)  \n图 3.7（A）S. aureus 的 BacLight 死/活染色；（B）MRSA 的 BacLight 死/活染色;（C）定量分析 S. aureus 的存活率; （D）定量分析 MRSA 的存活率; （E） S.aureus 的增殖曲线; （F）MRSA 的增殖曲线（ $^{\\ast}p<0.05$ ; $^{**}p<0.01$ ; ${}^{***}p<0.001\\rangle$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 155,
+        "chunk": "# 3.2.4 讨论  \n\n同章节 2.1 相同，我们利用 3D 打印技术制备孔径大小、形态和孔隙率可控，且微孔间互通性良好的仿生3D打印微孔钛合金支架。使用多功能化的CEC-PVA-AgNW 水凝胶作为雷帕霉素药物递送系统，与 3D 打印微孔钛合金支架复合成功构建了3D 打印生物活性界面。作为一种药物递送系统，药物的持续稳定释放对于生物应用至关重要。通过对 3D 打印生物活性假体界面在 48 天内雷帕霉素的释放分布曲线可知，在初始阶段雷帕霉素的释放速率稍快，而之后的释放曲线逐渐稳定且持续，表明该 3D 打印生物活性界面具有优良的缓释性能。初期阶段雷帕霉素较快的速释放可能与药物通过静电相互作用吸附在生物活性假体界面表面有关。随后，在稳定释放阶段，水凝胶的降解可能成为影响雷帕霉素释放的主要因素。CEC-PVA-AgNW 水凝胶的缓慢降解使雷帕霉素能够以稳定的方式持续释放 [155]。  \n\n此外，假体植入后，假体周围感染是导致植入术失败的一个主要原因。AgNW的引入赋予了生物活性界面独特的抗菌性能。银离子从超分子水凝胶的初始释放足以抑制试管中S. aureus 的增殖，并继续发挥抗菌作用。然而，MRSA 的抑菌曲线略有不同，即在12 小时的初始阶段，对MRSA 的抑制作用不如S. aureus 明显。  \n\n随着AgNW 释放量的增加，20 小时后细菌的吸光度降低，表明抗菌作用开始明显。值得注意的是，pTi 组的细菌增殖率高于 NC 组，这可能是由于多孔结构提供了利于细菌繁殖的场所 [248]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 156,
+        "chunk": "# 3.2.5 小结  \n\n我们通过 EBM 技术成功制备了 3D 打印微孔钛合金支架，并将其与负载雷帕霉素的功能化CEC-PVA-AgNW 水凝胶复合，构建了具有药物缓释功能和良好抗菌性能的3D 打印生物活性界面。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 157,
+        "chunk": "# 3.3 3D 打印生物活性界面激活 OP-BMSCs 自噬",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 158,
+        "chunk": "# 3.3.1 实验仪器与材料",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 159,
+        "chunk": "# 3.3.1.1 实验仪器  \n\n<html><body><table><tr><td>仪器名称</td><td>厂家</td></tr><tr><td>细胞培养箱</td><td>美国Thermo 公司</td></tr><tr><td>超净操作台</td><td>美国Airtech公司</td></tr><tr><td>荧光倒置显微镜</td><td>日本 Olympus 公司</td></tr><tr><td>蛋白电泳及转膜仪</td><td>中国 Tanon公司</td></tr><tr><td>Clinx Science Instruments</td><td>上海勤翔科学仪器有限公司</td></tr></table></body></html>\n\n其他仪器同 2.3.1.1。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 160,
+        "chunk": "# 3.3.1.2 主要试剂  \n\n<html><body><table><tr><td>试剂名称</td><td>厂家</td></tr><tr><td>Triton-X 100</td><td>美国Invitrogen 公司</td></tr><tr><td>蛋白裂解液</td><td>北京全式金生物技术有限公司</td></tr><tr><td>蛋白酶抑制剂</td><td>北京全式金生物技术有限公司</td></tr><tr><td>5x蛋白上样缓冲液</td><td>北京鼎国昌盛生物技术有限公司</td></tr><tr><td>BCA蛋白浓度测定试剂盒</td><td>上海碧云天生物技术有限公司</td></tr><tr><td>Protein leader</td><td>美国Thermo 公司</td></tr><tr><td>PVDF膜</td><td>美国Millipore公司</td></tr></table></body></html>  \n\n续表：  \n\n\n<html><body><table><tr><td>SDS-PAGE凝胶配制试剂盒</td><td>北京鼎国昌盛生物技术有限公司</td></tr><tr><td>脱脂奶粉</td><td>北京鼎国昌盛生物技术有限公司</td></tr><tr><td>山羊血清</td><td>上海源叶生物科技有限公司</td></tr><tr><td>目的蛋白一抗</td><td>北京博奥森生物技术有限公司</td></tr><tr><td>标记二抗</td><td>北京博奥森生物技术有限公司</td></tr><tr><td>Ad-McHery-GFP/LC3B</td><td>上海碧云天生物技术有限公司</td></tr><tr><td>雷帕霉素</td><td>美国 Sigma-Aldrich 公司</td></tr></table></body></html>\n\n其他试剂同 2.3.1.2。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 161,
+        "chunk": "# 3.3.1.3 溶液配制  \n\n1）电泳缓冲液（1L）  \n\nSDS 1.0 g 甘氨酸 14.4 g Tris 3.0 g  \n\n2）电转缓冲液（1L）  \n\n甲醛 200 ml甘氨酸 14.4 gTris 3.0 g  \n\n3）TBST 溶液（ $500\\mathrm{ml}\\cdot$ ）  \n\nNaCl 4.09 g Tris 0.605 g Tween 20 0.5 ml  \n\n4）Western Blot 封闭液： $5\\%$ 脱脂奶粉  \n\n称取 1g 脱脂奶粉加入 20mlTBST 溶液中，置于摇床上摇匀。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 162,
+        "chunk": "# 3.3.2 实验方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 163,
+        "chunk": "# 3.3.2.1 各组细胞的 mTOR、LC3Ⅱ/Ⅰ和 P62 的蛋白水平检测  \n\nOP-BMSCs 的获取、培养与鉴定同章节 2.2。随后，通过 Western Blot 检测细胞中mTOR、LC3Ⅱ/Ⅰ和P62 的蛋白表达水平，评估 3D 打印生物活性界面对细胞的自噬水平的影响，具体步骤如下：  \n\n1）将 OP-BMSCs 以 $1\\times10^{4}/$ 每孔种植在 12 孔板中，OP-BMSCs 不接受任何处理（NC 组）、与微孔支架共培养（pTi 组）、与填充 CEC-PVA-AgNW 水凝胶的微孔支架共培养（ $\\left(\\mathfrak{p}\\mathrm{Ti}\\ @\\mathrm{Gel}\\right.$ 组）和与填充负载雷帕霉素的 CEC-PVA-AgNW 水凝胶的微孔支架共培养（pTi-Rap $\\ @\\mathrm{Gel}$ 组）；  \n\n2）将接受不同处理3 天后的细胞收集并提取蛋白，BCA 法测定总蛋白浓度，Western Blot 检测，具体步骤同章节 2.3.2.2；  \n\n3）使用 Image J 软件计算各条带灰度值，以 $\\upbeta$ -actin 为内参计算各组蛋白的表达量。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 164,
+        "chunk": "# 3.3.2.2 Ad-mCherry-GFP-LC3B 双荧光腺病毒感染细胞  \n\n1）为了分析不同条件下的自噬通量，将 OP-BMSCs 以 $1\\times10^{4}/$ 每孔种植在在6 孔培养板上，并在达到 $50\\%-60\\%$ 的融合时进行感染；  \n\n2）用 PBS 洗涤三次后，用浓度为 10 摩尔的表达 mCherry-GFP-LC3B 融合蛋白的腺病毒（Ad-mCherry-GFP/LC3B）感染细胞。 $24\\mathrm{h}$ 后， $4\\%$ 多聚甲醛固定，PBS 洗涤 3 遍，通过荧光显微镜观察 mCherry 和 GFP 的表达来显示自噬体和自噬溶酶体的变化。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 165,
+        "chunk": "# 3.3.2.3 数据统计分析  \n\n同章节 2.1.2.3。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 166,
+        "chunk": "# 3.3.3 实验结果",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 167,
+        "chunk": "# 3.3.3.1 自噬关键蛋白 mTOR、LC3Ⅱ/Ⅰ和 P62 的表达水平  \n\n为了确认 OP-BMSCs 中自噬相关蛋白在 3D 打印生物活性界面中的变化，我们利用 Western Blot 技术检测了各组细胞中这些的蛋白表达水平。如图 3.8A 显示，NC 组中LC3Ⅱ/Ⅰ比值下降、P62 表达水平增高，表明 OP-BMSCs 的自噬水平低下，而将细胞与 pTi 和pTi@Gel 共培养并不会逆转这种趋势。而通过与具有雷帕霉素缓释功能的 3D 打印生物活性界面共培养，可以发现 OP-BMSCs 的中的mTOR 蛋白表达受到显著抑制（图 3.8B），增加 LC3Ⅱ的形成和提高 LC3Ⅱ/Ⅰ比值（图3.8C），和减少 P62 表达（图3.8D），证明细胞自噬被激活。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 168,
+        "chunk": "# 3.3.3.2 Ad-mCherry-GFP-LC3B 双荧光腺病毒感染细胞观察自噬通量变化  \n\n如图 3.8E 所示，Ad-mCherry-GFP-LC3B 感染细胞后，mCherry 和 GFP 荧光融合形成的黄色斑点表明自噬体（白色箭头），其未与溶酶体融合。绿色荧光蛋白可以在酸性环境中降解，因此红色斑点代表与溶酶体融合的自噬体（红色箭头）。在NC 组和pTi 组中观察到的黄点和红点均较少，表明这两组中的 OP-BMSCs 中自噬活性水平较低。然而，在 pTi-Rap@Gel 组中，细胞中的自噬体形成增多（图3.8F），且自噬溶酶体也相应增多（图 3.8G），表明 3D 打印生物活性界面可以激活OP-BMSCs 的自噬，且保持通畅。  \n\n![](images/a8af6e09b30c5719c2dcc701d290c33565537375221da937c0748234dc0cc747.jpg)  \n图 3.8（A）Western Blot 显影条带及相应分子量， $\\upbeta$ -actin 为内参分子；（B-D）各组蛋白条带灰度值统计结果;（E）Ad-mCherry-GFP-LC3B 双荧光腺病毒感染细胞，白色箭头表示自噬体，红色箭头表示自噬溶酶体；（F）定量统计高倍视野下自噬体数量；（G）定量统计高倍视野下自噬溶酶体数量（ ${}^{*}p<0.05$ ; $**_{p}<0.01\\dot{.}$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 169,
+        "chunk": "# 3.3.4 讨论  \n\nBMSCs 是一种多能干细胞，它具有干细胞的所有共性，即自我更新和多向分化能力。BMSCs 是在哺乳动物的骨髓基质中发现的一种具有分化形成骨、软骨、脂肪、神经及成肌细胞等多种分化潜能的细胞亚群，在骨损伤或者骨科假体植入后的骨再生和骨整合过程中发挥关键作用。基线水平的自噬活性可以维持BMSCs 的干性和分化能力。然而，在骨质疏松状态下，OP-BMSCs 的自噬水平低下、失衡，导致细胞衰老、数量减少和功能受损，可能是骨损伤后成骨能力不94  \n\n足的重要原因。  \n\n在第 2 章中我们已经证明通过超声介导的雷帕霉素递送可以有效激活 OP-BMSCs 的自噬水平，在本章节，我们通过改变药物递送的策略，即将药物通过水凝胶复合到微孔支架中，构建一个可以稳定释放雷帕霉素的 3D 打印生物活性界面。通过 Western Blot 评估自噬关键蛋白 mTOR、LC3Ⅱ/Ⅰ和 P62 的表达和Ad-mCherry-GFP-LC3B 双荧光腺病毒感染细胞观察自噬通量，证明 3D 打印生物活性界面可以有效的激活 OP-BMSCs 的自噬，并保持通畅。然而，相较于 NC 组和 pTi 组，pTi@Gel 组中的自噬体增多（图 3.8F），但是自噬溶酶体并没有相应的增多（图 3.8G），表明单纯的 CEC-PVA-AgNW 水凝胶对 OP-BMSCs 自噬可能具有潜在的影响，但并不能上调其整体的自噬水平，这一点通过对自噬关键蛋白mTOR、LC3Ⅱ/Ⅰ和 P62 的 Western Blot 检测也可证明，即这些蛋白的表达在 NC组、pTi 组和 pTi@Gel 组之间并无显著性差异。这些结果提示单纯的 CEC-PVA-AgNW 水凝胶加入并不会对细胞自噬产生实质性的影响，只有通过稳定释放雷帕霉素的3D 打印生物活性界面才可有效激活 OP-BMSCs 的自噬水平。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 170,
+        "chunk": "# 3.3.5 小结  \n\n通过 Western Blot 评估自噬关键蛋白 mTOR、LC3Ⅱ/Ⅰ和 P62 的表达和 Ad-mCherry-GFP-LC3B 双荧光腺病毒感染细胞观察自噬通量，证明 3D 打印生物活性界面可以有效的激活 OP-BMSCs 的自噬，并保持通畅。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 171,
+        "chunk": "# 3.4 3D 打印生物活性界面调节 OP-BMSCs 功能",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 172,
+        "chunk": "# 3.4.1 实验仪器与材料",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 173,
+        "chunk": "# 3.4.1.1 实验仪器  \n\n<html><body><table><tr><td>仪器名称</td><td>厂家</td></tr><tr><td>超净操作台</td><td>美国Airtech 公司</td></tr><tr><td>细胞培养箱</td><td>美国 Thermo 公司</td></tr><tr><td>光学显微镜</td><td>日本 Olympus 公司</td></tr><tr><td>荧光倒置显微镜</td><td>日本Olympus 公司</td></tr></table></body></html>  \n\n续表：  \n\n\n<html><body><table><tr><td>Transwell 孔板</td><td>美国Corning公司</td></tr><tr><td>PCR板</td><td>瑞士Roche 公司</td></tr><tr><td>LightCycler 480</td><td>瑞士Roche 公司</td></tr><tr><td>分光光度计 NanoDrop 2000</td><td>美国Thermo 公司</td></tr></table></body></html>  \n\n其他仪器同 2.4.1.1。  \n\n3.4.1.2 主要试剂  \n\n\n<html><body><table><tr><td>试剂名称</td><td>厂家</td></tr><tr><td>CCK-8试剂盒</td><td>上海贝博生物科技有限公司</td></tr><tr><td>Calcein-AM/PI染色试剂盒</td><td>上海贝博生物科技有限公司</td></tr><tr><td>多聚甲醛</td><td>上海Aladdin 生化科技有限公司</td></tr><tr><td>Phalloidin-鬼笔环肽染色试剂盒</td><td>北京索莱宝科技有限公司</td></tr><tr><td>油红〇染色液</td><td>北京索莱宝科技有限公司</td></tr><tr><td>总 RNA提取试剂盒</td><td>上海Promega生物产品有限公司</td></tr><tr><td>RNA逆转录试剂盒</td><td>日本 Takara 公司</td></tr><tr><td>SYBR Green Master mix</td><td>瑞士Roche 公司</td></tr><tr><td>qPCR引物</td><td>上海生工生物有限公司</td></tr><tr><td>RT-qPCR试剂盒</td><td>北京全式金生物技术有限公司</td></tr><tr><td>茜素红染液</td><td>北京索莱宝科技有限公司</td></tr><tr><td>氯化十六烷基吡啶</td><td>美国 Sigma-Aldrich 公司</td></tr><tr><td>鼠抗兔Runx-2 抗体</td><td>美国Abcam公司</td></tr><tr><td>鼠抗兔ALP抗体</td><td>美国Abcamy公司</td></tr><tr><td>鼠抗兔OCN抗体</td><td>美国Abcam公司</td></tr><tr><td>鼠抗兔OPN抗体</td><td>美国Abcam公司</td></tr><tr><td>山羊抗兔Cy3荧光二抗</td><td>北京博奥森生物技术有限公司</td></tr><tr><td>山羊抗小鼠 AlexaFluor?488 荧光二抗</td><td>美国 Thermo 公司</td></tr><tr><td></td><td></td></tr><tr><td>DAPI</td><td>北京索莱宝生物科技有限公司</td></tr><tr><td>含 DAPI抗淬灭封片剂</td><td>美国Vector 公司</td></tr></table></body></html>\n\n其他试剂同 2.4.1.2。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 174,
+        "chunk": "# 3.4.1.3 溶液配制",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 175,
+        "chunk": "# 1）免疫荧光封闭液  \n\n在 $20~\\mathrm{ml}$ PBS 中加入 $0.2{\\mathrm{~g~BSA}}$ ，置于水平摇床室温摇 $20~\\mathrm{min}$ ，再加入 200ul 山羊血清封闭液并混匀， $4^{\\circ}\\mathrm{C}$ 保存。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 176,
+        "chunk": "# 3.4.2 实验方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 177,
+        "chunk": "# 3.4.2.1 CCK-8 法测试细胞增殖情况  \n\n将 pTi、pTi@Gel 和 pTi-Rap $@\\mathrm{Gel}$ 预先放置在 24 孔板中，然后将细胞以$1\\times10^{4}/$ 孔的密度种植在孔板中，OP-BMSCs 直接接种在平板中被视为对照 NC 组。在第1，4 和7 天时使用 CCK-8 试剂盒检测细胞增殖情况，具体操作如下：  \n\n1）在预定检测时间点，更换培养基后加入 $10\\%$ 体积的CCK-8 反应液；2）将 24 孔板放入 $37^{\\circ}\\mathrm{C}$ 、 $5\\%\\mathrm{CO}_{2}$ 的孵箱中避光孵育 $2\\mathrm{h}$ ；3）取出 24 孔板，在每个样品中吸取 $100~\\upmu\\mathrm{l}$ 的液体转移到96 孔板；4）转移结束后，迅速将 96 孔板放置在酶标仪内检测各组 OD 值，检测波长为 $450\\ \\mathrm{nm}$ ；5）收集所得数据，进行统计分析。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 178,
+        "chunk": "# 3.4.2.2 Calcein-AM/PI 细胞活死染色  \n\n将 pTi、pTi@Gel 和 pTi-Rap $@\\mathrm{Gel}$ 预先放置在 24 孔板中，然后将细胞以  \n$1\\times10^{4}/$ 孔的密度种植在孔板中，OP-BMSCs 直接接种在平板中被视为对照 NC 组。  \n在第3 天时使用 Calcein-AM/PI 试剂盒检测细胞活死情况，具体操作如下：1）配制染色工作液：Calcein-AM 工作液： $0.5\\operatorname{ml}\\mathrm{C}+10\\operatorname{ul}\\mathrm{A}+4.5\\operatorname{ml}$ 无菌去  \n离子水，PI 工作液： $0.5\\mathrm{ml}\\mathrm{C}+5\\mathrm{ul}\\mathrm{B}+4.5\\mathrm{ml}$ 无菌去离子水。2）细胞固定：吸取培养基， $4\\%$ 多聚甲醛溶液固定 $10~\\mathrm{min}$ ，PBS 清洗 3 次；3）每孔加入 $0.3{\\mathrm{ml}}$ Calcein-AM 工作液避光孵育 $15\\mathrm{min}$ ，随后避光环境下加  \n入PI 工作液 $0.3{\\mathrm{~ml}}$ 继续避光孵育 $5\\mathrm{min}$ ；4）而完成后迅速到暗室中，荧光显微镜下拍照观察。5）收集所得图片，Image J 分析细胞存活率。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 179,
+        "chunk": "# 3.4.2.3 Phalloidin-鬼笔环肽染色  \n\n将 pTi、pTi@Gel 和 pTi-Rap $@\\mathrm{Gel}$ 预先放置在 24 孔板中，然后将细胞以$1\\times10^{4}/$ 孔的密度种植在孔板中，OP-BMSCs 直接接种在平板中被视为对照 NC 组。在第 3 天时使用 Phalloidin-鬼笔环肽试剂盒染色观察细胞形态，具体操作如下：  \n\n1）去除培养液，将细胞用 PBS 清洗3 次， $4\\%$ 多聚甲醛在室温下固定 $10\\mathrm{min}$ ；  \n2）去除固定液，PBS 清洗细胞3 次；  \n3）室温下， $0.5\\%$ 的 triton X-100 对细胞进行透化处理 $5\\mathrm{min}$ ，再次用PBS 清洗细胞3 次；  \n4）吸取 $300~\\upmu\\mathrm{l}$ 配置好的 Phalloidin-鬼笔环肽工作液加入孔板中，室温避光孵育 $30\\mathrm{min}$ ，PBS 清洗 3 次；  \n5）吸取 $300~\\upmu\\mathrm{l}$ 的DAPI 溶液（浓度 $100~\\mathrm{{nM}}$ ）对细胞核复染 $2~\\mathrm{min}$ ；  \n6）在荧光显微镜下进行观察并拍照，Image J 分析细胞荧光强度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 180,
+        "chunk": "# 3.4.2.4 茜素红染色  \n\n将细胞以 $1\\times10^{4}/$ 孔的密度种植在各组 24 孔板中，待细胞贴壁后换液，使用成骨诱导培养基，在成骨诱导后的第14 天和第21 天后进行茜素红染色，具体步骤如下：  \n\n1）去除培养基， $4\\%$ 多聚甲醛固定 $15\\mathrm{min}$ 后去除固定液，PBS 清洗3 次；2）将 PBS 完全吸净后，加入 $2\\%$ 茜素红 S 染色液 $0.3\\mathrm{\\ml}$ ，染色 $15~\\mathrm{min}$ ，去除染色液，PBS 洗涤 3 次；3）然后将染色好的细胞样品拍照，并放置在显微镜下进行观察；4）为半定量分析钙结节，孔板中加入氯化十六烷基吡啶 $0.6\\ \\mathrm{ml}$ ，并将孔板置于摇床上摇晃过夜，充分溶解沉积的钙结节。吸取孔中上清液转移到 96 孔板中，使用酶标仪在 $570\\mathrm{nm}$ 波长评估各组样品的吸光度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 181,
+        "chunk": "# 3.4.2.5 RT-qPCR  \n\n将细胞以 $1\\times10^{4}/$ 孔的密度种植在各组 24 孔板中，待细胞贴壁后，更换成骨诱导培养基，在成骨诱导 14 天和21 天后，通过 1）总RNA 的提取；2）总RNA浓度测量；3）逆转录合成 cDNA；及 4）RT-qPCR 分析细胞中 Runx-2、ALP、OCN 和 OPN 的基因表达情况，具体步骤同章节 2.4.2.7。采用 $2^{-\\Delta\\Delta\\mathrm{Ct}}$ 计算方法，98  \n\n各引物信息见表2.1，以 $\\upbeta\\cdot$ -actin 为内参。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 182,
+        "chunk": "# 3.4.2.6 油红 O 染色  \n\n将细胞以 $1\\times10^{4}/$ 孔的密度种植在各组 24 孔板中，待细胞贴壁后，更换成脂诱导培养基培养 14 和 21 天，进行油红 O 染色观察细胞内成脂情况，具体步骤如下：  \n\n1）待细胞贴壁后更换成脂诱导培养基 A 液进行培养，3 天后换用成脂诱导培养基B 液进行培养 $24\\mathrm{h}$ ，如此A、B 培养基交替使用培养至第 14 和21 天；2） $10\\%$ 多聚甲醛固定细胞 $10\\mathrm{min}$ ，弃去固定液，PBS 洗涤，加入油红 O 染色液 $400~\\upmu\\mathrm{l}$ 孵育 $30~\\mathrm{min}$ ，移除油红 O 染液，并用 PBS 洗涤 2 次，光镜下观察；3）使用甲醇洗脱染色 $30\\mathrm{min}$ ，并使用酶标仪在 $510\\mathrm{nm}$ 处测量吸光度进行定量。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 183,
+        "chunk": "# 3.4.2.7 数据统计分析  \n\n同章节 2.1.2.3。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 184,
+        "chunk": "# 3.4.3 结果",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 185,
+        "chunk": "# 3.4.3.1 细胞增殖与活性  \n\n为了探究 3D 打印生物活性界面缓释雷帕霉素对 OP-BMSCs 增殖和存活的影响，我们使用 CCK-8 法、Calcein-AM/P 染色和鬼笔环肽染色对各组中的细胞情况进行分析。图 3.9A 所示，在培养到第 7 天时，pTi-Rap $@\\mathrm{Gel}$ 组中的 OP-BMSCs 增殖速率显著高于 $\\mathtt{p T i}\\ @\\mathbf{Gel}$ 组（ $\\scriptstyle\\cdot\\mathtt{p}^{<0.05)}$ ）、pTi 组（ $\\cdot\\mathrm{p}{<}0.05$ ）和 NC 组（ $_{\\cdot\\mathrm{{p}<0.01}})$ ）。随后，Calcein-AM/PI 染色对活死细胞的标记显示，与 pTi-Rap@Gel组相比，NC 组、pTi 组和 $\\mathtt{p T i}\\ @\\mathtt{G e l}$ 组中可见更多红染的死细胞（图 3.9B）。如图3.9C 所示，对 Calcein-AM/PI 染色的定量分析显示 pTi-Rap@Gel 组中的细胞存活率显著高于其余 3 组（ $\\cdot\\mathrm{p}{<}0.05\\$ ）。Phalloidin-鬼笔环肽染色显示与 NC 组、pTi 组和 $\\mathsf{p T i}\\ @\\mathsf{G e l}$ 组相比，pTi-Rap@Gel 组中的 OP-BMSCs 显示出更好的铺展状态和更多的板足延伸，细胞骨架沿长轴排列并具有更强的荧光强度（图 3.9D、E）。  \n\n![](images/df99f7a43ed5fb38563d07c653707611b35ab6efe21ce4345bc6506767df8721.jpg)  \n\n图 3.9（A）CCK-8 法检测细胞增殖情况；（B）Calcein-AM/PI 染色标记活死细胞；（C）定量分析细胞存活率；（D）Phalloidin-鬼笔环肽染色图像；（E）定量分析Phalloidin-鬼笔环肽染色荧光强度（ $^{*}p<0.05$ ; $^{**}p<0.01\\$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 186,
+        "chunk": "# 3.4.3.2 细胞成骨分化  \n\n为研究 3D 打印生物活性界面对 OP-BMSCs 成骨分化能力的影响，我们首先通过茜素红染色评估细胞中钙结节沉积情况，如图 3.10A 所示，在第 14 天时NC组、pTi 组和 pTi@Gel 组中的钙沉积均较少，但是 pTi-Rap@Gel 组已有肉眼可见明显的细胞矿化基质形成，这种差异在第 21 天时仍明显存在。此外，如图 3.10B所示，通过氯化十六烷基吡啶洗脱平板上和支架微孔内着色的钙结节，通过半定量分析进一步验证相比于 NC 组、pTi 组和 $\\mathsf{p T i}\\ @\\mathsf{G e l}$ 组，该 3D 打印生物活性界面可以显著促进OP-BMSCs 的矿化形成（ $\\cdot\\mathrm{\\ttp}{<}0.05)$ ）。  \n\n随后，我们通过 PCR 实验分析各组细胞样品中成骨相关基因的表达水平。如图 3.10C、D，早期成骨标志物 ALP 和 Runx-2 在 pTi-Rap $@\\mathrm{Gel}$ 组中的表达无论是在第 14 天还是第 21 天都显著高于其余 3 组（ $\\mathsf{p}{<}0.05\\rangle$ ）。而晚期成骨标志物OCN 和 OPN 的表达情况略有差异。如图 3.10E，在 pTi-Rap@Gel 组中 OCN 的表达至第21 天时才显著高于其余 3 组（ $(\\mathtt{p}{<}0.05)$ ）；而 OPN 的表达在第 14 天时相较于NC 组上调（ $(\\mathtt{p}{<}0.05)$ ），至第21 天时才显著高于其余3 组（ $\\cdot\\mathrm{p}{<}0.05\\$ ）（图3.10F）。  \n\n由此可见，3D 打印生物活性界面可以通过促进钙结节沉积和上调成骨相关基因的表达，显著激活 OP-BMSCs 成骨分化能力。  \n\n![](images/90577c679c13417657a6ddbc17c1f44cb479199be78eaccac2ed383006a4d1d6.jpg)  \n图3.10（A）茜素红染色图像；（B）茜素红染色半定量分析；(C-F) PCR 检测成骨相关基因 ALP、Runx-2、OCN 和 OPN 的表达（ $^{*}p<0.05)$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 187,
+        "chunk": "# 3.4.3.4 细胞成脂分化  \n\n对细胞进行成脂诱导分化 14 和 21 天后，进行油红 O 染色观察 OP-BMSCs成脂分化的趋势（图 3.11A）。如图3.11B 所示，在第 14 天时，NC 组、pTi 组和$\\mathtt{p T i}\\ @\\mathrm{Gel}$ 组中的脂滴数量增加，显著高于 pTi-Rap $@\\mathrm{Gel}$ 组（ $\\cdot\\mathtt{p}^{<0.05)}$ ）；在第 21 天时这种差异更显著（ $\\scriptstyle({\\mathfrak{p}}<0.01)$ ）。这些结果表明 3D 打印生物活性界面可以显著地抑制 OP-BMSCs 成脂分化。  \n\n![](images/b40cae687e45b11481f292f1e2c117df964aa6dd4bad5cc27fb2f5691e52529c.jpg)  \n图3.11（A）油红 O 染色图像；（B）油红O 染色定量分析（ $^{*}p<0.05$ ; $^{**}p<0.01$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 188,
+        "chunk": "# 3.4.4 讨论  \n\n既往研究及本研究第二章部分证明在骨质疏松症骨髓中的OP-BMSCs 增殖、活性和迁移能力受到抑制，细胞功能衰退，成骨分化能力不足而成脂分化潜能增加。细胞活力和功能的衰退延缓了干细胞在骨损伤部位的募集和成骨分化，从而导致骨修复受损 [209]。且这些现象被证明与 OP-BMSCs 的低下的自噬水平有关[210, 211]。在本论文的第二章，我们设计了一种经皮超声介导的雷帕霉素递送策略，可以有效的激活 OP-BMSCs 自噬活性，改善成骨微环境。为了开发一种更便捷的可替代策略，我们构建一种了由 3D 打印金属微孔假体和负载雷帕霉素的水凝胶构成的“3D 打印生物活性界面”作为一站式植入物，并成功地通过缓释雷帕霉素上调 OP-BMSCs 的自噬水平。在本章节，我们验证了被激活自噬之后 OP-BMSCs 的细胞增殖、活性和多向分化潜能。  \n\n随着培养时间的延长，OP-BMSCs 在 NC 组、pTi 组和 pTi@Gel 组中的增殖较缓慢，而与3D 打印生物活性界面共培养的 OP-BMSCs 增殖能力显著提升，且具有更好的细胞存活率和更具铺展性的细胞骨架形态。除了促进细胞增殖和活性外，更重要的是，3D 打印生物活性界面可以通过促进钙结节沉积和上调成骨相关基因（ALP、Runx-2、OCN 和 OPN）的表达，显著激活 OP-BMSCs 成骨分化能力，且同时抑制 OP-BMSCs 成脂分化。BMSCs 被认为是骨损伤或者骨科假体植入后参与骨修复的成骨细胞的主要来源，BMSCs 的成骨分化是假体界面骨整合过程中的关键性事件。然而，骨质疏松微环境中的 BMSCs 数量不足，部分丧失了自我更新和成骨分化能力。此外，在雌激素缺乏的骨质疏松微环境中，OP-BMSCs 具有潜在分化为脂肪细胞而不是成骨细胞的趋势，会进一步导致骨丢失和脂肪积聚 [217, 218]。因此，我们构建的 3D 打印生物活性界面成功地调节 OP-BMSCs 成骨-成脂分化的平衡，为促进骨质疏松症患者假体植入后增强界面骨整合提供了潜在的替代策略。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 189,
+        "chunk": "# 3.4.5 小结  \n\n具有雷帕霉素缓释功能的3D 打印生物活性界面可以有效地提高OP-BMSCs的增殖、存活和成骨分化能力，且抑制其成脂肪分化的趋势。这种 3D 打印生物活性界面的构建策略，通过恢复衰老 OP-BMSCs 的细胞功能，有望为骨质疏松症患者假体植入后界面骨整合提供替代策略。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 190,
+        "chunk": "# 3.5 3D 打印生物活性界面促进骨质疏松状态下假体界面骨整合",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 191,
+        "chunk": "# 3.5.1 实验仪器与材料  \n\n3.5.1.1 实验仪器   \n\n\n<html><body><table><tr><td>仪器名称</td><td>厂家</td></tr><tr><td>Micro-CT</td><td>比利时 Bruker 公司</td></tr><tr><td>硬组织切片机</td><td>德国Leica 公司</td></tr><tr><td>冰冻切片机</td><td>德国Leica公司</td></tr><tr><td>光学显微镜</td><td>日本 Olympus 公司</td></tr><tr><td>荧光倒置显微镜</td><td>日本Olympus 公司</td></tr><tr><td>万能力学测试机</td><td>日本 Shimadzu 公司</td></tr></table></body></html>\n\n其他仪器同 2.5.1.1。  \n\n3.5.1.2 主要试剂  \n\n\n<html><body><table><tr><td>试剂名称</td><td>厂家</td></tr><tr><td>碘伏毒液</td><td>山东利尔康医疗科技有限公司</td></tr><tr><td>兽用青霉素</td><td>华北制药集团有限责任公司</td></tr><tr><td>戊巴比妥钠</td><td>北京索莱宝科技有限公司</td></tr><tr><td>多聚甲醛</td><td>上海Aladdin生化科技有限公司</td></tr><tr><td>苏木精和伊红（H&E）染料</td><td>美国Thermo 公司</td></tr><tr><td>马松染料</td><td>美国Thermo 公司</td></tr><tr><td>钙黄绿素</td><td>上海源叶生物科技有限公司</td></tr><tr><td>小鼠抗Runx-2抗体</td><td>美国Abcam公司</td></tr><tr><td>兔抗 ALP 抗体</td><td>美国Abcamy公司</td></tr><tr><td>小鼠抗OCN抗体</td><td>美国Abcam公司</td></tr><tr><td>兔抗OPN抗体</td><td>美国Abcam公司</td></tr><tr><td>山羊抗兔Cy3荧光二抗</td><td>北京博奥森生物技术有限公司</td></tr><tr><td>山羊抗小鼠 AlexaFluor?488 荧光二抗</td><td>美国Thermo 公司</td></tr><tr><td>DAPI</td><td>北京索莱宝生物科技有限公司</td></tr></table></body></html>  \n\n续表：  \n\n\n<html><body><table><tr><td>含DAPI抗淬灭封片剂</td><td>美国Vector公司</td></tr><tr><td>其他试剂同2.5.1.2。</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 192,
+        "chunk": "# 3.5.2 实验方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 193,
+        "chunk": "# 3.5.2.1 骨质疏松兔股骨远端假体植入和组织获取  \n\n使用双侧卵巢切除术制备骨质疏松动物模型，同章节 2.5.2.1。卵巢切除术后10 个月骨质疏松模型建立，植入 3 种不同的 3D 打印微孔假体至兔左侧股骨远端外侧髁，即 3D 打印微孔支架（pTi 组）、填充 CEC-PVA-AgNW 水凝胶的 3D 打印微孔支架（ $\\left({\\mathfrak{p}}\\mathrm{Ti}@\\mathrm{Gel}\\right.$ 组）和填充负载雷帕霉素的 CEC-PVA-AgNW 水凝胶的3D打印微孔支架（pTi-Rap@Gel 组）。具体假体植入手术操作步骤同章节 2.5.2.1。动物实验共分为 3 个组，每组 8 只。所有动物在处死前第 14 天和第 4 天肌肉注射钙黄绿素（ $(8~\\mathrm{mg/kg})$ ），以检测骨形成过程中的矿物质沉积率。术后第 12 周，过量麻醉法处死实验动物，收集左侧股骨样本，并将其固定在 $4\\%$ 多聚甲醛中或储存在- ${\\cdot}80^{\\circ}\\mathrm{C}$ 冰箱中，用于进一步研究。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 194,
+        "chunk": "# 3.5.2.2 H&E 染色  \n\n收集动物内脏，进行H&E 染色以评估3D 打印生物活性界面植入的安全性。具体步骤同章节2.5.2.2。制备好切片行H&E 染色后显微镜镜检，图像采集分析。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 195,
+        "chunk": "# 3.5.2.3 Micro-CT 评估骨长入  \n\n使用Micro-CT 对收集的股骨远端组织进行扫描，工作参数设置为电压：90V，电流： $114~\\upmu\\mathrm{A}$ ，扫描分辨率： $18~{\\upmu\\mathrm{m}}$ ，并选用 $\\mathsf{A l/C u}$ 滤片以避免金属伪影。具体步骤同章节 2.5.2.3。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 196,
+        "chunk": "# 3.5.2.4 硬组织切片评估骨整合效果  \n\n收集股骨远端样本，制备未脱钙硬组织切片，马松染色观察再生骨组织与假体微孔界面整合情况，具体步骤如下：  \n\n（1）样本固定脱水及硬切片制备同章节 2.5.2.4；  \n\n（2）有机溶剂脱去有机树脂，无菌水冲洗，Weigert 氏苏木素染液染 $20\\mathrm{min}$ ，并流水冲洗 $10\\mathrm{min}$ ；使用Masson 代丽春红-复红染料染色 $10\\mathrm{min}$ ；104  \n\n（3）滤纸吸干染液，将切片置于 $0.5\\%$ 冰醋酸分色处理 $1~\\mathrm{min}$ ，蒸馏水洗涤后用亮绿-冰醋酸染色 $5\\mathrm{min}$ ；  \n\n（4）放入二甲苯中两次，其浓度为 $10\\%$ ，透明后置于载玻片上用加拿大胶封固。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 197,
+        "chunk": "# 3.5.2.5 力学测试评估界面骨整合与周围骨质情况  \n\n1）支架推出实验评估假体-骨界面的整合强度，具体步骤同章节 2.5.2.5 中1）。  \n\n2）三点弯曲实验评估周围骨质强度，具体步骤同 2.5.2.5 中2）。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 198,
+        "chunk": "# 3.5.2.6 界面周围骨质中 mTOR、LC3Ⅱ/Ⅰ和 P62 的蛋白水平检测  \n\n在力学测试推出支架后，收集假体界面周围骨质，通过 Western Blot 检测骨质中mTOR、LC3Ⅱ/Ⅰ和P62 的蛋白水平，以评估假体界面周围的自噬情况。具体步骤同章节 2.5.2.6。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 199,
+        "chunk": "# 3.5.2.7 界面周围骨质中成骨相关基因检测  \n\n在力学测试推出支架后，收集假体界面周围骨质，通过 RT-qPCR 法检测骨质中成骨相关基因 ALP、Runx-2、OCN 和 OPN 的表达水平。具体步骤同章节2.5.2.7。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 200,
+        "chunk": "# 3.5.2.8 界面周围骨质中成骨相关蛋白免疫荧光染色  \n\n在力学测试推出支架后，收集股骨远端样本，通过免疫荧光染色检测骨质中成骨相关蛋白 ALP、Runx-2、OCN 和 OPN 的表达水平。具体步骤同章节 2.5.2.8。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 201,
+        "chunk": "# 3.5.2.9 数据统计分析  \n\n同章节 2.1.2.3。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 202,
+        "chunk": "# 3.5.3 结果",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 203,
+        "chunk": "# 3.5.3.1 3D 打印生物活性界面植入体内安全性分析  \n\n为了探究3D 打印生物活性界面植入体内的安全性，我们收集动物主要脏器，包括心、肝、脾、肺和肾，进行 H&E 染色。钛合金材料被认为是骨科的理想材料，具有较好的生物相容性，已被广泛应用于临床。如图3.12 显示，与微孔钛合金 pTi 组相比，植入 3D 打印生物活性界面后动物主要脏器的组织形态学结构并未发生显著改变，均显示保持正常的组织形态，表明 3D 打印生物活性界面在体内具有良好的安全性。  \n\n![](images/6783f1c344232a4c6da3a18d1046ed2387b2067f2295c09d814faada8c957da1.jpg)  \n图3.12 主要脏器，包括心、肝、脾、肺和肾的 H&E 染色。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 204,
+        "chunk": "# 3.5.3.2 影像学评估假体界面骨整合效果  \n\n图 3.13A 所示，将 Micro-CT 所得图像进行 3D 重建可见与 pTi 组和 $\\mathsf{p T i}\\ @\\mathsf{G e l}$ 组相比，pTi-Rap@Gel 组中假体表面和孔隙中具有更多的骨组织（黄色）形成。将假体所在的圆柱形区域设为感兴趣区域，进一步的骨形态计量分析显示pTi组、$\\mathsf{p T i}\\ @\\mathsf{G e l}$ 组和 pTi-Rap@Gel 组的 BV/TV 值分别为 $14.1{\\pm}3.6\\%$ 、 $14.6{\\pm}3.3\\%$ 和$19.4{\\pm}2.0\\%$ 。与 pTi 组和 $\\mathsf{p T i}\\ @\\mathsf{G e l}$ 组相比，pTi-Rap $@\\mathrm{Gel}$ 组在假体植入后 12 周时表现出明显增加的骨体积分数（BV/TV， $\\mathsf{p}{<}0.05\\AA)$ ）、骨小梁数量（Tb.N， $\\mathsf{p}{<}0.01$ ）和骨小梁厚度（Tb.Th， $\\mathsf{p}{<}0.05\\AA)$ ），并降低了骨小梁分离度（Tb.Sp， $\\scriptstyle\\mathbf{p}<0.05.$ ）（图3.13B-E）。这些结果表明，3D 打印生物活性界面可以有效促进骨质疏松状态下的微孔假体表面的骨形成与长入。  \n\n![](images/f7fa34d853ac1943d0362a60a366887f9311c188def8d793ac745ba17d9ef440.jpg)  \n\n图3.13（A）Micro-CT 3D 重建图像，白色为支架，黄色为骨组织；（B-E）根据Micro-CT 结果定量分析 BV/TV，Tb.Th，Tb.N 和 Tb.Sp 参数（ ${\\displaystyle:*_{p}<0.05}$ ; $\\ast\\ast_{p}<$ 0.01）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 205,
+        "chunk": "# 3.5.3.3 组织学评估假体界面骨形成与整合效果  \n\n为了观察周围骨组织与假体界面的骨形成与整合效率，我们制备不脱钙硬组织切片，并在荧光显微镜下直接观察钙黄绿素荧光双标图像（图3.14A）。动态组织形态计量分析表明，与 pTi 组和 pTi@Gel 组相比，pTi-Rap@Gel 组加快了骨缺损区域的新骨形成速率，如 MAR，MS/BS，BFR/BS 显著增加（图 3.14B-D）。随后将硬组织切片进行马松染色观察骨整合情况。如图 3.14E 所示，pTi 组和pTi@Gel 组的骨再生有限，只有少量骨组织结合到假体界面上；而在 pTi-Rap@Gel 组中可见再生骨与假体界面形成较为致密的结合，并长入表面微孔结构内部。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 206,
+        "chunk": "# 3.5.3.4 力学评估假体界面骨整合效果  \n\n为了进一步验证假体界面和宿主骨之间的骨整合强度，我们进行了生物力学测试来记录支架推出时的峰值力。pTi 组、pTi@Gel 组和 pTi-Rap@Gel 组的支架推出力峰值分别为 $209.58{\\pm}31.74\\mathrm{N}.234.86{\\pm}52.26\\mathrm{N}$ 和 $417.07{\\scriptstyle\\pm58.95\\mathrm{N}}($ （图 3.14F）。力学测试结果与影像学和组织学评估结果一致，即新骨生成量和骨长入与假体界面骨整合强度成正比。这些结果表明，3D 打印生物活性界面有利于促进在骨质疏松状态下的骨形成和骨整合，从而减少假体植入后松动和移位等术后并发症的发生。  \n\n![](images/61fec0a3d05c40766486882e94d539898ed6ffb77034f0d84552415ceaeeed57.jpg)  \n\n图3.14（A）不脱钙硬组织切片观察钙黄绿素荧光双标；（B-D）通过钙黄绿素荧光双标对MAR、MS/BS 和BFR/BS 进行定量统计；（E）马松染色观察假体界面骨长入与整合（黑色区域表示假体，蓝色区域表示骨组织）；（F）植入 12 周后通过生物力学测试评估骨整合（ $^{*}p<0.05$ ; $^{**}p<0.01$ ; ${***p}<0.001\\rangle$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 207,
+        "chunk": "# 3.5.3.5 假体界面周围骨量与骨质情况分析  \n\n除了假体界面的骨整合，假体界面周围的骨量与骨质的提高对于术后关节假体使用寿命也是至关重要的。通过 Micro-CT 扫描获得的股骨远端代表性横断面图像表明，与pTi 组和 $\\mathsf{p T i}\\ @\\mathsf{G e l}$ 组相比，pTi-Rap@Gel 组的假体远端具有更致密的骨小梁结构，而假体近端具有更厚的皮质骨（图 3.15A）。如图3.15B 所示，选取股骨远端 $2\\ \\mathrm{cm}$ 区域（包含假体）为感兴趣区域，pTi 组、 $\\mathsf{p T i}\\ @\\mathsf{G e l}$ 组和 pTi-Rap@Gel 组的 BV/TV 值分别为 $24.93{\\scriptstyle\\pm4.22\\%}$ 、 $27.33{\\scriptstyle\\pm4.16\\%}$ 和 $36.12{\\scriptstyle\\pm6.73\\%}$ 。此外，对骨小梁微观结构的分析同样显示相比于pTi 组和 $\\mathsf{p T i}\\ @\\mathsf{G e l}$ 组，pTi-Rap@Gel组假体界面周围松质骨的和 Tb.N（图 3.15C）和 Tb.Th（图 3.15D）显著增加，Tb.Sp（图 3.15E）显著降低。  \n\n另外选取假体近端水平及近处 1 cm 区域为感兴趣区域分析皮质骨厚度（Ct.Th）和皮质骨面积（Ct.Ar）。如图 3.15F 所示，pTi-Rap@Gel 组的 Ct.Th 和Ct.Ar 参数明显优于 pTi 组和 $\\mathtt{p T i}\\ @\\mathtt{G e l}$ 组（ $\\cdot\\mathtt{p}^{<0.01}\\$ ）。随后，三点弯曲实验被用于进一步验证假体周围骨质的抗折强度（图 3.15G）。在 pTi-Rap@Gel 组的远端股骨中观察到明显更大的最大失效载荷，其约为 pTi 组和 $\\mathsf{p T i}\\ @\\mathsf{G e l}$ 组的 1.33 倍和1.25 倍。这些结果显示具有雷帕霉素缓释功能的 3D 打印生物活性界面可显著改善假体界面周围骨量和骨质，并有望减少在骨质疏松模型中假体植入后假体周围骨折的发生率。  \n\n![](images/d340da1b93c69d01a94d4255608a6dde4cb368a1bbb412eb86a6749b66f118c2.jpg)  \n第 3 章  功能化水凝胶介导的雷帕霉素局部递送通过激活自噬和调控成骨微环境促进骨质疏松状态下假体界面骨整合  \n图3.15（A）Micro-CT 观察假体界面远段和近端的骨量和骨质情况；（B-E）股骨远端 $2\\ \\mathrm{cm}$ 区域（包含假体）的骨形态学参数分析，包括 BV/TV、Tb.Th、Tb.N和 Tb.Sp；（F）假体近端水平及近处 1 cm 区域皮质骨参数分析，包括 Ct.Th 和Ct.Ar；（G）生物力学三点弯曲实验分析该节段骨的抗折强度（ $^{\\cdot}\\ast_{p}<0.05$ ; $^{**}p<$ 0.01）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 208,
+        "chunk": "# 3.5.3.6 假体界面周围自噬激活情况  \n\n为了研究 3D 打印生物活性界面增强骨质疏松状态下骨整合的体内机制，我们收集了假体界面表面和孔隙中的骨组织，通过 Western Blot 检测自噬通路关键蛋白以评估局部骨组织中的自噬水平（图 3.16A）。结果表明，3D 打印生物活性界面可显著抑制假体周围组织中mTOR 表达（图3.16B），激活LC3 II/I（图3.16C），并清除累积的 P62 蛋白（图 3.16D），从而上调骨质疏松状态下假体界面周围的自噬活性。  \n\n![](images/be8bb2a8d4f23f9d8256ce96df927528c91546c6561ae82014d4baa2025e5160.jpg)  \n图 3.16（A）Western Blot 显影条带及相应分子量， $\\upbeta$ -actin 为内参分子；（B-D）各组蛋白条带灰度值统计结果（ $^{*}p<0.05$ ; $**_{p}<0.01\\dot{.}$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 209,
+        "chunk": "# 3.5.3.7 假体界面周围成骨标志物表达分析  \n\n收集 3D 打印假体表面、孔隙中以及邻近假体界面的骨组织，通过 RT-qPCR检测和免疫荧光染色以分析局部微环境中的成骨标记物表达情况。如图3.17A 所示，RT-qPCR 分析显示与 pTi 组和 $\\mathtt{p T i}\\ @\\mathtt{G e l}$ 组相比，pTi-Rap $@\\mathrm{Gel}$ 组中的成骨相关基因 Runx-2、ALP、OCN 和 OPN 的表达水平显著提高（ $\\cdot\\mathrm{\\ttp}^{<0.05)}$ ）。随后，对脱钙骨组织进行免疫荧光染色以评估周围骨组织中成骨相关蛋白的表达（图3.17B）。如图 3.17C 所示，荧光强度的定量分析显示，相较于 pTi 组和 $\\mathsf{p T i}\\ @\\mathsf{G e l}$ 组，植入 3D 打印生物活性界面后显著增加了假体界面周围Runx-2、ALP、OCN和 OPN 的表达（ $_{(\\mathrm{p}<0.01)}$ ）。这些结果显示 3D 打印生物活性界面能够显著促进骨质疏松状态下界面周围骨组织中成骨标记物的表达。  \n\n![](images/2f69ee499e19c0550fbd2c491932f7aff27ea6f87c42834ea11f47a53444a50f.jpg)  \n图 3.17（A）RT-qPCR 分析成骨相关基因 Runx-2、ALP、OCN 和 OPN 在假体界面周围骨组织中的表达情况；（B）假体界面周围骨组织的 Runx-2、ALP、OCN和OPN 免疫荧光染色；（C）定量分析成骨相关蛋白的荧光强度（ $^{*}p<0.05$ ; $\\ast\\ast_{p}$ $\\phantom{+}<0.01\\$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 210,
+        "chunk": "# 3.5.4 讨论  \n\n接受关节置换术的患者常常伴随有骨质疏松症，这类患者骨再生能力受限，常导致假体界面骨整合不足，以及周围骨量低、骨质差，面临植入术后假体移位和松动以及假体周围骨折等灾难性并发症的风险。考虑到 OP-BMSCs 低下的自噬水平可能是骨质疏松状态下低下的骨再生与骨整合不足的重要原因，使用经典的自噬激活剂——雷帕霉素来促进假体界面骨整合是一个可利用的方法。其中，为了避免雷帕霉素的全身副作用，通过局部给药的策略调节 OP-BMSCs 的自噬水平，恢复其衰退的细胞功能，促进其成骨分化和与界面骨整合，是一种潜在的替代方法。本论文在第二章部分设计了一种经皮超声介导的雷帕霉素递送策略，可以有效的激活 OP-BMSCs 自噬活性，改善成骨微环境，成功地促进了假体界面骨整合。但是，通过特制的超声电导仪频繁的经皮给药，可能导致患者依从性差，且增加了经济和时间负担，在做到个体化局部给药的同时也带来了诸多不便。因此，在本章节我们构建一种了由 3D 打印金属微孔假体和负载雷帕霉素的水凝胶构成的“3D 打印生物活性界面”作为一站式植入物，并成功地通过缓释雷帕霉111  \n\n素上调 OP-BMSCs 的自噬水平，并利于其在金属微孔表面的增殖和存活，激发其成骨分化潜能而抑制成脂分化，有望成为促进骨质疏松状态佳假体界面骨整合的新型植入物。  \n\n在动物体内骨整合研究中，我们首先观察了 3D 打印生物活性界面在体内的安全性，即在植入12 周后对主要内脏进行H&E 染色。钛合金材料被认为是骨科的理想材料，具有较好的生物相容性，已被广泛应用于临床。与微孔钛合金 pTi组相比，植入3D 打印生物活性界面后动物的心、肝、脾、肺和肾的微观形态结构并未发生改变，均与 pTi 组一样显示保持正常的组织学形态，表明 3D 打印生物活性界面在体内具有良好的安全性，这为新型假体界面的体内应用提供了初步的理论依据。  \n\n随后，我们在骨质疏松动物模型体内验证该 3D 打印生物活性界面的骨整合效果。Micro-CT 和组织学切片结果显示各组假体表面微孔中均有一定骨组织长入，表明3D 打印微孔假体这种与缺损高度匹配、具有互联多孔结构的植入物确能提供适当的初始稳定性和诱导骨长入。但是，在骨质疏松状态下，pTi 组和pTi@Gel 组未负载自噬激活剂——雷帕霉素，获得的骨长入以及力学结合强度明显不足，难以提供长期可靠的稳定性。我们在构建的 3D 打印生物活性界面中引入雷帕霉素，获得一个局部药物缓释的效果，通过激活 OP-BMSCs 自噬，调节成骨微环境，以期促进骨质疏松状态下的假体界面骨整合。随后，我们通过一系列检测，包括影像学、组织学和生物力学分析，可以直观地观察到假体界面上新生骨组织的长入，新生骨与假体界面结合牢固，显示了优越的骨整合效果。这些结果表明，3D 打印生物活性界面可以显著促进骨质疏松状态下的假体周围的骨形成和界面骨整合，从而减少假体植入后松动和移位等术后并发症的发生。此外，除了假体松动和移位，假体周围骨折也是假体植入后一个重要的术后并发症，通常与关节置换术后假体周围的骨量和骨质情况有关 [232, 233]。我们通过 Micro-CT评估和生物力学测试分析了假体界面周围的骨量和骨质，以及骨组织的抗折强度，以预测假体周围骨折发生的概率。结果显示，3D 打印生物活性界面植入后可以改善整个股骨远端的骨微观结构，增加局部的骨量，以及增加假体近端皮质骨的厚度和面积，同时显著提高假体周围骨组织的抗折强度，从而减少假体植入后假体周围骨折等术后并发症的发生。  \n\n为了进一步探究3D 打印生物活性界面植入后在局部促进骨再生与骨整合的机制，我们对假体界面骨组织中的自噬关键蛋白进行分析。结果显示 3D 打印生物活性界面植入后可以显著抑制 mTOR 蛋白的表达，（自噬体）膜型蛋白 LC3-II比例升高，自噬降解蛋白 P62 降低，表明局部微环境中自噬启动，且保持通畅，可有效清除代谢废物。这与既往研究结果相一致，即雷帕霉素可以通过抑制雷帕霉素敏感的 mTOR 靶点来激活细胞自噬 [234]。此外，雷帕霉素通过抑制 mTOR靶点激活干细胞自噬后，可通过激活 BMP/Smad 信号，诱导干细胞向成骨细胞分化 [234]。从而增加骨密度、骨体积百分比、骨小梁数量目和骨小梁厚度，可以有效减轻骨质疏松模型的骨丢失 [45, 196]。因此，在证明 3D 打印生物活性界面可激活 OP-BMSCs 自噬后，我们从基因和蛋白层面进一步观察界面周围的成骨微环境中成骨相关标志物 Runx-2、ALP、OCN 和 OPN 的表达。结果显示 3D 打印生物活性界面显著上调一系列成骨相关标志物的表达，极大地改善了假体界面周围的成骨微环境，促进细胞成骨分化、诱导骨长入，从而获得稳定的界面骨整合和改善界面周围骨微观结构，为减少假体置换术后松动、移位和假体周围骨折等并发症的发生提供基础。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 211,
+        "chunk": "# 3.5.5 小结  \n\n3D 打印生物活性界面具有良好的生物安全性，可以通过局部缓释雷帕霉素有效的激活假体界面周围微环境中的自噬活性，改善成骨微环境，从而获得良好的界面骨整合和周围骨量、骨质提升，有效的减少假体置换术后松动、移位和假体周围骨折等并发症的发生。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 212,
+        "chunk": "# 3.6 3D 打印生物活性界面促进感染状态下假体界面骨整合",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 213,
+        "chunk": "# 3.6.1 实验仪器与材料",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 214,
+        "chunk": "# 3.6.1.1 实验仪器  \n\n<html><body><table><tr><td>仪器名称</td><td>厂家</td></tr><tr><td>Micro-CT</td><td>比利时Bruker 公司</td></tr><tr><td>硬组织切片机</td><td>德国Leica公司</td></tr></table></body></html>  \n\n续表：  \n\n\n<html><body><table><tr><td>冰冻切片机</td><td>德国Leica公司</td></tr><tr><td>光学显微镜</td><td>日本Olympus 公司</td></tr><tr><td>荧光倒置显微镜</td><td>日本Olympus 公司</td></tr><tr><td>万能力学测试机</td><td>日本Shimadzu公司</td></tr><tr><td>细胞计数板</td><td>日本WC2公司</td></tr></table></body></html>\n\n其他仪器同 2.5.1.1。  \n\n3.6.1.2 主要试剂  \n\n\n<html><body><table><tr><td>试剂名称</td><td>厂家</td></tr><tr><td>碘伏毒液</td><td>山东利尔康医疗科技有限公司</td></tr><tr><td>兽用青霉素</td><td>华北制药集团有限责任公司</td></tr><tr><td>戊巴比妥钠</td><td>北京索莱宝科技有限公司</td></tr><tr><td>马松染料</td><td>美国Thermo 公司</td></tr><tr><td>钙黄绿素</td><td>上海源叶生物科技有限公司</td></tr><tr><td>多聚甲醛</td><td>上海Aladdin生化科技有限公司</td></tr><tr><td>金黄色葡萄球菌（S.aureus）</td><td>ATCC</td></tr><tr><td>耐甲氧西林金黄色葡萄球菌（MRSA)</td><td>ATCC</td></tr></table></body></html>\n\n其他试剂同 2.5.1.2。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 215,
+        "chunk": "# 3.6.2 实验方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 216,
+        "chunk": "# 3.6.2.1 骨质疏松兔股骨远端假体植入和组织获取  \n\n同章节 2.5.2.1，在骨质疏松兔左侧股骨远端外侧髁制备圆柱形骨缺损，500$\\upmu\\mathrm{l}$ 含有 $1\\times10^{5}$ CFU S. aureus 和 $1\\times10^{5}$ CFU MRSA 的菌液通过缺损注入骨髓腔内。随后，在缺损中分别植入 3D 打印微孔支架（pTi 组）、填充CEC-PVA-AgNW 水凝胶的3D 打印微孔支架（ $\\operatorname{\\dot{p}T i}(\\varnothing\\mathrm{Gel}$ 组）和填充负载雷帕霉素的 CEC-PVA-AgNW水凝胶的 3D 打印微孔支架（pTi-Rap $@\\mathrm{Gel}$ 组）。植入术后用可吸收缝线闭合切口。动物实验共分为 3 个组，每组8 只，术后未使用抗生素。  \n\n植入后第 3 周和第 6 周，抽取静脉血进行白细胞计数，以评估全身感染。在处死前第 14 天和第 4 天肌肉注射钙黄绿素（ $\\mathrm{~(~8~mg/kg)~}$ ，以检测骨形成过程中的矿物质沉积率。术后第 6 周，过量麻醉法处死实验动物，收集左侧股骨样本，并将其固定在 $4\\%$ 多聚甲醛中，以进行后续的 Micro-CT、组织学检查和生物力学分析，具体操作步骤同章节 3.5.2。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 217,
+        "chunk": "# 3.6.2.2 数据统计分析  \n\n同章节 2.1.2.3。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 218,
+        "chunk": "# 3.6.3 结果",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 219,
+        "chunk": "# 3.6.3.1 血液学检查评估全身感染状态  \n\n对于局部骨感染性模型，外周血白细胞（WBC）计数是反映全身感染严重程度的重要指标。如图 3.18 所示，在第0 周，即细菌（S. aureus 和MRSA）和假体界面植入术前的血液学检查表明各组之间的白细胞计数没有显著差异，计数指标处于生理范围内。然而，在植入后的第 3 周和第 6 周，pTi 组的白细胞计数随着时间的延长而持续增加，显著高于 pTi@Gel 组和pTi-Rap $@\\mathrm{Gel}$ 组（ $_{\\cdot\\mathrm{p}<0.01}\\cdot$ ）。这些结果表明，假体界面在局部释放的 AgNW 可以限制骨髓腔内的细菌增殖，并控制感染的全身扩散。  \n\n![](images/791f2e345611060513f7eade09f59904ebf719d7b544e7448ac8de651dd24416.jpg)  \n图3.18 外周血白细胞计数评估全身感染情况（ $**_{p}<0.01\\dot{.}$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 220,
+        "chunk": "# 3.6.3.2 影像学评估假体界面骨整合效果  \n\n如图 3.19A 所示，X 线图像显示pTi 组植入物松动和移位，而 $\\mathsf{p T i}\\ @\\mathsf{G e l}$ 组和pTi-Rap@Gel 组固定在股骨远端外侧髁上，无明显松动迹象。假体界面的三维重建图像显示，pTi 组界面周围的骨再生受到明显限制。然而，在 pTi@Gel 组和pTi-Rap@Gel 组中可以观察到更多新生的骨组织在界面上和微孔内（图 3.19B）。Micro-CT 扫描后的骨形态学定量分析表明，相比于 pTi 组，pTi@Gel 和 pTi-  \n\nRap@Gel 组显示明显增加的骨体积分数（BV/TV）、骨小梁数量（Tb.N）和骨小梁厚度（Tb.Th），以及显著降低的骨小梁分离度（Tb.Sp）（图3.19C-F）。以上结果表明，感染性微环境中的骨形成受到明显阻碍，AgNW 抗菌水凝胶修饰的假体界面可以显著改善这种不利环境，从而促进骨再生。  \n\n![](images/ae3464b520332f6c7a0d4324534c708a8aa8286db1efb73b9c236ed1f4a754e5.jpg)  \n图3.19（A）左股骨远端 X 线正位片；（B）Micro-CT 3D 重建图像，白色为支架，黄色为骨组织；（C-F）Micro-CT 结果定量分析 BV/TV，Tb.N，Tb.Th，和 Tb.Sp参数（ $^{\\cdot}\\ast_{p}<0.05$ ; $^{**}p<0.01$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 221,
+        "chunk": "# 3.6.3.3 组织学评估假体界面骨形成与整合效果  \n\n为了观察周围骨组织与假体界面的骨形成与整合效率，我们制备不脱钙硬组织切片，并在荧光显微镜下直接观察钙黄绿素荧光双标图像（图3.20A）。动态组织形态计量分析表明，与 pTi 组相比，pTi@Gel 和 pTi-Rap@Gel 组显著提高了骨缺损区域的新骨形成速率，如 MAR，MS/BS，BFR/BS 显著增加（图 3.20B-D）。随后将硬组织切片进行马松染色观察骨整合情况。如图 3.20E 所示，pTi 组中假体微孔内有大量黄色脓液，假体界面周围骨组织未见骨整合的迹象。然而，pTi@Gel 和 pTi-Rap@Gel 组的微孔支架内部及周边并无脓液聚集，且可见部分新生骨组织与假体界面接触、甚至长入微孔内部。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 222,
+        "chunk": "# 3.6.3.4 力学评估假体界面骨整合效果  \n\n为了评估宿主骨和假体界面之间的结合强度，我们进行了支架推出试验。结果如图 3.20F 所示，pTi 组、pTi@Gel 组和 pTi-Rap@Gel 组的支架推出力峰值分别为 179.6±34.5 N、 $316.3{\\scriptstyle\\pm43.1}\\mathrm{N}$ 和 $345.4{\\scriptstyle\\pm44.6\\mathrm{N}}$ ，即与 pTi 组相比，pTi@Gel 组  \n\n和 pTi-Rap@Gel 组的支架推出峰值力显著增加了 1.76 倍和 1.92 倍（ $\\mathrm{p}{<}0.001\\rangle$ ）。  \n\n![](images/1736e8285a49f5a756e00090d4ad0f277b6746a6b1524eff7d97887ee62e8ff3.jpg)  \n图3.20（A）不脱钙硬组织切片观察钙黄绿素荧光双标；（B-D）通过钙黄绿素荧光双标对MAR、MS/BS 和BFR/BS 进行定量统计；（E）马松染色观察假体界面骨长入与整合（黑色区域表示假体，蓝色区域表示骨组织）；（F）植入 12 周后通过生物力学测试评估骨整合（ $^{*}p<0.05$ ; $^{**}p<0.01$ ; $^{***}p<0.001\\rangle$ ）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 223,
+        "chunk": "# 3.6.4 讨论  \n\n除了假体界面的骨整合不良导致的松动、移位和假体周围骨折等严重并发症，假体周围感染也是导致植入手术失败不可忽视的因素。临床回顾性分析显示人工髋关节置换术后发生假体周围感染的概率约为 $1\\%$ ，而膝关节置换术后感染率在$1-2\\%$ 之间 [249, 250]。也有报道表明初次人工关节置换术后的感染率可能比既往文献中报道的更高（ $(>2\\%)$ ）[251]。此外，术后假体周围感染是膝关节置换术后最常见的翻修原因（ $25.2\\%$ ），也占据髋关节翻修术的 $14.8\\%^{[252,253]}$ 。即使近年来由于无菌观念的提高，在膝关节翻修术中，假体周围关节感染（ $20.4\\%$ ）仍是仅次于无菌性松动（ $23.1\\%$ ）的第二大原因 [254]。大多数的早期感染可能源于假体的植入过程，主要包括内源性皮肤菌群和手术室来源的外源性菌群。针对假体周围感染的病例，除了实行翻修手术外，通常还需进行一个较长周期的抗生素治疗。但是在过去的几十年里，由于抗生素的广泛、不规范使用，细菌对抗生素产生的耐药性以及新型抗菌剂的研发缓慢成为假体周围感染治疗的一项挑战[255]。S. aureus是骨感染最常见的微生物 [256]。S. aureus 在化脓性骨髓炎中的检出率达到 $80\\%$ -$90\\%$ [257]。值得注意的是，MRSA 引起的骨感染比例增加 [258, 259]。对从假体周围感染中分离出的细菌分析显示，高达 $46.7\\%$ 的 S. aureus 对甲氧西林耐药，高达  \n\n$23\\%$ 的肠球菌对万古霉素耐药 [260]。分离获得的 MRSA 亚群显示对万古霉素敏感性降低 [252]。这些耐药生物的出现可导致患者关节置换术后假体周围感染的发病率和死亡率增加，因此，亟需研发具有新作用机制的新药来对抗这些感染对患者和医疗系统日益增加的负担 [261]。  \n\n纳米银是一种广谱抗菌剂，它通过多种机制对抗微生物，从而大大降低耐药性的机会。与离子银相比，纳米银具有更好的渗透和保留效果，因此被认为具有更优越的抗菌性能 [262]。银纳米粒子与体内的水分、血液或渗出液一旦接触即可被氧化，并释放出银离子。这些离子在局部微环境中可附着到细菌膜上，通过与细菌膜中的硫蛋白发生相互作用而损伤细菌膜, 随后进入细菌内破坏 DNA 结构。此外，还可通过攻击细菌的呼吸链，抑制细胞分裂，并最终导致细胞死亡。同时，银离子产生的自由基可诱导氧化应激，从而进一步加强杀菌能力 [262, 263]。银以其抗菌性能和低毒性而闻名，迄今为止，已在许多不同的产品中以离子和纳米颗粒的形式广泛使用，且已被证明对 E. Coil、S. aureus、肺炎克雷伯菌和 MRSA 等细菌有显著的抗菌效果 [264]。AgNW 除了以类似于银离子和银纳米颗粒的方式发挥其抗菌活性，与其他银纳米材料相比，由于它们的一维结构具有更高的长径比，使其具有不同的物理化学性质。与银纳米颗粒相比，AgNW 具有进一步增强含纳米银产品性能的潜力，因为它们似乎具有更高的抗菌效果和更低的细胞毒性 [264,265]。  \n\n假体周围感染严重影响宿主骨与假体界面的骨整合，甚至导致术后翻修。一般来说，具有抗菌活性的生物活性假体界面可以有效促进感染情况下假体界面周围的骨再生和骨整合。在本章节中，我们通过掺杂低浓度的 AgNW 赋予功能化水凝胶高效的抗菌性能，构建的 3D 打印生物活性界面可以有效减少假体周围感染的发生率，促进假体界面周围的骨形成与骨长入，提供合适的稳定性，进一步优化生物活性界面植入后的成功率。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 224,
+        "chunk": "# 3.7 本章总结  \n\n本研究中，我们成功制备了由 3D 打印微孔钛合金假体和负载雷帕霉素的超分子多功能水凝胶组成的新型 3D 打印生物活性界面。该生物活性界面能够通过上调 OP-BMSCs 的自噬水平，从而恢复 OP-BMSCs 衰退的细胞活性，具体表现为促进其增殖、存活和成骨分化，抑制其成脂肪分化。此外 3D 打印生物活性界面具有良好的抗菌性能，对 S. aureus 和 MRSA 表现出优异的抗菌活性。在体内研究表明，3D 打印生物活性界面可显著改善骨质疏松微环境中假体界面的骨长入和骨整合，并抑制潜在的感染发生。总的来说，这种新型假体界面的设计，为自噬能力低下导致骨生成缺陷的患者提供了一种促进假体界面骨整合和预防术后假体周围感染的有效策略。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 225,
+        "chunk": "# 第 4 章 全文结论与展望",
+        "category": " Conclusions"
+    },
+    {
+        "id": 226,
+        "chunk": "# 4.1 全文结论  \n\n在本研究中，我们通过 3D 打印技术成功构建了微孔钛合金假体，采用不同的局部雷帕霉素递送策略（即经皮超声介导的雷帕霉素递送和水凝胶负载雷帕霉素构建3D 打印生物活性假体界面），激活 OP-BMSCs 自噬活性， 以恢复其下降的细胞活性，如细胞增殖、存活和成骨分化，并且抑制其成脂分化，从而改善骨质疏松状态下假体界面的骨整合。以下是本研究的具体结论：  \n\n（1）以 $\\mathrm{Ti_{6}A l_{4}V}$ 粉末为原料，通过3D 打印技术成功制备了孔径为 $800\\upmu\\mathrm{m}$ ，孔隙率约为 $70\\%$ 的仿生微孔钛合金假体。此定制式假体具有互连的多孔结构、良好的生物相容性和合适的力学性能。  \n\n（2）成功提取骨质疏松兔 OP-BMSCs，并对其三向分化能力和细胞表型进行了鉴定。证实 OP-BMSCs 自噬活性低下，细胞增殖、存活和成骨分化能力不足且成脂肪分化增加；以不同的局部雷帕霉素递送策略为干预手段，可以改善OP-BMSCs 自噬水平，促进细胞增殖和存活，纠正成骨-成脂分化平衡。  \n\n（3）将3D 打印微孔钛合金假体植入骨质疏松兔股骨远端后，基于影像学、组织学和生物力学分析，证实经皮超声介导的雷帕霉素递送可通过激活自噬和调控成骨微环境，促进骨质疏松状态下假体界面骨整合。  \n\n（4）将 3D 打印微孔钛合金假体与负载雷帕霉素的功能化水凝胶复合成功构建了3D 打印生物活性界面，通过影像学、组织学和生物力学分析，证实功能化水凝胶介导的雷帕霉素局部递送可通过激活自噬、调控成骨微环境和预防潜在的假体周围感染，促进骨质疏松状态下假体界面骨整合。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 227,
+        "chunk": "# 4.2 本论文关键创新点  \n\n（1）根据骨质疏松微环境中 OP-BMSCs 自噬活性下降导致的细胞功能衰退为切入点，设计不同的药物递送策略以激活自噬、恢复细胞活性，促进微孔假体界面的骨整合。  \n\n（2）提出了一种 3D 打印微孔假体植入后，通过体外无创、个体化的经皮雷帕霉素递送策略，激活假体界面周围微环境中的自噬水平和调控成骨分化，从而促进界面骨整合的思路。  \n\n（3）构筑了一种 3D 打印微孔钛合金假体与负载雷帕霉素的功能化水凝胶复合的“3D 打印生物活性界面”，该无机-有机杂化界面激活自噬和调控成骨微环境，促进界面骨整合的同时还可预防潜在的假体周围感染，进一步提高假体植入的成功率。  \n\n（4）创新性的提出仿生 3D 打印假体结合不同雷帕霉素递送策略促进界面骨整合的理念，为提高骨质疏松等特殊骨质不良人群人工假体的研发提供新的思路。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 228,
+        "chunk": "# 4.3 研究展望  \n\n虽然我们在通过不同的雷帕霉素递送策略在骨质疏松状态下促进3D 打印微孔假体界面骨整合中取得了显著性进展，但是从策略优化、分子机制及临床转化应用等方面仍然存在一些亟需解决的问题。基于以上问题，提出了本研究相关的不足与展望，以在后续研究中完善验证：  \n\n（1）考虑到雷帕霉素系统给药潜在的毒副作用，本研究的体内实验缺乏局部药物递送与全身给药的对比，未能充分确证局部药物递送在骨整合方面的低剂量、高效率的优势。  \n\n（2）对于局部雷帕霉素递送的药物释放节律和给药剂量有待进一步优化，以确定利于调节 OP-BMSCs 活性和促进界面骨整合的最优的药物释放策略和最佳的药物剂量。  \n\n（3）缺乏系统全面地揭示不同策略激活 OP-BMSCs 自噬和调控成骨微环境的深层分子生物学机制，后续研究中拟通过转录组学测序技术结合生物信息学分析，详细阐明内在机制，为提高骨质疏松等特殊骨质不良人群人工假体的研发提供更坚实的理论依据。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 229,
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+[
+    {
+        "id": 1,
+        "chunk": "# 聚醚改性多面体低聚倍半硅氧烷构筑耐水性亲水防雾涂层  \n\n吴城锋 a，朱卫彪 a，何瑾馨 a,b，董霞 a,c（东华大学 a.化学化工与生物工程学院 b.纺织面料技术教育部重点实验室c.国家染整工程技术研究中心，上海 201620）  \n\n摘  要：目的 制备一种高耐水性的亲水防雾涂层。方法 通过光引发巯基-烯点击化学反应，合成聚醚改性多面体低聚倍半硅氧烷（POSS），得到聚醚改性 POSS（POSS- ${\\cdot\\mathrm{SH}_{6}}$ -PEGMA2），采用 FT-IR、 $^1\\mathrm{H}$ -NMR 表征合成产物的结构。将其与亲水性UV 树脂混合，在聚碳酸酯基板上涂布、光固化，形成高耐水性亲水防雾层。采用 X 射线光电子能谱仪（XPS）分析涂层表面元素，通过超景深三维显微镜对涂层表面形貌进行分析，使用接触角分析仪表征涂层的亲水性，并评价涂层的耐水性和防雾性能。结果 通过 XPS 得到的结果表明，POSS 在涂层中发生迁移，富集在涂层表面。通过超景深三维显微镜观察涂层表面发现，表面产生了一系列不同的微观结构，表面粗糙度增大。随涂层中 POSS- ${\\cdot}\\mathrm{SH}_{6}$ -PEGMA2 的含量增大，涂层的耐水性、亲水性以及防雾性能增强。当 $\\mathrm{POSS{-}S H_{6}{-}P E G M A_{2}}$ 的含量为 $55\\%$ 时（POSS 含量为 $9.71\\%$ ），涂层的耐水性（吸水率为 $7.3\\%$ ）、亲水性（水接触角为 $7.41^{\\circ}\\pm2.35^{\\circ}$ ）和防雾性能最佳。结论 在聚乙二醇二丙烯酸酯涂层中添加一定量聚醚改性 POSS（ $\\mathrm{\\POSS{-}S H_{6}{-}P E G M A_{2}}$ 的含量为 $55\\%$ ），能获得高耐水性的亲水防雾涂层。  \n\n关键词：多面体低聚倍半硅氧烷；光固化；亲水防雾；耐水性  \n中图分类号：TQ637.2   文献标识码：A    文章编号：1001-3660(2020)08-0123-09  \nDOI：10.16490/j.cnki.issn.1001-3660.2020.08.013",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# Water Resistant Hydrophilic Anti-fog Coating Constructed by Polyether Modified Polyhedral Oligosilsesquioxanes  \n\nWU Cheng-fenga, ZHU Wei-biaoa, HE Jin-xina,b, DONG Xiaa,c (a.School of Chemistry, Chemical Engineering and Biotechnology, b.Key Lab of Textile Science & Technology, Ministry of Education, c.National Engineering Research Center for Dyeing and Finishing of Textiles, Donghua University, Shanghai 201620, China)  \n\nABSTRACT: The work aims to fabricate a water resistant hydrophilic anti-fog coating. Polyether modified POSS (POSS- $\\mathrm{SH}_{6}$ -  \n\nPEGMA2) was prepared by synthesizing polyether polyhedral oligosilsesquioxanes through thiol-ene click chemistry. The structure of the reaction products were characterized by FT-IR and $\\mathrm{^{1}H}$ -NMR. Then, the reaction products were mixed with hydrophilic UV resin. The mixture was coated and UV-cured on a cleaned polycarbonate sheet to form a hydrophilic anti-fog coating with high water resistance. The X-ray photoelectron spectroscopy was used to analyze surface elements of the coating. The 3d optical microscope was used to analyze the surface topography of coatings. The contact angle measurement was used to characterize the hydrophilic property of coatings. The water resistance and anti-fog performance were also evaluated. The XPS results indicated that POSS migrated in the coating and enriched on the surface. With the help of the 3D optical microscope, a series of different micro structures were found on the surface, indicating that the surface roughness was increased. The hydrophilic and anti-fog properties and water resistance of the coating were improved with the increase of the content of 1 $\\mathrm{\\Delta^{2}O S S{-}S H_{6}{-}P E G M A_{2}}$ within a certain range, and the coating had the best water resistance (the water absorption rate was $7.3\\%$ ), hydrophilic property (the water contact angle was $7.41^{\\circ}\\pm2.35^{\\circ}.$ ) and anti-fog performance when the content of POSS- ${\\cdot\\mathrm{SH}_{6}}$ -PEGMA2 was $55\\%$ $9.71\\%$ POSS). Adding polyether modified POSS into PEGDMA coating (the content of POSS- ${\\cdot\\mathrm{SH}_{6}}$ -PEGMA2 is $55\\%$ ) can obtain a hydrophilic and anti-fog coating with high water resistance.  \n\nKEY WORDS: POSS, UV curing; hydrophilic and anti-fog property; water resistance  \n\n硅酸盐玻璃、聚碳酸酯（PC）、聚甲基丙烯酸甲酯（PMMA）等透明材料在生活中有着广泛的应用，如眼镜镜片、汽车挡风玻璃、太阳能光电板和温室顶部玻璃等。这些疏水性透明材料存在起雾问题，严重影响使用性能，甚至造成生命财产的损失。为达到防雾的目的，通常对材料进行超亲水改性[1-4]，组装特殊结构的亲水表面[5-7]，或通过亲疏水平衡调节涂层吸水性[8-12]等。  \n\n在亲水防雾涂层的生产过程中，UV 固化是一种被广泛选择的方法。但通过 UV 固化制得的亲水防雾涂层，耐水性较差。一般选择向其树脂中添加交联剂或一些疏水组分，提高其耐水性，但交联剂或疏水组分的加入会影响涂层的亲水性。亲水性与耐水性相矛盾，限制了通过UV 固化制得的亲水防雾涂层的应用。为解决此问题，本文选择向涂层中添加一种特殊的多面体低聚倍半硅氧烷（POSS）。POSS 及其衍生物是一种有机无机杂化的纳米材料，其构造包括由化学惰性的 Si—O—Si 键组成的无机笼形内核以及周围与Si 相连的氢或有机基团[13]。通过化学反应将所需结构的有机物引入 POSS，进而对其进行各种改性，增加其与材料的相容性，可使 POSS 在有机物中以纳米尺度均匀分散。添加POSS 能够提高涂层的耐水性[14]，并调节水分子在涂层中的扩散[12]。  \n\n高亲水性聚醚类化合物常用于制备亲水表面[2,15-16]，其中，采用聚乙二醇丙烯酸酯类树脂，通过 UV 固化制备亲水涂层是较为简便的方法。但聚乙二醇丙烯酸酯类亲水涂层容易吸水溶胀，耐水性不佳。为提高聚醚类亲水涂层的耐水性，本研究合成了一种聚醚改性POSS，并将其添加进涂层中，以提高涂层耐水性。同时，将聚醚链段的化合物引入 POSS，可以增加POSS 与聚乙二醇丙烯酸酯类树脂的相容性。此外，将POSS 引入涂层，可以调节水分子在涂层中的扩散，提高涂层的防雾性能。本文选用分子中 Si 原子数为 8的 POSS，通过巯基-烯点击化学反应，将含聚醚链段的丙烯酸酯（PEGMA， $M_{\\mathrm{n}}{\\sim}475$ ）接枝到 POSS 上，得到聚醚改性 POSS（POSS- ${\\cdot\\mathrm{SH}_{6}}$ -PEGMA2），并将聚醚改性 POSS 与 PEGDMA（ $M_{\\mathrm{n}}{\\sim}600$ ）按一定比例混合，加入一定量的光引发剂，在 UV 灯下照射 $30~\\mathrm{s}$ ，制得透明涂层。利用 X 射线光电子能谱仪、超景深三维显微镜、接触角分析仪对涂层表面形貌、亲水性进行分析，研究了不同涂层的耐水性、防雾性能，并分析了聚醚改性 POSS 在涂层中所起的作用。",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# 1 实验",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1.1 原料  \n\n八乙烯基 POSS 购自苏州矽索新材料有限公司，乙二硫醇购自上海泰坦科技股份有限公司，2-甲基-4-甲基硫代-2-吗啉苯丙酮（I907）、聚乙二醇单甲基丙烯酸酯（PEGMA， $M_{\\mathrm{n}}{\\sim}475$ ）、聚乙二醇二丙烯酸酯（PEGDMA， $M_{\\mathrm{n}}{\\sim}600$ ）、季戊四醇四（巯基乙酸）酯（PTMP）购自上海阿拉丁生化科技有限公司，季戊四醇三丙烯酸酯（PETA）购自上海麦克林生化科技有限公司，无水乙醇、四氢呋喃（THF）、无水乙醚购自国药集团化学试剂有限公司。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 1.2 PTMP、八乙烯基 POSS 的亲水改性",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 1.2.1 POSS-SH8的合成  \n\n称取 $5\\mathrm{~g~}(\\ 0.0079\\mathrm{~mol})$ ）纯化八乙烯基 POSS 溶于$50~\\mathrm{mL}$ THF 中，制得A 液。另将 $14.8734\\ \\mathrm{g}$ （ $0.158~\\mathrm{mol}$ ）乙二硫醇溶于 $30~\\mathrm{mL}$ THF 中，并向其中加入 $0.15\\mathrm{~g~}$ I907，制得 B 液。在 $600~\\mathrm{~W~}$ 汞灯的照射下，将 A 液以 $100~\\mathrm{{mL/h}}$ 的流速滴加至 B 液中，滴加完毕后，再继续反应 $30\\mathrm{min}$ 。将反应后的溶液倒入离心管中，并向其中加入一定量的无水乙醇作为沉淀剂使产物析出，在 $8000~\\mathrm{r/min}$ 的离心转速下，离心 $10\\mathrm{min}$ 。倒去上层清液，再用无水乙醇反复洗涤粗产物 $8{\\sim}10$ 次，除去未反应的乙二硫醇以及少量 I907，得到白色黏稠状粗产物。接着在索氏提取器中用无水乙醇回流处理3 天，进一步除去未反应的乙二硫醇和 I907。最后在$70\\ \\mathrm{^{\\circ}C}$ 真空烘箱中放置 $24\\mathrm{~h~}$ ，除去产物中的无水乙醇。最终得到无色透明黏稠状液体。合成路线见图 1。  \n\n![](images/bff041692a029128d32d79f061324ee418cc19277f02537a1d18bbc3e66e7026.jpg)  \n图 1  POSS- $\\mathrm{SH_{8}}$ 合成路线Fig.1 Synthesis route of $\\mathrm{POSS–SH_{8}}$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 1.2.2 POSS-SH6-PEGMA2的合成  \n\n称取 $4.1185\\mathrm{~g~(~0.008~67~mol}$ ）PEGMA 溶于 $20~\\mathrm{mL}$ THF 中，制得 A 液。另将 $6~\\mathrm{g}(\\ 0.004\\ 34\\ \\mathrm{mol}$ ）POSS- $\\mathrm{\\cdot{sH_{8}}}$ 溶于 $15~\\mathrm{mL}$ THF 中，并向其中加入 $0.06\\mathrm{~g~}\\mathrm{I907}$ ，制得B 液。将 A 液以 $10~\\mathrm{\\mL/h}$ 的流速滴加至 B 液中，滴加完毕后，再继续反应 $30~\\mathrm{min}$ 。用聚四氟乙烯注射器滤膜滤去反应后溶液中的不溶物，再在 $35\\mathrm{~}^{\\circ}\\mathrm{C}$ 的温度下，旋蒸除去部分溶剂，然后将剩余溶液转移至离心管中，并向其中加入一定量的无水乙醚作为沉淀剂使产物析出，在 $8000~\\mathrm{r/min}$ 的离心转速下，离心 $10~\\mathrm{{min}}$ 。白色蜡状物质（聚乙二醇单丙烯酸酯聚合物）沉淀在最底层，中间层为产物层，上层为乙醚/THF 混合溶剂层。将产物提取出，用无水乙醚反复洗涤 5\\~8 次，除去 I907。最后在 $30\\ \\mathrm{^{\\circ}C}$ 真空烘箱中放置 $24\\mathrm{h}$ ，除去乙醚。最终得到无色透明黏稠状液体。合成路线见图 2。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 1.2.3 PTMP-PEGMA1的合成  \n\n称取 $2.196\\mathrm{~g~}$ （ $0.0046~\\mathrm{mol}$ ）PEGMA 溶于 $20~\\mathrm{mL}$ THF 中，制得 A 液。另将 $\\ensuremath{2\\mathrm{~g~}}$ （ $0.0046~\\mathrm{mol}$ ）PTMP溶于 $3~\\mathrm{mL}$ THF 中，并向其中加入 $0.02\\mathrm{~g~}\\mathrm{I907}$ ，制得B 液。将 A 液以 $10~\\mathrm{\\mL/h}$ 的流速滴加至 B 液中，滴加完毕后，再继续反应 $30~\\mathrm{\\min}$ 。然后按照合成POSS- $\\mathrm{SH}_{6}$ -PEGMA2 的后处理过程进行后处理，最终得到无色透明液体，合成路线见图 3。  \n\n![](images/b88403d5fe437921d4d58005452bb5be8c28b23fb62b76c4201e8504f9a635f3.jpg)  \n图 2  POSS- ${\\cdot\\mathrm{SH}_{6}}$ -PEGMA2 合成路线Fig.2 Synthesis route of POSS- $\\mathrm{\\DeltaSH_{6}}$ -PEGMA2  \n\n![](images/c0840ee885c6af4a32771e40e35dff902d712666c6715ec9a97b4139c9963d10.jpg)  \n图 3  PTMP-PEGMA 合成路线Fig.3 Synthesis route of PTMP-PEG $\\mathbf{MA}_{1}$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 1.3 涂层制备  \n\n按表 1 所列的配比制备亲水防雾树脂。向各组树脂中加入总质量 $1\\%$ 的 I907，混合均匀后，使用刮涂仪在 PC 板（聚碳酸酯）表面涂布，涂层厚度为$10~\\upmu\\mathrm{m}$ 。接着在 3000 W 汞灯下固化 $30\\mathrm{~s~}$ ，得到一系列亲水涂层。  \n\n表 1  各组亲水防雾树脂组成Tab.1 Composition of each hydrophilic anti-fog resinwt.%  \n\n\n<html><body><table><tr><td>Label</td><td>PEGDMA600</td><td>POSS-SH6- PEGMA2</td><td>PETA</td><td>PTMP- PEGMA</td></tr><tr><td>0</td><td>100</td><td>一</td><td>一</td><td>一</td></tr><tr><td>A</td><td>95</td><td>5</td><td>一</td><td>一</td></tr><tr><td>A2</td><td>85</td><td>15</td><td>一</td><td>一</td></tr><tr><td>A3</td><td>65</td><td>35</td><td>一</td><td>一</td></tr><tr><td>A4</td><td>45</td><td>55</td><td>一</td><td>一</td></tr><tr><td>B1</td><td>90</td><td>一</td><td>10</td><td>一</td></tr><tr><td>B2</td><td>80</td><td>一</td><td>20</td><td>一</td></tr><tr><td>B3</td><td>70</td><td>一</td><td>30</td><td>一</td></tr><tr><td>B4</td><td>60</td><td>一</td><td>40</td><td>一</td></tr><tr><td>C1</td><td>95</td><td>一</td><td>一</td><td>5</td></tr><tr><td>C2</td><td>80</td><td>一</td><td>一</td><td>20</td></tr><tr><td>C3</td><td>65</td><td>一</td><td>一</td><td>35</td></tr><tr><td>C4</td><td>50</td><td>一</td><td>一</td><td>50</td></tr></table></body></html>  \n\nA 组树脂 POSS 含量分别为 $0.88\\%$ 、 $2.65\\%$ 、$6.32\\%$ 、 $9.71\\%$ ，C 组树脂 PTMP 含量分别为 $2.38\\%$ 、$9.53\\%$ 、 $16.68\\%$ 、 $23.83\\%$ 。涂层 ${\\bf A}_{4}$ 中 $\\mathrm{POSS–SH}_{6}.$ -$\\mathrm{PEGMA}_{2}$ 与 PEGDMA 的摩尔比接近完全反应摩尔比$2:3$ ，涂层 $\\mathrm{C}_{4}$ 中 PTMP-PEGMA 与 PEGDMA 的摩尔比也接近完全反应摩尔比。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 1.4 测试与表征  \n\n采用 PerkinElmer 傅里叶变换红外光谱仪（FT-IR）表征反应产物结构。将产物溶解在氘代 $\\mathrm{CHCl}_{3}$ 中，采用 $\\mathrm{AV}400\\mathrm{~M~}$ 核磁共振波谱仪表征反应产物结构。采用 Escalab 250Xi X 射线光电子能谱仪分析涂层表面元素。采用 KEYENCF VHX-6000 超景深三维显微镜观察涂层表面形貌。采用 DSA30 接触角分析仪表征涂层表面的亲水性。  \n\n涂层耐水性表征：将 PC 基材裁剪为 $5\\ \\mathrm{cm}\\times5$ cm大小，并对其称量，记作 $m_{0}$ 。刮涂涂层并 UV 固化后，称取涂层与基材的总质量，记作 $m_{1}$ 。将涂层在水中浸泡 $24\\mathrm{~h~}$ 后，擦干涂层表面，称取总质量，记作 $m_{2}$ 。涂层的吸水率计算公式如下[17]：  \n\n$m{=}(m_{2}{-}m_{1})/(m_{1}{-}m_{0}){\\times}100\\%$  \n\n涂层防雾性能测试：将PC 基材裁剪为 $6\\:\\mathrm{cm}\\times5$ cm大小，刮涂涂层并 UV 固化。向 $200~\\mathrm{mL}$ 烧杯中加入$90\\ \\mathrm{^\\circC}$ 以上的热水 $100~\\mathrm{mL}$ ，将涂层面向下盖在烧杯上，$15\\mathrm{~s~}$ 后观察涂层起雾情况。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 2 结果及分析  \n\n2.1 POSS-SH8 及 POSS-SH6-PEGMA2 结构表征  \n\n![](images/5169f1eed99e7f47d407f9c86031711a2536989ace0437ec63181a16b1ac8206.jpg)  \n图 4 为乙烯基 POSS、 $\\mathrm{POSS–SH_{8}}$ 和 $\\mathrm{POSS–SH}_{6}.$ -  \n图 4  POSS 及合成物的红外光谱图和核磁共振氢谱图 Fig.4 Infrared spectrum and nuclear magnetic resonance hydrogen spectrum of POSS and its compounds: a) FTIR of octavinyl-POSS; b) $\\mathrm{^{1}H}$ NMR spectra of octavinyl-POSS; c) FTIR of POSS- $\\mathrm{\\cdot{sH_{8}}}$ ; d) $\\mathrm{^{1}H}$ NMR spectra of $\\mathrm{POSS–SH_{8}}$ ; e) FTIR of POSS- ${\\cdot\\mathrm{sH}_{6}}$ - $\\mathrm{PEGMA}_{2}$ ; f) $\\mathrm{^{1}H}$ NMR spectra of POSS $-\\mathrm{SH}_{6}–\\mathrm{PEGN}$ MA2  \n\n$\\mathrm{PEGMA}_{2}$ 的红外光谱图以及核磁共振氢谱图。在图4a 中， $1084~\\mathrm{{cm}^{-1}}$ 处为乙烯基 POSS 中 Si—O—Si 键振动特征峰， $1600~\\mathrm{{cm}^{-1}}$ 处为碳碳双键的振动特征峰。在图 4c 中， $1600~\\mathrm{{cm}^{-1}}$ 处碳碳双键的振动特征峰消失，在 $1000~\\mathrm{{cm}^{-1}}$ 出现 C—S—C 键的振动特征峰，表明双键与乙二硫醇发生了点击化学反应， $2500~\\mathrm{cm}^{-1}$ 是S—H 键振动特征峰，表明产物中有巯基存在，这与目标产物 $\\mathrm{POSS–SH_{8}}$ 的结构一致。在图 4e 中， $2500\\mathrm{cm}^{-1}$ 处 S—H 键振动特征峰减弱，在 $3510,1735,1094\\mathrm{cm}^{-1}$ 分别出现 O—H、 $\\scriptstyle{\\mathrm{C}}={\\mathrm{O}}$ 、C—O—C 键的振动特征峰，$1600~\\mathrm{{cm}^{-1}}$ 处也不存在特征峰，说明经过巯基-烯点击化学反应，PEGMA 接枝到 POSS 上，而且 POSS- $\\mathrm{\\cdot{sH_{8}}}$ 的巯基没有完全参与反应。在图 4b 中， $6~\\mathrm{mg/L}$ 处的信号为碳碳双键氢原子的信号。在图 4d 中不存在该信号，新产生 a、b、c、d 处的信号。a、b、d 处的积分面积比为 $2.12:0.94:1.00$ ，与目标产物 $\\mathrm{POSS–SH_{8}}$ 的比例 $2:1:1$ 相符。在图 4f 中， $6~\\mathrm{mg/L}$ 处不存在信号，f、g、 $\\mathbf{k}$ 处的信号为 $\\mathrm{POSS–SH_{8}}$ 中亚甲基氢原子的信号，三者间的积分面积比为 $2.03:1.02:1.04$ ，与图 4d 中 a、b、d 的积分面积比一致。e、d 两处的信号峰是经过巯基烯点击化学反应后，新生成的亚甲基、次甲基氢的信号，a、b、c、j 信号为 PEGMA 中亚甲基、甲基氢的信号。其中 k 信号与 j 信号之间的积分面积比为 $8.28:3.02$ ，与目标产物 POSS- $\\mathrm{SH}_{6}$ -$\\mathrm{PEGMA}_{2}$ 的比例 $8:3$ 相符。综上所述，POSS- ${\\cdot\\mathrm{SH}_{8}}$ 与POSS- ${\\cdot\\mathrm{SH}_{6}}$ -PEGMA2 均成功合成。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 2.2 PTMP-PEGMA 结构表征  \n\n图 5 为 PTMP 以及 PTMP-PEGMA1 的红外光谱图以及核磁共振氢谱图。在图 5a 中， $2500~\\mathrm{{cm}^{-1}}$ 处为S—H 键的振动特征峰， $1728~\\mathrm{{cm}^{-1}}$ 处为羰基的振动特征峰。在图 5c 中， $2500~\\mathrm{{cm}^{-1}}$ 处 S─H 键的振动特征峰减弱，新产生 3504、 $1098~\\mathrm{{cm}^{-1}}$ 处 O—H、C—O—C 的振动特征峰， $1600~\\mathrm{cm}^{-1}$ 处也不存在特征峰。这与POSS- $\\mathrm{SH}_{6}$ -PEGMA2 相同，经过巯基-烯点击化学反应，PEGMA 接枝到 PTMT 上，而且 PTMP 的巯基没有完全参与反应。在图 5b 中，a、b 为 PTMP 上亚甲基的共振信号，其积分面积比为 $1:0.95$ 。在图 5d 中，e、f 两处的信号是经过巯基烯点击化学反应后，新生成的亚甲基、次甲基上的氢的信号，其他信号为PTMP 以及 PEGMA 中甲基、亚甲基氢的信号。其中d 信号与 i 信号的积分面积比为 $2.25:3.00$ ，与目标产物 PTMP-PEGMA1 的比例 $2:3$ 相符。综上所述，PTMP-PEGMA1 成功合成。  \n\n![](images/95235bdbfd63a5a18c2da731589e892a8174a0a5a11a86fd1e3c6f53d82ba689.jpg)  \n图 5  PTMP 及合成物的红外光谱图和核磁共振氢谱图Fig.5 FTIR and $\\mathrm{^{1}H}$ NMR spectra of PTMP and its compounds: a) FTIR of PTMP; b) $\\mathrm{^{1}H}$ NMR spectra of PTMP; c) FTIR ofPTMP-PEG $\\mathrm{\\Delta\\Psi_{MA_{1}}}$ ; d) $\\mathrm{^{1}H}$ NMR spectra of PTMP-PEGMA1",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 2.3 涂层表面元素分析  \n\n表 2 为由 XPS 测得的涂层 ${\\bf A}_{4}$ 表面 C、O、Si、S四元素的原子数分数，表面 O、Si 元素的含量比理论含量高，Si 的含量增加了一倍有余。 $\\mathrm{POSS–SH}_{6}$ -PEGMA2在树脂中定向分布，聚醚链段与 PEGDMA 的极性相似，指向 PEGDMA，而低极性的 POSS 无机组分指向表面，部分 POSS 迁移至表面，并在表面富集。这与其他研究者的报道相符[12,18]。  \n\n图 6a 为涂层 ${\\bf A}_{4}$ 的表面全谱 XPS 分析，在结合能 531.8、285、162.2、 $101.6\\ \\mathrm{~eV}$ 处出现的峰分别为O1s、C 1s、S 2p、Si 2p。图 6b 为高分辨率 C 1s 分峰表 2  涂层 ${\\mathsf A}_{4}$ 表面 C、O、Si、S 原子数分数  \n\nTab.2 Atomic ratio of C, O, Si and S on the surface of coating ${\\bf A}_{4}$   \n\n\n<html><body><table><tr><td>Peak</td><td>C1s</td><td>O1s</td><td>Si 2p</td><td>S 2p</td></tr><tr><td>Practical ratio/%</td><td>55.39</td><td>34.79</td><td>6.66</td><td>3.17</td></tr><tr><td>Theoretical ratio/%</td><td>59.68</td><td>30.58</td><td>3.25</td><td>6.49</td></tr></table></body></html>  \n\nXPS 图，根据涂层组成，可将 C 1s 分成 $\\scriptstyle{\\mathrm{O=}}C$ —O（ $287.7\\mathrm{eV}$ ）、C—S（ $286.7\\mathrm{eV}$ ）、C—O（285.1 eV）、C—C（ $283.9\\ \\mathrm{eV}$ ）、C—Si（ $283.4\\mathrm{eV}$ ）五个高斯拟合峰[19]。C—O 峰所在区域面积较大，表明表面聚醚链段含量较高，可赋予表面较高的亲水性。C—S 峰所在区域面积最小，这与 S 原子数分数最低相符。图6c 为高分辨率 Si 2p 分峰 XPS 图，根据 POSS 的分子式，可将 Si 2p 分成 Si—O（101.6 eV）、Si—C（ $100.9\\mathrm{eV}$ ）两个高斯拟合峰[20]。Si—O 峰所在区域面积大于Si—C，进一步说明 POSS- $\\mathrm{\\cdot\\mathrm{sH}}_{6}$ -PEGMA2 在涂层中定向分布，POSS 无机组分指向表面，而聚醚链段指向涂层内部。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 2.4 聚醚改性 POSS 含量对涂层表面形貌的影响  \n\n图 7 为超景深三维显微镜拍摄的涂层表面形貌。a、b、c、d、e 分别为涂层 O、 $\\mathbf{A}_{1}$ 、 $\\mathbf{A}_{2}$ 、 $\\mathbf{A}_{3}$ 、 ${\\bf A}_{4}$ 的表面。表面突起量随 POSS- $\\mathrm{SH}_{6}$ -PEGMA2 含量的增加而增加，表面粗糙程度也随之增大（涂层 ${\\bf A}_{3}$ 和涂层 ${\\bf A}_{4}$ 的 $R a$ 分别为 $0.2,0.31\\ \\upmu\\mathrm{m}$ ， $R z$ 分别为 $0.86,1.1\\upmu\\mathrm{m}$ ）。在 UV 光固化过程中，涂层中同时发生光引发巯基烯点击化学反应和光引发自由基聚合反应。如 XPS 分析所述，在涂层中，由于 $\\mathrm{POSS–SH_{6}–P E G M A_{2}}$ 在涂层中定向排列，部分 POSS 会向表面迁移，表面POSS- ${\\cdot\\mathrm{SH}_{6}}$ -PEGMA2 含量高于涂层内部。由于两组分表面张力不同， $\\mathrm{POSS{-}S H_{6}{-}P E G M A_{2}}$ 的表面张力高（HLB 值 ${>}13$ ），PEGDMA 的表面张力低（HLB 值为 6\\~8），在固化的过程中，产生 Bénard-Marangoni对流[21]。如图 8 所示，由于界面吉布斯自由能总有减小的趋势，因而在涂层形成过程中，涂料中低表面张力组分总有向高表面张力组分流动的趋势，表现为高表面张力区域向中间收缩，低表面张力区域向四周扩散，使得表面出现高低起伏的微观结构。在本文所制涂层中，表面 POSS-SH -PEGMA 含量高的区域表面张力高，PEGDMA 含量高的区域表面张力低。高表面张力能区域向中间收缩，低表面能区域向四周扩散，最终形成图 7 中微米级粗糙结构。  \n\n![](images/5f3e207ad2181404e21c3fcfb006f8a26774b5c435bbaa7b992cf2c23b305ca6.jpg)  \n图 6  涂层 ${\\bf A}_{4}$ 表面 XPS 谱图Fig.6 XPS spectra of coating ${\\bf A}_{4}$ : a) XPS wide-scan curves; b) C 1s core-level XPS spectra; c) Si $2\\mathfrak{p}$ core-level XPS spectra  \n\n![](images/6bb853878ffa16822efb23f095b961fccf682a5e1c9c9ea7c454a2e6635ca1f7.jpg)  \n图 7  不同涂层表面形貌Fig.7 Surface morphology of different coatings  \n\n![](images/47f05298098e2824b35091a9d5398d842fd54ac2e4a93afd17f9094ab7b643e2.jpg)  \n图 8  光固化过程中发生 Bénard-Marangoni 对流Fig.8 Bénard-Marangoni convection during UV curing",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 2.5 聚醚改性 POSS 含量对涂层表面亲水性的影响  \n\n图 9 为 A 组涂层接触角变化折线图，随着POSS- $\\mathrm{SH}_{6}$ -PEGMA2 在涂层中的比例增加，接触角下降，表面亲水性提高。如表面形貌分析所述，表面粗糙度随 POSS-SH6PEGMA2 含量增加而增大。根据Wenzel 模型[22]，亲水表面的表面粗糙度增大，能降低表观接触角。Quéré 等人的研究结果[23-24]表明，水在亲水粗糙表面会发生 hemi-wicking 现象。亲水粗糙表面存在高低起伏的沟壑，水会在沟壑扩散，使表观接触角进一步降低。A 组涂层表面突起量随 POSS-$\\mathrm{SH}_{6}–\\mathrm{PEGMA}_{2}$ 含量的增加而增加，水滴在涂层表面形成凸起间隙铺展，接触角降低，直至形成水膜（图 10）。  \n\n![](images/e6f738f9d609641c3c58c7c85999df7f22a9277af663058b5bed9db7a7be04bd.jpg)  \n图 9  A 组涂层接触角变化 Fig.9 Variation of WCA on the coatings of group A  \n\n![](images/ef7e07fc987f8129ec16aa3725593ad640a2d685fb355d8c55b341ebdc48535d.jpg)  \n图 10  水滴在粗糙表面铺展Fig.10 Drop spreading on rough surface",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 2.6 涂层组分对其表面耐水性的影响  \n\n图 11 为 A、B、C 三组涂层及涂层 O 的吸水率直方图。A、B、C 三组涂层的吸水率均随 PEGDMA含量的下降而提高，这表明 $\\mathrm{POSS–SH}_{6}$ -PEGMA2、PETA、PTMP-PEGMA 三者在一定程度上均能提高涂层耐水性。B 组涂层耐水性能提高是由于 PETA 在固化过程中参与交联反应，且由于 PETA 的亲水性差，涂层的亲水性降低，耐水性提高。涂层 ${\\bf A}_{4}$ 的耐水性能与涂层 ${\\bf B}_{4}$ 相当，但涂层 $\\mathbf{A}_{4}$ 的亲水性远高于涂层 ${\\bf B}_{4}$ 。图 11 中，C 组涂层的吸水率随 PTMP-PEG $\\mathbf{\\cdot}\\mathbf{M}\\mathbf{A}_{1}$ 含量的增加而下降，但吸水率依然高于 $200\\%$ ，可以认为完全不耐水。这说明，涂层 ${\\bf A}_{4}$ 具有优异耐水性能的主要原因是 POSS 的存在。如 XPS 分析所述，涂层表面的POSS 含量相对较高，形成了一层拒水层，而且涂层内部也分布着 POSS，在浸泡时，水分子不易渗透进涂层。涂层 ${\\bf A}_{4}$ 在水中浸泡 $24\\mathrm{h}$ 前后，水接触角如图 12 所示，浸泡前为 $7.41^{\\circ}{\\pm}2.35^{\\circ}$ ，浸泡 $24\\mathrm{~h~}$ 并晾干后为 $8.09^{\\circ}\\pm2.64^{\\circ}$ ，浸泡 $24\\mathrm{~h~}$ 后涂层的亲水性没有变化，进一步说明涂层 ${\\bf A}_{4}$ 具有优异的耐水性能。  \n\n![](images/25b0a6c79654ca9236fe32c55922b60b4612c540c299b688a91f63a3e9b0b719.jpg)  \n图 11  三组涂层浸泡 $24\\mathrm{~h~}$ 后涂层吸水率 Fig.11 Water absorption rate of three groups of coatings after immersed in water for $24\\mathrm{~h~}$  \n\n![](images/85ac45b2aa1643535a9b96331b705f60c33a0c6216ff88ca8ac0a0ee278e41ee.jpg)  \nFig.12 WCA contrast of coating $\\mathrm{A}_{4}$ before and after immersed in water for $24\\mathrm{~h~}$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 2.7 涂层表面防雾性能研究  \n\n图 13 为各表面的防雾性能对比图，图 13a 为 PC基材防雾测试结果，底部的图案几乎不可见。图 13b是涂层 O 的防雾测试结果，底部图案模糊可见，其防雾性能与 PC 基材相比，有很大提高，但由于水蒸气冷凝形成的水滴在其表面不能完全铺展，光线透过时，仍会发生折射与散射，导致其透明度依然不高。图 13c—f 为 A 组涂层的防雾测试结果，其防雾性能随 POSS- ${\\cdot\\mathrm{SH}_{6}}$ -PEGMA 含量的增加而逐渐提高。结合A 组涂层的表面形貌、亲水性以及 wenzel 模型[22]和Quéré 等人的研究结果[23-24]，水蒸气冷凝形成的水滴在涂层表面的突起间扩散，在表面形成一层水膜，疏水性的 POSS 能调节水在涂层中的扩散[12]。如图 14 所示，突起表面的 POSS 促使水向涂层内部及周围扩散，突起内部的 POSS 阻止水向涂层内部扩散，水仅能向周围扩散至突起间隙，促进水膜的形成。水膜形成后，后续冷凝的水滴在表面迅速铺展，不影响表面的透明度。  \n\n![](images/981738fa35e6570e9f075a0f4c6f4df624ace7e9eedf538c6a959677bfeb9785.jpg)  \n图 12  涂层 ${\\bf A}_{4}$ 浸泡 $24\\mathrm{~h~}$ 前后接触角对比  \n图 13  不同表面防雾测试结果  \n\n![](images/c5a6638d5c9e380c83e5206e5624d86adc3a6b5534903bb6022c58a7e4e22fe3.jpg)  \nFig.13 Result of anti-fog test of surfaces: a) PC sheet; b) coating O; c) coating $\\mathbf{A}_{1}$ ; d) coating $\\mathbf{A}_{2}$ ; e) coating $\\mathbf{A}_{3}$ ; f) coating $\\mathrm{A}_{4}$   \n图 14  POSS 调节水在表面扩散 Fig.14 Regulation of water spreading by POSS",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# 3  结语  \n\n1）通过巯基-烯点击化学反应，合成了聚醚改性POSS（POSS- ${\\cdot\\mathrm{SH}_{6}}$ -PEGMA2）。聚醚改性 POSS 与聚乙二醇二丙烯酸酯具有较好的相容性，在涂层中以纳米尺度分散，不影响涂层的透明度。聚醚改性 POSS中聚醚链段与 POSS 无机组分极性不同，在涂层中定向分布，聚醚链段指向 PEGDMA，POSS 指向表面，部分 POSS 向表面迁移，表面 POSS 含量增大。在UV 固化的过程中，发生 Bénard-Marangoni 对流，表面产生微观结构，粗糙度增大，涂层表观接触角降低。通过POSS 调节水在表面扩散，提高涂层的防雾性能。疏水性 POSS 使水难以渗透进涂层，从而使涂层获得优异的耐水性。  \n\n2）研究了 $\\mathrm{POSS{-}S H_{6}{-}P E G M A_{2}}$ 含量对涂层亲水性、耐水性以及防雾性能的影响。涂层的亲水性、耐水性以及防雾性能随POSS- ${\\cdot\\mathrm{SH}_{6}}$ -PEGMA2含量的增加而增强。涂层 $\\mathbf{A}_{4}$ （POSS 含量为 $9.7\\%$ ）具有最佳的耐水性（吸水率为 $7.3\\%$ ）、最强的亲水性（水接触角为 $7.41^{\\circ}\\pm2.35^{\\circ}$ ）以及最好的防雾性能。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 19,
+        "chunk": "# 参考文献：  \n\n[1] DOMKE Matthias, SONDEREGGER Georg, KOSTAL Elisabeth, et al. Transparent laser-structured glasses with superhydrophilic properties for anti-fogging applications[J]. Applied physics A, 2019, 125(10): 675.   \n[2] JIANG $\\mathrm{Yu}$ -hang, LI Yao, WANG Xue-song, et al. Fabrication of new transparent and hydrophilic hybrid anti-fog coating from silane coupler modified by polyethylene glycols[J]. Chemical Research in Chinese Universities, 2017, 33(1): 150-154.   \n[3] GUO Hong-shuang, XU Tong, ZHANG Jia-min, et al. A multifunctional anti-fog, antibacterial, and self-cleaning surface coating based on poly(NVP-co-MA)[J]. Chemical engineering journal, 2018, 351: 409-417.   \n[4] EZZAT Metwally, HUANG Chun-jen. Zwitterionic polymer brush coatings with excellent anti-fog and anti-frost properties[J]. RSC advances, 2016, 66: 61695-61702.   \n[5] ESHAGHI Akbar, MOJAB Mohammadreza. Fabrication of antireflective antifogging nano-porous silica thin film on glass substrate by layer-by-layer assembly method[J]. Journal of non-crystalline solids, 2014, 405: 148-152.   \n[6] CHOI Moonhyun, XIANGDE Lin, PARK Joohee, et al. Superhydrophilic coatings with intricate nanostructure based on biotic materials for antifogging and antibiofouling applications[J]. Chemical engineering journal, 2017, 309: 463-470.   \n[7] DUAN Zong-fan, ZHU Yu, REN Peng-rong, et al. Non-UV activated superhydrophilicity of patterned Fe-doped $\\mathrm{TiO}_{2}$ film for anti-fogging and photocatalysis[J]. Applied surface science, 2018, 452: 165-173.   \n[8] ZHAO Jie, MEYER Anthony, MA Li, et al. Terpolymerbased SIPN coating with excellent antifogging and frostresisting properties[J]. RSC advances, 2015, 124: 102560- 102566.   \n[9] LI Yi-xuan, FANG Xu, WANG Yan, et al. Highly transparent and water-enabled healable antifogging and frost-resisting films based on poly (vinyl alcohol)— Nafion complexes[J]. Chemistry of materials, 2016, 28(19): 6975-6984.   \n[10] LEE Hyomin, GILBERT Jonathan, ANGILÈ Francesco, et al. Design and fabrication of zwitter-wettable nanostructured films[J]. ACS applied materials & interfaces, 2015, 7(1): 1004-1011.   \n[11] ZHAO Jie, MA Li, MILLIANS William, et al. Dualfunctional antifogging/antimicrobial polymer coating[J]. ACS applied materials & interfaces, 2016, 8(13): 8737- 8742.   \n[12] LI Chuan, LI Xiao-hui, TAO Chao, et al. Amphiphilic antifogging/anti-icing coatings containing POSS-PDMAEMAb-PSBMA[J]. ACS applied materials interfaces, 2017, 9(27): 22959-22969.   \n[13] CORDES David, LICKISS Paul, RATABOUL Franck. Recent developments in the chemistry of cubic polyhedral oligosilsesquioxanes[J]. Chemical reviews, 2010, 110(4): 2081-2173.   \n[14] JIA Meng-jun, HE Ling, LIANG Jun-yan, et al. Dispersant effect on coatings of POSS-based poly methylmethacrylate hybrids and their protective performance to sandstones[J]. Progress in organic coatings, 2019, 132: 388- 398.   \n[15] HU Yan, WANG Yuan-hao, YANG Hong-xing. TEOS/ silane coupling agent composed double layers structure: A novel super-hydrophilic coating with controllable water contact angle value[J]. Applied energy, 2017, 185: 2209- 2216.   \n[16] WANG Kai, HUANG Min, HUANG Yue, et al. Preparation and characterization of water absorbing and anti-fogging coatings[J]. Materials science forum, 2016, 848: 722-725.   \n[17] PI Pi-hui, CHEN Xi, WEN Xiu-fang, et al. Preparation and characterization of ambient-temperature self-crosslinkable water-soluble acrylic resin for PE film ink[J]. Journal of coatings technology and research, 2015, 13(1): 73-80.   \n[18] LEE Woojin, NI Suo-long, DENG Jian-jun, et al. Telechelic poly (ethylene glycol)—POSS amphiphiles at the air/ water interface[J]. Macromolecules, 2007, 40(3): 682-688.   \n[19] 李川. 含 POSS 和 SBMA 两亲性共聚物的合成及其防 雾、防冰和防天然气水合物聚集研究[D]. 天津: 天津 大学, 2018. LI Chuan. Synthesis of amphiphilic copolymers containing POSS and SBMA for anti-fogging, anti-icing, and antiaggregation of gas hydrates[D]. Tianjing: Tianjing University, 2018.   \n[20] 吴兵兵, 李乾富, 宋凯悦, 等. 低铂 Pt/SiC 制备及对氧 还原反应的催化性能表征[J]. 人工晶体学报, 2017, 46(12): 2443-2450. WU Bing-bing, LI Qian-fu, SONG Kai-yue, et al. Preparation and catalytic characterization of Pt/SiC with less platinum for oxygen reduction reaction[J]. Journal of synthetic crystals, 2017, 46(12): 2443-2450.   \n[21] UCHIYAMA Hiroaki, MATSUI Tadayuki, KOZUKA Hiromitsu. Spontaneous pattern formation induced by benard-marangoni convection for sol-gel-derived titania dip-coating films: Effect of co-solvents with a high surface tension and low volatility[J]. Langmuir, 2015, 31(45): 12497-12504.   \n[22] WENZEL Robert. Resistance of solid surfaces to wetting by water[J]. Industrial & engineering chemistry, 1936, 28(8): 988-994.   \n[23] BICO Jose´, THIELE Uwe, QUÉRÉ David. Wetting of textured surfaces[J]. Colloids and surfaces A: Physicochemical and engineering aspects, 2002, 206(1): 41-46.   \n[24] BICO J, TORDEUX C, QUÉRÉ D. Rough wetting[J]. Europhysics letters, 2001, 55(2): 214-220.",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# On-demand reverse design of polymers with PolyTAO  \n\nHaoke Qiu1,2 & Zhao-Yan Sun 1,2  \n\nThe forward screening and reverse design of drug molecules, inorganic molecules, and polymers with enhanced properties are vital for accelerating the transition from laboratory research to market application. Specifically, due to the scarcity of large-scale datasets, the discovery of polymers via materials informatics is particularly challenging. Nonetheless, scientists have developed various machine learning models for polymer structure-property relationships using only small polymer datasets, thereby advancing the forward screening process of polymers. However, the success of this approach ultimately depends on the diversity of the candidate pool, and exhaustively enumerating all possible polymer structures through human imagination is impractical. Consequently, achieving on-demand reverse design of polymers is essential. In this work, we curate an immense polymer dataset containing nearly one million polymeric structure-property pairs based on expert knowledge. Leveraging this dataset, we propose a Transformer-Assisted Oriented pretrained model for ondemand polymer generation (PolyTAO). This model generates polymers with $99.27\\%$ chemical validity in top-1 generation mode (approximately 200k generated polymers), representing the highest reported success rate among polymer generative models, and this was achieved on the largest test set. Importantly, the average $R^{2}$ between the properties of the generated polymers and their expected values across 15 predefined properties is 0.96, which underscores PolyTAO’s powerful on-demand polymer generation capabilities. To further evaluate the pretrained model’s performance in generating polymers with additional user-defined properties for downstream tasks, we conduct fine-tuning experiments on three publicly available small polymer datasets using both semi-template and template-free generation paradigms. Through these extensive experiments, we demonstrate that our pretrained model and its fine-tuned versions are capable of achieving the on-demand reverse design of polymers with specified properties, whether in a semi-template generation or the more challenging template-free generation scenarios, showcasing its potential as a unified pretrained foundation model for polymer generation.  \n\nThe array of potential materials available on Earth is staggering, with estimations reaching as high as $10^{601}$ . However, this figure may prove to be even more expansive in reality, considering factors such as lattice defects in inorganic materials and the stochastic, multi-scale structures inherent in polymers2.  \n\nMachine learning (ML) has emerged as a formidable tool in the quest for efficiently discovering candidate structures capable of serving as viable ‘materials’, showcasing notable accuracy and efficiency across various domains, including inorganic materials3,4, metal materials5,6, organic molecules7,8, and polymer materials9,10 with interpretation and explanation11. Yet, the journey towards developing polymer materials presents distinct challenges owing to the scarcity of data and the intricate crossscale structure-property relationships12–17. In the realm of ML-assisted polymeric materials discovery, two primary methodologies can be delineated: Forward Screening and Reverse Design. The Forward Screening entails the utilization of models to sift through candidate structures from a predetermined pool of potential polymers. A gamut of ML models, ranging from rudimentary to sophisticated, including feed-forward neural network18–20, convolutional neural networks21,22, graph neural networks23–26, recurrent neural networks27, and more recently, Transformer models17,28,29, have been used to establish surrogate models for polymer forward screening. Although this approach yields commendable efficacy, particularly with small polymer datasets15,30,31, there remains a risk of overlooking structures that transcend human imagination32,33.  \n\nConversely, the Reverse Design paradigm enables the direct, ondemand design of candidate structures tailored to meet performance specifications, obviating the necessity for a predetermined pool of candidates. This represents a more optimal strategy for bespoke polymer design and harbors the potential to yield candidate structures that elude expert intuition. At its core, this paradigm is underpinned by generative models, such as the variational autoencoder $\\left(\\mathrm{VAE}\\right)^{34,35}$ , diffusion models36,37, and Transformer38,39, and has witnessed groundbreaking advancements, particularly in the design of organic small molecules and drugs34,37,40, with the percentage of chemically valid molecules generated surpassing $99\\%^{37}$ .  \n\nInspired by the success of molecular generation models on small molecules and drugs, polymer scientists are also endeavoring to develop generative models tailored to the dynamic demands of polymer applications. Batra et al.32 introduced a modified VAE designed to generate polymer repeat units based on SMILES notation, while they found the chemical validity of the generated polymers was less than $30\\%$ . This stark contrast with the higher validity observed in generative models for small organic molecules is largely due to the presence of two unique characters $(^{\\ast\\ast})$ in polymer SMILES strings16,32. These characters, which do not correspond to any chemical elements but signify distinct polymerization points41, add complexity to polymer generation and diminish the performance of generative models trained on limited datasets16. Indeed, training on larger datasets holds promise for enabling the model to learn the intricacies of polymer chemistry17,28,29. Meanwhile, polymer scientists attempted to represent polymers using molecular graphs as an alternative representation method to enhance the chemical validity of generated polymers. Kim et al.16, Liu et al.42, and Gurnani et al.33 have respectively employed graph neural networks for training polymer generative models. These efforts have yielded significant improvements in the chemical validity of generated polymers, with success rates ranging from 16.07 to $89.40\\%$ , $44.03\\%$ , and $93\\%$ , respectively.  \n\nAlthough there has been improvement in the proportion of chemically valid polymers generated at present, current polymer generative models still encounter significant challenges: (1) Foundational models can help boost the performance of downstream tasks43, especially in the field of chemistry where the small data phenomenon is frequently encountered. The absence of pre-trained foundation models for polymer generation is a critical limitation. Due to constrained polymer datasets, polymer scientists often train polymer generative models from scratch using small, property-specific datasets, such as those tailored for dielectric performance33,42. However, a pre-trained foundation model holds the promise of leveraging small datasets for various polymer properties, facilitating the accurate generation of polymers with diverse properties. (2) Current polymer generative models are trained based on SMILES-to-SMILES translation32 or graph-to-graph translation16,33,42 (or reconstruction). The unsupervised nature of this strategy inherently requires more data to learn hidden chemical patterns. As a result, the ability of the current polymer generative models to generate chemically valid polymers is limited. (3) When generating new molecules, these unsupervised approaches typically involve modifying the numerical representations within the hidden layers of generative models, which are then decoded into new polymer structures. Thus this approach necessitates an initial template polymer with the desired properties, yet identifying such templates is a formidable challenge44. Besides, due to the large dimensionality of the editable numeric representation of the template polymer, the directionality of reverse design is partially out of control34,42, introducing uncertainty to the screening task. (4) Additionally, this generation often occurs within the neighborhood of the template polymer42, and it is difficult to efficiently explore the diverse polymer space as polymers with low structural similarity may exhibit similar properties. For instance, a polymer chain containing hydrogen bonding interactions may exhibit a similar glass transition temperature to another polymer chain containing multiple benzene rings44.  \n\nTo address these challenges, we refined a polymer structure-property dataset containing nearly 1,000,000 entries based on the largest unlabeled polymer dataset, $\\mathrm{PIlM}^{45}$ . Using this curated structure–property dataset, we propose PolyTAO, a polymer generative pre-trained large language model (LLM), via supervised learning (Fig. 1). The pre-trained model demonstrates impressive polymer generation capabilities, with chemical validity exceeding $99\\%$ when generating a total of approximately 200,000 polymers in top-1 mode. We calculated the 15 pre-defined fundamental properties of the generated polymers, showing extremely high prediction accuracy with the expected values (the average $R^{2}$ is 0.96). We further tested its ability to generate polymers with other user-defined properties in multiple downstream tasks and explored the feasibility of the progressive semi-template and completely template-free polymer generation. The results demonstrate its excellent performance in on-demand reverse polymer generation, and the generated polymers exhibit diverse structural features, which showcases the model’s ability to thoroughly explore the polymer space, as well as its capabilities as a foundational polymer generative model.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Results Performance of PolyTAO on polymer generation  \n\nWe first conducted top-1 generation experiments (i.e., generating one polymer for each input) using the pre-trained model on the test set, resulting in a total of 199,159 samples generated. Among them, $99.27\\%$ were chemically valid, which represents the highest value among existing polymer generative models to date on the largest test sample (Table 1). This demonstrates that the model has deeply learned the mapping between polymeric fundamental properties and SMILES after pretraining via largescale supervised learning.  \n\nWe conducted a statistical analysis of the types of chemical elements present in our polymer structure-property dataset and the generated polymers (Fig. 2). The most abundant elements are C, N, and O, followed by other inorganic elements such as S and F, while metal elements constitute a smaller proportion, which aligns with the empirical knowledge in polymer science. The distribution of element proportions in the training set (Fig. 2a) is similar to that in the test set (Fig. 2b), indicating a relatively uniform dataset partition. Interestingly, in the polymers generated using the top-1 mode, some metal elements are not generated (Fig. 2c). This is because each LLM generates tokens (i.e., chemical elements) based on the probability of each token’s occurrence, and tokens with very low probabilities may not be generated. If necessary, this can be optimized by increasing the proportion of metal polymers in downstream tasks.  \n\nIn order to demonstrate whether the generated polymers possess the expected fundamental properties specified in the input parameters, we examined the aforementioned properties of the generated polymers, where we found a high degree of agreement between them (Fig. 3). For the chemically valid and unique polymers generated by the pre-trained model, the average $R^{2}$ value across the 15 polymer properties is 0.96. This indicates that PolyTAO can preliminarily achieve the on-demand generation of polymers with specified properties. This result instills confidence in our model’s ability to generate polymers with other properties, as discussed in the Applications of PolyTAO in generating polymers with other user-defined properties section. Interestingly, for certain properties, such as the number of aliphatic carboncycles (NumAliphaticCarboncycles) and the number of aliphatic heterocycles (NumAliphaticHeterocycles), the generated polymers exhibit relatively poor consistency. However, these inconsistencies are advantageous for the model to produce structurally diverse polymers, facilitating the generation of various ring structures (as illustrated in S2 of SI).  \n\nDue to the stochastic and probabilistic nature of the generation of LLMs, to validate the generation stability of PolyTAO, we examined the model’s performance in top- $\\boldsymbol{\\cdot}\\boldsymbol{k}$ generation. Specifically, we generated three (top-3), five (top-5), and ten (top-10) samples for the same input, evaluating the Validity, Uniqueness, and Novelty of the generated polymers. Additionally, we assessed the Tanimoto similarity coefficient between the generated polymers and input samples, as well as the synthesizability (SAscore) of the generated polymers. The results are reflected in Table 2. In the top- $\\mathbf{\\nabla}_{\\cdot}k$ generation mode, the model tends to be “adventurous\" in its generation, resulting in polymers that maintain a high level of uniqueness and novelty. Compared to top-1 generation (Fig. 3b), top- $\\mathbf{\\nabla}\\cdot k$ generation expands the chemical space of generated polymers, even extending beyond the chemical space corresponding to the training set (Fig. 3c). Regardless of the value of k, the chemical similarity between the generated polymer and the polymer corresponding to the input prompt is consistently low. In contrast, generating new molecules based on artificially modified latent representations of molecules tends to produce molecules with very high similarity42. However, this “adventurous\" generation can also lead to the generation of chemically invalid polymers, resulting in a slight decrease in the chemical validity of the generated polymers compared to the top-1 generation, but still higher than previous polymer generative models. Impressively, for all valid, unique, and novel molecules generated under the top-10 mode (totaling 1,828,027), their synthesizability did not become more challenging, demonstrating a synthesizability similar to that of PI1M as illustrated in Fig. 3d.  \n\n![](images/00300faff6d6b75da368587c680d44fac49a80f80533c0d22cff234b962e1197.jpg)  \nFig. 1 | Polymer Generation with PolyTAO. a Model architecture of PolyTAO. Using a set of 15 predefined fundamental features related to polymers as input, it has demonstrated impressive accuracy in generating the SMILES of polymer repeat units that satisfy these features via supervised learning for conditional generation.   \nSubsequently, we validated the model’s ability to generate polymers with other userdefined properties by generating polymers with specified band gaps (b), atomization energy (c), and electron affinity (d).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 3,
+        "chunk": "# Applications of PolyTAO in generating polymers with other userdefined properties  \n\nThe above results demonstrate the impressive capability of PolyTAO in generating polymers with pre-defined foundational properties. Then we further assessed the model’s ability to generate polymers with other userdefined properties to demonstrate its robustness and universality in the on-demand design of polymers.  \n\nIn principle, polymer generation based on SMILES-to-SMILES translation or graph-to-graph translation requires a template polymer that meets the desired performance16,32,33,42. By editing the latent representation of the template polymer and decoding this representation, new polymers can be generated. We refer to this paradigm as template-based polymer generation, which is a strategy applicable to most previous polymer generation models. However, due to the randomness in editing the latent representation, achieving on-demand design through this method is limited42. Additionally, finding template polymers that meet the requirements is also an arduous and challenging task41,44,46–48. Instinctively, by incorporating the target properties directly into the input prompts in a similar manner to the pre-training phase of PolyTAO (Fig. 1b–d), there is potential to achieve on-demand generation of polymers without providing such template polymers. Though this approach represents an advancement compared to template-based polymer generation, the input at this stage includes not only the target properties but also the 15 fundamental polymer properties we defined. Therefore, for the sake of rigor, we define this paradigm as a semi-template generation.  \n\nTable 1 | Performance of the pre-trained model on the test set via top-1 generation   \n\n\n<html><body><table><tr><td>Model</td><td>Architecture</td><td>Mode</td><td># Data</td><td>#Gen.</td><td>Val./% ↑</td><td>Average R²↑</td></tr><tr><td>SD-VAE32</td><td>CNN</td><td>UNC</td><td>250k</td><td>1k</td><td>13-27</td><td>0.65a</td></tr><tr><td>polyG2G33</td><td>GNN</td><td>UNC</td><td>13k</td><td>58k</td><td>93</td><td></td></tr><tr><td>IGGM42</td><td>GNN</td><td>UNC</td><td>250k</td><td>10k</td><td>44.03</td><td></td></tr><tr><td>Mole. Chef16</td><td>GNN</td><td>UNC</td><td>120k</td><td></td><td>16.07-89.40</td><td>0.96b</td></tr><tr><td>Ours</td><td>Transformer</td><td>CND</td><td>800k</td><td>199k</td><td>99.27</td><td>0.96°</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# Data number of training data, # Gen. number of generated polymers, $V a I.$ validity, UNC unconditional, CND conditional. aResults for two polymer properties (glass transition temperature and band gap). bResults for one polymer property (i.e., the partition coefficient, logP). cResults for 15 polymer properties (as illustrated in “Methods”).  \n\n![](images/0748040b46828a822889a57c880c442494b734a0cf6119259f26d455cf5bfa9c.jpg)  \nFig. 2 | Statistical analysis of the types of chemical elements. a Train set. b Test set. c Generated polymers (Gen. generated).  \n\nThen, we tested the performance of the pre-trained model in the semitemplate generation scenario. We finetuned this pre-trained model on ten public polymer datasets of different properties (S3 of SI) to obtain expert LLMs for each property. However, since experimentally validating the properties of generated polymers on a large scale is resource-intensive, we attempted to train proxy models for each dataset to efficiently validate the properties of the generated polymers on a large scale. To be specific, we utilized graph neural networks, known for their excellent performance in molecular property prediction, to train proxy models for each property.  \n\n![](images/45a39a95cadb14a7d8a15b174ab6eba4ae822adbbfeb14e90cdd209f1f92d648.jpg)  \nFig. 3 | Generation of polymers with PolyTAO on the 15 predefined tasks. a The fitting plots of the properties generated by the model (Generation) against the expected properties (Ground Truth). b, c The chemical space of polymers after t-SNE dimensionality reduction, with the background color indicating the randomly   \nselected training set from PI1M and b represents top-1 generation, with c representing top-10 generation. d illustrates the SAscore of PI1M and the valid, unique, and novel molecules generated under the top-10 mode.  \n\nTable 2 | Performance of the pre-trained model on the test set via top- $\\pmb{\\cdot}\\pmb{k}$ $\\pmb{(k=3}$ , 5, 10) generation   \n\n\n<html><body><table><tr><td> Metric</td><td>Top-3</td><td>Top-5</td><td>Top-10</td></tr><tr><td>Validity ↑</td><td>97.75 ± 0.0001</td><td>97.76 ± 0.0002</td><td>97.75 ± 0.0004</td></tr><tr><td>Uniqueness ↑</td><td>99.07 ± 0.0001</td><td>99.06 ± 0.0002</td><td>99.08 ± 0.0001</td></tr><tr><td>Novelty ↑</td><td>93.56 ± 0.0009</td><td>93.73 ± 0.0005</td><td>94.01 ± 0.0006</td></tr><tr><td>Similarity ↓</td><td>0.302 ± 0.0002</td><td>0.303 ± 0.0002</td><td>0.306 ± 0.0002</td></tr><tr><td>SAscore↓</td><td>3.84 ± 0.77</td><td>3.83 ±= 0.77</td><td>3.85 ± 0.77</td></tr></table></body></html>  \n\nSince the accuracy, i.e., coefficient of determination $(R^{2})$ , of the proxy models, is crucial in assessing the properties of the generated polymers and the performance of expert LLMs, we selected the top three proxy models with the highest $R^{2}$ (exceeding 0.9, detailed in S3 of SI) and the corresponding dataset as subsequent case studies. These proxy models are tailored for the following polymer properties: band gap, atomization energy, and electron affinity. We then finetuned the pre-trained model using these datasets individually, with the same data partitioning as when training the respective proxy models. Each polymer property served as an additional vector added to the input prompt (see Fig. 1b–d). After fine-tuning, the loss of the expert LLMs exhibited convergence (Figs. 4a, 5a, and 6a).  \n\nIn the generation of expert LLMs, we conducted top-5 generation (i.e., generating five samples for each input) and repeated the process for three rounds, to mitigate the randomness of LLM and assess the model’s ability to generate multiple polymers satisfying the target properties. Here, our main focus is to investigate the feasibility and reliability of the LLM-based polymer generative model in practical usage. Therefore, we do not delve into detailed discussions regarding the uniqueness of generated polymers in the following sections.  \n\nWe selected samples from the test sets for each property, following the criterion that the proxy model’s prediction for the sample closely matches the ground truth, aiming to enhance the rationality of utilizing the proxy model to assess the properties of generated polymers (i.e., at least, the proxy model should be sufficiently accurate in predicting the properties of input samples). Moreover, we also aimed to ensure that the selected samples exhibit outstanding properties whenever possible.  \n\n![](images/cf2f1a9ff08a0d4f24ba5d6ad9a68c8b68b7c43d178668208e3d3fdb5c73ee06.jpg)  \nFig. 4 | Generation of polymers with targeted band gap with PolyTAO through semi-template generation. Loss of the expert LLM on band gap and the input sample (a) and on-demand inverse generation on band gap task (b–d). The numbers in subfigures b–d represent the band gaps predicted by the proxy model (relative to the   \nsimilarity with the input sample), i.e., the predicted band gap(similarity). During the fine-tuning of this task, the training set consisted of 3042 samples, while the test set comprised 338 samples.  \n\nBand gap. The band gap of polymer holds significant importance in the advancement of polymer-based electronic and photonic devices, as it profoundly impacts their functionality across domains such as organic photovoltaics and light-emitting diodes. We take the example of generating polymers with wide band gaps (greater than $6\\mathrm{eV})^{33}$ . Following the aforementioned selection criteria, we opted for the structure depicted in Fig. $\\mathtt{4a}$ as the input sample, whose band gap is $6.23\\mathrm{eV}$ measured by the proxy model, with its 15 fundamental properties plus its band gap serving as the input prompt. Across 3 rounds of top-5 generation, the expert LLM on band gap yielded 14 out of 15 chemically valid polymers, with 13 out of 14 showcasing novel structures from the input sample. Impressively, the predictions of the proxy model showcased that these 13 novel samples demonstrate properties that align with the target band gap (with a margin of error of $5\\%$ from 6.23).  \n\nAtomization energy. The atomization energy of polymers reflects the strength and stability of the bonds within polymer molecules. Similarly, from the test set of the atomization energy database, we selected a polymer with high atomization energy as the input sample (Fig. 5a), and its atomization energy is $-6.18\\mathrm{eV}$ measured by the proxy model. The 15 fundamental properties plus the atomization energy of this polymer are used as the input prompt. After three rounds of top-5 generation, the expert LLM on atomization energy generated $100\\%$ chemically valid and novel polymers. It is noteworthy that the data size of this dataset is too small for an LLM, resulting in a slight decrease in the accuracy of generated polymers. According to the predictions of the proxy model, 11 out of 15 polymers exhibit properties that align with the target atomization energy (with a margin of error of $5\\%$ from $-6.18\\rangle$ ).  \n\nElectron affinity. The electron affinity of polymers reflects the polymer molecule’s ability to accept electrons, a property crucial in photovoltaic applications and other electronic applications of polymers. Unfortunately, the dataset for this property is also relatively small. During the generation, we chose the 15 fundamental properties plus the electron affinity of the structure depicted in Fig. 6a as the input prompt. The electron affinity of this polymer is 3.14 (measured by the proxy model). From the results of three rounds of top-5 generation, $100\\%$ of the generated polymers were chemically valid, with 14 out of 15 being novel. According to predictions from the proxy model, 10 out of 14 polymers exhibit properties that align with the target electron affinity (with a margin of error of $5\\%$ from 3.14).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# Template-free generation: an ambitious task towards ondemand polymer design  \n\nCompared to previous template-based approaches16,32,33,42, the semitemplate method introduced above takes target properties as part of the input, enabling the generation of polymers with specified properties. This represents an advancement over entirely template-based polymer generation. However, one more challenging goal is to achieve template-free polymer generation. The potential scenario for this paradigm is to provide the generative model with only a desired property value, allowing the model to freely generate structures that meet the requirements. Clearly, this design paradigm is ambitious yet more challenging due to the contradiction between the infinite chemical space of polymers and the limited training data available. To assess the feasibility of our pre-trained model in this challenging task, we conducted fine-tuning tests using the band gap dataset due to its larger number of data entries. During the implementation, we utilized only the value of the band gap as input, with the corresponding polymer repeat unit SMILES as output (Fig. 7a).  \n\nMeanwhile, in order to simultaneously achieve a meaningful objective, our aim is to have the fine-tuned expert LLM generate polymers with higher band gaps. We used $6.5\\mathrm{eV}$ (higher than the previous semi-template generation task) as a target, and then the model was expected to generate polymer structures with band gaps around $6.5\\mathrm{eV}$ . Throughout the generation process, we continued to utilize the top-5 generation mode and repeated the process for three rounds to assess the stability of the LLM-based polymer generative model. The generation results in Fig. 7b indicate that the proportion of chemically valid molecules generated is $100\\%$ , which is a significant prerequisite for the success of this task. Furthermore, in this novel task previously unexplored by polymer scientists, as verified by the proxy model, the expert LLM can produce no fewer than 2 samples with a target band gap (with a margin of error of $5\\%$ ) in each round of generation (marked in red font in Fig. 7b). In total, 9 polymers exhibit properties that align with the target band gap (with a margin of error of $5\\%$ ). Interestingly, compared to template-based and semi-template-based polymer generation methods mentioned earlier, the template-free approach generates a more diverse range of polymer structures, showcasing the model’s freedom to explore the polymer space. These results demonstrate the feasibility of ondemand reverse polymer generation without the template.  \n\n![](images/2f9dd2a9554e1447fcc3dc5f9f92b6d32b47dae839813d12682df885fd9c6f49.jpg)  \nFig. 5 | Generation of polymers with targeted atomization energy with PolyTAO proxy model (relative to the similarity with the input sample), i.e., predicted atothrough semi-template generation. Loss of the expert LLM on atomization energy mization energy(similarity). During the fine-tuning of this task, the training set and the input sample (a) and on-demand inverse generation on atomization energy consisted of 351 samples, while the test set comprised 39 samples. task (b–d). The numbers in subfigures b–d represent the band gaps predicted by the",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# Discussion  \n\nIn this work, we proposed a generative pre-trained model based on LLMs for on-demand reverse polymer design. The pre-trained model was trained on a meticulously curated dataset containing nearly one million polymer structures and fundamental properties, crafted based on expert knowledge. Evaluation of a test set of nearly 200,000 samples revealed that the model generated chemically valid molecules with a proportion of $99.27\\%$ . Through further top-10 generation, the pre-trained model designed over 1.8 million valid and novel polymer structures, effectively doubling the entries of the off-the-shelf polymer datasets. These data, along with widely known datasets like PI1M, can offer a richer candidate pool for paradigms based on forward screening. To achieve the generation of polymers with other specific properties, we fine-tuned the pre-trained model on three publicly available polymer property datasets, resulting in expert LLMs tailored to each property. The generation results of these expert LLMs demonstrate the powerful capability of the model in on-demand reverse generation. However, for more precise on-demand design, we advocate for greater efforts from the polymer community to expand polymer property datasets. Additionally, we attempted an ambitious task using the dataset with a relatively large amount of data on band gaps, aiming for completely template-free polymer generation. The results indicate that the fine-tuned expert LLM can achieve on-demand reverse polymer generation based solely on the provided values of the desired polymer properties.  \n\nIn summary, we have demonstrated a pre-trained model for an ondemand reverse generation of polymers, and its performance on multiple downstream datasets indicates its broad applicability and transferability. We will explore the application of polyTAO to on-demand generation tasks for a broader spectrum of polymer properties, including thermal conductivity12.  \n\nBeyond this work, by employing more advanced polymer representations, such as BigSMILES49, coupled with a larger amount of polymer data, there is potential to further enhance the model’s performance in ondemand polymer generation. More efforts, including but not limited to advancing the acquisition of large-scale BigSMILES strings and collecting multimodal, multiscale polymer data, need to be put into practice50. Although this work demonstrates the efficacy of string-based representations for polymers, graph-based representations still hold significant potential. They have shown remarkable capabilities in the realm of small molecule generation, with the prospect of achieving up to $100\\%$ validity in generated molecules, such as MoFlow and GraphAF51,52. A promising direction is to explore the integration of the advantages of both string and graph representations, such as in models like GraphFormers53.  \n\n![](images/65038cc2416745ceee68d9f7e03073140957bac4a020938662d22fa5a6fef8e4.jpg)  \nFig. 6 | Generation of polymers with targeted electron affinity with PolyTAO proxy model (relative to the similarity with the input sample), i.e., predicted electron through semi-template generation. Loss of the expert LLM on electron affinity and affinity(similarity). During the fine-tuning of this task, the training set consisted of the input sample (a) and on-demand inverse generation on electron affinity task 331 samples, while the test set comprised 37 samples. (b–d). The numbers in subfigures b–d represent the band gaps predicted by the",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# Methods Polymer structure–property dataset  \n\nThe largest publicly available polymer structure-property dataset currently is PolyInfo, containing around 20,000 polymer structure-property pairs. However, this dataset is insufficient for training a LLM. Recently, a virtual polymer database, $\\mathrm{PIlM}^{45}$ , has been extended from PolyInfo, comprising nearly one million polymer structures but lacking corresponding property values. Researchers have utilized PI1M for unsupervised pretraining for polymer generation but this unsupervised pretraining paradigm results in the limited capacity of generating chemically valid polymers42. To achieve unprecedented large-scale supervised learning on this largest polymer dataset, we opted to compute foundational properties for each polymer structure in PI1M as descriptors. Due to the significant influence of molecular interactions and chain structure on the properties of polymers at the microscopic level, we carefully selected 15 descriptors related to the factors mentioned above. Specifically, we considered: (1) Molecular weight, providing an approximate constraint on the number and types of atoms in the repeat unit. (2) Hydrogen bonds, including the types and quantities of hydrogen bond donors and acceptors. (3) Atom types, including the number of heteroatoms apart from the common carbon and hydrogen atoms in polymers. (4) Chain structure, including the types and quantities of rings and the number of rotatable bonds, which account for the flexibility of polymer molecules. For the specific list and the corresponding description, please refer to Section 1 (S1) of the Supporting Information (SI). The above foundational properties and their corresponding SMILES constitute our polymer structure-property dataset.  \n\n![](images/29558024d85ad1c46aa38cefd6f8717df83c6d627c66d5ac7cf8304138548712.jpg)  \n\n![](images/265c597100670e1986a41f872421ccda42bb845d9b4b6354755a46f0dff5a4d0.jpg)  \nFig. 7 | Generation of polymers with targeted band gap with PolyTAO through template-free generation. a Fine-tuning the pre-trained model for the template-free generation. b The generation results via template-free generation. The model will aim to generate polymer structures that meet the specified target values.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# Prompt engineering  \n\nLike any LLM, designing high-quality prompts is crucial for on-demand generation by the model. We computed 15 fundamental physicochemical properties for each polymer repeat unit’s SMILES and concatenated them to form the input prompts for PolyTAO. Except for molecular weight, all other physicochemical properties are of integer type. To reduce the input token size and improve training efficiency, we also converted the molecular weight to an integer type. In fact, this approach, imprecisely specifying the molecular weight and instead slightly “fuzzifying” it, increases the model’s freedom when generating new molecules, thus facilitating the generation of structurally diverse molecules (as shown in S2 of SI).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# Model settings  \n\nCurrently, there are many open-source large language models (LLMs) available for pretraining in chemical tasks. However, our previous research demonstrates that LLM based on a deep understanding of chemical knowledge may perform better even on less data29. Taking into account both model complexity and computational device requirements, we have chosen our previously developed PolyNC29 as the foundational model. PolyNC is an LLM based on polymer structures with over 22 million parameters, capable of predicting various properties such as the glass transition temperature of polymers, benefiting from the crossattention mechanism54. Therefore, during the training process of PolyTAO, we utilized PolyNC as the initial weights and reconstructed the input and output data types as described in Section “Prompt engineering”. After training, PolyTAO was employed to generate polymer structures based on the pre-defined (and user-defined) properties of the given polymers—a capability that was not available in most previous polymer LLMs, including PolyNC.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# Polymer generative pretraining via large-scale supervised learning  \n\nDuring the pretraining, the foundational properties will be concatenated as input, while the corresponding structures (SMILES) serve as the output (Fig. 1a). Compared to generative models using SMILES-to-SMILES translation and graph-to-graph translation, our paradigm of property-to-SMILES aims to enable the model to capture more foundational properties of polymers and their corresponding structures (SMILES). We randomly partitioned the polymer structure-property dataset into a training set $80\\%$ , ${\\sim}0.8$ million) and a test set $20\\%$ , ${\\sim}0.2$ million) for pretraining. During fine-tuning for “semitemplate” generation with other user-defined properties, we added other polymer properties as additional vectors to the input prompt (Fig. 1b–d). At this point, the input feature dimension of the model is 16 (15 pre-defined $+1$ user-defined). In template-free generation, the input dimension is reduced to just one, which is the value of the target polymer property. To the best of our knowledge, the proposed semi-template generation and template-free generation have not been studied in the polymer generative models.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# Model metrics  \n\nFor molecular generative models, the primary metric of interest is chemical Validity (the percentage of chemically valid molecules), which is our foremost consideration. Additionally, LLM can produce multiple outputs for the same input (i.e., top- $k$ generation), which is beneficial for generating structurally diverse candidate molecules and helps assess the stability of the model’s generation capability. Therefore, for top- $\\mathbf{\\nabla}\\cdot k$ generation scenarios, we also evaluate the Uniqueness (the percentage of chemically valid molecules generated that are mutually unique in each generation of the k times generation) and Novelty (the percentage of generated valid molecules not in the training set and the test set in each generation of the k times generation) of the generated polymers.  \n\nIt is worth mentioning that previous polymer generative models rarely discussed the similarity of generated polymers to existing polymers and, more importantly, the synthetic feasibility of the generated polymers. Thus, in top- $\\mathbf{\\nabla}_{\\cdot}k$ generation scenarios, we additionally assess the Similarity (i.e., Tanimoto similarity55) and synthetic feasibility56 (SAscore) of the generated polymers.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# Data availability  \n\nThe PI1M dataset is publicly available at https://github.com/RUIMINMA1996/ PI1M. The 15 fundamental properties in the pre-training stage were calculated using the RDKit package (version: 2023.3.2). Our pre-trained model is publicly available at https://huggingface.co/hkqiu/PolymerGenerationPretrainedModel. Any other data and code related to reproducing the results will be provided promptly upon request.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# Code availability  \n\nThe source codes of demos for generation polymers via semi-template and template-free are available at https://github.com/hkqiu/PolymerGeneration PretrainedModel.  \n\nReceived: 23 July 2024; Accepted: 4 November 2024; Published online: 29 November 2024",
+        "category": " References"
+    },
+    {
+        "id": 14,
+        "chunk": "# References  \n\n1. Sanchez-Lengeling, B. & Aspuru-Guzik, A. Inverse molecular design using machine learning: generative models for matter engineering. Science 361, 360–365 (2018).   \n2. Gormley, A. J. & Webb, M. A. Machine learning in combinatorial polymer chemistry. Nat. Rev. Mater. 6, 642–644 (2021).   \n3. Merchant, A. et al. Scaling deep learning for materials discovery. Nature 624, 80–85 (2023).   \n4. Szymanski, N. J. et al. An autonomous laboratory for the accelerated synthesis of novel materials. Nature 624, 86–91 (2023).   \n5. Pétuya, R. et al. Machine-learning prediction of metal-organic framework guest accessibility from linker and metal chemistry. Angew. Chem. Int. Ed. 61, e202114573 (2022).   \n6. Nandy, A. et al. Computational discovery of transition-metal complexes: from high-throughput screening to machine learning. Chem. Rev. 121, 9927–10000 (2021).   \n7. Burger, B. et al. A mobile robotic chemist. Nature 583, 237–241 (2020).   \n8. Li, X. et al. Combining machine learning and high-throughput experimentation to discover photocatalytically active organic molecules. Chem. Sci. 12, 10742–10754 (2021).   \n9. Lu, H. et al. Machine learning-aided engineering of hydrolases for PET depolymerization. Nature 604, 662–667 (2022).   \n10. McDonald, S. M. et al. Applied machine learning as a driver for polymeric biomaterials design. Nat. Commun. 14, 4838 (2023).   \n11. Oviedo, F., Ferres, J. L., Buonassisi, T. & Butler, K. T. Interpretable and explainable machine learning for materials science and chemistry. Acc. Mater. Res. 3, 597–607 (2022).   \n12. Wu, S. et al. Machine-learning-assisted discovery of polymers with high thermal conductivity using a molecular design algorithm. npj Comput. Mater. 5, 66 (2019).   \n13. Kuenneth, C. et al. Polymer informatics with multi-task learning. Patterns 2, 100238 (2021).   \n14. Yang, J., Tao, L., He, J., McCutcheon, J. R. & Li, Y. 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Accelerating discovery of polyimides with intrinsic microporosity for membrane-based gas separation: synergizing physics-informed performance metrics and active learning. Adv. Funct. Mater. https://doi.org/10.1002/adfm.202314683 (2024).   \n27. Simine, L., Allen, T. C. & Rossky, P. J. Predicting optical spectra for optoelectronic polymers using coarse-grained models and recurrent neural networks. Proc. Natl Acad. Sci. USA 117, 13945–13948 (2020).   \n28. Kuenneth, C. & Ramprasad, R. polyBERT: a chemical language model to enable fully machine-driven ultrafast polymer informatics. Nat. Commun. 14, 4099 (2023).   \n29. Qiu, H. et al. PolyNC: a natural and chemical language model for the prediction of unified polymer properties. Chem. Sci. 15, 534–544 (2024).   \n30. Bradford, G. et al. Chemistry-informed machine learning for polymer electrolyte discovery. ACS Cent. Sci. 9, 206–216 (2023).   \n31. Qiu, H., Qiu, X., Dai, X. & Sun, Z.-Y. 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Guided diffusion for inverse molecular design. Nat. Comput. Sci. 3, 873–882 (2023).   \n38. Bagal, V., Aggarwal, R., Vinod, P. K. & Priyakumar, U. D. Molgpt: molecular generation using a transformer-decoder model. J. Chem. Inf. Model. 62, 2064–2076 (2022).   \n39. Chang, J. & Ye, J. C. Bidirectional generation of structure and properties through a single molecular foundation model. Nat. Commun. 15, 2323 (2024).   \n40. Swanson, K. et al. Generative AI for designing and validating easily synthesizable and structurally novel antibiotics. Nat. Mach. Intell. 6, 338–353 (2024).   \n41. Ma, R., Zhang, H. & Luo, T. Exploring high thermal conductivity amorphous polymers using reinforcement learning. ACS Appl. Mater. Interfaces 14, 15587–15598 (2022).   \n42. Liu, D.-F. et al. High-temperature polymer dielectrics designed using an invertible molecular graph generative model. J. Chem. Inf. Model. 63, 7669–7675 (2023).   \n43. Ahmad, W., Simon, E., Chithrananda, S., Grand, G. & Ramsundar, B. Chemberta-2: towards chemical foundation models. Preprint at arXiv https://doi.org/10.48550/arXiv.2209.01712 (2022).   \n44. Qiu, H., Wang, J., Qiu, X., Dai, X. & Sun, Z.-Y. Heat-resistant polymer discovery by utilizing interpretable graph neural network with small data. Macromolecules 57, 3515–3528 (2024).   \n45. Ma, R. & Luo, T. PI1M: a benchmark database for polymer informatics. J. Chem. Inf. Model. 60, 4684–4690 (2020).   \n46. Webb, M. A., Jackson, N. E., Gil, P. S. & de Pablo, J. J. Targeted sequence design within the coarse-grained polymer genome. Sci. Adv. 6, eabc6216 (2020).   \n47. Tao, L. et al. Discovery of multi-functional polyimides through highthroughput screening using explainable machine learning. Chem. Eng. J. 465, 142949 (2023).   \n48. Xu, X. et al. Discovery of thermosetting polymers with low hygroscopicity, low thermal expansivity, and high modulus by machine learning. J. Mater. Chem. A 11, 12918–12927 (2023).   \n49. Lin, T.-S. et al. BigSMILES: a structurally-based line notation for describing macromolecules. ACS Cent. Sci. 5, 1523–1531 (2019).   \n50. Haoke, Q. & Zhao-Yan, S. Is bigsmiles the friend of polymer machine learning? Preprint at ChemRxiv https://doi.org/10.26434/chemrxiv2024-bxxhh (2024).   \n51. Zang, C. & Wang, F. Moflow: an invertible flow model for generating molecular graphs. Proc. 26th ACM SIGKDD International Conference on Knowledge Discovery & Data Mining 617–626 (2020).   \n52. Chence,S.etal.Graphaf:aflow-basedautoregressivemodelformolecular graph generation. Proc. Int. Conf. Learn. Represent. (2020).   \n53. Junhan, Y. et al. Graphformers: Gnn-nested transformers for representation learning on textual graph. Proc. Adv. Neural Inf. Process. Syst. (2021).   \n54. Raffel, C. et al. Exploring the limits of transfer learning with a unified text-to-text transformer. J. Mach. Learn. Res. 21, 1–67 (2020).   \n55. Bajusz, D., Rácz, A. & Héberger, K. Why is tanimoto index an appropriate choice for fingerprint-based similarity calculations? J. Cheminform. 7, 20 (2015).   \n56. Ertl, P. & Schuffenhauer, A. Estimation of synthetic accessibility score of drug-like molecules based on molecular complexity and fragment contributions. J. Cheminform. 1, 8 (2009).",
+        "category": " References"
+    },
+    {
+        "id": 15,
+        "chunk": "# Acknowledgements  \n\nWe thank the support from the National Key R&D Program of China (No. 2022YFB3707303), and the National Natural Science Foundation of China (No. 52293471). We sincerely thank Prof. Rampi Ramprasad, Prof. Ryo Yoshida, Prof. Ying Li, Prof. Zhi-Min Dang, Prof. Nicholas E. Jackson, Prof. Arash Khajeh, and their colleagues for their pioneering works in the field of polymer generation models. We also thank Ms. Jiatong Lyu from Jilin University for her creativity and inspiration for our work. The work is also supported by the hardware in the Network and Computing Center at Changchun Institute of Applied Chemistry, Chinese Academy of Sciences.",
+        "category": " Acknowledgements"
+    },
+    {
+        "id": 16,
+        "chunk": "# Author contributions  \n\nH.K.Q. designed, trained, and evaluated the generative models and drafted this paper. Z.-Y.S. supervised the work; all authors modified and approved the paper.",
+        "category": " References"
+    },
+    {
+        "id": 17,
+        "chunk": "# Competing interests  \n\nThe authors declare no competing interests.  \n\nAdditional information   \nSupplementary information The online version contains supplementary material available at   \nhttps://doi.org/10.1038/s41524-024-01466-5.  \n\nCorrespondence and requests for materials should be addressed to Zhao-Yan Sun.  \n\nReprints and permissions information is available at http://www.nature.com/reprints  \n\nPublisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.  \n\nOpen Access This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License, which permits any non-commercial use, sharing, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if you modified the licensed material. You do not have permission under this licence to share adapted material derived from this article or parts of it. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/bync-nd/4.0/.  \n\n$\\circledcirc$ The Author(s) 2024",
+        "category": " Conclusions"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# 聚合物水凝胶的高度溶胀  \n\n聚合物水凝胶由交联的长链聚合物和大量浸入的溶剂分子构成。通过控制聚合物网络的化学特性、交联程度和溶剂种类，可以制造出多种类型的水凝胶。这些材料因其独特的性质，在医疗设备、药物的靶向释放、仿生组织材料的设计以及对环境刺激敏感的执行器等领域有着广泛的应用（参考资料 1）。  \n\n聚合物凝胶在受到机械载荷或周围溶剂化学势变化的影响时，可能会发生显著的变形。在溶剂分子扩散时间远小于典型时间尺度的情况下，凝胶的力学响应是等体积的，这意味着只会发生形状变化而不改变体积。然而，随着时间的推移，溶剂分子有足够的时间重新分布，因此凝胶可以同时发生形状和体积的显著变化。  \n\n本例演示了如何在 COMSOL Multiphysic $\\textsuperscript{\\textregistered}$ 中，根据参考资料 1 的研究成果，实现聚合物水凝胶的大变形与溶剂扩散耦合的非线性场理论。通过与两个基准问题的对比验证了模型的有效性：一个是凝胶与刚性基底黏合的非均质膨胀问题（参考资料 2），另一个是在蠕变载荷下的单轴固结问题 （参考资料 1）。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 2,
+        "chunk": "# 理论背景  \n\n凝胶被视为一种均质、连续的单相材料。溶剂的存在可以通过摩尔浓度 $c(\\mathbf{X},t)$ 来描述，即，在特定位置 $\\mathbf{X}$ 和时间 $t$ ，聚合物凝胶每单位参考体积中的溶剂摩尔数。通常情况下，参考构型被选为干燥的聚合物网络 （即 $c({\\bf X},0)=0$ ）。由于凝胶能够与周围环境交换溶剂分子，它被视为一个开放系统，浓度 $\\boldsymbol{\\mathbf{\\mathit{c}}}$ 必须遵循局部体积平衡方程  \n\n$$\n\\dot{c}+\\nabla\\cdot\\overline{{\\mathbf{Q}}}=0\n$$  \n\n其中， $\\overline{{\\mathbf{Q}}}=\\mathbf{Q}/V_{\\mathrm{m}}$ 表示溶剂的摩尔通量 （SI 单位： $\\mathrm{mol}/(\\mathrm{m}^{2}{\\cdot}\\mathrm{s}))$ ）， $\\mathbf{Q}$ 表示体积通量，$V_{\\mathrm{m}}$ 表示溶剂的摩尔体积 （SI 单位： $\\mathrm{m}^{3}/\\mathrm{mol}\\dot{.}$ ）。当忽略惯性时，局部动量平衡方程的表达式如下  \n\n$$\n\\nabla\\cdot\\mathbf{P}+(\\uprho_{\\mathrm{{S}}}+M_{\\mathrm{{m}}}c)\\mathbf{B}=\\mathbf{0}\n$$  \n\n其中， $\\mathrm{~\\bf~P~}$ 表示凝胶中的第一类皮奥拉- 基尔霍夫应力， $\\uprho_{\\mathrm{S}}$ 表示聚合物网络的质量密度， $M_{\\mathrm{m}}$ 表示溶剂的摩尔质量， $\\mathbf{B}$ 表示作用在单位质量上的体力。在接下来的讨论中，我们将忽略体力。  \n\n聚合物凝胶的自由能密度通常可分为两个相加的部分（参考资料 1）：一部分与聚合物链的拉伸有关，另一部分与聚合物和溶剂分子的混合有关，即：  \n\n$$\n\\Psi(\\mathrm{F},c)=\\Psi_{\\mathrm{s}}(\\mathrm{F})+\\Psi_{\\mathrm{mix}}(c)\n$$  \n\n其中，拉伸的自由能被定义为  \n\n$$\n\\Psi_{\\mathrm{s}}(\\mathrm{F})=\\frac{G}{2}(I_{1}-3-2\\mathrm{log}J)\n$$  \n\n混合的自由能采用以下形式  \n\n$$\n\\Psi_{\\mathrm{mix}}(c)=-K_{\\mathrm{mix}}\\bigg[V_{\\mathrm{m}}c\\mathrm{log}\\bigg(1+\\frac{1}{V_{\\mathrm{m}}c}\\bigg)+\\frac{\\chi}{1+V_{\\mathrm{m}}c}\\bigg]\n$$  \n\n在这些表达式中， $G$ 是聚合物网络的初始剪切模量， $I_{1}$ 是右柯西- 格林变形张量$\\mathrm{C=F^{T}F}$ 的第一不变量， ${\\boldsymbol{J}}=\\operatorname*{det}({\\boldsymbol{\\mathrm{F}}})$ 是体积比， $K_{\\mathrm{mix}}$ 是混合的本体刚度， $\\boldsymbol{\\chi}$ 是与混合焓相关的无量纲常数。需要注意的是，自由能密度以单位参考体积表示，是以变形梯度 F和溶剂浓度 $\\mathbf{\\Psi}_{c}$ 为变量的函数。  \n\n对于大多数水凝胶而言，通常认为其体积变化仅由溶剂含量的变化引起，而聚合物和溶剂本身是不可压缩的。这一约束条件建立了溶剂浓度与体积比之间的直接联系，即，  \n\n$$\nJ=1+V_{\\mathrm{m}}c\n$$  \n\n由于这个约束条件，我们可以通过 Legendre 变换引入另一种形式的自由能密度，见参考资料 2。设  \n\n$$\n\\Psi(\\mathrm{F},\\bar{\\upmu})=\\uppsi(\\mathrm{F},c)-\\bar{\\upmu}c\n$$  \n\n其中， $\\bar{\\upmu}$ 表示溶剂的化学势，单位为 $\\mathrm{J}/\\mathrm{mol}$ 。通过应用热力学限制，第一类皮奥拉 - 基尔霍夫应力、溶剂浓度和溶剂通量的表达式如下  \n\n$$\nP=\\frac{\\partial\\Psi}{\\partial\\mathrm{F}},\\quad c=-\\frac{\\partial\\Psi}{\\partial\\overset{\\cdot}{\\mu}},\\quad\\mathbf{Q}=-\\mathbf{M}\\nabla\\upmu\n$$  \n\n其中，二阶张量 M （SI 单位： $\\mathrm{m^{4}/(N s)}$ ）称为迁移率张量，必须对称且正定。为方便起见，我们还引入了以压力为单位的化学势， $\\upmu=\\Bar{\\upmu}/V_{\\mathrm{m}}$ 。需要注意的是，溶剂通量的本构定律类似于多孔介质中的达西定律；实际上，我们可以根据溶剂黏度 $\\upmu_{\\mathrm{f}}$ 确定材料渗透率张量 $\\mathbf{\\boldsymbol{\\kappa}}=\\upmu_{\\mathrm{f}}\\mathbf{\\boldsymbol{M}}$ （SI 单位： $\\mathrm{m}^{2}$ ）。在参考资料 1 中，基于溶剂的扩散系数 $D$ 推导出了空间溶剂迁移率张量的表达式，该扩散系数在当前构型中被假设为各向同性。经过单位转换，对材料坐标系进行回拉操作，并应用分子不可压缩性约束，我们得到了与参考资料 1 中方程 (30) 相似的材料迁移率张量，如下所示  \n\n$$\n\\mathbf{M}=J\\mathbf{F}^{-1}\\bigg({V_{\\mathrm{m}}\\frac{c V_{\\mathrm{m}}}{J}\\frac{D}{N_{\\mathrm{A}}k_{\\mathrm{B}}T}\\mathbf{I}}\\bigg)\\mathbf{F}^{-\\mathrm{T}}=(J-1)\\frac{V_{\\mathrm{m}}D}{N_{\\mathrm{A}}k_{\\mathrm{B}}T}\\mathbf{C}^{-1}\n$$  \n\n其中， $N_{\\mathrm{A}}$ 和 $k_{\\mathrm{B}}$ 分别表示阿伏加德罗数和玻尔兹曼常数。自由能密度 （方程 7）和局部体积平衡方程 （方程 1）现已完全转换为使用新的因变量。利用分子不可压缩性约束，我们推导出了自由能密度  \n\n$$\n\\Psi(\\mathrm{{F},\\upmu})\\ =\\ {\\frac{G}{2}}(I_{1}-3-2\\log J)-K_{\\operatorname*{mix}}{\\biggl[}(J-1)\\log\\biggl({\\frac{J}{J-1}}\\biggr)+{\\overset{\\zeta}{J}}{\\biggr]}-\\upmu(J-1)\n$$  \n\n此外，将溶剂通量的本构方程 （方程 $8_{3}$ ）代入局部体积平衡方程（方程 1），并利用分子不可压缩性约束，可以得到  \n\n$$\n\\dot{\\boldsymbol{J}}=\\nabla\\cdot(\\mathbf{M}\\nabla\\upmu)\n$$  \n\n最后，将方程 10 导入方程 $8_{1}$ ，即可得到第一类皮奥拉 - 基尔霍夫应力  \n\n$$\n{\\mathrm{\\bf~P}}=G({\\mathrm{\\bfF}}-{\\mathrm{\\bfF}}^{-\\mathrm{\\bfT}})+K_{\\mathrm{mix}}\\biggl[J\\mathrm{log}\\biggl(1-\\frac{1}{J}\\biggr)+1+\\frac{\\chi}{J}\\biggr]{\\mathrm{\\bfF}}^{-\\mathrm{\\bfT}}-J\\mathrm{{\\bf\\upmu}}{\\mathrm{\\bfF}}^{-\\mathrm{\\bfT}}\n$$  \n\n因此，所有方程均已改用 F 和 $\\upmu$ 作为因变量，替代了原来的 F 和 $\\scriptstyle{\\begin{array}{l}{c}\\end{array}}$ 。这种因变量选择更适合处理边界条件，因为化学势在边界上具有连续性，而溶剂浓度则不连续。当边界值问题求解完成后，可以利用方程 6 通过体积比 $J$ 来计算 $\\mathbf{\\Psi}_{c}$ 。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 3,
+        "chunk": "# 有限元实施的参考构型  \n\n到目前为止，我们一直以干燥的聚合物网络作为参考构型。然而，实际上，水凝胶通常包含大量的溶剂。此外，在数值计算中，干燥状态存在问题，因为在体积比 $J$ 趋向于 1 的极限情况下，混合的自由能密度是奇异的。出于这些原因，我们选择了一种新的参考状态，假设凝胶处于自由膨胀状态，即没有受到外力的作用，并且与化学势为$\\upmu_{\\mathrm{ref}}$ 的溶剂达到平衡，见参考资料 2。由于凝胶是均质且各向同性，这种自由膨胀状态可以用变形梯度 $\\mathrm{F}_{0}=\\lambda_{0}\\mathrm{I}$ 来描述。因此，变形梯度 F 可以乘法分解为 $\\mathrm{F}=\\mathrm{F}^{\\prime}\\mathrm{F}_{0}$ ，其中，F' 表示从自由膨胀参考构型到当前构型的变形梯度。 $\\lambda_{0}$ 的值可以通过求解自由膨胀边界值问题来计算，这个问题可以简化为一个代数方程，  \n\n$$\nG{\\left(\\frac{1}{\\lambda_{0}}-\\frac{1}{\\lambda_{0}^{3}}\\right)}+K_{\\mathrm{mix}}{\\left[\\log\\left(1-\\frac{1}{\\lambda_{0}^{3}}\\right)+\\frac{1}{\\lambda_{0}^{3}}+\\frac{\\chi}{\\lambda_{0}^{6}}\\right]}-\\upmu_{\\mathrm{ref}}=0\n$$  \n\n确定了 $\\lambda_{0}$ 之后，我们可以通过 Piola 变换得到新参考构型中的自由能密度和迁移率张量  \n\n$$\n\\Psi^{\\prime}(\\mathrm{F},\\upmu)=\\frac{1}{J_{0}}\\Psi(\\mathrm{FF}_{0},\\upmu),\\quad\\mathrm{~\\mathrm{~M}\"=\\frac{1}{J_{0}}F_{0}M F_{0}^{\\mathrm{T}}}\n$$  \n\n其中， $J_{0}=\\operatorname*{det}(\\mathrm{F}_{0})={\\lambda_{0}}^{3}$ 。在 COMSOL Multiphysics 中实现时，所需的 $\\Psi^{\\prime}$ 和 $\\mathbf{M}^{\\prime}$ 的表达  \n式具体如下：  \n拉伸自由能的表达式为  \n\n$$\n\\Psi_{\\textrm{s}}^{*}=\\frac{G}{2J_{0}}(\\lambda_{0}^{2}I_{1}-3-2\\log(J_{0}J))\n$$  \n\n混合自由能的表达式为  \n\n$$\n\\Psi_{\\mathrm{mix}}=-K_{\\mathrm{mix}}\\left[\\left(J-\\frac{1}{J_{0}}\\right)\\log\\left(\\frac{J_{0}J}{J_{0}J-1}\\right)+\\frac{\\chi}{J_{0}^{2}J}\\right]\n$$  \n\n迁移率张量相对于膨胀参考构型的表达式为  \n\n$$\n\\mathbf{M}^{\\prime}=\\left(J-{\\frac{1}{J_{0}}}\\right){\\frac{V_{\\mathrm{m}}D}{N_{\\mathrm{A}}k_{\\mathrm{B}}T}}(\\mathbf{C}^{\\prime})^{-1}\n$$  \n\n需要注意的是，变量 ${\\boldsymbol{J}}^{\\prime}=\\operatorname*{det}({\\boldsymbol{\\mathrm{F}}}^{\\prime})$ 、 $\\mathrm{C^{\\prime}=F^{\\mathrm{T}}F^{\\prime}}$ 和 $I_{1}=\\mathrm{tr}(\\mathrm{C}^{\\prime})$ 是变形梯度 F' 的函数，后者描述了材料线单元从膨胀参考构型到当前构型的映射过程，这种变形是我们所要求解的问题。如果没有内在的非弹性过程，这些变量可以在 “固体力学”接口中找到，分别对应于 solid.Jel、 solid.Cel 和 solid.I1Cel。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# 基准问题  \n\n我们通过研究两个轴对称基准问题来验证模型的实现。首先，计算一个圆柱形凝胶在纯溶剂中膨胀并黏合在刚性基底上的长期稳态解，并将结果与参考资料 2 中的结果进行比较。通过参数化扫描改变凝胶的纵横比，并将结果与半解析方法得到的均匀自由膨胀和单轴膨胀的极限情况（柱状和圆盘状凝胶几何形状）进行比较。对于宽而短的（即圆盘状）凝胶，其侧边会严重变形，并与刚性表面接触。尽管此基准问题只关注长期稳态解，但我们也采用瞬态研究来演示如何实现接触相关的溶剂通量边界条件。  \n\n第二个基准问题是研究圆柱形凝胶在蠕变压缩条件下的瞬态单轴固结问题，见参考资料 1。在这个分析中，圆柱形凝胶受到径向约束，其上边界施加载荷，下边界固定。流体可通过顶部的多孔过滤器自由流动。我们采用二维轴对称几何模型求解耦合问题，并将结果与参考资料 1 中简化为一维扩散微分方程的固结问题的结果进行比较。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# 模型参数  \n\n下表给出了两个基准问题所使用的模型参数。  \n\n表格 1：两个基准问题的模型参数。  \n\n\n<html><body><table><tr><td>参数</td><td>非均质膨胀 (参考资料2)</td><td>单轴固结 (参考资料1)</td></tr><tr><td>G</td><td>40 kPa</td><td>40 kPa</td></tr><tr><td>Kmix</td><td>40 MPa</td><td>40 MPa</td></tr><tr><td></td><td>0.1</td><td>0.2</td></tr><tr><td>Vm</td><td>6.022-10-5 m3/mol</td><td>6.022-10-5 m3/mol</td></tr><tr><td>D</td><td>10 m2/s</td><td>8·10-10m2/s</td></tr></table></body></html>  \n\n表格 1：两个基准问题的模型参数。  \n\n\n<html><body><table><tr><td>参数</td><td>非均质膨胀 (参考资料2)</td><td>单轴固结 (参考资料1)</td></tr><tr><td>Mref</td><td>-2.6376·105 Pa</td><td>O Pa</td></tr><tr><td>入0</td><td>2.0</td><td>3.215</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 结果与讨论  \n\n图 1 显示了圆柱形凝胶与刚性基底黏合后，在纯溶剂中膨胀至平衡状态时相对于干燥聚合物网络的膨胀比 J。其中展示了三种不同纵横比 $(D/H)$ 的凝胶，它们的结果与参考资料 2 中的变形图（见该参考资料的图 7）高度吻合。需要注意的是，在 $D/H=10$ 的情况下，可以明显观察到自由侧边因折叠而严重变形，并与刚性基底接触。此外，凝胶内部及其外部边界的膨胀比（以及由此决定的溶剂浓度）是不均匀的。  \n\n![](images/e440767ecbf6050c756806610dbf69dfe6ecc6281a1bf460e1327487deb491a1.jpg)  \n图 1：与刚性基底黏合的圆柱形聚合物水凝胶的膨胀比。  \n\n图 2 显示了随着圆柱体纵横比的变化，凝胶高度的变化情况。对于柱状的薄凝胶，其高度趋近于均质自由膨胀理论预测的高度（绿色曲线），这是因为凝胶的大部分域不受约束条件的影响。而对于较宽的圆盘状凝胶 （即 $D/H$ 比值较高的情况），由于在面内方向受到约束，其膨胀状态更接近于单轴膨胀 （红色曲线）。  \n\n![](images/278988390e224c28f1a8ce4eb2ddcc48f077190852d953931b15754118619f25.jpg)  \n图 2：厚度方向上的平衡膨胀比随凝胶纵横比变化的情况。  \n\n接下来，我们将求解单轴固结下的瞬态解。图 3 以表面图形式显示了在无量纲时间$D t/H_{0}^{2}=200$ 时，正应力和化学势在空间坐标系中的分布情况。可以看出，正应力在凝胶整个厚度方向上保持不变，这符合动量平衡原理。在凝胶底部，大部分的载荷通过流体压力来支撑，而在顶部，载荷主要由聚合物网络来承担。  \n\n图 4 显示了在特定时间点，凝胶在厚度方向上的拉伸程度与归一化参考坐标的关系。为了让结果更易于与参考资料 1（见该参考资料的图 4）进行比较，我们将 Z 轴的方向反转，即从顶部指向底部。无论是短期还是长期极限，以及随时间的演变过程，都与参考资料 1 中的结果非常一致。  \n\n![](images/2c4fa33b8a18bbfe4fead03d8293d7ce2a7f95b52fa79ba04cd6e9fbd6419324.jpg)  \n图 3：在无量纲时间 $D t/H_{0}=200$ 时，单轴固结过程中凝胶的正应力（左）以及化学势和溶剂通量（右）。可以看出，正应力在整个厚度方向 $\\mathcal{L}$ 保持不变。化学势在底面达到最大值，在顶面达到最小值，此处通过多孔过滤器施加载荷，并应用自由流动边界条件。  \n\n![](images/4db11235e49a43783a79cc1b3cb25e607bd42bb797d5854786ceb24309a8c338.jpg)  \n图 4：单轴固结过程中，凝胶在不同无量纲时间点的厚度方向上的拉伸程度与凝胶厚度方向上位置的函数关系。图中的数据与 参考资料 1 中的基准数据（以圆圈标出）非常吻合。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# COMSOL 软件功能实现说明  \n\n本多物理场模型是通过结合“固体力学”接口和 “达西定律”接口，并使用多孔弹性多物理场耦合来求解动量和体积平衡的耦合方程。由于聚合物网络和溶剂都被视为不可压缩材料，因此采用了双相多孔弹性模型。同时，利用“全局常微分和微分代数方程”接口求解自由膨胀和单轴均质膨胀的非线性代数方程。在几何和位移场的离散化过程中，采用了二次拉格朗日单元 形函数，而化学势则采用了线性形函数；这些选择确保了计算应力时的插值阶数一致性。  \n\n自由能密度作为用户定义的超弹性材料来实现，其中化学势对载荷的影响会自动添加到多孔弹性耦合节点中。请注意，应力变量 solid.sij 表示的是不考虑孔隙压力的有效应力。而与方程 12 相对应的总柯西应力可以通过多物理场耦合节点中的变量poro1.sij 来获取，其中，poro1 是多孔弹性节点的名称。  \n\n在仿真过程中，如果接触区域发生变化，溶剂通量的边界条件将取决于接触状态。如果凝胶与不透水表面接触，那么与表面接触的凝胶边界部分适用无流动边界条件，而其他区域则适用自由流动边界条件。这种复杂的边界条件可以通过在压力节点中嵌入 if语句来实现。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 参考资料  \n\n1. W. Hong, X. Zhao, J. Zhou, and Z. Suo, “A theory of coupled diffusion and large deformation in polymeric gels,” J. Mech. Phys. Solids, vol. 56, pp. 1779–1793, 2008.  \n\n2. W. Hong, Z. Liu, and Z. Suo, “Inhomogeneous swelling of a gel in equilibrium with a solvent and mechanical load,” Int. J. Solids Struct., vol. 46, pp. 2382–3289, 2009.  \n\n案例库路径： Nonlinear_Structural_Materials_Module/Hyperelasticity/ hydrogel_swelling",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# 建模操作说明  \n\n从文件菜单中选择新建。  \n\n新建在新建窗口中， 单击 > 模型向导。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 模型向导  \n\n1 在模型向导窗口中， 单击 二维轴对称。  \n2 在选择物理场树中选择结构力学 $>$ 多孔弹性 $>$ 多孔弹性，大变形，实体。  \n3 单击添加。  \n4 单击 研究。  \n5 在选择研究树中选择一般研究 $>$ 瞬态。  \n6 单击 完成。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 全局定义  \n\n几何参数  \n\n1 在模型开发器窗口的全局定义节点下，单击参数 1。  \n2 在参数的设置窗口中， 在标签文本框中键入“几何参数”。  \n\n3 定位到参数栏。 在表中输入以下设置：  \n\n<html><body><table><tr><td>名称</td><td>表达式</td><td>值</td><td>描述</td></tr><tr><td>height</td><td>1[mm]</td><td>0.001m</td><td>凝胶高度</td></tr><tr><td>ar</td><td>0.2</td><td>0.2</td><td>凝胶纵横比</td></tr><tr><td>radius</td><td>ar*height/2</td><td>1E-4 m</td><td>凝胶半径</td></tr><tr><td>elsize_sw</td><td>if(ar<=2,0.05*height,0.10* height)</td><td>5E-5 m</td><td>单元大小，膨胀载 荷工况</td></tr><tr><td>elsize_c</td><td>0.01*height</td><td>1E-5 m</td><td>单元大小，固结载 荷工况</td></tr></table></body></html>  \n\n材料参数  \n\n1 在主屏幕工具栏中单击 $\\mathsf{P}_{\\mathsf{i}}$ 参数，然后选择添加 $>$ 参数。  \n\n2 在参数的设置窗口中， 在标签文本框中键入“材料参数”。  \n\n3 定位到参数栏。 在表中输入以下设置：  \n\n<html><body><table><tr><td>名称</td><td>表达式</td><td>值</td><td>描述</td></tr><tr><td>G</td><td>4e4[Pa]</td><td>40000 Pa</td><td>初始剪切模量</td></tr><tr><td>Kmix</td><td>4e7[Pa]</td><td>4E7 Pa</td><td>混合的体积模量</td></tr><tr><td>chi</td><td>0.1</td><td>0.1</td><td>混合含</td></tr><tr><td>temp</td><td>293.15[K]</td><td>293.15K</td><td>参考温度</td></tr><tr><td>Vm</td><td>1e-28[m^3]*N_A_const</td><td>6.0221E-5 m/mol</td><td>溶剂摩尔体积</td></tr><tr><td>D</td><td>1e3[m^2/s]</td><td>1000 m²/s</td><td>溶剂扩散系数</td></tr><tr><td>MO</td><td>Vm*D/(N_A_const* k_B_const*temp)</td><td>2.4707E-5 m·s/kg</td><td>溶剂迁移率</td></tr><tr><td>rhof</td><td>1[g/cm^3]</td><td>1000 kg/m</td><td>溶剂密度</td></tr><tr><td>muf</td><td>1e-3[mPa*s]</td><td>1E-6 Pa·s</td><td>溶剂黏度</td></tr><tr><td>kappa0</td><td>MO*muf</td><td>2.4707E-11 m²</td><td>渗透率</td></tr></table></body></html>  \n\n模型参数  \n\n1 在主屏幕工具栏中单击 $\\mathsf{P}_{\\mathsf{i}}$ 参数，然后选择添加 $>$ 参数。  \n2 在参数的设置窗口中， 在标签文本框中键入“模型参数”。  \n\n3 定位到参数栏。 在表中输入以下设置：  \n\n<html><body><table><tr><td>名称</td><td>表达式</td><td>值</td><td>描述</td></tr><tr><td>stretcho</td><td>2</td><td>2</td><td>自由膨胀拉 伸</td></tr><tr><td>JO</td><td>stretch0^3</td><td>8</td><td>自由膨胀体 积比</td></tr><tr><td>mu_ref</td><td>G/J0*(stretch0^2-1)+Kmix* (log(1-1/J0)+1/J0+chi/(J0^2))</td><td>-2.6376E5 Pa</td><td>参考化学势</td></tr><tr><td>mu_sw</td><td>O[Pa]</td><td>O Pa</td><td>纯溶剂的化 学势</td></tr><tr><td>poroo</td><td>1-1/J0</td><td>0.875</td><td>初始孔隙率</td></tr><tr><td>t_end</td><td>1000[s]</td><td>1000 s</td><td>持续时间</td></tr></table></body></html>  \n\n插值 1 (int1)  \n\n1 在主屏幕工具栏中单击 $\\mathsf{f}({\\mathsf{x}})$ 函数，然后选择全局 $>$ 插值。  \n\n2 在插值的设置窗口中， 定位到定义栏。  \n\n3 在表中输入以下设置：  \n\n<html><body><table><tr><td>t</td><td>f(t)</td></tr><tr><td>0</td><td>mu_ref</td></tr><tr><td>t_end</td><td>mu_sw</td></tr></table></body></html>  \n\n4 定位到单位栏。 在函数表中，输入以下设置：  \n\n<html><body><table><tr><td>函数</td><td>单位</td></tr><tr><td>int1</td><td>Pa</td></tr></table></body></html>  \n\n5 在变元表中，输入以下设置：  \n\n<html><body><table><tr><td>变元单位</td><td></td></tr><tr><td>t</td><td>S</td></tr></table></body></html>  \n\n几 何 1  \n\n1 在模型开发器窗口中展开组件 1 (comp1)> 几何 1 节点，然后单击几何 1。  \n\n2 在几何的设置窗口中， 定位到单位栏。  \n\n3 从长度单位列表中选择 $\\mathbf{m}\\mathbf{m}$ 。  \n\n矩形 1 (r1)  \n\n1 在几何工具栏中单击 矩形。  \n\n2 在矩形的设置窗口中， 定位到大小和形状栏。  \n\n3 在宽度文本框中键入 “radius”。  \n\n4 在高度文本框中键入 “height”。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# 矩形 2 (r2)  \n\n1 在几何工具栏中单击 矩形。  \n2 在矩形的设置窗口中， 定位到大小和形状栏。  \n3 在宽度文本框中键入 “1. $4^{\\star}$ radius”。  \n4 在高度文本框中键入 “ $0.1^{\\star}$ height”。  \n5 定位到位置栏。 在 $\\textbf{z}$ 文本框中键入 “-0.1\\*height”。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# 分割边1 (pare1)  \n\n1 在几何工具栏中单击 布尔操作和分割，然后选择分割边。  \n\n2 在对象r2 中，选择 “边界” 3。  \n\n3 在分割边的设置窗口中， 定位到位置栏。  \n\n4 在表中输入以下设置：  \n\n<html><body><table><tr><td>相关弧长参数</td></tr><tr><td>1/1.4</td></tr></table></body></html>  \n\n5 在几何工具栏中单击 全部构建。  \n\n形成联合体(fin)  \n\n1 在模型开发器窗口的组件 1 (comp1)> 几何 1 节点下，单击形成联合体 (fin)。  \n2 在形成联合体/ 装配的设置窗口中， 定位到形成联合体/ 装配栏。  \n3 从动作列表中选择形成装配。  \n4 清除创建对复选框。  \n5 在几何工具栏中单击 全部构建。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 14,
+        "chunk": "# 组 件 1  ( C O M P 1 )  \n\n将几何形函数设置为二次拉格朗日单元多项式，我们将使用与位移场相同的几何形函数。  \n\n1 在模型开发器窗口中，单击组件 1 (comp1)。  \n2 在组件的设置窗口中， 定位到弯曲网格单元栏。  \n3 从几何形函数列表中选择二次拉格朗日单元。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# 定义  \n\n在刚性基底的自由边 （源）和凝胶的横向边 （目标）之间创建一个接触对，当凝胶膨胀时，这两条边会发生接触。  \n\n接触对1 (p1)  \n\n1 在定义工具栏中单击 对，然后选择接触对。  \n2 选择“边界” 4。  \n3 在对的设置窗口中， 定位到目标边界栏。  \n4 选择 激活选择切换按钮。  \n5 选择“边界” 9。  \n\n变量 1  \n\n为自由能密度、溶剂迁移率和渗透率张量定义变量，这些信息以单独的文本文件提供。  \n\n1 在模型开发器窗口中，右键单击定义并选择变量。  \n2 在变量的设置窗口中， 定位到几何实体选择栏。  \n3 从几何实体层列表中选择域。  \n4 选择“域” 2。  \n5 定位到变量栏。 单击 从文件加载。  \n6 浏览到该 App 的 “案例库”文件夹，然后双击文件  \nhydrogel_swelling_variables.txt。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 16,
+        "chunk": "# 固 体 力 学 ( S O L I D )  \n\n1 在模型开发器窗口的组件 1 (comp1) 节点下，单击固体力学 (solid)。  \n2 在固体力学的设置窗口中， 单击以展开离散化栏。  \n3 从位移场列表中选择二次拉格朗日单元。  \n\n刚性材料 1  \n\n1 在物理场工具栏中单击 $\\bullet$ 域，然后选择刚性材料。  \n2 选择“域” 1。  \n\n固定约束 1  \n\n在物理场工具栏中单击 属性，然后选择固定约束。  \n\n超弹性材料 $\\boldsymbol{\\mathrm{\\Pi}}_{l}$  \n\n1 在物理场工具栏中单击 $\\bullet$ 域，然后选择超弹性材料。  \n2 选择“域” 2。  \n3 在超弹性材料的设置窗口中， 定位到超弹性材料栏。  \n4 从材料模型列表中选择用户定义。  \n\n5 在 ${\\boldsymbol{W}}_{\\mathrm{s}}$ 文本框中键入 “Psi_s+Psi_mix”。  \n6 单击以展开高级栏。 在 $E_{\\mathrm{eq}}$ 文本框中键入 “ $3^{\\star}\\mathsf{G}^{\\prime}$ ”。模拟接触时，使用等效杨氏模量来估算接触压力。对于像凝胶这样的软材料，若使用过高的默认值，会导致问题变得难以求解。  \n\n接触 1  \n\n1 在模型开发器窗口中，单击接触 1。  \n2 在接触的设置窗口中， 定位到接触压力罚因子栏。  \n3 从罚因子控制列表中选择手动调节。  \n4 在 $f_{\\mathfrak{p}}$ 文本框中键入 “10”。  \n\n固定约束 1  \n\n1 在物理场工具栏中单击 边界，然后选择固定约束。  \n2 选择“边界” 7。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 17,
+        "chunk": "# 达 西 定 律 ( D L )  \n\n接下来，在水凝胶域中设置达西定律接口来求解体积平衡方程。通过模型向导添加多孔弹性，大变形接口时，默认将压力自由度的形函数设置为线性，对位移和压力启用标准P2-P1 插值。  \n\n1 在模型开发器窗口的组件 1 (comp1) 节点下，单击达西定律 (dl)。  \n2 选择“域” 2。  \n3 在达西定律的设置窗口中， 单击以展开因变量栏。  \n4 在压力 (Pa) 文本框中键入 “mu”。  \n\n流体 1  \n\n1 在模型开发器窗口的组件 1 (comp1) $\\mid>$ 达西定律 $\\mathbf{\\Pi}(\\mathbf{dI})>$ 多孔介质 1 节点下，单击流体 1。  \n\n2 在流体的设置窗口中， 定位到流体属性栏。  \n3 从流体类型列表中选择不可压缩。  \n4 从 $\\uprho_{\\mathrm{ref}}$ 列表中选择用户定义。 在关联文本框中键入 “rhof”。  \n5 从 $\\upmu$ 列表中选择用户定义。 在关联文本框中键入 “muf”。  \n\n多孔基体 1  \n\n1 在模型开发器窗口中，单击多孔基体 1。  \n2 在多孔基体的设置窗口中， 定位到基体属性栏。  \n3 从 $\\mathfrak{e}_{\\mathfrak{p}}$ 列表中选择用户定义。 在关联文本框中键入 “poro0”。  \n4 从 $\\boldsymbol{\\kappa}$ 列表中选择用户定义。 从列表中选择对称。  \n\n5 在 $\\boldsymbol{\\kappa}$ 表中，输入以下设置：  \n\n<html><body><table><tr><td>KRR</td><td>KRZ</td></tr><tr><td>KRZ</td><td>KZZ</td></tr></table></body></html>  \n\n初始值 1  \n\n1 在模型开发器窗口的组件 1 (comp1) $\\mid>$ 达西定律 (dl) 节点下，单击初始值 1。  \n2 在初始值的设置窗口中， 定位到初始值栏。  \n3 在 mu 文本框中键入 “mu_ref”。  \n\n连续性 1  \n\n禁用接触对的默认连续性条件，本例中需要手动设置适当的接触条件。  \n\n1 在模型开发器窗口中，单击连续性 1。  \n2 在连续性的设置窗口中， 定位到高级栏。  \n3 选中断开连接对复选框。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# 接触（膨胀）  \n\n1 在物理场工具栏中单击 边界，然后选择压力。  \n2 在压力的设置窗口中， 在标签文本框中键入“接触（膨胀）”。  \n3 选择“边界” 9。  \n4 定位到压力栏。 在 $p_{0}$ 文本框中键入 “if(incontact_p1,mu,int1(t))”。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 19,
+        "chunk": "# 自由流动（膨胀）  \n\n1 在物理场工具栏中单击 边界，然后选择压力。  \n2 在压力的设置窗口中， 在标签文本框中键入 “自由流动（膨胀）”。  \n3 定位到压力栏。 在 $p_{0}$ 文本框中键入 “int1(t)”。  \n4 选择“边界” 8。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 20,
+        "chunk": "# 多物理场  \n\n多孔弹性1 (poro1)  \n\n1 在模型开发器窗口的组件 1 (comp1) $\\mid>$ 多物理场节点下，单击多孔弹性 1 (poro1)。  \n2 在多孔弹性的设置窗口中， 定位到多孔弹性耦合属性栏。  \n3 从多孔弹性模型列表中选择双相。  \n4 从 $p_{\\mathrm{ref}}$ 列表中选择参考压力水平 (dl)。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 21,
+        "chunk": "# 网 格 1  \n\n映射 $\\boldsymbol{\\mathrm{\\Pi}}_{I}$  \n\n1 在网格工具栏中单击 映射。  \n\n2 在映射的设置窗口中， 定位到域选择栏。  \n\n3 从几何实体层列表中选择域。  \n\n4 选择“域” 2。  \n\n分布 $\\boldsymbol{\\mathrm{\\Pi}}_{I}$  \n\n1 右键单击映射 1 并选择分布。  \n\n2 选择“边界” 7 和8。  \n\n3 在分布的设置窗口中， 定位到分布栏。  \n\n4 在单元数文本框中键入 “floor(radius/elsize_sw) $+1$ ”。  \n\n分布 2  \n\n1 在模型开发器窗口中，右键单击映射 1 并选择分布。  \n\n2 选择“边界” 6 和9。  \n\n3 在分布的设置窗口中， 定位到分布栏。  \n\n4 在单元数文本框中键入 “floor(height/elsize_sw) $+1$ ”。  \n\n映射 2  \n\n1 在网格工具栏中单击 映射。  \n2 在映射的设置窗口中， 定位到域选择栏。  \n3 从几何实体层列表中选择域。  \n4 选择“域” 1。  \n\n分布 $\\boldsymbol{I}$  \n\n1 右键单击映射 2 并选择分布。  \n\n2 选择“边界” 2。  \n\n3 在分布的设置窗口中， 定位到分布栏。  \n\n4 在单元数文本框中键入 “floor(1.4\\*radius/elsize_sw)+1”。  \n\n分布 2  \n\n1 在模型开发器窗口中，右键单击映射 2 并选择分布。  \n\n2 选择“边界” 1 和5。  \n\n3 在分布的设置窗口中， 定位到分布栏。  \n\n4 在单元数文本框中键入“1”。  \n\n5 单击 全部构建。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 22,
+        "chunk": "# 非均质膨胀  \n\n建立一个参数化的瞬态研究，计算随外部化学势的变化，不同纵横比的受约束水凝胶的非均质膨胀。请注意，扩散系数被设置为一个较大的值，以确保在研究持续时间内达到溶剂的平衡状态。  \n\n1 在模型开发器窗口中，单击研究 1。  \n2 在研究的设置窗口中， 在标签文本框中键入“非均质膨胀”。  \n3 定位到研究设置栏。 清除生成默认绘图复选框。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 23,
+        "chunk": "# 参数化扫描  \n\n1 在研究工具栏中单击 参数化扫描。  \n\n2 在参数化扫描的设置窗口中， 定位到研究设置栏。  \n\n3 单击 添加。  \n\n4 在表中输入以下设置：  \n\n<html><body><table><tr><td>参数名称</td><td>参数值列表</td><td>参数单位</td></tr><tr><td>ar(凝胶纵横比)</td><td>0.1 0.61.0 2.06.0 10.0 20.0100.0</td><td></td></tr></table></body></html>  \n\n步骤 1：瞬态  \n\n1 在模型开发器窗口中，单击步骤 1： 瞬态。  \n2 在瞬态的设置窗口中， 定位到研究设置栏。  \n3 在输出时步文本框中键入 “range(0,0.1,1)\\*t_end”。  \n\n求解器配置  \n\n修改默认求解器建议以提高收敛性。  \n\n解 1 (sol1)  \n\n1 在模型开发器窗口中，右键单击求解器配置并选择显示默认求解器。  \n2 展开解 1 (sol1) 节点。  \n3 在模型开发器窗口中展开非均质膨胀 $\\because$ 求解器配置 $>$ 解 1 (sol1) $\\mid>$ 因变量 1节点，然后单击  \n压力 (comp1.mu)。  \n4 在场的设置窗口中， 定位到缩放栏。  \n5 从方法列表中选择手动。  \n6 在比例因子文本框中键入 “1e5”。  \n7 在模型开发器窗口中，单击位移场 (comp1.u)。  \n8 在场的设置窗口中， 定位到缩放栏。  \n9 在比例因子文本框中键入 “height”。  \n10 在模型开发器窗口中，单击瞬态求解器 1。  \n11 在瞬态求解器的设置窗口中， 单击以展开时间步进栏。  \n12 清除在结束时间插值解复选框。  \n13 在模型开发器窗口中展开非均质膨胀 $>$ 求解器配置 $>$ 解 1 (sol1) $\\mid>$ 瞬态求解器 1节点，然后  \n单击直接。  \n14 在直接的设置窗口中， 定位到常规栏。  \n15 从求解器列表中选择 PARDISO。  \n16 在模型开发器窗口中，单击全耦合 1。  \n17 在全耦合的设置窗口中， 单击以展开方法和终止栏。  \n18 从非线性方法列表中选择恒定 （牛顿）。  \n19 从雅可比矩阵更新列表中选择每个时步一次。  \n20 在最大迭代次数文本框中键入 “10”。  \n21 在研究工具栏中单击 ${}={}$ 计算。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 24,
+        "chunk": "# 添加预定义的绘图  \n\n基于应力的预定义绘图，创建一个表面图，以直观显示三种不同纵横比的凝胶在变形构型下的膨胀比。  \n\n1 在主屏幕工具栏中，单击 添加预定义的绘图以打开添加预定义的绘图窗口。  \n2 转到添加预定义的绘图窗口。  \n3 在模型树中选择非均质膨胀/ 参数化解 1 (sol2) $\\mid>$ 固体力学 $>$ 应力 (solid)。  \n4 单击窗口工具栏中的添加绘图。  \n5 在主屏幕工具栏中，单击 添加预定义的绘图以关闭添加预定义的绘图窗口。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 25,
+        "chunk": "# 结果  \n\n膨胀比  \n\n1 在二维绘图组的设置窗口中， 在标签文本框中键入 “膨胀比”。  \n2 单击以展开标题栏。 从标题类型列表中选择手动。  \n3 在标题文本区中键入 “表面：膨胀体积比 (1)”。  \n4 定位到绘图设置栏。 清除绘制数据集的边复选框。  \n\n表面 1  \n\n1 在模型开发器窗口中展开膨胀比节点，然后单击表面 1。  \n2 在表面的设置窗口中， 定位到表达式栏。  \n3 在表达式文本框中键入 “comp1.J”。  \n4 定位到数据栏。 从数据集列表中选择非均质膨胀/ 参数化解 1 (sol2)。  \n5 从参数值 (ar) 列表中选择 0.6。  \n6 定位到着色和样式栏。 单击 更改颜色表。  \n7 在颜色表对话框中，选择模型树中的 Rainbow>Rainbow。  \n8 单击确定。  \n9 在表面的设置窗口中， 定位到着色和样式栏。  \n10 从颜色表类型列表中选择离散。  \n\n网格 1  \n\n1 在模型开发器窗口中，右键单击膨胀比并选择网格。  \n2 在网格的设置窗口中， 定位到数据栏。  \n3 从数据集列表中选择非均质膨胀 / 参数化解 1 (sol2)。  \n4 从参数值 (ar) 列表中选择 0.6。  \n5 定位到着色和样式栏。 从单元颜色列表中选择无。  \n6 单击以展开继承样式栏。 从绘图列表中选择表面 1。  \n\n变形 1右键单击网格 1 并选择变形。  \n\n网格1, 表面1  \n\n1 在模型开发器窗口的结果 $>$ 膨胀比下，按住 Ctrl 并单击以选择表面 1 和网格 1。  \n2 右键单击并选择复制粘贴。  \n\n表面 2  \n\n1 在模型开发器窗口中，单击表面 2。  \n2 在表面的设置窗口中， 定位到数据栏。  \n3 从参数值 (ar) 列表中选择 2。  \n4 单击以展开继承样式栏。 从绘图列表中选择表面 1。  \n\n平移 1  \n\n1 右键单击表面 2 并选择平移。  \n2 在平移的设置窗口中， 定位到平移栏。  \n3 在 $\\textbf{x}$ 文本框中键入 “1.25”。  \n\n网格 2  \n\n1 在模型开发器窗口的结果 $>$ 膨胀比节点下，单击网格 2。  \n2 在网格的设置窗口中， 定位到数据栏。  \n3 从参数值 (ar) 列表中选择 2。  \n\n平移 1  \n\n1 右键单击网格 2 并选择平移。  \n2 在平移的设置窗口中， 定位到平移栏。  \n3 在 $\\textbf{x}$ 文本框中键入 “1.25”。  \n\n网格2, 表面2  \n\n1 在模型开发器窗口的结果 $>$ 膨胀比下，按住 Ctrl 并单击以选择表面 2 和网格 2。  \n2 右键单击并选择复制粘贴。  \n\n表面 3  \n\n1 在模型开发器窗口中，单击表面 3。  \n2 在表面的设置窗口中， 定位到数据栏。  \n3 从参数值 (ar) 列表中选择 10。  \n\n平移 1  \n\n1 在模型开发器窗口中展开表面 3 节点，然后单击平移 1。  \n2 在平移的设置窗口中， 定位到平移栏。  \n3 在 $\\textbf{x}$ 文本框中键入 “3.5”。  \n\n网格 3  \n\n1 在模型开发器窗口的结果 $>$ 膨胀比节点下，单击网格 3。  \n2 在网格的设置窗口中， 定位到数据栏。  \n3 从参数值 (ar) 列表中选择 10。  \n\n平移 1  \n\n1 在模型开发器窗口中展开网格 3 节点，然后单击平移 1。  \n2 在平移的设置窗口中， 定位到平移栏。  \n3 在 $\\textbf{x}$ 文本框中键入 “3.5”。  \n\n膨胀比  \n\n在模型开发器窗口的结果节点下，单击膨胀比。  \n\n表格注释 1  \n\n1 在膨胀比工具栏中单击 更多绘图，然后选择表格注释。  \n2 在表格注释的设置窗口中， 定位到数据栏。  \n3 从源列表中选择局部表。  \n\n4 在表中输入以下设置：  \n\n<html><body><table><tr><td>x坐标</td><td>y坐标</td><td>注释</td></tr><tr><td>0.2</td><td>-0.35</td><td>D/H = 0.6</td></tr><tr><td>2.0</td><td>-0.35</td><td>D/H = 2</td></tr><tr><td>6.0</td><td>-0.35</td><td>D/H = 10</td></tr></table></body></html>  \n\n5 定位到着色和样式栏。 清除显示点复选框。  \n\n6 从锚点列表中选择居中。  \n\n7 在膨胀比工具栏中单击 绘制。  \n\n![](images/3a462422871fe797def4cdb5676e162cdd9806ff5cdf3fe9151ac372ba9df041.jpg)  \n\n![](images/066956e5c702be0a4b4b772833caec85597b79cf70b4c5f1846b8b7aeefad34d.jpg)  \n\n凝胶高度  \n\n创建一个类似于参考资料 2 中图 6 的归一化凝胶高度图。  \n\n1 在结果工具栏中单击 $\\sim$ 一维绘图组。  \n2 在一维绘图组的设置窗口中， 在标签文本框中键入 “凝胶高度”。  \n3 定位到数据栏。 从数据集列表中选择非均质膨胀/ 参数化解 1 (sol2)。  \n4 从时间选择列表中选择最后一个。  \n5 单击以展开标题栏。 从标题类型列表中选择手动。  \n6 在标题文本区中键入 “平衡凝胶高度”。  \n7 定位到绘图设置栏。  \n8 选中 $\\textbf{x}$ 轴标签复选框。 在关联文本框中键入 “凝胶纵横比 (1)”。  \n9 选中y 轴标签复选框。 在关联文本框中键入 “归一化凝胶高度 h/H<sub>0</sub>”。  \n10 定位到轴栏。 选中手动轴限制复选框。  \n1 在 $\\textbf{x}$ 最小值文本框中键入 “0.1”。  \n12 在 $\\textbf{x}$ 最大值文本框中键入 “100”。  \n13 在 $\\textbf{y}$ 最小值文本框中键入 “3.2”。  \n14 在y 最大值文本框中键入 “5”。  \n15 选中 $\\textbf{x}$ 轴对数刻度复选框。  \n16 定位到栅格栏。 选中手动间距复选框。  \n17 在y 间距文本框中键入“0.2”。  \n18 定位到图例栏。 清除显示图例复选框。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 26,
+        "chunk": "# 点结果图 1  \n\n1 右键单击凝胶高度并选择点结果图。  \n2 选择“点” 7。  \n3 在点结果图的设置窗口中， 定位到 $\\textbf{y}$ 轴数据栏。  \n4 在表达式文本框中键入 “(height $+\\boldsymbol{\\mathsf{w}}$ )/(height/stretch0)”。  \n5 定位到 $\\textbf{x}$ 轴数据栏。 从轴源数据列表中选择ar。  \n6 单击以展开着色和样式栏。 从宽度列表中选择2。  \n7 找到线标记子栏。 从标记列表中选择圆。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 27,
+        "chunk": "# 添加物理场  \n\n为了进行比较，需要计算凝胶均质膨胀时的膨胀伸长率，这可以通过求解两个非线性全局微分代数方程来计算出自由膨胀和单轴膨胀的伸长率。  \n\n1 在主屏幕工具栏中，单击  \n\n![](images/0e19cf9ff43d8dd5b42c8e2c041e329248cd7d95269b735db96d81372c2f6ee8.jpg)  \n\n添加物理场以打开添加物理场窗口。  \n\n2 转到添加物理场窗口。  \n\n3 在模型树中选择数学 $>$ 常微分和微分代数方程接口 $>$ 全局常微分和微分代数方程 (ge)。  \n\n4 单击窗口工具栏中的添加到“组件 1”。  \n\n5 在主屏幕工具栏中，单击 添加物理场以关闭添加物理场窗口。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 28,
+        "chunk": "# 全局常微分和微分代数方程 ( G E )  \n\n全局方程1 (ODE1)  \n\n1 在模型开发器窗口的组件 1 (comp1) $\\mid>$ 全局常微分和微分代数方程 (ge)节点下，单击全局方程 1 (ODE1)。  \n\n2 在全局方程的设置窗口中， 定位到全局方程栏。  \n\n3 在表中输入以下设置：  \n\n<html><body><table><tr><td>名称</td><td>f(u,ut,utt,t) (1)</td><td>初始值 (u_0) (1)</td><td>初始值 (u_t0) (1/s)</td><td>描述</td></tr><tr><td>lam0_free</td><td>G/(lam0_free^3)* (lam0_free^2-1)+Kmix*(log(1- lam0_free^(-3))+lam0_free^（- 3)+chi*lam0_free^(-6))-mu_sw</td><td>2</td><td>0</td><td>自由膨胀比</td></tr><tr><td>lam0_ua</td><td>G/(stretcho^2*lam0_ua)* (lam0_ua^2-1)+Kmix*(log(1-1/ (stretch0^2*lam0_ua))+1/ (stretch0^2*lam0_ua)+chi/ (stretch0^4*lam0_ua^2)）- mu_sw</td><td>2</td><td>0</td><td>单轴膨胀比</td></tr></table></body></html>  \n\n![](images/85a43ce84a1c510fe4443992173c8d6a1f74671988787cccbb8dda375ab4aab2.jpg)  \n\n5 在源项物理量表中，输入以下设置：  \n\n<html><body><table><tr><td>源项物理量</td><td>单位</td></tr><tr><td>定制单位</td><td>Pa</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 29,
+        "chunk": "# 添加研究  \n\n1 在主屏幕工具栏中，单击 添加研究以打开添加研究窗口。  \n\n2 转到添加研究窗口。  \n\n3 找到研究子栏。 在选择研究树中选择一般研究 $>$ 稳态。  \n\n4 单击窗口工具栏中的添加研究。  \n\n5 在主屏幕工具栏中，单击 添加研究以关闭添加研究窗口。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 30,
+        "chunk": "# 均质膨胀  \n\n1 在模型开发器窗口中，单击研究 2。  \n2 在研究的设置窗口中， 在标签文本框中键入“均质膨胀”。  \n3 定位到研究设置栏。 清除生成默认绘图复选框。  \n\n步骤 1：稳态  \n\n禁用除全局常微分和微分代数方程接口外的所有物理场接口。此外，由于只求解全局自由度，因此不需要网格。  \n\n1 在模型开发器窗口的均质膨胀节点下，单击步骤 1： 稳态。  \n\n2 在稳态的设置窗口中， 定位到物理场和变量选择栏。  \n\n3 选中修改研究步骤的模型配置复选框。  \n\n4 在模型树中选择组件 1 (comp1) $\\mid>$ 定义 $>$ 接触对 1 (p1)。  \n\n![](images/25c984bad178739f05a48290bb96c55e81f48b9030a941966b6f6cbbc025f8f4.jpg)  \n\n6 在树结构中，选择组件 1 (comp1) $>$ 固体力学 (solid), 控制空间坐标系和组件 1 (comp1)>达西定律 (dl)。  \n\n![](images/474abbac645bc55c3e17d0c12246d260cfb23cc253bd8cdac93786c9ba9a4c73.jpg)  \n\n8 在模型树中选择组件 1 (comp1) $\\mid>$ 多物理场 $>$ 多孔弹性 1 (poro1)。  \n\n![](images/1301a2af0cb28e7a367010382ac30957e5d55280882fe2667a266e2464e9170d.jpg)  \n\n10 单击以展开网格选择栏。 在表中输入以下设置：  \n\n<html><body><table><tr><td>组件</td><td>网格</td></tr><tr><td>组件1</td><td>无网格</td></tr></table></body></html>  \n\n11 在研究工具栏中单击 ${}={}$ 计算。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 31,
+        "chunk": "# 结果  \n\n创建一个计算组，用于读取均质膨胀伸长率，以便在凝胶高度图中使用。  \n\n均质膨胀伸长率  \n\n1 在结果工具栏中单击 计算组。  \n\n2 在计算组的设置窗口中， 在标签文本框中键入 “均质膨胀伸长率”。  \n\n3 定位到数据栏。 从数据集列表中选择均质膨胀 / 解 11 (sol11)。  \n\n全局计算 1  \n\n1 右键单击均质膨胀伸长率并选择全局计算。  \n\n2 在均质膨胀伸长率工具栏中单击 ${}={}$ 计算。  \n\n全局 1  \n\n1 在模型开发器窗口中，右键单击凝胶高度并选择全局。  \n\n2 在全局的设置窗口中， 定位到 y 轴数据栏。  \n\n3 在表中输入以下设置：  \n\n<html><body><table><tr><td>表达式</td><td>单位</td><td>描述</td></tr><tr><td>3.3900</td><td>1</td><td>自由均质膨胀</td></tr><tr><td>4.7815</td><td>1</td><td>单轴均质膨胀</td></tr></table></body></html>  \n\n4 定位到 $\\textbf{x}$ 轴数据栏。 从轴源数据列表中选择ar。  \n\n5 单击以展开着色和样式栏。 从宽度列表中选择2。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 32,
+        "chunk": "# 凝胶高度  \n\n在模型开发器窗口中，单击凝胶高度。  \n\n表格注释 1  \n\n1 在凝胶高度工具栏中单击 $\\sim$ 更多绘图，然后选择表格注释。  \n\n2 在表格注释的设置窗口中， 定位到数据栏。  \n\n3 从源列表中选择局部表。  \n\n4 在表中输入以下设置：  \n\n<html><body><table><tr><td>x坐标</td><td>y坐标</td><td>注释</td></tr><tr><td>3.2</td><td>3.45</td><td>自由膨胀</td></tr><tr><td>3.2</td><td>4.85</td><td>单轴膨胀</td></tr></table></body></html>  \n\n5 定位到着色和样式栏。 清除显示点复选框。  \n\n6 从锚点列表中选择居中。  \n\n7 在凝胶高度工具栏中单击 绘制。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 33,
+        "chunk": "# 全局定义  \n\n接下来，设置单轴固结载荷工况。首先，修改部分材料参数，请参见表格 1。  \n\n材料参数  \n\n1 在模型开发器窗口的全局定义节点下，单击材料参数。  \n\n2 在参数的设置窗口中， 定位到参数栏。  \n\n3 在表中输入以下设置：  \n\n<html><body><table><tr><td>名称</td><td>表达式</td><td>值</td><td>描述</td></tr><tr><td>chi</td><td>0.2</td><td>0.2</td><td>混合</td></tr><tr><td>D</td><td>8e-10[m^2/s]</td><td>8E-10 m²/s</td><td>溶剂扩散系数</td></tr></table></body></html>  \n\n模型参数  \n\n1 在模型开发器窗口中，单击模型参数。  \n\n2 在参数的设置窗口中， 定位到参数栏。  \n\n3 在表中输入以下设置：  \n\n<html><body><table><tr><td>名称</td><td>表达式</td><td>值</td><td>描述</td></tr><tr><td>stretcho</td><td>3.215</td><td>3.215</td><td>自由膨胀拉伸</td></tr><tr><td>mu_ref</td><td>O[Pa]</td><td>O Pa</td><td>参考化学势</td></tr><tr><td>stress</td><td>0.05*Kmix/(stretch0^2)</td><td>1.9349E5 Pa</td><td>标称应力</td></tr></table></body></html>  \n\n阶跃 1 (step1)  \n\n添加一个平滑的阶跃函数，用于施加蠕变载荷。  \n\n1 在主屏幕工具栏中单击 $\\mathsf{f}({\\mathsf{x}})$ 函数，然后选择全局 $>$ 阶跃。  \n2 在阶跃的设置窗口中， 定位到参数栏。  \n3 在位置文本框中键入 “0.05”。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 34,
+        "chunk": "# 固 体 力 学 ( S O L I D )  \n\n在模型开发器窗口的组件 1 (comp1) 节点下，单击固体力学 (solid)。  \n\n边界载荷 1  \n\n1 在物理场工具栏中单击 边界，然后选择边界载荷。  \n\n2 选择“边界” 8。  \n\n3 在边界载荷的设置窗口中， 定位到力栏。  \n\n4 将 $\\mathbf{F_{A}}$ 矢量指定为",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 35,
+        "chunk": "# -stress\\*step1(t/(1[s])) z  \n\n辊支承 1  \n\n1 在物理场工具栏中单击 边界，然后选择辊支承。  \n\n2 选择“边界” 9。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 36,
+        "chunk": "# 达 西 定 律 ( D L )  \n\n在模型开发器窗口的组件 1 (comp1) 节点下，单击达西定律 (dl)。  \n\n自由流动（固结）  \n\n1 在物理场工具栏中单击 $\\circleddash$ 边界，然后选择压力。  \n2 在压力的设置窗口中， 在标签文本框中键入 “自由流动（固结）”。  \n3 选择“边界” 8。  \n4 定位到压力栏。 在 $p_{0}$ 文本框中键入 “mu_ref”。  \n\n网 格 2在网格工具栏中单击添加网格，然后选择添加网格。  \n\n映射 1  \n\n1 在网格工具栏中单击 映射。  \n2 在映射的设置窗口中， 定位到域选择栏。  \n3 从几何实体层列表中选择域。  \n4 选择“域” 2。  \n\n分布 1  \n\n1 右键单击映射 1 并选择分布。  \n2 选择“边界” 7 和8。  \n3 在分布的设置窗口中， 定位到分布栏。  \n4 在单元数文本框中键入“1”。  \n\n分布 2  \n\n1 在模型开发器窗口中，右键单击映射 1 并选择分布。  \n\n2 选择“边界” 6 和9。  \n\n3 在分布的设置窗口中， 定位到分布栏。  \n\n4 在单元数文本框中键入 “floor(height/elsize_c)+1”。  \n\n映射 2  \n\n1 在网格工具栏中单击 映射。  \n2 在映射的设置窗口中， 定位到域选择栏。  \n3 从几何实体层列表中选择域。  \n4 选择“域” 1。  \n\n分布 $\\boldsymbol{I}$  \n\n1 右键单击映射 2 并选择分布。  \n2 选择“边界” 1 和5。  \n3 在分布的设置窗口中， 定位到分布栏。  \n4 在单元数文本框中键入“1”。  \n5 单击 全部构建。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 37,
+        "chunk": "# 添加研究  \n\n添加一个新的瞬态研究，用于计算固结载荷工况。修改研究的模型构型，以排除特定于膨胀载荷工况的边界条件。  \n\n1 在研究工具栏中，单击  \n\n![](images/55a07f3ee56ab2cfb3fdeef11548e3c3243ccbe5b8889fc3893f76766646f079.jpg)  \n\n添加研究以打开添加研究窗口。  \n\n2 转到添加研究窗口。  \n\n3 找到研究子栏。 在选择研究树中选择一般研究 $>$ 瞬态。  \n\n4 单击窗口工具栏中的添加研究。  \n\n5 在研究工具栏中，单击 添加研究以关闭添加研究窗口。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 38,
+        "chunk": "# 单轴固结  \n\n1 在模型开发器窗口中，单击研究 3。  \n2 在研究的设置窗口中， 定位到研究设置栏。  \n3 清除生成默认绘图复选框。  \n4 在标签文本框中键入 “单轴固结”。  \n\n步骤 1：瞬态  \n\n1 在模型开发器窗口的单轴固结节点下，单击步骤 1： 瞬态。  \n\n2 在瞬态的设置窗口中， 定位到研究设置栏。  \n\n3 在输出时步文本框中键入 “{0 1 2 5 10 20 50 100 200 1000}\\*(height/stretch0) ${\\bf\\hat{\\mu}}_{2/\\mathsf{D}}^{\\prime\\prime}$ 。  \n\n4 定位到物理场和变量选择栏。 选中修改研究步骤的模型配置复选框。  \n\n5 在模型树中选择组件 1 (comp1) $\\mid>$ 定义 $>$ 接触对 1 (p1)。  \n\n![](images/c4ddbd44f0443bbdb1cc4c426630a5e60c9853bd230e83f14d1178e2a4bff464.jpg)  \n\n7 在树结构中，选择组件 1 (comp1)> 达西定律 $(\\mathbf{d}\\mathbf{l})>$ 接触（膨胀）和组件 1 (comp1) $>$ 达西定律 $\\mathbf{\\Pi}(\\mathbf{d}\\mathbf{I})>$ 自由流动 （膨胀）。  \n\n![](images/92cdb3447c6d48437b807be8c9fdf76ac848b41e862b474c24c35326c593e2fd.jpg)  \n\n9 在模型树中选择组件 1 (comp1) $\\mid>$ 全局常微分和微分代数方程 (ge)。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 39,
+        "chunk": "# 10 单击 $\\oslash$ 模型中禁用。  \n\n解 $12\\ (s o l I2)$  \n\n1 在模型开发器窗口中，右键单击求解器配置并选择显示默认求解器。  \n\n2 展开解 12 (sol12) 节点。  \n\n3 在模型开发器窗口中展开单轴固结 $\\scriptstyle>,$ 求解器配置 $>$ 解 12 (sol12) $\\mid>$ 因变量 1节点，然后单击压力 (comp1.mu)。  \n\n4 在场的设置窗口中， 定位到缩放栏。  \n\n5 从方法列表中选择手动。  \n\n6 在比例因子文本框中键入 “1.0e5”。  \n\n7 在模型开发器窗口中，单击位移场 (comp1.u)。  \n\n8 在场的设置窗口中， 定位到缩放栏。  \n\n9 在比例因子文本框中键入 “height”。  \n10 在模型开发器窗口中，单击瞬态求解器 1。  \n11 在瞬态求解器的设置窗口中， 定位到时间步进栏。  \n12 从求解器采用的步长列表中选择精确。  \n13 选中初始步长复选框。  \n14 在模型开发器窗口中展开单轴固结 $\\mathrm{\\dot{>}}$ 求解器配置 $>$ 解 12 (sol12) $\\mid>$ 瞬态求解器 1节点，然后  \n单击直接。  \n15 在直接的设置窗口中， 定位到常规栏。  \n16 从求解器列表中选择 PARDISO。  \n17 在模型开发器窗口中，单击全耦合 1。  \n18 在全耦合的设置窗口中， 定位到方法和终止栏。  \n19 从雅可比矩阵更新列表中选择每个时步一次。  \n20 在最大迭代次数文本框中键入 “10”。  \n21 在研究工具栏中单击 ${}={}$ 计算。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 40,
+        "chunk": "# 结果  \n\n在 “单轴固结”研究的数据集中添加一个选择，以便在创建表面图时排除刚性基底。  \n\n单轴固结/ 解12 (sol12)  \n\n在模型开发器窗口中展开结果 $>$ 数据集节点，然后单击单轴固结 / 解 12 (sol12)。  \n\n选择  \n\n1 在结果工具栏中单击 属性，然后选择选择。  \n2 在选择的设置窗口中， 定位到几何实体选择栏。  \n3 从几何实体层列表中选择域。  \n4 选择“域” 2。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 41,
+        "chunk": "# 添加预定义的绘图  \n\n1 在主屏幕工具栏中，单击 添加预定义的绘图以打开添加预定义的绘图窗口。  \n2 转到添加预定义的绘图窗口。  \n3 在模型树中选择单轴固结 / 解 12 (sol12) $\\mid>$ 固体力学 $>$ 应力 (solid)。  \n4 单击窗口工具栏中的添加绘图。  \n5 在主屏幕工具栏中，单击 添加预定义的绘图以关闭添加预定义的绘图窗口。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 42,
+        "chunk": "# 结果",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 43,
+        "chunk": "# 压力和化学势  \n\n1 在模型开发器窗口中展开结果 $>$ 应力 (solid) 节点，然后单击应力 (solid)。  \n2 在二维绘图组的设置窗口中， 在标签文本框中键入 “压力和化学势”。  \n3 定位到数据栏。 从时间 (s) 列表中选择24187。  \n4 单击以展开绘图阵列栏。 选中启用复选框。  \n5 从位移列表中选择绝对。  \n6 在单元位移文本框中键入 “0.4”。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 44,
+        "chunk": "# 混合物应力  \n\n1 在模型开发器窗口的结果 $>$ 压力和化学势节点下，单击表面 1。  \n2 在表面的设置窗口中， 在标签文本框中键入“混合物应力”。  \n3 定位到表达式栏。 在表达式文本框中键入 “-poro1.sGpzz”。  \n4 从单位列表中选择 $\\mathbf{kPa}$ 。  \n5 选中描述复选框。 在关联文本框中键入 “正应力”。  \n6 右键单击混合物应力并选择复制粘贴。  \n\n化学势  \n\n1 在模型开发器窗口的结果 $>$ 压力和化学势节点下，单击混合物应力 1。  \n2 在表面的设置窗口中， 在标签文本框中键入“化学势”。  \n3 定位到表达式栏。 在表达式文本框中键入 “mu”。  \n4 在描述文本框中键入 “化学势”。  \n5 定位到继承样式栏。 从绘图列表中选择混合物应力。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 45,
+        "chunk": "# 面上箭头 1  \n\n1 在模型开发器窗口中，右键单击压力和化学势并选择面上箭头。  \n2 在面上箭头的设置窗口中， 定位到表达式栏。  \n3 在R 分量文本框中键入“dl.u”。  \n4 在Z 分量文本框中键入“dl.w”。  \n5 定位到箭头位置栏。 找到R 栅格点子栏。 在点数文本框中键入 “4”。  \n6 找到 $\\textbf{z}$ 栅格点子栏。 在点数文本框中键入 “20”。  \n7 单击以展开继承样式栏。 从绘图列表中选择混合物应力。  \n8 清除箭头比例因子复选框。  \n9 清除颜色复选框。  \n10 清除颜色和数据范围复选框。  \n11 单击以展开绘图阵列栏。 选中手动编制索引复选框。  \n12 在索引文本框中键入 “1”。  \n\n变形 1右键单击面上箭头 1 并选择变形。  \n\n表格注释 1  \n\n1 在压力和化学势工具栏中单击 更多绘图，然后选择表格注释。  \n2 在表格注释的设置窗口中， 定位到数据栏。  \n3 从源列表中选择局部表。  \n\n4 在表中输入以下设置：  \n\n<html><body><table><tr><td>x坐标</td><td>y坐标</td><td>注释</td></tr><tr><td>0.05</td><td>-0.015</td><td>正应力 $-\\sigma_{zz}$</td></tr><tr><td>0.45</td><td>-0.015</td><td>化学势 $\\mu$</td></tr></table></body></html>  \n\n5 选中 LaTeX 标记复选框。  \n6 定位到着色和样式栏。 清除显示点复选框。  \n7 从锚点列表中选择居中。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 46,
+        "chunk": "# 压力和化学势  \n\n1 在模型开发器窗口中，单击压力和化学势。  \n2 在二维绘图组的设置窗口中， 定位到标题栏。  \n3 从标题类型列表中选择手动。  \n4 在标题文本区中键入 “表面：正应力 (kPa) 表面：化学势 (kPa)  \n5 在压力和化学势工具栏中单击 绘制。  \n6 在图形工具栏中单击 缩放到窗口大小按钮。  \n\n厚度伸长率  \n\n按照以下操作说明重现参考资料 1 中的图 4。  \n\n1 在结果工具栏中单击 $\\sim$ 一维绘图组。  \n2 在一维绘图组的设置窗口中， 在标签文本框中键入 “厚度伸长率”。  \n3 定位到数据栏。 从数据集列表中选择单轴固结 / 解 12 (sol12)。  \n4 定位到绘图设置栏。  \n5 选中 $\\textbf{x}$ 轴标签复选框。 在关联文本框中键入 “Z/H”。  \n6 选中 y 轴标签复选框。在关联文本框中键入 “\\lambda<sub>3</sub>”。  \n7 定位到轴栏。 选中手动轴限制复选框。  \n8 在 $\\textbf{x}$ 最小值文本框中键入 “0”。  \n9 在 $\\textbf{y}$ 最小值文本框中键入 “0.5”。  \n10 在y 最大值文本框中键入 “3.5”。  \n11 定位到栅格栏。 选中手动间距复选框。  \n12 在 $\\textbf{x}$ 间距文本框中键入“0.2”。  \n13 在y 间距文本框中键入“0.5”。  \n14 定位到图例栏。 清除显示图例复选框。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 47,
+        "chunk": "# 线结果图 1  \n\n1 右键单击厚度伸长率并选择线结果图。  \n2 选择“边界” 6。  \n3 在线结果图的设置窗口中， 定位到 y 轴数据栏。  \n4 在表达式文本框中键入 “solid.stchp3\\*stretch0”。  \n5 选中描述复选框。 在关联文本框中键入 “第三主伸长率”。  \n6 定位到 $\\textbf{x}$ 轴数据栏。 从参数列表中选择表达式。  \n7 在表达式文本框中键入 “1-Z/height”。  \n8 单击以展开着色和样式栏。 从颜色循环列表中选择Long。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 48,
+        "chunk": "# 厚度伸长率  \n\n在模型开发器窗口中，单击厚度伸长率。  \n\n表格注释 1  \n\n1 在厚度伸长率工具栏中单击 $\\sim$ 更多绘图，然后选择表格注释。  \n2 在表格注释的设置窗口中， 定位到数据栏。  \n3 从源列表中选择局部表。  \n\n4 在表中输入以下设置：  \n\n<html><body><table><tr><td>x坐标</td><td>y坐标</td><td>注释</td></tr><tr><td>0</td><td>3.2</td><td>$0^+$</td></tr><tr><td>0.06</td><td>2.9</td><td>1</td></tr><tr><td>0.09</td><td>2.8</td><td>２</td></tr><tr><td>0.14</td><td>2.7</td><td>5</td></tr><tr><td>0.2</td><td>2.6</td><td>10</td></tr><tr><td>0.28</td><td>2.5</td><td>20</td></tr><tr><td>0.43</td><td>2.2</td><td>50</td></tr></table></body></html>  \n\n<html><body><table><tr><td>x坐标</td><td>y坐标</td><td>注释</td></tr><tr><td>0.59</td><td>2.0</td><td>100</td></tr><tr><td>0.76</td><td>1.5</td><td>$Dt/H_0^2 = 200$</td></tr><tr><td>0.8</td><td>0.8</td><td>1000</td></tr></table></body></html>  \n\n5 选中 LaTeX 标记复选框。  \n6 定位到着色和样式栏。 清除显示点复选框。  \n7 从锚点列表中选择左下角。  \n8 在厚度伸长率工具栏中单击 绘制。  \n\n参考数据，Hong 等人(2008)， $\\scriptstyle t=2$ 将结果与参考资料 1 中若干时间点的数据进行比较。  \n\n1 在结果工具栏中单击 表格。  \n2 在表格的设置窗口中， 在标签文本框中键入“参考数据，Hong 等人 (2008)， $t=2^{\\prime}$ ”。  \n3 定位到数据栏。 单击 导入。  \n4 浏览到该 App 的 “案例库”文件夹，然后双击文件  \nhydrogel_swelling_uniaxial_t2.txt。  \n\n参考数据，Hong 等人(2008)， $t=20$   \n1 在结果工具栏中单击 表格。  \n2 在表格的设置窗口中， 在标签文本框中键入 “参考数据， Hong 等人 (2008)，$t=20^{\\prime}$ ”。  \n3 定位到数据栏。 单击 导入。  \n4 浏览到该 App 的 “案例库”文件夹，然后双击文件hydrogel_swelling_uniaxial_t20.txt。参考数据，Hong 等人(2008)， $t=I O O$   \n1 在结果工具栏中单击 表格。  \n2 在表格的设置窗口中， 在标签文本框中键入 “参考数据， Hong 等人 (2008)，${\\bf t}={\\bf1}00^{\\prime\\prime}$ 。  \n3 定位到数据栏。 单击 导入。  \n4 浏览到该 App 的 “案例库”文件夹，然后双击文件hydrogel_swelling_uniaxial_t100.txt。  \n\n参考数据，Hong 等人(2008)， $\\scriptstyle t=2$  \n\n1 右键单击厚度伸长率并选择表图。  \n\n2 在表图的设置窗口中， 定位到着色和样式栏。  \n\n3 找到线样式子栏。 从线列表中选择无。  \n4 找到线标记子栏。 从标记列表中选择圆。  \n5 从颜色列表中选择来自主题。  \n6 在标签文本框中键入 “参考数据， Hong 等人 (2008)， $\\scriptstyle\\mathbf{t}=2^{\\prime\\prime}$ ”。  \n7 右键单击参考数据， Hong 等人 (2008)， $\\scriptstyle\\mathbf{t}=2$ 并选择复制粘贴。  \n参考数据，Hong 等人(2008)， $t=20$   \n1 在模型开发器窗口中，单击参考数据，Hong 等人 (2008)， $\\scriptstyle\\mathbf{t}=2.1$ 。  \n2 在表图的设置窗口中， 定位到数据栏。  \n3 从表格列表中选择参考数据，Hong 等人 (2008)， $\\scriptstyle\\mathbf{t}=2\\mathbf{0}$ 。  \n4 在标签文本框中键入 “参考数据， Hong 等人 (2008)， $t=20$ ”。  \n5 右键单击参考数据， Hong 等人 (2008)， $\\scriptstyle\\mathbf{t}=2\\mathbf{0}$ 并选择复制粘贴。  \n参考数据，Hong 等人(2008)， $\\scriptstyle t=I O O$   \n1 在模型开发器窗口的结果 $>$ 厚度伸长率节点下，单击参考数据，Hong 等人 (2008)，$\\scriptstyle\\mathbf{t}=2\\mathbf{0}.\\mathbf{1}$ 。  \n2 在表图的设置窗口中， 在标签文本框中键入 “参考数据， Hong 等人 (2008)，$\\displaystyle\\mathbf{\\boldsymbol{t}}=\\mathbf{\\boldsymbol{1}}00^{\\prime\\prime}$ 。  \n3 定位到数据栏。 从表格列表中选择参考数据，Hong 等人 (2008)， $\\scriptstyle\\mathbf{t=100}$ 。  \n4 在厚度伸长率工具栏中单击 绘制。  \n\n若需重新计算膨胀载荷工况，可在非均质膨胀研究节点下的步骤 1：瞬态设置中更改材料参数并禁用为固结研究添加的边界条件。",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/╝╫╗∙▒√╧йїг╢р░═░╖.json b/task2/task2-chunks/╝╫╗∙▒√╧йїг╢р░═░╖.json
new file mode 100644
index 0000000..0f9edf2
--- /dev/null
+++ b/task2/task2-chunks/╝╫╗∙▒√╧йїг╢р░═░╖.json
@@ -0,0 +1,17 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Supplemental Information",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# Mechanism and effects of polyphenol derivatives for modifying collagen  \n\nLeping Wu1, Hui Shao1, Zehui Fang1, Yuancong Zha $O^{2}$ , Ying Cao1, Quanli Li1\\*  \n\n1 Key Lab. of Oral Diseases Research of Anhui Province, College ＆ Hospital of Stomatology, Anhui Medical University, Hefei, 230032, China  \n\n2 Key Lab. of Advanced Technology for Materials of Education Ministry, School of Materials Science and Engineering, Southwest Jiaotong University, Chengdu, 610031, China  \n\nCorresponding Author’s email address: ql-li $@$ 126.com",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# Synthesis of N-2-(3,4-dihydroxyphenethyl) acrylamide (dopamine acrylamide) (DAA)  \n\nThe N-2-(3,4-dihydroxyphenethyl) acrylamide (DAA) was synthesized according to the reported method (Patil N, Falentin-Daudré C, Jérôme C, Detrembleur C. Mussel-inspired protein-repelling ambivalent block copolymers: controlled synthesis and characterization. Polym. Chem., 2015, 6, 2919–2933) (Scheme 1). $\\mathrm{Na_{2}B_{4}O_{7}{\\cdot}10H_{2}O\\left(6.0g\\right)}$ and $\\mathrm{Na}_{2}\\mathrm{CO}_{3}\\left(3.0\\mathrm{g}\\right)$ were added in a three-neck round-bottom flask containing $250.0\\mathrm{mL}$ of deionized water. This basic aqueous solution was stirring and degassed by argon bubbling with high pure argon $(99.999\\%)$ for 2h, and then dopamine hydrochloride $(1.5~\\mathrm{g})$ was added under argon atmosphere. After the solution was stirring for another 30 minutes, the acryloyl chloride $(3.0~\\mathrm{mL})$ ) was drop-wise added in flask at $0~^{\\circ}\\mathrm{C}$ , $\\ensuremath{4.5\\mathrm{~g~}}$ of ${\\bf N a}_{2}{\\bf C O}_{3}$ was added subsequently to keep the pH above 9 during the reaction. After the reaction was carried out with stirring for 12h at room temperature, the solution was adjusted to $\\mathsf{p H}1-2$ with HCl solution $\\mathrm{\\hbar(6mol/L)}$ . The solution was extracted with ethyl acetate. The organic layer washed with diluted HCl solution $\\mathrm{(0.1~mol/L)}$ and dried over $\\mathrm{Mg}\\mathrm{SO}_{4}$ . The solvent was removed in vacuum to yield crude product, and the pure product was further purified by flash silica gel column chromatography eluting with ethyl acetate and petroleum ether (white solid, $80\\%$ yield).  \n\n![](images/6f5e2cabdc578380b3616fd14a60a9257c99434fb7d3cf8053c4fafbd968eb57.jpg)  \nScheme S1. Synthesis of N-2-(3,4-dihydroxyphenethyl) acrylamide (DAA) monomer.  \n\n$^{1}\\mathrm{H}$ -NMR spectra of DAA was measured on a Bruker AV II-400 spectrometer (400 MHz), and tetramethylsilane (TMS) was used as an internal standard in DMSO- $d_{6}$ (Fig. 1). $\\mathrm{^{1}H}$ -NMR ( $\\delta\\mathsf{p p m}_{,}^{\\cdot}$ : 8.12 (t, 1H, -NH-C=O), 6.40-6.65 (m, 3H, Ph), 6.19 (dd, 1H, - ${\\mathrm{CH}}{=}\\mathrm{CH}_{2}\\backslash$ ), 6.08 (dd, 1H, $\\mathrm{CH}_{2}{=}\\mathrm{CH}{-}$ ) 5.57 (dd, 1H, $\\mathrm{CH}_{2}{=}\\mathrm{CH}{-}$ ), 3.27 (q, 2H, - ${\\mathrm{-CH}}_{2}{\\mathrm{-CH}}_{2}$ NH-), 2.55 (t, 2H, ${\\mathrm{-C}}{\\underline{{\\mathrm{H}}}}_{2}$ - $\\mathrm{CH}_{2}$ -NH-).  \n\n![](images/79478d262c81d45e63483331894fab03ff291eb24d255b1d5773484a19d3a002.jpg)  \nFigure S1. $^{1}\\mathrm{H}\\cdot$ -NMR spectral analysis of DAA  \n\nThe high resolution mass spectrometer analysis (HRMS) of DAA was recorded on Mass spectrometer ICS90. HRMS $(\\mathrm{ESI^{+}})$ : calcd for $\\mathrm{C}_{11}\\mathrm{H}_{13}\\mathrm{N}0_{3}(\\mathrm{N}$ M): 207.0895, Found: 208.0953 $(\\mathsf{M}{+}\\mathsf{H})^{+}$ , 230.0778(M+Na)+.  \n\n![](images/f83052a25d82957edd45945c378c638e80c4c5000b3ea92f4d9034f5b7e63f0f.jpg)  \nFigure S2. High resolution mass spectrometer analysis of DAA",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/╡ч│┴╗¤Janus▓─┴╧.json b/task2/task2-chunks/╡ч│┴╗¤Janus▓─┴╧.json
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+[
+    {
+        "id": 1,
+        "chunk": "# Single Step Assembly of Janus Porous Biomaterial by Sub-Ambient Temperature Electrodeposition  \n\nMiao Lei, Haitao Liao, Shijia Wang, Hang Zhou, Zhiling Zhao, Gregory F. Payne, Xue Qu,\\* and Changsheng Liu\\*  \n\nJanus porous biomaterials are gaining increasing attention and there are considerable efforts to develop simple, rapid, and scalable methods capable of tuning micro- and macro-structures. Here, a single-step electro-fabrication method to create a Janus porous film by the electrodeposition of the amino-polysaccharide chitosan is reported. Specifically, a Janus structure emerges spontaneously when electrodeposition is performed at sub-ambient temperature $(0-5^{\\circ}\\mathsf{C})$ . Sub-ambient temperature electrodeposition experiments show that: a Janus microstructure emerges (potentially as the result of a subtle alteration of the intermolecular interactions responsible for self-assembly); important microstructural features (pore size, porosity, and thicknesses) can be tuned by conditions; and this method is readily scalable (vs serial printing) and can yield complex tubular structures with Janus faces. In vitro studies demonstrate anisotropic cell guidance, and in vivo studies using a rat calvarial defect model further confirm the beneficial features of such Janus porous film for guided bone regeneration. In summary, these results further demonstrate that electro-fabrication provides a simple and scalable platform technology for the controlled functional structures of soft matter for applications in regenerative medicine.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1. Introduction  \n\nAdvanced “Janus” interface materials refer to materials with asymmetric chemistry, morphology, and properties on each face.[1–3] Such materials are widely present in living organisms and integral to important biological functions. For example, cell membranes, blood vessel walls, mucous membranes, and skin all have a highly asymmetric structure, giving them unique mass transfer, mechanical, barrier, and protective properties that enable them to perform distinct physiological tasks.[4,5] These natural Janus interface structures have inspired the development of artificial Janus materials to enable multiple advanced biological functions. For instance, advanced Janus tissue dressings with asymmetric wettability have been reported to confer antibacterial and antifouling properties while promoting tissue regeneration for wound healing.[6–8] Janus adhesives with asymmetric adhesion on each face have been shown to integrate dual functions by allowing tissue bonding on one face while limiting detrimental post-operative adhesions on the opposite face.[9] Janus films with asymmetric topological morphologies (e.g., porous, microgroove patterned, aligned fiber structured) had altered spatial distributions of cells to enable the anisotropic biological response important for bone regeneration.[10,11]  \n\nPorous materials and their composites have extensive applications in the industrial field of mass separation, mechanical protection, optics transition, and heterogeneous catalysts.[12] For instance, porous boron nitride foam with high surface area and high absorption capacity potentially enables an efficient gas absorption and laser irradiation protection material.[13] Porous multiple-phase composites with tunable stiffness and even optics that potentially allow them as advanced protection materials.[14,15] More importantly, porous materials also play an indispensable role in biomedical applications. Porosity is an important structural feature of biomedical porous materials, which provides necessary space and beneficial mass-transport microenvironment for cell growth and proliferation for many regenerative medicine applications (e.g., guided bone regeneration). Janus porous materials with different pore structures on the different faces have been reported to offer beneficial asymmetries in wettability,[16,17] adhesion,[18,19] mass transport,[20,21] cell guidance.[22,23] In this context, there is a growing interest to explore advanced processing techniques to generate structure-controlled Janus porous films. These approaches generally include additive and subtractive methods to create the different morphological structures and sometimes these structural differences are also accompanied by differences in chemical compositions on each face. For instance, additive methods include direct/sequential additive assembly of materials with different porous characteristics by using sequential filtration,[24,25] electrospinning,[26–28] heterogeneous-polymerization,[17,29,30] asymmetric surface coating (e.g., atomic layer deposition, ALD),[31,32] heterogeneously freeze-drying[33,34] or electrodeposition.[22,35] In addition, subtractive methods mainly refer to non-homogeneous pore etching.[36–38] These fabrication approaches have different levels of cost and technological complexity.  \n\nElectrofabrication is an emerging fabrication approach that uses imposed electrical signals (generally ${<}5\\mathrm{~V~}$ ) to guide the assembly of thin films at (or near) an electrode surface.[24,27,39–41] Recently, electrofabrication (i.e., electrodepostion) has shown considerable capabilities for the precise structural control of porous metal architectures (i.e., pore size, surface area, pore structure, etc.) to meet specific requirements for various advanced applications.[42–46] The strengths of electrofabrication are that the methods are generally simple, rapid (minutes), reagentless, and offer unprecedented capabilities for controlling materials’ structure and function. Chitosan is a pH-responsive self-assembling amino-polysaccharide that can be electrodeposited through a cathodic neutralization mechanism.[47] Scheme 1A shows that cathodic reactions can yield high pH conditions near the electrode surface that can induce chitosan’s deprotonation and self-assembly (i.e., gelation) through the formation of physical crosslinks (e.g., crystalline network junctions).[48] Despite this seemingly simple mechanism, there is a subtle balance of macromolecular interactions (e.g., among electrostatic, hydrogen bonding, and hydrophobic interactions) that dramatically control the emergence of hydrogel structure.[49]  \n\nPrevious studies have focused on the importance of the electric field on chitosan’s cathodic electrodeposition and demonstrated that salt-screening can dramatically alter the fieldinduced migration and alignment of the chitosan chains[50,51] and also the chain-chain interactions responsible for selfassembly [48,49]. While these field effects are subtle and incompletely understood, they are reproducible and have been used to fabricate a Janus film with dense/porous asymmetric faces by a sequential two-step deposition: i) electrodeposition without salt generated the dense face, and ii) electrodeposition in the presence of salt generated the porous face.[22] Scheme 1B shows that such a Janus film can provide dual functions: the dense face acts as a barrier to prevent the infiltration of fibroblast cells and the development of undesired fibrous tissue, while the porous layer serves as a scaffold to guide osteoblast ingrown and alveolar bone regeneration.[52–54]  \n\nTemperature is another readily controllable process variable that is expected to have complex but subtle effects on chitosan’s emergent structure during electrodeposition. Increases in temperature are expected to enhance entropically-driven hydrophobic interactions but weaken enthalpically-driven hydrogen bonding. However, it is not possible to predict the temperature effects because of the large effect of the water solvent on the energetics of self-assembly. For instance, the formation of polymer-polymer interchain hydrogen bonds likely displaces water-polymer hydrogen bonds resulting in small net energy differences of uncertain sign (i.e., conditions might slightly favor or disfavor assembly).  \n\nHere, we report that lowering the temperature (ranges from $0{-}5~^{\\circ}\\mathrm{C})$ for chitosan’s electrodeposition significantly alters the deposition process and ultimate structure of the deposited hydrogel enabling a Janus porous film to be controllably fabricated in a single step, as shown in Scheme  1C. When electrodeposition was performed at sub-ambient temperatures, we observed the emergence of a chitosan-based dense/porous Janus film with structural parameters (i.e., pore size, porosity, and layer thicknesses) that could be reproducibly adjusted by deposition conditions (i.e., time and current density), although the detailed molecular-level mechanisms are not fully understood. Initial cell studies demonstrate the biologically-relevant functionality of the individual faces of this chitosan-based Janus film, while studies with a rat calvarial bone defect model further confirms the beneficial features of this Janus film for guided bone regeneration. Overall, this work demonstrates that sub-ambient temperature mediated electro-fabrication provides a simple, rapid (minutes), and scalable approach for the preparation of Janus porous hydrogel films and further suggests the versatility of electro-fabrication as an additive manufacturing method for applications in regenerative medicine.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2. Results and Discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2.1. Electro-Fabrication of Chitosan at Different Temperatures and the Related Characterization  \n\nThe reversible self-assembly of biopolymer hydrogels generally involves non-covalent physical crosslinking mechanisms. Compared to synthetic hydrogels that typically employ covalent crosslinks, the physical crosslinks (i.e., network junctions) of many biopolymer networks are less well defined. In the case of chitosan hydrogels, the network junctions are crystalline regions that form when the chains are neutralized.[55] Upon neutralization, chitosan’s interchain electrostatic repulsions are eliminated while attractive hydrogen bonding and hydrophobic interactions enable the chains to undergo interchain association (e.g., Scheme  1A). Chitosan’s self-assembly is reversible because a decrease in pH can re-protonate chitosan and induce dissociation of the assembled chains. Qualitatively, this self-assembly mechanism is well understood; however, many important details are unresolved and remain inaccessible to experimental observation. For instance, it is unclear how many chains or sugar residues are present in the crystalline network junctions and if/how these numbers can be controllable by deposition conditions.  \n\nFigure 1a shows experimental results for the electro-fabrication of chitosan films at two different temperatures. Experimentally, electrodeposition experiments were performed from chitosan solutions ( $1\\%$ chitosan; pH 4.5; 0.1 M $\\mathrm{H}_{2}\\mathrm{O}_{2})$ at sub-ambient temperature (typically $0{-}5~^{\\circ}\\mathrm{C})$ and room temperature (typically $25\\mathrm{-}27\\ ^{\\circ}\\mathrm{C})$ . $\\mathrm{H}_{2}\\mathrm{O}_{2}$ was included in the deposition solution to enable the cathodic generation of $\\mathrm{OH^{-}}$ . To perform initial experiments, we used a microfluidic device [56] (shown in Figure S1, Supporting Information) that allowed the in situ observation of chitosan’s electrodeposition onto a sidewall of titanium foil cathode (an adjacent platinum foil was used as the anode).  \n\n![](images/6010d9dd1bd235ed3fef06a44f834c6e4e13b32676851e5d5d91b688d43d245b.jpg)  \nScheme 1.  The illustration of a) chitosan’s sol-gel transition during the electrodeposition process and the involved inter-molecular interactions that determine the molecular chains arrangement; b) Altering electrodeposition conditions allows to fabricate of free-standing chitosan film with Janus face for dual functionalization in regenerative medicine: the dense face acts as a barrier to prevent the infiltration of fibroblast cells, while the porous layer serves as a scaffold for osteoblast ingrown. As thus such Janus film has potential applications for guiding alveolar bone regeneration (GBR) by eliminating the interference of fibrous tissue; c) The illustration of a novel sub-ambient temperature mediated single step electrodeposition of Janus porous film. Presumably, sub-ambient temperature subtly tunes the balance of physical interactions in chitosan molecular chains which leads to a dynamic structural reorganization.  \n\nAfter filling the fluidic channel with the chitosan solution, the power was set to a constant current density (i.e., $6.67\\mathrm{mAcm^{-2}}.$ ). The videos (Movies S1 and S2, Supporting Information) show the kinetic process of chitosan electrodeposition at 5 and $27^{\\circ}\\mathrm{C},$ while the micrographs in Figure  1a show the representative images of chitosan’s assembly on the cathode from 0 to $300\\mathrm{~s~}$ .  \n\n![](images/0ea4bbe734611a55cf9919f69d30b482c7840cc207a200b790e3a02b52830755.jpg)  \nFigure 1.  Different structures emerge when chitosan is electrodeposited at two different temperatures. a) The in situ micro-channel observation of the chitosan electrodeposition process under room temperature $(E T_{\\mathsf{R o o m}}$ -Chit, ${\\approx}27^{\\circ}\\mathsf{C})$ and sub-ambient temperature $(\\mathsf{E T}_{\\mathsf{S a}^{-}}\\mathsf{C h i t},\\approx\\mathsf{S}^{\\circ}\\mathsf{C})$ (see Movies S1 and S2, Supporting Information); b) Optical photographs, SEM images of $E T_{\\mathsf{R o o m}}$ -Chit and $\\mathsf{E T}_{\\mathsf{S a}}$ -Chit, as well as the contact angles of the films’ solution-contacting face (SolcFace) and electrode-contacting face (ElecFace); c) XRD spectra show the chitosan electrodeposited under sub-ambient temperature suppresses the emergence of crystallinity in the $\\mathsf{E T}_{\\mathsf{S a}}$ -Chit, and d) rheological measurements show the decreased modulus of $\\mathsf{E T}_{\\mathsf{S a}}$ -Chit compared with $E T_{R\\circ\\circ m}$ -Chit; e) The stress-strain curves of the electrodeposited films, further show the more flexible mechanical properties of wet $\\mathsf{E T}_{\\mathsf{S a}^{-}}\\mathsf{C h i t}$ .  \n\nThe images in the first row of Figure 1a and Movie S1 (Supporting Information) illustrate the complicated dynamics of chitosan’s electrodeposition at room temperature $(\\approx27\\ ^{\\circ}\\mathrm{C})$ . For simplicity, we divide the process into three stages. In the initial growth stage (time $<30$ s), the gel grows (the gel front is marked with a purple dotted line) along the direction perpendicular to the electrode (marked with a purple arrow). As noted in Scheme 1A, gel formation is a complex process resulting from an interplay between $\\mathrm{OH^{-}}$ generation and $\\mathrm{OH^{-}}$ diffusion; chitosan’s migration toward the electrode, chitosan’s deprotonation, and the formation of chitosan interchain associations responsible for gel formation. The initial rapid growth of the transparent chitosan hydrogel presumably involves the formation of a network with a low density of inter-chain interactions. In the second stage (time from 30 to $90\\mathrm{~s~}$ ), the hydrogel was observed to contract despite the continued imposed current and electric field; presumably, this contraction is associated with a reorganization of the chains (potentially an electric field induced chain alignment)[50,51] to form a denser network of inter-chain associations. In the third stage (time $>90:$ ), the hydrogel grows more slowly presumably forming a higher density network.  \n\nThe second row of images in Figure 1a and Movie S2 (Supporting Information) shows a similar three-stage process for chitosan’s electrodeposition at sub-ambient temperature $({\\approx}5^{\\circ}\\mathrm{C})$ . However, during the second stage, contraction of the hydrogel appears to be non-uniform (illustrated by a red arrow) with a porous structure emerging on the solution-contacting face (designated as “SolcFace”) and a non-porous compact structure forming on the electrode-contacting face (designated as “ElecFace”). Both the thicknesses of dense and porous layers increased with time. We should note that initial efforts to electrodeposit chitosan at a higher temperature $(50~^{\\circ}\\mathrm{C})$ were unsuccessful (data not shown).  \n\nIn general, we believe there are two general conclusions from the above observations. First, the temperature significantly affects the kinetics of chitosan’s electrodeposition process and the structure of the emergent hydrogel. Electrodeposition at room temperature $({\\approx}27^{\\circ}\\mathrm{C})$ appeared to yield a chitosan hydrogel with a rather dense and homogeneous structure, while electrodeposition at sub-ambient temperature $({\\approx}5^{\\circ}\\mathrm{C})$ yielded a Janus film with a rather dense structure at the ElecFace, and a porous structure at the SolcFace. Second, the film formed during the initial deposition appears to be dynamic allowing structural reorganizations during subsequent stages of the electrodeposition process. We should note that results in Figure S2 (Supporting Information) indicate that Joule heating effects during these experiments are small that is not surprising given the relatively low voltages (3 V) and current densities $(6.67\\mathrm{\\mA\\cm^{-2}},$ ) used for electrodeposition, and there is not a severe flow of electrolyte during the process of electrodeposition (as shown in Movies S2 and S3, Supporting Information). The formation of the Janus porous structure at sub-ambient temperature is believed relative to a complex interdependence of field and selfassembly dynamics modulated by temperature.  \n\nTo further examine the dependence of the emergent microstructure on the electrodeposition temperature, chitosan’s electrodeposition was performed on a Ti plate under 27 or $5^{\\circ}\\mathrm{C}.$ , and the resultant materials were measured. Briefly, a Ti foil $(2\\thinspace{\\mathrm{cm}}\\times2\\thinspace{\\mathrm{cm}})$ ) working electrode was immersed into a chitosan deposition solution $1\\%$ chitosan; $\\mathrm{pH}5.5$ ) containing $\\mathrm{H}_{2}\\mathrm{O}_{2}(0.1\\mathrm{M})$ and a cathodic potential was applied $(6.67~\\mathrm{mA}~\\mathrm{cm}^{-2}$ , 1000 s). The temperature during the deposition process was strictly controlled using an incubator (Beaver, China). After deposition, the foil with the electrodeposited chitosan was removed from the deposition solution, rinsed with deionized (DI) water, and the chitosan film was peeled from the Ti foil. The photographs in Figure 1b show the electrodeposited chitosan film deposited at room temperature of $27^{\\circ}\\mathrm{C}$ (designated as $^{\\mathrm{*}}\\mathrm{ET_{Room}\\mathrm{\\cdotChit^{\\prime\\prime}}})$ was transparent but became translucent after freeze-drying. In contrast, the films deposited at a sub-ambient temperature of $5~^{\\circ}\\mathrm{C}$ (designated as $^{\\mathrm{*}}\\mathrm{ET_{Sa}}.$ Chit”) were semi-transparent and became white and opaque after freeze-drying. Presumably, this difference in optical appearance is related to differences in their internal microstructure.  \n\nThe SEM images in Figure 1b show such differences in the microstructure. The $\\mathrm{ET_{Room}}$ -Chit has a dense and uniform structure with smooth surfaces on both the ElecFace and the SolcFace, and a rather homogeneous cross-section. In contrast, the $\\mathrm{ET_{Sa}}$ -Chit shows a Janus structure, with the ElecFace showing a uniform dense structure and the SolcFace showing a honeycomb porous structure, and the cross-section shows a dramatic transition between these two faces but without a definite boundary. The insets in the SEM images show the contact angles for the various film-faces and specifically indicate that the SolcFace of the $\\mathrm{ET_{Sa}}$ -Chit has a greater hydrophobicity (contact angle about $111.5^{\\circ}\\pm4.7^{\\circ}.$ compared to the other, hydrophilic faces. Overall, these results show that a Janus structure emerges when a chitosan film is electrodeposited at sub-ambient temperature, which is consistent with the observations in Figure 1a.  \n\nThe X-ray diffraction (XRD) patterns in Figure  1c further show the crystalline structural differences between $\\mathrm{ET_{Room}}$ -Chit and $\\mathrm{ET_{Sa}}$ -Chit. The diffraction peaks at $10.2^{\\circ}$ and $20.1^{\\circ}$ are characteristic crystallization peaks of chitosan chains.[57–59] Compared with $\\mathrm{ET_{Room}}$ -Chit, the diffraction pattern for the $\\mathrm{ET_{Sa}}$ -Chit is lacking the peak at $10.2^{\\circ}$ and has a low intensity for the peak at $20.1^{\\circ}$ , which indicates that the $\\ensuremath{\\mathrm{ET}_{\\mathrm{Sa}}}$ -Chit has lower crystallinity. The ATR-FTIR spectra of Figure S3 further show the chemical structural details of $\\mathrm{ET_{Room}}$ -Chit and $\\mathrm{ET_{Sa}}$ -Chit. Figure 1d shows the rheologically measured storage modulus (i.e., G′) and loss modulus (i.e., $G^{\\prime\\prime})$ of $\\mathrm{ET_{Room}–C h i t}$ and $\\mathrm{ET_{Sa}\\mathrm{-Chit}}$ , which indicates the $\\mathrm{ET_{Room}}$ -Chit with uniform dense structure has the higher mechanical modulus (i.e., higher $\\ensuremath{\\mathbf{G}}^{\\prime}$ and $\\mathbf{{G}^{\\prime\\prime}}$ ), while the $\\mathrm{ET_{Sa}}$ -Chit with Janus porous structure has the lower modulus. The stress-strain curves of $\\mathrm{ET_{Room}}$ -Chit and $\\mathrm{ET_{Sa}}$ -Chit under wet states are shown in Figure  1e, which further shows the higher strength and ductility of the wet $\\mathrm{ET_{Sa}\\mathrm{-Chit}.}$ (Note: the quantitative data and mechanical properties under dry state are shown in Figure S4 and Table S1, Supporting Information).  \n\nIn summary, the above results demonstrate that the temperature significantly affects the dynamics of chitosan’s electrodeposition, and the structure and properties of the resultant gel. Importantly, electrodeposition at sub-ambient temperature (i.e., $5~^{\\circ}\\mathrm{C})$ enabled the fabrication of a Janus porous structure by one-step electro-fabrication. Presumably, this Janus structure emerged as the result of a subtle tuning of the balance of physical interactions and the ability of these interactions to undergo a dynamic sorting at sub-ambient temperature.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2.2. Sub-Ambient Temperature Electro-Fabrication of Janus Film with Tunable Janus Porous Structure  \n\nThe above results illustrate that a Janus porous structure emerges in a time-dependent manner when chitosan is electrodeposited at sub-ambient temperature (i.e., $5~^{\\circ}\\mathrm{C}$ ). To further study this time-dependence, we electrodeposited chitosan films for varying times (t) at sub-ambient temperature $(\\approx5^{\\circ}\\mathrm{C})$ using a chitosan deposition solution (chitosan $1\\%$ ; $\\mathrm{pH}~4.5\\}$ , a Ti foil electrode $(2\\ \\mathrm{cm}\\times2\\ \\mathrm{cm})$ ) and a constant current density $(6.67\\mathrm{mA}\\mathrm{cm}^{-2},$ . Representative SEM images in Figure 2a show how the pore structure for the Janus film emerges during the deposition process. Initially, small pores are generated on the SolcFace but these pores expand with increasing deposition time. For quantitative analysis, we analyzed 100 images from 10 separately-deposited films and used Image J Plus software. Figure  2b shows the pore size increased from 30 to $150~{\\upmu\\mathrm{m}}$ with increasing deposition time. The growth of the pores further indicates that the chitosan chains in the initially-deposited hydrogels can dynamically reconfigure. While the observed time-dependent pore size alteration is reproducible, the underlying mechanism at molecular-level is not understood at present. While the $\\mathrm{ET_{Room}}$ -Chit films electrodeposited at room temperature $(\\approx~27~^{\\circ}\\mathrm{C})$ show the time-dependent increase of thickness, and show dense structures without pore formation, as shown in Figure S5 (Supporting Information).  \n\n![](images/98570ae102c6073924e4f8614ea308fa28784e9c39232a8e0fbe8b9dbeb707cf.jpg)  \nFigure 2.  The varying Janus porous structure as the function of electrodeposition time at sub-ambient temperature $(E T_{\\mathsf{S a}}{\\mathsf{-C h i t}})$ and constant current density. a) The surface and cross-sectional SEM images of deposited films indicate controllability of the Janus porous structure by using different deposition times; b) Histograms of pore size distribution for the $\\mathsf{E T}_{\\mathsf{S a}}$ -Chit’s solution-contacting face (SolcFace; ${\\mathsf n}=700^{\\cdot}$ ). During deposition, c) the thickness of the Janus film and the individual porous layer (X) and dense layer (Y) increased; d) the thickness ratio of porous-to-dense layer (X/Y) decreased, and e) the “average” porosity of the Janus film decreased $(\\mathsf{n}=4)$ .  \n\nThe cross-sectional images of the $\\mathrm{ET_{Sa}}$ -Chit films in Figure 2a show further details of the deposited films’ Janus porous structure. Figure 2c summarizes these results and shows how the thickness of the entire Janus film and the individual porous layer ( $\\therefore30{\\mathrm{-}}100\\ \\upmu\\mathrm{m}$ thick) and dense layer (Y; $5{\\mathrm{-}}40~{\\upmu\\mathrm{m}}$ thick) increase with deposition time. The thickness of the porous layer $(\\mathrm{X})$ was always greater than that of the dense layer (Y), and the relative thickness of the porous to dense layers (X/Y)  \n\nwas observed to decrease with deposition time (Figure  2d). In addition, the $\\mathrm{ET_{Sa}}$ -Chit films in Figure S6 (Supporting Information) indicate that it may be possible to further tune the relative thicknesses of the dense and porous layers by altering deposition conditions (e.g., by using salt). The time-dependent increase in pore size and decrease in the ratio of porous to dense layer thickness $(\\mathrm{X}/\\mathrm Y)$ is expected to lead to decreases in the film’s “average” porosity. The porosity of freeze-dried films was measured experimentally using a standard $\\mathrm{N}_{2}$ gravimetric method and Figure  2e shows the decrease in average porosity (from $90\\%$ to $75\\%$ ) with deposition time. (Note: Figure S7 of the Supporting Information also shows the pore structure and relative parameters (i.e., layer thickness and porosity) for the Janus film are also sensitive to the current density during subambient temperature electrodeposition.)  \n\nIn summary, the results in Figure  2 demonstrate that the sub-ambient temperature electrodeposition of chitosan offers a rapid, single-step method for the electro-fabrication of a Janus porous film. Further, important structural features (porosities and thicknesses) of these films can be tuned by varying the deposition conditions (e.g., time and current).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.3. Scalability of Sub-ambient Temperature Electro-fabrication of Janus Porous Materials  \n\nScalability is a key advantage of electrodeposition compared to other additive manufacturing methods that require serial processing (e.g., printing). To illustrate this capability, we performed a 100-fold upscaling of Janus film fabrication (from a $2.5\\:\\mathrm{cm}\\times2.5\\:\\mathrm{cm}$ film to a $25\\:\\mathrm{cm}\\times25\\:\\mathrm{cm}$ film) using the same electrodeposition time (1000 s). As illustrated in Figure S8 (Supporting Information), we used a Ti foil $(25\\mathrm{cm}\\times25\\mathrm{cm})$ working electrode and a ruthenium-iridium titanium plate as an anode. The deposition was performed from a deposition solution $1\\%$ chitosan; $\\mathrm{pH}~5.5$ ; $0.1\\mathrm{~M~}$ $\\mathrm{H}_{2}\\mathrm{O}_{2}$ ; $5~^{\\circ}\\mathrm{C})$ using an applied cathodic potential $(6.67~\\mathrm{mA}~\\mathrm{cm}^{-2}$ for 1000 s). After peeling the film from the electrode surface, the photograph in Figure 3a shows the film is stable and has an opaque appearance. After freeze-drying, this dried $\\mathrm{ET_{Sa}}$ -Chit film has a white paper-like appearance that can be folded and written (Figure  3b shows the scalable $\\mathrm{ET_{Sa}}$ - Chit after cutting). The surface and cross-sectional SEM images in Figure 3c and Figure 3d show the scaledup $\\mathrm{ET_{Sa}}$ -Chit film has a uniform Janus porous structure.  \n\nAnother advantage is that because electrodeposition allows conformal coating of electrode surfaces, hydrogels can be fabricated with complex (i.e., nonplanar) geometries. To illustrate this capability, we fabricated a hydrogel tube with a Janus microstructure. Tubular biomedical implants are widely used in the tissue regeneration field (e.g., artificial blood vessels,[60,61] nerve conduits,[62,63] and lacrimal duct,[64] etc.), and introducing a Janus microstructure may offer potential benefits (e.g., directional drug/factors transfer[65–67] and anisotropic cell/ tissue guidance[68]). Experimentally, Figure  3e shows we fabricated this tube using a Ti rod (i.e., 2 mm diameter and $60~\\mathrm{mm}$ length) as the working electrode and cylindrical rutheniumiridium titanium “cage” as an anode (i.e., $20~\\mathrm{mm}$ diameter and 40 mm length). (More details of the customized anode were shown in Supporting Information. We also used the same deposition conditions as described above (e.g., $6.67\\mathrm{\\mA\\cm^{-2}}$ for 1000 s) and after deposition peeled the deposited tube from the Ti rod). Figure  3f shows the electrofabricated $\\mathrm{ET_{Sa}}$ -Chit tubes were translucent in appearance, while Figure  3g,h shows the cross-section and surface microstructures. These micrographs demonstrate the Janus structure of the $\\mathrm{ET_{Sa}}$ -Chit tubes with a dense inner layer and porous outer layer.  \n\nIn summary, Figure  3 illustrates that this single-step, subambient temperature electrodeposition of chitosan can be scaled and adapted to non-planar geometries while preserving the resulting porous Janus structure.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.4. Anisotropic Cell Guidance of Janus Porous Films  \n\nAs noted in the Introduction, Janus porous films offer advantages for guided bone regeneration (GBR) by allowing bone defects to be closed and tissue to recover its original structure and function. During the healing period (weeks to months), the dense face of the film should prevent the fibroblasts from connective tissue from invading the bone defect, while the porous face should allow osteoblasts to ingrow and promote their proliferation. To test this dual functionality for the chitosan Janus porous films, we performed cell studies to evaluate if L929 fibroblast cells could penetrate through the different faces of an $\\mathrm{ET_{Sa}}$ -Chit film $(6.67\\mathrm{mA}/\\mathrm{cm}^{2}$ for 1000 s, the dense layer is ${\\approx}50~\\upmu\\mathrm{m}$ and the porous layer is ${\\approx}100~\\ensuremath{\\upmu\\mathrm{m}})$ . These experiments were performed using the system shown in Figure 4a, in which the cell crown insert was sealed with an $\\mathrm{ET_{Sa}}$ -Chit film (dense face up or porous face up) and set on a well plate to isolate two volumes. Then L929 cells were seeded in the upper volume and the distribution of cells in $\\mathrm{ET_{Sa}}$ -Chit was evaluated after different incubation periods. For analysis, we stained live/dead cells at different times and evaluated live cells using confocal laser microscopy (green staining).  \n\nThe fluorescence image in Figure  4b shows the distribution of the cells when seeded on the dense face. The film surface (top image) and optical cross-section (bottom image) show an increasing quantity of live cells, indicating that these fibroblasts continuously proliferated during the 7-day incubation. The fluorescent cross-section images show that the cells were only distributed in a narrow area near the dense layer surface of $\\mathrm{ET_{Sa}}$ -Chit during the whole culturing period. In contrast, Figure 4c shows that when these fibroblast cells were seeded on the porous face, they proliferated continuously and penetrated into the porous face. Furthermore, the penetration depth of cells on different surfaces of $\\mathrm{ET_{Sa}}$ -Chit was further estimated using cross sections from the fluorescence images (since the film is not completely flat, it is difficult to locate the film surface and quantify the penetration distance, so this analysis is semi-quantitative). Figure 4d shows that fibroblasts are narrowly located near the surface of the dense layer of the $\\mathrm{ET_{Sa}}$ -Chit, and cell distribution depth does not appear to change during 7 days of culturing. In contrast, cells were observed to grow from the porous face into the internal space of $\\mathrm{ET_{Sa}}$ -Chit, and the depth of ingrown increases with time.  \n\nIn summary, these results suggest that the Janus porous structure of $\\mathrm{ET_{Sa}}$ -Chit enables the dual functions required for GBR: the dense face serves as a barrier for fibroblast invasion while the porous face permits cell-ingrown.  \n\n![](images/8d4ac3fd2be589134d8003b9143ce7f1d5bf2bc0dc0c0283f47036e12275eeb3.jpg)  \nFigure 3.  Large-scaled preparation and 3D structural customization of Janus porous materials. Optical images show a) the amplified $\\mathsf{E T}_{\\mathsf{S a}}$ -Chit gel $(25\\ c m\\times25\\ c m)$ ) and b) the $\\mathsf{E T}_{\\mathsf{S a}}$ -Chit film after freeze-drying can be folded and written; The c) surface and d) cross-sectional SEM images show the uniform Janus porous structure in a large area; e) The schematic and optical image of an electro-fabrication device for a tube, a Ti rod $(2\\mathsf{m m}$ in diameter and $60~\\mathsf{m m}$ in length) as working electrode and a cylindrical ruthenium-iridium titanium substrate ( $20~\\mathsf{m m}$ in diameter and $40\\mathsf{m m}$ in length) as an anode, and f) the optical image of $\\mathsf{E T}_{\\mathsf{S a}}$ -Chit tube; g) The surface and h) cross-sectional SEM images of $\\mathsf{E T}_{\\mathsf{S a}}^{}$ Chit tube, which show the expected Janus porous structure with inner dense layer and outer porous layer.  \n\n![](images/c72d14fc8e966847debce701f0239c482ec93a81b41482c9a3e76fad95ae56a9.jpg)  \nFigure 4.  The Anisotropic Cell Guidance of the Janus Porous $\\mathsf{E T}_{\\mathsf{S a}}$ -Chit Film. a) A cell crown insert is sealed with a piece of film (the dense face up or the porous face up) and set onto a well plate to isolate the upper and lower volumes for anisotropic cell guidance study. L929 fibroblasts were seeded in the upper volumes isolated by $\\mathsf{E T}_{\\mathsf{S a}}$ -Chit. The b) cell barrier or c) cell ingrowth functions were evaluated using 3D fluorescence images. d) Quantitation of cell distribution depth in $\\mathsf{E T}_{\\mathsf{S a}}$ -Chit. $(^{*}p<0.05$ , $\\because10<0.01$ ; ${\\mathsf n}=4$ ).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.5. In Vivo Studies of Guided Bone Regeneration  \n\nFinally, the in vivo guided bone regeneration capacity of the Janus porous film was assessed using a calvarial defect model with 18 rats. In this study, two critical-size defects $(5~\\mathrm{mm})$ were created in the skulls of these animals and the defects in each animal were treated in the same way. After these defects were created, different films were implanted to cover the defect and the results were compared with the “nofilm control” group as illustrated in Figure 5a. For this test, we selected the $\\mathrm{ET_{Sa}}$ -Chit film $(6.67~\\mathrm{mA}~\\mathrm{cm}^{-2}$ for $1000\\mathrm{~s~}$ , the dense layer is ${\\approx}50~\\upmu\\mathrm{m}$ and the porous layer is ${\\approx}100~\\upmu\\mathrm{m}$ ) as our experimental film because the in vitro results showed it offers the GBR-required dual functionalities: acts as a barrier for fibroblast invasion (associated with the dense layer) and permits osteoblast ingrown (associated with the porous layer). An $\\mathrm{ET_{Room}}$ -Chit film control that lacked a porous layer allows assessment of the importance of the porous layer on bone regeneration. And all procedures were approved by the Animal Research Committee.  \n\nAnimals were sacrificed after 4, 8, and 12 weeks post-surgery, and high-resolution micro-CT scanning was performed to observe the dynamics of new bone formation (Figure 5b shows representative images of each group at three-time points). New bone regeneration (newly formed bone on the left and right is marked in green and blue respectively) was observed in all groups within 12 weeks, but the extent of new tissue and its regeneration rate differed among the three groups. The two groups of calvarial defects covered with films showed more newly formed bone tissue compared to the “no-film control” group post-surgery. From the top and cross-sectional views of Micro-CT, it can be observed that during the healing cycle, the bone regeneration rate of the group covered with Janus porous structure $\\mathrm{ET_{Sa}}$ -Chit film was slightly faster than the group covered with $\\mathrm{ET_{Room}}$ -Chit film. At 12 weeks after surgery, the left bone defect (marked in green) in the group covered with $\\mathrm{ET_{Sa}}$ -Chit film had basically recovered completely while the group covered with $\\mathrm{ET_{Room}}$ -Chit film still had some defects in both sides. Quantitative morphometric analysis using microCT analysis showed that various morphological indicators of new bone in the two groups covered with films were significantly higher than those in the “no-film control” group at all time points. Among them, the trabecular bone volume/total volume ratio (Tb. BV/TV) in the $\\mathrm{ET_{Sa}}$ -Chit group $(0.33\\pm0.05)\\$ was higher than that in the $\\mathrm{ET_{room}}$ -Chit group $(0.24\\pm0.05)$ at 12 weeks $(p<0.05)$ (Figure  5c). Additionally, the trabecular bone mineral density (Tb. BMD) of the newly formed bone in the $\\mathrm{ET_{Sa}}$ -Chit group $(1.29\\pm0.01\\mathrm{g}\\mathrm{cm}^{-3})$ was slightly higher than for the $\\mathrm{ET_{Room}}$ -Chit group $(1.22\\pm0.04\\mathrm{g}\\mathrm{cm}^{-3})$ (Figure 5d). Comparison of the thickness of trabeculae (Tb. Th) showed a similar trend (Figure 5e).  \n\n![](images/2e32b5a11c93a4455fd27092b7e69116752a65c88b76ff0aa3c65ba587bae580.jpg)  \nFigure 5.  Evaluation of the Janus Porous $\\mathsf{E T}_{\\mathsf{S a}}$ -Chit Film for Guided Bone Regeneration. a) Illustrative images showing surgical placement of different film materials $E T_{R\\circ\\circ m}$ -Chit and $\\mathsf{E T}_{\\mathsf{S a}}$ -Chit films) placed on rat calvarial defects and no-film placed on the defects as control groups; b) Micro-CT imaging of treated calvarial defects taken at 4, 8, and 12 weeks after surgery; c) Trabecular bone volume to tissue volume (Tb. BV/TV); d) trabecular bone mineral density (Tb. BMD) and e) trabecular thickness (Tb. Th) evaluated by morphometric analysis; f) H&E staining and g) Masson-trichrome (MT) staining images comparing the newly formed bone in different groups after 12 weeks repair period (NB, new bone; HB, host bone; M, materials; FT, fibrous tissue; red line, the bone defect gap), $(\\mathsf{n}=4)$ .  \n\nHistological analysis based on H&E and Masson-trichrome (MT) staining further supported the micro-CT finding. Representative histological images of each group are shown in Figure 5f,g. Low- magnification optical microscopy images show the overall repair effect of the defects in the three groups at 12 weeks after surgery. A large amount of bone tissue (identified by “NB”) was newly formed between the host bone tissue (identified by “HB”) in the two film-covered groups, and the gap between bone defects was significantly narrower than that in the control group. In the locally enlarged images at the bottom, we found that the control group was filled with fibrous tissue (FB) in the bone defect gap without mature bone tissue. In contrast, an amount of mature bone tissue with dense structure was observed in the $\\mathrm{ET_{Room}}$ -Chit group and $\\mathrm{ET_{Sa}}$ -Chit group, as well as new blood vessels (marked with yellow arrows) surrounding these newly formed bone tissue. In addition, implanted films (identified by $^{\\omega}\\mathrm{M}^{\\prime\\prime}$ ) in two groups showed significant degradation at 4, 8, and 12 weeks after surgery (Figure S9, Supporting Information). These histological results above confirmed the consistency with the micro-CT results, further indicating that the $\\mathrm{ET_{Sa}}$ -Chit with porous Janus structure can effectively guide new bone formation.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 3. Conclusions  \n\nPrevious studies demonstrated the potential of a chitosanbased Janus structure for guided bone regeneration. Compared to those traditional step-by-step processing technologies, we here report a single-step electro-fabrication method to create such a Janus film. Specifically, we report that a Janus structure emerges spontaneously when electrodeposition is performed at sub-ambient temperature $(\\approx5^{\\circ}\\mathrm{C})$ . From a fundamental standpoint, the imposed electrical inputs induce chitosan’s self-assembly through a subtle balancing of electrostatic, hydrophobic, and hydrogen-bond interactions. Experimental observations that the pore size increases while the film is depositing provide evidence for dynamic reconfigurations of the hierarchical structure. While it is not possible to provide a direct explanation for the emergence of a Janus structure, it is possible that the electric field contributes to this structural gradient as prior simulations suggest the field has a distance-dependent effect on chitosan’s chain alignment.[50] While theory cannot yet fully explain the emergence of macroscopic structure, the experiment shows that electrodeposition: allows a tuning of the Janus porous structure (layer thickness and porosity of film, pore size of the porous face): is readily scalable to larger areas, and can yield complex shapes (e.g., Janus porous tube). In vitro and in vivo studies further demonstrate that such porous Janus structure can provide structural functionalities for guiding bone regeneration. Thus, from a practical perspective, these results further illustrate the potential of electro-fabrication as an additive manufacturing method for organizing complex soft matter for applications in regenerative medicine.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 10,
+        "chunk": "# 4. Experimental Section  \n\nMaterials and Devices: Chitosan ( $85\\%$ deacetylation and $200\\mathsf{k D a})$ were purchased from Sigma-Aldrich (USA). Concentrated hydrochloric acid and ${\\sf H}_{2}{\\sf O}_{2}$ were purchased from Shanghai Ling Feng Chemical Reagent Co.,Ltd (China). Chitosan was centrifuged to remove insoluble impurities and residual proteins before use. The three-electrode system (CHI 660E) was used for electrodeposition, and Ti plate $(2\\mathsf{c m}\\times2\\mathsf{c m})$ ) as a working electrode and Pt plate as a counter electrode, $\\mathsf{A g/A g C l}$ as a reference electrode.  \n\nElectro-Fabrication of Chitosan Films Under Different Temperatures: Chitosan $(7\\%\\ w/\\mathsf{v})$ was dissolved in 2M hydrochloric acid ( $[{\\mathsf{p H}}$ range from 4.5–5.0), followed by the addition of 0.1 M ${\\sf H}_{2}{\\sf O}_{2}$ . The temperatures of electrolytes were controlled at 27 and $5^{\\circ}C$ via a dry bath incubator (Beaver, China) during the whole film’s electro-fabrication. The chitosan films’ electro-fabrication was performed with a specific constant current density (0.83 to $20.01\\ m\\mathsf{A\\ c m}^{-2}$ , with potential ranging from 3 to 8 V) and designated time (from 100 to $\\mathsf{l o o}00\\ s_{\\prime}^{\\prime}$ ). After electro-deposition, the chitosan-coated electrode was washed with ultra-pure water for three times, then the deposited chitosan was peeled from the cathode to be as a free-standing film for further characterization.  \n\nIn Situ Visual Monitoring of the Chitosan’s Electrodeposition in MicroChannels: Titanium plate and platinum plate with thickness of $0.05~\\mathsf{m m}$ were used as the working electrode and counter electrode respectively, which were fixed on the quartz glass plate to form a $1.5\\ m m$ distance microchannel. The working area of the two electrodes was $2\\mathsf{m m}\\times2\\mathsf{m m}$ , as shown in Figure S1 (Supporting Information) The two ends of the electrode pair are respectively connected with the electrochemical workstation (CHI 660E) by wires, and the temperature of the electrolyte in the micro-flow channel was precisely controlled at a sub-ambient (i.e., $5^{\\circ}()$ or room temperature (i.e., $27^{\\circ}\\mathsf{C})$ through a water bath, then electrodeposition was performed under the current density of $6.67\\ m A\\ c m^{-2}$ , and the kinetic growth of hydrogel was observed and record under the open field mode of an inverted microscope.  \n\nCharacterization of $E T_{\\mathsf{R o o m}}$ -Chit and $E T_{\\mathsf{S a}}$ -Chit: The morphological analysis was performed on the scanning electron microscope (S-4800, Hitachi). The mechanical properties of the film (Samples: $3.5\\mathsf{m m}\\ \\times$ $20~\\mathsf{m m}$ strips) were measured using a universal tensile test (CMT6104). Crystalline phases of the lyophilized films were assayed on an X-ray diffractometer (Rigaku D/max2550 VB/PC, Bruker).  \n\nA gravimetric method was used for film’s porosity estimation, [69] the apparent density and porosity of the films were calculated by using Equations (1) and (2), respectively:[70]  \n\n$$\n\\begin{array}{r l}&{\\mathsf{A p p a r e n t\\mathop{d e n s i t y}}(\\mathsf{g}/\\mathsf{c m}^{3})}\\\\ &{\\qquad=\\mathsf{M a s s o f}\\mathsf{F i l m}(\\mathsf{g})/\\Bigl[\\mathsf{F i l m}\\mathsf{t h i c k n e s s}(\\mathsf{c m})\\times\\mathsf{F i l m}\\mathsf{a r e a}\\bigl(\\mathsf{c m}^{2}\\bigr)\\Bigr]}\\end{array}\n$$  \n\n$$\n\\mathsf{P o r o s i t y}\\big(\\mathcal{U}\\big)=[1-\\mathsf{A p p a r e n t\\ d e n s i t y}(\\mathsf{g}/\\mathsf{c m}^{3})/\\mathsf{B u l k\\ d e n s i t y}(\\mathsf{g}/\\mathsf{c m}^{3})]\\times100\\%\n$$  \n\nPore Size Estimation: Image Pro 5.0 (Media Cybernetic, USA) software was used to estimate pore size distributions statistically from the film surface and cross-sectional images. Water content estimation: Dry films obtained by vacuum drying at $37^{\\circ}\\mathsf{C}$ were weighed to get Wd. And then they were saturated with water and weighed to get Ww. the water content is calculated according to Eq (3):[71]  \n\n$$\n\\sf r{c o n t e n t\\%}=\\left[\\left(\\sf{W w}-\\mathbb{W d}\\right)/\\mathbb{W}\\right]\\times100\\%\n$$  \n\nTo determine the surface hydrophilicity of chitosan film fabricated under room temperature $(\\approx27^{\\circ}{\\mathsf C})$ and sub-ambient temperature $(\\approx5^{\\circ}{\\mathsf{C}})$ , the water contact angle was measured using a contact angle test instrument (JC2000D2, China).  \n\nSub-ambient Temperature Electro-fabrication of Chitosan Janus materials in large scale and 3D shape: The 2D scalable electro-fabrication of $\\mathsf{E T}_{\\mathsf{S a}}.\\mathsf{C h i t}$ was performed using a large size Ti working electrode $(25c m\\times25c m$ , and ruthenium iridium titanium mesh acts as an anode, distance in $\\mathsf{1.5c m}$ ) with a constant current density of $6.67~\\mathsf{m A c m}^{-2}$ for $\\boldsymbol{\\mathsf{1000}}\\boldsymbol{\\mathsf{s}}$ under a sub-ambient temperature $(\\approx5^{\\circ}{\\mathsf{C}})$ condition. The $\\mathsf{E T}_{\\mathsf{S a}}$ -Chit tube was fabricated using an iron wire with $1.8\\mathsf{c m}$ diameter as a working electrode (a ruthenium-iridiumtitanium mesh barrel around the wire acts as an anode) under the same electrodeposition parameters (i.e., $6.67\\ m\\mathsf{A}\\mathsf{c m}^{-2}$ for 1000 s).  \n\nIn Vitro Cell Studies: Films were cut into circles with $20~\\mathsf{m m}$ in diameter, sterilized, fixed with the dense face up or porous face up on a Cell Crown™ (Sigma) and then put into a 24-well plate without touching the bottom of the well. L929 cells were resuspended in culture medium at a density of $4.0\\times10^{4}$ cells $m L^{-1}$ . Then $7m L$ of culture medium without cells was added to the well from the outside of the Cell Crown™, and ${900\\upmu\\up L}$ of culture medium plus $700\\upmu\\upiota$ of cell resuspension was added to the sample. After incubation for 1, 4, and 7 days, the live/dead staining (DOJINDO) was performed on the cells. The distribution of cells in the films were observed by confocal laser microscopy CLSM (Nikon A1R).  \n\nIn Vivo Animal Studies: All procedures were approved by the Animal Research Bioethics Committee, East China University of Science and Technology (ECUST-2022-048). In vivo test was performed on eighteen male SD rats (8 weeks, average weight approximately $250\\ \\mathrm{g})$ using a calvarial defect model. These animals were anesthetized by intraperitoneal injection of Shutai 50, and two defects $5~\\mathsf{m m}$ in diameter) were created on the bilateral sides of the skull in sterile condition using a trephine. All 36 defects were divided into three groups: no film covered groups $({\\mathsf n}~=~{\\mathsf{7}}2)$ , covered with $\\mathsf{E T}_{\\mathsf{R o o m}^{-}}\\mathsf{C h i t}$ groups $(n~=~72)$ and $\\mathsf{E T}_{\\mathsf{S a}}$ -Chit groups $(n=72)$ ), and animals in the three groups were sacrificed at 4, 8, and 12 weeks post-operation respectively. Micro-CT was performed to observe the new bone regeneration, and the specimens were scanned using a micro-CT system (Venus001, PINGSENG Healthcare, Kunshan) with $37~\\mathsf{m m}$ slice thickness and 294 threshold value. Then, 3D histo-morphometric analysis was produced using the auxiliary histomorphometric software (PINGSENG Healthcare Ctvox, Shanghai). The parameters of bone volume fraction (BV/TV), number of trabeculae (Tb. Th), and bone mineral density (BMD) were harvested in this study. For histological observation, the skulls were firstly fixed in a $10\\%$ neutral formaldehyde solution and paraffin-embedded after decalcification. Paraffin sections were stained with hematoxylin-eosin and Masson staining, then observed by optical microscopy. The measurement of areas of newly formed bone was quantified using an image analysis system (Image Pro 5.0, Media Cybernetic, Silver Springs, MD).  \n\nStatistical Analysis: All data were expressed with mean standard deviation (SD) and analyzed using one-way ANOVA with post hoc tests. Significance was set at $p<0.05$ $(\"<\"<\")<0.007$ , $\\because p<0.01$ , ${\\displaystyle{}^{*}p<0.05}$ ).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# Supporting Information  \n\nSupporting Information is available from the Wiley Online Library or from the author.",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# Acknowledgements  \n\nM.L. and H.L. contributed equally to this work. Support from the National Natural Science Foundation of China (31922041, 32171341, 11932012), National key research and development program of the Ministry of Science and Technology (2021YFB3800800), the Science and Technology Innovation Project and Excellent  Academic  Leader  Project of Shanghai Science and Technology Committee (21S31901500, 21XD1421100) and the 111 project (B14018)are acknowledged. G.F.P. acknowledges the support from the U.S. National Science Foundation (CBET-1932963).",
+        "category": " References"
+    },
+    {
+        "id": 13,
+        "chunk": "# Conflict of Interest  \n\nThe authors declare no conflict of interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 14,
+        "chunk": "# Data Availability Statement  \n\nThe data that support the findings of this study are available from the corresponding author upon reasonable request.",
+        "category": " References"
+    },
+    {
+        "id": 15,
+        "chunk": "# Keywords  \n\ndynamic organization, electro-fabrication, guided bone regeneration, hydrogen bonds, Janus porous structures, sub-ambient temperature  \n\nReceived: August 7, 2022   \nPublished online: October 7, 2022  \n\n[1]\t F. X. Liang, C. L. Zhang, Z. Z. Yang, Adv. Mater. 2014, 26, 6944. [2]\t L.  Yan, X.  Yang, Y.  Zhang, Y.  Wu, Z.  Cheng, S. B.  Darling, L.  Shao, Mater. Today 2021.   \n[3]\t A. Walther, A. H. E. Muller, Chem. Rev. 2013, 113, 5194. [4]\t J. A.  Bouwstra, P. L.  Honeywell-Nguyen, G. S.  Gooris, M.  Ponec, Prog. Lipid Res. 2003, 42, 1.   \n[5]\t V.  Hearnden, V.  Sankar, K.  Hull, D. V.  Juras, M.  Greenberg, A. R.  Kerr, P. B.  Lockhart, L. L.  Patton, S.  Porter, M. H.  Thornhill, Adv. Drug Delivery Rev. 2012, 64, 16.   \n[6]\t F.  Bao, G.  Pei, Z.  Wu, H.  Zhuang, Z.  Zhang, Z.  Huan, C.  Wu, J. Chang, Adv. Funct. Mater. 2020, 30, 2005422. [7]\t B. Xu, A. Li, R. Wang, J. Zhang, Y. Ding, D. Pan, Z. Shen, Adv. Funct. 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Soc. 2015, 137, 13024.   \n[49]\t C. C. Tsai, B. H. Morrow, W. Chen, G. F. Payne, J. Shen, Macromolecules 2017, 50, 5946.   \n[50]\t P.  Mahinthichaichan, C. C.  Tsai, G. F.  Payne, J.  Shen, ACS Omega 2020, 5, 12016.   \n[51]\t K.  Yan, Y.  Liu, J. T.  Zhang, S. O.  Correa, W.  Shang, C. C.  Tsai, W. E. Bentley, J. Shen, G. Scarcelli, C. B. Raub, X. W. Shi, G. F. Payne, Biomacromolecules 2018, 19, 364.   \n[52]\t S. Q. Ma, Z. Chen, F. Qiao, Y. C. Sun, X. P. Yang, X. L. Deng, L. Cen, Q. Cai, M. Y. Wu, X. Zhang, P. Gao, J. Dent. 2014, 42, 1603.   \n[53]\t S. B.  Qasim, R. M.  Delaine-Smith, T.  Fey, A.  Rawlinson, I. U. Rehman, Acta Biomater. 2015, 23, 317.   \n[54]\t L.  Yang, W. T.  Lu, Y. C.  Pang, X. F.  Huang, Z. K.  Wang, A.  Qin, Q. L. Hu, RSC Adv. 2016, 6, 71567.   \n[55]\t Y. Cheng, K. M. Gray, L. David, I. Royaud, G. F. Payne, G. W. Rubloff, Mater. Lett. 2012, 87, 97.   \n[56]\t Y. Cheng, X. L. Luo, J. Betz, G. F. Payne, W. E. Bentley, G. 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Rapid Commun. 2015, 36, 1200.   \n[66]\t C. L. Lu, M. W. Urban, Prog. Polym. Sci. 2018, 78, 24.   \n[67]\t A.  Mohr, N.  Chatain, T.  Domoszlai, N.  Rinis, M.  Sommerauer, M. Vogt, G. Muller-Newen, Eur. J. Cell Biol. 2012, 91, 524.   \n[68]\t J. B. Gilbert, J. S. O’Brien, H. S. Suresh, R. E. Cohen, M. F. Rubner, Adv. Mater. 2014, 247.   \n[69]\t Q. L. Loh, C. Choong, Tissue Eng., Part B 2013, 19, 485.   \n[70]\t J.  Ruan, X.  Wang, Z.  Yu, Z.  Wang, Q.  Xie, D.  Zhang, Y.  Huang, H.  Zhou, X.  Bi, C.  Xiao, P.  Gu, X.  Fan, Adv. Funct. Mater. 2016, 26, 1085.   \n[71]\t J.  Xue, M.  He, H.  Liu, Y.  Niu, A.  Crawford, P. D.  Coates, D.  Chen, R. Shi, L. Zhang, Biomaterials 2014, 35, 9395.",
+        "category": " References"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/╡═─ж▓┴╧╡╩¤╦о─¤╜║═┐▓у JACS.json b/task2/task2-chunks/╡═─ж▓┴╧╡╩¤╦о─¤╜║═┐▓у JACS.json
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+[
+    {
+        "id": 1,
+        "chunk": "# Synthesis of Hydrogels with Extremely Low Surface Friction  \n\nJian Ping Gong, Takayuki Kurokawa, Tetsuharu Narita, Go Kagata, Yoshihito Osada,\\* Goro Nishimura,† and Masataka Kinjo†  \n\nDiVision of Biological Sciences, Graduate School of Science Hokkaido UniVersity, Sapporo 060-0810, Japan  \n\nReceiVed October 20, 2000  \n\nDesign and production of hydrogels with a low surface friction are crucially important in the biomedical applications of hydrogels as contact lens, catheter, artificial articular cartilage, artificial esophagus, etc. Great efforts to pursue suitable polymer systems have been made on designing and production of artificial organs with a sufficient lubrication.1,2 We report here a method to prepare hydrogels with an extremely low surface friction.  \n\nUsually a hydrogel is synthesized in glassware or on a glass substrate, and it has a mirrorlike smooth surface. This is the same when a hydrogel is synthesized on other hydrophilic substrates such as mica and sapphire. Focusing on the smooth surface of the gels, we have made systematic studies on the surface sliding friction of gels,3-5 and found that the frictional behavior of hydrogels does not conform to Amonton’s law $F=\\mu W$ , which well describes the friction of solids. Instead, the frictional force is strongly dependent on the sliding velocity and the normal load. Hydrogels exhibit a wide range of frictional coefficients from an order of $10^{-3}$ to $10^{0}$ in magnitude, depending on the interfacial interaction between the polymer network and the opposing substrate. When the interfacial interaction is attractive, the force to detach the adsorbing chain from the substrate appears as friction to give a high frictional coefficient. When the interfacial interaction is repulsive, a water layer is retained at the interface even under large normal loads, to give a very low frictional coefficient.3,4 Polyanionic gels, for example, exhibit frictional coefficients in an order of $1\\bar{0}^{-2}$ when slide on a piece of glass substrate in pure water due to the electrostatic repulsion between the gel and the glass.5  \n\nHowever, we discovered recently that, even for the same chemical structure, a hydrogel exhibits a much lower surface friction when it is synthesized on a hydrophobic substrate such as polytetrafluoreoethylene (Teflon) and polystyrene (PS). The differences in the surface nature of the gels synthesized on different substrates are so obvious that they can be easily distinguished by touching with one’s finger.  \n\nThe poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS) gel was synthesized by the radical polymerization. An aqueous solution of $1.0\\mathrm{~M~}2$ 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), $5.0\\ \\mathrm{mol}$ $\\%$ cross-linking agent, $\\mathbf{\\Psi}_{N,N^{\\prime}}$ - methylenebisacrylamide(MBAA), and $0.1\\mathrm{mol}\\%$ initiator, 2-oxoglutaric acid, in the reaction cell was purged with nitrogen gas for $30{-}45~\\mathrm{min}$ and was irradiated with UV light for $^{5\\mathrm{~h~}}$ at 20 $^{\\circ}\\mathrm{C}$ . The reaction was carried out between a pair of polystyrene substrates or glass substrates, separated with a spacer $2\\mathrm{mm}$ thick. After polymerization, the gel was immersed in a large amount of water for 1 week to equilibrate and to wash away the residual chemicals. The swollen PAMPS gels (swelling degree $q=21$ on glass and $q=27$ on PS) were ca. $0.4\\mathrm{cm}$ thick and they were cut into square shapes of $1.0\\times1.0\\mathrm{cm}^{2}$ for the friction measurement using a commercialized rheometer (3ARES-17A, Rheometric Scientific F. E. Ltd.) with a coaxial two parallel planar geometry. The gel was crapped on the upper surface of the platen and a glass plate was fixed at the lower platen of the rheometer. The torque and the normal force were detected when the lower platen rotated with an angular velocity at a strain-constant mode in water at $25~^{\\circ}\\mathrm{C}$ . The average frictional force was calculated from the torque. Details of the measurements were described in ref 5.  \n\n![](images/63754ad2a262b8f1b87fdbbc425723a08843d67f63a3b820c67a3decfac6901f.jpg)  \nFigure 1. Normal pressure dependence of the frictional force (a) and the frictional coefficient (b) of PAMPS gels slid against a glass plate in water at an angular velocity of $0.01~\\mathrm{rad/s}$ : $\\mathbf{\\Pi}(\\bullet)$ prepared on glass, swelling degree, 21; $\\mathbf{\\tau}(\\mathbf{\\overline{{u}}})$ prepared on PS, swelling degree, 27; and $\\left(\\bigcirc\\right)$ containing linear polymer chains, swelling degree, 15.  \n\nFigure 1 shows the normal load dependence of the frictional force (Figure 1a) and the frictional coefficient (Figure 1b) for PAMPS gel synthesized on a glass plate and on a PS plate. Figure 2 is the angular velocity dependence of the frictional coefficient for two gels. As shown in Figures 1 and 2, the frictional coefficient of the gel prepared on PS is at least two orders lower in magnitude than that of the gel synthesized on glass in the low pressure and the low velocity ranges, attaining a value as low as $10^{-4}$ . Our previous studies showed that the frictional force between two pieces of PAMPS gels in water only weakly increase with the decrease in the swelling degree of the gels,5 therefore, the large difference observed here should not be attributed to the small difference in the water content or the ionic strength, but to the different surface nature of the gels.  \n\nSuch a substrate effect is observed in a wide variety of hydrogels prepared from water-soluble vinyl monomers, such as the sodium salt of styrene sulfonate, acrylic acid, and acrlyamide, on various hydrophobic substrates, such as Teflon, polyethylene, polypropylene, poly(vinyl chloride), and polymethyl methylacrylate (PMMA).6  \n\nAs has been reported in the preceding papers, when a hydrogel is prepared in water, the gelation on the hydrophobic substrate is suppressed to give a heterogeneous structure of the gel.6,7 The suppression of the gelation on the hydrophobic surface brings about an extensive diffusion of monomers in the surface region to the adjacent region where the monomer has already been consumed and leads to a gradient network density. One can assume from this result that such a suppressed polymerization near the hydrophobic substrate cannot make an efficient crosslinking reaction, but leads to the formation of branched dangling polymer chains.  \n\n![](images/9159f8b78803106ae2510212c01c0f7e99d7f586b91ed9dd4086ca883c010176.jpg)  \nFigure 2. Angular velocity dependence of the frictional coefficient of PAMPS gels slid against a glass plate in water under a normal pressure of $4\\times10^{3}$ Pa: $\\mathbf{\\Pi}(\\bullet)$ prepared on glass;, $\\mathbf{\\eta}(\\mathbf{\\overline{{u}}})$ prepared on PS; and $(\\bigtriangledown)$ containing linear polymer chains.  \n\nThe lower cross-linking density of the gel close to the hydrophobic substrate is coincident with the fact that the surface layer synthesized on PS showed a lower compressive modulus of ${\\sim}10^{3}$ Pa while that in the bulk layer or the surface layer prepared on glass showed a value of ${\\sim}10^{4}$ Pa.8  \n\nTo prove the inhomogeneity of the network, a diffusion experiment of bovine serum albumin (BSA) in the surface layer of two kinds of gels, one synthesized on the glass and the other on PMMA plate, was made by using Fluorescence Correlation Spectroscopy (FCS). BSA is an oval-shaped protein with a molecular dimension of $14\\times4\\times4\\mathrm{nm}^{3},$ 9 which is large enough to sensitively recognize the network size of the gel. Poly(styrene sulfonate sodium salt) (PNaSS) gels with various equilibrium swelling degrees were synthesized on a glass or a PMMA, and were washed in phosphate buffered solution $\\mathrm{(pH}7.4)$ before being immersed in Alexa Fluor 488-labeled BSA (A-BSA, Molecular Probes, Eugene, OR) $\\mathrm{(0.01\\mg/mL)}$ ) solution containing unlabeled BSA $\\mathrm{(10~mg/mL)}$ ) overnight. FCS measurements were performed at $25~^{\\circ}\\mathrm{C}$ using a Fluorescence Correlation Measurement System (ConfoCor, Carl Zeiss Jena GmbH, Jena, Germany). Details were described in ref 10.  \n\n![](images/a2b5bcfa6f09d9e2a75404889900800d4e71355171c58483e07efabea571862f.jpg)  \nFigure 3. Polymer concentration dependence of the relative diffusion coefficient ${D}/{D_{0}}$ of BSA in the surface layers (ca. $200\\ \\mu\\mathrm{m}$ beneath the surface) of PNaSS gels prepared on PMMA $\\mathbf{\\eta}(\\mathbf{\\equiv}\\mathbf{\\breve{I}})$ and on glass $\\mathbf{\\Pi}(\\bullet)$ . The relative diffusion coefficient of BSA in the PNaSS solution is also shown in the figure (0). $D_{0}$ is the diffusion coefficient of BSA in water.  \n\nFigure 3 shows the diffusion constant, $D$ , ca. $200\\mu\\mathrm{m}$ beneath the gel surface. As shown in Figure 3, $D$ of BSA in the gel prepared on PMMA is much higher than that in the gel prepared on the glass and the former is the same value as that in the corresponding linear PNaSS solution. Since the $D$ of BSA strongly depends on the cross-linking density of the gel, this result suggests that the gel surface synthesized on PMMA has branched dangling chains on the cross-linked network.  \n\nTo elucidate the effect of branched dangling chains on friction, we additionally synthesized the PAMPS gels containing free  \n\nPAMPS chains inside the network and studied its frictional behavior. The free chain containing gel was prepared as follows: An aqueous solution of $1.0\\ \\mathrm{M}$ AMPS, $8.0\\ \\mathrm{mol}$ $\\%$ MBAA, and $0.1\\mathrm{mol}\\%$ 2-oxoglutaric acid was polymerized between two glass plates under the conditions described in the previous section and then immersed in a $5.0\\ensuremath{\\mathrm{M}}$ AMPS monomer solution until reaching equilibrium. Next, the polymerization without the cross-linking agent was performed in the PAMPS gel. The gel thus prepared consists of the polymer network entangled with linear polymer chains. From the weight change in the dry gels before and after the second polymerization, the weight ratio of the network to the linear chains was found to be 4:6. By the same method, it was found that only $<0.2\\%$ of the linear chains inside the gel diffused out after being immersed in water for 2 weeks. Therefore, the linear chains were effectively trapped in the gel network.  \n\nThe free polymer chains existing near the gel surface may exert a similar effect as that of branched dangling chains to reduce the friction. The results are shown in Figures 1 and 2, which show nearly the same behavior as those of the polymer gel prepared on PS substrate. Thus, incorporating linear polymers into the network, like the dangling chains, might bring about a substantial reduction in the friction coefficient.  \n\nThe reduced frictional coefficients of the gel in the presence of the branched polymer chains might be associated with the enhanced hydrodynamic thickness of the solvent layer. As has been discussed in our previous work,3-5 when the interfacial interaction is repulsive between gel and the substrate on which the gel is slid, a water layer is retained at the interface even under large normal loads to give a low friction. Under the same pressure, the static solvent layer thickness should be the same for both the chemically cross-linked gel and the gel having polymer brushes on its surface. However, under a shear flow, the polymer brushes are deformed more easily than that of the cross-linked network and this would increase the effective thickness of the hydrodynamic layer to reduce the shear resistance. Further study is needed to exploit the mechanism.  \n\nAs far as we know, neither experimental results nor theoretical models accounting for the substantial reduction of the frictional force by the polymer brushes on the gel surface have been reported. This discovery may be useful in finding novel approaches in the design of low-friction artificial organs or even informative for understanding the efficient lubrication mechanism observed in biological systems.  \n\nJA003794Q",
+        "category": " Introduction"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "分  类  号： O631  \n研究生学号： 2020331140  \n\n单位代码：10183密   级： 公开",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# 吉 林 大 学博士学位论文  \n\n多功能凝胶修饰碳纤维增强聚醚醚酮植入物的制备 及骨整合性能研究 Preparation and osseointegration investigation of multifunctional gel modified carbon fiber reinforced polyetheretherketone implants  \n\n作者姓名：董文英  \n专    业：高分子化学与物理  \n研究方向：高分子基生物医用复合材料  \n指导教师：姜振华 教授  \n培养单位：化学学院",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 多功能凝胶修饰碳纤维增强聚醚醚酮植入物的制备及骨整  \n\n合性能研究  \n\nPreparation and osseointegration investigation of multifunctional gel modified carbon fiber reinforced polyetheretherketone implants  \n\n作者姓名：董文英专业名称：高分子化学与物理指导教师： 姜振华 教授学位类别：理学博士  \n\n论文答辩日期： 2023 年  5 月 24 日授予学位日期： 年    月    日  \n\n答辩委员会组成：  \n\n姓名 职称 工作单位  \n主席 王献红 研究员 中科院长春应化所  \n委员 孙昭艳 研究员 中科院长春应化所吴广峰 教授 长春工业大学刘佰军 教授 吉林大学岳喜贵 教授 吉林大学",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# 中文摘要",
+        "category": " Abstract"
+    },
+    {
+        "id": 5,
+        "chunk": "# 多功能凝胶修饰碳纤维增强聚醚醚酮植入物的制备及骨整合性能研究  \n\n骨组织是人体的重要组成部分，不仅起到固定身体结构的作用，而且由于骨骼的独特组成和复杂的结构使其具有保护、支持、运动、储存和造血等重要功能。在天然骨骼中，有机成分提供韧性，无机成分提供刚度。有机和无机成分的结合使骨组织表现出高强度和足够的韧性。骨骼的再生和恢复损伤组织的能力有限，对于超过临界尺寸的骨缺损则不能通过骨骼的再生能力自愈。为了改善损伤骨的重建能力，骨组织工程成为一种很有前途的治疗方法，逐渐替代自体骨移植和异体骨移植等传统治疗方法。在超过临界尺寸的骨缺损的愈合过程中，骨组织工程植入物需要协调不同愈合阶段（免疫、血管化和骨再生）以恢复缺损处的骨组织功能。目前，骨组织工程植入物主要包括金属材料、聚合物材料、陶瓷材料等。其中，聚合物材料是近年来的研究热点，特别是碳纤维增强聚醚醚酮（CFRPEEK）的深入研究对解决超过临界尺寸骨缺损的治疗具有显著的应用价值。CFRPEEK具有无毒、耐腐蚀、耐磨性、高强度、耐高温、高韧性、自然射线可透过性、与皮质骨相匹配的弹性模量、灭菌性能优异等优点。但是，CFRPEEK 的生物惰性和骨结合性差极大地限制了它的临床应用。因此，从骨缺损愈合所需要的生物功能的角度出发，结合临床对超过临界尺寸骨缺损植入物的需求，本论文通过磺化处理和紫外接枝等表面改性技术，将负载地塞米松的甲基丙烯酰化明胶-聚丙烯酰胺复合凝胶、氧化石墨烯-羟基磷灰石冷冻凝胶和金属有机框架水凝分别修饰CFRPEEK，从而开发了三种具有多功能生物活性凝胶修饰 CFRPEEK 骨科植入物，用于满足骨愈合环境下所需的多种生物功能，拓宽了 CFPEEK 复合材料在生物医学领域中的应用范围，为其临床应用提供了新的研发思路和科学参考。  \n\n1.从提升骨愈合所需的生物相容性和成骨能力的角度出发，设计制备了负载地塞米松（Dex）的复合凝胶修饰 CFRPEEK 植入物，用于治疗超过临界尺寸的骨缺损。采用磺化处理和紫外接枝的表面改性方法将负载地塞米松（Dex）的甲基丙烯酰化明胶/聚丙烯酰胺（GelMA/PAAM）修饰到 CFRPEEK 植入物的表面上，构建出了具有三维（3D）凝胶网络表面的 CFRPEEK 植入物。通过 SEM 图像观察到CFRPEEK 表面上的复合水凝胶网络结构，厚度为 $50\\upmu\\mathrm{m}$ ，水接触角为$48.8~\\pm~0.45^{\\circ}$ °，具有优异的亲水性。负载 Dex 的复合凝胶修饰 CFRPEEK 在21天内的 Dex 释放效率为 $53\\%$ ，缓慢持续的 Dex 释放能力有利于成骨分化。它在模拟体液中能够形成更多的骨状磷灰石结节，具有优异的体外矿化能力。体外细胞实验证实了 GelMA/PAAM/Dex 修饰 CFRPEEK 具有良好的体外生物相容性和优异的体外成骨性能，其中，SCP/GP/Dex 上的BMSC 细胞增殖相较于 SCP 上的提高了 $42.11\\%$ ，ALP 活性提高了 $28.29\\%$ 。体内大鼠的颅骨缺损实验表明，GelMA/PAAM/Dex 修饰 CFRPEEK 具有优异的体内成骨性能并且能够促进骨缺损的愈合。  \n\n2.从提升骨愈合所需的成血管和成骨能力的角度出发，设计制备了氧化石墨烯-羟基磷灰石（GO-HAP）冷冻凝胶修饰 CFRPEEK 植入物，用于提高 CFRPEEK植入物的成血管和成骨能力。首先，采用原位键合法制备 GO-HAP 纳米复合材料。然后，采用磺化处理和基于自由基光聚合的冷冻凝胶方法将负载 GO-HAP 的冷冻凝胶接枝到CFRPEEK 植入物表面上，构建了具有 3D 海绵状大孔凝胶网络表面的 CFRPEEK 植入物。该冷冻凝胶层主要由氧化石墨烯-羟基磷灰石（GO-HAP）纳米复合材料和甲基丙烯酰化明胶/聚乙二醇二丙烯酸酯（GelMA/PEGDA）组成。体外成血管实验结果表明，在GH100 上形成的管的分支长度相较于 SCP 增长了 $111.18\\%$ ，血管网络结构最密集，这说明该多功能植入物表面的 3D 海绵状大孔结构和 GO 促进了人脐静脉内皮细胞（HUVEC）的长入和迁移，增强了CFRPEEK 植入物的体外成血管能力。良好的亲水性和 $\\mathrm{Ca}^{2+}$ 的受控释放协同增强了CFRPEEK 植入物的增殖、粘附和成骨分化能力，其中BMSC 细胞在 GH100 上的增殖相较于 SCP 提高了 $24.41\\%$ ，ALP 活性提高了 $157.08\\%$ 。大鼠颅骨缺损实验进一步表明，GelMA/PEGDA/GO-HAP 冷冻凝胶修饰的 CFRPEEK 植入物可以迅速诱导体内的新骨和新血管的生成，显著提高了 CFRPEEK 植入物的成骨固定和骨重塑能力。  \n\n3.从进一步提升骨愈合所需的抗炎能力、成血管和成骨分化的角度出发，设计制备了 pH 响应性金属有机框架（MOF）凝胶修饰 CFRPEEK 植入物来增强CFRPEEK 在植入后的抗炎、成血管和成骨能力。首先，通过纳米羟基磷灰石（HAP）、没食子酸（GA）和镁离子（ $\\mathrm{Mg}^{2+}$ ）之间的配位和耦合作用设计制备了具有核壳结构的羟基磷灰石 $@$ 镁-没食子酸（HAP@Mg-GA）金属有机框架（MOF）纳米颗粒。然后，通过磺化处理和紫外接枝的方法将负载 HAP@Mg-GA MOF 纳米颗粒的甲基丙烯酰化壳聚糖（CSMA）凝胶接枝到 CFRPEEK 植入物表面。CSMA 不仅具有可光聚合性，还具有 pH 响应性，所以该凝胶基质可以随着骨缺损处生理环境 $\\mathsf{p H}$ 值的变化来控制 HAP@Mg-GA MOF 纳米颗粒中 GA、 $\\mathrm{Mg}^{2+}$ 和$\\mathrm{Ca}^{2+}$ 的释放，从而提高CFRPEEK 植入物的抗炎、血管化和成骨分化能力。体外抗炎和成血管实验结果表明，相较于 SCP，在 MGH 上促炎因子 TNF- $\\mathbf{\\nabla}\\cdot\\mathbf{a}$ 分泌减少了 $67.09\\%$ ，抗炎因子 IL-10 分泌增加了 $284.19\\%$ ，管的分支长度增长了 $81.82\\%$ 这说明负载在CSMA 水凝胶上的 $\\mathrm{HAP}@\\mathrm{Mg-GA}$ 首先准确地释放抗炎药物GA 和微量元素 $\\mathrm{Mg^{2+}}$ 来应对炎症反应，为接下来的成骨分化创造良好的免疫微环境，同时， $\\mathrm{Mg^{2+}}$ 还可以促进血管的原位生成。体内动物实验表明，MGH 周围的新生骨的骨小梁厚度相较于 SCP 提高了 $99.53\\%$ ，这说明在骨形成阶段， $\\mathrm{Ca}^{2+}$ 的持续长期释放有利于新骨的形成和植入物周围的骨稳态的恢复以及促进骨-植入物的整合。  \n\n综上所述，本论文通过多种表面改性方法，制备了一系列的多功能凝胶表面修饰碳纤维增强聚醚醚酮植入物。对多功能凝胶修饰的碳纤维增强聚醚醚酮的表面性能表征、体外细胞反应和体内骨整合能力等均进行了探究，为进一步开发具有多功能生物活性表面的 CFRPEEK 骨科植入材料及其未来临床应用提供了科学参考及开发新思路。",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 关键词：  \n\n碳纤维增强聚醚醚酮，凝胶，表面改性，多功能，骨整合",
+        "category": " Abstract"
+    },
+    {
+        "id": 7,
+        "chunk": "# Abstract",
+        "category": " Abstract"
+    },
+    {
+        "id": 8,
+        "chunk": "# Preparation and osseointegration investigation of multifunctional gel modified carbon fiber reinforced polyetheretherketone implants  \n\nBone tissue plays an important role in the life of a human. Bones serve crucial roles such protection, support, mobility, storage, and hematopoietic cell generation thanks to their distinctive composition and intricate structure. In natural bones, toughness is provided by organic components whereas stiffness is provided by inorganic components. Bone tissue has high strength and sufficient toughness due to the combination of organic and inorganic components. However, t bone has a limited capacity for tissue regeneration and recovery, especially for bone defects beyond critical size. Bone tissue engineering has emerged as a possible substitute for established treatment modalities like autograft and allograft in order to enhance the reconstruction of broken bones. In the process of healing a supercritical-size bone defect, bone tissue engineering implants need to coordinate different healing stages (immune regulation, vascularization, and bone regeneration) to restore bone tissue function at the defect. Currently, the primary materials used in bone tissue engineering implants are metal, polymer, ceramic, etc. The study of carbon fiber reinforced polyetheretherketone (CFRPEEK), which offers excellent practical potential for the treatment of supercritical-sized bone lesions, has received particular attention from researchers in recent years. CFRPEEK has the advantages of non-toxic, corrosion resistance, wear resistance, high strength, high temperature resistance, high toughness, natural ray transmittability, elastic modulus matching with cortical bone, excellent sterilization performance, etc. However, the bioinertness and poor bone binding of CFRPEEK greatly limit its clinical application. From the perspective of biological function required for bone defect healing, combined with clinical demand for bone defect implants with larger than critical size, this paper adopts surface modification technologies such as sulfonation treatment and ultraviolet grafting. Three multifunctional bioactive gel-modified CFRPEEK orthopedic implants were developed by modifying dexamethasone-loaded methylacrylyl gelatine-polyacrylamide composite hydrogel, graphene oxide-hydroxyapatite cryogel and metal-organic framework hydrogel, respectively, to meet a variety of biological functions required in the bone healing environment. The application range of CFPEEK composite material in the biomedical field is expanded, which provides a new research and development idea and scientific reference for its clinical application.  \n\nA dexamethasone (Dex)-loaded composite hydrogel modified CFRPEEK implant was designed and prepared for the treatment of supercritical-sized bone defects. Methacryloyl gelatin/polyacrylamide (GelMA/PAAM) loaded with dexamethasone (Dex) was modified onto the surface of the CFRPEEK implant by sulfonation treatment and ultraviolet grafting. The modified CFRPEEK had a 3D composite hydrogel network surface. The composite hydrogel network structure on the surface of CFRPEEK with a thickness of $50~{\\upmu\\mathrm{m}}$ was observed by SEM images. Its water contact angle is $48.8\\pm0.45^{\\circ}$ , showing excellent hydrophilicity. The Dex release efficiency of modified CFRPEEK was $53\\%$ within 21 days, and the slow and sustained Dex release ability was conducive to osteogenic differentiation. It formed more bone apatite in simulated body fluid and had excellent in vitro mineralization ability. In vitro cell results confirmed that GelMA/PAAM/Dex modified CFRPEEK demonstrated outstanding in vitro osteogenic performance and acceptable in vitro biocompatibility. The proliferation of bone marrow mesenchymal stem cells (BMSC) on SCP/GP/Dex was increased by $42.11\\%$ and the activity of ALP was increased by $28.29\\%$ compared with that on SCP. In vivo experiments of rat cranial defects showed that GelMA/PAAM/Dex modified CFRPEEK had excellent in vivo osteogenic properties and could promote the healing of bone defects.  \n\nA graphene oxide-hydroxyapatite (GO-HAP) cryogel modified CFRPEEK implant was designed and prepared with the goal of enhancing the angiogenesis and osteogenesis processes necessary for bone healing. First, GO-HAP nanocomposites were prepared using in situ bonding method. Then, the cryogel loaded with GO-HAP was grafted onto the surface of the CFRPEEK implant by sulfonation, and the cryogelation technique based on free radical photopolymerization. The cryogel layer was mainly composed of GO-HAP nanocomposite and methacryloyl gelatin/polyethylene glycol diacrylate (GelMA/PEGDA). The results of in vitro angiogenesis experiments showed that the total branching length of the tube formed on GH100 increased by $111.18\\%$ compared with that of SCP, and the vascular network structure was the most dense, indicating that the 3D sponge-like macroporous structures on the surface of the multifunctional implant and GO promoted the growth and V  \n\nmigration of human umbilical vein endothelial cells (HUVEC). The in vitro angiogenesis ability of modified CFRPEEK implants was enhanced. The excellent surface hydrophilicity and controlled release of $\\mathrm{Ca}^{2+}$ of modified CFRPEEK promoted proliferation, adhesion, and osteogenic differentiation of BMSCs. The proliferation of BMSCs on GH100 was increased by $24.41\\%$ compared with SCP, and the activity of ALP was increased by $157.08\\%$ . The rat cranial defect experiment further demonstrated that the GelMA/PEGDA/GO-HAP cryogel modified CFRPEEK implant could rapidly induce bone regeneration and new blood vessel formation in vivo and significantly improve the osteogenesis and bone remodeling ability of the CFRPEEK implant.  \n\nA pH-responsive metal-organic framework (MOF) hydrogel modified CFRPEEK implant was designed and prepared to enhance the anti-inflammatory, vascularization, and osteogenic properties of CFRPEEK after implantation. Firstly, hydroxyapatite $@$ magnesium-gallic acid (HAP@Mg-GA) metal-organic frame (MOF) nanoparticles with core-shell structure were prepared through coordination and coupling between HAP, gallic acid (GA) and magnesium ion $(\\mathrm{Mg}^{2+})$ . Methacryloyl chitosan (CSMA) hydrogel loaded with HAP $@$ Mg-GA MOF nanoparticles was then grafted onto the surface of the CFRPEEK implant by sulfonation and ultraviolet grafting. Methacryloyl chitosan was not only a photopolymer but also pH-responsive. Therefore, the hydrogel could control the release of GA, $\\mathrm{Mg}^{2+}$ , and $\\mathrm{Ca}^{2+}$ in HAP@Mg-GA MOF nanoparticles with the change of $\\mathsf{p H}$ of the physiological environment at the bone defect, so as to improve the anti-inflammatory, vascularization, and osteogenic differentiation abilities of the CFRPEEK implant. In vitro anti-inflammatory and angiogenesis experiments showed that, compared with SCP, the secretion of pro-inflammatory factor TNF- $\\mathbf{\\nabla}\\cdot\\mathtt{a}$ decreased by $67.09\\%$ , the secretion of anti-inflammatory factor IL-10 increased by $284.19\\%$ and the total branching length of the tube increased by $81.82\\%$ on MGH. In vitro cell experiments showed that HAP $@$ Mg-GA loaded on CSMA hydrogel first actively and accurately released anti-inflammatory drug GA and microelement $\\mathrm{Mg}^{2+}$ in response to inflammation in the inflammatory reaction stage, which created a good immune microenvironment for osteogenic differentiation in the following stage. Meanwhile, the released magnesium also promoted the formation of blood vessels in situ. The experiments of tibial defect in rabbits further showed the trabecular thickness of new bone around MGH was increased by $99.53\\%$ compared with SCP, indicating that the sustained long-term release of $\\mathrm{Ca}^{2+}$ facilitated new bone formation and restoration of bone homeostasis around the implant and promoted bone-implant VI  \n\nintegration.  \n\nA series of multifunctional gel surface modified CFRPEEK implants were prepared through a variety of surface modification methods in this work. The surface properties, in vitro cell reactions, and in vivo osteointegration of multifunctional gelmodified carbon fiber reinforced polyether ether ketone implants were investigated, which provided scientific reference and new development ideas for further development and future clinical application of multifunctional bioactive carbon fiber reinforced polyetheretherketone orthopedic implants.",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# Keywords:  \n\nCarbon fiber reinforced polyetheretherketone, Gel, Surface modification, Multifunctional, Osteointegration",
+        "category": " Abstract"
+    },
+    {
+        "id": 10,
+        "chunk": "# 目  录  \n\n第 1 章 绪论..  \n\n1.1 前言.  \n1.1.1 骨骼的构成与结构 .  \n1.1.2 骨缺损的修复过程 . 2  \n1.2 骨植入物材料 . .4  \n1.2.1 金属生物材料. 5  \n1.2.2 生物活性陶瓷 7  \n1.2.3 聚合物生物材料 .9  \n1.2.4 复合生物材料 .13  \n1.3 碳纤维增强聚醚醚酮 . .14  \n1.3.1 碳纤维增强聚醚醚酮的概述. ...14  \n1.3.2 聚醚醚酮及其复合材料表面生物功能化研究现状 ..15  \n1.4 水凝胶在骨组织工程中的应用研究 . .22  \n1.5 本论文设计思想 . .24  \n第 2 章 负载地塞米松的复合水凝胶修饰 CFRPEEK 的制备及其成骨  \n能力的研究 .. 27  \n2.1 前言. ..27  \n2.2 实验部分. ..29  \n2.2.1 实验材料与仪器 .29  \n2.2.2 磺化 CFRPEEK 复合材料的制备 ..31  \n2.2.3 甲基丙烯酰化明胶(GelMA)的制备与表征. ..33  \n2.2.4 负载 Dex 的复合水凝胶修饰 CFRPEEK 的制备 .. ..33  \n2.2.5 力学性能测试 ..34  \n2.2.6 Dex 释放行为研究 . ..34  \n2.2.7 体外矿化行为研究 . ..35  \n2.2.8 细胞实验 ..35  \n2.2.9 大鼠颅骨缺损实验 . ..39  \n2.2.10 统计与分析 .. ..41  \n2.3 结果与讨论 ...41  \n2.3.1 甲基丙烯酰化明胶(GelMA)的制备 ..41  \n2.3.2 负载 Dex 的复合水凝胶修饰 CFRPEEK 的制备 ... ...41  \n2.3.3 机械性能 . ...45  \n2.3.4 药物(Dex)缓释行为 .45  \n2.3.5 体外矿化性能 .46  \n\n2.3.6 体外 BMSC 细胞相容性.. .47  \n2.3.7 体外 BMSC 成骨分化潜能 ..48  \n2.3.8 体内骨整合性能 ..50  \n2.4 本章小结 .53  \n第 3 章 GO-HAP 冷冻凝胶修饰 CFRPEEK 的制备及其成血管/成骨  \n能力的研究 . ..55  \n3.1 前言 . ..55  \n3.2 实验部分 ...57  \n3.2.1 实验材料与仪器 .57  \n3.2.2 氧化石墨烯-羟基磷灰石(GO-HAP)纳米复合材料的制备与  \n表征 . .58  \n3.2.3 磺化 CFRPEEK 复合材料的制备 ..59  \n3.2.4 GO-HAP 冷冻凝胶修饰 CFRPEEK 的制备 .... .59  \n3.2.5 冷冻凝胶层的附着力测试 .. ...60  \n$3.2.6\\mathrm{Ca}^{2+}$ 的释放行为 ... ..61  \n3.2.7 体外矿化行为研究 .. ...61  \n3.2.8 细胞实验 . ...61  \n3.2.9 大鼠颅骨缺损实验 . ...64  \n3.2.10 统计与分析 . ...65  \n3.3 结果与讨论 . ....65  \n3.3.1 氧化石墨烯-羟基磷灰石(GO-HAP)的制备 ...65  \n3.3.2 GO-HAP 冷冻凝胶修饰 CFRPEEK 的制备 . ....66  \n3.3.3 冷冻凝胶层的附着力 . ..70  \n$3.3.4\\mathrm{Ca}^{2+}$ 的释放行为 ... ...70  \n3.3.5 体外矿化性能 ..71  \n3.3.6 体外 BMSC 细胞相容性. ...71  \n3.3.7 体外成骨性能 . ..74  \n3.3.8 体外成血管性能 .. ...76  \n3.3.9 体内成骨整合性能探究 . ..79  \n3.4 本章小结 .. .82  \n第 4 章 pH 响应性 MOF 水凝胶修饰 CFRPEEK 的制备及其免疫/  \n成血管/成骨能力的研究 .. .83  \n4.1 前言 . ...83  \n4.2 实验部分 . ...85  \n4.2.1 实验材料与仪器 ....85  \n4.2.2 HAP@Mg-GA MOF 纳米颗粒的制备与表征 .. ....87  \n4.2.3 甲基丙烯酰化壳聚糖(CSMA)的制备与表征 .. ...88  \n4.2.4 磺化 CFRPEEK 复合材料的制备 . .88  \n4.2.5 MOF 水凝胶修饰磺化 CFRPEEK 的制备 . 88  \n4.2.6 水凝胶层的附着力测试 . ..89  \n4.2.7 表面 zeta 电势测试 ..89  \n4.2.8 蛋白吸附能力测试 . ..90  \n$4.2.9\\mathrm{Ca}^{2+}$ 、 $\\mathbf{M}\\mathbf{g}^{2+}$ 和 GA 在不同 pH 下的缓释行为测试 ....90  \n4.2.10 体外矿化行为研究. ..90  \n4.2.11 细胞实验 . ..90  \n4.2.12 体内动物实验 ..94  \n4.2.13 统计与分析 ..96  \n4.3 结果与讨论 ..96  \n4.3.1 HAP@Mg-GA MOF 纳米颗粒的制备 . ..96  \n4.3.2 甲基丙烯酰化壳聚糖(CSMA)的制备 ..98  \n$4.3.3\\mathrm{MOF}$ 水凝胶修饰磺化 CFRPEEK 的制备 ..98  \n$4.3.4\\:\\mathrm{MOF}$ 水凝胶层的附着力 ... .101  \n4.3.5 表面 zeta 电势 .. .101  \n4.3.6 蛋白吸附能力 . .102  \n$4.3.7\\mathrm{Ca}^{2+}$ 、 $\\mathbf{M}\\mathbf{g}^{2+}$ 和 GA 的在不同 pH 下的缓释行为 .103  \n4.3.8 体外矿化行为 .. .104  \n4.3.9 体外炎症反应 .104  \n4.3.10 体外成血管性能 .107  \n4.3.11 体外成骨性能 111  \n4.3.12 体内炎症反应和血管生成性能 . .114  \n4.3.13 体内成骨整合性能 .118  \n4.4 本章小结. .123  \n第5 章 结论与展望 .125  \n5.1 结论 . .125  \n5.2 展望 .127  \n129  \n\n参考文献 .",
+        "category": " Introduction"
+    },
+    {
+        "id": 11,
+        "chunk": "# 第1 章 绪论",
+        "category": " Introduction"
+    },
+    {
+        "id": 12,
+        "chunk": "# 1.1 前言  \n\n骨是一种坚硬的结缔组织，由基质、细胞和生物活性因子构成，具备层次结构[1]。骨骼也是一种具有自我更新能力的再生器官，为了保持其结构和功能而进行不断的重塑。在骨组织中，持续的重塑保持了骨的完整性[2]。临界尺寸骨缺损是指无法通过自身再生能力修复的最小骨缺损，或在生长周期内再生不足 $10\\%$ 的骨缺损。对于低于临界尺寸的骨缺损可以通过骨自身的重塑来愈合。骨重塑并不能修复由肿瘤、先天性疾病、感染性疾病以及车祸、创伤等意外因素引起的大型创伤和缺损[3]。目前，为了治愈临界或超临界骨缺损，临床实践中提出了多种骨缺损再生治疗方法，尤其是硬骨组织再生的治疗方法，包括异体骨移植、异种骨移植和自体骨移植等，但这些方法仍存在许多安全问题，如供体部位感染、供应有限、感染性疾病和免疫排斥等[4]。骨组织工程在近几十年作为一种很有前途的骨缺损治疗策略出现，研发人员开发了许多了生物活性材料作为骨移植替代品以恢复缺陷和患病的骨组织的功能[5]。",
+        "category": " Introduction"
+    },
+    {
+        "id": 13,
+        "chunk": "# 1.1.1 骨骼的构成与结构  \n\n骨骼是骨骼系统的主要组成部分，还是人体复杂而协调的多部分“机器”的重要组成部分[6]。除了作为矿物库（如钙、磷酸盐和镁）和造血组织（如骨髓）的宿主外，骨骼还具有一系列的机械功能，它不仅负责保护内部器官（如大脑）和组织（如骨髓），也负责身体的支持和运动[7, 8]。骨骼是一种多层次结构的组织。在亚微结构水平上，骨骼主要由Ⅰ型胶原蛋白、矿物晶体、水和非胶原蛋白组成[9]。如Figure 1.1 所示，骨骼的有机和无机成分混合在一起形成矿化胶原纤维。骨骼中的矿物成分以薄的多晶片的形式分布在胶原纤维之间[10]，这种胶原-矿物系统平行排列在薄片中称为骨板。有机相和无机相的力学性能及其分层排列决定了骨的强度和韧性[11]。矿物质的含量主要有助于骨的硬度和强度[12, 13]。在宏观层面上，骨骼中有两种类型的骨组织：松质骨（也称为小梁或海绵状骨）和皮质（或致密）骨。每种类型的骨骼都以不同特定百分比的皮质骨和松质骨构成 [14]。皮质骨为骨髓间隙周围致密的外骨，而松质骨是由内骨小梁板和棒状体组成，在骨髓腔室中形成蜂窝状网络[15]，这两种骨组织的孔隙率和代谢水平也有所不同。松质骨是多孔的（孔隙率在 $40\\%$ 到 $90\\%$ 之间），密度比皮质骨小，这使得松质骨的结构更灵活、更脆弱，松质骨也比皮质骨有更强的代谢活性[16]。在微观层面上，皮质骨主要由骨单位构成，每个骨单位由 10-30 个骨板排列成同轴圆柱体并围绕着神经血管通道构成。松质骨主要由骨小梁构成，并散布在充满骨髓的空间中[17]。骨量是指单位体积内骨组织的质量，它由机体的机械应变维持并适应机体的日常活动[18]。机械转导过程是指骨细胞将外界机械力转化为生化反应，协调骨重塑的过程。机械转导过程是由骨骼中各种类型的细胞进行复杂的相互作用而完成的[19]。  \n\n![](images/711cd900faf6b95b49220985bf8a1ced62de285a8f22ce7a2e56af0cb57b2a48.jpg)  \nFigure 1.1 Bone hierarchical structure [20].",
+        "category": " Introduction"
+    },
+    {
+        "id": 14,
+        "chunk": "# 1.1.2 骨缺损的修复过程  \n\n骨骼系统结构和功能的完整性不仅能维持身体基本运动，还保护着脆弱的内脏器官。骨组织具有很强的维持内稳态的能力，并在骨吸收和再生的动态平衡中不断重建。骨组织一旦被病理性损伤，受损部分的各种细胞被激活并有序的参与愈合过程从而重建骨结构和功能[21]。由病理创伤引起的骨修复与自然的骨发育不完全相同一般包括三个阶段；炎症、修复和重塑阶段（Figure 1.2）,深入了解骨缺损的修复过程是设计骨组织工程支架的基础[22]。  \n\n炎症是骨缺损修复的起始，决定骨缺损愈合的结果[23]。当骨组织受伤时，骨缺损处的血管就会被破坏，血液进入骨缺损区，形成血肿。血肿中的纤维蛋白凝固形成一个临时基质，其中包含来自血液、骨组织和周围组织的成分。血肿的特征是局部缺氧、酸性、细胞变形和运动引起机械应力以及钙、磷和碱性磷酸酶的表达增加[24]。免疫细胞渗透到血肿处并通过分泌一系列的生物分子来触发炎症。具体来说，中性粒细胞在受伤 24 小时内被招募到骨损伤处吞噬细菌和碎片，分解受损伤组织并分泌促炎和趋化因子 [25]。促炎和趋化因子进一步招募单核/巨噬细胞和淋巴细胞，并分泌其他的生物因子，这些生物分子在骨缺损处进一步发挥作用[26, 27]。M1 巨噬细胞分泌的促炎因子（如 TNF- $\\mathbf{\\nabla}\\cdot\\mathbf{a}$ 、TGF- $\\cdot\\upbeta$ 和 $\\mathrm{IL}{-}1\\upbeta$ 等）可以进一步招募炎症细胞并吞噬坏死区域。M2 巨噬细胞分泌的促成骨因子（如 BMP-2）可以招募骨髓间充质干细胞（BMSCs）并调节其增殖、分化和促进骨的形成，同时，M2 巨噬细胞分泌的促血管生成因子（如 PDGF-BB 和 VEGF）可以招募内皮细胞参与新血管的形成和侵袭[28, 29]。  \n\n当炎症阶段完成时，缺损处的骨组织的代谢和修复逐渐增强[30]。在血肿内，纤维蛋白肉芽组织开始形成，BMSCs 从周围血管被招募到骨缺损区域。在各种生长因子/信号和缺氧环境的刺激下，BMSCs 分化为成纤维细胞、成软骨细胞和成骨细胞[23]。成纤维细胞增殖并分泌纤维基质，逐渐用纤维组织代替肉芽组织[31]。成软骨细胞/软骨细胞分泌半刚性无血管软骨基质，逐渐将富含纤维的肉芽组织转化为富含纤维软骨和透明软骨的软骨痂组织，这些软骨痂组织将骨缺损区域填充并提供临时的机械支持。在软骨细胞分泌基质并诱导矿化时，它们也会释放血管内皮生长因子（VEGF）以促进新血管的生长并与骨形态发生蛋白（BMP）协同合作增强骨愈合效果[32, 33]。在血管重建完成后，成熟的肥大软骨细胞发生凋亡或分化为成骨细胞样细胞并与成骨细胞参与细胞外基质矿化将软骨痂组织转化为硬骨痂组织[34]。硬骨痂组织外有血管化的基质修复骨膜，这一过程再现了胚胎骨发育过程中的膜内和软骨内骨化。在这个修复阶段之后，缺损区域可以恢复足够的机械性能来支持低强度的运动。为了进一步恢复正常的功能结构和机械强度，骨组织的修复进入了下一个阶段。  \n\n骨重塑是骨缺损修复的最后阶段。在这个阶段，骨痂的中心被致密的骨所取代，边缘被层状骨所取代，缺损处的血管网络恢复到骨缺损前水平，最终骨骼恢复到原始状态[35]。虽然骨修复过程可以使受损骨骼的细胞组成、结构和生物力学功能恢复到损伤前状态，但是对于大体积骨缺损不能正常愈合，这就需要合理的临床干预。骨组织工程植入材料的应用已成为解决这个问题很有前途的方法[30]。  \n\n![](images/4d9d7caa49f118de08ba159a78f83e356a4ee6d5664aa4a9a0727d6776c48853.jpg)  \nFigure 1.2 A complex and well-orchestrated bone repair process involving three phases; inflammation, repair, and remodelling phases [36].",
+        "category": " Introduction"
+    },
+    {
+        "id": 15,
+        "chunk": "# 1.2 骨植入物材料  \n\n骨组织工程（BTE）能够有效地避免自体骨移植和异体骨移植的缺点，在骨组织再生领域引起了广泛的关注。它旨在创造一种单独或联合使用生物材料、细胞和生长因子的生物功能组织，可以在体内整合和降解，以治疗病变或损伤的组织（Figure 1.3）。开发骨组织工程材料有多种临床原因，包括需要更好的“可用于重建大型骨科缺损的新型材料”，以及需要在机械上更适合其生物环境的骨科植入物。治疗大型骨缺损的骨移植替代品材料大致可分为金属、陶瓷，聚合物以及它们的复合材料[37-39]。  \n\n![](images/62008697cb5b2b1fb3963277cc06ef77fb1b304cbeec4b6ed1d4c11d509d4d12.jpg)  \nFigure 1.3 Bone tissue engineering strategies [40].",
+        "category": " Introduction"
+    },
+    {
+        "id": 16,
+        "chunk": "# 1.2.1 金属生物材料  \n\n金属生物材料由于其力学性能和可加工性优于生物陶瓷和生物聚合物材料，已被广泛应用于功能性和承重骨替代品[41]。大多数金属的力学性能远高于天然骨的力学性能，产生的应力不匹配使得骨与植入物接触的界面不稳定，导致纤维组织在植入物界面处向内生长，骨整合被破坏，植入物松动从而引起炎症反应，最终需要二次手术[42]。金属过高的力学性能可以通过增加其孔隙率来调整，增加金属生物材料的孔隙率不仅可以降低其力学性能，还可以提高其对细胞和营养物质的通透性，促进血管生成和骨长入[43]。目前，用作生物材料的主要金属合金是钛（Ti）合金，钴-铬（Co-Cr）合金和不锈钢，以及可生物降解镁（ $\\mathbf{Mg}^{\\mathrm{\\cdot}}$ ）合金。  \n\n钛（Ti）因其独特的医学适用性（如良好的生物相容性，高比强度，低重量和耐腐蚀性）而在骨科中广泛使用[44-46]。纯钛的较低的屈服强度值（小于 $480\\mathrm{MPa})$ ）和抗拉伸强度（小于 $550~\\mathrm{MPa})$ ），使其不足以作为承重骨植入物的材料，但是它的合金因有更好的机械性能成为承重骨植入物的首选材料[47]。与固体钛基植入物相比，多孔钛基植入物为骨的生长和沉积提供了更高的表面积，也为生物活性物质的添加提供了更多的选择[48, 49]。Li 等[50]通过电子束熔融法（EBM）制备了具有聚多巴胺-羟基磷灰石涂层的多孔 Ti6Al4V 支架。该支架增强了 MC3T3-E1细胞的体外增殖和成骨分化，在植入到兔股骨侧上髁后促进了植入物的骨整合和成骨分化能力（Figure 1.4）。  \n\n![](images/81f4b5221bf3c35c57fab1ccde836eb6e285a06229149d3af0b32d40e2f8192c.jpg)  \nFigure 1.4 HA/pDA-pTi morphologies and their biological functions prepared by electron beam melting [50].  \n\n与Ti 合金相比，钴（Co）-铬（Cr）合金具有良好的耐磨性和相对较高的强度[51]，其中钴增加了合金的强度，铬增强了合金的耐腐蚀性 [52]。由于良好的机械性能、可制造性以及对人体关节的生理环境的耐腐蚀性，Co-Cr 合金成为内源性假体和骨合成装置的首选材料[53]。Paolo 等[54]通过选择性激光熔化（SLM）技术制造的Co-Cr 多孔支架具有仿骨小梁的结构和机械性能，最大限度地减少骨科植入物的应力屏蔽，而且提高了 Co-Cr 合金的体外细胞活力和增殖性能以及体内的定植（Figure 1.5）。但是，Co-Cr 合金的摩擦腐蚀会造成Co、Ni 等离子的溶出对成骨细胞的毒性大，在体内引起细胞和组织的坏死[55]。  \n\n![](images/79acefc08e290b1e72cb96b7f6796911922320326c30aa844e82ed8783e5b75f.jpg)  \nFigure 1.5 Overview of the study workflow, showing graphical details of the modeling (left), manufacturing (central), and testing (right) subphases. The images report CoCr samples obtained via SLM and images from the topographical and biological evaluations [54].  \n\n由于易于制造，耐腐蚀性，良好的机械性能，以及相对较低的生产成本，医用不锈钢（MSS）是最常用的骨科植入材料之一，广泛应用于人体骨置换、牙科、心脏外科、冠状动脉支架置入等领域。不锈钢较差的生物相容性，使它不会自然地与骨骼结合，并且摩损会释放致畸、致癌作用的 Ni 等元素，这可能导致植入物失效。因此，提高不锈钢的耐腐蚀性是其作为骨科植入物放入关键。据报道，表面晶粒细化能够在不锈钢上制造表面层，从而有效地增强不锈钢的耐腐蚀性[56]。  \n\n镁（Mg）和镁合金作为一种可生物降解金属，因其低密度、优良的生物相容性、高生物可吸收性和适当的力学性能成为具有发展潜力的骨科植入物[57]。相对于天然骨，镁及其合金具有更高的强度，但它们的杨氏模量与皮质骨非常接近，这意味着它们可以减少种植体与骨界面之间的应力屏蔽[58]（Figure 1.6）。镁合金释放的镁离子不仅能促进干细胞分化成成骨细胞，还能促进成骨相关基因的表达[59, 60]。镁离子还能增强新骨组织的血管化，这对骨缺损处骨组织的恢复是至关重要的[57]。镁基金属在体液中过快的降解速率会释放过量镁离子导致局部毒性，还会使得植入物界面与周围骨组织形成空腔从而导致植入失败。因此，控制镁基金属在体液中的降解速率是其作为医用植入物临床应用的关键[61, 62]。目前，研究人员通过提高镁金属的纯度、合金化和表面改性来实现对镁基金属植入物降解速率的初步调控[63, 64]。例如，Hahn 等[65]在镁合金上通过喷涂技术制备了 HA 涂层以增强镁合金的生物相容性和耐腐蚀性。  \n\n![](images/5e8538d922ae7a641bb2e3382ae34edd28d5ec7d1805fb67ca21ac497ba28907.jpg)  \nFigure 1.6 (A) The distribution range of tensile yield strength of natural bone, commercially available orthopedic implants made of polymers and inert metals, and biodegradable $\\mathbf{Mg}$ and its alloys; (B) The peak stress distribution in a finite element analysis (FEA) model composed of a femur and an inserted titanium (Ti) or Mg-based screw [58].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 1.2.2 生物活性陶瓷  \n\n生物活性陶瓷是指一类具有特定生物或生理功能的陶瓷材料。它们在植入后能够直接与骨组织结合，所以被广泛应用于骨组织工程领域[66]。目前广泛使用的生物活性陶瓷包括磷酸钙（CaP）、生物活性玻璃（BG）和硅酸钙（CS）[67-69]，这些生物活性陶瓷在组成与结构上与骨的矿物相相似并且能够在体内自降解。这些生物陶瓷在组织工程领域的有效应用必须考虑它的生物吸收的程度和较差的机械强度[70-71]。目前，研究人员对生物活性陶瓷的化学成分、生物活性、制备工艺及其改性等之间的关系进行了大量的研究来提高它们的临床应用潜力。  \n\n磷酸钙（CaP）是骨组织工程中最常用的生物活性陶瓷。目前，最常用的磷酸钙基生物陶瓷包括磷酸三钙（TCP）和羟基磷灰石（HAP）。基于 HAP 植入物在植入后可与周围组织形成化学键，以促进新骨的生成 [72]。TCP 具有优良的生物活性、生物降解性和生物相容性，可以提高干细胞增殖能力并诱导骨再生[73]。不论是致密的 HAP 陶瓷还是通过 3D 打印技术制作的抗压的 TCP 支架的力学性能都远低于承重骨。因此，为了解决这些材料力学性能差的问题，研究人员通常采用与聚合物复合制备复合材料的方法来提高它们的强度和韧性。例如，Davila等[74]通过3D 迷你螺杆挤出打印制造PCL/ $\\mathrm{^{\\prime}\\beta}$ -TCP 支架。该支架的孔隙率为 $55\\%$ ，孔径为 $450~{\\upmu\\mathrm{m}}$ ，表现出良好的机械性能和亲水行为（Figure 1.7）。  \n\n![](images/9a4ed955214bc422f3c0870fc1b3ff128f34392db454e3ed7029b7ff1f47f48f.jpg)  \nFigure 1.7 SEM micrographs of scaffolds: (a) P100C0, (b) P90C10, (c) P80C20, and (d) P70C30. (At row 1 is presented the $0^{\\circ}/90^{\\circ}$ architecture, at row 2 the strand surface and at row 3 the cross section of the strand) [74].  \n\n生物活性玻璃（BG）作为一种骨修复材料，可以促进骨钙素基因的表达[75]。该材料的典型特征是与活组织相互作用的能力强，特别是能与周围的骨组织牢固结合[76]。生物活性玻璃的这种骨结合特性是由于其表面的离子的浸出与交换以及玻璃网络的溶解，这促进骨样磷灰石的沉淀和生长[77]。生物活性玻璃还能吸引相关（骨）细胞的粘附、增殖和分化。最近的研究证明，生物活性玻璃的离子溶解和释放能够激活骨生成细胞的基因表达，从而增强骨再生[78]。Wang 等[79]通过3D 打印技术制备了聚己内酯/生物活性玻璃支架，含有生物活性玻璃的支架具有更高的亲水性和更高的抗压强度，并且 $\\mathrm{Ca}^{2+}$ , $\\mathbf{P}^{5+}$ 和 ${\\mathrm{Si}}^{4+}$ 的释放促进细胞的成骨分化和体内的骨再生（Figure 1.8）。  \n\n![](images/c0841e64753280fa1684a8989288dae80a6be9b0c11ee502d9a4159abda9659f.jpg)  \nFigure 1.8 (a) Micro-CT and X-ray radiographs images. (b) Histological analysis of bone regeneration in tibial defects by scaffolds with different ratios (5, 10 and 20 $w t\\%$ ) bioactive glass at 8 weeks after surgery[79].  \n\n硅酸钙（CS）因其优异的生物活性而引起人们的广泛关注。目前，硅酸钙（CS）基生物陶瓷的生物医用范围包括修复硬组织裂纹、作为骨支架、骨水泥或植入物涂层[80]。硅酸钙（CS）基生物陶瓷具有良好的生物活性和与活骨和软组织结合的能力。特别是，硅离子能够在模拟体液（SBF）中诱导骨样磷灰石的形成[73]（Figure 1.9）。为了利用硅酸钙（CS）基生物陶瓷离子释放的有益作用，并提高它在特定宿主响应方向上的生物性能，科研人员通过各种制造技术和不同的生物分子的添加使其尽可能接近骨组织再生的力学和生物特性。  \n\n![](images/a10eff705cdee052a7dd49164af9e0cef286bbed6c6f63d4c171131d8fdc8c6c.jpg)  \nFigure 1.9 Schematic illustration of the mechanism of apatite formation on calcium silicate ceramics in SBF [80].",
+        "category": " Introduction"
+    },
+    {
+        "id": 18,
+        "chunk": "# 1.2.3 聚合物生物材料  \n\n聚合物生物材料因其灵活的可设计性、广泛的可用性、低毒性/无毒、生物降解性、生物相容性、化学多功能性和固有的功能而在骨组织工程材料开发中受到了广泛的关注[81]。聚合物生物材料可分为天然聚合物材料和合成聚合物材料[82-88]。  \n\n天然聚合物是由多个单体或化合物单体连接在一起形成的长链。天然聚合物是组织本身的组成部分，具有优异的生物相容性和生物降解性，可以提高细胞粘附，促进细胞趋化反应，从而增强支架与组织之间的生物相互作用[89]。如图Figure  \n\n1.10 所示，最常用的天然聚合物包括壳聚糖、海藻酸盐、胶原蛋白、明胶、透明质酸和纤维素等 [90]。明胶是通过酸水解或碱水解胶原蛋白获得的一种天然蛋白质[91]。明胶广泛存在于哺乳动物中，具有良好的生物相容性，如促进细胞粘附、细胞增殖和细胞分化[92]。它还含有丰富的精氨酸 - 甘氨酸 - 天冬氨酸（RGD）序列，参与细胞信号传导[93]。在骨组织工程中，明胶及其衍生物已被用作骨修复的支架。例如，Liu 等[94]通过 3D 打印技术制备了负载细胞的纳米凹凸棒石/甲基丙烯酰化明胶（cell-laden nano-ATP/GelMA）复合水凝胶支架用于骨组织修复（Figure 1.11）。该支架可有效改善骨再生，促进血管生成。  \n\n![](images/b88faf3cc6f27484fcc6dcf99d384bc1ca37daef618e14ee38315d2b07d48aeb.jpg)  \nFigure 1.10 various types of natural polymers have been used in bone tissue engineering [90].  \n\n![](images/bb6ecb3d87d9205b24e582c95e59bfe68ce4d0f2f2c7b34f73c0542288501ef2.jpg)  \nFigure 1.11 Schematic illustration of the preparation and characterization of cellladen nano-ATP/GelMA composite hydrogel scaffolds [94].  \n\n在天然聚合物中，壳聚糖是另一种可用于骨再生和修复的聚合物。壳聚糖是一种由甲壳素脱乙酰化而得的线性带正电荷多糖，是虾、蟹等甲壳类动物外骨骼的主要成分 [95, 96]。壳聚糖在体内酶的作用下降解为 N-乙酰氨基葡萄糖和氨基葡萄糖，对人体无毒，可被机体充分吸收[97, 90]。壳聚糖的特点是具有更好的细胞相容性、生物降解性、无毒性和黏液粘附性。它还对骨髓间充质干细胞（BMSCs）具有良好的亲和力和成骨诱导能力，在骨再生中具有广阔的应用前景[98-103]。壳聚糖较差的机械强度妨碍了它的应用，所以需要它与不同的材料（磷酸钙、羟基磷灰石等）结合来提高机械性能。例如，Tuğrul 等[104]将壳聚糖/羟基磷灰石复合水凝胶与MC3T3-E1 细胞混均，并作为 3D 打印的生物墨水。研究分析表明，通过3D 打印制备的新型支架在生理条件下能够保持粘弹性和稳定性，并且在支架中的MC3T3-E1 细胞具有优异的细胞活力和成骨相关基因的高水平表达（Figure1.12）。  \n\n![](images/30dcd7a2e260fdb33e1d4087b90fbc5c8f25b3a86051d08745274fc42f74a9dd.jpg)  \nFigure 1.12 Live/Dead assay and viability of MC3T3-E1 cells encapsulated in hydrogel discs [104].  \n\n与天然聚合物相比，合成聚合物可以避免在人体内引发免疫反应，并且可以通过适当设计聚合物官能团来呈现定制的结构，以满足生物材料所需的功能。这些优势保证了合成聚合物可预测、可重复和可调的特性，可以根据具体应用而变化。目前，研究最多的合成聚合物包括：聚乳酸（PLA/PLLA）、聚己内酯（PCL）、聚乳酸-乙醇酸（PLGA）、聚醚醚酮（PEEK）和聚乙二醇（PEG）等[81, 89, 105-107]。聚乳酸（PLA/PLLA）具有低成本、生物相容性和生物降解性等优点[108]，但它在降解过程中会产生乳酸副产物。在降解的早期阶段，乳酸可以自行代谢；在降解后期，过多的乳酸副产物可形成局部酸性环境，导致组织炎症和细胞死亡[109, 110]。PLA 适用于制备复合材料以增强支架的生物活性并达到良好的治疗效果。例如，Holmes 等[111]通过 3D 生物打印技术制备的 PLA/羟基磷灰石支架具有良好的机械性能，并与骨骼的抗压强度相似，体外人间充质细胞实验也表明它的细胞粘附、增殖和骨分化能力更强，这使其适用于骨组织工程（Figure 1.13）。  \n\n![](images/69519dd40320ffa280c58525977877026700487ceff2faf3dba4e5756316fe98.jpg)  \nFigure 1.13 Flow chart showing the overall experimental design [111].  \n\n聚醚醚酮（PEEK）是一种半结晶型热塑性芳香族聚合物[112, 113]。如 Figure1.14 所示，PEEK 具有耐高温、耐化学性、耐磨性、耐疲劳性、机械强度高、易于加工、自然射线可透过性和与正常人骨相似弹性模量等特性，使其成为具有广阔应用前途的骨科植入物材料之一[114-117]。为了将PEEK 作为承重植入材料，如口腔种植体，研究人员使用了羟基磷灰石（HA）、碳纤维（CF）和玻璃纤维（GF）等填料来增强PEEK 基质材料，以提高其力学性能[118-120]。聚醚醚酮的生物惰性限制了其在骨修复领域的应用。因此，研究人员对聚醚醚酮材料的进行了改性研究，旨在提高其生物活性和骨结合性能，以期拓宽聚醚醚酮的临床应用范围[121]。  \n\n![](images/0e4a0270f9cec809d41f799e6861fba92432dcb96d93ac19a1edcc277f38f551.jpg)  \nFigure 1.14 Schematics of the mechanical, chemical, biological and other properties of PEEK and its composites [122].",
+        "category": " Introduction"
+    },
+    {
+        "id": 19,
+        "chunk": "# 1.2.4 复合生物材料  \n\n复合生物材料旨在结合两种或多种材料来提高支架的加工性能、印刷性能、机械性能和生物活性，以获得理想的骨植入物。复合植入物按其连续相成分可分为金属基、陶瓷基和聚合物基[123]。金属基复合植入物具有优异的力学性能、生物相容性、热稳定性和耐腐蚀性，在临床医疗中得到了广泛的应用。Ti6Al4V 是具有代表性的金属基复合材料。具有合适孔径的多孔 Ti6Al4V 支架的杨氏模量可与天然骨相似，从而减少了应力屏蔽导致的骨质疏松[124, 125]。Ti6Al4V 支架通过包覆钽涂层[126]，加入含有辛伐他汀的水凝胶[127]，或包覆羟基磷灰石/聚多巴胺涂层 [128]，显著促进Ti6Al4V 支架的骨长入、骨整合和成骨能力。尽管金属基复合植入物表现出许多优点，但金属基复合植入物的非生物降解性妨碍了其成为理想植入物。目前，聚合物基复合材料和陶瓷基复合材料在骨组织工程上的应用获得了很大的进展。聚合物材料具有多种适用于骨组织工程的性能，如可生物降解性和可调节的机械性能[129-133]。陶瓷材料在植入后能够直接与骨组织结合 [134]。由陶瓷和聚合物制备的复合材料具有成为骨组织工程植入物的理想性能[135, 136]。例如，Zhao 等[137]将铌掺杂生物活性玻璃（NbBG）分散在具有自溶胀特性的双交联明胶-透明质酸水凝胶（GH）网络中制备了 GH-NbBG 水凝胶（Figure 1.15）。NbBG 的加入显著改善了水凝胶的力学性能，GH-NbBG 水凝胶促进血管生成，  \n\n并通过自身溶胀增加更多的骨的长入。  \n\n![](images/cf5cece71c804e31c12619f12a120fd8977243bbc1cd3baf2c9fedf994ffa7a6.jpg)  \nFigure 1.15 Preparation and biological function diagram of GH-NbBG hydrogel [137].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# 1.3 碳纤维增强聚醚醚酮",
+        "category": " Introduction"
+    },
+    {
+        "id": 21,
+        "chunk": "# 1.3.1 碳纤维增强聚醚醚酮的概述  \n\n碳纤维增强聚醚醚酮（CFRPEEK）复合材料能够提供承重骨所需的刚度、韧性和耐磨性[138]。CFRPEEK 保留了 PEEK 的优势特性，例如：（1）优异的化学稳定性，常温下能够耐受浓硫酸外的所有化学试剂；（2）自然射线可透过性，这一特性有助于对植入物进行放射影像学探究；（3）易于加工性，CFRPEEK 可以通过多种加工方法制备[114-117, 139]。CFRPEEK 具有承重应用所需的机械性能，如作为关节置换和断裂稳定板，并且在植入后能适应机体的磨损和高应力[140, 141]。  \n\nCFRPEEK 可以通过改变碳纤维的体积分数、方向和长度精确的控制  \n\nCFRPEEK 的弹性模量以精确匹配骨的模量（18-20 GPa）[142]，从而避免在金属植入物中经常出现的应力屏蔽现象，这使 CFRPEEK 成为许多骨科植入物的合适选择。CFRPEEK 具有非常高的韧性和刚度，特别是其优异的抗疲劳性，堪比金属材料 [143]。CFRPEEK 还具有优异的自润滑和耐磨性能，CFRPEEK 的磨损量是超高分子量聚乙烯（UHMWPE）的一半，这些性能有助于 CFRPEEK 成为骨科植入物 [144-145]。CFRPEEK 的耐腐蚀性使其不会像金属植入物一样被体液腐蚀，从而释放出有毒的金属离子，最终引起毒性效应。  \n\nCFRPEEK 优异的理化性能使其非常适合在骨科中应用，但其表面具有生物惰性，严重限制了其临床应用[146]。由于植入后的体内排异反应， CFRPEEK 植入物不会直接锚定在周围的骨骼上，而是倾向于被纤维组织包裹或被细菌感染[147-150]，这种现象使得 CFRPEEK 植入物在体内不稳定并且会发生迁移导致植入失败[151]。CFRPEEK 表面极易被细菌粘附，这增加了植入物周围组织感染的风险[152, 153]，这些不太理想的植入情况会使得 CFRPEEK 表面形成炎性纤维囊而不是形成新骨[154]。所以，CFRPEEK 的表面需要进一步进行处理来增强它的生物活性。",
+        "category": " Introduction"
+    },
+    {
+        "id": 22,
+        "chunk": "# 1.3.2 聚醚醚酮及其复合材料表面生物功能化研究现状  \n\n为了改善聚醚醚酮及其复合材料的骨整合能力，目前广泛研究的改性策略有两种：（1）研发含有羟基磷灰石或生物活性玻璃等活性材料的复合材料；（2）通过表面改性策略来提高植入物的骨结合性能[145]。虽然复合材料可以改善骨整合能力，但在聚醚醚酮及其复合材料中掺入脆性材料（如HA）会降低聚醚醚酮及其复合材料的机械性能，这可能会缩短植入物的使用寿命[112]。表面改性策略致力于采用多种物理化学方法在聚醚醚酮及其复合材料表面上构建生物活性结构或引入生物活性物质，以提高材料表面的生物相容性和成骨能力。表面改性策略作用于聚醚醚酮及其复合材料表面，不会改变聚醚醚酮及其复合材料的机械性能[155, 156]。表面改性策略可分为直接表面改性和表面涂层沉积。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# （1）直接表面改性  \n\n表面等离子体处理技术、加速中性原子束技术和激光技术等高能粒子处理方法以及表面化学处理等表面处理方法都可用于聚醚醚酮的表面处理。  \n\n$\\textcircled{1}$ 等离子体  \n\n等离子体处理是指利用 $\\mathrm{N}_{2}$ 、 NH3、 O2、 Ar 和 H2 等气体等离子体对聚醚醚酮及其复合材料植入物表面进行处理，改变其表面形态或在其表面构建具有生物活性的官能团结构[157-160]，从而提高聚醚醚酮及其复合材料的表面亲水性、生物活性和生物相容性[161-163]。  \n\n等离子体浸没离子注入（PIII）是另一种等离子体处理方法，可在聚醚醚酮及其复合材料表面上引入金属元素或官能团，而不受传统等离子体处理的限制[164]。例如，Zhao 等[163]通过水（ $:{\\mathrm{H}}_{2}{\\mathrm{O}}\\ \\cdot$ ） 和氨（NH3）等离子体浸没离子注入（PIII）技术改变了PEEK 表面的亲水性和表面粗糙度，显著增强了 PEEK 的体外成骨分化和体内的骨整合能力（Figure 1.16）。等离子体处理的方法可重复、便宜且易于操作，可应用于各种形状和结构材料的改性。但是，等离子体处理产生的修饰效果无法长期维持，修饰后的材料表面只能维持短期的生物活性。  \n\n![](images/b6e93bdc850a7c96d730357990e572759851c7a65fc0728b4566673370023222.jpg)  \nFigure 1.16 Diagram of preparation and biological function of PEEK modified by plasma immersion ion implantation (PIII) [163].  \n\n$\\textcircled{2}$ 加速中性原子束  \n\n加速中性原子束（ANAB）技术采用中性气体原子的强定向束来修饰聚醚醚酮及其复合材料。该方法可以控制每个原子的平均能量为 10eV 到 $100\\mathrm{eV}$ 的范围内，ANAB 对材料表面的改性深度仅为 2-3 纳米，是一种超浅表面处理技术，对基体结构的影响远远小于其它改性方法[165-167]。目前，Khoury 等证实了ANAB 技术可以通过改变 CFRPEEK 表面形貌和增加粗糙度来增强聚醚醚酮及其复合材料生物活性，有利于聚醚醚酮及其复合材料与周围组织和骨骼的结合 [165, 168, 169]。  \n\n$\\textcircled{3}$ 激光  \n\n激光技术是利用激光辐照改变材料表面形貌和化学性质。在这种方法中，激光束直接发射到聚醚醚酮及其复合材料表面上，激光提供的光能被材料表面吸收，温度升高使得表面熔化或汽化，从而导致材料表面粗糙度的改变[170]。相关研究表明，粗糙的表面能够促进细胞的粘附和增殖[171, 172]。这种方法具有成本低、分辨率高、操作速度快等优点。激光技术不改变植入体的形状，只处理材料的表面[173]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# $\\textcircled{4}$ 紫外线  \n\n紫外线的辐照可以破坏聚醚醚酮主链结构中的酮羰基，产生自由基，诱导生物活性烯烃或其他活性单体聚合，从而使生物活性物质接枝到聚醚醚酮及其复合材料表面[174, 175]。紫外线（UV）辐照接枝对设备的要求比较低，操作相对简单，不影响材料的结构和性能。例如，Pang 等[176]通过紫外诱导丙烯酸（AAc）接枝聚合将羧基引入PEEK 表面，再通过 AAc 的羧基与壳聚糖（CS）的氨基反应将CS固定在PEEK表面，从而提高了PEEK表面的亲水性和抗菌性能（Figure 1.17）。  \n\n![](images/60cc78a9d3d02439046821f8a3a3cb7aca8b06a8a79b4d2a2fbf6078984efc71.jpg)  \nFigure 1.17 Immobilization of chitosan on polyether ether ketone surface modified with acrylic acid by UV-induced graft polymerization [176].  \n\n$\\textcircled{5}$ 磺化处理  \n\n磺化处理是通过浓硫酸处理，在聚醚醚酮及其复合材料表面形成三维、多孔、纳米结构网络，引入磺酸基团，以增强聚醚醚酮及其复合材料生物活性的改性方法。通过磺化处理获得的孔径范围为 $0.5{\\sim}1.0{\\upmu}\\mathrm{m}$ 。磺化处理促进了成骨细胞在PEEK 上的粘附、增殖、分化、骨再生和磷灰石形成[177-180]。残留的硫会对成骨细胞的行为和新骨的形成产生影响[177, 181]。适当的后处理方法，如水热处理[182]、丙酮洗涤[183]和氢氧化钠冲洗[184]，有助于去除多余的硫。例如，Ma 等[185]比较了不同后处理方法（丙酮冲洗，水热处理，和氢氧化钠浸没）处理磺化 PEEK，发现不同后处理方法对去除残留硫酸和细胞相容性表现出相同的效果，并且没有改变 PEEK 表面形貌（Figure 1.18）。  \n\n![](images/a675fb671be70ab581aebc00ca5ba0da4301ee5b489bf596f43607a0119adf41.jpg)  \nFigure 1.18 (a) Schematic diagram of optimization of the sulfonation time and post-treatment method of sulfonated PEEK. (b) Cell viability of MC3T3-E1 cells on the surface of SPEEKs with different post-treatment methods, (T1: acetone rinsing,  \n\nT2: hydrothermal treatment, T3: NaOH immersion) [185].  \n\n$\\textcircled{6}$ 其它化学处理方法  \n\n除了磺化处理外，科研工作者还利用多种化学物质来还原或水解聚醚醚酮及其复合材料表面，从而在聚醚醚酮及其复合材料表面引入氨基、羧基等活性基团[186, 187]。对于PEEK 的表面羧基化，首先通过硼氢化钠（ $\\mathrm{NaBH_{4}}$ ）将其表面的羰基还原为羟基，接下来羟基化预处理的 PEEK 用有机硅烷溶液处理，从而形成羧基（-COOH）化的功能性表层，最后PEEK表面的羧基与肽的氨基之间形成-CONH，从而实现了生物活性分子的固定[188]。  \n\n（2）表面涂层沉积  \n\n表面涂层沉积是将能与骨结合或促进骨生长的材料沉积在聚醚醚酮及其复合材料表面以改善它们的骨整合性能。用于表面涂层沉积的材料包括： $\\textcircled{1}$ 生物活性离子； $\\textcircled{2}$ HA、Ti 和二氧化钛（TiO）等骨传导材料； $\\textcircled{3}$ 蛋白质、多肽和/或药物[145]。  \n\n$\\textcircled{1}$ 生物活性离子  \n\n目前已知的能够促进成骨的生物活性离子，包括：钙（Ca）、镁（ $(\\mathbf{Mg})$ ）和锌（Zn）等。将这些生物活性离子直接作为涂层或者间接用作生物玻璃基涂层的掺杂剂来增强PEEK 及其复合材料的表面粗糙度，从而达到提高 PEEK 及其复合材料成骨性能的目的[189-192]。  \n\n钙（Ca）是骨的主要成分之一， $\\mathrm{Ca}^{2+}$ 调节成骨细胞的分化以及胶原蛋白和骨蛋白的表达[193]。Lu 等[193]通过钙等离子体浸没离子注入（Ca-PIII）技术将纯钙涂层沉积到 PEEK 表面（Figure 1.19）。大鼠骨髓间充质干细胞 （BMSC） 在 Ca-PIII 处理的PEEK 表面上的粘附、增殖和骨分化得到改善。  \n\n![](images/a7001dd4e74eaec0e3b0c7b8e3f3fce9eb74248521a59b412ad70309dbc38e60.jpg)  \nFigure 1.19 A schematic illustration of calcium plasma immersion ion implantation (Ca-PIII) modified PEEK [193].  \n\n镁 $(\\mathbf{Mg})$ ）参与了许多细胞过程，如 $\\mathrm{Na^{1+}}$ 和 $\\mathrm{Ca}^{2+}$ 离子通道的调节、细胞附着、生长和增殖，以及骨代谢和结晶[194]。例如，Ren 等[195]通过微波辅助工艺在PEEK上制备了具有生物活性的无定形磷酸镁（AMP）涂层。无定形磷酸镁（AMP）涂层作为 PEEK 植入物和宿主组织之间的生物活性界面，通过释放 $\\mathrm{Mg^{2+}}$ 促进了MC3T3-E1 细胞在PEEK 上的增殖和成骨分化，改善了 PEEK 的骨整合性能。  \n\n锌（Zn）为一些参与骨形成过程的蛋白质提供结构支持，并通过促进细胞增殖和成骨基因的表达来调节成骨细胞的代谢[196]。Lu 等[197]采用锌和氧等离子体双重浸没离子注入来修饰 CFRPEEK 表面，同时实现了锌的掺入以及独特的微/纳米结构的形成（Figure 1.20），促进了 MC3T3-E1 细胞的粘附和增殖， $Z\\mathrm{n}^{2+}$ 的释放增强了结构化CFRPEEK 表面BMSC 的成骨分化。  \n\n![](images/8cc834f8ed614dc9eacaa0a65671e23b4f8997b3165f5999448252ef91d9c9ef.jpg)  \nFigure 1.20 Surface views of CFRPEEK (a) and Zn–O (b) samples. The inset on the top right corner is high magnification of the sample [197].  \n\n$\\textcircled{2}$ HA、Ti 和二氧化钛（TiO2）  \n\n钛（Ti）具有高疲劳强度、生物相容性和促进骨生长的骨传导特性[198]。在Ti表面形成的二氧化钛氧化层可以促进 SBF 溶液中磷灰石的形成[199]。Ti 具有促进骨整合的优异能力，已经作为涂层应用于 PEEK 和 CFRPEEK 植入物。例如，Stefan 等[200]将等离子喷涂钛涂层的 PEEK 和 CFRPEEK 植入到绵羊骨盆中发现在 2 周和 12 周移除植入物所需的力显著增加，这说明钛涂层增加了 PEEK 和CFRPEEK 植入物与周围骨组织之间的结合力。Lu 等[201]利用高能离子轰击和表面微电荷协同作用在CFRPEEK 上制备了 $\\mathrm{TiO}_{2}$ 纳米孔（Figure 1.21）。纳米多孔的 CFRPEEK 表面促进 BMSC 的粘附、增殖和成骨分化。 $\\mathrm{TiO}_{2}$ 纳米颗粒独特的多层纳米孔结构还能够杀死金黄色葡萄球菌和大肠杆菌。  \n\n![](images/e41ba465b268cc1536b37eea30dcde1933e0e60bf209c7b7168ce1cf8acb868f.jpg)  \nFigure 1.21 (a) Schematic illustration of the formation mechanism of nanopores with $\\mathrm{TiO}_{2}$ walls. (b) Cross-sectional morphology of CFRPEEK and Ti-120 samples [201].  \n\nHA 是骨骼的主要无机成分，是一种骨传导磷酸钙材料，不仅能够增强细胞粘附，还可以与周围骨骼整合[202]。由于 HA 能够与天然骨紧密结合，许多研究已经在 PEEK 植入物上制备 HA 涂层，以改善植入物的骨结合性能。Li 等[203]采用冷喷涂方法在形貌复杂的三维 PEEK 植入物表面制备了生物相容性 HA 涂层。将冷喷涂的HA-PEEK 脊椎笼植入小型猪的髂骨缺损中，植入物与周围骨的结合率和新生骨的骨密度显着提高。经过等离子喷涂 Ti 和/或HA 涂层的 PEEK 脊髓笼已被FDA 批准用于临床，这些涂层也被用于改善 CFRPEEK 的骨整合能力。  \n\n$\\textcircled{3}$ 蛋白质、多肽和/或药物  \n\n在聚醚醚酮及其复合材料表面附着的生物分子可以诱导特定的细胞反应。蛋白质和/或多肽涂层为细胞提供了粘附位点，在接下来的信号传导中起重要作用[204, 205]。具有促成骨作用的生物分子和蛋白质能够增强细胞粘附、增殖和成骨分化[206, 207]。  \n\n骨形态发生蛋白（BMP），如 BMP-2 和 BMP-7，能够促进骨折后的骨生成和修复[208, 209]。Shah 等[210]通过逐层沉积（LBL）方法在 PEEK 表面制备了含有HA 和BMP-2 的涂层，该涂层能够控制 BMP-2 的释放，避免了 BMP-2 局部的高浓度释放，极大地提高了 PEEK 的骨整合能力。BMP-2 的逐渐释放使其在周围骨基质中积累，从而在植入后第一个月促进了骨髓细胞的体外和体内成骨分化以及PEEK 植入物周围的新骨生成。  \n\n精氨酸 - 甘氨酸 - 天冬氨酸（RGD）序列是纤连蛋白中发现的最小细胞粘附序列，能够促进细胞粘附[211]。将 RGD 肽共价固定在化学预处理的 PEEK 表面，显著改善了细胞的初始粘附和增殖[212]。Zhu 等[213]通过聚多巴胺（PDA）涂层将 RGD 肽共价接枝到 SPEEK 表面（Figure 1.22）。在第 7 天和第 14 天，RGD肽修饰的PEEK 促进细胞增殖，显著上调了碱性磷酸酶（ALP）和骨钙素的基因表达，说明RGD 肽可以促进 MC3T3-E1 细胞成骨分化。  \n\n![](images/cb0de71c1f1218ccde4535420d6f730d06e88577935c7c8ec58ad45e06c9991b.jpg)  \nFigure 1.22 (a) Chemical structure of RGD peptide. (b) Schematic Diagram of the Preparation of a Functional PEEK Surface in Various Stages of Surface Modifications with the Chemical Structure Diagram of the RGD Peptide. (c) Biological function diagram of modified PEEK [213].  \n\n染料木素是一种天然存在于大豆中的异黄酮，可以促进新骨生成和成骨相关基因的表达。Cai 等[192]将染料木素负载到复合介孔镁-钙-硅酸盐生物玻璃的纳米孔中，并通过喷砂处理对PEEK 进行了表面改性。染料木素的掺入进一步增强了PEEK 的成骨性能，显著改善了 MC3T3-E1 细胞的粘附、增殖、ALP 活性和体内骨整合能力。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 25,
+        "chunk": "# 1.4 水凝胶在骨组织工程中的应用研究  \n\n在骨骼的再生过程中，细胞外基质（ECM）在骨组织间的信号传递和物质交换中发挥着至关重要的作用[214]。水凝胶是水溶胀聚合物，具有通过各种交联反应形成的3D 网络结构，适用于细胞生长和生物活性分子的转移[215]。与骨修复过程中的其他生物活性材料相比，水凝胶材料在促进干细胞的粘附、增殖和分化能力方面具有天然的优势[216]。近年来，科研工作者利用理化方法制备了多种水凝胶，以增强骨再生能力[217-219]。  \n\n物理交联水凝胶是利用离子间相互作用、氢键结合、结晶等作用制备的水凝胶 [220, 221]。离子水凝胶是通过离子作为交联剂而形成的水凝胶。矿物质作为基本营养元素，对于维持正常的身体功能很重要。铁、铜、锌和钙等矿物离子在调节或维持细胞行为和生物体平衡方面起关键作用[222, 223]。将这些矿物离子引入到凝胶体系中不仅能起到交联剂的作用，还能调节骨组织愈合过程中的细胞行为和生理环境稳态。例如，Zhen 等[224]制备了一种铜掺杂双交联可注射水凝胶，用于骨组织修复。在植入初期，该水凝胶可用于光热治疗，光热剂的降解和铜离子的释放可以促进骨组织修复（Figure 1.23）。离子水凝胶最显著的特点是其自愈能力，凝胶网络可以在高剪切力下被破坏，并在剪切力去除后进行修复。由于离子相互作用是物理交联方法，较差的机械性能严重限制了这类水凝胶在骨和其他硬组织修复中的应用[225]。  \n\n![](images/b2d90b4fbfc04bbf0f8829103c91ee52ce0f8f5ae291413723d850cf3078b00e.jpg)  \nFigure 1.23 Schematic illustration for the formation of injectable SA/PEG-CuBGM composite hydrogels with photothermal therapy and bone regeneration [224].  \n\n温度响应型水凝胶会对温度做出反应，温度变化会使这类凝胶的体积发生变化[226]。温度响应型水凝胶在温度变化后具有独特的溶胶凝胶特性，所以特别适用于骨组织工程[227]。生物医学领域常见聚合物几乎没有热敏行为，通常将热响应链共价交联到聚合物中来制备温度响应型水凝胶。作为热响应聚合物的典型代表，聚 (N-异丙基丙烯酰胺)（PNIPAAm）因其温度在 $32^{\\circ}\\mathrm{C}$ （较低临界溶液温度）时的相平移能力成为最受欢迎的材料[228]。由于线性的 PNIPAAm 在室温下状态不稳定，所以要将 PNIPAAm 与其他聚合物链结合来提高其稳定性和机械性能[229]。例如，Ekerdt 等[230]将透明质酸（HA）掺入热响应水凝胶系统中以增强水凝胶基质的机械性能。HA-PNIPAAm 水凝胶的机械行为受到温度的调控以适应特定的干细胞分化，较硬的水凝胶对 BMSCs 的成骨分化有更好的促进作用（Figure1.24）。  \n\n![](images/738f25e126cc160251f47a8396d8462eb7956936b406eaeea1bb9575c07ff464.jpg)  \nFigure 1.24 (A) Schematic of HA-PNIPAAm. (B–D) The steps for cell encapsulation [230].  \n\n化学交联水凝胶是利用化学交联方法，使得水凝胶体系中的分子链之间形成共价键，包括小分子交联，光诱导交联等。与物理交联方法相比，通过化学交联方法制备的水凝胶具有优异的机械性能和稳定性[225]。在水凝胶体系中掺入特定的小分子交联剂，包括戊二醛、染料木酚、多巴胺和单宁酸（TA），是调节水凝胶功能和机械性能的有效方法。由于对细胞和组织的毒副作用，戊二醛的应用受到限制[231]。受贻贝生物粘附机制的启发，儿茶酚化合物（如多巴胺、咖啡酸）  \n\n因其官能团赋予其强大的表面粘附力而常被用于组织再生工程。例如，Li 等[232]制备的 $\\mathrm{Fe}_{3}\\mathrm{O}_{4}$ 纳米颗粒和多巴胺修饰的 PEG 水凝胶具有受控的机械性能和自愈能力，适用于那些软（皮肤伤口）或硬（骨缺损）组织。  \n\n光触发水凝胶是骨组织工程中最有前途的水凝胶之一。它可以由特定波长（紫外线或可见光）的光触发，并诱导凝胶三维网络的形成和形态变化[233]。由于原位凝胶化和简便的制备条件，该方法满足了骨相关疾病的各种要求。许多基于天然和合成的聚合物都用光响应交联基团改性。例如，Qiao 等[234]人在紫外光下通过成骨生长肽（OGP）和甲基丙烯酰化明胶（GelMA）之间的共价连接制备了一种新型 GelMA 水凝胶（Figure 1.25），这种光交联水凝胶不仅延长了 OGP的作用时间，而且为调节细胞行为提供了稳定的微环境，从而增强了骨缺损处新组织的再生。  \n\n![](images/2dda8f580506c9f79d777191659ea0e3823aaf19a31f8bbb778812aa41077bc6.jpg)  \nFigure 1.25 Flow chart of GelMA-c-OGP hydrogel construction and its mechanical properties [234].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 26,
+        "chunk": "# 1.5 本论文设计思想  \n\nCFRPEEK 复合材料因其优异的物理、化学、机械性能和与人体骨骼相匹配的弹性模量，被认为是潜在的骨科植入物，受到国内外研究人员的广泛关注。CFRPEEK 植入物的生物惰性导致它与骨组织和细胞的整合能力差，极大限制了其临床应用。改善CFRPEEK 植入物的生物惰性成为研究 CFRPEEK 复合材料作为骨科植入物的主流趋势。除此之外，在超过临界尺寸的骨缺损的愈合过程中，改性的 CFRPEEK 植入物应该能够协调不同愈合阶段（免疫、血管化和骨再生）以恢复缺损处的骨组织功能。从骨缺损愈合所需要的生物功能的角度出发，结合临床对超过临界尺寸骨缺损植入物的需求，本论文将通过磺化处理和紫外接枝等表面改性技术，用负载地塞米松的甲基丙烯酰化明胶-聚丙烯酰胺复合凝胶、氧化石墨烯-羟基磷灰石冷冻凝胶和金属有机框架水凝分别修饰 CFRPEEK，从而开发三种具有多功能生物活性凝胶修饰 CFRPEEK 骨科植入物，用于满足骨愈合环境下所需的多种生物功能，以拓宽 CFPEEK 复合材料在生物医学领域中的应用范围，为其临床应用提供了新的研发思路和科学参考。根据超过临界尺寸的骨缺损愈合过程中所需要的生物相容性和成骨能力，设计负载地塞米松的复合凝胶修饰CFRPEEK 植入物；在第一个工作基础上，为进一步提升骨缺损愈合过程中所需要的成血管和成骨能力，设计氧化石墨烯-羟基磷灰石冷冻凝胶修饰CFRPEEK 植入物；将在前两个工作基础上，为进一步提升骨缺损愈合过程中所需要的免疫调节、成血管和骨再生能力，设计 pH 响应性金属有机框架凝胶修饰CFRPEEK 植入物。将对制备的具有生物活性的多功能凝胶表面修饰 CFRPEEK植入物进行理化性能、体外生物学和体内骨缺损修复能力的探究，以期为CFRPEEK 植入物的开发及临床应用提供新的思路和建设策略。  \n\n1. 对于超过临界尺寸的骨缺损的治疗所需的植入物不仅需要它具备与骨骼适配的机械性能，还应该具有生物相容性和成骨能力。从提升骨愈合所需的生物相容性和成骨能力的角度出发，设计制备负载地塞米松的复合凝胶修饰CFRPEEK 植入物。采用磺化处理和紫外接枝的表面改性方法将负载地塞米松（Dex）的甲基丙烯酰化明胶/聚丙烯酰胺复合水凝胶（GelMA/PAAM）修饰到CFRPEEK 植入物上，构建出具有三维凝胶网络表面的 CFRPEEK 植入物。该三维凝胶网络的表面能够增强CFRPEEK 植入物的生物相容性和成骨能力。  \n\n2. 骨骼是一个高度血管化的组织，在骨缺损愈合的过程中还伴随着血管的重塑。在骨愈合过程中的血管生成不及时会造成氧气和营养物质的供应不足，从而导致后期的成骨能力差。从提升骨愈合所需的成血管和成骨能力的角度出发，设计制备氧化石墨烯-羟基磷灰石冷冻凝胶修饰 CFRPEEK 植入物用于提高CFRPEEK 植入物的成血管和成骨能力。首先，通过原位键合的方法制备氧化石墨烯-羟基磷灰石（GO-HAP）纳米复合材料，再采用磺化处理和基于自由基光聚合的冷冻凝胶方法将负载氧化石墨烯-羟基磷灰石的冷冻凝胶接枝到 CFRPEEK植入物表面上，构建具有3D 海绵状大孔凝胶网络表面的CFRPEEK 植入物。该冷冻凝胶层主要由氧化石墨烯-羟基磷灰石（GO-HAP）纳米复合材料和甲基丙烯酰化明胶/聚乙二醇二丙烯酸酯（GelMA/PEGDA）组成。GO-HAP 纳米复合材料既能促进血管的新生又能提高成骨能力，并且 3D 海绵状大孔凝胶网络也能够促进血管的长入与迁移。  \n\n3. 骨缺损的愈合发生在良好的炎症、血管化和成骨分化的基础上，植入物在植入早期过度的炎症反应和不及时的血管化会影响后期新骨的生成。从提升骨愈合所需的抗炎、成血管和成骨分化的角度出发，设计制备 $\\mathsf{p H}$ 响应性金属有机框架（MOF）凝胶修饰CFRPEEK 植入物来增强 CFRPEEK 植入后的抗炎、血管化和成骨能力。首先，通过纳米羟基磷灰石（HAP）、没食子酸（GA）和镁离子（ $\\mathrm{(Mg^{2+})}$ ）之间的配位作用设计制备具有核壳结构的羟基磷灰石 $@$ 镁-没食子酸（ $\\mathbf{\\chi}_{\\mathrm{HAP}@\\mathbf{M}\\mathbf{g}-}^{\\prime}$ GA）金属有机框（MOF）纳米颗粒。然后，通过磺化处理和紫外接枝的方法对CFRPEEK 植入物进行表面改性，在 CFRPEEK 植入物上构建出负载 ${\\mathrm{HAP}}@{\\mathrm{Mg-}}$ GA MOF 纳米颗粒的水凝胶层。水凝胶基质选择的是具有 $\\mathfrak{p H}$ 响应性的甲基丙烯酰化壳聚糖，该凝胶基质可以随着骨缺损处生理环境 $\\mathsf{p H}$ 值的变化来控制HAP@Mg-GA MOF 纳米颗粒中 GA、 $\\mathrm{Mg}^{2+}$ 和 $\\mathrm{Ca}^{2+}$ 的释放，从而提高 CFRPEEK植入物的抗炎、血管化和成骨分化能力。  \n\n本论文拟解决的CFRPEEK植入物的瓶颈问题以及具体的研究思路如Figure1.26 所示：",
+        "category": " Introduction"
+    },
+    {
+        "id": 27,
+        "chunk": "# 碳纤维增强聚醚醚酮植入物的瓶颈问题  \n\n生物情性导致它与骨组织和细胞的整合能力差，极大限制了其临床应用。  \n\n从骨缺损愈合所需要的生物功能的角度出发，结合临床对超临界尺寸骨缺损植入物的需求，构建具有多功能凝胶修饰碳纤维增强聚醚醚酮植入物。  \n\n![](images/f81fcc6ec79e3813db4cfd9feeb8951b9575c7771a041cadd1439957c10623db.jpg)  \nFigure 1.26 Schematic diagram of the main problems to be solved and the research methods of this paper.",
+        "category": " Introduction"
+    },
+    {
+        "id": 28,
+        "chunk": "# 第2 章 负载地塞米松的复合水凝胶修饰 CFRPEEK 的制备及其成骨能力的研究",
+        "category": " Introduction"
+    },
+    {
+        "id": 29,
+        "chunk": "# 2.1 前言  \n\n随着临床医学技术的发展，传统的金属骨科植入材料（如：钛和不锈钢）得到了广泛的应用[235]。这些植入物存在的一些缺点会导致植入失败，例如由于体内生理环境腐蚀而导致的金属离子释放、应力屏蔽和磁共振成像 （MRI） 不相容[236]。与传统的骨科植入物相比，本研究团队采用三维（3D）针刺方法制备的长碳纤维（ $\\mathrm{.40mm}\\cdot$ ）增强聚醚醚酮（CFRPEEK）是一种高性能复合材料，具有优异的机械强度 （ ${400}{-700}\\mathrm{MPa})$ ）、低密度 （ $1.43\\:\\mathrm{g}/\\mathrm{cm}^{3}$ ）和各向同性[237]。设计制备的 CFRPEEK（ $C\\mathrm{F}{:}30{-}60\\ \\mathrm{wt}^{\\mathrm{0}}\\mathrm{\\Omega}_{\\mathrm{0}}$ ）具有可调节的弹性模量（ $18{-}35\\ \\mathrm{GPa})$ ），接近于人类皮质骨的弹性模量（ ${\\sim}20\\mathrm{GPa})$ ），这会最大限度地减少应力屏蔽。除了优异的机械性能外，制备的 CFRPEEK 还保留了 PEEK 的优点，即无毒，化学稳定性，计算机断层扫描和MRI 兼容性[201, 238]，因此，CFRPEEK 在骨科植入物中具有广泛的潜在应用。CFRPEEK 复合材料具有生物惰性，与骨组织的结合较差，增加了松动的风险，最终会导致植入失败，从而限制了其临床应用[156, 178]。所以，有必要对制备的CFRPEEK 进行改性以获得具有生物功能的植入物，从而实现它的最佳临床应用。  \n\n材料的表面改性是一种非常有效的改进材料生物活性技术，利用这一技术可以提高CFRPEEK 的生物相容性和骨结合性。它可以在不改变材料优异性能的情况下改善材料与骨组织之间的结合性能[239]。对于 PEEK 及其复合材料，通过表面磺化处理和光诱导自由基接枝聚合等方法可以改善其生物活性。浓硫酸的磺化处理可以在PEEK 及其复合材料表面上制备多孔结构[177, 240, 241]。高能电子束，如紫外线或伽马射线等，可以破坏 PEEK 及其复合材料表面的化学键，从而在材料表面接枝活化的单体或聚合物，以增强 PEEK 及其复合材料的生物活性[242-246]。  \n\n甲基丙烯酰化明胶（GelMA）是一种可光聚合的明胶衍生物。GelMA 结构中包含的RGD 序列可以促进细胞粘附、增殖和分化，广泛应用于组织工程。尽管 GelMA 水凝胶表现出优异的生物相容性，但较快的降解速率限制了它在组织工程中的应用[247-249]。研究人员设计了由天然聚合物和合成聚合物制备的复合水凝胶，以调整GelMA 的降解性能，从而拓宽它的应用范围。GelMA 制备的复合水凝胶不仅具有生物相容性，还具有良好韧性[250-252]。聚丙烯酰胺（PAAM）水凝胶是一种光交联的合成聚合物水凝胶，具有优异的柔韧性和变形性能[253-256]。糖皮质激素是维持身体正常运转的重要物质。在正常情况下，糖皮质激素参与控制人体骨骼的生长和发育[257]。地塞米松（Dex）， 一种糖皮质激素， 广泛用于治疗传染病和免疫疾病。之前的一项研究发现，低浓度的 Dex 能够促进 BMSC细胞的成骨分化[258]。  \n\n本章设计了一种负载 Dex 的复合凝胶修饰 CFRPEEK 植入物，通过浓硫酸的磺化处理和紫外（UV）照射将 GelMA/PAAM 复合水凝胶接枝在 CFRPEEK 植入物的多孔表面上，随后通过浸泡 Dex 溶液将 Dex 负载在 CFRPEEK 表面的GelMA/PAAM 复合水凝胶上，从而提高 CFRPEEK 的生物相容性和成骨能力。对改性的CFRPEEK 植入物的宏观及微观形貌、亲水性、Dex 的长期控释能力和体外矿化能力进行了研究，探究了改性 CFRPEEK 植入物的体外生物相容性和成骨能力。通过大鼠临界颅骨缺损实验进一步研究了改性 CFRPEEK 植入物的骨修复及骨整合能力。Figure 2.1 为设计的技术路线示意图。  \n\n![](images/bd163fa166c8a28dff98db949416a11ba027fb0c9d0622a25d92c017fd4d1ab5.jpg)  \nFigure 2.1 Schematic illustration of the modification processes on the surface of",
+        "category": " Introduction"
+    },
+    {
+        "id": 30,
+        "chunk": "# 2.2 实验部分",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 31,
+        "chunk": "# 2.2.1 实验材料与仪器",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 32,
+        "chunk": "# 1.实验材料  \n\nTable 2.1 The materials and reagents.   \n\n\n<html><body><table><tr><td>名称</td><td>缩写</td><td>产品规格</td><td>生产厂家</td></tr><tr><td>聚醚醚酮纤维</td><td>PEEK fiber</td><td>MI= 42 g/10min</td><td>实验室自制</td></tr><tr><td>碳纤维</td><td>CF</td><td>T700-24k,</td><td>日本东丽</td></tr><tr><td></td><td></td><td>密度1.8 g/cm²,</td><td></td></tr><tr><td></td><td></td><td>细度1650 tex</td><td></td></tr><tr><td>明胶</td><td>Gel</td><td>A 型,源自猪皮,</td><td>上海昂一生物科技有限</td></tr><tr><td>丙烯酰胺</td><td></td><td>试剂级</td><td>公司</td></tr><tr><td></td><td>AM</td><td>AR,99%</td><td>上海易恩化学技术有限 公司</td></tr><tr><td>甲基丙烯酸酐</td><td>MA</td><td>AR, 94%</td><td>北京百灵威科技有限公</td></tr><tr><td></td><td></td><td></td><td>司</td></tr><tr><td>透析膜</td><td></td><td>12-14 kDa</td><td>赛默飞世尔科技 (中国) 有限公司</td></tr><tr><td>浓硫酸</td><td>H2SO4</td><td>95~98%</td><td>北京化工厂</td></tr><tr><td>丙酮</td><td></td><td>AR</td><td>北京化工厂</td></tr><tr><td>无水乙醇</td><td></td><td>AR</td><td>北京化工厂</td></tr><tr><td>改良模拟体液</td><td>SBF</td><td>1.5X</td><td>飞净科技</td></tr><tr><td>罗丹明标记的</td><td></td><td>AR</td><td>翊圣生物科技</td></tr><tr><td>鬼笔环肽 4',6-二基-2-</td><td>DAPI</td><td>AR</td><td>索莱宝</td></tr><tr><td>苯基吲哚 培养基</td><td></td><td></td><td></td></tr><tr><td></td><td>DMEM</td><td></td><td>赛默飞世尔科技 (中国) 有限公司</td></tr><tr><td>胎牛血清</td><td></td><td></td><td></td></tr><tr><td></td><td>FBS</td><td></td><td>美国Clark 公司</td></tr></table></body></html>  \n\n<html><body><table><tr><td colspan=\"4\"></td></tr><tr><td>名称</td><td>缩写</td><td>产品规格</td><td>生产厂家</td></tr><tr><td>青霉素-链霉素</td><td></td><td></td><td>赛默飞世尔科技 (中国)</td></tr><tr><td>CCK-8试剂盒</td><td>CCK-8</td><td></td><td>上海碧云天公司</td></tr><tr><td>碱性磷酸酶试 ALP</td><td></td><td></td><td>上海碧云天公司</td></tr><tr><td>剂盒</td><td></td><td></td><td></td></tr><tr><td>BCIP/NBT染色</td><td></td><td></td><td>上海碧云天公司</td></tr><tr><td>试剂盒</td><td></td><td></td><td></td></tr><tr><td>氯化十六烷基</td><td></td><td></td><td>上海碧云天公司</td></tr><tr><td>吡啶 Trizol试剂</td><td></td><td></td><td>赛默飞世尔科技 (中国)</td></tr><tr><td></td><td></td><td>有限公司</td><td></td></tr><tr><td>PrimeScriptTM</td><td></td><td></td><td>日本 Takara Bio 公司</td></tr><tr><td>RT试剂盒</td><td></td><td></td><td></td></tr><tr><td>TB GREEN 试</td><td></td><td></td><td>日本 Takara Bio 公司</td></tr><tr><td>剂盒</td><td></td><td></td><td></td></tr><tr><td>苏木精-伊红染 H&E</td><td></td><td></td><td>武汉赛维尔生物科技有</td></tr><tr><td>色剂</td><td></td><td>限公司</td><td></td></tr><tr><td>Van Gieson 染色</td><td></td><td></td><td>武汉赛维尔生物科技有</td></tr><tr><td>试剂盒</td><td></td><td>限公司</td><td></td></tr><tr><td>Masson 三色染</td><td></td><td></td><td>武汉赛维尔生物科技有</td></tr><tr><td>色试剂盒</td><td></td><td>限公司</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 33,
+        "chunk": "# 2. 实验仪器  \n\nTable 2.2 The experimental apparatus.   \n\n\n<html><body><table><tr><td>仪器名称</td><td>型号</td><td>生产厂家</td></tr><tr><td>真空热压机</td><td>P 400PV</td><td>德国科林</td></tr><tr><td>超声波清洗器</td><td>YQ-1003A</td><td>上海易净超声波仪器有限公司</td></tr><tr><td>真空干燥箱</td><td>DZF-6050</td><td>上海博迅实业有限公司</td></tr><tr><td>真空冷冻干燥机</td><td>SCIENTZ-10 N</td><td>宁波新芝生物科技有限公司</td></tr><tr><td>紫外灯</td><td>10 mW/cm²，365nm</td><td>中山市宇固电器厂</td></tr></table></body></html>  \n\n第2 章 负载地塞米松的复合水凝胶修饰CFRPEEK 的制备及其成骨能力的研究  \n\n\n<html><body><table><tr><td>仪器名称</td><td>型号</td><td>生产厂家</td></tr><tr><td>核磁共振波谱仪</td><td>400MHz</td><td>德国 Bruker 公司</td></tr><tr><td>场发射扫描电子显微</td><td>Nova Nano</td><td>450美国 FEI公司</td></tr><tr><td>镜</td><td>(SEM)</td><td></td></tr><tr><td>能量色散X射线谱仪</td><td>S2 RANGER (EDS)</td><td>德国布鲁克</td></tr><tr><td>傅里叶红外光谱仪</td><td>iS10 (ATR-FTIR)</td><td>赛默飞世尔科技（中国)有限公</td></tr><tr><td></td><td></td><td>司</td></tr><tr><td>X射线光电子能谱仪</td><td>AHIS-HS (XPS)</td><td>英国 Kratos 公司</td></tr><tr><td>电子万能材料试验机</td><td>AGX</td><td>日本岛津株式会社</td></tr><tr><td>静态接触角测量仪</td><td>SL200B</td><td>上海梭伦信息科技有限公司</td></tr><tr><td>恒温摇床</td><td>OS-60</td><td>莱普特科学仪器有限公司</td></tr><tr><td>紫外-可见分光光度计</td><td>UV-1900i</td><td>日本岛津株式会社</td></tr><tr><td>恒温培养箱</td><td>371</td><td>赛默飞世尔科技（中国）有限公</td></tr><tr><td></td><td></td><td>司</td></tr><tr><td>共聚焦激光扫描显微 镜</td><td>FV3000</td><td>日本奥林巴斯株式会社</td></tr><tr><td>酶标仪</td><td>iMark</td><td>美国 Bio-Rad 公司</td></tr><tr><td>PCR 仪</td><td></td><td>美国 Bio-Rad 公司</td></tr><tr><td>实时荧光定量 PCR480</td><td></td><td></td></tr><tr><td></td><td></td><td>美国罗氏公司</td></tr><tr><td>仪</td><td></td><td></td></tr><tr><td>Micro-CT</td><td>Skyscan 1172</td><td>德国 Bruker 公司</td></tr><tr><td>脱水机</td><td>Donatello</td><td>DIAPATH</td></tr><tr><td>包埋机</td><td>JB-P5</td><td>武汉俊杰电子有限公司</td></tr><tr><td>组织切片机</td><td>SP1600</td><td>德国徕卡仪器有限公司</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 34,
+        "chunk": "# 2.2.2 磺化 CFRPEEK 复合材料的制备  \n\n长碳纤维PEEK 纤维的重量比为30:70 的CFRPEEK 复合材料的模量与皮质骨的模量最接近。选择这一比例按照本研究团队之前报道的方法[237]制备CFRPEEK 复合材料。（Figure 2.2）  \n\n（1）将PEEK 长纤维（ $70\\mathrm{wt\\%}$ ，长 $40\\mathrm{mm}$ ）和碳纤维长纤维（ $30\\mathrm{wt\\%}$ ，长$40\\mathrm{mm}$ ）通过混合、梳理、铺设和针刺制备 3D CFRPEEK 复合针刺毡；（2）将针刺毡修整成专用模具的尺寸，放入真空热压机中进行热压成型。热压的工艺参数设定如下：成型温度为 $400^{\\circ}\\mathrm{C}$ ，成型时间为 $20\\mathrm{min}$ ，冷却速度为$20^{\\circ}\\mathrm{C/min}$ ，成型压力为 $4\\mathrm{MPa}$ ；（3）通过脱模得到黑色的板状 CFRPEEK 复合材料；（4）为了去除 CFRPEEK 复合材料表面污染物，体外和体内探究中使用的CFRPEEK 样品依次在超声波清洗器中用丙酮，乙醇和超纯水清洗，各 $10~\\mathrm{min}$ ；（5）在室温下，CFRPEEK 样品在浓硫酸中磁力搅拌 $5\\mathrm{min}$ ，以获得均匀的多孔表面；（6）反应后的 CFRPEEK 样品依次浸入超纯水和丙酮中，并在超声波清洗器中清洗；（7）将得到的磺化 CFRPEEK 复合材料在真空干燥箱中 $60^{\\circ}\\mathrm{C}$ 干燥 24 小时以备后续使用；（8）尺寸为 $\\Phi14\\times1.5\\mathrm{mm}$ 的磺化CFRPEEK 用于表面表征和体外细胞实验，尺寸为 $\\Phi5{\\times}1.5\\ \\mathrm{mm}$ 的磺化 CFRPEEK 用于动物体内实验。  \n\n![](images/b193835ec0868fc1669aa581e370558102acec99fc291d18a6a844826f76d73d.jpg)  \nFigure 2.2 Schematic diagram of preparation process of 3D needle-punched CFRPEEK composite[237].",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 35,
+        "chunk": "# 2.2.3 甲基丙烯酰化明胶（GelMA）的制备与表征  \n\n甲基丙烯酰化明胶（GelMA）按照文献报道的方法制备（Figure 2.3） [259]。  \n\n在 $60^{\\circ}\\mathrm{C}$ ，5 克明胶于50 毫升磷酸盐缓冲溶液（PBS，CELLCOOK，中国）中溶解；向明胶溶液中缓慢滴入 4 毫升甲基丙烯酸酐， $50^{\\circ}\\mathrm{C}$ 磁力搅拌 3 小时进行酰化反应；在 $50^{\\circ}\\mathrm{C}$ 下，将反应完的溶液用 200 毫升的PBS 稀释，装入透析袋中用去离子水透析3 天，以除去未反应的甲基丙烯酸酐；将透析后的反应液在真空冷冻干燥机中冻干，获得白色泡沫状的甲基丙烯酰化明胶（GelMA）。  \n\n![](images/45d7b557cafe0c7299419c1aee18ca9d21bfb8def68b3ba686db3fbe35645ed2.jpg)  \nFigure 2.3 The fabrication synthesis of GelMA.  \n\n在常温条件下，将少量的明胶和甲基丙烯酸酰化明胶分别溶解于氘代重水（ $\\mathrm{\\cdot}\\mathrm{D}_{2}\\mathrm{O}),$ ），通过 $400\\mathrm{MHz}$ 核磁共振波谱仪来测试样品的 $\\mathrm{^{1}H N M R}$ 光谱，以确定所制备的甲基丙烯酸酰化明胶（GelMA）的分子结构。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 36,
+        "chunk": "# 2.2.4 负载 Dex 的复合水凝胶修饰 CFRPEEK 的制备  \n\n负载Dex 的复合水凝胶修饰 CFRPEEK 的制备按照如下步骤操作：  \n\n在避光条件下，将 GelMA 和 AM 按照 $10{:}5\\mathrm{\\wt\\%}$ 的比例溶解到去离子水中，得到无色透明的 GelMA/AM 凝胶前体液；将按照 2.2.2 制备的磺化 CFRPEEK 浸入到 GelMA/AM 凝胶前体液中；将含有磺化 CFRPEEK 的混合溶液置于波长为$365~\\mathrm{nm}$ 、光强度为 $10\\mathrm{\\mW/cm}^{2}$ 的紫外灯下 45 分钟；为了去除未反应的 GelMA和AM，将接枝后的样品浸入到去离子水中；将紫外接枝后的样品在浓度为 250$\\upmu\\mathrm{g/mL}$ 的Dex 溶液中孵育24 小时；最后，在真空冷冻干燥机中冻干孵育后的样品。  \n\n各组CFRPEEK 样品用如下缩写表示：  \n\nCP:未经处理的 CFRPEEK 复合材料; SCP: 磺化 CFRPEEK 复合材料;  \nSCP/GP: GelMA/PAAM 复合水凝胶接枝的磺化 CFRPEEK 复合材料;  \n\nSCP/GP/Dex: 负载 Dex 的 GelMA/PAAM 复合水凝胶接枝的磺化 CFRPEEK复合材料。  \n\n采用场发射扫描电子显微镜（SEM）对各组样品的表面形貌和截面形貌进行表征；X 射线光电子能谱仪（XPS）和全反射傅里叶红外光谱仪（ATR-FTIR）用于表征各组样品的表面化学组成；使用接触角测量仪测量每组试样的水接触角，每个试样测量3 个不同的区域，每组试样重复测量 2 次。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 37,
+        "chunk": "# 2.2.5 力学性能测试  \n\n使用AGX电子万能材料试验机测定CFRPEEK在表面改性前后的机械性能，所有机械性能测试均在 $23^{\\circ}\\mathrm{C}$ 和 $50\\%$ 相对湿度下进行。  \n\n拉伸性能参照 ASTM-D3039 进行测量，将各组样品切割成 $150\\ \\mathrm{mm}\\times\\ 12.5$ $\\mathrm{mm}{\\times}1.5\\mathrm{mm}$ 的样条，拉伸测试速率为 $1\\mathrm{mm/min}$ 。弯曲性能根据 ASTM-D7264 使用三点弯曲法测量，各组样条的尺寸为 $120\\mathrm{mm}{\\times}12.5\\mathrm{mm}{\\times}3\\mathrm{mm}$ ，弯曲测试的加载速度为 $1\\mathrm{mm/min}$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 38,
+        "chunk": "# 2.2.6 Dex 释放行为研究  \n\n（1）在进行Dex 释放实验之前，首先测量复合水凝胶修饰 CFRPEEK 的Dex负载率。将复合水凝胶修饰CFRPEEK 置于 $4\\mathrm{mL}$ 浓度为 $250~\\upmu\\mathrm{g/mL}$ 的 Dex 溶液中，随后将其放在 $25^{\\circ}\\mathrm{C}.$ 恒温摇床上，以 $50~\\mathrm{rpm}$ 的速度匀速振荡；孵育 $24\\mathrm{~h~}$ 后，取出载药的复合水凝胶修饰CFRPEEK；使用紫外-可见分光光度计测量剩余Dex溶液在 $240~\\mathrm{nm}$ 处的吸光度。复合水凝胶修饰 CFRPEEK 的Dex 负载率的计算公式如下：  \n\nDex 负载率（%）= （M0-MT） $\\mathrm{'}\\mathbf{M}_{0}\\times100\\%$ ·  \n\n其中 MT 为剩余 Dex 溶液的药物质量， $\\mathbf{M}_{0}$ 为总的药物质量。最后，计算出的复合水凝胶修饰 CFRPEEK 的 Dex 负载率为 $28.77\\%$ 。  \n\n（2）对于体外 Dex 释放实验，将 SCP/GP/Dex 样品浸入到装有 2 mL PBS 的离心管中，置于 $37^{\\circ}\\mathrm{C}$ 的恒温摇床以 $100\\mathrm{rpm}$ 的速度振荡；在预定时间收集含有释放 Dex 的 PBS，并加入等体积的新鲜 PBS；通过紫外-可见分光光度计测量释放的Dex 浓度。按照如下公式计算 Dex 的释放效率：  \n\nDex 的释放效率 $(\\%)\\ =\\mathrm{Rt}/\\mathrm{R}_{0}{\\times}100\\%$  \n\n其中 $\\mathbb{R}_{\\mathrm{t}}$ 为释放的 Dex 的质量， ${\\bf R}_{0}$ 为复合水凝胶修饰 CFRPEEK 负载的 Dex的总质量。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 39,
+        "chunk": "# 2.2.7 体外矿化行为研究  \n\n将 CP、SCP、SCP/GP 和 SCP/GP/Dex 浸入到 $2\\mathrm{mL}$ 的 SBF 溶液中，置于 $37^{\\circ}\\mathrm{C}$ 恒温摇床中，以 $100\\mathrm{rpm}$ 的速度匀速振荡；每两天更换等量新鲜的 SBF 溶液，在14 天后，将试样取出，在真空冷冻干燥机中冷冻干燥；利用 SEM 及能量色散光谱仪（EDS）测量试样的微观形貌和化学构成。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 40,
+        "chunk": "# 2.2.8 细胞实验",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 41,
+        "chunk": "# 2.2.8.1 骨髓间充质干细胞（BMSC）的提取、培养与传代  \n\n细胞实验采用的细胞是从 Sprague Dawley（SD）大鼠提取出的 BMSC 细胞。SD 大鼠购自北京维通利华实验动物技术有限公司，性别为雄性，体重为 $100\\mathrm{g}$ 左右。提取的步骤如下：  \n\n（1）采用深度麻醉状态下颈椎脱臼法处死大鼠，在 $75\\%$ 乙醇中浸泡 $10\\mathrm{min}$ 消毒；（2）将大鼠转移至超净台中，取出大鼠的两根胫骨及两根股骨，用手术器械去除长骨上附着的肌肉组织；（3）用剪刀剪去长骨两端，将骨髓腔内的细胞用含有 $1\\%$ 青霉素-链霉素和$10\\%$ FBS 的DMEM 完全培养基冲洗到培养皿内；（4）在 $37^{\\circ}\\mathrm{C}$ 和 $5\\%$ $\\mathrm{CO}_{2}$ 的细胞培养箱中培养提取的细胞，首次更换培养基在72 小时后，此后2 天更换一次；（5）当培养皿中的贴壁 BMSC 细胞达 $90\\%$ 融合时，吸出全部完全培养基，再用PBS 洗涤；（6）将 $0.25\\%$ 胰蛋白酶加入到培养皿中，消化 1\\~2 分钟，用倒置显微镜观察细胞，当细胞开始变圆时，加入完全培养基，终止胰蛋白酶消化；（7）用吸管反复吹吸消化后的细胞，收集细胞于 $15\\mathrm{mL}$ 离心管中，用离心机以 $1000\\mathrm{rpm}$ 离心 $5\\mathrm{min}$ ，弃上清液。  \n\n（8）在完全培养基中重悬细胞，以 $2{\\sim}5{\\times}10^{5}\\mathrm{cell/ml}$ 的密度传代到新的培养皿中，此时得到的是第一代 BMSC 细胞，本细胞实验中采用的是第三代 BMSC细胞。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 42,
+        "chunk": "# 2.2.8.2 细胞相容性测试  \n\n1. CCK-8 试剂盒用于检测材料表面BMSC 细胞的增殖情况。操作步骤如下：（1）将处在对数生长期的第三代 BMSC 细胞制成密度为 $1{\\times}10^{4}~\\mathrm{cell/mL}$ 细胞悬液;（2）将经过 Cobalt 60 灭菌（15KGy， $20\\mathrm{h}$ ）的样品放入 24 孔培养板中，用PBS 清洗一遍后，每孔滴加 $1\\mathrm{mL}$ 细胞悬液;（3）将培养板置于培养箱中，每 2-3 天更换培养基;（4）细胞培养1、4 和7 天后，向培养板中加入 $100\\upmu\\mathrm{L}$ 含有 $10\\%$ CCK-8 溶液的新培养基；（5）在培养箱中孵育 $2\\mathrm{h}$ 后，从每孔吸出 $100\\upmu\\mathrm{L}$ 培养基，放入 96 孔板中，使用酶标仪测量各孔的吸光度。2. 通过扫描电镜（SEM）观察 BMSC 细胞在材料表面的生长情况，具体操作步骤如下：（1）（2）（3）和上述CCK-8 的实验步骤相同；（4）细胞培养1 和4 天后，吸去培养基，用PBS 轻轻冲洗样品，再用电镜固定液固定 $2\\mathrm{h}$ ；（5）吸出固定液，样品在生物组织快速脱水仪中脱水，再在临界点干燥仪内干燥；（6）将样品固定在样品台上，放入离子溅射仪中喷金，随后用 SEM 进行观察。3. BMSC 细胞在不同样品上的粘附与扩散用罗丹明标记的鬼笔环肽和 DAPI染色法进行检测。方法如下：（1）（2）（3）和上述CCK-8 的实验步骤相同；（4）7 天后，吸出培养基，用PBS 轻轻冲洗样品，用 $4\\%$ 多聚甲醛溶液固定样品表面的细胞 $30\\mathrm{min}$ ；  \n\n（5）吸除 $4\\%$ 多聚甲醛溶液，再用 PBS 清洗样品，向孔板中加入 $0.5\\%$ 的TritonX-100 通透 $15\\mathrm{min}$ ，吸除 TritonX-100 后用 PBS 清洗样品表面；  \n\n（6）将 $100~\\mathrm{{nM}}$ 的 $200~\\upmu\\mathrm{L}$ 罗丹明标记的鬼笔环肽溶液加入到孔板中，以染色细胞膜上的F-肌动蛋白， $37^{\\circ}\\mathrm{C}$ 孵育 $^{\\textrm{1h}}$ ，再用PBS 清洗样品表面；  \n\n（7）将 $200\\upmu\\mathrm{L}5\\upmu\\mathrm{g/mL}$ 的 DAPI 溶液加入到孔板中，以对细胞核进行复染，$5\\mathrm{min}$ 后吸去染色液，并用PBS 清洗;  \n\n（8）用激光共聚焦显微镜观察细胞在样品上的粘附扩散情况，并拍照留存。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 43,
+        "chunk": "# 2.2.8.3 体外成骨性能测试  \n\n1. 通过碱性磷酸酶（ALP）活性定量和染色实验检测BMSC 细胞在不同样品表面的早期成骨分化情况，具体操作步骤如下：  \n\n（1）将处在对数生长期的第三代 BMSC 细胞制成密度为 $3{\\times}10^{4}$ cell/mL 细  \n胞悬液；（2）将经过Cobalt 60 灭菌的样品放入24 孔培养板中，用PBS 清洗一遍后，  \n每孔滴加1 mL 细胞悬液；（3）培养板放入培养箱 $24\\mathrm{h}$ 后，完全培养基更换为成骨诱导培养基，其中  \n成骨诱导培养基：向完全培养基中添加 $50\\upmu\\mathrm{M}$ 维生素C， $10\\mathrm{mM}\\upbeta$ -甘油磷酸钠和  \n$100~\\mathrm{{nM}}$ 地塞米松；（4）培养 7 天和 14 天后，收集成骨诱导培养基，用 PBS 清洗孔板中各组  \n样品， $4\\%$ 多聚甲醛固定30 分钟，再用 PBS 清洗；（5）根据BCIP / NBT 染色试剂盒说明配制工作液，在每孔中加入 1mL 工  \n作液，并置于 $37^{\\circ}\\mathrm{C}$ 水浴箱放置 45 分钟；（6）弃去染色工作液，用 PBS 冲洗，晾干，拍照；（7）按照 ALP 试剂盒说明书检测收集的成骨诱导培养基中 ALP 的活性，  \n用酶标仪检测 $520\\mathrm{nm}$ 处的 OD 值。2. 通过茜素红（ARS）染色和定量分析检测 BMSC 细胞在不同样品表面的  \n晚期成骨分化情况，具体操作步骤如下：（1）（2）（3）和上述碱性磷酸酶（ALP）活性定量和染色实验步骤相同；（4）各组样品与 BMSC 细胞共培养 21 天后，吸除成骨诱导培养基，每组  \n\n样品用 PBS 洗涤， $4\\%$ 多聚甲醛固定 $30\\mathrm{min}$ ，然后用PBS 洗涤；  \n\n（5）每孔加 $0.1\\%$ 茜素红溶液 $1\\mathrm{mL}$ ， $37^{\\circ}\\mathrm{C}$ 水浴 $45\\mathrm{min}$ ；  \n\n（6）用PBS 洗涤，去除多余的染液，晾干，拍照；  \n\n（7）拍照后的样品浸没在 $1\\mathrm{mL}10\\%$ （w/v）氯化十六烷基吡啶溶液中，在$37^{\\circ}\\mathrm{C}$ 下溶解样品上的染色，3 小时后用酶标仪检测 $550\\mathrm{nm}$ 处的 OD 值。  \n\n3. 通过实时荧光定量分析聚合酶链式反应（RT-PCR）来探究BMSC 细胞在不同样品表面的成骨相关基因的表达情况，具体操作步骤如下：  \n\n（1）（2）（3）和上述碱性磷酸酶（ALP）活性定量和染色实验步骤相同；（4）总 RNA 提取  \n\n培养7 天和14 天后，吸出成骨诱导培养基，每组样品用 PBS 清洗，加入 1mL Trizol 试剂，用枪头吹破细胞，移至离心管中；将离心管置于高速离心机，以 $12000~\\mathrm{rpm}$ 速度离心 $10~\\mathrm{min}$ ，收集上清液，加入 $250~\\upmu\\mathrm{L}$ 氯仿，混匀，静置 3min，再次离心 $10\\mathrm{min}$ ，将 $400{\\upmu\\mathrm{L}}$ 上清液转移到新的EP 管中；向上清液中加入等体积异丙醇，混匀， $-20^{\\circ}\\mathrm{C}$ 静置 $15\\mathrm{min}$ ， $12000\\mathrm{rpm}$ 离心 $10\\mathrm{{min}}$ ，管底白色沉淀为RNA；弃去上层液体，加入 $75\\%$ 乙醇洗涤沉淀， $12000\\mathrm{rpm}$ 离心 $5\\mathrm{min}$ ，重复2 次；将离心管置于超净台上吹 $3\\mathrm{min}$ ，加入 $15\\upmu\\mathrm{LRNA}$ 溶解液溶解 RNA， $55^{\\circ}\\mathrm{C}$ 孵育 $5\\mathrm{min}$ ；提取的 RNA 浓度和纯度使用 Nanodrop 2000 检测。  \n\n（5）反转录 cDNA  \n\n将 Table 2.3 逆转录反应体系均匀混合，放入 PCR 仪，设定程序： $37^{\\circ}\\mathrm{C}$ 15min， $85^{\\circ}\\mathrm{C}\\ 5\\ \\mathrm{sec}$ ， $4^{\\circ}\\mathrm{C}$ 保存。  \n\nTable 2.3 Reverse transcription reaction system.   \n（6）RT-PCR   \n\n\n<html><body><table><tr><td>反应试剂</td><td>体积（μL)</td></tr><tr><td>5× PrimeScript RT Master Mix （Perfect Real Time）</td><td>２</td></tr><tr><td>100 ngTotalRNA对应的体积</td><td>X</td></tr><tr><td>RNase Free dH2O</td><td>8-X</td></tr></table></body></html>  \n\n按 Table 2.4 配制 PCR 反应液，并加入到 Roche 480 孔板内；  \n\nTable 2.4 The PCR reaction system.   \n\n\n<html><body><table><tr><td>反应试剂</td><td>体积(μL)</td></tr><tr><td>TB Green Premix Ex Taq II</td><td>10</td></tr><tr><td>上游引物</td><td>0.8</td></tr><tr><td>下游引物</td><td>0.8</td></tr><tr><td>ROX Reference Dye or Dye II</td><td>0.4</td></tr><tr><td>cDNA 溶液</td><td>２</td></tr><tr><td>RNase Free dH2O</td><td>６</td></tr></table></body></html>\n\n将孔板置于 RT-PCR 仪内，程序设置： $95^{\\circ}\\mathrm{C}$ 预变性 30 sec，PCR 反应 $95^{\\circ}\\mathrm{C}$ 下 3 sec，然后 $60^{\\circ}\\mathrm{C}$ 下 $30\\mathrm{sec}$ ，共经历 40 个循环；  \n\n通过 $2^{\\wedge}{\\lrcorner}\\Delta\\Delta\\mathrm{Ct}$ 法计算目的基因的表达量。  \n\n（7）RT-PCR 所需的成骨相关基因的引物对，如表 Table 2.5  \n\nTable 2.5 Primer pairs used in real-time PCR analysis.   \n\n\n<html><body><table><tr><td>Genes</td><td>Sequence (5'-3')</td></tr><tr><td>ALP</td><td>F: ATCGGAACAACCTGACTGACC</td></tr><tr><td rowspan=\"2\">Col-I</td><td>R: CTGCCTCCTTCCACTAGCAA F: ATGCCATCAAGGTCTACTGCAA</td></tr><tr><td>R: GAACCTTCGCTTCCATACTCG</td></tr><tr><td rowspan=\"2\">GAPDH</td><td>F: TATGACTCTACCCACGGCAAG</td></tr><tr><td>R: ATACTCAGCACCAGCATCACC</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 44,
+        "chunk": "# 2.2.9 大鼠颅骨缺损实验",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 45,
+        "chunk": "# 2.2.9.1 建立大鼠颅骨缺损模型  \n\n动物实验采用大鼠颅骨缺损实验模型来探究负载 Dex 的复合水凝胶修饰CFRPEEK 植入物的体内成骨能力。动物实验的所有程序均经吉林大学实验动物福利与伦理委员会批准（批准号：2021129），并按照相关机构指南和法律进行。将24 只购买自北京维通利华的雄性 SD 大鼠（8 周，体重 $200{\\pm}25\\mathrm{g}$ ）随机分为四组：CP，SCP，SCP/GP 和SCP/GP/Dex。所有动物均用异氟烷麻醉，颅骨用碘伏消毒，在颅骨中央做 $3\\ \\mathrm{cm}$ 纵切口，钝性剥离皮下组织，露出颅骨骨板。使用外径为 $5\\mathrm{mm}$ 去骨钻在颅骨中缝两侧造出 2 个全层圆形骨膜骨质缺损。将植入物随机植入缺损部位（Figure 2.4）。大鼠在 4 周和 12 周被安乐死，然后收集含有样品的头骨和内脏（心、肝、脾、肺和肾），并固定在 $4\\%$ 多聚甲醛中以进行后续分析。  \n\n![](images/ba40deabe3ba415ab34ce4dbb86d8897c10006e1bfcb82e45287fb95ab96cb21.jpg)  \nFigure 2.4 Construction of the rat cranial defect model.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 46,
+        "chunk": "# 2.2.9.2 显微计算机断层扫描 （micro-CT）  \n\n通过 micro-CT 扫描固定后的头骨，扫描图像经过 NRecon 软件和 CTvox 软件处理，以重建颅骨缺损的2D 和3D 图像。利用 CTAn 软件计算新骨的骨参数：骨体积/总体积（BV/TV）、骨小梁数目（Tb.N）和骨小梁厚度（Tb.Th）。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 47,
+        "chunk": "# 2.2.9.3 组织学研究",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 48,
+        "chunk": "# 1. 颅骨硬组织切片及染色  \n\n将颅骨组织先经过乙醇梯度脱水，再用二甲苯脱水 $12\\mathrm{h}$ ；将脱水后的组织放入浸塑液中，在 $4^{\\circ}\\mathrm{C}$ 浸塑 $24\\mathrm{~h~}$ ，重复 3 次；将浸塑后的颅骨组织放入包埋瓶中，加入适量的包埋液进行包埋；通过硬组织切片机常规切片，厚度约 $10\\upmu\\mathrm{m}$ ，将切片置于 $60^{\\circ}\\mathrm{C}$ 烘箱中烘干；切片用 Van Gieson 染色，Masson 三染色和 H & E 染色法进行染色；通过显微镜镜检，采集图像并分析颅骨缺损的修复情况。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 49,
+        "chunk": "# 2. 内脏石蜡切片及染色  \n\n新鲜内脏用固定液固定 $24\\mathrm{~h~}$ 以上，将内脏从固定液取出放于脱水盒内；将脱水盒放进脱水机内使用乙醇对内脏梯度脱水，乙醇的浓度次序为 $75\\%85\\%$ -  \n\n$90\\%{-}95\\%{-}100\\%$ ，然后将脱水的内脏浸没在融化的石蜡中；浸蜡后，将内脏组织在包埋机内包埋；包埋好的内脏组织用石蜡切片机切片，厚度为 $4~{\\upmu\\mathrm{m}}$ ；采用 H& E 染色法对切片染色；最后，通过倒置显微镜获取染色切片的图像。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 50,
+        "chunk": "# 2.2.10 统计与分析  \n\n使用 SPSS v10.0 对数据进行统计分析。数据以 $\\mathrm{SD\\pm}$ 平均值表示，使用单因素方差分析比较测量值。 $^{*}p<0.05$ 表示具有统计学意义。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 51,
+        "chunk": "# 2.3 结果与讨论",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 52,
+        "chunk": "# 2.3.1 甲基丙烯酰化明胶（GelMA）的制备  \n\n明胶和甲基丙烯酰化明胶的 $\\mathrm{^{1}H N M R}$ 谱如 Figure 2.5 所示。在 GelMA 的 $^1\\mathrm{H}$ NMR 谱中可以观察到在 $5.4\\mathrm{ppm}$ 和 $5.6\\mathrm{ppm}$ 处有清晰可见的峰(Figure 2.5a)，这是 $\\mathrm{CH}_{2}{=}\\mathrm{CH}\\left(\\mathrm{CH}_{3}\\right)$ 的质子峰。 $1.87\\mathrm{ppm}(\\mathrm{Figure}2.5\\mathbf{b})$ 的峰值对应的是甲基丙烯基中的甲基，这说明甲基丙烯基已被接枝到明胶的分子链上。  \n\n![](images/b35c9345cf9e8657c68fd998ab4b61e59226eedd8c71e13941fc3a38d2fdb9cf.jpg)  \nFigure 2.5 $\\mathrm{^{1}H}$ NMR spectra of gelatin and GelMA.  \n\n2.3.2 负载 Dex 的复合水凝胶修饰 CFRPEEK 的制备  \n\nFigure 2.6 是经过磺化处理和紫外接枝的不同 CFRPEEK 样品的实物图和SEM 图像。CP 具有黑色平滑的表面。磺化处理后，SCP 变为白色粗糙的表面。  \n\n紫外接枝后，SCP/GP 和 SCP/GP/Dex 表面被白色的水凝胶覆盖。与表面相对平坦的CP 不同，在 SCP 表面上观察到粗糙的多孔结构和许多暴露的碳纤维。在紫外接枝后，SCP/GP 和 SCP/GP/Dex 表面形成了三维复合水凝胶网络。  \n\n![](images/0000fc37fa11cf299546ee81218ec2f7573c7d2a648acd58a02ad4856e7022ae.jpg)  \nFigure 2.6 SEM images of: CP, SCP, SCP/GP and SCP/GP/Dex, at high and low magnifications and the macroscopic views of each sample.  \n\nCP、SCP 和 SCP/GP 样品经过切片后的横截面如 Figure 2.7 所示。在 SCP 样品的横截面图像中可以观察到浓硫酸的扩散途径。在 SCP/GP 样品上可以观察到3D 多孔GelMA/PAAM 复合水凝胶网络，水凝胶层的厚度约为 $50\\upmu\\mathrm{m}$ 。由于复合水凝胶的接枝，SCP 顶层的孔被水凝胶网络填充。  \n\n![](images/4325afe64cd7f8e0a69221767b2659f1d1f66d766347a6f0e4d189e84b9ae5fd.jpg)  \nFigure 2.7 SEM images of different sample cross-sections: (a) CP, (b) SCP, and (c)  \n\nFigure 2.8 是不同 CFRPEEK 样品的 ATR-FTIR 光谱图。在 CP 和 SCP 光谱中，二苯甲酮的吸收峰出现在 $1593\\mathrm{cm}^{-1}$ 、 $1486\\mathrm{cm}^{-1}$ 和 $925\\mathrm{cm}^{-1}$ 处，在 $1184\\mathrm{cm}^{-1}$ 和 $1156~\\mathrm{cm}^{-1}$ 处的峰值则对应的是 C-O-C，在 $1600~\\mathrm{{cm}^{-1}}$ 处检测到苯的 $\\scriptstyle{\\mathrm{C=C}}^{[240}$ ,260]。在 SCP/GP 和 SCP/GP/Dex 中， $1237~\\mathrm{cm}^{-1}$ 和 $1538~\\mathrm{cm}^{-1}$ 的峰值与 GelMA 结构中的酰胺Ⅰ和Ⅱ和Ⅲ键的N-H 的伸缩振动有关， $1646\\mathrm{cm}^{-1}$ 的峰值与 GelMA 结构中的酰胺Ⅲ键的 $\\scriptstyle{\\mathrm{C=O}}$ 的伸缩振动有关， $2930~\\mathrm{cm}^{-1}$ 处的峰值对应的是 C-H，在 $3294~\\mathrm{{cm}^{-1}}$ 观察到 N-H，这表明 SCP/GP 和 SCP/GP/Dex 表面有大量氢键[261,262]。ATR-FTIR 结果表明，GelMA/PAAM 已经成功接枝到磺化 CFRPEEK 表面。  \n\n![](images/0eb9797c64c8d2ebe04c6fd3a5b902ae8dc06ed60ae6956a59ec9215e81530e7.jpg)  \nFigure 2.8 ATR-FTIR spectra of CP, SCP, SCP/GP and SCP/GP/Dex.  \n\nFigure 2.9 和 Table 2.6 是 CP、SCP、SCP/GP 和 SCP/GP/Dex 样品的 XPS检测结果。如 Figure 2.9a 所示，在不同样品的 XPS 谱图中观察到 C 1s（284.6eV）、N 1s（ $400.0\\ \\mathrm{eV}.$ ）、O 1s（ $533.0\\ \\mathrm{eV}$ ）、S 2p（ $167.1\\ \\mathrm{eV}$ ）和 F 1s（ $686.7\\ \\mathrm{eV})$ ）峰。除碳元素和氧元素外，在 SCP 表面还观察到硫元素，这是 CFRPEEK 经过浓硫酸磺化处理造成的。与 CP 和 SCP 相比，在 SCP/GP 和 SCP/GP/Dex 表面均检测到氮元素，这表明 GelMA/PAAM 复合水凝胶已成功接枝到 CFRPEEK 上。Figure 2.9b 和 Table 2.6 分别为 SCP/GP/Dex 的高分辨率氟峰（F 1s）光谱和不同样品的元素含量。结果表明，SCP/GP/Dex 中的碳和氧元素的含量相较于 SCP/GP增加，氮元素的含量减少，还检测到了 $1.43\\%$ 的氟元素，表明 Dex 已成功负载到CFRPEEK 上。XPS 分析结果表明成功制备了负载 Dex 的复合水凝胶修饰CFRPEEK。  \n\n![](images/66f069197f9540e5f6f5c41b09edae90c34668482cb1dc7c027974e68a060e13.jpg)  \nFigure 2.9 (a) XPS spectra of CP, SCP, SCP/GP, SCP/GP/Dex and (b) high-resolution fluorine peak (F 1s) spectra of SCP/GP/Dex.  \n\nTable 2.6 Elemental composition of different substrate surfaces as determined by XPS.   \n\n\n<html><body><table><tr><td>Sample</td><td>C (%)</td><td>0 (%)</td><td>N (%)</td><td>S (%)</td><td>F (%)</td></tr><tr><td>CP</td><td>63.84</td><td>36.16</td><td></td><td></td><td></td></tr><tr><td>SCP</td><td>63.72</td><td>35.00</td><td></td><td>1.28</td><td></td></tr><tr><td>SCP/GP</td><td>43.25</td><td>37.71</td><td>19.04</td><td></td><td></td></tr><tr><td>SCP/GP/Dex</td><td>49.96</td><td>33.27</td><td>15.34</td><td></td><td>1.43</td></tr></table></body></html>  \n\n材料表面的水接触角是验证表面改性成功与否的重要证据。改性前后样品表面的水接触角如Figure 2.10 所示。CP 的水接触角为 $65.2{\\pm}0.69^{\\circ}$ 。经磺化处理后，SCP 的水接触角增加到 $93.1{\\pm}2.09^{\\circ}$ 。SCP 表现为疏水性，这是 SCP 表面的粗糙多孔结构造成的。以前的研究表明，增加表面粗糙度会增加材料表面积，从而增加材料表面对液体的亲和力。所以，材料表面粗糙度增加会使亲水表面更加亲水，使疏水表面更加疏水[263, 264]。未经过任何处理的 CFRPEEK（CP）具有较大的水接触角，并且具有疏水性和生物惰性。同时，浓硫酸处理后 CFRPEEK 表面粗糙度显著增加，这导致了 SCP 的水接触角增大。经过紫外接枝处理后，SCP/GP 和SCP/GP/Dex 的水接触角显著降低，分别为 $53.7{\\pm}1.84^{\\circ}$ 和 $48.8{\\pm}0.45^{\\circ}$ ，这表明接枝在CFRPEEK 表面的复合水凝胶具有显著的亲水性。  \n\n![](images/38dc75dfbd9a360ffaa9456280b1f6916fcc00120eb0b99b4bd1c245079adf70.jpg)  \nFigure 2.10 Water contact angles of CP, SCP, SCP/GP and SCP/GP/Dex ( $^{*}p<0.05)$ .  \n\n紫外辐照接枝的原理如Figure 2.11 所示，PEEK 由交替的芳醚和二苯甲酮组成。在紫外线(UV)照射下，二苯甲酮单元可以产生自由基，并引发 GelMA 和AM的烯基双键的聚合反应，从而与 PEEK 形成 C-C 共价键生成接枝共聚物，表现为在 CFRPEEK 表面形成 GelMA/PAAM 复合水凝胶层。GelMA/PAAM 水凝胶层进一步作为药物载体，通过氢键吸附骨诱导药物地塞米松（Dex）。  \n\n![](images/9767efb1c564934f364a86ae769f2a5ad734481636e8e7212732517b571f5f7b.jpg)  \nFigure 2.11 Schematic illustration of the free radical polymerization on the surface of CFRPEEK.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 53,
+        "chunk": "# 2.3.3 机械性能  \n\nTable 2.7 为经过磺化处理和紫外接枝的不同样品的机械性能。与 CP 相比，SCP 的拉伸和弯曲性能略有降低，这是因为 CFRPEEK 表面磺化处理形成的多孔结构削弱了基底的机械性能[265]。SCP/GP 的力学性能与 SCP 的力学性能没有显著性差异，这表明复合水凝胶对 SCP 力学性能的影响有限。综上所述，复合水凝胶改性的CFRPEEK 仍具有优异的力学性能。  \n\nTable 2.7 Mechanical properties of different samples.   \n\n\n<html><body><table><tr><td>Sample</td><td>Tensile Strength (MPa)</td><td>Tensile Modulus (GPa)</td><td>Flexural Strength (MPa)</td><td>Flexural Modulus (GPa)</td></tr><tr><td>CP</td><td>323.36 ± 22.79</td><td>34.83 ± 0.73</td><td>416.06 ± 13.92</td><td>21.15 ± 1.00</td></tr><tr><td>SCP</td><td>303.47 ± 12.24</td><td>29.77 ± 1.75</td><td>380.80 ± 14.74</td><td>18.91 ± 1.80</td></tr><tr><td>SCP/GP</td><td>317.72 ± 9.41</td><td>31.19 ± 1.39</td><td>385.38 ± 17.65</td><td>19.30 ± 0.66</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 54,
+        "chunk": "# 2.3.4 药物（Dex）缓释行为  \n\n为了进一步增强 CFRPEK 复合材料的成骨分化能力，将成骨诱导药物地塞米松（Dex）负载到 GelMA/PAAM 复合水凝胶上。Figure 2.12 是 SCP/GP/Dex 在  \n\n21 天内的 Dex 释放效率图。结果表明，SCP/GP/Dex 在 21 天内释放的 Dex 效率为 $53\\%$ ，这说明GelMA/PAAM 复合水凝胶修饰 CFRPEEK 具有长期持续的药物释放特性，这归因于复合水凝胶中的 GelMA 含有丰富的极性基团，如-COOH 和$\\mathrm{-NH}_{2}$ ，可以与 Dex 形成氢键，这能够有效的固定大量的药物并控制药物释放。同时，CFRPEEK 表面上的 GelMA/PAAM 复合水凝胶的 3D 网络结构进一步阻碍了药物的快速扩散[259]。  \n\n![](images/6783de84485f121088aa69bc9661dcb1d5d0a522ae3ab818b6504ac466a1bcd0.jpg)  \nFigure 2.12 Dex release profile of SCP/GP/Dex over 21 d.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 55,
+        "chunk": "# 2.3.5 体外矿化性能  \n\n材料表面形成骨状磷灰石表明该材料与骨组织之间具有良好的结合能力，这可以增强材料的骨传导性能[260]。Figure 2.13a 是不同样品在 SBF 中浸泡 14 天后表面形貌的 SEM。在 CP 和 SCP 表面上可以观察到圆形结节，在 SCP/GP 上则观察到明显的球形颗粒，SCP/GP/Dex 表面几乎完全被球形颗粒覆盖。先前的研究表明，由于GelMA 的羧基与钙离子之间可以形成化学键，GelMA 可以作为矿物沉积的成核剂或骨状磷灰石沉积的成核位点[266, 267]。因此，GelMA/PAAM 复合水凝胶层增强了 CFRPEEK 的骨状磷灰石的形成能力。Figure 2.13b 和 c 分别是SCP/GP 和 SCP/GP/Dex 的 EDS 谱图。经 EDS 证实，在 SCP/GP 和 SCP/GP/Dex上观察到沉积物含有Ca 和P 元素， $\\mathrm{Ca/P}$ 摩尔比为 2.21，高于 SCP/GP 的 2.07，这是由于 SCP/GP/Dex 中的地塞米松促进了体外生物矿化。这些结果表明，由GelMA/PAAM/Dex 复合凝胶层修饰的 CFRPEEK 具有出色的体外生物活性和体外骨结合能力。  \n\n![](images/e63c2df15580db39fd7005311c7fc53fe8af4db52f7ea3cda213beaddbb48806.jpg)  \nFigure 2.13 (a) SEM images of different specimens after soaking in SBF for $14{\\mathrm{d}}$ , and EDS spectra of (b) SCP/GP and (c) SCP/GP/Dex soaked in SBF for $\\boldsymbol{14\\mathrm{d}}$ .",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 56,
+        "chunk": "# 2.3.6 体外 BMSC 细胞相容性  \n\n细胞增殖能力反映了材料的 BMSC 细胞相容性。Figure 2.14 是细胞与改性前后的 CFRPEEK 样品共培养 1、4 和 7 天后的细胞增殖图。在 7 天时，SCP 的细胞增殖情况最差，这是由于 SCP 的疏水表面不利于细胞增殖。SCP/GP 和SCP/GP/Dex 的细胞增殖相对于 SCP 分别提高了 $42.11\\%$ 和 $39.82\\%$ ，这是因为GelMA 水凝胶的胶原样骨架能够促进细胞粘附、增殖和分化[268, 269]。SCP/GP/Dex的细胞增殖在 4 天和 7 天时略低于 SCP/GP，这是因为从 SCP/GP/Dex 释放的地塞米松诱导BMSC 细胞分化为成熟的成骨细胞，而成熟的成骨细胞不再增殖[270,271]。综上所述，复合水凝胶修饰 CFRPEEK 可以促进BMSC 细胞的增殖。  \n\n![](images/cf4e10af74381ddbb3c858f60af36af4e0a1518ff72da0a5d0d6946b190447e5.jpg)  \nFigure 2.14 Cell proliferation after culturing for 1, 4 and 7 days on different samples  \n\n$$\n(^{\\ast}p<0.05).\n$$  \n\n不同 CFRPEEK 与 BMSC 细胞共培养 1 天和 4 天后，通过 SEM 观察 BMSC细胞的形态。如Figure 2.15 所示，培养 1 天后，在CP 和SCP 上发现梭形细胞，这说明 CP 和 SCP 的细胞粘附性差。在 SCP/GP 和 SCP/GP/Dex 上观察到更大的细胞扩散区域，而且在这两个样品上都观察到更多的细胞丝状伪足，这表明GelMA/PAAM 复合水凝胶层促进了细胞扩散和粘附。培养 4 天后，细胞在所有样品上都进行了扩散，特别是在 SCP/GP 和SCP/GP/Dex 上，扩散的细胞几乎覆盖了整个表面。这些结果表明，复合水凝胶层增强了 CFRPEEK 表面的细胞相容性，为细胞生长和粘附提供了合适的环境。  \n\n![](images/00dd1d65282487c5c5d862bdfa6e75d2384bccc54271488af98cd2314d326d03.jpg)  \nFigure 2.15 SEM images demonstrated the morphologies of BMSCs adhered to different materials after incubation for 1 and 4 days. Scale bars ${=}50\\upmu\\mathrm{m}$ and $10\\upmu\\mathrm{m}$ .  \n\n为了进一步探索 BMSC 的细胞粘附和扩散行为，细胞骨架被罗丹明标记的鬼笔环肽染成红色，细胞核被 DAPI 染成蓝色。Figure 2.16 是培养 7 天后不同CFRPEEK 样品上的细胞形态。与 CP 和 SCP 相比，SCP/GP 和 SCP/GP/Dex 表面上的 BMSC 细胞具有许多板状伪足，这些伪足相互连接和重叠并产生了更成熟的F-肌动蛋白，这表明复合水凝胶修饰 CFRPEEK 有利于细胞粘附和扩散。综上所述，CFRPEEK 表面的复合水凝胶层具有优异的细胞相容性。  \n\n![](images/7dcd5c4d8c678f58fa231fb0c9599fec9a485cfee4657e5bed99f60412918760.jpg)  \nFigure 2.16 CLSM of BMSCs incubated for 7 days on different substrates. Scale bars",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 57,
+        "chunk": "# 2.3.7 体外 BMSC 成骨分化潜能  \n\nALP 活性、钙沉积和成骨相关基因表达可以用来衡量 GelMA/PAAM/Dex 修饰CFRPEEK 的成骨分化能力。ALP 是关键的早期成骨标志物，它参与了细胞成骨分化过程并影响细胞矿化[241, 272]。如 Figure 2.17a 所示，SCP 的 ALP 活性低于CP，这归因于 SCP 的疏水表面阻碍了细胞增殖，从而降低了 ALP 活性[273, 274]。培养 14 天后，SCP/GP/Dex 的 ALP 活性相对于 CP 和 SCP 分别提高了 $35.43\\%$ 和$28.29\\%$ ，与 ALP 染色结果一致（Figure 2.17b），SCP/GP/Dex 的 ALP 染色呈紫黑色，比其他三组要深。ALP 活性结果与细胞增殖和粘附测定的结果一致。综上所述，随着更多的 BMSC 细胞粘附在 SCP/GP 和 SCP/GP/Dex 上，ALP 活性增加，这是因为GelMA结构中的RGD序列是一种细胞识别位点，它能够促使BMSC细胞进入早期分化阶段，并通过改善细胞粘附和增殖来提高 ALP 活性[275]。  \n\n![](images/1b06458028ca6415f344297f9065965c6db43b1ae5463c5de05292c75ed96212.jpg)  \nFigure 2.17 (a) Alkaline phosphatase (ALP) activity of different samples after 7 and 14 days of osteogenic induction ( $^{*}p<0.05)$ . (b) ALP staining on different samples.  \n\n钙沉积是晚期成骨标志物，通过 BMSC 细胞在不同 CFRPEEK 样品上的钙沉积进一步探究了 GelMA/PAAM/Dex 复合水凝胶层的成骨能力。如 Figure 2.18所示，在 SCP/GP/Dex 表面检测到更多鲜红色的钙结节。定量检测结果也表明SCP/GP/Dex 上的细胞比其他三组细胞产生更多的钙结节，并且 SCP/GP/Dex 上产生的钙结节量相对于 SCP/GP 提高了 $53.56\\%$ ，这是由于从 GelMA/PAAM/Dex复合水凝胶层释放的 Dex 促进了成骨晚期分化[276]。综上所述，ALP 和 ARS 检测表明，GelMA/PAAM/Dex 修饰 CFRPEEK 具有优异的体外骨诱导能力。  \n\n![](images/abef037d6b2289747a2a8e76ef127b447888e18677b4329795316869a08630ef.jpg)  \nFigure 2.18 (a) Calcium deposition after culture of BMSCs on different CFRPEEK substrates for 21 d ( $^{*}p<0.05)$ . (b) Alizarin red staining (ARS) on different samples.  \n\n为了进一步了解 CFRPEEK 表面修饰的 GelMA/PAAM/Dex 复合水凝胶层对成骨的积极作用，在不同样品与 BMSC 共培养 14 天后，通过 RT-PCR 检测了BMSC 细胞成骨相关基因的表达情况，包括早期成骨分化标志物 ALP 和细胞外基质标志物 Col-Ⅰ。如 Figure 2.19 所示，BMSC 在 CP 和 SCP 上的两个成骨相关基因的表达水平没有显著差异，而 SCP/GP 和 SCP/GP/Dex 大大加速 BMSC 细胞向成骨细胞的分化。SCP/GP/Dex 的成骨相关基因表达水平最高，这表明GelMA/PAAM 复合水凝胶和 Dex 的协同作用对成骨有很好的促进作用。  \n\n![](images/11fe9820181d4c7416a00b2cbcda04113497f3d287cad1308f8cec292ae3ed36.jpg)  \nFigure 2.19 Quantification by RT-PCR of (a) ALP and (b) Col-Ⅰ expression by BMSCs cultured on different samples for $\\boldsymbol{14\\mathrm{d}}$ ( $^{*}p<0.05)$ .",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 58,
+        "chunk": "# 2.3.8 体内骨整合性能  \n\nCFRPEEK 复合材料具有高强度、低密度、近皮质骨模量和材料各向同性等优点，在骨科植入物方面具有广阔的应用前景[237]。为了提高 CFRPEEK 植入物的 生 物 相 容 性 和 骨 整 合 能 力 ， 在 CFRPEEK 的 多 孔 表 面 上 制 备 了GelMA/PAAM/Dex 复合水凝胶层。体外 BMSC 细胞实验证实 GelMA/PAAM/Dex复合水凝胶增强了 CFRPEEK 的生物相容性和成骨分化能力。研究GelMA/PAAM/Dex 修饰 CFRPEEK 的体内骨整合特性是 CFRPEEK 成为骨科人工植入物的关键指标。为探究功能性 CFRPEEK 植入物的体内骨整合和骨缺损重塑能力，建立了大鼠颅骨缺损模型。将不同的 CFRPEEK 样品随机植入到颅骨缺损中，在饲养 4 或 12 周后，取出带有植入物的大鼠颅骨，并进行骨整合和骨缺损重塑能力的分析。  \n\n植入4 周和12 周后，利用 Micro-CT 扫描了颅骨标本，观察植入物周围新生骨的细节和变化。通过软件重建了颅骨缺损处的 2D/3D 图像，并得到了植入物周围新骨的组织参数[239, 277]。如 Figure 2.20a 所示，与纯 PEEK 类似，CFRPEEK植入物在 Micro-CT 中没有产生伪影，这为跟踪 CFRPEEK 植入物周围骨组织的愈合过程提供了有利的条件[175]。在第 4 周和第 12 周，CP 周围的新生骨均多于SCP，SCP/GP 和 SCP/GP/Dex 的新生骨多于其他两组，并且 SCP/GP/Dex 生成的新骨组织最厚，这表明功能性 CFRPEEK 植入物具有优异的体内骨整合和成骨固定能力。Figure 2.20b-d 依次是新生骨的骨体积/总体积（BV/TV）、骨小梁数目（Tb.N）和骨小梁厚度（Tb.Th）的结果。在第 4 周和第 12 周，SCP/GP/Dex 的BV/TV、Tb.Th 和 Tb.N 都是最高的。在第 12 周，SCP/GP/Dex 的 BV/TV、Tb.Th和 Tb.N 相比于 SCP 分别提高了 $105.90\\%$ 、 $57.99\\%$ 和 $86.82\\%$ ，这表明GelMA/PAAM/Dex 修饰 CFRPEEK 明显增强了新骨的生成，上述结果与体外BMSC 细胞实验探究结果一致。有研究表明，Dex 能够促进骨骼相关蛋白质的分泌和钙化骨的形成[239]。SCP/GP/Dex 具有长期持续的药物释放性能，从SCP/GP/Dex 中释放的Dex 会促进成骨细胞的增殖，最终促进植入物周围新骨的生成，这些结果表明 GelMA/PAAM/Dex 复合水凝胶修饰 CFRPEEK 增强了骨缺损周围的骨生成和骨整合。  \n\n![](images/fd4b0c24f4ad431c1bba481e9eba218bfc8b24c4ca38623263cacbcfc794eafd.jpg)  \nFigure 2.20 (a) Micro-CT 2D and 3D reconstruction images after 4 and 12 weeks  \n\nimplantion (Red dotted frame denoted the bone defect site). Quantitative analysis of Micro-CT data including (b) BV/TV, (c) Tb.N, and (d) Tb.Th ( $^{*}p<0.05)$ at 4 and 12 weeks.  \n\n为了进一步分析不同CFRPEEK 植入物的骨整合能力，对颅骨标本进行了组织学染色（H & E，Masson 和 Van Gieson 染色）。Figure 2.21 是不同 CFRPEEK周围新骨的组织学染色结果，棕色区域（PEEK 基质）和黑点（长碳纤维）的混合区域代表不同 CFRPEEK 植入物。在植入 4 周和 12 周后，不同的 CFRPEEK植入物都直接与新生成的骨结合而没有发生移位，植入物周围的组织没有产生炎症或坏死，这表明 CFRPEEK 植入物是非毒性和术后长期生物相容性的。在Masson 和Van Gieson 染色结果观察到不同的植入物周围有一层类骨基质（黑色箭头）[278]。SCP/GP/Dex 植入物在植入 4 周后形成了比其他三组更多的新成熟骨（红色箭头）。在H & E 染色图像中也观察到在 SCP/GP/Dex 植入物周围生成了更大面积的新骨。植入12 周后，不同植入物周围形成的新骨量更多。SCP/GP/Dex植入物周围的新成熟骨牢固附着在植入物界面，表现出优异的骨结合性能。GelMA/PAAM/Dex 复合水凝胶能够加速骨沉积，进一步增强 CFRPEEK 植入物表面的骨化，从而提高CFRPEEK 植入物的骨整合性能。上述体内探究结果表明，GelMA/PAAM/Dex 修饰 CFRPEEK 植入物具有良好的生物相容性和优越的骨结合能力，为其作为骨科植入物的临床应用提供了参考。体内和体外一致的研究结果表明，GelMA/PAAM/Dex 复合水凝胶明显的改善了CFRPEEK 的骨整合性能。  \n\n![](images/b97c01f825c19f85ad5040bb1f9b0d4a1330ebb0ce982612b87f781abc8a72c1.jpg)  \n\n![](images/85758b0ebe5e01f70dfe06d2f74ce2925ca5340893109db4ad95c67de4c74293.jpg)  \nFigure 2.21 H & E, Masson and Van Gieson staining of the calvarial defect regions after treatment with CP, SCP, SCP/GP and SCP/GP/Dex for 4 and 12 weeks. [M, Materials; NB, new bone (red arrows); OM, osteoid matrix (black arrows)]. Scale bars  \n\n考虑到生物安全问题，在植入 12 周后，对实验大鼠的心脏，肝脏，脾脏，肺和肾脏进行H & E 染色，检测植入物在生物体内的毒性，以探究不同CFRPEEK植入物的体内生物毒性。如Figure 2.22 所示，植入12 周后实验大鼠没有明显的器官损伤或炎症病变，表明功能性 CFRPEEK 作为骨科植入物没有明显的生物毒性。  \n\n![](images/8418355e66efb1ae791bd2ed1a63c03a63fe42a4998843783d1db4067f6c85dc.jpg)  \nFigure 2.22 H & E staining of heart, liver, spleen, lung, and kidney after 12 weeks of treatments. Scale bar $=40\\upmu\\mathrm{m}$ .",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 59,
+        "chunk": "# 2.4 本章小结  \n\n设计并制备了负载Dex 的复合凝胶修饰 CFRPEEK 植入物。  \n\n（1）采用磺化处理和紫外接枝的表面改性方法将负载 Dex 的GelMA/PAAM  \n\n修饰到 CFRPEEK 植入物的表面上，构建出了具有三维凝胶网络的表面的CFRPEEK 植入物。通过 SEM 图像观察到 CFRPEEK 表面上的复合水凝胶网络结构，厚度为 $50~{\\upmu\\mathrm{m}}$ 。  \n\n（2）GelMA/PAAM/Dex 修饰 CFRPEEK 的表面水接触角为 $48.8\\pm0.45^{\\circ}$ ，具有优异的亲水性。  \n\n（3）GelMA/PAAM/Dex 修饰 CFRPEEK 在 21 天内的 Dex 释放效率为 $53\\%$ ，缓慢长期的Dex 释放能力有利于 BMSC 细胞的成骨分化。它在 SBF 中能够形成更多的骨状磷灰石结节，具有优异的体外矿化能力。  \n\n（4）体外细胞实验证实了 GelMA/PAAM/Dex 修饰 CFRPEEK 具有良好的体外生物相容性和优异的体外成骨性能，其中，SCP/GP/Dex 上的 BMSC 细胞增殖相较于SCP 上的提高了 $42.11\\%$ ，ALP 活性提高了 $28.29\\%$ 。  \n\n（5）体内大鼠的颅骨缺损实验表明，SCP/GP/Dex 周围的新生骨的骨小梁数目相较于 SCP 提高了 $86.82\\%$ ，这说明 GelMA/PAAM/Dex 修饰 CFRPEEK 具有优异的体内成骨性能，能够促进骨缺损的愈合。  \n\n综上所述，本研究团队制备的功能性 CFRPEEK 植入物具有作为骨科植入物实现临床应用的潜力。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 60,
+        "chunk": "# 第 3 章 GO-HAP 冷冻凝胶修饰 CFRPEEK 的制备及其成血管/成骨能力的研究",
+        "category": " Introduction"
+    },
+    {
+        "id": 61,
+        "chunk": "# 3.1 前言  \n\n骨组织工程是一种治疗超过临界骨缺损的新型替代方法，它通过植入与原始骨组织特征相匹配的人工植入物来诱导骨再生。在前面的研究中，虽然制备的负载 Dex 的复合水凝胶修饰 CFRPEEK 植入物能够增强 CFRPEEK 的生物相容性和成骨性能，但是骨骼是一种高度血管化的组织，在骨缺损愈合过程中也伴随着血管的重塑。如果在骨愈合过程中血管生成不及时，氧气和营养物质的供给就会不足，从而导致后期的成骨能力差。除了出色的成骨特性外，促进新血管形成对于骨科植入物的成骨和长期固定至关重要。开发具有良好血管化和成骨性能的多功能CFRPEEK 植入物对于 CFRPEEK 的临床应用至关重要。  \n\n纳米羟基磷灰石（HAP）具有出色的骨诱导、离子交换和生物相容性，经常用于促进植入物的成骨性能[279]。较差的力学性能限制了纳米羟基磷灰石在骨组织工程中的应用[280]。氧化石墨烯（GO）是一种 2D 纳米材料。氧化石墨烯（GO）因其独特的结构和优异的机械性能，在生物医学应用中发挥着越来越重要的作用[281]，特别是在骨组织工程中引起了极大的关注。GO 在低浓度下对生物体没有明显的毒性作用, 具有良好的生物相容性，能够加速细胞贴壁和扩散来促进细胞生长。GO 具有可降解性，且降解产物无明显毒性。GO 还可以大大提高 HAP 的成核和结晶能力[280, 282]。GO 表面的含氧官能团（如-COOH、-OH 和-O-）可以促进纳米羟基磷灰石的形成和均匀分散[283-286]。一些研究人员致力于研究 GO-HAP 纳米复合材料。目前的几项研究表明，低浓度的 GO 可以通过调节细胞中活性氮（RNS）和活性氧（ROS）的产生来刺激骨再生过程中的血管生成[278, 287-289]。  \n\n在紫外线照射下，CFRPEEK 中PEEK 主链上的二苯甲酮单元的碳氧双键会断裂一个键而形成自由基，它能引发活性单体或聚合物接枝到 CFRPEEK 植入物表面，从而形成三维（3D）凝胶网络[243-245]。冷冻凝胶是一种由凝胶前体溶液在零下温度形成的3D 海绵状大孔水凝胶，其相互连接的大孔结构和机械稳定性促进了内皮细胞向内生长和迁移，从而形成血管网络[290]。甲基丙烯酰化明胶  \n\n（GelMA）是一种可生物降解的明胶衍生物。GelMA 具有出色的的生物学特性和细胞相容性，可以显着刺激骨细胞分化并加速骨骼再生[291, 292]。聚乙二醇二丙烯酸酯（PEGDA）是一种具有可生物降解性和低细胞毒性的聚合物，通常用于制备凝胶支架。例如，Singh 等[293]开发了一种 PEGEDA/GelMA 冷冻凝胶用以模拟体内细胞外基质。  \n\n基于上述考虑，在本章工作中，首先利用原位键合法制备了 GO-HAP 纳米复合材料，然后通过基于自由基光聚合的冷冻凝胶技术在惰性磺化 CFRPEEK 植入物表面上制备了多功能 3D 海绵状大孔 GelMA/PEGDA/GO-HAP 冷冻凝胶层来增强CFRPEEK 的成血管和成骨能力。GO-HAP 纳米复合材料中 GO 的添加促进了HAP 在冷冻凝胶层的分散，细胞的增殖、粘附和扩散。同时，GO 与冷冻凝胶层的 3D 海绵状大孔结构协同增强了 CFRPEEK 植入物的血管生成能力。GO-HAP 纳米复合材料中的 HAP 提高了 CFRPEEK 植入物的成骨能力。该改性CFRPEEK 植入物具有一系列特性，包括 3D 海绵状大孔结构，出色的表面润湿性，良好的骨状磷灰石形成能力和钙离子的受控释放等。通过一系列表面表征检测分析了冷冻凝胶层对CFRPEEK 植入物理化性能的影响；通过体外细胞实验探究了 GO-HAP 冷冻凝胶表面改性的 CFRPEEK 植入物的生物相容性、成血管能力和成骨能力；通过大鼠颅骨缺损体内植入实验分析了该改性 CFRPEEK 植入物的血管化和骨整合性能。Figure 3.1 为本研究的技术路线示意图。  \n\n![](images/201c6289dc2e6b6247b529096517457dd687cd5df0e0503ee2d609915d285831.jpg)  \nFigure 3.1 (a) The modification procedures on the sulfonated CFRPEEK surface and (b) its biological functions: angiogenesis and osteogenesis.",
+        "category": " Introduction"
+    },
+    {
+        "id": 62,
+        "chunk": "# 3.2 实验部分",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 63,
+        "chunk": "# 3.2.1 实验材料与仪器",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 64,
+        "chunk": "# 1. 实验材料  \n\nTable 3.1 The materials and reagents.   \n\n\n<html><body><table><tr><td>名称</td><td>缩写</td><td>产品规格</td><td>生产厂家</td></tr><tr><td>聚乙二醇二丙烯</td><td>PEDGA,</td><td>AR</td><td>上海易恩化学技术有限公司</td></tr><tr><td>酸酯</td><td>MW: 700</td><td></td><td></td></tr><tr><td>无水氯化钙</td><td>CaCl2</td><td>AR</td><td>北京化工厂</td></tr><tr><td>磷酸氢二钠</td><td>Na2HPO4</td><td>AR</td><td>北京化工厂</td></tr><tr><td>氧化石墨烯</td><td>GO</td><td></td><td>深圳市图灵进化科技有限公司</td></tr></table></body></html>  \n\n<html><body><table><tr><td>名称 缩写</td><td>产品规格</td><td>生产厂家</td></tr><tr><td>氢氧化钠 NaOH</td><td>AR</td><td>北京化工厂</td></tr><tr><td>24孔 Transwell 小</td><td>3422</td><td>美国康宁公司</td></tr><tr><td>室</td><td></td><td></td></tr><tr><td>基质胶</td><td>无酚红</td><td>BD 生物科学技术有限公司</td></tr><tr><td>结晶紫</td><td>AR</td><td>北京索莱宝科技有限公司</td></tr></table></body></html>\n\n涉及的其它实验材料与第二章相同，详见 2.2.1 的Table 2.1。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 65,
+        "chunk": "# 2. 实验仪器  \n\nTable 3.2 The experimental apparatus.   \n\n\n<html><body><table><tr><td>仪器名称</td><td>型号 生产厂家</td></tr><tr><td>高分辨率激光拉曼光谱仪</td><td>LabRAM HR Horiba</td></tr><tr><td></td><td>Evolution</td></tr><tr><td>透射电子显微镜</td><td>HT7800 (TEM) 日立株式会社</td></tr><tr><td>电感耦合等离子体发射光谱仪</td><td>Agilent 725 (ICP- 安捷伦科技（中国)有限公</td></tr><tr><td></td><td>OES) 司</td></tr><tr><td>X射线衍射仪 PosiTestAT-M附着力测试仪 ATM50A</td><td>Empyrean (XRD) 荷兰帕纳科公司 美国DeFelsko公司</td></tr></table></body></html>\n\n涉及的其它实验仪器与第二章相同，详见 2.2.1 的Table 2.2。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 66,
+        "chunk": "# 3.2.2 氧化石墨烯-羟基磷灰石（GO-HAP）纳米复合材料的制备与表征  \n\n通过GO 中丰富的含氧官能团（-COOH、-OH 和-O-）与 $\\mathrm{Ca}^{2+}$ 键合制备GO-HAP 纳米复合材料[280, 282]。Figure 3.2 是 GO-HAP 制备路线图。原位键合法的原理是 GO 上丰富的含氧官能团（-COOH、-OH 和-O-）可以与 $\\mathrm{Ca}^{2+}$ 形成有效的成核位点，随后 $\\mathrm{PO}_{4}{}^{3.}$ -的加入会在成核位点上形成纳米羟基磷灰石。以制备 $150\\mathrm{mg}$ GO-HAP 为例，GO： $\\mathrm{HAP{=}1{:}2(G O{:}33\\%)}$ ），具体步骤如下：  \n\n先把 $185\\mathrm{mg}$ 无水氯化钙（ $\\mathrm{CaCl}_{2}$ ）溶于 $15\\mathrm{mL}$ 去离子水中；再配制 $13.2\\mathrm{mL}$ 浓度为 $3.8\\mathrm{mg/mLC}$ O 悬液，超声处理 $30\\mathrm{min}$ ；将上述GO 悬液缓慢滴加到 $\\mathrm{CaCl}_{2}$ 溶液中，磁力搅拌 $30~\\mathrm{min}$ ；配制 $1.7~\\mathrm{mL}0.6~\\mathrm{M}$ 的 $\\mathrm{\\DeltaNa_{2}H P O_{4}}$ 溶液，并缓慢滴加到上述混合液中；用 $1\\ \\mathrm{M\\NaOH}$ 溶液调节 $\\mathsf{p H}$ 在 9\\~11 之间， $45^{\\circ}\\mathrm{C}$ 水浴搅拌 $12\\mathrm{~h~}$ ；  \n\n最后，将 GO-HAP 沉淀物用去离子水洗涤， $8000~\\mathrm{rpm}$ 离心 3 次， $60^{\\circ}\\mathrm{C}$ 真空烘箱干燥 $24\\mathrm{h}$ ，备用。  \n\n![](images/f42c37407518b02b877754ae9851e047c7f38a0e4cb75f6428915c81db4dd7d3.jpg)  \nFigure 3.2 Schematic diagram of preparation of GO-HAP nanocomposites.  \n\n利用 XRD 和 ATR-FTIR 检测 GO-HAP 的晶体结构和组成；使用高分辨率激光拉曼光谱仪分析 GO-HAP 的结构；采用 TEM 和 SEM 分析 GO-HAP 形貌，使用 EDS 检测 GO-HAP 的元素组成。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 67,
+        "chunk": "# 3.2.3 磺化 CFRPEEK 复合材料的制备  \n\n磺化CFRPEEK 复合材料的制备步骤具体如下：  \n\n（1）（2）（3）（4）与第二章 2.2.2 的实验步骤相同；（5）在室温下，CFRPEEK 复合材料在浓硫酸中磁力搅拌 $3\\mathrm{min}$ ，以获得均匀的多孔表面；（6）反应后的 CFRPEEK 复合材料依次浸入超纯水和丙酮中，并在超声波清洗器中清洗；（7）将得到的磺化CFRPEEK 复合材料在真空干燥箱中 $60^{\\circ}\\mathrm{C}$ 干燥24 小时，以备后续使用；（8）尺寸为 $\\Phi8{\\times}1.5~\\mathrm{mm}$ 的磺化 CFRPEEK 用于表面表征和体外细胞实验，尺寸为 $\\Phi5{\\times}1.5\\ \\mathrm{mm}$ 的磺化 CFRPEEK 用于动物体内实验。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 68,
+        "chunk": "# 3.2.4 GO-HAP 冷冻凝胶修饰 CFRPEEK 的制备  \n\n（1）GelMA/PEGDA/GO-HAP 凝胶前体液的制备  \n\n采用与第二章相同的方法制备 GelMA，详见 2.2.3 甲基丙烯酰化明胶（GelMA）的制备与表征。  \n\n避光条件下，按 $10{:}5\\mathrm{wt\\%}$ 配制 GelMA/PEGDA 溶液；将 $0.5\\mathrm{mg/mL}$ GO-HAP悬液超声分散1 小时，然后以 $25,50,100(\\upmu\\mathrm{g/mL})$ ）的浓度添加到 GelMA/PEGDA溶液中；将混合溶液 $37^{\\circ}\\mathrm{C}$ 磁力搅拌 8 小时，得到不同浓度的 GelMA/PEGDA/GO-HAP 凝胶前体液。Figure 3.3 是添加不同浓度 GO-HAP 的 GelMA/PEGDA 凝胶前体液的图像，可见 GelMA/PEGDA 溶液（a）是透明无色的，GelMA/PEGDA/GO-HAP 凝胶前体液（b-d）为褐色。  \n\n![](images/3bdc64a9ea199b3356f95d5cdcaf2d6af95d5aded29edee835d2f75ce5a15610.jpg)  \nFigure 3.3 Gel precursors of GelMA/PEGDA with different concentrations of GOHAP: (a) $0\\upmu\\mathrm{g/mL}$ , (b) $25\\upmu\\mathrm{g/mL}$ , (c) $50~\\upmu\\mathrm{g/mL}$ , (d) $100~\\mathrm{\\upmug/mL}$ .  \n\n（2）GO-HAP 冷冻凝胶修饰 CFRPEEK 的制备  \n\n避光条件下，将 3.2.3 制备的磺化 CFRPEEK 按 $60~{\\upmu\\mathrm{L}}/{\\upmathrm{c m}}^{2}$ 的比例浸没到GelMA/PEGDA/GO-HAP 凝胶前体液中；静置 10-15 分钟，让凝胶前体液均匀覆盖在磺化CFRPEEK 表面；浸泡在前体液中的磺化CFRPEEK 先 $4^{\\circ}\\mathrm{C}$ 冷藏1 小时，再- ${\\bf\\nabla}\\cdot20^{\\circ}\\mathrm{C}$ 冷冻 12 小时；冷冻后，将磺化 CFRPEEK 置于波长 $365~\\mathrm{nm}$ 、光强 10$\\mathrm{mW}/\\mathrm{cm}^{2}$ 的紫外灯下 15 分钟；光照后，将改性的磺化 CFRPEEK 浸入蒸馏水中，以去除未反应的前体液，得到GelMA/PEGDA/GO-HAP 冷冻凝胶修饰CFRPEEK。  \n\n各组CFRPEEK 样品用如下缩写表示：  \n\nSCP：磺化 CFRPEEK；  \n\nGP10-5：GelMA/PEGDA 修饰的磺化 CFRPEEK；  \n\nGHX（ $X=25$ ，50 和 100）：GelMA/PEGDA/GO-HAP 修饰的磺化 CFRPEEK，$\\mathrm{\\DeltaX\\upmug/mL}$ 代表 GO-HAP 的浓度。  \n\n通过SEM 对每组样品的表面和截面形貌进行表征； ATR-FTIR 和XPS 用于表征每组样品表面的化学构成；采用静态接触角测量仪检测每组样品的水接触角，每个样品测量3 个不同的区域，并且每组样品重复测量 2 次。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 69,
+        "chunk": "# 3.2.5 冷冻凝胶层的附着力测试  \n\n根据 ASTM D4541-02，使用 PosiTest AT-M 附着力测试仪采用拉出法测试了  \n\n冷冻凝胶层的附着力。Figure 3.4a 是拉出法的实验装置示意图。具体如下：  \n\n（1）将锭子用环氧胶垂直粘在尺寸为 $50\\mathrm{mm}{\\times}50\\mathrm{mm}{\\times}1.5\\mathrm{mm}$ 的 $\\mathbf{GP}_{10-5}$ 样品上，静置24 小时等待环氧胶完全干透（Figure 3.4b）；  \n\n（2）沿着锭子的边缘用切割器切划冷冻凝胶层，清除切划过程中产生的碎屑（Figure 3.4c）；  \n\n（3）将附着力测试仪的套筒套在锭子上，然后打开仪器进行测试；  \n\n（4）测试完成后，观察锭子和被测表面的状况并记录附着力。  \n\n![](images/011ec5124f603bb940b4a92c6e1cf059c11e771d7dc74e012750d0ef3d39ca27.jpg)  \n\nFigure 3.4 (a) Diagram of the experimental device of the pull-off method. (b) Image of $\\mathrm{GP}_{10-5}$ after adhering the dolly with epoxy glue. (c) Image of $\\mathrm{GP}_{10-5}$ after cutting by the cutter.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 70,
+        "chunk": "# $3.2.6\\mathrm{Ca}^{2+}$ 的释放行为  \n\n将 $\\mathrm{GH}_{25}$ ， $\\mathrm{GH}_{50}$ 和 $\\mathrm{{GH}_{100}}$ 分别浸泡在 2 mL PBS 中，并在 $37^{\\circ}\\mathrm{C}$ 恒温摇床上以$100\\mathrm{rpm}$ 匀速振荡；在规定的时间点，收集含有释放 $\\mathrm{Ca}^{2+}$ 的PBS 并加入等体积的新鲜 PBS；通过 ICP-OES 检测 $\\mathrm{Ca}^{2+}$ 的浓度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 71,
+        "chunk": "# 3.2.7 体外矿化行为研究  \n\nSCP，GP10-5， $\\mathrm{GH}_{25}$ ， $\\mathrm{GH}_{50}$ 和 $\\mathrm{GH}_{100}$ 体外矿化研究的实验步骤与第二章相同，详见2.2.7 体外矿化行为研究。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 72,
+        "chunk": "# 3.2.8 细胞实验",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 73,
+        "chunk": "# 3.2.8.1 细胞的培养  \n\n采用大鼠骨髓间充质干细胞（BMSC）探究改性CFRPEEK 的成骨能力。大鼠骨髓间充质干细胞（BMSC）的提取、培养与传代实验步骤与第二章相同，详  \n\n见2.2.8.1。利用购自中国医学科学院基础医学研究所细胞资源中心的人脐静脉内皮细胞（HUVEC），探究改性 CFRPEEK 的成血管能力。将 BMSC 和 HUVEC 接种到DMEM 完全培养基中，然后培养在 $37^{\\circ}\\mathrm{C}$ 、 $5\\%$ CO2 的培养箱中。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 74,
+        "chunk": "# 3.2.8.2 体外 BMSC 细胞相容性测试  \n\n1. CCK-8 试剂盒用于检测材料表面 BMSC 细胞的增殖情况，实验步骤与第  \n二章相同，详见2.2.8.2 的实验 1。2.通过扫描电镜观察BMSC 细胞在材料表面的生长情况，具体实验步骤与第  \n二章相同，详见2.2.8.2 的实验 2。3. BMSC 细胞在不同样品上的粘附与扩散用罗丹明标记的鬼笔环肽和 DAPI  \n染色法进行检测，具体实验步骤与第二章相同，详见 2.2.8.2 的实验3。4. BMSC 细胞在不同样品上的迁移性能通过 Transwell 实验进行探究，具体  \n的实验步骤如下：（1）将处在对数生长期的第三代 BMSC 细胞用无血清培养基制成密度为  \n$5{\\times}10^{5}\\mathrm{cell/ml}$ 细胞悬液；（2）取细胞悬液 $100\\upmu\\mathrm{L}$ 加入 Transwell 小室；（3）将经过 Cobalt 60 灭菌（15KGy， $20\\mathrm{h}$ ）的样品放入 24 孔板下室中，用  \nPBS 清洗一遍后，每孔滴加 $600~\\upmu\\mathrm{L}$ 含 $1\\%$ FBS 的 DMEM 培养基；（3）将接种 BMSC 细胞的 Transwell 小室插入不同样品相应的孔中，培养  \n$24\\mathrm{h}$ ；（4）取出小室，吸出培养基，PBS 洗涤两次， $4\\%$ 多聚甲醛固定 30 分钟，  \n适当风干小室；（5） $0.1\\%$ 结晶紫染色20 分钟，擦去小室上层未迁移细胞，PBS 清洗三遍；（6）随机选择6 个视野，在显微镜下观察和计数细胞。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 75,
+        "chunk": "# 3.2.8.3 体外成骨性能测试  \n\n1. 通过碱性磷酸酶（ALP）活性定量和染色实验检测 BMSC 细胞在不同样品表面的早期成骨分化情况，具体实验步骤与第二章相同，详见 2.2.8.3 的实验1。  \n\n2. 通过茜素红（ARS）染色和定量分析检测 BMSC 细胞在不同样品表面的晚期成骨分化情况，具体实验步骤与第二章相同，详见 2.2.8.3 的实验2。  \n\n3. 通过实时荧光定量聚合酶链式反应（RT-PCR）探究BMSC 细胞在不同样品表面的成骨相关基因的表达情况，具体实验步骤与第二章相同，详见 2.2.8.3 的实验3。其中RT-PCR 所需的成骨相关基因的引物对如 Table 3.3 所示。  \n\nTable 3.3 Primer pairs used in RT-PCR analysis.   \n\n\n<html><body><table><tr><td>Genes</td><td>Sequence (5'-3')</td></tr><tr><td>BMP-2</td><td>F:ATTAGCAGGTCTTTGCACCA R:ACGCTTTTCTCGTTTGTGGA</td></tr><tr><td>Runx2</td><td>F: GGCAGCACGCTATTAAATCCAA</td></tr><tr><td></td><td>R:GACTCATCCATTCTGCCGCTA F: ATCGGAACAACCTGACTGACC</td></tr><tr><td rowspan=\"2\">ALP</td><td>R:CTGCCTCCTTCCACTAGCAA</td></tr><tr><td>F: ATGCCATCAAGGTCTACTGCAA</td></tr><tr><td rowspan=\"2\">COL-I</td><td>R: GAACCTTCGCTTCCATACTCG</td></tr><tr><td></td></tr><tr><td>GAPDH</td><td>F: TATGACTCTACCCACGGCAAG R:ATACTCAGCACCAGCATCACC</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 76,
+        "chunk": "# 3.2.8.4 体外成血管性能测试  \n\n1. Cell Counting Kit（CCK-8）试剂盒检测 HUVEC 细胞在材料表面的增殖情况，具体实验步骤与第二章相同，详见 2.2.8.2 的实验1。2. HUVEC 细胞在不同样品上的粘附与扩散用罗丹明标记的鬼笔环肽和DAPI 染色法进行检测，具体实验步骤与第二章相同，详见 2.2.8.2 的实验3。3. HUVEC 细胞在不同样品上的迁移性能通过 Transwell 实验进行探究。具体的实验步骤与 BMSC 细胞的在不同样品上的迁移性能实验相同，详见 3.2.8.2的实验4。4. 利用基质胶 Matrigel 血管样网络结构形成来检测材料的成血管性能。具体操作方法如下：  \n\n（1）将经过 Cobalt 60 灭菌（15KGy， $20\\mathrm{h}$ ）的不同样品放入 24 孔板中，用PBS 清洗一遍后，每孔滴加 $1~\\mathrm{mL}$ 含 $1\\%$ FBS 的 DMEM 培养基， $24\\mathrm{~h~}$ 后收集培养基；  \n\n（2）使用上述收集的培养基将对数生长期的HUVEC 细胞制备成细胞悬液，密度为 $1{\\times}10^{5}\\mathrm{cell/ml}$ ；  \n\n（3）将基质胶Matrigel 均匀铺在24 孔板中，放置 $37^{\\circ}\\mathrm{C}$ 培养箱凝聚；  \n（4）1 h 后，将 $1\\mathrm{mL}$ 上述 HUVEC 细胞悬液接种到基质胶表面；  \n（5）在 $37^{\\circ}\\mathrm{C}$ 培养箱培养 6 h 后，用显微镜观察血管样网络结构的形成情况。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 77,
+        "chunk": "# 3.2.9 大鼠颅骨缺损实验",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 78,
+        "chunk": "# 3.2.9.1 建立大鼠颅骨缺损模型  \n\n采用大鼠颅骨缺损实验模型来探究 GO-HAP 冷冻凝胶修饰的 CFRPEEK 植入物的体内成骨能力。动物实验的所有程序均经吉林大学实验动物福利与伦理委员会批准（批准号：2021128），并按照相关机构指南和法律进行。大鼠颅骨缺损模型建立的具体操作步骤与第二章相同，详见 2.2.9.1 建立大鼠颅骨缺损模型。Figure 3.5 大鼠颅骨缺损模型建立的示意图。  \n\n![](images/819dbe7afc78f57c57144149760e264f7ed2ac1a37de878bc27f9d1a2874073b.jpg)  \nFigure 3.5 (a) Construction of the rat cranial defect model and (b) implantation of different implants",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 79,
+        "chunk": "# 3.2.9.2 显微计算机断层扫描 （micro-CT）  \n\n具体操作步骤与第二章相同，详见2.2.9.2 显微计算机断层扫描 （micro-CT）。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 80,
+        "chunk": "# 3.2.9.3 组织学探究",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 81,
+        "chunk": "# 1. 颅骨硬组织切片及染色  \n\n具体操作步骤与第二章相同，详见 2.2.9.3 实验1。  \n\n2 内脏石蜡切片及染色  \n\n具体操作步骤与第二章相同，详见 2.2.9.3 实验2。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 82,
+        "chunk": "# 3.2.10 统计与分析  \n\n使用 IBM SPSS Statistics 22 软件对数据进行了统计学分析。统计显著性（ $(p$ $<0.05$ ）是通过Tukey 事后检验的单因素方差分析（ANOVA）获得的。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 83,
+        "chunk": "# 3.3 结果与讨论",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 84,
+        "chunk": "# 3.3.1 氧化石墨烯-羟基磷灰石（GO-HAP）的制备  \n\n采用原位键合法制备 GO-HAP 纳米复合材料，用以促进磺化 CFRPEEK 表面的成骨和血管生成能力。Figure 3.6a 为 GO-HAP 的 SEM 图像，Figure 3.6b 为GO-HAP 的 TEM 图像。在 GO-HAP 纳米复合材料中，长 $20{-}70~\\mathrm{nm}$ ，宽 $3{-}8~\\mathrm{nm}$ 的针棒状 HAP 均匀分布在 GO 纳米片上，这是因为 GO 表面的含氧官能团有利于纳米 HAP 的形成和均匀分散[294]，纳米 HAP 已被证明比微米 HAP 更有利于成骨[295-297]。  \n\n![](images/8945ddb3e0c16784e791ea307643c6bc2d2c3cbb844924acca2992ec3b877d8f.jpg)  \nFigure 3.6 (a) The SEM and (b) TEM images of the GO–HAP nanocomposite.  \n\nFigure 3.7a 是 GO-HAP 和 HAP 的 XRD 图谱，XRD 结果表明，原位键合法制备的 GO-HAP 的衍射峰与 HAP 的标准峰（JCPDS 09-0432）匹配良好，这说明 GO 的引入没有改变 HAP 的晶体结构。Figure 3.7b 是 GO-HAP 和 GO 的拉曼光谱，在GO-HAP 拉曼光谱的 $942\\mathrm{cm}^{-1}$ 处检测到HAP 峰的存在，这表明 GO-HAP 的合成是成功的。  \n\n![](images/323def8aabaae15e426731fff94d30f5c06cc502020e383ed74342b37f0cea60.jpg)  \nFigure 3.7 (a) XRD patterns of GO, HAP and the GO–HAP nanocomposite; and (b) Raman spectra of GO and the GO–HAP nanocomposite.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 85,
+        "chunk": "# 3.3.2 GO-HAP 冷冻凝胶修饰 CFRPEEK 的制备  \n\n为了探究不同比例的 GelMA/PEGDA 冷冻凝胶层对 CFRPEEK 表面形貌的影响，用不同比例的 GelMA/PEGDA（GelMA:PEGDA $\\scriptstyle\\operatorname{\\underline{{\\}}}10:0$ ，10:5 和 $15{:}5\\mathrm{wt}^{0}/\\$ ）来改性 CFRPEEK。Figure 3.8a 是不同比例的 GelMA/PEGDA 改性 CFRPEEK 表面 SEM 图像，不同比例的 GelMA/PEGDA 都在 CFRPEEK 表面形成了 3D 凝胶网络结构。如 Figure 3.8b 所示， $\\mathrm{GP}_{10-0,}\\mathrm{GP}_{10-5}$ 和 $\\mathbf{GP}_{15-5}$ 的孔径分别为 $88.34{\\pm}25.48\\$ $\\upmu\\mathrm{m},\\ 95.87{\\pm}28.98\\ \\upmu\\mathrm{m}$ 和 $53.04{\\pm}15.71\\upmu\\mathrm{m}$ 。与 $\\mathbf{GP}_{10-0}$ 相比，GP10-5 的孔径增大，这应该与PEGDA 的加入有关。当 GelMA/PEGDA 的比例增加时，冷冻凝胶层的孔径减小。以前的研究表明，孔径对于细胞迁移和增殖至关重要，组织工程的理想孔径范围为 $100{-}200\\upmu\\mathrm{m}^{[298-300]}$ 。因此，在后续研究中 GelMA:PEGEDA=10:5 wt%。  \n\n![](images/6f89507827b66717c0644daafdb81d1c275f6b2aa8fd0ef1ebf32cc23ff1c996.jpg)  \nFigure 3.8 (a) SEM images of: GP10-0, GP10-5 and GP15-5 at high and low  \n\nmagnifications. Scale bars $=50\\upmu\\mathrm{m}$ and $150~{\\upmu\\mathrm{m}}$ . (b) The pore diameters of $\\mathrm{GP_{10-0}}$ , GP10-5 and GP15-5, \\* and # represented $p<0.05$ when compared with $\\mathrm{GP_{10-0}}$ and $\\mathbf{GP}_{10}.$ - 5, respectively.  \n\nFigure 3.9a 是磺化 CFRPEEK 改性前后的 SEM 图像。在 SCP 表面观察到均匀的微孔结构和少量裸露的碳纤维。在基于自由基光聚合冷冻凝胶技术处理后，GP10-5 上形成了3D 海绵状大孔冷冻凝胶网络。当GO-HAP 的浓度低于 $100\\mathrm{ng/mL}$ 时，磺化 CFRPEEK 表面的冷冻凝胶层的形貌基本不受影响，并且 GO-HAP 纳米复合材料均匀分散在冷冻凝胶层中。当 GO-HAP 的浓度高于 $100~\\mathrm{{ng/mL}}$ 时，由于 GO 优异的光热转换效果，GelMA/PEGDA/GO-HAP 的上层冰晶在紫外辐照下会融化[301, 302]，使得冷冻凝胶层的大孔结构被上部塌陷的孔壁覆盖，这不利于营养物质和氧气的运输以及细胞迁移。此外，相关文献显示，低于 $1\\upmu\\mathrm{g/mL}$ 的低浓度GO 能够刺激细胞增殖，为成骨和血管生成创造有利的免疫环境[288]。因此，在本章中选择GO-HAP 的浓度低于 $100\\mathrm{ng/mL}$ 。Figure 3.9b 是 $\\mathbf{GP}_{10-5}$ 切片的横截面SEM 图像，磺化CFRPEEK 表面的GelMA/PEGDA 冷冻凝胶层厚度约为 $45\\upmu\\mathrm{m}$ ，并且可以观察到3D 海绵状大孔冷冻凝胶网络结构。  \n\n![](images/ba7024794d29e8db376bacc8b00a580060f6205f9b09ce02ab5cf831a968526a.jpg)  \nFigure 3.9 (a) SEM images of SCP, GP10-5, $\\mathrm{GH}_{25}$ , $\\mathrm{GH}_{50}$ , $\\mathrm{\\GH_{100}}$ , $\\mathrm{GH}_{150}$ and $\\mathrm{GH}_{200}$ , scale bars $=10\\upmu\\mathrm{m}$ and $200~{\\upmu\\mathrm{m}}$ . (b) SEM images of the $\\mathrm{GP_{10-5}}$ cross-section, scale bar  \n\n通过 XPS 测量不同样品的表面化学成分如 Figure 3.10 和 Table 3.4 所示。Figure 3.10a 为不同样品的 XPS 谱图。在 SCP 中，检测到 C 1s、O 1s 和 S 2p 峰。除了 C 1s 和 O 1s 峰外，在 $\\mathbf{GP}_{10-5}$ 中还检测到 N 1s 峰，这表明 GelMA/PEGDA冷冻凝胶已经成功接枝到磺化 CFRPEEK 表面。除了 C 1s、 O 1s 和 N 1s 峰外，$\\mathrm{GH}_{100}$ 还观察到约 $1.6~\\mathrm{wt\\%}$ Ca（Figure 3.10b）和 $0.96\\mathrm{wt\\%P}$ （Figure 3.10c），表明GO-HAP 纳米复合材料已成功掺入 GelMA/PEGDA 冷冻凝胶层中。SCP、 $\\mathbf{GP}_{10}.$ -$_5$ 和 $\\mathrm{GH}_{100}$ 的高分辨率C 1s 光谱进一步证明了每个改性步骤后表面化学状态的变化（Figure 3.10d）。SCP 的 C 1s 光谱在 $284.8~\\mathrm{eV}$ 、 $285.7\\ \\mathrm{eV}$ 和 $286.5\\ \\mathrm{eV}$ 处分别对应 C-C、C-O 和 $\\scriptstyle{\\mathrm{C=O}}$ 。在基于自由基光聚合冷冻凝胶技术处理后，在 GP10-5和 $\\mathrm{\\GH_{100}}$ 中观察到C-N（ $285.7\\mathrm{eV}$ ）和 COOH（ $288.7\\mathrm{eV}$ ）两个额外的峰，这进一步证明冷冻凝胶层已经成功地接枝在磺化 CFRPEEK 表面。  \n\n![](images/3f1f6ea90e2da74bf368bc002580da6e4d57e061dddd74a7e9e11af4c969b136.jpg)  \nFigure 3.10 (a) XPS spectra of SCP, $\\mathbf{GP}_{10-5}$ , $\\mathrm{GH}_{100}$ and high-resolution (b) $\\mathrm{Ca}2\\mathrm{p}$ and (c) $\\boldsymbol{\\mathrm{~P~}}2\\boldsymbol{\\mathrm{p}}$ spectra of GH100. (d) High-resolution C 1s spectra acquired from SCP, $\\mathbf{GP}_{10}.$ - 5 and GH100.  \n\nTable 3.4 Elemental composition of different substrate surfaces as determined by XPS.   \n\n\n<html><body><table><tr><td>Material</td><td>C (%)</td><td>N (%)</td><td>0(%)</td><td>S (%)</td><td>Ca (%)</td><td>P(%)</td></tr><tr><td>SCP</td><td>58.84</td><td></td><td>40.06</td><td>1.09</td><td></td><td></td></tr><tr><td>GP10-5</td><td>41.17</td><td>10.11</td><td>48.72</td><td></td><td></td><td></td></tr><tr><td>GH100</td><td>44</td><td>12.46</td><td>40.97</td><td>---</td><td>1.6</td><td>0.96</td></tr></table></body></html>  \n\nFigure 3.11 是不同样品的水接触角测定结果，SCP 的水接触角为$110.75^{\\circ}\\pm3.46^{\\circ}$ ，显示出疏水特性。基于自由基光聚合冷冻凝胶技术处理后， $\\mathbf{GP}_{10}.$ 5 的水接触角为 $51.18^{\\circ}\\pm5.46^{\\circ}$ ，极大提高了磺化 CFRPEEK 的亲水性。在引入 GO-  \n\nHAP 后，GelMA/PEGDA/GO-HAP 修饰的磺化 CFRPEEK 仍然具有亲水性，并且水接触角随着GO-HAP 浓度的增加而增加（ $\\mathrm{GH}_{25}{\\cdot}43.60^{\\circ}{\\pm}3.39^{\\circ}$ ， $\\mathrm{GH}_{50}\\colon55.70^{\\circ}\\pm1.72^{\\circ}$ 和 GH100： $62.86^{\\circ}\\pm2.69^{\\circ}.$ ），亲水性的表面有利于细胞附着和增殖 [303]。  \n\n![](images/c99d1ea2c785c1a1805261f6c77c210fcd3112f5557dfc23f5f42c70fe5b6c72.jpg)  \nFigure 3.11 Water contact angles of SCP, GP10-5, GH25, GH50 and GH100. \\* and # represent $p{<}0.05$ when compared with SCP and $\\mathrm{GH}_{25}$ , respectively.  \n\n基于自由基光聚合的冷冻凝胶技术的原理如 Figure 3.12 所示。在零下温度（ $\\cdot-20^{\\circ}\\mathrm{C}$ ）下，在磺化 CFRPEEK 上的 GelMA/PEGDA/GO-HAP 凝胶前体液中的溶剂水会形成冰晶并与溶质发生相分离。在聚合之前或期间，冰晶会充当致孔剂，使得 GelMA/PEGDA/GO-HAP 能够在磺化 CFRPEEK 表面形成 3D 海绵状大孔结构。该大孔结构不仅提供了更多的营养和氧气，而且连通的孔结构还促进了细胞迁移和血管形成[304-306]( Figure 3.12a)。紫外辐照会使得 CFRPEEK 中的二苯酮结构产生自由基，并引发聚合物 GelMA 和 PEGDA 的烯基双键发生聚合反应，与CFRPEEK 形成 C-C 共价键，从而生成 GelMA 和 PEGDA 与 PEEK 的接枝共聚物，所以在 CFRPEEK 表面形成了一层 3D 海绵状大孔冷冻凝胶网络。GO-HAP纳米复合材料与GelMA/PEGDA 形成氢键以提高冷冻凝胶结构的稳定性( Figure3.12b)。  \n\n![](images/36800505b5f700f1cfed50bb63d0b82cf5b03e5e45ee3bef64836b2a4a999d57.jpg)  \n\n![](images/9f21dcc129a472d09215783bb4f2739601d41732fc3fd6ff58edd62a7ccb1ee5.jpg)  \nFigure 3.12 (a) Schematic depiction of the GelMA/PEGDA/GO-HAP cryogel on the surface of the sulfonated CFRPEEK formation. (b) Schematic illustration of the free radical polymerization on the surface of CFRPEEK.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 86,
+        "chunk": "# 3.3.3 冷冻凝胶层的附着力  \n\n通过拉出法探究冷冻凝胶层在 CFRPEEK 表面上的附着力。如 Figure 3.13a所示，通过观察被测样品的断裂表面（红色圆圈），发现磺化 CFRPEEK 表面仍有残留的冷冻凝胶，并且基材未暴露，这表明冷冻凝胶层的拉伸强度低于冷冻凝胶层与磺化 CFRPEEK 表面的粘附强度[307]。如 Figure 3.13b 所示，当样品和锭子分离时，拉伸应力为 $3.94\\mathrm{MPa}$ 。先前的文献表明，仅通过等离子体处理的 PEEK表面的附着强度为 $1.1{-}3.0\\ \\mathrm{MPa}^{[308]}$ 。拉出试验有效证明了冷冻凝胶层在磺化CFRPEEK 表面具有良好的粘附稳定性。  \n\n![](images/5892dd233a3d93ea82ec48216e6c61efdea611c623f509aee0abd597344d9d9b.jpg)  \nFigure 3.13 (a) Image of $\\mathbf{GP}_{10-5}$ and the dolly after pull-off test. (b) Adhesion data of GP10-5.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 87,
+        "chunk": "# $3.3.4\\mathrm{Ca}^{2+}$ 的释放行为  \n\nGH25、GH50 和 $\\mathrm{{GH}_{100}}$ 在 PBS 中孵育 7 天后， $\\mathrm{Ca}^{2+}$ 的释放行为如 Figure 3.14所示。在第5 天时， $\\mathrm{GH}_{25}$ 中的 $\\mathrm{Ca}^{2+}$ 几乎被完全释放（ $.\\sim100\\%$ ），这不利于细胞的成骨分化；在 7 天内，GH50 和 $\\mathrm{{GH}_{100}}$ 的 $\\mathrm{Ca}^{2+}$ 连续释放，第 7 天的累计释放浓度分别为 $5.13{\\pm}0.10$ 和 $6.97{\\scriptstyle\\pm0.10}~{\\upmu\\mathrm{g/mL}}$ 。 $\\mathrm{GH}_{50}$ 和 $\\mathrm{GH}_{100}$ 中钙离子的长期稳定释放70  \n\n有利于CFRPEEK 植入物的长期成骨固定。  \n\n![](images/16e2b51f7784c3736d2e456b478a84a23aff20ee7e8b763faa02f3be161eaf75.jpg)  \nFigure 3.14 $\\mathrm{Ca}^{2+}$ release profile of $\\mathrm{GH}_{25}$ , GH50 and GH100 over 7 days.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 88,
+        "chunk": "# 3.3.5 体外矿化性能  \n\n植入物浸泡在 SBF 溶液中时产生骨状磷灰石的能力是探究体外骨结合能力的重要指标[260]。Figure 3.15 是在 SBF 中浸泡 7 天后不同样品表面形貌 SEM 图。在SCP 上几乎没有形成圆形结节，在 GP10-5 上沉积了一些结节，这是由于 GelMA的成核位点促进了骨状磷灰石的形成 [266, 267]。当引入GO-HAP 时，GHX（ $X=25$ ，50 和 100）表面几乎被球形颗粒完全覆盖，并且随着 GO-HAP 浓度的增加颗粒变大，这是因为GO-HAP 中的 HAP 为骨状磷灰石沉积物的形成提供了许多成核位点。上述结果表明，GO-HAP纳米复合材料促进了CFRPEEK的体外矿化性能，磺化 CFRPEEK 表面的 GelMA/PEGDA/GO-HAP 冷冻凝胶层具有良好的体外骨结合能力。  \n\n![](images/0578e24d79ac8b5eb3c7b146f0106179c96ce0f927d933dff58ec3547205ddd6.jpg)  \nFigure 3.15 SEM views of various specimens after 7 days of soaking in SBF.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 89,
+        "chunk": "# 3.3.6 体外 BMSC 细胞相容性  \n\nBMSC 常用于探究生物材料的生物相容性和成骨能力，从 BMSC 的细胞增殖、粘附、扩散和迁移等方面研究各组的细胞相容性。通过 CCK-8 检测 BMSC细胞增殖情况如 Figure 3.16 所示。在 BMSC 与各组样品共培养 4 天后， SCP 的生物惰性使得它在促进细胞增殖方面表现最差， $\\mathrm{\\GH_{100}}$ 表现最好；当培养延长至7 天后，各组BMSC 的细胞活力均显著提高，且 $\\mathrm{\\GH_{100}}$ 的细胞活力相较于 SCP 提高了 $24.41\\%$ 。根据上述细胞增殖结果，BMSC 细胞在 GelMA/PEGDA/GO-HAP冷冻凝胶修饰CFRPEEK 表现出更好的细胞活力。  \n\n![](images/2bed2e4c44b1580fdbde62c02146fd27dfcf1c13e16ea067d45b5058c0bae520.jpg)  \nFigure 3.16 Cell proliferation after 1, 4 and 7 days of culture on various substrates, \\*, # and & represented $p<0.05$ when compared with SCP, GP10-5 and $\\mathrm{GH}_{25}$ , respectively.  \n\nBMSC 细胞在不同样品上的形态如Figure 3.17 所示。SCP 上的细胞呈球状，细胞边缘有少量附着的丝状伪足，这是由于 SCP 的生物学惰性表面阻碍了细胞的粘附和扩散。除SCP 外，其他各组上的细胞以纺锤形扩散，在培养 24 小时后，几乎覆盖了整个样品表面。  \n\n![](images/f8f00b4d7853c1fa0f54395a55d37a27e9f97eb30a3ee0364a2a478ed02151c8.jpg)  \nFigure 3.17 SEM images of BMSCs adhered to various substrates after one day of incubation.  \n\n为了进一步研究 BMSC 细胞在不同 CFRPEEK 样品上的粘附行为，通过CLSM 图像观察 BMSC 细胞在所有样品上培养 24 小时后的细胞骨架和细胞核。如Figure 3.18 所示，BMSC 细胞在除 SCP 外的样品上扩散良好，细胞间有更多的互联和重叠，产生更成熟的肌动蛋白，这表明冷冻凝胶层有利于细胞的粘附和扩散。BMSC 细胞的 SEM 和 CLSM 图像及细胞增殖结果表明，磺化 CFRPEEK植入物表面的 GelMA/PEGDA/GO-HAP 冷冻凝胶层具有更优异的细胞相容性。上述实验结果归因于冷冻凝胶层的亲水三维海绵状大孔网络结构为细胞提供了丰富的附着位点，并且 GelMA 的 RGD 序列和 GO-HAP 中的 GO 能够协同促进细胞粘附和增殖[291, 309]。  \n\n![](images/12c0f5bb75f0b6bebfbd035f82d3a264e1d99b88ae57f11385b956b62b5554c9.jpg)  \nFigure 3.18 CLSM of BMSCs incubated for 24 hours on various substrates. TRITCphalloidin staining in red represented cytoskeleton, whereas DAPI staining in blue represented cell nuclei, scale bar ${\\tt\\operatorname=}50\\upmu\\mathrm{m}$ .  \n\n通过体外 Transwell 细胞迁移实验探究不同样品对 BMSC 细胞的迁移影响。如 Figure 3.19a 所示，培养 24 小时后，在 SCP 和 $\\mathbf{GP}_{10-5}$ 中仅观察到少量迁移的BMSC 细胞。 $\\mathrm{GH_{X}}$ （ $X=25$ ，50 和 100）显著增强了 BMSC 细胞的迁移，并且从Figure 3.19b 中可以观察到 $\\mathrm{GH}_{100}$ 的 BMSC 细胞迁移数量相对于 SCP 增加了$101.06\\%$ ，这是由于 GelMA/PEGDA/GO-HAP 冷冻凝胶释放的 $\\mathrm{Ca}^{2+}$ 可以促进BMSC 的迁移。  \n\n![](images/9cc4bdb5f75682c3d5b5930e6ababa8f547857931703664a7e604346c2388648.jpg)  \nFigure 3.19 (a) Migration assay of BMSCs exposed to different substrates for $24\\mathrm{h}$ ,  \n\nscale bar ${\\tt\\mathrm{=}}200\\ {\\upmu\\mathrm{{m}}}$ . (b) Number of migrated BMSCs on different substrates,\\* and # represented $p<0.05$ when compared with SCP and GP10-5, respectively.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 90,
+        "chunk": "# 3.3.7 体外成骨性能  \n\nFigure 3.20a 是不同 GelMA/PEGDA/GO-HAP 冷冻凝胶修饰 CFRPEEK 样品和 BMSC 细胞共培养 7 天和 14 天的 ALP 活性定量分析图。SCP 表现出最差的ALP 活性，与其他组之间有显著性差异。GHX（ $X=25$ ，50 和 100）的 ALP 活性高于 GP10-5，并且 GH100 在第 14 天的 ALP 活性相较于 SCP 提高了 $157.08\\%$ ，这与 ALP 染色结果一致（Figure 3.20b）。在培养 14 天后， $\\mathrm{\\GH_{100}}$ 表面ALP 染色是最深的。以上的结果说明 GelMA/PEGDA/GO-HAP 冷冻凝胶修饰 CFRPEEK 可以促进BMSC 细胞的早期分化。  \n\n![](images/dcfe65883a2f59f51aae87452c4ba9d4486dd51320e1e8c10c657bde2089a54a.jpg)  \nFigure 3.20 (a) Alkaline phosphatase (ALP) activity after osteogenic induction on various samples for 7 and 14 days, \\* represented $p<0.05$ when compared with SCP.  \n\n(b) ALP staining on various samples.  \n\n细胞外基质矿化是成骨细胞晚期分化的标志[276]。在与BMSC 细胞共培养 21天后，利用ARS 染色法探究不同样品表面的细胞外基质矿化情况。Figure 3.21a为不同样品表面的ARS 染色结果。与ALP 染色结果相似，在第 21 天时，在 $\\mathbf{GP}_{10}.$ -5 表面观察到比SCP 更多、更大的红色钙化结节。在 $\\mathrm{GH_{X}}$ （ $X=25$ ，50 和 100）表面上观察到更多的深红色结节区域，特别是 $\\mathrm{GH}_{100}$ ，这表明 GelMA/PEGDA/GO-HAP 冷冻凝胶修饰 CFRPEEK 成骨能力显著增强。Figure 3.21b 为不同样品表面细胞外基质矿化的定量分析结果， $\\mathrm{GH}_{100}$ 表面的钙化结节量相对于 SCP 增多了$65.18\\%$ 。根据上述研究结果，多功能的三维海绵状大孔冷冻凝胶层参与了成骨分化过程，并进一步促进了磺化 CFRPEEK 的晚期成骨分化。  \n\n![](images/7d6287b15bf0d737576f3fc7c0050ef98ff1bc9b558e8eb44b5ca80afbd187c6.jpg)  \nFigure 3.21 (a) Calcium deposition on various sulfonated CFRPEEK substrates after culture of BMSCs for 21 days, \\* and # represented $p<0.05$ when compared with SCP and GH25, respectively. (b) Alizarin red staining (ARS) on various samples.  \n\n为了进一步验证GelMA/PEGDA/GO-HAP冷冻凝胶修饰CFRPEEK对BMSC细胞成骨分化的影响，通过 RT-PCR 探究了不同样品上 BMSC 细胞成骨相关基因（ALP、Col-Ⅰ、BMP-2 和 Runx2）的表达水平。结果如 Figure 3.22 所示，与SCP 相比， $\\mathbf{GP}_{10-5}$ 和 $\\mathrm{GH_{X}}$ （ $X=25$ ，50 和100）的成骨相关基因的表达均增加。在培养14 天时， $\\mathrm{GH}_{100}$ 中的 ALP、Col-Ⅰ、BMP-2 和 Runx2 的表达水平相关比 SCP中 的 分 别 提 高 了 $151.11\\%$ 、 $89.79\\%$ 、 $150.19\\%$ 和 $116.36\\%$ ， 这 表 明GelMA/PEGDA/GO-HAP 冷冻凝胶修饰 CFRPEEK 具有显著的促进成骨的能力。GelMA/PEGDA/GO-HAP 冷冻凝胶层的 3D 海绵状大孔、GO 和 $\\mathrm{Ca}^{2+}$ 在促进CFRPEEK 成骨性能方面具有协同作用。3D 海绵状大孔冷冻凝胶层具有适当的孔径和良好的孔隙渗透性，能够促进 BMSC 细胞的粘附、迁移和矿化[292, 310]。以往研究表明，GO 能在一定程度上促进成骨细胞和干细胞的成骨分化[311]。GO 还作为 HAP 的载体和释放平台，可以不断释放 $\\mathrm{Ca}^{2+}$ ，促进细胞骨架与细胞外基质间的识别和粘附，从而增强成骨细胞的增殖和分化能力[292, 298]。因此，3D 海绵状大孔冷冻凝胶和 GO-HAP 纳米复合材料在增强磺化 CFRPEEK 的成骨能力、促进BMSC 细胞中ALP 的分泌和细胞外基质矿化、刺激成骨相关基因的表达方面发挥了重要作用。  \n\n![](images/23b78c0afd267846fe47f77ae9e3d080d4465c161e9b0307408adc9020a82191.jpg)  \nFigure 3.22 Quantification the expression of ALP, Col-Ⅰ, BMP-2 and Runx2 after BMSCs culturing on various samples for 7 and 14 days by RT-PCR, \\*, # and & represented $p<0.05$ when compared with SCP, GP10-5 and GH25, respectively.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 91,
+        "chunk": "# 3.3.8 体外成血管性能  \n\n内皮细胞的血管生成和干细胞的成骨在骨重塑过程中是相辅相成的[312]。通过对 HUVEC 在 GelMA/PEGDA/GO-HAP 冷冻凝胶修饰 CFRPEEK 上的细胞增殖、粘附、扩散、迁移和管的形成能力等的研究来判断 GelMA/PEGDA/GO-HAP冷冻凝胶修饰 CFRPEEK 的血管生成潜力。HUVEC 在不同样品上培养 1 和 3 天后的增殖结果如Figure 3.23 所示。1 天后，每组样品间细胞增殖无显著差异； 3天后，所有样品的细胞增殖均明显提高； $\\mathrm{GH_{X}}$ （ $X=25$ ，50 和 100）的细胞增殖明显高于其他两组，其中GH100的HUVEC细胞增殖水平相较于SCP提高了 $14.53\\%$ ，这表明 GelMA/PEGDA/GO-HAP 冷冻凝胶修饰 CFRPEEK 具有优越的 HUVEC细胞相容性。  \n\n![](images/f5e9c52a1738ecdba66a41af254f5737b5be620798dce6bdc1ce88e205bcf3d2.jpg)  \nFigure 3.23 HUVEC proliferation on various samples after culturing for 1 and 3 days,\\*, #, $\\&$ and $\\mathfrak{a}$ represented $p<0.05$ when compared with SCP, GP10-5, GH25 and GH50.  \n\n利用 CLSM 图像观察 HUVEC 细胞在不同样品上的细胞骨架（红色）和细胞核（蓝色），如Figure 3.24a 所示。与SCP 相比，其他样品上的 HUVEC 细胞，特别是GH100，扩散良好、产生更成熟的肌动蛋白，并且生成更多的微血管结构。使用 Image J 软件分析 HUVEC 在不同 CFRPEEK 表面的相对位置，以判断HUVEC 在不同样品表面上的迁移能力。结果如 Figure 3.24b 所示，在 GP10-5 和GHX（ $X=25$ ，50 和 100）上的 HUVEC 细胞比 SCP 扩散得更深，这是由于冷冻凝胶层相互连接的大孔结构能够吸收大量的水，提供足够的氧气和营养物质，促进HUVEC 细胞生长、扩散并向下迁移，从而形成三维微血管结构[296]。  \n\n![](images/cdf663b76a2a7ac6febdd058fecca0f814b32f0c48974c86c3857413a54d736f.jpg)  \nFigure 3.24 (a) CLSM of HUVECs incubated on different substrates for 3 day.  \n\nTRITC-phalloidin staining in red represented cytoskeleton, whereas DAPI staining in blue represented cell nuclei, scale bar ${\\tt\\mathrm{=}}40{\\upmu\\mathrm{m}}$ . (b) Representative 3D CLSM images of HUVEC migration into different substrates stained using TRITC-phalloidin for cytoskeletal organization. scale bars $=40~{\\upmu\\mathrm{m}}$ .  \n\n利用体外Transwell 细胞迁移实验研究不同样品对HUVEC 细胞的迁移影响，结果如 Figure 3.25a 所示。培养 24 小时后，在 SCP 仅观察到少量的 HUVEC 细胞迁移，在 GHX（ $X=25$ ，50 和 100）中观察到明显的细胞迁移。定量分析结果表明 HUVEC 细胞在 GH100 上的迁移数量相对于 SCP 增多了 $166.62\\%$ （Figure3.25b），这说明 GelMA/PEGDA/GO-HAP 冷冻凝胶修饰 CFRPEEK 能够促进HUVEC 细胞迁移。  \n\n![](images/b3387c5621a2e59e9bc71f54f4cc967d513f84c2ea1e99598395fca2fef7159c.jpg)  \nFigure 3.25 (a) Migration assay of HUVECs exposed to different substrates for $24\\mathrm{h}$ , Scale bar ${\\tt\\tau}=200{\\upmu\\mathrm{m}}$ . (b) Number of migrated HUVECs on different substrates,\\* and # represented $p<0.05$ when compared with SCP and GP10-5, respectively.  \n\n通过在基质胶上培养 HUVEC 研究 GelMA/PEGDA/GO-HAP 冷冻凝胶修饰CFRPEEK 的管形成能力，分析结果如 Figure 3.26a 所示。暴露于 SCP 的 HUVEC仅有少量的管形成。与 SCP 相比， GH100 上的 HUVEC 的管形成明显增加。使用 Image J 计算形成管的总分支长度，结果如 Figure 3.26b 所示。在 GH100 上形成的管的分支长度最长，相较于 SCP 增长了 $111.18\\%$ ，血管网络结构最密集，这说明 GelMA/PEGDA/GO-HAP 冷冻凝胶修饰 CFRPEEK 能够在体外诱导血管生成。根据之前的报道，许多研究人员已经将 GO 用于组织工程植入物，并发现适当浓度的GO 可以有效地诱导血管生成。石墨烯基材料还能够从已有的血管系统中形成新的毛细血管[313, 314]。  \n\n![](images/7d65787470a9672e96c755e6bcb288f503da2f17686e5589b2cf46943edb345d.jpg)  \n\nFigure 3.26 (a) Tube forming ability of HUVECs cultured on Matrigel, Scale bar   \n${\\tt\\tau}=200\\ \\upmu\\mathrm{m}$ . (b) Total branching length the formed tube on different samples, ,\\*, #, & and a represent $p<0.05$ when compared with SCP, GP10-5, GH25 and GH50, respectively.  \n\n综上所述，3D 海绵状大孔 GelMA/PEGDA/GO-HAP 冷冻凝胶修饰 CFRPEEK增强了HUVEC 的增殖、粘附和迁移并加速了管的形成，这些结果与之前的研究一致，即3D 海绵状大孔结构有利于细胞的粘附和扩散，GO-HAP 中的GO 进一步促进了细胞的迁移和血管生成。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 92,
+        "chunk": "# 3.3.9 体内成骨整合性能探究  \n\n细胞实验结果表明 GelMA/PEGDA/GO-HAP 冷冻凝胶修饰 CFRPEEK 表现出优异的体外血管化和成骨特性，说明这类材料具备了作为骨科植入物的基本条件。它的骨整合性能的优劣还需要通过体内组织对 GelMA/PEGDA/GO-HAP 冷冻凝胶修饰CFRPEEK 的反应来研究。为此，本研究团队建立了大鼠颅骨缺损模型，以探究多功能磺化CFRPEEK 植入物的体内骨重塑能力。基于在体外细胞实验中表现出优越性能，选择 $\\mathrm{GH}_{100}$ 进行大鼠颅骨缺损植入实验。将不同的CFRPEEK 植入物（SCP、GP10-5、GH100）植入大鼠颅骨两侧，其中以空白孔（Blank）作为对照组。在术后4 周和12 周，用micro-CT 扫描含有植入物的颅骨，以探究新骨的生成情况。各组 CFRPEEK 植入物周围新生骨组织的 2D 和 3D 重建图像如Figure 3.27a 所示。在术后 4 周，每组植入物周围都有少量新骨生成。植入 12周后，SCP 植入物周围新生骨的数量大于空白组， $\\mathbf{GP}_{10-5}$ 和 $\\mathrm{\\GH_{100}}$ 周围的新生骨数量均明显大于其他两组，其中 GH100 植入物几乎完全被新生骨组织包围，这表明 GelMA/PEGDA/GO-HAP 冷冻凝胶的修饰促进了磺化 CFRPEEK 植入物的骨修复能力。Figure 3.27b 是新生骨组织参数的定量分析结果，包括骨体积/总体积（BV/TV）、骨小梁数（Tb.N）和骨小梁厚度(Tb. Th)。在第 12 周， $\\mathrm{\\GH_{100}}$ 的新生骨的 BV/TV、 Tb.N 和 Tb. Th 相较于 SCP 增加了 $72.96\\%$ 、 $78.95\\%$ 和 $34.98\\%$ ，这说明 GelMA/PEGDA/GO-HAP 冷冻凝胶层显著的提升了 CFRPEEK 的骨重塑和骨整合能力。  \n\n![](images/772ce123815b4b28730db83c2b6e2dc1bd32cb07d405f92bd5251765bbc15f11.jpg)  \nFigure 3.27 (a) 2D and 3D reconstruction images by micro-CT scanning after 4 and  \n\n12 weeks implantation (red dotted frame denotes the bone defect site). (b)   \nQuantitative analysis of Micro-CT data including BV/TV, Tb.N, and Tb.Th at 4 and   \n12 weeks, \\*, # and $\\&$ represent $p<0.05$ when compared with the blank, SCP and GP10-5, respectively.  \n\n为了进一步探究不同 CFRPEEK 植入物周围新生骨组织和新血管的生成情况，在植入 4 周和 12 周后对颅骨标本进行组织学染色（H & E、Masson 和 VanGieson 染色）。如 Figure 3.28 所示，黑点（长碳纤维）和棕色（PEEK 基质）的混合区域代表CFRPEEK 植入物。在实验动物的颅骨中未发现炎症或坏死，这说明植入物无毒且具有长期的生物相容性。H  &  E、Masson 和 Van Gieson 染色结果显示，在手术4 周后，SCP 植入物周围形成了一层薄薄的骨样基质（红色箭头）。GP10-5 和 $\\mathrm{\\GH_{100}}$ 比SCP 形成了更广泛的类骨基质区域。当时间延长到 12 周时，不同植入物周围的新生骨增加，更多成熟的新骨（黑色箭头）牢固地附着在GH100 上，并在其表面扩张，这表明 GelMA/PEGDA/GO-HAP 冷冻凝胶修饰CFRPEEK 植入物具有良好的新骨生成能力。GH100 上还生成了更多的新血管（绿色箭头）[278, 315]，这与体外血管生成结果一致。上述结果表明，3D 海绵状大孔GelMA/PEGDA/GO-HAP 冷冻凝胶层能显著加速体内的骨沉积和新血管的生成，提高了CFRPEEK 植入物的骨整合能力，为多功能骨科植入物的开发提供了更多的可能。  \n\n![](images/665c283a8d34fda3f7fb6ab1462f6e600457de49b2ac24e62863730fb02843a2.jpg)  \nFigure 3.28 H & E, Masson and Van Gieson staining of the calvarial defect regions after treatment with different samples for 4 and 12 weeks. [M, Materials; NB, new bone (black arrows); NV, new vessels (green arrows); OM, osteoid matrix (red arrows)].  \n\n除体内骨整合能力外，体内生物毒性是 CFRPEEK 能否作为骨科植入物的重要标准。植入12 周后，用H & E 染色法探究实验动物的主要器官是否发生病变。  \n\nFigure 3.29 为实验大鼠的心、肝、脾、肺和肾的组织染色图像。从染色结果可以看出，实验大鼠的主要器官的结构保持正常，没有明显的器官损伤或炎性损伤，这说明多功能磺化CFRPEEK 植入物作为成骨植入物没有明显的生物毒性。  \n\n![](images/5e2fcd4b06a09c32bd1bb983e0f397db6f8503fcf88104bff81cba8aa2ea3797.jpg)  \nFigure 3.29 Histological observation of H & E staining of tissues (heart, liver, spleen, lung, and kidney) after 12 weeks of treatments, scale bar $=40\\upmu\\mathrm{m}$ .",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 93,
+        "chunk": "# 3.4 本章小结  \n\n通过原位键合法制备了 GO-HAP 纳米复合材料，再基于自由基光聚合的冷冻凝胶技术开发了一种多功能GelMA/PEGDA/GO-HAP 冷冻凝胶修饰CFRPEEK植入物。  \n\n（1）体外成血管实验表明，在 GH100 上形成的管的分支长度最长，相较于SCP 增长了 $111.18\\%$ ，血管网络结构最密集，这说明该多功能植入物表面的 3D海绵状大孔结构和GO 促进了 HUVEC 细胞的长入和迁移，增强了 CFRPEEK 植入物的体外成血管能力。  \n\n（2）优异的表面亲水性和钙离子的受控释放有利于 BMSC 细胞的增殖、粘附和成骨分化，其中 BMSC 细胞在 $\\mathrm{\\GH_{100}}$ 上的增殖相较于 SCP 提高了 $24.41\\%$ ，ALP 活性提高了 $157.08\\%$ 。  \n\n（3）大鼠颅骨缺损实验进一步表明， $\\mathrm{GH}_{100}$ 周围的新生骨的骨小梁数目相较于SCP 提高了 $78.95\\%$ ，这说明 GelMA/PEGDA/GO-HAP 冷冻凝胶修饰 CFRPEEK植入物可以迅速诱导新骨生成和新血管生成，显著提高了 CFRPEEK 植入物的成骨固定和骨重塑能力。  \n\n综上所述，本研究为开发具有血管生成能力的骨科植入物提供了新的思路，并扩大了CFRPEEK 材料的临床应用范围。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 94,
+        "chunk": "# 第 4 章 pH 响应性 MOF 水凝胶修饰 CFRPEEK 的制备及其免疫/成血管/成骨能力的研究",
+        "category": " Introduction"
+    },
+    {
+        "id": 95,
+        "chunk": "# 4.1 前言  \n\n骨缺损处的骨整合是一个复杂的动态过程，包括三个阶段：炎症反应、血管生成和新骨生成[316, 317]，这三个阶段不是孤立的，而是相互重叠和协同的。巨噬细胞的免疫反应、内皮细胞的血管生成和成骨细胞的骨新生，每个阶段都可以通过一些共同的细胞间信号通路与其它阶段相互作用[318-320]。植入物和组织之间的相互作用总是发生在植入物表面上，控制和改善植入物的表面特性来优化植入物的生物相容性和生物活性是一种有效的促进骨整合方法[321]。在植入物植入后，如果上述细胞能够首先到达并占据植入物表面，则可以促进界面处的骨结合，延长植入物在体内的寿命。在前两章工作的基础上，本章工作拟进一步通过表面多功能设计提高 CFRPEEK 植入物的抗炎、血管生成和成骨能力，从而增强CFRPEEK 的骨整合性能以保持植入物与组织界面的长期稳定性。  \n\n羟基磷灰石以纳米针状晶体存在人体骨骼中 [322, 323]，这些纳米晶体的有序排列使得骨组织具有机械性能[324]。在骨科植入物中掺入纳米羟基磷灰石有望改善骨科植入物的超微结构和骨传导性[325]。  \n\n金属有机框架（MOF）是具有多孔结构的有机-无机杂化材料，通过在金属离子/团簇和有机配体之间形成配位键而制成 [326-329]。因其多变的结构、大的比表面积、优异的载药能力和生物降解性受到研究人员的广泛关注[330]。  \n\n$\\mathrm{Mg^{2+}}.$ 是人体骨骼中的一种微量元素，在骨代谢过程中维持着局部微环境的平衡。近年来，研究人员试图通过在骨植入物中添加生物活性 $\\mathrm{Mg^{2+}}$ 来诱导血管化骨愈合[331, 332]。 $\\mathrm{Mg^{2+}}$ 可以调节细胞行为，包括增强细胞粘附和促进细胞分化，还可以促进新血管生成并刺激骨局部再生和愈合，从而增强骨整合[333, 334]。 $\\mathrm{Mg^{2+}}$ 能影响巨噬细胞的极化，控制炎性细胞因子的释放，抑制骨微环境中的炎症反应[335]。  \n\n没食子酸（GA）是一种低分子量的植物衍生有机茶多酚[336]。它在抗炎和抗氧化方面具有良好的治疗作用，在免疫细胞分化、激活和维持免疫系统稳定性的过程中发挥一系列作用[337, 338]。多项研究证明，GA 通过影响巨噬细胞相关蛋白的表达以及M1 型巨噬细胞极化来调整炎症反应[339, 340]。  \n\n由 GA 和 $\\mathrm{Mg^{2+}}$ 制备的Mg-GA 金属有机框架（MOF）具有生物相容性、血管生成和抗炎特性[334,341]。虽然先前的研究表明，将 HAP 或Mg-GA 单独结合到骨植入物中可以增强植入物在体内的骨整合，但同时使用它们来促进骨植入物的骨整合和骨生成的实例很少。  \n\n本研究考虑到植入物在植入后的不同骨整合阶段所需的炎症反应、血管生成和成骨特性，设计并开发了核壳结构的羟基磷灰石 $@$ 镁-没食子酸（HAP@Mg-GA）MOF 纳米颗粒，其中纳米羟基磷灰石为核层，Mg-GA 为壳层。通过紫外辐照的方法在磺化 CRPEEK 表面上制备羟基磷灰石 $@$ 镁-没食子酸/甲基丙烯酰化壳聚糖（HAP@Mg-GA/CSMA）MOF 水凝胶层。CSMA 是可以通过光引发聚合且对pH 高度敏感，所以它不仅可以将核壳结构的 MOF 纳米颗粒负载到磺化CFRPEEK 的表面，还可以在低 pH 条件下控制 $\\mathrm{HAP}@\\mathrm{Mg-GA~MOF}$ 纳米颗粒中生物活性物质的持续释放。在骨整合早期阶段（低 $\\mathrm{\\pH}\\mathrm{\\cdot}$ ），负载在 CSMA 水凝胶上的HAP@Mg-GA 首先准确地释放抗炎药物GA 和微量元素 $\\mathrm{Mg}^{2+}$ 来应对炎症反应，为接下来的成骨分化创造良好的免疫微环境。同时，释放的 $\\mathrm{Mg}^{2+}$ 还可以促进血管的原位生成。在骨整合的晚期（pH 值为 7.4），钙的长期持续释放有利于新骨的生成，恢复植入物周围的骨稳态，以及促进骨-植入物的整合。在磺化CFRPEEK 植入物的表面上构建 pH 响应的 MOF 水凝胶，有利于 CFRPEEK 植入物适应植入后的动态骨整合过程。本章通过对改性CFRPEEK 植入物的表面形貌、亲水性、表面电势、蛋白吸附能力、不同 pH 下的缓释行为和体外矿化能力进行研究，探究了 pH 响应性 MOF 水凝胶修饰 CFRPEEK 植入物的性能优势；通过体外细胞实验，研究了改性CFRPEEK 植入物的抗炎、成血管和成骨能力；通过大鼠皮下植入和兔胫骨缺损实验，研究了该植入物在体内抗炎、成血管和成骨分化行为。总的来说，研究结果为设计改进骨科植入物提供了一种新颖的策略，并为惰性生物材料表面的多功能设计提供了一个实用的选择。Figure 4.1 为本章的技术路线示意图。  \n\n![](images/64558ed95cc44ea92260c21f5c2cc3a240a7730f8429f05dbfcf320db941e325.jpg)  \nFigure 4.1 (a) Diagram depicting the synthesis of HAP@Mg-GA MOF nanoparticles.  \n\n(b) Preparation of stimuli-responsive metal–organic framework hydrogel-decorated sulfonated CFRPEEK implants. (c) Schematic illustration of stimuli-responsive metal–organic framework hydrogel-decorated sulfonated CFRPEEK implants for enhanced osseointegration (regulation of inflammation response, angiogenesis, and bone regeneration).",
+        "category": " Introduction"
+    },
+    {
+        "id": 96,
+        "chunk": "# 4.2 实验部分",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 97,
+        "chunk": "# 4.2.1 实验材料与仪器",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 98,
+        "chunk": "# 1. 实验材料  \n\nTable 4.1 The materials and reagents.   \n\n\n<html><body><table><tr><td>名称</td><td></td><td>缩写　产品规格</td><td>生产厂家</td></tr><tr><td>纳米羟基磷灰石</td><td>HAP</td><td>≥97%</td><td>上海阿拉丁生化科技股份有限公司</td></tr></table></body></html>  \n\n<html><body><table><tr><td>名称</td><td>缩写</td><td>产品规格</td><td>生产厂家</td></tr><tr><td>氯化镁</td><td>MgCl2</td><td>AR</td><td>上海阿拉丁生化科技股份有限公司</td></tr><tr><td>壳聚糖</td><td>CS</td><td>200-</td><td>上海阿拉丁生化科技股份有限公司</td></tr><tr><td></td><td></td><td>400</td><td></td></tr><tr><td></td><td></td><td>mPa.s</td><td></td></tr><tr><td>没食子酸</td><td>GA</td><td>AR</td><td>上海易恩化学技术有限公司</td></tr><tr><td>氢氧化钾</td><td>KOH</td><td>AR</td><td>北京化工厂</td></tr><tr><td>牛血清白蛋白</td><td>BSA</td><td>>98%</td><td>上海碧云天公司</td></tr><tr><td>IL-10/ TNF-α 酶联免</td><td></td><td></td><td>美国英杰生命技术有限公司</td></tr><tr><td>疫试剂盒</td><td></td><td></td><td>（ Invitrogen）</td></tr><tr><td>脂多糖</td><td>LPS</td><td>AR</td><td>上海碧云天公司</td></tr><tr><td>FITC 抗小鼠 CD206</td><td></td><td></td><td>BioLegend</td></tr><tr><td>抗体</td><td></td><td></td><td></td></tr><tr><td>PE 抗iNOS 抗体</td><td></td><td></td><td>BioLegend</td></tr><tr><td>活性氧检测试剂盒</td><td>ROS</td><td></td><td>上海碧云天公司</td></tr><tr><td></td><td>Assay</td><td></td><td></td></tr><tr><td></td><td>Kit</td><td></td><td></td></tr><tr><td>-氧化氮检测试剂盒</td><td></td><td></td><td>上海碧云天公司</td></tr><tr><td>24孔 Transwell 小室</td><td></td><td>3422</td><td>美国康宁公司</td></tr><tr><td>基质胶</td><td></td><td>无酚红</td><td>BD 生物科学技术有限公司</td></tr><tr><td>结晶紫</td><td></td><td>AR</td><td>北京索莱宝科技有限公司</td></tr><tr><td>CD86一抗</td><td></td><td></td><td>武汉赛维尔生物科技有限公司</td></tr><tr><td>CD163一抗</td><td></td><td></td><td>武汉赛维尔生物科技有限公司</td></tr><tr><td>CD31一抗</td><td></td><td></td><td>武汉赛维尔生物科技有限公司</td></tr><tr><td>Zoletil 50</td><td></td><td></td><td>法国virbac 公司</td></tr><tr><td>速眠新</td><td></td><td></td><td>吉林省敦化市圣达动物药品有限公</td></tr><tr><td colspan=\"2\"></td><td>司</td><td></td></tr></table></body></html>\n\n涉及的其它实验材料与第二章相同，详见 2.2.1 表 Table 2.1。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 99,
+        "chunk": "# 2. 实验仪器  \n\nTable 4.2 The experimental apparatus.   \n\n\n<html><body><table><tr><td>仪器名称</td><td>型号</td><td>生产厂家</td></tr><tr><td>Revetest划痕测试仪</td><td>Revetest</td><td>安东帕（上海）商贸有限 公司</td></tr><tr><td>透射电子显微镜</td><td>HT7800 (TEM)</td><td>日立株式会社</td></tr><tr><td>接触角测量仪</td><td>DSA25</td><td>德国KRUSS公司</td></tr><tr><td>固体表面 Zeta电位分析</td><td>SurPASS (EDS)</td><td>安东帕（上海）商贸有限</td></tr><tr><td>仪</td><td></td><td>公司</td></tr><tr><td>流式细胞仪</td><td>FACS Calibur</td><td>美国BD生物科学公司</td></tr><tr><td>电感耦合等离子体发射光</td><td>（ ICP-</td><td></td></tr><tr><td></td><td>Agilent  725</td><td>安捷伦科技（中国）有限</td></tr><tr><td>谱仪</td><td>OES)</td><td>公司</td></tr></table></body></html>\n\n涉及的其它实验仪器与第二章相同，详见 2.2.1 表 Table 2.2。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 100,
+        "chunk": "# 4.2.2 HAP@Mg-GA MOF 纳米颗粒的制备与表征  \n\nHAP@Mg-GA MOF 纳米颗粒是通过纳米羟基磷灰石、 $\\mathrm{Mg}^{2+}$ 和GA 之间的库仑相互作用和螯合作用制得的，即纳米羟基磷灰石的 $\\mathrm{Ca}^{2+}$ 与没食子酸的-COO-之间的库仑相互作用和螯合作用首先诱导没食子酸在纳米羟基磷灰石上沉积。当纳米羟基磷灰石表面的 $\\mathrm{Ca}^{2+}$ 完全被没食子酸覆盖，没食子酸暴露出的-COO-与 $\\mathrm{Mg}^{2+}$ 之间的库仑相互作用和螯合作用使得 Mg-GA 壳沉积到纳米羟基磷灰石上，最后形成了核壳结构的 HAP@Mg-GA MOF 纳米颗粒[342, 343]。Figure 4.1a 是 ${\\mathrm{HAP}}@{\\mathrm{Mg-}}$ GA 制备技术路线图。具体实验步骤如下：  \n\n将1g 的纳米羟基磷灰石超声分散到 $100\\mathrm{mL}$ 的去离子水中，随后用 $10\\mathrm{M}$ 的KOH 水溶液调节 pH 在 8-9 之间；将 $0.19\\mathrm{g}$ 没食子酸和 $0.05\\mathrm{g}$ 氯化镁分别加入到纳米羟基磷灰石分散液中，将此混合液放入三颈烧瓶中，于 $120^{\\circ}\\mathrm{C}$ 回流搅拌，反应 $24\\mathrm{h}$ ，冷却至室温，然后进行高速离心处理，取 $\\mathrm{HAP}@\\mathrm{Mg-GA}$ 沉淀物；沉淀物用蒸馏水和无水乙醇分别洗涤三次，并以 $10000\\mathrm{rpm}$ 高速离心回收；将回收的沉淀物在 $60^{\\circ}\\mathrm{C}$ 的真空烘箱中干燥 $24\\mathrm{~h~}$ ，得到棕褐色的核壳结构的羟基磷灰石 $@$ 镁-没食子酸MOF 纳米颗粒（ $\\mathrm{HAP}@\\mathrm{Mg-GA})$ ）。  \n\n使用 XRD 和 XPS 检测了 HAP $@$ Mg-GA 的晶体结构和组成；通过 TEM 和  \n\nSEM 分析了 GO-HAP 的形貌。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 101,
+        "chunk": "# 4.2.3 甲基丙烯酰化壳聚糖（CSMA）的制备与表征  \n\n甲基丙烯酰化壳聚糖（CSMA）是按照文献报道的方法制备的[344]。具体如下：  \n\n配制 $200\\mathrm{mL}1.5\\%$ 壳聚糖溶液，溶剂为 $4\\%$ （v/v）醋酸溶液， $40^{\\circ}\\mathrm{C}$ 磁力搅拌直至壳聚糖溶解；向上述溶液中缓慢滴加 $16~\\mathrm{mL}$ 的甲基丙烯酸酐， $40^{\\circ}\\mathrm{C}$ 避光磁力搅拌反应 3 小时；反应完成后，将反应液置于透析袋中，用蒸馏水透析 7 天，除去未反应的甲基丙烯酸酐；将透析液在真空冷冻干燥机中干燥，得到甲基丙烯酰化壳聚糖（CSMA）。  \n\n在常温条件下，将少量的壳聚糖和甲基丙烯酰化壳聚糖（CSMA）分别溶解于含 $2\\%$ 氘代乙酸的氘代水（ $\\mathrm{\\DeltaD}_{2}\\mathrm{O}$ ）中，通过 $400\\mathrm{MHz}$ 核磁共振波谱仪测定它们的 $^1\\mathrm{H}$ NMR 谱，以判断甲基丙烯酰化壳聚糖（CSMA）的分子结构。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 102,
+        "chunk": "# 4.2.4 磺化 CFRPEEK 复合材料的制备  \n\n磺化 CFRPEEK 复合材料的制备步骤与第三章相同，详见 3.2.3 磺化CFRPEEK 复合材料的制备，其中尺寸为 $\\Phi\\ 8{\\times}1.5\\ \\mathrm{mm}$ 的磺化 CFRPEEK 用于表面表征、体外细胞实验和大鼠的皮下植入实验，尺寸为 $\\Phi\\ 5\\times6\\ \\mathrm{mm}$ 的磺化CFRPEEK 用于兔的胫骨缺损实验。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 103,
+        "chunk": "# 4.2.5 MOF 水凝胶修饰磺化 CFRPEEK 的制备  \n\n（1）CSMA/ HAP@Mg-GA 凝胶前体液的制备  \n\n在避光条件下，将 HAP@Mg-GA 按照 $0.5\\ \\mathrm{wt\\%}$ 的浓度加入到配制好的 3wt%CSMA 水溶液中。为了使 HAP@Mg-GA 均匀的混合到 CSMA 水溶液中，将混合溶液先超声分散 $30\\ \\mathrm{min}$ 再在室温下磁力搅拌 $8\\mathrm{~h~}$ ，这样就得到了CSMA/HAP@Mg-GA 凝胶前体液。  \n\n（2）MOF 水凝胶修饰 CFRPEEK 的制备  \n\n在避光条件下，将磺化 CFRPEEK 复合材料按 $100~{\\upmu\\mathrm{L}}/{\\mathrm{cm}}^{2}$ 的比例浸入含有HAP@Mg-GA/CSMA 水凝胶前体液 $(\\mathrm{HAP}@\\mathrm{Mg-GA:0.5wt^{0}/_{0},C S M A:3w t^{0}/_{0}})$ 中，在室温下静置 $15{-}30\\ \\mathrm{min}$ ，使得具有多孔结构的磺化 CFRPEEK 复合材料与  \n\nHAP@Mg-GA/CSMA 混合溶液充分接触。在保护气氛下，将浸没在溶液中的CFRPEEK 置于在波长 $365~\\mathrm{nm}$ 、光强 $10\\mathrm{\\mW/cm^{2}}$ 的紫外灯下辐照 $60~\\mathrm{{min}}$ 。完成后，将上述CFRPEEK 浸泡在蒸馏水中，以除去未反应的水凝胶前体液，最后在冷冻干燥机里进行干燥备用。  \n\n各组CFRPEEK 样品用如下缩写表示：  \n\nSCP：磺化 CFRPEEK；  \n\nMACS: 甲基丙烯酰化壳聚糖（CSMA）修饰的磺化 CFRPEEK（CSMA:3wt%）;HAP: 纳米羟基磷灰石/甲基丙烯酰化壳聚糖（Nano-HAP/CSMA）修饰的磺化CFRPEEK（HAP:0.5wt%,CSMA:3wt%）;  \n\nMGH: 羟基磷灰石 $@$ 镁-没食子酸/甲基丙烯酰化壳聚糖（HAP@Mg-GA/CSMA）修饰的磺化 CFRPEEK（HAP@Mg-GA:0.5wt%,CSMA:3wt%）。  \n\n采用SEM 对各组样品的表面形貌和截面形貌进行表征； ATR-FTIR 和EDS 用于表征各组样品的表面化学组成；每个样品组的水接触角使用接触角测量仪测定，每个样品在3 个不同的区域进行测定，每组样品重复测定 2 次。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 104,
+        "chunk": "# 4.2.6 水凝胶层的附着力测试  \n\n水凝胶层与磺化CFRPEEK 之间的附着力由 Revetest 划痕测试仪确定。安装在划痕测试仪上的声发射（AE）传感器能捕捉水凝胶层产生裂纹时的声音，可用于检测划痕过程中裂纹的产生。利用划痕测试仪上的划痕自动全景成像装置观察划痕形态。具体如下：  \n\n设置仪器模式为渐进加载模式，划痕长度设置为 $5\\mathrm{mm}$ ，法向力设置为从 1N线性增加到 $100\\mathrm{N}$ ，划痕速率设为 $2\\mathrm{{mm}/\\mathrm{{min}}}$ ，采样频率为 $30\\mathrm{Hz}$ ；将 MACS 样品放入仪器中，金刚石压头在设定的法向力(Fn)和划痕速率下对 MACS 表面进行划刻，以获得声发射信号；由仪器自带的全景成像装置拍摄划痕的形貌；对获得的声发射信号和划痕形貌进行分析。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 105,
+        "chunk": "# 4.2.7 表面 zeta 电势测试  \n\n不同 CFRPEEK 样品表面的 zeta 电势是用固体表面 Zeta 电位分析仪测定的。将不同的CFRPEEK 样品裁切成 $35\\times15\\times1.5~\\mathrm{mm}^{3}$ 大小，以 $0.001\\mathrm{~M~}$ 氯化钾  \n\n（KCl）溶液作为流动电解液，电解液的 $\\mathsf{p H}$ 使用 $0.1\\mathrm{~M~HCl}$ 和 $0.1\\mathrm{~M~NaOH}$ 溶液进行调整，范围为5.0-8.0，探究样品表面的 zeta 电位和pH 的关系曲线。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 106,
+        "chunk": "# 4.2.8 蛋白吸附能力测试  \n\n将不同样品浸泡在 $0.5~\\mathrm{mL}$ 的 $0.5~\\mathrm{mg/mL}$ 牛血清白蛋白（BSA）溶液中，在规定的时间间隔内，收集BCA 溶液并用新鲜的溶液替换。使用 BCA 蛋白检测试剂盒测定收集到的BCA 溶液的浓度，并进一步计算出不同样品的 BSA 蛋白的吸附量。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 107,
+        "chunk": "# $4.2.9\\mathrm{Ca}^{2+}$ 、 $\\mathrm{Mg}^{2+}$ 和GA 在不同 $\\mathsf{p H}$ 下的缓释行为测试  \n\n将HAP 和 MGH 两组样品分别浸没到 $2\\mathrm{mL}$ 的 $\\mathrm{pH}{=}5.5$ 、6.5 和 7.4 的 PBS 溶液中，置于恒温 $37^{\\circ}\\mathrm{C}$ 、转速为 $100\\mathrm{rpm}$ 的摇床；在 1、3、5、7、14、21 天吸出缓释液并重新加入 $2{\\mathrm{~mL~}}$ 的新鲜的 PBS 溶液；用电感耦合等离子体光谱仪测定$\\mathrm{Ca}^{2+}$ 和 $\\mathrm{Mg^{2+}}$ 的缓释效率，用紫外分光光度计测定 GA 的缓释效率。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 108,
+        "chunk": "# 4.2.10 体外矿化行为研究  \n\nSCP，MACS，HAP 和 MGH 的体外矿化研究的实验步骤与第二章相同，详见2.2.7 体外矿化行为研究。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 109,
+        "chunk": "# 4.2.11 细胞实验",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 110,
+        "chunk": "# 4.2.11.1 细胞的培养  \n\n细胞实验使用小鼠单核巨噬细胞白血病细胞（RAW264.7），研究改性CFRPEEK 的抗炎能力；采用人脐静脉内皮细胞（HUVEC），研究改性 CFRPEEK的成血管能力；采用大鼠骨髓间充质干细胞（BMSC），研究改性 CFRPEEK 的成骨能力。大鼠骨髓间充质干细胞（BMSC）的提取培养与传代实验步骤与第二章相同，详见 2.2.8.1。RAW264.7 和 HUVEC 都购自中国医学科学院基础医学研究所细胞资源中心。RAW264.7、HUVEC 和 BMSC 都在 DMEM 完全培养基中常规培养。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 111,
+        "chunk": "# 4.2.11.2 体外炎症反应测试  \n\n1. 采用流式细胞术检测不同样品的体外巨噬细胞极化情况。具体如下：（1）将处在对数生长期的 RAW264.7 细胞首先用 $1~\\mathrm{mL}$ 含 $100~\\mathrm{{ng/mL}}$ 脂多  \n糖（LPS）的 DMEM 培养基孵育 24 小时，再用常规培养基制成密度为 $1\\times10^{5}$   \ncell/mL 细胞悬液；（2）将经过Cobalt 60 灭菌的样品放入48 孔培养板中，用PBS 清洗一遍后，  \n每孔滴加 $1\\mathrm{mL}$ 上述细胞悬液；（3）细胞在培养箱培养 1 天后，弃去原始培养基，细胞通过胰蛋白酶消化  \n收集，用含 $1\\%$ BSA 的 PBS 洗涤细胞两次；（4）使用含有 $1\\%$ BSA 的 PBS 把细胞制成 $1{\\times}10^{7}\\mathrm{cell/mL}$ 的细胞悬液，取  \n$100~\\upmu\\mathrm{L}$ 细胞悬液置于EP 管中待用；（5）按照说明书的推荐用量加入荧光标记的抗体（FITC 抗小鼠 CD206 抗  \n体和PE 抗iNOS 抗体），混匀后置于 $4^{\\circ}\\mathrm{C}$ ，避光孵育30 分钟， $300\\mathrm{g}$ 离心5 分钟，  \n弃掉上清液；（6）在 $0.2~\\mathrm{mL}$ 含 $1\\%$ BSA 的 PBS 中重悬细胞，通过流式细胞仪检测和分  \n析。2. 不同样品上巨噬细胞分泌的炎症因子通过酶联免疫吸附试验（ELISA）测  \n定。具体如下：（1）（2）和上述流式细胞术检测 RAW264.7 细胞极化实验步骤相同；（3）培养3 天后，收集培养基， $300\\mathrm{g}$ 离心培养基5 分钟，取上清液；（4）按照IL-10/ TNF-α酶联免疫试剂盒的说明书将上述收集的上清液制备  \n成反应液（5）在 $450\\mathrm{nm}$ 波长下测定各样品反应液的 OD 值；（6）建立标准曲线，通过标准曲线计算出样品中 IL-10/ TNF-α的浓度。3. 通过实时荧光定量聚合酶链式反应（RT-PCR）研究RAW264.7 细胞在 LPS  \n刺激后在不同样品表面的炎症相关基因的表达情况，具体实验步骤与第二章相同，  \n详见 2.2.8.3 的实验 3。其中 RT-PCR 所需的炎性相关基因的引物对，如 Table 4.3  \n\n所示。  \n\nTable 4.3 Primer pairs to measure inflammation-related genes in RT-PCR.   \n\n\n<html><body><table><tr><td>Genes</td><td>Sequence (5'-3')</td></tr><tr><td>IL-6</td><td>F: GACTTCCATCCAGTTGCCTT R: ATGTGTAATTAAGCCTCCGACT</td></tr><tr><td>IL-10</td><td>F: GAAGACAATAACTGCACCCACT</td></tr><tr><td rowspan=\"2\">iNOS</td><td>R: AGTCGGTTAGCAGTATGTTGT</td></tr><tr><td>F: CCTTTGCTCATGACATCGACCA R: TCCTGCCCACTGAGTTCGT</td></tr><tr><td rowspan=\"2\">CD206</td><td>F: GTCATACCGTGTTGAACCTCT</td></tr><tr><td>R: ACACAATCATTCCGTTCACCAG</td></tr><tr><td rowspan=\"2\">GAPDH</td><td></td></tr><tr><td>F: GAACATCATCCCTGCATCCACT R: GATCCACGACGGACACATTGG</td></tr></table></body></html>  \n\n4. 用活性氧检测试剂盒来检测不同 CFRPEEK 样品上 RAW264.7 细胞的活性氧水平。具体操作方法如下：  \n\n（1）在 DMEM 完全培养基中将处于对数生长期的 RAW264.7 细胞制成细胞，密度为 $5{\\times}10^{4}~\\mathrm{cell/mL}$ ；  \n\n（2）将经过Cobalt 60 灭菌的样品放入48 孔培养板中，用PBS 清洗一遍后，每孔滴加 $1\\mathrm{mL}$ 上述细胞悬液；  \n\n（3）培养 $24\\mathrm{h}$ 后，用含有 $100\\mathrm{ng/mL}$ 脂多糖（LPS）的 DMEM 替换原培养基；  \n\n（4）继续培养 $24\\mathrm{~h~}$ 后，收集细胞，用无血清 DMEM 培养基配制的 $10~\\upmu\\mathrm{M}$ 二氯荧光素-二乙酸酯（DCFH-DA）溶液重悬细胞， $37^{\\circ}\\mathrm{C}$ 孵育 20 分钟后；  \n\n（5）洗涤 3 次，去除残留的 DCFH-DA，用 $0.5~\\mathrm{mL}$ 无血清 DMEM 培养基重悬细胞，荧光显微镜下观察并拍照。  \n\n5. 采用一氧化氮检测（NO）试剂盒检测不同 CFRPEEK 样品上 RAW264.7细胞中的一氧化氮的水平。具体如下：  \n\n（1）（2）（3）和上述RAW264.7 细胞活性氧检测实验步骤相同。（4）继续孵育 $24\\mathrm{h}$ 后，取培养基， $300\\mathrm{g}$ 离心 $5\\mathrm{min}$ ，收集上清液；（5）用 Griess 试剂 I 和 II 依次处理上述上清液，在 $540~\\mathrm{nm}$ 波长处测定各  \n\n孔的OD 值以探究 NO 水平。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 112,
+        "chunk": "# 4.2.11.3 体外成血管性能测试  \n\n1. Cell Counting Kit（CCK-8）试剂盒检测 HUVEC 细胞在材料表面的增殖情况，具体实验步骤与第二章相同，详见 2.2.8.2 的实验1。  \n2. 通过扫描电镜观察 HUVEC 细胞在材料表面的生长情况，具体实验步骤与第二章相同，详见2.2.8.2 的实验 2。  \n3. HUVEC 细胞在不同样品上的粘附与扩散用罗丹明标记的鬼笔环肽和DAPI 染色法进行检测，具体实验步骤与第二章相同，详见 2.2.8.2 的实验3。  \n4. 通过Transwell 实验研究 HUVEC 细胞在不同样品上的迁移性能，具体的实验步骤与第三章相同，详见 3.2.8.2 的实验4。  \n5. 利用基质胶 Matrigel 研究 HUVEC 细胞在不同样品上的血管样网络结构的生成，具体的实验步骤与第三章相同，详见 3.2.8.4 的实验 4。  \n6. 通过实时荧光定量聚合酶链式反应（RT-PCR）研究 HUVEC 细胞在不同样品表面的成血管相关基因的表达情况的具体实验步骤与第二章相同，详见  \n2.2.8.3 的实验 3。其中 RT-PCR 所需的成血管相关基因的引物对，如 Table 4.4。Table 4.4 Primer pairs to measure angiogenesis-related genes in RT-PCR.  \n\n<html><body><table><tr><td>Genes</td><td>Sequence (5'-3')</td></tr><tr><td>VEGF</td><td>F: AGTGGTGAAGTTCATGGATGT</td></tr><tr><td></td><td>R: GGATGGCTTGAAGATGTACTCGA</td></tr><tr><td>HIF-1α</td><td>F: TCACCACAGGACAGTACAGGA</td></tr><tr><td></td><td>R: CGTGCTGAATAATACCACTCACA</td></tr><tr><td>GAPDH</td><td>F: CTCTGACTTCAACAGCGACACC R: TCCACCACCCTGTTGCTGTA</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 113,
+        "chunk": "# 4.2.11.4 体外成骨性能测试  \n\n1. BMSC 细胞在材料表面的增殖情况通过 CCK-8 试剂盒测定，具体实验步骤与第二章相同，详见2.2.8.2 的实验1。  \n\n2. 通过扫描电镜观察 BMSC 细胞在材料表面的生长情况，具体实验步骤与第二章相同，详见2.2.8.2 的实验 2。3. BMSC 细胞在不同样品上的粘附与扩散用罗丹明标记的鬼笔环肽和 DAPI染色法进行检测，具体实验步骤与第二章相同，详见 2.2.8.2 的实验34. 通过 Transwell 实验研究 BMSC 细胞在不同样品上的迁移性能，具体的实验步骤与第三章相同，详见 3.2.8.2 的实验4。5. 通过碱性磷酸酶（ALP）活性定量和染色实验检测 BMSC 细胞在不同样品表面的早期成骨分化情况，具体实验步骤与第二章相同，详见 2.2.8.3 的实验1。6. 通过茜素红（ARS）染色和定量分析检测 BMSC 细胞在不同样品表面的晚期成骨分化情况，具体实验步骤与第二章相同，详见 2.2.8.3 的实验2。7. 通过实时荧光定量聚合酶链式反应（RT-PCR）研究BMSC 细胞在不同样品表面的成骨相关基因的表达情况，具体实验步骤与第二章相同，详见 2.2.8.3 的实验3，其中RT-PCR 所需的成骨相关基因的引物对详见Table 3.3。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 114,
+        "chunk": "# 4.2.12 体内动物实验  \n\n动物实验采用大鼠皮下植入模型研究 MOF 水凝胶修饰磺化 CFRPEEK 植入物的体内抗炎和成血管能力。采用兔胫骨缺损模型来探究 MOF 水凝胶修饰的磺化CFRPEEK 植入物的体内成骨能力。所有动物实验程序均已通过吉林大学基础医学学院动物福利与伦理委员会批准（批准号：2021268），并按照相关机构指南和法律进行。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 115,
+        "chunk": "# 4.2.12.1 大鼠皮下植入实验  \n\n1. 大鼠皮下植入模型的建立：将 12 只购买自北京维通利华的雄性 SD 大鼠（8 周，体重 $200{\\pm}25\\mathrm{g}$ ）随机分为四组：SCP，MACS，HAP 和MGH。所有动物均用异氟烷麻醉，起效后在大鼠背部备皮、消毒、铺巾并使大鼠呈俯卧位，在大鼠背部做一个 $1{-}2~\\mathrm{cm}$ 的纵向伤口，并在伤口的相对两侧建立两个皮下袋，随机植入两个样品并缝合。大鼠在 3 天和 5 天被安乐死，收集样品周围的皮肤组织，将组织样本固定在 $4\\%$ 多聚甲醛中以进行后续分析。  \n\n2.不同样品周围皮肤组织的成血管和炎症情况：将组织样本从固定液取出并拍照，以观察新血管的生成情况。组织样本包埋在石蜡中，蜡块放入石蜡切片机中，并切成为 $4~{\\upmu\\mathrm{m}}$ 厚的切片。通过 CD31 免疫荧光染色对切片进行染色，进一步研究不同样品对新血管生成的影响。通过苏木精-伊红（H & E）染色法对切片进行染色，以检测样品周围皮肤组织的炎症情况。通过 CD86/CD163 免疫荧光染色对切片进行染色，以研究不同样品的体内抗炎能力。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 116,
+        "chunk": "# 4.2.12.2 建立兔胫骨缺损模型  \n\n1.兔胫骨缺损模型的建立：将购自长春市亿斯实验动物技术有限责任公司雄性日本大耳白兔24 只（体重 $2\\mathrm{kg}$ ），随机分为 4 组：SCP，MACS，HAP 和 MGH。所有动物均用 Zoletil 50 $(5\\mathrm{mg/kg)}$ 和速眠新 $(0.2\\mathrm{mL}/\\mathrm{kg})$ 肌肉注射麻醉，起效后在兔的右后肢的胫骨区备皮、消毒、铺巾，作 1cm 纵切口，切开皮肤，钝性剥离皮下组织，露出胫骨。用 $5\\mathrm{mm}$ 外径的去骨钻在胫骨制造圆形骨缺损，将植入物随机植入缺损部位，用手术线缝合。在左侧后胫骨，进行相同的手术。实验动物每天肌肉注射一次抗生素，连续三天，以避免感染。兔在 4 周和 8 周被安乐死，收集含有样品的胫骨和内脏（心、肝、脾、肺和肾），固定在 $4\\%$ 多聚甲醛中以进行后续分析。 Figure 4.2 是兔胫骨缺损建立的示意图。  \n\n![](images/052ee10f263bcf59391338a34048550cfb6afa2aa29fd1c20a16b89f97e2872b.jpg)  \nFigure 4.2 Diagram of the rabbit tibial bone defect model.  \n\n2. 显微计算机断层扫描  \n\n具体操作步骤与第二章相同，详见2.2.9.2 显微计算机断层扫描 （micro-CT）  \n\n3. 组织学探究  \n\n（1）胫骨硬组织切片及染色  \n具体操作步骤与第二章相同，详见 2.2.9.3 实验1。（2）内脏石蜡切片及染色  \n具体操作步骤与第二章相同，详见 2.2.9.3 实验2。  \n\n4. 通过推出实验研究不同样品与骨组织的结合力。Figure 4.3 为推出实验的示意图。在 $23^{\\circ}\\mathrm{C}$ 和 $50\\%$ 相对湿度下，使用 AGX 电子万能材料试验机进行测量。将含不同样品的胫骨置于实验台上，施加轴向压缩应力，并以 $5.0\\ \\mathrm{mm/min}$ 的速度将样品推出，记录载荷-位移曲线和最大载荷情况。为了进一步观察新生骨的状况，对推出的不同CFRPEEK 植入物进行了SEM 和EDS 测试。  \n\n![](images/786d8e1063ed7637b5e4b2221fcc5c554e8a0cdf41b02ea77105bfef27bc4c57.jpg)  \nFigure 4.3 Schematic diagram of the push-out experiment.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 117,
+        "chunk": "# 4.2.13 统计与分析  \n\nIBM SPSS Statistics 22 软件用于数据的统计分析。统计显著性（ $(p<0.05$ ）是通过Tukey 事后检验的单因素方差分析（ANOVA）得出的。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 118,
+        "chunk": "# 4.3 结果与讨论  \n\n4.3.1 HAP@Mg-GA MOF 纳米颗粒的制备  \n\nFigure 4.4 是 HAP@Mg-GA MOF 纳米颗粒的 SEM（a）和 TEM（b）图像，HAP@Mg-GA MOF 纳米颗粒呈针棒状。通过 Figure 4.4b 可以观察到 HAP@Mg-GA MOF 纳米颗粒具有核壳结构，经过测量得出 HAP@Mg-GA MOF 纳米颗粒长度为 $132.08\\pm41.18\\mathrm{{nm}}$ ，壳厚为 $6.02\\pm0.97\\mathrm{nm}$ 。HAP@Mg-GA MOF 纳米颗粒的核壳结构能够控制生物分子 $\\mathrm{Mg}^{2+}$ 、GA 和 $\\mathrm{Ca}^{2+}$ 的释放。  \n\n![](images/3b896d577412bb62ba441e5ebfc4d2c37372a2cb7da6c0e623cbadb03fed179c.jpg)  \nFigure 4.4 (a) SEM (scale bars $=100\\mathrm{nm}$ and $200\\mathrm{nm}$ ) and (b) TEM (scale bars $=25$ nm and $50\\mathrm{nm}$ ) images of HAP $@$ Mg-GA MOF nanoparticles.  \n\nFigure 4.5a 是纳米羟基磷灰石和 $\\mathrm{HAP}@\\mathrm{Mg-GA}$ 的 XRD 谱图。XRD 结果表明，HAP@Mg-GA MOF 纳米颗粒的衍射峰与纳米羟基磷灰石颗粒的标准峰（JCPDS 09-0432）匹配良好，说明 $\\mathbf{Mg-GA}$ 的壳层对羟基磷灰石核层的晶体结构没有影响。Figure 4.5b 是 HAP@Mg-GA 的 XPS 谱图。在 $\\mathrm{HAP}@\\mathrm{Mg-GA}$ 上除检测到了 Ca 2p 和 P 2p 峰外，还检测到了 C 1s、O 1s、 $\\mathrm{Mg2p}$ 峰，这表明 Mg-GA成功沉积到纳米羟基磷灰石上。上述实验结果证明，我们成功制备了 $\\mathrm{HAP}@\\mathrm{Mg-}$ GA MOF 纳米颗粒。  \n\n![](images/62660be7b41dfa61b8a08dd31eeea44a040ff4ae3c14f99f8a8d6e806e065696.jpg)  \nFigure 4.5 (a) XRD spectra of hydroxyapatite and HAP@Mg-GA nanoparticles. (b) XPS analysis of HAP $@$ Mg-GA MOF nanoparticles.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 119,
+        "chunk": "# 4.3.2 甲基丙烯酰化壳聚糖（CSMA）的制备  \n\nFigure 4.6 为 CSMA 的合成原理图及壳聚糖改性前后的 $\\mathrm{^{1}H N M R}$ 谱图。从壳聚糖的 $\\mathrm{{}^{1}H\\ N M R}$ 谱图中，可以观察到在 $1.9\\ \\mathrm{ppm}$ 处出现了壳聚糖乙酰化部分的峰， $3.0{-}3.8\\mathrm{ppm}$ 处则代表壳聚糖中的葡萄糖胺环。在 CSMA 的 $\\mathrm{^{1}H N M R}$ 谱图中，除了检测到上述壳聚糖的峰外，还在 $5.6\\mathrm{ppm}$ 和 $6.0\\mathrm{ppm}$ 处检测到亚甲基和甲基丙烯酰胺峰，表明壳聚糖改性成功。通过计算得出甲基丙烯酰胺的含量为壳聚糖上葡萄糖胺环的 $36\\%$ 。  \n\n![](images/78c248f6b23ebc40c749d108e9f5c303384a383e8d30d4d3ee6035891983bde5.jpg)  \nFigure 4.6 Schematic diagram of the synthesis of methacryloyl chitosan and $^{1}\\mathrm{HNMR}$ spectra of chitosan and methacryloyl chitosan.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 120,
+        "chunk": "# 4.3.3 MOF 水凝胶修饰磺化 CFRPEEK 的制备  \n\n将 HAP@Mg-GA MOF 纳米颗粒与 CSMA 的凝胶前体溶液混合，通过紫外线照射接枝到磺化CFRPEEK 植入物的表面。接枝后，磺化的 CFRPEEK 的表面变成淡黄色。采用 SEM 分析了不同 CFRPEEK 的表面形貌，如图 Figure 4.7a 所示，在 SCP 表面观察到少量的裸露碳纤维和 3D 多孔网络结构。在紫外接枝后，3D 多孔结构和裸露的碳纤维被水凝胶覆盖。与 MACS 相比，HAP 和MGH 的表面不平整且纳米颗粒均匀分散在磺化 CFRPEEK 表面的水凝胶内。Figure 4.7b 为MACS 切片的横截面 SEM 图像，磺化 CFRPEEK 表面上的水凝胶厚度约为 22μm。  \n\n![](images/bcc3b8561285bed7eb5dfc184aa770365182e4da2635db45dc6adeeef13e0124.jpg)  \nFigure 4.7 (a) SEM images of different elements for SCP, MACS, HAP and MGH， scale bars ${\\bf\\mu}=1{\\bf\\mu}{\\bf m}$ and $5\\upmu\\mathrm{m}$ . (b) The cross-sectional image of MACS, scale bar $=50$ μm.  \n\nFigure 4.8 是不同 CFRPEEK 的表面 EDS 面谱（a）和元素的相对浓度（b）的分析结果。如Figure 4.8a 所示，在 SCP 表面观察到大量的碳和氧元素，还有由于磺化处理残留的少量硫元素。甲基丙烯酰化壳聚糖的紫外接枝使得 MACS、HAP 和MGH 中检测出了氮元素，除此之外，MGH 中还含有钙、磷和少量的镁（Figure 4.8b），这表明 HAP@Mg-GA MOF 纳米颗粒成功的掺入到水凝胶中，实现了最初的设计目标。  \n\n![](images/2ecd3c774d52336eccd5a50f2b13301b52dc2ffe02ba38a51e94625c5c55c679.jpg)  \nFigure 4.8 (a) EDS maps of different elements for SCP, MACS, HAP and MGH. (b) EDS-determined atomic percentages SCP, MACS, HAP and MGH.  \n\nATR-FTIR 光谱显示了不同 CFRPEEK 样品上化学基团的变化。如 Figure 4.9所示，在 MACS, HAP 和 MGH 谱图中的 $2922\\mathrm{cm}^{-1}$ 处观察到了-CH3 的伸缩振动吸收峰。 $1642~\\mathrm{cm^{-1}}$ , $1542~\\mathrm{cm^{-1}}$ , $1320\\mathrm{cm}^{-1}$ 依次为酰胺Ⅰ，Ⅱ和Ⅲ的峰，这表明甲基丙烯酰化壳聚糖已成功接枝到磺化 CFRPEEK 上[345, 346]。在 MGH 谱图中的 1030$\\mathrm{cm^{-1}}$ 处检测到了 $\\mathrm{PO}_{4}{}^{3\\cdot}$ -的伸缩振动吸收峰，表明了 MOF 纳米颗粒的成功掺入。  \n\nEDS 和 ATR-FTIR 实验结果表明，在磺化的 CFRPEEK 表面成功制备了 MOF 水凝胶层。  \n\n![](images/d09ee684b08447fb72ad41846bcdde6b4fc0b91aee02f0296ffe002bf2a704b0.jpg)  \nFigure 4.9 ATR-FTIR spectra of SCP, MACS, HAP and MGH.  \n\n为了进一步证明 MOF 水凝胶层的成功构建，通过水接触角检测了不同CFRPEEK 样品的表面亲水性。如 Figure 4.10 所示，SCP 的水接触角为 $116.3\\pm$ $1.3^{\\circ}$ ，表明SCP 的表面是疏水的。经过紫外接枝改性后，其他三组的水接触角显著降低，MACS 为 $63.6\\pm1.5^{\\circ}$ ，HAP 为 $57.1\\pm2^{\\circ}$ ，MGH 为 $42.2\\pm3.7^{\\circ}$ 。以前的文献研究表明，亲水表面可以促进成骨细胞的原始粘附[347]。  \n\n![](images/21f415eece191e7253bedcdf8fdbe2f3ee25e7f4c46ed429256826050a53c13b.jpg)  \nFigure 4.10 Water contact angles of SCP, MACS, HAP and MGH. \\*, & and # represents $p<0.05$ when compared with SCP, MACS and HAP, respectively.  \n\nMOF 水凝胶修饰磺化 CFRPEEK 的制备原理图如 Figure 4.1b 所示，经磺化处理的CFRPEEK 具有多孔的结构。当磺化处理的 CFRPEEK 在紫外线(UV)照射下，CFRPEEK 复合材料中的 PEEK 的二苯甲酮单元可以产生自由基，光引发聚合物甲基丙烯酰化壳聚糖（CSMA）的烯基双键可以与 PEEK 形成 C-C 共价键，从而诱导接下来的接枝聚合，CFRPEEK 表面就会形成 CSMA 水凝胶层。HAP@Mg-GA MOF 纳米颗粒会与 CSMA 形成氢键，从而增加了凝胶结构的稳定性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 121,
+        "chunk": "# 4.3.4 MOF 水凝胶层的附着力  \n\nMOF 水凝胶层与磺化 CFRPEEK 之间的附着强度采用划痕法测定。Figure4.11 为渐进加载条件下MACS 的划痕形态和AE 信号曲线。当 Fn 分别为 $3.96\\mathrm{N}$ 和7.12 N 时出现了第一和第二个 AE 信号，结合相应的划痕形态，水凝胶层并没有被完全破坏。因此，它们并不能代表水凝胶层与磺化 CFRPEEK 之间的粘附强度。当Fn 为 $10.98\\mathrm{N}$ 时出现了第三个 AE 信号，划痕形态表明在此力下 MOF 水凝胶层被完全破坏。因此，水凝胶层与磺化 CFRPEEK 之间的附着强度为 10.98N。  \n\n![](images/6427d19b413db5d72e4c7c6b61a0b2329f7988215a8b67c260e3de9976aeda87.jpg)  \nFigure 4.11 Scratch morphology and AE signal curve of MACS under progressive loading.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 122,
+        "chunk": "# 4.3.5 表面 zeta 电势  \n\n不同CFRPEEK 样品的表面电荷情况通过表面 zeta 电势测定。结果如 Figure4.12 所示，在 $\\mathfrak{p H}$ 为 5-8 范围内，随着 $\\mathsf{p H}$ 的升高，所有样品表面的 zeta 电势减弱，zeta 电势的顺序为 $\\mathrm{MGH}>\\mathrm{MACS}>\\mathrm{HAP}>\\mathrm{SCP}$ 。由于甲基丙烯酰化壳聚糖是一种带正电荷的阳离子聚合物[348]，MGH、MACS 和 HAP 比 SCP 具有更高的zeta 电势。在氯化钾溶液中，纳米羟基磷灰石的 zeta 电势为负值[349]，所以HAP的 zeta 电势有所降低。由于在 HAP@Mg-GA MOF 纳米颗粒中存在 $\\mathrm{Mg}^{2+}$ ，MGH  \n\n的zeta 电势增加。  \n\n![](images/2ca2fa95d91277ef5866a04c4e2dab87a2538952c274a285b91c82bb558f64fd.jpg)  \nFigure 4.12 Zeta potential of SCP, MACS, HAP and MGH.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 123,
+        "chunk": "# 4.3.6 蛋白吸附能力  \n\n以牛血清白蛋白（BSA）为参考蛋白，研究了各组样品的蛋白质吸附能力。如Figure 4.13 所示，各组的蛋白质吸附量随着培养时间的延长呈增加趋势。SCP在孵育 $^{4\\mathrm{~h~}}$ 后基本不能再吸附 BSA。各组的蛋白质吸附能力为 $\\mathrm{MGH}>\\mathrm{HAP}>$ $\\mathbf{MACS}>\\mathbf{SCP}$ ，与表面电荷的结果一致。在成骨整合的早期阶段，植入物在植入后最初识别的是蛋白质、纤维、离子、细胞因子以及血液环境中的其他成分[350]。能够立即识别并结合蛋白质到植入物表面是植入物骨整合的关键特征。正常人血液中的大部分蛋白质都带负电荷，即使在成骨细胞表面也是如此[351]。带负电荷的蛋白会因为静电相互作用而迅速粘附在带正电荷的植入物表面，从而极大提高植入物的生物相容性。根据上述实验结果，MOF 水凝胶修饰磺化 CFRPEEK 具有良好的蛋白质吸附能力。  \n\n![](images/1ea7030d334985c4694efc16283da7b6afd699fec8061a79b0e546de6533aa5f.jpg)  \nFigure 4.13 Protein adsorption capacity of different samples within 4 days.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 124,
+        "chunk": "# $4.3.7\\mathrm{Ca}^{2+}$ 、 $\\mathrm{Mg^{2+}}$ 和GA 的在不同 $\\mathsf{p H}$ 下的缓释行为  \n\n磺化 CFRPEEK 表面的 $\\mathsf{p H}$ 响应性水凝胶中的甲基丙烯酰化壳聚糖和HAP@Mg-GA 在生理液体中会发生降解，从而导致生物相容性的羟基磷灰石、没食子酸（GA）和镁离子的释放。ICP-OES 和UV-vis 用于测量 21 天内不同 $\\mathsf{p H}$ 值（5.5、6.5 和 7.4）下 HAP 和 MGH 中 $\\mathrm{Ca}^{2+}$ 、 $\\mathrm{Mg}^{2+}.$ 和 GA 的释放量。HAP 和MGH 的生物分子释放行为如 Figure 4.14a-c 所示。Figure 4.14a 是不同 $\\mathsf{p H}$ 下$\\mathrm{Mg}^{2+}$ 在MGH 中的释放曲线。在正常 $\\mathsf{p H}$ （ $\\mathsf{p H}=7.4$ ）条件下，MGH 中 $\\mathrm{Mg}^{2+}$ 的释放率明显低于弱酸（ $\\mathrm{\\pH}=5.5$ 和 6.5）环境下的。在初始阶段（第一天） $\\mathrm{Mg}^{2+}$ 的释放出现了突释现象，这是由于靠近水凝胶表层的 $\\mathrm{HAP}@\\mathrm{Mg-GA}$ 释放 $\\mathrm{Mg}^{2+}$ 引起的。随着时间的增加，弱酸环境会削弱甲基丙烯酰化壳聚糖的氢键，使得甲基丙烯酰化壳聚糖逐渐膨胀和降解，从而导致生物分子逐渐释放[352]。GA 在MGH 中的释放曲线与 $\\mathrm{Mg^{2+}}$ 相似（Figure 4.14b），这些结果表明弱酸环境有利于水凝胶层中 $\\mathrm{Mg}^{2+}$ 和 GA 的释放。 $\\mathsf{p H}$ 响应性 MOF 水凝胶修饰磺化 CFRPEEK 能够在炎症反应阶段（弱酸环境）释放足够的 GA 和 $\\mathrm{Mg}^{2+}$ ，为骨整合初始阶段的炎症调节和血管生成提供更好的微环境。如 Figure 4.14c 所示，由于 $\\mathrm{HAP}@\\mathrm{Mg-GA}$ 壳层的存在，MGH 中 $\\mathrm{Ca}^{2+}$ 的释放效率比 HAP 低，并且在正常 $\\mathfrak{p H}$ （ $\\mathrm{\\Phi}_{\\mathrm{pH}}=7.4\\$ ）下$\\mathrm{Ca}^{2+}$ 能够长期且缓慢的释放，这为骨整合后期生成新骨提供了良好的微环境。上述实验结果符合预期，即 $\\mathsf{p H}$ 响应性 MOF 水凝胶修饰磺化 CFRPEEK 能够持续释放 GA 和 $\\mathrm{Mg}^{2+}$ ，并在炎症环境（低 $\\mathfrak{p H}$ ）下调节炎症反应和促进新血管生成，而 $\\mathrm{Ca}^{2+}$ 的长期释放能够促进骨整合后期（正常 $\\mathfrak{p H}$ ）新骨的生成。  \n\n![](images/d7839471842f678c2e8037b5bb9690f0bdac184dd9280e3df51e2c42b839c5ad.jpg)  \nFigure 4.14 The efficiency of released (a) $\\mathrm{Mg}^{2+}$ and (b) GA from MGH over time in the presence of PBS at $\\mathrm{pH}7.4$ , 6.5, and 5.5. (c) The efficiency of released $\\mathrm{Ca}^{2+}$ from HAP and MGH at various pH values (7.4, 6.5 and 5.5).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 125,
+        "chunk": "# 4.3.8 体外矿化行为  \n\n将不同CFRPEEK 样品浸入模拟体液（SBF）中研究它们生成骨样磷灰石的能力。Figure 4.15 为不同样品在 SBF 中浸泡 7 天后的表面形态变化的SEM 图像（a）和 EDS 分析（b）。如 Figure 4.15a 所示，在 SCP 和 MACS 上的沉积物数量相对较少。在 HAP 和 MGH 中均观察到明显圆形结节，特别是 MGH 组，它几乎完全被致密和均匀的球形沉积物所覆盖。如 Figure 4.15b 所示，MGH 上的球形沉积物的组成与骨样磷灰石相似。纳米羟基磷灰石和没食子酸是 MGH 中HAP@Mg-GA 的成分，可以作为矿物沉积的成核剂或诱导模拟体液中的 $\\mathrm{Ca}^{2+}$ ,OH-,和 $\\mathrm{PO}_{4}{}^{3-}$ 在 CFRPEEK 表面生成骨样磷灰石。MOF 水凝胶层增强了磺化CFRPEEK 生成骨样磷灰石的能力，表明其具有良好的体外骨结合能力。  \n\n![](images/b0e27760e32f619cd28a1abafa65f2fbedf5ba60660aed76c611be08febcd243.jpg)  \nFigure 4.15 (a) SEM images of different samples after 7 days in SBF, scale bar $=10$ $\\upmu\\mathrm{m}$ . (b) The EDS spectra of different specimens after soaking in SBF for 7 days.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 126,
+        "chunk": "# 4.3.9 体外炎症反应  \n\n在骨整合的早期阶段，当宿主免疫细胞被吸引或分化到植入物界面时，免疫细胞介导的炎症反应立即开始[316]。巨噬细胞是在免疫调节中发挥关键作用的主要炎症细胞。M1 和M2 分别是具有促炎功能和抗炎功能的巨噬细胞[353]。将促炎性M1 及时、准确地转成抗炎性 M2 对于恢复正常体内平衡至关重要[354]。因此，在磺化CFRPEEK 表面设计和构建 $\\mathsf{p H}$ 响应生物分子递送系统来调节炎症微环境，如改善低 $\\mathfrak{p H}$ 、缺氧和高ROS 环境，这是提高宿主受损组织再生能力的有效方法[341]。虽然 GA 和 $\\mathrm{Mg}^{2+}$ 的释放速率在弱酸环境中较快，但是 GA 和 $\\mathrm{Mg}^{2+}$ 的持续释放仍然可以使 $\\mathsf{p H}$ 响应的MOF 水凝胶能够实现精确的免疫调节功能。  \n\n采用脂多糖（LPS）处理 RAW264.7 巨噬细胞以模拟低pH 炎症环境[355]，使用 LPS 处理的 RAW264.7 作为对照组进行流式细胞术分析，以研究磺化CFRPEEK 表面上的 $\\mathsf{p H}$ 响应性 MOF 水凝胶是否可以主动和准确地进行免疫调节。iNOS 为 M1 的标记物，CD206 为 M2 的标记物。如 Figure 4.16 所示，与对照相比，在培养一天后暴露于 MGH 的 RAW264.7 巨噬细胞中，iNOS 显著减少$(5.55~\\%)$ ），CD206 明显增加（ $1.16\\ \\%$ ），这表明在低 $\\mathfrak{p H}$ 炎症环境下 MGH 可降低 M1 巨噬细胞极化，促进 M2 巨噬细胞极化。在先前的研究中，GA 已被证明可以通过抑制多种信号通路来阻碍 M1 巨噬细胞的极化[356]。 $\\mathrm{Mg}^{2+}$ 可以通过TRPM7 离子通道进入巨噬细胞，促进 M1 向M2 巨噬细胞转化[335]。  \n\n![](images/9c357cbc351cfc1aff29d2966e41c2bbdf0a227967313cf4141b25bd717ac979.jpg)  \nFigure 4.16 (a) In vitro flow cytometry detection of macrophage polarization after 1 day of culture.  \n\n采用 RT-PCR 测定暴露于不同 CFRPEEK 的 RAW264.7 的基因表达水平，以进一步探索促炎基因（IL-6），M1 表面标记物（iNOS），抗炎基因（IL-10）和M2表面标记物（CD206）的表达情况。如 Figure 4.17a 所示，在培养 5 天后，与 SCP组相比，MGH 中 IL-6 表达减少了 $66.28\\%$ ，IL-10 表达增加了 $137.39\\%$ ，同时，M2 标记物 CD206 表达水平显著升高，这表明 MGH 可以大大减弱 LPS 诱导的炎症反应。ELISA 用于跟踪 M1 和M2 相关细胞外细胞因子的分泌，其中 TNF- $\\mathbf{\\nabla}\\cdot\\mathbf{a}$ 为促炎细胞因子，IL-10 为抗炎细胞因子。正如预测的那样，相对于 SCP，MGH中的 TNF- $\\mathbf{\\sigma}\\cdot\\mathbf{a}$ 的分泌减少了 $67.09\\%$ （Figure 4.17b），IL-10 的分泌增加了 $284.19\\%$ （Figure 4.17c），这与炎性基因表达结果一致。上述所有发现都证实了我们的假设，即磺化 CFRPEEK 表面的 $\\mathsf{p H}$ 响应 MOF 水凝胶可以通过释放 GA 和 $\\mathrm{Mg^{2+}}$ 来促进 M1/M2 巨噬细胞极化和减轻炎症反应，这有利于损伤组织的修复（Figure4.17d）。  \n\n![](images/86df4432239f5913007bb8d7e5ea7d09cda48c2a9ee11485947759bd73baf21f.jpg)  \n\nFigure 4.17 (a) Heat map indicating expression of M1 marker (iNOS) and pro  \ninflammatory gene (IL-6) and M2 marker (CD206) and anti-inflammatory gene (IL  \n10) detected by RT-PCR after 5 days of incubation. Secretion of (b) TNF- $\\mathfrak{a}$ and (c) IL  \n10 after incubation for 3 days. (d) Schematic illustration of the accurate and proactive immunomodulation properties of the stimuli-responsive MOF hydrogel-modified   \nsulfonated CFRPEEK implant. \\*, #, & and a represents $p<0.05$ when compared with SCP + LPS, MACS $^+$ LPS, HAP $+$ LPS and $\\mathrm{MGH+LPS}$ , respectively.  \n\n在炎症反应阶段，植入产生的炎症环境可能会使 ROS 不受控制的产生和持续的氧化应激，从而导致细胞凋亡并进一步引发不利于骨愈合的炎症反应[357]。适当的氧化应激会减少细胞凋亡，减轻炎症反应，有利于新骨生成。利用二DCFH-DA 荧光技术探究巨噬细胞内 ROS 的量，结果如 Figure 4.18a 所示。经过LPS 处理后，对照组细胞内 ROS 生成增多，MGH 抑制了过量的 ROS 产生。通过流式细胞术进一步分析细胞内 ROS 水平，结果如 Figure 4.18b 所示。与其他组相比，MGH 的曲线向左移动，这表明 MGH 具有优异的抗氧化作用。根据早期的研究，GA 可以清除细胞内过量的 ROS，减轻ROS 诱导的炎症反应[341]。因此，pH 响应性MOF 水凝胶修饰磺化 CFRPEEK 可以通过释放 GA 来缓解巨噬细胞氧化应激，使其能够减轻炎症反应。  \n\n![](images/516465fde7e38ddbeed682606cb31b4899b01fa696c939d2720ff7fc861b999f.jpg)  \nFigure 4.18 The intracellular ROS fluorescence intensity of RAW264.7 cells treated with different samples is analyzed by (a) fluorescence microscopy and (b) flow cytometry, scale bar $=100\\upmu\\mathrm{m}$ .  \n\n有研究表明，LPS 诱导 RAW264.7 后，iNOS 的表达增加，大量生成 NO，导致生理功能障碍[358]。因此，适量的 NO 生成有利于调节生理稳态。在 LPS 刺激24 小时后，检测不同样品中 RAW264.7 的 NO 释放，结果如 Figure 4.19 所示。MGH 中的 NO 释放相较于 SCP 降低了 $52.45\\%$ ，表明 MGH 抑制了 LPS 诱导的NO 释放并减轻了炎症反应。  \n\n![](images/26e8cdfb68dd657bc0ac2ee5e1f7cad092206c501de9248ae72cff10ec46ff32.jpg)  \nFigure 4.19 Release levels of NO in various samples after $24\\mathrm{h}$ of LPS induction. \\*, #, & and a represents $p<0.05$ when compared with $\\mathrm{SCP+LPS}$ , $\\mathrm{MACS+LPS}$ , HAP + LPS and $\\mathrm{MGH+LPS}$ , respectively.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 127,
+        "chunk": "# 4.3.10 体外成血管性能  \n\n当巨噬细胞发挥作用时，血管也会逐渐重塑。血管生成是骨折愈合和骨整合过程中新骨生成的关键[359, 360]。如果植入界面的血管化过程缓慢，不充足的氧气和营养缺失会致使细胞死亡。因此，植入后快速和持续的血管生成是植入物的基本功能。HUVEC 用于研究 MOF 水凝胶修饰磺化 CFRPEEK 的细胞相容性和血管生成能力。Figure 4.20a 显示了在不同 CFRPEEK 上培养的 HUVEC 的形态。培养 1 天后，HUVEC 在所有样品的表面扩散。SCP 上的 HUVEC 细胞呈梭形，并且具有最小的丝状伪足，这表明 SCP 不利于 HUVEC 细胞的粘附。MGH 上的HUVEC 细胞的扩散面积最大，并且细胞之间已经相互连接，这说明 HUVEC 细胞的融合效果相较于其他组更好。Figure 4.20b 是不同 CFRPEEK 样品的 CLSM图像，细胞骨架用罗丹明标记的鬼笔环肽（红色）染色，进一步证实了扫描电镜的结果。与 SCP 相比，有更多的 HUVEC 细胞粘附和扩散到其他 CFRPEEK 样品上。特别是，在 MGH 上观察到更多、更成熟的 F-肌动蛋白，这要归因于MGH粗糙的表面、高表面电位和亲水性，这些特性有利于细胞的粘附[361]。  \n\n![](images/a1d8a082ee586aea00a8ae2d6011795609eb50010fff0aa5797623fb65986ebb.jpg)  \nFigure 4.20 HUVEC morphologies after culturing on different samples for $24\\mathrm{h}$ detected by (a) SEM (Cells are false-colored to green for easier visualization) and (b) CLSM (Red staining represents the cytoskeletal organization), scale bars ${\\it\\Delta\\phi}=5{\\it\\Psi}\\upmu\\mathrm{m}$ and  \n\nCCK-8 进一步证实了 MOF 水凝胶修饰磺化 CFRPEEK 的 HUVEC 细胞相容性。如 Figure 4.21 所示，培养 1 天后，不同样品的细胞活力排序为 $\\mathrm{SCP}{<}\\mathrm{MACS}$ $<_{\\mathrm{HAP}}<_{\\mathrm{MGH}}$ 。当培养时间延长到 5 天时，每组样品的细胞活力显著增加，其中MGH 细胞活力相较于 SCP 增加了 $29.32\\%$ 。MGH 上的细胞存活率明显高于 HAP上，这是由于MGH向周围环境中持续释放 $\\mathrm{Mg}^{2+}$ ，促进了细胞增殖和粘附[333, 334]，这些结果表明，MGH 具有较高水平的细胞生物相容性。  \n\n![](images/faec55bbee3e82c4c2acec3767a4d35ae8d091891de6ebb23e5b9899b9a4b1e4.jpg)  \nFigure 4.21 Cell proliferation of HUVECs after 1, 3 and 5 days seeding on different substrates. \\* represents $p<0.05$ when compared with SCP.  \n\n采用 Transwell 实验研究了 MOF 水凝胶修饰磺化 CFRPEEK 对 HUVEC 细胞迁移的影响。如 Figure 4.22a 所示，培养 24 小时后，SCP 中只有少量的 HUVEC细胞发生迁移。与 MACS 和 HAP 相比，在 MGH 中的 HUVEC 细胞在 24 小时后发生明显的迁移。Figure 4.22b 是细胞迁移的定量分析结果，MGH 中迁移的HUVEC 细胞数量相较于 SCP 增多了 $598.25\\%$ 。  \n\n![](images/ca0a8a0fb940dd16d38c5736fef90d9cd30e03c41abf2f9192f491cc23e02ebd.jpg)  \nFigure 4.22 (a) Images and (b) quantitative analysis of migrating HUVECs exposed to different samples after $24\\mathrm{h}$ of incubation, scale bar $=200\\upmu\\mathrm{m}$ . \\*, # and & represents $p<0.05$ when compared with SCP, MACS and HAP, respectively.  \n\nFigure 4.23a 是体外管形成实验结果。体外管形成实验表明，MACS 和HAP比SCP 生成了更多的毛细管样管，值得注意的是，MGH 的管形成明显增加。通过Image J 统计了不同样品管的总分支长度和分支数，结果如Figure 4.23b 所示。  \n\n与SCP 组相比，MGH 管的总分支长度和分支数分别增加了 $88.44\\%$ 和 $81.82\\%$ 。  \n\n![](images/33bcc04b853d8715f02f5ab99c331e635a4ef933cc21be1fab1f8f4c10a3e1b6.jpg)  \nFigure 4.23 (a) Tube formation and (b) corresponding parameter analysis of HUVECs exposed to different samples for $6\\mathrm{{h}}$ , scale bar $=200\\ {\\upmu\\mathrm{m}}$ . \\*, # and & represents $p<$ 0.05 when compared with SCP, MACS and HAP, respectively.  \n\n利用 RT-PCR 实验检测与血管生成相关基因（VEGF 和 HIF- $1\\upalpha$ ）的表达水平，以此来量化 MOF 水凝胶修饰磺化 CFRPEEK 的血管生成能力。如 Figure 4.24所示，在 MGH 上培养的 HUVEC 细胞的 VEGF 和 HIF- $1\\upalpha$ 的表达水平最高，相较于 SCP 分别提高了 $75.76\\%$ 和 $287.15\\%$ ，这表明 MGH 中镁离子的释放可以显著刺激血管生成。镁已被证明可以通过 TRPM7 和 MagT1 离子通道改善血管内皮细胞的增殖、粘附和运动[362]，从而提高细胞骨架蛋白和相关基因的表达，并显着加速新血管的形成[334]。综上所述，MOF 水凝胶层可以通过释放镁离子显著提高CFRPEEK 的血管生成能力。  \n\n![](images/45fe83040e6f29d062647782de6f91a3dc5d0193c0d77f576bc28db12ea67a21.jpg)  \nFigure 4.24 Detection of relative expression of angiogenesis-related genes VEGF and  \n\nHIF- $1\\upalpha$ by RT-PCR after 3 days of incubation. \\*, # and $\\&$ represents $p<0.05$ when compared with SCP, MACS and HAP, respectively.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 128,
+        "chunk": "# 4.3.11 体外成骨性能  \n\n骨整合最终是通过成骨细胞在免疫调节和血管生成后在植入物表面沉积新骨来实现的。优异的成骨活性对于植入物的成功植入和长期稳定性至关重要。BMSC 细胞用于研究 pH 响应 MOF 水凝胶在磺化 CFRPEEK 表面的体外成骨特性。如Figure 4.25a 所示，通过 SEM 观察在不同样品上培养的 BMSC 细胞的形态。 培养一天后，在所有样品上观察到 BMSC 细胞是随机扩散的。在 SCP 上的BMSC 细胞和 HUVEC 细胞一样呈纺锤形，这表明 BMSC 细胞在 SCP 上的粘附性较差。相比之下，在MACS 上培养的BMSC 细胞具有突出的丝状伪足。HAP和 MGH 上的 BMSC 细胞的扩散区域更广泛，这是由于 HAP 和 MGH 中的纳米羟基磷灰石和HAP@Mg-GA 纳米颗粒为BMSC 细胞附着提供了更多的锚定位点[363]。Figure 4.25b 是不同 CFRPEEK 样品的 CLSM 图像。与 SCP，MACS 和 HAP相比，MGH 上的BMSC 细胞的粘附拉伸更好，产生了更多的 F-肌动蛋白，细胞之间相互连接，这证明MOF 水凝胶修饰磺化CFRPEEK 具有更好的 BMSC 细胞粘附和扩散特性。  \n\n![](images/4f8355d7e327aaa099c8de74bf11fe24985d4e2173c4123c3a7accffdab50072.jpg)  \n\nFigure 4.25 BMSC morphologies after culturing on different samples for $24\\mathrm{h}$   \ndetected by (a) SEM (Cells are false-colored to green for easier visualization) and (b)   \nCLSM (Red staining represents the cytoskeletal organization), scale bars $=10\\upmu\\mathrm{m}$ and $50\\upmu\\mathrm{m}.$  \n\nBMSC 的细胞增殖是新骨生成的基础。通过 CCK-8 检测了 BMSC 在各种底物上的增殖情况，如 Figure 4.26 所示，BMSC 细胞在各种底物上的增殖方式与HUVEC 相当，并且它们在 MGH 上的活力远大于其他三组，表明 MOF 水凝胶修饰磺化CFRPEEK 具有良好的 BMSC 细胞相容性。  \n\n![](images/1553029623ee382e4047d8ce3632aa2b705ecfecd202d80c8b6343742d48f44d.jpg)  \nFigure 4.26 Cell proliferation of BMSCs after 1, 4 and 7 days seeding on different substrates. \\* represents $p<0.05$ when compared with SCP.  \n\n通过迁移实验研究不同样品对 BMSC 细胞的趋化性，结果如 Figure 4.27a 所示。培养 24 小时后，在 SCP 和 MACS 中仅观察到少量迁移的 BMSC 细胞，在HAP 和 MGH 中视野几乎被迁移的 BMSC 细胞充满。Figure 4.27b 是定量分析结果，从定量结果可以看出，HAP 和 MGH 比其他两组迁移的 BMSC 细胞更多，其中 MGH 中迁移的 BMSC 细胞的数量是 SCP 的 14.54 倍，这是由于 $\\mathrm{Ca}^{2+}$ 的长期缓慢释放，能够刺激BMSC 细胞的迁移。  \n\n![](images/c88602c4acf1d7b32ec8f3e84525a4cd222587e7603a24d992601ee693dda906.jpg)  \nFigure 4.27 (a) Images and (b) quantitative analysis of migrating BMSCs exposed to different samples after $24\\mathrm{h}$ of incubation, scale bar $=200~{\\upmu\\mathrm{m}}$ .  \n\n利用 ALP 活性、基质矿化和成骨相关基因表达来探究 BMSC 细胞在 MOF水凝胶修饰磺化CFRPEEK 上的成骨分化能力。为了验证各种底物的早期成骨分化潜力，采用ALP 染色和定量分析来测定在不同底物上培养的 BMSC 中的ALP活性。如 Figure 4.28a 所示，随着时间的推移，不同底物上的 ALP 活性显着增加，HAP 和 MGH 的 ALP 活性高于其他两组。在第 14 天，MGH 的 ALP 活性相较于SCP 提高了 $25.41\\%$ 。值得一提的是，MGH 比HAP 的ALP 活性更高，这是由于 MGH 中的纳米羟基磷灰石和 $\\mathrm{Mg^{2+}}$ 的协同作用促进了 BMSC 细胞的早期分化。Figure 4.28b 是不同底物的 ALP 染色图像，在培养 14 天，在 MGH 上观察到紫黑色物质，并且MGH 的 ALP 染色比其他三组深，这说明 MOF 水凝胶修饰磺化CFRPEEK 促进了 BMSC 细胞的早期成骨分化。  \n\n![](images/df84b2ecaa5321414b40f77b208662d63ec75de876774e036e55fec231c91e70.jpg)  \nFigure 4.28 (a) ALP activity of various samples after osteogenic induction for 7 and 14 days. \\* and # represents $p<0.05$ when compared with SCP and MACS, respectively. (b) ALP staining of various samples, scale bar $=2{\\mathrm{~mm}}$ .  \n\n基质矿化是晚期成骨分化的标志，通过 ARS 染色研究BMSC 细胞在不同底物上的基质矿化，染色结果如 Figure 4.29a 所示。培养21 天后，在 SCP 上观察到一些钙结节。HAP 和 MGH 上沉积的钙结节更多，在MGH 中观察到的钙结节最多、最密集。半定量分析基质矿化的结果如 Figure 4.29b 所示，MGH 在21天的钙沉积最多，相较于 SCP 增加了 2.67 倍。ARS 染色结果与 ALP 活性结果一致，这表明磺化CFRPEEK 表面的 MOF 水凝胶可有效刺激 ALP 分泌和基质矿化。  \n\n![](images/fcc8cd638e82ac446031812bfeed966301ff89cabc0372e0b46636b3ad761e19.jpg)  \nFigure 4.29 (a) Alizarin Red staining (ARS) of various samples, scale bar $\\cdot=2\\mathrm{mm}$ . (b)  \n\nQuantitative analysis of ARS staining after osteogenic induction for 21 days. \\*, # and & represents $p<0.05$ when compared with SCP, MACS and HAP, respectively.  \n\n利用 RT-PCR 研究 BMSC 细胞成骨相关基因（ALP，Col-I，BMP-2 和 Runx2）在各种样品上的表达水平，进而探究 MOF 水凝胶修饰磺化 CFRPEEK 的成骨分化特征。如 Figure 4.30 所示，所有成骨相关基因的表达水平都随着培养时间的增加而提高。在 14 天，与 SCP 相比，ALP，Col-I，BMP-2 和 Runx2 在 MGH 上的表达水平分别提高了 $58.62\\%$ 、 $173.98\\%$ 、 $141.59\\%$ 和 $121.68\\%$ 。这些结果证明，与单独的纳米羟基磷灰石相比， $\\mathrm{HAP}@\\mathrm{Mg-G}_{\\mathit{i}}$ A 纳米颗粒显著提高了CFRPEEK 的成骨分化能力。根据报道，羟基磷灰石具有细胞相容性，并通过提高成骨相关基因的表达水平来刺激BMSC 分化成成骨细胞[364]。镁离子可以促进 BMSC 细胞增殖，迁移和粘附，激活成骨信号通路，并提高成骨相关基因表达以促进成骨分化[365]。 因此，磺化 CFRPEEK 表面的 MOF 水凝胶可以增强 BMSC 的粘附、增殖和迁移，并促进成骨分化。  \n\n![](images/3fa5b965bd439f4ecb88c7ddc24ab723fd99820309fe3318c268d1e7f61da301.jpg)  \nFigure 4.30 Heat map showing the expression of osteogenesis-related genes of BMSCs after osteogenic induction for 7 and 14 days. \\*, # and & represents $p<0.05$ when compared with SCP, MACS and HAP, respectively.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 129,
+        "chunk": "# 4.3.12 体内炎症反应和血管生成性能  \n\n采用SD 大鼠皮下植入模型研究体内炎症反应和血管生成。在植入 3 和5 天后，取出植入物周围的皮下组织，利用 H & E 染色和免疫荧光染色观察植入物周围组织的炎症状态。Figure 4.31 是（a）H & E 染色结果图像及（b）纤维层的厚度统计图。在植入 3 天和 5 天后，所有植入物周围的皮下组织都产生了纤维层（黑色箭头）。在植入 3 天后，SCP 周围有致密的连续纤维层，厚度为$1203.32{\\pm}162.46\\upmu\\mathrm{m}$ 。MACS 和 HAP 周围的纤维层较薄，厚度分别为 $524.20{\\scriptstyle\\pm65.19}$ $\\upmu\\mathrm{m}$ 和 $460.34{\\pm}108.07~{\\upmu\\mathrm{m}}$ ，这表明 MACS 和HAP 在体内的炎症水平较低。MGH周围的纤维层最薄，厚度为 $330.36{\\pm}30.34~\\upmu\\mathrm{m}$ ，这表明 MOF 水凝胶修饰磺化CFRPEEK 植入物具有与体外抗炎结果一致的抗炎特性。与第 3 天相比，在第 5天所有植入物周围的纤维层变薄，MGH 周围的纤维层仍然最薄且厚度为$128.37{\\scriptstyle\\pm38.56\\ \\upmu\\mathrm{m}}.$ 。  \n\n![](images/0969e163a1bd00b48594b8b69480819be05fec64ed912893ec9a2fcb10a034c1.jpg)  \nFigure 4.31 (a) H & E staining of the subcutaneous tissue around different implants, scale bar $=500\\upmu\\mathrm{m}$ . (b) Quantitative analysis of fibrous layer thickness. \\*, # and & represents $p<0.05$ when compared with SCP, MACS and HAP, respectively.  \n\n利用CD86（M1 表面标记物）或 CD163（M2 表面标记物）的免疫荧光染色表征植入物-宿主界面巨噬细胞的表型改变情况，结果如 Figure 4.32 所示。在植入 3 天后，SCP 周围的 M1 巨噬细胞（CD86）的数量上升，并随着植入时间的增加而下降。与其他三组相比，MGH 周围的 M2 巨噬细胞（CD163）水平显著升高。定量分析结果如 Figure 4.33 所示，在植入 3 天和 5 天后，MGH 的 M1 巨噬细胞与M2 巨噬细胞的比例相较于 SCP 分别降低了 $57.23\\%$ 和 $58.90\\%$ ，这表明pH 响应性MOF 水凝胶修饰磺化 CFRPEEK 具有准确和及时的免疫调节特性。  \n\n![](images/a65149f64326606cadda14eed4f95c4a97cb9e1c18073d13ef2e7b59773ca5b2.jpg)  \nFigure 4.32 Immunofluorescence staining results of macrophages in the subcutaneous tissue around different implants 3 and 5 days after implantation: red (CD86, M1 marker), green (CD163, M2 marker) and blue (DAPI), scale bars $=200$ and $50~{\\upmu\\mathrm{m}}$ .  \n\n![](images/f91a37b211a10401a0b6d383dc325189aa9278e92e34c4282d20f5b15ac983ae.jpg)  \nFigure 4.33 The ratio of CD86-positive cells to CD163-positive cells in subcutaneous tissue around different implants. \\*, # and $\\&$ represents $p<0.05$ when compared with SCP, MACS and HAP, respectively.  \n\n植入3 和5 天后，取出植入物周围的皮下组织，并在整个过程中跟踪血管的形成。如 Figure 4.34a 所示，在植入第 3 天后，MGH 周围生成的毛细血管数量高于SCP 周围的毛细血管。在植入第 5 天后，HAP 和MGH 的血管生成均升高，MGH 的血管生成仍然是最高的，这表明 MOF 水凝胶修饰磺化 CFRPEEK 植入物有利于血管网络重塑。通过免疫荧光 CD31（一种内皮细胞生物标记物）染色进一步研究体内新生血管。如 Figure 4.34b 所示，MGH 的CD31 阳性血管增加。定量分析显示，MGH 的新血管数量在植入5d 后明显高于其他三组（Figure 4.34c），其中 MGH 的 CD31 阳性血管数量相较于 SCP 增加了 1.30 倍，这表明 MOF 水凝胶修饰磺化 CFRPEEK 植入物促进了血管的生成。上述研究结果表明用 MOF 水凝胶修饰磺化CFRPEEK 植入物具有良好的体内抗炎和血管生成特性。  \n\n![](images/26e25440851c119ac22405fab79915be8a420a5149672e41236ab6d72900dab2.jpg)  \n\n(b)  \n\n![](images/81f1aa81deb5dd0567d9a030a7734c1c50847547b83e2a56acb832ccc547d42e.jpg)  \nFigure 4.34 (a) In vivo vascularization assessment, scale bar $=2{\\mathrm{~mm}}$ . (b)  \n\nImmunofluorescence staining of CD31 in the subcutaneous tissue around different implants 3 and 5 days after implantation, scale bars $=200$ and $50~{\\upmu\\mathrm{m}}$ . (c) Quantitative analysis of CD31 immunofluorescence staining. \\*, # and & represents $p<0.05$ when compared with SCP, MACS and HAP, respectively.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 130,
+        "chunk": "# 4.3.13 体内成骨整合性能  \n\n体外细胞研究结果表明，磺化 CFRPEEK 表面上的 MOF 水凝胶具有良好的骨结合特性（包括优异的抗炎、血管生成和成骨特性）。创建兔胫骨缺损模型，以验证 MOF 水凝胶修饰磺化 CFRPEEK 植入物的体内骨整合特性。在手术后 4周和8 周，将兔子进行安乐死，并收取含样品的胫骨进行组织形态学和生物力学检测。在植入4 周和8 周后，利用显微计算机断层扫描（micro-CT）重建植入物周围的新骨结构，以分析植入物的新骨生成能力和骨-植入物界面的结合。Figure4.35a 和 b 是 micro-CT 的 2D 和 3D 重建的图像。在植入 4 周和 8 周后可以观察到所有植入物与周围的骨组织有明显的融合，没有发生移位，这表明植入物的长期骨固定。Figure 4.36a 和 b 是植入物周围新生骨的 3D 重建图像。在植入 4 周后，所有植入物都被薄薄的新骨层包围。与其他组相比，MGH 被更均匀和高质量的新生骨组织包围，这说明了 MGH 能促进缺损处的早期成骨。当植入时间延长至8 周时，与其他组相比，MGH 周围的骨体积更大，骨组织更致密，表明 MGH在宏观水平上具有出色的体内成骨能力。Figure 4.36c 和d 是新骨组织的厚度图像和骨组织参数的定量分析结果，MGH 具有最厚的骨组织，并且在植入 8 周以后MGH中新生骨的BV / TV和Tb.Th相较于SCP分别提高了 $28.08\\%$ 和 $99.53\\%$ 。上述结果表明， pH 响应性 MOF 水凝胶修饰磺化 CFRPEEK 植入物周围的新生骨在组织形态学上优于其他组，并且具有优越的早期成骨能力和长期骨生成能力。  \n\n![](images/e833040c7479d2d8e6303e1a52c995ca15ab9afa04b04eb76e48ccb36c76d50b.jpg)  \nFigure 4.35 (a and b) Reconstructed images of micro-CT and cross resection 4 and 8  \n\nweeks after surgery.  \n\n![](images/3092c3730da2bb26043018228838aac6171e344e60a0319e03bade8794b684d3.jpg)  \nFigure 4.36 (a and b) The 3D reconstructed micro-CT images of newborn bone with  \n\nimplants and without implants at 4 and 8 weeks, yellow represents sample, purple represents newly regenerated bone, scale bar $=2{\\mathrm{mm}}$ . (c) Representative images of Tb.Th at  4 and 8 weeks. (d) Quantitative analysis of micro-CT data including BV/TV and Tb.Th. \\*, # and & represents $p<0.05$ when compared with SCP, MACS and HAP, respectively.  \n\n通过组织学染色（H & E 和Masson 染色）进一步研究植入物和骨组织之间的整合。如 Figure 4.37 和 Figure 4.38 所示，在植入 4 周后，所有植入物周围都有一层薄薄的新生组织。在 SCP 植入界面观察到纤维组织（用红色箭头表示）。过度的免疫反应会导致持续性炎症，从而在植入物周围滋生纤维囊，并妨碍植入物的骨整合[316]。相比之下，MGH 周围的新生骨（用黑色箭头表示）与植入物直接接触。在 8 周时，所有植入物中的纤维囊减少，新生骨增多。MGH 植入物周围没有明显的纤维囊，并且与新生骨组织紧密结合，这表明 MOF 水凝胶修饰磺化CFRPEEK 植入物能够最大限度地减少免疫炎症反应并增强成骨性能，从而提高成骨固定能力。  \n\n![](images/e7ad246c1de3e4661e82311968963bbfcacae401457d550995b3e8206dac0322.jpg)  \nFigure 4.37 H & E staining and Masson staining at 4 weeks (Red arrows mark the fibrous capsule; Black arrows mark the direct contact between new bone and the implants), scale bars $=100$ and $20~\\upmu\\mathrm{m}$ .  \n\n![](images/f66deb1179861392c3afbdd72315c58d50583a5bb162c7c8c368af79d3f6d839.jpg)  \nFigure 4.38 H & E staining and Masson staining at 8 weeks (Red arrows mark the fibrous capsule; Black arrows mark the direct contact between new bone and the implants), scale bars $=100$ and $20~\\upmu\\mathrm{m}$ .  \n\n植入物与周围骨组织之间的稳定安全连接是骨植入物临床应用的关键要素之一[306, 366]。通过机械推出测试来研究不同植入物的骨-植入物接触强度。不同植入物在植入 8 周后的载荷-位移曲线以及植入 4 周和 8 周后的最大推出力（Fmax） 结果如 Figure 4.39a 和 $\\mathbf{b}$ 所示。正如预期的那样，MGH 的Fmax 值远高于 SCP、MACS 和 HAP 的值，在 4 周和 8 周时分别为 $61.00{\\scriptstyle\\pm2.00\\ \\mathrm{N}}$ 和$122.67{\\scriptstyle\\pm14.01\\mathrm{N}}$ ，相较于SCP 分别增加了1.61 倍和1.69 倍，这说明MOF 水凝胶修饰磺化CFRPEEK 植入物界面处的骨固定强度提高。  \n\n![](images/4cd509c9ff6447e38a36f5500238f167ca2420782e53cab02445675b5d7a692f.jpg)  \nFigure 4.39 (a) The load–displacement curves of different implants at 8 weeks. (b)  \n\nThe maximum push-out force (Fmax) of the implants at 4 and 8 weeks, \\*, # and & represents $p<0.05$ when compared with SCP, MACS and HAP, respectively.  \n\n通过SEM 和EDS 进一步分析附着在植入物上的新生骨组织。如 Figure 4.40所示，植入4 周后，所有植入物上都附着有新生骨组织。SCP 植入物上观察到多孔表面，表明覆盖其表面的骨组织很少。在 SCP 植入物的 EDS 面谱图上观察到少量Ca 和P 元素的沉积进一步证实了这一点，这也解释了为什么 SCP 更容易被推出。与其他三组相比，MGH 植入物周围的新骨生成更为广泛。当植入 8 周时，MGH 植入物的表面几乎完全被更规则，致密的新生骨组织覆盖，MGH 的Fmax增加。总的来说，上述所有数据都表明，MOF 水凝胶修饰磺化 CFRPEEK 植入物能够促进其周围高质量、连续的新骨组织的生成，从而提升植入物的机械锚定和长期成骨固定能力。  \n\n![](images/774e1ffae20ac556c796b3edc0893a2075925cee04f09111a44590bdd31cae4b.jpg)  \nFigure 4.40 The attachment and growth of bone tissue on the implant surface at 4 and 8 weeks analyzed by SEM and EDS maps (Green arrows indicate the calcified tissues, blue arrows point to the collagen, and yellow asterisks also represent the calcified tissues), scale bar $=25$ and $5\\upmu\\mathrm{m}$ .  \n\n植入物的另一个重要问题是体内生物毒性。对于 MOF 水凝胶修饰磺化CFRPEEK 植入物，MOF 水凝胶层的降解产物，如 $\\mathrm{Mg^{2+}}$ ，会循环到宿主血液中，从而对宿主器官产生毒副作用。在植入后 8 周后，收集实验动物的主要器官（包括心，肝，脾脏，肺和肾）进行 H & E 染色。如Figure 4.41 所示，在主要器官中未见病理性改变，证明本章中使用的所有植入物都没有明显的生物毒性。  \n\n![](images/254392db5ddd8a1db9f104d063bc907a4f9380f67ca80be5115cee34a6b49882.jpg)  \nFigure 4.41 H & E staining of major organs 8 weeks after implantation, scale bar $\\O=$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 131,
+        "chunk": "# 4.4 本章小结  \n\n考虑到植入物在植入后不同骨整合阶段所需的抗炎、血管生成和成骨特性，本研究团队在磺化CFRPEEK 植入物表面上设计并成功构建了多功能 pH 响应的MOF 水凝胶层。  \n\n（1）通过纳米羟基磷灰石、镁离子、没食子酸之间的耦合以及配位作用，设计制备了 HAP@Mg-GA MOF 纳米颗粒，并通过甲基丙烯酰化壳聚糖与磺化CFRPEEK 之间的紫外接枝作用在磺化 CFRPEEK 表面制备了负载 HAP@Mg-GAMOF 纳米颗粒的水凝胶层。该 pH 响应MOF 水凝胶层表现出出色的蛋白质吸附能力和pH 响应的生物分子释放能力，优异的亲水性和骨状磷灰石形成能力。  \n\n（2）高度生物相容性的 pH 响应MOF 水凝胶层能够缓慢释放 GA， $\\mathrm{Mg}^{2+}$ 和$\\mathrm{Ca}^{2+}$ ，这为磺化CFRPEEK 植入物修复受损骨组织提供了有利的生理环境。体外抗炎实验结果表明，相较于SCP，在MGH 上促炎因子TNF- $\\mathbf{\\sigma}\\cdot\\mathbf{a}$ 分泌减少了 $67.09\\%$ ，抗炎因子IL-10 分泌增加了 $284.19\\%$ ，这说明水凝胶层可以释放足够的生物分子以减轻早期急性炎症反应，并在炎症环境刺激下创造有利于骨再生的骨免疫微环境。  \n\n（3）体外成血管实验表明，MGH 上形成的管的分支长度相较于 SCP 增长了 $81.82\\%$ 。MOF 水凝胶层释放的 $\\mathrm{Mg}^{2+}.$ 促进植入物周围的血管生成，为新的骨形成阶段提供足够的氧气和营养成分。  \n\n（4）体内动物实验表明，MGH 周围的新生骨的骨小梁厚度相较于 SCP 提高了 $99.53\\%$ ，这说明在骨结合晚期， $\\mathrm{Ga}^{2+}$ 的长期和持续释放确保了细胞外骨基质的钙化并促进新骨的形成。  \n\n考虑到骨结合的不同阶段，构建多功能刺激响应性骨植入物的策略在惰性医疗植入物的表面生物工程中具有巨大潜力，特别是满足多功能植入物的临床需求。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 132,
+        "chunk": "# 第 5 章 结论与展望",
+        "category": " Conclusions"
+    },
+    {
+        "id": 133,
+        "chunk": "# 5.1 结论  \n\n本论文对骨骼的构成与结构、骨缺损的修复过程、骨组织工程、碳纤维增强聚醚醚酮表面生物功能化研究现状以及水凝胶在骨组织工程中的应用等进行了概述。针对CFRPEEK 植入物的生物惰性和成骨整合能力差这一瓶颈问题，从骨缺损愈合所需要的生物功能（抗炎、成血管和成骨）的角度出发，结合临床对超过临界尺寸骨缺损植入物的需求，本论文通过磺化处理和紫外接枝等表面改性技术，将负载地塞米松的甲基丙烯酰化明胶-聚丙烯酰胺复合凝胶、氧化石墨烯-羟基磷灰石冷冻凝胶和金属有机框架水凝分别修饰 CFRPEEK，从而开发了三种具有多功能生物活性凝胶修饰 CFRPEEK 骨科植入物，用于满足骨愈合环境下所需的多种生物功能，拓宽了 CFPEEK 复合材料在生物医学领域中的应用范围，为其临床应用提供了新的研发思路和科学参考。通过对表面改性 CFRPEEK 植入物的理化性能、体外细胞反应和体内骨整合性能进行分析，得出了以下结论：  \n\n1.从骨愈合所需的的生物相容性和成骨能力的角度出发，设计制备了负载Dex 的复合凝胶修饰CFRPEEK 植入物，用于治疗超临界尺寸的骨缺损。采用磺化处理和紫外接枝的表面改性方法将负载Dex 的GelMA/PAAM 复合水凝胶接枝到 CFRPEEK 植入物上，构建出了具有三维凝胶网络表面的 CFRPEEK 植入物。形貌分析表明，CFRPEEK 表面上成功构建了复合水凝胶网络结构，并且厚度为$50\\upmu\\mathrm{m}$ 。GelMA/PAAM/Dex 修饰 CFRPEEK 具有优异的亲水性，在 21 天内的 Dex释放效率为 $53\\%$ ，缓慢长期的 Dex 释放能力有利于 BMSC 细胞的成骨分化，并且它具有优异的体外矿化能力。体外细胞实验表明，BMSC 细胞在GelMA/PAAM/Dex 修饰 CFRPEEK 上能够较好的增殖、粘附和扩散，具有良好的体外生物相容性。 ALP、ARS 和RT-PCR 证明了它具有优异的体外成骨性能。体内大鼠的颅骨缺损实验表明，GelMA/PAAM/Dex 修饰 CFRPEEK 植入物具有优异的体内成骨性能，并且能够促进骨缺损的愈合。  \n\n2. 骨骼是一个高度血管化的组织，在骨缺损愈合的过程中伴随着血管的重塑。如果在骨愈合过程中的血管生成不及时，会造成氧气和营养物质的供给不足，从而导致后期的成骨能力差。针对这种情况，设计制备了多功能 GO-HAP 冷冻凝胶修饰 CFRPEEK 植入物，用于提高 CFRPEEK 植入物的成血管和成骨能力。首先，通过原位键合的方法制备 GO-HAP 纳米复合材料。然后，采用磺化处理和基于自由基光聚合的冷冻凝胶方法将负载 GO-HAP 的冷冻凝胶接枝到CFRPEEK 植入物表面上，构建了具有 3D 海绵状大孔冷冻凝胶网络表面的CFRPEEK 植入物。该冷冻凝胶层主要由 GO-HAP 纳米复合材料和GelMA/PEGDA 组成。在 CFRPEEK 表面构建的 3D 海绵状大孔冷冻凝胶的孔径为 $100~{\\upmu\\mathrm{m}}$ 左右，能够促进细胞的增殖、迁移和新血管的长入。冷冻凝胶层的厚度为 $45~{\\upmu\\mathrm{m}}$ 。细胞实验证明，该多功能植入物表面的 3D 海绵状大孔结构和 GO促进了 HUVEC 细胞的长入和迁移，增强了 CFRPEEK 植入物的体外成血管能力。GO-HAP 冷冻凝胶修饰CFRPEEK 植入物表面优异的亲水性和 $\\mathrm{Ca}^{2+}$ 的受控释放有利于BMSC 细胞的增殖、粘附和成骨分化。大鼠颅骨缺损实验进一步表明，GO-HAP 冷冻凝胶修饰 CFRPEEK 植入物可以迅速诱导新骨生成和新血管生成，显著提高了CFRPEEK 植入物的成骨固定和骨重塑能力。  \n\n3. 骨缺损的愈合发生在良好的炎症、血管化和成骨分化的基础上。植入物在植入早期过度的炎症反应和不及时的血管化会影响后期新骨的生成。为此，设计制备了 pH 响应性 MOF 水凝胶修饰磺化 CFRPEEK 植入物，以增强 CFRPEEK在植入后的抗炎、血管化和成骨能力。通过纳米羟基磷灰石、GA 和 $\\mathrm{Mg}^{2+}$ 之间的配位和耦合作用制备了具有核壳结构的 HAP@Mg-GAMOF 纳米颗粒。然后通过磺化处理和紫外接枝的方法将负载 HAP@Mg-GA MOF 纳米颗粒的甲基丙烯酰化壳聚糖水凝胶接枝到磺化 CFRPEEK 植入物表面。甲基丙烯酰化壳聚糖具有pH 响应性，所以 MOF 水凝胶修饰 CFRPEEK 植入物可以随着骨缺损处生理环境pH 值的变化来控制HAP@Mg-GA MOF 纳米颗粒中GA、 $\\mathrm{Mg}^{2+}$ 和 $\\mathrm{Ca}^{2+}$ 的释放，从而提高CFRPEEK 植入物的抗炎、血管化和成骨分化能力。实验结果表明，pH响应MOF 水凝胶修饰磺化CFRPEEK 植入物表现出优异的蛋白质吸附能力和 $\\mathsf{p H}$ 敏感的生物分子释放能力，以及出色的亲水性和良好的骨状磷灰石形成能力。MOF 水凝胶层的厚度为 $22\\upmu\\mathrm{m}$ 。体外和体内实验结果表明，磺化 CFRPEEK 表面的MOF 水凝胶层可以释放足够的抗炎药 GA 和营养元素 $\\mathrm{Mg}^{2+}$ ，减轻植入早期的炎症反应，并为接下来的新骨生成提供有利的骨免疫微环境。 $\\mathrm{Mg}^{2+}$ 还促进了植入物周围的血管重塑，为新骨的形成提供了足够的氧气和营养。 $\\mathrm{Ga}^{2+}$ 缓慢长期的释放促进了新骨的生成和植入物的骨整合。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 134,
+        "chunk": "# 5.2 展望  \n\n本论文通过表面改性设计制备了一系列多功能凝胶修饰 CFRPEEK 植入物，使CFRPEEK 植入物的骨整合能力得到了改善。然而，由于实验周期和实验条件的限制，有些科学问题仍需要进一步探究：  \n\n1. 虽然第 2 章中制备的负载 Dex 的复合凝胶层增强了 CFRPEEK 植入物的生物相容性和成骨能力，但是该凝胶层的骨缺损修复机理尚不明确，这还需要我们从生物分子信号传导角度进一步深入探讨。  \n\n2.  冷冻凝胶的孔结构影响细胞的粘附、增殖与迁移。关于 3D 海绵状大孔结构的设计，在第3 章中通过对 GelMA/PEDGA 的比例、反应温度、紫外接枝时间、后处理工艺等影响孔结构的因素进行了探讨，使得冷冻凝胶层的孔径约为$100\\upmu\\mathrm{m}$ ，但是冷冻凝胶层的孔结构（形状、孔间连通情况）还是不可控的。所以，在未来的研究中我们计划通过 3D 打印技术来调控孔结构，并通过细胞动力学来分析孔结构对细胞的粘附、增殖与迁移等的影响。  \n\n3. 骨整合主要包括巨噬细胞的免疫反应、内皮细胞的血管生成和成骨细胞的骨再生，每个阶段都可以通过一些共同的细胞间信号通路与其它阶段相互作用。对于第 4 章中制备的 MOF 水凝胶修饰磺化 CFRPEEK 植入物，本研究团队证明了它具有抗炎、成血管和成骨性能，但是各个阶段之间的协调机制还有待于在后续的研究中进一步探讨。  \n\n参考文献   \n[1] Qin D, Wang N, You X-G, et al. Collagen-based biocomposites inspired by bone hierarchical structures for advanced bone regeneration: ongoing research and perspectives [J]. Biomaterials Science, 2022, 10 (2): 318-353.   \n[2] Battafarano G, Rossi M, De Martino V, et al. Strategies for Bone Regeneration: From Graft to Tissue Engineering [J]. 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Mechanism of Exosomes Involved in Osteoimmunity Promoting Osseointegration Around Titanium Implants With SmallScale Topography [J]. Frontiers in Bioengineering and Biotechnology, 2021, 9: 682384. [320] Zhou A, Yu H, Liu J, et al. Role of Hippo-YAP Signaling in Osseointegration by Regulating Osteogenesis, Angiogenesis, and Osteoimmunology [J]. Frontiers in Cell and Developmental Biology, 2020, 8: 780.   \n[321] Berger M B, Slosar P, Schwartz Z, et al. A Review of Biomimetic Topographies and Their Role in Promoting Bone Formation and Osseointegration: Implications for Clinical Use [J]. Biomimetics, 2022, 7 (2): 46.   \n[322] Radulescu D E, Neacsu I A, Grumezescu A M, et al. Novel Trends into the Development of Natural Hydroxyapatite-Based Polymeric Composites for Bone Tissue 159  \n\nEngineering [J]. Polymers, 2022, 14 (5): 899.  \n\n[323] Shuai C, Feng P, Nie Y, et al. Nano-hydroxyapatite improves the properties of $\\upbeta$ - tricalcium phosphate bone scaffolds [J]. International Journal of Applied Ceramic Technology, 2013, 10 (6): 1003-1013.  \n\n[324] Roohani-Esfahani S I, Nouri-Khorasani S, Lu Z, et al. The influence hydroxyapatite nanoparticle shape and size on the properties of biphasic calcium phosphate scaffolds coated with hydroxyapatite-PCL composites [J]. Biomaterials, 2010, 31 (21): 5498-5509.   \n[325] Zhou C, Luo C, Liu S, et al. Pearl-inspired graphene oxide-collagen microgel with multi-layer mineralization through microarray chips for bone defect repair [J]. Materials Today Bio, 2022, 15: 100307.   \n[326] Feng A, Wang Y, Ding J, et al. Progress of stimuli-responsive nanoscale metal organic frameworks as controlled drug delivery systems [J]. Current Drug Delivery, 2021, 18 (3): 297-311.   \n[327] Zhang S, Jia Z, Cheng B, et al. Recent progress of perovskite oxides and their hybrids for electromagnetic wave absorption: a mini-review [J]. Advanced Composites and Hybrid Materials, 2022, 5 (3): 2440-2460.   \n[328] Liu Y, Zhou X, Jia Z, et al. Oxygen Vacancy-Induced Dielectric Polarization Prevails in the Electromagnetic Wave-Absorbing Mechanism for Mn-Based MOFsDerived Composites [J]. Advanced Functional Materials, 2022, 32 (34): 2204499. [329] Jia Z, Kong M, Yu B, et al. Tunable Co/ZnO/C $@$ MWCNTs based on carbon nanotube-coated MOF with excellent microwave absorption properties [J]. Journal of Materials Science and Technology, 2022, 127: 153-163.   \n[330] Yu M, You D, Zhuang J, et al. Controlled release of naringin in metal-organic framework-loaded mineralized collagen coating to simultaneously enhance osseointegration and antibacterial activity [J]. ACS Applied Materials and Interfaces, 2017, 9 (23): 19698-19705.   \n[331] Wei X, Zhou W, Tang Z, et al. Magnesium surface-activated 3D printed porous PEEK scaffolds for in vivo osseointegration by promoting angiogenesis and osteogenesis [J]. Bioactive Materials, 2023, 20: 16-28.   \n160 [332] Zhang X, Huang P, Jiang G, et al. A novel magnesium ion-incorporating dualcrosslinked hydrogel to improve bone scaffold-mediated osteogenesis and angiogenesis [J]. Materials Science and Engineering C, 2021, 121: 111868.   \n[333] Gao P, Fan B, Yu X, et al. Biofunctional magnesium coated Ti6Al4V scaffold enhances osteogenesis and angiogenesis in vitro and in vivo for orthopedic application [J]. Bioactive Materials, 2020, 5 (3): 680-693.   \n[334] Kang Y, Xu C, Meng L, et al. Exosome-functionalized magnesium-organic framework-based scaffolds with osteogenic, angiogenic and anti-inflammatory properties for accelerated bone regeneration [J]. Bioactive Materials, 2022, 18: 26-41. [335] Qiao W, Wong K H M, Shen J, et al. TRPM7 kinase-mediated immunomodulation in macrophage plays a central role in magnesium ion-induced bone regeneration [J]. Nature Communications, 2021, 12 (1): 2885.   \n[336] Sharma A, Kumar A, Li C, et al. A cannabidiol-loaded Mg-gallate metal-organic framework-based potential therapeutic for glioblastomas [J]. Journal of Materials Chemistry B, 2021, 9 (10): 2505-2514.   \n[337] Sohrabi F, Dianat M, Badavi M, et al. Gallic acid suppresses inflammation and oxidative stress through modulating Nrf2-HO-1-NF- $\\mathbf{\\sigma}\\cdot\\kappa\\mathbf{B}$ signaling pathways in elastaseinduced emphysema in rats [J]. Environmental Science and Pollution Research, 2021, 28 (40): 56822-56834.   \n[338] Wu Y, Li K, Zeng M, et al. Serum Metabolomics Analysis of the AntiInflammatory Effects of Gallic Acid on Rats With Acute Inflammation [J]. Frontiers in Pharmacology, 2022, 13: 830439.   \n[339] Ahn C B, Jung W K, Park S J, et al. Gallic Acid- $\\mathbf{\\cdotg}$ -Chitosan Modulates Inflammatory Responses in LPS-Stimulated RAW264.7 Cells Via NF- $\\mathbf{\\sigma}_{\\kappa\\mathrm{B}}$ , AP-1, and MAPK Pathways [J]. Inflammation, 2016, 39 (1): 366-374.   \n[340] Ge G, Bai J, Wang Q, et al. Punicalagin ameliorates collagen-induced arthritis by downregulating M1 macrophage and pyroptosis via NF- $\\boldsymbol{\\kappa}\\mathrm{B}$ signaling pathway [J]. Science China Life Sciences, 2022, 65 (3): 588-603.   \n[341] Zheng Z, Chen Y, Guo B, et al. Magnesium-organic framework-based stimuliresponsive systems that optimize the bone microenvironment for enhanced bone 161  \n\nregeneration [J]. Chemical Engineering Journal, 2020, 396: 125241.  \n\n[342] Cooper L, Hidalgo T, Gorman M, et al. A biocompatible porous Mg-gallate metalorganic framework as an antioxidant carrier [J]. Chemical Communications, 2015, 51 (27): 5848-5851.   \n[343] Chen F F, Zhu Y J, Xiong Z C, et al. Hydroxyapatite Nanowires $@$ Metal–Organic Framework Core/Shell Nanofibers: Templated Synthesis, Peroxidase-Like Activity, and Derived Flexible Recyclable Test Paper [J]. 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Amphiphilic quaternized chitosan: Synthesis, characterization, and anti-cariogenic biofilm property [J]. Carbohydrate Polymers, 2022, 277: 118882.   \n[349] Djordjevic A, Ignjatovic N, Seke M, et al. Synthesis and characterization of hydroxyapatite/fullerenol nanocomposites [J]. Journal of Nanoscience and Nanotechnology, 2015, 15 (2): 1538-1542.   \n[350] Raphel J, Karlsson J, Galli S, et al. Engineered protein coatings to improve the osseointegration of dental and orthopaedic implants [J]. Biomaterials, 2016, 83: 269- 282.   \n[351] Lv L, Li K, Xie Y, et al. Enhanced osteogenic activity of anatase TiO2 film: Surface hydroxyl groups induce conformational changes in fibronectin [J]. Materials 162  \n\nScience and Engineering C, 2017, 78: 96-104.  \n\n[352] Yang G, Wang X, Fu S, et al. pH-triggered chitosan nanogels via an ortho esterbased linkage for efficient chemotherapy [J]. Acta Biomaterialia, 2017, 60: 232-243. [353] Wang N, Liang H, Zen K. Molecular mechanisms that influence the macrophage m1-m2 polarization balance. Frontiers in immunology, 2014, 28(5): 614.   \n[354] Pajarinen J, Lin T, Gibon E, et al. Mesenchymal stem cell-macrophage crosstalk and bone healing [J]. Biomaterials, 2019, 196: 80-89.   \n[355] Lee S M, Son K N, Shah D, et al. Histatin-1 attenuates LPS-induced inflammatory signaling in RAW264.7 macrophages [J]. International Journal of Molecular Sciences, 2021, 22 (15): 7856.   \n[356] Lin W H, Kuo H H, Ho L H, et al. Gardenia jasminoides extracts and gallic acid inhibit lipopolysaccharide-induced inflammation by suppression of JNK2/1 signaling pathways in BV-2 cells [J]. Iranian Journal of Basic Medical Sciences, 2015, 18 (6): 555-562.   \n[357] Domazetovic V, Marcucci G, Iantomasi T, et al. Oxidative stress in bone remodeling: Role of antioxidants [J]. Clinical Cases in Mineral and Bone Metabolism, 2017, 14 (2): 209-216.   \n[358] Sun H, Zheng K, Zhou T, et al. Incorporation of zinc into binary SiO2-CaO mesoporous bioactive glass nanoparticles enhances anti-inflammatory and osteogenic activities [J]. Pharmaceutics, 2021, 13 (12): 2124.   \n[359] Tsai Y L, Theato P, Huang C F, et al. A 3D-printable, glucose-sensitive and thermoresponsive hydrogel as sacrificial materials for constructs with vascular-like channels [J]. Applied Materials Today, 2020, 20: 100778.   \n[360] Cheng K-C, Huang C-F, Wei Y, et al. Novel chitosan–cellulose nanofiber selfhealing hydrogels to correlate self-healing properties of hydrogels with neural regeneration effects [J]. NPG Asia Materials, 2019, 11 (1): 25.   \n[361] Cai S, Wu C, Yang W, et al. Recent advance in surface modification for regulating cell adhesion and behaviors [J]. Nanotechnology Reviews, 2020, 9 (1): 971-989. [362] Zhu D, You J, Zhao N, et al. Magnesium Regulates Endothelial Barrier Functions through TRPM7, MagT1, and S1P1 [J]. Advanced Science, 2019, 6 (18): 1901166. [363] Germaini M M, Detsch R, Grünewald A, et al. Osteoblast and osteoclast responses to A/B type carbonate-substituted hydroxyapatite ceramics for bone regeneration [J]. Biomedical Materials (Bristol), 2017, 12 (3): 035008.   \n[364] Zhou M, Geng Y M, Li S Y, et al. Nanocrystalline hydroxyapatite-based scaffold adsorbs and gives sustained release of osteoinductive growth factor and facilitates bone regeneration in mice ectopic model [J]. Journal of Nanomaterials, 2019, 2019.   \n[365] Yuan Z, Wei P, Huang Y, et al. Injectable PLGA microspheres with tunable magnesium ion release for promoting bone regeneration [J]. Acta Biomaterialia, 2019, 85: 294-309.   \n[366] Liu Y, Rath B, Tingart M, et al. Role of implants surface modification in osseointegration: A systematic review [J]. Journal of Biomedical Materials Research Part A, 2020, 108 (3): 470-484.",
+        "category": " Conclusions"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Material-Independent Surface Chemistry beyond Polydopamine Coating  \n\nHaesung A. Lee,† Yanfei Ma,‡,§ Feng Zhou,\\*,‡,∥ Seonki Hong, $\\ast,\\bot\\textcircled{\\dag}$ and Haeshin Lee\\*,†  \n\n†Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), 291 University Road, Daejeon 34141,   \nSouth Korea   \n‡State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000,   \nChina   \n§University of Chinese Academy of Sciences, Beijing 100049, China   \n∥State Key Laboratory of Solidification Processing, College of Materials Science and Technology, Northwestern Polytechnical   \nUniversity, 127 YouyiXi Road, Xi’an 710072, China   \n⊥Department of Emerging Materials Science, Daegu Gyeongbuk Institute of Science and Technology (DGIST), 333 Techno   \nJungang-daero, Daegu 42988, South Korea  \n\n![](images/5a5cdf2b531f44cb5c329e92a716cdbfe07351cdc688a6f1e34dc8459672d9fd.jpg)  \n\nCONSPECTUS: Various methods have been developed in surface chemistry to control interface properties of a solid material. A selection rule among surface chemistries is compatibility between a surface functionalization tool and a target material. For example, alkanethiol deposition on noble metal surfaces, widely known as the formation of a self-assembled monolayer (SAM), cannot be performed on oxide material surfaces. One must choose organosilane molecules to functionalize oxide surfaces. Thus, the surface chemistry strictly depends on the properties of the surface. Polydopamine coating is now generally accepted as the first toolbox for functionalization of virtually any material surface. Layer-by-layer (LbL) assembly is a widely used method to modify properties of versatile surfaces, including organic materials, metal oxides, and noble metals, along with polydopamine coating. On flat solid substrates, the two chemistries of polydopamine coating and LbL assembly provide similar levels of surface modifications. However, there are additional distinct features in polydopamine. First, polydopamine coating is effective for two- or three-dimensional porous materials such as metal−organic frameworks (MOFs), synthetic polyolefin membranes, and others because small-sized dopamine $\\mathrm{'MW}=153.18~\\mathrm{u},$ ) and its oxidized oligomers are readily attached onto narrow-spaced surfaces without exhibiting steric hindrance. In contrast, polymers used in LbL assembly are slow in diffusion because of steric hindrance due to their high molecular weight. Second, it is applicable to structurally nonflat surfaces showing special wettability such as superhydrophobicity or superoleophobicity. Third, a nonconducting, insulating polydopamine layer can be converted to be a conducting layer by pyrolysis. The product after pyrolysis is a N-doped graphene-like material that is useful for graphene or carbon nanotube-containing composites. Fourth, it is a suitable method for engineering the surface properties of various composite materials. The surface properties of participating components in composite materials can be unified by polydopamine coating with a simple one-step process. Fifth, a polydopamine layer exhibits intrinsic chemical reactivity by the presence of catecholquinone moieties and catechol radical species on surfaces. Nucleophiles such as amine and thiolate spontaneously react with the functionalized layer.  \n\nApplications of polydopamine coating are exponentially growing and include cell culture/patterning, microfluidics, antimicrobial surfaces, tissue engineering, drug delivery systems, photothermal therapy, immobilization of photocatalysts, Li-ion battery membranes, Li−sulfur battery cathode materials, oil/water separation, water detoxification, organocatalysts, membrane separation technologies, carbonization, and others. In this Account, we describe various polydopamine coating methods and then introduce a number of chemical derivatives of dopamine that will open further development of material-independent surface chemistry.",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1. ADVANCES IN POLYDOPAMINE COATING TECHNIQUES",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 1.1. Understanding the Formation of Polydopamine  \n\nUnderstanding the chemistry of polydopamine formation is a challenging subject despite the extensive studies over a decade because of its chemical diversity and heterogeneity. A consensus in polydopamine chemistry begins with spontaneous oxidation of dopamine to dopamine quinone followed by further oxidative conversion to 3,4-dihydroxyindole (DHI), which is considered as an acceptable pathway for a polydopamine monomer since 2007.1 However, recent studies have proposed the existence of other intermediates in polydopamine formation: (1) there is always found to be a detectable level of uncyclized dopamine monomer (i.e., the presence of $\\mathrm{-NH}_{2,}^{\\cdot}$ ) in polydopamine chains,2,3 which indicates that the conversion yield from dopamine to DHI is not $100\\%$ (various reactions are discussed in sections 1.2 and 1.3); (2) DHI alone is insufficient for coating;4 (3) degradation of a catechol ring generates pyrroles with carboxylic acid in polydopamine;5,6 (4) DHI−dopamine oligomer intermediates participate in diverse non-covalent interactions (details are provided in section 1.1.2).2,7 Therefore, supramolecular assembly of various combinations of DHI-, dopamine-, and pyrrole-containing oligomers is a current structural insight for polydopamine. Thus, further understanding of the chemical diversity of oligomers that constitute polydopamine is critical in the future. Questions related to the topic include identifications of major repeating units in oligomers and molecular weight distributions. Finally, mechanisms to drive assembly of the oligomers should be address. In sections 1.1.1 and 1.1.2 we introduce a few very recent studies that address these questions related to polydopamine formation.  \n\n![](images/d123b7019d1fa30fddb109295106bea2d16266eb3c9a0a40aae59f423c0097e4.jpg)  \nFigure 1. Programmable disassembly and reassembly of polydopamine coatings by alternating non-covalent and cation $-\\pi$ interactions between oligomers. Adapted from ref 7.  \n\n1.1.1. Synergistic Effect of Amine and Catechol in Material Independence. Polydopamine coating is the first reported material-independent surface chemistry that can be applicable to virtually all kinds of substrates, regardless of surface properties.1 Catechol can interact with substrates via various types of molecular interactions: coordination bonding to metals,8 Michael-type addition and Schiff base formation with amine groups,8 hydrogen bonding on metal oxides,9 and so on. However, this dynamic bonding to various substrates is insufficient to explain the material independence shown in polydopamine coating because amine-free catechol analogues often fail to show such versatile surface modifications.10 A recent study performed using a surface force apparatus subsequently emphasized the synergistic effect of amine and catechol. Amine groups play an important role in displacing hydrated salts on the surface and then bring catechols near the surface to form strong molecular bonds.11  \n\n1.1.2. Non-covalent Interactions in Polydopamine. The identification of a physical trimer, (dopamine) $_{2}/\\mathrm{DHI}$ , in polydopamine suggested that non-covalent interactions between low-molecular-weight intermediates could be strong enough to generate a three-dimensional molecular assembly. Subsequent studies have suggested various types of noncovalent interactions, such as $\\pi$ effects, electrostatic forces, and van der Waals forces.12,13 Recently, Hong and co-workers7 suggested a new type of non-covalent interactions, cation $-\\pi$ interactions, upon revealing the important role of protonated amine groups in polydopamine. It was found that polydopamine disassembled from the surface under strongly basic conditions $\\mathrm{\\langlepH>10\\rangle}$ as a result of loss of cation−π interactions because the amine cationic species of dopamine became deprotonated. However, under the same $\\mathrm{\\tt{pH}}$ conditions in the presence of additional cations, it can mediate strong non-covalent interactions. For the first time, the authors demonstrated the pH-sensitive disassembly and subsequent reassembly of a polydopamine coating by re-establishing cation− $\\pi$ interactions using additional cations (Figure 1). Because catechol in DHI is not a strongly $\\pi$ -conjugated system, the coexistence of protonated uncyclized amines is a critical factor in the formation of polydopamine. However, recent studies have raised new questions about the origin of the material-independent coating properties of polydopamine, as systems of catecholic compounds and diamines have also succeeded in generating material-independent coating capabilities similar to those of polydopamine even though DHI is not generated during the process.14,15  \n\n![](images/01eb60f478bac53f90b70aa04c4c504f56e0a4dc37d8e5727ab71081af918374.jpg)  \nFigure 2. Nature-derived catechol/gallol families. $\\left({\\mathfrak{a}}{-}{\\mathfrak{g}}\\right)$ Representative plant-derived polyphenol molecules (section 2.1): (a) tannic acid; (b) catechin; (c) epigallocatechin (EGC); (d) epicatechin gallate (ECG); (e) epigallocatechin gallate (EGCG); (f) hydroxyhydroquinol; (g) morin. $\\left(\\mathrm{h-}\\right.$ j) Polymerization pathway of norepinephrine, a catecholic neurotransmitter (section 2.2): (h) norepinephrine; (i) dihydroxybenzaldehyde (DHBA); (j) norepinephrine−DHBA conjugate.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1.2. Importance of Oxygen in Polydopamine Growth",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 1.2.1. Thin-Film Formation at the Air−Water Interface  \n\nBall and co-workers observed that the growth of a polydopamine film at the air−water interface was twice as fast as that in solution and that the film was able to be transferred to a solid support.16 Independently, Hong et al.17 showed that amine-rich polymers such as polyethylenimine (PEI) dramatically enhanced interfacial film growth, allowing the film to be free-standable. Whereas the air-exposed side of the film was composed largely of nonswellable nonporous catechols resulting from oxidation, the solution side exhibited micropillar-rich water-swellable porous structures that displayed a Janus-type morphology.17 Interfacial free-standing films can also be produced by phenolic compounds called pyrogallols.18 The formation of films containing pyrogallol and PEI was rapid and occurred in a few minutes. In addition, the damaged area in the film was rapidly resealed by film regeneration because of re-exposure of the solution to the air−water interface.18  \n\n1.2.2. Gradient Polydopamine Coating. Limited oxygen diffusion naturally generates an oxygen gradient from the top air−water interface to the deep bulk solution. Xu and co-workers utilized the natural oxygen gradient to achieve a polydopamine coating showing gradients in thickness and hydrophilicity simply by tilting the surface in the solution during the coating process.19 Repeated draining and replenishing of the surface by cyclic tilting in the solution resulted in a similarly graded polydopamine coating that possessed gradient antibacterial properties.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 1.3. Various Polydopamine Coating Methods",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 1.3.1. Polydopamine Coating at Acidic/Neutral pH.  \n\nThe $\\mathrm{p}K_{\\mathrm{al}}$ of the catechol group in dopamine is approximately 9; at this $\\mathrm{\\tt{pH}}_{\\mathrm{\\tt{f}}}$ , dissolved oxygen can uptake an electron from the deprotonated catechol anion, producing an oxidized species called catechol quinone. However, a decrease in $\\mathrm{\\ttpH}$ to neutral or acidic does not produce deprotonated catechol anions. Thus, chemical oxidants can be an option for oxidants to trigger polydopamine coating at acidic $\\mathrm{\\tt{pH}}$ The chemical structure of polydopamine can be altered depending on the oxidant used: it is noteworthy that the DHI subunits were partially degraded by the action of the oxidants during the oxidant coating, causing the surface to become more hydrophilic.21 A hydrothermal process in an autoclave can trigger polydopamine synthesis without oxidants.22 Also, plasma-activated water can initiate dopamine polymerization even in the absence of oxygen.23  \n\n1.3.2. Polydopamine Coating with Rapid Kinetics. The combination of basic $\\mathrm{\\tt{pH}}$ and chemical oxidants provides a dramatic increase in coating rate. The addition of 2 molar equiv of sodium periodate to dopamine at $\\mathrm{\\pH\\}9.5$ resulted in an approximately 200-fold increase in the coating rate.24 The coating could be applied to a large surface via a simple spray approach.24 Microwaves are another emerging trigger for catechol oxidation. Lee et al.25 reported that microwaves successfully reduced the coating time from $6\\mathrm{~h~}$ to $15\\ \\mathrm{min}$ They suggested that microwave-assisted rapid polydopamine coating can be achieved by the synergistic action of thermal acceleration followed by radical generation.25  \n\n1.3.3. Polydopamine Coating in Organic Solvents. Poor access of water molecules to hydrophobic surfaces is a major drawback of aqueous-based polydopamine coating methods despite the unique material-independent applicability. However, it has been reported that polydopamine coating of hydrophobic surfaces can be performed in the presence of watermiscible solvents such as alcohols.26 Furthermore, by the addition of an organic base such as piperidine, organic solvents that cannot be mixed with water can also be used as solvents for hydrophobic surface coating.27  \n\n1.3.4. Phototriggered Polydopamine Coating. Photoillumination followed by photoreaction is a facile method that can be turned on and off in a spatiotemporally controllable manner. This approach has been useful in the fabrication of twodimensional patterns on surfaces. Levkin’s group reported the photo-cross-linking reaction of catechol and gallol derivatives. UV irradiation at $260\\ \\mathrm{nm}$ triggered the oxidation of both dopamine28 and plant polyphenols29 and generated a coating in a few hours.  \n\n1.3.5. Dopamine One-Pot Coating with Desired Molecules. Polydopamine-coated surfaces can be further functionalized via various chemical modes of surface-decorated catechols. However, this two-step process is time-consuming and labor-intensive. In 2012, Kang and co-workers developed a single-step surface functionalization method, denoted as “onepot” coating, which introduces the desired molecule to the surface during polydopamine coating. It was found that biopolymers inserted in the one-pot polydopamine coating retained their biological activity.30",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2. NATURE-DERIVED CATECHOL/GALLOL FAMILIES",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.1. Plant Polyphenol Family  \n\n2.1.1. Tannic Acid. In nature there exist a number of catechol/gallol chemical derivatives in addition to dopamine. Gallol is trihydroxyphenol, which is biochemically synthesized by hydroxylation of catechol. Gallol-containing molecules are generally superior in intermolecular binding, particularly for proteins. A representative gallol-containing small molecule is tannic acid (Figure 2a). In 1969 it was reported that tannic acid binds to proteins, producing complexes instantaneously.31 At neutral $\\mathrm{\\tt{pH}}_{\\mathrm{\\tt{f}}}$ , the gallol moieties in tannic acid are not fully protonated, and parts of the hydroxyl groups are deprotonated to form galloquinone. The hydrogen-bond configuration of the gallol moieties in complexes shows the alternating presence of hydrogen-bond donors and acceptors. The coexistence of donors and acceptors is closely related to cytosine base pairing in DNA as well as $\\alpha$ -helix and $\\beta$ -sheet formation in proteins. In this developing hypothesis, tannic acid is superior in the formation of protein/tannic acid complexes. A recently published study in 2018 demonstrated that proteins and peptides are complexed with tannic acid to form soluble nanoparticles in particular stoichiometric ranges. For example, nanoparticles are stably formed in aqueous solutions with a [tannic acid]/[green fluorescent protein] stoichiometry between 70 and 140. Surprisingly, when the nanocomplexes are injected via an intravenous route, they effectively target the myocardium. In addition to the extracellular matrix (ECM) proteins in the myocardium, mucin, found in the oral cavity as well as the gastrointestinal tract, is readily complexed with tannic acid.32 Although the exact binding sites in mucin are not known, the abundant hydroxyl groups of tannic acid could interact with surface-exposed oligo/polysaccharides via hydrogen bonds. The consumption of hydroxyl groups of tannic acid to anchor and mask the lubricating oligo/polysaccharides of mucin results in exposure of the phenolic moieties of tannic acid to the outermost layer. Thus, an increased feeling of friction is produced within the oral cavity, and this phenomenon is described as the unique taste called “astringency”.33 In addition to interactions with proteins, tannic acid is able to bind with a zwitterionic polymer, poly(sulfobetaine methacrylate) (PSBMA). This zwitterionic hydrophilic surface exhibits protein adsorption resistance (i.e., antifouling) properties.34 Similar to the material-independent surface chemistry of polydopamine, tannic acid also shows versatility in surface modifications. Surfaces of metal oxides and even hydrophobic polymers have been functionalized with a thickness of $\\overline{{20}}\\ \\mathrm{nm}$ .35 The surface wettability is controlled by tannic acid. Dense coating onto a polypropylene membrane with tannic acid-functionalized carbon nanotubes generates superoleophobicity upon vacuum filtration of the carbon nanotube solution.36 An additional important ability of tannic acid is the formation of metal−gallol coordination bonds, which are the basis of a second materialindependent surface chemistry.37,38 Metal ion/tannic acid coordination complexes result in the formation of thin adherent films on virtually any type of substrate. This surface chemistry is known as a metal−phenolic network (MPN). Beyond the thinfilm form adhered on surfaces, MPNs can be combined with polymer scaffolds such as polysaccharides to make freestandable hydrogel or fiber forms.39,40 Compared with polydopamine coating, an advantage of MPN surface chemistry is its rapid kinetics. Thus, MPN is suitable to functionalize “living” cell surfaces. Choi and co-workers reported the single-cell encapsulation of individual Saccharomyces cerevisiae by artificial shells (or spores).41 The yeast surfaces protected by MPN layers showed resistance to external stimuli such as UV radiation, lytic enzymes, and toxic silver nanoparticles.  \n\n2.1.2. Catechin Derivatives. Catechin (Figure 2b) is a nondegradable phenolic molecule that is a plant secondary metabolite. Similar to tannic acid, catechin also exhibits surface modification and intermolecular interaction capabilities. Catechin does functionalize various surfaces, such as polycarbonate (PC), nylon, poly(dimethylsiloxane) (PDMS), poly(tetrafluoroethylene) (PTFE), polystyrene (PS), Au, and $\\mathrm{SiO}_{2}$ .42 Interestingly, functionalized surfaces triggered the photografting of polymer brushes of PSBMA and poly(2- ((methacryloyloxy)ethyl)trimethylammonium chloride).43 The antioxidative and calcium-binding properties of surface-coated catechin resulted in the osteogenic differentiation of human adipose-derived stem cells (hADSCs).44 This was the first study to demonstrate the effectiveness of a polyphenol coating in stem cell culture. Catechin is poorly water-soluble. However, it can form complexes with poly(ethylene glycol) (PEG) by lyophilization processes. After freeze-drying, catechin/PEG complexes became highly water-soluble, demonstrating therapeutic effects for dry eye.45  \n\n2.1.3. Urushiol and Alkanecatechol. Beginning prior to the fifth century B.C., a series of catechol derivatives with unsaturated hydrocarbons, collectively called “urushiols”, have been used. Urushiols form protective and polishing coating layers on the surfaces of various wooden furniture. Oxidative cross-linking between catechol in urushiol coatings has similar aspects to polydopamine and other aforementioned polyphenol coatings. However, this cross-linking is largely mediated by the enzyme copper-containing laccase.46 Recently, saturated (i.e., hydrogenated) urushiol (h-urushiol) was prepared in a synthetic manner to investigate the physicochemical contributions of the saturated hydrocarbon in natural urushiols.47 Curing with hurushiol takes a long time $(\\sim12\\ \\mathrm{h})$ compared with the time required for natural urushiol $(<1\\mathrm{~h~})$ . Strain-induced elastic buckling occurs easily in $\\mathbf{h}$ -urushiol, indicating that the double bonds in natural urushiol form abundant cross-links between molecules. Further systematic molecular engineering studies performed by changing the hydrocarbon length were reported by the Ruiz-Molina group.48 The key purpose of the study was to provide hydrophobicity on polyester fabric surfaces. Applications include oil-absorbent and water-repellent materials after the formation of alkanecatechol coatings.  \n\n![](images/abae4057295553a2fc069f86d372f05c08660a52aa5fb1f32924958040a8bd6c.jpg)  \nFigure 3. Small-molecule dopamine conjugates. $(\\mathsf{a},\\mathsf{b})$ Catecholic derivatives. (c) Catechol-containing acrylate. (d) Diels−Alder (DA) reaction. (e) Cycloaddition reactions for click chemistry. (f) Catecholic liquid lubricant. $\\mathbf{\\eta}(\\mathbf{g})$ Zwitterionic polymers in biosurface formation and resistance to fouling. (h) Polydopamine gradient.",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.2. Neurotransmitters: Norepinephrine  \n\nThe oxidative polymerization of norepinephrine was the first use of a small catecholamine derivative for material-independent coating and was reported shortly after polydopamine.49 In the process of polydopamine coating, oligo-DHI undergoes uncontrolled intermolecular interactions with other intermediates, producing massive aggregation. In contrast, the poly(norepinephrine) coating shows extremely smooth surface functionalization.50 As a result of the presence of additional alkyl hydroxyl groups in norepinephrine, tautomerization occurs, producing catechol aldehyde, which subsequently reacts with the amine group of norepinephrine, resulting in the formation of 3,4-dihydroxybenzaldehyde (DHBA) (Figure $\\mathrm{2h,i}^{\\cdot}$ . DHBA acts as the key molecule in reducing surface roughness by preventing the intermolecular aggregation of norepinephrine intermediates. The smooth poly(norepinephrine) nanolayer allows the functionalization of surfaces with micro/nanoscale structures without increasing surface roughness. Furthermore, the secondary alkylamine in DHBA provides a suitable platform for NONO-ate surface immobilization as a nitric oxide (NO) depot. The alkyl hydroxyl group of norepinephrine is effective in initiating surface-initiated ring-opening metathesis polymerization (SI-ROMP) on surfaces.49 In the cited study, the authors demonstrated the surfaceinitiated polymerization of $\\beta$ -caprolactone in a materialindependent manner. Later, the same group also showed surface-initiated atomic transfer radical polymerization (SIATRP) by a catechol-conjugated bromine initiator.51 As the redox activity of polydopamine layers originates from catechol oxidation and reduction, poly(norepinephrine) layers also show redox-active properties. Graphene oxide (GO) spontaneously receives electrons from poly(norepinephrine) layers to create reduced GO (rGO) by simple mixing.52 The advantage of using poly(norepinephrine) reduction is that the surfaces of rGO are simultaneously functionalized and used in additional metal ion doping or SI-ROMP. Biomedical applications of poly(norepinephrine) coatings have been published. Compared with polydopamine, surfaces coated by poly(norepinephrine) show increased hydrophilicity and provide versatile platforms for material-independent mammalian cell cultures. In particular, such coating is effective in neural stem cell cultures, even for lowsurface-energy materials such as PDMS and PTFE.53 By the coimmobilization of biomolecules and other molecules during poly(norepinephrine) layer formation (see section 1.3.5), researchers have demonstrated controlled cell adhesion and proliferation.54",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3. SMALL-MOLECULE DOPAMINE CONJUGATES FOR APPLICATIONS",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3.1. Surface-Initiated Polymerization  \n\n3.1.1. SI-ATRP. In 2005, a mussel-inspired SI-ATRP initiator was first reported (Figure 3a). The phenolic hydroxyl in the initiator can work as an anchor site for attachment on various surfaces.55 This biomimetic surface-grafting strategy is a highly versatile tool for functionalizing various substrates, such as Au, Ti, stainless steel, Si, quartz, glass, polypropylene, PDMS, PS, and nylon.56−58 By means of this strategy, researchers successfully brush-grafted poly(3-sulfopropyl methacrylate potassium salt) (PSPMA) onto very inert diamond-like carbon (DLC) films. The as-prepared functionalized DLC film surface showed good superhydrophilicity and excellent water lubrication properties.59 Moreover, this biomimetic surface-grafting strategy is applicable to rough surfaces such as fibrils and particles.60,61 Kuang and Messersmith56 synthesized a biomimetic tripeptide bromide (BrYKY). BrYKY was successfully assembled onto the substrate surface, and then PSBMA was grafted to form a high-density polymer brush layer. This method is a water-based reaction, which can avoid erosion from solvent to substrate. In addition, macromolecules functionalized with catechol groups have also been directly synthesized to realize the one-step modification of substrates. For example, zwitterionic sulfobetaine polymers with catechol groups (DOPA-PSB) were prepared to decorate a hydrophobic substrate surface.58  \n\n3.1.2. SI-ROMP. SI-ROMP based on catechol-functionalized initiators has also been reported. Perfluoroalkyl-substituted polymer brushes can be successfully grafted onto the surface of various metals and metal oxides. The grafted polymer brushes have good adhesion strength and thermal stability under ambient conditions (Figure 3b).62 By means of microcontact printing $\\left(\\mu\\mathrm{CP}\\right)$ and the combination of SI-ROMP with SIATRP, patterned microstructures have been fabricated, providing potential applications in hybrid surfaces, biochips, and biosensors.57 A multi-initiator coating was achieved by coadsorption, which can anchor hydroxyl and bromide moieties on the substrate to initiate ROMP and ATRP, respectively.51 Another step of research progress in the universal surfaceinitiated polymerization method was to initiate the free radical polymerization from a polydopamine layer under UV radiation or sunlight.63 Because polydopamine can be deposited on any substrate, it can also be brush-grafted from anywhere.  \n\n3.1.3. Catecholic Polyacrylates. To prepare coatings with long-term adhesion stability, researchers introduced catechols into the polymer chain. It was found that when a catechol group was incorporated into a perfluoropolymer, the polymer could adsorb onto a variety of substrates with high stability and render them superhydrophobic and superoleophobic.64 Zhang and coworkers reported terpolymer coatings containing pendant catechol, oligo(ethylene glycol) (OEG), and perfluoroalkyl functional groups (Figure 3c). The coatings exhibited robust adhesion ability and low biofouling.65 In addition, a highly stable catechol acrylate adhesive in wet environments was demonstrated by the Yoshie group.66 This study is informative in that two phenolic adhesion functional groups, catechol acrylate and gallol acrylate monomers, were radical-polymerized with $n$ -butyl acrylate. It was demonstrated that the gallol-incorporated copolymer showed about 7 times higher adhesive strength than the one with the catechol-incorporated adhesive. This comparative study is meaningful because both adhesives showed improved performance compared with an isocyanate-based commercial adhesive. Antioxidant and adsorption properties were also presented with the catecholic polyacrylates by the same group.67 Similar catecholic acrylates coordinate with seawater-rich cations such as ${\\mathrm{Ca}}^{2+}$ and $\\mathrm{\\dot{M}g^{2+}}$ , exhibiting a selfhealing property against external damage through reformation of metal−catechol coordination and hydrogen bonds.68",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3.2. Surface Anchoring for Chemoselective Bio-orthogonal Chemistry  \n\n3.2.1. Diels−Alder Reaction. The Diels−Alder reaction is a temperature-dependent coupling process. Upon assembly of catechol-based biomimetic anchors (Figure 3d), the Diels− Alder cycloaddition reaction can be easily performed to immobilize different macromolecules onto Ti substrates, resulting in changes in their surface properties.69  \n\n3.2.2. Click Chemistry. Similarly, a straightforward strategy based on dopamine derivatives has been reported for titanium surface modification by the use of click chemistry (Figure 3e).70 A similar strategy can also be applied to modify nanoparticles, which can endow new functionalities, such as good water dispersibility and thermal responsiveness.71 In addition, with azide-terminated dopamine, this method was able to functionalize graphene oxide (GO), wherein the reduction of GO and decoration with catechol occurred at the same time.72 By means of this strategy, micro/nanopatterns have successfully been prepared using photolithography and $\\mu\\mathrm{CP}$ techniques.  \n\n3.2.3. Ni-NTA. Xu et al.74 first demonstrated the surface modification of the iron oxide shells of magnetic nanoparticles with nitrilotriacetic acid (NTA). Upon chelation to $\\bar{\\bf N i}^{2+}$ , the functionalized $\\mathrm{Fe}_{2}\\mathrm{O}_{3}$ system could efficiently separate histidinetagged proteins from a cell lysate. This modification strategy broadens the possibility for the application of nanoparticles in biomedicine.  \n\n3.2.4. LbL Method. Longo et al.75 developed a new method for enzyme immobilization on surfaces by combining the catechol chemistry with the layer-by-layer (LbL) method. Alkaline phosphatase (ALP), an enzyme that aids hydrolysis of phosphoryl bonds, has its isoelectric point at $\\mathrm{pH}7.$ As a result, ALP allows the formation of multilayer films with highly negatively charged catechol-conjugated alginate in an LbL manner at $\\mathrm{pH}5.0$ . By subsequent oxidant treatment after LbL film formation, oxidative catechol chemistry successfully turned the multilayer film into a firmly cross-linked architecture without loss of enzyme activity. By means of this combination method, biomolecules can be easily and stably displayed while maintaining their functionalities.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.3. Antibiofouling  \n\n3.3.1. Zwitterionic Antifouling. Hydration plays a significant role in mitigating surface biofouling. Grafting of hydrophilic polymers on surfaces can create a high degree of surface hydration and prevent direct contact from foulants. Jiang and co-workers brush-grafted PSBMA onto a substrate based on the catechol initiator via ATRP.76 The grafted surface was highly resistant to bacterial adhesion. Higher-molecular-weight brushes showed better antifouling properties.58 In addition, a zwitterionic sulfobetaine dopamine (SB-DA) can be easily assembled on the substrate surface to form one layer of stable hydration film for effectively resisting protein and bacterial adsorption (Figure $3\\mathbf{g}{\\dot{}}$ ).77 To simplify the process for preparation of zwitterionic coatings, Emrick and co-workers reported a one-step surface modification strategy by the codeposition of polydopamine and poly(methacryloyloxyethyl phosphorylcholine), making the surface less prone to bacterial fouling. 78  \n\n3.3.2. PEGylation. Hwang, Hawker and co-workers found a removable and recoverable self-assembled monolayer by exploiting strong and reversible catechol−metal coordinative interactions.79 The recyclable surface coating successfully realized excellent antifouling properties as well as controllable wettability.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3.4. Friction and Wetting Control  \n\n3.4.1. Friction Control. Micro/nanoelectromechanical systems play an important role in many areas of research, but serious adhesive and frictional behavior in miniaturized devices restricts their operational lifetime and durability. Zhou and coworkers combined ionic liquids, which possess good lubrication and antiwear properties, with dopamine derivatives to realize the successful self-assembly of compounds with significantly improved lubrication and antiwear properties (Figure 3f).80  \n\n3.4.2. Wetting Control. A perfluorinated dopamine derivative and polyacrylate were prepared and then assembled on a substrate to achieve superhydrophobic properties.62,81 Haag and co-workers achieved a surface with special wettability properties by coating with mussel-inspired dendritic polyglycerol (MI-dPG), which can adhere to the substrate to control the roughness by adjustment of the coating time. By this method, superhydrophobic/superhydrophilic surfaces were obtained by combining nano/micrometer-sized MI-dPG particles modified with perfluorinated acid chloride.82 Engineered surfaces with gradient features are important for diverse applications, such as mimicking biological systems,83 determining minimal drug inhibition concentrations, and constructing various superwetting systems.82 Perfluoroalkyl catechols and nitrodopamine were used in self-assembly to generate a surface hydrophobicity gradient.84 Furthermore, it can be realized on a hydrophobic surface using a microfluidic device, which can create protein or cell gradients for tissue engineering applications.83 In addition, a general technology of cyclic draining and replenishing (CDR) was used to generate a polydopamine gradient on hydrophobic surfaces (Figure 3h).20",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 4. CONCLUSION  \n\nCatecholamine molecules such as dopamine, norepinephrine, and others have been studied primarily by neurobiologists. Also, their protective roles in forms of catecholamine polymers known as melanins have been studied. Surface chemistry to control properties at interfaces using catecholamine molecules is a recent research direction that began with the invention of polydopamine surface chemistry.1,85 Surface functionalizations utilizing catecholamines are the simplest and most versatile approaches for material-independent surface functionalization. This Account has introduced a variety of catecholamine derivatives for applications in many fields. However, there is still room for catecholamine derivatives to provide interface functions that have not yet been explored.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 17,
+        "chunk": "# AUTHOR INFORMATION",
+        "category": " References"
+    },
+    {
+        "id": 18,
+        "chunk": "# Corresponding Authors  \n\n$^{*}\\mathrm{E}$ -mail: haeshin@kaist.ac.kr (H.L.). $^{*}\\mathrm{E}$ -mail: seonkihong@dgist.ac.kr (S.H.). \\*E-mail: zhouf@licp.cas.cn (F.Z.). ORCID  \n\nHaesung A. Lee: 0000-0002-1035-8036   \nFeng Zhou: 0000-0001-7136-9233   \nSeonki Hong: 0000-0003-1440-5167   \nHaeshin Lee: 0000-0003-3961-9727",
+        "category": " References"
+    },
+    {
+        "id": 19,
+        "chunk": "# Notes  \n\nThe authors declare no competing financial interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 20,
+        "chunk": "# Biographies  \n\nHaesung A. Lee obtained his B.S. in Chemistry and Biological Sciences from KAIST in 2015 and is a Ph.D. candidate in the group of Prof. Haeshin Lee. His research interests include polyphenol-conjugated biopolymers and their applications.  \n\nYanfei Ma received his B.S. in chemistry from Northwest Normal University in China in 2015. He is currently a Ph.D. candidate in the group of Prof. Feng Zhou at the Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences. His research interests include wet friction/adhesion control of soft matter and bionic adhesion.  \n\nFeng Zhou is a Professor at the State Key Laboratory of Solid Lubrication at the Lanzhou Institute of Chemical Physics and an adjunct professor at Northwestern Polytechnical University. He got his Ph.D. in 2004 from the Lanzhou Institute of Chemical Physics. He spent three years (2005−2008) in the Department of Chemistry at the University of Cambridge as a research associate. His research interests include surfaces and interfaces of soft matter, drag reduction and antifouling, and biolubrication.  \n\nSeonki Hong is an Assistant Professor in the Department of Emerging Materials Science at DGIST. She pursued her Ph.D. studies in the Department of Chemistry at KAIST and worked as a postdoctoral research fellow at Massachusetts General Hospital and Harvard Medical School. Her research interests have been focused on the design of innovative molecular glues/adhesives by mimicking the chemical structures of unique natural polyphenolic materials and the development of point-of-care bioassays for the precise detection of circulating biomarkers by utilizing these molecular glues.  \n\nHaeshin Lee is Professor in the Department of Chemistry at KAIST. He obtained his Ph.D. in Biomedical Engineering from Northwestern University in 2008. He invented polydopamine coating in 2007 with P. B. Messersmith. His research interests include bioinspired chemistry of catechol and gallol derivatives, adhesive hydrogels and sols, and drug delivery systems. Currently he is an associate editor of Biomaterials Science.",
+        "category": " References"
+    },
+    {
+        "id": 21,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nThis research was supported by National Research Foundation of Korea (NRF) grants funded by the Government of Korea (MSIT): Basic Science Research Program (NRF2018R1D1A1B07045249 to S.H.), Midcareer Researcher Program (NRF-2017R1A2A1A05001047 to H.L.), and Center for Multiscale Chiral Architectures, Science Research Center (SRC) Program (2018R1A5A1025208 to H.L.). This work was also supported by the KIST Institutional Program (Project 2V06630 to H.L.). This work was carried out with the support of the Cooperative Research Program for Agriculture Science and  \n\nTechnology Development (Project PJ01323201 to S.H.) from the Rural Development Administration of the Republic of Korea. This work was also supported by the National Key R e s e a r c h a n d D e v e l o p m e n t P r o g r a m o f C h i n a (2016YFC1100401 to F.Z.) and the National Natural Science Foundation of China (21434009 to F.Z.)",
+        "category": " References"
+    },
+    {
+        "id": 22,
+        "chunk": "# REFERENCES  \n\n(1) Lee, H.; Dellatore, S. M.; Miller, W. M.; Messersmith, P. B. Mussel-Inspired Surface Chemistry for Multifunctional coatings. Science 2007, 318, 426−430.   \n(2) Hong, S.; Na, Y. S.; Choi, S.; Song, I. T.; Kim, W. Y.; Lee, H. NonCovalent Self-Assembly and Covalent Polymerization Co-Contribute to Polydopamine Formation. Adv. Funct. Mater. 2012, 22, 4711−4717. (3) Liebscher, J.; Mrówczyński, R.; Scheidt, H. A.; Filip, C.; Hădade, N. D.; Turcu, R.; Bende, A.; Beck, S. Structure of Polydopamine: A Never-Ending Story? Langmuir 2013, 29, 10539−10548.   \n(4) Alfieri, M. L.; Micillo, R.; Panzella, L.; Crescenzi, O.; Oscurato, S. L.; Maddalena, P.; Napolitano, A.; Ball, V.; d’Ischia, M. Structural Basis of Polydopamine Film Formation: Probing 5,6-Dihydroxyindole-Based Eumelanin Type Units and the Porphyrin Issue. ACS Appl. Mater. Interfaces 2018, 10, 7670−7680.   \n(5) Della Vecchia, N. F.; Avolio, R.; Alfè, M.; Errico, M. E.; Napolitano, A.; d’Ischia, M. Building-Block Diversity in Polydopamine Underpins a Multifunctional Eumelanin-Type Platform Tunable Through a Quinone Control Point. Adv. Funct. Mater. 2013, 23, 1331−1340.   \n(6) Ding, Y.; Weng, L.-T.; Yang, M.; Yang, Z.; Lu, X.; Huang, N.; Leng, Y. Insight into the Aggregation/Deposition and Structure of a Polydopamine Film. Langmuir 2014, 30, 12258−12269.   \n(7) Hong, S.; Wang, Y.; Park, S. Y.; Lee, H. Progressive fuzzy cation−π assembly of biological catecholamines. Sci. Adv. 2018, 4, No. eaat7457. (8) Lee, H.; Scherer, N. F.; Messersmith, P. B. Single-molecule mechanics of mussel adhesion. Proc. Natl. Acad. Sci. U. S. A. 2006, 103, 12999−13003.   \n(9) Anderson, T. H.; Yu, J.; Estrada, A.; Hammer, M. U.; Waite, J. H.; Israelachvili, J. N. The Contribution of DOPA to Substrate-Peptide Adhesion and Internal Cohesion of Mussel-Inspired Synthetic Peptide Film. Adv. Funct. Mater. 2010, 20, 4196−4205.   \n(10) Hong, S.; Yeom, J.; Song, I. T.; Kang, S. M.; Lee, H.; Lee, H. Pyrogallol 2-Aminoethane: A Plant Flavonoid-Inspired Molecule for Material-Independent Surface Chemistry. Adv. Mater. Interfaces 2014, 1, 1400113.   \n(11) Maier, G. P.; Rapp, M. V.; Waite, J. H.; Israelachvili, J. N.; Butler, A. Adaptive synergy between catechol and lysine promotes wet adhesion by surface salt displacement. Science 2015, 349, 628−632. (12) Chen, C.-T.; Martin-Martinez, F. J.; Jung, G. S.; Buehler, M. J. Polydopamine and eumelanin molecular structures investigated with ab initio calculations. Chem. Sci. 2017, 8, 1631−1641.   \n(13) Micillo, R.; Panzella, L.; Iacomino, M.; Prampolini, G.; Cacelli, I.; Ferretti, A.; Crescenzi, O.; Koike, K.; Napolitano, A.; d’Ischia, M. Eumelanin broadband absorption develops from aggregation-modulated chromophore interactions under structural and redox control. Sci. Rep. 2017, 7, 41532.   \n(14) Suárez-García, S.; Sedó, J.; Saiz-Poseu, J.; Ruiz-Molina, D. Copolymerization of a Catechol and a Diamine as a Versatile Polydopamine-Like Platform for Surface Functionalization: The Case of a Hydrophobic Coating. Biomimetics 2017, 2, 22.   \n(15) Iacomino, M.; Paez, J. I.; Avolio, R.; Carpentieri, A.; Panzella, L.; Falco, G.; Pizzo, E.; Errico, M. E.; Napolitano, A.; del Campo, A.; d’Ischia, M. Multifunctional Thin Film and Coatings from Caffeic Acid and a Cross-Linking Diamine. Langmuir 2017, 33, 2096−2102. (16) Ponzio, F.; Payamyar, P.; Schneider, A.; Winterhalter, M.; Bour, J.; Addiego, F.; Krafft, M.-P.; Hemmerle, J.; Ball, V. Polydopamine Films from the Forgotten Air/Water Interface. J. Phys. Chem. Lett. 2014, 5, 3436−3440.   \n(17) Hong, S.; Schaber, C. F.; Dening, K.; Appel, E.; Gorb, S. N.; Lee, H. Air/Water Interfacial Formation of Freestanding, StimuliAdv. Mater. 201 587   \n(18) Wang, Y.; Park, J. P.; Hong, S. H.; Lee, H. Biologically Inspired Materials Exhibiting Repeatable Regeneration with Self-Sealing Capabilities without External Stimuli or Catalysts. Adv. Mater. 2016, 28, 9961−9968.   \n(19) Yang, H.-C.; Wu, Q.-Y.; Wan, L.-S.; Xu, Z.-K. Polydopamine gradients by oxygen diffusion controlled autoxidation. Chem. Commun. 2013, 49, 10522−10524.   \n(20) Zhao, M.-X.; Li, J.; Gao, X. Gradient Coating of Polydopamine via CDR. Langmuir 2017, 33, 6727−6731.   \n(21) Ponzio, F.; Barthès, J.; Bour, J.; Michel, $|\\mathrm{\\mathbf{M}}.\\mathrm{\\mathbf{;}}$ Bertani, P.; Hemmerlé, J.; d’Ischia, M.; Ball, V. Oxidant Control of Polydopamine Surface Chemistry in Acids: A Mechanism-Based Entry to Superhydrophilic-Superoleophobic Coatings. Chem. Mater. 2016, 28, 4697− 4705.   \n(22) Zheng, W.; Fan, H.; Wang, L.; Jin, Z. Oxidative SelfPolymerization of Dopamine in an Acidic Environment. Langmuir 2015, 31, 11671−11677.   \n(23) Chen, T.-P.; Liu, T.; Su, T.-L.; Liang, J. 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+        "category": " References"
+    }
+]
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+    {
+        "id": 1,
+        "chunk": "# Functional hydrogel coatings  \n\nJunjie Liu1,2,3, Shaoxing $\\boldsymbol{0\\mathsf{u}}^{1,2}$ , Zhigang Suo4 and Wei Yang1,∗  \n\n1Center for   \nX-Mechanics, Key   \nLaboratory of Soft   \nMachines and Smart Devices of Zhejiang   \nProvince and   \nDepartment of   \nEngineering   \nMechanics, Zhejiang University, Hangzhou 310027, China; 2State Key Laboratory of   \nFluid Power and   \nMechatronic System, Zhejiang University,   \nHangzhou 310027,   \nChina; 3Applied   \nMechanics and   \nStructure Safety Key Laboratory of Sichuan Province, School of   \nMechanics and   \nEngineering,   \nSouthwest Jiaotong University, Chengdu   \n610031, China and   \n4John A. Paulson   \nSchool of Engineering and Applied Sciences, Kavli Institute for   \nBionano Science and Technology, Harvard University, Cambridge, MA 02138, USA  \n\n∗Corresponding author. E-mail: yangw@zju.edu.cn  \n\nReceived 8 March 2020; Revised 22 September 2020; Accepted 23 September 2020",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# ABSTRACT  \n\nHydrogels—natural or synthetic polymer networks that swell in water—can be made mechanically, chemically and electrically compatible with living tissues. There has been intense research and development of hydrogels for medical applications since the invention of hydrogel contact lenses in 1960. More recently, functional hydrogel coatings with controlled thickness and tough adhesion have been achieved on various substrates. Hydrogel-coated substrates combine the advantages of hydrogels, such as lubricity, biocompatibility and anti-biofouling properties, with the advantages of substrates, such as stiffness, toughness and strength. In this review, we focus on three aspects of functional hydrogel coatings: (i) applications and functions enabled by hydrogel coatings, (ii) methods of coating various substrates with different functional hydrogels with tough adhesion, and (iii) tests to evaluate the adhesion between functional hydrogel coatings and substrates. Conclusions and outlook are given at the end of this review.  \n\nKeywords: hydrogel coatings, coating methods, coating tests, adhesion, hydrogel applications",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# INTRODUCTION  \n\nHydrogels, a family of soft matter [1], are aggregates of water molecules and hydrophilic polymer networks. The high water content, which can exceed $95\\%$ by weight ratio, enables hydrogels to dissolve and transport ions and many small molecules. The polymer networks, which are often sparsely crosslinked, lead to hydrogels being soft and elastic. Hydrogels may have originated with the beginning of life on earth. They are ubiquitous in nature, from muscle and cartilage in animal tissues to xylems and phloems in plants [2–4]. The first report on synthetic hydrogels used in biomedicine was published in 1960 in literature [5]. Since then, the development of hydrogels with new applications and enhanced mechanical robustness has attracted researchers across chemistry, physics, engineering and medicine.  \n\nIn industrial applications, hydrogels are relatively new compared with metals, ceramics and many other forms of polymer. The diversity of hydrogels, natural and synthetic, with different polymer topologies and chemical compositions, makes them highly adaptive to a vast array of applications [6]. Functional hydrogels can chemically, mechanically and electrically mimic the functions of biological tissues [4]. Established medical applications of functional hydrogels include tissue engineering [7], wound dressing (Fig. 1a) [8,9], contact lenses [10] and drug delivery (Fig. 1b) [11,12]. Hydrogels also play key roles in stretchable devices and soft robotics, such as muscle-like actuators (Fig. 1c) [13–15], hydrogel fish (Fig. 1d) [16], soft displays [17], stretchable ionotronics (Fig. 1e) [18,19], skin-like sensors (Fig. 1f) [20] and axon-like interconnects [21,22].  \n\nOne critical challenge in the application of hydrogels is achieving strong bonding between hydrogels and other materials. For instance, hydrogels have long been developed as adhesives for wound closure, however for decades the adhesion was limited below the order of $10\\mathrm{J}/\\mathrm{m}^{2}$ [23]. A transformative advance took place when Yuk et al. adhered hydrogels to nonporous surfaces [24] and elastomers [25] with adhesion greater than $1000\\mathrm{J}/\\mathrm{m}^{2}$ . The high adhesion was achieved through the synergy of two effects: the covalent bonds between the polymer network in the hydrogel and the substrate, and the energydissipating sacrificial bonds in the hydrogel. Since the publication of these studies, other strategies for achieving tough hydrogel adhesion have been reported, such as stitching wet materials (tissues and hydrogels) with biocompatible polymer chains [26], and in situ bonding of dissimilar polymer networks by bulk modification using silanes [27]. Hydrogel adhesion is a supramolecular synergy of chemistry, topology and mechanics [28].  \n\n![](images/aa2d9b8c42acad2c8a811a86c904e8bae77c33aea09a36efd307cd88ba2fccbe.jpg)  \nFigure 1. Typical applications of hydrogels. (a) A hydrogel seals a cut on a pig heart with strong adhesion. The figure is redrawn from ref [9]. Reprinted with permission from AAAS (American Association for the Advancement of Science). (b) Hydrogels in drug delivery applications. The feature size of the drug-loaded hydrogel dictates the pertinent delivery routes. The figure is redrawn with permission from ref [12], Springer Nature. (c) A hydrogel actuator, used as a bladder detrusor, can help to shrink an animal bladder. The figure is adapted with permission from ref [14], John Wiley and Sons. (d) An optically and sonically camouflaged hydraulic hydrogel fish in water. The figure is adapted with permission from ref [16], Springer Nature. (e) A novel transparent loudspeaker made from ionically conductive hydrogel and dielectric elastomer. The figure is adapted from ref [33]. Reprinted with permission from AAAS. (f) Hydrogel sensors for stretch and compression testing. The figure is adapted with permission from ref [20], John Wiley and Sons.  \n\nFunctional hydrogels have been successfully coated onto various substrates of arbitrary shapes with strong bonds [24,25,29–32]. The hydrogelcoated substrates combine the functions of both the substrates and hydrogels, enabling new functions and applications, for example as biocompatible medical devices [31], lubricious nitinol guidewire in medicine [32] and a transparent loudspeaker [33]. In addition, hydrogel coatings play an essential role as structural components in the emerging field of hydrogel machines, which focuses on devices and robotics that incorporate hydrogels. Liu et al. reviewed recent advances in hydrogel machines [34], describing the functions enabled by hydrogel coatings and various interactions between hydrogel coatings and substrates.  \n\nThis paper reviews the emerging topic of functional hydrogel coatings. Emphasis is placed on their functions and applications, fabrication, and methods to evaluate their adhesion. We list the functions and potential applications of hydrogel coatings reported in literatures. Methods that allow various hydrogels to be coated onto different types of substrate with arbitrary shapes are addressed. Finally, we highlight the thickness-dependent adhesion of hydrogel coatings and the experimental methods for evaluating the adhesion. Conclusions and outlook are given at the end of this review.  \n\nTable 1. Hydrogel coatings in medical area.   \n\n\n<html><body><table><tr><td>Function/property</td><td>Hydrogel</td><td>Substrate/device</td><td>Bonding</td><td>Drug/nanoparticle</td><td>Reference</td></tr><tr><td>Drug delivery</td><td>Hyaluronan and poly-D, L-Lactide</td><td>cobalt-chrome, polyethylene, titanium</td><td>PA</td><td>vancomycin, amikacin, tobramycin, gentamicin,</td><td>[35] </td></tr><tr><td></td><td>Gelatin</td><td>titanium alloy</td><td>PA</td><td>sodium salicylate antimicrobial peptide, laponite nanosilicate</td><td>[36] </td></tr><tr><td></td><td>PEG-heparina</td><td>polyurethane</td><td>CA</td><td>silver nitrate</td><td>[37]</td></tr><tr><td></td><td>PMBV/PVA</td><td>titanium alloy</td><td>CA</td><td>paclitaxel (PTX)</td><td>[38] </td></tr><tr><td></td><td>PHEMA</td><td> titanium alloy</td><td>PA</td><td>ciprofloxacin (CIP)</td><td>[39] </td></tr><tr><td></td><td>PEGPLA</td><td>iridium oxide</td><td>PA</td><td>nerve growth factor (NGF)</td><td>[40] </td></tr><tr><td></td><td>PEGDA-co-AA</td><td>titanium</td><td>PA</td><td>silver nanoparticle</td><td>[41] </td></tr><tr><td></td><td>PEGDA</td><td>stainless steel</td><td>PA</td><td>copper nanoparticles</td><td>[42] </td></tr><tr><td></td><td>PHEMA</td><td>silicone</td><td>CA</td><td> nerve growth factor (NGF)</td><td>[43] </td></tr><tr><td>Lubricity</td><td>Chitosan/PVA</td><td>polyurethane urethral catheter</td><td>CA</td><td></td><td>[44]</td></tr><tr><td></td><td>PAAm</td><td>nitinol guidewire</td><td>CA</td><td></td><td>[32] </td></tr><tr><td></td><td>Chitosan</td><td>polyethylene tube</td><td>CA</td><td></td><td>[45] </td></tr><tr><td></td><td>Chitosan</td><td>endovascular catheter</td><td>CA</td><td></td><td>[46] </td></tr><tr><td>Anti-biofouling</td><td>PEG</td><td> polyamide composite</td><td>CA</td><td></td><td>[47]</td></tr><tr><td></td><td>PEG/polycarbonate</td><td>silicone rubber</td><td>CA</td><td></td><td>[48]</td></tr><tr><td></td><td>Zwitterionic PCB</td><td> powdered carbon</td><td>PA</td><td></td><td>[49]</td></tr><tr><td></td><td>HEMA-co-DHPMA</td><td>glucose sensor</td><td>PA</td><td></td><td>[50] </td></tr><tr><td></td><td>pCBAA</td><td>gold/silicon dioxide</td><td>PA</td><td></td><td>[51]</td></tr><tr><td></td><td>PEGMA</td><td>gold</td><td>CA</td><td></td><td>[52] </td></tr><tr><td>Conductive</td><td>PVA/PAA</td><td>iridium oxide</td><td>CA</td><td></td><td>[53,54]</td></tr><tr><td>coatings for</td><td>PU</td><td>iridium oxide</td><td>CA</td><td></td><td>[55]</td></tr><tr><td>neural electrode</td><td>Alginate/PPy</td><td>gold</td><td>PA</td><td></td><td>[56] </td></tr><tr><td></td><td>Alginate/PEDOT</td><td>gold</td><td>PA</td><td></td><td>[57]</td></tr><tr><td></td><td>PVA/PEDOT</td><td> platinum</td><td>PA</td><td></td><td>[58] </td></tr></table></body></html>\n\naAA, acrylic acid; CA, covalent anchorage; DHPMA, $^{2,3}$ -dihydroxypropyl methacrylate; PA, physical attachment; PAA, poly(acrylic acid); PAAm, polyacrylamide; PCB, poly(carboxybetaine); pCBAA, poly(carboxybetaine acrylamide); PEDOT, poly(3,4-ethylenedioxythiophene); PEG, poly(ethylene glycol); PEGDA, poly(ethylene glycol diacrylate); PEGMA, poly(ethylene glycol) methacrylate; PEGPLA, poly(ethylene glycol)-poly(lactic acid); PHEMA, poly(2-hydroxyethyl methacrylate); PMBV, poly(2-methacryloyloxyethyl phosphorylcholine-co-n-butyl methacrylate-co-p-vinylphenylboronic acid); PPy, polypyrrole; PVA, polyvinyl alcohol; PU, polyurethane.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# Drug delivery",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# FUNCTIONS AND APPLICATIONS OF HYDROGEL COATINGS  \n\nHydrogel coatings endow the coated bulk materials with new functions, while having negligible influence on the mechanical properties of the bulk materials. The diversity of hydrogels in chemical components and network topologies makes them appealing candidates as coating materials. The functions and applications enabled by hydrogel coatings can be roughly classified as medical (Table 1) and non-medical applications (Table 2). The details of these applications will be discussed in the sequel.  \n\nHydrogels are appealing candidates for use as carriers in drug delivery systems that transport drugs to target sites and release them at a controlled rate. This drug delivery, controlled in both space and time, improves the accuracy of drug allocation and results in fewer side effects. The feature size of a hydrogel dictates the possible delivery routes. For example, a drug-loaded transdermal hydrogel patch releases a drug by attaching to the human body and a drug-loaded microgel transports a drug via oral or pulmonary delivery. Details for the design of hydrogels for controlled drug delivery can be found in a recent review [12]. The main functions of drugs or nanoparticles loaded into hydrogel coatings on implanted medical devices such as stents [59] (Fig. 2a) and neural electrodes [40,43] include anti-bacterial [36,37,41,42], anti-coagulation [37], anti-inflammatory activities [37], nutrient delivery to surrounding tissues [40,43], and prevention of implant-related infection in orthopedics [35,39]. Examples of drug-loaded hydrogel coatings are listed in Table 1, including the loaded drugs or nanoparticles, the constituents of the hydrogel coatings and the nature of the bonding between the hydrogel coatings and substrates. In order to load drugs into hydrogel coatings, the drugs are generally dispersed in the hydrogel precursor, and the subsequent curing entraps the drugs inside the hydrogel coating. Another approach is to immerse a cured hydrogel coating in a drug solution. The release rate of the loaded drugs is determined by the diffusion of the drugs into the surrounding tissues and can be accelerated by using a biodegradable polymer network to construct the hydrogel coating. Moreover, by tailoring the molecular interactions between the hydrogel polymer network and the drugs—i.e. covalent linkage, electrostatic interaction and hydrophobic interaction—the drug release rate can be efficiently tuned.  \n\nTable 2. Hydrogel coatings in non-medical area.   \n\n\n<html><body><table><tr><td colspan=\"7\">Sensing</td></tr><tr><td>Hydrogel</td><td>Substrate</td><td>Bonding</td><td>Detection</td><td>Output</td><td></td><td>Reference</td></tr><tr><td>Poly(HEMA-co-AAc)</td><td>silicon wafer</td><td></td><td>CA</td><td>volatile vapor</td><td> optical signal</td><td>[67] </td></tr><tr><td>Poly(AAm-co-AAc) poly(AAm-co-AAc-co</td><td>silicon wafer, glass, PET, PDMS</td><td>CA</td><td></td><td>copper ions, glycoprotein</td><td> optical signal</td><td>[68] </td></tr><tr><td>-AAene) with imidazole ligands or PBAa</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Gelatin</td><td>long-period grating (LPG)</td><td></td><td>CA</td><td>humidity</td><td>optical signal</td><td>[69] </td></tr><tr><td>GPBS imprinted PAH</td><td>gold</td><td></td><td>CA</td><td>glucose</td><td>SPR spectrum</td><td>[70] </td></tr><tr><td>PAAm</td><td>FBG</td><td></td><td>PA</td><td>salt concentration</td><td>transmission spectrum</td><td>[71]</td></tr><tr><td colspan=\"7\">Actuation</td></tr><tr><td>Hydrogel</td><td></td><td>Substrate</td><td>Bonding</td><td></td><td>Stimulation</td><td>Reference</td></tr><tr><td>PAA</td><td>PDMS</td><td></td><td>CA</td><td></td><td>pH</td><td>[32] </td></tr><tr><td>PNIPAM, PAA,</td><td>hydrogel</td><td></td><td>IP</td><td></td><td> pH, ionic strength</td><td>[72]</td></tr><tr><td>PEODA</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>PVA-DEEDA-borax gel PNIPAM</td><td>BOPP</td><td></td><td>HB</td><td></td><td>moisture, temperature, light temperature</td><td>[73]</td></tr><tr><td>PAAm</td><td>Glass</td><td></td><td>CA</td><td></td><td>humidity</td><td>[74]</td></tr><tr><td>PNIPAM/PVA</td><td>PDMS PDMAEMA/PSS</td><td></td><td>CA IP</td><td></td><td>temperature, pH</td><td>[75] [76]</td></tr><tr><td colspan=\"7\">Anti-marine creature fouling</td></tr><tr><td>Hydrogel</td><td>Substrate</td><td>Bonding</td><td></td><td></td><td>Marine creature</td><td>Reference</td></tr><tr><td>PAMPA/PAAm, PVA</td><td>polyethylene</td><td>FA</td><td></td><td> algae, sea squirts, barnacles</td><td></td><td>[77]</td></tr><tr><td>PVA-glycerol</td><td>stainless steel</td><td></td><td>FA</td><td>diatom</td><td>barnacle (balanus albicostatus)</td><td>[78]</td></tr><tr><td>PEG</td><td>stainless steel, nylon</td><td></td><td>HB</td><td></td><td></td><td>[79]</td></tr><tr><td>PEG MMA-co-AA-co-</td><td>glass, silicon, PS</td><td></td><td>CA</td><td></td><td>barnacle, algal zoospores, diatom</td><td>[80] </td></tr><tr><td>TBSM</td><td>glass</td><td></td><td>FA</td><td></td><td>barnacle</td><td>[81] </td></tr><tr><td>PEG</td><td>glass</td><td></td><td>CA</td><td></td><td>marine bacteria and diatom</td><td>[82]</td></tr><tr><td colspan=\"7\">Oil-water separation</td></tr><tr><td>Hydrogel</td><td>Substrate</td><td>Bonding</td><td></td><td></td><td>Contaminant</td><td>Reference</td></tr><tr><td>DKGM Hydrogel</td><td> glass fabric</td><td>PA</td><td></td><td>oil, organic dyes, and heavy metals</td><td></td><td>[83] </td></tr><tr><td>PAAm</td><td>magnetic nickel foam</td><td></td><td>PA</td><td></td><td>oil, dichloromethane</td><td>[84]</td></tr><tr><td>PAAm</td><td>stainless steel mesh</td><td></td><td>PA</td><td></td><td>vegetable oil, gasoline, diesel, and crude oil</td><td>[85] </td></tr><tr><td>Alginate</td><td>PAA-g-PVDF</td><td></td><td>IB</td><td></td><td>crude oil</td><td>[86] </td></tr><tr><td>Alginate</td><td>filter paper</td><td></td><td>PA</td><td></td><td>crude oil</td><td>[87] </td></tr></table></body></html>\n\naBOPP, polypropylene; DEEDA, N, N-diethylethane-1,2-diamine; DKGM, deacetylated konjac glucomannan; GPBS, glucose phosphate barium salt; HB, hydrogen bond; IB, ionic bond; IP, interfacial penetration; NaCl, sodium chloride; PAA, polyacrylic acid; PAAm, polyacrylamide; PAH, poly(allylamine hydrochloride); PBA, phenylboronic acid; PBG, fiber Bragg grating; PDMAEMA, poly(2-(dimethylamino)ethyl methacrylate); PDMS, poly(dimethylsiloxane); PEG, polyethylene glycol; PET, poly(ethylene terephthalate); PNIPAM, poly(Nisopropylacrylamide); PS, polystyrene; PSS, poly(sodium-p-styrenesulfonate); PVA, poly(vinyl alcohol); PVDF, poly(vinylidene fluoride); $\\operatorname{SPR},$ surface plasmon resonance.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# Lubricity  \n\nSome lubricious biological surfaces, such as the cartilage of animal joints, are essentially hydrogels consisting of fibrous collagen and proteoglycans.  \n\n![](images/62ca76b32889d8de96c4b4dc6b8fb3c879785bc7489f6d0b8c76816dc11c3d81.jpg)  \nFigure 2. Examples of hydrogels in coating applications. (a) Drug-loaded hydrogel-coated metallic stents. The figure is modified with permission from ref [59], John Wiley and Sons. (b) Slippery hydrogel coating on biomedical tubing and a Foley catheter. The figure is modified with permission from ref [31], John Wiley and Sons. (c) Lubricious hydrogel coating on a nitinol guidewire used in surgical operation. The figure is redrawn with permission from ref [32], John Wiley and Sons. (d) Biocompatible and conductive hydrogel coating on cochlear electrode arrays made from platinum. The figure is adapted with permission from ref [58], IEEE (Institute of Electrical and Electronics Engineers). (e) Stimuli-responsive hydrogel coatings in a sensing system based on the interference of light. The figure is modified with permission from ref [67], John Wiley and Sons. (f) Anti-oil fouling hydrogel coating on a model boat. The figure is redrawn with permission from ref [32], John Wiley and Sons.  \n\nSynthetic hydrogels, with non-adhesive dangling chains on their surfaces, are able to achieve an extremely low coefficient of friction, on the order of $10^{-4}$ [60]. The tribological behavior of hydrogels is significantly different to that of solids and is influenced by several factors including the chemical structure of the hydrogel, the surface properties of the sliding surface and the measurement [61]. One explanation attributes the low friction to the presence of a hydrated layer between the hydrogel and the sliding substrate [61]. The lubricity of the hydrogel-coated surface is important for some medical applications, such as contact lenses [10], catheters [45,46,62] and medical guidewire [32]. For example, a catheter with a thin tube structure serves a broad range of functions in treating diseases or performing surgical procedures. Catheters are inserted into a body cavity, duct or vessel, allowing drainage and administration of fluids or gases and access for other surgical instruments, such as guidewire. The typical biomaterials for the construction of catheters are polymers, such as silicone and poly(vinyl chloride) (PVC), which are inert and unreactive to body fluids but experience high friction with surrounding tissues and are likely to suffer biofouling. Direct insertion of an uncoated catheter is likely to cause trauma to the surrounding tissue during the operation. Lubricious biocompatible hydrogel coatings enable the insertion of catheters into tortuous anatomical pathways with reduced tissue irritation (Fig. 2b) [31]. Another example is metal guidewire, which is a medical device used to deliver implants such as stents to a desired site. Making guidewire surface lubricious is instrumental to easing surgical operation and alleviating patient discomfort (Fig. 2c) [32].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# Anti-biofouling  \n\nThe term biofouling describes the contamination of surfaces by the adhesion of organisms and their by-products [63]. Surface biofouling of implanted medical devices is caused by the adhesion of microbial or thrombotic agents due to foreign body response [64]. Biofouling limits the lifetime of implanted medical devices, and can even result in their removal and replacement [50]. Biofouling is a complex process related to the physical and chemical properties of the target surface. The anti-biofouling properties of implanted medical devices can be enhanced by surface modifications, including controlling surface hydrophilicity and charge, biomolecule functionalization, and drug elution [64]. For hydrophilic surfaces, resistance to the adhesion of fouling agents is ascribed to the hydration layer formed between the coating and the surrounding environment. This hydration layer serves as a physical barrier to resist the adhesion of fouling agents. Hydrogels, as wellknown hydrophilic materials, can substantially enhance the hydrophilicity of the coated surface. Hydrogels commonly used as anti-biofouling coatings on implanted medical devices include poly(vinyl alcohol) (PVA), polyethylene glycol (PEG) and natural polysaccharides, such as chitosan and dextran [47,48,50,52]. PEG has been credited as a gold standard material [64]. The positive charges on the backbone of polysaccharide hydrogels are thought to be effective in disrupting the lipid membrane of microbes, resulting in antimicrobial activity. Another category of anti-biofouling hydrogel coatings is zwitterionic hydrogels, which are neutral but have an equal number of positive and negative charges along the polymer network [49,51]. The most frequently studied zwitterionic materials are prepared by adhering poly(sulfo-betaine) and poly(carboxybetaine) to methacrylate or acrylamide backbones. The hydration layer formed on the surface of the zwitterionic hydrogel coatings is strongly bonded to the coating surface through electrostatic interactions.  \n\nA hydrogel-based ionic cable mimics the function of an axon in terms of ionic conductivity [20]. A hydrogel-based ionic conductor can transmit electrical signals at high speed, 16 orders of magnitude higher than the diffusivity of ions in solution, enabling the ionic conductor to transmit electrical signals with high frequency (up to $100~\\mathrm{MHz}$ ) over a distance of $10\\ \\mathrm{cm}$ . Furthermore, an ionic conductor can transmit enough power to turn on a lightemitting diode, even if the resistivity of the ionic conductor is several orders of magnitude higher than that of an electronic conductor [20]. In medical applications, hydrogel ionic conductors inherit the biocompatibility of the hydrogel and are ideal conductive coatings for neural electrodes. Neural electrode probes, which mainly consist of rigid metals, such as platinum, gold and iridium for the electrode, and silicon, polyimide and ceramic for the construction material, are electronic medical devices implanted into the brain or other electrically excitable tissue to record electrical signals or stimulate neurons with electrical impulses. Hydrogel coatings serve as a mechanical buffer between a rigid neural electrode and soft tissue, attenuating the formation of glial scars resulting from the trauma induced by the micro-motion between the electrode and tissue [44,55,65,66]. Glial scar encapsulation on the electrode surface increases the impedance between the electrode and tissue, resulting in the failure or degradation of the neural signal transmission. When coated with conductive hydrogel, the chronically implanted neural electrode maintains a low impedance over 1 billion stimulations (Fig. 2d) [58]. The biocompatibility of the hydrogel coating also effectively reduces the loss of the neural cells around the electrode [44]. Furthermore, the conductivity between the electrode and tissue can be enhanced by depositing a layer of conductive polymer—poly(3, 4- ethylenedioxythiophene) (PEDOT)—on the metal electrode before coating with the hydrogel [56,57]. Nerve growth factor-loaded hydrogel coating is able to enhance neuron survival and promote the differentiation of neural cells around the electrode [40.43]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# Conductive coatings for neural electrode  \n\nMobile ions obtained by dissolving salt in the water component of hydrogels endow hydrogels with ionic conductivity. The resistivity of salt-containing hydrogel can be reduced to ${\\sim}10^{1}~\\Omega\\mathrm{m},$ , compared with ${\\sim}18.2\\:\\mathrm{M}\\Omega\\mathrm{m}$ for pure water [19]. Living matter mostly uses ions to conduct electrical signals, while machines exclusively use electrons. An emerging research field, known as hydrogel ionotronics, has been rapidly evolving in recent years [19].",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# Sensing  \n\nThe diversity of hydrogel chemistry enables a wide range of responses, for example deformation and change of transparency, to various stimuli such as temperature, $\\mathrm{\\boldmath~\\pH,}$ magnetic field and chemicals. Stimuli-responsive hydrogels are appealing candidates for soft actuator and soft sensor applications. Stimuli-responsive hydrogel coatings incorporated with other substrates or devices generate several new sensing systems. Hydrogel interferometry prepared by coating stimuli-responsive hydrogel on silicon wafer is sensitive to volatile vapor, humidity, copper ions and glycoprotein through the change of hydrogel thickness, presenting different visible structure colors due to the interference of the light reflected by the hydrogel and silicon wafer surface (Fig. 2e) [67,68]. As the detection is based on the diffusion of target small molecules to the hydrogel coating through the thickness direction, the thin hydrogel coating (on the order of $100\\mathrm{nm}$ ) used in this sensing system enables a fast response to an equilibrium state. The implementation of this sensing system is the result of the synergy of chemistry, mechanics and optics. A hydrogel-coated fiber Bragg grating (FBG) allows the measurement of salinity. Under different saline concentrations, the hydrogel coating swells to reach different equilibrium states, resulting in varied FBG stretching and the corresponding shifts in the wavelength of the reflected ‘Bragg’ signal. In principle, this sensing system can be extended for the detection of other chemical species through modification of the gel chemistry with the same sensor construction [71]. Based on surface plasmon resonance spectroscopy, glucose phosphate barium saltimprinted hydrogel coating on a gold surface yields a selective sensor for glucose. When gold nanoparticles are incorporated into the hydrogel coating to give a higher refractive index, the sensitivity of the sensor is significantly enhanced, making the sensor capable of detecting glucose at a level of $\\mu\\mathrm{g/mL}$ in deionized water [70].  \n\nstructure is the most commonly used configuration for the construction of a stimuli-responsive hydrogel coating-based actuator [73,76]. The two layers can be prepared from different stimuli-responsive hydrogel coatings, achieving reversible and bidirectional actuation. Using the bilayer structure as a primary element, complex configuration transformation from 2D to 3D can be achieved via structure design or patterned active hydrogel coating [72,75]. Furthermore, temperature-responsive hydrogel coatings can drive the motion of fluids in microfluidic devices by cyclic swelling and deswelling stimulated by temperature [74]. For more information on hydrogel actuators, please refer to previous reviews [88].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# Anti-marine creature fouling",
+        "category": " Introduction"
+    },
+    {
+        "id": 11,
+        "chunk": "# Actuation  \n\nThe stimuli-responsive hydrogels used as active materials for actuation feature a relatively large actuation deformation triggered by external stimuli, such as $\\mathrm{\\tt{pH}}$ , temperature, magnetic field and hydraulic or pneumatic pressure. The stimuli responses of hydrogels are readily implemented by using a stimuliresponsive polymer network for hydrogel formation (e.g. poly( $\\mathrm{\\Delta}N$ -isopropylacrylamide) for temperature response, and polyacrylic acid for $\\mathrm{\\tt{pH}}$ response); embedding active elements in the hydrogel matrices (e.g. magnetic particles for magnetic field response); and designing structures with chambers or channels for actuation by hydraulic or pneumatic pressure [34]. Active hydrogels for actuation that are in coating form are mostly based on stimuli-responsive polymer networks. Under stimuli, the conformational transformation or change of crosslink density of the polymer network induces swelling/deswelling of the hydrogel, resulting in an expansion or contraction for actuation. A bilayer  \n\nA submerged surface in the marine environment suffers the accumulation of marine fouling organisms, such as algae, diatoms and barnacles, known as marine creature fouling [89]. Marine creature fouling slows vessels, resulting in additional energy consumption and vessel maintenance costs. Furthermore, the life of the hull can be shortened owing to the corrosion caused by the attached organisms. The fouling process is affected by several physical and chemical properties of the surface, such as the surface tension, wettability, modulus, roughness and chemistry. Coating the target surface with anti-fouling materials is the mostly widely adopted approach to achieving anti-fouling properties for submerged substrates in the marine environment [89]. The earliest coating materials include pitch, tar, wax and heavy metals such as lead. However, these materials have a low durability and limited anti-fouling performance. In the mid-1960s, a more durable tributyltin (TBT)-containing self-polishing anti-fouling coating was formulated, which shows prolonged anti-fouling efficiency for up to five years as a result of the continuous release of TBT from the coating. However, TBT was banned in 2008 owing to its adverse effects on aquatic life [82]. Exploring environmentally friendly, durable anti-marine creature fouling coatings has since been urgently pursued to protect submerged surfaces and the marine environment. Examples of such functional coatings include natural anti-fouling compounds, silicone and fluorocarbon polymers with low surface energy, and hydrogels. The anti-fouling characteristic of hydrogel coatings is attributed to their highly hydrated surfaces. Several functional hydrogel coatings, such as PVA and poly(2-acrylamide2-methyl-propanesulfonic acid)/polyacrylamide (PAMPS/PAAm) double network tough hydrogel,  \n\nPEG and zwitterionic hydrogels, have been shown to be effective in inhibiting the attachment of marine creatures in experiments [77–82]. For example, a polyacrylamide hydrogel-coated model boat floating in a water-filled tank contaminated with oil shows anti-oil fouling properties (Fig. 2f) [32]. Functional hydrogel coatings therefore have potential for application where adhesion by marine creatures is undesired.  \n\n$380\\mu\\mathrm{m},$ with rough nanostructured hydrogel [85]. This hydrogel-coated mesh exhibited selective and effective $(>99\\%)$ separation of water from various oil/water mixtures including vegetable oil and even crude oil. These superhydrophilic and underwater superoleophobic hydrogel-coated filtration films for oil/water mixture separation have the advantages of non-fouling and cyclic usage, which make them appealing candidates in industrial oily wastewater treatment and oil spill cleanup.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# Oil-water separation  \n\nOily wastewater pollution is becoming a worldwide threat to marine and aquatic ecosystems owing to increasing oily wastewater from industry and frequent oil spill accidents [86]. The demand for reusable oil-water separation materials with high efficiency and low cost is becoming increasingly urgent. Due to the intrinsic immiscibility of water and oil, materials with extreme affinity either to water or oil are promising candidates for application in oil-water separation [90]. ‘Oil removing’ materials are superhydrophobic or superoleophilic materials that allow the infiltration of oil while leaving the water on the other side [83]. Examples of these materials include polyester textiles, carbon-based materials, hydrophobic aerogels, polystyrene and polytetrafluoroethylene (PTFE) coating mesh. However, these materials are prone to pore clogging and surface fouling by oil due to their intrinsic oleophilic properties, resulting in the degradation of separation efficiency and a short life.  \n\nIn contrast to ‘oil removing’ materials, ‘water removing’ materials are superhydrophilic and underwater superoleophobic and do not suffer the limitations of ‘oil removing’ materials. Hydrogels are well-known hydrophilic materials whose water component can exceed $95\\%$ in weight. Hydrogels themselves as base materials for oil-water separation have the disadvantage of low water flux—below $30\\mathrm{L}/\\mathrm{m}^{2}\\mathrm{~h}^{-1}$ bar−1—as the mesh size is on the order of $10\\ \\mathrm{nm}$ [91]. Coating commercial filtration films with hydrogels combines the advantages of the high flux of the filtration film and the hydrophilicity of the hydrogel [83,84,87]. Gao et al. coated a thin alginate hydrogel film onto the surface of a polyacrylic acid-grafted-poly(vinylidene fluoride) (PAA$g{\\mathrm{-PVDF}},$ ) filtration membrane via layer-by-layer selfassembly of sodium alginate and ${\\mathrm{Cu}}^{2+}$ . This hydrogel coated PAA- $g$ -PVDF filtration film achieved a high water flux of up to $1230~\\mathrm{L/m^{2}~h^{-1}}$ bar−1 with high separation efficiency—above $99.8\\%$ —and an outstanding cyclic performance [86]. Instead of coating hydrogel on the surface of the filtration membrane, Xue et al. coated micro-scale porous metal substrates, with mesh sizes ranging from 34 to",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# HYDROGEL COATING METHODS  \n\nAn ideal hydrogel coating method should achieve two goals: strong adhesion to the substrate and conformation to a substrate with an arbitrary shape. Strong adhesion requires a strong interaction, such as covalent bonding, at the interface of the hydrogel coating and substrate, and strong cohesive strength of the hydrogel coating itself. The strong adhesion prevents the delamination or fracture of the hydrogel coating due to cyclic swelling or repeated sliding against the surroundings, while a method of coating a substrate with an arbitrary shape is important. Uniform hydrogel coatings can easily be cast on a flat substrate with a mold, but coating on a substrate with a complex shape can be challenging. In the following section we only describe the coating methods that meet the above two requirements.",
+        "category": " Introduction"
+    },
+    {
+        "id": 14,
+        "chunk": "# The surface bridge method  \n\nThe adhesion of hydrogels to other substrates by simple attaching is intrinsically low owing to the presence of abundant water at the interface [17]. Strong hydrogel adhesion is the result of strong interaction between the polymer network of the hydrogel and the target substrate. The surface bridge method for strong adhesion complies with the following principle: the two ends of a bridge molecule can form a strong interaction with the hydrogel and substrate separately, establishing strong bonding at the substrate-coating interface.  \n\nThe commonly used bridge molecules for hydrogel coatings are silanes or silane-coupling agents such as 3-(trimethoxysilyl) propyl methacrylate (TMSPMA) and (3-aminopropyl) triethoxysilane (APTES), as shown in Fig. 3a [24,92]. The alkoxy groups at one end hydrolyze into silanol groups in an aqueous environment and condense with hydroxyl groups on the target surface to form siloxane bonds, enabling strong bonding between the target substrate and the bridge molecules. The other end of the APTES has an amino group that can condense with a carboxyl group on the polymer network of hydrogels such as alginate and hyaluronan by EDCSulfo NHS chemistry. For TMSPMA, the vinyl group at the other end can participate in the polymerization of the hydrogel-coating precursor, enabling covalent bonding between the hydrogel coating and the TMSPMA.  \n\n![](images/5633758ace4ed042f64ae5c27e3a84abd5aebf90db42d087787f5a209760614b.jpg)  \nFigure 3. Hydrogel coating methods. (a) The surface bridge method. The bridge molecules used are (3-aminopropyl) triethoxysilane (APTES) and 3-(trimethoxysilyl) propyl methacrylate (TMSPMA). The two ends of the molecules form covalent bonds with the substrate and hydrogel coating separately, enabling strong bonding of the hydrogel coating to the substrate. The figure is redrawn with permission from ref [24], Springer Nature. (b) and (c) The surface initiation method. Hydrophobic benzophenone photo-initiator is adsorbed onto the surface of the target substrate by diffusion or an additional primer. The subsequent curing of a hydrogel precursor on the treated substrate enables a hydrogel coating to be strongly bonded to the substrate. (b) is adapted with permission from ref [31], John Wiley and Sons. (c) is adapted with permission from ref [30], John Wiley and Sons. (d) The hydrogel paint method. A paste-like hydrogel paint is applied to a pre-treated substrate using common painting operations such as brushing and dipping. The crosslinking of the hydrogel coating and strong bonding formation between the coating and substrate complete in the curing process of the hydrogel paint. The figure is adapted with permission from ref [32], John Wiley and Sons.  \n\nA hydrogel coating can be firmly bonded to a target substrate through bridge molecules. This method was first used by Yuk et al. for bonding tough hydrogels to non-porous surfaces, such as metal, glass, silicon and ceramics, enabling adhesion of more than  \n\n$1000\\mathrm{J}/\\mathrm{m}^{2}$ to be achieved [24]. In principle, as long as the substrate is rich in surface hydroxyl groups the method is valid. Inorganic solids, such as glasses, metals and ceramics naturally have hydroxyl groups on their clean surface exposed to the air. While for some organic solids, such as elastomers and plastics, the hydroxyl groups can be obtained by surface treatments such as oxygen plasma and UV ozone [32].  \n\nA hydrogel precursor is usually cast on the treated substrate and then cures in a mold to hold the shape and to isolate oxygen, which prohibits the polymerization of hydrogel precursor [24,25]. In principle, coating hydrogel on a substrate with an arbitrary shape can be readily achieved by the surface bridge method as long as the hydrogel precursor can be grafted onto the substrate without a mold. A printable hydrogel precursor, which behaves like a paste, meets this requirement and can be applied to the target substrate by brushing or dipping. The printable hydrogel precursor can be prepared by adding a rheology modifier, such as nanoclay, micro-gel or long natural or synthetic polymer chains to the water-like hydrogel precursor [93]. To spread the hydrogel precursor on the target substrate steadily, the surface energy of the substrate should be higher than the surface tension of the hydrogel precursor. The surface energy of the target surface can be increased using numerous techniques including plasma treatment, corona treatment and acid etching. Conversely, additives such as surfactants can be added to the hydrogel precursor to reduce its surface tension. The subsequent curing of the hydrogel precursor can be carried out in an oxygen-free environment, usually in a nitrogen-filled chamber. The loss of water during curing is another consideration. Humectants such as lithium chloride can be added to the hydrogel precursor or the chamber humidity can be kept high to alleviate the water loss.  \n\nThe validity of the surface bridge method in hydrogel coating formation relies on the functional groups in the bridge molecules. For example, the widely used TMSPMA works for substrates with abundant hydroxyl groups on the surface and hydrogels prepared by free-radical polymerization of vinyl monomers. In contrast, APTES is suitable for hydrogels that are rich in carboxyl groups in the polymer network. Furthermore, it is possible to design new bridge molecules and incorporate different functions, such as on-demand breakage. For example, Li et al. designed a bridge molecule containing a carboxylic acid group at one end, which realized strong bonding with the metal surface through coordination of deprotonated carboxylate groups to metal ions, and electrostatic and hydrophobic interactions, and a methacrylic group at the other end, which chemically bonded with the hydrogel network through copolymerization. By introducing a breakable disulfide bond in the bridge molecule, they achieved on-demand debonding of the hydrogel–metal interface by stimulation with reduction agents such as glutathione [94].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# The surface initiation method  \n\nBenzophenone is a hydrophobic photo-initiator that can diffuse into the surface of polymers such as polydimethylsiloxane (PDMS), polyurethane, latex,  \n\nVHB (Very High Bond) and Ecoflex with the help of an appropriate organic solvent. The benzophenone absorbed in the elastomer serves as a grafting agent to bond the polymer network of the hydrogel to that of the elastomer and as an oxygen scavenger to alleviate the oxygen inhibition effect [25]. When exposed to ultraviolet (UV) light, a benzophenone molecule abstracts a hydrogen atom from the polymer network of the substrate and generates a free radical, mediating the grafting of the hydrogel network to the polymer network of the elastomer [25]. The validity of the surface initiation method using benzophenone is limited to polymers that can swell in benzophenone organic solution and supply hydrogen to benzophenone for free-radical generation. Two different methods of forming a hydrogel coating on benzophenone-adsorbed polymers have been adopted. The first involves the application of a pastelike hydrogel precursor to the target surface and then exposing it to UV light for curing, as described for the surface bridge method [29]. Owing to the lower surface energy of most polymers compared with that of the hydrogel precursor, which mainly comprises water, additional treatment of the polymer surface to increase its surface energy—for example with oxygen plasma—is necessary to ensure a steady spread of the hydrogel precursor on the polymer. Otherwise, the hydrogel precursor might bead on the hydrophobic polymer surface.  \n\nAn alternative method is to immerse the treated polymers in a water-like hydrogel precursor, which is a mixture of water, hydrogel monomer and hydrophilic initiator, as shown in Fig. 3b [31]. The hydrophilic initiator initiates the polymerization of hydrogel monomers within and above the surfacebound diffusion layer of the substrate. Meanwhile, the hydrophobic initiator initiates the polymerization inside the diffusion layer of the polymer, grafting the hydrogel polymer chains to the network of the substrate. In addition to the hydrophobic photoinitiator (benzophenone), a hydrophobic thermoinitiator (benzoyl peroxide) has also been used as another example of this method. Thermal initiation is advantageous in cases where reaching the desired hydrogel coating site with the light required to initiate polymerization is challenging [31]. As a result, the polymer networks of the substrate and hydrogel interpenetrate at the interface and form covalent linkages, achieving strong bonding. The weakly attached polymer chains on the surface of the elastomer can be rinsed away with water, leaving a strongly bonded ‘hydrogel skin’ on the target substrate. This method enables a ‘hydrogel skin’ on polymers with an arbitrary shape, a tunable thickness ranging from 5 to $25\\mu\\mathrm{m}$ and resistance to prolonged shear forces.  \n\nThe surface initiation method was further developed by Takahashi et al. to achieve hydrogel coating of substrates that are unable to adsorb benzophenone directly by diffusion [30]. Their method consists of two steps, as shown in Fig. 3c. The target substrate, regardless of whether it is plastic, rubber, ceramic or metal, is coated with a primer, which is a mixture of benzophenone and poly(vinyl acetate) (PVAc). This primer layer physically bonds with the target substrate with strong adhesion. A paste-like hydrogel precursor is then applied to the treated surface, followed by photo-initiated polymerization in an oxygen-free environment. High adhesion of over $1000\\mathrm{J}/\\mathrm{m}^{2}$ was achieved. The coatings are wear resistant and stable after soaking in pure water in an ambient environment for 282 days.  \n\nIn principle, the surface initiation method is suitable for hydrogel coating formation on most substrates. For polymers, the hydrophobic initiators can diffuse into their surface with the help of an appropriate solvent (e.g. ethanol, acetone). For other substrates, such as metals and ceramics, an initiator containing primer, such as poly(vinyl acetate), can be applied on the target surface to introduce the initiators. The surfaces of most polymers have low surface energy compared with that of water, which hinders the wetting of the hydrogel precursor on the target substrate. To achieve steady spreading of a paste-like hydrogel precursor on the substrate or better diffusion of the hydrogel monomers into the target surface, a substrate with high surface energy is preferred for better wetting. To meet this requirement, surface treatment (e.g. plasma treatment, corona treatment and acid etching) of the target surface can be carried out for a higher surface energy, or additives (e.g. surfactant) can be added to the hydrogel precursor to lower the surface tension.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# The hydrogel paint method  \n\nIn general, hydrogel coating formation using freeradical polymerization involves three processes: polymerizing hydrogel monomers to polymer chains, crosslinking the polymer chains to give a hydrogel network, and bonding the network to the target substrate. These processes occur concurrently in one step. For example, a polyacrylamide hydrogel coating on a silica substrate is completed in a one-step polymerization between the vinyl groups of the acrylamide monomers, the crosslinker (N, $\\mathbf{N}^{\\prime}$ -Methylenebisacrylamide, MBAA) and the silane molecules (TMSPMA) anchored on the silica substrate. The disadvantages of this traditional approach are clear: (i) the handling of the toxic hydrogel monomers and initiators is not user-friendly;  \n\n(ii) free-radical polymerization usually applies to an oxygen-free environment; (iii) a liquid-like hydrogel precursor requires a mold to hold its shape before solidification, which hinders the implementation of hydrogel coatings on complex structures.  \n\nRecently, a new method known as the hydrogel paint method has been put forward for coating different substrates with various hydrogels, as delineated in Fig. 3d [32,95]. To make a hydrogel paintable, the key is the decoupling of the three processes of hydrogel coating formation given above. As schematically illustrated in Fig. 3d, the hydrogel paint is a solution of copolymers of hydrogel monomers and coupling agents, and behaves like a viscous liquid or a common paint. The functional groups on the coupling agents have tunable kinetics to interact with each other and with the complementary functional groups on the substrate for hydrogel paint curing and strong bond formation after applying the hydrogel paint to the target substrate using various painting technologies. Several embodiments of hydrogel paint are achieved by copolymerizing various hydrogel monomers, such as acrylamide for lubricious, acrylic acid for pH-sensitive and N-isopropylacrylamide for temperature-responsive applications, with silane coupling agent (TMSPMA) through vinyl groups. The condensation rate of silanol groups in hydrolyzed TMSPMA molecules in the copolymers and the hydroxyl groups on the target substrate can be tuned using $\\mathrm{\\tt{pH}}$ and curing temperature. Accordingly, the shelf life or curing time of hydrogel paint can be tuned from hours to days. Furthermore, the shelf life of the hydrogel paints can be significantly extended to months by freeze drying, storing and re-dissolving in water.  \n\nThe hydrogel paint strategy enables the division of labor. The paint maker is responsible for paint formation using sophisticated chemistry, while the paint user need not be hampered by the need for sophistication and is responsible for substrate preparation, painting and curing. The toxic monomer and initiator are mostly consumed during paint formation so that the paint user does not need to handle the toxic compounds. The tunable viscosity of hydrogel paint, using either water content or rheology modifiers, allows it to be applied and grafted onto substrates with complex structures. The oxygen insensitivity of hydrogel paint curing and bonding with the substrate, for example through silane condensation, ensures the hydrogel coating formation is successful in an ambient environment. All of these advantages make the hydrogel paint method an appealing way of hydrogel coating formation in real applications.  \n\nThe functional groups or coupling agents in hydrogel paints determine their applications and validities. For example, silanol groups can condense with hydroxyl groups on target substrates for strong bonding, and condense with each other for solidification of the hydrogel paint. Silane condensation is oxygen insensitive. Thus, the bonding and curing of hydrogel paint can be carried out without precluding oxygen. The hydrogel paint method of hydrogel coating was relatively recently introduced and is open for further exploration and development.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# Purification of hydrogel coatings  \n\nFree-radical polymerization of hydrogel precursors, which mainly consist of monomers, crosslinkers and initiators, is a prevailing method in hydrogel preparation. The conversion efficiency of hydrogel monomers to a hydrogel network does not reach $100\\%$ , which leaves unreacted monomers and initiators that are toxic and may leach out of the hydrogel matrix. The removal of these residual small molecules before use is important in real applications, particularly in biomedical areas. The common procedure for removing these undesirable small molecules is by incubating the cured hydrogel in excess deionized (DI) water for several hours to days with regular replenishment of the DI water [96–99]. The time for the diffusion of these small molecules out of the hydrogel depends on the characteristic size of the hydrogel sample $L$ , which can be estimated as $L^{2}/D$ , where $D$ is the diffusion coefficient of these small molecules in DI water (typically on the order of $10^{-9}\\mathrm{m}^{2}/\\mathrm{s}$ at room temperature).  \n\n![](images/76b118d6cc7cb39b4ab403030a1c24966fbe27fa6d0e8f80a6bb1694ffcd1904.jpg)  \nFigure 4. Fractocohesive length of a hydrogel. (a) The fractocohesive length of a hydrogel, estimated by the ratio of $\\Gamma/W_{f}$ , determines the transition flaw length of the hydrogel—from flaw insensitive to flaw sensitive—with the existence of a flaw. The figure is adapted with permission from ref [101], Elsevier. (b) The rupture stretch of a piece of polyacrylamide hydrogel is almost a constant with pre-existing flaws or cracks of lengths smaller than the fractocohesive length (around 1 cm in this case). Otherwise, it decreases with increasing flaw size. The figure is redrawn with permission from ref [100], Elsevier. (c) Left: schematic diagrams of the adhesion of a hydrogel coating as a function of coating thickness in a peel test. Right: experimental results for the adhesion of polyacrylamide hydrogel coatings with various coating thicknesses in peel tests. The figure is adapted with permission from ref [102], Elsevier.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# ADHESION OF HYDROGEL COATINGS  \n\nAdhesion between the hydrogel coating and substrate, which is the energy needed to peel away a unit area of hydrogel coating and has units of J/ $\\mathbf{m}^{2}$ , quantifies the resistance to debonding of the coating. However, rigorous characterization of the adhesion of hydrogel coatings is lacking for three main reasons: first, strong adhesion of hydrogel coatings to substrates is relatively new. Second, hydrogels have only recently been integrated with other materials such as dielectric elastomers in hydrogel ionotronics and metals in biomedical devices. Third, the thickness of the hydrogel coating can be as thin as several microns, which makes testing adhesion challenging. In this section, we discuss the origin of the thicknessdependent adhesion of hydrogel coatings and the test methods used to test the adhesion.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# Thickness-dependent adhesion  \n\nA material-specific length, termed the fractocohesive length, was recently defined [100]. This length is the ratio of $\\Gamma/W_{f}$ , where $\\Gamma$ is the material toughness obtained by stretching a sample with a crack and $W_{f}$ is the fracture work obtained by stretching a sample without a crack. The fractocohesive length is comparable to the flaw sensitivity length of the material. The ultimate strength of the material, such as ultimate stretch, is not affected by the existence of a crack that has a feature size smaller than the flaw sensitivity length (Fig. 4a and b) [100,101]. The fractocohesive length can be compared with the size of the fracture process zone, which is a highly stretched zone in the vicinity of the crack tip. The material in the fracture process zone is highly stretched, dissipating energy through inelastic processes (such as viscoelasticity, poroelasticity for hydrogels and chain scission) and storing elastic energy by elastic deformation. A recent theory indicates that both the energy dissipated during loading and the release of the stored elastic energy corresponding to crack propagation contribute to the toughness as well as the adhesion of the hydrogel coating [102,103].  \n\nPeeling away a hydrogel coating involves two length scales: the thickness of the hydrogel coating and the fractocohesive length of the hydrogel. The difference between the two length scales defines two cases: small-scale and large-scale inelasticity peel. If the coating thickness is smaller than the fractocohesive length, the fracture process zone is bounded by the coating thickness. We call this case the largescale inelasticity peel. In this case, the adhesion increases as the coating thickness increases. Otherwise, the fracture process zone is bounded by the fractocohesive length, which is a constant and independent of the coating thickness (Fig. 4c). The thickness dependent adhesion of viscoelastic adhesive has been well studied both in theory and experiment [104,105]. In light of thickness-dependent adhesion, it is important to clarify the thickness of the hydrogel coating when specifying the adhesion.  \n\nAnother commonly used length scale is called the elasto-adhesive length, defined as $\\Gamma/E$ , where $E$ is the Young’s modulus [106]. This length scale defines the size of a nonlinear elastic region at the crack front where linear elastic fracture mechanics (LEFM) are no longer valid. Considering the high stretchability of soft materials, the elasto-adhesive length can be greater than the fractocohesive length by several orders of magnitude.  \n\n![](images/94272925eac8fa09ee95536bc14c35130a962679464b200a05bc5953170368d5.jpg)  \nFigure 5. Test methods for the adhesion of hydrogel coatings. (a) The 90 degree peel test. A hydrogel coating is peeled off the substrate by a backing attached at an angle of 90 degrees to the substrate. (b) The simple stretch test. A stretchable substrate coated with hydrogel coating is loaded by uniaxial stretch, resulting in debonding of the coating under a critical load. (c) The scratch test. A rigid stylus is drawn across the surface of the coating, accompanied by a synchronous movement in the thickness direction of the coating. (d) The probe pull test. A flat tipped indenter is bonded to a hydrogel coating and then pulled away. (e) The double cantilever beam test (left) and contoured double cantilever beam test (right). A hydrogel coating is sandwiched between two cantilever beams. The two beams are pulled apart, resulting in fracture of the hydrogel coating.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# The peel test  \n\nTo test the strength of the adhesion of a hydrogel coating to a target substrate, the coating must be peeled off the substrate either through the substrate/hydrogel interface or through the hydrogel coating. The peel test is typically used to evaluate the adhesion of adhesive tapes [107] and has been further developed to test the adhesion of metal and ceramic films [108,109]. Recently, this method has been adopted to test the adhesion of hydrogel coatings. To peel off a hydrogel coating, a flexible and inextensible backing layer (typically a polyester film with a thickness of around $100\\:\\mu\\mathrm{m}\\rangle$ is generally attached to it (Fig. 5a). A peeling result is related to many factors, including the peel speed, the backing layer used, the mode of bonding the backing to the hydrogel coating, and the angle through which the hydrogel coating is peeled off. The interpretation of the peel results is based on the work balance in steady crack propagation, in which the crack propagates at a constant speed while the peel force is invariant over peel distance. Considering the constant elastic energy stored in the hydrogel coating and neglecting the elastic energy stored in the flexible and inextensible backing, the work imparted by the steady peel force is a direct reflection of the adhesion of the hydrogel coating. For simplicity, the backing layer can be pulled at an angle of 90 (Fig. 5a) or 180 degrees to the substrate, giving an adhesion of $F_{s s}/h\\mathrm{or}2F_{s s}/h,$ where $F_{s s}$ is the steady peel force and $h$ is the width of the hydrogel coating. A general expression is $\\Gamma=F_{s s}/h(1-\\cos\\theta),$ where $\\theta$ is the peel angle with respect to the substrate. It is noted that the steady peel force is a function of the peel angle $\\theta$ [110]. At different peel angles, the deformation states at the crack front of the hydrogel are different, resulting in different crack modes. Although the peel test gives a global result for adhesion, namely the energy needed to peel off a unit area of hydrogel coating, it reveals nothing about the mechanism of debonding [106].  \n\nAn experimental challenge of the peel test is how to firmly bond the backing layer to the hydrogel coating without disrupting the coating or debonding during the test. Cyanoacrylates (known as superglues) are commonly used to achieve strong bonding. Cyanoacrylate monomers diffuse into the hydrogel polymer network and form polycyanoacrylate chains through anionic polymerization in topological entanglement with the hydrogel polymer network. Meanwhile, the polycyanoacrylate chains cause densely packed non-covalent interaction with the non-permeable plastic backing [111]. When the hydrogel coating is very thin, the diffusion of the cyanoacrylate into the hydrogel leads to appreciable influence on the integrity of the hydrogel coating, compromising the peel results. The diffusion depth of cyanoacrylate into hydrogel has been found to reach $\\sim10\\mu\\mathrm{m}$ [112]. The peel test requires a new approach for achieving strong bonding between the coating and the backing layer. Nevertheless, if the thickness of the hydrogel coating is much greater than the diffusion depth of the cyanoacrylates, the side effects induced by the adhesive are negligible.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 21,
+        "chunk": "# The simple stretch test  \n\nThis method is effective for testing weakly bonded hydrogel coatings on stretchable substrates, for example a weakly bonded hydrogel coating on an elastomer such as PDMS or VHB [113]. When applying stretch to the specimen, as shown in Fig. 5b, the coating and substrate deform and store elastic energy. Assuming the specimen undergoes uniaxial tension, we denote the stretch in the coating/substrate bilayer segment $\\lambda^{\\prime\\prime}$ and that in the substrate single layer segment $\\lambda^{\\prime}$ . The combination of the elastic energy stored in the specimen and the potential energy of the applied force give the potential energy of the system as $U=C\\left[\\bar{U_{s}}\\left(\\lambda^{\\prime}\\right)-P\\lambda^{\\prime}\\right]+$ $\\bigl(L-C\\bigr)\\bigl[U_{b}\\bigl(\\lambda^{\\prime\\prime}\\bigr)-P\\lambda^{\\prime\\prime}\\bigr],$ where $U_{s}$ is the elastic energy stored in a unit area of the substrate, $U_{b}$ is the elastic energy stored in a unit area of the coating/substrate bilayer, and $P$ is the force per unit width of the hydrogel coating. The applied energy release rate is $G=-\\partial U/\\partial C$ . Accordingly, we get $G=U_{b}(\\lambda^{\\prime\\prime})-U_{s}(\\lambda^{\\prime})+P\\left(\\lambda^{\\prime}-\\lambda^{\\prime\\prime}\\right)$ . Considering that the hydrogel coating is usually thin and has low modulus, the bonded hydrogel coating has negligible influence on the deformation of the substrate, yielding $\\lambda^{\\prime\\prime}=\\lambda^{\\prime}$ . The energy release rate is therefore simplified to $G=U_{b}\\left(\\lambda^{\\prime}\\right)-U_{s}\\left(\\lambda^{\\prime}\\right).$ , which implies that the release of the elastic energy stored in the hydrogel coating contributes to the crack propagation. If the hydrogel coating is much stiffer than the substrate (for example, one bonds an inextensible backing on the other side of the hydrogel coating), the stretch of the bilayer segment is negligible, thus $\\lambda^{\\prime\\prime}=1$ . In this case, the energy release rate is $G=-U_{s}\\left(\\lambda^{\\prime}\\right)+P\\left(\\lambda^{\\prime}-1\\right)$ . This energy release rate is ascribed to the release of the elastic energy in the substrate and the change of the potential energy by the applied force. The energy release rate $G_{c}$ corresponding to the propagation of the crack under critical pull force $P_{c}$ gives the adhesion of the hydrogel coating.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 22,
+        "chunk": "# The scratch test  \n\nIn this test, a rigid stylus is drawn on the surface of the coating, accompanied by a synchronous movement in the thickness direction of the coating in a continuous or stepwise manner, as shown in Fig. 5c. The force on the stylus is recorded during scratching and the critical force at which the failure of the coating occurs is determined [114]. The scratch test is regarded as semi-quantitative in determining the adhesion of the coating because the critical scratch force extracted from the test is affected by numerous factors that are not adhesion-related, such as scratching speed, stylus tip radius and substrate hardness, among others. Interpreting the critical scratch force in terms of the adhesion using a mechanical model is intractable [115]. Efforts have been made for limited cases, such as hard coating/soft substrate systems, and for limited failure modes, such as coating detachment ahead of the stylus [116,117]. Careful theoretical considerations or simulations are required to relate the experimental results to the adhesion of the coating. Fortunately, the scratch test has the advantages of being easy to use and no special specimen preparation being required. The critical scratch force obtained is effective as quantitative but relative data to evaluate adhesion between coatings [118].",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 23,
+        "chunk": "# The probe pull test  \n\nIn the probe pull test, a cylindrical, flat or hemispherical-ended probe is bonded to the hydrogel coating. The probe then pulls the coating off the substrate with a constant velocity, as schematically shown in Fig. 5d [119]. The pull force as a function of pull distance is recorded, which is mainly characterized by four parameters: the peak stress $\\sigma_{\\mathrm{max}},$ the maximum extension $\\varepsilon_{\\mathrm{max}},$ the plateau stress $\\sigma_{p}$ and the work of debonding $W_{\\mathrm{deb}}$ . Like the adhesion obtained in the peel test, the four parameters obtained in the probe pull test are quantitative evaluations of different hydrogel coatings under various test conditions. The probe pull test has the same issue with bonding the probe and the hydrogel coating together as the peel test. If the probe debonds along the interface with the coating during the test, the pull result fails to reflect the bonding between the hydrogel coating and the target substrate.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 24,
+        "chunk": "# The double cantilever beam test  \n\nIn this test, a coating is bonded between two cantilever beams, as illustrated in Fig. 5e [120]. A load is then applied vertically to the end of the beam. The load is denoted $P$ and the deflection between the two ends of the beams is denoted δ. The coating between the beams has a pre-crack of length $a$ . Based on a simple beam model, in which the length of the beam equals the crack length $a$ and the boundary of the beam at the crack tip is fixed, the energy relweiadstehraotfetihsegisvpencibmy $\\begin{array}{r}{G_{I}=\\frac{3B P^{2}a^{2}}{2b}}\\end{array}$ $b$ nbge angc tohne$\\begin{array}{r}{B=\\frac{64}{E b h^{3}}}\\end{array}$ stant of the beam ( $E$ is the Young’s modulus of the beam, and $h/2$ is the thickness of each beam). If the modulus of the coating is much lower than that of the two bonded beams, the soft coating will give rise to a deflection of the beams in the uncracked zone. The simple beam theory is not sufficient for this case. Instead, the energy release rate $G$ was derived from a model of a beam on an elastic foundation [121–123]. The shortcoming of the traditional double cantilever beam test is the requirement for accurate measurement of the crack length. A modified double cantilever beam test, known as the contoured double cantilever beam test, was subsequently devised as shown in Fig. 5e [124,125]. If the critical energy release rate is irrelevant to the crack length $a$ , one requirement is that the value of $B a^{2}/b$ is a constant. Thus, the height of the cantilever beams $h$ satisfies $a^{2}/h^{3}=$ constant, which gives a contoured profile of the beam. The energy release rate of the coating is obtained once the critical load for crack propagation is measured.  \n\ncoatings also show huge potential in non-medical applications, such as environmentally friendly anti-fouling coatings for marine vessels, lubricious coatings for soft devices and ionic conductors in stretchable ionotronics. Functional hydrogel coatings are expected to play a key role in various applications.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 25,
+        "chunk": "# CONCLUSIONS AND OUTLOOK  \n\nIn this paper, we review the recent advances in functional hydrogel coatings, with focus on coating functions and applications, coating methods, and coating tests. The majority of the established applications of functional hydrogels are in the field of biomedicine. Hydrogel coating acts as a versatile solution for improving the biocompatibility of preformed materials or devices that will interact with living tissues, such as implants for plastic surgery, artificial menisci, implanted neural electrodes and biosensors. Furthermore, drug-loaded and anti-bacterial hydrogel coatings can reduce the risk of infection and inflammation of living tissues. Functional hydrogel  \n\nHydrogel coating methods have started to achieve tough adhesion in laboratories, but some gaps remain in the translation to mass production. The requirement for surface bridge and initiation methods, such as treatment of the target substrate for strong bonding and an oxygen-free chamber with high humidity for hydrogel coating curing, are accepted in research but may not be economical for mass production in many applications. In addition, the surface initiation method leads to substantial wastage of the hydrogel precursor. The hydrogel paint method uses traditional painting techniques for coating. The paint user is only responsible for the painting and waiting for curing and is free of any involvement with the preparation of the hydrogel paint. However, the current hydrogel paint strategy is only suitable for functional hydrogel coatings with single network and is unable to achieve a very tough hydrogel coating. The compatibility of the hydrogel paint strategy with tough hydrogel formulation approaches such as double networks, and nanoparticle and fiber reinforced composites, has not been investigated so far. The development of tough hydrogel paint requires immediate action.  \n\nThe strong adhesion between hydrogel coatings and target substrates is the main mechanical consideration in evaluating the quality of functional hydrogel coatings. The incorporation of strong interaction at the coating-substrate interface and the significant dissipation of energy in the bulk of the coating or substrate would give an adhesion of more than $1000\\mathrm{J}/\\mathrm{m}^{2}$ under static loading conditions. However, the adhesion under cyclic loading conditions has been reported in only a few cases [126–128]. It has been shown that the toughness of a piece of hydrogel under cyclic loading can be two orders of magnitude lower than that under static loading conditions [129]. It is therefore questionable whether the adhesion of the hydrogel coating under cyclic loading is the same as that under static loading. This question is open to substantial further investigation. Several mechanisms have been put forward to improve the fatigue threshold of hydrogels [130–132], and attention should be paid to preparing fatigue-resistant hydrogel coatings.  \n\nThe long-term stable adhesion of functional hydrogel coatings in harsh environments—such as in seawater and in biological conditions including body fluids and blood—is important for their application.  \n\nHowever, studies in this field are limited and scattered. Both the interfacial bonding between hydrogel coatings and substrates and the functional hydrogel coating itself might degrade after extended soaking in these environments, resulting in the failure of the coating by delamination or fracture. For example, a lightly stretched siloxane bond adopted in achieving strong adhesion of a hydrogel coating will hydrolyze into two silanol groups in the aqueous environment [133]. The design of hydrogel coatings that require long-term survival should therefore be carefully considered.  \n\nA versatile test method for measuring the adhesion of hydrogel coatings is lacking, particularly when the coatings are extremely thin. The essential difficulty is how to peel the coating off in a quantitative manner. For example, in a peel test, a hydrogel coating is peeled away from a substrate uniformly, assisted by a backing, and the steady peel force is a direct measurement of the adhesion. The peel test is an ideal method for obtaining the adhesion owing to its simple preparation and interpretation, provided that the attachment survives throughout the peel test and its adherence to the coating induces negligible influence on the integrity of the coating. Cyanoacrylate adhesive (commonly used to bond a PET backing to a hydrogel coating) might not be suitable for thin hydrogel coatings owing to the diffusion of the adhesive into the hydrogel. A thin hydrogel coating requires an adhesive-free backing that can bond strongly to the hydrogel coating by attaching, like an adhesive tape. A possible method is to use dense physical bonds, such as hydrogen bonds, to achieve adhesion of a backing to the hydrogel coating. A flexible backing adhered to an acid hydrogel through hydrogen bonds was demonstrated by growing polyacrylic acid (PAA) chains on an elastomer film [134]. The bonding was instant and tough and is attributed to the fast formation of dense hydrogen bonds. The enormous diversity of noncovalent bonds makes the design space for hydrogel adhesive tape applicable to various hydrogels. The development of hydrogel adhesive tapes that are valid for use with various hydrogels and compatible with the peel test is a promising direction for establishing a versatile testing platform for hydrogel coating adhesion. Using this platform, the adhesion test can be completed through a simple attaching and peeling procedure without concerns about the diffusion of additional adhesive into the hydrogel coatings. Because of the size effect in peeling hydrogel coatings and the intrinsic viscoelastic response of polymeric networks, the adhesion of functional hydrogel coatings is specific to the thickness and loading speed. We suggest that the coating thickness and loading speed are made clear when specifying the coating adhesion.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 26,
+        "chunk": "# FUNDING  \n\nThis work was supported by the National Natural Science Foundation of China (11525210, 91748209) and the Fundamental Research Funds for the Central Universities (2020XZZX005– 02) to J.L. and S.Q. This work was also supported by the National Science Foundation (DMR-14–20570) to Z.S.",
+        "category": " References"
+    },
+    {
+        "id": 27,
+        "chunk": "# AUTHOR CONTRIBUTIONS  \n\nW.Y. conceived the idea. All authors contributed to the writing of the manuscript.  \n\nConflict of interest statement. None declared.",
+        "category": " References"
+    },
+    {
+        "id": 28,
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+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,107 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Light-Assisted 3D-Printed Hydrogels for Antibacterial Applications  \n\nLiwen Zhang, Naufal Kabir Ahamed Nasar, Xumin Huang, Chenyang Hu, Xuan Pang, Xuesi Chen, Ruirui Qiao,\\* and Thomas Paul Davis\\*  \n\nLight-assisted 3D printing technology, which uses a light source to solidify a photopolymerizable prepolymer solution, has shown great potential in the development of antibacterial hydrogels with high-resolution, specific features and functionalities. 3D-printed hydrogels with customized structures and antibacterial functions are widely used in tissue engineering, regenerative medicine, wound healing, and implants to advance the modeling and treatment of diseases. In the current review, an overview of light-assisted 3D printing technologies is first provided for the development of antibacterial hydrogels. Novel strategies involving the integration of inorganic nanomaterials, antibiotics, and functional polymers into 3D-printed hydrogels for the enhancement of antibacterial effects are then discussed. Finally, the perspective of advanced design using artificial intelligence and machine learning is proposed, providing a comprehensive yet succinct examination of 3D-printed hydrogels for antibacterial purposes.  \n\nstrategies against antimicrobial resistance. In recent years, antibacterial biomaterials have been increasingly recognized as promising alternatives in combating bacterial infectious diseases for their antibiotic resistance, biocompatibility, as well as versatility in various biomedical products to prevent infections.[4]  \n\nHydrogels, i.e., highly hydrated 3D porous polymer networks, have been extensively studied in antibacterial applications. By either integrating antibacterial agents (e.g., metal ions or metal-based nanoparticles, antibiotics) or utilizing inherent antibacterial activity derived from polymeric structures, hydrogels have shown great promise as an alternative solution to traditional antibiotic treatments.[5] Due to high water-holding capacity, biocompatibility,",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1. Introduction  \n\nCurrently, ${\\approx}13$ million patients globally face perilous bacterial infections each year. Particularly noteworthy is the estimation that during the COVID-19 pandemic, up to $95\\%$ of pneumonia-related deaths were attributed to secondary Streptococcus pneumonia (S. pneumonia) infections.[1] Antibiotics have historically effectively treated bacterial ailments since Fleming discovered penicillin in 1928.[2] However, the overuse and long-term use of antibiotics have spurred the emergence of multidrug-resistant bacteria, including superbugs.[3] Therefore, it is highly demanded to develop antibiotic-free and network structures, hydrogel effectively improves the loading and release of antibacterial agents and reduces the cytotoxic impact of antibacterial agents.[6] Nevertheless, a significant obstacle in the conventional fabrication of hydrogels is the difficulty of shaping them in predesigned geometries.[7]  \n\nOver the last few decades, significant efforts have been devoted to developing hydrogels with intricate structures and functional properties using 3D printing techniques, facilitating the design of patient-specific constructs with optimized antibacterial properties.[8] Some 3D printing methods, including direct ink writing[9] and fused deposition modeling (FDM),[10] have been used in the fabrication of materials with antibacterial activities to produce customized medical devices with antibacterial properties, such as meniscus replacement,[11] wound dressings,[12] and osteochondral repair.[13] Despite exciting advantages, certain 3D techniques with higher printing temperatures $(>100^{\\circ}\\mathrm{C})$ often lead to the degradation of thermosensitive drugs and biological agents, such as proteins, RNA, and enzymes, resulting in a reduced antibacterial effect.[14] In contrast, light-assisted 3D printing methods utilize a light source, such as a laser or a projector, to selectively solidify liquid resins at room temperature, showing great promise in printing hydrogels with thermosensitive components.[15] Moreover, light-assisted 3D printing, like stereolithography (SLA) and digital light processing (DLP),[16] offers superior spatial resolution, finer details, better pattern fidelity, and faster fabrication speeds,[15a] enabling the fabrication of hydrogel structures with high resolution and designed geometries.  \n\nDespite previous review articles focusing on the topic of antibacterial hydrogels,[5,17] the scope of this article is to provide a comprehensive review of antibacterial hydrogels fabricated by current state-of-the-art light-assisted 3D printing technologies. We first present a detailed overview of the light-assisted 3D printing strategies for the development of antibacterial hydrogels. The fundamental principles, advantages, and disadvantages of various light-assisted 3D printing techniques are introduced. Second, we describe the progress in the development of natural and synthetic hydrogels using light-assisted 3D printing techniques and highlight their antibacterial effects. Subsequently, we focus on various strategies for enhancing the antibacterial effects of 3D-printed hydrogels by integrating 1) inorganic nanoparticles; 2) antibiotics; and 3) functional polymers. Future perspectives on novel artificial intelligence-based additive manufacturing techniques are presented, aiming to underpin the potential of next-generation antibacterial hydrogels for applications in tissue engineering and regenerative medicine fields.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2. Light-Assisted 3D Printing Techniques for Antibacterial Materials  \n\n3D printing, also known as additive manufacturing, is a process that builds 3D objects in a layer-by-layer manner from digital models designed by computer-aided design (CAD) software.  \n\nThe CAD files are sliced into discrete layers, each printed on top of the other until the target object is fully formed.[18] In contrast with conventional manufacturing techniques, 3D printing offers unparalleled design freedom, enabling the production of complex geometries and customized parts with ease. Its ability to rapidly prototype and manufacture low-volume, high-value items at a reduced cost makes it a valuable tool for various industries, from aerospace and automotive to healthcare and consumer goods.[19] Its minimal material waste and on-demand manufacturing capabilities also contribute to sustainability efforts and resource efficiency. In the last decades, numerous 3D printing techniques have been extensively explored to develop and fabricate materials, presenting innovative avenues for antibacterial functions. Particularly, light-assisted 3D printing systems, like DLP and SLA, enable the production of objects with a spectrum of geometrical complexities through precise spatiotemporal control over localized photopolymerization of resins. An overview of the strengths and weaknesses of each light-assisted 3D printing technique is presented in Figure 1.  \n\nFurthermore, light-assisted 3D printing techniques have been applied across various domains, including electronics, bioengineering, drug delivery, and antibacterial therapy. In the field of electronics, this technology enables the precise fabrication of intricate circuits and components directly onto diverse substrates, facilitating the development of compact, flexible electronic devices that are crucial for advancing wearable technologies and smart devices. In bioengineering, it plays a crucial role in producing customized, biocompatible implants and scaffolds with controlled microarchitectures, enhancing cellular interactions and tissue integration. Additionally, light-assisted 3D printing contributes to the development of advanced drug delivery systems capable of dispensing medications in a controlled manner, adapted to the patient’s specific physiological conditions. Moreover, this technology supports the production of objects with antibacterial properties, which are important for manufacturing medical devices and hospital equipment that minimize bacterial growth and mitigate infection risks.  \n\n![](images/c6fc0388fa8ccf2eaef28c28c14b8e445e14f3a9a8d50c3f0a50ed07b1b738be.jpg)  \nFigure 1. Summary of advantages and disadvantages of main light-assisted 3D printing techniques.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2.1. Vat Photopolymerization  \n\nVat photopolymerization is a general term for SLA and its related 3D printing process, where the curing of 3D constructs is induced by laser. This light-assisted method, pioneered by Chuck Hill in the early 1980s, is rooted in traditional SLA principles. SLA utilizes a process where liquid resin undergoes solidification via a photopolymerization reaction, building up layer-by-layer to create 3D-printed objects. The UV laser is used to trace each layer of the 3D object onto the surface of the liquid resin, initiating a photochemical reaction with the monomer resin and causing solidification.[20] The process of SLA photopolymerization is conducted in a point-by-point fashion, where the solidification takes longer to create an object, but it does so with complex geometries, high resolution, and a smooth surface finish. SLA not only overcomes limitations of resolution and precision in traditional nozzle-based 3D printing but also achieves a superior surface finish.[21] Aside from the resins’ compatibility with various solvents, chemicals, and reagents, SLA is favored for its versatile material selection, thereby expanding the range of available printing materials. Despite their relatively slower printing speed, SLA 3D printers have become immensely popular for their ability to accurately produce precise parts with high fidelity in various photopolymer-based materials, featuring fine details and a smooth surface finish.[22]  \n\nSLA 3D printing has been able to fabricate antibacterial materials using biocompatible composite materials. Vidakis et al. utilized a commercially available urethane dimethacrylate-based resin conjugated with copper nanoparticles (CuNPs) for antibacterial applications. It was found that $2\\%$ CuNPs have an intensified zone of inhibition for both Escherichia coli (E. coil) and Staphylococcus aureus (S. aureus), at 4.3 and $5.6\\mathrm{mm}$ , respectively.[23] Similarly, Marin and co-workers used poly(methyl methacrylate, PMMA)-based resin conjugated with ceramic powders to create antibacterial conjugate materials through SLA 3D printing. It was found that PMMA in conjugation with aluminum nitride demonstrated the most effective antibacterial effect against E. coli, with a $30\\mathrm{-}60\\%$ reduction in optical density.  \n\nThe DLP method originated in the 1980s when Texas Instruments developed the Digital Micromirror Device (DMD), initially developed for projection displays and is a critical component of DLP printing.[25] DMDs consist of many micromirrors, each acting as individual pixels capable of being either illuminated or unilluminated in a binary system. DMDs in DLP printing can precisely control these microscopic mirrors to modulate light, generating precise patterns for each layer of a 3D object.[26]  \n\nWhile SLA relies on laser technology and sequential printing spot-by-spot, DLP utilizes the DMD to simultaneously project cross-sectional images derived from the CAD models, resulting in enhanced printing speeds compared to spot-by-spot SLA 3D printing. Furthermore, there are similar features between DLP and SLA, where DLP and SLA 3D printing are all based on liquid resin containing monomer or oligomer photopolymers that are solidified to a solid object via light-mediated polymerization.[27] SLA- and DLP-derived objects require postprocessing, including eliminating excess resin and UV curing for increased solidification.  \n\nThe DLP 3D printing technique shares some advantages with SLA 3D printing. DLP technology is also proficient in generating intricate geometrics with exceptional printing speeds, high resolution, and smooth surface finish without any visible layer lines. DLP’s versatile material selection allows for tailored solutions, each offering distinct physical characteristics to accommodate various applications, including soft robots, wearable devices,[28] tissue engineering, complex tissue modeling,[29] and drug delivery.[30] For example, Du and co-workers have used crosslinkable polydimethylsiloxane–thiourea-based resin for DLP 3D printing.[31] The resultant elastomeric parts were produced to have tunable mechanical characteristics and robust elasticity. As such, high-resolution human hand models, lattices, and porous structures were fabricated, with potential applications in the rapid fabrication of medical devices. Additionally, Hone and co-workers have used DLP technology to fabricate a fibroin-based hydrogel for tissue engineering. To recapitulate cartilage tissue laden with chondrocytes, silk fibroin polymer combined with glycidyl methacrylate shows promise for applications in chondrogenesis and in vivo transplantation of engineered cartilage.[32] Furthermore, DLP 3D printing has created intricate composite structures with graphene oxide $\\bar{(\\mathsf{G O})}^{[33]}$ and sliver nanoparticles[34] for antibacterial applications.  \n\nComputed axial lithography (CAL) is an innovative lightassisted 3D printing technique that aims to develop 3D-printed objects in a single step without needing a layer-by-layer deposition.[35] CAL represents the intersection between typical SLA and computed tomographic imaging. Photopolymers are illuminated from multiple angles along a single axis to form the 3D-printed object.[36] The volumetric polymerization occurs through the photosensitive resin in an enclosed vat, where 2D images are projected using a DLP projector, and the convergence from different angles produces a 3D-printed object. The unique benefit of CAL is the ability to render 3D objects from high-viscosity resin without support structures. Meanwhile, the time taken to print is reduced drastically compared to traditional layer-by-layer methods.[37] Despite its promising capabilities, CAL is still in the early stages of development, focusing on refining the printing process and compatibility with different types of photopolymers. As such, CAL 3D printing has yet to be fully explored for its potential in biomedical applications.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2.2. Light-Assisted Inkjet Printing  \n\nThe material jetting technique, also known as Inkjet 3D printing, utilizes gravity, pressure, and another mechanism to expel the droplets of the bioink to the working platform, solidifying under specific wavelengths of light to fabricate 3D objects.[38] The critical point is that each printed layer must be cured by applying an appropriate curing step between successive deposition cycles. In this regard, UV light is directed onto the droplets on the build platform in the Material Jetting machine for curing. This photopolymerization/photocuring process utilizes a specific wavelength of light to solidify monomers/oligomers from a liquid state into solid objects.[39] Unlike the wavelengths used by other light-assisted 3D printing techniques such as SLA and DLP, which are confined per the 3D printer manufacturers’ specifications, material jetting’s light source has no wavelength restrictions, allowing for increased versatility.[40] Material jetting 3D printing has benefits, including multimaterial integration, high resolution, smooth surface finish, and the ability to produce complex geometries with fine details. Material jetting 3D printing significantly reduces ink consumption by restricting ink ejection only to the intended deposition areas on the surface. Mugnaini et al. synthesized photocrosslinkable methacrylic pullulan, utilizing it as a bioink. The aqueous dispersions of methacrylated pullulan served as the substrate for inkjet printing.[41] However, material jetting does have some limitations. It has a relatively slow printing speed and high price compared to other 3D printing techniques. Similarly, the choice of bioinks is limited to ones that process low viscosity, optimal degradation, and the ability to remain liquid during printing.[42] Additionally, printed materials often exhibit lower mechanical strength and are prone to fracturing under mechanical stress compared to structures fabricated using traditional approaches. Particularly within the UV curing process, some materials with limited photostability may compromise their properties upon prolonged exposure to ambient light. The ongoing development of new ink materials holds significant promise in overcoming these persistent limitations. Although there are some shortcomings, material jetting printing has been successfully employed in antibacterial, tissue engineering, and pharmaceutical agents.[43]  \n\nMultiJet 3D printing is another nozzle-based 3D printing technology renowned for its precision and versatility. Similar to Inkjet 3D printing, this technique deposits photopolymer droplets layer-by-layer to create a 3D object. The distinguishing characteristic of MultiJet 3D printing is its capability to use multiple materials simultaneously, enabling the fabrication of complex structures with diverse properties within a single print job. The MultiJet printer utilizes multiple UV-curable liquid plastics that are thermosensitive or photosensitive, which are jetted through a multiextruder to print multimaterial objects simultaneously.[44] The deposition of multiple materials as the core function of MultiJet printing allows for highly accurate and finely designed objects with multiple components to be fabricated, which have a better surface finish than material extrusion methods.[45] MultiJet printing allows for certain advantages, such as exceptional precision and ease of use when incorporating multiple photopolymers. Multimaterial 3D printing has been applied to fabricate cardiac microphysiological devices to mimic native cardiac tissues in vitro.[46] Using six different bioinks and multistep lithography allowed for the fabrication of cardiac devices that can reconstruct tissue mechanics. As such, this method of 3D printing has been applied in many biomedical settings such as antibacterial and fluidic systems,[47] tissue engineering,[48] and drug delivery.[49] For example, He et al. utilized inkjet 3D technology to synthesize materials to combat biofilm formation due to bacterial colonization. It was found that polytricyclodeadimethanol diacrylate-based 3D-printed objects had a $99\\%$ reduction in biofilm formation from P.C aeruginosa compared to traditional silicon-based prosthetics.[50] Similarly, Adarkwa and co-workers, using a hybrid inkjet 3D printing system, synthesized 3D-printed coating using poly(lactic-co-glycolic) acid (PLGA) and polycaprolactone (PCL) coupled with amorphous calcium phosphate and vancomycin. The release kinetics of the material were shown to have high bioactivity against S. aureus, as demonstrated by the zone of inhibition, where the concentration of vancomycin released was above the inhibitory and bactericidal concentrations.[51]",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.3. Light-Assisted Extrusion Printing  \n\nMaterial extrusion-based 3D printing is an additive manufacturing technique that uses a nozzle to continuously extrude the ink, depositing material layer-by-layer to yield 3D structures.[52] One of the extrusion-based 3D printing techniques is FDM, which has become a standard tool for manufacturing businesses, prototyping, jewellery, science, and education design on both desktop and industrial scales. FDM technology employs thermal energy to liquefy the filament or wire and extrude materials through a nozzle.[53] The liquified biomaterial harnesses gravity, fluidics, and other pressure-driven mechanisms to expel the droplets to fabricate a range of constructs. In this approach, the printing nozzle traverses the $X$ and $Y$ axes to generate each layer, while the vertical motion in the $Z$ axis permits incremental layer-bylayer material deposition.[54] The prominent advantages of FDM encompass its cost-efficiency, user-friendliness, versatility, and capacity to fabricate intricate structures employing a variety of polymer filaments.[55] Specifically, FDM is known for its process simplicity, where the thermosensitive filament is melted and then solidified at ambient temperature, contributing to its costeffectiveness and making it a viable option for various applications. This 3D printing technique allows for well-controlled and precise geometries and structure architecture.  \n\nHowever, the limitations of FDM printing are its slow printing speed, the presence of layer lines, and reduced resolution, which are the side effects of using the printing nozzles.[56] Meanwhile, the reliance on a nozzle-based continuous printing system constrains the production of high-resolution scaffolds, where the size of nozzles, generally from 0.4 to $0.6\\mathrm{mm}$ , results in layer lines and restricted resolution.[57] Moreover, the high temperature required to melt certain materials leads to compromises in material quality. The high temperature of the nozzle also possibly leads to the loss of control of extrusion during the nozzle movement, resulting in the stringing phenomenon. FDM 3Dprinted objects need additional postprocessing operations to improve their appearance and strength, such as sanding, polishing, vapor smoothing, and hydrodipping with customized patterns.[58] These limitations constrain the potential applicability of FDM in fabricating antibacterial materials, particularly for biomaterials necessitating robust mechanical strength. However, the FDM printing technique still exhibits its potential in creating antibacterial materials. Nyabadza et al. demonstrated increased antibacterial efficacy against E. coli using 3D-printed polylactic acid (PLA) objects coated with CuNPs, exhibiting a $12.33\\mathrm{mm}$ zone of inhibition.[59] Bayraktar et al. also utilized PLA filament embedded with silver nanowires to fabricate antibacterial materials, showcasing antibacterial activity against E. coli and S. aureus, with a $100\\%$ killing rate for both pathogens after 2 h.[60] These studies underscore the potential of FDM printing in combating bacterial contamination, offering versatile applications in healthcare, food packaging, and beyond.  \n\nWith the development of material extrusion techniques, light-assisted extrusion printing offers a strategy to address the limitations of high temperatures in traditional extrusion printing. The light can be integrated into any stage of extrusion printing: during printing,[61] postprinting,[62] or after the deposition of each extrusion layer.[63] For example, Ouyang et al. developed a generalizable in situ-crosslinking strategy in which the light was introduced immediately before the deposition to achieve high encapsulated cell viability $(\\approx95\\%)$ .[61]",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.4. Selective Laser Sintering  \n\nSelective laser sintering (SLS) 3D printing utilizes a high-power laser to heat and fuse powdered materials layer-by-layer. In SLS 3D printing, a layer of powdered material is spread across the build platform and then selectively fused by a laser according to the CAD model.[64] This process is repeated layer by layer until the object is fully formed, allowing for the creation of complex and precise 3D structures.[65] The major benefit of this 3D printing technique is the enhanced strength and durability of the material, which can be applied in the automotive[66] and healthcare industries.[67] However, a significant limitation of SLS 3D printing is its lower resolution compared to other light-assisted 3D printing techniques such as SLA and DLP, resulting in less detailed and defined structure. Due to the higher temperature used in the printing process, the application of SLS technology in producing antibacterial materials remains challenging.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 3. Light-Assisted 3D-Printed Hydrogels  \n\nHydrogels are widely recognized for their significance and versatility in biomedical applications. Hydrogels are polymeric network structures with inherent hydrophilic properties, derived from natural and synthetic polymers. Their defining features encompassed the ability to uptake water many times their dry weight and insolubility in water.[68] Typically, the crosslinking of the polymer network involves the reaction between one or more monomers, where the number of monomer and functional groups attached to the polymer backbone determines the degree of crosslinking. Currently, developing antibacterial hydrogels has become a main focus of biomedical research. Numerous cuttingedge antibacterial hydrogels have been created, each with its exceptional characteristics, such as high water swellability, elevated oxygen permeability, enhanced biocompatibility, facile drug loading and release, and structural diversity. However, in numerous applications, the capacity to shape hydrogels into intricate 3D structures is indispensable. For instance, when hydrogels are regarded as a tissue scaffold, internal channels with high liquid flow permeability are necessary to sustain cell viability. Therefore, the versatility of light-assisted 3D printing technology in creating complex structures and superior spatial resolution makes it a revolutionary tool for fabricating hydrogel-based scaffolds for tissue engineering and antibacterial application. Moreover, light-activation mechanisms in 3D-printing were used in control structures of hydrogels from the millimeter scale to the submicrometer scale.  \n\nHydrogels can be classified into natural and synthetic categories. Natural hydrogels typically consist of polymers derived from biological sources such as collagen, gelatine, hyaluronic acid (HA), and alginate.[69] These hydrogels possess excellent biocompatibility, enabling their integration into biological systems and minimizing the risk of adverse reactions.[70] Applications in complex scenarios are limited due to insufficient mechanical strength.[71] In contrast, synthetic hydrogels, composed of polymers such as poly(ethylene glycol) (PEG),[72] poly(acrylamide) (PAM),[73] or PCL,[74] have robust mechanical properties.[75] However, synthetic hydrogels exhibit limited biocompatibility and generate degradation byproducts that are not found in nature.[76] Despite their respective advantages and disadvantages, both natural and synthetic hydrogels are widely employed in light-assisted 3D printing to create antibacterial hydrogels (Table 1).",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 3.1. Natural Hydrogels  \n\nNatural hydrogels are generally referred to as biopolymers derived from humans, animals, plants, and bacteria. Natural hydrogels can be divided into three groups according to their chemical structure difference: polysaccharides, glycosaminoglycans (GAGs), and polypeptides/proteins.[77] These naturally derived materials can form a natural extracellular matrix a)GelMA, gelatine methacryloyl. b)SLA, stereolithography; DLP, digital light processing; CAL, computed axial lithography. c)PEGDA, polyethylene glycol diacrylate.  \n\nTable 1. Summary of light-assisted 3D-printed hydrogels and their properties.   \n\n\n<html><body><table><tr><td>Hydrogels</td><td>Light-assisted 3D printing</td><td>Properties</td><td>Refs.</td></tr><tr><td>GelMAa)</td><td>SLA, DLP, CALb)</td><td>Easy antibiotic loading</td><td>[37,163,164]</td></tr><tr><td>Collagen</td><td>SLA,DLP</td><td>Biocompatible antibacterial effect against bacteria</td><td>[165,166]</td></tr><tr><td>HA</td><td>SLA,DLP</td><td>Prolonged antibacterial activity with wound-healing properties</td><td>[167-169]</td></tr><tr><td>Alginate</td><td>SLA,DLP</td><td>Potent antibacterial effect against bacteria</td><td>[170,171]</td></tr><tr><td>Chitosan</td><td>SLA,DLP</td><td>Antibacterial Scaffold for bone tissue engineering</td><td>[172,173]</td></tr><tr><td>Acrylic acid</td><td>SLA,DLP</td><td>Self-healing hydrogel with antibacterial effect</td><td>[112,174]</td></tr><tr><td>PEGDA)</td><td>SLA,DLP</td><td>Stimuli-responsive and antibacterial</td><td>[175,176]</td></tr><tr><td>Poly(vinyl alcohol)</td><td>DLP</td><td>Strong antibacterial effect and self-healing</td><td>[123,177]</td></tr></table></body></html>  \n\n(ECM) with the assistance of various proteins, leading to excellent biocompatibility and cell affinity.[78]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3.1.1. Polysaccharides-Based 3D-Printed Hydrogels  \n\nIn the last decades, various polysaccharides have been successfully employed to fabricate functional natural hydrogels, including but not limited to alginate,[79] methylcellulose,[80] and chitosan.[81] Among them, chitosan and alginate have been approved by the U.S. Food and Drug Administration due to superior safety and biocompatibility. Chitosan is one type of cationic polyelectrolyte composed of D-galactose and $N$ -acetyl-Dglucosamine. Amine groups make chitosan more easily dissolved in acidic solutions and provide higher chelation affinity to metal cations, especially antibacterial cation metals.[82] Srikanthan et al. utilized inkjet printing to fabricate hydrogel composed of chitosan and polyethylene oxide $(M_{\\mathrm{w}}=10000000\\mathrm{g}\\mathrm{mol}^{-1})$ .[83] The 3D printing parameters displayed a printing speed of $17{-}29\\mathrm{mms^{-1}}$ , extrusion pressure between 21 and $24\\mathrm{kPa}$ , and printing times of $0.3\\mathrm{-}0.5\\mathrm{h}$ . These 3D-printed scaffolds exhibited meshy structures capable of incorporating antibacterial zinc oxide nanoparticles. Notably, the hydrogel was very sensitive in acidic $\\mathsf{p H}$ conditions to release zinc oxide nanoparticles for inhibiting the growth of Gram-positive (S. aureus) and Gram-negative (E. coli) bacteria. As 3D printing resolutions are highly dependent on the size of the printer nozzle and the postcuring process, it is difficult to manufacture materials with precise control and high resolution. The limitations of chitosan-based materials are low mechanical resistance, poor control over pore size, and low solubility in neutral pH.[84]  \n\nAlginate is a water-soluble linear polysaccharide extracted from brown algae or bacteria.[85] The gelation mechanism of alginate is different from chitosan, in which alginate self-assembles into acidic gels in a lower $\\mathsf{p H}$ environment. A distinctive feature of alginate is its biodegradability and decreased mechanical properties over time, making them ideal candidates for tissue engineering and regenerative medicine. Meanwhile, alginate-based materials can cooperatively bind with metal cations, including ${\\mathsf{C a}}^{2+}$ , $\\mathrm{Mg}^{2+}$ , $\\operatorname{Sr}^{2+}$ , $\\mathrm{\\DeltaBa}^{2+}$ , or $\\mathbb{A}l^{3+[86]}$ providing a new opportunity for antibacterial hydrogel composites. For instance, Hadi et al. employed inkjet printing to manufacture cell-laden hydrogel composites containing alginate and methylcellulose (Figure 2).[87] In this study, gallium chloride not only induces the gelation of alginate but also endows the hydrogel composites with superior antibacterial effects. The results showed that the galliumcrosslinked bioink exhibited potent antibacterial activity toward both S. aureus and P. aeruginosa bacteria, with a growth rate of $99.99\\%$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3.1.2. GAG-Based 3D-Printed Hydrogels  \n\nGAG-based hydrogels are biomaterials composed of GAGs, long unbranched polysaccharides with repeating disaccharide units.  \n\n![](images/ad2a3463a082b15327986b63a9aad6c7f2e8556faf70c467b863904ede410156.jpg)  \nFigure 2. a) Schematic illustration of the 3D printing process of methylcellulose and alginate hydrogel composites. b) Surface antibacterial activity of the hydrogel toward S. aureus and P. aeruginosa bacteria. Surviving S. aureus and P. aeruginosa colonies on agar plates after contact with $0.5\\mathrm{wt\\%}$ galliumcrosslinked hydrogels. The gallium-crosslinked hydrogel kills almost all bacteria in contact with the hydrogel surface. c) Schematic illustration of the antibacterial activity of gallium-crosslinked hydrogel. Accordingly, the antibacterial activity of the hydrogel stems from the presence of gallium cations on the hydrogel surface. Reproduced with permission.[87] Copyright 2021, Elsevier.  \n\nGAGs have several species, including HA, chondroitin sulfate, and heparin.[88] HA is one of the most representative anionic GAGs, composed of D-galactose and N-acetyl-D-glucosamine and commonly found in various connective and support tissues.[89] HA has unique properties, such as viscoelasticity similar to in vivo structures, biocompatibility, and increased water retention capacity.[90] As a critical component of the ECM, HA also possesses essential functions in proliferation, migration, and tissue hydration. HA has been widely applied in biomedical applications, such as drug delivery,[91] tissue regeneration,[92] osteoarthritis treatments,[93] and so on. Additionally, HA-based hydrogels have become a popular topic in biomedicine. These hydrogels provide a supportive, robust matrix that mimics a natural tissue environment and can be safely degraded by hyaluronidases, allowing for absorption and metabolism within living systems without adverse effects.  \n\nMore importantly, HA can be regarded as a photocrosslinker to generate stable hydrogels when exposed to light of specific wavelengths. A standard method to modify HA involves methacrylate substitution, generating hyaluronic acid methacryloyl (HAMA) with multiple chemical crosslinking sites (acrylamide groups).[94] This chemical-modified HA can be used as a bioink in light-assisted 3D printing processes (SLA and DLP), where the hydrogel can be selectively solidified layer-by-layer to create complex structures. Interestingly, HAMA, a natural ECM component with anti-inflammatory effects promoting cell adhesion and proliferation, has become an exciting candidate for tissue engineering and regenerative medicine. Si et al. developed a doublecrosslinked HA bioink containing UV-crosslinker HAMA and click-reaction crosslinked $_{3,3^{\\prime}}$ -dithiobis (propionyl hydrazide)  \n\n(DTP)-modified HA (Figure 3).[95] This bioink was successfully employed in the 3D extrusion printing process, and UV light $(365\\mathrm{nm})$ was applied to crosslink the samples to obtain the final product. By mixing them at different ratios of two crosslinkers, the hydrogels exhibited controllable degradation rates and high swelling capacities, making them suitable for wound healing applications by incorporating the antibacterial drug nafcillin. However, the HA-based hydrogels are generally brittle or have weak mechanical strength. Although HA is generally well tolerated by the body, there is still a risk of immunogenicity.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3.1.3. Polypeptide/Protein-Based 3D-Printed Hydrogels  \n\nThere are numerous natural polypeptides and proteins adopted into light-assisted 3D printing, including but not limited to gelatine,[96] fibrin,[97] and collagen.[98] Gelatine methacryloyl (GelMA), a chemically modified form of gelatine via a methacrylate process pioneered by Van Den Bulcke and co-workers,[99] is a notable example. This modification enables GelMA to become a crosslinkable polymeric monomer, allowing photoinitiated polymerization reactions to form stable polymer networks. GelMA, as a popular bioink, has been applied in light-assisted 3D printing techniques to fabricate biomedical hydrogels with highresolution and complicated structures owing to their inherent biocompatibility, biodegradability, low immunogenicity, and overall printability.[100] Interestingly, the mechanical properties of 3D-printed GelMA hydrogels are directly influenced by the degree of substitution, as methacryloyl groups replace reactive hydroxyl and amine groups on gelatine amino acid residues.[101]  \n\nA higher degree of substitution typically increases crosslinking density, enhancing the hydrogel network’s stiffness and strength to cater to various application requirements.  \n\n![](images/d4cc39999f5efc181a3113a48f862611a5083f47e701e4330c96687818266d13.jpg)  \nFigure 3. The schematic illustrates the fabrication process of double-crosslinked materials, incorporating a UV-crosslinker, HAMA, and click-reaction crosslinked DTP-modified HA. In vitro cytotoxicity testing revealed the potential of the drug-loaded HA hydrogel for wound dressings. Reproduced with permission.[95] Copyright 2021, MDPI.  \n\n3D-printed GelMA hydrogels are a promising candidate for antibacterial applications. Vigata and co-workers have developed a GelMA-based local drug delivery system, aiming to increase the effectiveness of antibiotics at the site of infection and reduce the systematic side effects of antibiotics. GelMA hydrogel discs were loaded with Cefazolin with a loading efficiency of $99\\%$ . Additionally, the effectiveness and bioactivity of Cefazolin were tested against S. aureus, demonstrating a dose-dependent manner of antibiotic activity and growth inhibition.[102] Visscher and co-workers integrated 3D printing with conventional saltleaching techniques to fabricate a novel scaffold for loading and delivering antibiotics.[103] This scaffold comprised PCL for antibiotic loading, specifically Cefazolin, with a surface-coated GelMA layer for prolonged antibiotic release. The results indicated that Cefazolin release was augmented in the 3D-printed scaffolds and sustained for up to 3 days, exhibiting efficacy against S. aureus. It was found that 3D-printed scaffolds containing the antibiotics had minimal reduction in the viability of fibroblast cells, indicating its excellent biocompatibility. Furthermore, Yang et al. printed hydrogel by combining GelMA and Xanthan gum (Figure 4).[104] In addition to antibiotics, N-halamines with potent biocidal properties were introduced as the primary antibacterial component in the 3D-printed hydrogels. Irradiation with a $365\\mathrm{nm}$ UV light (10 W) was utilized to finalize the products. The 3D-printed hydrogels demonstrated antibacterial solid activity, achieving complete inactivation of E. coil O157:H7 and S. aureus after $60\\mathrm{min}$ of culture. Moreover, biofilm tests revealed the hydrogels’ ability to inhibit bacterial biofilm formation. These dressings exhibited excellent biocompatibility, and in vivo experiments in a mouse model demonstrated significant acceleration of wound healing, underscoring their potential as promising candidates for wound treatment.  \n\nCollagen, derived from different animal sources, is a widely used natural polypeptide in synthesizing hydrogels and other biomaterials.[105] Approximately 28 types of collagens have different tissue distributions, functions, and cell identities. Type 1 collagen is the most prevalent, which consists of three alpha helices forming an overall helical structure. Like other naturally derived polymers in hydrogels, collagen offers advantages such as enhanced biocompatibility, reduced toxicity, and lower immunogenicity.[98] Collagen-based hydrogels have emerged as favorable environments for cell adhesion, proliferation, and tissue regeneration research, given collagen’s structural resemblance to the native ECM.[106] Moreover, collagen-based hydrogels are a great candidate for wound healing and anti-infection by providing structural support, promoting cellular migration, and facilitating tissue regeneration. Collagen as ECM regulates various stages of the healing process, ultimately contributing to effective wound closure and tissue repair. 3D printing is becoming a popular method for manufacturing collagen-based hydrogels with precise resolution and customizable shapes.[107] It is worth noting that 3D printing of collagen relies heavily on maintaining precise temperature conditions to obtain optimal printability. Collagen-based inks undergo a thermoreversible gelation process, where increasing the temperature to $37^{\\circ}\\mathrm{C}$ induces gelation while reducing the temperature leads to melting.[108] Therefore, light-assisted 3D printing techniques present an excellent option for fabricating collagen-based materials, as they typically involve minimal heat generation during printing. Municoy and co-workers developed 3D-printed collagen scaffolds through in situ synthesizing sliver nanoparticles (AgNPs) by UV irradiation.[109] Compared with AgNPs alone, collagen materials containing Ag exhibited enhanced antimicrobial activity against two bacterial strains, E. coli and S. aureus, possibly attributed to collagen’s inherent hydration, which enhances the diffusion of silver ions.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3.2. Synthetic Hydrogels  \n\nSynthetic hydrogels consist of 3D swelling networks formed by the covalent or ionic crosslinking of hydrophilic homopolymers or copolymers.[75] The polymerization of different synthetic monomers was employed for synthesizing hydrogels, including acrylic acid (AA), acrylamide (AAm), N-isopropyl acrylamide (NIPAM), and PEG and polyvinyl alcohol (PVA).[110] In contrast to natural hydrogels, synthetic hydrogels are typically fabricated from either low molecular weight monomers or high molecular weight polymers. These monomers can generate various types of hydrogels through diverse synthesis methods:[111] 1) homopolymer hydrogels that consist of a crosslinked network of one hydrophilic unit; 2) copolymer hydrogels, which have two or more monomers, with at least one hydrophilic monomer; 3) interpenetrating polymer hydrogels, which are synthesized through a dual gelation process, whereby secondary monomers infiltrate the initial hydrogel, creating a secondary intermeshing network.  \n\nAA, an anionic monomer, has been widely developed to fabricate hydrogels with water retention and stretchability, making them valuable for applications in cosmetics and biomedicine. Wang et al. successfully utilized a commercial DLP 3D printer (405 nm UV light) to manufacture hydrogels using AA as the monomer, trimethylolpropane trimethacrylate as the crosslinker, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide as the photoinitiator.[112] These hydrogels as soft actuators demonstrated significant deformation (up to $43^{\\circ}.$ ), rapid actuation speed (up to $1.08^{\\circ}\\mathrm{s}^{-1})$ , and consistent bending performance across cycles under relatively low actuation voltage (4–6 V). Poly(acrylic acid) (PAA)-based materials have also been applied in the antibacterial. Gratzel et al. reported PAA-diblock copolymers, where some factors such as $\\mathsf{p H}$ , electrolytes, salts, and polymer structure alterations impact the material’s antimicrobial activity.[113] Antimicrobial tests indicated that acid PAA copolymers had the highest antimicrobial efficacy on E. coli under slightly acidic conditions, attributed to the ion-exchange effect.  \n\nNIPAM is a monomer commonly used to synthesize temperature-responsive polymers, hydrogels, and other smart materials. NIPAM-based hydrogels exhibit unique swelling and deswelling in response to changes in temperature, particularly around the lower critical solution temperature (LCST) of NIPAM, which is ${\\approx}32^{\\circ}\\mathrm{C}$ . This responsiveness makes NIPAMbased hydrogels useful in various biomedical and technological applications, including wound dressing, skin replacement, antibacterial applications, grippers, soft robots, smart valves, and bionics.[114] As several studies have revealed the potential of hydrogels based on NIPAM produced through photopolymerization, NIPAM-based hydrogels are fabricated using cutting-edge light-based 3D printing techniques, which is a departure from traditional manufacturing methods. Solis et al. pioneered the fabrication of poly(N-isopropyl acrylamide) (PNIPAM) hydrogels utilizing a DLP 3D printer.[115] The unique LCST feature of NIPAM determined the properties of the final products, encompassing swelling capacity, water retention, stress resilience, and deformation ability, where these properties can be finely tuned by adjusting various printing parameters, such as temperature, ranging from 5 to $15^{\\circ}\\mathrm{C}$ Furthermore, Mi et al. reported thermoresponsive NIPAM hydrogels with antimicrobial activity for wound dressing.[116] These positively charged hydrogels were polymerized through reversible addition– fragmentation chain transfer polymerization, and then the antibacterial drug, salicylate, was absorbed within the structure of the hydrogel via electrostatic interaction. The betaine ester bond in the hydrogel is susceptible to hydrolysis, facilitating the release of the antibacterial drug. Experimental results demonstrated that salicylate was efficiently released within $12\\mathrm{h}$ , leading to the complete inhibition of bacteria, specifically E. coli K12 growth. Can et al. also reported PNIPAM hydrogels by encapsulating antibacterial peptides (AMPs).[117] This study efficiently encapsulated the AMP $\\mathrm{G}(\\mathrm{IIKK})3\\mathrm{I}{\\cdot}\\mathrm{N}\\mathrm{H}_{2}$ into NIPAM solution at lower temperatures. Upon increasing the temperature above $33^{\\circ}\\mathrm{C}$ , gelation occurred, leading to rapid drug release.  \n\n![](images/995ba69be09c706f035d0009eebbca5969d55c043587b433558ded6a97a305e2.jpg)  \nFigure 4. a) Schematic illustration of the fabrication of antibacterial 3D printing dressings. b) Biocidal results of $\\mathtt{G}{\\times}2$ , $\\mathsf{C X}2\\cdot\\mathsf{T i O}_{2}$ , and $\\mathsf{C X}2\\cdot\\mathsf{T i O}_{2}$ -PSPH-Cl dressings with shake flask test against S. aureus and E. coli O157:H7. c) Cell viability of GX2 and $_{\\mathsf{G}}{\\mathsf{X}}2{\\mathsf{-}}\\mathsf{T i O}_{2}$ -PSPH-Cl dressings after 4, 12, 24, and $48\\mathsf{h}$ incubation $(^{*}p\\leq0.05$ , $\\because\\xi_{p}\\leq0.01$ , and $\\because\\mu\\ll\\mu\\leq0.001)$ ). d) Representative photographs of wounds treated with gauze, GX2, and $_{\\mathsf{G}}{\\mathsf{X}}2{\\mathsf{-}}\\mathsf{T i O}_{2}$ -PSPH-Cl dressings at 0–16 days. Reproduced with permission.[104] Copyright 2021, Elsevier.  \n\nPEG, a hydrophilic polymer, is employed in making hydrogels for drug delivery, tissue engineering, and antibacterial materials,[118] as PEG polymers possess various advantages, including nontoxic nature, minimal adverse reactions, degradability, and prolonged blood circulation. Liu et al. developed an injectable, self-healing, antibacterial hydrogel by incorporating silver-based liposomes into PEG materials (Figure 5).[119] ${\\mathrm{Ag}}^{+}$ was utilized not only as a crosslinking agent but also as an antibacterial agent, achieving an inhibition rate of $89.7\\%\\pm2.3\\%$ against S. aureus. Additionally, due to its tunable mechanical properties, PEG is often employed to enhance the mechanical properties of hydrogels with poor mechanical strength.[120] Although the thermoresponsive behavior of NIPAM has garnered significant attention, simple NIPAM hydrogels often lack sufficient physical and mechanical properties, limiting further application. Sun et al.  \n\ndiscovered that increasing the molecular weight of PEG in hydrogels enhances their mechanical properties by investigating the properties of different molecular weights of PEG in PNIPAM hydrogels.[121] Poly(ethylene glycol) diacrylate (PEGDA), a derivative of PEG, is utilized to fabricate PEG-based hydrogels, which are suitable carriers for drug delivery and other biomedical applications. More importantly, when exposed to light, PEGDA undergoes rapid photopolymerization to generate a crosslinked network. Therefore, PEGDA has been employed as an ink in light-based 3D printing processes, facilitating the precise fabrication of hydrogels with excellent mechanical properties and biocompatibility.  \n\nPVA has been widely used to prepare high-strength and roughness hydrogels. Hydroxyl groups of PVA facilitate strong intermolecular hydrogen bonding within the polymer network, resulting in enhanced mechanical strength of the hydrogel. Additionally, the abundant hydroxyl groups provide multiple sites for crosslinking with other molecules or polymers, further reinforcing the structure of the hydrogel. Recently, Ni et al. reported on a high-speed underwater hydrogel robot based on PNIPAM and PVA. The incorporation of PVA not only enhances the mechanical properties of PNIPAM hydrogel but also improves its actuation angle.[122] PVA has also found application in resin for light-based 3D printing, where a DLP 3D printer was employed to fabricate PVA materials with tunable mechanical properties and cell compatibility.[123] Overall, synthetic polymers have unique, superior, and exclusive physiochemical properties in contrast with natural polymers. Synthetic polymers are essential materials in light-based 3D printing, enabling the fabrication of complex structures with tunable mechanical properties and biocompatibility, making them versatile for a wide range of applications in fields.  \n\n![](images/44bb3de62f53702ffdc0647c7c383b6d37f70ed3c77881bb96c6249fdf2c653e.jpg)  \nFigure 5. a) Schematic illustration of the formation of liposome hydrogel and ${\\mathsf{A}}{\\mathsf{g}}^{+}$ . b) The formation of an adhesive, liposome-laden, injectable, selfhealing, and antibacterial hydrogel via the Ag-S coordination. c) The hydrogel was locally injected into an osteoporotic fracture and the bone marrow cavity for the release of drugs. Reproduced with permission.[119] Copyright 2019, Springer Nature.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 4. 3D-Printed Hydrogel Composites for Antibacterial Applications  \n\nHydrogels themselves typically lack inherent antibacterial properties. Therefore, hydrogel composites composed of hydrogels combined with metal ions/metal-based inorganic nanomaterials, antibiotics, and antibacterial polymers have been developed to improve their antibacterial efficacy. In addition, the incorporation of polymers or nanoparticles into hydrogel not only improves their mechanical properties, such as strength and stiffness, but also serves as crosslinkers to endow stimuli-responsive behaviors in hydrogels.[124] The following section will mainly focus on light-based 3D-printed hydrogel composites and their antibacterial properties.",
+        "category": " Introduction"
+    },
+    {
+        "id": 15,
+        "chunk": "# 4.1. Inorganic Nanomaterials  \n\nInorganic nanoparticles have attracted tremendous attention in the biomaterial era due to their small size, large surface area,[125] biodegradability,[126] and intrinsic antibacterial properties.[127] AgNPs, as one of the presentative metal-based antibacterial agents, have been widely applied in antibacterial therapy.[128] Various antibacterial mechanisms of AgNPs have been proposed, including disruption of the cell wall and cytoplasmic membrane, denaturation of ribosomes, interruption of adenosine triphosphate production, and production of reactive oxygen species (ROS).[129] Particularly, the positive charge of the AgNPs allows for attachment to the bacterial membrane, creating structural changes in the cell membrane, promoting penetration into the cell, and ultimately leading to cell death.[130] Furthermore, silver ions released from the nanoparticles can interact with thiol groups of proteins in bacteria, disrupting critical cell functions while generating ROS to further damage the bacteria.[131] Integrating AgNPs into 3D printing techniques offers a valuable strategy to enhance the antibacterial properties of 3D-printed hydrogels. These materials serve as a platform for the controlled and sustained release of silver ions, making AgNP composites more suitable for long-term antibacterial therapy. Bergonzi and co-workers innovatively developed 3D-printed hydrogels incorporating AgNPs and alginate, enhancing antimicrobial properties.[132] This novel approach demonstrated heightened effectiveness against pathogens and exhibited promising reductions in the risk of infections and toxicity. Experimental results found that S. aureus and $P_{\\cdot}$ . aeruginosa growth was inhibited by ALG/CNC-AgNPs growth in higher inhibition zones with concentrations of 10 and $100\\upmu\\mathrm{g}\\mathrm{mL}^{-1}$ . DLP technology has been reported to fabricate antimicrobial hydrogel composites by utilizing methacrylate $O$ -acetyl-galactoglucomannan (GGMA) as the photopolymer, AgNPs as the antimicrobial agent, and lignin nanoparticles (LNPs).[133] The LNPs’ joint action of antioxidant activity and UV shielding allows in situ reduction and stabilization of metal-based nanoparticles. It was found that GGMMA/ $\\operatorname{LNP}@\\operatorname{Ag}$ hydrogel exhibited consistent release of ${\\mathrm{Ag}}^{+}$ to the surrounding environment, resulting in a high antibacterial activity on E. coli and S. aureus. Wang et al. reported the DLP 3D printing of antimicrobial hydrogel embedded with AgNPs by using methacrylate-substituted GGMA-based resin. It was found that $10\\%$ GGMA with $0.5\\%$ AgNPs had the highest bactericidal ratio against both E. coli and S. aureus (Figure 6).[34] Furthermore, AgNPs have been conjugated with PAAm/hydroxypropyl methylcellulose (HPMC) and synergized with 3D printing for wound healing.[134] The hydrogel was shown to have sufficient biocompatibility and biosafety on L929 fibroblast cell lines, indicating a low dose of AgNPs leaking from the crosslinked networks. Additionally, the AgNP-PAAm/HPMC hydrogel composite was shown to have high levels of antibacterial effects on E. coli and S. aureus, achieving efficiencies of up to 86. $5\\pm3.2\\%$ and $75.8\\pm2.7\\%$ , respectively. Animal experiments showed that 3D-printed hydrogel composite had increased wound healing in vivo mouse models, leading to faster wound closure with smoother surfaces and reduced scarring.  \n\nCopper also has gained popularity as a natural antibacterial agent. There are various antibacterial mechanisms. One widely accepted mechanism is the generation of ROS in the blasting reaction taking place within phagocytes.[135] As with many metal-based nanoparticles, the leached metal ions from CuNPs are positively charged and prone to interact with the surfaces of Gram-positive and Gram-negative bacteria. Additionally, copper ions from nanoparticles can interact with phosphorus and sulfur-containing biomolecules, such as DNA and proteins, within bacterial cells.[136] These interactions can lead to structural distortions within the bacteria, ultimately resulting in bacterial cell death. Mrialles-Comins and co-workers have developed a series of 3D printable polymerizable ionic liquids for DLP printing. In this study, the researchers prepared PEGDA-based ink with $2\\mathrm{wt\\%}$ copper dinitrate to fabricate materials using a DLP printer.[137] It was found the addition of CuNPs in 3D-printed materials boosts the antibacterial activity against Staphylococcus epidermidis $(98\\%)$ and a significant inhibition zone with ${\\approx}4.5\\mathrm{mm}$ wide was measured. Notably, they proposed a novel approach to synthesize copper materials in situ within the 3Dprinted films, simplifying the fabrication of antibacterial materials through light-assisted 3D printing.  \n\nZinc oxide nanoparticles (ZnO NPs), another metal oxide nanoparticle, have also been reported to serve as a 3D-printed antibacterial agent. Mandler and co-workers developed a 3D printable resin consisting of PEGDA and $z\\mathrm{nO}$ NPs to fabricate materials with similar mechanical properties to human cartilage.[138] In this study, the $z\\mathrm{nO}$ NPs embedding matrix showed potent antibacterial activity against E. coli and S. aureus. The amount of ZnO NPs embedded in the matrix has only a minor effect on the mechanical properties but achieves strong antibacterial properties in the case of $1.5\\mathrm{wt\\%}$ ZnO NPs (Figure 7). Titanium dioxide nanoparticles have a large spectrum of activity against microorganisms, including Gram-negative and Grampositive bacteria and fungi. Titania–polymer nanocomposites are environmentally friendly and exert a noncontact biocidal action.[139] Cristache and co-workers reported that the $\\mathrm{TiO}_{2}$ was subjected to DLP 3D printing for denture manufacturing, exhibiting superior antibacterial efficacy. The prepared PMMA– $\\cdot\\mathrm{TiO}_{2}$ nanocomposite, containing $0.4\\%$ , $1\\%$ , and $2.5\\%$ $\\mathrm{TiO}_{2}$ nanoparticles, inhibited the growth of the Candida scotti strain under standard conditions.[140]  \n\n![](images/1e49bbdb799b9b50e6c217ea11bffc6b874ebe9e5c9f7d535b03355af6a54bd2.jpg)  \nFigure 6. a) The design strategy for the sustainable resin and antimicrobial hydrogel involves the following steps: i) Preparation of laccasepolymerized lignin in alkaline aqueous media from well-defined lignin fractions. ii) Fabrication of lignin nanoparticles. iii) In situ reduction of ${\\mathsf{A}}{\\mathsf{g}}^{+}$ on the surface of alkali-resistant lignin nanoparticles. iv) Scheme of the molecular structure of photo crosslinkable resin. v) Scheme of the molecular structure of photo crosslinkable hydrogel. b) Fabrication of 3D objects by projection lithography. c) In vitro release profiles of ${\\sf A g}^{+}$ from hydrogels. d) Viability assays of E. coli and S. aureus on hydrogels. Reproduced with permission.[34] Copyright 2022, Royal Society of Chemistry.  \n\nGold nanoparticles (AuNPs) exhibit adjustable optical and electronic features, making them indispensable in various applications, including photovoltaics, sensors, diagnostic imaging, and drug delivery.[141] The critical property of AuNPs lies in their robust photothermal effects, enabling them to convert absorbed near-infrared (NIR) efficiently light energy into heat. This feature positions AuNPs as a promising antibacterial material for ablating bacteria.[142] For instance, when exposed to NIR light $(808\\mathrm{nm})$ for $10\\mathrm{min}$ , the temperature of a hybrid comprising AuNPs and PEG increased significantly from 23 to $55^{\\circ}\\mathrm{C}$ .[143] The in vivo photothermal antibacterial properties were initially validated using a subcutaneous implantation animal model. Moreover, hydrogel incorporated with AuNPs offers new options for fabricating next-generation antibacterial materials.  \n\nBatool et al. have synthesized an AuNP-doped hydrogel for antimicrobial and wound healing potential.[144] The hydrogel nanoparticle composite was shown to be effective against Bacillus simplex, Bacillus subtilis, P. aeruginosa, E. coli, and S. aureus, with the highest zone of inhibition for E. coli, B. subtilis, and P. aeruginosa at 18, 17, and $16\\mathrm{mm}$ , respectively. Results showed that wound-healing mouse models had $90\\%$ wound closure in treatment groups with AuNPs compared to the control groups. Furthermore, light-assisted 3D printing technology has the potential in creating hydrogel composites containing AuNPs for antibacterial applications. To date, only a few articles have reported on the application of AuNPs in light-based 3D-printed materials for the photothermal treatment of bacteria. This limited use is primarily due to the significant amount of nanoparticles required in 3D printing processes, and AuNPs are relatively more expensive compared to other types of nanoparticles.  \n\n![](images/896face3ef413d1f5791cc57be9b586d55de2aba86269a53537b1c7bef0f7250.jpg)  \nFigure 7. a) Schematics depict DLP printed PEGDA hydrogels containing ZnO NPs for antibacterial application; b) SEM images of DLP printed samples containing $1.5\\mathrm{wt}\\%$ ZnO NPs; and c) E. coli and S. aureus viability percentage for different $Z n O N P\\mathrm{wt\\%}$ in UV-cured samples. Reproduced with permission.[138] Copyright 2023, MDPI.  \n\nCarbon-based nanoparticles include graphene, carbon nanotubes, and carbon dots, which have been used for diagnostics, biosensing, imaging, and tissue engineering, owing to their unique properties such as high surface area and electrical conductivity.[145] Another benefit of carbon-based nanoparticles is their biocompatibility. Compared to metal-based nanoparticles such as silver or copper, which tend to show cytotoxic effects,[146] carbon-based nanoparticles generally show lower toxicity.[147] Furthermore, carbon-based materials have emerged as a critical component in developing antibacterial applications. The mechanisms of carbon nanoparticles’ antibacterial action are diverse, primarily disrupting bacterial cell walls through interactions that induce cell death. The high surface area of the carbon-based nanoparticles allows for efficient interactions with bacteria, which inhibit or neutralize bacteria.[148] Furthermore, carbon nanoparticles possess photothermal capabilities under NIR light irradiation, enabling antibacterial therapy.[149] Integrating carbon nanoparticles into 3D printing techniques offers a valuable approach to creating composites with enhanced benefits. Incorporating carbon nanoparticles can notably boost the mechanical properties of 3D-printed hydrogels. For instance, graphene-reinforced hydrogels demonstrate exceptional tensile strength, expanding the potential for this technology to be applied in medical scenarios requiring robust hydrogel strength.[150] Carbon materials additionally offer photothermal or electrical properties when incorporated into 3D-printed hydrogels. 3D-printed composites containing carbon nanoparticles hold great potential for antibacterial therapy. Edaugal et al. operated DLP printing to fabricate polymer-based GO nanocomposites as efficient antimicrobial materials (Figure 8).[33] They employed the noncovalent $\\pi{-}\\pi$ interactions between poly(N-vinyl carbazole) carbazole groups and GO to stabilize the dispersion of the nanofiller within the resin. The nanocomposites’ antibacterial efficacy was assessed against Gram-negative E. coli and Gram-positive S. aureus. The outcomes of this research exhibit the straightforward production of nanocomposites with exceptional antibacterial attributes using the DLP technique. These findings provide a basis for leveraging DLP as an efficient and economical manufacturing method for generating advanced antimicrobial materials, which could help reduce the incidence of bacterial-related infections in biomedical devices, thus mitigating postoperative complications.  \n\nMetal–organic frameworks (MOFs), assembled by inorganic clusters and organic ligands through strong coordination bonds, exhibit high porosity, excellent stability, tunability, and advanced bio-related features. These properties make MOFs attractive in bioimaging, drug delivery, biocatalysis, biosensing, and antibacterial applications.[151] MOFs have emerged as an ideal material for diverse antibacterial applications due to their advantageous functions, including controlled or stimulated decomposition, strong interaction with bacterial membranes, formation of ROS under irradiation, and the capability for high loading and controlled release of other antibacterial agents.[152] Integrating MOFs into 3D printing is an excellent way to improve the antibacterial ability of materials. For example, we have employed the SLA printing technique to PEGDA materials containing 2D porphyrinic MOFs.[153] When exposed to light irradiation, 2D porphyrinic MOFs can transform oxygen into singlet oxygen, killing bacteria by inducing oxidative damage to cellular lipids, proteins, and DNA, disrupting essential cellular processes and leading to cell death. 3D-printed materials have remarkable efficacy against both Gram-positive and Gram-negative bacteria at $98\\%$ and $93\\%$ , respectively, under an LED light $(\\lambda_{\\operatorname*{max}}=565\\mathrm{nm}$ , $10\\mathrm{mW}\\mathrm{cm}^{-2},$ ).  \n\n![](images/45e7514bc298798c4d6e006eed66736495eeefd59c52496bff21c6ac0cf9a1a5.jpg)  \nwww.small-science-journal.com   \nFigure 8. a) DLP printing of polymer-based GO nanocomposite as an efficient antibacterial coating for surgical implants; b) DLP printed gyroid structures with 0.1 and $0.5\\mathrm{wt\\%}$ nanocomposites; Quantitative culture of c) E. coli UTI and (b) S. aureus at $24\\ h$ postinoculation onto DLP printed materials. Reproduced with permission.[33] Copyright 2023, Springer Nature.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 4.2. Antibiotics  \n\nAntibiotics, since their inception with Alexander Fleming’s discovery of penicillin in 1928, have significantly reduced mortality from bacterial diseases.[154] There are different types of antibiotics, including penicillin, cephalosporins, quinolones, tetracyclines, macrolides, and aminoglycosides. Each antibiotic targets specific bacterial strains, necessitating tailored selection for optimal clinical efficacy.[155] This personalized approach ensures effective treatment while mitigating antibiotic resistance. However, the indiscriminate use of antibiotics has led to antibiotic resistance, where bacteria can rapidly develop mechanisms to bypass the antibiotics’ mode of action. Developing hydrogel composites, which combine antibiotics, is an excellent way to solve this issue.[5] Leveraging the high-water content and customizable nature of hydrogels, antibiotics can be precisely delivered in a controlled manner. The goal is to selectively administer antibiotics, minimizing bacterial exposure and localized to specific areas of concern.[5] Martinez-Perez and co-workers have employed 3D printing technology, utilizing GelMA and PLGA hydrogel as a platform, to develop a delivery system for rifampicin and vancomycin for antibiotic-resistant bacteria.[156] The amount of drug release and associated parameters were found to be dependent on the molecular weight of PLGA, with a lower molecular weight of PLGA associated with faster drug release. Erkus et al. used DLP printing techniques to manufacture a microneedle platform for transdermal drug delivery of amoxicillin (Figure 9).[157] These 3D-printed microneedles exhibited rapid release of amoxicillin within the initial $6\\mathrm{{h}}$ . Moreover, in vitro assessment revealed the effective antibacterial activity of the microneedles against both E. coli and S. aureus, with substantial zones of inhibition measuring 22 and $25\\mathrm{mm}$ respectively. This innovative approach demonstrates the potential for efficient transdermal delivery of antibiotics and effective treatment of bacterial infections.  \n\n![](images/aa517ddb911a39940b9cdbd260d8c30b6db1940d941b73f405846940eb1646e6.jpg)  \nFigure 9. a) Schematic illustration of the design and DLP 3D printing of GelMA microneedles containing amoxicillin; b) drug release profile from the amoxicillin-loaded GelMA microneedles; and c) antibacterial activities of the amoxicillin-loaded GelMA microneedles: 1) GelMA microneedles and 2) AMX-loaded GelMA microneedles. Reproduced with permission.[157] Copyright 2023, Elsevier.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 4.3. Cationic Polymer-Based Antibacterial Materials  \n\nIn the last decades, there has been a growing interest in developing cationic polymers containing quaternary, phosphonium, and pyridinium cations as antimicrobials because of their low cost, broad spectrum, and antibacterial activity.[158] In general, cationic polymers act antibacterial effects upon the negatively charged membrane of the bacteria through electrostatic interaction, followed by insertion of their hydrophobic segments into the lipid domains to kill the bacteria.[159] However, these cationic polymers also inevitably damage human cell membranes during antimicrobial therapy, causing toxicity.[160] Developing cationic polymer-based materials with low toxicity is an urgent priority. Ting et al. developed a bilayer asymmetric hydrogel to replicate the skin’s epidermis and dermis gradient structure, utilizing a combination of electrostatic spinning and 3D printing techniques. The hydrogel exhibited surface hydrophilicity, hydrophobicity, porosity, mechanical strength, and antibacterial capabilities. The inner layer, composed of sodium alginate/ PVA/chitosan quaternary ammonium salt, demonstrated significant antibacterial activity against S. aureus, with an inhibition zone measuring 1.61 \u0004 0.35 cm.[161]  \n\nIn addition, AMPs, one of the antibacterial cationic polymers, exhibit sensitivity toward a wide range of bacteria, fungi, and viruses. Like cationic polymers and some metal nanoparticles, AMPs can bind to bacterial cell membranes, inducing the formation of pores on the surface of membranes, ultimately leading to bacterial death. For example, Maleki and co-workers printed hybrid scaffolds containing AMPs for repairing bone defects and antibacterial.[162] Experiments conclusively confirmed that the 3D-printed material exhibited a significant zone of bacterial inhibition against Gram-positive bacteria, which was significantly better than the antimicrobial effect against Gram-negative bacteria. This is because of the presence of lipopolysaccharides in the outer membrane of Gram-negative bacteria, which functions as a protective shield by impeding the access of CM-RGD to the inner cytoplasmic membrane.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# 5. Conclusion  \n\nLight-assisted 3D printing is a revolutionary technique that provides the possibility of fabricating advanced antibacterial hydrogels for more diverse and intricate clinical scenarios. There are several advantages, including a wide selection of photopolymer materials, the creation of highly precise, customized antibacterial materials crafted to meet specific applications or requirements, as well as the ability to exert precise control over the distribution and release of antibacterial agents within 3D-printed hydrogels. In this review, we summarized the unique properties, antibacterial ability, and potential applications of natural and synthetic hydrogels fabricated by light-assisted 3D printing. Moreover, we discussed current approaches to improve and prolong the antimicrobial efficacy of 3D-printed hydrogels through the combination of potent antibacterial agents. The objective of our review is to provide researchers with an up-to-date understanding of the advancements in light-assisted 3D-printed hydrogels.  \n\nIt is noteworthy that there are issues in both light-assisted 3D printing and antibacterial hydrogels that require attention in the future. 1) The main light source of light-assisted 3D printing (such as SLA and DLP) is UV light/beams, which inevitably causes damage to living cells; 2) A standard 3D printing antibacterial resin entails a complex formulation, which is composed of photoinitiators, monomers/crosslinkers, cells, and other functional compounds. The development of ideal resins that balance optimal biocompatibility and potent antibacterial properties remains a critical pursuit; and 3) The introduction of lightassisted 3D printing has not effectively addressed the issues posed by the weak mechanical performance and fragility of hydrogels, thus restricting their specific applications, like bone implants and vascular tissue engineering.  \n\nInnovation in 3D printing techniques and hydrogel formulations is expected to tackle current obstacles, broadening scenarios of antibacterial materials. For instance, researchers have developed a novel visible light-assisted 3D printer, which is able to mitigate the potential side effects of UV light/beams in biomedicine. Furthermore, incorporating artificial intelligence and machine learning algorithms into the field of 3D-printed hydrogels can revolutionize the printing parameters and formulation design. Artificial intelligence and machine learning can identify intricate patterns and relationships, facilitating the optimization of 3D printing parameters for the fabrication of antibacterial hydrogels. This data-driven approach accelerates the process of developing and designing new resins while maintaining precision and efficacy. Artificial intelligence and machine learning also predict hydrogel behaviors, aiding in customizing formulations tailored to specific applications. Therefore, collaborative interdisciplinary initiatives involving materials scientists, bioengineers, computer scientists, and healthcare practitioners will propel advancements in this field and address the multifaceted challenges associated with bacterial infections.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 19,
+        "chunk": "# Acknowledgements  \n\nL.Z. and N.K.A.N. contributed equally to this work. The authors would like to acknowledge the support from the National Health and Medical Research Council (grant nos. APP1196850, APP1197373, and 2019056), Queensland-Chinese Academy of Sciences (Q-CAS) Collaborative Science Fund (grant no. QCAS2022016), UQ Amplify Women’s Academic Research Equity (UQAWARE), UQ Foundation of Excellence Research Award (UQFERA), and Advance Queensland Women’s Research Assistance Program (AQWRAP), the Queensland node of the  \n\nNCRIS-enabled Australian National Fabrication Facility (ANFF), and the Centre for Microscopy and Microanalysis (CMM).  \n\nOpen access publishing facilitated by The University of Queensland, as part of the Wiley - The University of Queensland agreement via the Council of Australian University Librarians.",
+        "category": " Acknowledgements"
+    },
+    {
+        "id": 20,
+        "chunk": "# Conflict of Interest  \n\nThe authors declare no conflict of interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 21,
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Technol. 2023, 135, 199.  \n\n![](images/342fab2699b75d91cc4db6d5a925c40b9515b8c47f65b7af0efbc572a9cb10b1.jpg)  \n\nLiwen Zhang is a postdoctoral fellow at the Australian Institute for Bioengineering and Nanotechnology (AIBN), University of Queensland (UQ), Australia. He obtained his Ph.D. degree in 2022 from the Cluster for Advanced Macromolecular Design at the University of New South Wales (UNSW), Australia. His research interests span nanotechnology, 3/4D printing, antibacterial polymers, and soft robotics.  \n\n![](images/c76b7130cdcaf26894052483393074f6e88a9a238adf0e40180ee9a9c10359c8.jpg)  \n\nRuirui Qiao is a group leader and NHMRC Emerging Leadership Fellow in Australian Institute for Bioengineering and Nanotechnology (AIBN), University of Queensland (UQ). She earned her Ph.D. from the Chinese Academy of Sciences in 2014, along with an M.Sc. in 2007 and a B.Sc. in 2005 from Peking University, China. Leading a research group at AIBN, UQ, she is committed to advancing the field of functional polymer/inorganic nanohybrids for biomedical applications, including disease diagnosis, drug/ gene delivery, tissue engineering, antibacterial solutions, and soft robotics.  \n\n![](images/3df55a8ba4a41bcdd8839f2505474b97d0a7dba278b8c90093c45fb41b78991a.jpg)  \n\nThomas P. Davis is the Chair Professor of Precision Medicine at the AIBN at the University of Queensland. He is a NHMRC Leadership Investigator and his research focuses on the application of polymer science and nanotechnology to therapeutic applications.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Formation Theory and Printability of Photocurable Hydrogel for 3D Bioprinting  \n\nChao-Fan He, Yuan Sun, Nian Liu, Kang Yu, Ying Qian, and Yong He\\*  \n\nBio-ink has gradually transited from ionic-crosslinking to photocrosslinking due to photocurable bio-hydrogel having good formability and biocompatibility. It is very important to understand and quantify the crosslinking process of photocurable hydrogels, otherwise, bioprinting cannot be standardized and scalable. However, there are few studies on hydrogel formation process and its photocrosslinking behavior which cannot be accurately predicted. Herein, the photoinitiated radical polymerized bio-hydrogels are taken as an example to establish the formation theory. Three typical crosslinking reactions are first distinguished. It is further proposed that not all double-bonds consumed during crosslinking contributeequally to polymerization. Then the concept of effective double-bond conversion (EDBC) is elicited. Deriving from EDBC, several important formation indices are defined. According to theory, it is predicted that slow crosslinking can improve the crosslinking degree. Furthermore, based on the slow crosslinking effect, a new strategy of projectionbased 3D printing (PBP) is proposed, which significantly improved printing quality and efficiency. Overall, this work will fill the gap in hydrogel’s formation theory, making it possible to accurately quantify the formation process.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1. Introduction  \n\nHydrogel is a kind of polymer with 3D hydrophilic network. Depending on the properties of the monomer, crosslinking in hydrogels can occur either chemically or physically.[1] Among them, photocurable hydrogels, which are convenient for time and space regulation, have been widely used in biomedicine, such as tissue engineering scaffolds,[2] drug sustained-release carriers,[3] and wound repair dressing.[4]  \n\nPhotocurable hydrogels are usually synthesized by chemical reaction of biomaterials with methacrylic anhydride or acryloyl chloride to introduce “MA” or “DA” groups, such as gelatin methacryloyl (GelMA),[5] hyaluronic acid metha­ cryloyl (HAMA),[6] chitosan metha­ cryloyl (CSMA),[7] dextran methacryloyl (DexMA),[8] poly(ethylene glycol) diacrylate (PEGDA),[9] and polyether F127 diacrylate (F127DA).[10] These photosensitive groups usually have unsaturated double bonds, which polymerize with each other under light exposure of a certain wavelength and initiator to form the crosslinking network. The shape and area of the cured material can be adjusted by controlling the exposure parameters so that 3D controllable formation can be easily realized.  \n\nUnderstanding and quantifying the polymerization process of photocurable hydrogels is very important for the scale and standardization of bioprinting. The research on traditional polymers has lasted for nearly a hundred years,[11] and its crosslinking process has been very clear. However, as a new biomaterial, hydrogels have many different properties from traditional polymers, which makes the formation theory of traditional polymer not applicable to hydrogels. First, different from polymerization of small molecules $(10-10^{3}\\mathrm{{Da})}$ into macromolecules, the monomers of hydrogels are already macromolecules( $10^{5}–10^{6}$ Da). Second, the degree of functionalization (DoF) of traditional polymers is very high, up to $70\\%-90\\%$ .[12] However, most of the functional groups in hydrogels maintain hydrophilicity and biocompatibility. Only a small part of the functional groups is used for crosslinking, so the DoF is usually $<20\\%$ . Third, the polymerization process of small molecules is usually “head to tail” to form 1D linear structural units. The crosslinking process of hydrogels is that the photo-sensitive groups in side chains “hand in hand” form 2D network structural units. Finally, traditional small molecules are dominated by bulk polymerization, which can be viewed as a concentration of $100\\%$ . Hydrogels are mostly solution polymerization and the concentration is usually $<10\\%$ . These characteristics make the hydrogel poor printability and it is difficult to evaluate the formation state (Figure 1A).  \n\n![](images/832c4746f6ff8cf1454c96d167c513c670c5192478b9a1074fe890de54f4a962.jpg)  \nFigure 1.  A) The difference of radical polymerization process between hydrogel and traditional polymer; B) Evaluation method of hydrogel formation state.  \n\nAt present, there were some studies on the printability of hydrogels, and the qualitative analysis of hydrogel's formation process is relatively clear.[13] However, due to the complexity of the crosslinking process, there was still a lack of quantitative evaluation methods. Few studies had evaluated hydrogels’ formation state,[14] and the definition of formation state was still vague. Some current studies used the concentration of reaction substrate to describe the “crosslinking degree”,[15] which ignored the effect of different crosslinking conditions. There were also some studies to describe the “crosslinking degree”  \n\nby the conversion ratio of functional groups, such as double bond conversion (DBC),[16] which was accurate in describing traditional polymers, but not suitable for hydrogels. At present, the evaluation of hydrogel’s formation state was mostly based on the reverse deduction of application performance after crosslinking.[11a,b,17] This indirect method would cause large errors due to different testing methods.  \n\nIt should be noted that the formation state is an external independent parameter, which is only related to material properties and crosslinking conditions. The application performance refers to the corresponding output result under the action of certain external inputs. For example, mechanical properties refer to the strain under tensile or compressive stress, swelling properties refer to changes in volume under the action of osmotic pressure, and degradation properties refer to the destruction of materials under chemical or biological factors. Different formation states of the same material directly determine various application properties after crosslinking. Therefore, it is necessary to propose a forwarding reasoning method to evaluate the formation state of hydrogels more comprehensively and accurately.  \n\nThe factors affecting hydrogel's formation state were summarized into two aspects: original material properties and conditions during crosslinking. Material properties included molecular structure, DoF, and concentration. Crosslinking conditions included temperature, initiation rate, and crosslinking time. Based on this, taking the commonly used photocurable hydrogel GelMA[18] and photoactivatable radical initiator lithium pheny (2,4,6-trimethylbenzoyl) phosphinate (LAP)[19] as an example, a detailed definition and quantitative evaluation system of formation state were proposed to expound the formation process of photocurable radical polymerized hydrogels (Figure 1B).  \n\nFirst, we analyzed the formation characteristics of hydrogels from the macro and micro perspectives (Figure2A). Next, through the analysis of crosslinking reaction, we found that different polymerization reactions have different contributions to hydrogel formation. The formation theory based on contribution degree and the corresponding formation indices were proposed subsequently (Figure 2B). Furthermore, slow crosslinking effect and gel point effect were predicted (Figure 2C). Finally, a new (projection-based  3D  printing)PBP strategy was proposed according to the formation theory, namely fast crosslinking printing and slow crosslinking post-processing (F–S printing). Compared with traditional printing methods, F–S printing has significantly improved in efficiency, resolution, mechanical strength, and biocompatibility (Figure 2D).",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2. Double Bond Conversion (DBC) and Effective Double Bond Conversion (EDBC) of Hydrogel Crosslinking Process  \n\nCrosslinking refers to the process in which linear or branched molecular chains are connected by crosslinking bonds to form a network or bulk polymer. Hydrogels can be crosslinked by various methods, which are mainly divided into four types: radical polymerization,[20] cationic polymerization,[21] anionic polymerization,[22] and metal catalyst polymerization.[23] Among them, radical polymerization is a commonly used method in 3D printing.[24] The clear majority of radical polymerization uses ethylenic monomers containing unsaturated double bonds as raw materials. By destroying the double bonds in the monomer molecules, repeated addition reactions are carried out between the molecules to form macromolecules. The most common methods of generating radicals are to decompose the initiator by heating[25] or ultraviolet (UV) radiation.[26]  \n\nDuring the crosslinking process, unsaturated double bonds are destroyed by radical to form crosslinked bonds, thereby crosslinking with each other to form polymers. Therefore, the ratio of double bonds consumed is directly related to the degree of crosslinking, which can be used as an ideal parameter to describe the formation state. Based on this, the conventional evaluation method is to measure the content of double bonds before and after crosslinking, and then calculate the double bond conversion (DBC) to evaluate formation state. The mono­mer structure of traditional small-molecule (such as ethylene) is simple and the crosslinking reaction is very thorough.[27] It is reasonable to use DBC to describe the formation state. However, for hydrogels with large monomer molecular weight and low DoF, simply using DBC to represent the formation state will produce considerable errors. This is because the converted double bonds do not contribute equally to the formation of hydrogels during the crosslinking. In order to measure the contribution of converted double bonds to formation, the concept of effective double bond conversion (EDBC) was proposed. The EDBC represents the ratio of double bonds converted to crosslinked bonds. The higher the EDBC, the greater the contribution of converted double bonds to polymerization.  \n\nThe photo-initiated radical polymerization is mainly divided into two processes: initiation and polymerization.[28] The initiation reaction means that the initiator decomposes into primary radical under the exposure of UV light, and primary radical with unpaired electron captures an electron of the carbon–carbon double bond in the monomer to generate monomer radical. The monomer radical faces three different polymerization reactions. The first is the propagation reaction, in which monomer radical breaks the double bonds in another monomer again. The propagation reaction has the highest EDBC. Assuming that n monomers undergo propagation reactions, $n$ double bonds are broken and $n{-}1$ crosslinked bonds are generated. Therefore, the EDBC is $(n{-}1)/n$ . The second is the termination reaction, that is, monomer radical pairs with another monomer radical or chain radical to form inert saturated molecules. Termination reactions are usually divided into coupling termination and disproportionation termination. Disproportionation termination is usually related to oxygen inhibition and is not considered here. If there are $n$ monomers undergo termination reactions, n double bonds are broken and $\\scriptscriptstyle m2$ crosslinked bonds are generated. Therefore, the EDBC is 1⁄2. In addition, as a special case of termination reaction, which is called blocking reaction. The blocking reaction is the polymerization of monomer radical with primary radical. If there are $n$ monomers that undergo blocking reaction, the EDBC is 0. Increasing of blocking reaction significantly reduces the EDBC. The proportions of three polymerization reactions directly determine EDBC. However, since the double bonds in three reactions are all consumed, DBC cannot distinguish these three types of reactions. Therefore, EDBC characterizes the formation state better (Figure 3A). DBC could be calculated from double bond content before and after crosslinking. Double bond content could be measured by nuclear magnetic resonance (NMR),[29] Fourier transform infrared spectroscopy (FTIR)[30] and RAMAN spectroscopy.[16c] However, there is no direct method to measure EDBC. Therefore, we proposed a method to derive EDBC by combining characteristic element content with DBC. Taking LAP and GelMA as an example, the decomposition of LAP produces two kinds of primary radical, one of which contains phosphorus element (P element) and lithium element (Li element).[19] The other type does not contain these two elements. GelMA also does not contain these two elements. These two radicals equally participate in the crosslinking reaction. Therefore, EDBC can be comprehensively characterized by P element content combined with DBC. Specifically, the results after crosslinking can be divided into four cases. The first case is high DBC and low element content. In this case, the formation state is that most of the monomers have not been initiated, so the EDBC is low. The second case is low DBC and high element content, which is almost non-existent in single-component crosslinking. The third case is high DBC and high element content. At this time, the formation state is that most of the monomers are initiated, but the polymerization reaction is mainly the termination and blocking reaction, so the EDBC is low. The fourth case is high DBC and low element content. In this case, most of the monomers have undergone the propagation reaction, so the EDBC is high (Figure 3B).  \n\n![](images/5a972c487deb339a6bc62599c0dfda6cd781f2551bb89da1dbf358979978c41f.jpg)  \nFigure 2.  Roadmap of formation theory. A) Analysis of hydrogel formation characteristics; B) Formation theory based on crosslinking contribution and corresponding formation indices; C) Inference of formation theory: slow crosslinking effect and gel point effect; D) F–S printing strategy guided by formation theory and its advantages.  \n\n![](images/e23074444e9384ee7c6c351df21d6850ce178bab1487e34e7586fb569bf0355c.jpg)  \nFigure 3.  A) DBC and EDBC of three reactions in radical polymerization; B) Relationship between DBC and EDBC.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# 3. Definition of Formation State  \n\nThe monomer of traditional small-molecular polymer has small molecular weight and high functionalization degree, so the polymerization reaction is mainly based on propagation reaction, and the proportion of termination and blocking reaction is very small. Therefore, it can be seen that all the double bonds consumed in polymerization are converted into covalent crosslinked bonds with the same contribution to the formation (Figure 4A). However, the proportion of propagation reaction in the hydrogel formation is not high, but the termination and blocking reaction account for a considerable proportion.  \n\nTherefore, it is not accurate and comprehensive to use DBC to describe the formation state of hydrogels.  \n\nBased on the concept of EDBC, the hydrogel formation state is divided into four concepts for accurate quantification. They are: average crosslinking steps (ACS), degree of crosslinking (DGC), density of crosslinking (DSC), and density of molecular network (DMN). These four parameters describe hydrogels’ formation state from different perspectives.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# 3.1. Average Crosslinking Steps (ACS)  \n\nThe average crosslinking steps refers to the average number of chain reaction steps of hydrogel monomer in a statistical sense, which is used to characterize the molecular weight of crosslinked hydrogel. ACS is a dimensionless number directly related to crosslinking, which can help us understand the crosslinking process of hydrogels.[31] The larger the ACS, the more monomers undergo propagation reactions during the crosslinking process.  \n\n![](images/64da753604b2de62235ab2447fc85b9b8b4a302359063423acef06864fa16b81.jpg)  \nFigure 4.  Definition of formation state.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 3.2. Degree of Crosslinking (DGC)  \n\nThe degree of crosslinking refers to the completion degree of crosslinking reaction, which ranges from $0\\%$ to $100\\%$ . The closer the DGC is to $100\\%$ , the closer the crosslinking reaction is to the upper limit. The ACS of small molecules can usually reach $10^{3}–10^{5}$ ,[32] which also means that the reaction is very thorough, and almost all of the crosslinkable bonds are converted into crosslinked bonds. The DGC is very close to $100\\%$ . However, the ACS of hydrogels is usually only $10{-}10^{2}$ (Figure 8Fii), so a considerable part of the crosslinkable bonds is not converted into crosslinked bonds, and the DGC is usually ${<90\\%}$ (Figure  8Fii). Therefore, it is necessary to propose the concept of DGC to describe crosslinking limits accurately.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 3.3. Density of Crosslinking (DSC)  \n\nThe density of crosslinking is the proportion of crosslinked bonds in total binding bonds, which ranges from $0\\%$ to $100\\%$ . For the same material, the larger the DSC, the more crosslinked bonds per unit volume, the denser the molecular network formed, and the higher the corresponding application performance.[33] DSC can be used to compare the formability of the same material under different crosslinking conditions",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 3.4. Density of Molecular Network (DMN)  \n\nFurther, to establish a unified evaluation standard for different hydrogels’ formation states, we proposed the concept of density of molecular network. DSC describes the proportion of crosslinking bonds, which can characterize the density of the molecular network after crosslinking of the same hydrogel. However, different hydrogels have different sized structural units.[31] When the DSC is equal, the smaller the structural unit and the higher the concentration of hydrogels, the denser the molecular network. Therefore, DMN can be used to uniformly evaluate the formation state of different hydrogels, which can help us measure the printability of bioinks[34] (Figure 4B).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 4. Quantification of Formation State",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 4.1. Measurement and Calculation of Average Crosslinking Steps (ACS)  \n\nACS refers to the number of crosslinking reaction steps that can be initiated by one primary radical statistically. It should be noted that most of the crosslinking reactions end in combination termination. That is, most of the crosslinked molecules have two initiator residues,[31,33] so the calculation formula of ACS is as follows:  \n\n$$\n\\mathsf{A C S}=2\\cdot\\frac{N_{\\mathrm{(DB)}}}{N_{\\mathrm{(ini-res)}}}-1\n$$  \n\nWhere $N_{(\\mathrm{DB)}}$ is the number of double bonds in a crosslinked chain; $N_{\\mathrm{(ini-res)}}$ is the number of initiator residues in a crosslinked chain.  \n\n$$\nN_{_\\mathrm{(DB)}}=\\frac{x\\cdot\\mathrm{DBC}\\cdot\\mathrm{DoF}}{M_{\\mathrm{ave}}}{\\times}10^{-3}\\cdot N_{\\mathrm{A}}\n$$  \n\nWhere $x\\ (\\mathrm{mg})$ is the mass of GelMA after curing; DBC is double bond conversion (Equation  8); DoF is the degree of functionalization;[17a] $M_{\\mathrm{ave}}$ is the average molecular weight of  \n\n![](images/ecbb07b18e604bd4ec107953f7960535e5db04821ea88597ce3edbfebd5f5e62.jpg)  \nFigure 5.  Measurement and calculation method of ACS, DGC, DSC A) and DMN B).  \n\nthe basic unit in GelMA, which is amino acid; $N_{\\mathrm{A}}$ is Avogadro’s constant.  \n\nDoF can be calculated as follows:  \n\n$$\n\\mathrm{DoF}=P_{\\left(-\\mathrm{NH2}\\right)}\\cdot P_{\\left(\\mathrm{MA}\\right)}\n$$  \n\nWhere $P_{\\mathrm{(-NH}2)}$ is the ratio of amino acids containing amino groups in $R$ group in gelatin (Figure  8D); $P_{\\mathrm{(MA)}}$ is the substitution rate of MA group (Table 1; Figure  S1, Supporting Information).  \n\n$M_{\\mathrm{ave}}$ can be calculated by the following formula:  \n\n$$\nM_{\\mathrm{ave}}=\\sum_{\\mathrm{af}=1}^{\\mathrm{m}}P_{\\mathrm{af}}\\cdot M_{\\mathrm{af}}+\\sum_{\\mathrm{ac}=1}^{\\mathrm{n}}P_{\\mathrm{ac}}\\cdot\\left(M_{\\mathrm{ac}}+{\\frac{M_{\\mathrm{LAP}}}{2}}\\cdot P_{\\mathrm{(MA)}}\\right)\n$$  \n\nWhere $P_{\\mathrm{af}}$ and $M_{\\mathrm{af}}$ are the proportion and molecular weight of amino acids without amino group in $R$ group, respectively; $P_{\\mathrm{{ac}}}$ and $M_{\\mathrm{ac}}$ are the proportion and molecular weight of amino acids with amino group in $R$ group, respectively; $M_{\\mathrm{LAP}}$ is the molecular weight of photoinitiator LAP. Relevant data are shown in Figure 8D and Tables S1 and S2 (Supporting Information).  \n\nHowever, only one of the two kinds of primary radical generated after the decomposition of LAP contains P element and Li element. Under the assumption that the activities of two kinds of primary radicals are equal,[35] the total initiator residue content should be twice the element content. Li element exists in the form of ions and is easily interfered by other cations, so the P element is used as the judgment standard. Therefore, the number of initiator residues can be calculated as follows:  \n\n$$\nN_{(\\mathrm{ini-res})}=\\frac{2V\\cdot\\rho_{\\mathrm{(P)}}}{M_{\\mathrm{P}}}\\times10^{-9}\\cdot N_{\\mathrm{A}}\n$$  \n\nWhere $M_{\\mathrm{P}}$ is the molecular weight of $\\mathrm{\\DeltaP}$ element, V (mL) is the volume of solution after nitric acid digestion and dilution; $\\rho_{\\mathrm{(P)}}\\ \\left(\\upmu\\mathrm{g/L}\\right)$ is the $\\mathrm{\\DeltaP}$ element concentration measured using inductively coupled plasma mass spectrometry (ICP-MS) (Figure 8E).  \n\nFurther, ACS is calculated as follows (Figure 5A):  \n\nTable 1.  Abbreviations of different types of GelMA.   \n\n\n<html><body><table><tr><td>Abbreviation</td><td>GM30</td><td>GM60</td><td>GM90</td></tr><tr><td>Product model</td><td>EFL-GM-30</td><td>EFL-GM-60</td><td>EFL-GM-90</td></tr><tr><td>Degree of substitution</td><td>29.6% (-NH2)</td><td>61.2% (-NH2)</td><td>93.4% (-NH)</td></tr></table></body></html>  \n\n$$\n{\\mathrm{ACS}}=2\\cdot{\\frac{\\frac{\\boldsymbol{x}\\cdot{\\mathrm{DBC}}\\cdot{\\mathrm{DoF}}}{M_{\\mathrm{ave}}}\\times10^{-3}\\cdot N_{\\mathrm{A}}}{\\frac{2V\\cdot\\rho_{\\mathrm{(P)}}}{M_{\\mathrm{P}}}\\times10^{-9}\\cdot N_{\\mathrm{A}}}}-1={\\frac{\\boldsymbol{x}\\cdot{\\mathrm{DBC}}\\cdot{\\mathrm{DoF}}\\cdot M_{\\mathrm{P}}}{V\\cdot\\rho_{\\mathrm{(P)}}\\cdot M_{\\mathrm{ave}}}}\\times10^{6}-1\n$$  \n\nIt can be seen that ACS is a dimensionless number.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 4.2. Measurement and Calculation of Degree of Crosslinking (DGC)  \n\nFurther, EDBC can be derived by ACS. Specifically, $\\mathsf{A C S+1}$ represents the number of consumed double bonds in a crosslinked chain and ACS represents the number of cross­ linked bonds in a crosslinked chain.[31] Therefore, EDBC is calculated by the following formula:  \n\n$$\n{\\mathrm{EDBC}}={\\frac{\\mathrm{ACS}}{{\\mathrm{ACS}}+1}}\\times100\\%\n$$  \n\nAt present, FTIR is commonly used to measure the DBC of hydrogels, but FTIR is a semi-quantitative analysis method. Due to the many uncertainties in sample preparation and measurement, FTIR tends to produce large errors (Figure S2A, Supporting Information). In contrast, NMR is a quantitative measurement method often used to accurately measure the amount of a functional group in a liquid substance (Figure S2B, Supporting Information). Since this method can only be used in liquids, it cannot be applied to crosslinked hydrogels. However, based on the degradable properties of hydrogels, taking GelMA as an example, a liquid substance can be obtained by degrading the crosslinked hydrogel with collagenase. The enzyme only specifically recognizes peptide bonds and does not break other chemical bonds. Thus, the double bond content after crosslinking can be measured accurately by NMR. Further, the DBC of crosslinked hydrogels can be calculated as follows:  \n\n$$\n{\\mathrm{DBC}}=\\left(1-{\\frac{A_{\\mathrm{(after)}}}{A_{\\mathrm{(before)}}}}\\right)\\times100\\%\n$$  \n\nWhere $A_{\\mathrm{(before)}}$ is the integral area of characteristic peaks of carbon–carbon double bond in NMR spectrum before crosslinking; $A_{\\mathrm{(after)}}$ is the integral area after crosslinking;  \n\nThe DGC can be calculated by the following formula (Figure 5A):  \n\n$$\n{\\mathrm{DGC}}={\\mathrm{DBC}}\\cdot{\\mathrm{EDBC}}\\times100\\%\n$$  \n\nThe value range of DGC is $0\\%-100\\%$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# 4.3. Measurement and Calculation of Density of Crosslinking (DSC)  \n\nTaking GelMA as an example, the main chain of GelMA is essentially a peptide chain.[36] Crosslinking of GelMA is the interconnection of MA groups on the side chains. Therefore, the DSC of GelMA can be calculated as follows:  \n\n$$\n\\mathrm{DSC}=\\frac{N_{(\\mathrm{crosslinked\\bond})}}{N_{(\\mathrm{peptide\\bond})}+N_{(\\mathrm{crosslinked\\bond})}}\\times100\\%\n$$  \n\nwhere $N_{\\mathrm{(crosslinked\\bond)}}$ is the number of crosslinked bonds;   \n$N_{\\mathrm{(peptidebond)}}$ is the number of peptide bonds.  \n\nFurther, for the convenience of calculation. Statistically speaking, the ratio of chemical bonds in the entire molecular network is equal to the ratio in repeating units. Therefore, the case of chemical bonds in one crosslinked chain is considered. The number of peptide bonds on main chain in a crosslinked chain can be calculated as follows:  \n\n$$\nN_{\\mathrm{(peptidebond)}}^{\\ast}=\\left(\\mathrm{ACS}+1\\right)\\cdot{\\frac{1}{\\mathrm{DoF}}}\n$$  \n\nThe number of crosslinked bonds on main chain in a crosslinked chain can be calculated as follows:  \n\n$$\nN_{\\mathrm{(crosslinkedbond)}}^{\\ast}=\\mathrm{ACS}\n$$  \n\nTherefore, the calculation formula of DSC is as follows (Figure 5A):  \n\n$$\n{\\mathrm{DSC}}={\\frac{\\mathsf{A C S}}{\\mathsf{A C S}+{\\frac{\\mathsf{A C S}+1}{\\mathsf{D o F}}}}}={\\frac{{\\mathsf{D o F}}\\cdot{\\mathsf{A C S}}}{{\\bigl(}{\\mathsf{D o F}}+1{\\bigr)}\\cdot{\\mathsf{A C S}}+1}}\\times100\\%\n$$  \n\nThe value range of DSC is $0\\%-100\\%$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# 4.4. Measurement and Calculation of Density of Molecular Network (DMN)  \n\nDMN is related to the density of the molecular network, so the molecular structure of monomers needs to be considered. The following assumptions are made according to the actual situation to facilitate the analysis and calculation:  \n\nA.\t The main chains and crosslinked chains of monomer molecules are usually composed of carbon atoms with only a small number of other atoms, such as nitrogen, oxygen, phosphorus, etc. Therefore, the bond energies are considered to be similar.   \nB.\t The stress and deformation of the material are all in the elastic range, and there is no chemical bond breakage. That is, only the elastic potential energy between molecules changes in this process.   \nC.\t The monomer molecules are freely distributed and fully stretched in the solution, and there is no mutual entanglement between the molecules. That is, the concentration of the solution is low.  \n\nD.\tThe monomers and initiators are uniformly distributed in the solution, and the crosslinking reaction between the mono­mers conforms to the normal distribution law. For ease of calculation, the average value is used instead.  \n\nThe tensile force exerted on the 3D network formed by the hydrogel is not evenly distributed to each molecular chain, but is related to the formation state. This force is distributed more to the mutually crosslinked molecular chains, while the uncrosslinked molecules are hardly affected by the force. Therefore, the following formula is used to describe the equivalent tensile force in a single molecular chain in the 3D network:  \n\n$$\nF_{\\mathrm{e}}=F\\cdot{\\frac{{\\mathrm{ACS}}+1}{{\\mathrm{ACS}}}}\n$$  \n\nwhere $F_{\\mathrm{e}}$ is the equivalent tensile force; $F$ is the actual applied tensile force.  \n\nThis formula can be tested with two extreme cases. For example, the ACS of the solution before crosslinking can be regarded as 0, then the $F_{\\mathrm{e}}$ of the solution is:  \n\n$$\nF_{\\mathrm{e}}=\\operatorname*{lim}_{\\mathrm{ACS}\\to0}F\\cdot{\\frac{{\\mathrm{ACS}}+1}{{\\mathrm{ACS}}}}=\\infty\n$$  \n\nSince the liquid cannot bear the tensile force, applying the tensile force will cause infinite deformation. For the sake of understanding, we regard $F_{\\mathrm{e}}$ as infinite. Correspondingly, for pure solids, such as metals, the ACS can be regarded as infinite. Then there are:  \n\n$$\nF_{\\mathrm{e}}=\\operatorname*{lim}_{\\mathrm{ACS}\\to\\infty}F\\cdot{\\frac{{\\mathrm{ACS}}+1}{{\\mathrm{ACS}}}}=F\n$$  \n\nThis means that the equivalent force on a solid is the force it applied actually, which is also consistent with the actual situation.  \n\nThen, the equivalent stress of the crosslinking unit is:  \n\n$$\n\\sigma={\\frac{F_{\\mathrm{e}}}{m\\cdot n}}\n$$  \n\nwhere m (nm) is the equivalent main chain length, the equivalent main chain length is defined as the chain length between two adjacent substitution sites on the molecular chain (Table S3, Supporting Information), which is used to measure the effect of DoF; $n$ (nm) is the length of crosslinked bond. The product of $m$ and $n$ represents the area of the structural unit.  \n\nAccording to assumption $A$ , the bond energies of the molecules are similar, then the strain of the crosslinking unit can be described by the following formula:  \n\n$$\n\\varepsilon={\\frac{D}{\\operatorname{ACS}\\cdot P_{\\mathrm{c}}}}\n$$  \n\nwhere $D$ is the deformation of the whole 3D network under force $F_{:}$ ; $P_{\\mathrm{c}}$ is the concentration of the solution.  \n\nIn addition, considering that the deformation direction of crosslinking unit is not always parallel to the stress direction, adding an angle corrects it:  \n\n$$\n\\varepsilon^{\\prime}=\\varepsilon\\cdot{\\frac{1}{\\cos\\left(45^{\\circ}-\\tan^{-1}\\left(\\left|{\\frac{m}{n}}\\right|\\right)\\right)}}\n$$  \n\nwhere $\\varepsilon^{\\prime}$ is the corrected strain.  \n\nTherefore, there is the following formula:  \n\n$$\n\\frac{\\sigma}{\\varepsilon^{\\prime}}=\\frac{\\mathrm{~}F\\cdot\\frac{\\operatorname{ACS}+1}{\\operatorname{ACS}\\cdot m\\cdot n}}{\\frac{D}{\\operatorname{ACS}\\cdot P_{\\mathrm{c}}}}{\\cos\\left(45^{\\circ}-\\tan^{-1}\\left(\\left|\\frac{m}{n}\\right|\\right)\\right)}=\\frac{F}{D}\\cdot\\frac{\\operatorname{ACS}+1}{m\\cdot n}\\cdot\\cos\\left(45^{\\circ}-t a\\mathrm{n}^{-1}\\left(\\left|\\frac{m}{n}\\right|\\right)\\right)\\cdot P_{\\mathrm{c}}\n$$  \n\nThe formula for calculating DMN is as follows (Figure 5B):  \n\n$$\n\\mathrm{DMN}={\\frac{\\mathrm{ACS}+1}{m\\cdot n}}\\cdot\\cos\\left(45^{\\circ}-\\tan^{-1}\\left(\\left|{\\frac{m}{n}}\\right|\\right)\\right)\\cdot P_{\\mathrm{c}}\\left[{\\mathrm{nm}}^{-2}\\right]\n$$  \n\nThe unit of DMN is $\\mathrm{nm}^{-2}$ , which represents the density of the molecular network after crosslinking",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 14,
+        "chunk": "# 5. Kinetic Analysis of Chemical Reaction during Crosslinking  \n\nThe chemical reactions involved in the photo-initiated radical polymerization process are as follows.[31,33,35]  \n\n1)\t Initiation reaction  \n\n$$\n\\begin{array}{c}{{I=2R^{*}}}\\\\ {{R^{*}+M=R M^{*}}}\\end{array}\n$$  \n\nSpecifically, the initiation reaction is divided into two steps. The first step is the decomposition of the initiator into primary radicals $\\left(\\boldsymbol{R}^{*}\\right)$ . The second step is the addition reaction of primary radical and monomer $(M)$ to generate monomer radical $(R M^{*})$ . The rate of monomer radical formation is much higher than initiator decomposition, so the rate of initiation reaction is usually determined only by the rate of initiator decomposition:[37]  \n\n$$\n\\nu_{i}={\\frac{2\\varphi\\varepsilon f\\lambda I_{0}C_{\\mathrm{i}}}{N_{\\mathrm{A}}h c}}\n$$  \n\nwhere $\\varphi$ is the photoinitiation efficiency, $\\varepsilon$ is the material absorbance; $\\lambda$ is the wavelength of the exposure light; $f$ is the initiation efficiency; $I_{0}$ is the light exposure intensity; $C_{\\mathrm{i}}$ is the initiator concentration; $N_{\\mathrm{A}}$ is the Avogadro constant; $h$ is Planck constant; $\\boldsymbol{c}$ is light speed.  \n\n2)\t Propagation reaction  \n\n$$\nR M_{\\mathrm{n}}^{\\ast}+M=R M_{\\mathrm{n+1}}^{\\ast}\n$$  \n\nThe rate of propagation reaction is:  \n\n$$\n\\nu_{p}=k_{p}C_{(M)}C_{\\left(R^{*}\\right)}\n$$  \n\nwhere $k_{\\mathrm{p}}$ is the propagation reaction rate constant; $C_{(M)}$ is the monomer concentration and $C_{(R^{*})}$ is the radical concentration.  \n\n3)\t Termination reaction  \n\n$$\nR M^{*}+R M^{*}=R M_{2}\n$$  \n\nThe rate of termination reaction is:  \n\n$$\n\\nu_{t}=2k_{t}C_{\\left(R^{*}\\right)}^{2}\n$$  \n\nwhere $k_{\\mathrm{t}}$ is the termination reaction rate constant.  \n\n4)\t Blocking reaction  \n\n$$\n\\boldsymbol{R}\\boldsymbol{M}^{*}+\\boldsymbol{R}^{*}=\\boldsymbol{R}_{2}\\boldsymbol{M}\n$$  \n\nThe rate of blocking reaction is:  \n\n$$\n\\nu_{\\mathrm{b}}=2k_{\\mathrm{b}}C_{\\left(R^{*}\\right)}^{2}\n$$  \n\nwhere $k_{\\mathrm{b}}$ is the blocking reaction rate constant.  \n\nIt has been demonstrated above that the EDBC of the propagation reaction is higher than termination and blocking reactions. Therefore, increasing the proportion of propagation reaction can increase the EDBC of the overall polymerization reaction. Based on this, the ratio of propagation reaction to termination reaction and blocking reaction is proportional to DGC, and the derivation formula is as follows:  \n\n$$\n\\mathrm{DGC}\\propto\\frac{\\mathrm{Propagation}}{\\mathrm{Termination}+\\mathrm{Blocking}}\\propto\\frac{k_{p}C_{(M)}C_{\\left({R^{*}}\\right)}}{2\\left(k_{t}+k_{b}\\right)C_{\\left({R^{*}}\\right)}^{2}}=\\frac{k_{p}C_{(M)}}{2\\left(k_{t}+k_{b}\\right)}\\cdot\\frac{1}{C_{\\left({R^{*}}\\right)}}\n$$  \n\nThe chemical reaction rate constant is used to measure the speed of the reaction, which is unrelated to the concentration of reaction substrates, but is affected by many factors, such as temperature, reaction medium, and catalyst type. Here, the reaction rate constant is characterized according to the reactivity of reactants and molecular diffusion rates. The increase of molecular activity and diffusion rate can lead to an increase in the rate constant. In terms of molecular activity, primary radical, monomer radical and chain radical with unpaired electron have low activation energy and high activity, while $M$ without unpaired electron has high activation energy and low activity. For macromolecules in liquid solutions, the Stokes– Einstein equation can be used to describe the diffusion rate:  \n\n$$\nD=\\frac{k T}{6\\pi\\mu r}\n$$  \n\nwhere $k$ is the Boltzmann constant; $T$ is the temperature; $\\mu$ is the viscosity of the medium and $r$ is the radius of the diffusing molecule.  \n\nIn the same temperature and medium, the diffusion rate is inversely proportional to the size of molecules, which is directly related to the molecular weight. It should be noted that with the progress of the crosslinking reaction, the molecules combined with each other, the viscosity of the system also increased, and the rate constant also changed. For the convenience of analysis, it starts from the case where the viscosity of the system is equal at the beginning. Molecules with a faster diffusion rate in the system have a greater impact on the overall diffusion rate, so the components with smaller molecular weights in the reaction substrate determine the overall diffusion rate. In the system of small molecule polymerization, the molecular weight of radical is usually larger than that of monomers, so the following relationship can be drawn:  \n\n$$\nr_{\\left(R^{*}\\right)}\\approx r_{\\left(R M^{*}\\right)}>r_{\\left(M\\right)}\n$$  \n\nAccordingly, the relationship between the reaction rate constant is as follows  \n\n$$\nk_{p}>k_{t}\\approx k_{b}\n$$  \n\nIn the macromolecular polymerization system, the molecular weight of the monomer is much larger than that of the radical, and the following relationship can be obtained:  \n\n$$\nr_{\\left(R^{*}\\right)}<<r_{\\left(R M^{*}\\right)}\\approx r_{\\left(M\\right)}\n$$  \n\nCorrespondingly, the relationship between the reaction rate constant is:  \n\n$$\nk_{p}<k_{t}<<k_{b}\n$$  \n\nTherefore, the DGC of small molecules is higher than that of macromolecules, which is consistent with the situation observed in experiments. It also explains why the ACS of hydrogel is much lower than that of small molecular polymers.  \n\nFurthermore, in addition to the effect of molecular weight, the light exposure intensity also influences the formation state. It can be seen from Equation  21 that the exposure intensity directly affects the rate of initiation reaction. In the curing process, lower exposure intensity generates radicals more slowly, which means fewer radicals exist in the reaction system. It can be seen from Equation  27, DGC is inversely proportional to radical concentration, so low exposure intensity will increase the DGC (Figure 6).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 6. Regulation Method of Formation State  \n\nCompared with traditional polymers, the printability of hydrogels in PBP is poor, which is mainly caused by the following reasons:  \n\n1)\t DoF is closely related to the crosslinking of monomers. According to Equation  3, the DoF of hydrogels is usually $<20\\%$ (Table 3), while the DoF of traditional polymers is usually high, up to $70\\%-90\\%$ .[12]   \n2)\t The high biocompatibility of the hydrogel requires that it contains as few chemicals as possible. Therefore, the diluents, stabilizers, modifiers, and many other additives that are beneficial to polymerization cannot be used in hydrogels.   \n3)\t The hydrogel is polymerized in an aqueous solution, and the concentration is usually $<10\\%$ . In addition, a large amount of dissolved oxygen in the water will further hinder the crosslinking process.  \n\n![](images/a9276c1d5206f5a14421d503a83e9468b72b3bf4e564964de2e4bbef2a0f2ae2.jpg)  \nFigure 6.  Kinetic analysis of chemical reaction during crosslinking.  \n\n4)\t The molecular weight of the hydrogel monomer is large, and the viscosity of the solution is also high. Therefore, the molecular diffusion rate is low, and the crosslinking efficiency is low.  \n\nBased on the above limitations of hydrogels, the current method to adjust the formation state is mainly to control the exposure time. The conventional understanding of regulating the formation state was that with the increase of the exposure time, the DBC gradually increased, and the DGC also gradually increased. After a certain exposure time, DBC approaches $100\\%$ and DGC can no longer be improved. However, according to the previous derivation, the concentration of radicals in the system can be controlled by reducing the exposure intensity to further increase the DGC. The upper limit of DGC depends on not only how many double bonds are consumed, but also on how many crosslinked bonds are formed.  \n\nUnder the same exposure dose, the exposure intensity has a significant effect on DGC. Specifically, termination and blocking reactions are the main reactions under high-intensity and short-time exposure, so the DGC is low. On the contrary, propagation reaction is dominant under low-intensity and longtime exposure, so the EDBC and DGC are high. Therefore, by controlling the exposure intensity, the DGC can be further increased, approaching a higher upper limit (Figure 7), which was called the slow crosslinking effect.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 7. Experimental Results and Analysis  \n\nIn order to verify the slow crosslinking effect, the application performance of GM30 (Figure  8C; Figure  S1A, Supporting Information) hydrogels cured with different exposure intensities were tested, including tensile (Figure  8Ai), compression (Figure  8Aii), degradation (Figure  8Aiii), and swelling (Figure  8Aiv; Figure  S3, Supporting Information) tests. The abbreviations (Table  1) were used to refer to different types of GelMA (Suzhou Intelligent Manufacturing Research Institute, Suzhou, China). The curing conditions were shown in Table 2. It should be noted that the excessive exposure dose was used to ensure the complete poly­ merization. The test results of DBC (Figure  8B) showed that the exposure dose of 9.5  J $\\mathrm{cm}^{-2}$ could destroy almost all double bonds. DBC for all three curing conditions was close to $100\\%$ . The results of these experiments all indicated that the slow crosslinking GelMA had higher tensile and compressive strengths, slower degradation rate, denser internal network (Figure S4, Supporting Information), and lower swelling ratios compared to the fast crosslinked GelMA. Therefore, the slow crosslinked hydrogel had a denser crosslinked network. Not only that, the same results were obtained from PEGDA hydrogels (Figure S5A,B, Supporting Information), indicating that the slow crosslinking effect was generally applicable to the different hydrogels.  \n\nTable 2.  Different crosslinking conditions.   \n\n\n<html><body><table><tr><td>Crosslinking type</td><td>Exposure intensity</td><td>Exposure time</td><td>Exposure dose</td><td>Temperature</td></tr><tr><td> Slow crosslinking</td><td>0.3 mW/cm2</td><td>8.8 h</td><td>9.5 J/cm2</td><td>37 ℃</td></tr><tr><td>Medium-crosslinking</td><td>30 mW/cm²</td><td>320 s</td><td>9.5J/cm²</td><td>37 °℃</td></tr><tr><td>Fast crosslinking</td><td>600 mW/cm2</td><td>16 s</td><td>9.5 J/cm²</td><td>37°℃</td></tr></table></body></html>  \n\n![](images/4442531b0be808a183608a2b5cbed6ed5abd3994571d728d22b1c59cb8b2834c.jpg)  \nFigure 7.  Formation state regulation method based on exposure intensity.  \n\nThe amino acid content in gelatin was measured by an amino acid analyzer, and the results showed that the ratio of amino acids containing amino groups in $R$ group in gelatin was ${\\approx}19.4\\%$ (Figure  8D). The test results of NMR and liquid chromatography showed that the substitution degree of GM30, GM60, and GM90 were $29.63\\%$ , $61.2\\%$ , and $93.44\\%$ , respectively (Figure  8C; Figure  S1A–C, Supporting Information). The $\\mathrm{\\DeltaP}$ element concentration test results of GelMA and PEGDA cured with different exposure intensities showed that the hydrogels cured with low exposure intensity had low $\\mathrm{~P~}$ element content. Low DoF hydrogels had low P element content. The content of $\\mathrm{\\DeltaP}$ element in small molecule hydrogel PEGDA was lower than macromolecular GelMA (Figure  8E). According to the previous analysis, the content of $\\mathrm{\\DeltaP}$ element was inversely proportional to DGC, so reducing the molecular weight, reducing the exposure intensity, and increasing DoF could increase the DGC. These test results were in full agreement with the predictions. The application performance of hydrogels cured with different exposure intensities was shown in Figure  8Fi and Figure  S4C (Supporting Information). The exposure intensity could directly affect the application performance. For further analysis, the indices describing the formation state were shown in Figure  8Fii. It could be seen that the DBC were all close to $100\\%$ , which cannot be used to explain the slow crosslinking effect. According to our evaluation system, this result could be well explained. The calculation results showed that the EDBC, ACS, DGC, DSC, and DMN of slow crosslinking hydrogels were higher than those of the fast crosslinked hydrogels, which proved the theory from a qualitative point of view.  \n\nTable 3.  Properties of different hydrogels.   \n\n\n<html><body><table><tr><td>Hydrogel type</td><td>DoF</td><td>Concentration</td><td>Crosslinking rate</td><td>Monomer molecular weight</td></tr><tr><td>GM30FC</td><td>5.74%</td><td>10%</td><td>Fast</td><td>=90 000 Da</td></tr><tr><td>GM30 MC</td><td>5.74%</td><td>10%</td><td>Medium</td><td>90 000 Da</td></tr><tr><td>GM30 SC</td><td>5.74%</td><td>10%</td><td>Slow</td><td>90000</td></tr><tr><td>GM60 MC</td><td>11.9%</td><td>10%</td><td>Medium</td><td>90000</td></tr><tr><td>GM90MC</td><td>18.1%</td><td>10%</td><td>Medium</td><td>=90 000 Da</td></tr><tr><td>PEGDA FC</td><td>15.4%</td><td>10%</td><td>Fast</td><td>=700 Da</td></tr><tr><td>PEGDA MC</td><td>15.4%</td><td>10%</td><td>Medium</td><td>=700 Da</td></tr><tr><td>PEGDA SC</td><td>15.4%</td><td>10%</td><td>Slow</td><td>=700 Da</td></tr></table></body></html>  \n\nSince both DGC and DSC were defined based on ACS, the accuracy of ACS needed to be verified first. In order to prove the correctness of ACS from a quantitative level, the fast crosslinked and slow crosslinked GelMA were hydrolyzed with the hydrochloric acid solution to break all the peptide bonds on the main chain, leaving only the covalently crosslinked molecular chain (Figure S6, Supporting Information). The molecular weight distribution of the solution after hydrolysis was measured by gel permeation chromatography (GPC) (Figure  8G). The results showed that the slow crosslinked GelMA had a larger molecular weight, indicating that the ACS was higher than fast crosslinked GelMA. In addition, the molecular weight of the covalently crosslinked chain was calculated according to ACS:  \n\n$$\nM_{\\mathrm{cc}}=\\left(A C S+1\\right)\\cdot M_{\\mathrm{m}}+M_{\\mathrm{LAP}}\n$$  \n\n![](images/c4918461e9bf1804a8bba819a89b5c67db27fc3681ba7d7d1b3cd7314743aca5.jpg)  \nFigure 8.  Quantitative calculation of formation state indices and influence of exposure intensity on formation state. Ai–Aiv) Tension, compression, degradation and swelling properties of fast, medium and slow crosslinked GelMA; B) DBC of fast, medium and slow crosslinked GelMA; C) 1H NMR spectra of GelMA with different substitution rates; D) Proportion of amino acids containing amino group in $R$ group in gelatin; E) Content of P element in various hydrogels cured with LAP. Comparison of application performance (Fi) and formation indices (Fii) of fast, medium and slow crosslinked GelMA hydrogels; G) Comparison of theoretical calculation and measurement results of molecular weight of crosslinked chains; H) Linear fitting relationship between DMN and Young’s modulus.  \n\nwhere $M_{\\mathrm{cc}}$ is the molecular weight of the crosslinked chain; $M_{\\mathrm{m}}$ is the average molecular weight of GelMA monomer. It can be calculated according to the molecular weight and proportion of different amino acids in gelatin. Then corrected according to the substitution rate and the molecular weight of the substitution group. $M_{\\mathrm{LAP}}$ is the molecular weight of the initiator LAP.  \n\nThe calculated results showed that the molecular weight of slow crosslinked GelMA was 7768 Da, which was very close to the measured molecular weight distribution peak of 11081 Da. The calculated result for fast crosslinked GelMA was $2218~\\mathrm{Da}$ , which was also very close to the measured molecular weight distribution peak of 1800  Da. Considering some error factors in hydrolysis and testing, the calculated results were in good agreement with the measured results. This verified the accuracy of the evaluation system to describe the ACS from a quantitative level.  \n\nCorrespondingly, the DMN of different kinds of hydrogels cured with different exposure intensities were calculated. To ensure the universality of the evaluation system, hydrogels with different monomer molecular weights and different DoF were selected. The hydrogels were also cured with different exposure intensities (Table  3). The calculated DMN was linearly correlated with the measured Young’s modulus (Figure 8H), which verified the accuracy of the evaluation model to describe the DMN from a quantitative level.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 8. Hydrogel Projection-Based 3D Printing (PBP) Strategy",
+        "category": " Introduction"
+    },
+    {
+        "id": 18,
+        "chunk": "# 8.1. The Principle and Process of Fast Crosslinking Printing and Slow Crosslinking Post-Processing (F–S Printing)  \n\nAccording to the previous analysis, slow crosslinking could improve DGC, resulting in higher strength of hydrogels. The improvement in mechanical properties can significantly improve hydrogel’s printability. Therefore, the slow crosslinking effect could be used to optimize the printing process.  \n\nDuring the photocuring process, with the increase of the exposure time, the storage modulus $(\\mathrm{G}^{\\prime})$ gradually increases, while the loss modulus $(\\mathrm{G}^{\\prime\\prime})$ remains basically unchanged, and the viscosity of the solution gradually increases. After reaching a certain exposure time, $\\boldsymbol{\\mathrm{G^{\\prime}}}$ equals $G^{\\prime\\prime}$ , which is also called the gel point (GP) (Figure 9B). In the early stage of crosslinking, the system contains a lot of monomers, so the propagation reaction dominates. After reaching the GP, the viscosity of the system increases greatly, the number of monomers decreases, and the termination reaction dominates. Therefore, during the crosslinking process, before reaching the GP, the DGC rises rapidly, and after reaching the GP, the DGC rises at a slower rate. The ACS showed a trend of increasing first and then decreasing (Figure 9B,C), which was the gel point effect. Therefore, using a high exposure intensity for curing in the early stage can shorten the reaction time and improve the printing efficiency. Then the slow crosslinking after GP can further increase the DGC and improve the mechanical strength.  \n\nIn traditional printing, due to the hydrogel’s poor printability, the exposure time of GP usually fails to maintain structural fidelity (Figure 9Di). It requires continued exposure for a period to further improve DGC. Typically, 2–3 times the GP exposure time is required to maintain sufficient structural strength. However, due to the refraction and scattering of UV light, the longer the exposure time, the lower the printing resolution. Although excessive exposure time ensures structural fidelity, it reduces print resolution. To solve this problem, the F–S printing strategy was proposed. That is, the exposure time is precisely controlled near the GP time, and then the printed hydrogel structure is placed in a solution containing an initiator. Although the GPprinted hydrogel deforms or even collapses (Figure 9Di), when it was immersed in a liquid, the surface tension of the liquid allowed it to return to its original shape (Figure  9Dii). Finally, low exposure intensity is used for post-processing for a period of time (Figure  9A and Table 4) to improve the DGC, thereby ensuring structural fidelity (Figure  9Diii). It can be seen that the ACS of F–S printing is 59.1, and the DGC is $92.9\\%$ , while the ACS of traditional printing is 50.7, and the DGC is $67.6\\%$ (Figure 9C).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 8.2. Printability Comparison between F–S and Traditional Printing  \n\nThe apparent description of printability usually includes printing resolution, printing efficiency and mechanical properties, etc. Based on our previous work (Figure S7, Supporting Information),[13a,17a] the XY and $Z$ resolution of F–S printing and traditional printing were compared. The radial stripe structure was used to evaluate the XY resolution, and the rotating stepped structure was used to evaluate the $Z$ resolution (Figure  9E). It can be seen that the XY resolution has increased from 484 to $159\\upmu\\mathrm{m}$ , and the $Z$ resolution has increased from 821 to $288\\upmu\\mathrm{m}$ (Figure  9Fi). The printing time of each layer is also shortened from 25 to 10s (Figure  9Fii). At the same time, Young’s modulus of cured hydrogel increased from 35.3 to $63.7~\\mathrm{KPa}$ (Figure 9Fiii,I). The printability of F–S printing has been comprehensively improved. Solid (Figure 9G) and porous structures (Figure 9H) can be well printed by F–S printing strategy.  \n\nIt is known that the essential reason for hydrogels’ poor printability is the low crosslinking degree. However, due to the lack of quantitative evaluation methods for crosslinking status, the printability of hydrogels is always in the stage of macro analysis. According to this work, it can be calculated that the DMN of GelMA and other macro-molecular hydrogels is only $10^{-1}-10^{0}\\mathrm{nm}^{-2}$ , the DMN of PEGDA and other small-molecule hydrogels is $10^{0}-10^{1}~\\mathrm{nm}^{-2}$ , and the DMN of traditional polymers, such as polyethylene can be as high as $10^{4}-10^{6}\\mathrm{nm}^{-2}$ . It revealed a huge gap between hydrogels and traditional polymer formation processes. To be clear, the F–S strategy could improve the printability of hydrogels by 2–4 times, but it was still difficult to reach the level of conventional polymers. However, in the previous printability research, researchers usually start by optimizing the printing process and material components. There is little knowledge of the formation process and formation theory for hydrogels. The concept of printability itself also lacks quantifiable indicators. This work is expected to provide quantifiable indicators and evaluation criteria for printability.  \n\nHydrogels are often used for cell-laden 3D printing, so it is also important to ensure cell viability during printing. In the photocuring process, the main cause of cell damage is radicals (Figure  S8C, Supporting Information), while UV light at $405\\ \\mathrm{nm}$ hardly damages cells (Figure S8A,B, Supporting Information). Hydrogels can reduce the damage of radicals to cells to a certain extent (Figure  S8C,D, Supporting Information). However, under a radical-rich environment for a long time also resulted in massive cell death (Figure  S8E, Supporting Information). Therefore, it is very important to control the radical flux during cell-laden 3D printing.  \n\n![](images/6c405373ba9952162f3511da2db740bd21763db23f9973b01440cdd57c870309.jpg)  \nFigure 9.  F–S printing strategy and its advantages. A) Process of F–S printing; B) Comparison of rheological properties and DBC between traditional and F–S printing; C) Comparison of DGC and ACS of traditional and F–S printing; D) Structural fidelity changes of hydrogels during F–S printing; E) Test method of XY printing resolution and $Z$ printing resolution; Comparison of printing resolution Fi), printing time Fii) and mechanical strength Fiii); Photographs of printed solid G) and porous structures H) by F–S printing; I) Comparison of tensile stress–strain curves. Double asterisk $(\"x^{*})$ indicates statistically significant $p$ -value $<0.01$ , quadruple asterisk $(^{14-x^{2}+3(-x^{2})})$ indicates statistically significant $p$ -value $<0.000\\rceil$ $(\\mathsf{n}=3)$ .  \n\nTable 4.  Comparison of F–S and traditional PBP parameters.   \n\n\n<html><body><table><tr><td>Method</td><td>Material</td><td>Exposure time</td><td>Exposure intensity</td><td>Post-processing</td></tr><tr><td>F-S</td><td>10%GM90</td><td>10 s/layer</td><td>30 mW/cm-2</td><td>0.3 mW/cm²×30min</td></tr><tr><td>Traditional</td><td>10% GM90</td><td>25s/layer</td><td>30 mW/cm-2</td><td></td></tr><tr><td>GP</td><td>10%GM90</td><td>10s/layer</td><td>30 mW/cm-2</td><td></td></tr></table></body></html>  \n\nWhen printing simple plane structures, both traditional and F–S printing have high cell viability $(>90\\%$ at day 0 and $>95\\%$ at day 3 ). It can be seen that the cell viability of GP printing is the highest, close to $100\\%$ (Figure 10Ai,ii; Figures S9 and S10, Supporting Information). However, the incomplete crosslinking of the hydrogel at this time leads to poor structural fidelity, which is difficult to be applied in practice. Traditional printing could also achieve high cell viability $(\\approx90\\%$ at day 0 and $\\approx97\\%$ at day 3) (Figure  10Ai,ii; Figures  S9 and S10, Supporting Information), which showed that PBP is an ideal bioprinting method. At this time, the DBC was close to $100\\%$ . The F–S printing further improved the crosslinking density while maintaining better cell activity $(\\approx95\\%$ at day 0 and $\\approx98.5\\%$ at day 3) (Figure  10Ai,ii; Figures  S9 and S10, Supporting Information), which showed that F–S strategy has advantages in bioprinting $p$ -value $<0.05$ ). In addition, the staining results of the nucleus/skeleton showed that different printing methods had a high cell spreading rate $(>90\\%)$ . Specifically, GP printing has the highest spreading rate $(\\approx100\\%)$ (Figure 10Bi,ii), followed by traditional printing $(\\approx96\\%)$ (Figure 10Bi,ii), and F–S has the lowest stretching rate $(\\approx90\\%)$ (Figure 10Bi,ii). This result proved that the F–S printed hydrogel has a denser 3D network.  \n\nWhen printing simple plane structures, F–S printing has higher cell viability than traditional printing, but this advantage is not significant. This is because the overall time for printing plane structures is short, and the damage of radicals to cells is not very obvious. However, in practical tissue engineering applications, it is often necessary to print complex structures. These structures have more layers in total, F–S printing has more obvious efficiency advantages than traditional printing and cells are less damaged. When printing three-period minimal surface (TPMS) structure, prolonged high-intensity exposure leads to $44.3\\%$ apoptosis (Figure  10Ci,D), which is very unfavorable for bioprinting. F–S printing shortens the time of high intensity exposure. The post-processing of slow crosslinking has less damage to cells due to the lower concentration of radicals. Therefore, F–S printing can reduce the apoptosis rate to $18.1\\%$ (Figure 10Cii,D).  \n\nOverall, the F–S printing strategy has greatly improved the printing resolution, printing efficiency, mechanical properties and cell compatibility, which is expected to be a new strategy for hydrogel bioprinting.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# 8.3. Biological Application of F–S Printing Strategy  \n\nDifferent 3D bioprinting behaviors or biofabrication processes can directly or indirectly regulate the physiological and biochemical state of cells.[38] Differences in printing strategies determine cell fate by reconstructing microenvironments with different mechanical properties.[39] By changing the exposure parameters of post-processing, F–S printing could further adjust the crosslinking degree and mechanical properties in the cured hydrogel, thus regulating the cell fate. For example, bone marrow derived mesenchymal stem cells (BMSCs) with differentiation potential have been reported to tend to osteogenic differentiation in hydrogel with high mechanical properties[40] and chondrogenic differentiation in hydrogel with low mechanical properties.[41] To identify miRNA that may be significant in cells under different 3D bioprinting strategies, miRNA sequencing was performed to compare miRNA expression in BMSCs under F–S printing strategies with different post-processing times $\\ensuremath{\\left[30\\mathrm{\\min}\\right.}$ of F–S (30) or $60~\\mathrm{{min}}$ of F–S (60)) and other printing strategies (GP or TD). F–S printing has significantly differentially expressed genes (DEGs) in cells compared with other printing strategies (Figure 11A). Specifically, a total of 7793 out of all the 40372 annotated unigenes that were significantly differentially expressed between cells under different printing strategies were identified (Figure 11A, TD vs. F–S (60), $^{>2}$ fold; $p<0.05)$ ). Among these, the transcription levels of 6175 were upregulated and 1816 were downregulated in cells under F–S printing. Compared with other printing strategies (GP or TD), F–S printing produced more upregulated or downregulated genes in cells at both gene level and transcript level (Figure 11B; Figure  S11, Supporting Information). Then, the number of DEGs in cells under different printing strategies was compared. There were 373 and 278 annotated genes expressed only in cells under F–S printing (Figure 11C). This result hinted that F–S printing can reconstruct specific microenvironments that trigger specific biological behaviors in cells.  \n\nTo be specific, based on the DEGs analysis compared with the GP printing and TD printing, the F–S printing showed consistent upregulation of genes correlated to osteogenic differentiation, such as BSP, RUNX2, and BMP2 (Figure 11D; Figure S12, Supporting Information). Meanwhile, chondroblast differentiation-related genes, such as SOX9, COL2A1, and ACAN, were uniformly downregulated (Figure  11D; Figure  S12, Supporting Information). These results underlined that F–S printing can realize hydrogel bioprinting with high mechanical properties and promote the osteoblastic differentiation of cells in the hydrogel. The GP printing utilizes the incomplete hydrogel cross-linking system to achieve low mechanical properties of hydrogel bioprinting, which promotes chondrogenic differentiation of cells in hydrogel. In addition, the cells undergoing F–S printing showed higher expression levels of mechanical stimulation-related signals, such as LMNA, YAP1, and ICAM1, which further indicated that F–S printing improved the mechanical properties of hydrogels (Figure 11D). Interestingly, the oxidative stress of cells was increased by TD printing, while the oxidative stress of cells was alleviated by GP printing or F–S printing, which may be caused by reactive oxygen species (ROS) produced by radicals during hydrogel crosslinking (Figure  11D). In the process of TD printing, there are more ROS produced by radicals, and the residual ROS attack cells randomly, resulting in oxidative stress. In the process of GP printing, radical tends to crosslink hydrogel monomers due to the incomplete crosslinking state of hydrogel. In the process of F–S printing, smaller exposure intensity enables radical to more fully promote the crosslinking of hydrogel monomer, thus reducing the production of ROS and relieving the oxidative stress of cells. A summary of in vitro gene expression data is shown in Figure 11E.  \n\n![](images/b7def6b95641ba30b21003c4b419fd9399aeb3924fa153facdccac6dfd07a34e.jpg)  \nFigure 10.  Biocompatibility comparison between traditional and F–S printing. Ai) Confocal fluorescence microscopy images of LIVE/DEAD staining of bioprinting (plane structure) at day 3; Aii) Comparison of cell viability of printing plane structure; Bi) Confocal fluorescence microscopy images of F-actin/nucleus markers of bioprinting (plane structure) at day 3; Bii) Comparison of cell spreading of printing plane structure; Flow cytometry analysis of apoptosis in traditional Ci) and $\\mathsf{F}\\mathrm{-}\\mathsf{S}\\mathsf{C i i}$ ) bioprinting (complex structure) at day 0; D) Comparison of apoptosis rate of printing complex structure. Single asterisk $(^{*})$ indicates statistically significant $p$ -value $<0.05$ , double asterisk $(\"x^{2})$ indicates statistically significant $p$ -value $<0.01$ , triple asterisk $(^{x+x+x})$ indicates statistically significant $p$ -value $<0.00\\rceil$ $(\\mathsf{n}=3)$ ).  \n\n![](images/ec873649cd8870c4be979e470aed02e15e432b8eb90b2557917747ad416e50b9.jpg)  \nFigure 11.  Unique biological mechanism of F–S printing. A) Volcano plot of differentially expressed genes (DEGs) among different printing strategy (GP: Gel point printing; TD: Traditional printing; F–S: printing atisfyin th criter (fold-change) value ${>}1$ or $\\leftrightharpoons\\right]\\mathrm{\\Sigma}<\\mathrm{-}\\mathrm{\\right]}$ and $P<0.05$ . Significantly upregulated or downr gulated cate nonsignificant results. B) The number of upregulated or down genes (Transcri dia number among different groups. D,F) Heatmap and Pe elat chanical stimulation, and oxidative stress among differen tering results for the differentially expressed miRNAs groups for each heatmap were visualized ript level in different groups. H) Circular of the notation enrichment analysis. I,J) The most significant GO terms and KEGG enrichment analyses of the upregulated genes related to cells in F–S printing versus traditional printing.  \n\nPearson correlation coefficients were calculated for representative DEGs correlated to osteogenesis, chondrogenesis, mechanical stimulation, and oxidative stress among different groups to generate similarity matrices. Similarity matrix analysis indicated that GP printing and TD printing showed similar gene expression patterns to each other in the biological processes of osteogenic differentiation and chondrogenic differentiation (Figure 11F). In addition, TD printing strategies exhibited unique gene expression profiles in terms of oxidative stress compared to GP printing strategies or F–S printing strategies (Figure  11F). In general, the GP printing and TD printing presented similar gene expression patterns, while the F–S printing demonstrated different gene expression patterns, suggesting that the F–S printing could create a new micro­ environment with different mechanical properties (Figure 11F). The results of principal component analysis (PCA) also implied that the transcription profiles of cells under $\\mathrm{F}{-}\\boldsymbol{\\mathrm{S}}$ printing were significantly different from those of other printing strategies (GP or TD), no matter at the gene level or transcript level (Figure  11Gi,ii). Specifically, F–S printing can promote cell differentiation toward osteoblast and can activate the expression of mechanical stimulus signaling molecules in cells, while reducing oxidative stress during cell-laden bioprinting, with better cell compatibility. The results of gene enrichment analysis also proved that the F–S printing could cause cells to enrich the expression of genes related to osteogenic differentiation and mechanical stimulation signal. GP printing caused cells to enrich chondroblast differentiation-related genes, while TD printing caused cells to activate more oxidative stress, raising concerns about cell compatibility (Figure 11H).  \n\nDifferences in gene expression in BMSCs exposed to different printing strategies (GP vs. F–S (60)) were detected using RNA-seq to determine the molecular mechanism of the printing strategies–cell interaction. The results of gene ontology (GO) enrichment analysis showed that certain DEGs were enriched in the biological adhesion, extracellular matrix component, and binding (Figure  11I). We further focused on several typical signaling pathways to better understand the causes of major differences for cell behaviors within GP or F–S (60) printing strategies. Among the enriched typical signaling pathways, the Hippo signaling pathway was demonstrated as one of the essential signaling pathways that led to the differences in cell behavior under different printing strategies (Figure  11J). The hippo signaling pathway is a mechanotransduction signaling pathway, activated by mechanical cues generated from altered cell–cell junctions, extracellular matrix (ECM) stiffness or microenvironment.[42] The results of Kyoto Encyclopedia of Genes and Genomes (KEGG) enrichment analysis suggested that the changes in mechanical properties of hydrogel microenvironment triggered during F–S printing may guide specific cell behaviors and determine cell fate by activating hippo signaling pathway. In addition, KEGG enrichment analysis also indicated that the F–S printing significantly activated the cellular processes of signaling pathways regulating pluripotency of stem cells and focal adhesion, as well as improved the biosynthesis efficiency of chondroitin sulfate, which may be the potential mechanism of F–S printing guiding the osteogenic differentiation and adhesion of BMSC (Figure 11J).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# 9. Conclusion  \n\nIn this study, we summarized the differences between hydrogels and traditional polymer formation processes and established a theoretical system for the formation of photo-crosslinked hydrogels. The formation indices of hydrogels were defined in detail, and the quantitative measurement and calculation method were demonstrated together. According to formation theory, it was predicted that slow crosslinking could improve the degree of crosslinking, thereby obtaining better application performance. Further, based on slow crosslinking effect, an F–S printing strategy was proposed. Compared with traditional printing, F–S printing could achieve higher printing efficiency, printing resolution, mechanical strength and biocompatibility. In addition, by changing the exposure parameters of postprocessing, F–S printing could further adjust the mechanical properties in the cured hydrogel, thus regulating the cell fate. We believe that the formation theory can help us understand hydrogel’s crosslinking process better and provide guidance for the manufacturing and application of photocurable hydrogels.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 22,
+        "chunk": "# 10. Discussion  \n\nDifferent hydrogels have different properties, and multi-component hydrogels are often necessary to achieve performance requirements in actual use. The formation theory can only be used to describe the crosslinking process and formation state of single-component hydrogels, and further research is needed for multi-component hydrogels.  \n\nOxygen inhibition has a great influence on the radical poly­ merization process. Especially, the water content of hydrogels is usually $590\\%$ , which contains a lot of dissolved oxygen, so the effect of oxygen inhibition is particularly obvious. However, the formation theory does not fully take this into account. In fact, in the process of slow crosslinking, due to the long reaction time, oxygen continuously penetrates the hydrogel, and the effect of oxygen inhibition is very obvious. To avoid it, the hydrogel was cured in a nitrogen atmosphere. However, in the actual printing process, it is inevitable to encounter oxygen, and the bioink also contains dissolved oxygen. Therefore, it is necessary to further analyze the influence of the oxygen inhibition effect on the hydrogel photo-crosslinking process.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# Supporting Information  \n\nSupporting Information is available from the Wiley Online Library or from the author.",
+        "category": " References"
+    },
+    {
+        "id": 24,
+        "chunk": "# Acknowledgements  \n\nC.-F.H., Y.S., and N.L. contributed equally to this work. The authors acknowledge the physical and chemical analysis Lab. of analysis center of agrobiology and environmental sciences with inductively coupled plasma mass spectrometer. The authors acknowledge the NMR spectrometer of the instrument platform of the State Key Laboratory of Plant Physiology and Biochemistry, College of Life Sciences, Zhejiang University. This work was financially supported by the National Key Research and Development Program of China (2018YFA0703000) and National Natural Science Foundation of China (T2121004 andU1909218). A project supported by Scientific Research Fund of Zhejiang Provincial Education Department (Y202250802)",
+        "category": " Acknowledgements"
+    },
+    {
+        "id": 25,
+        "chunk": "# Conflict of Interest  \n\nThe authors declare no conflict of interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 26,
+        "chunk": "# Data Availability Statement  \n\nThe data that support the findings of this study are available in the supplementary material of this article.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 27,
+        "chunk": "# Keywords  \n\nformation theory, hydrogels, photo-crosslinking, printability, projectionbased 3D printing  \n\nReceived: February 1, 2023   \nRevised: March 8, 2023   \nPublished online: April 12, 2023  \n\n[1]\t M. J. Rowland, M. Atgie, D. Hoogland, O. A. Scherman, Biomacromolecules 2015, 16, 2436.   \n[2]\t a) Z.  Atoufi, S. K.  Kamrava, S. M.  Davachi, M.  Hassanabadi, S. S.  Garakani, R.  Alizaleh, M.  Farhadi, S.  Tavakol, Z.  Bagher, G. H.  Motlagh, Int. J. Biol. Macromol. 2019, 139, 1168; b) Y. N.  Liu, D. D. Fan, Int. J. Biol. Macromol. 2019, 141, 700.   \n[3]\t a) F.  Su, Y. D.  Wang, X.  Liu, X.  Shen, X. J.  Zhang, Q. S.  Xing, L. H. Wang, Y. S. Chen, J. Biomater. Sci., Polym. Ed. 2018, 29, 1515; b) Z. G.  Ma, R.  Ma, X.  Wang, J. L.  Gao, Y. F.  Zheng, Z. J.  Sun, Eur. Polym. J. 2019, 118, 64.   \n[4]\t a) X. C.  Fan, L.  Yang, T.  Wang, T. D.  Sun, S. T.  Lu, Eur. Polym. J. 2019, 121, 109290; b) H.  Xue, L. C.  Hu, Y.  Xiong, X. W.  Zhu, C. Y.  Wei, F. 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+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Recent advances in photo-crosslinkable hydrogels for biomedical applications  \n\nJane Ru Choi\\*,‡,1,2, Kar Wey Yong\\*\\*,‡,3, Jean Yu Choi4 & Alistair C Cowie4",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# ABSTRACT  \n\nPhoto-crosslinkable hydrogels have recently attracted significant scientific interest. Their properties can be manipulated in a spatiotemporal manner through exposure to light to achieve the desirable functionality for various biomedical applications. This review article discusses the recent advances of the most common photocrosslinkable hydrogels, including poly(ethylene glycol) diacrylate (PEGDA), gelatin methacryloyl (GelMA) and methacrylated hyaluronic acid (MeHA), for various biomedical applications. We first highlight the advantages of photopolymerization and discuss diverse photosensitive systems used for the synthesis of photo-crosslinkable hydrogels. We then introduce their synthesis methods and review their latest state of development in biomedical applications, including tissue engineering and regenerative medicine, drug delivery, cancer therapies and biosensing. Lastly, the existing challenges and future perspectives of engineering photocrosslinkable hydrogels for biomedical applications are briefly discussed.",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# KEYWORDS:  \n\nbiosensing $\\cdot$ cancer therapies $\\cdot$ drug delivery • photo-crosslinkable hydrogels $\\cdot$ tissue engineering",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# INTRODUCTION  \n\nHydrogels have been widely investigated as matrices for biomedical applications (e.g., tissue engineering and biosensing) owing to their crosslinking abilities under mild conditions, excellent biocompatibility, and tunable biochemical and biophysical properties  [1–5]. As the structure and properties of hydrogels resemble the microenvironment of many human body tissues, they have been broadly used in a diverse range of biomedical applications [6,7]. To date, stimuli-responsive hydrogels have increasingly gained scientific interest. These materials can respond to various stimuli, including light, chemical and temperature to induce structural or morphological transitions  [8,9]. Among various stimuli, light stimulus (e.g.,  ultraviolet [UV] light and visible light) is considered as an ideal external control method to manipulate the properties of hydrogels owing to their several unique advantages. These include the abilities to: (i) control the stimulus easily by switching the light on and off; (ii) regulate light dosage precisely to achieve functional tunability; (iii) obtain independent spatial or temporal control of different biological processes in a wavelength-specific manner; (iv) direct the light to a confined location at user-defined times; as well as (v) to regulate a range of cellular processes in vivo in the optical tissue window [10,11]. These advantages have led to the extensive use of light for better control and modulation of hydrogels for numerous potential ­applications.  \n\nPhoto-crosslinkable hydrogels, including poly(ethylene glycol) diacrylate (PEGDA), gelatin methacryloyl (GelMA) and methacrylated hyaluronic acid (MeHA), have been extensively explored in biomedical fields, especially as 3D tissue engineered constructs, biosensing medium and drugcontrolled release matrices. This is due to their outstanding properties, such as good biocompatibility, hydrophilicity and biodegradability. For example, PEGDA hydrogel has been used in cartilage tissue engineering to mimic both static and dynamic mechanical properties of articular cartilage based upon their tunable mechanical properties [12]. GelMA hydrogel has been successfully used in the development of various 3D biomimetic in vitro healthy and disease tissue models for pathology and therapeutic studies [8]. MeHA hydrogels have been used in cancer therapy due to their abilities to target tumors for drug delivery applications [13].  \n\nThe escalating demand for photocrosslinkable hydrogel as a platform for biomedical applications presents a strong need for a timely review on a wide range of their biomedical applications, including tissue engineering and regenerative medicine, biosensing, drug delivery and cancer therapies. This review discusses the latest advances of photo-crosslinkable hydrogels for biomedical applications. The three commonly used photo-crosslinkable hydrogels, including PEGDA, GelMA and MeHA, are highlighted. The advantages of using these hydrogels along with their different synthesis methods are summarized. Their most recent advances in biomedical applications, including studies published between 2013 and 2018, are subsequently reviewed (Table 1). Finally, the existing challenges and future perspectives of photo-crosslinkable hydrogels are briefly discussed.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# PHOTOSENSITIVE SYSTEMFOR THE SYNTHESIS OFPHOTO-CROSSLINKABLEHYDROGELS  \n\nTo date, a variety of photo-crosslinkable hydrogels have been developed with tunable mechanical and chemical properties (e.g.,  swelling rate, degradability and mechanical strength) for various biomedical applications  [14]. As aforementioned, compared with other stimuli (e.g., pH or temperature), light stimulus is an interesting option as it can be easily controlled to precise locations at defined times and produce hydrogel structures with desirable properties [15]. A photosensitive system usually consists of photoinitiators, pre-polymers, and/or other components such as therapeutic molecules, cells and so on. The use of light energy (i.e., visible light [400–800 nm] or UV [200–400 nm]) enables polymerization of pre-polymer at low initiating radical doses under mild reaction conditions (i.e., in physiological aqueous solution at room temperature) [16]. The spatiotemporal control and resolution conferred by the light are essential to trigger the photopolymerization of pre-polymer in the presence of photoinitiator and induce the photosensitive bond cleavage to introduce specific biochemical functionalities to the hydrogel. The photopolymerization reaction and photoinitiators will be briefly discussed in the following sections.  \n\nTABLE 1. Properties and biomedical applications of photo-crosslinkable hydrogels.   \n\n\n<html><body><table><tr><td colspan=\"3\"></td></tr><tr><td>Hydrogel</td><td>Properties</td><td>Biomedical applications</td></tr><tr><td>PEGDA</td><td>Low degradation rate</td><td>Drug delivery [35,38-40.47] and detoxification [45]</td></tr><tr><td>PEGDA</td><td>Non-cell adhesive and tunable mechanical strength</td><td>In vitro cancer model []</td></tr><tr><td>PEGDA - HA/GelMA/collagen</td><td>Cell-adhesive and tunable mechanical prop- erties</td><td>Tooth [31l, vascular [32], bone [41]l and heart valve tissue engineering [52]; invitro liver tis- sue model [51]</td></tr><tr><td>PEGDA- polyaniline</td><td>Enhancement of electrical conductivity</td><td>Nerve tissue engineering [48]</td></tr><tr><td>PEGDA</td><td>High resistance to swelling in aqueous en- vironment</td><td>Biosensing [36]</td></tr><tr><td>GelMA</td><td>Cell-adhesive and tunable mechanical strength</td><td>Tooth [62],cartilage [78]and nerve tissue engi- neering73l;invitrofibroticcardiac69thro- bosis [79], liver tissue [80] and glioblastoma model [81]</td></tr><tr><td>GelMA</td><td>Tissue-adhesive</td><td>Lung and skin wound healing [67,74]</td></tr><tr><td>GelMA - MeHA/heparin/gellan gum</td><td>Chondroinductive</td><td>Cartilage tissue engineering [82-85]</td></tr><tr><td>GelMA-nanosilicate/hydroxyapatite</td><td>Osteoinductive</td><td>Bone tissue engineering 68,7,86]</td></tr><tr><td>GelMA - graphene oxide/carbon nanotubes</td><td>Enhancement of electrical conductivity</td><td>Cardiac tissue engineering [87,88</td></tr><tr><td>GelMA - methacryloyl-substituted tropoelastin</td><td>Enhancement of tissue adhesive strength</td><td>Skin wound healing [92] and nerve repair [72]</td></tr><tr><td>GelMA-dopamine</td><td>Neuroinductive</td><td>Nerve repair [91]</td></tr><tr><td>GelMA - polyacrylamide/ chitosan nanopar- ticles</td><td>Reduction of degradation rate</td><td>Drug delivery [75,93]</td></tr><tr><td>GelMA- nickel nanoparticles + reduced graphene oxide</td><td>Enhancement of electron transfer capacity and glucose catalytic oxidation activity</td><td>Glucose biosensing [95]</td></tr><tr><td>MeHA</td><td>High tumour targeting ability</td><td>Drug delivery for cancer therapy [101,108,109]</td></tr><tr><td>MeHA</td><td>Cell-adhesive and tunable mechanical strength</td><td>Cartilage and bone tissue engineering [104,106]; in vitro CNS tissue model [110]</td></tr><tr><td>MeHA - methacrylated chondroitin sulfate/ devitalized cartilage microparticles/N-cad- herin mimetic peptides</td><td>Chondroinductive</td><td>Cartilage tissue engineering [98,112,113]</td></tr><tr><td>MeHA - puramatrix peptide</td><td>Neuroinductive</td><td>Nerve repair [111]</td></tr><tr><td>MeHA</td><td>Excellent hydrating function</td><td>Biosensing [102]</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# Photopolymerization reaction  \n\nIn general, photopolymerization reactions can be categorized into free-radicalinitiated chain polymerization and bio-orthogonal click reactions [17]. The former is the most common reaction used in the synthesis of hydrogels, which is normally based on methacrylate-functionalized pre-polymers and happens through a chain growth mechanism. The general processes of synthesizing three common photo-crosslinkable hydrogels, PEGDA, GelMA and MeHA, based on this reaction are shown in Figure 1. Briefly, in the presence of a light source, the photons absorbed by the photoinitiators promote their cleavage, leading to the formation of free radical molecules. These reactive molecules then react with the vinyl bonds in the pre-polymer (i.e., PEGDA, GelMA or MeHA), leading to the formation of chemical crosslinks between the polymer chains [18]. This polymerization reaction allows the synthesis of hydrogels with tunable $\\blacktriangleright$ $\\blacktriangleright$ mechanical properties and degradation rate. However, radical-initiated chaingrowth polymerization possesses a few limitations. First, the inhibition effect of oxygen in the reaction has always been a key issue, as it leads to the production of peroxy radicals that can hardly contribute to the polymerization reaction [17,19]. This issue also causes a decrease in both polymerization rate and final conversion ratio, which results in the production of undesirable, highly viscous substances. Other limitations of radical-initiated chaingrowth polymerization include nonstructural heterogeneities in the polymer network, inefficient control of crosslinking polymerization kinetics, and the residual unreacted double bonds that might react negatively with biological molecules, which stem from the random chain p­olymerization [20].  \n\nBio-orthogonal click reaction enables the development of hydrogels with consistent structure and minimal network defects based on the step-growth polymerization reaction  [21]. Compared with chain-growth polymerization, this reaction is insensitive to oxygen and water, and is able to perform under mild conditions with faster kinetics, greater efficiency and selectivity [22]. The thio-norbornene (thiol-ene) photoclick reaction, in particular, has emerged as a widely used method for synthesis of hydrogel. In the presence of light irradiation, the thiol-ene reaction triggers the addition of thiols to carbon– carbon double bonds in pre-polymers in a rapid manner, generating thioether bonds [23]. Like free-radical-initiated chain polymerization, this reaction enables the manipulation of mechanical properties and degradation rate of hydrogel [22,24]. Importantly, this reaction induces a low risk of cytotoxic effects to the cells, which makes it suitable for diverse biomedical applications, especially for tissue engineering a­pplications [22]. To date, the practical applications of thiol-ene photoclick reaction remain challenging, as thiolcontaining small molecules have limited shelf life stability (several hours to several days) and they rely on stabilizers [25].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# Photoinitiators for photopolymerization  \n\nSelecting a suitable photoinitiator is imperative to ensure a desirable polymerization rate and to achieve optimum functionality for biomedical applications. For instance, using an appropriate photoinitiator could prevent undesirable cytotoxic effects for encapsulation of cells in tissue engineering applications [26]. Several key characteristics should be considered when selecting a photoinitiator, which include absorption spectrum, molar extinction coefficient, water solubility, stability and ability to produce free radicals [23,26].  \n\nGenerally, there are two main categories of photoinitiators that are currently used in the synthesis of hydrogels for biomedical applications: radical and cationic photoinitiators [26]. The former represents the most widely used photoinitiator owing to their excellent biocompatibility. By contrast, the utilization of cationic photoinitiators would lead to the formation of protonic acids that might be harmful to cells, which significantly restricts their applications [16]. In fact, radical photoinitiators are divided into two types: photo-cleavable (type I) and biomolecular (type II) photoinitiators, based on their mechanism in the production of free radicals. Type I photoinitiators such as benzoin derivatives and acetophenone derivatives have been commonly used [24]. Upon exposure to light, type I photoinitiators take up incident photons and decay into two primary radicals that initiate the photocrosslinking reaction. Type II photoinitiators, such as camphorquinone, thioxanthone and benzophenone, extract the hydrogen present in co-initiator to generate secondary radicals for the crosslinking process [23]. They have attracted considerable attention due to their utility in visible light-mediated polymerization.  \n\nWhen selecting the photoinitiators, the main concern is the potential cytotoxicity effect of free radicals produced by photoinitiators, especially for the application of tissue engineering [27]. Free radicals in turn can react with major cell ­components such as nucleic acids or proteins, which may reduce cell viability and even cause DNA damage. The commonly used photoinitiators for biomedical applications are summarized in Table 2. Irgacure 2959 (1-[4-(2-hydroxyethoxy)-phenyl]- 2-hydroxy-2-methyl-1-propane-1-one) is the most broadly used UV light-sensitive photoinitiator, especially in the field of tissue engineering, due to its fascinating characteristics such as moderate water solubility, low cytotoxicity and minimal immunogenicity [27]. However, its low initiation efficiency and low molar extinction coefficient in the UV-A spectral range have motivated the search for alternative photoinitiators that exhibit enhanced efficiency and biocompatibility such as $^{2,2^{\\prime}}$ -azobis[2- methyl-N-(2-hydroxyethyl)propionamide] (VA-086) and lithium phenyl-2,4,6-trimethylbenzoylphosphinate (LAP)  [28]. Numerous efforts have been devoted to create the formulation of photosensitive systems that consists of visible-lightsensitive photoinitiators such as Eosin-Y, riboflavin and camphorquinone to alleviate possible harmful effects of UV irradiation on the encapsulated cells [23]. Compared with UV light-sensitive photoinitiators, visible light-sensitive photoinitiators are relatively less cytotoxic and highly watersoluble [29]. Their exceptional properties offer great promise for diverse applications. However, the key challenge is the rapidity of curing under visible light, as the energy level of the visible light is lower than that of UV light [16]. Therefore, more studies should be performed to improve the curing efficiency of pre-polymer under visible light. In short, selecting suitable photoinitiators is important to achieve desirable function of hydrogel for biomedical applications. The type and characteristics of each photoinitiator as well as the comparisons of both UV and visible photopolymerizations are summarized in Table 2.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# SYNTHESIS, PROPERTIES& RECENT BIOMEDICALA­PPLICATIONS OFPHOTO-CROSSLINKABLEHYDROGELS  \n\nPhoto-crosslinkable hydrogels basically consist of a photoreactive moiety that is usually made up of photochromic chromophore, and a polymeric network. The photochromic chromophore is photoresponsive upon light irradiation [3]. Generally, the optical signal is first captured by the photochromic chromophore, which in turn converts the optical signal to a chemical signal via a photoreaction, including isomerization, cleavage or dimerization [30]. The chemical signal is then transferred to the functional group of the hydrogel and attunes to its properties. The change in hydrogel properties may vary depending on their molecular structures and the photo-irradiation set-up [3]. The changes of hydrogel properties include elasticity, degree of swelling, and degradation, which are of interest for multiple biomedical applications. For instance, in the field of tissue engineering, the tunable properties of photo-crosslinkable hydrogels provide the dynamic and native cell microenvironment. These properties offer tremendous potential to study the unknown mechanisms of the complex cell microenvironment  [31–33]. For drug delivery, photo-crosslinkable hydrogels offer the opportunity for on-demand delivery of different therapeutics (e.g., drugs and growth factors) in a single cytocompatible hydrogel-based drugdelivery system with high loading efficiency. The hydrogel could achieve dose-controlled and timed release of drugs at desired sites for therapeutic a­pplications [34].",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# PEGDA hydrogel  \n\nPEG is a hydrophilic, water soluble and biocompatible polymer, which has been suggested for use in various biomedical applications [35]. The polymer is nontoxic at molecular weighs above 400 Da, has low immunogenicity, and is readily excreted from the human body. It has been approved by the US FDA for internal consumption. The PEG molecule is neutral, highly mobile and hydrated in aqueous solution [36]. It is naturally resistant to protein adsorption due to its limited protein binding sites and high mobility, and hence it does not support cell attachment [37]. PEGDA is a PEG derivative fabricated through substituting terminal hydroxyl groups of PEG with acrylates. It contains double-bond acrylate groups at each end of the PEG chain, allowing it to undergo free radical initiated chain photopolymerization in the presence of a photoinitiator molecule (e.g., Irgacure 2959) to form a 3D polymer network.  \n\nWhile PEGDA can be crosslinked by various methods, the utilization of photopolymerization is especially versatile for use in biomedical applications. In this regard, crosslinking can be induced through the addition of biocompatible photoinitiators in the presence of UV or visible light source [38]. PEGDA hydrogels can be synthesized rapidly and easily, and their mechanical properties can be readily tuned by varying the concentration or molecular weight (MW) of the polymer  [39]. These properties make it a promising biomaterial for various biomedical applications, including drug delivery, tissue engineering and biosensing [40–42].  \n\n![](images/45a05ea0093ff5ad8a074048ed6b56f16b761e23079e96ccf3b1bc7c78e06f5f.jpg)  \nFigure 1. Photopolymerization of PEGDA (A), GelMA (B) and MeHA (C) hydrogels via free-radical initiated chain polymerization. These images were adapted with permission from [109] $\\circledcirc$ Royal Society of Chemistry (2016) and [16]. GelMA: Gelatin methacryloyl; MeHA: Methacrylated hyaluronic acid; PEGDA: Poly(ethylene glycol) diacrylate.",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# Synthesis of photo-crosslinkable PEGDA hydrogel  \n\nTo synthesize PEGDA, PEG diol is first dissolved in benzene, followed by the removal of water through azeotropic distillation in toluene using a Dean-Stark trap  [43]. This is to ensure that the acrylation of PEG is carried out in a dry condition. The PEG acrylation is then carried out under argon by dissolving PEG in dichrolomethane solution with acryloyl chloride and triethylamine at a molar ratio of 1:1.5:1.5 of OH-groups of PEG: acryloyl chloride: triethylamine, respectively. The mixture is stirred in the dark at room temperature overnight. The product is then precipitated by the addition of diethyl ether and chilled to $4^{\\circ}\\mathsf{C}$ to eliminate toluene and subsequently recovered using filtration. Finally, the recovered PEGDA product is dried in a vacuum oven overnight.  \n\nTo synthesize PEGDA-based hydrogel, the PEGDA powder is dissolved in deionized water at a predetermined mass proportion (e.g., 0.25 g PEGDA/ml deionized water) [38]. Photoinitiator Irgacure 2959 is usually added to the PEGDA solution at $0.1\\%$ (w/v) and is subsequently exposed to UV light for a few minutes (e.g., $10{-}20\\mathrm{min})$ to complete photopolymerization. The mechanical properties of PEGDA hydrogel are tunable by varying MW cut-offs (MWCOs), which generally lie in the $\\mathsf{1}-50\\ \\mathsf{k D a}$ range; pre-polymer concentration; photopolymerization conditions, and so on. For example, by increasing the pre-polymer concentration from 5 to $25\\%$ , compressive modulus of PEGDA hydrogel was increased from 5 to 70 kPa [44] (Table 3). On the other hand, when the pre-polymer concentration was increased from 5 to $10\\%$ , hydrolytic degradation of PEGDA hydrogel was decreased from 20 to $10\\%$ after 28 days of $\\blacktriangleright$ $\\blacktriangleright$ incubation in phosphate-buffered saline (PBS). Due to its low degradation rate, PEGDA hydrogel acts as a stable medium to protect encapsulated drugs or functional nanoparticles for long-term drug release or detoxification, respectively [39,45]. However, in order to use PEGDA hydrogel for tissue engineering applications, the degradation rate of PEGDA hydrogel should be increased to allow cells to remodel their microenvironment or extracellular matrix [46]. The degradation rate of PEGDA hydrogel can be improved by combining it with other enzymatically or hydrolytically degradable materials [32]. For instance, degradation of PEGDA was increased up to $80\\%$ after 14 days of immersion in collagenase solution in which GelMA was added to form PEGDA/GelMA hybrid hydrogel for tooth tissue engineering [31].  \n\nTABLE 2. Types of photoinitiator commonly used for photo-crosslinking of PEGDA, GelMA and MeHA hydrogels.   \n\n\n<html><body><table><tr><td colspan=\"3\"></td><td colspan=\"4\">Photopolymerization system</td></tr><tr><td></td><td>Photoinitiator Type of</td><td></td><td>Hydro- Irradiation</td><td>Advantages</td><td>Disadvantages</td><td>Ref.</td></tr><tr><td>photoinitiator Irgacure 2959 (12959)</td><td>initiator Type I</td><td>Chemical structure</td><td>gel PEGDA GelMA</td><td>source UV light (320- 390 nm)</td><td>Moderate water solubility Low cytotoxic-</td><td>Low initiation efficiency Low molar extinction</td><td>[37, 40] [67,</td></tr><tr><td>Lithium phe- nyl-2,4,6-tri- methylbenzo-</td><td>Type I</td><td></td><td>MeHA PEGDA</td><td>UV light (320-</td><td>ity and minimal immunogenicity Rapid curing High water solubility</td><td>coefficient in the UV-A spectral range (320- 400 nm) UV rays may affect human health By using visible light polym- erization, the energy level</td><td>79] [104, 108] [45] </td></tr><tr><td rowspan=\"2\">ylphosphinate (LAP)</td><td></td><td></td><td>GelMA</td><td>390 nm) UV light (320-</td><td>Broader spectral</td><td>of the visible light is lower than UV light, therefore, the curing rate is usually slower than that of UV</td><td>[86] </td></tr><tr><td></td><td></td><td>GelMA</td><td>390 nm) Blue light (405 nm)</td><td>range (applicable with both UV and visible light source) Low health and safety riskswhen curing with blue</td><td>Low molar extinction coefficient in the visible light spectral range</td><td>[120]</td></tr><tr><td>Eosin-Y</td><td>Type II</td><td>Br Br HO1 Br Br OH</td><td>PEGDA GelMA light (450- 550 nm)</td><td>Visible light (400- 800 nm) Visible</td><td>light High water solubility High molar extinc- tion coefficient in thevisilaligbt (400-800 nm) Low health and safety risks</td><td>(400-800 nm) By using visible light poly- merization, the energy level of the visiblelight is lower than Uv light, therefore, the cuainthrate isusually slower Requires additional reagents for crosslinking reaction,</td><td>[52]</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# RECENT BIOMEDICAL APPLICATIONS OF PHOTO-CROSSLINKABLE PEGDA HYDROGEL",
+        "category": " Introduction"
+    },
+    {
+        "id": 12,
+        "chunk": "# Drug delivery  \n\nPhoto-crosslinkable PEGDA hydrogel is primarily used in drug delivery for therapeutic applications. UV-crosslinked PEGDA hydrogel was made into pharmaceutical tablets using 3D inkjet printing to control the release of ropinorole hydrochloride, a drug used for the treatment of Parkinson’s disease [38]. It has also been made into microneedles using a micromolding approach to deliver gap junction inhibitor (Gap 26) for repair of keloid scars via the transdermal route [40] (Figure 2A). In addition, PEGDA hydrogel can be used as an implant to control a sustained release of stromal cell-derived factor 1/glycoprotein VI, which promotes migration and engraftment of bone marrow-derived stem cells at the ischemic region of cardiovascular tissues for angiogenesis and cardiac regeneration  [35]. Due to the non-cell adhesive property of PEGDA hydrogel, it was used to encapsulate islets of Langerhans and maintain their round morphology, preserving their insulinsecreting ability. By combining with a vascularized hydrogel, this construct can be implanted for the treatment of diabetes [37]. To deliver the drug in harsh conditions in the human body (e.g., highly impermeable endothelium and extremely low pH), PEGDA hydrogel requires combination with other materials. For instance, a stent coated with swellable PEGDA/ polylactic acid-co-caprolactone hybrid hydrogel was developed to deliver the drug mitomycin C through the highly impermeable barrier of urothelium for treating diseases. This hybrid hydrogel firmly adheres to the urothelial mucosa and swells upon urine absorption, which enhances bioavailability of the drug at the urothelial diseased site  [39]. PEGDA/ chitosan-grafted-glycidyl methacrylate hybrid hydrogel functionalized with bone ash has been used to efficiently control the release of antibiotic amoxicillin in an extremely low pH condition (pH: 1.2, pH of the gastric environment), suggesting great potential as a drug carrier for treatment of gastric diseases [47].  \n\nTable 3. Modification of mechanical properties of photo-crosslinkable hydrogels for biomedical application.   \n\n\n<html><body><table><tr><td>Hydrogel</td><td>Pre-polymer concentration (w/v)</td><td>UV light exposure duration</td><td>Photoinitiator concentration (w/v)</td><td>Mechanical properties</td><td>Biomedical application</td></tr><tr><td>PEGDA</td><td>5-25%</td><td>5 min</td><td>1%</td><td>Compressive modulus (2- 70 kPa)</td><td>PEGDA hydrogel with different compressive modulus can be used to develop various types of 3D in vitro cancer models, such as breast cancer (5 kPa), gastrointestinal cancer (25 kPa), and bone cancer (50 kPa) [44].</td></tr><tr><td>GelMA</td><td>10-25%</td><td>3 min</td><td>0.5%</td><td>Adhesive strength (5- 49 kPa)Elastic modulus(175- 262 kPa)</td><td>25% GelMA hydrogel is an excel- lent sealant of air leakage for highly stressed elastic lung tissues due to its great adhesive strength (49 kPa) and elastic modulus (262 kPa) [67].</td></tr><tr><td>GelMA</td><td>5-15%</td><td>30 s</td><td>0.1%</td><td>Elastic modulus (1.5-12 kPa)</td><td>15% GelMA hydrogel with an elas- tic modulus of 12 kPa supported growth of odontoblast for engineer- ing of dental pulp tissue construct for tooth regeneration [62].</td></tr><tr><td>GelMA</td><td>3%</td><td>15-40 s</td><td>0.5%</td><td>Compressive modulus (0.68- 2.03 kPa)</td><td>UV light exposure for 15 s produced a more softer GelMA hydrogel (0.68 kPa), which is similar to that of native brain tissue, allowing neuro- nal differentiation of stem cells en- capsulated in the hydrogel for spinal cord repair [73],</td></tr><tr><td>GelMA</td><td>7%</td><td>2-10 min</td><td>10%</td><td>Young's modulus (290-350 kPa) Tensile strength (310-360 kPa)</td><td>UV light irradiation for 10 min gen- erated a GelMA hydrogelwith high elasticity (350 kPa) and tensile strength (360 kPa), which is com- parable with that of natural skin, for</td></tr><tr><td>MeHA</td><td>1-3%</td><td>10 min</td><td>0.1%</td><td>Elastic modulus (1.3-10.6 kPa)</td><td>efficient wound healing [74]. 2.5% MeHA hydrogel with an elastic modulus of 6.8 kPa is the optimal gel formulation for 3D bioprinting and bone tissue engineering [106],</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# Tissue engineering  \n\nIn addition to  drug delivery, PEGDA hydrogel has also been used for tissue engineering. The pristine PEGDA lacks cell adhesive properties. Due to this, it allows growth of cancer cells and formation of tumorspheres, indicating its great potential in developing various types of 3D in vitro cancer model, such as a breast cancer model, gastrointestinal cancer model and bone cancer model  [44]. However, in order to utilize it as a 3D cell culture platform for developing tissueengineered constructs or implants, it has to be combined with other biomaterials possessing cell adhesive properties, such as HA, GelMA, collagen and polyaniline [31,32,41,48]. PEGDA/GelMA hybrid hydrogel and PEGDA/collagen hybrid hydrogel were loaded with adult stem cells, respectively, for tooth and vascular r­egeneration [31,32]. PEGDA/HA hybrid hydrogel was employed to promote bone regeneration, which can be functionalized with laponite XLG nanoclay (a composite that releases bioactive ions ${\\mathsf{M}}{\\mathsf{g}}^{2+}$ and $\\blacktriangleright$  \n\n$\\mathsf{S i^{4+}}$ ) to create a favorable microenvironment for in vivo osteogenesis  [41] (Figure 2B). Besides providing matrix for cell adhesion, polyaniline also enhances electrical conductivity of PEGDA hydrogel and neuronal differentiation, making this hybrid hydrogel suitable for regeneration of nerve cells [48]. Moreover, a low-level laser treatment can be conducted on a cell-laden PEGDA-based hydrogel to promote neuronal differentiation for neural tissue regeneration. For example, a red laser light $(633\\mathsf{n m})$ with a low power output $(750\\mathsf{m w})$ has been used to induce neuronal differentiation and suppress glial differentiation of neural stem cells encapsulated in UV light-crosslinked PEGDA/GelMA hybrid hydrogel [49]. On the other hand, it is suggested that uniform-sized embryoid bodies (EBs) derived from embryonic stem cells should be formed in order to efficiently differentiate EBs into neuronal cells. To this end, a 3D PEGDA microwell was developed to enhance aggregation of embryonic stem cells due to its cell-repellent property, thus promoting formation of uniformsized EBs. Following encapsulation of such EBs in GelMA hydrogel, neurites were found to extend into both hydrogels to form neuronal networks. This construct can be used to develop various in vitro neural disease models, such as Alzheimer’s disease, for exploring new and effective therapies [50]. Aside from UV light-crosslinked PEGDA hydrogel, visible light-crosslinked PEGDA hydrogel functionalized with RGD peptides can also be used to develop in vitro liver tissue models and tissue engineered heart valves [51,52].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# Biosensing  \n\nPEGDA hydrogels have been used in the biosensing or fabrication of microfluidic devices due to their high resistance to swelling in an aqueous environment, thus reducing sample loss [36]. For instance, one study has introduced PEG-based microfluidic chips integrated with functionalized nanoporous alumina membrane for simultaneous electrochemical detection of Escherichia coli O157:H7 and Staphylococcus aureus [36]. In another study, PEGDA hydrogel was made into microparticles and conjugated with a specific antibody for the detection of clinically relevant markers (e.g., VEGF) based on silver precipitation, achieving a rapid and highly sensitive assay for pointof-care testing [53]. PEGDA have also been used in microfluidic devices as a barrier between the cell culture chambers and sensing chambers [42] (Figure 2C). Growth factors produced by hepatocytes diffuse into the sensing chamber through the hydrogel barrier, which were bound to the beads coated with fluorescence-tagged antibody. The fluorescence signal was then detected to determine the concentration of growth factors.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# Others  \n\nBesides mammalian cell culture, PEGDA hydrogel may be used as a barrier in a microbial cell culture platform for nutrient and oxygen transport to microbes, owing to its tunable mesh size [54]. Polydiacetylene nanoparticle-laden PEGDA hydrogel with liver-mimetic 3D microstructure has been used as a detoxification device to effectively capture and remove toxins from the human body [45] (Figure 2D).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# GelMA hydrogel  \n\nGelatin is a FDA-approved material for food processing. It is an attractive base material of hydrogels due to its biodegradability, biocompatibility and low antigenicity [55,56]. Gelatin is a hydrolysis product of collagen that contains many arginine-glycine-aspartic acid (RGD) sequences and target sequences of matrix metalloproteinase (MMP) that enhance cell attachment and remodeling of the cellular microenvironment, respectively [8,57]. However, gelatin hydrogel exhibits a relatively rapid degradation behavior and poor mechanical strength [58], restricting its biomedical applications. GelMA hydrogel, a gelatinbased hydrogel functionalized with methacrylic anhydride (MA), was first introduced in the year 2000 [59]. The methacrylation process has been proven to control degradation rate and improve the mechanical strength of gelatin [60,61]. This makes GelMA hydrogel suitable for various biomedical applications, including tissue engineering and regenerative medicine, drug, growth factor and gene delivery [62–64].",
+        "category": " Introduction"
+    },
+    {
+        "id": 17,
+        "chunk": "# Synthesis of photo-crosslinkable GelMA hydrogel  \n\nTo synthesize GelMA in the conventional manner, the first step is to methacrylate gelatin (substitution of methacryloyl groups on the hydroxyl and reactive amine groups of gelatin) in PBS $\\{{\\mathsf{p H}}=7.4\\}$ ) at $50^{\\circ}\\mathsf{C},$ producing the GelMA pre-polymer solution [59]. The next step is to terminate the methacrylation reaction by adding phosphate buffer solution followed by dialysis against deionized water using a dialysis tubing with MW cut-offs that range from 12 to $14~\\mathsf{k D a}$ for 5 to 7 days. The purpose of this step is to remove all the impurities with low MW (e.g., MA byproducts and unreacted MA) that are potentially cytotoxic. Finally, GelMA pre-polymers are produced by freeze-drying the dialyzed solution [8]. However, the conventional method requires MA concentrations more than tenfold higher than that of gelatin to produce GelMA with a high degree of methacrylation $(>85\\%)$ . This is because PBS is insufficient to maintain the pH of the reaction solution at neutral for methacrylation to take place efficiently due to the presence of a byproduct, methacrylic acid, which causes the solution to become acidic. Therefore, a novel and efficient GelMA synthesis method that involves the use of carbonate–bicarbonate (CB) buffer has been developed. Gelatin can be methacrylated in a CB buffer at a pH of 9 at $35-50^{\\circ}\\mathsf{C}$ to successfully reduce the concentration ratio of MA to gelatin down to 2.2-fold and generate GelMA with a higher degree of methacrylation $(96\\%)$ compared with  the conventional synthesis method [65].  \n\nGelMA pre-polymers (1 to $15\\%$ ) (w/v) form GelMA hydrogel constructs in the presence of an energy source (UV or visible light) and a photoinitiator using various microfabrication strategies (e.g.,  photopatterning, micromolding and bioprinting)  [8,55]. By increasing the pre-polymer concentration, elastic modulus and adhesive strength of GelMA hydrogel can be tuned [66,67]. For instance, when the pre-polymer concentration was increased from 10 to $25\\%$ , elastic modulus of GelMA hydrogel was found to increase from 175 to $262\\mathsf{k P a}$ , while the adhesive strength was increased from 5 to 49 kPa [67] (Table 3). Moreover, by adjusting the amount of MA, different degrees of methacrylation can be achieved, generating GelMA hydrogels with different mechanical properties. It has been reported that increasing the degrees of methacrylation enhanced the compressive modulus of GelMA hydrogel and reduced its degradation rate  [66,68,69]. Photo-crosslinking of GelMA via radical polymerization is usually performed using Irgacure 2959 in the presence of UV light [66,70]. Irgacure 2959, a water-soluble photoinitiator is usually added into GelMA, and dissociates into a ketyl- and benzoyl-free radical, which has a low risk of cytotoxicity upon UV light exposure [71]. Photoinitiator concentration and light exposure duration are other parameters that can be used to tune the mechanical properties of GelMA hydrogel [59]. For example, by increasing concentration of Irgacure 2959 from 0.1 to $0.5\\%$ (w/v), elastic modulus of GelMA hydrogel was increased from 7 to $10~\\mathsf{k P a}$ [62,72]. On the other hand, compressive modulus of GelMA hydrogel was increased from 0.68 to $2.03\\mathsf{k P a}$ when UV light exposure duration was increased from 15 to $40\\thinspace\\thinspace s$ (Table 3) [73] .  \n\nBesides mechanical properties, degradation rate of GelMA hydrogel can be tuned by varying the pre-polymer concentration and light exposure duration [62,67,74]. For instance, when the pre-polymer concentration was increased from 5 to $15\\%$ , enzymatic degradation of GelMA hydrogel was decreased from 83 to $22\\%$ after 1 day of incubation in collagenase solution [62]. On the other hand, when UV light exposure duration was increased from 2 to 10 min, degradation of GelMA hydrogel was decreased from 90 to $60\\%$ after 28 days of immersion in collagenase solution [74]. Moreover, some organic and inorganic materials such as chitosan nanoparticle, 4-arm PEG-tetraacrylate (PEGTA), methacryloyl-substituted tropoelastin and nickel have been shown to reduce the degradation rate of GelMA hydrogel [72,75–77]. In fact, the degradation rate of the GelMA-based hydrogel construct should match with the pace of neo-tissue formation for tissue engineering applications, or the drugrelease kinetics for drug-delivery applications [72,75].  \n\n![](images/3a33a9dedace78a6c94e09fc7f4231f1bfb509471d9790325352538b8338d741.jpg)  \nFigure 2. Biomedical applications of PEGDA hydrogel. (A) Microneedle-based drug delivery for treatment of skin disease; adapted with permission from [40]. (B) Bone regeneration; adapted with permission from [41]. (C) Sensing of cell-secreted GFs; adapted with permission from [42]. (D) Detoxification; adapted with permission from [45]. Cap: Capture; Det: Detector; GF: Growth factor; PDA: Polydiacetylene; PDLSC: Periodontal ligament stem cell; PEGDA: Poly(ethylene glycol) diacrylate.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# RECENT BIOMEDICAL APPLICATIONS OF PHOTO-CROSSLINKABLE GELMA HYDROGEL",
+        "category": " Introduction"
+    },
+    {
+        "id": 19,
+        "chunk": "# Tissue engineering  \n\nPhoto-crosslinkable GelMA hydrogel is primarily used for tissue engineering and regenerative medicine. UV light-crosslinked GelMA hydrogel has been used to create tissue engineered cartilage- and pre-vascularized dental pulp-like constructs for cartilage and tooth regeneration (Figure 3A), respectively [62,78]. Bioprinted articular cartilage-resident chondroprogenitor cellladen GelMA hydrogel construct was shown to be more effective in nonhypertrophic neo-cartilage formation than chondrocyteor mesenchymal stem cell-laden GelMA hydrogel construct [78]. In addition, GelMA hydrogel has been used for the engineering of 3D in vitro fibrotic cardiac and blood coagulation tissue models to study the fibrotic remodeling process in the heart, and thrombosis, respectively [69,79]. It has also been used to develop a liver-on-a-chip platform for drug toxicity assessments (e.g., acetaminophen toxicity) [80]. Moreover, transplantation of neural stem cells encapsulated in GelMA hydrogel was found to enhance neuronal regeneration and suppress glial scar formation in mouse spinal cord transection models, suggesting the potential therapeutic application of the construct in spinal cord injury [73]. Apart from UV light-crosslinked GelMA hydrogel, visible light-crosslinked GelMA hydrogel has been used to engineer 3D in vitro glioblastoma multiform tissue models for monitoring cancer progression and drug screening [81]. On the other hand, implantation of a cell-free UV light-crosslinked GelMA hydrogel into animal models of lung injury was found to be effective at sealing $\\blacktriangleright$ $\\blacktriangleright$ air leak (Figure 3B) and promote in vivo wound healing for skin regeneration [67,74]. GelMA sealant appears to be more suitable for clinical applications as it displays excellent adhesive properties compared with the commonly used PEG- and fibrin-based glues [67].  \n\nUsing GelMA hydrogel as a sole material may be suboptimal for biomedical applications. Therefore, incorporating other inorganic or organic components into GelMA is important to further improve its mechanical and chemical properties, as well as cell behavior (e.g., cell differentiation, proliferation and viability) [8]. For example, it was found that chondrocyte-laden pristine GelMA hydrogel shows deposition of extracellular matrix consisting of mainly collagen type I instead of collagen type II, indicating a poor quality of cartilage tissue construct [82]. By adding MeHA, heparin or gellan gum into the GelMA hydrogel construct, chondrocytes encapsulated in such 3D hybrid hydrogels maintain their chondrogenic phenotypes and increase the deposition of collagen type II [82–85]. For bone tissue engineering applications, GelMA hydrogel loaded with nanosilicate or hydroxyapatite was shown to enhance osteogenic differentiation of mesenchymal stem cells and bone mineralization in the absence of any osteoinducting factors [77,86]. Moreover, by incorporating a bioprinted vascular tissue construct into the nanosilicatemodified GelMA hydrogel, the osteogenic potential of mesenchymal stem cells and bone mineralization were further enhanced in the presence of osteoinducting factors and VEGF, suggesting that this vascularized 3D bone tissue construct could be potentially used as a bone transplant for bone regeneration [68]. A more stable and large-scale 3D vascularized tissue construct can be bioprinted by using a blended bioink consisting of GelMA hydrogel, sodium alginate and PEGTA, offering great promise for tissue repair and regeneration [76]. For cardiac tissue engineering, other materials such as reduced graphene oxide or carbon nanotubes were incorporated into GelMA hydrogel to increase its electrical conductivity for maturation of cardiomyocytes. Upon electrical stimulation, cardiomyocytes encapsulated in such hybrid hydrogels demonstrate higher expression of cardiac markers and faster spontaneous beating than those encapsulated in the pristine GelMA hydrogels [87,88]. GelMA/ black phosphorus hybrid hydrogel could also be a promising scaffold for such application [89]. For skin regeneration, it was shown that GelMA/MeHA hybrid hydrogels loaded with adipose-derived stem cells exhibit an excellent angiogenic potential for wound healing [90]. Additionally, dopamine (a neurotransmitter that regulates neuronal development) can be added into GelMA hydrogel to improve neuronal differentiation of neural stem cells [91]. To promote sutureless peripheral nerve repair, GelMA hydrogel can be functionalized with methacryloyl-substituted tropoelastin to enhance its adhesive strength to nerve tissue, which is approximately 15-fold higher than that of conventional fibrinbased adhesives [72]. With the incorporation of methacryloyl-substituted recombinant human tropoelastin into a visible light-crosslinked GelMA hydrogel, it exhibits excellent adhesive properties that are capable of promoting sutureless wound healing [92].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# Drug delivery  \n\nGelMA hydrogels have also been used in controlling the delivery of drugs and growth factors for therapeutic applications. For instance, GelMA/polyacrylamide hybrid hydrogel has been used to control the release of sodium nafcilin monohydrate, an antibiotic against Staphylococcus sp. bacteria  [93]. Moreover, by integrating a dielectrophoresis system with gold microparticleladen GelMA hydrogels, the controlled release of drugs was achieved with a concentration gradient for highthroughput drug screening applications  [34]. On the other hand, by incorporating chitosan nanoparticles into GelMA hydrogel, which provides a sustained release of basic fibroblast growth factor, this hybrid hydrogel can be used for angiogenesis in various diseases, par ticularly ischemic diseases [75]. Furthermore, a coacervate microdroplet-laden hydrogel consisting of GelMA and oxidized, methacrylated alginate was developed for the controlled release of growth factors to the encapsulated stem cells for stem-cell-based therapies [63] (Figure 3C). Last but not least, GelMA hydrogel functionalized with polyethylenimine and graphene oxide nanosheets has been used as a nonviral gene delivery system to exert gene therapy for the treatment of acute myocardial infarction [94].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# Biosensing  \n\nFor biosensing applications, GelMA hydrogel was functionalized with nickel nanoparticles and reduced graphene oxide to create a glucose sensor [95]. These nanomaterials enhance electron transfer capacity and glucose catalytic oxidation activity for electrochemical sensing of glucose. This sensor was successfully used to determine the concentration of glucose in human blood serum [95]. On the other hand, an intelligent wound dressing consisting of a GelMA hydrogel encapsulating a bacterial infection-responsive lipid vesicle and antimicrobials was developed for fluorescent detection and inhibition of pathogenic bacteria (e.g., S. aureus and Pseudomonos aeruginosa) [64] (Figure 3D). In the presence of pathogenic bacteria, the lipid vesicles were hydrolyzed by the enzymes or toxins secreted by the bacteria, thereby releasing detectable fluorescence signal (an indicator for infection) and antimicrobials. This sensor was used to detect and treat drug-resistant bacterial infections, which will potentially be useful for future clinical therapies.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# MeHA hydrogel  \n\nHA is a biocompatible nonsulfated glycosaminoglycan composed of repeating disaccharide units of N-acetylglucosamine and D-glucuronic acid that is abundantly present in large amounts in tissues, including cartilage, neuron and skin  [96]. HA contains target sequences of hyaluronidases that can promote remodeling of the cellular microenvironment [97], and can specifically bind to hyaluronan receptors (CD44 and CD168), which are highly expressed by most tumor cells  [98]. However, HA hydrogel exhibits poor mechanical properties and rapid degradation [99], limiting its use in biomedical applications. To this end, manipulating methacrylation of HA is essential to achieve its optimum mechanical properties and control its degradation rate  [99,100], making MeHA hydrogel suitable for various biomedical applications, including tissue engineering and regenerative medicine, drug delivery and biosensing [98,101,102].",
+        "category": " Introduction"
+    },
+    {
+        "id": 23,
+        "chunk": "# Synthesis of photo-crosslinkableMeHA hydrogel  \n\nTo synthesize MeHA, the first step is to methacrylate HA (substitution of methacryloyl groups on the hydroxyl and reactive amine groups of HA) in deionized water $\\mathsf{\\langle p H}=8.0{-}8.5)$ at $4^{\\circ}\\mathsf{C}$ for producing the MeHA pre-polymer solution  [98,103]. Subsequently, the pre-polymer solution is dialyzed using a dialysis tubing with MW cut-offs that range from 6 to $8~\\textmu\\textmu$ for 2–3  days to remove all the MA byproducts and unreacted MA [98,104]. Finally, the MeHA pre-polymers are produced by freeze-drying the dialyzed solution. These pre-polymers (0.25 to $4.0\\%\\AA)$ ) (w/v) can be used to fabricate MeHA hydrogel constructs in the presence of UV light and Irgacure 2959 through various microfabrication strategies (e.g., electrospinning, micromolding and bioprinting)  [105,106]. Similar to GelMA hydrogel, the mechanical properties of MeHA hydrogel can be tuned by varying the pre-polymer concentration or light exposure duration [106,107]. For instance, elastic modulus of MeHA hydrogel was increased from 1.3 to $10.6~\\mathsf{k P a}$ when the pre-polymer concentration was increased from 1 to $3\\%$ (w/v) [106] (Table 3). Besides mechanical properties, the degradation rate of MeHA hydrogel can be adjusted by varying its pre-polymer concentration. When the pre-polymer concentration was increased from 1 to $3\\%$ , enzymatic degradation of MeHA hydrogel was decreased from 100 to $50\\%$ after 1  day of incubation in hyaluronidase solution  [106]. High degradability of MeHA hydrogel is imperative for cell remodeling in 3D tissueengineered constructs [103].  \n\n![](images/52e90e1ae5ab44c59c8a6717e3e5e3c82a187435ed7a46c4222ae6a4aa4470ba.jpg)  \nFigure 3. Biomedical applications of GelMA hydrogel. (A) Tooth regeneration; adapted with permission from [62]. (B) Air leak sealant; adapted with permission from [67] $\\circledcirc$ Elsevier (2017). (C) Growth factor delivery for stem-cell based therapy; reproduced with permission from [63] $\\circledcirc$ John Wiley & Sons (2015). (D) Sensor in wound dressing for the detection and inhibition of pathogenic bacteria; adapted with permission from [64] $\\circledcirc$ Elsevier (2018). GelMA: Gelatin methacryloyl; hMSCs: Human mesenchymal stem cells; OMA: Oxidized, ­methacrylated alginate.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 24,
+        "chunk": "# RECENT BIOMEDICAL A­PPLICATIONS OF P­HOTOCROSSLINKABLE MEHA HYDROGEL",
+        "category": " Introduction"
+    },
+    {
+        "id": 25,
+        "chunk": "# Drug delivery for cancer therapy  \n\nMeHA hydrogel has a high tumor targeting capability. For example, HA is a natural ligand to hyaluronan receptor (e.g., CD44), which is overexpressed in various types of tumors, suggesting its great potential in drug delivery and cancer therapy [108]. UV light-crosslinked MeHA hydrogel was incorporated with upconversion nanoparticles to deliver carboxyl group-modified zinc phthalocyanines (a photosensitizer), which can generate an abundance of singlet oxygen upon activation using near-infrared light to kill gastric cancer cells [109]. MeHA hydrogel was also incorporated with drug-loaded mesoporous silica nanoparticles (a sonosensitizer) to achieve a chemotherapy-sonodynamic therapy for the treatment of breast cancer [101] (Figure 4A). To further increase tumor target and drug delivery efficiency, endosome membrane components from cancer cells have been used to encapsulate  \n\nMeHA hydrogel loaded with doxorubicin. This enables the drug-loaded hydrogel to be uptaken easily and specifically by cancer cells for effective cancer chemotherapy [108] (Figure 4B).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 26,
+        "chunk": "# Tissue engineering  \n\nAs HA is a major ECM component for CNS development, UV light-crosslinked MeHA hydrogels were used to engineer 3D in vitro CNS normal and disease tissue models for the study of CNS diseases and regeneration [110]. MeHA hydrogels have also been used to generate tissue engineered cartilageand bone-like tissue constructs for cartilage and bone regeneration, respectively [104,106]. To further improve biofunctionality of MeHA hydrogel, incorporating other organic or inorganic components into it can enhance its mechanical and chemical properties. For nerve repair, combination of MeHA hydrogel with puramatrix peptide hydrogel could improve neurite extension or outgrowth [111]. Moreover, MeHA hydrogels have been electrospun into aligned nanofibers and incorporated with poly-lactic-co-glycolic $\\blacktriangleright$ images generated from computer-aided design software. Stereolithography has many advantages over other bioprinting techniques. First, it is nozzle-free, indicating that cells are not subjected to external force during printing of cell-laden hydrogel constructs, which ensures high cell viability. Moreover, compared with other bioprinting techniques, it has a relatively faster printing speed, greater vertical printing ability and higher resolution at minimal cost. Stereolithography has been used to fabricate a 3D detoxifier with four layers of liver-mimetic structure made up of PEGDA-based hydrogel [45]. Additionally, stereolithography has demonstrated its capability to print 3D in vitro cell-laden tissue models made up of GelMA-based hydrogel, such as a tumor angiogenesis model, skeletal muscle model and tendon-to-bone insertion model [117]. However, most of the stereolithographybased bioprinting systems still rely on harmful UV light. Therefore, many efforts have been devoted to printing 3D photocrosslinkable hydrogel structures for biomedical applications using stereolithography under visible light.  \n\n![](images/c1e9bd3c0a9ad29d2928042aee83601591a7dd00b457d17b1d687e9fea1b9856.jpg)  \nFigure 4. Biomedical applications of MeHA hydrogel. (A) Synergistic cancer chemotherapy and sonodynamic therapy; adapted with permission from [101] $\\circledcirc$ Royal Society of Chemistry (2017). (B) Targeted cancer chemotherapy; adapted with permission from [108]. (C) Cartilage tissue engineering; adapted with permission from [98]. (D) Microneedle-based extraction of skin ISF for metabolite sensing; adapted with permission from [102] $\\circledcirc$ John Wiley & Sons (2017). COL2: Collagen type 2; CS: Chondroitin sulphate; Dox: Doxorubicin; EM-NG: Endosome membranenanogel; HAase: Hyaluronidase; ISF: Interstitial fluid; MeHA: Methacrylated hyaluronic acid; MN: Microneedle; ROS: Reactive oxygen species; UV: Ultraviolet.  \n\n$\\blacktriangleright$ microspheres to control the release of nervous growth factor for peripheral nerve repair and regeneration [105]. Cells (chondrocytes or mesenchymal stem cells) are encapsulated in MeHA hydrogels functionalized with methacrylated chondroitin sulfate, devitalized cartilage microparticles or N-cadherin mimetic peptides (Figure 4C). These encapsulated cells demonstrate increased expression of cartilage markers and deposition of collagen type II compared with those encapsulated in pristine MeHA hydrogels  [98,112,113]. In addition, MeHA/GelMA hybrid hydrogel has been used to engineer 3D in vitro fibrotic heart valve tissue models for understanding the process of fibrotic remodeling and calcification in heart valve diseases [107,114,115].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 27,
+        "chunk": "# Biosensing  \n\nDue to the excellent hydrating functions of HA, MeHA hydrogel has been used to make a microneedle patch for extraction of skin interstitial fluid (ISF) for biosensing applications. This microdevice is capable of detecting and analyzing the metabolites in ISF, such as cholesterol and glucose, in a rapid and minimally invasive manner [102] (Figure 4D).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 28,
+        "chunk": "# FUTURE PERSPECTIVE  \n\n3D bioprinting techniques (e.g., inkjet printing, extrusion printing, laser-assisted printing and stereolithography) are valuable tools for the fabrication of 3D tissue-engineered constructs and hydrogel-based biomedical devices due to their ability to precisely fabricate external geometries and complex internal architectures  [116]. Specifically, stereolithography is the most advanced technique for printing photo-crosslinkable hydrogels. In fact, stereolithography produces complex 3D structures using a layer-by-layer approach by spatially controlling photopolymerization of photo-crosslinkable hydrogel solutions under UV or visible light based on  \n\nThere are many challenges associated with the clinical translation of photocrosslinkable hydrogels that need to be addressed. As aforementioned, the sole PEGDA hydrogel is lacking strong cell adhesion peptides, making it less effective for 3D cell culturing. Therefore, more studies should focus on combining PEGDA with other materials with strong cell adhesive properties (e.g., GelMA, HA, etc) to produce a hybrid ECM-mimicking hydrogel. This can effectively help to rebuild new ECM for tissue engineering and drug delivery applications. Recently, it was reported that type B GelMA hydrogel that contains bovine gelatin exhibits good biocompatibility. However, type A GelMA that contains porcine gelatin may induce inflammatory reactions [118]. Therefore, further biosafety assessments on GelMA-based tissue-engineered constructs are required prior to clinical applications to minimize biosafety concerns. Other challenges in clinical translation of GelMAbased tissue engineered constructs are potential disease transmission associated with the use of animal-based materials and batch-to-batch variations. Hence, it is imperative to develop a human-derived gelatin as an alternative to animal-based gelatin.  \n\nIn addition, a standardized protocol for synthesis of GelMA should also be established and implemented across all laboratories. MeHA hydrogel can only be used to culture limited types of cells (e.g., chondrocytes, neurons), compared with GelMA hydrogel, due to the inherent properties of HA. Therefore, incorporating functional peptide (e.g., RGD peptides) into MeHA is important, in particular to achieve a broader range of tissue engineering applications.  \n\nPhoto-crosslinkable tissue-engineered hydrogel constructs have not been fully applied in clinical applications due to restrictions with regard to their biosafety concerns associated with exposure to UV light, for example oxidative damage to cellular DNA, cancer formation and accelerated tissue aging, limiting their use as implants for tissue repair and regeneration  [119]. To address these issues, visible light with wavelengths of $450\\mathrm{-}550\\ \\mathrm{nm}$ could be an alternative light source for crosslinking of photo-crosslinkable hydrogels. Visible light can deeply penetrate tissues with relatively low energy, making it suitable for the development of in situ injectable hydrogels for in vivo applications in a minimally invasive manner. Additionally, near-infrared irradiation, which is harmless and able to penetrate tissues, could also be used to induce the in situ formation of hydrogel for various biomedical applications (e.g., cancer therapy). Biosafety assessments of both cell-free and cell-laden photo-crosslinkable hydrogels are important to ensure the safe and effective use of hydrogels.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 29,
+        "chunk": "# CONCLUSION  \n\nIn conclusion, photo-crosslinkable hydrogels such as PEGDA, GelMA and MeHA can be readily photo-crosslinked to achieve desirable mechanical properties and biological responses in a spatiotemporal manner, making them a versatile platform for various biomedical applications (e.g.,  tissue engineering, drug delivery and cancer therapy). In particular, PEGDA hydrogel is highly tunable and is more easily synthesized than GelMA and MeHA, and its mechanical and physical properties can be readily tuned by varying the concentration and molecular weight of the polymers. These properties make it highly suitable for a wide range of biomedical applications. As for the GelMA hydrogel, its tunable mechanical properties and the presence of functional RGD peptides make it an essential material for the development of various types of 3D tissueengineered implants and in vitro tissue models for regenerative medicine. MeHA hydrogel has high tumor target efficiency, and hence it is widely used for cancer therapy. With many opportunities and remaining challenges, we envision that there will be more studies focusing on photo-crosslinkable hydrogels dedicated to biomedical applications in the future.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 30,
+        "chunk": "# AUTHOR CONTRIBUTIONS  \n\nJRC and KWY contributed to the conception and design of the work. All authors participated in the discussions and writing of the manuscript. All authors reviewed and approved the final version of the manuscript for submission.",
+        "category": " References"
+    },
+    {
+        "id": 31,
+        "chunk": "# FINANCIAL & COMPETING INTERESTS DISCLOSURE  \n\nThis work was supported by Michael Smith Foundation for Health Research; and Office of Vice President Research, University of Calgary. The authors have no other relevant affiliations or financial involvement with any organization or entity with a financial interest in or financial conflict with the subject matter or materials discussed in the manuscript apart from those disclosed.  \n\nNo writing assistance was utilized in the production of this manuscript.",
+        "category": " References"
+    },
+    {
+        "id": 32,
+        "chunk": "# OPEN ACCESS  \n\nThis work is licensed under the AttributionNonCommercial-NoDerivatives 4.0 Unported License. To view a copy of this license, visit http://creativecommons.org/licenses/by-ncnd/4.0/",
+        "category": " Abstract"
+    },
+    {
+        "id": 33,
+        "chunk": "# REFERENCES  \n\nPapers of special note have been highlighted as: • of interest; •• of considerable interest  \n\n1.\t Choi JR, Yong KW, Tang R et al. Lateral flow assay based on paper–hydrogel hybrid material for sensitive pointof-care detection of dengue virus. Adv. Healthcare Mater.   \n6(1), (2017).   \n2.\t Li J, Mo L, Lu C-H, Fu T, Yang H-H, Tan W. Functional nucleic acid-based hydrogels for bioanalytical and biomedical applications. Chem. Soc. Rev. 45(5), 1410–1431 (2016).",
+        "category": " References"
+    },
+    {
+        "id": 34,
+        "chunk": "# EXECUTIVE SUMMARY",
+        "category": " Abstract"
+    },
+    {
+        "id": 35,
+        "chunk": "# PHOTOPOLYMERIZATION REACTION  \n\n●● There are two photopolymerization reactions: free radical initiated chaingrowth polymerization and bio-orthogonal click reaction. ●● Photo-crosslinkable hydrogels such as poly(ethylene glycol) diacrylate (PEGDA), gelatin methacryloyl (GelMA) and methacrylated hyaluronic acid (MeHA), are generally synthesized through free radical initiated chain-growth polymerization.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 36,
+        "chunk": "# PHOTOINITIATORS FORP­HOTOPOLYMERIZATION  \n\n●● Commonly used radical photoinitiators for photopolymerization of PEGDA, GelMA and  \n\nMeHA are Irgacure 2959, lithium phenyl2,4,6-hydroxyethyl)propionamide and Eosin-Y.  \n\n●● Both UV light-sensitive photoinitiators (e.g.,  Irgacure 2959) and visible lightsensitive photoinitiators (e.g., Eosin-Y) have some advantages and disadvantages.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 37,
+        "chunk": "# PEGDA HYDROGEL  \n\n●● PEGDA hydrogel is mainly used in drug delivery, as it acts as a stable medium to protect encapsulated drugs for long-term controlled release of drugs, due to its low degradation rate.",
+        "category": " Introduction"
+    },
+    {
+        "id": 38,
+        "chunk": "# GELMA HYDROGEL  \n\n●● GelMA hydrogel contains functional arginine, glycine, and aspartat peptides, making it an essential material in tissue engineering especially for the development of various types of biomimetic 3D tissueengineered implants and in vitro tissue models.",
+        "category": " Introduction"
+    },
+    {
+        "id": 39,
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Yield stress determines bioprintability of hydrogels based on gelatin-methacryloyl and gellan gum for cartilage bioprinting. Biofabrication 8(3), 035003 (2016).   \n86.\t Wenz A, Borchers K, Tovar GE, Kluger PJ. Bone matrix production in hydroxyapatite-modified hydrogels suitable for bone bioprinting. Biofabrication 9(4), 044103 (2017).   \n87.\t Shin SR, Zihlmann C, Akbari M et al. Reduced graphene oxide-gelMA hybrid hydrogels as scaffolds for cardiac tissue engineering. Small 12(27), 3677–3689 (2016).   \n88.\t Ahadian S, Yamada S, Ramón-Azcón J et al. Hybrid hydrogel-aligned carbon nanotube scaffolds to enhance cardiac differentiation of embryoid bodies. Acta Biomater. 31, 134–143 (2016).   \n89.\t Choi JR, Yong KW, Choi JY et al. Black phosphorus and its biomedical applications. Theranostics 8(4), 1005–1026 (2018).   \n90.\t Eke G, Mangir N, Hasirci N, Macneil S, Hasirci V. Development of a UV crosslinked biodegradable hydrogel containing adipose derived stem cells to promote vascularization for skin wounds and tissue engineering. Biomaterials 129,  \n\n188–198 (2017).  \n\n92.\t Annabi N, Rana D, Sani ES et al. Engineering a sprayable and elastic hydrogel adhesive with antimicrobial properties for wound healing. Biomaterials 139, 229–243 (2017).   \n93.\t Serafim A, Tucureanu C, Petre D-G et al. One-pot synthesis of superabsorbent hybrid hydrogels based on methacrylamide gelatin and polyacrylamide. Effortless control of hydrogel properties through composition design. New J. Chem. 38(7), 3112–3126 (2014).   \n94.\t Paul A, Hasan A, Kindi HA et al. Injectable graphene oxide/hydrogel-based angiogenic gene delivery system for vasculogenesis and cardiac repair. ACS Nano 8(8), 8050–8062 (2014).   \n95.\t Darvishi S, Souissi M, Kharaziha M, Karimzadeh F, Sahara R, Ahadian S. Gelatin methacryloyl hydrogel for glucose biosensing using Ni nanoparticles-reduced graphene oxide: an experimental and modeling study. Electrochim. Acta 261, 275–283 (2018).   \n96.\t Burdick JA, Prestwich GD. Hyaluronic acid hydrogels for biomedical applications. Adv. Mater. 23(12), (2011).   \n97.\t Lei Y, Gojgini S, Lam J, Segura T. The spreading, migration and proliferation of mouse mesenchymal stem cells cultured inside hyaluronic acid hydrogels. Biomaterials 32(1), 39–47 (2011).   \n98.\t Bian L, Guvendiren M, Mauck RL, Burdick JA. Hydrogels that mimic developmentally relevant matrix and N-cadherin interactions enhance MSC chondrogenesis. Proc. Natl Acad. Sci. USA 110(25), 10117–10122 (2013).   \n99.\t Tavsanli B, Okay O. Mechanically strong hyaluronic acid hydrogels with an interpenetrating network structure. Eur. Polym. J. 94, 185–195 (2017).   \n100.\tSahoo S, Chung C, Khetan S, Burdick JA. Hydrolytically degradable hyaluronic acid hydrogels with controlled temporal structures. Biomacromolecules 9(4), 1088–1092 (2008).   \n101.\tDing Y, Song Z, Liu Q et al. An enhanced chemotherapeutic effect facilitated by sonication of MSN. Dalton Trans. 46(35), 11875–11883 (2017). MeHA hydrogel was incorporated with drug-loaded mesoporous silica nanoparticles (a sonosensitizer) to effectively kill target cancer cells through synergistic chemotherapy and sonodynamic therapy.   \n102.\tChang H, Zheng M, Yu X et al. A swellable microneedle patch to rapidly extract skin interstitial fluid for timely metabolic analysis. Adv. Mater. 29(37), (2017). MeHA hydrogel was made into a microneedle patch to extract skin interstitial fluid for the sensing of metabolites, such as glucose and cholesterol, in a rapid and minimally invasive manner.   \n103.\tGwon K, Kim E, Tae G. Heparin-hyaluronic acid hydrogel in support of cellular activities of 3D encapsulated adipose derived stem cells. Acta Biomater. 49, 284–295 (2017).   \n104.\tLin S, Lee WYW, Feng Q et al. Synergistic effects on mesenchymal stem cell-based cartilage regeneration by chondrogenic preconditioning and mechanical stimulation. Stem Cell Res. Ther. 8(1), 221 (2017).   \n105.\tWhitehead TJ, Avila COC, Sundararaghavan HG. Combining growth factor releasing microspheres within aligned nanofibers enhances neurite outgrowth. J. Biomed. Mater. Res., Part A 106(1), 17–25 (2018).   \n106.\tPoldervaart MT, Goversen B, De Ruijter M et al. 3D bioprinting of methacrylated hyaluronic acid (MeHA) hydrogel with intrinsic osteogenicity. PloS One 12(6), e0177628 (2017).   \n107.\tDuan B, Yin Z, Kang LH, Magin RL, Butch  \n\n91.\t Zhou X, Cui H, Nowicki M et al. Three-dimensional-bioprinted dopamine-based matrix for promoting neural regeneration. ACS Appl. Mater. Interfaces 10(10), 8993–9001 (2018).  \n\ner JT. Active tissue stiffness modulation controls valve interstitial cell phenotype and osteogenic potential in 3D culture. Acta Biomater. 36, 42–54 (2016).   \n108.\tYu J, Zhang Y, Sun W et al. Internalized compartments encapsulated nanogels for targeted drug delivery. Nanoscale 8(17), 9178–9184 (2016).   \n109.\tZhou L, Chen E, Jin W, Wang Y, Zhou J, Wei S. Monomer zinc phthalocyanine/ upconversion nanoparticle coated with hyaluronic acid crosslinked gel as NIR light-activated drug for in vitro photodynamic therapy. Dalton Trans. 45(38), 15170–15179 (2016).   \n110.\tWu S, Xu R, Duan B, Jiang P. Three-dimensional hyaluronic acid hydrogel-based models for in vitro human iPSC-derived NPC culture and differentiation. J. Mater. Chem. B 5(21), 3870–3878 (2017).   \n111.\tKhoshakhlagh P, Moore MJ. Photoreactive interpenetrating network of hyaluronic acid and Puramatrix as a selectively tunable scaffold for neurite growth. Acta Biomater. 16, 23–34 (2015).   \n112.\tHayami JW, Waldman SD, Amsden BG. Chondrocyte generation of cartilage-like tissue following photoencapsulation in methacrylated polysaccharide solution blends. Macromol. Biosci. 16(7), 1083–1095 (2016).   \n113.\tBeck EC, Barragan M, Libeer TB et al. Chondroinduction from naturally derived cartilage matrix: a comparison between devitalized and decellularized cartilage encapsulated in hydrogel pastes. Tissue Eng., Part A 22(7–8), 665–679 (2016).   \n114.\tDuan B, Hockaday LA, Kapetanovic E, Kang KH, Butcher JT. Stiffness and adhesivity control aortic valve interstitial cell behavior within hyaluronic acid based hydrogels. Acta Biomater. 9(8),   \n7640–7650 (2013).   \n115.\tDuan B, Kapetanovic E, Hockaday LA, Butcher JT. Three-dimensional printed trileaflet valve conduits using biological hydrogels and human valve interstitial cells. Acta Biomater. 10(5), 1836–1846 (2014).   \n116.\tWang Z, Abdulla R, Parker B, Samanipour R, Ghosh S, Kim K. A simple and high-resolution stereolithography-based   \n3D bioprinting system using visible light crosslinkable bioinks. Biofabrication 7(4),   \n045009 (2015).   \n117.\tMiri AK, Nieto D, Iglesias L et al. Microfluidics-enabled multimaterial maskless stereolithographic bioprinting. Adv. Mater.   \n30(27), 1800242 (2018).   \n118.\tSirova M, Vlierberghe SV, Matyasova V et al. Immunocompatibility evaluation of hydrogel-coated polyimide implants for applications in regenerative medicine. J. Biomed. Mater. Res., Part A 102(6),   \n1982–1990 (2014).   \n119.\tBryant SJ, Nuttelman CR, Anseth KS. Cytocompatibility of UV and visible light photoinitiating systems on cultured NIH/3T3 fibroblasts in vitro. J. Biomater. Sci., Polym. Ed. 11(5), 439–457 (2000).   \n120.\tCalderon G, Thai P, Hsu C et al. Tubulogenesis of co-cultured human iPS-derived endothelial cells and human mesenchymal stem cells in fibrin and gelatin methacrylate gels. Biomater. Sci.   \n5(8), 1652–1660 (2017).  \n\n![](images/c9a46c1f88914b967c67948554116f9710bded354950aba3cb9e0875d00da7bd.jpg)",
+        "category": " Results and discussion"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,4007 @@
+[
+    {
+        "id": 1,
+        "chunk": "# 光固化材料性能及应用手册  \n\nGUANG GUHUA CAILIAO XINGNENGJIYINGYONGSHOUCE",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# 光固化材料",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 性能及应用手册  \n\nGUANG GUHUA CAILIAO XINGNENGJIYINGYONGSHOUCE",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# 光固化材料",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 性能及应用手册  \n\n6  \n\nGUANGGUHUA CAILIAO XINGNENGJIYINGYONGSHOUCE  \n\n本书共有14章，第1章为概述；第 $\\scriptstyle2\\sim5$ 章介绍了光固化原材料的结构和性能，附有350多个合成方法；第 ${\\mathsf{6}}{\\sim}12$ 章介绍了光固化产品的性能要求，附有680多个参考配方；第13章为光源与设备；第14章简介了电子束固化。附录中摘录了光引发剂的吸收谱图、光固化材料性能测试方法和涂料、油墨、胶黏剂的性能测试方法。书中还收集了近500家企业生产的UV产品。  \n\n本书适合于从事光固化材料开发和生产的工程技术人员、生产管理人员和营销人员阅读，也可供从事光固化技术研究或与光固化技术相关的大专院校师生参考。  \n\n![](images/a195a6a1f8952e2a37ee62f220c086a8537ac78df78047a5b7b487048b988d85.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 图书在版编目（CIP）数据  \n\n光固化材料性能及应用手册/金养智编著．一北京：化学工业出版社，2010.5ISBN 978-7-122-07905-3  \n\nI．光Ⅱ．金Ⅲ．高分子材料-手册IV.TB324-62  \n\n中国版本图书馆CIP数据核字（2010）第039417号  \n\n责任编辑：仇志刚责任校对：郑捷文字编辑：冯国庆装帧设计：刘丽华  \n\n出版发行：化学工业出版社 (北京市东城区青年湖南街13号邮政编码100011)  \n印刷：北京永鑫印刷有限责任公司  \n装订：三河市万龙印装有限公司  \n$787\\mathrm{mm}\\times1092\\mathrm{mm}$ 1/16印张 $39\\%$ 字数995千字 2010年7月北京第1版第1次印刷  \n\n购书咨询：010-64518888（传真：010-64519686) 售后服务：010-64518899网址：http://www.cip.com.cn凡购买本书，如有缺损质量问题，本社销售中心负责调换。  \n\n作者在北京化工大学工作，有幸自1973年以来一直从事感光材料的研究开发工作。1976年成立感光材料研究室后，开始接触感光性树脂的合成和应用，1986 年参加了国家“七五”科技攻关项目“光固化阻焊剂研制”，后来又参与了光固化环氧丙烯酸树脂和聚氨酯丙烯酸树脂的开发、UV纸张上光油、UV光盘油墨、UV皮革涂料和UV喷墨油墨等课题的研发工作，较早地投身于光固化领域，亲自参加了光固化原材料和产品的实际开发和应用工作。1981年参与了中国感光学会的筹建和成立工作，1993 年又参与了辐射固化专业委员会的成立工作，并一直在辐射固化专业委员会工作，参加了组织1995年、2001年、2005年三届亚洲辐射固化国际会议、历届中国辐射固化年会、四届中国国际UV/EB固化展览会以及辐射固化技术培训班等工作，也到有关的光固化生产企业学习和讲课等活动。这些经历使我学到了宝贵的知识，积累了丰富的资料和心得。  \n\n进入21世纪，随着人们对环境保护和节约能源日益关注，各国政府都加强了控制挥发性有机物排放和温室气体排放的立法，我国又提出保护生态环境，实现经济可持续发展，建立和谐社会的宏伟蓝图。在全球节能减排的大背景推动下，具有高效、环保、节能、优质特点的光固化技术得到了迅速的推广和发展。众多的企业和人们纷纷加盟到光固化事业中，我国的光固化产业得到了前所未有的发展，这极大地激发了作者编写一本较全面地反映光固化技术手册的想法，把学到的知识、积累的资料和亲身实践的经验奉献给对光固化事业感兴趣的人们，与正在从事或准备从事光固化技术的同仁们共享。  \n\n本书分14章，第1章概述了光固化技术的发展历史和应用；第 $2{\\sim}5$ 章介绍了光固化原材料的结构和性能，附有350多个合成方法；第 $_{6\\sim12}$ 章介绍了光固化产品的性能要求，附有680多个参考配方；第13章为光源和设备；第14章简介了电子束固化。附录刊登了光引发剂的紫外吸收谱图，光固化材料性能的测试方法，涂料、油墨、胶黏剂性能的测试方法。书中还收集了近500家企业生产的光固化产品。  \n\n光固化技术涉及光化学、高分子科学、材料科学、表面化学等多种学科，是一门综合性很强的技术，受作者学术水平所限，书中疏漏之处在所难免，恳切希望读者提出批评和宝贵意见，以便再版时改正。本书的编写得到了中国感光学会辐射固化专业委员会和辐射固化同行的大力支持、关心和鼓励，也得到了商春华、终晨和出版社同志的帮助，在此深表感谢。  \n\n编者2009年11月于北京化工大学  \n\n、",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "#  \n\n第1章 概述  \n1.1光固化技术的特点  \n1.1.1 高效  \n1.1.2 适应性广  \n1.1.3 节能  \n1.1.4 环境友好  \n1.1.5 经济 2  \n1.2 光固化技术的发展· 2  \n1.2.1 光固化技术的发展历史  \n1.2.2 光固化产业发展现状  \n1.3 光固化技术的应用  \n第2章活性稀释剂  \n2.1 概述 6  \n2.2 活性稀释剂的合成 9  \n2.2.1 直接酯化法 9  \n2.2.2 酯交换法 9  \n2.2.3 酰氯法 10  \n2.2.4 相转移法 10  \n2.2.5 加成酯化法 10  \n2.3 单官能团活性稀释剂 11  \n2.3.1 丙烯酸烷基酯 12  \n2.3.2 （甲基）丙烯酸羟基酯 13  \n2.3.3 带有环状结构或苯环的（甲基）丙烯酸酯 13  \n2.3.4 乙烯基活性稀释剂 14  \n2.4 双官能团活性稀释剂 14  \n2.4.1 乙二醇类二丙烯酸酯 15  \n2.4.2 丙二醇类二丙烯酸酯 15  \n2.4.3 其他二醇类二丙烯酸酯 16  \n2.5 多官能团活性稀释剂 16",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.6烷氧基化丙烯酸酯 19  \n\n2.7 丙烯酸二茂酯 20  \n2.8 烷氧基化双酚A二(甲基)丙烯酸酯 21  \n2.9 乙烯基醚类活性稀释剂 23  \n2.10 第三代(甲基)丙烯酸酯类活性稀释剂 24  \n2.11 含磷的阻燃型丙烯酸酯 26  \n2.12 杂化型活性稀释剂 26  \n2.13 新型光固化阳离子活性稀释剂 27  \n2.14 具有特殊功能的(甲基)丙烯酸酯类活性稀释剂 28  \n2.14.1 提高附着力的活性稀释剂 28  \n2.14.2 提高光固化速率的活性稀释剂 29  \n2.14.3 改善颜料分散性的活性稀释剂 29  \n2.14.4 高纯度活性稀释剂 29  \n2.15 活性稀释剂的毒性 30  \n2.16 活性稀释剂的贮存和运输 31  \n2.17 活性稀释剂丙烯酸酯的合成方法… 31",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 第3章 低聚物",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "#  \n\n3.1 概述· 41  \n3.2 不饱和聚酯· 44  \n3.2.1 不饱和聚酯的合成 44  \n3.2.2 不饱和聚酯的性能和应用 45  \n3.3 环氧丙烯酸酯 45  \n3.3.1 环氧丙烯酸酯的合成 46  \n3.3.2 环氧丙烯酸酯的性能与用途 47  \n3.4聚氨酯丙烯酸酯 51  \n3.4.1 聚氨酯丙烯酸酯的合成 51  \n3.4.2 聚氨酯丙烯酸酯的性能和应用 56  \n3.5 聚酯丙烯酸酯·…· 59  \n3.5.1 聚酯丙烯酸酯的合成…. 59  \n3.5.2 聚酯丙烯酸酯的性能和应用 61  \n3.6 聚醚丙烯酸酯……· 62  \n3.6.1 聚醚丙烯酸酯的合成. 62  \n3.6.2 聚醚丙烯酸酯的性能和应用… 63  \n3.7 纯丙烯酸树脂……· 64  \n3.7.1 纯丙烯酸树脂的合成… 64  \n3.7.2 纯丙烯酸树脂的性能和应用 64  \n3.8 有机硅低聚物... 65  \n3.8.1 有机硅低聚物的合成. 65  \n3.8.2 有机硅低聚物的性能和应用.. 66",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3.9 环氧树脂 67  \n\n3.10 水性UV低聚物 68  \n3.11 超支化低聚物 71  \n3.12 双重固化低聚物 74  \n3.13 自引发功能的低聚物 74  \n3.14 脂肪族和脂环族环氧丙烯酸酯…. 77  \n3.15 低黏度低聚物 78  \n3.16 光固化聚丁二烯低聚物 79  \n3.17 UV固化粉末涂料用低聚物 81  \n3.18 杂化低聚物- 一含金属的丙烯酸低聚物 82  \n3.19 其他低聚物 83  \n-3.19.1 含羧基的丙烯酸酯低聚物 83  \n3.19.2 氨基丙烯酸酯低聚物 85  \n3.20 低聚物的合成方法 86  \n3.20.1 环氧丙烯酸酯低聚物的合成 86  \n3.20.2 聚氨酯丙烯酸酯低聚物的合成 93  \n3.20.3 聚酯丙烯酸酯的合成 99  \n3.20.4 有机硅丙烯酸酯低聚物的合成 100  \n3.20.5 UV水性低聚物的合成 103  \n3.20.6 其他丙烯酸低聚物的合成 116  \n3.20.7 超支化丙烯酸低聚物的合成 · 122",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# 第4章 光引发剂  \n\n4.1 概述 126  \n4.2 裂解型自由基光引发剂 129  \n4.2.1 苯偶姻及其衍生物 . 130  \n4.2.2 苯偶酰及其衍生物 130  \n4.2.3 苯乙酮衍生物 131  \n4.2.4 $\\alpha$ 羟基酮衍生物…. . 132  \n4.2.5 $\\alpha$ -氨基酮衍生物 133  \n4.2.6 苯甲酰甲酸酯类 135  \n4.2.7 酰基麟氧化物 135  \n4.2.8 含硫的光引发剂 136  \n4.3 夺氢型自由基光引发剂 137  \n4.3.1 二苯甲酮及其衍生物 137  \n4.3.2 硫杂葱酮及其衍生物 138  \n4.3.3 葱及其衍生物 139  \n4.3.4 助引发剂 140  \n4.4 阳离子光引发剂 140  \n4.4.1芳基重氮盐 141  \n4.4.2 二芳基碘盐 141  \n4.4.3 三芳基硫盐 143  \n4.4.4 芳茂铁盐 144  \n4.5 大分子光引发剂 145  \n4.5.1 KIP系列大分子光引发剂…· 145  \n4.5.2 大分子二苯甲酮光引发剂OmnipolBP 146  \n4.5.3 大分子硫杂葱酮光引发剂OmnipolTX. 146  \n4.5.4 大分子氨基苯乙酮光引发剂Polymeric910 147  \n4.5.5 大分子 $\\alpha$ -羟基酮光引发剂Irgacure127 147  \n4.5.6 大分子苯甲酰甲酸酯光引发剂Irgacure 754.. 147  \n4.5.7 大分子酮酯光引发剂Irgacure OXE01 148  \n4.5.8 大分子酰基麟化氧光引发剂 148  \n4.5.9 大分子胺烷基酮光引发剂Rad-StartN-1414 148  \n4.5.10 大分子阳离子光引发剂 149  \n4.5.11 可聚合光引发剂 149  \n4.5.12 大分子助引发剂PPA 150  \n4.5.13 含夺氢型和裂解型双引发基的混杂光引发剂 .. 150  \n4.6 水基光引发剂 151  \n4.7 可见光引发剂 152  \n4.7.1 樟脑 152  \n4.7.2 钛茂 152  \n4.7.3 硫代叮啶酮/碘盐体系 153  \n4.7.4 有机过氧化物体系 154  \n4.7.5 硼酸盐/染料体系 154  \n4.7.6 六芳基双咪唑/染料体系 155  \n4.7.7 香豆素酮类/染料体系· 157  \n4.8 无光引发剂体系 157  \n4.9 光引发剂的合成方法 . 161  \n4.10 光引发剂主要生产厂商、产品及应用领域 203",
+        "category": " Introduction"
+    },
+    {
+        "id": 13,
+        "chunk": "# 第5章 添加剂",
+        "category": " Introduction"
+    },
+    {
+        "id": 14,
+        "chunk": "# 5.1 颜料和染料 208  \n\n5.1.1 白色颜料 210   \n5.1.2 黑色颜料 211   \n5.1.3 彩色颜料 212   \n5.2 填料 217   \n5.3 助剂 217   \n5.3.1 消泡剂 218   \n5.3.2 流平剂 219   \n5.3.3 润湿、分散剂 222   \n5.3.4 消光剂 225   \n5.3.5 阻聚剂 226   \n第6章 光固化涂料   \n6.1 概述 227   \n6.1.1 低聚物 228   \n6.1.2 活性稀释剂 228   \n6.1.3 光引发剂 229   \n6.1.4 颜料、填料 229   \n6.1.5 助剂 229   \n6.2 UV纸张上光油 231   \n6.3 UV木器涂料 234   \n6.3.1 UV腻子漆· 234   \n6.3.2 UV木器底漆 ·235   \n6.3.3 UV木器面漆…. 235   \n6.4 UV塑料涂料 ：237   \n6.5 UV真空镀膜涂料 240   \n6.5.1 真空镀膜 241   \n6.5.2 UV真空镀膜涂料底漆 242   \n6.5.3 UV真空镀膜涂料面漆. 243   \n6.5.4 UV真空镀膜涂料施工工艺 244   \n6.6 UV金属涂料 .... 244   \n6.7 UV 玻璃、陶瓷、石材涂料 247   \n6.8 UV皮革涂饰剂 248   \n6.9 UV汽车涂料 249   \n6.9.1 汽车塑料部件涂装涂料 ：249   \n6.9.2 汽车修补漆 250   \n6.9.3 汽车整车UV面漆 ：250   \n6.9.4 UV摩托车涂料.…. 251   \n6.10 UV 氟碳涂料 · 252   \n6.11 UV粉末涂料 253   \n6.11.1 UV粉末涂料特点 253   \n6.11.2 UV粉末涂料的组成和制造工艺 254   \n6.11.3 UV粉末涂料的应用 256   \n6.12 UV水性涂料 257   \n6.12.1 UV水性涂料的特点 257   \n6.12.2 UV水性涂料的组成 258   \n6.12.3 UV水性涂料的应用 259   \n6.13 UV涂料参考配方 260   \n6.13.1UV纸张上光油参考配方 …260   \n6.13.2 UV木器涂料参考配方 265   \n6.13.3 UV塑料涂料参考配方 278   \n6.13.4 UV金属涂料参考配方 287   \n6.13.5 其他UV涂料参考配方 292   \n6.13.6 UV粉末涂料参考配方 295   \n6.13.7 UV水性涂料参考配方 298   \n6.13.8 双重固化涂料参考配方 301   \n6.13.9 阳离子UV涂料、油墨参考配方 . 304   \n6.13.10 EB涂料、油墨参考配方 307",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# 第7章 光固化油墨  \n\n7.1 概述 309   \n7.1.1 低聚物 310   \n7.1.2 活性稀释剂 310   \n7.1.3 光引发剂 311   \n7.1.4 颜料 ..▪ 312   \n7.1.5 填料 314   \n7.1.6 助剂 314   \n7.2 UV网印油墨 315   \n7.3 UV装饰性油墨 320   \n7.3.1 UV折光油墨 320   \n7.3.2 UV皱纹油墨 321   \n7.3.3 UV珊瑚油墨 321   \n7.3.4 UV冰花油墨 321   \n7.3.5 UV磨砂油墨· 322   \n7.3.6 UV宝石油墨· 322   \n7.3.7 UV珠光油墨· 322   \n7.3.8 UV立体光栅油墨 323   \n7.3.9 UV香味油墨 323   \n7.3.10 UV发泡油墨 323   \n7.3.11 UV凹印和柔印装饰性油墨 324   \n7.4 UV胶印油墨 324   \n7.5 UV凸印油墨 326   \n7.6 UV柔印油墨 326   \n7.7 UV凹印油墨 327   \n7.8 UV移印油墨 328   \n7.9 UV喷墨油墨 329   \n7.10 UV印刷油墨参考配方·. 331",
+        "category": " Introduction"
+    },
+    {
+        "id": 16,
+        "chunk": "# 第8章 光固化胶黏剂  \n\n8.1 概述 348   \n8.2 光固化胶黏剂的组成 351   \n8.2.1 低聚物 351",
+        "category": " Introduction"
+    },
+    {
+        "id": 17,
+        "chunk": "# 8.2.2 活性稀释剂 351  \n\n8.2.3 光引发剂 352  \n8.2.4 添加剂 352  \n8.3 UV结构胶 353  \n8.4 UV密封胶 354  \n8.5 UV光学胶和UV玻璃胶 355  \n8.6 辐射固化压敏胶 356  \n8.7 UV离型剂 357  \n8.8 UV导电胶 358  \n8.9 UV胶黏剂参考配方 359",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# 第9章 感光性树脂印刷版  \n\n9.1 概述 370  \n9.2 感光性树脂凸版 371  \n9.2.1 液体感光性树脂凸版 371  \n9.2.2 固体感光性树脂凸版 371  \n9.3 感光性柔性版 372  \n9.3.1 固体感光性树脂柔性版 372  \n9.3.2 液体感光性树脂柔性版 373  \n9.3.3 CTP柔性版 374  \n9.4 预涂感光平版 374  \n9.4.1 阳图PS版 374  \n9.4.2 阴图PS版 375  \n9.4.3 无水胶印PS版· 375  \n9.5 计算机直接制版PS版 375  \n9.5.1 CTP版的性能要求 376  \n9.5.2 CTP版材的类型 376  \n9.5.3 UV-CTP版 377  \n9.6 网印制版感光材料 378  \n9.6.1 网印感光胶 378  \n9.6.2 网印感光膜 379  \n9.6.3 计算机直接制作网印版 379  \n9.7 感光性树脂和感光剂的合成方法……· 379  \n9.8 感光性树脂印刷版参考配方.. 385",
+        "category": " Introduction"
+    },
+    {
+        "id": 19,
+        "chunk": "# 第10章 光电子工业用光固化材料  \n\n10.1 光刻胶 391  \n10.1.1 光刻技术的发展 391  \n10.1.2 光刻工艺 393  \n10.1.3 光刻胶分类 395  \n10.1.4 重铬酸盐-胶体聚合物系负型光刻胶 395  \n10.1.5 聚乙烯醇肉桂酸酯系负型光刻胶 395  \n10.1.6 环化橡胶-双叠氮型负型光刻胶 397  \n10.1.7 邻重氮萘-酚醛树脂系正型紫外光刻胶……. 398  \n10.1.8 深紫外光刻胶 399  \n10.1.9 电子束光刻胶 403  \n10.1.10 X射线光刻胶… 403  \n10.1.11 离子束光刻胶 404  \n10.1.12 厚膜光刻胶 404  \n10.1.13 无显影气相光刻 405  \n10.1.14 光刻胶的合成方法 405  \n10.1.15 光刻胶参考配方 418  \n10.2印制电路板制造用的光固化材料 419  \n10.2.1 概述 419  \n10.2.2 印制电路板的制作 420  \n10.2.3 UV抗蚀油墨 421  \n10.2.4 UV阻焊油墨 422  \n10.2.5 UV字符油墨 422  \n10.2.6 干膜 423  \n10.2.7 光成像抗蚀油墨 425  \n10.2.8 光成像阻焊油墨 426  \n10.2.9 电沉积光致抗蚀剂 427  \n10.2.10 挠性印制板用UV油墨 428  \n10.2.11 积层多层板用光固化材料 430  \n10.2.12 UV印制电路用油墨和干膜参考配方 432  \n10.3 保形涂料 439  \n10.4 光敏聚酰亚胺… 441  \n10.5 UV光纤涂料 445  \n10.5.1 概述 445  \n10.5.2 UV光纤涂料 446  \n10.5.3 UV光纤着色油墨、UV并带涂料和UV胶黏剂 447  \n10.6 光盘用UV涂料、UV油墨和UV胶黏剂· 448  \n10.7 电子标签用光固化材料 450  \n光固化技术在平板显示器产业中的应用 · 452  \n10.8.1 平板显示器的结构及显示原理 453  \n10.8.2 光刻胶在平板显示器制造中应用 . 453  \n10.8.3光固化胶黏剂在平板显示器制造中的应用 456  \n10.8.4 光学功能膜材料. 457",
+        "category": " Introduction"
+    },
+    {
+        "id": 20,
+        "chunk": "# 第11章 光聚合和光接枝  \n\n11.1光聚合 461  \n\n11.1.1 光引发溶液聚合 461  \n11.1.2 光引发分散聚合 461  \n11.1.3 光引发反相乳液聚合 462  \n11.1.4 表面光引发聚合 462  \n11.2 光交联. 462  \n11.3 光引发前线聚合 464  \n11.4 双光子光聚合… 465  \n11.4.1 双光子光聚合的特点．. 465  \n11.4.2 双光子光聚合的光引发体系 466  \n11.4.3 双光子光聚合技术的应用 467  \n11.5 表面光接枝.….. 468  \n11.5.1 表面光接枝原理 468  \n11.5.2 表面光接枝方法 469  \n11.5.3 表面光接枝应用 470  \n11.6 光接枝与光聚合合成方法 472",
+        "category": " Introduction"
+    },
+    {
+        "id": 21,
+        "chunk": "# 第12章光固化材料在其他领域应用",
+        "category": " Introduction"
+    },
+    {
+        "id": 22,
+        "chunk": "# 12.1 立体快速成型….. 484  \n\n12.1.1 快速成型制造技术. 484  \n12.1.2 立体光刻 485  \n12.2 光固化软模压复制技术 487  \n12.2.1 光固化软模压全息复制技术 488  \n12.2.2 光纳米图像印刷技术 488  \n12.2.3 光软刻技术… 489  \n12.3 光固化牙科修复树脂 490  \n12.3.1 牙科修复树脂 490  \n12.3.2 可见光牙科修复树脂的组成 491  \n12.3.3 牙科修复树脂的种类 492  \n12.4 UV医用导电压敏胶 494  \n12.5 光聚合水凝胶… 495  \n12.5.1 光聚合水凝胶特点 495  \n12.5.2 光聚合水凝胶所用单体 496  \n12.5.3 光聚合水凝胶的应用 497",
+        "category": " Introduction"
+    },
+    {
+        "id": 23,
+        "chunk": "# 第13章 紫外光源和设备  \n\n13.1 光化学基础· 499  \n13.2 紫外光及其波段分类 500  \n13.3 紫外光源.· 502  \n13.3.1 汞弧灯 502  \n13.3.2 金属卤素灯 504  \n13.3.3 无极灯 504",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 24,
+        "chunk": "# 13.3.4 氙灯 506  \n\n13.3.5 UV发光二极管 506  \n13.3.6 准分子紫外灯 507  \n13.3.7 UV-等离子体固化 508  \n13.4 紫外光固化设备 508  \n13.4.1 紫外光固化设备组成 508  \n13.4.2 紫外光固化设备类型 510  \n13.5 分散与分散设备 511  \n13.5.1 搅拌机 511  \n13.5.2 三辊研磨机 511  \n13.5.3 球磨设备 512  \n13.6 涂装与涂装设备 514  \n13.6.1 辊涂及辊涂机 514  \n13.6.2 淋涂及淋涂机 514  \n13.6.3 喷涂及喷涂设备 515  \n13.6.4 静电喷涂及喷涂设备 517",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 25,
+        "chunk": "# 第14章 电子束固化  \n\n14.1 电子束· 519  \n14.2 电子加速器· 520  \n14.3 电子束固化· 521  \n14.3.1 电子束固化的技术优势 521  \n14.3.2 电子束固化机理 522  \n14.3.3 电子束固化的氧阻聚 523  \n14.3.4 电子束固化材料的组成 523  \n14.4 电子束固化材料的应用 523  \n14.4.1 电子束固化在涂料上的应用 523  \n14.4.2 电子束固化在印刷油墨上的应用 523  \n14.4.3 电子束固化在胶黏剂上的应用 524  \n14.4.4 电子束固化在复合材料上的应用 ·.. 524  \n14.4.5 电子束在高分子加工改性中的应用 .. 524",
+        "category": " Introduction"
+    },
+    {
+        "id": 26,
+        "chunk": "# 附录",
+        "category": " References"
+    },
+    {
+        "id": 27,
+        "chunk": "#",
+        "category": "ovide the text segment about hydrophilic polymers for analysis. Once you share it, I will classify it accordingly."
+    },
+    {
+        "id": 28,
+        "chunk": "# 附录1光引发剂吸收光谱图· 526  \n\n附录2 光固化原材料有关性能的测试方法 535  \n附录3 涂料性能检测方法 542  \n附录4 油墨质量检验方法.. 563  \n附录5 胶黏剂的性能测试方法.. 573  \n附录6 已发布的光固化产品标准 587  \n附录7 光固化常用名词英文及英文缩写 · 593  \n附录8 活性稀释剂主要生产企业 ·. 602  \n附录9 低聚物主要生产企业 605  \n附录10 光引发剂主要生产企业 607  \n附录11 UV涂料主要生产企业 609  \n附录12 UV印刷油墨主要生产企业 612  \n附录13 印制电路及电子用UV油墨和干膜主要生产企业… 615  \n附录14 光固化胶黏剂主要生产企业 616  \n附录15 UV光源主要生产企业 619  \n\n参考文献  \n\n![](images/42941012d7711c37f6171ab558cf722957e56fe0a9bcea8d6512d87f3d13ea7c.jpg)  \n\n紫外光（UV）固化是20世纪60年代出现的一种材料表面处理的先进技术，它与电子束（EB）固化统称为辐射固化（Rad Tech)。它是利用紫外光引发具有化学活性的液态材料快速聚合交联，瞬间固化成固态材料。",
+        "category": " References"
+    },
+    {
+        "id": 29,
+        "chunk": "# 1.1 光固化技术的特点  \n\n光固化技术是一种高效、环保、节能、优质的材料表面处理技术，被誉为面向21世纪绿色工业的新技术。2004年5月在美国夏洛特市召开的北美辐射固化国际会议上，光固化和电子束固化技术被归纳为具有“5E”特点的工业技术：efficient（高效)；enabling（适应性广）；economical（经济）；energy saving（节能)；environmental friendly（环境友好）。",
+        "category": " Introduction"
+    },
+    {
+        "id": 30,
+        "chunk": "# 1. 1. 1 高效  \n\n光固化产品最常见的为UV涂料、UV油墨和UV胶黏剂，它们的最大特点是固化速率快，一般在几秒到几十秒之间，最快的可在0.05～0.1s的时间内固化，是目前各种涂料、油墨、胶黏剂中干燥固化最快的。如UV光纤涂料最快的已达1500～3000m/min，UV胶印油墨也可适应100～400m/min 的印刷速度，这就能满足大规模自动化流水线的生产要求，大大提高了生产效率，还节省了半成品堆放的空间。而通常溶剂型或热固型涂料、油墨和胶黏剂干燥固化的时间需要数小时甚至几天，需要很大的生产车间来堆放半成品。",
+        "category": " Introduction"
+    },
+    {
+        "id": 31,
+        "chunk": "# 1.1.2 适应性广  \n\n光固化产品可适用于多种基材，如纸张、木材、塑料、金属、皮革、石材、玻璃、陶瓷等，特别对一些热敏感材质（如纸张、塑料或电子元器件等）尤其适用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 32,
+        "chunk": "# 1.1.3 节能  \n\n光固化产品是常温快速固化，其能耗只有热固化配方产品的1/10～1/5。光固化仅需要用于激发光引发剂的辐射能，而不像热固化那样需要加热基质、材料和周围空间，还要蒸发除去稀释用的溶剂或水，耗费大量能量。",
+        "category": " Introduction"
+    },
+    {
+        "id": 33,
+        "chunk": "# 1. 1. 4 环境友好  \n\n光固化产品的另一个优势是它基本不含挥发性溶剂，所用的活性稀释剂都是高沸点有机物——丙烯酸多官能单体，而且固化时都参与交联聚合，成为交联网状结构的一部分，因此不会造成空气的污染，也减少了对人体的危害及火灾的危险性，是一类环境友好的产品。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 34,
+        "chunk": "# 1. 1.5 经济  \n\n光固化产品的生产效率高、能耗低；而且光固化设备投资相对较低，易实现流水线生产，厂房占地面积较少，可节省大量投资；不含溶剂，减少污染，也节省资源，综合考虑是经济的。  \n\n随着世界各国对生态环境保护的重视，对大气排放物VOC进行严格的立法限制，光固化产品的优越性就显得更为突出。美国、欧洲和日本等发达国家及地区均将采用光固化技术作为减少VOC 排放的重要手段之一。我国自改革开放以来，国民经济得到了快速发展，2008年国内生产总值（GDP）达300670亿元，约合4.33万亿美元，超过德国成为仅次于美国、日本的第三大经济体。为了实现持续的发展，建立和谐的社会，加大了对环境的治理和保护，这无疑为光固化产业发展提供了机遇。可以相信，随着国家的发展，社会的进步，人与自然和谐相处，绿色环保的光固化产业一定会与日俱进，欣欣向荣。",
+        "category": " Introduction"
+    },
+    {
+        "id": 35,
+        "chunk": "# 1.2.1光固化技术的发展历史  \n\n1968年德国拜耳公司首先开发了以不饱和聚酯/苯乙烯体系的第一代紫外光固化木器涂料，使光固化技术实现了产业化。  \n\n实际上，光固化技术最早的应用可以追溯到19 世纪，当时主要用于印刷照相制版。1826年法国化学家尼普斯利用沥青的光固化特性，将天然沥青涂在石板上，经光学镜头长时间曝光后，用松节油除去未固化的沥青，得到照相图像；1832年德国人舒柯发现了重铬酸盐具有感光性；1852 年美国人塔尔博特将重铬酸盐与明胶涂在钢板上制得照相凹版；1855年柏依蒂文用重铬酸盐与明胶研制成珂版；1942年美国人彼尔发明了印制电路技术，重铬酸盐作为光刻胶用于制造印制电路板，这是最早应用于电子工业的光固化材料；1945年盖茨利用烯类化合物的光聚合反应，制得了光聚合型印刷凹版；1946年美国Inmont公司首先发表了不饱和聚酯/苯乙烯体系的光固化油墨的专利；1954年柯达公司明斯克等研究聚乙烯醇肉桂酸酯为代表的感光性高分子，成功地用作光刻胶（KPR)，开创了合成高分子在微电子工业用光刻胶的历史，并应用于照相制版和印制电路板的制作；1958年柯达公司又发明了双叠氮化合物-环化橡胶系光刻胶；1963年杜邦公司用甲基丙烯酸乙二醇酯与聚乙烯醇，以葱作光引发剂，制得感光性树脂凸版（Dycril)；1968年杜邦公司开发了光敏抗蚀于膜；1970年杜邦公司又开发了感光性树脂柔性版（Cyrel）。",
+        "category": " Introduction"
+    },
+    {
+        "id": 36,
+        "chunk": "# 1.2.2光固化产业发展现状  \n\n随着科学技术的发展，光固化技术应用从最早的印制版材、光刻胶发展到光固化涂料、油墨、胶黏剂，应用领域不断扩大，形成了一个新的产业。为了加强光固化行业内的企业、研究院所和高等院校之间的交流，促进它们相互间的合作，推动光固化技术的发展，各大洲先后成立了行业协会。1974年北美辐射固化协会最早成立，接着在1983年欧洲也成立了辐射固化协会，1997年在中日两国辐射固化协会共同倡议下成立了亚洲辐射固化协会。  \n\n我国的光固化技术开发起步于20世纪70年代初，当时上海、北京和天津等地先后开展了UV木器涂料和UV印刷油墨的研发，但限于原材料尚无商品供应，都需自己合成开发；紫外光源也在研发中，不能配套，无法实现工业化生产。进人20世纪80年代，由于改革开放，家电、建材和印刷包装工业发展迅速，引进了多条印制电路、木器加工和纸张上光生产线，都需要使用光固化涂料和油墨，推动了国内企业和研究院所、高校对光固化材料的研究开发。到了20世纪90年代，国内开始生产UV纸张上光油、UV木器涂料、UV网印油墨、UV阻焊油墨等光固化产品。同时光固化原材料活性稀释剂、低聚物和光引发剂也开始工业生产。1993年5月，国内从事光固化产业的企业、研究院所和高校同仁成立了辐射固化分会，1996年设立了辐射固化信息网站，并出版了《辐射固化通讯》。2001年11月经民政部正式批准为中国感光学会辐射固化专业委员会。进入21世纪，我国的光固化产业获得了快速的发展，成为仅次于美国和日本的光固化原材料和配方产品的生产大国，特别是光引发剂已成为世界上最大的生产和出口国，已初步形成一个新的高新产业。表1-1列举了$2001{\\sim}2008$ 年我国光固化产品统计情况。  \n\n表1-12001～2008年我国光固化产品统计 单位：t  \n\n\n<html><body><table><tr><td colspan=\"2\">项目</td><td>2001年</td><td>2002年</td><td>2003年</td><td>2004年</td><td>2005年</td><td>2006年</td><td>2007年</td><td>2008年</td></tr><tr><td colspan=\"2\">统计企业/家</td><td>87</td><td>81</td><td>95</td><td>109</td><td>122</td><td>116</td><td>129</td><td>127</td></tr><tr><td rowspan=\"4\">原材料</td><td>活性稀释剂</td><td>8879</td><td>13862</td><td>24739</td><td>24350</td><td>36528</td><td>48034</td><td>49213</td><td>77150</td></tr><tr><td>低物</td><td>3390</td><td>7037</td><td>8930</td><td>14120</td><td>19825</td><td>27420</td><td>31595</td><td>43655</td></tr><tr><td>光引发剂</td><td>9042</td><td>9520</td><td>13898</td><td>14723</td><td>16995</td><td>22053</td><td>29531</td><td>25561</td></tr><tr><td>合计</td><td>21311</td><td>30419</td><td>47567</td><td>53193</td><td>73348</td><td>97507</td><td>110339</td><td>146366</td></tr><tr><td rowspan=\"4\">配方产品</td><td>UV涂料</td><td>15245</td><td>16741</td><td>19007</td><td>23300</td><td>25024</td><td>29027</td><td>32530</td><td>31938</td></tr><tr><td>UV油墨</td><td>3416</td><td>3968</td><td>6514</td><td>9057</td><td>11039</td><td>12894</td><td>14648</td><td>18028</td></tr><tr><td>UV胶黏剂</td><td></td><td>23</td><td>76</td><td>242</td><td>363</td><td>488</td><td>846</td><td>1120</td></tr><tr><td>合计</td><td>18661</td><td>20732</td><td>25597</td><td>32599</td><td>36426</td><td>42409</td><td>48024</td><td>51086</td></tr><tr><td colspan=\"2\">总计</td><td>39972</td><td>51151</td><td>73164</td><td>85792</td><td>109774</td><td>139916</td><td>158363</td><td>197452</td></tr></table></body></html>  \n\n在北美、欧洲和日本等发达国家和地区，从事光固化和电子束固化生产的企业发展迅速，巴斯夫、拜耳、陶氏化学、大日本油墨、汽巴、氰特、沙多玛等跨国公司纷纷加盟，已形成具有一定市场规模的产业，其中光固化约占95%，电子束固化约占5%，见表1-2和表1-3。  \n\n表1-2北美、欧洲、日本UV/EB市场  \n\n\n<html><body><table><tr><td>产品</td><td>北美</td><td>欧洲</td><td>日本</td></tr><tr><td>涂料 油墨 胶黏剂 光致抗蚀剂</td><td>63250 24700 4450</td><td>64000 12400 2900 3600</td><td>18130 10470 1900 22720</td></tr><tr><td>其他 总计</td><td>92400</td><td>1100 84000</td><td>90 53310</td></tr></table></body></html>\n\n$\\mathbb{\\Phi}$ 北美为2007年统计数据，欧洲为2002年统计数据，日本为2006年统计数据。  \n\n单位：t  \n\n表1-3全球2004年辐射固化原材料消耗量  \n\n\n<html><body><table><tr><td>原材料</td><td>欧洲</td><td>美国</td><td>中国</td><td>日本</td><td>其他国家</td><td>总计</td></tr><tr><td>低聚物</td><td>38750</td><td>34160</td><td>14200</td><td>14600</td><td>13030</td><td>114740</td></tr><tr><td>活性稀释剂</td><td>27850</td><td>29000</td><td>24350</td><td>20200</td><td>19771</td><td>121171</td></tr><tr><td>光引发剂</td><td>5100</td><td>5000</td><td>2300</td><td>1980</td><td>1909</td><td>16289</td></tr><tr><td>总计</td><td>71700</td><td>68160</td><td>40850</td><td>36780</td><td>34710</td><td>252206</td></tr></table></body></html>  \n\n光固化技术由于具有快速固化、生产效率高、节能、环保、优质、经济、适用于多种基材等优点，已广泛应用于印刷、包装、广告、建材、装潢、电子、通信、计算机、家电、汽车、航空、航天、仪器仪表、体育、卫生等各行各业。光固化产品主要以UV涂料、UV油墨、UV胶黏剂、感光性印刷版材、光刻胶、光快速成型材料等形式出现，在人们日常生活中，光固化产品到处可见，光固化产品的使用已是无处不在。  \n\nUV木器涂料是最早应用也是目前用量最大的UV产品。在实木地板、复合实木地板、竹地板、复合地板生产过程中，大多采用UV腻子、UV底漆和UV面漆进行涂装；中密度板使用UV罩光清漆或色漆；家具UV涂装也从过去板式家具辊涂或淋涂，发展到喷涂、三维固化，可以实现雕花家具的UV立体涂装。PVC 扣板、PVC 地板砖、塑料地板革、人造石材、玻璃钢、石材等经UV涂装后提高了耐磨、抗划伤和耐抗性，也大大提高了装饰效果。玻璃的蚀刻、黏合、彩色印刷，安全玻璃的制造也离不开UV技术。UV耐磨涂料还广泛应用于橱柜、铝合金门窗和塑料门窗的涂装保护及装饰中。  \n\n印刷行业上，UV胶印油墨的使用一改过去印刷品因油墨不干而需喷粉的弊病，并且色彩更鲜艳饱和，清晰度更佳。目前UV油墨已在凸印、柔印、凹印、涂印、移印等不同印刷方式中得到应用。尤其开发出多种具有特殊效果的UV装饰性油墨，如冰花油墨、仿金属磨砂油墨、折光油墨、皱纹油墨、锤纹油墨、水晶油墨、发泡油墨等，它们都成了高档烟酒、保健品、化妆品和食品包装的重要印刷材料。进入21世纪，UV喷墨油墨开发成功，成为户外大型广告和指示牌制作的生力军。另外，纸张的UV上光、局部上光，已成为书刊封面、明信片、广告宣传品、画张、外包装纸盒、装饰纸袋的重要装饰方法。生产不干胶标签最理想的方式是采用UV压敏胶和UV印刷，而用UV有机硅离型涂料制作的离型纸又是不干胶标签的理想封底。饮料用易拉罐、食品用金属容器的涂装和装饰大量使用UV涂料和UV油墨。真空镀铝保护、塑料包装盒的金属化涂装，都需使用UV底漆和面漆，目前用来大量制作化妆品包装。 足本  \n\n印刷版材制造是光固化技术最早应用的领域，胶印用PS版，凸印用的固体树脂和液体树脂版，柔印用的液体感光性柔性液和固体感光性柔性版，凹印用感光性树脂凹版，网印用感光胶和感光菲林膜，以及近年来发展的计算机直接制版（CTP）版材中的胶印高感PS版、紫激光版、UV-CTP版、CTP柔性版和网印CTS版，都是光固化产品。  \n\n在光电子、信息和通信工业中，光固化技术更是大有作为。光刻胶也是较早应用的光固化产品，如早期的聚乙烯醇肉桂酸酯、环化橡胶和邻叠氮萘，到目前制造大规模集成电路用的远紫外光刻胶和电子束光刻胶；近年来光刻胶又在平板显示器制作上大放光彩，液晶显示器、等离子体显示器、有机电致发光显示器的制作都离不开光刻胶。  \n\n，光纤制造是光固化技术成功应用的领域之一。石英经熔融拉丝后，马上涂覆UV光纤内层涂料和UV光纤外层涂料，再涂覆UV着色油墨，制成光纤；12种不同颜色的光纤用UV并带涂料黏结为并带，最后组合成光缆。光纤之间的连接则要使用UV胶黏剂。  \n\n光盘制造是光固化技术应用的又一亮点。母盘制作需用光刻胶，碟片复制需用UV光盘涂料保护，DVD碟片制作需用UV胶黏剂，然后再经网印或胶印UV油墨得到成品。  \n\n印制电路板（PCB）制造是光固化技术应用的又一成功领域。单面板和挠性板制作需用UV抗蚀油墨、UV阻焊油墨、UV字符油墨；双面板和多层板制作需用抗蚀干膜或光成像抗蚀油墨、阻焊干膜或光成像阻焊油墨以及UV字符油墨；积层印制板则需用UV树脂进行光致成孔。  \n\n各种家用电器，如电视机、电冰箱、空调和笔记本电脑等塑料外壳需用UV耐磨涂料进行涂装保护。手机制作中，UV涂料、UV油墨和UV胶黏剂用于手机塑料壳体保护涂层、键盘的制作、键盘的表面印刷、手机机芯的多层板、液晶显示器和多种元器件的拼装黏合。磁卡、IC卡的保护涂层和文字图案印刷，电子标签（RFID）芯片和天线制作，重要仪器和设备主板的“三防”保护涂层，电子元器件的封口、黏合和固定，线圈的黏结、密封和固定，触摸开关的制作等，都是各种光固化产品大显身手的领域。  \n\n汽车工业中，汽车的前灯和后灯反光镜都是由工程塑料经UV金属化涂装制得，而车灯的灯罩则是用聚碳酸酯经UV耐磨涂料涂装而成，汽车轮毂也可用UV耐磨涂料涂装，汽车内部塑料部件很多都使用UV涂料涂装，汽车修补也开始用UV底漆和UV面漆。摩托车油箱和防护板也需用UV涂料涂装保护。  \n\n机械行业快速成型制作模具，利用激光立体光铸是最快速、方便和有效的一种途径。钢材和钢管可用UV防锈涂料保护，彩涂钢板可用UV彩钢涂料。金属标牌的制作和保护，螺帽、螺栓固定和粘接也需用光固化材料。显微镜、照相机、望远镜等各种光学仪器中光学棱镜组合的定位和粘接，激光器和探头、反射镜、透镜及光栅等组装是UV胶黏剂的最佳使用场合，快速、高效又能提高精度。  \n\n光固化技术很早就在牙科修补中应用，现在使用的是可见光固化牙科材料。光聚合制备水凝胶，可作为药物缓释载体、组织工程支架材料。UV医用导电压敏胶已成功地用于理疗电极、一次性使用心电电极和高频电刀用板电极等。注射用针头与注射针筒黏合，各种医疗器械上的阀门、多向接头及其他配件的粘接大量使用UV胶黏剂。  \n\n雪、钓鱼竿、高尔夫球杆、防震头盔等体育用具，也是经UV耐磨涂料涂装制成的。  \n\n总之，随着光固化技术的发展，将有更多、更新、更好的光固化产品被开发出来，光固化技术的应用领域将更加广泛，作为面向21世纪的绿色工业的新技术，将更有效地服务于社会，造福于人类。 Y 5F  \n\n![](images/89c393194ce7c9774a4d4e1a53f177aa4f2e884533cc5be9b78976dde8aac108.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 37,
+        "chunk": "# 第2章 活性稀释剂  \n\n活性稀释剂（reactivediluent）通常称单体（monomer）或功能性单体（functionalmonomer)，它是一种含有可聚合官能团的有机小分子，在光固化产品的各种组分中活性稀释剂也是一个重要的组成，它不仅溶解和稀释低聚物，调节体系的黏度，而且参与光固化过程，影响光固化产品的光固化速率和固化膜的各种性能，因此选择合适的活性稀释剂也是光固化产品配方设计的重要环节。  \n\n从结构上看，自由基光固化用的活性稀释剂都是具有“ C ”不饱和双键的单体，如丙烯酰氧基、甲基丙烯酰氧基、乙烯基、烯丙基，光固化活性依次为：  \n\n丙烯酰氧基>甲基丙烯酰氧基>乙烯基>烯丙基因此，自由基光固化活性稀释剂主要为丙烯酸酯类单体。阳离子光固化用的活性稀释剂为具有乙烯基醚“HC—CH—O—”或环氧基“CH—CH—”的单体。乙烯基醚类单体也可参与自由基光固化，因此可用作两种光固化体系的活性稀释剂(表2-1)。  \n\n表2-1活性稀释剂的种类  \n\n\n<html><body><table><tr><td>名称</td><td>官能团</td><td>实 例</td><td>光固化类型</td></tr><tr><td>丙烯酸酯</td><td>H2C=CH-COO一</td><td>HC—CHCOO-(CH—CH—O)COCH-CH2 CH3 三缩丙二醇二丙烯酸酯（TPGDA）</td><td>自由基</td></tr><tr><td>甲基丙烯酸酯</td><td>HC=C(CH)—COO-</td><td>HC—C（CH)-COO—CHCH—OH 甲基丙烯酸β-羟乙酯（HEMA)</td><td>自由基</td></tr><tr><td>乙烯基类</td><td>H2C—CH-</td><td>H2C—CH 苯乙烯(St)</td><td>自由基</td></tr></table></body></html>  \n\n<html><body><table><tr><td>名称</td><td>官能团</td><td>实例</td><td>光固化类型</td></tr><tr><td>乙烯基醚类</td><td>HC—CH—O—</td><td>CH—CH-O(CHCHO)CH=CH 三乙二醇二乙烯基醚（DVE-3）</td><td>自由基、阳离子</td></tr><tr><td>环氧类</td><td>CH-CH-</td><td>O--CH:—-CH—CH 苯基缩水甘油醚(PGE)</td><td>阳离子</td></tr></table></body></html>  \n\n活性稀释剂按其每个分子所含反应性基团的多少，可以分为单官能团活性稀释剂、双官能团活性稀释剂和多官能团活性稀释剂。每个分子中含有官能团的数目称为官能度，所以单官能团活性稀释剂的官能度为1，双官能团活性稀释剂的官能度为2，多官能团活性稀释剂的官能度可以是3、4或更多。活性稀释剂中含有可参与光固化反应的官能团越多，官能度越大，则光固化反应活性越高，光固化速率越快，从光固化活性看：  \n\n多官能团活性稀释剂>双官能团活性稀释剂>单官能团活性稀释剂  \n\n随着活性稀释剂官能度的增加，除了增加光固化反应活性外，同时增加固化膜的交联密度。单纯的单官能团单体光聚合后，只能得到线型聚合物，不发生交联。当官能度≥2的活性稀释剂存在时，光固化后得到交联聚合物网络，官能度高的活性稀释剂可得到高交联度的网状结构。交联度的高低对固化膜的物理力学性能和化学性能产生极大的影响。表2-2列出了活性稀释剂官能度和分子量对固化膜性能的影响规律。  \n\n表2-2活性稀释剂官能度和分子量对固化膜性能的影响规律  \n\n\n<html><body><table><tr><td>固化膜性能</td><td>固化速率</td><td>交联度</td><td>伸长率</td><td>硬度</td><td>柔韧性</td><td>耐磨性</td><td>耐冲击性</td><td>热稳定性</td><td>耐化学性</td><td>收缩率</td></tr><tr><td rowspan=\"3\">官能度提高</td><td>慢</td><td>低</td><td>高</td><td>软</td><td>柔</td><td>差</td><td>好</td><td>差</td><td>差</td><td>低</td></tr><tr><td>↓</td><td>↓</td><td>↓</td><td>↓</td><td>↓</td><td>↓</td><td></td><td>↓</td><td></td><td>↓</td></tr><tr><td>快</td><td>高</td><td>低</td><td>硬</td><td>脆</td><td>好</td><td>差</td><td>好</td><td>好</td><td>高</td></tr><tr><td rowspan=\"3\">分子量增加</td><td>慢</td><td>高</td><td>低</td><td>硬</td><td>脆</td><td>好</td><td>差</td><td>好</td><td>好</td><td>高</td></tr><tr><td>√</td><td>↓</td><td>↓</td><td></td><td>↓</td><td></td><td>↓</td><td></td><td>↓</td><td>↓</td></tr><tr><td>快</td><td>低</td><td>高</td><td>软</td><td>柔</td><td>差</td><td>好</td><td>差</td><td>差</td><td>低</td></tr></table></body></html>  \n\n活性稀释剂自身的化学结构对固化膜的性能有很大影响，因此在制备光固化产品时，要根据配方产品性能的要求，选择合适的活性稀释剂。表2-3列出了活性稀释剂化学结构对固化膜性能的影响。  \n\n续表  \n表2-3活性稀释剂化学结构对固化膜性能的影响  \n\n\n<html><body><table><tr><td>活性稀释剂结构</td><td>固化膜性能特点</td></tr><tr><td>链烷结构</td><td>耐高温，疏水性，耐候性，抗黄变，耐化学药品，促进附着力</td></tr><tr><td>酯结构</td><td>耐候性（耐高温，耐黄变，抗紫外)，耐溶剂，但遇碱易水解，良好的附着力</td></tr><tr><td>芳香环结构</td><td>耐高温，耐化学药品，提供硬度、附着力、疏水性，易黄变</td></tr><tr><td>酯环结构</td><td>耐高温，耐候性，不黄变，耐化学药品，提供附着力、疏水性</td></tr><tr><td>醚结构</td><td>固化快，耐碱和链烷类溶剂，对环氧和聚氨酯溶解力良好，一且氧化易黄变</td></tr></table></body></html>  \n\n活性稀释剂中随着官能团的增多，其分子量也相应增加，分子间相互作用增大，因而黏度也增大，这样稀释作用就减少。从活性稀释剂的黏度看：多官能团活性稀释剂>双官能团活性稀释剂 $>$ 单官能团活性稀释剂。从活性稀释剂的稀释作用看：单官能团活性稀释剂 $>$ 双官能团活性稀释剂>多官能团活性稀释剂。表2-4列出了常用活性稀释剂对体系黏度和固化速率的影响。  \n\n表2-4常用活性稀释剂对体系黏度和固化速率影响  \n\n\n<html><body><table><tr><td>活性稀释剂</td><td>官能度f</td><td>体系黏度/mPa·s</td><td>固化速率/s</td></tr><tr><td>2-EHA</td><td>1</td><td>1180</td><td>12.5</td></tr><tr><td>NVP</td><td>1</td><td>1400</td><td>75</td></tr><tr><td>POEA</td><td>1</td><td>5000</td><td>110</td></tr><tr><td>IBOA</td><td>1</td><td>13000</td><td>75</td></tr><tr><td>HDDA</td><td>2</td><td>2088</td><td>200</td></tr><tr><td>TEGDA</td><td>2</td><td>4050</td><td>125</td></tr><tr><td>TPGDA</td><td>２</td><td>7550</td><td>100</td></tr><tr><td>TMPTMA</td><td>3</td><td>10400</td><td>15</td></tr><tr><td>PETA</td><td>3</td><td>25000</td><td>110</td></tr><tr><td>TMPTA</td><td>3</td><td>25400</td><td>200</td></tr><tr><td>OTA-480</td><td>3</td><td>46250</td><td>125</td></tr></table></body></html>\n\n$\\mathbb{O}$ 活性稀释剂：低聚物 $\\mathbf{\\zeta}=30:70$ 。$\\textcircled{2}$ 甘油衍生物三丙烯酸酯。  \n\n制备光固化产品选择活性稀释剂时，应考虑以下因素。  \n\n$\\textcircled{1}$ 低黏度：稀释能量强。  \n$\\textcircled{2}$ 低毒性：低气味、低挥发、低刺激。  \n$\\textcircled{3}$ 低色相：特别在无色体系、白色体系必须加以考虑。  \n$\\textcircled{4}$ 低体积收缩：增加对基材的附着力。  \n$\\textcircled{5}$ 高反应性：提高光固化速率。  \n$\\textcircled{6}$ 高溶解性：与树脂相容性好，对光引发剂溶解性好。  \n$\\textcircled{7}$ 高纯度：水分、溶剂、酸含量、聚合物含量低。  \n$\\textcircled{8}$ 玻璃化温度： $T_{\\mathrm{{g}}}$ 适合涂层性能的要求。  \n$\\textcircled{9}$ 热稳定性好：利于生产加工、运输和贮存。  \n$\\textcircled{1}$ 价格便宜：降低成本。  \n\n要根据光固化产品应用时需要的黏度、固化速率、基材的附着性能、涂层所要求的物理力学性能（如光泽、硬度、柔韧性、耐冲击性、拉伸强度、耐磨性、耐化学品性、耐黄变性等）综合考虑，进行选择。单一的活性稀释剂不能满足上述要求，大多数要选择两种或多种不同官能度的活性稀释剂进行搭配，以获得综合性能最佳的光固化产品配方。表2-5为部分活性稀释剂的固化收缩率和表面张力。  \n\n表2-5部分活性稀释剂的固化收缩率和表面张力  \n\n\n<html><body><table><tr><td>产品代号</td><td>化学名称</td><td>分子量</td><td>官能度</td><td>收缩率/%</td><td>表面张力/（mN/m）</td></tr><tr><td>IOBA</td><td>丙烯酸异冰片酯</td><td>208</td><td>1</td><td>8.2</td><td>32</td></tr><tr><td>EB114</td><td>乙氧基化丙烯酸氧苯酯</td><td>236</td><td>1</td><td>6.8</td><td>39</td></tr><tr><td>ODA</td><td>丙烯酸十八烷基酯</td><td>200</td><td>1</td><td>8.3</td><td>30</td></tr><tr><td>TCDA</td><td>三环葵基二甲醇二丙烯酸酯</td><td>304</td><td>2</td><td>5.9</td><td>40</td></tr><tr><td>EB145</td><td>丙氧基化新戊二醇二丙烯酸酯</td><td>328</td><td>2</td><td>9.0</td><td>31</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>产品代号</td><td>化学名称</td><td>分子量</td><td>官能度</td><td>收缩率/%</td><td>表面张力/（mN/m)</td></tr><tr><td>DPGDA</td><td>二丙二醇二丙烯酸酯</td><td>242</td><td>2</td><td>13.0</td><td>35</td></tr><tr><td>TPGDA</td><td>三丙二醇二丙烯酸酯</td><td>300</td><td>2</td><td>18.1</td><td>34</td></tr><tr><td>HDDA</td><td>己二醇二丙烯酸酯</td><td>226</td><td>2</td><td>19.0</td><td>36</td></tr><tr><td>EB160</td><td>乙氧基化三羟甲基丙烷三丙烯酸酯</td><td>428</td><td>3</td><td>14.1</td><td>39</td></tr><tr><td>OTA 480</td><td>丙氧基化甘油三丙烯酸酯</td><td>480</td><td>3</td><td>15.1</td><td>36</td></tr><tr><td>TMPTA</td><td>三羟甲基丙烷三丙烯酸酯</td><td>296</td><td>3</td><td>25.1</td><td>38</td></tr><tr><td>EB 40</td><td>烷氧基化季戊四醇四丙烯酸酯</td><td>571</td><td>4</td><td>8.7</td><td>40</td></tr><tr><td>EB140</td><td>二羟甲基丙烷四丙烯酸酯</td><td>438</td><td>4</td><td>10.0</td><td>38</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 38,
+        "chunk": "# 2.2 活性稀释剂的合成  \n\n丙烯酸酯类活性稀释剂的合成方法主要有直接酯化法、酯交换法、酰氯法、相转移法和加成酯化法等，但大多数是通过直接酯化法制得的。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 39,
+        "chunk": "# 2.2.1 直接酯化法  \n\n直接酯化法常用催化剂为浓硫酸、 $\\mathbf{H_{3}C}-\\textcircled{\\mathrm{~\\\"~}}\\mathbf{so_{3}H}$ —SOH、CHSOH等。用浓硫酸作酯化反应的催化剂，常使反应物发生脱水、氧化和自身酯化等副反应，产生多种副产物，给产物的精制和原料回收带来困难，使后处理过程复杂化，影响产品质量，同时腐蚀设备，所以目前生产中大多用对甲苯磺酸作催化剂，它具有用量少、反应温度低、转化率高、产品质量好等优点；反应结束后，催化剂和产物容易分离，工艺流程简便。  \n\n酯化反应生产的水，通过脱水剂除去。常用的脱水剂有苯、甲苯、二甲苯、环己烷、正庚烷等，利用与酯化反应产生的水形成共沸液而带走水。烷烃价格贵，挥发性强；二甲苯沸点高；苯沸点偏低，挥发性大，不易回收，其毒性大。故一般选用甲苯作脱水剂，甲苯沸点为110℃，与水共沸点为84℃，在减压蒸馏脱溶剂中易于冷凝，回收率高，甲苯毒性比苯低，价格也较便宜。但近年来，涂料、油墨和胶黏剂对苯系溶剂限制使用，因此不少生产企业已不再使用甲苯作脱水剂，而改用烷烃类脱水剂。  \n\n酯化反应必须要加阻聚剂，以防止原料丙烯酸和产物丙烯酸酯聚合。常用的有对苯二酚、叔丁基对苯二酚等酚类化合物，噻吩嗪，对苯二胺等胺类化合物，二甲氨基二乙基氨基酸铜、二丁基二硫代氨基甲酸铜等铜配位化合物，由一种或几种组成。 限 t  \n\n对丙烯酸高级酯也可以用熔融酯化法进行酯化反应，不必用脱水剂，催化剂和阻聚剂用量也可减少，在110～120℃回流反应后，进行脱水，最后减压蒸馏除去未反应的丙烯酸和残余水，得到纯度较高的丙烯酸高级酯，产率也高。 3",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 40,
+        "chunk": "# 2.2.2 酯交换法  \n\n$$\n\\mathrm{H_{2}C-C H C O O C H_{3}\\ +R O H\\mathrm{\\sideset{}{'}\\Sigma\\Sigma\\Sigma\\Sigma\\Sigma\\Sigma\\Sigma\\Sigma\\Sigma\\Sigma\\Sigma\\Sigma\\Sigma\\Sigma\\Sigma+C H_{3}O H\\Sigma\\Sigma}}\n$$  \n\n酯交换法制备丙烯酸高级醇或官能性丙烯酸酯时，低级酯大多用丙烯酸甲酯，由于其沸点较低（80℃)，故酯化反应只能在较低的温度下进行，使反应时间延长；产物甲醇又能与丙烯酸甲酯形成共沸物，其沸点为 $62\\sim63^{\\circ}C$ ，会将反应物丙烯酸甲酯带走，从而降低高级醇的收率。丙烯酸甲酯和丙烯酸高级酯容易发生共聚和均聚，也使高级酯产率降低，因此常要使用更多的阻聚剂。从成本和后处理困难考虑，工业上本法已不用于制备丙烯酸高级醇和官能性丙烯酸酯。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 41,
+        "chunk": "# 2.2.3 酰氯法  \n\n$$\n\\mathrm{H}_{2}\\mathrm{C}\\mathrm{-CHCOOH+SOCl}_{2}\\longrightarrow\\mathrm{H}_{2}\\mathrm{C}\\mathrm{-CHCOCl}\\ +\\mathrm{HCl}+\\mathrm{SO}_{2}\n$$  \n\n本方法先将丙烯酸与二氯亚矾反应制得丙烯酰氯，再与醇发生酯化反应，不用催化剂和脱水剂，由于反应温度低，不用加阻聚剂，酯化反应几乎定量进行，产品纯度高。但要经两步反应，成本高。反应中有大量HCl和 $\\mathsf{s o}_{2}$ 产生，要用多级稀碱液和水吸收。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 42,
+        "chunk": "# 2.2.4 相转移法  \n\n甲基丙烯酸钠是固体，环氧氯丙烷是液体，无催化剂存在时，它们之间很难发生反应，需用相转移催化剂进行催化反应。相转移催化剂有季铵盐、季磷盐、冠醚等，但以季铵盐最常见，如十六烷基三甲基溴化铵、苄基三甲基氯化铵、四甲基氯化铵等。在反应体系中有水存在时，会有副反应发生，因此要提高产率就应该保持原料和系统干燥无水。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 43,
+        "chunk": "# 2.2.5 加成酯化法  \n\n$$\n\\begin{array}{r l}{\\mathsf{R}_{1}}&{{}\\qquad\\mathsf{R}_{1}}\\\\ {\\mathsf{H}_{2}\\mathrm{C}-\\mathsf{C}\\mathsf{H}-\\mathsf{C}\\mathsf{O}\\mathsf{O}\\mathsf{H}\\ +}&{{}\\mathsf{H}_{2}\\mathsf{C}\\overbrace{\\mathbf{C}\\mathbf{H}-\\mathsf{R}_{2}}^{\\mathsf{O}}\\xrightarrow{\\mathsf{M}(\\mathscr{U}\\cdot\\mathscr{R})}\\mathrm{H}_{2}\\mathbb{C}-\\mathsf{C}\\mathbf{H}-\\mathsf{C}\\mathsf{O}\\mathsf{O}-\\mathsf{C}\\mathsf{H}_{2}-\\mathsf{C}\\mathbf{H}-\\mathsf{R}_{2}}\\end{array}\n$$  \n\n将环氧乙烷或环氧丙烷直接通入（甲基）丙烯酸，在催化剂存在下发生开环加成酯化反应，制得（甲基）丙烯酸羟基酯。  \n\n阳离子光固化活性稀释剂乙烯基醚可以通过以下方法合成。  \n\n（1）乙烯氧化法  \n\n$$\n\\mathrm{{ROH}+H_{2}C=C H_{2}+\\frac{1}{2}O_{2}\\xrightarrow[]{\\mathrm{{\\#E}\\{\\mathscr{k}\\}\\{\\mathscr{n}\\}}}\\mathrm{{ROCH}\\mathrm{{-CH}_{2}+H_{2}O}}}\n$$  \n\n将醇、乙烯和氧气在催化剂PdCl·CuCl·HCl存在下反应，生成乙烯基醚和水。 （2）乙烯酯交换法  \n\n$$\n\\mathrm{ROH}+\\mathrm{H_{2}C}=\\mathrm{CH_{2}O C O C H_{3}}\\xrightarrow[]{\\#\\#\\#\\mathbb{K}\\mathbb{K}}\\mathrm{ROCH}-\\mathrm{CH_{2}}+\\mathrm{CH_{3}C O O H}\n$$  \n\n将醇与醋酸乙烯酯在催化剂 $\\mathrm{PdCl}_{2}\\cdot\\mathrm{Na}_{2}\\mathrm{WO}_{4}$ 存在下反应，生成乙烯基醚和醋酸。  \n\n（3）乙炔法  \n\n$$\n\\mathrm{HC=CH\\+ROH{\\stackrel{\\textstyle\\qquad}{\\longrightarrow}}\\ \\mathrm{ROCH{\\mathrm{-CH_{2}}}}}\n$$  \n\n在高温高压下，醇与乙炔直接反应制得乙烯基醚，但本法使用高压高温设备，收率低，  \n\n特别是乙炔有爆炸危险（乙炔的爆炸极限范围宽，与空气的体积比为 $2.5\\%\\sim81\\%)$ ，操作稍有不慎就会引发爆炸。为此改用 $\\mathbf{CaC}_{2}$ ，不直接使用乙炔气与醇反应制备乙烯基醚。  \n\n$$\n\\mathrm{CaC}_{2}+\\mathrm{ROH}\\longrightarrow\\mathrm{ROCH}{=}\\mathrm{CH}_{2}+\\mathrm{Ca}(\\mathrm{OR})_{2}\n$$  \n\n（4）脱卤化氢法  \n\n$$\n\\mathrm{XCH_{2}\\mathrm{-}C H_{2}O R\\ {\\frac{\\hbar\\hbar}{-\\hbar\\mathrm{X}}}\\ C H_{2}\\mathrm{-}C H O R}\n$$  \n\n催化剂用碱金属化合物如KOH、 $\\mathbf{NaOH}$ 等；通常需要高压反应釜并在 $220^{\\circ}\\mathrm{C}$ 以上高温反应，使用相转移催化剂如季铵盐等，可使反应更为温和， $150^{\\circ}\\mathrm{C}$ 反应即可。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 44,
+        "chunk": "# （5）缩醛热分解法  \n\n$$\n{\\bf R}_{1}{\\bf R}_{2}\\mathrm{CHCY(OR_{3})}_{2}\\xrightarrow[\\bigtriangleup]{\\#\\mathcal{k}/\\mathcal{k}\\mathcal{W}_{1}}{\\bf R}_{1}{\\bf R}_{2}\\mathrm{C}\\mathrm{-}\\mathrm{CY-OR}_{3}\n$$  \n\n式中， ${\\bf R}_{1}$ ， ${\\bf R}_{2}$ 为 $\\mathbf{C}_{1}{\\sim}\\mathbf{C}_{3}$ 烷基、芳基、 $\\mathtt{H}$ $\\mathbf{R}_{3}$ 为 $\\mathrm{CH}_{3}$ ， $\\mathrm{C}_{2}\\mathrm{H}_{5}$ ； $\\mathbf{Y}$ 为 $\\mathbf{H}$ ， $\\mathrm{CH}_{3}$  \n\n以前用气相裂解法，催化剂为铂等贵金属，价格昂贵，裂解设备要求耐压，反应条件控制要求严格，产物复杂，后处理困难。  \n\n用液相分解，设备简单，反应条件温和，容易控制，催化剂为 $85\\%$ $\\mathrm{H_{3}P O_{4}}$ 、 $98\\%$ $\\mathrm{H}_{2}\\mathrm{SO}_{4}$ 或 $\\mathrm{H}_{3}\\mathrm{C}-\\bigoplus_{-}-\\mathrm{SO}_{3}\\mathrm{H}$ ，但仍存在转化率较低的问题。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 45,
+        "chunk": "# 2.3 单官能团活性稀释剂  \n\n单官能团活性稀释剂每个分子中仅含一个可参与光固化反应的活性基团，分子量较低，因此具有如下的特点。  \n\n$\\textcircled{1}$ 黏度低，稀释能力强。  \n\n$\\textcircled{2}$ 光固化速率低，这是因为单官能团活性稀释剂的反应基团含量低，导致光固化速率低。  \n\n$\\textcircled{3}$ 交联密度低，只含一个光活性基团，因此在光固化反应中不会产生交联点，使反应体系交联密度下降。  \n\n$\\textcircled{4}$ 转化率高，由于单官能团活性稀释剂的碳碳双键的含量低，黏度小，容易参与聚合，故转化率高。  \n\n$\\textcircled{5}$ 体积收缩率低，在自由基加成聚合时，碳碳双键转化成单键，分子间距变小，密度增大，造成体积收缩。但单官能团活性稀释剂因碳碳双键含量低，所以体积收缩较少。  \n\n$\\textcircled{6}$ 挥发性较大，气味大、易燃，毒性也相对较大。  \n\n常见单官能团活性稀释剂的物理性能见表2-6，部分活性稀释剂的挥发性和闪点见表2-7。 L  \n\n表2-6常见单官能团活性稀释剂的物理性能  \n\n\n<html><body><table><tr><td>活性稀 释剂</td><td>分子量</td><td>沸点 /℃C</td><td>密度(25℃) /（g/cm3)</td><td>黏度（25℃) /mPa·s</td><td>折射率 (25℃)</td><td>表面张力 /(X10-3N/m)</td><td>玻璃化温度 /℃</td></tr><tr><td>St</td><td>104</td><td>145</td><td>0.906</td><td>0.78</td><td>1.5468</td><td rowspan=\"2\"></td><td rowspan=\"2\">100 30</td></tr><tr><td>VA</td><td>86</td><td>72</td><td>0.9312(20℃)</td><td>0.43(20℃)</td><td>1.3959</td></tr><tr><td>NVP</td><td>111</td><td>123(6666Pa)</td><td>1.04</td><td>2.07</td><td>1.5110</td><td rowspan=\"2\"></td><td rowspan=\"2\">-56</td></tr><tr><td>BA</td><td>128</td><td>147</td><td>0.894</td><td>0.9</td><td>1.4160</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>活性稀 释剂</td><td>分子量</td><td>沸点 /℃</td><td>密度（25℃) /（g/cm3)</td><td>黏度（25℃） /mPa·s</td><td>折射率 (25℃)</td><td>表面张力 /(×10-3N/m)</td><td>玻璃化温度 /C</td></tr><tr><td>2-EHA</td><td>184</td><td>213</td><td>0.881</td><td>1.54</td><td>1.4330</td><td>28.0</td><td>-74</td></tr><tr><td>IDA</td><td>212</td><td>158(6666Pa)</td><td>0.885</td><td>5</td><td>1.440</td><td>28.6</td><td>-60</td></tr><tr><td>LA</td><td>240</td><td></td><td>0.88</td><td>8</td><td></td><td>29.8</td><td>65</td></tr><tr><td>HEA</td><td>116</td><td>202</td><td>1.1038(20℃)</td><td>5.34</td><td>1.4505(20℃)</td><td></td><td>-60</td></tr><tr><td>HPA</td><td>130</td><td>205</td><td>1.057(20℃)</td><td>5.70</td><td>1.4450(0℃)</td><td></td><td>-60</td></tr><tr><td>HEMA</td><td>130</td><td>205</td><td>1.064</td><td></td><td>1.4505</td><td></td><td>55</td></tr><tr><td>HPMA</td><td>144</td><td>96(1333Pa)</td><td>1.027</td><td></td><td>1.4456</td><td></td><td>26</td></tr><tr><td>POEA</td><td>192</td><td>134(1333Pa)</td><td>1.10</td><td>12</td><td></td><td>39.2</td><td>5</td></tr><tr><td>IBOA</td><td>208</td><td>275</td><td>0.990</td><td>9</td><td>1.4744</td><td>31.7</td><td>94</td></tr><tr><td>GA</td><td>128</td><td>83(2666Pa)</td><td></td><td>5</td><td>1.4472</td><td></td><td></td></tr><tr><td>GMA</td><td>142</td><td>176</td><td>1.073</td><td>3.39</td><td>1.4482</td><td></td><td>41</td></tr></table></body></html>  \n\n表2-7部分活性稀释剂的挥发性和闪点  \n\n\n<html><body><table><tr><td>活性稀释剂</td><td>失重速率/(mg/min)</td><td>闪点/℃</td></tr><tr><td>St</td><td>19.0</td><td>31</td></tr><tr><td>BA</td><td>17.0</td><td>49</td></tr><tr><td>2-EHA</td><td>0.5</td><td>90</td></tr><tr><td>IBOA</td><td>0.2</td><td></td></tr><tr><td>IDA</td><td>0.08</td><td>127</td></tr><tr><td>NPGDA</td><td>0.07</td><td>115</td></tr><tr><td>HDDA</td><td>0.02</td><td>151</td></tr></table></body></html>  \n\n单官能团活性稀释剂按结构上的不同可分为丙烯酸烷基酯、（甲基）丙烯酸羟基酯、带有环状结构或苯环的（甲基）丙烯酸酯和乙烯基活性稀释剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 46,
+        "chunk": "# 2.3. 1 丙烯酸烷基酯  \n\n(1）丙烯酸丁酯（BA)  \n\n$$\n\\begin{array}{c}{{\\mathrm{0}}}\\\\ {{\\mathrm{H_{2}C=C H C-O-C H_{2}C H_{2}C H_{2}C H_{3}}}}\\end{array}\n$$  \n\n低黏度，稀释效果好，早期作为活性稀释剂使用；但气味大、挥发性大，易燃，故现在已基本上不用。  \n\n(2）丙烯酸异辛酯（2-EHA)  \n\n$$\n\\begin{array}{c}{{0}}\\\\ {{{\\underbrace{\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom{\\left|\\sum_{i=1}^{9}\\phantom\\bigg{\\left|}\\sum_{\\sum}\\phantom{\\left|\\sum_{i \n$$  \n\n低黏度，稀释效果好，低 $T_{\\mathrm{g}}$ ，有较好的增塑效果，早期作为活性稀释剂使用；因有气味、挥发性稍大，影响使用。  \n\n(3）丙烯酸异癸酯(IDA)  \n\n$$\n\\begin{array}{r l}{0}&{{}}\\\\ {1}&{{}}\\\\ {\\mathrm{H}_{2}\\mathrm{C}\\mathrm{-}\\mathrm{CHC}\\mathrm{-}0\\mathrm{-}(\\mathrm{CH}_{2}),\\mathrm{CH}(\\mathrm{CH}_{3})_{2}}\\end{array}\n$$  \n\n低黏度，稀释效果好，低 ${{T}_{8}}$ ，有较好的增塑效果，挥发性较小。  \n\n(4）丙烯酸月桂酯（LA)  \n\n$$\n\\begin{array}{c}{{\\displaystyle0}}\\\\ {{\\mathrm{H}_{2}\\mathrm{C}\\mathrm{-}\\mathrm{CHC}\\mathrm{-}\\mathrm{0}\\mathrm{-}(\\mathrm{CH}_{2})_{11}\\mathrm{CH}_{3}}}\\end{array}\n$$  \n\n低黏度，低挥发，有疏水性脂肪族长主链，低 $T_{\\mathrm{{g}}}$ ，有较好的增塑效果。  \n\n（5）丙烯酸乙氧基乙氧基乙酯（EOEOEA)  \n\n$$\n\\begin{array}{c}{{0}}\\\\ {{\\ l\\mathrm{_{2}C-C H C-O-C H_{2}C H_{2}-O-C H_{2}C H_{2}-O C H_{2}C H_{3}}}}\\end{array}\n$$  \n\n低黏度、低挥发、低 ${{T}_{\\mathrm{{g}}}}$ ，有较好增塑效果。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 47,
+        "chunk": "# 2.3.2（甲基）丙烯酸羟基酯  \n\n（1）丙烯酸羟乙酯（HEA）和丙烯酸羟丙酯（HPA)  \n\n$$\n\\begin{array}{c}{0}\\\\ {\\scriptstyle{\\begin{array}{c}{{\\scriptstyle{\\mathsf{I}}}}\\\\ {{\\scriptstyle{\\mathsf{H}}}_{2}{\\scriptstyle{\\mathsf{C}}}\\end{array}}-{\\mathrm{CHC}}-0-{\\scriptstyle{\\mathsf{C H}}}_{2}{\\scriptstyle{\\mathsf{C H}}}_{2}{\\scriptstyle{\\mathsf{O H}}}}\\\\ {0}\\\\ {{\\scriptstyle{\\mathsf{I}}}}\\\\ {{\\scriptstyle{\\mathsf{H}}}_{2}{\\scriptstyle{\\mathsf{C}}}\\longrightarrow{\\scriptstyle{\\mathsf{C H}}}{\\scriptstyle{\\mathsf{C}}}-0-{\\scriptstyle{\\mathsf{C H}}}_{2}{\\scriptstyle{\\mathsf{C H}}}_{2}{\\scriptstyle{\\mathsf{C H}}}_{2}{\\scriptstyle{\\mathsf{O H}}}}\\end{array}}}\\end{array}\n$$  \n\n高沸点，低黏度，低 $T_{\\mathrm{~g~}}$ ，反应活性适中，带有羟基，有利于提高对极性基材的附着力，是早期最常用的活性稀释剂；但皮肤刺激性和毒性较大，目前也较少使用。由于HEA 和HPA分子带有丙烯酰氧基，并含有羟基，可与异氰酸基反应，现主要用于制备PUA 的原料。  \n\n（2）甲基丙烯酸羟乙酯（HEMA）和甲基丙烯酸羟丙酯（HPMA)  \n\n高沸点，低黏度，因是甲基丙烯酸酯，所以固化速率比HEA和HPA慢，但皮肤刺激性和毒性又低于HEA和HPA，带有羟基，有利于提高对极性基材的附着力，HEMA 是阻焊剂常用的活性稀释剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 48,
+        "chunk": "# 2.3.3带有环状结构或苯环的（甲基）丙烯酸酯  \n\n（1）甲基丙烯酸缩水甘油酯（GMA)  \n\n沸点较高，低黏度，带有环氧基，有利于提高附着力，但价格贵，因属于甲基丙烯酸酯类，所以固化速率较慢。  \n\n(2）甲基丙烯酸异冰片酯(IBOA)  \n\n![](images/9c956489831b948a31455ed2fa5ca4657d9aa00db4b6cf7c11fd8bb30738aacb.jpg)  \n\n高沸点，黏度较低，高折射率和高 $\\ensuremath{T_{\\mathrm{{g}}}}$ ，固化收缩率低 $(8.2\\%)$ ，有利于提高附着力，低皮肤刺激性，但价格高，又有气味，影响其使用。  \n\n(3）丙烯酸四氢呋喃甲酯（THFA)  \n\n$$\nH_{2}C-C H-C-0-C H_{2}-C O\n$$  \n\n高沸点，黏度较低，低 ${T_{\\mathrm{g}}}$ ，含有极性的四氢呋喃环，有利于附着力提高。（4）丙烯酸苯氧基乙酯（POEA、2-PEA)  \n\n$$\n\\begin{array}{c}{{0}}\\\\ {{\\mathrm{H_{2}C-C H C-0-C H_{2}C H_{2}-0-\\bigcup}}}\\end{array}\n$$  \n\n高沸点，黏度较低，低 $T_{\\mathbf{g}}$ ，反应活性较高，低皮肤刺激性，但有酚的气味。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 49,
+        "chunk": "# 2.3.4乙烯基活性稀释剂  \n\n(1）苯乙烯（St)  \n\n![](images/a4307611ef189aaedb2e5894ef39bb44d8d35702fc90b25949c3d909a02ae4f9.jpg)  \n\n最早与不饱和聚酯配合作为第一代光固化涂料应用于木器涂料，虽然价廉，黏度低，稀释能力强，但因其高挥发性、高易燃性、气味大、毒性大以及固化速率较慢，目前在光固化产品中很少使用St作活性稀释剂。  \n\n(2）醋酸乙烯酯（VA)  \n\n价廉，低黏度，稀释能力强，反应活性较高，但低沸点，高挥发性，易燃易爆，实际上光固化产品中不采用VA作活性稀释剂。  \n\n（3）N-乙烯基吡咯烷酮（NVP)  \n\n![](images/882a02d5f90ff9cd58133ce8f5156caf9cedb98e956cf56187fe550ba6570d6a.jpg)  \n\n低黏度，稀释能力强，反应活性高，低皮肤刺激性，曾是最受欢迎的活性稀释剂。但因价格贵，气味大，有致癌毒性，限制了它的应用，目前已很少使用。一般用量不能超过$10\\%\\sim20\\%$ ，因 NVP及其聚合物都是水溶性的，加入量大会影响涂料的耐水性。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 50,
+        "chunk": "# 2.4 双官能团活性稀释剂  \n\n双官能团活性稀释剂每个分子中含有两个可参与光固化反应的活性基团，因此光固化速率比单官能团活性稀释剂要快，成膜时发生交联，有利于提高固化膜的物理力学性能和耐抗性。由于分子量增大，黏度也相应增加，但仍保持良好的稀释性，挥发性较小，气味较低，因此双官能团活性稀释剂大量应用于光固化产品中。表2-8列出了常用双官能团活性稀释剂的物理性能。  \n\n表2-8常用双官能团活性稀释剂的物理性能  \n\n\n<html><body><table><tr><td>活性稀释剂</td><td>分子量</td><td>沸点 /℃</td><td>密度（25℃) /（g/cm3)</td><td>黏度(25℃) /mPa·s</td><td>折射率 (25℃)</td><td>表面张力 /(X10-N/m)</td><td>玻璃化温度 /℃</td></tr><tr><td>BDDA HDDA NPGDA DEGDA TEGDA PEG(200)DA PEG(400)DA</td><td>198 226 212 214 258 302 508</td><td>275 295 100(400.0Pa) 162(266.6Pa)</td><td>1.057(20℃) 1.03 1.03 1.006 1.109 1.110 1.12</td><td>8 9 10 12 15 25 57</td><td>1.458 1.452 1.467</td><td>36.2 35.7 33.8 38.2 39.1 41.3</td><td>45 43 107 100 70</td></tr></table></body></html>  \n\n双官能团活性稀释剂从二元醇结构上可分为乙二醇类二丙烯酸酯、丙二醇类二丙烯酸酯和其他二醇类二丙烯酸酯。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 51,
+        "chunk": "# 2.4.1 乙二醇类二丙烯酸酯  \n\n(1）二乙二醇二丙烯酸酯(DEGDA)  \n\n$$\n\\begin{array}{c}{{0}}\\\\ {{1}}\\\\ {{\\mathrm{H}_{2}\\mathrm{C}\\mathrm{-}\\mathrm{CH}\\mathrm{-}\\mathrm{C}\\mathrm{-}\\mathrm{O}\\mathrm{-}\\mathrm{CH}_{2}\\mathrm{-}\\mathrm{CH}_{2}\\mathrm{-}\\mathrm{O}\\mathrm{-}\\mathrm{CH}_{2}\\mathrm{-}\\mathrm{CH}_{2}\\mathrm{-}\\mathrm{CH}_{2}\\mathrm{-}\\mathrm{O}\\mathrm{-}\\mathrm{C}\\mathrm{-}\\mathrm{CH}\\mathrm{-}\\mathrm{CH}_{2}}}\\end{array}\n$$  \n\n低黏度，光固化速率快，但对皮肤刺激性严重，故现在很少使用。  \n\n（2）三乙二醇二丙烯酸酯（TEGDA）  \n\n$$\n\\begin{array}{c c}{{0}}&{{0}}\\\\ {{1}}&{{1}}\\\\ {{\\mathrm{H}_{2}C-\\mathrm{CH}-\\mathrm{C}-0-\\mathrm{CH}_{2}-\\mathrm{CH}_{2}-0-\\mathrm{CH}_{2}-\\mathrm{CH}_{2}-\\mathrm{CH}_{2}-0-\\mathrm{CH}_{2}-\\mathrm{CH}_{2}-0-\\mathrm{C}-\\mathrm{CH}-\\mathrm{CH}_{2}}}&{{-\\mathrm{C}-\\mathrm{CH}_{2}}}\\end{array}\n$$  \n\n低黏度，光固化速率快，因对皮肤刺激性大，现在很少使用。  \n\n（3）聚乙二醇二丙烯酸酯系列  \n\n聚乙二醇(200)二丙烯酸酯[PEG(200)DA] 聚乙二醇(400)二丙烯酸酯[PEG(400)DA] 聚乙二醇(600)二丙烯酸酯［PEG(600)DA]  \n\n$$\n\\begin{array}{c}{{0}}\\\\ {{1}}\\\\ {{\\mathrm{H_{2}C-C H-C-0-\\left(C H_{2}-C H_{2}-O\\right)_{n}-O-C-C H-C H_{2}}}}\\end{array}\n$$  \n\n这是聚乙二醇二丙烯酸酯系列，PEG(200)DA中n4，PEG(400)DA中n=8～9,PEG(600)DA中n13，随着n增大，黏度变大，Tg下降，毒性和对皮肤刺激性降低，因此，膜柔韧性增加，亲水性也增加。 创迎",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 52,
+        "chunk": "# 2.4.2丙二醇类二丙烯酸酯  \n\n（1）二丙二醇二丙烯酸酯（DPGDA)  \n\n低黏度，稀释能力强，光固化速率快，但对皮肤刺激性稍大，是常用的活性稀释剂之一。  \n\n(2）三丙二醇二丙烯酸酯（TPGDA)  \n\n黏度较低，稀释能力强，光固化速率快，体积收缩较小，皮肤刺激性也较小，价格较低，是目前最常用的双官能团活性稀释剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 53,
+        "chunk": "# 2.4.3其他二醇类二丙烯酸酯  \n\n(1）1,4-丁二醇二丙烯酸酯(BDDA)  \n\n$$\n\\begin{array}{c c}{{0}}&{{0}}\\\\ {{\\downarrow}}&{{\\parallel}}\\\\ {{{\\mathrm{H}}_{2}\\mathrm{C}\\mathrm{-}\\mathrm{CH}\\mathrm{-}\\mathrm{C}\\mathrm{-}0\\mathrm{-}\\mathrm{CH}_{2}\\mathrm{-}\\mathrm{CH}_{2}\\mathrm{-}\\mathrm{CH}_{2}\\mathrm{-}\\mathrm{CH}_{2}\\mathrm{-}\\mathrm{CH}_{2}\\mathrm{-}0\\mathrm{-}\\mathrm{C}\\mathrm{-}\\mathrm{CH}\\mathrm{-}\\mathrm{CH}_{2}}}}\\end{array}\n$$  \n\n低黏度，对低聚物溶解性好，稀释能力强，但对皮肤刺激性大。  \n\n(2）1,6-己二醇二丙烯酸酯(HDDA)  \n\n$$\n\\begin{array}{c c}{{0}}&{{0}}\\\\ {{\\ l}}&{{\\ l}}\\\\ {{{\\bf H}_{2}{\\bf C}-{\\bf C}{\\bf H}-{\\bf C}-0-{\\bf C}{\\bf H}_{2}-{\\bf C}{\\bf H}_{2}-{\\bf C}{\\bf H}_{2}-{\\bf C}{\\bf H}_{2}-{\\bf C}{\\bf H}_{2}-{\\bf C}{\\bf H}_{2}-{\\bf C}{\\bf H}_{2}-{\\bf C}{\\bf H}_{2}-0-{\\bf C}-{\\bf C}{\\bf H}-{\\bf C}{\\bf H}_{2}}}\\end{array}\n$$  \n\n低黏度，稀释能力强，对塑料的附着力好，可改善固化膜的柔韧性，但对皮肤刺激性较大，价格较高，是常用的活性稀释剂之一。  \n\n(3）新戊二醇二丙烯酸酯（NPGDA)  \n\n$$\n\\begin{array}{c}{{0}}\\\\ {{\\big\\downarrow}}\\\\ {{\\mathrm{H_{2}C-C H-C-O-C H_{2}-C-C H_{2}-O-C-C H-C H-C H-C H_{2}}}}\\\\ {{\\big\\downarrow}}\\\\ {{\\mathrm{CH_{3}}}}\\end{array}\n$$  \n\n低黏度，稀释能力强，高活性，光固化速率快，对塑料附着力好，高 $\\boldsymbol{T}_{8}$ ，但对皮肤刺激性较大，是常用的活性稀释剂之一。  \n\n(4）邻苯二甲酸乙二醇二丙烯酸酯(PDDA)  \n\n价廉，光固化速率快，是我国自行开发的活性稀释剂，因黏度高，稀释效果稍差。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 54,
+        "chunk": "# 2.5 多官能团活性稀释剂  \n\n多官能团活性稀释剂每个分子中都含有三个或三个以上可参与光固化反应的活性基团，因此不仅光固化速率快，而且交联密度大，相应地固化膜硬度高，脆性大，耐抗性优异。分子量大，黏度高，稀释性较差；高沸点，低挥发性，收缩率大。常用的多官能团活性稀释剂的物理性能见表2-9。  \n\n表2-9常用的多官能团活性稀释剂的物理性能  \n\n\n<html><body><table><tr><td>活性稀释剂</td><td>分子量</td><td>密度（25℃） /(g/cm3)</td><td>黏度（25℃） /mPa·s</td><td>折射率 (25℃)</td><td>表面张力 /(X10-3N/m)</td><td>玻璃化温度 1℃</td></tr><tr><td>TMPTA</td><td>296</td><td>1.11</td><td>106</td><td>1.475</td><td>36.1</td><td>62</td></tr><tr><td>PETA</td><td>298</td><td>1.18</td><td>520</td><td>1.477</td><td>39.0</td><td>103</td></tr><tr><td>PETTA</td><td>352</td><td>1.185(20℃)</td><td>342(38℃)</td><td></td><td>40.1</td><td>103</td></tr><tr><td>DTMPTTA</td><td>482</td><td>1.11</td><td>600</td><td></td><td>36.0</td><td>98</td></tr><tr><td>DPPA</td><td>524</td><td>1.18</td><td>13600</td><td>1.491</td><td>39.9</td><td>90</td></tr></table></body></html>  \n\n(1）三羟甲基丙烷三丙烯酸酯（TMPTA)  \n\n![](images/7c2ab485d60810fca62876634e7f285b670a58639f2ddfe837b08266aee4e5c6.jpg)  \n\n黏度较大，但在多官能团活性稀释剂中是最低的一种；光固化速率快，交联密度大；固化膜坚硬而发脆，耐抗性好。价格较廉，虽然对皮肤的刺激性较大，但仍是最常用的多官能团活性稀释剂。  \n\n（2）季戊四醇三丙烯酸酯（PETA）和季戊四醇四丙烯酸酯（PETTA)  \n\n![](images/8d44b92f8347ddccf5880f45709c3167bc3c53a2e216393697bd461c5a7a5211.jpg)  \n\n黏度大，稀释性差；光固化速率快，交联密度大；固化膜硬而脆，耐抗性好。PETA有羟基，有利于提高附着力；但PETA 毒性大，怀疑有致癌性，因而限制其使用。  \n\n（3）二缩三羟甲基丙烷四丙烯酸酯（DTMPTA)  \n\n![](images/26175b40e7b2d00a066b771435f5eb7c45402905e7c89bc0debc2d58a9fbe58c.jpg)  \n\n高黏度，高反应活性，高交联密度，极低的皮肤刺激性；固化膜硬，富有弹性而不脆，耐拉伸性优良。在光固化产品中不作活性稀释剂，而为提高光固化速率和交联密度使用。  \n\n（4）二季戊四醇五丙烯酸酯（DPPA）和二季戊四醇六丙烯酸酯（DPHA)  \n\n![](images/20dae615c0aa8e2101b6dd2cf4ad9a2031ab07f17bf461bf12869dbdd12aca32.jpg)  \n\n<html><body><table><tr><td>活性稀释剂</td><td>官能度</td><td>沙多玛</td><td>优比西</td><td>巴斯夫</td><td>科宁</td><td>新中村</td><td>美源</td><td>长兴</td><td>石梅</td><td>天骄</td><td>天津试剂所</td><td>东方亚克力</td><td>宏辉</td><td>利田</td><td>高科</td></tr><tr><td>2-EHA</td><td>１</td><td>SR440</td><td></td><td></td><td></td><td></td><td></td><td>EM216</td><td></td><td></td><td></td><td>2-EHA</td><td></td><td></td><td></td></tr><tr><td>IDA</td><td>1</td><td>SR395</td><td></td><td></td><td>4810</td><td></td><td></td><td>EM219</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>LA</td><td>1</td><td>SR335</td><td></td><td>LA</td><td>4812</td><td></td><td></td><td>EM215</td><td></td><td>LA</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>GMA</td><td>1</td><td>SR379</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>GMA</td><td></td><td></td><td></td></tr><tr><td>IBOA</td><td>1</td><td>SR506</td><td>IBOA</td><td></td><td></td><td>A-IB</td><td></td><td>EM70</td><td></td><td>IBOA</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>POEA</td><td>1</td><td>SR339</td><td>EB110</td><td>POEA</td><td>4035</td><td>AMP-10G</td><td></td><td>EM210</td><td></td><td>PHEA</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>BDDA</td><td>2</td><td>SR213</td><td></td><td>BDDA</td><td></td><td></td><td></td><td>EM2241</td><td></td><td>BDDA</td><td>BDDA</td><td></td><td></td><td>BDDA</td><td>BDDA</td></tr><tr><td>HDDA</td><td>2</td><td>SR238</td><td>HDDA</td><td>HDDA</td><td>4017</td><td>A-HD-N</td><td>M-200</td><td>EM221</td><td>VM2001</td><td>HDDA</td><td>HDDA</td><td>HDDA</td><td>HDDA</td><td>HDDA</td><td></td></tr><tr><td>PDDA</td><td>2</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>PDDA</td><td>PDDA</td><td>PDDA</td><td></td><td>PDDA</td></tr><tr><td>NPGDA</td><td>2</td><td>SR247</td><td></td><td></td><td></td><td></td><td></td><td>EM225VM2003</td><td></td><td></td><td>NPGDA</td><td>NPGDA</td><td>NPGDA</td><td>NPGDA</td><td>NPGDA</td></tr><tr><td>DEGDA</td><td>2</td><td>SR230</td><td></td><td></td><td></td><td>APG-100</td><td></td><td></td><td></td><td></td><td></td><td>DEGDA</td><td></td><td>DEGDA</td><td></td></tr><tr><td>TEGDA</td><td>2</td><td>SR272</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>TEGDA</td><td></td><td></td><td></td></tr><tr><td>PEG(200)DA</td><td>2</td><td>SR259</td><td></td><td></td><td>4050</td><td>A200</td><td>M-240</td><td>EM224</td><td></td><td></td><td>PEG(200)DAPEG(200)DAPEG(200)DA</td><td></td><td></td><td></td><td></td></tr><tr><td>PEG(400)DA</td><td>2</td><td>SR344</td><td></td><td></td><td>4226</td><td>A400</td><td>M-280</td><td>EM226</td><td>VM2005</td><td></td><td></td><td>PEG(400)DA</td><td></td><td></td><td></td></tr><tr><td>DPGDA</td><td>2</td><td>SR508</td><td>DPGDA</td><td>DPGDA</td><td>4061</td><td></td><td></td><td>EM222</td><td>VM2004</td><td>DPGDA</td><td>DPGDA</td><td></td><td>DPGDA</td><td>DPGDA</td><td>DPGDA</td></tr><tr><td>TPGDA</td><td>2</td><td>SR306</td><td>TPGDA</td><td>TPGDA</td><td>4006</td><td>APG-200</td><td>M-220.</td><td>EM223</td><td>VM2002</td><td>TPGDA</td><td>TPGDA</td><td>TPGDA</td><td>TPGDA</td><td>TPGDA</td><td>TPGDA</td></tr><tr><td>TMPTA</td><td>3</td><td>SR351</td><td>TMPTA</td><td>TMPTA</td><td></td><td>TMPT</td><td>M-300</td><td>EM231</td><td>VM3001</td><td>TMPTA</td><td>TMPTA</td><td>TMPTA</td><td>TMPTA</td><td>TMPTA</td><td>TMPTA</td></tr><tr><td>PETA</td><td>3</td><td>SR444</td><td></td><td></td><td></td><td>A-TMM-3</td><td>M-340</td><td>EM235</td><td></td><td></td><td></td><td></td><td></td><td>PETA</td><td>PETA</td></tr><tr><td>PETTA</td><td>4</td><td>SR295</td><td>PETA</td><td></td><td></td><td>A-TMM-4</td><td></td><td>EM241</td><td></td><td></td><td></td><td></td><td></td><td></td><td>PETA4</td></tr><tr><td>DTMPTTA</td><td>4</td><td>SR355</td><td></td><td></td><td></td><td>D-TMP</td><td></td><td>EM242</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>DPPA</td><td>5</td><td></td><td>EB140</td><td></td><td>4399</td><td></td><td></td><td></td><td>VM5001</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>DPHA</td><td>6</td><td>SR399</td><td>DPHA</td><td></td><td></td><td>A-DPH</td><td></td><td></td><td>VM6001</td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n高黏度，极高的反应活性和交联密度，极低的皮肤刺激性；固化膜有极高的硬度、耐刮性和耐抗性。同样在光固化产品中不作活性稀释剂，而为提高光固化速率和交联密度使用。常用的单、双、多官能团活性稀释剂的主要生产厂家产品代号见表2-10。  \n\n这是第二代的丙烯酸酯活性稀释剂，都是由乙氧基化（—CHz—CH—O—）或丙氧基化（—CH—CH2—CH一O—）的醇类丙烯酸酯构成的。  \n\n乙氧基化或丙氧基化的醇类丙烯酸酯活性稀释剂的开发是为了改善第一代丙烯酸酯活性稀释剂存在的皮肤刺激性和毒性偏大及固化收缩率大的病，同时仍保持其较快的光固化速率。由表2-11和表2-12可知丙烯酸酯母体经乙氧基化或丙氧基化后，皮肤刺激性和固化收缩率有明显的降低，有的黏度也有降低。  \n\n表2-11活性稀释剂烷氧基化性能比较  \n\n\n<html><body><table><tr><td>活性稀释剂</td><td>性能</td><td>母体</td><td>乙氧基化</td><td>丙氧基化</td></tr><tr><td>NPGDA</td><td>黏度(25℃)/mPa·s PII</td><td>10 4.96</td><td>13 0.2</td><td>15 0.8</td></tr><tr><td>TMPTA</td><td>黏度（25℃）/mPa·s PII</td><td>106 4.8</td><td>60： · 1.5</td><td>85 1.0</td></tr><tr><td>PETA</td><td>黏度(25℃)/mPa·s PII</td><td>600 2.8</td><td></td><td>225 1.0</td></tr></table></body></html>\n\n注：PII为初期皮肤刺激指数。  \n\n表2-12 乙氧基化、丙氧基化及甲氧基化活性稀释剂固化收缩率  \n\n\n<html><body><table><tr><td>活性稀释剂</td><td>固化收缩率/%</td><td>活性稀释剂</td><td>固化收缩率/%</td></tr><tr><td>TMPTA</td><td>26</td><td>HDDA</td><td>14</td></tr><tr><td>TMP(EO)TA</td><td>17~24</td><td>HDDMEMA</td><td>8</td></tr><tr><td>TMP(PO) TA</td><td>12~15</td><td>TEGDA</td><td>20</td></tr><tr><td>TMP(EO)MEDA</td><td>19</td><td>TEGMEMA</td><td>9</td></tr><tr><td>TMP(PO)MEDA</td><td>6</td><td></td><td></td></tr></table></body></html>  \n\n表 2-13列出部分烷氧基化丙烯酸酯活性稀释剂的物理性能，表2-14为不同乙氧基化的TMPTA的物理性能，显然，随着分子中乙氧基增加，黏度增加，表面张力也增大，而玻璃化温度下降，亲水性也增加，TMP(EO)15TA也易溶于水了。  \n\n表2-13部分烷氧基化丙烯酸酯活性稀释剂的物理性能  \n\n\n<html><body><table><tr><td>烷氧基化活性稀释剂</td><td>分子量</td><td>黏度（25℃） /mPa·s</td><td>表面张力 /(X10-3N/cm)</td><td>玻璃化温度 /℃</td></tr><tr><td>NPG(PO)DA</td><td>328</td><td>15</td><td>32.0</td><td>32</td></tr><tr><td>BP(EO)3DA</td><td>468</td><td>1600</td><td>43.6</td><td>67</td></tr><tr><td>TMP(EO)TA</td><td>428</td><td>60</td><td>39.6</td><td>13</td></tr><tr><td>TMP(PO)3TA</td><td>470</td><td>90</td><td>34.0</td><td>115</td></tr><tr><td>PE(EO)TA</td><td>528</td><td>150</td><td>37.9</td><td>2</td></tr><tr><td>GP(PO)TA</td><td>428</td><td>95</td><td>36.1</td><td>18</td></tr></table></body></html>  \n\n表2-14不同乙氧基化TMPTA的物理性能  \n\n\n<html><body><table><tr><td>乙氧基化TMPTA</td><td>分子量</td><td>黏度(25℃)</td><td>表1面张力/m)</td><td>玻璃化温度</td><td>其他</td></tr><tr><td>TMP(EO)TA</td><td>328</td><td>60</td><td>39.6</td><td>13</td><td></td></tr><tr><td>TMP(EO)6TA</td><td>560</td><td>95</td><td>38.9</td><td>-8</td><td></td></tr><tr><td>TMP(EO)gTA</td><td>692</td><td>130</td><td>40.2</td><td>-19</td><td></td></tr><tr><td>TMP(EO)15TA</td><td>956</td><td>168</td><td>41.5</td><td>-32</td><td>易溶于水</td></tr><tr><td>TMP(EO)20TA</td><td>1176</td><td>225</td><td>41.8</td><td>-48</td><td>水分散性</td></tr></table></body></html>  \n\n乙氧基化的三羟甲基丙烷三丙烯酸酯［TMP(EO)TA]分子式如下。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 55,
+        "chunk": "# 2.7 丙烯酸二茂酯  \n\n丙烯酸二茂酯是一类杂环结构的活性稀释剂，具有低皮肤刺激性的特点。它是由丙三醇和酮在对甲苯磺酸催化下，脱水生成缩醇；再与丙烯酸甲酯，在锡催化剂和正已烷中，经酯交换反应制得。  \n\n![](images/876bfc456d87dc330a4bf71ddddbefe5adb0d585c148f7817d6915495cf41e87.jpg)  \n\n已商品化的丙烯酸二茂酯为MEDOL10、MIBDOL10、CHDOL10，它们的理化性能见表2-15。从表中看到MEDOL10和MIBDOL10 都有较低黏度，三个活性稀释剂皮肤刺激指数都较低，尤其是CHDOL10 仅为0.6。DOL系列活性稀释剂与低聚物相容性良好，光固化速率CHDOL10>MEDOL10>MIBDOL10。表 2-16和表2-17是 DOL系列活性稀释剂的粘接性能和固化膜性能。显示CHDOL10 粘接性能最好，除 PET 外，对其他塑料和玻璃与铝都有极好的粘接性能；弹性拉伸模量也最好。  \n\n表2-15DOL系列活性稀释剂的理化性能  \n\n\n<html><body><table><tr><td>商品名称</td><td>MEDOL10</td><td>MIBDOL10</td><td>CHDOL10</td></tr><tr><td>化学名称</td><td>丙烯酸（2-乙基-2-甲基-1， 3-二氧戊环)4-甲酯</td><td>丙烯酸（2-异丙基-2-甲基- 1,3-二氧戊环)4-甲酯</td><td>丙烯酸（5-环乙基-2-甲基-1， 4-二氧戊环)2-甲酯</td></tr><tr><td>化学结构</td><td></td><td></td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>商品名称</td><td>MEDOL10</td><td>MIBDOL10</td><td>CHDOL10</td></tr><tr><td>分子量</td><td>200.2</td><td>228.3</td><td>226.3</td></tr><tr><td>密度（20℃）/(g/m3)</td><td>1.056</td><td>1.017</td><td>1.104</td></tr><tr><td>折射率（20℃)</td><td>1.447</td><td>1.447</td><td>1.475</td></tr><tr><td>溶解性（20℃，水中)/%</td><td>1.2</td><td>0.7</td><td>0.9</td></tr><tr><td>固化膜T/℃</td><td>-7</td><td>-19</td><td>22</td></tr><tr><td>表面张力/（×10-3N/m)</td><td>32.3</td><td>29.9</td><td>37.4</td></tr><tr><td>黏度（20℃）/mPa·s</td><td>5.1</td><td>5.3</td><td>16.9</td></tr><tr><td>沸点/C</td><td>100(0.7kPa)</td><td>115(0.7kPa)</td><td>135(0.7kPa)</td></tr><tr><td>闪点/℃</td><td>113</td><td>124</td><td>一</td></tr><tr><td>pH值</td><td>1.3</td><td>1.0</td><td>0.6</td></tr><tr><td>艾姆斯氏试验</td><td>阴性</td><td>阴性</td><td>阴性</td></tr></table></body></html>  \n\n表2-16DOL系列活性稀释剂的粘接性能（划格法）  \n\n\n<html><body><table><tr><td rowspan=\"2\">类别</td><td colspan=\"6\">基材</td></tr><tr><td>玻璃</td><td>铝</td><td>PC</td><td>PVC</td><td>ABS</td><td>PET</td></tr><tr><td>MEDOL10</td><td>12</td><td>52</td><td>100</td><td>100</td><td>100</td><td>0</td></tr><tr><td>MIBDOL10</td><td>23</td><td>32</td><td>100</td><td>100</td><td>100</td><td>0</td></tr><tr><td>CHDOL10</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td><td>0</td></tr></table></body></html>\n\n注：试验配方为PUA70、DOL30、11734。100表示最好，0表示最差。  \n\n表2-17 DOL系列固化膜性能  \n\n\n<html><body><table><tr><td>类别</td><td>弹性拉伸模量/MPa</td><td>拉伸率/%</td><td>铅笔硬度</td></tr><tr><td>MEDOL10</td><td>50</td><td>55.8</td><td>H</td></tr><tr><td>MIBDOL10</td><td>39</td><td>57.6</td><td>H</td></tr><tr><td>CHDOL10</td><td>205</td><td>47.4</td><td>H</td></tr></table></body></html>\n\n注：试验配方为PUA70、DOL30、11734。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 56,
+        "chunk": "# 2.8 烷氧基化双酚A二（甲基）丙烯酸酯  \n\n烷氧基化双酚A二(甲基)丙烯酸酯（简称为BPA活性稀释剂）是一类含有双酚A结构且不同程度乙氧基化或丙氧基化的活性稀释剂，这类活性稀释剂结构为：  \n\n![](images/2dcbb47d5c1e4b68b42aaabba99519b3cd356d9a383ef0d54c6b7b0e1a69375b.jpg)  \n\n长兴化学工业股份公司的BPA活性稀释剂结构与名称见表2-18。  \n\n表2-18BPA活性稀释剂结构与名称  \n\n\n<html><body><table><tr><td>化学名称</td><td>商品名</td><td>R1</td><td>R2</td><td>m+n</td></tr><tr><td>二乙氧基双酚A二丙烯酸酯</td><td>EM2260</td><td>H</td><td>H</td><td>2</td></tr><tr><td>四乙氧基双酚A二丙烯酸酯</td><td>EM2261</td><td>H</td><td>H</td><td>4</td></tr><tr><td>十乙氧基双酚A二丙烯酸酯</td><td>EM2265</td><td>H</td><td>H</td><td>10</td></tr><tr><td>十丙氧基双酚A二丙烯酸酯</td><td>EM2268</td><td>H</td><td>CH3</td><td>10</td></tr></table></body></html>  \n\n<html><body><table><tr><td>化学名称</td><td>商品名</td><td>R1</td><td>R2</td><td>m+n</td></tr><tr><td>二乙氧基双酚A二丙烯酸酯</td><td>EM3260</td><td>CH3</td><td>H</td><td>2</td></tr><tr><td>四乙氧基双酚A二丙烯酸酯</td><td>EM3261</td><td>CHg</td><td>H</td><td>4</td></tr><tr><td>十乙氧基双酚A二丙烯酸酯</td><td>EM3265</td><td>CHa</td><td>H</td><td>10</td></tr><tr><td>三十乙氧基双酚A二丙烯酸酯</td><td>EM3269</td><td>CH3</td><td>H</td><td>30</td></tr></table></body></html>  \n\n从表2-19～表2-22可以看到BPA类活性稀释剂具有如下特点。  \n\n$\\textcircled{1}$ 比一般低聚物，如标准型双酚A环氧双丙烯酸酯（621）黏度低很多；而且随烷氧基化增加，黏度有逐渐下降趋势。  \n\n② 含有双酚A结构，具有较高的折射率；用于配方产品中可以获得高光泽。  \n\n③ 随着乙氧基化或丙氧基化程度增加，涂层的Tg下降、柔性增加、耐冲击性能提高。  \n\n④二乙氧基化的两种BPA，对提高配方产品硬度的作用超过了双酚A环氧丙烯酸酯和 TMPTA.  \n\n③ 随着乙氧基化程度增加，使BPA活性稀释剂由亲油疏水过渡到亲水疏油，甚至溶解于水。  \n\n表2-19BPA活性稀释剂的物理性质   \n\n\n<html><body><table><tr><td>单体名</td><td>度</td><td>表面张力</td><td>射率</td><td>心</td><td>分子量</td><td>与水相溶性</td></tr><tr><td>EM2260</td><td>固态</td><td>一</td><td>1.5482</td><td>101.9</td><td>424</td><td>不溶于水</td></tr><tr><td>EM2261</td><td>1222</td><td>42.9</td><td>1.5387</td><td>87.5</td><td>512</td><td>水油分离</td></tr><tr><td>EM2265</td><td>678</td><td>43.0</td><td>1.5166</td><td>5.8</td><td>776</td><td>乳化</td></tr><tr><td>EM2268</td><td>927</td><td></td><td>1.4921</td><td>一</td><td>916</td><td>水油分离</td></tr><tr><td>EM3260</td><td>1492</td><td>38.7</td><td>1.5436</td><td>98.6</td><td>452</td><td>水油分离</td></tr><tr><td>EM3261</td><td>676</td><td>40.7</td><td>1.5330</td><td>55</td><td>540</td><td>水油分离</td></tr><tr><td>EM3265</td><td>474</td><td>41.9</td><td>1.5137</td><td>1</td><td>804</td><td>乳化</td></tr><tr><td>EM3269</td><td>714</td><td>一</td><td>1.4914</td><td>一</td><td>1684</td><td>溶解于水</td></tr><tr><td>EA621</td><td>4000~7000(60℃)</td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n表2-20BPA活性稀释剂应用配方的性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">配方中所含 活性稀释剂</td><td rowspan=\"2\">黏度（20℃) /mPa·s</td><td rowspan=\"2\">固化速率 /(m/min)</td><td colspan=\"2\">固化膜光泽（60°)</td><td rowspan=\"2\">固化膜硬度 /H</td></tr><tr><td>银白色底材</td><td>黑色纸材</td></tr><tr><td>EM2260</td><td>1290</td><td>20</td><td>97.7</td><td>92.6</td><td rowspan=\"9\">4 3 2 2 4 3</td></tr><tr><td></td><td>1070</td><td>19.5</td><td>97.5</td><td>92.0</td></tr><tr><td>EM2261 EM2265</td><td>800</td><td>18.5</td><td>95.7</td><td>89.4</td></tr><tr><td>EM2268</td><td>1150</td><td>9.2</td><td>95.4</td><td>90.4</td></tr><tr><td>EM3260</td><td>992</td><td>7.4</td><td>96.6</td><td>91.8</td></tr><tr><td>EM3261</td><td>746</td><td>8.5</td><td>96.1</td><td>91.1</td></tr><tr><td>EM3265</td><td>605</td><td>10</td><td>96.2</td><td>91.4</td></tr><tr><td>EM3269</td><td>750</td><td>-13</td><td>94.3</td><td>90.6</td></tr><tr><td>TPGDA</td><td></td><td></td><td>93.8</td><td>86.9</td></tr><tr><td>TMPTA</td><td></td><td></td><td>94.3</td><td>89.3</td><td>3 3</td></tr><tr><td>EA(621A-80)</td><td></td><td></td><td>96.1</td><td>89.8</td><td>3</td></tr></table></body></html>\n\n①脂肪族PUA30份、BPA活性稀释剂40份、TMPTA18份、1843份、BP4份、活性胺5份、助剂0.2份。②脂肪族PUA30份、BPA及比较材料40份、TMPTA25份、1845份、助剂0.2份。  \n\n表2-21新中村化学工业株式会社乙氧基化双酚A二（甲基）丙烯酸酯物理性质  \n\n\n<html><body><table><tr><td rowspan=\"2\">品名</td><td rowspan=\"2\">R1</td><td rowspan=\"2\">Rz</td><td rowspan=\"2\">m+n</td><td rowspan=\"2\">分子量</td><td rowspan=\"2\">色度 APHA</td><td rowspan=\"2\">黏度(25℃) /mPa·s</td><td rowspan=\"2\">折射率</td><td rowspan=\"2\">T /℃</td><td>皮肤剌</td></tr><tr><td>激性PII</td></tr><tr><td>ABE-300</td><td>H</td><td>H</td><td>3</td><td>466</td><td>30</td><td>1500</td><td>1.543</td><td></td><td></td></tr><tr><td>A-BPE-4</td><td>H</td><td>H</td><td>4</td><td>512</td><td>150</td><td>1100</td><td>1.537</td><td>82</td><td>0.7</td></tr><tr><td>A-BPE-6</td><td>H</td><td>H</td><td>6</td><td>600</td><td>70</td><td>710</td><td>1.528</td><td></td><td></td></tr><tr><td>A-BPE-10</td><td>H</td><td>H</td><td>10</td><td>776</td><td>70</td><td>550</td><td>1.516</td><td>-12</td><td></td></tr><tr><td>A-BPE-20</td><td>H</td><td>H</td><td>20</td><td>1216</td><td>200</td><td>700</td><td>1.504</td><td></td><td></td></tr><tr><td>A-BPE-30</td><td>H</td><td>H</td><td>30</td><td>1656</td><td>100</td><td>750</td><td>1.493</td><td></td><td></td></tr><tr><td>BPE-80N</td><td>CH3</td><td>H</td><td>2.3</td><td>452</td><td>50</td><td>1200</td><td>1.543</td><td></td><td></td></tr><tr><td>BPE-100N</td><td>CH3</td><td>H</td><td>2.6</td><td>478</td><td>50</td><td>1000</td><td>1.540</td><td></td><td></td></tr><tr><td>BPE-200</td><td>CH3</td><td>H</td><td>4</td><td>540</td><td>50</td><td>600</td><td>1.532</td><td></td><td>1</td></tr><tr><td>BPE-300</td><td>CH3</td><td>H</td><td>6</td><td>628</td><td>50</td><td>500</td><td>1.525</td><td></td><td></td></tr><tr><td>BPE-500</td><td>CH3</td><td>H</td><td>10</td><td>804</td><td>150</td><td>400</td><td>1.512</td><td>7.5</td><td>0.9</td></tr><tr><td>BPE-900</td><td>CH</td><td>H</td><td>17</td><td>1112</td><td>50</td><td>500</td><td>1.502</td><td></td><td></td></tr><tr><td>BPE-1300N</td><td>CH3</td><td>H</td><td>30</td><td>1680</td><td>50</td><td>650</td><td>1.491</td><td>-65</td><td></td></tr></table></body></html>  \n\n表2-22美国沙多玛公司乙氧基化双酚A二（甲基)丙烯酸酯物理性质  \n\n\n<html><body><table><tr><td rowspan=\"2\">品名</td><td rowspan=\"2\">R1</td><td rowspan=\"2\">Rz</td><td rowspan=\"2\">m+n</td><td rowspan=\"2\">黏度(25℃) /mPa·s</td><td rowspan=\"2\">色度APHA</td><td rowspan=\"2\">表面张力(20℃) /(X10-3N/m)</td><td rowspan=\"2\">T</td></tr><tr><td></td></tr><tr><td>SR349</td><td>H</td><td>H</td><td>3</td><td>1600</td><td>80</td><td>43.6</td><td>67</td></tr><tr><td>SR601</td><td>H</td><td>H</td><td>4</td><td>1080</td><td>130</td><td>36.6</td><td>60</td></tr><tr><td>SR602</td><td>H</td><td>H</td><td>10</td><td>610</td><td>80</td><td>37.6</td><td>2</td></tr><tr><td>CD540</td><td>CH3</td><td>H</td><td>4</td><td>555</td><td>100</td><td>35.2</td><td>108</td></tr><tr><td>CD541</td><td>CH3</td><td>H</td><td>6</td><td>440</td><td>50</td><td>35.3</td><td>54</td></tr><tr><td>CD542</td><td>CH3</td><td>H</td><td>8</td><td>420</td><td>40</td><td></td><td></td></tr><tr><td>SR101</td><td>CH3</td><td>H</td><td>2</td><td>1100</td><td>2.5</td><td>41.0</td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 57,
+        "chunk": "# 2.9乙烯基醚类活性稀释剂  \n\n乙烯基醚类是20世纪90年代开发的一类新型活性稀释剂，它是含有乙烯基醚C $\\mathrm{^{\\prime}H_{2}C-C H-0-})$ 或丙烯基醚（HC—CH- $\\cdot\\mathrm{CH}_{2}$ 一O一）结构的活性稀释剂。氧原子上的孤对电子与碳碳双键发生共轭，使双键的电子云密度增大，所以乙烯基醚的碳碳双键是富电子双键，反应活性高，能进行自由基聚合、阳离子聚合和电荷转移复合物交替共聚。因此，乙烯基醚可在多种辐射固化体系中应用，例如在自由基固化体系、阳离子固化体系以及混杂体系（自由基光固化与阳离子光固化同时存在）中作为活性稀释剂使用。另外，如与马来酰亚胺类缺电子双键配合，则乙烯基醚与马来酰亚胺形成强烈的电荷转移复合物（CTC)，经光照后，可在没有光引发剂存在下发生聚合，这也是正在研究开发中的无光引发剂的光固化体系。  \n\n乙烯基醚与丙烯酸酯类活性稀释剂相比，具有低黏度、稀释能力强、高沸点、气味小、毒性小、皮肤的刺激性低、优良的反应活性等特点，但价格较高，影响了它在光固化产品中的应用。  \n\n目前商品化的乙烯基醚类活性稀释剂如下。  \n\n（2）1，4-环己基二甲醇二乙烯基醚（CHVE)  \n\n(3）4-羟丁基乙烯基醚（HBVE) H2C—CH—O—CH—CH2—CH—CH—OH (4）甘油碳酸酯丙烯基醚(PEPC)  \n\n(5）十二烷基乙烯基醚（DDVE)  \n\n$$\n\\mathbf{H}_{3}\\mathbf{C}-(\\mathbf{C}\\mathbf{H}_{2})_{11}\\mathbf{\\overline{{\\Gamma}}}\\mathbf{O}\\mathbf{-}\\mathbf{C}\\mathbf{H}\\mathbf{-}\\mathbf{C}\\mathbf{H}\n$$  \n\n这5个乙烯基醚类活性稀释剂的物理性能见表2-23。  \n\n表2-23乙烯基醚类活性稀释剂的物理性能  \n\n\n<html><body><table><tr><td>物理性能</td><td>DVE-3</td><td>CHVE</td><td>HBVE</td><td>PEPC</td><td>DDVE</td></tr><tr><td>化学品名</td><td>三甘醇二乙烯 基醚</td><td>1,4-环已基二 甲醇二乙烯基醚</td><td>4-羟丁基乙烯 基醚</td><td>甘油碳酸酯丙 烯基醚</td><td>十二烷基乙烯 基醚</td></tr><tr><td>官能度数/个</td><td>2</td><td>2</td><td>2</td><td>1</td><td>1</td></tr><tr><td>外观</td><td>澄清液体</td><td>澄清液体</td><td>澄清液体</td><td>澄清液体</td><td>澄清液体</td></tr><tr><td>气味</td><td>淡</td><td>特殊气味、持久</td><td>淡</td><td>淡</td><td>淡</td></tr><tr><td>沸点(13332.2Pa)/℃</td><td>133</td><td>130</td><td>125</td><td>155</td><td>120~142(666.6Pa)</td></tr><tr><td>凝固点/℃</td><td>-8</td><td>6</td><td>-39</td><td>-60</td><td>-12</td></tr><tr><td>闪点/℃</td><td>119</td><td>110</td><td>85</td><td>165</td><td>115</td></tr><tr><td>密度（25℃)/(g/cm3）</td><td>1.0016</td><td>0.9340</td><td>0.94</td><td>1.10</td><td>0.82</td></tr><tr><td>黏度(25℃)/mPa·s</td><td>2.67</td><td>5.0</td><td>5.4</td><td>5.0</td><td>2.8</td></tr><tr><td>急性经口毒性/（mg/kg)</td><td>>5000</td><td>>5000</td><td>2050</td><td>5000</td><td>7500</td></tr><tr><td>皮肤接触毒性/(mg/kg)</td><td>>2000</td><td>>2000</td><td></td><td></td><td></td></tr><tr><td>皮肤刺激性</td><td>极小</td><td>中等</td><td>弱</td><td>无刺激</td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 58,
+        "chunk": "# 2.10 第三代（甲基）丙烯酸酯类活性稀释剂  \n\n最新开发的第三代（甲基）丙烯酸酯类活性稀释剂为含甲氧端基的（甲基）丙烯酸酯类活性稀释剂，它们除了具有单官能团活性稀释剂的低收缩性和高转化率外，还具有高反应活性。目前已商品化的有沙多玛公司的CD550、CD551、CD552、CD553和科宁公司的8061、8127、8149。  \n\n（1）甲氧基聚乙二醇（350）单甲基丙烯酸酯（CD550)  \n\n（2）甲氧基聚乙二醇（350）单丙烯酸酯（CD551)  \n\n（3）甲氧基聚乙二醇（550）单甲基丙烯酸酯（CD552)  \n\n（4）甲氧基聚乙二醇（550）单丙烯酸酯（CD553)  \n\n(5）甲氧基三丙二醇单丙烯酸酯(8061)  \n\n(6）甲氧基丙氧基新戊二醇单丙烯酸酯(8127)  \n\n$$\n\\begin{array}{r l r}{\\mathrm{{CH}}_{3}}&{0}\\\\ {\\mathrm{{I}}}&{-{\\mathrm{C}}\\mathrm{{C-CH}}_{2}-\\mathrm{{C-CH}}_{2}-({\\mathrm{OCH}}_{2}-{\\mathrm{CH}})_{\\overline{{\\mathfrak{n}}}}{\\mathrm{{O-CH}}}-\\mathrm{{CH}}-{\\mathrm{CH}}_{2}}\\\\ {\\mathrm{{CH}}_{3}}&{\\mathrm{{CH}}_{3}}\\end{array}\n$$  \n\n（7）甲氧基乙氧基三羟甲基丙烷二丙烯酸酯(8149)  \n\n表2-24介绍了甲氧基化丙烯酸酯活性稀释剂的物理性能。  \n\n表2-24甲氧基化丙烯酸酯活性稀释剂的物理性能  \n\n\n<html><body><table><tr><td>公司</td><td>活性稀释剂</td><td>黏度(25℃) /mPa·s</td><td>密度（25℃） /(g/cm3)</td><td>表面张力 /(X10-3N/m)</td><td>玻璃化温度 /℃</td></tr><tr><td rowspan=\"3\">沙多玛</td><td>CD550</td><td>19</td><td rowspan=\"3\"></td><td rowspan=\"3\"></td><td>-62</td></tr><tr><td>CD551</td><td>22</td><td></td></tr><tr><td>CD552</td><td>39</td><td>-65</td></tr><tr><td rowspan=\"2\"></td><td>CD553</td><td>50</td><td>0.99</td><td>30.1</td><td></td></tr><tr><td>8061</td><td>8</td><td></td><td></td><td></td></tr><tr><td rowspan=\"2\">科宁</td><td>8127</td><td>8</td><td>0.96</td><td>25.7</td><td></td></tr><tr><td>8149</td><td>28</td><td>1.08</td><td>35.2</td><td></td></tr></table></body></html>  \n\n此外，SNPE 公司产品的 Acticryl CL-960、Acticryl CL-959 和 Acticryl CL-1042为含氨基甲酸酯、环碳酸酯的单官能团丙烯酸酯，却显示出高反应活性和高转化率，见表2-25。  \n\n![](images/9f98b9421678f2934a88f3ffe9252af7dd0a5ad2f649cba0aa1a2903f7e830cf.jpg)  \n\n表2-25不同活性稀释剂的光固化特性比较  \n\n\n<html><body><table><tr><td>低聚物</td><td>活性稀释剂</td><td>官能度</td><td>相对反应活性</td><td>敏感度/（J/m²)</td><td>不饱和键残余量/%</td></tr><tr><td rowspan=\"6\">PUA</td><td>EDGA</td><td>1</td><td>1</td><td>1.0</td><td>2</td></tr><tr><td>Acticryl CL-960</td><td>１</td><td>10</td><td>0.06</td><td>4</td></tr><tr><td>Acticryl CL-959</td><td>1</td><td>14</td><td>0.05</td><td>3</td></tr><tr><td>Acticryl CL-1042</td><td>1</td><td>18</td><td>0.04</td><td>4</td></tr><tr><td>TPGDA</td><td>2</td><td>3</td><td>0.4</td><td>10</td></tr><tr><td>HDDA</td><td>2</td><td>3</td><td>0.43</td><td>15</td></tr><tr><td rowspan=\"6\">EA</td><td>TMPTA</td><td>3</td><td>11</td><td>0.1</td><td>36</td></tr><tr><td>EDGA</td><td>1</td><td>1</td><td>0.9</td><td>5</td></tr><tr><td>Acticryl CL-960</td><td>1</td><td>7</td><td>0.13</td><td>9</td></tr><tr><td>Acticryl CL-959 Acticryl CL-1042</td><td>1</td><td>13</td><td>0.06</td><td>10</td></tr><tr><td>TPGDA</td><td>1</td><td>17</td><td>0.05</td><td>18</td></tr><tr><td>HDDA</td><td>2 2</td><td>3 3</td><td>4 4</td><td>20 23</td></tr></table></body></html>  \n\n阻燃剂的发展趋向于低烟、低毒和无卤化，故含磷化合物成为重要的高效、无卤阻燃剂。普通的丙烯酸酯都为易燃有机物，而丙烯酸麟酸酯则有较好的阻燃效果，见表2-26。  \n\n![](images/ef86f3f4ec54ce52af461870330d190d866ce32fbd170a74779c7e109631e9e7.jpg)  \n\n表2-26含磷的阻燃型丙烯酸酯  \n\n\n<html><body><table><tr><td>代号</td><td>化学名称</td><td>代号</td><td>化学名称</td></tr><tr><td>DEAMP</td><td>丙烯酸甲基麟酸二乙酯</td><td>DEMMP</td><td>甲基丙烯酸甲基麟酸二乙酯</td></tr><tr><td>DEAEP</td><td>丙烯酸乙基麟酸二乙酯</td><td>DEMEP</td><td>甲基丙烯酸乙基麟酸二乙酯</td></tr><tr><td>DAP</td><td>丙烯酸乙基麟酸二甲酯</td><td></td><td></td></tr></table></body></html>  \n\n阻燃性试验结果如下。  \nPMMA: $480^{\\circ}\\mathrm{C}$ ，93s自燃；氧指数17.2。  \nPMMA $+10\\%$ DEMMP: $480^{\\circ}\\mathrm{C}$ ，未自燃；氧指数22.8。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 59,
+        "chunk": "# 2.12 杂化型活性稀释剂  \n\n杂化型活性稀释剂是指含有自由基光固化和阳离子光固化两种不同光聚合机理的活性基团的活性稀释剂，由于杂化型活性稀释剂中分子内部两种活性基团相互作用，使得自由基光  \n\n聚合和阳离子光聚合可以相互促进，从而加快光聚合速率，提高转化率。  \n\n日本大阪有机化学公司开发的新产品OXE-10和OXE-30就是杂化型活性稀释剂。  \n\n![](images/6c0dccd9fdae2810a409af89686c8f58d923a0cbb403b160234626fe6e7a155f.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 60,
+        "chunk": "# 2.13 新型光固化阳离子活性稀释剂  \n\n阳离子光引发体系具有不受氧阻聚影响、体积收缩小、光照后还能后固化等优点，其应用和研究范围日益广泛。以往阳离子光引发体系使用的活性稀释剂主要为乙烯基醚类和环氧类稀释剂，品种较少。近年来，研究开发了多种阳离子光固化用的活性稀释剂，对促进和推动阳离子光引发体系的应用起了重要的作用。  \n\n（1）1-丙烯基醚类（I）、1-丁烯基醚类（Ⅱ）、1-戊烯基醚类（Ⅲ）  \n\n![](images/c32c708254ed873690c5bf2af8a13258e6a31596b6296c2312eb0696897dc945.jpg)  \n\n此类活性稀释剂多为无色、高沸点、低黏度液体，都具有很高的阳离子聚合活性。（2）乙烯酮缩二乙醇类  \n\n![](images/c1bd598cbc05019d9daffc9d764bc95db574a3f24e8b8aeca3fe887730863393.jpg)  \n\n此类活性稀释剂中双键与两个强的释电子基集团相连，因此特别易被亲电子试剂进攻，所以比乙烯基醚类活性稀释剂更活泼，更易进行阳离子聚合。  \n\n(3）环氧类  \n\n![](images/34f650ad20464ef185809e92487a78203e882f7d9e4525b8c2ecee3bd2c71fec.jpg)  \n\n此类活性稀释剂阳离子聚合活性比常用的环氧单体3,4-环氧环已基甲基-3，4-环氧环己基甲酸酯M快，聚合转化率高。由于后者有酯羧基，会使反应活性降低。  \n\n（4）环氧化三甘油酯  \n\n自然界中不少植物的种子含有不饱和三甘油酯，如已经大规模商业生产的大豆油、亚麻油、向日葵籽油和麻油等。经环氧化可以得到各种环氧化单体，进行阳离子光聚合，它们原料丰富、合成容易、价格低廉、毒性低，是一类很有潜力的阳离子光固化的活性稀释剂。  \n\n（5）氧杂环丁烷类  \n\n![](images/22ce22c788eb7925cc265235d6874c1c359b5200cfa83bbca992d8bf1f34a1d4.jpg)  \n\n氧杂环丁烷类都可以进行阳离子光聚合，也是一类低黏度阳离子活性稀释剂。  \n\n（6）含有环氧基和烯醇醚基团的混合型活性稀释剂  \n\n![](images/e8a2eeb7a95ece03ce479fc5e6fd506f65b2833d0c6ac5ad2f1c6d5045925e1e.jpg)  \n\n这一类活性稀释剂含有环氧基和烯醇醚基，都可以进行阳离子光聚合，而且由于烯醇醚基的存在，使环氧基聚合活性显著增强。  \n\n除了以上介绍的各种（甲基）丙烯酸酯类活性稀释剂外，还有一类具有特殊功能的活性稀释剂，它们不仅参与光固化反应，还可提高对基材（金属、塑料等）的附着力，或能提高光固化速率，有的能改善颜料分散等功能。",
+        "category": " Introduction"
+    },
+    {
+        "id": 61,
+        "chunk": "# 2.14.1提高附着力的活性稀释剂  \n\n最常用的是为了提高对金属附着力的（甲基）丙烯酸磷酸酯PM-1和PM-2。  \n\n沙多玛公司的SR9008、SR9009、SR9011、SR9012和 SR9016，氰特公司的 EB111、EB112、EB1039，科宁公司的4703、4846、4173等都是属于提高附着力的活性稀释剂，其性能特点见表2-27。  \n\n表2-27提高附着力的活性稀释剂  \n\n\n<html><body><table><tr><td>公司</td><td>产品代号</td><td>化学名称</td><td>产品性能特点</td></tr><tr><td rowspan=\"7\">沙多玛公司</td><td>PM-1</td><td>甲基丙烯酸磷酸单酯</td><td>金属附着力促进剂</td></tr><tr><td>PM-2</td><td>甲基丙烯酸磷酸双酯</td><td>金属附着力促进剂</td></tr><tr><td>SR9008</td><td>烷氧基三官能团丙烯酸酯</td><td>快速固化，金属、塑料附着力促进剂，低收缩率，柔韧性好</td></tr><tr><td>SR9009</td><td>三官能团甲基丙烯酸酯</td><td>快速固化，金属、塑料附着力促进剂</td></tr><tr><td>SR9011</td><td>三官能团甲基丙烯酸酯</td><td>快速固化，金属、塑料附着力促进剂</td></tr><tr><td>SR9012</td><td>三官能团丙烯酸酯</td><td>快速固化，金属、塑料附着力促进剂</td></tr><tr><td>SR9016</td><td>二丙烯酸金属盐</td><td>溶于水，对金属附着力强，低皮肤刺激</td></tr><tr><td rowspan=\"5\">氰特公司</td><td>EB111</td><td>脂肪族单丙烯酸酯</td><td>低黏度，低气味，柔韧性好，对塑料、木器等底材有良好附着力</td></tr><tr><td>EB112</td><td>脂肪族单丙烯酸酯</td><td>低气味，良好反应活性，柔韧性好，可增强对塑料附着力</td></tr><tr><td>EB1039</td><td>氨基甲酸酯单丙烯酸酯</td><td>低黏度，优异的柔韧性，增强附着力</td></tr><tr><td>EB168</td><td>甲基丙烯酸磷酸酯</td><td>金属附着力促进剂</td></tr><tr><td>EB170</td><td>丙烯酸磷酸酯</td><td>金属附着力促进剂</td></tr><tr><td>科宁</td><td>4703</td><td>高酸值丙烯酸磷酸酯</td><td>低黏度，对塑料和玻璃附着力有促进作用</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 62,
+        "chunk": "# 2.14.2提高光固化速率的活性稀释剂  \n\n这是一类带叔胺基团的丙烯酸酯，俗称活性胺，它们作为助引发剂，与二苯甲酮等夺氢型自由基光引发剂配合使用，能提高光固化速率；能减少氧阻聚的影响，有利于改善表面固化；带有可聚合的丙烯酸基团，参与光固化反应，避免以往用低分子叔胺气味大、不能参与光固化反应、残留易迁移的病。表2-28列举了国内外企业生产的活性胺。  \n\n表2-28提高光固化速率的活性稀释剂—活性胺  \n\n\n<html><body><table><tr><td>公司</td><td>产品代号</td><td>化学名称</td><td>性能特点</td></tr><tr><td rowspan=\"7\">沙多玛</td><td>活性胺</td><td>叔胺丙烯酸酯</td><td>低黏度，高效助引发剂</td></tr><tr><td>CN371</td><td>叔胺丙烯酸酯</td><td>高效助引发剂</td></tr><tr><td>CN373</td><td>叔胺丙烯酸酯</td><td>低迁移，低刺激，高效助引发剂</td></tr><tr><td>CN381</td><td>叔胺丙烯酸酯</td><td>低迁移，低刺激，表面不起花，高效助引发剂</td></tr><tr><td>CN383</td><td>叔胺丙烯酸酯</td><td>低黏度，低气昧，高效助引发剂</td></tr><tr><td>CN384</td><td>叔胺丙烯酸酯</td><td>低气味，降低褪色能力，高效助引发剂</td></tr><tr><td>CN386</td><td>叔胺丙烯酸酯</td><td>低黏度，低迁移，低刺激性，表面不起花，高效助引发剂</td></tr><tr><td rowspan=\"2\">氰特</td><td>P115</td><td>叔胺丙烯酸酯</td><td>低黏度，高效助引发剂</td></tr><tr><td>7100</td><td>叔胺丙烯酸酯</td><td>有良好附着力，高效助引发剂</td></tr><tr><td rowspan=\"2\">科宁</td><td>4771</td><td>叔胺丙烯酸酯</td><td>耐黄变，高效助引发剂</td></tr><tr><td>4967</td><td>叔胺丙烯酸酯</td><td>低黏度，高效助引发剂</td></tr><tr><td>巴斯夫</td><td>LR8956</td><td>叔胺丙烯酸酯</td><td>低黏度，高效助引发剂</td></tr><tr><td rowspan=\"6\">长兴</td><td>641</td><td>叔胺丙烯酸酯</td><td>低黏度，高效助引发剂，提高光泽</td></tr><tr><td>645</td><td>叔胺丙烯酸酯</td><td>低黏度，高效助引发剂</td></tr><tr><td>6420</td><td>叔胺丙烯酸酯</td><td>低气味，低黏度，高效助引发剂，稳定性佳</td></tr><tr><td>6421</td><td>叔胺丙烯酸酯</td><td>低气味，低黏度，高效助引发剂，稳定性佳</td></tr><tr><td>6422</td><td>叔胺丙烯酸酯</td><td>低气味，低黏度，高效助引发剂，促进对塑料附着力</td></tr><tr><td>6430</td><td>叔胺丙烯酸酯</td><td>低气味，低黏度，高效助引发剂</td></tr><tr><td rowspan=\"2\">石梅</td><td>M8300</td><td>叔胺丙烯酸酯</td><td>低气味，高效助引发剂</td></tr><tr><td>M8400</td><td>叔胺丙烯酸酯</td><td>高效助引发剂</td></tr></table></body></html>  \n\n国内长沙新宇化工实业公司、佛山顺德现代化工公司、浙江洞头恒立印刷材料公司、浙江洞头美利丝油墨涂料公司、陕西喜莱坞实业公司、无锡科润特种化学品公司、天津天骄化工公司、天津市化学试剂研究所、中山博海精细化工公司、深圳鼎好光化科技公司等企业都有生产。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 63,
+        "chunk": "# 2.14.3改善颜料分散性的活性稀释剂  \n\n沙多玛公司的CD802为烷氧基化二丙烯酸酯就属于此类活性稀释剂，黏度不高，对颜料的稳定性好，还能增加已磷化钢材表面的附看力。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 64,
+        "chunk": "# 2.14.4高纯度活性稀释剂  \n\n高纯度活性稀释剂具有极低的酸含量和残留溶剂含量（如沙多玛公司的高纯度活性稀释  \n\n剂，残留溶剂含量只有 $10\\times10^{-6}$ )，因此固化后几乎没有溶剂逸出，都用于高性能产品中。  \n表2-29为高纯度活性稀释剂。  \n\n表2-29 高纯度活性稀释剂  \n\n\n<html><body><table><tr><td>公司</td><td>产品代号</td><td>化学名称</td></tr><tr><td>沙多玛</td><td>SR306HP SR351HP SR454HP</td><td>高纯度DPGDA 高纯度TMPTA 高纯度三乙氧基化TMPTA</td></tr><tr><td>， 氰特</td><td>SR9020HP DPGDA DE0 TMPTADE0 TPGPADE0</td><td>高纯度三丙氧基化丙三醇三丙烯酸酯 高纯度DPGDA 高纯度TMPTA 高纯度TPGPA</td></tr></table></body></html>  \n\n目前光固化产品中常用的活性稀释剂大多数沸点很高，蒸气压很小，不易挥发，在光固化过程中又都参与固化反应，所以在生产和涂装中极少挥发到大气中，也就是说具有很低的挥发性有机物（VOC）含量，这就使光固化产品成为低污染的环保型产品。  \n\n从化学品的毒性看，光固化产品所用的丙烯酸酯类活性稀释剂具有较低的毒性；但在生产和使用时，长时间暴露在丙烯酸酯的气氛下，则会引起对皮肤、黏膜和眼睛的刺激，直接接触会产生刺激性疼痛，甚至出现过敏、灼伤；由于沸点高，室温下蒸气压很低，对呼吸系统没有明显的伤害。  \n\n化学毒性通常用半致死计量 $\\mathrm{ID}_{50}$ （LethalDose-50）来表示毒性程度，通过实验动物（鼠、兔）的口服吸收、皮肤吸收和吸人吸收造成死亡 $50\\%$ 来确定毒性大小，见表2-30。  \n\n表2-30半致死计量 $\\mathbf{LD_{50}}$ 的毒性表示  \n\n\n<html><body><table><tr><td>LD5o/(mg/kg)</td><td><1</td><td>1~50</td><td>50~500</td><td>500～5000</td><td>5000~15000</td><td>>15000</td></tr><tr><td>毒性程度</td><td>剧毒</td><td>高毒</td><td>中毒</td><td>低毒</td><td>实际上无毒</td><td>相当非毒品</td></tr></table></body></html>  \n\n皮肤刺激性可用初期皮肤刺激指数PII（primary skininitiationindex）来表示，见表2-31。 5  \n\n表2-31初期皮肤刺激指数PII的皮肤刺激性程度表示  \n\n\n<html><body><table><tr><td>PII</td><td>0~0.03</td><td>0.04~0.99</td><td>1.00~1.99</td><td>2.00~2.99</td><td>3.00~5.99</td><td>6.00~8.00</td></tr><tr><td>皮肤刺激性程度</td><td>无刺激</td><td>略感刺激</td><td>弱刺激</td><td>中刺激</td><td>刺激性较强</td><td>强刺激</td></tr></table></body></html>  \n\n表2-32和表2-33分别列出了部分活性稀释剂的半致死计量 $\\mathrm{LD}_{50}$ 和初期皮肤刺激指数PII。  \n\n表2-32部分活性稀释剂的半致死计量 $\\mathbf{LD_{50}}$   \n\n\n<html><body><table><tr><td>活性稀释剂</td><td>BA</td><td>2-EHA</td><td>IDA</td><td>HEA</td><td>HPA</td><td>IBOA</td><td>DEGDA</td><td>TMPTA</td><td>PETA</td><td>NGA(PO)2DA</td></tr><tr><td>LD50/(mg/kg)</td><td></td><td></td><td>10885</td><td>600</td><td>1120</td><td>2300</td><td>1568</td><td>>5000</td><td>1350</td><td>15000</td></tr><tr><td>口服 皮肤</td><td>3730 3000</td><td>5600 7488</td><td>3133</td><td></td><td></td><td></td><td></td><td>5170</td><td>>2000</td><td>5000</td></tr></table></body></html>  \n\n表2-33部分活性稀释剂的初期皮肤刺激指数PII  \n\n\n<html><body><table><tr><td>活性稀释剂</td><td>NVP</td><td>IDA</td><td>POEA</td><td>IBOA</td><td>DEGDA</td><td>TEGDA</td><td>PEG(200)DA</td><td>PEG(400)DA</td><td>NPGDA</td></tr><tr><td>PII</td><td>0.4</td><td>2.2</td><td>1.5</td><td>1.8</td><td>6.8</td><td>6.0</td><td>3.0</td><td>0.9</td><td>4.96</td></tr><tr><td>活性稀释剂</td><td>DPGDA</td><td>TPGDA</td><td>BDDA</td><td>HDDA</td><td>TMPTA</td><td>PETA</td><td>PETTA</td><td>DTMPTTA</td><td>DPPA</td></tr><tr><td>PII </td><td>5.0</td><td>3.0</td><td>5.5</td><td>5.0</td><td>4.8</td><td>4.3</td><td>0.4</td><td>0.5</td><td>0.54</td></tr></table></body></html>  \n\n在生产和使用过程中，应避免直接接触活性稀释剂，一旦接触应立即用清水冲洗有关部位。若发现出现红斑甚至水泡，应立即去医院请医生治疗。  \n\n（1）贮存容器活性稀释剂要存放在不透明、深色、干燥的内衬酚醛树脂或聚乙烯的铁桶或深色的聚乙烯桶内。铁或铜类容器会引发聚合，因此应避免接触这类材料。  \n\n注意容器中要留有一定空间，以满足阻聚剂对氧气的需要。  \n\n（2）贮存温度贮存温度低于 $30^{\\circ}\\mathrm{C}$ ，最好 $10^{\\circ}\\mathrm{C}$ 左右。大批贮存推荐温度为 $16\\sim27^{\\circ}C$ 如果发生冻结，请将材料加热至30℃，并低温搅拌混合，使阻聚剂均匀混在材料中。这些预防措施对于保持产品的性能指标是必要的，否则容易发生聚合反应，而使产品固化报废。  \n\n（3）贮存条件贮存时除注意温度条件外，应避免阳光直射，避免与氧化剂、引发剂和能产生自由基的物质接触。  \n\n贮存时需加人足量的阻聚剂对甲氧基苯酚（MEHQ）和对苯二酚（HQ）以增强在贮存时的稳定性。  \n\n注意定期检查阻聚剂含量及材料黏度的变化以防聚合。  \n\n产品在收到六个月内使用可得到最好的效果。  \n\n（4）运输运输时，注意避免阳光直射；温度不要超过 $30^{\\circ}\\mathrm{C}$ ；要防止局部高温，以免发生聚合；同时不能与氧化剂、引发剂等物质放于一起。 0  \n\n在生产过程中输送活性稀释剂时，必须要用不锈钢、聚乙烯管或其他塑料管道。  \n\n（1）丙烯酸十八酯的合成在带有分水器的三口烧瓶加人0.1mol十八醇和适量环已烷、 $1.5\\%$ 对苯二酚，搅拌升温 $60^{\\circ}\\mathrm{C}$ ，加人 $0.12\\mathrm{mol}$ 丙烯酸和 $1.5\\%$ 对甲苯磺酸，加热至$80{\\sim}86^{\\circ}\\mathrm{C}$ ，使反应液处于微沸状态，待分水器分出水量达到理论值时（约6h）停止反应。反应液先用 $5\\%$ 硝酸钠洗涤，去除下层，再用 $10\\%$ 碳酸钠或氢氧化钠洗至微碱性，最后用饱和氯化钠溶液和蒸馏水洗至中性。用无水硫酸镁干燥过夜、过滤减压蒸馏除去环已烷和微量丙烯酸，得到黏稠液体，冷却后即为丙烯酸十八酯蜡状固体，酯化产率89%，提纯收率95%以上。  \n\n（2）丙烯酸十八酯的合成在装有回流冷凝管、分水器的三口瓶中，加入lmol正十八醇、1.1mol丙烯酸、1.5mol甲苯和对甲苯磺酸（正十八醇重的4%～6%）、对甲氧基苯酚适量，升温至110～115℃，反应3.5～4h停止，冷却后用5%氢氧化钠中和至pH≈7，水洗至pH=7，在温度<80℃下减压蒸馏至甲苯全部除去，得无色透明液体，产品收率80%。  \n\n（3）熔融酯化法制备丙烯酸十八酯在三口烧瓶中加入计量的十八醇和对苯二酚（总量0.5%)，加热至60℃使其全部溶解，再加人丙烯酸（n醇：n酸=1.2：1.0）和1%对甲苯磺酸，先升温至110～120℃回流反应2.5h，装上分水器脱水，分出较多水后升温至140℃，当脱水量与理论值相当时，减压蒸馏除去未反应的丙烯酸及残余水，用5%氢氧化钠中和及洗涤，清水洗至中性，真空低温干燥，得白色蜡状固体丙烯酸十八酯，收率90%。  \n\n（4）熔融酯化法合成丙烯酸高碳醇酯在装有分水器的三口烧瓶中加入1mol高碳醇（C12～C18）、投料量1%对甲苯磺酸和投料量0.6%对苯二酚，加热至60℃固体全部溶解，再加入1.2mol丙烯酸，在120～130℃回流，当分水器中水量与理论值相当时停止反应。常压蒸出未反应的丙烯酸，先用70℃、5%NaOH水溶液洗涤，再用热的去离子水洗涤，真空干燥24h，得丙烯酸高碳醇酯，精制后酯化率95%以上。高碳醇酯的物理性能见表2-34。  \n\n表2-34高碳醇酯的物理性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">高碳醇酯</td><td colspan=\"2\">折射率0</td><td colspan=\"2\">沸点(1.33×10Pa)/℃</td></tr><tr><td>实验值</td><td>文献值</td><td>实验值</td><td>文献值</td></tr><tr><td>C12</td><td>1.4435</td><td>1.4439</td><td>159</td><td>158</td></tr><tr><td>C1</td><td>1.4461</td><td>1.4469</td><td>184</td><td>185</td></tr><tr><td>C16</td><td>1.4497</td><td>1.4494</td><td>206</td><td>209</td></tr><tr><td>C18</td><td>1.4467</td><td>1.4458</td><td>234</td><td></td></tr></table></body></html>  \n\n（5）丙烯酸十六酯的微波合成在带有揽拌、冷凝器和油水分离器的250mL微波反应器（三乐牌W-650型，总功率650W，频率2450MHz，南京陵江科技开发公司生产）中依次加入丙烯酸、十六醇（酸：醇=1.3：1，摩尔比）、0.7%（质量分数）对甲苯磺酸和0.6%（质量分数）对苯二酚，微波功率260W，辐射时15min，辐射结束，用热的0.lmol/L的NaOH洗涤反应产物，冷却过滤，以除去未反应的物质，用热水洗至中性，冷却过滤，40℃下真空干燥至恒重，得蜡状固体丙烯酸十六酯，产率97.5%。熔点26.5～27.9℃，沸点（ $20\\mathbf{Pa})$ $148{\\sim}150^{\\circ}\\mathrm{C}$ ，折射率（ $35\\mathrm{^\\circC}$ ）1.4450。  \n\n（6）丙烯酸高级酯的微波合成在带有搅拌、冷凝器、油水分离器的250mL微波反应器（三乐牌W-650型，总功率650W，频率2450Hz，南京陵江科技开发公司生产）中依次加入丙烯酸、相应的高级醇［酸：醇为（1.2：1)～(1.4：1)，摩尔比］、0.7%（质量分数)对甲苯磺酸、0.3%（质量分数）对苯二酚，在微波功率260W的条件下，辐射时间10～16min，反应结束后，分别制得相应的粗丙烯酸高级酯，将粗酯减压蒸馏提纯，收集 20Pa下112～115℃、132～135℃、148～150℃及152～156℃的馏分，即为十二酯、十四酯、十六酯、十八酯。  \n\n用微波合成法比传统酯化法反应速率可提高20倍以上，酯产率≥96%，所得产物的物理性质、分子结构与传统方法加热制备的产物无明显差异。微波合成丙烯酸高级酯的反应条件见表2-35。  \n\n表2-35微波合成丙烯酸高级酯的反应条件  \n\n\n<html><body><table><tr><td>条件</td><td>十二酯</td><td>十四酯</td><td>十六酯</td><td>十八酯</td></tr><tr><td>酸·醇(摩尔比)</td><td>1.2:1</td><td>1.3:1</td><td>1.4·1</td><td>1,41</td></tr><tr><td>辐射时间/min</td><td>10</td><td>12</td><td>14</td><td>16</td></tr><tr><td>精馏条件(20Pa)/C</td><td>112~115</td><td>132~135</td><td>148~150</td><td>152~156</td></tr></table></body></html>  \n\n（7）IBOMA的合成在三口烧瓶中加人 $\\scriptstyle20_{\\mathbf{\\mathbf{g}}}$ 杂多酸催化剂 (锆铵酸)°、 $0.018{\\bf g}$ 盼噻嗪阻聚剂和 $_{50\\mathrm{mL}}$ ? $\\left(0.59\\mathrm{mol}\\right.$ ）MAA，搅拌下在 $40^{\\circ}\\mathrm{C}\\pm2^{\\circ}\\mathrm{C}$ 、2h内缓慢滴加 ${\\mathsf{50m L}}$ $\\left(0.59\\mathrm{mol}\\right)$ ）MAA和 $136{\\bf g}$ （lmol）3,3-二甲基亚甲基双环[2.2.1」庚烷混合液，加毕保温反应 $5\\mathord{\\sim}8\\mathrm{h}$ ，用气相色谱跟踪反应无茨烯峰，停止反应。过滤，用石油醚（ $60{\\sim}90^{\\circ}\\mathrm{C}$ ）洗涤3次（每次 $30\\mathrm{mL}$ )，滤液用水泵回收石油醚和未反应的MAA，减压收集 $98\\sim102^{\\circ}\\mathrm{C}/2\\sim$ $3\\mathbf{kPa}$ 馏分，即为IBOMA，收率 $86.1\\%$ a  \n\n（8）相转移法合成丙烯酸缩水甘油酯用丙烯酸和氢氧化钠溶液在 $24\\sim43^{\\circ}\\mathrm{C}$ 中和至$\\mathbf{pH}{=}7{\\sim}8$ ，得到丙烯酸钠(SA)，用喷雾干燥器干燥得粉末状丙烯酸钠含水量 $1\\%$ 。  \n\n在三口烧瓶中加人粉末状丙烯酸钠、环氧氯丙烷（EPC）（EPC：SA=5：1，摩尔比）、三乙基苄基氯化铵 $(6.9\\%$ SA)，升温至 $90\\mathrm{^\\circC}$ ，反应 $2\\mathrm{h}$ ，反应结束后水洗，控制水温 $30\\sim$ $40^{\\circ}\\mathsf{C}$ ，加人水量与生成 $\\mathbf{NaCl}$ 的质量比为 $1:0.36$ 。反应液明显分为水层和有机层，水层在下层， $\\mathbf{NaCl}$ 可完全溶于水，有机层减压蒸馏，除去EPC，收集 $266,4\\mathrm{Pa}/83^{\\circ}\\mathrm{C}$ 馏分即为丙烯酸缩水甘油酯，含量 $97\\%$ ，折射率（ $20^{\\circ}\\mathrm{C}$ ）1.4472，收率 $78.2\\%$ 0  \n\n（9）甲基丙烯酸缩水甘油酯的合成在三口烧瓶中加人 $95\\mathbf{g}50\\%$ 的 $\\mathbf{NaOH}$ 溶液、$\\scriptstyle500\\scriptstyle{\\mathrm{mL}}$ 已烷、 $100\\mathrm{mL}$ 乙醇和 $0.25{\\bf g}$ 对苯二酚，搅拌下慢慢滴 $125\\mathrm{mL}$ 甲基丙烯酸甲酯，发生皂化反应，生成甲基丙烯酸钠白色沉淀，反应完后，过滤，回收溶剂，产物风干，得 $124\\pmb{\\mathrm{g}}$ 收率 $98\\%$ 。  \n\n在三口烧瓶中加入 $20\\mathbf{g}$ 甲基丙烯酸钠、 $70\\mathrm{mL}$ 环氧氯丙烷、 $0.25{\\bf g}$ 对苯二酚和 $1.2\\mathbf{g}$ 四丁基溴化铵，升温至 $100\\sim150^{\\circ}{\\mathrm{C}}$ 反应4h，冷却、过滤，用 $15\\sim20\\mathrm{mL}$ 环氧氯丙烷洗固体物$\\scriptstyle2\\sim3$ 次，分开滤液，减压蒸馏，先在 $60\\sim70^{\\circ}\\mathrm{C}$ ， $13332.2\\mathrm{Pa}$ 下蒸出过剩的环氧氯丙烷，再收集 $76{\\sim}77\\ensuremath{^{\\circ}}\\ensuremath{\\mathrm{C}}/1333.22\\ensuremath{\\mathrm{Pa}}$ 馏分为甲基丙烯酸缩水甘油酯，纯度 $98\\%$ ，收率 $83.6\\%$ 。  \n\n（10）甲基丙烯酸缩水甘油酯的合成在三口烧瓶中加人 $100\\mathrm{mL}$ 甲基丙烯酸、 $100\\mathrm{mL}$ 正庚烷，搅匀缓慢滴加 $103g50\\%$ 的 $\\mathbf{NaOH}$ 溶液，反应温度不超过 $55^{\\circ}\\mathrm{C}$ ，加毕搅拌 $30\\mathrm{{min}}$ ，加人 $_{0.28}$ 对羟基苯甲醚，在 $85{\\sim}90^{\\circ}\\mathrm{C}$ ， $30.7{\\sim}36.0\\mathbf{k}\\mathbf{Pa}$ 条件下减压脱水干燥得甲基丙烯酸钠盐。  \n\n在三口烧瓶中加人 $_{40\\mathbf{g}}$ 干燥的甲基丙烯酸钠盐， $0.2\\mathbf{g}$ 对羟基苯甲醚，1. $_{2\\mathbf{g}}$ 三乙基苄基氯化铵， $\\mathbf{250g}$ 环氧氯丙烷，升温至 $105{\\sim}110^{\\circ}\\mathrm{C}$ 搅拌反应3h，过滤除去 $\\mathbf{NaCl}$ ，滤液在 $80\\sim$ $85\\mathrm{^\\circC}$ ， $6.7{\\sim}8.0\\mathbf{k}\\mathbf{Pa}$ 条件下减压蒸馏出环氧氯丙烷，再在 $100{\\sim}105^{\\circ}\\mathrm{C}$ ， $1.1{\\sim}1.6\\mathbf{k}\\mathbf{Pa}$ 条件下减压蒸馏出无色透明的液体即为甲基丙烯酸缩水甘油酯，收率 $80\\%$ 。  \n\n（11）酯交换法合成甲基丙烯酸高碳烷基酯在三口烧瓶中加入lmol高碳醇、 $\\scriptstyle2,5{\\mathrm{mol}}$ 甲基丙烯酸甲酯、0.1%氮氧自由基阻聚剂和3%有机锡催化剂，加热回流，控制一定回流比，使甲醇-甲基丙烯酸甲酯共沸物不断移出反应体系，反应3h。反应结束，在5.3kPa下蒸出未反应的甲基丙烯酸甲酯，然后在0.67kPa下蒸馏得到产品，蒸馏残液作为催化剂重复使用。各种甲基丙烯酸高碳烷基酯的合成结果见表2-36。  \n\n表2-36各种甲基丙烯酸高碳烷基酯的合成结果  \n\n\n<html><body><table><tr><td>高碳烷基酯</td><td>转化率/%</td><td>产品收率/%</td><td>反应温度/℃</td></tr><tr><td>2-乙基已酯</td><td>99.6</td><td>96.6</td><td>111~126</td></tr><tr><td>正癸酯</td><td>99.5</td><td>96.5</td><td>115~130</td></tr><tr><td>正十二酯</td><td>99.6</td><td>96.2</td><td>117~132</td></tr></table></body></html>  \n\n（12）丙烯酸缩乙二醇酯的阳离子交换树脂催化合成在装有分水器的三口烧瓶中加人缩乙二醇、丙烯酸（羟基：羧基摩尔比为1：1.1）以及3%的742型酸性阳离子交换树脂、0.1%对羟基苯甲醚和适量甲苯，加热至回流，在回流温度下共沸脱水5h。除湿过滤，滤液减压蒸馏除去溶剂和过量的丙烯酸得到丙烯酸缩乙二醇酯。双酯产率见表2-37。  \n\n表2-37 双酯产率  \n\n\n<html><body><table><tr><td>缩乙二醇</td><td>乙二醇</td><td>一缩二乙二醇</td><td>二缩三乙二醇</td></tr><tr><td>双酯产率/%</td><td>63.7</td><td>46.50</td><td>39.06</td></tr></table></body></html>  \n\n（13）HDDA的合成将己二醇59g、丙烯酸78g及甲苯250mL置于装有分水器的三口烧瓶中，加入对苯二酚2g、对甲苯磺酸3.5g，在105～108℃进行回流反应，直到没有水分离出来为止，冷却后用5%的NaOH中和到pH为7，再水洗两次，用无水CaCl干燥过夜，在60℃/2666.4Pa下将甲苯蒸去，最后40℃/1333.2Pa以下真空蒸馏至无甲苯，产品为无色透明（或浅黄色）液体己二醇二丙烯酸酯（HDDA)，收率≥90%。  \n\n（14）酯交换法制备甲基丙烯酸缩乙二醇双酯在三口烧瓶中加入二缩三乙二醇450g（3mol)、甲基丙烯酸甲酯1500g（15mol）、氯化亚铜30g、浓硫酸30mL，油浴加热至100～110℃，控制分馏柱塔顶温度64～68℃，8～10h蒸出甲醇-甲基丙烯酸甲酯混合液约500mL，冷却，用5%硫酸洗四次，饱和氯化钠溶液洗两次（每次500mL)，分出油层加人30g活性炭，搅拌1～2h，放置过夜，溶液在搅拌下减压蒸馏除去甲基丙烯酸甲酯，先在60～70℃/7999.2～13332.2Pa条件下蒸出大部分，再在90℃/2666.4Pa条件下蒸尽甲基丙烯酸甲酯，得浅黄色油状液体600～680g，折射率n=1.4570，收率70%～80%。各二元醇双酯的性能见表2-38。  \n\n表2-38各二元醇双酯的性能  \n\n\n<html><body><table><tr><td>二元醇双酯</td><td>双酯分子量</td><td>平均产率/%</td><td></td></tr><tr><td>一缩二乙二醇双酯</td><td>242</td><td>62.5</td><td>1.4566</td></tr><tr><td>二缩三乙二醇双酯</td><td>286</td><td>72</td><td>1.5470</td></tr><tr><td>三缩四乙二醇双酯</td><td>330</td><td>70</td><td>1.4590</td></tr><tr><td>混缩二乙醇双酯</td><td>300~330</td><td>72</td><td>1.4576</td></tr></table></body></html>  \n\n（15）二缩三乙二醇甲基丙烯酸酯的合成在带有精馏柱的三口烧瓶中，加人二缩三乙二醇（TEG)、甲基丙烯酸甲酯（MMA）（TEG：MMA=1：6)、对甲氧基苯酚和催化剂，加热反应至沸腾，反应生成的甲醇与MMA形成共沸物（沸点64.2℃左右)，经精馏除去。  \n\n反应4h左右，当精馏柱头温度下降至室温时，停止反应，冷却、沉淀并分离除去催化剂，在 55℃下减压蒸馏除去残余的MMA 和甲醇，得产品二缩三乙二醇双甲基丙烯酸酯（TEG-DMA)，收率95.77%，TEG转化率97.25%，双酯：单酯为33.1：1。  \n\n（16）三羟甲基丙烷三丙烯酸酯的合成在三口烧瓶加人164.5g丙烯酸、74g三羟甲基丙烷、17g对甲苯磺酸、0.4g对苯二酚和150g苯，搅拌加热并通人空气10～25mL/min，在80℃回流反应8h，从分水器中收集到水3lmL时，反应结束，冷却至60℃，加人苯120g和水55g，搅拌20min，静置15min，分去水层，油层用15%氢氧化钠溶液中和洗涤2～3次，再用200mL水洗2～3次，加人0.02g对甲氧基苯酚，减压蒸馏60～80℃，蒸出苯和水，得无色透明三羟甲基丙烷三丙烯酸酯174g，收率95%。  \n\n（17）三羟甲基丙烷三丙烯酸酯的合成在装有回流冷凝管、分水器和搅拌的三口烧瓶中，加人三羟甲基丙烷67g、丙烯酸135g、甲苯250mL、对苯二酚2g、对甲苯磺酸3.5g，在103～108℃进行回流反应，直到没有水分离为止，冷却后，用5%NaOH中和到pH为7，水洗两次，经无水CaCl干燥过夜，60℃/2666.4Pa条件下将甲苯蒸出，再在40℃/1333.2Pa条件下减压蒸馏至无甲苯，得产品为无色透明到浅黄色黏稠液体，收率78%。  \n\n（18）三羟甲基丙烷三丙烯酸酯的合成在三口烧瓶中加人50g三羟甲基丙烷、50gD72树脂（大孔强酸型阳离子交换树脂)、0.5g3#阻聚剂、2g4#阻聚剂、100mL苯和151mL丙烯酸搅拌加热，体系开始回流计时，反应8h，冷却、过滤，固相重复使用，液相减压蒸馏回收丙烯酸，再水洗减压蒸馏得浅黄色透明液体三羟甲基丙烷三丙烯酸酯，n26=1.666，收率70%。  \n\n（19）三羟甲基丙烷三甲基丙烯酸酯的合成在装有分水器的三口烧瓶中，加人0.1mol三羟甲基丙烷、0.35mol甲基丙烯酸、3g对甲苯磺酸、0.08g苯二酚，通人空气2mL/min，加适量溶剂，控制反应温度<85℃，回流反应9h。冷却，加10mL水搅拌10min分出水相，油层用10%NaOH溶液和水洗至中性，加人对甲氧基苯酚，减压蒸馏除去溶剂和水，得浅黄色液体三羟甲基丙烷三甲基丙烯酸酯，收率93.3%。  \n\n（20）酯交换法制备甲基丙烯酸三羟甲基丙烷三酯在三口烧瓶中加人804g（6mol）三羟甲基丙烷、3000g（30mol）甲基丙烯酸甲酯、60g氯化亚铜、60mL浓硫酸，升温油浴至100～115℃，经10～12h，共蒸出甲醇-甲基丙烯酸甲酯混合液1000～1200mL，冷却，用5%浓硫酸洗4次，饱和氯化钠溶液洗2次（每次800mL)，分出油层，加人50g活性炭，揽拌1～2h放置过夜，滤液搅拌减压蒸除甲基丙烯酸甲酯，得浅黄色甲基丙烯酸三羟甲基丙烷三酯1500～1600g（收率为70%～80%)，折射率n=1.4670。  \n\n（21）酰氯法合成季戊四醇三丙烯酸酯在三口烧瓶中加人氯化亚矾，搅拌下缓慢滴加等物质的量的丙烯酸，加毕升温至35～40℃，继续反应30min，用水泵抽除氯化氢和二氯化硫，得到丙烯酰。  \n\n在三口烧瓶中加入季戊四醇，边搅拌边滴加丙烯酰氯（醇：酰氯=1：3.1，摩尔比)，除去副产物氯化氢，使反应完全，依次用5%稀碱液和去离子水洗涤产物，并用有机溶剂将产物从水洗液中萃取出来，干燥，蒸除溶剂，得浅黄色黏稠液体季戊四醇三丙烯酸酯，黏度720mPa·s，纯度>97%，收率>96%。  \n\n（22）四甲基丙烯酸季戊四醇酯的合成在三口烧瓶中加人0.1mol季戊四醇、0.46mol甲基丙烯酸、4g对甲苯磺酸、0.108g对苯酚和适量的溶剂，并通过补加溶剂控制反应温度低于90℃，通人空气量为2mL/min，搅拌回流10h，冷却，加10mL水搅拌10min，分出水相，油层经10%NaOH和水洗至中性后过滤，加少量溶剂、少量对甲氧基苯酚，减压蒸馏出溶剂，得白色固体，真空干燥恒重得四甲基丙烯酸季戊四醇酯，收率89.8%。  \n\n（23）双季戊四醇五丙烯酸酯的合成在装有分水器的三口烧瓶中加人双季戊四醇10.0g、丙烯酸16mL、对甲苯磺酸1.3g、甲苯50mL、对甲氧基苯酚1.0g 和2,2,6,6-四甲基-4-羟基哌啶氮氧自由基，升温至110～120℃反应，至无水带出，冷至室温，加入80mL甲苯，30mL20%的NaOH溶液，搅拌10min，分液，油层用5%的NaOH溶液中和至pH=9，水洗3次，分去水层，油层加人无水NazSO干燥过夜，过滤，40～50℃减压蒸馏除去甲苯，得橙色黏稠油状液体，再加入一定量甲醇和活性炭，加热至45℃搅拌0.5h，过滤，减压蒸去甲醇，得浅黄色黏稠状液体为双季戊四醇五丙烯酸酯，收率94%。  \n\n（24）双季戊四醇六丙烯酸酯的合成在三口烧瓶加人19.8g经重结晶的双季戊四醇（羟值39.6）、40g丙烯酸、70mL甲苯、4.0g对甲苯磺酸和1.6g阻聚剂YD（自制)，回流反应4h，冷至室温，加人80mL甲苯和 30mL水，分去水层，油层由10%氢氧化钠中和，水洗至中性，减压蒸馏，回收溶剂，得黏稠液体32.1g，即双季戊四醇六丙烯酸酯，收率$71.4\\%$ 。阻聚剂用量与黏附物的关系见表 2-39。  \n\n表2-39阻聚剂用量与黏附物的关系  \n\n\n<html><body><table><tr><td>阻聚剂用量/g</td><td>对苯酚</td><td>对苯酚-硫酸酮</td><td>YD</td></tr><tr><td>0.8</td><td>+++</td><td>+++</td><td>++</td></tr><tr><td>1.2</td><td>+++</td><td>+++</td><td>++</td></tr><tr><td>1.6</td><td>+++</td><td>十十</td><td></td></tr><tr><td>2.0</td><td>++</td><td>++</td><td>+</td></tr></table></body></html>\n\n注： $+$ 代表黏附物极少； $++$ 代表少许黏附物； $+++$ 代表较多黏附物。  \n\n（25）全氟辛酸甲基丙烯酰氧乙酯的合成在无水条件下，在装有碱液吸收装置的三口烧瓶中加人全氟辛酸和过量亚硫酰氯（全氟辛酸：亚硫酰氯=1：2，摩尔比）和催化剂二甲基甲酰胺（全氟辛酸的 $3.2\\%$ ，质量分数)，加热至 $70\\sim75^{\\circ}C$ 反应 $2\\mathrm{h}$ ，无气体产生时停止反应，用分液漏斗静止分层，下层白色透明、具有强烈刺激气味的液体为全氟辛酰氯，减压蒸馏除去过量的亚硫酰氯，平均收率为 $97.1\\%$ 。  \n\n将计量的甲基丙烯酸羟乙酯加入装有碱液吸收装置的三口烧瓶中，搅拌下，于 $20\\%$ 以下缓慢滴加等物质的量的全氟辛酰氯，升温至 $60\\sim62^{\\circ}\\mathrm{C}$ ，反应时间 $^{\\mathrm{11h}}$ 。冷至室温，加入一定量的乙醚和5%的氢氧化钠溶液，有机层用蒸馏水洗1次，减压蒸馏除去溶剂，得到全氟辛酸甲基丙烯酰氧乙酯，平均收率 $75.2\\%$ ，总收率 $73\\%$ 。  \n\n（26）甲基丙烯酸2,2,3,4，4,4-六氟丁酯的合成在装有HCl及 $\\mathsf{s o}_{2}$ 吸收装置的三口烧瓶中加入 $120\\mathbf{g}$ 二氯亚矾，在 $40\\sim45^{\\circ}C$ 下缓慢滴加 $\\mathfrak{s}\\mathfrak{z}$ 甲基丙烯酸，加毕升温到 $60^{\\circ}\\mathrm{C}$ 保温$5\\mathrm{h}$ 。再缓慢滴加 $164\\mathbf{g}\\ 2,2,3,4,4,4-$ 六氟丁醇，加毕，升温到 $80^{\\circ}\\mathrm{C}$ 保温反应 $^\\mathrm{4h}$ 。降至室温，冷却下用 $20\\%$ 的 $\\mathbf{NaOH}$ 中和至中性，分出有机层，用饱和食盐水洗涤，用无水 $\\mathbf{MgSO_{4}}$ 干燥，减压蒸馏，收集 ${77}\\mathrm{\\sim}87^{\\circ}\\mathrm{C}$ 馏分，得到 $210\\mathbf{g}$ 无色透明液体，收率 $93\\%$ 。  \n\n（27）低皮肤刺激性二茂烷结构丙烯酸酯的合成（DOL系列）DOL系列是由丙三醇与酮在酸催化下脱水缩合成缩醇，再与（甲基）丙烯酸甲酯经酯交换反应合成。  \n\n![](images/ae6498f8a081b358e66b2a215c87cb6df1809b6161f82f5b57c9aa0fdc75f1ba.jpg)  \n\n甲乙酮和丙三醇通过对甲苯磺酸催化，用环已烷作脱水剂，反应制得产物A。溶液中和后，经蒸馏提纯，可得A纯度为 $98\\%$ 。然后A和丙烯酸甲酯，加入锡催化剂和正己烷，利用甲醇和正已烷共沸带出反应生成物甲醇，未反应的原料、甲醇、正已烷和过量的丙烯酸除去后，所得蒸馏产物B含量可达 $98\\%$ （2-乙基-2-甲基-1，3-二茂）4-丙烯酸甲酯，商品名称为MEDOL10。DOL系列单体的理化性能见表2-40。  \n\n表2-40DOL系列单体的理化性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">性能</td><td colspan=\"3\">商品名</td></tr><tr><td>MEDOL10</td><td>MIBDOL10</td><td>CHDOL10</td></tr><tr><td>结构式</td><td></td><td>0</td><td></td></tr><tr><td>分子量 密度（20℃）/(g/m）</td><td>200.2</td><td>228.3</td><td>226.3</td></tr><tr><td>折射率(20℃)</td><td>1.056</td><td>1.017</td><td>1.104</td></tr><tr><td></td><td>1.447</td><td>1.447</td><td>1.475</td></tr><tr><td>沸点(0.7kPa)/℃</td><td>100</td><td>115</td><td>135</td></tr><tr><td>溶解性（水中，25℃）/%</td><td>1.2</td><td>0.7</td><td>0.9</td></tr><tr><td>表面张力/（×10-3N/m）</td><td>32.3</td><td>29.9</td><td>37.4</td></tr><tr><td>黏度(20℃)/mPa·s</td><td>5.1</td><td>5.3</td><td>16.9</td></tr><tr><td>闪点/℃</td><td>113</td><td>124</td><td>一</td></tr><tr><td>固化膜Tg/C</td><td>-7</td><td>-19</td><td>22</td></tr><tr><td>pH值</td><td>1.3</td><td>1.0</td><td>0.6</td></tr><tr><td>艾姆斯氏试验</td><td>阴性</td><td>阴性</td><td>阴性</td></tr></table></body></html>  \n\nDOL系列单体与各种低聚物和活性稀释剂有很好的相容性，固化速率CHDOL $^{10>}$ MEDOL $^{10>}$ MBDOL10，接近THFA。固化膜CHDOL10有很好的伸展性，但强度不如IBOA，MEDOL10和MIBDOL10 的强度和伸展性则和POEA差不多，铅笔硬度都与POEA相同。CHDOL10对玻璃、铝、PC、PVC、PET 和 ABS 基材有优异的粘接性，其他两种对玻璃和铝的粘接性较差。  \n\n（28）UV粘接性单体的合成（10-甲基丙烯酰氧葵基硫磷酸二氯）在三口烧瓶中加入$_{19.17_{8}}$ （0.1lmol）1,10-癸二醇、 $30\\mathrm{mL}$ 环已烷，加热至 $72^{\\circ}\\mathrm{C}$ 全部溶解，加人 $0.40\\mathbf{g}$ 对甲苯磺酸作催化剂，滴加8.6lg（0.10mol）甲基丙烯酸，加热至80℃，换上分水装置，回流至水层高度不增加时停止反应（约6h)，降温，减压蒸馏去除环已烷，用二氯甲烷稀释产物，用5%的 $\\mathsf{N a O H}$ 水溶液洗至中性，水洗3次，用无水 $\\mathrm{Na}_{2}\\mathrm{SO}_{4}$ 干燥、过滤、减压蒸馏蒸出二氯甲烷，得淡黄色油状液体，用硅胶色谱柱对粗产品提纯，展开剂为二氯甲烷，得甲基丙烯酸10-羟癸酯。  \n\n在三口烧瓶中加人 $\\mathbf{2.55g}$ 二氯硫磷和 $_{15\\mathrm{mL}}$ 四氢呋喃，缓慢滴加 $3.10{\\bf g}$ 甲基丙烯酸-10-羟癸酯和四氢呋喃溶液，开始滴加时反应剧烈，有大量白色沉淀生成，放热，加毕在氮气保护下反应3h，过滤除去沉淀，减压蒸馏除去四氢呋喃，得黄色10-甲基丙烯酰氧癸基硫磷酸二氯，加人二氯甲烷，水洗3次，用无水 $\\mathrm{Na}_{2}\\mathrm{SO}_{4}$ 干燥过夜，减压蒸馏除去二氯甲烷，得淡黄色油状液体，用硅胶色谱柱对粗产品提纯，展开剂为二氯甲烷。  \n\n10-甲基丙烯酰氧癸基硫磷酸二氯与水、三乙胺混合溶液能促进复合树脂与钛合金、钻铬合金的粘接，剪切强度分别达到17.3MPa、18.1MPa。  \n\n（29）丙烯酸羟乙酯基羟氯丙基顺丁烯二酸酯的合成  \n\n![](images/5e6845a48a7f1f23bccc81c3c03c95fe64076b0bf8ff6d5628264ca94ae22f52.jpg)  \n\n在三口烧瓶中加人 $\\scriptstyle1.02{\\mathrm{mol}}$ 丙烯酸羟乙酯、1mol顺丁烯二酸酐、 $0.3\\%$ 投料量对甲苯磺酸（催化剂）和适量2，6-叔丁基对甲酚，升温至 $85\\sim90^{\\circ}C$ ，反应0.5h，测量酸值在 $240\\sim$ $260\\mathrm{mg}~\\mathrm{KOH/g}$ （理论酸值为 $260\\mathrm{mg}\\ \\mathrm{KOH/g})$ 时停止反应。再加入 $\\mathbf{1.07mol}$ 环氧氯丙烷和$0.15\\%$ （总投料量）的二甲基咪唑，升温至 $120^{\\circ}\\mathrm{C}$ ，反应 $\\mathsf{2}\\sim\\mathsf{2}.\\mathsf{5h}$ ，测酸值 $<10\\mathrm{mg}~\\mathrm{KOH/g}$ 停止反应（环氧值控制 $<0.01\\mathrm{mol/L}100\\mathrm{g})$ ，得到带羟基的单丙烯酸酯：丙烯酸羟乙酯基羟氯丙基顺丁烯二酸酯，黏度（ $25\\mathrm{{^circC}}$ ）为 $20\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$ 。  \n\n（30） $\\beta$ 丙烯酰氧基丙酸甲氧基乙酯的合成  \n\n$$\n\\mathrm{2}\\mathrm{\\:\\:\\mathrm{\\:H_{2}C\\mathrm{-}C H C O O H\\xrightarrow{A l C l_{3}}\\mathrm{\\:\\:H_{2}C\\mathrm{-}C H C O O C H_{2}C O O H}}}\n$$  \n\n$$\n\\mathrm{H_{2}C-C H C O O C H_{2}C O O H+H O-C H_{2}C H_{2}-O C H_{3}\\xrightarrow[-H_{2}O]{X i\\ne6n t e n t}}\n$$  \n\n$$\n\\mathrm{H_{2}C}\\mathrm{-CHCOOCH_{2}C O O-C H_{2}C H_{2}\\mathrm{-OCH_{3}}}\n$$  \n\n在三口烧瓶中加人 $300\\mathbf{g}$ 丙烯酸、 $_{13{\\bf g}}$ 无水三氯化铝及少量对苯二酚，搅拌下升温至 $156\\sim$ $158^{\\circ}\\mathrm{C}$ 反应2h，过滤残留物和沉淀，减压蒸馏除去未反应的丙烯酸，得到 $\\beta$ 丙烯酰基内酸，转化率 $80\\%$ 左右。  \n\n将1molβ丙烯酰氧基丙酸、1mol乙二醇单甲醚和配方量的苯、对甲苯磺酸加入装有分水器的三口烧瓶内，加少量沸石升温，84℃左右沸腾，反应6～7h，停止反应，用稀NaOH溶液洗至pH=7.0，分液，上层苯和酯层用无水硫酸镁干燥后减压蒸馏除去苯，得到β丙烯酰氧基丙酸甲氧基乙酯，转化率 $96\\%$ ，该单体均聚物 $T_{\\mathrm{{s}}}=-54^{\\circ}\\mathrm{{C}}$ 。  \n\n（31）含酰氨基的活性稀释剂的合成  \n\n![](images/6f2303f129c97245a118b7eeaf990c4da38b0a8afec4a80ade1d0ae9733701a9.jpg)  \n\n在三口烧瓶中加人1mol马来酸酐和乙酸乙酯，搅拌溶解，滴加lmol吗啉，加热回流1h，冷却过滤，干燥得白色粉末A，收率 $98\\%$ 0  \n\n称取0.1mol产物A，以乙醇为溶剂，三乙胺为催化剂，与0.lmol甲基丙烯酸缩水甘油回流反应5h，真空蒸出溶剂，得淡黄色黏稠液体即为含酰氨基的甲基丙烯酸酯。  \n\n（32）UV-磷睛阻燃单体的合成将7.8g（0.06mol）丙烯酸羟丙酯、6.06g（0.06mol)三乙胺、0.05g氯化亚铜溶于四氢呋喃中，加人三口烧瓶中，再将3.48g（0.01mol）六氯环三磷酯（50℃干燥2h）溶于四氢呋喃并稀释至50mL，在氮气保护下在冰水浴中逐滴滴人三口烧瓶中，在室温反应4h，减压过滤，滤液在65℃时蒸馏除去四氢呋喃，制得UV-磷睛阻燃单体，收率 $80.3\\%$ 。各单体氧指数见表2-41。  \n\n表2-41 各单体氧指数  \n\n\n<html><body><table><tr><td>单体</td><td>不含磷睛单体</td><td>含磷睛单体</td></tr><tr><td>氧指数</td><td>23</td><td>27</td></tr></table></body></html>  \n\n由于P—O键能（625.8kJ）比C—O键能（1079.4kJ）低，因此含磷睛阻燃单体固化物的起始热分解温度低。受热后能放出CO、 $\\mathrm{NH}_{3}$ 、 $\\mathbf{N}_{2}$ 、 $\\mathbf{H}_{2}\\mathbf{O}$ 气体，会阻断氧的供应，实现阻燃增效。燃烧时有PO·形成，可与火焰区域中的H、HO 自由基结合，起到抑制火焰的作用，终止链反应。磷睛单体表面成炭更容易，延缓了材料的热分解，故燃烧后残余物增加很多。  \n\n（33）三羟甲基丙烷二烯丙基醚的合成将120g氢氧化钠溶于1000mL水中，加入三口烧瓶中，升温至60℃，加人134g（1mol）三羟甲基丙烷，待全部溶解后加人质量比0.1%的季铵盐催化剂，升温至70℃，开始滴加19lg（2.5mol）氯丙烯，滴加速度使温度保持70℃为宜，加人一半氯丙烯时出现明显的淡黄色有机相和白色沉淀，经2～2.5h加毕，保温反应2h，升温至75℃，反应2h，停止反应，分去水相和盐，有机相用磷酸中和至pH=7～8，用少量热水（总质量的20%）洗去中和时生成的盐，分去水相，在有机相加人阻聚剂减压蒸馏，先蒸出水和丙烯醇，收集110℃/35×133Pa以上馏分，收率94.90%。  \n\n（34）氨酯乙烯基醚结晶性单体的合成在三口烧瓶中加人46.46g（0.4mol）羟丁基乙烯基醚（HBVE)，通氮气，60℃下缓慢滴加33.64g（0.2mol）HDI，加毕加人适量二月桂酸二丁基锡，升温至100℃，反应2～3h得粉状白色固体产物氨酯乙烯基醚结晶性单体(UVE)，熔点 $101{\\sim}102\\%$ 。  \n\n用20%～40%的正辛醇、乙二醇单丁醚或乙二醇单乙醚代替HBVE，得到改性UVE，熔点75～90℃，适合UV粉末涂料中应用，并且有自由基/阳离子双重光引发功能。  \n\n（35）杂化单体丙烯氧基丙氧基丙烯酸酯的合成  \n\n![](images/b6ef219af26c9f3d07d7829169bafe3ecb88bf1ffd8167dfb83ebee31ad62a6c.jpg)  \n\n在三口烧瓶中加入22.8g（0.3mol）1,3-丙二醇和75mL甲苯，通氮气，升温至40℃，加入0.4g四丁基溴化铵，升至50℃时加人4g（0.1mol）氢氧化钠，搅匀升温至65℃，滴加12.1g（0.lmol）烯丙基溴和15g甲苯混合液，6h滴完，继续反应1h，继续通氮气至体系冷至室温。抽滤除去固体，旋转蒸发出溶剂，减压蒸馏，1333.2Pa下收集78～80°℃的馏  \n\n分，得烯丙基羟丙基醚A。  \n\n将11.6g（0.1mol）烯丙基羟丙基醚和50mL二甲基亚矾加人三口烧瓶中，搅拌，加人2.26g（0.2mol）叔丁醇钾，加热至100～110℃，恒温1h，冷至室温，抽滤除去固体，加人100mL蒸馏水，用乙醚：正已烷1：1（体积比）萃取洗3～4次，有机相旋转蒸发除去溶剂，得产物烯丙基羟丙基醚B。  \n\n将7.05g（0.06mol）烯丙基羟丙基醚、6.14g（0.06mol）三乙胺和80mL甲苯加入三口烧瓶中搅拌，置于冰浴中，滴加5.50g丙烯酰氯和20mL甲苯混合液，3h 滴完。抽滤，滤液用0.1mol/L盐酸洗3次，再用0.1mol/L碳酸氢钠溶液洗3次，加入无水硫酸钠过夜，旋转蒸发得产物丙烯氧基丙氧基丙烯酸酯。  \n\n丙烯氧基丙氧基丙烯酸酯在硫盐作用下可以发生有效的杂化光聚合反应，与自由基光固化速率相当，特别对羟基阻聚作用不敏感，为对湿度不敏感的烯基醚型单体。  \n\n（36）杂化单体4-(1-丙烯基)氧丁基缩水甘油醚的合成  \n\n![](images/0a20db3dc17b098292790ec76632e7aff7f55f7e37a98b84f14178abf7b812ae.jpg)  \n\n在三口烧瓶中加人0.6mol1,4-丁二醇及85mL甲苯，通氮气，升温至30℃，加人1.2g四丁基溴化铵搅拌溶解，加热至40℃，加人6g（0.15mol）氢氧化钠，搅匀，升温至65℃，滴加18.15g（0.15mol）烯丙基溴和10mL甲苯混合液，先滴加1～2滴，约半小时开始反应，用6h滴加完，前4h慢滴，加毕反应1～2h，通氮气搅拌冷至室温，抽滤，旋转蒸发除去溶剂，减压蒸馏，收集相应馏分为4-羟丁基烯丙基醚（A)。  \n\n在三口烧瓶中加人0.1mol4-羟丁基烯丙基醚，加热至80℃，加人3.45g（0.03mol）叔丁醇钾，升温至100～110℃，恒温1h后，冷至室温，过滤除去固体，加人400mL蒸馏水，用乙醚：正已烷=1：1（体积比）洗5～6次，合并有机相，用无水硫酸镁干燥过夜，旋转浓缩除去溶剂，得4-羟丁基烯丙基醚(B)。  \n\n在三口烧瓶中加人10.6g（0.115mol）环氧氯丙烷及40mL甲苯，30℃加人1.07g苄基三乙基氯化铵，完全溶解后，缓慢加人4.2g（0.105mol）氢氧化钠，恒温35℃，缓慢滴加0.lmol4-羟丁基烯丙基醚，加毕，升温至40℃，恒温5.5h，抽滤除去固体，用10mL甲苯洗涤滤并再用100mL、70℃蒸馏水洗涤滤液4次，用甲苯萃取水相2次，合并所有有机相，用无水碳酸钠干燥过夜，常压蒸馏除去甲苯，粗产品先用氯仿-乙酸乙酯混合液（氯仿：乙酸乙酯=12：1，质量比）洗涤，再用正已烷-乙酸乙酯混合液（正已烷：乙酸乙酯=4：1，1质量比）为洗脱剂进行柱色谱分离，得到4-(1-丙烯基)氧丁基缩水甘油醚。  \n\n杂化单体的光聚合性能见表2-42。  \n\n表2-42杂化单体的光聚合性能  \n\n\n<html><body><table><tr><td>光引发剂(4%用量)</td><td>环氧基转化率/%</td><td>双键转化率/%</td></tr><tr><td>硫盐(UV1-6976)</td><td>69</td><td>71</td></tr><tr><td>碘盐（Omnicat-440）</td><td>35</td><td>60</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 65,
+        "chunk": "# 第3章低聚物  \n\n光固化产品用的低聚物（oligomer）也称预聚物（prepolymer），原译为“齐聚物”，这一概念现已过时，故用低聚物较恰当。它是一种分子量相对较低的感光性树脂，具有可以进行光固化反应的基团，如各类不饱和双键或环氧基等。在光固化产品的各组分中，低聚物是光固化产品的主体，它的性能基本上决定了固化后材料的主要性能，因此，低聚物的合成和选择无疑是光固化产品配方设计的重要环节。  \n\n自由基光固化产品用的低聚物都是具有 $^{\\ast}\\rangle_{^{\\mathrm{c-c}^{\\prime}}}\\langle^{\\prime}\\rangle$ 不饱和双键的树脂，如丙烯酰氧基（ $_{\\mathrm{H}_{2}\\mathrm{C}=\\mathrm{CH}}$ -COO—)、甲基丙烯酰氧基 $\\mathrm{^{-}{H_{2}C}=C(C H_{3}).}$ )—COO—]、乙烯基（）、烯丙基（ $_{\\mathrm{H}_{2}\\mathrm{C=CH}}$ 一 $\\cdot\\mathrm{CH}_{2}$ 一）等。按照自由基聚合反应速率快慢排序：丙烯酰氧基 $>$ 甲基内烯酰氧基>乙烯基〉烯丙基。因此，自由基光固化用的低聚物主要是各类丙烯酸树脂，如环氧丙烯酸树脂、聚氨酯丙烯酸树脂、聚酯丙烯酸树脂、聚醚丙烯酸树脂、丙烯酸酯化的丙烯酸酯树脂或乙烯基树脂等。其中实际应用最多的是环氧丙烯酸树脂、聚氨酯丙烯酸树脂和聚酯丙烯酸树脂。表3-1列举了常用低聚物的性能。  \n\n阳离子光固化产品用的低聚物，具有环氧基团 ）或乙烯基醚基团C ${\\bf H}_{2}{\\bf C}{\\bf-C}{\\bf H}{-}0{-})$ ，如环氧树脂、乙烯基醚树脂。  \n\n表3-1常用低聚物的性能  \n\n\n<html><body><table><tr><td>低聚物</td><td>固化速率</td><td>拉伸强度</td><td>柔性</td><td>硬度</td><td>耐化学药品性</td><td>耐黄变性</td></tr><tr><td>环氧丙烯酸树脂(EA)</td><td>高</td><td>高</td><td>不好</td><td>高</td><td>极好</td><td>中</td></tr><tr><td>聚氨酯丙烯酸树脂(PUA)</td><td>可调</td><td>可调</td><td>好</td><td>可调</td><td>好</td><td>可调</td></tr><tr><td>聚酯丙烯酸树脂(PEA)</td><td>可调</td><td>中</td><td>可调</td><td>中</td><td>好</td><td>不好</td></tr><tr><td>聚醚丙烯酸树脂</td><td>可调</td><td>低</td><td>好</td><td>低</td><td>不好</td><td>好</td></tr><tr><td>纯丙烯酸酯树脂</td><td>慢</td><td>低</td><td>好</td><td>低</td><td>好</td><td>极好</td></tr><tr><td>乙烯基树脂</td><td>慢</td><td>高</td><td>不好</td><td>高</td><td>不好</td><td>不好</td></tr></table></body></html>  \n\n光固化产品中低聚物的选择要综合考虑下列因素。  \n\n（1）黏度选用低黏度树脂，可以减少活性稀释剂的用量；但低黏度树脂往往分子量低，会影响成膜后的物理力学性能。  \n\n(2）光固化速率选用光固化速率快的树脂是一个很重要的条件，不仅可以减少光引发剂用量，而且可以满足光固化涂装生产线快速固化的要求。一般来说，官能度越高，光固化速率越快，环氧丙烯酸酯光固化速率快，胺改性的低聚物光固化速率也快。  \n\n（3）物理力学性能光固化产品漆膜的物理力学性能主要由低聚物固化膜的性能来决定，而不同品种的光固化产品其物理力学性能要求也不同，所选用的低聚物也不同。漆膜的物理力学性能主要有下列几种。  \n\n$\\textcircled{1}$ 硬度环氧丙烯酸酯和不饱和聚酯一般硬度高；低聚物中含有苯环结构也有利于提高硬度；官能度高，交联密度高， $T_{\\mathrm{g}}$ 高，硬度也高。  \n\n$\\textcircled{2}$ 柔韧性聚氨酯丙烯酸树脂、聚酯丙烯酸树脂、聚醚丙烯酸树脂和纯丙烯酸酯一般柔韧性都较好；低聚物含有脂肪族长碳链结构，柔韧性好；分子量越大，柔韧性也越好；交联密度低，柔韧性变好； $\\boldsymbol{T_{\\mathrm{8}}}$ 低，柔韧性好。  \n\n$\\textcircled{3}$ 耐磨性聚氨酯丙烯酸树脂有较好的耐磨性；低聚物分子间易形成氢键的，耐磨性好；交联密度高的，耐磨性好。  \n\n$\\textcircled{4}$ 拉伸强度环氧丙烯酸酯和不饱和聚酯有较高的拉伸强度；一般分子量较大、极性较大、柔韧性较小和交联度大的低聚物有较高的拉伸强度。  \n\n$\\textcircled{5}$ 耐冲击性聚氨酯丙烯酸树脂、聚酯丙烯酸树脂、聚醚丙烯酸树脂和纯丙烯酸酯有较好的耐冲击性；低 $T_{\\mathrm{s}}$ 、柔韧性好的低聚物一般耐冲击性好。  \n\n$\\textcircled{6}$ 附着力收缩率小的低聚物对基材的附着力好；含—OH、—COOH等基团的低聚物对金属的附着力好；低聚物表面张力低，对基材润湿铺展好，有利于提高附着力。  \n\n$\\textcircled{7}$ 耐化学品性环氧丙烯酸酯、聚氨酯丙烯酸树脂和聚酯丙烯酸树脂都有较好的耐化学品性，但聚酯丙烯酸树脂耐碱性较差；提高交联密度，耐化学品性增强。  \n\n$\\textcircled{8}$ 耐黄变脂肪族聚氨酯丙烯酸树脂、聚醚丙烯酸树脂和纯丙烯酸酯有很好的耐黄 变性。  \n\n$\\textcircled{9}$ 光泽环氧丙烯酸酯和不饱和聚酯有较高的光泽；交联密度增大，光泽增加； $\\scriptstyle{T_{8}}$ 高，折射率高的低聚物光泽好。  \n\n$\\textcircled{10}$ 颜料的润湿性一般脂肪酸改性和胺改性的低聚物有较好的颜料润湿性；含—OH和一COOH的低聚物也有较好的颜料润湿性。  \n\n（4）低聚物的玻璃化温度 $T_{\\mathrm{g}}$ 低聚物的 ${T_{\\mathrm{g}}}$ 高，一般硬度高，光泽好；低聚物的 $\\pmb{T_{8}}$ 低，柔韧性好，耐冲击性也好。表3-2为常用低聚物的折射率和玻璃化温度。  \n\n表3-2常用低聚物的折射率和玻璃化温度  \n\n\n<html><body><table><tr><td>产品代号</td><td>化学名称</td><td>折射率 (25℃)</td><td>玻璃化温度T /℃</td><td>拉伸强度 /Pa</td><td>伸长率 1%</td></tr><tr><td>CN111</td><td>大豆油EA</td><td>1.4824</td><td>35</td><td></td><td></td></tr><tr><td>CN120</td><td>EA</td><td>1.5556</td><td>60</td><td></td><td></td></tr><tr><td>CN117</td><td>改性EA</td><td>1.5235</td><td>51</td><td>5400</td><td>6</td></tr><tr><td>CN118</td><td>酸改性EA</td><td>1.5290</td><td>48</td><td></td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>产品代号</td><td>化学名称</td><td>折射率 (25℃)</td><td>玻璃化温度Tg /℃</td><td>拉伸强度 /Pa</td><td>伸长率 /%</td></tr><tr><td>CN2100</td><td>胺改性EA</td><td></td><td>60</td><td>1900</td><td>6</td></tr><tr><td>CN112C60</td><td>酚醛EA(含40%TMPTA)</td><td>1.5345</td><td>40</td><td></td><td></td></tr><tr><td>CN962</td><td>脂肪族PUA</td><td>1.4808</td><td>一38</td><td>265</td><td>37</td></tr><tr><td>CN963A80</td><td>脂肪族PUA(含20%TPGDA)</td><td>1.4818</td><td>48</td><td>7217</td><td>6</td></tr><tr><td>CN929</td><td>三官能度脂肪族PUA</td><td>1.4908</td><td>13</td><td>1628</td><td>58</td></tr><tr><td>CN945A60</td><td>三官能度脂肪族PUA(含40%TPGDA)</td><td>1.4758</td><td>53</td><td>1623</td><td>6</td></tr><tr><td>CN983</td><td>脂肪族PUA</td><td>1.4934</td><td>90</td><td>2950</td><td>2</td></tr><tr><td>CN972</td><td>芳香族PUA</td><td>1.4811</td><td>-47</td><td>142</td><td>17</td></tr><tr><td>CN970E60</td><td>芳香族PUA(含40%EOTMPTA)</td><td>1.5095</td><td>70</td><td>6191</td><td>4</td></tr><tr><td>CN2200</td><td>PEA</td><td></td><td>-20</td><td>700</td><td>20</td></tr><tr><td>CN2201</td><td>PEA</td><td></td><td>93</td><td>5000</td><td>4</td></tr><tr><td>CN292</td><td>PEA</td><td>1.4681</td><td>1</td><td>1345</td><td>3</td></tr><tr><td>CN501</td><td>胺改性聚醚丙烯酸酯</td><td>1.4679</td><td>24</td><td></td><td></td></tr><tr><td>CN550</td><td>胺改性聚醚丙烯酸酯</td><td>1.4704</td><td>-10</td><td></td><td></td></tr></table></body></html>  \n\n（5）低聚物的固化收缩率低的固化收缩率有利于提高固化膜对基材的附着力，低聚物官能度增加，交联密度提高，固化收缩率也增加。表3-3为常见低聚物固化收缩率。  \n\n表3-3常见低聚物固化收缩率①  \n\n\n<html><body><table><tr><td>低聚物</td><td>分子量M</td><td>官能度f</td><td>收缩率/%</td></tr><tr><td>EA</td><td>500</td><td>2</td><td>11</td></tr><tr><td>酸改性EA</td><td>600</td><td>2</td><td>9</td></tr><tr><td>大豆油EA</td><td>1200</td><td>3</td><td>7</td></tr><tr><td>芳香族PUA(1)</td><td>1000</td><td>6</td><td>10</td></tr><tr><td>芳香族PUA(2)</td><td>1500</td><td>2</td><td>5</td></tr><tr><td>脂肪族PUA(1)</td><td>1000</td><td>6</td><td>10</td></tr><tr><td>脂肪族PUA(2)</td><td>1500</td><td>2</td><td>3</td></tr><tr><td>聚醚</td><td>1000</td><td>4</td><td>6</td></tr><tr><td>PEA(1)</td><td>1000</td><td>4</td><td>11</td></tr><tr><td>PEA(2)</td><td>1500</td><td>4</td><td>14</td></tr><tr><td>PEA(3)</td><td>1500</td><td>6</td><td>10</td></tr></table></body></html>\n\n$\\Phi$ 100%低聚物， $5\\%$ I500光引发剂；在 $120\\mathrm{w/cm}$ ， $10\\mathrm{m/min}$ 条件下固化。  \n\n（6）毒性和刺激性低聚物由于分子量都较大，大多为黏稠状树脂，不挥发，不是易燃易爆物品，其毒性也较低，对皮肤刺激性也较低。表3-4 为部分低聚物的皮肤刺激性。  \n\n续表  \n表3-4部分低聚物的皮肤刺激性  \n\n\n<html><body><table><tr><td>产品代号</td><td>化学名称</td><td>官能度</td><td>PII </td></tr><tr><td>EB600</td><td>双酚A型EA</td><td>2</td><td>0.2</td></tr><tr><td>EB860</td><td>大豆油EA</td><td>3</td><td>0.4</td></tr><tr><td>EB3600</td><td>胺改性双酚A型EA</td><td>2</td><td>0.1</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>产品代号</td><td>化学名称</td><td>官能度</td><td>PII</td></tr><tr><td>EB3608</td><td>脂肪酸改性EA</td><td>2</td><td>0.5</td></tr><tr><td>EB210</td><td>芳香族PUA</td><td>2</td><td>2.2</td></tr><tr><td>EB230</td><td>高分子量脂肪族PUA</td><td>2</td><td>2.3</td></tr><tr><td>EB270</td><td>脂肪族PUA</td><td>2</td><td>1.7</td></tr><tr><td>EB264</td><td>三官能度脂肪族PUA(含15%HDDA)</td><td>3</td><td>3.0</td></tr><tr><td>EB220</td><td>六官能度脂肪族PUA</td><td>6</td><td>0.7</td></tr><tr><td>EB1559</td><td>PEA（含40%HEMA)</td><td>2</td><td>1.8</td></tr><tr><td>EB810</td><td>四官能度PEA</td><td>4</td><td>1.3</td></tr><tr><td>EB870</td><td>六官能度PEA</td><td>6</td><td>0.6</td></tr><tr><td>EB438</td><td>氯化PEA(含40%OTA480)</td><td></td><td>2.2</td></tr><tr><td>EB350</td><td>有机硅丙烯酸酯</td><td>2</td><td>0.9</td></tr><tr><td>EB1360</td><td>六官能度有机硅丙烯酸酯</td><td>6</td><td>1.2</td></tr></table></body></html>  \n\n不饱和聚酯（unsaturated polyester，UPE）是最早用于光固化材料的低聚物。1968年德国拜耳公司开发的第一代光固化材料就是不饱和聚酯与苯乙烯组成的光固化涂料，用于木器涂装。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 66,
+        "chunk": "# 3.2.1不饱和聚酯的合成  \n\n![](images/113302a5b71529429d5d42c3525190b81dd6b998b5363656e54eb10961c7f3a8.jpg)  \n\n不饱和聚酯是由二元醇和二元酸加热缩聚而制得。其中二元醇有乙二醇、多缩乙二醇、丙二醇、多缩丙二醇、1，4-丁二醇等。二元酸必须有不饱和二元酸或酸酐，如马来酸、马来酸酐、富马酸；并配以饱和二元酸如邻苯二甲酸、邻苯二甲酸酐、丁二酸、丁二酸酐、己二酸、己二酸酐等。不饱和二元酸通常用马来酸酐，价廉易得，而且随马来酸酐用量增加，光固化速率也会增加，并达到一个最佳值，通常马来酸酐的摩尔分数应不低于总羧酸量的一半。加入饱和二元酸可改善不饱和聚酯的弹性，起到增塑作用，还可减少体积收缩，但会影响树脂的光固化速率。一般使用酸酐和二元醇反应制备不饱和聚酯，可减少水的生成量，有利于缩聚反应的进行，特别是马来酸酐不易发生均聚，可在较高反应温度下进行脱水缩聚。  \n\n将二元酸、二元醇和适量阻聚剂（如对苯二酚）加人到反应器中，通入氮气，搅拌升温到 $160^{\\circ}\\mathrm{C}$ 回流，测酸值至 ${\\bf200m g~K O H/g}$ 左右，开始出水，升温至 $175{\\sim}200^{\\circ}\\mathrm{C}$ ，当酸值达到设定值时，停止反应，降温至 $80^{\\circ}\\mathrm{C}$ 左右，加人 $20\\%\\sim30\\%$ 的活性稀释剂（苯乙烯或丙烯酸酯类活性稀释剂）和适量阻聚剂出料。  \n\n反应中通氮气，可促进脱水，也能防止树脂在反应中因高温而颜色变深。反应程度通过测定反应体系的酸值来监控；反应结束可以通过测定产物的碘值了解产物的双键含量。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 67,
+        "chunk": "# 3.2.2不饱和聚酯的性能和应用  \n\n不饱和聚酯由于原料来源方便、价廉，合成工艺简单，与苯乙烯配合使用，价格便宜，得到的固化涂层硬度好，耐溶剂和耐热，在木器涂装上涂成厚膜，产生光泽丰满的装饰效果，故至今仍在欧洲、美国、日本木器涂装生产线上使用，用作光固化木器涂料的填充料、底漆和面漆，我国基本不使用。  \n\n不饱和聚酯光固化基团是乙烯基 $\\scriptstyle{\\mathsf{C}}={\\mathsf{1}}$ C双键，反应活性低，因此光固化速率慢，表干性能差，涂层不够柔软，聚酯主链上大量酯基耐酸碱性差。苯乙烯作为不饱和聚酯的活性稀释剂价廉，黏度低，稀释效果好，反应活性也较高，但它是挥发性易燃易爆液体，有特殊臭味，具有较大毒性，使用受到限制。可以用部分丙烯酸酯活性稀释剂来代替苯乙烯，克服上述病。常用不饱和聚酯低聚物的性能和应用见表3-5。  \n\n表3-5常用不饱和聚酯低聚物的性能和应用  \n\n\n<html><body><table><tr><td>公司</td><td>产品代号</td><td>化学名称</td><td>黏度/mPa·s</td><td>特点和应用</td></tr><tr><td rowspan=\"4\">拜耳</td><td>300/1</td><td>UPE 含30%St</td><td>650</td><td>坚硬，柔韧，耐划擦性优异，丰满度好，用于高光或亚光木 器上</td></tr><tr><td>500</td><td>UPE 含32%St</td><td>1600</td><td>柔韧性优，抛光性优，丰满度好，用于亮光木器上</td></tr><tr><td>UAVPLS2380</td><td>UPE 含30%TPGDA</td><td>29000</td><td>漆膜坚硬，光泽高，良好的附着力及打磨性，用于木器及家 具底漆和面漆</td></tr><tr><td>UAVPLS2110</td><td>UPE 含30%TPGDA</td><td>17000</td><td>耐黄变，更佳的抗刮擦性，用于木器及家具底漆和面漆</td></tr><tr><td rowspan=\"4\">盖斯塔夫</td><td>UV78</td><td>UPE 含30%St</td><td></td><td>抛光性、丰满度好，用于淋涂木器着色底漆和面漆</td></tr><tr><td>UV82</td><td>UPE 含30%St</td><td></td><td>抛光性，用于辊涂木器底漆</td></tr><tr><td>UV92</td><td>UPE 含25%St</td><td></td><td>高反应活性，用于木器打磨底漆</td></tr><tr><td>G650</td><td>UPE 含30%St</td><td></td><td>高反应活性，高光泽，高硬度，极好的抛光性，用于木器清漆 和色漆</td></tr><tr><td>巴斯夫</td><td>UP35D</td><td>UPE 含45%DPGDA</td><td>3000～6000</td><td>高硬度，高耐抗性，良好的砂磨性能，用于木器漆</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 68,
+        "chunk": "# 3.3 环氧丙烯酸酯  \n\n环氧丙烯酸酯（epoxy acrylate，EA）是目前应用最广泛、用量最大的光固化低聚物，它是由环氧树脂和（甲基）丙烯酸酯化而制得。环氧丙烯酸酯按结构类型不同，可分为双酚A环氧丙烯酸酯、酚醛环氧丙烯酸酯、环氧化丙烯酸酯和改性环氧丙烯酸酯，其中以双酚A环氧丙烯酸酯最为常用，用量也最大。",
+        "category": " Introduction"
+    },
+    {
+        "id": 69,
+        "chunk": "# 3.3.1环氧丙烯酸酯的合成  \n\n环氧丙烯酸酯的合成反应如下。  \n\n![](images/ae96e210e471514166bdba738d4610c4033f3e15d9df3f4ac98ddd3b85126c66.jpg)  \n\n环氧丙烯酸酯是用环氧树脂和丙烯酸在催化剂作用下经开环酯化而制得。为了得到高光固化速率的环氧丙烯酸酯，要选择高环氧基含量和低黏度的环氧树脂，这样可引人更多的丙烯酸基团。因此双酚A环氧丙烯酸酯一般选用E-51［环氧值为 $(0.51\\pm0.03)\\mathrm{eq}/100\\mathrm{g}]$ 或E-44[环氧值为 $\\left(0.44\\pm0.03\\right)\\mathrm{eq}/100\\mathrm{g}]$ ；酚醛环氧树脂选用F-51[环氧值为（ $(0.51\\pm$ $0.03)\\mathbf{eq}/100\\mathbf{g}]$ 或F-44［环氧值为 $(0.44{\\pm}0.03)\\mathrm{eq}/100\\mathrm{g}]$ 0  \n\n催化剂一般用叔胺、季铵盐，常用三乙胺、 $N,N-$ 二甲基苄胺、 $N,N-$ 二甲基苯胺、三甲基苄基氯化铵、三苯基磷、三苯基锑、乙酰丙酮铬、四乙基溴化铵等，用量 $0.1\\%\\sim3\\%$ （质量分数)。三乙胺虽然价廉，但催化活性相对较低，产品稳定性稍差；季铵盐催化活性稍强，但成本稍高；三苯基磷、三苯基锑、乙酰丙酮铬催化活性高，产物黏度低，但色泽较深。  \n\n丙烯酸和环氧基开环酯化是放热反应，因此反应初期控制温度是非常重要的，通常采用将环氧树脂升温至 $80{\\sim}90^{\\circ}\\mathrm{C}$ ，滴加丙烯酸、催化剂和阻聚剂混合物，控制反应温度 $100^{\\circ}\\mathrm{C}$ ，同时取样测定酸值，到反应后期升温至 $110{\\sim}120^{\\circ}\\mathrm{C}$ ，使酸值降至小于 $5\\mathrm{mg}\\ \\mathrm{KOH/g}$ 停止反应（一般反应时间需要 $4\\mathrm{\\sim}6\\mathrm{h})$ ，冷却到 $80^{\\circ}\\mathrm{C}$ 出料。由于环氧丙烯酸酯黏度较大，可以在冷至 $80^{\\circ}\\mathsf{C}$ 时，加人 $20\\%$ 的活性稀释剂（三丙三醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯）和适量阻聚剂。  \n\n由于反应温度较高，为防止丙烯酸和环氧丙烯酸酯的聚合必须加入阻聚剂，常用的阻聚剂为对甲氧基苯酚、对苯二酚、2,5-二甲基对苯二酚、2,6-二叔丁基对甲苯酚等，加入量为$0.01\\%\\sim1\\%$ （质量分数）。  \n\n丙烯酸和环氧树脂投料比，大多数情况下控制在环氧树脂稍微过量，即丙烯酸：环氧树脂环氧基 $=(1:1)\\sim(1:1.05)$ ，以防止残存的丙烯酸对基材和固化膜有不良影响。残留的环氧基也会影响树脂的贮存稳定性。  \n\n环氧丙烯酸酯的合成（以双酚A-环氧丙烯酸酯为例）主反应为：  \n\n其中，R为：  \n\n![](images/46a8e9849ba429f697949b1e7359fdf3186c09be6e17a1bfa385aacad0ace2a8.jpg)  \n\n副反应为：  \n\n后三个副反应都可以引起树脂发生交联而凝胶，因此反应时要控制好反应温度，反应初期和中期温度不宜过高，极为重要。反应程度通过测定反应体系的酸值来控制；反应结束可以通过产物的碘值测量，了解合成过程中双键的损失，还可以通过产物的环氧值了解残存的环氧基含量。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 70,
+        "chunk": "# 3.3.2环氧丙烯酸酯的性能与用途  \n\n（1）双酚A环氧丙烯酸酯双酚A环氧丙烯酸酯分子中含有苯环，使树脂有较高的刚性、强度和热稳定性，同时侧链的羟基有利于极性基材的附着，也有利于颜料的润湿。  \n\n双酚A环氧丙烯酸酯在低聚物中是光固化速率最快的一种，固化膜具有硬度大、高光泽、耐化学药品性能优异、较好的耐热性和电性能，加之双酚A环氧丙烯酸酯原料来源方便，价格便宜，合成工艺简单，因此广泛地用作光固化纸张、木器、塑料、金属涂料的主体树脂，也用作光固化油墨、光固化胶黏剂的主体树脂。  \n\n双酚A环氧丙烯酸酯的缺点主要是固化膜柔性差，脆性高，同时耐光老化和黄变性差，不适合户外使用，这是由于双酚A环氧丙烯酸酯含有芳香醚键，漆膜经阳光（紫外线）照射后易降解断链而粉化所致。  \n\n（2）酚醛环氧丙烯酸酯酚醛环氧丙烯酸酯为多官能团丙烯酸酯，因此比双酚A环氧丙烯酸酯反应活性更高，交联密度更大；苯环密度大，刚性大，耐热性更佳。其固化膜也具有硬度大、高光泽、耐化学药品性优异、电性能好等优点。只是原料价格稍贵，树脂的黏度较高，因此目前主要用作光固化阻焊油墨，一般很少用于其他光固化产品。  \n\n（3）环氧化油丙烯酸酯环氧化油丙烯酸酯具有价格便宜、柔韧性好、附着力强等特点，对皮肤刺激性小，特别是对颜料有优良的润湿分散性；但光固化速率慢，固化膜软，力学性能差，因此在光固化产品中不单独使用，只是与其他活性高的低聚物配合使用，以改善柔韧性和对颜料的润湿分散性，环氧化油丙烯酸酯主要有环氧大豆油丙烯酸酯、环氧麻油丙烯酸酯。 汉乐  \n\n（4）改性环氧丙烯酸酯  \n\n① 胺改性环氧丙烯酸酯利用少量的伯胺或仲胺与环氧树脂中部分环氧基缩合，余下的环氧基再丙烯酸酯化，得到胺改性环氧丙烯酸酯。  \n\n$\\textcircled{2}$ 脂肪酸改性环氧丙烯酸酯先将少量脂肪酸与环氧树脂中部分环氧基酯化，余下的环氧基再丙烯酸酯化，得到脂肪酸改性环氧丙烯酸酯。  \n\n$\\textcircled{3}$ 磷酸改性环氧丙烯酸酯先用不足量的丙烯酸酯化环氧树脂，余下的环氧基用磷酸  \n\n酯化，得到磷酸改性环氧丙烯酸酯。  \n\n④ 聚氨酯改性环氧丙烯酸酯利用环氧丙烯酸酯侧链上的羟基与二异氰酸和丙烯酸羟乙酯摩尔比 $1:1$ 的半加成物中异氰酸根反应，得到聚氨酯改性环氧丙烯酸酯。  \n\n③ 酸酐改性环氧丙烯酸酯酸酐与环氧丙烯酸酯侧链上的羟基反应，得到带有羧基的酸酐改性环氧丙烯酸酯。  \n\n③ 有机硅改性环氧丙烯酸酯环氧树脂的环氧基与少量带氨基或羟基的有机硅氧烷缩合，再与丙烯酸酯化得到有机硅改性的环氧丙烯酸酯。  \n\n上述几种改性环氧丙烯酸酯的性能特点见表3-6，不同酸酐改性环氧丙烯酸酯的性能见表 3-7。表3-8列举了国内外生产厂商的环氧丙烯酸酯低聚物的性能和应用。  \n\n表3-6改性环氧丙烯酸酯的性能特点  \n\n\n<html><body><table><tr><td>改性环氧丙烯酸酯</td><td>性能特点</td></tr><tr><td>胺改性</td><td>提高光固化速率，改善脆性、附着力和对颜料的润湿性</td></tr><tr><td>脂肪酸改性</td><td>改善柔韧和对颜料的润湿性</td></tr><tr><td>磷酸改性</td><td>提高阻燃性，对金属附着力</td></tr><tr><td>聚氨酯改性</td><td>提高耐磨性、耐热性、弹性</td></tr><tr><td>酸酐改性</td><td>变成碱溶性光固化树脂作光成像材料的低聚物；经胺或碱中和后，作水性UV固化材料的低聚物</td></tr><tr><td>有机硅改性</td><td>提高耐候性、耐热性、耐磨性和防污性</td></tr></table></body></html>  \n\n表3-7不同酸酐改性环氧丙烯酸酯性能比较①  \n\n\n<html><body><table><tr><td>性能</td><td>EA</td><td>丁二酸酐 改性EA</td><td>戊二酸酐 改性EA</td><td>马来酸酐 改性EA</td><td>苯酐改性 EA</td><td>四溴苯酐 改性EA</td><td>四氢苯酐 改性EA</td></tr><tr><td>硬度</td><td>3H</td><td>3H</td><td>3H</td><td>4H</td><td>4H</td><td>4H</td><td>4H</td></tr><tr><td>耐磨性 /(mg/1000r)</td><td>8.4</td><td>7.5</td><td>7.6</td><td>6.8</td><td>6.8</td><td>6.8</td><td>6.8</td></tr></table></body></html>\n\n$\\textcircled{1}$ 低聚物50份，TMPTA20份，TPGDA25份，光引发剂6515份；在 $80\\mathrm{\\textperthousand}$ ， $30m/\\mathrm{min}$ 条件下固化。  \n\n表3-8环氧丙烯酸酯低聚物的性能和应用  \n\n\n<html><body><table><tr><td>公司</td><td>产品代号</td><td>化学名称</td><td>官能度</td><td>黏度（25℃） /mPa·s</td><td>特点和应用</td></tr><tr><td rowspan=\"6\">沙多玛</td><td>CN104</td><td>双酚AEA</td><td>2</td><td>18900(49C)</td><td>高反应性，硬度高，耐化学药品性好，用于木器、纸 张、金属涂料</td></tr><tr><td>CN121</td><td>低黏度EA</td><td>2</td><td>57500</td><td>快速固化，高光泽，用于纸张、木器、塑料涂料、压 敏胶</td></tr><tr><td>CN2100</td><td>胺改性EA</td><td></td><td>43000(65C)</td><td>快速固化，柔韧性好、耐化学药品性好，润湿性好， 用于木器、纸张、金属涂料，油墨</td></tr><tr><td>CN2101</td><td>脂肪酸改性 EA</td><td></td><td>43000</td><td>快速固化，柔韧性和强度兼有，适用柔印、胶印、凹 印、丝印油墨</td></tr><tr><td>CN111</td><td>大豆油EA</td><td></td><td>25100</td><td>柔韧性、附着力、颜料润湿性好，用于油墨以及木 器、纸张、金属涂料</td></tr><tr><td>CN 112C60</td><td>酚醛EA（含 20%TMPTA)</td><td>3</td><td>57900</td><td>高反应活性、耐热性、硬度好，用于阻焊剂以及纸 张、木器、金属涂料</td></tr></table></body></html>  \n\n<html><body><table><tr><td>公司</td><td>产品代号</td><td>化学名称</td><td>官能度</td><td>黏度（25℃） /mPa·s</td><td>特点和应用</td></tr><tr><td rowspan=\"6\">氰特</td><td>EB 600</td><td>双酚AEA</td><td>2</td><td>3000(60℃)</td><td>极低的皮肤刺激性(pII=0.2)，快速固化，高光 泽、抗溶剂性好，用于罩光清漆</td></tr><tr><td>EB6040</td><td>低黏度改性</td><td>2</td><td>25000</td><td>低黏度、高光泽、固化速率快，良好的耐溶解性，用 于罩光清漆</td></tr><tr><td>EB 3600</td><td>EA 胺改性EA</td><td></td><td>2200(60℃)</td><td>快速固化，优异的耐溶剂性，适用于罩光清漆</td></tr><tr><td>EB 3702</td><td>脂肪酸改性 EA</td><td></td><td>3800(60℃)</td><td>低气味，润湿性和流平性好，用于丝印油墨</td></tr><tr><td>EB 860</td><td>大豆油EA</td><td></td><td>25000</td><td>低皮肤刺激性(pI=0.4)，良好的流平性、颜料润 湿性和黏附性，用于胶印油墨</td></tr><tr><td>EB639</td><td>酚醛EA（含 30%TMPTA和 5%HEMA)</td><td>3</td><td>10000</td><td>高反应活性、高交联密度，耐热性好，用于阻焊剂 和金属、木器涂料</td></tr><tr><td>盖斯塔夫</td><td>104.</td><td>EA（含25% TPGDA)</td><td>2</td><td></td><td>高黏度、高活性、高硬度，用于清漆和色漆</td></tr><tr><td rowspan=\"5\">科宁</td><td>3015</td><td>双酚AEA</td><td>2</td><td>85000</td><td>高活性，高光泽、柔韧性好，用于罩光清漆、胶印 油墨</td></tr><tr><td>3215</td><td>低黏度EA</td><td>2</td><td>15000</td><td>低黏度，高活性，高光泽，用于罩光清漆、胶黏剂、 印刷版材</td></tr><tr><td>3660</td><td>胺改性EA</td><td></td><td>7000</td><td>低黏度，高硬度，耐化学药品性好，用于罩光清漆、 木器涂料、柔印油墨</td></tr><tr><td>3005</td><td>大豆油EA</td><td></td><td>16500</td><td>低黏度，柔韧性和颜料润湿性好，用于罩光清漆、 胶印油墨</td></tr><tr><td>3082</td><td>亚麻油EA</td><td></td><td>100000</td><td>颜料润湿性、附着力、柔韧性好，用于胶印、丝印 油墨</td></tr><tr><td rowspan=\"4\">巴斯夫</td><td>EA 81</td><td>EA（含20%</td><td>2</td><td>8000~14000</td><td>硬度高，固化快，耐化学药品性优异，用于各种 涂料</td></tr><tr><td>LR8986</td><td>HDDA) 改性EA</td><td>2.5</td><td>3000～6000</td><td>低黏度，硬度好，耐化学药品性优异，用于各种</td></tr><tr><td>LR 8765</td><td>脂肪族EA</td><td>2</td><td>600～1200</td><td>涂料 高反应活性、柔韧性好，用于各种涂料</td></tr><tr><td>LR9022</td><td>脂肪族EA</td><td>2</td><td>20000～30000</td><td>低黏度，低黄变，耐化学药品性优异，提高附着力，</td></tr><tr><td>拜耳</td><td>UAVPLS 2266</td><td>EA和PEA混</td><td></td><td>8000(23℃)</td><td>用于各种涂料 高反应活性，用于塑料、纸张、木器涂料，层压胶</td></tr><tr><td rowspan=\"5\">长兴</td><td>621A-80</td><td>合物 双酚AEA(含</td><td>2</td><td>28500~40000</td><td>黏剂 快速固化，高光泽，硬度、耐化学药品性好，用于纸</td></tr><tr><td>6210G</td><td>20%TPGDA) 改性EA</td><td>2</td><td>30000~35000</td><td>张、塑料、木器涂料以及油墨 快速固化，硬度高，耐溶剂性好，用于清漆、木器、 纸张、塑料涂料以及胶印、丝印油墨</td></tr><tr><td>622A-80</td><td>脂肪酸改GEA</td><td>1.9</td><td>18000～25000</td><td>张低气味,润湿性和流平性佳,促进柔韧性,用于纸</td></tr><tr><td>6261</td><td>大豆油EA</td><td>3~4</td><td>25000</td><td>柔韧性和颜料分散性佳，用于纸张、塑料清漆、木 器涂料</td></tr><tr><td>625C-45</td><td>酚醛EA（含</td><td>3~4</td><td>6000～9000</td><td>快速固化，高硬度，耐热性、耐化学药品性极佳，用 于阻焊剂以及丝印油墨</td></tr><tr><td>石梅</td><td>M6200</td><td>55%TMPTA) 双酚AEA(含 20%TPGDA)</td><td>2</td><td>300000～ 500000</td><td>快速固化，硬度高，耐化学药品性好，用于纸张、木 器涂料以及丝印油墨</td></tr><tr><td>德谦</td><td>UE-1</td><td>双酚AEA(含 20%TPGDA)</td><td>2</td><td></td><td>快速固化，硬度高，用于纸张、木器、硬塑料、金属 涂料</td></tr></table></body></html>  \n\n<html><body><table><tr><td>公司</td><td>产品代号</td><td>化学名称</td><td>官能度</td><td>黏度（25℃) /mPa·s</td><td>特点和应用</td></tr><tr><td rowspan=\"4\">江苏三木</td><td>6104</td><td>双酚AEA</td><td>2</td><td>7000～ 10000(60℃)</td><td>低色相，高光泽，硬度佳，耐化学品性佳，用于纸 张、地板、摩托车涂料以及油墨、胶黏剂</td></tr><tr><td>61040</td><td>低黏度双酚 AEA</td><td>2</td><td>3000～ 5000(60℃)</td><td>低色相，流平性佳，高反应活性，用于纸张、木器、 塑料涂料</td></tr><tr><td>6109</td><td>脂肪酸改性EA (含20%TPGDA)</td><td>2</td><td>3000～ 6000(60℃)</td><td>润湿性、流平性佳，高反应活性，用于亚光化、金 属、塑料涂料</td></tr><tr><td>6118</td><td>澳化双酚AEA (含20%TPGDA)</td><td>2</td><td>2000～ 8000(60℃)</td><td>阻燃性、耐热性佳，用于木器、塑料涂料以及油墨</td></tr><tr><td rowspan=\"5\">陕西喜 莱坞</td><td>EA 200</td><td>EA</td><td>2</td><td>800～ 1300(50℃)</td><td>低黏度，高硬度，高光泽，快速固化，低刺激性，良 好的耐溶剂性，用于纸张、木器、塑料涂料以及油墨、 胶黏剂</td></tr><tr><td>EA 205</td><td>多元醇改性EA</td><td>2</td><td>800～ 1300(50℃)</td><td>高光泽，快速固化，良好的柔韧性，较强的附着力， 用于金属、纸张、塑料涂料以及油墨、胶黏剂</td></tr><tr><td>EA 210</td><td>多元酸改性EA</td><td>2</td><td>2000～ 3000(50℃)</td><td>高光泽，快速固化，良好的柔韧性，优异的颜料润 湿性，用于纸张、塑料涂料，胶印、丝印、金属油墨以</td></tr><tr><td>EA 215</td><td>脂肪酸改性EA</td><td>2</td><td>1500~2000</td><td>及胶黏剂 高光泽，优异的柔韧性，中等固化速率和黏度，对 颜料润湿性好，用于胶印油墨、罩光油</td></tr><tr><td>EA 220</td><td>大豆油EA</td><td>2</td><td>900～1500</td><td>低黏度，优异的柔韧性，优异的颜料润湿性，良好 的流平性和附着力，固化速率慢，用于胶印、丝印</td></tr><tr><td rowspan=\"2\">中山千 叶合成</td><td>UV1000</td><td>EA（含20% TPGDA)</td><td>2</td><td>10000～ 16000</td><td>油墨 高硬度，高固化速率，低色相，低黏度，用于纸张、 木器、塑料、金属涂料以及胶印油墨、金属油墨</td></tr><tr><td>UV1100</td><td>酸改性EA(含 20%TPGDA)</td><td>2</td><td>20000～ 30000</td><td>低色相，高硬度，高固化速率，耐溶解性好，用于纸 张、木器、塑料、金属涂料以及胶印、丝印油墨</td></tr><tr><td rowspan=\"3\">无锡树 脂厂</td><td>WSR-U120</td><td>酚醛EA</td><td>3</td><td>16500± 50(65C)</td><td>高反应活性，耐热性好，用于阻焊剂，耐热性涂料</td></tr><tr><td>WSR-U125</td><td>双酚AEA</td><td>2</td><td>4100± 50(65C)</td><td>高反应活性，气味小，色泽浅，用于上光油，罩光</td></tr><tr><td>WSR-U133</td><td>低黏度EA</td><td>2</td><td>10000±</td><td>漆，各种涂料 黏度低，柔韧性好，反应活性高，用于柔韧性涂料</td></tr><tr><td rowspan=\"5\">顺德永大</td><td>EP102</td><td>EA</td><td>2</td><td>500(40℃) 25000±500</td><td>固化快，高光泽，高硬度，耐化学品性好，用于纸 张、木器、塑料涂料以及胶印、丝印油墨、胶黏剂</td></tr><tr><td>EP 104</td><td>多元酸改性EA</td><td>≤2</td><td></td><td>固化快，高光泽，高黏度，柔性好，对颜料润湿性 80000士2000|好，用于纸张、木器、塑料涂料以及胶印、丝印油墨、</td></tr><tr><td>EP 105</td><td>多元醇改性EA</td><td></td><td>50000±1000</td><td>胶黏剂 固化快，高光泽，高柔韧性，附着力好，用于木器、 金属、塑料、纸张涂料以及油墨、胶黏剂</td></tr><tr><td>EP107</td><td>脂肪酸改性EA</td><td>2</td><td></td><td>低黏度，高光泽，高柔韧性，分散润湿性好，附着力 10000±2000好，固化速率稍差，用于胶印、丝印金属油墨以及金 属、纸张、木器涂料</td></tr><tr><td>EP 108</td><td>大豆油EA</td><td>2</td><td></td><td>高柔韧性，润湿分散性、流平性好，附着力好，低黏 10000±2000度，用于纸张、PVC、木器涂料以及胶印、丝印、金属 油墨</td></tr></table></body></html>  \n\n聚氨酯丙烯酸酯（polyurethane acrylate，PUA）是又一种重要的光固化低聚物。它是用多异氰酸酯、长链二醇和丙烯酸羟基酯经两步反应合成。由于多异氰酸酯和长链二醇有多种结构可选择，通过分子设计来合成设定性能的低聚物，因此是目前产品牌号最多的低聚物，广泛应用在光固化涂料、油墨、胶黏剂中。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 71,
+        "chunk": "# 3.4.1聚氨酯丙烯酸酯的合成  \n\n聚氨酯丙烯酸酯的合成是利用异氰酸酯中异氰酸根—NCO与长链二醇和丙烯酸羟基酯中羟基—OH反应，形成氨酯键—NHCOO—（氨基甲酸酯）而制得。  \n\n（1）多异氰酸酯用于聚氨酯丙烯酸酯合成的多异氰酸酯为二异氰酸酯，又有芳香族二异氰酸酯和脂肪族二异氰酸酯两大类，主要有下列几种。  \n\n① 甲苯二异氰酸酯（简称TDI）为水白色或浅黄色液体，是最常用的芳香族二异氰酸酯，它有2,4-体和2,6-体两种异构体，商品TDI有TDI-80（80%2,4-体和 20%2,6-体)、TDI-65（65%2,4-体和 35%2,6-体）、TDI-100（100% 2,4-体）三种。TDI价格较低，反应活性高，所合成的聚氨酯硬度高，耐化学品性优良，耐磨性较好；但耐黄变性较差，其原因是在光老化中会形成有色的或偶氮结构。TDI有强烈的刺激性气味，对皮肤、眼睛和呼吸道有强烈的刺激作用，毒性较大。国际标准规定，空气中允许浓度为0.2mg/m。  \n\n![](images/ae0252dc1bad42dc53677ab086f7fd09457c1ec26d5952a1f2ebf393f2ed51b4.jpg)  \n\n②二苯基甲烷二异氰酸酯（MDI）为白色固体结晶，室温下易生成不溶解的二聚体，颜色变黄，要低温贮存，又是固体使用不方便。为此商品化有液体MDI供应，为淡黄色透明液体，—NCO含量为28.0%～30.0%。MDI毒性比TDI低，由于结构对称，故制成涂料漆膜强度、耐磨性、弹性优于TDI，但其耐黄变性比TDI更差，在光老化中，更易生成有色的鼠式结构。  \n\n![](images/b3908ad4955ddd04a23787d1c1acab08afbf3d28791a1416af9d55ff1b0e83d5.jpg)  \n\n$\\textcircled{3}$ ③苯二亚甲基二异氰酸酯（XDI）为无色透明液体，由71%间位XDI和29%对位XDI 组成。XDI虽为芳香族二异氰酸酯，但苯基与异氰酸基之间有亚甲基间隔，因此不会像 TDI和MDI那样易黄变，接近脂肪族二异氰酸酯。它的反应性比MDI快，但泛黄性和保光性比TDI稍差，比MDI优越。  \n\n![](images/10be0cc14955d1d61506e550e2b279514978e3e67bd8f3e0ee87165a8257dba4.jpg)  \n间XDI  \n\n![](images/0c3eab535510a3719a56bec8726b2a6d6e51d834468c4c7042f677924fa3d33a.jpg)  \n对XDI  \n\n④六亚甲基二异氰酸酯（HDI）为无色或浅黄色液体，是最常用的脂肪族二异氰酸酯，反应活性较低，所合成的聚氨酯丙烯酸酯有较高的柔韧性和较好的耐黄变性。  \n\n③异佛尔酮二异氰酸酯（IPDI）为无色或浅黄色液体，是脂环族二异氰酸酯，所合成的聚氨酯丙烯酸酯有优良的耐黄变性、良好的硬度和柔顺性。  \n\n![](images/5a92a4fcb21f9045ce04cadce2bf985ad4393ee5eb50604dcbdc4afbb7090936.jpg)  \n\n![](images/d5026be404bff9cd149192fc8f4210016f8923406072c06a87849a19de908294.jpg)  \nHMDI  \n\n③二环已基甲烷二异氰酸酯（HMDI）为无色或浅黄色液体，也是脂环族二异氰酸酯，其反应性低于TDI，所合成的聚氨酯丙烯酸酯有优良的耐黄变性、良好的挠性和硬度。常见二异氰酸酯的物理性能、应用性能和毒性见表3-9～表3-11。  \n\n表3-9常见二异氰酸酯的物理性能  \n\n\n<html><body><table><tr><td>二异氰酸酯</td><td>分子量</td><td>密度（25℃) /(g/cm3)</td><td>沸点 /℃</td><td>闪点 /℃</td><td>蒸气压 /Pa</td><td>—NCO含量 /%</td></tr><tr><td>TDI</td><td>174</td><td>1.22</td><td>120(1333Pa)</td><td>127</td><td>3.3(25℃)</td><td>48.2</td></tr><tr><td>MDI</td><td>250</td><td>1.19</td><td>190(667Pa)</td><td>202</td><td>107(160℃)</td><td>33.5</td></tr><tr><td>XDI</td><td>188</td><td>1.202</td><td>161(1333Pa)</td><td>185</td><td></td><td>44.6</td></tr><tr><td>HDI</td><td>168</td><td>1.05</td><td>112(667Pa)</td><td>130</td><td>1.5(20℃)</td><td>50.0</td></tr><tr><td>IPDI</td><td>222</td><td>1.058</td><td>153(1333Pa)</td><td>155</td><td>0.09(20°℃)</td><td>37.8</td></tr><tr><td>HMDI</td><td>258</td><td>1.07</td><td>160~165(110Pa)</td><td>>202</td><td></td><td>32.5</td></tr></table></body></html>  \n\n表3-10常见二异氰酸酯的应用性能  \n\n\n<html><body><table><tr><td>二异氰酸酯</td><td>反应活性</td><td>耐黄变性</td><td>相容性</td><td>价格</td></tr><tr><td>TDI</td><td>高</td><td>差</td><td>好</td><td>低</td></tr><tr><td>MDI</td><td>较高</td><td>最差</td><td>较好</td><td>低</td></tr><tr><td>XDI</td><td>较高</td><td>较好</td><td>好</td><td>较低</td></tr><tr><td>HDI</td><td>低</td><td>好</td><td>差</td><td>高</td></tr><tr><td>IPDI</td><td>最低</td><td>好</td><td>好</td><td>高</td></tr><tr><td>HMDI</td><td>低</td><td>好</td><td>好</td><td>高</td></tr></table></body></html>  \n\n表3-11常见二异氰酸酯的毒性  \n\n\n<html><body><table><tr><td>二异氰酸酯</td><td>饱和蒸气浓度(20℃) /(mg/m3)</td><td>LD50经口服(大鼠) /(mg/kg)</td><td>LD5o吸入(大鼠) /(mg/kg)</td><td>危险品操作等级</td></tr><tr><td>TDI</td><td>142</td><td>5800</td><td>110(气溶胶，4h)</td><td>有毒</td></tr><tr><td>MDI</td><td>0.8</td><td>>1500</td><td>370(气溶胶，4h)</td><td>有害健康</td></tr><tr><td>HDI</td><td>47.7</td><td>913</td><td>150(气溶胶，4h)</td><td>有毒</td></tr><tr><td>IPDI</td><td>3.1</td><td>4700</td><td>123(气溶胶，4h)</td><td>有毒</td></tr><tr><td>HMDI</td><td>3.5</td><td>>11000</td><td></td><td>有毒</td></tr></table></body></html>\n\n$\\Phi$ 欧洲经济共同体采用的危险品标识。  \n\n二异氰酸酯中一NCO基团与醇羟基反应活性和二异氰酸酯结构有关，芳香族二异氰酸  \n酯比脂肪族二异氰酸酯活性要高；—NCO基团邻位若有—CH3等其他基团，由于空间位阻  \n影响反应活性，所以TDI中4位—NCO活性明显高于2位--NCO；二异氰酸酯中，第一个-NCO基团的反应活性又高于第二个一NCO，见表3-12。（2）长链二醇用于合成聚氨酯丙烯酸酯的长链二醇，主要有聚醚二醇和聚酯二醇两大类。  \n$\\textcircled{1}$ 聚醚二醇有聚乙二醇、聚丙二醇、环氧乙烷-环氧丙烷共聚物、聚四氢呋喃二醇等。  \n\n表3-12二异氰酸酯醇羟基反应活性比较   \n\n\n<html><body><table><tr><td>二异氰酸酯</td><td>第一个—NCO基团反应活性</td><td>第二个—NCO基团反应活性</td></tr><tr><td>TDI</td><td>400(4位)</td><td>33(2位)</td></tr><tr><td>XDI</td><td>27</td><td>10</td></tr><tr><td>HDI</td><td>1</td><td>0.5</td></tr></table></body></html>  \n\n$$\n\\mathrm{HO\\mathrm{+}C H_{2}C H_{2}C H_{2}C H_{2}O\\}_{\\overline{{n}}}H\n$$  \n\n由于聚醚中的醚键内聚能低，柔性好，因此合成的聚醚型聚氨酯丙烯酸酯低聚物黏度较低，固化膜的柔性好，但是力学性能和耐热性稍差。  \n\n$\\textcircled{2}$ 聚酯二醇传统的聚酯二元醇，由二元酸和二元醇缩聚制得，或由聚已内酯二醇制得。  \n\n聚酯键一般机械强度较高，因此合成的聚酯型聚氨酯丙烯酸酯低聚物具有优异的拉伸强度、模量、耐热性。若聚酯为苯二甲酸型，则硬度好；若为已二酸型，则柔韧性优良。若酯中二元醇为长链碳，则柔韧性好；但如用短链的三元醇或四元醇代替二元醇，则可得到具有高度交联能力的刚性支化结构，固化速率快，硬度高，力学性能更好。但聚酯遇碱易发生水解，故聚酯型聚氨酯丙烯酸酯耐碱性较差。  \n\n（3）（甲基）丙烯酸羟基酯有丙烯酸羟乙酯（HEA)、丙烯酸羟丙酯（HPA)、甲基丙烯酸羟乙酯（HEMA)、甲基丙烯酸羟丙酯（HPMA)、三羟甲基丙烷二丙烯酸酯（TMP-DA)、季戊四醇三丙烯酸酯（PETA)。  \n\n![](images/200989181bc68c486dd65de1fd5a9ba79139fa10ac72847a67352216fbd6ab7b.jpg)  \n\n由于丙烯酸酯光固化速率要比甲基丙烯酸酯快得多，故绝大多数用丙烯酸羟基酯。  \n\n异氰酸根与醇羟基的反应活性：伯醇 $>$ 仲醇 $>$ 叔醇，相对反应速率约为伯醇：仲醇：叔$\\mathtt{M H}{=}1:0.3:(0.003{\\sim}0.007)$ ，因此大多数用HEA（伯醇）与异氰酸酯反应，而较少用HPA(仲醇)。  \n\n为了制备多官能度的聚氨酯丙烯酸酯，需用TMPDA和PETA与异氰酸酯反应。  \n\n（4）催化剂虽然二异氰酸酯中—NCO比醇羟基反应活性高，容易进行，但为了缩短反应时间，加快反应速率，引导反应沿着预期的方向进行，反应中都需要加人少量催化剂，常用的催化剂有叔胺类、金属化合物和有机磷，不同催化剂的催化活性不同，见表3-13。实际应用上，常用催化剂为月桂酸二丁基锡，用量为总投料量的",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 72,
+        "chunk": "# $0.01\\%\\sim1\\%_{\\circ}$  \n\n表3-13不同催化剂的作用情况  \n\n\n<html><body><table><tr><td rowspan=\"2\">催化剂</td><td colspan=\"3\">—NCO·—OH=1：1,密封后凝胶时间/min</td></tr><tr><td>TDI</td><td>XDI</td><td>HDI</td></tr><tr><td>无</td><td>>240</td><td>>240</td><td>>240</td></tr><tr><td>三乙醇胺</td><td>120</td><td>>240</td><td>>240</td></tr><tr><td>三亚乙基二胺</td><td>4</td><td>80</td><td>>240</td></tr><tr><td>月桂酸二丁基锡</td><td>6</td><td>3</td><td>3</td></tr><tr><td>辛酸亚锡</td><td>. 4</td><td>3</td><td>4</td></tr><tr><td>辛酸钻</td><td>12</td><td>4</td><td>4</td></tr><tr><td>辛酸铅</td><td>2</td><td>１</td><td>2</td></tr><tr><td>环烷酸锌</td><td>60</td><td>6</td><td>10</td></tr></table></body></html>  \n\n叔胺对芳香族TDI有显著催化作用，但对脂肪族HDI催化作用极弱；金属化合物对芳香族和脂肪族异氰酸酯都有强烈的催化作用，但环烷酸锌对芳香族TDI催化作用弱，而对脂肪族HDI作用较强。  \n\n在2，4-TDI中，4位—NCO与2位—NCO反应活性有较大差距，但温度升高，则两者差距缩小，见表3-14。  \n\n表3-14甲苯二异氰酸酯中—NCO反应速率  \n\n\n<html><body><table><tr><td>反应温度/℃</td><td>29</td><td>49</td><td>72</td><td>100</td></tr><tr><td>2位—NCO</td><td>1.5×10-5</td><td>1.8X10-5</td><td>7.2X10-5</td><td>3.2X10-4</td></tr><tr><td>4位—NCO</td><td>4.5X10-5</td><td>1.2X10-</td><td>3.4X10-4</td><td>8.5X10-5</td></tr><tr><td>相差倍数</td><td>7.9</td><td>6.7</td><td>4.7</td><td>2.7</td></tr></table></body></html>\n\n①反应速率是指用已二酸与一缩二乙二醇制得的聚酯，取0.2mol聚酯与0.02mol的2,4-TDI在氯苯中反应，不同温度下的反应速率常数k，单位为 $\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{s})$ 。  \n\n在较低温度下，2，4-TDI主要是4位—NCO与醇羟基反应，因此利用二异氰酸酯中—-NCO基团与醇羟基反应活性的差别，可以选择性地进行反应，制得分子量分布较均匀的半加成物和聚氨酯丙烯酸酯低聚物。  \n\n（5）聚氨酯丙烯酸酯的合成工艺聚氨酯丙烯酸酯的合成路线有两条，第一条合成路线是二异氰酸酯先与二醇反应，再与丙烯酸羟基酯反应。  \n\n![](images/26e75b25816b137733a2e1c31c4e478069cf1dea36f25e91b499ae2585dbc8a4.jpg)  \n\n第二条合成路线是二异氰酸酯先与丙烯酸羟基酯反应，再与二醇反应。  \n\n![](images/3a7f5875c24e75d42ac4d4fd4cfd1aaff90fa67bb18fd81b25c583b26e49afb2.jpg)  \n\n两条合成路线比较，由于第一条合成路线是异氰酸酯先扩链，再丙烯酸酯酯化，这样丙烯酸酯在反应釜内停留时间较短，有利于防止丙烯酸酯受热时间过长而容易聚合、凝胶。虽然丙烯酸酯封端反应可能不彻底，会存在少量没有反应的丙烯酸羟基酯，但不会影响使用。而第二条合成路线，由于二异氰酸酯先与丙烯酸羟基酯反应生成丙烯酸酯，再与二醇反应时，丙烯酸酯受热聚合可能性增加，需加入更多阻聚剂，这对产品的色度和光聚合反应活性会产生不良影响。 10.  \n\n对芳香族2,4-TDI来讲，由于4位—NCO基团反应活性远高于2位—NCO基团活性，可以在较低温度下与二醇反应，生成4位半加成物，再在较高温度下，2位—NCO基团与丙烯酸羟基酯反应制得分子结构和分子量较均匀的聚氨酯丙烯酸酯。· 茶  \n\n由于异氰酸基团与羟基反应是放热反应，为避免反应因放热而使反应温度升高，以致发生凝胶化，故反应物要采取滴加方法，将二醇慢慢滴加到含有催化剂的二异氰酸酯中。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 73,
+        "chunk": "#  \n\n异氰酸基团也极易与水反应，生成胺，可继续与异氰酸酯反应，形成缩脲结构。  \n\nOI在碱性条件下，二异氰酸酯与二醇生成的氨基甲酸酯（\\~\\~NH-C—O—）会继续与",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 74,
+        "chunk": "# -NCO基团反应。  \n\n这两个副反应会使聚氨酯丙烯酸酯合成过程中黏度增大，甚至发生交联而凝胶化，因此所用二醇和丙烯酸羟基酯都需进行脱水处理和清除微量碱离子。  \n\n聚氨酯丙烯酸酯的合成是将2mol二异氰酸酯和月桂酸二丁基锡加人反应器中，升温到40～50℃，慢慢滴加lmol二醇，反应1h后，可升温到60℃，测定—NCO值到计算值，加入2mol丙烯酸羟基酯和阻聚剂对苯二酚，升温至70～80℃，直至—NCO值为零。鉴于—NCO有较大毒性，反应时可以适当使丙烯酸羟基酯稍微过量一点，以使—NCO基团完全反应。反应完毕，考虑到聚氨酯丙烯酸酯黏度较大，可加入适量的丙烯酸酯活性稀释剂，如用三丙二醇二丙烯酸酯进行稀释，搅拌均匀出料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 75,
+        "chunk": "# 3.4.2聚氨酯丙烯酸酯的性能和应用  \n\n聚氨酯丙烯酸酯（PUA）分子中有氨酯键，能在高分子链间形成多种氢键，使固化膜具有优异的耐磨性和柔韧性，断裂伸长率高，同时有良好的耐化学药品性和耐高、低温性能，较好的耐冲击性，对塑料等基材有较好的附着力，总之，PUA具有较佳的综合性能。  \n\n由芳香族异氰酸酯合成的PUA称为芳香族PUA，由于含有苯环，因此链呈刚性，其固化膜有较高的机械强度和较好的硬度及耐热性。芳香族PUA价格相对较低，最大的缺点是固化膜耐候性较差，易黄变。  \n\n由脂肪族和脂环族异氰酸酯制得的PUA称为脂肪族PUA，主链是饱和烷烃和环烷烃，耐光、耐候性优良，不易黄变，同时黏度较低，固化膜柔韧性好，综合性能较好，但价格较贵，涂层硬度较差。  \n\n由聚酯多元醇与异氰酸酯反应合成的PUA，主链为聚酯，一般机械强度高，固化膜有优异的拉伸强度、模量和耐热性，但耐碱性差。由聚醚多元醇与异氰酸酯合成的PUA，有较好的柔韧性，较低的黏度，耐碱性提高，但硬度、耐热性稍差。  \n\nPUA虽然有较佳综合性能，但其光固化速率较慢，黏度也较高，价格相对较高，在中高档的光固化产品中作主体树脂用，在一般的低档的光固化产品中较少用PUA作为主体树脂，常常为了改善涂料的某些性能，如增加涂层的柔韧性、改善附着力、降低应力收缩、提高耐冲击性而作为辅助性功能树脂使用。芳香族PUA在光固化纸张、木器、塑料涂料上应用，脂肪族PUA在光固化摩托车涂料、汽车车灯涂料和手机涂料上应用。表3-15为芳香族聚氨酯丙烯酸酯低聚物的性能和应用，表3-16为脂肪族聚氨酯丙烯酸酯低聚物的性能和应用。  \n\n表3-15芳香族聚氨酯丙烯酸酯低聚物的性能和应用  \n\n\n<html><body><table><tr><td>公 司</td><td>产品代号</td><td>化学名称</td><td>官能度</td><td>黏度（25℃）/mPa·s</td><td>特点和应用</td></tr><tr><td rowspan=\"3\">沙多玛</td><td>CN 972</td><td>芳香族PUA</td><td>2</td><td>4155</td><td>低T，柔韧性好，用于纸张、木 器、金属涂料，油墨，胶黏剂</td></tr><tr><td>CN 997</td><td>六官能度芳香族PUA</td><td>6</td><td>25000</td><td>快速固化，耐化学药品性好，用 于金属、塑料涂料，油墨</td></tr><tr><td>CN999</td><td>经济型芳香族PUA</td><td>2</td><td>1200</td><td>低黏度，杰出的耐摩擦性，比 EA更好的耐磨性和耐候性，用于 高耐磨涂料</td></tr><tr><td rowspan=\"3\">氰特</td><td>EB210</td><td>芳香族PUA</td><td>2</td><td>3900(60C)</td><td>具有广泛的通用性，用于各种 罩光清漆</td></tr><tr><td>EB205</td><td>三官能度芳香族PUA（含 25%HDDA)</td><td>3</td><td>17000</td><td>非常好的反应活性和耐磨性， 用于各种罩光清漆</td></tr><tr><td>EB2220</td><td>六官能度芳香族PUA</td><td>6</td><td>28500</td><td>极快固化速率，高硬度和耐溶剂 性，常加入涂料、油墨中加快固化 速率</td></tr><tr><td rowspan=\"2\">科宁</td><td>6363</td><td>芳香族PUA</td><td>2</td><td>5200(60℃)</td><td>快速固化，优异的柔性，用于纸 张、木器涂料，柔印、胶印、丝印 油墨</td></tr><tr><td>6572</td><td>芳香族PUA</td><td>2</td><td>10000(23℃)</td><td>高柔韧性和弹性，用于纸张、塑 料、金属涂料，柔印、丝印油墨，胶 黏剂</td></tr><tr><td>拜耳</td><td>UAVPLS 2298/1</td><td>芳香族PUA</td><td>2</td><td></td><td>耐磨性优异，适合于各种应用， 尤为地板漆</td></tr><tr><td>盖斯塔夫</td><td>303</td><td>芳香族PUA(含15%TPG- DA)</td><td>2</td><td>5000～ 10000(23℃)</td><td>高反应活性，高柔韧性，适用于 抗划伤木器漆</td></tr><tr><td>巴斯夫</td><td>UA9031V</td><td>芳香族PUA</td><td>2.1</td><td>43000(65C)</td><td>高反应活性，坚韧，良好的耐磨 性能</td></tr><tr><td>石梅</td><td>M1772</td><td>芳香族PUA</td><td>2</td><td>30000～50000</td><td>硬度高，韧性佳，用于纸张、木 器、金属涂料，油墨</td></tr><tr><td rowspan=\"3\">长兴</td><td>6120F-80</td><td>芳香族聚酯PUA(含20% TPGDA)</td><td>2</td><td>30000</td><td>柔韧性、耐刮性和附着力佳、耐 化学药品性好，用于纸张、木器清 漆，胶印、丝印油墨</td></tr><tr><td>6146-100</td><td>六官能度芳香族PUA</td><td>6</td><td>25000</td><td>固化速率快，耐磨性、柔韧性、 耐溶剂性佳，用于纸张、塑料涂</td></tr><tr><td>UR-23</td><td>芳香族PUA（含25%HD- DA)</td><td>2</td><td>25000~40000</td><td>料，油墨 固化速率快，兼具硬度与耐磨 性，适用于纸张、木器、塑料涂料，</td></tr><tr><td rowspan=\"2\">德谦</td><td>UR-33</td><td>芳香族PUA（含25%稀释</td><td>2.5</td><td></td><td>丝印油墨 交联密度高，耐溶剂性好，用于</td></tr><tr><td>SM 6201</td><td>单体) 芳香族聚醚PUA(含20%</td><td>2</td><td>8000～12000</td><td>各种涂料和油墨 柔韧性和附着力佳，用于各种</td></tr><tr><td rowspan=\"2\">江苏三木</td><td>SM6318</td><td>TPGDA) 三官能度芳香族聚醚PUA</td><td>3</td><td></td><td>涂料和油墨 好反应活性高，度高，耐刮性</td></tr><tr><td></td><td></td><td></td><td>30000～60000 3500～</td><td>高光泽，固化速率快，优良的柔</td></tr><tr><td>陕西喜莱坞</td><td>UA315 UV2000</td><td>芳香族聚酯PUA</td><td>2</td><td>4500(50℃)</td><td>韧性，用于各种涂料、油墨和胶黏剂</td></tr><tr><td rowspan=\"4\">中山千叶合成</td><td>UV2100</td><td>芳香族聚酯PUA</td><td>2</td><td>50000±5000</td><td>色相低，刺激性小，耐磨，柔韧</td></tr><tr><td>UV 2300</td><td>芳香族聚醚PUA</td><td>2</td><td>15000±3000</td><td>性和附着力好，耐化学品性和耐 冲击性优，用于木器、塑料耐磨涂</td></tr><tr><td></td><td>三官能度芳香族PUA</td><td>3</td><td>35000±5000</td><td></td></tr><tr><td>UV2600</td><td>六官能度芳香族PUA</td><td>6</td><td>100000</td><td>料，印刷油墨、胶黏剂</td></tr></table></body></html>  \n\n表3-16脂肪族聚氨酯丙烯酸酯低聚物的性能和应用  \n\n\n<html><body><table><tr><td>公司</td><td>产品代号</td><td>化学名称</td><td>官能度</td><td>黏度(25 ℃)</td><td>特点和应用</td></tr><tr><td rowspan=\"4\">沙多 玛</td><td>CN965</td><td>脂肪族PUA</td><td>2</td><td>9975(60℃)</td><td>柔韧性好，耐黄变，用于金属涂料、 丝印油墨、胶黏剂</td></tr><tr><td>CN968</td><td>低黏度脂肪族PUA</td><td>2</td><td>350(60C)</td><td>低黏度，耐黄变，固化速率快，用于 地板、塑料、木器涂料，油墨</td></tr><tr><td>CN 981</td><td>脂肪族PUA</td><td>2</td><td>6190(60℃)</td><td>用高柔韧性，耐黄变,颜料润湿性好，</td></tr><tr><td>CN929</td><td>三官能度脂肪族PUA</td><td>3</td><td>15600</td><td>低黏度，耐黄变，固化速率快，用于 各种涂料，移印、胶印油墨</td></tr><tr><td rowspan=\"4\">氰特</td><td>EB 245</td><td>脂肪族PUA（含25%TPG- DA)</td><td>2</td><td>2500(60℃)</td><td>良好的柔韧性，耐黄变，低刺激性， 用于塑料等各种涂料，胶黏剂</td></tr><tr><td>EB4858</td><td>低黏度脂肪族PUA</td><td>2</td><td>7000</td><td>低黏度，快速固化，良好的耐候性和 耐化学药品性，用于各种涂料，丝印</td></tr><tr><td>EB 264</td><td>三官能度脂肪族PUA（含 15%HDDA)</td><td>3</td><td>4500</td><td>油墨 良好的反应活性，耐候性，抗磨损 性，用于地板、PVC涂料，丝印油墨</td></tr><tr><td>EB 5129</td><td>六官能度脂肪族PUA</td><td>6</td><td>700(60℃)</td><td>良好的抗划伤性，抗磨损性和柔韧 性，用于各种涂料、油墨、胶黏剂</td></tr><tr><td rowspan=\"4\">科宁</td><td>6008</td><td>三官能度脂肪族PUA</td><td>3</td><td>15000(60℃)</td><td>高反应活性，低气味，低刺激，耐黄 变，耐候性，抗磨损性，用于金属、塑料</td></tr><tr><td>6010</td><td>脂肪族PUA</td><td>2</td><td>5900(60C)</td><td>涂料，丝印油墨、胶黏剂 不黄变，耐候性、耐磨性、柔韧性好， 用于塑料涂料，上光油，柔印、丝印</td></tr><tr><td>6891</td><td>低黏度脂肪族PUA</td><td>2</td><td>8500</td><td>油墨 低黏度，耐黄变，优良的表面硬度和 耐老化性，用于木器和塑料涂料</td></tr><tr><td>6019</td><td>三官能度脂肪族PUA</td><td>3</td><td>3300(60℃)</td><td>优良的柔韧性和耐候性，用于木器、 塑料、金属涂料，上光油，柔印、丝印</td></tr><tr><td rowspan=\"2\">盖斯 塔夫</td><td>306</td><td>六官能度脂肪族PUA</td><td>6</td><td></td><td>油墨 高反应活性，高光泽，优异的耐化学</td></tr><tr><td>305</td><td>释脂肪族 PUA(含 24% 903 稀</td><td>2</td><td></td><td>品性，用于各种涂料 于通用型PUA,极好的耐黄变性,用</td></tr><tr><td rowspan=\"5\">拜耳</td><td>UAVPLS 2258</td><td>脂肪族PUA</td><td>2</td><td>7300(23℃)</td><td>低黏度，耐磨性优异，适合各种应 用，尤其地板涂料</td></tr><tr><td>UAVPLS 2265</td><td>脂肪族PUA</td><td>2</td><td>800(23℃)</td><td>低黏度，硬度好，高耐磨，用于木器、 塑料涂料，层压胶黏剂</td></tr><tr><td>UA VP LS</td><td>脂肪族PUA</td><td>2</td><td>60000(23C)</td><td>无磨性、柔韧性好，适合各种应用，</td></tr><tr><td>UAVP LS</td><td>双重固化脂肪族PUA（含</td><td></td><td>12500(23℃)</td><td>硬度高，增进附着力，双重固化，适</td></tr><tr><td>2337 UAVPLS</td><td>12.5%—NCO基) 双重固化脂肪族PUA（含</td><td></td><td>12500(23C)</td><td>合各种应用 柔韧性好，增进附着力，双重固化， 适合各种应用</td></tr><tr><td rowspan=\"3\">巴斯夫</td><td>2396 UA9030V</td><td>7.5%—NCO基) 脂肪族PUA（含30% LR8887)</td><td>1.7</td><td>8000~15000</td><td>高弹性，低黄变性，低温下有良好的 柔韧性和附着力，用于各种涂料</td></tr><tr><td>LR8987</td><td>脂肪族PUA(含30%HDDA)</td><td>2.8</td><td>2000～6000</td><td>低黏度，良好的室外耐候性、耐老化 性、硬度和反应活性，用于各种涂料</td></tr><tr><td>UA19T</td><td>脂肪族PUA</td><td>2</td><td>20000~35000</td><td>低黄变性、柔韧性和黏附性佳，用于 各种涂料</td></tr></table></body></html>  \n\n<html><body><table><tr><td>公司</td><td>产品代号</td><td>化学名称</td><td>盲能度</td><td>黏度（25℃) /mPa·s</td><td>特点和应用</td></tr><tr><td>石梅</td><td>M1800</td><td>脂肪族PUA(含10%EHA)</td><td>2</td><td>12000~15000</td><td>柔韧性和可挠性佳，用于塑料、 PVC、金属涂料</td></tr><tr><td rowspan=\"4\">长兴</td><td>611B-85</td><td>脂肪族PUA(含15%HDDA)</td><td>2</td><td>22000~32000</td><td>耐黄变，硬度、光泽与柔韧性佳，用 于清漆，木器、PVC涂料</td></tr><tr><td>615-100</td><td>聚醚脂肪族PUA</td><td>2</td><td>13000</td><td>光固化快，柔韧性佳，低色泽，用于</td></tr><tr><td>6130B-80</td><td>三官能度脂肪族PUA</td><td>3</td><td>40000~60000</td><td>亚光清漆、涂料、油墨、胶黏剂 木器味低，交联密度，硬度佳，用于</td></tr><tr><td>6145-100</td><td>六官能度脂肪族PUA</td><td>6</td><td>55000~75000</td><td>固化速率快，高硬度，高光泽，促进 附着力，用于纸张、木器涂料，硬涂料，</td></tr><tr><td rowspan=\"3\">德谦</td><td></td><td></td><td>2</td><td></td><td>阻焊剂 耐黄变，兼具硬度和柔韧性佳，用于</td></tr><tr><td>UR-21 UR-22</td><td>脂肪族PUA(含15%HDDA) 脂肪族PUA（含20%EHA)</td><td>2</td><td></td><td>PVC、木器涂料，油墨 低黏度，耐黄变，延展性佳，改善树</td></tr><tr><td>UR-25</td><td>脂肪族PUA（含25%TPG-</td><td>2</td><td></td><td>脂韧性，用于木器、PVC涂料，油墨 耐黄变，兼具硬度和柔韧性佳，用于</td></tr><tr><td>陕西喜 莱坞</td><td>UA320</td><td>DA) 脂肪族聚酯PUA</td><td>2</td><td></td><td>木器、塑料涂料，油墨 耐黄变，优异的柔韧性、耐磨性和耐 3500～4800（50℃）化学性，用于柔性塑料和弹性涂料，丝 印油墨，胶黏剂</td></tr><tr><td rowspan=\"3\">中山 千成</td><td></td><td></td><td></td><td></td><td rowspan=\"3\">良好的柔韧性，优异的耐候性，耐磨</td></tr><tr><td>UV 3000</td><td>脂肪族 PUA</td><td>22</td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td rowspan=\"9\">中山 杰事达</td><td>UV 300</td><td>三能度脂肪族PUA</td><td>36</td><td></td><td>性、耐溶剂性好,用于各种耐磨涂料,</td></tr><tr><td>UA1006</td><td>五官能度低分子量脂肪族 PUA(含20%醋酸丁酯/甲苯）</td><td>5</td><td>35000±3000</td><td>高硬度，耐化学品性好，对塑料有很 好密着性，用于塑料涂料</td></tr><tr><td>UA1106</td><td>五官能度中分子量脂肪族 PUA(含30%醋酸丁酯/甲苯)</td><td>5</td><td>45000±3000</td><td>高韧性和密着性，用于塑料涂料</td></tr><tr><td>UA1101</td><td>五官能度中分子量脂肪族 PUA(含25%醋酸丁酯/甲苯)</td><td>5</td><td>45000±3000</td><td>高韧性和密着性，用于塑料涂料</td></tr><tr><td>UA8702M</td><td>五官能度中分子量脂肪族 PUA(含30%醋酸丁酯/甲苯）</td><td>5</td><td>≥100000</td><td>高韧性和消光性，用于塑料涂料</td></tr><tr><td>UA1009</td><td>P三官能度高分子量脂肪族</td><td>3</td><td></td><td>涂低收缩,高韧性和密着性,用于塑料</td></tr><tr><td>UA 1109</td><td>三官能度高分子量脂肪族 PUA(含甲苯/醋酸丁酯/异丁酯)</td><td>3</td><td></td><td>低收缩，高韧性和密着性，用于塑料 涂料 高光泽，透明性好，高硬度，用于塑</td></tr><tr><td>UA2000</td><td>六官能度中分子量脂肪族 PUA（含20%醋酸丁酯/甲苯）</td><td>6</td><td></td><td>料涂料</td></tr><tr><td>UA2001</td><td>六官能度中分子量脂肪族 PUA(含20%醋酸丁酯/甲苯)</td><td>6</td><td></td><td>高光泽，高韧性，透明性好，高硬度， 用于塑料涂料</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 76,
+        "chunk": "# 3.5 聚酯丙烯酸酯",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 77,
+        "chunk": "# 3.5.1聚酯丙烯酸酯的合成  \n\n聚酯丙烯酸酯（polyester acrylate，PEA）也是一种常见的低聚物，它是由低分子量聚酯二醇经丙烯酸酯化而制得，合成方法可有下列几种。  \n\n（1）二元酸、二元醇、丙烯酸一步酯化。2H00C- $\\cdot\\mathbf{R}^{\\prime}$ —COOH $^+$ 2HO—R—OH+2CH2—CH—COOH- 催化剂$\\mathrm{H}_{2}\\mathrm{C}\\mathrm{-CH}\\mathrm{-COO}\\mathrm{-R}\\mathrm{-OOC}\\mathrm{-R}^{\\prime}\\mathrm{-COO}\\mathrm{-ROOC}\\mathrm{-OH}\\mathrm{-CH}_{2}$ （2）先将二元酸与二元醇反应得到聚酯二醇，再与丙烯酸酯化。  \n\n催化剂2HOOC—R'—COOH+2HO—R—OH- HO-R—OOC- $\\cdot\\mathbf{R^{\\prime}}$ --COOR-OH催化剂HO-R-OOC- $\\cdot{\\bf{R}}^{\\prime}$ —COO-R--OH+2HC-CH—COOH-$\\mathrm{H_{2}C-C H-C O O-R-O O C-R^{\\prime}-C O O-R O O C-C H-C H_{2}}$ （3）二元酸与环氧乙烷加成后，再与丙烯酸酯化。  \n\n2HOOC-R-COOH $+2n$ CH—CH→H(OCHCH）OCO—R—COO-(CHCH）OH 0  \n\n$\\mathrm{H-\\ell\\mathrm{OCH_{2}C H_{2}}\\supset\\overline{{\\mathfrak{n}}}\\mathrm{OCO-\\ell\\mathrm{R-COO-\\ell\\mathrm{CH_{2}C H_{2}}\\supset\\overline{{\\mathfrak{n}}}O H\\ +2H_{2}C-C H\\mathrm{-COOH\\\\mathrm{-}\\overline{{\\mathfrak{n}}}\\mathrm{\\overline{{\\mathrm{t}}}\\mathrm{\\overline{{\\mathfrak{n}}}\\mathrm{\\overline{{\\mathfrak{n}}}}}}}}}}}$ $\\mathrm{H_{2}C-C H-C O O-(O C H_{2}C H_{2})_{\\overline{{\\pi}}}O C O-R-C O O-(C H_{2}C H_{2})_{n}-O C O-C H-C H_{2}}$ (4)丙烯酸羟基酯与酸酐反应，制得酸酐半加成物，再与聚酯二醇酯化。  \n\n![](images/185ca84cbbf09b15f10d1255fb4e5ff33f8a708503e0721e9a8711232b796cc4.jpg)  \n\n(5)聚酯二元酸与（甲基)丙烯酸缩水甘油酯反应。  \n\n![](images/94406118812562a930c6bb45f0f5167e2efbcbef940ed551f90838a58d7c78af.jpg)  \n\n(6)用少量三元醇或三元羧酸代替部分二元醇或二元酸，制得支化的多官能度聚酯。  \n\n![](images/e6bd8760eed53f2fbd56c2dc1e70ac674b39377a9ab0e6aa9fdbc1302cfd1083.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 78,
+        "chunk": "# 3.5.2聚酯丙烯酸酯的性能和应用  \n\n聚酯丙烯酸酯价格低和黏度低是最大的特点，由于黏度低，聚酯丙烯酸酯既可作为低聚物，也可作为活性稀释剂使用。此外，聚酯丙烯酸酯大多具有低气味，低刺激性，较好的柔韧性和颜料润湿性，适用于色漆和油墨。为了提高光固化速率，可以制备多官能度的聚酯丙烯酸酯;采用胺改性的聚酯丙烯酸酯，不仅可以减少氧阻聚的影响，提高固化速率，还可以改善附着力、光泽和耐磨性，见表3-17。  \n\n氯化聚酯丙烯酸酯是由聚酯丙烯酸酯经氯化反应制得的，这是一种对金属和塑料基材具有优异附着力的低聚物，并有良好的耐磨性、柔韧性和耐化学性，应用于金属和塑料色漆及油墨中，见表3-18。  \n\n表3-17聚酯丙烯酸酯低聚物的性能和应用  \n\n\n<html><body><table><tr><td>公司</td><td>产品代号</td><td>化学名称</td><td>官能度</td><td>黏度（25℃） /mPa·s</td><td>特点和应用</td></tr><tr><td rowspan=\"4\">沙多玛</td><td>CN2200</td><td>PEA</td><td>2</td><td>52000</td><td>快速固化，流平性和流动性好，可增加颜料用量， 专用于柔印、凹印、胶印、丝印油墨</td></tr><tr><td>CN2251</td><td>三官能度PEA</td><td>3</td><td>1300(60℃)</td><td>高固化速率，高光泽，耐磨性好，耐化学品性好，用 于纸张、木器、塑料、PVC涂料，层压胶黏剂</td></tr><tr><td>CNUVP 220</td><td>四官能度PEA</td><td>4</td><td>10000</td><td>快速固化，高硬度并保持柔韧性，对木器、塑料附着 力好，用于木器、塑料涂料，丝印、柔印、凹印油墨</td></tr><tr><td>CN293</td><td>六官能度PEA</td><td>6</td><td>7700</td><td>快速固化，优良的颜料润湿性，耐磨性好，用于耐</td></tr><tr><td rowspan=\"5\">氰特</td><td>EB84</td><td>PEA</td><td>2</td><td>5000</td><td>磨涂料，胶印、柔印、凹印油墨 高反应活性，塑料附着力好，用于各种罩光清漆</td></tr><tr><td>EB81</td><td>低黏度PEA</td><td>2.5</td><td>100</td><td>极低黏度，高反应活性，用于各种罩光清漆</td></tr><tr><td>EB810</td><td>四官能度PEA</td><td>4</td><td>500</td><td>低黏度，低刺激性，用于各种罩光清漆，有色涂料</td></tr><tr><td>EB657</td><td>四官能度PEA</td><td>4</td><td>3500(60℃)</td><td>低气味，低刺激性，突出的颜料润湿性和胶印印刷</td></tr><tr><td>EB830</td><td>六官能度PEA</td><td>6</td><td>50000</td><td>性，用于胶印油墨，胶黏剂 快速固化，高硬度，耐磨损性好，用于耐磨涂料</td></tr><tr><td rowspan=\"3\">科宁</td><td>5429</td><td>四官能度PEA</td><td>4</td><td>300</td><td>极低黏度，低刺激性，高反应活性，柔韧性好，用于 木器、塑料、金属涂料，柔印油墨</td></tr><tr><td>5430</td><td>四官能度PEA</td><td>4</td><td>3000</td><td>高反应活性，柔韧性、附着力和颜料润湿性好，用</td></tr><tr><td>5010</td><td>PEA</td><td>2</td><td>3000</td><td>于木器、塑料、金属涂料，胶印、柔印、丝印油墨 低光泽，柔韧性好，用于木器、工业涂料，丝印油墨</td></tr><tr><td>拜耳</td><td>UAVP LS2380</td><td>PEA（含30% TPGDA)</td><td>2</td><td>29000</td><td>反应活性高，耐划伤性和附着力好，用于家具、地 板涂料，层压胶黏剂</td></tr><tr><td rowspan=\"4\">巴斯夫</td><td>PE56F (LR8793)</td><td>PEA</td><td>2.5</td><td>20000~40000 (23C)</td><td>高反应活性，柔韧性和弹性好</td></tr><tr><td>PE44F (LR8799)</td><td>PEA</td><td>3.5</td><td>2000～5000 (23C)</td><td>低气味，柔韧性好 TO</td></tr><tr><td>LR8800</td><td>PEA</td><td>3.5</td><td>4000~8000 (23℃)</td><td>高硬度，低气味，耐化学品性优异</td></tr><tr><td>LR8992</td><td>四官能度改性PEA</td><td>4</td><td>4000~8000</td><td>优良的耐化学品性和耐磨性，用于地板涂料</td></tr><tr><td rowspan=\"3\">盖斯塔夫</td><td>201</td><td>（含15%TPGDA） 芳香族PEA</td><td>3</td><td>(23℃)</td><td>高活性，高黏度，高硬度，易打磨，适用于木器涂料</td></tr><tr><td>203</td><td>芳香族PEA</td><td>4</td><td></td><td>高活性，极好的颜料润湿性，适用于色漆和油墨</td></tr><tr><td>206</td><td>芳香族、脂肪族混 合PEA</td><td>2</td><td></td><td>高活性，低黏度，适用于木器清漆和色漆</td></tr></table></body></html>  \n\n<html><body><table><tr><td>公司</td><td>产品代号</td><td>化学名称</td><td>官能度</td><td>黏度（25℃） /mPa·s</td><td>特点和应用</td></tr><tr><td>石梅</td><td>M2100</td><td>PEA</td><td>2</td><td>1500(60℃)</td><td>固化速率快，附着力佳，用于木器、金属、塑料涂 料，油墨</td></tr><tr><td rowspan=\"3\">长兴</td><td>6331</td><td>PEA</td><td>2</td><td>18000</td><td>高光泽和表面硬度，耐溶剂性佳，用于纸张、木材、 金属、塑料涂料，油墨</td></tr><tr><td>6331-100</td><td>四官能度PEA</td><td>4</td><td>3000~4000（60C）</td><td>低气味和刺激性，颜料润湿性佳，利于胶印，用于 纸张、木材、金属、塑料涂料，胶印、丝印油墨</td></tr><tr><td>6312-100</td><td>六官能度PEA</td><td>6</td><td>40000~60000</td><td>快速固化，颜料润湿性、耐刮性、耐溶剂性佳，利于 胶印，用于胶印油墨，清漆</td></tr><tr><td>陕西喜 莱坞</td><td>PEA 400</td><td>PEA</td><td>2</td><td>400~700</td><td>极低黏度，柔韧性好，用于上光油、涂料、油墨、胶 黏剂</td></tr><tr><td rowspan=\"3\">中山千 叶合成</td><td>UV 701</td><td>PEA</td><td>2</td><td>23000±3000</td><td rowspan=\"2\">快速固化，低气味和刺激性，良好的硬度，用于罩 器涂料 光清漆，涂装PU革，软硬PVC、皮革、金属装饰、木</td></tr><tr><td>UV702</td><td>三官能度PEA</td><td>3</td><td>16000±3000</td></tr><tr><td>UV703</td><td>脂肪族改性PEA</td><td>2</td><td>16000±3000</td><td>器涂料，胶印和丝印油墨 快速固化，低刺激性，良好的流平性和对颜料润湿 性，用于涂装PU革，软硬PVC、皮革、金属装饰、木</td></tr></table></body></html>  \n\n表3-18氯化聚丙烯酸酯低聚物的性能和应用  \n\n\n<html><body><table><tr><td>公司</td><td>产品代号</td><td>化学名称</td><td>黏度(25℃)</td><td>密</td><td>特点和应用</td></tr><tr><td rowspan=\"5\">氰特</td><td>EB408</td><td>氯化PEA（含27%甘 油衍生物三丙烯酸酯)</td><td>1750(60℃)</td><td>1.31</td><td>固化速率快，良好的胶印性能，对金属、塑 料、纸张的附着力强，用于上光清漆，胶印、丝</td></tr><tr><td>EB436</td><td>氯化PEA（含40% TMPTA)</td><td>1500(60℃)</td><td>1.28</td><td>印油墨 高反应活性，对金属、塑料附着力强，用于 金属、塑料涂料，上光清漆，胶印、丝印油墨</td></tr><tr><td>EB584</td><td>氯化PEA（含40% HDDA)</td><td>2000</td><td>1.32</td><td>固化速率快，对塑料附着力强，用于金属、 塑料涂料，上光清漆，玻璃粘接</td></tr><tr><td>EB585</td><td>氯化PEA（含40% TPGDA)</td><td>4700</td><td>1.3</td><td>固化速率快，对塑料附着力强，用于塑料涂 料，玻璃粘接</td></tr><tr><td>EB3438</td><td>高纯度氯化PEA</td><td>1350(60℃)</td><td>1.26</td><td>固化速率快，对金属、塑料附着力强，用于 金属、塑料涂料，胶印、丝印油墨</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 79,
+        "chunk": "# 3.6 聚醚丙烯酸酯",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 80,
+        "chunk": "# 3.6.1聚醚丙烯酸酯的合成  \n\n聚醚丙烯酸酯（polyether acrylate）是又一种低聚物，主要指聚乙二醇和聚丙二醇结构的丙烯酸酯。这些聚醚是由环氧乙烷或环氧丙烷与二元醇或多元醇在强碱中经阴离子开环聚合，得到端羟基聚醚，再经丙烯酸酯化得到聚醚丙烯酸酯。由于酯化反应要在酸性条件下进行，而醚键对酸敏感会被破坏，所以都用酯交换法来制备聚醚丙烯酸酯。一般将端羟基聚醚与过量的丙烯酸乙酯及阻聚剂混合加热，在催化剂（如钛酸三异丙酯）作用下发生酯交换反应，产生的乙醇和丙烯酸乙酯形成共沸物而蒸馏出来，经分馏塔，丙烯酸乙酯馏分重新回到反应釜，而乙醇分馏出来，使酯交换反应进行彻底，再把过量的丙烯酸乙酯真空蒸馏除去。  \n\n![](images/15c10c16b62ce5ed591f3ab1cbb2e6e3e0608ceb62e5eb67f30259684312dce7.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 81,
+        "chunk": "# 3.6.2聚醚丙烯酸酯的性能和应用  \n\n聚醚丙烯酸酯的柔韧性和耐黄变性好，但机械强度、硬度和耐化学品性差，因此，在光固化涂料、油墨中不作为主体树脂使用，但其黏度低，稀释性好，所以用作活性稀释剂。国外公司还采用胺改性等方法，使聚醚丙烯酸酯不仅具有极低黏度，而且有极高的反应活性，有的还具有较好的颜料润湿性，可用于色漆和油墨，见表3-19。  \n\n表3-19聚醚丙烯酸酯低聚物的性能和应用  \n\n\n<html><body><table><tr><td>公司</td><td>产品代号</td><td>化学名称</td><td>官能度</td><td>黏度（25℃）/mPa·s</td><td>特点和应用</td></tr><tr><td rowspan=\"2\">沙多玛</td><td>CN 501</td><td>胺改性聚醚丙烯 酸酯</td><td></td><td>64</td><td>极低黏度，快速固化，用于纸张、木材 涂料</td></tr><tr><td>CN551</td><td>胺改性聚醚丙烯酸酯</td><td></td><td>525</td><td>快速固化，用于纸张、木材涂料</td></tr><tr><td rowspan=\"4\">科宁</td><td>5025F</td><td>改性聚醚丙烯酸酯</td><td>2</td><td>120</td><td>低黏度，用于木器喷涂涂料</td></tr><tr><td>5026F</td><td>四官能度聚醚丙烯 酸酯</td><td>4</td><td>600</td><td>高反应性，耐黄变，用于纸张、木器 涂料</td></tr><tr><td>5662F</td><td>四官能度改性聚醚 丙烯酸酯</td><td>4</td><td>3000</td><td>高反应性，用于木器、塑料、金属涂料， 柔性油墨</td></tr><tr><td>5850F</td><td>改性聚醚丙烯酸酯</td><td>2</td><td>100</td><td>极低黏度，高反应性，用于纸张、木器 涂料</td></tr><tr><td rowspan=\"8\">巴斯夫</td><td>PO43F(LR8945)</td><td>改性聚醚丙烯酸酯</td><td>2.9</td><td>200~400(23C)</td><td>低黏度，硬度高，耐化学品性，用于纸</td></tr><tr><td>LR8967</td><td>三官能度改性聚醚</td><td>3</td><td>120~190(23℃)</td><td>张、木器涂料 低黏度，硬度高，耐化学品性，用于纸</td></tr><tr><td>PO94F(LR8894)</td><td>丙烯酸酯 胺改性聚醚丙烯</td><td>3.5</td><td>400~800(23C)</td><td>张、木器涂料 高反应性，耐黄变和耐化学品性，用于</td></tr><tr><td>PO77F(LR8946)</td><td>酸酯 胺改性聚醚丙烯</td><td>3.2</td><td>1000~3000(23℃)</td><td>涂料 高反应性，打磨性好，耐化学品性，用 于木器涂料</td></tr><tr><td>LR8985</td><td>酸酯 改性聚醚丙烯酸酯</td><td>1.5</td><td>55000~85000(23℃)</td><td>优良的颜料润湿性，低体积收缩率和 低气味，用于塑料、金属涂料，油墨</td></tr><tr><td>PO33F</td><td>聚醚丙烯酸酯</td><td>3</td><td>70~130(23℃)</td><td>低黏度，耐黄变，抗划伤，用于涂料</td></tr><tr><td>LR8863</td><td>聚醚丙烯酸酯</td><td>3</td><td>70～110(23℃)</td><td>更低黏度，用于涂料</td></tr><tr><td>PO9026F</td><td>聚醚丙烯酸酯</td><td>3</td><td>500~3000(23C)</td><td>黏度较低，优异的耐划伤性能，用于 涂料</td></tr><tr><td>PE9027V</td><td>聚醚丙烯酸酯</td><td>3.5</td><td>7000~85000(23℃)</td><td>中等黏度，优异的耐划伤性能，用于 涂料</td></tr><tr><td>拜耳</td><td>UAVPLS2299</td><td>胺改性聚醚丙烯 酸酯</td><td></td><td>800(23C)</td><td>高反应性，硬度好，低黏度，用于纸张、 木器涂料</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 82,
+        "chunk": "# 3.7.1 纯丙烯酸树脂的合成  \n\n光固化涂料用的纯丙烯酸树脂低聚物是指丙烯酸酯化的聚丙烯酸酯或乙烯基树脂，它是通过带有官能基的聚丙烯酸酯共聚物与丙烯酸缩水甘油酯、丙烯酸羟基酯或丙烯酸反应，在侧链接上丙烯酰氧基而制得。  \n\n如丙烯酸、丙烯酸甲酯、丙烯酸丁酯和苯乙烯共聚物与丙烯酸缩水甘油酯反应，共聚物中丙烯酸的羧基和丙烯酸缩水甘油酯中环氧基开环加成酯化，把丙烯酰氧基引入成为光固化树脂。  \n\n![](images/5eccfb63491143b0f725ab4cadd402524f2743b39519bb6938272ab9b120ed4c.jpg)  \n\n再如苯乙烯和马来酸酐共聚物与丙烯酸羟乙酯反应，丙烯酸羟乙酯中的羟基与马来酸酐作用，引人丙烯酰氧基，成为光固化树脂。  \n\n![](images/967bbf4a59d645b6145d3ee9c0c0eec54427b2d908be6e9ae8fd4032672b0b09.jpg)  \n\n上述共聚物要求低分子量，去除溶剂时有一定流动性。若分子量太大，黏度很高，丙烯酸酯化后处理麻烦，溶剂不易除去。 5A",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 83,
+        "chunk": "# 3.7.2纯丙烯酸树脂的性能和应用  \n\n纯丙烯酸酯低聚物具有极好的耐黄变性，良好的柔韧性和耐溶剂性，对各种不同基材都有较好的附着力，但机械强度和硬度都很低，耐酸碱性差。因此，在实际应用中纯丙烯酸树脂不作主体树脂使用，只是为了改善光固化涂料、油墨某些性能，为提高耐黄变性，增进对基材的附着力和涂层间附着力而配合使用，见表3-20。  \n\n表3-20纯丙烯酸树脂低聚物的性能和应用  \n\n\n<html><body><table><tr><td>公司</td><td>产品代号</td><td>化学名称</td><td>黏度（25℃）/mPa·s</td><td>特点和应用</td></tr><tr><td rowspan=\"3\">氰特</td><td>EB705</td><td>丙烯酸树脂（含47%TPGDA)</td><td>18000</td><td>可增强较难黏附基材上的附着力，有良 好的柔韧性和涂层间附着力</td></tr><tr><td>EB745</td><td>丙烯酸树脂（含25%TPGDA和 25%HDDA)</td><td>20000</td><td>对聚酯类塑料有极好的附着力，反应活 性较低，用于罩光清漆，丝印油墨</td></tr><tr><td>EB1401</td><td>丙烯酸树脂（含25%TPGDA)</td><td>10000(60℃)</td><td>对纸张、塑料有良好的附着力，非常适用 于复合胶黏剂</td></tr><tr><td rowspan=\"3\">长兴</td><td>6530B-40</td><td>丙烯酸树脂（60%HDDA)</td><td>13000~16500</td><td>快速固化，硬度和耐候性佳，对不同基材 增强附着力，用于纸张、木材、塑料、金属涂 料，油墨</td></tr><tr><td>6531B-40</td><td>丙烯酸树脂(60%HDDA)</td><td>90000</td><td>增强不同基材附着力，柔韧性佳，用于纸 张、木材、塑料、金属涂料，油墨，胶黏剂</td></tr><tr><td>6532B-40</td><td>丙烯酸树脂(60%HDDA)</td><td>18000</td><td>高光泽和表面硬度，耐溶剂性好，用于纸 张、木材、塑料、金属涂料，油墨</td></tr><tr><td rowspan=\"3\">中山千 叶合成</td><td>UB101</td><td>丙烯酸树脂(50%活性稀释剂)</td><td>30000±3000</td><td>良好的柔韧性、涂层间附着力，可增强较</td></tr><tr><td>UB104</td><td>丙烯酸树脂（50%活性稀释剂）</td><td>30000±3000</td><td>难黏附基材上的附着力，极好的耐候性，用</td></tr><tr><td>UB105</td><td>丙烯酸树脂(50%活性稀释剂）</td><td>40000±5000</td><td>于复合膜印刷、上光油墨及金属、塑料喷漆</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 84,
+        "chunk": "# 3.8.1有机硅低聚物的合成  \n\n光固化有机硅低聚物是以聚硅氧烷中重复的Si一O键为主链结构的聚合物，并具有可进行聚合、交联的反应基团，如丙烯酰氧基、乙烯基或环氧基等。从目前光固化应用上来看，主要为带丙烯酰氧基的有机硅丙烯酸酯低聚物。  \n\n在聚硅氧烷中引入丙烯酰氧基主要有下列几种方法。  \n\n（1）用二氯二甲基硅烷单体和丙烯酸羟乙酯在碱催化下水解缩合，HEA作为端基引人到聚硅氧烷链上。  \n\n0 CH3 0 CH3 02HC=CHCOCHCHOH + nCI--Si—CI 缩合 HC--CHCOCHCHO-—Si—O),CHCHO—C—CH—CHzCH3 CH3  \n\n（2）由二乙氧基硅烷和丙烯酸羟乙酯经酯交换反应引人丙烯酰氧基。  \n\n0 0 RO-(Si—O)R +2HC—CHCOOCHCHOH- 酯交换 HC—CHCOCHCHO(Si—O)CHCHO—C—CH—CH  \n\n（3）利用端羟基硅烷与丙烯酸酯化，引入丙烯酰氧基。  \n\nHO—RSi—O)Si—R—OH+2HCCHCOOH  \n\n![](images/23f12b03e06607f5eaacb7ca1fbd05f75980d78216b7f86f3b0a3ff19f870a91.jpg)  \n\n（4）用端羟基硅烷与二异氰酸酯反应，再与丙烯酸羟乙酯反应，或用端羟基硅烷与二异  \n\n氰酸酯-丙烯酸羟乙酯半加成物反应，引入丙烯酰氧基。  \n\n![](images/f2ad86b5e7f00ceaba6619b1a2f97cc6ef4217ebfcf460ba6059e8b78cf7a6b5.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 85,
+        "chunk": "# 3.8.2有机硅低聚物的性能和应用  \n\n有机硅丙烯酸酯是一种有特殊性能的低聚物，它具有较低的表面张力，因此作压敏胶的防粘纸中的离型剂，涂覆在纸或塑料薄膜上；固化后形成黏附力很低的表面，与压敏胶材料复合，制成不干胶、尿不湿和卫生巾的辅助材料。有机硅低聚物主链为硅氧键，有极好的柔韧性、耐低温性、耐湿性、耐候性、电性能，常用作保护涂料，如电器和电子线路的涂装保护及密封，特别是用作光纤保护涂料。此外，也能用作玻璃和石英材质光学器件的胶黏剂，见表3-21。表3-22则为聚硅氧烷MDI丙烯酸酯在不同基材上的性能。  \n\n表3-21有机硅丙烯酸酯低聚物的性能和应用  \n\n\n<html><body><table><tr><td>公司</td><td>产品代号</td><td>化学名称</td><td>宜能度</td><td>黏度（25℃)/mPa·s</td><td>特点和应用</td></tr><tr><td>沙多玛</td><td>CN990</td><td>聚硅氧烷化PUA</td><td></td><td>50000</td><td>低气味，柔韧，降低划擦系数；用于纸张、木 器、金属涂料，油墨</td></tr><tr><td rowspan=\"2\">氰特</td><td>EB350</td><td>有机硅丙烯酸酯</td><td>2</td><td>350</td><td>低黏度，提供基材良好的润湿性和爽滑性， 无迁移；用作保护清漆和涂料</td></tr><tr><td>EB1360</td><td>六官能度丙烯酸酯</td><td>6</td><td>2100</td><td>提供基材良好的润湿性和爽滑性，无迁移； 用作保护清漆和涂料</td></tr><tr><td>长兴</td><td>6225</td><td>有机硅聚醚丙烯 酸酯</td><td></td><td>200～900</td><td>低色度，低黏度，光固化速率快，耐磨性佳； 用作保护清漆，纸张、木器、塑料涂料，胶印和 丝印油墨</td></tr></table></body></html>  \n\n表3-22聚硅氧烷MDI丙烯酸酯在不同基材上的性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">性能</td><td colspan=\"5\">基材</td></tr><tr><td>钢</td><td>铝</td><td>玻璃</td><td>木材</td><td>聚苯乙烯</td></tr><tr><td>固化时间/s</td><td>30</td><td>30</td><td>30</td><td>30</td><td>30</td></tr><tr><td>膜厚/μm</td><td>30</td><td>28</td><td>30</td><td>30</td><td>32</td></tr><tr><td>附着力</td><td>好</td><td>好</td><td>好</td><td>好</td><td>好</td></tr><tr><td>铅笔硬度</td><td>3H</td><td>3H</td><td>3H</td><td>3H</td><td>3H</td></tr><tr><td>耐冲击性</td><td>好</td><td>好</td><td></td><td>好</td><td>好</td></tr><tr><td>拉伸强度</td><td>好</td><td>好</td><td></td><td></td><td></td></tr><tr><td>挠性</td><td>好</td><td>好</td><td></td><td></td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td colspan=\"2\">性能</td><td colspan=\"5\">基材</td></tr><tr><td colspan=\"2\"></td><td>钢</td><td>铝</td><td>玻璃</td><td>木材</td><td>聚苯乙烯</td></tr><tr><td rowspan=\"6\">耐化学品性</td><td>5%HCl</td><td>好</td><td>好</td><td>好</td><td>好</td><td>好</td></tr><tr><td>5%NaOH</td><td>好</td><td></td><td>好</td><td>好</td><td>好</td></tr><tr><td>5%NaCl</td><td>好</td><td>好</td><td>好</td><td>好</td><td>好</td></tr><tr><td>3%CHCOOH</td><td>好</td><td>好</td><td>好</td><td>好</td><td>好</td></tr><tr><td>CHOH</td><td>不好</td><td>不好</td><td>不好</td><td>不好</td><td>不好</td></tr><tr><td>耐水性 耐洗涤性</td><td>好 好</td><td>好 好</td><td>好 好</td><td>好 好</td><td>好 好</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 86,
+        "chunk": "# 3.9 环氧树脂  \n\n环氧树脂（epoxyresin）是用作阳离子光固化涂料的低聚物，环氧树脂在超强质子酸或路易斯酸作用下，容易发生阳离子聚合。  \n\n双酚A型环氧树脂在阳离子光固化时，反应活性低，聚合速率慢，黏度较高，因此使用不多。脂肪族环氧树脂，低黏度，低气味，低毒性，反应活性高，固化膜收缩率低，耐候性好，有优异的柔韧性和耐磨性，成为阳离子光固化涂料最主要的低聚物。如3,4-环氧环已基甲酸-3,4-环氧环己基甲酯（UVR6110）和己二酸双（3,4-环氧环已基甲酯）（UVR6128)。  \n\nUVR 6110可以由环己烯-3-甲酸和环己烯-3-甲醇先酯化反应，再用过氧乙酸对碳碳双键环氧化而制得。  \n\n![](images/2c55328e20555e54c68cc2069214f661af0f8c95ec2b58414b0fb119c4fb57b2.jpg)  \n\n3,4-环氧环已基甲酸-3，4-环氧环已基甲酯  \n\nUVR6128则由环已烯-3-甲醇与已二酸酯化，再由过氧乙酸环氧化而制得。  \n\n![](images/ee76c3664489d19fecca8e9f83f27c5a45557955af42d2e679d7207515bcf2ea.jpg)  \n\n在脂环族环氧化合物基础上开发的一些多环化合物，如原甲酸酯也可用作阳离子光固化低聚物，它们在聚合时可以发生体积膨胀。  \n\n阳离子光固化用脂环族环氧树脂具有低气味、低毒性、低黏度和低收缩率，柔韧性、耐磨性和透明度好，对塑料和金属有优异的附着力，主要用于软硬包装材料的涂料，如罐头罩光漆、塑料、纸张涂料，电器/电子用涂料，丝印、胶印油墨，胶黏剂和灌封料等，见表3-23。  \n\n表3-23阳离子光固化用脂环族环氧树脂低聚物的性能和应用  \n\n\n<html><body><table><tr><td>公司</td><td>产品代号</td><td>化学名称</td><td>黏度（25℃) /mPa·s</td><td>环氧当量</td><td>特点和应用</td></tr><tr><td rowspan=\"5\">氰 特</td><td>UVACURE1500</td><td>脂肪族环氧 树脂</td><td>235</td><td>134</td><td>低黏度，残留气味低，对塑料、金属有极性好附 着力；用于金属，塑料涂料，柔印油墨</td></tr><tr><td>UVACURE1533</td><td>改性环氧树脂</td><td>15000(60℃)</td><td>262</td><td>残留气味低，良好的附着力和柔韧性；用于罩光 清漆，胶黏剂</td></tr><tr><td>UVACURE1534</td><td>脂肪族环氧 树脂</td><td>2700</td><td>268</td><td>良好的柔韧性和抗水性；用于罩光清漆，胶黏 剂，胶印油墨</td></tr><tr><td>UVACURE1561</td><td>部分丙烯酸酯 化的双酚A型EA</td><td>1100(60℃)</td><td>431</td><td>具有自由基、阳离子双重固化特点；用于混杂固 化和双重固化体系的涂料、油墨、胶黏剂</td></tr><tr><td>UVACURE1562</td><td>脂肪族EA</td><td>3750</td><td>223</td><td>极低收缩率，良好的附着力，低残留气味；用于 混杂固化体系的涂料、油墨、胶黏剂</td></tr><tr><td rowspan=\"6\">陶 氏 化 学</td><td>UVR6110</td><td>脂环族环氧 树脂</td><td>350~450</td><td>131~143</td><td>低黏度、低气味、低毒性，快速固化，优异的柔韧 性、耐磨性，对塑料、金属附着力好；用于纸张、塑料、 金属涂料、丝印、凸印油墨，电器/电子涂料和灌封料</td></tr><tr><td>UVR6105</td><td>脂环族环氧 树脂</td><td>220~250</td><td>130~135</td><td>低黏度、低气味、低毒性，快速固化，优异的柔韧 性、耐磨性，对塑料、金属附着力好；用于纸张、塑料、 金属涂料，丝印、凸印油墨，电器/电子涂料和灌封料</td></tr><tr><td>UVR6128</td><td>脂环族环氧 树脂</td><td>550~750</td><td>190~210</td><td>低气味，低毒性，快速固化，更优的柔韧性，耐磨 性和对塑料、金属附着力好；用于罩光清漆，软硬 包装材料的印刷油墨，电器/电子涂料和灌封料</td></tr><tr><td>UVR6100</td><td>氧混合脂环族环</td><td>80~115</td><td>130~140</td><td>黏非常低的黏度；用作阳离子UV固化涂料降低</td></tr><tr><td>UVR6216</td><td>线型脂环族环 氧树脂</td><td><15</td><td>240~280</td><td>极低黏度；用作阳离子UV固化涂料降低黏度</td></tr></table></body></html>  \n\n乙烯基醚类化合物是另一大类用于阳离子光固化的低聚物或活性稀释剂，它们具有固化速率快、黏度低、毒性低、相容性好等优点，它们还可以与环氧化合物、丙烯酸酯、聚酯、聚氨酯得到相应的低聚物，与脂环族环氧树脂配合使用。有关乙烯基醚类化合物已在第2章中详细介绍。  \n\n水性UV低聚物是随着20世纪末水性UV固化材料的开发而产生的，它可分为乳液型、水分散型和水溶性三类，见表2-24。  \n\n表3-24水性UV低聚物的分类  \n\n\n<html><body><table><tr><td>类型</td><td>粒径/nm</td><td>外观</td></tr><tr><td>水溶型</td><td><5</td><td>透明</td></tr><tr><td>水分散型</td><td>20~100</td><td>半透明</td></tr><tr><td>乳液型</td><td>>100</td><td>乳液</td></tr></table></body></html>  \n\n（1）乳液型水性UV低聚物早期采用外加乳化剂，低聚物不含亲水基团，靠机械作用，使低聚物分散于水中，得到低聚物的乳液。但是由于乳化剂的加人，影响了固化膜的耐水性和光泽，力学性能也大幅下降。这是由于表面活性剂在界面定向吸附，对紫外光有一定的干扰作用，使转换率下降而造成的。  \n\n现在多采用自乳化型，即在低聚物中引人亲水基团（如羧基、亲水性聚乙二醇)，在水中有自乳化作用，故不用外加乳化剂。固化后，固化膜的耐水性和光泽不受影响。  \n\n（2）水分散型水性UV低聚物这类低聚物中，亲水性基团和疏水性基团要巧妙平衡，在水中分散后，粒径在 ${20}\\mathrm{{\\sim}}100\\mathrm{{nm}}$ ，形成半透明的水分散体。  \n\n（3）水溶型水性UV低聚物这类低聚物中，含有足够量的羧基或季铵基，羧基经与氨或有机胺中和后生成铵盐，就成为水溶性的低聚物。  \n\n目前水性UV低聚物主要有三类。  \n\n（1）水性聚氨酯丙烯酸酯在合成聚氨酯丙烯酸酯时，加入一定量的二羟甲基丙酸DMPA)，从而引进羧基。  \n\n![](images/aa554930a0ff95e2720310e6e423b86d19be05e8606c8a0c0ae2e71502634c16.jpg)  \n\n此低聚物分子中，二羟甲基丙酸引人量少时，就为水乳型，随着二羟甲基丙酸引入量增加，就变为水分散型，当羧基用氨和有机胺中和后变成羧酸铵盐，就成为水溶性UV低聚物。  \n\n（2）水性环氧丙烯酸酯  \n\n$\\textcircled{1}$ 将环氧丙烯酸酯中的羟基与酸酐反应得到含羧基的环氧丙烯酸酯，再用有机胺中和后变成羧酸铵盐，就成为水溶性UV低聚物。  \n\n![](images/2fb6c32a34839e7e52aa5972be4cd2f54fc284d5d842442b35cb08ae0e2467a7.jpg)  \n\n随着酸酐用量增加，引人羧基增加，水溶性增加；随着有机胺中和程度增加，水溶性也增加。  \n\n$\\textcircled{2}$ 用叔胺与酚醛环氧树脂中部分环氧基反应，生成部分带季氨基的酚醛环氧树脂，然后再丙烯酸酯化，得到水溶性带季氨基的酚醛环氧丙烯酸树脂。  \n\n![](images/c9bb2433e5cffc232ef857ea4adf835f9f5124aae326f9ae42e5739d96352e2a.jpg)  \n\n![](images/9eccbdba092e179c21ddb27b1fc5262364c5a097c263323571b84dc7e1d1cc47.jpg)  \n\n（3）水性聚酯丙烯酸酯使用偏苯三甲酸酐或均苯四甲酸二酐与二元醇反应，制得带有羧基的端羟基聚酯，再与丙烯酸反应，得到带羧基的聚酯丙烯酸酯，再用氨或有机胺中和成羧基铵盐，成为水溶性聚酯丙烯酸酯。  \n\n实际应用上，水性UV低聚物主要为水性聚氨酯丙烯酸酯，它具有优良的柔韧性，耐磨性，耐化学品性，有高耐冲击和拉伸强度；芳香族的硬度好，耐黄变性差，而脂肪族的有优异耐黄变性和柔韧性。水性UV低聚物已在纸张上光油、木器清漆、水性丝印油墨领域中获得实用，正在开发用于柔印油墨、凹印油墨和水显影型光成像抗蚀剂和阻焊剂。  \n\n表3-25是水性UV低聚物与热塑性和热固性涂层材料的涂膜性能比较，表3-26介绍了水性UV低聚物的性能和应用。  \n\n表3-25各种涂层材料的涂膜性能比较  \n\n\n<html><body><table><tr><td>性能</td><td>热塑型丙烯酸树脂</td><td>二液型聚氨酯树脂</td><td>光固化PUA分散体</td><td>光固化丙烯酸酯乳液</td></tr><tr><td>耐划伤性</td><td>4</td><td>10</td><td>10</td><td>10</td></tr><tr><td>热印刷性(65C，4h,0.03MPa)</td><td>3</td><td>6</td><td>10</td><td>9</td></tr><tr><td>丙酮</td><td>2</td><td>9</td><td>10</td><td>9</td></tr><tr><td>乙醇</td><td>8</td><td>10</td><td>10</td><td>9</td></tr><tr><td>10%氨水(16h)</td><td>9</td><td>10</td><td>10</td><td>10</td></tr><tr><td>醋(16h)</td><td>6</td><td>10</td><td>6</td><td>10</td></tr><tr><td>耐磨(1h)</td><td>3</td><td>8</td><td>9.</td><td>9</td></tr></table></body></html>\n\n$\\Phi$ 溶剂型涂料。$\\textcircled{2}$ 1173为 $2\\%$ ；UV曝光量为 $1.6\\mathrm{J}/\\mathrm{cm}^{2}$ 。注：数字以10为最好。  \n\n表3-26水性UV低聚物的性能和应用  \n\n\n<html><body><table><tr><td>公司</td><td>产品代号</td><td>化学名称</td><td>官能度</td><td>黏度（25℃） /mPa·s</td><td>固含量 /%</td><td>特点和应用</td></tr><tr><td rowspan=\"6\">氰 特</td><td>EB11</td><td>水溶性PEGDA</td><td>2</td><td>120</td><td>100</td><td>良好的柔韧性，与水完全混溶；用于丝印油 墨，木器，纸张涂料</td></tr><tr><td>EB2002</td><td>水溶性脂肪 族PUA</td><td>2</td><td>25000</td><td>95</td><td>快速固化，良好的柔韧性和附着力，流变性 优异，最多可加70%的水；用于纸张、木器涂 料和油墨</td></tr><tr><td>IRR210</td><td>三官能度水溶性 丙烯酸酯</td><td>3</td><td>155</td><td>100</td><td>低黏度，良好反应活性，最多可加人45%的 水；用于纸张、木器涂料，丝印油墨</td></tr><tr><td>IRR213</td><td>三官能度水溶性 脂肪族PUA（含有 30%HDDA)</td><td>3</td><td>16500</td><td>100</td><td>良好的反应活性、柔韧性、抗磨损性和耐污 性，最多可加水15%；用于纸张、木器涂料，丝 印油墨</td></tr><tr><td>IRR390</td><td>PUA水分散体</td><td></td><td><200 (Brookfield)</td><td>35</td><td>水挥发后，固化前不指粘；用于地板涂料</td></tr><tr><td>IRR400</td><td>PUA水分散体</td><td></td><td><250 (Brookfield)</td><td>40</td><td>水挥发后，固化前不指粘；用于地板涂料和 水性油墨</td></tr><tr><td>IRR422</td><td>PUA水分散体</td><td></td><td><200 (Brookfield)</td><td>35</td><td>水挥发后，固化前不指粘；用于地板涂料</td></tr></table></body></html>  \n\n<html><body><table><tr><td>公司</td><td>产品代号</td><td>化学名称</td><td>官能度</td><td>黏度（25℃） /mPa·s</td><td>固含量 /%</td><td>特点和应用</td></tr><tr><td rowspan=\"4\">拜 耳</td><td>UVLS 2282</td><td>PUA水分散体</td><td></td><td><50s</td><td>40</td><td>力学性能和耐化学品性优异；用于木器和 地板涂料</td></tr><tr><td>UVLS 2280</td><td>PUA水分散体</td><td></td><td><90s</td><td>39</td><td>力学性能和耐化学品性优异，硬度好；用于 地板、家具涂料</td></tr><tr><td>UVLS 2317</td><td>PUA水分散体</td><td></td><td><80s</td><td>37</td><td>力学性能和耐化学品性优异，分散性更好； 用于地板、家具涂料</td></tr><tr><td>850W</td><td>水乳化型UP</td><td></td><td>12000</td><td>100</td><td>易于乳化，优异的木纹展现性；用于地板、 家具涂料的面漆和底漆</td></tr><tr><td rowspan=\"4\">巴 斯 夫</td><td>PE55WN</td><td>水溶性PEA</td><td>3.5</td><td>250~650(23C)</td><td>50</td><td>反应活性高，柔韧性和耐化学品性好；用于 PVC、塑料涂料、胶黏剂</td></tr><tr><td>PE22WN (LR8895)</td><td>水溶性PEA</td><td>3.5</td><td>150~500</td><td>50</td><td>硬度高，耐化学品性好，打磨性和附着力优 异；用于木器涂料</td></tr><tr><td>LR8949</td><td>脂肪族PUA水 分散体</td><td>1.5</td><td>40~100(23C)</td><td>40</td><td>优良的耐化学品性、柔韧性、高硬度；用于 木器、钢铁与塑料涂料</td></tr><tr><td>LR9005</td><td>芳香族PUA水 分散体</td><td>1.7</td><td>20~250(23C)</td><td>40</td><td>耐化学性和抗划伤性好，优异的干燥性，高 硬度；用于木器、钢铁与塑料涂料</td></tr><tr><td>盖斯塔夫</td><td>2000</td><td>四官能度水性芳 香族PEA</td><td>4</td><td></td><td>100</td><td>快干，用于木器涂料</td></tr><tr><td rowspan=\"2\">德 谦</td><td>UV-14</td><td>阴离子型PUA 乳液</td><td>>3</td><td>20～100</td><td>40</td><td>兼具高硬度及柔韧性，优异的耐磨性，耐划 伤性，抗粘连性，对木材、非铁金属和塑料基 材有极佳附着力；用于木器、钢铁与塑料涂料</td></tr><tr><td>UV-20</td><td>阴离子型PUA 乳液</td><td>>3</td><td>20～100</td><td>40</td><td>兼具高硬度及柔韧性，优异的耐磨性，抗划 伤性，抗粘连性，对木材、金属、塑料基材附着 力好，层间附着力良好；用于薄涂木器涂料</td></tr><tr><td rowspan=\"4\">扬州展化</td><td>CH-960</td><td>TDI型聚氨酯丙 烯酸酯水分散体</td><td></td><td></td><td>35±1</td><td>纸张、皮革、人造革、塑料涂料</td></tr><tr><td>CH-970</td><td>TDI型聚氨酯丙 烯酸酯水分散体</td><td></td><td></td><td>35±1</td><td>纸张、皮革、塑料涂料</td></tr><tr><td>CH-980</td><td>TDI型聚氨酯丙 烯酸酯水分散体</td><td></td><td></td><td>35±1</td><td>地板、塑料、金属涂料</td></tr><tr><td>CH-990</td><td>TDI型聚氨酯丙 烯酸酯水分散体</td><td></td><td></td><td>35±1</td><td>地板、塑料、金属涂料，混凝土</td></tr><tr><td>上海 多森</td><td>UVW-150</td><td></td><td></td><td></td><td>40</td><td>油墨</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 87,
+        "chunk": "# 3.11 超支化低聚物  \n\n超支化聚合物是由AB型（x≥2；A、B为反应性基团）单体制备，链增长在不同分子之间（A和B两种官能团之间）进行，一层一层向外扩散，形成树枝状大分子，具有球形的外观。超支化聚合物与同样分子量的线型大分子相比，在性能上有很大不同。  \n\n（1）超支化聚合物终端官能度非常大，端基又是具有反应活性的基团，因此反应活性极高，这样可将丙烯酰氧基引入成为光固化低聚物；还可引人亲水基团，成为水溶性树脂；甚  \n\n至可引人光引发基团，成为大分子光引发剂。  \n\n（2）超支化聚合物有球状分子外形，分子之间不易形成链段缠绕，因此比相同分子量的线型大分子黏度低很多，这对光固化低聚物来讲是非常有利的。  \n\n目前，超支化聚合物可以用一步法或准一步法来合成，合成方法简便，较易控制，因此在光固化低聚物应用上会有良好的发展前景。  \n\n下面简单介绍几种超支化光固化低聚物。  \n\n（1）季戊四醇和间苯三甲酸酐反应，得到带有8个端羧基的聚酯，再与（甲基）丙烯酸缩水甘油酯开环酯化反应，引入8个（甲基）丙烯酰氧基，同时有八个羟基形成，还可与（甲基）丙烯酸酐反应，再引人8个（甲基）丙烯酰氧基，反应全部完成，得到有16个（甲基）丙烯酰氧基的超支化低聚物。  \n\n(2）以二乙醇胺和丙烯酸甲酯经迈克尔加成反应制得N，N-二羟乙基-3-胺-丙酸甲酯单体（A)。  \n\n$$\n\\scriptstyle\\sum_{\\begin{array}{c}{{\\mathrm{HOCH}_{2}\\mathrm{CH}_{2}}}\\\\ {{\\mathrm{NH}}}\\\\ {{\\mathrm{HOCH}_{2}\\mathrm{CH}_{2}}}\\end{array}}\\overset{\\mathrm{HOCH}_{2}\\mathrm{CH}_{2}}{\\sim}\\overset{\\mathrm{HOCH}_{2}\\mathrm{CH}_{2}}{\\longrightarrow}\\overset{\\mathrm{NCH}_{2}\\mathrm{CH}_{2}\\mathrm{COOCH}_{3}}{\\longrightarrow}\\overset{\\mathrm{NCH}_{2}\\mathrm{CH}_{2}\\mathrm{COOCH}_{3}}{\\longrightarrow}\\overset{\\mathrm{NCH}_{2}\\mathrm{CH}_{2}\\mathrm{COOCH}_{3}}{\\longrightarrow}\\overset{\\mathrm{NCH}_{2}\\mathrm{CH}_{2}\\mathrm{CH}_{2}}{\\longrightarrow}\\overset{\\mathrm{NCH}_{2}\\mathrm{CH}_{2}\\mathrm{CH}_{2}}{\\longrightarrow}\\overset{\\mathrm{NCH}_{2}\\mathrm{CH}_{2}}{\\longrightarrow}\\overset{\\mathrm{NCH}_{2}\\mathrm{CH}_{2}}{\\longrightarrow}\\overset{\\mathrm{NCH}_{2}\\mathrm{CH}_{2}}{\\longrightarrow}\\overset{\\mathrm{NCH}_{2}\\mathrm{CH}_{2}}{\\longrightarrow}\\overset{\\mathrm{NCH}_{2}\\mathrm{CH}_{2}}}\\end{array}\n$$  \n\n单体（A）与三羟甲基丙烷经酯交换反应，生成第一代超支化树脂（有六个羟基）和第二代超支化树脂（有十二个羟基）(B)  \n\n$$\n\\begin{array}{r l}&{\\mathrm{Re-sch}}\\\\ &{\\mathrm{~\\gamma~}}\\\\ &{\\mathrm{HOCH}_{2}\\mathrm{CH}_{2}}\\\\ &{\\mathrm{~\\gamma~}}\\\\ &{\\mathrm{HOCH}_{2}\\mathrm{CH}_{2}}\\end{array}\\sum_{\\mathrm{N-CH}_{2}\\mathrm{CH}_{2}\\mathrm{COOCH}_{3}\\mathrm{~~+~}\\mathrm{HO-CH}_{2}\\mathrm{~-~}\\stackrel[\\mathrm{CH}_{2}\\mathrm{CH}_{3}}\\quad\\stackrel{\\mathrm{{\\scriptsize~RO~}}}{\\longrightarrow}\\stackrel{\\mathrm{{\\scriptsize~OH}~}}{\\longrightarrow}\\stackrel{\\mathrm{{\\scriptsize~OH}~}}{\\longrightarrow}\\stackrel{\\mathrm{{\\scriptsize~OH}}}{\\longrightarrow}\\stackrel{\\mathrm{{\\scriptsize~OH}}}{\\longrightarrow}\\quad\\stackrel{\\mathrm{{\\scriptsize~OH}}}{\\longrightarrow}\\stackrel{\\mathrm{{\\scriptsize~OH}}}{\\longrightarrow}\\quad\\stackrel{\\mathrm{{\\scriptsize~OH}}}{\\longrightarrow}\\stackrel{\\mathrm{{\\scriptsize~OH}}}{\\longrightarrow}}\\\\ &{\\mathrm{\\gamma~}}\\\\ &{\\mathrm{CH}_{2}\\mathrm{OH}}\\end{array}\n$$  \n\n超支化树脂B若与（甲基）丙烯酸酐或二异氰酸酯与丙烯酸羟基酯半加成物反应，就可引入丙烯酰氧基，成为超支化光固化低聚物。  \n\nB的部分羟基与马来酸酐等反应，则可引入羧基，经胺中和成铵盐就可成为水性超支化低聚物。  \n\nB的部分羟基与二异氰酸酯和光引发剂D2959 的半加成物反应，就可引人光引发基团，成为大分子光引发剂。  \n\n（3）用乙二胺与三羟基甲基丙烷三丙烯酸酯，经迈克尔加成反应，可得到带8个丙烯酰氧基的超支化低聚物。  \n\n![](images/d4d235542ceea7ace689d5a5b55b93aca9e31630bde7787a9719a7593a49ff0c.jpg)  \n\n（4）将间苯三甲酸和环氧氯丙烷反应，得到端酸酐基和大量羧基的超支化聚合物，再与（甲基）丙烯酸缩水甘油酯反应，引入（甲基）丙烯酰氧基，成为超支化光固化低聚物，由于羧基含量高，是一个碱溶型低聚物，若将光引发剂1173与端酸酐反应，则引入光引发基团成为大分子光引发剂。表3-27～表3-31介绍了超支化聚丙烯酸酯的性能和应用。  \n\n表3-27超支化多元醇和超支化聚丙烯酸酯的性能  \n\n\n<html><body><table><tr><td>性能</td><td>超支化聚丙烯酸酯</td><td>超支化多元醇</td></tr><tr><td>分子量</td><td>2700</td><td>1600</td></tr><tr><td>丙烯酸酯含量/(mmol/g)</td><td>5.5</td><td>一</td></tr><tr><td>羟基/(mgKOH/g)</td><td></td><td>590</td></tr><tr><td>酸值/(mgKOH/g)</td><td>2.0</td><td>≤3</td></tr><tr><td>非VOC/%</td><td>>99</td><td></td></tr><tr><td>密度/(g/cm3）</td><td>1.168</td><td></td></tr><tr><td>黏度(25℃)/mPa·s</td><td>750</td><td>14000</td></tr><tr><td>收缩率/%</td><td>10</td><td></td></tr><tr><td>折射率(22℃)</td><td>1.513</td><td></td></tr><tr><td>固化膜T/C</td><td>90</td><td></td></tr></table></body></html>  \n\n表3-28超支化聚丙烯酸酯和多官能团丙烯酸酯固化膜性能  \n\n\n<html><body><table><tr><td>性能</td><td>DPHA</td><td>PP50S</td><td>超支化聚丙烯酸酯</td></tr><tr><td>黏度（25℃)/mPa·s</td><td>1400</td><td>200</td><td>700</td></tr><tr><td>最低固化速率（12μm厚）/（m/min）</td><td>15</td><td>12</td><td>15</td></tr><tr><td>辐射剂量/(mJ/cm²）</td><td>200</td><td>300</td><td>200</td></tr><tr><td>铅笔硬度(40μm厚/玻璃)</td><td>6H/7H</td><td>4H/5H</td><td>5H/6H</td></tr><tr><td>摆杆硬度(40um厚/玻璃)</td><td>163</td><td>156</td><td>165</td></tr><tr><td>柔度（12μm厚）/mm</td><td>2.2</td><td>2.2</td><td>0.4</td></tr><tr><td>耐水性（40μm，48h)</td><td>5</td><td>4</td><td>4</td></tr><tr><td>耐溶剂性（40μm,48h水：乙醇=1：1）</td><td>4</td><td>3</td><td>4</td></tr><tr><td>附着力（12μm，PC基材）</td><td>3</td><td>5</td><td>5</td></tr><tr><td>耐磨性(40μm，200次85°的光洁度）</td><td>88</td><td>66</td><td>92</td></tr></table></body></html>  \n\n表3-29沙多玛公司超支化聚酯丙烯酸酯的性能和应用  \n\n\n<html><body><table><tr><td rowspan=\"2\">商品名</td><td rowspan=\"2\">官能度</td><td rowspan=\"2\">丙烯酸 当量</td><td rowspan=\"2\">黏度（25℃) /mPa·s</td><td rowspan=\"2\">表面张力（25℃） /(X10-3N/m)</td><td colspan=\"4\">固化膜性能</td><td rowspan=\"2\">应用</td></tr><tr><td>拉伸强度 /psi</td><td>伸长率 /%</td><td>模量 /psi</td><td>Tg /℃</td></tr><tr><td>CN2300</td><td>8</td><td>163</td><td>600</td><td>32.6</td><td>5360</td><td>4.5</td><td>98800</td><td>96</td><td>喷墨、柔印油墨</td></tr><tr><td>CN2301</td><td>9</td><td>153</td><td>3500</td><td>38.4</td><td>4880</td><td>3.8</td><td>194950</td><td>77</td><td>涂料</td></tr><tr><td>CN2302</td><td>16</td><td>122</td><td>350</td><td>37.8</td><td>7400</td><td>9.1</td><td>162800</td><td>87</td><td>油墨、涂料</td></tr><tr><td>CN2303</td><td>6</td><td>194</td><td>320</td><td>40.3</td><td>7675</td><td>1.9</td><td>237423</td><td>60</td><td>喷墨油墨、硬涂料</td></tr><tr><td>CN2304</td><td>18</td><td>96</td><td>750</td><td>32.6</td><td>8750</td><td>1.1</td><td>204356</td><td>181</td><td>涂料</td></tr><tr><td>DPHA</td><td>6</td><td>102</td><td>13000</td><td>39.9</td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>\n\n注： $1\\mathtt{p s i}{=}6894.76\\mathtt{P a}$ ，下同。  \n\n表3-30Bomar公司超支化聚酯丙烯酸酯的性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">商品名</td><td rowspan=\"2\">官能度</td><td rowspan=\"2\">低聚物 种类</td><td rowspan=\"2\">黏度（25℃) /mPa·s</td><td rowspan=\"2\">T /℃</td><td colspan=\"3\">固化膜性能</td><td rowspan=\"2\">涂料黏度（25℃） /（X10-3N/m）</td></tr><tr><td>硬度</td><td>拉伸强度 /psi</td><td>断裂伸长率 /%</td></tr><tr><td>BDE-1025</td><td>8</td><td>脂肪族</td><td>1350</td><td>3</td><td>530</td><td>2594</td><td>26</td><td>180</td></tr><tr><td>BDE1029</td><td>14</td><td>脂肪族</td><td>350</td><td>83</td><td>580</td><td>5503</td><td>4</td><td>95</td></tr></table></body></html>\n\n$\\textcircled{1}$ $30\\%$ IBOA $+2\\%$ Omnirad481。  \n\n表3-31Perstorp公司超支化聚酯丙烯酸酯的性能  \n\n\n<html><body><table><tr><td>商品名称</td><td>黏度(25℃) /mPa·s</td><td>最小UV固化 剂量/（mJ/cm²）</td><td>柔韧性 /mm</td><td>铅笔硬度</td><td>耐刮擦性60° 保光性/%</td><td>PC板上粘 接牢度</td><td>附着力180° 弯曲试验</td></tr><tr><td>BoltornP500丙</td><td>700</td><td>200</td><td>0.4</td><td>3H/4H</td><td>90</td><td>3</td><td>好</td></tr><tr><td>烯酸酯 DPHA</td><td>14000</td><td>200</td><td>2.2</td><td>2H/3H</td><td>91</td><td></td><td>良好</td></tr></table></body></html>  \n\n低聚物中含有两种不同类型的活性基团。丙烯酰氧基可以进行自由基光固化，而另一个基团可以进行阳离子光固化、湿固化、羟基固化、热固化等，成为具有双重固化功能的低聚物。  \n\n用双酚A环氧树脂和丙烯酸［环氧基：羧基为 $(1.5{\\sim}2.0):1]$ 开环酯化反应，制得带有环氧基的环氧丙烯酸树脂，其中丙烯酸基团可以进行自由基光聚合，而环氧基可进行阳离子光聚合。研究结果表明，这两种活性基团之间存在着分子内的相互作用，可有效促进自由基和阳离子光聚合的进行，使反应速率和最终转化率有明显的提高，而且大大降低了氧阻聚作用；双重固化低聚物所形成的固化膜具有更好的力学性能。  \n\n将六亚甲基二异氰酸酯和 $N$ ， $N\\cdot$ 二(氨丙基三乙氧基)硅烷反应，再与丙烯酸羟乙酯作用，制得具有自由基光固化/湿固化双重固化性能的硅氧烷型聚氨酯丙烯酸酯，可用于光固化保型涂料。  \n\n合成含有环氧基的酚醛环氧丙烯酸树脂，具有自由基光固化/热固化双重固化功能，可用于光成像阻焊剂。  \n\n德国拜耳公司、巴斯夫公司和上海多森化工公司都有商品化的双重固化低聚物，见表3-32。  \n\n表3-32拜耳双重固化树脂  \n\n\n<html><body><table><tr><td>商品名</td><td>结构</td><td>含量/%</td><td>黏度（23℃）/mPa·s</td><td>应用</td></tr><tr><td>UAVP LS 2337</td><td>含—NCO基的脂肪族聚氨酯丙烯 酸酯，—NCO含量12.5%</td><td>100</td><td>12500</td><td>光/羟基双重固化体系</td></tr><tr><td>UAVPLS2396</td><td>含—NCO基的脂肪族聚氨酯丙烯 酸酯，-NCO含量12.5%</td><td>100</td><td>12500</td><td>光/羟基双重固化体系</td></tr></table></body></html>  \n\n巴斯夫公司的 $\\mathrm{LR9000}$ 为双重固化低聚物，既含有丙烯酸基，可进行光固化，又含有异氰酸基，可进行羟基、氨基或热固化。上海多森化工公司的UVDC-2700为双固化低聚物，含有丙烯酸基和异氰酸基，可进行自由基光固化，也可进行羟基、氨基或热固化。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 88,
+        "chunk": "# 3.13 自引发功能的低聚物  \n\n具有自引发功能的低聚物有两类：  \n\n$\\textcircled{1}$ 低聚物自身具有光引发功能，在配方中可以少用甚至不用加光引发剂；  \n\n$\\textcircled{2}$ 在低聚物中接入光引发基团，成为大分子光引发剂，在配方中既作低聚物又作光引发剂使用。  \n\n第一类自身具有光引发功能的低聚物，是美国亚什兰公司开发的新产品，它通过多官能团丙烯酸酯与 $\\beta$ 酮酯（如乙酰乙酸乙酯、乙酰乙酸烯丙酯、甲基丙烯酸-2-乙酰乙酸乙酯)发生迈克尔加成反应， $\\beta$ 酮酯中活性亚甲基上碳与丙烯酸酯碳碳双键端基碳形成新的共价键， $\\beta$ 酮酯中基与一个完全被取代的碳原子相连，该键对紫外光具有不稳定性，吸收紫外光之后，很容易断键，生成乙酰基自由基和另外一个大分子自由基，具有自引发功能。因此，使用具有自引发功能的低聚物的UV涂料、油墨、胶黏剂的配方中，可以不添加光引发剂，从而避免了添加光引发剂所造成的气味、黄变、难以混入、析出、迁移以及价格昂贵等问题。  \n\n![](images/3960d0bd4a901f9b136c7ab813d6b5738b64ea321091a0d562b959816e2a02ac.jpg)  \n\n自身具有光引发功能的低聚物还可以通过多种丙烯酸酯与多种迈克尔反应而制得，形成系列产品。  \n\n![](images/a85b8490401c3736f0dbc7e5bc984fa2f7e0ead969639a93a86b97bb28d2e1a1.jpg)  \n\n美国亚什兰公司开发自引发低聚物Drewrad系列产品见表3-33和表3-34。  \n\n表3-33 亚什兰Drewrad系列产品和用途  \n\n\n<html><body><table><tr><td>商品代号</td><td>用途</td><td>商品代号</td><td>用途</td><td></td></tr><tr><td>300系列</td><td>清漆</td><td>D系列</td><td>颜料、填料分散</td><td></td></tr><tr><td>1000系列</td><td>木器漆</td><td>500系列</td><td>印刷油墨</td><td></td></tr><tr><td>1100系列</td><td>木器填充底漆</td><td>M系列</td><td>消光</td><td></td></tr><tr><td>100系列</td><td>上光油</td><td></td><td></td><td></td></tr></table></body></html>  \n\n表3-34亚什兰自引发低聚物Drewrad系列部分产品的性能  \n\n\n<html><body><table><tr><td colspan=\"2\" rowspan=\"2\">性能</td><td colspan=\"9\">商品名称</td></tr><tr><td>130</td><td>150 530</td><td>540</td><td>331</td><td></td><td>1010</td><td>1040</td><td>1110</td><td>1120</td></tr><tr><td colspan=\"2\" rowspan=\"4\">密度/(g/mL) 黏度（25℃）/mPa·s 平均分子量</td><td>1.09 400～500|200~300</td><td>1.09</td><td>1.12 1100</td><td>1.13 1650</td><td>1.10 500~1000</td><td>1.11 1200</td><td>1.09 350</td><td>1.14 4500</td><td>1.18 10000</td></tr><tr><td></td><td>650</td><td>1275</td><td>750</td><td>3000</td><td>800</td><td>700</td><td>800</td><td>1100</td></tr><tr><td>650 2.1</td><td>2.1</td><td>2.4</td><td>2.1</td><td>2.1</td><td>2.5</td><td>2.3</td><td>4.7</td><td>3.3</td></tr><tr><td></td><td>220</td><td></td><td>1200</td><td>11.7</td><td>12</td><td>10</td><td>19</td><td>--10</td></tr><tr><td>固化膜性能 铅笔硬度</td><td>750 完全固化能量/（mJ/cm²）</td><td></td><td>900 6</td><td></td><td></td><td>1040 5.0</td><td>70 10</td><td>730 11</td><td>1300 3</td><td>260 10</td></tr><tr><td colspan=\"2\">伸长度/% 拉伸强度/psi</td><td colspan=\"10\">5 6 8</td></tr><tr><td colspan=\"2\">附加特性</td><td colspan=\"9\">1300 650 800 600 通过美国FDA认证</td></tr></table></body></html>\n\n注： $1\\mathtt{p s i}{=}6894.76\\mathtt{P a}$ 。  \n\n第二类具有自引发功能的低聚物大多利用含有羟基的光引发剂（安息香、1173、184、2959）与带异氰酸基的低聚物反应，将光引发剂接入低聚物，成为具有光引发基的低聚物。  \n\n接枝光引发剂的低聚物优点：  \n\n①光固化速率接近于普通低聚物与小分子光引发剂的固化速率，甚至更快；  \n$\\textcircled{2}$ 与体系的相容性好；  \n③大大降低了光引发剂的迁移能力；  \n④大大降低了光引发剂有害的光分解产物（如苯甲醛）产生；  \n③光引发剂无毒无害，可以用于食品包装涂料和油墨中。  \n\n表3-35为接枝光引发剂的低聚物与普通低聚物加小分子光引发剂固化后从固化膜中抽提出光引发剂和苯甲醛的实验结果。  \n\n表3-35从固化膜抽提出光引发剂和苯甲醛浓度  \n\n\n<html><body><table><tr><td>序号</td><td>光引发剂</td><td>体系中光引发剂浓度 （质量分数）/%</td><td>抽提出光引发剂浓度 /×10-6</td><td>抽提出苯甲醛浓度 /X10-5</td></tr><tr><td>1-1</td><td>184</td><td>4.0</td><td>1150</td><td>8.0</td></tr><tr><td>1-2</td><td>接枝184</td><td>4.0</td><td>48</td><td>0.5</td></tr><tr><td>2-1</td><td>184</td><td>4.0</td><td>400</td><td>3.0</td></tr><tr><td>2-2</td><td>接枝184</td><td>4.0</td><td>19</td><td>0.3</td></tr><tr><td>3-1</td><td>2959</td><td>4.0</td><td>801</td><td>100</td></tr><tr><td>3-2</td><td>接枝2959</td><td>4.0</td><td>89</td><td>40</td></tr><tr><td>4-1</td><td>安息香</td><td>4.0</td><td>725</td><td>30</td></tr><tr><td>4-2</td><td>接枝安息香</td><td>4.0</td><td>18</td><td>10</td></tr></table></body></html>  \n\n数据表明，光引发剂的接枝反应大大降低了引发剂碎片的迁移能力和浸出能力，而且“接枝的”固化膜中生成的苯甲醛量也大大减少，因此接枝在低聚物上的光引发剂，实质上就是一类大分子光引发剂，无毒无害，可以用在食品和药品包装用的涂料及油墨中。2006年美国食品和药物管理局（FDA）宣布用大分子光引发剂生产的UV涂料和油墨可以用于食品及药品包装印刷中，彻底改变了以往UV油墨和涂料不能用于食品及药品包装的惯例，开创了UV油墨和涂料应用的新领域。Bomar公司已商品化带光引发剂的低聚物产品及性能见表3-36。  \n\n表3-36Bomar公司带光引发剂低聚物的性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">商品名称</td><td rowspan=\"2\">官能度</td><td rowspan=\"2\">低聚物结构</td><td rowspan=\"2\">黏度(50℃) /mPa·s</td><td colspan=\"3\">固化膜性能</td><td rowspan=\"2\">涂料黏度(25℃) /mPa·s</td></tr><tr><td>硬度</td><td>拉伸强度/psi</td><td>断裂伸长率/%</td></tr><tr><td>XP-144LS</td><td>2</td><td>脂肪族PUA</td><td>125000</td><td>77D</td><td>7536</td><td>7</td><td>28000</td></tr><tr><td>XP-144LS-B</td><td>2</td><td>脂肪族PUA</td><td>10500</td><td>81D</td><td>5780</td><td>6</td><td>19250</td></tr><tr><td>XP-543LS</td><td>2</td><td>脂肪族PUA</td><td>30000</td><td>53A</td><td>725</td><td>343</td><td>30750</td></tr></table></body></html>\n\n$\\Phi$ 30%IBOA $+2\\%$ Omnirad 481。注： $1\\mathrm{{psi}=6894,76\\mathrm{{Pa}}}$ 。  \n\n韩国Miwon公司利用季戊四醇三丙烯酸酯与酸酐反应，制得端羧基季戊四醇三丙烯酸酯；用双季戊四醇五丙烯酸酯与酸酐反应，制得端羧基双季戊四醇五丙烯酸酯。然后再与二缩水甘油醚反应，制得了一系列多官能团脂肪族与脂环族环氧丙烯酸酯，其黏度见表3-37。  \n\n表3-37多官能团环氧丙烯酸酯的化学结构与黏度  \n\n\n<html><body><table><tr><td>类 型</td><td>低聚物</td><td>官能度</td><td>骨架结构</td><td>黏度(40℃)/mPa·s</td></tr><tr><td rowspan=\"2\">I</td><td>MEA-1</td><td>6</td><td>烷基环氧-三丙烯酸酯</td><td>4700</td></tr><tr><td>MEA-2</td><td>10</td><td>烷基环氧-五丙烯酸酯</td><td>2800</td></tr><tr><td rowspan=\"2\">Ⅱ</td><td>MEA-3</td><td>6</td><td>环已基环氧-三丙烯酸酯</td><td>64000</td></tr><tr><td>MEA-4</td><td>10</td><td>环已基环氧-五丙烯酸酯</td><td>8000</td></tr><tr><td rowspan=\"2\">Ⅱ</td><td>MEA-5</td><td>9</td><td>烷基环氧-三丙烯酸酯</td><td>75000</td></tr><tr><td>MEA-6</td><td>15</td><td>烷基环氧-五丙烯酸酯</td><td>5700</td></tr></table></body></html>  \n\n![](images/77e5c77514ecaccd5d45470ac146ab638107a0580cfb68aeec79024b7d549e64.jpg)  \n\n![](images/3a6e02abc4c84284ce30449756a2c6cf05b85308e1753a3f1ff52238d003837e.jpg)  \n\n同一系列中，官能度大，黏度反而小；带刚性基团的环已基环氧黏度明显比烷基环氧黏度大。随着官能度的增加，硬度增加，耐磨性增加，耐化学腐蚀性也增加；拉伸强度增加，但拉伸率降低；塑料附着力随官能度的增加而降低；随官能度的增加，耐黄变性变差，含环己基耐黄变性更差。与对应的聚氨酯丙烯酸酯相比，环氧丙烯酸酯的大部分性能要好，尤其是耐化学品腐蚀性更好。 10.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 89,
+        "chunk": "# 3.15 低黏度低聚物  \n\nUV喷墨打印是20世纪末发展起来的光固化材料新技术。喷墨打印是一种非接触式印刷，不需印版，通过喷射墨滴到基材上而形成图像的过程。通过计算机编辑好图形和文字，并控制喷墨打印机喷头喷射墨滴获得精确的图像，完全是数字化成像的过程，是目前发展最迅速的一种数字成像方式，具有按需打印、高速度、高质量、色彩饱和等优点。  \n\nUV喷墨打印的主要耗材为UV喷墨油墨，它要求油墨低黏度、高固化速率和颜料稳定性好，不发生沉降。  \n\n美国沙多玛公司开发了专为UV喷墨油墨使用的聚酯丙烯酸酯CN2300和CN2301，其性能见表3-38。  \n\n表3-38 CN 2300和CN2301的性能  \n\n\n<html><body><table><tr><td>性能</td><td>CN2300</td><td>CN2301</td></tr><tr><td>黏度(25℃)/mPa·s</td><td>200</td><td>700</td></tr><tr><td>官能度</td><td>8</td><td>8</td></tr><tr><td>体积收缩率/%</td><td>9</td><td>8</td></tr></table></body></html>  \n\n美国氰特公司也为UV喷墨油开发了专用低聚物Viajet100和Viajet400，其性能见表3-39。  \n\n表3-39 Viajet100和Viajet400的性能   \n\n\n<html><body><table><tr><td>性能</td><td>Viajet 100</td><td>Viajet 400</td></tr><tr><td>黏度（25℃）/mPa·s</td><td>107</td><td>20</td></tr><tr><td>密度（21.5℃）/(g/cm）</td><td>1.09</td><td>1.07</td></tr><tr><td>色泽（Gardner)</td><td>5</td><td>1.6</td></tr></table></body></html>  \n\nViajet100用于颜料分散，制成色浆；而Viajet400用于稀释色浆加上光引发剂和助剂 制成喷墨油墨。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 90,
+        "chunk": "# 8.16 光固化聚丁二烯低聚物  \n\n光固化聚丁二烯低聚物是在聚丁二烯中接入丙烯酸酯基或环氧基，使其可以通过UV光交联形成兼备橡胶、聚丙烯酸酯或环氧树脂的性能。这类低聚物在常温下是液态的可以按常规的光固化工艺加工。由于其主链上聚丁二烯结构具有高韧性（尤其低温时)、耐水稳定性、耐酸碱性、优良的电性能，特别适用于电子化学品、柔性印刷版、胶黏剂和密封胶（图3-1)。  \n\n![](images/595cc7ee3021452370d9a6ce0f7dc7a1a18bc137d9b98ab73fd46d6372cd328b.jpg)  \n图3-1光固化聚丁二烯低聚物结构  \n\n在自由基光固化时，聚丁二烯丙烯酸酯中（甲基）丙烯酸酯双键转化率远远高于聚丁二烯上1,4-双键和1,2-双键转化率（表3-40)，但由于1,4-双键和1,2-双键可引发总数大，故它们对形成聚合物网络交联密度的贡献仍是显著的。  \n\n表3-40聚丁二烯丙烯酸酯Ricacryl3801光固化双键转化率①  \n\n\n<html><body><table><tr><td>双键</td><td>(甲基)丙烯酸酯基</td><td>1,2-双键</td><td>1,4-双键</td></tr><tr><td>双键数</td><td>8</td><td>26</td><td>10</td></tr><tr><td>双键转化率/%</td><td>80以上</td><td>14</td><td>27</td></tr></table></body></html>\n\n①3%KIP-100F， ${\\mathrm{5J/cm}}^{2}$ 0  \n\n鉴于聚丁二烯具有卓越的水解稳定性、低透湿性和极好的耐酸碱性，而光聚合形成的交联网络又赋予固化膜更好的耐化学品性质，特别是耐酸碱性。将聚氨酯丙烯酸酯和聚丁二烯丙烯酸酯固化膜在50%的硫酸溶液中室温下浸泡120h，聚丁二烯丙烯酸酯固化膜的拉伸强度几乎没有变化，而聚氨酯丙烯酸酯固化膜的拉伸强度大幅度下降，仅保留不足原强度的10%，这是由于在60℃、50%的硫酸作用下发生了酯键水解和随之对聚合物网络结构的破坏而引起的。用50%的NaOH溶液进行耐碱实验结果亦完全相同。  \n\n沙多玛公司、Bomer公司和大阪有机化学公司商品化的光固化聚丁二烯低聚物见表3-41～表3-44。  \n\n表3-41沙多玛公司聚丁二烯丙烯酸酯低聚物的性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">商品名称</td><td colspan=\"5\">官能度</td><td rowspan=\"2\">黏度 /mPa·s</td><td colspan=\"6\">固化膜性能</td></tr><tr><td>分子量AA基</td><td></td><td>M基A</td><td>1,2</td><td>1.4键</td><td>固化速率</td><td>拉伸强度</td><td>断翠</td><td>模</td><td>耐冲击强</td><td>T</td></tr><tr><td>Ricaryl 3801</td><td>3200</td><td>2</td><td>6</td><td>26</td><td>10</td><td>25000(45℃)</td><td>50</td><td>1659</td><td>6.6</td><td>52846</td><td><2</td><td>-18.02</td></tr><tr><td>CN301</td><td>3000</td><td></td><td>2</td><td></td><td></td><td>920(60℃)</td><td>20</td><td>639</td><td>15.2</td><td>6979</td><td>48</td><td>--44.45</td></tr><tr><td>CN302</td><td>3000</td><td>2</td><td></td><td></td><td></td><td>17000(60℃)</td><td>20</td><td>166</td><td>36.2</td><td>724</td><td>75</td><td>一39.83</td></tr><tr><td>CN303</td><td>3000</td><td></td><td>2</td><td></td><td></td><td>4125(60℃)</td><td>10</td><td>235</td><td>35.2</td><td>1185</td><td>28</td><td>-38.93</td></tr></table></body></html>\n\n注：1ft=0.30m；1psi=6894.76Pa;1lb=0.45kg；lin=2.54cm。  \n\n表3-42Bomar公司聚丁二烯氨基甲酸酯丙烯酸酯低聚物的性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">商品名称</td><td rowspan=\"2\">官能度</td><td rowspan=\"2\">低聚物种类</td><td rowspan=\"2\">黏度（50℃) /mPa·s</td><td colspan=\"4\">固化膜性能</td></tr><tr><td>硬度</td><td>拉伸强度/psi</td><td>断裂伸长率/%</td><td>涂料黏度(25C）/mPa·s</td></tr><tr><td>BR-641</td><td>2</td><td>脂肪族</td><td>62000</td><td>85D</td><td>3030</td><td>36</td><td>18885</td></tr><tr><td>BR-643</td><td>2</td><td>脂肪族</td><td>65000</td><td>85A</td><td>11230</td><td>57</td><td>15250</td></tr></table></body></html>\n\n①30%IBA+2%Omnirad 481。注： $1\\mathtt{p s i}{=}6894.76\\mathtt{P a}$ 0  \n\n表3-43大阪有机化学公司聚丁二烯丙烯酸酯低聚物的性能  \n\n\n<html><body><table><tr><td>商品名称</td><td>化学名称</td><td>平均分子量</td><td>黏度/mPa·s</td></tr><tr><td>BAC-45</td><td>聚丁二烯二丙烯酸酯</td><td>3000</td><td>4000~8000</td></tr><tr><td>BAC-15</td><td>聚丁二烯二丙烯酸酯</td><td>1000</td><td>1000~3000</td></tr><tr><td>PIPA</td><td>聚异戊二烯二丙烯酸酯</td><td>2700</td><td>5000~12000</td></tr></table></body></html>  \n\n该低聚物皮肤刺激性极低（PII≈0)，低黏度，卓越的UV/EB灵敏度。  \n\n表3-44沙多玛公司环氧聚丁二烯低聚物的性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">商品名称</td><td rowspan=\"2\">环氧值</td><td rowspan=\"2\">环氧当量</td><td rowspan=\"2\">环氧含量</td><td>顺式</td><td>反式</td><td>1,2-</td><td>1,4-</td><td>断开</td><td>黏度</td><td>密度</td><td>羟值</td></tr><tr><td>1%</td><td>环氧基</td><td>环氧基 双键</td><td>双键</td><td>环氧基</td><td>/mPa·s</td><td>/（g/cm）</td><td>/(mgKOH/g)</td></tr><tr><td>PolyBD-600E</td><td>2~2.5</td><td>400~500</td><td>3.4</td><td>7~10</td><td>8~12</td><td>22</td><td>53~60</td><td>3~4</td><td>7000</td><td>1.01</td><td>1.70</td></tr><tr><td>PolyBD-605E</td><td>3~4</td><td>260~330</td><td>4.8~6.2</td><td>7~10</td><td>8~12</td><td>22</td><td>53~60</td><td>3~4</td><td>22000</td><td>1.01</td><td>1.74</td></tr></table></body></html>  \n\nUV固化粉末涂料是20世纪90年代开发的一种新型涂料，是一种将传统粉末涂料和UV固化技术相结合的新技术，兼有粉末涂料和液态UV涂料的优点（见表3-45)；具有固化速率快、熔融温度低（100～140℃）、无VOC排放、原料利用率高等特点，可用于木材、塑料、纸张、热敏合金和含有热敏零件的金属元件等热敏基材的涂装，非常适合三维及复杂工件的涂装，见表3-45。  \n\nUV固化粉末涂料是由光固化低聚物、光引发剂、助固化剂、颜料、填料和各种助剂组成的。用作UV固化粉末涂料的光固化低聚物，要求能赋予粉末良好的贮存稳定性，在高达40℃条件下贮存3～6个月不结块；低聚物必须在较低的温度（≤100℃）下具有较低的熔融黏度，以保证涂料在光固化之前和光固化过程中具有良好的流动性及流平性。这就要求低聚物Tg应在50～70℃（至少在40℃以上），平均分子量在1000～4000，分子量分布要窄。目前已开发的低聚物有不饱和聚酯、乙烯基醚树脂、聚酯丙烯酸树脂、聚氨酯丙烯酸树脂和环氧丙烯酸树脂，近年来超支化聚合物因有高官能度、低黏度、高活性和互容性好等特点，可应用于粉末涂料中作成膜树脂或黏度改性剂等，以提高漆膜的各种性能。  \n\n氰特公司、道化学公司和DSM公司都已有商品化的UV固化粉末涂料低聚物，见表3-46和表3-47。  \n\n表3-45UV固化粉末涂料的特点  \n\n\n<html><body><table><tr><td>传统粉末涂料优点（√）和缺点（×）</td><td>液体UV涂料优点（√）和缺点（X）</td></tr><tr><td>√无溶剂排放，安全环保 √可回收使用，利用率高</td><td>√固化速率快，固化温度范围宽 √可薄涂</td></tr><tr><td>√施工简单方便</td><td>√漆膜硬度高，耐化学品性好</td></tr><tr><td>√漆膜物化性能优异，边角覆盖好</td><td>×有VOC释放可能性</td></tr><tr><td>√适合三维工件</td><td>×涂料不可回收，利用率不高</td></tr><tr><td>×不适合各热敏基材，固化温度高，时间长</td><td>×漆膜收缩率高，边角覆盖不好</td></tr><tr><td>×漆膜流平性、硬度一般</td><td>×漆膜较脆，与底材附着力较差 ×不适合三维工件</td></tr></table></body></html>  \n\n表3-46氰特公司UV粉末涂料树脂  \n\n\n<html><body><table><tr><td>商品名称</td><td>树脂形态</td><td>Tg/C</td><td>黏度（175℃）/mPa·s</td><td>应 用</td></tr><tr><td>Uvecoat2000</td><td>无定形甲基丙烯酸聚酯</td><td>47</td><td>3300(200℃)</td><td>金属部件，热敏合金</td></tr><tr><td>Uvecoat 2100</td><td>无定形甲基丙烯酸聚酯</td><td>57</td><td>5500(200℃)</td><td>金属部件，热敏合金</td></tr><tr><td>Uvecoat 2200</td><td>无定形甲基丙烯酸聚酯</td><td>54</td><td>4500</td><td>金属部件，热敏合金</td></tr><tr><td>Uvecoat 2300</td><td>无定形</td><td>53</td><td>2500(200℃)</td><td></td></tr><tr><td>Uvecoat 3000</td><td>无定形</td><td>51</td><td>6000</td><td>中密度板花纹漆、清漆，PVC地板漆</td></tr><tr><td>Uvecoat 3001</td><td>无定形</td><td>43</td><td>2000</td><td>平整度高的木器清漆</td></tr></table></body></html>  \n\n<html><body><table><tr><td>商品名称</td><td>树脂形态</td><td>T/℃</td><td>黏度(175℃)/mPa·s</td><td>应用</td></tr><tr><td>Uvecoat 3002</td><td>无定形</td><td>49</td><td>4500</td><td>中密度板花纹漆，清漆</td></tr><tr><td>Uvecoat3003</td><td>无定形</td><td>49</td><td>3500</td><td>PVC地板漆</td></tr><tr><td>Uvecoat3101</td><td>无定形</td><td>43</td><td>1800</td><td></td></tr><tr><td>Uvecoat9010</td><td>半结晶</td><td>80(Tm)</td><td>300(100℃)</td><td>配合3000系列使用，降低熔融黏度</td></tr></table></body></html>  \n\n表3-47道化学和DSM公司UV粉末涂料树脂  \n\n\n<html><body><table><tr><td>公司</td><td>商品名称</td><td>树脂类型</td><td>黏度/Pa·s</td><td>T/℃</td></tr><tr><td rowspan=\"2\">道化学</td><td>XZ 92478.00</td><td>环氧丙烯酸树脂</td><td>2~4(150℃)</td><td>85~105</td></tr><tr><td>Uracross p3125</td><td>无定形不饱和聚酯</td><td>30~50</td><td>48</td></tr><tr><td rowspan=\"4\">DSM</td><td>Uracross zw4892P</td><td>无定形不饱和聚酯</td><td>50～100</td><td>51</td></tr><tr><td>Uracross zw4901p</td><td>无定形不饱和聚酯</td><td>30~70</td><td>54</td></tr><tr><td>Uracross p3307</td><td>半结晶乙烯基醚氨基树脂</td><td></td><td>90～110(Tm)</td></tr><tr><td>Uracrossp3898</td><td>半结晶乙烯基醚氨基树脂</td><td></td><td>90~130（Tm）</td></tr></table></body></html>  \n\n杂化低聚物是指含有金属离子的丙烯酸低聚物，它的结构组成既有有机部分，如聚氨酯、聚酯，又有金属离子，通过丙烯酸基、甲基丙烯酸基、羧基、羟基等功能基团与有机部分相连（图3-2)。这种金属离子与有机物的杂化结构既可以形成常规的共价键交联，又有离子键的交联，因此赋予一些特殊性能，应用于涂料、油墨、胶黏剂等产品可具有导电性、抗菌性、高折射率以及催化性能等，也可改善与金属和玻璃等基材的附着力。  \n\n有机组成一 $\\mathbf{\\nabla}\\cdot\\mathbf{M}^{2+}$ 一有机组成$\\scriptstyle\\mathbf{M}=\\mathbf{Z}_{\\mathtt{n}}$ 、AI、Ca、 $\\mathbf{M}_{\\mathbf{B}}$ 有机组成如下。功能基团：丙烯酸基、甲基丙烯酸基、羧基、羟基主体结构：聚氨酯、聚酯  \n\n杂化低聚物具有憎水特征，但它们可以溶解于典型的活性稀释剂（如TPGDA、TMP-TA）中，因此，可以用于高档的UV产品配方。由于杂化低聚物可以形成含有可移动的和可逆的离子交联键，具有高温流动性，而室温则回归离子交联。所以杂化低聚物可以用于生产UV固化金属涂料、胶黏剂以及粉末涂料。  \n\n![](images/031df2383af0592a7b75cb85609277cf088ca393d15faf3ace91c0355e95487c.jpg)  \n图3-2杂化低聚物  \n\n![](images/42ecb4c4781e8b5c4ae9b3292896cee7aa0877045904239f7b348ce8c46af2ea.jpg)  \n图3-3和图3-4介绍了两种杂化低聚物的合成方法。  \n图3-3杂化聚酯丙烯酸酯的低聚物  \n图3-4杂化聚氨酯丙烯酸酯的低聚物  \n\n表 3-48是加入杂化低聚物的UV涂料基本配方，可添加1～16 份的含锌杂化低聚物(CN2404或CN2405)，表3-49为烘烤前后与基材粘接性的变化。  \n\n表3-48添加杂化低聚物的UV涂料基本配方  \n\n\n<html><body><table><tr><td>配方及性能</td><td>指标</td></tr><tr><td>PUA/份</td><td>63.5</td></tr><tr><td>IBOA/份</td><td>31.7</td></tr><tr><td>HDDA/份</td><td>4.8</td></tr><tr><td>SR1135/份</td><td>0.95</td></tr><tr><td>CN2404或CN2405/份</td><td>1~6</td></tr><tr><td>固化条件（300W/in双灯）/（ft/min） 涂层厚度/mil</td><td>25 5~6</td></tr></table></body></html>\n\n$\\mathrm{1in{=}2.54c m,~\\ 1f t{=}0.30m,~\\ 1m i l{=}25.4\\times10^{-6}m,}$  \n\n表3-49烘烤前后添加杂化低聚物的UV涂料粘接性比较  \n\n\n<html><body><table><tr><td>性能比较</td><td>CN2404</td><td>CN2405</td><td>CN2405</td><td>CN2405</td><td>CN2405</td></tr><tr><td>基材</td><td>铝</td><td>铝</td><td>马口铁</td><td>冷轧钢板</td><td>玻璃</td></tr><tr><td>200℃烘烤时间/min</td><td>5</td><td>5</td><td>8</td><td>12</td><td>8</td></tr><tr><td>烘烤前粘接性/%</td><td>85</td><td>45</td><td>92</td><td>85</td><td>87</td></tr><tr><td>烘烤后粘接性/%</td><td>100</td><td>100</td><td>100</td><td>100</td><td>100</td></tr></table></body></html>  \n\n沙多玛公司商品化杂化低聚物性能及应用见表3-50。  \n\n表3-50沙多玛公司商品化金属丙烯酸酯低聚物  \n\n\n<html><body><table><tr><td>商品名</td><td>化学名称</td><td>黏度（25℃） /mPa·s</td><td>颜色 APHA</td><td>折射率</td><td>T/C</td><td>产品特点</td><td>建议应用领域</td></tr><tr><td>CN2400</td><td>金属丙烯酸酯</td><td>275</td><td>100</td><td></td><td></td><td>很好的附着力，很好的耐刮 擦性，用量1%～20%</td><td>涂料，柔印、凹 印、丝印油墨</td></tr><tr><td>CN2401</td><td>金属丙烯酸酯</td><td>1800</td><td>50</td><td>1,4816</td><td></td><td>很好的附着力，很好的耐刮 擦性，用量1%～20%</td><td>涂料，丝印油墨</td></tr><tr><td>CN2402</td><td>金属丙烯酸酯</td><td>240</td><td>50</td><td>1.4811</td><td></td><td>很好的附着力，很好的耐刮 擦性，用量1%～20%</td><td>金属涂料</td></tr><tr><td>CN2404</td><td>金属聚酯丙烯 酸酯</td><td>500(60℃)</td><td>1G</td><td>1.4824</td><td>18.7</td><td>双官能团，对金属和塑料有 出色的附着力和柔韧性，高温 流回性能</td><td>层压胶黏剂，压 敏胶黏剂，涂料、 油墨</td></tr><tr><td>CN2405</td><td>金属聚氨酯丙 烯酸酯</td><td>21000 (60℃)</td><td>3G</td><td>1.4792</td><td>48.6</td><td>双官能团，对金属和塑料有 出色的附着力和柔韧性，高温 流回性能</td><td>层压胶黏剂，压 敏胶黏剂，涂料， 油墨</td></tr><tr><td>CN2470</td><td>混酯丙烯酸酯</td><td>28000</td><td>2.5G</td><td></td><td></td><td>收对塑料有出色的附着力，低</td><td>胶黏剂，油墨</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 91,
+        "chunk": "# 3.19.1含羧基的丙烯酸酯低聚物  \n\n这也是20世纪末发展起来的一类光固化低聚物，它是在低聚物中引入羧基，对金属附着力有增强作用，特别因羧基存在，具有碱溶性，成为光成像型光固化材料的主体树脂。同  \n\n时羧基含量足够高时，与胺中和后，就可以得到水溶性UV固化低聚物，成为水性UV 固化材料主体树脂。  \n\n低聚物引人羧基可以通过下列方式。  \n\n（1）用马来酸酐共聚物与丙烯酸羟乙酯反应，生成马来酸酐半酯，从而引人羧基和丙烯酰氧基。  \n\n![](images/80986e228d87a61996abe22281559e57f6b65bdb3a4351e9f8a67f51db67be88.jpg)  \n\n（2）用环氧丙烯酸酯中羟基与酸酐反应，生成带羧基的环氧丙烯酸酯。  \n\n![](images/87816c5be6f2f7c29d35290e9bfcb1a9fd72b0f75685b0eb9b8427b68385a5e6.jpg)  \n\n（3）由偏苯三酸酐或均苯四酸二酐与丙烯酸、二元醇缩聚和酯化得到含有羧基的聚酯丙烯酸酯。  \n\n![](images/1069322d04e8a2c01d67df9dcb0da4b947ab1a3ea22b306ce931291632263ea7.jpg)  \n\n（4）二异氰酸酯与二元醇、二羟甲基丙酸反应，再与丙烯酸羟基酯反应，制得带有羧基的聚氨酯丙烯酸酯。  \n\n![](images/7cc0ec16fec2c9e1d44f14744f54409cc36a293ac1cb0ba79fe4983da18384a9.jpg)  \n\n：（5）由二异氰酸酯与丙烯酸羟基酯半加成物与部分酸酐化的环氧丙烯酸酯反应，制得带有羧基的既有环氧丙烯酸酯又有聚氨酯丙烯酸酯结构的低聚物。  \n\n![](images/41e7a564ddc2e01bc757abe03f5c1f50a799f751074bb334351c2cbfd54e10dd.jpg)  \n\n![](images/d6e70b580d9232810be46de70c707e3b49505d075023f350c5cb4284b1c071fd.jpg)  \n\n含羧基丙烯酸酯低聚物的性能和应用见表3-51。  \n\n表3-51含羧基丙烯酸酯低聚物的性能和应用  \n\n\n<html><body><table><tr><td>公司</td><td>产品代号</td><td>化学名称</td><td>官能度</td><td>黏度（25℃） /mPa·s</td><td>酸值 /(mg KOH/g)</td><td>特点和应用</td></tr><tr><td rowspan=\"3\">沙 多 玛</td><td>SB404</td><td>芳香酸丙烯酸半酯 （含PM醋酸酐溶剂）</td><td></td><td>5170</td><td></td><td>快速固化，碱溶性，塑料润湿性好， 可双重固化；用于塑料、木材涂料，抗 蚀剂，阻燃剂</td></tr><tr><td>SB520M35</td><td>芳香酸丙烯酸半酯 （含35%POEA)</td><td></td><td>5332</td><td></td><td>快速固化，与金属、塑料黏合性好， 润湿性、流动性好；用于金属、纸张、塑 料、木材胶黏剂，移印、凹印、丝印油墨</td></tr><tr><td>SB 520A20</td><td>芳香酸甲基丙烯酸 半酯（含20%TPG- DA)</td><td></td><td>579</td><td></td><td>快速固化，高酸值，容易用碱脱除， 铜黏合性好，高光泽、耐溶剂性和酸， 可混杂固化；用于金属、塑料、木材涂 料，抗蚀剂和阻焊剂</td></tr><tr><td>氰特</td><td>EB770</td><td>含羚基的PEA（含 40%HEMA)</td><td>1</td><td>100</td><td></td><td>碱溶性；用于抗蚀剂</td></tr><tr><td rowspan=\"3\">科宁</td><td>5424</td><td>含羚基的PEA</td><td>2</td><td>7000～10000</td><td>85~95</td><td>增强附着力，颜料润湿性好；用于金属、 塑料、木器涂料，胶印、丝印、柔印油墨</td></tr><tr><td>4703</td><td>含羧基的低聚物</td><td></td><td>173</td><td>260</td><td>低黏度，附着力好，耐化学性好，碱 溶性；用于塑料和玻璃涂料，层压胶黏 剂，光成像抗蚀剂</td></tr><tr><td>4173</td><td>含羚基的低聚物</td><td></td><td>4000</td><td>190</td><td>硬度好，附着力好，耐化学性好，碱 溶性；用于金属、塑料涂料，胶黏剂，光 成像抗蚀剂</td></tr><tr><td rowspan=\"3\">长兴</td><td>6173</td><td>含羚基的芳香酸丙 烯酸酯</td><td>1</td><td>3000</td><td></td><td>附着力好，用于金属涂料，胶黏剂</td></tr><tr><td>648</td><td>含羧基的丙烯酸酯</td><td>1</td><td>6000</td><td>210</td><td>碱溶性好，对金属附着力好，耐化学 品性好；用于抗蚀剂</td></tr><tr><td>649</td><td>含羧基的甲基丙烯 酸酯</td><td>1</td><td>4000</td><td>200</td><td>碱溶性好，对金属附着力好，耐化学 品性好；用于抗蚀剂</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 92,
+        "chunk": "# 3.19.2氨基丙烯酸酯低聚物  \n\n这是氨基树脂（包括三聚氰胺树脂、聚酰胺树脂）经丙烯酸酯化而制得的低聚物。  \n\n三聚氰胺经甲醛加合，再与醇醚化后，得到甲醚化或丁醚化三聚氰胺树脂，通过与丙烯酸羧基酯酯交换引入丙烯酰氧基，就成为氨基丙烯酸酯低聚物，具有硬度高，耐热性和耐候性好，优良的耐化学品性和机械强度。因低聚物中存有大量烷氧基，也可热固化，作为光固化和热固化双重固化材料。  \n\n聚酰胺树脂中氨基与多官能度丙烯酸酯，经过迈克尔加成，引人丙烯酸酯，成为氨基丙烯酸酯低聚物，具有很好的柔韧性和力学性能，用于涂料和油墨。表3-52 列举了氨基丙烯酸酯低聚物的性能和应用。  \n\n表3-52氨基丙烯酸酯低聚物的性能和应用  \n\n\n<html><body><table><tr><td>公司</td><td>产品代号</td><td>化学名称</td><td></td><td>官能度黏度(25℃)/mPa·s</td><td>特点和应用</td></tr><tr><td rowspan=\"3\">江苏三木</td><td>6115</td><td>基以脲酸树脂为基础的氨</td><td>1~2</td><td>600～1000</td><td>低黏度，柔韧性好，附着力佳</td></tr><tr><td>6116</td><td>为基矿酵三氨胺树脂</td><td>2~3</td><td>800~1200</td><td>高反应活性，高硬度</td></tr><tr><td>6117</td><td>以甲醚化三聚氰胺树脂 为基础的氨基丙烯酸酯</td><td>3~4</td><td>1200~2000</td><td>快速固化，高交联密度</td></tr><tr><td rowspan=\"2\">中山千叶 合成</td><td>UN111</td><td>三聚氰胺丙烯酸树脂</td><td>3</td><td>90~160s</td><td>固化速率快，光泽好，硬度高，黏 度低，丰满度好，耐黄变，用于PVC</td></tr><tr><td>UN112</td><td>聚丙烯酰胺树脂</td><td>2</td><td>100～150s</td><td>扣板、摩托车、机壳涂料 耐黄变，黏度低，柔韧性好；用于 塑料油墨和各种油墨</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 93,
+        "chunk": "# 3.20.1环氧丙烯酸酯低聚物的合成  \n\n（1）环氧大豆油丙烯酸酯的合成  \n\n![](images/9c96e9d6bf626ca1afb39280d09d9d8d90b18cda5b5f0998f9a80e35132cc232.jpg)  \n\n在三口烧瓶中加人一定量环氧大豆油（环氧值0.42)，升温至85℃，滴加含1.5%的三苯基磷、0.1%的对甲氧基苯酚和一定量AA（环氧基：羧基=1.1：1，摩尔比）混合液，加毕升温至 $110^{\\circ}\\mathrm{C}$ ，反应至酸值 $<8\\mathrm{mg}~\\mathrm{KOH}/\\mathbf{g}$ ，停止反应得到环氧大豆油丙烯酸酯，得率$95\\%$ 。反应配比对酯化率的影响见表3-53。  \n\n表3-53 反应配比对酯化率的影响①  \n\n\n<html><body><table><tr><td>环氧基·羧基(摩尔比)</td><td>1:1</td><td>1.1:1</td><td>1.2 : 1</td></tr><tr><td>酯化率/%</td><td>84.3</td><td>95.0</td><td>96.1</td></tr></table></body></html>\n\n$\\Phi$ 反应温度 $110^{\\circ}\\mathsf{C}$ ，反应时间8h，催化剂三苯基磷 $1.5\\%$  \n\n（2）不同催化剂下环氧丙烯酸酯的合成在三口烧瓶中加入 $\\boldsymbol{1.05}\\mathbf{mol}\\ 828$ 环氧树脂（环氧值0.548）和0.02%的阻聚剂，加热搅拌，升温至一定温度，滴加1mol丙烯酸和1%的环氧树脂量的催化剂混合液，1h滴完，控制反应温度，定时取样测酸值，当反应体系酸值 ${\\bf<3m g~K O H/g}$ 时停止反应，得到环氧丙烯酸酯，见表3-54。  \n\n![](images/d4bc967c39eb533d926e18bada0e1ff8e6aa91c1fcead83bc3738b197446bb8e.jpg)  \n表3-54不同催化剂下环氧丙烯酸酯的合成  \n\n<html><body><table><tr><td>序号</td><td>催化剂</td><td>反应温度/℃</td><td><3mgKOH/g所需时间/h</td><td>产品外观</td><td>固化速率/s</td></tr><tr><td>1</td><td>三乙胺</td><td>95</td><td>8</td><td>略带蓝色</td><td>4</td></tr><tr><td>2</td><td>三乙胺</td><td>105</td><td>3.5</td><td>略带蓝色</td><td>4</td></tr><tr><td>3</td><td>三乙胺</td><td>115</td><td>1.5</td><td>明显偏黄色</td><td>7</td></tr><tr><td>4</td><td>四乙基溴化铵</td><td>95</td><td>5</td><td>近似于无色</td><td>4</td></tr><tr><td>5</td><td>四乙基溴化铵</td><td>105</td><td>3</td><td>近似于无色</td><td>4</td></tr><tr><td>6</td><td>四乙基溴化铵</td><td>115</td><td>1.5</td><td>明显偏黄色</td><td>7</td></tr><tr><td>7</td><td>三苯基磷</td><td>95</td><td>6</td><td>近似于无色</td><td>4</td></tr><tr><td>8</td><td>三苯基磷</td><td>105</td><td>3</td><td>近似于无色</td><td>4</td></tr><tr><td>9</td><td>三苯基磷</td><td>115</td><td>1.5</td><td>明显偏黄色</td><td>7</td></tr><tr><td>10</td><td>三苯基磷：四乙基溴化铵1：1</td><td>95</td><td>6</td><td></td><td></td></tr><tr><td>11</td><td>三苯基磷：三乙胺2：3</td><td>105</td><td>3.5</td><td></td><td></td></tr><tr><td>12</td><td>三苯基磷：三乙胺3：2</td><td>105</td><td>4.5</td><td></td><td></td></tr><tr><td>13</td><td>多元催化剂</td><td>95</td><td>4.5</td><td></td><td></td></tr><tr><td>14</td><td>多元催化剂</td><td>105</td><td>2.5</td><td></td><td></td></tr></table></body></html>  \n\n（3）环氧丙烯酸酯的合成在三口烧瓶中加人25g环氧树脂（E-44)，加人适量甲苯溶解，加热至85℃，滴加溶有0.15g对苯二酚、0.6g二甲苯胺和7.8g丙烯酸的混合溶液，反应1h，升温至95℃反应4h，体系酸值<3mgKOH/g，减压蒸馏，除去甲苯和未反应的丙烯酸得到环氧丙烯酸酯。  \n\n(4）环氧丙烯酸酯的合成在三口烧瓶中加入计算量环氧树脂（E-44)、对甲氧基苯酚，升温，缓慢滴加计算量的丙烯酸（羧基与环氧基摩尔比为1：1）和0.6～0.9份催化剂三甲基苄基溴化铵，100～105℃反应2h，酸值<5mgKOH/g，停止反应，得环氧丙烯酸酯，反应转化率≥95%。不同催化剂种类的影响见表3-55。  \n\n表3-55不同催化剂种类的影响  \n\n\n<html><body><table><tr><td>催化剂</td><td>反应时间/min</td><td>残余酸值率P</td><td>丙烯酸转化率/%</td></tr><tr><td>四丁基澳化铵</td><td>100</td><td>0.039</td><td>96.1</td></tr><tr><td>三甲基苄基溴化铵</td><td>100</td><td>0.064</td><td>93.6</td></tr><tr><td>三甲基苄基氯化铵</td><td>100</td><td>0.096</td><td>90.4</td></tr><tr><td>N,N-二甲基苄铵</td><td>100</td><td>0.165</td><td>83.5</td></tr></table></body></html>  \n\n（5）酚醛环氧丙烯酸树脂（FA）的合成  \n\n![](images/39a7bed97d81ed1f574e8169c5da1c4eb783987429ef8ae3198a91dd2894d379.jpg)  \n\n在三口烧瓶中加入酚醛环氧树脂（F-51）和适量对甲氧基苯酚，升温至 $90^{\\circ}\\mathrm{C}$ 搅匀，滴加丙烯酸（羧基与环氧基等摩尔比）和适量 $N,N^{\\prime}$ -二甲基苄胺，维持反应温度 $100^{\\circ}\\mathrm{C}$ 反应5h左右，至酸值 ${\\leqslant}5\\mathrm{mg}\\mathrm{KOH}/\\mathbf{g}$ ，趁热出料，或降温至 $60^{\\circ}\\mathrm{C}$ ，加入适量稀释剂甲基丙烯酸羟乙酯搅匀后出料。  \n\n（6）甲基酚醛环氧丙烯酸树脂的合成在三口烧瓶中加人 $50\\mathbf{g}$ 甲基酚醛环氧树脂JE43、$\\scriptstyle22g$ 醋酸丁氧基乙酯，加热至 $80^{\\circ}\\mathrm{C}$ 搅匀，加人 $0.2{\\bf g}$ 对甲氧基苯酚、 $_{15.58}$ 丙烯酸以及催化剂 $\\left(0,25\\mathrm{mmol}\\right.$ 四丁基溴化铵、 $0.25\\mathrm{mmol}$ 三乙酰丙酮铬)，搅匀后升温至 $120^{\\circ}\\mathrm{C}$ 反应6h得到甲基酚醛环氧丙烯酸树脂。  \n\n（7）低黏度环氧丙烯酸酯的合成在三口烧瓶中加人1mol聚乙二醇200、2mol双酚A环氧树脂、 $0.1\\%$ 的三乙胺， $100^{\\circ}\\mathrm{C}$ 反应 $5\\mathrm{h}$ 。降温至 $80^{\\circ}\\mathrm{C}$ 加入计算量的丙烯酸（与环氧基等摩尔比)、 $0.1\\%$ 的对甲氧基苯酚，升温至 $100{\\sim}110^{\\circ}\\mathrm{C}$ ，反应至酸值 ${\\leqslant}5\\mathrm{mg}\\ \\mathrm{KOH}/\\mathbf{g}$ 得到低黏度环氧丙烯酸酯。不同双羟基化合物改性EA的黏度见表3-56。  \n\n表3-56不同双羟基化合物改性EA的黏度  \n\n\n<html><body><table><tr><td>项 目</td><td>乙二醇</td><td>一缩二乙醇</td><td>聚乙二醇200</td><td>聚乙二醇300</td><td>聚乙二醇400</td><td>双酚A</td><td>未改性</td></tr><tr><td>平均醚键数/个</td><td>2</td><td>3</td><td>4.1</td><td>6.4</td><td>8.6</td><td>一</td><td>一</td></tr><tr><td>环氧树脂黏度/s</td><td>2.81</td><td>2.53</td><td>1.94</td><td>2.71</td><td>3.31</td><td>4.47</td><td>2.69</td></tr><tr><td>环氧丙烯酸酯黏度/s</td><td>36.97</td><td>12.60</td><td>8.53</td><td>16.72</td><td>19.90</td><td>19.43</td><td>14.00</td></tr></table></body></html>  \n\n![](images/e3dff03f43c8b7e19132cdc84941dc539a586b386698adcda37e51b1c014b9bd.jpg)  \n\n（8）低黏度环氧丙烯酸酯的合成在三口烧瓶中加人1mol双酚A环氧树脂、 $0.2\\mathrm{mol}$ 聚醚多元醇、 $0.25\\%$ 的催化剂三乙胺，升温至 $110^{\\circ}\\mathrm{C}$ ，反应2.5h，测环氧值，降温加人0.1%的对羟基苯甲醚，缓慢滴加1.2mol丙烯酸（与测定环氧等值）并缓慢升温至115℃，反应 $^{3\\mathrm{h}}$ ，测酸值 ${\\bf\\ K O H/g}$ ，停止反应，趁热放料，得低黏度环氧丙烯酸酯。  \n\n未改性环氧丙烯酸酯 $\\eta_{60}=10\\mathrm{{Pa}\\cdot\\mathrm{{s}}}$  \n\n柔性 $\\boldsymbol{0.9}\\mathbf{mm}$ 柔性 $0.5\\mathrm{mm}$  \n\n（9）低黏度环氧丙烯酸酯的合成在三口烧瓶中加人100g828环氧树脂、20g二缩三乙二醇（扩链剂）和 $0.5{\\bf g}$ 三乙胺(催化剂)，升温 $(70\\pm5)^{\\circ}\\mathrm{C}$ 反应，每隔 $30\\mathrm{{min}}$ 测环氧值至所需时停止反应。按环氧值：丙烯酸为 $1:1$ 加人丙烯酸、三乙胺（改性环氧与丙烯酸量的 $1\\%$ )、对苯二酚（改性环氧的 $0.02\\%$ ）升温至（ $100\\pm5)^{\\circ}\\mathrm{C}$ ，反应至酸值 ${\\bf<5m g~K O H/g}$ 得到低黏度环氧丙烯酸酯。  \n\n（10）低黏度环氧丙烯酸酯的合成在三口烧瓶中加人一缩二乙二醇与环氧树脂E-44（摩尔比为1：10）和催化剂四丁基溴化铵（或四甲基氯化铵、三乙基苄基氯化铵)，100℃反应2h，得改性环氧树脂，黏度低于原环氧树脂（表3-57)，降温至80℃缓慢滴加计算量丙烯酸（羧基与环氧基摩尔比为1：1）和0.6～0.9份催化剂，100～105℃反应2h，当酸值<5mgKOH/g时停止反应，得低黏度环氧丙烯酸酯。  \n\n表3-57催化剂种类对产物黏度的影响  \n\n\n<html><body><table><tr><td>催化剂</td><td>四丁基溴化铵</td><td>四甲基氯化铵</td><td>三乙基苄基氯化铵</td><td>N,N-二甲基苄胺</td><td>E-44</td></tr><tr><td>黏度/Pa·s</td><td>5.4</td><td>6.0</td><td>6.4</td><td>8.6</td><td>10.3</td></tr></table></body></html>  \n\n（11）脂肪族环氧丙烯酸酯的合成  \n\n在三口烧瓶中加人lmol丙烯酸和lmol一缩二乙二醇二缩水甘油醚，1%的催化剂N,N-二甲基苄胺和0.2%的阻聚剂对甲氧基苯酚，升温至100℃反应，至酸值<5mgKOH/g停止反应，得脂肪族环氧丙烯酸酯一缩二乙二醇二缩水甘油醚二丙烯酸酯。25℃黏度为800mPa·s，仅为双酚A环氧丙烯酸酯的1/1000，固化速率也比双酚A环氧丙烯酸酯快。  \n\n（12）脂肪族环氧丙烯酸酯的合成在三口烧瓶中加人0.5mol丁二醇缩水甘油醚、0.3%的对羟基苯甲醚、0.8%的三苯基麟，升温至80℃，滴加1mol丙烯酸，100～105℃反应2～6h，当酸值<6mgKOH/g时停止反应，得脂肪族环氧丙烯酸酯：丁二醇二缩水甘油醚二丙烯酸酯，为黏状淡黄色透明液体，酸值为5.5mgKOH/g时，黏度（25℃）为$975\\mathbf{m}\\mathbf{Pa}\\cdot\\mathbf{s}$ ，密度为 $1.065\\mathrm{g}/\\mathrm{cm}^{3}$ 。  \n\n（13）脂环族环氧丙烯酸酯的合成  \n\n![](images/c11576dcfd73a6597dae09cf4e58962dbb48e21d196b5d0b9f2b160fa290c8ef.jpg)  \n\n在三口烧瓶中加入TDE-85环氧树脂（4,5-环氧已烷-1,2-二甲酸二缩水甘油酯）和1%的四甲基氯化铵，缓慢升温，并滴加丙烯酸（酸当量/环氧当量为1.02～1.05：1)，在105～115℃反应3.5～4h，当酸值降至15mgKOH/g以下时停止反应，得到脂环族环氧丙烯酸酯树脂。  \n\n外观：浅黄色黏稠树脂。  \n\n黏度： $2.6\\mathrm{Pa}\\cdot\\mathrm{s}$ 卷固化速率（ $4\\%$ 的1173)： ${\\bf40s}$ 。  \n\n（14）脂环族环氧双甲基丙烯酸酯的合成  \n\n![](images/8fd9cddce735175f08be9ac216ad85c042eb0048611a37d48a3f4723972d02a8.jpg)  \n\n在三口烧瓶中加人50g（3,4-环氧基）环已基甲酸（3,4-环氧基）环已基甲酯（EPC)和400×10-6的对甲氧基苯酚，搅匀，升温至80℃，滴加27.5g甲基丙烯酸和0.4g三乙基苄基氯化铵混合液，90℃反应2h，升温至100～108℃反应5～6h，当酸值<5mgKOH/g时停止反应，趁热出料，得脂环族环氧双甲基丙烯酸酯EPCDMA。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 94,
+        "chunk": "# （15）己二酸改性环氧丙烯酸酯的合成  \n\n![](images/418f4d0dffb7db23c5c30fad3ed15ba69ee4fb71b97accc9ab99e0072b51359a.jpg)  \n\n在三口烧瓶中加人一定量的环氧树脂（E-51)、已二酸（E-51：已二酸=1：0.3，质量比）和四甲基氯化铵，升温至 $90\\%$ ，反应至酸值接近零时，滴加计量的丙烯酸和2,6-二叔丁基对甲酚混合物， $30\\mathrm{\\sim}40\\mathrm{min}$ 加毕，升温至 $95\\sim100\\mathrm{^{\\circ}C}$ ，反应至酸值 $\\leq5\\mathrm{mg}\\ \\mathrm{KOH/g}$ ，降温过滤出料，得己二酸改性环氧丙烯酸酯，无色或接近无色透明黏稠体，黏度（ $50^{\\circ}\\mathrm{C}$ ）为$3{\\sim}4\\mathrm{Pa}\\cdot\\mathbf{s} $ 。己二酸用量对树脂黏度的影响见表3-58。  \n\n表3-58 己二酸用量对树脂黏度的影响  \n\n\n<html><body><table><tr><td>己二酸：环氧树脂</td><td>树脂黏度（50℃）/Pa·s</td></tr><tr><td>0.5:1</td><td>>10</td></tr><tr><td>0.4:1</td><td>≥6</td></tr><tr><td>0.3:1</td><td>3~4</td></tr></table></body></html>  \n\n（16）已二酸改性环氧丙烯酸酯的合成在三口烧瓶中加入环氧树脂、催化剂三乙胺或2-甲基吡啶、抗氧剂、对羟基苯甲醚及己二酸（环氧树脂量的 $30\\%$ ，搅拌 $3\\mathrm{{min}}$ ，通人 $\\mathbf{N}_{2}$ ，加热至 $(120\\pm2)^{\\circ}\\mathrm{C}$ ，保温2h，测酸值达到理论值时，加入计算量的丙烯酸（剩余环氧基与羧基等摩尔比)， $(110\\pm2)^{\\circ}\\mathrm{C}$ 反应，至酸值 ${<}5\\mathrm{mg}\\mathrm{KOH/g}$ ，得己二酸改性EA，加人 $20\\%$ 的TPGDA搅匀出料，其性能：黏度（ $25\\mathrm{^\\circC}$ ） $85\\mathrm{{Pa}\\cdot\\mathrm{{s}}},$ ：折射率1.5482。不同催化剂的催化性能见表3-59。  \n\n表3-59不同催化剂的催化效果  \n\n\n<html><body><table><tr><td rowspan=\"2\">性能</td><td colspan=\"4\">催化剂</td></tr><tr><td>无</td><td>三乙胺</td><td>2-甲基吡啶</td><td>三苯基麟</td></tr><tr><td>反应时间/h</td><td>20(酸值45mgKOH/g)</td><td>5.5</td><td>4.5</td><td>5.0</td></tr><tr><td>黏度(25℃)/Pa·s</td><td>150</td><td>95</td><td>80</td><td>75</td></tr><tr><td>外观(Fe-Co比色)</td><td>3#</td><td>2#</td><td>1#</td><td>2#</td></tr><tr><td>外观</td><td>透明</td><td>透明</td><td>透明</td><td>透明</td></tr></table></body></html>\n\n$\\Phi$ 酸值 ${<}5\\mathrm{m}\\mathbf{g}\\ \\mathbf{K}{\\mathrm{OH/}}\\mathbf{g}$ 量  \n\n（17）马来酸酐改性环氧丙烯酸酯的合成在三口烧瓶中加入计算量的马来酸酐和不同分子量的聚乙二醇（按马来酸酐：聚乙二醇 $=1.05:1$ ，摩尔比)， $75\\mathrm{^\\circC}$ 反应 $100\\mathrm{{min}}$ ，制得不同分子量的马来酸聚乙二醇单酯，通过测定体系酸值，确定转化率在 $93\\%$ 。 3  \n\n将合成的一系列马来酸聚乙二醇单酯与环氧树脂（618环氧树脂）的甲苯溶液，按与环氧基当量比 $0.1:1$ 的比例加人三口烧瓶中，再加入适量催化剂三乙胺和阻聚剂对苯二酚，在 $100^{\\circ}\\mathrm{C}$ 反应0.5h，当体系酸值为 $1.5\\mathrm{mg}\\ \\mathrm{KOH}/\\mathbf{g}$ 时，滴加计算量的丙烯酸，1h加毕，保温，至体系酸值 ${<}5\\mathrm{mg}\\ \\mathrm{KOH/g}$ 停止反应，减压蒸馏除去甲苯，得到改性环氧丙烯酸树脂。  \n\n改性环氧丙烯酸酯的性能见表3-60。  \n\n（18）丁二酸酐改性甲基酚醛环氧丙烯酸树脂的合成将50g线型甲基酚醛环氧树脂(JF43)、22g醋酸丁氧乙酯加入到三口烧瓶中，加热到80℃搅拌至溶解，加入0.2g阻聚剂、15.5g丙烯酸及1.25mol复合催化剂［四丁基溴化铵/乙酰丙酮（Ⅲ)］，升温至120℃反应至酸值基本不变，得JFA树脂溶液。  \n\n表3-60改性环氧丙烯酸酯的性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">试样</td><td rowspan=\"2\">聚乙二醇</td><td rowspan=\"2\">涂料黏度 (涂-4杯)/s</td><td colspan=\"7\">涂膜性能</td></tr><tr><td>柔韧性 /mm</td><td>附着力 /级</td><td>硬度 /H</td><td>耐冲击强度 /kg·cm</td><td>光泽度 /%</td><td>15%NaCl 48h</td><td>10%NCO3 48h</td></tr><tr><td>EPo</td><td></td><td>147</td><td>4</td><td>2</td><td>5</td><td>20</td><td>92</td><td>无变化</td><td>无变化</td></tr><tr><td>EP1</td><td>乙二醇</td><td>74</td><td>2</td><td>1</td><td>3</td><td>40</td><td>111</td><td>无变化</td><td>无变化</td></tr><tr><td>EP2</td><td>聚乙二醇200</td><td>69</td><td>1</td><td>1</td><td>3</td><td>≥50</td><td>101</td><td>无变化</td><td>发白</td></tr><tr><td>EP3</td><td>聚乙二醇300</td><td>66</td><td>1</td><td>1</td><td>2</td><td>≥50</td><td>105</td><td>发白</td><td>溶解</td></tr><tr><td>EP</td><td>聚乙二醇400</td><td>60</td><td>1</td><td>1</td><td>2</td><td>≥50</td><td>105</td><td>发白</td><td>发白</td></tr></table></body></html>  \n\n将40gJFA树脂溶液（65%固含量）、适量醋酸丁氧乙酯（使体系溶剂含量35%）、0.05g阻聚剂加入到三口烧瓶中，搅拌加热至80～90℃，加人9.8g丁二酸酐于120℃反应4h，得丁二酸酐改性甲基酚醛环氧丙烯酸树脂。  \n\n（19）丁二酸酐改性酚醛环氧丙烯酸酯的合成在三口烧瓶中加入48g质量分数为61.7%的含环氧基丙烯酸改性酚醛环氧F-44树脂的二氧六环溶液，0.05g对苯二酚、0.5g溴化季铵盐和31g质量分数为22.5%的丁二酸酐的二氧六环溶液，95℃反应3h，得到碱溶性的酸酐改性FA树脂。不同投料比时产物的性能见表3-61。  \n\n表3-61不同投料比时产物的性能  \n\n\n<html><body><table><tr><td>投料比(环氧基：羟基：丁二酸酐)</td><td>产物碱溶性</td><td>UV固化后附着力</td><td>热固化后附着力</td></tr><tr><td>3:7:8</td><td>溶于1%的NazCO3</td><td>3</td><td>1</td></tr><tr><td>3:7:7</td><td>溶于1%的NaCO3</td><td>3</td><td>1</td></tr><tr><td>3:7:6</td><td>溶于1%的NazCO3</td><td>3</td><td>1</td></tr><tr><td>3:7:5</td><td>溶于1%的NazCO3</td><td>3</td><td>1</td></tr><tr><td>5·5·6</td><td>溶于5%的NazCO3</td><td>1</td><td>1</td></tr><tr><td>5:5·5</td><td>溶于5%的Na2CO3</td><td>1</td><td>1</td></tr><tr><td>5:5:4</td><td>稍溶于5%的NaCO3</td><td>1</td><td>1</td></tr><tr><td>5:5:3</td><td>不溶于5%的NaCOs</td><td>1</td><td>1</td></tr></table></body></html>\n\n注：投料比：环氧基：羟基：丁二酸酐=3：7：（5～6）为最佳。  \n\n（20）偏苯三酸酐改性的甲基丙烯酸环氧酯的合成在三口烧瓶中加人一定量的双酚A环氧树脂和甲基丙烯酸（环氧基和羧基的摩尔比为1：1)、1.5%的催化剂四乙基氯化铵和适量的对甲氧基苯酚，升温至90～110℃反应1.5h，降温至60℃，加人偏苯三酸酐，100℃继续反应1.5h，停止反应得到偏苯三酸酐改性的甲基丙烯酸环氧酯。  \n\n（21）碱溶性环氧丙烯酸酯（或酚醛环氧丙烯酸酯）的合成在三口烧瓶中加人一定量的环氧树脂E-51（或F-51）和少量对甲氧基苯酚，搅拌升温至65℃，滴加一定量的丙烯酸（环氧基：羧基的摩尔比为1：1）和苄基三甲基氯化铵，1h滴完，在90～100℃反应至酸值<5mgKOH/g时停止反应，降温至60℃，加人一定量的马来酸酐，升温至75～80℃，当酸值达到所需值时停止反应，得到马来酸酐改性环氧丙烯酸树脂E-51AM（或F-51AM)。  \n\n马来酸酐改性环氧丙烯酸树脂的性能见表3-62。  \n\n表3-62马来酸酐改性环氧丙烯酸树脂的性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">性能</td><td colspan=\"4\">马来酸酐：OH</td></tr><tr><td>0:1</td><td>0.3:1</td><td>0.7:1</td><td>1:1</td></tr><tr><td>黏度/Pa·s</td><td></td><td></td><td></td><td></td></tr><tr><td>E-51AM</td><td>77</td><td></td><td>96</td><td>160</td></tr><tr><td>F-51AM</td><td>108</td><td></td><td>180</td><td>320</td></tr><tr><td>碱溶性</td><td></td><td></td><td></td><td></td></tr><tr><td>E-51AM</td><td>不溶</td><td>留有余膜</td><td>全溶</td><td>全溶</td></tr><tr><td>F-51AM</td><td>不溶</td><td>留少量余膜</td><td>全溶</td><td>全溶</td></tr><tr><td>最低固化光量/（mJ/cm²）</td><td></td><td></td><td></td><td></td></tr><tr><td>E-51AM</td><td>1.26</td><td>1.02</td><td>0.51</td><td>0.36</td></tr><tr><td>F-51AM</td><td>0.94</td><td>0.72</td><td>0.36</td><td>0.26</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 95,
+        "chunk": "# (22）碱溶性甲基酚醛环氧丙烯酸酯的合成  \n\n![](images/1601c271d05e55308a60df852ed5fb5a70bc2721fb8dd6a08d6d97e3f63d29ce.jpg)  \n\n在三口烧瓶中加人 $50\\mathbf{g}$ 甲基酚醛环氧树脂JF43（环氧值0.428)、 $22g$ 醋酸丁氧乙酯，加热至 $80^{\\circ}\\mathrm{C}$ ，搅拌至树脂全溶，加入 $0.2{\\bf g}$ 对甲氧基苯酚、 $15.5\\mathbf{g}$ 丙烯酸及 $\\boldsymbol{1.25\\mathrm{mmol}}$ 催化剂［四丁基溴化铵和乙酰丙酮铬（Ⅲ）等摩尔比]，升温至 $120^{\\circ}\\mathrm{C}$ ，反应至体系酸值基本不变为止，得甲基酚醛环氧丙烯酸树脂JFA溶液。  \n\n将 $40\\mathbf{g}$ JFA树脂溶液（ $65\\%$ 固含量)、适量醋酸丁氧乙酯（用于调节体系溶剂含量至$35\\%$ ）及 $0.05\\mathbf{g}$ 对甲氧基苯酚加人三口烧瓶中，搅拌升温至 $80\\sim90^{\\circ}{\\mathrm{C}}$ ，加人 $0.098\\mathrm{mol}$ 多元羧酸酐·于 $120^{\\circ}\\mathrm{C}$ 反应至酸值基本不变为止。羧基化甲基酚醛环氧丙烯酸酯的性能见表3-63。  \n\n表3-63羧基化甲基酚醛环氧丙烯酸酯的性能  \n\n\n<html><body><table><tr><td>酸酐</td><td>树脂酸值/(mgKOH/g)</td><td>酸酐转化率/%</td><td>黏度(60℃)/mPa·s</td></tr><tr><td>苯酐</td><td>93.5</td><td>84.3</td><td>4120</td></tr><tr><td>马来酸酐</td><td>112.1</td><td>76.4</td><td>4850</td></tr><tr><td>丁二酸酐</td><td>104.5</td><td>84.4</td><td>880</td></tr><tr><td>四氢苯酐</td><td>88.1</td><td>89.6</td><td>1700</td></tr><tr><td>六氢苯酐</td><td>87.7</td><td>89.5</td><td>1830</td></tr><tr><td>甲基六氢苯酐</td><td>86.9</td><td>87.4</td><td>1500</td></tr><tr><td>偏苯三酸酐</td><td>128.4</td><td>98.4</td><td>8500（90℃)</td></tr><tr><td>甲基纳迪克酸酐</td><td>94.6</td><td>55.1</td><td>548</td></tr></table></body></html>\n\n（23）碱溶性聚氨酯改性环氧丙烯酸酯（或酚醛环氧丙烯酸酯）的合成在三口烧瓶中  \n\n加入一定量的环氧树脂E-51（或F-51）和少量对甲氧基苯酚，搅拌升温至 $65^{\\circ}\\mathrm{C}$ ，滴加一定量的丙烯酸（环氧基与羧基的摩尔比为 $1:1$ ）和苄基三甲基氯化铵，1h滴完，在 $90\\sim$ $100^{\\circ}\\mathrm{C}$ 反应至酸值 ${<}5\\mathrm{mg}\\ \\mathrm{KOH/g}$ 时停止反应，降温至 $60^{\\circ}\\mathrm{C}$ ，加人一定量的马来酸酐（马来酸酐：羟基 $=0.7:1)$ ，升温至 $75{\\sim}80^{\\circ}\\mathrm{C}$ 反应，当酸值达到所需值时停止反应，得到马来酸酐改性环氧丙烯酸树脂。再加人一定量TDI-HEA半加成物（ $\\mathrm{OH^{-}}$ 与—NCO摩尔比为$1:1)$ ，在 $65^{\\circ}\\mathrm{C}$ 反应至—NCO消失，得聚氨酯改性环氧丙烯酸树脂EATH(或FATH)。聚氨酯改性环氧丙烯酸树脂的性能见表3-64。  \n\n表3-64聚氨酯改性环氟丙烯酸树脂性能  \n\n\n<html><body><table><tr><td>样品</td><td>黏度/Pa·s</td><td>碱溶性</td><td>最低固化光量/（mJ/cm²）</td></tr><tr><td>EATH</td><td>280</td><td>全溶</td><td>0.72</td></tr><tr><td>FATH</td><td>400</td><td>全溶</td><td>0.51</td></tr></table></body></html>  \n\n（24）聚酯改性环氧丙烯酸酯的合成在装有氮气管的三口烧瓶中加人 $2\\mathrm{mol}$ 马来酸酐和 $\\scriptstyle1{\\mathrm{mol}}$ 端羟基聚丁二烯橡胶及少量对甲苯磺酸，升温通氮气至 $100^{\\circ}\\mathrm{C}$ 反应至酸值降到理论值。停止反应得到端羧基聚酯。加人环氧丙烯酸酯（由1mol环氧树脂与1mol丙烯酸反应制得)、 $0.8\\%$ 总量的四正丁基溴化铵和适量对羟基苯甲醚， $95\\mathrm{^{\\circ}C}$ 反应2h，当酸值降到 $_{5\\mathrm{m}\\tt g}$ $\\mathtt{K O H/g}$ 时停止反应，制得聚酯改性环氧丙烯酸酯。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 96,
+        "chunk": "# 3.20.2聚氨酯丙烯酸酯低聚物的合成",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 97,
+        "chunk": "# （1）芳香族聚氨酯丙烯酸酯的合成  \n\n![](images/66cc6d8a1ccb7090d467d49b516791bf7551af9d23c223862731e7f22501aa7f.jpg)  \n\n在三口烧瓶中加人 $0.5\\mathrm{mol}$ 聚醚二元醇（PPO210）、1mol甲苯二异氰酸酯（TDI)、0.1%的二月桂酸二丁基锡、0.05%的对甲氧基苯酚，60℃反应至—NCO值到计算值，再加人lmol丙烯酸羟乙酯（HEA)，升温至70～75℃，反应至—NCO值接近于0，得到聚醚型聚氨酯丙烯酸酯。不同组分的聚氨酯丙烯酸酯的性能见表3-65。  \n\n表3-65不同组分的聚氨酯丙烯酸酯的性能  \n\n\n<html><body><table><tr><td>序号</td><td>组成比(摩尔比)</td><td>碘值/(mgKOH/g)</td><td>固化速率/s</td><td>硬度/H</td><td>附着力</td></tr><tr><td>1</td><td>PPO210:HEA:TDI=0.5:1.0:1</td><td>61.2</td><td>7</td><td>2</td><td>差</td></tr><tr><td>2</td><td>PPO210:HEA:TDI=0.4:1.2:1</td><td>72.6</td><td>7</td><td>2</td><td>中</td></tr><tr><td>3</td><td>PPO210:HEA:TDI=0.3:1.4；1</td><td>78.8</td><td>7.5</td><td>>3</td><td>优</td></tr><tr><td>4</td><td>PPO210·HEA:TDI=0.2:1.6:1</td><td>90.4</td><td>7.5</td><td>>3</td><td>中</td></tr><tr><td>5</td><td>PPO210:HEA:TDI=0.1:1.8:1</td><td>104.9</td><td>8</td><td>>3</td><td>中</td></tr></table></body></html>  \n\n（2）芳香族聚醚聚氨酯丙烯酸酯的合成在三口烧中加人1mol聚乙二醇、 $100\\%$ （质量分数）溶剂乙酸丁酯，滴加 $2\\mathrm{mol}$ 甲苯二异氰酸酯和 $0.3\\%$ （质量分数）的二月桂酸二丁基锡混合液，升温至 $70^{\\circ}\\mathrm{C}$ 反应1.7h，降至 $50^{\\circ}\\mathrm{C}$ 反应 $1.5\\mathrm{h}$ 。然后降至室温，加人 $2\\mathrm{mol}$ 丙烯酸羟乙酯，升温至 $70^{\\circ}\\mathrm{C}$ ，反应至—NCO基团消失，得到聚醚聚氨酯丙烯酸酯。不同聚乙二醇合成聚氨酯丙烯酸酯的性能见表3-66。  \n\n表3-66不同聚乙二醇合成聚氨酯丙烯酸酯的性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">PEG分子量</td><td rowspan=\"2\">PUA分子量</td><td colspan=\"4\">固化膜性能</td></tr><tr><td>柔韧性/mm</td><td>拉伸强度/MPa</td><td>断裂伸长率/%</td><td>硬度</td></tr><tr><td>400</td><td>1.76×103</td><td>5</td><td>20.2</td><td>21.2</td><td>1.45</td></tr><tr><td>800</td><td>2.85×103</td><td>2.5</td><td>16.7</td><td>35.7</td><td>0.85</td></tr><tr><td>2000</td><td>3.08×103</td><td>1</td><td>15.5</td><td>62.4</td><td>0.85</td></tr><tr><td>4000</td><td>1.87×10</td><td>0.5</td><td>7.5</td><td>67.9</td><td>0.87</td></tr></table></body></html>  \n\n(3)芳香族聚醚聚氨酯丙烯酸酯的合成在三口烧瓶中加入聚氧化丙烯醚N210(经真空加热脱水，含水量<0.1%)和甲苯二异氰酸酯(—OH：—NCO=0.4：1),用少量有机酸调体系 $\\mathsf{p H}$ 值到5，加人 $0.05\\%$ 的二月桂酸二丁基锡 $20\\%$ 的乙酸丁酯溶液),升温至 $35\\mathrm{{^\\circC}}$ ,维持反应温度 $(40\\pm2)^{\\circ}\\mathrm{C}$ ，反应1h，测体系—NCO含量，当达到理论值时，升温至 $60^{\\circ}\\mathrm{C}$ ，滴加丙烯酸羟丙酯 $(\\mathrm{~-~}0\\mathrm{H}:-\\mathrm{NCO}{=}1:1)$ 、二月桂酸二丁基锡、2,6-二叔丁基对甲酚混合物， $^\\mathrm{1h}$ 滴加完毕，$60{\\sim}65^{\\circ}\\mathrm{C}$ 反应1h，当—NCO含量 ${<}1\\%$ 时，升温至 $(80\\pm2)^{\\circ}\\mathtt{C}$ ，反应至—NCO含量 $<0.5\\%$ ，再加入封端剂丁醇，继续反应得到无色透明的聚醚聚氨酯丙烯酸酯树脂。酸的选择对聚氨酯丙烯酸酯树脂性能的影响见表3-67。  \n\n表3-67酸的选择对聚氨酯丙烯酸酯树脂性能的影响  \n\n\n<html><body><table><tr><td>性能</td><td>磷酸</td><td>硫酸</td><td>有机酸A</td><td>复合有机酸B</td><td>不加</td></tr><tr><td>体系pH</td><td>5</td><td>5</td><td>5</td><td>5</td><td>7</td></tr><tr><td>反应条件</td><td>40℃/1h</td><td>40℃/1h</td><td>40℃/1h</td><td>40℃/1h</td><td>40℃/1h</td></tr><tr><td>树脂色泽</td><td>3#</td><td>4</td><td>2#</td><td>1#</td><td>2#</td></tr></table></body></html>  \n\n（4）芳香族聚酯聚氨酯丙烯酸酯的合成在三口烧瓶中加入计量的己二酸、三羟甲基丙烷及二甘醇，升温，搅拌全溶解，约2h升温至 $160^{\\circ}\\mathrm{C}$ ，加入抗氧剂，通氮气和二甲苯，升温至 $190{\\sim}195^{\\circ}\\mathrm{C}$ ，保温 ${\\bf6}\\sim{\\bf8}{\\bf h}$ ，反应至酸值 ${\\bf<3m g~K O H/g}$ ，停止加热，抽真空1h，除去二甲苯和水，得到淡黄色黏稠状端羟基聚酯，羟值控制在 $100\\sim130\\mathrm{mg}~\\mathrm{KOH/g}$ ，分子量 $800{\\sim}1000$ 。 入  \n\n将甲苯二异氰酸酯加人到三口烧瓶中，用少量复合有机酸调节 $\\mathsf{p H}=4\\sim5$ ，升温至$40^{\\circ}\\mathrm{C}$ ，滴加聚酯与二月桂酸二丁基锡混合物，1h加完，升温至（ $(68\\pm2)^{\\circ}\\mathrm{C}$ 保温1h，当—NCO值达到理论值时降温至 $60^{\\circ}\\mathrm{C}$ ，滴加丙烯酸羟丙酯、二月桂酸二丁基锡、2，6-二叔丁基对甲酚混合物， $1\\mathord{\\sim}1.5\\mathrm{h}$ 加毕，保温1h，当一 $N C O<1\\%$ 后，升温至 $(88\\pm2)^{\\circ}\\mathrm{C}$ ，继续反应至$-\\mathrm{NCO}{<}0.2\\%$ ，加入无水乙醇，反应0.5h，降温得聚酯聚氨酯丙烯酸酯。聚酯用量对聚氨酯丙烯酸酯的影响见表3-68。  \n\n（5）三官能团芳香族聚氨酯丙烯酸酯的合成在三口烧瓶中加入 $1.5\\mathrm{{mol}}$ 三丙二醇二丙烯酸酯、 $3\\mathrm{{mol}}$ 丙烯酸羟乙酯、 $3\\mathrm{mol}$ 甲苯二异氰酸酯 TDI、 $400\\times10^{-6}$ 的甲氧基苯酚和$100\\times10^{-6}$ 的苯甲酰氯，搅拌升温至 $58\\sim62^{\\circ}C$ ，保温 $^{\\mathrm{1h}}$ ，反应至一NCO接近理论值。加入1mol乙氧基化三羟甲基丙烷（或丙氧基化三羟甲基丙烷)、0.05%的二月桂酸二丁基锡，58～62℃保温3h，反应至—NCO≤0.1%出料，得三官能团聚氨酯丙烯酸酯，其性能见表3-69。  \n\n表3-68聚酯用量对聚氨酯丙烯酸酯的影响   \n\n\n<html><body><table><tr><td rowspan=\"2\">性能</td><td colspan=\"3\">聚酯用量/mol</td></tr><tr><td>0.2</td><td>0.4</td><td>0.6</td></tr><tr><td>光固化时间/s</td><td>2</td><td>3</td><td>4</td></tr><tr><td>铅笔硬度/H</td><td>3</td><td>3</td><td>2</td></tr><tr><td>柔韧性/mm</td><td>2.0</td><td>1.0</td><td>0.5</td></tr><tr><td>附着力/级</td><td>1</td><td>1</td><td>1</td></tr><tr><td>黏度/mPa·s</td><td>5000</td><td>3000</td><td>2000</td></tr></table></body></html>  \n\n表3-69三官能团聚氨酯丙烯酸酯的性能  \n\n\n<html><body><table><tr><td>性能</td><td>(EO)TMP/TDI-HEA</td><td>(PO)3TMP/TDI-HEA</td></tr><tr><td>黏度（23℃）/mPa·s</td><td>64800</td><td>47200</td></tr><tr><td>—NCO/%</td><td>0.06</td><td>0.05</td></tr><tr><td>固化速率/s</td><td>11</td><td>8</td></tr><tr><td>硬度/H</td><td>3</td><td>2</td></tr><tr><td>附着力</td><td>优</td><td>优</td></tr><tr><td>柔韧性/mm</td><td>3</td><td>3</td></tr><tr><td>耐丙酮（2min）</td><td>无变化</td><td>无变化</td></tr><tr><td>耐乙醇(16h)</td><td>无变化</td><td>无变化</td></tr><tr><td>耐水(24h)</td><td>无变化</td><td>无变化</td></tr></table></body></html>  \n\n（6）六官能度芳香族聚氨酯丙烯酸酯低聚物的合成在三口烧瓶中加人30g甲苯二异氰酸酯，18滴二月桂酸二丁基锡，升温至35℃，缓慢滴加聚酯二元醇（分子量530）45.65g，40～50℃反应至红外检测3400cm-1处—OH峰消失，3300cm-1处有—NH峰出现说明第—步反应完成。称取102.8g季戊四醇三丙烯酸酯和对甲氧基苯酚0.18g，混匀后缓慢加人到反应物中，温度控制在60～70℃，反应至红外检测2700cm-1处—NCO峰消失，停止反应，加人20%的三丙二醇二丙烯酸酯搅匀出料。  \n\n（7）低黏度芳香族聚氨酯丙烯酸酯的合成在三口烧瓶中加人0.8mol甲基丙烯酸羟乙酯，升温至50℃，滴加0.5mol甲苯二异氰酸酯，1h内加毕，保温1h，再滴加0.1mol聚乙二醇400，反应每隔 30min 测—NCO含量，当—NCO降幅变缓时，加人反应物总量0.015%的二月桂酸二丁基锡，反应至一NCO低于2%时，停止反应，得到低黏度聚氨酯丙烯酸酯，黏度为26.5mPa·s，固化速率15s。  \n\n（8）脂肪族聚酯型聚氨酯丙烯酸酯的合成在三口烧瓶中加入113.2g（0.1mol）聚酯二元醇和0.1%的二月桂酸二丁基锡，在氮气保护下，慢慢加人33.6g（0.2mol）己二异氰酸酯，70～75℃反应3～4h，降温至60℃，加人23.6g（0.2mol）丙烯酸羟乙酯和0.1%的对苯二酚，在60～65℃反应3～4h，加人0.5%的无水乙醇，反应0.5h，得到脂肪族聚酯型聚氨酯丙烯酸酯树脂。  \n\n相对密度：1.18黏度 $(38^{\\circ}\\mathsf{C}$ ):28500mPa·s  \n\n$M_{\\mathrm{n}}$ ：1700挥发分： $1\\%$  \n\n（9）三官能脂肪族聚氨酯丙烯酸酯的合成在三口烧瓶中加入0.3mol己二异氰酸酯、适量二月桂酸二丁基锡、抗氧剂、对甲氧基苯酚，搅匀，滴加0.3mol丙烯酸羟乙酯，控制温度  \n\n45～50℃，反应2～3h，测定—NCO值达到理论值（—NCO反应 50%)，加人0.1mol三官能度聚酯三元醇，缓慢升温至（75士2)℃，反应3～4h，测定—NCO含量<0.2%，停止反应，得到三官能度聚酯聚氨酯丙烯酸酯，黏度（25℃）90Pa·s，折射率（25℃）1.4916。  \n\n（10）多官能脂肪族聚氨酯丙烯酸酯的合成在三口烧瓶中加人1mol己二异氰酸酯三聚体、0.08%的二月桂酸二丁基锡，加热，滴加3mol丙烯酸羟乙酯和适量对甲氧基苯酚混合液，升温至80℃，30min加毕，80℃反应3.5h，—NCO转化率>98%，加人少许无水乙醇反应30min，降温得到多官能聚氨酯丙烯酸酯。  \n\n4（11）脂环族聚氨酯丙烯酸酯的合成在三口烧瓶中加人2mol异佛尔酮二异氰酸酯(IPDI)、lmol聚醚乙二醇（PEG1000）和0.1%的二月桂酸二丁基锡，在70℃反应至—NCO量消耗接近50%，降温至50℃加人2mol甲基丙烯酸羟丙酯、0.1%的对苯二酚，在50℃反应至—NCO<0.5%，再加人少量乙醇搅拌1h，得脂环族聚氨酯丙烯酸酯。  \n\nIPDI脂肪族聚氨酯丙烯酸酯比芳香族（TDI）PUA耐候性好，有更好的柔韧性和耐冲击性。  \n\n（12）脂环族聚氨酯甲基丙烯酸酯的合成在三口烧瓶中加人22.2g异佛尔酮二异氰酸酯，通Nz，搅拌下滴加含0.68g二月桂酸二丁基锡的聚醚二元醇（PTMG2000）100g，$65^{\\circ}\\mathrm{C}$ 65℃反应3h，升温至75℃，滴加甲基丙烯酸羟丙酯14.4g和适量对苯二酚，继续反应4h，加入乙醇终止反应冷至室温，加人少量稀释剂1,6-已二醇二丙烯酸酯，出料。  \n\n（13）亚麻油改性聚氨酯丙烯酸酯的合成将0.3mol亚麻油和1.5mol甘油加人到三口烧瓶中，通Nz，搅拌，0.5h内升温至120℃，加人少许氧化钙，在2h内升温至（220士5)℃，保温并取样测定体系的95%乙醇容忍度为5（25℃）时，即为醇解终点，慢慢降温至190℃，分批加人0.9mol邻苯二甲酸酐，搅拌5min，加人适量的二甲苯，1h内升温至（210士5)℃，保持2h。再用1h升温至230℃，反应1h，取样测酸值，当酸值<3mgKOH/g后，停止加热，冷却过滤，得A测羟值待用。  \n\n在装有滴液漏斗、氮气导人管的四口烧瓶中，加人0.3molTDI和适量的HDDA，通氮气，升温至45℃，1h内慢慢滴加0.3molHEA，再升温至55℃反应1h，滴加几滴二月桂酸二丁基锡，在60℃时1h 内滴加0.lmolA，再在60℃下反应1h，得亚麻油改性聚氨酯丙烯酸酯。  \n\n（14）麻油改性聚氨酯丙烯酸酯的合成在三口烧瓶中通入干燥的氮气，排除残留潮气，加入0.8mol异佛尔酮二异氰酸酯和阻聚剂1010，升温至70℃，加人真空除水后的聚酯二元醇0.9mol（羟值=52～60mgK0H/g，Tg=—55℃）、氢化麻油0.4mol（羟值=178～185mgKOH/g，分子量为938)，滴加催化剂后反应2h，加入活性稀释剂丙烯酸-2-苯氧基乙酯和丙烯酸-2-(2-乙氧基）乙酯各10%（反应原料总质量)，当—NCO到理论值时，加人0.3mol丙烯酸羟乙酯，继续反应，当体系—NCO小于0.1%时，升温至90℃，保温0.5h，消耗剩余的—NCO，最后减压蒸馏，去除低分子物质，得到麻油改性聚氨酯丙烯酸酯。  \n\n（15）有机硅改性聚氨酯丙烯酸酯的合成将1mol烯丙醇和适量0.5%的氯铂酸异丙醇溶液加人三口烧瓶中，升温至90℃，在2h内将1mol含氢硅油滴加到三口烧瓶中，加毕升温至 $100^{\\circ}\\mathrm{C}$ 反应 $2\\mathrm{h}$ ，得到羟丙基硅油，并测羟值。  \n\n将1mol丙烯酸羟乙酯在1.5h内滴加到装有异佛尔酮二异氰酸酯和适量二月桂酸二丁基锡的三口烧瓶中，反应温度70℃，加毕保温30min，升温至85℃，反应2h，取样测—NCO值。按—OH：—NCO=1：1.05的比例将羟丙基硅油加人三口烧瓶中，70℃反应  \n\n3h，再升温至85℃反应1h，105℃反应1h，然后加人少量丙烯酸羟乙酯，在85℃下反应至—NCO含量 ${<}2\\mathrm{mg}\\ \\mathrm{KOH/g}$ 时，停止反应，出料，得有机硅改性聚氨酯内烯酸酯。  \n\n（16）聚氨酯改性丙烯酸酯树脂的合成在三口烧瓶中加人50mL丁酮和1g偶氮二异丁睛，通Nz，升温至80℃，滴加25mL丙烯酸丁酯（0.174mol)、10mL苯乙烯（0.087mol)、4mL甲基丙烯酸羟乙酯（0.033mol）和3mL丙烯酸（0.044mol）混合单体，3h内滴加完，继续反应 $^{12\\mathrm{h}}$ ，得丙烯酸共聚物，测定羟值。  \n\n在三口烧瓶中加人9mL甲苯二异氰酸酯（TDI）（0.063mol)、1滴二月桂酸二丁基锡及阻聚剂对甲氧基苯酚，加热至40℃，滴加8mL甲基丙烯酸羟乙酯（HEMA)(0.066mol)，1h加完，加人20mL丁酮，取样用二正丁胺测定溶液中—NCO浓度不变，停止反应得TDI-HEMA半加成物。  \n\n在丙烯酸共聚物溶液中加人2滴二月桂酸二丁基锡、50mL丁酮及适量的对甲氧基苯酚，升温至 $60^{\\circ}\\mathrm{C}$ ，滴加计算量的TDI-HEMA半加成物（以 $[-\\mathbf{NCO}]:[-\\mathbf{OH}]=1:1$ 计算量)，1h加完，反应至—NCO的2270cm-1吸收峰基本消失，加入计量的三乙胺中和，蒸出丁酮，滴加蒸馏水至蒸出温度 $81^{\\circ}\\mathrm{C}$ 停止，树脂数均分子量为 $2000{\\sim}3000$ ，粒径 $200\\mathrm{nm}$ 。  \n\n（17）聚氨酯改性聚酰胺树脂的合成在三口烧瓶中加人1mol甲苯二异氰酸酯、1mol丙烯酸羟乙酯、适量的二月桂酸二丁基锡和阻聚剂，60℃反应3～4h，至—NCO为理论值，慢慢加入适量的低分子量聚酰胺树脂，体系黏度明显增大，反应2～3h至—NCO消失，加人适量的丙烯酸羟乙酯调节黏度，得丙烯酸聚氨酯改性聚酰胺树脂(PA)。不同低聚物的涂膜性能见表3-70。PA-PUA共混体系性能见表3-71。  \n\n表3-70不同低聚物的涂膜性能  \n\n\n<html><body><table><tr><td>涂膜性能</td><td>PA</td><td>PUA</td><td>EA</td><td>涂膜性能</td><td>PA</td><td>PUA</td><td>EA</td></tr><tr><td>固化速率/s 柔韧性</td><td>2 优</td><td>3~5 优</td><td>3 差</td><td>附着力 耐酸碱性</td><td>优 耐碱</td><td>优 耐酸</td><td>良 耐酸碱</td></tr></table></body></html>  \n\n表3-71PA-PUA共混体系涂膜性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">涂膜性能</td><td colspan=\"5\">PA:PUA</td></tr><tr><td>5:0</td><td>4:1</td><td>3:2</td><td>2:3</td><td>1:4</td></tr><tr><td>固化速率/s</td><td>2</td><td>2</td><td>2</td><td>2</td><td>3</td></tr><tr><td>光泽度(60°)/%</td><td>101</td><td>94</td><td>95</td><td>97</td><td>102</td></tr><tr><td>柔韧性</td><td>优</td><td>优</td><td>优</td><td>优</td><td>优</td></tr><tr><td>附着力</td><td>优</td><td>优</td><td>优</td><td>优</td><td>优</td></tr><tr><td>耐酸碱性</td><td>耐碱</td><td>耐酸碱</td><td>耐酸碱</td><td>耐酸碱</td><td>耐酸</td></tr></table></body></html>  \n\n（18）聚氨酯改性梳型聚酰胺低聚物的合成在三口烧瓶中加入60份二聚脂肪酸（由棉籽油酸聚合而成，酸值195mgKOH/g)、30份麻油酸、0.5份己二酸，通Nz搅拌升温至120～130℃，滴加9.5份乙二胺（防止溢锅)，并于130～135℃保温2～3h，升温180℃反应2h，负压反应1h，再通Nz使压力恢复正常，测酸值、胺值合格后降温出料，得低分子量聚酰胺（A)。  \n\n在三口烧瓶中加入60份TDI-HEA半加成物，升温至60℃，缓慢加入40份加热熔化的A，加毕保温反应3h，至异氰酸酯完全反应，即可出料，得到异氰酸酯改性的梳型聚酰胺低聚物，若体系黏度过大，可加入适量丙烯酸羟乙酯调节黏度。该低聚物适用于UV塑料  \n\n(PE、PP、PS、PET、PA、ABS 等）涂料。  \n\n（19）含叔氨基聚氨酯丙烯酸酯的合成在三口烧瓶中加人70g丁酮，通Nz，升温至70℃，滴加溶有2.7g偶氮二异丁腈的甲基丙烯酸甲酯（20g）、丙烯酸丁酯（20g)、甲基丙烯酸羟乙酯（20g）和甲基丙烯酸-N,N-二甲胺乙酯的混合单体，2～3h加毕，保温反应1.5～2h，再升温至80℃，追加0.3g偶氮二异丁睛，继续反应至单体转化率98%以上，得到含羟基的丙烯酸树脂。  \n\n在三口烧瓶中加人22g异佛尔酮二异氰酸酯（IPDI）和0.1%的二月桂酸二丁基锡，通Nz，于25℃下滴加含少量阻聚剂的13g甲基丙烯酸羟乙酯（HEMA)，测定—NCO含量至转化率达到5O%，停止反应，得到IPDI-HEMA半加成物。  \n\n在含羟基的丙烯酸树脂中，加人0.1%的二月桂酸二丁基锡和0.2%的三乙胺复合催化剂，升温至70℃，滴加IPDI-HEMA半加成物（—OH：—NCO=1：1)，反应至—NCO含量为零，得到的含有叔氨基的聚氨酯丙烯酸树脂可用于制备电泳漆（其性能为固化速率30s，铅笔硬度4H，附着力优，耐冲击30kg·cm，光泽度95，柔韧性1mm，耐水性>500h)。  \n\n（20）含全氟基团的聚氨酯丙烯酸酯的合成在三口烧瓶中加入全氟辛酸和亚硫酰氯(SOCl）（全氟辛酸：SOClz=1：2，摩尔比）和催化剂3.35%的N,N-二甲基甲酰胺，加热至85℃，反应1h，减压蒸馏除去多余的SOCl，在1.07kPa下，收集60～72℃的馏分，得白色透明有强烈刺激气味的全氟辛酰氯（A)，平均收率为92.6%。  \n\n将2.5g（0.04mol）乙醇胺、10mL四氢呋喃加人三口烧瓶中，用冰盐浴冷至5℃以下，搅拌下缓慢滴加8.5g全氯辛酰氯（0.02mol)，半小时滴完，加完后升温至30℃，继续反应3h得黄色膏状物，减压蒸馏除去四氢呋喃，加人10mL70℃的热水洗涤，并趁热分液，用盐酸调pH值至7.5～8.0，再用热水洗1次，产物用氯仿重结晶，即得成品晶体N-羟乙基全氟辛酰胺 (B)。  \n\n在干燥的三口烧瓶中加人1.74g（0.0lmol）甲苯二异氰酸酯、4mL甲基异丁基甲酮、1滴二月桂酸二丁基锡，Nz保护，升温至65～70℃，1h内缓慢滴加4.57g（0.0lmol）B和12mL甲基异丁基甲酮溶液，反应3h，补加2滴二月桂酸二丁基锡，升温至75～80℃，缓慢滴加1.6g（0.0lmol）甲基丙烯酸羟乙酯，反应4h，减压蒸馏除去甲基异丁基甲酮，用四氢呋喃重结晶得浅棕色透明的晶体含全氟基团的聚氨酯丙烯酸酯，得率 $81\\%$ 。  \n\n（21）聚氨酯丙烯酸酯/蒙脱土插层复合材料的制备在三口烧瓶中加人lmol甲苯二异氰酸酯（TDI)、0.5mol聚醚二元醇和一定量的有机蒙脱土·，先通氮气30min，在通氮气下升温至 $65\\mathrm{^\\circC}$ ，反应至体系—NCO值接近理论值，加人lmol丙烯酸羟乙酯、适量二丁基二月桂酸锡和对甲氧基苯酚，75℃反应至—NCO值接近零时结束，制得聚氨酯丙烯酸酯/蒙脱土插层复合物。  \n\n（22）UV固化有机/无机杂化聚氨酯丙烯酸酯的合成  \n\n![](images/70c32d530c00503103a5147d6dc8e8759dea82cff52ecb6297ebc3c6637ddb08.jpg)  \n\n![](images/e2d77fc46ccdacdf0a00ff7806dd5534223bb2e27ffa89372a272428151fe3cb.jpg)  \n\n在三口烧瓶中加人58.06g（0.5mol）丙烯酸羟乙酯、55.34g（0.25mol）硅烷偶联剂$\\mathtt{K H}550$ ，在 $30^{\\circ}\\mathrm{C}$ 以下反应 $20\\mathbf{h}$ ，得到透明黏稠液杂化二元醇HD113. $_{40\\mathbf{g}}$ 。  \n\n将45.36g（0.lmol）HD和34.83g（0.2mol）甲苯二异氰酸酯在70℃下反应6h，然后在50℃下滴加丙烯酸羟乙酯23.23g（0.2mol)，70℃下反应3h，得浅黄色黏稠液体，即杂化聚氨酯丙烯酸酯低聚物HUA。  \n\n将10.34gHUA在70℃下溶解于等量的异丙醇（含0.18g0.1mol/L的甲酸）中，回流反应8h，减压除去挥发物，即得到透明的黏稠体，即具有无机网络结构的有机/无机杂化聚氨酯丙烯酸酯。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 98,
+        "chunk": "# 3.20.3聚酯丙烯酸酯的合成  \n\n（1）双官能团聚酯丙烯酸酯的合成在三口烧瓶中加人410g已二酸、40g马来酸酐、80g三羟甲基丙烷、312g新戊二醇、lg30%的磷酸（催化剂)，加热至110℃，搅拌，通Nz，升温至150～160℃开始出水时，加人80g二甲苯和0.2g抗氧剂，180℃反应4～6h，反应至酸值<5mgKOH/g，停止通N，抽真空，当抽出的二甲苯与加入的二甲苯相当时，停止反应，降温出料，测羟值和酸值，得端羟基聚酯。  \n\n将600g端羟基聚酯（羟值以100计）加入三口烧瓶中，升温至90℃，加人对甲苯磺酸0.8g、丙烯酸85g对苯二酚0.2g和甲苯80g，0.5h内加完，升温至110～115℃，回流反应4h，测酸值<10mgKOH/g，真空蒸馏除去甲苯，得到黄色的透明树脂，黏度（25℃）1000～3000mPa·s，固含量≥95%，为双官能团聚酯丙烯酸酯。  \n\n（2）多官能聚酯丙烯酸酯的合成在三口烧瓶中加人3.35g（25mmol）三羟甲基丙烷、14.9g（149mmol）丁二酸酐、6.9g（75mmol）环氧氯丙烷、适量的四乙基溴化铵和N,N-二甲基甲酰胺溶剂，升温至90℃反应，测酸值计算反应程度，当反应程度超过98%时，加入5.54g（mmol）环氧丙醇，继续反应，用测酸值的方法跟踪反应，当转化率超过97%后，加入32.1g（321mmol）丁二酸酐和15.8g（17lmmol）环氧氯丙烷，反应至体系酸值达到设计值时，降温至70℃，加人适量的对甲氧基苯酚和28.4g（200mmol）甲基丙烯酸缩水甘油酯，反应到酸值接近零。得到六官能度丙烯酸化聚酯，测得数均分子量为3600（理论最大分子量为3980)，重均分子量接近7000，聚合分散度1.9，黏度为 $58.6\\mathrm{{Pa}\\cdot\\mathrm{{s}}}$ 3  \n\n（3）多官能团的聚酯丙烯酸酯合成  \n\n$$\n\\begin{array}{r l}&{\\mathrm{{CH}_{2}O H}}\\\\ &{\\mathrm{{2HOOC-(CH_{2})_{4}-C O O H\\ +\\ H O-C H_{2}-\\overbrace{\\sum_{\\ell=0}^{\\ell}C H_{2}O H\\ell+6C H_{2}}-C H C O O H\\frac{1}{\\ell-H_{2}O}^{\\star}}}}\\\\ &{\\mathrm{{CH}_{2}O H}}\\end{array}\n$$  \n\n$$\n\\begin{array}{r l r}{\\mathrm{H}_{2}\\mathrm{C}\\mathrm{-}\\mathrm{CHCOOCH}_{2}}&{}&{\\mathrm{CH}_{2}\\mathrm{OOCCH}\\mathrm{-}\\mathrm{CH}_{2}}\\\\ {\\mathrm{H}_{2}\\mathrm{C}\\mathrm{-}\\mathrm{CHCOOCH}_{2}\\mathrm{-}\\mathrm{C}\\mathrm{-}\\mathrm{CH}_{2}\\mathrm{OOC-}\\mathrm{(CH}_{2}\\mathrm{)}_{4}\\mathrm{-}\\mathrm{COOCH}_{2}\\mathrm{-}\\mathrm{C}\\mathrm{-}\\mathrm{CH}_{2}\\mathrm{OOCCH}\\mathrm{-}\\mathrm{CH}_{2}}\\\\ {\\mathrm{H}_{2}\\mathrm{C}\\mathrm{-}\\mathrm{CHCOOCH}_{2}}&{}&{\\mathrm{CH}_{2}\\mathrm{OOCCH}\\mathrm{-}\\mathrm{CH}_{2}}\\end{array}\n$$  \n\n在三口烧瓶中加人1mol己二酸、2mol季戊四醇、6.3mol丙烯酸、溶剂（20%的苯)、催化剂（1.2%的对甲苯磺酸）和1.5%的对苯二酚，缓慢升温至80～90℃，开始回流，反应至分水器中不再有水产出（约10h)，即到反应终点，真空蒸馏除去苯和未反应的丙烯酸，经特殊处理后，得到黄色透明、酸值≤10mgKOH/g的多官能团聚酯丙烯酸酯。  \n\n多官能团聚酯丙烯酸酯的性能见表3-72。多官能团聚酯丙烯酸酯与双酚A环氧丙烯酸酯性能比较见表3-73。  \n\n表3-72多官能团聚酯丙烯酸酯的性能  \n\n![](images/290c30cefbd13ae2c52c1f04a64e1c139edbbc5be1c9ab47f4a2ed41cff50812.jpg)  \n\n表3-73多官能团聚酯丙烯酸酯与双酚A环氧丙烯酸酯性能比较   \n\n\n<html><body><table><tr><td>性能</td><td>聚酯丙烯酸酯</td><td>环氧丙烯酸酯</td><td>性能</td><td>聚酯丙烯酸酯</td><td>环氧丙烯酸酯</td></tr><tr><td></td><td>1015</td><td></td><td></td><td></td><td></td></tr><tr><td>/</td><td></td><td></td><td>/PVC)/</td><td></td><td></td></tr><tr><td></td><td></td><td>10338</td><td></td><td>B6</td><td>4B4</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 99,
+        "chunk": "# 3.20.4 有机硅丙烯酸酯低聚物的合成  \n\n（1）有机硅低聚物的合成（一）将八甲基环四硅氧烷及催化剂FeCl·6HzO（0.1%～$0.3\\%$ 0.3%）加人三口烧瓶中，搅拌下加人二甲基二氯硅烷，升温至80℃后反应6h，在80℃/1333.2Pa下减压蒸馏，再在8000r/min 的离心机下离心分离残留物，得淡黄色透明液体α，$\\omega$ 二氯聚二甲基硅氧烷。  \n\n在三口烧瓶中加入季戊四醇三丙烯酸酯、三乙胺（HCI吸收剂)、溶剂甲苯及阻聚剂对甲氧基苯酚，在冷水浴下搅拌滴加α,w-二氯二甲基硅氧烷，缓慢升温至40℃，反应1h，在40°℃/1333.2Pa下减压蒸馏溶剂甲苯和未反应的三乙胺，再在8000r/min 的离心机下二次离心分离沉淀物，得乳白色至无色透明液体即为聚硅氧烷丙烯酸酯低聚物。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 100,
+        "chunk": "# (2）有机硅低聚物的合成（二)  \n\n![](images/c9ce199b7ab83a15f602abe1014a4fae8c6d83cfb80a34c2f4d2c56e351a4e48.jpg)  \n\n在三口烧瓶中加人计算量的含氢硅油（H-20端氢硅油)、三丙二醇二丙烯酸酯和甲苯/二甲苯溶剂，搅匀通Nz保护，加（35～50)×10-6氯铂酸的异丙醇溶液、1%的对羟基苯甲醚，升温至90～120℃，反应4h，停止反应，减压蒸馏除去溶剂，即得有机硅丙烯酸酯低聚物。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 101,
+        "chunk": "# （3）有机硅低聚物的合成（三）  \n\nOCH3 HC-O- )CH +2HCCHCOOCHCHOH—CHOH OCH3 OCHg H2C—CHCOOCHCH—OSi--0 CH2CHOOCCH-CH2 OCHs  \n\n在三口烧瓶中加入1mol甲基硅氧烷、2mol丙烯酸羟乙酯、适量的催化剂（二辛酸锡）、阻聚剂（对甲氧基苯酚)，通干燥空气，90℃反应5h，得到UV固化有机硅低聚物。  \n\n（4）甲基丙烯酸聚硅氧烷合成  \n\n$$\n\\begin{array}{r l r}{\\mathrm{CH_{3}}}&{{}\\mathrm{OCH_{3}}}&{{\\mathrm{OCH_{3}}}}&{{\\mathrm{OCH_{3}}}}\\\\ {\\mathrm{\\large~\\Gamma~}}&{{}\\mathrm{\\large~|~}}&{\\mathrm{|~}}\\\\ {\\mathrm{H_{2}C-C C O O C H_{2}C H_{2}C H_{2}-\\overbrace{S i\\mathrm{\\cdots}\\mathrm{OCH_{2}}\\mathrm{-}S i\\mathrm{\\cdots}\\mathrm{O-}C H_{2}\\mathrm{-}S i C H_{2}C H_{2}C H_{2}O O C C-C H_{2}}^{\\mathrm{~}}}}\\\\ {\\mathrm{\\large~|~}}&{{}\\mathrm{\\large~|~}}&{{\\mathrm{\\large~|~}}}\\\\ {\\mathrm{OCH_{3}}}&{{}\\mathrm{OCH_{3}}}&{{\\mathrm{OCH_{3}}}}\\end{array}\n$$  \n\n将 2mol-甲基丙烯酰氧丙基三甲氧基硅烷、1mol二端羟基二甲基聚硅氧烷和适量二月桂酸二丁基锡催化剂加入到装有回流冷凝器、减压泵的三口烧瓶中，于80～100℃反应8h。反应过程中要及时排走副产物甲醇，以利反应顺利进行，最后减压蒸馏，除去剩下的甲醇和其他烷基醇，得到淡黄色的丙烯酸酯改性的聚硅氧烷低聚物。  \n\n（5）光敏有机硅丙烯酸酯的合成  \n\n$$\n\\begin{array}{r l r}&{\\mathrm{CH_{3}}\\mathrm{CH_{3}}\\mathrm{CH_{3}}\\mathrm{CH_{3}}}&{\\mathrm{CH_{3}}}\\\\ &{\\mathrm{~\\small~\\displaystyle~\\frac{CH_{3}}{\\mu_{0}C-\\mu_{1}}~\\frac{C H_{3}}{\\mu_{0}}~\\frac{\\mu_{0}}{\\mu_{1}}~+~\\mathrm{H_{2}C-C O O C H_{2}C H-C H_{2}}~\\longrightarrow~H_{3}C-\\mu_{3}^{\\prime}+\\left(0-\\frac{\\mu_{1}}{\\mu_{1}}\\right)\\mathrm{O-\\ensuremath{SH_{3}}-C H_{3}}}\\\\ &{\\mathrm{~\\small~\\displaystyle~\\frac{CH_{3}}{\\mu_{0}}~\\frac{H_{3}}{\\mu_{1}}~\\frac{C H_{3}}{C H_{3}}~\\ensuremath{C H_{3}}~\\phantom{\\Bigg[~\\frac{C H_{3}}{\\mu_{0}C H_{3}}~}}&{\\mathrm{CH_{3}}}&{\\mathrm{C-CH_{3}C H_{3}}}\\\\ &{\\mathrm{CH_{3}~H_{3}~\\ensuremath{C H_{3}}~}}&{\\mathrm{CH_{2}O O C C-C H_{2}}}\\\\ &{\\mathrm{~\\small~\\displaystyle~\\frac{CH_{2}O O C C-C H_{2}}{C H_{3}}~\\frac{H_{3}}{\\mu_{1}}~}}&{\\mathrm{CH_{3}}}\\end{array}\n$$  \n\n在三口烧瓶中加入计算量的甲基丙烯酸烯丙酯、反应物总重0.04%的三苯基麟氯化佬（催化剂）、反应物总重50%的甲苯（溶剂）和适量阻聚剂对甲氧基苯酚，通Nz保护，升温至65～70℃，滴加等物质的量的甲基含氢硅油（含量为0.35%)，反应过程中测定含氢硅油的含氢量至转化率达100%时，停止反应，得到光敏有机硅丙烯酸酯低聚物。  \n\n（6）光固化有机硅丙烯酸酯的合成  \n\n![](images/335d172c6c734fc02626bb8020b3e975a01b7d4baf0cd9c6ac1d6f5c84f713a8.jpg)  \n\n在三口烧瓶中加人17.4g（0.1mol）甲苯二异氰酸酯以及质量分数0.1%的二月桂酸二丁基锡，升温至40℃，滴加含有阻聚剂对羟基苯甲醚的29.8g（0.1mol）季戊四醇三丙烯酸酯（—NCO：—OH=2：1，摩尔比)，加毕，40℃继续反应4h，当—NCO含量达到预定值后，滴加双烷羟基硅油85g（0.05mol）（—NCO：—OH=1：1，摩尔比)，升温至70～75℃，反应至一NCO含量为零时，停止反应，得到光固化有机硅丙烯酸酯。  \n\n（7）环氧聚硅氧烷丙烯酸酯的合成以甲苯作溶剂，N,N-二甲基苄胺作催化剂，对羟基苯甲醚作阻聚剂，将环氧聚硅氧烷与等当量的丙烯酸于100～110℃反应6h，测定酸值和环氧转化率为90%左右，减压蒸馏除去溶剂和未反应的丙烯酸，得环氧聚硅氧烷丙烯酸酯(AEPS)。  \n\n光敏聚合物环氧聚硅氧烷丙烯酸酯（AEPS）固化膜硬度较高，表面光滑耐磨，吸水率低，电性能好，耐溶剂，耐酸和弱碱性好，不耐强碱，有高拉伸强度和模量，折射率较高，为1.4698，固化膜折射率达1.4918。AEPS固化膜的物理性能见表3-74。  \n\n表3-74AEPS固化膜的物理性能  \n\n\n<html><body><table><tr><td>物理性能</td><td>参数</td><td>物理性能</td><td>参数</td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td>模量/MPa</td><td>80.1</td><td>电击穿强度/（kv/mm）</td><td>50.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 102,
+        "chunk": "# （8）环氧有机硅丙烯酸酯的合成  \n\n![](images/a5a21b559cafc06098cf4c43f670567938b148bc3f68690127343da0f3c44646.jpg)  \n\n在三口烧瓶中加人一定量的环氧基硅油和丙烯酸（环氧基与羧基的摩尔比为1：0.95)、总量0.6%的催化剂三乙胺和适量的对甲氧基苯酚，搅匀后升温至100～110℃反应，当酸值<5mgKOH/g时，停止反应，得到环氧有机硅丙烯酸酯(PSAE)。  \n\nPSAE的感度值：  \n\nPSAE: $1173=100:2$ 感度值28.4mJ/cm²（光强2.84mW/cm²）PSAE：TEGDA：1173=60：40：4感度值16.78mJ/cm²（光强2.84mW/cm²）  \n\n（9）光固化有机硅/纳米SiOz杂化材料的合成在三口烧瓶中加人0.lmol异佛尔酮二异氰酸酯和总质量0.1%的二月桂酸二丁基锡，室温搅拌，氮气保护下滴加0.1mol丙烯酸羟乙酯，2h加毕，继续室温下反应4h，至—NCO含量达到预定值，滴加0.05mol双烷羟基硅油（K-50)，升温至60℃，反应至—NCO消失，停止反应，得光敏有机硅树脂PSUA，（  \n\n将一定量乙醇、正硅酸乙酯加入装有滴液漏斗的锥形瓶中，室温下搅拌，同时滴加用盐酸酸化的乙醇与去离子水混合液（各物质比为n正硅酸乙酯：n水：n乙醇：n盐酸=1：5：10：0.05），滴加完后继续反应24h。再滴加-定量硅偶联剂KH570，搅拌均匀后陈化24h制得硅溶胶_  \n\n将3份光敏有机硅树脂PSUA和2份三丙二醇二丙烯酸酯以及3%的光引发剂1173加人三口烧瓶中搅拌均匀，滴加1份硅溶胶剧烈搅拌至体系均匀透明，得到光固化有机硅/  \n\nSiO2杂化材料。杂化材料稳定，相容性好，有很好的韧性和较高的硬度(5～6H)。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 103,
+        "chunk": "# 3.20.5 UV水性低聚物的合成  \n\n（1）UV水性EA的合成在三口瓶中加人一定量的双酚A环氧树脂E-51和适量的对甲氧基苯酚，搅拌加热升温至60℃，缓慢滴加丙烯酸（与E-51环氧基摩尔比为1：1）和适量苄基三甲基氯化铵，1h滴完，升温至（100士5)℃，反应至酸值<5mgKOH/g，停止反应制得环氧丙烯酸树脂EA。降温至50℃，再加人一定量的偏苯三酸酐B（与EA中羟基摩尔比为0.4～0.5）和适量丙酮，升温至80℃，反应至酸值为理论值时，停止反应，得到酸酐改性EA（B-EA)。常温下加人三乙醇胺搅匀中和，在剧烈搅拌下加水稀释，得到UV水性EA。B-EA的性能见表3-75。  \n\n表3-75 B-EA的性能  \n\n\n<html><body><table><tr><td>B摩尔当量</td><td>0.05</td><td>0.1</td><td>0.2</td><td>0.3</td><td>0.4</td><td>0.5</td></tr><tr><td>60%固含量</td><td>不溶</td><td>不溶</td><td>不溶</td><td>溶</td><td>溶</td><td>溶</td></tr><tr><td>固化速率/s</td><td>0.9</td><td>1.0</td><td>1.2</td><td>2.3</td><td>2.5</td><td>3.0</td></tr><tr><td rowspan=\"2\">0.4molB-EA固化速率</td><td colspan=\"6\">中和程度</td></tr><tr><td colspan=\"2\">100%</td><td colspan=\"2\">80%</td><td colspan=\"2\">60%</td></tr><tr><td>预烘干/s</td><td colspan=\"2\">1.13</td><td colspan=\"2\">1.17</td><td colspan=\"2\">1.25</td></tr><tr><td>不烘干/s</td><td colspan=\"2\">0.6</td><td colspan=\"2\">0.65</td><td colspan=\"2\">0.8 “</td></tr></table></body></html>  \n\n（2）UV水性FA的合成在三口烧瓶中加人一定量的酚醛环氧树脂F-51和适量的对甲氧基苯酚，搅拌加热至60℃，缓慢滴加丙烯酸（与F-51环氧基摩尔比为1：1）和适量苄基三甲基氯化铵，1h滴完，升温至（100士5)℃，反应至酸值<5mgKOH/g，停止反应，制得酚醛环氧丙烯酸树脂FA。降温至50℃，再加人一定量的偏苯三酸酐（与FA中羟基摩尔比为0.5）和适量丙酮，升温至80℃，反应至酸值接近理论值时，停止反应，得到酸酐改性FA。常温下加人三乙醇胺搅匀中和，在剧烈搅拌下加水稀释，得到UV水性FA树脂。  \n\n（3）UV水性FA、EA的合成在三口烧瓶中加人一定量的双酚A环氧树脂E-51（或酚醛环氧树脂F-51)，加热至75～80℃，滴加一定量的丙烯酸、N,N-二甲基苄胺和对甲氧基苯酚混合液（环氧基与羧基摩尔比为2：1)，升温至90～100℃反应至酸值<5mgKOH/g，停止反应，加人适量乙二醇独乙醚作溶剂，再加人一定量的二甲基乙醇胺和磷酸（环氧基：二甲基乙醇胺：磷酸=3：3：1，摩尔比)，升温至50～55℃，反应3h左右，体系环氧值下降出现平缓趋势时，停止反应制得UV水性季铵化的环氧丙烯酸树脂。四种季铵化环氧丙烯酸树脂的水溶性见表3-76。  \n\n表3-76四种季铵化环氧丙烯酸树脂的水溶性  \n\n\n<html><body><table><tr><td>样品</td><td>发生基酰化</td><td>发生氧基化的</td><td>季铵传应率的环氧</td><td>水溶性</td><td>溶剂</td></tr><tr><td>E51 A-N1</td><td>48.4</td><td>35.2</td><td>68.3</td><td>透明溶液</td><td>水</td></tr><tr><td>Es1A-N2</td><td>56.1</td><td>25.9</td><td>59</td><td>乳状液</td><td>乙二醇独乙醚：水=1:1</td></tr><tr><td>Fs1A-N1</td><td>66.7</td><td>19.5</td><td>58.7</td><td>透明溶液</td><td>水</td></tr><tr><td>F51A-N2</td><td>81.6</td><td>8.5</td><td>46.2</td><td>乳状液</td><td>乙二醇独乙醚水=1:1</td></tr></table></body></html>  \n\n（4）UV水性FA的合成在三口烧瓶中加人 $50\\mathbf{g}$ 酚醛环氧树脂，加热至 $75\\mathrm{^\\circC}$ ，滴加一定量丙烯酸（丙烯酸与环氧基摩尔比为0.5)、体系质量 $0.5\\%\\sim2.0\\%$ 的 $N,N.$ 二甲基苯胺，反应 $3.5\\mathrm{h}$ ? $60^{\\circ}\\mathrm{C}$ 下热水洗涤，脱水后得酚醛环氧丙烯酸树脂FA，将三乙胺盐酸溶液按一定摩尔比（三乙胺盐酸盐：FA中环氧基 $=0.8\\sim0.5\\dot$ ）在 $80^{\\circ}\\mathrm{C}$ 下反应5h，以甲苯共沸脱水，经丙酮精制后得酚醛丙烯酸酯季铵盐感光树脂，具有良好的水溶性。  \n\n（5）UV含季铵基的FA的合成将三乙胺在搅拌下滴入在冰水浴中冷却的稀盐酸中，至 $\\mathtt{p H}$ 值为8，制得三乙胺盐酸盐（TC)。用 $0.1{\\mathrm{mol~AgNO}}_{3}$ ，以 $\\bf{K}_{2}C r O_{4}$ 为指示剂，滴定${\\bf C l^{-}}$ 求得TC浓度。  \n\n在三口烧瓶中加入酚醛环氧树脂F-48，搅拌下加人一定量TC（TC与F-48的环氧基摩尔比为0.5)，升温至 $80^{\\circ}\\mathrm{C}$ 反应 $5\\mathrm{h}$ ，减压脱去大部分水，加适量甲苯，加热共沸除去残余水分，减压蒸馏除去甲苯，得季铵盐酚醛环氧树脂。加热至 $75\\mathrm{^\\circC}$ ，滴加超过剩余环氧基摩尔比一半的丙烯酸和总量 $0.5\\%$ 的对苯二酚及 $2\\%$ 的 $N,N\\mathrm{.}$ -二甲苯胺，反应4h，使剩余环氧基开环生成丙烯酸酯基。加入适量甲苯升温至 $110^{\\circ}\\mathrm{C}$ ，使剩余的丙烯酸与开环反应生成的羟基进一步酯化，共沸脱水6h，减压蒸去甲苯和未反应的丙烯酸，加适量无水乙醇，搅拌溶解后加入乙醚至无不溶物析出，静置分层倾去上层液体，反复洗三次， $60^{\\circ}\\mathrm{C}$ 下真空干燥得含季铵基的FA树脂。  \n\n（6）UV含不同季铵盐结构的FA的合成取 $0.05\\mathrm{mol}$ 的不同酸或 ${\\bf N a H S O_{3}}$ ，加人$100\\mathrm{mL}$ 蒸馏水稀释，在冰水浴中滴加约 $80\\mathrm{mL}$ 的三乙胺，使 $\\mathbf{pH}{=}7{\\sim}8$ ，搅拌1h，制得三乙胺的各种不同酸的盐。  \n\n在三口烧瓶中，将已知浓度的三乙胺叔胺盐水溶液按0.5的摩尔比（叔胺盐/酚醛环氧树脂的环氧基）加至酚醛环氧树脂F-51中，搅拌下升温 $80^{\\circ}\\mathrm{C}$ 反应 $5\\mathrm{h}$ 。减压脱去大部分水，再加适量甲苯加热共沸除去残余水分，减压除去甲苯，得季铵盐酚醛环氧树脂。加热至$75\\%$ ，滴加摩尔比为0.6的（丙烯酸/酚醛环氧树脂的环氧基）丙烯酸、体系质量 $0.5\\%$ 的对苯二酚及 $2\\%$ 的 $N,N-$ -二甲基苯胺，在氮气保护下反应 $3.5\\mathrm{h}$ 。加适量丙酮搅拌 $10\\mathrm{{min}}$ ，使未反应的原料树脂溶解，静置分层倾去上层丙酮溶液，重复三次，蒸去丙酮得含季铵盐结构的FA树脂。不同季铵盐的UV-FA见表3-77。  \n\n表3-77 不同季铵盐的UV-FA  \n\n\n<html><body><table><tr><td>酸根</td><td>转化率/%</td><td>固化凝胶量/%</td><td>酸根</td><td>转化率/%</td><td>固化凝胶量/%</td></tr><tr><td>Cl-</td><td>94.1</td><td>25.6</td><td>Clg CCOO-</td><td>81.5</td><td>2.80</td></tr><tr><td>NO</td><td>90.7</td><td>23.2</td><td>NaSO</td><td>87.2</td><td>20.6</td></tr><tr><td>coo-</td><td>92.2</td><td>21.2</td><td></td><td></td><td></td></tr></table></body></html>  \n\n（7）UV水溶性FA季铵盐树脂的合成在三口烧瓶中加人 $50\\mathbf{g}$ 酚醛环氧树脂，加热至$75\\mathrm{{^\\circC}}$ ，滴加摩尔比为0.4（丙烯酸/环氧基）的丙烯酸、 $0.5\\%$ 的对苯二酚及 $2\\%$ 的 $N$ ， $N\\cdot$ 二甲基苯胺，在氮气保护下搅拌3.5h，停止反应，加入适量 $60^{\\circ}\\mathrm{C}$ 热水搅拌 $10\\mathrm{{min}}$ ，静置分层除去上层溶液，反复三次，以除去未反应的丙烯酸、阻聚剂和催化剂，最后除去水分，得酚醛环氧丙烯酸树脂FA。  \n\n将三乙胺盐酸盐溶液按摩尔比为0.6的比例（三乙胺盐酸盐/起始环氧值）加入FA中，升温 $80^{\\circ}\\mathrm{C}$ ，搅拌5h，用甲苯共沸除去体系中水分，加入适量丙酮搅拌，使未反应物溶解，静置分层除去上层丙酮溶液，反复三次，蒸去丙酮得酚醛环氧丙烯酸酯季铵盐树脂。  \n\n在酚醛环氧丙烯酸酯季铵盐树脂中加入适量甲苯和0.5%的对苯二酚，加热至110℃，滴加过量的丙烯酸（丙烯酸与起始环氧基摩尔比为3.0)，搅拌下共沸脱水5h，减压除去甲苯和丙烯酸，用无水乙醇和乙醚精制产物，蒸去残存溶剂，得到不饱和基相对含量较高的酚醛环氧丙烯酸酯季铵盐树脂。  \n\n当丙烯酸/环氧基 $<0.5$ 时，季铵化的树脂有良好的水溶性。  \n\n第二步丙烯酸化中有 $20\\%$ 的羟基被酯化。  \n\n（8）肉桂酸酯化酚醛树脂季铵盐的合成在三口烧瓶中加入 $\\boldsymbol{50}\\mathbf{g}$ 酚醛环氧树脂、41.4g肉桂酸（环氧基：羧基=1：0.5，摩尔比)、2%的N,N-二甲基苯胺和适量的丙酮，搅拌至溶解，升温至60℃，回流反应12h，蒸去溶剂洗涤精制，得肉桂酸酯化酚醛环氧树脂。  \n\n取一定量的三乙胺盐水溶液（三乙胺：环氧基=0.5：1，摩尔比）加入到上述酚醛环氧肉桂酸酯中，升温至80℃，搅拌反应5h后，除去体系中的水分，加人适量丙酮，洗涤产物，蒸去溶剂，60℃真空干燥一昼夜，得精制的肉桂酸酯化酚醛环氧树脂季铵盐，易溶于水，为水溶性感光树脂。  \n\n（9）UV水性PUA的合成在三口烧瓶中加入0.5mol聚醚二元醇PPG210、1.5mol二羟甲基丙酸和适量二月桂酸二丁基锡，低于40℃加人3mol甲苯二异氰酸酯，混合后缓慢升温至70～80℃，反应至—NOO值达预定值，加适量丙酮和对苯二酚，滴加2mol丙烯酸羟乙酯，反应至—NCO峰消失。室温下加人三乙醇胺中和，剧烈搅拌下加水得到UV水性PUA。  \n\n（10）UV水性PUA的合成在三口烧瓶中加人聚醚多元醇，低于40℃加入甲苯二异氰酸酯，缓慢升温至80～90℃反应2h。降温至50℃以下，加人二元醇和二羟甲基丙酸，70～80℃反应2h，加人适量丙酮，40～50℃滴加丙烯酸羟乙酯和适量对苯二酚，60～65℃反应2h，常温下加人三乙胺中和，剧烈搅拌下加水乳化得到水性UV-PUA，固含量在25%～30%。反应中控制n-NCo/n-OH值在3.5，乙烯基质量分数为3.0%较合适。  \n\n（11）UV水性PUA的合成在三口烧瓶中加人2mol甲苯二异氰酸酯和lmol聚醚二元醇PPG（分子量400、100或200），通氮气升温至65℃，反应至—NCO值达预定值，加人丙烯酸羟丙酯、二羟甲基丙酸和适量对苯二酚于75℃反应至—NCO基本消失，停止反应。降温加入适量丙酮，室温下加入三乙胺中和，并在剧烈搅拌下加水，制得水性UV-PUA、固含量30%左右，HPA链节质量分数为12.6%时综合性能最佳。  \n\n（12）UV水性PUA的合成在三口烧瓶中加人0.3mol聚醚二元醇PEG（分子量200～1000）、0.7mol二羟甲基丙酸和少量N-甲基吡咯烷酮，搅拌溶解后，加入1.5mol甲苯二异氰酸酯和适量二月桂酸二丁基锡，升温至75℃，反应2h，加人1mol丙烯酸羟丙酯，继续反应3h，降温至50℃，加人丙酮稀释，以三乙胺中和后加水分散，蒸出丙酮得固含量$30\\%$ 左右的UV水性PUA。  \n\n（13）水性聚醚型PUA的合成在三口烧瓶中加人聚乙二醇、二羟基丙酸、适量二月桂酸二丁基锡，搅拌下加人甲苯二异氰酸酯，升温至40℃，再升温到70～80℃反应至一NCO不变，降温至50℃，加人适量对甲氧基苯酚，滴加丙烯酸羟乙酯，加毕升温至70～75℃，反应至—NCO消失，降温至常温，加人三乙胺或三乙醇胺中和，在剧烈搅拌下加水得到UV固化水性PUA。不同基团比时PUA 210和PUA 220的性能见表3-78。  \n\n（14）UV水性阴离子型PUA的合成在三口烧瓶中加入2mol甲苯二异氰酸酯、lmol二羟甲基丙酸和1%的二月桂酸二丁基锡，通氮气，升温80℃反应至—-NCO值不变，再缓慢加人 $0.5\\mathrm{mol}$ 聚1,4-丁二醇（ $\\scriptstyle M=1000!$ )，反应至一NCO值不变。  \n\n表3-78不同基团比时PUA210和PUA220的性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">基团比</td><td>1</td><td>2</td><td>3</td><td>4</td><td>5</td></tr><tr><td>6:1:3:2</td><td>4.5:1:2:1.5</td><td>3.5:1: 1.25 :1.25</td><td>3:1:1:1</td><td>5:2:1:2</td></tr><tr><td colspan=\"6\">PUA210（聚环氧丙醚210)</td></tr><tr><td>HEA/%</td><td>15.7</td><td>14.3</td><td>13.4</td><td>10.9</td><td>13.0</td></tr><tr><td>DMPA/%</td><td>13.6</td><td>11.0</td><td>7.2</td><td>6.3</td><td>3.7</td></tr><tr><td>固化时间/s</td><td>0.3</td><td>1.0</td><td>2.4</td><td>5.2</td><td>20</td></tr><tr><td colspan=\"6\">PUA220(聚环氧丙醚220)</td></tr><tr><td>HEA/%</td><td>12.1</td><td>10.0</td><td>9.6</td><td>7.5</td><td>8.3</td></tr><tr><td>DMPA/%</td><td>10.1</td><td>7.7</td><td>5.1</td><td>4.4</td><td>2.4</td></tr><tr><td>固化时间/s</td><td>1.0</td><td>10.9</td><td>34.8</td><td>90.0</td><td>180</td></tr></table></body></html>\n\n注：基团比 $\\c=$ —NCO·—OH(PPO):—OH(DMPA):—OH（HEA)。  \n\n加人 $1\\%$ 的二月桂酸二丁基锡和 $2\\mathrm{mol}$ 甲基丙烯酸羟乙酯， $45^{\\circ}\\mathrm{C}$ 反应 $^{2\\mathrm{h}}$ ，再加入三乙胺，室温下搅拌反应 $^\\mathrm{1h}$ ，得阴离子PUA。  \n\n将 $36\\mathbf{g}\\ \\mathbf{EA}$ 、 $24\\mathbf{g}$ 阴离子PUA、 $1.8\\mathbf{g}$ BP混合揽匀，滴加 $140\\mathbf{g}$ 水/乙醇（80/20）混合溶剂，得EA-PUA复合水分散体。  \n\n（15）UV-水性聚醚型PUA的合成在三口烧瓶中加人一定量的聚乙二醇、二羟甲基丙酸和少量 $N\\cdot$ -甲基吡咯烷酮，搅拌溶解，加入计算量的甲基二异氰酸酯和适量的催化剂二月桂酸二丁基锡，升温至 $75^{\\circ}\\mathrm{C}$ ，反应2h，再加人适量丙烯酸羟丙酯，继续反应2h，降温至$50^{\\circ}\\mathrm{C}$ ，加人丙酮稀释，以三乙胺中和后加水分散，蒸出丙酮得固含量 $30\\%$ 左右UV水性PUA，其性能见表3-79。  \n\n表3-79UV水性PUA的性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">PEG分子量</td><td rowspan=\"2\">PEG/DMPA (摩尔比)</td><td rowspan=\"2\">DMPA含量 1%</td><td rowspan=\"2\">黏度 /Pa·s</td><td colspan=\"4\">固化膜性能</td></tr><tr><td></td><td>硬度（布氏）冲击强度/×10-MPa</td><td>附着力/级</td><td>防雾性能/级</td></tr><tr><td>200</td><td>0.3/0.7</td><td>15.24</td><td>0.05</td><td>0.435</td><td>4.9</td><td>1</td><td>4</td></tr><tr><td>600</td><td>0.4/0.6</td><td>10.41</td><td>0.09</td><td>0.394</td><td>4.9</td><td>1</td><td>5</td></tr><tr><td>600</td><td>0.3/0.7</td><td>12.75</td><td>0.27</td><td>0.498</td><td>4.9</td><td>1</td><td>5</td></tr><tr><td>600</td><td>0.2/0.8</td><td>15.34</td><td>0.85</td><td>0.524</td><td>4.9</td><td>1</td><td>5</td></tr><tr><td>1000</td><td>0.3/0.7</td><td>10.96</td><td>1.22</td><td>0.576</td><td>4.9</td><td>1</td><td>5</td></tr></table></body></html>  \n\n（16）水性聚醚PUA的合成在三口烧瓶中加人一定量的聚醚二元醇（PPG）和甲苯二异氰酸酯（TDI)，通氮气，升温至 $65^{\\circ}\\mathrm{C}$ ，反应至一NCO值达预定值，再加人一定量丙烯酸羟乙酯和二羟甲基丙酸，在 $75\\mathrm{^\\circC}$ 反应至—NCO基本消失，降温至 $50^{\\circ}\\mathrm{C}$ ，加人少量对苯二酚搅匀得PUA，室温下加适量丙酮和三乙胺中和，剧烈搅拌下加水进行乳化，得到水性PUA，固含量 $25\\%\\sim30\\%$ 。不同条件对PUA黏度及固化膜性能的影响见表 $3\\textbar{-}80\\sim$ 表3-83。  \n\n表3-80 不同投料方式对PUA黏度影响（PPG-1000）  \n\n\n<html><body><table><tr><td>投料方式</td><td>黏度(30℃)/mPa·s</td></tr><tr><td>TDI先与PPG反应，再与HEA、DMPA反应</td><td>18000</td></tr><tr><td>TDI先与HEA、DMPA反应，再与PPG反应</td><td>24500</td></tr></table></body></html>  \n\n表3-81聚醚分子量对PUA黏度影响  \n\n\n<html><body><table><tr><td>聚醚二醇</td><td>分子量</td><td>黏度/mPa·s</td></tr><tr><td>PPG-400</td><td>400</td><td>24500</td></tr><tr><td>PPG-1000</td><td>1000</td><td>18000</td></tr><tr><td>PPG-2000</td><td>2000</td><td>8600</td></tr></table></body></html>  \n\n<html><body><table><tr><td>聚醚二元醇</td><td>硬度(邵氏)</td><td>拉伸强度/MPa</td><td>断裂伸长率/%</td></tr><tr><td>PPG-400</td><td>69.3</td><td>35.9</td><td>11.2</td></tr><tr><td>PPG-1000</td><td>25.0</td><td>21.0</td><td>41.0</td></tr><tr><td>PPG-2000</td><td>21.0</td><td>12.0</td><td>60.0</td></tr></table></body></html>  \n\n表3-83丙烯酸羟乙基含量对固化膜性能影响PPG-1000   \n\n\n<html><body><table><tr><td>丙烯酸羟基链节的质量分数/%</td><td>硬度(邵氏)</td><td>拉伸强度/MPa</td><td>断裂伸长率/%</td></tr><tr><td>6.09</td><td>42.1</td><td>19.8</td><td>46.7</td></tr><tr><td>8.70</td><td>56.4</td><td>26.7</td><td>35.2</td></tr><tr><td>12.60</td><td>69.3</td><td>35.9</td><td>11.2</td></tr><tr><td>13.91</td><td>72.5</td><td>40.1</td><td>6.4</td></tr><tr><td>15.22</td><td>79.8</td><td>42.8</td><td>一</td></tr></table></body></html>  \n\n表3-82聚醚分子量对固化膜性能影响  \n\n\n<html><body><table><tr><td>HPA用量nHPA/（nTDI-N210-nDMPA）</td><td>乳液外观</td><td>乳液黏度/mPa·s</td></tr><tr><td>0</td><td>黄色透明带有蓝光</td><td>2.00</td></tr><tr><td>0.50</td><td>乳白色带有蓝光</td><td>1.50</td></tr><tr><td>0.75</td><td>乳白色带有蓝光</td><td>1.50</td></tr><tr><td>1.00</td><td>乳白色带有蓝光</td><td>1.42</td></tr><tr><td>1.50</td><td>乳白色带有蓝光</td><td>1.30</td></tr></table></body></html>  \n\n（17）UV水性聚醚型PUA的合成在三口烧瓶中加人一定量的聚醚二元醇(N210)、二羟甲基丙酸和TDI，在65℃反应至—NCO不变，加人适量的丁酮、一定量丙烯酸羟丙酯（HPA）和0.1%的二月桂酸二丁基锡，在75℃反应至—NCO基本消失，降温加人三乙胺中和，再加入水强烈搅拌乳化，配成 $20\\%$ 的乳液，制成UV水性聚醚型PUA。不同HPA用量对PUA乳液性能的影响见表3-84。不同HPA用量对固化膜溶胀性能的影响见表3-85。  \n\n表3-84不同HPA用量对PUA乳液性能的影响  \n表3-85不同HPA用量对固化膜溶胀性能的影响  \n\n\n<html><body><table><tr><td>HPA含量</td><td colspan=\"3\">24h浸泡溶胀比</td></tr><tr><td>NHPA/(nTDI-nN210-DMPA）</td><td>丙酮</td><td>乙酸乙酯</td><td>甲苯</td></tr><tr><td>0</td><td>7.80</td><td>3.02</td><td>2.34</td></tr><tr><td>0.50</td><td>1.95</td><td>2.15</td><td>1.94</td></tr><tr><td>0.75</td><td>1.77</td><td>1.91</td><td>1.77</td></tr><tr><td>1.00</td><td>1.73</td><td>1.89</td><td>1.74</td></tr><tr><td>1.50</td><td>1.65</td><td>1.72</td><td>1.64</td></tr></table></body></html>  \n\n（18）UV水性PUA分散体的合成在三口烧瓶中加人聚醚二元醇，于 $120^{\\circ}\\mathrm{C}$ 脱水30min，冷至室温，加入异佛尔酮二异氰酸酯（IPDI)，在90℃反应2h，降温加人二羟甲基丙酸， $80^{\\circ}\\mathrm{C}$ 反应1h，加入适量丙酮，降温通入氮气保护，加入丙烯酸酯二醇、丙烯酸羟乙酯和适量阻聚剂、催化剂， $50^{\\circ}\\mathrm{C}$ 反应3h，加入计算量的三乙酯中和，再加入定量去离子水，强烈搅拌，真空脱去丙酮，得UV水性PVA分散剂，乳液含固量 $35\\%$ ， $\\mathrm{pH}{=}7.8{\\sim}8.2$ 要固化膜性能见表3-86。  \n\n表3-86 固化膜性能 $(5\\%$ 光引发剂2959）  \n\n\n<html><body><table><tr><td>—NCO:-OH</td><td>双键含量/（meq/g)</td><td>固化速率/s</td><td>摆杆硬度</td><td>柔韧性/mm</td><td>耐MEK性/次</td></tr><tr><td>7.5:1</td><td>4.5</td><td>40</td><td>0.796</td><td>5</td><td>320</td></tr><tr><td>5:1</td><td>3.6</td><td>50</td><td>0.63</td><td>2</td><td>280</td></tr><tr><td>3.5:1</td><td>3.0</td><td>70</td><td>0.632</td><td>1</td><td>140</td></tr><tr><td>2:1</td><td>1.8</td><td>85</td><td>0.43</td><td>1</td><td>70</td></tr></table></body></html>  \n\n（19）UV水性聚酯型PUA的合成在三口烧瓶中加入一定量的甲苯二异氰酸酯、聚己二酸丁二醇酯二醇（PBA羟值为 $111\\mathbf{mg\\KOH/g})$ 和适量二月桂酸二丁基锡，于 $40^{\\circ}\\mathrm{C}$ 搅拌混合均匀后，缓慢升温至 ${70}{\\sim}80^{\\circ}\\mathrm{C}$ 反应 $2\\mathrm{h}$ ，然后降温至 $40^{\\circ}\\mathrm{C}$ 以下，加人一定量二羟甲基丙酸（DM-PA)，混合均匀后于 ${70}\\mathrm{\\sim}80^{\\circ}\\mathrm{C}$ 反应 $2\\mathrm{h}$ ，然后降温至 $40^{\\circ}\\mathrm{C}$ ，加入丙烯酸羟乙酯和少量对甲氧基苯酚，于 $60^{\\circ}\\mathrm{C}$ 反应4h至—NCO反应完，得到带羧基的聚酯型聚氨酯丙烯酸树脂。  \n\n以上各步反应以二正丁胺法测定—NCO浓度来确定反应终点。室温下加人三乙胺中和，搅拌下加水制得 $30\\%$ 的乳液。亲水基团含量对乳液性能的影响见表3-87。中和度对乳液性能的影响见表3-88。DMPA含量对固化膜性能的影响见表3-89。  \n\n表3-87亲水基团含量对乳液性能的影响  \n\n\n<html><body><table><tr><td>—COOH/(mmol/g)</td><td>外观</td><td>稳定性</td><td>粒径/nm</td></tr><tr><td>0.20</td><td>乳白</td><td>有沉淀</td><td>一</td></tr><tr><td>0.26</td><td>乳白</td><td>稳定</td><td>173.2</td></tr><tr><td>0.33</td><td>乳白，带蓝光</td><td>稳定</td><td>105.8</td></tr><tr><td>0.57</td><td>蓝光，半透明</td><td>稳定</td><td>29.2</td></tr><tr><td>0.76</td><td>蓝光，近透明</td><td>稳定</td><td>25.4</td></tr><tr><td>0.91</td><td>蓝光，近透明</td><td>稳定</td><td>23.7</td></tr></table></body></html>  \n\n表3-88中和度对乳液性能的影响  \n\n\n<html><body><table><tr><td>中和度/%</td><td>外观</td><td>稳定性</td><td>乳液黏度/mPa·s</td></tr><tr><td>100</td><td>蓝光，近透明</td><td>稳定</td><td>7.5</td></tr><tr><td>90</td><td>蓝光，近透明</td><td>稳定</td><td>一</td></tr><tr><td>80</td><td>蓝光，半透明</td><td>稳定</td><td>5.5</td></tr><tr><td>70</td><td>乳白，带蓝光</td><td>稳定</td><td>4.8</td></tr><tr><td>60</td><td>乳白</td><td>稳定</td><td>4.2</td></tr><tr><td>50</td><td>乳白</td><td>稳定</td><td>4.0</td></tr><tr><td>40</td><td>乳白</td><td>不稳定</td><td></td></tr></table></body></html>  \n\n表3-89 DMPA含量对固化膜性能的影响  \n\n\n<html><body><table><tr><td>DMPA/PBA(摩尔比)</td><td>T/℃</td><td>铅笔硬度/H</td><td>附着力（PVC板)/级 9</td></tr><tr><td>3/10</td><td></td><td>2</td><td>0</td></tr><tr><td>2/5</td><td>-27.3</td><td>3</td><td></td></tr><tr><td>1/2</td><td>-20.5</td><td>3</td><td>0</td></tr><tr><td>1/1</td><td>-15.1</td><td>>6</td><td>0</td></tr><tr><td>2/3</td><td></td><td>>6</td><td></td></tr><tr><td>2/1</td><td></td><td>>6</td><td></td></tr></table></body></html>  \n\n（20）UV水性PUA的合成在三口烧瓶中加人2mol甲苯二异氰酸酯、lmolPBA（聚乙二酸丁二醇酯二醇）及少量二月桂酸二丁基锡。40℃左右混合均匀，升温至70～80℃，反应2h后降温至40℃以下，加人lmol二羟甲基丙酯，混匀后于70～80℃反应2h，降温至40℃以下，加人2mol丙烯酸羟乙酯和少量对甲氧基苯酚，60℃反应4h 得到PUA，以上各步以二正丁胺法测定—NCO浓度以确定反应终点。然后用三乙胺中和PUA后，加去离子水制得UV水性PUA，固含量 $30\\%$ 。  \n\n(21）UV水性聚酯PUA的合成在三口烧瓶中加人lmol羧基聚酯多元醇（PCI210BA，日本产）加热至 $50{\\sim}60^{\\circ}\\mathrm{C}$ ，加人 $2\\mathrm{mol}$ 甲苯二异氰酸酯、适量二月桂酸二丁基锡，升温至70～80℃反应2～3h，再加人2mol甲基丙烯酸聚丙二醇单酯（PEM6LD，科宁公司产品）和适量MEHQ，保温反应2～3h，至—NCO峰消失。降温加入三乙胺和去离子水，剧烈搅拌制得UV水性聚酯PUA。  \n\n（22）UV水性脂肪族PUA的合成在三口烧瓶中加人一定量聚醚二元醇（N210）、二羟基丙酸和异佛尔酮二异氰酸酯，在65℃反应至—NCO不变，加入适量丁酮，加人一定量丙烯酸羟丙酯和0.1%的二月桂酸二丁基锡，在75℃反应至—NCO基本消失，降温加人三乙胺中和，再加人一定量的水，强烈搅拌乳化，配成20%的乳液，得UV水性脂肪族PUA。不同HPA用量对PUA乳液性能的影响见表 3-90。不同HPA 用量对固化膜溶胀性能的影响见表3-91。  \n\n表3-90不同HPA用量对PUA乳液性能的影响  \n\n\n<html><body><table><tr><td>HPA用量nHPA/（nTDI-nN210-DMPA）</td><td>乳液外观</td><td>乳液黏度/mPa·s</td></tr><tr><td>0</td><td>乳白色带有蓝光</td><td>2.15</td></tr><tr><td>0.50</td><td>乳白色带有蓝光</td><td>1.71</td></tr><tr><td>0.75</td><td>乳白色带有蓝光</td><td>1.65</td></tr><tr><td>1.00</td><td>乳白色带有蓝光</td><td>1.58</td></tr><tr><td>1.50</td><td>乳白色带有蓝光</td><td>1.56</td></tr></table></body></html>  \n\n表3-91不同HPA用量对固化膜溶胀性能的影响  \n\n\n<html><body><table><tr><td rowspan=\"2\">HPA用量nHPA/（nTDIN210-DMPA）</td><td colspan=\"3\">24h浸泡溶胀比</td></tr><tr><td>丙酮</td><td>乙酸乙酯</td><td>甲苯</td></tr><tr><td>0</td><td>溶</td><td>溶</td><td>溶</td></tr><tr><td>0.50</td><td>2.45</td><td>2.82</td><td>2.89</td></tr><tr><td>0.75</td><td>2.13</td><td>2.29</td><td>1.99</td></tr><tr><td>1.00</td><td>2.02</td><td>2.16</td><td>2.01</td></tr><tr><td>1.50</td><td>1.98</td><td>1.99</td><td>1.89</td></tr></table></body></html>  \n\n（23）带光引发剂的UV水性PUA低聚物的合成在三口烧瓶加人一定量的甲苯二异氰酸酯、聚四氢呋喃二醇和适量的二月桂酸二丁基锡，升温至60℃，反应2h，加人二羟甲基丙酸混匀，60℃反应1h，降温，加人计算量的Irgacure2925、丙烯酸羟乙酯和少量对甲氧基苯酚，70℃反应至—NCO消失，制得带光引发剂和羧基的PUA低聚物，再用三乙胺中和，加人去离子水强烈搅拌，得到带有光引发剂的UV水性PUA低聚物乳液，固含量30%（PI-PUA)。不同2925含量PI-PUA的性能见表3-92。  \n\n表3-92不同2925含量PI-PUA的性能  \n\n\n<html><body><table><tr><td>样品编号</td><td>2925含量 （质量分数）/%</td><td>30%含水量外观</td><td>70%含水量外观</td><td>70%黏度/mPa·s</td><td>固化30s凝 胶含量/%</td></tr><tr><td>PUA</td><td>0</td><td>近透明</td><td>蓝色荧光，半透明</td><td>6.5</td><td></td></tr><tr><td>PI-PUA-1</td><td>0.86</td><td>近透明</td><td>蓝色荧光，半透明</td><td>6.2</td><td>96.5</td></tr><tr><td>PI-PUA-2</td><td>1.42</td><td>近透明</td><td>蓝色荧光，半透明</td><td>5.9</td><td>95.7</td></tr><tr><td>PI-PUA-3</td><td>2.03</td><td>近透明</td><td>蓝色荧光，半透明</td><td>6.0</td><td>95.4</td></tr><tr><td>PI-PUA-4</td><td>5.50</td><td>近透明</td><td>蓝色荧光，半透明</td><td>6.1</td><td>89.3</td></tr><tr><td>PI-PUA-5</td><td>6.88</td><td>近透明</td><td>蓝色荧光，半透明</td><td>6.0</td><td>84.0</td></tr></table></body></html>  \n\n（24）UV水性环氧改性PUA树脂的合成在三口烧瓶中滴加一定量 TDI、聚醚二元醇 N210、二羟甲基丙酸、环氧树脂和少量 $N\\mathrm{\\Omega}$ 甲基吡咯烷酮，搅拌下升温，在 $60\\sim80^{\\circ}{\\mathrm C}$ 反应，当—NCO含量接近理论值时，加入1,4-丁二醇（BDO)，在反应过程中加人丙酮调节黏度，当—NCO含量接近设计值时，加入适量丙烯酸羟丙酯、二月桂酸二丁基锡和对甲氧基苯酚，反应至—NCO基本消失，降至室温，加人三乙胺中和，在高速搅拌下加水得UV水性环氧改性PUA分散液。—COOH和 BDO不同含量对乳液性能的影响见表 3-93和表3-94。  \n\n表3-93—COOH含量对乳液性能的影响  \n\n\n<html><body><table><tr><td>-COOH含量（质量分数）/%</td><td>黏度/mPa·s</td><td>吸水率/%</td></tr><tr><td>1.80</td><td>1.16</td><td>5.18</td></tr><tr><td>2.00</td><td>1.20</td><td>6.31</td></tr><tr><td>2.20</td><td>1.26</td><td>7.45</td></tr><tr><td>2.40</td><td>1.35</td><td>9.03</td></tr><tr><td>2.60</td><td>1.57</td><td>12.42</td></tr></table></body></html>  \n\n表3-94BDO含量对乳液的性能的影响（异氰酸酯指数1,2，—COOH质量分数 $2.2\\%)$   \n\n\n<html><body><table><tr><td>BDO(质量分数)/%</td><td>吸水率/%</td><td>黏度/mPa·s</td><td>BDO(质量分数)/%</td><td>吸水率/%</td><td>黏度/mPa·s</td></tr><tr><td>3.41</td><td>9.23</td><td>1.16</td><td>6.25</td><td>5.04</td><td>1.50</td></tr><tr><td>4.12</td><td>7.75</td><td>1.20</td><td>7.40</td><td>4.81</td><td>1.78</td></tr><tr><td>5.82</td><td>6.02</td><td>1.35</td><td></td><td></td><td></td></tr></table></body></html>  \n\n本实验中 HPA 含量 $15\\%$ ，BDO含量 $5.8\\%$ ，环氧树脂含量 $8.75\\%$ ，乳液性能较好。  \n\n（25）UV异氰酸酯改性水性EA的合成在三口烧瓶中加人一定量双酚A环氧树脂CYD-128，升温至 $80^{\\circ}\\mathrm{C}$ ，按 $1:1$ 当量比滴加含有适量阻聚剂和催化剂的丙烯酸，缓慢升温至 $110^{\\circ}\\mathrm{C}$ ，反应5h至酸值 ${<}5\\mathrm{mg}\\ \\mathrm{KOH/g}$ ，停止反应得EA，降温至 $50^{\\circ}\\mathrm{C}$ ，加人适量丁酮、二月桂酸二丁基锡和阻聚剂， $60^{\\circ}\\mathrm{C}$ 下滴加计算量的TDI-HEA半加成物的丁酮溶液（半加成物中一NCO量对EA中—OH值为 $1:2)$ ，1h加完，反应至一NCO的 $2270\\mathrm{cm}^{-1}$ 吸收峰基本消失，得异氰酸酯改性EA。加入计算量的酸酐「酸酐当量与异氰酸酯改性EA的羟基当量比为 $(0.60{\\sim}0.70):1.00]$ ，升温至 $80^{\\circ}\\mathrm{C}$ ，反应 $90\\mathrm{{min}}$ ，加碱中和，滴加蒸馏水，同时蒸除丁酮，至蒸馏出温度 $81\\%$ ，停止，得淡黄色透明UV异氰酸酯改性水性EA。酸酐当量与环氧当量及改性树脂水溶性的关系见表3-95。  \n\n表3-95酸酐当量和环氧当量与改性树脂水溶性关系  \n\n\n<html><body><table><tr><td>酸酐当量：环氧当量</td><td>树脂可溶于水的最小固含量/%</td></tr><tr><td>0.8:1.0</td><td>45</td></tr><tr><td>0.5:1.0</td><td>65</td></tr><tr><td>0.2:1.0</td><td>90</td></tr></table></body></html>  \n\n固化膜的性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">固化速率/s</td><td rowspan=\"2\">铅笔硬度/H</td><td rowspan=\"2\">附着力/级</td><td rowspan=\"2\">柔韧性/级</td><td colspan=\"2\">耐化学品性能</td><td rowspan=\"2\">贮存稳定性</td></tr><tr><td>5% NaCl</td><td>5%NaOH</td></tr><tr><td>16</td><td>>4</td><td>3</td><td>3</td><td>48h</td><td>48h</td><td>>6个月</td></tr></table></body></html>  \n\n（26）UV水性PUA/EA的合成  \n\n①UV水性PUA的合成在三口烧瓶中，在氮气保护下加入4mol异佛尔酮二异氰酸酯，慢速滴加含1%二月桂酸二丁基锡的二羟甲基丙酸（2mol）的N,N-二甲基乙酰胺溶液，保持反应温度80℃，至-NCO浓度不变化时，在80℃缓慢加入lmol聚丁二醇醚。最后加人含1%二月桂酸二丁基锡的2mol甲基丙烯酸羟乙酯，45℃反应12h，直至反应混合物在红外光谱中2274cm-1吸收峰完全消失，加人计算量的三乙胺，室温下中和反应1h，制得水性UV-PUA。  \n\n② EA的合成在三口烧瓶中加人E-51环氧树脂、适量对苯二酚和N,N-二甲基苯胺，100℃以下缓慢滴加与环氧值等物质的量的丙烯酸，1.5h滴完，120℃反应4～5h至酸值<$3\\mathrm{mg}\\ \\mathrm{KOH}/\\mathbf{g}$ 费  \n\n③ UV水性PUA/EA制备在三口瓶中加人EA和 30%的PUA，搅拌下以0.18g/min速度滴加水与乙醇（80：20体积比）的混合溶液制备30%的水性UV-PUA/EA。  \n\n固化膜性能见表3-96。  \n\n表3-96 固化膜性能  \n\n\n<html><body><table><tr><td>PUA/EA</td><td>铅笔硬度/H</td><td>磨耗失重/mg</td><td>附着力/级</td></tr><tr><td>0</td><td>4</td><td>0.8</td><td>1</td></tr><tr><td>10</td><td>4</td><td>0.8</td><td>1</td></tr><tr><td>20</td><td>4</td><td>0.7</td><td>1</td></tr><tr><td>30</td><td>4</td><td>0.6</td><td>1</td></tr><tr><td>40</td><td>3</td><td>0.6</td><td>1</td></tr></table></body></html>\n\n注：1.PUA加人，PUA/EA分散体系稳定性增加。2.PUA加人，改善了EA柔韧性。3.PUA加人，改善了EA耐磨性，磨耗失重从0.8mg降至0.6mg。4. $30\\%$ PUA加入，对硬度影响不大，4H。  \n\n（27）UV水性聚氨酯改性丙烯酸树脂的合成在三口烧瓶中加入单体质量1.5倍的丁酮，升温至80℃，缓慢滴加100g甲基丙烯酸甲酯、22g丙烯酸丁酯、44.4g甲基丙烯酸羟乙酯和一定量的甲基丙烯酸二甲胺乙酯（DMAEMA)，3%的偶氮二异丁腈混合液，1h加毕，反应4h，使单体转化率达98%以上。降温加人适量二月桂酸二丁基锡，在60℃下1h内滴加42.4g甲基丙烯酸异氰酸乙酯（MOI)，反应3h后加人适量无水乙醇，除去未反应的MOI，真空抽除溶剂得聚氨酯改性丙烯酸树脂，加入光引发剂1173和184，用乳酸中和至pH值为6.0，用去离子水稀释到固含量为15%，经高速分散配成电泳漆。不同DMAEMA",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 104,
+        "chunk": "# 含量树脂的水溶性见表3-97。  \n\n表3-97不同DMAEMA含量树脂的水溶性  \n\n\n<html><body><table><tr><td>样品</td><td>DMAEA(质量分数)</td><td>外观</td><td>透明度（480nm）/%</td><td>稳定性/月</td></tr><tr><td>D-1</td><td>0.050</td><td>乳白色</td><td>55.1</td><td><6</td></tr><tr><td>D-2</td><td>0.078</td><td>半透明</td><td>59</td><td>>6</td></tr><tr><td>D-3</td><td>0.144</td><td>半透明</td><td>66.8</td><td>>6</td></tr><tr><td>D-4</td><td>0.252</td><td>半透明</td><td>73.0</td><td>>6</td></tr></table></body></html>\n\n注：固化55s，固化膜硬度 ${\\bf\\tau}>6\\mathbf{H}$ ，耐丁酮160次，对不锈钢附着力0级。  \n\n（28）UV水性聚甲基丙烯酸酯改性PUA的合成在三口烧瓶中加人甲基丙烯酸甲酯（MMA）和甲基丙烯酸缩水甘油酯（GMA）（质量比 $85:15)$ ，再加人丁酮和过氧化苯甲酰，通氮气于（ $75\\pm5)^{\\circ}\\mathrm{C}$ 搅拌反应8h制得MMA-GMA共聚物。  \n\n在三口烧瓶中加人适量聚乙二醇（PEG，分子量400、600、1000和2000）和二羟甲基丙酸(DMPA)，通氮气，搅拌下慢慢滴加质量比 $0.03:100$ 的二月桂酸二丁基锡和甲苯二异氰酸酯混合液， $45^{\\circ}\\mathrm{C}$ 反应至一NCO不变化，加人计算量的甲基丙烯酸羟乙酯，直至红外光谱中 $2274\\mathrm{cm}^{-1}$ 吸收峰消失。再加入 $20\\%$ 的MMA-GMA丁酮溶液， $45^{\\circ}\\mathrm{C}$ 反应2h，直至红外光谱中 $910\\mathrm{cm}^{-1}$ 、 $835\\mathrm{cm}^{-1}$ 吸收峰消失。搅拌下边加人计算量的三乙胺中和，边滴加水，边蒸馏除去丁酮，得UV水性聚甲基丙烯酸酯改性PUA分散液。PUA 和接枝PUA分散液表面张力与粒径见表3-98。固化膜的性能见表3-99。  \n\n表3-98PUA和接枝PUA分散液表面张力与粒径  \n\n\n<html><body><table><tr><td rowspan=\"2\">PEG(M)</td><td colspan=\"2\">表面张力/(mN/m)</td><td colspan=\"2\">粒径/mm</td></tr><tr><td>PUA</td><td>接枝PUA</td><td>PUA</td><td>接枝PUA</td></tr><tr><td>400</td><td>43.6</td><td>39.3</td><td>一</td><td></td></tr><tr><td>600</td><td>41.3</td><td>41.5</td><td>一</td><td>一</td></tr><tr><td>1000</td><td>40.2</td><td>42.9</td><td>187</td><td>167</td></tr><tr><td>2000</td><td>37.0</td><td>43.6</td><td>一</td><td>一</td></tr></table></body></html>\n\n$\\textcircled{1}$ 接枝PMA20%。  \n\n表3-99 固化膜的性能  \n\n\n<html><body><table><tr><td>样品</td><td>PEG(M)</td><td>附着力/级</td><td>硬度</td><td>冲击强度/MPa</td><td>柔韧性/mm</td></tr><tr><td rowspan=\"4\">PUA</td><td>400</td><td>2</td><td>0.50</td><td>>4.9</td><td>1</td></tr><tr><td>600</td><td>2</td><td>0.31</td><td>>4.9</td><td>1</td></tr><tr><td>1000</td><td>2</td><td>0.28</td><td>>4.9</td><td>1</td></tr><tr><td>2000</td><td>1</td><td>0.24</td><td>>4.9</td><td>1</td></tr><tr><td rowspan=\"4\">接枝PUA</td><td>400</td><td>2</td><td>0.78</td><td>>4.9</td><td>1</td></tr><tr><td>600</td><td>2</td><td>0.90</td><td>>4.9</td><td>1</td></tr><tr><td>1000</td><td>1</td><td>0.86</td><td>>4.9</td><td>1</td></tr><tr><td>2000</td><td>1</td><td>0.57</td><td>>4.9</td><td>1</td></tr></table></body></html>  \n\n（29）UV水性丙烯酸树脂接枝PUA树脂的合成在三口烧瓶中加人 $_{42g}$ 丙烯酸、$223.5\\mathbf{g}$ 丙烯酸丁酯、 $90.6\\mathbf{g}$ 苯乙烯和 $42.98\\$ 甲基丙烯酸羟乙酯，以过氧化苯甲酰为引发剂，以丁酮为溶剂，在 $80^{\\circ}\\mathrm{C}$ 共聚反应，制得丙烯酸树脂溶液，以分子筛干燥。  \n\n在三口烧瓶中加入 $46.1g$ 甲苯二异氰酸酯、 $_{30g}$ 二缩三乙醇（TEG）及适量丁酮进行反应，测定体系—NCO至接近平衡值，加人—OH为—NCO量0.6倍的季戊四醇三丙烯酸酯，加热反应至—NCO接近平衡值，制得聚氨酯丙烯酸酯 TPU-PETA（用聚乙二醇400代替TEG 得到PPU-PETA)。  \n\n将丙烯酸树脂与PU-PETA按不同比例投料，60℃反应，红外光谱法追踪 2274cm-1—NCO基团吸收强度，直至该吸收峰基本消失，停止反应，冷却，搅拌下加入三乙胺水溶液，得到稠状乳白液，蒸馏除去丁酮，得到黏度较小的丙烯酸树脂接枝PUA乳液。树脂固化膜的性能见表3-100。  \n\n表3-100 树脂固化膜的性能  \n\n\n<html><body><table><tr><td>样品</td><td>吸水率/%</td><td>耐擦次数/次</td><td>硬度</td><td>光泽</td><td>附着力/级</td><td>冲击强度/kgf·cm</td><td>柔韧性/mm</td></tr><tr><td>TPU-PETA(5/5)</td><td>7</td><td>212</td><td>77</td><td>89</td><td>2</td><td>50</td><td>2</td></tr><tr><td>TPU-PETA(6/4)</td><td>15</td><td>119</td><td>76</td><td>89</td><td>1</td><td>50</td><td>1</td></tr><tr><td>TPU-PETA(7/3)</td><td>40</td><td>94</td><td>74</td><td>87</td><td>1</td><td>50</td><td>1</td></tr><tr><td>TPU-PETA(8/2)</td><td>107</td><td>80</td><td>70</td><td>90</td><td>1</td><td>50</td><td>1</td></tr><tr><td>TPU-PETA(9/1)</td><td>236</td><td>23</td><td>66</td><td>87</td><td>2</td><td>50</td><td>1</td></tr><tr><td>PPU-PETA(5/5)</td><td>17</td><td>157</td><td>69</td><td>97</td><td>1</td><td>50</td><td>1</td></tr><tr><td>PPU-PETA(6/4)</td><td>30</td><td>128</td><td>66</td><td>96</td><td>2</td><td>50</td><td>1</td></tr><tr><td>PPU-PETA(7/3)</td><td>65</td><td>106</td><td>66</td><td>91</td><td>１</td><td>50</td><td>1</td></tr><tr><td>PPU-PETA(8/2)</td><td>112</td><td>52</td><td>61</td><td>98</td><td>I</td><td>50</td><td>1</td></tr><tr><td>PPU-PETA(9/1)</td><td>230</td><td>6</td><td>53</td><td>94</td><td>2</td><td>50</td><td>2</td></tr></table></body></html>\n\n注；PUA含30%～50%性能较好，TPU-PETA比PPU-PETA更佳。1kgf=9.8N，下同。  \n\n（30）UV水性聚氨酯改性丙烯酸树脂的合成在三口烧瓶中加人50mL丁酮，通氮气，升温至80℃，滴加25mL丙烯酸丁酯（0.17mol)、10mL苯乙烯（0.087mol)、一定量丙烯酸（0.036～0.057mol)、甲基丙烯酸羟乙酯（0.033～0.037mol）及过氧化苯甲酰引发剂溶液，3h滴完，继续反应12h制得含有一COOH和一OH的丙烯酸树脂。  \n\n加入2滴二月桂酸二丁基锡、50mL丁酮和适量对苯二酚，升温至60℃，滴加计算量的TDI-HEMA半加成物（半加物—NCO与丙烯酸树脂—OH之比为0.67～1.0)，1h加完，红外监测—NCO的2274cm—吸收峰基本消失，停止反应，加入计量的三乙胺中和搅拌，蒸除丁酮，滴加蒸馏水至馏出温度81℃，停止反应，得白色自乳化UV水性聚氨酯改性丙烯酸树脂。树脂性能及对固化膜影响因素见表3-101～表3-104。  \n\n表3-101接枝丙烯酸树脂的分子量  \n\n\n<html><body><table><tr><td>样品</td><td>AA/mol</td><td>HEMA/mol</td><td>[—NCO]/[—OH]</td><td>M/×103</td><td>Mw/X103</td><td>Mw/Mn</td></tr><tr><td>A3</td><td>0.044</td><td>0.033</td><td>1:1</td><td>2.90</td><td>8.59</td><td>2.98</td></tr><tr><td>B3</td><td>0.051</td><td>0.037</td><td>0.67:1</td><td>2.33</td><td>7.68</td><td>3.29</td></tr><tr><td>B5</td><td>0.051</td><td>0.037</td><td>0.89·1</td><td>3.03</td><td>9.37</td><td>3.09</td></tr></table></body></html>  \n\n表3-102自乳化接枝丙烯酸树脂粒径  \n\n\n<html><body><table><tr><td>样品</td><td>AA/mol</td><td>HEMA/mol</td><td>[--NCO]/[—OH]</td><td>粒径/nm</td><td>分散性</td></tr><tr><td>A3</td><td>0.044</td><td>0.033</td><td>1:1</td><td>200.9</td><td>0.606</td></tr><tr><td>A4</td><td>0.051</td><td>0.033</td><td>1:1</td><td>176.0</td><td>1.000</td></tr></table></body></html>  \n\n表3-103AA用量对固化膜性能的影响（HEMA $_{,=0,033\\mathrm{mol}}$ ，[—NCO]/[--OH]=1:1)  \n\n\n<html><body><table><tr><td>样品</td><td>AA/mol</td><td>附着力/级</td><td>柔韧性/mm</td><td>光泽</td><td>硬度/S</td><td>冲击强度/kgf·cm</td><td>耐水性</td><td>膜厚/μm</td></tr><tr><td>A1</td><td>0.029</td><td>3</td><td>1</td><td>105</td><td>57</td><td>30</td><td>19</td><td>43</td></tr><tr><td>A2</td><td>0.036</td><td>2</td><td>1</td><td>108</td><td>61</td><td>30</td><td>17</td><td>44</td></tr><tr><td>A3</td><td>0.044</td><td>2</td><td>1</td><td>114</td><td>61</td><td>40</td><td>14</td><td>48</td></tr><tr><td>A</td><td>0.051</td><td>2</td><td>1</td><td>116</td><td>61</td><td>40</td><td>10</td><td>44</td></tr><tr><td>As</td><td>0.058</td><td>2</td><td>1</td><td>122</td><td>65</td><td>40</td><td>7</td><td>41</td></tr><tr><td>A6</td><td>0.066</td><td>1</td><td>1~2</td><td>124</td><td>65</td><td>45</td><td>5</td><td>41</td></tr></table></body></html>  \n\n表3-104[—NCO]/[—OH]对固化膜性能影响（[HEMA] $=0.037\\mathrm{mol}$ ，[AA] =0.051mol)  \n\n\n<html><body><table><tr><td>样品</td><td>[—NCO]/[—OH]</td><td>附着力/级</td><td>柔韧性/mm</td><td>光泽</td><td>硬度/S</td><td>冲击强度/kgf·cm</td><td>耐水性</td><td>膜厚/μm</td></tr><tr><td>B</td><td>0.44</td><td>1</td><td>1</td><td>119</td><td>61</td><td>35</td><td>3</td><td>43</td></tr><tr><td>B</td><td>0.56</td><td>2</td><td>1</td><td>114</td><td>62</td><td>35</td><td>3</td><td>46</td></tr><tr><td>B3</td><td>0.67</td><td>2</td><td>1~2</td><td>114</td><td>61</td><td>40</td><td>5</td><td>42</td></tr><tr><td>B</td><td>0.78</td><td>2</td><td>1~2</td><td>114</td><td>66</td><td>40</td><td>7</td><td>41</td></tr><tr><td>Bs</td><td>0.89</td><td>2</td><td>1</td><td>108</td><td>67</td><td>40</td><td>9</td><td>43</td></tr><tr><td>B6</td><td>1.0</td><td>2</td><td>1~2</td><td>106</td><td>67</td><td>45</td><td>11</td><td>45</td></tr></table></body></html>  \n\n乳液于 $6\\%$ 避光放置3个月，体系无沉降、板结等劣化现象，UV固化涂层综合性能仅有轻微下降。  \n\n（31）有机硅改性UV水性PUA树脂的合成在三口烧瓶中加人聚醚二元醇（PT-MG)、聚二端羟丁基二甲基硅氧烷、异佛尔酮二异氰酸酯和二羟甲基丙酸， $80^{\\circ}\\mathrm{C}$ 反应至—NCO达到理论值，加入适量丙酮，降温通氢气保护，加入丙烯酸酯二醇、丙烯酸羟乙酯、适量阻聚剂和催化剂， $50^{\\circ}\\mathrm{C}$ 反应至一NCO消失，加入计算量的三乙胺中和，加人定量去离子水强烈搅拌，真空脱去丙酮，得到有机硅改性UV水性PUA树脂，乳液固含量 $35\\%$ ，$\\mathbf{pH}{=}7.8{\\sim}8.2$ 。硅氧烷含量对树脂涂层接触角的影响见表3-105。  \n\n表3-105硅氧烷含量对树脂涂层接触角影响  \n\n\n<html><body><table><tr><td>硅氧烷含量/%</td><td>接触角/(°)</td><td>硅氧烷含量/%</td><td>接触角/(°)</td></tr><tr><td></td><td>70.1</td><td>7</td><td>95</td></tr><tr><td>2</td><td>89.3</td><td>11</td><td>95</td></tr><tr><td>4</td><td>93.2</td><td>15</td><td>95</td></tr></table></body></html>  \n\n（32）溶胶-凝胶法制备UV-PUA杂化材料将一定量的乙醇、正硅酸乙酯加人装有滴液漏斗的锥形瓶中，室温下，边搅拌边滴加用盐酸酸化过的乙醇与水的混合液（n正硅酸乙酯：水‘nz醇‘n盐酸=1：6：6：0.06）滴完后继续反应12h，得硅溶胶（A)。在室温下向A中滴人 $\\gamma$ 甲基丙烯酰氧丙基三甲氧基硅烷（TMSPM)，磁力揽拌均匀后陈化 $24\\mathrm{h}$ ，得改性硅溶液 (B)。  \n\n将聚氨酯丙烯酸酯EB-270（氰特公司产品）、己二酸二丙烯酸酯按 $4:1$ 的比例加入三口烧瓶中，再加人 $2\\%$ 的光引发剂1173和 $0.5\\%$ 的乳化剂吐温-80，剧烈搅拌得C，在C中滴人B，剧烈搅拌直至体系均匀透明为止，得到PUA-TMSPM/ $\\mathrm{SiO}_{2}$ 杂化体系，该杂化体系是以聚氨酯丙烯酸酯为基材，以己二酸二丙烯酸酯为活性稀释剂，以TMSPM为偶联剂，正硅酸乙酯为无机前驱体，通过溶胶-凝胶法制备的UV杂化材料。  \n\n当 $\\mathrm{C/B}{<}6/4$ 时，得到的杂化材料是透明的， $\\mathbf{C}/\\mathbf{B}\\geqslant8/2$ 时光固化膜呈白雾状。杂化材料固化膜的性能见表3-106。  \n\n表3-106杂化材料固化膜的性能  \n\n\n<html><body><table><tr><td>样品</td><td>C/B</td><td>膜厚/μm</td><td>光泽/%</td><td>附着力/级</td><td>铅笔硬度</td><td>冲击强度/kgf·cm</td><td>柔韧性/mm</td></tr><tr><td>PUA/HDDA</td><td>0</td><td>18</td><td>189.4</td><td>1</td><td>F</td><td>50</td><td>1</td></tr><tr><td>PUA-TMSPM/SiO2</td><td>1/6</td><td>28</td><td>143.0</td><td>1</td><td>H</td><td>50</td><td>1</td></tr><tr><td>PUA-TMSPM/SiO2</td><td>2/8</td><td>14</td><td>147.5</td><td>1</td><td>H</td><td>50</td><td>1</td></tr><tr><td>PUA-TMSPM/SiO2</td><td>4/6</td><td>12</td><td>160.3</td><td>1</td><td>2H</td><td>50</td><td>1</td></tr><tr><td>PUA-TMSPM/SiO2</td><td>5/5</td><td>28</td><td>137.7</td><td>1</td><td>2H</td><td>50</td><td>1</td></tr><tr><td>PUA-TMSPM/SiO2</td><td>6/4</td><td>20</td><td>143.3</td><td>1</td><td>3H</td><td>50</td><td>1</td></tr><tr><td>PUA-TMSPM/SiO2</td><td>8/2</td><td>15</td><td>126.5</td><td>1</td><td>3H</td><td>50</td><td>1</td></tr><tr><td>PUA-TMSPM/SiO2</td><td>6/1</td><td>19</td><td>150.7</td><td>1</td><td>3H</td><td>50</td><td>1</td></tr></table></body></html>  \n\n（33）UV水性PEA的合成在三口烧瓶中加人一定量的季戊四醇、邻苯二甲酸酐和总量0.2%的钛酸丁酯，加热至150～160℃，反应60min，冷却至100℃以下，加入计算量的丙烯酸羟乙酯、0.1%的（质量分数）对苯二酚和0.5%（质量分数）的对甲苯磺酸 早 甲苯回流去水，计算出水值至一定值后停止反应，减压蒸出甲苯。室温下加入二甲基乙醇胺中和，剧烈搅拌下加水至一定固含量，即得UV水性PEA。其配比、水溶性及固化性能的影响见表3-107～表3-109。  \n\n<html><body><table><tr><td>序号</td><td>季戊四醇：邻苯二甲酸酐(摩尔比)</td><td>末端感光基团P</td><td>亲水基团W</td></tr><tr><td>A1</td><td>1:4</td><td>2</td><td>2</td></tr><tr><td>A2</td><td>2:7</td><td>3.2</td><td>2.8</td></tr><tr><td>A3</td><td>3:10</td><td>4.8</td><td>3.2</td></tr></table></body></html>  \n\n表3-108不同固含量的 $(\\mathbf{A}_{2}$ ）树脂水溶性  \n\n\n<html><body><table><tr><td>固含量/%</td><td>90</td><td>80</td><td>70</td><td>60</td><td>50</td></tr><tr><td>水溶性</td><td>透明溶液</td><td>透明溶液</td><td>半透明溶液</td><td>乳液</td><td>乳液</td></tr></table></body></html>\n\n注：放置半年，无分层、沉降、板结等现象。  \n\n表3-107 不同摩尔比聚酯P、W值  \n\n\n<html><body><table><tr><td>序号</td><td>A1</td><td>A</td><td>As</td></tr><tr><td>末端感光基团P</td><td>2</td><td>3.2</td><td>4.8</td></tr><tr><td>固化时间/s</td><td>15</td><td>10</td><td>7</td></tr></table></body></html>\n\n注： $3\\%$ 的1173加人后，在1kW紫外灯 $5.5\\mathrm{cm}$ 处的固化时间。  \n\n（34）UV水性超支化聚酯合成（一）在三口烧瓶中加入4.8g偏苯三酸酐、0.2g四乙基溴化铵，升温至70℃，将208g环氧氯丙烷缓慢滴加至体系中，反应约5h，至酸值恒定。再加人1.42g甲基丙烯酸缩水甘油酯（MGA)，反应3h，冷至室温，加入1g三乙胺（TEA）中和，加20%的水，制得UV水性超支化聚酯（HBPE)。不同GMA和 TEA 的HBPE见表3-110，HBPE（4.4）树脂黏度随温度和含水量的变化见表3-11l。  \n\n表3-109感光官能度对树脂固化性能的影响  \n表3-110不同GMA和TEA的HBPE  \n\n\n<html><body><table><tr><td rowspan=\"3\">树脂</td><td colspan=\"2\">GMA的量</td><td colspan=\"2\">TEA的量</td></tr><tr><td>/g</td><td>/mmol</td><td>/g</td><td>/mmol</td></tr><tr><td>HBPE(2.6)</td><td>3.08</td><td>21.7</td><td>6.61</td><td>65.3</td></tr><tr><td>HBPE(4.4)</td><td>5.85</td><td>41.2</td><td>4.03</td><td>39.8</td></tr><tr><td>HBPE(5.3)</td><td>7.19</td><td>50.6</td><td>3.06</td><td>30.2</td></tr><tr><td>HBPE(6.2)</td><td>8.96</td><td>63.1</td><td>1.99</td><td>19.2</td></tr></table></body></html>\n\n注：含水 $20\\%$ ， $20\\mathrm{\\sim}50^{\\circ}\\mathrm{C}$ ，四种树脂水溶液 $_2$ 个月保持外观半透明和稳定。  \n\n表3-111HBPE（4.4）树脂黏度随温度和含水量变化  \n\n\n<html><body><table><tr><td rowspan=\"2\">含水量/%</td><td colspan=\"4\">黏度/mPa·s</td></tr><tr><td>20℃</td><td>30℃</td><td>40℃</td><td>50℃</td></tr><tr><td>0</td><td>6530</td><td>4320</td><td>2750</td><td>1490</td></tr><tr><td>5</td><td>4620</td><td>3140</td><td>2210</td><td>1550</td></tr><tr><td>10</td><td>3240</td><td>1930</td><td>1320</td><td>980</td></tr></table></body></html>  \n\n（35）UV水性超支化聚酯的合成（二）在装有冷凝器、恒压漏斗、搅拌的三口烧瓶中，加人4.8g偏苯三酸酐、3g甲基四氢苯酐、0.2g四乙基溴化铵和10gN,N-二甲基甲酰胺，升温至90℃后，将4.6g环氧氯丙烷缓慢滴加至体系中，反应5h后，加入0.03g对甲氧基苯酚，降温至70℃后向体系中滴加2.6g甲基丙烯酸缩水甘油酯，反应至酸值恒定。最后用三乙胺中和，制得UV水性超支化聚酯。  \n\n（36）UV水性超支化聚酯的合成（三）按CN1248586A合成第二代超支化聚酯HBP，测定羟基含量，加人一定量 TDI-HEA半加成物、适量二月桂酸二丁基锡和对甲氧基苯酚混合搅匀，升温至70～80℃反应2h，测定羟值，加人等摩尔比的马来酸酐，升温至70～80℃反应，测定酸值至理论值停止反应，降至室温，加人三乙胺中和，得UV水性超支化聚酯。不同羧基含量树脂的水溶性见表3-112。  \n\n表3-112不同羧基含量树脂的水溶性  \n\n\n<html><body><table><tr><td>超支化聚酯</td><td>羚基含量/%</td><td>10%水含量</td><td>30%水含量</td><td>50%水含量</td></tr><tr><td>1</td><td>1.32</td><td>透明</td><td>微透明</td><td>沉淀分层</td></tr><tr><td>2</td><td>2.57</td><td>透明</td><td>半透明</td><td>沉淀分层</td></tr><tr><td>3</td><td>3.75</td><td>透明</td><td>半透明</td><td>沉淀分层</td></tr><tr><td>4</td><td>4.81</td><td>透明</td><td>透明</td><td>有沉淀</td></tr><tr><td>5</td><td>5.93</td><td>透明</td><td>透明</td><td>半透明</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 105,
+        "chunk": "# 3.20.6其他丙烯酸低聚物的合成  \n\n（1）聚丙烯酸酯低聚物的合成在三口烧瓶中加入一定量的甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、琉基乙酸、甲苯和偶氮二异丁腈，依次抽真空，充氮气重复3次，升温至85℃，反应10h，制得分子链一端带有羧基官能团的低聚物P，用甲醇沉淀，再用甲苯重新溶解，重复3次，红外干燥真空干燥至恒重。  \n\n将低聚物P和甲基丙烯酸缩水甘油酯（摩尔比为1：1.5)、催化剂1.5%苄基氯化三乙胺及高温阻聚剂混合，氮气保护下，升温到138℃，反应9～12h，制得聚丙烯酸酯低聚物，精制方法同P。单体组成对聚丙烯酸酯低聚物玻璃化温度的影响见表3-113，不同催化剂种类对合成聚丙烯酸低聚物的影响见表3-114。  \n\n表3-113单体组成对聚丙烯酸酯低聚物玻璃化温度的影响  \n\n\n<html><body><table><tr><td rowspan=\"2\">序号</td><td colspan=\"4\">组成 DX</td></tr><tr><td>MMA/%</td><td>EA/%</td><td>BA/%</td><td>T/℃ 9</td></tr><tr><td>1</td><td>60</td><td>10</td><td>30</td><td>24.1</td></tr><tr><td>2</td><td>70</td><td>10</td><td>20</td><td>41.5</td></tr><tr><td>3</td><td>75</td><td>10</td><td>15</td><td>50.6</td></tr><tr><td>4</td><td>80</td><td>10</td><td>10</td><td>61.7</td></tr></table></body></html>\n\n注：环氧丙烯酸酯按10%，甲基丙烯酸甲酯（MHA）按75%～80%，丙烯酸丁酯（BA）按10%～15%，使Tg在$50\\sim60^{\\circ}C$  \n\n表3-114不同催化剂种类对合成聚丙烯酸低聚物的影响  \n\n\n<html><body><table><tr><td>催化剂</td><td>聚丙烯酸低聚物得率/%</td><td>催化剂</td><td>聚丙烯酸低聚物得率/%</td></tr><tr><td>未加</td><td>59.5</td><td>N,N-二甲基苄胺</td><td>95.9</td></tr><tr><td>异丙胺</td><td>70.8</td><td>苄基氯化三乙胺</td><td>99.5</td></tr><tr><td>二乙胺</td><td>87.5</td><td></td><td></td></tr></table></body></html>\n\n注；P：GMA=1：1.5，催化剂用量1.5%（摩尔分数)，反应温度138℃C，反应时间12h。  \n\n（2）大豆油脂肪酸改性丙烯酸酯的合成在三口烧瓶中加人366g二甲苯加热至138℃，滴加13.2g丙烯酸、190.3g苯乙烯、180.8g甲基丙烯酸甲酯及7.73g过氧化苯甲酰混合液，2h内加完，第3h及第4h再各添加lg过氧化苯甲酰（溶于34mL二甲苯）生成三元共聚物AA-St-MMA。  \n\n上述反应5h后，降温至100℃，加人140.3g三羟甲基丙烷，升温至230℃，发生酯化反应，反应完后1h内滴加231g大豆油脂肪酸继续在230℃酯化反应，降温至100℃，通Nz再加120g邻苯二甲酸酐，升温至230℃，反应2h，降温至50℃，缓慢滴加TDI-HEA半加成物，1h加完，反应至—NCO<0.2%，得到大豆油脂肪酸性丙烯酸酯。  \n\n（3）三（环氧丙基）异氰脲酸丙烯酸树脂的合成在三口烧瓶中加人1mol三环氧丙基异氰脲酸酯（TGlC)、2.79mol丙烯酸、适量阻聚剂2,6-二叔丁基对甲苯酚，加热至80℃，使反应物溶化，搅拌下，加人适量催化剂N,N-二甲基苯胺（用量为0.7%的TGIC)，反应温度105℃，反应3h后，取样测酸值，当酸值<5mgKOH/g时，停止反应，得淡黄色黏稠透明液体即为三（环氧丙基）异氰脲酸丙烯酸酯。  \n\n（4）丙烯酸化聚磷酸酯的合成  \n\n![](images/b3b750e60406140120f18ef4ed2a7b0dab415add66dbad0e8310587ba4e9f59d.jpg)  \n\n在装有回流冷凝管、滴液漏斗、氮气管的四口烧瓶中加人20g氧氯化磷（0.13mol）和乙醚250mL，在冰浴中缓慢滴人17.4g丙烯酸羟乙酯（0.15mol）和30.8g吡啶（0.39mol)，25℃下反应24h，得POHEA。27.5g双酚A（0.12mol）预溶在适量的乙醚中，慢慢滴加到上述反应瓶中，25℃下继续反应24h。过滤，除去滤液中的乙醚，加人40mL二氯甲烷，待完全溶解，加人大量的水，用稀盐酸调至酸性。分液，油相用饱和碳酸氢钠溶液洗涤，再用蒸馏水洗至中性。用无水硫酸钠干燥后将二氯甲烷抽出，得到无色透明的丙烯酸  \n\n化聚磷酸酯（APP)，产率 $82.4\\%$ D（5）含磷阻燃性聚氨酯丙烯酸酯的合成  \n\n① 含磷二醇合成在三口烧瓶中加人适量双酚A二缩水甘油醚，搅拌加热至70℃，缓慢加入与环氧基等物质的量的磷酸二异辛酯（或磷酸二丁酯)，1h加完，升温至90℃，再反应3h，最终反应的酸值<10mgKOH/g（必要时可加人少量环氧化合物)，环氧值<$0.01\\mathrm{mol}/100\\mathrm{g}$ 。  \n\n② 含磷阻燃性聚氨酯丙烯酸酯的合成在三口烧瓶中加人3mol甲苯二异氰酸酯和适量对苯二酚、二月桂酸二丁基基锡，缓慢加人2mol丙烯酸羟乙酯，在30～50℃反应，再将4mol的含磷二醇和适量已二醇二丙烯酸酯在1h内加人，升温至60～70℃反应，当—NCO<1%时，加入少量抑制剂，升温到90℃反应至—NCO<0.5%（必要时加人少量丙烯酸羟乙酯)，得到含磷阻燃性聚氨酯丙烯酸酯。  \n\n(6）磷酸酯改性的环氧聚氨酯丙烯酸酯的合成  \n\n①含磷二醇（p-diol）合成将lmol双酚A二缩水甘油醚加人三口烧瓶中，升温至70℃，在1h 内缓慢滴加1mol磷酸二丁酯，升温90℃反应3h，制得含磷二醇（p-diol)，最终反应物酸值<10mgKOH/g，环氧值<0.0lmol/100g。  \n\n：②含磷环氧聚氨酯丙烯酸酯（P-EUA）的合成将lmol甲苯二异氰酸酯加人三口烧瓶中，加热至40～50℃，加入适量对苯二酚和二月桂酸二丁基锡，再将1mol的丙烯酸羟乙酯缓慢加热至40～50℃，反应至—NCO值不变化，再加入1mol含磷二醇和适量活性稀释剂三丙二醇二丙烯酸酯，升温至70℃，反应至—NCO<0.5%，停止反应，制得阻燃型磷酸酯改性的环氧-聚氨酯丙烯酸酯 (P-EUA)。  \n\n当P-EUA：TPGDA：TMPTA=3：1.5：0.5，I1700 5%，活性胺 5%，固化速率4.3s，涂层含磷2.9%，600℃碳渣23.8%，800℃碳渣22.8%，极限氧指数LOI为26.3。  \n\n（7）含氟丙烯酸磷酸酯的合成  \n\n$$\n\\begin{array}{r l r}{\\lefteqn{\\mathrm{Cl-~}\\overset{0}{\\underset{\\mathrm{Cl-~}}{\\longrightarrow}}\\mathrm{Cl~}+\\mathrm{C}_{2}\\mathrm{F}_{s}\\mathrm{OH}\\underset{\\bigcirc_{\\mathrm{N}}^{\\mathrm{()}}}{\\longrightarrow}\\mathrm{Cl-~}\\overset{1}{\\underset{\\mathrm{OF}_{s}\\mathrm{C}_{2}}{\\longrightarrow}}\\quad\\overset{\\mathrm{H}0-\\mathrm{(CH_{2})}_{4}-\\mathrm{OH}}{\\underset{\\bigcirc_{\\mathrm{N}}^{\\mathrm{()}}}{\\longrightarrow}}\\star\\mathrm{~H}0-\\mathrm{(CH_{2})}_{4}-\\mathrm{O}-\\overset{1}{\\underset{\\mathrm{DF}_{s}\\mathrm{C}_{2}}{\\longrightarrow}}\\mathrm{O}-(\\mathrm{CH_{2}})_{4}-\\mathrm{OH}}}\\\\ &{}&{\\overset{\\mathrm{O}}{\\underset{\\longrightarrow}{\\longrightarrow}}\\frac{\\mathrm{H}_{2}\\mathrm{C}-\\mathrm{CH}\\mathrm{CoCl}}{\\underset{\\bigcirc_{\\mathrm{N}}^{\\mathrm{()}}}{\\longrightarrow}}\\mathrm{H}_{2}\\mathrm{C}-\\mathrm{CH}\\mathrm{COO}-(\\mathrm{CH_{2}})_{4}-\\mathrm{O}-\\overset{1}{\\underset{\\mathrm{DF}_{s}\\mathrm{C}_{2}}{\\longrightarrow}}\\mathrm{O}-(\\mathrm{CH_{2}})_{4}-\\mathrm{OOCCH}-\\mathrm{CH}_{2}}\\\\ &{}&{\\overset{\\mathrm{O}}{\\longrightarrow}\\mathrm{OF}_{s}\\mathrm{C}_{2}}\\end{array}\n$$  \n\n在三口烧瓶中加入10.00g（0.065mol）三氯氧磷和200mL乙醚，置于冰浴中，缓慢滴加29.50g（0.065mol）全氟烃基乙醇和5.10g（0.065mol）吡啶混合物，在25℃时搅拌反应8h。再缓慢滴加8.8g（0.098mol）1,4-丁二醇、15.5g（0.196mol）吡啶和适量乙醚混合物，25℃搅拌12h。然后缓慢滴加11.80g（0.130mol）丙烯酰氯，并加人12.30g（0.156mol）吡啶，25℃搅拌反应12h。反应产物经过滤，滤饼经中和、洗涤和干燥，蒸去溶剂，得到青灰色固体A，为光固化含氟丙烯酸磷酸酯，具有优异的阻燃性，氧指数LOI为38，固化膜的表面张力 $20,3\\mathrm{mN/m}$ ，与水接触角 $109^{\\circ}$ ，与溴代萘接触角 $82^{\\circ}$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 106,
+        "chunk": "# （8）含氟丙烯酸磷酸酯的合成  \n\n在三口烧瓶中加人 $\\eta,67_{\\mathbf{8}}$ 1 $\\left(0.050\\mathbf{m}\\mathbf{o}1\\right)$ 三氯氧磷和 $200\\mathrm{mL}$ 乙醚，置于冰浴中，缓慢滴加 $22.80\\mathbf{g}$ + $\\left(0,050\\mathrm{mol}\\right)$ ）全氟烃基乙醇和 $5.10{\\bf g}$ （0.050mol）三乙胺混合物，在 $25^{\\circ}\\mathrm{C}$ 搅拌反应 $^{8\\mathbf{h}}$ 。再滴加 $\\boldsymbol{5.81g}$ 1 $\\left(0.050\\mathrm{mol}\\right)$ ）丙烯酸羟乙酯、 $5.10\\mathbf{g}$ $(0.050\\mathrm{mol})$ 三乙胺和适量乙醚混合物， $25\\mathrm{^\\circC}$ 搅拌反应 $^{12\\mathrm{{h}}}$ 。然后再缓慢滴加 $\\scriptstyle2,43\\mathbf{g}$ （ $\\mathrm{0.027mol}$ ）1,4-丁二醇、 $5.5{\\bf g}$ $(0,054\\mathrm{mol})$ ）三乙胺和适量乙醚混合物， $25\\mathrm{^\\circC}$ 搅拌反应 $^{12\\mathrm{{h}}}$ 。反应产物经过滤，滤饼经中和、洗涤和干燥，蒸去溶剂，得到淡黄色固体B，为光固化含氟丙烯酸磷酸酯，具有优异的阻燃性，氧指数LOI为36；固化膜的表面张力 $20.8\\mathrm{mN/m}$ ，与水接触角 $\\boldsymbol{105^{\\circ}}$ ，与溴萘的接触角 $86^{\\circ}$ 。  \n\n（9）不饱和聚酯-环氧树脂嵌段共缩聚型UV低聚物的合成在三口烧瓶中加入计算量的丙二醇/苯酐和马来酸酐（羧基过量 $30\\%\\sim35\\%$ ，摩尔分数)，升温至 $195\\sim200^{\\circ}\\mathrm{C}$ ，反应至酸值降至150左右，加入与不饱和聚酯酸值等物质的量的环氧树脂，继续反应一定时间后，降温至 $110^{\\circ}\\mathrm{C}$ ，按计算量加入丙烯酸封闭端基，当酸值降至10以下时停止反应，得到不饱和聚酯-环氧树脂嵌段共缩聚型UV低聚物。羧基过量不同时聚合物的性能比较见表3-115。  \n\n表3-115羧基过量不同时聚合物的性能比较  \n\n\n<html><body><table><tr><td>序号</td><td>羧基过量/%</td><td>不饱和聚酯分子量</td><td>共缩聚光敏低聚物固化速率/s</td><td>附着力/级</td><td>柔韧性/级</td><td>硬度/H</td></tr><tr><td>A</td><td>30</td><td>730</td><td></td><td>１</td><td>1</td><td>3~4</td></tr><tr><td>B</td><td>35</td><td>600</td><td>18</td><td>1</td><td>1</td><td>2</td></tr></table></body></html>  \n\n（10） $^{2,2^{\\prime},5,5^{\\prime}}$ -四甲酸丙烯酸（2-羟基）丙二酯苯甲酸对环己二酯的合成  \n\n![](images/7b0dc1e25ef9cb019d5ea584d31737395fd284a2065184fadd3dbb4c25280362.jpg)  \n\n在三口烧瓶中加入偏苯三酸酐38.4g、1，4-环己二醇 $12.6\\mathbf{g}$ 、对甲苯磺酸 $0.2\\mathbf{g}$ ，加热至 $150^{\\circ}\\mathrm{C}$ ，回流 $9\\mathrm{{min}}$ 搅拌至体系均匀反应，当酸值为 $20\\mathrm{mg}\\ \\mathrm{KOH/g}$ 时，停止加热，出料得 $^{2,2^{\\prime},5,5^{\\prime}}$ -四羧基苯甲酸对环己二酯(A)，粉碎成粉末。取 $24.7_{8}\\mathrm{A}$ 和 $30\\mathrm{mL}$ 甲苯，升温至 $98^{\\circ}\\mathrm{C}$ 搅拌溶解，加入 $24.7{\\mathrm{g}}$ 环氧氯丙烷和催化剂苄基三乙基氯化铵 $_{0.158}$ ，升温至$105^{\\circ}\\mathrm{C}$ ，反应 $150\\mathrm{min}$ 至酸值为 $8\\mathrm{mg}\\ \\mathrm{KOH/g}$ ，减压蒸馏除去甲苯和过量环氧氯丙烷。加入  \n\n$15\\mathrm{mL}$ 甲苯搅匀，取 $40\\mathrm{mL}$ 丙烯酸钠水溶液（由 $40\\mathrm{mL}$ 丙烯酸溶于 $100\\mathrm{mL}20\\%$ 的 $\\mathbf{NaOH}$ 配成)，再加入相转移转化剂四丁基氯化铵 $_{0.15g}$ ，在 $105\\mathrm{^\\circC}$ 反应 $180\\mathrm{min}$ ，根据 $\\mathbf{NaOH}$ 浓度变化判定终点，停止反应后，分液，取出下层无色黏稠物，加人甲苯，减压蒸馏共沸蒸出水分，得到2,2',5,5'-四甲酸丙烯酸（2-羟基）丙二酯苯甲酸对环己二酯，用于UV粉末涂料作交联剂。  \n\n(11) $^{6,6^{\\prime}}$ 碳酸 $^{-1,1^{\\prime}.}$ -已二醇二丙烯酸酯的合成  \n\n在三口烧瓶加人 $0.02{\\bmod{1}},6.$ 己二醇和 $\\scriptstyle5\\mathbf{mL}$ 四氢呋喃，搅拌溶解，再加人碳酸二甲酯0.0lmol和2滴磷酸催化剂，加热回流反应 $\\mathsf{6h}$ 。用旋转蒸发器除去四氢呋喃和未反应的碳酸二甲酯，得到 $^{6,6^{\\prime}}$ 碳酸 $^{-1,1^{\\prime}}$ 已二醇酯（I)。  \n\n将 $0.01\\mathrm{mol}$ I溶解在 $25\\mathrm{mL}$ 二氯甲烷中，加人 $0.02\\mathrm{mol}$ 三乙胺，缓慢滴加 $0.02\\mathrm{mol}$ 丙烯酰氯，有大量雾出现，当烟雾消失后，继续搅拌过夜，反应产物抽滤除去三乙胺盐酸盐，用10mLNaCl溶液洗涤，分出油层，蒸去溶剂二氯甲烷，得黄色液体Ⅱ3. $_{10\\mathbf{g}}$ ，产率 $83.8\\%$ 。  \n\n（12）光敏聚酰亚胺的合成在三口烧瓶中加人 $16.848g$ 邻联甲苯胺和 $136.6\\mathrm{mL}$ 溶剂二甲基亚矾，搅拌溶解，缓慢地加入 $17.31_{8}$ 均苯四酸二酐，室温下反应，搅拌使均苯四酸二酐全部溶解后静置约 $20\\mathrm{h}$ ，制成聚酰胺酸溶液（约 $20\\%$ 。  \n\n称取聚酰胺酸溶液 $2.8\\mathsf{g}$ 置于三口烧瓶中，滴加 $\\scriptstyle1\\arg L$ 丙烯酸羟乙酯，浓盐酸13滴，再滴加四氯化碳，加热至沸，保持1h后，停止滴加四氯化碳，待温度下降时，停止加热，将黏稠反应液趁热倒人10倍体积蒸馏水中，过滤，收集沉淀，在空气中干燥24h，得光敏聚酰亚胺（最高耐热热温度为 $350^{\\circ}\\mathrm{C}$ )。  \n\n（13）自引发四丙烯酸酯低聚物的合成  \n\n![](images/09820670f8b544cad6ed17ebe82d09134e0881f29396ad1abc1dc8337ddf52e6.jpg)  \n\n将1mol乙酰乙酸乙酯和 $2\\mathrm{mol}$ 三羟甲基丙烷三丙烯酸酯在碱催化下发生亚甲基加成反应，得到自引发四丙烯酸酯低聚物。 E  \n\n（14）带光引发基团聚丙烯酸酯低聚物合成在三口烧瓶中加人 $70\\mathbf{g}$ 乙二醇苯甲醚，通 $\\mathbf{N}_{2}$ 半小时，升温到 $80^{\\circ}\\mathrm{C}$ ，慢慢滴加甲基丙烯酸甲酯 $_{12.58}$ （ $125\\mathrm{mmol})$ 、丙烯酸 $25.0\\mathbf{g}$ $(347,2\\mathrm{mmol})$ 、丙烯酸丁酯 $12.5{\\bf g}$ （97.7mmol）和偶氮二异丁腈 $0.75{\\bf g}$ 混合物， $85^{\\circ}C$ 反应 $5\\mathord{\\sim}6\\mathrm{h}$ 停止反应，冷却，反应物倒入水中使聚合物析出，反复洗涤， $50^{\\circ}\\mathrm{C}$ 真空干燥 $24\\mathrm{h}$ ，得丙烯酸聚合物A，分子量测定 $M_{\\mathrm{n}}=6956$ ， $\\scriptstyle M_{\\mathrm{w}}=13223$ ，多分散性1.90；酸值 $436.8\\mathrm{mg}\\mathrm{KOH}/\\mathbf{g}.$  \n\n在三口烧瓶中加入 $5.0\\mathbf{g}$ A、 $60\\mathrm{mL}$ 四氢呋喃，使完全溶解，升温 $60^{\\circ}\\mathrm{C}$ ，慢滴 $6.0\\mathbf{g}$ （50.8mmol）二氯亚矾，使反应液保持微沸，反应 $6\\sim7\\mathrm{h}$ ，冷却旋转蒸发除去溶剂，用正己烷多次洗涤， $30^{\\circ}\\mathrm{C}$ 真空干燥 $24\\mathrm{h}$ ，得含丙烯酰氯聚合物B。  \n\n将 $2.80{\\bf g}\\mathrm{~B~}$ 完全溶解于 ${\\bf60m L}$ 四氢呋喃中，倒入用铝箔包裹的三口烧瓶中，加入 $\\mathbf{3.03g}$ （30mmol）三乙胺，升温至 $60^{\\circ}\\mathrm{C}$ ，慢慢滴加光引发剂 $\\mathbf{1173~0.432g}$ 1 $\\left(2,63\\mathrm{mmol}\\right)$ ，回流反应6h，再慢滴 $2,6973{\\bf g}$ 1 $\\scriptstyle(23,3\\mathrm{mmol})$ ）丙烯酸羟乙酯，保温反应6h，冷却，避光旋转蒸发，除去溶剂，用正已烷洗涤，真空干燥 $48\\mathbf{h}$ ，得带光引发基团聚丙烯酸酯低聚物。  \n\n（15）有机/无机杂化脂环族环氧的合成  \n\n![](images/d393be6d506a1bafd8ff2d6abfe9f89914634e9150fd4522bfbb29d59d89293f.jpg)  \n\n将100g2-(3,4-环氧环已基）乙基三甲氧基硅烷 $\\mathbf{(KBM3030.406mol)}$ 和14 $1.488~3\\cdot\\mathsf{Z}$ 基羟甲基氧杂丁烷（ $\\mathbf{\\langleDXT-1011.22mol\\rangle}$ 置于一个圆底烧瓶中，抽真空在 $100^{\\circ}\\mathrm{C}$ 下搅拌 $^{3\\mathrm{h}}$ 除去甲醇，得有机/无机杂化脂环族环氧化合物。该有机/无机杂化脂环族环氧化合物加入阳离子光固化体系，可提高阳离子光聚合速度，并具有良好的热稳定性。  \n\n（16）含环氧基的酚醛环氧丙烯酸酯的合成在三口烧瓶中加入含 $36.2g$ 质量分数为 $70\\%$ 的F-44酚醛环氧树脂的二氧六环溶液（含 $0.1\\mathrm{mol}$ 环氧基)， $2.47\\mathrm{mL}$ 质量分数为 $2\\%$ 的对苯二酚的二氧六环溶液， $0.5\\mathbf{g}$ 四丁基溴化铵(催化剂)， $3.60\\mathbf{g}$ 丙烯酸 $(0.05\\mathrm{mol})$ 。升温至 $95\\%$ 反应，至酸值为零停止反应，得到含环氧基的酚醛环氧丙烯酸树脂为自由基和阳离子双固化UV低聚物。  \n\n（17）光潮气双固化有机硅聚氨酯丙烯酸酯的合成在三口烧瓶中加人一定量己二异氰酸酯和适量二月桂酸二丁基锡，搅拌升温至 $60^{\\circ}\\mathsf{C}$ ，滴加计算量的N,N-二（氨丙基三乙氧基）硅烷（G402硅烷偶联剂）（NCO与氨基摩尔比为 $2:1\\AA$ ，在 $70^{\\circ}\\mathrm{C}$ 反应2h，加入丙烯酸羟乙酯（NCO与OH摩尔比为 $1:1$ ）和适量对甲氧基苯酚，保温反应至一NCO消失，得到光/潮气双固化的硅氧烷型聚氨酯丙烯酸酯，可用作光固化保型涂料低聚物。  \n\n（18）双重固化水性PUA的合成在三口烧瓶中加入 $30.0{\\bf g}$ 甲苯二异氰酸酯、 $\\mathbf{30g}$ 聚醚二元醇（分子量1900）和适量二月桂酸二丁基锡， $80^{\\circ}\\mathrm{C}$ 反应至一NCO达到理论计算值。降温加人5.1g二羟甲基丙酸和 $_{5g1,6}$ 己二醇， $70^{\\circ}\\mathrm{C}$ 反应到一NCO达到理论计算值。加入适量丙酮，降温，加人 $_{10.1\\mathbf{g}}$ 季戊四醇二丙烯酸酯、适量阻聚剂对甲氧基苯酚， $60^{\\circ}\\mathrm{C}$ 反应到--NCO达到理论计算值。降温至 $40^{\\circ}\\mathrm{C}$ 加入 $3.4\\mathbf{g}$ 封闭剂3，5-二甲基吡唑，反应至—NCO峰完全消失。降至室温，加人 $4.4\\mathbf{g}$ 三乙胺中和，再加人定量的去离子水，强烈搅拌，真空蒸馏除去丙酮，即得UV和热双重固化的水性聚氨酯丙烯酸树脂分散体，固含量 $35\\%$ ， $\\mathfrak{p H}$ 为 $\\phantom{-}7.8\\sim8.2$ 。  \n\n该低聚物在 $90^{\\circ}\\mathrm{C}$ 时即会发生解封， $130^{\\circ}\\mathrm{C}$ 可进行热固化， $35\\mathrm{{min}}$ 完成热固化（表3-116）。  \n\n表3-116热固化性能  \n\n\n<html><body><table><tr><td>性 能</td><td>硬度(摆杆)/S</td><td>附着力/级</td></tr><tr><td>UV固化</td><td>226</td><td>4</td></tr><tr><td>UV固化+热固化(120C×30min)</td><td>308</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 107,
+        "chunk": "# 3.20.7超支化丙烯酸低聚物的合成  \n\n（1）超支化聚酯甲基丙烯酸酯的合成在三口烧瓶中加入一定量季戊四醇、相对于季戊四醇羟基过量 $20\\%\\sim50\\%$ 的1,2,4-苯三酸酐和适量催化剂氯化亚锡及溶剂二甲基甲酰胺，在氮气保护下，升温至 $100^{\\circ}\\mathrm{C}$ 反应16h，得到端羧基超支化聚酯。在甲苯和二甲基甲酰胺混合溶剂中加入$2.5\\%$ 的苄基二甲胺和氢，上述端羧基超支化聚酯及相对于超支化聚酯中羧基过量 $5\\%$ （摩尔分数）的甲基丙烯酸缩水甘油酯，在 $70^{\\circ}\\mathrm{C}$ 下反应至羧基消失，得超支化聚酯甲基丙烯酸酯。  \n\n（2）超支化聚酯甲基丙烯酸树脂的合成在三口烧瓶中加入1mol季戊四醇、 $_{4\\mathrm{mol}}$ 偏苯三酸酐和溶剂二甲基甲酰胺，在氮气保护下，搅拌升温至 $110\\sim115^{\\circ}\\mathrm{C}$ ，每半小时取样测酸值至恒定。加人计算量的环氧丙烷，反应至酸值恒定；加入计算量的偏苯三酸酐，反应至酸值恒定，如此重复反应至设计要求，得到超支化聚酯树脂。  \n\n将上述反应所得超支化聚酯树脂冷却至 $60^{\\circ}\\mathrm{C}$ 以下，加入配方量二甲基甲酰胺、计算量的甲基丙烯酸缩水甘油酯及适量的以羟基苯甲醚，升温至 $90\\sim95^{\\circ}\\mathrm{C}$ 反应至酸值恒定，得到超支化聚酯甲基丙烯酸树脂。  \n\n（3）UV氨基超支化聚酯的合成在三口烧瓶中加人 $8.6\\mathbf{g}$ （0.1mol）丙烯酸甲酯、$_{10.58}$ （0.1mol）二乙醇胺和 $10\\mathrm{mL}$ 甲醇，通 ${\\bf N}_{2}$ ，室温下搅拌 $30\\mathrm{min}$ ，升温 $35\\mathrm{^\\circC}$ ，反应4h，抽真空除去甲醇，得到无色透明油状物 $\\begin{array}{r}{N,N.}\\end{array}$ 二羟乙基-3-氨基丙烯酸甲酯A，产率 $94\\%$ a  \n\n在三口烧瓶中加人 $\\mathbf{1.34g}$ （0.01mol）三羟甲基丙烷、 $5.748(0.035\\mathrm{mol})$ A和 $35.4\\mathrm{mg}$ 对甲苯磺酸，升温 $120^{\\circ}\\mathrm{C}$ 反应2h，减压蒸馏除去生成的甲醇，得 $6.4{\\bf g}$ 淡黄色油状物。继续加入11.5g $\\left(0.06\\mathrm{mol}\\right)$ ）A和 $23\\mathrm{mg}$ 对甲苯磺酸，升温至 $120^{\\circ}\\mathrm{C}$ 反应 $^{2\\mathrm{h}}$ ，减压蒸馏除去生成的甲醇，得到 $14.48$ 淡黄色油状物（HPAE-2)，即为第二代羟端基氨基超支化聚酯，产率$92\\%$ ，羟值 $432\\mathrm{mg}\\ \\mathrm{KOH/g}$ 。继续加入 $22.95\\mathbf{g}$ （0.12mol）A和 $\\mathbf{30mg}$ 对甲苯磺酸，升温至$100^{\\circ}\\mathrm{C}$ 反应3h，减压蒸馏1h，除去生成的甲醇，得到 $38.62g\\cdot$ 淡黄色油状物，即为第三代羟端基氨基超支化聚酯（HPAE-3)，产率 $91\\%$ ，羟值 $387\\mathrm{mg}~\\mathrm{KOH/g}$ 9  \n\n$\\textcircled{1}$ HPAE-2-MAA的制备在三口烧瓶中加人 $8.46g$ $\\left(0.05\\mathrm{mol}\\right)^{\\cdot}$ ）HPAE-2和 $\\mathbf{35mg}$ 对甲氧基苯酚，缓慢滴加9.25g（0.06mol）甲基丙烯酸酐，25℃反应2h，将产物溶于二氯甲烷，用NaOH水溶液中和至中性，水洗除去NaOH，用十氯甲烷重复萃取产物三次，减压蒸馏抽去油层二氯甲烷，得到黏稠液体即为UV氨基超支化聚酯甲基丙烯酸酯（HPAE-2-MAA）产率 $85\\%$ ，双键值 $4.54\\mathrm{mmol}/\\mathbf{g}$ ，黏度 $2300\\mathrm{{mPa}\\cdot\\mathrm{{s}}}$ 1 $(20^{\\circ}\\mathrm{C})$ 。  \n\n② HPAE-2-AA的制备在三口烧瓶中加人8.46g（0.05mol）HPAE-2、60mL甲苯、49mg 对甲氧基苯酚和0.12g硝基苯，80℃搅拌下缓慢滴加4.32g（0.06mol）丙烯酸，加毕升温至120℃反应至酸值<10mgKOH/g，减压蒸馏除去甲苯后，得到黄色黏稠液体即为UV氨基超支化聚酸丙烯酸酯（HPAE-2-AA)，产率 $87\\%$ ，双键值 $4.733\\mathrm{mmol/g}$ Q 55  \n\n$\\textcircled{3}$ HPAE-2-TDI-HEA的制备在三口烧瓶中加入 $^{17}{\\bf g}$ （0.1mol）甲苯二异氰酸酯(TDI)、适量二月桂酸二丁基锡和对甲氧基苯酚， $30^{\\circ}\\mathrm{C}$ 搅拌下滴加11. $\\mathfrak{6}\\mathfrak{g}$ （0.05mol）丙烯酸羟乙酯（HEA)，加毕升温至 $50^{\\circ}\\mathrm{C}$ 反应2h得到TDI-HEA半加成物，降温至 $30^{\\circ}\\mathrm{C}$ 以下，滴加6.5g（0.04mol）HPAE-2-二氯甲烷溶液，加毕升温至 $40^{\\circ}\\mathrm{C}$ 反应 $^{3\\mathrm{h}}$ ，减压蒸馏除去二氯甲烷，得到淡黄色黏稠状物质，即为UV氨基超支化聚酯-丙烯酸聚氨酯树脂HPAE-2-TDI-HEA，产物双键值 $\\mathbf{2.1mmol/g}$ 口  \n\n$\\textcircled{4}$ HPAE-2-SA的制备在三口烧瓶中加人 $8.46g$ C $\\left(0,05\\mathbf{mol}\\right.$ ）HPAE-2和二丁酸酐$6.0\\mathbf{g}$ + $(0,06\\mathrm{mol})$ ，再加入 $20\\mathrm{mL}$ 四氢呋喃作溶剂， $\\boldsymbol{70}\\mathbf{mg}$ 氯化亚锡为催化剂，升温 $60^{\\circ}\\mathrm{C}$ ，反应 $^{3\\mathrm{h}}$ ，减压蒸馏除去四氢呋喃，得到黄色黏稠液体为羧端基氨基超支化聚酯B。  \n\n取 $_{14.45\\mathbf{g}}$ 1 $\\left(0,05\\mathrm{mol}\\right)$ B，溶人 $20\\mathrm{mL}$ N,N-二甲基甲酰胺中，加入 $46\\mathbf{m}\\mathbf{g}$ 对甲氧基苯酚和 $0,23{\\bf g\\ }N,N.$ -二甲基苄胺，缓慢滴加 $8.55\\mathbf{g}$ $\\left(0.06\\mathbf{mol}\\right)^{\\cdot}$ ）甲基丙烯酸缩水甘油酯，升温至$100^{\\circ}\\mathrm{C}$ ，反应至酸值小于 $10\\mathrm{mg}\\ \\mathrm{KOH/g}$ ，减压蒸馏除去 $N,N\\mathrm{.}$ -二甲基甲酰胺，得到黄色黏稠液体，即为UV固化氨基超支化聚酯HPAE-2-SA，双键值 $\\mathbf{2.4mmol/g}$ a  \n\n（4）马来酸酐改性脂肪族超支化聚酯的合成按 $1:9$ 的质量比将三羟甲基丙烷和二羟甲基丙酸加入到三口烧瓶中，再加入适量的对甲苯磺酸，升温到 $140^{\\circ}\\mathrm{C}$ ，在氮气保护下反应1h，抽真空（真空度为 $400\\mathbf{Pa}$ ）1h，得端羟基脂肪族超支化聚酯。升温至 $90^{\\circ}\\mathsf{C}$ 。加入过量$10\\%$ （质量分数）的马来酸酐，在氮气保护下继续反应 $^{3\\mathbf{h}}$ 。冷却后加入丙酮使产物溶解，再沉淀到乙醚中，以除去过量的马来酸酐，收集底部沉淀物，干燥后得马来酸酐改性脂肪族超支化聚酯，收率为 $71.3\\%$ 。  \n\n![](images/db5a747b957d663aeb89e813e60e2632a8a224c892314791b7ce9851b7b75e79.jpg)  \n（5）超支化聚酯聚氨酯丙烯酸酯的合成  \nHBPE-OH  \n\n将1mol季戊四醇、4mol偏苯三酸酐、适量二甲基甲酰胺（DMF）和 $0.25\\%$ （质量分数）的氯化亚锡催化剂加人到装有通 ${\\bf N}_{2}$ 和干燥管的三口烧瓶中，升温至 $120^{\\circ}\\mathrm{C}$ 反应至红外光谱中 $1850\\mathrm{cm}^{-1}$ 处酸酐吸收峰消失。冷却到 $60^{\\circ}\\mathrm{C}$ ，缓缓滴加含有 $3\\%$ （质量分数） $N$ ,N-二甲基苄胺的环氧丙烷，反应至酸值 ${\\bf<5m g~K O H/g}$ 。减压蒸馏除去DMF，得到浅黄色黏稠液体，即为羟端基超支化聚酯（HBPE-OH)，并测定羟值。  \n\n将lmol甲苯异氰酸酯（TDI）与lmol丙烯酸羟乙酯（HEA）在二丁基二月桂酸锡催化下，在丙酮中 $40^{\\circ}\\mathrm{C}$ 反应，至—NCO含量达到理论值，得 TDI-HEA半加成物。  \n\n将 HBPE-OH 和 TDI-HEA 按一 $\\mathbf{\\cdotOH}:\\mathbf{-NCO}{=}1:1$ 的比例加入三口烧瓶中，在 $70\\%$ 下反应至红外光谱 $2270\\mathrm{cm}^{-1}$ 处—NCO基吸收峰消失。产物用蒸馏水洗，过滤，真空干燥，得到白色粉末即为超支化聚酯聚氨酯丙烯酸酯 (HUA)。  \n\n（6）超支化聚酯丙烯酸酯的合成在三口烧瓶中加人 $\\mathbf{15.1g\\Boltom^{TM}H}20^{\\mathbf{0}}$ （超支化聚酯)、二氯甲烷和三乙胺（ $(2.5:1$ ，体积比)，在冰水浴中缓慢加入 $_{15\\mathrm{mL}}$ 丙烯酰氯，室温反应至红外光谱 $3500{\\sim}3400\\mathrm{cm}^{-1}$ 处羟基峰完全消失，将此反应混合物用 $\\scriptstyle2{\\mathrm{mol/L}}$ 的盐酸和碳酸氢钠水溶液依次洗涤，去除过量的三乙胺，用无水硫酸钠干燥，减压蒸馏得到淡黄色黏稠液体即为超支化聚酯丙烯酸酯。  \n\n（7）超支化聚酯丙烯酸酯的合成在三口烧瓶中加入端羟基超支化聚酯（BoltonTMH20）溶于二氧六环中，以 $\\mathbf{SnCl}_{2}$ 为催化剂， $100^{\\circ}\\mathrm{C}$ 下与丁二酸酐与羟基摩尔比 $_{1}:2$ ，回流搅拌反应 $36\\mathrm{h}$ ，得到端羧基超支化聚酯（Boltom $\\mathbf{\\Delta}^{\\mathsf{T M}}$ H20-COOH)；加人与羧基等物质的量的甲基丙烯酸缩水甘油酯，在N,N-二甲基苄胺催化下，升温到90℃，反应至酸值≤5mg$\\mathtt{K O H/g}$ ，得到超支化聚酯丙烯酸酯。  \n\n（8）超支化PEMA的合成将 $_{3\\mathrm{mol}}$ 双酚A环氧树脂、1mol均苯三酸和 $3\\mathrm{{mol}}$ 甲基丙烯酸加人三口烧瓶中，在四丁基溴化铵催化下， $80^{\\circ}\\mathrm{C}$ 反应 $^{18\\mathbf{h}}$ ，得超支化聚酯甲基丙烯酸树脂（HB-PEMA)，产率 $72\\%$ ，数均分子量5900，甲基丙烯酰基接枝率 $98\\%$ α  \n\n（9）超支化聚酯甲基丙烯酸树脂的合成在三口烧瓶中加入6mmol3-乙基苯氧甲基氧环丙烷（EPMO)、1mmol均苯三酸、 $\\scriptstyle3\\mathrm{mmol}$ 甲基丙烯酸、5mL $N\\cdot$ 甲基吡咯、 $0.05\\mathrm{mmol}$ 氯化四苯基磷和适量对苯二酚，升温至 $140^{\\circ}\\mathrm{C}$ ，反应 $^{12\\mathrm{{h}}}$ ，得超支化聚酯甲基丙烯酸树脂(PEMA)。  \n\n（10）超支化聚酯甲基丙烯酸树脂的合成  \n\n在三口烧瓶中加人 $3\\mathrm{mol}1,4$ -双[（3-乙基3氧环丙烷）甲氧基甲基］苯（BEOP)、lmol均苯三酸（TMA）和 $\\mathsf{3}{\\sim}\\mathsf{9}{\\bmod{\\ell}}$ 甲基丙烯酸（MAA)、适量对苯二酚和催化剂 $5\\%$ （摩尔分数）的氯化四苯基磷，在溶剂 $N\\cdot$ -甲基吡咯中，升温至 $140^{\\circ}\\mathrm{C}$ 反应 $24\\mathrm{h}$ ，得超支化聚酯甲基丙烯酸树脂（PEMA)。不同配比反应物得到超支化聚酯的性能见表3-117。  \n\n(11）碱溶性超支化聚酯合成在三口烧瓶中加入超支化聚酯甲基丙烯酸酯（HB-PE-MA)、1,2,3,6-四氯邻苯二甲酸酐（0.6倍HB-PEMA摩尔比）、催化剂三苯基磷和溶剂乙酸乙氧基乙酯，升温至 $80^{\\circ}\\mathrm{C}$ 反应4h，得到带有 $55\\%$ 羧基的碱溶性超支化聚酯甲基丙烯酸酯（碱溶性HB-PEMA)。  \n\n表3-117不同配比反应物得到超支化聚酯的性能  \n\n\n<html><body><table><tr><td>BEOP/mol</td><td>TMA/mol</td><td>MAA/mol</td><td>数均分子量M</td><td>Mw/M</td><td>产率/%</td><td>MAA与聚合物比例/%</td></tr><tr><td>3</td><td>2</td><td>0</td><td>交联</td><td>交联</td><td>>99</td><td>交联</td></tr><tr><td>3</td><td>1</td><td>0</td><td>5.3X103</td><td>2.93</td><td>68</td><td>0</td></tr><tr><td>3</td><td>1</td><td>3</td><td>6.3X103</td><td>2.17</td><td>59</td><td>11</td></tr><tr><td>3</td><td>1</td><td>6</td><td>4.5X103</td><td>2.25</td><td>46</td><td>20</td></tr><tr><td>3</td><td>1</td><td>9</td><td>3.7X103</td><td>2.43</td><td>55</td><td>36</td></tr></table></body></html>  \n\nHB-PEMA和碱溶性HB-PEMA都溶于氯仿、四氢呋喃和二甲基甲酰胺，HB-PEMA不溶于 $1\\%$ 的 $N a_{2}C O_{3}$ ，而碱溶性HB-PEMA可溶于 $1\\%$ 的 $\\mathrm{Na}_{2}\\mathrm{CO}_{3}$ ，可用作负性光致抗蚀剂。  \n\n（12）超支化聚氨酯甲基丙烯酸酯的合成将1mol二环己基亚甲基二异氰酸酯、 $2\\mathrm{mol}$ 三羟甲基丙烷和 $2\\mathrm{mol}$ 甲基丙烯酰氧乙基异氰酸酯加入三口瓶中，加入 $2\\%$ （摩尔分数）的二月桂酸二丁基锡和溶剂四氢呋喃，在 $50^{\\circ}\\mathrm{C}$ 条件下反应6h，得超支化聚氨酯甲基丙烯酸树脂，产率 $92\\%$ ，数均分子量为2900，其中甲基丙烯酰氧基接枝率 $66\\%$ 口  \n\n（13）含磷阻燃超支化PUA的合成在三口烧瓶中加入 $1\\mathrm{mol}85\\%$ 的磷酸，通 ${\\bf N}_{2}$ ，在冰浴中搅拌下缓慢滴加 $3\\mathrm{mol}$ 环氧丙烷，加毕在冰浴中反应1h，再在 $30^{\\circ}\\mathrm{C}$ 反应，至酸值 ${<}3\\mathrm{mg}\\ \\mathrm{KOH/g}$ ，得到混合物，在 $80^{\\circ}\\mathrm{C}$ 下抽真空，除去残余的环氧丙烷和磷酸中的水，得到淡黄色含磷三元醇。 $25\\mathrm{^\\circC}$ 时加入二月桂酸二丁基锡，甲苯二异氰酸酯（ $\\left.1.5\\sim\\right.$ $3,0\\mathrm{mol})$ ，加毕反应0.5h，再加入对羟基苯甲醚，缓慢滴加丙烯酸羟乙酯，升温至$70^{\\circ}\\mathrm{C}$ 反应4h，得到含磷的超支化PUA（HPUA-P)。  \n\nHPUA-P经UV固化后，在点燃后迅速膨胀并自熄，氧指数27.0。  \n\n（14）树枝状丙烯酸酯低聚物的合成  \n\nHNCHCHNH+CHCHC(CHOOCCH—CH）3—  \n\n![](images/648f052f09ad2a1009b8edea216dc2d52ed78bf4e6c93672c8f38cd6182a8e9c.jpg)  \n\n在三口烧瓶中依次加人 $15\\mathrm{mL}$ 甲醇、 $29.68(0.1\\mathrm{mol})$ 三羟甲基丙烷三丙烯酸酯、 $_{1,2g}$ $\\left(0.02\\mathrm{mol}\\right)$ 乙二胺，于 $30^{\\circ}\\mathrm{C}$ 下搅拌反应6h，体系分别用 $200\\mathrm{{mL},150\\mathrm{{mL},100\\mathrm{{mL}}}}$ 甲醇洗涤3次，$30^{\\circ}\\mathrm{C}$ 真空于燥，得无色透明黏稠状液体即为带有8个丙烯酸酯双键的树枝状丙烯酸酯低聚物(DAO)。DAO与EA、PUA性能比较见表3-118。 点  \n\n表3-118DAO与EA、PUA性能比较  \n\n\n<html><body><table><tr><td>低聚物</td><td>结构</td><td>分子量</td><td>黏度/mPa·s</td><td>指触干时间/s</td></tr><tr><td>DAO</td><td>树枝状丙烯酸酯</td><td>1244</td><td>5100(25C)</td><td>56.5</td></tr><tr><td>EA(EB 600)</td><td>双酚A环氧丙烯酸酯</td><td>500</td><td>3000(60℃)</td><td>480</td></tr><tr><td>PUA(EB270)</td><td>脂肪族聚氨酯丙烯酸酯</td><td>1500</td><td>3000(60℃)</td><td>640</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 108,
+        "chunk": "# 第4章 光引发剂  \n\n光引发剂（photoinitiator，PI）是光固化产品的关键组分，它对光固化产品的光固化速率起决定性作用。光引发剂是一种能吸收辐射能，经激发发生化学变化，产生具有引发聚合能力的活性中间体（自由基或阳离子）的物质。在光固化产品中，光引发剂含量比低聚物和活性稀释剂要低得多，一般在3%～5%，不超过7%～10%。在实际应用中，光引发剂本身或其光化学反应的产物均不应对固化后涂层的化学和物理力学性能产生不良影响。  \n\n光引发剂因吸收辐射能不同，可分为紫外光引发剂（吸收紫外光区250～420nm）和可见光引发剂（吸收可见光区400～700nm）。光引发剂因产生的活性中间体不同，可分为自由基型光引发剂和阳离子型光引发剂两类。自由基型光引发剂因产生自由基的作用机理不同，又可分为裂解型光引发剂和夺氢型光引发剂两类。  \n\n目前，光固化技术主要为紫外光固化，所用的光引发剂为紫外光引发剂。可见光引发剂因对日光和普通照明光源敏感，在生产和使用上受到限制，仅在少数领域如牙科、印刷制版上应用。此外，光引发剂还包括一些特殊类别，如混杂型光引发剂、水基光引发剂、大分子光引发剂等。  \n\n在光固化体系中，有时光引发剂与其他辅助组分一起使用，可以促进自由基或阳离子等活性中间体的产生，提高光引发效率。这些辅助组分包括光敏剂（photosesitizer）和增感剂(sesitizer)。光敏剂是指该分子能吸收光能跃迁至激发态，通过能量转移给光引发剂，光引发剂接受能量后由基态跃迁至激发态，本身发生化学变化，产生活性中间体，从而引发聚合反应，而光敏剂将能量传递给光引发剂后，自身又回到初始非活性状态，其化学性质未发生变化。增感剂自身并不吸收光能，也不引发聚合，但在光引发过程中，协同光引发剂并参与光化学反应，从而提高了光引发剂的引发效率，也称助引发剂（coinitiator)。配合夺氢型光引发剂的氢供体三级胺就属于增感剂。  \n\n对光引发剂的选择要考虑以下因素。  \n\n①光引发剂的吸收光谱与光源的发射光谱相匹配。目前，光固化的光源主要为中压汞灯（国内称高压汞灯)，其发射光谱中365nm、313nm、302nm、254nm谱线非常有用，许多光引发剂在上述波长处均有较大吸收（见附录1)。光引发剂分子对光的吸收，可以用此波长时的摩尔消光系数反映（表4-1和表4-2)。  \n\n单位： $\\mathbf{L}/(\\mathbf{mol}\\cdot\\mathbf{cm})$  \n\n表4-1部分光引发剂在高压汞灯各发射光波的摩尔消光系数  \n\n\n<html><body><table><tr><td>光引发剂</td><td>254nm</td><td>302nm</td><td>313nm</td><td>365nm</td><td>405nm</td><td>435nm</td></tr><tr><td>184</td><td>3.317×10</td><td>5.801×10²</td><td>4.349×10²</td><td>8.864X101</td><td></td><td></td></tr><tr><td>369</td><td>7.470×103</td><td>3.587×104</td><td>4.854×10</td><td>7.858X103</td><td>2.800×102</td><td></td></tr><tr><td>500</td><td>6.230×104</td><td>1.155×103</td><td>5.657×10²</td><td>1.756×10²</td><td></td><td></td></tr><tr><td>651</td><td>4.708X104</td><td>1.671×103</td><td>7.223X102</td><td>3.613×10²</td><td>·</td><td></td></tr><tr><td>784</td><td>7.488×105</td><td>1.940×104</td><td>1.424×10</td><td>2.612×103</td><td>1.197X105</td><td>1.124×103</td></tr><tr><td>819</td><td>1.953×10</td><td>1.823×104</td><td>1.509X10</td><td>2.309X103</td><td>8.990×10²</td><td>3.000×101</td></tr><tr><td>907</td><td>3.936×103</td><td>6.063×10</td><td>5.641×104</td><td>4.665X102</td><td></td><td></td></tr><tr><td>1300</td><td>3.850×104</td><td>1.240×104</td><td>1.560×10</td><td>2.750×103</td><td>9.300X101</td><td>9.000×10</td></tr><tr><td>1700</td><td>3.207×104</td><td>5.750×103</td><td>4.162×103</td><td>8.316×10²</td><td>2.464X10²</td><td></td></tr><tr><td>1800</td><td>2.660×10</td><td>6.163×103</td><td>4.431×103</td><td>9.290×10²</td><td>2.850×10²</td><td></td></tr><tr><td>1850</td><td>2.235×104</td><td>1.280×10*</td><td>8.985X103</td><td>1.785×103</td><td>5.740×10²</td><td></td></tr><tr><td>2959</td><td>3.033×104</td><td>1.087×10</td><td>2.568×103</td><td>4.893X101</td><td></td><td></td></tr><tr><td>1173</td><td>4.064×104</td><td>8.219×10²</td><td>5.639X102</td><td>7.388×10</td><td></td><td></td></tr><tr><td>4265</td><td>2.773×10</td><td>4.903×103</td><td>3.826×103</td><td>7.724×102</td><td>2.176×10²</td><td></td></tr></table></body></html>  \n\n表4-2部分光引发剂的摩尔消光系数  \n单位： $\\mathbf{L}/(\\mathbf{mol}\\cdot\\mathbf{cm})$   \n\n\n<html><body><table><tr><td>光引发剂</td><td>260nm</td><td>360nm</td><td>405nm</td><td>光引发剂</td><td>260nm</td><td>360nm</td><td>405nm</td></tr><tr><td>IPBE</td><td>11379</td><td>50</td><td></td><td>CTX</td><td>42000</td><td>3350</td><td>1780</td></tr><tr><td>BP</td><td>14922</td><td>51</td><td></td><td>DETX</td><td>42000</td><td>3300</td><td>1800</td></tr><tr><td>MK</td><td>8040</td><td>37500</td><td>1340</td><td>DEAP</td><td>5775</td><td>19</td><td></td></tr></table></body></html>  \n\n$\\textcircled{2}$ 光引发效率高，既具有较高的产生活性中间体（自由基或阳离子）的量子产率，同时产生的活性中间体有高的反应活性。  \n\n$\\textcircled{3}$ 对有色体系，由于颜料的加入，在紫外区有不同的吸收，因此，必须要选用受颜料紫外吸收影响最小的光引发剂。  \n\n$\\textcircled{4}$ 在活性稀释剂和低聚物中有良好的溶解性，见表4-3和表4-4。  \n\n表4-3部分光引发剂的溶解性（一） 单位：%（质量分数）  \n\n\n<html><body><table><tr><td>光引发剂</td><td>丙酮</td><td>正丁酯</td><td>IBOA</td><td>IDA</td><td>PEA</td><td>HDDA</td><td>TPGDA</td><td>TMPTA</td><td>TMPEOTA</td><td>1173</td></tr><tr><td>184</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td></tr><tr><td>500</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td></tr><tr><td>1173</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>一</td></tr><tr><td>2959</td><td>19</td><td>3</td><td>5</td><td>5</td><td>5</td><td>10</td><td>20</td><td>5</td><td>5</td><td>35</td></tr><tr><td>MBF</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>V50</td><td>>50</td><td>>50</td></tr><tr><td>651</td><td>>50</td><td>V50</td><td>40</td><td>30</td><td>>50</td><td>40</td><td>25</td><td>>50</td><td>45</td><td>>50</td></tr><tr><td>369</td><td>17</td><td>11</td><td>10</td><td>5</td><td>15</td><td>10</td><td>6</td><td>5</td><td>5</td><td>25</td></tr><tr><td>907</td><td>>50</td><td>35·</td><td>35</td><td>25</td><td>45</td><td>35</td><td>22</td><td>25</td><td>20</td><td>>50</td></tr><tr><td>1300</td><td>>50</td><td>45</td><td>>50</td><td>35</td><td>>50</td><td>>50</td><td>35</td><td>25</td><td>25</td><td>>50</td></tr><tr><td>TPO</td><td>47</td><td>25</td><td>15</td><td>7</td><td>34</td><td>22</td><td>16</td><td>14</td><td>13</td><td>>50</td></tr><tr><td>4265</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td></tr><tr><td>819</td><td>14</td><td>6</td><td>5</td><td>5</td><td>15</td><td>5</td><td>5</td><td>5</td><td>>5</td><td>30</td></tr><tr><td>2005</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td></tr><tr><td>2010</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td></tr><tr><td>2020</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td></tr><tr><td>784</td><td>30</td><td>10</td><td>5</td><td>不溶解</td><td>15</td><td>10</td><td>5</td><td>5</td><td>不溶解</td><td>7</td></tr></table></body></html>\n\n注：在将固态光引发剂溶人液态单体中时，应加热至 $50\\sim60^{\\circ}C$ 并混合均匀。溶解后的液体应在室温下贮存24h，如无结晶出现则说明溶解成功。  \n\n表4-4部分光引发剂的溶解性（二）  \n\n\n<html><body><table><tr><td>光引发剂</td><td>MMA</td><td>HDDA</td><td>TPGDA</td><td>TMPTA</td><td>芳香族PUA</td><td>DMB</td></tr><tr><td>ITX</td><td>43</td><td>25</td><td>16</td><td>15</td><td>24</td><td>31</td></tr><tr><td>CTX</td><td>2</td><td>3.3</td><td></td><td>1.5</td><td></td><td>4.7</td></tr><tr><td>CPTX</td><td></td><td>6</td><td>4</td><td>3</td><td></td><td>9</td></tr><tr><td>DEAP</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td>>50</td><td></td></tr><tr><td>BMS</td><td>26</td><td>13.5</td><td></td><td>2.4</td><td></td><td>3.3</td></tr><tr><td>EDAB</td><td>50</td><td>45</td><td>40</td><td>30</td><td>40</td><td></td></tr></table></body></html>  \n\n![](images/97ba1e96514ac9d251f6697cee076be75d8cffcb51ad49c9439a46cf25fa9806.jpg)  \n\n![](images/7ac3e74fddb3a1a5a007b23f826ecc5359c08ce2a2f7d7be77fc2e44c7c2891f.jpg)  \n\n③气味小，毒性低，特别是光引发剂的光解产物要低气味和低毒。  \n$\\textcircled{6}$ 不易挥发和迁移，见表4-5和表4-6。  \n\n表4-5部分光引发剂的挥发性  \n\n\n<html><body><table><tr><td>光引发剂</td><td>结晶时损失/%</td><td>在10%TMPEOTA 浓度时损失/%</td><td>光引发剂</td><td>结晶时损失/%</td><td>在10%TMPEOTA 浓度时损失/%</td></tr><tr><td>184</td><td>17.4</td><td>2.6</td><td>1300</td><td>6.7</td><td>2.0</td></tr><tr><td>369</td><td>0</td><td>0</td><td>1800</td><td>26.0</td><td>3.5</td></tr><tr><td>500</td><td>25.9</td><td>2.8</td><td>1850</td><td>23.8</td><td>3.1</td></tr><tr><td>651</td><td>7.0</td><td>2.8</td><td>2959</td><td>0.8</td><td>0</td></tr><tr><td>819</td><td>0</td><td>0.9</td><td>BP</td><td>26.6</td><td>2.8</td></tr><tr><td>907</td><td>0.7</td><td>0</td><td>1173</td><td>98.6</td><td>8.6</td></tr></table></body></html>\n\n注：0.5g样品溶于2mL甲苯中，在（110±5)℃烘60min。  \n\n单位： $\\%$ （质量分数）  \n表4-6部分光引发剂的热失重性能  \n\n\n<html><body><table><tr><td rowspan=\"2\">光引发剂</td><td colspan=\"3\">失重所需温度/℃</td><td rowspan=\"2\">光引发剂</td><td colspan=\"3\">失重所需温度/℃</td></tr><tr><td>5%</td><td>10%</td><td>15%</td><td>5%</td><td>10%</td><td>15%</td></tr><tr><td>184</td><td>155</td><td>170</td><td>179</td><td>1300</td><td>157</td><td>174</td><td>185</td></tr><tr><td>369</td><td>248</td><td>264</td><td>274</td><td>1700</td><td>104</td><td>119</td><td>127</td></tr><tr><td>500</td><td>142</td><td>156</td><td>165</td><td>1800</td><td>153</td><td>169</td><td>179</td></tr><tr><td>651</td><td>170</td><td>184</td><td>194</td><td>1850</td><td>157</td><td>174</td><td>185</td></tr><tr><td>784</td><td>213</td><td>217</td><td>220</td><td>2959</td><td>204</td><td>218</td><td>228</td></tr><tr><td>819</td><td>241</td><td>254</td><td>261</td><td>BP</td><td>153</td><td>167</td><td>176</td></tr><tr><td>907</td><td>198</td><td>214</td><td>224</td><td>1173</td><td>101</td><td>115</td><td>123</td></tr><tr><td>1000</td><td>116</td><td>130</td><td>140</td><td>4265</td><td>156</td><td>174</td><td>185</td></tr></table></body></html>\n\n注：在 ${\\bf N}_{2}$ 下，升温速度 $10\\%$ 0  \n\n?光固化后不能有黄变现象，这对白色、浅色及无色体系特别重要；也不能在老化时引起聚合物的降解。$\\textcircled{8}$ 热稳定性和贮存稳定性好，见表4-7。  \n\n表4-7不同光引发剂的贮存稳定性  \n\n\n<html><body><table><tr><td>光引发剂</td><td>环氧丙烯 酸酯体系</td><td>不饱和聚酯- 苯乙烯体系</td><td>光引发剂</td><td>环氧丙烯 酸酯体系</td><td>不饱和聚酯- 苯乙烯体系</td></tr><tr><td>无</td><td>>40</td><td>35</td><td>3%IPBE</td><td>3</td><td>14</td></tr><tr><td>3%651</td><td>>40</td><td>35</td><td>2%IBBE</td><td>1</td><td>25</td></tr><tr><td>3%184</td><td>>40</td><td></td><td>3%BP+5%MDEA</td><td>1</td><td></td></tr></table></body></html>\n\n注：表中数据为 $60^{\\circ}$ 下贮存的天数。IPBE为安息香异丙醚；IBBE为安息香异丁醚；MDEA为甲基二乙醇胺。  \n\n$\\textcircled{9}$ 合成容易，成本低，价格便宜。  \n常见光引发剂的物理性能见表4-8。  \n\n表4-8常见光引发剂的物理性能  \n\n\n<html><body><table><tr><td>光引发剂</td><td>外观</td><td>分子量</td><td>熔点 /℃</td><td>密度 /(g/cm3)</td><td>UV吸收峰/nm</td></tr><tr><td>184</td><td>白色或月白色结晶粉末</td><td>204.27</td><td>44~49</td><td>1.17</td><td>240~250 320~335</td></tr><tr><td>369</td><td>微黄色粉末</td><td>366.5</td><td>110～114</td><td>1.18</td><td>325～335</td></tr><tr><td>500</td><td>清澈、浅淡黄色液体</td><td>192.62</td><td><18(有结晶)</td><td>1.11</td><td>240~260 375～390</td></tr><tr><td>651</td><td>白色到浅黄色粉末</td><td>256.30</td><td>63~66</td><td>1.21</td><td>330~340</td></tr><tr><td>784</td><td>橙色粉末</td><td>534.39</td><td>190~195</td><td></td><td>380~390 460~480</td></tr><tr><td>819</td><td>浅黄色粉末</td><td>417.97</td><td>131～135</td><td>1.23~1.25</td><td>360～365 405</td></tr><tr><td>907</td><td>白色到浅褐色粉末</td><td>279.4</td><td>70~75</td><td>1.21</td><td>320～325</td></tr><tr><td>1300</td><td>浅黄色粉末</td><td>277.13</td><td>55~60</td><td></td><td></td></tr><tr><td>1700</td><td>清澈、亮黄色液体</td><td>196.94</td><td></td><td>1.01</td><td>245 325</td></tr><tr><td>1800</td><td>浅黄色粉末</td><td>239.13</td><td>48~55</td><td>1.10~1.20</td><td>325～330 390～405</td></tr><tr><td>1850</td><td>浅黄色粉末</td><td>288.34</td><td>≥45</td><td>1.201</td><td>325~330 390~405</td></tr><tr><td>2959</td><td>月白色粉末</td><td>224.26</td><td>86.5~89.5</td><td>1.270</td><td>275~285 320~330</td></tr><tr><td>1173</td><td>清澈、浅黄色液体</td><td>164.2</td><td>4 (沸点80~81)</td><td>1.074~1.078</td><td>265~280 320～335</td></tr><tr><td>4265</td><td>清澈、浅黄色液体</td><td>223.20</td><td></td><td>1.12</td><td>270~290 360~380</td></tr><tr><td>1000</td><td>清澈、浅淡黄色液体</td><td>172.2</td><td><4</td><td>1.10</td><td>245 280 331</td></tr></table></body></html>\n\n注：500为50%184／50%BP；1000为 $80\\%1173/20\\%184$ ；1300为 $30\\%369$ /70%651；1700为25%BAPO/75% 1173；1800为25%BAPO/ $75\\%184$ ；1850为 $50\\%$ BAPO/50%184；4265为 $50\\%\\mathrm{TPO}/50\\%1173$ 。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 109,
+        "chunk": "# 4.2 裂解型自由基光引发剂  \n\n自由基光引发剂按光引发剂产生活性自由基的作用机理不同，主要分为两大类：裂解型自由基光引发剂，也称PI1型光引发剂；夺氢型自由基光引发剂，又称PI2型光引发剂。  \n\n裂解型自由基光引发剂是指光引发剂分子吸收光能后跃迁至激发单线态，经系间窜跃到激发三线态，在其激发单线态或激发三线态时，分子结构呈不稳定状态，其中的弱键会发生均裂，产生初级活性自由基，引发低聚物和活性稀释剂聚合交联。  \n\n裂解型自由基光引发剂从结构上看，多是芳基烷基酮类化合物，主要有苯偶姻及其衍生物、苯偶酰及其衍生物、苯乙酮及其衍生物、α-羟烷基苯乙酮、α-胺烷基苯乙酮、酰基麟氧化物等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 110,
+        "chunk": "# 4.2.1苯偶姻及其衍生物  \n\n苯偶姻及其衍生物的常见结构如下。  \n\n![](images/5fa0deac72bf25ba017b69a4f999aa0ce65cfa302eb71c88ea1b402c869f2725.jpg)  \n\nR:H、 $\\mathbf{CH_{3}}$ ， $C_{2}\\mathbf{H}_{5}$ 、 $\\mathrm{CH}(\\mathrm{CH}_{3})_{2}$ ， $\\mathbf{CH_{3}C H(C H_{3})_{2}}$ ， $\\mathbf{C_{4}H_{9}}$  \n\n苯偶姻（benzoin，BE）为二苯乙醇酮，俗名安息香，是最早商品化的光引发剂，在早期第一代光固化涂料不饱和聚酯-苯乙烯体系中广泛应用。主要品种为安息香乙醚、安息香异丙醚和安息香丁醚。该类光引发剂在 $300\\sim400\\mathrm{nm}$ 有较强吸收，最大吸收波长（ $\\lambda_{\\operatorname*{max}}$ ）在320nm处，吸收光能后能裂解生成苯甲酰自由基和苄醚自由基，均能引发聚合。  \n\n![](images/ec08c3c3b835dca0c171c5e4ba55e080281a1a8fc8b7e4b06ff87e8feb31ef4e.jpg)  \n\n安息香醚类光引发剂在苯甲酰基邻位碳原子上的a-H，受苯甲酰基共轭体系吸电子的影响特别活泼，在室温不见光时，比较容易失去α-H产生自由基，导致暗聚合反应的发生，特别当涂料配方中混有重金属离子或与金属器皿接触时，重金属离子会促进暗反应的发生，严重影响贮存稳定性。容易发生暗反应，热稳定性差，这是安息香醚类光引发剂最大的弊病。同时苯甲酰基自由基夺氢后，生成苯甲醛有一定的臭味。  \n\n安息香醚类光引发剂的另一缺点是易黄变，这是因为光解产物中含有类结构的缘故。  \n\n![](images/15e8f53dfec69f2d62d9ae143454040fa7bb78ac7b3aa9186f83535e7f2f9ff8.jpg)  \n\n安息香醚类光引发剂虽然合成容易，成本较低，但因热稳定性差，易发生暗聚合和易黄变，目前已较少使用。 Y",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 111,
+        "chunk": "# 4.2.2苯偶酰及其衍生物  \n\n苯偶酰（benzil）又名联苯甲酰，通过光解虽然可产生两个苯甲酰自由基，但因效率太低，溶解性不好，一般不作光引发剂使用。其衍生物α,α'-二甲基苯偶酰缩酮就是最常见的光引发剂Irgacure651（DMPA、DMBK、BDK)，简称651。  \n\n651是白色到浅黄色粉末，熔点64～67℃，在活性稀释剂中溶解性良好，max为  \n\n$254\\mathrm{nm}$ ， $337\\mathrm{nm}$ ，吸收波长可达 $390\\mathbf{nm}$ 。651在吸收光能后裂解生成苯甲酰自由基和二甲氧苯基自由基，二甲氧苯基自由基可继续发生裂解，生成活泼的甲基自由基和苯甲酸甲酯。  \n\n![](images/72dd1b4a76e5a25286bae60f22471d2e8a1a1cce741dc37d7d820244af9c9fc9.jpg)  \n\n651有很高的光引发活性，因此广泛地应用于各种光固化涂料、油墨和胶黏剂中，651分子结构中苯甲酰基邻位没有 $\\alpha\\mathrm{H}$ ，所以热稳定性非常优良。651合成较容易，价格较低。但651与安息香醚类光引发剂一样，易黄变，其原因也是光解产物有式结构形成。  \n\n![](images/a66786ef1c31095aea6669fecc3c47fe003bf18a1e91dfdef074db9a458e36ed.jpg)  \n\n另外，光解产物苯甲醛和苯甲酸甲酯有异味，这些缺点都影响了它的应用，特别是易黄变性，使651不能在有耐黄变要求的清漆中使用，但它与ITX、907等光引发剂配合常用于光固化色漆和油墨中。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 112,
+        "chunk": "# 4.2.3 苯乙酮衍生物  \n\n苯乙酮（acetophenone）衍生物中作为光引发剂的主要是 $\\alpha,\\alpha-\\sum Z$ 氧基苯 $z$ 酮(DEAP)，它是浅黄色透明液体，与低聚物和活性稀释剂相容性好； $\\lambda_{\\operatorname*{max}}$ 在 $242\\mathrm{nm}$ 和 $325\\mathrm{nm}$ 处。DEAP在吸收光能后有两种方式裂解。  \n\n![](images/561371d972e43e8eab2e96c23e10e44584f99b27863df3d1fd42a24e45fd61bf.jpg)  \n\nDEAP按NorrishI型机理裂解产生苯甲酰自由基与二乙氧基甲基自由基，都是引发聚合的自由基，后者还可进一步裂解产生乙基自由基和甲酸乙酯。  \n\nDEAP还能经过六环中间态A，形成双自由基B，并裂解成2-乙氧基苯乙酮和乙醛，此过程为NorrishⅡ型裂解，或者双自由基B发生分子内闭环反应得到C。由于双自由基B引发聚合的活性很低，故此反应历程不能产生有效的活性自由基。  \n\nDEAP的光解历程主要为NorrishI型裂解，产生的苯甲酰自由基与二乙氧基甲基自由基以及二次裂解产物乙基自由基都可引发聚合，所以DEAP的光引发活性也很高，几乎与651相当。而且DEAP光解产物中没有导致黄变的取代苄基结构，因此与651相比不易黄变。但DEAP与安息香醚类一样，在苯甲酰基邻位有α-H存在，活泼性高，热稳定性差；相对价格较高，在国内较少使用。DEAP主要用于各种清漆，同时可与ITX等配合用于光固化色漆或油墨中。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 113,
+        "chunk": "# 4.2.4 $\\pmb{\\alpha}.$ -羟基酮衍生物  \n\nα羟基酮（a-hydroxyketone）类光引发剂是目前最常用，也是活性很高的光引发剂。已经商品化的光引发剂主要有如下几类。  \n\n![](images/631c1f13f4098816c43a9a9feada5afdd7d1d1e92dad3eab4c7921bf526fccd2.jpg)  \nDarocur1173（HMPP)，简称1173  \n\n![](images/85130ae478a320f79cb384c23e3bd83878c0c72de78bf89c9ce7dd3aba4ac9dd.jpg)  \nIrgacure184（HCPK)，简称184  \n\n![](images/7e24a6ca44dd6456e3c7c7bb333d8ad3960d6a1bacf1f70cd343e58faef67bbb.jpg)  \nDarocur2959（HHMP)，简称2959  \n\n1173（2-羟基-2-甲基-苯基丙酮-1）为无色或微黄色透明液体，沸点为80～81℃，与低聚物和活性稀释剂溶解性良好；^max在245nm、280nm和331nm处。1173吸收光能后，经裂解产生苯甲酰自由基和α-羟基异丙基自由基，都是引发聚合的自由基。发生氢转移后可形成苯甲醛和丙酮。  \n\n$$\n\\bigcirc-\\stackrel{\\mathrm{~I~}}{\\underbrace{\\mathrm{~C~-~C~-oH~}}}\\limits_{\\mathrm{C}\\mathrm{H}_{3}}^{\\mathrm{~O~}\\mathrm{CH}_{3}}\\xrightarrow{\\mathrm{~\\iota~o~}}\\bigcup_{\\mathrm{C}\\mathrm{H}_{3}}^{\\mathrm{~O~}}\\mathrel{\\underbrace{\\mathrm{~CH}_{3}}}^{\\mathrm{CH}_{3}},\\qquad\\bigcirc-\\underset{\\mathrm{CH}_{3}}{\\underbrace{\\mathrm{~I~}}}\\mathrel{\\underbrace{\\mathrm{~C~-oH~}}}\\bigcirc\\bigcirc\\bigcirc\\bigcirc\\bigcirc\\bigcirc\\bigcirc\\begin{array}{l}{{\\mathrm{~CH}_{3}}}\\\\ {\\mathrm{~\\iota~}}\\\\ {\\big|}\\\\ {\\mathrm{~CH}_{3}}\\end{array}\n$$  \n\n1173分子结构中苯甲酰基邻位没有α-H，所以热稳定性非常优良。光解时没有导致黄变的取代苄基结构，有良好的耐黄变性。1173合成也较容易，价格较低；又是液体，使用方便，是用量最大的光引发剂之一。在各类光固化清漆中，1173是主引发剂，也可与其他光引发剂907，特别是TPO、819等配合用于光固化色漆和油墨。1173的缺点是光解产物中苯甲醛有不良气味，同时挥发性较大。  \n\n184（1-羟基-环已基苯甲酮）为白色到月白色结晶粉末，熔点为45～49℃，在活性稀释剂中有良好的溶解性； $\\lambda_{\\operatorname*{max}}$ 在 $246\\mathrm{nm}$ 、 $280\\mathrm{nm}$ 和 $333\\mathrm{nm}$ 处。184吸收光能后，经裂解产生苯甲酰自由基和羟基环己基自由基，都是引发聚合的自由基。  \n\n![](images/e4d65c242b3c9c2d12b87e499415fe0421389d2a0822d6b3d5287952fd2bb8ce.jpg)  \n\n184与1173一样，分子结构中苯甲酰基邻位没有 $\\alpha\\mathrm{{H}}$ ，有非常优良的热稳定性。光解时没有取代苄基结构，耐黄变性优良，也是最常用的光引发剂，是耐黄变要求高的光固化清漆的主引发剂，也常与其他光引发剂配合用于光固化有色体系。184的缺点是光解产物中苯甲醛和环己酮带有异味。  \n\n2959（2-羟基-2-甲基-对羟乙基醚基苯基丙酮-1）为白色晶体，熔点为 $86.5\\sim89.5^{\\circ}\\mathrm{C}$ ，$\\lambda_{\\operatorname*{max}}$ 在 $276\\mathrm{nm}$ 和 $331\\mathrm{nm}$ 处。2959吸收光能后，经裂解产生对羟乙基醚基苯甲酰自由基和 $\\alpha$ 羟基异丙基自由基，它们都是引发聚合的自由基。  \n\n2959与1173一样，分子结构中苯甲酰基邻位无 $\\scriptstyle\\alpha-\\mathrm{\\mathrm{H}}$ ，有优良的热稳定性；光解产物无取代苄基结构，耐黄变性优良，可以用于各种光固化清漆，也可与其他光引发剂配合用于光固化有色体系。但因2959价格比1173和184高，加之在活性稀释剂中溶解性也差，在实际光固化中很少使用。2959分子结构中在苯甲酰基对位引入羟乙基醚基，水溶性比1173要好，1173在水中溶解度仅为 $0.1\\%$ ，而2959在水中溶解度为 $1.7\\%$ ，可以作为水性UV光固化涂料的光引发剂。另外，2959熔点比184高40多摄氏度，所以也可在UV光固化粉末涂料中作光引发剂使用。  \n\n为了使用方便，还有两种液态 $a$ 羟基酮复合光引发剂：Irgacure500，简称500；Irga-cure1000，简称 $1000$ 。  \n\n500为浅淡黄色透明液体，低于 $18^{\\circ}\\mathrm{C}$ 时会有结晶，组成为 $1173:\\mathrm{BP}=50:50$ （质量比)，是与裂解型光引发剂和夺氢型光引发剂配合的复合光引发剂， $\\lambda_{\\operatorname*{max}}$ 在 $250\\mathrm{nm}$ 和$332\\mathrm{nm}$ 处。  \n\n1000为浅淡黄色透明液体，组成为 $1173:184=50:50$ （质量比)，是与两种裂解型光引发剂配合的复合光引发剂， $\\lambda_{\\operatorname*{max}}$ 在 $245\\mathrm{nm}$ 、 $280\\mathrm{nm}$ 、 $331\\mathrm{nm}$ 处。  \n\n500和1000这两种复合光引发剂常用于各种光固化清漆中。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 114,
+        "chunk": "# 4.2.5 $\\pmb{\\alpha}$ -氨基酮衍生物  \n\n$\\alpha$ 氨基酮（ $\\alpha$ -aminoketone）类光引发剂也是一类反应活性很高的光引发剂，常与硫杂葱酮类光引发剂配合，应用于有色体系的光固化，表现出优异的光引发性能。已经商品化的光引发剂如下。 上米  \n\n![](images/002b198076d0e8d72e9434d62f695e7ff4b61b823a4d577d3ede91de9f1d73fb.jpg)  \nIrgacure907（MMMP)，简称907  \n\n![](images/472ac4a8c4157437f5847d71d84df80e696080f69d612ac38926b6034077fc1a.jpg)  \nIrgacure369（BDMB)，简称369  \n\n907［2-甲基1-(4-甲硫基苯基)-2-吗啉丙酮-1］为白色到浅褐色粉末，熔点为70～75℃，在活性稀释剂中有较好的溶解度; $\\lambda_{\\operatorname*{max}}$ 在 $232\\mathrm{nm}$ ， $307\\mathrm{nm}$ 处。907光解时产生对甲巯基苯甲酰自由基和吗啉异丙基自由基，都能引发聚合。  \n\n$$\nH_{3}C-S-\\bigcup_{i=1}^{0}{\\underset{C\\cdot H_{3}}{\\overset{\\mathrm{C}\\cdot H_{3}}{\\longrightarrow}}}{\\underset{C\\cdot H_{3}}{\\overset{\\mathrm{C}\\cdot H_{3}}{\\longrightarrow}}}{\\underset{C\\cdot H_{3}}{\\overset{h^{\\prime}}{\\longrightarrow}}}{\\underset{C\\cdot H_{3}}{\\overset{h^{\\prime}}{\\longrightarrow}}}{\\mathrm{H}}_{3}C-S-\\bigcup_{i=1}^{0}{\\underset{C\\cdot H_{3}}{\\overset{\\mathrm{C}\\cdot H_{3}}{\\longrightarrow}}}+{\\underset{C\\cdot\\bigcup_{i=1}}{\\overset{\\mathrm{C}\\cdot\\operatorname{h}}{\\longrightarrow}}}0\n$$  \n\n在光固化有色体系中，907与硫杂葱酮类光引发剂配合使用，有很高的光引发活性。由于有色体系中颜料对紫外光的吸收，使907光引发效率大大降低，但硫杂葱酮类光引发剂的存在，它的吸收波长可达380～420nm，在360～405nm处有较高的摩尔消光系数，能在有色体系中与颜料竞争吸光，从而激发至激发三线态，与907光引发剂发生能量转移，使907由基态跃迁到激发三线态，间接实现光引发剂907光敏化，而硫杂葱酮类光引发剂变回基态。  \n\n![](images/cb336d92150e01f74ae7b22ff06ce56ef4d9409aa1f670f4d3fcc1994a912819.jpg)  \n\n另外，907分子中有吗啉基，为叔胺结构，它与夺氢型硫杂葱酮类光引发剂形成激基复合物并发生电子转移，产生自由基引发聚合，在这种双重作用下，呈现在有色体系的光固化时有很高的光引发活性。  \n\n907光引发剂其光解产物为含硫化合物即对甲琉基苯甲醛，有明显的臭味，使其应用受到限制。另外907也因耐黄变性差，故不能用于光固化清漆和白漆中。  \n\n369[2-苄基-2-二甲氨基-1-(4-吗啉苯基）丁酮-1]是微黄色粉末，熔点为110～114℃；入max在233nm、324nm处。369光解时有两种裂解方式：α裂解和β裂解，其中以α裂解为主。  \n\n![](images/9e5ef27cbb52e4b1ca6621e501e8aa1f7637bde023bde41bcf7fdf02efe91e9e.jpg)  \n\n369光解后， $\\alpha$ 裂解产生的对吗啉基苯甲酰基自由基和胺烷基自由基都能引发聚合。369和907光引发剂一样，与硫杂葱酮类光引发剂配合，在光固化有色体系中有很高的光引发活性，因此特别适用于光固化色漆和油墨中，尤其是黑色涂料和油墨。但369也存在黄变性，故不能在光固化清漆和白漆中使用。369分子中没有含硫结构，同时光解产物对吗啉基苯甲醛气味也较小。369 因合成工艺较907复杂，价格也贵，在活性稀释剂中溶解性也比不上  \n\n907，所以不如907应用广泛。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 115,
+        "chunk": "# 4.2.6苯甲酰甲酸酯类  \n\n苯甲酰甲酸酯光引发剂可通过草酸单酯酰氯与取代苯经Friedel-Crafts 反应合成，操作简单，成本较低，已商品化的有MBF。  \n\n![](images/94e90f8eb6bb15c41dc3487b5e46bd483da021891824ca20e9b5ff8a497fa5b5.jpg)  \n\nMBF常温下为液体，熔点为17℃，沸点为246～248℃；^max在255nm、325nm处，光引发活性略低于1173。  \n\nMBF 的酯基上有y-H，吸光后发生两种光解，经NorrishⅡ型裂解，形成六元环中间态，没有产生有效的活性自由基；经分子间发生夺氢历程，产生基自由基和烷基自由基，后者进一步裂解，可形成高引发活性的苯甲酰甲酰自由基和苯基自由基。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 116,
+        "chunk": "# 4.2.7 酰基膦氧化物  \n\n酰基麟氧化物（acylphosphineoxide）光引发剂是一类光引发活性很高、综合性能较好的光引发剂，已商业化的产品主要有如下几类。  \n\n![](images/f9b507fe5f23678da8d3c4d754158e1de53688b044634bf1fdc1d7d8ee0afffe.jpg)  \nBAPOIrgacure819，简称819  \n\nTEPO（2,4，6-三甲基苯甲酰基-乙氧基-苯基氧化麟）为浅黄色透明液体，与低聚物和活性稀释剂溶解性好；入max在380nm处，吸收波长可达430nm。光解产物为三甲基苯甲酰基自由基和苯基-乙氧基-麟酰自由基，都是引发活性很高的自由基。 55  \n\n![](images/ab15a63d3339e536073870aa98d5e08a6592e312643a956640f4b2a96e826fa7.jpg)  \n\nTPO(2,4，6-三甲基苯甲酰基-二苯基氧化麟）为浅黄色粉末，熔点为90～94℃，在活性稀释剂中有足够的溶解度；^max在269nm、298nm、379nm、393nm处，吸收波长可达430nm。光解产物为三甲基苯甲酰基自由基和二苯基麟酰自由基，都是引发活性很高的自  \n\n由基。  \n\n![](images/d0e9bd16db3ec0ce852865f7f75244de7dec08ed80de1ad1cac726345395dbdf.jpg)  \n\nTPO和TEPO的 $\\lambda_{\\operatorname*{max}}$ 均在 $380\\mathrm{nm}$ 处，可见光区 $430\\mathrm{nm}$ 还有吸收，因此特别适合于有色体系的光固化。其光解产物的吸收波长是向短波移动，具有光漂白效果，有利于紫外光透过，可适用于厚涂层的固化。其热稳定性优良，加热至 $180^{\\circ}\\mathrm{C}$ 无化学反应发生，贮存稳定性好。虽然自身都带有浅黄色，但光解后变为无色，不发生黄变。TEPO与低聚物、活性稀释剂溶解性能好，但光引发效果不如TPO，所以市场上的应用主要为TPO，在有色涂层（特别是白色涂层)、厚涂层和透光性较差的涂层光固化中广泛应用，鉴于TPO在可见光区也有吸收，因此在生产制造和贮存运输时应注意避光。  \n\n819也称BAPO[双（2，4，6-三甲基苯甲酰基）苯基氧化麟]，为浅黄色粉末，熔点为$127{\\sim}133^{\\circ}\\mathrm{C}$ ， $\\lambda_{\\operatorname*{max}}$ 在 $370\\mathrm{nm}$ 、 $\\scriptstyle405\\mathrm{nm}$ 处，最长吸收波长可达 $450\\mathrm{nm}$ 。光解产物有两个三甲基苯甲酰基自由基和一个苯基麟酰自由基，都是引发活性很高的自由基，所以比TPO的光引发活性更高。  \n\n![](images/37a8b108ca44b3a1e2beac0d0a1d12f24b7b7257dd810ebb09aff89d54b837eb.jpg)  \n\n由于TPO特别是BAPO光引发活性高，加之价格较贵，所以配制了与 $\\alpha$ 羟基酮光引发剂复配的组分即复合光引发剂。  \n\n1700 25%819/75%1173   \n1800 25%819/75%184   \n1850 50%819/50%184   \n4265 50%TPO/50%1173   \n819DW 819稳定的水分散液  \n\n1700和4265都是液体，使用也更方便，819DW用于水性UV体系。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 117,
+        "chunk": "# 4.2.8 含硫的光引发剂  \n\nC—S键的键能较低，约为 $272\\mathrm{kJ/mol}$ ，只需较少的能量即可使其均裂为两个自由基，如与适当的吸光基团连接，在吸收光能后，就可实现C—S键的光裂解，已商品化的产品有BMS。  \n\n![](images/21381b0c6aee6bd0847f95bfb61e2dec89514ddea061a49ad29a257a88464aac.jpg)  \n\nBMS（4-对甲苯硫基二苯甲酮）为奶黄色结晶粉末，熔点为 $73{\\sim}83^{\\circ}\\mathrm{C}$ ， $\\lambda_{\\operatorname*{max}}$ 在 $245\\mathrm{nm}$ 小$315\\mathrm{nm}$ 处，BMS吸收光能后，可以发生两种方式的C—S键裂解，产生取代苯基自由基和芳巯基自由基，都可引发聚合。  \n\n，如有叔胺时，还可同时发生二苯甲酮与叔胺之间的夺氢反应，产生活性很高的胺烷基自由基。BMS虽然有较好的光引发活性，由于光解后的产物中有极其难闻的硫醇化合物，故  \n\n影响其应用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 118,
+        "chunk": "# 4.3 夺氢型自由基光引发剂  \n\n夺氢型光引发剂是指光引发剂分子吸收光能后，经激发和系间窜跃到激发三线态，与助引发剂— 氢供体发生双分子作用，经电子转移产生活性自由基，引发低聚物和活性稀释剂聚合交联。  \n\n夺氢型光引发剂从结构上看，都是二苯甲酮或杂环芳酮类化合物，主要有二苯甲酮及其衍生物、硫杂葱酮类、葱酿类等。  \n\n与夺氢型光引发剂配合的助引发剂——氢供体主要为叔胺类化合物，如脂肪族叔胺、乙醇胺类叔胺、叔胺型苯甲酸酯、活性胺（带有丙烯酰氧基，可参与聚合和交联的叔胺）等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 119,
+        "chunk": "# 4.3. 1 二苯甲酮及其衍生物  \n\n二苯甲酮（benzophenone，BP）为白色到微黄色结晶，熔点为 $47\\sim49^{\\circ}C$ ， $\\lambda_{\\operatorname*{max}}$ 在253nm、345nm处。BP吸收光能后，经激发三线态与助引发剂叔胺作用形成激基复合物(exciplex)，发生电子转移，BP得电子形成二苯甲醇负离子和胺正离子，二苯甲醇负离子从胺正离子中夺氢生成无引发活性的二苯甲醇自由基（羰基自由基，ketylradical）和活性很高的胺烷基自由基，后者引发低聚物和活性稀释剂聚合交联。  \n\n![](images/a77b4fb4145a5f94930d1121a7bbe0a40235d3c0e38231f428645a2e68fa34cb.jpg)  \n\nBP由于结构简单，合成容易，是价格最便宜的一种光引发剂。但光引发活性不如651、1173等裂解型光引发剂，光固化速率较慢，容易使固化涂层泛黄，与助引发剂叔胺复配使黄变加重。另外，BP熔点较低，具有升华性，易挥发，不利于使用。但BP与活性胺配合使用，有一定的抗氧阻聚功能，所以表面固化功能较好。  \n\nBP的衍生物有很多都是有效的光引发剂，如下面所列7种结构的BP衍生物。  \n\n![](images/c55d16ea1d9e75789c8f3e2f44edd7529f6b1621f554d0024bfa8798eb3d6bfc.jpg)  \n4,4'-双（二甲氨基）二苯甲酮，俗称米酮（Michler'sketone，简称MK)  \n\n![](images/4322f7012d5d734b1817fc28f1683fc1e5540d0e4012f25d5ce698debc5e6502.jpg)  \n\n2,4，6-三甲基二苯甲酮和4-甲基二苯甲酮的混合物即光引发剂EsacureTZT，为无色透明液体，沸点 $310\\sim330^{\\circ}\\mathrm{C}$ ，与低聚物和活性稀释剂有很好的溶解性； $\\lambda_{\\operatorname*{max}}$ 在 $250\\mathrm{nm}$ ， $340\\mathrm{nm}$ 处，吸收波长可达 $400\\mathrm{nm}$ 。与助引发剂叔胺配合使用有很好的光引发效果，可用于各种光固化清漆，但因价格比BP贵，一般仅用于高档光固化清漆中。  \n\nMK为黄色粉末，在 $365\\mathrm{nm}$ 处有很强的吸收，本身有叔胺结构，单独使用就是很好的光引发剂，与BP配合使用，其光引发活性远远高于BP/叔胺或MK/叔胺体系，光聚合速率是后两者的10倍左右，因此是早期色漆和油墨光固化中首选的光引发剂组合。但MK被确认为是致癌物，不宜推广使用。DEMK虽然毒性比MK小，但溶解性较差，也与MK一样易黄变；MEMK溶解性有改善，可与BP配合用于有色体系的光固化中。  \n\n![](images/239e8f7b2dcef32534c2c4f1d261ef8a8db0c63f3d7724bda8274c15b5911a42.jpg)  \n$^{4,4^{\\prime}}$ -双（甲基、乙基氨基）二苯甲酮，俗称甲乙基米酮（MEMK)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 120,
+        "chunk": "# 4.3.2 硫杂葱酮及其衍生物  \n\n硫杂葱酮（thioxanthone，TX）是常见的夺氢型自由基光引发剂，但TX在低聚物和活性稀释剂中的溶解性很差，现多用其衍生物作光引发剂，已商品化的产品主要有如下几种。  \n\n目前，应用最广、用量最大的为ITX。  \n\nITX为淡黄色粉末，熔点为 $66\\sim77^{\\circ}C$ ，在活性稀释剂和低聚物中有较好的溶解性。 $\\lambda_{\\operatorname*{max}}$ 在 $257.5\\mathrm{nm}$ 、 $382\\mathrm{nm}$ 处，吸收波长可达 $430\\ \\mathrm{nm}$ ，已进人可见光吸收区域。ITX吸收光能后，经激发三线态必须与助引发剂叔胺配合，形成激基复合物发生电子转移，ITX得电子后形成无引发活性的硫杂葱酮酚氧自由基和引发活性很高的 $\\alpha$ -胺烷基自由基，引发低聚物和活性稀释剂聚合、交联。  \n\n![](images/a05062bddfff94faf09fceae2dd892499ac9a513656e6634c8396f3b0e65a637.jpg)  \n\n![](images/0610e24fbac7459f7714d34b76541d50c8e246105b6c3a6f1340f95f56d2a771.jpg)  \n\n与ITX配合使用的助引发剂以4-二甲氨基苯甲酸乙酯（EDAB）最好，其不仅引发活性高，而且黄变较小。ITX有较高的吸光波长，较强的吸光性能，与907、369 等 $\\alpha$ -氨基酮光引发剂配合，特别适用于有色体系的光固化。ITX也常与阳离子光引发剂二芳基碘盐配合使用，ITX吸光后激发，经电子转移使二芳基碘盐发生光解，产生阳离子和自由基引发光聚合。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 121,
+        "chunk": "# 4.3.3 葱醒及其衍生物  \n\n葱酿（anthraquinone）类光引发剂是又一类夺氢型自由基光引发剂，葱溶解性很差，难以在低聚物和活性稀释剂中分散，故多用溶解性好的2-乙基葱作光引发剂。  \n\n![](images/c8ddbb1ba4ee685e13ac0e51b5221581ed7876952ddd05e12a41fd767ef5a626.jpg)  \n2-乙基蕙醒（2-EA)  \n\n2-EA为淡黄色结晶，熔点为 $107{\\sim}111\\ensuremath{\\mathrm{^{\\circ}C}}$ ， $\\lambda_{\\operatorname*{max}}$ 在 $256\\mathbf{nm}$ $275\\mathrm{nm}$ 和 $325\\mathrm{nm}$ 处，吸收波长可达 $430\\mathrm{nm}$ ，已进人可见光吸收区域。2-EA吸收光能后，在激发三线态与助引发剂叔胺作用，夺氢后生成没有引发活性的酚氧自由基（A）和引发活性很高的胺烷基自由基，后者引发低聚物和活性稀释剂聚合、交联。酚氧自由基经双分子歧化生成9，10-葱二酚（B）和2-EA，而酚氧自由基和葱二酚都能被 $\\mathrm{O}_{2}$ 氧化又都生成2-EA。因此在有氧条件下，光引发剂效率比无氧时高，也就是说2-EA对氧阻聚敏感性小，这是葱类光引发剂的特点。  \n\n![](images/b8bd1ca6ce99a2d28528eb48d3eb2e30ed1c90b683bdb170f61747547e8381b3.jpg)  \n\n葱类光引发剂虽然对氧阻聚敏感性小，但酚氧自由基和葱二酚都是自由基聚合的阻聚剂，它们虽然可以经氧化再生为葱，但与自由基或链增长自由基的结合也是一种有利的竞争反应，导致聚合过程受阻，因此，葱类光引发剂的光引发活性并不高。2-EA主要用于阻焊剂，而且酚醛环氧丙烯酸酯低聚物有较多活性氢存在，可不再加助引发剂活性胺。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 122,
+        "chunk": "# 4.3.4 助引发剂  \n\n与夺氢型自由基光引发剂配合的助引发剂———供氢体，从结构上看都是至少有一个α-C的叔胺，与激发态夺氢型光引发剂作用，形成激基复合物，氮原子失去一个电子，N邻位α-C上的H呈强酸性，很容易呈质子离去，产生以C为中心的活泼的胺烷基自由基，引发低聚物和活性稀释剂聚合交联。  \n\n叔胺类化合物有脂肪族叔胺、乙醇胺类叔胺、叔胺型苯甲酸酯和活性胺（带有丙烯酰氧基的叔胺）。  \n\n（1）脂肪族叔胺最早使用的叔胺如三乙胺，价格低，相容性好，但挥发性太大，臭味太重，现已不使用。  \n\n（2）乙醇胺类叔胺有三乙醇胺、N-甲基二乙醇胺、N,N-二甲基乙醇胺、N,N-二乙基乙醇胺等。三乙醇胺虽然成本低，活性高，但亲水性太大，影响涂层性能，黄变严重，所以不能使用。其他三种取代乙醇胺，活性高，相容性好，不少配方中仍在使用。  \n\n（3）叔胺型苯甲酸酯有 N,N-二甲基苯甲酸乙酯、N,N-二甲基苯甲酸-2-乙基己酯和苯甲酸二甲氨基乙酯。  \n\n![](images/4873d8485f468b39328f19fc27b734920b3348824fb4601381e9f33904c091af.jpg)  \n苯甲酸二甲氨基乙酯（QuantacureDMB）  \n\n这三个叔胺都是活性高、溶解性好、低黄变的助引发剂，特别是EDAB（max为315nm）和ODAB（Amax为310nm）在紫外区有较强的吸收，对光致电子转移有促进作用，有利于提高反应活性。但价格较贵，主要与TX类光引发剂配合，用于高附加值油墨中。  \n\n（4）活性胺带有丙烯酰氧基的叔胺既有很好的相容性，气味也低，又能参与联合交联，不会发生迁移。这类叔胺是由仲胺（二乙胺或二乙醇胺）与二官能团丙烯酸酯或多官能团丙烯酸酯经迈克尔加成反应直接制得的。在表2-28中可看到各种牌号的活性胺。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 123,
+        "chunk": "# 4.4 阳离子光引发剂  \n\n阳离子光引发剂（cationicphotoinitiator）是又一类非常重要的光引发剂，它是在吸收光能后到激发态，分子发生光解反应，产生超强酸即超强质子酸（也叫布朗斯特酸Bronstedacid）或路易斯酸（Lewisacid)，从而引发阳离子低聚物和活性稀释剂进行阳离子聚合。阳离子光聚合的低聚物和活性稀释剂主要有环氧化合物和乙烯基醚，已在第3章和第2章中讲述，另外还有内酯、缩醛、环醚等。  \n\n阳离子光固化与自由基光固化比较有下列特点。  \n\n①阳离子光固化不受氧影响；而自由基光固化对氧敏感，发生氧阻聚。  \n\n②阳离子光固化对水汽、碱类物质敏感，导致阻聚；而自由基光固化对水汽、碱类物  \n\n质不敏感。  \n\n$\\textcircled{3}$ 阳离子光固化时体积收缩小，有利于对基材的附着；而自由基光固化时体积收缩大。  \n\n$\\textcircled{4}$ 阳离子光固化速率较慢，升高温度有利于光固化速率提高；而自由基光固化速率快， 温度影响小  \n\n$\\textcircled{5}$ 阳离子光固化的活性中间体超强酸在化学上是稳定的，由于所带正电荷不会发生偶合而消失，在链终止时也会产生新的超强酸，因此光照停止后，仍能继续引发聚合交联，进行后固化，寿命长，适合于厚涂层和有色涂层的光固化；自由基光固化因自由基很容易偶合而失去引发活性，一旦光照停止，光固化就马上停止，没有后固化现象。表4-9反映了两种光固化的比较。  \n\n表4-9 阳离子光固化与自由基光固化比较  \n\n\n<html><body><table><tr><td>项 目</td><td>自由基光固化</td><td>阳离子光固化</td></tr><tr><td>低聚物</td><td>（甲基)丙烯酸酯树脂、不饱和聚酯 (甲基)丙烯酸酯、乙烯类单体</td><td>环氧树脂、乙烯基醚树脂 乙烯基醚、环氧化合物</td></tr><tr><td>活性稀释剂 光引发活性中间体</td><td>自由基</td><td>阳离子</td></tr><tr><td></td><td>短</td><td></td></tr><tr><td>活性中间体寿命</td><td></td><td>长</td></tr><tr><td>光固化速率</td><td>快</td><td>．慢</td></tr><tr><td>后固化</td><td>可忽略</td><td>强</td></tr><tr><td>体积收缩</td><td>高(7%~15%)</td><td>低(3%~5%)</td></tr><tr><td>对氧的敏感性</td><td>强</td><td>无</td></tr><tr><td>对潮气的敏感性</td><td>无</td><td>强</td></tr><tr><td>对碱的敏感性</td><td>无</td><td>强</td></tr><tr><td>气味</td><td>高</td><td>低</td></tr><tr><td>价格</td><td>低</td><td>高</td></tr></table></body></html>  \n\n阳离子光引发剂主要有芳基重氮盐、二芳基碘盐、三芳基硫盐、芳基茂铁盐等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 124,
+        "chunk": "# 4.4. 1 芳基重氮盐  \n\n芳基重氮盐（aryldiazo salt）吸收光能后，经激发态分解产生氟苯、多氟化物和氮气，多氟化物是强路易斯酸，直接引发阳离子聚合，也能间接产生超强质子酸，再引发阳离子聚合。  \n\n但芳基重氮盐热稳定性差，且光解产物中有氮气释放，会在涂层中形成气泡，应用受到限制，因此目前已不再使用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 125,
+        "chunk": "# 4.4.2二芳基碘盐  \n\n二芳基碘盐（diaryliodoniumsalt）是一类重要的阳离子光引发剂，由于合成较方便，热稳定性较好，体系贮存稳定性好，光引发活性高，已商品化。  \n\n二芳基碘盐在最大吸收波长处的摩尔消光系数可高达 $10^{4}$ 数量级，但吸光波长比较短，绝大多数吸收波长在 $250\\mathrm{nm}$ 以下，即使苯环上引入各种取代基，对吸光性能也无显著改善作用，与紫外光源不匹配，利用率很低。只有当碘盐连接在吸光性很强的芳酮基团上时，才可使碘盐吸收波长增至300nm以上（表4-10)。  \n\n表4-10 碘绘盐的最大吸收波长  \n\n\n<html><body><table><tr><td>碘盐</td><td>最大吸收波长/nm</td><td>摩尔消光系数/[L/（mol·cm)]</td></tr><tr><td>< BFT</td><td>227</td><td>17800</td></tr><tr><td>CHO- BF4</td><td>246</td><td>15400</td></tr><tr><td>+ AsF6 ON NO2</td><td>245</td><td>17000</td></tr><tr><td>CH- + CH3 BF</td><td>236</td><td>18000</td></tr><tr><td>CHg T CH3 PF</td><td>237</td><td>18200</td></tr><tr><td>(CH3)3C (CH)C BF</td><td>238</td><td>20800</td></tr><tr><td>0 + X- 0</td><td>335</td><td></td></tr><tr><td>0 X-</td><td>296,336</td><td></td></tr></table></body></html>  \n\n二芳基碘盐的阴离子对吸光性没有影响，但对光引发活性有较强影响，阴离子为SbF。时，引发活性最高，这是因为SbF。亲核性最弱，对增长链碳正离子中心的阻聚作用最小。当阴离子为BF时，碘盐引发活性最低，因BF比较容易释放出亲核性较强的F-，导致碳正离子活性中心与F一结合，终止聚合。从光引发活性看，不同阴离子活性大小依次为：  \n\n$$\n\\mathbf{SbF_{6}}>\\mathbf{AsF_{6}^{-}}>\\mathbf{PF_{6}^{-}}>\\mathbf{BF_{4}^{-}}\n$$  \n\n二芳基碘盐吸收光能后，发生光解时有均裂和异裂，既产生超强酸，又产生自由基。因此，碘盐既可引发阳离子光聚合，又能引发自由基光聚合。 y  \n\n![](images/1827dafaeb5280e75869400cecd77be4d93b72637ab79c62b40c8bf40af32bf1.jpg)  \n超强酸  \n\n二芳基碘盐只对波长250nm附近的UV光有强的吸收，对大于300nm的UV光和可见光吸收很弱，故对UV光源的能量利用率很低。为了提高UV光引发效率和体系对UV光的能量利用率，通常使用光敏剂和自由基光引发剂来拓宽体系和UV吸收谱带，光敏剂和自由基光引发剂首先吸收UV光能而激发，再通过电子转移给碘盐，进而产生超强酸引发阳离子光聚合和自由基引发自由基光聚合。所以硫杂葱酮和二苯甲酮等自由基光引发剂时常与碘盐配合使用，以提高碘盐的光引发效率和UV光吸收效率。  \n\n碘盐在活性稀释剂中溶解性较差，同时碘盐的毒性较大，特别是六氟锑酸盐是剧毒品，无法在商业上应用，这是制约碘盐作为阳离子光引发剂推广应用的两个问题。目前通过在苯环上增加取代基的方法，使这两个问题得到克服，如苯环上引人十二烷基后碘盐溶解性大为改善，在苯环上引人 $8\\sim10$ 个碳的烷氧基链，碘盐的半致死量 $\\mathrm{LD}_{50}$ 从 $40\\mathrm{mg/kg}$ （剧毒）提升至 $\\mathbf{5000mg/kg}$ (基本无毒)。  \n\n![](images/2ec927d25c6b0268dc02209ff6ce10174d25e94e9073ba2cbec25b2f2a2cabdb.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 126,
+        "chunk": "# 4.4.3 三芳基硫盐  \n\n三芳基硫盐（triarylsulfonium salt）是又一类重要的阳离子光引发剂。三芳基硫盐的热稳定性比二芳基碘盐更好，加热至300℃不分解，与活性稀释剂混合加热也不会引发聚合，故体系贮存稳定性极好（表4-11)，光引发活性高，也已商品化。  \n\n![](images/281f72f47773c241f363ecf2b912cd8302502b790527508cab182d7ddaa0038b.jpg)  \n\n① 阳离子光引发剂加人到3,4-环氧环已酸和3',4'-环氧环已基甲酯混合物中，40℃避光保存。  \n\n三芳基硫盐的最大吸收波长为230nm，因此对紫外光源的利用率很低，但苯环取代物吸收波长明显增加，如苯硫基苯基二苯基硫盐的最大吸收波长为 $316\\mathrm{nm}$  \n\n![](images/6f4e76b16a784fabbe0bdf9f2634c20e737183fd6a685e5d4c0e248f6df3f83a.jpg)  \n\n三芳基硫盐的阴离子对吸光性影响不大，但对光引发活性有较强影响，其阴离子活性大小与二芳基碘盐一样，依次为：  \n\n$$\n\\mathrm{SbF_{6}^{-}>A s F_{6}^{-}>P F_{6}^{-}>B F_{4}^{-}}\n$$  \n\n三苯基硫盐与二芳基碘盐相似，吸收光能后发生光解反应，既产生超强酸引发阳离子光聚合，又能产生自由基引发自由基光聚合。  \n\n![](images/5f885762a3dff85a298ebc85e3b8916817591cd6b85d8f5960fa2b4decaa4622.jpg)  \n超强酸  \n\n三苯基硫盐在活性稀释剂中溶解性不好，所以商品化的三苯基硫盐都是 $50\\%$ 的碳酸丙烯酯溶液。  \n\n三苯基硫盐也和二芳基碘盐一样吸光波长在 $250\\mathrm{nm}$ 以下，不能充分利用UV光源的UV光能，为此要与一些稠环芳烃化合物（葱、、等）配合使用，以使三芳基硫盐光敏化，从而发生光解，产生阳离子超强酸和自由基引发聚合。三芳基硫盐的另一个缺点是光解产物二苯基硫醚有臭味。商品化的三芳基硫盐为陶氏化学公司的UVI6976和UVI 6992.  \n\n![](images/0905f497ef3a72505b425d37970c75733d46024c7b10c013197ab5057c0aafae.jpg)  \n双（4，4'-硫醚三苯基硫）六氟锑酸盐  \n\n![](images/62e0b4a05f3905ab0cd8067a3490b5689f0c1303ae387b1f2be6307abbe1e5b5.jpg)  \n苯硫基苯基，二苯基硫铺六氟锑酸盐  \n\nUV16976是上述两种三芳基硫盐的 $50\\%$ 碳酸丙烯酯溶液。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 127,
+        "chunk": "# 4.4.4 芳茂铁盐  \n\n芳茂铁盐（arylFerrocenium salt）是继二芳基碘盐和三芳基硫盐后，又开发的一种阳离子光引发剂，已商品化的是Irgacure26l，简称261。  \n\n![](images/b756af6fb7fae28555a3e4d4541b9e4e3c42da45fb7ae22a7c39d42ff691fc54.jpg)  \n异丙苯茂铁六氟磷酸盐，简称261  \n\n261为黄色粉末，熔点为85～88℃，它在远紫外（240～250nm）和近紫外（390～$_{400\\mathrm{nm}})$ ）均有较强吸收，在可见光 $530{\\sim}540\\mathrm{nm}$ 也有吸收，因此是紫外光和可见光双重光引发剂。261吸光后发生分解，生成的异丙苯和茂铁路易斯酸可引发阳离子聚合。 5  \n\n![](images/5ebebbfd32a968f051c5bb01a0a8ed4ebfbc0dcf6a7e174968b02ceacb2cd010.jpg)  \n茂铁路易斯酸",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 128,
+        "chunk": "# 4.5.1KIP系列大分子光引发剂  \n\n目前使用的光引发剂都为有机小分子，在使用中存在下面的问题。  \n\n（1）相容性一些固体光引发剂在低聚物和活性稀释剂中溶解性差，需加热溶解，当放置时遇到低温，引发剂可能会析出，影响使用。  \n\n（2）迁移性涂层固化后残留的光引发剂和光解产物会向涂层表面迁移，影响涂层表观和性能，也可能引起毒性和黄变性。  \n\n（3）气味有的光引发剂易挥发，大多数光引发剂的光解产物有不同程度的异味，因此在卫生和食品包装材料上影响其使用。  \n\n为了克服小分子光引发剂的上述病，人们设计了大分子光引发剂或可聚合的光引发剂，最早商品化的大分子光引发剂为宁柏迪公司EsacureKIP150 以及Esacure KIP 150为主的KIP系列和KT系列，沙多玛公司的SR1130也是类似结构的大分子光引发剂。  \n\n![](images/2e6f1e21a578aac69fc4b9b25cf4a8f8dcae358f66b20f1ca0ad96b032be81bc.jpg)  \n2-羟基-2-甲基-1-（4-甲基乙烯基-苯基）丙酮（KIP150)  \n\nKIP150为橙黄色黏稠物，分子量在2000左右，在大多数活性稀释剂和低聚物中有较好的溶解性。它实际上可看作将1173连接在甲基乙烯基上组成的低聚物，属于 $\\alpha$ 羟基酮类光引发剂， $\\lambda_{\\operatorname*{max}}$ 在 $245\\mathrm{nm}$ 、 $325\\mathrm{nm}$ 处。 $\\kappa\\ensuremath{\\mathrm{IP}}150$ 是一个不迁移、低气味和耐黄变的光引发剂，虽然其光引发效率只有1173的 $\\overline{{1/4}}$ （表4-12)，但KIP150在光照后，可在大分子上同时形成多个自由基，局部自由基浓度可以很高，能有效克服氧阻聚，提高光聚合速率，在使用时有较好的光引发作用，可应用于各种清漆和涂料，也可用于油墨、印刷版和胶黏剂。  \n\n表4-121173、KIP150光引发效率  \n\n\n<html><body><table><tr><td>光引发剂</td><td>激发三线态寿命/ns</td><td>光聚合速率/s</td><td>光引发效率/%</td></tr><tr><td>1173</td><td>1.4</td><td>41</td><td>0.28</td></tr><tr><td>4-十二烷基1173</td><td>4.0</td><td>30</td><td>0.12</td></tr><tr><td>KIP150</td><td>8.0</td><td>26</td><td>0.07</td></tr></table></body></html>  \n\n为使用方便，KIP150由活性稀释剂稀释或与其他液态光引发剂配成各种新的组成物如下。  \n\nKIPLE：为KIP150和TMPTA组成物。  \nKIP75LT：为 $75\\%$ 的KIP150和 $25\\%$ 的 TPGDA组成物。  \nKIP100F：为 $70\\%$ 的KIP150和 $30\\%$ 的1173组成物。KIP/KB：为 $73.5\\%$ 的KIP150和 $26.5\\%$ 的651组成物。  \nKIPEM：为 $\\mathtt{K I P150}$ 的稳定的水乳液。  \nKIP55：为 $50\\%$ 的KIP150和 $50\\%$ 的TZT组成物。  \nKIP37：为 $30\\%$ 的KIP150和 $70\\%$ 的TZT组成物。  \nKIP46：为 $\\mathtt{K I P150}$ 、TZT和TPO组成物。  \n除了KIP/KB是黏稠物外其他都是液体，使用方便，KIPEM用于水性UV体系。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 129,
+        "chunk": "# 4.5.2大分子二苯甲酮光引发剂OmnipolBP  \n\n![](images/ff17a8decac8782a1e0a3ead38e653ac1a61f8a53b77e32edb764561cabd1e5b.jpg)  \n\n这是一种夺氢型双官能度大分子自由基光引发剂， $\\lambda_{\\operatorname*{max}}$ 在 $280\\mathrm{nm}$ 处，吸收可延伸至$380\\mathrm{nm}$ 。它的光引发活性和BP相近，颜色比BP略黄，为黄色黏稠液体，而BP是白色片状物；OmnipolBP在固化膜中的迁移性远低于BP，气味也略低于BP。这是因为Omnipol BP分子量远高于BP 的缘故。由于Omnipol 是液体，在活性稀释剂中的溶解度明显好于 BP(表4-13)。  \n\n表4-13 两种BP在不同活性稀释剂中溶解度 $(20\\%$ > 单位： $\\mathbf{g}/100\\mathbf{g}$   \n\n\n<html><body><table><tr><td>光引发剂</td><td>HDDA</td><td>TPGDA</td><td>TMPTA</td></tr><tr><td>BP</td><td>40</td><td>37</td><td>30</td></tr><tr><td>OmnipolBP</td><td>>100</td><td>>100</td><td>>100</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 130,
+        "chunk": "# 4.5.3大分子硫杂葱酮光引发剂OmnipolTX  \n\n![](images/7657016181a914b57604f808927046cbe8cae2d08b384dad87abfd25bda592b1.jpg)  \n\n这也是一种夺氢型双官能度大分子自由基光引发剂， $\\lambda_{\\operatorname*{max}}$ 在 $395\\mathrm{nm}$ 处，吸收可延伸至$430\\mathrm{nm}$ 。它的光引发活性（等物质的量添加时）比ITX稍低，颜色也比ITX更黄，为深黄色黏稠液体；但它在固化膜中的迁移性远低于ITX，而且气味也特别低，这也是因为Om-nipol TX分子量远远高于ITTX 的缘故。加之Omnipol TX是液体，与低聚物相容性好，在活性稀释剂中溶解度也明显好于ITX(表4-14)  \n\n表4-14ITX型光引发剂在不同活性稀释剂中溶解度 $(20^{\\circ}\\mathsf{C}$ > 单位： $\\pmb{\\mathrm{g}}/100\\mathbf{\\mathrm{g}}$   \n\n\n<html><body><table><tr><td>光引发剂</td><td>HDDA</td><td>TPGDA</td><td>TMPTA</td></tr><tr><td>ITX</td><td>25</td><td>16</td><td>15</td></tr><tr><td>Omnipol TX</td><td>>100</td><td>>100</td><td>>100</td></tr></table></body></html>  \n\n2005年欧洲发生了在雀巢奶粉中检测出微量ITX，引起世人震惊，分析其原因是雀巢奶粉包装材料中UV油墨所含的光引发剂ITX残留因迁移而造成对奶粉的污染。现改用大分子TX后，此弊病得到解决。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 131,
+        "chunk": "# 4.5.4大分子氨基苯乙酮光引发剂Polymeric910  \n\n![](images/45987a7b18081905be467909ccecae0809b59ad0fb47123d725db3d071a88ff8.jpg)  \n\n这是一种裂解型双官解度大分子自由基光引发剂， $\\Omega_{\\mathrm{max}}$ 在 $240\\mathrm{nm}$ 、 $330\\mathrm{nm}$ 处，以等物质的量加人配方中，Polymeric910在光引发活性、黄变性、迁移性、气味等与369相当（表4-15)。但Polymeric910在活性稀释剂中的溶解性明显高于369（表4-16)。  \n\n表4-15Polymeric910与369性能比较  \n\n\n<html><body><table><tr><td rowspan=\"2\">光引发剂</td><td rowspan=\"2\">黄变指数</td><td rowspan=\"2\">固化膜硬度</td><td colspan=\"2\">迁移性</td><td rowspan=\"2\">固化膜气味</td></tr><tr><td>水</td><td>3%的乙酸水溶液</td></tr><tr><td>Polymeric 910</td><td>1.05</td><td>0.620</td><td>未检出</td><td>未检出</td><td>2</td></tr><tr><td>369</td><td>1.05</td><td>0.624</td><td>未检出</td><td>未检出</td><td>2</td></tr></table></body></html>  \n\n表4-16光引发剂在不同活性稀释剂中溶解度（ $20\\%$ D 单位： $\\mathbf{g}/100\\mathbf{g}$   \n\n\n<html><body><table><tr><td>光引发剂</td><td>HDDA</td><td>TPGDA</td><td>TMPTA</td><td>Eo-TMPTA</td><td>PEA</td></tr><tr><td>369</td><td>10</td><td>6</td><td>5</td><td>5</td><td>15</td></tr><tr><td>Polymeric 910</td><td>>100</td><td>>100</td><td>>100</td><td>>100</td><td>>100</td></tr></table></body></html>  \n\n所以Polymeric910非常适用于UV有色体系中，特别是UV胶印油墨。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 132,
+        "chunk": "# 4.5.5大分子 $\\pmb{\\alpha}.$ -羟基酮光引发剂Irgacure127  \n\n![](images/a6473b6f3fcb150cecf593b01fa182d93d3e48dc7697bf7c1222638a71e4059c.jpg)  \n\n这也是一种裂解型双官能度大分子自由基光引发剂，又称双1173，已于2004年6月上市。Irgacure127光引发剂活性与1173、184相当；对氧敏感性较低，表面固化效果较好，适用于低黏度、薄涂层UV涂料。由于分子量大，挥发性低，自身气味及光解产物气味较低，特别适用于对气味要求低的UV清漆。与379、819等光引发剂组合使用，能获得出色的光引发活性，可用于UV油墨和UV喷墨油墨。 乐",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 133,
+        "chunk": "# 4.5.6大分子苯甲酰甲酸酯光引发剂Irgacure754  \n\n![](images/63c6e8a8fb34051d760d4ec797ce5a7e6fd57d836abaf0cca1b3d8ad4a218011.jpg)  \n\n这也是一种裂解型双官能度大分子自由基光引发剂，为液态光引发剂，光引发活性与1173相当或稍低；具有低挥发、低气味、低黄变和低迁移的特点，因此可作为低气味UV清漆配方的首选光引发剂。同时，Irgacure754也适用于水性UV固化体系。  \n\n![](images/2f805cc406de5f47325911a70a05bec7bb2aeed194909de4078642149752dc5a.jpg)  \n\n剂，主要用于UV粉末涂料体系。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 134,
+        "chunk": "# 4.5.7大分子酮酯光引发剂IrgacureOXE01  \n\n![](images/8bcd355bd2433c04ceccea44f156f4c0547a146ead689bf65a73663b04e1278c.jpg)  \n\nIrgacureOXE01对365nm波长光感度较高，耐黄变性较好，适用于有色体系光固化材料，还可用于难固化的黑色颜料体系；并可利用其对热不稳定性，用于光固化后需要后烘的加工工艺。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 135,
+        "chunk": "# 4.5.8大分子酰基麟化氧光引发剂  \n\n![](images/a11364b436c977a59d7d7090688039d9e32ee6f5f23925499886b797c35434a1.jpg)  \n\n该双官能度大分子酰基麟化氧光引发剂具有高光引发活性和非黄变性，紫外吸收可达230～450nm；与芳香酮类光引发剂混合使用，可产生协同作用，因此性能优于TPO。主要用于光固化速率快的UV表面涂料、印刷油墨和胶黏剂，也可用于可见光牙科材料固化。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 136,
+        "chunk": "# 4.5.9大分子胺烷基酮光引发剂Rad-StartN-1414  \n\n![](images/80153c65a881b476941982f17ecdd4e32bf8e3c1ba194ba4a9036abe72162b8a.jpg)  \n\nRad StartN-1414是裂解型双官能度大分子自由基光引发剂，光引发活性高，与TPO相当，而且对氧敏感性低；辐照后黄变程度高于TPO，但好于369；ITX对其敏化作用小，远不如907/ITX组合。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 137,
+        "chunk": "# 4.5.10 大分子阳离子光引发剂  \n\n（1）大分子碘盐光引发剂CD-1012  \n\n![](images/43e5604800ae71ed40b06241c077b346940b04796120a151d2c1e57f5a23d557.jpg)  \n\n大分子碘盐CD-1012是阳离子光引发剂，与低聚物相容性好，而且水解稳定性也好。（2）大分子硫盐光引发剂Uvacure1590  \n\n![](images/fd05894eba49075d11ede543dde9de456703998d9f2a056d87f37cf3ac733129.jpg)  \nUvacure 1590  \n\nUvacure1590是一个双官能度大分子阳离子硫盐光引发剂，光引发效率很高，有良好的热稳定性和溶解度。  \n\n（3）大分子硫盐光引发剂Esacure1187  \n\n![](images/d69b101936066a2182690f3a352c30e7846737f1845e7b29cbc9de92bb4bf3a6.jpg)  \n\n大分子阳离子硫盐光引发剂巧妙地把盐硫原子设计在噻葱环内，因此其光解产物中没有难闻的硫醚产生。  \n\n![](images/a004b45521f0ad3f4fab87f2abfa53365360430b7de0a59e3784fc8fe426de6d.jpg)  \n\n虽然Esacure1187光引发活性比阳离子光引发剂三苯基硫六氟磷酸盐低，但与碘盐相差不大；通过与葱类光引发剂复合使用，可弥补与三苯基硫盐的活性差距。但Es-acurell87与低聚物相容性好，可减少溶剂碳酸异丙酯的用量。而且使用Esacure1187不发生黄变，不释放难闻的气味，光分解产物无对人体有害的影响，也无迁移现象发生。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 138,
+        "chunk": "# 4.5.11 可聚合光引发剂  \n\n可聚合光引发剂通常在小分子光引发剂上引人不饱和基团（乙烯基、丙烯酰氧基、甲基丙烯酰氧基)，或由a-羟基酮类光引发剂（1173、184、2959等）与含—NCO、环氧基的单体反应制得。可聚合光引发剂既具有光引发基团起光引发作用，又具有可聚合的不饱和基团，在光固化中参加聚合交联反应，因此不易发生光固化后残留光引发剂以及迁移问题。已商品化的可聚合光引发剂EbecrylP36，它是在二苯甲酮苯环对位接上丙烯酸酯基团；Quan-tacure ABQ是在二苯甲酮苯环对位甲氨基上接上丙烯酸酯基团。  \n\n![](images/f4fbebd18c726fe3c47a99d47d58a866cdf551a644224cccc59e84bbfb61be92.jpg)  \n\n此外用苯乙烯与苯甲酰氯经付克反应能制得可聚合的二苯甲酮光引发剂。  \n\n![](images/e74e236c05ac7c939aaadbc39e0961c8bd9ab2e844243440ce9b68f01b99b166.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 139,
+        "chunk": "# 4.5.12 大分子助引发剂PPA  \n\n![](images/6a339111460e926bca10c3d2d54f524f75b05a6220a2ee43c461abea9db984e5.jpg)  \n\nPPA  \n\nPPA是一种双官能度的哌嗪基苯乙酮引发剂，为无味的浅黄色液体，在 $\\lambda{=}332\\ \\mathrm{nm}$ 处有较强吸收，能增强或拓宽夺氢型光引发剂的紫外线吸收，提供更高效的固化性能。  \n\nPPA 有很好的溶解性，与大多数活性稀释剂和低聚物是互溶的；能与多种光引发剂配合使用，具有很高的活性；在固化过程中没有有害的副产物，也没有迁移。PPA不仅适用于UV清漆，也适用于UV有色体系和厚涂层固化。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 140,
+        "chunk": "# 4.5.13含夺氢型和裂解型双引发基的混杂光引发剂  \n\n将夺氢型光引发基团和裂解型光引发基团组合在同一个分子中，可形成双引发基的混杂光引发剂，已商品化的有Esacure 1001。  \n\n![](images/ad22e130430a410ad65c93e0d02d489c280c8af548404e6c0f5966afabe2dcaa.jpg)  \n\n其光裂解过程为：  \n\n![](images/4f7b435edff17c112e41dffa907fe557c5fa2944508458436db80bc82252a703.jpg)  \n\n由于有二苯甲酮结构，也可发生夺氢反应。Esacure1001光分解后，分解产物无气味，而且毒性低。其 $\\lambda_{\\operatorname*{max}}$ 为 $316\\mathrm{nm}$ ，在 $370\\mathrm{nm}$ 处摩尔消光系数达到 $1000\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{cm})$ ，因此可用于UV油墨和UV色漆中。  \n\n此外还有将二苯甲酮与 $\\alpha$ 羟基酮、硫杂葱酮与 $\\alpha$ -羟基酮设计在一个分子中的双引发基的混杂光引发剂。  \n\n![](images/7830d266d10191b8b79867e60b498a7c7641a8d379a6d35b5512846c6b3102c8.jpg)  \n\n水性光固化涂料和油墨是光固化产品最新发展的一个领域，它是用水作为稀释剂，代替活性稀释剂来稀释低聚物调节黏度，没有活性稀释剂的皮肤刺激性和臭味，价廉，不燃不爆，又安全。水性光固化涂料和油墨是由水性低聚物和水性光引发剂组成，它要求水性光引发剂在水性低聚物中相容性好，在水介质中光活性高，引发效率高，以及其他光引发剂要求的低挥发性、无毒、无味、无色等。水性光引发剂可分为水分散型和水溶性两大类，目前常规光固化涂料和油墨所用光引发剂大多为油溶性的，在水中不溶或溶解度很小，不适用于水性光固化涂料和油墨，所以近年来水性光引发剂的研究和开发已成为热门课题，并取得了可喜的进展。不少水性光引发剂是在原来油溶性光引发剂结构中引人阴离子、阳离子或亲水性的非离子基，使其变成水溶性。已经商品化的水性光引发剂有KIPEM、819DW、BTC、BPQ和QTX等。  \n\nKIPEM是高分子型光引发剂KIP150稳定的水乳液，含有 $32\\%$ 的KIP150， $\\lambda_{\\operatorname*{max}}$ 在$245\\mathrm{nm}$ ， $325\\mathrm{nm}$ 处。  \n\n819DW是光引发剂819稳定的水乳液， $\\lambda_{\\operatorname*{max}}$ 在 $370\\mathrm{nm}$ 、 $405\\mathrm{nm}$ 处。  \n\nQTX为2-羟基-3-( $2^{\\prime}$ -硫杂葱酮氧基) ${\\bf\\nabla}\\cdot{\\bf N}$ ，N，N-三甲基-1-丙胺氯化物，黄色固体，熔点$245\\sim246^{\\circ}C$ ，为水溶性光引发剂， $\\lambda_{\\operatorname*{max}}$ 为 $405\\mathrm{nm}$ 。BTC、BPQ都是水溶性的二苯甲酮衍生物季铵盐。  \n\n![](images/b36860da218e5d1f4824893ef530526c0948a36853fb8c1f4759641d309a12cc.jpg)  \n\n另外，光引发剂2959 由于在1173苯环对位引人了羟基乙氧基（ $\\mathrm{HOCH}_{2}\\mathrm{CH}_{2}$ 一）使其在水中溶解度从 $0.1\\%$ 提高 $1.7\\%$ ，因此也常用在水性光固化涂料中。  \n\n以上介绍的大多数光引发剂都是紫外光引发剂，它们对紫外光（主要指 $300\\sim400\\mathrm{nm})$ ，特别是紫外光源 $365\\mathrm{nm}$ 敏感，吸收光能后光解产生自由基或阳离子引发聚合；对可见光几乎无响应，便于生产、应用和贮运。但随着信息技术、计算机技术、激光技术和成像技术的发展，不少光信息记录材料需要采用可见光和红外光波段，进行光化学反应，为此可见光引发剂的研究也引起人们的重视，目前已经商品化的有樟脑和钛茂可见光引发剂。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 141,
+        "chunk": "# 4. 7.1 樟脑  \n\n樟脑（camentholquinone，CQ）， $\\lambda_{\\operatorname*{max}}$ 在 $470\\mathrm{nm}$ 处，为可见光引发剂。CQ吸收光能后，在激发三线态与助引发剂叔胺作用，夺氢后产生游基自由基和引发剂活性很高的胺烷基自由基，引发聚合。  \n\n![](images/c45ce595ded5335f63829fa9715ec1ec8a016759179004cec72814b567a183ec.jpg)  \n\n樟脑由于对人体无毒害，生物相容性好，光解反应后其长波吸光性能消失，具有光漂白作用，因此非常适合在光固化牙科材料上应用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 142,
+        "chunk": "# 4.7. 2 钛茂  \n\n很多金属有机化合物具有光聚合引发活性，如过渡金属乙酰丙酮络合物、8-羟基喹啉络合物、多羰基络合物等，由于引发效率不高，热稳定性差，毒性也较大，没有实用意义。  \n\n氟代二苯基钛茂具有良好的光活性、热稳定性和较低的毒性，可作为光引发剂使用，并商品化。  \n\n![](images/cd47336676e93410a96d64561504d502ecfad5230ec50a37a2fb805cdbc6c219.jpg)  \n\n双［2,6-二氟-3-(1H-吡咯基-1）苯基］钛茂，商品名Irgacure 784，简称784。784为橙色粉末，熔点 $160{\\sim}170^{\\circ}\\mathrm{C}$ ； $\\lambda_{\\operatorname*{max}}$ 在 $398\\mathrm{nm}$ 、 $470\\mathrm{nm}$ 处，最大吸收波长可达 $560\\mathbf{nm}$ 。784与氩离子激光器 $488\\mathrm{nm}$ 发射波长匹配，是很好的可见光引发剂。氟代二苯基钛茂784光引发剂的光引发过程既不属于裂解型，也不属于夺氢型，而是784吸收光能后，光致异构变为环戊基光反应中间体（A)，与低聚物和活性稀释剂中丙烯酸酯的酯基发生配体置换，产生自由基（B）引发聚合和交联。  \n\n![](images/dbeb0bbe2186023fd7a71d75850fbc9d9dc71e440f17ac9e10e9078d6e5c0673.jpg)  \n\n784在可见光处吸收良好，光解后有漂白作用，非常适合于厚涂层的可见光固化，可固化 $70\\mu\\mathrm{m}$ 以上厚度的涂层。热分解温度 $230^{\\circ}\\mathrm{C}$ ，可在醋酸或氢氧化钠溶液中煮沸几个小时不发生变化，有极好的热稳定性。784的感光灵敏度和光引发活性都很高，在丙烯酸酯体系中，只需 $0.8\\mathrm{mJ}/\\mathrm{cm}^{2}$ 的 $488\\mathrm{nm}$ 光照就可引发聚合； $0.3\\%$ 的784的光引发效率比 $2\\%$ 的651高 $\\scriptstyle2\\sim6$ 倍。但因在UV光区摩尔消光系数太大，光屏蔽作用强，只能用于薄涂层固化。784主要用于高技术含量和高附加值领域，如氩离子激光扫描固化、全息激光成像、聚酰亚胺光固化以及光固化牙科材料中。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 143,
+        "chunk": "# 4.7.3硫代叮啶酮/碘盐体系  \n\n由于叮啶酮分子结构中同时具有二苯甲酮及三级胺结构，因此具有较好的光敏性，引起人们重视，但其不具备可见光吸收。而硫代叮啶酮，其硫取代了氧，由炭基变成了硫代基，由于硫的电负性小于氧，打开碳硫双键产生电子跃迁所需的能量比碳氧双键低，因而它的光谱吸收向长波方向移动，成为对可见光敏感的引发剂。  \n\n![](images/1a10fda7d88bad15b31b1dd737482d35cca492c3b0c61601c687444aa039723f.jpg)  \n叮啶酮  \n\n![](images/ee38342da264add16848afa075930c487ecf1e3daf7ac0b4d59655f1d8bf2730.jpg)  \n硫代叮啶酮  \n\n将硫代叮啶酮的长波长吸光特性与二苯基碘盐的高化学反应活性相结合，组成一种在可见光区域内具有较高引发效率的光敏体系。  \n\n同时加人活性剂如硫代水杨酸等供氢体，能更有效地提高光敏体系的光引发效率，实验结果见表4-17。  \n\n表4-17不同结构硫代叮啶酮的吸收光谱和感光性能  \n\n\n<html><body><table><tr><td rowspan=\"3\">名称</td><td rowspan=\"3\">Amax /nm</td><td rowspan=\"3\">Erax /CL/(mol·cm)]</td><td colspan=\"2\">曝光时间(留膜级数)</td></tr><tr><td>12min</td><td>18min</td></tr><tr><td></td><td></td></tr><tr><td>N-丁基硫代叮啶酮</td><td>490</td><td>2.6×104</td><td>g</td><td></td></tr><tr><td>N-丙基硫代叮啶酮</td><td>490</td><td>2.8X10</td><td>7</td><td></td></tr><tr><td>N-苄基硫代叮啶酮</td><td>485</td><td>2.3×10</td><td>6</td><td></td></tr><tr><td>N-苯基硫代叮啶酮</td><td>483</td><td>2.3×104</td><td>8</td><td></td></tr><tr><td>4-甲基硫代叮啶酮</td><td>478</td><td>5.7×103</td><td>4</td><td>7</td></tr><tr><td>N-正丙基-4-甲基硫代叮啶酮</td><td>478</td><td>1.5×10*</td><td>5</td><td>7</td></tr><tr><td>4-甲氧基硫代叮啶酮</td><td>478</td><td>5.6X103</td><td>3</td><td>6</td></tr><tr><td>N-正丙基-4-甲氧基硫代叮啶酮</td><td>478</td><td>5.6X103</td><td>0</td><td>7</td></tr><tr><td>4-氯硫代叮啶酮</td><td>478</td><td>3.6X103</td><td>0</td><td>6</td></tr><tr><td>N-正丙基-4-氯硫代叮啶酮</td><td>481</td><td>5.3×10²</td><td></td><td>5</td></tr></table></body></html>\n\n① 苯乙烯-马来酐共聚物5份，EA5份，PETA10份，硫代叮啶酮1份，二苯基碘盐1份，硫代水杨酸1份。$\\textcircled{2}$ 留膜级数越高，表示体系感度越好。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 144,
+        "chunk": "# 4.7.4有机过氧化物体系  \n\n有机过氧化物中，过氧键（—O—O—）的离解能为125～210kJ/mol。这类化合物对紫外光有强烈的吸收，通过引入新基团或进行光谱增感即可成为可见光引发剂：  \n\n![](images/7970b0df71aae31d33c753f13899c914c0682f8213b6aba3e2dc2427e36fdf12.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 145,
+        "chunk": "# 4.7.5硼酸盐/染料体系  \n\n由阳离子染料与四烃基硼（三芳基-烷基硼或二芳基-二烷基硼）的碱金属盐形成的离子型络合物，作为可见光引发剂，对引发丙烯酸系单体的光聚合特别有效，最常用的有机硼为丁基三苯基硼酸盐。光照时，电子由硼酸盐向激发态染料转移，硼酸盐离子活化氧化产生的自由基裂解成三苯基硼酸盐和丁基自由基，丁基自由基引发光聚合反应。  \n\n$$\n\\begin{array}{r}{\\begin{array}{c}{+}\\\\ {\\mathrm{Dye~}+\\mathrm{C_{4}H_{9}B^{-}(C_{6}H_{5})_{3}\\xrightarrow{h\\nu}~D y e~}+[\\mathrm{C_{4}H_{9}B(C_{6}H_{5})_{3}}]\\tilde{\\cdot}}\\\\ {\\downarrow}\\\\ {\\cdot\\mathrm{C_{4}H_{9}}+\\mathrm{B(C_{6}H_{5})_{3}}}\\end{array}}\\end{array}\n$$  \n\n有机硼/染料体系可见光引发剂见表4-18。  \n\n表4-18有机硼/染料体系可见光引发剂  \n\n\n<html><body><table><tr><td>染料阳离子</td><td>有机硼阴离子</td><td>Amax/nm</td></tr><tr><td>CH- CH CH15 CH15</td><td>(CH5）B-CHg</td><td>568</td></tr><tr><td>0 CH—CH—CH- CH1a CH1a</td><td>(CH5)3B-CHg</td><td>492</td></tr><tr><td>0 CH—CH—CH CHs CH5</td><td>（HC- B-CHg</td><td>590</td></tr><tr><td>HC CH3 H3C CH3 CH-CH—CH C(CH)3 C(CH)3</td><td>(CH5)3B-C4Hg</td><td>640</td></tr><tr><td>HC HC CH3 CH-CH- CH C4H CHg CH3</td><td>(CH5)3B-CHg</td><td>550</td></tr><tr><td>COOCH (H5C）2N N(CH5)2</td><td>(CHs）8B-CHg</td><td>633</td></tr><tr><td>(H5C）2N -N(CH5)2 C CH- (H5C）2N N(CH5)2</td><td>(CgH5)2B-(CHg)2</td><td>633</td></tr><tr><td>(HsC）2N- N(CHs)2 (H5C)2N-</td><td>(CgHs）2B-(CHg）2</td><td>633</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 146,
+        "chunk": "# 4.7.6六芳基双咪唑/染料体系  \n\n六芳基双咪唑/染料体系（hexarylbiimidazole，HABI'S）在自由基光成像体系中作引发剂，是一种热致和光致变色化合物。在光和热的作用下，它裂解为一对带色的三芳基咪唑自由基L，但三芳基咪唑自由基中三个苯环位阻较大，使活性减小，从而影响引发效率。但是电子给体通过电子转移，易使L产生引发聚合反应的自由基；L也很容易与氢给体通过直接提氢或电子转移产生自由基。  \n\n$$\n{\\cal L}_{2}\\stackrel{h v}{\\longrightarrow}2L\\cdot\\quad\\quad{\\cal L}\\cdot+\\mathrm{RH}\\longrightarrow\\mathrm{LH}+\\mathrm{R}\\cdot\n$$  \n\nHABI'S的吸收光谱为 $\\lambda_{\\mathrm{max}}=255\\sim275\\mathrm{nm}$ ，它与适当的染料增感剂配合使用，可使吸收  \n\n光谱延伸到可见光区，可在氩离子激光（488nm)、氪离子激光（568nm）、氮氛激光$(632.8\\mathrm{nm})$ ）下感光成像。  \n\n表4-19介绍了部分六芳基双咪唑/染料可见光引发体系。  \n\n![](images/a9368b8c336ddb61e24f8860dff9ad8baac9132da230581066d81f586cb78c94.jpg)  \n2,3，5-三芳基咪唑二聚体（HABI'S）  \n\n表4-19六芳基双咪唑/染料可见光引发体系  \n\n\n<html><body><table><tr><td>染 料</td><td>Amax/nm</td></tr><tr><td>0 CH</td><td>452</td></tr><tr><td>H5C 0 CH5 N CH CH- HsC2 CH HC CH5 0</td><td>481</td></tr><tr><td>HC CH5 CH- N CH5 CH3 HC</td><td>443</td></tr><tr><td>CH- CH CH3 0</td><td>450</td></tr><tr><td>CH CH HC CH3 0 CH3 H3C</td><td>496</td></tr><tr><td>CH- CH- CH- CH CH3 CH3 0</td><td>520</td></tr><tr><td>CH-CH- CH- CH- CHs CH5</td><td>556</td></tr><tr><td>0 CH- CH- H CH5 CH5 CH</td><td>582</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 147,
+        "chunk": "# 4.7.7香豆素酮类/染料体系  \n\n香豆素酮类染料对He-Cd激光（ $\\cdot441.6\\mathbf{nm},$ ）敏感，在氩离子激光（ $488\\mathbf{nm}$ ， $514\\mathrm{nm}^{\\cdot}$ ）光照下，是光交联和光聚合的高效引发剂。香豆素酮类染料（KC）与活化剂或共引发剂一起使用，其引发机理为：  \n\n![](images/2118bdd8bac47baf80c0ee013c989b2738f0dd7cc5338942e6789e63461c8996.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 148,
+        "chunk": "# 香豆素酮与活化剂光引发体系见表4-20。  \n\n表4-20香豆素酮/活化剂光引发体系引发效率  \n\n\n<html><body><table><tr><td>活化剂</td><td>香豆素酮染料</td><td>X</td><td>相对光引发量子效率</td></tr><tr><td rowspan=\"7\">(HC)2N- COOC2H5 HCO</td><td rowspan=\"3\">OR O=</td><td>CN</td><td>3.8</td></tr><tr><td>H</td><td>3.0</td></tr><tr><td>OCH3</td><td>2.7</td></tr><tr><td>RO OR o- OR RO 00 OR</td><td></td><td>2.0</td></tr><tr><td>0 (H5C)2N 0</td><td></td><td>1.6</td></tr><tr><td rowspan=\"2\">OR Oi OCH2COOH</td><td>CN</td><td>2.3</td></tr><tr><td>H</td><td>1.7</td></tr><tr><td rowspan=\"2\">RO RO NHCHCOOH</td><td>0 X OR O1</td><td>OCH3 1.5</td></tr><tr><td></td><td>3~4 2~4</td></tr><tr><td>OCH3BF</td><td>RN 0 OR 0 (HC）2N</td><td></td><td>1.5~2.0</td></tr></table></body></html>\n\n$\\textcircled{1}$ 量子效率是相对于米酮/二苯甲酮引发体系的量子效率为1比较。  \n\n近年来研究发现电子给体单体和电子受体单体结合，在无光引发剂存在下，经紫外光照可直接光引发共聚合，完成光固化过程。其中电子受体单体有马来酸酐、富马酸二甲酯、马来酰亚胺等；电子给体单体有N-乙烯基吡咯烷酮、苯乙烯基醚和丙烯基醚等，如图4-1所示。  \n\n![](images/3446cb7e1ccb00472c495caba16ff4678408fd59c321e73132ac48959dab4738.jpg)  \n图4-1电子受体和电子给体单体的化学结构  \n\n同时还发现由双基化合物（如乙酰乙酸乙酯）与丙烯酸酯多官能单体或低聚物反应得到的含季酮结构的丙烯酸低聚物，在紫外光照下，不需加光引发剂就能直接光固化，此类含季酮结构的丙烯酸低聚物如下所示。  \n\n![](images/f01d4004f3427312d085be800cf7d9197623f6d37d791ec0549e7df717ba6ca4.jpg)  \n\n这两类无光引发剂体系，紫外光直接作用于马来酰亚胺或含酮结构的丙烯酸低聚物产生自由基，引发体系中活性稀释剂和低聚物聚合。这里马来酰亚胺或含季酮的丙烯酸低聚物实际上既起光引发剂的作用，又起可聚合的活性稀释剂或低聚物的作用。其光引发机理目前有如下几种。  \n\n（1）直接提氢机理在乙烯基醚、胺、硫醇可给氢的化合物存在下，马来酰亚胺的激发三线态可直接提取氢产生两个可引发聚合的自由基，类似于二苯甲酮的光引发机理，如图4-2所示。  \n\n![](images/4d3dff7fbacef43567a3788ac6b1b1c41259c1fd10f00d11afda27978e6c939b.jpg)  \n图4-2直接提氢机理  \n\n（2）电子和质子转移处理在乙烯基醚电子给体存在下，激发三线态的马来酰亚胺能有效地接受给体转移的电子，生成阳离子自由基/阴离子自由基，然后阳离子自由基中的氢质子转移给阴离子自由基马来酰亚胺，生成两个可引发聚合的自由基，如图4-3所示。  \n\n![](images/4feadec60cdb8d0590fb5c10c8af82e81e08c022d13f358926745ff73e8fb347.jpg)  \n图4-3电子和质子转移机理  \n\n（3）电荷转移机理电子给体单体和电子受体单体通过电荷转移，生成激发复合物，再进行电子重排形成双自由基或阴阳离子对，引发聚合。而激发复合物可以通过两种途径生成：  \n\n$\\textcircled{1}$ 电子给体单体和电子受体单体在基态生成络合物，经紫外光照变成激发复合物；  \n\n$\\textcircled{2}$ 电子受体单体经紫外光照吸收光能跃迁到激发态，再与基态的电子给体单体生成激发复合物，如图4-4所示。  \n\n![](images/efa74bd8625a7e15b25d9a6ef4677c716de710215896709acacaa5610d647fae.jpg)  \n图4-4电荷转移机理  \n\n（4）含季酮结构的丙烯酸低聚物的光固化机理含季酮结构的丙烯低聚物中，酮基碳和邻位的季碳原子之间的键是很弱的，在紫外光的直接作用下，很容易发生裂解生成酰基自由基，引发聚合，如图4-5所示。  \n\n![](images/b6b674cc6a5a06afd644cf9ee5b8843895c97f496c01365bd91b857c17465edc.jpg)  \n图4-5季酮结构丙烯酸酯的光固化机理  \n\n无光引发剂体系为光固化技术开拓了一个新的领域，由于不用或少用光引发剂，避免和减少了用光引发剂带来的病：光分解产物的气味和毒性，残留的光引发剂的迁移，引起涂后的黄变和老化等。同时在无光引发剂体系的光固化过程中，氧的阻聚作用较小；光引发机理中发生提氢过程，对提高涂层与基材之间附着力非常有利；光引发机理中还有光漂白功能，可解决深层固化和复合材料的有效固化问题。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 149,
+        "chunk": "# 4.9光引发剂的合成方法  \n\n（1）苯偶姻（安息香）的合成  \n\n![](images/77e77ac5cc0120ec1b3250edb6179d9453cabad6cc4b8d2e9e61f3fdb73ab7a3.jpg)  \n\n在装有 $\\pmb{200}\\mathbf{g}$ 、 $50\\%$ 的乙醇的三口烧瓶中加人 $_{197g}$ 苯甲醛、 $_{40\\mathbf{g}}$ 四乙基溴化铵和 $80\\mathbf{g}$ 氰化钠，升温至 $90\\mathrm{^\\circC}$ ，回流搅拌2h。冷却过滤，得淡黄色结晶，用乙醇重结晶得产品 $184\\mathbf{g}$ .熔点 $134{\\sim}135\\mathrm{^\\circC}$ ，收率 $92\\%$ (过滤母液含剧毒氰化钠，必须用氯气在碱性条件下处理)。  \n\n（2）苯偶姻（安息香）的超声辐射合成  \n\n![](images/03461136d2e891d51c0d2758fd78b6ab31854a6f75550b542fdd969e4a5748c0.jpg)  \n\n将 $\\mathsf{50m m o l}$ 新蒸苯甲醛、 $12\\mathrm{mmol}$ 氰化钠、 $12.5\\mathrm{mL}95\\%$ 的乙醇和 $0.8\\mathrm{mol}$ 氢氧化钠$(5\\%)$ 加入 $100\\mathrm{mL}$ 锥形瓶中，置于超声波清洗器中超声辐射3h（保持水温 $25{\\sim}35^{\\circ}\\mathrm{C}^{\\prime}$ ，反应液颜色逐渐变黄，并有淡黄色沉淀析出，用薄层色谱跟踪直至芳醛的斑点消失。冷却后抽滤，用乙醇重结晶得到产物苯偶姻，产率 $85\\%$ 。  \n\n（3）苯偶酰（联苯甲酰）的合成（一)  \n\n![](images/2e290cef5d4e886215381c86d0492c574256207da42a84833a380a982b258999.jpg)  \n\n在三口烧瓶中加人 ${\\displaystyle100{\\bf g}}$ 安息香、 $\\mathbf{250g}$ 冰醋酸和 $250\\mathbf{g}$ 浓硝酸，加热至 $85\\sim95^{\\circ}\\mathrm{C}$ ，回流4h，冷却，过滤，用甲醇重结晶得黄色结晶 $132\\mathbf{g}$ ，熔点 $94{\\sim}95\\mathrm{^\\circC}$ ，收率 $97\\%$ 。  \n\n（4）苯偶酰（联苯甲酰）的合成（二)  \n\n![](images/42a3ed4dcbb249f2f8ec9da6a5c8ba05d2a956033d7de05cc6b2b7bb84a0a078.jpg)  \n\n由二苯基乙炔，在氧化剂氧化下，直接反应合成苯偶酰(表4-21)。  \n\n表4-21用二苯基乙炔合成苯偶酰的工艺  \n\n\n<html><body><table><tr><td>氧化剂</td><td>溶剂</td><td>反应时间/min</td><td>反应温度/℃</td><td>产率/%</td></tr><tr><td>ZnCr2O,</td><td>CCl4</td><td>480</td><td>室温</td><td>50</td></tr><tr><td>Zn(MnO)2</td><td>CHCl2</td><td>45</td><td>40</td><td>67</td></tr><tr><td>NaOAc/HOAc/ACO</td><td></td><td>360</td><td>60</td><td>81</td></tr><tr><td>cis-[LRuO(CFCOO)]+</td><td>乙腈</td><td>几分钟</td><td></td><td>60</td></tr><tr><td>[(CFCOO)IPh]2O</td><td>CHCIs</td><td>1080</td><td>室温</td><td>94</td></tr><tr><td>Co-Mn-Br</td><td>水</td><td>180</td><td>109</td><td>90</td></tr></table></body></html>  \n\n(5）苯偶酰(联苯甲酰）的合成（三)  \n\n![](images/04b71de1d75cca697b2b793e4869220649fb18e46a3b631a33724cb927e2950e.jpg)  \n\n用苯偶姻，在氧化剂氧化下直接反应合成苯偶酰（表4-22)。  \n\n表4-22用苯偶姻合成苯偶酰的工艺  \n\n\n<html><body><table><tr><td>氧化剂</td><td>溶剂</td><td>反应时间/min</td><td>反应温度/℃</td><td>产率/%</td></tr><tr><td>HNO3</td><td>水</td><td>300</td><td>室温～110</td><td>95</td></tr><tr><td>CuSO</td><td>吡啶/水</td><td>120</td><td>沸腾</td><td>86</td></tr><tr><td>ZnCrO7</td><td>CHClz</td><td>120</td><td>室温</td><td>90</td></tr><tr><td>过氧化镍</td><td>苯</td><td>300</td><td>50</td><td>98.5</td></tr><tr><td>FeCl3</td><td>HOAc</td><td>45~60</td><td>沸腾</td><td>90~95</td></tr><tr><td>NHNO3/CuSO</td><td>HOAc</td><td>60~90</td><td>90</td><td>94</td></tr><tr><td>PhCHEt3 NBr3</td><td>CHCN</td><td>120</td><td>(PhCO)O催化剂</td><td>90</td></tr><tr><td>PhMe NBrg</td><td>THF</td><td>60</td><td></td><td>98</td></tr><tr><td>NBS</td><td>CCl4</td><td>50</td><td>(PhCO)2O2催化剂</td><td>97</td></tr><tr><td>NBS</td><td>CCl4</td><td>60</td><td></td><td>94</td></tr><tr><td>PhPBr2</td><td>CHCN</td><td>20</td><td></td><td>90</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 150,
+        "chunk": "# （6）安息香甲醚的合成  \n\n![](images/b63eade4bf67a6fbef9d134ff192fabb1c233445e5b28391f1ed87b39335a397.jpg)  \n\n在装有气体吸收装置的三口烧瓶中加人212g（1mol）安息香和320g（10mol）甲醇，升温至60～70°℃，慢慢滴加160g（1.4mol）二氯亚矾，加毕保温2h，至反应液澄清停止反应，减压蒸馏回收甲醇，浓缩液过滤后放置冷冻结晶，粗品经乙醇重结晶，得产物165g，凝固点 $31\\mathrm{{^{q}C}}$ ，产率 $73\\%$ 。  \n\n（7）安息香乙醚的合成  \n\n![](images/7141ab5ad2106d7889bbb2a7f94cdadd94f23872422255a54d6bfb14fda3a3b2.jpg)  \n\n在装有气体吸收装置的三口烧瓶中加入106g（0.5mol）安息香和115g（2.5mol）无水乙醇，升温至75～80℃，慢慢滴加72g（0.6mol）二氯亚矾，加毕保温1h，反应液澄清后停止反应，减压蒸馏回收乙醇，浓缩液放冷结晶，过滤得粗品 $115g$ ，熔点 $55\\sim57^{\\circ}\\mathrm{C}$ ，再重结晶精制得产品熔点 $60{\\overset{\\cdot}{\\sim}}62^{\\circ}\\mathrm{C}$ ，收率 $95\\%$ 以上。  \n\n（8）安息香异丙醚的合成  \n\n![](images/fb17093f8923f52b15f0c94ba203a240e51efbf79d5779d06636bde1e3dd9891.jpg)  \n\n在装有气体吸收装置的三口烧瓶中，加人106g（0.5mol）安息香、60g（lmol）异丙醇，升温至70～80℃，慢慢滴加72g（0.6mol）二氯亚矾，加毕保温1h，待反应液澄清后停止反应，减压蒸馏回收异丙醇，放置冷却，过滤得粗品，经重结晶后得成品120g，熔点$74{\\sim}76^{\\circ}\\mathrm{C}$ ，收率 $91\\%$ 。  \n\n（9）安息香双甲醚（651）的合成  \n\n$$\n\\textcircled{1}\\stackrel{\\mathrm{~0~0~}}{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{v}}}}}}}}\\stackrel{\\mathrm{~0~}}{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{d}}}}}}+2\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{EH}}}}}}}\\mathord{\\operatorname{\\operatorname{\\operatorname{\\operatorname{ov}}}}}\\mathord{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{van}}}}}}+\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\csc}}}}\\mathord{\\operatorname{\\operatorname{\\operatorname{cH}}}}_{3}\\operatorname{\\operatorname{\\operatorname{\\operatorname{SO}}}}_{4}\\longrightarrow\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{v}}}}}}}}\\stackrel{\\mathrm{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{v}}}}}}}}}}}{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{v}H}}}}}}}}}+\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{van}}}}}}}_{2}\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{vot}}}}}}}\\mathord{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{\\operatorname{vot}}}}}}}}\n$$  \n\n在装有带4A分子筛干燥管的三口烧瓶中加入联苯甲酰 $\\scriptstyle21_{\\mathbf{\\deltag}}$ 、硫酸二甲酯 $17.7{\\bf g}$ 、二氧六环 $80\\mathrm{mL}$ ，加热至 $39^{\\circ}\\mathrm{C}$ ，1h内分批加入 $7.8\\mathbf{g}$ 甲醇钠，加完后反应液呈黑色黏稠液体，然后加入5.6g氢氧化钠和100mL水，回流1h，冷却，分离出有机相（深黄色)，减压蒸馏蒸去溶剂，残余物倒人冷水中，析出黄色固体，水洗数次，晾干得微黄色固体 $_{13.5g}$ ，熔点$60{\\sim}62^{\\circ}\\mathrm{C}$ ，产率 $55\\%$ 。  \n\n（10）安香息双甲醚（651）的合成  \n\n![](images/c5f4537058ff86094f6d03eb5ba39e7436a35f89fbe059774b6b0f35ced9b984.jpg)  \n\n在装有气体吸收装置的三口烧瓶中，将 $840{\\bf g}$ 二苯甲酰悬浮于 $800\\mathrm{mL}$ 二氯亚矾中，搅拌下在 $0\\sim7\\ensuremath{\\mathrm{^circC}}$ 滴加 $800\\mathrm{mL}$ 甲醇，得清黄色溶液，半小时升温至 $50^{\\circ}\\mathrm{C}$ ，再反应 $\\pmb{2\\mathrm{h}}$ ，升温至$90^{\\circ}\\mathrm{C}$ ，用水泵减压蒸出亚硫酸二甲酯，冷却，加入 $100\\mathbf{g}$ 无水碳酸钾及 $1600\\mathrm{mL}$ 异丙醇，过滤，用50%的异丙醇水溶液重结晶，得白色结晶640g，熔点62～63℃，收率63%。  \n\n（11）一缩二乙二醇改性安息香双甲醚的合成  \n\n![](images/313de9082f37e799cab534f63782d9fe7ca59c2d38f5300050a47bdc5c37735d.jpg)  \n\n在三口烧瓶中加人1mol安息香双甲醚和lmol一缩二乙二醇及催化剂对甲苯磺酸（总量的2%)，升温至100℃反应5h，中和反应液，水洗至中性，干燥，得到一缩二乙二醇安息香双甲醚，可溶于 $80^{\\circ}\\mathrm{C}$ 的蒸馏水中（ $(0.1\\mathbf{g}/50\\mathbf{m}\\mathrm{L})$ 。  \n\n（12）三羟甲基丙烷改性安息香双甲醚的合成  \n\n![](images/849205180b415021e9ce549a5b42f1db9fadb8db7a99c6b9eaa5eb2c8182544c.jpg)  \n\n在三口烧瓶中加人1mol安息香双甲醚、4mol三羟甲基丙烷及催化剂对甲苯磺酸（总量的2%)，升温至100℃，溶解反应5h，中和反应液，水洗至中性，干燥得三羟甲基丙烷改性安息香双甲醚，可溶于 $80^{\\circ}\\mathrm{C}$ 的蒸馏水中！ $({0.18}/{50}\\mathrm{mL})$  \n\n（13）马来酸酐改性羟甲基安息香甲醚的合成  \n\n![](images/2bee72347752aa5c81cb9d9a4401b96da421ef346b0f139544a04aeeaa9ca776.jpg)  \n\n在三口烧瓶中加人128g羟甲基安息香甲醚、49g马来酸酐、200mL二氧六环和催化剂2mL三乙胺，搅拌升温，回流30min减压蒸馏除去溶剂，用热水洗两次，在烘箱中60℃干燥5h，得到淡黄色粉末 $168\\mathbf{g}$ ，为马来酸酐改性羟甲基安息香甲醚，产率 $95\\%$ ， $\\lambda_{\\operatorname*{max}}=$  \n\n$330\\mathrm{nm}$ ，在 $1\\%$ 的 $\\mathbf{NaOH}$ 中能分散。  \n\n（14）a-羟基酮光引发剂1173的合成（一)  \n\n![](images/619eb245557584a805943fe80aab9bed9e5239e7f45e472b45eca0d7baba72de.jpg)  \n\n在三口烧瓶中加人78g苯、140g无水氯化铝和250mL石油醚，置于冰水浴中，搅拌下缓慢滴加106g异丁酰氯，温度控制<25℃，反应4h，再滴加冰水，分液，有机层水洗至中性，干燥，减压蒸馏除去溶剂得A，收率93%。  \n\n在三口烧瓶中加入60gA、200mL石油醚和50mL氯化亚矾，反应6～8h，水洗至中性，收集有机层，干燥，减压蒸馏除去溶剂，得产物B，收率95%。  \n\n在三口烧瓶中加人74gB、240mL甲苯、48mL50%的氢氧化钠水溶液和1.6g四丁基溴化铵，反应5h后，加人80mL水，再反应0.5h，收集有机层，干燥，蒸去溶剂后，减压蒸馏收集50～100Pa时75～85℃的馏分，即光引发剂1173，产率75%。  \n\n（15）a-羟基酮光引发剂1173的合成（二)  \n\n$$\n\\begin{array}{r l}&{\\underbrace{0}_{\\begin{array}{c}{\\left[\\begin{array}{l}{0}\\\\ {\\left(\\mathbf{C}\\mathbf{H}_{3}\\right)_{2}\\mathbf{C}\\mathbf{H}\\mathbf{C}\\mathbf{C}\\mathbf{l}}\\end{array}\\right]}\\underbrace{\\mathrm{AlCl}_{3}}_{\\begin{array}{c}{\\left[\\begin{array}{l}{0}\\\\ {\\mathbf{C}\\mathbf{H}_{3}}\\end{array}\\right]}\\\\ {\\left[\\begin{array}{l}{0}\\\\ {\\mathbf{C}\\mathbf{H}_{3}}\\end{array}\\right]}\\\\ {\\left[\\begin{array}{l}{\\mathbf{l}_{1}^{\\mathrm{~[~]}}}\\\\ {\\mathbf{C}\\mathbf{C}_{\\mathbf{H}}^{\\mathrm{~C~H}}}\\\\ {\\mathbf{C}\\mathbf{H}_{3}}\\end{array}\\right]}\\underbrace{\\overbrace{\\left(\\mathbf{C}_{4}\\mathbf{H}\\mathbf{p}\\right)\\mathbf{N}\\mathbf{B}\\mathbf{r}}^{\\mathrm{~[~]}}}_{\\begin{array}{c}{\\left[\\begin{array}{l}{\\mathbf{C}-\\mathbf{C}\\mathbf{H}}\\\\ {\\mathbf{C}\\mathbf{H}_{3}}\\end{array}\\right]}\\\\ {\\mathbf{C}\\mathbf{H}_{3}}\\end{array}}}\\end{array}\\underbrace{,}}\\end{array}\n$$  \n\n在三口烧瓶中加人38g无水氯化铝和90g苯，置于冰水浴中，搅拌下慢慢滴加45g异丁酰氯，温度控制在0～25℃，直至无HCI气体放出。将反应液倒人冰水，用乙醚萃取，分离出有机层，减压蒸馏，收集5300Pa下86℃的馏分，即为A，产率55%。  \n\n在三口烧瓶中加入135gA、150mL甲苯、120mL四氯化碳和1.5g四丁基溴化铵，分批加入45g氢氧化钠，室温下搅拌8h后，再加入250mL甲苯，用500mL蒸馏水洗涤三次，分出有机层，蒸出溶剂，减压蒸馏收集50～100Pa时75～85℃的馏分，即为1173，产率大于 $85\\%$ 。  \n\n（16）a-羟基酮光引发剂184的合成（一)  \n\n![](images/72705521f6527229e4cba7c511cd6ed2f32f4cd086a3780e01db7258af9bb060.jpg)  \n\n![](images/be4de3def7f455ee432af64a56e1784b8c52cd6027297161485fbad34837a7c2.jpg)  \n\n在三口烧瓶中加入 $_{5g}$ 镁粉，加人少量氯代环已烷与无水乙醚（体积比 $1:4$ ）混合液至刚好覆盖镁粉为止，加入少量单质碘，微热至碘的颜色消失，搅拌下滴加 $20\\mathbf{g}$ 氯化环已烷与$80\\mathrm{mL}$ 无水乙醚混合液，使反应液保持弱回流，加毕室温下搅拌1h，慢慢滴加 $20\\mathrm{mL}$ 经无水硫酸镁干燥处理的苯甲醛与 $20\\mathrm{mL}$ 无水乙醚混合液，滴加时需用冷水冷却，加完后室温反应$0.5\\mathrm{h}$ 。快速搅拌下加人 $10\\%$ 的稀硫酸至溶液澄清，分液，水层用乙醚萃取，合并有机层，碱洗、水洗，再用无水硫酸镁干燥，蒸去乙醚，经处理得白色固体A，烘干重 $_{31.58}$ ，熔点$44\\sim45\\mathrm{\\textperthousand}$ ，收率 $83\\%$ 。  \n\n在三口烧瓶中加入 $38\\mathbf{g}$ A和 $60\\mathrm{mL}$ 溶剂，搅拌和流水冷却下滴加含 $22g$ 重铬酸钠的硫酸溶液，加完后在室温搅拌1h，分液，经处理得白色固体 $\\textbf{B}35\\mathbf{g}$ ，熔点 $55\\sim56^{\\circ}C$ ，收率 $93\\%$  \n\n取 $57_{\\mathbf{\\deltaB}}\\mathbf{\\deltaB}$ 溶于冰醋酸，加热至回流，搅拌下滴加含 $\\mathbf{65g}$ 溴的 ${50}\\mathrm{mL}$ 冰醋酸混合液，产生大量白烟，加毕继续弱回流反应 $^{3\\mathrm{h}}$ ，反应液倾入 ${500}\\mathrm{mL}$ 碎冰中，析出胶状物，烘干，用石油醚重结晶得白色固体 $\\mathrm{~C~}73.5\\mathbf{g}$ ，熔点 $50{\\sim}51^{\\circ}\\mathrm{C}$ ，收率 $92\\%$ 。  \n\n取 $53g\\mathrm{~C~}$ ，加人 $10\\%$ 的氢氧化钠水溶液，使碱过量一倍，再加入少许相转移催化剂季铵盐，加热弱回流 $^{2\\mathrm{h}}$ ，静止，分液，有机层倾人大量冷水中，过滤，烘干，用石油醚重结晶得白色固体 $_{37.28}$ 即为 $\\alpha$ -羟基酮光引发剂184，熔点 $48\\sim49^{\\circ}C$ ，收率 $91\\%$  \n\n（17） $\\alpha$ -羟基酮光引发剂184的合成（二）  \n\n![](images/fe52d39d7e0a90afd2211ec94d98e21909166fa85cfd26d5ae5ed7839c04d0a4.jpg)  \n\n取 $_{15{\\bf g}}$ 无水三氯化铝于三口烧瓶中，加入 $40\\mathrm{mL}$ 精制苯，搅拌下先滴加几滴环已基甲酰氯至反应开始，再缓慢滴加 $_{15{\\bf g}}$ 环己基甲酰氯，加毕继续弱回流反应 $^{2\\mathrm{h}}$ ，冷却下滴加冷水并剧烈搅拌，再加浓盐酸使沉淀溶解，分液，苯层用活性炭脱色，干燥，蒸去苯，经处理得白色固体A $_{15.58}$ ，熔点 $54{\\sim}56^{\\circ}\\mathrm{C}$ ，收率 $82\\%$ 。  \n\n取 $38\\mathbf{g}$ A于三口烧瓶中，水浴加热至 $60^{\\circ}\\mathrm{C}$ 使A全熔，加一滴液溴，搅拌使溴的颜色消失，然后滴加 $_{44g}$ 液溴后， $60^{\\circ}\\mathrm{C}$ 下再搅拌 $2\\mathrm{h}$ ，经处理得白色固体 $\\textrm{B}48.5\\mathrm{g}$ ，熔点 $50{\\sim}51^{\\circ}\\mathrm{C}$ ，收率 $91\\%$  \n\n将 $_{538}\\mathrm{~B~}$ 置于三口烧瓶中，加人溶剂 ${\\bf60m L}$ ，剧烈搅拌下加入浓碱水溶液，使碱过量$30\\%$ ，加完继续在室温下搅拌2h，经处理得白色固体 $38.5{\\bf g}$ ，即为 $\\alpha$ 羟基酮光引发剂184，熔点 $48\\sim49^{\\circ}C$ ，收率 $94\\%$  \n\n(18) $\\pmb{\\alpha}$ -羟基酮光引发剂2959的合成  \n\n$$\n\\mathrm{HOCH_{2}C H_{2}O-}\\bigcup\\mathrm{+CH_{3}C O O H{\\longrightarrow}~C H_{3}C O O C H_{2}C H_{2}O-}\\bigcup\\mathrm{CH_{3}C O O C H_{2}C H_{2}O-}\\bigcup\\mathrm{CH_{3}C O O C H_{3}}.\n$$  \n\n![](images/d4aff2177ab8d63a8ce23c95128f4c2bb2b6fe7d047c602f0dc7c666977311bc.jpg)  \n\n用羟乙基苯基醚和乙酸进行酯化反应，减压蒸馏纯化后与异丁酰氯和无水三氯化铝进行Friedel-Crafts酰基化反应制备烷基取代芳基酮，纯化后再用溴/四氯化碳溶液进行溴化反应，将溴化产物置于甲醇钠-甲醇溶液中进行水解反应，用乙酸乙酯对水解混合物进行多次萃取，干燥、过滤，并浓缩萃取液，最后用丙酮-石油醚混合溶剂进行重结晶，即得产物α-羟基酮光引发剂2959{1-[4(2-羟乙氧基）苯基]-2-羟基-2-甲基-1-丙酮)，为白色结晶，熔点 $42\\sim43^{\\circ}C$ a  \n\n（19） $\\alpha$ -氨基苯乙酮类光引发剂369的合成  \n\n![](images/bb811c6d31dffdd14f489206c1d1d247f241abbeca5024b30d87867b5fa60a5d.jpg)  \n\n在三口烧瓶中加人 $340\\mathbf{g}$ 无水三氯化铝、 ${\\mathfrak{g}}5{\\mathrm{mL}}$ 氟苯和适量溶剂，在 ${<}10^{\\circ}\\mathrm{C}$ 时缓慢滴加$156\\mathrm{mL}$ 正丁酰氯，加毕升温至 $35{\\sim}45^{\\circ}\\mathrm{C}$ 搅拌 $4\\sim6\\mathrm{h}$ ，反应物冷却后倒入盐酸-冰水中，分出有机层，洗至中性，干燥、减压蒸馏，收集 $138{\\sim}140^{\\circ}\\mathrm{C}/3445\\mathrm{Pa}$ 的馏分 $112g$ 即为A，收率 $74\\%$ 。  \n\n在三口烧瓶中加人 $16\\mathbf{g}$ （0.lmol）A和溶剂，在 $30\\sim40^{\\circ}C$ 下滴加 $\\mathbf{8mL}$ （0.1mol）二氯亚矾，通氮气除去氯化氢。水洗分出有机层，干燥，回收溶剂，得18g淡黄色液体B，收率 $93.3\\%$ 。  \n\n在三口烧瓶中加人含 $\\mathbf{45g}$ 二甲胺的乙醚溶液，置于冰水浴中，搅拌下缓慢滴加 $\\textbf{B}61_{\\pmb{\\mathrm{g}}}$ 在 $(0\\pm2)^{\\circ}\\mathsf{C}$ 下搅拌反应。通氮气除去过量二甲胺，将反应液倒人水中，分出有机层，水洗至中性，干燥，蒸出乙醚，经酸化、提取、加碱、水洗后，减压蒸馏收集 $139\\sim141^{\\circ}\\mathrm{C}/$ 2340Pa的馏分，得淡黄色油状液体C。  \n\n将 $8.4\\mathbf{g}\\mathrm{~C~}$ 和溶剂加入三口烧瓶中，搅拌下缓慢滴加 $6.2g$ 苄氯，升温搅拌 $^{12\\mathbf{h}}$ ，蒸馏回收溶剂，加水升温至 $50\\mathrm{\\sim}70^{\\circ}\\mathrm{C}$ ，加入碱液回流反应 $0.5\\sim1\\ensuremath{\\mathrm{h}}$ ，冷却后分离有机层，经提取、干燥后得橘黄色膏状物，用乙醇重结晶，得黄色晶体D，熔点 $64{\\sim}65\\ensuremath{\\mathrm{^circC}}$ ，收率 $93.7\\%$ 。  \n\n$\\textcircled{1}$ 三口烧瓶中依次加入D、吗啉、溶剂和适量的碱，升温至 $120{\\sim}160^{\\circ}\\mathrm{C}$ 反应 $\\mathbf{30h}$ ，冷至室温倒入水中，析出棕色膏状物，经提取、水洗、干燥得红褐色糊状物，用乙醇重结晶，得淡黄色针状晶体，即为 $\\alpha$ 氨基酮类光引发剂369（1-对吗琳苯基-2-二甲氨基-2-苄基-1-丁酮)，熔点 $115{\\sim}116^{\\circ}\\mathrm{C}$ ，收率 $>55\\%$ 。  \n\n$\\textcircled{2}$ 若分别用二正丁胺、二乙醇胺、二环己胺和吡咯代替吗啉，可合成出不同 $\\alpha$ 氨基酮类光引发剂（表4-23)。  \n\n表4-23不同 ${\\pmb\\alpha}$ 氨基酮光引发剂的物理性质  \n\n\n<html><body><table><tr><td>序号</td><td>α-氨基酮取代基</td><td>外观</td><td>熔点/℃</td><td>Amax/nm</td></tr><tr><td>1</td><td>吗啉</td><td>淡黄色结晶</td><td>115~116</td><td>323</td></tr><tr><td>2</td><td>二正丁胺</td><td>黄色油状液体</td><td></td><td>344</td></tr><tr><td>3</td><td>二乙醇胺</td><td>棕黄色固体</td><td>154~156</td><td>340</td></tr><tr><td>4</td><td>二环己胺</td><td>红褐色膏状物</td><td></td><td>336</td></tr><tr><td>5</td><td>吡咯</td><td>深棕色膏状物</td><td></td><td>333</td></tr></table></body></html>  \n\n（20） $\\alpha\\cdot$ -氨基苯乙酮衍生物的合成  \n\n![](images/120f3dbd32b64d4ca8a5e83a475e03c1e0e8a189687397a62fbda5c857d90675.jpg)  \n\n$\\textcircled{1}$ 在三口烧瓶中加入新制的甲醇钠/甲醇溶液，室温下滴加 $18\\mathbf{g}$ B（见光引发剂369合成)，升温至 $60{\\sim}70^{\\circ}\\mathrm{C}$ 反应 $0.5\\mathrm{h}$ ，回收溶剂，反应混合物用乙醚萃取，经水洗、干燥、减压蒸馏，收集 $73{\\sim}75^{\\circ}\\mathrm{C}/120\\mathrm{Pa}$ 的馏分 $10.7{\\bf g}$ ，即为E，收率 $61.8\\%$ ，折射率 $n_{\\mathrm{D}}^{23}=1.4790$ 。  \n\n$\\textcircled{2}$ 在三口烧瓶中加入E和哌啶（摩尔比 $1:1)$ ，在 $90{\\sim}110^{\\circ}\\mathrm{C}$ 下反应 $10\\sim20\\mathrm{h}$ ，冷至室温，用稀盐酸溶解反应混合物，加人甲苯振摇，分出水层合，将 $\\mathtt{p H}$ 调至明显碱性，将析出的油状物经萃取、洗涤、干燥、重结晶，得到橙色晶体F，熔点 $41\\sim43^{\\circ}\\mathrm{C}$ ，收率 $86.3\\%$ 。  \n\n③在三口烧瓶中加人10g（0.05mol）F和适量溶剂，滴加4.6g（0.06mol）3-氯丙烯，在40～50℃反应20h，回收溶剂后加人稀氢氧化钠溶液，加热回流 20min。冷却，经萃取、干燥、回收溶剂，用柱色谱法精制，得到橙红色油状物G（R为烯丙基)，收率为73.6%。  \n\n④在三口烧瓶中加人8.4g（0.04mol）G、7.6g（0.09mol）吗啉，适量溶剂和碳酸钾，在130～150℃反应30h。冷却后经萃取、洗涤、干燥、回收溶剂，用柱色谱法精制得到红色蜡状产品H（R为烯丙基，Y为吗啉基）1-对吗啉苯基-2-哌啶基-2-烯丙基-1-丁酮(MPAB)，收率 $72.5\\%$ 。  \n\na.在三口烧瓶中加人8.4g（0.04mol）G、7.4g（0.09mol）哌啶，按与④相同反应条件，可制得7.8g黄色晶体，为1-对哌啶基-2-哌啶基-2-烯丙基-1-丁酮（PPAB)，熔点74～$76^{\\circ}\\mathrm{C}$ ，收率 $75.7\\%$ 。  \n\nb.用13.3g（0.1mol）氯化苄代替③反应中3-氯丙烯，在相同条件下反应，可得到黄色油状产品1-对氟苯基-2-哌啶基-2-节基-1-丁酮。按与④相同条件反应可得到1-对吗啉基-2-$\\alpha$ 氨基苯乙酮衍生物，物理性质见表4-24。  \n\n表4-24 $\\pmb{\\alpha}$ 氨基苯乙酮衍生物的物理性质  \n\n\n<html><body><table><tr><td>产品</td><td>产品状态</td><td>Amax/nm</td></tr><tr><td>MPAB</td><td>红色蜡状液体</td><td>334</td></tr><tr><td>MPBB</td><td>红色蜡状液体</td><td>348</td></tr><tr><td>PPAB</td><td>黄色晶体</td><td>337</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 151,
+        "chunk": "# (21）二苯甲酮（BP）的合成（一)  \n\n![](images/b83eb135223bbcb3e5c3dcc291909d78541f56a472481f80f8ce470deb77e54e.jpg)  \n\n在三口烧瓶中加人 ${700}\\mathrm{mL}$ 苯和 $1.5\\mathbf{g}$ 无水氯化铝，升温搅拌，在 $40\\sim42^{\\circ}C$ 下将 $138\\mathrm{mL}$ 氯化苄和 ${50}\\mathrm{mL}$ 苯混合物滴加，3h加毕，继续反应1.5h，以蒸馏水洗涤，用 $\\bf N a_{2}C O_{3}$ 中和，粗产物收率 $95\\%$ ，减压蒸馏，取 $40{\\sim}70^{\\circ}\\mathrm{C}/1862{\\sim}2394\\mathrm{Pa}$ 馏分，得二苯甲烷精制品。  \n\n将 $100\\mathbf{g}$ 二苯甲烷、 $1.5{\\bf g}$ 三水乙酸铅和沸石数粒加入三口烧瓶中，加热至 $100{\\sim}110^{\\circ}\\mathrm{C}$ ，在 $2\\mathord{\\sim}2.5\\mathrm{h}$ 内滴加 $d=1.5\\mathrm{g}/\\mathrm{cm}^{3}$ 的浓硝酸 $120\\mathbf{g}$ ，继续反应 $6\\mathbf{h}$ ，冷至 $80^{\\circ}\\mathrm{C}$ ，分去水相，以$80^{\\circ}\\mathrm{C}$ 蒸馏水和 $1\\%$ 的 $\\mathrm{Na}_{2}\\mathrm{CO}_{3}$ 各洗3次，减压蒸馏收集 $145\\sim180^{\\circ}\\mathrm{C}/665\\sim1197\\mathrm{Pa}$ 的馏分，即为二苯甲酮，收率 $91\\%$ 。用石油醚重结晶可得精品。  \n\n(22）二苯甲酮（BP）的合成（二)  \n\n![](images/6d8301adcd11c577a75bb8d544d237ad0d63539dd44c92adf1eb879041c9997c.jpg)  \n\n在反应瓶中依次加入 $355\\mathrm{mL}$ 苯和 $_{133g}$ 无水三氯化铝，搅拌升温至 $60{\\sim}70^{\\circ}\\mathrm{C}$ ，按 $60\\mathbf{g}/\\mathbf{h}$ 的速度通入光气 $120\\mathbf{g}$ ，光气通毕加热至沸腾，以去除未反应光气。加入冰水 $18g$ 进行水解，用分液漏斗分离水相和有机相。有机相用饱和食盐水洗涤3次；水相用苯萃取3次。萃取液与有机相合并，常压蒸馏除去苯，再减压蒸馏得二苯甲酮，收率 $91.5\\%$ 。  \n\n(23）二苯甲酮（BP）的合成（三)  \n\n![](images/71dda40a16d5f81c1e8a660c4e8e0455c5bf0d2befed01d3a930fb0f73f7d985.jpg)  \n\n将苯和氯化锌溶液加人反应釜中，加热至 $70^{\\circ}\\mathrm{C}$ ，滴加氯，在 $70\\mathrm{\\sim}75^{\\circ}\\mathrm{C}$ 搅拌反应10h，经分离得到二苯甲烷粗品，收率 $95\\%$ 。  \n\n在 $100{\\sim}115^{\\circ}\\mathrm{C}$ 下，向二苯甲烷中滴加相对密度为1.4的硝酸进行氧化反应，经分层、洗涤、蒸馏得到产物二苯甲酮，收率 $90\\%$ 。  \n\n(24）二苯甲酮（BP）的合成（四)  \n\n![](images/30ac68a98fe7a8761437155466fe0d7e93baf9a91da979338e2f8baf0613c4f0.jpg)  \n\n将2/3量的无水四氯化碳和三氯化铝加人反应釜中，冷却至 $10\\mathrm{\\sim}15\\mathrm{\\textperthousand}$ ，加入1/12量的苯进行反应；继续冷至 $5\\sim10^{\\circ}\\mathrm{C}$ ，滴加其余1/3量的四氯化碳和11/12量的苯混合物，于$10^{\\circ}\\mathrm{C}$ 反应 $^{3\\mathrm{h}}$ 。加水，回收过量的四氯化碳后，进行水蒸气蒸馏，除尽四氯化碳，同时将二苯二氯甲烷水解为二苯甲酮。取油层结晶，过滤得二苯甲酮粗品，减压蒸馏，收集 $157\\sim$ $176^{\\circ}\\mathrm{C}/1.33{\\sim}2.67\\mathrm{kPa}$ 馏分得二苯甲酮精品。  \n\n（25）2-乙基葱（2-EA）的合成  \n\n![](images/c5b3292e248df636b709a513dfc1f0fd9ba4d2a180eb9b16b2f0176651ca82f4.jpg)  \n\n在干燥的三口烧瓶中加人 $_{144g}$ 乙苯和 $\\mathbf{296g}$ 无水三氯化铝，维持在 $20\\sim30^{\\circ}{\\mathrm{C}}$ 下，分批加人 $150\\mathbf{g}$ 苯酐，控制温度 ${<}40^{\\circ}\\mathrm{C}$ ，反应2h，至无氯化氢逸出，反应完毕，得橘红色溶液。冷却后慢慢滴加 $10\\%$ 的盐酸溶液进行水解，快速搅拌，控制温度 ${<}40^{\\circ}\\mathrm{C}$ ，物料变为乳白色油状，分离，油状物在 $55\\sim60^{\\circ}\\mathsf{C}/4\\mathbf{k}\\mathsf{P a}$ 减压蒸馏，得A。  \n\n将A置于三口烧瓶中，加热至 $110{\\sim}120^{\\circ}\\mathrm{C}$ ，搅拌下慢慢滴加 $20\\%$ 的发烟硫酸，使反应温度 ${<}120^{\\circ}{\\mathrm{C}}$ 。反应完毕得深黄色液体，倾入冰水混合物中，析出黄色的2-乙基葱粗品，经过滤、碱洗、水洗得浅黄色固体，熔点 $104{\\sim}106^{\\circ}\\mathrm{C}$ ，产率 $89\\%$ 。  \n\n粗品加入硫代硫酸钠和 $10\\%$ 的 $\\mathbf{NaOH}$ 溶液，中和至 $\\mathfrak{p H}=11$ ，于 $95\\mathrm{^\\circC}$ 反应 $20\\mathrm{{min}}$ ，得无色2-乙基氢，通空气氧化，得2-乙基。用 $500\\mathrm{mL}95\\%$ 的乙醇萃取，再于 $79\\sim85\\mathrm{^{\\circ}C}$ 蒸去乙醇，再 $80^{\\circ}\\mathrm{C}$ 恒温干燥得浅黄色固体即为2-乙基葱结晶，熔点 $110{\\sim}111\\%$ 。  \n\n（26）硫杂葱酮类光引发剂ITX的合成  \n\n![](images/99c128b14dec1d4ebbb73484cb5f07c2f8d8b6b1614cff4ef5d3b7d24b187d99.jpg)  \n\n在三口烧瓶中加人二硫代水杨酸59.8g（90%，0.176mol)，搅拌下加人浓硫酸115g$(90\\%$ ， $\\boldsymbol{1.0565}\\mathrm{mol})$ 搅匀。冷至 $10^{\\circ}\\mathsf{C}$ ，滴加异丙苯 $_{192g}$ （ $99\\%$ ， $\\boldsymbol{1.582m o l})$ ，时间约3h，控制温度在10～15℃。加毕升温至100℃，在100～105℃下缓慢通人SO3，经中控分析维持体系硫酸浓度。5～6h后降温至室温，滴加32mL水，揽匀，反应液用150g异丙苯于20～$30^{\\circ}\\mathrm{C}$ 搅拌萃取。合并异丙苯液，先用 $60\\mathrm{mL}$ ， $2\\%$ 的氢氧化钠水溶液洗至 $\\mathbf{pH}=7\\sim8$ ，再用$100\\mathrm{mL}$ 水于 $40{\\sim}50^{\\circ}\\mathrm{C}$ 洗涤，减压蒸馏回收异丙苯 $217\\mathbf{g}$ ，残留浅棕色ITX粗品约 $83.4{\\bf g}$ ，含量 $97.33\\%$ ，收率 $90\\%$ a  \n\nITX粗品 $80.3\\mathbf{g}$ 在氮气保护下，用高真空蒸馏提纯，收集 $185{\\sim}190\\%\\mathrm{~/0}.133\\mathrm{kPa}$ 馏分，得淡黄色产品 $71.7{\\bf g}$ ，含量 $99.5\\%$ ，蒸馏收率 $91.23\\%$ ，以二硫代水杨酸为原料，ITX总收率 $982\\%$ 。  \n\n（27）取代硫杂葱酮光引发剂的合成  \n\n![](images/89778dee3843047472f00288ae8182f0a871988a6caabcfa5f2fbc1be140ce22.jpg)  \n\nR：烷基、—OCH、—OC2Hs  \n\n在三口烧瓶中加入邻硫基苯甲酸和浓硫酸混合搅拌，慢慢加入烷基苯，在室温下搅拌数小时后，再在 $50{\\sim}100^{\\circ}\\mathrm{C}$ 水浴上加热数小时，倒人10倍于反应液体积的冰水中，待冰化后，过滤，洗涤至中性，干燥后重结晶，得烷基取代硫杂葱酮。  \n\n用同样的合成方法合成甲氧基取代硫杂葱酮和乙氧基取代硫杂葱酮。  \n\n（28）2-羟基硫杂葱酮的合成  \n\n![](images/786bac3631818fc2292425256d36f96a718214a76c2b077ff2f6293c75c7628e.jpg)  \n\n在三口烧瓶中加人邻硫基苯甲酸和浓硫酸混合搅拌，加人稍过量的苯酚，控制在 $40\\sim$ $80^{\\circ}\\mathrm{C}$ 反应数小时，再在沸水浴上加热数小时，反应液倒人沸水中，冷却，过滤，以稀碱液洗涤，水洗至中性，干燥后重结晶，即得2-羟基硫杂葱酮。 5丙氧基、丁氧基、戊氧基取代硫杂葱酮的合成：  \n\n![](images/995b07d9aa27eabc431f077db2ec27fb2cd2fc7406e7f001e5194097f1568c31.jpg)  \n\nR:CgH7、CHg、 $\\mathbf{C}_{5}\\mathbf{H}_{11}$  \n\n在三口烧瓶中加入2-羟基硫杂葱酮、溴代烷（正溴丙烷、正溴丁烷、正溴戊烷）、氢氧化钾、溶剂和相转移催化剂，在一定温度下搅拌反应数小时。用水蒸气蒸馏除去溶剂，过滤、洗涤至中性，结晶，即得丙氧基、丁氧基、戊氧基取代硫杂葱酮，其性能见表4-25。  \n\n表4-25取代硫杂愿酮的物理性质  \n\n\n<html><body><table><tr><td>序号</td><td>化合物名称</td><td>收率/%</td><td>熔点/℃</td><td>Amax/nm</td><td>E/[L/(mol·cm)]</td></tr><tr><td>1</td><td>2-甲基硫杂葱酮</td><td>43.3</td><td>110～112</td><td>382</td><td>6600</td></tr><tr><td>2</td><td>2,4-二甲基硫杂葱酮</td><td>57.4</td><td>143~145</td><td>385</td><td>5700</td></tr><tr><td>3</td><td>1,2,4-三甲基硫杂葱酮</td><td>35.9</td><td>116~118</td><td>381</td><td>6200</td></tr><tr><td>4</td><td>1,4-二甲基硫杂葱酮</td><td>48.0</td><td>107～110</td><td>380</td><td>6000</td></tr><tr><td>5</td><td>2-乙基硫杂葱酮</td><td>13.4</td><td>98～100</td><td>385</td><td>6300</td></tr><tr><td>6</td><td>2-羟基硫杂葱酮·</td><td>60.0</td><td>>250</td><td>398</td><td>①</td></tr><tr><td>？</td><td>2-甲氧基硫杂葱酮</td><td>25.3</td><td>129~130</td><td>399</td><td>5700</td></tr><tr><td>8</td><td>2-乙氧基硫杂葱酮</td><td>32.0</td><td>115~118</td><td>399</td><td>4000</td></tr><tr><td>9</td><td>2-丙氧基硫杂葱酮</td><td>74.1</td><td>81~83</td><td>399</td><td>6100</td></tr><tr><td>10</td><td>2-丁氧基硫杂葱酮</td><td>70.4</td><td>76~79</td><td>399</td><td>6100</td></tr><tr><td>11</td><td>2-戊氧基硫杂葱酮</td><td>72.0</td><td>80~82</td><td>400</td><td>7400</td></tr><tr><td>12</td><td>2-硝基硫杂葱酮</td><td>69.0</td><td>225~227</td><td>345</td><td>①</td></tr></table></body></html>\n\n$\\Phi$ 溶解性较差，摩尔吸光系数e没有测定。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 152,
+        "chunk": "# （29）2-硝基硫杂葱酮的合成  \n\n![](images/fdf8b527c98a9f626fd0e0f646f38ab81ca875aaac52b26ef75fa253d85450c2.jpg)  \n\n将邻氯苯甲酸控制反应条件硝化，得到2-氯-5-硝基苯甲酸，再和硫酚反应，所得产物与浓硫酸缩合得粗品，重结晶得2-硝基硫杂葱酮精品。  \n\n（30）硫杂葱酮羧酸及其衍生物的合成$\\textcircled{1}$ 硫杂葱酮-1-羧酸的合成  \n\n![](images/72b118fbaec6c6da2bfd24fcfd6d19911ee24c61f15bf60ac936ee1f7a91d50b.jpg)  \n\n![](images/9db151026b0d7423f6fa45fd31f3e5568bdc8b6a86b7c7e57c4901985d4fce3b.jpg)  \n\n在三口烧瓶中加人2.20g硫酚、5.64g3-硝基-N-对甲苯基-邻苯二甲酰亚胺和50mL二甲基甲酰胺，搅拌溶解，在氮气保护下慢慢加入2.8mL三乙胺，混合物迅即转黄，颜色加深，待再转成淡黄色后，搅拌20min，把混合物倒人稀盐酸/冰水中，经过滤、干燥，得$6,86{\\bf g\\ A}$ ，熔点 $187{\\sim}188^{\\circ}\\mathrm{C}$ ，收率 $95\\%$ 。  \n\n将3.5gA加到35mL、20%的氢氧化钠溶液中，在100℃搅拌30min，冷却，用浓盐酸酸化，过滤，将滤饼转至30mL浓盐酸中回流1h，冷却、过滤，真空干燥得2.2gB，熔点${>}270^{\\circ}\\mathrm{C}$ ，收率 $81\\%$ 。  \n\n将6.9gB和70mL多聚磷酸在200℃下搅拌100min，冷却至室温，倒人200mL冷水中，过滤，干燥，再溶于二甲基甲酰胺中，加活性炭升温脱色，加水重新析出产品，过滤、干燥，用冰醋酸重结晶得6.2g黄色的硫杂葱酮-1-羧酸，熔点260～262℃，收率96%。  \n\n$\\textcircled{2}$ 硫杂葱酮-4-羧酸的合成  \n\n![](images/0a5953a24851bc8ab16a29098f1acd99103ed8d27aaeed51ebc11e439d1fcc8d.jpg)  \n\n在三口烧瓶中加人3.75g邻硫基苯甲酸、3.95g邻氯苯甲酸、5g无水碳酸钾、0.1g铜粉及50mL二甲基甲酰胺，搅拌溶解，升温至155℃，氮气保护下反应2.5h，冷却后加水和活性炭煮沸脱色，过滤，滤液用浓盐酸酸化，过滤，真空干燥得4.87gC，熔点>270℃，收率 $73.1\\%$ 。  \n\n将5gC和 $50\\mathrm{mL}$ 浓硫酸在 $25^{\\circ}\\mathrm{C}$ 搅拌 $^{10\\mathbf{h}}$ ，然后倒入冷水中，在沸水浴上加热 $30\\mathrm{min}$ ，冷却、过滤，用水洗涤滤饼，干燥，用二甲基甲酰胺和冰醋酸混合溶剂重结晶，得3.46g硫杂葱酮-4-羧酸，熔点 ${>}300^{\\circ}\\mathrm{C}$ ，收率 $74.1\\%$ 。  \n\n$\\textcircled{3}$ 硫杂葱酮-2-羧酸的合成  \n\n![](images/7ef9e86307d8f02997c5643d952f56a7ef7a53088bf8dfa8d59aaeab2f2d2f92.jpg)  \n\n![](images/26e6a8ccdcd64fc36dcca9e11f60dc22c2926fce5e3b4a5307c44d3f33b13366.jpg)  \n\n以邻硫基苯甲酸和对溴苯甲酸为原料，合成方法见步骤 $\\textcircled{2}$ ，最终产物为硫杂葱酮-2-羧酸，熔点 ${>}270^{\\circ}\\mathrm{C}$ ，收率 $59.7\\%$ α  \n\n$\\textcircled{4}$ 硫杂葱酮-3-羧酸的合成  \n\n![](images/c1cae7962bd1221e04289d67fb150a8c7862a5faa78c9d905635d613834b1156.jpg)  \n\n以硫酚和2-硝基-1，4-苯二甲酸甲酯为原料，合成方法见步骤 $\\textcircled{1}$ ，制得硫杂葱酮-3-羧酸，熔点 ${>}250^{\\circ}\\mathrm{C}$ ，收率 $70.5\\%$ 中  \n\n$\\textcircled{5}$ 硫杂葱酮-1-羧酸甲酯的合成  \n\n将 ${\\mathfrak{s}}_{\\mathbf{g}}$ 硫杂葱酮-1-羧酸和 $23\\mathrm{mL}$ 二氯亚矾回流5h后，蒸发至干。再慢慢加人 $100\\mathrm{mL}$ 甲醇，反应剧烈时用冷水冷却，加完后升温回流2h，蒸去甲醇，向固体物中加入饱和碳酸氢钠溶液，以除去未反应的酸。过滤、干燥，用甲醇重结晶，得 $3.25\\mathbf{g}$ 硫杂葱酮-1-羧酸甲酯，熔点 $138{\\sim}140^{\\circ}\\mathrm{C}$ ，收率 $78\\%$ 。  \n\n其他各种甲酯和乙酯的合成，参照步骤 $\\textcircled{5}$ 的合成。  \n\n$\\textcircled{6}$ 硫杂葱酮-4-羧酸异丁酯的合成  \n\n将 $\\mathfrak{s}_{\\mathbf{g}}$ 硫杂葱酮-4-羧酸和 $\\scriptstyle30\\mathrm{mL}$ 二氯亚矾回流3h后，蒸发至干，然后加人 $100\\mathrm{mL}$ 二氧六环和 $6\\mathrm{mL}$ 异丁醇，加热回流 $^{\\mathfrak{s h}}$ ，蒸去溶剂，加入饱和碳酸氢钠溶液，以除去未反应的酸。过滤、干燥，用甲醇重结晶，得 $4.25\\mathbf{g}$ 硫杂葱酮-4-羧酸异丁酯，熔点 $140{\\sim}142^{\\circ}\\mathrm{C}$ ，收率 $69.9\\%$ 。  \n\n其他各种异丁酯的合成，参照步骤 $\\textcircled{6}$ a硫杂葱酮羧酸及衍生物的性质见表4-26。  \n\n![](images/8c677a2a6a7d9ef37acbb4df69840cf4142bfec346e1d36eef2cfb57dd72173e.jpg)  \n\n表4-26硫杂葱酮羧酸及衍生物的性质  \n\n\n<html><body><table><tr><td>序号</td><td>化合物</td><td>收率/%</td><td>熔点/℃</td><td>Amax/nm</td><td>ε/[L/(mol·cm)]</td></tr><tr><td>1</td><td>硫杂葱酮-1-羧酸</td><td>73.8</td><td>260~262</td><td>380.4</td><td>6250</td></tr><tr><td>2</td><td>硫杂葱酮-1-羧酸甲酯</td><td>78.0</td><td>138～140</td><td>385.6</td><td>6450</td></tr><tr><td>3</td><td>硫杂葱酮-1-羧酸乙酯</td><td>73.9</td><td>140～141</td><td>383</td><td>6450</td></tr><tr><td>４</td><td>硫杂葱酮-1-羧酸异丁酯</td><td>70.6</td><td>140~142</td><td>383.8</td><td>6450</td></tr><tr><td>5</td><td>硫杂葱酮-2-羧酸</td><td>59.7</td><td>>270</td><td>375.2</td><td>5300</td></tr><tr><td>6</td><td>硫杂葱酮-2-羧酸甲酯</td><td>76.0</td><td>191~193</td><td>375.2</td><td>5750</td></tr><tr><td>7</td><td>硫杂葱酮-2-羧酸乙酯</td><td>79.9</td><td>126~127</td><td>374.8</td><td>5750</td></tr><tr><td>8</td><td>硫杂葱酮-2-羧酸异丁酯</td><td>65.0</td><td>121~123</td><td>375.2</td><td>5750</td></tr><tr><td>9</td><td>硫杂葱酮-3-羧酸</td><td>70.5</td><td>>270</td><td>394</td><td>5850</td></tr><tr><td>10</td><td>硫杂葱酮-3-羧酸甲酯</td><td>74.0</td><td>161.5~163</td><td>395.2</td><td>6050</td></tr><tr><td>11</td><td>硫杂葱酮-3-羧酸乙酯</td><td>68.0</td><td>144.5~146</td><td>395.6</td><td>6050</td></tr><tr><td>12</td><td>硫杂葱酮-3-羧酸异丁酯</td><td>70.0</td><td>123~124.5</td><td>395.2</td><td>6050</td></tr><tr><td>13</td><td>硫杂葱酮-4-羧酸</td><td>54.2</td><td>>300</td><td>384.4</td><td>7000</td></tr><tr><td>14</td><td>硫杂葱酮-4-羧酸甲酯</td><td>78.0</td><td>192~193</td><td>386.8</td><td>7750</td></tr><tr><td>15</td><td>硫杂葱酮-4-羧酸乙酯</td><td>85.4</td><td>149~150</td><td>386</td><td>7750</td></tr><tr><td>16</td><td>硫杂葱酮-4-羧酸异丁酯</td><td>69.9</td><td>140~142</td><td>386</td><td>7750</td></tr></table></body></html>  \n\n（31）硫杂葱酮酰胺类光引发剂的合成  \n\n![](images/150f71492933cfefce37d13fb02cb6e4154eee1ebfa53307d3823c819a97da22.jpg)  \n\n① 硫杂葱酮-1-苯酰胺的合成在三口烧瓶中加入3.0g硫杂葱酮-1-羧酸和 30mL二氯亚矾，加热回流5h，蒸除二氯亚矾，加入30mL二氯乙烷，搅拌使其溶解。滴加4mL苯胺和10mL二氯乙烷混合物，加毕继续反应1h，蒸除二氯乙烷，残渣用稀盐酸及水各洗三次，再用二甲基甲酰胺/水混合溶剂重结晶两次，得3.5g硫杂葱酮-1-苯酰胺，熔点180～181℃，收率 $90.2\\%$ 。  \n\n以同样方法合成表4-27中化合物2、3。  \n\n②硫杂葱酮-2-苯酰胺的合成在三口烧瓶中加入3.0g硫杂葱酮-2-羧酸和50mL二氯亚矾，回流5h，蒸除二氯亚矾，加人 $80\\mathrm{mL}$ 二氧六环， $50^{\\circ}\\mathrm{C}$ 下滴加 $\\scriptstyle4\\mathrm{mL}$ 苯胺与 $20\\mathrm{mL}$ 二氧六环的混合物，加毕再回流 $^\\mathrm{1h}$ 。冷却，加冷水搅拌，过滤、水洗、干燥得 $\\mathbf{2.5g}$ 硫杂葱酮-2-苯酰胺，熔点 $208{\\sim}209\\mathrm{\\textC}$ ，收率 $84\\%$ 。以同样方法合成表4-27中化合物5、6。  \n\n$\\textcircled{3}$ 硫杂葱酮-3-对甲苯酰胺的合成在三口烧瓶中加人 $3.0\\mathbf{g}$ 硫杂葱酮-3-羧酸、 ${50}\\mathrm{mL}$ 二氯亚矾，回流5h，蒸除二氯亚矾。加人 ${50}\\mathrm{mL}$ 二氧六环，再加入含 $2.6\\mathbf{g}$ 对甲苯胺的 $10\\mathrm{mL}$ 二氧六环溶液，继续反应2h，加人 ${\\mathsf{50m L}}$ 水，过滤、水洗、干燥，得 $3.58$ 硫杂葱酮-3-对甲苯酰胺，熔点 $279{\\sim}280^{\\circ}\\mathrm{C}$ ，收率 $86.6\\%$ 。  \n\n用同样方法合成表4-27中化合物 $_{8\\sim12}$ a（32）新型高效光引发剂丙烯酸甲酯基三乙酰基甲烷的合成  \n\n表4-27硫杂葱酮酰胺衍生物的性能  \n\n\n<html><body><table><tr><td>序号</td><td>化合物</td><td>熔点/℃</td><td>产率/%</td><td>Amax/nm</td><td>ε/[L/(mol·cm)]</td></tr><tr><td>１</td><td>硫杂葱酮-1-苯酰胺</td><td>180~181</td><td>90.2</td><td>383</td><td>2350</td></tr><tr><td>2</td><td>硫杂葱酮-1-对甲苯酰胺</td><td>163~164</td><td>85.2</td><td>385</td><td>7741</td></tr><tr><td>3</td><td>硫杂葱酮-1-对硝基苯酰胺</td><td>>300分解</td><td>89.0</td><td>368</td><td>13404</td></tr><tr><td>4</td><td>硫杂葱酮-2-苯酰胺</td><td>208~209</td><td>84.4</td><td>383</td><td>5299</td></tr><tr><td>5</td><td>硫杂葱酮-2-对甲苯酰胺</td><td>245~246</td><td>85.5</td><td>385</td><td>7693</td></tr><tr><td>6</td><td>硫杂葱酮-2-对硝基苯酰胺</td><td>140~141</td><td>80.1</td><td>381</td><td>2317</td></tr><tr><td>7</td><td>硫杂葱酮-3-苯酰胺</td><td>240~241</td><td>80.4</td><td>381</td><td>3177</td></tr><tr><td>8</td><td>硫杂葱酮-3-对甲苯酰胺</td><td>279~280</td><td>86.6</td><td>380</td><td>3346</td></tr><tr><td>9</td><td>硫杂蕙酮-3-对硝基苯酰胺</td><td>>300分解</td><td>79.5</td><td>335</td><td>26978</td></tr><tr><td>10</td><td>硫杂葱酮-4-苯酰胺</td><td>280~281</td><td>57.1</td><td>384</td><td>9926</td></tr><tr><td>11</td><td>硫杂葱酮-4-对甲苯酰胺</td><td>293~294</td><td>85.4</td><td>385</td><td>7431</td></tr><tr><td>12</td><td>硫杂葱酮-4-对硝基苯酰胺</td><td>263~264</td><td>80.0</td><td>380</td><td>7935</td></tr></table></body></html>  \n\n![](images/a9c14392949f4c5902e643e5e71e971ea1c97b13755011f88da638ac74114f91.jpg)  \n\n在三口烧瓶中加人 $80\\mathbf{g}$ （0.8mol）乙酰丙酮，再加入 $0.3\\mathbf{g}$ 1 $(0,013\\mathrm{mol}$ ）金属钠，反应比较激烈，温度很快上升，等温度冷到室温后，控制温度 ${<}35^{\\circ}\\mathrm{C}$ ，滴加 $34.48$ (0.4mol）丙烯酸甲酯，滴加1h后，将反应温度降至室温。用GC-MASS对反应加成产物确认，从GC图上看 $92\\%$ 的单加成产物，用盐酸把反应液调到中性，过滤掉盐，减压蒸馏得 $_{72g}$ 纯度为$98\\%$ 的丙烯酸甲酯基乙酰丙酮A。  \n\n在三口烧瓶加人 $35{\\bf g}$ ( $\\phantom{+}0.188\\mathbf{mol}$ ）A和 $200\\mathrm{mL}$ 干燥的乙醚，再缓慢加人 $4.33\\mathbf{g}$ $\\left(0,88\\mathrm{mol}\\right)$ ）金属钠，反应剧烈，温度很快上升，等温度无变化后，用GC检测不到A，说明金属钠与A反应完全。降温到 $20\\mathrm{{^\\circC}}$ ，把蒸馏过的 $14.76\\mathbf{g}$ （0.188mol）乙酰氯滴加到三口烧瓶中，在加热回流条件下反应3h，用GC检测反应，减压蒸馏，得到纯度 $98.6\\%$ 的丙烯酸甲酯基三乙酰甲烷 $33.9{\\bf g}$ ，总收率 $85\\%$ 。  \n\n（33）阳离子光引发剂二苯基碘盐的合成  \n\n$$\n\\begin{array}{r l}&{2\\displaystyle\\bigcap_{\\mathbf{\\alpha}^{+}\\mathbf{\\Theta}}+\\mathbf{\\scriptscriptstyle{K}}\\mathbf{\\log}_{3}+2\\mathbf{\\alpha}\\mathbf{\\textsc{K}}_{4}+2(\\mathbf{\\mathrm{C}}\\mathbf{\\textsc{H}}_{3}\\mathbf{C}{\\mathbf{\\to}}_{0}{\\mathbf{\\to}}\\mathbf{\\Lambda}_{\\mathbf{\\Lambda}}^{+}}\\\\ &{\\qquad\\Big[\\mathbf{\\mu}_{\\bigstar}^{\\mathrm{i}}\\Big\\langle\\mathbf{\\Xi}\\mathbf{\\hat{\\mathbf{\\Lambda}}}\\Big\\rangle^{+}\\mathbf{\\scriptscriptstyle{K}}\\mathbf{\\textsc{S}}_{4}^{-}+\\mathbf{\\bar{K}}\\mathbf{\\textsc{s}}\\mathbf{\\textsc{F}}_{6}-\\Big[\\mathbf{\\mu}_{\\bigstar}^{\\mathrm{i}}\\Big\\langle\\mathbf{\\Xi}\\Big\\rangle^{+}\\mathbf{\\scriptscriptstyle{K}}\\mathbf{\\Sigma}\\mathbf{\\Sigma}\\mathbf{\\Sigma}^{+}\\mathbf{\\bar{K}}\\mathbf{H}\\mathbf{S}{\\mathbf{\\Lambda}}_{4}^{-}+\\mathbf{\\bar{K}}\\mathbf{H}\\mathbf{S}{\\mathbf{O}}\\mathbf{H}+\\mathbf{\\Lambda}[\\mathbf{\\Lambda}_{\\mathbf{\\tilde{\\mathbf{G}}}}\\mathbf{\\Lambda}]\\Big]^{+}}\\end{array}\n$$  \n\n将三口烧瓶置于干冰-丙酮浴中，加入 $25g$ （0.116mol）碘酸钾、6mol二氯甲烷、 $\\scriptstyle50\\mathrm{mL}$ 乙酸酐和 $_{32\\mathbf{g}}$ （0.4lmol）苯，在温度 $-10^{\\circ}\\mathrm{C}$ 下缓慢滴加 $25\\mathrm{mL}$ 浓硫酸，控制温度在 $-5\\%$ 以下。加毕在一 $10\\mathrm{\\sim}\\mathrm{-}5\\mathrm{\\textdegreeC}$ 反应3h，再在室温放置 $^{16\\mathrm{h}}$ 。缓慢加入 $100\\mathrm{mL}$ 蒸馏水，以水解螯合残余乙酸酐。再加入用 $26.5\\mathbf{g}$ （0.116mol）六氟砷酸钾和 $100\\mathrm{mL}$ 水配成的溶液，搅拌1h，进行复分解反应，用分液漏斗分出有机相，水层用 $\\scriptstyle50\\mathrm{mL}$ 二氯甲烷分两次萃取，与有机相合并，加乙醚一起研磨，产生 $36.7\\mathbf{g}$ 二苯基碘六氟砷酸盐，产率 $67\\%$ ，熔点 $192\\sim195\\mathrm{^\\circC}$ 。二芳基碘盐的结构和性质见表4-28。  \n\n表4-28二芳基碘盐的结构和性质  \n\n\n<html><body><table><tr><td>正离子</td><td>负离子</td><td>熔点/℃</td><td>Amax/nm</td><td>emax/[L/(mol·cm)]</td></tr><tr><td rowspan=\"3\">I+ HC ON NO2</td><td>BF</td><td>136</td><td>227</td><td>17800</td></tr><tr><td>BF</td><td>96~100</td><td>246</td><td>15400</td></tr><tr><td>AsF6</td><td>192~195</td><td>215,245</td><td>35000,17000</td></tr><tr><td>HC CH3 HC 1 CH3</td><td>BF</td><td>95～100</td><td>236</td><td>18000</td></tr><tr><td>HgC + CH3</td><td>PF6</td><td>169～173</td><td>237</td><td>18200</td></tr><tr><td>ci C1</td><td>AsF</td><td>166~167</td><td>237</td><td>17500</td></tr><tr><td>CHCONH-</td><td>AsF</td><td>194~195</td><td>240</td><td>23000</td></tr><tr><td>-NHCOCH3</td><td>AsF</td><td>232~234</td><td>275</td><td>30000</td></tr><tr><td></td><td>AsF</td><td>258~270</td><td>264</td><td>17300</td></tr></table></body></html>  \n\n（34）阴离子光引发剂取代二苯基碘盐的合成2CHCONH- +KIO+2HSO+2(CHCO)O→  \n\n![](images/b79ec084131b78bd2077bdd1304decd4d70c84406288dc870a780e75212c966d.jpg)  \n\n![](images/ac8765a9a3a13895fd3a33094da09d2010de5c9f65ef4bb60e5b0e9119dd698c.jpg)  \n\n![](images/6520c0b7a6844105f9b76b380915abe4adbc2139c136c4bc42a1d541b90c3848.jpg)  \n\n在三口烧瓶中加人27.8g（0.206mol）乙酰苯胺、乙酸酐 $35\\mathrm{mL}$ 、乙酸 $100\\mathrm{mL}$ 和浓硫酸$17\\mathrm{mL}$ ，冷至 ${<}20^{\\circ}\\mathrm{C}$ ，缓慢加人碘酸钾 $\\scriptstyle22g$ ? $\\mathrm{\\langle0.103mol\\rangle}$ ，室温搅拌反应 $24\\mathrm{h}$ 。抽滤，滤液中加入少量亚硫酸氢钠，再加入 $18.95{\\bf g}$ 1 $\\left(0.103\\mathrm{mol}\\right)$ ）六氟磷酸钾水溶液 $100\\mathrm{mL}$ ，立即有絮状沉淀生成。抽滤，沉淀经洗涤，重结晶，得到淡褐色针状结晶A $(4,4^{\\prime})$ -二乙酰氨基苯基碘盐六氟磷酸盐) $26.53g$ ，熔点 $230{\\sim}231\\mathrm{{^circ}C}$ ，产率 $47.6\\%$ ， $\\lambda_{\\operatorname*{max}}=280\\mathrm{nm}$ 。  \n\n用碘化钾代六氟磷酸钾，则得到浅黄色针状结晶碘代碘盐，熔点 $173{\\sim}1749\\mathrm{C}$ （文献 值 $176.5\\mathrm{^{\\circ}C}\\cdot$ ， $\\lambda_{\\operatorname*{max}}=280\\mathrm{nm}$ a  \n\n（35）阳离子光引发剂取代二苯基碘盐的合成  \n\n$$\n\\mathrm{I}_{2}+\\mathrm{KIO}_{3}+\\mathrm{H}_{2}\\mathrm{SO}_{4}\\longrightarrow(\\mathrm{IO})_{2}\\mathrm{SO}_{4}\n$$  \n\n$$\na_{n}\\sum\\limits_{\\mathrm{{IoH}}}+\\bigcap_{\\mathrm{NO}_{2}}\\frac{\\sqrt{\\mathrm{{IsO}}_{4}^{-}}}{2}\\left(\\bigcap\\limits_{\\mathrm{{O}}_{2}\\backslash\\square}\\bigcap\\limits_{\\mathrm{{I}}^{-}}\\bigcap_{\\mathrm{{I}}^{-}}\\prod_{\\mathrm{{I}}^{+}}\\right)^{+}\\mathbf{H}\\mathbf{S}\\mathbf{O}_{4}^{-}(\\mathbf{A})\n$$  \n\n在三口烧瓶中依次加入碘 $7.7{\\bf g}$ $\\left(0,03\\mathrm{mol}\\right)$ 、碘酸钾 $\\pmb{20}\\mathbf{g}$ 1 $\\left(0,093\\mathrm{mol}\\right)$ ，室温搅拌下滴加浓硫酸 $80\\mathrm{mL}$ ，加毕，控制温度 ${<}10^{\\circ}\\mathrm{C}$ ，剧烈搅拌下缓慢滴加硝基苯 $39.36\\mathbf{g}$ 1 $\\left(0,32\\mathrm{mol}\\right)$ ，加毕室温反应24h，升温 $40\\sim50^{\\circ}C$ 反应 $40\\mathrm{{h}}$ ，用冷水稀释反应液，析出大量沉淀，真空抽滤，用水和乙醚洗涤得淡黄色晶体A（ $(3,3^{\\prime}$ 二硝基苯基碘硫酸氢盐） $31.37g$ ，熔点 $196\\sim$ $197^{\\circ}\\mathrm{C}$ ，产率 $89.24\\%$ 。  \n\n将A $30.24\\mathbf{g}$ ? $\\left(0,08\\mathrm{mol}\\right.$ ）加人 $\\scriptstyle200\\mathrm{mL}$ 水和 $13.8\\mathbf{g}$ （0.075mol）六氟磷酸钾水溶液$100\\mathrm{mL}$ ，搅拌1h，抽滤，用水、乙醇和乙醚分别洗涤，重结晶得淡黄色晶体B（3， $3^{\\prime}$ 二硝基苯基碘盐） $12.44\\mathbf{g}$ ，熔点 $196{\\sim}198^{\\circ}\\mathrm{C}$ ， $\\lambda_{\\operatorname*{max}}=256\\mathrm{nm}$ ，产率 $32.15\\%$ 。  \n\n将硝基苯换成苯，用相同的方法制得二苯基碘六氟磷酸盐白色针状结晶，产率$51.39\\%$ ，熔点 $138{\\sim}140^{\\circ}\\mathrm{C}$ （文献值 $139\\sim141^{\\circ}\\mathrm{C}$ ， $\\lambda_{\\operatorname*{max}}{=}227\\mathrm{nm}$ 。  \n\n将六氟磷酸钾换成氧化银和氟硼酸，上述产物得到二苯基碘氟硼酸盐白色针状结晶，产率 $60\\%$ ，熔点 $137{\\sim}139^{\\circ}\\mathrm{C}$ （文献值 $136^{\\circ}\\mathrm{C}$ )， $\\lambda_{\\operatorname*{max}}=227\\mathrm{nm}$ 。  \n\n将六氟磷酸钾换成氯化铵，则得到二苯基碘盐酸盐，白色针状结晶，产率 $60\\%$ ，熔点 $227{\\sim}228^{\\circ}\\mathrm{C}$ （文献值 $225^{\\circ}\\mathrm{C}$ )， $\\lambda_{\\operatorname*{max}}=227\\mathrm{nm}$ 。  \n\n（36）阳离子光引发剂取代二苯基碘盐的合成  \n\n![](images/1c1d5c39e802dd887737f38b1b3b7dfb2332313a693c904faf90f53a0e5d37a8.jpg)  \n\n在三口烧瓶中加入氢氧化钠 $0.8\\mathbf{g}$ 1 $\\left(0.\\ 02\\mathrm{mol}\\right)$ 、丁基缩水甘油醚 $13.0{\\bf g}(0.1{\\bf m o l})$ 和苯酚$10.3{\\bf g}$ (0.1lmol)，升温至 $130^{\\circ}\\mathrm{C}$ ，搅拌反应4h，冷却后反应物溶于水，用乙醚提取，有机相用10mol/LKOH溶液洗涤后，无水硫酸镁干燥，回收溶剂得到无色液体A $19.0\\mathbf{g}$ ，产率 $85\\%$ 。  \n\n在三口烧瓶中加人 $20.4\\mathbf{g}$ （0.lmol）碘代苯、质量分数 $30\\%$ 的过氧化氢溶液 $51.0\\mathbf{g}$ $\\left(0,45\\mathrm{mol}\\right)$ 、乙酸酐 $76.58\\$ (0.75mol)，在 $45\\%$ 水浴中搅拌反应9h后，再加人对甲苯磺酸$20.9{\\bf g}$ (0.1lmol)， $45\\%$ 继续反应 $^{2\\mathrm{h}}$ ，冷却析出白色固体，抽滤，用乙醚洗涤、烘干，得B$_{19.2g}$ ，熔点 $136{\\sim}137\\mathrm{^{\\circ}C}$ （文献值 $136{\\sim}138^{\\circ}\\mathrm{C};$ ，产率 $49\\%$ （以碘代苯计)。  \n\n在三口烧瓶中加人 $\\pmb{2},688\\mathbf{g}$ (0.012mol）A、 $\\scriptstyle50\\mathrm{mL}$ 二氯甲烷，搅拌溶解，再加人 $4,7048$ $\\left(0.012\\mathrm{mol}\\right)$ ）B和 $\\scriptstyle4\\mathrm{mL}$ 冰醋酸，在 $40^{\\circ}\\mathrm{C}$ 回流4h，反应完旋转蒸发除去二氯甲烷，得淡黄色油状物，加人 $\\scriptstyle50\\mathrm{mL}$ 乙醇和 $3.108g$ （0.012mol）六氟锑酸钠，搅拌，立刻生成对甲苯磺酸钠白色沉淀，抽滤，旋转蒸发去乙醇，得黄色油状物，避光放置，结晶，用二氯甲烷/甲苯重结晶，得白色粉末C（[4-(2-羟基-3-丁氧基-1-丙氧基）苯基］苯碘六氟锑酸盐}，产率$79\\%$ ，熔点 $120.4{\\sim}121.8^{\\circ}\\mathrm{C}$ ， $\\lambda_{\\operatorname*{max}}=245\\mathrm{nm}$ D  \n\n(37) $_{4,4^{\\prime}}$ -二甲基二苯基碘盐的合成  \n\n$$\nH_{3}C-\\bigcup\\left.\\bigcup\\left.+\\mathbf{K}\\mathbf{I}\\mathbf{0}_{3}+\\mathbf{H}_{2}\\mathbf{S}\\mathbf{0}_{4}+\\ (\\mathbf{C}\\mathbf{H}_{3}\\mathbf{C}\\mathbf{0})_{2}\\mathbf{0}_{3}-\\left(\\bigcup\\limits_{\\mathbf{H}_{3}\\mathbf{C}}^{\\mathbf{i}}\\prod_{\\mathbf{C}_{H_{3}}}^{\\mathbf{i}}\\right)^{+}\\mathbf{H}\\mathbf{S}\\mathbf{0}_{4}^{-}\\right|_{\\mathbf{C}\\mathbf{H}_{3}}^{-}\n$$  \n\n在三口烧瓶中加人 $20.0\\mathbf{g}$ 碘酸钾、 $90.\\mathrm{{0mL}}$ 冰醋酸、 $40.0\\mathrm{mL}$ 醋酸酐和 $_{30\\mathrm{mL}}$ 甲苯，用冰/氯化钙浴冷至 $0\\%$ ，在大力搅拌下滴加 $30.\\ 0\\mathrm{mL}$ 冰醋酸和 $\\scriptstyle20.0\\mathrm{mL}$ 浓硫酸混合液（用冰水浴冷却，将浓硫酸在搅拌下缓慢地加人到 $0^{\\circ}\\mathrm{C}$ 冰醋酸中）滴加时温度不超过 $3^{\\circ}\\mathrm{C}$ ，体系由无色逐渐变为黄色，加毕，在冷浴下继续搅拌3h，放置过夜，溶液为棕色，还有白色固体，用冰醋酸将体系转人漏斗过滤，使滤液总体积为 $210\\mathrm{mL}$ 。在冰浴冷却和搅拌下加入 $210\\mathrm{mL}$ 蒸馏水，溶液变浑浊，最后成为橙色溶液（下层，大量）和棕色溶液（上层，少量)，将上述溶液分为两份，每份用 $200\\mathrm{mL}$ 乙醚萃取4次，合并后得黄色溶液，再加人 $11.0\\mathbf{g}$ 研细的氯化铵，一会就出现白色结晶，放置过夜，抽滤，用乙醚和蒸馏水各洗两遍，抽干，将固体用 $\\scriptstyle50\\mathbf{m}\\mathbf{L}$ 甲醇溶解，活性炭脱色，趁热过滤，旋蒸除去溶剂甲醇，得极浅黄色晶体，用 $20\\mathrm{mL}$ 甲醇重新溶解，置于冰箱中，出现无色沉淀，抽滤，用冰冻甲醇洗两遍，真空干燥，得无色粒状结晶A：4， $4^{\\prime}$ -二甲基二苯基碘盐酸盐，熔点 $86.0{\\sim}186.5\\mathrm{^\\circ}\\mathrm{C}$ 。  \n\n将 $25.0{\\mathrm{mL}}2.0{\\mathrm{mol/L}}$ 氢氧化钠溶液和 $\\scriptstyle2.0{\\mathrm{mol/L}}$ 硝酸银溶液均匀混合，产生氧化银。倾去水溶液，用蒸馏水洗三遍，抽滤，再用蒸馏水洗三遍，用 $8.6{\\bf g}$ A和 $9.3{\\tt g}$ 上述氧化银和少量水在研钵中研磨，直到看不到浅黄色固体，用 $\\scriptstyle90{\\mathrm{mL}}$ 蒸馏水将黑色浆状物洗下抽滤，再用蒸馏水洗两遍，冷却滤液，加人 $7.0\\mathrm{mL}$ 氟硼酸（ $40\\%$ ）搅拌，产生大量白色沉淀，慢慢升温至室温，抽滤 $60^{\\circ}\\mathrm{C}$ 真空干燥，得无色颗粒状晶体B：4， $4^{\\prime}\\cdot$ -二甲基二苯基碘四氟硼酸盐，熔点 $83.5\\sim86.5^{\\circ}\\mathrm{C}$ 。  \n\n（38）4， $4^{\\prime}$ -二溴二苯基碘盐的合成  \n\n$$\n2\\mathrm{I}_{2}+6\\mathrm{KIO}_{3}+11\\mathrm{H}_{2}\\mathrm{SO}_{4}\\longrightarrow5(\\mathrm{IO})_{2}\\mathrm{SO}_{4}+6\\mathrm{KHSO}_{4}+8\\mathrm{H}_{2}\\mathrm{O}\n$$  \n\n$$\n\\mathrm{Br\\longleftrightarrow(CO)_{2}S O_{4}+H_{2}S O_{4}\\longleftrightarrow(\\Delta_{B r}\\bigcup\\Sigma\\dot{\\Gamma}\\longrightarrow\\dot{\\Gamma}\\longrightarrow\\Delta_{\\Gamma}\\Delta_{\\Gamma})^{+}H S O_{4}^{-}}\n$$  \n\n$$\n(\\mathrm{~\\it~\\mathrm{{ar}~\\{~\\sum~\\dot{}~-\\langle~\\sum~-B r~\\dot{}~\\}~^{+}~\\mathrm{{RS}~\\dot{}~\\cdot~\\mathrm{{R}}~\\Omega~^{+}~\\mathrm{{RH}}_{4}C l}~}}}\\left(\\mathrm{~\\it{\\ap-\\elp-i\\elp-\\elp}~^{+}~\\cdot~\\{~\\sum~\\dot{}~-\\langle~\\sum~-B r~\\dot{}~\\epsilon~\\cdot~\\dot{}~\\epsilon~\\dot{}~\\epsilon~\\dot{}~\\epsilon~\\dot{}~\\cdot~\\ e l p-B r~\\epsilon~\\dot{}~\\cdot~\\mathrm{{RT}}~{~\\dot{}~\\cdot~\\mathrm{{R}}~\\dot{}~\\cdot~\\ e l p-\\ i\\omega^{2}~\\mathrm{{RT}}~{~\\cdot~\\mathrm{{RT}}~{~\\cdot~\\ e l p-\\ i\\omega^{2}~\\mathrm{{RT}}~{~\\cdot~\\mathrm{{RT}}~{~\\cdot~\\mathrm{{RT}}~{~\\cdot~\\ e l p-\\ i\\omega^{2}~\\mathrm{{RT}}~{~\\cdot~\\mathrm{{RT}}~{~\\cdot~\\mathrm{{RT}}~{~\\cdot~\\mathrm{{RT}}~{~\\cdot~\\mathrm{{RT}}~{~\\cdot\\mathrm~{{R T}}~{~\\cdot\\mathrm{{RT}}~{~\\cdot\\mathrm{{RT}}~{~\\cdot\\mathrm{{RT}}~{~\\cdot\\mathrm{{RT}}~{~\\cdot\\mathrm{{RT}}~{\\cdot\\mathrm{{RT}}~{~\\cdot\\mathrm{{RT}}~{\\cdot\\mathrm{{RT}}~{\\cdot\\mathrm{{RT}}~{\\cdot\\mathrm{{RT}}~{\\cdot\\mathrm{{RT}}~{\\cdot\\mathrm{{RT}}~{\\cdot\\mathrm{{RT}}~\\mathrm{{}\\cdot\\Omega}~\\mathrm{{{RT}}~\\cdot\\mathrm{{RT}}~\\mathrm{{{RT}}~\\cdot\\mathrm{{RT}}~\\mathrm{{{RT}}~\\mathrm{{~\\Omega}~\\cdot\\mathrm{{RT}}~\\mathrm{{{RT}}~\\mathrm{{~\\uT}~\\mathrm{}\\Omega~\\mathrm{{RT}}~\\mathrm{{{RT}~\\ u}~\\mathrm{{}\\Omega~\\mathrm{{RT}}~\\mathrm{{{RT}~\\ u}~\\mathrm{{}\\Omega\\Omega}~\\mathrm{{{RT}~\\ u}~\\mathrm{{}\\Omega\\Omega\\mathrm{{}\\Omega\\Omega}~\\mathrm{{{RT}~\\mathrm{\\Omega}\\Omega\\Omega{\\Omega}~\\mathrm{\\Omega\\Omega{\\Omega}\\mathrm{\\Omega\\Omega{\\Omega}\\mathrm{\\Omega\\Omega{\\Omega\\Omega}\\mathrm{\\Omega\\Omega{\\Omega\\Omega}\\mathrm{\\Omega\\Omega{\\Omega\\Omega}\\Omega\\Omega{\\\n$$  \n\n在冷水浴和剧烈搅拌下，加人 $10.0\\mathbf{g}$ （0.047mol）碘、31.2g（0.14mol）碘酸钾和$125\\mathrm{mL}$ 浓硫酸，搅拌 $^{3\\mathrm{h}}$ ，溶液由深棕色变为黄色，放置一天一夜，继续搅拌3h溶液中黄色固体增多，放置冷至 $0^{\\circ}\\mathrm{C}$ ，在大力搅拌下滴加 $525\\mathrm{mL}$ 溴苯，加毕，继续搅拌1h体系为棕灰色，慢慢升温至 $20^{\\circ}\\mathrm{C}$ ，变为棕色，搅拌 $24\\mathrm{h}$ 转为深棕色，再冷至 $5\\mathrm{^\\circC}$ ，在大力搅拌下滴加$200\\mathrm{mL}$ 蒸馏水，产生黄色浑浊， $5\\mathrm{^{\\circ}C}$ 滴加 $20\\mathrm{mL}$ 乙醚，溶液为浅黄色，下面有棕色物质，过滤，向棕色残余物加人 $100\\mathrm{mL}$ 蒸馏水，滴加 $20\\mathrm{mL}$ 乙醚，过滤，合并所有滤液，加人 $22g$ 氯化铵，迅速产生白色沉淀，过滤，用蒸馏水和乙醚各洗三遍，得无色固体，用二甲基甲酰胺重结晶两次（放热过滤不溶物)，真空干燥，得无色鳞片状晶体4， $4^{\\prime}$ -二溴二苯基碘盐酸盐，熔点 $209{\\sim}210^{\\circ}\\mathrm{C}$ ， $\\lambda_{\\operatorname*{max}}=241.5\\mathrm{nm}$ ， $\\epsilon{=}1.8{\\times}10^{4}\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{cm})$ 。  \n\n（39）二芳基碘盐型阳离子光引发剂的合成  \n\n$\\textcircled{1}$ 在三口烧瓶中加人乙酰苯胺 $27.88$ ? $\\left(0,206\\mathrm{mol}\\right)$ 、乙酸 $100\\mathrm{mL}$ 、乙酸酐 $35\\mathrm{mL}$ 和浓硫酸 $17\\mathrm{mL}$ ，冷至 $<20^{\\circ}\\mathrm{C}$ ，缓慢加人碘酸钾 $22\\mathbf{g}$ ? $\\left(0.103\\mathrm{mol}\\right)$ ，室温搅拌反应 $24\\mathrm{h}$ 。抽滤，滤液中加人少量亚硫酸氢钠，然后加人六氟磷酸钾 $18.95\\mathbf{g}$ （0.103mol）的水溶液 $100\\mathrm{mL}$ ，立即有絮状沉淀生成。抽滤沉淀经洗涤，重结晶，得到淡褐色针状晶体4,4'-二乙酰氨基苯基碘六氟磷酸盐（I）产率 $47.6\\%$ ，熔点 $230{\\sim}231^{\\circ}\\mathrm{C}$ 。  \n\n$\\textcircled{2}$ 在三口烧瓶中依次加入 $\\phantom{+}7.78$ 1 $\\left(0,03\\mathrm{mol}\\right)$ （I）、碘酸钾 $20\\mathbf{g}(0.093\\mathrm{mol})$ ，室温下搅拌滴加浓硫酸 $80\\mathrm{mL}$ ，加毕，控制温度 ${<}10^{\\circ}\\mathrm{C}$ ，剧烈搅拌下缓慢滴加硝基苯 $39.36g(0.32\\mathrm{mol})$ ，加毕室温反应 $24\\mathrm{h}$ ，升温至 $40\\mathrm{\\sim}50^{\\circ}\\mathrm{C}$ 反应 $40\\mathbf{h}$ ，冷却反应液，析出大量沉淀，真空抽滤，用水和乙醚洗涤，得淡黄色晶体3， $3^{\\prime}$ -二硝苯基碘硫酸氢盐 $31.37_{\\mathrm{{g}}}$ ，产率 $89.24\\%$ ，熔点  \n\n$196{\\sim}197\\mathrm{{\\textperthousand}}$ 。上述产物 $30.24\\mathbf{g}(0.08\\mathbf{mol})$ ，加人 $\\scriptstyle200\\scriptstyle{\\mathrm{mL}}$ 水和含六氟磷酸钾 $13.8g(0.075\\mathrm{mol})$ 的水溶液 $100\\mathrm{mL}$ ，搅拌反应1h，抽滤，用水、乙醇和乙醚分别洗涤。重结晶得到淡黄色晶体3， $\\mathbf{3^{\\prime}}$ 二硝基苯碘六氟磷酸盐（Ⅱ） $12.44g$ ，产率 $32.15\\%$ ，熔点 $196{\\sim}198^{\\circ}\\mathrm{C}$ 。  \n\n$\\textcircled{3}$ 将 $\\textcircled{2}$ 中硝基苯换成苯，用相同方法制得二苯基碘六磷酸盐（Ⅲ)，产率 $51.39\\%$ ，熔点 $138{\\sim}140^{\\circ}\\mathrm{C}$ （文献值 $139{\\sim}141\\bar{\\mathrm{\\subset}}\\rangle$ 。  \n\n$\\textcircled{4}$ 将 $\\textcircled{3}$ 产物（Ⅲ）制备中的六氟磷酸钾换成银和氟硼酸，可得到二苯基碘氟硼酸盐（IV)，产率 $60\\%$ ，熔点 $137{\\sim}139\\%$ （文献值 $136^{\\circ}\\mathrm{C}^{\\cdot}$ 。  \n\n$\\textcircled{5}$ 将 $\\textcircled{3}$ 产物（Ⅲ）制备中的六氟磷酸钾换成氯化铵，可得到二苯基碘酸盐（V），产率$60\\%$ ，熔点 $227{\\sim}228^{\\circ}\\mathrm{C}$ （文献值 $225\\%$ 。  \n\n$\\textcircled{6}$ 将 $\\textcircled{1}$ 产物（I）制备中的六氟磷酸钾换成碘化钾，可得到碘化4， $4^{\\prime}$ -二乙酰氨基苯基碘盐（VI)，熔点 $173{\\sim}174^{\\circ}\\mathrm{C}$ （文献值 $176.5\\%$ 。  \n\n（40）阳离子光引发剂三苯基硫盐的合成  \n\n![](images/f91c5a4b210f4a485560776e9cd4ba1c9420f28770767a4065324cf58af87aa7.jpg)  \n\n在三口烧瓶中加入11. $75g$ （0.025mol）二苯基碘六氟砷酸盐、 $4.65\\mathbf{g}(0.025\\mathbf{mol})\\ \\stackrel{-}{=}$ 苯基硫醚和 $0.2{\\tt g}$ 苯甲酸铜，在氮气保护下，升温至 $120{\\sim}125^{\\circ}\\mathrm{C}$ 搅拌反应 $^{3\\mathbf{h}}$ 。趁热倒入烧杯中结晶，产物用乙醚萃取三次以除去碘苯。空气干燥后得 $10.9{\\bf g}$ 亮黄色产物，产率 $96.5\\%$ .再用 $95\\%$ 的乙醇/水重结晶，得三苯基硫六氟砷酸盐，熔点 $194\\sim197^{\\circ}\\mathrm{C}$ ， $\\lambda_{\\operatorname*{max}}=227\\mathrm{nm}$ $[\\pmb{\\varepsilon}{=}21000\\mathbf{L}/(\\mathbf{mol}\\cdot\\mathbf{cm})]$ 或 $298\\mathrm{nm}$ $[\\varepsilon=10000\\mathbf{L}/(\\mathbf{mol}\\cdot\\mathbf{cm})]$ 。  \n\n（41）阳离子光引发剂取代三苯基硫盐的合成  \n\n![](images/4946270b214ba6e523ca299c88af584ed462b54610d7b4f620f324cf185455bb.jpg)  \n\n在三口烧瓶中加人 ${300}\\mathrm{mL}$ 溶剂，搅拌下加入 $55.8g$ 二苯基硫醚和适量路易斯酸催化剂，溶解后，室温下滴加 $_{35,2g}$ ， $30\\%$ 的双氧水，控制温度 ${<}30^{\\circ}\\mathrm{C}$ ，加毕室温下反应 $40\\mathbf{h}$ 。蒸去溶剂，加人 $100\\mathrm{mL}$ 蒸馏水，分出油层，水层用 $\\mathbf{3}\\times\\mathbf{3}0\\mathbf{m}\\mathbf{L}$ 氯仿萃取，合并有机层，加人无水硫酸镁干燥，蒸去溶剂，得白色固体结晶A（二苯亚矾） $59.8g$ ，收率 $98.7\\%$ ，熔点 $71{\\sim}72^{\\circ}\\mathrm{C}$ 。  \n\n在三口烧瓶中加人 $100\\mathrm{mL}$ 甲烷磺酸和五氧化二磷， $40\\sim50^{\\circ}C$ 搅拌 $\\mathsf{2}\\sim\\mathsf{3h}$ ，加入二苯亚讽 $\\mathbf{27.5g}$ 0 $\\left\\langle0.136\\mathrm{mol}\\right\\rangle$ ）和二苯基硫醚 $\\mathbf{25.3g}$ (0.136mol)， $40\\sim50^{\\circ}\\mathrm{C}$ 反应3h，将反应物倒人$200\\mathrm{mL}$ 蒸馏水中，加人 $\\mathbf{3}\\times40\\mathbf{m}\\mathbf{L}$ 二氯甲烷萃取，去掉有机层，水层加人 $25g$ 六氟磷酸钾的$\\scriptstyle500{\\mathrm{mL}}$ 水溶液搅拌 $30\\mathrm{{min}}$ ，过滤，得白色固体，真空干燥，粗品用甲醇重结晶，得产品B(4-苯硫基-苯基)-二苯基硫六氟磷酸盐，熔点 $90{\\sim}92^{\\circ}\\mathrm{C}$ ， $\\lambda_{\\operatorname*{max}}{>}300\\mathbf{nm}$ 。  \n\n（42）阳离子光引发剂取代三苯基硫盐的合成  \n\n![](images/b812bc48a35c0fae9b53d074fa8347ecf9b0efde2a5736d569b0c3d5c0fe7e71.jpg)  \n\n在三口烧瓶中依次加人 $4.53{\\bf g}$ （10mmol）二间硝基苯基碘六氟磷酸盐，二苯基硫醚$20\\mathrm{mL}(60\\mathrm{mmol})$ 和苯甲酸铜 $_{0.92g}$ （3mmol)，在氮气保护下搅拌升温至 $120^{\\circ}\\mathrm{C}$ ，反应3h，趁热将反应液倒入烧杯中自然冷却结晶，过滤，滤饼用乙醚和已烷洗涤，用乙醇-丙酸乙酯重结晶，得淡黄色晶体间硝基苯基-二苯基硫六氟磷酸盐，产率 $49.6\\%$ ，熔点 $148\\sim$ $150^{\\circ}\\mathrm{C}$ ， $\\lambda_{\\operatorname*{max}}=259\\mathrm{nm}$ 0  \n\n（43）阳离子光引发剂三苯基硫对甲苯磺酸盐的合成  \n\n![](images/4479090420a5d9b0a5d791172512e8ff9a9a0a90038f07d221b492cb4dc76532.jpg)  \n\n在三口烧瓶中加人 $3.36\\mathbf{g}$ ? $\\mathrm{:0.14mol}\\rangle$ ）镁屑和 $20\\mathrm{mL}$ 乙醚，再滴加 $23.38\\$ （0.15mol）漠苯与20mL乙醚混合液，先滴加5mL，微热使反应引发，再缓慢滴加，使体系呈微沸状态，反应平稳进行。加毕再补30mL乙醚，回流30min，使镁屑作用完全，得到黑褐色油状液体。升温至 $80^{\\circ}\\mathrm{C}$ 蒸除低沸点馏分，加入 $25\\mathrm{mL}$ 苯，将6.1g（ $\\left(0,03\\mathrm{mol}\\right)$ ）二苯亚矾溶于 $\\mathbf{35mL}$ 苯中，1h内滴加到反应体系中，回流3h，冷至室温，在冰盐浴冷却下加人 $100\\mathrm{mL}$ 、 $25\\%$ 的氢溴酸，放置，分出有机层，用 $\\scriptstyle2\\times15\\mathrm{mL}$ 、 $5\\%$ 的氢溴酸萃取两次，合并上述水层，用 $\\phantom{-}3\\times30\\mathrm{mL}$ 二氯甲烷萃取三次，合并有机层，用无水硫酸镁干燥，过滤，减压蒸馏除去溶剂，将残余物溶液置于少量二氯甲烷中，再用4倍其体积的乙醚沉淀，得到A（溴化三苯基硫盐） $5,66g$ ，产率 $55.2\\%$ （以二苯亚矾计），熔点$285\\sim287^{\\circ}\\mathrm{C}$ ，与文献值相等。 -1  \n\n在三口烧瓶中加人8.6g（0.05mol）对甲苯磺酸、5.lg（0.022mol）氧化银、100mL乙晴，避光操作，室温下搅拌反应6h，过滤除去不溶物，减压蒸馏除去溶剂，得白色固体，抽滤，用丙酮洗三次风干，得白色固体对甲苯磺酸银 $12.0\\mathbf{g}$ ，产率 $97.7\\%$ （以氧化银计)。  \n\n在三口烧瓶中加人3.43g（0.0lmol）溴化三苯基硫盐和 $_{30\\mathrm{mL}}$ 乙腈，溶解；将 $2.798$ （0.0lmol）对甲苯磺酸银溶于 $30\\mathrm{mL}$ 乙晴中(避光操作)，加入三口烧瓶中，室温搅拌反应  \n\n$22\\mathrm{h}$ ，过滤除去不溶物，减压蒸馏除去部分溶剂，冷至室温有固体析出，加入乙醚，有大量白色沉淀析出，抽滤，用 $z$ 醚洗涤，风干，得白色固体B(三苯基硫对甲苯磺酸盐)$4.2g$ ，产率 $96.8\\%$ ，重结晶时可用少量乙晴溶解，再加人乙醚析出沉淀。  \n\n（44）阳离子光引发剂二烷基苯甲酰甲基硫盐的合成  \n\n$$\n\\bigcup{\\zeta={\\bf\\zeta}_{C-\\mathrm{CH_{2}B r\\ +R_{1}S R_{2}}}^{0}}\\frac{\\mathrm{{KSbF_{6}}}}{{\\mathrm{T}{\\bf\\zeta}_{\\mathrm{H}}}}\\bigcup{\\zeta={\\bf\\zeta}_{C-\\mathrm{CH_{2}}-\\mathrm{S}+S b F_{6}}^{0}}\n$$  \n\n2-溴化苯乙酮和二烷基硫化物在非亲核阴离子的碱金属盐（如六氟锑酸钾）存在下，在丁酮（或丙酮、4-甲基戊基酮）溶剂中一步反应，生成溴化钾沉淀，反应结束，过滤除去溴化钾，再蒸馏除去溶剂，经重结晶后即得到二烷基苯甲酰甲基硫盐，为阳离子光引发剂。不同二烷基苯甲酰甲基硫盐的产率和熔点见表4-29。  \n\n表4-29不同二烷基苯甲酰甲基硫盐的产率和熔点  \n\n\n<html><body><table><tr><td>R1</td><td>R</td><td>MtXn-</td><td>产率/%</td><td>熔点/℃</td></tr><tr><td>CH3 CH</td><td>C8 H1? C12H25</td><td>SbFs PF6</td><td>84</td><td>75~76 49~51</td></tr><tr><td>CH3</td><td>C12H25</td><td>AsF6</td><td>82 87</td><td>48~50</td></tr><tr><td>CH3</td><td>C12H25</td><td>SbF6</td><td>50</td><td>58.5~60</td></tr><tr><td>CzH5</td><td>C12H25</td><td>SbF6</td><td>90</td><td>油状物</td></tr><tr><td>CzH5</td><td>C4Hz9</td><td>SbF6</td><td>77</td><td>50~52</td></tr><tr><td>CH7</td><td>Ci8 H37</td><td>SbF6</td><td>67</td><td>72~74</td></tr><tr><td>C Hg</td><td>C Hg</td><td>SbF6</td><td>60</td><td>88~89</td></tr><tr><td>C4Hg</td><td>C18 H37</td><td>SbF6</td><td>72</td><td>50~51</td></tr><tr><td>Cg H13</td><td>C6 H13</td><td>SbFs</td><td>85</td><td>油状物</td></tr><tr><td>C8H</td><td>C8 H17</td><td>SbF6</td><td>67</td><td>油状物</td></tr><tr><td>C1oH21</td><td>CoH21</td><td>SbF6</td><td>53</td><td>油状物</td></tr></table></body></html>  \n\n（45）双[4-（二苯基硫)苯基」硫化物-双氟磷酸盐的合成  \n\n![](images/ce874b246ba5732853393c894b280cfe8c078fc3512e5d105be46c9e136d54a0.jpg)  \n\n在三口烧瓶中将100g六氟磷酸钾分散在1L二氯甲烷中，搅拌下加入工业品级三苯硫盐 $50\\%$ 的水溶液{含 $50\\%\\sim60\\%$ 双［4-（二苯基硫）苯基］硫化物-氯化物），室温下搅拌2h，反应物转移到分液漏斗，用 $800\\mathrm{mL}$ 水洗3次，溶剂相浓缩至 $\\mathsf{300m L}$ ，先冷却至室温，再至0℃，每步都有沉淀，过滤收集沉淀，60℃真空干燥，得产物77.4g，用二氯甲烷重结晶，先用沸腾的二甲苯洗涤，再用已烷洗涤，60℃真空干燥得双［4-（二苯基硫）苯基］硫化物-双氟磷酸盐，熔点 $247{\\sim}250^{\\circ}\\mathrm{C}$ 。  \n\n三芳基硫盐的结构和性能见表4-30。  \n\n表4-30三芳基硫盐的结构和性质  \n\n\n<html><body><table><tr><td>正离子</td><td>负离子</td><td>熔点/℃</td><td>Amax/nm</td><td>max/[L/(mol·cm)]</td></tr><tr><td>(<)</td><td>BF</td><td>191～193</td><td>227</td><td>21000</td></tr><tr><td>(<)</td><td>AsF</td><td>195～197</td><td>227 298</td><td>21000 10000</td></tr><tr><td>CHOYK)。</td><td>PF</td><td>133~136</td><td>237 249</td><td>20400 19700</td></tr><tr><td>CH,OI<{sK).</td><td>AsF</td><td></td><td>225</td><td>21740</td></tr><tr><td>CH<YK).</td><td>BF</td><td>162~165</td><td>243 278</td><td>24700 4900</td></tr><tr><td>CH3 s+K<) CH</td><td>AsF6</td><td>111~112</td><td>275 307</td><td>42100 24000</td></tr><tr><td>HC HO- S+ HC</td><td>BF</td><td>168~169</td><td>263 277</td><td>25200 25000</td></tr><tr><td></td><td>AsF</td><td>245~251</td><td>232 280 316</td><td>3100 22400 7700</td></tr></table></body></html>  \n\n（46）阳离子光引发剂二茂铁四氟硼酸盐的合成  \n\n![](images/cfd7e33ef4e10d783ffc5103b692065b871bc32159e65bc5824744600f00f74c.jpg)  \n\n将二茂铁1.86g（0.01mol）溶解在30mL乙醚中，对苯2.16g（0.02mol）配成50mL的乙醚溶液，与二茂铁的乙醚溶液混合，然后加人含四氟硼酸3.52g（0.04mol）的50mL碘水溶液，析出蓝紫色粉末状固体，过滤并提纯，用无水乙醚充分洗涤，然后真空干燥24h，得到二茂铁四氟硼酸盐1.72g，收率63%；入=355nm［ε=1230L/(mol·cm）],$\\lambda{=}620\\mathrm{nm}$ $[\\varepsilon=221\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{cm})]$ D 足楼（47）阳离子光引发剂芳茂铁四氟硼酸盐的合成  \n\n![](images/12961749373befb0454084ea5792cf7544fcba43bc4365f2ea89771df73a2897.jpg)  \n\n![](images/cfaeed8a2dfbc05e2b7cf10c37e8def0d95b6c1c0a286261b2c273b32c1054d4.jpg)  \n\n在三口烧瓶中加入二茂铁/芳烃/三氯化铝/铝，物料摩尔比为 $1/1/3/1$ ，在回流状态下反应5h。反应结束后用冰水冷却，缓慢加人少量无水乙醇，再将反应混合物倒入装有冰水的烧杯中，分层，加人少量浓盐酸，分出水相。有机相用水萃取，合并水相。水相用环己烷萃取后，向水相加人过量四氟硼酸钠，用二氯甲烷萃取，蒸馏浓缩后加入大量环己烷，析出固体，经柱层析，蒸干溶剂，用二氯甲烷/苯（摩尔比 $^{1:1}$ ）重结晶，得芳茂铁四氟硼酸盐。  \n\n芳茂铁四氟硼酸盐的性质见表4-31。  \n\n表4-31芳茂铁四氟硼酸盐的性质  \n\n\n<html><body><table><tr><td>芳茂铁四氟硼酸盐</td><td>外观</td><td>熔点/℃</td><td>收率/%</td></tr><tr><td>环戊二烯基-铁-苯</td><td>黄色粉末状固体</td><td>173(分解)</td><td>39.7</td></tr><tr><td>环戊二烯基-铁-甲苯</td><td>黄色粉末状固体</td><td>158(分解)</td><td>43.4</td></tr><tr><td>环戊二烯基-铁-对二甲苯</td><td>黄色粉末状固体</td><td>191（分解）</td><td>72.6</td></tr><tr><td>环戊二烯基-铁-2,5-二甲基苯乙酮</td><td>黄色粉末状固体</td><td></td><td>28.1</td></tr><tr><td>乙酰基环戊二烯基-铁-对二甲苯</td><td>红色粉末状固体</td><td></td><td>52.7</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 153,
+        "chunk": "# （48）阳离子光引发剂取代芳茂铁的合成  \n\n![](images/134eaeaa9de62322c156291e2936e52885678fa13e44650fb1ea615ab88205ef.jpg)  \n\n在三口烧瓶中加入9.3g $\\left(0,05\\mathrm{mol}\\right)$ 二茂铁、 $20\\mathbf{g}$ 无水三氯化铝、1.4g铝粉、 ${50}\\mathrm{mL}$ 二苯醚，加热至 $140^{\\circ}\\mathrm{C}$ ，搅拌反应 $16\\sim24\\mathrm{h}$ ，将反应混合物倒人 $50\\mathrm{mL}$ 冰水中，分出水层，将水层用环已烷反复洗涤，向水层中加入六氟磷酸钠，析出固体，过滤，提纯、干燥，得淡黄色粉末状固体（环戊二烯基-铁-二苯醚）六氟磷酸盐，熔点 $132{\\sim}133^{\\circ}\\mathrm{C}$ ，收率 $63.2\\%$ $\\lambda{=}243\\mathrm{nm}$ $[\\epsilon=19400\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{cm})]$ ， $\\lambda{=}394\\mathrm{nm}$ $[\\pmb{\\varepsilon}=140\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{cm})]$ ， $\\lambda{=}462\\mathrm{nm}$ $[\\pmb{\\varepsilon}=75\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{cm})]$ a相比较已商品化的芳茂铁光引发剂I261（汽巴公司） $\\lambda{=}243\\mathrm{nm}\\ \\left[\\mathfrak{e}{=}12900\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{cm})\\right]$ $\\lambda{=}386\\mathrm{nm}$ $[\\varepsilon=88\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{cm})]$ ， $\\lambda{=}454\\mathrm{nm}$ $[\\pmb{\\varepsilon}{=}51\\mathbf{L}/(\\mathbf{mol}\\cdot\\mathbf{cm})]$ 8  \n\n（49）可聚合大分子光引发剂和的合成在三口烧瓶中加入 ${\\bf5.22g}$ ? $\\left(0,03\\mathrm{mol}\\right)$ ）甲苯二异氰酸酯（TDI)、3滴二月桂酸二丁基锡和无水乙酸乙酯，通氮气升温至 $45\\%$ ，缓慢滴加光引发剂2-羟基-2-甲基-1-苯基丙酮（即1173，英文缩写HAPK） $4.92g$ ? $\\left(0.\\ 03\\mathbf{mol}\\right)$ ，升温至$50^{\\circ}\\mathrm{C}$ ，反应3h，得HAPK-TDI半加成物。  \n\n在三口烧瓶中加人 $5.22g$ 1 $\\left(0,03\\mathrm{mol}\\right)$ ）甲苯二异氰酸酯、3滴二月桂酸二丁基锡和无水乙酸乙酯，通氮气，升温至 $45\\mathrm{^\\circC}$ ，缓慢滴加丙烯酸羟乙酯（HEA） $3.48g$ （0.03mol)，升温至 $50^{\\circ}\\mathrm{C}$ ，反应 $^{2\\mathrm{h}}$ ，得HEA-TDI半加成物。  \n\n将 $18\\mathbf{g}$ 1 $(\\dot{0},03\\mathbf{mol})$ 聚乙二醇加人到HAPK-TDI反应容器中，通氮气加热至 $70^{\\circ}\\mathrm{C}$ ，反应 $_{3\\sim4\\mathrm{h}}$ ，再加入HEA-TDI， $70^{\\circ}\\mathrm{C}$ 反应 $3\\sim4\\ensuremath{\\mathbf{h}}$ ，真空蒸馏除去乙酸乙酯，得到可聚合大分子光引发剂HAPK-TDI-PEG600-TDI-HEA。  \n\n（50）可聚合大分子光引发剂的合成在三口烧瓶中加入 $\\mathbf{1.74g}$ （0.01mol）甲苯二氰酸酯（TDI)、 $0.2\\mathrm{mL}$ 二月桂酸二丁基锡、无水乙酸乙酯，通氮气，升温至 $45\\mathrm{^\\circC}$ ，缓慢滴加2-羟基-2-甲基-1-苯基丙酮（光引发剂1173，英文缩写HAPK） $\\mathbf{1.64g}$ （0.0lmol)，加毕 $50^{\\circ}\\mathrm{C}$ 反应3h，得TDI-HAPK半加成物。  \n\n再加人 $\\phantom{-}7.68g$ （0.0lmol）双酚A环氧丙烯酸酯（环氧丙烯酸酯）和 $0.2\\mathrm{mL}$ 二月桂酸二丁基锡，加热至 $70^{\\circ}\\mathrm{C}$ ，反应 $_{3\\sim4\\mathrm{h}}$ ，真空蒸馏除去乙酸乙酯，得到可聚合大分子光引发剂1MAPK-TDI-环氧丙烯酸酯。若用 $0.02\\mathrm{mol}$ TDI-HAPK与0.01molEA反应，得2HAPK-TDI-环氧丙烯酸酯；用 $0.03\\mathrm{mol}$ TDI-HAPK与 $0.01\\mathrm{mol}$ EA反应，得3HAPK-TDI-环氧丙烯酸酯。  \n\n（51）乙烯基二苯酮-苯乙烯共聚物的合成  \n\n![](images/791aad9b7d08cc62833e64583c08bfaad93c240467abbe732e0614f493fb8809.jpg)  \n\n在硝基苯中，以无水三氯化铝为催化剂，使线型聚苯乙烯与苯甲酰氯反应，用盐酸溶液处理，水洗至中性，用甲醇析出，再沉淀提纯，真空干燥。  \n\n（52）大分子二苯甲酮衍生物光引发剂的合成  \n\n![](images/20cfd04ea018150c9748d8ae0ec9e748bc937d1fef3845808414bb10219d7bbb.jpg)  \n\n在三口烧瓶中加人51.3g（0.20mol）4-苯甲酰基苯氧乙酸（A)、10.4g（0.10mol）新戊二醇（B)、1.6g对甲苯磺酸和 250mL甲苯，共沸回流10h。加人100mL含有2.0g碳酸氢钠的水溶液，室温搅拌0.5h，分出水相，上层甲苯溶液用去离子水200mL洗涤两次。再回流甲苯溶液并用分水器分出水分，在旋转蒸发器上除去甲苯，得到浅黄色黏稠物新戊二醇二(4-苯甲酰基苯氧乙酸)酯(C) $55.48$ ，收率 $95.4\\%$ 。  \n\n用同样的方法将4-苯甲酰基苯氧乙酸（或2-苯甲酰基苯氧乙酸）与1,2-丙二醇，1,4-丁二醇，1,5-戊二醇，1,6-已二醇，1,9-壬二醇，2,4-二乙基，1,5-新戊二醇，3-甲基-1,5-新戊二醇，2-甲基-1,3-丙二醇，三羟甲基丙烷反应，合成大分子二苯甲酮衍生物光引发剂。  \n\n不同种类二苯甲酮的性能见表4-32～表4-34。  \n\n表4-32大分子二苯甲酮衍生物性能  \n\n\n<html><body><table><tr><td>化合物名称</td><td>收率/%</td><td>熔点/℃</td><td>HDDA中溶解度(25C)/g</td></tr><tr><td>新戊二醇(2-苯甲酰基苯氧乙酸)酯</td><td>95.0</td><td>黏稠液体</td><td>>100</td></tr><tr><td>新戊二醇二(4-苯甲酰基苯氧乙酸)酯</td><td>95.4</td><td>黏稠液体</td><td>>100</td></tr><tr><td>2,4-二乙基-1,5-新戊二醇(4-苯甲酰基苯氧乙酸)酯</td><td>96.2</td><td>黏稠液体</td><td>>100</td></tr><tr><td>3-甲基-1,5-新戊乙醇二(4-苯甲酰基苯氧乙酸)酯</td><td>95.1</td><td>黏稠液体</td><td>>100</td></tr><tr><td>3-甲基-1,3-丙二醇二(4-苯甲酰基苯氧乙酸)酯</td><td>94.8</td><td>黏稠液体</td><td>>100</td></tr><tr><td>1,4-丁二醇二(4-苯甲酰基苯氧乙酸)酯</td><td>96.4</td><td>118.9~119.4</td><td>1</td></tr><tr><td>1,2-丙二醇二(4-苯甲酰基苯氧乙酸)酯</td><td>80.0</td><td>113.7~118.0</td><td>5</td></tr><tr><td>1,5-戊二醇二(4-苯甲酰基苯氧乙酸)酯</td><td>94.6</td><td>51.0~53.4</td><td>>100</td></tr><tr><td>1,6-己二醇二(4-苯甲酰基苯氧乙酸)酯</td><td>95.8</td><td>107.5~108.3</td><td>1</td></tr><tr><td>1,9-壬二醇二(4-苯甲酰基苯氧乙酸)酯</td><td>93.2</td><td>69.9~72.8</td><td>10</td></tr><tr><td>三羟甲基丙烷三(4-苯甲酰基苯氧乙酸)酯</td><td>90.0</td><td>松香状固体</td><td>>100</td></tr></table></body></html>  \n\n表4-33不同种类二苯甲酮光引发剂的固化速率与硬度关系  \n\n\n<html><body><table><tr><td>固化速率/(m/min)</td><td>BP</td><td>PL2505</td><td>A</td><td>B</td></tr><tr><td></td><td>0.740</td><td>0.607</td><td>0.476</td><td>一</td></tr><tr><td>6</td><td>0.833</td><td>0.631</td><td>0.569</td><td>一</td></tr><tr><td>4</td><td>0.833</td><td>0.736</td><td>0.702</td><td>0.433</td></tr><tr><td>3</td><td>0.833</td><td>0.829</td><td>0.798</td><td>0.489</td></tr><tr><td>2</td><td>0.833</td><td>0.833</td><td>0.833</td><td>0.516</td></tr></table></body></html>\n\n注：试验配方为6145-10035份，EO-TMPTA30份，HDDA30份，ED2.5份，光引发剂7.5份。BP 为二苯甲酮（工业品)，PL2505为新戊二醇二(4-苯甲酰基苯氧乙酯)酯（小试样品)，A与B为市售大分子二苯甲酮类光引发剂。  \n\n表4-34不同种类二苯甲酮光引发剂的性能比较  \n\n\n<html><body><table><tr><td>性能</td><td>BP</td><td>PL2505</td><td>A</td><td>B</td></tr><tr><td>黄变性 迁移性(水) 迁移性(3%的乙酸)</td><td>0.56 100.0 100.0</td><td>0.55 9.1 3.6</td><td>0.56 41.9. 14.8</td><td>0.56 37.8 31.2</td></tr></table></body></html>  \n\n（53）大分子二苯甲酮光引发剂的合成  \n\n![](images/9e1d4257c2b0c48858a7124b8c0c186dfa1b350b2a77302fe4ee24e73af00520.jpg)  \n\n在三口烧瓶中加入 $5.2g$ （ $\\scriptstyle30\\mathrm{mmol})$ ）甲苯二异氰酸酯、1mL二月桂酸二丁基锡和 $150\\mathrm{mL}$   \n乙酸乙酯，搅拌升温至 $50^{\\circ}\\mathrm{C}$ ，滴加 $6\\mathbf{g}$ （ $\\mathsf{30m m o l},$ ）4-羟基二苯甲酮和 $60\\mathrm{mL}$ 乙酸乙酯溶液，  \n加毕升温至 $60^{\\circ}\\mathrm{C}$ 反应 $^{3\\mathrm{h}}$ ，红外监测 $\\mathsf{3400c m^{-1}-O H}$ 峰消失，再加人 $3.4\\mathbf{g}$ (16mmol) $_{4,4^{\\prime}}$   \n二羟基二苯甲酮和 $\\scriptstyle60\\mathbf{m}\\mathbf{L}$ 乙酸乙酯溶液，加毕升温至 $78\\%$ 反应3h，红外监测 $2272\\mathrm{cm}^{-1}$   \n—NCO峰消失反应结束，分别用 $10\\%$ 的氢氧化钠溶液和去离子水洗涤3次，减压蒸馏除去  \n溶剂得固体产物大分子二苯酮光引发剂， $\\lambda_{\\operatorname*{max}}{=}284\\mathrm{nm}$ ， $\\bullet{=}1960\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{cm})$ ，产率 $85\\%$ 。（54）大分子二苯甲酮光引发剂的合成  \n\n![](images/4fd5799eaf7555cc09050bf7ef75ef491541de8b23b67b85596aa0ca1b5b4a8b.jpg)  \n\n在三口烧瓶中加入甲苯二异氰酸酯 ${\\mathfrak{s}},2{\\mathfrak{g}}$ （ $\\mathsf{30m m o l},$ 、1mL二月桂酸二丁基锡和 $150\\mathrm{mL}$ 乙酸乙酯，搅拌升温至 $50\\mathrm{^\\circC}$ ，滴加 $6.4\\mathbf{g}$ （ $\\mathsf{30m m o l}.$ ）4-羟甲基二苯甲酮和 $60\\mathrm{mL}$ 乙酸乙酯混合液，加毕升温至 $60^{\\circ}\\mathrm{C}$ 反应3h，红外监测 $3400\\mathsf{c m}^{-1}$ 一OH峰消失，再滴加 $1.8\\mathbf{g}$ ? $\\scriptstyle(16\\mathrm{mmol})$ 对苯二酚和 $60\\mathrm{mL}$ 乙酸乙酯混合液，升温至 $78\\mathrm{{^\\circC}}$ 反应 $^{3\\mathrm{h}}$ ，红外监测 $2250\\mathsf{c m}^{-1}$ —NCO峰消失，停止反应，用 $10\\%$ 的氢氧化钠溶液和蒸馏水各洗3次，用无水硫酸镁干燥过夜，旋蒸除去溶剂，得浅黄色粉末状产物大分子二苯甲酮光引发剂， $\\lambda_{\\operatorname*{max}}=252.5\\mathrm{nm}$ ， $\\varepsilon=5700\\mathrm{L}/\\$ $(\\mathbf{mol}\\cdot\\mathbf{cm})$ ，产率 $73.4\\%$ 。  \n\n（55）大分子二苯甲酮光引发剂的合成  \n\n![](images/4f16e87d0855d3cb74d306e2549120281e264105658e66a0ede41897f01f0df0.jpg)  \n\n![](images/7902e26573de15b935bd9f9be8602d82bc3af4a29ae6aaed89c610adce9f9428.jpg)  \n\n将5.2g（30mmol）甲苯二异氰酸酯、1mL二月桂酸二丁基锡和150mL乙酸乙酯加人三口烧瓶中，升温至60℃，缓慢滴加含有4-羟基二苯甲酮6.0g（30mmol）的60mL乙酸乙酯溶液，反应3h，当红外监测3450cm-1—OH峰消失时，再加入含对苯二酚1.7g（16mmol）的20mL乙酸乙酯溶液，升温至78℃，反应3h，当红外监测无2272cm-1—NCO峰时，反应结束，分别用10%的氢氧化钠溶液和去离子水洗3次，减压蒸馏除去溶剂，得到产物大分子二苯甲酮光引发剂，max=283nm，e=30086L/(mol·cm)，产率85%。  \n\n（56）4(4-二甲氨基苯乙烯基)二苯甲酮的制备  \n\n![](images/131e1d507e0c0af248127055c1663557d90b46613736b7b24cf0fb1c9a30cbcb.jpg)  \n\n在三口烧瓶中加入150mL干燥苯、25g对甲基苯甲酸，加热至沸腾，在快速搅拌下滴加45mL二氯亚矾，回流4h，停止反应，减压蒸馏，收集60～77℃/5333Pa馏分，得对甲基苯甲酰氯A。  \n\n在三口烧瓶中加入100mL千燥苯、16.8g三氯化铝，加热至沸腾，滴加13.3g新制备的A，回流3h，停止反应，冷却，以12%的HCl破坏掉三氯化铝，有机相减压蒸馏，收集$180{\\sim}181^{\\circ}\\mathrm{C}/333\\mathrm{Pa}$ 馏分，产物为白色固体B (对甲基二苯甲酮)，熔点 $56\\sim57^{\\circ}C$ ..p  \n\n在三口烧瓶中加人10gB、10g溴代丁二酰胺、100mL四氯化碳，加热回流，溶液逐渐变红，冷却，停止反应，析出固体，过滤，固体用无水乙醇重结晶两次，得浅黄色晶体C(对溴甲基二苯甲酮)，熔点104～106℃。 X 梦  \n\n在三口烧瓶中加入45mL苯、10.49g（0.04mol）三苯基麟和1lg（0.04mol）C，待全部溶解后，室温搅拌，逐渐有固体生成，3h停止反应，抽滤所得固体为D（溴化三苯基麟亚甲基二苯甲酮)，用苯洗涤，真空干燥备用。 8  \n\n在三口烧瓶中加人20mL二氯甲烷、3g（0.02mol）对二甲氨基苯甲醛及10.7g（0.02mol）D，待全部溶解后，在剧烈搅拌下，滴人150mL的50%的氢氧化钠水溶液，反应液逐渐变为橘红色，加毕，继续反应1h，补加10mL蒸馏水和10mL苯，再用分液漏斗除去水相，有机相用饱和食盐水洗涤5次，并用无水碳酸钾干燥，蒸去有机溶剂，得黄色固体，用无水甲醇重结晶两次，得浅黄色片状结晶 $(4,4^{\\prime}$ -二甲氨基苯乙烯基)二苯甲酮， $\\lambda_{\\operatorname*{max}}=396\\mathrm{nm}$ 4 $\\epsilon{=}4.18\\times10^{4}\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{cm})$ ，熔点 $197^{\\circ}\\mathrm{C}$ 。  \n\n（57）含硅大分子二苯甲酮光引发剂的合成  \n\n![](images/b277847fb3c7df2860a19d9cfd16bdc10182223026a7f73045a451e8d6e99a7f.jpg)  \n\n在三口烧瓶中加人 $7.0\\mathbf{g}$ （2.5mmol）端羧基甲基硅烷（德固萨公司C-Si2342)、二环己基碳化二亚胺（DCC）1.133g（5.5mmol）和150mL乙酸乙酯，搅拌30min，滴加0.99g(5mmol）4-羟基二苯甲酮和 $10\\mathrm{mL}$ 乙酸乙酯溶液，室温反应 $24\\mathrm{h}$ ，过滤，滤液用 $5\\%$ 的氢氧化钠溶液和去离子水洗三次，减压蒸馏除去溶剂，得到液态产物，含硅大分子二苯甲酮光引发剂。  \n\n（58）含硅大分子光引发剂的合成  \n\n![](images/63b00fdb8494872fe83cd98041702c433962924d77655ad45135433735e18aa9.jpg)  \n\n在三口烧瓶中加入 $\\boldsymbol{7}.0\\mathbf{g}$ （ $\\cdot2.\\ 5\\mathrm{mmol})$ 端羧基甲基硅烷（德固萨公司C-Si2342）、二环己基碳化二亚胺（DCC） $1.1338$ $\\left(5,5\\mathrm{mmol}\\right)$ 和 $150\\mathrm{mL}$ 乙酸乙酯，搅拌 $30\\mathrm{min}$ ，滴加 $\\mathbf{1.02g}$ （5mmol）光引发剂184和 $10\\mathrm{mL}$ 乙酸乙酯溶液，室温反应 $24\\mathrm{h}$ ，过滤，滤液用 $5\\%$ 的氢氧化钠溶液和去离子水洗3次，减压蒸馏除去溶剂，得到液态产物含硅大分子光引发剂。  \n\n（59）含硅光引发剂的合成  \n\n![](images/5d3e29b1d8d232697d87d0242345a2c7fa0f5a92422fe3ade6e216051eb8cf47.jpg)  \n\n在三口烧瓶中加入 $12.52g$ ? $\\left(0.05\\mathrm{mol}\\right)$ ）异氰酸酯基丙基三乙氧基硅烷（IPS）、 $50\\mathrm{mL}$ 无水乙酸乙酯和 $0.2g$ 二月桂酸二丁基锡，搅拌升温至 $75\\mathrm{^\\circC}$ ，滴加 $6.56g$ ? $\\left(0,05\\mathrm{mol}\\right)$ 光引发剂1173，2h内加毕，在 $75\\mathrm{^\\circC}$ 避光条件下反应3h，当红外检测 $3463c m^{-1}$ 的-OH峰和$2268\\mathsf{c m}^{-1}$ 的—NCO峰消失后，停止反应，旋转蒸除去溶剂后再得用乙酸乙酯/正已烷（1/3，体积比）为洗脱剂对合成产物进行柱色谱分离，得到无色透明的液体，即为含硅的光引发剂，产率 $87\\%$ 口  \n\n（60）大分子阳离子光引发剂聚苯乙烯-碘盐六氟锑酸盐的合成  \n\n![](images/1d1a2420a5644fa727da743af9591d650f4c20c7aeda461111ce4bb19dd3e3f5.jpg)  \n\n在三口烧瓶中加入20.4g（0.1mol）碘代苯，滴加38g（0.2mol）40%的过氧乙酸，在$40\\%$ 水浴中搅拌反应2h后，再分批加入 $20.9{\\bf g}$ （0.11mol）对甲苯磺酸继续在此温度下反应2h，析出白色固体，经抽滤，用乙醚洗涤，烘干，得到羟基对甲磺酰氧基碘苯。以碘代苯计产率 $80\\%$ ，熔点为 $136{\\sim}137^{\\circ}\\mathrm{C}$ 。  \n\n将 ${\\ 5.2g\\ }$ 聚苯乙烯溶解在 $30\\mathrm{mL}$ 二氯甲烷中，再加人 $\\ 3.\\ 92g$ $\\left(0.01\\mathrm{mol}\\right.$ ，相当于苯乙烯单元物质的量的1/5）羟基对甲磺酰氧基碘苯和冰醋酸1mL，在40℃下反应12h，反应完后旋转蒸发蒸去二氯甲烷。在所得的淡黄色油状物中加人 $2.59g$ （0.01mol）六氟锑酸钠，搅拌，有对甲苯磺酸钠白色沉淀产生，抽滤除去沉淀，取上层液体用甲醇/水沉淀三次，抽滤后真空干燥得到固体至恒重，为聚苯乙烯-碘六氟锑酸盐（PS-ISbF6）。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 154,
+        "chunk": "# （61）带光引发基的低聚物的合成  \n\n将甲基丙烯酸甲酯 $12.50\\mathbf{g}$ （ $125\\mathrm{mmol})$ 、丙烯酸 $25.00\\mathbf{g}$ （347.2mmol）、丙烯酸丁酯$12.50\\mathbf{g}$ （97.7mmol）混合，加人 $0.75{\\bf g}$ 偶氮二异丁腈使之溶解，倒入滴液漏斗中。在三口烧瓶中加入 $70\\mathbf{g}$ 乙二醇单甲醚，升温到 $80^{\\circ}\\mathrm{C}$ ，通氮气0.5h，慢慢滴加混合单体， $85^{\\circ}\\mathrm{C}$ 反应$5\\mathord{\\sim}6\\mathbf{h}$ ，冷却，反应物倒人水中使聚合物析出，反复洗涤，真空干燥 $50^{\\circ}\\mathrm{C}\\times24\\mathrm{h}$ ，得高分子酸，数均分子量6956，重均分子量13223，多分散性1.90；酸值 $436.88\\mathrm{mg}\\mathrm{KOH/g}.$ 。  \n\n在三口烧瓶中加人高分子酸 $5.00\\mathbf{g}$ 、 $60\\mathrm{mL}$ 四氢呋喃，超声振荡 $15\\mathrm{{min}}$ ，得清澈溶液，升温至 $60^{\\circ}\\mathrm{C}$ ，慢慢滴加二氯亚矾，使其保持微沸反应 ${\\mathfrak{6}}\\sim7{\\mathrm{h}}$ ，停止加热，旋蒸除去溶剂，用正己烷多次洗涤，真空干燥 $30^{\\circ}\\mathrm{C}$ ， $24\\mathbf{h}$ ，得高分子酰氯。  \n\n将高分子酰氯 $2.80\\mathbf{g}$ 完全溶于 $60\\mathrm{mL}$ 四氢呋喃中，倒人用铝箔包裹的三口烧瓶中，加人三乙胺 $\\phantom{-}3.\\phantom{-}03g$ C $\\mathbf{\\left(30.0mmol\\right)}$ ，升温到 $60^{\\circ}\\mathrm{C}$ ，慢慢滴加光引发剂1173（2-羟基-2-甲基苯基丙酮） $0.432g$ ? $\\left(2.63\\mathrm{mmol}\\right)$ ）回流反应 $6\\mathrm{h}$ 。再慢慢滴加丙烯酸羟乙酯 $2.697_{8}$ （23.3mmol)，保温 $40^{\\circ}\\mathrm{C}$ ，反应 $6\\mathrm{h}$ ，避光旋转蒸除溶剂，用正已烷洗涤，真空干燥 $48\\mathrm{h}$ 制得带光引发基的低聚物。  \n\n（62）含光引发基的超支化低聚物的合成  \n\n![](images/7a699cabd7b708af18329c417ee5f83a80a1dbef2e2470bf9cc999e27486c94f.jpg)  \n\n![](images/27d99f98a1ab41847baa04dcec375e5b829333202484e45ae1415d5c3a4a9a2e.jpg)  \n\n在三口烧瓶中加人 $10.00\\mathbf{g}$ 丁二酸酐、 $19.90\\mathbf{g}$ 光引发剂184（1-羟基环已基苯基酮）、$100\\mathrm{mL}$ 二甲基甲酰胺，在搅拌和氮气保护下升温至 $110{\\sim}115^{\\circ}\\mathrm{C}$ 开始反应，每0.5h取样测酸值至酸值恒定，得A。  \n\n搅拌下在2h内将A滴加到盛有 $30.77_{\\mathbf{g}}$ 乙二醇二缩水甘油醚的三口烧瓶中，反应至体系酸值恒定。在反应中控制乙二醇二缩水甘油醚的量，使其环氧物质的量是丁二酸酐物质的量的两倍，反应结束后在产品B中保留一个环氧基（用盐酸-丙酮法测反应开始和反应结束时体系的环氧值为 $2:1)$ 。  \n\n在三口烧瓶中加入 $1.36g$ 季戊四醇、 $7.68g$ 偏苯三酸酐和适量二甲基甲酰胺，在搅拌和氮气保护下，升温至 $110{\\sim}115^{\\circ}\\mathrm{C}$ ，每0.5h取样测酸值至恒定；加人 $7.40\\mathbf{g}$ 环氧氯丙烷，反应至酸值恒定；加人 $15.36\\mathbf{g}$ 偏苯三酸酐反应至酸值恒定，如此重复反应至超支化聚合物C分子外围含32个羧基。  \n\n在三口烧瓶中加人 $9.97{\\tt g}$ 甲基丙烯酸缩水甘油酯（GMA)、 $8.88\\mathbf{g}$ B、二甲基甲酰胺，升温至 $90{\\sim}95\\mathrm{^\\circC}$ ，滴加 $67.72g\\mathrm{~C~}$ ，反应至酸值恒定，得到含光引发基团的超支化低聚物D。含光引发剂的超支化低聚物的酸值和黏度见表4-35。  \n\n表4-35含光引发剂的超支化低聚物的酸值和黏度  \n\n\n<html><body><table><tr><td>n(GMA):n(--COOH)</td><td>n(184):n(—COOH)</td><td>酸值/(mgKOH/g)</td><td>黏度/mPa·s</td></tr><tr><td>8:32</td><td>2:32</td><td>214.5</td><td>88.0</td></tr><tr><td>8:32</td><td>4:32</td><td>175.3</td><td>132.0</td></tr><tr><td>8:32</td><td>6:32</td><td>169.1</td><td>228.0</td></tr><tr><td>8:32</td><td>8:32</td><td>163.0</td><td>190.8</td></tr><tr><td>8:32</td><td>10:32</td><td>141.1</td><td>65.7</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 155,
+        "chunk": "# （63）带叔胺基的大分子光引发剂的合成  \n\n![](images/538617aff2001ddebac346881e6bd90c81738b43a4d9ff3a0a7b6f1f1d883bd3.jpg)  \n\n在三口烧瓶中加人 ${\\ 5.2g}$ 甲苯二异氰酸酯、 $\\scriptstyle1\\arg L$ 二月桂酸二丁基锡和 $150\\mathrm{mL}$ 乙酸乙酯，加热至 $50^{\\circ}\\mathrm{C}$ ，搅拌下滴加 $68~4\\AA$ -羟基二苯甲酮和 $60\\mathrm{mL}$ 乙酸乙酯混合液，加毕升温至 $60^{\\circ}\\mathrm{C}$ ，保温反应 $^{3\\mathrm{h}}$ 。再滴加 $2,78\\ N,N\\mathrm{-}$ 二甲基乙醇胺和 ${60}\\mathrm{mL}$ 乙酸乙酯混合液，加毕升温至 $78\\%$ ，反应 $^{3\\mathrm{h}}$ ，将反应后的有机层分别用 $10\\%$ 的 ${\\tt N a O H}$ 和蒸馏水洗2次，再用无水 $\\mathrm{Na_{2}S O_{4}}$ 干燥，用旋转蒸发除去乙酸乙酯，得到浅黄色的产品—带叔胺基的大分子光引发剂。  \n\n（64）可见光引发剂樟脑的合成  \n\n![](images/d5416754db3cdc54e024aa054b8ef6f855e946cbb961be737c679c33dc59bab4.jpg)  \n\n在三口烧瓶中加入 $38\\mathbf{g}$ （ $\\scriptstyle250\\ m\\mathbf{m}\\circ1$ ）樟脑，油浴加热至 $80^{\\circ}\\mathrm{C}$ ，搅拌滴加溴 $_{40\\mathbf{g}}$ $\\scriptstyle(250{\\mathrm{mmol}})$ ， $30\\mathrm{{min}}$ 滴完，在 $80^{\\circ}\\mathrm{C}$ 搅拌反应3h。直到无溴化氢气体放出为止。把反应后的溶液倒入 $\\scriptstyle400\\mathrm{mL}$ 冰水中，得到粗品A（3-溴樟脑)，再用 $_{30\\mathrm{mL}}$ 无水乙醇重结晶，得到产品$38g$ （164.5mmol)，熔点 $74{\\sim}76^{\\circ}\\mathrm{C}$ 。  \n\n在三口烧瓶中加人 $_{5{\\bf g}}$ （ $33.3\\mathrm{mmol}$ ）碘化钠、 $0.5{\\bf g}$ 醋酸钴、 $30\\mathrm{mL}$ 二甲亚矾、 $_{5{\\bf g}}$ （21.6mmol）3-溴樟脑，鼓入空气，加热到 $150^{\\circ}\\mathrm{C}$ ，反应6h后将反应液倒人 ${500}\\mathrm{mL}$ 水中，加入少量硫代硫酸钠，用 $100\\mathrm{mL}$ 乙酸乙酯萃取，水层用乙酸乙酯提取5次（ $\\scriptstyle\\left.30\\mathbf{m}\\mathbf{L}\\times5\\right)$ ，合并有机层，水洗2次，用无水硫酸钠除水。过滤、减压蒸馏除去溶剂，得樟脑粗品，用正已烷重结晶得黄色针状结晶 $2.6g$ C $\\mathbf{\\langle15.7mmol\\rangle}$ ，熔点 $196{\\sim}198^{\\circ}\\mathrm{C}$ ，收率 $72\\%$ 。  \n\n（65）N-取代硫代叶啶酮的合成  \n\n![](images/9b8a775cb95b45dffd98e5f3a64f1e2c9bf30f8f7729334d1d9d186818374a27.jpg)  \n\n在三口烧瓶中加入 $0.26\\mathrm{mol}$ 邻氯苯甲酸、1mol苯胺、 $0.3\\mathrm{mol}$ 的缚酸剂和 $0.0125\\mathrm{mol}$ 的催化剂，混合后加热回流 $_{2\\sim3\\mathrm{h}}$ ，除去未反应的原料，用盐酸将反应产物沉淀析出，过滤得灰白色粗品，用醇-水混合物重结晶，得纯的2-羧酸二苯胺衍生物A。  \n\n将 $20\\mathbf{g}$ A溶于 $\\scriptstyle8\\mathrm{mol}$ 浓硫酸中，加热 $15\\mathrm{min}$ ，然后将产物注入水中，析出沉淀，过滤，水洗，重结晶得到黄色固体吖啶酮B。  \n\n将5gB、 $20\\mathrm{mol}$ 丁酮、 $40\\%$ 的氢氧化钠溶液 $20\\mathrm{mL}$ 、 $\\boldsymbol{150}\\mathbf{mg}$ 相转移催化剂加入三口烧瓶中，水浴加热，搅拌下滴加 $\\scriptstyle4\\mathrm{mL}$ 烷基化试剂，反应1h，反应完后将反应混合物注人热水中沉淀，析出产物，过滤、洗涤、烘干，得到 $N\\cdot$ 取代吖啶酮C。  \n\n将 $\\scriptstyle2_{\\mathbf{{\\mathbf{g}}}}\\mathbf{\\mathbf{\\mathbf{C}}}$ 和 $_{\\mathbf{14mL}}$ 三氯氧磷混合，水浴加热， $75^{\\circ}\\mathsf{C}$ 反应1h，将反应物倒人 $100\\mathrm{mL}$ 冰水混合物中，溶液呈橘黄色，加入 $\\scriptstyle1{\\mathrm{mol/L}}$ 硫代硫酸钠，马上有砖红色产物析出，过滤、水洗，用苯重结晶，得到N-取代硫代吖啶酮（D)。  \n\n五种硫代吖啶酮的结构与性能见表4-36。  \n\n表4-36五种硫代吖啶酮的结构与性能  \n\n\n<html><body><table><tr><td>编号</td><td>硫代吖啶酮</td><td>/nm Amax</td><td>Emax /L/(mol·cm)]</td><td>光分解速度 /(K/s)</td><td>相对感度 (留膜级数)</td></tr><tr><td>1</td><td>S</td><td>483</td><td>2.304×104</td><td>0.2365</td><td>7</td></tr><tr><td>2</td><td>CH2 S</td><td>485</td><td>2.309×104</td><td>0.2048</td><td>？</td></tr><tr><td>3</td><td>CH7 S</td><td>490</td><td>2.76×104</td><td>0.1981</td><td>00</td></tr><tr><td>4</td><td>S C3HrOCH3</td><td>478</td><td>0.36×10</td><td>0.0186</td><td>4</td></tr><tr><td>5</td><td>CHrC1 S</td><td>481</td><td>0.053×104</td><td>0.0185</td><td>2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 156,
+        "chunk": "# (66）双-(对-二甲氨基亚苄基)丙酮的合成  \n\n![](images/af614d3e022afe4caa4ea501ad30869449a83eca631b3bfc2d34e50094eee7bd.jpg)  \n\n在三口烧瓶中加人45mL无水乙醇，再加人4.50g（0.03mol）对二甲氨基苯甲醛，待全部溶解后，再加人0.89g（0.015mol）丙酮，混合均匀后，滴加15%的氢氧化钠水溶液10mL，边加边搅拌，加毕室温下反应1.5h，出现黄色浑浊，再在45℃继续反应2h，出现大量橙色固体，冷却、抽滤，用甲苯重结晶两次，得橙色片状结晶，即为对-(对-二甲氨基亚苄基)丙酮， $\\lambda_{\\operatorname*{max}}{=}432\\mathrm{nm}$ ， $\\epsilon{=}5.81{\\times}10^{4}\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{cm})$ ，熔点 $194^{\\circ}\\mathrm{C}$ 。  \n\n（67）双-亚苄基丙酮的合成  \n\n$$\n2\\bigcup-\\mathrm{CHO}+\\mathrm{H}_{3}\\mathrm{C}-\\mathrm{CH}_{3}\\xrightarrow[\\mathrm{NaOH}]{0}\\bigcup-\\mathrm{CH}-\\mathrm{CH}-\\mathrm{CH}-\\mathrm{CH}-\\bigcup \n$$  \n\n参照上述反应，类似条件，用苯甲醛代对二甲氨基苯甲醛，合成双-亚苄基丙酮，max=$322\\mathrm{nm}$ ， $\\epsilon{=}3.21{\\times}10^{4}\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{cm})$ ，熔点 $111^{\\circ}\\mathrm{C}$ 。  \n\n![](images/268b06eac990385c00698068121aa7596993f70d0067827f5ed75b35fd8e50c4.jpg)  \n\n用亚苄基丙酮代对二甲氨基苯甲醛，合成对二甲氨基双亚苄基丙酮，max=418nm，$\\epsilon{=}3.21{\\times}10^{4}\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{cm})$ ，熔点 $158^{\\circ}\\mathrm{C}$ 。  \n\n![](images/9822ade1ebe078ec5a0b96ef47c0d23012701c9f114420f4b584dc9cdff8998f.jpg)  \n\n用环戊酮合成双（对二甲氨基双亚苄基）环戊酮， $\\lambda_{\\mathrm{max}}{=}472\\mathrm{nm},\\ \\varepsilon{=}6.10{\\times}10^{4}\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{cm})$ 熔点 $198^{\\circ}\\mathrm{C}$ 。  \n\n（68）4-二甲氨基亚苄基-苯乙酮的合成  \n\n$$\n(C H_{3})_{2}N-C_{2}\\rightarrow C H O+C H_{3}\\overrightarrow{C}-\\Bigg<C H_{3}\\xrightarrow[]{\\mathrm{~NaOH~}}(C H_{3})_{2}N-C_{2}\\Bigg>-C H_{3}-C H-C-\\Bigg<_{2}O\n$$  \n\n在三口烧瓶中加入 $4.5{\\bf g}$ 1 $\\left(0,03\\mathrm{mol}\\right)$ 对二甲氨基苯甲醛、 $30\\mathrm{mL}$ 无水乙醇，待全部溶解后，再加人 $3.6g$ $\\left(0,03\\mathrm{mol}\\right)$ 苯乙酮，混匀，在快速搅拌下，慢慢滴加 $6\\mathrm{mL}$ ， $15\\%$ 的氢氧化钠水溶液，开始滴人时溶液逐渐变为橘红色，然后析出大量黄色固体，室温下反应4h后停止，抽滤，样品以无水甲醇重结晶两次，得黄色晶形固体为4-二甲氨基亚苄基苯乙酮， $\\lambda_{\\operatorname*{max}}=$ $406\\mathrm{nm}$ ， $\\epsilon{=}3.8{\\times}10^{4}\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{cm})$ ，熔点 $109.5^{\\circ}\\mathrm{C}$ 。  \n\n按类似合成方法合成：  \n\n$$\n(\\mathrm{CH_{3}})_{2}\\mathrm{N}-\\bigcup_{i=1}^{\\infty}-\\mathrm{CH}0+\\mathrm{CH}_{3}^{0}\\bigcup_{i=1}^{\\infty}-\\bigcup_{j=1}^{\\infty}-\\mathrm{OCH}_{3}\\xrightarrow[\\mathrm{NaOH}]{\\mathrm{NaOH}}(\\mathrm{CH}_{3})_{2}\\mathrm{N}-\\bigcup_{i=1}^{\\infty}-\\mathrm{CH}-\\mathrm{CH}-\\bigcup_{i=1}^{0}-\\bigcup_{j=1}^{\\infty}\n$$  \n\n用4-甲氧基苯乙酮代苯乙酮，得4-二甲氨基亚苄基， $4^{\\prime}$ -甲氧基苯乙酮， $\\lambda_{\\operatorname*{max}}=402\\mathrm{nm}$ $\\varepsilon{=}4.\\ 0{\\times}10^{4}\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{cm})$ ，熔点 $137.5\\mathrm{^{\\circ}C}$ 。  \n\n$$\n(C H_{3})_{2}N-C=C H_{3}+C H_{3}C-C_{2}=C l\\xrightarrow[]{\\mathrm{0}}C H_{3}\\uparrow(C H_{3})_{2}N-C_{2}-C H-C H-C_{2}(C)-C u\n$$  \n\n用4-氯苯乙酮代苯乙酮，得4-二甲氨基亚苄基， $4^{\\prime}$ -氯苯乙酮 $\\lambda_{\\operatorname*{max}}=406\\mathrm{nm}$ ， $\\varepsilon{=}3.50\\times$ $10^{4}\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{cm})$ ，熔点 $140^{\\circ}\\mathrm{C}$ 。  \n\n（69）水性 $\\alpha$ -氨基酮光引发剂的合成  \n\n![](images/c9aba79e02cae5d09e79a1af0537cb27b488cd4e79ad50001703e2aaca9e3763.jpg)  \n\n![](images/2f087d52370de9d98460fd49d7fef12e42921652ac913dab19074bd26b568baa.jpg)  \n\n在三口烧瓶中加人 $50\\mathbf{g}$ ? $\\left(0,37\\mathrm{mol}\\right)$ 乙酰苯胺、 $120\\mathbf{g}$ C $\\left.0,90\\mathrm{mol}\\right)$ ）无水三氯化铝和适量溶剂，室温搅拌下缓慢滴加 $42\\mathrm{mL}$ （0.48mol）丙酰氯，回流5h，冷至室温，将反应液在剧烈搅拌下缓慢倒人冰水-盐酸中，析出沉淀经水洗、重结晶得到A $40.5{\\bf g}$ ，熔点 $167\\sim169^{\\circ}\\mathrm{C}$ ，产率 $57.3\\%$ 8  \n\n取23g（ $\\scriptstyle\\left(0,12{\\bmod{\\right)}}$ ）A和适量乙醇，剧烈搅拌下缓慢滴加 $20.8\\mathbf{g}$ （0.13mol）溴-乙醇溶液，6h加毕， $35\\sim45^{\\circ}C$ 反应 $2\\sim3\\mathrm{h}$ ，冷至 $0^{\\circ}\\mathrm{C}$ ，得橙红色溶液，减压回收溶剂，沉淀经过滤、洗涤、干燥，得乳黄色晶体 $\\textrm{B}22.8\\textmu$ ，熔点 $131{\\sim}133^{\\circ}\\mathrm{C}$ ，产率 $70.4\\%$ 。  \n\n取 $_{40.58}$ （0.15mol）B和少量水，室温下滴加 $15\\mathrm{mL}$ $(0.15\\mathrm{mol}$ ）哌啶，然后在 $30\\sim$ $40^{\\circ}\\mathsf{C}$ 下反应 $2\\mathrm{h}$ 。将反应混合物去水，经萃取、洗涤、干蒸馏，残留物用氯化氢- $z$ 醇溶液处理，析出沉淀，重结晶得到易溶于水的白色粉末C[1-(4-乙酰氨基苯基)-2-哌啶基-1-丙酮盐酸盐］ $29.2{\\bf g}$ ，熔点 $240^{\\circ}\\mathrm{C}$ （分解)，产率 $62.6\\%$ 。  \n\n将 $1.558$ （0.05mol）C在 $20\\mathrm{mL}$ 、 $15\\%$ 的盐酸中回流0.5h，除去溶剂后得到乳白色沉淀，用无水乙醇重结晶得白色粉末D[1-(4-氨基苯基)-2-哌啶基-1-丙酮盐酸盐］ $1.18g$ ，熔点 $202^{\\circ}\\mathrm{C}$ （分解)，易溶于水，产率 $97.0\\%$ a  \n\n用吗啉、二乙胺、正丁胺代替哌啶，采用相同方法可合成其他三种 $\\alpha$ -氨基酮水性光引发剂（表4-37中的 $\\scriptstyle2\\sim4)$ 。  \n\n表4-37 $\\pmb{\\alpha}$ 氨基酮水性光引发剂  \n\n\n<html><body><table><tr><td>序号</td><td>A</td><td>外观</td><td>水溶性</td><td>熔点/℃</td><td>Amax/nm</td></tr><tr><td>1(D)</td><td>哌啶基</td><td>白色晶体</td><td>易溶</td><td>202(分解)</td><td>334</td></tr><tr><td>2</td><td>吗啉基</td><td>白色晶体</td><td>易溶</td><td>210(分解）</td><td>335</td></tr><tr><td>3</td><td>二乙氨基</td><td>白色晶体</td><td>易溶</td><td>140（分解）</td><td>337</td></tr><tr><td>4</td><td>正丁氨基</td><td>白色晶体</td><td>易溶</td><td>206（分解）</td><td>330</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 157,
+        "chunk": "# （70）水性硫杂葱酮季铵盐光引发剂的合成（一）  \n\n![](images/31d3b38866943ddc07dfcd9d6c78c3a1c8cf908eed6ca6c7f172fcae00e5af05.jpg)  \n\n在三口烧瓶中加入 ${\\bf40g}$ 三甲胺盐酸盐和 $80\\mathrm{mL}$ 无水乙醇，加热至 $30^{\\circ}\\mathrm{C}$ ，搅拌滴加 $42.58\\$ 环氧氯丙烷，加毕反应3～4h，有大量白色晶体产生，过滤，用无水乙醇洗涤，干燥后得粗品，用乙醇重结晶，得纯品A（3-氯-2-羟基丙基三甲氯化铵)，熔点186～188℃，收率 $38.4\\%$ 。  \n\n在干燥的三口烧瓶中加人0.27g金属钠和27mL无水乙醇，待钠反应完全后，加人2.28g2-羟基硫杂葱酮，搅拌加热至回流，加人2.14gA回流反应20h。加几滴2mol/L盐酸异丙醇溶液，调pH=4，趁热过滤，滤液用冰水冷却得黄色晶体，甲醇洗涤，干燥得黄色固体，熔点245～246.5℃，用乙醇与甲醇混合溶剂重结晶，再用乙醇洗涤，真空干燥，得亮黄色晶体B[2-羟基-3-(2'-硫杂葱酮氧基)-N，N,N-三甲基-1-丙胺氯化物]，收率 $62.8\\%$ 。  \n\n用同样方法可合成表4-38中化学物 $\\scriptstyle2\\sim4$ 。  \n\n![](images/f0f287152e4a0a1eb9882e97706df4bcd0bd05f962d6e33cbd442e270ed569d3.jpg)  \n\n表4-38水性硫杂葱酮季铵盐光引发剂（一）  \n\n\n<html><body><table><tr><td>序号</td><td>R1</td><td>R2</td><td>R3</td><td>A</td><td>收率 /%</td><td>熔点 /℃</td><td>Amax /nm</td><td>/[L/(mol·cm)]</td></tr><tr><td>1</td><td>H</td><td>H</td><td>H</td><td>OH -OCHCHCH2N(CH3)3CI-</td><td>62.8</td><td>245~246</td><td>404.6</td><td>5680</td></tr><tr><td>2</td><td>H</td><td>H</td><td>CH3</td><td>OH OCHCHCHN(CH)3CI-</td><td>42.1</td><td>253~255</td><td>405.8</td><td>4850</td></tr><tr><td>3</td><td>H</td><td>CHs</td><td>H</td><td>OH -OCHCHCHN(CHg)3CI-</td><td>28.9</td><td>232～235</td><td>402.0</td><td>5100</td></tr><tr><td>4</td><td>CH</td><td>H</td><td>H</td><td>OH -OCHCHCHN(CH)CI-</td><td>30.0</td><td>248~251</td><td>393.0</td><td>5260</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 158,
+        "chunk": "# （71）水性硫杂葱酮季铵盐光引发剂的合成（二）  \n\n![](images/0324f5bb89650b23d2de52be96df10877aba79a8319bb7ed0705cddb9ac30e31.jpg)  \n\n在三口烧瓶中加入浓硫酸、邻琉基苯甲酸，搅拌下分批加人2,5-二甲基苯酚，室温揽拌1h，升温至85℃，反应2h静置过夜，反应液倒入冰水中，过滤，用100g/L氢氧化钠水溶液洗涤滤饼，过滤，用稀盐酸中和，得粗品，用冰醋酸重结晶，得浅绿色晶体A（2-羟基-1,4-二甲基硫杂葱酮)，熔点220.3～220.8℃，产率63.2%。  \n\n上述反应中用2,3-二甲基苯酚代替2,5-二甲基苯酚，用同样的方法合成2-羟基-3，4-二  \n\n甲基硫杂葱酮，熔点 ${>}300^{\\circ}\\mathrm{C}$ ，产率 $36.4\\%$ @  \n\n在三口烧瓶中加入A、3-氯-2-羟基丙基三甲基氯化铵和二甲基甲酰胺，搅拌5min升温至 $100^{\\circ}\\mathrm{C}$ ，加入乙醇钠乙醇溶液（ $30\\mathbf{g}/\\mathbf{L})$ ，调 $\\mathtt{p H}$ 值至9，反应24h后滴加 $\\scriptstyle2{\\mathrm{mol/L}}$ 盐酸异丙醇溶液调 $\\mathsf{\\Pi}_{\\mathsf{P}}\\mathsf{H}$ 值至4，过滤，冷却得黄绿色晶体，过滤，真空干燥，用乙醇与水（ $20:1$ 体积比）混合溶剂重结晶，得到B［2-羟基 $\\cdot3\\ –(1^{\\prime},4^{\\prime})$ 二甲基 $\\cdot2^{\\prime}$ -硫杂葱酮氧基)-N,N,N-三甲基-1-丙胺氯化物]，熔点 $254.6{\\sim}255.8\\%$ ，收率 $76.8\\%$ a  \n\n用同样方法可合成表4-39中化合物 $\\scriptstyle2\\sim4$ 。  \n\n![](images/d2df96661273c707178cdb1ecf808bde7e669f914a2b1722973a103f2127fc74.jpg)  \n\n表4-39水性硫杂葱酮季铵盐光引发剂（二）  \n\n\n<html><body><table><tr><td>序号</td><td>R1</td><td>R2</td><td>R3</td><td>A</td><td>收率 1%</td><td>熔点 /℃</td><td>/nm 入max</td><td>E /[L/(mol·cm)]</td></tr><tr><td>1</td><td>CH3</td><td>H</td><td>CH</td><td>OH OCHCHCHN(CH)CI-</td><td>76.8</td><td>254.6~255.8</td><td>404.8</td><td>5192</td></tr><tr><td>2</td><td>H</td><td>CH3</td><td>CH3</td><td>OH OCHCHCHN(CH)3CI-</td><td>30.4</td><td>261.1~262.2</td><td>403.2</td><td>4370</td></tr><tr><td>3</td><td>CH3</td><td>H</td><td>CHs</td><td>OH OCHCHCHN(CHs)3Br</td><td>30.4</td><td>135.3~136.6</td><td>406.2</td><td>3578</td></tr><tr><td>4</td><td>H</td><td>CH3</td><td>CH3</td><td>OH OCHCHCHN(CH5）Br</td><td>65.0</td><td>243.6~244.4</td><td>404.2</td><td>4790</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 159,
+        "chunk": "# （72）水性硫杂葱酮磺酸盐光引发剂的合成（一）  \n\n![](images/2f319de91bdc733bbf4ce064dbe89827f303edffaa095eb469370bb7bfe123d5.jpg)  \n\n在三口烧瓶中加入 $32.4\\mathbf{g}$ 亚硫酸氢钠、 $12.6\\mathbf{g}$ 亚硫酸钠和 $52.58\\$ 去离子水，边搅拌边滴加 $25\\mathbf{g}$ 环氧丙烷，温度控制在 $18\\sim30^{\\circ}\\mathrm{C}$ ，反应 $1\\mathord{\\sim}1.5\\mathrm{h}$ ，沉降，过滤、水洗、干燥，得高纯度白色结晶A，熔点 $262{\\sim}263^{\\circ}\\mathrm{C}$ ，得率 $95\\%$ 。  \n\n在三口烧瓶中加人 $2.15\\mathbf{g}\\ 2\\cdot$ -羟基硫杂葱酮的钠盐、 $1.7{\\bf g}$ A和 $38\\mathrm{mL}$ 二甲苯甲酰胺及少量四丁基溴化铵，搅拌、加热至回流反应 $\\pmb{2\\mathrm{h}}$ ，冷却倒入 $200\\mathrm{mL}$ 丙酮中，有大量固体析出，过滤，用丙酮多次洗涤，烘干，粗品用甲醇重结晶，得化合物B(表4-40中1) 7  \n\n用同样方法可合成表4-40中化合物 $\\scriptstyle2\\sim4$ 。  \n\n![](images/fb0c6d257027b855c747bbdbedc8173c1927994c47bc99bacba59ba595722b50.jpg)  \n\n表4-40水性硫杂葱酮磺酸盐光引发剂（一）  \n\n\n<html><body><table><tr><td>序号</td><td>R1</td><td>Rz</td><td>Rs</td><td>A</td><td>收率 1%</td><td>熔点 /℃</td><td>/nm Amx</td><td>w /[L/(mol·cm)]</td></tr><tr><td>1</td><td>H</td><td>H</td><td>H</td><td>—O—CHCH—CHSONa 1 OH</td><td>40.0</td><td>>300</td><td>405.4</td><td>33300</td></tr><tr><td>2</td><td>H</td><td>H</td><td>CH</td><td>—O—CH—CH—CHSONa OH</td><td>28.0</td><td>>300</td><td>406.0</td><td>2520</td></tr><tr><td>3</td><td>H</td><td>CHs</td><td>H</td><td>-O—CH—CH—CHSONa OH</td><td>18.0</td><td>>300</td><td>402.2</td><td>5770</td></tr><tr><td>4</td><td>CH</td><td>H</td><td>H</td><td>-O—CHz—CH—CHSO3Na OH</td><td>21.0</td><td>>300</td><td>394.4</td><td>4860</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 160,
+        "chunk": "# （73）水性硫杂葱酮磺酸盐光引发剂的合成（二）  \n\n![](images/87aa225c4d2acffb60a03f607e813197d8b51b1f9b0f32d5937ddda87cad21e2.jpg)  \n\n(A)  \n\n在三口烧瓶中加入2-羟基-1,4-二甲基硫杂葱酮的钠盐、3-氯-2-羟基丙基磺酸钠、二甲基甲酰胺和少量三乙基苄基氯化铵，搅拌5min，升温至回流，反应2h，冷至室温，反应液用大量丙酮洗涤，过滤、烘干得粗品，用无水甲醇重结晶得A［2-羟基-(1',4'-二甲基-2'-硫杂葱酮氧基)-丙基磺酸钠，熔点 ${>}300^{\\circ}\\mathrm{C}$ ，产率 $26.1\\%$  \n\n用同样方式可合成表4-41中化合物 $\\scriptstyle2\\sim4$ 。  \n\n![](images/865713bb5687b8cfc2e716c9de1ca2506d573267860aaa513b34b3346cfdbcc8.jpg)  \n\n表4-41水性硫杂葱酮磺酸盐光引发剂（二）  \n\n\n<html><body><table><tr><td>序号</td><td>R</td><td>R2</td><td>R3</td><td>A</td><td>收率 /%</td><td>熔点 /℃</td><td>/nm 入max</td><td>E /[L/(mol·cm)]</td></tr><tr><td>1</td><td>CH3</td><td>H</td><td>CH</td><td>OH --OCH—CH—CHSONa</td><td>26.1</td><td>>300</td><td>405.2</td><td>4111</td></tr><tr><td>2</td><td>H</td><td>CH</td><td>CH3</td><td>OH -QCH2-CH—CHSONa</td><td>27.0</td><td>>300</td><td>404.6</td><td>2400</td></tr><tr><td>3</td><td>CH3</td><td>H</td><td>CH</td><td>—OCHCHCHSONa</td><td>20.9</td><td>>300</td><td>403.0</td><td>4543</td></tr><tr><td>4</td><td>H</td><td>CH</td><td>CH:</td><td>—OCHCHCHSONa</td><td>13.0</td><td>>300</td><td>402.6</td><td>3347</td></tr></table></body></html>  \n\n（74）水性二苯甲酮季铵盐光引发剂的合成  \n\n![](images/009049535ec6e6c65f8bface6b4ae4fa1e26d2b0fb5998c22afda3080f7f1386.jpg)  \n\n![](images/e2d78907be855f2bef6218ee81e2eb84a990146c333f5e51d1dfbd7a64638be9.jpg)  \n\n在三口烧瓶中加人 $19.8\\mathbf{g}$ （0.1mol）4-羟基苯甲酮、 $38\\mathbf{g}$ （0.4mol）环氧氯丙烷，加热至$80{\\sim}85^{\\circ}\\mathrm{C}$ ，剧烈搅拌下滴加 $9g45\\%$ 的氢氧化钠，1.5h加毕，继续反应1h，冷至室温，抽滤，固相以 $10\\mathrm{mL}$ 环氧丙烷洗涤两次，有机相用 $\\scriptstyle50\\mathrm{mL}$ 、 $50^{\\circ}\\mathrm{C}$ 热水洗涤两次，无水硫酸钠干燥0.5h后，减压蒸馏除去未反应的环氧氯丙烷，得淡黄色黏稠液体A，含量约 $94\\%$ ，产率为 $92\\%$ 。  \n\nA中加人 $9.3\\mathbf{g}$ （0.1mol）三甲胺盐酸盐、 $50\\mathrm{mL}$ 无水乙醇，混合物用 $33\\%$ 的三甲胺水溶液调 $\\mathtt{p H}$ 值为8.5，在 $30^{\\circ}\\mathrm{C}$ 下搅拌反应1h，减压蒸馏，残余物用石油醚、三氯甲烷洗涤三次，用石油醚/乙酸乙酯混合溶剂重结晶，真空干燥，得到水性二苯甲酮光引发剂氯化[2-羟基-3-(4-苯甲酰基苯氧基) $\\mathbf{\\nabla}\\cdot N,N,N.$ 三甲基-1-丙胺]，熔点 $105{\\sim}107^{\\circ}\\mathrm{C}$ ，收率 $90\\%$ 。  \n\n（75）水溶性光引发剂（4-苯甲酰苄基）磺酸钠的合成  \n\n![](images/2d11230458d955b4464011c4e266793140e4e69663ce855adffa14fac8f67975.jpg)  \n\n在三口烧瓶中加人12.5g（0.065mol）对甲基二苯甲酮、 $12.5\\mathbf{g}$ ? $\\left(0.07\\mathrm{mol}\\right)$ ）N-溴代琥珀酰亚胺、 $100\\mathrm{mL}$ 四氯化碳，加热至沸腾回流3h，反应后剩余的 $N_{\\sun}$ -漠代琥珀酰亚胺浮于四氯代碳溶液表面，冷却后过滤除去，滤液旋蒸除去溶剂，产物经乙醇重结晶两次，干燥，得微黄色晶体，对溴甲基二苯甲酮 $9.5{\\bf g}$ ，熔点 $97{\\sim}101\\ensuremath{\\mathrm{^{\\circ}C}}$ ，产率 $55\\%$ 。  \n\n在三口烧瓶中加人2.0g对溴甲基二苯甲酮、20g亚硫酸钠、100mL水：乙醇（1：1，体积比）混合剂，加热回流反应10h，得无色反应液，旋蒸除去溶剂得白色固体，用乙醇溶解、过滤除去无机盐，蒸去乙醇，再用甲醇重结晶，经烘干，得0.8g白色晶体为4-苯甲酰苄基磺酸钠，收率 $38.4\\%$ ， $\\lambda_{\\operatorname*{max}}=263.5\\mathrm{nm}$ ， $\\varepsilon{=}18000\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{cm})$ 。  \n\n（76）水溶性光引发剂（对苯甲酰基）苯甲酸十二烷基二甲基铵盐的合成  \n\n$$\n\\mathrm{C_{12}H_{25}N H_{2}}+H C H O+H C O O H\\longrightarrow\\mathrm{C_{12}H_{25}N(C H_{3})_{2}}\n$$  \n\n![](images/c29bc229e10a75f0ddf2a1eda95d45901ddf9b16c3eb458f21be10328790d736.jpg)  \n\n在三口烧瓶中加人2.0g十二胺、8mL37%的甲醛、8mL甲酸，在沸水浴中加热即有二氧化碳产生，反应约 $30\\mathrm{{min}}$ 后，冷却，用 $10\\%$ 的氢氧化钠溶液中和，再加入氯化钠盐析，此时胺即浮于水溶液之上，用石油醚萃取，水洗至中性，加无水硫酸钠于燥，蒸去石油醚，真空干燥得无色液体十二烷基二甲基胺。  \n\n圆底烧瓶中加人等摩尔比的十二烷基二甲基胺和对羧基二苯酮，一边振荡，一边滴加内酮，得到透明溶液，室温放置 $\\mathtt{2h}$ ，旋蒸除去溶剂，得无色黏稠的液体，真空十燥，为（对-苯甲酰基）苯甲酸十二烷基二甲基铵盐。  \n\n（77）含葡萄糖胺的水溶性高分子型硫杂葱酮的合成  \n\n![](images/d4080af9c949a7b57e3488e2dbcdc25d3b641ab44c25a07a428150c792527b5c.jpg)  \n\n在三口烧瓶中加人 $3\\mathbf{g}\\ 2\\cdot$ 羟基硫杂葱酮， $15\\mathrm{mL}$ 1-甲基吡咯烷酮和 $_{\\mathrm{10mL}}$ 三乙胺，待溶解完全后，室温下滴加 5mL1-甲基-2-吡咯烷酮和10mL丙烷酰氯混合液，反应24h，过滤，将滤液加人水中沉淀，过滤，真空干燥，得产物ATX。  \n\n称取一定比例ATX和甲基丙烯酸缩水甘油酯于三口烧瓶中，用甲苯作溶剂，偶氮二异晴为引发剂，在氮气保护下，升温至90℃反应6h，再升温至120℃反应3h，用乙醇沉淀产物，过滤，收集沉淀，真空干燥得到PTX。  \n\n称取一定量的PTX和N-甲基-D-葡萄糖胺于三口烧瓶中，用N,N-二甲基乙酰胺为溶剂，油浴90℃反应24h，用乙酸乙酯和甲醇混合液沉淀产物，过滤，收集沉淀真空干燥，得产物含葡萄糖胺的水溶性高分子型硫杂葱酮光引发剂（PTX-GA)。PTX-GA 的一些物理化学性质见表4-42。  \n\n表4-42PTX-GA的一些物理和化学性质  \n\n\n<html><body><table><tr><td>光引发剂</td><td>mn</td><td>M/X10</td><td>Amax/nm</td><td>/[L/(mol·cm）]</td></tr><tr><td>PTX-GA1</td><td>1:4</td><td>1.48</td><td>390</td><td>3312</td></tr><tr><td>PTX-GA2</td><td>1:8</td><td>1.63</td><td>390</td><td>3453</td></tr><tr><td>PTX-GA3</td><td>1:10</td><td>1.58</td><td>390</td><td>3576</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 161,
+        "chunk": "# （78）助引发剂对二氨基苯甲酸酯的合成  \n\n![](images/f97ed2d862d39a9f9657295e6c8d4fa6cf24b66501622f25ae5e8ac26a7fa012.jpg)  \n\n将对二甲氨基苯甲醛溶于乙醇中，加入盐酸羟胺反应，得到对二甲氨基苯甲，收率$100\\%$ ，熔点 $142{\\sim}144^{\\circ}\\mathrm{C}$ 。  \n\n将对二甲氨基苯甲与醋酸反应，得到对二甲氨基苯晴，收率 $90\\%$ ，熔点 $70.2{\\sim}71.9^{\\circ}\\mathrm{C}$ 。  \n\n，将对二甲氨基苯腈与氢氧化钠溶液在相转移催化剂存在下反应得对二甲氨基苯甲酸，收率 $97.9\\%$ ，熔点 $235{\\sim}237\\mathrm{^{\\circ}C}$ 。  \n\n将对二甲氨基苯甲酸分别与硫酸二甲酯、硫酸二乙酯或溴丁烷、溴戊烷、溴己烷、溴辛烷在相转移催化剂存在下反应，分别得到不同的对二甲氨基苯甲酸酯。不同对二甲氨基苯甲酸酯的收率和性能见表4-43。  \n\n表4-43不同对二甲氨基苯甲酸酯的收率和性能  \n\n\n<html><body><table><tr><td>名称</td><td>收率/%</td><td>熔点/℃</td><td>沸点/℃</td></tr><tr><td>对二甲氨基苯甲酸甲酯</td><td>93.1</td><td>94.7~96.5</td><td></td></tr><tr><td>对二甲氨基苯甲酸乙酯</td><td>82.9</td><td>56.6~58.2</td><td></td></tr><tr><td>对二甲氨基苯甲酸丁酯</td><td>93.3</td><td></td><td>150(1.3kPa)</td></tr><tr><td>对二甲氨基苯甲酸戊酯</td><td>76.0</td><td></td><td>140(0.7kPa)</td></tr><tr><td>对二甲氨基苯甲酸己酯</td><td>74.2</td><td></td><td>140(0.7kPa)</td></tr><tr><td>对二甲氨基苯甲酸辛酯</td><td>75.6</td><td></td><td>165(0.7kPa)</td></tr></table></body></html>  \n\n![](images/0fa423f7dc474f88d041110b69a16b43a099ebafaa200b17b2a6c909ca557f47.jpg)  \n\n![](images/a3fbd7461fe3b884db3ce50b7ab8fa0e100ae049e3492b865f1d518fdaee9f8c.jpg)  \n\n在三口烧瓶中加人 $83.81g$ 甲基丙烯酸羟乙酯、 $105\\mathrm{mL}$ 三乙胺和 $250\\mathrm{mL}$ 无水甲苯，搅匀，在冰浴中控制温度 $0\\sim5\\mathrm{{\\ttC}}$ ，4h内慢慢滴加 $79.79g$ 丙烯酰氯和 $\\mathfrak{s o}_{\\mathbf{g}}$ 无水甲苯混合物，加毕，静置过夜，抽滤除去生成的季铵盐，用 $\\scriptstyle40\\mathrm{mL}$ 甲苯洗2遍，滤液依次用 ${75}\\mathrm{mL}$ 蒸馏水、$\\mathtt{50m L1m o l/L}$ 盐酸、 $\\mathrm{50mL~1mol/L}$ 碳酸氢钠洗涤，然后用无水硫酸钠干燥。过滤、旋转蒸发除去甲苯，得浅黄色A(乙二醇丙烯酸酯甲基丙烯酸酯)。  \n\n在三口烧瓶中加人 $0.05\\mathrm{mol}$ A和 $25\\mathrm{mL}$ 无水甲醇，搅匀，冰浴中、氮气保护下慢慢滴加0.05mol吗啡啉和25mL无水甲醇混合物，红外监控反应至N—H峰（330cm-1）消失，旋转蒸发除去甲醇。以乙酸乙酯：正己烷 $=1:1$ 为淋洗剂、 $200\\sim300$ 目硅酸为固定相进行柱分离得可聚合助引光剂B。用 $0.05\\mathrm{mol}$ 二乙胺代吗啡啉，同样的方法合成得到可聚合助引发剂C。  \n\n$\\begin{array}{r l r}{\\mathrm{CH_{3}}}&{}&{\\mathrm{CH_{3}}}\\\\ {\\mathrm{H_{2}C\\longrightarrow}}&{\\mathrm{C-COOCH_{2}C H_{2}O C O C H-C H_{2}}}&{+\\mathrm{HN(C_{2}H_{5})_{2}}\\longrightarrow}&{\\mathrm{H_{2}C-C O O C H_{2}C H_{2}O C O C H_{2}C H_{2}N(C_{2}H_{3})_{2}}}\\end{array}$ H5)2 (C) 用 $0.10{\\bmod{\\ N}},l$ N-二甲基丙二胺代吗啡琳，同样的方法合成得到可聚合物引发剂D。 CH3 CHa HCC—COOCHCHOCOCH—CH+HN(CH)N(CH)2-→HC—C—COOCHCHOCOCHCHN(CH)N(CH)2  \n\n助引发剂引发效率： $\\mathtt{B}>$ DMEM>C>D。DMEM为甲基丙烯酸-2-二甲氨基乙酯：  \n\n（80）不同链长助引发剂的合成  \n\n在三口烧瓶中加人 $0.1\\mathrm{mol}$ 丙烯酸酯（甲酯、乙酯、丁酯、异辛酯）氮气保护和搅拌下缓慢滴加 $0.05\\mathrm{mol}$ 正辛胺与 $15\\mathrm{mL}$ 乙醇混合溶液，红外监控丙烯酸酯 $1634\\mathsf{c m}^{-1}\\mathsf{C}=\\mathsf{C}$ 双键峰和 $3330\\mathsf{c m}^{-1}\\mathbf{N}\\mathrm{-}\\mathbf{H}$ 峰变化。反应结束后，旋转蒸发除去乙醇，用乙酸乙酯和正已烷为洗脱剂，柱分离提纯产品，得不同链长叔胺助引发剂。  \n\n（81）自由基和阳离子混杂型光引发剂苯基-二苯甲酮基碘盐的合成  \n\n![](images/3dc47d676a8d4ed3a7b93d551de953f11fdbd04f229e9fa0e17f529a3beafeee.jpg)  \n\n在三口烧瓶中加人14mL过氧化氢（30%）、61mL乙酸酐，在40℃避光搅拌4h，加入10g碘苯，保持40℃过夜，冷却析出白色晶体，过滤后，将母液旋蒸，析出大量白色晶体，将全部白色晶体用乙醚洗涤两次，再干燥得产物A，熔点163～165℃，产率80.4%。  \n\n，将对甲苯碘酸-水化合物38.05g溶于少量乙晴中，将A溶于225mL乙腈中，溶解好后将两溶液混合，溶液立即变清，颜色变黄，放置不久，析出白色略带黄色的针状晶体B，熔点 $112{\\sim}114^{\\circ}\\mathrm{C}$ ，产率 $76.26\\%$ 。  \n\n将2gB和1.86g二苯甲酮混合加热，搅拌，反应物逐渐熔融形成黄色透明溶液，停止加热，继续搅拌2h，停止搅拌，放置不久，形成白色略带黄色的油状物，用乙醚洗两次再加人10.2mL丁酮，有少量不溶物出现，过滤不溶物得无色溶液，加入0.82g六氟磷酸钾，产生白色沉淀，过滤去掉沉淀物，将所得溶液旋蒸至干，得黄色固体C，即为自由基和阳离子混杂型光引发剂苯基-二苯甲酮基碘六氟磷酸盐。  \n\n（82）自由基和阳离子混杂型光引发剂二苯基碘-4-二苯甲酮甲酸盐的合成在三口烧瓶中加人 $50\\pmb{\\mathrm{g}}$ 碘酸钾、 $\\scriptstyle50\\mathrm{mL}$ 乙酸酐和 $45\\mathrm{mL}$ 苯，将体系冷到一5℃（用冰-氯化钙浴)。同时在冰水浴冷却下将 35mL浓硫酸缓慢地在搅拌下加入到50mL乙酸酐中。在大力搅拌下将此浓硫酸和乙酸酐混合液滴加到三口烧瓶中，温度控制在 $5\\%$ 以下，体系由无色变为黄色，慢慢回到室温，放置 $24\\mathrm{h}$ 再冷却到 $5\\mathrm{^c}$ 以下，搅拌下滴加 $100\\mathrm{mL}$ 蒸馏水，温度不超过 $10^{\\circ}\\mathrm{C}$ ，有气体放出，产生白色沉淀。向体系中滴加 $38\\mathrm{mL}$ 乙醚，过滤反应产生的硫酸氢钾，得黄色溶液。再用 $120\\mathrm{mL}$ 乙醚萃取两次，取水溶液，用 $_{60\\mathrm{mL}}$ 石油醚萃取一次，此时溶液为黄色，加入 $26.8g$ 已研细的氯化铵，立即产生白色沉淀，为使反应更好进行，加入 $20\\mathrm{mL}$ 蒸馏水，过滤并用乙醚，蒸馏水各洗两次，抽滤得白色固体A，为氯化二苯基碘盐，熔点 $231{\\sim}233^{\\circ}\\mathrm{C}$ ，产率 $67.95\\%$ 。  \n\n![](images/99e74f489499a529289874c19cadc9162e1fe2d5034f402929e022b18b3eb614.jpg)  \n\n用 $27.67_{8}$ 硝酸银和 $_{0.51\\mathbf{g}}$ 氢氧化钠分别溶于少量蒸馏水中，再混合立即产生黑色沉淀氧化银，用蒸馏水洗数次抽滤后与 $20.03\\mathbf{g}$ A混合，研磨1h，研磨时为使反应充分，加入少量蒸馏水，然后用蒸馏水洗涤多次，过滤得无色溶液，然后与4.33g4-二苯甲酮甲酸混合搅拌，此时 $\\mathtt{p H}$ 值在 $\\mathfrak{s}\\sim10$ ，搅拌一天，测 $\\scriptstyle\\mathbf{pH}=8\\sim9$ ，过滤得白色固体，用甲醇重结晶得白色晶体B，为二苯基碘-4-二苯甲酮甲酸盐，熔点 $180{\\sim}182^{\\circ}\\mathrm{C}$ ，产率 $33.8\\%$ 。  \n\n（83）自由基和阳离子双重光引发剂的合成  \n\n![](images/8002d1abdcb42440c82c68b4ef1765887f3f746704d8148c812a36053435f279.jpg)  \n\n在三口烧瓶中加入 ${\\mathfrak{s}}_{\\mathbf{g}}$ $\\left(0,02{\\bmod{1}}\\right)$ ）异丙基硫杂葱酮溶解于 $320\\mathrm{mL}$ 的乙腈和水混合溶剂（乙腈 $75\\%$ ，水 $25\\%$ ， $35\\sim55^{\\circ}\\mathrm{C}$ 下搅拌至大部分溶解，加人 $43.17_{\\bf{g}}$ 1 $\\left(0,08\\mathrm{mol}\\right).$ ）硝酸铈铵，室温搅拌1h。加入 $200\\mathrm{mL}$ 去离子水，用无水乙醚萃取，醚层用无水硫酸镁干燥，旋转蒸发除去乙醚，得黄色固体A异丙基硫杂葱酮氧化物，产率 $84\\%$ 。  \n\n将 $2.205\\mathbf{g}$ C $\\left(0.0075\\mathrm{mol}\\right),$ ）A和 $1.604{\\tt g}$ $\\left(0.0104\\mathrm{mol}\\right)$ ）联苯溶解于 $7\\mathrm{mL}$ 二氯甲烷中，搅拌，加人$7\\mathrm{mL}$ 乙酸酐，用冰水浴降温至 ${<}15^{\\circ}\\mathrm{C}$ ，滴加 $2.6\\mathrm{mL}$ 浓硫酸，温度维持 ${<}15\\mathrm{\\textperthousand}$ ，加毕升温至室温，搅拌2h，加入 $100\\mathbf{mL}$ 去离子水，用 $200\\mathrm{mL}$ 二氯甲烷萃取两次，合并二氯甲烷溶液用无水硫酸镁干燥，旋转蒸发除去二氯甲烷，将得到中间产物溶于少量乙酸，然后倒入六氟磷酸钾水溶液（4g六氟磷酸钾溶于 $130\\mathrm{mL}$ 水中)，搅拌，得到黏稠物用二氯甲烷萃取，并用无水硫酸镁干燥，旋蒸除去二氯甲烷，得粗产品为棕色黏稠物，色谱柱用合适流动相，得到棕色固体物质B，熔点 $\\mathfrak{s}7\\sim$ $100^{\\circ}\\mathrm{C}$ ，产率 $90\\%$ ，B为自由基和阳离子双重光引发剂，也是光产酸剂。  \n\n光引发剂的生产厂家国外主要有瑞士汽巴精化公司（Ciba）（现被巴斯夫公司收购)、意大利宁柏迪公司（Lamberti）、英国大湖公司（GreatLakes)、美国氰特（Cytec）、德国巴斯夫公司（BASF)、德国科宁公司（Cogis）、美国道化学公司（DowChemical）、美国沙多玛（Sartomer）等。国内主要有北京英力科技发展公司、天津久日化工公司、天津化学试剂研究所、大连大雪集团精细化工公司、甘肃金盾化工公司、上海泰禾集团公司、优缔贸易（上海）公司、南京贸桥化工公司、常州强力电子新材料公司、常州华钛化学公司、宁勃迪化工（江阴）公司、杭州佳圆化工公司、靖江宏泰化工公司、大丰德尔明化工公司、连云港德泽化工公司、浙江德清县美联医药化学公司、荆门昱奎化工公司、浙江寿尔福化工公司、长沙新宇化工实业公司等。它们的主要产品及商品名称见表4-44和表4-45。常见光引发剂的应用领域见表4-46。  \n\n<html><body><table><tr><td>光引 发剂</td><td>651</td><td>184</td><td></td><td>907</td><td>369</td><td>500</td><td>1000</td><td>819</td><td>1700</td><td></td><td>1800</td><td>261</td><td>784</td><td>1173</td><td>2959</td><td>4265</td><td></td><td colspan=\"2\">TPO</td></tr><tr><td>原瑞士 汽巴精化 (现巴斯 夫)</td><td>Irgacure 651</td><td>Irgacure 184</td><td></td><td>Irgacure 907</td><td>Irgacure 369</td><td>Irgacure 500</td><td>Irgacure 1000</td><td></td><td>Irgacure 819</td><td>Irgacure 1700</td><td>Irgacure 1800</td><td>Irgacure 261</td><td>Irgacure 784</td><td>1173 Darocur</td><td>2959 Darocur</td><td></td><td>4265 Darocur</td><td colspan=\"2\">Darocur 4263</td></tr><tr><td>光别</td><td>BP</td><td>651</td><td>1173</td><td>184</td><td>ITX</td><td>CTX</td><td>CPTX</td><td>BMS</td><td>TPO</td><td>DEAP KIP150</td><td>TZT</td><td>TZM</td><td>KTO</td><td>硫盐</td><td>硫盐</td><td></td><td></td><td></td><td></td></tr><tr><td>意大利 宁柏迪</td><td>Esacure BZO</td><td>KB1 Esacure</td><td>Esacure Esacure KL200</td><td>KS300</td><td>Esacure ITX</td><td></td><td></td><td></td><td></td><td></td><td>KIP150 Esacure</td><td>Esacure TZT</td><td>Esacure TZM</td><td>KTO Esacure</td><td></td><td></td><td></td><td>EAB</td><td></td></tr><tr><td>美国沙 多玛</td><td></td><td>SR1120</td><td>SR1021</td><td>SR1122</td><td>SR1124</td><td></td><td></td><td></td><td></td><td></td><td>SR1130</td><td>SR1137</td><td>SR1136</td><td>SR1135</td><td>SR1010</td><td>SR1011</td><td>SR1012</td><td>SR1125</td><td></td></tr><tr><td>美国第 一化学</td><td></td><td>Firstcure BDK</td><td></td><td></td><td>Firstcure ITX</td><td></td><td></td><td></td><td></td><td>Firsteure DEAP</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Firstcure Firstcure EDAB</td><td>ODAB</td></tr><tr><td>美国道 化学公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>UV169 76</td><td>UV169 92</td><td></td><td></td><td></td></tr><tr><td>英国大 湖</td><td></td><td></td><td></td><td></td><td>QuantacureQuantacure ITX</td><td>CTX</td><td>Quantacure Quantacure CPTX</td><td>BMS</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>QuantacureQuantacure EPD</td><td>EHA</td></tr><tr><td>德国巴 斯夫</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Lucirin TPOTPO-LO</td><td>Lucirin</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>德国科 宁</td><td>BP 4Photomer</td><td>51 Photomen</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Photomer 81</td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>光引发剂</td><td>BP</td><td>651</td><td>1173</td><td>184</td><td>369</td><td>907</td><td>ITX</td><td>TPO</td><td>BMS</td><td>500</td><td>1000</td><td>4265</td><td>4-MBPΦ</td><td>MBB@</td><td>助引发剂</td><td></td></tr><tr><td rowspan=\"2\">北京英力</td><td rowspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\">YL-PI</td><td rowspan=\"2\">YI-PI</td><td rowspan=\"2\"></td><td rowspan=\"2\">YL-PI</td><td rowspan=\"2\">YLPI</td><td rowspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\">EDAB</td><td></td><td rowspan=\"2\">ODAB</td></tr><tr><td></td></tr><tr><td>天津久日</td><td></td><td></td><td></td><td></td><td></td><td></td><td>ITX</td><td>YL-PI</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>天津试剂所</td><td></td><td>二苯甲酮安息香双</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>大连大雪</td><td>二苯甲酮</td><td>甲醚</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>甘肃金盾</td><td></td><td></td><td></td><td></td><td>369</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>南京贸桥</td><td>BP</td><td>Chemcure 651</td><td>Chemcure 1173</td><td>Chemcure</td><td></td><td>Chemcure</td><td>ChemcureChemcure</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>常州华钛</td><td></td><td></td><td>RuntecureRuntecureRuntecureRuntecure</td><td>184</td><td></td><td>907 Runtecure Runtecure</td><td>ITX</td><td>TPO Runtecure</td><td>Runtecure</td><td>Runtecure</td><td></td><td>RuntecureRuntecureRuntecureRuntecureRuntecureRuntecure</td><td></td><td></td><td></td><td></td></tr><tr><td>宁柏迪（江</td><td>1020</td><td>1065</td><td>1103</td><td>1104</td><td></td><td>1107</td><td>1105</td><td>1108</td><td>1030</td><td>1500</td><td>1100</td><td>1265</td><td>1024</td><td>1056</td><td>1101</td><td>1098</td></tr><tr><td></td><td>二苯甲酮</td><td></td><td>XT1173</td><td>XT184</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海秦禾 杭州佳圆</td><td>BP</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>靖江宏泰</td><td>CHC21</td><td>651</td><td>CHC651CHC1173CHC184</td><td></td><td></td><td>CHC907</td><td>ITX</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>明大丰德尔</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>二苯甲酮</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>连云港德泽二苯甲酮 德清美联</td><td></td><td></td><td>D73</td><td>D84 184</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>浙江寿尔福</td><td></td><td></td><td></td><td></td><td></td><td>YF-TI</td><td>YF-TI</td><td>YF-TI</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>长沙新宇</td><td>BP</td><td>BDK</td><td>UV1173</td><td>UV184</td><td>UV369</td><td>907 UV907</td><td>ITX ITX</td><td>TPO TPO</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>荆门昱奎</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>TPO</td><td></td><td>UV500</td><td></td><td>UV4265</td><td>4-MBP</td><td>MBB</td><td>EPD</td><td>EHA</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n（  \n\n\n<html><body><table><tr><td>应用领域</td><td></td><td>184261369</td><td></td><td>500 651</td><td></td><td>784819907</td><td></td><td>1000</td><td></td><td></td><td>1800|2959|1173</td><td>4265</td><td>TPO DEAP</td><td></td><td>BP</td><td>TZM</td><td></td><td></td><td></td><td></td><td></td><td>TZT BMS2-EAITX KIP150KIP100FKTO/46KIP/EM</td><td></td></tr><tr><td>不饱和聚酯木器漆</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>0</td><td></td><td></td><td></td><td></td><td></td><td>0</td><td>△</td><td>0</td><td></td><td></td><td></td><td>0</td><td></td><td></td></tr><tr><td>丙烯酸系木器清漆</td><td></td><td></td><td></td><td></td><td></td><td>△</td><td></td><td></td><td></td><td></td><td>0</td><td>△</td><td></td><td>△</td><td>△</td><td>0</td><td></td><td></td><td>△</td><td></td><td></td><td>0</td><td></td></tr><tr><td>白木器漆</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>0</td><td></td><td></td><td>△</td><td>△</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>塑料、金属清漆</td><td></td><td></td><td></td><td>△</td><td></td><td></td><td></td><td></td><td></td><td>0</td><td>△</td><td></td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>0</td><td></td><td></td></tr><tr><td>纸张上光油</td><td>0</td><td></td><td></td><td>0</td><td></td><td>A</td><td>△</td><td></td><td></td><td></td><td></td><td>△</td><td></td><td></td><td>0</td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>耐UV清漆</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>0</td><td></td><td></td><td></td></tr><tr><td>阳离子光固化涂料</td><td></td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>UV粉末涂料</td><td></td><td></td><td></td><td></td><td></td><td>0</td><td></td><td></td><td>△</td><td>0</td><td></td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>水性UV油墨和涂料</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>△</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>低挥发、低气味涂层</td><td></td><td></td><td>0</td><td></td><td></td><td>0</td><td></td><td>-</td><td></td><td>0</td><td></td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>0</td><td></td><td></td><td></td></tr><tr><td>厚涂层</td><td>△</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>光纤涂料</td><td></td><td></td><td></td><td></td><td>△</td><td>0</td><td></td><td></td><td>△</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>胶黏剂</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>△</td><td></td><td>△ △</td><td>0</td><td>△</td><td></td><td></td><td>0</td><td></td><td></td><td></td><td>0</td><td></td><td></td><td></td></tr><tr><td>PCB用抗蚀剂</td><td></td><td></td><td>0</td><td></td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td>△</td><td></td><td></td><td></td><td></td><td></td><td></td><td>0</td><td>△</td><td></td><td></td><td></td></tr><tr><td>阻焊剂</td><td></td><td></td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td>0</td><td></td><td></td><td></td><td></td></tr><tr><td>环氧抗蚀剂</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>柔性版</td><td></td><td></td><td></td><td></td><td>。</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>△</td><td>△</td><td></td><td></td></tr><tr><td>CTP版</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>胶印油墨 丝印油墨</td><td>△</td><td></td><td></td><td>△ ##</td></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 162,
+        "chunk": "# 第5章添加剂  \n\n光固化产品用的添加剂（additive）主要包括颜料和染料、填料、助剂等，虽然它们不是光固化产品的主要成分，而且在产品中占的比例很小，但它们对完善产品的各种性能起着重要作用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 163,
+        "chunk": "# 5.1 颜料和染料  \n\n颜料（pigment）是一种微细粉末状有色物质，不溶于水或溶剂等介质中，而能均匀分散在涂料和油墨的基料中，涂于基材表面形成色层，呈现一定的色彩。颜料应当具有适当的遮盖力、着色力、高分散度，鲜明的颜色和对光稳定性等特性。染料（dye）也是一种微细粉末状物质，但它能溶解于涂料和油墨的基料中，得到透明的、艳丽的色泽，但对基材无遮盖作用，耐光性不如颜料。有色涂料和油墨主要用颜料作为着色剂，而染料用作透明清漆和油墨的着色剂。  \n\n涂料和油墨用的颜料分无机颜料和有机颜料两大类。无机颜料价格便宜，有比较好的耐光性、耐候性、耐热性，大部分无机颜料有较好的机械强度和遮盖力；但色光大多偏暗，不够艳丽，品种较少，色谱也不齐全，不少无机颜料有毒，有些化学稳定性较差。有机颜料色谱比较宽广、齐全，有比较鲜艳、明亮的色调，着色力比较强，分散性好，化学稳定性比较好，有一定的透明度；但生产比较复杂，价格较贵。由于有机颜料综合性能比无机颜料好，正在逐渐取代无机颜料。白色和黑色颜料基本选自无机颜料，而彩色颜料则以有机颜料为主。  \n\n颜料是涂料和油墨制造过程中不可缺少的原料之一。颜料在涂料和油墨中有如下功能：$\\textcircled{1}$ 提供颜色； $\\textcircled{2}$ 对底材的遮盖； $\\textcircled{3}$ 改善涂层的性能，如提高强度、附着力，增加光泽，增强耐光性、耐候性、耐磨性等； $\\textcircled{4}$ 改进涂料和油墨的强度性能。部分颜料还具有防锈、耐高温、防污等特殊功能。 O  \n\n固态粉末状的颜料加入涂料和油墨基料黏稠的液态体系中，必须进行分散、研磨和稳定的加工过程，其结果将影响到涂料和油墨的应用性能。特别对光固化涂料和光固化油墨，由于颜料对紫外光存在着吸收与反射、散射作用，使紫外光照射到涂层后，强度发生变化，影响光引发剂的引发效率，从而影响到涂料和油墨的光固化速率。表5-1为部分颜料的紫外透过率。  \n\n单位：%  \n\n表5-1部分颜料的紫外透过率 $(0.92\\mu\\mathrm{m}$ 颜料层的透过率)  \n\n\n<html><body><table><tr><td rowspan=\"3\">颜料</td><td colspan=\"6\">光的波长/nm</td><td rowspan=\"2\">吸收365.5nm的光 的颜料层厚度/μm</td></tr><tr><td>435.8</td><td>404.7</td><td>365.5</td><td>334.2</td><td>313.1</td><td>302.3</td></tr><tr><td>铅白</td><td>69</td><td>66</td><td>61</td><td>57.5</td><td>55</td><td>54</td><td>27.0</td></tr><tr><td>锌钡白</td><td>56</td><td>52</td><td>43</td><td>32</td><td>15</td><td>5</td><td>10.0</td></tr><tr><td>钛白</td><td>35</td><td>32</td><td>18</td><td>6</td><td>0.5</td><td>0</td><td>3.1</td></tr><tr><td>锌白</td><td>44~46</td><td>38~40</td><td>0</td><td>0</td><td>0</td><td>0</td><td>0.9</td></tr><tr><td>硫化锌</td><td>30</td><td>28</td><td>22</td><td>10.5</td><td>0</td><td>0</td><td>6.2</td></tr><tr><td>重晶石</td><td>68</td><td>67</td><td>65</td><td>64.5</td><td>64</td><td>63.5</td><td>一</td></tr><tr><td>二氧化硅</td><td>88</td><td>88</td><td>85</td><td>82</td><td>80</td><td>79</td><td>一</td></tr><tr><td>天然碳酸钙</td><td>71</td><td>69</td><td>68</td><td>67</td><td>66</td><td>65.5</td><td>一</td></tr><tr><td>炭黑</td><td>0</td><td>0</td><td>0</td><td>0</td><td>0</td><td>0</td><td>0.6</td></tr><tr><td>油烟</td><td>1.5</td><td>1</td><td>0.7</td><td>1</td><td>1</td><td>1</td><td>1.5</td></tr><tr><td>铁蓝</td><td>41.5</td><td>40</td><td>40</td><td>39</td><td>26</td><td>24</td><td>5.5</td></tr><tr><td>氧化铬(98%)</td><td>13</td><td>12</td><td>10</td><td>10</td><td>10.5</td><td>11</td><td>2.2</td></tr><tr><td>黄丹</td><td>2.5</td><td>3</td><td>4.5</td><td>4.5</td><td>4</td><td>4</td><td>1.5</td></tr><tr><td>锌黄</td><td>35</td><td>33</td><td>32</td><td>32</td><td>32</td><td>31.5</td><td>3.0</td></tr><tr><td>铁红</td><td>50</td><td>43</td><td>45</td><td>43</td><td>50</td><td>50</td><td>5.8</td></tr><tr><td>耐晒黄</td><td>10</td><td>10</td><td>10</td><td>13</td><td>12</td><td>13</td><td>1.9</td></tr><tr><td>茜素色淀（42%）</td><td>31</td><td>43</td><td>50</td><td>40</td><td>37</td><td>28</td><td>5.2</td></tr><tr><td>（茜素色淀)茜草红色淀（70%）</td><td>15.5</td><td>23</td><td>20</td><td>12</td><td>2</td><td>0</td><td>3.1</td></tr><tr><td>甲苯胺色原</td><td>9</td><td>9</td><td>21</td><td>20</td><td>8</td><td>8.5</td><td>2.1</td></tr><tr><td>黄光颜料红</td><td>50</td><td>43</td><td>45</td><td>43</td><td>50</td><td>50</td><td>5.8</td></tr><tr><td>群青</td><td>88</td><td>88</td><td>81</td><td>81</td><td>77</td><td>75</td><td>52.3</td></tr></table></body></html>  \n\n颜料的颜色、遮盖能力通常可用着色力和遮盖力来表示。  \n\n着色力（tinting strength）是指颜料对其他物质的染（着）色能力。在涂料和油墨中，通常是以白色颜料为基准，用颜料与白色颜料混合后形成颜色的强弱，衡量该颜料对白色颜料的着色能力。着色力是颜料对光线吸收和散射的结果，着色力主要取决于对光线的吸收，颜料的吸收能力越强，其着色力越高。着色力还与颜料的化学组成、粒径大小、分散度等有关，着色力一般随颜料粒径的减小而增强，但到最大值后，随粒径变小反而减小，存在着色力最强的最佳粒径；分散度越高，着色力越大，但分散度增大到一定后，着色力上升平缓。  \n\n遮盖力（coveringpower或hiding power）是指有色涂料和油墨涂膜中颜料能遮盖底材的表面，使它不能透过涂膜而显露的能力，通常以覆盖每平方米底材所含干颜料的质量${\\bf\\zeta}(\\bf{g}/\\bf{m}^{2}$ ）来表示。遮盖力是由于颜料与涂料和油墨基料折射率之差所造成的。当颜料与基料折射率相等时，就是透明的；当颜料的折射率大于基料的折射率时，就出现遮盖力，两者之差越大，遮盖力越强。表5-2为光固化涂料部分材质的折射率。  \n\n表5-2光固化涂料部分材质的折射率  \n\n\n<html><body><table><tr><td>颜料与填料</td><td>折射率</td><td>稀释剂</td><td>折射率</td><td>常用低聚物</td><td>折射率</td></tr><tr><td>金红石型TiOz</td><td>2.76</td><td>St</td><td>1.54</td><td>EA</td><td>1.56</td></tr><tr><td>锐钛型TiOz</td><td>2.55</td><td>2-EHA</td><td>1.43</td><td>酸改性EA</td><td>1.53</td></tr><tr><td>ZnO</td><td>2.03</td><td>HEMA</td><td>1.45</td><td>FA</td><td>1.53</td></tr><tr><td>BaSO4·ZnS</td><td>1.84</td><td>HDDA</td><td>1.01</td><td>环氧大豆油丙烯酸酯</td><td>1.48</td></tr><tr><td>BaSO4</td><td>1.64</td><td>TPGDA</td><td>1.46</td><td>脂肪族PUA</td><td>1.48~1.49</td></tr><tr><td>AlO·3HO</td><td>1.54</td><td>TMPTA</td><td>1.47</td><td>芳香族PUA</td><td>1.48~1.49</td></tr><tr><td>CaCO3</td><td>1.68</td><td>(PO)2NPGDA</td><td>1.45</td><td>聚酯丙烯酸酯</td><td>1.46~1.54</td></tr><tr><td>SiOz</td><td>1.58</td><td>(EO)DDA</td><td>1.54</td><td></td><td></td></tr><tr><td>AlzO·2SiO·3H2O</td><td>1.56</td><td>(EO)TMPTA</td><td>1.47</td><td></td><td></td></tr></table></body></html>\n\n遮盖力也是颜料对光线产生散射和吸收的结果，主要靠散射。对于白色颜料的遮盖力散  \n\n射起决定作用；对于彩色颜料则吸收也要起一定作用，高吸收能力的黑色颜料具有很强的遮盖力。颜料的遮盖力还随粒径大小而变化，存在着体现该颜料最大遮盖力时的最佳粒径，对大多数颜料粒径在 $0.2\\mu\\mathrm{m}$ 左右时遮盖力最佳。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 164,
+        "chunk": "# 5. 1.1 白色颜料  \n\n白色颜料有二氧化钛、氧化锌、锌钡白、铅白等，它们都为无机颜料。白色颜料既要求有较高的白度，还要要求对基材有较高的遮盖力。颜料的遮盖力和颜料的折射率有关，折射率越大，与成膜物折射率的差也越大，颜料的遮盖力越强。表5-3介绍了几种白色颜料的折射率、遮盖力和着色力，很显然，二氧化钛是最佳的白色颜料。  \n\n表5-3几种白色颜料的折射率、遮盖力和着色力  \n\n\n<html><body><table><tr><td>性能</td><td>（红化）</td><td>二氧化）</td><td>氧化锌</td><td>锌钡白</td><td>铅白</td></tr><tr><td>折射率</td><td>2.76</td><td>2.55</td><td>2.03</td><td>1.84</td><td>2.09</td></tr><tr><td>遮盖力/(g/m²)</td><td>414</td><td>333</td><td>87</td><td>118</td><td>97</td></tr><tr><td>着色力</td><td>1700</td><td>1300</td><td>300</td><td>260</td><td>106</td></tr></table></body></html>  \n\n（1）二氧化钛（TiOz）通常叫做钛白粉，是无毒无味的白色粉末，具有良好的光散射能力，因而白度好、着色力高、遮盖力强，是目前使用中最好的白色颜料。同时具有较高的化学稳定性（耐稀酸，耐碱，对大气中的氧、硫化氢、氨等都很稳定)，有较好的耐候性、耐热性、耐光性，对人体无刺激作用。  \n\n二氧化钛有两种不同的晶型：锐钛型和金红石型。金红石型二氧化钛由于折射率高，比锐钛型有更好的遮盖力和着色力，但其本身白度不如锐钛型二氧化钛。  \n\n使用二氧化钛颜料时存在粉化的问题，因为它在紫外区有较强的吸收（图5-1)，可催化聚合物老化。特别是锐钛型二氧化钛更为严重。其原因是在紫外光作用下，二氧化钛可和Oz形成电荷转移络合物（CTC)，CTC可分解成单线态氧或和HO反应生成游离基，它们都可引起聚合物老化、降解，导致涂膜出现失光、变色和粉化现象。  \n\n$$\n\\mathrm{TiO}_{2}+\\mathrm{O}_{2}\\longrightarrow\\mathrm{[TiO_{2}^{+}....O_{2}^{-}]}\n$$  \n\n$$\n\\lbrack\\mathrm{TiO}_{2}^{+}.....{\\mathrm{O}}_{2}^{-}]\\longrightarrow\\mathrm{TiO}_{2}+^{1}{\\mathrm{O}}_{2}^{+}\n$$  \n\n$$\n\\mathrm{[TiO_{2}^{+}....O_{2}^{-}]\\ +H_{2}O\\longrightarrow\\mathrm{TiO_{2}+H O\\cdot+H O O}.}\n$$  \n\n$$\n2\\mathrm{HOO}\\cdot\\longrightarrow\\mathrm{H}_{2}\\mathrm{O}_{2}+\\mathrm{O}_{2}\n$$  \n\n$$\n\\mathrm{H}_{2}\\mathrm{O}_{2}\\longrightarrow2\\mathrm{HO}\\cdot\n$$  \n\n为了降低二氧化钛的光催化活性，常用二氧化硅、氧化铝、氧化锌等进行表面包覆处理，使其表面情性化。还可以用脂肪酸、聚丙二醇、山梨糖醇等有机物进行表面处理，以改善其分散性。  \n\n从图5-1可看到金红石型二氧化钛的透光窗口在370nm以上，锐钛型二氧化钛则在390nm以上，金红石型二氧化钛对紫外光的吸收、散射和反射比锐钛型弱，有利于光固化的进行，而且遮盖力和着色力也高，不易粉化。尽管价格稍贵，但现在白色光固化涂料和油墨大多用金红石型二氧化钛。  \n\n二氧化钛的粒径对白度和光固化效果有较大的影响，二氧化钛的粒径在0.17～0.23um较好，这时二氧化钛粒子反射更多的蓝光和绿光，并减少对红光和黄光的反射，因而显得更白，还可提高遮盖力；对400nm左右的紫外光散射相对较弱，有利于380～450nm 的光线  \n\n的透过，也有利于光固化的进行。  \n\n（2）氧化锌（ZnO）又称锌白，是无臭无味的白色粉末，受热变成黄色，冷却后又恢复白色。在涂料中使用有抑制真菌的作用，能防霉，防止粉化，提高耐久性，涂层较硬，有光泽。但白度、遮盖力、着色力和稳定性都不如二氧化钛，因此在白色涂料和油墨中用量日渐减少。  \n\n（3）锌钡白 $(\\mathrm{BaSO_{4}}\\cdot\\mathrm{ZnS})$ 又名立德粉，是白色晶状粉末。具有良好的化学稳定性和耐碱性，遇酸则会分解释放出 $\\mathrm{H}_{2}\\mathrm{S}$ ，耐候性差，易泛黄，遮盖力只是二氧化钛的 $20\\%\\sim25\\%$ d  \n\n（4）铅白 $\\mathbf{\\bar{\\tau}}_{2\\mathbf{Pb}\\mathbf{CO}_{3}}\\cdot\\mathbf{Pb}(\\mathbf{OH})_{2}]$ 白  \n\n色粉末，是最古老的白色颜料。有优良的耐候性和防锈性，亦可杀菌。但因对人体毒性很大，目前已禁止使用。  \n\n![](images/e34684986b5dfcf03bcc4bb5eca66f973edce5f259d676743e2c91eefe0e1805.jpg)  \n图5-1两种二氧化钛的吸光谱线",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 165,
+        "chunk": "# 5.1.2 黑色颜料  \n\n黑色颜料有炭黑、石墨、氧化铁黑、苯胺黑等，炭黑价格低，实用性能好，所以光固化涂料和油墨主要用炭黑作黑色颜料。  \n\n（1）炭黑的组成主要是碳，碳含量为 $83\\%\\sim99\\%$ ，还含有少量的氧和氢。涂料和油墨用的炭黑亦称色素炭黑，按炭黑的粒径和黑度可分为以下几类。  \n\n高色素炭黑：粒径范围在 $\\mathfrak{s}\\sim17\\mathrm{nm}$ @中色素炭黑；粒径范围在 $18\\mathrm{\\sim}25\\mathrm{nm}$ a普通色素炭黑：粒径范围在 $26\\sim35\\mathrm{nm}$ 中  \n\n炭黑的粒径大小、结构和表面活性对应用性能影响很大。炭黑的粒径越小，则黑度越好，着色力也越好(图5-2)。炭黑的结构表示形成链状聚集体的大小和多少，高结构炭黑有较多且大的链状聚集体，黑度较低，黏度增高。炭黑的表面除了有氧、氢外，还有、羧酸、硫、氮等基团，这些表面挥发物影响着它在成膜物中的流变性、润湿性以及黏附性等。  \n\n![](images/e64f46e50925283c63695b7cace528f4ba0dbe41c2bac367f982b4d21f9e4e56.jpg)  \n图5-2炭黑的粒径与着色力和黑色关系  \n\n炭黑表面酸性（挥发物）和表面活性增加时，分散性增加，这是因为炭黑表面挥发物可作为它的有效分散剂，有利于低聚物和活性稀释剂的润湿、渗透，涂料黏度降低，黑度和亮度增加。表面惰性的炭黑与低聚物黏附力较差，流动性不好，颜色表现力差，具有触变性。表5-4显示了炭黑的特性与应用性能的关系。  \n\n表5-4炭黑的特性与应用性能关系  \n\n\n<html><body><table><tr><td>应用性能</td><td>粒径变小(表面积增加)</td><td>结构增大</td><td>表面酸性和活性增大</td></tr><tr><td>分散性</td><td>减少</td><td>增加</td><td>增加</td></tr><tr><td>黏度</td><td>增加</td><td>增加</td><td>减少</td></tr><tr><td>黑度</td><td>增加</td><td>减少</td><td>增加</td></tr><tr><td>亮度</td><td>减少</td><td>减少</td><td>增加</td></tr></table></body></html>  \n\n炭黑对紫外光和可见光的吸收很强，几乎找不到“透光”的窗口，因此炭黑着色黑色涂料和油墨是光固化涂料及光固化油墨中最困难的。炭黑由于生产方法不同，品种也不同，性能差别较大。色素炭黑在生产时要经过氧化处理，使炭黑黑度增加，吸油量降低，同时大大增加表面空隙，这样会吸附不同杂质，影响在光固化涂料和油墨中的应用性能。有些杂质会捕捉自由基，使光固化涂料和油墨在紫外光照后，导致诱导期延长，影响固化速率；有些杂质则促进固化，使光固化涂料和油墨在生产及贮存过程中黏度迅速增大，直至凝胶。因此在研制黑色光固化涂料和油墨时，需仔细筛选炭黑颜料。  \n\n目前，德国赢创德固萨公司、美国卡博特公司和日本三菱公司都有专门为光固化涂料和油墨开发的炭黑。  \n\n（2）氧化铁黑（FeO·FezO或FeO4）简称铁黑，也是一种无机颜料。它有较好的耐酸、碱性、耐光性，几乎是无毒的，折射率为2.42。  \n\n（3）苯胺黑（ $\\mathbf{\\nabla}[\\mathbf{PBI\\1})^{\\bullet}$ 结构式如下式，又叫钻石黑，它是一种有机颜料。苯胺黑与炭黑相比，光扩散效应比较低，配制的涂料光泽小。由于它的遮盖力高，吸收性强，可产生非常深的黑色，可与炭黑拼用以达到改善炭黑颜色的目的。  \n\n![](images/5e63e685ea1c9833f45ddf7c4cbc6669442c14553d904d8cdb2197e549318b90.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 166,
+        "chunk": "# 5.1.3 彩色颜料  \n\n彩色颜料因颜色不同又分为红色、黄色、蓝色、绿色、橙色、紫色、棕色等多种颜料，每种颜料的颜色又有有机颜料和无机颜料之分，光固化涂料和油墨中所用彩色颜料主要为有机颜料，同时包括部分无机颜料。  \n\n（1）红色颜料  \n\n$\\textcircled{1}$ 金光红（PR21)，分子式 $\\mathrm{C}_{23}\\mathrm{H}_{17}\\mathrm{N}_{3}\\mathrm{O}_{2}$ ，结构式如下。  \n\n![](images/407f2d30145a93cad9b77acd3a1704941a1fc456cc8ee9fb58f5154eb60a33ab.jpg)  \n\n金红光为 $\\beta$ 萘酚类单偶氮颜料，是粉粒细腻、质轻疏松的黄光红色粉末；着色力较强，有一定透明度，耐酸耐碱性好，耐晒性一般；色光显示带有金光的艳红色。  \n\n$\\textcircled{2}$ 立索尔大红（ $\\mathbf{PR}49:1)$ ，分子式 $\\mathrm{C}_{40}\\mathrm{H}_{26}\\mathrm{BaN}_{4}\\mathrm{O}_{8}\\mathrm{S}_{2}$ ，结构式如下。  \n\n![](images/116b0d51c5cdea7d664085a6d42edf09709223710113c41f3372e466d48a36cc.jpg)  \n\n立索尔大红为 $\\beta$ 萘酚类单偶氮颜料，红色粉末，微溶于热水、乙醇和丙酮；着色力强，耐晒、耐酸、耐热性一般，无油渗性，微有水渗性，遮盖力差。  \n\n$\\textcircled{3}$ 颜料红G（PR37)，分子式 $\\mathrm{C}_{32}\\mathrm{H}_{26}\\mathrm{N}_{8}\\mathrm{O}_{4}$ ，结构式如下。  \n\n![](images/066b9da036e11c7bec2262b4dbc79fd7ea80203f0dabf4f0b97998ab7fb2d327.jpg)  \n\n颜料红G为吡唑啉酮联苯胺类双偶氮颜料，红色粉末，有较好的耐溶剂性和耐光坚牢度。  \n\n$\\textcircled{4}$ 颜料红171（PR171)，分子式 $\\mathrm{C}_{25}\\mathrm{H}_{18}\\mathrm{N}_{6}\\mathrm{O}_{6}$ ，结构式如下。  \n\n![](images/19d7728a144221978bc2044b2a33506a03bdd02ca64340b1d2d37b7f8c8cc1dd.jpg)  \n\n颜料红171为苯并咪唑酮类单偶氮颜料，红色粉末，具有优良的耐光性和耐热性，而且耐候性和耐迁移性好。  \n\n$\\textcircled{5}$ 氧化铁红（ $\\mathrm{Fe}_{2}\\mathrm{O}_{3}.$ )，又叫铁红，是铁的氧化物中最稳定的化合物，随粒径由小变大，色相由黄红向蓝相变化到红紫。具有很高的遮盖力（<7g/m²），仅次于炭黑，着色力较好，耐化学性、耐热性、耐候性、耐光性都很好。但能强烈吸收紫外光，因此不宜在光固化涂料和油墨中使用。  \n\n（2）黄色颜料  \n\n$\\textcircled{1}$ 耐晒黄G（PY1)，又称汉沙黄G，分子式 $\\mathrm{C_{17}H_{16}N_{4}O_{4}}$ ，结构式如下。  \n\n![](images/b4dc664ee6e646b96cae6eb6593b56fc87842fe2a75b06b81a340640fda47da5.jpg)  \n\n耐晒黄G为乙酰芳胺类单偶氮颜料，微溶于乙醇、丙酮、苯；色泽鲜艳，着色力强，耐光坚牢度好，耐晒和耐热性颇佳，对酸碱有抵抗力，但耐溶剂性差。  \n\n$\\textcircled{2}$ 汉沙黄R（PY10)，分子式 $\\mathbf{C}_{16}\\mathbf{H}_{12}\\mathbf{N}_{3}\\mathbf{O}$ ，结构式如下。  \n\n![](images/1fc66c7f7d3cfce397f54947de34ae2732a39f8d885afb5b44fe6820b19230e2.jpg)  \n\n汉沙黄R为吡唑啉酮类单偶氮颜料，红光黄色粉末，耐光性、耐热性、耐酸性和耐碱性都较好。  \n\n$\\textcircled{3}$ 永固黄GR（PY13)，分子式 $\\mathrm{C}_{36}\\mathrm{H}_{34}\\mathrm{Cl}_{2}\\mathrm{N}_{6}\\mathrm{O}_{4}$ ，结构式如下。  \n\n![](images/929e2caae4490e3289b81481b6023bba8659842340ceca85f63c53c510f06a0e.jpg)  \n\n永固黄GR为联苯类双偶氮颜料，淡黄色粉末，不溶于水，微溶于乙醇，色彩鲜明，着色力强。  \n\n$\\textcircled{4}$ 颜料黄129（PY129)，又称亚甲胺颜料黄，分子式 $\\mathrm{C}_{17}\\mathrm{H}_{11}\\mathrm{NO}_{2}\\mathrm{Cu}$ ，结构式如下。  \n\n![](images/473ea3a5939ad4e158ce5d8d5d1d153ba6912de53eb9ec45f16fe0286542dd30.jpg)  \n\n颜料黄129 为甲亚胺金属络合颜料，黄橙色均匀粉末，具有较好的耐久性和耐晒性。  \n\n③铁黄，分子式FeO3·HzO或FeOOH，又称氧化铁黄，黄色粉末，是一种化学性质比较稳定的碱性氧化物。色泽带有鲜明而纯洁的赭黄色，并有从柠檬黄到橙色一系列色光。具有着色力高、遮盖力强（不大于 $\\scriptstyle15g/\\mathbf{m}^{2}$ )、耐光性好的特点，不溶于碱，微溶于酸。  \n\n（3）蓝色颜料  \n\n$\\textcircled{1}$ 酞菁蓝（PB15)，分子式 $\\mathrm{C}_{32}\\mathrm{H}_{16}\\mathrm{CuN}_{8}$ ，结构式如下。  \n\n![](images/ee6f1c8d3d9602c3090fe43deb199c035c8b8de7d77246600226cf64c12f2764.jpg)  \n\n酞菁蓝为铜酥菁颜料，深蓝色红光粉末。有鲜明的蓝色，具有优良的耐光、耐热、耐酸、耐碱和耐化学品性能，着色力强，为铁蓝的2倍，群青的20倍。极易扩散和加工研磨，是蓝色颜料中主要的一种。酰菁蓝有 $\\alpha$ 型（ $\\mathbf{\\cdotPB15:1})$ ）和 $\\beta$ 型（ $\\mathbf{PB15:3})$ 两类，因酞菁蓝晶型不同、芳环上取代基不同，共有六种不同型号的酞菁蓝。  \n\n$\\textcircled{2}$ 靛葱酮（PB60)，又叫阴丹士林蓝，属葱酮类颜料，分子式为 $\\mathrm{C}_{28}\\mathrm{H}_{14}\\mathrm{N}_{2}\\mathrm{O}_{4}$ ，结构式如下。  \n\n![](images/d4382e681bf1a6dcc2970ce0fb30930f9381a4e7cfa28516c153febb771c75cc.jpg)  \n\n靛葱酮为深蓝色粉末，有较好的耐光、耐候和耐溶剂性能。  \n$\\textcircled{3}$ 射光蓝浆AG（PB61)，又叫碱性蓝，分子式为 $\\mathrm{C}_{37}\\mathrm{H}_{29}\\mathrm{N}_{3}\\mathrm{O}_{3}\\mathrm{S}$ ，结构式如下。  \n\n![](images/7c23fd23b46b10c15d28db3752253d80f9a082dcc5d443b8701655c9c6e68483.jpg)  \n\n射光蓝浆AG为蓝色浆状物，颜色鲜艳，能闪射金属光泽；不溶于冷水，溶于热水（蓝色)、乙醇（绿光蓝色)，有很高的着色力和良好的耐热性，添加黑色油墨中增加艳度，是黑色油墨良好的辅助剂，增加黑度和遮盖力。  \n\n$\\textcircled{4}$ 铁蓝，又称氧化铁蓝，用通式 $\\mathrm{Fe(M)Fe(CN)}_{6}\\mathrm{H}_{2}\\mathrm{O}$ 表示，M为K或 $\\overline{{\\mathbf{NH}_{4}}}$ ，深蓝色，细而分散度大的粉末，不溶于水及醇，有很高的着色力。着色力越强颜色越亮，有高的耐光性，在空气中于 $140^{\\circ}\\mathrm{C}$ 以上时即可燃烧。  \n\n$\\textcircled{5}$ 群青，是含有多硫化钠的具有特殊结晶构造的铝硅酸盐，分子表示式为 $\\scriptstyle2(\\mathbf{Na}_{2}0$ ·$\\mathrm{\\bfAl_{2}O_{3}}\\cdot2\\mathrm{\\bfSiO_{2}})\\cdot\\mathrm{Na}_{2}\\mathrm{\\bfS}_{2}$ ，蓝色粉末，折射率 $1.50{\\sim}1.54\\$ ，不溶于水和有机溶剂，耐碱、耐高温、耐日晒和耐风雨极稳定，但不耐酸，遮盖力和着色力弱。具有清除或减低白色涂料中含有蓝光色光的效能，在灰、黑色中掺入群青可使颜色有柔和光泽。  \n\n（4）绿色颜料  \n\n$\\textcircled{1}$ 酞菁绿G（PG7)，分子式 $\\mathrm{C}_{32}\\mathrm{H}_{1\\sim2}\\mathrm{Cl}_{14\\sim15}\\mathrm{CuN}$ ，结构式如下。  \n\n![](images/e65823f832b2cc2de290f8cbdac3ef896960d0047a92ee6565008b1a6995e2c7.jpg)  \n\n酞菁绿G为多氯代铜酞菁。深绿色粉末，不溶于水和一般有机溶剂，颜色鲜艳，着色力高，耐晒性和耐热性优良，属于不褪色颜料，耐酸碱性和耐溶剂性亦佳。  \n\n$\\textcircled{2}$ 颜料绿(PG8)，分子式 $\\mathrm{C}_{30}\\mathrm{H}_{18}\\mathrm{O}_{6}\\mathrm{N}_{3}\\mathrm{FeNa}$ ，结构式如下。  \n\n颜料绿为深绿色粉末，不溶于水和一般有机溶剂，着色力好，遮盖力强，耐晒、耐热、耐油性优良，无迁移性。 1$\\textcircled{3}$ 黄光铜酞菁（PG36)，分子式 $\\mathrm{C_{32}B_{6}C l_{10}C u N_{8}}$ ，结构式如下。  \n\n![](images/d125486d768e1944f0a87f19c713ef105e969148cbf530c699970bc2735953d3.jpg)  \n\n黄光铜酞菁为黄光深绿色粉末，颜色鲜艳，着色力强，不溶于水和一般有机溶剂，为溴代不褪色颜料。  \n\n④ 氧化铬绿，CrO3，深绿色粉末，有金属光泽，不溶于水和酸，耐光、大气、高温及腐蚀性气体（SOz、HS等)，极稳定，耐酸、耐碱，具有磁性，但色泽不光亮。  \n\n（5）橙色颜料  \n\n$\\textcircled{1}$ 永固橙G（PO13)，分子式 $\\mathrm{C}_{32}\\mathrm{H}_{24}\\mathrm{Cl}_{2}\\mathrm{N}_{8}\\mathrm{O}_{2}$ ，结构式如下。  \n\n![](images/714f0ace3440ba7ef722a9c254a50a3d45dc1a93d8033bd98d35cd49a6ded627.jpg)  \n\n永固橙G为联苯胺类双偶氮颜料，黄橙色粉末，体质轻软细腻，着色力高，牢度好。  \n$\\textcircled{2}$ 永固橙HL（PO36)，分子式 $\\mathrm{C_{17}H_{13}C l N_{6}O_{5}}$ ，结构式如下。  \n\n![](images/831675c32ff5da1002db1690e546e147c1c13196b7ed21c9a522eef903653eff.jpg)  \n\n永固橙HL为苯并咪唑酮系单偶氮颜料，橙色粉末，色泽鲜艳。耐热、耐晒和耐迁移性较好。  \n\n（6）紫色颜料  \n\n① 喹吖啶酮紫（PV19)，又称酞菁紫，分子式C2oH12NO2，结构式如下。  \n\n![](images/f42df840694c744bb3d565dce8346ef93737efc033f5575fa6e14032b15fa646.jpg)  \n\n喹吖啶酮紫为喹吖啶酮类颜料，艳紫色粉末，色光鲜艳，具有优良的耐有机溶剂、耐晒性和耐热性。  \n\n②永固紫RL（PV23），分子式C34H22ClN4O2，结构式如下。  \n\n![](images/04354c87c10277f026da2b71b583af6212db80b50dfc5fca35958e4c58827657.jpg)  \n\n永固紫RL为咔唑二嗪类颜料，蓝光紫色粉末，色泽鲜艳，着色强度高，耐晒牢度 好，耐热性及抗渗性优异。 Ar 1o.  \n\n③ 锰紫（PV16)，分子式NH4MnPO7，紫红色粉末。耐酸但不耐碱，耐光好，耐高温，但着色力和遮盖力不高。微量锰紫加入白色颜料中可起增白作用。  \n\n（7）棕色颜料  \n\n①永固棕HSR（PBr25），分子式C24H15ClzN5O3，结构式如下。  \n\n![](images/98d30afc33978380e8e7796a9f2423594e0dfced02aab6ae3bb3268f81643f27.jpg)  \n\n永固棕HSR为苯并咪唑酮类偶氮颜料，棕色粉末，具有优异的耐热性、耐晒性和耐迁  \n\n移性。  \n\n$\\textcircled{2}$ 苝枣红紫（ $\\mathtt{P r26}$ )，分子式 $\\mathrm{C}_{24}\\mathrm{H}_{10}\\mathrm{N}_{2}\\mathrm{O}_{4}$ ，结构式如下。  \n\n![](images/ef0962b393642668c4d1e6fced81b8bccb0a4a4a7e4081e18f40336497b678d8.jpg)  \n\n花枣红紫为系颜料，暗红色粉末，具有优异的化学稳定性、耐渗性、耐光性及耐迁移性。  \n\n$\\textcircled{3}$ 氧化铁棕（ $\\mathbf{PBr}6\\rangle$ ，通常是由氧化铁黄、氧化铁红和氧化铁黑拼色而成，分子式常用$(\\mathrm{FeO})_{x}\\bullet(\\mathrm{Fe}_{2}\\mathrm{O}_{3})_{y}\\bullet(\\mathrm{H}_{2}\\mathrm{O})_{z}$ 表示。棕色粉末，无毒，有良好的着色力，耐光和耐候性均佳，耐热性稍差。  \n\n填料（filler）也称体积颜料或惰性颜料，它们的特点是化学稳定性好，便宜，来源广泛，能均匀分散在涂料和油墨的基料中。加入填料主要是为了降低涂料和油墨的成本，但同时对涂料和油墨的流变性及物理力学性能起重要作用，可以通过增加涂膜厚度的方式提高涂层的耐磨性和耐久性。  \n\n常用填料有碳酸钙、硫酸钡、氢氧化铝、高岭土、滑石粉等，都是无机物，它们的折射率与低聚物和活性稀释剂接近，所以在涂料和油墨中是“透明”的，对基材无遮盖力。  \n\n$\\textcircled{1}$ 碳酸钙（ $\\mathrm{CaCO_{3}}$ )，无嗅无味的白色粉末，是用途最广的无机填料之一。其比表面积为 ${\\mathfrak{s m}}^{2}/{\\mathfrak{g}}$ 左右，白度为 $90\\%$ 左右。在涂料和油墨中碳酸钙大量作为填充剂起骨架作用。  \n\n$\\textcircled{2}$ 硫酸钡（ $\\mathrm{BaSO_{4}}$ )，又称钡白，无嗅无味白色粉末，化学性质稳定。在涂料和油墨中作填充剂用。  \n\n$\\textcircled{3}$ 二氧化硅（ $\\mathrm{\\SiO}_{2}$ )，又叫白炭黑，是无毒、无味、质轻而蓬松的白色粉末状物质。因生产方式不同又分沉淀白炭黑和气相白炭黑，气相白炭黑属于纳米级精细化学品，粒径在$\\scriptstyle7\\sim20{\\mathfrak{n m}}$ 范围，比表面积 $130{\\sim}400\\mathbf{m}^{2}/\\mathbf{g}$ ，在涂料和油墨中应用，具有卓越的补强性、增稠性、触变性、消光性、分散性、绝缘性和防粘性。目前使用的二氧化硅大多数是经有机或无机表面处理，可防止结块，改善分散性能，以提高其应用性能。  \n\n$\\textcircled{4}$ 高岭土（ $\\mathrm{\\Delta(Al_{2}O_{3}\\bullet S i O_{2}\\bullet\\mathtt{n}H_{2}O)}$ ，通常也称瓷土，是无毒、无味的白色粉末，在涂料和油墨中作填充剂。  \n\n$\\textcircled{5}$ 滑石粉 $3\\mathrm{MgO}\\cdot4\\mathrm{SiO}_{2}\\cdot\\mathrm{H}_{2}\\mathrm{O}$ ，白色粉末，无毒无味，有滑腻感，在涂料和油墨中作填充剂。 5",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 167,
+        "chunk": "# 5.3.1 消泡剂  \n\n消泡剂（defoamer，anti-foamer agent）是一种能抑制、降低或消除涂料和油墨中气泡的助剂。涂料和油墨所用原材料如流平剂、润湿剂、分散剂等表面活性剂会产生气泡，颜料和填料固体粉末加人时会挟带气泡；在生产制造时，因搅拌、分散、研磨过程中，容易卷入空气而形成气泡；在涂料施工和油墨印刷过程中，因使用前搅拌、涂覆也会产生气泡。气泡的存在会影响颜料或填料等固体组分的分散，更会使涂料施工和油墨印刷后涂膜质量变劣，因此必须加入消泡剂来消除气泡。  \n\n在不含表面活性剂的体系中，形成的气泡因密度低而迁移到液面，在表面形成液体薄层，薄层上液体受重力作用向下流动，导致液层厚度减小。通常当层厚减小到大约10nm时液体薄层就破裂，气泡消失。当体系含有表面活性剂时，气泡中的空气被表面活性剂的双分子膜所包裹，由于双分子膜的弹性和静电斥力作用，使气泡稳定，小气泡就不易变成大气泡，并在涂料和油墨表面堆积。  \n\n消泡剂的作用与表面活性剂相反，它具有与体系不相容性、高度的铺展性和渗透性以及低表面张力特性，消泡剂加入体系后，能很快地分散成微小的液滴，与使气泡稳定的表面活性剂结合并渗透到双分子膜里，快速铺展，使双分子膜弹性显著降低，导致双分子膜破裂；同时降低气泡周围的液体表面张力，使小的气泡聚集成大的气泡。最终使气泡破裂。有些消泡剂含有疏水性颗粒（如二氧化硅）时，疏水性颗粒渗透到气泡的表面活性剂膜上，吸收表面活性剂的疏水基团，导致气泡层因缺乏表面活性剂而破裂。  \n\n常用的消泡剂有低级醇（如乙醇、正丁醇）、有机极性化合物（如磷酸三丁酯、金属皂)、矿物油、有机聚合物（聚醚、聚丙烯酸酯)、有机硅树脂（聚二甲基硅油、改性聚硅氧烷）等。对光固化涂料和油墨最常用的消泡剂为有机聚合物和有机硅树脂。  \n\n选择消泡剂除了有高效消泡效果外，还必须没有颜料凝聚、缩孔、针孔、失光、缩边等副作用，而且消泡剂能力持久。根据生产厂家提供的消泡剂技术资料，结合涂料使用的原材料，经分析，通过实验进行筛选，以获得最佳的消泡剂品种、最佳用量和最合适的添加方法。  \n\n消泡剂的消泡性能初步筛选可通过量筒法或高速搅拌法来实现。  \n\n（1）量筒法适用于低黏度的涂料、油墨或乳液。在具有磨口塞的50mL量筒内，加入试样20～30mL，再加人定量的消泡剂，用手指按紧磨口塞来回激烈摇动20次，停止后立即记录泡沫高度，间歇一定时间再记录泡沫高度，然后对各种消泡剂进行比较，泡沫高度越低，消泡效果越好。该法简单方便，但结果较粗糙。  \n\n（2）高速搅拌法本法适用面广，方法简单方便，结果较正确。对低黏度的涂料、油墨或乳液，可用泡沫液体测定法：在有1mL刻度的200mL高型烧杯内，加人100mL试样，添加定量消泡剂，再用高速搅拌器，以恒定的3000～4000r/min转速搅拌，测定固定时间里泡沫的高度。泡沫高度越低，消泡效果越好。或测定泡沫达到一定高度时所需时间，所需时间越短消泡效果越差。  \n\n对高黏度的涂料和油墨可用比重杯法：在200mL容器中，称入试样150g，添加定量消泡剂后，用高速搅拌器在恒定的 2000～6000r/min下搅拌120s后，停止搅拌，立即测定密度，15min后再测定一次，与高速搅拌前样品比较，密度变化越小越好。  \n\n消泡剂在光固化涂料和油墨中一般使用量为0.05%～1.0%，大多数可在涂料和油墨研磨时加入，也有的可用活性稀释剂稀释后，加入涂料和油墨中，要搅拌均匀。表5-5介绍了用于光固化体系的消泡剂。  \n\n表5-5用于光固化体系的部分消泡剂  \n\n\n<html><body><table><tr><td>公司</td><td>商品名称</td><td>组成</td><td>含量/%</td><td>溶剂</td><td>适用范围</td><td>添加量(总 量的比例) 1%</td><td>使用方法</td></tr><tr><td rowspan=\"3\">德谦</td><td>2700</td><td>非聚硅氧烷高分子</td><td>10.0~11.5</td><td>芳香族碳氢 溶剂</td><td>光固化涂料（淋 涂)</td><td>0.1~1.0</td><td>研磨前添加</td></tr><tr><td>3100</td><td>非聚硅氧烷高分子</td><td>44~46</td><td>芳香族碳氢 溶剂</td><td>光固化涂料（淋 涂)</td><td>0.1~1.0</td><td>研磨前添加</td></tr><tr><td>5300</td><td>改性聚硅氧烷</td><td>0.46~0.53</td><td>环己酮/芳香族 碳氢溶剂</td><td>光固化体系（辊 涂、喷涂)</td><td>0.1~0.7</td><td>研磨前添加</td></tr><tr><td rowspan=\"4\">迪高</td><td>Foamex 810</td><td>聚硅氧烷-聚醚共聚 物，含气相SiOz</td><td>100</td><td></td><td>光固化清漆</td><td>0.2~0.8</td><td>直接加人或稀释 后加入研磨料中</td></tr><tr><td>Foamex N</td><td>二甲基聚硅氧烷，含 气相SiOz</td><td>100</td><td></td><td>光固化丝印 油墨</td><td>0.1~0.5</td><td>用前需搅拌，加 人研磨料中</td></tr><tr><td>Airex920</td><td>有机高分子</td><td>100</td><td></td><td>光固化体系</td><td>0.3~1.0</td><td>直接加入或稀释 后在调匀时或清漆 中加人</td></tr><tr><td>Airex 986</td><td>具有硅氧烷端基的 聚合物溶液</td><td>30</td><td>二甲苯</td><td>光固化涂料</td><td>0.1~1.0</td><td>在调匀时或清漆 中加人</td></tr><tr><td rowspan=\"4\">毕克</td><td>BYK055</td><td>非硅聚合物</td><td>7</td><td>烷基苯/丙二醇 甲醚醋酸酯(12/1)</td><td>光固化木器家 具涂料</td><td>0.1~1.5</td><td>研磨前加入</td></tr><tr><td>BYK088</td><td>聚硅氧烷和聚合物 的混合物</td><td>3.3</td><td>支化酯族溶剂</td><td>光固化木器家 具涂料</td><td>0.1~1.0</td><td>研磨前加入</td></tr><tr><td>BYK020</td><td>聚醚改性二甲基聚 硅氧烷共聚物</td><td>10</td><td>乙二醇丁醚/乙 基乙醇/溶剂汽油</td><td>光固化金属、木 材、纸张涂料</td><td>0.1~1.0</td><td>研磨前加人</td></tr><tr><td>BYK067A</td><td>破泡聚硅氧烷非水 乳液</td><td>89</td><td>(6/2/1) 丙二醇</td><td></td><td>0.1~0.7</td><td>研磨前加人</td></tr><tr><td rowspan=\"2\">埃夫卡</td><td>Efka 2720</td><td>非硅聚合物</td><td></td><td></td><td>光固化体系电子</td><td></td><td></td></tr><tr><td>Efka 2721</td><td>非硅聚合物</td><td></td><td></td><td>束体系</td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 168,
+        "chunk": "# 5.3.2 流平剂  \n\n流平剂（levelingagent）是一种用来提高涂料和油墨的流动性，使涂料和油墨能够流平的助剂。涂料和油墨不管用何种涂装方法或印刷方法，经施工后，都有一个流动与干燥成膜的过程，形成一个平整、光滑、均匀的涂膜。涂膜能否达到平整光滑的特性，称为流平性。在实际施工和印刷时，由于流平性不好，刷涂时出现刷痕，喷涂时出现橘皮，辊涂时产生辊痕，印刷时产生印痕，在干燥和固化过程中，出现缩孔、针孔、橘皮、流挂等现象，都称为流平性不良。而克服这些病的有效方法就是添加流平剂。鉴于涂料的主要作用是装饰及保护，油墨的主要作用是再现文字和图形等信息，如果涂层不平整，出现缩孔、橘皮、痕道等病，不仅起不到装饰效果，而且将降低或损坏其保护功能，也无法再现文字和图形信息。因此涂膜外观的平整性是涂膜的重要技术指标，是反映涂料和油墨质量优劣的主要参数之一。  \n\n涂层缺陷的产生与表面张力有关。表面张力是由气相/液相界面的力场与液体内部的力场差异而引起的(图5-3)。  \n\n![](images/7320e656765229269f53bd58b47d0ae9c0c6ae1052903cddbeffe0f06a289edb.jpg)  \n图5-3液体内部与气/液界面的力场分布示意  \n\n分子之间存在着范德瓦尔斯力、氢键等作用而相互吸引。在液体内部的分子受到各个方向对称的力吸引而处于平衡状态。而界面的分子受到液相和气相不同的引力作用，液相的引力大于气相的引力，故处于不平衡状态，这种不平衡的力试图将表面分子拉向液体内部，所以液体表面有自动收缩的趋势。便液体成为液膜（图5-4)，为保持表面平  \n\n衡，就需要有一个与液面相切的力f作用于宽度为的液膜上。平衡时，液体存在的与f大小相等而方向相反的力就是表面张力，其值为  \n\n$$\n_{f=r l\\times2}\n$$  \n\n此处由于液膜有两个，故乘以2，比例系数r称为表面张力系数，单位为N/m（过去单位为dyn/cm，1dyn/cm=10-3N/m)，它表达为单位长度液体收缩表面的力。表面张力系数通常简称为表面张力（surfacetension）。  \n\n当液体滴在固体表面时，由于表面张力形成液滴凸面，液面的切线和固体表面的夹角叫做接触角（contactangle）（图5-5)。通过测量接触角可以反映表面张力的大小。一系列不同表面张力的液体在某固体上作接触角，将各液体的表面张力与对应的接触角余弦作图，将此线外推至cos0=1，它对应的表面张力即为固体表面张力。  \n\n![](images/abe63340d30a4e06eae7a7efeadf208ad6292086005283eb785a50012c21acd7.jpg)  \n图5-4表面张力的本质  \n\n![](images/7b6f392af64eaeec5eb656798b910d09f8c5e7b54a346b92638b7289ae722f67.jpg)  \n图5-5液滴的接触角  \n\n表面张力具有使液体表面积收缩到最小的趋势，同时，也具有低表面张力的液体向高表面张力的液体表面铺展的趋势。因此表面张力是涂料和油墨流平的推动力。当涂料涂装或油墨印刷到底材后，由于表面张力作用使涂料和油墨铺展到底材上；同时表面张力有使涂膜表面积收缩至最小的趋势，这样涂层的刷痕、皱纹等缺陷消失，变成平整光滑的表面。此外，涂料和油墨在底材上的流平性还与涂料和油墨的黏度、底材表面的粗糙程度、溶剂的挥发速率、环境温度、干燥时间等因素有关。一般来说，涂料和油墨的黏度越低，流动性越好，流平性也好；底材表面粗糙，不利于流平；溶剂挥发快，也不利于流平；施工时，环境温度高，有利于流平；干燥时间长，也利于流平。对光固化涂料和油墨，不存在溶剂挥发，涂料和油墨只要经紫外光照就瞬间固化，干燥时间极短，故对涂料和油墨的流平性要求更高。因此选择好合适的流平剂就显得更为重要。有时在生产线上光照前适当有一段流平时间，再经光固化装置进行固化，以保证涂装和印刷的质量。  \n\n鉴于表面张力是涂料和油墨流平的最关键因素，因此在配方设计中都要考虑涂料和油墨组分与底材的表面张力大小以及施工方式上对涂料和油墨表面张力的要求。表5-6 列举了常  \n\n见溶剂、稀释单体和底材的表面张力值。  \n材料的表面张力值  \n\n\n<html><body><table><tr><td>溶剂与树脂</td><td>表面张力</td><td>活性稀释剂</td><td>表面张力</td><td>底材</td><td>表面张力</td></tr><tr><td>水</td><td>72.7</td><td>PEG(400)DA</td><td>42.6</td><td>玻璃</td><td>70</td></tr><tr><td>甲苯</td><td>28.4</td><td>(EO)TMPTA</td><td>39.6</td><td>钢铁</td><td>36～50</td></tr><tr><td>石油溶剂油</td><td>26.0</td><td>PETA</td><td>39.0</td><td>铝</td><td>37~45</td></tr><tr><td>乙酸丁酯</td><td>25.2</td><td>TMPTA</td><td>36.1</td><td>PET</td><td>43</td></tr><tr><td>丙酮</td><td>23.7</td><td>HDDA</td><td>35.7</td><td>PC</td><td>42</td></tr><tr><td>乙醇</td><td>22.8</td><td>(PO)TMPTA</td><td>34.0</td><td>PVC</td><td>39~42</td></tr><tr><td>环氧树脂</td><td>45~60</td><td>TPGDA</td><td>33.3</td><td>PS</td><td>36~42</td></tr><tr><td>三聚氰胺树脂</td><td>42~58</td><td>NPGDA</td><td>32.8</td><td>PE</td><td>32</td></tr><tr><td>醇酸树脂</td><td>33~60</td><td>IBOA</td><td>31.7</td><td>PP</td><td>30</td></tr><tr><td>丙烯酸树脂</td><td>32~40</td><td>2-EHA</td><td>28.0</td><td>PTFE</td><td>20</td></tr></table></body></html>  \n\n流平剂种类较多，常见的有溶剂类、改性纤维素类、聚丙烯酸酯类、有机硅树脂类和氟表面活性剂等，而用于光固化涂料和油墨的流平剂主要有聚丙烯酸酯、有机硅树脂和氟表面活性剂三大类。聚丙烯酸酯流平剂为低分子量（ $6000{\\sim}20000,$ ）的丙烯酸酯均聚物或共聚物，分子量分布窄，玻璃化温度 $\\overline{{\\boldsymbol{T}_{\\mathrm{*}}}}$ 一般在一 $20^{\\circ}\\mathrm{C}$ 以下，表面张力在 $(25\\sim26)\\times10^{-3}\\mathrm{N/m}$ 。加人涂料和油墨中可以降低表面张力，提高对底材的润湿性，能迁移到涂层表面形成单分子层，使涂膜表面的表面张力均匀，避免缩孔产生，改善涂膜的光滑平整性。这类流平剂不影响重涂性。  \n\n氟表面活性剂为氟碳树脂，是具有最低表面张力和最高表面活性的涂料助剂。加入涂料和油墨中可以有效地改善润湿性、分散性和流平性，故用量极低，一般在 $0.03\\%0\\sim0.05\\%$ 但这种流平剂对层间附着力和重涂性影响很大，加之价格昂贵，只用于涂装表面张力低的底材（如PE)涂料中。表5-7介绍了用于光固化体系的流平剂。  \n\n表5-6部分  \n表5-7用于光固化体系的流平剂  \n\n\n<html><body><table><tr><td>公司</td><td>商品名</td><td>组成</td><td>含量 /%</td><td>溶剂</td><td>适用范围</td><td>添加量（占总量 的比例)/%</td><td>使用方法</td></tr><tr><td rowspan=\"5\">德谦</td><td>431</td><td>聚醚改性聚硅 氧烷</td><td>24~27</td><td>芳香族碳氢 溶剂</td><td>光固化涂料</td><td>0.1~0.5</td><td>研磨后加入</td></tr><tr><td>432</td><td>改性聚硅氧烷</td><td>13~14</td><td>二甲苯/丁基溶 纤剂</td><td>光固化涂料</td><td>0.1~0.5</td><td>研磨后加入</td></tr><tr><td>488</td><td>改性聚硅氧烷</td><td>>94.5</td><td></td><td>光固化涂料</td><td>0.1~0.5</td><td>任何阶段添加</td></tr><tr><td>495</td><td>聚丙烯酸酯</td><td>48~52</td><td>二甲苯</td><td>光固化涂料</td><td>0.2~1.5</td><td>任何阶段添加</td></tr><tr><td>810</td><td>聚醚改性聚硅 氧烷</td><td>≥88</td><td></td><td>光固化涂料</td><td>0.01~0.2</td><td>任何阶段添加</td></tr><tr><td rowspan=\"8\">迪高</td><td>Glide 100</td><td>聚硅氧烷-聚醚</td><td>100</td><td></td><td>光固化清漆</td><td>0.05~0.5</td><td>以原装物或稀 释后加入</td></tr><tr><td>Glide432</td><td>共聚物 聚硅氧烷-聚醚 共聚物</td><td>100</td><td></td><td>光固化涂料</td><td>0.05~1.0</td><td>以原装物或稀 释后加人</td></tr><tr><td>Glide435</td><td>聚硅氧烷-聚醚 共聚物</td><td>100</td><td></td><td>光固化体系</td><td>0.05~1.0(清漆） 0.1~0.5（油墨）</td><td>以原装物或稀 释后加人</td></tr><tr><td>Glide 440</td><td>聚硅氧烷-聚醚 共聚物</td><td>100</td><td></td><td>光固化清漆</td><td>0.05~1.0</td><td>以原装物或稀 释后加入</td></tr><tr><td>Flow300</td><td>聚丙烯酸酯 溶液</td><td>48~52</td><td>二甲苯</td><td>光固化清漆</td><td>0.1~0.8</td><td>以原装物或稀 释后加人</td></tr><tr><td>Flow 425</td><td>聚硅氧烷-聚醚 共聚物</td><td>100</td><td></td><td>光固化清漆</td><td>0.1~1.0</td><td>以原装物或稀 释后加人</td></tr><tr><td>FlowZFS460</td><td>聚丙烯酸酯 溶液</td><td>70</td><td>二甲苯、甲基正 丙二醇乙酸酯</td><td>光固化清漆</td><td>0.03~0.5</td><td>以原装物或稀 释后加人</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>公司</td><td>商品名</td><td>组成</td><td>含量</td><td>溶剂</td><td>适用范围</td><td>添加量(占总量</td><td>使用方法</td></tr><tr><td rowspan=\"4\">毕克</td><td>BYK333</td><td>聚醚改性二甲 基聚硅氧烷共 聚物</td><td>≥97</td><td></td><td></td><td>0.05~1.0</td><td>任何阶段添加</td></tr><tr><td>BYK371</td><td>性酸酯改</td><td>40</td><td>二甲苯</td><td>光固化辊涂 清洗固化淋涂 体系</td><td>0.1~5.0</td><td>任何阶段添加</td></tr><tr><td>BYK373</td><td>聚改性羟基</td><td>50</td><td>丙二醇甲醚</td><td>具光科化木材、家</td><td>0.05~0.4</td><td>任何阶段添加</td></tr><tr><td>BYK361</td><td>丙烯酸酯共 聚物</td><td>>98</td><td></td><td></td><td>0.05~0.5</td><td>任何阶段添加</td></tr><tr><td>TROY</td><td>Troysol S366</td><td>非离子型聚硅 氧烷共聚物</td><td>60</td><td></td><td>光固化体系</td><td>0.2~0.6</td><td>最后添加</td></tr><tr><td rowspan=\"2\">科宁</td><td>Perenol S7luv</td><td>丙烯酸酯化聚 硅氧烷</td><td>100</td><td></td><td>光固化体系</td><td>0.5~1.5</td><td></td></tr><tr><td>Perenol S83uv</td><td>聚硅氧烷</td><td>100</td><td></td><td>光固化体系</td><td>0.5~1.5</td><td></td></tr><tr><td>埃夫卡</td><td>Efka3883</td><td>反应性有机硅 氧烷</td><td></td><td></td><td>光固化木器漆 和油墨</td><td></td><td></td></tr></table></body></html>  \n\n涂料和油墨流平性能的评价方法详见附录3、附录4。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 169,
+        "chunk": "# 5.3.3 润湿、分散剂  \n\n颜料分散是有色体系涂料和油墨制造技术的重要环节。把颜料研磨成细小的颗粒，均匀地分布在涂料和油墨基料的连续相中，得到一个稳定的悬浮体。颜料分散要经过润湿、粉碎和稳定三个过程。润湿是用树脂或助剂取代颜料表面上吸附的空气或水等物质，使固/气界面变成固/液界面的过程；粉碎是用机械力把凝聚的颜料聚集体打碎，分散成接近颜料原始状态的细小粒子，构成悬浮分散体；稳定是指形成的悬浮体在无外力作用下，仍能处于分散悬浮状态。要获得良好的涂料和油墨分散体，除与颜料、树脂（低聚物）、溶剂（活性稀释剂）的性质及相互间作用有关外，往往还需要使用润湿分散剂才能达到最佳效果。  \n\n润湿剂（wettingagent）、分散剂（dispersant）是用于提高颜料在涂料和油墨中悬浮稳定性的助剂。润湿剂主要是降低体系的表面张力；分散剂吸附在颜料表面上产生电荷斥力或空间位阻，防止颜料产生絮凝，使分散体系处于稳定状态。润湿剂和分散剂作用有时很难区分，往往兼备润湿和分散功能，故称为润湿分散剂。润湿分散剂大多数是表面活性剂，由亲颜料的基团和亲树脂的基团组成，亲颜料的基团容易吸附在颜料的表面，替代原来吸附在颜料表面的水和空气及其他杂质。亲树脂基团部分则很好地与涂料基料相容，克服了颜料固体与涂料基料之间的不相容性。在分散和研磨过程中，机械剪切力把团聚的颜料破碎到接近原始粒子，其表面被润湿分散剂吸附，由于位阻效应或静电斥力，不会重新团聚结块。  \n\n涂料和油墨常用的润湿分散剂主要有天然高分子类（如卵磷脂)、合成高分子类（如长链聚酯肪酸和多氨基盐，属于两性高分子表面活性剂)、多价羧酸类、硅系和钛系偶联剂等，用于光固化涂料和油墨的润湿分散剂主要为含颜料亲和基团的聚合物。表5-8介绍了用于光固化体系的润湿分散剂。  \n\n表5-8用于光固化体系的润湿分散剂  \n\n\n<html><body><table><tr><td>公司</td><td>商品名</td><td>组 成</td><td>含量/%</td><td>溶剂</td><td>适用范围</td><td>添加量/%</td><td>使用方法</td></tr><tr><td rowspan=\"2\">德谦</td><td>DP983</td><td>高分子聚合物</td><td>57.4~54.5</td><td>醋酸丁酯/二 甲苯</td><td>光固化涂料</td><td>2～5（无机 颜料) 10～40（有 机颜料)</td><td>先与低聚物、单 体混合后，再加人 颜料研磨</td></tr><tr><td>912</td><td>电中性聚酰胺 与聚酯混合物</td><td>48~52</td><td>二甲苯/异 丁醇=9/1</td><td>光固化体系</td><td>1～5（无机 颜料) 0.2~5.0 （有机颜料)</td><td>颜料加人前添加</td></tr><tr><td rowspan=\"4\">毕克</td><td>BYKP-105</td><td>低分子量不饱 和羧酸聚合物</td><td>100</td><td></td><td>光固化体系</td><td>2～5(无机 颜料) 5～10(有机 颜料) 0.5~1(TiO)</td><td>先预热，加入到 研磨料中</td></tr><tr><td>Disperbyk-111</td><td>含酸性基团的 共聚物</td><td>100</td><td></td><td>光固化涂料</td><td>2.5~5（无 机颜料) 1~3(TiO)</td><td>加入研磨料中， 再加入颜料</td></tr><tr><td>Disperbyk-180</td><td>含酸性基团的 嵌段共聚物的烷 烃基铵盐</td><td>100 30</td><td>二羧酸酯</td><td>光固化涂料</td><td>5～10（无机 颜料) 1.5~2.5 (TiO)</td><td>加人研磨料中， 再加入颜料</td></tr><tr><td>Disperbyk-168</td><td>含颜料亲和基 团的高分子量嵌 段共聚物溶液</td><td></td><td></td><td>光固化体系</td><td>10～15（无 机颜料) 30～90(有 机颜料） 5~6(TiO) 70～140(炭</td><td>加人研磨料中， 再加人颜料</td></tr><tr><td rowspan=\"4\">迪高</td><td>Dispers 680UV</td><td></td><td></td><td></td><td></td><td>黑) 10～25（炭</td><td>50℃熔化后用单 体稀释至20%使用</td></tr><tr><td>Dispers 681UV</td><td></td><td></td><td></td><td></td><td>黑) 10～25（有 机颜料）</td><td>50℃熔化后用单 体稀释至20%使用</td></tr><tr><td>Dispers 710</td><td></td><td></td><td></td><td></td><td>10～25（有 机颜料、填料）</td><td></td></tr><tr><td>Dispers 652</td><td></td><td></td><td></td><td></td><td>5~15(TiO、 亚光粉)</td><td></td></tr><tr><td>科宁</td><td>Texaphor P61</td><td>聚氨酯衍生物</td><td>30</td><td></td><td>光固化体系</td><td>2~30(颜料)</td><td></td></tr><tr><td>埃夫卡</td><td>Efka4800</td><td>聚丙烯酸酯</td><td></td><td></td><td>光固化体系</td><td></td><td></td></tr></table></body></html>  \n\n使用润湿分散剂后，颜料分散质量好坏的评价详见附录3、附录4。  \n\n随着光固化涂料和油墨的广泛应用，一些专用于光固化体系的助剂被研究开发，并应用于生产。这类专用助剂除了可以改善对基材的润湿，涂料的流动和流平、消泡和脱泡，提高涂膜的平滑、抗划伤性能、防黏着性外，在结构上都含有丙烯酰氧基，可以参与光固化体系反应，不会发生迁移。迪高公司开发的Rad 系列助剂就是专用于光固化体系的助剂，它们都是丙烯酰氧基改性的有机硅氧烷，结构示意图如下。  \n\n![](images/b25de142d389c54ea9549cc515fe5bf2b80249f5e3605f451a18ddbaef37df2d.jpg)  \n\n表5-9介绍了迪高公司专用于光固化体系的助剂的组成、性能、使用方法。此外，毕克、科宁、埃夫卡等公司也都有类似带有丙烯酰氧基的专用于光固化体系的助剂，见表5-10。  \n\n表5-9迪高公司专用于光固化体系的助剂  \n\n\n<html><body><table><tr><td rowspan=\"2\">商品名</td><td rowspan=\"2\">组成</td><td rowspan=\"2\">含量</td><td rowspan=\"2\">添加量(占总量</td><td rowspan=\"2\">使用方法</td><td colspan=\"5\">性 能</td></tr><tr><td>流动促 进性</td><td>透明性</td><td>平滑 作用 作用</td><td>脱气防缩孔 作用</td><td>防结块 作用</td></tr><tr><td>Rad 2100</td><td>烷交联型聚硅氧</td><td>100</td><td>木器涂料0.05~0.4 印刷油 ~.1 ~1. 0 塑料涂料0.05~0.6</td><td>稀料原装物或</td><td>5</td><td>5</td><td>1 0</td><td>3</td><td>1</td></tr><tr><td>Rad 2200N</td><td>交联型有机硅 聚醚丙烯酸酯</td><td>100</td><td>清漆0.1~1.0 木器涂料0.05～0.4 塑料涂料0.05～0.6</td><td>以原装物或 稀释后加人</td><td>4</td><td>4</td><td>4 4</td><td>4</td><td>3</td></tr><tr><td>Rad2250</td><td>聚交联型有机硅</td><td>100</td><td>清漆0.1~1.0 器涂料0.05~0. 5</td><td>稀料原装物或</td><td>4.5</td><td>4</td><td>4 0</td><td>4</td><td>3</td></tr><tr><td>Rad2500</td><td>烷交丙联型酯硅氧</td><td>100</td><td>丝印油墨0.1～1.0 凸印、凹印油墨0.05～0.5 器涂.料0.05~ 0.5 塑料涂料0.05～0.5</td><td>以原装物或 稀料后加到研 稀时加人</td><td>2</td><td>2</td><td>4 4</td><td>1</td><td>4</td></tr><tr><td>Rad2600</td><td>烷交联型硅氧</td><td>100</td><td>胶印油 0. 1~1. 5</td><td>料加人到研磨</td><td>0</td><td>0</td><td>4.5</td><td>4 0</td><td>4.5</td></tr><tr><td>Rad2700</td><td>烷交联型聚硅氧</td><td>100</td><td>丝印油 ~.1~1. 0</td><td>料加人到研磨</td><td>0</td><td>0</td><td>5 4</td><td>0</td><td>5</td></tr></table></body></html>\n\n$\\textcircled{1}$ 数字表示：0无效—→5强效。  \n\n表5-10其他公司专用于光固化体系的助剂  \n\n\n<html><body><table><tr><td>公司</td><td>商品名</td><td>组成</td><td>含量 1%</td><td>溶剂</td><td>适用范围</td><td>添加量（占总 量的比例）/%</td><td>使用方法</td></tr><tr><td rowspan=\"3\">毕克</td><td>BYKUV3500</td><td>聚醚改性丙烯酸类 官能基聚二甲基硅 氧烷</td><td>≥96</td><td></td><td>水性光固化和光固 化体系</td><td>0.05~2.0</td><td>任何阶段添加</td></tr><tr><td>BYKUV3530</td><td>聚醚改性丙烯酸类 官能基聚二甲基硅 氧烷</td><td>≥96</td><td></td><td>水性光固化和光固 化体系</td><td>0.05~1.0</td><td>任何阶段添加</td></tr><tr><td>BYKUV3570</td><td>聚酯改性丙烯酸类 官能基聚二甲基硅 氧烷</td><td>70</td><td>PONPGNA</td><td>光固化和电子束固 化涂料</td><td>0.1~3.0</td><td>任何阶段添加</td></tr><tr><td>科宁</td><td>Perenol S71UV</td><td>丙烯酸酯化聚硅 氧烷</td><td>10</td><td></td><td>光固化体系</td><td>0.5~1.5</td><td></td></tr><tr><td>埃夫卡</td><td>Efka 3883</td><td>反应性有机硅氧烷</td><td></td><td></td><td>光固化木器漆和 油墨</td><td></td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 170,
+        "chunk": "# 5.3.4 消光剂  \n\n光泽是物体表面对光的反射特性。当物体表面受光线照射时，由于表面光泽程度的不同，光线朝一定方向反射能力也不同，通常称为光泽。光泽是涂料成膜后涂层的一个重要性能，涂料因不同的使用目的和环境，除了保护作用、色彩要求外，对所涂表面涂层的光泽性能也有不同的要求。如汽车的外壳表面希望光泽越高越好，以显示它的豪华和高贵；学校和医院则要求室内的光线柔和，以给人安静、舒适的感觉；军事装备和设施为隐蔽、保密和安全的目的，其表面涂层是半光，甚至无光。涂料按光泽可分为有光漆、半光漆和亚光（平光）漆。  \n\n光线照射到涂膜表面，一部分被涂膜吸收，一部分发生反射和散射，还有一部分发生折射，透过涂膜再反射出来。涂膜表面越平整，则反射光越多，光泽越高；如涂膜表面凹凸不平，非常粗糙，则反射光减少，散射光增多，光泽就低。所以涂膜表面粗糙程度对光泽影响很大。制造高光泽涂料，就要采用一切方法降低涂膜表面的粗糙度；而制造低光泽或亚光涂料，则应提高涂膜表面凹凸不平的程度。添加消光剂是制造亚光涂料的有效措施。  \n\n消光剂（flattingagent）是能使涂膜表面产生预期粗糙度、明显地降低其表面光泽的助剂。涂料中使用的消光剂应能满足下列基本要求：消光剂的折射率应尽量接近成膜树脂的折射率$(1.40{\\sim}1.60)$ ，这样配制的消光清漆透明无白雾，色漆的颜色也不受影响；消光剂的颗粒大小为3～5μm，此时消光效果最好，具有良好的分散与再分散性。消光剂在涂料中能长时间保持均一稳定的悬浮分布，不发生沉降。涂料常用的消光剂有金属皂（硬脂酸铝、锌、钙盐等)、改性油（桐油)、蜡（聚乙烯蜡、聚丙烯蜡、聚四氟乙烯蜡)、功能性填料（硅藻土、气相$\\mathrm{\\overline{{SiO_{2}}}}$ )。光固化涂料使用的消光剂主要为 $\\mathrm{SiO}_{2}$ 和高分子蜡，采用粒径为 $3\\sim5\\mu\\mathrm{m}$ 时效果最好。消光剂除了配成浆状物后加人到涂料内分散外，也可以直接加入涂料中分散。采用高速分散，切勿过度研磨，尽量避免使用球磨或三辊机分散。采用高分子蜡作消光剂，对光固化涂料还有提高光固化速率的作用，因蜡迁移到表面，可以阻隔氧的进人，减少氧阻聚效应的缘故。  \n\n表5-11介绍了用于UV光固化体系的消光剂。  \n\n表5-11用于UV光固化体系的消光剂  \n\n\n<html><body><table><tr><td>公司</td><td>商品名</td><td>组 成</td><td>适用范围</td><td>添加量 （占总量 的比例)/%</td><td>使用方法</td></tr><tr><td>毕克</td><td>Ceraflour 950</td><td>微粉化改性高密度聚乙烯蜡 混合物</td><td>光固化家具和地板 涂料</td><td>1.0~10.0</td><td>在生产过程前期加人，以 保证足够的分散</td></tr><tr><td rowspan=\"5\">德谦</td><td>UV55C</td><td>特殊的蜡处理消光粉</td><td>光固化涂料</td><td></td><td></td></tr><tr><td>UV70C</td><td>特殊的蜡处理消光粉</td><td>光固化涂料</td><td></td><td></td></tr><tr><td>FA-110</td><td>高分子聚乙烯蜡浆9.5%～ 10.5%(二甲苯/乙酸丁酯)</td><td>光固化涂料</td><td>10~20</td><td>直接加入成品，搅匀，无 需研磨</td></tr><tr><td>11MW-611</td><td>微粉化改性PP蜡</td><td>光固化涂料</td><td>0.5~5.0</td><td>以高速搅拌的方式直接 分散于涂料中</td></tr><tr><td>MW-612</td><td>微粉化PTFE改性PE蜡</td><td>光固化涂料</td><td>0.5~3.0</td><td>以高速搅拌的方式直接 分散于涂料中</td></tr><tr><td rowspan=\"2\">格雷斯</td><td>Rad 2005</td><td>有机物表面处理SiO2</td><td>光固化涂料</td><td>5~15</td><td>任何阶段添加</td></tr><tr><td>Rad 2105</td><td>有机物表面处理SiOz</td><td>光固化涂料(厚涂层)</td><td>5~15</td><td>任何阶段添加</td></tr><tr><td>微粉</td><td>Propyltex200SF</td><td></td><td></td><td></td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 171,
+        "chunk": "# 5.3.5 阻聚剂  \n\n光固化产品是一种聚合活性极高的特殊产品。它的主要组成———低聚物和活性稀释剂都是高聚合活性的丙烯酸酯类，另一重要组成———光引发剂又是极易产生自由基或阳离子的物质。在这样一个混合体系中，极易因受外界光、热等影响而发生聚合，必须加入适量的阻聚剂。  \n\n阻聚剂（polymerizationinhibitor）顾名思义是阻止发生聚合反应的助剂。阻聚剂能终止全部自由基，使聚合反应完全停止。常用的阻聚剂有酚类、类、芳胺类、芳烃硝基化合物等。空气中氧是很好的阻聚剂，因氧自身是双自由基，极易与自由基结合，生成过氧化自由基，引发活性大大降低，最后生成单体和过氧键交替的低聚物。光固化产品阻聚剂主要用酚类，如对羟基苯甲醚（HO—《_CH）、对苯二酚（HO-《_OH）和2,6-二叔丁基对C(CH)3甲苯酚［HC— OH 」等。由于对苯二酚的加人，有时会引起体系颜色变深，往往不C(CHg)s被采用。但是酚类阻聚剂必须在有氧气的条件下才能表现出阻聚效应，其阻聚机理如下。  \n\n在酚类阻聚剂存在下，使过氧化自由基很快终止，保证体系中有足够浓度的氧，延长了阻聚时间。因此光固化产品除了加酚类阻聚剂以提高贮存稳定性外，还必须注意存放的容器内产品不能盛得太满，以保证有足够的氧气。  \n\n美国雅宝公司介绍了应用于光固化体系的两种高效阻聚剂FIRSTCUREST-1和ST-2，ST-1 和 ST-2 的活性成分均为NPAL［三(N-亚硝基-N-苯基羟胺)铝盐]，分子式为C18H15NOgAl，分子量为438。NPAL可以用于烯烃树脂体系，它在60℃下均可使体系保持稳定。ST-1和 ST-2继承了NPAL优良的稳定性且为厌氧型的阻聚剂。有关ST-1 和 ST-2产品说明见表5-12。  \n\n![](images/784e468aff5f2a4ba1591566767f3b809a48dda4ea09e6c8e2d829f52940c6c2.jpg)  \n\n表5-12 ST-1和ST-2产品说明  \n\n\n<html><body><table><tr><td>名称</td><td>外观</td><td>活性组分含量/%</td><td>使用量/%</td><td>应 用</td></tr><tr><td>ST-1</td><td>黄色或棕色溶液</td><td>8</td><td>0.1~1</td><td rowspan=\"2\">用于延长活性稀释剂和光敏树脂的有效期；也用于 光固化涂料、光固化胶黏剂、光固化油墨等制品</td></tr><tr><td>ST-2</td><td>黄色或棕色溶液</td><td>4</td><td>0.1~2</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 172,
+        "chunk": "# 第6章 光固化涂料  \n\n涂料是一种重要的、用途广泛的化工材料，涂布于物体表面形成一层薄膜，是保护和装饰物体表面的涂装材料，它能提高被涂物的使用寿命和使用效能，还能赋予物体一些特殊功能。  \n\n涂料品种繁多，按溶剂来分类可分为溶剂型涂料、高固体分涂料、粉末涂料、水性涂料、辐射固化涂料等；按被涂物来分类有纸张涂料、木器涂料、塑料涂料、金属涂料、皮革涂料等；按用途来分类有建筑涂料、家具涂料、汽车涂料、卷材涂料、罐头涂料、光纤涂料等；还有按特殊功能需要分类的如绝缘涂料、导电涂料、高温涂料、防污涂料、防辐射涂料、防锈涂料等。国内采用的是以成膜树脂为基础的分类法，如醇酸树脂漆、环氧树脂漆、硝基漆、氨基树脂漆、聚氨酯漆、聚酯漆、丙烯酸漆等。  \n\n紫外光固化（UV）涂料是一种新型的环保型涂料。它的干燥速率极快，只要几秒钟UV光照就能固化，最快的可到1/10s，像光纤涂料，固化速率已达2500～3000m/min，所以生产效率较高。UV涂料没有溶剂，VOC排放几乎为零，不污染环境，属于环境友好型涂料。另外UV涂料节能，与热固型涂料和粉末涂料相比，能耗仅为其1/5～1/10。自1968年德国拜耳公司首先研发了第一代苯乙烯/不饱和聚酯UV木器涂料以来，UV涂料的生产和应用发展迅速。UV涂料已成为光固化产业领域产销量最大的产品，规模远大于UV油墨和UV胶黏剂。UV涂料所适用的基材已由木材扩展至纸张、塑料、金属、石材、织物、皮革等；涂料的外观也由最初的高光型，发展出亚光型、磨砂型、金属闪光型、珠光型、纹理型等；涂料涂装有辊涂、淋涂、喷涂、浸涂和甩涂等不同方式。 汉装  \n\nUV涂料与普通涂料所用主要原材料比较见表6-1。  \n\n表6-1UV涂料与普通涂料所用主要原材料比较  \n\n\n<html><body><table><tr><td>UV涂料</td><td>普通涂料</td><td>UV涂料</td><td>普通涂料</td></tr><tr><td>低聚物</td><td>成膜物</td><td>颜料</td><td>颜料</td></tr><tr><td>活性稀释剂</td><td>溶剂</td><td>填料</td><td>填料</td></tr><tr><td>光引发剂</td><td>催化剂</td><td>助剂</td><td>助剂</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 173,
+        "chunk": "# 6. 1. 1 低聚物  \n\n成膜物是涂料的主体组成，它是涂料中的流体组成部分，将涂料中颜料、填料等固体粉状物质连接起来，经研磨分散后形成浆状分散体，施工涂覆在基材上，干燥后固定下来。涂料的涂膜性能、施工性能和其他的特殊性能主要取决于成膜物。UV涂料的成膜物是低聚物，它的性能基本上决定了固化前涂料的施工性能和光固化速率、固化后涂膜性能和其他特殊性能，因此低聚物的选择是UV涂料配方设计的最重要环节。  \n\nUV涂料主要是自由基光固化体系，所以所用的低聚物为各类丙烯酸树脂。最常用的为环氧丙烯酸酯、聚氨酯丙烯酸酯、聚酯丙烯酸酯和丙烯酸酯化的聚丙烯酸树脂，它们的一般性能见表6-2。阳离子UV涂料低聚物则为环氧树脂和乙烯基醚类化合物。  \n\n表6-2光固化涂料用低聚物的一般性能  \n\n\n<html><body><table><tr><td></td><td>性能</td><td>环氧丙烯酸酯</td><td>聚氨酯丙烯酸酯</td><td>聚酯丙烯酸酯</td><td>丙烯酸酯化聚丙烯酸树脂</td></tr><tr><td rowspan=\"4\">固化前性能</td><td>释性</td><td>商</td><td></td><td></td><td></td></tr><tr><td></td><td></td><td>较高般</td><td>易可变释</td><td>较高股</td></tr><tr><td>固化速率</td><td>较快</td><td>可变（大多数较慢）</td><td>可变(大多数较慢)</td><td>较慢</td></tr><tr><td>相对成本</td><td>低</td><td>较高</td><td>低</td><td>较高</td></tr><tr><td rowspan=\"5\">固化后性能</td><td>拉伸强度</td><td>较高</td><td>可变(大多数低)</td><td>中等</td><td>较低</td></tr><tr><td>柔韧性</td><td>较差</td><td>较好</td><td>可变</td><td>较好</td></tr><tr><td>耐化学药品性</td><td>优秀</td><td>较好</td><td>较好</td><td>较好</td></tr><tr><td>硬度</td><td>较高</td><td>可变(一般较低)</td><td>中等</td><td>较低</td></tr><tr><td>耐黄变性</td><td>中等至较差</td><td>可变（脂肪族好）</td><td>较差</td><td>优秀</td></tr></table></body></html>  \n\n环氧丙烯酸酯合成较容易，价格低，其固化速率、固化膜硬度、耐抗性、耐腐蚀性、拉伸强度以及对大多数基材的附着性能等都较为优异，具有较高的性价比，已成为UV涂料大多数常规配方的首选主体树脂。主要缺点是柔韧性差，固化膜硬而脆；固化收缩率较大，影响附着力；耐黄变性也较差。  \n\n聚氨酯丙烯酸酯的特点是柔韧性好，对大多数基材附着力和耐腐蚀性、耐抗性都很优异，脂肪族聚氨酯丙烯酸酯耐黄变性优秀，因此在UV塑料涂料和耐黄变性高的UV涂料上作为首选主体树脂。主要缺点是价格较高，固化速率较慢。在UV涂料中常常与环氧丙烯酸酯配合使用，获得较为理想的性价比。  \n\n聚酯丙烯酸酯一般在UV涂料中很少单独用作主体树脂，往往与环氧丙烯酸酯和聚氨酯丙烯酸酯合用。聚酯丙烯酸酯对颜料润湿性好，有利于颜料分散，在色漆配方中常使用。  \n\n丙烯酸酯化聚丙烯酸树脂在UV涂料中也不作主体树脂单独使用。因分子量较大，黏度大，固化速率低，但其固化收缩率较低，对改善附着力有帮助。  \n\n不饱和聚酯早期作为UV木器涂料主体树脂使用，因性能不如丙烯酸类低聚物，在我国基本上不使用。 木",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 174,
+        "chunk": "# 6.1.2 活性稀释剂  \n\n活性稀释剂是UV涂料的又一个重要组分，它除了稀释降黏外，还具有调节固化膜的性能。丙烯酸酯类功能性单体具有高反应活性和低挥发性而普遍用于UV涂料中。选择活性稀释剂除了考虑低黏度外，光固化反应活性与固化交联后膜的性能也是要考察的指标，对一些强调卫生安全的涂料配方，还要考虑活性稀释剂的气味、皮肤刺激性和毒性。  \n\nUV涂料常用的单官能度丙烯酸酯有HEMA、EOEOEA、2-POEA等，1BOA体积收缩率低、折射率高，但气味大。过去用NVP，因为含有致癌物而不再使用。双官能度丙烯酸酯有TPGDA、DPGDA、HDDA、NPGDA、PO-NPGDA 和 PEGDA等。早期用的 DEG-DA、TEGDA因皮肤刺激性太强，现也不用。多官能度丙烯酸酯有TMPTA、PETA、EO-TMPTA、PO-TMPTA、GPTA等。为了增加交联度，提高硬度，还可使用双三羟甲基丙烷四丙烯酸酯和双季戊四醇五/六丙烯酸酯。实际配方中往往将单、双、多官能度丙烯酸酯配合使用，以性能互补，达到综合效果好的目的。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 175,
+        "chunk": "# 6. 1.3 光引发剂  \n\n光引发剂是UV涂料中专用的催化剂，它也是UV涂料中一个重要组成，决定UV涂料的光固化速率。对于无色清漆类UV涂料，光引发剂常使用1173、184、651和BP/叔胺。1173为首选光引发剂，因价格较低，又是液体，光引发活性高、不黄变；但挥发性较大，光分解产物苯甲醛有味。651价格也较低，光引发活性高；但易黄变，不能用于耐黄变性能要求高的UV涂料中。BP/叔胺价格低，但BP易升华，BP/叔胺光引发活性也不高，又易黄变，只能用于低档的UV涂料中。184高活性、低气味、耐黄变，是耐黄变UV涂料首选的光引发剂，为了提高光固化速率，往往与TPO配合使用。对于有色UV涂料，光引发剂则要用ITX、907、369、TPO、819等。白色UV涂料以TPO、819或TPO/184、819/184等为佳；其他颜料UV涂料，则可用ITX/907、ITX/369，或加上651、1173、184和TPO复合体系。有时UV涂料为了减少氧阻聚、提高光固化速率，往往加入少量活性胺。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 176,
+        "chunk": "# 6.1.4 颜料、填料  \n\n目前UV涂料大多数为无色清漆类，不用颜料。有色UV涂料主要用于UV木器涂料，以在层压板、中密度板上使用为主，单色居多。可用颜料也可用染料，染料透明性好，颜料耐光性好。  \n\nUV涂料有时要加人一些填料，以减轻涂料固化后的体积收缩，对改善附着力有益；同时能增强固化膜的强度、耐磨性和耐热性。如耐磨UV涂料常常会加人氧化铝、二氧化硅等填料。但填料的加入，会使涂料黏度增加，透明度变差，固化涂层柔韧性下降，所以加入量要适当。现在使用的填料大多是经表面处理的填料，在涂料中容易分散，对黏度影响较低。近年来纳米技术发展快速，纳米材料使用日益广泛，纳米填料在涂料上应用受到人们的重视，纳米二氧化硅、纳米碳酸钙、纳米碳酸钙/二氧化硅复合填料都开始用于UV涂料。实验表明UV涂料加人纳米二氧化硅后，由于纳米二氧化硅对400nm以内的紫外光吸收率高达70%以上，相对减弱了UV涂料吸收UV辐照的强度，从而降低了UV涂料的固化速率，但明显提高了UV涂料固化膜的硬度和附着力（表6-3)。  \n\n表6-3纳米二氧化硅对UV涂料固化膜硬度和附着力影响  \n\n\n<html><body><table><tr><td>项目</td><td colspan=\"5\">参数</td><td colspan=\"6\"></td></tr><tr><td>纳米二氧化硅添加量/%</td><td>0</td><td>0.25</td><td></td><td>0.50</td><td>1.0</td><td></td><td>1.5</td><td></td><td>2.0</td><td></td></tr><tr><td>涂膜硬度/H</td><td>2</td><td></td><td>3</td><td>4</td><td></td><td>4</td><td></td><td>5</td><td></td><td>5</td></tr><tr><td>附着力/%</td><td>86</td><td></td><td>89</td><td>92</td><td></td><td>97</td><td>99</td><td></td><td>99</td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 177,
+        "chunk": "# 6.1.5 助剂  \n\n助剂是UV涂料的辅助成分。助剂的作用是改善涂料的加工性能、贮存性能和施工性能，防止涂膜病产生，提高涂膜性能和赋予涂膜某些特殊功能等。  \n\nUV涂料常用助剂有消泡剂、流平剂、润湿分散剂、附着力促进剂、消光剂、阻聚剂等，它们在UV涂料中各起着不同的作用。  \n\n（1）消泡剂在涂料生产中，由于机械的操作，会产生气泡和泡沫，延长生产周期，还会给涂膜留下缩孔、针孔、鱼眼等病，既影响漆膜的外观，又妨碍漆膜的保护作用。最适用的方法是使用消泡剂和抑泡剂消泡。抑泡剂加人可避免泡沫的形成，而消泡剂加人能消除已形成的泡沫。由于消泡剂的表面张力低，特别是消泡作用强的消泡剂表面张力更低，所以添加量应以解决泡沫为准，过量添加，易造成缩孔。消泡剂用量一般为涂料总量的0.05%～1.0%。UV涂料常用的消泡剂为聚硅氧类、改性有机硅类和聚合物型，毕克、迪高和德谦等公司有专用于UV涂料的消泡剂。近年来又出现了含氟的消泡剂，消泡效果好，用量也极少。  \n\n（2）流平剂涂料施工后，都有一个流动及干燥成膜的过程。施涂后的湿涂膜能流动而消除涂痕，在干燥后得到均匀平整涂膜的程度称为流平性。在实际施工时，常出现刷痕、辊痕、橘皮、缩孔、针孔等流平不良现象，为克服和防止这些病最有效的方法是添加流平剂。加人流平剂后，可增加涂料对底材的润湿性，改善涂料的流动性，延长流平时间，在涂膜表面形成单分子层，提供均匀的表面张力，具有平整、光滑的效果，从而改善涂膜流平，提高光滑度和光泽。用于UV涂料的流平剂主要有聚丙烯酸酯类、有机硅树脂类和氟表面活性剂三类，目前也都有专用于UV涂料的流平剂。  \n\n（3）润湿分散剂颜料在漆基中的润湿和分散是色漆制造的重要环节，包括颜料的润湿、研磨破碎、分散稳定三个过程。润湿剂、分散剂是提高色漆研磨效率，保持分散体系稳定所必需的一类助剂。润湿剂、分散剂都具有较低的表面张力，与树脂体系有良好的相容性。润滑剂所含活性基团可定向吸附在颜料表面，增加与树脂的亲和性，同时降低漆料的表面张力，加速漆基树脂渗透进人颜料粒子的孔隙之中，帮助研磨分散设备将颜料团粒打开，减少研磨时间。分散剂除具有润湿剂同样的润湿作用外，其活性基一端能吸附在粉碎成细小颗粒的颜料表面，另一端进人漆基形成吸附后，产生电荷斥力或空间位阻，使颜料粒子能长期分散悬浮于漆基中，避免絮凝，保证制成的色漆贮存稳定。用于UV涂料的润湿分散剂主要为含颜料亲和基团的聚合物。  \n\n（4）附着力促进剂涂膜与基材之间可通过机械结合、物理吸附形成氢键或化学键、互相扩散及静电作用结合在一起。这些作用所产生的黏附力决定了涂膜与基材之间的附着力。附着力促进剂是一种能提高涂料与基材间附着力的助剂，对于一些涂料较难附着的基材如金属、塑料、玻璃等，在涂料中往往要加人附着力促进剂。对金属基材的附着力促进剂大多为带有羧基和羟基等极性基团的化合物，UV涂料常用的有甲基丙烯酸磷酸酯：甲基丙烯酸磷酸单酯PM-1，甲基丙烯酸磷酸双酯 PM-2。对玻璃基材，通常用硅偶联剂作附着力促进剂，如KH570（甲基丙烯酸化的硅氧烷)。塑料基材由于塑料品种较多，大多数塑料通过选择合适的低聚物和活性稀释剂就可基本解决附着力问题；对表面能低、为非极性结构的聚烯烃除了选用表面能较低的低聚物和活性稀释剂，提高涂料对聚烯烃基材的表面润湿外，配方上要考虑降低固化收缩率。目前聚烯烃基材主要通过涂装前用电晕处理或火焰喷射处理，以使其表面产生羟基、羰基和羧基等极性基团，解决与涂料的附着力问题。  \n\n（5）消光剂光泽是涂料成膜后涂层的一个重要性能。光线照射到涂膜表面，一部分被涂膜吸收，一部分发生反射和散射，还有一部分发生折射，透过涂膜再反射出来。涂膜表面越平整、光滑，则反射光就越多，光泽越高；若涂膜表面凹凸不平，非常粗糙，则反射光减少，散射光增多，光泽就低。涂料因使用目的、环境和个人的喜爱不同，对其的光泽要求也不同，如学校、医院要求室内光线柔和，军事装备和设施要求表面涂层半光，甚至无光，现在人们对家具和地板也从过去喜爱高光转向亚光，因此制造低光泽或亚光涂料，就需要通过在涂料中添加消光剂来实现。消光剂要求折射率尽量接近树脂的折射率（1.40～1.60)，这样配制消光涂料透明度好，也不影响色漆的颜色。UV涂料常用的消光剂为二氧化硅和高分子蜡，粒径在3～5um时效果最好。消光剂可配成浆状物加入涂料中分散，也可直接加入涂料中分散，一般采用高速分散，不宜用研磨机分散。  \n\n（6）阻聚剂这是用于UV涂料在生产、运输和贮存时避免发生热聚合，提高UV涂料贮存稳定性而添加的助剂。UV涂料常用的阻聚剂为对苯二酚、对甲氧基苯酚和2,6-二叔丁基对甲苯酚等酚类化合物。它们必须在有氧气存在下才能产生阻聚作用，所以UV涂料存放的容器，必须留出足够空气，保证存在足够的氧气。近来还有一种高效阻聚剂三（N-亚硝基-N-苯基羟胺）铝盐，因溶解性差而配成活性稀释剂溶液使用，代号ST-1（8%含量)和 ST-2（4%含量)，用量：ST-1为0.1%～1.0%，ST-2为0.1%～2.0%。  \n\nUV涂料是由固体（如颜料、填料等)、液体（活性稀释剂等）和树脂状物质（低聚物等）组成，要成为均匀的混合物，就需要用机械进行研磨分散，这是涂料生产的主要工艺。鉴于目前大多数UV涂料是清漆，所以生产上都采用高速搅拌机进行研磨分散。对于UV色漆则大多采用砂磨机或球磨机进行研磨分散。  \n\nUV涂料由于施工方式不同（有辊涂、淋涂、喷涂等)、基材不同（有纸张、木器、塑料、金属、石材、皮革等)、颜色不同，所以UV涂料品种繁多，要求UV涂料产品能系列化。  \n\n纸张上光涂料是一种罩光漆，属于印刷后加工的一种重要方法，应用于书刊杂志画册封面、广告宣传画、商标、商品外包装纸盒、装饰纸袋等的涂布装饰，以增强纸印刷品的外观效果，改善纸印刷品的使用性能，增进纸印刷品和商品的保护性能，提高商品档次，增加附加值。以前的纸张罩光方法是采用覆膜，在纸上覆合一层聚氯乙烯或聚乙烯或聚丙烯薄膜，但覆膜成本较高，在温度和湿度变化时，因薄膜与纸的膨胀收缩不一致，引起翘边，容易发生剥离，特别是覆膜后纸张不能回收再利用，所以慢慢地被涂料上光所替代。涂料上光剂中溶剂型上光油上光因上光速率慢，生产效率低，耐抗性差，尤其是有机溶剂挥发，污染环境，对人体有害，涂层存在有机物残留，应用受到限制，有被替代和淘汰的趋势。水性上光油上光虽然无溶剂排放，属环保产品，印后加工适性也好，但也存在光泽和耐抗性较差、容易造成印品尺寸变形等问题。而VU上光油上光由于上光速率快，瞬间固化，可以联机上光，上光与印刷同步，可立刻进行后加工，生产效率高；光泽度、耐抗性、附着力都优异；无溶剂排放，不污染环境；可满足印刷品多样化要求，可全面上光、局部上光、特殊上光，提高产品档次，因此UV上光已成为纸印刷品印后加工的一种重要手段。纸张罩光的不同加工方法比较见表6-4。  \n\n表6-4纸印刷品罩光的不同加工方法比较  \n\n\n<html><body><table><tr><td colspan=\"2\">试验项目</td><td>PVC覆膜</td><td>BOPP覆膜</td><td>UV上光</td><td>涂料压光</td><td>涂料上光</td><td>测试方法</td></tr><tr><td colspan=\"2\">平滑性 光泽</td><td>好 77</td><td>好 77</td><td>好 90</td><td>很好 75</td><td>一般 40</td><td>目视 60°镜面反射</td></tr><tr><td colspan=\"2\">附着力 耐粘连性</td><td>很好 很好</td><td>很好 很好</td><td>很好 很好</td><td>好 好～一般</td><td>很好 一般</td><td>胶带试验 50℃，80%RH</td></tr><tr><td colspan=\"2\">耐磨性 耐稳定性 污染性</td><td>好 很好</td><td>好 好好</td><td>很好 好</td><td>差 好～一般</td><td>差 好很好般</td><td>500g/m2,.10 褪色试验机200h</td></tr><tr><td>耐</td><td>水</td><td>一般 很好</td><td>好～-般 很好</td><td>很好 很好</td><td>差 差</td><td>差</td><td>标记24h后，乙醇擦拭</td></tr><tr><td></td><td>1%NaOH</td><td>好～一般</td><td></td><td></td><td></td><td>差</td><td></td></tr><tr><td>化</td><td></td><td></td><td>好～一般</td><td>很好</td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td>差</td><td>差</td><td></td></tr><tr><td>学</td><td>2%HC1</td><td>好</td><td>好</td><td>好</td><td></td><td></td><td></td></tr><tr><td></td><td>5%CHgCOOH</td><td>好</td><td></td><td></td><td>差</td><td>差</td><td></td></tr><tr><td>药</td><td></td><td></td><td>好</td><td>好</td><td>差-</td><td>差</td><td></td></tr><tr><td>品</td><td>乙醇</td><td>很好～好</td><td>优</td><td>很好</td><td>差</td><td>差</td><td>室温，点滴30min</td></tr><tr><td>性</td><td>汽油</td><td>好～一般</td><td>优</td><td>很好</td><td></td><td></td><td></td></tr><tr><td></td><td>甲苯</td><td>差</td><td>一般</td><td></td><td>差</td><td>差</td><td></td></tr><tr><td></td><td></td><td></td><td></td><td>很好</td><td>差</td><td>差</td><td></td></tr><tr><td>后加工适</td><td>熟压</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td>很好</td><td></td><td>好</td><td>好</td><td>很好</td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>性</td><td>烫金</td><td>很好</td><td>一般</td><td>好</td><td>很好～好</td><td>很好</td><td>乳液型</td></tr></table></body></html>\n\n$\\textcircled{1}18\\mathrm{f}/\\mathrm{cm}^{2}=98\\mathrm{Pa}$ 典  \n\n纸印刷品UV上光按上光设备可分为单机上光和联机上光两种。单机上光又称脱机上光，是用独立的上光设备，若用专用上光设备上光，多采用辊涂式上光机，能一机多用，既可整幅面上光，也可局部上光，可水性上光与UV上光两用。也可利用现有的印刷机上光，减少上光设备投资，生产效率高，套印精度高，既可整幅面上光，又可局部上光。胶印机、柔印机、凹印机和丝网印刷机都可以用于上光。联机上光是印刷机组同上光机组联成一体化，印刷完成后随即进行上光，上光速率与印刷速率同步，生产效率高，同样可整幅面上光，又可局部上光，上光和印刷都由质量控制中心监控，所以，印刷和上光质量稳定。多色胶印机、多色凹印机、多色柔印机、胶凹柔组合印刷机、丝网印刷机都可以联机上光。现在生产的胶印机、凹印机和柔印机很多都在机器上加设上光设备组合，供纸印刷品上光使用。  \n\n纸印刷品按上光效果可分整幅面上光、局部上光、消光（亚光）和特效上光。整幅面上光是对纸印刷品表面全部涂布一层上光涂料，目前大多数印刷品采用此法上光；有些印刷品只需要画面设计部分上光，利用上光部分的高亮度与未上光部分所形成的对比亮度差，产生奇妙的艺术效果，就可采用局部上光；有些印刷品要稳重、高雅或爽滑、耐折，不需要上光增亮，就可采用消光；有些印刷品要使上光后产生特种艺术效果，如磨砂、冰花、金银色、珠光等，就需要特效上光。  \n\nUV纸印刷品上光的底材是印刷后的纸张，纸质材料由纤维素和其他添加成分构成，具有多孔极性的表面，因此UV纸张上光油对纸质底材的附着力较强，但对油墨印刷区域的附着力，则因印刷油墨性质不同而不同。印刷采用胶印，因胶印油墨往往使用蜡和有机硅系列的消泡剂或流平剂，使油墨印刷区域表面张力较低，UV上光油对这些区域的润湿附着能力大大下降。为保证UV上光油对纸质区域和油墨印刷区域同时具有良好的附着力，应尽量避免使用含蜡和有机硅的印刷油量。在联机上光时，印刷油墨并未干燥就UV上光，湿油墨和光油可能会渗透扩散，造成印刷分辨率下降，因此需在UV上光油配方上作调整以适应联机上光。应用于包装纸盒UV上光时，大面积平面纸板经印刷、上光后，经模切、折叠，在待粘接部位涂胶、贴合。若UV上光油中含有有机硅类助剂，则会影响包装盒的粘接，对这类材料UV上光，上光油配方中应尽量不用有机硅助剂。对一些要求无气味的包装材料上光，则在配方中要选用低气味的活性稀释剂、光引发剂和叔胺助引发剂。  \n\nUV纸张上光油所用材料主要选用环氧丙烯酸酯，价格低，固化速率快，附着力、硬度、光泽和耐抗性能都优异；缺点是脆性大，耐黄变性差。适当地配以乙氧基化TMPTA或丙氧基化甘油三丙烯酸酯，可基本满足涂层柔韧性要求。聚氨酯丙烯酸酯也是合适的低聚物，特别是可提供优良的柔韧性，但固化速率较慢和价格较高，影响了实际使用。活性稀释剂最常用的是TMPTA、烷氧基化TMPTA和TPGDA。光引发剂一般以1173为主，有时为降低成本，配以二苯甲酮/叔胺引发体系，为了减少氧阻聚影响，往往加人活性胺。流平剂和消泡剂可使用有机硅类助剂，但对于需粘接、烫金等后加工的上光油尽量改用聚合物类助剂或少用有机硅类助剂。  \n\n纸印刷品的UV上光除了专用涂布机上光外，传统的四种印刷方式（胶印、凸印、凹印、网印）均可进行纸印刷品上光，尤其印刷联机上光已逐渐成为上光工艺的主流方式，而不同印刷方式对UV上光油要求是不相同的，所以在UV纸张上光油配方上要加以考虑。利用胶印机上光涂布一般有两种方式：一种是利用胶印机的润版系统稍加改进，进行上光涂布；另一种是利用输墨系统像油墨印刷一样进行上光涂布。上光涂料由着液辊转移到上光涂布辊筒再涂布到印品上，是间接涂布方式。UV上光涂料黏度较高，一般在 $30\\sim40\\mathrm{s}$ （涂-4杯， $25\\mathrm{^\\circC}$ ）最高不超过50s；表面张力要略小于印刷品表面油墨层的表面张力，这样能较好地润湿、附着于印刷品的表面，得到均匀、光滑的涂层。胶印机上光涂层较薄，一般在2μm左右，涂布速率较快，一般可达80～180m/min；可以整幅面上光，也可局部上光，精度高。柔印机上光有辊涂和网纹辊、刮刀涂布两种，后者上光质量稳定、均匀、一致，可获得高质量上光效果。柔印机上光涂层要比胶印的涂层厚，而且上光质量和精度都较高，大量用于高档印刷品的上光，特别是包装装潢等印刷品的局部上光，因此UV上光油在气味、色泽上要求高。柔印机印刷大多是印刷、上光、压痕、烫金、模切、折叠、粘贴等工序为一体，纸张一次通过印刷、上光和印后加工各道工序，因此UV上光油的性能要与这些印后加工工序相适应。凹印机上光多数是联机上光，速率快，一般在100～200m/min，生产效率高。凹印上光采用雕刻凹版网点上光，涂层均匀，光亮度高，一致性好。凹印上光，光油黏度低，涂布量小，上光成本低。凹印上光主要用于高档烟包装印刷上光，因此UV上光油不仅要低气味，而且还需要极低的苯系溶剂含量，这就要求活性稀释剂不能使用甲苯作除水剂，同时也要使用无苯工艺生产的光引发剂，低聚物也要注意苯系溶剂的含量。网印上光利用丝网印刷涂层厚、光泽度高的特点，主要用于纸印刷品局部上光，也可用于特效上光，如折光、磨砂、香味上光、珠光颜料上光等。网印UV上光油黏度较大，一般在 $\\mathrm{1}\\mathrm{{Pa}\\cdot{\\textbf{s}}}$ （25℃）左右。网印UV上光油涂布厚度与丝网目数大小有关，丝网目数越大网孔越小，涂布的光油层越薄；反之，丝网目数越小，网孔越大，涂布的光油就越厚。常用网印UV上光的丝网目数范围在 $180\\sim450$ 目/in（ $\\mathbf{1in{=}2.54c m})$ 。上光油涂层厚度一般在 $15\\sim30\\mu\\mathrm{m}$ 由于光油涂层厚，上光部分能产生浮凸效果。网印上光速率慢，手工网印速率在800 张/h，自动网印机速率在2000张/h，而轮转式网印机速率在4000张/h，由于印刷上光速率慢，有  \n\n利于厚涂层的网印UV上光油完全固化。  \n\n由于UV水性低聚物的开发，UV水性纸张上光油也已商品化，这是更为环保的UV产品，但价格上比油性UV纸张上光油贵，影响了推广应用。：  \n\nEB纸张上光油是比UV纸张上光油性能更优异的上光油(表6-5)，特别适用于安全、卫生要求高的食品、药品、烟酒包装和与人体接触的物品包装上，但因一次性设备投资较大（50万～80万美元)、需要有较稳定的大批量的产品以及人们对EB了解较少等因素的影响，目前推广应用也受到阻力，咨询的多，实施的很少。  \n\n表6-5EB和UV纸张上光油比较  \n\n\n<html><body><table><tr><td>项 目</td><td>UV纸张上光油</td><td>EB纸张上光油</td></tr><tr><td>光引发剂</td><td>需用</td><td>不用</td></tr><tr><td>固化方式</td><td>UV</td><td>低能EB</td></tr><tr><td>固化设备</td><td>UV固化机</td><td>低能EB加速器</td></tr><tr><td>情性气体保护</td><td>不用</td><td>需用</td></tr><tr><td>设备投资</td><td>低(1万～5万元)</td><td>高(50万～80万美元)</td></tr><tr><td>能耗</td><td>低</td><td>只有UV的1/3左右</td></tr><tr><td>固化速率</td><td>快(可达200m/min)</td><td>更快(可达900m/min)</td></tr><tr><td>固化程度(凝胶率)/%</td><td>约75</td><td>>98</td></tr><tr><td>气味</td><td>有</td><td>无</td></tr><tr><td>耐黄变性</td><td>一般～好</td><td>比UV更优异</td></tr><tr><td>耐抗性</td><td>良～好</td><td>比UV更优异</td></tr><tr><td>安全性</td><td>品包装上光受限制 对食品、药品等卫生、安全性要求高的产</td><td>包装上光 适用于食品、药品等卫生、安全性要求高的产品</td></tr></table></body></html>  \n\nUV木器涂料是最早产业化的光固化涂料。1968年德国拜耳公司首先研究成功的第一代光固化木器涂料，标志着辐射固化产业工业化开始。UV木器涂料也是目前光固化涂料中产量最大的一种，主要用于竹木地板、装饰板和家具的涂装。UV木器涂料包括UV 腻子漆、UV底漆和UV面漆三类，而UV面漆又有清漆和色漆两种。UV木器涂料的涂装以辊涂为主，也有部分淋涂、喷涂或刮涂等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 178,
+        "chunk": "# 6.3.1 UV腻子漆  \n\nUV腻子漆通常用于表面孔隙多、平滑度较差的木材与刨花板、纤维板等板材，其作用是填充底材孔隙及微细缺陷，密封底材表面，使随后涂装的装饰性涂料不会被渗入而引起表观不平整，减少涂料的浪费，也为粗材质板材提供光滑的表面。使用UV腻子漆时需先用橡胶砂轮对基材表面进行打磨清洁，刮涂一层腻子漆，经UV固化，再用砂轮打磨后，涂覆UV底漆和面漆。  \n\nUV腻子漆为膏状物，组分中除了含有低聚物、活性稀释剂、光引发剂等基本成分外，还含有较高比例的无机填料。低聚物早期用不饱和聚酯，后来主要用环氧丙烯酸酯。活性稀释剂也采用常规的TMPTA、TPGDA 等丙烯酸酯，性价比高。光引发剂也以651、1173等高效光引发剂为主，对含二氧化钛的腻子，则需要用TPO。填料选择应考虑对固化速率影响小，即折射率低且易打磨、填充性能好的填料。合适的填料可提高涂层硬度、抗冲击性能，降低固化收缩率，提高附着力。UV腻子漆中常用的无机填料有滑石粉、重质和轻质磷酸钙、重晶石粉、白云石粉等。滑石粉与重晶石粉都可起到补强、增加硬度、抗收缩等功能；滑石粉还能改善对木质基材的附着性能，重晶石粉偏重于改善打磨性能。白云石粉为含碳酸镁与碳酸钙的天然矿粉，可对粗糙基材表面起到补强作用。有的腻子为了提高遮盖作用，还加入少量钛白粉，做成白色腻子，对这类腻子，从低聚物到活性稀释剂都要考虑使用高活性的，光引发剂也需加人TPO等，以免固化不完全。由于UV腻子漆中含有大量无机填料（一般都超过 $60\\%$ ，质量分数）将不同程度产生折射和反射，降低UV光有效吸收，使固化速率降低。因此要选择合适的光引发体系，确保固化完全，否则打磨时会发生膜层掉粉、擦除、剥落等病。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 179,
+        "chunk": "# 6.3.2 UV木器底漆  \n\nUV木器底漆与UV腻子漆的使用场合和作用不同，UV腻子漆常用于表面有孔隙、光滑度较差的木材，而UV木器底漆则应用于表面较为光滑平整的木材。UV木器底漆与UV腻子漆相比，所含无机填料较少，黏度较低，接近于面漆的黏度。涂覆一层UV木器底漆后，低黏度的涂料可向木材细小开孔渗透，通过膜层的折射效果，保留和强化木纹的自然美感，UV固化后，经机械打磨，再用UV木器面漆罩光固化，获得平整、光滑、饱满的罩光效果。  \n\nUV木器底漆所用的低聚物主要为环氧丙烯酸酯或改性环氧丙烯酸酯，为了改善固化膜的柔韧性和耐冲击性能，可以加人聚氨酯丙烯酸酯或聚酯丙烯酸酯。活性稀释剂也以常用的TMPTA、TPGDA、DPGDA等为主。光引发剂则以1173、651等高效光引发剂为主，有时也可配用二苯甲酮/叔胺以降低成本。填料中除常用的滑石粉、碳酸钙、二氧化硅等外，有时还用少量的硬脂酸锌，其为半溶性粉体，浮于固化膜表层，打磨时起润滑作用，避免较大损伤出现，同时也有较弱的亚光效果。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 180,
+        "chunk": "# 6.3.3 UV木器面漆  \n\nUV木器面漆与UV腻子漆和UV木器底漆在成分上主要区别在于前者不含无机填料，只有亚光涂料，需添加消光剂。面漆主要起装饰和保护作用，而腻子漆和底漆只是起填充、平整作用。UV木器面漆有高光型和亚光型，也有清漆和色漆，还分辊涂漆、淋涂漆和喷涂漆。UV木器面漆广泛用于竹木地板、装饰板和家具的涂装。  \n\nUV木器面漆一般黏度较低，除了辊涂外，常常用于淋涂或喷涂。UV木器面漆配方中，低聚物首选环氧丙烯酸酯，性价比最高。也可选用改性环氧丙烯酸酯，如拼木地板涂料用酸酐改性的双酚A环氧丙烯酸酯作主体树脂，目的是引入极性的羧基，改善底漆对木材的黏附性能，同时增强与面漆的层间黏合性。酸酐改性使树脂分子量增加，固化膜的收缩率降低，耐冲击性和附着力得到增强。面漆中经常加人聚氨酯丙烯酸酯和聚酯丙烯酸酯与环氧丙烯酸酯配合使用，以改善固化膜的柔韧性、耐磨性、耐冲击性能。作为木地板涂料，固化后涂层的耐磨、耐冲击性能的要求很高，单纯追求高交联度，除导致硬度过高而柔韧性不足外，反而不利于耐磨和抗冲击性。活性稀释剂常用的有TMPTA、EOTMPTA、TPGDA、DPGDA、PO-NPGDA、PEGDA等，对低黏度面漆可少量加入EOEOEA等单官能度活性稀释剂。光引发剂也是以1173、651或配用二苯甲酮/叔胺，对有耐黄变性要求的可选用  \n\n184。助剂的使用上，消泡剂和流平剂一般用有机硅类，消泡和流平效果好。对亚光型UV木器面漆，必须加人消光剂，主要为二氧化硅消光剂，对耐磨性面漆，一般都需加入氧化铝和二氧化硅，特别是纳米氧化铝和纳米二氧化硅，加人UV木器面漆，分散性好，不仅提高了耐磨性，而且提高了硬度和附着力。采用氧化锌、二氧化钛、二氧化硅三种纳米材料组合，还具有明显的杀菌作用，可以用来制备抗菌木器涂料（表6-6)，抗菌率可达99%以上。对于橱柜用UV面漆大多是在中密度板、层压板上涂装，现在又提出了防污的要求；由于有机硅类低聚物和含氟低聚物具有很低的表面能，有优良的防污性，所以近年来又出现了防污性好的UV木器面漆。  \n\n表6-6纳米抗菌涂料的抗菌性能  \n\n\n<html><body><table><tr><td>测试细菌</td><td>“0\"接触时间试样上的菌落数/(efu/片)</td><td>24h培养后试样上的菌落数/(efu/片)</td><td>抗菌率/%</td></tr><tr><td>大肠埃希菌</td><td>2.4×105</td><td><50</td><td>99.98</td></tr><tr><td>金黄色葡萄球菌</td><td>2.1×105</td><td>8.5×102</td><td>99.60</td></tr></table></body></html>  \n\nUV木器涂料的涂装：对于板式家具、竹木地板、中密度板等装饰板，大多采用辊涂，面漆也有用淋除的；对于雕花家具、楼梯扶手等不规则形状的木器则要用喷涂。UV木器涂料的涂装多采用流水生产线，生产效率较高。素材进人生产线，涂装好的产品从生产线中产出，经检验合格后可出厂。如图6-1所示是一条UV地板涂装生产线示意图。  \n\n![](images/8a08ba07f048a810ad0e0d2a207d2a74280624b9c1fd10cd04729536d8eef7de.jpg)  \n图6-1UV地板涂装生产线示意图  \n\n塑料是当今社会应用十分广泛的高分子材料，但塑料类产品普遍存在抗划伤性能差、耐磨性不足等缺点，因此塑料制品的表面装饰和强化就显得特别重要。采用涂料对塑料表面进行涂装，可以起到良好的保护作用，防止机械磨损，提高抗划伤性能；可以赋予塑料表面多种装饰效果（高光、亚光、锤纹等)；也可以给塑料带来很多功能效果，如防静电、防反射等。传统的塑料表面涂装多采用挥发干燥型溶剂涂料，溶剂挥发、污染环境；生产效率低，设备占用空间大；需用烘烤设备能耗大，塑料易变形；固化膜性能（耐磨性、抗划伤性、耐化学药品性等）不高。而UV塑料涂料正好能较完美地解决上述溶剂涂料存在的问题，因此近年来得到了很快的发展。  \n\n塑料品种繁多，按成型方式有挤出成型的片材和薄膜及注射成型的塑料件；按化学结构有聚苯乙烯（PS)、聚氯乙烯（PVC)、聚甲基丙烯酸甲酯（PMMA)、聚酯（PET)、聚碳酸酯（PC)、聚乙烯（PE)、聚丙烯（PP)、ABS（丙烯腈/丁二烯/苯乙烯三元共聚物）等。由于各种塑料的结构和性能都不同，因此各种塑料所用的涂料也不相同。  \n\n塑料不同于木材和纸张，是一种非吸收性的基材。它不能依靠涂料向基材中的渗透产生各种机械锚合达到附着的目的。与同为非吸收性基材的金属相比，塑料属于“惰性”材料，表面几乎不存在能与涂层中各组分发生反应的活性点，也就不能形成达到有效附着所需的化学键。因此塑料与UV涂料之间的附着是相当困难的，通常只能依靠涂层与塑料表面之间通过极微弱的分子间的作用力而产生相互吸附，这就要求UV塑料涂料必须具有较低的表面张力和良好的对基材的润湿能力。如果涂料组分中含有一定数量的极性基团（如羟基、羧基等）能与某些极性较高的塑料表面，或经过预处理的塑料表面形成一定数量的氢键，将会大大促进UV塑料涂层与塑料表面间的附着。如果UV塑料涂料中使用的活性稀释剂能对塑料表面产生轻微的溶胀，从而在涂层与塑料的表面处形成一层很薄的互穿网络结构，则能明显提高UV塑料涂料与塑料表面的附着力。有时为了保证UV塑料涂料具有较高的表面硬度和优良的耐抗性，要求涂层有较高的交联密度、而高交联密度产生的体积收缩过大，对涂层的附着力是非常不利的。  \n\n为解决UV塑料涂料在塑料基材上难以附着的问题，应该从UV塑料涂料配方上和塑料基材表面两方面考虑。  \n\n（1）UV塑料涂料对附着力的影响  \n\n$\\textcircled{1}$ 使用低黏度、低表面张力的活性稀释剂和低聚物，有利于UV塑料涂料对塑料表面的润湿、铺展，可提高附着力。  \n\n$\\textcircled{2}$ 使用能对塑料有一定溶胀性的活性稀释剂，可提高涂料对塑料的附着力（表6-7)。  \n\n$\\textcircled{3}$ 使用固化体积收缩低的活性稀释剂和低聚物，有利于提高附着力。  \n\n$\\textcircled{4}$ 添加少量附着力促进型低聚物或树脂，可提高涂料对塑料的附着力（表 $6\\mathrm{-}8\\sim$ 表6-10）  \n\n$\\textcircled{5}$ 有时可在UV固化后，加用红外后烘工序，使UV固化后体积收缩引起涂层产生的内应力得以释放，同时固化更完全，有利于提高附着力。  \n\n（2）塑料基材对附着力的影响  \n\n$\\textcircled{1}$ 表面形态：粗糙的基材表面比光滑的基材表面有更多的接触面积，可提供更多的有  \n\n效吸附区域和连接点，有利于附着力提高。  \n\n表6-7对塑料基材有溶胀作用的活性稀释剂  \n\n\n<html><body><table><tr><td rowspan=\"2\">产品</td><td colspan=\"4\">可溶胀的塑料</td><td rowspan=\"2\">产品</td><td colspan=\"4\">可溶胀的塑料</td></tr><tr><td>PC</td><td>PVC</td><td>PET</td><td>PS</td><td>PC</td><td>PVC</td><td>PET</td><td>PS</td></tr><tr><td>HDDA</td><td>√</td><td><</td><td></td><td><</td><td>PEG(400)DA</td><td>√</td><td></td><td></td><td></td></tr><tr><td>四氢呋喃丙烯酸酯</td><td><</td><td>√</td><td><</td><td>√</td><td>丙烯酸异癸酯</td><td></td><td></td><td></td><td><</td></tr><tr><td>2-EOEOEA</td><td>√</td><td></td><td>√</td><td>√</td><td>丙烯酸十三烷基酯 IBOA</td><td></td><td></td><td></td><td><</td></tr><tr><td>TPGDA</td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>LA</td><td></td><td></td><td></td><td></td><td>NPG(PO)DA</td><td></td><td></td><td></td><td></td></tr><tr><td>2-PEA</td><td>√</td><td></td><td></td><td>√</td><td>烷氧化脂肪族二丙烯酸酯</td><td>√</td><td></td><td></td><td></td></tr></table></body></html>\n\n注： $^{\\ast}\\vee^{\\mathfrak{n}}$ 代表可选用，下同。  \n\n表6-8科宁公司对塑料附着力促进的低聚物  \n\n\n<html><body><table><tr><td rowspan=\"2\">商品牌号</td><td rowspan=\"2\">低聚物类型</td><td colspan=\"6\">塑料 基材</td></tr><tr><td>PC</td><td>PP</td><td>PE</td><td>PET</td><td>TPO</td><td>DF</td></tr><tr><td>ECX-4114</td><td>丙烯酸酯低聚物</td><td>√</td><td>√</td><td>√</td><td>√</td><td>√</td><td>√</td></tr><tr><td>ECX-5031</td><td>改性聚酯/聚醚低聚物</td><td>√</td><td>√</td><td>√</td><td><</td><td>√</td><td><</td></tr><tr><td>photomer 4703</td><td>酸官能低聚物</td><td></td><td></td><td></td><td><</td><td></td><td></td></tr><tr><td>photomer 4846</td><td>酸官能低聚物</td><td></td><td></td><td></td><td></td><td>√</td><td></td></tr><tr><td>ECX-4046</td><td>酸官能低聚物</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>ECX-6025</td><td>聚氨酯二丙烯酸酯</td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n表6-9氰特公司对塑料附着力促进的低聚物  \n\n\n<html><body><table><tr><td>商品牌号</td><td>低聚物类型</td><td>黏度/mPa·s</td><td>塑料基材</td></tr><tr><td>Ebecryl740-40TP</td><td>以TPGDA稀释的纯丙烯酸树脂</td><td>8500(60℃)</td><td>ABS、PS、PE、PP</td></tr><tr><td>Ebecryl 767</td><td>以IBOA稀释的纯丙烯酸树脂</td><td>8500(60℃)</td><td>ABS、PS、PE、PP</td></tr><tr><td>Ebecryl 745</td><td>以TPGDA和HDDA稀释的纯丙烯酸树脂</td><td>20000(25℃).</td><td>SMC、BMC、ABS、PS、PE、PP</td></tr><tr><td>Ebecryl 303</td><td>以HDDA稀释的高分子量树脂</td><td>900(20℃)</td><td>ABS、PS、PE、PP</td></tr><tr><td>Ebecryl 436</td><td>以TMPTA稀释的氯化聚酯树脂</td><td>1500(60℃)</td><td>ABS、PS、PE、PP</td></tr><tr><td>Ebecryl438</td><td>以OTA480稀释的氯化聚酯树脂</td><td>1500(60℃)</td><td>ABS、PS、PE、PP</td></tr><tr><td>Ebecryl 584</td><td>以HDDA稀释的氯化聚酯树脂</td><td>2000(25C)</td><td>SMC、BMC、ABS、PE、PP</td></tr><tr><td>Ebecryl 7100</td><td>氨基改性的丙烯酸酯</td><td>1200(25C)</td><td></td></tr><tr><td>Ebecryl 168</td><td>酸改性的甲基丙烯酸酯</td><td>1350(25C)</td><td></td></tr><tr><td>Ebecryl 170</td><td>酸改性的丙烯酸酯</td><td>3000(25℃)</td><td></td></tr></table></body></html>  \n\n表6-10长兴化学公司适用于塑料涂料的低聚物  \n\n\n<html><body><table><tr><td rowspan=\"2\">品种名称</td><td colspan=\"7\">塑料基材</td></tr><tr><td>PC</td><td>ABS</td><td>丙烯酸树脂</td><td>易黏合PET</td><td>未处理PP</td><td>PPO</td><td>TAC</td></tr><tr><td>UV-7600B</td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>UV-7605B</td><td><</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>UV-7610B</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>UV-7620EA</td><td>√</td><td>√</td><td></td><td>√</td><td>√</td><td>√</td><td>√</td></tr><tr><td>UV-7630B</td><td></td><td>√</td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>UV-7640B</td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>UV-1700B</td><td></td><td>√</td><td>√</td><td></td><td></td><td>√</td><td>√</td></tr><tr><td>UV-6300B</td><td>√</td><td>√</td><td></td><td>√</td><td></td><td></td><td>√</td></tr></table></body></html>\n\n② 表面处理可提高塑料基材的表面张力，有利于涂料的润湿和吸附，提高附着力。如  \n\n对塑料表面用溶剂或碱性溶液脱脂清洗，去除在塑料成型中低表面张力的脱模剂等；用火焰处理、电晕处理或等离子体处理塑料表面，使塑料表面能提高，表面生成一些极性基团（如羟基、炭基等)，有利于涂料润湿，提高对塑料基材的附着力。表6-11介绍了高分子材料经等离子体处理前后表面性能的变化。  \n\n表6-11高分子材料经等离子体处理前后的表面性能比较  \n\n\n<html><body><table><tr><td rowspan=\"2\">材料</td><td colspan=\"2\">表面张力 /(X10-5N/cm)</td><td colspan=\"2\">水接触角/(°)</td><td rowspan=\"2\">材料</td><td colspan=\"2\">表面张力 /(×10-5N/cm)</td><td colspan=\"2\">水接触角/(°)</td></tr><tr><td>处理前</td><td>处理后</td><td>处理前</td><td>处理后</td><td>处理前</td><td>处理后</td><td>处理前</td><td>处理后</td></tr><tr><td>聚丙烯</td><td>29</td><td>>73</td><td>87</td><td>22</td><td>聚氨酯</td><td>一</td><td>>73</td><td>一</td><td>一</td></tr><tr><td>聚乙烯</td><td>31</td><td>>73</td><td>87</td><td>42</td><td>丁苯橡胶</td><td>48</td><td>>73</td><td>一</td><td>一</td></tr><tr><td>聚苯乙烯</td><td>38</td><td>>73</td><td>72.5</td><td>15</td><td>PET</td><td>41</td><td>>73</td><td>76.5</td><td>17.5</td></tr><tr><td>ABS</td><td>35</td><td>>73</td><td>82</td><td>26</td><td>PC</td><td>46</td><td>>73</td><td>75</td><td>33</td></tr><tr><td>固化环氧树脂</td><td><36</td><td>>73</td><td>59</td><td>12.5</td><td>聚酰胺</td><td>40</td><td>>73</td><td>79</td><td>30</td></tr><tr><td>聚酯</td><td>41</td><td>>73</td><td>71</td><td>18</td><td>聚芳醚酮</td><td><36</td><td>>73</td><td>92.5</td><td>3.5</td></tr><tr><td>硬质PVC</td><td>39</td><td>>73</td><td>90</td><td>35</td><td>聚甲醛</td><td><36</td><td>>73</td><td>一</td><td>一</td></tr><tr><td>酚醛树脂</td><td>1</td><td>>73</td><td>59</td><td>36.5</td><td>聚苯醚</td><td>47</td><td>>73</td><td>75</td><td>38</td></tr><tr><td>乙烯-四氟乙烯共聚物</td><td>37</td><td>>73</td><td>92</td><td>53</td><td>PBT</td><td>32</td><td>>73</td><td>一</td><td>一</td></tr><tr><td>氟化乙-丙共聚物</td><td>22</td><td>72</td><td>96</td><td>68</td><td>聚矾</td><td>41</td><td>>73</td><td>76.6</td><td>16.5</td></tr><tr><td>聚偏二氟乙烯</td><td>25</td><td>>73</td><td>78.5</td><td>36</td><td>聚醚矾</td><td>50</td><td>>73</td><td>92</td><td>9</td></tr><tr><td>聚二甲基硅氧烷</td><td>24</td><td>>73</td><td>96</td><td>53</td><td>聚芳矾</td><td>41</td><td>>73</td><td>70</td><td>21</td></tr><tr><td>天然橡胶</td><td>24</td><td>>73</td><td>一</td><td>一</td><td>聚苯硫醚</td><td>38</td><td>>73</td><td>84.5</td><td>28.5</td></tr></table></body></html>  \n\n$\\textcircled{3}$ 有的塑料基材需涂一层底漆，赋予基材对涂料的附着力。  \n\nUV塑料涂料中低聚物是以聚氨酯丙烯酸酯为主体树脂，常用的是双官能度或三官能度聚氨酯丙烯酸酯。单官能度聚氨酯丙烯酸酯一般黏度较低，活性低，在涂料体系起降低交联密度、减小固化后体积收缩，增进柔韧性和附着力的作用。高官能度聚氨酯丙烯酸酯具有高反应活性，提高涂层抗划伤性和耐抗性，但黏度大，固化后体积收缩大，不利于附着，故在配方中用量不宜太高。环氧丙烯酸酯具有很高的反应活性，涂层光泽高，有优异的耐抗性和硬度，价格便宜。但缺点也明显：柔韧性差，黄变，对塑料附着力差等，黏度高，也限制了它在喷涂中的应用。目前只有一些低黏度的改性环氧丙烯酸酯用于对黄变性能要求不高的塑料涂料中。聚酯丙烯酸酯在UV塑料涂料中较少使用，但特种聚酯丙烯酸酯（氯化聚酯丙烯酸酯、酸改性聚酯丙烯酸酯等）常在聚烯烃塑料、PS、ABS中作为附着力促进树脂使用（表6-12)；在UV有色塑料涂料中，聚酯丙烯酸酯作为提高涂料分散性物质使用。聚丙烯酸酯分子量较大、黏度高，与别的低聚物混容性稍差，也较少使用，主要也是少量添加以改善附着力。氨基丙烯酸酯有较高的反应活性，涂层有优良的热稳定性、耐抗性和高硬度，而且低体积收缩和高极性，对提高与塑料附着力非常有利，可配合聚氨酯芮烯酸酯用于UV塑料配方中。此外有机硅丙烯酸酯有低表面张力，低摩擦系数、高柔韧性和耐热性，在UV塑料涂料中适量添加有助于提高涂层耐磨性和附着力。  \n\nUV塑料涂料的活性稀释剂选择要选用低表面张力、低体积收缩率、有溶胀塑料能力的丙烯酸酯。常用塑料优选的活性稀释剂见表6-13。  \n\nHDDA由于自身对塑料基材有一定溶胀能力，对于PC或PS仅需少量HDDA就可以达到良好的附着力效果；而对于硬度很高的PC，则需要HDDA的加入量要多一些。丙烯酸十八酯（ODA)，这种活性稀释剂由于自身表面张力比较低（ $30\\mathrm{mN/m};$ ，体积收缩也较低$(8.3\\%)$ ，因此它对PP和PE 基材来说是一种很有效的稀释性单体，但由于它与许多丙烯酸酯低聚物的相容性不是很好，因此往往添加量很小。丙氧基化所成的二醇二丙烯酸酯也因表面张力较低（ $\\mathbf{31mN/m})$ 和体积收缩较低 $(9.0\\%$ ）可适用于PC、PMMA和ABS等塑料。  \n\n表6-12常见氯化聚酯附着力促进剂  \n\n\n<html><body><table><tr><td>公司</td><td>商品名称</td><td>树脂类型</td><td>黏度/mPa·s</td><td>酸值/(mg KOH/g)</td></tr><tr><td rowspan=\"3\">氰</td><td rowspan=\"3\">EB436 EB438 EB3438</td><td>含40%TMPTA的氯化聚酯</td><td>1500(60℃)</td><td rowspan=\"3\">20 20</td></tr><tr><td>含40%GPTA的氯化聚酯</td><td>1500(60℃)</td></tr><tr><td>不含稀释剂的EB438</td><td>1350(60℃)</td></tr><tr><td rowspan=\"3\">特</td><td>EB584 EB585</td><td>含40%HDDA的氯化聚酯</td><td>2000(25℃)</td><td>12 25</td></tr><tr><td>EB586</td><td>含40%TPGDA的氯化聚酯</td><td>5000(25℃)</td><td>17</td></tr><tr><td>EB588</td><td>含40%TMPTA的氯化聚酯</td><td>46000(25℃)</td><td>18</td></tr><tr><td rowspan=\"5\">沙 多 玛</td><td>CN2201</td><td>含40%GPTA的氯化聚酯 高T氯化聚酯丙烯酸酯</td><td>45000(25℃) 83000(25℃)</td><td>16 一</td></tr><tr><td>CN 2202</td><td>氯化聚酯丙烯酸酯</td><td>一</td><td>一</td></tr><tr><td>CN 736</td><td>氯化聚酯丙烯酸酯</td><td>1500(60℃)</td><td></td></tr><tr><td>CN738</td><td></td><td>1500(60℃)</td><td>一</td></tr><tr><td>CN750</td><td>氯化聚酯丙烯酸酯 氯化聚酯丙烯酸酯</td><td>2500(60℃)</td><td>一</td></tr><tr><td>长兴</td><td>6314 C-60</td><td>含40%TMPTA的氯化聚酯</td><td>10000~15000(25℃)</td><td>14 25</td></tr></table></body></html>  \n\n表6-13常用塑料优选的活性稀释剂  \n\n\n<html><body><table><tr><td>塑料名称</td><td>活性稀释剂</td></tr><tr><td>PC</td><td>HDDA、氨基甲酸酯单丙烯酸酯、NPG(PO)2DA、DPGDA、乙氧基化丙烯酸苯氧酯</td></tr><tr><td>ABS</td><td>HDDA,NPG(PO)2DA</td></tr><tr><td>PMMA</td><td>HDDA、氨基甲酸酯单丙烯酸酯、NPG(PO)2DA、DPGDA、乙氧基化丙烯酸苯氧酯</td></tr><tr><td>PVC</td><td>HDDA、氨基甲酸酯单丙烯酸酯、乙氧基化丙烯酸苯氧酯、丙烯酸月桂酯、EHA</td></tr><tr><td>PS</td><td>HDDA</td></tr><tr><td>PE</td><td>丙烯酸十八酯</td></tr><tr><td>PP</td><td>丙烯酸十八酯</td></tr></table></body></html>  \n\n目前大量的UV塑料涂料是在塑料表面已经涂覆一层底漆上进行涂装，如手机、电视机、笔记本电脑、相机等外壳和部件都喷涂一层含有颜料的底漆(如铝粉漆和其他色漆)。目前市场上塑料底漆主要有以热塑性丙烯酸树脂为主的单组分底漆和二液反应型聚氨酯底漆，因此在配制UV塑料涂料时要尽量考虑选择同底漆树脂类似的低聚物，不能影响底漆中铝粉漆中铝粉的排列，更不能对底漆发生“咬底”现象。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 181,
+        "chunk": "# 6.5UV真空镀膜涂料  \n\nUV真空镀膜涂料是在UV塑料涂料基础上发展起来的一种新型UV涂料。随着塑料装饰技术发展，一种塑料制品金属化装饰技术随之产生，它是利用塑料基材涂装底漆后，经真空电镀或溅涂，涂装一层金属薄涂层，再涂覆面漆而成。经涂装后的塑料表面，完全闪烁着金属光泽，显出高贵和富丽堂皇的金属品质，根本看不出是塑料制品。塑料的金属化装饰不仅可以节约大量宝贵的金属材料，也大大减轻了制品的重量，近年来在化妆品包装瓶和包装盒、汽车车灯、酒瓶包装瓶盖、手机塑料按键、钟表外壳等制造中获得了广泛的应用。",
+        "category": " Introduction"
+    },
+    {
+        "id": 182,
+        "chunk": "# 6.5.1 真空镀膜  \n\n真空镀膜技术是指在真空环境下，将某种金属或金属化合物以气相的形式沉积到材料表面（通常是非金属材料)，属于物理气相沉积工艺，因为镀层常为金属薄膜，故也称为真空金属化。在所有被镀材料中，以塑料最为常见，其次为纸张镀膜。真空镀膜的功能是多方面的，这就决定了其应用场合非常广泛。真空镀膜的主要功能是赋予被镀件表面具有高度金属光泽和镜面效果，在薄膜材料上使膜层具有出色的阻隔性能，提供优异的电磁屏蔽和导电效果。.  \n\n塑料真空镀膜根据镀膜气相金属产生和沉积的方式可分为热蒸发镀膜法和磁控溅射镀膜法两种工艺。真空蒸发镀膜法就是在 $1.3{\\times}10^{-2}{\\sim}1.3{\\times}10^{-3}\\mathrm{Pa}$ 的真空中，以电阻加热镀膜材料，使它在极短时间内蒸发，蒸发了的镀膜材料分子沉积在塑料基材表面形成镀膜层。磁控溅射镀膜法是在 $1.3{\\times}10^{-1}\\mathbf{Pa}$ 左右的真空中充人情性气体，并在塑料基材（阳极）和金属靶材（阴极）之间加上高压直流电，由于辉光放电产生的电子激发情性气体，产生等离子体。等离子体将金属靶材的原子轰出，沉积在塑料基材上。磁控溅射法与蒸发法相比，具有镀膜层与基材的结合力强，镀膜层致密、均匀等优点，它们的比较见表6-14。  \n\n表6-14真空蒸发镀膜与磁控喷溅镀膜比较  \n\n\n<html><body><table><tr><td colspan=\"2\">真空镀膜方式</td><td>真空蒸发镀膜</td><td>磁控喷溅镀膜</td></tr><tr><td rowspan=\"2\">表面</td><td>镀前处理</td><td>基材上涂底漆，真空脱气</td><td>基材上涂底漆，真空脱气</td></tr><tr><td>离子穿透深度</td><td>只在表面附着</td><td>有一定深度的穿透</td></tr><tr><td rowspan=\"3\">处理过程</td><td>离子/%</td><td>一</td><td><0.1</td></tr><tr><td>中性激发电子/%</td><td>一</td><td><10</td></tr><tr><td>热中性粒子/%</td><td>100</td><td><90</td></tr><tr><td rowspan=\"2\">镀膜材料</td><td>可选用</td><td>金属、特别金属铝</td><td>金属、非金属</td></tr><tr><td>难选用</td><td>蒸气压特别低的金属、化合物等材料</td><td>易分解或蒸气压较高的金属，化合物等材料</td></tr><tr><td colspan=\"2\">可镀基材</td><td>金属、塑料、玻璃等</td><td>金属、塑料、玻璃等</td></tr><tr><td colspan=\"2\">附着力</td><td>略差</td><td>略差至较好</td></tr><tr><td colspan=\"2\">优缺点</td><td>可镀基材广泛，附着力差</td><td>可镀基材广泛，在低温可镀多种合金膜</td></tr><tr><td colspan=\"2\">应用</td><td>装饰膜、光学膜、电学膜、磁性膜等</td><td>装饰膜、光学膜、电学膜、磁性膜等</td></tr></table></body></html>  \n\n真空镀膜材料以金属和金属氧化物为主。金属型镀膜材料有铝、锡、铟、钴、镍、铜、锌、银、金、钛、铬、钼、钨等；合金型镀膜材料有镍-铬、镍-铁、铁-钴、金-银-金等；金属化合物型的镀膜材料有二氧化硅、二氧化钛、二氧化锡、二氧化铈、三氧化二秘、氟化镁、硫化锌等。其中以铝应用最多，这是因为铝在真空条件下，蒸发温度较低，易操作；铝镀膜层对塑料的附着力强，富有金属光泽；铝镀膜层能遮蔽紫外线，对气体阻隔性也很好；加之高纯度铝的价格比较便宜，这是其他镀膜材料所不及的。铝的导电性也好，镀层厚度达到 $0.9\\mathrm{nm}$ 即可导电，达到 $30\\mathrm{nm}$ 时，其性能就和铝材相同。铝的反射率高，厚度 $46\\mathrm{nm}$ 的铝镀膜层的反射率可达 $90\\%$ 。不同厚度铝镀膜层的反射率和透过率见表6-15。  \n\n表6-15不同厚度铝镀膜层反射率和透过率  \n\n\n<html><body><table><tr><td>铝镀层厚度/nm</td><td>5</td><td>7.5</td><td>10</td><td>12.5</td><td>15</td><td>20</td><td>25</td><td>30</td><td>40</td></tr><tr><td>反射率/%</td><td>11</td><td>25</td><td>55</td><td>74</td><td>78</td><td>84.5</td><td>88</td><td>89.5</td><td>90</td></tr><tr><td>透过率/%</td><td>70</td><td>45</td><td>25</td><td>12</td><td>8</td><td>4</td><td>2</td><td>一</td><td></td></tr></table></body></html>  \n\n真空涂膜的基材以塑料和其他高分子材料为主，作为真空镀膜的塑料基材其最基本的性能应包括附着性能、真空放气量和耐热性。  \n\n（1）附着性能被涂塑料基材应与真空镀膜材料有良好的附着力，一般聚酯类材料和镀铝膜层的结合力最强，在保证表面洁净的条件下可以直接进行真空镀膜。铝镀膜层对 PP、PE 等聚烯烃基材附着力差，PC 和硬质PVC则介于其间。塑料表面的清洁度也是影响镀层附着力的重要因素，真空镀膜前要对塑料表面进行清洗，去除表面污垢和油脂，并干燥。对表面能小于（33～35)×10-5N/cm的难附着塑料，要采用等离子体预处理加工，也可用火焰处理或化学侵蚀法来改善塑料表面性能，提高附着力。目前真空镀层与多数塑料基材间的附着力还可以通过实施底涂来加以提高。  \n\n（2）真空放气量塑料基材由于含易挥发的小分子，如水分、增塑剂、残留溶剂、未反应单体和添加剂等，在真空状态下将以气体形式逸出，破坏镀膜层的附着力、平整性和外观，同时影响工作仓的真空控制。对含较多易挥发杂质的塑料基材，在真空镀膜前，要对基材进行减压预烘处理，控制水分在0.1%以下。特别是采用底漆封闭方法，可起到封闭基材的作用，阻隔基材挥发性物质的逸出，这正是在真空镀膜工艺中充分发挥UV涂料优势的一个机会。  \n\n（3）耐热性真空镀膜无论采用何种工艺，塑料基材都面临升温的考验。蒸发源的辐射热、镀膜材料高能粒子（气化原子、分子、等离子体等）在基材上的冷凝热和动能都将使塑料基材表面温度迅速升高。如果塑料基材的耐热性较差，真空镀膜时将出现皱纹，甚至整体收缩，过度受热还可能导致塑料分解、镀膜起泡、剥落。不同的塑料耐热性是不同的，如PVC 的热稳定性较差，热变形温度较低，通常最高只能在60～70℃的温度下使用，多数工程塑料类可以在200℃以下使用。表6-16列出了几种适合UV涂料涂装的塑料基材热变形温度及相关特性。  \n\n表6-16适合UV涂料塑料基材热变形温度  \n\n\n<html><body><table><tr><td>塑料</td><td>热变形温度/℃</td><td>敏感溶剂</td><td>可涂装性</td><td>评价</td></tr><tr><td>ABS</td><td>80</td><td>酮类、酯类、芳烃溶剂</td><td>高</td><td>汽车内饰材料，化妆品盒</td></tr><tr><td>PS</td><td>63</td><td>酮类、酯类、芳烃溶剂</td><td>中</td><td>耐溶剂性差、强度低，廉价通用材料</td></tr><tr><td>尼龙</td><td>>204</td><td>无</td><td>中</td><td>高韧性，易吸水</td></tr><tr><td>PC</td><td>135</td><td>酮类、酯类、芳烃溶剂</td><td>中</td><td>耐冲击，透明度高，光碟</td></tr><tr><td>聚丙烯酸酯材料</td><td>82</td><td>酮类、酯类、芳烃溶剂</td><td>高</td><td>耐光老化，汽车尾灯透镜</td></tr><tr><td>PP</td><td>113</td><td>无</td><td>低</td><td>要求表面预处理及防火处理</td></tr><tr><td>BMC</td><td>>204</td><td>无</td><td>中</td><td>适用耐热反射灯罩，表面吸潮</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 183,
+        "chunk": "# 6.5.2UV真空镀膜涂料底漆  \n\nUV真空镀膜涂料底漆是涂覆在塑料基材表面的涂料，它的作用是封闭塑料基材，防止真空镀膜时基材中的挥发性杂质影响镀膜的质量。塑料表面较粗糙，通过底漆涂布能获得光滑平整的镜面效果，有利于获得更厚而匀的真空金属涂层，展现更高的金属光泽和反射效果。对一些极性较低的塑料基材，通过底漆过渡可以使真空电镀的金属涂层获得较好的附着性能。对部分耐热性较差的塑料基材，底漆可起到一定的热缓冲作用，保护基材免遭热致变形。UV真空镀膜涂料底漆的上述作用，就要求底漆必须要对塑料基材和真空镀膜金属层有较好的附着力，也就是说底漆既要与弱极性的塑料黏附好，又要与极性金属黏附好，这比  \n\nUV塑料涂料要求更高。同时底漆要有良好的流平性，以保证真空镀膜金属层具有高光泽和镜面效果。底漆固化后不应有挥发性小分子，如残留单体、挥发性添加剂、残留溶剂等，否则在真空镀膜条件下，小分子会逸出，从而破坏金属镀膜的质量和性能。对汽车前灯反光罩，UV底漆要有较好的耐热性，PC基材要求 $120^{\\circ}\\mathrm{C}$ 以上，而BMC（玻璃短纤维增强不饱和聚酯）则要求 $180^{\\circ}\\mathrm{C}$ 以上。对柔性塑料基材其底漆也要求有足够柔韧性，若底涂层柔韧性较差，会导致金属镀层开裂甚至崩脱。  \n\n根据UV真空镀膜涂料底漆性能要求，底漆配方上除了按UV塑料涂料要求进行设计外，在低聚物上要适当添加对金属附着力促进型树脂，在助剂中添加附着力促进剂如丙烯酸磷酸酯类要慎重，由于目前真空电镀大多数是镀铝，而铝是非常活泼的金属，对酸性较大的丙烯酸磷酸酯会发生反应，使铝涂层破坏。  \n\n由于UV真空镀膜涂料底漆和面漆都应是采用喷涂工艺来涂装，所以底漆和面漆都应适当加入溶剂稀释至喷涂所需黏度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 184,
+        "chunk": "# 6.5.3UV真空镀膜涂料面漆  \n\nUV真空镀膜涂料面漆是涂覆在真空镀膜金属膜上的涂料，它对金属镀膜起保护作用和一定的装饰作用。面漆要对金属镀膜有很好的附着力，并具有足够的耐磨性、抗划伤性、耐抗性和较高的阻隔性，面漆本身不能含有腐蚀金属镀层的组分或杂质，面漆也应有较高的透明性和光泽，以突显金属的亮度和光泽。实际上UV真空镀膜面漆不是塑料涂料，而是金属涂料，它的配方选择参见UV金属涂料部分，用于UV真空镀膜涂料的低聚物见表6-17和表6-18。  \n\n表6-17沙多玛公司推荐用于UV真空镀膜涂料的低聚物  \n\n\n<html><body><table><tr><td>产品</td><td>产品类型</td><td>特性</td></tr><tr><td>CN8000</td><td>高官能度脂肪族聚氨酯丙 烯酸酯（含量75%）</td><td>快速的固化速率，高硬度，优异的耐磨性和抗刮擦性，对塑料和金属有优 异的附着力；推荐用于真空电镀面漆</td></tr><tr><td>CN8001</td><td>高官能度脂肪族聚氨酯丙 烯酸酯（含量77%）</td><td>非常高的反应活性和硬度，出色的耐磨性和抗刮擦性，对塑料和金属有非 常好的附着力；推荐用于真空电镀面漆及其他塑料和金属涂料</td></tr><tr><td>CN8002</td><td>高官能度脂肪族聚氨酯丙 烯酸酯（含量70%） 双官能度脂肪族聚氨酯丙</td><td>在金属和塑料上有出色的附着力，良好的柔韧性和硬度；推荐用于真空电 镀面漆及其他塑料面漆</td></tr><tr><td>CN8003</td><td>烯酸酯</td><td>有出色的附着力和延展性，优异的柔韧性；推荐用于真空电镀底漆，也推 荐用于任何有韧性要求的涂料</td></tr><tr><td>CN8004</td><td>丙烯酸酯低聚物</td><td>对各种基材都有出色的附着力</td></tr></table></body></html>  \n\n表6-18长兴化学公司推荐用于UV真空镀膜涂料的低聚物  \n\n\n<html><body><table><tr><td>产 品</td><td>产品类型</td><td>特性</td></tr><tr><td>ETERCURE6233</td><td>双官能度改性环氧丙烯酸酯</td><td>优异的附着力，坚韧性和流平性佳，高光泽；适用于 ABS、PC、PMMA等基材、UV真空镀膜底漆</td></tr><tr><td>ETERCURE6215-100</td><td>双官能度改性环氧丙烯酸酯</td><td>附着力佳，固化收缩小，坚韧性佳，耐水煮优异；适用于 PC、ABS基材UV真空镀膜底漆</td></tr><tr><td>ETERCURE6315</td><td>改性聚酯丙烯酸酯</td><td>附着力佳，固化速率快、耐磨与坚韧性佳，耐水煮性佳；适 用于PC、ABS基材UV真空镀膜底漆</td></tr><tr><td>ETERCURE 6316</td><td>改性聚酯丙烯酸酯</td><td>附着力佳，固化速率快，耐磨与坚韧性佳，耐黄变性佳；适 用于PC、ABS基材UV真空镀膜底漆</td></tr></table></body></html>  \n\n<html><body><table><tr><td>产品</td><td>产品类型</td><td>特性</td></tr><tr><td>ETERCURE6233-1</td><td>双官能度改性环氧丙烯酸酯</td><td>附着力佳，流平性良好，硬度及坚韧性佳；适用于PPA、 酚醛基材用UV真空镀膜底漆</td></tr><tr><td>ETERCURE6145-100</td><td>六官能度脂肪族聚氨酯丙烯酸酯</td><td>耐磨性好、固化速率快、硬度高；适用于UV真空镀膜 面漆</td></tr><tr><td>ETERCURE6175-1</td><td>脂肪族聚氨酯丙烯酸酯</td><td>对金属附着力佳，光泽高，硬度高，耐磨性好，耐黄变性 佳；适用于UV真空镀膜面漆和各种金属UV面漆</td></tr><tr><td>ETERCURE6175-2</td><td>脂肪族聚氨酯丙烯酸酯</td><td>对金属附着力佳，高光泽，高硬度，耐黄变性佳，耐水性 好；适用于UV真空镀膜面漆和各种金属UV面漆</td></tr><tr><td>ETERCURE6196-100</td><td>十五宫能度聚氨酯丙烯酸酯</td><td>固化速率快、耐磨性好，硬度高，耐黄变;适用于UV真空 镀膜面漆</td></tr><tr><td>ETERCURE 6362-200</td><td>十三官能度超支化聚酯丙烯酸酯</td><td>低黏度、固化速率快、耐磨性佳；适用于UV真空镀膜 面漆</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 185,
+        "chunk": "# 6.5.4UV真空镀膜涂料施工工艺  \n\n一般的UV真空镀涂料施工工艺如下。  \n\n工件的前处理 $\\rightarrow$ 喷涂UV底漆 $\\nsim$ 室温流平 $\\rightarrow$ 红外线流平（ $60\\sim70^{\\circ}{\\mathrm C}$ /约 $3\\mathrm{min}){\\bf\\to}{\\bf U}{\\bf V}$ 固 化 $\\rightarrow$ 工件冷却 $\\mathbf{\\rightarrow}$ 真空镀膜 $\\rightarrow$ 喷涂UV面漆 $\\mathbf{\\rightarrow}$ 室温流平 $\\rightarrow$ 红外线流平（ $60\\sim70^{\\circ}C$ /约 $3\\mathrm{{min})\\rightarrow}$ UV固化 $\\cdot^{\\star}$ 下线检测包装  \n\n从涂装工艺中看到，在喷涂UV漆后，都经过了红外流平，这样做一则保证涂料充分流平，二来有利于附着力提高，并有助于UV固化完全。  \n\n金属也是当今社会应用最广泛的材料，但大多数金属均存在易腐蚀问题，有些金属的耐磨、抗刮伤性能较差，因此采用涂料涂装，达到既美观又可以保护金属表面的双重目的。UV金属涂料作为金属涂料的重要品种，主要应用于钢材防锈、预涂金属卷材、印铁制罐、易拉罐加工、金属标牌装饰、金属装饰板制造、铝合金门窗保护及钢管临时涂装保护等。  \n\n新鲜的金属表面有较高的表面自由能（500～5000mN/m)，远高于有机高分子材料的表面能（<100mN/m)，这种高表面自由能对涂层黏附非常有利。实际上，很多金属在空气中易氧化，表面生成一层氧化膜，表面自由能相对降低，影响涂料的附着力。但大多数金属氧化膜的表面自由能仍高于UV涂料，因此UV涂料对金属基材的润湿效果很好。但UV涂料应用于金属基材时常遇到的是涂层对金属的附着力不佳，如果不添加附着力促进功能的助剂，UV涂料对金属很难获得理想的附着力。这可能是因为金属基材表面致密，UV涂料难以渗透吸收，有效接触界面较小，不像纸张、木材表面粗糙且有孔隙，塑料可被涂料溶胀，形成渗透锚固结构。另外与UV涂料快速固化，体积收缩产生的内应力不能释放，反作用于膜层对金属基材黏附力，使附着力下降。金属表面往往容易被油腻沾污，这也不利于涂层黏附和金属防腐。  \n\n为了在金属表面获得良好的附着力、防腐蚀和洁净的表面，通常在涂料涂装之前要进行清洗、物理处理和化学处理。清洗最简便的方法是用溶剂浸湿的棉布擦拭金属表面，或直接将金属件浸泡在溶剂中洗涤；更有效的方法是蒸气去油，即将金属件挂在传送装置上，传送到槽罐中沸腾的卤代溶剂上，使溶剂在金属件表面冷凝并溶解油腻，达到清洗的目的。物理处理如对金属表面喷砂，将锈蚀表面除去，形成一个新的粗糙表面，这主要用于一些粗陋的工业制件上，如桥梁、槽罐等。此外还有氧化铝真空喷射法、钢砂或水溶性黏合剂清洗、塑料丸喷射法，有时高压喷水也用作表面清洗处理。化学处理常用含磷酸或磷酸盐对金属表面产生柔和的酸腐蚀作用，形成某种形态的磷酸铁/亚铁盐层能提高涂层的附着力，但防腐蚀性只是轻微提高。经过处理的金属表面必须彻底清洗，以除去可溶性盐。铝材表面附着了一层薄而密实的氧化铝，一般只需清洗表面。  \n\nUV金属涂料的核心问题也是要解决涂层与金属的附着力，涂料配方中低聚物和活性稀释剂能与金属表面形成氢键或化学键，可极大提高涂层与金属的附着力，一般来说含有羧基和羟基的低聚物和活性稀释剂，特别是含羧基的低聚物和活性稀释剂对金属基材的作用较为显著，对提高附着力作用明显(表6-19)。同时选用体积收缩小的低聚物和活性稀释剂也有利于提高附着力。  \n\n表6-19含羧基单体对UV涂料与金属附着力的影响  \n\n\n<html><body><table><tr><td>含羧基单体</td><td>化学结构</td><td>拉脱强度/MPa</td></tr><tr><td>丙烯酸</td><td>0 OH</td><td>0.25</td></tr><tr><td>甲基丙烯酸</td><td>0 OH</td><td>0.28</td></tr><tr><td>丙烯酸羟乙酯-马来酸酐半加成物</td><td>0 OH 0 0</td><td>0.75</td></tr><tr><td>丙烯酸-4-羟丁酯-马来酸酐半加成物</td><td>0 OH 0 0</td><td>1.85</td></tr></table></body></html>  \n\n添加附着力促进剂是UV金属涂料提高附着力的重要手段。常用的有带羧基的树脂、含羧基的丙烯酸酯、丙烯酸酯化磷酸酯、硅氧烷偶联剂、钛酸酯偶联剂等。硫醇因太臭，无法使用，但对惰性极高的黄金表面有较强的作用。适用于UV金属涂料的金属附着力促进剂见表6-20。酸性单体或树脂所含的酸性基团可对金属表面产生微腐蚀作用，并与表面金属原子或离子形成络合作用，加强了涂层与金属表面的粘接力。一般磷酸酯类附着力促进剂在配方中用量较低，不超过 $1\\%$ 。硅氧烷偶联剂对金属基材的附着力促进作用是因硅氧烷偶联剂水解后，可与金属表面的氧化物或羟基缩合，形成界面化学键，提高附着力。合适的硅氧烷偶联剂有KH550、KH560、KH570及一些硅氧烷改性的UV树脂。钛酸酯偶联剂用于UV金属涂料，可提高对金属基材的附着力，合适的钛酸酯偶联剂包括钛酸四异辛酯、钛酸四异丙酯、钛酸正丁酯等。  \n\n相对于自由基光固化体系，阳离子光固化涂料比较容易在金属上获得良好的附着性能。阳离子固化收缩率低，聚合后产生的大量醚键可作用于金属表面，这些都能提高附着力。但阳离子光引发剂光解产生的超强质子酸，除引发阳离子聚合交联外，还会对金属基材产生腐蚀作用，显然对涂层黏附有害，不利于提高附着力。只有降低阳离子光引发剂浓度，才能改善附着力。另外目前常用的阳离子光引发剂硫盐或碘盐，它们的紫外吸收 $<300\\mathbf{nm}$ ，与UV光源不匹配，光引发效率极低，必须加人少量自由基光引发剂如ITX，可在紫外长波段吸收光能，并将能量传递给硫盐，间接激发光引发剂，提高光引发效率。  \n\n表6-20UV金属涂料用附着力促进剂  \n\n\n<html><body><table><tr><td>公司</td><td>商品牌号</td><td>附着力促进剂类型</td><td>公司</td><td>商品牌号</td><td>附着力促进剂类型</td></tr><tr><td>沙多玛</td><td>SR9008</td><td>烷氧基化双官能度单体</td><td>科宁</td><td>Photomer 5424</td><td>酸性聚酯丙烯酸酯</td></tr><tr><td>沙多玛</td><td>SR9012</td><td>三官能度丙烯酸酯单体</td><td>诺地亚</td><td>Sipomer PAM-100</td><td>可共聚型磷酸酯</td></tr><tr><td>沙多玛</td><td>SR9016</td><td>丙烯酸锌盐（对钢等金属有效)</td><td>诺地亚</td><td>Sipomer PAM-200</td><td>可共聚型磷酸酯</td></tr><tr><td>沙多玛</td><td>CD9050</td><td>酸性单官能度丙烯酸酯</td><td>诺地亚</td><td>Sipomer BCEA</td><td>丙烯-β羧基乙酯</td></tr><tr><td>沙多玛</td><td>CD9051</td><td>酸性双官能度丙烯酸酯</td><td>氰特</td><td>EB168</td><td>酸性甲基丙烯酸酯</td></tr><tr><td>沙多玛</td><td>CD9052</td><td>酸性三官能度丙烯酸酯</td><td>氰特</td><td>EB170</td><td>酸性丙烯酸酯</td></tr><tr><td>科宁</td><td>Photomer 4713</td><td>酸性单官能度丙烯酸酯</td><td></td><td></td><td></td></tr></table></body></html>  \n\nUV金属涂料主要有UV卷材涂料、UV防腐涂料、UV印铁制罐涂料、UV金属装饰涂料等。  \n\n（1）UV卷材涂料卷材涂料（coilcoating）是一种以卷钢或卷铝为基材而具有装饰性和耐腐蚀的涂料。它涂装在卷钢或卷铝上后，使金属材料能直接进行切割、弯曲、深冲、咬合等机械加工，并具有优良的保光、保色、附着力、抗弯折、抗剥离、抗冲击、抗腐蚀和抗老化性能。卷材涂料涂装的钢板和铝板，由于质轻、性优和价廉而获得广泛应用，在建材、家电、汽车制造、船舶内装饰、家庭装潢等领域先后采用。  \n\n卷材涂料根据涂装次序和部位不同分为底漆、面漆和背面漆三类，一般金属基材正面涂装一道底漆和一道面漆，背面涂装一道背面漆。传统的卷材涂料主要是热固化溶剂型涂料，其涂装过程包括表面化学处理 $\\rightarrow$ 涂底漆 $\\rightarrow$ 升温固化 $\\star$ 冷却 $\\rightarrow$ 涂面漆 $\\cdot\\mathbf{\\lambda}$ 冷却等工序。涂料通过溶剂挥发热固化成膜，固化温度 $220{\\sim}240^{\\circ}\\mathrm{C}$ ，在 $40\\mathbf{m}$ 长、 $400^{\\circ}\\mathrm{C}$ 的烘道内进行，固化后还需冷却降温才可进行下一道工序，所以污染重、能耗高、效率低、成本高。而采用UV卷材涂料可以室温固化，降低能耗，节约成本；固化速率快，生产效率高；无溶剂排放，不污染环境；无需烘道和冷却带，减少厂房面积和投资。目前UV卷材涂料已商品化，UV固化卷材生产线也逐年增多，同时EB固化卷材也成功商业化。  \n\n（2）UV防腐涂料据报道全世界每年因腐蚀造成的经济损失大约在7000亿美元，占各国国民生产总值的 $2\\%\\sim4\\%$ ，约为地震、水灾、台风等自然灾害所造成损失总和的6倍。我国1995年统计，腐蚀损失约占当年国民生产总值的 $4\\%$ ，钢铁因腐蚀而报废的数量为当年钢铁产量的 $25\\%\\sim30\\%$ 。可见，材料特别是金属材料的防腐蚀，已成为全世界面临的一个重要课题。  \n\n在众多的防腐方法中，最广泛、经济而实用的是涂料的防腐涂装，防腐涂料应用领域极广：石油化工中炼油装置、化工设备及厂房、油（气）贮罐、输油（气）管道等，电力水利中火电站、水电站、风力电站、核电站、输电装置、各种水利设施等，交通运输中汽车、机车、船舶、铁路、桥梁、集装箱、港口设施等，冶金机械中各种机械、设备、农用机械等，建筑中钢材、铝材等，以及家电、国防军工等。事实上防腐涂料在整个涂料工业中占有举足轻重的地位，除了建筑涂料、木器涂料、特种功能涂料外，防腐涂料占了近一半。目前防腐涂料有环氧树脂型、聚氨酯型、酚醛树脂型、无机富锌型、硅氟树脂型等多种，但大多为溶剂型涂料，存在污染重、能耗高、效率低等弊病。而UV防腐涂料的出现，正好消除了上述病，发挥了UV涂料的优势，为防腐涂料家族增添了一个新的品种，已在钢管的防腐涂装保护和钢材的临时涂装保护上商品化。  \n\n（3）UV金属制罐涂料金属制罐外壁的涂装保护也是UV金属涂料的一个重要应用领域。金属制罐有“三件套”和“两件套”制罐工艺。“三件套”制罐工艺是由马口铁卷材压焊制成毛坯罐，罐体为简单圆筒，经底涂、印刷、上光后，在两端压合盖板，形成完整封闭罐体，市场上的八宝粥罐就用此工艺制得。“二件套”制罐工艺是由铝合金板冲压而得，底部与罐壁是一个无焊缝整体，同样经底涂、印刷、上光后，压合一端盖板形成封闭罐体，市场上盛装饮料的易拉罐即以此工艺制得。金属罐体外壁的底漆、油墨印刷和罩光清漆都可用UV工艺完成，但从安全、无毒的角度看，要制备出既满足涂层性能，又符合卫生安全标准的UV涂料和UV油墨还是有一定难度的。美国Coors制罐公司在1988年就采用阳离子UV金属涂料进行罐体涂装，当时生产线速度就已达到1500个 $\\mathbf{\\dot{min}}$ ，而且其UV涂装生产线的体积不到溶剂漆涂装生产线的1/3。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 186,
+        "chunk": "# 6.7UV玻璃、陶瓷、石材涂料  \n\n玻璃、陶瓷均以硅酸盐为主要成分，材质硬而脆，表面都具有一定的极性，因此，对UV涂料的柔韧性要求不高，关键是要解决好与基材的附着力问题。  \n\n玻璃表面涂覆涂料，可赋予玻璃更多的功能和作用。如装饰性涂料可拼镶成色彩鲜艳的艺术图案，用于建筑物门窗、幕墙和天花板的装饰；低辐射涂料，可阻挡热量的传递，可成为理想的节能窗玻璃材料；防反射涂料由多层涂层叠加构成，可对较大范围内的可见光起作用，减少反射损失；耐磨涂料可以增加玻璃容器的耐磨性；自洁净涂料，使玻璃表面具有良好的防止雨、雪黏附功能，从而赋予汽车挡风玻璃在雨雪天气中拥有良好的透明度，避免交通事故发生等。玻璃涂料中的平板玻璃涂料在现代建筑物和家居装潢及装饰方面应用最为广泛，而平板玻璃用UV涂料涂装和固化最为合适。  \n\n玻璃材料致密，UV涂料不能渗透，影响附着力。但玻璃表面有丰富的硅羟基结构，因此可以通过添加硅偶联剂来提高UV涂料与玻璃的粘接能力。常用的硅偶联剂KH570，为甲基丙烯酰氧基--丙基三甲氧基硅烷，具有较低的表面能（ $\\mathbf{28}\\times10^{-5}\\mathbf{N}/\\mathbf{cm})$ ，其中的甲基丙烯酰氧基可参与聚合交联，成为交联网络的一部分，硅氧烷基团易与玻璃表面的硅羟基缩合成牢固的Si-O-Si结构，使涂层对玻璃的附着力得到提高。UV玻璃涂料常用低聚物为环氧丙烯酸酯或聚氨酯丙烯酸酯，活性稀释剂为TMPTA、TPGDA等常用单体，光引发剂则以1173为主。为了提高附着力除了用硅偶联剂外，还可适量使用一些附着力促进低聚物，如沙多玛公司的三官能团酸酯CD9051等。  \n\n陶瓷表面涂覆涂料可起装饰作用，有的为提高耐磨防滑性能，有的为提高耐污性等。陶瓷具有多孔表面结构，UV涂料可向内渗透，固化后，涂层与陶瓷底材的有效接触面积大大增加，有利于提高附着力，但若涂层太厚，会影响深入表面微孔的涂料固化完全。在陶瓷上涂装UV高光涂料，可产生釉质般的视觉效果，提高陶瓷制品的档次。对UV陶瓷地砖涂料，重点是提高耐磨、抗刮和防滑性能。UV陶瓷涂料所选用的原材料与UV玻璃涂料相近，低聚物以聚氨酯丙烯酸酯和环氧丙烯酸酯为主，活性稀释剂以TMPTA、TPGDA、  \n\nDPGDA等常用单体为主，光引发剂以1173、651等为主，添加硅偶联剂采用纳米二氧化硅等无机填料。  \n\n石材涂料作用有三方面：在石材抛光前作填充、修补、平整用；作装饰、保护用；在维修时作修补用。由于石材大多为平面板材，特别适合UV涂料涂装和固化。石材UV涂装生产线由于节能、高效、节省投资和场地更值得推广应用。北京一条进口的石材生产线，其涂装部分由热固化改为光固化，能耗从 $200\\mathbf{k}\\mathbf{W}$ 降到 $20\\mathbf{k}\\mathbf{W}$ ，涂装部分操作工从4人降为2人，过去 $20\\mathrm{m}$ 长的红外烘道也可省去。抛光前用的UV石材涂料，主要将切割后的石材毛坏片材中出现的细小空洞、划痕等表面疵点，用涂料补平，UV固化后，在抛光阶段大多数涂料可除去。作修补用的UV石材涂料，主要用于宾馆、饭店、游乐场所大厅等经常人走的地方的石材地砖维护修补用，要采用喷涂方法，移动式UV固化灯照射固化后再用移动式抛光机抛光，达到修补整新目的。由于石材多为碳酸钙、硅酸盐成分，表面具有较粗糙和多微孔结构，故UV石材涂料对石材的粘接性能较好。UV石材涂料从配方上低聚物是以环氧丙烯酸酯为主，或配以部分聚氨酯丙烯酸酯；活性稀释剂可用常用的TPGDA、TMPTA;要提高硬度和光泽，则多官能度丙烯酸酯应增加用量；光引发剂也以1173、651等为主；填料有时采用石粉，这样色泽比较一致，也可少量添加碳酸钙、二氧化硅等补强。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 187,
+        "chunk": "# 6.8 UV皮革涂饰剂  \n\n皮革涂饰剂是用于皮革表面涂饰保护和美化皮革的皮革助剂，它是由成膜物质、着色剂、助剂和溶剂按一定比例配制而成，其中成膜物质是皮革涂饰剂的主体。皮革涂饰剂在皮革制造业中有非常重要的作用，可以增加皮革的美观、延长皮革的使用时间，显著提高皮革制品的质量和档次，增加商业价值。早在1933年德国首先将丙烯酸树脂乳液用于皮革涂饰，它与皮胶原结合力强，成膜强度高，富有弹性，耐候性和耐老化性能优良，成本又低廉，但丙烯酸树脂乳液是热塑性树脂，其涂膜存在热黏、冷脆和不耐溶剂等缺点，限制了它的使用。20世纪60年代，聚氨酯开始用于皮革涂饰，其成膜性能好、粘接牢固，涂层具有高光泽、高耐磨性、高弹性，耐水和耐化学药品，耐候、耐寒和耐热，涂饰的成品革手感丰满、舒适，能大大提高成品革的档次。20世纪70年代后又开发了水性聚氨酯皮革涂饰剂，使皮革涂饰剂品种增加，性能也不断提高。目前我国皮革行业，每年有2亿张标准牛皮，折合5亿平方米牛皮，年生产60亿双牛皮鞋，占世界皮鞋总产量 $55\\%$ 。但国内皮革涂饰剂仍以溶剂型和部分水性聚氨酯涂饰剂为主，水性聚氨酯涂饰剂也含有一定溶剂，因此在涂饰过程中，大量溶剂挥发，污染环境，也损害操作工人身体健康，同时也给生产安全带来隐患。另外皮革中还会残留部分溶剂，制成皮革制品后，溶剂残留超标，影响出口。进入21世纪后，国内北京美力科技公司、湖南本安亚大新材料公司等单位开始研发UV皮革涂饰剂，但都未能工业生产，2006年北京化工大学与温州鹿城油墨化学公司开发了拥有自主知识产权的纳米改性光固化皮革涂饰剂，批量生产，并将进一步开发UV水性皮革涂饰剂。  \n\nUV皮革涂饰剂既可用于真皮，也可用于人造革，涂装效果有高光、磨砂、绸面等多个品种，使皮革的美观程度大大提高。真皮材料为极性表面，有许多毛孔，有利于与UV皮革涂饰剂的附着。但皮革上革剂的存在会影响涂饰剂的附着力，需要添加与革剂相容的组分以改善附着力。UV皮革涂饰剂涂装工艺以喷涂为主，要求涂饰剂黏度较低，为防止低黏度涂饰剂渗人皮革内层，宜缩短喷涂与固化时间的间隔，因此要求涂饰剂流平性好。因为若涂饰剂渗人皮革内层，往往使固化不完全，就会有残留的活性稀释剂，不仅会有气味，而且会引起人体皮肤过敏刺激。对于皮革制品，如果要求保留皮革表面原始的孔粒结构，只要喷涂UV面漆即可；如果需要填补皮革表面坑凹结构，最终获得很平滑的革面，需要先辊涂一层UV底漆，UV底漆通常含有较多的颜料粒子，然后再喷涂UV面漆。UV皮革涂饰剂是涂饰在皮革上，其涂层要求有较高的柔韧性、耐磨性、抗刮伤性、断裂伸长率和透气性。在配方上低聚物首选是聚氨酯丙烯酸酯，可以提供良好的柔韧性、耐磨性和断裂伸长率，可适当拼用少量的改性环氧丙烯酸酯或聚酯丙烯酸酯。活性稀释剂要用低黏度丙烯酸酯，以利于喷涂，故较多地使用单官能度活性稀释剂，如EOEOEA、IBOA、2-EHA，较少的使用多官能度活性稀释剂。光引发剂清漆以1173为主，有色涂饰剂则需用907、ITX、651、369、819和TPO等光引发剂。  \n\n汽车工业是我国的支柱产业之一，用于汽车涂装的汽车涂料是高产值和高附加值的产品，它代表着涂料工业发展的最高水平和发展方向，是世界各国涂料界专家们关注的热点。汽车涂料作为汽车的“外衣”，不仅要求有良好的防腐、耐磨、耐候和抗冲击性能，而且还要求漆膜丰满、鲜映度高、不泛黄，并具有各种装饰效果。涂装后的汽车就像是一件艺术品，令人赏心悦目，美玉无暇。汽车壳体大部分为钢铁，但塑料也已广泛使用，因而对涂料也有不同要求。除此之外，汽车的修补漆也是汽车涂料的重要组成部分，目前汽车涂料中除了底漆是水溶性的电泳漆外，中涂和面漆大部分都是溶剂型的，因此涂装中大量有机溶剂挥发排放。随着世界范围内的工业环保要求越来越高，各国环保法规越来越严，早在1994年欧洲就提出了《溶剂控制指令—汽车涂装过程排放限制》，明确规定了轿车涂装线有机溶剂的排放量不得高于 $\\scriptstyle45g/\\mathbf{m}^{2}$ ，德国对挥发性有机物的排放要求更为严格，排放标准不得高于 $35\\mathrm{g}/\\mathrm{m}^{2}$ 。而溶剂型面漆的VOC为汽车涂料VOC之最，一辆表面积为 $80\\mathbf{m}^{2}$ 左右的普通轿车VOC排放量达 $10\\mathbf{kg}$ 左右，平均为 $\\scriptstyle125{\\bf g}/{\\bf m}^{2}$ ，远远高于上述标准，故VOC的削减是汽车涂装的当务之急。而UV涂料因其无污染、高效率等优点而开始在汽车涂装领域逐步得到应用，主要在下面三个领域中使用UV涂料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 188,
+        "chunk": "# 6.9.1汽车塑料部件涂装涂料  \n\n汽车的部件很多已采用工程塑料或者聚合物基复合材料，需要用涂料改善其表面性质。UV涂料在这方面具有十分突出的优势，可赋予塑料表面高硬度、高光泽、耐磨、抗划伤等性能。 4  \n\n汽车车灯灯罩已用PC代替玻璃灯罩，PC具有易加工成型、重量轻和柔性强、不易破碎等优点，但它的表面强度弱，不耐刻划和刮擦，而且耐候性差，易黄变。采用UV塑料涂料涂装，不仅可改变PC表面抗划伤、耐磨性，而且有很好的光学性能，可满足长期耐候性要求，同时大大节约了涂装的时间。UV涂料要考虑耐候、耐磨、抗划伤性好的低聚物，为了提高耐光老化性，配方中可添加UV吸收剂和受阻胺光稳定剂。  \n\n汽车前灯反光镜也是用塑料制备的，由于灯泡使用高热密集发光灯泡，因而反光镜塑料大多用BMC（bulk moldingcompound，玻璃短纤维增强不饱和聚酯树脂块状模塑料），它的热形变温度>204℃。为了达到表面有很高的反光性能，光在反光镜内表面喷涂一层UV底漆，固化后得到非常光滑的表面，再用磁控喷溅镀膜法镀上铬或铝形成高度光滑的反射镜面，最后喷涂一层UV面漆，阻隔氧气和潮气向铬或铝膜渗透。UV面漆长期与车灯近距离接触，特别要考虑涂料的耐热和耐光老化性，要选用耐热性和耐光老化性好的低聚物作主体树脂。  \n\n铝合金轮毂及塑料轮毂盖的涂装，传统涂料的聚氨酯双组分体系，涂后需烘烤30min，不但污染环境，又耗时、耗能；之后又采用水性保护涂料，但烘烤工序仍费时、耗能。采用UV涂料，则环保、节能、生产效率大大提高，但涂料配方上要考虑耐磨、耐候、附着力、抗冲击和防污等因素。  \n\n汽车的其他部件如保险杠、翼子板等也都用工程塑料制造，传统涂装大多用热固性涂料，现都可采用UV涂料来涂装。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 189,
+        "chunk": "# 6.9.2 汽车修补漆  \n\nUV固化的汽车修补漆最早由巴斯夫公司于2003年推向市场（牌号为Glasurit和R-M)。传统的汽车修补漆采用热固化聚氨酯漆，需要在加热数小时后才能完全固化，这样，操作人员必须要等待涂层完全固化和交联后，才能进行下一道涂层的施工。而采用UV汽车修补漆后，涂层仅需要几分钟就可以完全固化，操作工人即可进行下道涂刷工序。采用UV汽车修补漆，所使用的能源仅是一台移动式UV灯。所以UV固化汽车修补工艺的优点不仅是修补速度快，节省时间，同时不用烘烤，节省能源。  \n\n目前UV固化汽车修补有两种途径：一种是面漆用UV面漆，腻子和底漆采用传统的热固化漆；另一种是腻子、底漆和面漆全部采用UV固化漆。这两种UV固化汽车修补工艺在我国也开始推广应用，从修补汽车实际效果看，不仅节约了时间，节约能源，减少了VOC 排放；还减少了操作人员和节省了材料成本费用；特别要提到的是需修补的汽车可以快速修补后，马上开走，这对车主来讲是最受欢迎的。可以预料UV固化汽车修补这个新生事物必将会在我国获得迅速发展。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 190,
+        "chunk": "# 6.9.3汽车整车UV面漆  \n\n汽车面漆最重要的作用是装饰，除了要求有华丽的外观外，还必须具有抗光氧化、抗水解、抗酸雨、抗划伤、抗撞击、抗曝晒等性能。现在汽车面漆都采用两涂层面漆涂装工艺（即底色十罩光工艺)，下层涂料加有各种颜料，如彩色颜料、闪光颜料，以呈现不同颜色；上层涂料为罩光清漆，以赋予涂层高光泽，并满足面漆的各种要求。光固化透明清漆具有无溶剂、快速固化、耐划伤、高光泽和高硬度等优点，非常适合用于汽车面漆罩光，只是在耐候性、附着力和光固化可行性三个问题上，存在一些阻力，影响推广应用。这几年来，随着UV固化技术进展，广大科技工作者努力探索，这三个问题都有了解决方案。 Q)  \n\n（1）耐候性UV涂料涂层中残留未反应完全的成分和光引发剂的残余都会影响耐候性。此外为改善UV涂料的耐候性，往往要加入紫外吸收剂和光稳定剂，这些助剂在紫外区有较大的吸收，会与光引发剂发生竞争，使光固化反应不能充分、彻底。现在可采用酰基麟化氧类光引发剂，其吸收光谱范围可达到400nm，在紫外吸收剂和位阻胺等光稳定剂存在下，仍能很好地引发光固化反应，达到既有满意的固化速率，又有优良的耐候性。  \n\n日本油脂、巴斯夫涂料公司在冲绳对UV罩光涂层耐候性试验的结果表明（表6-21)：三种”底色漆经三年曝晒，光泽保持率结果良好，都超过 $90\\%$ ；保色性也良好，白色曝晒前后色差仅为 $\\Delta E{=}1.5$ ；目测检查外观，三种底色漆均未发生开裂缺陷。这证明UV罩光清漆的耐候性已具有适用于汽车面漆涂装的高耐久水平。  \n\n表6-21UV罩光涂层的耐候性试验结果  \n\n\n<html><body><table><tr><td rowspan=\"2\">底色漆的颜色</td><td colspan=\"3\">冲绳曝晒三年试验结果</td></tr><tr><td>光泽保持率/%</td><td>色差△E</td><td>外观</td></tr><tr><td>白色</td><td>93</td><td>1.5</td><td>未发生开裂</td></tr><tr><td>银灰金属色</td><td>98</td><td>0.8</td><td>未发生开裂</td></tr><tr><td>黑珍珠色</td><td>97</td><td>0.5</td><td>未发生开裂</td></tr></table></body></html>  \n\nUV汽车罩光清漆采用耐黄变性优异的脂肪族或脂环族聚氨酯丙烯酸酯，配合酰基麟化氧类光引发剂和光稳定剂，可以满足耐候性要求。事实上，摩托车涂装早已使用此类涂料。  \n\n（2）附着力UV涂料在刚性底材上附着曾经是一个问题，因为光固化速率很快，涂料由液体变成固体有体积收缩，在涂层与基材的界面上产生应力，特别是基材温度较低、固化涂层较硬时，在界面上涂层组分的分子键的热运动被冻结，应力将不能有效释放，影响涂层与基材的附着力。现在可以有多种方法来提高附着力：在工艺上采取光固化后再加热后烘，使界面的涂层分子通过热运动消除内应力；或在UV涂料中采用分子量较高的低聚物，或加人非反应性树脂作填料，可有效提高附着力；或在底漆中加人“抛锚剂”，使清漆和底漆间产生化学键联结，可极大地提高附着力；选用合适的UV光源和反射罩，提高光源的强度，保证涂层的深层固化完全，可提高附着力。  \n\n（3）光固化的可行性汽车的罩光清漆涂层较厚，一般干膜厚度在 $35\\sim40\\mu\\mathrm{m}$ （个别的为提高外观装饰性可达 $50\\mu\\mathrm{{m}})$ )；汽车形状复杂，会发生UV光照不到的阴影部分，产生固化不完全的现象，这是作为UV汽车涂料必须要解决的问题。  \n\n首先在UV汽车罩光清漆配方上选用高光引发活性，在长波紫外吸收强的酰基麟化氧类光引发剂。为了使光照弱的阴影部分也能完全固化，可采用光/热双固化体系，先UV固化使涂层表面快速干燥，然后再进入烘道进行热固化，使涂层深层和阴影部分涂层彻底固化，同时可释放应力。这种双固化复合体系可以利用现有的汽车涂装设备，将使现行设备的生产效率大幅提高。  \n\n同时要选用高强度的UV光源，保证UV涂料固化完全。辐深公司最近开发了UV车身涂装3D软件系统，通过计算机自动计算汽车车身各部位受UV辐照能量大小，并显示可能固化的效果；自动计算最少UV灯具的数量，调节灯具的位置和输出功率，使汽车车身的UV涂料完全固化。  \n\n虽然UV汽车面漆尚未产业化，但由巴斯夫、汽巴、DSM等公司组成的汽车涂装项目组已经涂装一辆福特跑车，底漆用“变色龙”颜料，配以UV罩光清漆的高光效果在2004年北美辐射固化国际会议展览上展出，让所有参观者都为之惊叹。UV技术独有的表面装饰效果，生产工艺的先进性，加上UV技术的环保性，将会使汽车涂装产生一次技术飞跃，这场变革已经到来。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 191,
+        "chunk": "# 6.9.4UV摩托车涂料  \n\nUV摩托车涂料在我国已经有十多年的生产和应用历史，目前大多数摩托车生产厂都在使用UV摩托车涂料涂装油箱、挡风板等部件，取得了节约生产用地、降低生产线投资费用、提高生产效率、节省能源和减少环境污染等经济效益、社会效益和生态效益。  \n\nUV摩托车涂料的主体树脂为耐候性好的脂肪族聚氨酯丙烯酸酯，有时可适量添加环氧丙烯酸酯；活性稀释剂要选用黏度低、体积收缩小、表面张力小的丙烯酸酯，如以丙烯酸异冰片酯、丙烯酸苯氧基乙酯等为主；光引发剂选用1173、184等耐黄变和光引发活性高的品种。由于UV摩托车涂料也是罩光清漆，为了提高与有色面漆的附着力，可在面漆中添加有光热两种官能团的活性物质，在面漆烘烤时热敏性基团与面漆树脂交联固化而留下具有光敏性的基团，在UV罩光清漆涂装后，UV固化时与清漆中活性基团发生层间化学交联，大大提高了附着力。  \n\nUV摩托车涂装生产工艺流程如下：  \n\n工件前处理→喷涂面漆→烘干→打磨→去灰→静电除尘→喷涂UV罩光清漆→红外流平→UV固化 $\\star$ 冷却 $\\rightarrow$ 检验 $\\rightarrow$ 成品  \n\nUV摩托车罩光清漆与丙烯酸罩光清漆、聚氨酯罩光清漆的主要性能和技术参数比较见表6-22，可以明显地看到UV罩光清漆不仅各种性能优异，而且固化速率快，生产效率高，能耗低，VOC排放极低，具有非常显著的经济效益和社会效益。  \n\n表6-22摩托车罩光清漆主要性能和技术参数比较  \n\n\n<html><body><table><tr><td>性能指标</td><td>丙烯酸罩光清漆</td><td>聚氨酯罩光清漆</td><td>UV罩光清漆</td></tr><tr><td>固含量/%</td><td>35~45</td><td>40~50</td><td>≥95</td></tr><tr><td>光泽/%</td><td>≥90</td><td>≥90</td><td>≥100</td></tr><tr><td>硬度/H</td><td>1~2</td><td>1~2</td><td>≥3</td></tr><tr><td>与面漆附着力/级</td><td>1</td><td>1</td><td>1</td></tr><tr><td>人工加速老化/h</td><td>≥400</td><td>≥600</td><td>≥1000</td></tr><tr><td>耐油性/h</td><td>4</td><td>24</td><td>360</td></tr><tr><td>耐强溶剂性</td><td>≥10s</td><td>≥30s</td><td>7d</td></tr><tr><td>保光性/年</td><td>>1</td><td>≥2</td><td>≥3</td></tr><tr><td>涂膜丰满度</td><td>中等</td><td>较好</td><td>好</td></tr><tr><td>抗划伤性</td><td>差</td><td>较好</td><td>好</td></tr><tr><td>鲜映度</td><td>0.2</td><td>约0.5</td><td>≥0.6</td></tr><tr><td>一次涂装厚度/μm</td><td>15~25</td><td>15~25</td><td>30~50</td></tr><tr><td>固化时间/min</td><td>30~60</td><td>30~60</td><td>0.25~0.75</td></tr><tr><td>能量消耗/kJ</td><td>1</td><td>0,5~0.75</td><td>0.1~0.3</td></tr><tr><td>溶剂含量/%</td><td>80</td><td>70</td><td>5</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 192,
+        "chunk": "# 10 UV氟碳涂料  \n\n氟碳涂料是在氟树脂基础上经改性加工而成的一种新型涂层材料。由于其基料氟树脂所含的氟碳键长度短，而氟原子电负性又是最强的，所以决定了氟碳涂料的优异性能。氟碳涂层具有突出的耐候性、耐腐蚀性、耐化学药品性。氟化合物的低表面能使其只能被液体或固体浸润或黏着，所以氟碳涂料具有优异的低摩擦系数、憎水、憎油、抗粘、耐沾污等性能。氟碳涂料已有40多年的发展历史，经历了熔融型、低温交联型、常温溶剂型、水基型的发展过程，水基型是发展方向，但目前普遍使用的还是溶剂型氟碳涂料。随着各国新环境保护法实施，VOC排放受到严格控制，溶剂型氟碳涂料显然不符合环保要求。近年来，UV固化技术进入氟碳涂料领域，意大利的Solvay Solexis公司成功开发了以氟碳聚氨酯丙烯酸酯为主体树脂的UV氟碳涂料，我国也开始UV氟碳涂料的开发与应用，并成功地应用于外墙建筑涂料及其他高性能装饰涂料。外墙建筑涂料由于低成本、低能耗、可防水、安全、色彩丰富和容易更新等优点，已成为国内外建筑装饰的主流。外墙建筑涂料经历了纯丙烯酸树脂、聚氨酯-丙烯酸树脂、有机硅-丙烯酸树脂和氟树脂型涂料的发展过程，纯丙烯酸树脂型涂料的耐候性能和耐污性能不够好，聚氨酯-丙烯酸树脂和有机硅-丙烯酸树脂型涂料的综合性能还不能满足高档外墙装饰材料的要求，而氟碳涂料以其超强的耐候性、耐腐蚀性、耐化学药品性和耐沾污性，已成为新一代户外装饰涂料，应用于内、外墙装饰板、铝塑板、塑钢型材和铝合金型材等建筑材料表面的涂装，以及厨房、浴室、卫生间和实验室等高湿热、易沾污场所表面装饰的涂装。  \n\n氟碳涂料的主体树脂是氟代烷烃改性的丙烯酸酯。它是通过丙烯酸含氟烷基酯自聚或与丙烯酸酯共聚，制得含氟量不同的丙烯酸酯树脂；也可以由三氟氯乙烯和烷基乙烯基醚共聚形成的共聚物接枝丙烯酰基合成含氟丙烯酸酯树脂。在配方中含氟丙烯酸酯树脂含量一般要$350\\%$ 。活性稀释剂可用TMPTA、TPGDA 的丙烯酸官能单体。光引发剂要用耐黄变性好、光引发活性高的TPO和184等。  \n\nUV氟碳涂料用于外墙涂料，其性能与溶剂型氟碳外墙涂料、溶剂型丙烯酸聚氨酯外墙涂料对比见表6-23，很显然UV氟碳外墙涂料具有无可比拟的优异性能和性价比。UV氟碳涂料是UV涂料发展的一个方向，同时也是新一代高性能装饰涂料的发展方向。  \n\n表6-23UV氟碳外墙涂料与其他外墙涂料性能对比  \n\n\n<html><body><table><tr><td>性能指标</td><td>UV氟碳外墙涂料</td><td>溶剂型氟碳外墙涂料</td><td>溶剂型丙烯酸聚氨酯外墙涂料</td></tr><tr><td>固含量/%</td><td>≥95</td><td>≤50</td><td>≤50</td></tr><tr><td>固化时间</td><td>实干3~5s</td><td>表干≥20min，实干>24h</td><td>表干≥20min，实干>24h</td></tr><tr><td>固化温度</td><td>常温固化</td><td>180~250℃烘烤</td><td>120～150℃烘烤</td></tr><tr><td>附着力/级</td><td>≤1</td><td>≤1</td><td>≤1</td></tr><tr><td>使用寿命/年</td><td>>20</td><td>15~20</td><td>8~10</td></tr><tr><td>人工加速老化/h</td><td>>5000</td><td>>4000</td><td></td></tr><tr><td>耐擦洗/次</td><td>>12000</td><td>>10000</td><td></td></tr><tr><td>耐盐雾/h</td><td>≥3000</td><td>≥1500</td><td>≥500</td></tr><tr><td>耐酸碱性</td><td>优异</td><td>优秀</td><td>易受侵蚀</td></tr><tr><td>耐水性</td><td>48h沸水蒸煮，无变化</td><td>3h沸水蒸煮后剥离</td><td>1h沸水蒸煮后剥离</td></tr><tr><td>耐沾污性</td><td>灰尘、油污不易黏附</td><td>灰尘、油污不易黏附</td><td>灰尘、油污易黏附、变脏</td></tr><tr><td>抗霉菌性</td><td>极好</td><td>好</td><td>较差</td></tr><tr><td>综合成本</td><td>涂装成本较溶剂型氟碳涂料低20%</td><td>涂装成本高</td><td>涂装成本低</td></tr><tr><td>维修保养</td><td>不需要维修保养</td><td>不需要维修保养</td><td>维修保养成本高</td></tr></table></body></html>  \n\n生产和施工与传统粉末涂料基本一致：预混、挤出、粉碎、喷涂。但固化方式不一样：喷粉后工件先进入红外熔融段，粉末快速升温至 $90{\\sim}140^{\\circ}\\mathrm{C}$ 熔融成膜，然后进人强制对流段，使熔融膜流平，但不发生固化，最后进人UV固化段。由于涂料的熔融和固化是两个过程，因此UV粉末涂料比热固性粉末涂料有更好的流平性；而且熔融温度较低，可以适用于热敏性基材涂装；能耗也低；固化时间也较短，生产效率比传统粉末涂料高（图6-2)。与UV液体涂料相比，UV粉末涂料无活性稀释剂，涂膜固化收缩率低，与基材附着力高；可适用三维工件涂装和厚涂层（ ${\\mathrm{?}}75{\\sim}125\\mu\\mathrm{m}{\\mathrm{)}}$ ，的涂装；喷涂溅落的UV粉末涂料可回收使用，利用率高。UV粉末涂料兼有粉末涂料和UV涂料的优点，是一种比热固粉末涂料和UV液体涂料更具有技术优势、经济优势和生态优势的环保型涂料（表6-24)。  \n\n![](images/da1c290c1bbd6c6bbdbed2edb4e23d0840ce96f856b0f2ac021561bfc1732fb3.jpg)  \n图6-2传统热固型粉末涂料与UV固化粉末涂料固化过程比较示意图  \n\n表6-24传统粉末涂料、UV液体涂料和UV粉末涂料特点对比  \n\n\n<html><body><table><tr><td>特点</td><td>传统粉末涂料</td><td>UV液体涂料</td><td>UV粉末涂料</td></tr><tr><td>固化方式</td><td>热固化</td><td>UV固化：</td><td>红外流平，UV固化</td></tr><tr><td>固化时间</td><td>慢（10~20min)</td><td>快(几秒~几十秒)</td><td>较快(1~2min)</td></tr><tr><td>热敏基材</td><td>困难</td><td>可以</td><td>可以</td></tr><tr><td>立体涂装</td><td>可以</td><td>困难</td><td>可以</td></tr><tr><td>固化收缩率</td><td>较低</td><td>高</td><td>较低</td></tr><tr><td>涂层厚度</td><td>可厚涂层</td><td>薄涂层</td><td>可厚涂层</td></tr><tr><td>附着力</td><td>好</td><td>较差</td><td>好</td></tr><tr><td>流平性</td><td>较差</td><td>好</td><td>好</td></tr><tr><td>涂料回收</td><td>可以</td><td>不可以</td><td>可以</td></tr><tr><td>能耗</td><td>高</td><td>低</td><td>较低</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 193,
+        "chunk": "# 6.11.2 UV粉末涂料的组成和制造工艺  \n\nUV粉末涂料也由主体树脂、光引发剂、颜料、填料和助剂等组成。  \n\n主体树脂是UV粉末涂料的主要成膜物质，是决定涂料的性质和涂膜性能的主要成分。UV粉末涂料所用树脂要求在较低的温度下（一般 ${<}100^{\\circ}\\mathrm{C}$ ）具有较低的熔融黏度，以保证在光固化之前和光固化过程中具有良好的流动和流平性能；同时要有良好的光固化速率和贮存稳定性。目前已商品化的主体树脂有不饱和聚酯、 $z$ 烯基醚树脂、环氧丙烯酸树脂、聚氨酯丙烯酸树脂等。近年来超支化聚合物因其结构有高官能度、球形三维结构、分子内不易发生链缠结等特点，同时黏度低、活性高、容易改性，已应用于涂料中作成膜物，在UV粉末涂料中可降低树脂的玻璃化温度，使流变性和涂膜性能得到改善。表6-25和表6-26为部分UV粉末涂料的主体树脂的主要性能指标。  \n\n表6-25氰特公司UV粉末涂料树脂Uvecoat主要性能指标  \n\n\n<html><body><table><tr><td>商品名称</td><td>树脂形态</td><td>Tg/C</td><td>黏度/mPa·s</td><td>应用</td></tr><tr><td>2000</td><td>无定形甲基丙烯酸聚酯</td><td>47</td><td>3300(200℃)</td><td>金属部件，热敏合金</td></tr><tr><td>2100</td><td>无定形甲基丙烯酸聚酯</td><td>57</td><td>5500(200℃)</td><td>金属部件，热敏合金</td></tr><tr><td>2200</td><td>无定形甲基丙烯酸聚酯</td><td>54</td><td>4500(175C)</td><td>金属部件，热敏合金</td></tr><tr><td>2300</td><td>无定形</td><td>53</td><td>2500(200℃)</td><td></td></tr><tr><td>3000</td><td>无定形</td><td>51</td><td>6000(175C)</td><td>中密度板花纹漆、清漆，PVC地板漆</td></tr><tr><td>3001</td><td>无定形</td><td>43</td><td>2000(175C)</td><td>平整度高的木器清漆</td></tr><tr><td>3002</td><td>无定形</td><td>49</td><td>4500(175C)</td><td>中密度板花纹漆、清漆</td></tr><tr><td>3003</td><td>无定形</td><td>49</td><td>3500(175C)</td><td>PVC地板漆</td></tr><tr><td>3101</td><td>无定形</td><td>43</td><td>1800(175C)</td><td></td></tr><tr><td>9010</td><td>半结晶</td><td>80(Tm)</td><td>300(100℃)</td><td>配合3000系列使用，降低熔融黏度</td></tr></table></body></html>  \n\n表6-26DowChemical及DSM公司UV粉末涂料树脂主要性能指标  \n\n\n<html><body><table><tr><td>公司</td><td>产品型号</td><td>树脂类型</td><td>黏度/Pa·s</td><td>T或Tm/℃</td></tr><tr><td>Dow Chemical</td><td>XZ92478.00</td><td>环氧丙烯酸树脂</td><td>2~4(150℃)</td><td>85~105</td></tr><tr><td>DSM</td><td>Uracross P3125</td><td>无定形不饱和聚酯树脂</td><td>30~50(165℃)</td><td>48</td></tr><tr><td>DSM</td><td>Uracross ZW4892P</td><td>无定形不饱和聚酯树脂</td><td>50~100(165℃)</td><td>51</td></tr><tr><td>DSM</td><td>Uracross ZW4901P</td><td>无定形不饱和聚酯树脂</td><td>30~70(165℃)</td><td>54</td></tr><tr><td>DSM</td><td>Uracross P3307</td><td>半结晶乙烯基醚氨基树脂</td><td></td><td>90~110(Tm)</td></tr><tr><td>DSM</td><td>Uracross P3898</td><td>半结晶乙烯基醚氨基树脂</td><td></td><td>90~130(Tm)</td></tr></table></body></html>  \n\nUV粉末涂料所用光引发剂要无毒无味，不易挥发，耐黄变性好，迁移性低，与树脂混容性好，贮存稳定性好。自由基固化UV粉末涂料常用184、651、2959、907、TPO和819等，阳离子固化UV粉末涂料用硫盐和碘盐，并配以少量自由基光引发剂以提高光引发效率。UV粉末涂料由于是有色涂层，而且涂层较厚，所以使用高引发活性且有光漂白性能的TPO和819更为有效。  \n\nUV粉末涂料所用颜料要尽量选用对光引发剂吸收光谱波段吸收和散射低的品种，以保证光引发剂发挥最大的引发效率。研究发现UV粉末涂料中黄色颜料较难固化，红色及蓝色相对来说较易固化。黑色颜料固化得益于黑涂层在曝光过程中对热量的吸收，但含量要低于 $1\\%$ ，白色颜料含 $25\\%$ 二氧化钛的涂层亦能很好固化。由于UV粉末涂料涂层一般较厚，颜料存在会影响涂层表面和底层的UV光强度，从而使表面和底层固化不一致，导致涂膜起皱，因此必须谨慎选择颜料并与主体树脂、光引发剂、助剂等匹配。  \n\n对于应用于户外的UV粉末涂料涂装的工件，不可避免地会受到日晒雨淋，要求UV粉末涂料有很好的耐候性和防老化性，因此要添加紫外吸收剂和光稳定剂，常用苯并三唑类和羟基苯叮嗪类紫外吸收剂配合受阻胺类光稳定剂。紫外吸收剂可防止涂层的变色及光化学降解，受阻胺光稳定剂可消除高聚物降解产生的有害自由基（过氧化氢自由基等)，从而防止光泽度及柔韧性的降低。但紫外吸收剂加入会参与光引发剂对UV光吸收的竞争，而影响引发自由基的产生。因此在选择紫外吸收剂和光稳定剂时，要选用对光引  \n\n发剂影响小的品种，以保证光固化完全。  \n\n在UV粉末涂料配方中还要使用流平剂、消泡剂、边角覆盖力改性剂、消光剂、固化促进剂等多种助剂。  \n\nUV粉末涂料的制备方法是将物料（树脂、光引发剂、颜料、填料和助剂等）经预混后在挤出机中熔融混炼、挤出、然后冷冻、粉碎、过筛（图6-3)。  \n\n![](images/8bd23819df2231bb9b5fc8c59d22194a0df7623b02b19812665ec41b3afec256.jpg)  \n图6-3UV粉末涂料的制备工艺流程示意图 1～4—树脂颜料填料助剂；5—预混合；6一挤出；7一冷却；8—研磨；9—滤尘； 10—过筛；11—产品；12—超尺寸产品",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 194,
+        "chunk": "# 6.11.3 UV粉末涂料的应用  \n\nUV粉末涂料由于可以用于对热敏感的基材，如木制品、塑料制品等，所以它的应用范围就扩大了。  \n\n（1）木制品UV粉末涂料用于中密度纤维板，是欧洲涂料工业开发成功的第一个应用领域。UV粉末涂料用静电喷涂技术进行涂装，不但可以涂饰中密度板的表面，对侧面和形状复杂的立体部件均可一次涂装。对于高密度木制品，使用UV粉末涂料也非常理想。对于低密度木制品，为了避免基材脱气的影响，需要对基材先涂一层液态涂料密封木制品基材的孔隙。  \n\n（2）塑料制品塑料的耐热温度不高，用传统的热固化粉末涂料进行涂装是不可能的。而UV粉末涂料的流平温度一般在 $120^{\\circ}\\mathrm{C}$ ，使用红外加热，基材表面温度往往不超过 $80^{\\circ}\\mathrm{C}$ ，因此可用UV粉末涂料涂装塑料制品，不会导致塑料变形。可以预料塑料制品将是UV粉末涂料又一重要的应用领域。  \n\n（3）合金及预制装配制品合金（如铝镁合金）的应用很广泛，但一直不能用粉末涂料来涂饰，这是因为在 $115\\mathrm{^\\circC}$ 时，合金的金相性能会受到影响。许多预制装配制品上都装有电子元件、塑料、橡胶密封圈、层压制品等热敏部件，它们的承受温度不能过高。UV粉末涂料涂装时流平和固化温度可以满足这些基材的要求，因此具有广阔的应用前景。  \n\n（4）大件金属涂装坏料或笨重金属部件时，UV粉末涂料可不必将整件物件全部加热而涂装，从而可使能耗大大降低，也可节省涂装时间。  \n\n（5）汽车涂料UV粉末涂料的一个潜在用途是汽车钢板的涂饰。汽车钢板的涂饰一直是传统的粉末涂料的领地，而UV粉末涂料在质感、外观、性能等方面均可与热固化粉末涂料媲美，同时具有节能、快速等优势，有望替代热固化粉末涂料，应用于汽车钢板的涂饰。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 195,
+        "chunk": "# 6.12.1 UV水性涂料的特点  \n\nUV光固化技术和材料40年来有了快速的发展，但它也存在一些问题，影响了它的应用和推广。特别是使用活性稀释剂调节体系黏度，而活性稀释剂主要为丙烯酸酯类，对人体的皮肤、黏膜和眼睛有刺激性，有的还有臭味；对低黏度UV体系（如喷涂）要用大量活性稀释剂，有时还要用有机溶剂，易燃易爆，生产和使用不安全；在光固化时，活性稀释剂难以完全反应，在固化涂层中残留少量活性稀释剂，不适用对安全卫生要求严格的食品、药品、婴儿产品的包装材料的印刷和涂装；油性光固化材料其生产设备、包装材料和施工设备的清洗仍需用有机溶剂。为了克服这些病，一种新的UV体系—UV水性体系应运而生。UV水性体系继承和发展了传统的UV固化技术和水性涂料、油墨的优点，已成为光固化技术研究和开发的一个非常活跃的领域，而且获得了实际应用。  \n\nUV水性涂料结合了传统UV涂料和水性涂料的各自特点，相对于传统油性UV涂料具有下列优点。  \n\n① 水是最方便获得、最廉价的原料，用水来代替活性稀释剂稀释低聚物，很容易调节黏度，可实现无活性稀释剂的UV涂料配方。  \n\n② 不用活性稀释剂就没有VOC排放、刺激性和臭味问题，安全、无害、环保。  \n\n③可适用各种涂装设备施工，UV水性涂料不会燃烧和爆炸，对喷涂特别安全。  \n\n④可避免由于用活性稀释剂所引起的固化体积收缩，有利于提高涂料附着力。  \n\n$\\textcircled{5}$ 可实现薄涂层涂布，降低成本。  \n\n③生产设备、涂装设备和容器可以用水性清洗液清洗。  \n\nUV水性涂料除了上述优点外，还有一个很突出的优点是解决传统UV涂料的硬度和柔韧性矛盾的一种有效途径。从分子结构与性能的关系分析，只有高分子量的物质才能具有高硬度和高柔韧性。传统UV涂料使用的低聚物分子量较低，同时加人大量低分子量活性稀释剂，因此难以兼顾硬度和柔韧性。而UV水性涂料的低聚物是高分子量的水性分散体，其黏度与聚合物的分子量无关，而只与固含量有关，因而在UV水性涂料中可以使用高分子量的低聚物，又不用低分子量的活性稀释剂，从而克服了UV涂料高硬度和高柔韧难以兼顾的矛盾。 艾#但UV水性涂料也存在一些缺点，需加以注意和克服。  \n\n①体系中存在水，在UV固化前大多需要进行干燥除水，而水的高蒸发热（40.6kJ/mol)，导致能耗增加，也使生产时间延长，生产效率下降。  \n\n② 水的高表面张力（70.8mN/m)，不易浸润基材，易引起涂布不匀；对颜料润湿性差，影响分散。  \n\n③固化膜的光泽较低，耐水性和耐洗涤性较差；体系的稳定性较差，对pH较为敏感。  \n\n$\\textcircled{4}$ 水的凝固点为 $0^{\\circ}\\mathrm{C}$ ，在北方运输和贮存过程中需添加防冻剂；水性体系容易滋生霉菌和细菌，需用防霉剂，使配方复杂化。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 196,
+        "chunk": "# 6.12.2 UV水性涂料的组成  \n\nUV水性涂料是由水性低聚物、光引发剂、助剂和水组成的，其中水性低聚物和光引发剂是最主要的成分。  \n\n（1）水性低聚物从结构上看：一要具有可以进行光聚合的基团，如丙烯酰氧基、甲基丙烯酰氧基、乙烯基、烯丙基等，由于丙烯酰氧基固化速率最快，所以水性低聚物主要为各类丙烯酸树脂；二要分子链上含有一定数量的亲水基团，如羧基、羟基、氨基、季铵基、醚基、酰胺基等。目前水性低聚物的制备大多采用在原油性低聚物中引入亲水基团，如羧基、季铵基、聚乙二醇等方式，使油性低聚物转变成水性低聚物。  \n\n水性低聚物中研究得最多的是水性聚氨酯丙烯酸酯，主要通过聚乙二醇引人非离子型的亲水链段；或用二羟甲基丙酸引入羧基，得到离子型水溶性低聚物。由于水性聚氨酯丙烯酸酯柔韧性好，有高耐冲击和拉伸强度，能提供好的耐磨性和耐抗性，综合性能优越，目前大多数商品化的水性低聚物是水性聚氨酯丙烯酸酯类型(表3-26)。  \n\n水性环氧丙烯酸酯是利用环氧丙烯酸酯中仲羟基与马来酸酐类反应而得到含羧基的低聚物；或采用环氧基引入季铵盐而成为水性环氧丙烯酸酯。水性环氧丙烯酸酯光固化速率快，硬度、强度和耐抗性都优异。  \n\n丙烯酸酯化聚丙烯酸酯一般可用丙烯酸与各种丙烯酸酯共聚引入亲水性的羧基，再用（甲基）丙烯酸羟乙酯或（甲基）丙烯酸缩水甘油酯共聚引入羟基或环氧基以便进一步引入丙烯酰氧基，获得光活性。水性丙烯酸酯化聚丙烯酸酯具有价廉易制备、涂膜丰满、光泽好、耐黄变和耐候性好等特点。  \n\n水性不饱和聚酯是以二元醇或多元醇与马来酸酐酯化反应制得，为了使树脂具有亲水性，可采用聚乙二醇引人亲水结构。  \n\n利用聚氨酯丙烯酸酯体系和丙烯酸酯体系，经接枝改性，形成互穿网络的“杂化”体系，制得的水性“杂化”树脂，其性能可互补甚至有协同的效果。  \n\n（2）光引发剂用于UV水性涂料的光引发剂可分为水分散型和水溶型两类。目前常规UV涂料所用的光引发剂大多为油溶性的，在水中溶解度很小，不适用UV水性涂料。近年来水性光引发剂研究开发成为热门课题，也取得了可喜的进展，不少水性光引发剂是由原来油溶剂光引发剂结构中引人阴离子、阳离子或亲水性的非离子基团，使其变成水溶性；或将油溶性光引发剂变成稳定的水乳液或水分散体使用。已经商品化的水性光引发剂有：KIPEM、819DW、QTX、BTC、BPQ等。  \n\nKIPEM是高分子型光引发剂KIP150稳定的水乳液，含有 $32\\%$ 的KIP150， $\\lambda_{\\operatorname*{max}}$ 为$245\\mathrm{nm}$ ， $325\\mathrm{nm}$ 。  \n\n819DW是麟化氧类光引发剂819稳定的水乳液， $\\lambda_{\\operatorname*{max}}$ 为 $370\\mathbf{nm}$ ， $405\\mathrm{nm}$ 。  \n\nQTX是硫杂葱酮的季铵盐，为水溶性光引发剂， $\\lambda_{\\operatorname*{max}}$ 为 $\\scriptstyle405\\mathbf{nm}$ 。  \n\nBTC和BPQ都是水溶性光引发剂，为二苯甲酮衍生物季铵盐。  \n\n另外，光引发剂2959由于在1173苯环对位引人了羟基乙氧基（ $\\mathrm{HOCH_{2}C H_{2}O-})$ ，使其在水中溶解度从 $0.1\\%$ 提高到 $1.7\\%$ ，因此也常用在UV水性涂料中。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 197,
+        "chunk": "# 6.12.3 UV水性涂料的应用  \n\n随着世界各国对环境生态保护的重视，环保立法日益完善，执法日益严格，推动了UV水性涂料的开发和应用，而UV水性涂料的优良性能也引起了人们的兴趣和重视。表6-27列举了UV水性涂料与溶剂型热塑性和热固性涂料的涂膜性能比较。  \n\n表6-27各种涂层材料的涂膜性能比较  \n\n\n<html><body><table><tr><td>性能</td><td>热塑性丙烯酸 树脂</td><td>二液型聚氨酯 树脂</td><td>UV聚氨酯丙烯酸酯 分散体②</td><td>UV丙烯酸酯 乳液</td></tr><tr><td>抗划伤性</td><td>4</td><td>10</td><td>10</td><td>10</td></tr><tr><td>热印刷性(65℃，4h,0.03MPa)</td><td>3</td><td>6</td><td>10</td><td>9</td></tr><tr><td>耐磨性(1h)</td><td>3</td><td>8</td><td>9</td><td>9</td></tr><tr><td>耐抗性</td><td></td><td></td><td></td><td></td></tr><tr><td>丙酮</td><td>2</td><td>9</td><td>10</td><td>9</td></tr><tr><td>乙醇</td><td>8</td><td>10</td><td>10</td><td>9</td></tr><tr><td>10%氨水（16h)</td><td>9</td><td>10</td><td>10</td><td>10</td></tr><tr><td>醋（16h)</td><td>6</td><td>10</td><td>6</td><td>10</td></tr></table></body></html>\n\n$\\Phi$ 溶剂型涂料$\\textcircled{2}$ $11732\\%$ ，UV曝光量 $1.6\\mathrm{J}/\\mathrm{cm}^{2}$ 。数字以10为最好。  \n\n目前UV水性涂料已在纸张上光油、木器清漆、电沉积光致抗蚀剂和丝印油墨等产品上获得实际应用，正在开发用于UV塑料涂料、UV皮革涂料、UV织物涂料、水显影型光成像阻焊剂、UV凹印油墨、UV柔印油墨、UV喷墨油墨等。  \n\n（1）纸张上光油这是UV水性涂料最早应用的领域之一，有UV水性底油和UV水性上光油，目前光泽度可达90以上，可联机上光或脱机单独上光。  \n\n（2）木器涂料UV水性涂料在木材和木器涂饰上有较高的应用价值，特别在胶合板与成型木器的涂装上比较有利。采用低含固量的清漆，有优异的木纹展现性，可增加木质的美感。  \n\n（3）电沉积抗蚀剂这是将抗蚀剂中感光性树脂进行亲水改性后变成水溶性感光性树脂，经电沉积后在覆铜板表面形成一层薄薄的均匀而致密的抗蚀膜，其分辨率可达0.02～0.03mm，高于UV抗蚀油墨、抗蚀干膜和光成像抗蚀油墨的分辨率。这是UV水性涂料在电子化学品中应用的实例。  \n\n（4）丝印油墨这也是UV水性涂料一个重要应用领域，由于更环保、更安全，适用于户外广告宣传和标牌制作。  \n\n（5）皮革涂料和织物涂料皮革（包括人造革）和各种织物都是穿戴在人的身体上，因此要求在生产中使用环保型涂料，才能最终穿着时不会受到污染。而UV水性涂料是一种最佳的选择，既环保、安全，又高效，优质，因此开发UV水性皮革涂料和织物涂料，也是UV水性涂料应用的一个重要方面。 Y S4  \n\n（6）凹印油墨和柔印油墨目前凹印和柔印大量使用水性油墨，正适合UV水性涂料拓展的应用领域，但要解决油墨的适印性和稳定性，才能成为实用。  \n\n（7）喷墨油墨喷墨印刷作为一种非接触式、无压力、无印版的数字化印刷方式，从20世纪90年代获得迅速发展，20世纪末又出现了UV喷墨印刷，在平台式喷绘机上，在大幅面、小批量的广告牌、指示牌生产中获得广泛应用，UV水性喷墨油墨则利用其低黏度、高性能、环保、安全、对人体无害等特点，将成为UV喷墨油墨研发方向之一。  \n\n以下配方单位为质量份。  \n\n<html><body><table><tr><td colspan=\"4\">6.13.1UV纸张上光油参考配方</td></tr><tr><td colspan=\"4\">（1）UV纸张上光油参考配方</td></tr><tr><td colspan=\"2\">改性EA（VPLS2266） 胺改性聚醚丙烯酸酯VPLS2299 TPGDA</td><td>75.0 25.0 89.0</td><td>500 15.0 MDEA 6.0</td></tr><tr><td colspan=\"2\">助剂（Rad2100） （2）UV纸张上光油参考配方</td><td></td><td>0.6</td></tr><tr><td colspan=\"2\">改性EA（VPLS2266） 胺改性聚醚丙烯酸酯（VPLS2299）</td><td>55.0 BP 18.8 184 21.2</td><td>2.6 2.6 Tego Rad 2100 0.3</td></tr><tr><td colspan=\"2\">TPGDA （3）UV纸张上光油参考配方</td><td></td><td></td></tr><tr><td colspan=\"2\">胺改性聚醚丙烯酸酯（VPLS2299） TPGDA</td><td>100.0 500 40.0</td><td>8.5 助剂（Rad2100） 0.4</td></tr><tr><td colspan=\"2\">（4）UV纸张上光油参考配方 EA(6104)</td><td>20 BP 10 1173</td><td>3 3</td></tr><tr><td colspan=\"2\">氨基丙烯酸酯（6117） 15 活性胺 TMPTA TPGDA</td><td>20 BYK333 20 润湿剂</td><td>2 0.5 0.2</td></tr><tr><td colspan=\"2\">（5）UV纸张上光油参考配方 低黏度低色度EA TPGDA</td><td>39 BP 16 活性胺</td><td>6 12</td></tr><tr><td colspan=\"2\">HDDA （6）UV纸张上光油参考配方</td><td>26 流平剂 10.0 BP</td><td>1</td></tr><tr><td colspan=\"2\">EA DPTTA 胺改性聚醚丙烯酸树脂</td><td>6.5 184 75.0 硅流平剂</td><td>6.0 2.0 0.5</td></tr><tr><td colspan=\"2\">（7）UV纸张上光油参考配方 EA</td><td>22.8 BP 23.0 MDEA</td><td>3.0 3.0</td></tr><tr><td colspan=\"2\">TMPTA TPGDA 1173</td><td>45.0 流平剂 3.0</td><td>0.2</td></tr><tr><td colspan=\"2\">（8）UV纸张上光油参考配方 EA</td><td>14.0 BP</td><td>7.0 4.0</td></tr><tr><td colspan=\"2\">PUA TMPTA HDDA 10.0 蜡</td><td>14.0 MDEA 49.5 润湿剂</td><td>0.5 1.0</td></tr></table></body></html>  \n\n（9）UV纸张上光油参考配方  \n\n\n<html><body><table><tr><td>EA GPTA</td><td></td><td>30.0 30.0 24.0</td><td>1173 有机硅丙烯酸酯 流平剂</td><td>5.0 0.5 0.5</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 198,
+        "chunk": "# （10）UV纸张上光油参考配方  \n\n<html><body><table><tr><td>EA</td><td>44.5 8.0</td><td>184 活性胺</td><td>1.0 5.0</td></tr><tr><td>丙烯酸环氧亚麻油酯 TPGDA</td><td>35.0 5.0</td><td>硅助剂</td><td>1.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 199,
+        "chunk": "# （11）UV纸张上光油参考配方  \n\n<html><body><table><tr><td>低黏度EA TPGDA</td><td>30 BP 1173</td><td>4 2</td></tr><tr><td>丙氧基甘油三丙烯酸酯</td><td>23 34</td><td>N-甲基二乙醇胺 4</td></tr><tr><td>DPPA</td><td>2</td><td>流平剂 1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 200,
+        "chunk": "# （12）UV纸张上光油参考配方  \n\n<html><body><table><tr><td>EA PUA TPGDA</td><td>55 10 8</td><td>651 3 活性胺 15 聚硅氧烷润滑剂 1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 201,
+        "chunk": "# （13）UV纸张上光油参考配方  \n\n<html><body><table><tr><td>EA UPE</td><td>40.5 10.0</td><td>BP TEA</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 202,
+        "chunk": "# （14）UV纸张上光油参考配方  \n\n<html><body><table><tr><td>EA(CN120A75)</td><td></td><td>62.4 29.4</td><td>BP DMEA</td><td>2.8 2.6</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 203,
+        "chunk": "# （15）UV纸张上光油参考配方  \n\n<html><body><table><tr><td>EA[CN10420含20%，NPG（PO）DA]</td><td>44.0</td><td>活性胺（CN366） 184</td><td></td><td>9.9</td></tr><tr><td>NPG(PO)2DA DTMPTA</td><td>30.9 3.2 6.0</td><td>Bentone27 氧化锌</td><td></td><td>2.0 0.4</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 204,
+        "chunk": "# （16）UV纸张上光油参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（CN970E60） DPPA</td><td>57.5 10.0 3.5</td><td>KIP100F TZT</td><td>3.0</td><td>3.0 3.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 205,
+        "chunk": "# （17）UV纸张上光油参考配方  \n\n<html><body><table><tr><td>EA</td><td>34.5</td><td>TMP（EO)TA 20.0</td></tr><tr><td>DPTTA</td><td>25.0</td><td>BP 2.0</td></tr></table></body></html>  \n\n<html><body><table><tr><td>KIP150 3.0 ITX 0.5</td><td>活性胺 12.0 有机硅丙烯酸酯 3.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 206,
+        "chunk": "# 注：高耐抗水和抗溶剂性，耐磨性和低气味。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 207,
+        "chunk": "# （18）UV纸张上光油参考配方  \n\n<html><body><table><tr><td>EA GPTA</td><td></td><td>36 25</td><td>184</td></tr><tr><td>TPGDA BP</td><td></td><td>活性胺 20 硅流平剂 6</td><td>10 1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 208,
+        "chunk": "# 注：快速固化和耐磨性好。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 209,
+        "chunk": "# （19）UV纸张上光油参考配方  \n\n<html><body><table><tr><td>附着力促进型PEA 低黏度芳香族单丙烯酸酯</td><td>71.3 9.5 184</td><td>附着力促进型带羧基三丙烯酸酯</td><td>4.0 3.9</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 210,
+        "chunk": "# （20）UV辊涂纸张上光油参考配方  \n\n<html><body><table><tr><td>EA</td><td></td><td>22.8</td><td>1173</td><td>3.0</td></tr><tr><td>TMPTA TPGDA</td><td></td><td>23.0 45.0 3.0</td><td>N-甲基二乙醇胺 流平剂</td><td>3.0 0.2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 211,
+        "chunk": "# （21）UV辊涂纸张上光油参考配方  \n\n<html><body><table><tr><td>EA[含20%NPG（PO）DA]</td><td>44.0</td><td>活性胺</td><td></td><td>9.9</td></tr><tr><td>NPG(PO)DA DTMPTA</td><td>30.9 3.2</td><td>184 触变剂</td><td>3.6</td><td>1.0 0.2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 212,
+        "chunk": "# （22）UV辊涂纸张上光油参考配方  \n\n<html><body><table><tr><td>EA（含20%TPGDA）</td><td></td><td>18.4 55.4</td><td>活性胺 1173</td><td></td><td>10.0</td></tr><tr><td>TPGDA TMP（EO)TA</td><td></td><td>10.0 5.0</td><td>流平剂</td><td></td><td>1.0 0.2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 213,
+        "chunk": "# （23）UV辊涂纸张上光油参考配方  \n\n<html><body><table><tr><td>OTA480 TPGDA 活性胺 BP</td><td></td><td>56.0 15.5 18.0 7.0</td><td>651 稳定剂 硅表面活性剂</td><td>3.0 0.2 0.3</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 214,
+        "chunk": "# （24）UV丝印纸张上光油参考配方  \n\n<html><body><table><tr><td>EA</td><td>46.0</td><td>1173 BP</td><td></td><td>1.0</td></tr><tr><td>TPGDA TMP（EO)TA</td><td>16.5 10.0</td><td>流平剂</td><td></td><td>5.0</td></tr><tr><td></td><td></td><td></td><td></td><td>0.5</td></tr><tr><td>活性胺</td><td>21.0</td><td></td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 215,
+        "chunk": "# （25）UV丝印纸张上光油参考配方  \n\n<html><body><table><tr><td>改性EA（623，A-80，含20%TPGDA） (PO)NPGDA BP 184 活性胺（Etercure6420） 二官能度脂肪族PUA（611A-85，含15%TPGDA）</td><td>60 消泡剂（FoamerxN） 20 平滑剂（Eyerslip70） 20 黏度（25C）/mPa·s 2 固化速率（m/min） 1 光泽（60°） 5 耐折性/次</td><td>0.2 3500 123 94.9 4</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 216,
+        "chunk": "# （26）UV凹印纸张上光油参考配方  \n\n<html><body><table><tr><td>低黏度EA（CN124A80） TPGDA</td><td>52 24</td><td>1173 2 活性胺 15</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 217,
+        "chunk": "# （27）UV凹印纸张上光油参考配方  \n\n<html><body><table><tr><td>低黏度EA（CN141） PEG（400)DA</td><td>13.5 15.0</td><td>非迁移光引发剂（SR1111） 流平剂（SR011）</td><td>30.0 0.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 218,
+        "chunk": "# （28）UV凹印纸张上光油参考配方  \n\n<html><body><table><tr><td>低黏度EA（CN124C60） HDDA</td><td>39 26</td><td>BP 6 活性胺 12</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 219,
+        "chunk": "# （29）UV凹印低光泽纸张上光油参考配方  \n\n<html><body><table><tr><td>低黏度EA</td><td>13.5 17.0 43.0</td><td>1173 SiO(OK-412)</td><td>7.0 9.0 1.0</td></tr><tr><td colspan=\"4\" rowspan=\"3\">PEG(400)DA TMP（EO)TA EOEOEA</td></tr><tr><td>润湿剂（SR021）</td></tr><tr><td>0.5</td></tr><tr><td>流平剂（SR011）</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 220,
+        "chunk": "# （30）UV柔印纸张上光油参考配方  \n\n<html><body><table><tr><td>EA</td><td></td><td>78 8</td><td>TEA 6 活性胺 5</td></tr><tr><td>BP 184</td><td colspan=\"3\"></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 221,
+        "chunk": "# （31）UV柔印底漆上光油参考配方  \n\n<html><body><table><tr><td>低黏度EA（CN124C60）</td><td>53 23</td><td>活性胺 流平剂（SR010）</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 222,
+        "chunk": "# （32）UV柔印纸张上光油参考配方  \n\n<html><body><table><tr><td>EA(CN120A75) DPPA GP(PO)TA</td><td>17.5</td><td>26.0 DMEA 2.0 流平剂（BYK301） 43.0 助剂（DC-57） 阻聚剂</td><td>4.0 1.0 1.0 3.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 223,
+        "chunk": "# （33）UV柔印纸张上光油参考配方  \n\n<html><body><table><tr><td>低黏度EA（CN141）</td><td>30</td><td>BP 4 1173 2</td></tr><tr><td>GPTA</td><td>34</td><td></td></tr><tr><td>TPGDA</td><td>23</td><td>DMEA 4</td></tr><tr><td>DPP/HA</td><td>2</td><td>流平剂（SR010） 1</td></tr></table></body></html>  \n\n（34）UV胶印纸张上光油参考配方   \n\n\n<html><body><table><tr><td>EA 丙烯酸环氧亚麻油酯 乙氧基双酚A二丙烯酸酯</td><td>40 BP 10 中国瓷土 20 1173</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 224,
+        "chunk": "# （35）UV胶印纸张上光油参考配方  \n\n（36）UV胶印纸张上光油参考配方  \n\n\n<html><body><table><tr><td>EA TMPTA</td><td rowspan=\"3\">40 20 2</td><td>BP 活性胺</td></tr><tr><td>TPGDA</td><td>7 15 瓷土 10</td></tr><tr><td>1173</td><td>聚乙烯蜡 1</td></tr></table></body></html>  \n\n（37）UV胶印纸张上光油参考配方  \n\n\n<html><body><table><tr><td>EA GPTA</td><td></td><td rowspan=\"2\">50.0 32.5 4.0 2.0</td><td rowspan=\"2\">硅流平剂 瓷土 SiO2</td><td rowspan=\"2\"></td><td rowspan=\"2\">1.5 9.0 2.0</td></tr><tr><td>184 聚乙烯蜡</td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>EA PEA 聚醚丙烯酸树脂 EO-TMPTA</td><td>20.0 12.0 30.0 18.0 10.0</td><td>184 TPO EDAB 消泡剂</td><td>4.0 0.5 1.5 0.5 0.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 225,
+        "chunk": "# （38）UV胶印纸张上光油参考配方  \n\n<html><body><table><tr><td>低黏度EA（CN124A80） 52 TPGDA 12 PEG(400)DA 12 BP 6</td><td>1173 2 活性胺 15 流平剂 1</td></tr><tr><td>（39）UV纸张潮气阻隔上光油参考配方</td><td></td></tr><tr><td>氯化橡胶（ParlonS10） 20 氯化石蜡（Chlorowax70） 10 VAc 29 TMPTA 30</td><td>苯偶姻乙醚 9 马来酸二丁基锡 1 二硫化四甲基秋兰姻 1</td></tr><tr><td>（40）UV无异味纸张上光油参考配方</td><td>非迁移光引发剂（SR1111）</td></tr><tr><td>低黏度EA（CN141） 13.5 PEG(400)DA 15.0 TMP(EO)3TA 41.0</td><td>30.0 流平剂（SR011） 0.5</td></tr><tr><td>（41）UV无气味纸张上光油参考配方</td><td>PEGDA</td></tr><tr><td>EA 10 PEA 18.5 脂肪族PUA 10</td><td>15 KIP150 10 流平剂 0.5</td></tr></table></body></html>  \n\n（42）UV低气味纸张上光油参考配方  \n\n\n<html><body><table><tr><td>EA</td><td>30.0</td><td>胺改性聚醚丙烯酸酯 10.0</td></tr><tr><td>GPTA</td><td>30.0</td><td>聚醚丙烯酸酯 5.0</td></tr><tr><td></td><td></td><td>LE-HK（低迁移性多官能a-羟基酮） 6.0</td></tr><tr><td>TPGDA</td><td>24.0</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 226,
+        "chunk": "# 6.13.2 UV木器涂料参考配方",
+        "category": " References"
+    },
+    {
+        "id": 227,
+        "chunk": "# 6.13.2.1UV木器腻子参考配方",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 228,
+        "chunk": "# （1）UV木器腻子参考配方  \n\n<html><body><table><tr><td>UPE/St（65/35)</td><td></td><td>36 重晶石 2 钛白粉</td><td></td><td>20 7</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 229,
+        "chunk": "# （2）UV木器腻子参考配方  \n\n<html><body><table><tr><td>EA TPGDA HEA</td><td>38 10 5 10</td><td>SiO2 BP 活性胺 184</td><td>0.01 4 5 1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 230,
+        "chunk": "# （3）UV木器腻子参考配方  \n\n<html><body><table><tr><td>EA TPGDA</td><td>25 8</td><td>超细滑石粉 651</td><td>24 1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 231,
+        "chunk": "# （4）UV辊涂木器腻子参考配方  \n\n<html><body><table><tr><td>EA(EB3500) 纯丙烯酸酯低聚物（EB745）</td><td>19.0 19.0 23.0 651</td><td>CaCO3 500</td><td>15.0 1.0 2.6</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 232,
+        "chunk": "# （5）UV辊涂木器腻子参考配方  \n\n<html><body><table><tr><td>四官能团PEA（CN920） PEG(400)DA</td><td>20.0 46.2 4.0</td><td>TEA 3.0 滑石粉 25.0 流平剂（SR011） 0.3</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 233,
+        "chunk": "# （6）UV白色木器腻子参考配方  \n\n<html><body><table><tr><td>EA TPGDA N-VP</td><td rowspan=\"3\">28.22 7.53 1.88</td><td rowspan=\"3\">重晶石粉 ITX EDAB 助剂</td><td></td><td rowspan=\"3\">28.22 1.00 4.80</td></tr><tr><td>TiO2 滑石粉</td><td></td></tr><tr><td colspan=\"2\" rowspan=\"2\">14.11</td><td rowspan=\"2\">0.13</td></tr><tr><td>14.11</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 234,
+        "chunk": "# （7）UV白色木器腻子参考配方  \n\n<html><body><table><tr><td>EA</td><td>7 63</td><td>ITX 651</td><td>1 1</td></tr><tr><td>TPGDA</td><td>11</td><td>EDAB</td><td>5</td></tr><tr><td>滑石粉 TiO2</td><td></td><td>12</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 235,
+        "chunk": "# （8）UV白色地板腻子参考配方  \n\n<html><body><table><tr><td>高光泽UP（VPLS2110） (BlancatalcSuper) (Mistron CFS)</td><td>33.53 16.77 16.77</td><td>(Leichtspat) (Aerosil300) DPGDA</td><td>16.77 0.34 13.40</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 236,
+        "chunk": "# 6.13.2.2UV木器底漆参考配方",
+        "category": " References"
+    },
+    {
+        "id": 237,
+        "chunk": "# （1）UV木器底漆参考配方  \n\n<html><body><table><tr><td>气干型UPE St.</td><td>71.5 17.8</td><td>气相SiO 651</td><td>1.7 4.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 238,
+        "chunk": "# （2）UV木器底漆参考配方  \n\n<html><body><table><tr><td>EA</td><td></td><td>27.0 1173 15.0 BP</td><td></td><td>1.5</td></tr><tr><td>四官能PEA TPGDA</td><td></td><td>46.5 4.0</td><td>硬脂酸锌 流平剂</td><td>5.0 0.5 0.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 239,
+        "chunk": "# （3）UV木器底漆参考配方  \n\n<html><body><table><tr><td>EA TMPTA</td><td>40 8 22</td><td>滑石粉 1173 BP</td><td></td><td>10 1</td></tr><tr><td>TPGDA HPA</td><td></td><td>7 DMEA 5</td><td></td><td>3 3</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 240,
+        "chunk": "# （4）UV竹木器底漆参考配方  \n\n<html><body><table><tr><td>改性EA</td><td>30.0 35.0</td><td>651 BP</td><td></td><td>2.0 3.0</td></tr><tr><td>TPGDA TMPTA</td><td></td><td>7.0 滑石粉 8.0</td><td>阻聚剂</td><td>15.0 0.1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 241,
+        "chunk": "# （5）UV竹木器底漆参考配方  \n\n<html><body><table><tr><td>改性EA</td><td>40 45</td><td>651 BP</td><td>2 3</td></tr><tr><td>TPGDA TMPTA</td><td rowspan=\"3\">7</td><td></td></tr><tr><td></td><td>滑石粉 25</td></tr><tr><td>8</td><td>2，6-二叔丁基对甲酚 0.1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 242,
+        "chunk": "# （6）UV辊涂木器底漆参考配方  \n\n<html><body><table><tr><td>EA(EB645) 胺改性丙烯酸酯（EB7100）</td><td>20.0 2.5</td><td>500 CaCO3</td><td></td><td>1.5 15.0</td></tr><tr><td>DPGDA 4265</td><td>21.0 2.5</td><td>TiO2 Disperbyk110</td><td></td><td>25.0 3.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 243,
+        "chunk": "# （7）UV-辊涂木器底漆参考配方  \n\n<html><body><table><tr><td>EA(EB6040) 胺改性PEA（EB81）</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 244,
+        "chunk": "# （8）UV辊涂木器底漆参考配方  \n\n<html><body><table><tr><td colspan=\"2\">PEA(PRO4663) 22.6 1173 1.8</td></tr><tr><td>DPGDA</td><td>71.0 滑石粉 4.6</td></tr><tr><td colspan=\"2\"></td></tr><tr><td colspan=\"2\"></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 245,
+        "chunk": "# （9）UV-辊涂木器底漆参考配方  \n\n<html><body><table><tr><td>PEA（EB800) OTA</td><td>40.0 36.0</td><td>651 滑石粉</td><td></td><td>1.5 5.0</td></tr><tr><td>活性胺（EBP115）</td><td>5.0 2.0</td><td>SiO2 BYK055</td><td></td><td>10.0 0.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 246,
+        "chunk": "# （10）UV辊涂木器底漆参考配方  \n\n<html><body><table><tr><td>四官能团PEA（CN920） PEG(400)DA</td><td>35.0 55.2</td><td>651 5.0 TEA 3.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 247,
+        "chunk": "# （11）UV辊涂、竹木器底漆参考配方  \n\n（12）UV喷涂木器底漆参考配方  \n\n\n<html><body><table><tr><td>低黏度EA（EB3500） OTA</td><td rowspan=\"3\">36 40 5 2</td><td rowspan=\"3\">滑石粉 SiO2 消泡剂（BYK055）</td></tr><tr><td>活性胺（EBP115）</td></tr><tr><td>0.5</td></tr></table></body></html>  \n\n<html><body><table><tr><td>PEA(PRO4662)</td><td>40.49 4.05</td><td>BP 活性胺（CN311）</td></tr><tr><td>单官能EA（CN152） DPGDA</td><td>36.44</td><td>4.05 Estearato de Zn 0.40</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 248,
+        "chunk": "# （13）UV喷涂木地板底漆参考配方  \n\n<html><body><table><tr><td>EA（25含%TPGDA）（EB608）</td><td>25.0</td><td>晶型SiO 21.0 滑石粉 4.0</td></tr><tr><td>低黏度EA（EB3500）</td><td>8.0 37.0</td><td>消光剂SiO（Aerosil380） 1.0</td></tr><tr><td>OTA</td><td></td><td></td></tr><tr><td>184</td><td>3.5</td><td>非硅消泡剂（BYK055） 0.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 249,
+        "chunk": "# （14）UV高温喷涂木器高填充底漆参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（含20%HDDA）（CN963B80） TPGDA TiO（RCL666) 1800</td><td>10.6 33.8 1.3 2.6 17.6</td><td>滑石粉 29.4 润湿分散剂（Dyspctbyk110） 2.2 润湿分散剂（Dyspecrbyk161） 2.2 双叔丁基对甲苯酚 0.3</td></tr></table></body></html>  \n\n注：升温至70～90℃，趁热喷涂到开孔木基材上，经流平，再UV固化。本涂料也适用于刨花板、纤维板、中密度板以及水泥、石材等制品涂装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 250,
+        "chunk": "# （15）UV木器白色底漆参考配方  \n\n<html><body><table><tr><td>EA TPGDA ITX</td><td rowspan=\"3\">7 63 1</td><td rowspan=\"2\">651</td></tr><tr><td>EDAB</td><td>二氧化钛 12 滑石粉 11</td></tr><tr><td rowspan=\"3\">5</td><td rowspan=\"2\"></td></tr><tr><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 251,
+        "chunk": "# （16）UV木器封边底漆参考配方  \n\n<html><body><table><tr><td>UA6010 Silica-3 Alumina-2</td><td></td><td>50.00 液态BP 2.00 TPO 2.00 活性胺 10.72 消泡剂 25.88</td><td>流平剂</td><td>0.20</td><td>2.00 2.00 5.00</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 252,
+        "chunk": "# （17）UV地板底漆参考配方  \n\n<html><body><table><tr><td>高光泽UP（VPLS2110）</td><td>74.6</td><td>黏度（23℃）/mPa·s 2000</td></tr><tr><td>DPGDA 2022</td><td>22.4 3.0</td><td>涂布量/（g/m²） 20</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 253,
+        "chunk": "# （18）UV辊涂地板底漆参考配方  \n\n<html><body><table><tr><td>高光泽UP（VPLS2110） TMPTA 1700</td><td>83.1 14.2 2.7</td><td>辊涂量（g/m²） 固化条件（汞灯80W/cm） 固化速率/（m/min）</td><td>20 1个 10</td></tr></table></body></html>  \n\n（19）UV淋涂地板底漆参考配方  \n\n<html><body><table><tr><td>高光泽UP（XP2490） DPGDA AAEMA</td><td>64.72 助剂（BYK020） 0.39 30.30 1173 2.65 1.94</td></tr><tr><td>黏度（23C，DIN6）/s 35 淋涂量/（g/m²） 200</td><td>固化条件/（mJ/cm²） 2000 固化速率/（m/min） 2</td></tr></table></body></html>  \n\n$\\textcircled{1}$ 淋涂前，基材该预热至 $50\\sim60^{\\circ}C$ 。  \n\n（20）UV地板封闭漆参考配方  \n\n知业（   \n\n\n<html><body><table><tr><td>三官能团脂肪族PUA（U100） TPGDA</td><td>79.0 黏度（23C）/mPa·s 18.0 涂布量/（g/m²）</td></tr></table></body></html>  \n\n（21）UV地板封闭漆参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（VPLS2265） (XP2430)</td><td>19.4 77.7</td><td>1700 2.9</td></tr><tr><td>黏度（23℃）/mPa·s 辊涂量/（g/m²）</td><td>5000 20</td><td>固化条件（汞灯80W/cm） 1个 固化速率/（m/min） 10</td></tr></table></body></html>  \n\n（22）UV辊涂地板封闭漆参考配方  \n\n<html><body><table><tr><td>高光泽UP（VPLS2110） TMPTA</td><td>AlodurZWSKF280 15.8 1700 2.3</td></tr><tr><td>15.4 黏度（23℃）/mPa·s 8000 辊涂量/（g/m²） 30</td><td>固化条件（汞灯80W/cm） 1个 固化速率/（m/min） 10</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 254,
+        "chunk": "# 6.13.2.3UV木器涂料参考配方  \n\n（1）UV木器涂料参考配方  \n\n<html><body><table><tr><td>EA(EB3720)</td><td>26.5</td><td>TMP(EO)TA</td></tr><tr><td>三官能团脂肪族PUA（EB264） 有机硅二丙烯酸酯（EB350）</td><td>30.00 1.00</td><td>BP 4.00 1173 1.50</td></tr></table></body></html>  \n\n<html><body><table><tr><td>胺促进剂（FirstcureAS） 2.00 氟表面活性剂（FC4430） 0.30</td><td>MEHQ 0.02</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 255,
+        "chunk": "# （2）UV木器涂料参考配方  \n\n<html><body><table><tr><td>EA</td><td>30</td><td>TPGDA BP</td><td></td><td>24 3</td></tr><tr><td>芳香族PUA 脂肪族PUA</td><td></td><td>10 6 1173 20</td><td>活性胺</td><td>2 5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 256,
+        "chunk": "# （3）UV木器涂料参考配方  \n\n<html><body><table><tr><td>EA</td><td>39</td><td>EO-TMPTA</td><td></td><td>3 2</td></tr><tr><td>TPGDA 丙氧基甘油三丙烯酸酯</td><td>26 10</td><td>BP TEA</td><td></td><td>1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 257,
+        "chunk": "# （4）UV木器涂料参考配方  \n\n（  \n\n\n<html><body><table><tr><td>芳香酸丙烯酸酯半酯（SB520E35） 45 NPG（EO)DA 38</td><td>EOEOEA 7 非迁移光引发剂（SR1112） 10</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 258,
+        "chunk": "# （5）UV辊涂木器涂料参考配方  \n\n<html><body><table><tr><td>低黏度EA（CN124A80）</td><td>41 36</td><td>184 MDEA</td></tr><tr><td>TPGDA 颜料分散单体（SR802）</td><td>10</td><td>5 流平剂（SR010） 1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 259,
+        "chunk": "# （6）UV辊涂木器涂料参考配方  \n\n<html><body><table><tr><td>EA</td><td>30</td><td>N-MDEA 3</td></tr><tr><td>PEA TPGDA</td><td>30 24</td><td>黏度（23C）/mPa·s 200</td></tr><tr><td></td><td></td><td>固化速率（80W/cm）/（m/min） 8~10</td></tr><tr><td>NVP</td><td>10</td><td>涂布量/（g/m²） 10</td></tr><tr><td>BP</td><td>3</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 260,
+        "chunk": "# （7）UV辊涂木器涂料参考配方  \n\n<html><body><table><tr><td>EA</td><td></td><td></td><td>85</td></tr><tr><td>PEA</td><td></td><td></td><td>40.0</td></tr><tr><td>TPGDA</td><td></td><td></td><td>30.0</td></tr><tr><td>BP</td><td></td><td></td><td>5.0</td></tr></table></body></html>  \n\n<html><body><table><tr><td>1173</td><td></td><td></td><td>1.0</td></tr><tr><td>活性胺</td><td></td><td></td><td>10.0</td></tr><tr><td>SiO2</td><td></td><td></td><td>5.0</td></tr><tr><td>流平剂</td><td></td><td></td><td>0.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 261,
+        "chunk": "# （8）UV辊涂木器涂料参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（CN964E75） DPP/HA TMP(EO)TA</td><td>50 PEG（400)DA 7 3 非迁移光引发剂（SR1112） 8 9 抗黄变助剂（Tinuvin290） 1 10 流平剂（SR010） 1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 262,
+        "chunk": "# （9）UV淋涂木器涂料参考配方  \n\n<html><body><table><tr><td>低黏度EA（CN124C60） TMPTA EOEOEA</td><td>61.75 36.00 7.00</td><td>BP 4.00 MDEA 4.00 流平剂（SR014） 0.25</td></tr></table></body></html>  \n\n（10）UV淋涂木器半光涂料参考配方  \n\n\n<html><body><table><tr><td>PEA</td><td>25.0 25.0</td><td>1173</td><td>4.0 7.0</td></tr><tr><td>TMPTA TPGDA</td><td></td><td>SiO2 37.0 醋酸丁酸纤维素 1.0 流平消泡剂</td><td>0.5 0.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 263,
+        "chunk": "# （11）UV淋涂竹木涂料参考配方  \n\nEA 40.0 1173 4.5   \nTPGDA 40.0 BYK307 0.1   \nHDDA 10.0 2,6-二叔丁基对甲酚 0.1   \nTMPTA 10.0",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 264,
+        "chunk": "# （12）UV喷涂木器涂料参考配方  \n\n<html><body><table><tr><td>EA TMPTA</td><td></td><td>18.0 24.0</td><td>活性胺 SiO2</td><td>5.0 7.0</td></tr><tr><td>TPGDA BP</td><td></td><td>32.0 3.0</td><td>流平消泡剂 乙酸乙酯</td><td>0.5</td></tr><tr><td>651</td><td></td><td>4.0</td><td></td><td>6.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 265,
+        "chunk": "# （13）UV喷涂木器涂料参考配方",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 266,
+        "chunk": "# 大苦越V（）  \n\n低黏度EA（CN140） 35.0 非迁移光引发剂（SR1112） 10.0  \nPEG(400)DA 54.7 流平剂（SR011） 0.3",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 267,
+        "chunk": "# （14）UV喷涂木器涂料参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（CN964E75）</td><td>33.33</td><td>KIP100F</td><td>6.00</td></tr><tr><td>TMP（EO)TA NPG(PO)DA</td><td>6.67 50.00</td><td>TZT</td><td>4.00.</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 268,
+        "chunk": "# （15）UV亮光木器涂料参考配方  \n\n农园买程器米VU（）  \n\n\n<html><body><table><tr><td>EA TMPTA</td><td>50 15</td><td>HPA 1173</td><td>9 3</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 269,
+        "chunk": "# （16）UV高光木器涂料参考配方  \n\n<html><body><table><tr><td>改性EA TMPTA</td><td></td><td rowspan=\"2\">36.0 11.0 25.5 5.0</td><td rowspan=\"2\">BP YP7815 BYK141 EFKA3031</td><td rowspan=\"2\">3.0 12.0 0.2</td></tr><tr><td>TPGDA HPA</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 270,
+        "chunk": "# （17）UV高光木器面漆参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（RoskydalUAUPLS2258）68.31700 3.0 TPGDA 28.7</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 271,
+        "chunk": "# （18）UV亚光木器涂料参考配方  \n\n<html><body><table><tr><td>EA TMPTA</td><td>45 15</td><td>184 ED-30</td><td>1 4</td></tr><tr><td>TPGDA</td><td>20</td><td>BYK-950</td><td>2</td></tr><tr><td>HPA</td><td>10</td><td>CAB381-2（30%)</td><td>5</td></tr><tr><td>1173</td><td>3</td><td></td><td></td></tr></table></body></html>  \n\n（19）UV亚光木器涂料参考配方  \n\n\n<html><body><table><tr><td>低黏度EA（CN141）</td><td>12.0</td><td>SiO(OK412)</td><td>12.0</td></tr><tr><td>TMP（EO)TA</td><td rowspan=\"3\">27.5 37.0 7.0</td><td>润湿剂（SR021）</td><td rowspan=\"3\"></td><td>1.0</td></tr><tr><td>NPG（EO)DA</td><td>流平剂（SR011）</td><td>0.5</td></tr><tr><td>EOEOEA</td><td></td><td></td></tr></table></body></html>\n\n注：光泽 $(60^{\\circ})$ $27\\%$ 。  \n\n（20）UV亚光木器涂料参考配方  \n\n\n<html><body><table><tr><td>改性EA 三官能度PUA</td><td>10.0 30.0</td><td>BP YP7815</td><td></td><td>3.0 12.0</td></tr><tr><td>TMPTA</td><td>13.0</td><td>EFKA-3031 EFKA-4010</td><td></td><td>0.3</td></tr><tr><td>TPGDA</td><td>15.0</td><td></td><td></td><td>0.3</td></tr><tr><td>EHA</td><td>8.0</td><td>EFKA-2022</td><td></td><td>0.2</td></tr><tr><td>ED-30</td><td>7.0</td><td>600-20X</td><td></td><td>0.2</td></tr><tr><td>TF1780</td><td>1.0</td><td></td><td></td><td></td></tr></table></body></html>  \n\n）  \n\n\n<html><body><table><tr><td>四官能PEA 80.5 消光剂SilicaED30 12.0</td><td>分散剂P61 3.5 1173 4.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 272,
+        "chunk": "# （21）UV亚光木器涂料参考配方  \n\n（22）UV亚光木器涂料参考配方  \n\n\n<html><body><table><tr><td>胺改性聚醚丙烯酸酯（CN502） PO-NPGDA</td><td>61 184 20 (Orgaso,3501)</td><td>1 15</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 273,
+        "chunk": "# （23）UV低光泽木器涂料参考配方  \n\n<html><body><table><tr><td>低黏度EA（CN124A80） TMPTA TPGDA</td><td>12.0 32.5 33.0 7.0</td><td>1173 SiO(OK412) 润湿剂（SR021）</td><td>2.0 12.0 1.0</td></tr></table></body></html>\n\n注：光泽 $60^{\\circ})$ $50\\%$ 。  \n\n（24）UV低光泽木材涂料参考配方  \n\n\n<html><body><table><tr><td>胺改性聚醚丙烯酸酯（CN502）</td><td>61</td><td>184 1</td></tr><tr><td>NPG(PO)DA BP</td><td>20 3</td><td>消光剂Qrgasol3501 15</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 274,
+        "chunk": "# （25）UV淋涂低光泽木器涂料参考配方  \n\n<html><body><table><tr><td>EA TPGDA 气相SiO2</td><td>34 48 11</td><td>N-MDEA 黏度（涂-4杯）/s 固化速率（80W/cm）/（m/min）</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 275,
+        "chunk": "# （26）UV喷涂木器涂料参考配方  \n\n<html><body><table><tr><td>脂肪族PUA (PEG）400DA</td><td>20 55 15</td><td>KIP100F TZT</td><td>6 4</td></tr></table></body></html>  \n\n（27）UV喷涂木器涂料参考配方  \n\n\n<html><body><table><tr><td>脂肪族PUA（CN964E75） TMP(EO)TA</td><td>26.67 8.33 TZT</td><td>KIP100F</td><td>6.00 4.00</td></tr></table></body></html>  \n\n欢迎生年业  \n\n\n<html><body><table><tr><td>PEA TMPTA</td><td>13.0 15.0</td><td>活性胺 SiO2 聚合物消光剂</td><td></td><td>8.0 2.0</td></tr><tr><td>TPGDA BP</td><td></td><td>50.0 5.0 4.0 流平消泡剂</td><td>有机硅丙烯酸酯</td><td>2.0 0.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 276,
+        "chunk": "# （28）UV喷涂木器涂料参考配方",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 277,
+        "chunk": "# （29）UV-耐磨木器涂料参考配方  \n\n<html><body><table><tr><td>胺改性聚醚丙烯酸酯（CN550） 胺改性聚醚丙烯酸酯（CN501） 芳香族PUA（CN976）</td><td>53.2 22.8 20.0</td><td>BP 184</td><td>2.0 2.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 278,
+        "chunk": "# （30）UV辊涂耐磨木器涂料参考配方  \n\n<html><body><table><tr><td>PEA（6315) 六官能团脂肪族PUA（6145-100） HDDA TMPTA 1173</td><td>45 10 15 10 4</td><td>BP 助引发剂（EC645） 耐磨粉 Elerslip70</td><td>0.1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 279,
+        "chunk": "# （31）UV耐黄变木器涂料参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（CN964E75） DPPA TMP(EO)TA TPGDA PEG(400)DA</td><td>49.9 NPG(PO)2DA 3.0 KIP100F 9.0 TZT 12.0 稳定剂（SandovurVSU） 7.0</td><td>11.0 5.0 3.0 0.1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 280,
+        "chunk": "# （32）UV白色木器涂料参考配方  \n\n<html><body><table><tr><td>EA 六官能PUA</td><td>10.0 5</td><td>TPO TiO2</td><td>1</td></tr><tr><td>TPGDA</td><td>36 3</td><td>BaSO4</td><td>30 15</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 281,
+        "chunk": "# （33）UV白色木器涂料参考配方  \n\n（34）UV白色木器涂料参考配方  \n\n\n<html><body><table><tr><td>低黏度、脂肪族PUA（CN981B88） TMP（EO)TA NPG(PO)DA</td><td>12.00 22.00 20.15 润湿剂（SR022）</td><td>非迁移、无黄变光引发剂（SR1113） TiO(R-900)</td><td>3.00 35.00</td></tr></table></body></html>  \n\n<html><body><table><tr><td>PEA</td><td>77.2</td><td>TPO 1173</td><td>2.5</td></tr><tr><td>HDDA</td><td rowspan=\"2\">5.9 2.9</td><td rowspan=\"2\">TiO2</td><td rowspan=\"2\">1.5 10.0</td></tr><tr><td>TMPTA</td></tr></table></body></html>\n\n（35）UV白色木器涂料参考配方  \n\n<html><body><table><tr><td>PEA HDDA</td><td>79.2 5.9</td><td>TiO2 10.0 TPO 0.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 282,
+        "chunk": "# （36）UV辊涂白色木器涂料参考配方  \n\n脂肪族PUA（EB264） 32.5 TiO 25.0   \nTMPTA 15.0 Disperbyk110 2.5   \nHDDA 14.0 DA57 2.5   \n184 2.0 LO-Vel HSF 2.5   \n4265 4.0",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 283,
+        "chunk": "# （37）UV着色木器涂料参考配方  \n\n<html><body><table><tr><td>自引发低聚物（DrewRad1012） 2-PEA（SR339) 颜料分散体</td><td>44.32 21.88 27.56 1.67 4.41</td><td>DrewFax860 Aerosil200 黏度（27C）/mPa·s 密度/（g/mL）</td><td>0.10 0.06 295 1.14</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 284,
+        "chunk": "# （38）UV着色木器涂料参考配方  \n\n<html><body><table><tr><td>自引发低聚物DrewRad1013 2-PEA（SR339) 颜料分散体 819 ITX</td><td>55.37 DrewFax860 10.82 Aerosil200 27.57 黏度（27C）/mPa·s 1.67 密度（g/mL） 4.41</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 285,
+        "chunk": "# （39）UV木器面漆参考配方  \n\n<html><body><table><tr><td>EA PUA（Photomer6008） TPGDA</td><td>32 10 651 38 BP 3 三乙醇胺</td><td>GP（PO)TA</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 286,
+        "chunk": "# （40）UV木器面漆参考配方  \n\n<html><body><table><tr><td>低黏度EA TMPTA</td><td>48.75 36.00</td><td>BP N-MDEA</td><td>4.00 4.00</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 287,
+        "chunk": "# （41）UV木器面漆参考配方  \n\n脂肪族PUA（UAU100） 30.8 Acematt OK412 6.5   \n胺改性聚醚丙烯酸酯（UAVPLS2299） 16.2 Acematt TS100 0.8   \nDPGDA 42.9 黏度（23℃）/mPa·s 约400   \n1700 2.8",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 288,
+        "chunk": "# （42）UV木器面漆参考配方  \n\n<html><body><table><tr><td>脂肪族PUA</td><td rowspan=\"3\">48 12 7 11</td><td>DPPA 3 非迁移性光引发剂 8</td></tr><tr><td>TPGDA PEG(400)DA</td><td>光稳定剂（Timuvin292） 1</td></tr><tr><td>NPG(PO)DA (EO）3TMPTA</td><td>流平剂 1</td></tr></table></body></html>\n\n注：用于红木、巴西花梨木等",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 289,
+        "chunk": "# （43）UV辊涂木器面漆参考配方  \n\nPEA（EB800) 32.5 1173 2.0   \nDPGDA 48.0 Syloid161 8.0   \n胺改性丙烯酸酯（EB7100） 5.0 TS100 2.0   \n500 2.0 EB350 0.5",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 290,
+        "chunk": "# （44）UV辊涂竹木器面漆参考配方  \n\n<html><body><table><tr><td>四官能PEA（EB800） DPGDA 胺改性丙烯酸酯（EB7100）</td><td>42 1173 40 消光剂SiO（Syloid161） 3 消光剂SiO（TS100）</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 291,
+        "chunk": "# （45）UV辊涂竹木器面漆参考配方  \n\n<html><body><table><tr><td>EA（含25%OTA）（EB608） 芳香族PUA（EB210） TPGDA 胺改性丙烯酸酯（EB7100）</td><td>31 1173 12 39 3 2 润湿增滑剂（EB350）</td><td>2 消光剂SiO（Syloid161） 8 消光剂SiO（TS100） 2 聚乙烯蜡粉（PP13621） 1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 292,
+        "chunk": "# （46）UV淋涂木器面漆参考配方  \n\n<html><body><table><tr><td>UPE St</td><td>52 39</td><td>含2%石蜡的苯乙烯溶液 4 苯偶姻甲醚 5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 293,
+        "chunk": "# （47）UV淋涂木器面漆参考配方  \n\n<html><body><table><tr><td>EA 32 PUA 10 TPGDA 38 TMP(EO)TA 3</td><td>GP(PO)TA 10 651 4 BP 2 三乙醇胺 1</td></tr><tr><td>黏度（25C）/mPa·s 1300 固化膜性能 光泽度（60°） ≥85 铅笔硬度/H 6</td><td>附着力（划格法） 100/100 耐丁酮擦拭 >100 Taber磨耗（S-17橡胶轮500圈，500g负 4 符）/mg</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 294,
+        "chunk": "# （48）UV淋涂竹木器面漆参考配方  \n\n<html><body><table><tr><td>EA TPGDA</td><td></td><td>35.3 40.0</td><td>1173 BYK307</td><td>4.5 0.1</td></tr><tr><td>HDDA TMPTA</td><td></td><td>10.0 10.0</td><td>阻聚剂</td><td>0.1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 295,
+        "chunk": "# （49）UV淋涂竹木器面漆参考配方  \n\n<html><body><table><tr><td>四官能PEA（EB810） 脂肪族PUA（含25%TPGDA）（EB265）27.5</td><td>27.5</td><td>500 184</td><td>0.5</td></tr><tr><td>HDDA</td><td>36.6</td><td>消光粉（LO-VOIHSF）</td><td>1.0 8.0</td></tr><tr><td></td><td></td><td></td><td></td></tr><tr><td>活性胺（EB7100）</td><td>3.0</td><td>非硅消泡剂（BYK055）</td><td>0.4</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 296,
+        "chunk": "# （50）UV淋涂或喷涂木器面漆参考配方  \n\n<html><body><table><tr><td>PEA</td><td>45 HDDA 10 TPGDA</td><td>15 10</td></tr></table></body></html>  \n\n<html><body><table><tr><td>光引发剂 共引发剂</td><td>5 5</td><td>耐磨粉 10 流平剂 0.1</td></tr></table></body></html>  \n\n<html><body><table><tr><td>共引发剂 5 （51）UV喷涂木器面漆参考配方 EA(EB608) 30.5</td><td>流平剂 1173</td></tr><tr><td>脂肪族PUA（EB210） 12.0 TPGDA 38.0 胺改性（EB7100） 5.0</td><td>2.0 Syloid161 8.0 TS100 2.0 EB350 0.5</td></tr><tr><td>500 2.0 （52）UV亚光木器面漆参考配方</td><td>500 2.8</td></tr><tr><td>脂肪族PUA（VPLS2258） 30.8 聚醚丙烯酸酯（VPLS2299） 16.2 DPGDA 42.9</td><td>SiO（AcemattOK412） SiO（Acematt TS100)</td></tr><tr><td>（53）UV辊涂亚光木器面漆参考配方 EA 22.5</td><td>0.8 BP 2.0</td></tr><tr><td>TMPTA 20.0 TPGDA 30.0</td><td>1173 SiO</td></tr><tr><td>UF/MF树脂 10.0 （54）UV辊涂亚光木器面漆参考配方</td><td>10.0 流平剂（BYK300）</td></tr><tr><td>PEA(PRO4663) 28.5 DPGDA 60.0</td><td>1173 2.6 消光剂（SyloidED30）</td></tr><tr><td>（55）UV喷涂亚光木器面漆参考配方 PEA(PRO 4663) 33.2</td><td>8.9 消光剂（GasilUV70C） 9.2</td></tr><tr><td>DPGDA 29.5 1173 2.0 BP 2.0</td><td>CAB381.01 1.0 流平剂BTK354 0.6 丁酮 18.3</td></tr><tr><td>活性胺（CN371） 2.3 （56）UV白色木器面漆参考配方</td><td>醋酸丁酯 1.9</td></tr><tr><td>PEA 15.0 脂肪族PUA 30.0 HDDA 11.3</td><td>TiO2 40.0 DEAP 2.5 TPO</td></tr><tr><td>（57）UV白色哑光木器面漆参考配方 PEA（VPLS211030%DPGDA) 14.78</td><td>1.2 TPGDA 35.47</td></tr><tr><td>Tronox RKB6 14.78 Blanc-fixe N 7.39</td><td>BYK300 0.15 BYK341 0.06</td></tr><tr><td>Lancowax HM1666 1.18 2.95</td><td>异丁醇 0.05 0.38</td></tr><tr><td>TPGDA 研磨至细度<10μm</td><td>819 1173 1.00</td></tr></table></body></html>  \n\n<html><body><table><tr><td>PEA 11.0 TPGDA 40.0 TMPTA 17.0 BP 7.0</td></tr></table></body></html>  \n\n<html><body><table><tr><td>651 1.0 清石粉 1173 3.0 聚合物消光剂 TPO 3.0 抗沉降剂 TiO2</td></tr><tr><td>5.2 流平/消泡剂 （59）UV木地板涂料参考配方</td></tr><tr><td>EA 36.0 184 1.0 PUA 24.0 1173 3.0</td></tr><tr><td>TMPTA 15.0 邻苯二甲酸二丁酯 5.0 TMGDA 10.0 BYK055 0.2 HPA 5.0 BYK330 0.5</td></tr><tr><td>（60）UV竹木地板涂料参考配方 EA(CN145) 40 EOEOEA 7</td></tr><tr><td>TMPTA 30 非迁移光引发剂（SR1112） 6 TPGDA 16 流平剂（SR013） 1</td></tr><tr><td>（61）UV木地板涂料参考配方 PEA 50.0 BP 1.5</td></tr><tr><td>TPGDA 27.0 651 2.5 GPTA 17.5 EDAB 1.5 （62）UV木地板涂料参考配方</td></tr><tr><td>PUA（含30%TPGDA) 39.0 叔胺 4.0 NVP 10.0 1173 1.5</td></tr><tr><td>HDDA 40.0 流平剂（DC190） 0.5 BP 5.0</td></tr><tr><td>（63）UV地板面漆参考配方 芳香族PUA（XP2614） 32.6 Acemaff412 7.4 0.8</td></tr><tr><td>胺改性聚醚丙烯酸酯（VPLS2299） 17.1 Acematt TS100 DPGDA 39.5 黏度（23℃）/mPa·s 500 500 2.6</td></tr><tr><td>（64）UV辊涂地板面漆参考配方 UP(XP2430) 30.2 Acematt412 6.4</td></tr><tr><td>胺改性聚醚丙烯酸酯（VPLS2299） 16.1 Acematt TS100 0.8 DPGDA 43.8 500 2.7</td></tr><tr><td>（65）UV辊涂地板亚光面漆参考配方 EA(VPLS2266) 53.95 SiO(Syloid ED 30） 5.40</td></tr><tr><td>DPGDA 21.57 助剂（BYK300） 0.19 滑石粉（10MOOS） 16.19 1173 2.70</td></tr></table></body></html>  \n\n（67）UV淋涂地板白色亚光面漆参考配方 沙木Y  \n\n<html><body><table><tr><td rowspan=\"6\">高光泽UP（VPLS2110） TromoxRKB6 Banc-fixeN LancowaxHM1666 TPGDA 研磨至<10μm 高光泽UP（VPLS2110）</td><td rowspan=\"6\">14.78 14.78 7.39 1.18 2.95 14.78</td><td>TPGDA</td><td>35.47</td></tr><tr><td>助剂（BYK300） 助剂（BYK341）</td><td>0.15 0.06</td></tr><tr><td>异丁醇 819</td><td>0.05</td></tr><tr><td>1173</td><td>1.00</td></tr><tr><td></td><td>1.00</td></tr><tr><td>MBF</td><td>1.12</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 297,
+        "chunk": "# （68）UV淋涂地板白色高光泽面漆参考配方  \n\n（69）UV淋涂高光泽地板面漆参考配方  \n\n\n<html><body><table><tr><td>高光泽UP（VPLS2110） TronoxRKB6 TPGDA 助剂（BYK300） 助剂（BYK341）</td><td>49.79 12.45 33.86 0.25 0.10</td><td>AEMA 异丁醇 819 1173 MBF</td><td>0.67</td><td>1.00 0.07 1.19 0.62</td></tr></table></body></html>  \n\n（70）UV喷涂地板面漆参考配方  \n\n\n<html><body><table><tr><td>高光泽UP（XP2490） DPGDA</td><td>53.42 42.74</td><td>助剂（BYK300） (1.07 1173 2.77</td></tr></table></body></html>  \n\n（71）UV喷涂地板半亚光面漆参考配方  \n\n\n<html><body><table><tr><td>三官能团胺改性PEA（VPLS2299）</td><td>66.5</td><td>助剂（BYKUV3500） 0.4</td></tr><tr><td>DPGDA 500</td><td>21.3 2.7</td><td>乙酸乙酯 9.1</td></tr></table></body></html>  \n\n<html><body><table><tr><td>EA(VPLS 2266)</td><td>44.54</td><td>GasilEBN 2.23</td></tr><tr><td>CAB381-0.5</td><td>4.45</td><td>184 0.90</td></tr><tr><td>AcemattTS100</td><td>1.56</td><td>乙酸乙酯/乙酸丁酯/丁酮/MPA（1/1/2/1） 46.32</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 298,
+        "chunk": "# （72）UV耐磨木地板涂料参考配方  \n\n加人顺序：  \n\n<html><body><table><tr><td>顺序： ①胺改性聚醚丙烯酸酯（LaromerLR8997）59.0 ③硅偶联剂（DynasilanMEMO） ④脱泡剂（TEGOAinex920） ③水 纳米SiO（Cab-O-SilMS粒径1~14nm） ②聚四氟乙烯微粉蜡（Ceraflour996）</td><td>3.1 12.2 ⑧500 2.0 5.1 18.6</td><td>务必按顺序加料，最后慢速加人SO剪切， 涂料成膏状 纳米AlO（AlodurZWSKF1200） 3.8 2.9 SiO（SyloidED80） 7.0 TPGDA 31.4</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 299,
+        "chunk": "# （73）UV辊涂耐磨木地板涂料参考配方  \n\n<html><body><table><tr><td>低黏度EA（CN141）</td><td>27</td><td>(PO）NPGDA 22</td></tr><tr><td>DPP/HA (EO）TMPTA</td><td>19 22</td><td>非迁移光引发剂（SR1112） 10</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 300,
+        "chunk": "# （74）UV亚光家具涂料参考配方  \n\n<html><body><table><tr><td>EA(EB608) OTA480 TPGDA</td><td></td><td>50.00 651 25.00 25.00 3.75</td><td>活性胺P115 消光剂G15</td><td>2.50 6.25 12.00</td></tr></table></body></html>  \n\n（75）UV硬木涂料参考配方  \n\n\n<html><body><table><tr><td>FA(CN112C60) TMPTA</td><td>50 21</td><td>附着力增强型丙烯酸树脂（SR9051） 5 非迁移光引发剂（SR1112） 8</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 301,
+        "chunk": "# （76）UV胶合板涂料参考配方  \n\n欢国自地柜儿  \n\n\n<html><body><table><tr><td>三甲基六亚甲基二异氰酸酯改性氢化双酚 35 F型环氧丙烯酸酯</td><td>(EO)TMPTA 31 184 3</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 302,
+        "chunk": "# 6.13.3 UV塑料涂料参考配方",
+        "category": " References"
+    },
+    {
+        "id": 303,
+        "chunk": "# （1）UV塑料涂料参考配方  \n\n<html><body><table><tr><td>EA 芳香族PUA 脂肪族PUA TMPTA</td><td>10 24 10 23</td><td>TPGDA HDDA 1173 活性胺</td><td>12 3 3</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 304,
+        "chunk": "# （2）UV-塑料涂料参考配方  \n\n<html><body><table><tr><td>改性EA PEA(5429) PUA(EB270)</td><td>15.0 20.0 20.0</td><td>BP 1173 活性胺</td></tr></table></body></html>  \n\n①乙酸乙酯：乙酸丁酯 $=6:4$ a  \n\n（3）UV-塑料涂料参考配方  \n\n\n<html><body><table><tr><td>改性EA PEA(5429) 脂肪族PUA（EB270） TMPTA TPGDA HDDA</td><td>15 20 20 10 15 15</td><td>BP 1173 活性胺 附着力促进剂 EFKA3777 乙酸乙酯：乙酸丁酯=6：4</td></tr></table></body></html>  \n\n欢迎##店水#饰  \n\n\n<html><body><table><tr><td>脂肪族PUA HDDA</td><td></td><td>46 BP 45 办 活性胺</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 305,
+        "chunk": "# （4）UV-塑料涂料参考配方",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 306,
+        "chunk": "# （5）UV-塑料涂料参考配方  \n\n<html><body><table><tr><td>PUA(CN981) DPPA</td><td>30.0 5.0 5.0</td><td>IBOA BP 1173 33.7</td><td></td><td></td><td>12.8 2.7 1.8</td></tr></table></body></html>  \n\n（6）UV-塑料涂料参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（photomer6019）</td><td>13 30</td><td>DPGDA BP</td><td>13</td></tr><tr><td>四官能团PEA（photomer5424） 改性聚醚（photomer5960） NPG(PO)DA</td><td>30 10</td><td>1173</td><td>2 2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 307,
+        "chunk": "# （7）UV-塑料涂料参考配方  \n\n<html><body><table><tr><td>脂肪族、芳香族、PEA混合物 活性胺（EB7100） TMPTA IBOA</td><td>31.0 7.0 12.0 35.0 颜料</td><td>消泡剂（FoamexN） 流平剂（Rad2250） Silica 光引发剂（ViaCureDX）</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 308,
+        "chunk": "# （8）UV-耐磨涂料参考配方  \n\n<html><body><table><tr><td>芳香族六官能团PUA 40 TMPTA 20 TPGDA 20 2-EHA 5</td><td>P115 5 1173 3 AlO3 5 聚四氟乙烯改性PE蜡 2</td></tr><tr><td colspan=\"2\">（9）UV-塑料涂料参考配方</td></tr><tr><td>九官能团PUA（NTX7674） 49 三官能团PUA（CN9008） 29 三环癸烷二甲醇二丙烯酸酯SR833S 16</td><td>184 5 流平助剂 1</td></tr></table></body></html>\n\nyv  \n\n，注：用于三醋酸纤维素塑料。  \n\n火金UV  \n\n\n<html><body><table><tr><td>脂肪族PUA（VPLS2265）</td><td>65.44</td><td>黏度（50℃，涂4杯）/s 27</td></tr><tr><td>TCDDMDA 184</td><td>32.72 1.64</td><td>喷涂温度/℃ 60 涂布量/（g/m²） 20 固化条件（一盏汞灯80W/cm）/（m/min） 2×5</td></tr></table></body></html>  \n\n（10）UV-喷涂耐候耐刮擦清漆参考配方  \n\n\n<html><body><table><tr><td>脂肪族PUA（VPLS2308） 脂肪族PUA（XP2513） HDDA 184/819（7：1）（含50%HDDA） BYK306</td><td>44.3 2.2 45.6 5.7 0.6 1.0</td><td>受阻胺（TinUVin292） 0.6 黏度（23℃）/mPa·s 150 涂布量（g/m²） 固化条件灯+汞灯（80W/cm）/（mJ/cm²） 2800 固化速率/（m/min） 2.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 309,
+        "chunk": "# （11）UV喷涂层压塑料清漆参考配方",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 310,
+        "chunk": "# （12）UV柔感涂料参考配方  \n\n<html><body><table><tr><td>PUA（XP2513） PUA（XP2491含20%IBOMA）</td><td>17.67 26.52</td><td>醋酸丁酯 33.14 黏度（23C）/mPa·s</td></tr><tr><td>EOEOEA</td><td>14.58</td><td>910 干膜厚度/μm 40</td></tr><tr><td>1173 Acematt3200</td><td>2.35 2.87</td><td>干燥条件（60℃）/min 5 固化条件（一盏汞灯80W/cm）/（m/min） 5</td></tr></table></body></html>\n\n中#",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 311,
+        "chunk": "# （13）UV喷涂含云母涂料配方  \n\n（14）UV三聚氰胺纸张涂料  \n\n\n<html><body><table><tr><td>EA PUA TMPTA DPGDA HEMA</td><td>20 15 34 15 5 4</td><td>TPO 助剂 云母（1095） 芳香烃 酮 酯</td><td></td><td>2 2 5 30 20 50</td></tr></table></body></html>  \n\n国YV  \n\n\n<html><body><table><tr><td>附着力促进型PUA（CN703）</td><td>71.3</td><td>附着力促进型三丙烯酸酯（SR9051） 4.0</td></tr><tr><td>低黏度芳香族丙烯酸低聚物（CN131） PO-NPGDA</td><td>9.5 11.3</td><td>184 3.9</td></tr></table></body></html>  \n\n（15）UV-PU底漆喷涂罩光漆配方  \n\n<html><body><table><tr><td>双官能团脂肪族PUA（50%醋酸丁酯） 六官能团PEA 三官能团脂肪族PUA（38%HPMA） 丙烯酸化丙烯酸酯（60%HDDA）</td><td>30.0 10.0 20.0 10.0</td><td>TPO CPK HDMAP 1.0</td><td>0.1 2.0 3.0</td></tr></table></body></html>  \n\n注：涂料与溶剂 $1:1$ 稀释，喷涂 $14\\mu\\mathrm{m}$ 0  \n\n（16）UV-塑料抗老化、耐化学品、耐划伤涂料参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（LPWOJ4060） 带—NCO基脂肪族PUA（VPLS2396）</td><td>79.4 三环癸烷二甲基二丙烯酸酯 8.8 184</td><td>8.8 3.0</td></tr><tr><td colspan=\"2\">黏度（25℃）/mPa·s 30000 固化条件（1盏汞灯，80W/cm）/（mJ/cm²） 500 手动涂厚（60℃）/μm 20 固化速率/（m/min） 10</td></tr></table></body></html>  \n\n注：用于ABS、PCPP。  \n\n（17）UV清漆配方  \n\n<html><body><table><tr><td>芳香族PUA（含20%TPGDA） EA（含20%TPGDA） PEA (EO)TMPTA NVP</td><td>57.80 5.60 5.69 11.50 10.90</td><td>ODA 2.54 1173 3.00 BP 1.77 润湿分散剂（BYKP105） 1.20</td></tr></table></body></html>  \n\n注：适用于木器、塑料、陶瓷、金属、水泥及层压板等多种基材。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 312,
+        "chunk": "# （18）UV-亚光罩光清漆参考配方  \n\n<html><body><table><tr><td>自引发低聚物（DrewRad150） EO-TMPTA DPGDA BP</td><td>43.4 1173 10.8 14.8 0.5</td><td>2.0 消光自引发低聚物（DrewRadm-15） 3.0 DrewFax860 1.0 31</td></tr><tr><td colspan=\"3\">黏度/mPa·S 250 光泽（60°） 固化条件Fusion300WH灯/（ft/min） 100 耐摩擦/圈</td></tr></table></body></html>\n\n注： $1\\mathrm{ft}{=}0.30\\mathrm{m}$ ，下同。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 313,
+        "chunk": "# （19）UV-罩光清漆参考配方  \n\n<html><body><table><tr><td>六官能团脂肪族PUA（PRO30000） 21.0 10.0 三官能团丙烯酸酯（SR9012） 7.0 三官能团酸酯（CD9051） 1.0 184 1.5 三官能团脂肪族PUA（CN970A60）</td><td>流平剂（Tego450） 0.1 乙酸乙酯 20.0 乙酸丁酯 23.0 正丁醇 17.0</td></tr><tr><td>（21）UV-PVC涂料参考配方 EA 23</td><td>HDDA 10</td></tr><tr><td>PUA 6 三聚氰胺丙烯酸树脂 21 TMPTA 10 NPGDA 13</td><td>1173 3 BP 4 活性胺 10</td></tr><tr><td>（22）UV-PVC涂料参考配方 30.7</td><td>BP 4.0</td></tr><tr><td>改性EA 双官能团氨基丙烯酸酯 10.0 HDDA 25.0 TPGDA 28.8</td><td>HDMAP 1.0 DC57 0.5 涂布5μm</td></tr><tr><td>（23）UV-PVC涂料参考配方 EA 47</td><td>2-EHA 3</td></tr><tr><td>TMPTA HDDA NDGDA</td><td>6 BP 3 651 7</td></tr><tr><td>（24）UV-PVC涂料参考配方 PUA 16</td><td>TZT 2</td></tr><tr><td>EA 24 TMPTA TEGDA</td><td>BP 50 助剂 3</td></tr><tr><td>（25）UV-PVC涂料参考配方 脂肪族PUA 36.0</td><td>BP 4.0 MDEA 2.0</td></tr><tr><td>DTTA 19.0 （PO)NPGDA 29.9 THFA 8.0</td><td>184 1.0 DC57 0.1</td></tr><tr><td>（26）UV-PVC涂料参考配方 脂肪族二官能团PUA（CN981） 30.0 DPPA</td><td>IBOA 12.8 5.0 BP 2.7</td></tr></table></body></html>  \n\n（27）UV-PVC涂料参考配方  \n\n\n<html><body><table><tr><td>PUA PEA N-乙烯基己内酰胺</td><td>45 21 5 15 硅助剂</td><td>BP 651 活性胺</td><td>5 3 5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 314,
+        "chunk": "# （28）UV辊涂PVC涂料参考配方  \n\n<html><body><table><tr><td>三官能团脂肪族PUA（U100） PEG(200)DA</td><td>67.8 1173 29.1 助剂（BYKUV3500）</td><td>2.9 0.2</td></tr><tr><td>黏度（23C）/mPa·s 辊涂量/（g/m²）</td><td>600 10 固化速率/（m/min）</td><td>固化条件（1盏汞灯，80W/cm）/（mJ/cm²） 200 >20</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 315,
+        "chunk": "# （29）UV辊涂PVC涂料参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（U200） DPGDA (ACematt412)</td><td>54.29 37.46 184 3.80</td><td>(ACemattTS100） 1.63 2.71 助剂（BYKUV3500） 0.11</td></tr><tr><td>黏度（23℃）/mPa·s 辊涂量/（g/m²）</td><td>850 20</td><td>固化条件（1盏汞灯，80W/cm）/（ml/cm²） 1000 固化速率/（m/min） 5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 316,
+        "chunk": "# （30）UV辊涂PVC涂料参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（U200） DPGDA</td><td>67.84 1173 29.10 助剂（BYKUV3500）</td><td>2.92 0.14</td></tr><tr><td>黏度（23C）/mPa·s 辊涂量/（g/m²）</td><td>800 20</td><td>固化条件（汞灯80W/cm）/（mJ/cm²） 1000 固化速率/（m/min） 5</td></tr></table></body></html>  \n\n（31）UV-PVC地板涂料参考配方  \n\n\n<html><body><table><tr><td>双官能脂肪族PUA（CN981）</td><td>30.0 33.7</td><td>IBOA BP</td><td></td><td>12.8</td></tr><tr><td>HDDA EO-TMPTA</td><td>5.0 5.0</td><td>1173</td><td></td><td>2.7 1.8</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 317,
+        "chunk": "# （32）UV-PVC地板涂料参考配方  \n\n（33）UV-PVC地板涂料参考配方  \n\n\n<html><body><table><tr><td>PUA PO-NPGDA</td><td>44.0 22.0</td><td>1173 活性胺</td><td></td><td>3.0 3.5</td></tr><tr><td>TMPTA EOEOEA</td><td>17.0 10.0</td><td>流平剂</td><td></td><td>0.5</td></tr></table></body></html>  \n\n<html><body><table><tr><td>脂肪族PUA</td><td></td><td>56 10</td><td>BP 二甲基乙醇胺</td><td></td><td>3 2</td></tr><tr><td>TMPTA HDDA</td><td></td><td>15 10</td><td>1173 流平剂</td><td></td><td>3 1</td></tr></table></body></html>\n\n（34）UV-PVC地板涂料参考配方  \n\n<html><body><table><tr><td>三官能度脂肪族PUA（EB294） NVP</td><td>68.42 10.53</td><td>BP 1173</td><td></td><td>3.15 1.05</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 318,
+        "chunk": "# （35）UV-PVC地砖涂料参考配方  \n\n<html><body><table><tr><td>脂肪族二官能团PUA（ECX-6025）</td><td>LA 8</td></tr><tr><td>EO-NPGDA(Photomer4039) 8 环氧大豆油丙烯酸酯（Photomer3005）</td><td>EHA 4</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 319,
+        "chunk": "# （36）UV-PVC地砖涂料参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（含15%HDDA）</td><td>64.0</td><td></td><td>光引发剂</td><td>5.3</td></tr><tr><td>PETA HDDA</td><td></td><td>5.0 10.0</td><td>共引发剂 流平剂</td><td>0.4 0.3</td></tr></table></body></html>  \n\n（37）UV-PVC地砖涂料参考配方  \n\n\n<html><body><table><tr><td>二官能团脂肪族PUA（611B-85） 50 HDDA 30 184 4 BP 2</td><td>活性胺（Etercure6410） 4 助剂（EtersTig70） 0.2 BYK055 0.1</td></tr><tr><td>固化速率/（m/min） 8.5 光泽（60°） 100 附着力（划格法） 100/100 硬度/H 1~2</td><td>耐刮性（硬币刮） 不破损 耐MEK（100次） 通过 耐热（60℃×8h） 无龟裂 磨耗（500g/1000次）/mg 8.5</td></tr><tr><td colspan=\"2\">（38）UV淋涂PVC涂料参考配方</td></tr><tr><td>低黏度PUA（CN989） 44 TMPTA 23 EO-NPGDA 22</td><td>EOEOEA 7 非迁移光引发（SR1112） 3 流平剂（SR010） 1</td></tr><tr><td colspan=\"2\">（39）UV淋涂PVC涂料参考配方</td></tr></table></body></html>  \n\n<html><body><table><tr><td>低黏度脂肪族PUA（CN985B88）</td><td>56</td><td>EOEOEA 7</td></tr><tr><td>三（2-羟乙基）异氰脲酸二丙烯酸树脂（SR368） EO-NPGDA</td><td>15 18</td><td>非迁移性光引发剂（SR1112） 3 流平剂（SR010） 1</td></tr></table></body></html>  \n\n（40）UV淋涂PVC涂料参考配方  \n\n<html><body><table><tr><td>低黏长脂肪族PUA（CN963E75） 41 EO-TMPTA 15 TMPTA 18 EO-NPGDA 15</td><td>EOEOEA 7 1173 3 流平剂（SR010） 1</td></tr><tr><td>（41）UV淋涂PVC地砖涂料参考配方 双官能团脂肪族PUA（6118-85） 64.0</td><td>光引发剂 5.5</td></tr><tr><td>PETA 5.0 HDDA 10.0 NVP 15.0</td><td>助引发剂（EC6420） 0.4 EtersTig70 0.3</td></tr></table></body></html>\n\n（42）UV淋涂PVC地砖涂料参考配方  \n\n<html><body><table><tr><td colspan=\"3\"></td></tr><tr><td>55 DPGDA HDDA 双官能团脂肪族PUA（6131） 双官能团脂肪族（6147B-8）</td><td>1173 15 BP 20 助引发剂（EC645） 10 EtersTig70</td><td>3 2 5 0.3</td></tr><tr><td>脂肪族PUA （43）UV淋涂PVC地砖涂料参考配方</td><td>55 1173 20 BP</td><td>3 2</td></tr><tr><td>DPGDA TMPTA 10 HDDA 5 （44）UV喷涂PVC扣板涂料参考配方</td><td>活性胺</td><td>5 25.0</td></tr><tr><td>三官能度脂肪族PUA（6130B-80） 20.0 EA(621A-80) PETA 13.8</td><td>PEG(200)DA(EM224) 10.0 184 30.0 助剂（ES70）</td><td>5.0 0.3 冷热循环（50℃×6h，20℃×6h三个循环） 通过</td></tr><tr><td>黏度（25℃，涂-4杯）/s 固化速率/（m/min） 附着力（划格法） 光泽（60°）</td><td>14.5 耐溶剂（耐MEK大于100次） 100/100 耐黄变性（QUV） 91.2</td><td>通过 良</td></tr><tr><td>（45）UV高光PVC地板涂料参考配方 脂肪族PUA</td><td>70.0 BP</td><td>5.0 1.0</td></tr><tr><td>N-VP 10.0 POEA 活性胺</td><td>1173 9.0 流平剂 4.0</td><td>1.0</td></tr><tr><td>（46）UV亚光PVC地板涂料参考配方 脂肪族PUA（EB294）</td><td>58.4 BP</td><td>3.1 1.0</td></tr><tr><td>N-VP 10.5 EHA</td><td>1173 21.0 6950光泽（60°） 消光剂（SYLOIDED3）</td><td>6.0 44</td></tr><tr><td>黏度/mPa·s （47）UV亚光弱弹性PVC底材面漆参考配方</td><td>Acematt TS100</td><td>1.63</td></tr><tr><td>脂肪族PUA（U200） 54.29 DPGDA 37.46 AcemattOK412 3.80</td><td>184 BYKUV3500</td><td>2.71 0.11</td></tr><tr><td>黏度（23℃）/mPa·s</td><td>850 固化速率/（m/min） 固化条件（一盏汞灯，80W/cm）/（mJ/cm²）</td><td>1000 5</td></tr><tr><td>辊涂涂布量/（g/m²） 20 （48）UV低光泽PVC地板仿瓷涂料参考配方</td><td></td><td></td></tr><tr><td>PUA（含20%HDDA） 烷氧基脂肪族二丙烯酸酯</td><td>33 EOEOEA 20 消光剂SiO</td><td>7 9</td></tr><tr><td>(EO)TMPTA TMPTA 9</td><td>15 1173 润湿剂</td><td>3 1</td></tr></table></body></html>\n\n（49）UV-PVC地板仿瓷涂料参考配方 欢#  \n\n<html><body><table><tr><td>烷氧化脂肪族二丙烯酸酯 (EO)3TMPTA TMPTA</td><td>18 15 15</td><td>1173 流平剂</td><td></td></tr><tr><td>（50）UV柔性PVC涂料参考配方 双官能团脂肪族PUA（CN967B80）</td><td>35 BP</td><td></td><td>4 2</td></tr><tr><td>DPEPA 15 (PO)NPGDA 30 THFA 13</td><td>N-MDEA 184</td><td colspan=\"2\">1</td></tr><tr><td colspan=\"5\">（51）UV柔性PVC涂料参考配方 37.9</td></tr><tr><td>脂肪族PUA（CN944B85） DPEPA 15.0 HDDA 9.0 (PO)NPGDA 9.0</td><td colspan=\"2\">活性胺（CN386） BP 184 FC430</td><td colspan=\"2\">3.0 0.1</td></tr><tr><td colspan=\"2\">THFA 10.0 （52）UV硬质PVC板材涂料参考配方 芳香族PUA（PPO210：HEA：TDI=03：14:1）</td><td colspan=\"2\">BP 4</td></tr><tr><td>EA TMPTA TPGDA TZT 2</td><td>10 24 助剂 50 固化速率/s 9 硬度/H 附着力</td><td></td><td>1 7.5 >3 优</td></tr></table></body></html>  \n\n<html><body><table><tr><td>双官能团脂肪族PUA（CN965）</td><td>36.0</td><td>BP 184</td><td></td><td>4.0</td></tr><tr><td>DTPTA (PO)NPGDA</td><td>19.0 29.9 8.0</td><td>N-MDEA</td><td>0.1</td><td>1.0 2.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 320,
+        "chunk": "# （54）UV耐黄变PVC涂料参考配方  \n\n<html><body><table><tr><td>三官能度脂肪族PUA（6130B-80）</td><td>40.0</td><td>184</td><td>5.0</td></tr><tr><td>PETA PEG(200)DA</td><td>30.0 25.0</td><td>ES70</td><td>0.3</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 321,
+        "chunk": "# （55）UV耐黄变PVC地砖涂料参考配方  \n\n<html><body><table><tr><td>三官能度脂肪族PUA（911B-85）</td><td>50.0</td><td>BP 2.0</td></tr><tr><td>HDDA TMPTA</td><td>30.0 10.0</td><td>活性胺（Etercure6410） 4.0 Eterslip70 0.2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 322,
+        "chunk": "# （56）UV-PVC薄膜涂料参考配方  \n\n<html><body><table><tr><td>六官能度芳香族PUA DPP5A</td><td>14.5 27.0</td><td>Etercoat 溶剂</td><td>6.0 49.5</td></tr></table></body></html>\n\n（57）UV辊涂PVC薄膜涂料参考配方 剂  \n\n<html><body><table><tr><td>六官能团芳香族PUA（6146-100） 14.5 DPEHA 27.0 光引发剂 3.0</td><td>助引发剂（EC4331） 6.0 Eterslip70 0.1 溶剂</td></tr><tr><td>（58）UV乙烯地板砖涂料参考配方</td><td>49.4</td></tr><tr><td>PO-NPGDA 30 EO-TAPTA 30</td><td>脂肪族PUA 36 1173 4</td></tr><tr><td>（59）UV乙烯基涂料参考配方</td><td></td></tr><tr><td>纯丙烯酸树脂 42 HDDA 15 TPGDA 10</td><td>EOTMPTA 8 907 3 活性胺 16</td></tr><tr><td>（60）UV亚光乙烯基塑料涂料参考配方</td><td></td></tr><tr><td>脂肪族四官能PEA 45.2 HDDA 27.1 651 7.7</td><td>SiO2 16.0 聚乙烯蜡 2.9 F40</td></tr><tr><td>（61）UV复合膜涂料参考配方</td><td>1.1</td></tr><tr><td>纯丙烯酸树脂 45 HDDA 26</td><td>184 5 907 3</td></tr><tr><td>EOTMPTA 8 （62）UV乙烯基薄膜涂料参考配方</td><td>活性胺 13</td></tr><tr><td>三（2-羟乙基）异氰脲酸二丙烯酸树脂（SR368） 45 HDDA 20</td><td>POEA 25 非迁移光引发剂（SR1112） 10</td></tr><tr><td>（63）UV触控面板ITO膜耐磨涂料参考配方</td><td></td></tr><tr><td>HC-103 15.0 DPEHA 15.0</td><td>Eterslip 70 0.1 溶剂 67.0</td></tr><tr><td>1173 3.0 （64）UV-PS涂料参考配方</td><td></td></tr><tr><td>(EO)TMPTA 85.5 HDDA 9.5</td><td>MDEA 2.0 1173 1.0</td></tr><tr><td>BP 3.0 （65）UV-PS涂料配方</td><td></td></tr><tr><td>六官能团脂肪族PUA（6145-100） 40 DPEHA 10 HDDA 40</td><td>BP 活性胺（EC6420） 5 流平剂（Eterslip70） 0.1 2</td></tr><tr><td>1173 3 （66）UV抗冲击PS涂料参考配方</td><td></td></tr><tr><td>(EO)TMPTA 85.5 HDDA 9.5 BP 3.0</td><td>N-MDEA 2.0 1173 1.0</td></tr></table></body></html>\n\n（67）UV耐黄变PS涂料配方 发林精y  \n\n<html><body><table><tr><td>六官能度脂肪族PUA（6145-100） DPEPA</td><td>40.0 8.0</td><td>184 活性胺（Etercure6410）</td></tr></table></body></html>  \n\n（68）UV-PMMA板材涂料配方  \n\n<html><body><table><tr><td>DPEHA双季戊四醇六丙烯酸酯</td><td rowspan=\"3\">30 30 20 184</td><td>硅偶联剂（KH570） 硅胶粉（OSCAL-1432）</td></tr><tr><td>TMPTA DEGDA</td><td>100</td></tr><tr><td>5</td><td>聚硅氧烷表面活性剂（Y7002） 0.03</td></tr></table></body></html>  \n\n（69）UV透明塑料板（PMMA）涂料参考配方  \n\n<html><body><table><tr><td>EA TMPTA HEMA</td><td></td><td>10 80 10 5 耐磨性</td><td>硬度/H 附着力 耐候性</td><td>8 优 优</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 323,
+        "chunk": "# 6.13.4UV金属涂料参考配方",
+        "category": " References"
+    },
+    {
+        "id": 324,
+        "chunk": "# （1）UV金属涂料参考配方  \n\n（2）UV金属涂料参考配方  \n\n\n<html><body><table><tr><td>EA PEA</td><td>13 39 12 10</td><td>TPGDA HEMA 1173</td><td></td><td>10 10 6</td></tr></table></body></html>  \n\n<html><body><table><tr><td>PUA</td><td></td><td>42 10</td><td>BP</td><td>2</td></tr><tr><td>PETA POEA</td><td></td><td>40</td><td>1173 活性胺</td><td>3 3</td></tr></table></body></html>  \n\n（3）UV金属涂料参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（CN965） 芳香酸甲基丙烯酸半酯</td><td>40 (EO)TMPTA 12 KIP100F</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 325,
+        "chunk": "# （4）UV金属涂料参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（含TPGDA） 低黏度芳香族单丙烯酸酯</td><td>1173 BP</td><td>3 3</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 326,
+        "chunk": "# （5）UV辊涂金属涂料参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（CN988） 42 低黏度单丙烯酸酯低聚物（CN131） 10</td><td>POEA 40 非迁移光引发剂（SR1112） 8</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 327,
+        "chunk": "# （6）UV淋涂金属涂料参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（CN966A80）</td><td>1173 BP</td><td></td><td>3 3</td></tr><tr><td>低黏度单丙烯酸酯低聚物（CN131） 三官能团丙烯酸树脂（SR9051）</td><td>39 5</td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 328,
+        "chunk": "# （7）UV金属保护漆参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（LPWDS4060） 49.41 增强附着力树脂（EB168） 4.13 POEA 16.49</td><td>滑石粉（AT1） 22.50 腐蚀抑制剂（HeucophosZPA） 5.50 2022 1.97</td></tr><tr><td>黏度（23C）/mPa·s 19700 涂层厚度/μm 30 固化条件/（mJ/cm²） 740</td><td>汞灯（80W/cm）/盏 1 灯（80W/cm）/盏 1 固化速率/（m/min） 10</td></tr><tr><td colspan=\"2\">（8）UV铝基涂料参考配方</td></tr><tr><td>PEA 29 乙氧基双酚A二丙烯酸酯 10 POEA 20 PO-TMPTA 33</td><td>BP 3 1173 3 TEA 2</td></tr><tr><td colspan=\"2\">（9）UV铝基涂料参考配方 15.0 BP</td></tr><tr><td colspan=\"2\">附着力促进型PEA 低黏度脂肪族二丙烯酸酯 35.0 184 （PO）NPGDA 35.0 Rad2200 附着力促进型带羧基三丙烯酸酯 7.0</td></tr><tr><td colspan=\"2\">（10）UV铝基涂料参考配方 （</td></tr><tr><td colspan=\"2\">低黏度脂肪族二丙烯酸酯 34 BP 6 （EO)TMPTA 15 184 4 IBOA 40 Rad2200 1</td></tr><tr><td colspan=\"2\">（11）UV铝基涂料参考配方 TDI-HEMA全加成物 80 氟表面活性剂（F-17） 0.5</td></tr><tr><td colspan=\"2\">HDDA 20 二甲苯-甲苯-异丙醇等比例混合溶剂 184 4</td></tr></table></body></html>\n\n注：用作ABS塑料表面喷涂，再真空镀铝用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 329,
+        "chunk": "# （12）UV铝基涂料参考配方  \n\n<html><body><table><tr><td>PUA DPPA</td><td>43.6 29.2</td><td>BP 184 4.0 丁酮：乙酸乙酯=4：1</td><td>4.0 4.0 15.2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 330,
+        "chunk": "# （13）UV铝罐涂料配方  \n\n<html><body><table><tr><td>EA(Novacure3700) 芳香族PUA（EB4827） IBA</td><td>19.0 13.5 46.0 3.0</td><td>聚硅氧烷双丙烯酸酯（EB350） 1.0 聚乙烯蜡粉（S395N） 2.5 氟化蜡粉（SST-3） 1.0 BP 5.0 8.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 331,
+        "chunk": "# （14）UV铝罐涂料参考配方  \n\n<html><body><table><tr><td>EA(Celrad3702) 脂肪族PUA（Chempol19-4883）</td><td rowspan=\"3\">20.00 13.50 9.00</td><td>丙烯酸酯化磷酸（EB19-6170） 1.00 丙烯酸酯化硅氧烷（EB19-6350）</td></tr><tr><td>PEA（Photomer5007）</td><td>1.00 丙烯酸酯化氟碳表面活性剂（FluoradFX-13） 3.00</td></tr><tr><td>IBOA 44.25 184 4.75</td><td>聚乙烯蜡（S394N1） 2.50 氟化蜡粉（SST-3） 1.00</td></tr></table></body></html>  \n\n附着力促进型PEA（CN704） 15.0BP 3.5  \n低黏度脂肪族双丙烯酸酯（CN132） 35.0 184 4.0  \nPO-NPGDA 35.0 Tego Rad2200 0.5  \n附着力促进型三官能团酯（SR9051） 7.0  \n\n（15）UV铝基耐热涂料参考配方  \n\n\n<html><body><table><tr><td>低黏度脂肪族双丙烯酸酯（CN132） EO-TMPTA</td><td>34BP 15 184</td><td>6 4</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 332,
+        "chunk": "# （16）UV铝基耐热涂料参考配方",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 333,
+        "chunk": "# （17）UV铝、钢涂料参考配方  \n\n<html><body><table><tr><td>芳香酸甲基丙烯酸半酯 DPHA</td><td>43.6 29.2</td><td>184 甲乙酮</td><td></td><td>4.0 12.2</td></tr><tr><td>带羚基三官能团丙烯酸酯 BP</td><td>4.0 4.0</td><td>乙酸乙酯</td><td></td><td>3.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 334,
+        "chunk": "# （18）UV钢材涂料参考配方  \n\n<html><body><table><tr><td>丙烯酸酯化蜜胺树脂 30 EA 70</td><td>651 2</td></tr></table></body></html>  \n\n$\\textcircled{1}$ 用138份丙烯酸羟乙酯/已内酯的加成产 与39份六羟甲基蜜胺，加人0.05份MEHQ在90℃，反应6h制得。  \n\n（19）UV钢板涂料参考配方  \n\n\n<html><body><table><tr><td>EA TMPDA</td><td>60 20 10</td><td>BP 3 二甲基乙醇胺 2 氟表面活性剂（FC430） 0.1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 335,
+        "chunk": "# （20）UV耐黄变金属涂料参考配方  \n\n<html><body><table><tr><td>低黏度脂肪族PUA（CN965） PO-TMPTA</td><td>40 12</td><td>POEA KIPIOOF</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 336,
+        "chunk": "# （21）UV铜导线涂料参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（Photomer6008） 乙氧基双酚A二丙烯酸酯</td><td>50 8 10</td><td>PETA 651 BP</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 337,
+        "chunk": "# （22）UV铜导线涂料参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（Photomer6008）</td><td>72 16</td><td>BP TEA</td><td></td><td>3 2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 338,
+        "chunk": "# （23）UV铝管上色涂料参考配方  \n\n<html><body><table><tr><td>聚醚改性EA 磷酸改性丙烯酸酯（科宁4703） IBOA 20</td><td>85 色浆（透明铁红、透明铁黄） 5 1173</td></tr></table></body></html>  \n\n<html><body><table><tr><td>固化性/（mJ/cm²） 400 延展性/（°） 附着力（划格法） 100/100 摆杆硬度 柔韧性/mm 1</td></tr><tr><td>（24）UV白色金属涂料参考配方 EA 10.0 EDAB 2.5</td></tr><tr><td>PEA 15.0 滑石粉 2.0 DDA 8.0 TiO2 53.5 BP 3.0 紫罗兰 1.0</td></tr><tr><td>TPO 4.0 蜡 1.0 （25）UV白色金属涂料参考配方</td></tr><tr><td>脂肪族PUA（CN964E75） 26.5 TPO 3.0 PEG(400)DA 26.0 TiO2 34.0 DPP/HA 4.9 分散剂（AntiterraU） 0.4</td></tr><tr><td>芳香酸丙烯酸酯半酯（SB502） 4.9 流平剂（DC57） 0.3 （26）UV蓝色金属涂料参考配方</td></tr><tr><td>芳香酸丙烯酸酯半酯[含（EO）3TMPTA] 46.0 907 4.5 低黏度芳香族单丙烯酸酯 22.0 ITX 0.5 POEA 20.0 BP 2.0</td></tr><tr><td>炭黑（Raven450） 4.0 流平剂 1.0 （27）UV金属防腐涂料参考配方</td></tr><tr><td>脂肪族PUA（EB4883） 18.0 丙烯酸锌（SR9016） 5.0 EHA 33.0 聚苯胺粉末 10.0 1173 5.0 铝粉 8.5 184 0.5 对甲苯磺酰胺（Uniplex108） 5.0</td></tr></table></body></html>\n\n$\\textcircled{1}$ 在光固化涂料中，添加活泼金属粉末，利用阳极牺牲原理，保护金属（如钢材）不被腐蚀。  \n\n<html><body><table><tr><td>附着力促进型PEA（CN704） 低黏度双丙烯酸酯低聚物（CN132）</td><td>15.0 30.0</td><td>三官能附着促进剂（SR9051） BP 184</td><td>7.0 2.5</td></tr><tr><td>EA(CN104)</td><td rowspan=\"3\">5.0 18.9 16.1</td><td></td><td>5.0</td></tr><tr><td>EOEOEA</td><td>Tego2200</td><td>0.5</td></tr><tr><td>(EO)TMPTA</td><td></td><td></td></tr></table></body></html>  \n\n（28）UV金属耐腐蚀涂料参考配方  \n（29）UV汽车修补底漆参考配方  \n\n\n<html><body><table><tr><td>脂肪族PUA（VPLS2258） 增强附着力树脂（EB168） POEA 滑石粉（AT1） 中国黏土级别B</td><td>55.17 1.65 10.98 10.98 10.98</td><td>腐蚀抑制剂（HeucophosZPA） TiO(R-KB-2） 助剂（Bayferrox303T） 184:819（3:1)</td></tr></table></body></html>  \n\n注：加人乙酸丁酯调节喷涂黏度，VOC为 $240_{\\mathbf{{g}}/\\mathrm{{L}}}$ 。900WUVA手提灯，5min直接固化深度可 达 $90\\mu\\mathrm{m}$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 339,
+        "chunk": "# （30）UV汽车修补底漆参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（LPWDJ4060） 增强附着力树脂（EB168） PEOA 滑石粉（ATI）</td><td>44.0 1.7 22.0 11.0 11.0</td><td>腐蚀抑制剂（HeucophosZPA） TiO(R-KB-2) 助剂（Bayferrox303T） 819 3.3</td><td>5.5 1.4 0.1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 340,
+        "chunk": "# （31）UV喷涂汽车修补底漆参考配方  \n\n<html><body><table><tr><td>EA(VPLS2266) 三官能团脂肪族PUA（U100） TiO(R-960)</td><td>20.6 20.6 1.4</td><td>滑石粉（Talc399） 24.5 助剂（Bayferrox318M） 0.3 附着力促进剂（CD9052） 12.4</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 341,
+        "chunk": "# （32）UV喷涂汽车修补底漆参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（LPWDS4060） POEA</td><td>49.41 16.47 1.65</td><td>819 3.29 颜料/添加剂 28.91</td></tr></table></body></html>\n\n注：加人乙酸乙酯，使黏度（ $25\\mathrm{^{\\circ}C}$ ，涂-4杯）为35s。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 342,
+        "chunk": "# （33）UV喷涂汽车修补底漆参考配方",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 343,
+        "chunk": "#  \n\n<html><body><table><tr><td>三官能团脂肪族PUA（U100）</td><td>55.17</td><td>819 3.29</td></tr><tr><td>POEA 增强附着力树脂（EB168）</td><td>10.98 1.65</td><td>颜料/添加剂 28.91</td></tr></table></body></html>\n\n注：加人乙酸乙酯，使黏度 $25^{\\circ}C$ ，涂-4杯）为35s。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 344,
+        "chunk": "# （34）UV汽车返修清漆参考配方  \n\n<html><body><table><tr><td>PUA PUA PETA</td><td></td><td>29.2 23.4 7.0 3.2</td><td>UV吸收剂（Tinuvin400） 1.3 受阻胺光稳定剂（Tinuvin292） 0.5 流平剂（BaysiloneOL） 0.03 乙酸丁酯 34.8</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 345,
+        "chunk": "# （35）UV汽车返修色漆参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（R5Bayer）</td><td>20.6</td><td>填料（VICRON15-15）</td><td>17.0</td></tr><tr><td>EA(R2,Bayer) 附着力增强型三官能团酸酯（CD9052）</td><td>20.6 12.4</td><td>颜料（TRONOXR-KB-2） 颜料（Bayforox303T）</td><td>1.4 0.3</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 346,
+        "chunk": "# （36）UV汽车罩光清漆参考配方  \n\n<html><body><table><tr><td>六官能度脂肪族PUA（EB5129） 乙氧基季戊四醇四丙烯酸酯（SR494） TPO</td><td>80 120 6 乙酸丁酯</td><td>受阻胺（TINUVIN292） 3 有机硅助剂BYK306 1 20</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 347,
+        "chunk": "# （37）UV汽车罩光涂料参考配方  \n\n<html><body><table><tr><td>二官能团脂肪族PUA（EB4858）</td><td>58.0</td><td>有机硅助剂BYK306</td></tr></table></body></html>  \n\n（38）UV喷涂汽车修补面漆参考配方  \n\n\n<html><body><table><tr><td>脂肪族PUA（LPWDJ4060） 脂肪族PUA（XP2513） PETA 184:TPO（3:1)</td><td>58.40 58.40 受阻胺（Sanduvor3058） 14.00 助剂（BYK331） 10.70 乙酸乙酯</td><td>紫外吸收剂（Sanduvor3206） 2.14 1.07 0.10 20.00</td></tr><tr><td>黏度（25℃，涂-4杯）/s 固含量/%</td><td>20 69</td><td>固化条件（50℃，汞灯900W）/（m/min） 5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 348,
+        "chunk": "# （39）UV喷涂耐候、耐刮伤涂料参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（VPLS2308） 脂肪族PUA（XP2513） HDDA 184:819（7:1)</td><td>44.30 (BYK306) 2.20 紫外吸收剂（TinUVin400） 48.45 受阻胺（TinUVin292） 2.85</td><td>0.60 1.00 0.60 1</td></tr><tr><td>黏度（23C）/mPa·s 150 喷涂量/（g/m²） 50 固化条件/（mJ/cm²） 2800</td><td>汞灯（80W/cm）/盏 灯（80W/cm）/盏 固化速率/（m/min）</td><td>1 2.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 349,
+        "chunk": "# 6.13.5其他UV涂料参考配方",
+        "category": " References"
+    },
+    {
+        "id": 350,
+        "chunk": "#  \n\n（1）UV皮革参考配方  \n\n\n<html><body><table><tr><td>脂肪族PUA EA 丙烯酸单体 光引发剂</td><td>20~40 0~15 10~50 0~5</td><td>染料 纳米材料 流平剂 消泡剂 0.1~0.5</td></tr><tr><td colspan=\"3\">（2）UV皮革涂料参考配方</td></tr><tr><td>脂肪族PUA EA 丙烯酸活性稀释剂 光引发剂 0.3~1</td><td>20~50 消泡剂 0~20 润湿剂 10~50 耐磨剂 1~5 溶剂</td><td>0.1~0.5 0.5~1.5 0.5~3 2~20</td></tr><tr><td colspan=\"3\">流平剂 （3）UV皮革涂料参考配方</td></tr><tr><td>高分子量PUA（含30%NVP） 四官能度PEA NVP IBOA</td><td>39.70 邻苯二甲酸二异辛酯 31.76 BP 7.94 184</td><td>8.66 2.00 2.00</td></tr><tr><td colspan=\"3\">7.94 （4）UV喷涂皮革涂料配方</td></tr><tr><td>芳香族PUA NVP</td><td>31.1 TMPTA 31.1 1173</td><td>4.7 2.0</td></tr><tr><td colspan=\"3\">EHA 31.1 （5）UV玻璃涂料参考配方</td></tr><tr><td>PUA 60.0 TMPTA 10.0 TPGDA 15.0</td><td>1173 硅烷偶联剂 助剂</td><td>4.0 0.5 0.5</td></tr></table></body></html>  \n\n（6）UV玻璃涂料参考配方  \n\n\n<html><body><table><tr><td>脂肪族PUA 甲氧基聚乙二醇（550）单丙烯酸酯（LD552） 聚乙二醇（200）二丙烯酸酯（SR259） HDDA</td><td>70 PETA 10 1173 8 硅烷偶联剂（KH-570） 2</td><td>6 2 0.5</td></tr><tr><td>铅笔硬度/H 附着力/级</td><td>4 1</td><td>光泽 90</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 351,
+        "chunk": "# （7）UV玻璃涂料参考配方  \n\n<html><body><table><tr><td>脂肪族PUA 48 EO-TMPTA 9</td><td>EOEOEA 40 1173 3</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 352,
+        "chunk": "# （8）UV玻璃涂料参考配方  \n\n<html><body><table><tr><td>脂肪族PUA</td><td>50 39 BP</td><td>1173 3 3</td></tr><tr><td colspan=\"4\">低黏度芳香族单丙烯酸酯 三丙烯酸附着力促进剂 5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 353,
+        "chunk": "# （9）UV玻璃磨砂涂料参考配方  \n\n<html><body><table><tr><td>EA</td><td>30</td><td>1173</td></tr><tr><td>PUA TPGDA</td><td>10 34</td><td>偶联剂KH-560 2 气相SiO2 5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 354,
+        "chunk": "# （10）UV辊涂玻璃抗蚀涂料参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（CN988） 42</td><td>POEA 40</td></tr><tr><td>低黏度单丙烯酸酯低聚物（CN131） 10</td><td>非迁移光引发剂（SR1112） 8</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 355,
+        "chunk": "# （11）UV陶瓷涂料参考配方  \n\n脂肪族PUA 20.0 184 4.0  \n氨基（甲基）丙烯酸酯 24.0 BYK306 0.5  \nTPGDA 30.0 BYK333 0.5  \n$({\\mathrm{PO}})_{3}$ TMPTA 20.0 BYK920 1.0",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 356,
+        "chunk": "# （12）UV石材涂料参考配方  \n\n<html><body><table><tr><td>EA TMPTA</td><td>30.0 25.0 25.0</td><td rowspan=\"2\">1173 MDEA 流平剂 消泡剂</td><td rowspan=\"2\"></td><td>3.5 2.0 0.2 0.2</td></tr><tr><td>TPGDA HEMA</td><td>13.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 357,
+        "chunk": "# （13）UV光盘保护涂料参考配方  \n\n<html><body><table><tr><td>PUA</td><td>26.0 17.0</td><td>HPA TPO</td><td></td><td>15.0 2.0</td></tr><tr><td>EA DEGDA (EO)TMPTA 2-羟基-3苯氧基丙烯酸酯</td><td>24.0 20.0 1.5</td><td>184 EDAB PM-1</td><td></td><td>4.0 0.3 0.2</td></tr></table></body></html>\n\n门面",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 358,
+        "chunk": "# （14）UV光盘保护涂料参考配方  \n\n<html><body><table><tr><td>脂肪族PUA</td><td>10.0</td><td>1173</td><td>4.0</td></tr><tr><td>低黏度EA</td><td>10.0</td><td>附着力促进剂</td><td>0.5</td></tr><tr><td>(PO)NPGDA</td><td>70.0</td><td>流平剂</td><td>0.5</td></tr><tr><td>（EO)TMPTA</td><td>5.0</td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 359,
+        "chunk": "# （15）UV光纤涂料参考配方  \n\n<html><body><table><tr><td>UV光纤涤科参考配方 EA NVP BP</td><td>100 DEMK 7 助剂 3</td></tr><tr><td colspan=\"2\">（16）UV光纤涂料参考配方</td></tr><tr><td>聚硅氧烷丙烯酸酯 50.0 PUA 40.0 EA 30.0 安息香乙醚 6.5 1.2</td><td>N,N-二甲基苯胺 1.2 增感剂 2.6 丙烯酸酯 2.4 MEHQ 0.12 UV吸收剂 0.036</td></tr><tr><td colspan=\"2\">BP （17）UV光纤涂料参考配方</td></tr><tr><td>PUA（TDI/HEA/聚丁二醇2000） 78.1 N-乙烯基己内酰胺 6.3 TBOA 35.5</td><td>LA 7.3 TPO-L 2.0</td></tr><tr><td>黏度（40℃）/mPa·s 激活能/（kJ/mol）</td><td>1100 杨氏模量/（kg/mm²） 61 50.3</td></tr><tr><td colspan=\"2\">（18）UV光纤并带涂料参考配方 EA 18 1173</td></tr><tr><td>脂肪族PUA（CN964） 36 VP 9 HDDA 19 EO-TMPTA 10</td><td>3 BP 2 EDAB 1 助剂 2</td></tr><tr><td colspan=\"2\">（19）UV光纤有色涂料参考配方 有机硅EA 60 增感剂 2~3</td></tr><tr><td colspan=\"2\">脂肪族EA 40 稳定剂 BP 3~5 染料</td></tr><tr><td colspan=\"2\">2 （20）UV触控面板ITO膜耐磨涂料参考配方</td></tr><tr><td colspan=\"2\">DPHA 15 1173 3 有机-无机凝胶 15 溶剂 67</td></tr><tr><td colspan=\"2\">（21）UV抗静电涂料参考配方 多官能度丙烯酸酯（EB1290） 50 1850 3</td></tr><tr><td colspan=\"2\">TMPTA 25 184 3 19 导电聚苯胺微凝胶（17.8%含固量） 100</td></tr><tr><td colspan=\"2\">（22）UV抗静电涂料参考配方 5.0 1173 0.6 2.0 丙二醇单甲醚 4.0</td></tr></table></body></html>  \n\n<html><body><table><tr><td colspan=\"3\">（23）UV保形涂料配方</td></tr><tr><td>PEA TEGDA HDDA</td><td>46.10 IBE 5.16 651 29.30</td><td>16.38 3.85</td></tr><tr><td colspan=\"3\">（24）UV保形涂料配方 PEA 38.26</td></tr><tr><td>TEGDA 4.28 HDDA 26.15 IBE 22.81</td><td>651 IBA 氟表面活性剂FL-171</td><td>3.85 3.20 0.55</td></tr><tr><td>（25）UV耐污木器消光面漆参考配方 含氟、聚硅氧烷低聚物（Etercure6154B-80）</td><td>50.0 消光粉（UV55C）</td><td>欢做！（） 10.0 0.4</td></tr><tr><td>TMPTA 184 BP 活性胺（6420）</td><td>30.0 分散剂（EFKA5065） 2.0 流平剂（EterSlip70） 2.0 消泡剂（BYK141） 5.0</td><td>0.5 0.1</td></tr><tr><td>黏度（25C）/mPa·s 固化条件/（mJ/cm²） 固化膜光泽度（60°）</td><td>2200 硬度（铅笔硬度）/H 200 附着力（划格法） 30±5 耐污性（奇异笔擦拭）</td><td>1 100/100 佳</td></tr><tr><td colspan=\"3\">（26）UV耐污PVC地板消光面漆参考配方 含氧、聚硅氧烷低聚物（Etercure6154B-80） 40.0</td></tr><tr><td>HDDA (EO)TMPTA 1173</td><td>15.0 分散剂（EFKA5065） 30.1 消泡剂（BYK）088） 4.0</td><td>0.2 0.1</td></tr><tr><td>黏度（25℃）/mPa·s 外观 固化条件/（mJ/cm²）</td><td>1400 硬度（铅笔硬度）/H 白色乳状 附着力（划格法） 300 耐污性（奇异笔擦拭）</td><td>1 100/100 佳</td></tr><tr><td colspan=\"3\">固化膜光泽度（60°） 50±5 （27）UV塑料（PC、PMMA）耐污涂料参考配方</td></tr><tr><td>含氟、聚硅氧烷低聚物（Etercure6154B-80） 40.5 DPHA 25.0 （PO)NPGDA 20.0</td><td>BP 活性胺（6420） 流平剂（EterSlip70）</td><td>2.0 10.0 0.5</td></tr><tr><td colspan=\"3\">184 2.0 黏度（25C）/mPa·s 1900</td></tr><tr><td>固化条件/（mJ/cm²） 固化膜光泽度（60°）</td><td>300 附着力（划格法） 93 耐污性（奇异笔擦拭）</td><td>100/100 佳</td></tr><tr><td colspan=\"3\">（28）激光快速成型光固化材料参考配方 EA 70.0</td></tr><tr><td></td><td>TEGDA 20.0 1173</td><td>10.0 3.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 360,
+        "chunk": "# 6.13.6UV粉末涂料参考配方",
+        "category": " References"
+    },
+    {
+        "id": 361,
+        "chunk": "# （1）UV粉末涂料参考配方  \n\n<html><body><table><tr><td>UP EA</td><td>50 50</td><td>安息香 184</td><td></td><td>0.4 3.0</td></tr></table></body></html>  \n\n<html><body><table><tr><td colspan=\"3\">①UP双键含量占总双键含量的50%。</td></tr><tr><td>（2）UV粉末涂料参考配方 Uvecoat2100 Uvecoat9010</td><td>80.0 14.4</td><td>Resiflow PV5 0.4 Worlee Add900 0.2</td></tr><tr><td>184 （3）UV粉末涂料参考配方</td><td>5.0</td><td></td></tr><tr><td>Uvecoat3001 Uvecoat9010</td><td>80.0 SiO2 10.0 流平剂 2.0</td><td>5.5 0.2 0.3</td></tr><tr><td>651 2959 （4）UV纸张罩光粉末涂料参考配方</td><td>消泡剂 2.0</td><td></td></tr><tr><td>Uracross P3125</td><td>830 184 BYK361</td><td>10 6</td></tr><tr><td>Uracross P3307 （5）UV木材粉末底漆参考配方</td><td>170</td><td></td></tr><tr><td>UvecoatTM1000 TiO2</td><td>66.0 10.0</td><td>184/819 2.5 流平剂 1.0</td></tr><tr><td>滑石粉/硅酸铝 （6）UV木材粉末涂料参考配方</td><td>20.0 消泡剂</td><td>0.5</td></tr><tr><td>UvecoatTM2100 184/819</td><td>97.0 消泡剂 2.5</td><td>0.5</td></tr><tr><td>（7）UV中密度板用粉末涂料参考配方</td><td></td><td></td></tr><tr><td>甲基丙烯酸聚酯树脂 EA</td><td>37.5 37.5 蜡 TiO</td><td>25.0 3.0</td></tr><tr><td>184 TPO （8）UV白色粉末涂料参考配方</td><td>1.0 流平剂 1.0</td><td>1.0</td></tr><tr><td>丙烯酸/丙烯酸异冰片酯共聚物 GMA</td><td>314.4 2959</td><td>12.5 12.5</td></tr><tr><td>TiO</td><td>121.2 819 250.0 ResiflowPV5</td><td>10.0</td></tr><tr><td>（9）UV白色粉末涂料参考配方 UvecoatTM3001</td><td>100 TiO2</td><td>20</td></tr><tr><td>DPHA 819</td><td>10 2</td><td>Modaflow Powder2000 1</td></tr><tr><td>（10）UV白色粉末涂料参考配方</td><td></td><td></td></tr><tr><td>UPE 乙烯基醚树脂 819</td><td>62.7 184 12.8 TiO 2.0 流平剂</td><td>1.0 20.0 1.5</td></tr></table></body></html>  \n\n<html><body><table><tr><td colspan=\"3\">（11）UV白色粉末涂料参考配方</td></tr><tr><td>马来酸酐不饱和聚酯 结晶型聚乙烯基树脂 TPO</td><td>68.0 184 14.0 TiO 1.0 助流动剂</td><td>0.5 15.0 1.5</td></tr><tr><td colspan=\"3\">（12）UV白色粉末涂料参考配方</td></tr><tr><td>丙烯酸不饱和聚酯 TPO 184</td><td>82.0 TiO2 1.0 助流动剂 0.5</td><td>15.0 1.5</td></tr><tr><td colspan=\"3\">（13）UV白色粉末涂料参考配方 Uralac XP3125 Resiflow P-67</td></tr><tr><td>Uralac2W3307P TPO Luperox Acp35</td><td>80.0 20.0 TiO(R-902) 2.0 1.0</td><td>1.5 20.0 Aluminum Oxide C 0.2</td></tr><tr><td colspan=\"3\">（14）UV白色粉末涂料参考配方</td></tr><tr><td>UvecoatTM2200 TiO 2959</td><td>72.0 819 25.0 流平剂 1.0</td><td>1.5 0.5</td></tr><tr><td colspan=\"3\">（15）UV白色木器粉末涂料参考配方 无定形PEA树脂（Tg=43C） 80 819</td></tr><tr><td>TiOz 184</td><td>20 流平剂 1</td><td>1 1</td></tr><tr><td colspan=\"3\">（16）UV白色亚光木器粉末涂料参考配方 无定形PEA树脂（Tg=43C）</td></tr><tr><td>半结晶PEA树脂（Tm=80C） TiO2 填料 20</td><td>40 184 15 819 25 流平剂</td><td>1 1 1 0.3</td></tr><tr><td colspan=\"3\">硅助剂 （17）UV黑色粉末涂料参考配方 Uralac XP3125 80.0 Resiflow P-67</td></tr><tr><td>Uralac2W3307P TPO Ciba RD97-275 5.0</td><td>20.0 炭黑Shepard Black 2.0 Aluminum OxideC</td><td>6.0 0.2</td></tr><tr><td colspan=\"3\">（18）UV粉末色漆参考配方</td></tr><tr><td>组成 白 UvecoatTM1100,2000,2100,2200 71.0</td><td>蓝 94.0</td><td>绿 黑 94.0 94.0</td></tr></table></body></html>  \n\n<html><body><table><tr><td>组成 UvecoatTM1100,2000,2100,2200</td><td>白</td><td>蓝 94.0</td><td>绿 94.0</td><td></td><td>黑</td></tr><tr><td>颜料</td><td>71.0 一</td><td>2.0</td><td>2.0</td><td></td><td>94.0 1.0</td></tr><tr><td>TiO2</td><td>25.0</td><td>一</td><td>一</td><td></td><td></td></tr><tr><td>光引发剂</td><td>2.5</td><td>2.5 1.0</td><td>2.5</td><td></td><td>3.5</td></tr><tr><td>流平剂 消泡剂</td><td>1.0 0.5</td><td>0.5</td><td>1.0 0.5</td><td></td><td>1.0 0.5</td></tr></table></body></html>\n\n$\\textcircled{1}$ 光引发剂为184、651、819、2959等。$\\textcircled{2}$ 配方中使用Uvecoat $\\mathtt{T M}_{2000}$ 或2100时不需要外加流平剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 362,
+        "chunk": "#木（！  \n\n（19）UV粉末金属涂料参考配方  \n\n\n<html><body><table><tr><td>UvecoatTM2000 97.0 消泡剂 0.5 184/819 2.5</td></tr></table></body></html>\n\n盛#来好白V山（）",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 363,
+        "chunk": "# 6.13.7 UV水性涂料参考配方  \n\n（1）UV水性纸张上光油参考配方  \n\n\n<html><body><table><tr><td colspan=\"3\">马来酸酐改性EA 47.9 2959 水性树脂 12.4 流平剂 AMP-95 14.7 消泡剂</td></tr><tr><td colspan=\"3\">HO 18.9 （2）UV水性纸张上光油参考配方</td></tr><tr><td>马来酸酐改性EA 水性树脂 AMP-95</td><td>59.5 2959 10.5 流平剂 14.8 消泡剂</td><td>3.0 0.8 0.5</td></tr><tr><td colspan=\"3\">HO 18.9 （3）UV水性亚光纸张上光油参考配方</td></tr><tr><td>水性EA 1173</td><td>70.0 水 3.0</td><td>19.5 润湿剂（FC430） 0.5</td></tr><tr><td colspan=\"3\">SiO(Syloid ED80) 7.0 （4）UV水性木器涂料参考配方</td></tr><tr><td>EA水分散体 PUA水分散体 1173</td><td>39.2 增稠剂 10.5 润湿剂 2.0 水</td><td>0.3 0.1 45.5</td></tr><tr><td colspan=\"3\">流平剂 2.4 （5）UV水性木器涂料参考配方</td></tr><tr><td>水性脂肪族PUA（VPLS2282） 1173 184 0.45</td><td>95.20 润湿分散剂（BYK110） 0.45 消泡剂（BYK066N）</td><td>0.50 0.80 2.60</td></tr><tr><td>固化膜性能： 光泽度/% 铅笔硬度/H 附着力/级 2</td><td>99.1 3</td><td>耐酸性（10%HSO，24h） 优良 耐碱性（8h）失重、溶出 一般 耐盐水性（10%NaCl，24h） 优良 耐丙酮（8h） 膜脱落</td></tr><tr><td colspan=\"3\">吸水率/% 16.67 耐水性（48h） 无变化 （6）UV水性木器涂料参考配方</td></tr><tr><td colspan=\"3\">UV水性PUA 100.0 1173 蜡分散体（35%） 3.0 流平剂 毛面剂（100%） 1.5 消泡剂</td></tr></table></body></html>  \n\n（7）UV水性缎纹亚光涂料参考配方 Tpt  \n\n<html><body><table><tr><td>PUA分散体（UVVPLS2317）</td><td>66.0</td><td>500</td><td>0.5</td></tr><tr><td>Hydropalat3275 KWO3826</td><td>1.0 13.4</td><td>BYK348 TafigelPUR50</td><td>0.5 1.6 16.2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 364,
+        "chunk": "# （8）UV水性喷涂木器涂料参考配方  \n\n<html><body><table><tr><td>PEA乳液（LRPE55W）</td><td>74.5</td><td>1173 BP</td><td></td><td>1.5 1.5</td></tr><tr><td>水性单体（CL959） NVP</td><td colspan=\"4\">17.5 4.8</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 365,
+        "chunk": "# （9）UV水性木地板底漆参考配方  \n\n<html><body><table><tr><td>水性PEA（PE55WIN） 70 500 脂肪族EA（LR8765） 30</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 366,
+        "chunk": "# （10）UV水性木地板底漆参考配方  \n\n<html><body><table><tr><td colspan=\"2\">水性PEA（PE22WIN） 70 500 1 亲水性聚醚丙烯酸酯（LR8982） 30</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 367,
+        "chunk": "# （11）UV水性地板底漆参考配方  \n\n（12）UV水性喷涂地板高光面漆参考配方  \n\n\n<html><body><table><tr><td>水可乳化型脂肪族PUA（XP2587）</td><td>63.7</td><td>黏度（23C）/mPa·s</td></tr><tr><td>水 KIP100F</td><td>34.4 19.0</td><td>涂布量/（g/m²） 10</td></tr></table></body></html>  \n\n<html><body><table><tr><td>水可乳化型脂肪族PUA（XP2587） 水</td><td>100 KIP100F 100</td><td>3</td></tr><tr><td>黏度（23℃，涂-4杯）/s 固含量/% 烘干时间（60C）/min</td><td>20 50.7 固化速率/（m/min） 5 光泽（60）/%</td><td>固化条件（汞灯80W/cm）/盏 1 5 80</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 368,
+        "chunk": "# （13）UV水性地板底漆参考配方  \n\n（14）UV水性喷涂地板半亚光面漆参考配方  \n\n\n<html><body><table><tr><td>脂肪族PUA乳液（LS2348） 500</td><td>78.0 0.8 3.5</td><td>流平剂（BYK348） 增稠剂（WT-105A） 水</td><td>0.5 0.5 16.0</td></tr></table></body></html>  \n\n（15）UV水性喷涂地板白色面漆参考配方  \n\n\n<html><body><table><tr><td>水可乳化型脂肪族PUA（XP2587） 100 Deuteron MK 4 GasilEBN 4</td><td>KIP100F 水</td><td>3 100</td></tr><tr><td>黏度（23℃，涂-4杯）/s 20 固含量/% 52.6 烘干时间（60C）/min 5</td><td>固化条件（汞灯80W/cm）/盏 固化速率/（m/min） 光泽（60°）</td><td>1 5 10</td></tr></table></body></html>  \n\n<html><body><table><tr><td>水可乳化型脂肪族PUA（XP2587） TronoxPKB-6</td><td>100 50.0</td><td>KIP100F 水</td><td>3 100</td></tr></table></body></html>  \n\n<html><body><table><tr><td>黏度（23℃，涂-4杯）/s 20 固含量/% 60.6 烘干时间（60℃，min） 固化条件</td><td>汞灯（80W/cm）/盏 灯（80W/cm）/盏 5 固化速率（m/min）</td></tr><tr><td colspan=\"2\">（16）UV水性橙色木材涂料参考配方</td></tr><tr><td>水性PUA分散体 81.8 橙颜料（PO131） 8.8 BAPO（50%水） 2.2</td><td>1173（50%乙二醇丁醚） 2.2 助剂 3.7 去离子水 1.3</td></tr><tr><td colspan=\"2\">（17）UV水性白色木材涂料参考配方</td></tr><tr><td>水性PUA分散体 75.2 白颜料（75%TiO） 16.2 BAPO(50%水） 2.0</td><td>1173（50%乙二醇丁醚） 2.0 助剂 3.3 去离子水 1.3</td></tr><tr><td colspan=\"2\">（18）UV水性喷涂木材色漆参考配方 组成 白 黑</td></tr><tr><td colspan=\"2\">红 IRR400 100.0 100.0 100.0 100.0 500 2.0 2.0 小 2.0 2.0 TPO 0.5 0.5 0.5 0.5 HO 7.0 7.0 7.0 7.0 颜料 2.5 2.0 3.0 4.5</td></tr><tr><td colspan=\"2\">（19）UV水性有色漆参考配方 181 颜料 21.0 光引发剂 2.2</td></tr><tr><td colspan=\"2\">分散剂 2.5 助溶剂 消泡剂 0.3 消泡剂 水 5.3 润湿剂 水性UV-PUD 66.7</td></tr><tr><td colspan=\"2\">（20）UV水性涂料参考配方 水性PUA 76.3 光稳定剂（Timuvin292） 2.5</td></tr><tr><td colspan=\"2\">溶剂 15.9 流平剂（BYK345） 1173 3.5</td></tr><tr><td colspan=\"2\">（21）UV水性PVC地板涂料参考配方</td></tr><tr><td>水性PUA（35%固含量） 100.0 流平剂 1.5 3.0</td><td>0.5 非离子型增稠剂（50%水溶液） 1.0</td></tr></table></body></html>  \n\n注：涂布厚度 $25\\mu\\mathrm{m}$ ， $80^{\\circ}\\mathrm{C}$ 干燥 $60\\mathrm{s}$ ，干后膜厚 $9\\mu\\mathrm{m}$ 0  \n\n（22）UV喷涂水性高光泽清漆参考配方  \n\n\n<html><body><table><tr><td>PUA分散体（UV2282） 500 Envirgem AD01 助剂（BYK381）</td><td>77.4 0.7 1.2 1.0 0.5 19.2</td><td>固含量/% 喷涂量/（g/m²） 固化条件 汞灯（80W/cm）/盏 50℃时/min 固化速率/（m/min）</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 369,
+        "chunk": "# （23）UV水显影保护涂层参考配方  \n\n<html><body><table><tr><td>PEA/脂肪族PUA分散体（UAVPLS2229） 90 2959 HEA 10</td></tr></table></body></html>  \n\n注： $45^{\\circ}C$ 干燥 $10\\mathrm{{min}}$ ，UV曝光，水/乙醇为28/1，显影。  \n\n<html><body><table><tr><td>附着力/% 100</td><td>铅笔硬度/H</td></tr><tr><td>（24）水性UV丝印纸和纸板油墨配方</td><td></td></tr><tr><td>EO-TMPTA</td><td>硅流平、消泡剂 水</td></tr><tr><td colspan=\"2\">80 水</td></tr></table></body></html>\n\n注：用于PVC塑料。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 370,
+        "chunk": "# 6.13.8双重固化涂料参考配方  \n\no,-  \n\n（1）双重固化涂料参考配方  \n\n<html><body><table><tr><td>双固化EA</td><td>50.0 7.5</td></tr><tr><td>TMPTA</td></tr><tr><td>TPGDA</td></tr><tr><td>HEA</td></tr><tr><td>660A（环氧丙烷丁基醚） 25.0</td></tr></table></body></html>\n\n注：UV固化4s， $120^{\\circ}\\mathrm{C}\\times30\\mathrm{min}$ 。  \n\n海##",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 371,
+        "chunk": "# （2）双重固化涂料参考配方  \n\n<html><body><table><tr><td>A组分： DesmophenAVPLS2099/1（30%BA） 21.1 RoskydalUAVPLS2308(20%BA) 32.3 184/819(911) 3.7 Sanduvor3206 1.3</td><td>Sanduvor3058 助剂 MPA B组分： RoskydalUAVPLS2337</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 372,
+        "chunk": "# （3）双重固化涂料参考配方  \n\n<html><body><table><tr><td>A组分： 多羟基丙烯酸酯AcryflowAl40（70%丙酮） 多羟基丙烯酸酯AcryflowP120 IBOA TMPTA HEA</td><td>16.10 3.75 2.50 2.50 2.50 2.50</td><td>B组分： HDI三聚体（80%丙酮） 819 锡催化剂（1%DBTDL） UV吸收剂（50%Tinuvin400） 光稳定剂（50%Tinunin292） 流平剂（BYK358）</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 373,
+        "chunk": "# （4）双重固化涂料参考配方  \n\n（5）UV产酸双重固化涂料参考配方  \n\n\n<html><body><table><tr><td>双酚A环氧树脂（环氧值500） 双酚F环氧树脂（环氧值170）</td><td>双氰胺 5 N-（对氯苯基）-N，N'-二甲基脲 1</td></tr></table></body></html>  \n\n<html><body><table><tr><td>部分丙烯酸化环氧树脂 脲醛树脂（5260） 三聚氰胺树脂（5860） TPGDA TMPTA</td><td>30 HPA 17.5 环氧丙烷丁基醚 1.7 环氧聚酰胺固化剂（650） 10.0 1173</td><td>光产酸引发剂IHT-PI860</td></tr></table></body></html>\n\n注：UV固化4s， $60^{\\circ}\\mathrm{C}\\times30\\mathrm{min}$ 烘烤。  \n\n（6）UV产酸双重固化涂料参考配方  \n\n<html><body><table><tr><td>EA(6104) 多元醇改性聚酯树脂（1370B）</td><td>2.8 33.3</td><td>HPA TMPTA</td><td>14.0</td></tr><tr><td>脲醛树脂（5260） 三聚氰胺树脂（5860）</td><td>36.9 1.7</td><td>1173 光产酸引发剂IHT-PI860</td><td>9.2 0.8 5.0</td></tr></table></body></html>\n\n注：UV固化4s， $60^{\\circ}\\mathrm{C}\\times30\\mathrm{min}$ 烘烤。  \n\n（7）双重固化地板底漆参考配方  \n\n（  \n\n<html><body><table><tr><td>含NCO的脂肪族PUA（VPLS2396）</td><td>68.25</td><td>184 2.5</td></tr><tr><td>脂肪族PUA（VPLS2365）</td><td>29.25</td><td></td></tr></table></body></html>  \n\n（8）双重固化喷涂地板面漆参考配方  \n\n<html><body><table><tr><td>带—NCO的脂肪族PUA（VPLS2337）</td><td>31.95 带—NCO的脂肪族PUA（VPLS2089） 25.61</td><td>助剂（BYKUV3500） 乙酸丁酯</td></tr></table></body></html>\n\n中",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 374,
+        "chunk": "# （9）双重固化塑料涂料参考配方  \n\n<html><body><table><tr><td>EA(EB3700)</td><td>48.3</td><td>硫盐（FX512）</td></tr><tr><td>三甘醇二乙烯基醚</td><td>48.3</td><td>1.0 助剂（FC430） 1.0</td></tr><tr><td>184</td><td>1.4</td><td></td></tr></table></body></html>  \n\n（10）双重固化喷涂SMC用底漆参考配方  \n\n<html><body><table><tr><td>带—NCO的脂肪族PUA（VPLS2337） 带一NCO的脂肪族PUA（VPLS2089）</td><td>32.43 27.32</td><td>BYK333 乙酸丁酯</td><td></td><td>0.10 38.61</td></tr></table></body></html>  \n\n注：配料后使用时间 $>$ 10h.  \n\n（11）双重固化喷涂SMC用弹性底漆配方  \n\n<html><body><table><tr><td>带—NCO的脂肪族PUA（VPLS2337）</td><td>30.41</td><td>184</td><td>1.54</td></tr><tr><td>带—NCO的脂肪族PUA（VPLS2396） 带—NCO的脂肪族PUA（VPLS2089）</td><td>1.54 25.61</td><td>助剂（BYK333） 乙酸丁酯</td><td>0.18 40.72</td></tr></table></body></html>\n\n注：配料后使用时间 ${\\tt>}10{\\bf h}$ 。  \n大昌幸出",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 375,
+        "chunk": "# （12）双重固化金属涂料参考配方  \n\n<html><body><table><tr><td>脂环族环氧树脂（Uvacurel500） 带环氧基杂化丙烯酸树脂（Uvacurel561）</td><td>40.0 硫盐（Uvacurel590） 34.0 500</td></tr></table></body></html>  \n\n注：用于铝基。  \n\n（13）双重固化金属涂料参考配方  \n\n《国者高（I  \n\n\n<html><body><table><tr><td>带—NCO的脂肪族PUA（VPLS2337） 6.5 脂肪族PUA（VPLS2307） 58.8 184</td><td>HDDA</td><td>32.7 2.0</td></tr></table></body></html>  \n\n<html><body><table><tr><td>A组分：</td><td>184 助剂</td><td>3.7 2.9</td></tr><tr><td>脂肪族PUA（VPLS2308） Desmophen A870</td><td rowspan=\"3\">32.3 21.1</td></tr><tr><td>B组分： 带—NCO的脂肪族PUA（VPLS2337） 14.0</td></tr><tr><td>MPA 26.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 376,
+        "chunk": "# （14）双重固化金属、塑料涂料参考配方",
+        "category": " References"
+    },
+    {
+        "id": 377,
+        "chunk": "# （15）双重固化保形涂料参考配方  \n\n<html><body><table><tr><td>硅氧烷接枝PUA</td><td>61.5</td><td>1173 3.0</td></tr><tr><td>硅氧烷改性丙烯酸酯</td><td>35.0</td><td>二月桂酸二丁基锡 0.5</td></tr></table></body></html>  \n\n（16）双重固化保形涂料参考配方  \n\n宝通安小干厅  \n\n\n<html><body><table><tr><td>A组分： 烯丙基醚改性PUA</td><td>45.0</td><td>B组分： EO-TMPTA 20.0</td></tr><tr><td>三甘醇二乙烯基醚（DVE-3）</td><td>10.0 20.0</td><td>1173 5.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 378,
+        "chunk": "# （17）双重固化喷涂保形涂料参考配方  \n\n<html><body><table><tr><td>A组分： 脂肪族PUA</td><td>15.0</td><td>B组分： 脂肪族PUA</td><td>15.0</td></tr><tr><td>TMPTA</td><td>30.0</td><td>TMPTA</td><td>30.0</td></tr><tr><td>HDDA</td><td>40.0</td><td>HDDA</td><td>40.0</td></tr><tr><td>HEMA</td><td>10.0</td><td>HEMA</td><td>10.0</td></tr><tr><td>1173</td><td>3.0</td><td>1173</td><td>3.0</td></tr><tr><td>环烷酸钻</td><td>1.0 0.8</td><td>过氧化叔丁酸 硅表面活性剂</td><td>1.0 0.8</td></tr><tr><td>硅表面活性剂 氟表面活性剂</td><td>0.2</td><td>氟表面活性剂</td><td>0.2</td></tr></table></body></html>  \n\n注：AB按 $1:1$ 混合，8h内用完。  \n\n（18）电荷转移体系UV涂料配方  \n\n<html><body><table><tr><td colspan=\"3\">乙烯基醚/马来酸酐不饱和聚酯（1：1） 94 1173</td></tr><tr><td colspan=\"3\">（19）无光引发剂UV木器涂料参考配方</td></tr><tr><td>EA(EB3720) 三官能度脂肪族PUA（EB264） 有机硅二丙烯酸酯（EB350）</td><td>24.88 28.40 1.00</td><td>(EO)TMPTA 33.80 胺协同剂（FirstcureAS） 3.00 氟表明活性剂（FC4430） 0.30</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 379,
+        "chunk": "# （20）三重固化涂料参考配方  \n\n<html><body><table><tr><td>A组分： 三重固化PUA PO-TMTA</td><td>49.0</td><td>B组分： 羟基聚酯树脂（181X）</td><td>10.0</td></tr><tr><td>1173 4%环烷酸钻</td><td>27.0 3.0 1.5</td><td>过氧化环已酮 乙酸丁酯 TPGDA 11.0</td><td>0.5 3.0</td></tr></table></body></html>\n\n注：A组分B组分混合搅拌均匀。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 380,
+        "chunk": "# 6.13.9阳离子UV涂料、油墨参考配方",
+        "category": " References"
+    },
+    {
+        "id": 381,
+        "chunk": "# （1）阳离子UV涂料参考配方  \n\n<html><body><table><tr><td>脂环族环氧树脂（Celloxide2021，环氧值145） 双酚A环氧树脂（Epokate-828，环氧值190） 双酚A环氧树脂（Epokate-1001，环氧值450）</td><td>30 20 50</td><td>硫盐 3 SiO粉末 60</td></tr><tr><td colspan=\"3\">（2）阳离子UV涂料参考配方</td></tr><tr><td>脂环族环氧树脂（UVR6110） 三环戊基二甲醇（TCDM）</td><td>70 阳离子光引发剂（6992） 25.5 润湿剂L7604</td><td>4.0 0.5</td></tr><tr><td colspan=\"3\">（3）阳离子UV涂料参考配方</td></tr><tr><td>脂环族环氧树脂（ERLX-4360） 76.7 三环戊基二甲醇（TCDM） 18.8</td><td>阳离子光引发剂（6992） 润湿剂L7604</td><td>4.0 0.5</td></tr><tr><td colspan=\"3\">（4）阳离子UV涂料参考配方</td></tr><tr><td>羟丁基乙烯基醚改性聚酯低聚物 1，4-环已基二甲醇二乙烯基醚 49.5</td><td>49.5 阳离子光引发剂（UVI-6974）</td><td>1.0</td></tr><tr><td colspan=\"3\">（5）阳离子UV涂料参考配方</td></tr><tr><td>脂环族环氧树脂（Uvacure1500） 改性脂环族环氧树脂（Uvacurel533） 1，6-已基二乙二醇醚 CAT003 6.4</td><td>61.2 乙二醇 20.4 硫盐（Uvacurel590） 6.4 硅润湿剂（SilwetL-7602）</td><td>3.2 2.4 0.4</td></tr><tr><td colspan=\"3\">（6）阳离子UV涂料参考配方</td></tr><tr><td>脂环族环氧树脂（CY179） 87.0 TMPTA 10.0</td><td>三苯基硫盐 BP</td><td>1.5 1.5</td></tr><tr><td colspan=\"3\">（7）阳离子UV涂料参考配方</td></tr><tr><td>双酚A环氧树脂（环氧值500） 双酚F环氧树脂（环氧值170） GMA HDDA</td><td>46.0 双氰胺 20.0 二苯基碘六氟磷酸盐 7.0 BP 20.0</td><td>3.5 2.0 1.5</td></tr><tr><td colspan=\"3\">（8）阳离子UV涂料参考配方</td></tr><tr><td>脂环族环氧树脂（Celloxide2021，环氧值145） 双酚A环氧树脂（Epokate-828，环氧值190） 双酚A环氧树脂（Epokate-1001，环氧值450）</td><td>18.5 三苯基硫盐 13.0 SiO2 30.0</td><td>2.0 36.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 382,
+        "chunk": "# （9）阳离子UV纸张上光参考配方  \n\n<html><body><table><tr><td>脂环族环氧树脂 乙烯基醚</td><td>三芳基硫盐 硅流平剂</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 383,
+        "chunk": "# （10）阳离子UV塑料涂料参考配方  \n\n<html><body><table><tr><td>脂环族环氧树脂（UVR6105） 环氧树脂（Heloxy48Epoxide） 环氧树脂（Vikolox14Epoxide）</td><td>72.5 10.0 5.0 7.0</td><td>三芳基硫盐（UVI6992） 润湿剂（SilwetL7604） 流平剂（ResiflowL37）</td><td>5.0 0.5 0.5</td></tr></table></body></html>  \n\n注：用于OPP、PE、PVC及PET等塑料薄膜。  \n\n（11）阳离子UV塑料涂料参考配方  \n\n<html><body><table><tr><td>脂环族环氧树脂（UVR6110） 三甘醇二乙烯基醚</td><td>76.9 19.2 FC430</td><td>阳离子光引发剂（UVI-6974） 1.0 1.0</td></tr></table></body></html>  \n\n（12）阳离子UV塑料涂料参考配方  \n\n<html><body><table><tr><td>环氧树脂（Uvacure1500） DEG</td><td>77.5 18.0</td><td>阳离子光引发剂（Uvacure1590） 4.0 SilwetL7602 0.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 384,
+        "chunk": "# （13）阳离子UV白色塑料涂料参考配方  \n\n<html><body><table><tr><td>脂环族环氧树脂（UVR6110） 1，4-环已基二甲醇二乙烯基醚</td><td>45.0 27.0 8.2</td><td>阳离子光引发剂（UVI6974） FC430 TiO2</td><td>0.9 0.9 16.4</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 385,
+        "chunk": "# （14）阳离子UV金属涂料参考配方  \n\n<html><body><table><tr><td>环氧化聚丁二烯（PolyBD605E） 环氧化聚丁二烯（SarcatK126）</td><td>100.0 90.0 10.0</td><td>Cyracure 6974 SilquestA189 BYK341</td></tr></table></body></html>  \n\n（15）阳离子UV金属涂料参考配方  \n\n<html><body><table><tr><td>环氧树脂（Epon828）</td><td>47.6</td><td>硫盐（FX512）</td></tr><tr><td colspan=\"3\">三甘醇二乙烯基醚 47.6 FC430</td></tr></table></body></html>  \n\n注：用于铝和钢基材。  \n\n（16）阳离子UV金属涂料参考配方  \n\n<html><body><table><tr><td>环氧树脂（DER335）</td><td>79.3</td><td>硫盐（KI85）</td></tr><tr><td>三甘醇二乙烯基醚</td><td>15.0</td><td>FC430</td></tr></table></body></html>  \n\n注：用于铝基。  \n\n（17）阳离子UV固化涂料参考配方  \n\n<html><body><table><tr><td>脂环族双环氧化物（UVR6105） 二乙烯基醚（DVE3）</td><td>79.0 15.5</td><td>碳酸丙酯 FC430</td></tr></table></body></html>  \n\n（18）阳离子UV固化涂料参考配方  \n\n\n<html><body><table><tr><td>乙烯基醚改性环氧树脂 二乙烯基醚（DVE-3）</td><td>71 三芳基硫六氟梯酸盐 15助剂</td></tr></table></body></html>  \n\n（19）阳离子UV铝基涂料参考配方  \n\n<html><body><table><tr><td>环氧树脂（Uvacure1500） 56.7 环氧树脂（Uvacure1530） 37.8</td><td>阳离子光引发剂（Uvacure1590） 5.0 SilweyL-7602 0.5</td></tr></table></body></html>  \n\n（20）阳离子UV铝基涂料参考配方  \n\n环氧树脂（Uvacure1500） 24.6 阳离子光引发剂（Uvacure1590） 5.0   \n环氧树脂（Uvacure1530） 69.9 SilweyL-7602 0.5  \n\n（21）阳离子UV铝基色漆参考配方  \n\n<html><body><table><tr><td>组成 脂环族环氧UVR6105</td><td>黄色 95.5</td><td>蓝色 90.5</td><td>红色 85.5</td><td></td><td>黑色 75.5</td></tr><tr><td>三乙二醇二乙烯基醚DVE-3</td><td>20.0</td><td>20.0</td><td>20.0</td><td></td><td>20.0</td></tr><tr><td>聚酯二醇TONEPoly0201</td><td>5.2</td><td>5.2</td><td>5.2</td><td></td><td>5.2</td></tr><tr><td>三芳基硫六氟磷酸盐UV1-6990</td><td>8.0</td><td>8.0</td><td>8.0 一</td><td></td><td>8.0</td></tr><tr><td>Yellow13</td><td>12.0</td><td>一</td><td></td><td></td><td>一</td></tr><tr><td>Blue15:4</td><td>一</td><td>12.0</td><td>一</td><td></td><td>一</td></tr><tr><td>Red210</td><td>一</td><td>一</td><td>12.0</td><td></td><td></td></tr><tr><td></td><td>一</td><td></td><td></td><td></td><td></td></tr><tr><td>Black250</td><td></td><td></td><td></td><td></td><td>12.0</td></tr></table></body></html>  \n\n（22）阳离子UV铝罐白色涂料配方  \n\n\n<html><body><table><tr><td>脂环族环氧树脂（cy179） 57 钛白粉 40</td><td>三芳基硫六氟磷酸盐 2.25 ITX 0.75</td></tr></table></body></html>  \n\n（23）阳离子UVPCB保护涂料参考配方  \n\n<html><body><table><tr><td>环氧树脂（Uvacurel500） 环氧树脂（Uvacurel530）</td><td>46.5 49.0</td><td>阳离子光引发剂（Uvacure1590） SilwetL</td><td>4.0 0.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 386,
+        "chunk": "# （24）阳离子UV塑料油墨参考配方  \n\n<html><body><table><tr><td>脂环族环氧树脂（UVR6105） 环氧树脂（Tone0301） 环氧树脂（Heloxy505）</td><td>53.8 5.0 5.0 5.0</td><td>三芳基硫盐（UVI6990） 颜料 分散剂（BYKp104s） 润湿剂（SilwetL7500）</td><td>15.0 15.0 0.4</td></tr></table></body></html>  \n\n注：用于OPP、PE、PP及PVC等塑料。  \n\n（25）阳离子UV柔印油墨参考配方  \n\n<html><body><table><tr><td>脂环族环氧树脂 聚酯二醇</td><td>50 10</td><td>三芳基硫盐 聚乙烯蜡 5 表面活性剂</td><td>4 1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 387,
+        "chunk": "# （26）阳离子UV黄油墨参考配方  \n\n<html><body><table><tr><td>3，4-环氧已烷甲酸-3，4-环氧环己烷 甲酯（ECC） 2-乙基-2-羟甲基氧杂丙烷</td><td>57.1 10.0</td><td>联苯基硫杂葱酮，六氟磷酸硫盐 BPITX-PF（23%碳酸丙酯） 黄颜料（Y13） 流平剂BYK361</td><td>17.4 15.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 388,
+        "chunk": "# 6.13.10EB涂料、油墨参考配方  \n\n<html><body><table><tr><td>EA(EB600) TMPTA TPGDA</td><td>15 EHA 45 聚硅氧烷丙烯酸酯 28</td></tr><tr><td>（2）EB木器腻子参考配方</td><td></td></tr><tr><td>EA 26 TMPTA 8</td><td>超细滑石粉 24 氧化钡 42</td></tr><tr><td>（3）EB木材封闭漆参考配方</td><td></td></tr><tr><td>EA 7.2 67.7</td><td>滑石粉 25.1</td></tr><tr><td>TPGDA （4）EB低光泽木器面漆参考配方</td><td></td></tr><tr><td>EA 25 NVP HDDA</td><td>25 消光剂SiO</td></tr><tr><td>TPGDA 10 二氧化钛 （5）EB木器涂料参考配方</td><td></td></tr><tr><td>EA（含20%TPGDA） 45.0 SiO毛面剂 四官能PEA</td><td>13.5 流平剂</td></tr><tr><td>TPGDA 31.0 （6）EB家具涂料参考配方</td><td></td></tr><tr><td>脂肪族PUA HDDA</td><td>75 颜料 15</td></tr><tr><td>（7）EB塑料涂料参考配方</td><td>聚硅氧烷丙烯酸酯（EB350）</td></tr><tr><td>PUA 10 TMPTA HDDA</td><td>45 聚乙烯蜡粉 30</td></tr><tr><td>（8）EB钢材防腐底漆参考配方 EA</td><td>aC 11.5 分散剂</td></tr><tr><td>PUA 11.5 二氧化钛 PEA 稀释剂</td><td>15.3 23.0 防腐蚀颜料 20.0 18.5</td></tr><tr><td colspan=\"2\">（9）EB钢材防腐底漆参考配方 脂肪族环氧树脂 20 阳离子光引发剂 多元醇 25 二氧化钛</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 389,
+        "chunk": "# （10）EB钢材面漆参考配方  \n\n<html><body><table><tr><td>四官能度PEA 52.5 PEGDMA 22.5</td><td>二氧化钛 25.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 390,
+        "chunk": "# （11）EB镀铬铝材涂料参考配方  \n\n<html><body><table><tr><td>EA TMPTA EHA</td><td>55 20 10 5</td><td>BP 二甲基乙醇胺 FC430</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 391,
+        "chunk": "# （12）EB磁带涂料参考配方  \n\n<html><body><table><tr><td>PEA 聚酯型PUA</td><td>2.3 2.3</td><td>三氧化二铝 分散剂</td><td></td><td>0.4 0.7</td></tr><tr><td>低聚合度氯乙烯-醋酸乙烯共聚物 钛改性FeO3</td><td>2.3 22.6</td><td>润滑剂 溶剂</td><td></td><td>0.7 67.6</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 392,
+        "chunk": "# （13）EB阻燃涂料参考配方  \n\n<html><body><table><tr><td>氯茵酸烯丙酯（SR383） 四溴双酚A（RXD56843）</td><td>18 三乙基烷基醚硫酸季铵盐（EMERSTAT6660） 10 40 阻燃剂（AGO-40） 30</td></tr></table></body></html>  \n\n$\\textcircled{1}$ 40份酸体 $\\mathrm{{\\bfSb_{2}O_{5}}}$ 分散于60份聚酯树脂中。  \n\n（14）EB涂料参考配方  \n\n\n<html><body><table><tr><td>亚麻油改性PUA 50 TMPTA 12</td><td>TPGDA 23 HDDA 15</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 393,
+        "chunk": "# （15）橙色纸箱印刷油墨参考配方  \n\n<html><body><table><tr><td>EA</td><td></td><td>30</td><td>双芳基黄</td><td></td><td>16</td></tr><tr><td>PEA 三官能度稀释剂</td><td></td><td>25 20</td><td>CaCO3 PE蜡</td><td></td><td>2 3</td></tr></table></body></html>  \n\n![](images/07be158a2e394945cf39fa5f3ada8cd43442d492ce8964ac434f48df0f7faaac.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 394,
+        "chunk": "# 第7章 光固化油墨  \n\n油墨是由有色体（颜料、染料等)、连结料、填料、添加物等物质组成的均匀混合物，主要用于印刷和包装行业，是印刷工业最重要的印刷材料之一。  \n\n油墨产品按印刷方式不同可分为胶印（平版）油墨、凹印油墨、凸印油墨、柔印油墨、网印油墨、移印油墨和喷墨油墨等。按承印物不同可分为纸张油墨、塑料油墨、金属油墨、玻璃油墨、陶瓷贴花油墨、织物印花油墨等。按干燥方法不同可分为挥发干燥型油墨、渗透干燥型油墨、氧化干燥型油墨、热固化油墨、光固化油墨和电子束固化油墨等。此外，用来防伪和特种需要的油墨有光敏油墨、热敏油墨、压敏油墨、发泡油墨、香味油墨、导电油墨、磁性油墨、液晶油墨、喷射油墨和微胶囊油墨等。  \n\n紫外光固化（UV）油墨是一种新型的环保型油墨，它与普通油墨相比，有很多优点：  \n\n$\\textcircled{1}$ 无溶剂排放，既环保又安全；  \n\n$\\textcircled{2}$ 生产效率高，印刷速度可达 $100{\\sim}500\\mathrm{m/min}$ ，光纤油墨更可高达 $1500{\\sim}2000\\mathrm{m}/\\mathrm{min}$  \n\n$\\textcircled{3}$ 快速固化，故印品是干燥的，叠放时不会因油墨未于而相互沾污，不用喷粉，印刷几和车间环境清洁，无粉尘污染；  \n\n$\\textcircled{4}$ 油墨印后立即固化，网点不扩大，油墨不会渗透到纸张中，故印品印刷质量优异，色饱和度、色强度和清晰度都明显好于普通油墨；  \n\n$\\textcircled{5}$ 可以在线加工作业；  \n\n$\\textcircled{6}$ 可适用对热敏感的承印物印刷。  \n\nUV油墨目前存在主要问题是：  \n\n$\\textcircled{1}$ 价格较贵，影响了广泛的应用推广；  \n\n$\\textcircled{2}$ 部分原材料（活性稀释剂、光引发剂）有气味、毒性或皮肤刺激性，影响了在食品和药品包装中的应用；  \n\n$\\textcircled{3}$ 瞬间固化，造成体积收缩，使涂层内应力大，降低了对承印物的附着力，影响了在金属制品中的广泛应用；  \n\n$\\textcircled{4}$ 需在避光、低温（ $.<30^{\\circ}\\mathrm{C}$ ）条件下运输和贮存。  \n\nUV油墨可适用于不同的印刷方式，几种常用印刷方式所用UV油墨的基本性能见表7-1。  \n\n表7-1适用于不同印刷方式的UV油墨基本性能  \n\n\n<html><body><table><tr><td>印刷方式</td><td>颜料含量/%</td><td>一般黏度范围/mPa·s</td><td>一般膜厚/μm</td><td>固化速率/（m/min）</td></tr><tr><td>凹印</td><td>6~g</td><td>20~300</td><td>9~20</td><td>70~300</td></tr><tr><td>凸印</td><td>12~16</td><td>10000~150000</td><td>3~,8</td><td>50~100</td></tr><tr><td>柔印</td><td>12~18</td><td>100～2000</td><td>2~5</td><td>60～300</td></tr><tr><td>网印</td><td>5~9</td><td>5000~10000</td><td>8~25</td><td>10~25</td></tr><tr><td>胶印</td><td>15~21</td><td>18000～30000</td><td>1~3</td><td>100~400</td></tr><tr><td>无水胶印</td><td>14~18</td><td>13000~18000</td><td>1~4</td><td>50～100</td></tr></table></body></html>  \n\nUV油墨与普通油墨所用主要原材料比较见表7-2。  \n\n表7-2UV油墨与普通油墨所用主要原材料比较  \n\n\n<html><body><table><tr><td>UV油墨</td><td>普通油墨</td><td>UV油墨</td><td>普通油墨</td></tr><tr><td>低聚物</td><td>联结料(树脂)</td><td>颜料</td><td>颜料</td></tr><tr><td>活性稀释剂</td><td>溶剂或油</td><td>填料</td><td>填料</td></tr><tr><td>光引发剂</td><td>催化剂</td><td>各种添加剂</td><td>各种添加剂</td></tr></table></body></html>  \n\n从表7-2中看到UV油墨用的连结料是低聚物，主要为丙烯酸类树脂；UV油墨不使用溶剂或油，而用活性稀释剂，主要为丙烯酸多官能酯；UV油墨的催化剂为光引发剂，在紫“外光照射下能发生光化学反应，产生自由基或阳离子，从而引发丙烯酸低聚物和丙烯酸多官能酯发生聚合和交联固化，使油墨干燥。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 395,
+        "chunk": "# 7. 1.1 低聚物  \n\n连结料是油墨的主体组成，它是油墨中的流体组成部分，是起联结作用。在油墨中将颜料等固体粉状物质联结起来，使之在研磨分散后形成浆状分散体，印刷后在承印物表面干燥并固定下来。油墨的流变性能、印刷性能和耐抗性能等主要取决于连结料。UV油墨的连结料是低聚物，它的性能基本上决定了固化后油墨层的主要性能：印刷适性、流变性能、耐抗性能和光固化速率等，因此低聚物的选择是UV油墨配方设计的最重要环节。  \n\n自由基光固化UV油墨的低聚物主要为各类丙烯酸树脂，最常用的是环氧丙烯酸树脂、聚氨酯丙烯酸树脂、聚酯丙烯酸树脂和环氧化油丙烯酸脂，它们的优缺点见表7-3。阳离子光固化UV油墨的低聚物则是环氧树脂和乙烯基醚类化合物。  \n\n表7-3UV油墨常用低聚物比较  \n\n\n<html><body><table><tr><td>低聚物</td><td>优点</td><td>缺点</td></tr><tr><td>环氧丙烯酸树脂</td><td>价格便宜，光固化速率快，光泽和硬度高， 耐抗性好，对颜料润湿性良好</td><td>柔韧性差，较易乳化</td></tr><tr><td>聚氨酯丙烯酸树脂</td><td>综合物性好，耐磨性、柔韧性好，附着力、耐 抗性好</td><td>价格较贵，黏度高</td></tr><tr><td>聚酯丙烯酸树脂</td><td>价格较低，对颜料润湿性好，综合物性较好</td><td>耐化学药品性较差，光固化速率较低</td></tr><tr><td>环氧化油丙烯酸树脂</td><td>价格便宜，黏度低，对皮肤刺激性小，对颜 料润湿性优良</td><td>光固化速率慢</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 396,
+        "chunk": "# 7.1.2 活性稀释剂  \n\n活性稀释剂是UV油墨中一个重要组成，它除了调节油墨的黏度外，也用来改善UV  \n\n油墨的光固化速率和固化后油墨层的性能。  \n\n用于自由基光固化UV油墨活性稀释剂都为丙烯酸多官能酯，单官能度和双官能度内烯酸酯稀释能力强，而多官能度丙烯酸酯有利于提高固化速率和耐抗性，通常根据UV油墨性能要求搭配混合使用。用于阳离子光固化UV油墨的活性稀释剂为乙烯基醚和环氧化合物。  \n\nUV油墨印品大多和人体直接接触，因此它的卫生安全性能格外受重视，一些挥发性高、气味大、易致过敏和有毒的活性稀释剂不应采用。如气味较大的丙烯酸异冰片酯(IBOA)，一般不用；DEGDA和TEGDA致过敏性和毒性太强，已基本淘汰；HDDA有一定刺激性，但对塑料有较好的提高附着力作用，主要用于塑料油墨；NPGDA和TMPTA也有较大的刺激性，可用乙氧基或丙氧基化单体来代替。  \n\n此外，选择对颜料润湿性能好的活性稀释剂，对制备UV油墨也很重要。HDDA对颜料润湿性较好，其他的如壬基酚四亚乙氧基丙烯酸酯、双三羟甲基丙烷四丙烯酸酯、双季戊四醇五丙烯酸酯等油性基团较长或比例较大的活性稀释剂有较好的对颜料的润湿性。  \n\n还需留意的是活性稀释剂对印刷机械中胶辊、印版等零部件是否有侵蚀溶胀作用，以免影响印刷机械正常运行。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 397,
+        "chunk": "# 7.1.3 光引发剂  \n\n光引发剂也是UV油墨中一个重要组成，它决定了UV油墨的光固化速率。  \n\n光引发剂的选择首先要考虑光引发剂的吸收光谱与光源的发射光谱相匹配。目前UV光源主要为中压汞灯，其发射光谱在紫外区的 $365\\mathrm{nm}$ 、 $313\\mathrm{nm}$ 、 $302\\mathrm{nm}$ 、 $254\\mathrm{nm}$ 等处有较强强度，而许多光引发剂在上述波长处均有较大吸收。  \n\nUV油墨是一个由颜料组成的有色体系，因颜料对紫外光有吸收、反射和散射，而不同颜色的颜料对紫外光的吸收和反射是不相同的，都会影响油墨中光引发剂对紫外光的吸收，从而影响UV油墨的光固化速率，因此UV油墨配方中对光引发剂的选择特别重要，要选用受颜料紫外吸收影响最小的光引发剂。颜料在紫外区吸收最小的波段俗称颜料“窗口”，此波段紫外光透过最多，最有利于光引发剂吸收。为了充分发挥不同光引发剂的协同作用，在UV油墨中往往都选用两种以上的光引发剂配合使用，以充分利用紫外光源发射的不同波段的紫外光和颜料“窗口”提供透射的紫外光，达到用最低的光引发剂用量，制成光固化速率最快的UV油墨。  \n\nUV油墨常用的光引发剂有BP、651、1173、184、ITX、907、369、TPO和819等。这里特别要指出，白色UV油墨一般都用TPO与184、819与184或TPO和819，它们都为酰基麟氧类光引发剂，光引发活性极高，有较长的紫外吸收波长，还有光漂白效果，适用各种颜料光固化，特别是白色颜料钛白粉；而184则不泛黄，配合使用，对白色油墨固化极佳。而其他颜色UV油墨常用TIX与907或ITX与369配合使用，有很高的光引发活性。这是因为颜料对紫外光吸收，使907的光引发效率大大降低，但ITX在360～405nm有较高的紫外吸收，与颜料竞争吸光，并激发至激发三线态，激发态ITX与907可发生能量转移，使907由基态跃迁至激发三线态，激发态907进而裂解生成自由基引发光聚合，而ITX 回到基态。同时907分子中的吗啉基叔胺结构与夺氧型ITX形成激基复合物，并发生电子转移，产生自由基引发聚合，在这双重作用下，ITX和907在有色体系中呈现很高的光引发活性，可在除白色外其他颜色UV油墨中应用（因ITX、907和369.都有一定颜色，影响白色油墨色泽)。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 398,
+        "chunk": "# 7. 1.4 颜料  \n\n颜料也是UV油墨的一个重要组成，它是以极小的颗粒分散在油墨成膜物中。颜料在油墨中主要提供颜色，同时起遮盖作用。由于油墨中颜料加入量较大，它对油墨的流变性能（如流动性、黏度等）会有较大影响。在UV油墨中，颜料对紫外光发生吸收、反射或散射，会降低光引发剂的光引发效率，对光固化速率产生不利影响。但颜料加入，可以减少UV固化时的体积收缩，从而有利改善附着力。  \n\n颜料可分为无机颜料和有机颜料，鉴于有机颜料综合性能比无机颜料好，UV油墨中主要使用有机颜料，但黑色和白色则用无机颜料。UV油墨常用颜料，如黄颜料有汉沙黄、联苯胺黄等；红颜料有金光红、立索尔宝红等；蓝颜料有菁蓝、碱性蓝等；绿颜料有酞菁绿等，这些颜料都是有机颜料。而黑色颜料则为炭黑，白色颜料为钛白粉，以金红石型钛白为主，它们都为无机颜料。不同颜料的吸收光谱、透射光谱和反射光谱如图7-1～图7-3所示。  \n\n从图7-1UV油墨常用三种彩色颜料的吸收光谱看到黄、红、蓝三种颜料在 $320{\\sim}420\\mathrm{nm}$ 范围内都有不同程度的弱吸收，这些弱吸收区域就是颜料的“窗口”。  \n\n![](images/6eef08b7421008f1b37973c1ae1d349f965e4d86b8bfcebe24ba911c7192bc0e.jpg)  \n图7-1UV油墨常用三种彩色颜料的吸收光谱  \n\n从图7-2不同颜料着色体系的透射光谱中看到，红、黄、蓝三种颜料在紫外区均有一定的透过率，特别是红色颜料透过率最高，透光性能由强到弱依次为：  \n\n红色颜料 $>$ 黄色颜料 $>$ 蓝色颜料 $>$ 炭黑  \n\n根据各种颜料的透光性能，在相同光引发剂条件下，UV油墨光固化速率由大到小依次为：  \n\n一般来说，UV油墨红色和黄色容易固化，蓝色和黑色相对困难，白色也较难固化。同一颜色的颜料，由于品种不同，结构不同，色相有所差别，所以紫外吸收和透射性能也有所不同，造成光固化速率有差别。各种颜色UV油墨光固化难易程度的定性比较可参见表7-4，以黄色油墨的固化速率为 $100\\%$ 作基准。  \n\n![](images/cdd2c911c5acc3a0345a252fa96b7374d6fddce664567e268fbf22f20622533f.jpg)  \n图7-2不同颜料着色体系的透射光谱  \n\n![](images/af4df7f7fe5057aa22cc2e94aa7c49f3748883dde194e6ea955d209052b32210.jpg)  \n图7-36种代表性颜料的相对反射光谱  \n\n表7-4各色UV油墨光固化速率的相对比较  \n\n\n<html><body><table><tr><td>油墨颜色</td><td>相对固化速率/%</td><td>油墨颜色</td><td>相对固化速率/%</td></tr><tr><td>黄色</td><td>100</td><td>蓝色</td><td>64</td></tr><tr><td>红色</td><td>86</td><td>黑色</td><td>28</td></tr></table></body></html>  \n\n正因为UV油墨不同颜色固化速率不同，在多色套印时，要将最难固化的颜色先印，容易固化的后印，这样可避免难固化色墨层对易固化色墨层的光屏蔽，同时也使得难固化色墨层有多次接受紫外光辐照的机会，利于固化完全。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 399,
+        "chunk": "# 7.1.5 填料  \n\n填料在油墨中可以改善油墨的流变性能，起补强、消光、增稠和防止颜料沉降等作用，填料价格低廉，也可降低油墨成本。填料基本上是透光的，并有较高的折射率，可使入射光线在墨层内发生折射和反射，增加有效光程，提高光引发剂接受光照射的机会，这对UV油墨将是非常有利的，可提高光固化速率。UV油墨常用的填料有碳酸钙、硫酸钡、氢氧化铝、二氧化硅、滑石粉和高岭土等。由于纳米技术的发展，纳米材料的应用，UV油墨也开始使用纳米填料，由于纳米微粒具有很好的表面润湿性，它们吸附在油墨中颜料颗粒的表面，能大大改善油墨的亲油性和可润湿性并能促进油墨分散体系的稳定，所以添加了纳米填料的油墨的印刷适性，得到较大的改善。油墨添加纳米二氧化硅后，具有防结块、消光、增稠和提高触变性，还有利颜料悬浮。油墨添加纳米碳酸钙，不仅可起到增白、扩容、降低成本的作用，还具有补强作用和良好的分散性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 400,
+        "chunk": "# 7. 1. 6 助剂  \n\n助剂是UV油墨的辅助成分。助剂的作用是调整印刷的适性，确保油墨在生产、应用、运输和贮存过程中性能的稳定。  \n\nUV油墨常用助剂有消泡剂、流平剂、润湿分散剂、触变剂、附着力促进剂、阻聚剂和蜡等。  \n\n（1）消泡剂这是一种能防止和消除油墨在制造和使用过程中产生气泡的添加剂。它具有与油墨体系不相容性、高度铺展性和渗透性以及低表面张力特性。消泡剂加人UV油墨中，能很快地分散成微小液滴，使气泡稳定地与表面活性剂结合，快速铺展，降低气泡周围液体的表面张力，使小气泡聚集成大气泡，最终使气泡破裂。  \n\nUV油墨常用的消泡剂为有机聚合物（聚醚、聚丙烯酸酯）和有机硅树脂（聚二甲基硅油、改性聚硅氧烷)。  \n\n（2）流平剂这是一种用来改善油墨层流平性，防止缩孔、起皱、印痕等病产生的添加剂。表面张力是油墨层流平的推动力。当油墨印刷到承印物后，表面张力作用使油墨铺展到承印物上；同时表面张力有使油墨层表面积收缩至最小的趋势，使油墨层的刷痕、皱纹等缺陷消失，变成平整光亮的表面。  \n\nUV油墨常用的流平剂为聚丙烯酸酯、有机硅树脂和氟表面活性剂三大类。  \n\n（3）润湿分散剂这是一种用于提高颜料在油墨中悬浮稳定性的添加剂。润湿剂主要是降低油墨体系的表面张力，使之铺展于承印物上；分散剂吸附在颜料表面上产生电荷斥力或空间位阻，防止颜料产生絮凝，使分散体系处于稳定状态。由于润湿剂和分散剂的作用有时较难区分，往往兼备润湿和分散功能，故称为润湿分散剂。  \n\n润湿分散剂大多数也是表面活性剂，由亲颜料的基团和亲树脂的基团组成。用于UV油墨的润湿分散剂主要为含颜料亲和基团的聚合物。  \n\n（4）触变剂这是一种加人油墨可提高油墨触变性的添加剂。对于厚油墨层油墨触变性尤为重要，可防止印刷后油墨横向扩散，提高印品清晰度。  \n\nUV油墨常用的触变剂为气相二氧化硅。  \n\n（5）附着力促进剂这是一种提高油墨与承印物附着性能的添加剂。对于一些油墨较难附着的承印物如金属、塑料、玻璃印刷时，油墨中往往要加入附着力促进剂，以提高油墨的附着力。  \n\n承印物为金属时，由于印刷油墨后需进行剪切、冲压等后加工工序，要求油墨层与金属基材有优异的附着力，为此常在油墨配方中添加附着力促进剂。用作金属附着力促进剂的大多为带有羟基、羧基的化合物，UV油墨最常用的为甲基丙烯酸磷酸酯PM-1和PM-2。  \n\n承印物为塑料时，由于塑料品种较多，除聚烯烃为聚乙烯或聚丙烯，大多数塑料只要选择合适的树脂和活性稀释剂，附着力问题基本上都可以解决。聚烯烃由于表面能较低，为非极性结构，除了要选择表面能低的树脂和活性稀释剂外，配方上还要考虑降低固化收缩率，有时可加少量氯化聚丙烯，以提高附着力。但目前对聚乙烯和聚丙烯基材主要通过印刷前用火焰喷射或电晕放电处理，以使其表面惰性的C—H结构转化成极性的羟基、羧基、炭基等极性结构，并带上电荷，聚乙烯和聚丙烯表面与油墨的树脂和活性稀释剂亲和性增加，提高了油基的附着力。  \n\n对玻璃承印物，常用硅烷偶联剂作附着力促进剂，如KH-570。KH570为甲基丙烯酸酯化的硅氧烷，其中甲基丙烯酸酯基可参与聚合交联，硅氧烷基团易与玻璃表面的硅羟基缩合成Si一O一Si结构，使油墨对玻璃的附着力提高。  \n\n（6）阻聚剂这是一种用来减少UV油墨在生产、运输和贮存时发生热聚合，提高油墨贮存稳定性的添加剂，因此也称稳定剂。  \n\n常用的阻聚剂有对苯二酚、对甲氧基苯酚、对苯和2，6-二叔丁基对甲苯酚等酚类化合物。但酚类化合物必须在有氧气条件下才能产生阻聚效应，所以UV油墨存放的容器内，油墨不能盛得太满，以留出足够的空间，保证有足够的氧气。  \n\n最近还有一种用于UV油墨的高效阻聚剂三（ $N\\cdot$ -亚硝基-N-苯基羟胺）铝盐，但溶解性差，因而常配成活性稀释剂溶液使用，代号为ST-1（含 $8\\%$ ）和ST-2（含 $4\\%$ )，它们都是厌氧型阻聚剂，并有优良的稳定性，在 $60^{\\circ}\\mathrm{C}$ 下可使体系保持稳定。  \n\n（7）蜡蜡是油墨制造中常用的一种添加剂，主要起改变油墨的流变性，改善抗水性和印刷适性（如调节黏性)，减少蹭脏、拔纸毛等病，并可改善印品的滑性，使印品耐摩擦。在UV油墨中，蜡加入起阻隔空气、减少氧阻聚的作用，有利于表面固化。  \n\n常用的蜡有聚乙烯蜡、聚丙烯蜡和聚四氟乙烯蜡等。  \n\n油墨成分是由固体（如颜料、填料等)、液体（如溶剂、水、活性稀释剂等）和树脂状物质（如天然树脂、高分子合成树脂、低聚物等）组成的，要成为均匀的混合物，就要用机械进行研磨，这是油墨生产的主要工艺。特别是颜料本身是极细颗粒的粒子，但在生产和放置过程中会形成聚集体，需要通过机械研磨使颜料聚集体粉碎至所需的程度，并分散于连结料中，形成均匀而稳定的分散体。通常在油墨制造过程中，采用捏合机或高速搅拌机进行预分散，然后再用高剪切的研磨机械如三辊机、球磨机或砂磨机等进行分散研磨，制得成品，实际生产时，往往先将颜料和少量连结料，加上分散剂，先研磨制成色浆，再用色浆和剩下连结料、填料等研磨制得油墨。  \n\nUV油墨的制造工艺也是如此，只是研磨过程中防止摩擦过热，以免发生暴聚，所以三辊机和砂磨机等研磨设备应注意通水冷却。另外整个UV油墨生产配制过程中避免阳光直射，特别是白色UV油墨。虽然普通照明光源不会对UV油墨有影响，但还是用黄色日光灯比较安全。  \n\n由于印刷方式不同、承印物不同、颜色不同，所以UV油墨品种繁多，要求UV油墨产品能系列化。  \n\n直接将感光胶或菲林安放在丝网上，印刷时用橡胶刮板使油墨通过丝网图文镂空部分漏印至网下承印物上。丝网模板是将蚕丝、尼龙丝、聚酯纤维或不锈钢丝绷在网框上，使其张紧固定而制得。网版印刷过程如图7-4所示。  \n\n![](images/d6d86fe2089721f3f431d258d67ed1e79fe3ab9d069fb4d92bfca5fea7447d69.jpg)  \n图7-4网版印刷过程示意图  \n\n丝网印刷的主要特点如下。  \n\n（1）油墨层厚一般胶印、凸印、柔印的油墨厚度只有几微米，凹印也只有 $9\\sim20\\mu\\mathrm{m}$ ，而网印油墨厚度可达 $30\\sim100\\mu\\mathrm{m}$ ，因此油墨的遮盖能力特别强。  \n\n（2）可使用各种油墨印刷网印可使用溶剂型、水性、辐射固化型多种不同种类的油墨，印品油墨干燥包括挥发干燥、渗透干燥、氧化聚合干燥、光热固化干燥、电子束干燥等。  \n\n（3）版面柔软，印刷压力小，可在各种承印物上印刷丝网印版柔软而富有弹性，所以不仅可在纸张、薄膜、纺织物等柔软的材料上印刷，而且还可在金属、硬质塑料、陶瓷等硬度高的材料上直接进行印刷；因为网印的印刷压力非常小，所以也可以在玻璃等易碎材料上印刷。  \n\n（4）承印物的形状和大小无限制网印能在特殊形状的成型物（瓶杯、工业零件）及各种展平物上印刷，而且能印刷超大型的广告、垂帘等材料，还能在厚膜集成电路等超小型、超高精度的物品上印刷。  \n\n网印的如上特点，使在胶印、凸印、柔印、凹印等难以印刷的情况下，都可以用网印来印刷，所以其用途是非常广泛的。网印可用于纸张、纸板、塑料、厚膜、金属、木材、玻璃、陶瓷、纤维等材料表面的印刷，不管它的形状、厚度和尺寸大小，既可手工操作，又有自动化的机器印刷，故广泛用于包装、装潢、广告、印制电路、电子元器件等领域。  \n\n网印油墨一般黏度较大（1～10Pa·s)，印速较低（5～30m/min），墨层较厚（10～30μm)，因此在制备UV网印油墨时要根据上述特点进行配方设计。 5  \n\nUV网印油墨最常用的低聚物为环氧丙烯酸树脂，固化速率快、综合性能好、价格便宜。也可适当加人聚氨酯丙烯酸树脂，改善脆性，提高柔韧性和附着力。适用于UV网印油墨的低聚物见表7-5和表7-6。  \n\nUV网印油墨使用的活性稀释剂，一般根据油墨黏度、固化速率等要求，选择单、双、多官能度丙烯酸酯搭配使用。对一些要求皮肤刺激性小的装饰性油墨，尽可能使用烷氧基化丙烯酸酯。常用于UV网印油墨的活性稀释剂见表7-7和表7-8。  \n\n表7-5氰特公司推荐用于UV网印油墨的低聚物  \n\n\n<html><body><table><tr><td>产品</td><td>产品类型</td><td>特性</td></tr><tr><td>Ebecryl 745</td><td>25%TPGDA+25%HDDA纯丙烯酸 酯树脂</td><td>对许多塑料都具有良好的附着力，如PE、PP等，并具 有良好的耐候性，但固化速率慢</td></tr><tr><td>Ebecryl 220</td><td>脂肪族聚氨酯丙烯酸酯</td><td>高的固化速率，有一定柔韧性，作助剂使用，特别用于 深色油墨，以促进固化</td></tr><tr><td>Ebecryl 245</td><td>含25%TPGDA的脂肪族聚氨酯丙烯 酸酯</td><td>在柔性或难附着的基材上，是提高附着力的最好树脂 之一，但黏度高</td></tr><tr><td>Ebecryl 2001</td><td>含5%水的脂肪族聚氨酯丙烯酸酯</td><td>可以用水稀释的树脂(可用90%水稀释)，快速固化， 良好的附着力和柔韧性</td></tr><tr><td>IRR376</td><td>含30%TMP(EO)TA的脂肪族聚氨 酯丙烯酸酯</td><td>低体积收缩，很好的附着力和反应速率，特别适用高光 泽和高反应速率的油墨</td></tr><tr><td>Ebecryl 83</td><td>胺改性的聚醚丙烯酸酯</td><td>固化速率快、残留气味低、低黏度，可改善表面固化</td></tr><tr><td>Ebecryl 7100</td><td>叔胺丙烯酸酯</td><td>固化速率快、对塑料出色的附着力；用于改善表面固 化，也可用作附着力促进剂，尤其是塑料基材</td></tr><tr><td>Ebecryl P115</td><td>可共聚的三级胺</td><td>高效助引发剂，改善表面固化；推荐用于纸张</td></tr><tr><td>Ebecryl 436</td><td>含40%TMPTA氯化聚酯丙烯酸酯</td><td>较好的颜料润湿性、良好的固化速率，对塑料和金属附 着力好；推荐用于塑料和金属</td></tr><tr><td>Ebecryl 524</td><td>含30%HDDA的聚酯</td><td>对难附着的基材有良好的附着力，和聚氨酯丙烯酸树 酯相容性好</td></tr><tr><td>Ebecryl 584</td><td>含40%HDDA的氯化聚酯</td><td>固化速率快，对塑料基材具有良好的附着力，不能用于 包装行业</td></tr><tr><td>Ebecryl 605</td><td>含25%TPGDA的标准双酚A环氧丙 烯酸酯</td><td>固化速率快，高光泽，出色的耐溶剂性，常常推荐用于 纸张</td></tr><tr><td>Ebecryl 3701</td><td>柔性的标准双酚A环氧丙烯酸酯</td><td>可改善柔韧性和附着力</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 401,
+        "chunk": "# 表7-6沙多玛公司推荐用于UV油墨的低聚物  \n\n<html><body><table><tr><td>产品</td><td>产品类型</td><td>特 性</td></tr><tr><td>CN929</td><td>三官能度脂肪族聚氨酯丙烯酸酯</td><td>低黏度，不黄变，快速固化；适用于UV柔印、胶印、喷 墨油墨</td></tr><tr><td>CN963B80</td><td>含20%HDDA双官能度脂肪族聚氨 酯丙烯酸酯</td><td>不黄变、耐候性好，坚硬的低聚物；适用于UV网印 油墨</td></tr><tr><td>CN966B85</td><td>含15%HDDA双官能度脂肪族聚氨 酯丙烯酸酯</td><td>高柔韧性，不黄变，改善附着力；适用于UV网印油墨</td></tr><tr><td>CN981</td><td>双官能度脂肪族聚氨酯丙烯酸酯</td><td>快速固化，耐候性好，出色的高拉伸强度和高伸长率； 适用于UV网印油墨</td></tr><tr><td>CN9001</td><td>双官能度脂肪族聚氨酯丙烯酸酯</td><td>对塑料和PC的附着力好，柔韧性和耐候性好；适用于 UV网印油墨</td></tr><tr><td>CN9008</td><td>三官能度脂肪族聚氨酯丙烯酸酯</td><td>快速固化，不黄变，低黏度；适用于UV胶印、凹印、柔 印油墨</td></tr><tr><td>CN9893</td><td>双官能度脂肪族聚氨酯丙烯酸酯</td><td>耐磨性和韧性好，不黄变，适用于UV网印油墨</td></tr><tr><td>CN293</td><td>六官能度聚酯丙烯酸酯</td><td>固化速率快，硬度佳、耐磨性、耐溶剂性和耐化学性好， 适用于UV胶印、柔印、凹印油墨</td></tr><tr><td>CN294</td><td>四官能度聚酯丙烯酸酯</td><td>固化速率快，良好的水墨平衡，对颜料润湿性好，良好 的印刷适性，适用于UV胶印、柔印、回印和网印油墨</td></tr></table></body></html>  \n\n表7-7氰特公司推荐用于UV网印油显的活性稀释剂和附着力促进剂  \n\n\n<html><body><table><tr><td>产品</td><td>产品类型</td><td>特性</td></tr><tr><td>CN750</td><td>三官能度氯化聚酯丙烯酸酯</td><td>对塑料良好的粘接力，耐化学性好，柔韧性好，低固化收缩； 适用于UV胶印、网印油墨</td></tr><tr><td>CN790</td><td>三官能度丙烯酸化聚酯附着力促 进剂</td><td>对聚烯烃良好的粘接力，与多数单体相容，较高黏度，柔韧 性好；适用于UV油墨</td></tr><tr><td>CN2203</td><td>四官能度聚酯丙烯酸酯</td><td>水墨平衡好，颤料分散性好，良好的附着力，柔韧性、耐冲击 性、耐水性好，低固化收缩；适用于UV胶印油墨</td></tr><tr><td>CN 2270</td><td>双官能度聚酯丙烯酸酯</td><td>低黏度，良好的附着力和颜料润湿性；适用于UV柔印、凹 印油墨</td></tr><tr><td>CN2278</td><td>双官能度聚酯丙烯酸酯混合物</td><td>专门为颜料分散的研磨树脂，可有效改进黏度、分散、流平 和光泽，低固化收缩，低黏度；适用于UV柔印、网印和喷墨 油墨</td></tr><tr><td>CN2281</td><td>双官能度聚酯丙烯酸酯</td><td>固化速率快，低黏度、粘接性好；适用于UV柔印、网印和喷 墨油墨</td></tr><tr><td>CN2282</td><td>四官能度聚酯丙烯酸酯</td><td>快速固化反应，颜料润湿性好；粘接性和柔韧性好；适用于 UV胶印、柔印、网印油墨</td></tr><tr><td>CN2284</td><td>聚酯丙烯酸酯</td><td>颜料润湿性好，粘接性好，柔韧性好；适用于UV柔印和喷 墨油墨</td></tr><tr><td>CN2295</td><td>六官能度聚酯丙烯酸酯</td><td>固化速率快，颜料润湿性好，硬度高，耐磨性和耐化学性好； 适用于UV油墨</td></tr><tr><td>CN 111</td><td>环氧大豆油丙烯酸酯</td><td>颜料润湿性、柔韧性和附着力好；适用于UV胶印油墨</td></tr><tr><td>CN118</td><td>双官能度改性环氧丙烯酸酯</td><td>颜料润湿性好，光泽、耐化学性、耐水性和附着力好；适用于 UV胶印、网印油墨</td></tr><tr><td>CN132</td><td>低黏度二丙烯酸酯低聚物</td><td>快速固化，低黏度，柔韧性好；推荐用于需高活性、低黏度的 UV柔印、网印油墨</td></tr><tr><td>CN133</td><td>低黏度三丙烯酸酯低聚物</td><td>快速固化、低黏度、硬度和耐化学性好；适用于各种UV 油墨</td></tr><tr><td>CN371</td><td>双官能度反应性胺助引发剂</td><td>提高深层固化和表面固化速率，低的挥发性和低气味，硬度 高；适用于各种UV油墨</td></tr><tr><td>CN386</td><td>双官能度反应性胺助引发剂</td><td>提高表面固化速率，低的挥发性和低气味，良好附着力；适 用于各种UV油墨</td></tr><tr><td>CN2301</td><td>八官能度超支化聚酯丙烯酸酯</td><td>较低黏度，高固化速率，低体积收缩，适用于UV喷墨油墨</td></tr><tr><td>CN2302</td><td>十五官能度超支化聚酯丙烯酸酯</td><td>低黏度，高固化速率，低体积收缩，适用于UV喷墨油墨</td></tr></table></body></html>  \n\n<html><body><table><tr><td>产品</td><td>产品类型</td><td>特性</td></tr><tr><td>IBOA</td><td>丙烯酸异冰片酯</td><td>良好的附着力和硬度，低体积收缩，但气味大 9</td></tr><tr><td>Ebecryl 1039</td><td>氨基甲酸酯单丙烯酸酯</td><td>非常高的柔韧性，低体积收缩和非黄变性</td></tr><tr><td>Ebecryl-114</td><td>酚乙氧基丙烯酸酯</td><td>低体积收缩，对塑料良好的附着力，柔韧性好</td></tr><tr><td>DPGDA</td><td>二丙二醇二丙烯酸酯</td><td>良好的固化速率、柔韧性和稀释性，在许多塑料上有良好的附 着力</td></tr><tr><td>HDDA</td><td>1,6-已二醇二丙烯酸酯</td><td>低黏度、柔韧性和稀释性好，对塑料有出色的附着力</td></tr></table></body></html>  \n\n续表  \n\n<html><body><table><tr><td>产品</td><td>产品类型</td><td>特性</td></tr><tr><td>TPGDA</td><td>三丙二醇二丙烯酸酯</td><td>良好的固化速率、柔韧性和稀释性</td></tr><tr><td>Ebecryl 140</td><td>双三羟甲基丙烷三丙烯酸酯</td><td>黏度较高，推荐用作助剂，以增加油墨的固化速率</td></tr><tr><td>TMP(EO)TA</td><td>乙氧基化三羟甲基丙烷三丙 烯酸酯</td><td>到良好的油墨流动性和稳定性 通用性好，具有合适的黏度和固化速率，和颜料润湿性好，可得</td></tr><tr><td>TMPTA</td><td>三羟甲基丙烷三丙烯酸酯</td><td>良好的附着力和固化速率，广泛用于网印油墨中</td></tr><tr><td>Ebecryl 168</td><td>酸化的甲基丙烯酸酯</td><td>对金属有附着力促进作用</td></tr><tr><td>Ebecryl 1710</td><td>含60%HDDA的丙烯酸 树脂</td><td>的比例 在不同的基材上具有出色的附着力，配方中需要占20%～30%</td></tr></table></body></html>  \n\n表7-8UV油墨常用的活性稀释剂  \n\n\n<html><body><table><tr><td>活性稀释剂</td><td>官能度</td><td>胶印</td><td>柔印</td><td>凹印</td><td>网印</td><td>喷墨</td></tr><tr><td>2-PEA</td><td>1</td><td></td><td>√</td><td>√</td><td></td><td>√</td></tr><tr><td>三羟甲基丙烷缩甲醛丙烯酸酯(CTFA)</td><td></td><td></td><td>√</td><td></td><td>√</td><td>√</td></tr><tr><td>THFA</td><td>1</td><td></td><td></td><td></td><td>√</td><td></td></tr><tr><td>IBOA</td><td>1</td><td></td><td></td><td></td><td>√</td><td></td></tr><tr><td>EOEOEA</td><td>１</td><td>1</td><td></td><td>√</td><td></td><td>√</td></tr><tr><td>单官能度酸酯(CD9050)</td><td>１</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>HDDA</td><td>2</td><td></td><td>√</td><td>√</td><td>√</td><td>√</td></tr><tr><td>DPGDA</td><td>2</td><td></td><td>√</td><td>√</td><td></td><td></td></tr><tr><td>HD(PO)DA</td><td>2</td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>BPA(EO)DA</td><td>2</td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>NPG(PO)DA</td><td>2</td><td>√</td><td>√</td><td></td><td></td><td>√</td></tr><tr><td>HD(EO)2DA</td><td>2</td><td></td><td>√</td><td></td><td></td><td>√</td></tr><tr><td>BPA(EO)DA</td><td>2</td><td></td><td>√</td><td>√</td><td>√</td><td></td></tr><tr><td>1,3-丁二醇二丙烯酸酯(BGDA)</td><td>2</td><td></td><td></td><td></td><td></td><td>√</td></tr><tr><td>TMP(EO)TA</td><td>3</td><td>√</td><td>√</td><td>√</td><td>√</td><td>√</td></tr><tr><td>TMP(PO)3TA</td><td>3</td><td>√</td><td>√</td><td>√</td><td></td><td></td></tr><tr><td>GPTA</td><td>3</td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>DTMPTA</td><td>４</td><td>√</td><td>√</td><td>√</td><td></td><td>√</td></tr><tr><td>DPETA</td><td>4</td><td></td><td></td><td></td><td>√</td><td>√</td></tr><tr><td>PE(EO)TA</td><td>4</td><td></td><td>√</td><td>√</td><td></td><td>√</td></tr><tr><td>DPEHA</td><td>5</td><td>√</td><td>√</td><td></td><td></td><td></td></tr></table></body></html>\n\n注：“√”代表可以选用。  \n\nUV网印油墨所用的光引发剂，通常以ITX与907配合为主，对红、黄两色油墨可加651，黑色油墨以369代替907，白色油墨则用TPO或819与184配合。要提高光固化速率，可适当加0.5%～1.0%TPO。  \n\nUV网印油墨所用颜料与一般油墨类似，由于油墨层厚，所以颜料用量较少，一般在$5\\%\\sim8\\%$ 。  \n\nUV网印油墨黏度较大，而颜料添加量又较少，可加入较多的填料调节黏度，特别加人折光性较好的透光填料，有利于墨层底部的固化。填料价格便宜，可降低油墨成本，填料加入时减少固化体积收缩，也可提高附着力。为了改善网印的滑爽性，常添加滑石粉。  \n\nUV网印油墨为了改善印刷适性，提高网印质量，也需添加助剂如消泡剂和流平剂，使用有机硅类或含氟类助剂时，要考虑重涂性，即套色印刷时，表面张力低的色墨印在表面张力高的色墨上，对厚油墨层或有触变性要求的墨层，要用触变剂气相 $\\mathrm{\\SiO}_{2}$ 。  \n\nUV网印油墨制造一般都将低聚物、活性稀释剂、光引发剂和颜料及填料用捏合机或高速搅拌机混合后，再用三辊机研磨至所需的细度，就得到成品。  \n\n在包装印刷行业中近年来也利用UV固化技术而开发出一系列具有特殊装饰效果的网印油墨。采用UV装饰性油墨，提高了包装印刷的档次，成为高档烟、酒、茶、保健品、礼品、工艺品印刷包装和请柬、贺卡、挂历、装饰材料印刷的重要材料。  \n\nUV装饰性油墨是人们利用油墨印刷过程中常会产生气泡、缩孔、疵点、皱纹、橘皮、晶纹等缺陷，人为地通过不同手段加以夸大，从而产生皱纹、磨砂、折光、珊瑚、冰花等图案。具有很好的装饰效果，并发展成新的UV网印油墨系列。  \n\nUV装饰性油墨种类很多，根据是否添加特殊填料，大致可有如下三类：$\\textcircled{1}$ 不添加填料，有折光油墨、皱纹油墨、珊瑚油墨、立体光栅油墨等；$\\textcircled{2}$ 添加特殊填料，有磨砂油墨、宝石油墨、珠光油墨等；$\\textcircled{3}$ 添加微胶囊填料，有香味油墨、发泡油墨等。由于UV装饰性油墨主要用于烟、酒、茶、保健品、化妆品、请柬、贺卡等高档包装印刷，所以必须要做到如下几点。（1）无味环保要不含有任何带有不愉快气味的成分，油墨和印刷过程均无气味，对印刷车间和包装车间没有污染。（2）安全无刺激油墨对人体皮肤无刺激，避免操作人员因不小心接触而造成皮肤过敏或灼伤，保障操作人员的安全。油墨组分固化后不易发生迁移，以免污染产品。（3）附着力好，耐刮性强油墨对纸质承印物，特别是通用的金银卡纸具有极好的附着牢度及表面硬度，印品的耐刮和耐划伤性要好。（4）高耐冲击性和柔韧性鉴于印品在印刷后，往往还要通过压凸、模切等具有冲击性的后道加工工序，要求油墨层在印品上有耐冲击性和一定柔韧性。  \n\n因此在生产UV装饰性油墨时，要选择好低聚物、活性稀释剂和光引发剂，特别要选用无味、皮肤刺激性小的活性稀释剂和迁移小、光解产物无味的光引发剂。 SIA",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 402,
+        "chunk": "# 7.3. 1 UV折光油墨  \n\n折光（镭射）油墨是用于折光（镭射）印刷的一种特殊油墨。折光实际上是指反射光而非折射光，所以折光印刷又称反光图纹印刷。折光印刷利用光的反射原理实现其特殊的装饰效果，它采用光反射率高的材料—通常是金银卡纸、涂铝薄膜或镜面不锈钢等作基材。传统的折光效果是通过精心设计制出带有折光纹理的铜锌版，用凸版印刷机在金银卡纸上压出不同角度的线条，产生折光（镭射）纹理，但该方法的缺点是制版成本高，效果也不甚理想。现可用精细的丝网制版技术与先进的桌面排版制作技术结合，用网印方法在镜面金银卡纸上印上折光油墨即可获得多彩的折光图案，这些有规律、凹凸状的图案在光的照射下，能产生有层次的光闪耀感以及三维立体的独特效果。折光图案精细、复杂，它是由几十段角度、弧度不同的线条通过同等距离的排列组成，其线条粗细在0.10～0.15mm，因此要求折光油墨具有高光泽、高分辨率和良好的触变性，保证网印后线条清晰。折光印刷现在大多采用网印印刷，使用UV折光油墨。折光印刷主要应用于烟、酒包装及工艺品、请柬、挂历、贺卡等商品包装印刷，印刷后不但能使包装商品光耀夺目、富丽华贵、立体感强，而且还具有一定的防伪效果。",
+        "category": " Introduction"
+    },
+    {
+        "id": 403,
+        "chunk": "# 7.3.2 UV皱纹油墨  \n\n通常情况下，油墨在干燥时，若表面层与底层的收缩不同，则会产生起皱现象。这种现象本来是印刷中的缺陷，但如果有意识地突出和控制起皱现象，使其形成一种图纹的独特装饰效果，就可以使印刷品别有一番韵味，能产生这种效果的油墨就是皱纹油墨。将皱纹油墨印刷在金银卡纸等承印物表面，经特定波长的紫外线照射后，墨膜表面收缩形成皱纹，具有金属锤打或折皱的表面效果，所以皱纹油墨也称锤纹油墨。其实皱纹漆早已存在，常涂装在电器设备或机器外壳上，但它需要经高温烘烤，才能得到满意的皱纹效果。此工艺无法应用于以纸为基材的包装材料上。而UV皱纹油墨巧妙利用了UV油墨两次固化的工艺，先用低压汞灯照射，使油墨表面局部固化，然后用中压汞灯照射彻底固化，由于油墨固化时体积收缩，引起油墨层分布不匀，产生了起皱现象。UV皱纹油墨采用网印印刷，要根据需要达到的皱纹效果选择不同的网目。选用的丝网目数越大，印品精度越高，油墨层就薄，则产生的皱纹效果越小；反之，选用丝网目数小，油墨层厚，产生的皱纹效果大。一般常用100～200目的丝网。UV皱纹油墨主要用于金银卡纸、塑料薄膜、金属、玻璃等基材，作高档烟、酒包装以及挂历、标牌、工艺制品的印刷，典雅高贵，有很好的装饰效果。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 404,
+        "chunk": "# 7.3.3 UV珊瑚油墨  \n\n墨层中有气泡出现本来是印刷时产生的缺陷，但如在墨层中有大量气泡聚集在一起并组成图案，则可产生特殊的装饰效果，UV珊瑚油墨就是利用该原理制成的。珊瑚油墨又可称为珍珠油墨，这是因为印得厚，气泡聚集在一起形成珊瑚状花纹；印得薄，则形成小珍珠粒状。使用UV珊瑚油墨时，要根据所需的花纹选择合适的丝网目数。通常要印小珍珠状花纹时，丝网用高网目，可用250～300目丝网印刷；如要印粗珊瑚状花纹，丝网要用粗网目，刮刀口钝些。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 405,
+        "chunk": "# 7.3.4 UV冰花油墨  \n\n有些涂料在干燥时，特别是受到二氧化氮、二氧化硫、二氧化碳等气体的影响，涂膜的表面会产生晶纹。而晶纹、霜花、网纹、丝纹都是皱纹的不同表现形式，是涂层的一种缺陷。但如能控制条件在涂层表面恰当地生成晶纹，则能产生晶莹透彻的类似于冰花的装饰效果，这就是制作冰花油墨的机理。冰花油墨包括热固化型和UV固化型，但只用于小批量的印刷，还未能在包装行业中大量使用。主要原因是产生冰花所需的UV照射时间过长，生产效率太低，耗能过高，承印的纸张易变形。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 406,
+        "chunk": "# 7.3.5 UV磨砂油墨  \n\nUV磨砂油墨又称UV仿金属蚀刻油墨。油墨中含有杂质时就会产生疵点，如果在UV油墨中加人大量的对光线产生散射效果的“杂质”，通过网印墨膜表面会产生许多小颗粒，这样在一般卡纸上印刷，墨膜可产生砂面效果。若印在高光泽的金银镜面卡纸上，油墨中小颗粒对光发生漫反射，看上去好像镜面被腐蚀，产生凹下去的错觉，而没有印刷上磨砂油墨的图文处，由于高光泽的金属镜面在光照下为正反射，金属光泽质感强烈显著，感到凸出来，这就是UV磨砂油墨的机理。UV磨砂油墨分粗砂、中砂和细砂三种规格，现广泛地应用于烟、酒、茶、化妆品、礼品及医药包装上，也常用于贺卡、挂历、请柬、广告等印刷中。磨砂油墨还可以产生绒面及亚光效果，可使印品柔、庄重、高雅、华贵，达到一般油墨难以达到的效果。",
+        "category": " Introduction"
+    },
+    {
+        "id": 407,
+        "chunk": "# 7.3.6 UV宝石油墨  \n\n宝石油墨又称大理石油墨或水晶透明（七彩）油墨。它是由高浓缩、高透明、高膨胀性的不黄变的UV光油演变而成。UV宝石油墨有极好的触变性，经丝网印刷和固化后在印刷部位从视觉和手感上都有十分厚实的效果，像水晶、雕刻、滴胶一样的感觉。若混合七彩粉、幻彩片一起印刷，效果像七彩宝石般美丽。UV宝石油墨一般用于印刷图案的轮廓或图案的局部区域，使图案显得十分丰满厚实。现广泛应用于包装、挂历、贺卡、书本、名片等各种纸张上和覆膜底材上。",
+        "category": " Introduction"
+    },
+    {
+        "id": 408,
+        "chunk": "# 7.3.7 UV珠光油墨  \n\n珠光油墨是将云母珠光颜料加人油墨中而制得的一种具有珠光效果的特种油墨。云母珠光颜料是利用云母片的反射或闪光效应，将其制作成表面具有珠光色彩的微粒。云母是天然硅酸盐，大多数云母矿不适合作珠光颜料，只有密度为2.7～3.lg/cm、硬度为2.0～3.0的单斜晶系的白云母KAlO1oSi(OH)z才适合制作云母珠光颜料。将透明的白云母晶体处理成颗粒状后，用化学方法将二氧化钛等金属氧化物涂覆于云母粉末表层，既可提高云母表面的耐光、耐候性，还可通过调节色膜厚度，来获得各种干涉色(表7-9 和表7-10)  \n\n表7-9氧化钛膜的色相与膜厚的关系  \n\n\n<html><body><table><tr><td>色相(反射、透射)</td><td>光学厚度/nm</td><td>几何厚度/nm</td><td>每平方米云母需TiOz的质量/mg</td></tr><tr><td>银</td><td>140</td><td>60</td><td>85</td></tr><tr><td>金紫</td><td>210</td><td>90</td><td>102</td></tr><tr><td>赤绿</td><td>265</td><td>115</td><td>186</td></tr><tr><td>紫黄</td><td>295</td><td>128</td><td>231</td></tr><tr><td>青橙</td><td>330</td><td>143</td><td>250</td></tr><tr><td>绿赤</td><td>395</td><td>170</td><td>275</td></tr></table></body></html>  \n\n表7-10云母钛粒度与氧化钛的附着力  \n\n\n<html><body><table><tr><td>粒度/μm</td><td>反射光</td><td>附着力/%</td><td>云母厚度/μm</td></tr><tr><td>1.0~130</td><td>银白</td><td>20</td><td>0.6</td></tr><tr><td>10~60</td><td>银白</td><td>28</td><td>0.4</td></tr><tr><td>5~30</td><td>银白</td><td>34</td><td>0.3</td></tr><tr><td>5~15</td><td>银白</td><td>40</td><td>0.25</td></tr><tr><td>10~60</td><td>金</td><td>39</td><td>0.35</td></tr><tr><td>10~60</td><td>红</td><td>45</td><td>0.35</td></tr><tr><td>10~60</td><td>紫</td><td>48</td><td>0.35</td></tr><tr><td>10~60</td><td>青</td><td>51</td><td>0.35</td></tr><tr><td>10~60</td><td>绿</td><td>55</td><td>0.35</td></tr></table></body></html>  \n\nUV珠光油墨可印在几乎所有的材料上，如纸张、塑料、金属、玻璃、陶瓷、织物等，特别以纸张、针织品上应用较多。网印珠光油墨时，最重要的是珠光颜料颗粒大小要同丝网目数相匹配，见表7-11。  \n\n表7-11丝印中的珠光颜料参数  \n\n\n<html><body><table><tr><td>颗粒大小/μm</td><td><15</td><td>5~25</td><td>10~60</td><td><200</td></tr><tr><td>丝网目数/（目/in）</td><td>160</td><td>140</td><td>60</td><td>22</td></tr></table></body></html>\n\n注： $\\scriptstyle1\\mathrm{in}=2,54\\mathrm{cm}$ 。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 409,
+        "chunk": "# 7.3.8 UV立体光栅油墨  \n\nUV立体光栅油墨主要用于印刷立体光栅模片。与传统的热压成型工艺不同，新工艺采用网印方法，将UV油墨印在透明膜片上，直接形成柱状光栅图形；也可将UV立体光栅油墨直接印在印刷品上，形成立体图案；还可选择性地印刷局部图案，使局部图案立体化。采用UV立体光栅油墨印出的图案立体效果明显，与热压光栅板不相上下，为三维印刷开辟了一种新方法。利用UV立体光栅油墨印刷光栅片可以大大降低生产成本，提高生产效率。印刷基材可以是透明的塑料薄膜，如 PVC、PC、PET，也可以是纸张、金属、玻璃、陶瓷等。丝网目数以200～350目为佳。UV立体光栅油墨是无色透明，固化膜不黄变，附着力好，韧性好。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 410,
+        "chunk": "# 7.3.9 UV香味油墨  \n\n人们在印刷上除了追求视觉美的效果外，香味印刷也是一个努力方向。最早是在印墨或纸中加入香料以得到香味，这种方法简单，但不易持久。后来人们发明了微胶囊技术，将香料封人微胶囊内，并制成香味油墨进行印刷。由于香料被微胶囊封闭，徐徐散发出来，故印品能持久飘香。在油墨固化后用手指轻轻摩擦，即可闻到浓郁的香味。微胶囊一般壁厚1μm或1μm以下，直径在10～30um，香味油墨采用网版印刷时丝网网目可选用200～300目；也可采用凸印或凹印。香味印刷主要应用于杂志、广告、传单、说明书、明信片、餐单、日历、数字挂图等方面，也可用于织物印花。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 411,
+        "chunk": "# 7.3.10 UV发泡油墨  \n\n发泡油墨是一种在承印物上形成立体图案的装饰性油墨，由于印刷图案富有立体感，可增强装饰艺术效果。发泡油墨也是采用微胶囊技术制备而成，在微胶囊中充人发泡剂，经加热处理，发泡剂释放气体，使微胶囊体积增大到原体积10～30倍，将此种微胶囊制成发泡油墨。常用发泡剂的性能见表7-12。  \n\n表7-12常用发泡剂的性能  \n\n\n<html><body><table><tr><td>发泡剂名称</td><td>分解温度/℃</td><td>分解气体</td><td>发气量/(mL/g)</td></tr><tr><td>对甲苯磺酸酰胺</td><td>105</td><td>N2</td><td>130</td></tr><tr><td>苯磺酸酰胺</td><td>105</td><td>Na</td><td>130</td></tr><tr><td>偶氮二甲酰胺</td><td>120</td><td>N2</td><td>230~250</td></tr></table></body></html>  \n\n发泡油墨主要采用网印，为提高发泡效果，需要增加油墨层厚度，一般采用低网目丝网 80～120目。当印刷批量大时，也可采用凹印。发泡油墨主要应用于棉织品、壁纸和盲文等印品。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 412,
+        "chunk": "# 7.3.11 UV凹印和柔印装饰性油墨  \n\nUV装饰性网印油墨品种繁多，性能单一，有的使用麻烦、生产能力低，为此人们又设法采用凹版印刷和柔版印刷来印刷具有装饰性图案，从而研制开发了UV装饰性凹印油墨和UV装饰性柔印油墨。这是我国自行研发的包装印刷技术和装饰性油墨，不但具有完美的装饰效果，而且具有很好的防伪效果。  \n\n（1）凹版印刷法印刷装饰性油墨，主要通过用电雕刻法或激光雕刻法对装饰性图案进行制版，同时研制了与其配套使用的UV装饰性凹版油墨，并在凹版印刷机上安装了UV固化设备来实现。凹印所产生的图案是由制版时的网点及线条的排布、大小及深浅来决定的，只要在一个印版上制作不同效果的磨砂、折光、冰花、皱纹或珊瑚等图案，用一种油墨就可印出不同的装饰性图案，使印品更富有艺术性。鉴于凹印的印刷一致性好，只要一个印版，用同一油墨及同一种纸，即使印上百万张，其统一性也很好，固化具有很好的防伪功能。由于凹版印刷速率快，墨层厚，难以彻底固化，为此UV装饰性凹印油墨除了采用新型低聚物、活性稀释剂与光引发剂，巧妙组合搭配外，还添加了能提高固化速率和克服氧阻聚的纳米材料，制备了印刷速度高于150m/min的UV装饰性凹印油墨。  \n\n（2）柔版印刷法印刷装饰性油墨则采用数字激光柔性版技术制作柔性版，传墨用网纹辊尽量达到可转移10μm以上的墨层厚度，用光学性能好（高折射率或高散射性）的材料制作UV油墨，经组合使用得到实现，印品不但装饰效果完满，同时还有很好的防伪效果。由于柔印工艺的限制，所印的油墨层较薄，如需印刷一些具有特殊效果的厚墨层，则可用辊筒式网印机进行印刷，为此又开发了适用于辊筒式网印机的UV装饰性网印油墨。  \n\n胶印又叫平版印刷，是在印刷领域内应用最广泛的一种印刷方法。胶印印版的图文部分和非图文部分基本上是处于同一平面上，仅有稍微的高低之差，利用油水相斥的原理印刷。图文部分是憎水性的(亲油墨)，非图文部分是亲水性的(斥油墨)。印刷时先用润版液润湿非图文部分，图文部分是斥润版液的；再由墨辊传递油墨，图文部分接受油墨，而非图文部分斥油墨；图文部分油墨再转移到橡胶辊筒，然后传给承印物，是间接印刷。胶印印刷过程如图7-5所示。  \n\n胶印的主要特点为：  \n\n$\\textcircled{1}$ 油墨厚度很薄，一般胶印油墨单色厚度 $2\\mu\\mathrm{m}$ 左右；  \n② 由于墨辊和水辊交替与印版接触，故对油墨印刷适性要求极高，同时要防止油墨乳化；  \n③胶印的印刷速度快，一般在100～400m/min;  \n$\\textcircled{4}$ 胶印油墨黏度高，颜料浓度高，着色力也高；  \n③套印精度高（压力小)，图文再现性好，网点清晰，层次丰满。  \n\n根据胶印的上述特点，UV胶印油墨配方设计应考虑低聚物和活性稀释剂要有较好的抗水性能，在印刷中墨辊和水辊不会交替接触，发生乳化现象。UV胶印油墨中颜料浓度高，为了更好地分散颜料，常选用对颜料分散性能好的聚酯丙烯酸酯作为主体树脂成分；由于胶印印刷速率快，低聚物和活性稀释剂要选用固化速率快、官能度高的树脂和单体，常用于  \n\n![](images/1d1d2edc4ad893b43778729d3b85cab8b3ba51fd2e8a685262ccd6cae34506ba.jpg)  \n图7-5胶印印刷过程示意图  \n\nUV胶印油墨的低聚物见表7-6、表7-13和表7-14，常用于UV胶印油墨的活性稀释剂见表 7-8。  \n\n表7-13氰特公司推荐用于UV胶印油墨的低聚物  \n\n\n<html><body><table><tr><td>产品</td><td>产品类型</td><td>特性</td></tr><tr><td>Ebecryl 436 Ebecryl 438</td><td>含40%TMPTA的氯化聚酯 含40%OTA480的氯化聚脂</td><td>中等的颜料润湿性，良好的固化速率，在塑料和金属上 有良好的附着力；推荐用于塑料、金属上</td></tr><tr><td>Ebecryl 450</td><td>六官能度聚酯丙烯酸酯</td><td>高固化速率，优良的颜料润湿性、良好的水油平衡性、 低黏度树脂，通常用于难以润湿的颜料（如黄色)，以得到</td></tr><tr><td>Ebecryl 657</td><td>四官能度聚酯丙烯酸酯</td><td>较好的油墨流动性；推荐用于纸张上 优良的颜料润湿性、出色的水油平衡性，通常用于单张</td></tr><tr><td>Ebecryl 870</td><td>六官能度聚酯丙烯酸酯</td><td>印刷工艺；推荐用于纸张上 非常快的固化速率，优良的颜料润湿性和水油平衡性，</td></tr><tr><td>Ebecryl 600</td><td>标准双酚A环氧丙烯酸酯</td><td>通常用于轮转印刷工艺；推荐用于纸张上 通用性强、高固化速率</td></tr><tr><td>Ebecryl 860</td><td>环氧大豆油丙烯酸酯</td><td>良好的流动性能和颜料润湿性，通常用作助剂</td></tr><tr><td>Ebecryl 954</td><td>标准双酚A环氧丙烯酸酯</td><td>低黏度，高固化速率、通用性强，最容易使用的产品</td></tr><tr><td>Ebecryl 2958</td><td>改性的标准双酚A环氧丙烯酸酯</td><td>通用性强，高固化速率，对无机颜料（白色、黑色）润湿性好</td></tr><tr><td>Ebecryl 3608</td><td>含15%OTA480的脂肪酸改性的环氧</td><td>优良的颜料润湿性、良好的水油平衡性，用于提高流动</td></tr><tr><td>Ebecryl 3700</td><td>丙烯酸酯 标准双酚A环氧丙烯酸酯</td><td>性的助剂，特别是红色 良好的颜料润湿性和固化速率，通用性强</td></tr><tr><td>Ebecryl 3702</td><td>脂肪酸改性的环氧丙烯酸酯</td><td>低气味、良好的流动性和流平性、非常好的颜料润湿性</td></tr><tr><td>Ebecryl 220</td><td>六官能度芳香族聚氨酯丙烯酸酯</td><td>和水油平衡，作增加油墨流动性助剂用 非常高的固化速率，通常作助剂，适用于深色油墨中， 以提高固化速率</td></tr></table></body></html>  \n\n表7-14沙多玛公司推荐用于UV油墨的新低聚物  \n\n\n<html><body><table><tr><td>产品</td><td>特性</td></tr><tr><td>PRO30185</td><td>良好的水墨平衡性和附着力，快的固化速率，无苯，低成本，用于UV胶印油墨 H</td></tr><tr><td>PRO 30187</td><td>良好的水墨平衡性和附着力，出色的颜料润湿性，无苯，低成本，用于UV胶印油墨</td></tr><tr><td>PRO30190</td><td>良好的水墨平衡性，出色的附着力，优异的柔韧性，好的流动性，用于UV胶印油墨</td></tr><tr><td>PRO30181</td><td>优异的附着力、拉伸性能、耐高温性能和良好的耐冲击性，用于UV网印油墨</td></tr></table></body></html>  \n\nUV胶印油墨所用的光引发剂，通常也是以ITX和907复合为主，对红、黄两色油墨可加651，而黑色油墨以369代替907，白色油墨则用TPO或819与184配合。为了提高光固化速率，可加人适量TPO、819等。现在一些新型大分子光引发剂，如大分子氨基苯乙酮光引发剂Polymerie9l0、大分子 $\\alpha$ 羟基酮光引发剂Irgacure127、大分子酮酯光引发剂IrgacureOXEOI、大分子酰基麟化氧光引发剂、大分子胺烷基酮光引发剂 Rad-Start N-1414都有较高的光引发活性，适合用于UV油墨的光引发。  \n\nUV胶印油墨所用颜料最大，一般都在 $15\\%\\sim21\\%$ ，所以研磨、分散非常重要，一般都用分散树脂和部分活性稀释剂先在砂磨机上研磨、分散制成色浆，再将色浆和其余组分用三辊机研磨制成油墨。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 413,
+        "chunk": "# 7.5UV凸印油墨  \n\n凸印是印刷工业的始祖，是最早利用的一种印刷方法，从宋代毕升发明的胶泥活字印刷，至元朝王桢发明的木刻活字印刷，15世纪德国人古登堡发明铅活字印刷都是凸版印刷。凸版印刷中，图文部分在印版表面凸起，油墨只施于图文部分，然后直接传给承印物。凸印有平台型和轮转型两种，平台型是以印版为平面，压印辊简为圆筒式，而轮转型指印版和压印辊简都是圆筒式结构。  \n\n凸版印刷由于印刷质量不如胶印和柔印，印刷速率也不如胶印和柔印，现在使用越来越少，因此凸印油墨生产也越来越少。UV凸印油墨可参考7.6节UV柔印油墨。  \n\n柔性版印刷也是凸版印刷的一种，它是一种应用柔软、带有弹性的橡皮版或弹性体版来印刷的轮转型凸版印刷。柔性版印刷最早应用于1890年，当时采用橡胶做版材，发展较慢，直到1970年杜邦公司发明了感光性树脂柔性版（Cyrel版)，使制版速率和精度大大提高，柔性版印刷进人了发展新时期。由于柔印工艺适应性广，对不同承印材料都能适用，除了传统的纸张，一些非吸收性承印材料如玻璃纸、塑料薄膜、塑料制品、金属箔（如铝箔)、玻璃制品等，以及在较厚的纸板、瓦楞纸上都能印刷。印刷成本较低，能进行多色套印，印刷质量接近胶印，印刷速率也较快（可达 $300\\mathrm{m/min})$ ；同时裁切、成型、模切、穿孔、折页、烫金、覆膜或上光等工序可以连成一条生产线，生产效率极高，自动化程度也很高，所以近年来发展很快，特别在包装印刷中广泛应用。目前软包装印刷、瓦楞纸箱印刷、不干胶标签、折叠纸盒的印刷几乎都用柔性版印刷，部分报纸和杂志印刷也采用柔印。  \n\n柔性版印刷过程是油墨经网纹传墨辊传到柔印印版，由墨刀刮去多余的油墨，柔性印版安在印刷辊筒上，由网纹辊将油墨转移到印版，再由印版直接转移压印到承印物表面（图7-6）  \n\n柔印油墨黏度较低，一般在 $0.1{\\sim}2\\mathrm{Pa}\\cdot\\mathbf{s}$ ，是一种接近于牛顿流体的油墨。因为主要用于印刷包装材料，所以要求油墨色彩要鲜艳，透明度要好，而且光泽也要好。柔性版印刷的墨层比较薄，一般在 $4\\mu\\mathrm{m}$ 左右，所以柔印油墨中颜料含量也较高，一般在 $12\\%\\sim18\\%$ 。  \n\nUV柔印油墨的配方设计上，低聚物要选用黏度低、固化速率快、对颜料分散润湿性好  \n\n![](images/48d1bf76161644faa643e1a6d50e55a4207547a0b57d2a03d6fe0ba933836855.jpg)  \n图7-6柔性版印刷过程示意图  \n\n的聚酯丙烯酸酯和环氧丙烯酸酯（表7-6和表7-15)；活性稀释剂选择见表7-8、表7-15，光引发剂选择可参见7-4UV胶印油墨。  \n\n表7-15氰特公司推荐用于UV柔印油墨的低聚物和活性稀释剂  \n\n\n<html><body><table><tr><td>产品</td><td>产品类型</td><td>特性</td></tr><tr><td>DPGDA</td><td>二丙二醇二丙烯酸酯</td><td>良好的固化速率和柔韧性，稀释性强</td></tr><tr><td>TMP(EO)3TA</td><td>三乙氧基三羟甲基丙烷三丙烯酸酯</td><td>良好的黏度、固化速率和颜料润湿性；所制得的油墨具 有良好的流动性和稳定性</td></tr><tr><td>Ebecryl 140</td><td>二缩三羟甲基丙烷四丙烯酸酯</td><td>黏度较高，建议作为助剂使用以提高油墨固化速率</td></tr><tr><td>Ebecryl 145</td><td>丙氧基化新戊二醇二丙烯酸酯</td><td>具有出色的附着力和固化速率</td></tr><tr><td>Ebecryl 40</td><td>聚醚四丙烯酸酯</td><td>固化速率快、不宜渗透，建议用于纸张类材料</td></tr><tr><td>Ebecryl 436</td><td>含40%TMPTA的氯化聚酯</td><td>中等的颜料润湿性，用于难附着的基材上，通常作助剂 使用；推荐用于塑料和金属上</td></tr><tr><td>Ebecryl 450</td><td>六官能度聚酯丙烯酸酯</td><td>固化速率快、非常好的颜料润湿性、低黏度，用于低黏 度、高印刷速度系统；推荐用于纸张</td></tr><tr><td>Ebecryl 657</td><td>四官能度聚酯丙烯酸酯</td><td>非常出色的颜料润湿性，对不同颜料通用性强，黏度较 高，但可用于柔印油墨；推荐用于纸张</td></tr><tr><td>Ebecryl812</td><td>四官能度聚酯丙烯酸酯</td><td>低黏度及出色的颜料润湿性，兼有良好的固化速率和 附着力；推荐用于塑料</td></tr><tr><td>Ebecry1 2958</td><td>改性的双酚A环氧丙烯酸酯</td><td>通用性强，特别适用于无机颜料（白色和黑色）</td></tr><tr><td>Ebecryl 3700</td><td>标准双酚A环氧丙烯酸酯</td><td>出色的颜料润湿性和固化速率快，通用性强</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 414,
+        "chunk": "# 7.7 UV凹印油墨  \n\n凹印与其他印刷方法不同的是它的印版上经过腐蚀或者雕刻；形成很多低于印版表面的不同容积的着墨孔，这些着墨孔形成了凹印印版的图文。在印刷过程中，印版辊筒表面浸入墨槽中，表面上的着墨孔填满了油墨；由刮墨刀将多余油墨刮掉，只在着墨孔内充满油墨；印版辊筒继续转动，着墨的印版辊筒与承印物和压印辊相互接触，在压力作用下，着墨孔内的油墨接触承印物，由于承印物具有吸附性，油墨转移到承印物上；随着印版辊筒继续转动，着墨印版与承印物分离，这时一部分油墨转移到承印物上，一部分油墨流回着墨孔中，完成印刷过程 (图7-7)。  \n\n在印刷过程中，凹印印刷工艺比胶印简单，不存在胶印的水墨平衡，而且是直接印刷，其颜色再现和色彩的一致性更好，而且废品率低，承印物浪费少，特别是耐印力远比胶印高，印数可达50万印以上，非常适用于高档烟酒包装的印刷。凹印最大特点是印品的墨膜比较厚，一般在${\\vartheta\\sim}20\\mu\\mathrm{m}$ ，比柔印的墨膜几乎要厚一倍，印品立体感强，层次清晰，色泽鲜艳和饱满。凹印油墨黏度很小，通常在 $20{\\sim}300\\mathrm{mPa}\\cdot\\mathrm{\\s}$ 之间，以保证油墨具有良好的传递性能，得到优良的印品质量。凹印的使用范围较广，纸张、薄膜、铝箔等都可印刷，而且印刷速率快（一般在 $100{\\sim}300\\mathrm{m/}$ $\\mathrm{{\\min}})$ 。凹印油墨由于墨层厚，所以油墨中颜料的含量相对比较低，一般在 $6\\%\\sim9\\%$ 之间。  \n\n![](images/0badcfa484250b623ac44b8026725b903fbdede43d792a4af4069ea96f7755b8.jpg)  \n图7-7凹版印刷过程示意图  \n\nUV凹印油墨在配方设计上与UV柔印油墨接近，要选用低黏度、固化速率快的低聚物和活性稀释剂，见表7-6和表7-8。光引发剂的选择可参见7.4节UV胶印油墨。  \n\n移印是使用可以变形的移印胶头将印版上的图文区的油墨转移到承印物上。移印的印刷过程是由供墨装置给移印印版供墨，刮墨装置刮去印版空白处的油墨，移印胶头压到移印印版上，蘸取图文区油墨，在胶头表面形成反向的图文，然后移印胶头在承印物上压印，把油墨转移到承印物上，完成印刷(图7-8)。移印工艺的印版和刮墨过程与凹印近似，而移印胶头转移油墨过程又与胶印中橡胶皮布转移油墨图像的间接印刷方式相似。但凹印的印版是辊筒式的，而移印印版则是平面式的；凹印采用黏度较低的油墨，而移印油墨则黏度较高。胶印的油墨转移方式是滚动传递，而移印油墨属于平动传递，因而移印的变形和误差要比胶印大得多。网印被誉为“万能印刷”，但对于小型工件如直径小于 $10\\mathrm{mm}$ 的玻璃球、较大曲率的曲面（如 $180\\mathbf{mm}$ 的球面）和非单一平面的工件难以施印，而移印工艺正可弥补网印的这些局限性，可对特殊表面进行印刷加工。因此移印犹如网印的“李生姐妹”，兼有网印的优点，如对承印物的适应性广、成本低廉，可使用绝大多数的网印油墨；又有其独到之处，如适合小面积、凹凸面的图文印刷，印刷灵活性大且易于套色等。移印是网印绝佳的搭档，互补双赢。  \n\n![](images/e4160da5aaa9d5a515a4946eba7e22bedb841337d75a648f30ade9404cb0c83a.jpg)  \n图7-8移印工艺流程示意图  \n\n移印工艺也是属于间接印刷，移印胶头表面传递的墨量有限，一般情况下，移印胶头能蘸取的墨量为移印印版凹处油墨总厚度的2/3，而移印到承印物的墨层厚度也只有移印胶头表面墨层厚度的2/3，因此承印物表面的墨层厚度大致是印版图文墨层深度的4/9，故印刷墨层较薄，要获得较醒目的图文，移印油墨中颜料含量要比网印油墨高，细度也更细。移印胶头是移印工艺所特有的，它具有优异的变形性和回弹性，移印胶头在压力作用下能与承印物的表面完全吻合以实现印刷。但移印过程中，一方面移印胶头靠压力产生的变形来传递油墨；另一方面移印胶头的变形也会造成印迹变形，网点增大。为减少这种影响，要求移印油墨的触变性好。  \n\nUV移印油墨配方设计，可参考7.2节UV网印油墨。  \n\n喷墨印刷是一种非接触式、无压力、无印版的印刷方式，由系统控制器、喷墨控制器、喷头和承印物驱动机构等组成。通过计算机编辑好图形和文字，并控制喷墨打印机喷头，喷射墨滴到承印物而获得精确的图像，完全是数字化印刷的过程。作为数字化技术和计算机技术相结合的产物，喷墨印刷已成为数字化印刷领域中发展最迅速、应用最广泛的一种印刷方式。  \n\n喷墨印刷作为一种全数字化印刷具有很多特点：  \n\n$\\textcircled{1}$ 完全脱离了传统印刷工艺的烦琐程序，对市场反应快速，作业准备时间和生产周期短。$\\textcircled{2}$ 可以用非常高的时间效率和低成本效率完成数字样张和短版作业的生产。$\\textcircled{3}$ 可以可变数据印刷和按需印刷，实现个性化印刷。$\\textcircled{4}$ 通过互联网传输，实现异地印刷。$\\textcircled{5}$ 可在不同材质：纸张、纸板、薄膜、塑料、金属、木材、陶瓷、玻璃、织物、皮革上印刷，毫不夸张地说，目前喷墨成像技术已经可以在除了水和空气以外的所有平面和非平面材质上印刷。  \n\n喷墨印刷按打印方式不同分为连续式打印和按需式打印。目前喷墨印刷主要形式是按需式打印。按需式打印有热喷式和压电式。热喷式喷墨装置是由墨腔、喷头和加热器组成，加热器为薄膜电阻器，在墨水喷出区将墨水加热，形成一个气泡。气泡瞬间（不到 $10\\mu\\mathbf{s}\\mathrm{\\dot{=}}$ ）膨胀并破裂，将墨水从喷头喷出。压电式喷墨装置是由压电陶瓷、隔膜、压力腔和喷头组成，对压电陶瓷施加电压使其产生形变，引起压力腔内墨水体积变化，产生高压而将墨水从喷头喷出。目前压电式喷墨由于喷墨速度更快，容易控制墨滴形状和大小，喷头寿命也长，可适用各种类型喷墨墨水，虽然设备价格稍贵，但使用成本低，因此大幅面喷绘机都采用压电式喷墨。  \n\n喷墨印刷中最重要的耗材就是喷墨墨水。喷墨墨水的化学组成和性能决定了打印图像的质量、墨滴喷射的特性和打印系统的可靠性。喷墨墨水目前有水性、溶剂型、弱溶剂型和近年来发展起来的UV喷墨油墨，它们各有所长，应用于不同的喷墨印刷领域。  \n\nUV喷墨印刷是20世纪末发展起来的一种新技术，它结合了喷墨印刷技术和UV固化技术的各自优点，既有喷墨印刷技术在使用和操作上的便利，又有UV固化技术在经济上和技术上的优势，其特点为：  \n\n$\\textcircled{1}$ 没有或极少有机溶剂的挥发，不污染环境，属于环保型产品；  \n\n$\\textcircled{2}$ 快速固化，生产效率高；  \n\n③ 固化前油墨不干燥，不堵塞喷头，减少喷头清洗，在喷墨过程中，油墨组成恒定；  \n④ 优良的印刷质量，色彩鲜艳，分辨力高，特别耐摩擦、抗划伤性和耐化学药品性好；  \n③适用于多种基材，如柔性或刚性、可吸收或非吸收性材料。  \n\nUV油墨早在20 世纪70 年代起，就在胶印、凸印、柔印、凹印、网印和移印等印刷过程中应用，到20世纪末，由于喷墨技术的进步，精度的提高，UV光源制作技术的发展，给喷绘机配上合适的UV光源，设计制造出UV喷绘机；加上制备UV油墨的新原料不断开发，终于使UV油墨进入喷墨印刷领域。  \n\nUV油墨用于喷墨印刷，要解决三个技术难点：低黏度、稳定性和氧阻聚。  \n\n（1）喷墨油墨必须具有低黏度，一般热喷式喷墨油墨在25℃时，黏度在3～5mPa·s，压电式喷墨油墨在25℃时的黏度在3～30mPa·s，而常用的UV油墨黏度远远高于此黏度范围。最低黏度的凹印油墨在25℃时也要150～300mPa·s。因此要把UV喷墨油墨做到黏度≤30mPa·s是有一定难度的。必须选择低黏度的低聚物和活性稀释剂，而低黏度的低聚物和活性稀释剂往往官能度也较低，这就不利于固化速率提高，也不利于颜料的分散和稳定。  \n\n（2）UV喷墨油墨用的着色剂是以颜料为主的，要求颜料细度在1μm或更低，然后分散在低黏度的树脂体系中，不发生聚集，放置时不产生沉降。因此要选用对颜料润湿性好的低聚物，分散性好的颜料和稳定性好的分散剂，经过研磨加工后，获得细度≤1μm、放置不沉降、不聚集的油墨。  \n\n（3）UV喷墨油墨从喷头中喷出微小墨滴，有极大的表面，空气接触面加大，有更多的氧溶入油墨中，严重地阻碍墨滴UV固化。目前大型喷绘机的喷头移动速度在30m/min 左右，这就要求油墨有较快的固化速率。所以UV喷墨油墨在配方上必须考虑克服氧阻聚，选用活性高的光引发剂和固化速率快的低聚物和活性稀释剂。  \n\n作为UV喷墨油墨用的低聚物希望有较低的黏度，较快的固化速率，对颜料有很好的润湿性和分散稳定性，对承印物有较好的附着力。现在沙多玛、氰特等公司推出用于喷墨油墨的低聚物，如沙多玛公司的CN2300和CN2301都是八官能度的聚酯丙烯酸树脂，黏度也较低；氰特公司的Viajet100，黏度为107mPa·s，专用于颜料分散，Viajet 400 黏度仅20mPa·s，可作稀释剂用。活性稀释剂同样要选择低黏度、高活性、对颜料润湿分散性好的丙烯酸官能单体，实际使用都将单、双、多官能度丙烯酸酯混用，以取得较好的综合性能。光引发剂选择也要考虑高活性、有利于表干的品种，加入量可稍高于一般UV油墨，采用多种光引发剂复合使用。近两年，由于UV光源在UV喷墨上已开始用UV-LED光源，它是冷光源，寿命长，无臭氧产生，是由若干UV-LED点光源组合成面光源，光强也高，但光谱峰很窄，10nm左右，不如汞弧灯丰富，因此与目前光引发剂吸收光谱不完全匹配，目前UV-LED光源发射光谱有365nm、375nm、385nm、395nm、405nm等。多在UV长波段，故光引发剂要用ITX、DETX、TPO、819等品种。此外要保证UV喷墨油墨稳定不沉降，选用分散性好的颜料和分散稳定性好的分散剂也极重要，采用合适的研磨设备，保证颗粒不大于 $1\\mu\\mathrm{m}$ 。  \n\nUV喷墨印刷虽是刚刚发展起来的一种崭新的数字印刷技术，但它在经济上、技术上和使用上的优势，使UV喷墨印刷已超越了喷墨印刷领域，扩展到计算机直接制版（CTP)、数字化制作印制电路板（PCB）等新领域。  \n\n（1）UV喷墨印刷最早应用于数字喷墨标记和编码上，为各种饮料、包装和标签上条形码的印刷和数据印刷，电线电缆、光纤、汽车胶管上标记和数据印刷。进入21世纪，UV喷墨印刷在广告市场大显身手，在平台式喷绘机制作大幅面、小批量的广告牌和户外指示牌上获得广泛应用，并扩展到包装和金属喷涂，纸箱、纸盒、软包装及标签印刷、织物数码印花、电话卡、信用卡、购物卡制作等领域，成为数字印刷的一支新的生力军。  \n\n（2）印制电路制作有丝印法、干膜法和湿膜（光致成像油墨）法，而在研究开发的数字化制作PCB技术，则采用喷墨打印技术，使PCB制作工艺大大简化。只要用计算机设计好抗蚀、阻焊和字符三种图形后，控制喷墨打印机，先用UV抗蚀油墨在覆铜板上直接喷涂获得抗蚀图形，UV固化，经腐蚀、电镀和去除抗蚀油墨；再喷涂UV阻焊油墨获得阻焊图形、UV固化，形成永久性保护膜；最后用UV字符油墨喷上字符图形，UV固化，就得到成品。新工艺完全省去胶片制作母片，不用制作丝网和使用各种UV油墨、干膜或光成像油墨，也不用显影加工，节省了这些工序的操作时间和材料成本，减少了对环境的污染，意味着生产周期更短，实现更快、更经济、更环保的生产。现在喷墨打印字符已在PCB生产开始商品化，抗蚀油墨和阻焊油墨的喷墨打印设备也研制成功，UV抗蚀喷墨油墨和UV阻焊喷墨油墨也已开发，用喷墨打印数字化制作PCB新技术所需硬件和软件都已具备，正在努力实现商品化。  \n\n（3）计算机直接制版（CTP）技术是20世纪90年代印刷工业取得突破性进展的一项新技术，从此印刷方式从模拟化进人了数字化印刷的新时期。CTP技术最早应用于胶印制版上，有光敏型和热敏型两大类，竞相发展，而喷墨CTP 则是CTP技术的一种崭新形式，它以工艺简单、无化学处理、无环境污染、明室操作、成本低廉等优点，引起人们关注，特别是UV喷墨CTP工艺最为简便、高效、环保、经济和快速。UV喷墨CTP工艺是用高精度喷墨打印机，直接在经过亲水处理的铝板上喷涂UV油墨，UV固化，得到具有图文的印版，由于UV油墨具有亲油墨特性，印版可直接上胶印机进行印刷。  \n\nUV喷墨CTP技术的关键是要有一台套印准确的高精度喷墨打印机，同时要研制出一种低黏度、固化速率快、与铝版附着力好、亲油墨性能好的UV喷墨油墨。目前，国外大公司已投人较大的财力和精力正在开发研究，预计不久将会在CTP市场上以一颗耀眼新星的形式登场。  \n\n（4）UV导电油墨已开发成功，若能进一步用在喷墨打印上，PCB的制作则可以直接用导电油墨通过喷墨打印来完成。那时，就不需要覆铜板通过腐蚀来制作导电线路图形，直接在环氧树脂基板上喷涂导电图形，再喷涂阻焊油墨和字符油墨，制成PCB。这将是PCB制造的一场具有划时代意义的革命。随着喷墨打印技术精度不断提高，新型高品质材料不断开发，特别是微米级和纳米新材料的开发和利用，可用来制作电阻、电感、电容等无源电子元件。只要这些材料开发成功，那么电阻、电感、电容等无源电子元件不用先制成电子元件，再插人PCB中，可以直接通过喷墨打印机，将电阻、电容、电感等无源电子元件材料打印在PCB上，制成集成元件印制板。  \n\n<html><body><table><tr><td>EA(CN2204) 36.0 四官能团PEA（CN294） 16.0</td><td>颜料 滑石粉</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 415,
+        "chunk": "# （2）UV胶印油墨参考配方  \n\n<html><body><table><tr><td>脂肪酸改性PEA EA</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 416,
+        "chunk": "# （3）UV胶印油墨参考配方  \n\nITX 2  \nEDAB 5  \n颜料 19  \n稳定剂（ST-1） 1  \n\n<html><body><table><tr><td>脂肪酸改性PEA</td><td></td><td></td></tr><tr><td>多官能PUA</td><td></td><td>20</td></tr><tr><td>EA</td><td></td><td>10</td></tr><tr><td>GPTA</td><td></td><td>22</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 417,
+        "chunk": "# （4）UV胶印油墨参考配方  \n\nITX 2  \nEDAB 2  \n颜料 19  \n聚乙烯蜡 1  \n稳定剂（ST-1） 1  \n\n<html><body><table><tr><td>四官能团PEA（CN294） 六官能团PEA（CN293） 二官能团PEA（CN2200）</td><td>30.0 颜料 19.0 滑石粉 5.0</td><td>18.6 2.0 活性胺（CN373） 5.0</td></tr></table></body></html>\n\n联",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 418,
+        "chunk": "# （5）UV胶印油墨参考配方财片  \n\n<html><body><table><tr><td>PEA EA 脂肪酸改性EA PUA</td><td>25.0 25.0 5.0 10.0</td><td>SiOz BP ITX ODAB</td><td></td><td>0.5 3.0 2.0</td></tr><tr><td>颜料 CaCO3</td><td>17.0 5.0</td><td>蜡 助剂</td><td></td><td>5.0 1.0 1.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 419,
+        "chunk": "# （6）UV胶印油墨参考配方  \n\n<html><body><table><tr><td>双官能度PEA（PRO7978） PEA(CN2203) GPTA 907 TZT</td><td>35.0 KS300 23.0 ITX 8.0 3.5 滑石粉</td><td>3.0 0.5 品颜料（CibaMagentaSMA） 20.0 4.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 420,
+        "chunk": "# （7）UV胶印油墨参考配方  \n\n<html><body><table><tr><td>FA(PRO8008A) PEA(CN2203) Di-TMPTA (EO)TMPTA 907</td><td>28 20 11 5 3</td><td>KBI 5 活性胺（CN373） 2 红颜料（P.R.57：1） 20 滑石粉 2 聚乙烯蜡 2</td></tr></table></body></html>  \n\nPEA(PRO30037) 27  \nPEA(CN2282) 20  \nDi-TMPTA 11  \n(EO)TMPTA 2  \n907 3  \nTZT 2  \n\n江吃管租   \n\n\n<html><body><table><tr><td>KBI</td><td></td><td></td></tr><tr><td>活性胺（CN373） 红颜料（P.R.57:1）</td><td></td><td></td></tr><tr><td>滑石粉</td><td></td><td></td></tr><tr><td>聚乙烯蜡</td><td></td><td>6 2</td></tr><tr><td></td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 421,
+        "chunk": "# （9）UV胶印油墨参考配方  \n\n（8）UV胶印油墨参考配方  \n\n\n<html><body><table><tr><td>PEA(PRO20071) PEA(CN790) Di-TMPTA (EO)TMPTA 907</td><td>20 30 10 5 2 2</td><td>KBI 活性胺（CN373） 黄颜料（P.R.57:1） 14 滑石粉 聚乙烯蜡</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 422,
+        "chunk": "# （10）UV无水胶印油墨参考配方  \n\n<html><body><table><tr><td>PEA PUA GPTA TPGDA 369</td><td>35 ITX 15 11 颜料 10 3</td><td>活性胺 17 滑石粉 聚乙烯蜡</td></tr><tr><td colspan=\"3\">2 （11）快固UV胶印金属装饰油墨参考配方</td></tr><tr><td>EA PUA PEA DDA 369</td><td>30 ITX 19 10 颜料 10 3</td><td>3 EDAB 5 17 滑石粉 1 聚乙烯蜡 2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 423,
+        "chunk": "# （12）UV红色胶印油墨参考配方  \n\n<html><body><table><tr><td>EA PEA</td><td></td><td>DEAP MDEA</td><td>3 2</td></tr><tr><td>TMPTA</td><td>10</td><td>CaCO3</td><td>17</td></tr><tr><td>TPGDA</td><td>14</td><td>聚乙烯蜡</td><td>3</td></tr><tr><td>BP</td><td></td><td>品红</td><td>16</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 424,
+        "chunk": "# （13）UV黄色胶印油墨参考配方  \n\n<html><body><table><tr><td>PEA</td><td>22.0</td><td>混合光引发剂 联苯胺黄GR</td><td></td><td>10.0</td></tr><tr><td>EA（含20%TPGDA） 芳香族PUA GPTA</td><td>15.0 22.0 10.0</td><td>助剂</td><td></td><td>18.0 3.0</td></tr></table></body></html>\n\n.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 425,
+        "chunk": "# （14）UV蓝色胶印油墨参考配方  \n\n<html><body><table><tr><td>EA PEA (EO)DDA BP</td><td></td><td>30.0 二甲氨基苯甲酸丁氧酯 18.0 菁蓝 10.0 炭黑 5.0 蜡 3.0 稳定剂</td><td></td><td>5.0 22.0 5.0 1.9 0.1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 426,
+        "chunk": "# （15）UV蓝色胶印油墨参考配方  \n\n的##  \n\n\n<html><body><table><tr><td>四官能度PEA 四官能度EA 四官能度GPTA 稳定剂12/1</td><td>25.0 37.0 填料 4.0 1.0 蜡</td><td>蓝颜料PB15:3 光引发剂</td><td>17.0 6.0 10.0 0.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 427,
+        "chunk": "# （16）UV蓝色胶印油墨参考配方  \n\n<html><body><table><tr><td>EA 六官能团芳香族PUA</td><td>37.3 10.4</td><td>润湿分散剂 LFC1001</td><td>1.5 3.0</td></tr><tr><td>TMPTA 菁蓝</td><td>31.9 18.0</td><td>EDAB ITX</td><td>2.25 1.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 428,
+        "chunk": "# （17）UV黑色胶印油墨参考配方  \n\n<html><body><table><tr><td>EA</td><td></td><td colspan=\"2\">35 651 23</td><td></td><td>1 1</td></tr><tr><td>PEA</td><td></td><td></td><td rowspan=\"3\">EDAB</td><td rowspan=\"3\">DEAP</td><td></td></tr><tr><td>GPTA</td><td></td><td>9 4</td><td>5</td></tr><tr><td>BP ITX</td><td></td><td>炭黑 蜡</td><td>18 2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 429,
+        "chunk": "# （18）UV黑色胶印油墨参考配方  \n\n<html><body><table><tr><td>多官能度PEA</td><td>23.0 蜡</td><td>2.0</td></tr><tr><td>PEA</td><td>28.0</td><td>滑石粉 1.0</td></tr><tr><td>三官能度脂肪族PUA</td><td>7.5</td><td>混合光引发剂 6.0</td></tr><tr><td>GPTA</td><td>12.5</td><td>炭黑MOGELE 20.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 430,
+        "chunk": "# （19）UV黑色胶印油墨参考配方  \n\n<html><body><table><tr><td>EA 多官能PUA 多官能PEA DPHA</td><td></td><td>21 369 10 184 10 EDAB 8 炭黑 15 颜料紫3 3 聚乙烯蜡</td><td>3 1 6 18 1</td></tr></table></body></html>  \n\n注：用于纸或卡纸。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 431,
+        "chunk": "# （20）UV黑色胶印油墨参考配方  \n\n<html><body><table><tr><td>PEA(EB657) 六官能团PUA（EB220） 环氧大豆油丙烯酸酯（EB860）</td><td>37.3 蜡 11.6 SiO2 6.3 分散剂 10.0 369 12.0</td><td>0.5 1.5 3.3 2.5 ITX 3.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 432,
+        "chunk": "# （21）UV白色胶印油墨参考配方  \n\n<html><body><table><tr><td>EA 多官能PEA DDA</td><td>25 20 10</td><td>TiO2 聚乙烯蜡 滑石粉</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 433,
+        "chunk": "# （22）UV胶印油墨参考配方（表7-16）  \n\n表7-16 UV胶印油墨参考配方  \n\n\n<html><body><table><tr><td>组成</td><td>黄</td><td>红</td><td>蓝</td><td>黑</td></tr><tr><td>颜料</td><td>PY13 17</td><td>PR57 17</td><td>PB15.4 17</td><td>SPecialblack25015 Heliogenblued 70922</td></tr><tr><td>颜料分散树脂</td><td></td><td></td><td></td><td></td></tr><tr><td>Laromer LR9013 改性聚醚丙烯酸酯</td><td>20</td><td>20</td><td>20</td><td>20</td></tr><tr><td>'Laromer LR8986 改性环氧丙烯酸酯</td><td>10</td><td>33</td><td>10</td><td>10</td></tr><tr><td>Laromer LR9004</td><td>43</td><td>20</td><td>43</td><td>43</td></tr><tr><td>聚酯丙烯酸酯 TPO-L</td><td>4</td><td>4</td><td>4</td><td>4</td></tr><tr><td>369</td><td>4</td><td>4</td><td>4</td><td>4</td></tr><tr><td>907</td><td>2</td><td>2</td><td>2</td><td>2</td></tr></table></body></html>  \n\n<html><body><table><tr><td colspan=\"4\">（23）UV柔印油墨参考配方</td></tr><tr><td>EA GPTA</td><td>15 30</td><td>TEA 颜料</td><td>3 14</td></tr><tr><td>TPGDA</td><td>31</td><td>聚乙烯酯</td><td>1</td></tr><tr><td colspan=\"4\">BP 6</td></tr><tr><td colspan=\"4\">（24）UV柔印油墨参考配方 814 26.9 颜料 6.9 Tego Prototgp Tego Airex920 六官能团PEA（EB870）</td></tr><tr><td colspan=\"4\">TPGDA 25.7 TMPTA 17.0 （25）UV柔印油墨参考配方 六官能团芳香族PUA（EB220）</td></tr><tr><td colspan=\"4\">三官能团PEA（EB657） 18.0 819 附着力促进树脂（EB40） 49.3 369 HDDA 9.2 颜料（Bluel5:3）</td></tr><tr><td colspan=\"4\">ITX 1.0 Solsperse5000 EDAB 1.7 SdsperseB9000 184 1.0 （26）UV低气味柔印油墨参考配方</td></tr><tr><td colspan=\"4\">PEA 10 活性胺 胺改性聚醚丙烯酸酯 45 颜料 TPGDA 21 聚乙烯蜡</td></tr><tr><td colspan=\"4\">369 3 稳定剂 ITX 2</td></tr><tr><td colspan=\"4\">（27）UV低气味柔印油墨参考配方 2 注：用于柔性包装材料印刷。</td></tr><tr><td colspan=\"4\">PEA 10 ITX EA 5 活性胺 GPTA 30 颜料 TPGDA 31 聚乙烯蜡 369 3 稳定剂</td></tr></table></body></html>  \n\n（28）UV蓝色柔印油墨参考配方  \n\n\n<html><body><table><tr><td rowspan=\"6\"></td><td rowspan=\"6\">20.0 10.0 11.0 10.5 15.0 3.5</td><td>KS300</td><td>3.0 1.0</td></tr><tr><td>TZT ITX</td><td>0.5</td></tr><tr><td>蓝颜料（BlueGLVO）</td><td>20.0</td></tr><tr><td></td><td>分散剂（LubrizolSolsperse3900）</td><td>5.0</td></tr><tr><td>硅流平剂（BYK-UV3510）</td><td></td><td></td></tr><tr><td></td><td></td><td>0.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 434,
+        "chunk": "# （29）UV柔印油墨参考配方$\\textcircled{1}$ 色浆配方 (表7-17)  \n\n表7-17 色浆配方  \n\n\n<html><body><table><tr><td>组成</td><td>黄</td><td>品</td><td>青</td><td>黑</td><td>白</td></tr><tr><td>颜料名称</td><td>汽巴 LBG</td><td>汽巴 LBD</td><td>汽巴 GLO</td><td>√德固萨 Black250</td><td>Kronos Titan2310</td></tr><tr><td>颜料的用量</td><td>35</td><td>35</td><td>35</td><td>35</td><td>50</td></tr><tr><td>PEA(Genomer 3611)</td><td>60</td><td>60</td><td>64</td><td>60</td><td>49</td></tr><tr><td>BYK168</td><td>4</td><td>4</td><td>±</td><td>4</td><td></td></tr><tr><td>稳定剂(Genorad 16)</td><td>1</td><td>1</td><td>1</td><td>1</td><td>1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 435,
+        "chunk": "# $\\textcircled{2}$ 油墨配方 (表7-18)  \n\n表7-18 油墨配方  \n\n\n<html><body><table><tr><td>组成</td><td>黄</td><td>品</td><td>青</td><td>黑</td><td>白</td></tr><tr><td>色浆</td><td>40.0</td><td>40.0</td><td>40.0</td><td>30.0 品3.0</td><td>52.0</td></tr><tr><td>低黏度EA(Genomer2259)</td><td>9.5</td><td>9.5</td><td>13.5</td><td>青7.0 10.0</td><td>10.0</td></tr><tr><td>高活性芳香族PUA(Genomer4622)</td><td>5.0</td><td>5.0</td><td>5.0</td><td>5.0</td><td></td></tr><tr><td>DiTMPTA</td><td></td><td></td><td></td><td></td><td>9.0</td></tr><tr><td>(EO)TMPTA</td><td>15.0</td><td>15.0</td><td>11.0</td><td>18.5</td><td>7.0</td></tr><tr><td>TPGDA</td><td>21.4</td><td>19.4</td><td>19.5</td><td>15.0</td><td>12.9</td></tr><tr><td>369</td><td>3.0</td><td>3.0</td><td>3.8</td><td>4.0</td><td></td></tr><tr><td>1173</td><td>1.9</td><td>1.9</td><td>2.4</td><td>2.5</td><td>2.0</td></tr><tr><td>TPO</td><td></td><td></td><td></td><td></td><td>1.5</td></tr><tr><td>ITX</td><td>0.8</td><td>0.8</td><td>0.9</td><td>1.0</td><td></td></tr><tr><td>GenocurePBZ</td><td>1.9</td><td>1.9</td><td>2.4</td><td>2.5</td><td>1.0</td></tr><tr><td>Genocure CPK</td><td></td><td></td><td></td><td></td><td>3.0</td></tr><tr><td>稳定剂 Genorad 16 Genorad 20 UVitexOB</td><td>0.5</td><td>0.5</td><td>0.5</td><td>0.5</td><td>0.5 0.1</td></tr></table></body></html>  \n\n（30）UV标签印刷用柔印油墨参考配方  \n\n\n<html><body><table><tr><td>EA 651</td><td rowspan=\"3\">15 BP 30 31 3</td><td>三乙醇胺</td></tr><tr><td>GPTA TPGDA</td><td>14</td></tr><tr><td></td><td>聚乙烯蜡 颜料</td></tr></table></body></html>  \n\n（31）UV纸盒包装印刷柔印油墨参考配方  \n\n\n<html><body><table><tr><td>PEA EA GPTA TPGDA ITX</td><td>10 5 30 31 2</td><td>907 活性胺 稳定剂 颜料 分散剂</td><td>2 3 1 14 1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 436,
+        "chunk": "# （32）UV柔印油墨参考配方",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 437,
+        "chunk": "# $\\textcircled{1}$ 色浆配方 (表7-19)  \n\n$\\textcircled{2}$ 柔印油墨配方（表7-20)   \n\n\n<html><body><table><tr><td>组成</td><td>黑</td><td>青</td><td>黄</td><td>品</td></tr><tr><td>颜料</td><td>PBK7</td><td>PB15:4</td><td>PY74</td><td>PR 57:1</td></tr><tr><td>颜料用量</td><td>25</td><td>25</td><td>25</td><td>25·</td></tr><tr><td>PEA(CN2297)</td><td>10</td><td>10</td><td>10</td><td>20</td></tr><tr><td>PEA(PR06467)</td><td>17</td><td>17</td><td>17</td><td>7</td></tr><tr><td>研磨树脂（PR04676)</td><td>46</td><td>46</td><td>46</td><td>46</td></tr><tr><td>三官能PEA(CN294)</td><td>2</td><td>2</td><td>2</td><td>2</td></tr></table></body></html>  \n\n表7-20 柔印油墨配方  \n\n\n<html><body><table><tr><td>组成</td><td>黑</td><td>青</td><td>黄</td><td>品</td></tr><tr><td>色浆</td><td>80.0</td><td>80.0</td><td>80.0</td><td>80.0</td></tr><tr><td>活性胺CN371</td><td>10.0</td><td>10.0</td><td>10.0</td><td>10.0</td></tr><tr><td>369</td><td>3.5</td><td>3.5</td><td>3.5</td><td>3.5</td></tr><tr><td>184</td><td>3.0</td><td>3.0</td><td>3.0</td><td>3.0</td></tr><tr><td>BP</td><td>1.0</td><td>1.0</td><td>1.0</td><td>1.0</td></tr><tr><td>ITX</td><td>0.5</td><td>0.5</td><td>0.5</td><td>0.5</td></tr><tr><td>UV636</td><td>1.0</td><td>1.0</td><td>1.0</td><td>1.0</td></tr><tr><td>BYKUV 3500</td><td>0.5</td><td>0.5</td><td>0.5</td><td>0.5</td></tr><tr><td>BYK088</td><td>0.5</td><td>0.5</td><td>0.5</td><td>0.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 438,
+        "chunk": "# （33）UV柔印油墨配方（表7-21)  \n\n表7-19 色浆配方  \n表7-21 UV柔印油墨配方  \n\n\n<html><body><table><tr><td>组成</td><td>黄</td><td>红</td><td>蓝</td><td>黑Q</td></tr><tr><td>颜料</td><td>PY13 15</td><td>PR 57 15</td><td>PB15·4 15</td><td>Specialblack25013 HeliogenblueD70922</td></tr><tr><td>颜料分散R9013</td><td>15</td><td>15</td><td>15</td><td>15</td></tr><tr><td>Laromer PO94F</td><td>47</td><td>52</td><td>55</td><td>55</td></tr><tr><td>DPGDA</td><td>13</td><td>8</td><td>5</td><td>5</td></tr><tr><td>TPO-L</td><td>4</td><td>4</td><td>4</td><td>400</td></tr><tr><td>369</td><td>4</td><td>4</td><td>4</td><td>4</td></tr><tr><td>907</td><td>2</td><td>2</td><td>2</td><td>2</td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td colspan=\"2\">（34）UV黄色柔印油墨参考配方 ①色浆</td></tr><tr><td>四官能PEA（EB657） 53稳定剂 DPGDA 13 分散剂 3</td><td>黄颜料（YellowBAW） 30</td></tr><tr><td>②油墨配方 色浆</td><td>EDAB 5.0</td></tr><tr><td>40.0 聚醚四丙烯酸酯（EB40） 51.5 DETX 3.0</td><td>流平剂 0.5</td></tr><tr><td colspan=\"2\">（35）UV红色柔印油墨配方 BPA(EO)DA 30.0 稳定剂UV1</td></tr><tr><td>NPG(PO)DA 17.0 DPGDA 12.0 TMP(EO)TA 10.0 颜料（红57：1） 16.0 分散剂SF73 4.5</td><td>0.5 稳定剂907 3.0 稳定剂ITX 1.0 稳定剂651 3.0 稳定剂TZT 3.0</td></tr><tr><td colspan=\"2\">（36）UV品红柔印油墨参考配方 ①色浆</td></tr><tr><td>四官能PEA（EB657） 48 DPGDA 13 分散剂 3</td><td>稳定剂 1 品红颜料（Magenta4BY） 35</td></tr><tr><td colspan=\"2\">②油墨配方 色浆 40.0</td></tr><tr><td>聚醚四丙烯酸酯（EB40） 51.5 DETX 3.0</td><td>EDAB 5.0 流平剂 0.5</td></tr><tr><td colspan=\"2\">（37）UV蓝色柔印油墨参考配方 ①色浆</td></tr><tr><td>四官能PEA（EB657） 47 DPGDA 14 分散剂 3</td><td>稳定剂 1 蓝色颜料（CyanBGLO) 35</td></tr><tr><td colspan=\"2\">②油墨配方</td></tr><tr><td>色浆 40.0 聚醚四丙烯酸酯（EB40） 51.5 DETX 3.0</td><td>EDAB 5.0 流平剂 0.5</td></tr><tr><td colspan=\"2\">（38）UV蓝色柔印油墨参考配方 PEA 26.9 菁蓝</td></tr><tr><td>六官能度芳香族PUA 5.0 PM-1 10.5 TPGDA 4.5 ITX HDDA 13.0 甘油三丙烯酸酯 19.0 651</td><td>11.1 1.3 有机硅助剂 0.7 2.0 EDAB 3.0 3.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 439,
+        "chunk": "# （39）UV蓝色柔印油墨参考配方  \n\nPEA(CN2285) 56.0 TZT 1.0  \nEA(CN116) 10.0 ITX 0.5  \n蓝颜料（lrgaliteBlue） 20.0 聚乙烯蜡UV636 1.0  \n分散剂（Solsperse3900） 4.0 硅消泡剂BYK088 0.5  \n369 3.5 硅流平剂BYKUV3510 0.5  \nKS300 3.0",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 440,
+        "chunk": "# （40）UV青色柔印油墨参考配方  \n\n<html><body><table><tr><td>三官能度PEA TMP（EO)TA DPGDA</td><td rowspan=\"3\">18 30 12 17</td><td>369 651 ITX EDAB</td></tr><tr><td></td><td></td></tr><tr><td>颜料分散稳定剂（ViaFlex100）</td><td>2</td></tr></table></body></html>  \n\nPEA 38.1 KS300 3.0  \nPE(EO)TA 30.5 TZT 1.0  \n颜料 23.3 ITX 0.5  \n助剂 8.1 活性胺 5.0  \nEsacure1001 3.5",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 441,
+        "chunk": "# （41）黑色UV柔印油墨参考配方",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 442,
+        "chunk": "# （42）UV黑色柔印油墨  \n\nPEA 39.3 Esacure 1001 3.5   \nPE(EO)TA 31.0 KT55 3.0   \n炭黑 23.3 651 3.0   \n助剂 6.4 活性胺 4.0",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 443,
+        "chunk": "# （43）UV白色柔印油墨参考配方  \n\n四官能度丙烯酸酯（EB40） 26.8 TPO 2.0  \nPEA（EB2958) 13.0 ITX 0.5  \n胺化丙烯酸酯（EB7100） 5.0 EDAB 5.0  \nDPGDA 5.5 Tego Rad2300 1.5  \nKronos 2063S 40.0 Tego Dispers 655 0.7",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 444,
+        "chunk": "# （44）UV白色柔印油墨参考配方  \n\n多官能度PEA 13.0 ITX 0.5  \n四官能度聚丙烯酸酯 26.8 EDAB 5.0  \n胺改性聚丙烯酸酯 5.0 胺改性聚丙烯酸酯 5.0  \nDPGDA 25.5 Rad2300 1.5  \n$T_{1}0_{2}$ 20.0 TEGODispers655 0.7  \nTPO 2.0",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 445,
+        "chunk": "# （45）UV凸印油墨参考配方  \n\n大汤生小健   \n\n\n<html><body><table><tr><td>EA GPTA</td><td>35 20 13</td><td>TEA 颜料 填料</td><td>3 17 5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 446,
+        "chunk": "# （46）UV凸印油墨参考配方  \n\nEA 20   \n丙烯酸环氧亚麻油酯 15   \n乙氨基双酚A二丙烯酸酯 20   \n丙氧基甘油三丙烯酸酯 10   \nBP 8   \nTEA 3   \n超细PTFE蜡 2   \nWhite EX-102 22",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 447,
+        "chunk": "# （47）UV红色凸印标记油墨参考配方  \n\n<html><body><table><tr><td>PEA</td><td>54 10</td><td>ITX EDAB</td><td>3 5</td></tr><tr><td>DDA TMPTA</td><td></td><td>立索玉红颜料 蜡</td><td>16 1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 448,
+        "chunk": "# （48）UV黑色凸印油墨参考配方  \n\n武#电集VU（0）  \n\n\n<html><body><table><tr><td>EA PEA</td><td></td><td>15 369 22 ODAB</td><td></td><td></td><td>4 4</td></tr><tr><td>氯化PEA</td><td></td><td>30</td><td>炭黑</td><td></td><td>16</td></tr><tr><td>GPTA</td><td></td><td>5</td><td>聚乙烯蜡</td><td></td><td>2</td></tr><tr><td>ITX</td><td></td><td>2</td><td></td><td></td><td></td></tr></table></body></html>\n\n明U",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 449,
+        "chunk": "# （49）UV白色凸印油墨参考配方  \n\n<html><body><table><tr><td>EA HDDA</td><td rowspan=\"3\">25 10 19 2</td><td rowspan=\"3\">1173 TiO2 滑石粉 SiOz</td><td></td><td rowspan=\"3\">3 24 15</td></tr><tr><td>TPGDA TPO</td><td>2</td></tr><tr><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 450,
+        "chunk": "# （50）UV凹印油墨参考配方",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 451,
+        "chunk": "# 照  \n\n<html><body><table><tr><td>聚酯四丙烯酸酯（EB657） 苯乙烯-马来酸酐共聚物（SMA1440F） (EO)4PETA(SR494) 819</td><td>30.0 10.0 17.0 4.9 5.0</td><td>巴西棕榈蜡 表面活性剂 磺化麻油 癸二酸二丁酯 UV稳定剂</td><td>3.0 4.0 2.0 3.0 1.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 452,
+        "chunk": "# （51）UV丝印油墨参考配方  \n\n<html><body><table><tr><td>TPGDA</td><td>30.0 184 15.0 651</td><td></td><td>2.5 2.0</td></tr><tr><td>丙烯酸树脂（Elvacite2013）</td><td rowspan=\"3\">5.0 活性胺 15.0 聚硅氧烷</td><td rowspan=\"3\"></td><td>1.5</td></tr><tr><td>TMP(EO)TA</td><td>1.0</td></tr><tr><td>N-乙烯基己内酰胺 20.0 颜料</td><td>7.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 453,
+        "chunk": "# （52）UV丝印油墨参考配方  \n\n<html><body><table><tr><td>PUA 丙烯酸树脂</td><td></td><td>20.0 活性胺 15.0 颜料</td><td></td><td></td><td>1.5 7.0</td></tr><tr><td>TPGDA</td><td rowspan=\"3\"></td><td rowspan=\"3\">30.0 5.0 1.0</td><td>填料</td><td></td><td>15.0</td></tr><tr><td>DPTTA</td><td>蜡</td><td>1.0</td></tr><tr><td>ITX</td><td>硅助剂</td><td>2.0</td></tr></table></body></html>  \n\n注：用于纸张和纸版。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 454,
+        "chunk": "# （53）UV丝印油墨参考配方",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 455,
+        "chunk": "# 飞新修司  \n\n<html><body><table><tr><td>脂肪族PUA TPGDA NVP</td><td>4.5</td><td>50.0 16.5 8.5 1.0</td><td>EDAB 颜料 填料 硅消泡剂</td><td>1.5 7.0 10.0 1.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 456,
+        "chunk": "# （54）UV丝印磨砂油墨参考配方  \n\no   \n\n\n<html><body><table><tr><td>二官能度脂肪族PUA（611A-85，含15%TPGDA） (PO)NPGDA PETA</td><td>80 10 10 2 磨砂料（5378）</td><td>活性胺（Etercure6420） 5 消泡剂（FoamexN）等 4 平滑剂（Eterslip70） 0.2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 457,
+        "chunk": "# （55）UV丝印发泡油墨参考配方  \n\n<html><body><table><tr><td>（PO)NPGDA 10 二官能度脂肪族PUA（611B-85，含15%HDDA） 改性EA（6231A-80，含20%TPGDA）</td><td>50 184 1 20 BP 2 活性胺（EterCure6420） 5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 458,
+        "chunk": "# （56）UV丝印皱纹油墨参考配方  \n\n<html><body><table><tr><td>二官能度脂肪族PUA（611A-85，含15%TPGDA） 25 (622A-80,20%TPGDA) 20 TMPTMA 15 (EO)TMPTA 20 HDDA 10</td><td>BP 4 活性胺（Etercure6420） 10 消泡剂等（FoamexN） 5 平滑剂（Eterslip70） 0.2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 459,
+        "chunk": "# （57）UV蓝色丝印油墨参考配方  \n\n<html><body><table><tr><td>EA PEA</td><td rowspan=\"3\">35.0 20.0 10.0 5.0 3.0</td><td rowspan=\"3\">EDAB 菁蓝 炭黑 石蜡 稳定剂</td><td></td><td rowspan=\"3\">5.0 15.0 5.0 1.9</td></tr><tr><td>DDA</td><td></td></tr><tr><td>BP CTX</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 460,
+        "chunk": "# （58）UV蓝色丝印油墨参考配方  \n\n<html><body><table><tr><td>Heliogenblue D7092 颜料分散树脂LaromerLR9013 PEALaromer LR9004 改性EALaromerLR8986 改性EALaromerLR9019 DPGDA TPO-L</td><td>5.0 907 5.0 助引发剂LaromerLR8956 12.0 助剂CAB551-00120%inTPGDA 6.0 BYK164 37.0 P.A.57:1 17.0 TegoRad2100 2.0 Aerosil200</td><td>1.0 40 4.5 1.0 0.8</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 461,
+        "chunk": "# （59）UV蓝色丝印油墨参考配方  \n\n<html><body><table><tr><td>EA PUA</td><td>20.0 10.0 2.5</td><td rowspan=\"2\">ITX EDAB 酞菁蓝 聚乙烯蜡</td><td rowspan=\"2\"></td></tr><tr><td>UPE TPGDA</td><td>25.0 30.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 462,
+        "chunk": "# （60）UV蓝色丝印油墨参考配方  \n\n<html><body><table><tr><td>A.丙烯酸树脂（SetalinAp560）</td><td>55.0</td><td>1-甲酸甲酯硫杂葱酮 4.0</td></tr><tr><td>蓝色颜料（lrgalithGISM）</td><td>22.0 17.6</td><td>N-甲基二乙醇胺 1.4</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 463,
+        "chunk": "# 先研磨A得到色浆，再加人B组分，继续研磨均匀即为UV蓝色印刷油墨。  \n\n（61）UV黑色丝印油墨参考配方  \n\n\n<html><body><table><tr><td>EA</td><td>59.3</td><td>炭黑</td></tr><tr><td>TMPTA HDDA</td><td>20.4 14.8</td><td>2.5 DETX 1.0 N-甲基二乙醇胺 2.0</td></tr></table></body></html>  \n\n我，！  \n\n\n<html><body><table><tr><td>EA DDA</td><td></td><td>43 EDAB 20 炭黑 3 菁蓝</td><td>7 15 2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 464,
+        "chunk": "# （62）UV黑色丝印油墨参考配方",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 465,
+        "chunk": "# （63）UV黑色丝印油墨参考配方  \n\n<html><body><table><tr><td>脂肪族PUA TPGDA</td><td></td><td>26.8 ITX 20.0 651 炭黑</td><td></td><td>0.5 4.0</td></tr><tr><td>TMP(EO)TA DPHA</td><td></td><td>28.0 10.0 润湿剂 4.5</td><td></td><td>6.0 0.2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 466,
+        "chunk": "# （64）UV蓝色丝印油墨参考配方  \n\n注：用于PVC承印。  \n\n<html><body><table><tr><td>脂肪族PUA（含20%TPGDA） EA（含25%TPGDA）</td><td>10.0 30.0 10.0</td><td>混合光引发剂 助剂和填料 菁蓝</td><td>10.0 5.0 5.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 467,
+        "chunk": "# （65）UV-塑料标签油墨参考配方  \n\n<html><body><table><tr><td>EA PUA PEA TMPTA</td><td></td><td>30 DEAP 24 EDAB 9 颜料 4 石蜡</td><td>3 3 18 2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 468,
+        "chunk": "# （66）UV-PET丝印油墨参考配方  \n\n<html><body><table><tr><td>EA TPGDA EO-TMPTA N-乙烯基己内酰胺 丙烯酸树脂（Elvacite2013）</td><td>30.0 15.0 15.0 20.0 5.0</td><td>1173 651 活性胺 颜料</td><td>2.5 2.0 1.0 7.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 469,
+        "chunk": "# （67）UV-PS丝印油墨参考配方  \n\nPUA 20.0   \nTPGDA 30.0   \n丙烯酸树脂（Elvaclte2031） 16.0   \nN-乙烯基己内丙基胺 10.0   \nITX 1.0   \n651 3.0   \nDMEA 1.5   \n颜料 7.0   \n填料 10.0   \n硅消泡剂 1.5  \n\n由样V！  \n\n（68）UV-PVC丝印油墨参考配方  \n\n\n<html><body><table><tr><td>脂肪族、双官能PUA TPGDA</td><td rowspan=\"3\">50.0 16.5 8.0</td><td rowspan=\"3\">DMEA 颜料 填料 硅消泡剂</td><td></td><td>1.5 7.0</td></tr><tr><td>N-乙烯己内酰胺</td><td></td><td>10.0</td></tr><tr><td>ITX 651</td><td></td><td>1.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 470,
+        "chunk": "# （69）UV-PE丝印油墨参考配方  \n\n<html><body><table><tr><td>胺改性EA TPGDA</td><td></td><td>60.0 20.0</td><td>TPO 颜料</td></tr><tr><td>LA</td><td></td><td>6.0</td><td>7.0 SiO2 1.5</td></tr><tr><td>ITX</td><td></td><td>1.5</td><td>硅流平消泡剂 1.5</td></tr><tr><td>184</td><td></td><td>1.5</td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td colspan=\"3\">ITX 1.5 硅流平消泡剂 184 1.5</td></tr><tr><td colspan=\"3\">（70）UV黑色PE油墨参考配方</td></tr><tr><td>脂肪族PUA（CN966，含10%EOEOEA） DPEPA(SR399) 低黏度双丙烯酸酯（CN132）</td><td>31.0 ITX 22.0 907 31.8 炭黑 4.0</td><td>0.5 4.5 6.0 润湿剂（SR022） 0.2</td></tr><tr><td colspan=\"3\">光引发剂（SR1111） （71）UV黑色PC丝印油墨参考配方</td></tr><tr><td>脂肪族PUA（CN961E80） TPGDA EO-TMPTA DPEPA 光引发剂（SR1111） 4.0</td><td>26.8 907 20.0 ITX 28.0 炭黑 10.0 润湿剂（SR022）</td><td>4.5 0.5 6.0 0.2</td></tr><tr><td colspan=\"3\">（72）UV白色PC丝印、油墨参考配方</td></tr><tr><td>脂肪族PUA（CN961E80） TPGDA EO-TMPTA DPEPA</td><td>20.0 光引发剂（SR1113） 20.0 TiO 20.8 润湿剂（SR022） 8.0</td><td>8.0 23.0 0.2</td></tr><tr><td colspan=\"3\">08 （73）UV白色丝印光盘油墨参考配方</td></tr><tr><td>PEA（EB525) 丙烯酸树脂（EB1710） EO-TMPTA TPGDA TiO2</td><td>20 TPO 20 1173 15 SiO(Aerosil 200） 10 消泡剂（Airex900） 25</td><td>2.5 2.5 3.0 2.0</td></tr><tr><td colspan=\"3\">（74）UV白色丝印油墨参考配方</td></tr><tr><td>PUA EA POEA 光引发剂SR1135（TPO/KIP150/TZT）</td><td>27.75 钛白粉 10.0 润湿剂SR022 30.0 流平剂SR012 6.0</td><td>25.0 0.25 1.0</td></tr><tr><td colspan=\"3\"></td></tr><tr><td>（75）UV绿色软管油墨参考配方 EA</td><td>35 369</td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>EA 氯化PEA</td><td></td><td></td><td></td><td>35</td></tr><tr><td>TMPTA</td><td></td><td></td><td></td><td>20 6</td></tr><tr><td>TPGDA</td><td></td><td></td><td></td><td>10</td></tr><tr><td>184</td><td></td><td></td><td></td><td>2</td></tr></table></body></html>  \n\n菁绿 20   \n助剂 1   \n混合溶剂 5  \n\n（76）UV黄色软管油墨参考配方  \n\n\n<html><body><table><tr><td>EA 氯化PEA</td><td></td><td></td><td></td><td>40 15</td><td></td></tr><tr><td>TMPTA</td><td></td><td></td><td></td><td></td><td>6</td></tr><tr><td>TPGDA</td><td></td><td></td><td></td><td></td><td>10</td></tr><tr><td>907</td><td></td><td></td><td></td><td></td><td>2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 471,
+        "chunk": "# （77）UV白色软管油墨参考配方  \n\n369 1  \n联苯胺黄 2  \n巴斯夫371 18  \n助剂 1  \n混合溶剂 5  \nEA 8 819 2  \nPUA 12 184 1  \n氯化PEA 10 $\\mathrm{TiO}_{2}$ 28  \nTMPTA 8 助剂 1  \nTPGDA 20 混合溶剂 10  \n\n<html><body><table><tr><td>EA PEA HDDA</td><td>25 5 25</td><td>EDAB 红颜料 CaCO3 聚乙烯蜡</td><td>3 10 15</td></tr><tr><td>TPGDA CTX</td><td>5 4</td><td>表面活性剂</td><td>3 1</td></tr><tr><td>DEAP</td><td>4</td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 472,
+        "chunk": "# （78）UV红色丝印油墨参考配方",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 473,
+        "chunk": "# （79）UV红色塑料标记油墨参考配方  \n\n<html><body><table><tr><td>氯化PEA PUA PEA TMPTA ITX</td><td></td><td>DEAP EDAB 红颜料 滑石粉 蜡</td><td>3 3 18 3 2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 474,
+        "chunk": "# （80）UV白色玻璃丝印油墨参考配方  \n\n<html><body><table><tr><td>低黏度PUA（CN987） 低黏度单丙烯酸酯低聚物（CN131） POEA</td><td>27.75 10.00</td><td>非迁移、无黄变光引发剂（SR1113） 润湿剂（SR022）</td><td>6.00 0.25</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 475,
+        "chunk": "# （81）UV黑色玻璃丝印油墨参考配方  \n\n（82）UV绿色金属油墨参考配方  \n\n\n<html><body><table><tr><td>芳香酸丙烯酸酯半酯（SB520E35） 46.0 低黏度单丙烯酸酯低聚物（CN131） 22.0 POEA 20.0 907 4.5</td><td>ITX 0.5 BP 2.0 炭黑（Raven450） 4.0</td></tr></table></body></html>  \n\n<html><body><table><tr><td>EA PUA BP ITX</td><td>40 18 6 4</td><td>菁绿 二芳酰胺黄 聚乙烯蜡</td></tr></table></body></html>  \n\n（83）UV白色金属油墨参考配方  \n\n\n<html><body><table><tr><td>低黏度脂肪族PUA（CN987） 低黏度单丙烯酸酯低聚物（CN131） 三官能团丙烯酸树脂（SR9051） 非迁移无黄变光引发剂（SR1113）</td><td>27.75 10.00 30.00</td><td>TiO2(R-900) 25.00 润湿剂（SR022） 0.25 非硅流平剂（SR012） 1.00</td></tr></table></body></html>  \n\n（84）UV帘涂黑色金属涂料参考配方  \n\n\n<html><body><table><tr><td>芳香酸丙烯酸酯半酯（SR520E35）</td><td>46.0 ITX BP</td><td>0.5</td></tr><tr><td>低黏度单丙烯酸酯低聚物（CN131）</td><td rowspan=\"3\">22.0 20.0</td><td>2.0</td></tr><tr><td>POEA</td><td>炭黑（Raven450） 4.0</td></tr><tr><td>4.5</td><td>非硅流平剂（SR012） 1.0</td></tr></table></body></html>  \n\n（85）UV曲面印刷油墨参考配方  \n\n\n<html><body><table><tr><td>EA GPTA</td><td></td><td>15 907 30 颜料 填料</td><td>3 14</td></tr><tr><td>TPGDA</td><td></td><td>31 2</td><td>2</td></tr><tr><td>651 ITX</td><td></td><td>聚乙烯蜡 2</td><td>1</td></tr></table></body></html>  \n\n<html><body><table><tr><td>EA DEGDA TMPTA 其他稀释剂</td><td>100 651 9 6</td><td>2~5 二苯胺 0.3 稀土荧光配合物 1~3</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 476,
+        "chunk": "# （86）UV荧光油墨参考配方  \n\n（87）UV防伪油墨参考配方  \n\n\n<html><body><table><tr><td>丙烯酸共聚物溶液（MAA/MMA/EA/BA 固含量45%）</td><td>132</td><td>荧光颜料（Y，Gd）BO：Eu3+ 140</td></tr><tr><td></td><td>40</td><td>低熔点玻璃黏结料 3</td></tr><tr><td>四乙二醇二丙烯酸酯</td><td></td><td>3b</td></tr><tr><td>369</td><td>3</td><td>丁酮</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 477,
+        "chunk": "# （88）UV光纤着色油墨参考配方（表7-22)  \n\n表7-22UV光纤着色油墨参考配方  \n\n\n<html><body><table><tr><td>组成</td><td>红</td><td>黄</td><td>绿</td></tr><tr><td>有机硅环氧丙烯酸酯 脂环族环氧丙烯酸酯</td><td>60 40</td><td>60 40 5</td><td>60 40 5</td></tr><tr><td>光引发剂BK 增感剂P</td><td>5 3 0.1</td><td>3 0.1</td><td>3 0.1</td></tr><tr><td>稳定剂 分散红氨基甲酸酯丙烯酸酯（RUA)</td><td>2</td><td>一</td><td></td></tr><tr><td>分散蓝氨基甲酸酯丙烯酸酯(BUA)</td><td></td><td>一</td><td>0.44</td></tr><tr><td>吖啶黄氨基甲酸酯丙烯酸酯（YUA)</td><td>1</td><td>2</td><td>1.56</td></tr><tr><td></td><td>1.17</td><td>1.12</td><td>1.15</td></tr><tr><td>密度/（g/cm）</td><td></td><td>8850</td><td>9720</td></tr><tr><td>黏度/mPa·s</td><td>9210</td><td>1.51</td><td>1.51</td></tr><tr><td>折光率nd25</td><td>1.51</td><td></td><td></td></tr><tr><td>固化时间/s</td><td>5</td><td>2</td><td>4</td></tr><tr><td>拉伸强度/MPa</td><td>5.79</td><td>9.92</td><td>9.32</td></tr><tr><td>断裂伸长率/%</td><td>1.92</td><td>23.1</td><td>22.9</td></tr><tr><td>模量/MPa</td><td>26.5</td><td>43.8</td><td>40.0</td></tr><tr><td>吸水率(25℃/24h)/%</td><td>4.5</td><td>3.6</td><td>4.2</td></tr><tr><td>T/C</td><td>-82</td><td>-82</td><td>82</td></tr></table></body></html>  \n\n（89）UV光纤着色涂料参考配方  \n\n\n<html><body><table><tr><td>改性EA 脂肪族PUA IBOA TPGDA</td><td></td><td>40 20 3 20</td><td>369 819 TPO 184</td><td></td></tr></table></body></html>  \n\n颜料：酥菁蓝、联苯胺橘黄、菁绿、炭黑、二氧化钛、永固红、联苯胺黄、永固紫八种及复配成棕、灰、桃红、胡蓝四种颜料，共十二色。 小车",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 478,
+        "chunk": "# （90）UV喷墨油墨参考配方  \n\n（91）UV喷墨油墨参考配方   \n\n\n<html><body><table><tr><td>脂肪族PUA（CN964B85）</td><td>20.0</td><td>819</td><td>2.5</td></tr><tr><td>TEGDA DPHA IBOA</td><td>42.0 10.0</td><td>有机颜料 Efka4046</td><td>9.0 3.0</td></tr></table></body></html>  \n\n）  \n\n\n<html><body><table><tr><td>组成</td><td>黑</td><td>青</td></tr><tr><td>颜料</td><td>PBK7</td><td>DB15:4</td></tr><tr><td>颜料用量</td><td>25</td><td>25</td></tr><tr><td>研磨树脂（DR04676）</td><td>75</td><td>75</td></tr></table></body></html>  \n\n<html><body><table><tr><td>EOTMPTA TPGDA 907</td><td>28.0 50.5 4.0 1.0</td><td>DETX ODAB 菁蓝 分散剂（Solsperse32000）</td><td>2.0 3.0 3.5 8.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 479,
+        "chunk": "# （92）UV喷墨油墨参考配方",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 480,
+        "chunk": "# $\\textcircled{1}$ 色浆配方 (表7-23)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 481,
+        "chunk": "# $\\textcircled{2}$ 喷墨油墨配方 (表7-24)  \n\n表7-24 喷墨油墨配方  \n\n\n<html><body><table><tr><td>组成</td><td>黑</td><td>青</td></tr><tr><td>色浆 稀释树脂（PR04677)</td><td>20.0 70.0</td><td>20.0 70.0 9.0</td></tr></table></body></html>  \n\n表7-23 色浆配方  \n\n\n<html><body><table><tr><td>颜料 低聚物</td><td>20 单体 10</td><td>68 润湿分散剂 2</td></tr><tr><td>②油墨</td><td></td><td></td></tr><tr><td>色浆 低聚物</td><td>25 2</td><td>单体 68 光引发剂 5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 482,
+        "chunk": "# （93）UV喷墨油墨参考配方  \n\n$\\textcircled{1}$ 色浆",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 483,
+        "chunk": "# UV喷墨油墨配方见表7-25。  \n\n表7-25UV喷墨油墨配方  \n\n\n<html><body><table><tr><td>组成</td><td>黄</td><td>品</td><td>青</td><td>黑</td></tr><tr><td>颜料 EOEOEA NPGDA</td><td>美利达 黄 45</td><td>汽巴 RT-355-D 34 45 21</td><td>汽巴 BLUE4GK 30 3 20</td><td>卡博特 R250 53 20</td></tr><tr><td>TPGDA DPGDA B（上海三正超润湿分散剂）</td><td>42 2</td><td></td><td>27 20 2</td><td>27</td></tr><tr><td>B(BYK润湿分散剂）</td><td></td><td>2</td><td></td><td>2</td></tr><tr><td>A3（氰特A）：颜料</td><td>1:2</td><td>1:3</td><td></td><td>1:4</td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td>1:2</td><td></td></tr><tr><td>TPO</td><td>/</td><td>/</td><td>2</td><td>2</td></tr><tr><td>907</td><td>/</td><td>/</td><td>/</td><td>/</td></tr><tr><td>1173</td><td></td><td>/</td><td>/</td><td>/</td></tr><tr><td>184</td><td>/</td><td>/</td><td>/</td><td>/</td></tr><tr><td>651</td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>2</td><td>/</td><td></td><td></td></tr></table></body></html>  \n\n（94）阳离子UV固化油墨参考配方  \n\n<html><body><table><tr><td>脂肪族双环氧化物（UVR6105） OXetane衍生物（UVR6000）</td><td>71.0</td><td>碳酸丙酯 9.5颜料</td><td>4.0 11.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 484,
+        "chunk": "# （95）阳离子UV柔印油墨参考配方  \n\n<html><body><table><tr><td>UVR6110 TMPO</td><td>54.0</td><td>BYK307 0.3</td></tr><tr><td>BoltomH2004</td><td>12.0 10.0</td><td>Solsperse5000 0.3 Solsperse 39000 1.4</td></tr></table></body></html>  \n\n（96）阳离子UV喷墨油墨参考配方  \n\n（97）阳离子UV喷墨油墨参考配方  \n\n\n<html><body><table><tr><td>脂环族双环氧化物（UVR6105）</td><td>58.9</td><td>阳离子光引发剂Omnicat550 2.5</td></tr><tr><td>-丁内酯 双三甲氧基丙烷杂环丁烷</td><td>15.0 21.4</td><td>颜料（蓝15：1） 2.1 表面活性剂MegafaceF479 0.1</td></tr></table></body></html>  \n\n<html><body><table><tr><td>端环氧基硅氧烷（SM-A） 端环氧基硅氧烷（SM-B） Vikoflex 9010 双酚A环氧树脂</td><td>12.0 18.0 24.0</td><td>BYK307 0.4 BYK501 0.2 白颜料（Krsnos2310） 36.4</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 485,
+        "chunk": "# （98）UV阳离子喷墨油墨参考配方  \n\n<html><body><table><tr><td>端环氧基硅氧烷（SM-A） 脂肪族单体（AM-D）</td><td>38.0 38.0</td><td>BYK30 0.2 白颜料（Kronos2020） 10.0</td></tr></table></body></html>  \n\n![](images/5dd507dfb398ed8c44e37ca4f59d36f8a4602adf01cb7345392f8cb50f121ae9.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 486,
+        "chunk": "# 第8章 光固化胶黏剂  \n\n借助胶黏剂而实现物体之间的连接称为粘接(黏合、胶黏、胶接)。  \n\n物体之间的连接可以焊接、铆接、螺接、嵌接和粘接，还可以混合连接，如粘接-焊接、粘接-铆接、粘接-螺接等。粘接技术是物体连接中历史最悠久的一种，并且随着合成高分子技术的发展而在现代生活中得到广泛的应用。  \n\n粘接技术发展迅速，这是因为粘接与焊接、铆接、螺接等连接方式相比，具有如下优点。  \n\n① 能连接同类或不同类的、软的或硬的、脆性的或韧性的、有机的或无机的各种材料，特别是异性材料的连接，超薄材料的连接。  \n\n② 粘接工艺方便简单，可以简化机械加工工艺，缩短生产周期，提高产品质量。  \n\n③减轻结构质量，用粘接可以得到挠度小、质量轻、强度大、装配简单的结构。  \n\n④应力分布连续均匀，延长结构件寿命。  \n\n③ 密封性能良好，可以减少密封结构，提高产品结构内部的器件耐介质性能。  \n\n③制造成本低，复杂的结构部件采用粘接可一次完成。  \n\n?有很好的绝缘、绝热、耐腐蚀和抗震性能。  \n\n③ 粘接工艺需要劳动量少、劳动强度也较小，操作人员不需要很高的技术水平，只需要工作认真、细致即可。 C LQ  \n\n③ 生产效率高，快速固化，胶黏剂可在几分钟甚至几秒钟内就将复杂构件牢固地连接在一起，无需专门设备。  \n\n但粘接也有不足之处，其主要缺点如下。  \n\n①某些胶黏剂的剥离力比较低，受力时有蠕变倾向。  \n\n②某些胶黏剂粘接过程比较复杂，因而使大型和复杂零件的粘接受到限制。  \n\n③某些胶黏剂易燃、有毒、对皮肤有刺激性等不良反应。  \n\n$\\textcircled{4}$ 导电、导热性不良。  \n\n③在冷、热、高温、高湿、日光、生化、化学作用下，胶黏剂发生老化，影响使用寿命。  \n\n$\\textcircled{6}$ 目前还缺乏准确度和可靠性方面都较好的无损检验粘接质量的方法。  \n\n材料之间的粘接过程是在材料与胶黏剂的表面、界面进行的一个复杂的物理、化学过程。依靠胶黏剂与被粘接材料之间通过相互作用产生的粘接力，完成粘接。胶黏剂与被粘接材料之间相互作用主要有如下几种。  \n\n（1）分子间的作用力即范德华力由于范德华力随距离增大而急剧减小，所以胶黏剂对被粘接材料表面润湿，是提高范德华力的重要前提。  \n\n（2）氢键氢键是一种特殊类型的分子作用力，可看作是一种静电力的作用。氢键形成条件必须是体系一方为氢给体（电子受体)；另一方为氢受体（电子给体)，两者匹配成对(图8-1)。在形成氢键的原子配对中，X原子电负性越大，半径越小时，对 $\\bar{\\mathbf{H}}^{\\delta^{+}}$ 原子形成的氢键键能就越大。增加氢键，有利于提高粘接力。常见氢键的键能见表8-1。  \n\n![](images/c3ffcd4363515a6d6af10f00293a45d42482214666aea190de383acb31ca151c.jpg)  \n图8-1氢键示意图  \n\n表8-1常见氢键的键能  \n\n\n<html><body><table><tr><td>氢键结构</td><td>键能/(kJ/mol)</td><td>氢键结构</td><td>键能/(kJ/mol)</td></tr><tr><td>F-—---FH H</td><td>26.4~29.3</td><td>H RO-H---O</td><td>13.4~25.6</td></tr><tr><td>HO-H---0- H</td><td>14.2~24.3</td><td>R R—-NH----NHR</td><td>13.0~18.8</td></tr><tr><td>NC------N=CH</td><td>13.8~18.4</td><td></td><td></td></tr></table></body></html>  \n\n（3）酸碱作用物质分子中的原子或基团都有给、受电子的能力。由于这种电子转移过程形成酸碱作用，在粘接过程中，胶黏剂与被粘接材料必须具有酸碱匹配才能获得较高的粘接性能。常用物质的酸碱属性见表8-2。  \n\n表8-2常用物质的酸碱属性  \n\n\n<html><body><table><tr><td>酸性物质(电子受体)</td><td>碱性物质(电子给体)</td><td>酸性物质(电子受体)</td><td>碱性物质(电子给体)</td></tr><tr><td>含氟聚合物</td><td>含氨基聚合物</td><td>环氧树脂(酸酐固化)</td><td>铝(氧化铝)</td></tr><tr><td>含氯聚合物</td><td>聚醋酸乙烯</td><td>铁(氧化铁)</td><td>石灰石</td></tr><tr><td>聚乙烯醇缩醛</td><td>聚甲基丙烯酸酯</td><td>二氧化硅</td><td>聚脲</td></tr><tr><td>酚醛树脂</td><td>聚丙烯酸酯</td><td>花岗石</td><td>钛酸钡</td></tr><tr><td>沥青</td><td>聚酰胺</td><td>各种有机酸</td><td>各种有机碱</td></tr><tr><td></td><td>玻璃</td><td></td><td></td></tr></table></body></html>  \n\n（4）化学键虽然胶黏剂和被粘材料在粘接界面不大可能达到原子之间的接触状态形成密集的化学键连接，但当两物质上有能够产生化学反应的活性基团时，有可能形成一定数量的化学键，这对提高粘接性能是十分有意义的。  \n\n$\\textcircled{1}$ 通过胶黏剂与被粘材料分子中含有的活性基相互反应形成化学键：  \n\n活泼氢与—NCO反应；  \n活泼氢与—COCI反应；  \n羟基与—NCO反应；  \n\n羟基与环氧基反应；  \n\n羟基与羟亚甲基反应。  \n\n$\\textcircled{2}$ 通过偶联剂作用使两种物质之间形成化学键结合。偶联剂是分子中含有能同时对胶黏剂和被粘材料表面分别产生化学反应的活性基团的化合物，常用的偶联剂有硅烷偶联剂和钛酸酯偶联剂。  \n\n$\\textcircled{3}$ 通过被粘物表面处理获得活性基团。如电晕放电、火焰处理、氧化处理、金属阳极处理、酸洗处理，使被粘物表面产生 $\\scriptstyle\\sum_{c=0}$ 、—OH、一 $\\cdot_{\\mathrm{ONO}_{2}}$ 等活性基团，都属于极性基团，使表面能及可润湿性随之增大，提高了粘接性能；在一定条件下，也有可能与胶黏剂发生化学反应，形成化学键，提高了粘接力。  \n\n（5）静电作用当金属与非金属物质（如聚合物）紧密接触时，由于金属物质对电子亲和力低，非金属物质对电子亲和力高，在界面区容易产生接触电势，并形成双电层。双电层导致的静电吸引力有利于提高粘接力。  \n\n（6）界面的扩散作用基于分子（或链段）热运动的界面扩散作用和物质的溶解过程相类似，它们都是一个“混合”的过程。胶黏剂/被粘物的界面扩散作用，结果导致模糊界面的产生，甚至界面的消失（如固体溶解于液体中)，有利于粘接性能提高。  \n\n（7）机械作用力当胶黏剂充满或部分充满被粘物的孔隙或凹面，通过固化在界面区形成各种形式的锚合结构，提供了机械连接力，有利于粘接性能提高。  \n\n目前在市场上销售的胶黏剂品种繁多，按固化方式可归纳为溶剂型、水基型、反应型、热熔型和辐射固化型五大类。它们的部分性能比较见表8-3。  \n\n表8-3各种胶黏剂比较  \n\n\n<html><body><table><tr><td>类型</td><td>溶剂</td><td>生产速度</td><td>透明性</td><td>耐热和耐化学品性</td><td>价格</td></tr><tr><td>溶剂型</td><td>有</td><td>中</td><td>尚可/好</td><td>尚可</td><td>低</td></tr><tr><td>水基型</td><td>无</td><td>低</td><td>尚可/好</td><td>尚可</td><td>低</td></tr><tr><td>反应型</td><td>无</td><td>低</td><td>尚可</td><td>非常好</td><td>高</td></tr><tr><td>热熔型</td><td>无</td><td>：高</td><td>尚可</td><td>尚可</td><td>低</td></tr><tr><td>辐射固化型</td><td>无</td><td>非常好</td><td>好</td><td>非常好</td><td>较高</td></tr></table></body></html>\n\n①包括双组分或单组分，热固化或湿气固化等。  \n\n辐射固化型胶黏剂包括了光固化胶黏剂和电子束固化胶黏剂，而光固化胶黏剂又分UV胶黏剂和可见光胶黏剂，UV胶黏剂又有自由基UV胶黏剂和阳离子UV胶黏剂，近年来又出现了UV双重固化胶黏剂和UV多重固化胶黏剂，如UV/厌氧、UV/热、UV/湿气、UV自由基/阳离子双重固化胶黏剂。  \n\n光固化胶黏剂与其他胶黏剂相比有如下优点：  \n\n①固化速率快，生产效率高，特别适合流水生产线工作；  \n$\\textcircled{2}$ 不用溶剂，环保、安全，改善劳动环境；  \n$\\textcircled{3}$ 低温固化，节省能源，特别适用于对热敏感的材料粘接；  \n$\\textcircled{4}$ 粘接的综合性能优异。  \n但光固化胶黏剂也存在缺点：①只能粘接一面可透过光的材料，表8-4列出部分材料的光透过性；$\\textcircled{2}$ 容易受被粘材料厚度的影响；  \n$\\textcircled{3}$ 胶黏剂中不能使用较多的填料；  \n$\\textcircled{4}$ UV光对人体皮肤和眼睛有较大的伤害；  \n$\\textcircled{5}$ 需要光源和设备。  \n\n表8-4部分材料的光透过性（光源：高压汞灯）  \n\n\n<html><body><table><tr><td rowspan=\"2\">被粘材料</td><td rowspan=\"2\">厚度/mm</td><td colspan=\"3\">透过光照度/（mW/cm²）</td></tr><tr><td>360nm</td><td>405nm</td><td>436nm</td></tr><tr><td>无</td><td></td><td>130</td><td>183</td><td>149</td></tr><tr><td>软质PVC</td><td>1</td><td>0.1</td><td>102</td><td>107</td></tr><tr><td>硬质PVC</td><td>3</td><td>0.3</td><td>97</td><td>122</td></tr><tr><td>PC</td><td>3</td><td>0</td><td>100</td><td>128</td></tr><tr><td>ABS</td><td>3</td><td>0.1</td><td>4</td><td>6</td></tr><tr><td>三氧化二铝</td><td>3</td><td>0.1</td><td>0.8</td><td>0.6</td></tr><tr><td>钠玻璃</td><td>3</td><td>83</td><td>145</td><td>117</td></tr></table></body></html>  \n\n从表8-4中可看到材料对可见光透过性比UV优异得多。因此可见光胶黏剂可比UV胶黏剂粘接更多的材料和较厚的材料；可见光胶黏剂的固化性能（光学性能、机械性能、电性能、化学性能等）也可在较宽的范围内调整；可见光对人的眼睛和皮肤损害小；可见光光源相对便宜，甚至可以利用太阳光来固化。但可见光胶黏剂在生产、贮存、运输和使用时必须避光，这也给生产和使用带来困难。  \n\n光固化胶黏剂也是由低聚物、活性稀释剂、光引发剂和各种添加剂组成。",
+        "category": " Introduction"
+    },
+    {
+        "id": 487,
+        "chunk": "# 8.2.1 低物  \n\n低聚物是光固化胶黏剂的主要成分，它的结构和分子量大小决定了胶黏剂的最终性能，如光固化速率、粘接性能、透明度、耐溶剂性、耐候性、柔韧性等。自由基光固化胶黏剂常用的低聚物为聚酯（甲基）丙烯酸酯、环氧（甲基）丙烯酸酯、聚氨酯（甲基）丙烯酸酯、（甲基）丙烯酸酯化丙烯酸树脂、聚醚（甲基）丙烯酸酯，此外还有聚丁二烯（甲基）丙烯酸酯、三聚氰胺丙烯酸树脂等。阳离子光固化胶黏剂常用的低聚物为环氧树脂和乙烯基醚树脂。大多数光固化胶黏剂首选的低聚物是环氧（甲基）丙烯酸酯和聚氨酯（甲基）丙烯酸酯，再配以其他低聚物。随着光固化技术的发展，一些新的低聚物如超支化低聚物、自由基阳离子杂化低聚物的开发，给光固化胶黏剂提供了新的、性能更佳的低聚物。另外，双重固化体系的出现，也使光固化胶黏剂的固化更方便和完全，一些双重固化光固化胶黏剂已商品化。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 488,
+        "chunk": "# 8.2.2 活性稀释剂  \n\n活性稀释剂是光固化胶黏剂的重要组成，它一方面起稀释剂作用，使胶黏剂具有施工的黏度；另一方面具有反应活性，光照时，与低聚物共聚形成网络结构，可以提高体系的光固化速率和改善某些物理力学性能。在自由基光固化胶黏剂中常用的活性稀释剂为功能性丙烯酸酯和功能性甲基丙烯酸酯，由于功能性甲基丙烯酸酯对人的皮肤刺激性远远低于功能性丙烯酸酯（表8-5)，所以在光固化胶黏剂中常常使用功能性甲基丙烯酸酯。阳离子光固化胶黏剂所用活性稀释剂则为乙烯基醚化合物或环氧化合物。  \n\n表8-5功能性丙烯酸酯与功能性甲基丙烯酸酯的比较  \n\n\n<html><body><table><tr><td rowspan=\"2\">(甲基)丙烯酸酯对应的醇</td><td colspan=\"2\">初期皮肤刺激性指数PII</td></tr><tr><td>丙烯酸酯</td><td>甲基丙烯酸酯</td></tr><tr><td>1,3-丁二醇</td><td>8.0</td><td>0.0</td></tr><tr><td>1,6-已二醇</td><td>5.5</td><td>0.5</td></tr><tr><td>新戊二醇</td><td>8.0</td><td>0.0</td></tr><tr><td>二甘醇</td><td>3.0</td><td>0.5</td></tr><tr><td>双酚A二甘醇</td><td>0.8</td><td>1.0</td></tr><tr><td>壬基苯氧基乙醇</td><td>4.2</td><td>1.0</td></tr><tr><td>四氢糠醇</td><td>8.0</td><td>1.3</td></tr><tr><td>苯氧基乙醇</td><td>3.3</td><td>1.4</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 489,
+        "chunk": "# 8.2.3 光引发剂  \n\n光引发剂也是光固化胶黏剂的重要组成，但不同类型的光固化胶黏剂使用不同类型的光引发剂。自由基UV胶黏剂主要用安息香醚、二苯甲酮、651、1173、184、500、TPO和819 等光引发剂；阳离子UV胶黏剂则以硫盐或碘盐阳离子光引发剂为主；而可见光胶黏剂则主要用樟脑或配合TPO、819、苯偶酰等光引发剂。光固化胶黏剂常常用叔胺类助引发剂配合，以减少氧阻聚的影响，如甲基丙烯酸二甲氨基乙酯、4-二甲氨基苯甲酸乙酯(EDAB)、4-二甲氨基苯甲酸异戊酯（ODAB)、三乙醇胺、三乙胺、N-甲基二乙醇胺等。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 490,
+        "chunk": "# 8.2.4 添加剂  \n\n光固化胶黏剂常用添加剂有增塑剂、偶联剂、阻聚剂、填料等。  \n\n（1）增塑剂这是一种能降低高分子化合物玻璃化温度、改善胶层脆性的物质。在胶黏剂中适量加入增塑剂可增加胶层的韧性、延伸率和耐寒性，降低其内聚强度、弹性模量。常用增塑剂为邻苯二甲酸酯类、磷酸酯类、乙二酸酯类和癸二酸酯等，邻苯二甲酸酯由于毒性大，已逐渐不再使用。  \n\n（2）偶联剂这是一种分子中同时具有极性和非极性部分的物质，能同时与极性材料和非极性材料产生一定结合力。因此胶黏剂中常适量加入偶联剂，增加了主体树脂分子本身的分子间作用力，提高了胶黏剂的内聚强度；增加了主体树脂与被粘物之间的结合，起了一定的“架桥”作用，提高了胶黏剂的粘接性能。常用的偶联剂为硅烷偶联剂（表8-6)。 55  \n\n（3）阻聚剂这是用来阻止或延缓胶黏剂中含有不饱和键的树脂、单体在贮存或运输过程中发生交联的物质，常用的为对苯二酚、对甲氧基苯酚等。  \n\n（4）填料这是一种不与主体材料起化学反应，但可以改善其性能，降低成本的固体物质。填料按成分分为无机填料和有机填料两类。无机填料主要为矿物填料，如瓷粉、高岭土粉、氧化铝粉、玻璃粉、玻璃纤维等，在胶黏剂中加入无机填料可改善耐热性，降低固化收缩，增加耐磨性和强度等，但使胶黏剂密度增加，脆性增加，透明度变差；有机填料如尼龙粉、塑料粉、植物纤维等，在胶黏剂中加入有机填料可改善胶层脆性，增加抗冲击韧性，减少固化收缩等，但透明度也变差。由于光固化胶黏剂中加入填料。都会影响光的透过，不利于光固化，因此在配方中尽量少加。常用有机硅偶联剂见表8-6。  \n\n表8-6常用有机硅偶联剂  \n\n\n<html><body><table><tr><td>商品牌号</td><td>偶联剂名称</td><td>表面能/（N/cm）</td></tr><tr><td>A-151</td><td>乙烯基三乙氧基硅烷</td><td>25X10-5</td></tr><tr><td>A-132</td><td>乙烯基三(β甲氧基乙氧基)硅烷</td><td></td></tr><tr><td>A-174(KH570)</td><td>-甲基丙烯酰氧基丙基三甲氧基硅烷</td><td>28X10-5</td></tr><tr><td>A-186</td><td>β（3，4-环氧环已基）乙基三甲氧基硅烷</td><td></td></tr><tr><td>A187(KH560)</td><td>-(2，3-环氧丙氧基)丙基三甲氧基硅烷</td><td>42.5×10-5</td></tr><tr><td>A1120(KH550)</td><td>-氨基丙基三乙氧基硅烷</td><td>35X10-5</td></tr><tr><td>A189</td><td>y-硫醇基丙基三甲氧基硅烷</td><td>41X10-5</td></tr><tr><td>A-1120</td><td>Y,β(氨基乙基）-氨基丙基三甲氧基硅烷</td><td></td></tr><tr><td>南大22</td><td>二乙基氨甲基三乙氧基硅烷</td><td></td></tr><tr><td>南大42</td><td>苯胺甲基三乙氧基硅烷</td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 491,
+        "chunk": "# 8.3UV结构胶  \n\n结构胶（structuraladhesive）是用于各种材料结构件之间粘接的胶黏剂，以代替铆接、焊接和螺栓等连接，具有质量轻、表面光滑、应力集中小、密封性好等优点。结构胶黏剂要求粘接强度高、耐久性好、固化快、使用方便、表面处理简单、耐温性好（可在 $-40\\sim$ $150^{\\circ}\\mathrm{C}$ 使用)、耐油性和耐水性好、对多种材料都有较好的粘接性能。20世纪50年代开发了第一代丙烯酸酯胶黏剂（first generation adhesive，简称FGA)；1975 年杜邦公司开发了第二代丙烯酸酯胶黏剂（second generation adhesive，简称 SGA）属于快固型丙烯酸酯胶黏剂；之后出现了UV/EB固化型丙烯酸酯胶黏剂称为第三代丙烯酸酯胶黏剂（third genera-tion adhesive，简称TGA)。这三类丙烯酸酯胶黏剂都属于反应型丙烯酸酯胶黏剂，都具有室温快速固化、粘接强度高、韧性好，可油面粘接、适应性强、工艺简便等特点，已广泛用于航空航天、汽车、船舶、铁路车辆、机械、电子、电器、仪表，建筑、家具、土木工程等行业的结构粘接、小件装配、大件组装、应急修复、防渗堵漏等，在尖端技术和高新科技方面也得到了较好的应用。  \n\nUV丙烯酸酯结构胶黏剂是由（甲基）丙烯酸类低聚物和单体、增韧树脂、光引发剂、稳定剂和其他助剂等组成。低聚物主要为环氧（甲基）丙烯酸酯、聚氨酯（甲基）丙烯酸酯、聚酯（甲基）丙烯酸酯等；单体为（甲基）丙烯酸单酯、双酯等。为了提高韧性、耐冲击性、耐疲劳性、耐久性和粘接强度，往往需加入一些弹性体作增韧树脂。弹性体加入，有的参与反应，产生接枝共聚物；有的会形成“海-岛”结构，提高粘接性能；同时还可调节黏度，降低固化收缩率。常用弹性体如丙烯酸酯橡胶、丁睛橡胶、SBS 等。光引发剂也由最早的安息香醚类改用1173、184、651等高效引发剂，并配以叔胺类助引发新剂，以减少氧阻聚的影响。助剂上，用酚类阻聚剂以提高贮存稳定性；加人气相二氧化硅，以提高触变性；加人硅烷偶联剂，以提高耐水性和粘接强度。  \n\nUV结构胶一般需具备以下性能：  \n\n<html><body><table><tr><td>剪切强度/MPa 剥离强度/（kN/m）</td><td>>10 硬度（shoreD） 40~80 >2 耐温范围/℃ -60~150</td></tr></table></body></html>  \n\n经过配方设计，UV结构胶可以达到传统结构胶的各种性能，而且在更短时间内达到最高强度，见表8-7。  \n\n表8-7常用结构胶达到最高强度比较  \n\n\n<html><body><table><tr><td>结构胶</td><td>初固时间</td><td>达到最高强度时间</td></tr><tr><td>室温固化环氧结构胶</td><td>10~120min</td><td>7d</td></tr><tr><td>第二代丙烯酸酯结构胶</td><td>1~30min</td><td>24h</td></tr><tr><td>UV结构胶</td><td>1~5s</td><td>1h</td></tr></table></body></html>  \n\n因此，UV结构胶可以满足自动化生产线的使用要求，这是其他类型结构胶无法比拟的。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 492,
+        "chunk": "# 8.4UV密封胶  \n\n密封表示密闭封住，起防止内部气体或液体的渗漏；防止外部灰尘和水分的侵人；防止机械松动、冲击损伤；还能起到隔音、隔热、阻尼、减震等作用。密封的方法很多，如金属垫圈，橡胶垫片、石棉毡垫、皮革片、纸垫、油灰、腻子等，而采用胶黏剂密封则是一种新的方法，是当代密封技术的重大进展。用于密封的胶黏剂简称密封胶（sealants)，同时具有粘接和密封作用，它与传统的密封材料相比有很多优越性。  \n\n（1）密封性好密封胶是以聚合物为主体的液态材料，涂在接合部位能填充表面凸凹不平处，干燥后便形成连续的黏弹性胶膜，起到可靠的耐压密封作用，不易泄漏。  \n\n（2）通用性强可用于耐油、耐水、耐化学物质的密封，一种密封胶可代替多种固体垫圈，用于多种场合的密封。  \n\n（3）耐久性优密封胶不易腐蚀、不易损坏、不易疲劳、使用寿命长。  \n\n（4）适应性广密封胶可在- $-60\\sim300^{\\circ}\\mathrm{C}$ 使用，有的还可耐超低温一 $253^{\\circ}\\mathrm{C}$ 和超高温 $600^{\\circ}\\mathrm{C}$ α  \n\n（5）降低成本密封胶用量少，降低加工精度，减少紧固件数量，减轻整体质量，节能耗、效率高。  \n\n（6）使用方便密封胶可自由成型，不受工件形状限制，施工简单，拆卸容易，更换快速。  \n\n密封胶种类很多，可分为弹性密封胶、非弹性密封胶和液体嵌缝垫料。按照补偿位移的能力，密封胶可分为下列五种。 木  \n\n<html><body><table><tr><td>类别 硬化密封胶 塑性密封胶 弹塑性密封胶</td><td>补偿位移的能力/% 类别 0 2~8 8~15</td><td>补偿位移的能力/% 塑弹性密封胶 15~20 弹性密封胶 20~25</td></tr></table></body></html>  \n\n密封是工程上极为重要的问题，密封胶在航天、航空、机械、电子、电气、电器、汽车、造船、建筑、石油化工、军工等领域都得到了广泛的应用。  \n\nUV密封胶是新发展起来的一种密封胶，它的主体树脂为环氧（甲基）丙烯酸酯、聚氨酯（甲基）丙烯酸酯或聚酯（甲基）丙烯酸酯，用量可占到胶黏剂的 $50\\%\\sim90\\%$ ，配以适当的活性稀释剂和光引发剂，另外根据需要还要选用一些相应的填料。  \n\nUV密封胶必须要UV光照射才能固化，所以UV密封胶必须要在一面能透过UV光的器件上才能应用，这是它的最大弱点。  \n\nUV光学胶主要用于粘接光学透明元件的特种胶黏剂，它必须符合如下要求：  \n\n$\\textcircled{1}$ 无色透明，在指定的光波波段内光透过率 $>97\\%$ ，并且固化后胶黏剂的折射率与被粘光学元件的折射率相近；  \n\n$\\textcircled{2}$ 在使用温度范围内，胶黏剂的粘接强度良好；  \n\n$\\textcircled{3}$ 胶黏剂的模量低，固化后延伸率大，同时固化收缩率小，不会引起光学元件表面的变化；  \n\n$\\textcircled{4}$ 吸湿性小；  \n\n$\\textcircled{5}$ 耐冷热冲击、耐振动、耐油、耐溶剂等；  \n\n$\\textcircled{6}$ 操作性能好，在维修时，可用简单的方法分离；  \n\n$\\textcircled{7}$ 对人体无害或低毒性。  \n\nUV玻璃胶又叫无影胶，也是一种光学胶黏剂，由于主要用于玻璃与玻璃、金属、塑料之间的粘接，对光学性能和固化收缩要求较低，但是要对玻璃的粘接性能好。  \n\n由于光学玻璃和玻璃是一种典型的脆性材料，十分易碎；同时又是热膨胀系数较小的材料，因此这两种胶黏剂都必须考虑其自身和材料之间由于温度变化，热膨胀系数差别大而产生热应力的问题。对UV光学胶，在考虑热膨胀系数的同时，也应特别注意固化体积收缩问题，要避免热膨胀系数差异过大或固化收缩过大而产生的应力过大，造成玻璃产生自然破裂或胶黏剂开裂现象。常用材料的线性热膨胀系数见表8-8。  \n\nUV光学胶和UV玻璃胶主体树脂，以环氧（甲基）丙烯酸酯最为理想，它的折射率和透光率优异，有较低的热膨胀系数，耐热性和耐寒性也良好，而且固化速率也快，但固化体积收缩稍大。另外也可选用聚氨酯（甲基）丙烯酸酯、有机硅（甲基）丙烯酸酯。适量地添加有机硅偶联剂如KH570等，有利于提高UV光学胶和UV玻璃胶的粘接力。  \n\n表8-8常用材料的线性热膨胀系数  \n\n\n<html><body><table><tr><td>材料</td><td>热膨胀系数/×10-6℃-1</td><td>材料</td><td>热膨胀系数/×10-5℃-1</td></tr><tr><td>石英玻璃</td><td>0.6</td><td>环氧树脂</td><td>45~65</td></tr><tr><td>钠玻璃</td><td>9.0</td><td>酚醛树脂</td><td>60~80</td></tr><tr><td>氧化铝</td><td>8.7</td><td>聚酯</td><td>55~100</td></tr><tr><td>铝</td><td>23</td><td>聚苯乙烯</td><td>60~80</td></tr><tr><td>钢</td><td>10~14</td><td>聚丙烯</td><td>100~200</td></tr><tr><td>石墨</td><td>7.8</td><td>聚氨酯树脂</td><td>100~200</td></tr><tr><td>黄铜</td><td>19</td><td>有机硅树脂</td><td>160~180</td></tr><tr><td>聚酰亚胺</td><td>33~54</td><td></td><td></td></tr></table></body></html>  \n\n压敏胶（pressure sensitive adhesives，简称为PSA）是制造压敏型胶黏带用的胶黏剂。压敏胶黏带是胶黏剂中一种特殊的类型，它通常是将胶黏剂涂于基材上，加工成带状并制成卷盘供应用户。它又是一种能长期处于黏弹状态的“半干性”特殊胶黏剂，只需略施压力即可实现瞬时粘接。  \n\n压敏胶带有单面压敏胶、双面压敏胶和胶黏片三种形式（图8-2)。单面压敏胶带是在基材正面涂底涂层后再涂压敏胶，反面涂背面处理剂后卷成筒；双面压敏胶带和胶黏片不用背涂处理处，但需在一个胶面上贴一层隔离纸。  \n\n![](images/f7713924905ec52d275644e5ffba7f4a3ea30fb69fcc5788b91b1fb3903cfcaa.jpg)  \n图8-2压敏胶带的结构示意图  \n\n（1）基材基材是支承压敏胶的基本材料。它必须有较好的机械强度，厚薄均匀，不易变形，并与压敏胶浸润较好等性能。常用的基材有聚丙烯、聚乙烯、聚酯、软质或半软质聚氯乙烯等塑料薄膜，棉布、玻璃布、合成纤维布等织物以及牛皮纸等纸张。  \n\n（2）底层处理剂也称底涂剂、底胶，涂布于胶黏剂与基材之间以增加胶黏剂对基材的黏附力，防止脱胶。底胶可以用对基材有亲和力的树脂和对压敏胶有亲和力的树脂混合而成；也可用对压敏胶有亲和力的聚合物为主链，用对基材有亲和力的化合物进行接枝共聚而成，有些压敏胶与基材黏附力强，也可不用底胶。  \n\n（3）背面处理剂单面压敏胶带基材背面应涂上一层化学物质以便胶黏带卷筒时起层间隔离作用，这种化学物质为背面处理剂。选择背面处理剂要考虑具有较好的层间隔离能力，揭剥胶带时背面不能带有下层的压敏胶，同时要有较好的透明性和非迁移性。常用的背面处理剂以有机硅化合物为主。对聚乙烯、聚丙烯、聚氯乙烯薄膜作基材则不用背面处理剂。  \n\n（4）隔离纸对双面压敏胶带、标签、黏结胶纸、胶黏片等用的压敏胶表面上应覆盖一层隔离纸，常用的隔离纸有半硬性聚氯乙烯薄膜、聚丙烯薄膜、涂有背面处理剂的牛皮纸等。  \n\n压敏胶的压敏性是它的黏附特性的表现，其黏附特性是由快粘力、黏合力、内聚力和粘基力四种黏附力决定。快粘力是压敏胶带与被粘物之间以最小的压力和最快的速度接触后立即分离时所表现出来的一种界面剥离力，它体现出压敏胶对被粘物表面进行粘接的难易程度。黏合力是进行适当粘贴后压敏胶带与被粘物表面之间所体现出的剥离力，其大小决定着压敏胶带的黏附性能。黏合力必须大于快粘力，否则就没有压敏性。内聚力即粘贴后压敏胶的内聚强度，内聚力必须大于黏合力，否则揭压敏胶带时，压敏胶层会破坏。粘基力是压敏胶与基材之间的黏附力，或压敏胶与底胶及底胶与基材间的黏附力。粘基力必须大于内聚力，否则压敏胶层与基材间容易脱开。因此对压敏胶带来说，必须满足粘基力 $>$ 内聚力>黏合力 $>$ 快粘力。  \n\n（5）压敏胶黏剂压敏胶黏剂是压敏胶带中的最重要组分，它给胶黏带以压敏黏附力。压敏胶黏剂由橡胶类或其他弹性体与增黏树脂、增塑剂、防老剂等组成。作为压敏胶黏剂的聚合物玻璃化温度一般应在一 $45\\mathrm{^\\circC}$ 左右。目前用作压敏胶的树脂以丙烯酸酯共聚物为主。选择合适的丙烯酸酯共聚使共聚物玻璃化温度控制在 $-45\\%$ ，并适当交联，以提高内聚力。由于采用乳液聚合，不用溶剂，无污染，操作方便、安全、符合环保要求。乳液型丙烯酸酯压敏胶不易水解、耐光性好、抗氧性好，对许多基材有优良的附着力，获得迅速发展成为压敏胶主体。  \n\n辐射固化压敏胶是一类新型无溶剂压敏胶，室温下处于黏稠液体状态。使用时将其涂布在基材上，经电子束或紫外光照射后，才成为具有实用性能的压敏胶制品。制备辐射固化压敏胶的原料主要为丙烯酸酯类单体及适当配以烯类单体。这些单体大致可分为三类：软单体、硬单体和官能单体。  \n\n软单体是压敏胶的主要单体，其作用是产生玻璃化温度 $T_{\\mathfrak{g}}$ 较低的、具有初黏性的聚合物，常用的有丙烯酸丁酯、丙烯酸2-乙基己酯等。这些低 $T_{\\mathrm{{g}}}$ 的聚合物内聚强度低，因此，通常不能单独用作压敏胶黏剂。  \n\n硬单体是能产生较高 $T_{\\mathrm{{g}}}$ 并能与软单体共聚的（甲基）丙烯酸酯或其他烯类单体，常用的有甲基丙烯酸甲酯、丙烯腈、醋酸乙烯酯、苯乙烯、甲基丙烯酸丁酯等。硬单体和软单体只有以适当配比共聚后，才能制得较高内聚强度和使用温度性能较好的压敏胶黏剂。  \n\n官能单体是带有各种官能基团并能与软、硬单体共聚的烯类单体，可使压敏胶产生一定程度的交联，使内聚强度、耐热性和耐老化性能大为提高。常用的官能单体有（甲基）丙烯酸、（甲基）丙烯酸羟乙酯、（甲基）丙烯酸羟丙酯、（甲基）丙烯酸缩水甘油酯、（甲基）丙烯酸乙二醇酯，（甲基）丙烯酰胺、 $N\\cdot$ -羟甲基丙烯酰胺、马来酸酐、衣康酸、二乙烯基苯等。也可用聚丁二烯类橡胶，利用其双键参与交联，本身又具有粘接性能。  \n\n除了丙烯酸酯类单体作压敏胶主体外，聚氨酯丙烯酸酯作压敏胶主体也非常有效，只是成本上要贵一些。  \n\n辐射固化压敏胶中，UV压敏胶还必须加人光引发剂。早期用安息香醚类和二苯甲酮，现在大多改用1173、184、651等效率更高的光引发剂。  \n\n有时为了改善压敏胶的某些性能，降低成本等，也可加入一些添加剂。如加人增黏剂提高对聚乙（丙）烯等难粘接材料的粘接强度；加入阻燃剂可使压敏胶具有阻燃性，但加入量均应不影响光固化速率为准。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 493,
+        "chunk": "# 8.7UV离型剂  \n\n离型剂（release agent）也叫隔离剂或防粘剂，是制备压敏胶的防粘层、自黏性标签的隔离层及其他各类黏性物质的包装材料所需的配套材料。目前，防粘离型剂产品大多是用有机硅材料制得，这是因为有机硅材料具有较低的表面能、优良的耐老化性能、低毒性和温度适用范围广。UV固化的有机硅离型剂是新一代的离型剂产品，它具有固化时间短、耗能低、效率高、不含有机溶剂、无污染等优点，非常适合用于压敏胶的防粘离型材料。  \n\nUV固化有机硅离型剂主要是聚硅烷光交联固化后形成低表面能的防粘膜。一般以聚硅氧烷作为分子主链，以端基为丙烯酸基作为光敏功能基团的有机硅丙烯酸酯低聚物，聚硅氧烷链段赋予低表面性能，而丙烯酸基团具有光固化性能，加人光引发剂并在UV光照后，迅速聚合并交联固化而制得。  \n\n有机硅丙烯酸酯低聚物常用端基含氯的聚硅氧烷与丙烯酸羟基酯或季戊四醇三丙烯酸酯缩合而成；光引发剂一般以651、1173、二苯甲酮或651、1173与二苯甲酮复合使用。为了提高光固化速率和减少氧阻聚作用，还需配以少量活性胺。将有机硅丙烯酸酯低聚物与光引发剂配成的涂布液涂覆在基材（纸基或塑料薄膜）上经UV固化就制得UV离型材料。  \n\n传统的导电连接用焊、铆等工艺方法，现正逐步被导电粘接所取代。用于导电粘接的胶黏剂称为导电胶黏剂，简称导电胶。导电胶固化或干燥后，具有一定的导电性和良好的粘接性能，使被粘接材料之间形成电的通路。导电胶在室温或较低温度下固化，可避免因高温焊接引起的材料变形、元件损坏，且可防止铆接的应力集中及电磁信号的损失、泄漏等。采用导电胶粘接不需要特殊的设备，因此，导电粘接作为一种新工艺，正得到广泛的应用。  \n\n导电胶是由粘接料、导电填料、增韧剂、偶联剂、固化剂和溶剂等组成。按粘接料的化学组成可分为无机导电胶和有机导电胶，常用的是有机导电胶。UV导电胶是最近开发的新产品，常用的粘接料为环氧丙烯酸树脂、酚醛环氧丙烯酸树脂、聚氨酯丙烯酸树脂、丙烯酸树脂等。  \n\n导电填料有金粉、银粉、铜粉、镍粉、铝粉、石墨、炭黑、碳纤维、镀银铜粉、镀银二氧化硅粉、镀银玻璃微珠等。一些导电填料的电阻率见表8-9。  \n\n表8-9常用导电填料的电阻率  \n\n\n<html><body><table><tr><td>导电填料</td><td>金</td><td>银</td><td>铜</td><td>铝</td><td>镍</td><td>锡</td><td>石墨</td><td>炭黑</td></tr><tr><td>电阻率/Ω·cm</td><td>2.40X10-°</td><td>1.62X10-</td><td>1. 69×10-62. 62×10-67.23×10-b1.14×10-5</td><td></td><td></td><td></td><td>1~10-3</td><td>1~10-2</td></tr></table></body></html>  \n\n银粉具有优良的导电性和化学稳定性，是比较理想和应用最多的导电填料。银粉的制备方法有电解法、化学还原法、热分解法、喷射法、碾磨法等。不同方法制得的银粉粒度和形状不同(表8-10)。为了保证银粉在胶层中紧密接触，最好使用电解法超细银粉与鳞片状银粉的混合填料。银粉在空气中氧化极慢，在胶层中几乎不氧化，即使氧化，生成的氧化物仍有一定的导电性，因而在电气可靠性要求高的产品上应用最多。银粉价格高，密度大，易沉淀，在潮湿环境中有迁移现象，但在导电胶配制中，银粉仍是最常用的导电填料。在导电胶中银粉用量一般为树脂的 $\\scriptstyle2\\sim3$ 倍，从导电性和粘接性综合考虑，树脂和银粉的比例为 $_{30}:$ 70较为适宜。  \n\n表8-10不同方法制得的银粉的性质  \n\n\n<html><body><table><tr><td>制备方法</td><td>电解法</td><td>化学还原法</td><td>热分解法</td><td>喷射法</td><td>碾磨法</td></tr><tr><td>银粉粒度/μm</td><td>0.2~10</td><td>0.2~2</td><td>一</td><td>约40</td><td>0.1~2</td></tr><tr><td>粒子形状</td><td>针状</td><td>球状或无定形</td><td>海绵状</td><td>球状</td><td>片状</td></tr></table></body></html>  \n\n金粉具有优异的化学稳定性和优良的导电性，是导电胶中最理想的导电填料，但价格昂贵，只能用于要求稳定性和可靠性非常高的产品上。  \n\n铜粉、铝粉和镍粉具有较好的导电性，成本较低，来源容易，无迁移现象，但在空气中易氧化，使导电性变坏，使用性能受到限制。由铜、铝、镍粉所配制的导电胶，其稳定性和可靠性不如银系导电胶，仅用于稳定性和可靠性要求不高的产品上。在使用铜粉和镍粉时，要加人叔胺或酚类助剂进行抗氧化保护，以提高导电性能。  \n\n炭粉和石墨粉成本低，密度小，分散性好，但导电性差，仅用于屏蔽和防静电的产品上。  \n\n现在还采用在铜粉上经化学还原方法镀银，制得镀银铜粉作为导电填料，既具有铜价格较低、无迁移的优点，又具有银导电性和化学稳定性好的优点，可以配制成UV导电胶的电阻率在 $10^{-4}\\Omega\\cdot\\mathrm{cm}$ ，是一种有发展前途的导电填料。  \n\n除了铜粉镀银外，还可将中空微玻璃球、二氧化硅、炭粉、铝粉等粒子镀银，得到镀银导电填料，具有导电性好、成本低、密度小等特点，可用于配制对导电性要求不高的导电胶。  \n\n由于UV导电胶含有大量的金属导电填料，严重阻碍UV光的穿透，影响UV导电胶的固化，特别是底层胶的固化。因此可采用双重固化体系来保证UV导电胶的固化完全。如用自由基光固化/阳离子光固化双重固化、自由基光固化/热固化双重固化，先UV固化，再经红外进行后固化，使导电胶完全固化。  \n\n导电胶中金属导电填料密度大，容易发生沉降，故在使用导电胶时必须充分搅匀，使金属导电填料均匀分散在胶液中，保证导电性能稳定。  \n\n以下配方单位为质量份。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 494,
+        "chunk": "# （1）UV胶黏剂参考配方  \n\n<html><body><table><tr><td>MMA-BA-HPA三元共聚物 PETA HDDA</td><td>50 HPA 10 651 12</td><td>25 3</td></tr><tr><td colspan=\"3\">（2）UV胶黏剂参考配方</td></tr><tr><td>HPMA 双甲基丙烯酸乙二醇酯 甲基丙烯酸四氢呋喃甲酯 AA</td><td>40 5 BEE 40 HQ 5</td><td>聚乙烯醇缩丁醛 10 2 0.1</td></tr><tr><td colspan=\"3\">（3）UV胶黏剂参考配方</td></tr><tr><td>聚醚增韧改性不饱和聚酯 苯乙烯 651 性能：</td><td>63 35 2</td><td>黏度/mPa·s 300 固化时间（250WUV灯）/min 5~20 透光率/% 98 剪切强度/mPa 玻璃破坏（玻璃/钢片）</td></tr><tr><td colspan=\"3\">（4）UV胶黏剂参考配方</td></tr><tr><td>EA NVP</td><td>48.0 651 32.0 BP</td><td>2.7 1.3</td></tr></table></body></html>\n\n\n\n<html><body><table><tr><td>EA NVP</td><td>48.0 32.0</td><td>651 BP</td><td>2.7 1.3</td></tr></table></body></html>  \n\n（5）UV胶黏剂参考配方 上！！大  \n\n<html><body><table><tr><td>EA 100 BEE TMPTA 40 偶联剂（KH570）</td></tr><tr><td>（6）UV胶黏剂参考配方 100 HQ</td></tr><tr><td>EA 0.15 邻苯二甲酸二烯丙基酯 35651 4</td></tr><tr><td>可用于玻璃、光学玻璃黏合 市 （7）UV胶黏剂参考配方 60</td></tr><tr><td>EA 20 HPA PUA 20 BEE 6</td></tr><tr><td>（8）UV胶黏剂参考配方 PUA 20.0 BEE 2.5</td></tr><tr><td>TMPTA 20.0 硅烷偶联剂（KH560） 2.5 MMA 55.0</td></tr><tr><td>（9）UV胶黏剂参考配方</td></tr><tr><td>PUA 25 BEE 2 POEA 70 硅烷偶联剂（KH550） 3</td></tr><tr><td>（10）UV胶黏剂参考配方</td></tr><tr><td>PUA 25.0 硅烷偶联剂（KH560） 2.5 MMA 70.0 BEE 2.5</td></tr><tr><td>（11）UV胶黏剂参考配方</td></tr><tr><td>PUA 100 BEE 0.5 20</td></tr><tr><td>EHA （12）UV胶黏剂参考配方</td></tr><tr><td>三官能聚氨酯甲基丙烯酸酯 50 BP 5 45</td></tr><tr><td>HPMA （13）UV胶黏剂参考配方</td></tr><tr><td>PUA 45.0 TPO 5.0 IBOA 22.0 助剂 2.5</td></tr><tr><td>HDDA 25.0 附着促进剂 2.0 （14）UV压敏胶参考配方</td></tr><tr><td>不饱和聚酯 80 BEE 2 邻苯二甲酸二烯丙酯 20</td></tr><tr><td>（15）UV压敏胶参考配方</td></tr><tr><td>带羧基的丙烯酸共聚物 50 BP TEGDA 50 HQ 0.005 3</td></tr><tr><td>异氰酸酯封端的聚氨酯预聚体 5</td></tr><tr><td>（16）UV压敏胶参考配方 EHA 64AA 5 MA 30 4-二苯酮基乙烯基碳酸酯 1</td></tr></table></body></html>  \n\n涂布量 $60\\mathbf{g}/\\mathbf{m}^{2}$ ，固化时间30s，粘接强度 $25\\mathrm{N}/2.5\\mathrm{cm}$ ，附着力 $85\\mathbf{N}/6.25\\mathbf{cm}$ 。  \n\n（17）UV压敏胶参考配方St-BA嵌段共聚物 $(\\mathbf{W_{n}}=47000$ ） $\\scriptstyle4\\mathbf{g}$ 溶解于4mL乙酸乙酯中，加入 $\\boldsymbol{0},2\\mathbf{g}\\ 2,4^{\\circ}$ -双（三氯甲基）-6-胡椒基-1，3，5-三嗪和 $0.2\\mathbf{g}\\ 4\\cdot$ 二氨基苯乙酮 (光敏剂)的丁酮稀释溶液。涂布于PET膜上，UV固化，得胶膜。对不锈钢粘接力为 $6.76\\mathrm{N}/20\\mathrm{mm}$ 。  \n\nBA-MMA-EOEA-EODEGDA共聚物（ $T_{\\mathrm{8}}=35^{\\circ}\\mathrm{C}$ ， $M_{\\mathrm{w}}=125000$ ）加入BP，涂布于PET膜上，UV固化，粘接力 $12\\mathrm{N}/25\\mathrm{mm}$ ，持粘 ${\\geqslant}1440\\min$ 。  \n\n（18）UV压敏胶参考配方  \n\n\n<html><body><table><tr><td>单官能团脂肪族PUA 37.5 改性UPE 丙烯酸丁基氨基甲酸乙酯</td><td>EOEOEA 23.0 1173 16.5 稳定剂</td></tr><tr><td colspan=\"2\">（19）UV压敏胶参考配方 单官能脂肪族PUA（Genomer4188/M22） 16 EOEOEA</td></tr><tr><td>双官能脂肪族PUA（Genomer4269/IBOA） 14 改性UP（Genomer6043/M22） 36 改性UP（Co-Resin02-819/M22） 12 DPGDA 1</td><td>14 907 2 1173 4 热稳定剂 1</td></tr><tr><td colspan=\"2\">（20）UV压敏胶参考配方 双官能团脂肪族PUA 35 EOEOEA</td></tr><tr><td>改性UPE 29 IBOA 12 丙烯酸丁基氨基甲酸乙酯 5</td><td>15 1173 3 稳定剂 1</td></tr><tr><td colspan=\"2\">（21）UV压敏胶参考配方</td></tr><tr><td>芳香族PUA（CN973J75） 15 PEA(CN3002) 83</td><td>光引发剂（SR1135） 2</td></tr><tr><td colspan=\"2\">（22）UV压敏胶参考配方</td></tr><tr><td colspan=\"2\">芳香族PUA（CN973含15%EOEOEA） 15.2 乙氧化壬基苯酚丙烯酸酯（SR504） PEA(CN3002) 80.2 光引发剂（SR1135）</td></tr><tr><td colspan=\"2\">（23）UV压敏胶参考配方 PUA 16.0 MEHQ</td></tr><tr><td colspan=\"2\">烃类增黏剂（S115） 32.0 抗氧剂 EOEOEA 21.8 1173 四乙氧基壬基苯酚丙烯酸酯 23.1</td></tr><tr><td colspan=\"2\">（24）UV压敏胶参考配方 聚酯型PUA 34.0 阻聚剂HEMQ 四乙氧基壬基苯酚丙烯酸酯 28.9 抗氧剂</td></tr><tr><td colspan=\"2\">C5~C碳氢树脂 20.0 1173 酸改性甲基丙烯酸烷基酯 6.0</td></tr><tr><td colspan=\"2\">（25）UV压敏胶参考配方 脂肪族PUA 76.0 石油树脂（NorsolentA-100） EOEOEA 7.6 184</td></tr></table></body></html>  \n\n（26）UV压敏胶参考配方  \n\n\n<html><body><table><tr><td>（26）UV压敏胶参考配方 脂肪族PUA 40 PUA 10 情性增黏树脂 25</td><td>Oligoamine IDA 1173</td></tr><tr><td>（27）低气味UV压敏胶参考配方</td><td>4 3</td></tr><tr><td>脂肪族PUA（CN966） 50 四乙氧基壬基酚丙烯酸酯（CD504） 40</td><td>二乙醇胺 KIP100F 3</td></tr><tr><td>BP （28）高黏度UV压敏胶参考配方</td><td>4</td></tr><tr><td>单官能PUA 18 增黏树脂（Tg为-18℃） 56</td><td>EOEOEA 22 1173 4</td></tr><tr><td>（29）高剥离强度UV压敏胶参考配方</td><td></td></tr><tr><td>情性增黏树脂（T为-12℃） 25 脂肪族PUA 53</td><td>Oligoamine 1173</td></tr><tr><td>IDA 14 （30）高剪切强度的UV压敏胶参考配方</td><td></td></tr><tr><td>脂肪族PUA 52 PUA 22</td><td>IDA 14 Oligoamine</td></tr><tr><td>三官能PEA （31）UV离型剂参考配方</td><td>4 1173 4 4</td></tr><tr><td>硅氧烷丙烯酸树脂（迪高RC705） 硅氧烷丙烯酸树脂（迪高RC720）</td><td>95 DEAP 5</td></tr><tr><td>（32）UV离型剂参考配方 有机硅丙烯酸树脂（氯丙基聚硅氧烷：</td><td>1173 1.5</td></tr><tr><td>86.0 丙烯酸羟丙酯=1：2） TMPTA 5.0</td><td>BP 1.5 活性胺 1.0</td></tr><tr><td>HDDA 5.0 （33）UV离型剂参考配方</td><td></td></tr><tr><td>丙烯酸酯化聚硅氧烷（RC-708） 20.0 LA 10.0 活性胺（UVecryl7100） 55.2</td><td>HDDA 9.8 TMPTA 5.0</td></tr><tr><td>（34）UV离型剂参考配方 丙烯酸酯化聚硅氧烷（RC-726） 18.0</td><td>活性胺（UVecryl7100） 56.7</td></tr><tr><td>丙烯酸酯化聚硅氧烷（SL-5030） 4.0 LA 10.0</td><td>HDDA 6.3 TMPTA 5.0</td></tr><tr><td>（35）UV-PP/纸层压胶黏剂参考配方</td><td></td></tr><tr><td>ECX-5031 78 TMPTA</td><td>184 2 15 1173</td></tr><tr><td>（36）UV层压胶黏剂参考配方</td><td>5</td></tr><tr><td colspan=\"2\">脂肪族PUA（CN966H90） 4.3 819</td></tr></table></body></html>  \n\n（37）UV层压胶黏剂参考配方  \n\n<html><body><table><tr><td>低官能度、低黏度低聚物（CN135） 91.0 脂肪族PUA（CN962） 6.0</td><td>PEA(CN2254) 2.5 819 0.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 495,
+        "chunk": "# （38）UV层压胶黏剂参考配方  \n\n<html><body><table><tr><td>PUA IBOA</td><td>33 33</td><td>651 4 颜料和稳定剂 5</td></tr></table></body></html>  \n\n（39）UV覆膜胶黏剂参考配方  \n\n<html><body><table><tr><td>BA</td><td>78</td><td>双丙酮丙烯酰胺</td><td>0.5</td></tr><tr><td>MMA</td><td>20</td><td>己二酸二酰肼</td><td>0.25</td></tr><tr><td>AA</td><td>2BP</td><td></td><td>0.6</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 496,
+        "chunk": "# 用过硫酸盐引发乳液聚合，用其乳液粘聚丙烯薄膜与纸板，UV固化。  \n\n（40）UV层压胶黏剂参考配方  \n\n<html><body><table><tr><td>PETA</td><td>63.0</td><td>表面活性剂</td></tr><tr><td>三乙二醇二乙烯基醚（DVE-3）</td><td>15.0</td><td>184</td></tr></table></body></html>  \n\n用于聚酯与聚酯层压。  \n\n（41）UV塑料膜层压胶黏剂参考配方  \n\n\n<html><body><table><tr><td>脂肪族PUA POEA</td><td>40 20 20</td><td>PETA HDDA 184</td></tr></table></body></html>  \n\n用于PVC/PVC与PVC/PET膜粘接。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 497,
+        "chunk": "# ！、  \n\n（42）UV塑料膜层压胶黏剂参考配方  \n\n<html><body><table><tr><td>脂肪族聚醚型PUA EO-TMPTA</td><td>40 20</td><td>HDDA NPGDA</td></tr></table></body></html>  \n\n（43）UV塑料膜层压胶黏剂参考配方  \n\n<html><body><table><tr><td>脂肪族聚醚型PUA 40 EO-TMPTA 35</td><td>HDDA 20 1173 5</td></tr></table></body></html>  \n\n（44）UV塑料膜层压胶黏剂参考配方  \n\n<html><body><table><tr><td>脂肪族PUA 40 PEG(400)DMA 35</td><td>PETA 20 184 5</td></tr></table></body></html>  \n\n用于PET、PVC薄膜黏合。  \n\n（45）UV-ABS胶黏剂参考配方  \n\n<html><body><table><tr><td>EA</td><td></td><td>15 IBOA 40</td><td>12</td></tr><tr><td>脂肪族PUA</td><td></td><td>1173</td><td>5</td></tr><tr><td>TPGDA</td><td></td><td>BYK307</td><td>0.2</td></tr></table></body></html>  \n\n（46）UV-PC胶黏剂参考配方  \n\n<html><body><table><tr><td>HEA 6 BMA 25</td><td>1,4-BDDMA 68 651 1</td></tr></table></body></html>\n\n大精！  \n\n用于PC/PC粘接。  \n\n<html><body><table><tr><td>外观</td><td>微黄色透明液体 固化速率/s</td><td><90</td></tr><tr><td>黏度/mPa·s</td><td rowspan=\"3\"><3</td><td rowspan=\"2\">拉伸剪切强度（PC/PC）/MPa 5.89</td></tr><tr><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 498,
+        "chunk": "# （47）UV-DVD胶黏剂参考配方  \n\n<html><body><table><tr><td>脂肪族PUA（VPLS2308） HDDA</td><td>65 助剂 30 1173</td><td>1 4</td></tr></table></body></html>  \n\n用于DVD粘接。  \n\n<html><body><table><tr><td>黏度（25℃）/mPa·s 折射率（25℃）</td><td>572.4±10.0 1.508±0.050</td><td>耐黄变参数△E（UV加速老化72h） 0.34 酸值/（mgKOH/g） 0.534±0.002</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 499,
+        "chunk": "# （48）UV胶黏剂参考配方  \n\n<html><body><table><tr><td>BEE PUA</td><td>30.0 MMA 2.0 KH-560</td><td>80.0 2.5</td></tr></table></body></html>  \n\n①由TDI、聚乙二醇、甲基丙烯酸羟乙酯合成的聚氨酯甲基丙烯酸酯。  \n\n用于微电机转子等微小零部件的粘接。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 500,
+        "chunk": "# （49）UV胶黏剂参考配方  \n\n用于LCD封口和TN-LCD金属管脚固定。  \n\n<html><body><table><tr><td>EA HEMA BA PETA</td><td>50.0 17.6 5.2 1.8 0.6</td><td>硅烷偶联剂KH-550 BEE BP 活性胺 HQ</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 501,
+        "chunk": "# （50）UV胶黏剂参考配方  \n\n<html><body><table><tr><td>EA</td><td>100.0 BP 17.5 活性胺</td><td>1.0 1.0 硅烷偶联剂</td></tr><tr><td>烯丙基双酚A丙烯酸酯</td><td rowspan=\"2\">17.5 2.0</td><td rowspan=\"2\">1.0</td></tr><tr><td>MMA 1173</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 502,
+        "chunk": "# （51）UV密封胶黏剂参考配方  \n\n<html><body><table><tr><td>EA TMPTA</td><td></td><td>70 20</td><td>三苯基磷 叔胺</td><td>4 4</td></tr><tr><td>651 伯胺</td><td></td><td>2 2</td><td>正丁胺</td><td>2</td></tr></table></body></html>  \n\n用于继电器件密封，还可用于塑料件或其他材料器件的密封。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 503,
+        "chunk": "# （52）UV光学胶黏剂参考配方  \n\n<html><body><table><tr><td>EA(CYD128)</td><td>100 偶联剂钛酸酯 35</td></tr><tr><td>邻苯二甲酸二烯丙基酯</td><td>邻苯二甲酸二丁酯 5 4 HQ 0.15</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 504,
+        "chunk": "# （53）UV玻璃胶黏剂参考配方  \n\n<html><body><table><tr><td>HEMA C16~C20二元羧酸二缩水甘油醚丙烯酸酯</td><td>85 UP 35 651 90</td><td>100 2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 505,
+        "chunk": "# （54）UV玻璃胶黏剂参考配方  \n\n<html><body><table><tr><td>聚酯芳香族PUA PEA(EB524)</td><td>20.0 1173 5.0 184</td><td>1.5 1.0</td></tr><tr><td>TPGDA</td><td rowspan=\"2\">12.0 3.0</td><td rowspan=\"2\">大分子表面活性剂 0.5 0.6</td></tr><tr><td>TMPTA</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 506,
+        "chunk": "# （55）UV塑料-玻璃胶黏剂参考配方  \n\n<html><body><table><tr><td>芳香族PUA</td><td>45</td><td>1173</td><td>3</td></tr><tr><td>IBOA</td><td>50 5</td><td>1700 增塑剂</td><td>1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 507,
+        "chunk": "# （56）UV安全玻璃胶黏剂参考配方  \n\n<html><body><table><tr><td>丙烯酸共聚物（MMA：BA：VAc：AA：MAA= 85 50:40:5:3:1.5) 二甲基丙烯酸乙二醇酯 2</td><td>BEE 1 增塑剂邻苯二甲酸二辛酯 10 硅烷偶联剂（A-171） 2</td></tr><tr><td>固化速率/s 3~5 耐热性（100℃水煮2h） 无气泡及缺陷 透射率/% 88.7</td><td>耐光老化/% 97.4 抗穿透性（钢球2.26kg，4m冲击） 不穿透 抗冲击性（40C钢球227g，12m落下） 不穿透</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 508,
+        "chunk": "# （57）UV安全玻璃胶黏剂参考配方  \n\n<html><body><table><tr><td>PUA EHA</td><td></td><td>45.0 20.0</td><td>增黏剂 5.0 BEE 0.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 509,
+        "chunk": "# （58）UV安全玻璃胶黏剂参考配方  \n\n<html><body><table><tr><td>MMA-BA-MA三元共聚物</td><td>60</td><td>增黏剂AA 3</td></tr><tr><td>增塑剂：邻苯二甲酸二丁酯</td><td>20</td><td>BBE 3</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 510,
+        "chunk": "# （59）UV热熔胶参考配方  \n\n<html><body><table><tr><td>2-EHA 760</td><td>AA</td><td>40</td></tr></table></body></html>  \n\n在丙酮-丙醇混合溶剂中自由基聚合，除去溶剂，混合 $0.5\\%$ 的907，制得UV热熔胶。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 511,
+        "chunk": "# （60）UV硅橡胶胶黏剂参考配方  \n\n<html><body><table><tr><td>脂肪族PUA</td><td>45.0</td><td>TPO</td><td>5.0</td></tr><tr><td>IBOMA HDDA</td><td></td><td>22.0 23.0</td><td>附着力促进剂 2.0 助剂 2.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 512,
+        "chunk": "# （61）UV光纤并带胶黏剂参考配方  \n\n<html><body><table><tr><td>EA 脂肪族PUA EO-TMPTA</td><td rowspan=\"3\">13 26</td><td>651</td></tr><tr><td></td><td>BP</td></tr><tr><td>28 活性胺</td><td>1 1</td></tr><tr><td>HDDA</td><td>14 14</td><td>硅偶联剂</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 513,
+        "chunk": "# （62）UV液晶显示器封口胶黏剂参考配方  \n\n<html><body><table><tr><td>F-44酚醛环氧丙烯酸酯</td><td>50.0</td><td>双官能度反应性引发剂 3.0</td></tr><tr><td>双酚A聚醚聚氨酯改性环氧丙烯酸酯 EM2308</td><td>30.0 7.5</td><td>氢键性硅烷偶联剂 2.0 球形气相法二氧化硅（S22LS0） 适量</td></tr></table></body></html>  \n\n<html><body><table><tr><td colspan=\"2\">（63）UV防龋黏合剂参考配方</td></tr><tr><td>A：双酚A环氧甲基丙烯酸树脂 60.0 甲基丙烯酸甲酯 19.0 B：安息香乙醚 3.4</td><td>过氧化苯甲酰 1.6 邻苯二甲酸二甲酯 16.0</td></tr><tr><td colspan=\"2\">（64）可见光固化牙科黏合剂参考配方</td></tr><tr><td>马来酸酐改性环氧甲基丙烯酸树脂 50.0 双甲基丙烯酸三甘醇酯 50.0 甲基丙烯酰氧乙基偏苯三酸酐酯 5.0</td><td>樟脑 1.6 甲基丙烯酸二甲氨基乙酯 4.8</td></tr><tr><td colspan=\"2\">（65）可见光固化牙科黏合剂参考配方 环氧甲基丙烯酸树脂和马来酸酐加成物 70 樟脑</td></tr><tr><td>三羟甲基丙烷三甲基丙烯酸酯 30 甲基丙烯酰氧乙基偏苯三酸酐酯 5</td><td>3.2 甲基丙烯酸二甲氨基乙酯 5</td></tr><tr><td colspan=\"2\">（66）可见光义齿软衬材料参考配方</td></tr><tr><td>脂肪族端羟基聚丁二烯PUA 90.00 甲基丙烯酸八氟戊酯 10.00</td><td>樟脑 0.55 甲基丙烯酸二甲氨基乙酯 0.30</td></tr><tr><td colspan=\"2\">（67）可见光固化补牙用充填复合材料参考配方</td></tr><tr><td>聚氨酯双甲基丙烯酸酯 95.0 1,3-丁二醇双甲基丙烯酸酯 5.0 樟脑 2.0</td><td>甲基丙烯酸3，4-亚甲基二氧基苯甲酯 5.0 硅硼酸钡玻璃粉（平均粒径6.5pm） 221.50 气相SiOAEROSILOX50（平均粒径40nm） 13.6</td></tr><tr><td colspan=\"2\">（68）可见光固化补牙用充填复合材料参考配方</td></tr><tr><td>双酚A缩水甘油双甲基丙烯酸酯 50.0 1.6-已二醇双甲基丙烯酸酯 50.0 樟脑 5.0</td><td>醋酸-3，4-亚甲基二氧基苯甲酯 1.5 气相SOAEROSILOX50（平均粒径40mm） 7.2 铝矽酸盐玻璃陶瓷 201.4</td></tr><tr><td colspan=\"2\">（69）可见光固化补牙用充填复合材料参考配方</td></tr><tr><td>三缩四乙二醇双甲基丙烯酸酯 40.0 聚氨醇双甲基丙烯酸酯 60.0 1.0</td><td>3,4-亚甲基二氧基苯甲酸（胡椒酸） 0.1 气相SOAEROSILOX50（平均粒径40nm） 4.2 气相SiOAEROSILOX50（平均粒径7nm） 21</td></tr><tr><td colspan=\"2\">樟脑 （70）阳离子UV胶黏剂参考配方</td></tr><tr><td>丙烯酸低聚物（Synocure3100） 69.0 环氧树脂（ERLA221） 29.5</td><td>651 0.5 二甲苯基碘六氟磷酸盐 1.0</td></tr><tr><td colspan=\"2\">（71）阳离子UV胶黏剂参考配方</td></tr><tr><td>环氧树脂（Uvacure1534） 87.3 TPG 9.7</td><td>阳离子光引发剂（Uvacure1590） 3.0</td></tr><tr><td colspan=\"2\">（72）阳离子UV胶黏剂参考配方</td></tr><tr><td>MMA 20 二芳基二缩水甘油醚 50 2,2-双（1，4，6三螺环-4，4-壬烷2-甲氧苯基）丙烷 50</td><td>651 2 二苯基碘六氟磷酸盐 3</td></tr></table></body></html>  \n\n用于玻璃-玻璃、玻璃-金属粘接。  \n\n（73）阳离子UV胶黏剂参考配方  \n\n<html><body><table><tr><td>EA(ERL-1000) 50 乙烯基 用于电绝缘材料、包封材料和液晶。</td></tr><tr><td>（74）阳离子UV密封胶参考配方</td></tr><tr><td>硅氧烷改性四官能脂环族环氧树脂 80 十二烷基苯碘六氟磷酸盐（含ITX） 2 环己烷二乙烯基醚 20 滑石粉 67</td></tr><tr><td>（75）阳离子UV液晶围边密封胶参考配方 硅氧烷改性四官能脂环族环氧树脂 80.0 二芳基碘四氟硼酸盐（Rhodorsil2074） 1.0</td></tr><tr><td>环已烷二乙烯基醚（CHDVE） 20.0 ITX 0.5</td></tr><tr><td>（76）阳离子UV液晶围边密封胶胶黏剂参考配方 双酚A环氧树脂（E828） 100 气相SiO</td></tr><tr><td>1 十二烷基碘六氟磷酸盐（9380C） 2</td></tr><tr><td>（77）UV阳离子层压胶黏剂参考配方</td></tr><tr><td>脂环族环氧树脂（UVR6105） 76 三芳基硫盐（UVI6990） 多元醇（TNONE0310） 20</td></tr><tr><td>（78）UV阳离子层压胶黏剂参考配方 脂环族环氧树脂（UVR6105） 79.5 三芳基硫盐（UVI6990） 3.0</td></tr><tr><td>PUA 10.0 三芳基硫盐（UVI6974） 1.0 线型脂环族环氧树脂（UVR6216） 6.5</td></tr><tr><td>（79）UV阳离子层压胶黏剂参考配方</td></tr><tr><td>BA-EHA-AA-GMA共聚物（45%乙酸乙酯溶液） 100 二芳基硫六氟酸盐（CD-1012） 0.5 GMA 1.5</td></tr><tr><td>（80）阳离子UV低VOC、低臭味胶黏剂参考配方 脂环族环氧树脂（UVR6100） 80.00 BP 0.75</td></tr><tr><td>乙烯基月桂酸酯（ExxarNeol2） 20.00 FC430 0.50 三芳基硫盐（UVI6990） 0.75</td></tr><tr><td>（81）阳离子UV光学胶黏剂参考配方 3，4-环氧环已基，3，4-环已烷甲酸酯 27 端环氧基二甲基硅氧烷 10</td></tr><tr><td>氢化双酚A环氧树脂 63 阳离子光引发剂硫盐 2 （82）双重固化光缆加强筋用浸胶参考配方</td></tr><tr><td>双酚A环氧单丙烯酸酯 51 651 1 DEGDA 30 N,N'-二甲基苯胺 2 TMPTA 10 流平剂467 1</td></tr><tr><td>TMPTMA 5</td></tr><tr><td>（83）双重固化胶黏剂参考配方 丙烯酸酯树脂（Synocure3100） 69.0 651 0.5</td></tr><tr><td>环氧树脂（ERL4221） 29.5 二甲苯基碘六氟磷酸盐 1.0</td></tr></table></body></html>\n\n（84）双重固化胶黏剂参考配方的画！出新，对热图  \n\n<html><body><table><tr><td>双酚A环氧单丙烯酸酯 51 TMPTA 10 TMPTMA 5 DEGDA 30</td><td>651 1 N,N'-二甲基苯胺 2 流平剂467 1</td></tr><tr><td>（85）双重固化胶黏剂参考配方 双酚A环氧树脂 50.0 二苯基碘六氟磷酸盐</td></tr><tr><td>EA 50.0 增感剂DA 0.5</td></tr><tr><td>（86）双重固化胶黏剂参考配方 环氧丙烯酸单酯 60 TPGDA 12</td></tr><tr><td>BA 12 1173 2 GMA 12 阳离子光引发剂445 2</td></tr><tr><td>（87）双重固化光学胶黏剂参考配方</td></tr><tr><td>A:EA 48 邻苯二甲酸二丁酯 8 新戊二醇二缩水甘油醚 8 安息香乙醚 0.2</td></tr><tr><td>B：多胺化合物与环氧化物加成物</td></tr><tr><td>A：B=4：1，光固化后，60C×6h。 （88）UV导电胶参考配方</td></tr><tr><td>环氧丙烯酸树脂 30 651 3 镀银铜粉 70 硅烷偶联剂（KH-570） 2</td></tr></table></body></html>\n\n电阻率 $1.5{\\sim}2.2{\\times}10^{-4}\\Omega\\cdot\\mathrm{cm},200\\%$ 时电阻率 $4.1\\times10^{-4}\\Omega\\cdot\\mathrm{cm}$ 9  \n\n（89）UV导电胶参考配方  \n\n① 铜粉预处理在铜粉中加人无水乙醇为介质，氮气保护下用行星式球磨机球磨20h，除去无水乙醇，得珠光色粒径1～10μm片状铜粉。用浓度5%的稀硫酸溶液洗两次，再用无水乙醇洗两次，加入质量分数4%的偶联剂KH-570快速放人真空干燥箱干燥备用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 514,
+        "chunk": "# $\\textcircled{2}$ 光敏树脂配制  \n\n<html><body><table><tr><td>EA N-VP</td><td>30</td><td>651 20 BP</td></tr></table></body></html>  \n\n<html><body><table><tr><td>光敏树脂 20 铜粉 80</td><td>偶氮二异丁晴</td></tr></table></body></html>  \n\n（90）UV导电胶参考配方  \n\n① 镀银铜粉制备将8.51gAgNO3溶于去离子水中，搅拌下缓慢放入氨水，至溶液呈透明无沉淀状态。再加去离子水至 $100\\mathrm{mL}$ ，配成银氨溶液。  \n\n将1.81g38%的甲醛加入到120mL无水乙醇中，搅拌混匀，配成还原液。  \n\n将10g200目铜粉在真空球磨机中球磨10h，取出用5%的稀HSO和无水乙醇分别洗涤两次，滤去清液，放置于250mL三口烧瓶中，加人还原液，搅拌均匀，升温至50℃，边搅拌边滴加银氨溶液，滴加完继续反应1.5h，过滤，将得到的粉末用5%的稀HzSO4和无水乙醇分别洗涤两次，滤去清液后再重复上面的步骤两次，将最后得到的粉末洗涤干燥后，",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 515,
+        "chunk": "# 真空球磨处理 $^{10\\mathbf{h}}$ ，得到片状镀银铜粉。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 516,
+        "chunk": "# $\\textcircled{2}$ 导电胶用光敏树脂  \n\n$\\textcircled{3}$ 导电胶的配方  \n\n\n<html><body><table><tr><td>EA N-VP</td><td></td><td>3.00 2.00</td><td>651 BP</td><td></td><td>0.08</td><td>0.16</td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>光敏树脂 100 镀银铜粉 70</td><td>偶氮二异丁晴 2 硅偶联剂KH-570 3</td></tr><tr><td>电阻率/Ω.cm 1.5×10-</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 517,
+        "chunk": "# 第9章 感光性树脂印刷版  \n\n光固化材料在印刷上主要用于制版，是应用历史最早、使用最广泛的一个领域。利用光固化材料可以制得各种印刷版材（图9-1)。  \n\n![](images/0b4a00c19e8e76f5985c3a413fa80a95cc17a97e9a479193f80bfbd60b16d815.jpg)  \n图9-1各种感光性树脂印刷版  \n\n早在1826年，法国化学家尼普斯（Niepce）就利用沥青的光固化特性，发明了照相术。几年后，尼普斯发现了沥青固化膜具有抗酸耐蚀性，他将沥青照相术应用到印刷业的制版过程中，从而发明了照相制版术。1850年美国人塔尔博特（Talbot）将重铬酸盐与明胶混合后，涂在钢板上制作照明凹版获得成功。由于重铬酸盐的感光度比沥青高得多，所以重铬酸盐被陆续应用到平版与凸版的制版过程中，使照相制版术得到了迅速的发展和广泛的应用。  \n\n1934年德国卡勒（Kalle）公司的施密特（Schmidt）发表了用重氮盐作感光剂的PS版专利，因第二次世界大战的干扰，第一块PS版在1946 年正式投放市场。1954 年德国卡勒公司用重氮化合物作感光剂制得印刷用PS 版感光层，制作阳图PS版。同年美国柯达公司明斯克（Minsk）等人将聚乙烯醇肉桂酸酯在紫外光照射下发生光二聚反应，从而用作光刻胶制造半导体和印制线路板，20世纪60 年代初并应用于印刷制版制作阴图PS 版。1970年美国杜邦公司率先推出感光性柔性版Cyrel。  \n\n计算机直接制版（computer-to-plate，简称CTP）是20世纪70年代国外就开始研究利用的电子和激光进行直接制版技术；1982年银盐涂布的聚酯版开始用于单色、套准精度较低的商业印刷；1990年杜邦公司和爱克发公司发布了银盐CTP版材，用于四色套印的商业印刷，不久富士公司和爱克发公司开发出光聚合CTP版；1995年在德国杜塞尔多夫举行的Drupa1995印刷展上，有42家厂商推出了与CTP技术相关的设备和器材，柯达公司还推出了热敏CTP版材，标志着CTP技术在印刷业进入发展新时期；在Drupa2000印刷展上又推出了紫激光（405～410mm）制版机，为光聚合CTP版提供了新的光源和制版设备，同时还出现了利用紫外光源和常规 PS 版进行直接制版的UV-CTP 技术。CTP 技术的出现，标志印刷进人了一个崭新的时代—数字化印刷时代，可望实现“按需印刷”、“可变信息印刷”、“远程异地印刷”的梦想。  \n\n感光性树脂凸版是以感光性树脂为材料，通过曝光、显影而制成的光聚合型凸版。感光 性树脂凸版分固体型和液体固化型两大类。",
+        "category": " Introduction"
+    },
+    {
+        "id": 518,
+        "chunk": "# 9.2.1液体感光性树脂凸版  \n\n液体感光性树脂凸版简称液体树脂版，指感光前树脂为液体状态，感光后成为固体的树脂版。液体树脂版的感光性树脂主要有不饱和聚酯和聚氨酯丙烯酸酯，交联剂为不饱和双烯类或烯类化合物，光引发剂主要用安息香醚类。  \n\n液体感光性树脂凸版制版工艺：涂覆感光性树脂→正面和背面同时UV曝光→显影→干燥 $\\star$ 后曝光→印刷（图9-2)。  \n\n在制版机玻璃板上安放阴图底片，覆盖聚酯薄膜，浇注液体感光性树脂至一定厚度，放上聚酯片基，然后用紫外灯上下同时曝光。下侧正面曝光，使见光部分树脂交联固化形成图文部分，上侧背面曝光，使图片部分黏附于聚酯片基上。曝光完毕，回收未曝光树脂，取出版材，经显影、干燥，再次UV充分曝光，使细小的图文部分彻底固化，制成印版。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 519,
+        "chunk": "# 9.2.2固体感光性树脂凸版  \n\n固体感光性树脂凸版采用固体高分子材料预制的感光性树脂版，其结构如图9-3所示。  \n\n固体树脂版是由饱和聚合物、交联剂和光引发剂组成。饱和聚合物采用聚乙烯醇衍生物、纤维素衍生物和聚酰胺三大类；交联剂为二乙烯基化合物，光引发剂主要用安息香醚类或葱类。将上述各组分混合均匀后，涂布到带有防光晕层的聚酯片基或铝基上，干燥后即制成固体感光性树脂凸版。也有将固体树脂版组分共混后，经挤出成型而制得。  \n\n固体感光性树脂凸版制版工艺：覆盖阴图底片→UV曝光→显影→干燥→后曝光→印版。  \n\n![](images/23124bf9dca40b75aeaf5cf71b3761914cff5a6859fe817e2a15f058a55db053.jpg)  \n图9-2液体感光树脂凸版的制版过程  \n\n![](images/41423502b72ec744328dd30e80f0a579cf38ab281c310b926e957eb8dc1c5744.jpg)  \n图9-3固体感光性树脂凸版结构示意图  \n\n固体树脂版揭去聚乙烯保护膜后，将阴图底片和感光树脂层真空贴合，UV曝光，见光部分交联固化形成图文部分，不见光部分在显影时除去，经干燥，二次UV充分曝光，使版材彻底固化，以提高印版硬度，制成印版。  \n\n固体感光性树脂凸版和液体感光性树脂凸版在20世纪 $70\\sim90$ 年代曾在新闻报刊印刷、标签、包装纸、信纸印刷上广泛使用，但由于印版分辨率低、耐印力低、印刷质量也差，因此逐渐被胶印和柔印所代替，退出印刷历史舞台。  \n\n感光性柔性版其光固化作用与感光性树脂凸版一样，不同的是版材除了有一定硬度外，还具备橡胶的弹性。感光性柔印版也有固体树脂版和液体树脂版两种，近年来又出现了计算机直接制版（CTP）柔性版。柔性版印刷，由于柔印设备投资比胶印、凹印设备低；制版工艺简单，耐印力高，装版迅速；随着印刷技术发展，印刷质量和精度不断提高；大量使用环保型水墨和UV墨，因此在包装印刷上正在逐步替代胶印和凹印，特别是塑料印刷和纸版印刷。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 520,
+        "chunk": "# 9.3.1 固体感光性树脂柔性版  \n\n固体感光性树脂柔性版组成主要是使用本身有弹性的合成橡胶类树脂如聚丁二烯、聚异戊二烯、聚丁二烯-苯乙烯共聚物、聚氨酯、聚乙烯-醋酸乙烯共聚物等；交联剂为丙烯酸多官能单体，如季戊四醇三/四丙烯酸酯、三羟甲基丙烷三丙烯酸酯；光引发剂为安息香醚类、葱鼠类、二苯甲酮类。版材如图9-4所示，版基为聚酯片基，上面是感光树脂层，再覆盖一层可剥离的聚乙烯保护膜。感光树脂层大多采用将橡胶类树脂、交联单体、光引发剂、热阻聚剂等共混合挤出成型。固体感光性树脂柔性版制版过程：  \n\n![](images/4aae143da4362e826cffd1533a0f2abbeb437cdc44461a1f9151f8317600ab0e.jpg)  \n图9-4固体感光树脂柔性版结构示意  \n\n背面曝光 $\\rightarrow$ 安置底片→正面曝光→显影 $\\star$ 干燥 $\\nrightarrow$ 后曝光 $\\rightarrow$ 防粘处理→印版  \n\n版材首先是背面UV预曝光，其目的是为了增加版基的厚度，曝光时间越长，版基越厚。再揭去保护膜，放上阴图底片，正面UV曝光，见光部分发生光交联固化形成图像部分；显影时未见光部分被溶解除去，经干燥后，为了使印版中单体完全固化，再进行后曝光，用紫外灯对版面全面曝光，经防粘处理后，制成印版。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 521,
+        "chunk": "# 9.3.2液体感光性树脂柔性版  \n\n液体感光性树脂柔性版与固体感光性树脂柔性版基本组成一样，只是制成液体树脂，即时制版。其制版过程为：  \n\n铺流 $\\rightarrow$ 背面曝光 $\\rightarrow$ 形成图文的正面曝光→背面全面曝光 $\\rightarrow$ 回收未固化树脂→显影→干燥 $\\rightarrow$ 后曝光 $\\rightarrow$ 印版  \n\n在曝光成型机中，在下玻璃板上铺上阴图底片，覆盖聚酯薄膜，涂覆液体感光树脂到所需厚度，覆盖聚酯片基，压好上玻璃板。再背面UV曝光，然后正面UV曝光，见光部分发生光交联固化，与背面曝光固化部分连接一起形成图文，接着背面全面UV曝光，形成版基，回收未固化的感光树脂后，再经显影、水洗、干燥，最后用紫外灯对版面全面曝光。制成印版（图9-5）。  \n\n![](images/a32c23452b080a5d5b9717a641c4df902aa96200eb065ac66a5523c71b7606f7.jpg)  \n图9-5液体感光树脂柔性版制版工艺",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 522,
+        "chunk": "# 9.3.3 CTP柔性版  \n\n20世纪末，美国杜邦公司率先推出的一种与计算机直接制版技术接轨，用先进的数字成像与柔印版制版技术相结合的柔性版数字成像系统和直接制版用柔性版(CTP柔性版)。CTP柔性版是复合结构版材，即在原杜邦感光性树脂柔性版Syrel版材上涂有一层黑膜(图9-6)，此层黑膜在受到激光束扫描时，能气化而露出Syrel版。经激光扫描后，黑膜即成为底片，再按常规Syrel制版工艺，经曝光显影后制得印版。所以CTP柔性版制版过程为：  \n\n![](images/c54fc213d47fec1ede072112e3ae0e2803931c5579b53fa742092b95f31a70f0.jpg)  \n图9-6 CTP柔性版结构示意  \n\n图文输入计算机→计算机控制激光烧蚀版材上黑膜形成底片 $\\rightarrow$ 背面曝光 $\\rightarrow$ 正面曝光 $\\rightarrow$ 显影→干燥 $\\rightarrow$ 后曝光 $\\rightarrow$ 防粘处理 $\\nrightarrow$ 印版  \n\n采用CTP柔性版，不用银盐胶片制作底片，省去了银盐胶片制作的设备、材料和时间；无需真空吸版，故无漫射，网点扩大小、分辨率高；印刷质量提高，可与胶印媲美。CTP柔性版技术是数字化制作柔性版，它代表了柔性版的发展方向。从版材上看，成本增加不大，主要是制版设备投资增加较大，这就影响了CTP柔性版技术的推广应用。  \n\n预涂感光平版（presensitigedplate，简称PS版)。是在铝基版上预先涂覆感光层，加工后贮备，随时用于晒版的胶印版。具有商品化贮存性（保存期在一年左右)；使用简便；分辨力高，印刷适应性好，耐印力高等特点，目前已成为胶印的主要印刷版材。  \n\nPS版一般分为阳图型PS版和阴图型PS版两种。",
+        "category": " Introduction"
+    },
+    {
+        "id": 523,
+        "chunk": "# 9.4. 1 阳图PS版  \n\n阳图型PS版是在表面处理的铝基材上涂布感光树脂层，经干燥后制成。目前阳图型PS版感光树脂层多采用光降解型邻-重氮萘类作感光剂，与线型酚醛树脂组成。在紫外光照射下，重氮基发生分解，析出氮气，同时发生分子内重排变为烯酮，在水存在下烯酮水解变为羧基。因为感光部分产生了羧基，用碱性显影液除去，露出的铝基亲水。不感光部分形成的图文亲油墨。得到阳图。我国目前PS版主要用的是阳图型PS版。  \n\n![](images/c59539fb2bd4bb329a42e66795d3e74c229b19074b371a9c359b3331c5397b6a.jpg)  \n\n阳图型PS版的制过程：",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 524,
+        "chunk": "# 曝光 $\\rightarrow$ 显影 $\\star$ 干燥→修版涂胶 $\\rightarrow$ 印版  \n\n将阳图底片与阳图型PS.版真空贴合，紫外曝光，一般采用金属卤素灯（如碘灯）或中压汞灯。显影一般采用硅酸钠、磷酸钠、碳酸钠或有机胺等碱性水溶液。版面经除脏、修补、干燥后，即成印版。有时为了提高耐印力，还可采用高温烤版。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 525,
+        "chunk": "# 9.4. 2 阴图PS版  \n\n阴图PS版与阳图PS版一样，是在表面处理的铝基材上涂布感光树脂层，经干燥后制成。只是阴图PS版所用感光树脂是采用光聚合型感光性树脂。常见的有重氮树脂与碱溶性树脂体系、带叠氮基的高分子体系和带肉桂酸基团的高分子体系，它们感光度比阳图PS 版高，但有一部分是溶剂显影，成本高，对人体有害，也污染环境。在紫外光照射下，见光部分发生聚合交联，形成图文部分亲油墨，不见光部分显影时除去，露出铝基材亲水，得到阴图。  \n\n阴图型PS版的制版过程为：  \n\n将阴图底片与阴图型PS版真空贴合，紫外曝光，一般采用金属卤素灯（碘灯）或中压汞灯。显影一部分是用稀碱液如碳酸钠，还有一部分是要用溶剂。版面经除脏、修补、干燥后，即成印版。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 526,
+        "chunk": "# 9.4.3 无水胶印PS版  \n\n无水胶印是用斥墨的硅橡胶层作为印版空白部分，不利用水、油相斥原理，当接触墨辊时不会受墨，在印刷时不用水或润版液，可以在版面干燥状态下进行印刷。由于印刷时不用润版液，不会造成纸张变形，无需考虑水墨平衡问题；印版耐印力高；制版方法简单；但成本比一般PS版高。  \n\n无水胶印PS版结构如图9-7所示。在铝基板上有底涂层，再涂上感光树脂层和硅橡胶层，上面覆盖保护膜。  \n\n无水胶印PS版制版工艺：  \n\n曝光晒版→剥离保护膜→显影→后处理→印版  \n\n将底片直接置于版材上，抽真空贴合，UV曝光(金属卤素灯或中压汞灯)，剥离保护膜。由于UV曝光时见光部分感光树脂发生光交联并与上层硅橡胶产生光黏结，使感光树脂层与硅橡胶黏结在一起，组成非图文部分，不亲油墨，显影时，显影液对未感光部分的硅橡胶有较强显影能力而除去，露出树脂形成图文部分，亲油墨，得到阳图。  \n\n![](images/b187c4211c6c522aa1b9f134f8372039432aaaec10eba8fae2e09efec1fb6e51.jpg)  \n图9-7无水胶印PS版结构示意图",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 527,
+        "chunk": "# 9.5 计算机直接制版PS版  \n\n计算机直接制版（computer to plate，简称CTP）技术是20 世纪80 年代开发的数字化制版技术。由于设备制造厂商与印刷厂、感光材料生产厂密切合作，进人20世纪90 年代CTP技术日渐成熟，代表了印刷技术最新的发展方向。  \n\nCTP技术是使用数字化数据通过激光制版机将图像、文字直接复制到印刷版上的技术。采用CTP工艺制版与传统胶印制版工艺相比，不需要银盐分色胶片，还可省去多道制版工序。CTP工艺和传统制版工艺比较如图9-8所示。  \n\n![](images/6015dd2176e5f27b25fd86d46fa1faa78eab8446783f04d06fc17b2aba7a035e.jpg)  \n图 9-8CTP工艺和传统制版工艺比较",
+        "category": " Introduction"
+    },
+    {
+        "id": 528,
+        "chunk": "# 9.5.1CTP版的性能要求  \n\nCTP直接将数字化图文传递到印版上。因此对CTP版要求有如下性能。  \n\n（1）着墨性印版影像部分有良好的着墨性，印刷时不会产生飞墨影响印刷效率。  \n\n（2）亲水性印版非影像区有良好的亲水性。现在使用的CTP版基多为铝基版，其表面经磨版和阳板氧化处理，具有优良的亲水性。而且表面处理后的铝基也有利于改进感光层和铝版基的黏附性，从而提高印版的耐印力。  \n\n（3）耐印力为单张印版所能印出的印品最多印数。为了提高印版的耐印力，常加热至230～250℃烤版1～2min，进一步除去溶剂以提高影像区成膜树脂的交联程度，使影像更加牢固，提高耐印力。  \n\n（4）分辨率指印版成像的精细和准确程度。常规的PS 版可得到175线，2%～98%的网点；而CTP版可得到175线，1%～98%的网点。  \n\n（5）感光度常规的PS版感光度在10～100mJ/cm²。CTP版中银盐扩散转移版感光度最高为1～100μJ/cm²，光聚合版在100～250μJ/cm，热敏版在100～200mJ/cm²。  \n\n（6）曝光光源常规PS版用UV曝光，主要用金属卤素灯和汞灯。CTP版用激光光源曝光，一般情况下光聚合版用紫激光（405～410nm）、氩离子激光（488nm）和FD-YAG激光（532nm)；银盐扩散转移版用紫激光（405～410nm）、FD-YAG 激光（532nm）和Red-LD激光（630nm）；热敏版用IR-ID激光（830nm）和YAG激光（1064nm）；UV-CTP版用UV光（365nm、375nm)。  \n\n（7）显影显影可使版材曝光部分和未曝光部分区分开来，形成影像。对不同CTP 版材，显影方法也不同：银盐CTP版都用银盐扩散转印显影方式；光聚合CTP版一般用碱水显影；热敏CTP版因不同版材显影方法也各不相同；UV-CTP 版则用常规PS版显影液显影；银盐复合CTP版则先要经银盐显影，然后用PS版显影液显影。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 529,
+        "chunk": "# 9.5.2 CTP版材的类型  \n\nCTP制版系统因结构不同，所选光源不同，所用的CTP版材也不同。目前主要有六种不同CTP版材；高感光聚合版、银盐复合版、银盐扩散转移版、热敏版、紫激光版以及UV-CTP版，但主要为高感光聚合版、银盐扩散转移版和热敏版，它们的版材结构、成像机理和性能不尽相同，各有特点(表9-1)。 仁  \n\n由于激光技术的发展，开发了紫激光（405～410nm)，2000年紫激光器功率还只有$\\mathsf{5m}\\mathbf{W}$ 5mW；2002年为30mW；2004年Drupa展会上，紫激光器已普遍为60mW；而2008年Drupa展会上，紫激光器功率已出现120mW，正在开发功率150mW、200mW甚至250mW的紫激光器。由于紫激光CTP版材成像所需的紫激光器功率60mW足够用，因此更高功率的紫激光器开发，无疑使紫激光CTP技术如虎添翼，紫激光CTP技术进展将更为迅速。  \n\n表9-1常见三种类型CTP版材性能对照表  \n\n\n<html><body><table><tr><td>性能</td><td>高感光聚合版</td><td>银盐扩散转移版</td><td>热敏版</td></tr><tr><td>曝光光源</td><td>紫激光（410nm) 氩离子激光（488nm） FD-YAG激光(523nm)</td><td>紫激光(410nm) 氩离子激光(488nm) FD-YAG激光(523nm) RED-LD激光(630nm)</td><td>IR-LD激光(830nm) YAG激光(1046nm)</td></tr><tr><td>版材感光度</td><td>100~200J/cm²</td><td>约1μJ/cm²</td><td>100~200mJ/cm²</td></tr><tr><td>影像形成</td><td>感光聚合物的光聚合交联 反应</td><td>银盐扩散转移方式</td><td>酚醛树脂的热交联反应</td></tr><tr><td>显影</td><td>碱显影</td><td>银盐扩散显影处理</td><td>热强化交联后显影</td></tr><tr><td>分辨力</td><td>175线，2%～98%网点再现</td><td>同银盐片解像力</td><td>175线，1%～98%网点再现</td></tr><tr><td>印刷适性</td><td>同PS版</td><td>不如PS版</td><td>同PS版</td></tr><tr><td>曝光后的潜影稳 定性</td><td>曝光后潜影继续，经显影前预 热处理停止</td><td>同银盐片</td><td>曝光而未显影的版材可长时间保存</td></tr><tr><td>耐印性</td><td>10万～20万印烤版可印100 万印</td><td>中印程以下</td><td>10万～20万印，烤版可印100万印</td></tr><tr><td>作业条件</td><td>黄灯</td><td>暗室</td><td>明室</td></tr></table></body></html>  \n\nCTP技术的另一个进展是免化学处理CTP印版的出现。各种CTP版材都需经显影加工处理，需用显影液、水冲洗，带来大量的废水，污染环境。因此从环保上看，免化学处理CTP印版的开发完全适应当前绿色生产需要和持续发展的需求，也为印刷行业一直难以克服的环境污染开辟了一条新路。目前免化学处理CTP印版实际上还是水显影和上胶，即不需用化学显影药剂，降低制版成本；水洗经循环使用，没有废液排放，更为环保；缩短制版周期，提高生产效率。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 530,
+        "chunk": "# 9.5.3UV-CTP版  \n\nUV-CTP是指利用UV光或UV激光在传统PS版上进行计算机直接制版的一种方式，最早也称为CTcP。UV-CTP最大的特色是采用常规的PS 版和显影液，价格低，综合成本低；而且制版机激光头寿命较长 $(3000{\\sim}20000\\mathrm{h})$ ，价格低，维护成本也较低。UV-CTP与热敏CTP、紫激光CTP有关性能对比见表9-2。  \n\n表9-2UV-CTP与热敏CTP、紫激光CTP有关性能对比  \n\n\n<html><body><table><tr><td>项 目</td><td>UV-CTP</td><td>热敏CTP</td><td>紫激光CTP</td></tr><tr><td>光源 波长/nm 激光头功率/mW 感度</td><td>紫外光 365、375 100 20~100mJ/cm²</td><td>红外激光 830 4X104 100~200mJ/cm² 200</td><td>紫激光 405、410 60 50~100μJ/cm² 350</td></tr></table></body></html>  \n\nUV-CTP版材与PS版一样，有阴图型和阳图型两种。  \n\n（1）阴图型UV-CTP版为光聚合/光交联型版，成像原理是利用感光层见光部分发生聚合/交联，形成图文部分，亲油墨，用于印刷；不曝光部分在显影时除去，形成非图文区，亲水，达到水墨平衡。阴图型UV-CTP版的制版速率较快，比同样感光度的阳图型版材高出 $30\\%$ 以上，因此阴图型更适合于UV-CTP制版。其耐印力较高，适合于商业包装印刷。  \n\n（2）阳图型UV-CTP版为光分解型版，成像原理是利用感光层见光部分解，在显影时除去，形成非图文区，亲水；不曝光部分形成图文区，亲油墨，用于印刷。因需除去的面积较大，就需较长的曝光时间，制版速率较慢。但因具有网点还原性好和显影加工适应性宽等优势，常应用于商业印刷和报业印刷。  \n\n网印刷版通常有四种方法，即直接法、间接法、直-间接混合法和计算机直接制版法(CTP)。直接法是直接涂布感光胶制版；间接法是用感光膜制版，而感光膜是用感光胶涂布到聚酯薄膜上制成；直-间接混合法，制版时既要用感光胶，也要用感光膜；数字化计算机制版法也要用感光胶。不同的是，前三种方法都要用底片制版，而数字化计算机制版不需要底片，只要将图像符号等资料先输入计算机，然后利用计算机在已涂布感光胶的网版上制版。相同的是，无论哪种制版方法都要应用感光胶。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 531,
+        "chunk": "# 9.6.1 网印感光胶  \n\n网印制版用感光胶主要有四大类：重铬酸盐系感光胶、醇溶性尼龙系感光胶、重氮树脂系感光胶和有机苯乙烯基吡啶盐树脂系感光胶。，  \n\n（1）重铬酸盐系感光胶是利用重铬酸盐的光敏性，与一些有机胶体（明胶、鱼胶、阿拉伯树胶、聚乙烯醇等）混合制成感光胶。但它只能现用现配，使用寿命短，有暗反应，解像力低，特别是铬盐毒性大，既损害人体健康，又污染环境，现在很少使用。  \n\n（2）醇溶性尼龙系感光胶多采用安息香及其衍生物作光引发剂，但因这类感光胶制版后不能去膜，网版无法重复使用，现在应用也不多。  \n\n（3）重氮树脂系感光胶多采用聚乙烯醇与非水溶性高分子乳液（聚醋酸乙烯乳液、醋-丙乳液等)；感光剂为重氮化合物，常用的有双重氮盐、重氮树脂或复合重氮树脂等配成。由于具有分辨率高、解像力好、感光速率快、耐磨性、耐水性和耐溶剂性都很好，又是用水显影，以及易去膜等突出优点，目前已成为应用最广泛的感光胶。  \n\n（4）有机苯乙烯基吡啶盐树脂系感光胶又叫SBQ感光胶，是日本村上丝网株式会社研制成功的一种单液型感光胶，它是利用苯乙烯基吡啶盐受紫外光照射发生光二聚反应，生成带四元环结构的不溶于水的二聚物，用水显影时留在丝网上形成图文。SBQ感光胶热稳定性好；感光度高，比重氮感光胶高4～5倍，感光光谱在315～430nm，最大吸收峰在370nm；分辨率高，图像清晰，印件质量高；显影性能好，用水显影；版膜与丝网黏结性能好，耐印率高；废旧版膜容易脱膜，有利于网版的回收再利用。主要缺点是成本比重氮感光胶高，影响推广使用。  \n\n此外还有光聚合体系的感光胶，也是单液型碱水显影。  \n\n用感光胶来制作丝网印版制版过程：  \n\n绷网 $\\rightarrow$ 涂覆感光胶 $\\rightarrow$ 晒版曝光 $\\rightarrow$ 显影 $\\div$ 干燥→印版  \n\n将选好一定目数的丝网（有尼龙、聚酯、不锈钢、铜、镍丝网等）在木框或铝框上绷紧，用绷网胶粘在网框上，使其具有一定的张力。再涂覆感光胶，在40℃士5℃烘箱中干燥。一般要涂两遍，最多三遍。放上底片，真空吸片；因网印感光胶吸收400nm左右的紫外光。采用制版荧光灯或金属卤素灯曝光。经用水显影后，干燥，修版，制成印版。丝网印版使用完后，还可以脱膜回收，使用脱膜液，除去感光胶后，丝网可重复使用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 532,
+        "chunk": "# 9.6.2 网印感光膜  \n\n感光膜又称感光菲林或菲林，是将丝网感光胶均匀地涂布在聚酯片基上，经干燥后卷存，即开即用，省时快捷。使用感光膜制版能保证网版印刷面光滑，并能容易控制网版厚度，精密耐用。使用感光膜的制版过程与感光胶一样：  \n\n绷网 $\\rightarrow$ 粘贴感光膜 $\\rightarrow$ 晒版曝光→显影 $\\rightarrow$ 干燥→印版  \n\n由于制作感光膜时使用不同的感光胶，因此得到不同的感光膜，用重氮感光胶制得重氮菲林，用SBQ感光胶则制得SBQ菲林。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 533,
+        "chunk": "# 9.6.3计算机直接制作网印版  \n\n计算机直接制网印版（CTS）是由计算机把输入的图像和文字直接输出到网印网版上，经显影处理后形成网印版。目前有两种途径可实现CTS：喷墨直接制版（jet screen）和直接曝光制版（directlightprocessing，简称DLP）。  \n\n（1）喷墨直接制版将网版涂布感光胶并干燥，或贴上菲林，通过喷墨系统把阻光的油墨喷涂在感光层上，待油墨干燥后用紫外光对网版进行全面曝光，未喷油墨的地方见光固化，而喷有油墨的部分，则在显影时被显影液（通常为水）除去，形成网版的图文。（2）直接曝光制版同样需将网版涂布感光胶并干燥或贴上菲林，通过计算机控制UV光源或激光光源直接对网版进行曝光，见光的部分感光胶发生交联固化，未见光的部分，则在显影时被显影液（通常为水）除去，形成网版的图文。  \n\n两种CTS系统都需要有较大的设备投资，这就影响了CTS的推广应用。但CTS作为数字化的网版制造技术，不仅减少了制版工序，节省了时间；还不用胶片，免除了银盐片冲洗加工，减少了“三废”；印刷信息保存方便，修改容易，还可以远程传送；多版套印时，数字化网版定位，减小了人为误差；可以通过网络与客户交流印刷信息，省时省力；对丝网目数没有要求，对网框无特别要求，感光胶也无需专用感光胶，网点形状和网点大小可设定，也无特别的暗房要求。CTS系统的上述优点，势必为网版印刷开拓更广阔的市场。随着数字化技术在印刷行业应用的深入发展，CTS系统也将与CTP一样逐步推广，引领着网版印刷的发展方向，代表着网版印刷发展趋势，得到更广泛、更普遍的使用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 534,
+        "chunk": "# 9.7 感光性树脂和感光剂的合成方法  \n\n（1）对重氮二苯胺氯化锌复盐的合成将18.4g（0.1mol）对氨基二苯胺溶于5%的盐酸溶液，冷至0℃，搅拌下慢慢滴加6.9g（0.1mol）亚硝酸钠的浓水溶液，保持0～5℃，加毕，继续搅拌 $0.5\\mathrm{h}$ 。加人 $6.8\\mathbf{g}$ ? $\\scriptstyle\\left\\{0,2{\\bmod{1}}\\right.$ ）理论量稍过量的氯化锌结晶，充分振荡后放置，析出对重氮二苯胺氯化锌复盐结晶，过滤后自然晾干，产率 $90\\%$ 以上。  \n\n（2）3-甲氧基-4-吗啉基苯基重氮四氯化锡复盐的合成  \n\n![](images/e585dfa0415c8eff159d2e41aad263aabb487ab7ad2deec050e759d488105fcb.jpg)  \n\n![](images/ac95f34dea17f9cfebc91c5dee44d1d2e4942896101db36be474c9ea723d8d65.jpg)  \n\n将 $9.4\\mathbf{g}$ （0.05mol）2-氯-5-硝基苯甲醚和 $11.5\\mathbf{g}\\left(0.13\\mathbf{mol}\\right).$ ）吗啉充分混合，升温至$155^{\\circ}\\mathrm{C}$ ，搅拌反应 $^{\\mathfrak{g}\\mathbf{h}}$ ，减压蒸馏除去未反应的吗啉，冷却加人 $40\\mathrm{mL}$ 水，析出固体，捣碎、抽滤，滤渣用 $\\scriptstyle40\\mathbf{m}\\mathbf{L}\\ 6\\mathbf{m}\\mathbf{ol}/\\mathbf{L}$ 硫酸加热溶解，冷却，在 ${<}15^{\\circ}\\mathrm{C}$ 放置过夜，此时未反应完全的原料2-氯-5-硝基苯甲醚以固相析出，过滤，滤渣回收，滤液用浓氨水中和至 $\\scriptstyle\\mathtt{p H}=7\\sim8$ ，析出黄色沉淀，冷却抽滤，水洗两次，真空干燥，得黄色固体产品 2-N-(2-甲氧基-4-硝基苯基）吗啉（A） $8.8{\\bf g}$ ，产率 $82.2\\%$ ，熔点 $102.5{\\sim}103.5^{\\circ}\\mathrm{C}$ 。  \n\n将 $13.7{\\bf g}$ 1 $\\left(0,06\\mathrm{mol}\\right)$ ）二氯化锡（ $\\mathrm{(SnCl_{2}}\\cdot2\\mathrm{H}_{2}\\mathrm{O})$ 溶于 $35\\mathrm{mL}$ 浓盐酸中，在剧烈搅拌下加人 $\\mathbf{3.57g}(0.015\\mathbf{mol})$ A，用冷水浴冷却，控制反应温度 ${<}70\\%$ ，约几分钟后，硝基化合物全部溶解，反应温度开始下降，同时析出大量白色不溶物， $70^{\\circ}\\mathsf{C}$ 反应2.5h，冷至室温，置冰水水浴中静置1.5h，充分沉淀，抽滤，白色滤渣用 $20\\mathrm{mL}$ 水溶解，用 $30\\%$ 的氢氧化钠溶液中和，直至所生成 $\\mathsf{S n}(\\mathrm{OH})_{4}$ 全部溶解，冷却抽滤，水洗至弱碱性，真空干燥，用1：3.5的乙醇水溶液重结晶，得白色产品3-甲氧基-4-吗啉基苯胺 $(\\mathbf{B})2,85\\mathbf{g}$ ，收率 $88.8\\%$ ，熔点 $130{\\sim}130.5^{\\circ}\\mathrm{C}$ 中  \n\n将 $2.088^{\\textrm{B}}$ 溶于 $\\boldsymbol{10}\\mathbf{mL}6\\mathbf{mol/L}$ 盐酸中，用冰水浴冷至 $0^{\\circ}\\mathrm{C}$ 后滴加 $0.85{\\bf g}$ (0.012mol）亚硝酸钠和 $2\\mathrm{mL}$ 水配成的溶液，控制滴加速率，使反应温度在 $2{\\sim}49\\$ ，加毕搅拌 $15\\mathrm{{min}}$ ，用淀粉KI试纸检验显蓝色，剧烈搅拌，滴加由 $\\mathbf{2.5g}(0.007\\mathbf{mol})$ $\\mathrm{SnCl}_{4}\\cdot5\\mathrm{H}_{2}\\mathrm{O}$ 和 $35\\mathrm{mL}$ 水所配成的溶液，很快析出黄色沉淀，在 $0^{\\circ}\\mathrm{C}$ 放置 $15\\mathrm{min}$ 充分沉淀，迅速抽滤，立即真空干燥，得产品3-甲氧基-4-吗啉基苯基重氮四氯化锡复盐（C） $3.8{\\bf g}$ ，收率 $99\\%$ ，该重氮盐紫外光谱吸收波长为 $320{\\sim}480\\mathrm{nm}$ ， $\\lambda_{\\operatorname*{max}}{=}408\\mathrm{nm}$  \n\n（3）重氮感光树脂的合成在三口烧瓶中加入浓硫酸 $_{40\\pmb{g}}$ ，冷至 $0^{\\circ}\\mathrm{C}$ ，慢慢加入 $\\mathbf{15g}$ 二苯胺重氮盐，维持反应温度 $0\\sim5\\mathrm{{C}}$ ，分批加人 $\\phantom{+}1.92g$ 经研磨的多聚甲醛，在 $0\\sim5\\%$ 反应$^{3\\mathrm{h}}$ ，加 ${\\bf60m L}$ 水使生成的重氮树脂溶解。加入 $_{10\\mathbf{g}}$ 氯化锌，得黄色沉淀，即为重氮树脂氯化锌复盐。过滤，将滤出的树脂复盐溶于水中，加人三甲苯磺酸 $_{198}$ ，析出黄色沉淀，干燥后得 $24\\mathbf{g}$ 三甲苯磺酸重氮树脂。  \n\n（4）重氮感光性树脂的合成  \n\n![](images/96383deffa91e009a84e6aa079c00455a28d91dbba9c3f04db8b42b2711035ee.jpg)  \n\n在三口烧瓶中加人7.5g干燥的对重氮二苯胺的氯化锌复盐和 $12.5\\mathrm{mL}98\\%$ 的浓硫酸，搅拌至重氮二苯胺的氯化锌复盐溶解，再加入1g聚甲醛， $10^{\\circ}\\mathrm{C}$ 下搅拌反应 $^{3\\mathrm{h}}$ 。反应完毕，将反应液倒至 $100\\mathrm{mL}$ 乙醇中，立即有沉淀析出，过滤，用乙醇多次洗涤，再过滤得固体物于暗处风干，得约 $5.8\\mathbf{g}$ 黄绿色粉末状重氮树脂。  \n\n（5）改进型重氮感光性树脂的合成在三口烧瓶中加人4-重氮二苯胺硫酸盐 $230\\mathbf{g}$ 和  \n\n$200\\mathbf{g}$ 磷酸，充分搅拌使其分散。加入 $\\boldsymbol{30}\\mathbf{g}$ 多聚甲醛， $40^{\\circ}\\mathrm{C}$ 搅拌反应24h，再加人苯酚 $\\mathfrak{g}_{4\\mathbf{g}}$ ，多聚甲醛 $_{15{\\bf g}}$ 和磷酸 $\\scriptstyle200{\\mathbf{g}}$ ，在 $50^{\\circ}\\mathrm{C}$ 搅拌反应 $24\\mathrm{h}$ 。将反应液在大量水中分散沉淀，过滤水洗，得黄色的重氮树脂(改进型)。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 535,
+        "chunk": "# （6）带叔氨基的聚乙烯醇系感光性树脂的合成（一）  \n\n![](images/97fec314f84179e322aa055562e2e942194b1ad1f5c93f27855cfe427451de56.jpg)  \n\n在三口烧瓶中加入 $_{10\\mathbf{g}}$ 聚乙烯醇（05-88)、5g对二甲氨基苯甲醛、 $100\\mathbf{g}$ 冰醋酸和 $0.3\\mathbf{g}$ 催化剂对甲苯磺酸，升温至 $80\\sim100\\mathrm{^{\\circ}C}$ ，反应2h，加人 $_{5g}$ 马来酸酐、 $0.01{\\bf g}$ 对苯二酚，升温至 $100{\\sim}115^{\\circ}\\mathrm{C}$ 反应 $^{2\\mathrm{h}}$ ，减压蒸馏除去溶剂，提纯，得到产物为聚乙烯醇环缩二甲基苯甲醛的马来酸酯，具有感光性。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 536,
+        "chunk": "# （7）带叔氨基的聚乙烯醇系感光性树脂的合成（二）  \n\n![](images/f2ffa6207f1e389ffbdd37dba1c88c5ea29e462c1e1d848f043b292c5ee1f86d.jpg)  \n\n在三口烧瓶中加人 $_{10\\mathbf{g}}$ 聚乙烯醇 (05-88)、 $_{2g}$ 对二甲氨基苯甲醛、 $100{\\dot{\\mathbf{g}}}$ 冰醋酸、 $\\phantom{-}0.38$ 对甲苯磺酸，升温至 $80{\\sim}100\\mathrm{^{\\circ}C}$ 反应 $\\mathbf{2h}$ ，加人 $_{10\\mathbf{g}}$ 羟甲基丙烯酰胺，在 $90^{\\circ}\\sim100^{\\circ}{\\mathrm{C}}$ 反应2h，减压蒸馏除去溶剂，提纯，得到黄色固体，为聚乙烯醇环缩二甲氨基苯甲醛的丙烯酰胺缩合物，具有感光性，产率 $85\\%$ o  \n\n（8）光交联剂 $N$ ， $\\mathbf{N}^{\\prime}$ -双丙烯基酒石酸酰胺的合成在三口烧瓶中加人 $0.1\\mathrm{mol}$ 酒石酸、0.4mol乙醇、适量对甲苯磺酸与甲苯，升温回流脱水反应 $_{3\\sim5\\mathrm{h}}$ ，脱水率 $997\\%$ 结束，蒸馏除去甲苯和未反应的乙醇，得酒石酸乙酯，收率 $96\\%$ 。 SA  \n\n在三口烧瓶中加入 $0.1\\mathrm{mol}$ 酒石酸乙酯和 $\\scriptstyle0.4\\mathrm{mol}$ 丙烯胺及少量对苯二酚，搅拌升温至回流，反应 $_{2\\sim3\\mathrm{h}}$ ，减压蒸馏回收未反应丙烯胺，最后加入适量乙醇搅拌 $0.5\\sim1\\ensuremath{\\mathrm{h}}$ ，降至室温，放置过夜，过滤，滤饼即为 $\\mathbf{\\delta}_{N,N^{\\prime}}$ -双丙烯基酒石酸酰胺粗品，收率 $65\\%$ 。用乙醇对粗品重结晶，晾干， $80^{\\circ}\\mathrm{C}$ 热风干燥，得白色针状结晶，最终收率 $53\\%$ ， $N$ $N^{\\prime}$ 双丙烯基酒石酸酰胺可作为PS版光交联剂。  \n\n（9）双鼠氮型感光剂2，2-双（3，4-叠氮苯）丙烷的合成  \n\n![](images/642abf500ce15dc20ae077d0f9bd0e76bb82cbe799aada1e9efb7215ffe92e39.jpg)  \n\n在三口烧瓶中加人34.2g（0.15mol）双酚A、100mL乙酸，在20℃滴加24mL(d=1.4g/mL，0.36mol）硝酸，加毕继续反应2h，抽滤洗涤，得粗品36.5g，产率76%，粗品用乙醇重结晶得纯品A[2,2-双-（3-硝基-4-羟基苯基）丙烷]，熔点130.5～131℃。  \n\n将6.4g(0.02mol）A溶于190mL无水乙醇中，加入1g雷尼镍，在常压下通氢气催化还原。当吸氢停止后，加热到70℃，过滤、浓缩，得白色至淡灰色的产物B4.6g，产率 $96\\%$ 。  \n\n在烧杯中依次加人3.9g（0.015mol）B、5.5mL乙酸、3g乙酸钠溶于5mL水的溶液，1g 硫酸钠溶于5mL水的溶液，置于冰浴中，在0℃时滴加2.7g亚硝酸钠的溶液，进行氮化，提取氮化合物得紫红色固体 $\\mathrm{~C~}2.5\\mathbf{g}$ ，产率为 $60\\%$ ，产品为2,2-双（3,4-叠氮苯)丙烷， $\\lambda_{\\operatorname*{max}}=373\\mathrm{nm}$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 537,
+        "chunk": "# (10）重氮萘感光剂的合成（一)  \n\n![](images/28c481b5ee7f32dc301b93ca979cca480640c1450d2321bd46e5bfcc6a41eece.jpg)  \n\n将6.3g $\\left(0,05\\mathbf{mol}\\right)$ 连苯三酚溶于 $\\mathbf{10.5mL}$ (0.1mol) $30\\%$ 的盐酸溶液中，搅拌，加热到 $80^{\\circ}\\mathrm{C}$ ，使连苯三酚全部溶解，再降温至 $55\\%$ ，缓慢滴加 $6.58$ $\\left(0,05\\mathrm{mol}\\right)$ 乙酰乙酸乙酯，滴加完缓慢升温至有棕黄色物质析出，停止反应，抽滤水洗，再用乙酸乙酯洗，抽滤， $50\\textcircled{\\times}$ 干燥，用乙醇重结晶，得A（7,8-二羟基-4-甲基香豆素)。  \n\n将2,1,5-重氮萘磺酰氯（或2,1,4-重氮萘磺酰氯）与A以摩尔比 $2:1$ 溶解在丙酮中，恒温 $40^{\\circ}\\mathsf{C}$ ，搅拌下2h内滴加2mol三乙胺，加毕再反应 $\\pmb{2}\\sim3\\mathbf{h}$ ，将反应液倒入十倍蒸馏水中洗涤，过滤水洗， $40^{\\circ}\\mathrm{C}$ 干燥至恒重，得到B，为重氮萘感光剂，整个过程避光。  \n\n![](images/eccda2ba96567055081e2fb22b74ffb778ad4a238b29c887d9b445e23604a2f9.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 538,
+        "chunk": "# （11）重氮萘鼠感光剂的合成（二）  \n\n将6.3g（0.05mol）连苯三酚溶解在31.5mL（0.3mol）盐酸溶液中，加热至65℃，全部溶解为黑色透明液体，降温至55℃，加人11.4g（0.05mol）二苯基羟基乙酸，升温至78℃，搅拌混合均匀，滴加40mol无水乙醇，在78℃反应5h，冷却旋蒸除去乙醇，用甲苯重结晶抽滤，50℃干燥，得无色结晶体A（6,7-二羟基-3,3-二苯基-3H-苯并呋喃-2-酮)，熔点 $186^{\\circ}\\mathrm{C}$ ，产率 $44.65\\%$ a  \n\n将2mol2,1,5-重氮萘磺酰氯（或2,1,4-重氮萘磺酰氯）与1molA溶解于丙酮中，恒温40℃，搅拌下于2h内滴加2mL三乙胺，加毕再反应2～3h，将反应液倒人十倍蒸馏水中洗涤，过滤、水洗，40℃干燥至恒重，得到B为重氮萘感光剂(整个过程需避光)。  \n\n(12）重氮萘感光剂的合成（三）将连苯三酚、二苯基羟基乙酸(1：1，摩尔比)和适量催化剂对甲苯磺酸加入到三口烧瓶中，以甲苯为溶剂进行回流分水。然后蒸出甲苯，再继续反应一段时间，得到产物A(6,7-羟基-3,3-二苯基-3H-苯并呋喃-2-酮)。  \n\n以丙酮为溶剂，将A和2，1,5-重氮萘磺酰氯 $(1:1$ ，摩尔比）进行酯化反应，滴加等物质的量的碳酸钠溶液，回流反应3h，经水洗，抽滤40℃干燥，得到重氮萘感光剂(整个反应需避光进行)。  \n\n（13）聚氨酯叠氮萘磺酸酯的合成在三口烧瓶中加人11.0g（0.10mol）对苯二酚、60mL丙酮搅拌溶解，升温，滴加8.0g（0.045mol）甲苯二异氰酸，回流反应2.5h。冷却，倒入适量去离子水中，析出白色沉淀，抽滤，固体真空干燥，得产物A16g，产率88.9%。熔点 $194{\\sim}196^{\\circ}\\mathrm{C}$ 。  \n\n在三口烧瓶中加人16gA和30mL二氧六环，搅拌溶解，滴加5.4g1,2-蒸二叠氮-5-磺酰氯和20mL二氧六环混合液，再加人2.5g碳酸钠固体和5mL去离子水，搅拌、升温至60℃反应1.5h，65℃反应1h，冷却后倒入盐酸水溶液中析出黄色沉淀，抽滤，用去离子水洗至中性，真空干燥，得产物 $\\tau_{\\mathbf{{g}}}$ ，为聚氨酯叠氮萘鼠磺酸酯， $\\lambda_{\\operatorname*{max}}$ 为 $346\\mathrm{nm}$ 和 ${\\bf395n m}$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 539,
+        "chunk": "# （14）光产酸剂硫盐的合成（一）  \n\n![](images/fbaa337f4fdd1f6767598cf064ba1c847934cebb0d0cbc58ef279ef198ddd979.jpg)  \n\n将（4-N，N-二苯氨基）-苯甲醛和磷叶立德试剂（摩尔比为1.5：1）和适量二甲基甲酰胺加人三口烧瓶中，通氮气，冰浴冷至0℃，加入等物质的量的甲醇钠，0℃搅拌30min，室温搅拌24h，用甲醇沉淀，过滤，用二氯甲烷/乙醇重结晶，得黄色固体A为4-[4-(甲硫基)苯乙烯基]-N,N-二苯基苯胺，产率70%，熔点185.4～187.2℃。  \n\n将A溶解在80mL干燥的二氯甲烷中，加入三氟磺酸甲酯（摩尔比为5.1：6.1)。室温避光搅拌反应4h，蒸出溶剂后，用乙醇沉淀，得黄绿色固体B，产率70%，熔点151.2～$159.5\\%$ ， $\\lambda_{\\operatorname*{max}}=393\\mathrm{nm}$ ，为硫盐光产酸剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 540,
+        "chunk": "# （15）光产酸剂硫盐的合成（二）  \n\n![](images/ac0b7cbb5a4d6801d808061131f9b0af1eb310565b87c6c1103904817f0b06b7.jpg)  \n\n将4-二乙氨基苯甲醛、磷叶立德试剂（摩尔比为1.5：1）和溶剂二甲基甲酰胺加人三口烧瓶中，通氮气，冰浴冷至0℃，加人等物质的量的甲醇钠，0℃搅拌30min，室温搅拌24h，用甲醇沉淀、过滤，滤饼用二氯甲烷/乙醇重结晶，得黄绿色固体A为4-［4-（甲硫基）苯乙烯基］-N,N-二乙基苯胺，产率30%，熔点143.5～144.7℃，max=368nm。  \n\n将A溶解在80mL干燥二氯甲烷中，加入三氟磺酸甲酯（摩尔比为5.1：6.1)，室温避光搅拌反应4h，蒸出溶剂，在乙醇中沉淀，乙腈/乙醚重结晶得浅黄色固B产率40%，max=$402\\mathrm{nm}$ ，为硫盐光产胶剂。  \n\n（16）光产酸剂空心酞菁磺酸对甲苯酯的合成在三口烧瓶中加人2.57g空心酞菁和15mL氯磺酸，搅匀，在氮气保护下，升温至130℃回流反应6h，冷至60℃滴加4mL氯化亚矾和0.4mL二甲基甲酰胺混合液，反应1.5h，降至室温，缓慢倒人250mL含有碎冰的水中，有大量絮状深蓝色沉淀产生，静置、过滤，滤饼依次用水、 $95\\%$ 的乙醇洗数次，至溶液呈中性，干燥过夜，得空心酞菁磺酰氯A，产率 $64\\%$ 。  \n\n在三口烧杯中将0.5g对甲苯酚溶于5%的氢氧化钠溶液中，再加入1gA，室温下，剧烈搅拌反应2h，反应液用二氯甲烷萃取，有机层用无水硫酸镁干燥，蒸去溶剂，用硅酸柱色谱分离以二氯甲烷：丙酮 $\\mathbf{\\delta}=\\mathbf{8}:1$ （体积比）收集深蓝色液体，蒸去溶剂后得紫黑色固体空心酞菁磺酸对甲苯酯，为光产酸剂。  \n\n（17）光热敏微胶囊的制备将取 $1.5\\mathbf{g}$ 黑染料ODB-2、 $_{10\\mathbf{g}}$ TMPTA、 $_{10\\mathbf{g}}$ TPGDA和${\\bf48}\\ \\mathrm{(PO)}_{2}\\mathrm{NPGDA}$ ，搅拌加热溶解，冷至室温，加人 $60\\mathbf{g}\\ \\mathbf{D}\\mathbf{-}110\\mathbf{N}$ ，在安全灯下加入光引发剂184溶液 $1.5\\mathrm{mL}$ （ $50\\%$ 的乙酸乙酯）和 $\\mathbf{8g}$ 乙酸乙酯得油相。  \n\n$\\scriptstyle400\\mathrm{mL}$ ， $4.5\\%$ 的聚乙烯醇PVA224和 $20\\mathrm{{mL}80\\mathbf{g}/L}$ 的十二烷基磺酸钠混匀得水相。  \n\n在安全灯下，用高速剪切 $9000\\mathrm{r/\\min}$ 搅拌速度下，将油相缓慢加人水相中，分散$10\\mathrm{{min}}$ 。加人去离子水 ${300}\\mathrm{mL}$ ，四乙烯五胺 $\\mathbf{88}$ ，在 $800\\mathbf{r}/\\mathbf{min}$ 搅拌速度下， $60^{\\circ}\\mathrm{C}$ 恒温反应$^{3\\mathrm{h}}$ ，得到光热敏微胶囊。  \n\n（18）光敏微胶囊的制备在三口烧瓶中加入一定量的乙氧基化季戊四醇（PP50）和丙烯酸（摩尔比为 $1:2)$ 、 $0.5\\%$ （质量分数）对甲苯磺酸、 $0.5\\%$ （质量分数）对甲氧基苯酚和适量甲苯，升温至 $97^{\\circ}\\mathrm{C}$ 反应8h，得到含有双键的聚酯丙烯酸酯（A-PP50)。  \n\n取 $4.75{\\bf g}\\ {\\bf A}–{\\bf P}{\\bf P}50$ ，加人到含 $\\phantom{+}2.508$ 甲苯二异氰酸酯的环已酮溶液中，加人 $0.1\\mathrm{mL}$ 的二月桂酸二丁基锡， $60^{\\circ}\\mathrm{C}$ 反应4h，得到含双键壁材预聚物的环已酮溶液。  \n\n在含 $18\\mathbf{g}$ 预聚物的环己酮溶液中加入 $0.5{\\bf g}$ 光引发剂1173和 $\\mathbf{2}.0\\mathbf{g}$ 黑染料ODB-2作为油相，投入到 $80\\mathrm{mL1\\%}$ 的聚乙烯醇PVA1788水溶液中，滴加 $0.1\\mathrm{mL}$ 的二月桂酸二丁基锡，室温搅拌反应 $^{8\\mathrm{h}}$ ，得到以ODB-2的环已酮溶液为芯材，含双键的聚氨酯丙烯酸酯为壁材的光敏微胶囊悬浮液，用 $30\\%$ 的乙醇溶液洗涤悬浮液，除去未被包覆的油相，滤出微胶囊，室温干燥 $24\\mathrm{h}$ 0  \n\n以下配方中没注明的单位为质量份。  \n\n（1）重铬酸盐明胶丝网感光液参考配方使用时将甲、乙液均匀混合。  \n\n<html><body><table><tr><td>明胶/g 500 水/mL 2500</td><td>蛋白液/mL 100 重铬酸铵/g 50</td></tr><tr><td>（2）重铬酸盐蛋白丝网感光液参考配方</td><td></td></tr><tr><td>鸡蛋清/mL 30 水/mL 200</td><td>氨水/mL 5 重铬酸铵/g 3.5</td></tr><tr><td>（3）蛋白版丝网感光液参考配方</td><td></td></tr><tr><td>水/mL 100 干蛋白/g 1000</td><td>重铬酸铵/g 275 氢氧化铵（氨水）/mL 250</td></tr><tr><td>（4）重铬酸盐虫胶丝网感光液参考配方</td><td>}1</td></tr><tr><td>甲液： 虫胶片/g 110 氨水/mL 275 水/mL 10000</td><td>乙液： 重铬酸铵/g 5 水/mL 150</td></tr></table></body></html>  \n\n（5）重铬酸盐聚乙烯醇丝网感光液参考配方  \n\n\n<html><body><table><tr><td>聚乙烯醇（聚合度1750）/g 500 水/mL 8000</td><td>磺酸钠 少量 重铬酸钠/g 50</td></tr><tr><td>（6）重氮丝网感光胶参考配方</td><td></td></tr><tr><td>部分皂化的聚乙烯醇水溶液（20%）（皂 60.0 化度88%，聚合度1400）</td><td>聚醋酸乙烯乳胶（50%） 40.0 对-重氮二苯胺-多聚甲醛缩合物 1.5</td></tr><tr><td>（7）丝网感光胶参考配方</td><td></td></tr><tr><td>皂化度40%的醋酸乙烯-甲基丙烯酸（97：3） 80 共聚物的甲醇水溶液（40%） PETA 40</td><td>安息香甲醚 4 甲醇 40 水 80</td></tr><tr><td>（8）液体感光性树脂凸版参考配方</td><td></td></tr><tr><td>偏苯三酸酐/马来酐/乙二醇 70.0 （46/24/30）不饱和聚酯 丙烯酰胺 30.0</td><td>苯偶姻 0.7 对苯二酚 0.01 丙酮 20.0</td></tr><tr><td>（9）液体感光性树脂凸版参考配方</td><td></td></tr><tr><td>[聚乙二醇（600）-乙二酸-富马酸] 100.0 不饱和聚酯（摩尔比1：0.5：0.5） 丙烯酸 20.0</td><td>丙烯酰胺 30.0 苯偶姻 2.0 对苯二胺 0.1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 541,
+        "chunk": "# （10）液体感光性树脂凸版参考配方  \n\n<html><body><table><tr><td colspan=\"3\">改性不饱和聚酯 100.0 安息香异丁醚 HEA 30.0 2,6-二叔丁基对甲苯酚 30.0</td></tr><tr><td colspan=\"3\">DEGDMA （11）液体感光性树脂凸版参考配方</td></tr><tr><td>不饱和聚酯 HEMA</td><td>100.0 双丙酮丙烯酰胺 20.0 安息香乙醚 20.0 对甲氧基苯酚</td><td>10.0 1.0 0.1</td></tr><tr><td colspan=\"3\">DEGDMA （12）液体感光性树脂凸版参考配方</td></tr><tr><td>不饱和聚氨酯 120.3 7.3</td><td>BP 2.6-二叔丁基对甲苯酚</td><td>1.5 0.1</td></tr><tr><td colspan=\"3\">季戊四醇疏基丙酸酯 （13）固体感光性树脂凸版参考配方</td></tr><tr><td>醇溶性聚酰胺 TEGDA 间-二甲苯双丙烯酰胺 N-羧甲基丙烯酰胺-双乙二醇醚</td><td>70.0 安息香甲醚 7.0 对甲氧基苯酚 14.0 甲醇 8.2</td><td>0.7 0.1 300.0</td></tr><tr><td colspan=\"3\">（14）感光性树脂凸版参考配方</td></tr><tr><td>醇溶性聚酰胺 对-苯二亚甲基双丙烯酰胺 六次甲基双丙烯酰胺 TEGDA 丙烯酸丁二醇酯</td><td>100 顺丁烯二酸酐 32 安息香甲醚 21 对苯二酚 10 甲醇</td><td>1 1 0.002 500</td></tr><tr><td colspan=\"3\">3 （15）感光性树脂凸版参考配方 大（</td></tr><tr><td>醋酸纤维素 醋酸丁酸纤维素 TMPTA</td><td>2.7 樟脑 4.2 米酮 13.5 丙酮</td><td>0.47 0.47 116.0</td></tr><tr><td colspan=\"3\">（16）感光性树脂凸版参考配方</td></tr><tr><td>不饱和聚酯 DEGDA 丙烯酰胺</td><td>70.0 安息香甲醚 15.0 对-叔丁基邻苯二酚 15.0</td><td>2.0 0.1</td></tr><tr><td colspan=\"3\">（17）感光性树脂凸版参考配方</td></tr><tr><td>聚乙烯醇肉桂酸酯 氯化苯</td><td>2.5甲苯 25.0 5-硝基</td><td>75.0 0.25</td></tr><tr><td colspan=\"3\">（18）醇显影尼龙版参考配方</td></tr><tr><td>尼龙66:610:6（35:35:30） TEGDA</td><td>70.0 7.0 安息香甲醚</td><td>N-羟甲基丙烯酰胺-乙二醇双醚 8.0 0.8 0.1</td></tr><tr><td colspan=\"3\">间苯二甲酰双丙烯酰胺 14.0 对甲氧基苯酚 （19）碱溶性感光性树脂凸版参考配方</td></tr><tr><td>醋酸纤维素琥珀酸酯 TEGDA</td><td>90.0 对甲氧基苯酚 50.0 聚氧乙烯</td><td>0.005 10.0 85.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 542,
+        "chunk": "# （20）碱水显影感光性树脂凸版参考配方  \n\n<html><body><table><tr><td colspan=\"2\">不饱和聚酯 70 安息香甲醚 DEGDA 15 对叔丁基邻苯二酚</td></tr><tr><td colspan=\"2\">丙烯酰胺 15 （21）水溶性感光树脂凸版参考配方</td></tr><tr><td>聚乙烯醇（皂化度80.5%，聚合度500） 70.0 聚乙烯醇（皂化度88.5%，聚合度500） 30.0 HEMA 100</td><td>安息香异丙醚 2.5 对甲氧基苯酚 0.2 二碘曙红5%水溶液 0.5 80.0</td></tr><tr><td colspan=\"2\">乙二醇双甲基丙烯酸酯 5.0 水 （22）水溶性感光尼龙凸版参考配方</td></tr><tr><td>水溶性尼龙树脂 100.0 亚甲基双丙烯酰胺 10.0</td><td>对苯二酚 0.2 甲醇 适量</td></tr><tr><td colspan=\"2\">安息香异丙醚 2.0 （23）感光柔性版参考配方</td></tr><tr><td>不饱和聚酯 100.0 丙烯酰胺 15.0</td><td>安息香 2.0 对苯二酚 0.1</td></tr><tr><td colspan=\"2\">N-羟甲基丙烯酰胺 20.0 （24）感光柔性版参考配方</td></tr><tr><td colspan=\"2\">SBS嵌段共聚物 10.0 2,6-二叔丁基对甲苯酚 TEGDA 10 环已烷</td></tr><tr><td colspan=\"2\">150 651 1.0 二甲苯 150</td></tr><tr><td colspan=\"2\">（25）感光柔性版参考配方 苯乙烯-异戊二烯-苯乙烯嵌段共聚物 90.16 乙基葱</td></tr><tr><td colspan=\"2\">0.55 TMPTA 9.23 对甲氧基苯酚 0.06 （26）感光柔性版参考配方</td></tr><tr><td>苯乙烯-异戊二烯-苯乙烯嵌段共聚物 82.3 2-甲基苯乙烯-乙烯基甲基醚共聚物 6.0 乙二醇二丙烯酸酯 5.3 乙二醇二甲基丙烯酸酯 3.7</td><td>651 1.4 2,6-二叔丁基对甲苯酚 0.166 对苯二酚 0.001 红染料 0.003</td></tr><tr><td colspan=\"2\">HEMA 0.13 微晶蜡 （27）感光柔性版参考配方</td></tr><tr><td>丙烯睛-丁二烯共聚物 48.3 HDDA 5.0 HDDMA 5.0</td><td>2,6-二叔丁基对甲酚 0.5 SiO2 1.0 染料 0.006 30.0</td></tr><tr><td colspan=\"2\">651 1.2 邻苯二甲酸二丁酯 （28）感光柔性版参考配方</td></tr><tr><td>反式1，2-聚丁二烯（15%结晶度） 100 30</td><td>甲基丙烯酸月桂酯 10 安息香异丙醚 3</td></tr><tr><td colspan=\"2\">乙二醇二甲基丙烯酸酯 （29）感光柔性版参考配方</td></tr><tr><td>苯乙烯-丁二烯共聚物（分子量1000） 30 TEGDA 16 TMPTA 10</td><td>BP 3 对甲氧基苯酚 0.01 甲苯 500</td></tr></table></body></html>  \n\n<html><body><table><tr><td colspan=\"3\">（30）感光柔性版参考配方</td></tr><tr><td>间规1，2-聚丁二烯 新戊二醇二甲基丙烯酸酯</td><td>100安息香异丙醚 30 阻聚剂</td><td>3 适量</td></tr><tr><td colspan=\"3\">（31）感光柔性版参考配方</td></tr><tr><td>苯乙烯-丁二嵌段共聚物 TMPTA</td><td>100 651 15 阻聚剂</td><td>2 适量</td></tr><tr><td>季戊四醇-β硫基丙烯酸酯 （32）感光柔性版参考配方</td><td>2</td><td></td></tr><tr><td colspan=\"3\">丁腈橡胶 100.0 BP</td></tr><tr><td>TMPTA</td><td>20.0 阻聚剂</td><td>适量</td></tr><tr><td colspan=\"3\">（33）感光柔性版参考配方 SIS橡胶 100.0 安息香甲醚</td></tr><tr><td>HDDMA （34）水显影感光柔性版参考配方</td><td>30 阻聚剂</td><td>适量</td></tr><tr><td colspan=\"3\">水溶性乙烯-乙烯醇共聚物 100 1173 DEGDA 25 阻聚剂</td></tr><tr><td>HEMA 10 （35）平凹版感光液参考配方</td><td></td><td>适量</td></tr><tr><td colspan=\"3\">聚乙烯醇/g 75 十二烷基磺酸钠（8°Be）/mL 重铬酸铵（16°Be）/mL</td></tr><tr><td>麦芽糖/g</td><td>125 水溶性紫染料（15%）/mL 1 水/mL</td><td>10 1000</td></tr><tr><td colspan=\"3\">（36）阳图PS版感光液参考配方 2,1,5-邻重氮萘磺酸酯/g 25 乙二醇单乙醚/mL</td></tr><tr><td>间甲酚醛树脂/g 碱性艳蓝/g</td><td>25 醋酸丁酯/mL 0.5</td><td>250</td></tr><tr><td colspan=\"3\">（37）阳图PS版感光液参考配方 2,1,5-邻重氮萘磺酸酯 9.0 油溶蓝 间甲酚醛树脂 17.0</td></tr><tr><td>叔丁基酚醛树脂 0.5 双酚A 0.3</td><td>乙二醇单甲醚醋酸酯 甲乙酮</td><td>150.0 80.0</td></tr><tr><td colspan=\"3\">（38）阳图PS版感光液参考配方 聚肉桂酰羟乙基丙烯酸甲酯 1.0 5-硝基</td></tr><tr><td>聚苯酚树脂与2，1，5-邻叠氮-2，1，5- 磺酰氯所成的酯 邻苯二甲酸二己酯</td><td>1,2-二氯乙烷 0.3 醋酸甲基纤维素酯</td><td>0.08 12.0 6.0</td></tr><tr><td colspan=\"3\">0.3 （39）阳图PS版感光液参考配方</td></tr><tr><td>A液： 间甲酚树脂/g 140 乙二醇独乙醚/mL 1000 B液： 酚醛树脂/g 140 乙二醇独乙醚/mL 1000</td><td>C液： 碱性艳蓝/g 乙二醇独乙醚/mL D液： 2,1,4-型感光性树脂/g 乙二醇独乙醚/mL</td><td>2 1000 40 1000</td></tr></table></body></html>  \n\n<html><body><table><tr><td>A液/mL 500 B液/mL 100</td><td>C液/mL 100 D液/mL 400</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 543,
+        "chunk": "# 四种溶液混合搅拌 $30\\mathrm{\\sim}40\\mathrm{min}$ ，抽滤置于棕色瓶中，避光、避潮湿待用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 544,
+        "chunk": "# （40）阴图PS版感光液参考配方  \n\n重氮树脂 0.65 乙二醇单甲醚 95.00  \n丙烯酸共聚树脂 5.00 二甲基甲酰胺 10.00  \n醇溶蓝 0.25  \n\n（41）阴图PS感光液配参考配方  \n\n改进型重氮树脂 1.0 聚乙二醇 0.05  \n水溶性聚丙烯酸 0.7  \n\n上述混合物溶解于混合溶剂中：  \n\n\n<html><body><table><tr><td></td><td>10 甲乙酮 20 水</td></tr></table></body></html>  \n\n（42）阴图PS版感光液参考配方  \n\n<html><body><table><tr><td>取代二苯胺重氮树脂</td><td>35</td><td>乙基罗丹明</td><td></td><td>4</td></tr><tr><td>聚乙烯醇缩甲醛</td><td></td><td>15 二丙酮醇</td><td></td><td>500</td></tr><tr><td>对甲苯磺酸</td><td></td><td>5 水</td><td></td><td>2000</td></tr></table></body></html>  \n\n（43）阴图PS版感光液参考配方  \n\n<html><body><table><tr><td>甲基丙烯酸羟乙酯/丙烯晴/甲基丙烯酸 甲酯/丙烯酸共聚物/g 二甲苯磺酸二苯胺重氮树脂/g</td><td>酸性艳蓝/g 二甲基甲酰胺/mL</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 545,
+        "chunk": "# （44）阴图PS版感光液参考配方  \n\n甲基丙烯酸烯丙酯-甲基丙烯酸共聚物 50.0 油性蓝603 1.0   \nTMPTA 20.0 二十二碳酸 1.5   \n4-重氮二苯胺-甲醛缩合物六氟化磷盐 3.0 乙二醇独甲醚 500.0   \n2，4-二甲基-硫杂葱酮 2.0 甲醇 150.0   \n2,4-二（三氯甲基）-6-（4-甲氧基）1，3，5均三嗪 2.0 甲基乙基酮 300.0",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 546,
+        "chunk": "# （45）阴图PS版感光液参考配方  \n\n<html><body><table><tr><td>甲基丙烯酸甲酯-甲基丙烯酸共聚物（摩 尔比9：1） PETA 特丁基慈 2.0</td><td>53.8 乙基紫 43.7 丁酮</td><td>对甲氧基苯酚 300.0</td><td>0.4 0.1</td></tr></table></body></html>  \n\n（46）阴图PS版感光液参考配方  \n\n甲基丙烯酸丙酯-甲基丙烯酸共聚物 3.2 结晶紫 0.1  \nPETA 1.7 甲基乙基酮 20.0  \n2，4-二甲基-硫杂葱酮 0.1 丙二醇单甲醚乙酸酯 20.0  \n2,4，6-三（三氯甲基）-1，3，5-均三嗪 0.1 含氟阴离子表面活性剂 0.03",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 547,
+        "chunk": "# （47）阴图PS版感光液参考配方  \n\n<html><body><table><tr><td>苯乙烯-马来酸酐共聚物 丙烯酸乙酯/甲基丙烯酸甲酸/丙烯酸共 聚物 TEGDMA 2.3</td><td>5.5 651 三氯甲烷 5.3 甲醇</td></tr><tr><td colspan=\"2\">（48）阴图PS版感光液参考配方</td></tr><tr><td>苯乙烯-马来酸酐共聚物（M=91000） 5.0 苯乙烯-马来酸酐（与PETA酯化）共聚物 30.0 PETA 10.0 乙二醇独甲醚</td><td>1700（光引发剂） 1.0 结晶紫 0.2 100.0</td></tr><tr><td colspan=\"2\">（49）光敏树脂版参考配方</td></tr><tr><td>甲基丙烯酸叔丁酯：甲基丙烯酸：苯乙 1.0 烯共聚物（1：2：0.5） 二乙烯基醚 0.1</td><td>三苯胺硫盐 0.1 1,4-二氧六环 9.0</td></tr><tr><td colspan=\"2\">（50）光敏CTP版参考配方</td></tr><tr><td>线型酚醛树脂 15.0 交联剂（双酚A/甲醛树脂） 5.0</td><td>三嗪类光产酸剂（溶于四氢味喃） 5.4 1%的四溴酚蓝乙二醇独甲醚溶液 1滴</td></tr><tr><td colspan=\"2\">乙二醇独甲醚 80.0</td></tr><tr><td>（51）紫激光CTP版材参考配方 聚氧乙烯接枝共聚物 58.7 DPET/PA 24.4</td><td>2,4,5-三芳基咪唑 2.0 Tolyi leuco Violet 4.5</td></tr></table></body></html>\n\n\n\n<html><body><table><tr><td>聚氧乙烯接枝共聚物 DPET/PA ITX</td><td>58.7 24.4 3.0 LeucoPropylViolet</td><td>2,4，5-三芳基咪唑 2.0 Tolyi leuco Violet 4.5</td></tr></table></body></html>  \n\n混合溶剂：正丁醇：水：戊酮 $=60:20:20,70\\mathrm{^{\\circ}C}$ 干燥75s涂层干重0. $75g/\\mathrm{m}^{2}$ 0  \n\n（52）紫激光CTP版材参考配方  \n\n<html><body><table><tr><td>丙烯酸低聚物（UR3447） 聚氧乙烯接枝共聚物 DTMPTA 2,4，5-三芳基咪唑</td><td>35.0 硫基三氮唑 32.4 9.0 BYK307</td><td>6.1 2-苯乙烯基-4，6-二（三氯甲基）均三嗪 3.3 0.2</td></tr></table></body></html>  \n\n混合溶剂：正丁醇：水：戊酮 $=60:20:20$ 涂层70℃干燥75s涂层干重1. $60g/\\mathrm{m}^{2}$ 。  \n\n（53）紫激光CTP版材参考配方  \n\n<html><body><table><tr><td>PUA(EB8301) 甲基丙烯酸聚合物（WS-96） 聚丙氧基-乙氧基嵌段共聚物 (PluruhicL43） 甲基丙烯酸甲酯聚合物（Acryloid A11) DPET/A(SR399)</td><td>3.59 18.07 ITX 4.79 Tolyl leucoViolet 荧光结晶紫 11.97 抗氧剂（BHT） 24.94 Irgamox1035</td><td>PETA衍生物（UR3447） 28.93 2.00 2,4，6-三（三氯甲基）-均三嗪 2.00 2.00 1.30 0.15 0.21</td></tr></table></body></html>\n\n混合溶剂：1-甲氧基-2丙醇：甲苯：甲乙酮：乙酸甲氧基丙酯=58.9：25：15：1.1。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 548,
+        "chunk": "# 第10章光电子工业用光固化材料  \n\n光刻胶（photoresist）又称光致抗蚀剂，是指通过紫外光、准分子激光、X射线、电子束、离子束等光源的照射或辐射，其溶解度发生变化的耐蚀刻薄膜材料。主要用于电子工业中集成电路和半导体分立器件的微细加工，同时在平板显示、发光二极管、倒扣封装、磁头及精密传感器等制作过程中也有着广泛的应用。利用光刻胶具有光化学敏感性，可进行光化学反应，将光刻胶涂覆在半导体、导体或绝缘体基片上，经曝光、显影后留下的部分对基片起保护作用，然后采用蚀刻剂进行蚀刻就可将所需要的微细图形从掩膜版（mask）转移到待加工的基片上，并进行扩散、离子注入、金属化等工艺。因此光刻胶是微细加工技术中的关键性化工材料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 549,
+        "chunk": "# 10. 1. 1 光刻技术的发展  \n\n光电子工业的发展离不开光刻胶的发展，这是由于电子工业微细加工的精度决定于光刻胶曝光、显影后成像分辨率。目前，光刻工艺中采用掩膜版曝光方式主要有接触式曝光和投影式曝光两种。  \n\n接触式曝光是将掩膜版直接放在光刻胶表面进行曝光的方式，该曝光方式的成像分辨率取决于以下公式。  \n\n$$\nL{=}3~\\sqrt{0.5\\lambda d}\n$$  \n\n式中 L 等距线宽；1- -曝光光源波长；$d$ 一光刻胶厚度。  \n\n接触式曝光的光效率虽然很高，但在基片和掩膜版对准过程中容易造成划伤而产生缺陷。为了减少由于硬接触造成的机械损伤，曝光时可在掩膜版和光刻胶表面之间留一道狭缝，即所谓接近式曝光，该方式的成像分辨率由以下公式决定。  \n\n$$\nL{=}3~\\sqrt{\\lambda~\\left(s{+}0.5d\\right)}\\approx}3~\\sqrt{s\\lambda}\n$$  \n\n式中L- 等距线宽；S- 掩膜版和光刻胶表面的距离， $\\textbf{\\^s}$ 最大值为 $10\\mu\\mathrm{m}$ 中  \n\n—曝光光源波长。  \n\n投影式曝光是目前集成电路制作中应用最广泛的曝光方式，它克服了接触式曝光的缺点，并降低了掩膜版的制作难度。该方式成像分辨率由以下公式表示。  \n\n$$\n\\therefore\\delta=k\\frac{\\lambda}{\\mathrm{NA}}\n$$  \n\n式中α——可分辨的两点或两线之间距离；  \n\n$\\lambda$ ——曝光光源波长；$k$ —常数，据Raleigh理论为0.5；NA——透镜开口数。  \n\n$$\n\\mathrm{NA}{=}\\frac{D/2}{f}\n$$  \n\n式中 $D$ 一透镜直径；$f$ —透镜焦距。  \n\n通过上述三个公式可以清楚地看到，成像分辨率都与曝光光源的波长有密切关系。光波长愈短，则成像分辨率愈高。因此，随着电子工业微细加工精度提高，线宽变窄，必然要求可使用的曝光光源波长变短；而曝光光源波长的变化，又必然要求光刻胶与之相匹配，促进了光刻胶的不断发展。  \n\n当今集成电路（IC）工业按照摩尔定律在不断发展，即集成电路的集成度每18个月翻一番；芯片的特征尺寸每3年缩小√2倍，芯片面积增加1.5倍，芯片中的晶体管数增加约4倍，每过3年便有一代新的集成电路产品问世（表10-1、表10-2)  \n\n表10-1光刻技术与集成电路发展的关系  \n\n\n<html><body><table><tr><td rowspan=\"2\">项目</td><td colspan=\"9\">时间</td></tr><tr><td>1986年</td><td>1989年</td><td>1992年</td><td>1995年</td><td>1998年</td><td>2001年</td><td>2004年</td><td>2007年</td><td>2010年</td></tr><tr><td>IC集成度</td><td>1M</td><td>4M</td><td>16M</td><td>64M</td><td>256M</td><td>1G</td><td>4G</td><td>16G</td><td>64G</td></tr><tr><td>技术水平/μm</td><td>1.2</td><td>0.8</td><td>0.5</td><td>0.35</td><td>0.25</td><td>0.18</td><td>0.13</td><td>0.10</td><td>0.07</td></tr><tr><td>技可能采用的光刻</td><td colspan=\"2\">g线</td><td colspan=\"2\">践线</td><td>i线F</td><td>KrF</td><td>KrF+RET</td><td>ArF+RET E呕吧</td><td></td></tr></table></body></html>\n\n注：g线为436nm光刻技术；i线为365nm光刻技术；KrF为248nm光刻技术；ArF为193nm光刻技术；F为157nm光刻技术；RET为光网增强技术；EPL为电子投影技术；PXL近X射线技术；IPL为离子投影技术；EUV为超紫外技术；EBOW为电子束直写技术。 新品  \n\n现在世界集成电路水平已由微米级（1.0μm）、亚微米级（1.0～0.35μm）、深微米级(0.35μm以下）进人到纳米级（90～65nm）阶段。光刻胶的光刻波长则经历了g线(436nm)→i线（365nm)→KrF激光（248nm)→ArF激光（193nm）→Fz激光（157nm）→极紫外（EUV13.4nm)→X射线（lnm）→更短波长的电子束（0.01～0.00lnm）、离子束$(<0.001\\mathrm{nm})$ 。  \n\n光刻胶曝光时，使用多种光源，光源的波长与能量关系见表10-3，从深紫外线开始光刻胶的反应以辐射化学为主，故又称辐射胶。  \n\n目前，在集成电路制作中使用的主要光刻胶见表10-4。  \n\n表10-2中央处理器（CPU）中集成的晶体管数和光刻胶制程  \n\n\n<html><body><table><tr><td>时间</td><td>CPU名称(内核名称)</td><td>集成晶体管数目/个</td><td>制程/μm</td></tr><tr><td>1971年</td><td>4004</td><td>2300</td><td>10</td></tr><tr><td>1974年</td><td>8080</td><td>6000</td><td>6</td></tr><tr><td>1978年</td><td>8086</td><td>29000</td><td>3</td></tr><tr><td>1982年</td><td>80286</td><td>134000</td><td>1.5</td></tr><tr><td>1985年</td><td>80386</td><td>275000</td><td>1.5</td></tr><tr><td>1989年</td><td>Intel 486</td><td>120万</td><td>1.0</td></tr><tr><td>1993年</td><td>Pentium</td><td>310万</td><td>0.8</td></tr><tr><td>1997年</td><td>Pentium ⅡI</td><td>750万</td><td>0.35</td></tr><tr><td>1999年2月</td><td>Pentium Ⅲ(destchut)</td><td>950万</td><td>0.25</td></tr><tr><td>1999年10月</td><td>Pentium II(coppermine)</td><td>2800万</td><td>0.18</td></tr><tr><td>2000年</td><td>Pentium IV (Willamette)</td><td>4200万</td><td>0.18</td></tr><tr><td>2002年</td><td>Pentium IV (Northwood)</td><td>5500万</td><td>0.13</td></tr><tr><td>2003年</td><td>Pentium IV(Banias)</td><td>7700万</td><td>0.13</td></tr><tr><td>2003年</td><td>Pentium IV(Prescott)</td><td>约1亿</td><td>0.09</td></tr></table></body></html>  \n\n表10-3光源的波长与能量关系  \n\n\n<html><body><table><tr><td>光源</td><td>相应波长/nm</td><td>能量/eV</td></tr><tr><td>紫外</td><td>350~450</td><td>2.7~3.5</td></tr><tr><td>深紫外</td><td>180~265</td><td>5~7</td></tr><tr><td>X射线</td><td>0.4~5.0</td><td>1000～5000</td></tr><tr><td>电子束</td><td>0.01~0.001</td><td>20000～200000</td></tr><tr><td>离子束</td><td><0.001</td><td>>200000</td></tr></table></body></html>  \n\n表10-4集成电路制作中使用的主要光刻胶  \n\n\n<html><body><table><tr><td>光刻胶</td><td>成膜树脂</td><td>感光剂</td><td>曝光机/曝光波长</td></tr><tr><td>聚乙烯醇肉桂酸酯负胶</td><td>聚乙烯醇肉桂酸酯</td><td>成膜树脂自身</td><td>高压汞灯/紫外全谱</td></tr><tr><td rowspan=\"4\">环化橡胶-双叠氮负胶 重氮萘酿-酚醛树脂正胶</td><td>环化橡胶</td><td>双叠氮化合物</td><td>高压汞灯/紫外全谱</td></tr><tr><td>酚醛树脂</td><td>重氮蔡化合物</td><td>高压汞灯/紫外全谱</td></tr><tr><td></td><td></td><td>g线/436nm</td></tr><tr><td></td><td></td><td>i线/365nm</td></tr><tr><td>248nm光刻胶</td><td>聚对羟基苯乙烯及衍生物</td><td>光致产酸剂</td><td>KrF准分子激光/248nm</td></tr><tr><td>193nm光刻胶</td><td>聚酯环族丙烯酸酯及共聚物</td><td>光致产酸剂</td><td>ArF准分子激光/193nm</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 550,
+        "chunk": "# 10. 1. 2 光刻工艺  \n\n光刻胶的种类很多，使用工艺条件依光刻胶的品种不同而有所不同，但大多工艺流程为：  \n\n基片处理 $\\rightarrow$ 涂胶 $\\rightarrow$ 前烘 $\\mathbf{\\rightarrow}$ 曝光 $\\rightarrow$ 中烘 $\\rightarrow$ 显影 $\\rightarrow$ 坚膜 $\\rightarrow$ 蚀刻（扩散、金属化） $\\Bumpeq$ 去胶  \n\n光刻工艺示意图如图10-1所示。  \n\n（1）基片处理基片处理包括脱脂清洗、高温处理，有时还需涂黏附增强剂进行表面改性处理。脱脂一般指采用溶剂或碱性脱脂剂进行清洗，然后再用酸性清洗剂清洗，最后用纯水清洗。高温处理通常是在 $150{\\sim}160^{\\circ}\\mathrm{C}$ 对基片进行烘烤去除表面水分。黏附增强剂的作用是将基片表面亲水性改变为憎水性，便于光刻胶的涂布，增加光刻胶在基片上的黏附性。  \n\n(2）涂胶光刻胶的涂布方式有旋转涂布（甩涂)、辊涂、浸涂及喷涂等多种，在光电子工业中应用较多的是旋转涂布。旋转涂布的涂胶厚度主要取决于光刻胶的黏度和旋涂时的  \n\n![](images/793b0abf28d07180e75e34c3226819e1dafb8ac375c8a557e77be79bff6a59a3.jpg)  \n图10-1光刻工艺示意图  \n\n转速。  \n\n（3）前烘前烘的目的是为了去除胶膜中残存的溶剂，消除胶膜的机械应力。烘烤方式通常有对流烘箱和热板两种。前烘温度和时间根据光刻胶种类和胶膜厚度而定。  \n\n（4）曝光正确的曝光量是影响成像质量的关键因素。曝光不足或曝过度都会影响复制图形的再现性。光刻胶的曝光量取决光刻胶的种类及膜厚。曝光宽容度大有利于光刻胶的应用。  \n\n（5）中烘中烘为曝光后显影前的烘烤，这对于光学增幅型光刻胶至关重要，中烘的好坏直接关系到复制图形的质量。  \n\n（6）显影光刻胶的显影过程一般分为两步：显影和漂洗。显影有浸人、喷淋等方式，在集成电路自动生产线上多采用喷淋方式显影。喷淋显影由于有一定压力，能较快显出图形，一般显影时间少于1min。漂洗的作用也十分重要，对环化橡胶-双叠氮系紫外负胶，在显影时有溶胀现象，经漂洗能使图形收缩，有助于提高图形质量。该类负胶常用正庚烷或专用显影液进行显影，用醋酸丁酯或专用漂洗液进行漂洗，近年来开发了混合型显影液实现了显影、漂洗两步工序合二为一。而重氮萘-酚醛树脂系紫外正胶则采用碱水显影，纯水漂洗，碱水显影液多为2.38%的四甲基氢氧化铵水溶液。  \n\n（7）坚膜坚膜亦叫后烘，其作用是去除残留的显影液，并使胶膜韧化。随后可进行刻蚀、扩散、金属化等工艺。（8）去胶在完成刻蚀、扩散、金属化等工艺后，通常要将胶膜从基片上去除。去胶一般采用专用去胶剂或氧等离子体干法去胶。对环化橡胶-双叠氮等负胶还采用硫酸-双氧水混合溶液进行去胶。  \n\n在实际制作集成电路或半导体分立器件时，往往需要多次甚至几十次的光刻，每次光刻都需要完成上述的工序循环。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 551,
+        "chunk": "# 10.1.3 光刻胶分类  \n\n光刻胶按光刻工艺，可分为正胶和负胶；按曝光波长可分为紫外光刻胶、深紫外光刻 胶、电子束光刻胶、X射线光刻胶、离子束光刻胶等。  \n\n紫外光刻胶是指感光波长为300～450nm的近紫外光刻胶。而感光波长为100～300nm 的光刻胶称为深紫外光刻胶。紫外光刻胶又分紫外负型光刻胶和紫外正型光刻胶。  \n\n紫外负型光刻胶指经紫外光（300～450nm）照射后，曝光区分子间发生光交联形成网状结构或光聚合使分子量变大，显影时，在显影液中溶解性变差，而未曝光区则容易在显影液中溶解，经显影后所得光刻胶图像与掩膜版图像相反。常见的紫外负型光刻胶有重铬酸盐-胶体聚合物系、聚乙烯醇肉桂酸酯系、环化橡胶-双叠氮型等。  \n\n紫外正型光刻胶是指经紫外光通过掩膜照射后，曝光区胶膜发生光分解或降解反应，溶解性能发生变化，溶于显影液，未曝光区胶膜则保留而形成正型图像的光刻胶。目前紫外正型光刻胶主要为邻重氮萘鼠-线型酚醛树脂系光刻胶。",
+        "category": " Introduction"
+    },
+    {
+        "id": 552,
+        "chunk": "# 10.1.4重铬酸盐-胶体聚合物系负型光刻胶  \n\n这是最早使用的光刻胶。早在1852 年美国人Fox Talbot首先使用重铬酸盐-明胶作为光刻胶材料涂覆在铜版上，以热水为显影液，三氯化铁为腐蚀液，制作印刷凹版。重铬酸盐-胶体聚合物系光刻胶的出现对推动当时印刷业的发展起了很大作用。  \n\n反应机理：重铬酸盐中六价铬经光还原反应变成三价铬，三价铬是一个很强的配位中心，它能与胶体聚合物分子上的活性官能团形成配位键而产生交联，如图10-2所示。  \n\n重铬酸盐-胶体聚合物系光刻胶主要由重铬酸盐和胶体聚合物组成。重铬酸盐多采用重铬酸铵，而常用的天然胶体聚合物有明胶、蛋白质、淀粉等；合成聚合物则有聚乙烯醇、聚乙烯吡咯烷酮、聚乙烯醇缩丁醛等。但重铬酸盐-胶体聚合物系光刻胶存放时有暗反应，即使在完全避光条件下放置数小时亦会有交联现象发生，因此必须在使用前现配现用。鉴于三价铬是致癌物，此类光刻胶有铬污染问题，因此早就停止使用。  \n\n![](images/244f45870f49faf3ec272e9ac3fa5c16113e8f7689d6c36e81a5d6da61307eda.jpg)  \n图10-2重铬酸盐交联示意图",
+        "category": " Introduction"
+    },
+    {
+        "id": 553,
+        "chunk": "# 10.1.5聚乙烯醇肉桂酸酯系负型光刻胶  \n\n聚乙烯醇肉桂酸酯系负型光刻胶是世界上最早发明的用合成高分子为原料的光刻胶，1954年美国柯达公司的明斯克（L.M.Minsk）等将肉桂酰基感光基团引入聚乙烯醇侧链，制得光刻胶，以商品名KPR投入市场。  \n\n反应机理：肉桂酰基中的双键在紫外光作用下打开，不同分子上的双键相互作用形成四元环，产生光二聚交联。这样曝光区的分子间发生交联，形成难溶的体型网状结构，未曝光区的分子性质不变，由此产生在显影液中溶解性差异，利用这种特性进行微细加工，如图10-3所示。  \n\n![](images/0bdedff40d365a0ffc064dce97720b6275aba3b83424fd28ade5d35d06997cf0.jpg)  \n图10-3聚乙烯醇肉桂酸酯类光刻胶的光反应过程  \n\n聚乙烯醇肉桂酸酯感光范围在230～350nm之间，最大吸收峰在280nm，为了提高其感度，常添加少量增感剂，使其感光范围向长波移动。如在聚乙烯醇肉桂酸酯中加入少量的5-硝基（因5-硝基为致癌物，已用其衍生物替代)，可使感光范围扩展到350～470nm，相对感度从2.2提高到84。  \n\n聚乙烯醇肉桂酸酯光刻胶与重铬酸盐-胶体聚合物系光刻胶比较，无暗反应，贮存期长(有效期一年)；感光灵敏度高；分辨率在3um左右。但在硅材料基片上的黏附性较差，影响了它在电子工业中的应用，现用量很少。  \n\n属于这类光二聚交联型光刻胶还有聚乙烯氧乙醇肉桂酸酯、聚肉桂亚丙二酸乙二醇酯等。聚乙烯氧乙醇肉桂酸酯感光范围在250～475nm，对436nm（g线）波长敏感，分辨率可达1um，感度比聚乙烯醇肉桂酸酯高一倍左右，而且黏附性、耐热性也好，曝光时受氧影响小，可不用氮气保护，但耐腐蚀性差，如图10-4所示。聚肉桂亚丙二酸乙二醇酯，感光区在350～470nm，分辨率在1～2μm，与二氧化硅、铝、铜、铬等基片有较强黏附力，抗蚀性也很好，如图10-5所示。  \n\n![](images/87eeaf97aee669a6119c8e4e6108c7aa72cbac45c137759c144fbc4330b84c17.jpg)  \n图10-4聚乙烯氧乙醇肉桂酸酯类光刻胶的光反应过程  \n\n![](images/8ad1c483f8ab4974b407421523f14eae9b7a29a250aafd44ed89564ec78fee14.jpg)  \n图10-5聚肉桂亚丙二酸乙二醇类光刻胶的光反应过程",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 554,
+        "chunk": "# 10.1.6环化橡胶-双叠氮型负型光刻胶  \n\n环化橡胶-双叠氮型负型光刻胶也是由美国柯达公司于1958年发明的。因该光刻胶具有黏附性好，特别对电子工业中最广泛应用的硅材料基片的黏附性好；感光速率快，最低曝光量可达 $3\\mathrm{mJ}/\\mathrm{cm}^{2}$ ；感光范围 $300{\\sim}450\\mathrm{nm}$ ；抗湿法刻蚀能力强等优点，已成为电子工业中应用的主导光刻胶品种，20世纪80年代初它的用量一度占电子工业中所用的光刻胶的 $90\\%$ o近年随着电子工业微细加工线宽的缩小，环化橡胶-双叠氮型负型光刻胶在集成电路制作中的应用逐渐缩小，但在半导体分立器件的制作中仍有较多的应用。 —  \n\n反应机理：环化橡胶-双叠氮型负型光刻胶是以带双键基团的环化橡胶为成膜树脂，以芳香族双叠氮化合物作为交联剂，在紫外光照射下，交联剂的叠氮基团分解形成氮宾，氮宾在聚合物分子骨架上夺取氢而产生自由基，使不同成膜聚合物分子间发生交联，变为不溶性聚合物，如图10-6所示。  \n\n![](images/a90ca9a52d3119572ef8e7cae4ea26c8e1fdf070c20aa4b1761fbe843e7b0562.jpg)  \n图10-6环化橡胶-双叠氮型光刻胶的光反应过程  \n\n成膜树脂环化橡胶由异戊二烯经聚合成为聚异戊二烯，再在酸性催化剂存在下环化反应而制得。环化程度越高，则光刻胶的分辨率越高，但会使抗蚀性和黏附性降低。因此高分辨率光刻胶要求环化程度较高，而高抗蚀性光刻胶，则要求环化程度较低。  \n\n可作为光交联剂的双叠氮类的化合物有很多：  \n\n![](images/872997e351b8ccb16bfa0ce6ac66a6a9493b0da16f60f5333d0201978d4c5b25.jpg)  \n\n![](images/3ba556190f4b9f898cd9c0c79d218175f3cf290016049d3d9d4d631057561c85.jpg)  \n\n![](images/3c48be02adc8b2f567daf3b2b70f2ad427e74ee1cbf24b0bf62766330509df2b.jpg)  \n\n其中以2,6-双(4-叠氮亚苄基)-4-甲基环已酮（1）应用最多。该化合物与环化橡胶的溶剂和环化橡胶相溶性好；感光范围 $\\mathbf{250}{\\sim}450\\mathbf{nm}$ ，峰值约在 $356\\mathrm{nm}$ ；感度高，最低曝光量 $\\ensuremath{3\\mathrm{mJ/\\ell}}$ $c m^{2}$ ；交联产物的抗蚀性好。",
+        "category": " Introduction"
+    },
+    {
+        "id": 555,
+        "chunk": "# 10.1.7邻重氮萘-酚醛树脂系正型紫外光刻胶  \n\n邻重氮萘-线型酚醛树脂系紫外正型光刻胶是目前电子工业中使用最多的光刻胶。早在1951年德国Kalle公司首先用重氮酮化合物作感光剂制得印刷用阳图PS版。后来Kalle公司所属美国Azoplate公司与Shipley公司合作，于1960年开发出以“AZ”商标的光刻胶用于半导体器件制造工艺中。它比环化橡胶-双叠氮系负型光刻胶分辨率高，抗干法蚀刻性好，耐热性好和去胶方便等；但也存在感光速率慢、黏附性和机械强度较差等缺点。  \n\n反应机理：经紫外光照射后，曝光区的邻重氮萘化合物发生光分解反应，经重排生成羧酸，使胶膜能溶于稀碱水溶液，未曝光区由于没有发生变化，不溶于稀碱水溶液，从而在曝光区和未曝光区经碱水显影后产生正性图像。目前邻重氮萘化合物主要有215邻重氮萘磺酸酯和214邻重氮萘磺酸酯，它们的光解反应历程如图10-7和图10-8所示。  \n\n![](images/09e24420c5afbe1fa1d61d0192fcac88edbc5cab0eef2ab614c5aceed22b924b.jpg)  \n图10-7215邻重氮萘磺酸酯光解反应机理  \n\n![](images/4b096d8d454097c8448cb0cdd6c2ab505150d33510ed5855de6cec43ab8ca988.jpg)  \n图10-8214邻重氮萘磺酸酯光解反应机理  \n\n邻重氮萘-线型酚醛树脂系紫外正型光刻胶的感光剂是215邻重氮萘磺酸酯或214邻重氮萘磺酸酯，它们均是由相应的邻重氮萘磺酰氯与多羟基化合物经酯化反应而制得的。目前常用的多羟基化合物如下。  \n\n2,3，4-三羟基二苯甲酮$^{2,3,4,4^{\\prime}}$ -四羟基二苯甲酮  \n\n![](images/26b1672adc9fa712e5d514d56ea7ad2f5a3522722ed4750d00f036469648211c.jpg)  \n\n从光敏性、成像质量及溶解性等综合考虑，感光剂的酯化度一般在60%～80%。  \n\n邻重氮萘-线型酚醛树脂系紫外正型光刻胶的成膜树脂是线型酚醛树脂，通常由甲酚和甲醛水溶液在酸催化下缩聚而成。  \n\n邻重氮萘-线型酚醛树脂系紫外正型光刻胶根据所用的曝光机不同又可分为宽谱紫外正胶、G线正胶和I线正胶。宽谱紫外正胶采用紫外全谱曝光，适用于2～3um、0.8～1.2μm集成电路的制作。G线紫外正胶采用g线（436nm）曝光，适用于0.5～0.6um集成电路的制作。I线紫外正胶采用i线（365nm）曝光，适用于0.35～0.5μm集成电路的制作。紫外正胶还用于液晶平面显示器等较大面积的电子产品制作。  \n\nI线光刻技术自20世纪80年代中期进入开发期，90年代初进入成熟期，90年代中期进人昌盛期。I线光刻胶最初分辨率只能达到0.5μm，随着i线光刻机的改进，I线紫外正胶已可制作0.25μm集成电路，I线光刻技术成为目前最为广泛应用的光刻技术。",
+        "category": " Introduction"
+    },
+    {
+        "id": 556,
+        "chunk": "# 10.1.8 深紫外光刻胶  \n\n随着电子工业微细加工临界线宽的缩小，对细微加工的分辨率的要求不断提高，而提高分辨率的重要方法之一就是使用更短的曝光波长，因此发展了深紫外光刻（deepUVphotoresist，也叫远紫外光刻)。深紫外光由于波长短，衍射作用小，因而具有高分辨率的特点。随着稀有气体卤化物准分子激发态激光（excimerlaser）的发展，使深紫外光刻工艺成为现实。目前氟化（ $\\mathbf{KrF}$ ， $248\\mathsf{n m})$ 、氟化氩（ $\\mathbf{ArF}$ ， $193\\mathrm{nm},$ ）和氟（ $\\mathbf{{\\tilde{F}}}_{2}$ ， $\\mathbf{157nm}.$ ）等分子激发态激光源的步进式曝光机已商品化，并且NA值大于0.6，为成像分辨率的提高奠定了良好的基础。  \n\n与紫外光刻胶不同的是，深紫外光刻胶均为化学增幅型光刻胶。化学增幅型光刻胶的特点是：在光刻胶中加入光产酸剂（photoacid generator，PAG)，在光辐射下，产酸剂分解出酸，在中烘时，酸作为催化剂催化成膜树脂脱去保护基团（正胶)，或催化交联剂与成膜树脂发生交联反应（负胶)；而且在脱去保护基反应和交联反应后，酸能被重新释放出来，没有被消耗，能继续起催化作用，大大降低了曝光所需的能量，从而大幅度提高了光刻胶的光敏性。化学增幅型光刻胶的感光机理如图10-9所示。  \n\n![](images/80c6b3c24cccedc93a9b9506307d86b2d2462e89c6e6f1562b429a7ddbf2475a.jpg)  \n图10-9化学增幅型光刻胶的感光机理  \n\n(1） $248n\\mathbf{m}$ 深紫外光刻胶 $248\\mathrm{nm}$ 深紫外光刻胶是以 $\\kappa\\mathbf{r}\\mathbf{F}$ 准分子激光为曝光源，其成膜树脂主要为聚对羟基苯乙烯及其衍生物：  \n\n![](images/a55811bae3e7b96d6f4d4831b52ebd7dada48290c63ecd965e518eda7eb5db2d.jpg)  \n\n这是由于聚对羟基苯乙烯及其衍生物在248nm处有很好的透过性。光产酸剂普遍使用能产生磺酸的碘盐和硫盐。  \n\n$248\\mathrm{nm}$ 光刻胶配合KrF准分子激光器可制作线宽 $0.25\\mu\\mathrm{m}$ 、 $256\\mathbf{M}$ 随机存储器及相关逻辑电路。通过提高曝光机的NA值及改进相配套的光刻技术，目前已成功用于线宽0.15～0.18μm、1G随机存储器及相关器件的制作。若采用移相掩膜、离轴照明，邻近效应校正等分辨率增强技术，已能制作出线宽小于 $0.1\\mu\\mathrm{m}$ 的图形。  \n\n(2） $193\\mathrm{nm}$ 深紫外光刻胶 $193\\mathrm{nm}$ 深紫外光刻胶是以ArF准分子激光为曝光源。由于用于 $248\\mathrm{nm}$ 深紫外光刻胶的成膜树脂含苯环，在 $193\\mathrm{nm}$ 处有较强的吸收，故不能应用于  \n\n193nm深紫外光刻胶。聚甲基丙烯酸酯在193nm处有良好的透过率，但抗干法腐蚀性差，无法实用化。后发现在聚甲基丙烯酸酯侧链上引人多元酯环结构可提高抗干法蚀刻性，引人极性基团可提高黏附性，故193nm深紫外光刻胶成膜树脂主要为侧链带多酯环结构的聚甲基丙烯酸酯，或带多酯环结构的马来酸酐共聚物。  \n\n![](images/6e0a3a024cc2b9c70dcb7b46f1921a7c2e6e5a059c6886cfb3b27065e3f5542f.jpg)  \n\n与 $248\\mathrm{nm}$ 光刻胶相比， $193\\mathrm{nm}$ 光刻胶中成膜树脂不含苯环，没有酚羟基，成膜树脂与光产酸剂之间没有能量转移，不存在光敏化产酸，因此在193nm光刻胶中，光产酸剂的产酸效率比 $248\\mathrm{nm}$ 低。故 $193\\mathrm{nm}$ 光刻胶中光产酸剂与 $248\\mathrm{nm}$ 类似外，人们正研究能大幅度提高光产酸剂的产酸效率的新型光产酸剂。  \n\n$193\\mathrm{nm}$ 深紫外光刻胶的分辨率可达 $0.15\\mu\\mathrm{m}$ 左右，可以满足制作1G随机存储器的要求。通过提高曝光机的NA值及改进配套的光刻技术， $193\\mathrm{nm}$ 光刻胶分辨率可达到 $0.10\\mu\\mathrm{m}$ 。目前已成熟地应用于0.13～0.10μm的4G的制程工艺，2007年可用于65nm制程工艺。近年因湿浸式光刻技术的出现，193nm光刻胶的应用将延伸到45nm工艺，甚至32nm、22nm工艺。  \n\n（3）157nm深紫外光刻胶157nm光刻的主要困难是当波长短到157nm时，大多数的光学镜头材料都是高吸收态，易将激光的能量吸收，受热膨胀后而造成球面成像差。目前只有氟化钙为低吸收材料，可供 $157\\mathrm{nm}$ 使用，但制作成本昂贵。  \n\n157nm光刻胶要解决的首要问题也是材料的吸收问题。目前发现在聚乙烯分子链上适当引入吸电子基团，如氧或氟原子，可使透过率明显提高。另外硅聚合物如硅氧烷等，在$157\\mathrm{nm}$ 有良好的透过性。目前 $\\mathbf{157nm}$ 光刻胶正处于研究之中，还不成熟，主要有氟代聚（甲基）丙烯酸酯衍生物、聚氟代环烯烃衍生物。  \n\n（4）光产酸剂（photoacid generator，PAG）和酸增殖剂（acid proliforation generator，APG）化学增幅光致抗蚀剂的成像过程主要包括光产酸剂的光照产酸，随后受热酸催化反应和显影，形成图像。光产酸剂在光照时发生量子效率不大于1的化学反应，产生少量酸，酸作为催化剂，催化随后的反应，达到增幅的目的。因此，产酸量多少直接决定体系的感度。然而，在光照过程中由于受到量子效率的限制，产生的酸是很有限的，使化学增幅抗蚀剂感度提高并不如人们原先希望的那样大。1995年日本的市村国宏等人首先提出了关于酸增殖剂概念。酸增殖剂是一种在光照时很稳定，但在光照后的加热烘烤时，它会被光产酸剂产生的少量酸所催化，产生新的强酸，并且产生的强酸还能催化其自身进一步产酸，即发生酸致产酸反应的物质。由于光产酸剂和酸增殖剂的协同作用，迅速产生大量的强酸，使化学增幅光致抗蚀剂体系表现出以非线性方式的迅速发生的酸催化反应，从而大大提高了光成像过程的感度 (图10-10)。  \n\n![](images/cff9884b9d1853e1dfcdaa2a8f137bcae829cbdb6f91e885e7ce4dbffe06e6b6.jpg)  \n图10-10光产酸剂和酸增殖剂协同产酸示意图  \n\n光产酸剂有许多种（图10-11)，目前应用最多的是能产生磺酸的碘盐、硫盐或非离子型的磺酸酯类。  \n\n![](images/5ba73b5018533fd0cdbe62f0a88e461a5eb82667a8a27d12b3d91ee75f9a573d.jpg)  \n图10-11光产酸剂分类示意图  \n\n酸增殖剂主要有各类磺酸酯，如苄基磺酸酯、乙酰乙酸酯磺酸衍生物、缩酮类磺酸酯、环己二醇磺酸酯、三烷磺酸酯等，它们的酸增殖机理如图10-12 和图10-13所示。  \n\n![](images/a5ea251991e45e73a9f9000ddb9485f8a281a58fadb9a2c20495a3639a0541de.jpg)  \n图10-12缩酮磺酸酯的酸增殖反应机理  \n\n![](images/4f44c34297dc9010461e519889352f02191b62ed4517b1212d07c144102f6341.jpg)  \n图10-13环己二酸双磺酸酯的酸增殖反应机理",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 557,
+        "chunk": "# 10.1.9 电子束光刻胶  \n\n电子束光刻是采用加速电子束作用于光刻胶在被加工物体上形成微细图像的一种方法，具有波长短、分辨率高（达 ${30}\\mathrm{nm})$ 、无需掩膜、可在基片上直接制作图形（直写）的特点，广泛应用于光学与非光学的掩膜制造。但由于曝光区域小，生产效率低，限制了它在集成电路制作中的应用。电子束曝光机一直朝着大功率、多光束方向发展以提高单位曝光速率。在过去“点”曝光的直写技术基础上，又研究出“面”曝光的投影曝光技术，使电子束曝光更接近现行采用的曝光技术。随着电子工业微细加工线宽的缩小，电子束光刻技术越来越多地应用在大批量的生产上，成为下一代光刻的有力竞争者。  \n\n电子束光刻胶的作用原理是因电子束进人光刻胶内部后，具有极高能量的电子束便丧失一部分能量成为低能量电子束，随之放出X射线、热能和二次电子。由于二次电子的作用而使光刻胶产生交联、断裂或降解等，从而使光刻胶在电子束辐射后引起溶解度和其他性能的差别。若经电子束照射后发生主链断裂而降解，被曝光区域的溶解度增大，这类光刻胶称之为正性光刻胶；反之，发生交联而使被曝光区域的溶解度减小，这类光刻胶称之为负性光刻胶。  \n\n由于电子束光刻没有紫外吸收问题，在光刻胶材料的选择上有更大的自由度。但因电子束曝光效率低，故电子束光刻胶的光敏性是首要问题。采用化学增幅技术是电子束光刻胶提高光敏性的必然选择。  \n\n（1）电子束正性光刻胶主要为聚甲基丙烯酸甲酯及其衍生物，其分辨率高，但感光灵敏度低，抗干法腐蚀差。  \n\n![](images/e0b08a72c4691b1e138cf1fd9c92ec580f43fdfc9f1756318e6d2d3017f777d5.jpg)  \n\n（2）电子束负性光刻胶主要有甲基丙烯酸缩水甘油酯-丙烯酸酯共聚物和氯甲基化聚苯乙烯等，其感光灵敏度高，但分辨率比电子束正性光刻胶差。  \n\n![](images/121bb4e36d460e510065febbfe69f16c0522e8e0a76eb77447cf057f23ed6770.jpg)  \n\n现在 $100\\mathrm{nm}$ 技术电子束光刻胶已批量生产，研究水平已达到 $70\\mathrm{nm}$ 水平。",
+        "category": " Introduction"
+    },
+    {
+        "id": 558,
+        "chunk": "# 10.1.10 $\\pmb{x}$ 射线光刻胶  \n\nX射线光刻是采用X射线作为曝光的辐射源来复制高分辨率的微细图形的一种加工技术。它具有波长短，几乎没有衍射的干扰，散射也比电子束小得多，可以获得高分辨率；曝光视场大，宽容度大，生产效率高；对环境不敏感等优点，因此很有可能成为新一代的光电子工业应用的光刻技术。  \n\nX射线光刻技术首先要解决的是X射线曝光机，目前X射线曝光机价格昂贵，严重影响了在实际生产中应用。其次是X射线掩膜版，因X射线具有穿透性，所以X射线掩膜版完全不同于普通光学光刻所用的铬版。X射线掩膜版采用低原子量材料作为低吸收材料代替玻璃，如硼化氮（BN)、硅化氮（SiN)、硅化碳（SiC）及某些有机聚合物所制成的使X射线充分透过的超薄膜。而掩膜版上不透光的图形则由高原子量材料组成，金是最常用的，其作用相当于铬版上的铬层。  \n\n因X射线和电子束辐射的化学效应是基本相似的，所以电子束光刻胶亦可用作X射线曝光，而且光刻胶材料的电子束光敏性和X射线光敏性有很好的线性关系，电子束曝光约需 $\\scriptstyle7\\mu\\mathbf{C}/\\mathbf{cm}^{2}$ ，则X射线曝光约需 $100\\mathrm{mJ/cm^{2}}$ 。",
+        "category": " Introduction"
+    },
+    {
+        "id": 559,
+        "chunk": "# 10.1.11 离子束光刻胶  \n\n离子束光刻是由气体离子源发出的离子束作为辐射源来制作微细图像的加工技术。由于离子束具有较高的能量，对各种光刻胶材料有更高的灵敏度；离子质量比电子大得多，散射比电子小得多，不存在邻近效应，比电子束光刻有更高的分辨率，在光刻技术中可以得到最细的线条，可适用于纳米级线宽的制作。目前离子束光刻工艺的重要应用是修补X射线掩膜版和其他高分辨图形中的阻光缺陷。各类电子束光刻胶大多可采用离子束进行曝光。",
+        "category": " Introduction"
+    },
+    {
+        "id": 560,
+        "chunk": "# 10.1.12 厚膜光刻胶  \n\n随着电子工业的迅速发展，微电子技术的应用领域不断拓宽，特别是集电子-机械一体化的微机电产品的出现，为微电子技术的发展提供了更加广阔的空间，并成为电子工业的一个重要发展分支。  \n\n为满足微机电产品发展的需要，厚膜光刻胶应运而生。厚膜光刻胶具有良好的光敏性和高纵横比（纵横比可达到 $20:1)$ ；能得到超厚涂层，一次涂布可得到 $500\\mu\\mathrm{m}$ 厚涂层，甚至可超过 $1000\\mu\\mathrm{m}$ 厚；在大多数基材上有良好的黏附性，已交联的胶膜有极佳的抗蚀性和热稳定性（可大于 $200^{\\circ}\\mathrm{C}$ )；具有耐碱性和良好的抗干法刻蚀性；既可复制图形，自身又可制作机械零件；可用环保型显影液显影，显影宽容度高。  \n\n典型的厚膜光刻胶为SU-8化学增幅型环氧树脂，其结构如图10-14所示。  \n\nSU-8厚膜光刻胶的感光机理如图10-15所示。  \n\n![](images/8e31b1c838a119329468ef713a27cdc6966e70a3399aa2210fcc70d145dc343d.jpg)  \n图10-14 SU-8结构  \n\n![](images/4891dc5cc5e0812d75cfa9adb7a6620ea5ff16b0a6be77ebfb94cf32d342fc68.jpg)  \n图10-15SU-8厚膜光刻胶的感光机理  \n\n厚膜光刻胶应用主要为微机电系统中传感器、传动装置、电铸微型齿、轮线圈的模具、磁头、异型微模件、LCD隔离层以及UV固化塑封材料等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 561,
+        "chunk": "# 10.1.13 无显影气相光刻  \n\n无显影气相光刻是我国在1980年发明的一种独特的光刻技术，其光刻过程如图10-16所示。  \n\n![](images/e6549d127be236d77b763d37df124f4884bdc314f89ceb8a7045d887f2eba9c4.jpg)  \n图10-16无显影气相光刻工艺  \n\n在硅片表面涂覆一层添加了5-硝基二氢的聚酯光刻胶，烘干后加上掩膜进行紫外曝光，曝光区光刻胶交联，然后在高于 $100^{\\circ}\\mathrm{C}$ 的温度下用HF气体进行刻蚀，HF气体穿透曝光区光刻胶涂层，对下面的 $\\mathrm{SiO}_{2}$ 进行腐蚀，而非曝光区不发生变化，去膜后就得到一个正性光刻图形。采用无显影气相光刻技术，不用显影就可实现光刻，完全避免了显影液的溶胀作用，从根本上消除了胶膜图形畸变对分辨率的影响，因而提高了刻蚀精度。用本方法与现有的亚微米曝光技术结合，可实现无显影亚微米刻蚀工艺。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 562,
+        "chunk": "# 10. 1.14 光刻胶的合成方法  \n\n（1）聚乙烯醇肉桂酸酯的合成（一）将 $\\mathbf{11g}$ 聚乙烯醇放到 $100\\mathrm{mL}$ 吡啶中，在水浴上加热使其溶解，补加 $100\\mathrm{mL}$ 吡啶，将温度降到 $50^{\\circ}\\mathrm{C}$ 以下，慢慢滴加 $50\\mathbf{g}$ 肉桂酸酰氯，加毕在$50^{\\circ}\\mathrm{C}$ 继续反应4h，生成的黏稠块状物溶于四倍丙酮中，过滤后注入水中析出聚乙烯醇肉桂酸酯，过滤，水洗，暗处晾干，得 $_{31\\pmb{g}}$ 聚乙烯醇肉桂酸酯。 .1Q.  \n\n（2）聚乙烯醇肉桂酸酯的合成（二）将精制的聚乙烯醇（聚合度1700士50，分子量分布指数1.8）放人 $95{\\sim}100^{\\circ}\\mathrm{C}$ 溶剂吡啶中膨润，在 $50^{\\circ}\\mathrm{C}$ 时，滴加肉桂酰氯［聚乙烯醇：肉桂酰氯摩尔比为1：（1.2～1.3)］，加毕，继续反应5h，再加丙酮稀释，在水中沉淀、洗净，干燥得到聚乙烯醇肉桂酸酯。  \n\n（3）聚乙烯醇肉桂酸酯的合成（三）将精制的聚乙烯醇（聚合度 $1700\\pm50$ ，分子量分布指数1.8）溶于温水中，加入氢氧化钠水溶液冷却至 $0^{\\circ}\\mathrm{C}$ ，成为碱溶液。在 $0^{\\circ}\\mathrm{C}$ 剧烈搅拌下滴加溶解在丁酮中的肉桂酰氯（与聚乙烯醇摩尔比为 $ 1.3:1)$ ，加毕继续在 $0^{\\circ}\\mathrm{C}$ 反应1.5h，反应完毕，在 $0^{\\circ}\\mathrm{C}$ 下静置，生成的聚乙烯醇肉桂酸酯溶于上层溶液中，分出上层溶液在汽油中沉析，过滤、脱水、干燥得到聚乙烯醇肉桂酸酯。  \n\n（4）聚乙烯醇肉桂酸酯的合成（四）将100mL浓度1mol/L（按羟基计）的聚乙烯醇溶液和100mL4mol/L的氢氧化钾溶液混合，加人100mL丁酮，在搅拌下加人24mL甲苯和116mL溶有1.2mol肉桂酰氯的丁酮溶液，在0～5℃反应2h，反应结束静置，将上层有机层滴入甲醇中，即可析出产物聚乙烯醇肉桂酸酯，产率几乎是100%。  \n\n（5）聚乙烯醇肉桂酸酯的合成（五）在三口烧瓶中加入精制的聚乙烯醇44g（lmol)、无水吡啶400mL，隔绝水汽下100℃溶胀24h。再加人3.5mL二氧六环，冷到45℃，滴加200g（1.2mol）肉桂酰氯和50mL二氧六环混合液，在50～55℃用1～1.5h加毕，继续揽拌 3h，再加人少量乙酸酐继续反应1h。冷却加丙酮稀释，过滤除去吡啶盐后，滤液沉析于大量去离子水中，过滤洗至无氯根，再用乙醇浸泡过夜，过滤产物在60℃下干燥，得到固体产物为聚乙烯醇肉桂酸酯，得率约90%。  \n\n（6）聚乙烯氧乙醇肉桂酸酯的合成将两分子氯乙醇在浓硫酸作用下脱水生成2，2'-二氯二乙基醚。  \n\n2,2'-二氯二乙基醚在氢氧化钠作用下，加热至200～220℃，制得2-氯乙基乙烯基醚。  \n\n用2-氯乙基乙烯基醚和肉桂酸钠在四甲基碘化铵存在下，回流反应4h，得到单体乙烯氧基肉桂酸乙酯。经精制后，在三氟化硼-乙醚催化剂作用下，于低温一178℃进行阳离子聚合，得到聚乙烯氧乙醇肉桂酸酯。  \n\n（7）聚肉桂亚丙二酸酯的合成  \n\n![](images/c50fb9e5f90a0d23bb4745572004850a64974eb0676c07c090c6778aaeb4622c.jpg)  \n\n将肉桂醛、丙二酸二乙酯、醋酐按一定摩尔比例加人，升温至138～140℃，回流反应6h，蒸馏除去乙酸，再减压蒸馏，收集在1～4mmHg（1mmHg=133.32Pa）下182～200℃馏分，为肉桂酸亚丙二酸二乙酯。  \n\n将肉桂酸亚丙二酸二乙酯与乙二醇按 $1:(2.1{\\sim}2.2)$ 的摩尔比加人三口瓶中，再加入适量催化剂醋酸锌，升温至 $160^{\\circ}\\mathrm{C}$ 通氮气进行酯交换反应，得到肉桂亚丙二酸乙二醇酯。加人催化剂氧化亚锑（ $S b_{2}O_{3}$ ）进行缩聚反应，减压蒸馏除去乙二醇，得到聚肉桂亚丙二酸酯。  \n\n（8）环化橡胶的合成在三口烧瓶中加人聚异戊二烯［分子量 $(1\\sim3)\\times10^{5}]$ 和 $_{8\\sim10}$ 倍胶重的二甲苯，升温搅拌至 $80\\sim90^{\\circ}C$ ，使橡胶全部溶解。升温至 $90\\sim95^{\\circ}\\mathrm{C}$ ，加人 $5\\%$ 的四氯化锡催化剂，反应3h。反应过程中取样测定黏度和不饱和度（碘值法)，到所需要求时，降温，加人与溶剂等量的水，使四氯化锡水解从而中止反应，搅拌30min，以充分洗涤。静置后反应物分为三层，乳浊状油层、中间不明显的过渡层、水-催化剂水解物层。乳浊状油层大部分是反应所得环化橡胶二甲苯溶液，内混少量水分和四氯化锡水解产物等杂质。将乳浊状油层高速离心分离，得澄清油状液，加入稀氢氧化铵溶液，搅拌、静置一天后，分出油、水两层，用离心法将油层中少量水分除去，再浓缩胶液，把胶液中残存的微量水分随溶剂蒸出，浓缩至反应液黏度在 $42\\mathrm{{mPa}\\bullet\\bullet(25^{\\circ}C)}$ ，浓度为 $10\\%\\sim15\\%$ 。  \n\n（9）环化橡胶的合成在三口烧瓶中加入聚异戊二烯橡胶小块和橡胶重16～30倍的二甲苯，升温至80～90℃，搅拌至橡胶全部溶解。加人对甲苯磺酸3%～10%，在氮气保护下，升温至90～100℃，反应2～5h，反应过程中取样测不饱和度（碘值法)，待符合要求时，降温冷却至室温，加入水或碳酸钙充分搅拌。用高速离心分离反应液，上层为透明澄清的环化橡胶二甲苯溶液。加人大量丙酮，析出环化橡胶，真空干燥即得到环化聚异戊二烯橡胶。  \n\n（10）环化橡胶的合成在三口烧瓶中加人聚异戊二烯橡胶小块和橡胶重15～30倍的二甲苯，升温 $80{\\sim}90^{\\circ}\\mathrm{C}$ ，搅拌至橡胶全部溶解。加人 $0.17{\\sim}0.46\\mathrm{mol/L}$ 对甲苯磺酸和 $\\phantom{-}0.80\\sim$ $2.13\\mathrm{mol/L}$ 苯酚，通氮气，升温至 $125{\\sim}130^{\\circ}\\mathrm{C}$ ，反应 $\\mathsf{2}\\sim\\mathsf{2}.\\mathsf{5h}$ ，反应停止后加入2606型乙烯吡啶叔胺离子交换树脂（或其他多孔性弱碱性离子交换树脂）处理胶液除去酸性，过滤，在甲醇中沉析，真空干燥即得到环化聚异戊二烯橡胶。  \n\n（11）环化橡胶的合成用干燥的高纯氮气通人反应器，加入干燥二甲苯、干燥精制的异戊二烯（纯度 $99.2\\%$ ，含 $0.8\\%$ 异戊二烯胺)，混合后内含水分应小于 $\\ 3\\times10^{-6}$ 。加入正丁基锂的正己烷溶液，在 $30\\sim85^{\\circ}C$ 反应1h，加入2,6-二叔丁基对甲酚的二甲苯溶液终止反应，有$99\\%$ 异戊二烯已聚合。再加入二甲苯，在 $80^{\\circ}\\mathrm{C}$ 减压，将未反应的异戊二烯和异戊二烯胺蒸出。再用干燥的高纯氮气使反应器恢复常压。升温 $80^{\\circ}\\mathrm{C}$ ，加入对甲苯磺酸的二甲苯溶液，反应3.5h后，加蒸馏水充分搅拌，静置后分去水层，反复数次清洗后，高速离心除去悬浮水分。在 $80^{\\circ}\\mathrm{C}$ ， ${\\mathsf{50m m H}}\\mathbf{g}$ $(1\\mathrm{{mmH}g=133.32\\mathrm{{Pa})}}$ 下蒸去溶剂二甲苯，浓缩酸液至一定浓度。  \n\n（12）2，1,5-型重氮萘鼠的合成  \n\n![](images/6593546813a8cf210a835c2c653cfca85facccb4c33140dcbe1062b05c457a00.jpg)  \n\n在三口烧瓶中加入1-蔡酚-5-磺酸270g和450mL水调成浆状，加22.5g氢氧化钠，使其全部溶解。加入101mL醋酸，在25℃下缓慢加人137mL30%的亚硝酸钠溶液，搅拌反应$2\\mathrm{h}$ ，溶液变为红棕色稠体。过滤，用饱和食盐水洗数次，得滤饼A $400\\mathbf{g}$ 。  \n\n在烧杯中加人上述A 400g和900mL水搅匀，再加 360mL40%的氢氧化钠，搅拌0.5h，在32℃下加保险粉（NazSzO4）187g（用保险粉试纸检查呈蓝色为适量），使pH值为9～10。升温至60～65℃，搅拌反应2h，过滤，滤液降至室温，加盐酸563mL，有大量灰白色沉淀析出，再搅拌10min，溶液pH值为2～3，抽滤，用0.3%的盐酸溶液洗数次，抽滤，在 $60^{\\circ}\\mathrm{C}$ 干燥，得 $\\textbf{B}90\\mathbf{g}$ 。  \n\n在三口烧瓶中加90gB，冰水450mL，8g硫酸铜（溶于50mL水中)，置冰盐浴中，在0～5℃下缓慢滴人70mL30%的亚硝酸钠溶液，使pH值保持在5～6，搅拌反应1.5h，加人盐酸 $225\\mathrm{mL}$ ，使 $\\mathtt{p H}$ 值为 $_{1\\sim2}$ ，溶液由黄绿色变成橙黄色后，再搅拌0.5h，加食盐 ${\\displaystyle60{\\bf g}{\\bf\\sigma}}$ 析出黄绿色晶体，抽滤，55℃干燥，得C。  \n\n在三口烧瓶中加人320mL氯磺酸，缓慢加人80gC，40～45℃保温0.5h，升温至55～60℃，反应5h，降至室温放置过夜，次日滴人冰水中，析出黄色细颗粒，反复水洗过滤至中性时抽干，40℃下风干，得黄色邻重氮萘-2,1,5-磺酸氯D。  \n\n（13）三羟基二苯甲酮-2-重氮萘酿-2，1，5-磺酸酯的合成  \n\n![](images/0c828b103d251ba227375b873ac43d7fb02f7bddcc97e92aa16569b608f096f3.jpg)  \n\n在三口烧瓶中加人焦性没食子酸660g和90%的乙醇1500mL，加热搅拌至沸腾，在回流下滴加1332g三氯甲苯，控制滴加速率使保持回流平稳。加毕继续回流反应2h，然后趁热倒入沸水中，冷却析出结晶。未溶物继续用沸水溶解至不再溶解为止。获得粗品再用水（或苯-乙醇）重结晶一次，得到黄色针状结晶三羟基二苯甲酮，熔点为138～140℃。  \n\n将23g三羟基二苯甲酮、54g重氮萘-2,1,5-磺酰氯室温搅拌下溶解于500mL二氧六环中，于30～40℃下滴加碳酸钠至溶液为中性后，仍在30～40℃搅拌反应1h，将反应物倒入稀盐酸溶液中，析出橙黄色固体，水洗至中性，于40℃真空干燥即得三羟二苯甲酮-2-重氮萘-2,1,5-磺酸酯。  \n\n（14）2，1，4-感光性树脂的合成  \n\n![](images/94d0185107eb4b1cb2a86a559287992c1ef15bef6893d6d0ebcb59f99bfa4f41.jpg)  \n在三口烧瓶中加入67mL氯磺酸（相对密度1.75)，搅拌下，40℃慢慢将25g4,2,1-酸  \n\n氧体加人，升温至72℃士1℃反应2h，降温至40℃以下，缓慢滴加29.3mL氯化亚矾，加毕升温至72℃士1℃搅拌反应2h，降温放置过夜。次日将反应液滴加到搅拌的冰水中，析出大量黄色固体分散物，滴毕过滤，用冰水反复洗至中性，抽滤，在40℃热风中干燥得A$21.3\\mathbf{g}$ ，产率 $80\\%$ ，熔点 $102{\\sim}104\\mathrm{^{\\circ}C}$ 。  \n\n在三口烧瓶中加人25.1g间-甲酚醛树脂（黏度170×10-3Pa·s）、100.4mL二氧六环，搅拌溶解，加入42.7gA（溶于214mL二氧六环中)，充分搅拌下缓慢滴加10%的碳酸氢钠300mL（至pH=7～8)，搅拌反应2h，静置0.5h，分去上层清液，在大量清水中捣碎黏稠物，反复水洗过滤，滤饼在60℃热风中干燥，得深黄色细粉末状2,1,4-型感光性树脂B，$47.5g$ ，收率约 $70.4\\%$ 。  \n\n（15）2，1,5-型感光性树脂的合成  \n\n![](images/f76eafdb1b27bafc2160e8b6fa71e697687d65e86f96ec3011a7fb142c6c63b0.jpg)  \n\n在三口烧瓶中加入 $49.6\\phantom{.0}8$ 聚苯酚树脂、 $80\\mathbf{g}$ 邻重氮萘2,1,5-磺酰氯、 $_{192\\mathrm{mL}}$ 丙酮，揽拌溶解，缓慢滴加约190mL10%的碳酸钠溶液（反应液pH=7～8为宜)，搅拌反应1h，静置0.5h，分去清液，将黏稠物倒人2000mL清水中，捣碎过滤，多次水洗至中性，抽滤，滤饼在 $50^{\\circ}\\mathrm{C}$ 下烘干，得黄色粉末状产物2,1,5-型感光性树脂 $\\mathbf{104g}$ 。  \n\n(16）2,1,5-型感光性树脂的合成在三口烧瓶中加入 $\\mathrm{1mol~3,3^{\\prime},5,5^{\\prime}.}$ 四溴双酚A、2.5mol邻重氮萘-2,1,5-磺酰氯和适量溶剂，再加人3g碳酸钠，升温至62～65℃反应3h，蒸去溶剂，在大量水中沉出捣碎，再用清水洗至中性，抽滤，滤饼在 $50^{\\circ}\\mathrm{C}$ 烘干，得到黄色（或深黄色）固体，2-重氮-1-萘-5-磺酰 $(3,3^{\\prime},5,5^{\\prime})$ -四溴双酚A酯光敏剂。  \n\n（17）线型酚醛树脂的重氮萘-2,1,5-磺酸酯的合成在三口烧瓶中加人70g氯磺酸，边搅拌边升温至 $45\\mathrm{^\\circC}$ ，将 $_{10\\mathbf{g}}$ 重氮萘-2,1,5-磺酸慢慢加人，因反应放热，注意冷却不使温度升得过高，加毕在 $55\\sim60^{\\circ}C$ 搅拌反应 $5\\mathrm{h}$ ，降温至 $20{\\sim}25^{\\circ}\\mathrm{C}$ ，将反应液注入冰水中，使之结晶析出，过滤，用少量水洗，在暗处真空干燥，得黄色固体重氮-2,1,5-磺酰氯。  \n\n将 $10.8\\mathbf{g}$ 重氮萘-2,1,5-磺酰氯和 $4.4{\\bf g}$ 线型酚醛树脂溶于 $90\\mathbf{g}$ 二氧六环中，在 $40^{\\circ}\\mathrm{C}$ 边搅拌慢慢加入 $40g10\\%$ 的碳酸钠水溶液，立刻生成白色沉淀，继续搅拌2h，则变成黏性油状物，倾去上层清液，加入大约10倍的水猛烈搅拌，油状物变为粉末，过滤、沉淀，用甲醇充分洗涤，40～50℃下干燥，得到10.3g线型酚醛树脂的重氮萘-2,1,5-磺酸酯。  \n\n（18）酚醛树脂-2-重氮萘-2,1,5-磺酸酯的合成在三口烧瓶中加入40g酚醛树脂、54g 2-重氮萘-2,1,5-磺酰氯和500mL二氧六环，搅拌下溶解，溶解完后于30～40℃下滴加碳酸钠饱和溶液至中性后再搅拌1h后，倒人稀盐酸水溶液中析出橙黄色固体，水洗，$40^{\\circ}\\mathsf{C}$ 下真空干燥即得酚醛树脂-2-重氮萘醒-2,1,5-磺酸酯。  \n\n（19）叠氮型感光性树脂的合成  \n\n![](images/7689a217a0bffaad1f5714a96aa39fb95bda388992e177084058f2346645e013.jpg)  \n\n在三口烧瓶中加人 $75\\mathbf{g}$ （ $\\begin{array}{r l}{0.54\\mathbf{mol}.}\\end{array}$ ）对硝基甲苯和 $\\scriptstyle450\\mathrm{mL}$ $95\\%$ 的乙醇，用氮气排除瓶内空气，加热使对硝基甲苯溶解。  \n\n将 ${\\mathfrak{s o o m L}}$ 蒸馏水用烧杯加热，并往水中通人氮气以排除水中的二氧化碳和氧气。再加人 $34\\mathbf{g}$ 氢氧化钠、 $_{45g}$ 硫化钠 $(\\mathrm{Na}_{2}\\mathbf{S}\\cdot\\mathbf{\\Hat{9}H}_{2}\\mathbf{O})$ 和 $_{19{\\bf g}}$ 升华硫，搅拌 $10\\mathrm{{min}}$ 溶液呈橘红色，趁热将此溶液加人到上述三口烧瓶中 (未溶解的升华硫同时加人)。在氮气保护下 $100^{\\circ}C\\pm$ $1^{\\circ}\\mathrm{C}$ 回流3h，马上进行水蒸气蒸馏，蒸毕，冷却，有红色油状物出现，剧烈摇动，析出金黄色结晶对氨基苯甲醛（A)，冷却2h后过滤，用 $0\\%$ 水分多次洗涤，干燥至恒重，得A$31.78$ ，产率 $47.5\\%$ ，熔点 $68{\\sim}70^{\\circ}\\mathrm{C}$  \n\n在三口烧瓶中加人 $18.38\\mathrm{~A~}$ ，用冰盐水冷却，加入 $60\\mathbf{m}\\dot{\\mathbf{L}}$ 冰水和 $75\\mathrm{mL}$ 浓盐酸，当内温冷至一 $5\\%$ 以下时，将 $16.7{\\bf g}$ 亚硝酸钠溶于 $64.2\\mathrm{mL}$ 水，滴人三口烧瓶中搅拌反应 $30\\mathrm{{min}}$ ，过滤除去少量不溶物，滤液转至干净的三口烧瓶中，冷至 $-2c$ ，搅拌下滴加 $14.98$ 的叠氮化钠（溶于 $64.2\\mathrm{mL}$ 水中)，加毕在 $-2\\%$ 下继续反应 $30\\mathrm{{min}}$ ，静止过夜，红棕色油状对叠氮苯甲醛（B）出现在溶液底层，分离出产物。用乙醚多次萃取悬浮于水层中的B，并与分离产物合并，多次用水清洗，分出油层用无水硫酸钠干燥，过滤，蒸出乙醚，得 $19.88\\mathrm{~B~}$ ，产率 $89\\%$ ， $20^{\\circ}\\mathrm{C}$ 下折射率为1.6225。  \n\n在三口烧瓶中加人部分皂化的聚乙烯醇 $_{5g}$ 和 $\\mathtt{50m L}$ 冰醋酸，使其溶解。加人 $\\texttt{B2.5g}$ 以浓硫酸为催化剂， $55\\sim60^{\\circ}\\mathrm{C}$ 搅拌反应3h，降至室温，加人 $40\\mathrm{mL}$ 丙酮稀释反应液，将其冲入水中析出纤维状树脂，充分水洗，室温风干，得5gC，即为叠氮型感光性树脂——聚乙烯醇缩对叠氮苯甲醛。  \n\n（20）2，2-双-(3，4-重氮苯酿)-丙烷的合成  \n\n![](images/a6e46d31581f3b8a528573e31393e532e6319671327561aa4183a07ee410fa54.jpg)  \n\n在三口烧瓶中加人34.2g（0.15mol）双酚A、 $100\\mathrm{mL}$ 醋酸，在 $20\\%$ 滴加 $24\\mathrm{mL}$ $d=$ $\\scriptstyle1,4\\mathbf{g}/\\mathbf{m}\\mathbf{L}$ 的硝酸，加毕继续反应 $^{2\\mathrm{h}}$ ，抽滤、洗涤得A粗品 $_{36.58}$ ，产率 $76\\%$ ，用乙醇重结晶，得精品，熔点 $130.5{\\sim}131^{\\circ}\\mathrm{C}$ 。  \n\n在三口烧瓶中加入6.4g（ $\\left\\langle0.02\\mathrm{mol}\\right\\rangle$ ）A、 $_{190\\mathrm{mL}}$ 无水乙醇和 $_{1\\pmb{\\mathrm{g}}}$ 雷尼镍，通入氢气常压催化还原。当吸氢停止后，加热 $70^{\\circ}\\mathrm{C}$ ，过滤浓缩得淡灰色 $\\textrm{B}4.6\\phantom{7}\\mathbf{g}$ ，产率 $90\\%$ 。  \n\n在三口烧瓶中依次加入 $3.9{\\pmb{\\mathrm{g}}}$ B（0.015mol)、 $5.5\\mathrm{mL}$ 醋酸、 $_{3\\mathbf{g}}$ 醋酸钠（溶于 ${\\mathsf{5m L}}$ 水中)、 $_{1\\pmb{\\upnu}}$ 硫酸铜（溶于 $\\scriptstyle5\\mathrm{mL}$ 水中)，在冰盐浴中 $\\textstyle0^{\\circ}\\mathsf{C}$ 时滴加 $2.78$ 亚硝酸钠溶液，进行氮化，提取氮化产物得到红色固体 $\\mathrm{~C~}2.5\\mathbf{g}$ ，即为2,2-双-(3,4-叠氮苯)-丙烷，产率 $60\\%$ 。  \n\n（21）氯甲基化聚苯乙烯的合成在三口烧瓶中加人 $6\\mathrm{mL}$ 二氯乙烷和 ${\\mathfrak{s}}_{*}2{\\mathfrak{g}}$ 聚苯乙烯 $\\omega_{\\mathrm{w}}$ 为 $9.2\\times10^{4}$ ）放置过夜，加入甲缩醛 $12.3\\mathrm{mL}$ ，搅拌下使聚苯乙烯溶解，滴加氯化硫酰$28.5\\mathrm{mL}$ ? $1\\mathord{\\sim}1.5\\mathrm{h}$ 内加完，温度保持 $25^{\\circ}C\\pm2^{\\circ}C$ ，搅拌1h，加入催化剂 $1.3\\mathbf{g}$ 氯化锌，反应 $4\\sim$ 6h，反应液黏度略增大，将反应液倒入盛有碎冰的蒸馏水中，氯甲基化聚苯乙烯呈膜状物析出。用冷蒸馏水洗 $3{\\sim}5$ 次，用冷甲醇浸泡洗涤 $3{\\sim}4$ 次，洗去未反应的甲缩醛以及氯化硫酰的分解产物，得白色海绵状产品氯甲基化聚苯乙烯，于 $45\\mathrm{{^\\circC}}$ 真空于燥8h，得产品为负性电子束抗蚀剂。  \n\n（22）氯甲基化聚苯乙烯的合成在三口烧瓶中加人 $600\\mathbf{g}$ ? $\\left(18.75\\mathrm{mol}\\right)$ ）甲醇、 $24\\mathrm{mL}$ 浓盐酸，在冰浴中于 $40\\mathrm{{min}}$ 内分批量逐渐加入 $\\boldsymbol{400}\\mathbf{g}$ 粉状无水氯化钙，放热不要让温度超过$20^{\\circ}\\mathrm{C}$ 。滴加 $\\scriptstyle400{\\mathbf{g}}$ 甲醛（ $37\\%$ ，4.9mol）于2h内加完。随着甲醛加人氯化钙逐渐溶解，当甲醛加毕，于 $45^{\\circ}\\mathrm{C}$ 加热 $15\\mathrm{{min}}$ 使反应完全。冷却转移分液漏斗中，放置6h以上，有机层用无水氯化钙干燥，蒸馏收集 $42\\sim46^{\\circ}C$ 馏分，得到 $370{\\sim}400\\mathrm{mL}$ 甲醇缩甲醛，收率为 $80\\%$ 。  \n\n在三口烧瓶中加人 $40\\mathbf{g}$ 聚苯乙烯（ $\\cdot M_{\\mathrm{w}}=8000{\\sim}27000$ ， $d{=}1.03{\\sim}2.20\\mathbf{g}/\\mathrm{cm}^{3},$ 、 $150\\mathrm{mL}$ 甲醇缩甲醛、 $\\scriptstyle450{\\mathrm{mL}}$ 氯仿和 $100\\mathrm{mL}$ 氯化亚矾，搅拌 $30\\mathrm{{min}}$ ，滴加四氯化锡溶液（ $7\\mathrm{mL}$ 四氯化锡溶于 $\\scriptstyle50\\mathrm{mL}$ 氯仿中)，反应 $^{10\\mathbf{h}}$ 。将反应液冲入 $\\scriptstyle2500{\\mathrm{mL}}$ 无水乙醇中，过滤、洗涤、干燥，得到氯甲基化聚苯乙烯 $_{45g}$ ，是一种高性能负性电子束光刻胶。  \n\n（23）氯甲基化聚苯乙烯的合成在三口烧瓶中加入 $5.4{\\pmb{\\mathrm{g}}}$ （60mmol）三聚甲醛、 $20\\mathrm{mL}$ $\\left(180\\mathbf{mmol}\\right)$ ）一氯三甲基硅烷和 $\\scriptstyle40\\mathrm{mL}$ 氯仿，搅拌2h后，加人 $6\\mathbf{g}$ 可溶性聚苯乙烯。在 $3\\%$ 下滴加四氯化锡溶液（ $\\mathrm{1.5mL}$ 四氯化锡溶于 $\\scriptstyle5\\mathbf{mL}$ 氯仿)，反应混合物颜色逐渐加深，由无色至红色。反应完毕，将反应液倒人 $300\\mathrm{mL}$ 乙醇中，过滤、洗涤、干燥，得到氯甲基化聚苯乙烯，其中氯甲基化比例达 $36\\%$ 中  \n\n（24）苯乙烯-叠氮甲基苯乙烯抗蚀剂的合成在三口烧瓶中加入 $_{108}$ ? $\\left(0.066\\mathbf{mol}\\right)$ ）对一氯甲基苯乙烯， $_{7\\mathbf{g}}$ （0.1lmol）叠氮钠， $_{100\\mathrm{mL}}$ 二甲基酰胺，室温下，搅拌2h反应。生成物用乙醚萃取提纯，得到叠氮甲基苯乙烯。 ..0.  \n\n将1mol叠氮甲基苯乙烯和4mol苯乙烯加人三口烧瓶中，加入适量苯作溶剂、偶氮二异丁腈（1%单体中量）通氮气，升温至回流温度反应8h，得苯乙烯-叠氮甲基苯乙烯，是一种耐干蚀剂的光致抗蚀剂。 1 S(25）聚降冰片烯-5-羧酸-(8-乙基三环癸基)酯的合成  \n\n![](images/1d77653a9c59a54a75c492787c3e26e3f68f84e1eece5def571f0dd8e9ae00fe.jpg)  \n\n安装具有氮气导人管、温度计、搅拌和橡胶隔片的四口烧瓶，通过双针头管向瓶内压人400g含25%无水氯化镁的四氢呋喃溶液，用干冰冷至一25～一30℃。用氮气向瓶内压入153.6g三环癸烷-8-酮和480g无水四氢呋喃，用时2h，压完后移去冷槽，搅拌反应2h，再把反应液冷至－25～—30℃，滴加108g丙烯酰氯，1～1.5h滴完，升温至室温搅拌过夜，从琥珀色透明溶液中出现白色沉淀。再滴加75g新裂解的环戊二烯，滴完升温至50℃反应68h，变成带白色沉淀的橙色液体。冷至室温，加去离子水至所有的盐均溶解并分成两层，上层有机层用500mL饱和碳酸钠洗，再用2×500mL去离子水洗后，用无水硫酸镁干燥、过滤蒸去四氢呋喃，得橙色油300g，减压蒸馏（158℃/5mmHg，1mmHg=133.32Pa）得189g纯降冰片烯-5-羧酸-(8-乙基三环癸基)酯（A)。  \n\n将A用四氢呋喃溶解，充氮气保护，加热回流下滴加偶氮二异丁腈-四氢呋喃溶液，回流反应过夜，反应液倒入正已烷中，析出聚合物，再用四氢呋喃溶解，用正已烷析出，得聚合物粉末，真空干燥得纯品为聚降冰片烯-5-羧酸-(8-乙基三环癸基)酯，是一种193nm 光刻胶。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 563,
+        "chunk": "# （26）聚羟基苯乙烯的合成  \n\nA:  \n\n![](images/cdaa0a08baed49d6de71ca08ab07d981fba5eef461f479fd33cc0a986f2f9437.jpg)  \n\n![](images/73a68188b329e0fcac5210152158aa9b228eb8f709deb562b21847454c7a1cc9.jpg)  \n\n在避光条件下，将 $\\pmb{\\alpha}$ 澳代-2-蔡乙酮 $20\\pmb{\\mathrm{g}}$ 、 $100\\mathrm{mL}$ 丙酮加入三口烧瓶中，在 $0^{\\circ}\\mathsf{C}$ 时加人$\\scriptstyle4,8\\mathrm{mL}$ 水，搅拌下缓慢滴加四氢噻吩 $_{14\\mathrm{mL}}$ ，加毕 $0\\%$ 搅拌1h，产生沉淀后，室温下继续搅拌1h，滤出固体，用无水乙醇重结晶两次，得淡粉色晶体S-(2-蔡甲酰)甲基四氢噻吩溴化物 $_{21.1\\mathbf{g}}$ ，产率 $78\\%$ ，熔点 $136{\\sim}137^{\\circ}\\mathrm{C}$ 。  \n\n将 $3.6\\mathbf{g}$ 上述溴化物、 $150\\mathrm{mL}$ 乙晴加人三口烧瓶中，避光操作，搅拌下缓慢滴加 $_{3{\\bf g}}$ 对甲苯磺酸银的 $70\\mathrm{mL}$ 乙腈溶液，室温反应 $\\pmb{24}\\mathbf{h}$ ，滤出不溶物，浓缩滤液，将浓缩滤液倾人大量无水乙醚中，滤出固体用乙睛溶解，重复上述操作三次，得到纯的白色晶体S-(-2-萘甲酰)甲基四氢噻吩对甲苯磺酸盐 $4.3{\\bf g}$ ，产率 $94\\%$ ，熔点 $146{\\sim}147^{\\circ}\\mathrm{C}$ 。  \n\n将 $8.6\\mathbf{g}$ 对甲苯磺酸、5.1g氧化银加人三口烧瓶中，加 $120\\mathrm{mL}$ 乙晴，避光操作，搅拌$5\\sim8\\mathrm{h}$ ，滤出不溶物，滤液旋蒸至干得到白色固体，用丙酮洗三次，得白色对甲苯磺酸银固体 $_{12.3g}$ ，产率 $97\\%$ 口  \n\n用同样方法制得亮白色的甲磺酸银，产率 $65\\%$ 。  \n\n用三氟甲磺酸代替对甲苯磺酸银，合成三氟甲磺酸盐，产率 $84\\%$ ，熔点 $158{\\sim}159^{\\circ}\\mathrm{C}$ 。 用甲磺酸银代替对甲苯磺酸银合成甲磺酸盐，产率 $88\\%$ ，熔点 $182\\sim183^{\\circ}\\mathrm{C}$ （ $\\lambda=$ ${\\bf193n m})$ 。硫盐的性能见表10-5。  \n\n表10-5硫盐的性能  \n\n\n<html><body><table><tr><td>硫盐</td><td>分解温度/℃</td><td>峰值温度/℃</td><td>ε(=193nm）/[L/(mol·cm)]</td></tr><tr><td>对甲苯磺酸盐</td><td>249~288</td><td>270</td><td>6.8X10</td></tr><tr><td>三氟甲磺酸盐</td><td>241~250</td><td>246</td><td>0.78×104</td></tr><tr><td>甲磺酸盐</td><td>224~276</td><td>253</td><td>0.78X104</td></tr></table></body></html>  \n\n这三种硫盐适用于 $193\\mathrm{nm}$ 光刻胶产酸剂。  \n\n（28）三嗪类光产酸剂合成  \n\n![](images/aca1458dd2630e928c5be66877f7f31cb4cfb486d8f93b27740279a8397dbcc5.jpg)  \n\n将 $3.3g$ （10mmol）2-甲基-4，6-双（三氯甲基)-1,3,5-三嗪（I）、 $1.6\\mathbf{g}$ （12mmol）4-甲氧基苯甲醛溶于 $30\\mathrm{mL}$ 甲苯中依次加入 $0.4{\\bf g}$ 冰醋酸、 $_{0.2g}$ 哌啶，加热回流分水， $40\\mathrm{{min}}$ 后冷至室温，减压蒸出甲苯，加人乙酸沉淀，过滤、干燥得棕黄色固体，用乙醇重结晶得产物，熔点 $191^{\\circ}\\mathrm{C}$ ，产率 $18\\%$ 。  \n\n将1.1g（3.3mmol）I、 $1.2{\\tt g}$ （4.3mmol）4-(N，N-二苯氨基)苯甲醛，溶于 $30\\mathrm{mL}$ 甲苯中同上反应，用乙醇重结晶得0.8g产物，产率 $41\\%$ ，熔点 $181.1{\\sim}182.7^{\\circ}\\mathrm{C}$ 。  \n\n用 $1.1\\dot{\\mathbf{g}}(3.3\\mathbf{mmol})\\mathrm{~I~},0.8\\mathbf{g}(0.45\\mathbf{mmol})4-\\mathcal{Z}\\dot{\\mathbf{z}}\\dot{\\mathbf{z}}\\dot{\\mathbf{z}}\\dot{\\mathbf{z}}\\dot{\\mathbf{z}}\\Psi\\equiv\\mathbf{mm}\\dot{\\mathbf{z}}\\dot{\\mathbf{z}}\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\Psi\\dot{\\mathbf{z}}\\Psi\\dot{\\mathbf{z}}\\Psi\\Psi\\dot{\\mathbf{z}}\\Psi\\Psi\\dot{\\mathbf{z}}\\Psi\\Psi\\dot{\\mathbf{z}}\\Psi\\Psi\\dot{\\mathbf{z}}\\Psi\\Psi\\dot{\\mathbf{z}}\\Psi\\Psi\\dot{\\mathbf{z}}\\Psi\\Psi\\Psi\\dot{\\mathbf{z}}\\Psi\\Psi\\Psi\\dot{\\mathbf{z}\\Psi\\Psi\\Psi\\mathbf{z}\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi{\\mathbf{z}\\Psi\\Psi\\Psi\\mathbf{z}\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi{\\mathbf{z}\\Psi\\Psi\\Psi\\Psi\\Psi\\mathbf{\\mathbf{z}\\Psi\\Psi\\mathbf{\\mathbf\\mathbf{z}\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi{\\mathbf\\mathbf{z}\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi\\Psi $ $20\\mathrm{mL}$ 甲苯中，同上反应，用四氢呋喃/乙醇重结晶，得 $1.22g$ 产物，产率 $74\\%$ ，熔点 $180.9\\mathrm{^{\\circ}C}$ 。  \n\n用1.1g(3.3mmol）I、1.0g(0.44mmol)N-乙基咔唑-3-醛，溶于 $30\\mathrm{mL}$ 申苯中，同上反应，用二氯甲烷/乙醇重结晶，得 $1.1\\mathbf{g}$ 产物，产率 $64\\%$ ，熔点 $192.7{\\sim}193.3^{\\circ}\\mathrm{C}$ 。  \n\n以上几种三嗪类化合物均为光产酸剂。  \n\n(29)三嗪类光产酸剂的合成  \n\n![](images/8adc9c79487b5b6852f55897e0663340b3e9b9a13d737bcf1b59a3e11ed5f320.jpg)  \n\n在三口烧瓶中加人9.9g(0.03mol)2-甲基-4,6-双-(三氯甲基)三嗪、对硝基苯甲醛 5.4g(0.036mol）和 $30\\mathrm{mL}$ 无水乙醇，搅拌、升温至 $30{\\sim}40^{\\circ}\\mathrm{C}$ ，约半小时后加入哌啶（固体反应物质量的5%～10%）和等物质的量的冰醋酸，恒温反应6h，再常温搅拌过夜，次日将析出固体抽滤， $40^{\\circ}\\mathsf{C}$ 烘干，得乳黄色粉末 $4.9{\\bf g}$ ，产率 $35\\%$ ，熔点 $78.5\\%$ ， $\\lambda_{\\mathrm{max}}=337\\mathrm{nm}$ [为$32000\\mathbf{L}/(\\mathbf{mol}\\cdot\\mathbf{cm})]$ 9  \n\n（30）三嗪类光产酸剂的合成  \n\n![](images/63f543e65ef4ba792e1093910e1f855cff6a32c56498084f736bfcc9775cbcff.jpg)  \n\n在三口烧瓶中加人冰醋酸和等物质的量的哌啶（为固体反应物质量的5%～10%）搅拌，再加人9.9g（0.036mol）2-甲基-4,6双-(三氯甲基)三嗪、5.9g（0.036mol）对乙酰氨基苯甲醛和30mL无水乙醇，升温40℃，恒温1h，常温搅拌48h，得到黄色粉末9.9g，产率 $70\\%$ ，熔点 $272.4{\\sim}273.8\\%$ ， $\\lambda_{\\operatorname*{max}}=380\\mathrm{nm}$ [为 $40500\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{cm})]$ 。  \n\n（31）三嗪类光产酸剂的合成在三口烧瓶中加入哌啶（固体反应物质量的5%～10%）、2-甲基-4,6-双三氯甲基三嗪9.9g（0.03mol）、4.3g（0.036mol）间甲苯甲醛和30mL无水乙醇，搅拌升温至40℃，恒温反应1h，常温搅拌24h，得到乳黄色粉末7.3g，产量 $56.2\\%$ ，熔点 $144.5\\mathrm{^\\circC}$ $\\lambda_{\\operatorname*{max}}=345\\mathrm{nm}$ [为 $33000\\mathrm{L}/(\\mathrm{mol}\\cdot\\mathrm{cm})\\]$ 。  \n\n（32）三嗪类光产酸剂的合成在三口烧瓶中加入哌啶（为固体反应物质量的 $5\\%\\sim$ 10%）9.9g（0.03mol)、2-甲基-4,6-双三氯甲基三嗪、4.3g（0.036mol）邻甲基苯甲醛和$\\scriptstyle30\\mathrm{mL}$ 无水乙醇，搅拌升温至 $40^{\\circ}\\mathsf{C}$ ，恒温1h，常温搅拌 $24\\mathrm{h}$ ，得乳黄色粉末 $6.6\\mathbf{g}$ ，产率$51\\%$ ，熔点 $127.3\\mathrm{\\sim}129.7\\mathrm{\\textperthousand}$ ， $\\lambda_{\\operatorname*{max}}=345\\mathrm{nm}$ [为 $38900~\\mathrm{L/(mol\\cdotcm)]}$ 。  \n\n（33）硫盐类光产酸剂的合成  \n\n![](images/8e332424b53d4bc31e6b34b4fa01006974abe0bf06ff0281ff32d06e0f3d11ee.jpg)  \n\n将 $^{4-(N,N-$ 二苯胺)、苯甲醛、磷叶立德试剂（摩尔比为 $4.4:29$ ）和二甲基甲酰胺加人三口烧瓶中，氮气保护，冰浴冷至 $0^{\\circ}\\mathrm{C}$ ，加人甲醇钠， $0^{\\circ}\\mathrm{C}$ 搅拌 $30\\mathrm{{min}}$ ，室温搅拌 $24\\mathrm{h}$ ，用甲醇沉淀、过滤，用二氯甲烷/乙醇重结晶，得黄色固体A，为4-[4-(甲硫基)苯乙烯基］-N,N-二苯基苯胺，产率 $70\\%$ ，熔点 $185.4{\\sim}187.2\\%$ ， $\\lambda_{\\operatorname*{max}}{=}368.5\\mathrm{nm}$ 。  \n\n将A溶解于 $\\scriptstyle80\\mathrm{mL}$ 干燥二氯甲烷中，加入三氟甲基磺酸甲酯（摩尔比为 $5.1:6.1)$ ，室温避光搅拌，蒸出溶剂，在乙醇中沉淀，得黄色固体B，为 $\\scriptstyle4-\\left[4-\\left(N,N-\\right)\\right]$ 二苯氨基)苯乙烯基]苯基二甲基硫三氟甲基磺酸盐， $\\lambda_{\\operatorname*{max}}=393\\mathrm{nm}$ ，光分解量子产率0.17，光产酸率0.05。  \n\n（34）硫盐类光产酸剂的合成  \n\n![](images/3ca743e13bedb4f17540d86a338b24a913ec18356c0cc8571a86583e29d2b557.jpg)  \n\n将4-(二乙基氨基)苯甲醛、磷叶立德试剂 (摩尔比为 $4.4:2.93$ ）和二甲基甲酰胺加入三口烧瓶中，氮气保护，冰浴冷至 $0^{\\circ}\\mathsf{C}$ ，加人甲醇钠， $0^{\\circ}\\mathrm{C}$ 搅拌 $30\\mathrm{min}$ ，室温搅拌 $\\pmb{24}\\mathbf{h}$ ，用甲醇沉淀、过滤，用二氯甲烷/乙醇重结晶，得黄绿色固体A，为4-[4-(甲硫基)苯乙烯基］-N,N-二乙基苯胺，产率 $30\\%$ ，熔点 $143.5\\sim144.7^{\\circ}\\mathrm{C}$ ， $\\lambda_{\\operatorname*{max}}{=}368\\mathrm{nm}$  \n\n将A溶解在 $80\\mathrm{mL}$ 干燥的二氯甲烷中，加人三氟甲基磺酸甲酯（摩尔比为 $5.1:6.1)$ ，室温避光搅拌，蒸出溶剂，在乙醇中沉淀，用乙腈/乙醚重结晶得浅黄色固体B，为4-[4-(二乙基氨基)苯乙烯基苯基，二甲基硫三氟甲基磺酸盐，产率 $40\\%$ ， $\\lambda_{\\operatorname*{max}}=402\\mathrm{nm}$ ，光分解量子产率0.3，光产酸效率0.08。  \n\n（35）光产酸剂-对乙氧基葱磺酸酯的合成  \n\n![](images/998310bf242e3c7bc5e60e24d9793fc84fb07c23b650ced3b9f00dc34ca23a29.jpg)  \n\n在三口烧瓶中加入锌粉 $\\scriptstyle40_{\\mathbf{\\mathbf{E}}}$ 、乙醇 ${}_{300\\mathrm{mL}}$ 、葱-2-磺酸钠 $\\pmb{200}\\mathbf{g}$ ，搅拌升温至回流，反应1h，滴加硫酸二乙酯 ${\\mathsf{500m L}}$ ，2h加完，再保温反应3h。冷至室温过滤，滤饼用亚硫酸氢钠溶液洗几次，把滤饼溶在 $\\scriptstyle2000{\\mathrm{mL}}$ 热水中，趁热过滤，滤液冷至室温后过滤，得黄绿色结晶状固体A，为对乙氧基葱-2-磺酸钠，产率 $73\\%$ 。  \n\n在三口烧瓶中加人 $100\\mathbf{g}\\mathbf{A}$ 、苯 $\\scriptstyle400{\\mathrm{mL}}$ ，搅拌分散 $10\\mathrm{{min}}$ ，室温下加人 $150\\mathbf{g}$ 五氯化磷，反应半小时，过滤，滤液用水洗至 $\\mathtt{p H}$ 值为中性或弱酸性，用分液漏斗分出苯层，用无水氯化钙干燥，再过滤，液减压蒸去溶剂，得黏稠状棕红色液体B，为对乙氧基葱-2-磺酰氯，产率 $51\\%$ 。  \n\n在三口烧瓶中加人 $80_{\\mathbf{8}}\\textbf{B}$ ， $30{\\bf g\\ 4}$ -硝基苯甲醇、 $\\scriptstyle250{\\mathrm{mL}}$ 四氢呋喃搅拌溶解，在冰盐浴中降温 $10^{\\circ}\\mathrm{C}$ 以下，滴加氢氧化钠溶液，半小时滴完，再反应 $^{3\\mathrm{h}}$ ，加入大量的水搅拌半小时，过滤，滤饼用水和甲醇依次洗涤，然后在 $30^{\\circ}\\mathrm{C}$ 以下干燥，得深黄色颗粒状固体C，为4-硝基苯基对乙氧基葱-2-磺酸酯，是一种磺酸酯类光产酸剂，产率 $83\\%$ 。  \n\n（36）化学增幅抗蚀剂叔丁酚酚醛树脂的合成  \n\n$$\n+(\\underbrace{\\sum_{i=1}^{\\mathrm{oH}}\\mathrm{cH}_{3}}_{\\mathrm{cc}(\\mathbf{CH}_{3})_{3}}+\\underbrace{\\sum_{i=1}^{\\mathrm{oH}}\\mathrm{cH}_{2}}_{\\mathrm{cc}(\\mathbf{H}_{3})_{3}}+\\underbrace{+\\left(m+n\\right)(\\mathrm{CH}_{3})_{3}\\mathrm{c}-0-0-0-0}_{\\mathrm{cc}(\\mathbf{C}-\\mathbf{H}_{3})_{3}}\\xrightarrow{\\mathbb{Q}\\mathrm{ZR}_{3}}.\n$$  \n\n![](images/2d359434d79f237db79ea11843bb34243c43320014cc794b17cb6b7dbbf159c7.jpg)  \n\n在三口烧瓶中加人1.3g叔丁酚醛树脂（含0.0lmol酚羟基)、40mL二氧六环，搅拌溶解后加人2.2g（0.0lmol）叔丁氧碳酸酐、催化剂0.2～0.3g三乙胺（或三乙醇胺)，缓慢升温至80℃，在80～100℃回流3～5h，冷至5℃得橙色液体，倒人1000mL热蒸馏水中，析出淡黄色固体，用蒸馏水热洗数次，干燥至恒重得产物A，软化点81℃左右，产率85%。  \n\n（37）分子玻璃光抗蚀剂酯缩醛的合成将甲基丙烯酸和二乙烯基醚按摩尔比2：1加入烧瓶中，用适量二甲苯作溶剂，电磁搅拌下升温至120～130℃反应3～5h，直到乙烯基在1610cm-1处红外吸收消失。然后将反应混合物中加人甲醇，析出产物，真空干燥，得到酯缩醛，为分子玻璃光致抗蚀剂。  \n\n（38） $N\\cdot$ -烷基马来酰亚胺的合成  \n\n![](images/6bf92b8bdbef5d1411600a053fe04631401eb9d353fcbb3dc2b698a33a7675b2.jpg)  \n\n在装有分水器的三口烧瓶中加入7.7g对甲苯磺酸和70mL二甲苯，加热至155～160℃将水除去，降温至100℃，加人马来酸酐19.6g（0.2mol）、醋酸5g和0.01g2,6-二叔丁基对甲酚。回流，在3h内滴加苄胺21.4g（0.2mol)。加毕，保温反应2h。降温至75℃，加蒸馏水30g，用分液漏斗分出油层，减压蒸馏除去溶剂，得到产物，用环已烷重结晶，减压下于40～50℃C烘干，得到N-苄基马来酰亚胺（BeMI）20.6g，收率55.3%。  \n\n采用相同的合成方法，滴加对应的胺，得到不同的N-取代马来酰亚胺，N-丁基马来酰亚铵（n-BuMI)、N-异丁基马来酰亚胺（i-BuMI)、N-环已基马来酰亚铵（CMI)、N-异丙基马来酰亚胺（i-PMI）和N-烯丙基马来酰亚胺（AMI)。  \n\n不同MI的性能见表10-6。  \n\n表10-6不同MI的性能  \n\n\n<html><body><table><tr><td>MI</td><td>外观</td><td>熔点/℃</td></tr><tr><td>BeMI CMI n-BuMI</td><td>白色晶体 白色晶体 无色液体</td><td>66.9~68.8 86.0~89.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 564,
+        "chunk": "# （39）光敏聚酰亚胺的合成  \n\n![](images/7e6f13e990b8351ce2dca76381ad4f769d1327f4aa0debac1f0b3851da5aa845.jpg)  \n\n将3.36g对乙酰氨基苯甲醛溶于50mL乙醇中，滴加到3.74g间乙酰氨基苯乙酮、20mL乙醇、20mL4%的氢氧化钠水溶液的混合液中，在冰浴下搅拌3h，抽滤得到黄色固体（I） $6.12{\\bf g}$ ，产率为 $86.2\\%$ a  \n\n将3.3lg（I）加到150mL5%的盐酸溶液中，加热回流3h，冷却抽滤得到红色固体，用去离子水重结晶得到红色固体（Ⅱ）1.85g，产率为71.9%。  \n\n将0.476g（Ⅱ）加人到三口烧瓶中，在氮气保护下，滴人6mL经蒸馏并用分子筛处理后的二甲基乙酰胺，搅拌溶解后加入0.436g均苯四甲酸二酐，室温搅拌48h，再加入3mL等摩尔比的乙酸酐和吡啶混合液，80℃下保温5h，随反应进行，体系黏度明显增大，搅拌变得困难，说明聚酰亚胺高分子形成。将反应液倒人大量冰水中，聚酰亚胺以丝状沉淀析出，抽滤后得深黄色固体，用乙醇洗涤，70℃下真空干燥8h，得黄色固体粉末即为光敏聚酰亚胺（Ⅲ）耐热 $400^{\\circ}\\mathrm{C}$ 以上，紫外吸收 $\\lambda_{\\operatorname*{max}}{=}365\\mathrm{nm}$ 。  \n\n（40）光敏二胺的合成  \n\n![](images/1b3c2bb4ceb73bd28fef596d0ebd22e743f08d7adf6aa6e9da91804e63ba686b.jpg)  \n\n在三口烧瓶中加入6.75g（0.05mol）对氨基苯乙酮和30mL苯，加热溶解，滴加6mL醋酸酐，回流2.5h，冷却，抽滤，滤液静置析出固体，用乙醇和水混合液（体积比1：3)重结晶，真空干燥，得A，为对乙酰氨基苯乙酮。 +  \n\n将50mL氢氧化钠的醇溶液、25mL乙醇及7.0g（0.04mol）A加入三口烧瓶中，加热搅拌至溶解，降至室温，剧烈搅拌下滴加2.7g（0.02mol）溶解于50mL乙醇的对苯二甲醛溶液，在冰浴中搅拌反应，反应完后放置冰箱中冷却，析出固体抽滤，得到B。  \n\n将B加入150mL7%的盐酸溶液，加热回流3h，用5%的氢氧化钠水溶液中和，调pH值至8，析出大量固体，抽滤，用去离子水重结晶，干燥，得产物C，为1,4-二[2-(4-氨基苯甲酰)乙烯基]苯，纯度96%，熔点293～295℃，为光敏二胺，是合成光敏聚酰亚胺的  \n\n原料。  \n\n（41）UV固化液晶单体的合成在三口烧瓶中加入4.60g胆甾醇氯甲酸酯、4.55g二乙氧基甲基丙烯酸羟乙酯（CD570)、 $\\phantom{+}0.83\\mathbf{g}$ 吡啶及适量甲苯，常温搅拌 $^{12\\mathbf{h}}$ ，滤去沉淀，倒入大量甲醇中沉淀，过滤得乳白色产物，即为可UV固化液晶单体。  \n\n（42）UV固化液晶单体的合成  \n\n![](images/0ab8cf49767c1d67d6b1b6dfb100f516cfb75bf7c3a606842178abcee8edfd86.jpg)  \n\n在三口烧瓶中加人17.8g氢氧化钾、169.57g对羟基苯甲酸及一定量的碘化钾溶于适量乙醇和去离子水的混合溶液，冷却后，升温至 $78^{\\circ}C$ ，滴加 $22.5g$ 氯乙醇，加毕回流 $\\mathbf{20h}$ ，停止反应，酸化至弱酸性滤出沉淀，用乙醇重结晶，真空干燥得 $19.44{\\bf g\\ A}$ 。  \n\n将 $6.0\\mathbf{g}$ A及 $_{3{\\tt g}}$ 三乙胺溶于适量1,4-二氧六环中，搅拌下滴加丙烯酰氯，常温搅拌24h，反应结束后，倒入水中沉淀，滤出沉淀，用乙醇重结晶，真空干燥，得到5.89gB。  \n\n将 $4.72_{8}\\mathrm{~B~}$ 、2.4lg4-甲氧基酚及一定量DCC和DMAP，溶于适量二氯甲烷中，常温揽拌2天，过滤除去沉淀，滤液倒人正已烷中沉淀，沉淀用乙醇重结晶，得到产物C为UV固化液晶单体4-(6-丙烯酰氧基)五基苯甲酸 $\\cdot4^{\\prime}$ -甲氧基苯酚酯。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 565,
+        "chunk": "# 10.1.15 光刻胶参考配方  \n\n(1）重铬酸盐-聚乙烯醇光刻胶参考配方(单位：质量份)  \n\n配方A：  \n\n<html><body><table><tr><td>高分子量聚乙烯醇 2 染料 低分子量聚乙烯醇 10</td><td>适量</td></tr></table></body></html>  \n\n<html><body><table><tr><td>配方B：</td></tr><tr><td>重铬酸铵 20</td></tr></table></body></html>  \n\n按 $\\mathbb{A}:\\mathbb{B}{=}3:1$ （质量比）混合后立即使用。  \n\n（2）聚乙烯醇肉桂酸酯光刻胶参考配方  \n\n<html><body><table><tr><td>聚乙烯醇肉桂酸酯 10g 5-硝基 0.07g</td><td>环己酮 100g 添加剂 适量</td></tr></table></body></html>  \n\n光刻胶感光区波长 $350{\\sim}470\\mathrm{nm}$ ，分辨率 $2\\sim4\\mu\\mathrm{m}$ .  \n\n（3）聚乙烯氧乙醇肉桂酸酯光刻胶参考配方  \n\n<html><body><table><tr><td>聚乙烯氧乙醇肉桂酸酯 15g 环已酮 5-硝基 0.75g 乙二醇乙醚醋酸酯</td></tr></table></body></html>  \n\n光刻胶感光区波长 $\\mathbf{350}{\\sim}450\\mathbf{nm}$ ，分辨率 ${\\leqslant}1\\mu\\mathbf{m}$ 中",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 566,
+        "chunk": "# （4）聚肉桂亚丙二酸乙二醇酯光刻胶参考配方  \n\n<html><body><table><tr><td>聚肉桂亚丙二酸乙二醇酯 12g 环已酮 5-硝基 0.3g</td></tr></table></body></html>  \n\n光刻胶感光区波长 $350\\sim470\\mathrm{nm}$ ，分辨率 $1\\sim2\\mu\\mathrm{m}$ 中  \n\n（5）环化橡胶光刻胶参考配方（单位：质量份）  \n\n<html><body><table><tr><td>环化聚异戊二烯 2,6-双（4-叠氮亚苄基）-4-甲基环已酮</td><td>15.0 0.4</td><td>2，6-二叔丁基对甲苯酚 N-苯基-a-萘胺</td><td>适量 适量</td></tr></table></body></html>\n\n光刻胶感光区波长 $300\\sim450\\mathrm{nm}$ 辨事  \n\n（6）邻重氮正性光刻胶参考配方（单位：质量份）i  \n\n<html><body><table><tr><td>酚醛树脂-2-重氮萘-2，1，5-磺酸酯 线型甲酚醛树脂</td><td>10 3.5 适量</td><td>乙二醇乙醚醋酸酯 二甲苯</td></tr></table></body></html>\n\n光刻胶感光区波长 $300\\sim450\\mathrm{nm}$ ，分辨率≤1μm。  \n\n（7）负型水性化学增幅抗蚀剂参考配方  \n\n邻甲酚醛树脂 $100{\\bf g}$ 六甲氧基甲基三聚氰胺 32g 对甲苯磺酸二苯基碘盐 $10\\mathbf{g}$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 567,
+        "chunk": "# （8）光敏聚酰亚胺光刻胶参考配方  \n\n<html><body><table><tr><td>光敏聚酰亚胺 米酮</td><td>30 2</td></tr></table></body></html>  \n\n（9）化学增幅型光刻胶参考配方  \n\n供具活摩理  \n\n\n<html><body><table><tr><td>吩噻嗪 乙二醇乙醚乙酸酯</td><td></td></tr></table></body></html>  \n\nN-甲基吡咯烷酮 80   \n环己酮 20  \n\n<html><body><table><tr><td>邻甲酚醛树脂</td><td>100g 35g</td><td>增感剂吩噻嗪</td></tr></table></body></html>  \n\n（10）化学增幅抗蚀剂参考配方（单位：质量份）  \n\n<html><body><table><tr><td>叔丁氧碳酰改性叔丁酚酚醛树脂 10 光产酸剂三溴甲基苯基矾 2</td><td>乙二醇独甲醚 100</td></tr></table></body></html>\n\n中电#大，中",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 568,
+        "chunk": "# 10.2印制电路板制造用的光固化材料",
+        "category": " Introduction"
+    },
+    {
+        "id": 569,
+        "chunk": "# 10.2.1 概述  \n\n印制电路板（printed circuitboard，简称PCB）是现代电器安装和连接元件的基板，是电子工业的重要基础器件。在电子工业发展中，PCB技术的出现是现代电器设备安装的整体化和小型化发展的一个重大突破。  \n\n印制电路是指在绝缘基材上，按预定设计，提供元器件之间电气连接的导电图形。印制电路的成品板称为印制电路板，印制电路板为晶体管、集成电路、电阻、电容、电感等元件提供了固定和装配的机械支撑；实现了晶体管、集成电路、电阻、电容、电感等元件之间的布线和电气连接、电绝缘来满足其电气特性；为电子装配工艺中元件的检查、维修提供了识别字符和图形，为波峰焊提供了阻焊图形。  \n\n印制电路板根据印制板基强度分类有刚性印制板（rigid printed board)，是用刚性基材制成的印制板；挠性印制板（flexible printed board)，是用柔性基材制成的印制板；刚挠性印制板（flexrigid printed board)，是利用性基材，并在不同区域与刚性基材结合制成的印制板。根据印制板导电结构分类有单面印制板（single-sided printed board)，是仅有一面有导电图形的印制板；双面印制板（double-sided printed board)，是两面均有导电图形的印制板；多层印制板（multilayer printedboard)，是由三层或三层以上导电图形与绝缘材料交替粘接在一起、层压而制成的印制板。目前印制电路板制作有减成法和加成法两种工艺，主要还是采用减成法工艺来制作印制电路板，是在覆铜箔层压板表面上，有选择性地除去部分铜箔来获得导电图形。  \n\n根据印制电路在商品上的使用量，可大致分成如下三类。  \n\n（1）信息类约占50%，包括电脑、笔记本电脑、计算机辅助设计和制造系统、汽车控制系统等。（2）通信类约占34%，如移动电话、通信网络系统、互联网、局域网、蓝牙卡板、调制解调器等。（3）消费类约占16%，如电视机、收录音机、数码相机、摄像机、打印机、复印机、电动玩具等。如今在工业、农业、医疗卫生、教育科研、军事工业等一切需要自动化和电气化的设备，都离不开印制电路板；在人们的日常生活中，电冰箱、空调、洗衣机、家庭影院、数码相机、手机等各种电器也都少不了印制电路板，可以说，在现代社会中印制电路板无所不在。  \n\n20 世纪40年代，英国人PaulEisler博士等第一个采用印制电路板制造收音机，并率先提出了印制电路板的概念，经过几十年的研究和发展，20世纪印制电路生产总值已超过400亿美元。我国从20世纪50年代中期开始研制单面印制电路板；60年代开发出国产的覆铜板，小批量生产双面印制电路板；1964年开始研制生产多层印制电路板；80年代引进国外先进的单面和双面印制电路板生产线，较快地提高了我国印制电路的生产技术水平；90年代以后，香港、台湾地区印制电路板厂家纷纷来大陆合资或独资建厂，使我国印制电路产业发展迅猛；至2006 年，我国印制电路生产超过日本、美国，成为世界最大的印制电路生产国。",
+        "category": " Introduction"
+    },
+    {
+        "id": 570,
+        "chunk": "# 10.2.2 印制电路板的制作  \n\n印制电路板有单面板、双面板、多层板和积层多层板，它们的制作过程和所用的材料也不同，目前大多数都用光固化材料：UV油墨、干膜（dry film photoresist或 dry film）、光成像油墨（photoimageable ink）和电沉积光刻胶（electrodeposited photoresist），它们的性能比较见表10-7。  \n\n目前印制电路板的制作主要有三种方法：网印法、干膜法和湿膜法（也叫液态感光成像法或光成像法)，如图10-17所示。网印法由于分辨率低，只能用于制作单面板，干膜法和湿膜法多用于制作双面板和多层板。  \n\n表10-7PCB用光固化材料的性能比较  \n\n\n<html><body><table><tr><td>项目</td><td>UV油墨</td><td>干膜</td><td>光成像油墨</td><td>电沉积光刻胶</td></tr><tr><td>分辨率/μm</td><td>≥150</td><td>80～100</td><td>50</td><td>20~30</td></tr><tr><td>图性重合精度/μm</td><td>±100</td><td>±20</td><td>±20</td><td></td></tr><tr><td>图形形成</td><td>丝网漏印</td><td>真空贴膜 隔片基曝光 显影成像</td><td>丝网满印、帘涂、喷涂 接触曝光 显影成像</td><td>电泳沉积成膜 接触曝光 显影成像</td></tr></table></body></html>  \n\n![](images/100be8ee61d4581c3bbb2712c229e48fd9f0a7ab84231bc892f788a86ba8289d.jpg)  \n图10-17印刷电路板制造工艺流程",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 571,
+        "chunk": "# 10.2.3 UV抗蚀油墨  \n\n单面板制作都用网印法，要网印三道油墨。制作工艺为：  \n\n覆铜板 $\\rightarrow$ 前处理 $\\star$ 网印UV抗蚀油墨 $\\nsim$ 紫外固化 $\\mathbf{\\rightarrow}$ 腐蚀（有时需电镀） $\\mathbf{\\rightarrow}$ 去膜→网印UV阻焊油墨 $\\rightarrow$ 紫外固化 $\\rightarrow$ 网印UV字符油墨 $\\rightarrow$ 紫外固化 $\\rightarrow$ 检验 $\\rightarrow$ 成品  \n\n印制电路板上的铜质电路是覆铜板经三氯化铁或氯化铜腐蚀而成，故不需腐蚀的线路部分要用抗蚀材料保护。在网印法中，要用抗蚀油墨（etch resist)，因固化方式不同分自干型和光固化型两种。油墨经有抗蚀图形的丝网漏印在覆铜板上固化后形成。覆铜板经腐蚀（有时还需电镀）形成铜质线路后，用稀碱液去膜，不留在印制板上，露出铜质电路。因此要求抗蚀油墨与金属铜黏附性好，能耐抗蚀和电镀，还要能被稀碱液完全去除。  \n\nUV抗蚀油墨一般都选用酸酐改性的环氧丙烯酸酯、高酸值的聚酯丙烯酸酯或改性的马来酸酐树脂等碱溶性感光树脂作为主体树脂，与丙烯酸官能单体配合，光引发剂常用651或葱酿类如2-乙基葱酮，颜料大多用酞菁蓝，一般 $1\\%$ 即可，还需加人较大量的填料如滑石粉；为提高触变性能，需加入气相二氧化硅等。这里特别要指出的是含有一定数量羧基的碱溶性感光树脂，交联固化成膜后，必须要能溶于 $3\\%$ 左右氢氧化钠溶液中，以便去除。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 572,
+        "chunk": "# 10. 2.4 UV阻焊油墨  \n\n印制电路板上铜质电路制成后，板面上除焊点外，其余部分均需覆盖一层阻焊剂，保证板面通过波峰焊时，仅焊点处有焊锡，其余线路图形部分不沾焊锡。在网印法中上阻焊剂就是用阻焊油墨（soldingink)。因固化方式不同，阻焊油墨也有热固型和光固型两种，目前主要用光固阻焊油墨。其阻焊图形也是由油墨通过丝网漏印经固化后形成，由于它是印制电路板上的永久涂层，因此要有优异的电性能和物理力学性能，还要能耐 $260^{\\circ}\\mathrm{C}$ （军品要耐$288^{\\circ}\\mathrm{C}$ ）高温（见表10-8)。  \n\n表10-8光固阻焊剂的性能要求  \n\n\n<html><body><table><tr><td>项 目</td></tr><tr><td>黏度(25℃)/Pa·s</td></tr><tr><td>2.0~10.0</td></tr><tr><td>细度/μm ≤20 硬度(铅笔硬度) ≥3H,≥2H(柔性板)</td></tr><tr><td>附着力(划格法) 100/100</td></tr><tr><td>0</td></tr><tr><td>耐热性[（260±2)℃×5s×2] 阻焊性[(260±2)℃×10s]</td></tr><tr><td>无沾锡</td></tr><tr><td>绝缘电阻/Ω ≥1010</td></tr><tr><td>常态</td></tr><tr><td>潮热 ≥109 ≥20</td></tr><tr><td>击穿强度/kV</td></tr><tr><td>高低温循环（-65℃/30min~125℃/30min）×100 不出现分层，起泡</td></tr><tr><td>耐化学药品性</td></tr><tr><td>HCl,10%（体积分数)，室温60min 无变化</td></tr><tr><td>NaOH，5%（质量分数)，室温60min 无变化</td></tr><tr><td>三氯乙烯，室温，60min 无变化</td></tr><tr><td>乙醇，室温，60min 无变化 V-0</td></tr><tr><td>阻燃性</td></tr></table></body></html>  \n\nUV阻焊油墨低聚物主要选择耐热性好、绝缘性好、与铜黏附性好的树脂，如双酚A-环氧丙烯酸酯、酚醛环氧丙烯酸酯和聚氨酯丙烯酸酯，目前常用的是酚醛环氧丙烯酸酯。活性稀释剂则以多官能度丙烯酸酯配以单官能团羟基酯，光引发剂则主要用651或2-乙基葱。颜料以菁绿为主，用量一般不超过1%，并可加入较多的填料，有利于提高耐热性和减少体积收缩。为了提高油墨与铜的附着力，还需加人 $1\\%\\sim2\\%$ 的附着力促进剂，如甲基丙烯酸磷酯单酯或双酯。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 573,
+        "chunk": "# 10.2.5 UV字符油墨  \n\n印制电路板上电路图及电子元件位置都需用线路和字符在电路板的正反两面进行标记，以供插件和维修使用，通常称为网印字符油墨（markingink)。有时在高频部分，为了提高绝缘性能，在阻焊油墨上再重涂字符油墨(标记油墨)。字符油墨也因固化方式不同而有热固型和光固型两种，都采用丝网漏印方式印在电路板上，也是印制电路板上永久涂层，其性能要求与阻焊剂相同。  \n\nUV字符油墨所用低聚物和活性稀释剂与UV阻焊油墨类似，由于大多用白色，颜料都选择二氧化钛，因此光引发剂要用TPO或819为好。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 574,
+        "chunk": "# 10.2.6 干膜  \n\n干膜是用于制作双面板或多层板的光固化材料，它的结构如图10-18所示，是由聚酯片  \n\n基、感光胶膜和聚乙烯薄膜三层组成。聚酯片基（ $25\\mu\\mathrm{m}$ 厚）是感光胶膜的支持体；聚乙烯薄膜（ $25\\mu\\mathrm{m}$ 厚）为保护膜，避免空气中灰尘污染感光胶膜，同时防止感光胶膜卷缠时粘连。感光胶膜是干膜的主体，根据用途不同有抗蚀干膜和阻焊于膜，其厚度也因用途不同从 $20{\\sim}100\\mu\\mathrm{m}$ 不等。  \n\n（1）抗蚀干膜抗蚀干膜由于显影的溶剂及方式不同，分为四类：溶剂型用有机溶剂显影及去膜；半水溶型用稀碱水溶液与有  \n\n![](images/975419f8b54aaa9da247422b8911a46c5745603916e8c245b18d96cb87916c09.jpg)  \n图10-18干膜结构示意  \n\n机溶剂混合显影及去膜；水溶型用稀碱水溶液显影及去膜；干剥离型不用溶剂，直接干法剥离。因溶剂型和半水溶型都会造成环境污染，所以现在抗蚀干膜主要为水溶型。  \n\n抗蚀干膜中的感光胶膜由胶黏剂、光聚合单体、光引发剂和其他添加剂组成，用溶剂配成感光涂布液，再涂覆在聚酯片基上经干燥制得。  \n\n$\\textcircled{1}$ 胶黏剂它是高分子类成膜物质，具有较好的柔韧性和拉伸强度，决定感光胶膜的物理力学性能。常用经酯化或酰胺化改性的苯乙烯-马来酸酐共聚物，还配以丙烯酸酯聚合物和纤维素醋酸丁二酸酯等树脂。  \n\n$\\textcircled{2}$ 光聚合单体在紫外曝光时进行光聚合，生成高度交联的网状结构，使胶膜有较强的抗蚀和抗化学性能。常用PETA、TMPTA、TPGDA等多官能团丙烯酸酯。  \n\n$\\textcircled{3}$ 光引发剂早期用安息香醚类、二苯甲酮和米酮等，现改用651、1173、184等光引发剂。  \n\n$\\textcircled{4}$ 其他添加剂阻聚剂用对苯二酚、对甲氧基苯酚等；增塑剂用二缩三乙二醇双醋酸酯、邻苯二甲酸二丁酯等；增黏剂用苯并三氮唑、苯并噻唑等；染料可用孔雀石绿等，色泽鲜艳，便于观察，又能透过 $300{\\sim}400\\mathrm{nm}$ 紫外光；光致变色物质，用螺吡喃、亚甲基蓝等，在紫外曝光时可变色，便于检查干膜是否曝光，曝光后可检查图像有否缺陷；溶剂为丙酮、丁酮或无水乙醇等。  \n\n抗蚀干膜在印制电路制作中有三种应用方法。  \n\n$\\textcircled{1}$ 印制-刻蚀法 主要适用于制单面板，其工艺流程为：  \n\n铜板 $\\nsim$ 贴膜前处理 $\\mathbf{\\Psi}\\to$ 贴膜 $\\mathrel{\\mathop:}\\mathrel{\\mathop\\to}\\mathbf{U}\\mathbf{V}$ 曝光 $\\star$ 显影 $\\star$ 修板 $\\mathbf{\\Psi}\\to$ 腐蚀 $\\star$ 去膜  \n\n$\\textcircled{2}$ 图形电镀-刻蚀法主要适用于制造孔金属化的双面板和多层板的外层线路，其工艺流程为：  \n\n覆铜板 $\\rightarrow$ 钻孔 $\\rightarrow$ 孔金属化→贴膜前处理 $\\rightarrow$ 贴膜 $\\rightarrow$ 曝光 $\\rightarrow$ 显影 $\\rightarrow$ 修板 $\\rightarrow$ 镀前处理→镀光亮铜→镀锡合金 $\\rightarrow$ 蚀刻→去膜  \n\n此时的抗蚀干膜也叫耐电镀干膜。  \n\n$\\textcircled{3}$ 孔掩蔽-刻蚀法采用阳底图，将干膜转移成焊盘和电路保护层，以便在蚀刻过程中金属化孔得到保护，其工艺流程为：  \n\n覆铜板 $\\rightarrow$ 钻孔 $\\rightarrow$ 化学镀铜 $\\star$ 孔金属化 $\\rightarrow$ 贴膜前处理 $\\nsim$ 贴膜→UV曝光 $\\mathbf{\\rightarrow}$ 显影 $\\rightarrow$ 蚀刻 $\\rightarrow$ 去膜此时的抗蚀干膜也叫掩孔干膜。  \n\n前处理的目的是除去铜箔表面的氧化物，制造出一定的铜表面微观粗糙度，保证干膜与铜箔表面有良好的附着力。前处理有手工清洗、机械清洗和化学清洗三种，处理后水洗干燥，马上进行贴膜。  \n\n贴膜：先从干膜上撕下聚乙烯保护膜，然后在加热加压条件下将干膜粘贴在铜箔上，温度控制在 $90{\\sim}100^{\\circ}\\mathrm{C}$ ，压力 $0.5{\\sim}0.6\\mathbf{kg}/\\mathbf{cm}^{2}$ ? $\\mathbf{\\langle1kg/cm^{2}=}0.098\\mathbf{MPa})$ 。贴膜是在贴膜机上完成（图10-19)。近年来又发展了湿法贴膜工艺，利用专用贴膜机，在贴膜前于铜箔表面形成一层水膜，在挤压下除去铜箔凹陷部位的气体，在加热和加压的贴膜过程中，水对干膜抗蚀剂起着增塑剂的作用，增加了干膜的流动性，使干膜在铜箔表面更紧密地贴合。湿法贴膜如图10-20所示，水由湿辊A（如图10-21）的两端进人，并由中心管子和孔喷出，喷出的水被海绵吸收，以保证均匀地把水挤压到基板上，当基板走到热压辊B时，水膜介于干膜和铜箔表面之间，C辊作用是将多余的水除去，D辊用来除去粘在B辊上多余的水。  \n\n![](images/fb9fd4dcd09d623e4b80f0fdab994320ddb8ef571b2c534b7fb1b71b222de041.jpg)  \n图10-19 贴膜示意  \n\n![](images/3c84b38eca9a0f407fa2291a71e71035ec77ff378b5e5d2be01facc93dbfc18e.jpg)  \n图10-20湿法贴膜示意A一给水辊；B—热辊；C—除水辊；D—除水辊；E一干膜  \n\nUV曝光：用银盐底片或重氮片与干膜聚酯片基贴合，隔片基接触曝光，UV光源用高压汞灯、碘灯或镝灯。  \n\n显影：常用 $1\\%\\sim2\\%$ 的碳酸钠溶液作显影液、液温 $30{\\sim}40^{\\circ}\\mathrm{C}$ ，大多采用机械喷淋显影。  \n\n修版：修补图像上的缺陷和除去与图像无关的疵点。  \n\n![](images/f9371ac4ef654026cc8af46152365a058b89ccfefcd721a8ac2483781bee6cbd.jpg)  \n图10-21 湿辊构造示意  \n\n检查抗蚀图像质量，对有缺陷和疵点要进行修补。  \n\n海绵辊作为湿辊上下配置；由海绵中空辊子内侧供水；由两侧供水以保证均匀润湿  \n\n蚀刻：大多用酸性氯化铜蚀刻液，温度$50^{\\circ}\\mathrm{C}$ 左右。  \n\n去墨用 $5\\%$ 的氢氧化钠溶液：温度50～  \n\n$60^{\\circ}\\mathrm{C}$ ，喷淋lmin或手工浸人后去墨。经热水洗、循环水洗、自来水冲洗，干燥后检查合格转入后序工艺上阻焊剂。  \n\n（2）阻焊干膜阻焊干膜是为了在双面板或多层板上制作阻焊图形的干膜。因显影时所用显影剂不同，有溶剂型和水溶型两大类。  \n\n阻焊干膜中的感光胶膜由耐热性好的感光性树脂、光聚合单体、光引发剂和其他添加剂组成，用溶剂配成感光涂布液，再涂覆在聚酯片基上，经干燥制得。  \n\n阻焊干膜与抗蚀干膜最大不同是其所用的树脂为耐热性好的感光性树脂，如环氧丙烯酸树脂、酚醛环氧丙烯酸树脂，对水溶性阻焊干膜，则要用带有羧基的环氧丙烯酸树脂或酚醛环氧丙烯酸树脂。  \n\n阻焊干膜由于耐热性稍差，与铜质电路贴合也易出现缺陷，成像分辨率不如光成像油墨，因此当光成像阻焊油墨一出现，便很快地取代阻焊干膜。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 575,
+        "chunk": "# 10.2.7光成像抗蚀油墨  \n\n湿膜法制作印制电路板所用的液态感光成像油墨（简称光成像油墨）是第三代光固化材料（第一代为光固化油墨，第二代为干膜)，由于它是接触曝光，所以形成图形的分辨率要高于干膜（隔片基曝光)，可以制作更精细的铜质电路。同时液体感光成像油墨厚度薄，有效利用率高，耗材少，对覆铜板铜箔表面平整度要求也不高，不易发生干膜。因铜箔表面平整度不高，往往产生与铜箔黏合缺陷，导致腐蚀或电镀时发生腐蚀液或电镀液渗液，造成导线断线、缺口或渗镀现象，影响产品合格率，故性价比高。因而液态感光成像油墨越来越多地应用在制作双面板和多层板中，液态感光阻焊油墨已替代阻焊干膜。  \n\n液态感光成像油墨有两大类：一类为制作电路时，起抗蚀（或耐电镀）作用的液态感光抗蚀（或耐电镀）油墨；另一类为液态感光阻焊油墨，起阻焊和绝缘作用。  \n\n光成像抗蚀油墨（photoimagealle etchink）在印制电路中的制作工艺流程为：  \n\n覆铜板 $\\rightarrow$ 前处理 $\\rightarrow$ 涂覆油墨 $\\rightarrow$ 预干燥 $\\rightarrow$ UV曝光 $\\cdots$ 显影 $\\rightarrow$ 水洗干燥 $\\rightarrow$ 检查 $\\rightarrow$ 蚀刻（或电度） $\\mathbf{\\rightarrow}$ 去膜 $\\star$ 水洗干燥 $\\rightarrow$ 检查 $\\rightarrow$ 转入上阻焊剂工序  \n\n前处理包括去油、酸洗、水洗、刷板和干燥，以去除覆铜板铜箔上的油污、灰尘。  \n\n油墨涂覆目前有丝网满版漏印、帘涂、辊涂和静电喷涂等。丝网满版漏印采用 $80\\sim150$ 目丝网，可手工或自动网印，设备简单，操作方便，投资小，目前仍在大量使用。帘涂（图10-22）对大批量生产适用，一般控制油墨干后厚度，双面板和多层板 $20\\mu\\mathrm{m}$ ，单面板 $10\\mu\\mathrm{m}$ 。帘涂自动化程度高，生产效率高，但投资大。近来又发展了辊（滚）涂法（图10-23)，可以双面涂覆，涂层均匀而且更薄，节省油墨，同时也缩短显影时间，减少显影液消耗。静电喷涂（图10-24）生产效率也高，但存在过喷和边缘效应问题，影响使用。  \n\n预干燥温度 $80^{\\circ}\\mathrm{C}\\pm5^{\\circ}\\mathrm{C}$ ，一般烘箱 $15\\sim20\\mathrm{min}$ ，远红外烘道 $5\\sim6\\mathrm{{min}}$ ，高红外烘道 $1\\sim$ $1.2\\mathrm{min}$ ，使油墨表干，不会沾污掩膜。 5+  \n\nUV曝光用银盐片或重氮片作掩膜，以中压汞灯或金属卤素灯为光源，接触曝光。  \n\n显影用 $1.0\\%\\sim1.5\\%$ 碳酸钠溶液， $30^{\\circ}\\mathrm{C}\\pm2^{\\circ}\\mathrm{C}$ 喷射显影 $30{\\sim}120\\mathbf{s}$ ；批量小时也可手工显影。  \n\n水洗干燥以洗去残留的显影液，热风干燥（ $50\\sim60^{\\circ}{\\mathrm{C}}$ ） $1\\mathrm{min}$ ，或烘箱干燥（ $100^{\\circ}\\mathrm{C}$ >$1\\sim2\\mathrm{min}$ 。  \n\n检查抗蚀图像质量，对有缺陷和疵点要进行修补。  \n\n蚀刻：大多用酸性氯化铜蚀刻液，温度 $50^{\\circ}\\mathrm{C}$ 左右。  \n\n![](images/c5b22d0838dabe815488f7dc5988707dc9049cebcd96e2d112aea8256c7640e5.jpg)  \n图10-22 帘涂示意  \n\n![](images/9a3e4361ee8550d9b84e76a566cc309eca0b0dd55c0b020ffb2bee2e11096ac8.jpg)  \n图10-23 辊涂工艺示意  \n\n![](images/dcce8a3224cd3abe63f1327d21a438a4d18bfd96303dce2df65c9898de306e52.jpg)  \n图10-24 静电喷涂示意  \n\n去墨：用 $5\\%$ 的氢氧化钠水溶液，温度 $50\\sim60^{\\circ}{\\mathrm C}$ ，喷淋 $1\\mathrm{min}$ ，或手工浸人后去墨。经 热水洗、循环水洗、自来水冲洗，干燥后检查合格，转人后序工艺上阻焊剂。“ n",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 576,
+        "chunk": "# 10.2.8光成像阻焊油墨  \n\n光成像阻焊油墨（photoimagealle solder ink）用于制造双面板或多层板阻焊图形，其制作工艺流程为：  \n\n经蚀刻、电镀的覆铜板→前处理→涂布油墨→烘干→第二面涂油墨→烘干→UV曝光→  \n\n显影→热固化 $\\star$ 检查前处理用机械磨刷或酸洗。  \n\n油墨涂布可采用 $80\\sim150$ 目丝网满板漏印，油墨厚度（干后） $20\\sim25\\mu\\mathrm{m}$ 。大批量生产可用帘涂、静电喷涂或辊涂。由于光成像阻焊油墨是双重固化体系油墨，为双组分油墨，网印前按比例充分混合均匀，才能使用。单面板只要印一面即可，双面板和多层板则需在印好第一面并干燥后，再印第二面，以除去油墨中少量溶剂，不使曝光时出现粘掩膜。  \n\n干燥多采用热风干燥，单面板 $70\\sim75^{\\circ}\\mathrm{C}$ ， $10\\mathrm{\\sim}15\\mathrm{min}$ ；双面板、多层板第一面 $70\\sim$ $75\\mathrm{^\\circC}$ ， $8\\mathrm{{min}}$ ，第二面 $70{\\sim}75\\mathrm{^\\circC}$ ， $10\\mathrm{\\sim}20\\mathrm{min}$ 。  \n\nUV曝光用银盐片或重氮片作掩膜，以中压汞灯或金属卤素灯为光源接触曝光。  \n\n显影用 $1.0\\%$ 的碳酸钠溶液， $20{\\sim}30^{\\circ}\\mathrm{C}$ ，喷射显影 $60{\\sim}120\\mathrm{s}$ ，再水洗除去显影液，热固化在 $140{\\sim}150^{\\circ}\\mathrm{C}$ 下 $30\\mathrm{{min}}$ ，以使油墨进一步发生热交联，提高耐热性等综合性能。  \n\n光成像阻焊油墨是光固化和热固化双重固化油墨，其主体树脂为碱溶性感光树脂，热固化树脂为环氧树脂，其他组成还有多官能活性稀释剂、光引发剂、热固化剂、颜料、填料及助剂等。  \n\n（1）碱溶性感光树脂主要有酸酐改性的环氧丙烯酸树脂、酸酐改性（甲基）酚醛环氧丙烯酸树脂、酸酐改性的聚氨酯丙烯酸树脂、丙烯酸化的苯乙烯-马来酸酐聚合物、含羧基的醇酸丙烯酸树脂等，但以前两种酸酐改性的环氧丙烯酸树脂最为常用。  \n\n（2）热固性树脂常用双酚A环氧树脂、（甲基）酚醛环氧树脂、脂环族环氧树脂、三缩水甘油基三聚异氰酸酯等，以其中一种或两种混合使用。  \n\n（3）活性稀释剂最常用TMPTA和PETA，以及TPGDA、PEGDA，还可用季戊四醇四丙烯酸酯、双季戊四醇五/六丙烯酸酯等有利于提高固化速率的活性稀释剂，也常加入HEA、HEMA等带羟基的单官能活性稀释剂，改善油墨黏度、提高树脂间相容性、有助于提高对铜箔的附着力。  \n\n（4）常用651、907、369、ITX等自由基裂解型光引发剂，由于过去阻焊剂都用绿色，现在颜料多样化，有红色、紫色、蓝色、黄色、甚至白色和黑色，故光引发剂需依据不同颜色而加以不同选择。一般都用 $2{\\sim}3$ 种光引发剂组合使用，以提高光引发效率。还可添加少量TPO，特别是白色，则要以TPO为主。  \n\n（5）一般使用二氰二胺、咪唑等高温固化剂，以保证油墨的贮存稳定性和使用安全性。  \n\n（6）过去主要用菁绿颜料，现在不同颜色就要选用不同耐热性和耐候性好的颜料，如酞菁蓝、双偶氮黄等。填料常用滑石粉、硫酸钡、二氧化硅等，选择热容大、热传导性好的填料对固化膜的耐热性有帮助。 C 10.  \n\n光成像阻焊油墨由于是双重固化型油墨现在都做成双组分油墨，将主体树脂、热固性树脂和部分活性稀释剂、颜料、填料作为A组分，光引发剂和热固化剂和部分活性稀释剂为B组分，使用前将A和B组分按一定比例搅拌均匀后进行涂覆。混合后油墨，不能长期保存，主要因热固化树脂在热固化剂作用下，缓慢发生化学反应，体系黏度逐步增大，影响使用，所以要现用现配，用多少配多少，不浪费油墨。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 577,
+        "chunk": "# 10.2.9电沉积光致抗蚀剂  \n\n电沉积光致抗蚀剂（eleclrodepositedphotoresist）是将光致抗蚀剂中的官能团经过亲水化后，分散到水中形成树脂基团，通电后树脂基团向着与基团极性相反的电极移动，在极板（铜基板）的表面形成一层树脂层，此过程为电沉积（electrodeposition，简称ED)，如图10-25所示。电沉积光致抗蚀剂根据官能团不同，分为两类：一类官能团是羧基，铜基板作为阳极，称为阴离子型；另一类官能团是氨基，铜基板为阴极，称为阳离子型。现在主要电沉积光致抗蚀剂为阴离子型，即为含羧基的感光性树脂，与有机胺中和反应后，变成亲水的羧基阴离子感光性树脂。  \n\n![](images/78035caa1d08418350ab4ab345b3372c3dda35428e6628ad27c2dfd0a581675a.jpg)  \n图10-25电沉积光致抗蚀剂原理  \n\n电沉积光致抗蚀剂法通过电解沉积过程在铜箔表面形成光致抗蚀剂保护膜，光致抗蚀剂与铜箔是以化学键形式黏合，能保证在制作精细图形时有足够的和强劲的黏合力。同时，电沉积光致抗蚀剂层能很好地迎合铜表面的凹凸，可以提高在显影、蚀刻时的可靠性。而且在线路板的通孔内也形成保护膜层，因此通孔内也能保护。  \n\n电沉积光致抗蚀剂具有光刻性，经过UV曝光使树脂结构发生变化，改变其对显影液的溶解性。如曝光部分不溶于显影液，保护层下面的铜箔在腐蚀液中不被腐蚀，就称为阴型电沉积光致抗蚀剂；若曝光部分溶于显影液，保护层下面的铜箔在腐蚀液中被腐蚀掉，就称为阳型电沉积光致抗蚀剂。阴型和阳型电沉积光致抗蚀剂的曝光、显影和剥离过程的反应如图10-26和图10-27所示。  \n\n电沉积光致抗蚀剂新工艺的优点是： $\\textcircled{1}$ 分辨率高，可达 $20\\sim30\\mu\\mathrm{m}$ ， $\\textcircled{2}$ 改善抗蚀层对基材的附着性； $\\textcircled{3}$ 对不平整基材表面的适应性良好； $\\textcircled{4}$ 在短时间内可以形成膜厚均匀的抗蚀膜； $\\textcircled{5}$ 涂层流体为水溶液，既可防止环境污染，又可防止发生不安全事故。  \n\n电沉积光致抗蚀剂工艺流程为：  \n\n铜箔表面清洁处理 $\\rightarrow$ 电沉积 $\\rightarrow$ 清洗 $\\rightarrow$ 烘烤 $\\mathbf{\\rightarrow}$ 外加保护膜 $\\mathbf{\\rightarrow}$ 干燥 $\\rightarrow$ 冷却 $\\rightarrow$ UV曝光→显影 $\\rightarrow$ 蚀刻 $\\rightarrow$ 去膜 $\\scriptstyle\\rightarrow$ 水洗干燥 $\\rightarrow$ 检查 $\\rightarrow$ 转人上阻焊剂工序 Y 55  \n\n电沉积光致抗蚀剂目前都用带羧基的感光性树脂，经亲水化后，再分散到水中。只是阴型电沉积光致抗蚀剂为带羧基的丙烯酸树脂，而阳型电沉积光致抗蚀剂为带羧基的邻重氮萘鼠树脂。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 578,
+        "chunk": "# 10.2.10 挠性印制板用UV油墨  \n\n挠性印制板（flexible printedboard）也叫柔性印制板，用于挠性电路。挠性电路是为提高空间利用率和产品设计灵活性而设计的，能满足更小型和更高密度安装的设计需要，也有助于减少组装工序和增强可靠性，是满足电子产品小型化、轻量化和移动要求的唯一解决方法。挠性电路可以移动、弯曲、扭转，而不损坏导线，可以有不同的形状和特别的封装尺寸。  \n\n早期挠性电路主要应用在小型或薄型电子产品及刚性印制板之间的连接领域，以后逐渐应用到计算机、笔记本电脑、数码相机、打印机、驱动器、汽车音响、摄像机、心脏起搏器、助听器、医疗设备等电子产品，目前几乎所有使用的电子产品里都有挠性电路。  \n\n![](images/afe849b4f8f8b3362ec78e8fbaea3154499e92bd52446d5dd5c2f4a15af44dfd.jpg)  \n图10-26阴型电沉积光致抗蚀剂曝光、显影和剥离示意  \n\n![](images/274306d1842921d98a6db071e5e64ad61cdfdb9ca2529108dff1a102f8c13a0c.jpg)  \n图10-27阳型电沉积光致抗蚀剂曝光、显影和剥离示意  \n\n![](images/1a8f2d511f94c2dfe1bf383f8e7f7b05e5db004794ced06e7b3de30a9072d964.jpg)  \n\n挠性印制板的结构其绝缘基材是一种可挠曲的绝缘薄膜，目前常用的有聚酰亚胺(polyimide，简写 PI）薄膜、聚酯（polyester，简写 PET）薄膜和聚四氟乙烯（polytet-rafluoroethylene，简写PTFE）薄膜，三种薄膜性能见表10-9，用环氧胶黏剂或丙烯酸胶黏剂，把薄膜与铜箔黏合而成。  \n\n表10-9聚酰亚胺、聚酯、聚四氟乙烯介质薄膜的性能  \n\n\n<html><body><table><tr><td>性能</td><td>聚酰亚胺</td><td>聚酯</td><td>聚四氟乙烯</td></tr><tr><td>极限张力/MPa</td><td>172</td><td>172</td><td>20.7</td></tr><tr><td>极限延伸率/%</td><td>70 ·</td><td>120</td><td>300</td></tr><tr><td>因蚀刻引起的尺寸变化/(mm/m)</td><td>2.5</td><td>5.0</td><td>5.0</td></tr><tr><td>介电常数(103Hz)</td><td>3.5</td><td>3.2</td><td>2.1</td></tr><tr><td>损耗角正切(103Hz)</td><td>0.0025</td><td>0.005</td><td>0.0001</td></tr><tr><td>体积电阻率/Ω·cm</td><td>1012</td><td>1012</td><td>1012</td></tr><tr><td>燃烧性</td><td>自熄</td><td>易燃</td><td>不燃烧</td></tr><tr><td>介电强度/(mV/m)</td><td>275</td><td>300</td><td>17</td></tr><tr><td>吸潮/%</td><td>2.7</td><td><0.8</td><td>0.01</td></tr><tr><td>耐热性能/℃</td><td>400</td><td>150</td><td>260</td></tr><tr><td>浮焊试验</td><td>通过</td><td>通过</td><td>通过</td></tr></table></body></html>  \n\n挠性印制板也有单面挠性板、双面挠性板和多层挠性板之分，还有刚挠性印制板。挠性印制板的制作也与刚性印制板相同，需要经蚀刻制成铜质电路，再涂覆绝缘阻焊层。蚀刻前涂布抗蚀剂也采用丝网法、干膜法和湿膜法，分别使用抗蚀油墨、抗蚀干膜和光成像抗蚀油墨。涂覆绝缘阻焊层多采用丝网法和湿膜法，分别使用挠性阻焊油墨和光成像阻焊油墨。由于挠性印制板需弯曲、折叠和移动，就要求挠性阻焊油墨能适应此种要求，故油墨的主体树脂要选用柔性好的聚氨酯丙烯酸酯，活性稀释剂也要选择柔韧性好的功能性丙烯酸酯，以保证在25个周期弯折后，固化的阻焊膜不应显示出分离、破裂或从基材、导线上分层等现象。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 579,
+        "chunk": "# 10.2.11 积层多层板用光固化材料  \n\n积层多层板（build up multilayer printedboard，简写BUM）是以一般多层板为内芯，在其表面制作由绝缘层、导体层和层间连接的通孔所组成的一层电路板，多次反复，采用层层叠积方式而制得的多层板。由于受板面平整度的限制，积层多层板积层的层数大多不超过四层。  \n\n积层多层板是为适应电子产品“轻、薄、短、小”化和低成本的要求而产生的新品种，特别适用近年来表面安装技术迅速地由扁平方形封装向球栅阵列方向发展和更高密度的芯板封装技术开发、发展和应用。这是由于积层多层板是用积层方法交替制作绝缘层和导电层，其层间可随意用盲孔进行导通，所以其积层厚度很薄（ $(<70\\mu\\mathrm{m})$ ，互连密度可很高（线宽/间距可小至 $40\\mu\\mathrm{m}/45\\mu\\mathrm{m}$ ，导通孔可小至 $\\phi100\\mu\\mathrm{m})$ ，表面安装密度可大大提高。而且积层多层板制造可充分利用现有印制电路板的生产设备和设施，只要增添小量轻型生产设备即能生产，其投资是很小的，生产成本也较低。  \n\n积层多层板的制造可分为感光树脂型和非感光树脂型两种制造方法，其最大区别在导通孔形式上，前者用光化学法蚀孔，而后者采用激光蚀孔或等离子体蚀孔（图10-28)。  \n\n![](images/ca70cc25483f6a06eeb565bf023c3b89a319836e1c0e224b14f3d95e9441430a.jpg)  \n图10-28各种BUM用绝缘材料制造BUM的工艺流程  \n\n（1）非感光树脂型制造积层多层板按常规生产技术制造多层板作内层；薄铜箔涂覆上绝缘介质材料（大多为环氧树脂)，形成黏结薄膜，烘干后，用激光或等离子体，蚀孔出导通孔；与内层印制板压在或层压形成积层结构，并经激光或等离子蚀孔，钻通孔；孔金属化和电镀；再用抗蚀干膜或光成像抗蚀油墨法制铜质电路导体层。如此重复上述过程再积层一层线路。  \n\n（2）感光树脂型制造积层多层板在内层芯板上涂覆一层感光型的绝缘介质材料（如光成像阻焊油墨)，烘干后，经曝光、显影形成所需互连的导通孔，经化学镀铜或电镀，再经图像转移，便可形成层间互连而表面层更高密度的导体层。如此重复再积层第二层、第三层，由于受板面平整度的限制大多不超过四层（图10-29)。  \n\n![](images/e9975d21f3d888bc36aec072f9a2fcbeba306d406f6937070a9744b2ac599071.jpg)  \n图10-291 BUM板制作（感光树脂）过程示意",
+        "category": " Introduction"
+    },
+    {
+        "id": 580,
+        "chunk": "# 10.2.12U UV印制电路用油墨和干膜参考配方  \n\n以下配方中单位为质量份。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 581,
+        "chunk": "# （1）UV抗蚀油墨参考配方  \n\n<html><body><table><tr><td>芳香酸甲基丙烯酸半酯[SB500含50% (EO)TMPTA] (EO）TMPTA HEMA 651</td><td>34.8 ITX 酞菁蓝 21.0 SiO2 21.0 滑石粉 2.0</td><td>1.0 0.2 3.0 14.0 流平剂（SR012） 1.0</td></tr><tr><td colspan=\"3\">BP 2.0 （2）UV抗蚀油墨参考配方</td></tr><tr><td>芳香酸甲基丙烯酸半酯[SB50050% (EO)TMPTA] 附着力增强型EA（CN142） (EO)TMPTA HEMA 651</td><td>45.0 ITX BP 5.0 菁蓝 10.0 滑石粉 17.0 SiO（Acrosil 200） 2.0 非硅流平剂（SR012）</td><td>1.0 1.0 0.2 14.0 3.0</td></tr></table></body></html>  \n\n（3）UV抗蚀油墨参考配方  \n\n\n<html><body><table><tr><td>酸酐改性EA</td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>SiO2 2-EA</td><td></td><td></td><td></td><td>3 2</td></tr><tr><td>651</td><td></td><td></td><td></td><td>1</td></tr><tr><td>流平消泡剂</td><td></td><td></td><td></td><td>1</td></tr><tr><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n（4）UV抗蚀油墨参考配方  \n\n\n<html><body><table><tr><td>马来酸酐共聚物</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 582,
+        "chunk": "# （5）UV抗蚀油墨参考配方  \n\n<html><body><table><tr><td>BaSO4</td><td></td><td></td><td></td><td>4</td></tr><tr><td>SiO2</td><td></td><td></td><td></td><td>3</td></tr><tr><td>酥菁蓝</td><td></td><td></td><td></td><td>1</td></tr><tr><td>2-EA 651</td><td></td><td></td><td></td><td>2 1</td></tr></table></body></html>  \n\n<html><body><table><tr><td>高酸值PEA</td><td></td><td></td><td></td><td>50</td></tr><tr><td>TPGDA</td><td></td><td></td><td></td><td>20</td></tr><tr><td>651</td><td></td><td></td><td></td><td>4</td></tr><tr><td>菁蓝</td><td></td><td></td><td></td><td>1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 583,
+        "chunk": "# （6）UV抗电镀油墨参考配方  \n\n<html><body><table><tr><td>滑石粉 SiO2</td><td></td><td></td><td></td><td></td><td>4</td><td>20</td></tr><tr><td>流平剂</td><td></td><td></td><td></td><td></td><td>1</td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>高酸值PEA EA</td><td></td><td>38.5 10.0 20.0</td><td>菁蓝 滑石粉 SiO2</td><td></td><td>0.5 20.0 6.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 584,
+        "chunk": "# （7）UV抗蚀刻喷墨油墨参考配方  \n\n<html><body><table><tr><td>EA</td><td>10.30 369 1.40 ITX</td><td></td><td>2.00 1.00</td></tr><tr><td>丙烯酸壬基苯氧基乙酯 （乙氧基）4双酚A二丙烯酸酯</td><td>3.40</td><td>LiNO3</td><td>0.30</td></tr><tr><td>(PO)TMPTA</td><td>1.00</td><td>FC-430</td><td>0.05</td></tr><tr><td>(PO）NPGDA</td><td>5.10</td><td>甲氧基苯酚</td><td>0.04</td></tr><tr><td>含羧基丙烯酸酯</td><td>14.80</td><td>甲醇</td><td>52.96</td></tr><tr><td>Rad Cure</td><td>5.10</td><td>丁酮</td><td>2.55</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 585,
+        "chunk": "# （8）UV阻焊油墨参考配方  \n\n<html><body><table><tr><td>EA TMPTA HEMA</td><td>25.0 30.0 10.0</td><td>滑石粉 SiO2 附着力促进剂</td><td>30.0 1.0 0.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 586,
+        "chunk": "# （9）UV阻焊油墨参考配方  \n\n<html><body><table><tr><td>附着力增强型EA（CN144） TMPTA (EO)TMPTA IBOA HEMA</td><td>24.0 ITX 14.0 BP 10.0 菁绿 7.0 滑石粉</td><td>0.5 2.0 0.5 19.0 SiO(Aerosil200） 3.0 非硅流平剂（SR012） 1.0</td></tr></table></body></html>  \n\n（10）UV阻焊油墨参考配方  \n\n\n<html><body><table><tr><td>附着力增强型EA（CN142）</td><td></td><td>30.0</td></tr><tr><td>TMPTA</td><td></td><td>24.0</td></tr><tr><td>HEMA</td><td></td><td>20.0</td></tr><tr><td>651 ITX</td><td></td><td>2.0 0.5</td></tr></table></body></html>  \n\n<html><body><table><tr><td>BP 酞菁绿</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 587,
+        "chunk": "# （11）UV阻焊油墨参考配方  \n\n<html><body><table><tr><td>EA TMPTA BP DEMK</td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>酞菁绿</td><td></td><td></td><td></td></tr><tr><td>BaSO 表面活性剂和助剂</td><td></td><td></td><td>25 3</td></tr><tr><td></td><td></td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 588,
+        "chunk": "# （12）UV阻焊油墨参考配方  \n\n<html><body><table><tr><td>FA</td><td></td><td></td><td></td><td>20</td></tr><tr><td>EA TMPTA</td><td></td><td></td><td></td><td>10 13</td></tr><tr><td>DPHA</td><td></td><td></td><td></td><td>3</td></tr><tr><td>HEMA</td><td></td><td></td><td></td><td>18</td></tr><tr><td>BaSO4</td><td></td><td></td><td></td><td>2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 589,
+        "chunk": "# （13）阻焊油墨参考配方  \n\n<html><body><table><tr><td>滑石粉 SiO2</td><td></td><td></td><td></td><td></td><td>25 3</td></tr><tr><td>2-EA</td><td></td><td></td><td></td><td></td><td>3</td></tr><tr><td>651</td><td></td><td></td><td></td><td></td><td>1</td></tr><tr><td>流平消泡剂</td><td></td><td></td><td></td><td></td><td>1</td></tr><tr><td>酞菁绿</td><td></td><td></td><td></td><td></td><td>1</td></tr></table></body></html>  \n\n<html><body><table><tr><td>FA</td><td></td><td></td><td>24</td></tr><tr><td>TMPTA</td><td></td><td></td><td>14 8</td></tr><tr><td>EO-TMPTA IBOA</td><td></td><td></td><td>12</td></tr><tr><td>HEMA</td><td></td><td></td><td>17</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 590,
+        "chunk": "# （14）UV阻焊油墨参考配方  \n\n<html><body><table><tr><td>滑石粉</td><td></td><td></td><td></td><td>19</td></tr><tr><td>菁绿</td><td></td><td></td><td></td><td>0.5</td></tr><tr><td>651</td><td></td><td></td><td></td><td>2</td></tr><tr><td>BP</td><td></td><td></td><td></td><td>2</td></tr><tr><td>ITX</td><td></td><td></td><td></td><td>0.5</td></tr></table></body></html>  \n\n<html><body><table><tr><td>脂肪族PUA</td><td>50 TPGDA 14 PETA</td><td></td><td>16 5 5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 591,
+        "chunk": "# （15）UV阻焊油墨参考配方  \n\n<html><body><table><tr><td>脂肪族PUA</td><td>40</td><td>HEMA</td><td>28</td></tr><tr><td>乙氧基双酚A二丙烯酸酯</td><td rowspan=\"2\">18 4</td><td rowspan=\"2\">PETA 651</td><td rowspan=\"2\">5 5</td></tr><tr><td>TMPTA</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 592,
+        "chunk": "# （16）UV柔性版阻焊油墨参考配方  \n\n<html><body><table><tr><td>PUA TMPTA HEMA</td><td>25.0 35.0 10.0</td><td>酞菁绿 滑石粉 SiO2</td><td></td><td>0.5 22.5 3.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 593,
+        "chunk": "# （17）UV柔性板阻焊油墨参考配方  \n\n<html><body><table><tr><td>PUA TPGDA</td><td></td><td>40.0 28.0</td><td>滑石粉 SiO2</td><td></td><td></td><td>20.0</td></tr><tr><td></td><td></td><td></td><td>5.0</td><td>流平剂</td><td></td><td>4.5</td></tr><tr><td>651</td><td></td><td></td><td></td><td></td><td></td><td>2.0</td></tr><tr><td>菁蓝</td><td></td><td>0.5</td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n（18）UV字符油墨参考配方  \n\n\n<html><body><table><tr><td>EA</td><td></td><td>41.3</td><td>1173</td><td></td><td>4.0</td></tr><tr><td>TMPTA</td><td></td><td>17.0</td><td>TiO2</td><td></td><td>10.0</td></tr><tr><td>NPGDA</td><td></td><td>8.5</td><td>滑石粉</td><td></td><td>17.0</td></tr><tr><td>TPO</td><td></td><td>2.0</td><td>有机硅助剂</td><td></td><td>0.2</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 594,
+        "chunk": "# （19）UV字符油墨参考配方  \n\n天海线中  \n\n\n<html><body><table><tr><td>FA TMPTA</td><td rowspan=\"3\"></td><td rowspan=\"3\">30 TiO2 30 滑石粉 10 SiO2 1 流平剂 3</td><td></td><td>10</td></tr><tr><td>HEMA</td><td></td><td>11 3</td></tr><tr><td>TPO 184</td><td></td><td>2</td></tr></table></body></html>  \n\n用光！  \n\n\n<html><body><table><tr><td>EA TMPTA HEMA ITX 对二甲氨基苯甲酸异戊酯</td><td>25.0 14.0 13.0 3.0 1.5 10.0</td><td>滑石粉 附着力促进剂PM-2 CaCO3 硅消泡剂 对甲氧基苯酚</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 595,
+        "chunk": "# （20）UV字符油墨参考配方",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 596,
+        "chunk": "# （21）UV字符喷墨油墨参考配方  \n\n<html><body><table><tr><td>三官能团脂肪族PUA（CN945B85） HDDA</td><td>20.0 15.0</td><td>819 1173</td><td>1.0 2.0</td></tr><tr><td>（EO)PETA</td><td>19.0</td><td>TiO2</td><td>20.0</td></tr><tr><td>THFA</td><td>10.0</td><td>BYK-LPN7057</td><td>1.0</td></tr><tr><td>双官能团胺助引发剂（CN386）</td><td>2.0</td><td>BYK333</td><td>0.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 597,
+        "chunk": "# （22）光成像抗蚀油墨参考配方  \n\n<html><body><table><tr><td>马来酸酐聚合物 DPHA HEMA</td><td>40 6 10 25</td><td>ITX 907 菁蓝 助剂</td><td></td><td>1 4 1 1</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 598,
+        "chunk": "# （23）光成像抗蚀油墨参考配方  \n\n<html><body><table><tr><td>改性苯乙烯/马来酸酐树脂 TMPTA</td><td>64.50 20.60 10.30 3.62</td><td>附着力促进剂 染料 抗氧剂 流平剂</td><td>0.17</td><td>0.17 0.13 0.11</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 599,
+        "chunk": "# （24）光成像抗蚀油墨参考配方  \n\n<html><body><table><tr><td>高酸值感光树脂 TPGDA</td><td></td><td>40.0 28.0 5.0</td><td>滑石粉 SiOz 流平剂</td><td></td><td>20.0 4.5 2.0</td></tr></table></body></html>\n\n$\\textcircled{1}$ 可为高酸值PEA或苯乙烯-马来酸酐树脂。  \n\n（25）光成像抗蚀油墨参考配方  \n\n\n<html><body><table><tr><td>碱溶性超支化聚酯甲基丙烯酸酯 酚醛环氧树脂 DPEHA</td><td>100.0 907 42.3 三聚氰胺 15.0 双氰胺</td><td>8.0 3.0 0.3</td></tr><tr><td colspan=\"3\">（26）光成像阻焊油墨参考配方 -气 MT</td></tr><tr><td>酸酐改性EA DPHA HEMA 滑石粉 BaSO4 SiO2 ITX</td><td>35.0 907 10.0 651 10.0 溶剂 10.0 流平剂（BYK405） 15.0 硅消泡剂 2.0 酞菁绿 1.0</td><td>3.0 2.0. 10.0 0.5 0.5 1.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 600,
+        "chunk": "# （27）光成像阻焊油墨参考配方  \n\n<html><body><table><tr><td>高酸值感光树脂 TMPTA 651</td><td>35 5 7 1</td><td>滑石粉 15 SiO2 5 流平剂 2</td></tr></table></body></html>  \n\n<html><body><table><tr><td>酸酐改性FA DPHA HEMA 滑石粉 BaSO4 菁绿</td><td></td><td>30.0 SiO2 15.0 ITX 10.0 907 20.0 流平剂（BYK405） 3.0 消泡剂（丙烯酸硅氧烷酯） 1.0 溶剂</td><td>12.0</td><td>2.0 1.5 4.5 0.5 0.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 601,
+        "chunk": "# （28）光成像阻焊油墨参考配方  \n\n童   \n\n\n<html><body><table><tr><td>酸酐改性FA 双酚A环氧树脂 乙基溶纤剂 PETA HEMA 滑石粉</td><td>40.0 5.0 5.0 8.0 9.0 15.0 10.0</td><td>对二甲胺基苯甲酸乙酯 流平消泡剂</td><td>0.8 2.0 2.0 1.0 1.0</td></tr></table></body></html>  \n\n（29）光成像阻焊油墨参考配方  \n\n\n<html><body><table><tr><td>酸酐改性FA PETA ITX 651 对二甲氨基苯甲酸乙酯</td><td>40.0 10.0 2.0 3.0 2.0 0.7</td><td>滑石粉 硫酸钡 SiO2 异氰酸三缩水甘油酯 乙纤溶纤剂 热固化剂</td><td>8.0 10.0 0.8 15.0 7.0</td></tr></table></body></html>  \n\n（30）光成像阻焊油墨参考配方  \n\n\n<html><body><table><tr><td>酸酐改性FA DPHA</td><td></td><td>50.0 5.0 菁绿</td><td>异氰酸三缩水甘油酯 5.0 0.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 602,
+        "chunk": "# （31）光成像阻焊油墨参考配方  \n\n<html><body><table><tr><td>滑石粉</td><td>11.4</td><td>907 1.5</td></tr><tr><td>651</td><td>2.0</td><td>双氰胺 1.0</td></tr><tr><td>ITX</td><td>1.5</td><td>乙基溶纤剂 2.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 603,
+        "chunk": "# （32）光成像阻焊油墨参考配方  \n\n<html><body><table><tr><td>酸酐改性FA</td><td></td><td>32.0 6.0</td><td>651 ITX</td><td></td><td></td><td>2.0 1.0</td></tr><tr><td>环氧树脂 TMPTA</td><td></td><td>8.0</td><td>907</td><td></td><td></td><td>2.0</td></tr><tr><td>HEMA</td><td></td><td>10.0</td><td>EDAB</td><td></td><td></td><td>1.0</td></tr><tr><td>溶剂</td><td></td><td>10.0 20.0</td><td>酞菁绿</td><td></td><td></td><td>0.5</td></tr><tr><td>滑石粉</td><td></td><td>5.0</td><td>消泡剂 流平剂</td><td></td><td></td><td>0.5</td></tr><tr><td>SiO2</td><td></td><td></td><td></td><td></td><td></td><td>0.5</td></tr><tr><td>咪唑</td><td></td><td>1.5</td><td></td><td></td><td></td><td></td></tr></table></body></html>\n\n于服",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 604,
+        "chunk": "# （33）多层板用光成像油墨参考配方  \n\nA组分：  \n\n\n<html><body><table><tr><td>六氢苯酐改性EA</td><td>55.0</td><td>SiO2</td><td>14.0</td></tr><tr><td>TPGDA</td><td>12.0</td><td>菁绿</td><td>0.5 1.0</td></tr><tr><td>三羟甲基丙烷二烯丙基醚</td><td>15.0</td><td>消泡剂BYK361</td><td></td></tr><tr><td>双氰胺</td><td>2.0</td><td>流平剂BYK346</td><td>0.5</td></tr></table></body></html>  \n\nB组分：  \n\n<html><body><table><tr><td>甲酚醛环氧树脂 双甲基丙烯酸丁二酯 907</td><td>55.0 25.0 5.0</td><td>184 三羟甲基丙烷二烯丙基醚</td><td>6.0 8.5 0.5</td></tr></table></body></html>  \n\nA $\\mathbf{B}=3:1$ 混合搅匀后使用。  \n\n（34）抗蚀干膜参考配方  \n\n<html><body><table><tr><td>聚甲基丙烯酸丁酯（Mw=200000） 氯化聚异戊二烯（Mw=19000） 氯化聚丙烯（M=62000） 三乙二醇二癸酸酯/三乙二醇二辛酸酯 混合物</td><td colspan=\"2\">6.0 二苯甲酮 12.0 米蛋酮 6.0 维多利亚绿染料 3.0 无色染料 氯甲烷</td></tr><tr><td colspan=\"2\">PETA 20.0 （35）抗蚀干膜参考配方</td></tr><tr><td>甲基丙烯酸甲酯/丙烯酰胺（97/3）共 聚物 TMPTA 38.5 二乙烯基乙撑脲 1.5 BP 2.5</td><td>54.0 结晶紫 0.011 酸敏变色染料 0.3 聚已二酸丙二醇酯 3.5 N-亚硝基二苯胺 0.025 硅油 0.3</td></tr><tr><td colspan=\"2\">1，4-双（二氯甲基）苯 1.5 醋酸乙酯 140.0 （36）抗蚀干膜参考配方</td></tr><tr><td>甲基丙烯酸（23）-甲基丙烯酸甲酯（66）- 40.00 丙烯酸丁酯（11）共聚物 苯氧基聚乙二醇单丙烯酸酯 10.00 EO-TMPTA 24.00 偶氮染料 9-苯基吖啶</td><td>增黏剂苯并三唑 0.05 增黏剂羟基苯并三唑 0.05 抗氧剂甲基氢 0.15 0.75 0.20 染料Flexoblue680 0.45</td></tr></table></body></html>\n\n加人适量增塑剂，用丁酮/异丙醇稀释，涂于PET膜上，干燥，得干膜。  \n\n<html><body><table><tr><td colspan=\"3\">（37）抗蚀干膜参考配方</td></tr><tr><td>丙烯酸（10）-甲基丙烯酸（15）-甲基丙烯酸 甲酯（60）-丙烯酸异辛酯（15）共聚物 二苯甲酮 4,4-二乙氨基二苯甲酮 结晶紫 对甲苯磺酸-水化物</td><td>50 钻石绿 单体9G 2.0 单体APG-400 1.0 单体BPE-500 3.0 丁酮 0.5</td><td>0.5 10.0 10.0 10.0 13.0</td></tr><tr><td colspan=\"3\">（38）抗蚀干膜参考配方 40</td></tr><tr><td>苯乙烯-甲基丙烯酸（7：3）共聚物 TMPTA</td><td>对-二甲氨基苯甲酸异戊酯 对苯二酚</td><td>0.04 900 9</td></tr><tr><td>ITX （39）抗蚀干膜参考配方</td><td>9 β甲氧基醋酸酯</td><td></td></tr><tr><td>甲基丙烯酸甲酯-丙烯睛-丙烯酸缩水甘1196.0 油共聚物（摩尔比65：10：25） 甲基丙烯酸甲酯-丙烯酸羟乙酯共聚物557.0 （摩尔比90：10） 丁酮</td><td>叔丁基 2,6-二叔丁基苯酚 乙基紫</td><td>142.0 34.5 2.5 8800.0</td></tr><tr><td colspan=\"3\">TEGDA 262.0 （40）抗蚀干膜参考配方</td></tr><tr><td>丙烯酸羟乙酯改性苯乙烯-马来酸酐共聚物68.5 PETA 22.0 651 2.5</td><td>二缩三乙二醇二醋酸酯 苯并三氮唑 亚甲基蓝 丁酮</td><td>6.0 0.3 0.5 300.0</td></tr><tr><td>对甲氧基苯酚 （41）抗蚀干膜参考配方 甲基丙烯酸甲酯-丙烯酸共聚物 56.0</td><td>0.2 无色结晶紫染料</td><td>0.5</td></tr><tr><td>TMPTA 双酚A二乙二醇二丙烯酸酯</td><td>18.5 二乙二醇二醋酸酯 16.5 醋酸乙酯</td><td>6.5 250.0</td></tr><tr><td colspan=\"3\">651 2.0 （42）抗蚀干膜参考配方</td></tr><tr><td>甲基丙烯酸甲酯-甲基丙烯酸丁酯-甲基15.00 丙烯酸羟丙酯共聚物（1：1：1） TEGDA 2.34</td><td>特丁基葱 三氯乙烯</td><td>1.41 106.25</td></tr><tr><td colspan=\"3\">（43）抗蚀干膜参考配方 100.0</td></tr><tr><td>聚氯乙烯树脂 甲基丙烯酸甲酯低聚物 TEGDA 丁二酸单-β甲基丙烯酸氧乙酯</td><td>对-二甲氨基苯甲酸异戊酯 40.0 对甲氧基苯酚 20.0 结晶紫 70.0 甲基乙基酮</td><td>1.0 0.1 0.3 300.0</td></tr><tr><td colspan=\"3\">DETX 3.0 （44）全息图软模压复制用光固化材料参考配方</td></tr><tr><td>EA 100.0 DEGDA MMA</td><td>邻苯二甲酸二丁酯 15.0 651 9.0 流平剂</td><td>9.0 2.0 1.0</td></tr></table></body></html>  \n\n（45）UV彩色点阵黑墨参考配方转成件  \n\n\n<html><body><table><tr><td>CabotRegal400R NPGDA NPGDMA 丙氧基甘油三丙烯酸酯（OTA-480） TPO</td><td>25.0 25.0 10.0 10.0 3.0</td><td>369 1.5 CPTX 0.5 炭黑（CAB551-0.1） 10.0 分散剂（Solsperse24000） 5.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 605,
+        "chunk": "# （46）UV彩色点阵蓝墨参考配方  \n\n<html><body><table><tr><td>芳香酸甲基丙烯酸半酯（SB500-E50）</td><td>5.4</td><td>Irganox1035 2.3</td></tr><tr><td>DPET/PA(SR-399)</td><td>40.8</td><td>CPTX 0.3</td></tr><tr><td>(EO)6TMPTA（SR-499)</td><td>15.2</td><td>蓝颜料（LionelBlueES） 11.5</td></tr><tr><td>I1850</td><td>1.0</td><td>分散剂BYK161（30%SR399） 3.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 606,
+        "chunk": "# （47）UV彩色点阵红墨参考配方  \n\n<html><body><table><tr><td>芳香酸甲基丙烯酸半酯（SB520E35） DPET/PA(SR399) (EO)3TMPTA(SR454)</td><td>7.9 Irganox1035 16.0 CPTX 20.0 红颜料（IrgaginRedABN） 5.0 黄颜料（PaliotolYellowD1819）</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 607,
+        "chunk": "# （48）UV彩色点阵绿墨参考配方  \n\n<html><body><table><tr><td>芳香酸甲基丙烯酸半酯（SR500E50） DPET/PA（SR399) (EO)6TMPTA(SR-499) Irganox1035</td><td>14.0 45.1 13.7 2.15 2.15</td><td>CPTX 绿颜料（HoliogenGreenL9361） 黄颜料（PolioTolYellowDl819） 分散剂BYK161（30%SR399）</td><td>0.7 15.2 3.5 3.5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 608,
+        "chunk": "# （49）光致全息材料参考配方  \n\n<html><body><table><tr><td>超支化聚酯（折射率1.586，由偏苯三酸100.0 酐和环氧氯丙烷反应苯甲酰氯封端） 丙烯酸四氟丙酯（折射率1.387）</td><td>TPGDA 20.0 二氯甲烷</td><td>光引发剂784</td><td>20.0 1.2 100.0</td></tr></table></body></html>  \n\n保形涂料（conformalcoating）就是涂覆在已焊插接元器件的印制电路板上的保护性涂料。它的作用是使电子器件免受外界有害环境的侵蚀，如尘埃、潮气、化学药品、霉菌的腐蚀作用，具有防水、防潮、防霉等性能，又能防刮损、防短路，可延长电子器件的寿命，提高电子产品使用稳定性。因此保形涂料在电子、通信、汽车、航空航天、造船、国防、生物工程等工业上广泛应用。  \n\n保形涂料按固化方式可分为光固化、热固化、潮气固化、电固化和空气固化等多种。而光固化型保形涂料具有固化速率快，生产效率高；适用于热敏性底材和电子器件；减少溶剂挥发，操作成本低；设备投资较低，节省空间等优点，已成为保形涂料涂装的首选工艺。  \n\n保形涂料是采用喷涂工艺来涂覆在已焊插接元器件的印制电路板上，元器件侧面和阴影区域的涂料的固化就成为光固化型保形涂料应用的关键。因此现在使用的光固化型保形涂料都采用双重固化体系，既可保证印制电路板上大部分区域涂料见光后迅速固化，又能在后固化阶段保证少量阴影区域和元器件侧面的涂料固化完全。常见的双重固化有自由基/阴离子双重固化、光/热双重固化、光/潮气双重固化、光/化学双重固化、光/化学-空气固化等。  \n\n自由基/阳离子双重固化是利用阳离子光固化在光照结束后，生成的阳离子还能继续进行阳离子反应，特别在加热条件下，使后固化继续进行。  \n\n光/热双重固化是在自由基光引发体系中添加过氧化物或偶氮化合物类热引发剂，光照后再加热，通过热引发进行后固化。  \n\n光/潮气双重固化，是利用硅烷与空气中潮气发生水解生成羟基硅烷，再与硅氧烷交联固化。也可利用带一NCO的聚氨酯丙烯酸酯与空气中水汽作用发生暗固化。  \n\n光/化学双重固化是在自由基光引发体系中添加环氧树脂和多元胺，利用氨基与环氧基加成开环进行后固化。也可利用带—NCO 的聚氨酯丙烯酸酯与带羟基化合物，发生—NCO与一OH反应交联进行后固化。  \n\n光固化保形涂料所用低聚物主要有聚氨酯树脂、丙烯酸树脂、环氧树脂或硅氧烷树脂，它们的性能见表10-10。  \n\n表10-10各种光固化保形涂料的性能比较   \n\n\n<html><body><table><tr><td>性能</td><td>丙烯酸树脂</td><td>聚氨酯树脂</td><td>环氧树脂</td><td>硅氧烷树脂</td></tr><tr><td>耐潮性</td><td>1</td><td>1</td><td>2</td><td>1 ·</td></tr><tr><td>耐磨性</td><td>3</td><td>2</td><td>1</td><td>4</td></tr><tr><td>机械强度</td><td>3</td><td>1</td><td>1</td><td>2</td></tr><tr><td>耐热性</td><td>2</td><td>3</td><td>3</td><td>1</td></tr><tr><td>耐酸性</td><td>2</td><td>1</td><td>1</td><td>2</td></tr><tr><td>耐碱性</td><td>3</td><td>1</td><td>1</td><td>2</td></tr><tr><td>耐有机溶剂性</td><td>4</td><td>1</td><td>1</td><td>2</td></tr><tr><td>介电常数（23℃，1MHz）</td><td>2.2~3.2</td><td>4.2~5.2</td><td>3.3~4.0</td><td>2.1~2.6</td></tr></table></body></html>\n\n注： $1{\\sim}4$ 表示其相对值，1最好。  \n\n光固化保形涂料采用喷涂工艺进行涂装，一般黏度较低，由于是双重固化体系，大多为双组分，使用前将双组分混合搅拌均匀，混合后一般都需在8h内用完，否则剩余部分因后固化，使黏度迅速增大，无法喷涂。  \n\n光固化保形涂料所用活性稀释剂既要考虑黏度，又要考虑固化速率，还要使物理力学性能得到保证，所以大多数单、双、多官能度复合使用。  \n\n光固化保形涂料光引发剂使用，也都采用复合光引发剂，一般使用高效的光引发剂651、1173、184与TPO、819复配。为了表面固化好，也需加入活性胺等减少氧阻聚影响。光固化保形涂料主要性能指标见表10-11。  \n\n表10-11光固化保形涂料主要性能指标  \n\n\n<html><body><table><tr><td>检测项目</td><td>性能指标</td><td>检测项目</td><td>性能指标</td></tr><tr><td>涂料黏度（涂-4杯，25℃）/s 铅笔硬度/H 冲击强度/kg·cm</td><td>14~20 ≥1 ≥50</td><td>介电损耗（1MHz) 体积电阻/Ω·cm 表面电阻/Ω 抗电强度/(kV/mm)</td><td>≤0.04 ≥1.0×1011 ≥1.0×1012 ≥70</td></tr></table></body></html>\n\n注：涂料性能在涂装固化后放置一天后测试。  \n\n聚酰亚胺（polyimide，简写为PI）是一类在分子主链结构中含有酰亚胺功能团的高分子聚合物，由于具有优异的耐热稳定性，而受到人们的重视，成为当今耐高温聚合物材料中最有实际意义的一类先进材料。  \n\n聚酰亚胺通常由有机芳香二酸酐和有机芳香二胺经缩合反应聚合而成，首先得到其前置体—聚酰胺酸，将其进行适当的热或化学处理（亚胺化或环化脱水）变成聚酰亚胺材料。  \n\n![](images/2f1280600d653897fff1af87370a24297a467912dcd71ab56f13d59c28553154.jpg)  \n聚酰亚胺  \n\n一般来说，聚酰亚胺材料是不溶不熔的，因此需要在它的前置体——聚酰胺酸阶段进行成型加工。聚酰亚胺刚性的骨架结构赋予了其优良的化学、物理力学和电性能。  \n\n$\\textcircled{1}$ 优异的耐热性能， $T_{\\mathfrak{s}}$ 在 $300^{\\circ}\\mathrm{C}$ 左右，热分解温度在 $500^{\\circ}\\mathrm{C}$ 左右，可耐 $350{\\sim}450^{\\circ}\\mathrm{C}$ 的高温。  \n\n$\\textcircled{2}$ 化学稳定性好，耐有机溶剂和潮气的侵湿。  \n\n$\\textcircled{3}$ 良好的绝缘性，体积电阻率可达 $10^{15}\\Omega\\cdot\\mathrm{cm}$ 。  \n\n$\\textcircled{4}$ 优良的介电性能，介电常数 $3.0{\\sim}3.4$ ，介电损耗 $10^{-3}\\sim10^{-4}$ ，具有比无机介电材料C $\\mathrm{SiO}_{2}$ 、 $\\mathrm{Si}_{3}\\mathrm{N}_{4}$ 等）更好的平面形成性能和力学性能。  \n\n$\\textcircled{5}$ 优良的力学性能，对器件有一定的增强作用。$\\textcircled{6}$ 对常用基体、金属和介电材料的粘接性优良。$\\textcircled{7}$ 较低的热膨胀系数，一般在 $2\\times10^{-5}{\\sim}3{\\times}10^{-5}{\\mathrm{^{\\circ}C}}^{-1}$ α$\\textcircled{8}$ 成型工艺简单、易行，根据需要可形成薄膜或厚膜。  \n\n聚酰亚胺由于其结构具有多样性及可控性，可以根据不同的应用要求，选择不同的二酐和二胺进行缩聚，得到性能满意的聚酰亚胺材料。常用的二酐和二胺见表10-12。 54  \n\n由于聚酰亚胺的优异的耐热性、电性能和其他性能，因而在航空、航天、电子等领域得到了广泛的应用，特别在微电子工业上显示出极其成功的一面。目前，聚酰亚胺在微电子工业中应用主要有：集成电路及微电子器件的封装材料，多层布线和多芯片组件中理想的绝缘隔层材料、表面钝化层材料和α粒子阻挡层材料，同时也是离子注入掩膜、多层抗蚀掩膜材料、柔性印制电路板的基体材料等。但是，通常使用的聚酰亚胺不具有光敏性，使其在微电子元器件中制作膜状图形时，需用光刻胶才能完成制图工艺。即将聚酰胺酸溶液涂覆在基板上，经部分或完全固化后，将光刻胶涂覆在聚酰胺酸膜的上面，经UV曝光、显影得到光刻胶图形。再用碱溶液将暴露出的聚酰胺酸溶解掉，然后，利用化学去膜剂除去覆在聚酰胺酸膜上的光刻胶层，最后，经热固化得到聚酰亚胺膜图形。工艺过程步骤多，周期长，环境污染大，成品率低。为此，开发了具有耐热与感光双重功能的光敏聚酰亚胺（photosensitivepolyimides，简写PSPI)。采用光敏聚酰亚胺制作图形非常简单：将光敏聚酰胺酸涂覆在基板上，经UV曝光、显影，再热固化后，就能得到聚酰亚胺膜图形（图10-30)。两者相比较，光敏聚酰亚胺的制图工艺比较简单，因此，可以获得分辨率很好的聚酰亚胺图形或通孔。  \n\n表10-12常用二酐、二胺的化学结构  \n\n\n<html><body><table><tr><td>物质</td><td>缩 写</td><td>结构式</td><td>物质</td><td>缩写</td><td>结构式</td></tr><tr><td rowspan=\"5\">二 酐</td><td>PMDA</td><td>0 0 0 0 0</td><td rowspan=\"5\"></td><td>ODA</td><td>H2N- -NH2</td></tr><tr><td>BTDA</td><td>0 0 0 0</td><td>PDA</td><td>HN- -NH2</td></tr><tr><td>BPDA</td><td>0 0 0 0 0</td><td>6FDAM 二</td><td>CF3 H2N- -NH2 CF3</td></tr><tr><td>TPDA</td><td>0 0 0 0</td><td>3FDAM 胺</td><td>CF3 HN- NH2</td></tr><tr><td>6FDA</td><td>0 CF3 0 0 CF3 0 0 0</td><td></td><td></td></tr><tr><td rowspan=\"2\"></td><td>3FDA</td><td>0 CF8 0 0 0 0</td><td rowspan=\"2\"></td><td>TFMB</td><td>CF3 H2N- NH2 CF</td></tr><tr><td>6FCDA</td><td>0 CF CF 0 0 0 0 0</td><td>APB</td><td>0 HN- NH2</td></tr></table></body></html>  \n\n目前，光敏聚酰亚胺按其制备方法不同可分为三类：酯类PSPI、离子型PSPI和自增感型 PSPI，商品化的PSPI都为负性胶。它们都是通过聚酰亚胺的前置体——聚酰胺酸来制得的。  \n\n（1）酯类PSPI将带光敏基团的分子与聚酰胺酸反应得到酯类PSPI（图10-31)。  \n\n![](images/b4505a8028e283580568070d91a8c1a0d68505e71f5eb1d3d623f2f6103b9111.jpg)  \n图10-30 两种聚酰亚胺制图工艺过程的比较  \n\n（2）离子型PSPI光敏基团通过其叔氨基与聚酰胺酸分子中羧酸相互作用，形成铵正离子和羧酸负离子，以盐的形式使光敏基团连接到聚合物主链上，得到离子型PSPI。  \n\n具有叔氨基的光敏基团如：  \n\n![](images/711e3c4b572377336ce992d69e1e6f0be002846ed5979c68ba5d20696179cdea.jpg)  \n\n（3）自增感型PSPI聚酰亚胺分子主链结构中含有光引发基团，无需加入光引发剂。在UV光照下，自身发生光交联。如下面结构的聚酰亚胺，主链中含有光引发剂二苯甲酮结构。  \n\n![](images/ce6cb2e7f9c8a921c8f1b02b0484fe58ece02d4764f106da115e077a9866ac58.jpg)  \n\n![](images/a690de09e21222aa310d124e79fe486d00367b4a6f0d60a30c6217e370223b4f.jpg)  \n图10-31酯型光敏聚酰亚胺制备示意图  \n\n1968年，人们发现了N-烷基马来酰亚胺在无光引发剂情况下可发生光聚合，即N-烷基马来酰亚胺具有既可引发聚合，又能参与聚合的特性。与传统的引发剂相比较，N-烷基马来酰亚胺作为光引发剂有三个优点： Q  \n\n①马来酰亚胺与乙烯基醚体系的光聚合对氧气的敏感性较低；② 激发态的马来酰亚胺提取一个氢后，形成了两个自由基，它们都能引发聚合，因此，  \n引发活性较高；③ 马来酰亚胺引发聚合反应后，就参与到聚合物中，形成丁二酰亚胺结构，而原有的  \n共轭结构消失，紫外吸收向短波长移动，产物在300nm以上基本无吸收。所以马来酰亚胺  \n\n的光引发反应是一个光漂白过程，随着反应的进行，固化物有利于紫外光的透过，因此光固化的深度提高，同时固化产物的耐候性也更好。  \n\n表10-13介绍了部分N-烷基马来酰亚胺的光敏特性  \n\n表10-13部分 $\\mathbf{\\delta}_{N}.$ -烷基马来酰亚胺的光敏特性  \n\n\n<html><body><table><tr><td rowspan=\"2\">代号</td><td rowspan=\"2\">R</td><td rowspan=\"2\">外观</td><td rowspan=\"2\">熔点/℃</td><td rowspan=\"2\">折射率</td><td colspan=\"2\">UV吸收</td></tr><tr><td>Amax/nm</td><td>e/[L/(mol·cm)]</td></tr><tr><td rowspan=\"3\">AMI</td><td rowspan=\"3\">CHzCH—CH</td><td rowspan=\"3\">无色晶体</td><td rowspan=\"3\">42~44</td><td rowspan=\"3\"></td><td>212</td><td>470</td></tr><tr><td>232</td><td>1900</td></tr><tr><td>296</td><td>325</td></tr><tr><td rowspan=\"2\">BeMI</td><td rowspan=\"2\">—CHz-</td><td rowspan=\"2\">无色晶体</td><td rowspan=\"2\">70~72</td><td rowspan=\"2\"></td><td></td><td></td></tr><tr><td>197</td><td>3610</td></tr><tr><td rowspan=\"3\">i-BuMI</td><td rowspan=\"3\">CHzCH(CHg)</td><td rowspan=\"3\">无色晶体</td><td rowspan=\"3\">44~46</td><td rowspan=\"3\"></td><td></td><td></td></tr><tr><td>212</td><td>450</td></tr><tr><td>230</td><td>1820</td></tr><tr><td rowspan=\"3\">CMI</td><td rowspan=\"3\"></td><td rowspan=\"3\">无色晶体</td><td rowspan=\"3\">87~89</td><td rowspan=\"3\"></td><td>302</td><td>250</td></tr><tr><td>210</td><td>142</td></tr><tr><td>226</td><td>540</td></tr><tr><td rowspan=\"2\">BuMI</td><td rowspan=\"2\">-CHg</td><td rowspan=\"2\">无色液体</td><td rowspan=\"2\"></td><td rowspan=\"2\">1.4746</td><td>305</td><td>45</td></tr><tr><td>232</td><td>450</td></tr><tr><td rowspan=\"3\">i-PMI</td><td rowspan=\"3\">—CH(CH)2</td><td rowspan=\"3\">无色液体</td><td rowspan=\"3\"></td><td rowspan=\"3\">1.4720</td><td>302</td><td>160</td></tr><tr><td>212</td><td>310</td></tr><tr><td>227 300</td><td>1350 150</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 609,
+        "chunk": "# 0.5 UV光纤涂料",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 610,
+        "chunk": "# 10.5.1 概述  \n\nUV固化光纤涂料是光固化技术在通信技术领域应用的突出代表，也是光固化涂料的一个非常成功的应用领域，它以快捷的固化速率、优良的防护和光学性能，在光纤的生产和使用中发挥了重要的作用。  \n\n光纤通信技术近年来发展飞速，这是因为与微波电缆通信相比，光纤通信具有通信容量大、传输距离远、抗电磁干扰、保密性强、体积小、重量轻、通话清晰、不怕雷（电）击、不产生短路、节省贵金属等优点，因而得到了广泛的应用。  \n\n光纤有石英光纤和塑料光纤两类。石英光纤主要成分是二氧化硅，透光性能优异，光信号衰减较小，适用于远距离光信号传输；但存在加工成本高、质量控制要求严、脆性高、易折断、难修复等缺点。塑料光纤以聚甲基丙烯酸甲酯及其共聚物为主，还有聚苯乙烯及其共聚物、聚碳酸酯等塑料基作塑料光纤，其特性正好与石英光纤相反，它柔软易于加工，也易于连接；但透光性能不好，光信号损耗较大，只能用于传感器、照明、医疗、装饰等短距离光信号传输。因此在光纤通信中，石英光纤占绝对优势地位。  \n\n石英光纤一般由五层结构组成（图10-32)，中心是由高折射率的石英组成纤芯，直径约5μm，再与低折射率石英组成直径约125μm的石英裸纤；外面涂覆一层软涂层，再涂一层硬涂层，两层涂层约 $50\\mu\\mathrm{m}$ 厚；最后涂覆一层着色油墨，约 $5\\mu\\mathrm{{m}}$ 厚。  \n\n![](images/3491961e044a21d2fbb8e878c509107d50f3ee55e0bcbb2fb4388020ef1b0aab.jpg)  \n图10-32光纤示意图",
+        "category": " Introduction"
+    },
+    {
+        "id": 611,
+        "chunk": "# 10.5.2 UV光纤涂料  \n\n石英光纤制作工艺是用先经掺杂的预制石英棒在高温石墨炉中 $2000^{\\circ}\\mathrm{C}$ 以上高温下熔融，拉丝成纤。此裸纤细而脆、易折断，在外界环境作用下，易发生刮伤、灰尘附着、吸附潮气、氧化，直接影响光信号传输质量，必须对裸纤进行涂装保护。涂装方法是裸纤拉出后，降温至 $150^{\\circ}\\mathrm{C}$ 以下，垂直穿过UV涂料液槽，采用浸涂工艺，涂覆上UV光纤涂料，再经过环形UV光源辐照，固化成膜。目前，光纤生产都用双层涂覆光纤涂料工艺，内层为软涂料，外层为硬涂料（图10-33)。·  \n\n![](images/1ef685dac9622e7f6d17f6153fc975ac449c961e1b2be390bdd04715cbdcef93.jpg)  \n图10-33 光纤拉丝示意图  \n\n双层涂覆光纤涂料工艺，要求内层软涂料与外层硬涂料是不同的。内涂层要求 $T_{\\mathrm{g}}$ 较低（低于室温)，高柔韧性，在较宽的温度范围内 $(-60\\sim100^{\\circ}\\mathrm{C}$ ）有较低模量，抗氧化、抗水解，有较高折射率，以保证光信号在光纤传输时能发生全反射而不至损失。外涂层则要求有较高的Tg和模量，以保证有足够的机械强度、较好的耐老化性能，对酸、碱、溶剂、盐水等物质有较强耐抗性。  \n\n光纤涂料早期是溶剂型和热固化型，因此光纤生产效率很低，采用了光固化工艺后，固化速率大大增加，光纤生产效率大大提高。20 世纪80年代就超过了100m/min，现在由于新的低聚物和光引发剂开发，加上光固化时用惰性气体保护，涂装速率最高可达2500～$\\mathbf{3000m/min}$ ，是目前光固化速率最快的光固化材料。  \n\nUV固化光纤涂料主体树脂主要有聚氨酯丙烯酸树脂、改性环氧丙烯酸树脂、有机硅丙烯酸树脂和聚酯丙烯酸树脂等。目前内层涂料的低聚物多采用聚氨酯丙烯酸树脂和有机硅丙烯酸树脂，前者韧性和弹性好、附着力强，但固化速率较慢、黏度大，后者弹性和低温性能优良，但强度低，黏附性差。外层涂料的低聚物多采用环氧丙烯酸树脂和聚氨酯丙烯酸树脂，环氧丙烯酸树脂固化速率快、强度高，但低温性质又较差。因此在设计UV固化光纤涂料时，应根据各类树脂的特性，结合涂料使用要求，采用混合树脂和树脂改性等方法，以求得最佳的综合效果。  \n\n活性稀释剂的选择对UV固化光纤涂料也极重要，它不仅直接影响到涂料的黏度、固化速率，而且对涂层的强度、收缩率、模量和折射率等起着决定性作用，常用的如丙烯酸羟乙酯、丙烯酸月桂酯有较低的 $\\textstyle T_{\\mathfrak{g}}$ ，增加柔性；丙烯酸异冰片酯有较低的收缩率和高折射率；双官能度TPGDA和三官能度TMPTA等，一般也采用复合活性稀释剂。  \n\n光引发剂的选择对UV固化光纤涂料更为重要，在 $2000{\\sim}3000\\mathrm{m/min}$ 高速固化条件下，虽然有惰性气体保护，必须使用高效的光引发剂，才能保证固化完全，常用651、1173、184与TPO、819复合光引发剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 612,
+        "chunk": "# 10.5.3UV光纤着色油墨、UV并带涂料和UV胶黏剂  \n\n光纤成缆时是由不同颜色的单根光纤结合成并带，再由并带组成光纤管，最后由光纤管组合成光缆（图10-34)。大型光缆是由12种不同颜色的光纤用UV固化并带涂料黏结为并带，再由6根并带组成光纤管，3根光纤管组成一根光缆。  \n\n为了能够在光纤连接或维修时，很容易识别每一根光纤，需要在光纤涂层的外表涂覆颜色编码，即涂装一层光纤着色油墨、根据电子工业联合会（EIA：Electronic IndustriesAssociation）规定12种用于光纤颜色编码见表10-14。  \n\n光纤着色油墨也是采用UV固化，而着色剂多采用颜料，由于颜料的加入，使UV固化光纤着色油墨必须考虑：固化速率、颜料的颗粒大小、颜料的迁移和与光纤涂层附着力、耐老化性等问题。实际生产中都将颜料与部分低聚物、活性稀释剂加上分散剂在高效研磨设备中制备色浆，色浆的颗粒应在 ${\\leqslant}1\\mu\\mathbf{m}$ 。然后再把色浆与剩余的低聚物、活性稀释剂、光引发剂和助剂（如消泡剂、流平剂、润湿剂和阻聚剂）等一起研磨制得光纤着色油墨。  \n\n![](images/de1d3a3a5b84980ffb4f4a06f49abe9ccc771e6f6d3c9bbf6470ebd8180eda4b.jpg)  \n图10-34光缆示意图  \n\n表10-14EIA有关光纤颜色编码  \n\n\n<html><body><table><tr><td>颜色名称</td><td>红</td><td>橙</td><td>棕</td><td>黄</td><td>绿</td><td>蓝</td><td>紫(紫红)</td><td>白</td><td>蓝灰(灰)</td><td>黑</td><td>玫瑰色</td><td>海水色</td></tr><tr><td>缩写</td><td>RD</td><td>OR</td><td>BR</td><td>YL</td><td>GR</td><td>BL</td><td>VI</td><td>WH</td><td>SL</td><td>BK</td><td>RS</td><td>AQ</td></tr><tr><td>蒙塞尔 标志</td><td>2.5R 4/12</td><td>2.5YR 6/14</td><td>2.5YR 3.5/6</td><td>5Y 8.5/12</td><td>2.5G 5/12</td><td>2.5PB 4/10</td><td>2.5P 4/10</td><td>N9/</td><td>N5/</td><td>N2/</td><td>10RP 8/6</td><td>10B 8/6</td></tr></table></body></html>\n\n注：N代表中性色。  \n\n光纤并带涂料，实际上是将多个不同颜色的光纤黏合在一起形成并带的材料，起胶黏剂作用。  \n\n光纤胶黏剂是将两根光纤连接在一起成为一根光纤而使用的UV胶黏剂，因此它不仅要对石英有很好的黏结力，而且要不影响光信号通过。  \n\n光缆通常是埋在地下或水中，使用寿命一般定为25年，因此对光纤涂料的性能要求非常全面而严格，表10-15是单层UV光纤涂料的各种性能要求。  \n\n表10-15Photomer9044单层UV光纤涂料的各种性能指标  \n\n\n<html><body><table><tr><td>液态涂料性能</td><td>指标</td><td>固化膜即时性能（25℃）</td><td>指标</td></tr><tr><td>表观</td><td>浑浊</td><td>折射率</td><td>1.53</td></tr><tr><td>黏度(25℃)/Pa·s</td><td>5.0~6.5</td><td>邵氏硬度/D</td><td>70~80</td></tr><tr><td>相对密度</td><td>1.07</td><td>拉伸强度/MPa</td><td>16~20</td></tr><tr><td>折射率</td><td>1.50</td><td>断裂伸长/%</td><td>4~8</td></tr><tr><td>表面张力（25℃）/（N/m）</td><td>28X10-3</td><td>表面静摩擦系数</td><td>0.33~0.35</td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>固化膜即时性能（25℃）</td><td>指标</td><td>老化性能</td><td>指标</td></tr><tr><td>钢块滑动摩擦系数 密度/（g/cm3） 固化收缩率/%</td><td>0.25 1.13~1.16 1~3</td><td>干燥状态，65℃加热30d 拉伸强度/MPa 断裂伸长/%</td><td>19~22 4~8</td></tr></table></body></html>  \n\n光盘是通过激光的作用直接记录、存储和传递信息的存储介质。光盘由于储存密度大，储存信息成本低，使用寿命长，存储条件要求低，并能与计算机、消费类数字电子产品和通信设备联机使用，已成为最普遍使用的信息记录材料之一。  \n\n自1958年发明了激光技术后，很快地在信息记录材料上获得应用。20 世纪60 年代末出现了镭射影碟（又叫激光视盘LD)，但信号类型为模拟信号；1979 年飞利浦公司和索尼公司联手制订光盘（CD）标准，为数字信息，但容量仅650MB左右；1995年制订双盘对接的光盘（DVD）标准，容量为4.7GB左右；进人21世纪又开发了新一代高清晰度DVD，目前蓝光DVD其容量已超过20GB。常用的光盘及性能见表10-16和表10-17。  \n\n表10-16常用光盘代号、名称、读写设备及性能  \n\n\n<html><body><table><tr><td>代号</td><td>中文名</td><td>读取设备</td><td>写人设备</td><td>性能特征</td></tr><tr><td>LD</td><td>镭射影碟</td><td>镭射影碟机</td><td>影碟生产线</td><td>以模拟方式存储音视信息</td></tr><tr><td>CD-ROM</td><td>只读光盘</td><td>电脑光驱</td><td>光盘生产线或 刻录机</td><td>只读型光盘。CD-ROM驱动器是大多数PC 机的标准设备</td></tr><tr><td>VCD</td><td>视频光盘</td><td>具有解码芯片的播 放器，如VCD播放器</td><td>光盘生产线或 刻录机</td><td>全动态、全屏播放的视频标准。可在电脑、电 视等显示终端上播放</td></tr><tr><td>MO</td><td>磁光盘</td><td>MO专用播放器</td><td>MO专用写人 设备</td><td>采用磁记录原理，利用激光读写数据的光盘， 是一种可擦写光盘</td></tr><tr><td>CD-R</td><td>一次写人光盘</td><td>根据写人数据内容 选择播放器</td><td>CD-R刻录机</td><td>一次写人，多次读取，是目前常用的刻录光盘</td></tr><tr><td>CD-RW</td><td>可擦写光盘</td><td>根据写人数据内容 选择播放器</td><td>CD-RW刻录机</td><td>可擦写型光盘。写入速度慢，反射率低，价格 较高</td></tr><tr><td>DVD</td><td></td><td>计算机光驱</td><td>DVD生产线 或刻录机</td><td>容量大，单面单层4.7GB；在功能上全面替代 CD-ROM</td></tr><tr><td>DVD-R</td><td>可写人DVD</td><td>根据写入数据内容 选择播放器</td><td>DVD刻录机</td><td>一次性写出多次读取的盘片，是目前广泛应 用的DVD刻录盘片标准，具有较好的兼用性， 主要用于消费类电子产品和电脑存储</td></tr><tr><td>DVD-RW</td><td>可多次写人DVD</td><td>根据写人数据内容 选择播放器</td><td>DVD刻录机</td><td>可重写式DVD，理论上可重擦写1500次</td></tr><tr><td>HD-DVD</td><td>高清DVD</td><td>高清DVD播放器</td><td>高清DVD生 产线或刻录机</td><td>主要用于音视播放领域，容量大，图像分辨率 高，可达1920×1080</td></tr><tr><td>BD-DVD</td><td>蓝光DVD</td><td>蓝光DVD播放器</td><td>蓝光DVD生 产线或刻录机</td><td>基本性能同HD-DVD，容量更高，20GB以上</td></tr></table></body></html>  \n\n表10-17四种基本光盘基本性能比较  \n\n\n<html><body><table><tr><td>名称</td><td>信号类型</td><td>读取激光光谱颜色</td><td>信息容量</td></tr><tr><td>LD</td><td>模拟</td><td>红</td><td>与数字信号之间不具有可比性</td></tr><tr><td>CD</td><td>数字</td><td>红</td><td>650MB左右</td></tr><tr><td>DVD</td><td>数字</td><td>红</td><td>“ 4.7GB左右</td></tr><tr><td>BD-DVD</td><td>数字</td><td>蓝</td><td>20GB以上</td></tr></table></body></html>  \n\n光盘存储技术是将具有很高的相干性和单色性的激光束汇集到光衍射极限的斑点（一般在 $1\\mu\\mathrm{m}$ 以下）上，使微光斑区域内存储介质产生物理或化学变化，从而导致该微区的某种光学性质（如折射率、反射率等）与四周介质形成较大的反衬度。用调制激光束载入要存储的数字信息 (写入过程)，而用另一激光束检测光信号，经过调制以取出信息 (读出过程)。  \n\n，光盘从信息记录、存储和读取分类，目前有三种类型。  \n\n（1）只读型（readonlymemory，ROM）其声音或图像信息事先在工厂光盘生产线上制得，根据信息记录的频率特性和用途，又可分为CD、VCD和DVD。用户使用时相当于使用唱片或电影胶片，在VCD或DVD播放器上播放，只能播放，不能录，也不能抹去。  \n\n（2）一次写入型（recordable，R）一次写入多次读出或写后直读，用户能通过刻录机自己记录和使用信息，但记录的信息不能抹掉重写。主要用于文件档案和资料信息的存储、计算机外存、办公编辑存档等。  \n\n（3）可擦写型（rewritable，RW）能抹去原来记录的信息，再记录新的信息。可分为磁光盘、相变型和有机色素型。  \n\n光盘的制造过程可由图10-35示意。  \n\n![](images/b2629d459596e0b16178a11243a712e96f95b0871ce997fb6aac342b32eeb82d.jpg)  \n图10-35 光盘制造示意图  \n\n光盘的基材是聚碳酸酯(PC)，在注塑机中熔融注塑模压成型。模压时由记录信号的母盘做成模压的母模，使模压成型的碟片带上信号。为了能读取信号，在记录层上制作一层金属化镀层，一般都通过溅射法镀铝方式实现。为了保护铝涂层，必须经旋涂一层UV光盘涂料；再在此涂料上用UV油墨印刷文字和图像，说明信息内容，目前有丝印和胶印两种，制成光盘。而DVD是将两张光盘用UV胶黏剂黏合而成的碟片。光盘的截面示意图如图10-36所示。从光盘的制造过程中看到使用了多种光固化产品：母盘的制作需要使用光刻胶，铝反射层保护需用UV涂料，光盘上文字和图像的印刷需用UV油墨，而DVD的制作需用UV胶黏剂。因此，光盘的制造是光固化技术应用的一个亮点。  \n\n![](images/df3c333d2497aa0d582113ee25b447ecb8b088ddc77c7dc3a070fe3c56c2e957.jpg)  \n图10-36光盘截面示意图  \n\n（1）母盘的制作是利用离心涂布，在一块检验合格的平整玻璃基片上，旋涂一层过渡层(有机胶黏剂)，然后再旋涂一层均匀、光滑的光刻胶，一般使用正性光刻胶，干燥后，用一束由待录信息调制光强并聚焦的激光束使光刻胶曝光，曝光处光刻胶发生光解反应，变成碱可溶性，经显影而除去，水洗、烘于后显示出凹凸结构的预刻槽图，把信息记录下来，成为母盘。再用母盘制备金属模具母模，从而进行大量生产光盘。  \n\n（2）UV光盘涂料是涂覆在铝反射层上，直接与铝膜接触，所以为UV金属涂料。对UV光盘涂料性能要求为：  \n\n$\\textcircled{1}$ 因为涂覆时采用旋涂法，故要求涂料黏度较低；  \n$\\textcircled{2}$ 与金属铝的附着力要好；  \n$\\textcircled{3}$ 作为信息存储材料的涂层，要求体积收缩小；  \n$\\textcircled{4}$ 因涂层上要印刷UV油墨，要对油墨附着力良好；  \n$\\textcircled{5}$ 作为保护涂层要耐磨、抗刮擦。  \n\nUV光盘涂料使用的低聚物以聚氨酯丙烯酸酯和环氧丙烯酸酯为主，它们对金属的附着力好，特别选用低黏度的低聚物。活性稀释剂也是单、双、多官能度丙烯酸酯单体搭配使用；由于烷氧基化丙烯酸单体体积收缩小、黏度也较低、毒性小比较适用；还可使用带羟基的丙烯酸酯单体，有利于增强对金属的附着力。鉴于光盘生产线上速度较快，光引发剂主要用α-羟基酮和麟氧类光引发剂，涂料中不要使用含有磷酸酯的附着力促进剂等酸性组分，容易造成铝反射膜被腐蚀破坏，影响光盘信号读出。同时也要避免使用含硅、含氟的低表面能助剂，以影响后面UV油墨的印刷。  \n\n（3）UV光盘油墨是印刷在UV光盘涂料上，用来标记光盘所存储信息内容的。最初都是用网印印刷的，现在大量使用胶印印刷，为无水胶印。UV光盘油墨低聚物对网印主要选用环氧丙烯酸酯和聚氨酯丙烯酸酯，对胶印则以聚酯丙烯酸酯为主体，配合环氧丙烯酸酯或聚氨酯丙烯酸酯。活性稀释剂和光引发剂都与UV油墨选择类似，大多采用单、双、多官能度丙烯酸酯混合搭配使用， $2{\\sim}3$ 种光引发剂复合使用。  \n\n（4）UV光盘胶黏剂是DVD盘制造时，用来黏合两张碟片的。除了要求粘接性能好以外，特别要求体积收缩要小，以免影响信息失真，同时要求透光性好，不影响激光读取信息。  \n\n电子标签即无线射频识别 RFID（radio frequency identification)，是应用射频识别信号对目标物进行识别的一种先进的非接触式自动识别技术。自动识别技术除电子标签外，还有条形码标签、磁条磁卡、光学字符识别、生物识别（指纹、虹膜、语音等）和智能卡（IC卡）等。电子标签功能类似于条形码，对被标识的物品进行识别。但条形码信息是存储在黑白相间条纹之中，借助光源扫描，实现数据的获取。而电子标签的信息是存储在半导体芯片内，依靠射频通信手段，通过无线电读取。因此电子标签与条形码相比，具有存储信息容量大，信息可读可写，数据可随时更新，速度快；使用寿命长，防水、防磁、耐高温，可在恶劣环境中使用；专用芯片，难以伪造，易于普及应用和实现自动化；使用中无需连线、无需电源、无需接触，且可在射频频率上进行丰富的变化，为防伪、物流管理领域提供了新的方法和工具。  \n\n无线射频识别（RFID）技术最早是在军事上应用，1937年美国海军研究试验室开发的敌我识别系统就是RFID最早的应用，20世纪70年代美国联邦政府开始在核材料上使用电子标签，1969 年保点公司将第一代射频技术防窃系统成功地应用到图书馆，80年代一些商业公司仓库开始用RFID来确定集装箱位置，后来日本东京世界博览会用RFID制作门票，我国第二代居民身份证采用RFID技术，成为全球RFID大规模应用一个重大项目，近年来国际上零售业巨头：美国沃尔玛、德国麦德龙、法国家乐福等公司推行RFID技术，要求全球供货商必须对自己的货物提供电子标签，从而极大地推动了电子标签应用。无线射频识别RFID已被视为20世纪最重要的前十大技术之一。  \n\n无线射频识别RFID系统由电子标签、读写器两大部分组成，在实际应用中还需要其他  \n\n硬件和软件的支持。其工作原理为：电子标签进人磁场后，接收读写器发出的射频信号，凭借感应电流所获得的能量，发送出存储在芯片中的产品信息，或主动发送某一频率的信号；读写器读取信号并解码后，送至中央信息系统进行有关数据处理（图10-37）。  \n\n（1）电子标签（tag，即射频卡）它是RFID系统的真正载体，被装置在被识  \n\n![](images/07784714fcba9a0cd57103e555a423c7acdfbb5219ff8a4bb90910b869530d6d.jpg)  \n图10-37无线射频识别（RFID）技术基本原理示意图  \n\n别的物体上，存储着一定形式的电子数据，即关于该物体的详细信息。电子标签由标签芯片和标签天线组成。标签芯片是具有无线收发功能和存储功能的单片系统，其中存储有约定格式的编码程序，用来唯一标识所附着的物体。它是射频识别系统的数据载体，具有智能读写及加密通信的功能。电子标签有自己的微型天线，用于电子标签和读写器之间传递射频信号。  \n\n（2）读写器（reader）又叫解读器、阅读器，是负责读取或写入标签信息的设备。它能够自动以无接触的方式读取电子标签所存储的电子数据，是RFID系统信息控制和处理中心。读写器与电子标签之间存在着通信协议，彼此互传信息。每当贴附有电子标签的物体通过它的读取范围时，就向电子标签发射无线电波，然后电子标签回送自身储存的物体信息，整个过程是非接触式的。典型的读写器包含有控制模块、射频模块、接口模块以及读写器天线。此外，许多读写器还有附加的接口，以便将获得的数据传给应用系统或从应用系统接收命令。读写器上的天线一般做成门框形式，放在被测物品进出的通道口，它一方面给无源的电子标签发射无线电信号提供电能，以激活电子标签；另一方面也接收电子标签发出的信息。  \n\nRFID读写器发送无线电信号使用的频率不同，可划分为低频（lowfrequency，LF)$30{\\sim}300\\mathbf{kHz}$ 、高频（high frequency，HF） $3\\sim30\\mathrm{MHz}$ 、超高频（ultra high frequency,UHF) $300{\\sim}968\\mathbf{MHz}$ 和微波（microwave，MW） $2.45\\sim5.8\\mathrm{GH}z$ 四个频段，不同频段的RFID系统具有不同的特性，见表10-18。  \n\n无线射频识别RFID成功地解决了无源（电子标签中无电源）和免接触读写这两个难题，是电子器件领域的一大突破。RFID目前在许多领域内广泛应用：物流及供应链管理、仓库管理、集装箱管理、机场行李处理与跟踪以及军事设备供应链管理，校园卡、身份证、户籍管理、门禁、物业/小区管理，交通管理、停车场管理、不停车收费、电子售票，药品防伪、病例信息管理、医药管理、血液管理、医疗设备管理、对疾病的追踪、手术跟踪监控，此外在金融系统、安全系统、进出口检验检疫RFID都大有用武之地。  \n\nRFID 作为新兴产业，电子标签和读写器是产业的两大主要产品，而电子标签中芯片和天线制作是产品的核心，这就给光固化技术带来了新的机遇。  \n\n表10-18不同工作频率的无线射频识别系统性能  \n\n\n<html><body><table><tr><td>比较项目</td><td>低频(LF)</td><td>高频(HF)</td><td>超高频(UHF)</td><td>微波（MW)</td></tr><tr><td>频率范围/MHz</td><td>0:03~0.3</td><td>3~30</td><td>100~968</td><td>2450~5800</td></tr><tr><td>常见工作频率/Hz</td><td>125K 134.2K</td><td>13.56M</td><td>(865~930)M</td><td>(2.45~5.8)G</td></tr><tr><td>读取距离/m</td><td>1.2</td><td>0.7~1.2</td><td>4.0</td><td>15</td></tr><tr><td>数据传输速率</td><td>低</td><td>高</td><td>中等</td><td>中等</td></tr><tr><td>潮湿环境</td><td>没有影响</td><td>没有影响</td><td>严重影响</td><td>严重影响</td></tr><tr><td>发送器和读写器的方向要求</td><td>没有</td><td>没有</td><td>部分必要</td><td>总是必要</td></tr><tr><td>芯片内存/B</td><td>64~1k</td><td>256~128k</td><td>64~512</td><td>16~64</td></tr><tr><td>技术程度</td><td>很成熟</td><td>成熟</td><td>新技术</td><td>开发中</td></tr><tr><td>读写价格</td><td>低</td><td>一般</td><td>高</td><td>很高</td></tr><tr><td>电子标签成本/美元</td><td>约1</td><td>约0.5</td><td>0.5</td><td>>25</td></tr><tr><td>对人体是否有害</td><td>无</td><td>无</td><td>有</td><td>有</td></tr><tr><td rowspan=\"3\">应用</td><td>门禁控制、校园卡、</td><td>智能卡</td><td>货盘记录</td><td rowspan=\"3\">高速公路收费</td></tr><tr><td>水、电、气表，加油站、</td><td>电子ID</td><td>卡车登记</td></tr><tr><td>洗衣店、锁车架</td><td>票务</td><td>拖车跟踪</td></tr><tr><td>市场份额/%</td><td>74</td><td>17</td><td>6</td><td>3</td></tr></table></body></html>  \n\n芯片的制作其关键工艺就是光刻，在硅的晶片上涂覆光刻胶，用紫外光通过掩膜曝光，经显影制得图像，再蚀刻、掺杂改性、去膜，硅晶片分割后，制成芯片。因此芯片的制作就需用光刻胶，它就是一种重要的光固化材料。  \n\n天线的制作可以有多种方法：如真空电镀、绕制布线、蚀刻法和印刷法等多种；蚀刻法和印刷法适宜用于大量制作。蚀刻法制作天线与印制电路板制作线路相似，在覆铜版上涂覆抗蚀油墨，用印有天线布线图案的掩膜贴合，紫外曝光、显影后，再腐蚀、去膜，制成铜质天线。蚀刻法制作天线需用抗蚀油墨为光成像抗蚀油墨，它也是一种光固化油墨。印刷法制作天线是近年来发展的新技术—印刷电子技术的一种，直接用导电油墨在基板上印刷导电线路，形成天线和电路。印刷导电油墨主要采用网印印刷，正在研究用柔印和胶印印刷导电油墨。导电油墨是由微细导电粒子组成的一种功能性油墨，导电粒子主要有银、铜、碳、导电金属氧化物、导电聚合物等，银导电浆使用最为广泛，特别是各种银包覆微粒浆料正在不断开发出来应用。导电油墨有溶剂型、热固型和光固型，光固型导电油墨由于填充导电粒子量大，多采用双固化体系，保证导电油墨固化完全。因此印刷法制作天线也离不开使用光固化材料：网印中网版制作需用网印感光胶或菲林，导电油墨用光固化导电油墨。  \n\n印刷法比蚀刻法制作天线有更多的优势：印刷法是加成法制作技术，而蚀刻法是减成法制作技术；印刷法工艺简单，节约材料，成本低，效率高，对环境污染小；印刷法对基材选择多样，而蚀刻法需用覆铜板；目前存在问题是导电油墨的导电性能还达不到铜质天线效果，正在设法改进中。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 613,
+        "chunk": "# 10.8光固化技术在平板显示器产业中的应用  \n\n在信息时代，人们获取信息的主要途径之一是集中在图像上，作为图像传输的载体，人们在日常生活和生产实践中对电视和计算机等显示器械的依赖性越来越强，显示器已经成为人与电视、计算机交流的主要界面。早期的显示器阴极射线管（cathode ray tule，CRT)，由于其体积大、功耗高，正在被高清晰度、低功耗、低辐射、体积轻而薄的平板显示器(flat panel display，FPD）所替代。平板显示器包括液晶显示器（liquid crystal display，LCD)、等离子体显示器（plasmadisplay panel，PDP）、有机电致发光显示器（organiclight emitting diode，OLED)、真空荧光显示器（vacuccm fluorescence display，VFD）和场致发射显示器（field emission display，FED)。近年来，液晶显示器和等离子体显示器由于技术成熟和成本降低，已经迅速进入人们的日常生活，有机电致发光显示器也由开发进人到试生产阶段。  \n\n平板显示器制造技术涉及光学、半导体、机电、化工、材料和印刷等众多领域，技术要求和技术复合性较高，所用的材料不但种类多而且领域不同，在平板显示器制造中，各类材料占显示器成本约六成。因此，材料制造技术是显示器质量和成本控制的关键。目前平板显示器的生产制造中有许多工艺是采用光固化技术，不少材料使用光固化材料；还有一些平板显示器所用的材料和制造工艺有望应用光固化材料和光固化技术来实现，或由光固化技术来提高显示器的性能和生产速率。故而平板显示器的发展也为光固化技术的应用提供了新的天地。",
+        "category": " Introduction"
+    },
+    {
+        "id": 614,
+        "chunk": "# 10.8.1平板显示器的结构及显示原理  \n\n（1）液晶显示器的结构及显示原理液晶显示器（LCD）是将液晶置于两片导电玻璃之间，通过驱动电路的电压改变，引起液晶分子的扭曲，控制光源的透射或遮蔽，在电源开关之间产生明暗而将影像显示出来。由于在两片玻璃基板上装有配向膜，所以液晶会沿着沟槽配向，当玻璃基板没加入电场时，透过上偏光板的光线跟着液晶做 $90^{\\circ}$ 扭转，通过下方偏光板，液晶面板显示白色；当玻璃基板加人电场时，液晶分子产生配列变化，光线通过液晶分子维持原方向，被下方偏光板遮蔽，光线被吸收无法透出，液晶面板显示黑色。因此液晶显示器是根据电压有无，由偏光片、液晶、驱动电路共同控制液晶显示器面板上光线明暗的变化，使液晶面板达到显示效果。  \n\n液晶显示屏的构造示意图如图10-38所示。  \n\n（2）等离子体显示器的结构及显示原理等离子体显示器（PDP）是一种利用气体放电的显示装置。在显示屏的两个玻璃基板之间由障壁材料分隔出多个气体小室被当作等离子管的发光元件，大量的等离子管排列在一起构成屏幕。每个小室内都充有氛氙气体，在等离子管电极间加上高压后，封在两层玻璃之间的等离子小室中的气体会产生紫外光，从而激发平板显示屏上的红、绿、蓝三基色荧光粉而发出可见光。每个等离子管成为一个像素，由这些像素的明暗和颜色变化组合，产生各种灰度和色彩的图像。  \n\n等离子体显示屏构造示意图如图10-39所示。  \n\n（3）有机发光显示器的结构及显示原理有机发光显示器（OLED）是将有机发光材料层镶嵌在两个电极之间，输入电压时载流子运动，穿过有机层，直至空穴输导层并重新结合。而当电流通过有机发光层时，过量的能量激发有机发光材料以光脉冲形式释放，发出可见光。  \n\n有机发光显示屏构造示意图如图10-40所示。",
+        "category": " Introduction"
+    },
+    {
+        "id": 615,
+        "chunk": "# 10.8.2光刻胶在平板显示器制造中应用  \n\n在平板显示器制造中，平板显示器电路的制作、PDP显示器障壁的制作、LCD显示器彩色滤光片的制作均需采用光刻技术，使用不同类型的光刻胶。  \n\n![](images/db79bb6515f214a2203948498ef6dca4cc41efa47d2f51454582ac0658f05fb7.jpg)  \n图10-38LCD显示屏构造示意图  \n\n![](images/d60912bcaa4d56d1b376ffcbf80280006b16dc177646164968350a0906287399.jpg)  \n图10-39 PDP显示屏构造示意图  \n\n![](images/e241fd5193c8e911bfb654270a464aff4369c533ba7ecbb7f2af315efe2dfb2c.jpg)  \n图10-40 OLED显示屏构造示意图  \n\n（1）氧化钢锡电极（ITO）制作在平板显示器制造中光刻胶的最主要应用是氧化锡透明电极的制作。LCD、PDP和OLED的显示材料（如液晶、有机发光材料等）都是密封在玻璃基板之间，而玻璃基板需要进行特殊的抛光、清洗、ITO镀膜和电路电板制作等工序（图10-41)。平板显示器是液晶、情性气体或有机发光材料在一定电压下使液晶发生扭曲控制光线通过与否或使情性气体产生气体放电或激发有机发光材料发光而产生可见光的显示器，所以制作精细电极是平板显示器的关键技术之一。早期使用感光厚膜法，以光刻导电银浆为电极制作材料，经印刷、光刻和烧结等工艺制作电极，分辨率在40μm左右。现改用溅射ITO透明导电层，然后采用光刻工艺制作电极，分辨率在10μm左右。光刻工艺的改进，对提高平板显示器的画面质量和分辨率起了重要作用。ITO电极制作中使用的光刻胶可为叠氮萘类正性光刻胶，也可用丙烯酸酯类负性光刻胶。  \n\n![](images/45658fe035db38b4955819dcab3ba2681fb26b7ef215ab5e7566bfdeba5368e5.jpg)  \n图10-41 ITO电极制作工艺  \n\n(2）PDP显示器障壁制作在PDP显示器中障壁制作是显示屏制造的关键之一。障壁不仅起到分隔放电单元的作用，而且起到防止相邻单元的光窜扰和电窜扰作用，障壁制作的精度决定PDP 显示器所能达到的分辨率的高低。PDP障壁可以通过喷砂法（图10-42)、丝网印刷法和光敏蚀刻等方法制作。喷砂法对障壁材料损失大，丝网印刷法需多次网印才能达到要求，而光刻法可以实现一次完成并可得到高精度障壁结构。用于制作障壁的光敏蚀刻材料由光固化树脂、光引发剂和无机填料组成，通过掩膜UV曝光，显影后树脂固化形成障壁。OLED显示器的阴极障壁制作方法与PDP相同，一般使用负性光刻胶。  \n\n![](images/269f13e62eaee706d15dccba381597d50682a35e36bd4bccb0b0a8e713ed77e7.jpg)  \n图10-42 障壁制作喷砂法工艺流程  \n\n（3）LCD衬垫料制作LCD显示器是将液晶注人间距为5～7μm的一对玻璃间，为防止玻璃基板间隙的变化，需要在显示区内均匀散布衬垫料。目前LCD 面板散布衬垫料工艺主要采用经过表面处理的球状树脂粉作为衬垫料，散布在LCD面板间，经加热固定在玻璃基板上的方法。  \n\n现在一种新的衬垫料制作技术正在研制和应用中，这就是通过光刻技术制作柱形衬垫料。将负性光刻胶在定位区域涂膜，用光刻工艺制成间隔柱。该工艺要求形成衬垫物的光刻胶不仅有精确的分辨率，还应有好的机械强度，足以支撑液晶盒的压力。固化后的衬垫物的耐久性和可靠性相当重要，保证在显示器寿命期间衬垫物不发生变化，不能对液晶材料产生  \n\n不利的影响。  \n\n（4）彩色滤光片制作彩色滤光片是LCD显示器彩色化的关键组件，其作用是实现LCD面板的彩色显示。液晶显示器是非主动发光显示，背光模块及外部人射光提供光源，通过驱动电路与液晶来控制光线形成灰阶显示，产生黑、白两色的显示画面。彩色画面的显示要靠光线透过彩色滤光片的红、绿、蓝彩色层后形成，因而含有红、绿、蓝三色滤光层的彩色滤光片成为液晶显示面板的关键部件。  \n\n彩色滤光片基本结构是由玻璃基板、黑色矩阵、彩色层、保护层和ITO导电组成，其结构如图10-43所示。  \n\n![](images/85ffc44d4525b43888869882828b70eca0293e01601c07e9e2de073853f55783.jpg)  \n图10-43彩色滤光片结构示意图  \n\n彩色滤光片制作有染色法、染料分散法、颜料分散法、电着法、印刷法等多种，染色法、颜料分散法和电着法均需用光刻技术。染料分散法滤光片制造是将分散有染料的树脂涂布于已有黑色矩阵的玻璃基板上，再涂布一层正性光刻胶，经掩膜曝光，碱水显影，剥离光刻保护层，如此反复三次完成红、绿、蓝滤光层。再涂布保护层及ITO透明电极，即得到彩色滤光片（图10-44）。  \n\n![](images/5faf9a7a27e05d7b756b03bf915455ac22efe812f7f02b88bb7788ab491d8dbc.jpg)  \n图10-44彩色滤色片制作流程 (染料分散法)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 616,
+        "chunk": "# 10.8.3 光固化胶黏剂在平板显示器制造中的应用  \n\n在平板显示器制造中，大量使用多种光固化胶黏剂，从LCD显示器封口胶、封框胶，到OLED边框密封，装配连接和层压都离不开光固化胶黏剂。  \n\n（1）LCD封口胶及封框胶LCD显示器的液晶盒是由两块ITO玻璃用胶黏剂封框制成，第一代～第四代LCD所用的封框胶主要是热固化环氧胶，经点胶划线形成边框并留出液晶滴人口，两块玻璃基片对应压合通过预留口真空灌注液晶。注入液晶后，为防止外渗和水分进人，再用光固化胶黏剂对注人孔进行封口。所用光固化胶黏剂必须对液晶材料无侵蚀性，对玻璃基片和封框胶有很好的黏合性、耐久性以及适宜的机械强度。  \n\n第五代LCD生产线在液晶灌注上采用液晶预滴新技术。液晶预滴技术是在玻璃基板上点胶划线为全封闭封框，不再预留封口，封框胶采用光固化胶黏剂，然后将液晶滴入封框至全部充满，再将另一块玻璃基板对位压合，UV光照使光固化胶黏剂固化制成液晶盒（图10-45)。液晶预滴技术优点为液晶利用率高，同时大大缩短了液晶灌注时间，生产效率提高20倍。液晶预滴技术所用的光固化胶黏剂可以是自由基光固化型、阳离子光固化型或双重固化型胶黏剂。  \n\n![](images/39dab9a31c63e4f8efa4f33405400ca55eb5cee15de2cde4bcf5cdd9786245b2.jpg)  \n图10-45 边框胶应用工艺  \n\n（2）OLED边框密封有机发光显示器是继LCD和PDP之后可产业化的平板显示器，虽然目前市场占有率还很小，但其发光亮度和发光效率高、响应速度快、功耗低等优点而受到人们的关注，开发和应用不断加快。有机发光材料的一个特性是对湿气敏感，空气中的氧和可能渗人的水分子可使发光层有机物氧化，从而破坏有机色素的分子结构，降低色素的发光强度和产品寿命。为避免使用中湿气对有机发光材料的损坏，保证显示画面品质，OLED封装显得更为重要。有机发光材料制备成显色层后，显示器的边缘要贴附干燥剂，并对边框进行密封，而光固化胶黏剂是能够较好满足密封边框的胶黏剂，尤其是离子型光固化胶黏剂具有可湿气固化的性能，是OLED封边用胶黏剂最好的选择。  \n\n（3）装配和层压应用乎板显示器制造工序均采用自动化流水生产线方式，而光固化胶黏剂具有无溶剂、 $100\\%$ 固含量、单组分、室温固化、固化速率快等特点，是最适合在线生产装配的胶黏剂品种，在装配工艺中既便于操作，又可得到性能可靠的组件连接。因此在显示屏电路引脚通过各向异性导电带与集成电路或印制电路及驱动电路的贴装连接，已广泛使用光固化胶黏剂。另外显示盒外不同功能性膜的复合、LCD中偏振膜及保护膜的粘接都可使用光固化胶黏剂。 Y 宏",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 617,
+        "chunk": "# 10.8.4光学功能膜材料  \n\n从图10-39LCD显示屏构造中看到，液晶组件中有多种光学功能薄膜，如偏光片及增大视角功能的广视角膜，改善视觉性能的防眩光膜和防反射膜，增加LCD显示亮度的增亮膜等。在背光组件中除用冷阴极荧光灯作光源外，需要使用棱镜片、扩散片等光学薄膜来调制背光源的发射，使显示器得到均匀的光线和亮度，满足人们的视觉需要。  \n\n早期光学功能膜的制作，主要以材料中添加功能作用的物料成膜或以溅射、蒸镀、电化学沉积等工艺制造，工艺复杂，成品率低，成本高，不适宜规模化连续生产。2000年以后，光学功能膜的湿法涂布技术逐渐成熟，使得光学薄膜生产简化，成本降低，并满足了大屏幕对光学功能膜的需要。光学功能膜的湿法涂布技术有多种类型，其中光固化技术是近年来出现的较成熟的一种、具有生产方便、安全环保、成本低廉和性能可靠等特点。  \n\n（1）PET抗划伤膜显示用触摸屏是一种位置传感器，它通过直接触摸显示屏上的显示图标，将触摸点的位置变成电信号，再经计算机处理转变成需要的信息，通过触摸功能可直接进行人机对话，应用越来越广泛。触摸屏由聚酯（PET）膜软上屏和含有导电点阵的玻璃下屏组成，PET膜软上屏需进行硬化处理和导电层制作，导电层是在PET薄膜一侧沉积ITO膜形成的（图10-46）由于PET薄膜是由双向拉伸生产，膜表面抗擦伤性能较弱，故膜的触摸面极易被刮擦产生痕迹，对此必须对PET膜表面进行硬化处理。光固化硬涂层具有高透明性和抗刮擦性，最适合显示触摸屏PET膜的硬化处理。因触摸屏所用PET膜是柔性薄膜材料，要求硬涂层有好的柔韧性、附着力、透光性、防水和附化学药品性及表面硬度。所以光固化硬涂层配方上大多选用多官能度聚氨酯丙烯酸酯和环氧丙烯酸酯，合理的组合使涂层获得优异的附着力、耐擦伤性。加入纳米二氧化硅或氧化铝填料提高耐磨抗划伤性；添加有机硅助剂使涂层获得滑爽性，也有利于抗划伤性提高。为了提高附着力，往往对PET膜进行电晕、腐蚀等处理。  \n\n![](images/a3f227e6b33f40f73ce181eda58da432b8f5314b4c57854fe7a2722340f00e54.jpg)  \n图10-46PET触摸屏结构  \n\n（2）防反射膜显示器的显示画面在被周围的光线如阳光或外界灯光照射时，会有镜面反射作用而产生映人的现象，造成显示图像质量的劣化，影响显示画面的观赏效果。克服这种现象的方法一般是对显示屏进行防反射处理或在屏幕外侧使用防反射膜。防反射膜的功能是减少入射光的反射量，保证屏幕画面的观赏质量。2000年以前防反射膜的生产主要采用溅射或化学气相沉淀的干法加工工艺，成本高，工艺条件复杂，特别因耐热性问题，不适用在一些塑料基材薄膜上制作，从而研究开发了湿法涂布技术来制作防反射膜。湿法涂布技术制作防反射膜一般至少要有四个涂层组成，基材选用三醋酸纤维素薄膜或聚酯薄膜，自下而上依次是硬涂层、高折射率层、低折射率层和防污抗划伤层，根据需要在透明基材背面涂布压敏胶和隔离膜（图10-47)。各涂层的成膜方法可以是催化固化、热固化或光固化，而光固化涂层是最佳选择。高折射率涂层和低折射率涂层是通过涂料中添加高折射率和低折射率物质，分散在涂料成膜树脂中，经涂布在基材薄膜硬涂层上，形成具有特定折射率的膜材料。当光线穿过防反射涂层时，由于涂层中不同折射率的层面产生光的干扰作用，达到防止外界光的反射作用。低折射率物质有氟化物和含氟的丙烯酸酯共聚物，它们的折射率一般在1.3～1.5之间，二氧化硅也是折射率较低的物质（1.45)。高折射率物质为一些金属氧化物，如二氧化钛（2.35）、二氧化锆（2.05）、氧化锌（2.01）、氧化铪（1.95）等，它们的折射率一般在1.9～2.4之间。通过将具有不同折射率的光固化涂料依次涂布并固化在聚酯基材硬涂层上，形成多层防反射结构，起防反射作用。  \n\n![](images/4428d1ce1b3ef05f871ff43798ec7a007bd34a844b8fbb2a7fe7c7d5e0789260.jpg)  \n图10-47 湿法涂布反射（AR）膜结构  \n\n（3）防眩光膜眩光是一种过强的光线照射，它可以引起头晕目眩，伤害人的眼睛，使被照者视力下降，因此眩光是一种光污染。在显示器使用时产生眩光有两个方面：一是显示器自身发光闪烁产生；二是室内照明及户外光线投射到显示屏后产生的反射眩光。这种眩光使显示器使用者眼睛不适，长时间使用造成眼睛疲劳。为了克服眩光的影响，必须对显示屏进行眩光消除。消除眩光的有效办法是采用防眩光膜，这是在光学薄膜内掺杂或表面镀上一层或数层光学折射材料，这些光学折射材料可以对光线产生散射现象，使得外界光线经过防眩光膜后发生散射变得柔和，不产生眩光。所以防眩光膜能显著减少显示屏玻璃表面对可见光的反射眩光，提高了画面的清晰度。防眩光膜一般是与偏光片一同用于LCD显示器，主要用于笔记本电脑和大型监视器等液晶显示屏。防眩光膜基材大多采用双折射性小的三醋酸纤维素薄膜；其生产方法有将抗眩光的无机材料混人薄膜树脂中，使薄膜自身有一定的光散射性能；或在薄膜成型过程中使用压花辊，在薄膜表面造成凹凸不平引起光线的散射；还可以用电化学沉积或溅射方法，将金属氢化物沉积在薄膜表面，形成不同折射率的透明薄层，对光线发生散射，而起到眩光作用。目前采用的液态涂布法适合大尺寸和连续化生产的要求，它是在薄膜基材上涂布一层或两层含有抗眩光物质经固化干燥后就形成防眩光膜，抗眩光物质可以是纳米无机氧化物和高分子微球（图10-48)。  \n\n![](images/4e08ec0f3efbdb39d814489121c711fca16c7921e57a4b2c164ae2b635859ce1.jpg)  \n图10-48光聚合层防眩光膜示意图  \n\n（4）其他还有许多材料和涂层的制造可采用光固化技术。LCD显示器中偏光板所用的离型膜，可利用光固化聚硅氧烷离型剂涂覆在PET膜上制成，无溶剂挥发，不污染环境，室温固化，能耗小。LCD显示器中背光源的棱镜片，可采用光固化浇注成型（图10-49）或光固化压制成型（图10-50)。LCD显示器中背光源的扩散片，可将粒径 $10\\mu\\mathrm{m}$ 的聚甲基内烯酸甲酯中空微球分散在光固化涂料中，经挤压涂布、网纹涂布或辊涂方式涂布于 $100\\mu\\mathrm{m}$ 的白色PET薄膜上，UV固化制得（图10-51)。此外如导光板底部的反射面上的反射点，也可使用UV油墨印刷来制作。总之，上述介绍的平板显示器中所用的光固化材料大多已经工业化生产，还有一些光固化材料正处在研究开发中。光固化技术的发展和应用，解决了平板显示器制造中存在的许多技术瓶颈，对平板显示器规模化生产和产品的普及应用起到了推动作用。而平板显示器产业的快速发展也为光固化技术的进步和应用提供了场所和发展机遇。  \n\n![](images/5e03628831f04609956c721cf89a76160141bfa189b64600b92710eed0d630a9.jpg)  \n图10-49紫外固化浇注成型制造棱镜片  \n\n![](images/9ebf75d10fde1a9437677b37a7e4af5ab587474db303488e523ec8f9a1e9d83c.jpg)  \n图10-50紫外固化压制成型制造棱镜片  \n\n![](images/ce2855d47eca3fe1feb00ab2112f366d126fa4389928d32165a7a89697d5e3ce.jpg)  \n图10-51 光聚合扩散片  \n\n![](images/b0ef52fcdd0c5afa162074eee91f2ab1f575b3ad0620b0cbc73545545dc86d2f.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 618,
+        "chunk": "# 第11章 光聚合和光接枝  \n\n一般的聚合反应以热引发为主，也有用 $\\pmb{\\gamma}$ 射线引发，而现今人们研究采用紫外光引发聚合，发现紫外光聚合可以在较低温度下进行；聚合反应速率快，故反应时间短；设备简单，投资少；实用性强。但紫外光聚合通常用于透明或半透明体系，如水溶液、微乳液、反相微乳液以及分散体系等。光引发聚合是由于光引发剂对紫外光的吸收及反应介质的散射效应，光强沿着辐射路径下降，使得体系光激发产生的活性中心浓度在各介质层的分布不均匀，形成浓度梯度，各部分聚合速率不同，故光引发聚合比热引发聚合复杂。光聚合可分为溶液聚合、乳液聚合、反相乳液聚合和分散聚合等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 619,
+        "chunk": "# 11.1.1光引发溶液聚合  \n\n对光引发丙烯酸溶液聚合的动力学研究，得到光聚合反应活化能 $E{=}9.53\\mathrm{kJ/mol}$ ，即$E{=}2.28\\mathrm{kcal/mol}$ ，而丙烯酸热引发聚合反应活化能需 $9.2\\mathrm{kcal/mol}$ ，氧化-还原聚合反应活化能也需 $6.68\\mathrm{kcal/mol}$ ，显然丙烯酸光引发聚合反应活化能低得多，这也反映了光引发聚合可在较低温度或室温下进行，体现了光引发聚合的特点。  \n\n研究了用光引发溶液聚合合成高吸水性树脂，以丙烯酸为原料，用氢氧化钠水溶液中和， $\\mathbf{\\Omega}_{N},N^{\\prime}.$ 亚甲基双丙烯酰胺为交联剂，651为光引发剂，混合后在UV灯下光照 $10\\mathrm{{min}}$ 后，交联率即可达 $90\\%$ 以上。当丙烯酸含量在 $40\\%\\sim50\\%$ （质量分数)，中和度 $80\\%$ ，交联剂用量 $0.01\\%$ （摩尔分数)，651用量 $0.1\\%$ （质量分数)，光照 $10\\mathrm{{min}}$ 后，得到的高吸水性树脂的吸水率可达到 $\\scriptstyle1500\\mathrm{mL}/\\mathbf{g}$ 。很显然用光引发溶液聚合方法具有工艺简单、反应时间短、容易操作等特点，为合成丙烯酸系高吸水性树脂开辟了一条新的途径。 一",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 620,
+        "chunk": "# 11.1.2 光引发分散聚合  \n\n分散聚合具有反应体系黏度低、传热方便、产物易于分离等特点。一般分散聚合以热引发为主，也可用 $\\pmb{\\gamma}$ 射线引发，而采用光引发则可在较低温度下进行，聚合反应速率快、设备简单、实用性强。  \n\n对丙烯酰胺光引发分散聚合研究，丙烯酰胺浓度 $100\\mathbf{g}/\\mathrm{L}$ ，分散剂聚丙烯酸接枝壬基酚聚氧乙烯浓度 ${10}\\mathbf{g}/\\mathrm{L}$ ，光引发剂651 $\\mathrm{(1.56\\times10^{-5}m o l/L)}$ ，溶剂叔丁醇/水（70/30，体积比)，充氮除氧30min，在氮气保护下，UV光照，聚合体系光照前是透明的均相溶液，光照60～90s后体系开始出现浑浊，随着反应的进行，体系逐渐发白，最终得到白色乳状液。光照40min时，转化率接近90%。相比通常丙烯酰胺热引发分散聚合转化率90%需用${\\mathsf{6}}{\\sim}10\\mathbf{h}$ ， $\\pmb{\\gamma}$ 辐射引发也需2h，显然光引发效率比前两者优越得多。同时聚丙烯酰胺的分子量也可达到 $6.5\\times10^{6}$ 。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 621,
+        "chunk": "# 11.1.3光引发反相乳液聚合  \n\n反相乳液聚合具有反应体系黏度低、散热容易、反应平稳、反应速率快和聚合物分子量比较高等优点。但热引发时一般反应时间较长，反应温度较高；而辐射引发设备又比较复杂。若采用光引发聚合可在较低温度下进行，反应时间大大缩短，设备简单，实用方便。但考虑光的传播和光能的有效利用，UV光引发聚合通常用于透明溶液体系或透明/半透明的微乳液体系，一般不用于反相乳液这种不透明的非均相体系。反相乳液体系，由于分散相和分散介质的折射率不同，人射光在反相乳液粒子表面可发生反射、折射和散射。一般反相乳液粒子粒径在微米级，反相乳液对可见光 $(0.4{\\sim}0.8\\mu\\mathrm{m})$ ）和UV光 $(0.2{\\sim}0.4\\mu\\mathrm{m})$ ）主要发生反射。因此在反相乳液聚合过程中辅以适当的搅拌，使反相乳液各部分都能均等暴露在UV光下。对丙烯酰胺光引发反相乳液聚合研究表明，体系中光引发剂可以吸收UV光引发聚合，约光照20min，聚合转化率即可接近100%，分子量高达107。这充分说明了UV光引发反相乳液聚合的可行性，为水溶性聚合物的制备提供了一种快速、简便的新方法。  \n\n上述各种光引发聚合中，由于UV光照射到反应体系中，会产生反射、折射、散射和吸收，光强很快衰减，因此实验中反应液厚度仅在30mm左右。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 622,
+        "chunk": "# 11.1.4表面光引发聚合  \n\n表面引发聚合反应是近年来发展起来的一种用来在纳米粒子表面接枝聚合物的接枝方法。在纳米粒子表面引入引发基团，引发单体聚合从而接枝在纳米粒子表面。由于接枝聚合反应从纳米粒子表面引发，因此可以制备高键合密度和高接枝率的聚合物接枝层，并且可以用于制备结构可控、设计有序的有机/无机纳米复合材料。纳米粒子表面若引入偶氮类化合物、过氧化基团等热引发剂基团，可通过热聚合来实现纳米粒子的表面引发接枝聚合。由于热聚合需要较高的引发聚合温度，因此生成副产物和均聚物的反应较难控制，反应时间较长，接枝率和接枝效率较低。而纳米粒子表面引人光引发基团，通过光聚合可实现纳米粒子的表面引发接枝聚合。由于光聚合可在室温条件下进行，操作方便、反应快捷，可得到较高的接枝率和接枝效率，因此表面光引发聚合是纳米粒子表面接枝改性的一种新的方法。例如纳米二氧化硅是目前聚合物改性中应用最为广泛的无机纳米材料之一，但是，由于它尺寸较小，表面能大，很容易团聚成聚集态而失去原有的各种特殊性能，与聚合物复合时，难以达到纳米尺寸的均匀分散。对纳米二氧化硅表面进行有机化处理，如进行表面光引发接枝改性，大大提高了纳米二氧化硅与聚合物的相容性，使其在聚合物基体中均匀分散。 一存在下，用UV光进行辐照引发，对高分子材料进行交联改性的一种新方法。与高能辐射法（Y射线或电子束）和化学交联法相比，紫外光交联的突出特点是：  \n\n$\\textcircled{1}$ 辐射能量低，不影响高分子材料本体性能；  \n$\\textcircled{2}$ 照射装置成本低，投资小；  \n$\\textcircled{3}$ 反应速率快，时间短，生产效率高；  \n$\\textcircled{4}$ 能耗低，不污染环境。  \n\n近年来，高分子材料的紫外光交联技术发展迅速，已成为聚合物科学的一个新的研究领域。通过对热塑性聚合物、热塑性弹性体、聚烯烃纤维等高分子材料的光交联改性研究发现，光交联改性后耐热性得到提高，物理力学性能得到改善，特别是耐抗性有较大提高。因此光交联是高分子改性的又一重要方法，并取得了实际应用。由中国科技大学自主研制、拥有自主知识产权的紫外光交联聚烯烃绝缘电线电缆生产新技术已投人生产。目前电线电缆的聚合物绝缘层或护层的交联方法主要有过氧化物交联法、高能辐射交联法、硅烷交联法和紫外光交联法。过氧化物法一般需要在高温高压、体积庞大的连续硫化管及其配套厂房和设备中进行，能耗高，生产效率低；高能辐射法的设备复杂，造价高，一次性投资大，需要专用厂房和配套设施以及严格的防护措施；而硅烷法存在交联时间长、工艺操作较为复杂、产品耐温、耐压等级不高等缺陷。过去光交联设备采用中压汞灯为紫外光源，其紫外光光强较低，仅在100～450mW/cm，只能光交联厚度小于3mm的聚烯烃材料，而绝大多数中、高压交联电缆的绝缘厚度在3mm以上，因此只能生产≤1kV的低压交联聚烯烃绝缘电线电缆，不能生产绝缘厚度在3mm以上的中、高压电缆。同时也很难使混有色母料的电线电缆达到满意的交联度，因此只能生产本色的低压交联聚烯烃绝缘电线电缆，不能生产分色的低压交联聚烯烃绝缘电线电缆。改进后的紫外光辐照交联设备，优选3～12支微波激发的紫外光强在1800mW/cm²以上的无极灯模块单元，沿待交联电线电缆中心轴线方向依次排列，距中心轴线40～80mm距离的360°空间圆周上均匀分布组合而成。由于光强在1800mW/cm以上，对光交联材料的穿透能力极大提高，本色聚烯烃绝缘材料均匀交联的厚度从原先3mm以下提高到15mm以上，混有色母料的低压电线电缆的聚烯烃绝缘材料也能实现均匀光交联。与此同时，聚烯烃光交联速率也极大地提高，达到满意交联度的紫外光辐照时间从原先的8～10s缩短到0.5～2s。新的光交联工艺采用了“2十1”挤出光照交联工艺，先在导电线芯上熔融双层共挤包覆内屏蔽层和绝缘层，随即进行绝缘层的紫外光交联，然后在光交联绝缘层上再挤出包覆一层外屏蔽层，从而避免了公知的带有炭黑的黑色外屏蔽层吸收紫外光能量而阻碍绝缘层中的光引发剂吸收紫外光引发交联反应，可实现绝缘层厚度在3～15mm、具有内外屏蔽层的10～66kV中、高压光交联聚烯烃绝缘电压的生产；也可根据需要在聚烯烃绝缘料中添加不同颜色的色母料后，实现分色低压光交联聚烯烃绝缘电线电缆的生产。  \n\n光交联聚烯烃绝缘电线电缆的基料为各种类型聚乙烯：低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、线型低密度聚乙烯、超低密度聚乙烯、乙烯与丙烯共聚物及接枝改性聚乙烯等；其中优选为低密度聚乙烯、线型低密度聚乙烯、高密度聚乙烯，或乙烯与乙烯-乙酸乙烯酯共聚物或乙烯丙烯二烯烃三元共聚物的共混物，其共混比例优选为70/30。光引发剂为安息香双甲醚、二烷氧基苯乙酮、硫杂葱酮、葱、苏酮、二苯甲酮及其带有长链取代基的大分子型二苯甲酮衍生物；优选的是4-十二烷基二苯甲酮，4-十六烷氧基二苯甲酮、4'-氯-4-十六烷氧基二苯甲酮，用量0.7%～2.0%（以100质量份聚烯烃为基准)。由于带有长碳链基团的大分子型二苯甲酮衍生物与聚烯烃相容性好，迁移速率低、挥发损失少，光交联聚烯烃电缆绝缘料的贮存期大大延长，加工过程中光引发剂的挥发也大大降低，既延长了UV灯管的寿命，也减少了对环境的污染。光交联剂为三聚氰酸三烯丙酯（TAC)、三聚异氰酸三烯丙酯（TAIC)、三羟甲基丙烷三(甲基)丙烯酸酯、三羟甲基丙烷三烯丙醚、季戊四醇三烯丙醚、季戊四醇四烯丙醚或三甘醇甲基丙烯酸酯或上述两种或两种以上交联剂的混合物;优选为TAC或 TAIC，用量为 $0.8\\%\\sim3.0\\%$ 。复合抗氧剂由两种或两种以上的酚类、亚磷酸酯类、磷酸酯类或含硫酯类抗氧剂组成；以酚类抗氧剂与亚磷酸酯类、含硫酯类为优选配合，以四[亚甲基-3 $\\mathbf{-}(3^{\\prime},5^{\\prime}$ 二叔丁基 $\\cdot4^{\\prime}$ -羟基苯基)丙酸］季戊四醇酯 (抗氧剂1010）与亚磷酸三苯酯（TPP)、亚磷酸三(2,4-二叔丁基苯基)酯（抗氧剂168）或硫代二丙酸二月桂酯的配合尤佳，两者优选比为 $1:1$ ，用量 $0.3\\%\\sim0.8\\%$ 。色母料包括红、黄、蓝、绿、白在内的各色母料，根据交联电缆产品的需要，可在光交联电缆料配方中加入不同色母料；优选用量为 $0.2\\%\\sim0.6\\%$ 。由于采用无极管紫外光辐照交联设备，生产紫外光交联聚烯烃绝缘电线电缆，具有设备结构独特、简单、工艺新颖、投资少、易于维护操作、交联效率高、产品成本低、质量好等优点，开创了光交联实用先例，取得了极大的社会影响和经济效益。  \n\n2008年中国科技大学再接再厉，又开发了紫外光交联膨胀型磷氮类阻燃聚烯烃绝缘电线电缆。该光交联聚烯烃绝缘电缆采用聚乙烯或接枝聚乙烯等为基料，加入光引发剂、多官能团交联剂、抗氧剂，再以膨胀型磷氮类无卤阻燃剂，配合阻燃增效剂、消烟剂和加工助剂，挤出造粒成光交联阻燃电缆料；然后在电缆导电线芯上熔融挤出包覆该阻燃料成绝缘层或护套层，随即对该绝缘层或护套层进行紫外光辐照交联。经检测，该绝缘层或护套层材料的氧指数大于 $30\\%$ ，垂直燃烧实验通过UL-94V0级，拉伸强度大于 $\\mathbf{12MPa}$ ，断裂伸长率大于 $350\\%$ ，体积电阻率大于 $8\\times10^{14}\\Omega\\cdot\\mathrm{cm}$ 。紫外光交联无卤阻燃聚烯烃绝缘电线电缆的开发是光交联技术在高分子材料改性上取得的又一个成功的例子，预示了光交联技术在高分子材料改性领域可大有作为，前景辉煌。  \n\n前线聚合（frontalpolymerigation）是一种以自身反应热为推动力，通过反应区域连续移动，并最终实现整体聚合转化的聚合反应模式。早在1967年前苏联化学物理研究所的Merzhanov和Borovinskaya首次发现了自蔓延高温合成反应，并在陶瓷、金属间化合物合成方面获得了成功应用。1972年Chechilo 和Enikolopyan研究了在高压下甲基丙烯酸甲酯的前线聚合，1991年美国南密西西比大学Pojman教授研究常压下甲基丙烯酸甲酯的前线聚合。 5A  \n\n前线聚合研究的经典方法是将单体和引发剂注入反应器中，在反应器一端加热引发聚合反应，临近加热面的单体开始聚合，并放出足够的热量引发下一层的引发剂分解，进而引发该薄层内单体聚合。聚合前线不断自发向前推进，直到整个容器内的单体聚合完全。前线聚合所需的外供能量是短暂一次性的，聚合启动后即可停止供热，在聚合反应过程中不需要外加热源来维持整个体系的聚合，具有可控性，且聚合反应时间较短、节能、无污染，是一种新型的聚合手段，近年来逐渐应用到工业化生产，显示出较高的  \n\n应用价值。  \n\n前线聚合作为一种新型聚合反应模式，如何获得稳定的聚合推进，如何提高完整前线的推进速率是人们所关注的基础问题。已发现合适的体系主要是丙烯酸酯类单体的热自由基聚合，当然并不局限于自由基聚合体系。实验研究揭示了与前线推进有关的因素：  \n\n$\\textcircled{1}$ 单体必须具有高于前线温度的沸点，这样可以抑制由于挥发而引起的热损失；②放热速率必须大于热损失速率，具有较高聚合热熔的单体通常有利于前线聚合反应的进行，具有绝热或隔热性质的反应容器可降低热损失，也有利于前线聚合持续推进；$\\textcircled{3}$ 反应容器的尺寸对前线聚合反应有很重要的影响，若体积对表面积比值太小，聚合前线界面的规整性可能被破坏，甚至前线推进受阻；$\\textcircled{4}$ 聚合反应速率在起始温度必须尽可能的小，但是在前线温度下快速增大。目前前线聚合研究和应用中最广泛的单体为乙烯基单体或乙烯基官能化的大单体；此外，环氧树脂交联固化、聚氨酯合成交联等反应体系也可以进行前线聚合。  \n\n光引发前线聚合是刚刚开始研究的前线聚合新领域，由于前线光聚合无需高压、高温条件，对单体的聚合热没有特别要求，聚合前线伴随着光引发剂的逐层光漂白而逐渐向前推进，聚合过程无高温现象伴随，突破了传统光聚合只适用于薄层体系的局限性，可实现厚涂层的光固化。光引发前线聚合的固化体系必须要满足下列条件：  \n\n（1）光固化体系有高的光吸收，特别是光引发剂对紫外光有高的吸收，即高的摩尔消光系数，才能有高的光分解作用，产生更多的活性基，引发光聚合反应。  \n\n（2）光引发剂为光漂白性光引发剂，光引发剂吸收某波长紫外光后，发生光分解反应，产生活性基。该波段紫外光吸收逐渐降低，向短波长移动，露出透光窗口，起到光漂白作用，使该波段紫外光向体系深层穿透，利于光引发剂吸收和光解，使聚合前线逐渐向样品深层移动。  \n\n（3）增加光强可以显著提高前线速率，因此使用高光强和高功率的紫外光源，也是实现光引发前线聚合一个重要条件。  \n\n中山大学高分子研究所对光引发前线聚合进行了初步研究，用TPO为光漂白性光引发剂，光引发前线聚合可以使 $2\\mathsf{c m}$ 厚的丙烯酸酯类样品在几分钟内得到完全固化。  \n\n光引发前线聚合有许多明显的和潜在的优势，例如可在常温下进行，不必像热引发前线聚合那样需剧烈的高温过程，热对流倾向降低，有利于提高产物的均匀性，也便于过程的可控性提高；可实现厚涂层材料的交联固化，扩大光固化技术的应用领域。预计光引发前线聚合将在梯度材料、原位杂化材料、非线性材料、厚尺寸水凝胶制造等方面有潜在的应用价值。 3",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 623,
+        "chunk": "# 1.4 双光子光聚合",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 624,
+        "chunk": "# 11.4.1双光子光聚合的特点  \n\n双光子光聚合的机理与普通光聚合的机理基本相同，只是第一步光引发剂吸收光子的过程不同。普通光聚合单光子吸收时，光引发剂只吸收一个波长为的光子就可以从基态 so激发到激发态 $s_{1}$ ；而发生双光子光聚合时，光引发剂同时吸收两个波长相同或波长不同的$\\lambda_{2}$ 和 $\\lambda_{3}$ 光子才能激发到激发态 $\\mathfrak{s}_{1},s_{2},s_{n}$ ，再经过无辐射跃迁到激发态 $s_{1}$ ，然后与单光子过程一样通过激发态 $s_{1}$ 发生电子转移或能量转移发生反应(图11-1)。一般单光子的吸收截面为 $10^{-18}\\mathrm{\\sim}10^{-17}\\mathrm{cm}^{2}\\cdot\\mathrm{s/photon}$ ，而双光子的吸收截面一般为 $10^{-50}{\\sim}10^{-46}\\mathrm{cm^{4}\\cdot\\ s/p h o t o n}$ 因此单光子吸收对光密度要求小，即使弱光也可发生，而双光子吸收只有在光强足够大的地方才可能发生。也就是说普通光聚合（单光子聚合）在光线通过的地方都会发生光聚合反应，是整体或面上的聚合；而在双光子光聚合体系中，光引发剂只有在激光光强足够强的地方，一般在两束光聚焦的焦点处（可有双光子双光束聚合和双光子单光束聚合，如图11-2与图11-3所示)，才能同时吸收两个光子，引发聚合反应，是发生在空间一点的聚合。由此可见，双光子光聚合具有空间选择“点”聚合能力。而且发生双光子吸收可采用长波长激光，因此穿透能力好，可以完成物质体内的定点操控，其聚合加工精度取决于焦点直径的大小，空间分辨率高。  \n\n![](images/b18166604b51c091c7b8e2d394394e9e6baca4b40a12509a7c569473565a3022.jpg)  \n图11-1双光子吸收与单光子吸收的区别  \n\n![](images/adb415967022f819be812a56872bc399eaa690a73bb624b6374639478098d2c1.jpg)  \n图11-2双光子双光束聚合  \n\n![](images/4a36d11fb5b6059768daacaeed4a9658ff5618087b282d7958df2c737afdb5a0.jpg)  \n图11-3双光子单光束聚合",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 625,
+        "chunk": "# 11.4.2双光子光聚合的光引发体系  \n\n从双光子光聚合机理中可见，其核心是双光子光聚合的光引发体系。双光子光聚合的光引发剂有两类：一类是本身具有双光子吸收的性质且可以直接引发聚合，在聚合反应中起光引发剂的作用；另一类是有机分子虽然具有双光子吸收的性质，但本身不能引发聚合，需要将能量转移给光引发剂从而实现光聚合，在光聚合反应中只起光敏剂的作用。  \n\n（1）可直接引发双光子光聚合的光引发剂此类双光子光引发剂分子结构中含有较大双光子吸收截面的基团，如连续的双键或连续的苯乙烯组成；结构中还含有能够产生高效引发聚合反应的部分，如含有UV光引发剂结构；分子受激发后易活化，发生电子转移或能量转移。如下面结构的双光子光引发剂：  \n\n![](images/9069b58947b5455d06e40dc5fa7b820b32eba486ccbe456d13378b716b33462e.jpg)  \n$\\scriptstyle n=0\\sim4$ ， $\\scriptstyle\\mathbf{R}=$ 烷基、烷氧基  \n\n![](images/5a9621b6887148b08d00db34b7c692290686f2547c016c69491ad9df042d5e2b.jpg)  \n\n但由于这些光引发剂合成十分复杂，成本较高，因此限制了它们广泛应用和实用化进程。  \n\n（2）由光敏剂和光引发剂组成的双光子光引发体系由于双光子光引发剂的引发效率与双光子吸收截面及其内部电子转移速度是相关的，可以互补。因此近年来，人们正在寻找双光子吸收截面不是很大，但具有很高的光引发效率的紫外光引发体系。这类光引发体系合成简单，有的已经商品化，这样可大大降低成本，加快双光子光聚合技术的应用。目前主要有香豆素类、荧光酮类和氧杂葱类。  \n\n① 香豆素类如3-苯并咪唑取代-7-N,N-二乙基氨基香豆素(DEDC）与六氟磷酸二苯基碘盐（DIHP）双光子引发体系，对甲基丙烯酸甲酯有很好的双光子光聚合效率。  \n\n![](images/6c5d57214f9674df6778033be22fb05dd3080bbf6632db2f0f480aaf3f35e79d.jpg)  \n\n② 荧光酮类如5,7-二碘-3-正丁氧基-6-荧光酮（FILU）与2,5-二异丙基-N,N-二甲基苯胺(BENA)双光子引发体系，可引发甲基丙烯酸甲酯快速聚合。  \n\n![](images/7295b890859a97940164e2814c82bdd36eecb4e1c87fd42836b9d6dde82211cd.jpg)  \n\n③氧杂葱类如四碘四氯荧光素、藻红和四溴荧光素与三乙醇胺组成双光子引发体系，可引发丙烯酰胺的聚合。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 626,
+        "chunk": "# 11.4.3双光子光聚合技术的应用  \n\n（1）双光子三维光存贮双光子光聚合由于是点聚合，空间分辨率高，可以进行空间多层排布，有可能应用于双光子三维光存贮，其存贮的容量理论上可达1.2×1014bits/cm3，而现在二维光存贮材料的容量，在200nm波长下，理论值仅为2.5×10°bits/cm²。  \n\n（2）双光子三维微细加工双光子光聚合仅在两束光焦点内聚合，因此具有空间调制的特征，可以通过计算机辅助设计，进行精细的主体复杂结构的微细加工，空间分辨率达到微米级，甚至可进人纳米级。  \n\n（3）光子晶体的加工双光子光聚合可以提供规律性很好的周期性的结构，可以成为光子晶体制造的有效方法；同时，双光子光聚合点的大小取决于聚焦的技术和所使用的光的波长，因此完全可以人为地控制晶体中点阵的形状和大小，制造出所需要的光子晶体。  \n\n（4）在生物材料和医疗中应用若采用无毒无味的双光子光引发体系，就有可能用于光交联医用材料，可实现生物体内涂层光固化；同时由于双光子光聚合具有亚微米甚至纳米级水平的空间准确定位，也有可能用于某些肿瘤的光疗。  \n\n由于现有材料的双光子吸收截面及引发效率距离实用化还有一定的差距，因此继续设计合成既具有较大的双光子吸收截面又具有较高的引发效率的新材料，是今后研究的重点。随着新的聚合材料的研究和不断发展，双光子光聚合技术不断完善，它的实际应用必将很快实现，前景极其广阔。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 627,
+        "chunk": "# 11.5.1表面光接枝原理  \n\n表面光接枝的研究最早见于1957年美国Oster 等人的工作，他们首先将光引发剂与聚乙烯混合制片，然后在片材的表面实现光接枝聚合。  \n\n表面光接枝基本原理是用紫外光照射涂有光引发剂和活性单体的有机材料制品表面，使其产生表面自由基从而引发表面接枝聚合(图11-4)。  \n\n![](images/5682d2dff2ca329c636893b8350d6da20f1b5bc6f5f04ab8e62ef1e04b3fb9d6.jpg)  \n图11-4表面光接枝原理  \n\n表面光接枝的首要条件是生成表面引发中心———表面自由基，依据产生方式不同，可分为三种方法。  \n\n(1）含光敏基聚合物辐照分解法对于一些含光敏基（如羰基)，特别是侧链含光敏基的聚合物，当UV光照射其表面时，会发生Norrish-I裂解，产生表面自由基。  \n\n![](images/288bcf8eff98852374d64b0b94adf184378b25391be516a7f433a27128ff792e.jpg)  \n\n这些自由基能引发乙烯基单体聚合，可同时生成接枝聚合物和均聚物  \n\n![](images/1e9991f3232ad65f477162f402313432fec87036fef0d08d2d0bc4a415c4a2f8.jpg)  \n\n（2）自由基链转移法光引光剂在UV照射下发生均裂，产生两种自由基，以651为例：  \n\n![](images/31c14152f664d5bd8214f4312bec62a124466e250554e3cc7c9344d3af2982e2.jpg)  \n\n在单体浓度很低的条件下，两个自由基均会向聚合物表面转移，产生表面自由基，引发单体聚合而生成表面接枝聚合物。  \n\n![](images/1be01e865303d44ee3cc6c9d55e7014d656f993f39fb4a3c1066091d026c2f61.jpg)  \n\n但这两个自由基也能引发单体生成均聚物，故表面接枝聚合物和均聚物能同时生成。只有在单体浓度很低、表面自由基浓度很大时才是一种有效的表面光接枝方法。  \n\n（3）氢消除反应法芳香酮及衍生物在吸收UV光后被激发到单线态，然后迅速回复到三线态，当聚合物表面氢为给予体时，该羰基夺取氢而被还原成羟基，同时也生成了一个表面自由基，引发单体聚合而生成表面接枝聚合物。  \n\n![](images/ca1d0dfefafdc8597094b24438570a3b0c9e66b73dcede6dd2b30d6536773ac9.jpg)  \n\n氢消除反应法具有下列优点： $\\textcircled{1}$ 光还原反应可以定量进行，一个二苯甲酮分子可以夺取一个氢原子产生一个表面自由基，容易控制； $\\textcircled{2}$ 表面自由基的活性远远高于半频哪醇自由基，因此接枝效率高； $\\textcircled{3}$ 因为引发反应起自于光引发剂和碳-氢键的反应，故本方法可适用于所有有机材料的表面接枝。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 628,
+        "chunk": "# 11.5.2表面光接枝方法  \n\n光聚合反应的特点是光辐射、引发、聚合同时发生。以紫外光引发的表面接枝聚合（表面光接枝）具有两个突出的优点： $\\textcircled{1}$ 紫外光与高能辐射相比对材料的穿透力差，故接枝聚合可严格地限定在材料的表面或亚表面进行，不会损坏材料的本体性能； $\\textcircled{2}$ 紫外辐射的光源和设备投资成本低，易于连续化操作。近年来对表面光接枝的研究进展较快，极具工业应用前景。  \n\n表面光接枝实施方法，大致有以下三种。  \n\n（1）气相法（图11-5）聚合物、单体和光引发剂置于一个密闭的玻璃容器中，加热使溶液蒸发，从而聚合物在单体和光引发剂的气氛中进行表面光接枝。光引发剂可以被加热成蒸气，也可以被预先涂在聚合物的表面。气相法表面光接枝有两个优点： $\\textcircled{1}$ 由于单体和光引发剂以蒸气状态存在，自屏蔽效应$\\textcircled{2}$ 聚合物表面的单体浓度极低，故光接枝效率高。缺点是反应慢，UV光照时间长。  \n\n![](images/f3a98bef69b7307100d98cc1d36b3e1c3873f67d42a2cc58a9c05050f78e823f.jpg)  \n图11-5气相表面光接枝反应装置  \n\n（2）液相法（图11-6）把光引发剂、单体与其他助剂配成溶液，直接将聚合物样品置于溶液中进行光接枝聚合；也可先将光引发剂涂到聚合物样品表面，再放人溶液中进行光接枝。液相法光接枝的缺点是均聚物难以避免，也不易实现连续化作业。  \n\n![](images/25de0f6cee1bf28901128f5eed0228f94d39e1d1e8843316bbe36ded089c979b.jpg)  \n图11-6液相表面光接枝反应装置  \n\n（3）连续液相法（图11-7）这是1986年Ranby教授等发明的表面光接枝方法。聚合物基材可为单股纤维、多股丝束或柔性薄膜，绕在转辊上，先通氮气进反应腔内以除去空气，在电机牵引下，聚合物基体经溶有光引发剂和单体的预浸液槽进人反应腔，UV光透过石英窗对其进行辐照。反应腔内除有饱和氮气外还有氮气鼓泡带出的光引发剂、单体的蒸气。光接枝聚合完毕后，用合适的溶剂除去基材上剩余的单体、光引发剂及均聚物，经丙酮清洗，置于空气中干燥并收卷。该法有两大优点： $\\textcircled{1}$ 基材通过预浸液后形成一层极薄的液层表面，因此自屏蔽效应最小；$\\textcircled{2}$ 实现了对纤维和薄膜的连续化光接枝反应，利于工业推厂。  \n\n![](images/54dd5ce0dbd1f6609cf5359953c6d9c33bb3fa70ff108576f6e3516dfe5681d3.jpg)  \n图11-7连续液相法表面光接枝装置  \n\n1—纤维进料辊；2—预浸液；3—热电偶；4—反应液蒸气人口；5—运输辊；6—盛单体的容器；7—石英窗； 8—冷却水管道；9—出气口；10—氮气进气口；11—空气出气口；12—紫外光灯；13—-抛物面反射镜； 14—空气进气口；15—灯匣；16—反应室；17—电子加热器；18—反应溶液；19—带驱动机的输出辊",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 629,
+        "chunk": "# 11.5.3表面光接枝应用  \n\n表面光接枝聚合是在有机材料的表面附加上一层由接枝聚合物形成的新表面，这样可以在原基材性能不变下，通过接枝单体的选择而对新表面进行设计与合成，从而实现表面改性、表面功能化和光接枝层合等应用。  \n\n（1）表面改性表面光接枝聚合主要是用来进行有机材料的表面改性。表面改性是指在保持材料的原性能前提下，赋予其表面新的性能。  \n\n① 亲水性大多数聚合物表面都为疏水性，因此利用表面光接枝对聚合物表面经亲水性单体接枝形成一层亲水层，使疏水性变为亲水性。用本法制备具有永久防雾滴的农用薄膜获得成功。  \n\n$\\textcircled{2}$ 印刷性聚合物材料的印刷性能不佳一直是包装印刷行业急需解决的一个难题。目前工业包装用的聚乙烯、聚丙烯、聚酯、聚氯乙烯薄膜，大多在印刷前要经电晕或火焰处理，或加涂一层底层涂料，才能印刷。但电晕或火焰处理耐久性不好，必须处理后立即印刷。采用表面光接枝技术可以将极性基团接上薄膜表面，并且由于接枝链与薄膜以化学键相连，该新表面具有持久性，从根本上改善塑料薄膜的印刷适性，所以表面光接枝处理的薄膜直接可以进行印刷。  \n\n③ 染色性聚乙烯、聚丙烯和聚酯都能抽丝纺织，但只有聚酯纤维能作纺织布料，即涤纶、的确良，而聚乙烯和聚丙烯均因染色问题不能商业化，由于染色性差，较大地限制了聚烯烃在纺织工业上的使用。而用表面光接枝处理后的纤维，大大改善了纤维的染色性，也可改善纤维的吸水性。  \n\n$\\textcircled{4}$ 光稳定性导致有机材料老化、使用寿命短的主要原因是材料吸收紫外光，引起光老化，为此常用加入紫外光稳定剂—紫外吸收剂或受阻胺来减缓老化。一般是以一定比例的光稳定剂混人聚合物材料中，这种方法的缺点是加入量较大，而且会影响聚合物材料性能。因此用表面光接枝技术在聚合物材料表面接枝上一层光稳定剂是一种经济和有效的方法，既可有效保护聚合物材料本体不受侵害，又能由于光稳定剂以化学键形式和聚合物表面相连，不会出现光稳定剂流失和迁移的问题。  \n\n（2）表面功能化表面光接枝技术除了用于进行材料表面改性外，近年来又向更高层次发展，即材料的表面高性能化或表面功能化。  \n\n$\\textcircled{1}$ 生物活性以生物用途为目的材料表面功能化是近年来研究的热点之一。通过表面光接枝可将具有疏水性表面的聚合物变为亲水性，以改善其生物相容性。还可以把一些具有生物活性的功能团通过直接或间接的方法接在聚合物材料的表面，使材料具有生物活性。  \n\n$\\textcircled{2}$ 催化性利用聚合物纤维、薄膜作为载体，通过表面光接枝直接或间接方法接枝上反应催化基团，制成大分子催化剂，接枝上功能基团，制成功能膜，如吸附膜、分离膜等。  \n\n（3）光接枝层合复合膜是通过特殊方法把具有不同材质和不同性能的薄膜层合在一起的多层膜，是塑料薄膜的一种发展趋势，目前已广泛应用于包装行业，特别是食品包装上。复合膜目前主要有两种生产方法：一种是共挤出技术，即由几台挤出机同时挤出并吹塑成膜，该技术一次性投资大，技术复杂，而且要求被挤出材料不仅能热熔，还要熔点相近、流变性能相吻合，故使产品种类受到很大限制；另一种方法是黏合技术，这是一种传统工艺，包括涂抹胶黏剂、溶剂挥发、压合、干燥或固化等步骤，污染环境，能耗大，发达国家已逐渐淘汰这种技术。这两种方法对聚烯烃（聚乙烯、聚丙烯等）与其他极性聚合物（如纤维素、聚酯、尼龙等）和无机及金属材料（如玻璃、铝箔等）很难粘接层合。而采用光接枝层合技术，就可以克服上述难题，制成各种类型的层合膜。  \n\n光接枝层合把光固化胶黏剂涂于两个待层合薄膜之间，压紧压匀，UV照射，光固化胶黏剂中光引发剂与两薄膜表面作用产生大量自由基，引发胶黏剂固化，固化反应和表面接枝反应同时进行，因此两薄膜与固化层之间靠化学键相接，无明显的界面，大大提高了剥离强度（图11-8和表11-1)。  \n\n![](images/a40676765d13fb35c761705d47e5aea5699398a500f5ca65c68c8ce2fa569365.jpg)  \n图11-8光接枝层合示意  \n\n表11-1复合膜的剥离强度  \n\n\n<html><body><table><tr><td>接枝层类型</td><td>层厚/mm</td><td>层合时间/s</td><td>破坏层</td><td>T-剥离强度/(N/m)</td></tr><tr><td>LDPE/LDPE</td><td>0.188/0.188</td><td>25</td><td>LDPE</td><td>1050</td></tr><tr><td>LDPE/LDPE</td><td>0.083/0.083</td><td>15</td><td>LDPE</td><td>520</td></tr><tr><td>PP/PP</td><td>0.10/0.10</td><td>45</td><td>PP</td><td>2310</td></tr><tr><td>HDPE/HDPE</td><td>0.04/0.04</td><td>100</td><td>HDPE</td><td>290</td></tr><tr><td>LDPE/PET</td><td>0.188/0.256</td><td>15</td><td>LDPE</td><td>1050</td></tr><tr><td>HDPE/PET</td><td>0.04/0.256</td><td>30</td><td>HDPE</td><td>530</td></tr><tr><td>PP/PET</td><td>0.10/0.256</td><td>20</td><td>PP</td><td>1580</td></tr><tr><td>OPP/PET</td><td>0.018/0.256</td><td>50</td><td>OPP</td><td>630</td></tr><tr><td>LDPE/Nylon66</td><td>0.188/0.12</td><td>10</td><td>LDPE</td><td>1340</td></tr></table></body></html>  \n\n用光接枝层合技术可以合成多种有机复合膜，如PET/LDPE 隔氧阻水复合膜，LDPE/PVDC高隔氧复合膜，LDPE/PVA/LDPE超级隔氧阻水复合膜，正在研究制备纸/塑复合膜、铝/塑复合膜及玻璃/塑料复合体等复合材料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 630,
+        "chunk": "# 11.6 光接枝与光聚合合成方法  \n\n（1）聚乙烯膜感光接枝丙烯酸将抽提过的聚乙烯膜浸入二苯甲酮/氯仿溶液中（ $(5\\sim$ $10\\mathrm{{min})}$ ，取出晾干，再真空干燥至恒重（为使二苯甲酮牢固地覆在聚乙烯膜上，二苯甲酮/氯仿溶液中加少量聚苯乙烯)。将该聚乙烯膜置于盛有丙烯酸（含 $0.1\\%$ 的阻聚剂）的石英容器中，用玻璃片压实，置于40W紫外光源下（灯距 $\\mathsf{10c m}\\mathrm{:}$ ）光照接枝反应。反应完，用温水充分洗涤，再用氯仿充分洗涤，干燥至恒重。聚乙烯膜感光接枝丙烯酸接枝率见表11-2。  \n\n表11-2聚乙烯膜感光接枝丙烯酸接枝率  \n\n\n<html><body><table><tr><td>时间/min</td><td>60</td><td>90</td><td>180</td></tr><tr><td>接枝率/%</td><td>8.4</td><td>18.1</td><td>23.6</td></tr><tr><td>二苯甲酮浓度/%</td><td colspan=\"3\">1</td></tr><tr><td>丙烯酸浓度/%</td><td colspan=\"3\">30</td></tr></table></body></html>  \n\n（2）低密度聚乙烯光接枝丙烯酸低密度聚乙烯（ $60\\mu\\mathrm{m}$ 厚， $M_{\\mathrm{n}}=17000$ ， $M_{\\mathrm{w}}=$ 180000，表观结晶度 $32\\%$ ）经丙酮抽提5h，涂上二苯甲酮的丙烯酸溶液 $5.5\\mu\\mathrm{m}$ 厚，盖上反应活性低的聚丙烯膜，夹入两块石英玻璃中，氮气保护，在紫外灯下光照一定时间，反应完用沸水除去均聚物和未反应单体、光引发剂，烘干，称重。低密度聚乙烯光接枝丙烯酸接枝率见表11-3。  \n\n表11-3低密度聚乙烯光接枝丙烯酸接枝率  \n\n\n<html><body><table><tr><td>光照时间/min</td><td>1</td><td>8</td></tr><tr><td>丙烯酸接枝率/%</td><td>2.2</td><td>6.22</td></tr><tr><td>二苯甲酮浓度/%</td><td>1.0</td><td></td></tr></table></body></html>  \n\n（3）低密度聚乙烯光接枝醋酸乙烯酯取两片低密聚乙烯膜，用微型注射器将 $20\\mu\\mathrm{L}$ 一定浓度光引发剂/醋酸乙烯酯溶液（预充氮气以除氧）注射到两片膜中间轻压膜使反应液均匀铺开，盖上石英玻璃片，在预定温度下用紫外光（1kW高压汞灯）照射，反应结束后，将膜取出，烘干除去未反应的单体，用丙酮抽提8h以除去均聚物和未反应光引发剂，将膜烘干称重。不同光引发剂的光接枝率见表11-4。  \n\n单位：%  \n\n表11-4不同光引发剂的光接枝率  \n\n\n<html><body><table><tr><td rowspan=\"2\">辐照时间 /s</td><td colspan=\"5\">光引发剂</td></tr><tr><td>BP</td><td>651</td><td>184</td><td>ITX</td><td>氧杂葱酮</td></tr><tr><td>90</td><td>39.9</td><td>10.8</td><td>9.9</td><td>25.6</td><td>25.0</td></tr><tr><td>120</td><td>59.9</td><td>25.3</td><td>19.7</td><td>28.9</td><td>27.3</td></tr><tr><td>150</td><td>70.4</td><td>26.9</td><td>25.3</td><td>36.3</td><td>29.0</td></tr><tr><td>180</td><td>76.9</td><td>27.7</td><td>26.7</td><td>41.9</td><td>33.5</td></tr><tr><td>210</td><td>77.4</td><td>30.6</td><td>27.8</td><td>45.1</td><td>34.9</td></tr><tr><td>240</td><td>78.3</td><td>31.3</td><td>29.4</td><td>39.1</td><td>35.7</td></tr></table></body></html>\n\n注：温度 $60^{\\circ}\\mathsf{C}$ ，光强 $50,10\\mathbf{W}/\\mathrm{m}^{2}$ ，光引发剂浓度 $3\\%$ 0  \n\n（4）低密度聚乙烯-丙烯酸酯光接枝及光交联低密度聚乙烯膜（厚 $63\\mu\\mathrm{m}$ ， $M_{\\mathrm{w}}=1.8\\times$ $10^{5}$ ， $M_{\\mathrm{n}}{=}1.7{\\times}10^{4}$ ，对紫外光 $\\lambda{=}254\\mathrm{nm}$ 透过率为 $75\\%$ ）经丙酮提抽 ${\\mathfrak{s h}}$ a  \n\n将引发剂BP直接溶于单体丙烯腈（AN)、丙烯酸甲酯（MA)、丙烯酸丁酯（BA)、丙烯酸（AA)、甲基丙烯酸甲酯（MMA)、甲基丙烯酸（MAA）中，BP与单体质量比为1：100；单体丙烯酰胺（AAM)，以丙酮为溶剂配成 $2\\mathrm{mol/L}$ ，BP与AAM质量比为 $1:100$ 。所有单体溶液反应前均通人氮气，以除去溶液中氧气。  \n\n取两片低密度聚乙烯膜，用微型注射器将 $20\\mu\\mathrm{L}$ 上述BP单体溶液注射到两片膜中间，轻压膜使反应液均匀铺开，盖上石英玻璃片，在预定温度下，用 $^{1\\mathbf{kW}}$ 高压汞灯照射，反应结束，将膜烘干除去未反应单体，用丙酮抽提 $^{8\\mathrm{h}}$ ，以除去均聚物和未反应的光引发剂，将膜烘干称量。  \n\n不同单体的转化率见表11-5，不同单体样品接枝效率见表11-6，膜的交联度见表11-7。  \n\n表11-5不同单体的转化率 单位： $9\\%$  \n\n<html><body><table><tr><td>辐照时间/s</td><td>AN</td><td>AA</td><td>BA</td><td>MMA</td><td>AAM</td><td>MA</td><td>AAM</td></tr><tr><td>90</td><td>22.4</td><td>56.7</td><td>36.1</td><td>3.7</td><td>6.6</td><td>45.8</td><td>35.3</td></tr><tr><td>120</td><td>36.0</td><td>69.0</td><td>47.8</td><td>4.3</td><td>9.4</td><td>50.0</td><td>36.6</td></tr><tr><td>150</td><td>45.3</td><td>78.6</td><td>60.6</td><td>9.6</td><td>18.5</td><td>58.9</td><td>38.1</td></tr><tr><td>180</td><td>52.2</td><td>84.3</td><td>65.0</td><td>12.2</td><td>28.7</td><td>65.8</td><td>41.6</td></tr><tr><td>210</td><td>54.1</td><td>84.9</td><td>66.1</td><td>17.0</td><td>33.9</td><td>66.3</td><td>42.5</td></tr><tr><td>240</td><td>53.0</td><td>84.0</td><td>64.9</td><td>17.3</td><td>33.0</td><td>64.2</td><td>45.0</td></tr></table></body></html>  \n\n表11-6不同单体样品接枝效率  \n单位：%   \n\n\n<html><body><table><tr><td>辐照时间/s</td><td>AN</td><td>AA</td><td>BA</td><td>MMA</td><td>AAM</td><td>MA</td><td>AAM</td></tr><tr><td>90</td><td>56.7</td><td>85.8</td><td>53.8</td><td>0</td><td>84.7</td><td>87.4</td><td>47.8</td></tr><tr><td>120</td><td>69.3</td><td>89.6</td><td>72.7</td><td>0</td><td>91.7</td><td>90.6</td><td>53.6</td></tr><tr><td>150</td><td>72.4</td><td>92.3</td><td>73.6</td><td>0</td><td>93.2</td><td>92.9</td><td>57.0</td></tr><tr><td>180</td><td>80.3</td><td>93.6</td><td>85.7</td><td>0</td><td>94.7</td><td>94.4</td><td>57.8</td></tr><tr><td>210</td><td>81.5</td><td>94.2</td><td>94.2</td><td>0</td><td>95.8</td><td>96.0</td><td>58.6</td></tr><tr><td>240</td><td>81.9</td><td>94.5</td><td>96.1</td><td>0</td><td>95.4</td><td>95.4</td><td>59.0</td></tr></table></body></html>  \n\n表11-7 膜的交联度  \n\n\n<html><body><table><tr><td>辐照时间/s</td><td>AN</td><td>AA</td><td>BA</td><td>MMA</td><td>AAM</td><td>MA</td><td>AAM</td></tr><tr><td>90</td><td>13.4</td><td>12.4</td><td>1.8</td><td>0.8</td><td>2.7</td><td>21.2</td><td>13.0</td></tr><tr><td>120</td><td>19.2</td><td>20.7</td><td>2.8</td><td>1.1</td><td>5.1</td><td>25.1</td><td>19.1</td></tr><tr><td>150</td><td>20.1</td><td>27.9</td><td>7.7</td><td>2.2</td><td>7.2</td><td>27.3</td><td>24.0</td></tr><tr><td>180</td><td>30.2</td><td>29.2</td><td>9.2</td><td>3.2</td><td>12.3</td><td>28.4</td><td>29.9</td></tr><tr><td>210</td><td>34.3</td><td>32.4</td><td>10.9</td><td>3.8</td><td>15.1</td><td>29.5</td><td>35.1</td></tr><tr><td>240</td><td>37.5</td><td>36.4</td><td>12.2</td><td>·4.4</td><td>16.8</td><td>30.9</td><td>38.0</td></tr></table></body></html>  \n\n（5）低密度聚乙烯光接枝含氟丙烯酸酯将低密度聚乙烯膜置于一定浓度的二苯甲酮和丙烯酸2,2,3,3,4,4,5,5,6,6,7,7-十二氟庚酯的丁酮溶液中，在一定温度、于氮气保护下，经紫外灯（1kW高压汞灯）照射一定时间，反应完毕，取出膜，用丁酮抽提12h以充分除去均聚物，烘干称量。低密度聚乙烯光接枝含氟丙烯酸酯的接枝率见表11-8。  \n\n表11-8低密度聚乙烯光接枝含氟丙烯酸酯的接枝率  \n\n\n<html><body><table><tr><td>UV光强/（mW/cm²）</td><td>18.6</td><td>21.4</td><td>28.6</td></tr><tr><td>接枝率/(mg/cm²)</td><td>1.76</td><td>4.95</td><td>8.58</td></tr></table></body></html>\n\n注：含氟丙烯酸酯浓度0.4mol/L，二苯甲酮0.05mol/L，70℃，光照30min。  \n\n（6）聚丙烯光接枝N-异丙基丙烯酰胺将聚丙烯膜浸泡于氧杂葱酮与聚醋酸乙烯酯的丙酮溶液中（0.3%氧杂葱酮、0.5%醋酸乙烯酯)，经一定时间后取出，干燥，置于N-异丙基丙烯酰胺与N,N-亚甲基双丙烯酰胺的水溶液中，通氮气10min，开启紫外光源（1kW 高压汞灯)，照射一定时间，反应后的膜以清水洗净后置于去离子水中搅拌12h，再用丙酮抽提12h，以除去单体、光引发剂和均聚物，烘干，称重。聚丙烯光接枝N-异丙基丙烯酰胺的接枝率见表11-9。  \n\n表11-9聚丙烯光接枝N-异丙基丙烯酰胺的接枝率  \n\n\n<html><body><table><tr><td>UV光强/（mW/cm²)</td><td>？</td><td>11</td><td>18</td><td>23</td></tr><tr><td>接枝率/(mg/cm²)</td><td>0.28</td><td>0.37</td><td>0.66</td><td>0.92</td></tr></table></body></html>\n\n注：N-异丙基丙烯酰胺浓度0.18mol/L，N,N-亚甲基丙烯酰胺为 N-异丙基丙烯酰胺重量的5%，60℃光照 20min。  \n\n（7）聚丙烯通过休眠基方式光接枝N-异丙基丙烯酰胺在两片待接枝的聚丙烯膜中间，注入适量的丙烯酸和二苯甲酮的丙酮溶液（丙烯酸2mol/L，二苯甲酮0.2mol/L)，压紧并置于紫外灯下（1kW高压汞灯）照射一定时间后，两片膜适度粘连，小心分开，以丙酮漂洗，除去粘在膜上的聚丙烯酸均聚物，室温下晾干待用，因在聚丙烯膜上接枝丙烯酸量非常少，不能通过称重方式测出。  \n\n将上述预接枝膜置于-定浓度的N-异丙基丙烯酰胺水溶液中，通氮10min后，开启紫外光源，在氮气保护下照射一定时间，反应后膜以清水洗净后置于去离子水中搅拌12h，再用丙酮抽提12h，以充分除去未反应单晶体和均聚物，烘干、称重。聚丙烯通过休眠基方式接枝 $N\\cdot$ -异丙基丙烯酰胺的接枝量见表11-10。 木  \n\n表11-10聚丙烯通过休眠基方式接枝N-异丙基丙烯酰胺的接枝量  \n\n\n<html><body><table><tr><td>光照时间/min</td><td>15</td><td>·30</td><td>40</td></tr><tr><td>休眠基方式光接枝/（mg/cm²）</td><td>0.36</td><td>0.70</td><td>0.86</td></tr><tr><td>-般光接枝/(mg/cm²）</td><td>0.30</td><td>0.50</td><td>0.62</td></tr></table></body></html>\n\n注：N-异丙基丙烯酰胺浓度0.18mol/L，UV光强17.6mW/cm²，光照15min。  \n\n(8）聚丙烯粉料固相光接枝马来酸酐将马来酸酐、二苯甲酮加入丙酮 (或乙酸乙酯)中配成一定浓度的浸渍液，投人定量聚丙烯粉， $50^{\\circ}\\mathrm{C}$ 浸渍一定时间取出，待溶剂挥发后，加人到沸腾床式光反应器中，在高纯氮吹动下进悬浮紫外辐照（400W)，光照后的聚丙烯粉用丙酮抽提 $^{10\\mathbf{h}}$ ，用化学滴定法接枝率(接枝马来酸酐占聚丙烯的质量百分比)，见表11-11。  \n\n表11-11 固相接枝率  \n\n\n<html><body><table><tr><td>二苯甲酮浓度/%</td><td>５</td><td>10</td><td>15</td><td>20</td><td>25</td><td>30</td></tr><tr><td>接枝率/%</td><td>0.28</td><td>0.71</td><td>0.69</td><td>0.59</td><td>0.57</td><td>0.50</td></tr></table></body></html>\n\n注：马来酸酐浓度 $30\\%$ ，浸渍 $40\\mathrm{{min}}$ ，光照 $\\mathsf{5m i n}$  \n\n固相光接枝的接枝率随二苯甲酮浓度增大而呈下降趋势，与溶液光接枝不同。  \n\n（9）UV辐射引发聚丙烯接枝马来酸酐-苯乙烯将 ${\\displaystyle100{\\bf g}}$ 聚丙烯和 $0.6g$ 二苯甲酮在转矩流变仪中于 $190^{\\circ}\\mathrm{C}$ 条件下共混 $3\\mathrm{{min}}$ ，再加人 $_{4\\mathbf{g}}$ 马来酸酐和 $_{4\\mathbf{g}}$ 苯乙烯，继续共混 $2\\mathrm{min}$ ，所得共混物用平板硫化仪在 $180^{\\circ}\\mathrm{C}$ 压制成 $80\\mathrm{mm}\\times80\\mathrm{mm}\\times30\\mathrm{mm}$ 片材，加热使其透明，立即置于 $2\\mathbf{k}\\mathbf{W}$ 高压汞灯（灯距 $\\mathbf{150mm}$ ）下，照射30s，进行接枝反应，接枝率可达 $1.58\\%$ a  \n\n（10）聚丙烯薄膜气相光接枝聚丙烯薄膜使用前用丙酮萃取1h。将丙烯酸、甲基丙烯酸、丙烯酰胺和二苯甲酮、联苯甲酰、安息香与丙酮配成不同单体和光引发剂的接枝液（单.体浓度 $\\scriptstyle2,0{\\mathrm{mol}}$ ，光引发剂 $0.2\\mathrm{mol})$ 中  \n\n将接枝液盛于烧杯中，并将烧杯置于一个气密性良好的铝质反应器中，反应器顶部装配一块石英玻璃，反应器放在 $50^{\\circ}\\mathrm{C}$ 恒温水浴中，待接枝的聚丙烯薄膜放于石英玻璃下方，与之平行。在接枝液中不断通人氮气除去氧气，并使接枝液鼓泡，以便使接枝单体、光引发剂进入气相。接枝后薄膜在 $0.1\\mathrm{{mol/L}\\ N a O H}$ 溶液中、 $80^{\\circ}\\mathrm{C}$ 下浸泡 $20\\mathrm{{min}}$ 以除去表面均聚物。再用 $0.05\\mathrm{mol/L}$ 的盐酸溶液浸泡 $20\\mathrm{{min}}$ ，再用蒸馏水充分漂洗后晾干，测定接枝率、水接触角和染色程度，见表11-12～表11-14。  \n\n表11-12不同单体的接枝结果  \n\n\n<html><body><table><tr><td>项目</td><td colspan=\"2\">丙烯酸</td><td colspan=\"2\">甲基丙烯酸</td><td colspan=\"2\">丙烯酰胺</td></tr><tr><td>光照时间/min</td><td>15</td><td>60</td><td>15</td><td>60</td><td>15</td><td>60</td></tr><tr><td>接枝率/%</td><td>15.6</td><td>36.7</td><td>4.06</td><td>28.3</td><td>1.04</td><td>9.10</td></tr><tr><td>水接触角/(°)</td><td>60.5</td><td>53.0</td><td>73.0</td><td>65.0</td><td>81.0</td><td>·68.0</td></tr><tr><td>染色程度</td><td>5.5</td><td>14.4</td><td>3.4</td><td>12.5</td><td>2.5</td><td>10.4</td></tr></table></body></html>  \n\n表11-13不同光引发剂的接枝结果  \n\n\n<html><body><table><tr><td>项目</td><td colspan=\"2\">二苯甲酮</td><td colspan=\"2\">安息香</td><td colspan=\"4\">联苯甲酰</td></tr><tr><td>光照时间/min</td><td>15</td><td>60</td><td>15</td><td>60</td><td></td><td>15</td><td>60</td><td></td></tr><tr><td>接枝率/%</td><td>15.6</td><td>36.7</td><td></td><td>4.59</td><td>21.1</td><td>6.3</td><td></td><td>32.0</td></tr><tr><td>水接触角/(°)</td><td>60.5</td><td>53.0</td><td>75.0</td><td>59.0</td><td></td><td>71.0</td><td>55.0</td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>13.8</td><td></td></tr><tr><td>染色程度</td><td>5.5</td><td>14.4</td><td>3.8</td><td>11.2</td><td></td><td>4.3</td><td></td><td></td></tr></table></body></html>  \n\n表11-14接枝膜稳定性  \n\n\n<html><body><table><tr><td>试验</td><td>接枝率/%</td><td>水接触角/(°)</td></tr><tr><td>接枝后（室温）</td><td>21.68</td><td>57</td></tr><tr><td>接枝后室温放置2个月</td><td>26.31</td><td>58</td></tr><tr><td>接枝后（噪晒）</td><td>36.71</td><td>53</td></tr><tr><td>接枝后日光曝晒16h</td><td>37.51</td><td>53</td></tr></table></body></html>  \n\n(11）聚酯薄膜光接枝马来酸酐/苯乙烯将马来酸酐在丙酮/乙醇混合溶剂中，配成lmol/L溶液，加人苯乙烯（马来酸酐重的20%）和光引发剂二苯甲酮（浓度3%）配好接枝单体溶液。  \n\n将双向拉伸聚酯膜夹在两个载玻片之间，用微量注射器注人接枝溶液，轻压载玻片使其均匀分布，用1kW高压汞灯（照度为7.0mW/cm）辐照60s，使马来酸酐/苯乙烯交替共聚物接枝在聚酯膜表面，接枝后将聚酯薄膜浸泡在丙酮中，以除去未反应的单体和均聚物，再用蒸馏水充分漂洗、晾干。接枝后聚酯薄膜接枝率67%表面张力由原38mN/m提高到$67\\mathrm{mN/m}$ .a  \n\n（12）聚酯核孔膜光接枝丙烯酸聚对苯二甲酸乙二酯核孔膜（孔密度1×108cm-，膜厚10μm，孔径0.4μm，）浸人一定浓度的丙烯酸和二苯甲酮的混合水溶液中，膜上保持一定的液层厚度，在氮气保护下，紫外光照（1kW 高压汞灯）一定时间后取出，在索氏提取器中用水抽提15h，以除去未反应单体和均聚物，60℃真空干燥至恒重。聚酯核孔膜光接枝丙烯酸的接枝率见表11-15。  \n\n表11-15聚酯核孔膜光接枝丙烯酸的接枝率  \n\n\n<html><body><table><tr><td>光照时间/s</td><td>20</td><td>40</td><td>60</td><td>90</td></tr><tr><td>接枝率/%</td><td>0.6</td><td>1.2</td><td>2.5</td><td>2.8</td></tr></table></body></html>\n\n注：丙烯酸浓度7mol/L，二苯甲酮浓度0.05mol/L。接枝层主要核孔膜的光照正面，膜的背面和孔内无接枝物。  \n\n（13）聚酯核孔膜本体光接枝N-异丙基丙烯酰胺聚酯核孔膜（孔径0.2μm 膜厚10μm，孔密度1×10°cm-2）经丙酮抽提后，浸入N-异丙基丙烯酰胺和二苯甲酮溶液中5min，取出在空气中室温干燥，然后夹在两片BOPP膜中间，用塑封机热辊在80℃碾压处理（辊速lcm/s)，使混合物熔化，在核孔膜表面形成均匀的混合物薄层，同时将BOPP 膜中间的空气排出。置于紫外灯下（1kW高压汞灯）并于一定温度下反应，反应后的膜用乙醇抽提20h，除去未反应的单体、光引发剂和均聚物，60℃下真空干燥至恒重。  \n\n50℃下光照2min后膜的接枝率见表11-16。  \n\n表11-1650℃下光照2min后膜的接枝率  \n\n\n<html><body><table><tr><td>二苯甲酮/N-二异丙基丙烯酰胺</td><td>0.02/1</td><td>0.05/1</td><td>0.08/1</td><td>0.12</td></tr><tr><td>接枝率/%</td><td></td><td>0.1</td><td>0.8</td><td>1.2</td></tr></table></body></html>\n\n注：光接枝聚酯核孔膜正面可接枝N-异丙基烯酰胺，膜的反面和膜孔内没有接枝。  \n\n（14）聚酯纤维非织造布光表面接枝聚酯纤维非织造布（100g/m²）经丙酮清洗后，再烘于，浸渍在单体和引发剂配成的预浸液中，取出放人紫外光反应器中，夹人两块石英玻璃片中，用50W高压汞灯进行两面紫外接枝处理，灯距20cm，照射时间10min、烘干，浸于苯丙胶乳，干燥，进行力学性能测试，见表11-17～表11-19。  \n\n表11-17不同单体对接枝率和力学性能影响  \n\n\n<html><body><table><tr><td>单体</td><td>接枝率/%</td><td>横向拉伸强度/N</td><td>横向撕裂强度/N</td></tr><tr><td>AM</td><td>23.60</td><td>114.00</td><td>37.0</td></tr><tr><td>St:MMA:BA=1:1:1</td><td>5.71</td><td>65.00</td><td>38.0</td></tr><tr><td>AA</td><td>5.71</td><td>56.50</td><td>39.5</td></tr><tr><td>AN</td><td>4.76</td><td>66.25</td><td>39.5</td></tr></table></body></html>\n\n注：引发剂为安息香，浓度0.1mol/L，溶剂为丙酮：水=2：1。  \n\n表11-18不同引发剂对接枝率、力学性能影响  \n\n\n<html><body><table><tr><td>引发剂</td><td>接枝率/%</td><td>横向拉伸强度/N</td><td>横向撕裂强度/N</td></tr><tr><td>二苯甲酮</td><td>5.71</td><td>68.25</td><td>35.5</td></tr><tr><td>安息香</td><td>23.80</td><td>114.0</td><td>37.0</td></tr><tr><td>联苯甲酰</td><td>6.20</td><td>55.62</td><td>36.0</td></tr></table></body></html>\n\n注：单体为丙烯酰胺，浓度 $\\scriptstyle1{\\mathrm{mol/L}}$ ，溶剂为丙酮：水 $\\mathbf{\\varepsilon}=\\mathbf{2}:1$ n  \n\n表11-19不同溶剂对接枝率、力学性能影响  \n\n\n<html><body><table><tr><td>单体</td><td>溶剂</td><td>接枝率/%</td><td>横向拉伸强度/N</td><td>横向撕裂强度/N</td></tr><tr><td>AM</td><td>丙酮：水=2：1</td><td>8.75</td><td>66.75</td><td>39.75</td></tr><tr><td>AM</td><td>乙醇</td><td>2.27</td><td>49.12</td><td>36.50</td></tr><tr><td>StMMA:BA=1:1:1</td><td>丙酮：水=1·1</td><td>7.60</td><td>66.00</td><td>33.00</td></tr><tr><td>St:MMA:BA=1:1:1</td><td>乙醇</td><td>2.27</td><td>59.00</td><td>35.75</td></tr></table></body></html>\n\n注：单体浓度 $1\\mathrm{mol/L}$ ，引发剂BP浓度 $0.1\\mathrm{mol/L}$ ，照射时间 $\\mathsf{5m i n}$ 中  \n\n（15）尼龙-6纤维光接枝丙烯酸改性将切短为 $2\\mathsf{c m}$ 长的尼龙-6纤维用 $5\\%$ 的氢氧化钠煮1h，除去油污和杂质，用蒸馏水清洗干净后烘干，在氮气保护下，用紫外光照一定时间。  \n\n在三口烧瓶中加人一定量六水合硫酸铁（Ⅱ）铵盐 $(0.05\\%$ ，质量分数)、硫酸 $0.01\\mathrm{mol}$ 和水100mL，通氮气，水浴加热，将称重好的经辐照的尼龙-6纤维加人，通氮气，70～73℃滴加丙烯酸15g，搅拌反应4h，将接枝后的尼龙-6纤维取出冲洗干净，用蒸馏水煮沸除去丙烯酸均聚物，烘干称重，尼龙-6接枝丙烯酸可达 $64.39\\%$ ，吸水率为 $53.94\\%$ （未接枝的尼龙-6吸水率几乎为0)，但拉伸强度从 $150\\mathbf{MPa}$ 下降为 $125\\mathrm{{MPa}}$ ，断裂伸长率由 $217\\%$ 提高到 $309\\%$ 。  \n\n（16）聚氨酯光接枝乙烯吡咯烷酮将医用聚氨酯薄膜浸泡在含有少量核黄素的N-乙烯吡咯烷酮中，24h后取出，在氮气保护下用紫外灯照射，接枝反应完放入100℃水中煮24h（每2h换1次水）取出烘干，称量，计算接枝密度（表11-20)，医用聚氨酯膜接枝改性后，提高了吸水性降低了摩擦系数。  \n\n表11-20 接枝密度  \n\n\n<html><body><table><tr><td>光照时间/min</td><td>40</td><td>60</td><td>80</td></tr><tr><td>接枝密度/（mg/cm²）</td><td>2.8</td><td>4.5</td><td>6.5</td></tr></table></body></html>\n\n注：N-乙烯吡咯烷酮浓度 $5m o l/L$  \n\n（17）丝绸的光接枝丙烯酸羟丙酯真丝双终用甲醇提取24h，以去除残留丝胶和表面油污与杂质。按浴比1：40，将丝绸样品在一定浓度的丙烯酸羟丙酯单体中浸泡一定时间，取出后轧液，称量，计量浸轧率，保持浸轧率在100%士1%，采用气密性良好的反应器，反应器顶部配有石英玻璃，样品平行置放于石英玻璃下方。在反应器中不断通入氮气以除去氧气，用直管型碘灯（3kW）照射样品，样品距光源30cm，光照完毕，用去离子水充分洗涤，用丙酮提取24h，以除去样品表面吸附的单体和均聚物，再用去离子水充分洗涤，低温真空于燥至恒重。不同溶剂的接枝率见表11-21。  \n\n单位：%  \n\n表11-21 不同溶剂的接枝率  \n\n\n<html><body><table><tr><td>丙烯酸羟丙酯浓度/（mol/L)</td><td>水</td><td>乙醇</td><td>丙酮</td></tr><tr><td>0.20</td><td>4.0</td><td>2.5</td><td>1.5</td></tr><tr><td>0.65</td><td>12.0</td><td>8.0</td><td>2.0</td></tr><tr><td>1.30</td><td>18.5</td><td>7.5</td><td>1.8</td></tr><tr><td>2.00</td><td>21.0</td><td>3.0</td><td>1.6</td></tr></table></body></html>  \n\n（18）丝绸低压的汞灯接枝丙烯酸羟丙酯02练白双终用甲醇抽提12h，以去除表面的油污和杂质。按浴比1：40将双置于一定浓度的丙烯酸羟丙酯的乙醇溶液中浸泡一定时间，取出、轧液、称量、计算浸轧率，使浸轧率在100%士1%，置于上下为石英玻璃板，两端有通气孔的辐照池中，不断通入氮气去除氧气，在四根直管形低压汞灯（每根功率20W，发射光谱主要为185nm和254nm）距离5cm下照射20min进行光接枝。接枝后，双终用大量去离子水充分洗涤，用丙酮索氏抽提24h，以除去吸附在双终表面的未反应单体和均聚物，用去离子水充分洗涤，在真空烘箱中低温烘干至恒重。丝绸低压的汞灯接枝丙烯酸羟丙酯的接枝率见表11-22。  \n\n表11-22丝绸低压的汞灯接枝丙烯酸羟丙酯的接枝率   \n\n\n<html><body><table><tr><td>丙烯酸羟丙酯浓度/(mol/L)</td><td>接枝率/%</td></tr><tr><td>0.65</td><td>11.5</td></tr><tr><td>1.30</td><td>20.8</td></tr><tr><td>1.63</td><td>27.0</td></tr></table></body></html>  \n\n（19）玉米淀粉光接枝丙烯腈将1g玉米淀粉用氢氧化钠糊化加水至50mL，使氢氧化钠浓度为0.185mol/L，搅拌通氮气30min，加酸中和，加入3.28g丙烯晴，光引发剂为安息香乙醚(18.9×10-mol/L)，置于石英玻璃反应器，30℃通氮气5min，用紫外光（2×125W）照射1h,得到产物，用二甲基甲酰胺萃取均聚物和未反应单体，再加入盐酸回流2.5h，将淀粉骨架水解、过滤，用水和甲醇洗涤，得接枝聚丙烯睛，接枝率为38.8%，接枝效率为46.7%。  \n\n（20）光引发淀粉反相乳液接枝聚合，将玉米淀粉用氢氧化钠水溶液糊化，调节pH为中性，配成淀粉水溶液，单体丙烯酰胺配成水溶液，将单体溶液与糊化淀粉溶液混合均匀成水相（淀粉浓度3.7%，单体浓度11.9%)。将乳化剂失水山梨醇单油酸酯（斯盘-80）和壬基酚聚氧乙烯醚（OP-10）溶于煤油中，配成9.3%浓度，成为油相。将上述水相滴加于油相中，搅拌乳化60min，配成反相乳液，其中质量浓度(水：油)=1/1.44，HLB=6.34，取定量上述配制好的反相乳液于石英玻璃反应器中，液面高1.7cm，通氮气30min，加人光引发剂置于250W 高压汞灯下室温反应30min，反应液面光强60.5W/m。反应完后，产物用60：40（体积比）冰醋酸-乙二醇混合溶剂抽提24h，剩余物用甲醇沉淀、丙酮洗涤后过滤、烘干得接枝物。不同光引发剂的淀粉接枝聚合物见表11-23。  \n\n表11-23 不同光引发剂的淀粉接枝聚合物  \n\n\n<html><body><table><tr><td>光引发剂</td><td>单体转化率/%</td><td>淀粉接枝率/%</td><td>单体接枝效率/%</td></tr><tr><td>BP</td><td>16.31</td><td>13.03</td><td>24.63</td></tr><tr><td>651</td><td>94.56</td><td>31.73</td><td>10.59</td></tr><tr><td>907</td><td>78.49</td><td>83.05</td><td>32.59</td></tr><tr><td>2959</td><td>59.26</td><td>23.54</td><td>12.23</td></tr><tr><td>184</td><td>88.55</td><td>92.03</td><td>31.99</td></tr><tr><td>819</td><td>90.04</td><td>52.19</td><td>17.84</td></tr><tr><td>TPO</td><td>77.70</td><td>36.32</td><td>14.39</td></tr><tr><td>184+819</td><td>93.79</td><td>76.12</td><td>25.16</td></tr><tr><td>184+TPO</td><td>93.28</td><td>33.82</td><td>11.15</td></tr></table></body></html>\n\n①光引发剂浓度为5.36×10-mol/L。  \n\n（21）聚矾与丙烯酸的紫外光辐射接枝共聚将10.0g聚矾、0.8g二苯甲酮和2.0g丙烯酸溶解于100mL四氢呋喃后装人石英器中，用1000W高压汞灯光照距离20cm，充氮气10min 后，光照一定时间，将光照后溶液倒入过量无水乙醚中沉淀，再用热水洗去均聚物，过滤烘干至恒重，得聚矾接枝丙烯酸。接枝率与水的接触角见表11-24。  \n\n表11-24接枝率与水的接触角  \n\n\n<html><body><table><tr><td>接枝率/%</td><td>水的接触角/(°)</td><td>接枝率/%</td><td>水的接触角/(°)</td></tr><tr><td>0</td><td>68±1</td><td>4.61</td><td>39±1</td></tr><tr><td>2.12</td><td>54±1</td><td>8.79</td><td>32±1</td></tr></table></body></html>  \n\n（22）纳米二氧化硅锚固光引发剂光接枝甲基丙烯酸甲酯在三口烧瓶中加人真空干燥12h 的纳米二氧化硅（平均粒径15～20nm)、70mL氯化亚矾、70mL苯超声分散5min，磁力搅拌回流50h，在反应温度下蒸出剩余的溶剂和氯化亚矾，在90℃下真空干燥，得到表面氯化的纳米二氧化硅粒子A。  \n\n将5gA、5g光引发剂2959、0.2g碳酸氢钠和100mL二甲基甲酰胺加人锥形瓶中，超声分散5min，室温搅拌反应12h，高速离心分离除去未反应的光引发剂2959和二甲基甲酰胺，再次分散到乙醇中离心分离，反复多次彻底除去表面吸附的光引发剂。50℃真空干燥12h，得到表面锚固了光引发剂的纳米二氧化硅粒子B，低温避光保存。  \n\n将0.3gB、5mL甲基丙烯酸甲酯和5mL甲苯加人到石英反应器中，超声分散5min，在磁力搅拌下向悬浮液通氮气以除氧10min，在氮气保护和搅拌下用紫外光照射（光强10.9mW/cm）180min关闭光源后，产物用少量甲醇沉淀，减压抽滤，在50℃下真空干燥12h。将产物超声分散到四氢呋喃中，高速离心分离，弃去上层清液，得到固体，经超声分散到四氢呋喃中，再次离心分离，反复进行数次，直到分离的上层清液中没有聚合物，在50℃下真空干燥12h，得C，为纳米二氧化硅光接枝甲基丙烯酸甲酯。  \n\n在搅拌条件下接枝率可高达 $110\\%$ ( $\\mathrm{180min)}$ 。  \n\n（23）光接枝法制备季铵盐抗菌聚乙烯膜在两片待接枝的聚乙烯膜中间，注入丙烯酸和二苯甲酮丙酮溶液（丙烯酸2mol/L，二苯甲酮0.2mol/L）压紧后，置于紫外灯下照射lmin 后，将两片聚乙烯膜分开，以丙酮漂洗除去粘在膜上的聚丙烯酸均聚物，室温晾干。  \n\n将上述聚乙烯膜置于浓度1.6mol/L的甲基丙烯酰氧乙基-苄基-二甲基氯化铵水溶液中，通氮气10min后，在氮气保护下，用紫外灯照射20min，反应完毕，取出膜，以清水清洗净，置于去离子水中搅拌12h，再用丙酮抽提12h，以充分除去均聚物，烘干，称重，用扫描电镜观察接枝层厚度估计约几微米。  \n\n(24）本体光接枝制备温敏核孔膜将N-异丙基丙烯酰胺和二苯甲酮(10：1，摩尔比)配成丙酮溶液，将聚酯核孔膜（孔径0.2μm，膜厚10um，孔密度1×10°cm-²）浸人溶液中5min，取出在空气中室温干燥，然后夹在两片聚丙烯薄膜中，用塑封机热辊在80℃碾压处理（辊速约lcm/s)，使混合物熔化在核孔膜表面形成均匀的混合物薄层，同时将聚丙烯膜中间的空气排出，在紫外灯下（1kW高压汞灯）及一定温度和光强下，光照180s，反应后的膜用乙醇抽提20h，以除去未反应的单体和均聚物，然后60℃真空干燥至恒重。水通量测试表明，接枝膜具有温敏性能。  \n\n（25）光接枝制备亲水性纳滤膜将酚酞基聚芳醚酮超滤膜［水通量在0.2MPa时为160L/(m²·h)，截留分子量为10000左右，膜对NazSO4溶液不截留］置于反应器底部，加人接枝单体苯乙烯磺酸钠（质量分数10%）和丙烯酸（质量分数5%）混合液10mL，在反应器上部放置饱和硫酸铜溶液，液面高度约1cm，用于滤去波长300nm以下的UV光以抑制单体的均聚。通氮5min除去单体溶液中的氧，在氮气氛中用紫外灯照射20min（光强8.7mW/cm，365nm)。反应结束取出接枝膜，放入乙醇/水溶液中，超声洗涤15min，重复3次，以除去未反应单体和黏附在膜表面及孔径内的均聚物，再用质量分数为5%的硫酸钠溶液浸泡2h进行离子交换，使其皂化，然后用蒸馏水清洗，获得接枝膜对二价盐离子的截留率 $590\\%$ ，其通量达 $23.3\\mathrm{L}/(\\mathrm{m}^{2}\\cdot\\mathrm{h})$ 。  \n\n（26）Ce3+/H+光催化引发糖类在聚丙烯膜表面偶合改性双向拉伸聚丙烯（BOPP厚30μm)，用三级水抽提24h，再用丙酮抽提36h，用丙酮进行表面擦洗，除去BOPP表面杂质， $50^{\\circ}\\mathrm{C}$ 烘干。  \n\n将三氯化铈（CeCl·7HzO）与糖类分子溶于稀盐酸中配制成改性溶液，均现用现配，用pH计测pH，改性溶液先通氮气10min 除去溶解氧，然后取 50μL改性溶液注人两片BOPP 膜中间，压成薄且均匀液膜，两端用石英玻璃夹住，放在高压汞灯下辐照反应，因Ce3+吸收峰入=253nm，实验中采用波长入=254nm的紫外光强度计量。  \n\n光照结束后将两片基材分开，用大量水冲洗表面，再浸泡到盛有三级水烧杯中搅拌洗涤3×20min，最后用丙酮冲洗除掉BOPP表面的水，通风放置晾干，再测接触角，见表11-25。  \n\n表11-25不同情况下的接触角  \n\n\n<html><body><table><tr><td>项目</td><td>空白BOPP</td><td>D-果糖改性</td><td>L-山梨糖改性</td><td>D-葡萄糖改性</td><td>D-半乳糖改性</td></tr><tr><td>接触角/(°)</td><td>107.8</td><td>43.6</td><td>47.4</td><td>66.9</td><td>66.3</td></tr><tr><td>糖类</td><td>0.2mol/L</td><td>[Ce3+ ]0.4mol/L</td><td>pH=0.00</td><td>光强12.0mW/cm²</td><td>光照12.5min</td></tr></table></body></html>  \n\n（27）聚乙烯纤维光交联将聚乙烯纤维在正庚烷中浸泡24h，取出后用丙酮洗涤多次，真空干燥至恒重，浸泡于不同浓度、不同溶剂的反应液中（反应液预先通氮气10min）24h，吸干后放入紫外光交联反应器中，用紫外光（500W高压汞灯）照射一定时间，再用二甲苯抽提24h。交联度用凝胶含量来表示。不同光照时间和不同交联剂浓度的交联度见表11-26和表11-27。  \n\n表11-26不同光照时间的交联度  \n\n\n<html><body><table><tr><td>光照时间/min</td><td>１</td><td>2</td><td>４</td><td>６</td><td>8</td></tr><tr><td>凝胶时间/%</td><td>4.83</td><td>8.67</td><td>11.35</td><td>21.40</td><td>21.23</td></tr></table></body></html>  \n\n表11-27不同交联剂浓度的交联度  \n\n\n<html><body><table><tr><td>TMPTA浓度/%</td><td>10</td><td>20</td><td>50</td></tr><tr><td>凝胶含量/%</td><td>8.47</td><td>11.35</td><td>23.83</td></tr></table></body></html>\n\n注：辐照时间 $4\\mathrm{{min}}$ 西  \n\n（28）光交联法制备乙烯-醋酸乙烯纳米复合材料将乙烯-醋酸乙烯共聚物（EVA260法国ATOFINA公司）95g、有机蒙脱土（经十六烷基三甲基氯化铵有机化处理）3g、二苯甲酮1g和三羟甲基丙烷三丙烯酸酯lg在转矩流变仪中共混10min，所得共混物用平板硫化仪在130℃下压制成1mm厚片材，加热100℃熔融后立即置于高压汞灯下（距离150mm）光照2min，使样品整体均匀交联。交联样品装人120目的钢丝网包内，用二甲苯回流提取12h，再更换二甲苯继续回流12h，取出网包，红外干燥至恒重，测定凝胶含量可达95%。  \n\n（29）SBS热塑性弹性体的光交联将SBS热塑性弹性体（SBS1301-1，苯乙烯：丁二烯=30：70）3%（质量比）光引发剂安息香乙醚配成甲苯溶液，浇铸得膜厚20μmSBS膜，在紫外光照射10min，光照后 SBS 膜试样浸泡在甲苯中12h，反复过滤洗涤，60℃下干燥至恒重，计算凝胶含量与溶胀比，9min光照后，凝胶含量可达100%，溶胀比可达10.0，Tg由原一 $45^{\\circ}\\mathrm{C}$ 提高到 $-15\\mathrm{^\\circC}$ 。  \n\n（30）光聚合法合成聚丙烯酸-聚氧乙烯水凝胶用丙烯酸溶解光引发剂安息香异丙醚，配成0.0025g/mL的溶液，取50mL。将称量好的聚氧乙烯（分子量150万用量占单体重的1%，质量分数）以适量的热水溶解，加入到上述丙烯酸-光引发剂溶液中。搅匀，再往其中加入氢氧化钠溶液（用量按中和度60%计算）搅拌中和冷却后，加入交联剂N,N-亚甲基双丙烯酰胺5mL（0.0042g/mL溶液），搅匀，将反应液倒入1000mL烧杯中，置于黑光灯箱中静置聚合，主产物不粘手时取出，将产物剪碎、烘干，即为聚丙烯酸-聚氧乙烯水凝胶。  \n\n（31）光聚合法合成聚（N,N-二甲基丙烯酰胺/N-异丙基丙烯酰胺）水凝胶将一定量的光引发剂 2959 及交联剂 N,N'-丙甲基双丙烯酰胺溶于一定体积的水/N,N-二甲基丙烯酰胺(DMAA)/N-异丙基丙烯酰胺（NipAm）的混合溶液中，搅拌30min，把样品装人4.5cm×4.5cm×0.5cm的透明石英反应器中，充氮5min后密封，分别在50℃和28℃将样品液置于紫外光源下（光强2.5mW/cm²）灯距20cm，反应完全，取凝胶并切块，用蒸馏水浸泡一周，每隔10h换水一次，以除去未反应的小分子化合物，洗涤后，将凝胶于60℃真空干燥得到干凝胶， $50^{\\circ}\\mathrm{C}$ 下制备的水凝胶具有较为疏松的网络结构和相对较快的溶胀速度及温度响应性。  \n\n（32）光聚合法合成聚甲基丙烯酸-N,N-二甲氨基乙酯水凝胶 将甲基丙烯酸-N,N-二甲氨基乙酯配成25%的水溶液，加人0.15%的交联剂N,N-亚甲基双丙烯酰胺，光引发剂20mmol/L过氧化氢，混合均匀后加人内径为18mm的石英试管中，通氮气10min，封管，室温下用500W中压汞灯辐照3h，制得凝胶切碎后，真空干燥，再用甲醇回流提取，干燥，得聚甲基丙烯酸-N,N-二甲氨基乙酯水凝胶，具有温度及pH敏感性。  \n\n（33）光聚合合成甲基丙烯酸羟乙酯/邻羟基环己基甲基丙烯酸酯水凝胶将甲基丙烯酸羟乙酯（HEMA）与邻羟基环已基甲基丙烯酸酯（HCMA）按6：1的摩尔配成水溶液，水的质量分数为40%，加入交联剂N,N-亚甲基丙烯酰胺（为单体摩尔比的1/200）和质量分数的1%的光引发剂2959置于1kW高压汞灯下进行光聚合反应，光照180s停止（有20s诱导期)，获得HEMA/HCMA水凝胶，双键转化率约 $60\\%$ .0  \n\n（34）光聚合合成N-羧乙基壳聚糖/甲基丙烯酸羟乙酯水凝胶将2.0g壳聚糖（相当于含有10mmolNH）加入到含有1.40mL丙烯酸的100mL水中，在50℃下持续搅拌2天。在反应液中加人lmol/L的氢氧化钠溶液，使 pH=10～12，使所有羧酸全部转化为钠盐，将混合液在丙酮中沉淀，透析（透析膜截取分子量为8000～12000）两天后晾干得到N-羧乙基壳聚糖（CECS)。  \n\n混合1.0%N-羧乙基壳聚糖水溶液、含有1.0%三丙二醇二甲基丙烯酸酯和0.5%光引发剂2959（相对于甲基丙烯酸羟乙酯）的甲基丙烯酸羟乙酯单体溶液（质量分数)，混合溶液注人两片载玻片所夹的带孔橡胶垫的图形孔中，室温下用光强为15mW/cm²的紫外灯照射10～30min进行光聚合，得到水凝胶用去离子水冲洗3次，60℃真空干燥48h，制得N-羧乙基壳聚糖/甲基丙烯酸羟乙酯水凝胶，见表11-28。 咔  \n\n表11-28光聚合合成 $\\mathbf{\\delta}_{\\mathbf{N}}$ -羧乙基壳聚糖/甲基丙烯酸羟乙酯水凝胶  \n\n\n<html><body><table><tr><td>项目</td><td>1</td><td>2</td><td>3</td></tr><tr><td>CECS：HEMA（质量比）</td><td>0.5:100</td><td>1:100</td><td>2:100</td></tr><tr><td>CECS溶液/%</td><td>33.3</td><td>50.0</td><td>66.7</td></tr><tr><td>HEMA/%</td><td>65.7</td><td>49.3</td><td>32.5</td></tr><tr><td>TEGDMA/%</td><td>0.67</td><td>0.50</td><td>0.33</td></tr><tr><td>2959/%</td><td>0.33</td><td>0.25</td><td>0.17</td></tr></table></body></html>  \n\n（35）光交联合成聚丙烯酸羟丙酯-N-肉桂酰氧甲基丙烯酰胺水凝胶在三口烧瓶中按一定量加人丙烯酸羟丙酯与N-肉桂酰氧甲基丙烯酰胺（97%～99%，3：1，摩尔比)、适量氯仿和5%的过氧化苯甲酰，搅拌均匀后，65℃避光通风干燥30min，在40℃烘箱干燥10h，将此共聚物置于300W高压汞灯下（距离20cm）照射10min，发生光交联，将交联体浸泡于无水乙醇中，经数次溶胀退胀处理后，干燥得透明聚丙烯酸羟乙酯-N-肉桂酰氧甲基丙烯酰胺水凝胶，有较灵敏的温敏行为。  \n\n（36）光交联法合成聚N-肉桂酰氧甲基丙烯酰胺-丙烯酸水凝胶在三口烧瓶中按一定量加入N-肉桂酰氧甲基丙烯酰胺和丙烯酸（5：95，摩尔比)，用氯仿作溶剂，避光升温70℃，反应12h后，升温1h，冷至室温，抽滤，固体用甲醇洗数次，再用二氯乙烷洗数次，除去未反应单体和丙烯酸均聚物，真空干燥得到共聚物，溶于一定体积水中，共聚物水溶液流延在洁净载玻片上，通风干燥30min，40°℃烘箱干燥10h，然后置于300W高压汞灯下光照10min发生光交联，用蒸馏水浸泡洗涤，得聚N-肉桂酰氧甲基丙烯酰胺-丙烯酸水凝胶。  \n\n（37）光聚合法合成聚丙烯酸-聚氧乙烯高吸水性树脂用丙烯酸溶解光引发剂安息香异丙醚，配成浓度为0.0025g/mL的溶液，取该溶液50mL，将称量好的聚氧乙烯（分子量为150万用量为单体重1%）以适量热水溶解，加入到丙烯酸-光引发剂溶液中，搅拌均匀后，再加人新鲜的氢氧化钠溶液（用量按中和度60%）搅匀冷却后加人5mL交联剂N，N-亚甲基双丙烯酰胺（以去离子水配成0.0042g/mL溶液)，搅匀后倒人1000mL烧杯中，置于黑光灯箱中（20W×25支)，至产物不粘手时取出，产物为片状，剪碎，烘干，得丙烯酸-聚氧乙烯高吸水性树脂，吸去离子水率为 $\\scriptstyle1400{\\mathbf g}/{\\mathbf g}$ α  \n\n（38）光聚合法合成聚丙烯酸-丙烯酸钠高吸水性树脂将一定量丙烯酸用氢氧化钠水溶液中和至80%，单体浓度在40%～50%，加入交联剂0.01%N,N'-亚甲基双丙烯酰胺（摩尔分数）和光引发剂0.1%的651（质量分数)，混合后放在UV灯下照射10min，烘干、粉碎后，得到聚丙烯酸-丙烯酸钠高吸水性树脂，吸水率可达到 $\\boldsymbol{1500}\\mathrm{mL}/\\mathbf{g}$ 。  \n\n（39）光聚合法合成聚丙烯酸钠高吸水性树脂将一定量的丙烯酸用氢氧化钠水溶液中和至60%～65%，单体浓度在33%～40%，加人交联剂0.07%N,N-亚甲基双丙烯酰胺和光引发剂0.1%安息香异丙醚，搅拌下混合后，放在UV灯下照射至反应物表面不粘手时取出，得聚丙烯酸钠高吸水性树脂，吸水率可达 $\\scriptstyle1300_{\\mathbf{g}}/\\mathbf{g}$ 。  \n\n（40）光聚合法合成聚丙烯酸-丙烯酸铵高吸水性树脂用氨水将丙烯酸中和至72%，加人交联剂N,N'-亚甲基丙烯酰胺0.005%，光引发剂1700（25%的819与75%的1173)0.1%，配成75%浓度水溶液，置于高压汞灯下，光照强度1.1mW/cm，照射20min，取出后烘干、粉碎，得到聚丙烯酸-丙烯酸铵高吸水性树脂，最高吸水率达835mL/g，交联率可达 $94.5\\%$ 。  \n\n（41）光引发三羟甲基丙烷三丙烯酸酯溶液聚合制备微凝胶在一个带通气口的直管反应瓶中，将定量光引发剂二苯甲酮溶于丁酮中（浓度1%)，然后加人三羟甲基丙烷三丙烯酸酯（在丁酮溶液中浓度35%)，混合均匀后取10mL反应溶液，液面高度为1cm，用聚丙烯膜封口通氮气10min，置于1kW高压汞灯下，光强100mW/cm²，光照3min，光照时持续通氮气，得到浅黄色透明澄清溶液，为稳定的凝胶分散液。  \n\n（42）紫外光引发丙烯酰胺分散聚合将1g分散剂聚丙烯酸接枝壬基酚聚氧乙烯加到100mL叔丁醇/水（70/30，体积比）混合溶剂中，待溶解完后再加入10g丙烯酰胺至完全溶解，将反应液加入到硬质玻璃反应瓶中，用微量注射器加入光引发剂651的叔丁醇溶液(10-5mol/L)  \n\n1.56mL，通氮气 $30\\mathrm{{min}}$ ，在 $25\\%$ 照射 $40\\mathrm{{min}}$ ，得白色乳状液，所得产物用大量乙醇洗涤，离心分离 $30m\\mathbf{\\dot{in}}$ 后于 $50^{\\circ}\\mathsf{C}$ 下烘干，得聚丙烯酰胺，平均粒径223nm，平均分子量 $4.1\\times10^{6}\\div$  \n\n（43）紫外光引发丙烯酰胺反相乳液聚合在三口烧瓶中加人定量煤油和乳化剂QP10，搅拌溶解配成4.18%浓度乳化剂溶液，通氮气15～20mm。将定量丙烯酰胺和适量乙酸钠、乙二胺四乙酸二钠溶于水中，搅拌溶解配成4.22mol/L浓度单体水溶液，通氮气1520min。将水相滴加人油相，搅拌乳化30mir，配成乳液。  \n\n硬质玻璃光聚合反应器，用双层聚丙烯膜封口，通氮气10min，注人50mL配好的乳液，加入2.5×10-mol/L的651煤油溶液，在250W直管中压汞灯下照射 20min，20℃时在甲醇中沉淀，以丙酮洗涤数次后，于40～50℃下真空干燥，得聚丙烯酰胺，转化率90%，分子量 $8.0\\times10^{6}$ 。  \n\n（44）紫外光引发醋酸乙烯酯溶液聚合在干净的反应瓶中加人0.005g光引发剂二苯甲酮，用注射器加入经减压蒸馏的醋酸乙烯5g和溶剂5g（四氢呋喃)，再用微量注射器加入三乙胺0.00lg，用橡皮筋在反应瓶口紧固上双层聚丙烯薄膜（反应所需紫外光可以全部透过)，在反应瓶侧管通氮气15min，以排出氧气，在紫外灯下光照 50min，将反应产物取出后，用去离子水进行沉淀，再将产物真空干燥恒重。  \n\n（45）光聚合法制备胺基磁性纳米凝胶在三口石英烧瓶中加入含有50μL烯丙基胺和5mg N,N-亚甲基双丙烯酰胺的58mL双蒸水，快速搅拌下通氮气30min，加入超声1min 的四氧化三铁磁流体2mL（固含量为7.3mg，平均粒径8nm士lnm），分散均匀后，搅拌下通氮气，用紫外光辐照（2支8W低压汞灯，254nm主波长）3min后，滴加含有550L烯丙基胺的水溶液10mL，8min加完，继续光照2min 后停止反应。所得液体作磁分离，洗涤数次后加5mL三蒸水超声重新分散，得到纯净的聚烯丙基胺-磁性纳米凝胶，平均粒径2lnm士5nm，其饱和磁化强度为50emu/g，具有超顺磁性和具有确定的生物素结合能力。  \n\n（46）光聚合法制备二苯甲酰-L-酒石酸手性分子印迹聚合物称取1mol二苯甲酰-L-酒石酸于玻璃试管中，加入4mmol丙烯酸和适量溶剂乙睛超声使其溶解，作用2h后加人10mmol三羟甲基丙烷三丙烯酸酯、光引发剂二苯甲酮（总重量的0.6%）和助引发剂三乙胺（总重量的1%）混合均匀，充氮气2min，然后抽真空并密封置于冰水浴中，用紫外光照射1.5h，将所得块状产物取出后粉碎、研磨，用甲醇/乙醇真空干燥得到二苯甲酰-L-酒石酸手性分子印迹聚合物，对二苯甲酰-L-酒石酸有很好的识别性，其分离因子可达5.41。  \n\n（47）光固化制备超疏水表面将聚二甲基硅氧烷（Sylgardl84道化学公司）原料预聚物和交联剂按质量比10：1混合均匀，静置20min后，浇注到平整的新鲜荷叶表面，放在40℃烘箱中反应4h，固化后将聚二甲基硅氧烷弹性体与母版剥离，得到复制有荷叶表面微结构的阴模软模板。  \n\n将质量分数68%的聚氨酯丙烯酸酯（沙多玛CN990)、20%的双季戊四醇五丙烯酸酯、10%的丙烯酸异冰片酯和2%的光引发剂651混合均匀，于0.085MPa真空烘箱中避光静置排除气泡，然后将溶液平铺在玻璃基板上，盖上复制有荷叶表面结构的软模板，置于紫外灯下曝光15min，揭起软模板，将样品在40℃烘箱中干燥5h，样品表面微结构与荷叶表面微结构十分类似，有大量微乳类，平均直径7～12μm，高度为10～18um，与水的接触角高达150°。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 631,
+        "chunk": "# 第12章 光固化材料在其他领域应用",
+        "category": " Introduction"
+    },
+    {
+        "id": 632,
+        "chunk": "# 12.1. 1 快速成型制造技术  \n\n快速成型制造技术（rapid prototyping &manufacturing，简称 RP&M）是 20 世纪后期发展起来的先进制造技术，是制造行业的一次革命。RP&M是将计算机控制技术和新材料科学融为一体的制造技术，它一改传统机械切、削、刨、磨等材料递减的方式，而是像造房子一样采用材料递增叠加的方式，是一种全新的全数字化的制造方法。它具有以下两大特点。  \n\n（1）快速化实现制造过程的快速设计、快速修改、快速生产，使产品在品种上、规格上、样式上都不断推陈出新、更新换代，达到产品小批量、多样化、个性化，并可实现无库存的生产方式。  \n\n（2）智能化整个制造过程自动化、连续化、快速化，全部由计算机控制，不需要人来操作。可以制造出非常复杂的形状，并容易修改，容易重复。  \n\n快速成型制造过程如图12-1所示。  \n\n![](images/5b749b07b070b1555c8aea43b96864b48ed641ea87c0efd61f323e6e3ff680ee.jpg)  \n图12-1快速成型制造过程示意  \n\n快速成型制造技术是由人们设计一个三维模型输人到计算机中，或将一个已知样件通过非接触测量系统直接输入到计算机中。计算机处理系统将得到的模型以一定的高度分层，得到每一层二维平面图形。计算机控制系统按照二维图形控制激光器或其他装置进行加工得到二维平面样件，同时将加工得到的一个个二维平面样件叠加起来就形成原设计模型或样件。由于每次制作的都是二维平面样件，像造楼房一样一层一层叠加往上造，所以使任何复杂形状的制造都变得很简单。  \n\n快速成型制造技术目前有下面几种快速制造方法。  \n\n（1）激光选择烧结法由热熔性的粉末固体微粒薄薄地铺一层，由计算机控制激光来扫描一个二维平面图形，将固体微粒烧结或黏结成固体平面样件，这样铺完一层再铺一层，最终形成三维实体。 联同你通的民生和  \n\n（2）熔融沉积成型法由计算机控制一个可 $_{x y}$ 方向移动的可控加热喷嘴，按计算机给定的二维平面图形移动时，将熔融的材料喷上，并冷凝成固态，这样一层层叠加成三维实体。  \n\n（3）薄层材料制造法由计算机控制激光束切割一个传动的膜带状的薄层材料，按二维平面图形的轮廓线切割的薄层材料，一张张地落下去叠加，黏合成所需要的三维模型。  \n\n![](images/793b4af5f66e01411bf7c81277cf96e17956bc87dde77c1c01d0a39dc8d4b5f0.jpg)  \n图12-2光固化快速成型工艺  \n\n（4）立体光刻法由计算机控制激光束在光固化树脂液面上扫描，见光部分固化形成一个二维平面图形，并控制图形下降，露出光固化树脂液面，重复扫描固化，叠加起来最后形成三维实体（图12-2)。通过不断研究和发展，立体光刻法已成为发展最快而且最有前景的一种快速成型方法。",
+        "category": " Introduction"
+    },
+    {
+        "id": 633,
+        "chunk": "# 12.1. 2 立体光刻  \n\n立体光刻（stereolithography，简称SL）所用的材料为光固化树脂，固化前类似于涂料，固化后属于工程材料。由于SL法的特殊制造工艺，对光固化树脂有特殊性能要求。  \n\n（1）高固化速率SL法制造时由计算机控制激光束扫描，束宽约 $1\\mathrm{mm}$ ，扫描速度在 $\\scriptstyle2\\mathbf{m}/\\mathbf{s}$ 以上，每扫描一层，固化厚度约 $0.1\\mathrm{mm}$ 。这就要求光固化树脂见到激光束应立刻固化，而当激光束离开后，树脂聚合反应必须立刻停止，不能向周围扩散，否则影响精度。  \n\n（2）低固化体积收缩率光固化树脂固化时发生的体积收缩，不仅造成样件尺寸大小误差，更严重时会造成样件卷曲变形，因此选择低体积收缩的光固化树脂，降低树脂固化时的体积收缩率是提高制造精度的关键。  \n\n（3）低黏度SL法制造过程是一层层树脂固化叠加而成的。每做完一层，由于表面张力作用，液体树脂很快自动覆盖已固化的固态树脂表面。所以每固化一层后，需用刮板自动将树脂液面刮平涂覆一次，待液面自动流平后，才能进行激光扫描，这样要求光固化树脂黏度越低越好。  \n\n（4）高贮存稳定性SL法制造中光固化树脂通常是一次性加入到液态树脂槽中，不再取出。随着使用不断消耗，不断添加，长期使用时，树脂性能应基本保持不变。这就要求光固化树脂有很好的光稳定性、热稳定性、化学稳定性和组成稳定性(低挥发性)。  \n\n（5）其他光固化树脂要清亮透明，无毒无味，不污染工作环境。固化后有很好的物理力学性能，如较高的断裂强度、抗冲击强度、硬度和韧性等。  \n\n立体光刻所用的光固化树脂是由低聚物、活性稀释剂光引发剂和助剂等组成。固化方式可为自由基光固化、阳离子光固化以及双重光固化。  \n\n低聚物的选择主要是考虑固化后制件的物理力学性能。对自由基固化体系，常用低聚物为环氧(甲基)丙烯酸酯、聚氨酯(甲基)丙烯酸酯和聚酯(甲基)丙烯酸酯等。对阳离子固化体系常用的低聚物主要是环氧树脂。  \n\n活性稀释剂主要为调节黏度和固化速率，通常选择单、双、多官能度丙烯酸酯配合使用，第三代丙烯酸酯单体具有高反应活性，黏度又低，聚合转化率高，非常合适用作主体光刻的活性稀释剂。乙烯基醚类既可阳离子固化，又可自由基固化，黏度也低，活性很高，也是理想的活性稀释剂。  \n\n光引发剂主要考虑与激光光源波长相匹配，以及高引发活性。目前立体光刻的激光光源，采用He-Cd激光器（325nm）或Ar激光器（35lnm、364nm），因此选用1173、184（对 $_\\mathrm{He\\mathrm{Cd}}$ 激光器）和651、TPO、819（对Ar激光器）最为合适。对于阳离子固化体系，则以硫盐、芳香茂铁盐。  \n\n立体光刻用的光固化树脂还需适量添加助剂，如消泡剂、流平剂、阻聚剂等，对有颜色要求的制件，则还需加入颜料。  \n\n立体光刻是20世纪90年代中期才发展起来的快速成型技术，目前已经在制造行业的各个领域获得广泛的应用，涉及的行业有汽车、航天航空、电子、通信、家电、铸造、塑料、建筑、装饰、玩具、艺术和医疗等行业，如汽车、航空航天、家电制造业中制造模具、模型和器具，建筑业中建筑物模型，医学中人体器官、骨骼模型，艺术行业的艺术模型、玩具业中玩具模型等。但目前对于大尺寸、高精度部件仍不能达到理想的结果。由于立体光刻中计算机控制软件和激光曝光装置及成型设备基本定型，故改进的焦点主要集中在制造材料—光固化树脂上，也就是要最大限度降低固化体积收缩率和体系黏度。目前有两种途径来实现此目的：一是开发低黏度、高活性、低体积收缩的低聚物，特别是超支化低聚物；二是进一步开发、完善阳离子固化体系，引人膨胀聚合物体系。利用一些螺环、桥环化合物开环聚合时，产生体积膨胀，有望使光固化树脂固化时实现零体积收缩，这无疑对立体光刻成型技术会有突破性进展。  \n\n聚合时的体积收缩是一般单体的固有属性，产生的原因有两方面。  \n\n（1）聚合时分子间由范德华作用距离（0.3～0.5nm）变为共价键距离（C—C共价键约0.154nm)，尽管C=-C双键变为C—C单键，由0.133nm增大到0.154nm，但分子间发生一次加聚反应距离就要缩短0.125～0.325nm，因而密度增大，出现体积收缩（图12-3)。表12-1为加成聚合时的体积收缩率。  \n\n![](images/04776efa7965c3d90e7f0ecfa1b2452f4e7a995ced59e97e5a6c26d8ae3bb96b.jpg)  \n图12-3加成聚合反应前后分子间距离变化  \n\n（2）杂乱无章的液态单体分子固化后规整性增加造成体积收缩，并且聚合物分子规整性越强，排列得越整齐，固化后体积收缩越大。  \n\n表12-1加成聚合时的体积收缩率（计算值）  \n\n\n<html><body><table><tr><td>单体</td><td>乙烯</td><td>丙烯</td><td>丁二烯</td><td>氯乙烯</td><td>丙烯腈</td><td>甲基丙烯酸甲酯</td></tr><tr><td>体积收缩率/%</td><td>66.0</td><td>39.0</td><td>36.0</td><td>34.4</td><td>31.0</td><td>21.2</td></tr><tr><td>单体</td><td>醋酸乙烯</td><td>苯乙烯</td><td>邻苯二甲酸二烯丙酯</td><td></td><td>N-乙烯咔唑</td><td>1-乙烯基花</td></tr><tr><td>体积收缩率/%</td><td>20.9</td><td>14.5</td><td>11.8</td><td></td><td>7.5</td><td>6.0</td></tr></table></body></html>  \n\n但阳离子引发开环聚合体系，体积收缩要比加成聚合小得多。这类单体在聚合时，因为开环，除形成C一C共价键，还有C—O键出现，减少了分子间距离缩短，故体积收缩率要减少（图12-4)。表12-2列举了部分开环聚合的体积收缩率。  \n\n![](images/ad4d8ac32b7b8ab042bacc811f17b9275eded032bad0e356c763bae2a9e5757e.jpg)  \n图12-4开环聚合反应前后分子间距离变化  \n\n对杂原子螺环、桥环化合物的开环聚合研究发现在聚合时，不仅不发生体积收缩，反而产生了体积膨胀（表12-3)。如果将这种膨胀聚合体系开发出来，并引人到立体光刻的光固化树脂中，就可以制备零体积收缩的立体光刻模具。  \n\n表12-2开环聚合时的体积收缩率（计算值）  \n\n\n<html><body><table><tr><td>单体</td><td>环氧乙烷</td><td colspan=\"2\">环氧异丁烯</td><td>环丁烯</td><td colspan=\"2\">环氧丙烷</td><td>环戊烯</td><td>环戊烷</td><td>四氢呋喃</td></tr><tr><td>体积收缩率/%</td><td>23</td><td colspan=\"2\">20</td><td>18</td><td colspan=\"2\">17</td><td>15</td><td>12</td><td>10</td></tr><tr><td>单体</td><td>环已烷</td><td colspan=\"2\">氧化苯乙烯</td><td>环庚烷</td><td colspan=\"2\">环辛烯</td><td colspan=\"2\">双酚A缩水甘油醚</td><td>环辛二烯</td></tr><tr><td>体积收缩率/%</td><td>9</td><td colspan=\"2\">9</td><td>5</td><td colspan=\"2\">5</td><td colspan=\"2\">5</td><td>3</td></tr><tr><td>单体</td><td colspan=\"2\">环十二碳三烯</td><td colspan=\"3\">5-氧杂-1，2-二硫杂环庚烷</td><td colspan=\"3\">氧化二甲基甲硅烷环状四聚体</td><td>环辛烷</td></tr><tr><td>体积收缩率/%</td><td colspan=\"2\">3</td><td colspan=\"3\">3</td><td colspan=\"3\">2</td><td>2</td></tr></table></body></html>  \n\n表12-3部分螺环、桥环化合物开环聚合时的体积膨胀  \n\n\n<html><body><table><tr><td>单体</td><td></td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>聚合温度/℃</td><td></td><td></td><td>25</td><td>25</td><td>108</td><td>30</td><td>25</td><td>130</td></tr><tr><td>体积膨胀/%</td><td>0</td><td></td><td>2.8</td><td>4</td><td>7</td><td>12</td><td>9</td><td>17</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 634,
+        "chunk": "# 2.2 光固化软模压复制技术  \n\n软模压复制技术是20世纪90年代出现的一种新型复制技术。它通过光固化型或热固化型胶态状高分子材料为信息受体，在适当的机械力和光或热引发作用下，对表面浮雕型模版进行复制而获得复制图像。软模压复制技术最早应用于全息复制，能在塑料片材、玻璃、陶瓷、木材和金属等各种不同质地的基材上完成全息图的精密复制，成为光子产业的一个重要组成部分。近年来，软模压复制技术与印刷技术结合，进入了“软印刷技术”之一的纳米图像印刷技术领域，发展成为一种制作纳米/微米结构的新技术，在纳米电子器件、纳米光学元件、纳米生物传感器及其他具有纳米结构的功能图形制作方面，将显现出其独特的技术优势，为微电子产业、生物与生命科学、环境与新能源技术等领域的加速发展带来重大的影响。光固化软模压技术由于操作方便，固化速率快，无环境污染，加工精度高等特点，受到人们的关注，成为精细加工的一种新方法、新手段。",
+        "category": " Introduction"
+    },
+    {
+        "id": 635,
+        "chunk": "# 12.2.1光固化软模压全息复制技术  \n\n软模压全息复制要求光固化材料具有以下的性能：  \n\n$\\textcircled{1}$ 较低的黏度，一般控制在 $(2.0\\pm0.5)\\mathrm{Pa}\\cdot\\textrm{s}$ ? $(25^{\\circ}\\mathsf{C})$ ，$\\textcircled{2}$ 较快的固化速率，控制在 ${<}60\\mathbf{s}$ $\\textcircled{3}$ 粘接选择性，对基材有较强的附着力，但对全息模版容易脱模；$\\textcircled{4}$ 较高的透光率，一般要求透光率 $93\\%$ ，以保证复制的全息图的光学性能和利于加工。  \n\n软模压全息复制技术首先用光致抗蚀剂制作金属母版：利用两束相干激光，相互成一定夹角，在光致抗蚀剂上相干形成全息图，制得表面浮雕型全息图，利用光致抗蚀剂表面的变化存储了全息图像信息。再经光致抗蚀剂表面上电铸，制得金属母版。全息金属母版通常由金属镍制成，其表面为浮雕全息图。将全息金属母版对热塑性塑料薄膜或片材进行压印，全息图通过全息金属母版转印到塑料薄膜或片材上，可以大量复制全息图。再利用带有全息图的薄膜，覆盖到涂有光固化树脂的基材上，UV曝光固化，固化的光固化树脂记录了薄膜上  \n\n![](images/ce26cf096fb7eb73f1220e06eadb4e8aefe769ac62ce0d31734e7d911226b5ba.jpg)  \n图12-5制作镭射玻璃的步骤  \n\n的全息图信息。  \n\n通过光固化软模压全息复制技术，不仅可以大量复制全息图，而且可以制作镭射玻璃、镭射装饰板等新型装饰材料。以镭射玻璃制作为例（图12-5)：将玻璃清洗、干燥后，涂覆一层光固化树脂；再用上述带有全息图的薄膜覆贴到涂有光固化树脂的玻璃上，紫外光透过玻璃照射到光固化树脂使固化，记录了全息图信息；取下薄膜，为了美观和装饰目的，在玻璃上丝印各种图案；再在形成浮雕型全息图的光固化树脂上真空镀铝，使玻璃板具有反射能力，产生反射全息图；最后铝表面涂一层UV光固化涂料作保护膜，制得了五光十色、色彩缤纷的镭射玻璃。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 636,
+        "chunk": "# 12.2.2光纳米图像印刷技术  \n\n纳米图像印刷技术是一种新型的压印转印技术，用于纳米凹凸图形的加工制作。它是将具有纳米凹凸图像的模具作“印版”，用预先涂有聚合物涂层的硅片或玻璃片作基板（被印物)，通过精确压印并定型后，再把模具与基板分离，这样便把模具表面的纳米凹凸图像准确地转印到基板表面的聚合物涂层上。逐个被转印出的图像与模具表面的凹凸图形大小相等，深浅一致，但形状正好相反，即阴图转为阳图，模具上凸出地方，在基板聚合物涂层上凹下地方，反之亦然。这种利用印刷压模的原理转印出具有纳米凹凸图形的技术叫纳米图像  \n\n印刷技术(图12-6)。  \n\n模具是实施纳米图像印刷的最重要部件，也是图像的“给体”。模具加工的精度决定了纳米图像转印质量的高低。目前模具加工通过干刻蚀来制作：在模版片材（金属、玻璃、硅、二氧化硅/硅等）上，涂布电子束抗蚀剂（如聚甲基丙烯酸甲酯）膜，然后按预先设计好的图形，通过电子束在该膜上直接扫描出掩膜，再以此掩膜为基础，用干刻蚀方法在模板表面刻蚀出相应的凹凸图像制成所用的模具。目前已能制作出转印精度 $10\\mathbf{nm}$ 图像的模具。  \n\n基板在纳来图像印刷中是图像的“受体”，它是由基材和聚合物薄膜组成的。基材一般为硅、二氧化硅/硅、玻璃等片材；聚合物薄膜则根据压印方式不同而不同。热压印  \n\n![](images/46e77158b2d2b0072c9dbf98ace623b6e070f40e7eb3bf5eb0ab2d89cbd80221.jpg)  \n图12-6纳米图像印刷原理  \n\n纳米图像印刷中聚合物薄膜为热塑性树脂，如聚甲基丙烯酸甲酯、聚苯乙烯、聚碳酸酯等；室  \n温压印纳米图像印刷中聚合物薄膜为溶胶-凝胶材料；光纳米图像印刷中聚合物薄膜则为光固化树脂。将聚合物溶液采用旋涂或其他涂布方式均匀地涂覆在基材表面，制得图像转印用的基板。  \n\n![](images/380129392d157ce8ec73bdeef94219bd401f8059217f80a9d4a481e3130930cc.jpg)  \n图12-7光纳光图像印刷原理  \n\n图像的转印在热压印工艺时，需将基板温度升高到聚合物玻璃化温度 $T_{\\mathrm{g}}$ 以上温度，聚合物变成柔软而可塑时，把模具压印到基板的聚合物膜上，柔软而富于可塑的聚合物被挤压并完全填满模具与基板间的缝隙中。当温度冷却至低于 $\\scriptstyle{T_{8}}$ 时，被压印成型的聚合物膜固化定型，分开模具，纳米图像就被转印到基板的聚合物膜上。  \n\n光纳米图像转印工艺其模具为透明性非常好的石英玻璃，而基板上的聚合物则为光固化树脂。由于光固化树脂分子量较小，黏度也较低，因此，在模具与基板压印中所需压力很小，一般在0.1MPa以下（热压印一般在 ${\\mathsf{S M P a}}$ ，压印中光固化树脂经UV光照射固化成型（图12-7)。光纳米图像印刷工艺其图像转印速度快，生产效率高；印刷压力小；印刷工艺在常温下进行，节省能耗；加工精度高，清晰度好，可制作出高度 $300\\mathbf{nm}$ 、线宽 ${50}\\mathrm{{nm}}$ 的凹凸图像，实验室更成功地加工出$\\mathsf{5n m}$ 的高精度图形。人们正企盼着这种新的制造工艺能在半导体器件制造中发挥作用。如果能把光功能、电功能、生物功能等功能性基团引入光固化树脂中，则可以非常简便地加工制作出各种用途的功能器件，成为制造纳米器件、纳米机器的重要手段之一。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 637,
+        "chunk": "# 12.2.3 光软刻技术  \n\n软刻技术是近年来发展起来的一种制作纳/微米结构的新方法。该方法利用弹性体材料聚二甲基硅氧烷等作为软印章或软模板，通过聚合物等材料的铸模、模塑、印刷等方式来制备各种微结构。而光软刻技术则结合了光固化技术发展成熟和应用广泛的优势及软刻技术的便捷、高效等特点，可以复制得到高质量的微结构。  \n\n光软刻技术应用的实例是制备具有仿荷叶表面结构的超疏水表面（图12-8)。将聚二甲基硅氧烷的预聚物和交联剂混合均匀，静置20min后浇注到平整的新鲜荷叶表面，在40℃烘箱中反应4h，固化后将聚二甲基硅氧烷弹性体与荷叶分离，得到复制有荷叶表面微结构的阴模软模板。将经真空避光排除气泡的光固化树脂涂覆在基板（玻璃片或硅片）上，盖上复制有荷叶表面结构的软模板，在UV灯下曝光，最后揭起软模板，并将样品放在40℃烘箱中5h，制得的仿荷叶表面结构的超疏水表面。扫描电镜观察到样品表面具有大量微乳突，类似于荷叶表面微结构特征，乳突的平均直径为 $\\scriptstyle7\\sim12\\mu\\m{\\mathrm{m}}$ ，高度为 $10\\sim18\\mu\\mathrm{m}$ 。样品表面与水的接触角测量可高达 $157^{\\circ}$ ，滚动角 $2^{\\circ}$ ；而超疏水的标志为接触角大于 $\\boldsymbol{150^{\\circ}}$ ，滚动角小于$3^{\\circ}$ ，因此用光软刻技术复制的仿荷叶表面可以实现表面超疏水性。  \n\n![](images/f0f4065f61a6b787a7953a70ab3c8b26cd46f1a37329d592174a7d5374ee5152.jpg)  \n图12-8光软刻技术示意",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 638,
+        "chunk": "# 12.3.1牙科修复树脂  \n\n牙科的治疗与一般疾病的治疗不同，除了使用药物以外，不少是为了修复牙齿的缺损和充填牙齿的洞，因此牙科用的修复材料是非常重要的医用材料。  \n\n牙科修复材料品种很多，用于修复因龋齿、外伤等原因造成牙体缺损的修复材料主要有三类：合金材料、烤瓷和复合树脂。银汞合金作为牙科充填材料已有160多年历史，现仍作为后牙充填的常用材料。但银汞合金与牙色匹配性差，易发生电化学腐蚀和蠕变，特别是在生产和使用环节中汞对环境造成严重污染以及对人体不安全，使许多发达国家已经限制和禁用银汞合金进行牙齿修复。20世纪60年代，复合树脂作为一种美容修复材料，因其操作简便、色泽选择灵活性大、理化性能优越等特点，极大地满足了临床医生和患者对牙齿美容修复的要求，而且弥补了以前树脂材料在硬度和耐磨性方面的不足，又能够与牙釉质及牙本质产生牢固的化学结合，减少了牙体切割，最大限度地保存了天然牙体硬组织，现已成为牙体缺损修复治疗必不可少的重要材料。  \n\n牙科修复用的复合树脂是一种由有机树脂基质和经过表面处理的无机填料以及引发体系组合而成的材料，由于应用于人体口腔中，使用环境比较特殊，因此其性能必须要符合：  \n\n$\\textcircled{1}$ 无毒，对牙齿组织及口腔黏膜没有危害；  \n\n$\\textcircled{2}$ 化学稳定性好，不受唾液、食物、细菌、酶等影响发生分解；  \n$\\textcircled{3}$ 耐水性好，不易老化，不溶解渗出有害物质；  \n$\\textcircled{4}$ 使用方便，固化迅速；  \n$\\textcircled{5}$ 固化后有较好的物理力学性能，如耐磨、硬度等。  \n\n牙科修复用的复合树脂，按照固化方式不同可分为化学固化型、光固化型和光-化学双重固化型，而光固化型又分为紫外光固化型和可见光固化型。  \n\n化学固化型复合树脂是双组分，由于固化过程中产热较高，固化后体积收缩较大，双组分混合后，操作时间短，不宜在患者口内直接修复，需要间接制作，给临床带来不便，因而渐渐被光固化型复合树脂所取代。光固化型复合树脂为单组分，具有固化速率快、使用方便、固化后树脂性能优异等特点。特别是随着新树脂和新型填料的开发和应用，湿性粘接技术的发展，牙科修复用光固化复合树脂的物理力学性能得到很大改善，在某些方面已经超过了传统的银汞合金修复材料，已逐步替代银汞合金材料用于前后牙牙科缺损修复。此外，它还可以用作防龋齿的窝沟封闭剂、修复体与牙体间的胶黏剂、假牙基托材料以及牙冠外形重建的核桩树脂材料等。由于皮肤、黏膜和眼睛长时间被紫外光照射会引起光致癌、光过敏反应以及组织烧伤等危险，为了避免紫外光对患者口腔组织的伤害和减少紫外光对医生眼睛的损伤，光固化型复合树脂由紫外光固化型发展为可见光固化型。目前，可见光固化技术已经广泛应用于牙科修复复合树脂的临床应用，包括牙科胶黏剂的固化。这三种复合树脂固化方式比较见表12-4。  \n\n表12-4牙科修复用复合树脂固化方式比较  \n\n\n<html><body><table><tr><td>项目</td><td>化学固化</td><td>UV固化</td><td>可见光固化</td></tr><tr><td>光源</td><td>无</td><td>金属卤素灯、中压汞灯</td><td>LED、金属卤素灯 380~540</td></tr><tr><td>波长/nm</td><td>一</td><td>250~380</td><td>470</td></tr><tr><td>Amax/nm</td><td>一</td><td>365</td><td>优于UV固化，固化深度深</td></tr><tr><td>光透过性</td><td>一</td><td>较差，固化深度浅</td><td></td></tr><tr><td>引发体系</td><td>氧化还原体系</td><td>安息香醚、二苯甲酮/叔胺</td><td>樟脑/叔胺</td></tr><tr><td>可操作时间</td><td>短</td><td>长</td><td>长</td></tr><tr><td>固化时间</td><td>几分钟</td><td>几秒至几十秒</td><td>几秒至几十秒</td></tr><tr><td>组分</td><td>双组分</td><td>单组分</td><td>单组分</td></tr><tr><td>安全性</td><td>安全</td><td>对皮肤、眼睛、黏膜有害</td><td>安全</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 639,
+        "chunk": "# 12.3.2 可见光牙科修复树脂的组成  \n\n可见光牙科修复用复合树脂是一种无机颗粒增强型聚合物复合材料，由美国学者Bowen于1962年最早提出。它是由有机树脂和经过处理的无机填料组成的非均相混合物。有机相中含有树脂基质、光引发剂、阻聚剂、稳定剂等；无机相为经过特殊表面处理的粉状无机填料，均匀分散于有机基质中，以增强树脂的强度和模量。在牙齿修复过程中，有机树脂基质作为复合树脂的连续相，将颗粒状的无机填料（分散相）包裹黏结在一起，于室温下以及在可见光照射下，较短时间内固化成型，并赋予材料一定的强度和形状。  \n\n（1）树脂基质（resin matrix）由低聚物和活性稀释剂组成。目前低聚物均为双甲基丙烯酸树脂，使用最普遍的是双酚A双甲基丙烯酸缩水甘油酯（bis-GMA)。bis-GMA分子量较大，有效地降低了一定体积内参加聚合反应的双键浓度，从而减小了反应造成体积收缩；分子中双键能在光固化时形成高度交联的三维网络结构，使材料的力学性能和耐化学药品性大大提高。  \n\n为了降低树脂的黏度，增加聚合度，还采用氨基甲酸双甲基丙烯酸酯（UDMA）作为基础树脂。为了获得较好的临床可操作性和较高的填料装载量，还要在基础树脂中添加活性稀释剂降低体系的黏度，最常用的活性稀释剂为二缩三乙二醇双甲基丙烯酸酯(TEGDMA)。  \n\n![](images/17929460f6b0b8a37917716df9921791b6547f0c60d76c7d8403dcdc0b01a6ed.jpg)  \nTEGDMA  \n\n（2）樟脑/胺可见光引发体系樟脑（CQ）又称茨菠酮，为双基化合物，作为可见光引发剂，属于夺氢型光引发剂，其最大吸收波长在470nm；具有毒性低、生物相容性好等优点，与叔胺助引发剂配合使用，在光固化牙科材料中成为首选的光引发剂。虽然其在470nm 处消光系数e只有20～50mol/(L·cm)，但系间窜跃量子效率可高达0.92以上，产生激发三线态的概率较高，并且樟脑在发生光化学反应后，其长波吸收性能消失，具有光漂白功能，因此非常适合填充体系和厚层材料的光固化。与樟脑配合使用的叔胺助引发剂最常用的是甲基丙烯酸二甲胺基乙酯（DMAEM)。樟脑吸收可见光能后，由基态跃迁到激发态，在激发态樟脑与叔胺助引发剂发生电子转移、夺氢历程，产生胺烷基自由基引发聚合。产生的羰基自由基可以偶合形成频哪醇，也可经夺氢反应生成醇。  \n\n（3）无机填料无机填料在复合树脂中作为复合材料的分散相可以增强材料的物理力学性能，特别是耐磨性和刚性，增加X射线的阻射性能，减少膨胀系数，又能减少有机树脂基体的含量，降低树脂固化收缩率和成本。增强型无机填料第一代使用石英粉，第二代为胶体二氧化硅，第三代为钡、锶、锆、玻璃粉和陶瓷粉。无机填料需经过偶联剂处理，最常用的偶联剂为有机硅偶联剂KH570（y-甲基丙烯酰氧丙基三甲氧基硅烷)，它能与无机填料表面的羟基反应，形成硅氧键，还因分子中含有甲基丙烯酰氧双键，可与树脂基质发生共聚合作用；将有机、无机两个相界面结合在一起，防止水分子沿填料与树脂间的界面渗入，提高水解稳定性，同时增强材料的物理力学性能。 .O",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 640,
+        "chunk": "# 12.3.3牙科修复树脂的种类  \n\n目前牙科修复材料临床应用根据所加填料颗粒大小不同，将复合树脂分为如下几种。  \n\n（1）传统型复合树脂，填料粒度1～100μm，平均8～12um，属于第一代复合树脂。由于填料颗粒度大，树脂表面不易抛光，现已基本不用。  \n\n（2）小颗粒型复合树脂，填料平均粒度 $1\\sim5\\mu\\mathrm{m}$  \n\n（3）超微型复合树脂，填料为粒径0.04～0.4μm的气相二氧化硅，具有良好的抛光性和持久的美观性能。但是，由于超微填料二氧化硅平均粒径大小，具有较大的比表面积，需更多的树脂才能润湿颗粒，因此，填料装载量受到限制。  \n\n（4）混合型复合树脂，由质量分数为 $10\\%\\sim20\\%$ 的超微填料 $(0,04\\sim0.4\\mu\\mathrm{m})$ ）和平均颗粒为 $1\\sim5\\mu\\mathrm{m}$ 的玻璃粉一起组成的总质量分数可达 $75\\%\\sim80\\%$ 的复合树脂，具有比超微型复合树脂更宽的颜色范围、较小的线膨胀系数、较小的边缘应力和较高的强度，是目前最流行的品种。但是，抛光性稍差。  \n\n（5）新型复合树脂，又称为理想颗粒型复合树脂，介于超微型和混合型复合树脂之间，通过对填料颗粒大小优化，使其同时具有超微型复合树脂的抛光性能和混合型复合树脂的物理力学性能。  \n\n近年来，混合型复合树脂根据牙科修复的不同用途又细分为如下几种：  \n\n（1）可流动型复合树脂这是一种较低黏度的复合树脂，主要组成与混合型复合树脂相似，只是填料含量较低，只占材料总体积的 $42\\%\\sim53\\%$ ，因此聚合体积收缩较大，物理力学性能也较差。但黏度小，在聚合时，处于复合树脂和胶黏剂之间的低黏度材料能缓解材料在聚合时产生的收缩应力，在一定程度上减小了边缘缝隙形成的概率。低黏度和流动性好；使其对非常小的龋齿空洞充填、较深的沟窝封闭操作非常方便和有效。此外，树脂具有较低填料含量和较高韧性的特点，也可作为其他类型复合树脂直接充填物的调衬应用，对缓冲应力非常有效。  \n\n（2）可压缩型复合树脂又称为后牙复合树脂，是探索替代银汞合金的复合树脂，固化深度可达 $\\mathsf{5m m}$ ，临床操作上可压缩充填，可雕刻，但尚未达到能像银汞合金一样，还有一定的技术难度。其无机填料为纤维状或多孔状及具有特殊表面微细结构的颗粒，填料含量占材料总体积的 $60\\%\\sim70\\%$ 。由于填料之间的相互作用，造成复合树脂具有可压缩性。其树脂采用三个以上功能基团的甲基丙烯酸酯，在固化后具有更高的交联密度，材料具有更大的刚性。可压缩型复合树脂具有固化深度高体积收缩小、低磨耗等特点，适用于多种类型齿洞的充填修复。临床操作时可用流动型复合树脂进行调衬，使用分层充填技术，在抛光调磨后，表面严格隔湿、酸蚀、干燥，再涂一层封闭剂，完成修复。  \n\n（3）间接修复用复合树脂是指口腔外环境中用复合树脂完成嵌体、贴面、冠桥等修复体，故又称做“冠桥树脂”。作为间接修复体，与金属、瓷修复体相比，其优点是对颌面的磨损较少，制作简单。间接修复用复合树脂因其聚合在口腔外进行，不受口腔条件的限制，一般采用双重固化，在初次光固化后，再采用热固化、光固化或热压聚合等二次固化，提高转化率，可接近 $100\\%$ 。其填料的种类、颗粒大小设计更合理，并采用有机纤维或无机纤维（晶须）加强结构，使其物理力学性能大为改善，耐磨性能提高，固化收缩减少。  \n\n（4）桩核复合树脂是为了修复牙冠的缺损，为最终修复体提供足够的固位性和抗力性而采用的复合树脂。桩的主要作用就是把桩核复合体固位于根管，核可看作是桩向龈上的延伸部分，为修复体提供固位和传递最终修复体的应力。因此要选择与牙体组织具有相似物理力学性能和最大固位力的根桩体系，最大限度地保留牙体组织，选用与牙体、材料都有很强黏结力的复合树脂胶黏剂。桩核复合树脂采用纤维增强，具有与牙体组织相似的物理力学性能，并有优良传递和吸收应力的性能，可以最大限度地分散缓冲牙根的应力，而且美观性也较好，特别适合于全瓷修复体。同时新型双重固化树脂胶黏剂作为桩核体系的重要组成部分，不仅与牙体、金属、瓷有较强的黏合能力，还具有优良的操作性能，外露部分可直接光照 $20\\sim40\\mathrm{s}$ 快速固化，减少了水分的影响，不能光照部分则通过化学聚合完成固化。  \n\n牙齿的修复需要经过磨蚀、酸蚀、清洗、干燥、涂抹光固化牙用胶黏剂、固化和涂抹光固化牙用修复树脂、固化和抛光等多个步骤，以保证牙用修复树脂能牢固地与牙体黏合。以下是龋齿修复的操作流程：龋齿孔内磨蚀 $\\rightarrow$ 冲洗吹干 $237\\%$ 磷酸酸蚀 $(15\\mathbf{s})\\to$ 冲洗(15s)轻吹空气干燥(5～10s)→涂抹光固化牙用胶黏剂(10s)→空气轻吹(5s)低功率光固化(10s)→光固化牙用树脂涂薄层 $\\mathbf{\\Psi}\\to$ 光固化 $(20\\mathbf{s})\\rightarrow$ 涂光固化牙用复合树脂 $\\mathbf{\\rightarrow}$ LED光固化(30s)→涂光固化纳米树脂 $\\rightarrow$ LED光固化(20s) $\\Bumpeq$ 抛光 $\\star$ 完成龋齿修补。  \n\n医用导电压敏胶是医疗器械行业中应用的一种新型的UV胶，它既是压敏型的，又具有导电性，在无溶剂存在下通过指压而活动的始终保持黏性的黏弹性材料。在用力较轻的指压条件下，胶面即可瞬间与人体皮肤表面相粘，与医疗专用设备组合后，能很好地传递电流信号。由于其具有良好的内聚力和不干性，使用结束可方便地与皮肤剥离，且在皮肤表面不留下残留物。  \n\n医用导电压敏胶除了有良好的导电性和压敏性外，还要求它与人体皮肤接触后，不会产生刺激和过敏等不良反应。按国家标准规定，医用导电压敏胶必须满足以下生物学性能要求： $\\textcircled{1}$ 细胞毒性 ${\\leqslant}1$ 级； $\\textcircled{2}$ 原发性皮肤刺激无或轻微； $\\textcircled{3}$ 致敏 ${\\leqslant}1$ 级。同时，国家标准还规定了卫生指标：要求产品的污染菌数 ${\\leqslant}1000{\\mathsf{c f u}}/{\\mathsf{g}}$ 口  \n\n采用UV固化技术生产医用导电压敏胶，用于制备各种医用电极、理疗电极、一次性使用心电电极、高频电刀用板电极等。  \n\n（1）理疗仪是一种保健治疗仪，对颈椎病、肩周炎、腰腿病、关节炎和软组织损伤等病症有较好的辅助治疗效果。它是以传统的针灸理论为基础，将低频脉冲与经络、神经理论相结合，采用皮肤电极对人体穴位进行电流刺激，达到激活经络机能、治疗疾病的目的。早期的理疗仪电极主要是用铜片外包绒布，使用时必须用水润湿绒布使其导电，并要在电极外用橡皮膏固定。而使用导电压敏胶型电极，由于电极上敷有压敏导电胶，可紧密地黏附于身体皮肤，使用方便、舒适，还可以反复使用。  \n\n（2）一次性使用心电电极是一种能与各种心电监护设备配套使用的电极，适用于医院临床对心脏病患者的心电检查及心电动/静态监护。早期心电电极采用的导电胶由含电解质的凝胶构成，主要成分为明胶、琼脂等生物胶，存在粘接力差、易发霉、易失水变干、丧失电性能等问题。现用UV固化导电压敏胶制作心电电极，有良好黏附性，也不会干涸和发霉，可长期贮存，使心电电极产品上一个新台阶，得到更新换代。 Tor  \n\n（3）高频电刀是一种取代机械手术刀进行组织切割的外科器械，它具有切割速度快、止血效果好、操作简便、安全方便的优点，已广泛应用在各种手术中。高频电刀使用时，需要配置与患者身体连接的面积比较大的电极，以提供低电流密度的高频电流回流，避免在人体组织中产生灼伤等有害的物理效应。高频电刀用的极板，称为板电极，早期使用的电刀板极为钢板，使用时用绷带把钢板电极绑在大腿或臀部，易发生灼伤人体的弊病。而采用UV固化导电压敏胶制成的电刀板电极，具有良好黏附性并且轻、薄和柔软的特性，确保与皮肤紧密粘贴，优越的导热效应，使病人免遭皮肤灼伤的痛苦，一次性使用，无交叉感染，安全可靠。  \n\nUV固化医用导电压敏胶是以一定配比的高分子单体、交联剂、光引发剂经UV光照聚合交联形成的凝胶状物质。通常选用丙烯酸与极性丙烯酸单体，丙烯酸经碱中和为羧酸盐就具有导电性。极性丙烯酸单体如丙烯酸羟基酯、甲基丙烯酸羟基酯，极性基团可改善共聚物本体的力学性质，如提高玻璃化温度，增加弹性模量、内聚强度和本体黏度等，从而影响压敏胶的剥离力和持粘性能。交联剂可选用双官能度或三官能度内烯酸酯，交联可提高共聚物的分子量和压敏胶的持粘力，还可提高压敏胶的使用温度，增强其耐溶剂能力和抗老化性能。但压敏胶自身的黏弹性及其对被粘材料表面良好的润湿性，是使其具有对压力敏感的黏合特性的主要原因。从而决定了压敏胶的交联必须是轻度的，若交联度过大，便会失去其压敏特性。一般控制交联剂用量在 $1\\%$ 之内，通过交联，使压敏胶的内聚力、初黏力和剥离强度三者保持平衡。光引发剂可用安息香醚类、 $\\pmb{\\alpha}$ 羟基酮类，为了减少光引发剂的残留，在保证光固化反应有效进行的前提下，光引发剂用量尽量少，以增加压敏胶贮存稳定性。压敏胶最终需用氢氧化钾中和。随着中和度增加，初黏力变化不大，持粘力增加，电极的交流阻抗呈线性下降，导电性增加。  \n\nUV固化医用导电压敏胶开发，是光固化材料在医疗应用上又一个成功例子，为光固化材料应用开辟了一个新的领域。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 641,
+        "chunk": "# 12.5.1光聚合水凝胶特点  \n\n水凝胶是一种亲水性聚合物网络，能够在水中溶胀、吸收并保持大量水分而又不溶解于水，具有优良的生物相溶性和渗透性，其物理性质接近软组织，是生物医药领域中一类重要的生物材料。水凝胶可用于药物控释载体、活性酶的固定、组织工程支架、人造肌肉组织、隐形眼镜、生物传感器等。  \n\n光聚合提供了一种快速可控形成水凝胶的方法。光聚合水凝胶是指借助光引发剂，通过可见光或紫外光引发聚合而形成的水凝胶。  \n\n通过光聚合方法制备水凝胶，与其他聚合方法相比有如下优点：  \n\n$\\textcircled{1}$ 产物几何形状易于控制；  \n$\\textcircled{2}$ 在室温或生理温度下，反应时间短；  \n$\\textcircled{3}$ 反应条件温和；  \n$\\textcircled{4}$ 较低的反应热；  \n$\\textcircled{5}$ 特别是可在体外或体内生理条件下，光聚合制备水凝胶。  \n\n因此可借助腹腔镜、导管或通过皮下注射方法，可在体内原位用光聚合技术形成水凝胶，从而减少病人创伤和痛苦，而且形成的凝胶结构形状类似缺损组织，贴附性好。  \n\n光聚合反应合成水凝胶，通常用本体光聚合和界面光聚合。  \n\n（1）本体光聚合是将光引发剂溶于水凝胶前驱体溶液（单体或大分子单体）中，在适当的光照条件下，前驱体溶液经聚合、交联转化为水凝胶状态。本体光聚合会在组织表面形成较厚的水凝胶膜，可以防止术后粘连或作为药物控释载体。  \n\n（2）界面光聚合是将光引发剂附着于细胞或组织表面，然后与水凝胶前驱体溶液接触，在适当波长的光照射下，在光引发剂和溶液界面就会形成水凝胶薄膜（<100μm)。通过界面光聚合所形成的水凝胶薄膜对营养物质传输的阻力较小，因而细胞成活率和包埋效率较高。通过界面光聚合可在胰腺细胞表面形成水凝胶薄膜，既提供了免疫隔离，又保证了营养物质和胰岛素的快速扩散；在血管表面形成水凝胶薄膜，可防止血栓和血管再狭窄的形成，同时也可用于血管内的药物释放系统。",
+        "category": " Introduction"
+    },
+    {
+        "id": 642,
+        "chunk": "# 12.5.2光聚合水凝胶所用单体  \n\n许多单体在可见光或紫外光辐照条件下可发生光聚合反应，但大多数单体由于具有细胞毒性而不能用于生物医药领域。用于生物医药领域的光聚合水凝胶通常由大分子水凝胶前驱体产生，这些大分子单体能溶于水，含有两个或多个反应基团，同时具有良好的生物相容性，对生物体无毒无害。常用于光聚合水凝胶的大分子单体可分为化学合成大分子和天然高分子两类。  \n\n（1）化学合成光活性大分子单体主要有聚乙二醇丙烯酸酯衍生物、聚乙二醇甲基丙烯酸酯衍生物、聚乙烯醇衍生物、聚氮取代丙烯酰胺衍生物、聚乳酸丙烯酸酯衍生物等，这些大分子单体末端含有光活性基团（甲基）丙烯酰氧基，在UV光照下发生聚合交联，制备水凝胶。如图12-9所示是聚乙二醇/聚 $\\alpha$ -羟基酸双丙烯酸酯大分子单体的合成、光聚合和降解过程。通过改变共聚物中 $\\alpha$ -羟基酸链段的长度和位置可控制其降解速率，通过大分子单体的浓度和聚乙二醇链段的长度控制水凝胶的渗透性和力学性能。  \n\n![](images/cf2ad3ef0651d7e4e758ae8a4d4c45a2852fe13f56035985ff92101924d9c4c8.jpg)  \n图12-9基于聚乙二醇/聚α-羟基酸双丙烯酸酯的大分子单体的水凝胶的合成、光聚合、降解过程  \n\n（2）光活性天然高分子单体是将含有反应活性基团的多糖类天然高分子通过酰化反应，制得相应的丙烯酸酯或丙烯酰胺衍生物，再通过光交联反应即可制得天然高分子光聚合水凝胶。常用的天然高分子单体为透明质酸衍生物、葡聚糖衍生物和壳聚糖衍生物等。透明质酸具有黏弹性和低剪切力，可用作药物、蛋白质和肽的转载系统，在组织工程中用于骨缺损的修复、伤口的愈合和软骨组织扩增。利用透明质酸与联乙烯矾交联而制得水凝胶，已在美国用来作为整容的皮下植入材料。通过透明质酸与甲基丙烯酸酐反应制得的具有光聚合活性的甲基丙烯酸透明质酸酯，经光聚合制得了透明质酸水凝胶，可作为生物活性载体。壳聚糖和葡聚糖具有良好的生物相容性、抗血栓性，能刺激宿主抵御病毒和细菌感染的免疫系统，促进创伤愈合以及软组织和硬组织重建。将壳聚糖两端引入叠氮基团和乳糖基团，经光交联形成水凝胶，具有上述性能。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 643,
+        "chunk": "# 12.5.3光聚合水凝胶的应用  \n\n光聚合水凝胶在生物医药领域应用极广，主要有下列应用。  \n\n（1）药物及生长因子释放体系载体细胞的增殖和分化需要各种生长因子和细胞因子的调节。生长因子在组织缺失部位的持续释放，才能刺激细胞生长，促进新组织形成，所以生长因子的应用有赖于开发适用的释放系统。光聚合水凝胶与许多生物活性分子有良好的相容性，并且通过改变溶胀比、交联密度和降解速率可以较好地控制其释放行为，从而使活性分子在需要的时间间隔内释放并防止其失活。将睫状神经营养因子与聚乳酸-聚乙二醇-聚乳酸双丙烯酸酯水溶液混合，在UV光照后形成PLA-PEG-PLA水凝胶，并将睫状神经营养因子包埋其中，用于视网膜移植治疗过程研究，发现长出的神经突的数量明显提高，显然这是水凝胶缓释睫状神经营养因子的缘故。  \n\n（2）组织工程支架材料光聚合水凝胶的前驱体具有良好的流动性，因而可用于异型修复材料的制备，成为当前组织工程支架材料的研究热点。如受损的软骨由于缺少血管很难自身修复，目前，较常用的治疗方法是移植同源软骨细胞，但这种方法要通过外科手术移植健康的软骨，并且受到软骨形状的限制。而软骨组织工程技术可以将软骨细胞包埋于具有生物相容性、可生物降解的由水凝胶组成的支架中，以完成软骨细胞的移植。用甲基丙烯酸缩水甘油酯与硫酸软骨素反应，制得硫酸软骨素的甲基丙烯酰衍生物，在UV光照下，与聚乙二醇丙烯酸酯共聚合，制得聚乙二醇-硫酸软骨素水凝胶用作组织工程支架材料，结果发现，由于硫酸软骨素引人，使包埋其中的软骨细胞具有更高的活性，可望用于软骨组织工程。  \n\n（3）细胞的受控生长通过模仿体内细胞与其周围环境的相互作用，进而引导细胞的分化和组织的形成。通过光聚合方法，可以将调节细胞功能的生物大分子按特定分布方式固定在材料表面，从而实现材料表面性能对细胞功能影响的可视性以及对细胞间微观组织的空间调控。将聚乙二醇或聚乙烯醇与多种短肽进行复合，可以用于不同类型细胞的受控组装。用光聚合技术制得的聚乙二醇双丙烯酸酯水凝胶为基材，以短肽基聚乙二醇单丙烯酸酯为肽载体，通过光印刷技术实现生物活性大分子肽在PEG-DA表面的图案化。因聚乙二醇具有抗蛋白质吸附及细胞黏附功能，若图案化的肽为纤连蛋白中重要的黏附系列，则可实现真皮或纤维细胞的区域化黏附及生长，从而控制细胞的生长方向。  \n\n（4）细胞微囊化，起免疫隔离作用通常患者在经历了移植手术后，仍需花费一生的时间进行免疫抑制治疗，以对抗免疫排斥这种人体的自然反应，因此对于同种异体或异体细胞/器官移植中免疫排斥成为当前医疗中亟待解决的问题。目前一个有发展前景的解决方案是将外源性的细胞或器官包埋在半透明的人工膜中进行隔离，然后再移植至体内，使之避免植入细胞或器官与免疫细胞和体液直接接触，从而起到免疫隔离的作用。由于细胞具有生物活性，易受损伤，因此人工膜的制备条件必须温和，避免细胞的包埋材料形成人工膜凝胶时，出现温度和 $\\mathtt{p H}$ 过高或过低造成对细胞的破坏。而光聚合水凝胶却因其温和的聚合条件、反应放热小等特点，在细胞微包囊过程中，充分发挥作用。将猪胰岛细胞分散于聚乙二醇双丙烯酸酯前驱体溶液中，通过光聚合形成了包埋有猪胰岛细胞的聚乙二醇双丙烯酸酯水凝胶，在注射到鼠体内30天后，仍具有活性，并释放胰岛素。  \n\n（5）原位可注射水凝胶利用组织工程原理，使用预成型支架可以把细胞“种植”在患者体内，从而起到治疗作用，但治疗需要外科手术。而可注射且能原位成型的水凝胶，借助针管注射技术，手术创口小；其初始材料为液体，可填充到特定形状部位，形成精确外形的聚合物水凝胶；聚合物在组织表面直接形成，其与周围组织的黏合力明显增强。因此，原位可注射水凝胶在医学领域得到了较为广泛的应用。利用可注射水凝胶的透皮光聚合技术，将牛关节软骨细胞悬浮于聚乙二醇双丙烯酸酯与聚乙二醇组成的水溶液中，再皮下注射于鼠背上，在体外用UV光照射30min 聚合，经四周后取出，发现有新生类软骨结构形成，实现了软骨的异位形成（图12-10）。  \n\n![](images/dcde703bd149471839c183f90b36f2748deecb57164cdbafecf7fa0b44e72678.jpg)  \n图12-10利用透皮光聚合技术，软骨组织的异位形成1一牛软骨细胞的分离，及其与PEG可注射水凝胶前驱体水溶液的混合；2—聚合物软骨细胞悬浮液；3一在鼠背部皮下注射；4一将老鼠置于UV灯下照射 $30\\mathrm{{min}}$  \n\n综上所述，由于有较好的生物相容性、渗透性和物理特性，光聚合水凝胶作为生物材料在医学领域和组织工程中具有良好的应用前景。但在应用过程中需注意以下几点。  \n\n（1）控制光聚合水凝胶的强度光聚合水凝胶可以应用于组织工程、生物膜、药物释放体系等不同领域，它们对水凝胶的物理力学性能有不同要求。可通过改变原料配比、交联密度等以控制光聚合水凝胶的强度等性能。 5（2）提高聚乙二醇类水凝胶生物活性聚乙二醇类水凝胶是光聚合水凝胶的主要品种之一，但PEG本身缺乏生物活性位点。可将其与多肽类生物活性分子复合，在一定程度上提高其生物活性。（3）光化学活性有待提高光聚合水凝胶多应用于生物体内，对反应条件有较高要求。如何进一步控制反应热，减少光照时间是光聚合水凝胶的一个发展方向。（4）仿生、天然光聚合水凝胶的开发与化学合成水凝胶相比，天然仿生光聚合水凝胶具有无毒、生物相容性好、易降解等特点，更具有发展潜力。  \n\n![](images/f861720c462a30caa5813c865a85beb8988d075ae780851c0a571f07ddfb2aaf.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 644,
+        "chunk": "# 第13章 紫外光源和设备  \n\n光化学是“研究光（包括紫外到红外）的化学效应的分支学科”。  \n\n光固化是一种在光的照射下进行的化学反应，为典型的光化学反应。这里所指的光主要是紫外光，也有少部分为可见光。  \n\n光化学反应为分子吸收了光能后引起的化学反应。光化学反应通常包括两个反应过程：第一个是激发过程，在此过程中，分子吸收光能从基态分子变成激发态分子；然后进人第二个化学反应过程，即激发态分子发生化学反应生成新产物，或经能量转移或电子转移生成活性物（自由基或阳离子)，发生化学反应生成新产物（图13-1)。  \n\n![](images/9306640924abd9556f95875c7bb5bd9bcaeabdad5837bad766ee3a56f73e87be.jpg)  \n图13-1光化学反应历程示意  \n\n光化学反应服从下面三个定律。  \n\n（1）光化学反应第一定律（Gothus-Draper定律）“只有被分子吸收的光才能引起光化学反应”。该定律说明进行光化学反应时，必须要使光源的波长与光反应物质的吸收波长相匹配，若不匹配，光不被物质吸收，是不会引起光化学反应的。 C  \n\n（2）光化学反应第二定律（Stark-Einstein定律）“一个分子只吸收一个光子。”或者说“分子的激发和随后的光化学反应是吸收一个光子的结果。”该定律说明物质分子吸收光子是量子化的，只吸收一个光子而不吸收半个或1/3个光子的能量。但近年来，光化学技术发展，发现某些物质在激光束强光照射下，一个分子也可能吸收2个或2个以上光子的能量。  \n\n（3）光吸收定律（Beer-Lambert定律）“只有被物质吸收的光可引起光化学反应”。光  \n\n的吸收服从光吸收定律：  \n\n$$\nI{=}I_{0}10^{-\\alpha t}\n$$  \n\n式中 ${{I}_{0}}$ —人射光强；I—透射光强；e 一摩尔消光系数；C 物质的摩尔浓度；1- 一通过物质的光程长度。  \n\n将上式移项取对数：  \n\n$$\n\\scriptstyle{\\log I_{0}}/{I=\\epsilon c l=A}\n$$  \n\n式中A——吸光度。  \n\n吸光度与消光系数及浓度成正比，而透射光强度 $\\boldsymbol{\\mathit{I}}$ 则随光程长度（即光透过深度）呈指数下降。因此，光在吸光物质中透过深度是有限的，所以光固化产品涂层厚度是受限的。  \n\n在光化学反应中，有时物质分子吸收一个光量子后通过连锁反应，可形成比一个多的产物分子；有时物质分子吸收一个光量子后，形成比一个少的产物分子，即需吸收几个光量子，才产生一个产物分子。把参与了预期反应的分子数（即生成产物分子数）和体系所吸收的光子数的比值定义为量子产率 $\\Phi$ 。  \n\n参与预期反应的分子数（即生成产物的分子数）",
+        "category": " Introduction"
+    },
+    {
+        "id": 645,
+        "chunk": "# 吸收的光量子数  \n\n光固化产品（UV涂料、UV油墨、UV胶黏剂）量子产率 ${\\bar{\\pmb{\\phi}}}{\\scriptstyle>}1$ ，表示光化学反应存在着链式反应，发生了自由基光聚合、阳离子光聚合。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 646,
+        "chunk": "# 13.2 紫外光及其波段分类  \n\n光的本质是一种电磁辐射，同时呈现波动性和微粒性的特点，即光的波动-微粒二象性，光量子和光波是光两种互为依存的形态。  \n\n在微观物质世界中，能量（E）的单位常用电子伏（electronvolt，简写eV）表示。leV在数量上等于1个电子在真空中通过1V电位差所获得的动能：  \n\n$$\n\\mathbf{1eV}{=}1.602176462{\\times}10^{-19}\\mathbf{J}\n$$  \n\n将自然界所有已知的电磁辐射按能量的高低（或波长的长短）可以编制成一幅电磁辐射全谱图(图13-2)。在电磁辐射全谱中，无线电波的波长最长（约 $10^{6}\\mathrm{nm})$ ，能量最低（约10-3eV)，然后依次为微波、红外线、可见光、紫外光、X射线、射线，直到宇宙射线，宇宙射线能量最高（>10°eV)，波长最短（<10-1nm)。紫外光（ultra violet，简写UV)在电磁辐射全谱中位置是波长 $100\\sim400\\mathrm{nm}$ 一段范围，能量在 $3.1{\\sim}12.4\\mathrm{eV}.$ 花妆  \n\n紫外光根据其波长大小又可分为三个波段：  \n\n①真空紫外光（vacuum ultraviolet，简写VUV)，波长100～200nm，能量在12.4～$6.2e\\mathbf{V}$ ，真空紫外光只有在真空中才能传播，在空气中被严重吸收，故在光化学和光固化中无实际应用；  \n\n$\\textcircled{2}$ 中紫外光，波长 ${200}\\sim300\\mathrm{nm}$ ，能量在 ${\\bf6.2}\\sim{\\bf4.1e V}$ $\\textcircled{3}$ 近紫外光，波长 ${\\ 300}\\mathrm{\\sim}400\\mathrm{nm}$ ，能量在 $4.1{\\sim}3.2\\mathrm{eV}$ 。  \n\n![](images/b53818cf29ae89d91f26552a800c9b7e1302f5378a6a355137c846fc0f0cc72b.jpg)  \n图13-2 紫外光在电磁辐射中的波段近紫外（UVA)—-UV固化广泛应用段；中紫外（UVB)—人类皮肤敏感段；远紫外（UVC)—杀菌消毒；真空紫外（VUV)——臭氧产生段  \n\n1970年在巴黎制定的国际照明词汇中，将中、近紫外光分为UVA、UVB和UVC三个波段。  \n\n（1）UVA长波紫外光，波长 $315\\sim400\\mathrm{nm}$ ，能量 $3.9\\sim3.2\\mathrm{eV}$ 。这是大多数光引发剂的最大吸收光谱所处波段，因此是光固化产品最敏感的紫外光波段。常用的UV光源汞弧灯其发射光主波长 $365\\mathrm{nm}$ 也在此范围。UVA也是人类皮肤在太阳光照射下变黑的重要原因，皮肤在UVA下过度曝晒，也能造成损伤。  \n\n（2）UVB中波紫外光，波长 $280\\sim315\\mathrm{nm}$ ，能量 $4.4{\\sim}3.9\\ensuremath{\\mathrm{eV}}$ 。不少光引发剂在此波段也有较大吸收，因此也是光固化产品可利用的紫外光波段。UVB波段紫外光又是太阳光灼烧人类皮肤主要射线成分。  \n\n（3）UVC短波紫外光，也称远紫外光、深紫外光，波长 $200\\sim280\\mathrm{nm}$ ，能量 $6.2\\sim$ $4.4\\mathsf{e V}$ 。UVC波段能量较高，易于引起分子化学键的激发，甚至发生光化学反应，部分光引发剂在此波段也有吸收，因此对光固化也有一定贡献。UVC波段小于 $240\\mathrm{nm}$ 紫外光，其能量（5.2eV）已超过空气中氧分子（Oz）的结合能，因而可产生强烈气味的臭氧（O3）。UVC波段 $254\\mathrm{nm}$ 紫外光常用于空气和水的消毒。 a为了评价和比较紫外光源功率，输出紫外光能量大小，常用下面几个物理量。  \n\n（1）功率密度也叫线功率，是指紫外光源单位长度的功率，单位为 $\\mathbf{w}/\\mathbf{cm}$ 。日常用的紫外光源其线功率为 $80\\mathrm{W/cm}$ ，已有线功率为 $\\mathbf{240W/cm}$ 甚至更高的紫外光源。 不  \n\n（2）光强是指涂层单位面积获得的紫外光能量，单位为 $\\mathrm{m}{\\bf W}/\\mathrm{cm}^{2}$ 。光强可用紫外光照度计测得（某一特定波长，如 $365\\mathrm{nm}$ 、 $254\\mathrm{nm};$ 。  \n\n紫外光源目前有汞弧灯、金属卤素灯、无极灯、氙灯、UV发光二极管、准分子紫外灯以及UV-等离子体。",
+        "category": " Introduction"
+    },
+    {
+        "id": 647,
+        "chunk": "# 13.3.1 汞弧灯  \n\n汞弧灯也叫汞蒸气灯，简称汞灯，是目前最常用的紫外光源。汞弧灯是封装有汞的、两端有钨电极的透明石英管，内充惰性气体（一般为氩)，通电加热灯丝时，温度升高，液体汞蒸发气化，石英管内基态汞原子受到激发跃迁到激发态，再由激发态回到基态时便释放出光子，即发射紫外光。  \n\n汞弧灯因管内汞蒸气压力不同，分为低压汞灯、中压汞灯和高压汞灯三类，它们发射的紫外光也有不同的光谱。  \n\n（1）低压汞灯汞蒸气压力在 $10\\mathrm{{\\sim}10^{2}P a}$ ，紫外区主要发射波长为 $254\\mathrm{nm}$ ，低压汞灯的功率较小，一般只有几十瓦。由于发射波长短，光强又低，因此在光固化中较少使用，目前主要用于空气和水的杀菌消毒，还有在管内壁涂以荧光物质，制成荧光灯作照明用。低压汞灯的使用寿命在 $2000{\\sim}4000\\mathrm{h}$ 。  \n\n（2）中压汞灯（我国习惯上称其为高压汞灯）汞蒸气压力在 $10^{5}\\mathrm{Pa}$ ，约为 $\\scriptstyle1\\mathtt{a t m}$ ，中压汞灯结构如图13-3所示。中压汞灯在紫外区主要发射波长为365nm，其次为313nm、303nm，与大多数光引发剂的吸收波长相匹配，目前常用的光引发剂在此波长区域都有强烈的吸收，对光固化过程极有价值，所以是光固化最常用的光源。中压汞灯主要谱线的相对强度见表13-1。  \n\n![](images/75a1013c96cf9bd0bccb273755e466b2ce1d451a09079b27d5e8f2978e1c6d8d.jpg)  \n图13-3中压汞灯结构示意  \n\n表13-1中压汞灯主要谱线相对强度  \n\n\n<html><body><table><tr><td>波长/nm</td><td>相对强度</td><td>波长/nm</td><td>相对强度</td></tr><tr><td>222.4</td><td>14.0</td><td>296.7</td><td>16.6</td></tr><tr><td>232.0</td><td>8.0</td><td>302.2~302.8</td><td>23.9</td></tr><tr><td>236.0</td><td>6.0</td><td>312.6~313.2</td><td>49.9</td></tr><tr><td>238.0</td><td>8.6</td><td>334.1</td><td>9.3</td></tr><tr><td>240.0</td><td>7.3</td><td>365.0~366.3</td><td>100.0</td></tr><tr><td>248.2</td><td>8.6</td><td>404.5~407.8</td><td>42.2</td></tr><tr><td>253.7</td><td>16.6</td><td>435.8</td><td>77.5</td></tr><tr><td>257.1</td><td>6.0</td><td>546.0</td><td>93.0</td></tr><tr><td>265.2~265.5</td><td>15.3</td><td>577.0~579.0</td><td>76.5</td></tr><tr><td>270.0</td><td>4.0</td><td>1014.0</td><td>40.6</td></tr><tr><td>275.3</td><td>2.7</td><td>1128.7</td><td>12.6</td></tr><tr><td>280.4</td><td>9.3</td><td>1367.3</td><td>15.3</td></tr><tr><td>289.4</td><td>6.0</td><td></td><td></td></tr></table></body></html>  \n\n中压汞灯的输出功率可以做到8～10kW，其线功率也可达到40～240W/cm，可装在不同类型的光固化设备上，用于不同材质上UV涂料、UV油墨、UV胶黏剂的固化。中压汞灯的使用寿命 ${\\leqslant}1000\\mathbf{h}$ a  \n\n中压汞灯发射紫外光外，还有可见光和红外线，其输出光谱的能量分布如图13-4所示。  \n\n![](images/e4d7039dfee8c5d6744796190f885916208b3c91728dcaa7849d92eeb2f72277.jpg)  \n图13-4中压汞灯的发射光谱  \n\n![](images/20066ac35140837af8ac7d859ea689e3ac7a814361d6b614c38b445518d49985.jpg)  \n图13-5 中压汞灯输出光谱的能量分布  \n\n从图13-5中可见，中压汞灯发射紫外光的效率约占 $30\\%$ ，而红外线和其他热辐射约占$60\\%$ ，大部分输入功率转变为热能，使灯管的温度上升到 ${700}\\mathrm{\\sim}800^{\\circ}\\mathrm{C}$ ，会对基材（特别是对热敏感的基材如塑料、薄膜、纸张）产生不利的影响。为了避免灯管和基材过热，需要冷却，主要靠风冷方式来实现，也可用水冷却。但红外辐射也能增高体系的温度，有助于促进光固化进行，从而提高固化速率。 福  \n\n中压汞灯需冷启动，灯泡通电加热，使汞在石英管内完全气化，故诱导期长，一般需$10\\mathrm{{min}}$ 左右才能达到完整的光谱输出。一旦关灯后，不能立刻启动，要等 $15\\sim20\\mathrm{min}$ 冷却后，才能重新启动。  \n\n中压汞灯在使用时会产生臭氧，对人体有害，利用风冷排气装置把臭氧排到室外。产生的紫外光对眼睛和皮肤都有害处，眼睛直视会造成永久性的伤害，而高强度的紫外光会使皮肤“灼伤”，故灯具和光固化机上都安装光罩，以避免紫外光直接泄露到工作场所。  \n\n![](images/3ae0fc46a33b053139f3e8fe6f4fd1e9b7f55127535d69f1ae8e8ca26e70bea6.jpg)  \n图13-6碘化灯的发射光谱  \n\n（3）高压汞灯（我国称为超高压汞灯）充有汞和氙的混合物，蒸气压力在 $10^{5}\\sim10^{6}\\mathrm{Pa}$ ，即 $1\\sim10\\mathsf{a t m}$ 。工作温度在 $800^{\\circ}\\mathrm{C}$ 以上采用水冷却，可以很快启动。输出线功率可达 ${50}\\mathrm{{\\sim}}1000\\mathrm{{w}}/\\$ $\\mathsf{c m}$ ，但使用寿命较短，约 $200\\mathbf{h}$ ，在光固化领域中一般不采用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 648,
+        "chunk": "# 13.3.2 金属卤素灯  \n\n利用金属卤化物（通常为碘化物)较易挥发而且化学性质不活泼的特性，加在汞中，置于汞弧灯石英管内，得到的发射光谱可以补充和加强汞弧灯的线光谱，拓宽紫外和可见光谱分布(表13-2)。如添加适量碘化亚铁，可  \n\n增强 $350\\sim390\\mathrm{nm}$ 紫外区的辐射能量（ $358\\mathrm{nm}$ 、 $372\\mathrm{nm}$ 、 $374\\mathrm{nm}$ 、 $382\\mathrm{nm}$ 、 $386\\mathbf{nm}$ 、 $388\\mathbf{nm}$ )碘化灯则增强 $400{\\sim}430\\mathrm{nm}$ 的辐射能量（ $403\\mathrm{nm}$ 、 $417\\mathrm{nm})$ ，如图13-6所示。  \n\n表13-2不同金属卤化物汞弧灯的特征UV发射波长  \n\n\n<html><body><table><tr><td>金属掺杂元素</td><td>特征UV发射波长/nm</td><td>金属掺杂元素</td><td>特征UV发射波长/nm</td></tr><tr><td>银(Ag)</td><td>328,338</td><td>(Bi)</td><td>228,278,290，299,307,472</td></tr><tr><td>镁(Mg)</td><td>280,285,309,383/4</td><td>锰(Mn)</td><td>268/9，260，280，290，323，355，357，382</td></tr><tr><td>镓(Ga)</td><td>403,417</td><td>铁(Fe)</td><td>358,372,374/5,382,386,388</td></tr><tr><td>铟(In)</td><td>304,326,410,451</td><td>钻(Co)</td><td>341,345,347,353</td></tr><tr><td>铅(Pb)</td><td>217,283,364,368,406</td><td>镍(Ni)</td><td>305,341,349,352</td></tr><tr><td>锑(Sb)</td><td>253,260,288,323,327</td><td></td><td></td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 649,
+        "chunk": "# 13.3.3 无极灯  \n\n无极灯也叫微波激发灯（图13-7)，它与汞弧灯不同之处是灯管内无电极，其石英灯管  \n\n直径较小，只有 $\\mathfrak{s}\\sim13\\mathrm{mm}$ ，利用微波启动灯泡。微波由磁控管产生，并被导入由无电极灯管和反射器组成的微波腔内，微波的能量激活灯管内汞和添加物分子形成一个等离子体，有效地发射出紫外光、可见光和红外线，其中紫外光占整个辐射 $33\\%\\sim42\\%$ ，高于中压汞灯 $30\\%$ 可见光约 $25\\%$ ，红外线约 $15\\%$ ，低于中压汞灯热效应；对流热约 $25\\%$ 。典型的无极灯管长度 $25\\mathrm{cm}$ ，输出线功率可达$240\\mathbf{W}/\\mathbf{cm}$ ，使用寿命高达 $8000\\mathbf{h}$ ，远远高于中压汞灯。  \n\n![](images/73aaff3c400d8cdeedb31582668889df2200a097aa1f5dc09228418b6b684644.jpg)  \n图13-7由磁控管激发的无极灯设备的结构  \n\n无极灯可快速启动（关灯后可在10s之内重新启动)，而不必像中压汞灯需冷却后再可启动。无极灯输出功率稳定，一旦灯管出现故障或到使用寿命，输出就降为零。但中压汞灯使用一段时间后，输出功率逐渐下降，即使输出功率已达不到固化效果，由于灯还亮着，往往会被误认为UV涂料或UV油墨质量上出现问题而造成未固化，实质上是由于灯的输出功率过低造成的。  \n\n无极灯由于充填不同金属元素有多种型号，主要为H灯、D灯和V灯三种，其发射光谱如图13-8所示。  \n\n![](images/79a35f4efe93118d15248e96f1e875d6bd13574da153c4d00972fdf1c19acc9d.jpg)  \n图13-8无极灯的发射光谱  \n\n（1）H灯为标准的无极灯，无充填物，主波段 $240\\sim320\\mathrm{nm}$ ，适用于多种UV清漆的固化。  \n\n（2）D灯管内有铁的填充物，发射光谱向长波长移动，主波段为 $350\\sim400\\mathrm{nm}$ ，适用于含颜料的UV色漆和UV油墨及厚涂层UV清漆的固化。  \n\n（3）V灯管内有镓的填充物，发射光谱更向可见光蓝、紫光移动，主波段为 $400\\sim$ $450\\mathrm{nm}$ ，适用于含 $\\mathrm{TiO}_{2}$ 的UV白油墨和白色底漆固化。  \n\n无极灯与中压汞灯相比，有不少优点，尤其是启动快、使用寿命长、紫外光输出效率高、红外辐射低、输出功率稳定。但由于灯管长度 $25\\mathsf{c m}$ ，对宽度大的基材光固化，需用多支灯管并排使用，目前价格较高，尽管性能上优于中压汞灯，但影响了推广使用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 650,
+        "chunk": "# 13.3.4 氙灯  \n\n氙灯也是一种电弧灯，灯管内充氙气，蒸气压力为 $2\\times10^{6}\\mathsf{P a}$ ，即药 $20\\mathsf{a t m}$ 。氙灯的发射光谱是连续光谱，在 $\\mathbf{250}{\\sim}1200\\mathbf{nm}$ ，寿命在 $200\\sim2000\\mathrm{h}$ 。由于紫外波段输出不多，在光固化中没有应用，主要用于人工大气老化试验中，作为模拟太阳光的光源。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 651,
+        "chunk": "# 13.3.5 UV发光二极管  \n\n发光二极管（lightemittingdiodes，缩写为LED）是一种半导体发光的新光源，可直接将电能转化为光和辐射能。发光二极管是由两种掺杂不同的半导体，即p型半导体和n型半导体之间形成 $\\mathtt{p-n}$ 结而构成，与一个 $\\mathbf{p}{-}\\mathbf{n}$ 结二极管类似。当向发光二极管两个半导体的 $\\mathbf{p}{-}\\mathbf{n}$ 结处外加一个电场，半导体的载流子，即p型半导体中的空穴和n型半导体中的电子顺电场相向移动，至 $\\mathtt{p-n}$ 结相遇，彼此复合而释放出能量。若释放的能量是非辐射性的，就如普通二极管，但当释放能量以辐射形式出现，即以光子形式放射出来，就是发光二极管。光子的发射波长取决于p-n结所使用半导体材料的能隙大小，采用不同的材料或对半导体进行不同的掺杂，可以得到不同的发射光谱。  \n\n20世纪60年代，最早采用砷的磷化物（GaAsP）制成LED光源，发红光（入=650nm)，以后半导体材料引入钢（In）和氮（N）等元素，使LED光源产生绿光（=555nm)、黄光（=590nm）和橙光（=610nm），特别是镓铟氮化物（GaInN）开发成功使LED光源发射蓝光，而将蓝色LED与红色、绿色混合便可产生出白光，从而使LED发光覆盖整个可见光波段。近年来，产生短波长的半导体材料氮化铝（AIN)、氮化(GaN)、铟氮化物（InGaN)、铝镓氮化物（AIGaN)、铝铟氮化物（AlIn Ga N）相继开发，制成的UV-LED发射近紫外光谱：365nm、375nm、385nm、390nm、395nm、405nm、415nm、437nm，成为新的UV光源并已开始用于辐射固化领域。  \n\nUV-LED与汞弧灯、微波无极灯等UV光源比较，具有体积小、重量轻、运行费用低、使有寿命长、效率高、安全性好、低电压、低温、无臭氧产生等优点，因此已引起人们广泛注意，将成为一种新的UV和可见光源，用于辐射固化产业(表13-3)。  \n\nUV-LED光谱分布集中在一个窄带（365～395nm），带宽在40nm左右，没有UVB（280～320nm）和UVC（250～260nm）输出，受半导体材料的限制，尚未开发出具有发射UVB和UVC的发光二极管，因此与常用的光引发剂的吸收光谱不能完全匹配。  \n\nUV-LED不能克服氧气在涂层表面的氧阻聚作用，而目前每个UV-LED能量输出在100～300mW，远远低于传统的UV光源的紫外光能量输出，故为最大限度利用UV-LED的能量，UV-LED 灯管到被固化物表面的距离很短，一般在1cm左右。正因为UV-LED 的紫外光波段和输出功率还受到限制，而且价格也较高，使UV-LED在辐射固化的应用还处于起步阶段。  \n\n表13-3UV-LED与汞弧灯、微波无极灯UV光源比较  \n\n\n<html><body><table><tr><td>比较项目</td><td>汞弧灯</td><td>微波无极灯</td><td>UV-LED管</td></tr><tr><td>运用费用</td><td>高</td><td>高</td><td>低</td></tr><tr><td>光源寿命/h</td><td>≤1000</td><td>8000</td><td>20000～40000</td></tr><tr><td>光输出衰减</td><td>逐渐衰减</td><td>衰减较小</td><td>几乎不衰减</td></tr><tr><td>光输出均一性</td><td>良好</td><td>良好</td><td>优秀</td></tr><tr><td>光谱分布</td><td>谱带宽</td><td>谱带宽</td><td>谱带窄（±10nm)</td></tr><tr><td>光源设备</td><td>灯管，电源变压器</td><td>灯管，磁控管</td><td>平面薄板</td></tr><tr><td>电压</td><td>高电压</td><td>高电压</td><td>低电压</td></tr><tr><td>臭氧</td><td>有</td><td>有</td><td>无</td></tr><tr><td>冷却</td><td>空气或水</td><td>空气或水</td><td>空气或水</td></tr><tr><td>光源热效应</td><td>高</td><td>较高</td><td>低</td></tr><tr><td>启动</td><td>慢启动，关闭后需冷却20min才能启动</td><td>较快</td><td>快，随时启动</td></tr></table></body></html>  \n\nUV-LED已在UV胶黏剂的粘接上广泛使用，特别是在UV-LED点光源固化机作UV光源，经聚焦由光纤输出，用于半导体产品、VCD、DVD磁头、液晶、光学镜头、精密电子元件和医用针头等粘接。最近UV-LED已应用于UV数码喷绘机上，作UV光源。特别是可见光发光二极管（ $\\mathsf{i}70\\mathsf{n m},$ ）用于口腔牙科修复树脂固化，已逐步取代金属卤素灯，它也是一种点光源。  \n\nUV-LED要用于一般UV涂料和UV油墨，必须采用矩阵排列多个UV-LED，组成线光源或面光源，但目前UV-LED成本较高，影响推广应用。由于UV-LED是属于半导体制作，按一般规律，每三年成本下降一倍，可以相信不久随着UV-LED 制造成本下降，其应用前景非常乐观。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 652,
+        "chunk": "# 13.3.6 准分子紫外灯  \n\n准分子（excimer是受激二聚体excited dimer 的缩写）是指该双原子分子不存在稳定的基态，只有在激发状态下两原子才能结合成为的分子，它是一种处于不稳定状态 (受激态)的分子，寿命极短，为纳秒（ns）级，然后准分子衰变，同时释放出具有很强单色性的紫外光子，即准分子辐射。  \n\n一些稀有气体原子和卤素分子在能量大于10eV的电子作用下可以形成稀有气体与卤素的准分子，它极不稳定，在几纳秒之内发射光子而分解，不同稀有气体与卤化物准分子发射光谱不同，都有各自的主峰波长，都在紫外光区(表13-4)。  \n\n表13-4稀有气体各种卤化物准分子的主峰波长  \n\n\n<html><body><table><tr><td>准分子</td><td>主峰波长</td><td>准分子</td><td>主峰波长</td></tr><tr><td>NeF</td><td>108</td><td>KrBr</td><td>207</td></tr><tr><td>ArF</td><td>193</td><td>KrI</td><td>190</td></tr><tr><td>ArCl</td><td>175</td><td>XeF</td><td>351</td></tr><tr><td>ArBr</td><td>165</td><td>XeCl</td><td>308</td></tr><tr><td>KrF</td><td>248</td><td>XeBr</td><td>282</td></tr><tr><td>KrC1</td><td>222</td><td>XeI</td><td>253</td></tr></table></body></html>\n\n$\\Phi$ 准分子灯商业化。  \n\n稀有气体卤化物准分子激光光源已商品化，氟化（KrF，248nm）、氟化氩（ArF，${\\mathfrak{193}}\\mathbf{nm})$ ）和氟（ $\\cdot\\mathtt{F}_{2}$ ， $157\\mathrm{nm}$ ）准分子激光光源已用于步进式曝光机，是与深紫外光刻胶配套的曝光光源。  \n\n已开发的准分子紫外灯有氙（Xe，172nm）、氯化氪（KrCl，222nm）和氯化氙C $\\mathbf{\\widetilde{XeCl}}$ ， $\\mathsf{308n m})$ ，它们的技术指标和主要应用见表13-5。  \n\n表13-5市场供应的准分子紫外灯的技术指标  \n\n\n<html><body><table><tr><td>准分子</td><td>峰值波长</td><td>单位灯管长度的</td><td>UV 辐射功率</td><td>最大灯</td><td>主要应用</td></tr><tr><td>Xez</td><td>172</td><td>15</td><td>1~1.5</td><td>175</td><td>物理消光，表面处理，臭氧产生</td></tr><tr><td>KrCl</td><td>222</td><td>50</td><td>5</td><td>100</td><td>UV氧化，干法刻蚀，光化学，UV固化，杀 菌消毒</td></tr><tr><td>XeCl</td><td>308</td><td>50</td><td>5</td><td>100</td><td>UV固化，光化学</td></tr><tr><td>KrBr</td><td>282</td><td></td><td></td><td></td><td></td></tr></table></body></html>\n\n$\\Phi$ 估计值。$\\textcircled{2}$ 正在研制。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 653,
+        "chunk": "# 13.3.7 UV-等离子体固化  \n\n等离子体（plasma）是物质的一种存在形式，它是由电子、离子和未电离的中性粒子组成的一种物质状态，是固态、液态、气态之外的物质第四态。固体物质通常在加热中变为液态，然后转为气态，温度极高时部分电离形成等离子体。太阳就是等离子体，宇宙空间$90\\%$ 以上的物质都是以等离子体的形式存在。  \n\n等离子体可以借助电能通过气体电离的方式而实现。等离子体在气体放电过程中通过原子激发而发射光子，光子能量有一定的分布，形成光谱。霓虹灯、荧光灯、氛灯、汞灯、无极灯等都是由灯管内气体在电能激励下通过放电形成等离子体并激发而发光。UV等离子体是选用氮（N）和氮（He）的混合气体为放电气体，经微波放电，形成等离子体发射光子，其光谱在 $200\\sim380\\mathrm{nm}$ 紫外区域。  \n\nUV-等离子体固化是将涂覆UV涂料的物体置于等离子腔中，然后抽真空，再充放电气体（如氮和氮的混合气体)，然后采用微波放电，使等离子体发射光子，输出紫外光（200～380nm)，此时被固化的物体都“浸没”在等离子腔的等离子体中，实现360°全方位的均匀的UV照射，不存在光照不到的阴影问题，也无氧阻聚效应，因此UV-等离子体固化特别适用结构复杂的物体和异型基材的UV固化。目前UV-等离子固化的主攻方向是汽车车身的UV涂装，在欧洲已完成了实验室试验，正进行中试的工程论证，一旦试验成功，意味着汽车工业的一次涂装革命。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 654,
+        "chunk": "# 13.4 紫外光固化设备",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 655,
+        "chunk": "# 13.4.1紫外光固化设备组成  \n\n常见的紫外光固化设备由五部分组成：UV光源、反射装置、冷却系统、辅助控制装",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 656,
+        "chunk": "# 置、输送系统。  \n\n（1）UV光源 为紫外光固化提供能量，是紫外光固化设备的核心。  \n\n（2）反射装置其作用是使光源产生的能量定向，提高光源的使用效率，最大限度地将紫外能量辐射到基材表面使涂层固化。  \n\n反射装置大多是由抛光成镜面的铝制成，通常有椭圆面型与抛物面型两种，如图13-9所示。椭圆面形反射装置将光束聚焦在基材表面上，将反射的能量集中，形成高的紫外光强度，达到最大的固化效率，适用于连续平面基材涂层的固化。抛物面型反射装置，提供平行的光束，紫外强度分布宽而均匀，产生的紫外光强度不如椭圆面型反射装置，适用于立体部件的涂层固化。  \n\n![](images/035dfe9234f820bcacbb5981fe69ffd6dea30ea5d88e06a2115f97a49af93b90.jpg)  \n图13-9 两种反射装置  \n\n（3）冷却系统中压汞灯工作时其输人能量有近60%转变为红外辐射，灯泡温度可升到700～800℃，灯管壁温度在500℃左右，产生的热量如不散发出去，会对基材有损害，尤其一些对热敏感的基材（纸、木器、塑料、纺织品、皮革和电子器件等）会产生不利影响，为此在紫外光固化设备中必须装有冷却系统（图13-10)。冷却系统大多为风冷装置，一可降低光源周围温度；二为排除光源开启后产生的臭氧。对较大功率的光源还可以增加水冷装置，包括对基材采用风冷和水冷。实际上，升高温度有利于固化反应的充分进行，因此冷却系统设计时要加以考虑。  \n\n![](images/d6474136b07c51f2b7824b33f7a1f8d4b2e782835f06b9eb03e2776c17b0b9cc.jpg)  \n图13-10紫外光固化设备的冷却系统  \n\n冷却系统另一种方法是使用冷镜反射器（图13-11)，冷镜反射器有分色反光镜、红外过滤镜和超级冷光镜，可不同程度降低红外辐射对基材温度的影响，见表13-6。  \n\n![](images/448cdd3e3839c84166da06cbca3c77637904c3c6cfb3871f3570e2c7c039e50b.jpg)  \n图13-11 反射器的示意  \n\n表13-6 三种反射器比较  \n\n\n<html><body><table><tr><td>项目</td><td>分色反射镜</td><td>分色反射镜十红外过滤器</td><td>冷镜反射系统</td></tr><tr><td>红外线减少量/%</td><td>40</td><td>60</td><td>80</td></tr><tr><td>对基材温度的降低/%</td><td>25</td><td>35</td><td>48</td></tr></table></body></html>  \n\n（4）辅助控制装置包括快门系统、光罩、变压器等。快门系统用于间断性固化，控制紫外光辐射能量；或流水线出现故障时，不用关闭光源，避免基材一直受光源照射，温度升高而造成损害（图13-12)。光罩是为屏蔽紫外光，避免紫外光直接泄漏到工作空间，保护现场操作人员而设。由于紫外光对人体眼睛和皮肤都有害，所以在紫外光源和紫外光固化设备中都装有光罩，不让紫外光外泄。中压汞灯是通过灯管内电极施以高电压而放电，因此都配有变压器。输送系统是为运送基材进行固化的装置，可采用金属网带或特氟纶网带，并带有变速装置，根据涂层固化能量需求，调节输送带的运行速度。  \n\n![](images/3b10e04a2e376a15f48d82ed182d6802058f5952cc3373a7347d98035540f1c4.jpg)  \n图13-12紫外光固化设备快门系统示意",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 657,
+        "chunk": "# 13.4.2紫外光固化设备类型  \n\n紫外光固化设备类型很多，大致可分为点光源固化机、移动式光固化机、台式光固化机、输送带式光固化机、立体固化光固化机、晒版机等。  \n\n点光源固化机采用将紫外光聚焦经光纤管输出，由于光照面积很小，所以照射部位获得光能较大，常用于UV胶黏剂粘接和牙科补牙用。  \n\n移动式光固化机有手提式和推移式两种。手提式用于UV胶黏剂、实验室及临时简单施工维修用；推移式则用于地板、石材施工或修补维修用。  \n\n台式光固化机：有输送装置，主要用于实验室科研或工厂小试光固化用。  \n\n输送带式光固化机：大量使用的光固化机属于此类型，可有双灯、三灯、四灯或更多，灯管轮流开启，输送带速度可调节。  \n\n立体固化光固化机：为一些立体涂装的物体光固化而设计的固化设备，主要是灯管排列上、下、左、右都有，以保证固化完全。  \n\n晒版机：为印刷制版专用的光固化机，光源采用碘灯。  \n\n涂料、油墨和胶黏剂是由树脂、稀释剂、颜料（清漆和胶黏剂不用)、填料和助剂组成的，而涂料、油墨和胶黏剂的生产过程就是把这些组分加工成涂料、油墨和胶黏剂的过程。这个加工过程就是要把颜料和填料固体组成尽可能均匀地分散在树脂、稀释剂液态组成中，这就是常说的分散过程。在整个分散过程中，颜料和填料实际上要完成润湿、粉碎和分散三次加工，为了达到这个目的，在生产时必须选用适当的分散设备，以强制手段来加速这个过程的进行。目前最常用的分散设备可包括以下四类：搅拌机、三辊研磨机、球磨机和捏和机，捏和机在UV涂料、UV油墨和UV胶黏剂中很少使用，不作介绍。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 658,
+        "chunk": "# 13.5.1 搅拌机  \n\n在涂料、油墨和胶黏剂工业中使用的搅拌设备很多，在多种搅拌机上安装不同的桨叶制得不同型号的搅拌机，如行星式搅拌机、蝶形桨搅拌机、高速叶轮揽拌机和高速叶轮与蝶形桨组合搅拌机等。最常用的是高速叶轮搅拌机，也叫高速分散机，是用作涂料、油墨预分散的较理想的设备。  \n\n高速叶轮搅拌机的结构比较简单，是一根可以通过液压装置上下升降的高速转动轴，轴的下端装有一个水平放置的并随轴转动的圆片状叶轮，最普通的叶轮是锯齿形，叶轮上锯齿都是相间地向上和问下与叶轮面有一定角度。当高速叶轮搅拌机运转时，分散料（包括树脂、稀释剂、颜料和填料）顺着叶轮的离心方向猛烈前进，冲到桶壁，并上下返流到叶轮中部，形成漩涡，同时在叶轮附近形成层流和湍流，产生撞击力和剪切力，达到润湿和分散颜料和填料的目的（图13-13)。但高速叶轮搅拌机不能提供很大的压力，比起三辊研磨机和球磨机来，分散能力小得多，它不能破碎硬的或粗颗粒的颜料，只能在低到中黏度系统中润湿和分散易分散的颜料。  \n\n![](images/521b82594788b196219ccb2fd131b67f3fcd89fd663ef824afc4330c1c32fa1d.jpg)  \n图13-13高速叶轮搅拌机墨料运动示意",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 659,
+        "chunk": "# 13.5.2 三辊研磨机  \n\n三辊研磨机也叫三辊机，是生产油墨、特别是比较黏稠的浆状油墨和涂料的主要分散设备。三辊机通常由三个直径相同的辊筒组成，三个辊简排列形式不同，有水平式和斜列式两种（图13-14)。不管是哪一种辊筒排列形式，三个辊筒的转速都不一样，前辊转速最快，中辊转速比前辊慢一些，后辊转速最慢；三辊转动方向也不同，后辊向前转，中辊向后转，前辊也向前转。机器运转时，分散料放在相向旋转的后辊和中辊之间的夹缝内，两辊的两端装有闸板，以防止墨料受辊筒间压力而被挤出辊简两端。在前辊简的前方装有出墨斗，用来将研磨好的油墨从前辊上刮下并收集起来，流人承接的容器内。三辊机上三个辊简之间的压力是通过手动或液压来调节的，用液压调整较先进。三个辊筒在一定速度和压力下运转，由  \n\n![](images/eb04473dcffc75d07a0bc97e54023406e7742a03eece92bdd367e0d4b3057bc5.jpg)  \n图13-14三辊机的两种主要排列形式  \n\n于摩擦的关系温度会逐渐升高，从而使墨料黏度下降，影响研磨质量和产量，为此三辊机都装有水冷装置，即辊筒都为空心辊，由通水管道进行水冷。三辊机还有供料装置，过去的手工用金属铲将墨料从料桶中一点一点地铲入机上，大量生产时已出现自动供料装置（图13-15)，  \n\n![](images/48c34d26496dffcb8f8c72bd014002bd4dca8da57b0be9570d850c315f2eff57.jpg)  \n图13-15三种自动供料装置示意图1—信号转换器；2—控制系统  \n\n对于具有一定流动性的浆状墨料大多采用倾倒式，比较稀的墨料则采用泵送式，比较稠的墨料则可采用挤压式。  \n\n三辊机中相邻的两个辊简是以不同速度运转的，因此会产生压力和剪切力；当墨料进人辊简夹缝时，受这两个力的作用，克服颜料的内聚力，使之破碎并分散。一般三辊机中三个辊筒的转速比为 $1:3:9$ 。而且三辊机辊筒直径越大，对颜料研磨所做的功也越多，研磨效果也越好，生产上常用的三辊机有260型（辊筒直径 $\\scriptstyle260{\\mathrm{mm}})$ 、405型（辊筒直径 $\\mathbf{405mm})$ ，还有150型、100型作小试打样用，更小的65型是实验室用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 660,
+        "chunk": "# 13.5.3 球磨设备  \n\n球磨设备是依靠球或砂（包括球状小珠）在不同容器和运动方式下通过对液状物料的撞击、摩擦和剪切而达到粉碎和分散作用的设备，可分球磨机和砂磨机两类。  \n\n（1）球磨机有卧式球磨机和立式球磨机两种。  \n\n卧式球磨机是比较老的常规球磨机，由一个水平放置并能旋转的圆筒和放在简中的一些球组成。圆筒一般是钢制的，也有特殊需要而内衬瓷或石等材料；球有钢制和瓷制的。需要研磨的墨料连同球一起在圆筒中旋转，由于球的作用，墨料被粉碎而分散。球磨机一般适用于分散较稀的墨料。使用球磨机不用预分散，颜料、填料和树脂、稀释剂等都可以一起投人，因此操作简便，管理和生产成本也较低。同时，由于球磨机是密封的，故机器运转时几乎没有挥发物和气味外逸，故不污染环境，比较安全。球磨机中一般装球量在圆筒容量$_{1/3\\sim1/2}$ 比较合适，1/2最理想；球的直径以 $1.3{\\sim}1.9\\mathrm{cm}$ 最常见；装料量在 $25\\%\\sim45\\%$ 之间。  \n\n立式球磨机也叫搅拌球磨机，这种研磨机在一个装有横臂式搅拌器的料桶中，加入适当大小和数量的钢球，并在料桶底部装一个钢质过滤网板，用泵将墨料通过网板强制打人料桶上部作循环，墨料中的颜料在钢球被搅动时受到撞击力、摩擦力和剪切力作用而被粉碎和分散。为了避免因长时间运转使墨料温度升高，料桶都带有夹套，通水控制温度(图13-16)。立式球磨机常用的球为碳钢球，要求颜色不变时可用不锈钢球，对要求颜色不变和避免金属污染时也可用陶瓷球；比较适用的球的直径范围在3～ $3\\sim$ $10\\mathrm{mm}$ ，立式球磨机搅拌的转速在 $60\\sim300\\dot{\\mathbf{r}}/\\operatorname*{min}$ 范围内。因为有搅拌装置，所以立式球磨机可以加比较黏稠的墨料，并且效率比三辊机高，还可以几台机器串联起来使用。  \n\n（2）砂磨机砂磨机是一种用来分散液体涂料和油墨的研磨机，根据它的结构分为立式开口型、立式密封型和卧式密封型三种。立式砂磨机不论开口型或密封型，其结构基本一样，是由一个直立并带有夹套的圆简组成，筒中放人一定大小的砂或小珠，用一个垂直的装有多个叶轮的高速转轴带动砂子运动，将经过预分散的墨料用泵连续地从筒的底部送入，上升到正在转动的砂子间，逐层地在叶轮之间接受研磨，最后到达筒的上部经筛网流出筒体，筛网将砂子留住，只让经过研磨的墨料通过（图13-17)。卧式砂磨机实际上是把立式砂磨机筒体横过来水平放置的一种砂磨机。因为转轴是水平的，所以叶轮的平面是垂直于水平面的(图13-18)。  \n\n![](images/31bddb5bfca2f9865c1a830ad4b7826d9f3dcc242681612605eb39349b7ea3ab.jpg)  \n图13-16两种不同的立式球磨机结构示意  \n\n![](images/afbbfe1d25b027c34ab3b7f3b8845cb46e8c695ea89eacbcd3bf20b7c66de332.jpg)  \n图13-17立式砂磨机示意 1一控制墨料流速的阀；2—送料口；3—稳定轮； 4一夹套；5—叶轮；6—搅拌轴；7—出料口  \n\n![](images/f18aeed4a99fbd0180efbdf345ec3fc332026b622f2480131e4f9228b7db0148.jpg)  \n图13-18 卧式密封砂磨机  \n\n1—主机；2—叶轮；3—墨料入口；4—压力表；  \n5—冷却水出口；6一电器及仪表箱；7一墨料出口；  \n8-冷却水人口；9一送料泵；10一送料泵出口  \n\n砂磨机中最早使用的研磨介质是天然砂子，现在有多种材料。一般砂子以球形或接近球形最好，直径在0.3～3.0mm范围内，实际上很少使用直径在0.6mm以下的砂子。由于砂磨机的研磨作用是以撞击力和剪切力为主，因此砂子密度大，所产生的撞击力和剪切力也大，研磨效果就更好，表13-7列出了几种用作研磨砂子的材料密度。砂子的用量常常为砂子体积量占筒体容积50%稍多一些，卧式砂磨机可达80%。砂磨机的搅拌速度可在旋转叶轮的圆周速度480～900m/min范围内，推荐使用600m/min的叶轮圆周速度。  \n\n表13-7常用研磨介质的相对密度  \n\n\n<html><body><table><tr><td>研磨介质</td><td>相对密度</td><td>研磨介质</td><td>相对密度</td></tr><tr><td>钢球</td><td>5.0</td><td>磁球(高铝含量）</td><td>2.0</td></tr><tr><td>石</td><td>1.7</td><td>磁球(冻石型)</td><td>1.5</td></tr><tr><td>高硬度球</td><td>10.0</td><td>玻璃球</td><td>1.6</td></tr></table></body></html>  \n\n砂磨机的分散效率很高，产量大，还可连续生产，并能确保分散质量均匀。但进入砂磨机的墨料必须经过良好的预分散，这样才能发挥砂磨机的工作效率。  \n\n选择施工涂装方式是UV涂料固化过程的重要环节。涂装方式包括刷涂、刮涂、辊涂、浸涂、淋涂、甩涂、喷涂和静电喷涂。液态UV涂料通常采用辊涂、淋涂、喷涂的涂装工艺，UV粉末涂料则用静电喷涂涂装工艺。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 661,
+        "chunk": "# 13.6.1 辊涂及辊涂机  \n\n辊涂又称滚涂，它是UV涂料应用最为广泛的涂装方法，适用于黏度较大的涂料，特别适用卷材和平面基材的高速涂布。由于辊涂机辊子转动方向不同而分为同向和逆向两类。  \n\n(1）同向辊涂机涂漆辊的转动方向与被涂物的前进方向一致，其被涂物因施加有辊的压力，涂料呈挤压状态分布，涂布量少，涂层也薄（图13-19)。  \n\n![](images/e8a60d5bbced28319c7edb350f21ce9369d796ebc39e40f46490fca1cf9f6001.jpg)  \n图13-19同向辊涂机工作示意 1-收集涂料盘；2—刮板；3—背撑辊；4—涂漆辊（橡胶)；5—供料辊（钢制); 6—涂料；7—涂料盘；8—修整辊（橡胶)  \n\n（2）逆向辊涂机的涂漆辊转动方向与被涂物的前进方向相反，被涂物面没有辊的压力，涂料呈自由状态分布，涂布量大，所得涂层厚（图13-20)。  \n\n辊涂法所用涂料黏度在 $40{\\sim}150\\mathbf{s}$ (涂-4杯)。辊涂法具有涂装效率高，涂膜外观质量较好，涂层厚度控制容易，适合流水线连续化生产，污染小，涂料不浪费，特别适用于大面积板材和带材的涂装，如纸张上光、木地板涂装、橱柜板材涂装、PVC扣板涂装、板式家具涂装、金属板材涂装等。辊涂不能涂装立体工件，不适合厚涂层涂装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 662,
+        "chunk": "# 13.6.2 淋涂及淋涂机  \n\n淋涂也叫帘涂，它是一种非接触式的涂布方法，适用于黏度较小的UV涂料。涂料通过喷嘴或窄缝从上淋下，涂布到下方通过传动装置的被涂物上，多余的涂料进人回收容器，再泵送到高位槽循环使用（图13-21）。  \n\n![](images/00c8427e803f6d44c357c05970f497c0d1cd737ac5711a2cffad14d1c90ff00c.jpg)  \n图13-20逆向辊涂机的工作示意1一涂料盘；2—供料辊（钢制）；3-涂漆辊（橡胶)；4一背撑辊；5-金属带；6—导向辊（钢制）  \n\n淋涂具有生产效率高、作业性好、在工艺参数稳定时涂膜外观优良丰满、可涂装较厚涂层、涂料损失很小等特点，适用于大批量生产的板材和带材的涂装，如竹木地板面漆涂装、彩涂钢板涂装、橱柜板材涂装、塑料板材涂装等。淋涂也不能涂装结构复杂的部件，不适用多品种、小批量的涂装。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 663,
+        "chunk": "# 13.6.3喷涂及喷涂设备  \n\n喷涂也是一种非接触式的涂布方法，适用于涂装结构复杂的部件。喷涂有空气喷涂和无空气喷涂两种。  \n\n![](images/5a7db5656c495b06ebf7ea7229796b6c302dcaecc57151529c87d2c779ce415b.jpg)  \n图13-21 淋涂示意图  \n\n1—涂料槽；2—泵；3—过滤器；4—调节阀； 5—压力表；6—输送机；7一防风玻璃； 8一狭缝；9—淋涂头；10—涂料接收器  \n\n（1）空气喷涂空气喷涂是利用压缩空气的气流使涂料雾化成雾状并在气流带动下涂到被涂物表面的一种涂装方式。一套比较完整的空气喷涂装置应包括空气压缩机、输气管、空气油水分离器、贮气罐、喷枪、涂料槽、喷漆室等。空气压缩机用来产生压缩空气；输气管是用来连接空气压缩机到喷枪各个设备之间的管道；空气油水分离器用于分离压缩空气中的水分、油分及其他杂质，以保证涂膜质量；贮气罐用于贮存压缩空气，可通过压力控制阀调节贮气罐的压力，以消除压力波动。  \n\n![](images/76cd3e8a526df0b8f7330cd3a3266cf54b82d4103fdc08bd8b06321f5eb6c71a.jpg)  \n图13-22吸上式喷枪结构1—漆罐；2-罐盖；3—涂料喷嘴；4一空气喷嘴；5一枪体；6一空气密封螺栓；7一空气接头；8一枪机  \n\n![](images/ece1f45987a9bcc71b27b778ebe1fd1c4c05a1ccea8e3197ef428a60da464163.jpg)  \n图13-23重力式喷枪结构  \n\n喷枪是空气喷涂的关键设备，常用空气喷枪有吸上式、重力式和压送式三种（图13-22～图13-24)，吸上式喷枪是现今应用最广泛的间歇式喷枪，这种喷枪的喷出量受涂料黏度和密度的影响较大，涂料杯中残存漆液会造成一定损失，但涂料喷出的雾化程度较好。重力式喷枪是将涂料杯安装在喷枪的斜上部，喷出量比吸上式大，但雾化程度不如吸上式。当涂装量大时，可将涂料杯换成高位槽，用胶管与喷枪连接，可实现连续操作。压送式喷枪依靠另外设置的增压箱供给涂料，它适用生产流水线涂装和自动涂装，增大增压箱压力，可供几支  \n\n![](images/b138fca949338d2f89af31b0cd3bb6e758addda0dde221cd5e64359ee9f690fb.jpg)  \n图13-24压送式喷枪工作原理示意1一喷枪；2一涂料增压箱  \n\n喷枪工作，涂装效率高。  \n\n常用喷枪一般由喷头、调节部件和枪身三部分组成。枪身为便于操作，做成能手握的形状；调节部分是用于调节涂料和空气喷出量的装置。喷头由喷嘴、空气帽和针阀组成，由它决定涂料的雾化、喷流图样的变化。喷嘴是喷枪的关键的部件，现在绝大多数喷枪采用涂料和空气在喷嘴外部混合方式，喷嘴有一个涂料出口和多个空气出口，使喷出的空气量和压力较均衡，涂料喷雾较细，分布均匀，喷涂幅度较宽（图13-25)。喷嘴口径在 $0.5\\mathrm{\\sim}5\\mathrm{mm}$ ，以适应不同黏度和不同种类的涂料。喷嘴口径大，可用于黏度大的涂料，而且涂料喷出量也多。涂料黏度对喷涂影响极大，黏度过大，涂料雾化困难；黏度过小，则易发生流挂。一般空气喷涂适宜的黏度在16～30s（涂-4杯）之间的涂料。  \n\n![](images/68be2d4504f66586d67db4b0289a353f591bb17e0092a5e16385ccf5bc36b363.jpg)  \n图13-25 喷嘴结构  \n\n空气喷涂法的优点是几乎可适用于任一种涂料和任何被涂物，并能涂装出质量优良的涂膜；不足之处是喷涂过程涂料飞散损失太大，污染环境而且不安全。  \n\n（2）无空气喷涂无空气喷涂是靠密闭容器内的高压泵压送涂料，获得高压的涂料从小孔中高速喷出，随着压力急剧下降，涂料体积骤然膨胀，溶剂迅速挥发而分散雾化，高速飞向被涂物。由于它是利用高液压而不是空气流速使涂料雾化喷出，所以又叫高压无气喷涂。无空气喷涂是涂料涂装的一项新工艺，它可解决高黏度涂料涂装困难、空气喷涂涂料损失大、飞散漆雾污染严重等病。  \n\n高压无气喷涂装置是由动力源、高压无气喷涂机、涂料槽、输漆高压软管、喷枪等组成(图13-26)。高压无气喷涂机的工作原理是在泵的上部有气动推动器或油压推进器的加压用活塞，推动泵下部的涂料活塞，加压活塞面积和涂料活塞面积之比越大，所产生的涂料压力也就越高。最常用的是气动式高压无气喷涂机，其体积小、重量轻、安全可靠。高压无气喷涂用喷枪与普通空气喷枪不同，没有压缩空气通道，由枪身、喷嘴、过滤网和连接部件组成，但对枪的强度和密封性要求更高（图13-27)。喷嘴口径在0.17～1.80mm之间，涂料黏度越大，需用喷嘴口径也大。涂料黏度不同，所需喷涂压力也不同。表13-8介绍不同涂料黏度与所需喷涂压力之间的关系。  \n\n除一些水性涂料和黏度过小的涂料外，高压无气喷涂几乎适合所有涂料的涂装，特别适用黏度比较高的厚涂层涂料、防污涂料、阻尼涂料的涂装，也适用建筑、船舶等大面积涂装和一次成膜厚度大的工件涂装。高压无气喷涂涂装效率高，几乎是空气喷涂的3倍；涂料压力高，能与基材形成极好的附着力；漆流中没有空气，可消除水分、油分或其他杂质带来的弊病；喷雾分散少，减少了空气污染；一次涂装涂层厚。其缺点是涂膜外观质量不如空气喷涂好；喷出涂料压力太高，一旦伤人会造成严重后果；操作时喷雾幅度与喷出量不能调节，必须更换喷嘴。  \n\n![](images/71f52a053554f90a43862a3152713cc15bdd90f2b2103ac645679cef9260fa53.jpg)  \n图13-26高压无气喷涂装置1一动力泵；2—柱塞泵；3一涂料容器；4—蓄压器；5—输漆管；6—喷枪  \n\n![](images/f3bc720be13cf2bd60045295f6c9979b75cddc3ea52a1368f87d1e3cfc1d6fe5.jpg)  \n图13-27高压无气喷涂用喷枪 1—枪身；2—扳机；3—喷嘴；4—过滤网； 5—衬垫；6—顶针；7一自由接头  \n\n表13-8涂料黏度与喷涂压力的关系  \n\n\n<html><body><table><tr><td>涂料黏度/Pa·s</td><td>喷涂压力/MPa</td><td>涂料黏度/Pa·s</td><td>喷涂压力/MPa</td></tr><tr><td>0.05</td><td>4</td><td>1.1</td><td>10</td></tr><tr><td>0.7</td><td>8</td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 664,
+        "chunk": "# 13.6.4静电喷涂及喷涂设备  \n\nUV粉末涂料多采用静电喷涂进行涂装，对于导电性基材，使用传统的电晕喷枪喷涂；对于非导电性基材，应使用摩擦起电喷枪喷涂；对于特别不导电基材，则要使被涂物表面带上与喷枪相反的电荷，以利于涂装。静电喷涂有高压静电喷涂和摩擦静电喷涂两种。  \n\n（1）高压静电喷涂高压静电是由高压静电发生器供给的，工件在喷涂时应先接地，在净化的压缩空气的作用下，粉末涂料由供粉器通过输粉管进人静电喷粉枪。喷枪头部装有端部具有尖锐边缘的金属环或极针作为电极，当电极接通高压静电后，尖端产生电晕放电，在电极附近产生了密集的负电荷。粉末从静电喷粉枪头部喷出时，捕获电荷成为带电粉末，在气流和电场作用下飞向接地工件，并吸附于工件表面上，完成涂装。高压静电喷涂的喷涂电压一般控制在60～80kV之间，喷粉量掌握在100～300g/min较为合适。粉末涂料在静电喷涂过程中，工件的上粉率在50%～70%左右，约有30%～50%的粉末飞扬，因此喷涂必须在喷粉柜（又称粉末喷涂室）中进行。同时要设置回收装置来搜集未涂装的粉末，经重新筛选后，送回供粉桶备用，减少浪费和对环境的污染。高压静电喷涂的工件可以在室温下涂装；粉末的利用率高，可达95%以上；涂膜质量高，薄而均匀、平滑、无流挂现象，即使在工件尖锐的边缘和粗糙的表面亦能形成连续、平整、光滑的涂膜；可在流水线上生产，效  \n\n率高。  \n\n（2）摩擦静电喷涂摩擦静电喷涂不需要高压静电发生器，喷枪枪体通常使用电阴极材料，喷粉时由于粉末粒子之间碰撞以及粉末与枪体之间摩擦，使粉末粒子带上正电荷，而枪体内壁则产生负电荷，此负电荷经接地电缆引入大地。带正电的粉末粒子在压缩空气的气流作用下飞向工件，并被吸附在工件表面上，完成涂装（图13-28)。摩擦静电喷涂的喷粉量，平面喷涂控制在 $80\\mathrm{\\sim}100\\mathrm{g/min}$ ，管道内壁喷涂时控制在 $100{\\sim}250\\mathbf{g}/\\operatorname*{min}$ ；上粉率一般小于$60\\%$ ，若采用摩擦静电热喷涂，上粉率可达 $80\\%\\sim85\\%$ 。摩擦静电喷涂不用高压静电发生器，节约了设备投资；摩擦静电喷枪无金属电极，喷涂中不会出现电极与工件短路引起的火花放电，消除了引起粉尘燃烧、爆炸的隐患，安全可靠；操作简捷，适用范围广，可喷涂较厚的涂层；可在流水线生产，效率高。但对摩擦带电效果差的粉末（如聚乙烯)，喷涂效果不理想；同时，摩擦静电喷涂工艺对环境、气源的要求严格，限制了它的应用范围；与高压静电喷涂相比，粉末摩擦带电量不充足，影响粉末对基材的吸附能力。  \n\n![](images/923e5517480428ca4da9b7eb3aa0488a1399acd186555de35f76e042072141b9.jpg)  \n图13-28摩擦静电喷涂原理",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 665,
+        "chunk": "# 第14章 电子束固化  \n\n电子束（electronbeam，缩写为EB）是指具有一定能量（运动的）电子在空间聚集在一起沿着同一方向运动的电子流。利用电子束使液态材料变成固态材料的过程就称为电子束固化。  \n\n电子在电场中，受正电极吸引而发生向正极移动，获得移动能量，此过程称为电子加速，这是电子获得能量的过程。要想达到可利用的具有足够能量的电子束，必须提供足够高的电压以形成足够强的电场使电子加速，这类使电子加速的设备为电子加速器（electrongenerator 或 electron accelerator)。几种类型的低能加速器如图14-l所示。  \n\n![](images/db392d14bc32b1b17e7e320509ae2288ba569a3fd893155c3e92e1c624a83ae1.jpg)  \n图14-1几种类型的低能加速器  \n\n1—产品；2—窗口；3—扫描线圈；4—格栅；5—灯丝；6—灯丝和格栅电子束的特性用电子束能量 $\\scriptstyle{E}$ 和电子束强度 $\\boldsymbol{\\mathit{I}}$ 来表示：  \n\n（1）电子束能量 $\\scriptstyle{E}$ 用电子伏特 $\\mathbf{eV}$ 来表示：  \n\n$$\n\\scriptstyle{E=e V}\n$$  \n\n式中e1个电子的电量；V—加速电场的电压。  \n\n1电子伏特（leV）表示一个电子通过电压差为1V电场时所获得的能量。常用的电子束能量单位有：  \n\n$$\n\\scriptstyle\\mathbf{GeV}=10^{9}\\mathbf{eV}\n$$  \n\n$$\n\\bf{T e V}\\mathrm{=}10^{12}e V\n$$  \n\n1eV=0.446×10-25kW·h(千瓦·小时)=1.602×10-J(焦耳)=1.602×10-6Gy(戈瑞）  \n\n(电能)  \n\n(热能)  \n\n(吸收剂量)  \n\n这是电子伏特对应于电能、热能和吸收剂量三个关系式。  \n\n（2）电子束的另一特性为电子束强度I，用安培A来表示。  \n\n$$\nI{=}\\frac{Q}{t}\n$$  \n\n式中 $\\alpha$ —电子束的电荷，C(库仑);t—一电荷通过的时间。  \n\n当单位时间电子束流过电荷的电量为1C时，其电子束强度（流强）为1A。常用电子束强度单位有：  \n\n与电子束固化有关的还有两个物理量：吸收剂量D和辐射化学产额G。  \n\n(1）吸收剂量D表示被辐照物质单位质量吸收辐照能量的多少，单位为戈瑞（Gy)。  \n\n$$\n{\\cal D}{\\cal=}E/m\n$$  \n\n$$\n16\\mathbf{y}{=}1\\mathbf{J}/\\mathbf{kg}\n$$  \n\n每千克物质吸收1J辐照能量为1Gy。  \n\n（2）辐射化学产额G表示被辐照的物质，每吸收100eV的辐照能量后，发生化学物理变化的数量，也称为化学产额。  \n\n例如氢原子受辐照后产生电离需要16eV，其G值为6.25；在空气中辐照形成1对离子需33.85eV，则可以说空气的G值约等于3。  \n\n部分被辐照物质的化学产额见表14-1。  \n\n表14-1部分被辐照物质的化学产额  \n\n\n<html><body><table><tr><td>辐照物质</td><td>1个化学物理变化 需吸收能量/eV</td><td>化学产额 (G)</td><td>辐照物质</td><td>1个化学物理变化 需吸收能量/eV</td><td>化学产额 (G)</td></tr><tr><td>氢</td><td>16</td><td>6.25</td><td>高分子改性</td><td></td><td>1~25</td></tr><tr><td>空气</td><td>33.85</td><td>2.95</td><td>乙烯基聚合</td><td></td><td>104~107</td></tr></table></body></html>",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 666,
+        "chunk": "# 14.2 电子加速器  \n\n电子束是由电子加速器产生的，作为工业应用的电子加速器是20世纪50年代发展起来的。1957年德国拜耳公司和意大利Pirelli公司发展了2MeV的电子加速器，用于研究和开发聚烯烃的交联技术：1967年荷兰将绝缘芯型电子加速器用于研究涂料的固化；1973年第一条木材表面涂层电子束固化生产线在荷兰Svedex公司投人运行；1978年德国WKP公司率先装备了 $200\\mathrm{cm}$ 宽的电子加速器固化系统，用于装饰制品的色漆固化；20世纪80年代初出现的电子帘型加速器是一种结构紧凑、体积小巧的电子加速器，也是对辐射固化应用最理想的加速器。  \n\n在辐射加工中通常将电子加速器按其能量高低来分类，分为低能电子加速器、中能电子加速器和高能电子加速器(表14-2)。  \n\n表14-2电子加速器的分类  \n\n\n<html><body><table><tr><td>项目</td><td>高能电子加速器</td><td>中能电子加速器</td><td>低能电子加速器</td></tr><tr><td>电子束能量/eV</td><td>10M~5M</td><td>5M~300k</td><td><300k</td></tr><tr><td>穿透能力</td><td>深</td><td>较深</td><td>浅</td></tr><tr><td>电流密度</td><td>小</td><td>不大</td><td>可很大</td></tr><tr><td>主要用途</td><td>辐射消毒，食品辐射处理</td><td>聚烯烃电线电缆的交联，制造聚烯烃热收缩材料</td><td>辐射固化</td></tr></table></body></html>  \n\n适用于电子束固化的电子加速器为低能电子加速器，有三种类型：扫描式、帘式（也叫电子帘）和多阴极式（图14-1)。  \n\n目前能生产电子束固化用的低能电子加速器仅有少数国家（表14-3)。  \n\n表14-3用于电子束固化的低能电子加速器的性能指标  \n\n\n<html><body><table><tr><td>型号</td><td>国家</td><td>能量/keV</td><td>功率/kW</td><td>束宽/m</td></tr><tr><td>Irelec</td><td>法国</td><td>200 300</td><td>20 22.5</td><td>0.3~1.8 0.3~1.8</td></tr><tr><td>Polymer Physik Nissin High Voltage</td><td>德国 日本</td><td>150~280 300</td><td>≤5~6 7.5</td><td>0.22~2.5 0.45</td></tr><tr><td></td><td></td><td>300 300</td><td>19.5</td><td>1.2</td></tr><tr><td></td><td>俄罗斯</td><td>300～500</td><td>30 25</td><td>1.8 0.5~2.0</td></tr><tr><td>Avora 2 Eol-400</td><td>俄罗斯</td><td>14000</td><td>≤2.0</td><td>一</td></tr><tr><td>Electrocurtain</td><td>美国</td><td>150~300</td><td></td><td></td></tr><tr><td></td><td></td><td></td><td>≤100</td><td>0.5~2.0</td></tr><tr><td>Broad Beam</td><td>美国</td><td>150~300</td><td>≤360</td><td>0.3~2.5</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 667,
+        "chunk": "# 14.3.1电子束固化的技术优势  \n\n电子束固化是一项高效、无污染、节能的加工技术，与热固化相比，有很多的技术优势(表14-4)。  \n\n电子束固化与紫外光固化相比，除了设备投资大，需要惰性气体保护外，也有技术优势(表14-5)。  \n\n（1）电子束固化不需用价格较贵的光引发剂，降低配方产品的成本；不会因残留光引发剂及光分解产物迁移和挥发，引起难闻的臭味，有利于材料的耐老化性能，并可应用于食品、医药等包装材料。  \n\n表14-4电子束固化和热固化技术比较  \n\n\n<html><body><table><tr><td>项目</td><td>电子束固化</td><td>热固化</td></tr><tr><td>能耗 固化速率 设备占地面积</td><td>低(室温) 快(几秒) 小（15～20m长) 无(无溶剂)</td><td>高（至少60～70℃，一般100℃以上） 慢(几小时) 大(30~90m长) 有(有溶剂)</td></tr></table></body></html>  \n\n表14-5电子束固化与紫外光固化技术比较  \n\n\n<html><body><table><tr><td>项目</td><td>电子束固化</td><td>紫外光固化</td><td>项目</td><td>电子束固化</td><td>紫外光固化</td></tr><tr><td>能源</td><td>电子加速器</td><td>紫外光源</td><td>辐射穿透性/μm</td><td></td><td></td></tr><tr><td>能耗</td><td>较低</td><td>较高</td><td>清漆</td><td>约500</td><td>约130</td></tr><tr><td>引发种</td><td>高能电子</td><td>自由基、阳离子</td><td>色漆</td><td>约400</td><td>约50</td></tr><tr><td>聚合反应引发剂</td><td>不需要</td><td>光引发剂</td><td>转化率/%</td><td>95～100</td><td>约90</td></tr><tr><td>情性气体</td><td>需要</td><td>不需要</td><td>设备投资</td><td>商</td><td>低</td></tr></table></body></html>  \n\n（2）对油墨和色漆等有色涂层，不存在光固化因颜料对光的吸收而难以透过的问题，避免了光固化必须使用量大而价贵的光引发剂的缺点。  \n\n（3）电子束穿透深度大，故电子束固化不仅可用于薄的表面涂层，也可用于厚达数毫米甚至数厘米的复合材料的固化以及双面固化，这在光固化是比较难以做到的。  \n\n（4）电子束固化可使涂层材料与基材产生化学结合（如接枝)，提高涂层与基材的附着力，这对光固化也是难以实现的。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 668,
+        "chunk": "# 14.3.2电子束固化机理  \n\n电子束固化机理与紫外光固化机理有本质区别。  \n\n紫外光固化机理是光引发剂吸收紫外光后，产生自由基（或阳离子)，引发带不饱和双键（或环氧基、乙烯基醚）的单体和低聚物聚合、交联，该体系中所有新键都是通过不饱和双键（或环氧基、乙烯基醚）的交联聚合而产生的。  \n\n电子束固化时，电子束在体系中随机产生自由基（包括阳离子自由基、阴离子自由基和单体、低聚物裂解自由基)，引发带不饱和双键的单体和低聚物聚合交联，而且随机产生的自由基本身也可交联或进攻不饱和体系产生交联，甚至与基材发生反应（接枝)，新键产生的范围更广、更复杂。 足龙  \n\n电子束固化过程可描述如下。  \n\nM+e\\*（高能电子束)—→M+（自由基阳离子)十e(M释放低能电子)$\\mathbf{M}^{+}\\cdot+\\mathbf{e}\\mathrm{-}\\mathbf{\\Gamma}\\{\\mathbf{M}^{*}$ （激发态)—→M·（自由基）M+·—→H·+M+或H++M·（自由基阳离子裂解)$\\mathbf{M}+\\mathbf{e}^{\\bullet}$ （高能电子束)一 $\\mathbf{\\Gamma}\\mathbf{\\rightarrow}2\\mathbf{R}\\cdot\\mathbf{\\Gamma}$ (裂解产生自由基)  \n\nM·自由基和R·自由基均能引发单体和低聚物聚合、交联。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 669,
+        "chunk": "# 14.3.3电子束固化的氧阻聚  \n\n电子束固化配方绝大多数是自由基聚合体系，因此都存在氧阻聚问题，此问题在电子束固化中更加严重，而且不能像光固化中那样用加大光强或提高光引发剂浓度等办法来解决。所以电子束固化为克服氧阻聚，一般采用惰性气体保护，特别是在氮气氛下辐照，所用氮气的含氧量应少于 $0.05\\%\\sim0.1\\%$ 。由于电子束固化必须在情性气体中进行，增加了辐照装置的复杂性及生产成本，成为制约其发展的因素之一。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 670,
+        "chunk": "# 14.3.4电子束固化材料的组成  \n\n电子束固化材料的组成与紫外光固化材料的组成基本上是一样的，只是电子束固化材料不用光引发剂。  \n\n电子束固化材料的基本组成是低聚物、活性稀释剂、颜料和填料及其他助剂，这些原材料与紫外光固化材料所用原材料是相同的。  \n\n电子束由于能量高，所以在电子束固化材料中不用加光引发剂，而且固化时双键转化率极高 $(95\\%\\sim100\\%)$ ）因此不存在小分子迁移和有害的光分解产物产生，产品表面硬度和光泽度很高，有色体系涂层、不透明涂层和厚涂层都易固化，这些都是紫外光固化较难做到的，因而电子束固化在涂料、油墨、胶黏剂和复合材料等产业中有着广泛的应用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 671,
+        "chunk": "# 14.4.1电子束固化在涂料上的应用  \n\n电子束固化最早应用的地方是木器涂料，当时还是第一代木器涂料为不饱和聚酯-苯乙烯体系，由于苯乙烯的毒性、沸点低、易挥发及刺激性，已为丙烯酸酯体系所取代。从腻子、底漆到面漆，从高光泽到低光泽、亚光，从清漆到色漆，特别是白漆，都可用电子束固化实现。  \n\n电子束固化用在瓷砖、PVC板、中密度板、石膏板等多种建材上，用浸渍了树脂的纸作贴面装饰，经电子束固化后，不仅增强了耐刮擦性和耐磨性，还赋予装饰效果。  \n\n电子束固化用于金属涂料上，主要用于钢材，特别是卷材的涂装，包括底漆和面漆（清漆和色漆)。与紫外光固化相比，电子束固化金属涂料固化速率更快、能耗低以及具有良好的附着力。 1.0  \n\n电子束固化用于纸张上光，主要是用于包装材料的纸制品上光，由于不用光引发剂，无小分子迁移、无光分解产物和低气味，可用于食品和药品的包装，这是与紫外光固化材料比较有很大优势的地方之一。 器  \n\n用于磁性介质的电子束固化涂料可制造录像带、录音带、磁盘等磁性记录材料。由于这类涂料含有大量的三氧化二铁或四氧化三铁，紫外光根本无法穿透到涂层底部，而电子束则很容易穿透到底部，使涂层很好固化。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 672,
+        "chunk": "# 14.4.2电子束固化在印刷油墨上的应用  \n\n电子束固化在有色体系上应用有极大优势，颜料对电子束无屏蔽作用，特别像白色或黑  \n\n色颜料对紫外光有很大吸收或反射，采用电子束则很易固化。对于四色套印的胶印、凹印和柔印，可以四色印刷、一次固化。同样电子束固化非常适用于食品包装的印刷，包括纸张包装材料、塑料薄膜和制品包装材料、金属包装材料。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 673,
+        "chunk": "# 14.4.3电子束固化在胶黏剂上的应用  \n\n电子束固化用在相同或不同的塑料薄膜的层合，如OPP/OPP（拉伸聚丙烯)、改性OPP/改性OPP、OPP/金属镀膜OPP、聚酯/低密度聚乙烯。  \n\n用于软包装层合，大量使用在食品包装和化妆品包装上，这也是由于电子束固化胶黏剂不用光引发剂且固化彻底。  \n\n电子束固化也应用于压敏胶和离型材料的生产上，由于固化速率快，可以大规模和低成本的生产。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 674,
+        "chunk": "# 14.4.4电子束固化在复合材料上的应用  \n\n电子束可以穿透不透明材料实现固化，特别适用于复合材料的制造，这是紫外光固化难以实现的。目前用于碳纤维增强复合材料、聚酰胺纤维增强复合材料和玻璃纤维增强复合材料等复合材料的制造，在航天航空、汽车制造、高压容器和军工上有广泛应用，已报道用电子束固化技术制造火箭发动机壳体，制造导弹的整体燃料箱和发动机进气道样件，修补A320飞机的整流罩等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 675,
+        "chunk": "# 14.4.5电子束在高分子加工改性中的应用  \n\n低能电子束除了在上述涂料、油墨、胶黏剂和复合材料等固化上应用外，还有一个重要的应用领域就是高分子加工改性。高分子加工改性包括高分子交联改性和高分子接枝改性。  \n\n（1）高分子交联改性过去高分子交联改性都采用化学交联工艺，不少高分子品种难以进行交联反应，而且成本高。若采用电子束（包括丫射线）交联工艺，就很容易进行各种高分子交联改性（表14-6)。  \n\n表14-6辐射交联与化学交联工艺比较  \n\n\n<html><body><table><tr><td rowspan=\"3\">项目</td><td rowspan=\"3\">辐射交联</td><td colspan=\"2\">化学交联</td></tr><tr><td>过氧化物</td><td>硅烷</td></tr><tr><td>加热(蒸汽，红外)</td><td>水</td></tr><tr><td>交联方法</td><td>EB或Y射线 O</td><td></td><td>O</td></tr><tr><td>LDPE</td><td></td><td></td><td>X</td></tr><tr><td>HDPE</td><td>O</td><td></td><td></td></tr><tr><td>橡胶</td><td>0</td><td>O</td><td>X</td></tr><tr><td>PVC</td><td>O</td><td></td><td></td></tr><tr><td>氟橡胶</td><td>O</td><td>×</td><td>×</td></tr><tr><td>其他</td><td>0</td><td>×</td><td>×</td></tr><tr><td>挤压加工性</td><td></td><td>×</td><td>×</td></tr><tr><td>复合物寿命</td><td></td><td>△</td><td></td></tr><tr><td>材料</td><td>标准</td><td>昂贵</td><td>昂贵</td></tr><tr><td>交联</td><td>量少较贵，量大便宜</td><td>细徽物较贵</td><td>接枝成本高</td></tr><tr><td>高频</td><td>良好</td><td>不适合</td><td>不适合</td></tr><tr><td>耐热变形</td><td>优</td><td>优</td><td>良</td></tr><tr><td>外观</td><td>优</td><td>粗糙</td><td>良</td></tr><tr><td>交联设备</td><td>复杂、昂贵</td><td>一般</td><td>简单</td></tr></table></body></html>\n\n注：“○”代表优秀；“”代表一般；“X”代表较差。  \n\n利用通用的高分子材料、通用高分子和不同交联剂混合体系或不同种类通用高分子共混体系，经电子束辐射交联，可以制得性能优异的工程化通用塑料。  \n\n（2）高分子接枝改性通过电子束辐射，可以用两种方法进行高分子接枝改性。一种为预辐射法，经电子束辐射，在高分子主链上生成游离基后，再与单分子进行接枝反应，得到接枝改性高分子；另一种为同时辐射法，在高分子与单分子共存条件下，用电子束辐照，进行接枝反应，得到接枝改性高分子。经接枝改性的高分子具有某些特殊的性能，成为功能化的通用高分子。用此接枝改性技术，可以制造如无滴膜、阻隔膜、吸附膜等功能膜。辐射交联与化学交联工艺比较见表14-6。  \n\n![](images/2c413970934ba8ead7fe94325bbe20c12131a6df5d097af80ecaddf510d2cdb6.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 676,
+        "chunk": "# 附录1 光引发剂吸收光谱图  \n\n![](images/f4561bd82d893e986b6c7c155b2787088b7ae4ac4a65cb23fdff67692325e379.jpg)  \n\n![](images/673f8de4152519931389d668b7a4e5dc0c55dc85b9bda8f3be1386336de37568.jpg)  \n\n![](images/4c9cb01ced3f59790f61f1990523d0c6c7db90b949c5a00408d0ff9b3ccf61b1.jpg)  \n\n![](images/0986148b012191416f6ffc0023ffe0045e818a1cf924be763ccaaba666bcc39d.jpg)  \n\n![](images/76c54ff6c8e2c69b3e7118d7759db46d954ec932a896a40159b6df47b9fa144c.jpg)  \n\n![](images/bbf268d428adea91998b24c7c0ca4c363bbf0918516cd15fe59d737a9f3b8887.jpg)  \n\n![](images/ac15f447ccc304655312869d8e58575d9a3e7cddae380d7ad0bd13978eae745c.jpg)  \n\n![](images/0c2b3df9dc036fe0c562ce13cbfb5ccb936015736baef72f63cf67220f3497a1.jpg)  \n\n![](images/ec36f9d1c2f1da4d4063b8a192257faa0791cd62b0ec62b648118a49145f7cfb.jpg)  \n\n![](images/ec4b8f726214f043dd5ee429dc2feda6323ec2ffef73d5a5d1405d959a61fded.jpg)  \n\n![](images/2299f526a42b45501b02008b1a1ecaefdb23cc32b8b34e5be55e6d4996546c25.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 677,
+        "chunk": "# 附录2 光固化原材料有关性能的测试方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 678,
+        "chunk": "# 一、酸值  \n\n酸值是衡量待测物中所含游离酸多少的物理量，它是用中和1g待测物中的酸性物质所消耗的氢氧化钾的质量（mg）来表示。",
+        "category": " Introduction"
+    },
+    {
+        "id": 679,
+        "chunk": "# 1.测试方法  \n\n准确称取一定量的待测试样，以乙醇或丙酮溶解（如较难溶，可以在水浴上温热)，加人 $2{\\sim}4$ 滴酚指示剂，在不停摇动下，以经过标定的 $0.1\\mathrm{mol/L}$ 左右的氢氧化钾溶液滴定至指示剂明显改变颜色为止，酸值按下式计算。  \n\n$$\n\\scriptstyle A={\\frac{56.1V N}{m}}\n$$  \n\n式中A-——酸值， $\\mathbf{mg/g}$ 。$\\boldsymbol{v}$ 一滴定用去的KOH的体积， $\\mathrm{\\mL}$ $N$ -—KOH摩尔浓度， $\\scriptstyle{\\mathrm{~mol/L~}}$  \n\n56.1- ---KOH的摩尔质量， $\\mathbf{g}/\\mathrm{mol}$ $\\mathbf{\\psi}_{m}$ 样品质量，g。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 680,
+        "chunk": "# 2.注意事项  \n\n（1）为使测定结果更准确，可按附表2-1所示称取样品。  \n\n附表2-1测定酸值的样品参考用量  \n\n\n<html><body><table><tr><td>酸值范围</td><td>样品量/g</td><td>酸值范围</td><td>样品量/g</td></tr><tr><td rowspan=\"2\">0~5</td><td>20.00±0.05</td><td>30～100</td><td>2.500±0.001</td></tr><tr><td>5~15</td><td>10.00±0.05</td><td>1,000±0.001</td></tr><tr><td>15~30</td><td>5.00±0.05</td><td>>100</td><td></td></tr></table></body></html>  \n\n（2）对较难溶解的样品，可尝试用乙醇与甲苯的混合溶液或丙酮与甲苯混合溶液代替纯乙醇或丙酮溶解样品。  \n\n（3）在测定颜色较深的样品时，指示剂可用甲酚红、6B碱蓝或麝香草酚蓝代替。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 681,
+        "chunk": "# 二、碘值  \n\n碘值是衡量体系不饱和程度的物理量，它用 $_{1\\mathbf{g}}$ 样品消耗碘的质量（mg）表示。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 682,
+        "chunk": "# 1.测试原理  \n\n卤素中氯、溴、碘与不饱和化合物皆能反应，但有差异：氯既能起加成反应，又能发生取代作用；溴只能与不饱和双键起加成反应，而碘则只能被不饱和体系缓慢吸收而起加成反应，但它不可能使不饱和体系完全变成饱和的化合物。故测定碘值不使用单质碘，一般用氯化碘、溴化碘等，不饱和体系的每一个双键可以加成一个氯化碘分子，由此可得饱和的化合物，根据氯化碘的用量，即可算出碘值。  \n\n实际测定时，在样品内加人过量的卤素，再用碘化钾还原反应余下的卤素，然后用淀粉作指示剂，用硫代硫酸钠溶液来滴定，反应如下所示：  \n\n$$\n\\mathbf{X}_{2}+2\\mathbf{KI}\\longrightarrow2\\mathbf{K}\\mathbf{X}+\\mathbf{I}_{2}\n$$  \n\n$$\n\\mathrm{I}_{2}+2\\mathrm{Na}_{2}\\mathrm{S}_{2}\\mathrm{O}_{3}\\longrightarrow2\\mathrm{N}a\\mathrm{I}+\\mathrm{Na}_{2}\\mathrm{S}_{4}\\mathrm{O}_{6}\n$$  \n\n碘值的测定方法很多，其中以维氏法应用较普遍，但它对有共轭双键体系的加成反应分步进行，因此效果不太理想。  \n\n2.试剂  \n\n（1）维氏溶液：将13g碘溶于1000mL冰醋酸内，不易溶时可稍加热，但温度不可太高。冷却后取出200mL，其余部分通人纯而干燥的氯气（氯气需经过洗气瓶水洗、酸洗)，则发生下列反应，至橘红色，游离碘消失为止。  \n\n$$\n_{\\mathrm{I}_{2}+\\mathrm{Cl}_{2}}\\longrightarrow2\\mathrm{ICl}\n$$  \n\n（2）氯气可用下列反应制取：  \n\n$$\n\\mathrm{MnO_{2}}+2\\mathrm{NaCl}+2\\mathrm{H_{2}S O_{4}}\\longrightarrow\\mathrm{Cl_{2}}+\\mathrm{MnSO_{4}}+\\mathrm{Na_{2}S O_{4}}+2\\mathrm{H_{2}O}\n$$  \n\n(3）0.1mol/L ${\\bf K}_{2}{\\bf C r}_{2}{\\bf O}_{7}$ 溶液。  \n\n（4）0.1mol/L ${\\bf N a}_{2}{\\bf S}_{2}{\\bf O}_{3}$ 溶液。  \n\n（5） $1\\%$ 淀粉指示剂：将可溶性淀粉 $_{10\\mathbf{g}}$ 以蒸馏水溶成糊状，然后将其倒人 $1000\\mathrm{mL}$ 煮沸的蒸馏水中，急速搅拌并冷却，如需长期存放，可加人1.25g水杨酸作防腐剂，存放于$4{\\sim}10^{\\circ}\\mathrm{C}$ 条件下。若终点不易判断，淀粉指示剂应重新配制。  \n\n(6) $15\\%$ KI溶液。  \n\n（7）氯仿 $\\mathrm{CHCl}_{3}$  \n\n(8)碘。  \n\n（9）冰醋酸：不能含有还原性杂质。如果有，则需精制：将 $800\\mathrm{mL}$ 醋酸中加入 $_{8\\sim10{\\mathbf g}}$ 高锰酸钾后，放于圆底烧瓶中，装上回流冷凝器，加热回流使其充分氧化后，移人蒸馏瓶内蒸馏，取 $118{\\sim}119^{\\circ}\\mathrm{C}$ 馏出物。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 683,
+        "chunk": "# 3.测试方法  \n\n于锥形瓶中称取样品（见附表2-2，精确至0.000lg)，加人10mL氯仿，摇动使其溶解。用滴定管加人维氏液25mL，塞严（塞口可涂以KI液，但不能流人瓶中)，于暗处在$20^{\\circ}\\mathrm{C}$ 存放 $30{\\sim}60\\mathrm{min}$ （一般碘值低于150时可存放 $30\\mathrm{{min}}$ ，高于150时可存放 $60\\mathrm{{min})}$ 。然后再加人KI液15～20mL，蒸馏水100mL，用0.1mol/LNazSzO3溶液滴定未被吸收的多余碘，至黄色将褪尽时，加入淀粉指示剂lmL，再以0.lmol/LNazSzO3 溶液滴至蓝色完全消失为止（同时做一空白试验，除不加样品外，其他完全相同)。  \n\n附表2-2样品称取量的范围   \n\n\n<html><body><table><tr><td>碘值范围</td><td>样品量/g</td><td>碘值范围</td><td>样品量/g</td></tr><tr><td>80～100</td><td>0.28~0.30</td><td>140~160</td><td rowspan=\"2\">0.17~0.19 0.15~0.17</td></tr><tr><td>100~120</td><td>0.23~0.25</td><td>160~180</td></tr><tr><td>120～140</td><td>0.19~0.21</td><td>180~200</td><td>0.14~0.16</td></tr></table></body></html>  \n\n碘值按下式计算：  \n\n$$\nI{=}\\frac{(V_{2}{-}V_{1})N{\\times}0.1269{\\times}100}{m}\n$$  \n\n式中I——碘值， $\\mathbf{mg/g}$ .  \n\n$\\scriptstyle{V_{2}}$ -—空白试验所用去 $\\mathrm{Na}_{2}\\mathsf{S}_{2}\\mathrm{O}_{3}$ 的体积，mL;$V_{1}$ ——样品试验所用去 $\\mathrm{Na}_{2}\\mathrm{S}_{2}\\mathrm{O}_{3}$ 的体积，mL;$N\\cdot$ — ${\\bf N a}_{2}{\\bf S}_{2}{\\bf O}_{3}$ 的摩尔浓度， $\\scriptstyle{\\mathrm{~mol/L~}}$  \n\n0.1269- 碘的毫克当量数；$\\mathbf{\\nabla}_{m}$ —样品质量，g。  \n\n4.注意事项  \n\n（1）滴定允许误差：碘值在100以下时为0.6，在100以上时为1.0。（2）维氏液自滴定管流出的速度应均匀，玻璃仪器应洁净干净，因为水能与氯化碘（ICI）反应放出游离碘。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 684,
+        "chunk": "# 三、羟值  \n\n羟值表示树脂中羟基的含量，以每克样品相当量的氢氧化钾质量（mg）表示。  \n\n羟值的分析有醋酐吡啶法、苯酐吡啶法及苯异氰酸酯法，以醋酐吡啶法采用最普遍。醋酐吡啶法对伯羟基反应迅速，但对仲羟基反应则比苯酐吡啶法缓慢。因此，对于兼有伯羟基和仲羟基的树脂，苯酐吡啶法测得的结果比醋酐吡啶法的数值为高。  \n\n1．苯酐吡啶法  \n\n（1）试剂$\\textcircled{1}$ 苯酐吡啶液： $_{42\\mathbf{g}}$ 苯酐溶于 $300\\mathrm{mL}$ 无水吡啶中。  \n$\\textcircled{2}$ 指示剂： $1\\%$ 酚酸吡啶溶液。  \n$\\textcircled{3}$ 滴定液： $0.5\\mathrm{{mol/L}}$ 氢氧化钾乙醇溶液。  \n$\\textcircled{4}$ 无水吡啶：含水量少于 $0.1\\%$ 。  \n\n（2）测试方法精确称取约 $\\scriptstyle2_{\\mathbf{\\deltag}}$ 样品（附表2-3)，加入带有回流冷凝器的磨口锥形瓶内，用移液管加入 $10\\mathrm{mL}$ 苯酐吡啶液，并用吡啶将瓶塞润湿，接上冷凝器置于油浴加热，在$115^{\\circ}\\mathrm{C}$ 下回流，间歇地摇荡，保持1.5h左右，冷却到室温，加 $15\\mathrm{mL}$ 吡啶冲洗冷凝器，加$15\\mathrm{mL}$ 蒸馏水以使多余的苯酐水解，加5滴指示剂，以 $0.5\\mathrm{{mol/L}}$ 氢氧化钾滴定至终点保持15s不褪色，同样条件做空白试验。  \n\n按下列计算羟值：  \n\n羟值 $\\scriptstyle={\\frac{(V-V_{0})_{C}\\times56.1}{m}}+$ 酸值羟基含量 $\\stackrel{}{}=\\frac{(V-V_{0})_{C}\\times1.7}{m}\\times100\\%$ 式中 $\\scriptstyle v_{\\circ}$ -——空白滴定消耗氢氧化钾的体积， $\\mathtt{m L}$ $\\boldsymbol{v}$ 样品滴定消耗氢氧化钾的体积， $\\mathrm{\\mL}$ C 氢氧化钾的浓度， $\\scriptstyle{\\mathrm{mol/L}}$ $m$ 1 样品质量，g。  \n\n附表2-3样品称取量的范围   \n\n\n<html><body><table><tr><td>预计羟值</td><td>样品量/g</td><td>预计羟值</td><td>样品量/g</td></tr><tr><td>390</td><td>1.1</td><td>165</td><td>2.7</td></tr><tr><td>， 210</td><td>2.1</td><td>45</td><td>7.0</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 685,
+        "chunk": "# 2.醋酐吡啶法  \n\n（1）试剂  \n\n①乙酰化试剂称取4.0g对甲苯磺酸于100mL醋酸乙酯（分析纯）中，搅拌至溶解。在搅拌下慢慢加入33mL醋酐（分析纯)，使最终取此液5mL消耗氢氧化钾滴定液$\\scriptstyle(0,5{\\mathrm{mol/L}})$ 。 $40\\mathrm{\\sim}50\\mathrm{mL}$ 。  \n\n$\\textcircled{2}$ 酚酞指示剂。  \n$\\textcircled{3}$ 吡啶与水混合液 $(3:1)$ 。  \n$\\textcircled{4}$ 甲苯/乙醇（1/2）混合液。  \n$\\textcircled{5}0.5\\mathrm{mol/L}$ 氢氧化钾乙醇溶液。  \n$\\textcircled{6}$ 醋酸乙酯（分析纯)。  \n\n（2）测试方法准确称取样品（附表2-3)，加入5mL醋酸乙酯到样品瓶中溶解样品，如需要可稍加热，然后准确加入（5.00士0.02）mL乙酰化试剂，在50℃水浴上加热回流20min。反应完毕后加人2mL水，用力振摇，再加入10mL吡啶与水（3：1）混合液，振摇，室温下放置10min，然后视样品溶液的浑浊情况，加人一定量的甲苯/丁醇（1/2）混合液，再加数滴酚肽指示剂，用0.5mol/L氢氧化钾乙醇标准溶液滴定至溶液呈粉红色，即为终点。  \n\n计算公式同苯酐吡啶法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 686,
+        "chunk": "# 四、环氧值  \n\n环氧值是表征环氧树脂中环氧基含量的物理量，它有多种表示方式：  \n\n（1）环氧值A表示100g环氧树脂中含有环氧基的物质的量，我国多采用此表示法；（2）环氧指数B表示每千克环氧树脂中含有环氧基的物质的量，汽巴公司用此表示法；（3）环氧当量C表示含有1mol环氧基的树脂质量，壳牌、道化学采用此种表示法。  \n\n三种表示法之间关系为：  \n\n环氧当量 ${\\tt=}1000\\$ /环氧指数 即 ${C=}1000/B$ 环氧当量 ${\\tt\\displaystyle-100}$ /环氧值 即 $c{=}100/A$ 环氧指数 ${\\tt\\left.\\sum\\tt_{\\alpha}\\right.}=10\\$ /环氧值 即 $\\scriptstyle{B=10/A}$ 。",
+        "category": " Introduction"
+    },
+    {
+        "id": 687,
+        "chunk": "# 1．高氯酸法  \n\n这是国际通用的分析方法，它适用于各种环氧树脂。  \n\n本法通过高氯酸与溴化四乙基铵反应，产生的溴化氢与环氧基定量地反应，以结晶紫为指示剂，滴定多余的溴化氢即可测出环氧值。  \n\n（1）试剂所有试剂的配制都应在通风橱中进行，并戴防护眼镜或面罩。  \n\n① 高氯酸溶液在烧杯中依次缓慢加人250mL冰醋酸（AR)、13mL浓度为60%的高氯酸（分析纯）和50mL醋酸酐（分析纯)，混匀后转移至1L的容量瓶中，以冰醋酸稀释至刻度，充分混合后静置8h以上，使醋酸酐与水充分反应。  \n\n高氯酸溶液的标定，有两种方法。  \n\na.邻苯二甲酸氢钾标定法准确称取约0.4g邻苯二甲酸氢钾（基准试剂)，加人50mL冰醋酸中，微热使其溶解，加人6～8滴结晶紫指示剂，在磁力搅拌下以高氯酸溶液滴定（滴定管应是底部进液贮瓶式，顶端装有干燥管）至由蓝变为绿色（持续2min不褪色)，高氯酸浓度由下式计算。  \n\n$$\nc(\\mathrm{HClO}_{4})=\\frac{1000m}{204.2V}\n$$  \n\n式中 $c(\\mathrm{{HClO_{4}}}$ )——高氯酸浓度，mol/L;$\\mathbf{\\nabla}_{m}$ ——称取邻苯二甲酸氢钾质量，g;$\\pmb{V}.$ —滴定用去的高氯酸溶液体积， $\\mathrm{\\mL}$ 。  \n\nb.双酚A二缩水甘油醚标定法准确称取约 $0.4\\mathbf{g}$ 双酚A二缩水甘油醚(分析纯)，溶入$_{10\\mathrm{mL}}$ 二氯甲烷中，在磁力搅拌下使之溶解，加入 $10\\mathrm{mL}$ 溴化四乙基铵试剂，再加人 $6{\\sim}8$ 滴结晶紫指示剂，以高氯酸溶液滴定至由蓝色变为绿色，高氯酸浓度由下式计算。  \n\n$$\nc(\\mathrm{HClO}_{4}){=}\\frac{1000m}{E V}\n$$  \n\n式中 $\\mathbf{\\nabla}_{m}$ -双酚A二缩水甘油醚质量，g;$\\scriptstyle{E}$ —标样的环氧当量，正常值为170.6；$\\boldsymbol{v}$ ——滴定用去的高氯酸溶液体积，mL。  \n\n开始时高氯酸溶液用方法a.标定，以后每周用方法b.或方法a.至少标定1次。  \n\n$\\textcircled{2}$ 二氯甲烷(分析纯);  \n$\\textcircled{3}$ 溴化四乙基铵（分析纯)；  \n$\\textcircled{4}$ 结晶紫指示剂。  \n\n（2）测试方法按估计样品的环氧当量（附表2-4）准确称取一定量的环氧树脂至三角烧瓶中，加入 $_{10\\mathrm{\\sim}15\\mathrm{mL}}$ 二氯甲烷，在磁力搅拌下加入 $100\\mathrm{mL}$ 溴化四乙基铵及 $6{\\sim}8$ 滴结晶紫指示剂，用高氯酸滴定，颜色由蓝变绿并持续 $2\\mathrm{min}$ 为终点。  \n\n附表2-4样品称取量的范围   \n\n\n<html><body><table><tr><td>环氧当量</td><td>样品量/g</td><td>环氧当量</td><td>样品量/g</td></tr><tr><td>170~375</td><td>0.4</td><td>1000~1500</td><td>1.3</td></tr><tr><td>375~600</td><td>0.6</td><td>1500~2000</td><td>1.8</td></tr><tr><td>600~1000</td><td>0.8</td><td>2000~2500</td><td>2.3</td></tr></table></body></html>  \n\n环氧当量 $\\scriptstyle{E}$ 由下列计算。  \n\n$$\n\\scriptstyle{E={\\frac{1000m}{V c}}}\n$$  \n\n式中E—环氧当量， $\\mathbf{g}/\\mathrm{mol}$ $\\mathbf{\\nabla}_{m}$ -环氧树脂样品质量，g;$\\boldsymbol{v}$ —滴定用去的高氯酸溶液体积，mL;C -高氯酸溶液的浓度， $\\scriptstyle{\\mathrm{~mol/L~}}$ 。  \n\n本方法由美国道化学公司提供，在由同一分析人员操作时，两次分析结果误差应小于$0.25\\%$ ；由不同实验室的不同人员操作，两次分析结果误差应小于 $0.5\\%$ D",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 688,
+        "chunk": "# 2.盐酸丙酮法  \n\n我国多用此法，该法适用于分子量在1500以下的环氧树脂。  \n\n本法利用盐酸可与环氧基定量发生加成反应，多余的盐酸由氢氧化钠滴定而测出环氧值。 修  \n\n（1）试剂  \n\n$\\textcircled{1}$ 盐酸丙酮溶液：1mL相对密度1.19的盐酸溶于 $40\\mathrm{mL}$ 丙酮中，混匀，现用现配。  \n\n$\\textcircled{2}$ 甲基红指示剂。  \n\n$\\textcircled{3}0.1\\mathrm{mol/L}$ 标准氢氧化钠溶液。  \n\n（2）测试方法按附表2-5精确称取0.5～1.5g树脂，放人具塞三角烧瓶中，用移液管加入20mL盐酸丙酮溶液，加塞摇荡使树脂完全溶解后，在阴凉处（15℃左右）放置1h，加甲基红指示剂3滴，用浓度约为0.lmol/L的氢氧化钠标准溶液滴定到颜色由红变黄为终点。同样操作，不加树脂，做空白试验。  \n\n附表2-5 取样范围   \n\n\n<html><body><table><tr><td>环氧树脂型号</td><td>样品量/g</td></tr><tr><td>E-51,E-44,E-42</td><td>0.5</td></tr><tr><td>E-20</td><td>1.0</td></tr><tr><td>E-12</td><td>1.5</td></tr></table></body></html>  \n\n按下式计算树脂的环氧值。  \n\n$$\nE V{=}\\frac{(V_{1}{-}V_{2})c}{10m}\n$$  \n\n式中 EV——环氧值；  \n\nVi——空白试验消耗氢氧化钠溶液的体积，mL;$\\boldsymbol{V}_{2}$ 样品消耗氢氧化钠溶液的体积， $\\mathrm{\\mL}$ .C 氢氧化钠标准溶液浓度， $\\scriptstyle{\\mathrm{mol/L}}$ $m$ 样品质量，g。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 689,
+        "chunk": "# 3.盐酸吡啶法  \n\n我国多用此法，该法适用于分子量在1500以上的环氧树脂。  \n\n本法利用盐酸与吡啶的加成产物可与环氧基定量发生开环反应，多余的盐酸由氢氧化钠滴定而测定环氧值。  \n\n（1）试剂  \n\n① 盐酸吡啶溶液：17mL相对密度1.19的盐酸加人984mL吡啶中混匀。  \n\n$\\textcircled{2}$ 酚酞指示剂。  \n\n$\\textcircled{3}0.1\\mathrm{mol/L}$ 标准氢氧化钠溶液。  \n\n$\\textcircled{4}$ 丙酮 (分析纯)。  \n\n（2）测试方法精确称取样品5g左右，放人250mL标准磨口的三角烧瓶中，用移液管加人25mL盐酸吡啶溶液，烧瓶装上磨口回流冷凝管，缓慢加热，回流40min后，冷却至室温，用20mL丙酮冲洗冷凝器，然后取下烧瓶加酚指示剂3滴，用氢氧化钠标准溶液滴定至显微红色，并在30s内不消失为终点。同样操作，不加树脂做空白试验。  \n\n树脂样品环氧值计算方法同盐酸丙酮法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 690,
+        "chunk": "# 五、异氰酸酯基  \n\n本法利用异氰酸酯基可与二丁胺定量反应生成脲，过量的胺以盐酸滴定而测定异氰酸酯基含量。  \n\n$$\n\\mathrm{RNCO+HN(C_{4}H_{9})_{2}\\qquad}\\mathrm{\\eRNHCON(C_{4}H_{9})_{2}}\n$$  \n\n干扰物质有光气、氨基甲酰氯、氯化氢以及某些劣质二异氰酸酯中所含少量焦油、酸或碱性杂质。在提纯合格的二异氰酸酯产品中，干扰物质含量极微，对分析的影响可忽略。 ，  \n\n1.试剂  \n\n$\\textcircled{1}$ 溴甲酚绿 $(0.1\\%$ ： $0.100{\\bf g}$ 溴甲酚绿指示剂加人1.5mL0.1mol/L的氢氧化钠溶液中，溶解后用水稀释至 $100\\mathrm{mL}$ 。  \n\n$\\textcircled{2}$ 二丁胺溶液（ $258\\mathbf{g}/\\mathrm{L})$ ：将 $258g$ 新蒸无水二丁胺，用无水甲苯稀释至1L，浓度为$\\scriptstyle2{\\mathrm{mol/L}}$ ，装入棕色瓶中。  \n\n$\\textcircled{3}$ 盐酸溶液：1mol/L。  \n\n$\\textcircled{4}$ 无水甲苯：经干燥处理。  \n\n$\\textcircled{5}$ 乙醇(分析纯)。  \n\n2.测试方法  \n\n（1）异氰酸酯的含量测定加 $40\\mathrm{mL}$ 无水甲苯于干燥、洁净的 $500\\mathrm{mL}$ 碘瓶内，用移液管加人 ${\\mathsf{50m L}}$ 二丁胺溶液，加人 ${\\mathsf{6}}.{\\mathsf{5}}{\\sim}7.0\\mathbf{g}$ 甲苯二异氰酸酯（TDI）样品到碘瓶内（精确到 $\\boldsymbol{0.0018})$ ，小心摇荡碘瓶，以 $10\\mathrm{mL}$ 无水甲苯洗涤瓶口，轻塞瓶口，在常温下放置 $15\\mathrm{min}$ ，待反应完毕后，加 $225\\mathrm{mL}$ 乙醇和 $\\boldsymbol{0.8\\mathrm{mL}}$ 溴甲酚绿指示剂，以浓度为$\\scriptstyle{1\\mathrm{mol/L}}$ 的盐酸溶液滴定至颜色从蓝变黄，且保持15s即为终点。用同样方法，不加试样做空白试验。  \n\n用下式计算异氰酸酯基含量：  \n\n式中 $\\boldsymbol{V_{\\circ}}$ ——空白试验所用盐酸的体积，mL；$\\boldsymbol{v}$ ———滴定样品耗用盐酸的体积，mL;$\\scriptstyle{E}$ ———TDI当量87.08，如测其他异氰酸酯，则换以相应的当量；$\\mathbf{\\nabla}_{m}$ -样品质量，g;$N\\cdot$ —盐酸准确浓度， $\\scriptstyle{\\mathtt{m o l}}/{\\mathtt{L}}$ 。  \n\n误差范围：同一分析者的误差应在 $0.4\\%$ 以内，不同实验室分析误差应在 $0.8\\%$ 以内。  \n\n（2）低聚物中异氰酸酯基（—NCO）含量的测定准确称取 $_{1g}$ 低聚物样品加入 $25\\mathrm{mL}$ 碘瓶中，加入无水甲苯 $25\\mathrm{mL}$ ，加塞瓶溶解（必要时可加热溶解)，用移液管加入 $0.1\\mathrm{mol/L}$ 的二丁胺溶液 $25\\mathrm{mL}$ ，加塞摇匀， $15\\mathrm{{min}}$ 后加人异丙醇 $_{100\\mathrm{mL}}$ ，溴甲酚绿指示剂 $4{\\sim}6$ 滴，用盐酸溶液滴定至黄色终点。同时做空白试验。 A  \n\n按下式计算异氰酸酯基（—NCO）含量：  \n\n$$\n-\\mathrm{NCO}(\\%)=\\frac{(V_{0}-V)N\\times4.2}{m}\n$$  \n\n式中 $\\boldsymbol{V_{\\circ}}$ 空白试验所用盐酸体积， $\\mathtt{m L}$ $\\boldsymbol{v}$ 滴定样品所用盐酸体积，mL；$N$ 盐酸准确浓度， $\\scriptstyle{\\mathrm{~mol/L~}}$ $\\mathbf{\\nabla}_{m}$ 样品质量，g。  \n\n误差范围：同一分析者的误差应不超过 $0.11\\%$ ；不同实验室分析误差应不超过 $0.40\\%$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 691,
+        "chunk": "# 附录3 涂料性能检测方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 692,
+        "chunk": "# 一、漆膜一般制备法（GB1727—1979)  \n\n本标准适用于测定漆膜一般性能的样板制备。将试样均匀涂于各种底材上制备漆膜。  \n\n1.材料和仪器设备  \n\n（1）马口铁板：25mm×120mm×(0.2～0.3)mm，50mm×120mm×(0.2～0.3)mm,$70\\mathrm{{mm}}\\times160\\mathrm{{mm}}\\times(0.2\\sim0,3)\\mathrm{{mm}}$ 中  \n\n(2）玻璃板： $90\\mathrm{{mm}}\\times120\\mathrm{{mm}}\\times(2\\sim3)\\mathrm{{mm}}$ 。  \n\n(3）钢板：50mm×120mm×(0.45～0.55)mm,65mm×150mm×(0.45\\~0.55)mm。  \n\n（4）铝板：Ly12 $50\\mathrm{mm}\\times120\\mathrm{mm}\\times(1{\\sim}2)\\mathrm{mm}$ a  \n\n（5）水泥石棉板。  \n\n（6）钢棒：直径（13士2）mm，长120mm，一端为圆滑面；另一端有孔或环。  \n\n(7） $0^{\\sharp}$ 砂布或 $200^{\\sharp}$ 水砂纸。  \n\n（8）漆刷：宽 $25\\sim35\\mathrm{mm}$  \n\n（9）喷枪：喷嘴内径 $0.75{\\sim}2\\mathrm{mm}$ 。  \n\n（10）腻子刮涂器：如附图3-1所示，由模型板与刮刀组成。  \n\n（11）涂-4黏度计。  \n\n（12）杠杆千分尺或测厚计：精确度为 $2\\mu\\mathrm{m}$ 。  \n\n（13）秒表：分度 $0.2{\\mathbf s}$ 。  \n\n（14）鼓风恒温烘箱。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 693,
+        "chunk": "# 2.底板的表面处理  \n\n（1）马口铁板或钢板均先用 $0^{\\sharp}$ 砂布或$200^{\\sharp}$ 水砂纸用打板机或手工沿纵向往复打磨除锈，去掉镀锡层。以溶剂（ $200^{\\#}$ 溶剂油或二甲苯）洗净，擦干使用。  \n\n（2）玻璃板用热肥皂水洗涤，清水冲净、擦干。涂漆前需用脱脂棉蘸溶剂擦净，晾干使用。  \n\n（3）铝板用溶剂洗净，擦干使用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 694,
+        "chunk": "# 3.制板方法  \n\n涂漆前将试样搅拌均匀，然后按产品标准规定选用下列方法制备涂膜。  \n\n![](images/a216a01582173a53a5e7eefab28008f91b3b1d1283e21fcf6cb17ccff6699b63.jpg)  \n附图3-1 腻子刮涂器  \n\n1一底座 $(215\\mathrm{mm}\\times125\\mathrm{mm}\\times15\\mathrm{mm})$ ；2一模框（内框 $145\\mathrm{mm}\\times$ $60\\mathrm{mm}\\times1\\mathrm{mm}$ ， $145\\mathrm{mm}{\\times}60\\mathrm{mm}{\\times}0.7\\mathrm{mm}$ 、 $145\\mathrm{mm}\\times60\\mathrm{mm}\\times$ $0.5\\mathrm{mm})$ ；3一刮刀框（内框 $155\\mathrm{mm}\\times70\\mathrm{mm}\\times2\\mathrm{mm})$ \\* 4一楔形卡；5一刮刀（刮刀宽 $70\\mathrm{{mm}}$ +  \n\n（1）刷涂法将试样稀释至适当黏度或按产品标准规定的黏度，用漆刷在规定的底板上快速均匀地沿纵横方向涂刷，使其成一层均匀的漆膜，不允许有空白或溢流现象，涂刷好的样板，平放于恒温恒湿处或鼓风恒温烘箱中干燥。  \n\n（2）喷涂法将试样稀释至工作黏度［在（25±1)℃条件下，以涂-4 黏度计测定，油基漆为20～30s，挥发性漆为15～25s]，然后在规定的底板上喷涂成均匀的漆膜，不得有空白或溢流现象。喷涂时，喷枪与被涂面之间的距离不小于 $200\\mathbf{mm}$ ，喷涂方向要与被涂面成适当的角度，空气压力为 $0.196{\\sim}0.392\\mathbf{M}\\mathbf{Pa}$ （空气应过滤去油、水及污物）喷枪移动速度要均匀。喷涂好的样板平放于恒温恒湿处或鼓风恒温烘箱中干燥。  \n\n(3）浸涂法将试样稀释至适当的黏度(使漆膜厚度符合产品标准的规定)，然后以缓慢均匀的速度将底材垂直浸入漆液中，停留30s后，以同样速度从漆中取出，放在洁净处滴干 $10\\mathrm{\\sim}30\\mathrm{min}$ 。滴干的样板或钢棒垂直悬挂于恒温恒湿处或鼓风恒温烘箱中干燥（干燥条件按产品标准规定)。将样板或钢棒倒转 ${180}^{\\circ}$ ，按第1次浸漆的方法进行第2次浸漆，滴干$10\\mathrm{\\sim}30\\mathrm{min}$ 后，按产品标准规定的条件干燥。浸漆的次数及干后漆膜厚度均按产品标准规定。制备同一产品的漆膜需采用相同的干燥条件。  \n\n（4）刮涂法将底板放于腻子刮涂器底座上，把模框及刮刀框套在其上并卡紧。再用金属刮刀将腻子均匀地刮涂在底板上使成均匀平整的腻子涂膜。取下腻子样板平放于恒温恒湿处或鼓风恒温烘箱中干燥（干燥条件按产品标准规定)。  \n\n上述制备的漆膜，在进行漆膜一般性能测试前的干燥时间规定如下：自然干燥的漆，在恒温恒湿条件下干燥 $48\\mathrm{h}$ 测试(挥发性漆干燥24h)；烘干漆按产品标准规定的时间烘干取出后在恒温恒湿条件下放置 $0.5\\mathord{\\sim}1\\mathrm{h}$ 测试。．  \n\n恒温恒湿是指温度（ $(25\\pm1)^{\\circ}\\mathrm{C}$ ，相对湿度 $(65\\pm5)\\%$ 。  \n\n底板表面处理和处理过程中，不允许手指直接接触样板表面。  \n\n4.各种涂膜干燥后涂膜厚度规定见附表3-1和附表3-2。  \n\n附表3-1各种涂膜干燥后涂膜厚度规定（一）  \n\n\n<html><body><table><tr><td>名称</td><td>清油、丙烯 酸清漆</td><td>酯胶、酚醛、 醇酸清漆</td><td>沥青、环氧、氨基、 硝基、过氯乙烯、 有机硅耐热清漆</td><td>磁漆、底漆、 烘漆</td><td>丙烯酸磁 漆、底漆</td><td>乙烯磷化 底漆</td><td>厚漆</td><td>腻子</td></tr><tr><td>厚度/μm</td><td>13±3</td><td>15±3</td><td>20±3</td><td>23±3</td><td>18±3</td><td>10±3</td><td>35±5</td><td>500±20</td></tr></table></body></html>  \n\n附表3-2各种涂膜干燥后涂膜厚度规定（二）  \n\n\n<html><body><table><tr><td>名称</td><td>防腐漆单一漆膜的耐酸、耐碱性及防锈漆 耐盐水性、耐磨性（均涂两道）</td><td>单一漆膜的 耐湿热性</td><td>防腐漆配套漆 膜的耐酸、耐碱性</td><td>磨光性</td></tr><tr><td>厚度/μm</td><td>45±5</td><td>23±3</td><td>70±10</td><td>30±5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 695,
+        "chunk": "# 二、漆膜颜色及外观测定法（GB1729—1979）  \n\n本标准适用于漆膜颜色及外观的测定。采用观察漆膜颜色及外观与标准色板、标准样品进行比较的方法评定结果。  \n\n1.材料和仪器设备  \n\n（1）标准色板。  \n（2）标准样品。  \n（3）马口铁板： $50\\mathrm{mm}\\times120\\mathrm{mm}\\times(0.2\\sim0.3)\\mathrm{mm},$ 。  \n\n2.测定方法  \n\n（1）标准样品法按《漆膜一般制备法》（GB1727—1979）将测定样品与标准样品，分别在马口铁板上制备漆膜。待漆膜实干后，将两板重叠 $1/4$ 面积，在天然散射光线下检查，眼睛与样板距离 $30\\mathrm{cm}$ 左右，约成 $120^{\\circ}{\\sim}140^{\\circ}$ ，根据产品标准检查颜色和外观，颜色应符合技术允差范围；外观应平整、光滑或符合产品标准规定。  \n\n（2）标准色板法按《漆膜一般制备法》（GB1727—1979）将测定样品在马口铁上制备漆膜。待漆膜实干后，将标准色板与待测色板重叠1/4面积，在天然散射光线下检查，眼晴与样板距离30cm左右，约成120°～140°，其颜色若在两块标准色板之间或与一块标准色板比较接近，即认为符合技术允差范围；外观检查按标准样品法规定进行。  \n\n注：标准色板、标准样品保存有效期为一年，或由制造厂和用户双方商定。  \n\n三、色漆和清漆漆膜厚度的测定（GB/T13452.2—1992，等效ISO2808—1974)  \n\n本标准规定了在一定条件下色漆和有关材料漆膜厚度的测量方法。  \n\n1.千分尺法测量干膜厚度（1）目的和使用范围  \n\n① 本方法规定了涂漆物体或涂漆试板上干膜厚度的测量方法，其精确度为士2um。  \n\n② 测量应在漆膜干燥到千分尺的卡头在与漆膜紧密接触时，在漆膜上不产生任何可见玉痕的状态以后进行。  \n\n③本方法适用于金属板或类似材料那种平整表面，也可用于圆棒涂层的测量。  \n\n(2）仪器千分尺：精确度为 $2\\mu\\mathrm{m}$ d  \n\n（3）操作步骤  \n\n① 选取若干千分尺能伸进的测试部位。该部位应表面平整，离任何漆膜的边缘不得小于20mm，其间隔约为50mm。在每一测试部位轻轻画一个直径约10mm的圆圈记号，其旁加注明显的号码。  \n\n② 将千分尺的固定卡头与试板底部水平接触，并且接触漆膜的第一个测试部位，轻轻捻动活动卡头到有顶住的感觉。读取千分尺上的读数，在测试记录单上记上读数和部位的有关编号。放开千分尺，在其余的每个测试部位重复以上步骤。  \n\n③用适当的溶剂或脱漆剂除去试板上每个测试部位圆圈内漆膜。  \n\n④在每个测试部位重复②步骤，测出底材厚度。  \n\n（4）计算  \n\n$\\textcircled{1}$ ① 将每个编号的第一次读数减去第二次读数来计算每个测试部位的漆膜厚度。  \n\n$\\textcircled{2}$ ② 根据各漆膜厚度计算试板漆膜的平均值，其结果应四舍五入至最接近2μm的倍数。  \n\n2.在磁性金属底材上漆膜厚度的测量  \n\n（1）原理该类仪器运转原理是磁体与磁性底材之间间隙的变化引起磁通量的改变。对涂漆底材来说，是依据磁通量随漆膜的非磁性层在磁体和底材之间的厚度而变化。磁体既可是电磁体也可是永久磁体。  \n\n（2）仪器装置  \n\n①电磁体该类仪器要求供有电力，并装有供给电磁头以稳定电流的装置。  \n\n磁头应置于与受试漆膜下金属底材相似的未涂漆金属表面上读取读数。然后在涂漆表面上重复操作读取读数。仪器上刻度经标定后，就可通过两次读数之间的差别指示漆膜厚度。 N  \n\n② 永久磁体该仪器有置于涂漆表面呈球形接触体状态的单极或多极永久磁体。将触头放置在与试板性质相似的未涂漆底材上，调节标盘读数至零。该仪器的校准通常是以仪器所提供的已知厚度的非磁性垫片来进行的，将其置于参照底材上并借控制旋钮调整读数以达到标准膜的厚度。校准后，将仪器置于涂漆表面上并注意标度盘上的读数，为避免底材上的任何磁性，仪器旋转 ${180}^{\\circ}$ 并在膜的同一部位取第二次读数，如果第二次读数与第一次不同，取平均值。以同样方式取几次读数，以获得涂漆物体全范围上的代表性结果。  \n\n$\\textcircled{3}$ 磁吸力脱离仪该类仪器以克服永久磁体与磁性底材之间磁引力所需的力来测量漆膜厚度的。该引力随磁体与底材间非磁性漆膜的厚度而改变，并且以连接在永久磁体上的弹簧圈张力所施与的力来测量。  \n\n（3）应遵守的预防措施仪器磁件不应置放在离测试件的任何边小于 $25\\mathrm{mm}$ 或者会使仪器的磁场强度不均一的地方。仪器应经常与标准垫片和参照表面校准，以确认标定仍是有效的。另外可以将垫片放置在测试表面上进行校准，以校对仪器在已知垫片厚度所得的相应读数增长是否在仪器所称的精确度限度以内。  \n\n试样在机械处理和加工时，很容易磁化，这将影响所得读数的准确性。为此，作为参照表面的对照试样，应在组成和测量前的处理等方面尽可能与试样相似。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 696,
+        "chunk": "# 3.在非磁性金属底材上的测量  \n\n（1）原理以涡流原理进行测量的仪器，其原理为感应涡流的大小是随仪器探头线圈与基础金属底材间漆膜厚度的大小而变化。通过感应涡流的变化可测出漆膜厚度。  \n\n该测量仪器可直接读出漆膜厚度。因为金属颜料有涡流感应，不能测量含金属颜料的漆膜。  \n\n（2）操作步骤将仪器放于相似于受试物体的参照表面上，小心地调至零位，然后用仪器附带的标准片校准。  \n\n放置仪器探头于涂漆件上，读取读数。在涂漆的部件上，以相似的方式，读取几个数据，以得到代表性结果。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 697,
+        "chunk": "# 4.湿膜厚度的测量（轮规）  \n\n（1）目的和使用范围用轮规测定湿漆膜厚度的方法，在施工后立即测量其厚度，并对应参照1中的有关步骤有可能估计出干膜的近似厚度。本法适用于适当形状的刚性底材，既可用于实验室又可用于生产控制。  \n\n(2）轮规  \n\n$\\textcircled{1}$ 仪器结构测量仪由三个等间隔的轮同轴组成，中间的一个略小于外轮，并偏心。当此仪器在湿膜上滚动时，能从中间轮边缘刚刚触及湿漆膜表面的位置，对应于外轮刻上的标尺，读出湿膜厚度。  \n\n$\\textcircled{2}$ 操作步骤色漆施工后立即放轮规仪于漆膜上，以使两个外轮的最大刻度处与底材接触，沿表面滚动轮子 ${180}^{\\circ}$ ，检查中间轮缘与湿膜表面首先接触的位置，标定的尺度将指出这一点的湿膜厚度。 A  \n\n在不同测试处以相似方式至少再取两个读数，以得到涂漆范围内的代表性结果。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 698,
+        "chunk": "# 四、涂料流平性测定法（GB1750—1979）  \n\n本标准适用于涂料流平性的测定，分为刷涂法和喷涂法。将涂料刷涂或喷涂于表面平整的底板上，以刷纹消失和形成平滑漆膜表面所需时间（s）表示。  \n\n1．材料和仪器设备  \n\n（1）马口铁板：表面平整 $50\\mathrm{{mm}{\\times}120\\mathrm{{mm}{\\times}(0.2{\\sim}0.3)}\\ \\mathrm{{mm}_{\\circ}}}$ (2）漆刷：宽 $25\\sim35\\mathrm{mm}$ 。  \n（3）喷枪。  \n（4）秒表。  \n\n2.测定方法  \n\n（1）刷涂法按《漆膜一般制备法》（GB1729—1979）中的刷涂法，在恒温恒湿的条件下，用漆刷在马口铁板上制备漆膜。刷涂时，应迅速先纵向后横向地涂刷，涂刷时间不多于2～3min。然后在样板中部纵向地由一边到另一边涂刷一道（有刷痕而不露底)。自刷子离开样板的同时，开动秒表，测定刷子划过的刷痕消失和形成完全平滑漆膜表面所需的时间，合格与否按产品标准规定。  \n\n（2）喷涂法按《漆膜—般制备法》（GB1727—1979）中的喷涂法，在马口铁板表面上制备漆膜，将样板置于恒温恒湿的条件下，观察涂漆表面达到均匀、光滑、无皱（无橘皮或鹅皮）状态所需的时间，合格与否按产品标准规定。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 699,
+        "chunk": "# 五、涂料黏度测定法（GB1723—1979）  \n\n本标准适用于涂料黏度的测定，采用涂-1、涂-4、落球黏度计，以“s”表示。涂-1、涂-4 黏度计测定的条件黏度是：一定量的试样，在一定的温度下从规定直径的孔所流出的时间。落球黏度计测定的条件黏度是：在一定的温度下，一定规格的钢球通过盛有试样的玻璃管上、下两刻度线所需的时间。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 700,
+        "chunk": "# 1.材料和仪器设备  \n\n（1）水银温度计：温度范围0～50℃，分度为0.1℃。（2）秒表：分度为0.2s。（3）永久磁铁。（4）水平仪。（5）承受瓶：50mL量杯、150mL糖瓷杯。（6）涂-1黏度计：用于测定黏度不低于20s（以本黏度计为标准）的涂料产品，以及按产品标准规定必须加温进行测定的黏度较大的涂料产品，如附图3-2所示。  \n\n![](images/8892054fbdaf1c80f5aef0627d58e6fe57ed107c95e4728d1bd9817f83ecbc28.jpg)  \n附图3-2涂-1黏度计  \n\n![](images/3e6616b262c8fef602721c86c1cae6c1ae34aa6ddb37bd3aabd75e4068779489.jpg)  \n附图3-3涂-4黏度计  \n\n（7）涂-4黏度计：用于测定黏度在150s以下（以本黏度计为标准）的涂料产品，如附图3-3所示。  \n\n（8）落球黏度计：用于测定黏度较高的透明液体的涂料产品，如附图3-4所示。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 701,
+        "chunk": "# 2.测定方法  \n\n（1）涂-1黏度计法每次测定前须用纱布蘸溶剂将黏度计内部擦拭干净，在空气中干燥或用冷风吹干，对光观察黏度计漏嘴应清洁，然后将黏度计置于水浴套内，插入塞棒。将试样搅拌均匀，有结皮和颗粒时用不少于567孔/cm²金属筛过滤，调整温度至（25士1)℃，然后将试样倒人黏度计内，调节水平螺钉使液面与刻度刚好重合。为使试样中气泡逸出应静置片刻，盖上盖子并插入温度计，试样保持在（25士1)℃。在黏度计漏嘴下面放置一个50mL量杯，当试样温度符合要求后，迅速将塞棒提起，试样从漏嘴流出并滴人杯底时，立即开动秒表。当杯内试样达到${\\mathsf{50m L}}$ 刻度线时，立即停止秒表，试样流人杯内 $\\scriptstyle50\\mathrm{mL}$ 所需时间(s)，即为试样的条件黏度，两次测定值之差不应大于平均值的 $3\\%$ 。  \n\n![](images/6a26c3faad61f5445dd2b2bc83f4c9c8885589792bb9819af1149874c2c29298.jpg)  \n附图3-4落球黏度计  \n\n（2）涂-4 黏度计法黏度计的清洁处理及试样的准备同涂-1黏度计法所述，调整水平螺钉，使黏度计处于水平位置，在黏度计漏嘴下面放置150mL的塘瓷杯，用于堵住漏嘴孔，将试样倒满黏度计中，用玻璃棒将气泡和多余的试样刮人凹槽，然后松开手指使试样流出，同时立即开动秒表，当试样流丝中断时停止秒表，试样从黏度计流出的全部时间（s)，即为试样的条件黏度。两次测定值之差不应大于平均值 $3\\%$ 。测定时试样温度为 $(25\\pm1)^{\\circ}\\mathrm{C}$ 。  \n\n（3）落球黏度计法将透明的试样倒人管中，使试样高于刻度线4cm，钢球也一同放人，塞上带铁钉的软木塞，用永久磁铁放置在带铁钉的软木塞上，将管子颠倒使铁钉吸住钢球，再翻转过来，固定在架上，并用铅锤调节使其垂直，然后将永久磁铁拿走，使钢球自由落下，当钢球通过上刻度线时立即开动秒表，至钢球落到下刻度线时停止秒表，记下钢球通过两刻度线的时间（s)，即为试样的条件黏度。两次测定值之差不应大于平均值的3%，测定时试样温度（ $(25\\pm1)\\mathsf{C}$ 。  \n\n六、涂料细度测定法（GB1724—1979)  \n\n本标准适用于涂料细度的测定。采用刮板细度计，以 $\\ensuremath{\\omega}_{\\mu\\ensuremath{\\mathbf{m}}^{\\prime\\prime}}$ 表示。  \n\n1．仪器设备  \n\n（1）小调漆刀。  \n（2）刮板细度计，如附图3-5所示。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 702,
+        "chunk": "# 2.测定方法  \n\n细度在 $30\\mu\\mathrm{m}$ 及 $30\\mu\\mathrm{m}$ 以下时应用量程为 $50\\mu\\mathrm{m}$ 的刮板细度计， $31\\sim70\\mu\\mathrm{m}$ 时应用量程为 $100\\mu\\mathrm{m}$ 的刮板细度计， $70\\mu\\mathrm{m}$ 以上时应用量程为 $150\\mu\\mathrm{m}$ 的刮板细度计。  \n\n刮板细度计在使用前必须用溶剂仔细洗净擦干，在擦洗时应用细软指布。  \n\n将符合产品标准黏度指标的试样，用小调漆刀充分搅匀，然后在刮板细度计的沟槽最深部分，滴人试样数滴，以能充满沟槽而略有多余为宜。  \n\n以双手持刮刀(附图3-5)，横置在磨光平板上端(在试样边缘处)，使刮刀与磨光平板表面垂直接触。在3s内，将刮刀由沟槽深的部位向浅的部位拉过，使漆样充满沟槽而平板上不留有余漆。刮刀拉过后，立即（不超过5s）使视线与沟槽平面成15°～30°交角，对光观察沟槽中颗粒均匀显露处，记下读数 (精确到最小分度值)。如有个别颗粒显露于其他分度线时，则读数与相邻分度线范围内，不得超过三个颗粒。  \n\n七、涂料遮盖力测定法（GB1726—1979)  \n\n本标准适用于涂料遮盖力的测定，即把色漆均匀地涂刷在物体表面上，使其底色不再呈现的最小用漆量，以“g/m²”表示。  \n\n1.材料和仪器设备（1）漆刷：宽 $\\mathbf{25}{\\sim}35\\mathbf{mm}$ a  \n\n（2）玻璃板：100mm×100mm×（1.2～2）mm，100mm×$250\\mathrm{mm}\\times(1.2\\sim2)\\mathrm{mm}$ 0  \n\n（3）木板： $100\\mathrm{{mm}}\\times100\\mathrm{{mm}}\\times(1.5\\sim2.5)\\mathrm{{mm}}$ n（4）天平：感量为 $0.01\\mathbf{g}$ ， $\\phantom{-}0.001\\mathbf{g}$ 。  \n\n（5）刷涂法黑白格玻璃板：如附图3-6所示。  \n\n（6）喷涂法黑白格木板：如附图3-7所示。  \n\n（7）木制暗箱：600mm×500mm×400mm，如附图3-8所示。  \n\n![](images/00c4b34702e029557d1e3936a1a50588790833ba754af335298e9eb55c787ac7.jpg)  \n附图3-6刷涂法黑白格玻璃板  \n\n![](images/b23a0813ae114aa20fca8cf69ab5bcc7cbfee408931d2734e1fd799576c8e484.jpg)  \n附图3-5刮板细度计 1—磨光平板；2一刮刀  \n\n![](images/edd81205e7ec85705b7cc050f10a0ef80f836608a3fd95fa082c226843073cd4.jpg)  \n附图3-7喷涂法黑白格木板  \n\n![](images/ccf4601c72439a375be4cf26efedacdab34e014bfd81ddef68a2a3ed017a0774.jpg)  \n附图3-8暗箱  \n\n1—磨砂玻璃；2—挡光板；3—电源开关；4—15W日光灯  \n\n2.测定方法（1）刷涂法  \n\n$\\textcircled{1}$ 测定步骤根据产品标准规定的黏度（如黏度稠无法涂刷，则将试样调至涂刷的黏度，但稀释剂用量在计算遮盖力时应扣除)，在感量为 $\\phantom{+}0.01\\mathbf{g}$ 天平上称出盛有涂料的杯子和漆刷的总重量。用漆刷将涂料均匀地涂刷于玻璃黑白格板上，放在暗箱内，距离磨砂玻璃片$15\\sim20\\mathrm{cm}$ ，有黑白格的一端与平面侧斜成 $30^{\\circ}\\sim45^{\\circ}$ 交角，在1支和2支日光灯下进行观察，都以刚看不见黑白格为终点。然后将盛有余漆的杯子和漆刷称重，求出黑白格板上涂料重量。涂刷时应快速均匀，不应将涂料刷在板的边缘上。  \n\n$\\textcircled{2}$ 计算方法及精确度遮盖力 $X(\\mathfrak{g}/\\mathbf{m}^{2}$ ）按下式计算（以湿漆膜计)：  \n\n$$\nX{=}\\frac{W_{1}{-}W_{2}}{S}{\\times}10^{4}{=}50(W_{1}{-}W_{2})\n$$  \n\n式中 $\\pmb{W}_{1}$ 一 -未涂刷前盛有涂料的杯子和漆刷的总重量，g;$\\pmb{W}_{2}$ —涂刷后盛有涂漆的杯子和漆刷的总重量，g;S- 黑白格板涂漆的面积， $\\mathsf{c m}^{2}$ 。  \n\n平行测定两次，结果之差不大于平均值的 $5\\%$ ，则取其平均值，否则必须重新试验。  \n\n(2）喷涂法  \n\n$\\textcircled{1}$ 测定步骤将试样调至适于喷涂的黏度，按《漆膜一般制备法》（GB1727—1979)喷涂法进行。先在感量 $\\phantom{-}0.001\\mathbf{g}$ 天平上分别称重两块 $100\\mathrm{cm}\\times100\\mathrm{cm}$ 的玻璃板，用喷枪薄薄地分层喷涂，每次喷涂后放在黑白格木板上，置于暗箱内距离磨砂玻璃片 $15\\sim20\\mathrm{cm}$ ，有黑白格的一端与平面倾斜成 $30^{\\circ}\\sim45^{\\circ}$ 交角，在1支和2支日光灯下进行观察，以都看不见黑白格为终点。然后把玻璃板背面和边缘的漆擦净，各种喷涂漆类按固体含量中规定的熔烘温度烘至恒重。  \n\n$\\textcircled{2}$ 计算方法及精确度遮盖力 $X(\\mathbf{g}/\\mathbf{m}^{2}$ ）按下式计算（以干膜计)：  \n\n$$\nX{=}\\frac{W_{2}{-}W_{1}}{S}{\\times}10^{4}{=}(W_{2}{-}W_{1}){\\times}100\\\n$$  \n\n式中 $\\pmb{W}_{1}$ ——未喷涂前玻璃板的重量，g;$\\pmb{W}_{2}$ ——喷涂漆膜恒重后的玻璃板重量，g；$s$ —玻璃板喷涂漆的面积， $\\mathrm{cm}^{2}$ 。  \n\n两次结果之差不大于平均值 $5\\%$ ，则取其平均值，否则需重新试验。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 703,
+        "chunk": "# 八、漆膜柔韧性测定法（GB1731—1979）  \n\n本标准适用于漆膜柔韧性的测定。用样板在不同直径的轴棒上弯曲而不引起漆膜破坏的最小轴棒的直径表示。  \n\n1．材料和仪器设备（1）4倍放大镜；  \n\n（2）马口铁板： $25\\mathbf{mm}\\times120\\mathbf{mm}\\times(0.2\\sim0.3)\\mathbf{mm},$ 身  \n\n（3）柔韧性测定器：如附图3-9所示，是由粗细不同的.6个钢制轴棒所组成，固定于底座上，底座可用螺钉固定在试验台边上。  \n\n轴棒尺寸如下：每个轴棒长度 $35\\mathrm{mm}$ 。  \n\n轴棒1：直径 $10\\mathrm{mm}$ 及外径 $15\\mathrm{mm}$ 套管。  \n\n![](images/3c6900690c28821536bab01992a984235c9ef4d8f966d1f1053aca03b6185355.jpg)  \n附图3-9柔韧性测定器  \n\n轴棒2：截面5mm×10mm，曲率半径为2.5mm。  \n轴棒3：截面4mm×10mm，曲率半径为2mm。  \n轴棒4：截面3mm×10mm，曲率半径为1.5mm。  \n轴棒5：截面2mm×10mm，曲率半径为1mm。  \n轴棒6：截面1mm×10mm，曲率半径为0.5mm。  \n\n2.测定方法  \n\n按《漆膜一般制备法》（GB1727—1979）在马口铁板（或按产品标准规定）上制备漆膜。待漆膜实干后，在恒温恒湿条件下，漆膜朝上，用双手将涂漆样板紧压于按产品标准规定直径的轴棒上，绕棒弯曲，弯曲后双手拇指应对称于轴棒中心线，弯曲动作必须在2～3s内完成。漆膜在弯曲后用4倍放大镜观察，如有网纹、裂纹及剥落等破坏现象，即为不合格。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 704,
+        "chunk": "# 九、漆膜耐冲击测定法（GB1732—1979）  \n\n本标准适用于漆膜耐冲击性能的测定。以重锤的重量与其落于样板上而不引起漆膜破坏的最大高度的乘积（kg·cm）表示。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 705,
+        "chunk": "# 1.材料和仪器设备  \n\n（1）马口铁板：50mm×120mm×(0.2～0.3)mm。(2）薄钢板（GB708—1965）：65mm×150mm×（0.45～0.55)$\\mathbf{m}\\mathbf{m}$ （供测腻子耐冲击性用）。（3）4倍放大镜。（4）冲击试验器（附图3-10)。（5）校正冲击试验器用的金属环及金属片规格如下。金属环：外径30mm，内径10mm，厚（3.00士0.05）mm。金属片：30mm×50mm，厚（1.00士0.05）mm。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 706,
+        "chunk": "# 2.测定方法  \n\n按《漆膜一般制备法》（GB1727—1979）在50mm×120mm×(0.2～0.3)mm的马口铁板（或按产品标准规定）上制备漆膜。待漆膜实干后，将涂漆样板漆膜朝上平放铁钻上，样板受冲击部分距边缘不少于15mm，每个冲击点的边缘相距不得少于15mm。重锤借控制装置维持在产品标准规定的高度，按压控制钮重锤即自由地落于冲头上。提起重锤，取出样板，用4倍放大镜观察，判断漆膜有无裂纹、皱纹及剥落现象。试验应在恒温恒湿的条件下进行。  \n\n![](images/7568e3d1b324c15379234ed48c3e42b315c372cb0397f8318228011483951c6d.jpg)  \n附图3-10冲击试验器",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 707,
+        "chunk": "# 十、漆膜耐磨性测定法  \n\n本标准适用于漆膜耐磨性能的测定。采用漆膜耐磨仪，在一定的负载下经规定的磨转次数后，以漆膜的失重g表示。  \n\n1．材料和仪器设备  \n\n（1）玻璃板：厚3mm，直径100mm，中心开直径9mm的小孔。  \n（2）天平：感量为 $\\boldsymbol{0.0018}$ 。  \n（3）漆膜耐磨仪：JM-1型，如附图3-11所示。  \n（4）砂轮修整机：如附图3-12所示。  \n\n![](images/85a1408ca144571634a3434c862156ce64dc5d176dceecb603323a9667f07768.jpg)  \n附图3-11JM-1型漆膜耐磨仪  \n\n1—底座；2—计数继电器；3—工作转盘； 4一加压轴（放载重去码）；5一吸尘风量调节盘； 6—平衡码；7一加压臂；8—橡胶砂轮； 9—吸尘嘴；10—螺帽  \n\n![](images/f0957e080afc519e8922ce6c82030b749bc1333c4d87041f7e00800d142601ad.jpg)  \n附图3-12 砂轮修整机  \n\n1-吸尘管；2—底座；3—电动机；4—罩盖； 5—橡胶砂轮；6—金刚钻磨头；7—滑块； 8一开关；9一手摇柄  \n\n（5）橡胶砂轮：JM-100、JM-120，厚 $10\\mathrm{mm}$ ，直径 $\\mathsf{50m m}$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 708,
+        "chunk": "# 2.测定方法  \n\n按《漆膜一般制备法》（GB1727—1979)，将试样刷涂或喷涂于清洁干燥的底板上。自干漆第一道干 $24\\mathrm{h}$ 后涂第二道，干燥 $48\\mathrm{h}$ 测试。挥发性漆第一道干2h后喷第二道，最后一道喷后，干燥 $\\mathsf{24h}$ 测试。  \n\n将样板固定于耐磨仪工作转盘上，加压臂上加所需的载重（加压臂自重 $250\\mathbf{g}$ 应计算在内）和经整新的橡胶砂轮，在臂的末端加上与砂轮重量相同的平衡码，轻轻放下加压臂。放下吸尘嘴，并调节至离样板 $1{\\sim}1.5\\mathrm{mm}$ 。依次开启总开关、吸尘器开关、转盘开关。把样板先磨50转，使之形成较平整的表面。关闭电源，取出样板。用毛笔轻轻抹去浮屑，称重（准确到 $_{0,001_{8})}$ a  \n\n按产品标准规定调整计数器进行试验。当达到规定耐磨转数时，即行停止。取出样板，抹去浮屑，称重，前后重量之差，即为漆膜失重。平行试验两次，每次平均值之差不大于平均值的 $7\\%$ ，结果取其算术平均值。  \n\n试验在恒温恒湿条件下进行。  \n\n每次试验橡胶砂轮必须整新。砂轮使用至直径为 $45\\mathrm{mm}$ 时停止使用。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 709,
+        "chunk": "# 十一、漆膜附着力测定法（GB1720—1979）  \n\n本标准适用于漆膜附着力的测定。漆膜对底材黏合的牢度即附着力，按圆滚线划痕范围内的漆膜完整程度评定，以级表示。  \n\n1.材料和仪器设备  \n\n（1）马口铁板： $50\\mathrm{mm}\\times100\\mathrm{mm}\\times(0.2\\sim0.3)\\mathrm{mm}.$ 。  \n（2）4倍放大镜。  \n（3）漆刷：宽 $25\\sim35\\mathrm{mm}$ 。  \n（4）附着力测定仪：如附图3-13所示。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 710,
+        "chunk": "# 2.测定方法  \n\n按《漆膜一般制备法》（GB1727—1979）在马口铁板上（或按产品标准规定的底材）制备样板3块，待漆膜实干后，于恒温恒湿的条件下测定。测前先检查附着力测定仪的针头，如不  \n\n![](images/3ea82b8b7a1c4c1861f43668b02c5f818718a020c544fba66cb1521cd4587e9b.jpg)  \n附图3-13附着力测定仪  \n\n1—荷重盘；2—升降棒；3—卡针盘；4—回转半径调整螺栓； 5—固定样板调整螺栓；6—试验台；7—半截螺帽；8—固定样 板调整螺栓；9—试验台丝杠；10—调整螺栓；11—摇柄  \n\n锐利应予更换。当发现划痕与标准回转半径不符时，应调整回转半径至5.25mm。测定时，将样板正放在试验台上，拧紧固定样板调整螺栓，向后移动升降棒，使转针的尖端接触到漆膜，如划痕未露底板，应酌加码。按顺时针方向，均匀摇动摇柄，转速以80～100r/min 为宜，圆滚线划痕标准图长为（7.5士0.5）cm。向前移动升降棒，使卡针盘提起，松开固定样板的有关螺栓，取出样板，用漆刷除去划痕上的漆屑，以4倍放大镜检查划痕并评级。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 711,
+        "chunk": "# 3.评级方法  \n\n以样板上划痕的上侧为检查目标，依次标出1、2、3、4、5、6、7七个部位。相应分为七个等级。按顺序检查各部位的漆膜完整程度，如某一部位的格子有70%以上完好，则定为该部位是完好的，否则应认为坏损。例如，部位1漆膜完好，附着力最佳，定为一级；部位1漆膜坏损而部位2完好，附着力次之，定为二级。以此类推，七级为附着力最差。结果以至少有两块样板的级别一致为准。  \n\n划痕附着力评级方法如附图3-14所示。  \n\n![](images/48164c81b52bf554e779064bbc0b48e316c05829180eaf7adf8286465eddcdb6.jpg)  \n附图3-14划痕附着力评级方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 712,
+        "chunk": "# 十二、色漆和清漆漆膜的划格试验（GB9286—1988)  \n\n本标准规定了评价色漆、清漆及有关产品的涂层性能的经验测试法。这是有关涂层对底材附着力的因素中，可采用的性能测定方法之一。然而不能把这种方法当作测定附着力本身的方法。本标准规定了一种简单的经验试验程序，当涂层按格阵图形被切割，并恰好穿透至底材时，评价色漆、清漆及有关产品的涂层从底材分离的抗性。当应用于多层涂层体系时，本方法也允许用来评价各涂层彼此抗分离的能力。  \n\n1.仪器  \n\n（1）切割刀具：可使用机械切割装置或手工切割刀具、刀口间距 $2\\mathrm{mm}\\times5$ 和 $1\\mathrm{mm}\\times10$ a（2）软毛刷。  \n\n2.测定方法  \n\n（1）制备试板试板材料应是符合GB9271规定的薄钢板、马口铁板、铝板或玻璃板，试板厚度应大于 $0.23\\mathrm{mm}$ 。此外，试验期间，试板有变形的危险时，应在试板下，提供一个硬而平的表面。并按GB6741的规定或产品标准的规定，制备样板。按GB1764 的规定测定干膜厚度（以微米计)，测厚应在划格位置附近进行。并应在温度（ $23\\pm2)^{\\circ}\\mathrm{C}$ 和相对湿度$(50\\pm5)\\%$ 环境中，放置不小于 $^{16\\mathrm{h}}$ 睿  \n\n（2）试验程序采用机械切割，应将试板紧固在试验平台上，使之完全平整。装上合格的刀具，调节刀臂的平衡。然后在刀具上部加适当重量的码，以便使刀口在切割中，正好能穿透涂层而触及底材。启动往复运动的平台，进行切割，平移至调定距离，完成切割。将平台旋转 $90^{\\circ}$ ，重复上述切割，即可获得格阵图形。  \n\n采用手工切割时，用力要均匀，速度要平稳无颤动，按机械切割方式，获得格阵图形。用软毛刷沿格阵两对角线方向，轻轻地往复各刷5次。  \n\n（3）试验的重复性至少在试板三个不同位置上完成试验，如果三个位置试验的结果用下述分级法判别为不一致时，应在另外三个位置上重复试验，同时记录全部结果。  \n\n（4）评价按附表3-3给出6级评价的分类，前三级通常能满足一般用途，并用“通过”或“不通过”来评价。特殊情况时，必须按六个级别分类评价。作为合理建议，经有关各方商定，可以利用黏胶带，对格阵部位进行撕拉，进行评价。  \n\n用正常视力查看试验涂层的切割表面，并与附表3-3中说明和附图进行对比，根据对比结果定级。  \n\n附表3-3检查结果分级表  \n\n\n<html><body><table><tr><td>分级</td><td>说 明</td><td>脱落表现(以6×6切割为例)</td></tr><tr><td>0</td><td>切割边缘完全平滑，无一格脱落</td><td></td></tr><tr><td>1</td><td>在切口交叉处涂层有少许薄片分离，但划格区受影响明显不大于5%</td><td></td></tr><tr><td>2</td><td>切口边缘或交叉处涂层脱落明显大于5%，但受影响明显不大于15%</td><td></td></tr><tr><td>3</td><td>涂层沿切割边缘部分或全部以大碎片脱落，或在格子不同部位上部分或全部剥 落，明显大于15%，但受影响明显不大于35%</td><td></td></tr><tr><td>4</td><td>涂层沿切割边缘，大碎片剥落，或一些方格部分或全部出现脱落，明显大于 35%，但受影响明显不大于65%</td><td></td></tr><tr><td>5</td><td>大于第四级的严重剥落</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 713,
+        "chunk": "# 十三、漆膜硬度测定法——摆杆阻尼试验（GB1730—1982）  \n\n本标准适用于漆膜硬度的测定。采用光电摆杆式漆膜阻尼试验仪，仪器的工作原理：表面越软接触这一表面的摆杆摆动的振幅衰减越快。漆膜硬度是以一定重量的摆置于被试漆膜上，在规定振幅中摆动衰减的次数与在玻璃板上于同样振幅中摆动衰减的次数的比值来表示。  \n\n1.仪器  \n\n（1）GD-200摆杆式漆膜阻尼试验仪，如附图3-15所示。  \n\n（2）秒表：分度为0.1s。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 714,
+        "chunk": "# 2.试板  \n\n玻璃板 $100\\mathrm{mm}\\times100\\mathrm{mm}\\times(3\\sim5)\\mathrm{mm}$ 按GB1727—1979《漆膜一般制备法》的规定进行表面处理和制备漆膜。试板的干燥按GB1727—1979规定进行，干涂层的厚度按GB1764一1979（杠杆千分尺法）测定，以$\"\\mu\\mathrm{m}^{\\prime\\prime}$ “μm”表示。测试应在温度（25士1)℃，相对湿度 $(60\\sim70)\\%$ 条件下进行。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 715,
+        "chunk": "# 3.测定方法  \n\n（1）仪器校正仪器在使用前应校正，测定其摆动周期和玻璃值。在标准玻璃板上，摆杆从6°摆动衰减到3°的玻璃值应为250s士10s(玻璃值次数应为178次士8次)，摆动周期应为（1.40士0.02）s。如果玻璃值和周期不在此范围内，应调节重锤的位置，使其符合规定。玻璃值和摆动周期的测定，应按以下步骤进行。  \n\n（2）操作步骤仪器和待测试板在测试环境条件下放置10min。调节仪器三组垫脚，使其成水平状态。用乙醚湿润的软绸布擦净支承钢球。测定接通电源，按下电源开关。核对标尺零点与摆的指针静止位置是否一致，  \n\n![](images/ddd58ce55c9ad43fe8b68b9e9a72ef60d4bb93c1f3087fc924286f57942483f8.jpg)  \n附图3-15 摆杆的形状和尺寸  \n\n如不一致则应调节。将被测试板漆膜朝上放置在试验平台上，再将钢球支点置于漆膜表面。慢慢地拨动摆杆手柄，将摆杆拨到超过6°位置，按动推钮，挡住摆杆。松开推钮，释放摆杆。此时摆杆将自由摆动，数字显示器将记录和显示6°～3°的阻尼次数。同一块试板可在三个不同位置上进行测量，记录每次测量的结果。取两次测量结果的平均值，两次结果之差不应大于平均值的 $5\\%$ 。 9（3）漆膜硬度的计算漆膜硬度 $x$ 按下式计算：  \n\n$$\n\\scriptstyle{X={\\frac{n}{n_{0}}}}\n$$  \n\n式中 $\\pmb{n}$ 1 摆杆在漆膜上从 $6^{\\circ}\\sim3^{\\circ}$ 的摆动次数；$^{n_{0}}$ 1 玻璃值，次数。  \n\n十四、涂膜硬度铅笔测定法（GB6739—1986）  \n\n本标准采用已知硬度铅笔测定有机涂膜硬度，适用于涂料的发展研究和工业生产控制。  \n\n1．材料和仪器  \n\n（1）一组中华牌高级绘图铅笔6H、5H、4H、3H、2H、H、HB、B、2B、3B、4B、5B、6B，其中6H最硬，6B最软，由 $6\\mathbf{H}{\\sim}6\\mathbf{B}$ 硬度递减。  \n\n(2）削笔刀。  \n（3）涂膜铅笔划痕硬度仪（附图3-16)。  \n\n![](images/f6b6ab2eb4f16e916b183a3bc2f96e6f17ec96c4f19be56ce81a1f6dc4502133.jpg)  \n附图3-16涂膜铅笔划痕硬度仪  \n\n(4) $400^{\\sharp}$ 砂纸。  \n\n2.测定方法  \n\n（1）试件制备按GB1727—1979《漆膜一般制备法》制备试件三块，或从涂漆件上切取具有代表性的试件三块。  \n\n（2）工具准备用削笔刀将铅笔削到露出柱形笔芯 $5\\sim6\\mathrm{{mm}}$ (切不可松动或削伤铅芯)，握住铅笔使其与 $400^{\\sharp}$ 砂纸面成 $90^{\\circ}$ ，在砂纸上不停划圈，以摩擦铅芯端面，直至获得端面平整、边缘锐利的笔端为止（边缘不得有破碎或缺口)。铅笔每使用一次后要旋转 $\\boldsymbol{180^{\\circ}}$ 再用，或重磨后再用。  \n\n（3）手工操作把涂漆试件固定于水平面上，握住已削好的铅笔，使其与涂膜成 $45^{\\circ}$ 角，用力（此力大小或使铅笔端缘破碎，或犁伤涂膜）以每秒约 $\\scriptstyle1\\ m\\ m$ 的速度向前推进（附图3-17)。从最硬的铅笔开始每级铅笔犁五道 $\\scriptstyle3\\mathbf{m}\\mathbf{m}$ 的痕，直至找出五道痕都不犁伤涂膜的铅笔为止，此铅笔硬度即代表所测涂膜的铅笔硬度。  \n\n（4）仪器试验把涂漆件置于试验仪的试件台上，涂漆面朝上。把通过试验仪去码重心的垂线调节到通过铅笔端与涂面的交点，把已削好的铅笔装入铅笔夹，使其与涂面成 $45^{\\circ}$ 角，用平衡码把铅笔上的负荷调到使铅笔刚好接触试件，拧紧止动螺钉，使铅笔端离开涂面。在磁码台上加 $(1.00\\pm0.05^{\\cdot}$ ） $\\mathbf{k}_{\\mathbf{B}}$ 的硅码，松开止动螺钉，以便铅笔端与涂面接触。摇动试台的移动摇臂，使试件与铅笔端反向移动 $3\\mathrm{mm}$ ，移动速度约 $0.5\\mathrm{mm/s}$ ，然后拧紧止动螺钉，转动铅笔180°（保证笔端面无损伤）并变换试件位置，依次犁出五道痕。用此方法从最硬的铅-笔开始测试，并相继换上低一级的铅笔，直至找出五道痕中只有一次犁伤涂膜的铅笔，以其下一级铅笔代表所测涂膜的铅笔硬度。如未犁伤涂膜，则以此级的铅笔代表所测涂膜的铅笔硬度。  \n\n![](images/df708c19d29a59a7f47836b4e30064fc8c84fbce952aaf8e58b6ffe7cd19f320.jpg)  \n附图3-17手工试验示意  \n\n试验按产品标准规定或施工要求的条件进行，仲裁试验要在温度为（23士2)℃，相对湿度（ $(50\\pm5)\\%$ 的标准条件下进行。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 716,
+        "chunk": "# 3.精密度  \n\n（1）重复性如果两个操作者在同一实验室内采用同样的铅笔和试板，用同样的方法，而得到的结果之差大于一个铅笔单位，则应予怀疑。  \n\n（2）再现性如果一些操作者在不同的实验室里，采用同样的铅笔和试板或铅笔不同而试板相同，每种方法至少测两次，所得的结果之差大于一个铅笔单位时应予怀疑。  \n\n卜五、色漆和清漆不含金属颜料的色漆漆膜之 $20^{\\circ}$ 、 ${60}^{\\circ}$ 和 $85^{\\circ}$ 镜面光泽的测定（GB 9754-1988)  \n\n本标准规定了以20°、60°、85°的几何角度测定漆膜镜面光泽的方法。60°法适用于所有色漆漆膜，但对于光泽很高的色漆或接近无光泽的色漆，20°或85°法则更为适宜。20°法对高光泽色漆可提高鉴别能力，适用于60°光泽高于70单位的色漆。85°法对低光泽色漆可提高鉴别能力，适用于60°光泽低于30单位的色漆。这些方法不适用于测定含金属颜料色漆的光泽。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 717,
+        "chunk": "# 1.仪器  \n\n（1）底材：除非另行商定，底材应是具有镜面特性的平板玻璃，厚度至少3mm，面积至少150mm×100mm。当用黑玻璃或背面及边缘是毛糙的并涂上黑漆的透明玻璃作为底材时，可以检验透明清漆。  \n\n(2）涂膜涂布器（在没有规定其他施工方法时使用)，为块状湿膜制备器。  \n\n（3）光泽计。  \n\n(4）标准板。  \n\n2.测定方法  \n\n(1）液体色漆试样的测定在（23士2)℃和相对湿度为（50士5)%条件下，使用块状湿膜制备器将 $2\\mathrm{mL}$ 色漆涂在刚脱脂的玻璃板上，以 $100\\mathrm{mm/s}$ 左右速度用恒定压力拉动涂布器，涂成平整的漆膜。试板应按产品标准规定的条件和时间进行干燥。除另有规定外，应将干燥试板在（23士2)℃，相对湿度（50士5)%条件下至少放置16h。按GB1764中所规定的适当方法测定漆膜的厚度 $(\\mu\\mathbf{m})$ 口 格  \n\n操作开始，先将仪器调整，并校准光泽计使其能正确读出高光泽工作标准板的光泽值，然后再读出低光泽工作标准板的光泽值。光泽计校准后，在试验漆膜的平行于涂布方向的不同位置取得3个读数，再用高光泽的工作标准校准仪器以确保读数没有偏差。若结果误差范围小于5个单位，则记录其平均值作为镜面光泽值。否则再进行3次测定，记录全部6个值的平均值及极限值。  \n\n（2）其他底材上漆膜的测定用本法测定光泽仅在平整性好的表面上的漆膜才有意义。因为底材的稍微弯曲或局部不平整都会严重地影响测定结果。刷痕、凸起的木纹或类似的有规则纹理的方向应该平行于仪器的入射和反射面。  \n\n按2、（1）中测定方法，在表面上不同区域或不同方向作6次测定，记录其平均值及极限值。若极限值间的误差大于10个单位或大于平均值的 $20\\%$ ，则废弃该试板。  \n\n3.精密度（仅适用于玻璃上的漆膜)  \n\n（1）重复性同一操作者在同一实验室，使用同一设备仪器，在较短的时间间隔内，采用标准的试验方法，对玻璃板上的漆膜进行测定，所得的两个平均值之间绝对误差低于一个光泽单位，可以认为有 $95\\%$ 的置信水平。  \n\n（2）再现性不同操作者在不同实验室，采用标准的试验方法，对玻璃板上的同一产品的漆膜进行测定，所得到的两个平均值之间的绝对误差低于平均值的 $5\\%$ 或一个光泽单位，可认为有 $95\\%$ 的置信水平。  \n\n某些类型的色漆，特别是半光色漆，对条件的变化及漆膜制备方法的变更是敏感的，所以由这些液体色漆产生的试验再现性比上面规定的要差些。当光泽大小的差异大于 $10\\%$ 时，漆膜制备应在不同实验室中互换进行。  \n\n十六、色漆和清漆 耐液体介质的测定（GB9274—1988）  \n\n本标准规定了色漆和清漆的漆膜（单一涂层或复合涂层）或涂漆试件耐受液体作用的测定方法，分浸泡法、吸收性介质法、点滴法三种测试方法。使用时要由测试材料的要求和涂料耐受性来定。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 718,
+        "chunk": "# 1.试件  \n\n（1）试板除非另有规定或商定，试板规定为马口铁板（ $\\mathrm{GB~2520}),\\ 50\\mathrm{mm}\\times$ $120\\mathrm{mm}\\times(0.2\\sim0.~3)\\mathrm{mm}$ ，钢板（ $_{\\mathrm{GB}~912}$ ）为普通碳素冷轧钢： $50\\mathrm{mm}\\times120\\mathrm{mm}\\times$ $(0.45\\sim0.55)\\mathrm{mm}$ ，铝板（ $\\mathbf{GB}3880\\ L\\mathbf{Y}12;$ ）为： $50\\mathrm{mm}\\times120\\mathrm{mm}\\times(1\\sim2)\\mathrm{mm}$ 。试板处理和涂漆除非另有规定或商定，应按GB9271的规定进行。通常最好试板背面涂适当的保护涂料或受试涂料，试样的边应以适当的方法封住。除非另有规定，漆膜的试件应按产品标准规定的时间和条件进行干燥，然后在恒温 $(23\\pm2)^{\\circ}\\mathrm{C}$ ，相对湿度（ $50\\pm$ $5)\\%$ 的条件下处置。处置时间按产品标准或按GB1727的规定，一般最少放置 $^{16\\mathrm{h}}$ 。漆膜厚度按GB1764测定厚度。  \n\n（2）试棒（仅适用于浸泡法）试棒一端应当磨圆，其圆弧半径接近棒本身的半径；另一端有孔或环，除非另有规定，棒应为钢的或铝的，尺寸为 $\\$150$ 。除非另有规定，试棒处理和涂漆应按GB1727的规定进行；按产品标准规定的时间和条件进行干燥；然后在恒温 $(23\\pm2)^{\\circ}\\mathrm{C}$ 、湿度（ $(50\\pm5)\\%$ 的条件下处置，处置时间按产品标准或按GB1727的规定，一般最少放置 $^{16\\mathrm{h}}$ 。漆膜厚度按GB1764测定厚度。  \n\n2.浸泡法  \n\n（1）测试用液体材料按产品标准规定的测试液体。  \n\n（2）测试温度除非另有规定，测试应在（ $23\\pm2)^{\\circ}\\mathrm{C}$ 下进行。  \n\n（3）测试注意事项  \n\n$\\textcircled{1}$ 最好采用单独试件浸入试液槽的方法，因为在使用高电导率的试液时，可能有电解效应存在，这样做就显得更必要了。$\\textcircled{2}$ 整个试件浸入试液槽可能较为方便，但试件应是同一性质，以保证试液不受试件的影响。$\\textcircled{3}$ 浸入的试件至少离槽内壁 $30\\mathrm{mm}$ ，如果数个试件浸入同一个槽中，互相间隔至少应为 $30\\mathrm{mm}$ 。试件并应与其支架绝缘。  \n\n（4）程序A 使用单相液体。  \n\n$\\textcircled{1}$ 将足够量的试液倒人一个适当容器中，以完全或部分（2/3）浸泡规定的试件（试棒或试板)，可用适当的支架使试件以几近垂直位置浸人。  \n\n$\\textcircled{2}$ 为减少试液由于蒸发或溅洒损失，容器要加盖。  \n\n$\\textcircled{3}$ 如果规定鼓入空气搅拌或循环这种液体时，鼓气应采用脱除油脂的缓慢空气流。如有此规定，就应在适当的时间补加测试液或蒸馏水，补偿液体损失，目的是保持原体积或浓度。 ，  \n\n$\\textcircled{4}$ 当达到规定的浸泡期终点时，如果用的是水溶液，就用水彻底清洗测试件；如果是非水测试液，则用已知对涂层无损害的溶剂来冲洗，以适宜的吸湿纸或布擦拭表面除去残留液体，并立刻检查试件涂层变化现象，可与未浸泡试件对比，如果规定有恢复期，那么应在规定恢复期后，重复这种检查和对比。  \n\n$\\textcircled{5}$ 如果需要检查底材侵蚀现象，用规定方法除去涂层。  \n\n（5）程序B 使用两相液体。  \n\n$\\textcircled{1}$ 涂漆试件以适当的支架使它在几近垂直的位置放入适当的容器中，对于试板，其宽边为水平的。  \n\n$\\textcircled{2}$ 在使用前即时制备每种试液。  \n\n$\\textcircled{3}$ 除非另有规定，将密度大的液体自容器边倾人，至试件（棒和板）被浸达 $60\\mathrm{{mm}}$ 深度。操作时要小心，务必不要沾染此水平以上的试件。  \n\n$\\textcircled{4}$ 除非另有规定，以同样方式加人第二种液体至试件全部浸没。盖上容器，不要搅动，让其放置。  \n\n③达到规定的浸泡期后，自试液中取出试件，用适当的吸湿纸或布轻轻擦去表面试液，并立即检查试件涂层与每一个液相接触部位的变化现象。如果需要，与同样制备的未浸泡的试件对比。如规定有恢复期，那么在所规定的恢复期后，重复此检查与对比。  \n\n③试件中途检查时，样板不必取出，否则要随即清洗并重复浸泡操作。  \n\n$\\textcircled{7}$ 如果需要检查底材侵蚀现象，用规定方法除去涂层。  \n\n3.使用吸收性介质（1）试验材料  \n\n$\\textcircled{1}$ 吸湿盘，本身应不受测试液影响，一般情况可采用厚 $1.25\\mathrm{mm}$ 、直径 $25\\mathrm{mm}$ 左右的层压纸板。  \n\n$\\textcircled{2}$ 按产品标准规定的测试液。  \n\n$\\textcircled{3}$ 适当尺寸的表面皿。  \n\n（2）测试温度除非另有规定，测试应在 $(23\\pm2)^{\\circ}\\mathrm{C}$ 进行。  \n\n（3）程序使吸湿盘浸人适当数量的试液，然后让多余液体滴干，将盘放至试板上，使盘均匀地分布，并且至少离试板边缘12mm。用直径约40mm，并且曲率接触不到圆盘的表面皿盖上盘子，使试板在受试期（这种测试期不应超过7d）妥善置于无风环境中。如采用挥发性液体，就可能有必要以新浸透的圆盘加以替换。规定的试验期后移去盘子，如果测试液是水溶液，就用水彻底清洗，如果是非水液体，则用对漆膜无损害的已知溶剂彻底清洗。用适当的吸湿纸或布蘸吸去残留液体，并立即检查试板涂层变化现象。如规定有恢复期，达到恢复期后，应重复检查和对比。如果需要检查底材的侵蚀现象，按规定方法除去涂层。  \n\n4.点滴法  \n\n（1）试验材料按产品标准规定的测试液。  \n\n（2）测试温度除非另有规定，测试应在 $(23\\pm2)^{\\circ}\\mathrm{C}$ 下进行。  \n\n（3）程序将试板置于水平位置，并在涂层上滴加数滴试液，每滴体积约0.lmL，液滴中心至少间隔 $20\\mathrm{mm}$ ，并且至少离试板边缘 $12\\mathrm{mm}$ 。除非另有规定或商定，温度维持在(23士2)℃，在规定时间内，使试板不受干扰，充分接触空气。如有规定在测试部位以适当方法覆盖以防止过度蒸发。达到规定期后，如果是水溶液就用水彻底清洗，如果是非水溶液，就用对涂层无损害的溶剂彻底冲洗，并立即检查涂层的变化现象。如果需要检查底材的侵蚀现象，用规定的方法除去涂层。  \n\n十七、家具表面漆膜耐液测定法（GB4893.1—1985）  \n\n本标准适用于测定木家具及其他家具木制件表面漆膜的耐液性能。用浸透试液的滤纸放在试样表面，经规定时间后移去，根据漆膜损伤的程度评级。  \n\n1.设备和材料  \n\n（1）试液（见附录A)。  \n（2）定性滤纸（GB1915—1980《定性滤纸》）。  \n（3）玻璃罩：直径约 $50\\mathrm{mm}$ ，高约 $\\pmb{25}\\mathbf{mm}$ 。  \n（4）不锈钢尖头镊子。  \n（5）观察箱。  \n（6）清洗液： $\\scriptstyle15\\mathbf{m}\\mathbf{L}$ 洗涤剂 $\\scriptstyle+100{\\mathrm{mL}}$ 蒸馏水。  \n\n2.试样  \n\n规格为 $\\mathbf{250mm}\\times\\mathbf{200mm}$ 。试样涂饰完工后至少存放10天，并达到完全干燥后，方可试验。试样表面应平整，漆膜无划痕、鼓泡等缺陷。  \n\n3.试验条件  \n\n（1）试验室温度（20士2)℃，相对湿度60%～70%。  \n\n（2）试验时间根据产品标准或供需双方协议。建议时间：10s、10min、1h、4h、8h、24h、80h。  \n\n4.试验步骤  \n\n（1）用软布擦净试样表面。  \n\n（2）在试样上任取三个试验区域和一个对比区域。试验区域中心距试样边缘不小于$40\\mathrm{mm}$ ，两试验区域中心相距不小于 $65\\mathrm{{mm}}$ a  \n\n（3）将25mm圆形滤纸放入试液中浸透，用镊子取出，在每个试验区域上分别放上五层纸，用玻璃罩罩住。试验过程中需保持湿润。  \n\n（4）达到规定时间后，取下玻璃罩，揭去圆形纸，用滤纸吸干残液，静置16～24h。用清洗液和清水洗净试样表面，软布擦干，静置 $30\\mathrm{min}$ 0 Y 54  \n\n（5）检查试验区域与对比区域的差异。  \n\n①将试样上的试验区域置于观察箱内距后背550mm正中处，目视距离为0.5～1m，检查印痕和变泽情况。 D  \n\n$\\textcircled{2}$ 再将试样置于室内自然光下，检查变色、鼓泡、皱纹情况。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 719,
+        "chunk": "# 5.试验结果的评定  \n\n（1）分级标准见附表3-4。  \n\n附表3-4漆膜耐液性分级  \n\n\n<html><body><table><tr><td>等级</td><td>说明</td><td>等级</td><td>说明</td></tr><tr><td>1</td><td>无印痕</td><td>3</td><td>轻微的变色或明显的变泽印痕</td></tr><tr><td>2</td><td>轻徽的变泽印痕</td><td>4</td><td>明显的变色、鼓泡、皱纹等</td></tr></table></body></html>  \n\n（2）必须有三名检测人员分别对每一试验区域进行评定，取多数相同值作为评定结果。  \n\n（3）同一试样上的三个试验区域须分别评定，以两个试验区域一致的评定值为最终试验值。不一致时，可复试一次。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 720,
+        "chunk": "# 附录A 试液  \n\n本附录中列举的试液是仿效家具表面漆膜日常可能接触的液体，根据需要也可选用其他试液。  \n\n试液中化学品采用化学纯以上试剂，用蒸馏水配制溶液。试液必须贮存在磨口试剂瓶内。使用时液温为试验室温度。家具漆膜耐液试验用液见附表3-5。  \n\n附表3-5家具漆膜耐液试验用试液   \n\n\n<html><body><table><tr><td>试液名称</td><td>规格要求</td><td>试液名称</td><td>规格要求</td></tr><tr><td>氯化钠</td><td>15%(质量分数)</td><td>碘酒</td><td>按《中华人民共和国药典》规定</td></tr><tr><td>碳酸钠</td><td>10%(质量分数)</td><td>花露水</td><td>70%～75%乙醇，2%～3%香精</td></tr><tr><td>乙酸</td><td>30%（质量分数）</td><td>茶水</td><td>10g云南滇红1级碎茶加人1000g沸水，不要</td></tr><tr><td>乙醇</td><td>70%医用乙醇</td><td></td><td>搅动，浸泡5min后倒出的茶水</td></tr><tr><td>洗涤剂</td><td>白猫洗洁精（25%脂肪醇环氧乙烷，75%水）</td><td>咖啡</td><td>40g速溶咖啡加人1000g沸水</td></tr><tr><td>酱油</td><td>SB70—1978《酱油质量标准》</td><td>甜炼乳</td><td>QB34—1960《甜炼乳》</td></tr><tr><td>蓝黑墨水</td><td>QB-551—1981《蓝黑墨水》</td><td>大豆油</td><td>QB1335—1979《大豆油》</td></tr><tr><td>红墨水</td><td>市售</td><td>蒸馏水</td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 721,
+        "chunk": "# 十八、清漆、清油及稀释剂颜色测定法（GB1722—1979）  \n\n本标准适用于清漆、清油及稀释剂颜色的测定，即将试样与铁钴比色计进行比较，其中与铁钴比色计颜色最近似的某号色阶溶液的颜色，即代表该试样的颜色，以号表示。  \n\n1．材料和仪器设备  \n\n（1）无色玻璃试管：内径（ $10.75{\\pm}0.05$ ） $\\mathbf{m}\\mathbf{m}$ ，高（114士1）mm。(2）比色架。  \n（3）半微量滴定管：1mL、 $\\scriptstyle5\\mathbf{m}\\mathbf{L}$ 。  \n（4）分析天平：感量为 $0.0001_{\\pmb{g}}$ a  \n（5）木制暗箱： $600\\mathrm{mm}\\times500\\mathrm{mm}\\times400\\mathrm{mm}$ 费  \n\n2.试剂  \n\n（1）三氯化铁（HG3-1085—1977)：分析纯或化学纯。  \n(2）氯化钻（GB1270—1977)：分析纯或化学纯。  \n（3）重铬酸钾（GB642—1977)：分析纯。  \n（4）盐酸（GB622—1977)：分析纯，相对密度1.19。  \n（5）硫酸（GB625—1977)：分析纯，相对密度1.84。  \n3.铁钻比色计标准色阶溶液的配制  \n\n（1）稀盐酸：1质量份的盐酸溶于17质量份的蒸馏水中。  \n\n（2）三氯化铁溶液：将约5质量份的三氯化铁溶于1.2质量份的稀盐酸中，调整其颜色相当于3.000g重铬酸钾溶于100mL硫酸中溶液的颜色（如重铬酸钾不全部溶解，可用水浴加热到温度不超过 $80^{\\circ}\\mathrm{C}$ 下溶解)。  \n\n（3）氯化钴溶液：1质量份的氯化钻溶于3质量份的稀盐酸中。  \n\n（4）将上述配制好的三氯化铁溶液、氯化钴溶液和稀盐酸按附表3-6所列的用量，配成18档色阶溶液，准确调整它们的颜色至相当于同行所列重铬酸钾溶于硫酸中的标准溶液的颜色。重铬酸钾必须准确配制，当日使用。然后分别装于18支试管中，将管口密封，按顺序列于架上，妥善保管，防止光照。铁钻比色计每三年校正一次。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 722,
+        "chunk": "# 4.测定方法  \n\n将试样装入洁净干燥的试管中，在（25士1)℃下于暗箱的透射光下与铁钴比色计进行比较，选出两个与试样颜色最接近的，或一个与试样颜色相同的标准色阶溶液。试样颜色的等级直接以标准色阶的号表示。如色相不同时，可比较其颜色的深浅。  \n\n附表3-6铁钻比色计及置铬酸钾标准溶液配合量单位：%(体积分数)   \n\n\n<html><body><table><tr><td rowspan=\"2\">色阶编号</td><td colspan=\"3\">配合量</td><td colspan=\"2\">重铬酸钾标准溶液配合量</td></tr><tr><td>三氯化铁溶液</td><td>氯化钻溶液</td><td>稀盐酸</td><td>3.000g重铬酸钾溶于100mL浓硫酸</td><td>浓硫酸</td></tr><tr><td>1</td><td>0.13</td><td>0.19</td><td>99.68</td><td>0.13</td><td>99.87</td></tr><tr><td>2</td><td>0.19</td><td>0.29</td><td>99.52</td><td>0.16</td><td>99.84</td></tr><tr><td>3</td><td>0.29</td><td>0.43</td><td>99.28</td><td>0.24</td><td>99.76</td></tr><tr><td>4</td><td>0.43</td><td>0.65</td><td>98.92</td><td>0.37</td><td>99.63</td></tr><tr><td>5</td><td>0.65</td><td>0.97</td><td>98.38</td><td>0.68</td><td>99.32</td></tr><tr><td>6</td><td>1.00</td><td>1.30</td><td>97.70</td><td>1.07</td><td>98.93</td></tr><tr><td>7</td><td>1.70</td><td>1.70</td><td>96.60</td><td>1.28</td><td>98.72</td></tr><tr><td>8</td><td>2.50</td><td>2.00</td><td>95.50</td><td>1.72</td><td>98.28</td></tr><tr><td>9</td><td>3.30</td><td>2.60</td><td>94,10</td><td>2.60</td><td>97.40</td></tr><tr><td>10</td><td>5.10</td><td>3.60</td><td>91.30</td><td>5.47</td><td>94.53</td></tr><tr><td>11</td><td>7.50</td><td>5.30</td><td>87.20</td><td>8.33</td><td>91.67</td></tr><tr><td>12</td><td>10.80</td><td>7.60</td><td>81.60</td><td>12.67</td><td>87.33</td></tr><tr><td>13</td><td>16.60</td><td>10.00</td><td>73.40</td><td>19.07</td><td>80.93</td></tr><tr><td>14</td><td>22.20</td><td>13.30</td><td>64.50</td><td>25.43</td><td>74,57</td></tr><tr><td>15</td><td>29.40</td><td>17.60</td><td>53.00</td><td>34.70</td><td>65.30</td></tr><tr><td>16</td><td>37.80</td><td>22.80</td><td>39.40</td><td>42.67</td><td>57.33</td></tr><tr><td>17</td><td>51.30</td><td>25.60</td><td>23.10</td><td>74.00.</td><td>26.00</td></tr><tr><td>18</td><td>100.00</td><td>0.00</td><td>0.00</td><td>100.00</td><td>0.00</td></tr></table></body></html>  \n\n在测试时试样若由于低温而引起浑浊，可在水浴上加热到50～55℃，保持5min，然后冷却至 $(25\\pm1)^{\\circ}\\mathrm{C}$ ，再保持 $\\mathsf{5m i n}$ 后进行测定。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 723,
+        "chunk": "# 十九、色漆和清漆用漆基酸值的测定法（GB6743—1986）  \n\n本标准是以滴定法测定色漆和清漆用漆基的酸值。本标准不适用于酚醛树脂。  \n\n1.定义酸值为中和lg产品的不挥发物中的游离酸所需氢氧化钾的质量（mg)。  \n\n2.试剂  \n\n（1）混合溶剂：由2份甲苯与1份95%（体积分数）乙醇按体积比配成，使用前应以氢氧化钾溶液中和该混合溶剂。  \n\n（2）氢氧化钾标准溶液：用95%（体积分数）乙醇配制成浓度为0.lmol/L的溶液，并脱除碳酸盐，以邻苯二甲酸氢钾标定其浓度。  \n\n（3）酚指示剂溶液：浓度为10g/L，由95%（体积分数）乙醇配制而成。  \n\n也可使用其他适宜的指示剂，如浓度为10g/L的溴百里酚蓝乙醇（94%，体积分数)溶液。  \n\n3.仪器  \n\n（1）锥形瓶：容量 $\\scriptstyle250{\\mathrm{mL}}$ 。  \n\n（2）滴定管：容量 $25\\mathrm{mL}$ 或 ${50}\\mathrm{mL}$ 。  \n\n（3）烧杯：容量 $\\scriptstyle150{\\mathrm{mL}}$ 。  \n\n若需电位滴定应备有  \n\n（1）电位滴定计，带有玻璃电极和参比电极；  \n\n（2）磁力搅拌器。  \n\n4.操作步骤  \n\n（1）试样为控制氢氧化钾溶液的消耗量在10～30mL范围内，试样的称取可参考附表3-7。  \n\n附表3-7试样秤取量的范围   \n\n\n<html><body><table><tr><td>估算的酸值/(mgKOH/g)</td><td>试样的质量/g</td><td>估算的酸值/(mgKOH/g)</td><td>试样的质量/g</td></tr><tr><td><10</td><td>10</td><td>50~150</td><td>1</td></tr><tr><td>10~25</td><td>5</td><td>>150</td><td>0.5</td></tr><tr><td>25~50</td><td>2.5</td><td></td><td></td></tr></table></body></html>  \n\n（2）测定称取试样放人锥形瓶中，精确至1mg，加人50mL混合溶剂，使试样完全溶解（如室温下试样不能溶解，可在良好的通风环境下适当加热，但在进行滴定前要使溶液冷却至室温)。向试样溶液中加人2～3滴酚酞指示剂溶液，立即用氢氧化钾溶液滴定至出现红色，至少10s不消失即为终点，记下所消耗的氢氧化钾体积（mL)。进行两份试样的平行测定。  \n\n对于聚酯树脂等以酚作指示剂，终点颜色变化判断不明显的物质，可改用溴百里酚蓝等指示剂。若对终点有怀疑或试样溶液有颜色时，最好采用电位滴定，至pH=7。  \n\n为防止滴定过程中产生沉淀，可适当增加混合溶剂至150mL，或者加入25mL丙酮。  \n\n（3）空白试验与测定平行进行空白试验，试验步骤同上，但不加人试样。因为混合溶剂是经过中和的，空白试验结果应为零。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 724,
+        "chunk": "# 5.结果表示  \n\n按下式计算酸值A：  \n\n$$\nA{=}56.1{\\times}\\frac{(V_{1}{-}V_{0})c}{m{\\times}\\mathrm{NV}}{\\times}100\n$$  \n\n式中A——酸值，以每克试样消耗氢氧化钾的质量计，mg;$\\boldsymbol{V_{\\circ}}$ ———空白试验所消耗氢氧化钾溶液的体积，mL；$\\boldsymbol{V}_{1}$ ———测定试样所消耗氢氧化钾溶液的体积，mL;  \n\n滴定用氢氧化钾溶液的实际浓度，mol/L；$\\mathbf{\\nabla}_{m}$ 试样的质量，g;NV———测定试样的不挥发物含量，以质量分数表示（按GB6740—1986《漆料挥发物和不挥发物的测定》)。  \n\n以两次测定的算术平均值作为结果，计算到小数第一位。  \n\n6.精密度  \n\n（1）重复性同一操作者在同一试验室，使用同一设备仪器，在较短的时间间隔内，采用标准的试验方法，所得到的结果绝对差值低于 $3\\%$ 时，则可以认为结果的概率为 $95\\%$ 。  \n\n（2）再现性不同操作者在不同的实验室，采用标准的试验方法，对同一种试样进行两次测定所得每一平均值作为各自的结果，其两个结果绝对差值低于 $5\\%$ 时，则可以认为结果的概率为 $95\\%$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 725,
+        "chunk": "# 附录 4 油墨质量检验方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 726,
+        "chunk": "# 一、油墨颜色检验方法（GB/T14624.1—1993）",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 727,
+        "chunk": "# 1.原理  \n\n将试样与标样以并列刮样方法对比，检视试样颜色是否符合标样。  \n\n2.工具与材料  \n\n（1）调墨刀：木柄锥形钢身，长 $\\scriptstyle200{\\mathrm{mm}}$ ，最宽处 $20\\mathrm{mm}$ ，最窄处 $8\\mathrm{mm}$ 。  \n（2）刮片：不锈钢片制， $\\mathfrak{g2m m}\\times59\\mathbf{mm}\\times0.5\\mathbf{mm}$ ，刃部宽 $\\mathfrak{g}_{\\mathbf{m}\\mathbf{m}}$ 处向外弯曲 $25^{\\circ}$ 角。  \n\n（3）玻璃板： $200\\mathrm{mm}\\times200\\mathrm{mm}\\times5\\mathrm{mm}$ D  \n\n（4）刮样纸：晒图原纸（符合ZBY32002），规格$110\\mathrm{mm}\\times65\\mathrm{mm}$ ，顶端往下 $60\\sim65\\mathrm{mm}$ 处有 $\\mathsf{5m m}$ 宽黑色实底横道。  \n\n（5）玻璃纸： $65\\mathrm{mm}\\times30\\mathrm{mm}$ a",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 728,
+        "chunk": "# 3.检验条件  \n\n（1）检验应在温度（ $25\\pm1)\\mathsf{\\bar{C}}$ 、相对湿度（ $65\\pm$ $5)\\%$ 条件下进行。  \n\n（2）检视面色及色光应在人射角 $45^{\\circ}\\pm5^{\\circ}$ 的 ${\\bf D}_{65}$ 标准照明体下进行。  \n\n（3）检视底色应将刮样对光透视。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 729,
+        "chunk": "# 4.检验步骤  \n\n（1）用调墨刀取标样及试样各约 $_{5g}$ ，置于玻璃板上，分别将其调匀。  \n\n（2）用调墨刀取样约 $0.5g$ 涂于刮样纸的左上方，再取试样约 $0.5{\\bf g}$ 涂于刮样纸右上方，两者应相邻不相连。  \n\n（3）将刮片置于涂好的油墨样品上方，使刮片主体部分与刮样纸呈 $90^{\\circ}$ 角。用力自上而下将油墨于刮样纸上  \n\n![](images/6548df32af80ffcac609473b76ad31aa01070edcfb818b8f09b7c4c54605c780.jpg)  \n附图4-1颜色刮样示意图（1：1)1—刮样纸；2—试样；3—标样；4—黑色横道；5—厚墨层  \n\n刮成薄层，至黑色横道下15mm 处时，减小用力，使刮片内侧角度近似25°，使油墨在纸上涂成较厚的墨层（附图4-1)。最终刮样形状应与示意图相似。  \n\n（4）刮样纸上的油墨薄层称为面色，刮样纸下部的油墨厚层称为墨色；刮样纸上的油墨薄层对光透视称为底色。（5）油墨颜色检验完毕，将玻璃纸覆盖在厚墨层上。  \n\n5.检验结果  \n\n（1）胶印油墨、凸印油墨重点检视试样的面色和底色是否与标样近似、相符。  \n（2）网印油墨、纸张用凹印油墨重点检视试样的面色是否与校样近似、相符。  \n（3）检验结果应以刮样后5min内观察的面色和底色为准，墨色供参考。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 730,
+        "chunk": "# 二、油墨着色力检验方法（GB/T14624.2—1993）",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 731,
+        "chunk": "# 1.原理  \n\n以定量标准白墨将试样和标样分别冲淡、对比冲淡后油墨的浓度，以百分数表示。  \n\n2．工具与材料  \n\n(1) 调墨刀。  \n(2) 刮片。  \n(3) 刮样纸。  \n(4) 标准白墨。  \n(5) 标准黑墨。  \n\n3.仪器  \n\n（1）分析天平：最大载荷 $\\scriptstyle200{\\mathbf{g}}$ ，感量 $\\bf{1m g}$ 。  \n（2）圆玻璃片：2mm、直径90～100mm。  \n\n4．检验条件  \n\n（1）检验应在温度（25士1)℃、相对湿度（65士5)%条件下进行。  \n（2）观察冲淡刮样时，应在D65标准照明体下进行。  \n\n5.检验步骤  \n\n（1）用分析天平在圆玻璃片上称取标准白墨2g，试样油墨0.2g。用同样方法，相同比例，称取标准白墨和标样油墨。将称好的墨样分别用调墨刀充分调匀。  \n\n（2）用调墨刀取调匀的标准样约0.5g涂于刮样纸的左上方，再取调匀的试样约0.5g 涂于刮样纸的右上方，两者应相邻而不相连。  \n\n（3）将刮片置于涂好的油墨样品上方，使刮片主体部分与刮样纸垂直。而后，自上而下将油墨于刮样纸上刮成薄层，刮至35～45mm时，减小用力，使刮刀内侧角度近似25°，将 $25^{\\circ}$ 油墨在纸上涂成较厚的墨层（如GB/T14624.1图所示)。最终刮样形状应与GB/T14624.1中的示意图相似。 花达  \n\n（4）观察试样与标样的面色、墨色是否一致，若不一致，则改变试样标准白墨的用量，至冲淡试样与标样达到一致，按公式计算，得出试样着色力百分数。  \n\n（5）刮样后，以30s内观察所反映的墨色为准。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 732,
+        "chunk": "# 6．检验结果  \n\n$$\nS{=}\\frac{B}{A}{\\times}100~.\n$$  \n\n式中S- 一 -着色力百分比（以标样为 $100\\%$ ， $\\%$ A—冲淡标样白墨用量，g;$B$ 一冲淡试样白墨用量，g。  \n\n注：测试白墨着色力时，则以标样和试样分别代替以上所用的标准白墨，按白墨 $\\scriptstyle2_{\\mathbf{\\deltag}}$ ，标准黑墨 $0.2{\\tt g}$ 称量，检验步骤同5，计算公式也同式（1)，但A为试样白墨量， $B$ 为标样白墨量。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 733,
+        "chunk": "# 三、油墨细度检验方法（QB559—1983）",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 734,
+        "chunk": "# 1．检验原理  \n\n按检验方法将油墨稀释后，以刮板细度仪测定其颗粒研细程度及分散状况称为油墨细度，以微米（ $_{[\\mu\\mathbf{m}]}$ ）表示。  \n\n2.工具及材料  \n\n(1) $0\\sim50\\mu\\mathrm{m}$ 刮板细度仪一套（每一刻度 $2.5\\mu\\mathrm{m})$ 。  \n(2） $0.1\\mathrm{mL}$ 吸墨管一支。  \n（3）酸式滴定管一支（容量为 $25\\mathrm{mL}$ 。  \n（4）调墨刀。  \n（5）放大镜 $(5\\sim20)$ 倍。  \n(6) $6^{\\sharp}$ 油［黏度 $140{\\sim}160\\mathrm{mPa}\\bullet\\mathrm{s}(25^{\\circ}\\mathrm{C})\\big]$ 。  \n(7）玻璃板一块。  \n\n3.检验方法  \n\n（1）以 $0.1\\mathrm{mL}$ 吸墨管量取受试油墨 $0.5\\mathrm{mL}$ D（2）根据流动度的大小加 ${\\mathfrak{6}}^{\\sharp}$ 油进行稀释。  \n\n范围：流动度在 $24\\mathrm{mm}$ 以下加18滴（或以每滴$0.02\\mathrm{mL}$ 计加人 $0.36\\mathrm{mL}$ )；流动度在 $25\\sim35\\mathrm{mm}$ 加14滴（或 $0.28\\mathrm{mL}$ )；流动度在 $36\\sim45\\mathrm{{mm}}$ 加10滴（或$0.20\\mathrm{mL})$ ；流动度在 $46\\mathrm{mm}$ 以上不加油。  \n\n（3）以调墨刀挑取已稀释均匀的油墨，置于刮板细度仪凹槽深度 $50\\mu\\mathrm{m}$ 处，将刮刀垂直横置于细度仪凹槽处的油墨上，刮刀保持垂直，双手均匀用力自上而下徐徐刮至零点处停止，使油墨充满刮板细度仪凹槽，如附图4-2所示。  \n\n（4）刮好后立即将细度仪表面以 $30^{\\circ}$ 角斜对光源，用${5\\mathord{\\sim}}10$ 倍放大镜检视颗粒密集数值（在一个刻度范围内超过15个颗粒算上刻度数值，不超过15个颗粒算下刻度数值)。  \n\n![](images/0ddb30915e572f8eab3be59fef31d9a6f0640d8c4e7e791302aec6bdf7a050a0.jpg)  \n附图4-2刮板细度仪操作示意图 1一带有微米刻度的凹槽；2一刮刀与 刮板垂直90°操作；3—刮刀  \n\n4.注意事项  \n\n（1）油墨稀释时，必须调匀，不能用力研磨。防止灰尘飞人。（2）双手横执刮刀时，用力不宜过猛，勿使一边偏重，细度板槽外两边油墨必须刮净。（3）油墨细度检验需重复 $2{\\sim}3$ 次，取平均值，如果相差一刻度应重新测试。（4）吸墨管与细度仪用后必须用软布或棉纱擦净，并涂油脂防止腐蚀。  \n\n（5）本方法仅适用于非溶剂型浆状油墨。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 735,
+        "chunk": "# 四、油墨流动度检验方法（GB/T14624.3—1993）  \n\n1.原理  \n\n一定体积的油墨样品在规定压力下，经一定时间，所扩展成圆柱体，直径大小以毫米$\\bf(m m)$ 表示。  \n\n2.工具与材料  \n\n（1）调墨刀。  \n（2）玻璃板： $200\\mathrm{mm}\\times200\\mathrm{mm}\\times5\\mathrm{mm}$ a（3）乙醇：工业用。  \n(4）棉纱。  \n\n3.仪器  \n\n（1）流动度测定仪［由重量为（200.00士0.05）g码一个，重量为（50.00±0.05)g、厚度为5～6mm、直径为65～70mm圆玻璃两片，金属固定盘一个组成，如附图4-3所示]。  \n\n![](images/9df8d8c9d2f8aa0d5e96c68fb74130afe02eb9d40ac482d8a6204bbe22e021a6.jpg)  \n附图4-3 流动度测定仪  \n\n1一防止玻璃片滑动的金属固定盘；2一重50g的圆玻璃片；  \n3一受测的油墨；4一重50g的圆玻璃片；5一重200g的磁码  \n\n（2）吸墨管：容量 $0.1\\mathrm{mL}$ Q（3）透明度量尺：分度值 $1\\mathrm{mm}$ 。（4）定时钟。  \n\n4.检验条件  \n\n检验应在温度(25士1)℃、相对湿度（65士5)%条件下进行。  \n\n5.检验步骤  \n\n（1）油墨试样及流动度测定仪应事先置于恒温室内保温20min。（2）用调墨刀取油墨试样2～3mL，在玻璃板上调动15次（往返为一次)。用吸墨管吸取试样0.1mL，将管口及周围余墨刮去，使试样与管口齐平，管内油墨不得含有气泡。（3）将吸墨管内油墨挤出，用调墨刀把墨刮置于金属固定盘内的圆玻璃片中心，并将吸墨管芯的余墨刮掉，抹于上圆玻璃片中心。（4）将上圆玻璃片放在金属固定盘内的圆玻璃片上，使中间有墨部分重叠，立即压上码，开始记时（注意金属固定盘保持水平)。  \n\n（5）15min时移去法码，用透明度量尺测量油墨圆柱体直径，交叉测量两次。  \n\n6．检验结果  \n\n交叉测量的平均值为流动度数据，如交叉测量相差大于等于2mm，则试验必须重做。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 736,
+        "chunk": "# 五、油墨黏性检验方法（GB/T14624.5—1993）  \n\n1.原理  \n\n用油墨黏性仪测试油墨薄层分层或被扯开的阻力的大小，以数字表示之。  \n\n2.材料  \n\n(1）棉纱。  \n（2）擦洗溶剂：NY-200溶剂油（符合GB1922)。  \n\n3.仪器  \n\n（1）油墨黏性仪：MODELRGV-3型（日本)，如附图4-4所示。  \n\n![](images/6855af09fff17f2d3281fdbd44814bba79ebacf9ef60e24f6259690c0cf16a19.jpg)  \n附图4-4油墨黏性测试仪示意  \n\n1—水平调节螺丝；2—弹簧；3—水管；4—杠杆；5—游标；6—手柄；7一杆尺； 8—合成胶辊；9—金属辊；10—匀墨胶辊；11—电动机；12—齿轮组箱；13—变速棒； 14—曲柄；15—制动器；16—水平仪；17—吸墨器；18—横梁；19—底座  \n\n（2）秒表：分度值 $0.2\\mathbf{s}$ D",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 737,
+        "chunk": "# 4.检验条件  \n\n检验应在温度（25士1)℃、相对湿度（65士5)%条件下进行。  \n\n5.检验步骤  \n\n（1）接通仪器电源，调节恒温箱水温至32℃，保持恒温。（2）把仪器变速杆置于低速位置，将合成胶辊及匀墨胶辊压在金属辊上。（3）启动仪器，运转15min后，将游标置于标尺“0”标。调节仪器，使标尺处于平衡状态。（4）将调好的试样油墨灌入金属吸墨器后，再把试样油墨由金属吸墨器内挤出，均匀转涂在合成胶辊上，用于转动马达，使墨均匀涂于金属辊和匀墨辊上。  \n\n（5）启动仪器，匀墨。30s时移开制动器，移动游标，使标尺平衡，lmin 时读出黏性数据。（6）如需测取仪器中速和高速运转时的黏性值，将仪器变速杆移至中速或高速位置则可，检验步骤与低速相同。  \n\n6．检验结果  \n\n当5中（5）的标尺平衡时，游标所指数字，即为黏性值。  \n\n六、油墨黏性增值检验方法（GB/T14624.6—1993）  \n\n1.原理  \n\n延长油墨黏性的测定时间，观察油墨黏性值的变化情况，以数字表示。  \n\n2.材料  \n\n(1）棉纱。  \n(2）擦洗溶剂：NY-200溶剂油（符合GB1922)。  \n\n3.仪器  \n\n（1）油墨黏性仪：MODELRGV-3型（日本）。  \n\n（2）秒表：分度值0.2s。  \n\n4.检验条件  \n\n检验应在温度（25士1)℃、相对湿度（65士5)%条件下进行。  \n\n5.检验步骤  \n\n（1）接通仪器电源，调节恒温箱水温至32℃，保持恒温。（2）把仪器变速杆置于低速位置，将合成胶辊及匀墨辊压在金属辊上。（3）启动仪器，运转15min后，将游标置于标尺“0”位，调节仪器，使标尺处于平衡  \n状态。（4）将调好的试样油墨灌入金属吸墨器后，再把试样油墨由金属吸墨器内挤出，均匀涂  \n在合成胶辊上，用手转动马达，使墨均匀涂于金属辊和匀墨辊上。（5）启动仪器，匀墨。30s时移开制动器，移动游标，使标尺平衡，lmin 时读出黏性  \n数据。（6）仪器继续运转，记录第15min时的黏性数值。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 738,
+        "chunk": "# 6.检验结果  \n\n15min时的黏性值与1min时的黏性值之差，即为黏性增值。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 739,
+        "chunk": "# 七、油墨飞墨检验方法（QB566—1983）  \n\n1．检验原理  \n\n油墨飞墨是观察油墨在印刷时，油墨脱离墨辊的离散情况。测定飞墨是利用测定黏性时，观察油墨表横梁上白纸的粘墨情况。 D8 S  \n\n2．工具及材料  \n\n与QB564—1983油墨黏性检验方法相同。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 740,
+        "chunk": "# 3.检验方法  \n\n按 QB564—1983油墨黏性检验方法进行测定，当油墨表开1min后，在横梁上放一张白纸，继续转动1min后取下白纸，观察白纸上是否有墨，根据白纸上飞墨多少情况来判断飞墨程度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 741,
+        "chunk": "# 八、油墨、油脂黏度检验方法（QB574—1983）",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 742,
+        "chunk": "# 1.检验原理  \n\n物质在外力作用下，液层发生位移，分子间发生摩擦，对摩擦所表现的抵抗性称为绝对黏度，单位以 $u_{\\mathrm{{m}}}\\mathrm{{Pa}}\\cdot\\mathrm{{s}}^{\\mathfrak{n}}$ 表示。  \n\n2.仪器及材料  \n\n（1）旋转式黏度计，如附图4-5所示。  \n(2）超级恒温器。  \n\n3.检验方法  \n\n（1）测定前检查仪器的液池是否干净，并校正零点。  \n\n（2）将试样慢慢地注入液池内，注意不应太满或太浅，开启超级恒温器以 $25\\mathrm{^\\circC}$ 保温。  \n\n（3）按试样的黏度大小放入合适的旋转锤，见附表4-1。右手开动仪器开关，左手大拇指从左向右搓动启动齿轮，使旋转系统运转或自行启动。  \n\n（4）经 $15\\mathrm{{min}}$ 保温运转，待仪器上读数指针保持在一个固定点时记录所指数据，关闭仪器让指针回到零点上，然后再用同样方法开启仪器，待指针稳定后，再记录所指数据，核对两次数据是否相同。相同即为正确数据，并进行换算。  \n\n![](images/ee448f6b064399e90f7702e2951871c6fa8183d539c042ae62571ba4fce547d1.jpg)  \n附图4-5旋转式黏度仪  \n\n附表4-1旋转黏度计黏度换算  \n\n\n<html><body><table><tr><td>测试黏度范围/mPa·s</td><td>应用转子型号</td><td>计算公式</td></tr><tr><td>1～100</td><td>大型</td><td>指针数据×1</td></tr><tr><td>110～1000</td><td>中型</td><td>指针数据×10</td></tr><tr><td>1100～10000</td><td>小型</td><td>指针数据×100</td></tr><tr><td>11000~100000</td><td>小型加10F变速器</td><td>指针数据×1000</td></tr><tr><td>110000~1000000</td><td>小型加100F变速器</td><td>指针数据×10000</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 743,
+        "chunk": "# 九、油墨光泽检验方法（QB573—1983）",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 744,
+        "chunk": "# 1.检验原理  \n\n油墨光泽的测定是采用DFH-80型光电光泽计进行的，在定光源的照射下，试样与标准面反射光量度的比，用来表达试样油墨的光量度（以标准面的反射光量度为100%）。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 745,
+        "chunk": "# 2.检验方法  \n\n（1）按QB570—1983油墨固着速度检验方法（甲）通过印刷适性仪或按QB570-1983固着速度检验方法（乙)，通过小型手摇打样机打样。  \n\n（2）将测头插头拧紧，然后打开电源，预热 $10\\mathrm{{min}}$ 。  \n\n（3）调零：将测量头拿起，旋转调旋钮，使表头指针为零。  \n\n（4）将测头置于标准板上，旋转定标旋钮，使指针指向标准板的标准值。  \n\n（5）重复本检验方法（3)、（4）直至指针仍然能指零和指示标准值，方可进行测量。  \n\n3.注意事项  \n\n（1）测定同一类型的各种油墨时，要注意使用同一种纸张规定的标准纸张，否则影响测定数据。  \n\n（2）印片的干燥程度对测量有影响，印片要干燥 $\\pmb{24}\\mathbf{h}$ 。（3）测头在试样的不同位置上，会得到不同的光量度，故要选择三点，求其平均值为该油墨的光泽的光量度。（4）接线时必须仔细，接线后要反复检查，防止输人端与输出端接反，造成仪器的损坏。（5）测头的灯泡位置对测量影响很大，不可随意更改，当换灯泡时，应按使用说明书调整位置。油凰耐7醇耐碱耐酸耐水检验方法（浸泡法）甲（QB568—1983)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 746,
+        "chunk": "#",
+        "category": "ovide the text segment about hydrophilic polymers that you would like me to analyze, and I will classify it accordingly."
+    },
+    {
+        "id": 747,
+        "chunk": "# 1.检验原理  \n\n经干燥的油墨刮样，分别浸泡于规定浓度的酸、碱、醇及水中经一定时间后取出刮样，根据刮样变化情况评级，并以其表示油墨耐酸、碱、醇及水的性能。  \n\n2.工具及材料  \n\n(1) 调墨刀。   \n(2) 刮墨刀。   \n(3) 刮样纸。   \n(4) 试管。   \n(5) 蒸馏水。   \n(6) $1\\%$ 氢氧化钠溶液。   \n(7） $1\\%$ 盐酸溶液。   \n（8） $95\\%$ 乙醇溶液。   \n（9）小镊子。  \n\n3.检验方法  \n\n（1）将受检油墨用调墨刀放于道林纸中上方，持刮墨刀自上而下用力刮于刮样纸上，呈均匀的刮样，然后使之在常温条件下放置，干燥24h（个别品种可适当延长)。  \n\n（2）将干燥后刮样剪下面色部分小块，分别置于规定浓度的酸、碱、醇、水各试管内浸泡。  \n\n（3）浸泡24h后，用镊子取出刮样。与未经浸泡的刮样对比，检视刮样变色情况，根据附表4-2评定受检油墨耐酸、碱、醇、水的级别。  \n\n注：当刮样变色程度与溶液染色程度不在同一级别时，以两者中较差的级别评定之。  \n\n4.注意事项  \n\n（1）耐乙醇试验因试剂挥发较快，所以此实验要在密封条件下进行。（2）做空白实验对比，以便观察纸张在溶液中变化情况，定级时应减除其纸张变化因素。 （3）测定时室温不宜过低，通常情况下应在20～25℃之间测定。 戏啦  \n\n附表4-2油墨耐酸、碱、醇和水的级别（浸泡法）  \n\n\n<html><body><table><tr><td>级别</td><td>刮样变色程度</td><td>溶液染色程度</td><td>级别</td><td>刮样变色程度</td><td>溶液染色程度</td></tr><tr><td>1</td><td>严重变色</td><td>严重染色</td><td>4</td><td>基本不变色</td><td>基本不染色</td></tr><tr><td>2</td><td>明显变色</td><td>明显染色</td><td>L</td><td>不变色</td><td>无色</td></tr><tr><td>3</td><td>稍变色</td><td>稍染色</td><td></td><td></td><td></td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 748,
+        "chunk": "# 十一、油墨耐乙醇、耐酸、耐碱、耐水检验方法乙（滤纸渗透法）（QB569—1983)  \n\n1.检验原理  \n\n经干燥的油墨刮样与规定浓度的酸、碱、醇和水溶液浸透的滤纸接触，在一定压力、一定时间后，根据油墨刮样变化情况及渗透染色滤纸张数评级并以之表示油墨耐酸、碱、乙醇及水的性能。  \n\n2.工具及材料  \n\n（1）调墨刀。  \n（2）刮墨刀。  \n（3）小玻璃板 $(9,5\\mathrm{cm}\\times6\\mathrm{cm})$ 。  \n(4) $1000\\mathbf{g}$ 码。  \n（5）定性滤纸（直径 $11\\mathrm{cm})$ 。  \n(6) $\\scriptstyle100\\mathbf{m}\\mathbf{L}$ 蒸发皿。  \n（7）蒸馏水。  \n(8) $1\\%$ 氢氧化钠溶液。  \n(9） $1\\%$ 盐酸溶液。  \n(10) $95\\%$ 乙醇溶液。  \n（11）小镊子。  \n\n3．检验方法  \n\n（1）将受检油墨用调墨刀调少量放于刮样纸中上方，刮墨刀自上而下用力刮于刮样纸上，呈均匀的刮样，剪去墨色部分，然后置于常温放置 $\\boldsymbol{24\\mathrm{h}}$ ，使之干燥。个别品种可适当延长。  \n\n（2）取小玻璃板置于平面工作台上，将刮样的1/2平放于玻璃板之上。  \n\n(3）在 $100\\mathrm{mL}$ 蒸发皿中注入溶液，取定性滤纸10张以镊子夹在一端浸入溶液中至完全侵透，取出覆盖于油墨刮样1/2部分。  \n\n（4）将另一块玻璃板压在滤纸上，并加一个码静置24h后拿下码及玻璃板，稍干后，检视刮样变色情况（可同不压滤纸部分比较）及染渗滤纸数量（张)，按附表4-3标准评定等级。  \n\n附表4-3油墨耐酸、碱、醇和水级别（滤纸渗透法）  \n\n\n<html><body><table><tr><td>级别</td><td>滤纸染色数量/张</td><td>刮样变化程度</td><td>级别</td><td>滤纸染色数量/张</td><td>刮样变化程度</td></tr><tr><td>1</td><td>8~9</td><td>严重改变</td><td>4</td><td>1~3</td><td>基本不变</td></tr><tr><td>2</td><td>6~7</td><td>明显改变</td><td>5</td><td></td><td>不变</td></tr><tr><td>3</td><td>4~5</td><td>稍变</td><td></td><td></td><td></td></tr></table></body></html>  \n\n4.注意事项  \n\n（1）接触油墨刮样的第一张滤纸不计在内。（2）试验中如滤纸不染色，可根据附表4-3中刮样变化程度评级。（3）耐乙醇试验因试剂挥发较快，所以测试时要放到可封闭的盒内，其他操作相同。（4）做空白试验对比，以便观察纸张在溶液中的变化，定级时应减除变化因素。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 749,
+        "chunk": "# 十二、油墨渗色性检验方法（QB571—1983）",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 750,
+        "chunk": "# 1.检验原理  \n\n将油墨置于滤纸上经一定时间后，观察滤纸吸收油墨渗出之油圈上是否带色，以检视油墨的渗色情况。  \n\n2.工具及材料（1）调墨刀。  \n\n（2）定性滤纸。  \n\n3．检验方法  \n\n（1）用调墨刀充分搅拌受试油墨，并取少量堆放在定性滤纸上。  \n（2）1h后观察油墨四周渗透的颜色，以渗出的油圈不带蓝色、黄褐色或其他颜色为佳。  \n\n十三、涂膜硬度铅笔测定法（GB6739—1986)  \n\n本标准采用已知硬度铅笔测定有机涂膜硬度，适用于涂料的发展研究和工业生产控制。为了使此法达到最大精确度，要采用一套同一批号的“中华牌”高级绘图铅笔。操作可用手工方法或仪器试验方法，但作为仲裁试验要用仪器试验方法。  \n\n1．材料和仪器  \n\n（1）一组“中华牌”高级绘图铅笔6H、5H、4H、3H、2H、H、HB、B、2B、3B、4B、5B、6B，其中6H最硬，6B最软，由6H～6B硬度递减。  \n\n(2）削笔刀。  \n（3）涂膜铅笔划痕硬度仪。  \n(4) $400^{\\#}$ 砂纸。  \n\n2.测定步骤和条件  \n\n（1）制备试件按照GB1727——1979《漆膜一般制备法》制备试件三块，或从涂漆件上切取具有代表性的试件三块。  \n\n(2）工具准备用削笔刀将铅笔削到露出柱形笔芯5～6mm（切不可松动或削伤铅芯)，握住铅笔使其与400#砂纸面成90°，在砂纸上不停划圈，以摩擦铅芯端面，直至获得端面平整、边缘锐利的笔端为止(边缘不得有破碎或缺口)。铅笔每使用一次后要旋转 ${180}^{\\circ}.$ 再用，或重摩后再用。  \n\n![](images/a0a2296449cc03c714d7ee66b1fbab8599110ba135db9df07116a4cb29af4cea.jpg)  \n附图4-6手工操作示意  \n\n（3）手工操作把涂漆试件固定于水平面上，握住已削好的铅笔，使其与涂膜成45°，用力（此力大小或使铅笔端缘破碎，或犁伤涂膜）以每秒约1mm的速度向前推进(附图4-6)。从最硬的铅笔开始每级铅笔犁五道  \n\n3mm的痕，直至找出五道痕都不犁伤涂膜的铅笔为止，此铅笔的硬度即代表所测涂膜的铅笔硬度。 DX  \n\n（4）仪器试验把涂漆件置于试验仪的试件台上，涂漆面朝上，把通过试验仪磁码重心的垂线调节到通过铅笔端与涂面的交点，把已削好的铅笔装人铅笔夹，使其与涂面成45°，用平衡码把铅笔上的负荷调到使铅笔刚好接触试件，拧紧止动螺钉，使铅笔端离开涂面。在码台上加（1.00士0.05）kg的码，松开止动螺钉，以便铅笔端与涂面接触。摇动试台的移动摇臂使试件与铅笔端反向移动3mm，移动速度约0.5mm/s，然后拧紧止动螺钉，转动铅笔180°（保证铅笔端面无损伤）并变换试件位置，依次犁出五道痕。用此方法（附图4-7)，从最硬的铅笔开始测试，并相继换上低一级的铅笔，直至找出五道痕中只有一次犁伤涂膜的铅笔，以其下一级铅笔代表所测涂膜的铅笔硬度。如未犁伤涂膜，则以此级的铅笔代表所测涂膜的铅笔硬度。  \n\n![](images/e3ebddc7b9fdff419f18e39abce57b3df1ad6a986ae788a100ffd52795cfaf5b.jpg)  \n附图4-7 仪器试验示意  \n\n（5）试验条件按产品标准规定或施工要求的条件进行，仲裁试验要在温度为（ $^{(23\\pm}$ $2)\\mathsf{\\bar{C}}$ 、相对湿度（ $50\\pm5)\\%$ 的标准条件下进行。  \n\n（6）试验报告  \n\n$\\textcircled{1}$ 试验铅笔的生产厂及产品批号。  \n$\\textcircled{2}$ 试验涂膜名称、底材及测定的铅笔硬度。  \n$\\textcircled{3}$ 试验日期、人员。  \n$\\textcircled{4}$ 特殊条件的情况。  \n\n3.精密度  \n\n重复性如果两个操作者在同一实验室内采用同样的铅笔和试板，用同样的方法，而得到的结果之差大于1、（1）中所述的一个铅笔单位，则应予怀疑。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 751,
+        "chunk": "# 附录5 胶黏剂的性能测试方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 752,
+        "chunk": "# 一、外观  \n\n通过外观观察可以初步判定胶黏剂的质量，但具体操作为经验性。  \n\n（1）将 $20\\sim50\\mathrm{g}$ 液体胶黏剂倒人 ${\\mathsf{50}}\\sim100{\\mathrm{mL}}$ 的烧杯中，用干燥洁净的玻璃棒或匙勺放人胶黏剂中，然后将玻璃棒或匙勺提起，提起的高度约距离烧杯口 $20\\mathrm{cm}$ ，观察流动的胶液，胶液应该均匀，不含其他机械杂质或凝结物。  \n\n（2）取一个玻璃瓶，装人一定数量的胶黏剂，将瓶子倾斜，让胶液润湿瓶子上部，然后将瓶子竖直，观察从瓶子上部沿玻璃瓶壁下流的胶液均匀情况。  \n\n对于使用寿命较短的胶黏剂，必须使用新配制的试样。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 753,
+        "chunk": "# 二、相对密度  \n\n物质单位体积的质量为该物质的绝对密度。由于物质的体积是温度的函数，因此表示某  \n\n一物质的密度时必须标明温度。相同温度下物质的密度与水的密度的比值为相对密度。相对密度可用比重瓶法、比重计法和注射器法来测定。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 754,
+        "chunk": "# 1．比重瓶法  \n\n液体胶黏剂相对密度的测定，选用比重瓶法测定最精确。在精确度为万分之二的天平上，将25mL的比重瓶装满蒸馏水，放人25℃恒温槽中恒温半小时，称重；再将比重瓶装满待测的液体胶黏剂，放人25℃恒温槽中恒温半小时，称重。按下式求得液体胶黏剂的相对密度：  \n\n$$\nd=\\frac{w}{w_{\\star}}d_{\\star}\n$$  \n\n式中 $\\boldsymbol{\\mathsf{z}}\\boldsymbol{\\mathsf{\\Sigma}}$ 液体胶黏剂的质量；${\\pmb w}_{\\star}$ -水的质量；$d_{\\star}$ ， 一 $25^{\\circ}\\mathrm{C}$ 蒸馏水的密度；$d$ $25\\mathrm{^\\circC}$ 液体胶黏剂的相对密度。  \n\n固体胶黏剂也可用比重瓶法来测定其相对密度。所不同的是比重瓶中装入固体胶黏剂的1/2～2/3，然后加满蒸馏水。固体胶黏剂的相对密度可由下式来求得：  \n\n$$\nd=\\frac{w}{{\\bf w}_{1}+{\\bf w}-{\\bf w}_{2}}d_{\\star}\n$$  \n\n式中 $\\boldsymbol{\\mathbf{\\rho}}_{\\boldsymbol{\\w}}$ $\\mathbf{\\cdot25^{\\circ}C}$ 蒸馏水重加瓶重； $\\pmb{w}_{1}$ 一 -固体胶黏剂质量； $\\scriptstyle{\\boldsymbol{w}}_{2}$ 一 固体胶黏剂加 $25\\mathrm{^\\circC}$ 蒸馏水加瓶重。  \n\n对于糊膏状的胶黏剂，采用比重瓶法测定比较复杂，当其黏度特别大时不宜用比重瓶法测定，可用注射器法测定。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 755,
+        "chunk": "# 2．比重计法  \n\n用比重计测定液体胶黏剂的相对密度较简单迅速。将液体胶黏剂沿玻璃棒小心注人量筒内，试样温度与周围环境温度相差不超过士5℃。用手拿住比重计上端，将其小心慢慢地放入试样中，当比重计在试样中停止摇动后，立即记下相当于液面上边缘的读数，即为该胶黏剂的相对密度。  \n\n含有沉淀物的胶黏剂不适用本方法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 756,
+        "chunk": "# 3.注射器法  \n\n取15～30mL医用注射器一支，装满胶黏剂（若为液体，注射器上装粗针头；若为糊膏状，则不装针头)，排掉气泡，将胶黏剂注入已经称量过的带磨口锥形瓶中精确称重，算出胶黏剂的质量。同样，用注射器向锥形瓶注人同体积的蒸馏水，精确称重，得到同体积蒸馏水的质量，即可用下式求得胶黏剂的相对密度：  \n\n$$\nd=\\frac{w-w_{\\Re}}{w_{\\Re}-w_{\\Re}}d_{\\Re}\n$$  \n\n式中 $\\pmb{w}$ 胶黏剂和锥形瓶质量；${\\boldsymbol{w}}_{\\star}$ 同体积水和锥形瓶质量；W瓶 锥形瓶质量；$^{d_{\\star}}$ 测定温度时水的密度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 757,
+        "chunk": "# 三、黏度  \n\n黏度是物体抵抗流动变形能力的一种量度，它是评价胶黏剂质量的一项重要指标。黏度  \n\n的国际单位制为 $\\mathtt{P a}\\cdot\\mathbf{s}$ 。  \n\n胶黏剂的黏度一般比较高，大多为非牛顿流体，因此普遍采用旋转式黏度计来测定其黏度。在工业生产上，也有用涂-4杯黏度计或落球黏度计。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 758,
+        "chunk": "# 四、针入度  \n\n针人度是指在规定的荷重下，尖针在一定的时间插入胶液试样中的深度。针入度越大，表示胶液越软，即黏度越小；反之，则表示胶液越硬，即黏度越大。测定时，需先将试样放在（100士5)℃下干燥，待溶剂完全挥发后，才可在装置上测定。其标准试验条件见附表5-1。  \n\n附表5-1针入度试验条件  \n\n\n<html><body><table><tr><td>条件</td><td>温度/℃</td><td>荷重/g</td><td>时间/s</td></tr><tr><td>I</td><td>0</td><td>200</td><td>60</td></tr><tr><td>Ⅱ</td><td>25</td><td>100</td><td>5</td></tr><tr><td></td><td>40</td><td>50</td><td>5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 759,
+        "chunk": "# 五、不挥发物含量  \n\n为便于涂胶量的确定，以及确定相应的配方，含有溶剂的胶黏剂必须测定组分中的不挥发物含量或固体含量(浓度)。  \n\n称取1～1.5g试样（对于浓度较小的可适当增加称量)，置于干燥洁净的称量瓶中，将称量瓶置于通风橱中，用250W红外灯加热（控制灯下的温度不超过实验温度)，干燥至试样不流动后，放入已按实验温度调好的鼓风恒温箱内加热1.5h［以丙酮、乙醇、乙酸乙酯等作溶剂时（80士2)℃，以甲苯、汽油等作溶剂时（110士2)℃］，取出放入干燥器中，冷却至室温，称重。然后再次将试样放人鼓风恒温箱内加热0.5h，取出，放人干燥器中冷却至室温，称重。实验至两次称量的质量差不大于0.01g为止。全部称量准确至0.001g。不挥发物含量按下式计算：  \n\n$$\n\\scriptstyle{X=\\frac{G_{1}}{G}\\times100\\%}\n$$  \n\n式中 $x$ —不挥发物含量， $\\%$ 。$G_{1}$ —干燥后试样的质量，g;$G$ —干燥前试样的质量，g。  \n\n实验结果取两次平行实验数值的平均值，两次平行实验数值之差不大于1%。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 760,
+        "chunk": "# 六、酸值  \n\n某些胶黏剂中含有酸性物质，当这种胶黏剂应用于金属或木材时，会引起金属腐蚀或木质纤维素水解，因此必须测定其酸值。  \n\n酸值测定方法有容量法、试纸法、比色法、电位差法（pH计法）四种，容量法测得的酸值单位为每克胶黏剂，氢氧化钾的质量（mg)，其他三种方法测得的是pH值。 米  \n\n（1）容量法工厂普遍采用本法，具体测试方法见附录2。（2）试纸法用pH试纸测定相当简便，但较粗略。（3）电位差法测得pH值精确。测试时取试样10g（准确至0.01g）于洁净烧杯内，加人30mL蒸馏水，上面覆盖表面皿，在电热板上加热，微沸10min，冷却至室温后用pH计测定。  \n\n（4）比色法将胶黏剂试样涂覆在玻璃板上，制成厚度为0.5mm左右的胶膜室温干燥$_{12\\sim15\\mathbf{h}}$ ，取胶膜，用研钵磨成细粉，称取 $_{2g}$ 左右试样粉末，放人石英玻璃杯中，加人$10\\mathrm{mL}$ 蒸馏水， $15\\mathrm{{min}}$ 后用比色计测定 $\\mathtt{p H}$ 值。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 761,
+        "chunk": "# 七、灰分  \n\n测定胶黏剂组分的灰分含量以及分析灰分成分，目的是确定无机填料的数量及其化学性质。  \n\n精确称取一定质量的胶黏剂，放在坩埚中小心地灼烧，直至灼烧完全。可先用喷灯灼烧，再放人高温炉中；为了加速灼烧，并使灼烧完全，可滴入少量硝酸或 $30\\%$ 的过氧化氢，但氧化剂的加人应在主要成分燃尽、坩埚冷却后加入。灼烧后，冷至室温称量，按下式计算灰分的百分含量：  \n\n$$\nX{=}\\frac{d_{1}}{d}{\\times}100\\%\n$$  \n\n式中 $x$ —灰分(百分含量)， $\\%$ $d$ —胶黏剂试样质量，g；$d_{1}$ -—灼烧完全后灰分质量，g。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 762,
+        "chunk": "# 八、流动性  \n\n流动性是指胶黏剂在涂布后处于垂直状态下的流动速度，它是衡量胶黏剂施工性能的参数之一。  \n\n![](images/cac2c9cdee93d79b5e8e598290c961df26996b46ccf3f39f31953bada7818fe9.jpg)  \n附图5-1胶黏剂流动性测试试片(单位：mm)  \n\n流动性测试试片如附图5-1所示。  \n\n测定时先将试样涂布于试片凹槽刻度以上的部位，然后立刻把试片垂直放置，固定在架上，并开始用秒表计时。流动性 $\\boldsymbol{v}$ 可用下式计算：  \n\n$$\n\\scriptstyle{V={\\frac{S}{T}}}\n$$  \n\n式中S 流动距离，cm;$\\boldsymbol{\\tau}$ 一流动时间，s。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 763,
+        "chunk": "# 九、适用期  \n\n胶黏剂的适用期（使用寿命）是使用中检验胶黏剂质量的重要工艺指标。适用期指胶黏剂从各组分混合均匀开始，到能维持其可用性能的时间，即胶黏剂黏度增大到不宜涂覆到被粘物表面为止的时间。  \n\n把待测胶黏剂的各组分放置在（23士2)℃的实验温度下，至少4h。在比配胶量大1/3体积的烧杯中，按胶黏剂配比配制不少于250mL的胶黏剂，待各组分充分混匀开始计时，作为适用期的起始进间。然后把配制好的胶黏剂尽快地均分成若干份（不少于5份)，保存在60mL的带盖容器内，至少充满容器体积的3/4。从适用期起始时间起，经一定的时间间隔，按国家标准重复进行黏度测定和制备粘接试样测定粘接强度，将黏度和粘接强度对时间作图，以黏度迅速突变上升的时间和粘接强度下降到产品标准指标值以下的时间中，取较短的时间确定为胶黏剂的适用期。  \n\n对于混合放热量较多的胶黏剂，其一次混合物量一般以25g为宜；对于放热量较小的溶剂型胶黏剂，若其近似适用期为8h，则用量以 ${\\mathsf{500m L}}$ 为宜。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 764,
+        "chunk": "# 十、耐介质性  \n\n耐介质性为耐水、耐油、耐蒸汽、耐有机溶剂和耐化学药品性能等的总称。目前，耐介质性的测定，一般是测定胶黏剂在一定介质中浸渍一定时间后的质量变化百分率。不同介质有不同的浸渍温度：通常水为（25士5)℃，非燃料油类为（80士5)℃，燃料油类（如120#溶剂汽油）为（25士5)℃，浸渍时间为48h。也可按产品标准规定的温度和时间来测定。  \n\n测试试片为一个带70mm×20mm×1.5（或2）mm凹槽的金属板（类同流动性测试试片)，精确称重测试试片质量，将待测胶黏剂涂于试片凹处，置于80℃烘箱中干燥2h，在干燥箱中放置室温后称重，至恒重为止。然后将试片浸于介质中，在规定的温度下放置一定时间（温度和时间可按产品标准选定或自定)，取出后用乙醇（介质为水）或石油醚（介质为油类）洗涤晾干，再于80℃烘箱烘2h，在干燥器内放至室温后称重直至恒重。质量变化率$\\kappa$ （耐介质性）从下式求得：  \n\n$$\nK{=}\\frac{{{w}_{2}}-{{w}_{3}}}{{{w}_{2}}-{{w}_{1}}}{\\times}100\\%\\\n$$  \n\n式中 $\\pmb{w}_{1}$ ： 测试试片的质量，g；$\\scriptstyle{\\boldsymbol{w}}_{2}$ 一 浸渍前测试试片和试样的质量，g;$\\boldsymbol{w}_{3}$ 浸渍后测试试片和试样的质量，g。  \n\n耐介质性还可以在一定条件下，胶黏剂浸入介质后的力学性能如剪切强度变化百分率来表示。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 765,
+        "chunk": "# $+-$ 、耐热变形性  \n\n胶黏剂固化物在热变形温度上下性能变化很大，因此测定胶黏剂热变形温度是非常重要的。测热变形温度是让被测试材料的样品承受一定机械力的作用，并以一定的速度升高试样所承受的温度，记下变形达到一定程度时的某一临界温度，以该温度作为被测试材料耐热变形性的指标。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 766,
+        "chunk": "# 1.环球法  \n\n环球法是测量材料软化点的方法，环球法仪器装置如附图5-2所示。  \n\n![](images/e8ed73f850b01821cf0c451ce55fa29ea3ad488e3b9ee010ca2576d5f3a156ad.jpg)  \n附图5-2环球法仪器装置1—环；2一球；3一被试材料；4一架子；5—控制板  \n\n![](images/430246f3d37f793bea3c5f9f7f2c5f50d15ab04839213c275a98ed811be2bf8d.jpg)  \n\n附图5-3马丁氏耐热性试验仪   \n1一试样；2—下夹头；3—底板；4—上夹头；   \n5—横杆；6—负荷；7-恒温箱；8—温度计； 9—指针联动杆；10—指针；11一标尺  \n\n测定时将熔融的测试材料注人黄铜环内直到环的边缘，待冷却后，用热刀片削去高出环边的材料。把钢球放在环中央的材料层上。将准备好的环与试样（不超过4个）放置在仪器架上，整个仪器架放人盛水或甘油（用于软化点高的材料）的烧杯中，以每分钟 $5\\%$ 的速度加热上述装置，同时记录温度，温度计的水银球应放在最靠近试样的位置。取试样受热变软，被钢球压出触及离环的下边 $25\\mathrm{mm}$ 处的控制板时的温度作为软化点。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 767,
+        "chunk": "# 2.马丁耐热性测定法  \n\n如附图5-3所示为马丁耐热性试验仪。  \n\n试样1为截面 $10\\mathrm{mm}\\times10\\mathrm{mm}$ 、长度（ $(120\\pm2)\\mathrm{mm}$ 的长条，插在固定于底板3的下夹头2中。在试样上端套上上夹头4，横杆5固定在上夹头4上，负荷6可以沿横杆移动。全部装置（通常备有同时试验三个试样的三对夹头）放在恒温箱7中，恒温箱的温度用温度计8测量，温度计的水银球应放在临近试样处。在离试样中心轴线 $240\\mathrm{mm}$ 处的横杆5上安放指针联动杆9，杆上有指针10，指针的位置在标尺11上记录。负荷6的质量和离试样的距离均要经计算确定。  \n\n负荷6按计算确定的位置放好后，在常温下记录指针10沿标尺11的位置。然后调节恒温箱的自动控制系统，使恒温箱以每小时（ $(50\\pm3)^{\\circ}\\mathrm{C}$ 的速度升温。当指针10从起始位置下降 $6\\mathrm{{mm}}$ 时，记录温度计所示温度，即为试样的马丁耐热性的温度值。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 768,
+        "chunk": "# 十二、电性能  \n\n胶黏剂尤其是电子材料灌封胶等用于电子材料的胶黏剂，其电性能是极其重要的性能参数。电性能包括体积电阻和体积电阻系数、表面电阻和表面电阻系数、介电常数、击穿强度(介电强度)、电阻率等。  \n\n测定胶黏剂电性能的试样一般制成直径 $100\\mathrm{{mm}}$ （或 $\\mathsf{50m m}^{\\mathrm{~\\cdot~}}$ 、厚 $_{1\\sim2\\mathrm{mm}}$ 的光滑平整圆盘，要求在（ $25\\pm2)^{\\circ}C$ 和相对湿度 $(65\\pm5)\\%$ 的条件下处理不低于 $^{16\\mathrm{h}}$ 。  \n\n1．表面电阻 $\\scriptstyle{R_{\\mathrm{S}}}$ 和表面电阻系数 $\\rho_{\\mathsf{S}}$ 、体积电阻 $R_{\\mathbf{V}}$ 和体积电阻系数 $\\rho_{\\mathsf{V}}$ 的测定  \n\n用高阻计法测定，将充分放电后的试样（未加电压时，应在高阻计上设有明显的指示值）（接入高阻计检测端，调整仪器，加上试验电压（ ${\\bf\\chi}_{100}{\\sim}1000{\\bf V})$ ? $1\\mathrm{min}$ ，读取电阻的指示值）(或电压、电流)，按下式计算表面电阻系数 $\\rho_{\\mathrm{{s}}}$ 和体积电阻系数 $\\rho_{\\tt V}$  \n\n$$\n\\rho_{\\mathrm{s}}{=}R\\mathrm{s}\\times\\frac{2\\pi}{\\ln(D_{2}/D_{1})}\n$$  \n\n$$\n\\rho_{\\mathrm{v}}=R\\mathrm{v}{\\frac{S}{d}}\n$$  \n\n式中 $\\rho_{\\mathrm{s}}$ —表面电阻系数；  \n\n$D_{2}$ 环电极直径， $\\mathbf{cm}$ $D_{1}$ 一 测量电阻直径， $\\mathsf{c m}$ ${\\rho_{\\mathrm{v}}}$ 体积电阻系数；$d$ 试样厚度，cm;$s$ -电极有效面积， $\\mathsf{c m}^{2}$ @  \n\n表面电阻 $R_{{\\mathrm S}}$ 可直接读取，或用电压、电流值换算；  \n体积电阻 $R_{\\mathbf{V}}$ 可直接读取，或用电压、电流值换算。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 769,
+        "chunk": "# 2.介电常数E  \n\n介电常数试验如附图5-4所示。把试样放置在两个电极之间，测量电容。然后，将空气  \n\n取代试样，再测一次电容，以两个电容的比值计算介电常数。  \n\n$$\n\\scriptstyle\\varepsilon={\\frac{C}{C_{\\mathfrak{S}}}}\n$$  \n\n式中 $c$ 一试样的电容；$c_{\\mathfrak{L}}$ 空气的电容。  \n\n介电常数受许多因素如频率、电压、温度和湿度等影响。  \n\n![](images/f7115afcccb8ccf2abb3fedf65ceac2fc0ff6969ab1a8a6db935aeee1b5797bd.jpg)  \n附图5-4介电常数试验示意  \n\n![](images/7ed4faf2977a16668e3e046ea006d92b18ec37faf74a7a0c4852ff3504d12e6b.jpg)  \n附图5-5击穿强度试验示意",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 770,
+        "chunk": "# 3.击穿强度（介电强度） $\\scriptstyle{E}$  \n\n采用连续均匀升压或逐级升压的方式对试样施加交流电压直到击穿为止。测定方法如附图5-5所示，测出击穿电压 $\\boldsymbol{\\upsilon}$ ，计算击穿强度 $\\scriptstyle{E}$ 。  \n\n$$\n\\scriptstyle{E={\\frac{U}{d}}}\n$$  \n\n式中U——击穿电压，V;$d$ —试样厚度， $\\mathbf{mm}$ 9  \n\n用连续升压测定时，升压速度为1kV/s(U<20kV）和2kV/s(U≥20kV)。用逐级升压测定时，按连续升压法所测得击穿电压U的50%为起点，每点停留1min，直至试样被击穿为止，读取试样被击穿的前一段的电压值。逐级升压电压值（升压应迅速）的规定见附表5-2。  \n\n附表5-2电压值逐级升压要求  \n\n\n<html><body><table><tr><td>U(连续升压所测)/kV</td><td><5</td><td>5~25</td><td>25~50</td><td>>50</td></tr><tr><td>每级升压的电压/kV</td><td>0.5</td><td>1</td><td>2</td><td>5</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 771,
+        "chunk": "# 4.电阻率  \n\n测导电胶的电阻率方法如附图5-6所示。选择厚度为1～2mm的平板玻璃，分别截割成  \n\n$160\\mathrm{mm}\\times10\\mathrm{mm}$ 和 $120\\mathrm{mm}\\times10\\mathrm{mm}$ 的玻璃条，每长短各一片为一组，用酒精或丙酮清洗干净，十燥，用刻度值不大于0.002的千分尺，沿整个玻璃条长度方向选测3个点的厚度，取其算术平均值作为玻璃条的厚度。按所测试的导电胶涂胶工艺，在每个玻璃条的一个面上均匀涂胶。然后涂两片干净的尺寸为 $\\mathbf{30mm}\\times10\\mathbf{mm}\\times(0.03\\sim0.05)\\mathbf{mm}$ 的铜箔或铝箔分别粘在短玻璃条的两端，作为测量引线。将涂有导电胶的长短玻璃条叠合，用夹子夹好，除去被挤出来的导电胶，进行固化，即可进行测量。每组试样 $3{\\sim}5$ 个，用双臂电桥或精密电位差计测量试样两引线间的电阻值，每一试样测量两次，取其算术平均值即为试样的电阻 $\\scriptstyle R_{x}$ ，并按下式计算电阻率：  \n\n![](images/6c8c5fe1d94e932dad202c11ad53747f81f8cd52edeac75119abdcf1ae9afb9d.jpg)  \n附图5-6测量导电胶 电阻率用试样  \n\n式中 $\\scriptstyle R_{x}$ 一 试样的电阻， $\\mathfrak{a}$ $\\delta\\cdot$ 1 胶层的厚度(一般取三个点的平均值)， $\\mathsf{c m}$ $d$ —胶层的宽度，cm;$L$ 胶层的长度，或电极引线间距， $\\mathsf{c m}$ a",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 772,
+        "chunk": "# 十三、力学性能  \n\n胶黏剂的力学性能是衡量胶黏剂粘接性能的最重要指标。胶黏剂的力学性能包括剪切强度、拉伸强度、剥离强度、冲击强度、扯断强度、撕裂强度、持久强度、疲劳强度等。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 773,
+        "chunk": "# 1.剪切强度  \n\n剪切强度表示胶黏剂在受切线方向的应力时单位面积上的最大断裂负荷。根据受力方式可分为拉伸剪切、压缩剪切、扭转剪切、弯曲剪切强度等几种，其中拉伸剪切强度最常用。  \n\n拉伸剪切强度测定试片一般为 $125\\mathrm{mm}\\times20\\mathrm{mm}\\times2\\mathrm{mm}$ ，采用单面搭接，搭接面长约15mm。测定时将试片经过表面处理后，将胶黏剂均匀涂在试片上，然后将两片试片叠合，在规定条件下进行固化，两片试片叠合后宽度方向的错位不超过0.5mm。试片在拉伸试验机上以10mm/min的恒定拉伸速度施加负荷，直到试片胶层破坏为止。记下试验机刻度盘上的破坏负荷，并按下式计算剪切强度 $\\tau$  \n\n$$\n\\tau{=}\\frac{P}{F}{=}\\frac{P}{a b}\n$$  \n\n式中 $P$ 破坏负荷，N;$F$ 搭接面积， $\\mathrm{cm}^{2}$ $\\alpha$ 搭接面长，cm；$\\textbf{\\em b}$ 搭接面宽， $\\mathbf{cm}$ 。  \n\n测试片不少于5对，搭接面积应根据每对试片破坏后，实际测量的数值进行计算，精确到0.0lcm²。在较高、较低温度下长期工作的胶黏剂应测不同温度下的强度。通常的测试温度为一60℃、0℃、60℃、100℃、150℃、200℃、250℃，测试时应在试验机上装上加热或冷却装置，测试样应在测试温度下保持 $30{\\sim}45\\mathrm{min}$ C",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 774,
+        "chunk": "# 2.拉伸强度  \n\n拉伸强度指试件在受到与粘接平面垂直并均匀分布的单位面积上的拉应力。拉伸强度包括均匀拉伸强度和不均匀拉伸强度。  \n\n（1）均匀拉伸强度均匀拉伸试验的特征是力的作用线通过试样中心，受力时粘接面上的应力是均匀分布的。均匀拉伸试验适用于刚性材料与刚性材料、刚性材料与弹性材料、塑性材料粘接时胶黏剂拉伸强度的测定，这是最常用的一种拉伸强度。所用试片有菌型试样、圆形试样和方形试样（附图5-7)，一般用菌型试样。测定方法与剪切强度测定相同。  \n\n（2）不均匀拉伸强度当作用在试片上的拉伸应力分布在整个接合面上，但并不是均匀分布时，这种情况被称为不均匀拉伸，也称为不对称拉伸或弯曲拉伸，此时所测得的破坏强度即为不均匀拉伸强度。  \n\n不均匀拉伸强度不是单位面积，而是单位长度上的最大破坏负荷。这是因为当粘接面上形成不均匀拉伸情况时，负荷多集中于胶层的两个边缘或一个边缘上。不均匀拉伸强度一般是衡量粘接型胶黏剂柔韧性的参数。  \n\n![](images/55ebbe6330626098e464fbeddae3eb597ea1acfb5ce2eedda452627993c9799a.jpg)  \n附图5-7胶黏剂均匀拉伸强 度测定试样  \n\n![](images/f13862094f46c8db89eddb5277420a58ec028d45187170721ccd9b4485d699ec.jpg)  \n附图5-8胶黏剂不均匀 拉伸强度测定试样  \n\n不均匀拉伸强度测定常用的测试试片如附图5-8所示。测定前，先精确测量黏合部位的宽度，然后将试片固定在专用夹具上，使两夹头之间的距离为 $200\\mathrm{mm}$ 。调整接合面中心线，使其与夹具的横梁中心线重合，最后以 $10\\mathrm{mm/min}$ 的恒定拉伸速度施加负荷，直到试片胶会破坏为止。试片应不少于3对，不均匀拉伸强度 $_B$ 按下式计算：  \n\n$$\nB{=}\\frac{P}{b}\n$$  \n\n式中 $P$ 一破坏负荷，N；$\\boldsymbol{b}$ 一试片宽度， $\\mathbf{cm}$ ，一般标准为 $3\\mathsf{c m}$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 775,
+        "chunk": "# 3.剥离强度  \n\n当刚性材料（如金属）与橡胶、织物等粘接时，一般需测定剥离强度。剥离强度是当应力不是均匀分布在整个接合面，而是集中在试片胶缝边附近时的拉伸强度。剥离强度必须在电子材料试验机上测定，而不能在摆锤式材料试验机上测定。测定剥离强度的方法很多，目前常用的是90°、180°剥离测定法。由于胶黏剂剥离强度测定时剥离力波动性较大，因此数据处理用求积仪法。测定时，将试片从上方插到下夹具上，并用销钉固定，然后在（100士5)mm/min的恒定拉伸速度下施加负荷，在自动记录仪上可得到应力-应变曲线图，当胶层破坏后，可用下式计算剥离强度 $\\sigma_{\\mathbf{b}}$  \n\n$$\n\\sigma_{\\mathrm{b}}=\\frac{K F}{a b}\n$$  \n\n式中 $\\kappa$ 曲线图上单位高度所代表的负荷量， $\\mathbf{N}/\\mathbf{cm}$ $F$ 曲线图形面积， $\\mathsf{c m}^{2}$ $a$ 曲线图形底线的长度， $\\mathsf{c m}$ $^b$ 试片宽度， $\\mathsf{c m}$ 中",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 776,
+        "chunk": "# 4.冲击强度  \n\n冲击强度表示胶黏剂在冲击负荷作用下，达到破坏时其单位面积所需的功。冲击强度分为剪切冲击强度和弯曲冲击强度两种。测试两种冲击强度的试片如附图5-9所示。  \n\n（1）剪切冲击强度测定时，将试片用专用夹具固定在摆锤式冲击机上，摆锤的一端具有平整的冲击表面，其宽度略大于试片受力部位的宽度（25mm)。当试片受冲击时，摆锤端部的冲击表面应与试片上半部全面接触，摆锤的冲击速度为3.5m/s。试片断裂后，再将破坏的试片端部紧靠在一起，重新进行一次冲击试验，求得摆锤对空白试片所消耗的功。测量接合面的长度和宽度，求出接合面积，精确到0.0lcm，然后按下式计算剪切冲击强度W：  \n\n![](images/97f9ec676d1942536928a9f6fa236d2792da50296a7fb0f46bb69bd95863dbb2.jpg)  \n附图5-9胶黏剂冲击强度测定试样  \n\n$$\n\\mathbf{\\delta}\\mathbf{W}{=}\\frac{\\mathbf{\\bar{W}}_{1}-\\mathbf{\\bar{W}}_{0}}{\\mathbf{\\varepsilon}{S}}\n$$  \n\n式中 $\\pmb{W}_{1}$ 一试片断裂功，J；$\\pmb{W}_{0}$ —空白试片消耗功，J;S- 一接合面积， $\\mathsf{c m}^{2}$ 。  \n\n（2）弯曲冲击强度测定试片由两个端面为正方形的金属长条对接而成，粘接后胶层两边的错位不能超过0.1mm。接合面应平整，并与试片的纵轴垂直。然后将试片置于摆锤式冲击机的支架上，支架间的距离为40mm。松开摆锤，让摆锤自由落下。试片断裂后，再求得摆锤对空白试片所消耗的功。弯曲冲击强度A可用下式计算：  \n\n$$\nA{=}\\frac{A_{1}-A_{0}}{S}\n$$  \n\n式中 $\\mathbf{A}_{1}$ ——试片断裂功，J；$\\scriptstyle A_{0}$ —空白试片消耗功，J;S- 一接合面积， $\\mathsf{c m}^{2}$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 777,
+        "chunk": "# 5.扯断强度  \n\n扯断强度是弹性型胶黏剂重要的力学性能。在测定胶黏剂试样扯断强度的同时，一般还可以得到扯断伸长率、扯断永久变形率和扯断伸长永久变形率。  \n\n扯断强度的测定是在拉力试验机上进行的，试样厚度为（2.0士0.3）mm，分A型、B型和C型三种如附图5-10所示。  \n\n测定时将试样的工作部位印上两条平行线作为标距，把试样垂直夹在试验机夹具上，并使下夹具以（500士10）mm/min的速度拉伸，直到扯断为止。并按下列公式计算扯断强度$\\pmb{\\sigma}$ 、扯断伸长率 $\\pmb\\varepsilon$ 、扯断永久变形率 $H_{\\mathsf{d}}$ 和扯断伸长永久变形率 $H_{\\mathrm{dd}}$  \n\n$$\n\\begin{array}{l}{{\\displaystyle{\\sigma=\\frac{P}{b h}}}}\\\\ {{\\displaystyle{\\varepsilon=\\frac{L_{1}-L_{0}}{L_{0}}\\times100\\%}}}\\\\ {{\\displaystyle{H_{\\mathrm{d}}=\\frac{L_{2}-L_{0}}{L_{0}}\\times100\\%}}}\\end{array}\n$$  \n\n$$\nH_{\\mathrm{{dd}}}=\\frac{L_{2}-L_{0}}{L_{1}-L_{0}}\\times100\\%\n$$  \n\n式中 $P$ 试样所受负荷， $\\mathbf{N}$ $\\textbf{\\textit{b}}$ -试样工作部分宽度， $\\mathsf{c m}$ $\\boldsymbol{h}$ 试样工作部分厚度， $\\mathsf{c m}$ 中$L_{0}$ 试样试验前标距， $\\mathbf{m}\\mathbf{m}$ $L_{1}$ 试样扯断时标距， $\\mathbf{mm}$ L2- 一试样扯断并停放3min后对接起来的  \n标距， $\\mathbf{mm}$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 778,
+        "chunk": "# 6.撕裂强度  \n\n撕裂强度直接影响胶黏剂的使用寿命。它是指胶料在规定温度下、在均匀拉伸应力作用下被撕裂时单位厚度所需的负荷。测定撕裂强度的方法很多，目前用得较多的是起始型撕裂试验法。  \n\n![](images/04a31762641b67a7ccd0f6defb5fff0321d248175156182b4db5fca5a834cb94.jpg)  \n附图5-10 胶黏剂扯断强度测定试样  \n\n起始型撕裂试验法也称为直角型撕裂试验法，试样的形状尺寸如附图5-11所示。测定时，温度一般控制在室温（ $23\\pm5)^{\\circ}\\mathrm{C}$ ，试验机以（ $500\\pm10)$ . $\\mathbf{mm}/\\mathbf{min}$ 的速度拉伸，直到撕断，撕裂强度 $\\phi_{\\mathrm{s}}$ 由下式计算求得：  \n\n$$\n\\phi_{\\mathrm{s}}=\\frac{P}{h}\n$$  \n\n式中 $P$ —试样撕断时的最大负荷，N；$\\boldsymbol{h}$ -—试样直角部位的厚度， $\\mathsf{c m}$ 。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 779,
+        "chunk": "# 7.持久强度  \n\n持久强度也称蠕变性能，是指胶黏剂固化后反伸恒定负荷随时间作用的能力。对粘接接头施加一个小于静态破坏力的负荷 $P$ ，胶黏剂层在长时间应力作用下内部会发生塑性蠕动，粘接接头失去尺寸稳定性，粘接强度也不断下降，到一定时间接头便产生破坏。因此，把在规定时间、一恒定温度下胶黏剂所能持续承受的最高静态强度称为持久强度。  \n\n![](images/f1d812c1ed5f12fbba542cba27625d214e59643e2d99df60e9b487b22d442ba8.jpg)  \n附图5-11胶黏剂起始 型撕裂试验试片  \n\n持久强度试验是考核粘接接头的强度稳定性，它是在不考虑变形的情况下测定温度、时间、强度三者之间的关系。试验时一般都在温度恒定的条件下测定时间与强度之间的关系。通过持久强度试验，能够提供试验温度下规定时间内的强度依据；或者是使用温度下要求的负荷作用时的寿命依据。本试验还可在室外曝露条件下或实际使用的环境中进行，提供模拟数据；也可对多种胶黏剂在相同的放置条件下，以持久强度试验进行评价或筛选。  \n\n持久强度试验用高温蠕变—持久强度试验机（如RD2-3型)，最高试验温度为350℃，测试时，必须保证整个加载平稳，不产生冲击力。  \n\n持久强度又分持久剪切强度和持久拉伸强度，分别用剪切试样（单搭接试样）和拉伸试样作测试试样。持久剪切强度用表示，持久拉伸强度用表示，右上角T表示测试温度（℃），右下角t表示破坏持续时间（h)。如5与表示测试温度为150℃、持续破坏时间 $400\\mathrm{{h}}$ 的持久强度。  \n\n关于测试条件，可选择恒定载荷分别为静态破坏负荷的 $90\\%$ 、 $80\\%$ 、 $70\\%$ 等，温度可根据实际范围选择一 $60^{\\circ}\\mathrm{C}$ 、 $-40^{\\circ}\\mathrm{C}$ 、 $-20^{\\circ}\\mathrm{C}$ 、 $60^{\\circ}\\mathsf{C}$ 等。  \n\n通常又把在10000h的工作时间下的持久强度称为持久强度极限。在给定的应力标准下，接头发生破坏的时间称为持久寿命。由于这种在应力作用下，胶层沿力作用方向发生的位移为蠕变，因此测持久强度的同时，还能测定蠕变长度。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 780,
+        "chunk": "# 8.疲劳强度  \n\n![](images/d532ab2fb9a4c3267c817414cb6e0eafe8a49f1383e394ea4d92dc7a9a0414ff.jpg)  \n附图5-12等幅正弦波动态负荷${\\pmb\\sigma}_{\\operatorname*{max}}$ 一最大应力； $\\pmb{\\sigma}_{\\mathrm{min}}$ 一最小应力；${\\pmb\\sigma}_{\\mathtt{m}}$ 一平均应力； $\\sigma_{\\circ}$ 一动态负荷幅值  \n\n疲劳强度是指在给定条件下，对试样重复施加一定负荷至规定次数而不引起破坏的最大应力。参照金属疲劳极限强度的规定，一般把 $1\\times10^{7}$ 次时的疲劳强度称为疲劳极限强度。在规定的疲劳应力条件下，造成试片破坏的交变应力循环次数，称为疲劳寿命。  \n\n虽然在实际使用下，接合部位承受的负荷是无规则的，但在测定疲劳强度的过程中，一般均采用有规则的动态负荷。目前用得最多的是等幅正弦波动态负荷（附图5-12)。  \n\n测定时，循环振幅（应力值的变化）对结果有很大影响。这种应力值的变化可用振幅系数 $\\gamma$ 表示：  \n\n$$\n\\gamma=\\frac{\\sigma_{\\operatorname*{min}}}{\\sigma_{\\operatorname*{max}}}\n$$  \n\n疲劳强度一般在测定金属疲劳强度的振动试验机上测定，振幅系数为0.1或小于0.1，负荷振幅频率为 $1000\\sim3000$ 周/ $\\mathbf{min}$ 。施加的负荷可选择瞬时静态强度的 $70\\%$ 、 $60\\%$ 或$50\\%$ ，直到试片破坏为止。记录负荷循环次数，求得不同振动负荷和循环次数下的试片断裂强度，即为疲劳强度。根据所得到的数据，作断裂强度和断裂时的循环次数关系图，所得曲线即为疲劳强度曲线。  \n\n疲劳强度可分为剪切疲劳强度、均匀拉伸疲劳强度和不均匀拉伸疲劳强度三种。它们所用的测试试片与剪切强度、均匀拉伸强度、不均匀拉伸强度基本相同。测定时试片不应少于3对，施加负荷的相对误差在 $\\pm2\\%$ 范围内，试片环境温度偏差不超过 $\\pm1\\%$ 。  \n\n在测试疲劳强度过程中，试片的破坏往往是由于胶层产生小裂缝或其他局部损坏而引起的，不同形式的应力集中都会影响疲劳强度的测定数据，使试片过早遭到破坏。因此，为了获得较理想的结果，应当在准备试片、表面处理和涂胶粘接每个环节都需认真操作。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 781,
+        "chunk": "# 十四、使用寿命  \n\n温度、环境、使用时间、功能性指标为胶黏剂使用寿命的四要素。使用温度与环境气氛直接影响使用寿命，功能性指标如活性降低值、绝缘材料耐电压的最低值等都属于寿终指标，使用时间即使用寿命。四个要素缺一不可，但要同时考虑则很复杂，通常先固定某个或几个因素进行研究。例如在研究绝缘材料的使用寿命时可将绝缘材料寿命规定为2000h，在这一指标下求最高使用温度，最高使用温度越高，材料就越耐老化，在相同条件下材料的使用寿命也就越长。  \n\n通常采用由实验总结出的经验公式寿命方程来求得使用寿命 $\\tau$  \n\n$$\n\\frac{\\mathrm{d}a}{\\mathrm{d}t}{=}A\\mathrm{e}^{-E/R T}(1{-}a)^{n}\n$$  \n\n$$\n\\scriptstyle1_{\\mathbf{g}\\tau=\\alpha}{\\frac{1}{T}}+b\n$$  \n\n式中 $^{b}$ 常数；a- $\\scriptstyle\\alpha=E/R$ .$\\scriptstyle{E}$ 活化能；$R$ 气体常数；$T_{\\mathbf{\\delta}}$ 使用温度。  \n\n根据寿命方程，在 $T_{1}$ 和 $T_{2}$ 两个温度下，测定两个使用寿命值，就可以计算出 $a$ 和 $\\textbf{\\textit{b}}$ 值。从而可以求出其他使用温度下的寿命；反之，有了使用时间，也可以计算最高使用温度。  \n\n根据寿命方程，将lgt对 寸作图可以得到寿命曲线，从曲线的斜率可以求出活化能E。一般通过几个高温点实验，然后作图外推来确定寿命值。从理论上看，寿命方程是合理的，但实验烦琐费时。  \n\n大量实验证明，用热重法预测寿命比较准确可靠。具体做法是首先从TG 曲线求活化能$\\scriptstyle{E}$ ，从而求得寿命方程中的 $\\alpha$ 值，再用常规方法测定一个温度高一点的寿命值，这样就可推断其他温度下的寿命值。这种方法称为点斜法。所谓“点”，就是指用常规法在某温度下测得的寿命；“斜”是指斜率，即 $\\alpha$ 值。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 782,
+        "chunk": "# 十五、老化试验  \n\n胶黏剂使用过程中，胶接接头受到太阳光、空气中的氧、水分、臭氧、工业腐蚀气体、盐雾、霉菌和其他介质以及湿热环境的长期作用，会使胶黏剂及胶接接头的各种性能破坏，这种现象称为胶黏剂的老化。老化试验的目的是了解胶黏剂耐受各种介质的情况，以确定胶黏剂适应各种介质的能力，估计并进而确定胶接接头的使用寿命。  \n\n胶黏剂的老化涉及胶料的老化、助剂的迁移、散失等。由于胶料是胶黏剂的成膜物质，而胶料绝大多数为高分子材料，因此胶黏剂老化研究所用的方法和理论也多沿用高分子材料老化的惯用方法，常用的研究方法有大气老化、大气加速老化、人工模拟气候加速老化、湿热老化和盐雾试验等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 783,
+        "chunk": "# 1.大气老化  \n\n即大气曝晒试验。试验时先将曝晒架安装在指定的地点，曝晒架一般用钢材经焊接制成，涂浅灰色或草绿色保护漆。场地四周必须空旷，周围障碍物至曝晒场地边缘的距离至少超过障碍物高度的3倍。然后将试样用不锈金属丝固定在曝晒架上，试样之间距离不少于 $10\\mathrm{mm}$ 。  \n\n试样曝晒时间一般至少1年。曝晒1年的试样，每月测定一次性能；曝晒3年的试样，一季度测定一次性能；曝晒5年的试样，半年测定一次性能；超过5年，每年测定一次性能。将老化以后测定的各种粘接件的各种性能与老化前的情况进行对比，一般把降到原设计允许的最小承受负荷作为该胶黏剂的老化指标，或者把降到原始性能的 $50\\%$ 作为老化指标。  \n\n为了获得比较全面的耐各类气候环境的数据，大致可将我国分为湿热带气候区、亚热带气候区、寒冷带气候区、沙漠气候区、高原气候区五个气候区，有关单位分别在这些地区设有大气曝晒试验场。进行试验时必须使试件充分受到太阳光及大气中各种不同环境介质的综合作用，通过观察其外观、物理性能及力学性能的变化来评定耐大气老化性能。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 784,
+        "chunk": "# 2.大气加速老化  \n\n大气曝晒试验可靠，但费时且试验结果重现性不好，采用加速老化试验可缩短试验周期，提高试验水平。  \n\n加速老化试验通常是在特制的老化试验机内进行，以人工的方法模拟或强化大气中的光、热、降雨、湿度等影响因素，以期在较短的时间内再现接近于天然条件大气老化的结果。  \n\n该试验机是一种户外使用、全天候跟踪太阳的自动曝晒架，当太阳光线偏转时，其光电设备及运动机构可使反射镜始终对准太阳，使其始终受到比自然曝晒时强得多的光照。采用该机器，通常能使试件受到的紫外光能量增加2.5倍，可见光能量增加3.5倍，红外光能量也增加3.5倍，从而加速了其老化的过程。另外，试验机还装有运转时间光电自动累积仪器，可以自动记录试验时间，为计算加速倍数和推算老化寿命提供计算数据。  \n\n实践证明，老化试验机模拟性好，比普通大气老化缩短很多时间，不足之处是对外界依赖性较大，但它是一种有发展前途的老化试验方法。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 785,
+        "chunk": "# 3.人工模拟气候加速老化  \n\n这是一种用人工制造的模拟老化光源代替阳光进行加速老化的试验方法。目前试验光源主要有紫外线碳弧灯、阳光碳弧灯、氙灯。试验时，试件应在无应力的情况下装在试架上，保持空气流通。对大多数胶黏剂，目前还设有系统的实验证明上述三种光源中哪一种加速老化作用较好。有人曾研究过与胶黏剂在某些方面相似的某些涂料的人工老化情况。实验证明阳光型人工加速老化设备（WE-SUN型)，在温度（ $(50\\pm2)^{\\circ}\\mathrm{C}$ 、相对湿度（ $(75\\pm5)\\%$ 、降雨$\\scriptstyle2\\mathbf{m}\\mathbf{m}/\\mathbf{h}$ 的条件下，比大气曝晒速度快，少者快 $2\\sim3$ 倍，大多数快 $5{\\sim}6$ 倍，甚至有的快10倍左右，而紫外光型人工老化设备（WE-SH型）较阳光型慢 $2{\\sim}3$ 倍。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 786,
+        "chunk": "# 4.湿热老化  \n\n高温和高湿的共同作用是胶黏剂老化的主要原因，因为湿气在高温和高湿作用下能渗进胶层，破坏胶层的组成与结构，从而降低性能。  \n\n湿热试验一般都在调温调湿箱中进行的。调温调湿箱能够借助空气流动使供湿装置产生一定量的水蒸气并鼓人试验箱内，通过温度、湿度控制系统的调节而获得规定的温度、湿度。试验中要严格注意当试验箱的温湿度达到控制数值后，其有效试验空间内的任何一点温度、相对湿度与控制值的偏差范围应控制在温度 $\\pm2\\%$ 、相对湿度 $\\pm3\\%$ 内。试验箱内任意一处的空气应流动其风速不大于 $\\bf{1m/s}$ 。如采用喷水雾法或加泡法加湿时，所用的水应洁净，一般采用蒸馏水。受试样品试验前应除去灰尘、油污，试件应完整无损；受试样品应尽可能按工作状态放置，并不能影响箱内温度、湿度为宜；样品放置时不能相互重叠、接触，并应避免上层样品的冷却水滴落在下层样品上。  \n\n试验多为恒湿，这种试验多数仅用于考核各种胶黏剂相对耐湿热的性能，或考核在一定温度和湿度条件下，某种胶黏剂耐湿热老化的变化趋势。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 787,
+        "chunk": "# 5.盐雾试验  \n\n本试验主要是反映沿海及沿海陆地的大气中的盐雾会加速粘接接头的腐蚀、粘接性能劣化的情况。盐雾的破坏过程大体是当盐雾微粒沉降在粘接件上，便迅速吸潮溶解成氯化物的水溶液，在一定的温度、湿度条件下，这样的氯化物水溶液或离解后的氯离子，具有很大的渗透能力，能渗人胶层内部，加速电化学腐蚀反应引起老化和对被粘材料的腐蚀。  \n\n盐雾实验可在各种盐雾试验箱内进行，所用试片的处理与大气老化相同，按有关标准配制含 $\\mathbf{NaCl}$ ， $\\mathbf{MgCl_{2}}$ ， $\\mathbf{CaCl}_{2}$ 、KCI等一定浓度的盐水溶液，控制 $\\mathtt{p H}$ 值为 $6.5{\\sim}7.2$ (附表5-3)。  \n\n附表5-3 盐水配方  \n\n\n<html><body><table><tr><td>盐</td><td>NaCl</td><td>MgCl（无水）</td><td>CaCl（无水）/KCl</td><td>HO</td></tr><tr><td>用量/g</td><td>27</td><td>6</td><td>1</td><td>67(mL)</td></tr></table></body></html>  \n\n试片从试验箱取出后，用少量棉花蘸水，去除试片上的盐粒，存放 $24\\mathbf{h}$ 后测定各种性能，将其与空白试验比较，判断该种胶黏剂的耐盐雾腐蚀性能。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 788,
+        "chunk": "# 附录 6 已发布的光固化产品标准",
+        "category": " References"
+    },
+    {
+        "id": 789,
+        "chunk": "# 一、紫外光（UV）固化木器漆（HG/T3655—1999)  \n\n本标准规定了紫外光固化木器漆的要求、试验方法、标志、标签、包装及贮存和运输。本标准适用于木质地板、家具或其他木器的装饰与保护用紫外光固化漆。",
+        "category": " Introduction"
+    },
+    {
+        "id": 790,
+        "chunk": "# 1.要求  \n\n产品应符合附表6-1的要求。  \n\n附表6-1紫外光（UV）固化木器漆要求  \n\n\n<html><body><table><tr><td rowspan=\"2\">项 目</td><td colspan=\"2\">指 标</td><td rowspan=\"2\">测试方法</td></tr><tr><td>底漆</td><td>面漆</td></tr><tr><td>容器中状态</td><td colspan=\"2\">搅拌后呈均匀状态</td><td>打开容器后目视观察。容器底部允许 有少量沉淀，经用调刀揽拌后，易于混合</td></tr><tr><td>细度/μm ≤</td><td>70</td><td>有光：10 半光和无光：35</td><td>均匀时，可定为“揽拌后呈均匀状态” 按GB/T1724规定进行测定</td></tr><tr><td>固化速率</td><td colspan=\"2\">商定</td><td>可用单一的紫外灯或生产线用紫外光 固化装置进行测量，其测量单位为 s或</td></tr><tr><td>漆膜外观</td><td colspan=\"2\">平整</td><td>m/min。漆膜干燥的判定按GB/T 1728—1979(1989)中第3章的甲法进行 目视观察</td></tr><tr><td>光泽(60°)</td><td></td><td>有光：90 半光和无光：商定</td><td>按GB/T9754的规定进行测定，人射 角为60°</td></tr><tr><td>划格试验/级 ≤</td><td>2</td><td>2</td><td>按GB/T9286的规定进行底漆与底 材间（1mm间距）、复合层与底材间</td></tr><tr><td>硬度 V</td><td>0.60</td><td>有光：0.60 半光和无光：0.50</td><td>(2mm间距)划格试验 按GB/T1730—1993中第4章的规 定进行测定</td></tr><tr><td>复合层耐水性</td><td></td><td>72h不起泡，不起皱，不脱落</td><td>按GB/T9274中甲法进行测定。试 验用水应符合GB/T6682中三级水的</td></tr><tr><td>复合层耐醇性</td><td></td><td>8h不起泡，不起皱，不脱落</td><td>要求</td></tr><tr><td>耐磨性(750g/500r)/g ≤</td><td></td><td>0.030</td><td>按GB/T9274中甲法进行测定 按GB/T1768的规定进行测定</td></tr><tr><td>复合层耐干热性[（90士2)℃]/级 ≤</td><td></td><td>2</td><td>按GB/T4893.3的规定进行测定</td></tr></table></body></html>  \n\n2.试验方法  \n\n（1）采样按GB3168的规定进行。  \n\n（2）试板除硬度、光泽和耐磨性三项使用玻璃板外，其余检测项目均使用枫木面三夹板。玻璃板应符合GB/T9271的规定；枫木面三夹板应符合附录A的要求。  \n\n（3）漆膜制备采用GB/T1727—1992中6.2或6.4.2的方法，并可用线棒涂布器或辊涂法涂漆。  \n\n$\\textcircled{1}$ 单层漆膜试板的制备：试板涂漆后，静置 $1\\mathrm{\\sim}10\\mathrm{min}$ （具体时间按产品标准规定），然后用紫外光固化装置固化。  \n\n$\\textcircled{2}$ 复合层试板的制备。  \n\na.紫外光固化面漆和非紫外光固化底漆复合：按生产单位的规定选用和施涂非紫外光固化底漆，再涂面漆后用紫外光固化装置固化。涂料使用单位也可自行选用非光固化底漆，但应做与光固化面漆的配套性试验，以确认所选用的底漆与光固化面漆复合体系均符合本标准1的要求。  \n\nb.紫外光固化面漆和紫外光固化底漆复合：将表面处理过的试板涂一遍底漆，用紫外光固化装置固化，然后用 $400^{\\#}$ 砂纸按GB/T9271—1988中3.4的规定将试板打磨平整；用同样的方法再涂一遍底漆，固化、打磨，最后涂面漆，用紫外光固化装置固化。  \n\n$\\textcircled{3}$ 制备光固化漆膜时，应记录紫外光固化装置的以下参数：紫外灯盏数、灯的发射波长范围、灯型、灯的线功率、灯管长度、灯功率、灯所使用过的时间、照射距离、反射罩形状。如需要，还应补充其他参数。  \n\n④ 试板制成后，在GB9278规定的标准环境条件下放置24h后进行各项检验。  \n\n（4）漆膜厚度及涂布量漆膜厚度按GB/T13452.2的规定进行测量；涂布量按附录B的规定进行测量。除另有规定外，试板为玻璃板时，干漆膜厚度为：底漆（ $18\\pm3)$ $\\scriptstyle\\mu\\ m$ ，面漆（13士3）μm，耐磨性试验的漆膜厚度为（45士5）μm。试板为三夹板时，涂布量以干膜计：底漆涂布量为30～40g/m2；复合涂层中底漆的总涂布量为30～40g/m，面漆的涂布量为 $20\\sim30\\mathrm{g}/\\mathrm{m}^{2}$ 。  \n\n（5）检验方法见附表6-2测试方法中规定。  \n\n(6）检验结果的判定检验结果的判定按GB/T1250中修约值比较法进行。  \n\n3.检验规则  \n\n（1）按 $\\mathrm{HG/T~2458}$ 进行。  \n\n（2）本标准中所列全部技术要求均为形式检验项目。其中容器中状态、细度、固化速率、漆膜外观、光泽、划格试验和硬度为出厂检验项目。在正常生产情况下，每半年至少进行一次形式检验。  \n\n4．标志、标签、包装（1）标志按GB/T9750规定进行。  \n\n（2）标签产品应附有标签，标明：产品的标准号、型号、名称、净含量、合格标记、厂名、厂址及生产日期、批号、贮存期。  \n\n（3）包装按GB/T13491的规定进行。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 791,
+        "chunk": "# 5.贮存和运输  \n\n按HG/T2458的规定进行。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 792,
+        "chunk": "# 附录A 枫木面三夹板  \n\n为了保证处理过的枫木面三夹板的洁净表面在涂漆前不直接用手触模或与其他污物接触，通常应戴洁净手套后方可处理。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 793,
+        "chunk": "# 1.要求  \n\n本附录规定了紫外光固化木器漆所采用的枫木面三夹板及其涂漆前表面处理程序。  \n\n2.试板  \n\n（1）材料试板含水率低于 $12\\%$ （按GB/T1931测试)，枫木面要求平整、光滑、无油污、无节疤拼缝和其他缺陷，纹理应与板的长度方向一致。试板厚度为 $\\mathbf{2.5{\\sim}4.0m m}$ ，试板的其他尺寸应符合试验方法的规定。  \n\n（2）试板表面处理应使用试板的枫木面作涂装表面。用干布擦去试板上的灰尘，用$0^{\\#}$ 砂布或 $200^{\\sharp}$ 水砂纸按GB/T9271—1988中3.4规定的操作程序将试板打磨平整。用干布将试板两面及边缘的灰尘擦净，置于温度 $(23\\pm2)^{\\circ}\\mathrm{C}$ 和相对湿度（ $(50\\pm5)\\%$ 的环境中存放一周以上。使用试板前，应将板面灰尘擦净。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 794,
+        "chunk": "# 附录B 涂布量的测定",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 795,
+        "chunk": "# 1.要求  \n\n本附录规定了紫外光固化木器漆涂布量（以干膜计）测定方法。  \n\n2.底漆涂布量的测定  \n\n（1）使用按附录A规定处理且称量的试板。  \n（2）按本标准规定进行漆膜制备。  \n（3）称量涂过漆且经过干燥的试板，计算出每平方米干膜的质量，即涂布量！ $\\scriptstyle({\\mathbf{g}}/{\\mathbf{m}}^{2}$ )。  \n\n3.复合层涂布量的测定  \n\n（1）使用按附录A规定处理且称量的试板。（2）按本标准规定进行两层底漆漆膜的制备并打磨。（3）称量涂过底漆且经过干燥和打磨的试板，计算出每平方米干漆膜的质量，即为底漆的涂布量 $\\scriptstyle(\\mathbf{g}/\\mathbf{m}^{2}$ )。（4）按本标准规定在制备好的底漆漆膜上制备面漆漆膜。（5）称量试板，计算出每平方米面漆于漆膜的质量，即为面漆的涂布量 $\\scriptstyle(\\mathbf{g}/\\mathbf{m}^{2}$ )。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 796,
+        "chunk": "# 二、印制板用阻焊剂（SJ/T10309—1992)  \n\n本标准规定了印制板用阻焊剂的通用性能、检验方法及验收、包装和贮存等要求。本标准适用于印制板用各类阻焊剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 797,
+        "chunk": "# 1.分类和表示  \n\n（1）按成像方式分类和表示网印成像型用“S”表示；液态光致成像型用“L”表示；干膜光致成像型用“D”表示。  \n\n（2）按工艺加工特点分类和表示网印成像型阻焊剂按固化方式分为光固型用“11”表示，热固型用“12”表示；液态光致成像型阻焊剂按涂布方式分为网印型用“21”表示，流布型用“22”表示；干膜光致成像型按显影剂分为水溶性用“31”表示，半水溶性用“32”表示，溶剂性用“33”表示。  \n\n(3）阻焊剂颜色的表示本色（NAT)，黑色（BLK)，红色（RED)，橙色（ORG)，黄色（YEL)，绿色（GRN，优选)，蓝色（BLU，优选)，白色（WHT)。  \n\n（4）阻焊剂型号的表示 生产单位的阻焊剂型号用四位阿拉伯数字表示。  \n\n（5）阻焊剂名称的表示方法应由五组符号表示，第一组表示成像方式，第二组“”为连字符，第三组表示加工特点，第四组表示颜色，第五组表示生产单位的阻焊剂型号。  \n\n![](images/5e0e75f662bcae0cab34fdba9a1fa11c9bea4d63bb2762823981a56452962322.jpg)  \n\n2.技术要求和测试方法见附表 $6\\mathrm{-}3\\sim$ 附表6-8。  \n\n附表6-2阻焊剂固化前后的性能检验   \n\n\n<html><body><table><tr><td>检测 名称</td><td>项目名称</td><td>技术要求</td><td>测试方法</td></tr><tr><td rowspan=\"7\">固化 前的 性能 检验</td><td>颜色</td><td>均匀一致，并符合有关规范</td><td>目测或3倍放大镜直观检查，10倍放大 方法为仲裁方法</td></tr><tr><td>外观</td><td>网印型和液态光致成像型阻焊剂流动性应一致，无起 皮、无沉淀和无凝胶等现象。干膜光致成像型阻焊剂厚 度应均匀一致，应无针孔、皱折、粘连、转移等现象</td><td>目测或3倍放大镜直观检查，10倍放大 方法为仲裁方法</td></tr><tr><td>黏度</td><td>网印型和液态光致成像型阻焊剂黏度2.0～10.0Pa·s (25℃)</td><td>按GB5547在25℃下检测</td></tr><tr><td>细度</td><td>网印型和液态光致成像型阻焊剂不大于20μm</td><td>按GB6753.1规定检测，取三个试样的 最大值作为细度值</td></tr><tr><td>网印性</td><td>漏印性好，涂层应无气泡，针孔、粘网和飞白等现象，渗 展不得影响使用 线宽和间距等级为1级0.2mm；2级，0.3mm；3方法为仲裁方法</td><td>目测或3倍放大镜直观检查，10倍放大</td></tr><tr><td>光致成像性</td><td>级，0.4mm 应按有关规范规定</td><td>按有关规范规定</td></tr><tr><td>干膜尺寸</td><td>干膜光致成像型阻焊剂厚度、宽度均应符合有关规范</td><td>按有关规范规定的测量方法测定，宽度 可用直尺测量，测量精度1mm</td></tr><tr><td rowspan=\"6\">固化 后的 性能 检验</td><td>固化后外观</td><td>应呈现均匀一致，不出现发黏、起泡、分层、外表变色和 开裂等现象</td><td>目测或3倍放大镜直观检查，10倍放大 方法为仲裁方法</td></tr><tr><td>铅笔硬度</td><td>刚性印制板基材或铜箔表面上固化的阻焊膜3H 挠性印制板基材或铜箔表面上固化的阻焊膜2H</td><td>按GB6739规定检测</td></tr><tr><td>附着力</td><td>刚性印制板：浮焊前，划格法试验(1mm)，胶带粘后，不 应有阻焊膜粘附现象； 浮焊后，用胶带粘后，各种基底材料上的阻焊膜脱落百后，阻焊膜按GB4677.2用胶带测试 分数应不超过附表6-4规定 显示出分离、破裂或从基材、导线上分层现象 挠性印制板：经25个周期弯折后，固化的阻焊膜不应挠曲疲劳强度的方法分别弯曲25个周</td><td>浮焊前，阻焊膜按GB9286划格，间距 1mm，再按GB4677.2用胶带测试浮焊 挠性印制板按GB/T13557第4章测试 期，弯曲内径3mm</td></tr><tr><td>阻焊性</td><td>阻焊膜上不得沾锡</td><td>按GB4677.11中方法2浮焊法进行浮 焊试验</td></tr><tr><td>绝缘电阻</td><td>在正常的试验大气条件下，最小绝缘电阻应不小于1× 100Ω 在按附表6-5规定的潮热试验条件试验，并经恢复后，</td><td>正常试验大气条件下测定固化阻焊膜绝 缘电阻，应按GB4677.1进行。潮热试验 后绝缘电阻，取出1～2h，按GB4677.1</td></tr><tr><td>耐化学性</td><td>最小绝缘电阻应不小于1×10°Ω 按规定条件试验时，固化后的阻焊膜应不显现出溶胀、 表面粗糙、厚度变化、气泡或变色等损坏现象。</td><td>进行 将试样按附表6-6规定分别在各种试剂 中浸泡，取出后采用目测或3倍放大镜直 观检查</td></tr></table></body></html>  \n\n附表6-3阻焊剂的周期检验   \n\n\n<html><body><table><tr><td>项目名称</td><td>技术要求</td><td>测试方法</td></tr><tr><td>高低温循环</td><td>各种基体材料上固化的阻焊膜，按附表6-7 规定的高低温循环试验条件试验后，阻焊剂 应不出现分层、起泡等现象</td><td>按附表6-5规定的高低温循环试验条件和GB 2423.22的“一、试验Na\"进行高低温循环试验，检查 试样</td></tr><tr><td>绝缘电阻</td><td>固化的阻焊膜经附表6-5规定的潮热试验 后，经恢复最小绝缘电阻应不小于1×10°Ω</td><td>按附表6-5规定的潮热试验条件下，按GB2423.3进 行试验，取出恢复1～2h后，按GB4677.1进行测试[测 试电压500V(DC)]</td></tr><tr><td>击穿强度</td><td>固化的阻焊膜的击穿强度不小于直流电压 20kV/mm</td><td>先按GB4677.8测量固化后阻焊膜的厚度，精确到 0.0020mm。采用至少能容纳10kV的直流高压装置， 将电板放在试样尺寸为100mm×100mm的阻焊膜的 中部，接好试验电路，接通电源，以500V/s速率升压， 直至击穿。击穿强度应按下式计算： 式中E——击穿强度，kV/mm; U—击穿电压,kV; E=U</td></tr><tr><td>阻燃性</td><td>固化的阻焊膜不应使覆有阻焊膜的印制板 阻燃性能下降一级</td><td>8——阻焊膜厚度，mm 应按GB4722中的垂直燃烧法进行</td></tr><tr><td>防霉性</td><td>固化后的阻焊膜应无支持生物生长的营养 成分或不因生物生长而变质</td><td>应按GB2423.16试验进行，取出后目测阻焊膜外观</td></tr><tr><td></td><td>按试验条件，印制板的阻焊膜应无粉化、龟 耐湿性(老化试验)裂、气泡和溶胀等现象。耐湿性的等级应符 合附表6-8的规定。</td><td>将饱和硫酸钾水溶液（每100mL蒸馏水中约35g硫 酸钾)倒入干燥器陶瓷板下，干燥器相对湿度不超过 98%，将试样垂直放在陶瓷板上（互不接触），用硅油涂 抹干燥器盖沿，封盖干燥器，最后将干燥器放人按附表 6-8选定等级温度的试验烘箱中放置规定的时间，取出 后，目测阻焊膜外观</td></tr></table></body></html>  \n\n附表6-4阻焊膜经浮焊后在刚性印制板上的附着力  \n\n\n<html><body><table><tr><td rowspan=\"2\">基底材料</td><td colspan=\"4\">允许阻焊膜脱落的最大百分数/%</td></tr><tr><td>1级</td><td>2级</td><td>3级</td><td></td></tr><tr><td>裸钢 金或镍</td><td>0 5</td><td>2 10</td><td>5 25 5</td><td></td></tr></table></body></html>  \n\n附表6-5绝缘电阻的潮湿试验条件  \n\n\n<html><body><table><tr><td>等级</td><td>温度/℃</td><td>相对湿度/%</td><td>时间/d</td><td>直流偏压/V</td><td></td></tr><tr><td>1</td><td>25,65</td><td>90～98</td><td>7(交变)</td><td>100</td><td></td></tr><tr><td>2</td><td>50</td><td>90~98</td><td>7(恒定)</td><td>100</td><td></td></tr><tr><td>3</td><td>40</td><td>90~98</td><td>4(恒定)</td><td>100</td><td></td></tr></table></body></html>  \n\n附表6-6耐化学性所用试剂和试验条件  \n\n\n<html><body><table><tr><td>化学试剂</td><td>规格</td><td>试验条件</td><td>化学试剂</td><td>规格</td><td>试验条件</td></tr><tr><td>盐酸</td><td>10%(体积分数)，化学纯</td><td>室温，60min</td><td>三氯乙烯</td><td>化学纯</td><td>煮沸1min或室温，60min</td></tr><tr><td>氢氧化钠</td><td>5%(质量分数)，化学纯</td><td>室温，60min</td><td>乙醇</td><td>化学纯</td><td>室温，60min</td></tr></table></body></html>  \n\n附表6-7高低温循环试验条件  \n\n\n<html><body><table><tr><td rowspan=\"2\">等级</td><td colspan=\"2\">低温</td><td colspan=\"2\">高温</td><td>循环次数</td></tr><tr><td>温度/C</td><td>时间/min</td><td>温度/℃</td><td>时间/min</td><td>/次</td></tr><tr><td>1</td><td>-65</td><td>30</td><td>十125</td><td>30</td><td>100</td></tr><tr><td>2</td><td>-40</td><td>30</td><td>+125</td><td>30</td><td>100</td></tr><tr><td>3</td><td></td><td colspan=\"4\">不要求</td></tr></table></body></html>  \n\n附表6-8耐湿性等级  \n\n\n<html><body><table><tr><td>等级</td><td>温度/℃</td><td>相对湿度/%</td><td>时间/d</td></tr><tr><td>1</td><td>97</td><td>90~98</td><td>28</td></tr><tr><td>2</td><td>85</td><td>90~98</td><td>7</td></tr><tr><td>3</td><td>40</td><td>90～98</td><td>4</td></tr></table></body></html>  \n\n3.检验规则  \n\n（1）验收检验包括固化前的性能检验和固化后的性能检验。  \n$\\textcircled{1}$ 固化前的性能检验检验项目及其合格质量水平AQL应按附表6-9的规定。  \n\n附表6-9固化前的性能检验的AQL  \n\n\n<html><body><table><tr><td>项目名称</td><td>每样本单位试样数/个</td><td>AQL (每百单位产品不合格数)</td></tr><tr><td>颜色</td><td>1</td><td>4.0</td></tr><tr><td>外观</td><td>1</td><td>4.0</td></tr><tr><td>黏度</td><td>2</td><td>4.0</td></tr><tr><td>细度</td><td>3</td><td>2.5</td></tr><tr><td>网印性</td><td>2</td><td>2.5</td></tr><tr><td>光致成像性</td><td>2</td><td>2.5</td></tr><tr><td>干膜尺寸</td><td>１</td><td>4.0</td></tr></table></body></html>  \n\n如果固化前的性能检验有一项不合格，应拒收。拒收后检验严格度的转移规则应按GB2828的规定。  \n\n$\\textcircled{2}$ 固化后的性能检验检验项目及其合格质量水平AQL应按附表6-10 的规定。  \n\n附表6-10 固化后的性能检验的AQL   \n\n\n<html><body><table><tr><td>项目名称</td><td>AQL (每百单位产品不合格数)</td><td>项目名称</td><td>AQL （每百单位产品不合格数）</td></tr><tr><td>固化后外观</td><td>4.0</td><td>阻焊性</td><td>1.0</td></tr><tr><td>铅笔硬度</td><td>2.5</td><td>绝缘电阻</td><td>1.0</td></tr><tr><td>附着力</td><td>1.0</td><td>耐化学性</td><td>2.5</td></tr></table></body></html>  \n\n如果固化后的性能检验有一项不合格，应拒收。拒收后的检验严格度的转移规则应按GB2828的4.6.3条规定。  \n\n（2）周期检验当阻焊剂生产厂更改材料或工艺时，亦应作周期检验。在检验结果得出之前，不影响已通过固化前和固化后性能检验的产品交付，如果检验结果不符合要求，则按不合格的处理。  \n\n周期检验应按附表6-11规定。  \n\n附表6-11 周期检验规定  \n\n\n<html><body><table><tr><td>项目名称</td><td>检验周期/月</td><td>项目名称</td><td>检验周期/月</td></tr><tr><td>高低温循环</td><td>6</td><td>阻燃性</td><td>6</td></tr><tr><td>绝缘电阻</td><td>3</td><td>防霉性</td><td>改变成分时</td></tr><tr><td>击穿强度</td><td>6</td><td>耐湿性</td><td>6</td></tr></table></body></html>  \n\n如果周期检验中样品有一项性能不合格，则周期检验不合格。供货方应停止产品的交收检验，并应对材料和工艺采取改进措施。改进后，应在更多的试样上重复作周期检验全部性能试验，只有当周期检验全部合格时，才能恢复对固化前和固化后的性能检验。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 798,
+        "chunk": "# 4.包装、运输和贮存  \n\n（1）包装阻焊剂应装人不影响其性能和不透光的容器中，并密封，不得有渗漏痕迹。每个容器上应标明制造厂名、商标、阻焊剂名称、生产日期、批号、质量或规格、有效日期、检验合格证等。  \n\n（2）运输阻焊剂若为易燃品，则应按GB190 的图与规定在外包装上注明“易燃物品”字样及等极标志。运输途中应防止日晒、雨淋和避热。  \n\n（3）贮存阻焊剂应在 $30^{\\circ}\\mathrm{C}$ 以下避光阴凉处保存。贮存寿命从生产日算起应至少半年，性能仍符合要求。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 799,
+        "chunk": "# 附录7 光固化常用名词英文及英文缩写  \n\nAbrasion   \nABS Acrylonitrile butadiene styrene   \nAcid modified   \nAcrylated acrylic oligomer   \nAdditive   \nAdhesion   \nAdhesive   \nAliphalic   \nAlkali develop   \nalpha amino ketone   \nalpha hydroxy ketone   \nAmine acrylate   \nAmine modified   \nAmine synergist  \n\n划伤、擦伤丙烯晴-丁二烯-苯乙烯三元共聚物酸改性丙烯酸酯化聚丙烯酸酯2 助剂、添加剂附着力胶黏剂脂肪族碱显影$a-$ 氨基酮$a$ 羟基酮氨基丙烯酸酯，活性胺胺改性胺增感剂，胺促进剂  \n\n<html><body><table><tr><td>Antioxidant</td><td>抗氧化剂 抗静电剂</td></tr><tr><td>Anti-static agent</td><td></td></tr><tr><td>Aromatic</td><td>芳香族</td></tr><tr><td>Aryldiazo salt</td><td>芳香族重氮盐</td></tr><tr><td>Aryl ferrocenium salt</td><td>芳香族茂铁盐</td></tr><tr><td>Automotive paint (coating)</td><td>汽车漆</td></tr><tr><td>BA Butyl acrylate</td><td>丙烯酸丁酯</td></tr><tr><td colspan=\"2\">BAPO Bis-(2、6dimethoxy-benzoyl)-phenyl phosphine oxide</td></tr><tr><td></td><td>二（2,6-二甲氧基苯甲酰基）苯基麟化氧，819</td></tr><tr><td>BBE Benzoin butyl ether</td><td>安息香丁醚</td></tr><tr><td>BDDA Butanediol diacrylate</td><td>丁二醇二丙烯酸酯</td></tr><tr><td>BD-DVD Blue ray-digital versatile disc</td><td>蓝光DVD</td></tr><tr><td>BDK Benzil dimethyl ketal</td><td>安息香双甲醚，651</td></tr><tr><td>BE Benzoin ether</td><td>安息香醚</td></tr><tr><td>BEE Benzoin ethyl ether</td><td>安息香乙醚</td></tr><tr><td>Benzil</td><td>苯偶酰，联苯甲酰</td></tr><tr><td>Benzoil</td><td>苯偶姻，安息香</td></tr><tr><td>Benzoylformate</td><td>苯甲酰甲酸酯</td></tr><tr><td>Bis-GMA Bisphenal A glycidyl dimethylacrylate</td><td>双酚A双甲基丙烯酸缩水甘油酯</td></tr><tr><td>BMS 4-Benzoyl-4'methyldiphenylsulfide</td><td>4-苯甲酰基-4'-甲基二苯硫醚</td></tr><tr><td>BP Benzophenone</td><td>二苯甲酮</td></tr><tr><td>Bronsted acid</td><td>超强质子酸，布朗斯特酸</td></tr><tr><td>BUM Build-up multilayer printed loard</td><td>积层多层板</td></tr><tr><td>CAD Computer aided design</td><td>计算机辅助设计</td></tr><tr><td>Car-refinish</td><td>汽车修补漆</td></tr><tr><td>Catalyst</td><td>催化剂</td></tr><tr><td>Cation</td><td>阳离子</td></tr><tr><td>CCD Charge coupled device</td><td>电荷耦合器</td></tr><tr><td>CCL Copper Clad laminate</td><td>覆铜板</td></tr><tr><td>CD Compact disc</td><td>光盘，光碟</td></tr><tr><td>CD-R Compact disc recordatle</td><td>一次写人光盘</td></tr><tr><td>CD-ROM Compact disc read only memory</td><td>只读光盘</td></tr><tr><td>CD-RW Compact disc rewritable</td><td>可擦写光盘</td></tr><tr><td>Chlorinaled polypropylene</td><td>氯化聚丙烯</td></tr><tr><td>CHVE Cyclohexanedimethanol divinylether</td><td>环已烷二甲醇基-二乙烯基醚</td></tr><tr><td>CMOS Complimentory metal oxide semiconductor</td><td>互补性金属氧化物半导体</td></tr><tr><td>Coating</td><td>涂料</td></tr><tr><td>Colour paste</td><td>色浆</td></tr><tr><td>Conformal coating</td><td>保型涂料</td></tr><tr><td>Coupling agent</td><td>偶联剂</td></tr><tr><td>CPTX 1-chloro-4-propoxy thioxanthone</td><td>1-氯-4-丙氧基硫杂葱酮</td></tr><tr><td>CPU Central processing unit</td><td>中央处理器</td></tr></table></body></html>  \n\nCQ Camenthol quinone 樟脑，菠酮 CRT Cathode ray tule 阴极射线管 CTC Charge transfer complex 电荷转移复合物 CTCP Computer to conventional plate 传统版材上计算机直接制版 CTP Computer to plate 计算机直接制版 CTX Chlorothioxanthone 氯代硫杂葱酮 Cure speed 固化速率 Curing agent 固化剂 Curtain coating 帘涂，淋涂 CVE Cyclohexylvinylether 环已基乙烯基醚 3D Three dimension 三维图形 DBMP 2-Benzyl-2-N,N-dimethylamino-1-(4-morpholino-phenyl)-1-lutanone   \n2-苄基-2-N,N-二甲基-4-吗啡琳苯基酮，369 DDA Bisphenol A diacrylate 双酚A二丙烯酸酯 DDVE Dodecyl vinylether 十二烷基乙烯基醚 DEAP 2,2-Diethoxyacetophenone 2,2-二乙氧基苯乙酮 Defoamer 消泡剂 DEGDA Diethylene glycol diacrylate 二乙二醇二丙烯酸酯 Dendrimer 树枝状聚合物 DETX Diethyl thioxanthone 二乙基硫杂葱酮 DI Digital imaging 数字成像 Diaryliodonium salt 二芳基碘盐 Dilute monomer 稀释单体 Dip coating 浸涂 Dispersant 分散剂 DMB 2-Dimethyl aminoethyl benzoate 苯甲酸二甲氨基乙酯 DMEA Dimethyl ethanolamine 二甲基乙醇胺 DMPA 2,2-Dimethoxy-2-phenyl acetophenone 2,2-二甲氧基-2-苯基苯乙酮，651 DMPT N,N-Dimethyl-para-toluidine 对二甲氨基甲苯 双季戊四醇六丙烯酸酯 DPEHA Dipentaerythrital hexaacrylate   \nDPEPA Dipentaerythrital pentaacrylate 双季戊四醇五丙烯酸酯 DPGDA Dipropylene glycol diacrylate 二丙二醇二丙烯酸酯 DSB Double sided printed board 双面印制板 DTMPTA Ditrimethylolpropane tetraacrylate 双三羟甲基丙烷四丙烯酸酯 双重固化 Dual cure   \nDVD Digital versatile disc DVD DVD-R Digital versatile disc-recordable 可写人DVD DVD-ROM Digital versatile disc-read only memory 只读DVD DVD-RW Digital versatile disc-rewritable 可多次写人DVD DVE-3 Triethylene glycol divinylether 三乙二醇二乙烯基醚 Dye 染料 FA Fnovv acrvlate 环氧丙烯酸酯  \n\nEB Electronic team 电子束 ECA Bis-(3,4-epoxycyclohexyl) adipate 二-(3,4-环氧环已基）已二酸酯 ECC 3, 4-Epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate 3,4-环氧环已基甲酸-3,4-环氧环已基甲酯 ED Electrodeposite 电沉积 EDAB Ethyl-para-N,N-dimethylamino lenzoate 对二甲氨基苯甲酸乙酯 EE Epoxy equivalent 环氧当量 EHA 2-Ethyl hexyl acrylate 丙烯酸2-乙基已酯，丙烯酸异辛酯 EHA 2-Ethyl hexyl $\\pmb{\\rho}$ dimethylaminolenzoate 对-二甲氨基苯甲酸-2-乙基己酯 EHVE Ethyl hexye vinylether 乙基己基乙烯基醚 EI Epoxy index 环氧指数 EL Electro luminescence 电致发光 Electron accelerator (generator) 电子加速器 Elongation 伸长率 EMK 4,4-Bis-(diethylamino)-benzophenone 四乙基米酮 Emulsifier 乳化剂 EOBPADA Ethoxy bisphenol A dicrylate 乙氧基双酚A二丙烯酸酯 EOEOEA 2(2-Ethoxyethoxy) ethyl acrylate 2(2-乙氧基乙氧基）乙基丙烯酸酯 EOTMPTA Ethoxylated trimethylol propane triacrylate 乙氧基三羟甲基丙烷三丙烯酸酯 Epoxidiged soy bean oil acrylate 环氧大豆油丙烯酸酯 EPD Ethyl-4-dimethylamino-benzoate 4-二甲氨基苯甲酸乙酯 Epoxy resin 环氧树脂 ES Excited state 激发态 Etch resist (ink) 抗蚀油墨 EV Epoxy value 环氧值 Excimer 激基缔合物 Exciplex 激基复合物 FA Epoxy novolac acrylate 酚醛环氧丙烯酸酯 Filler 填料 Fineness 细度 Flash point 丙点 Flat 亚光，平光 Flexible printed board 挠性印制板 Flexographic printing 柔印 Flowing 流平性 FPD Flatbed plate display 平板显示器 Functional monomer 功能性单体 GA Glycidyl acrylate 丙烯酸缩水甘油酯 Glossy 光泽 GMA Glyciclyl methacrylate 甲基丙烯酸缩水甘油酯 GPTA Glyceryl propoxy triacrylate 丙氧基甘油三丙烯酸酯 Gravure printing 凹印",
+        "category": " References"
+    },
+    {
+        "id": 800,
+        "chunk": "#  \n\nGRP Glass reinforced plastics 玻璃纤维增强塑料 GS Ground state 基态 Hardness 硬度 HCPK 1-Hydroxy-l-cyclohexyl-phenyl-ketone 1-羟基-1-环己基苯基甲酮，184 HDDA Hexandiol diacrylate 己二醇二丙烯酸酯 HDI 1,6-Hexamethylene diisocyanate 六亚甲基二异氰酸酯，己二异氰酸酯 HEA 2-Hydroxy ethyl acrylate 丙烯酸-2-羟基乙酯 HEMA 2-Hydroxy ethyl methacrylate 甲基丙烯酸-2-羟基乙酯 Hiding power 遮盖能力 HF High frequency 高频 HMDI Hydrogenated $^{4,4^{\\prime}}$ -diphenylmethane diisocyanate 二环已基甲烷二异氰酸酯 HMPP 2-Hydroxy-2-methyl-1-phenyl-1-propanone 2-羟基-2-甲基-1-苯基丙酮(1)，1173 HPA 2-Hydroxy propyl acrylate 丙烯酸-2-羟基丙酯 HPMA 2-Hydroxy propyl methacrylate 甲基丙烯酸-2-羟基丙酯 HPML High pressure mercury lamp 高压汞灯 HTBN Hydroxy terminated butadliene 端羟基-1,2-聚丁二烯 Hybrid 杂化 Hybrid ink 混合型油墨 Hyperbranched polymer 超支化聚合物 IBOA Isobomyl acrylate 丙烯酸异冰片酯 IBOMA Isobomyl methacrylate 甲基丙烯酸异冰片酯 IC Integrated circuit 集成电路 Inhibitor 阻聚剂 Intaglio printing 凹印 IPDI 3-Isocyanatemethyl-3,5,5-trimethylcyclohexylisocyanate 3-异氰酸甲酯-3,5,5-三甲基环已基异氰酸酯，异佛尔酮二异氰酸酯 IR Infrared 红外线 ITX Isopropyl thioxanthone 2-异丙基硫杂葱酮 Jet printing 喷墨印刷 Ketyl 炭游基 LA Lauryl acrylate 丙烯酸月桂酯 Laser 激光 Laser holographic lithography 激光全息 Latent image staliliger 潜影稳定剂 LBP Liquid benzophenone 液体二苯甲酮 LCD Liquid crystal display 液晶 LD Lethal dose 致死剂量 LD Laser disc 镭射影碟 $\\mathrm{LD}_{50}$ Lethal dose-50 $50\\%$ 死亡率剂量，半致死剂量 LDI Laser direct image 激光直接成像 LDPE Low density polyethylene 低密度聚乙烯 LED Light emitted diode 发光二极管 Letterpress printing 凸印  \n\nLewis acid 路易斯酸 LF Low frequency 低频 Light stabilizer 光稳定剂 Lime plaster 腻子 Lithographic printing 胶印 Low odour 低气味 LPIER Liquid photoimageable etch resist 液态光成像抗蚀油墨 LPISM Liquid photoimageable solder mask 液态光成像阻焊油墨 LPML Low pressure mercury lamp 低压汞灯 LSI Large scale integrated circuit 大规模集成电路 LSL Laser stereolithography 激光立体成型 Mask 掩膜 MAPO Bis-(2,6-dimethoxy benzoyl)-2,4,4-trimethyl pentyl phosphine oxide   \n二(2,6-二甲氧基苯甲酰基)-2,4,4-三甲基戊基麟化氧 Marking ink 字符油墨 Matt 亚光，平光 MBB Methyl-o-Benzoylbenzoate 邻-苯甲酰基苯甲酸甲酯 MBF Methyl benzoylformate 苯甲酰甲酸甲酯 MBP 4-Methyl benzophenone 4-甲基二苯甲酮 MDEA Methyl diethanolamine 甲基二乙醇胺 MDF Medium density fibreboard 中密度板 MDI Diphenylmethane diisocyanate 二苯基甲烷二异氰酸酯 MEAB4,4-(Bis $N$ methyl-N-ethyl amino)benzophenone $_{4,4^{\\prime}}$ -二甲乙氨基二苯甲酮 Melamine 三聚氰胺，蜜胺 MFA Multifunctional acrylate 多官能度丙烯酸酯 Microgel 微凝胶 MLB Multilayer printed Board 多层印制板 MK Michler's ketone 米酮 MMMP 2-Methyl-1-[4(methylthio)phenyl]-2-morpholino propanone(1)   \n2-甲基-1-(4-甲硫基苯基)-2-吗啡啉丙酮,907 MO Magneto optical 磁光盘 Monofunctional monomer 单官能度单体 Monomer 单体 MOS Metal oxide semiconductor 金属氧化物半导体 Motorcycles paint 摩托车漆 Moving printing 移印 MW Micro wave 微波 Non-yellowing 耐黄变 nm Nanometre 纳米 NPGDA Neopentyl glycol diacrylate 新戊二醇二丙烯酸酯 NVP N-vinyl pyrralidone N-乙烯基吡咯烷酮 ODA Octyldecyl acrylate 丙烯酸辛癸酯 ODAB Octyl-para-N,N-dimethylamino benzoate 对二甲胺基苯甲酸异辛酯  \n\nOdour free 无气味 Offset printing 胶印 OLED Organic light emitting diode 有机发光二极管 Oligomer 低聚物 Optical filer 光纤 Optical filer calle 光缆 PA polyacrylate 聚丙烯酸酯 PAA polyacrylic acid 聚丙烯酸 PAG photoacid generator 光致产酸剂 Paint 涂料 PBG photobase generator 光致产碱剂 PBZ 4-phenylbenzophenone 4-苯基二苯甲酮 PC polycarbonate 聚碳酸酯 PCB printed circuit loard 印制电路板 PDDA phthalic diglycol diacrylate 邻苯二甲酸二乙二醇二丙烯酸酯 PDP plasma display panel 等离子体显示器 PE polyethylene 聚乙烯 PEA polyester acrylate 聚酯丙烯酸酯 2-PEA(POEA)2-phenoxyethyl acrylate 丙烯酸-2-苯氧基乙酯 pencil hardness 铅笔硬度 PEG polyethylene glycol 聚乙二醇 PEGDA polyethylene glycol dicrylate 聚乙二醇二丙烯酸酯 PET polyethylene glycol terephthalate 聚对苯二甲酸乙二醇酯,涤纶 PETA pentaerythritol triacrylate 季戊四醇三丙烯酸酯 Photon 光子 Photonic crystale 光子晶体 Photopolymer 感光性高分子，感光性树脂 Photoresist 光致抗蚀剂，光刻胶 Photo sensitiger 光敏剂 PI photo initiator 光引发剂 PI polyimide 聚酰亚胺 Pigment 颜料 PIl initial period index 初期皮肤刺激指数 PMAA polymethylacrylic acid 聚甲基丙烯酸 PMMA polymethyl methacrylate 聚甲基丙烯酸甲酯,有机玻璃 PO phosphine oxide 氧化麟 Polyester 聚酯 Polyether 聚醚 PONPGDA propoxylated neopentyl glycol diacrylate 丙氧基新戊二醇二丙烯酸酯 POTMPTA propoxylated trimethylol propane triacrylate 丙氧基三羟甲基丙烷三丙烯酸酯 Powder coating 粉末涂料 PP Polypropylene 聚丙烯 PPG Polypropylene glycol 聚丙二醇  \n\nPrepolymers   \nPrimer coating   \nPrinting ink   \nPS polystyrene   \nPS presensitiged plate   \nPSA pressure sensitive adhesive   \nPSPI photosensitive polyimide   \nPTFE polytetrafluoroethylene   \nPU polyurethane   \nPUA polyurethane acrylate   \nPutty   \nPVA polyvinyl alcohol   \nPVAc polyvinyl acetate   \nPVC polyvinyl chloride   \nPVC pigment volume concentration   \nPVDC polyvinylidene chloride  \n\n损来伪底漆印刷油墨聚苯乙烯预涂感光版，PS版压敏胶光敏聚酰亚胺聚四氟乙烯聚氨酯聚氨酯丙烯酸酯腻子聚乙烯醇聚醋酸乙烯酯聚氯乙烯颜料体积浓度聚偏二氯乙烯反应性稀释剂重涂修补漆离型剂凸印树脂树脂基质无线射频识别，电子标签刚性印制板辊涂快速成型制造丙烯酸硬脂酸酯，丙烯酸十八酯打磨耐刮擦性网印，丝印密封胶抗剪切强度保质期移印网印，丝印立体光刻表面贴(组)装技术阻焊油墨溶解抑制剂溶剂旋涂，甩涂喷涂  \n\nReactive diluent   \nRecoat   \nRefinish coating   \nRelease adhesive   \nRelief printing   \nResin   \nResin matrix   \nRFID radio frequency identification   \nRigid printed loard   \nRoller coating   \n$\\mathtt{R P}\\&\\mathbf{M}$ rapid prototyping and manufacturing   \nSA stearyl acrylate   \nSanding   \nScratch resisting   \nScreen printing   \nSealants   \nShear strength   \nShelf life   \nShift printing   \nSilk printing   \nSL stereolithography   \nSMT surface mount technology   \nSoldering ink   \nSolution inhibitor   \nSolvent   \nSpin coating   \nSpray coating  \n\nSSB single sided printed board 单面印制板 ST Styrene 苯乙烯 Surface preparation 表面处理 Surfactants 表面活性剂 TDI Tolylene diisocyanate 甲苯二异氰酸酯 TDS Technocal data sheet 技术说明书 TEA Triethylamine 三乙胺 TEGDA Triethylene glycol diacrylate 三乙二醇二丙烯酸酯 TEOA Triethanolamine 三乙醇胺 Tensile strength 抗张强度 TEPO 2,4,6-Trimethyl-benzoyl-ethoxyl phenyl phosphine oxide 2,4,6-三甲基苯甲酰基-乙氧基-苯基麟化氧 TFT Thin film transistor 薄膜晶体管 $T_{\\mathrm{g}}$ Glass(transition)temperature 玻璃化(转变)温度 THFA Tetrahydrofurfuryl acrylate 丙烯酸四氢呋喃酯 Thinner 稀释剂 Thixotropy 触变性 TMBP 2,4,6-Trimethyl benzophenone 2,4,6-三甲基二苯甲酮 Top coating 面漆 Touch dry 表干，指触干 TPO 2,4,6-Trimethyl-benzoyl diphenyl phosphine Oxide 2,4,6-三甲基苯甲酰基-二苯基麟化氧 Transparent 透明 Triarylsulfonium salt 三芳基硫盐 Two pack 双组分 UDMA Urethane dimethylacrylate 氨基甲酸双甲基丙烯酸酯 UHF Ultra high frequency 超高频 UPE Unsaturated polyester 不饱和聚酯 UV Ultraviolet 紫外光 UV absorber 紫外吸收剂 Varnish 清漆，上光油 VE Vinyl ether 乙烯基醚 VFD Vacuum fluorescence display 真空荧光显示屏 Viscosity 黏度 Visible light 可见光 VLSI Very large scale integrated circuit 超大规模集成电路 VOC Volatile organic content 挥发性有机物 Volume Shrinkage 体积收缩 Volume solid 固含量，固体分 Water base(Borne) 水性 Water develop 水显影 Water proof 防水 Weatherabilily 耐候性 Wetting agent 润湿剂  \n\n8瓷   \n\n\n<html><body><table><tr><td rowspan=\"2\">公司</td><td rowspan=\"2\"></td><td rowspan=\"2\">TMPTA</td><td rowspan=\"2\">TPGDADPGDA</td><td rowspan=\"2\"></td><td rowspan=\"2\">HDDA NPGDA</td><td rowspan=\"2\">PDDA</td><td rowspan=\"2\">PETA</td><td rowspan=\"2\"></td><td rowspan=\"2\">TMPTATPTANPDA</td><td rowspan=\"2\"></td><td rowspan=\"2\">OTA</td><td rowspan=\"2\">GPTA</td><td rowspan=\"2\">HEA </td><td rowspan=\"2\">HMA IOMA</td><td rowspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\">其他</td></tr><tr><td></td><td></td></tr><tr><td>北京东方亚科力化工科技公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>LA、SA、EOEOEA</td></tr><tr><td>天津天骄辐射固化材料公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td>PEGDA、DPHA等</td><td>LA、HA、PEGDA、BO</td></tr><tr><td>天津市化学试剂研究所</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td>DA等</td><td></td></tr><tr><td>天津高科化工公司</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>PETA、BODA</td><td>PEGDA、EO-BPDA</td></tr><tr><td>辽宁奥克集团</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>EO-TMPTMA</td><td></td></tr><tr><td>上海泰禾(集团)公司</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>LA、POEA、BODA</td></tr><tr><td>江苏利田科技公司</td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>PEGDA,TMPTMA等</td></tr><tr><td>江苏三木集团</td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td>√</td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td>TMPTMA等</td><td>BODA、TMPTMA 等</td></tr><tr><td>宜兴宏辉化工公司 常州三龙化工公司</td><td>L</td><td>√</td><td></td><td></td><td></td><td></td><td>√ √</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>江苏银燕化工股份公司</td><td>?</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td></tr><tr><td>无锡金盏助剂厂</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td>√</td><td></td><td></td></tr><tr><td>无锡杨市三联化工厂</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>无锡博尼尔化工公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>无锡万博涂料化工公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>含氟单体</td><td></td></tr><tr><td>常熟三爱富中昊化工新材料</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>含氟单体</td><td></td></tr><tr><td>公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>南通新兴树脂公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>南京大有精细化工公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>TMPTMA</td><td></td></tr><tr><td>上海忠诚精细化工公司</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>池州通达林产化工公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>洞头美利丝油墨涂料公司</td><td><</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n表续  \n\n\n<html><body><table><tr><td rowspan=\"2\">公司</td><td rowspan=\"2\"></td><td rowspan=\"2\">TMPTATPGDA</td><td rowspan=\"2\">DPGDA</td><td rowspan=\"2\">HDDA</td><td rowspan=\"2\">NPGDA</td><td rowspan=\"2\">PDDA</td><td rowspan=\"2\">PETA</td><td rowspan=\"2\"></td><td rowspan=\"2\">TMPTATMOTANPODA</td><td rowspan=\"2\"></td><td rowspan=\"2\">OTA</td><td rowspan=\"2\">GPTA HPA </td><td rowspan=\"2\"></td><td rowspan=\"2\">HPMA OMA</td><td rowspan=\"2\">其他</td><td rowspan=\"2\"></td></tr><tr><td></td></tr><tr><td>岳阳昌德化工实业公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>丙烯酸羟基环己酯、1.2 环己二醇二缩水甘油醚</td></tr><tr><td>江门恒光新材料公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>江门君力化工实业公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>中山千叶合成化工厂</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>恒昌涂料(惠阳)公司</td><td></td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>POEA、EOEOEA、PEG-</td></tr><tr><td>长兴化学材料(珠海)公司</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>DA、BPADA、DPHA、DT- MPTA、MAA酯等</td></tr><tr><td>东莞宏德化工公司</td><td>√</td><td>√</td><td></td><td>√</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>PEGDA、DPHA等</td></tr><tr><td>台湾 Sicchem公司</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>LA、THFA、POEA、EO-</td></tr><tr><td>台湾新力美科技股份公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>EOEA、BPADA等 DTMPTA、DPHA、</td></tr><tr><td>氰特</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>MAA酯、高纯度单体等 LA、SA、EOEOEA、 POEA、THFA、DPHA、</td></tr><tr><td>美国沙多玛(广州)化学公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>MAA酯、高纯度单体等</td></tr><tr><td>美国国际特品公司 美国道化学(中国)投资公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>乙烯基醚阳离子单体 乙烯基醚、环氧阳离子</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td>单体</td><td>LA、SA、POEA、EOEO- EA、BPADA、PEGDA、氧</td></tr><tr><td>日本大阪有机化学公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>杂环、含氟单体等</td><td>POEA、PEGDA、PPG-</td></tr><tr><td>日本新中村化学工业株式会社</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>?</td><td></td><td></td><td></td><td></td><td></td><td></td><td>BPADA、环酯等</td><td>DA、DPHA、MAA酯、</td></tr><tr><td>日本化药株式会社</td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td>></td><td></td><td></td><td>DTMPTA等</td><td>BPADA、DPHA、环酯、</td></tr></table></body></html>  \n\n<html><body><table><tr><td rowspan=\"2\">公司</td><td rowspan=\"2\"></td><td rowspan=\"2\">TMPTATPGDADPGDA HDDA</td><td rowspan=\"2\"></td><td rowspan=\"2\"></td><td rowspan=\"2\">NPGDA</td><td rowspan=\"2\">PDDA</td><td rowspan=\"2\">PETA</td><td rowspan=\"2\">TMPTATMPTANPGDA</td><td rowspan=\"2\"></td><td rowspan=\"2\">OTA</td><td rowspan=\"2\">GPTA</td><td rowspan=\"2\">HPA </td><td rowspan=\"2\">HMA IROMA</td><td rowspan=\"2\"></td><td rowspan=\"2\">其他</td></tr><tr><td></td></tr><tr><td>日本共荣社化学株式会社</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>单体等</td><td>PEGDA、PPGDA、POEA, DPHA、环酯、MAA酯、含氟</td></tr><tr><td>日本油脂株式会社</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>LA、SA、GMA、PEG- DA、PPGDA、MAA酯、</td></tr><tr><td>日本东亚合成株式会社</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>BPADA等 DPHA</td><td></td></tr><tr><td>日本Arakawa化学工业株式 会社</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>BPADA、DPHA</td></tr><tr><td>日本Toagosei化学工业株式 会社</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>PEGDA,PPGDA、POEA、</td></tr><tr><td>张家港东亚迪爱生化学公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>BPADA,DPHA PPGDA、DPHA、DT- MPTA</td></tr><tr><td>韩国美源特殊化工株式会社</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>PEGDA、BPADA、DPHA、</td></tr><tr><td>美国Akcros化学公司</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>DTMPTA 、MAA 酯 DTMPTA</td></tr><tr><td>美国 Performance 化学公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>PEGDA,PPGDA、MAA 酯</td></tr><tr><td>美国Crodamer化学公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>罗地亚公司上海办事处</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>β-CEA</td></tr><tr><td>德国赢创德固赛(中国)投资 公司上海分公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td>MAA 酯</td></tr><tr><td>德国赫斯公司上海办事处</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td><</td><td></td><td>SA</td></tr><tr><td>巴斯夫(中国)公司</td><td></td><td><</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>LA、POEA、BDDA、阳离</td></tr><tr><td>上海科宁油脂化学公司</td><td></td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td>子单体等 PEGDA、高纯度单体等</td></tr><tr><td>达质化学(马亚西亚)公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n6瓷   \n\n\n<html><body><table><tr><td>公司</td><td>EA</td><td>FA</td><td>改性EA芳香族PUA脂肪族PUA</td><td></td><td></td><td>PEA</td><td>AA类</td><td>氨基</td><td>UP</td><td>有机硅</td><td>光成像 活性胺</td><td></td><td>其他</td></tr><tr><td>天津天骄辐射固化材料公司</td><td>√</td><td></td><td></td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>天津市化学试剂研究所</td><td>√</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>鞍山兴业高分子化工公司</td><td>√</td><td></td><td>?</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海高点化工公司</td><td>√</td><td></td><td></td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>水性UV树脂，双重固化树脂</td></tr><tr><td>上海多森化工有限公司 上海雷呈化工公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海泰禾(集团)公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海元邦涂料制造公司</td><td></td><td><</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>江苏三木集团</td><td>√</td><td></td><td>√</td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>南京贸桥化工公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td></tr><tr><td>无锡博强高分子材料科技公司</td><td>√</td><td></td><td></td><td>√</td><td>>：</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td>环氧大豆油</td></tr><tr><td>无锡树脂厂</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>无锡诺克斯化工科技公司</td><td></td><td>?</td><td></td><td></td><td><</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>扬州晨化科技集团公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>水性PUA</td></tr><tr><td>浙江洞头县恒立印刷材料公司</td><td></td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td>环氧大豆油，自引发树脂</td></tr><tr><td>广州宝会树脂公司</td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>广州深兰聚合物公司</td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>自引发树脂、水性UV树脂、</td></tr><tr><td>广州博兴化工科技公司</td><td></td><td></td><td>√</td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>附着力促进树脂</td></tr><tr><td>广州金东有限公司</td><td>√</td><td></td><td></td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td>环氧大豆油，澳化EA</td></tr><tr><td>江门君力化工实业公司</td><td></td><td></td><td></td><td></td><td><</td><td>L</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td>超支化树脂</td></tr><tr><td>江门市制漆厂</td><td></td><td></td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>江门恒光新材料公司 广东同步化工公司</td><td>√</td><td></td><td>√</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td>√</td><td>√</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td>环氧大豆油，水性EA，水性</td></tr><tr><td>中山千叶合成化工厂</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td><</td><td><</td><td></td><td>√</td><td>PUA，超支化树脂，带光敏</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>中山博海精细化工公司</td><td>√</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td><</td><td>√</td><td><</td><td>√</td><td>√</td><td><</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>剂PUA</td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td></table></body></html>  \n\n<html><body><table><tr><td>公司</td><td>EA</td><td>FA</td><td>改性EA芳香族PUA</td><td></td><td>脂肪族PUA</td><td>PEA</td><td>AA类</td><td>氨基</td><td>UP</td><td></td><td>有机硅 光成像 活性胺</td><td></td><td>其他</td></tr><tr><td>中山科田电子材料公司</td><td></td><td></td><td></td><td>√</td><td></td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td>超支化树脂</td></tr><tr><td>佛山市顺德区东阳化工公司</td><td>√</td><td></td><td><</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td></tr><tr><td>佛山市顺德区永大化工实业公司</td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td>环氧大豆油</td><td></td></tr><tr><td>东莞金溢彩树脂实业公司</td><td>√</td><td></td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td>√</td><td></td><td></td><td>√</td><td></td><td>环氧大豆油、超支化树脂</td></tr><tr><td>深圳鼎好光化科技公司</td><td>√</td><td></td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td>√</td><td></td><td>附着力促进树脂</td></tr><tr><td>欧宝迪树脂(深圳)公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>水性PUA、水性AA</td></tr><tr><td>深圳科立孚实业公司</td><td></td><td></td><td></td><td>√</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td>√</td><td></td></tr><tr><td>深圳华信行公司 陕西喜莱坞实业公司</td><td>√</td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>长兴化学材料(珠海)公司</td><td>√</td><td></td><td>√</td><td><</td><td><</td><td>√</td><td><</td><td></td><td></td><td></td><td>√</td><td>√</td><td></td></tr><tr><td>东莞宏德化学工业公司</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td>√</td><td>√</td><td>氯化PEA</td></tr><tr><td>台湾Sicchem</td><td></td><td></td><td></td><td></td><td>√</td><td>L</td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td></tr><tr><td>台湾新力美科技股份公司</td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>台湾力勤实业股份公司</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海奇钛化工科技公司</td><td>√ √</td><td>√</td><td>√</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>德谦(上海)化学公司</td><td>√</td><td></td><td>√</td><td>√ √</td><td>√</td><td></td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>氰特公司</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>阳离子树脂、水性UV树 双固化树脂、UV粉末涂料</td></tr><tr><td></td><td></td><td></td><td></td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td>√</td><td>脂、高纯树脂</td></tr><tr><td>美国Bomar公司 美国亚什兰集团德鲁工业部</td><td></td><td></td><td></td><td><</td><td><</td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td>超支化树脂、自引发树脂</td></tr><tr><td>沙多玛(广州)化学公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td>自引发树脂</td></tr><tr><td></td><td></td><td></td><td><</td><td></td><td></td><td>√</td><td>√</td><td>√</td><td></td><td></td><td>√</td><td><</td><td>聚丁二烯、附着力促进树 超支化树脂</td></tr><tr><td>道化学(中国)投资公司上海分公司 日本大阪有机化学公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>阳离子树脂</td></tr><tr><td>日本合成化学工业株式会社</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>聚丁二烯、氟树脂</td></tr><tr><td>日本Arakawa化学工业株式会社</td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td>水性UV树脂</td></tr><tr><td>日本Toagosei化学工业株式会社</td><td></td><td></td><td>√</td><td><</td><td><</td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td><</td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>日本新中村化学工业株式会社</td><td></td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>超支化树脂</td></tr><tr><td>日本化药株式会社</td><td>√</td><td></td><td></td><td><</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td><</td><td></td><td></td></tr><tr><td>日本共荣社化学株式会社</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>公司</td><td>BP</td><td>651</td><td>1173</td><td>184</td><td>907</td><td>ITX</td><td>TPO</td><td>369</td><td>819</td><td>500</td><td>2959</td><td>硫锚盐</td><td>其他</td></tr><tr><td></td><td></td><td></td><td><</td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td>√</td><td>大分子光引发剂</td></tr><tr><td>北京美力科技发展公司 北京美力精化技术发展公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>EHA、EDB、215等</td></tr><tr><td>天津市化学试剂研究所</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>安息香醚</td></tr><tr><td>天津久日化工公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td>DETX</td><td></td></tr><tr><td>大连三源精细化工公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>辽宁华海兰帆化工科技公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>214、215</td></tr><tr><td>本溪市轻化工研究所</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>214、215</td></tr><tr><td>上海东奇化工公司</td><td></td><td></td><td></td><td>√</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td>√</td><td></td><td>PBZ、BBMB、MBF等</td></tr><tr><td>优缔贸易(上海)公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td>EMK、NPG、TPS、LCV、双咪唑、三嗪类、酯等</td></tr></table></body></html>  \n\nO登   \n\n\n<html><body><table><tr><td>公司</td><td>EA</td><td>FA</td><td>改性EA芳香族PUA</td><td></td><td>脂肪族PUA</td><td>PEA</td><td>AA类</td><td>氨基</td><td>UP</td><td></td><td>有机硅 光成像活性胺</td><td></td><td>其他</td><td></td><td></td></tr><tr><td>日本东亚合成株式会社</td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>日本三菱公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>韩国美源特殊化工株式会社</td><td><</td><td></td><td></td><td>√</td><td></td><td><</td><td></td><td></td><td></td><td>√</td><td></td><td></td><td>水性UV树脂</td><td></td><td></td></tr><tr><td>韩国YooSang化学公司</td><td><</td><td></td><td>√</td><td></td><td></td><td>√ <</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td>水性UV树脂</td><td></td><td></td></tr><tr><td>美国Akcros化学公司</td><td></td><td><</td><td></td><td>√</td><td></td><td>√ <</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>水性UV树脂</td><td></td></tr><tr><td>美国科罗达玛公司</td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td>√ √</td><td></td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td>环氧大豆油，超支化树脂、聚</td><td></td></tr><tr><td>上海科宁油脂化学品公司</td><td>√</td><td></td><td>√</td><td></td><td></td><td>√ √</td><td></td><td></td><td></td><td></td><td></td><td>√</td><td>醚AA</td><td></td><td></td></tr><tr><td>拜耳(中国)有限公司</td><td>√</td><td></td><td></td><td>√</td><td></td><td>√</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td>聚醚AA</td><td>水性UV树脂、双固化树脂、</td><td></td></tr><tr><td>巴斯夫(中国)有限公司</td><td>√</td><td></td><td></td><td>√</td><td><</td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td>聚醚AA</td><td>水性UV树脂、双固化树脂、</td><td></td></tr><tr><td>荷兰帝斯曼利康树脂公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>水性UV树脂</td><td></td></tr><tr><td>意大利盖斯塔夫综合树脂公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>瑞典柏斯托精细化学品公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>超支化树脂</td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>公司</td><td>BP</td><td>651</td><td>1173</td><td>184</td><td>907</td><td>ITX</td><td>TPO</td><td>369</td><td>819</td><td>500</td><td>2959</td><td>硫盐</td><td>其他</td></tr><tr><td>上海泰禾集团公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>南京贸桥化工公司</td><td>√</td><td>√</td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td>DETX、BMS、PBZ、EPD、EHA、MBP、液态 BP</td></tr><tr><td>常州华钛化学股份公司</td><td></td><td>√ √</td><td>√</td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td>√</td><td></td><td>√</td><td></td></tr><tr><td>常州花山化工公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>PBZ、TBP、CIBP、MBZ、BEM</td></tr><tr><td>常州强力电子新材料公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td>DBM、NPG、TPS、LCV、双唑、TPS、HA、</td></tr><tr><td>江阴维宏精细化工公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>宁柏迪化工(江阴)公司 昆山玉山化工厂</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>BDM</td></tr><tr><td>靖江宏泰化工公司</td><td></td><td></td><td></td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td></tr><tr><td>大丰德尔明化工公司</td><td></td><td>√</td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td>苯偶酰、安息香</td></tr><tr><td>大丰三立化工公司</td><td>√ √</td><td>√</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>浙江扬帆精细化工公司</td><td></td><td></td><td></td><td></td><td></td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>浙江德清县美联医药化学公司</td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>DETX、MBF</td></tr><tr><td>杭州佳圆企业集团</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>苯偶酰、安息香、MBF</td></tr><tr><td>海宁光华化工公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>荆门市昱奎化工公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td>二茂钛</td></tr><tr><td>长沙新宇化工实业公司</td><td>√</td><td><</td><td>√</td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td>DETX、EPD、EMA、PBZ、MBP、液态 BP</td></tr><tr><td>兰州长欣精细化工公司</td><td></td><td></td><td></td><td></td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td>DETX</td></tr><tr><td>甘肃金盾化工公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td>L</td><td></td><td></td></tr><tr><td>上海奇钛化工科技公司</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td>EMK、BMS、MBP、LBP、水性光引发剂</td></tr><tr><td>长兴化学工业股份公司</td><td>V</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>氰特公司</td><td></td><td>√</td><td>√</td><td></td><td></td><td>√</td><td><</td><td></td><td></td><td></td><td></td><td></td><td>EPD、EHA</td></tr><tr><td>沙多玛(广州)化学公司 道化学(中国)投资公司上海分公司</td><td></td><td>√</td><td>√</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td>√</td><td>EPD、TZT、KIP 等</td></tr><tr><td>日本化药株式会社</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>DETX、CTX、BMS、EPD、EHA</td></tr><tr><td>韩国美源特殊化工株式会社</td><td>√</td><td></td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>BMS、EPD、EHA、MBP、MBB、MBF、PBZ、CTX 等</td></tr><tr><td>美国大湖公司</td><td></td><td><</td><td></td><td><</td><td></td><td><</td><td><</td><td></td><td></td><td></td><td></td><td></td><td>CTX、DETX、CPTX、EPD、EHA</td></tr><tr><td>巴斯夫(中国)有限公司</td><td></td><td>√</td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td><td>TPO-L</td></tr><tr><td>汽巴精化(中国)公司</td><td></td><td><<</td><td>〈</td><td><</td><td></td><td><<</td><td></td><td>√</td><td></td><td></td><td></td><td>√</td><td></td></tr><tr><td>意大利宁柏迪公司</td><td></td><td>√</td><td>√</td><td>√</td><td></td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td>EHA、EDB、TZT、TZM、KIP、1001等</td></tr></table></body></html>  \n\n<html><body><table><tr><td>公司</td><td>纸张</td><td>木器</td><td>塑料</td><td>PVC</td><td>真空电镀</td><td>摩托车</td><td>家电</td><td>金属</td><td>手机</td><td>石材</td><td>光盘 车灯</td><td></td><td>其他</td><td></td></tr><tr><td>北京力拓达科技公司</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>北京中石阳光科技公司</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>保定乐凯高分子材料科技发展公司 大连锐信新材料开发公司</td><td>√</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>汽车修补漆</td><td></td></tr><tr><td>鞍山兴业高分子化工公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>沈阳西迈涂料化工公司</td><td>√</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>丹东森泽化工厂</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>哈尔滨东风油漆厂</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>威海佳和涂料公司</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>威海东华特种涂料厂</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>威海望岛渔具专用配套总厂</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>威海瀚玉化纺公司</td><td>√</td><td>√</td><td></td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>威海冠盛化工公司</td><td></td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>青岛光科技术公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>青岛丽彩华工贸公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海长悦涂料公司</td><td>.</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>欧美化工(上海)公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>华阳油墨(上海)公司 上海东洋油墨公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海维格拉印刷器材公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>彩皇(上海)精密化学公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海韩盛化工涂料公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>无锡诺克斯化工科技公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>建筑</td><td></td></tr><tr><td>无锡金桥精细油墨公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>无锡胡油墨公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>无锡寿光油墨公司</td><td>√</td><td>√</td><td><</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td>.</td><td></td><td></td><td></td></tr><tr><td>江阴宇维高分子化工公司</td><td></td><td></td><td>√</td><td></td><td></td><td><</td><td></td><td></td><td>」<</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>江阴优利科化工公司</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>公司</td><td>纸张</td><td>木器</td><td>塑料</td><td>PVC</td><td>真空电镀</td><td>摩托车</td><td>家电</td><td>金属</td><td>手机</td><td>石材 光盘</td><td>车灯</td><td></td><td></td><td>其他</td></tr><tr><td>宜兴宏泰化工公司</td><td></td><td></td><td>√</td><td></td><td>√</td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>宜兴万源化工涂料公司</td><td></td><td>√</td><td>√</td><td>√</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>南京祥和轰化工公司</td><td>L</td><td></td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>富士化研(昆山)公司</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>万航科技(苏州)公司</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>苏州明大高分子科技材料公司</td><td></td><td>√</td><td>√</td><td></td><td></td><td><</td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>盐城达隆涂料公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>浙江安瑞森信息材料公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>浙江美浓涂料公司</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>浙江美尔诺油墨公司</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>浙江恒勃塑胶科技公司</td><td></td><td></td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>杭州科望特种油墨公司</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td>陶瓷，玻璃</td><td></td></tr><tr><td>杭州杭华油墨化学公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>浙江永在化工公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上虞佑谦特种材料公司</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>龙游新迪高分子材料公司</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>武汉三亿科技公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>武汉印刷包装材料研究所</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>湖南本安五大新材料公司</td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td><</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>湖南金海化工公司</td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>泉州天益油墨发展公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>广东华润涂料公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>广东嘉宝莉化工公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>广州宏聿涂料公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>广州雷辐科技公司</td><td>L</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>番禺龙珠化工公司</td><td></td><td>√</td><td><</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>顺德现代化工公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>公司</td><td>纸张</td><td>木器</td><td>塑料</td><td>PVC</td><td>真空电镀</td><td>摩托车</td><td>家电 金属</td><td></td><td>手机 石材</td><td>光盘</td><td>车灯</td><td></td><td>其他</td><td></td></tr><tr><td>顺德希贵</td><td></td><td>√</td><td>√</td><td></td><td></td><td>√</td><td></td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>顺德永大化工实业公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>顺德东阳化工公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>中山恒美油墨涂料公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>中山博海精细化工公司</td><td>√</td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>中山中益油墨涂料公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>东莞龙达油墨公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>东莞柏林涂料厂</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>东莞华营油墨公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>深圳美联兴油墨公司</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>深圳仙人掌制漆公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>深圳美丽华油墨涂料公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>深圳正伟化工公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td><</td><td>√</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>深圳海中辉油墨制品公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td>皮革、内外墙、建材</td><td></td></tr><tr><td>珠海东城化工公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td><</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>恒昌涂料(惠阳)公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>成都万盛化工实业公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>绵阳彩馥兰科技公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>陕西新世纪印刷材料公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>广西防城港市韩进化学材料公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>昆山东周涂料工业股份公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>金甲化工企业(中山)公司</td><td></td><td></td><td></td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>韩国三和涂料工业株式会社</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>精工油墨（四会)公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>PPG涂料(天津)公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>公司</td><td>胶印</td><td>网印</td><td>凹印</td><td>柔印</td><td>移印</td><td>凸印</td><td>喷墨</td><td>金属</td><td>玻璃</td><td>光盘 装饰油墨</td><td>水性</td><td></td><td></td><td>其他</td></tr><tr><td>北京大学德力科技公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>防伪墨</td><td></td></tr><tr><td>北京力拓达科技公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>北京丽色达油墨化学科技公司</td><td>√</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td></tr><tr><td>天津天女化工集团股份公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>天津东洋油墨公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>石家庄恒日化工公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>保定乐凯高分子材料科技发展公司 济南色太可油墨公司</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>济南皇冠油墨公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海隆臣实业公司</td><td>√ √</td><td></td><td></td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>华阳油墨(上海)公司</td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>好连金印刷器材贸易(上海)公司 上海文华科贸公司</td><td>√</td><td>√</td><td>√</td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td>金银墨</td><td></td></tr><tr><td>上海捷彩数码喷墨科技公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td>√ √</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海美威喷墨科技公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海优伟油墨涂料公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>通利丝印器材(上海)公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>无锡金桥精细油墨公司</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>无锡大哲油墨公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>无锡春光油墨公司</td><td></td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>无锡胡油墨公司</td><td></td><td>√</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td>√</td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>无锡爱赛雅印刷器材公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td><</td><td></td><td></td><td></td></tr><tr><td>苏州科斯伍德油墨股份公司</td><td></td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>富士化研(昆山)公司</td><td>√</td><td></td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>< <</td><td></td><td></td></tr><tr><td>昆山亿美油墨公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>昆山美丽华油墨涂料公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>昆山新美光油墨公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td></table></body></html>  \n\n<html><body><table><tr><td>公司</td><td>胶印</td><td>网印</td><td>凹印</td><td>柔印</td><td>移印</td><td>凸印</td><td>喷墨</td><td>金属</td><td>玻璃</td><td>光盘</td><td>装饰油墨</td><td>水性</td><td>其他</td><td></td></tr><tr><td>徐州华阳油墨化学公司</td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>浙江永在化工公司</td><td></td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>浙江美浓油墨涂料公司</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>杭州科望特种油墨公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td>√</td><td><</td><td></td><td>√</td><td></td><td>双固化油墨</td><td></td></tr><tr><td>杭州杭华油墨化学公司</td><td>√</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>杭州星桥丝印油墨厂</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>杭州恒基油墨涂料公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td><</td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>杭州诺桑油墨公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>苍南县金贸油墨公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>苍南县友利油墨公司</td><td></td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td><</td><td></td><td></td><td></td></tr><tr><td>缙云感光助剂厂</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td>√</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>宁波大胡印刷器材公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>台州巨皇油墨科技公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>广州雅力诺高分子材料公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>广州旭威精细化工研究院</td><td>√</td><td>√</td><td>L</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>番禺龙珠化工公司</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>深圳百利宝环保油墨公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>深圳海中辉油墨制品公司</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>深圳宝荣盛印刷材料科技公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td><</td><td></td><td></td><td></td></tr><tr><td>深圳深佳恒油墨公司</td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>深圳美联兴油墨公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>深圳美丽华油墨涂料公司</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>深圳美尔诺油墨公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>大兴柯式印刷材料(深圳)公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>中山美嘉印刷器材公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td><</td><td></td><td></td><td></td></tr><tr><td>中山中益油墨涂料公司</td><td></td><td>√</td><td></td><td></td><td>√</td><td><</td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>中山博海精细化工公司</td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>叶氏油墨(中山)公司</td><td></td><td></td><td>：</td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>金甲化工企业(中山)公司</td><td></td><td></td><td>√</td><td>√</td><td></td></table></body></html>  \n\n<html><body><table><tr><td>公司</td><td>胶印</td><td>网印</td><td>凹印</td><td>柔印</td><td>移印</td><td>凸印</td><td>喷墨</td><td>金属</td><td>玻璃</td><td>光盘</td><td>装饰油墨</td><td>水性</td><td></td><td>其他</td></tr><tr><td>东莞贝特利新材料公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>东莞华营油墨公司</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>珠海乐通油墨公司</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>?</td><td></td><td></td><td></td></tr><tr><td>珠海鑫诺美公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>顺德威雅化工公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>恒昌涂料(惠阳)公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>惠州华阳光学技术公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>陕西新世纪印刷材料公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>东周化学工业股份公司</td><td>√</td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>正中印刷器材股份公司昆山分公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td><</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>台湾三皇化工股份公司</td><td></td><td></td><td></td><td>√</td><td></td><td></td><td>√</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>台湾广鑫科技股份公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td>无水胶印</td><td></td></tr><tr><td>美国诺固国际私人公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>美国瀚森特殊化学公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>美国Nazdar亚太区办事处</td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海盛威科油墨公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>富士色丽可油墨公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>日本神户印刷器材株式会社</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>江门新会共荣油墨涂料公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海DIC油墨公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海东洋油墨公司 谷口油墨(烟台)公司</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>彩皇(上海)精密化学公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>息荧光油蚤、番光油盈、</td><td></td></tr><tr><td>精工油墨(四会)公司 迪爱生校资公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>杜比油墨(上海)公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td><</td><td></td><td></td><td></td></tr><tr><td>高氏(广州)涂料公司</td><td></td><td></td><td></td><td></td><td>?</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>金银墨</td><td></td></tr><tr><td>德国迪高油墨东莞经营部</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td>√</td><td></td><td>一<</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>爱卡公司</td><td></td><td></td><td></td><td></td><td></td></table></body></html>  \n\n附录13 印制电路及电子用UV油墨和干膜主要生产企业  \n\n\n<html><body><table><tr><td>公司</td><td>抗蚀</td><td>阻焊</td><td>字符</td><td>光成像抗蚀光成像阻焊</td><td></td><td>干膜</td><td>光盘</td><td>光纤</td></tr><tr><td>北京力拓达科技公司</td><td></td><td>√</td><td></td><td>√ <</td><td>√</td><td></td><td>√</td><td></td></tr><tr><td>北京太平桥印刷材料厂 大连兰天电子油墨开发公司</td><td></td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海网谊丝印油墨公司</td><td>√</td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>无锡玉祁胜达油墨厂</td><td></td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>无锡赛特化工公司</td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>无锡阿尔梅新材料公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>富士化研(昆山)公司</td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>昆山一展电子公司</td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td></tr><tr><td></td><td>√</td><td>√</td><td><</td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>杭州科望特种油墨厂</td><td>√</td><td></td><td>√</td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>台州新韩电子油黑公司</td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td>√</td></tr><tr><td>嘉善贝尔光学材料公司</td><td>√</td><td>√</td><td><</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>广州键科电子材料公司</td><td>√</td><td>√</td><td></td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>广州玻尔电子材料公司</td><td></td><td></td><td>√</td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>广州回天精细化工公司</td><td></td><td></td><td></td><td></td><td>√</td><td></td><td>√</td><td></td></tr><tr><td>广州科怡科技实业公司</td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>番禺广信丝印材料公司</td><td>√</td><td><</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td>·</td></tr><tr><td>番禺惠桥电子材料公司</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>番禺普林斯电子材料公司</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>南亚化工(番禺)公司</td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>佛山长岛化工公司 佛山友联油墨及用品公司</td><td>√</td><td>√</td><td></td><td>√</td><td><</td><td></td><td></td><td></td></tr><tr><td>佛山三求化工公司</td><td>√</td><td>√</td><td><</td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>佛山南海正化工公司</td><td>√</td><td>√</td><td>√</td><td><</td><td>√</td><td></td><td></td><td></td></tr><tr><td>深圳爱达化工公司</td><td>√</td><td></td><td></td><td><</td><td></td><td></td><td></td><td></td></tr><tr><td>深圳容大电子材料公司</td><td>√</td><td></td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>深圳正伟化工公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>深圳泳翰科技股份公司</td><td></td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>东莞图达化工公司</td><td><</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>惠州超亮实业公司</td><td><</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>恒昌涂料(惠阳)公司</td><td>√</td><td><</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>珠海东通油墨公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>珠海丰洋化工公司</td><td></td><td><</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>南宝树脂(中国)公司 金甲化工企业(中山)公司</td><td>√</td><td></td><td>√</td><td>√</td><td></td><td></td><td>√</td><td></td></tr><tr><td>长春化工(江苏)公司</td><td></td><td></td><td></td><td></td><td></td><td><</td><td></td><td></td></tr><tr><td>长兴化学工业股份公司</td><td></td><td></td><td></td><td></td><td></td><td><</td><td></td><td></td></tr><tr><td>美国杜邦公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td></tr><tr><td>日本旭化成公司 日本太阳油墨株式会社</td><td>√</td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>日本东洋油墨公司</td><td>√</td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>上海祥乐田村电化工公司</td><td>√</td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>日本三和化学工业株式会社</td><td></td><td>√</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>美国太阳化学丝印油墨部</td><td><</td><td>√</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>高氏(广州)油墨公司</td><td>√</td><td>√</td><td>√</td><td>√·</td><td></td><td></td><td></td><td>√</td></tr></table></body></html>  \n\n<html><body><table><tr><td>公司</td><td>UV胶</td><td>可见光胶</td><td>UV厌氧胶</td><td>双固化胶</td><td>多重固化胶</td><td>医用胶</td><td>牙科用胶</td><td>LCD胶</td><td>LED胶</td><td>光盘胶</td><td>压敏胶</td></tr><tr><td>北京天山新材料技术公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>北京兴有丰科科技发展公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>北京力拓达科技公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>北京科拉斯化工技术公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>北京嘉联诚亚医疗器械销售公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>涿州兰天特灯发展公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>黑龙江省石油化学研究院</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>济南北方泰和新材料公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>济南晟林伟业工贸公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>青岛海誉新材料公司 青岛海洋化工研究院</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>烟台德邦科技公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>烟台福山义昌精细化工厂</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>烟台泰盛精化新材料公司</td><td><</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>威海瀚玉化纺公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>威海望岛渔具专用配套总厂</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>威海东华特种涂料厂</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>威海佳和涂料公司</td><td>√ √</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海赛沃化工材料公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海康达化工公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海裕光胶粘剂公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海路嘉胶粘剂公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>欧美化工(上海)公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海雷呈化工公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海申风医疗保健用品公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></table></body></html>  \n\n<html><body><table><tr><td>公司</td><td>UV胶</td><td>可见光胶</td><td>UV厌氧胶</td><td>双固化胶</td><td>多重固化胶</td><td>医用胶</td><td>牙科用胶</td><td>LCD胶</td><td>LED胶</td><td>光盘胶</td><td>压敏胶</td></tr><tr><td>上海复星牙科技术公司</td><td></td><td></td><td></td><td>√</td><td></td><td></td><td><</td><td></td><td></td><td></td><td></td></tr><tr><td>上海创代医疗器械公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td>L</td><td></td><td></td><td></td><td></td></tr><tr><td>达任胶粘剂(南京)公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>南京万国生物医学工程技术公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>依工聚合工业(吴江)公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>浙江金鹏化工股份公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>浙江安瑞森信息材料公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>泉州昌德化工公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>泉州金固胶业公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>厦门铂丰化工公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>厦门超锐科技公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>襄樊航天化学动力总公司</td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>长沙把兄弟胶粘剂公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>广东恒大新材料科技公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>广东然生化工公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>广州回天精细化工公司</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>广州天河海元(玻璃)技术部</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>番禺龙珠化工公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>深圳朗博万精细化工公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>深圳宏升华科技公司</td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>深圳泛能工业粘合材料公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>深圳国联胶粘剂公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>深圳瑞泰科技发展公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>深圳再兴行粘合剂公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>深圳金三秒胶粘剂公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>深圳诚信康胶粘剂公司</td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>深圳信鸿鑫化工公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>深圳正伟化工公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>东莞托克电子材料公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>顺德大良邦特合成剂公司</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>公司</td><td>UV胶</td><td>可见光胶</td><td>UV厌氧胶</td><td>双固化胶</td><td>多重固化胶</td><td>医用胶</td><td>牙科用胶</td><td>LCD胶</td><td>LED胶</td><td>光盘胶</td><td>压敏胶</td></tr><tr><td>珠海恒新化工公司</td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>成都拓利化工实业公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>成都伽信新材料技术公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>泉州立施棒高分子材料公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>漳州元皓化工公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>台山友顺化工公司</td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>东莞欧特工业材料公司</td><td></td><td><</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>昆山德渊工业材料公司</td><td><</td><td>√</td><td></td><td>√ √</td><td>√</td><td>√</td><td></td><td></td><td>√ √</td><td></td><td></td></tr><tr><td>汉高乐泰(中国)公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td></tr><tr><td>美国3M(中国)公司</td><td></td><td><</td><td></td><td></td><td></td><td></td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>美国Parson Adhesives Inc.</td><td>√</td><td><</td><td></td><td>√ √</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>美国Cyberbond LLC</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>戴乐博森(烟台)公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>三友(天津)高分子技术公司</td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>三键化工(上海)公司</td><td>√</td><td>√</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>安特固科技(无锡)公司</td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>日本德山齿科株式会社</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>日本可东丽株式会社</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td><</td><td></td><td></td><td></td></tr><tr><td>天津峻成科技发展公司</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>韩国倍丽康公司 雅川化学公司苏州营业处</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>澳大利亚SDI股份公司</td><td>√</td><td></td><td></td><td></td><td>√</td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>苏州金士通化工公司</td><td></td><td>√</td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>德国沃柯公司上海代表处</td><td></td><td>√</td><td></td><td>√</td><td></td><td></td><td>L</td><td></td><td></td><td></td><td></td></tr><tr><td>德国柯梅林公司北京代表处</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>德国好乐公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>德国Yingying Handels GmbH上海办</td><td><</td><td><</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>瑞士康特齿科集团中国代表处</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>意大利乐赛尔工程胶粘剂公司</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>√</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></table></body></html>  \n\n附录15 UV光源主要生产企业  \n\n\n<html><body><table><tr><td>公司</td><td>中压汞灯</td><td>金属卤素灯</td><td>无极灯</td><td>LED灯</td><td>牙科用灯</td></tr><tr><td>北京电光源研究所</td><td><</td><td><</td><td></td><td></td><td></td></tr><tr><td>北京世纪鑫特电光源技术开发公司</td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>北京中瑞达电光源公司</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>北京爱华新业照明器材公司</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>北京大兴电光研究所</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>北京亚明电光源发展公司</td><td></td><td>√</td><td></td><td></td><td></td></tr><tr><td>北京汇忆鑫电光源技术开发公司</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>北京同岭鑫电光源厂</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>北京凌业特种光源技术公司</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>北京鹏光电光源公司</td><td>√</td><td><</td><td></td><td></td><td></td></tr><tr><td>北京隆泰森电光源公司</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>北京亚尔电光源公司</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>北京岩田博远科技股份公司</td><td></td><td></td><td></td><td>√</td><td></td></tr><tr><td>北京东昇玻璃光源厂</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>北京科达光源电器公司</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>北京辉煌电光源公司</td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>北京兴翌苑特种光源公司</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>涿州兰天特灯发展公司</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>涿州兰源特灯厂</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>涿州兰宇特灯厂</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>保定宏兴电子设备厂</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>保定光亮特种UV光源厂</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>保定市特种光源电器厂</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>上海珏晖电光源公司</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>上海科信印刷器材公司</td><td>√</td><td><</td><td></td><td></td><td></td></tr><tr><td>上海煜业电光源制造公司</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>上海华陀灯泡厂</td><td>√</td><td>√</td><td></td><td>√</td><td></td></tr><tr><td>上海芯怡印刷器材公司</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>上海尚信化工科技公司</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>上海亚明灯泡厂</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>上海罗曼电光源公司</td><td>√</td><td>√ √</td><td></td><td>√</td><td>√</td></tr><tr><td>上海捷仪经贸公司 江苏奥雷光电公司</td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>南京世纪特种光源公司</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>无锡邦钰光源公司</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>无锡威恪特印刷器材行</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>广州海达(UV)光源公司</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>广州宏伟特种(UV)光源公司</td><td><</td><td></td><td></td><td></td><td></td></tr><tr><td>广州巍泰机电公司</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>广州泛亚光电公司</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>广州迅辉UV光源公司</td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>香港同乐印刷器材公司广州办</td><td>√</td><td></td><td></td><td></td><td></td></tr><tr><td>深圳大东行印刷设备材料公司</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>深圳凯世光电(集团)公司</td><td>√</td><td>√</td><td></td><td></td><td></td></tr><tr><td>深圳勇诚特光科技公司</td><td>√</td><td><</td><td></td><td></td><td></td></tr><tr><td>光科技公司 深圳普瑞电光源设备公司</td><td>√ √</td><td>√ √</td><td></td><td></td><td></td></tr></table></body></html>  \n\n续表  \n\n\n<html><body><table><tr><td>公 司</td><td>中压汞灯</td><td>金属卤素灯</td><td>无极灯，</td><td>LED灯</td><td>牙科用灯</td></tr><tr><td>成都英吉莱科技公司 咸阳荷立医疗器材公司 志圣科技(广州)公司 志翔科技(昆山)公司</td><td>√ √ √ √</td><td>√ √ √ √</td><td></td><td>√</td><td>√</td></tr></table></body></html>",
+        "category": " References"
+    },
+    {
+        "id": 801,
+        "chunk": "# 参考文献  \n\n［1］魏杰，金养智．光固化涂料．北京：化学工业出版社，2005.  \n［2］杨建文，曾兆华，陈用烈．光固化涂料及应用．北京：化学工业出版社，2005.  \n［3］陈用烈，曾兆华，杨建文．辐射固化材料及其应用．北京：化学工业出版社，2003.  \n[4]王德海，江．紫外光固化材料—理论和应用．北京：科学出版社，2001.  \n[5］［英］霍尔曼R，奥尔德林P．印刷油墨、涂料、色漆紫外光和电子束固化配方．徐茂均等译．北京：原子能出版社，1994.  \n[6] 聂俊，肖鸣等．光聚合技术与应用．北京：化学工业出版社，2009.  \n[7] 李善君，纪才圭等．高分子光化学原理及应用．上海：复旦大学出版社，1993.  \n[8] 邓莉莉，程康英，金银河．非银盐感光材料．北京：印刷工业出版社，1993.  \n[9] 大森英三．功能性丙烯酸树脂．张育川，朱传榮，余尚先，周明义译，北京：化学工业出版社，1993.  \n［10］罗菲CG，光聚合高分子材料及应用．黄毓礼，王平，庞美珍，裘照耀译．北京：科学技术文献出版社，1990.  \n[11] 金养智，魏杰，刁振刚，陈胜恩．信息记录材料．北京：化学工业出版社，2003.  \n[12] 金关泰，高分子化学的理论和应用进展，北京：中国石化出版社，1995.  \n[13] 山下晋三，金子车助．交联剂手册．纪奎江，刘世平，竺玉书译．北京；化学工业出版社，1990.[14] 王德中．功能高分子材料．北京：中国物资出版社，1998.  \n[15] 周学良．功能高分子材料．北京：化学工业出版社，2002.  \n[16] 永松元太郎，乾英夫，感光性高分子．丁一，余尚先，金昱泰译．北京：科学出版社，1984.[17] 马庆麟．涂料工业手册．北京：化学工业出版社，2001.  \n[18] [19] 虞兆年．涂料工艺(增订本)．北京：化学工业出版社，1996. 洪啸吟，冯汉保．涂料化学．北京：科学出版社，1997. 武  \n[20] 张学敏，郑化，魏铭．涂料与涂装技术．北京：化学工业出版社，2006. 李树[21] 李荣兴．油墨．北京：印刷工业出版社，1988.  \n券[22] 钱军浩．油墨配方设计与印刷手册，北京：中国轻工业出版社，2004.  \n[23] 周震．印刷油墨，第2版．北京：化学工业出版社，2006.  \n[24] 阎素斋，李文信，特种印刷油墨．北京：化学工业出版社，2004. AH[25] 朱梅生，程冠清．印刷品上光技术．北京：化学工业出版社，2005.  \n[26] 张国瑞，刘漪．印刷应用UV固化技术．北京：化学工业出版社，2006.  \n[27] 程时远，李盛彪，黄世强．胶粘剂．北京：化学工业出版社，2000.  \n[28] 肖卫东，何培新，张刚升，曹杰．电子电器用胶粘剂．北京：化学工业出版社，2004.[29］陆企亭．快固型胶粘剂．北京：化学工业出版社，1992.  \n[30]孙忠贤．电子化学品．北京：化学工业出版社，2001.  \n[31]、金鸿，陈森，印制电路技术，北京：化学工业出版社，2003.  \n[32]- Lowe C et al. Chemistry and Technology for UV and EB Formulation for Coatings, Inks and Paints.  \nLondonUK,1997..  \n[33] 'Fouassier J P, Rabek J F.\" Radiation Curing in Polymer Science and Technology. London:UK，1993.  \n[34] 面向21世纪中国辐射固化技术和市场研讨会论文集．威海，2000，10.  \n[35] 2002全国辐射固化技术研讨会论文集．上饶．2002，4.  \n[36] 2004全国辐射固化技术研讨会论文集．重庆，2004，5.  \n[37] Rad Tech Asia，Conference Proceedings 200l. Kunming，China. 2001，5.  \n[38] Rad Tech Asia，Conference Proceedings 2003. Yok hama， Japan. 2003，12.  \n[39] Rad Tech Asia，Conference Proceedings 20o5. Shanghai，China，2005，5.  \n[40] Rad Tech Asia，Conference Proceedings 20o7. Kuantan，Malaysia. 2007，9.  \n[41] Rad Tech Europe，Conference Proceedings 2001. Basle，Switzland. 2001，10.  \n[42] Rad Tech Europe，Conference Proceedings 2003. Berlin，Germany. 2003，11.  \n[43] Rad Tech Europe，Conference Proceedings 2005. Spain. 2005，10.  \n[44] Rad Tech Europe，Conference Proceedings 2007.Vienna，Austria. 2007，11.  \n[45] Technical Conference Proceedings，Rad Tech 20o2. Indianapolis，USA. 2002，4.  \n[46] Technical Conference Proceedings，Rad Tech 2004.Charlatte，USA.2004，5.  \n[47] Technical Conference Proceedings，Rad Tech 2006.Chicago，USA.2006，4.  \n[48] Technical Conference Proceedings，Rad Tech 2008. Chicago，USA. 2008，5.",
+        "category": " References"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/╤к╦и╨н═м┐╣╛· ╓╨╬─.json b/task2/task2-chunks/╤к╦и╨н═м┐╣╛· ╓╨╬─.json
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@@ -0,0 +1,57 @@
+[
+    {
+        "id": 1,
+        "chunk": "# 心血管医疗设备上的超薄和坚固水凝胶涂层可缓解血栓栓塞和感染并发症  \n\nGerman Parada、Yan Yu、William Riley、Sarah Lojovich、Diane Tshikudi、Qing Ling、Yefang Zhang、Jiaxin Wang、Lei Ling、Yueying Yang、Seemantini Nadkarni、Christoph Nabzdyk\\*和Xuanhe Zhao\\*  \n\nzhaox@mit.edu Y. Yu, Y.  \nYang 博士  \n光学与电子信息学院  \n华中科技大学 湖北武汉 430064  \nW.Riley, S. Lojovich 灌注服  \n务部  \n美国马萨诸塞州波士顿市麻省总医院  \n邮编：02114  \n本文作者的 ORCID 识别码可在  \nhttps://doi.org/10.1002/adhm.202001116 下找到。DOI: 10.1002/adhm.202001116  \n\n血管内导管等心血管设备是诊断和治疗许多急性和慢性疾病的关键。  \n\nG. 帕拉达博士  \n美国马萨诸塞州剑桥市麻省理工学院化学工程  \n系 邮编：02139  \nDr. G. Parada, Dr. Y. Yu, Y. Yang, Prof. X. Zhao  \nMassachusetts Institute of Technology  \nCambridge, MA 02139, USA 机械工程系  \n电子邮件:  \n\nAdv.2020, 2001116",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1-10]由于慢性病发病率较高以及人口整  \n\n因使用心血管医疗器械而引发的血栓栓塞和感染并发症仍很常见，并导致严重的发病率和死亡率。迄今为计止增，还长没率有为一 4种.7策%略[11能,12同]。时[有11,1效2]解由决于这使两用个难题。人们提出了各种表面改性策略（广如银泛、，肝感素染和（液5体%-浸15渍%表）面[），但和每血种栓策形略都有一些局限性和缺点。本文显示，加入超薄、机械坚固的水凝胶层可将细菌在医用管材上的附着力降低 $95\\%$ 。此外，通过结合体外和体内测试，还证明了水凝胶层可显著减少血凝块的形成和对管道的粘附，而不会影响血液的内在凝结能力。在体外模型中，血块对管道壁的粘附减少了 $90\\%$ 发以症上，在这使用得中猪心体静内模脉型导中管的（设C备V闭C塞时间（因血块形成而关闭前的时间））增加、了血 $\\approx60\\%$ 析。这导种管被和动外涂周层的置优入势中特心性导使其成为与血液连接的医疗设备的理想表面材料。  \n\n，因为这些导管的使用时间通常较长（数周至数月）[1,2,4,5,8,14-1G]。此外，导管相关并发症的治疗成本高昂且具有挑战性，因为依赖这些导管的患者很可能体弱多病和/或病情危重（如重症监护室患者、严重感染患者、癌症患者）。除了增加  \n\n这些并发症和相关的护理费用给整个医疗系统带来了沉重的负担。  \n\n这些并发症并非导管设备所独有，其他与血液接触的设备，如支架、人工旁路移植、透析设备、心室辅助设备（VAD）、人工心脏瓣膜和体外膜肺氧合（ECMO）设备也有此类并发症的报道。[17-22]尽管做出了巨大努力，但与使用心血管医疗设备相关的感染和血栓栓塞仍是一个尚未解决的重大临床难题，尤其是考虑到依赖这些设备的慢性病患者人数不断增加。  \n\n目前还没有同时充分解决血栓形成和感染并发症的 商业解决方案。大多数市售技术都针对感染并发症。这些方法包括伤口防腐敷料、抗生素涂层导管和抗生素浸渍导管。[7,13,23-28]这些技术可适度减少菌血症，但仅适用于特定患者群体和短期导管使用。这些方法都不能使设备表面从本质上减少细菌粘附，从而减轻细菌生物膜的形成。此外，导管使用的其他副作用（包括血栓形成）也没有得到改善，长期应用的临床效益也没有得到证实[23,24] 另有一套可用技术旨在解决血栓形成和随后的装置闭塞问题。这些方法依赖于在设备表面附着生物惰性聚合物或生物活性分子，如粟米胰蛋白酶抑制剂、肝素或血栓弹力蛋白。[G,10,29-32] 尽管前期临床数据前景看好，但临床试验结果却喜忧参半，只有部分肝素涂层技术能够显示出临床效益。  \n\n同时解决血栓形成和感染问题的技术寥寥无几。33-35] 这种表面可同时排斥细菌和血液成分，但由于担心血液中含有含氟液体，因此尚未应用于临床。第二种方法是在器械表面接枝亲水性聚合物。这是一种成熟的技术，最初开发于 20 世纪80 年代，用于减少导尿管的摩擦和刺激，尽管只涉及表面聚合物接枝而非三维聚合物网络， 但 在 市场上仍被称为 \"水凝胶涂层 \"技术。目前，大多数主要品牌都提供 \"水凝胶涂层\"导尿管，品牌名称包括 Biocath 和 Lubri-sil（Bard）、Flocath（ Teleflex ） 、 Serpia （ Braun ） 、 Convey 和 HydroPlus （Boston Scientific）以及 HydroPicc（Access Vascular）[41-43]。尽管临床表现良好，并被医护人员采用，但由于这些接枝涂层通常只有几十纳米厚，因此人们担心涂层失效和脱层会造成不良影响。[41,42] 这些证据促使 FDA 于 2015 年发布了一份安全通报，并于 2019 年发布了一份标签指南，以解决这些并发症。  \n\n在不断发展的心血管和重症监护设备领域。  \n\n在这项研究中，我们对医疗设备表面引入的超薄水凝胶层的机械、抗菌和抗血栓性能进行了表征。韧性水凝胶材料的强力粘附是我们小组最近开发的一项技术[4G-48]，它显示出增强基于弹性体的医疗界面的界面特性的潜力。在本文讨论的实验中，我们使用了医用级聚氯乙烯（Ty-gon）管，这是一种标准的医疗设备，用于透析和心肺旁路设置中的血液管理。任何使用导管进行的测试都需要一个外容器（不同材料）来容纳血液，这是不可取的，因为这可能会使分析复杂化。涂层表面的摩擦系数很低，可承受生理流速下的流体流动长达 12 小时，且无任何可测量的变化。与未涂层表面相比，细菌和纤维蛋白的粘附性明显降低。此外，通过一系列体外试验和流动循环测试，我们发现透明凝胶涂层可减少血凝块的形成和对设备表面的粘附，同时不影响血液的正常凝结能力。此外，我们还在猪身上展示了植入全身循环（动脉与动脉连接）的水凝胶涂层 PVC 管的良好通畅率。这些初步结果表明，血液接触装置的水凝胶涂层可减轻心血管装置的感染和血栓相关并发症，从而可避免采用旨在单独解决这些临床问题的技术。",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 水凝胶涂层的制备方法如前所述  \n\n[48]之所以选择这种方法，是因为它可以对平面以及圆柱形设备（如导管和管道）的内表面和/或外表面进行涂层。按照已公布的操作规程，本研究中的涂层首先将洁净的医疗表面浸没在乙醇中的二苯甲酮溶液中。除去溶液后，在活化表面加入含有 N,N-二甲基丙烯酰胺（DMAA）和生物相容性光引发剂（Irgacure 2595）的预凝胶水溶液。[49]然后用紫外线照射表面，使水凝胶层聚合。彻底冲洗多余的聚合物和副产品后，在设备上均匀涂上一层超薄（ $(\\approx10~\\upmu\\mathrm{m})$ ）的水凝胶，如图 1a 中Tygon CPB 管的示意图所示。与静脉导管的典型外径（5-G 毫米）或血液管理管道的内径（0.75-1.5 厘米）相比，这层水凝胶非常薄。图 1b 中显示了原始管材和涂层管材（仅内腔）的宏观图像，表明水凝胶涂层是均匀的，并且由于其尺寸仅为微米级，因此不会影响设备的整体尺寸。横截面的显微镜图像见图 S1（佐证资料）。关于水凝胶涂层的化学成分、制造工艺和粘附机制的更多详情，请参阅以前的出版物[48]。  \n\n测定了水凝胶层的弹性模量以前的值为 $E\\approx30\\mathrm{kPa}$ ，[48] 与现在的值相差两个数量级。  \n\n![](images/c45311c28f1054694f2abee7c857e2bb0c684e4e560fb131d12fb4cb2fdb3643.jpg)  \n图 1.a) 使用建议的超薄水凝胶涂层减轻血管医疗器械上细菌粘附和血栓形成的示意图。 b) 本研究中使用的医疗器械是 Tygon 心肺旁路（CPB）管，既有原始管，也有水凝胶涂层。水凝胶涂层的示意图显示了其微米级的厚度。  \n\nc) 涂覆管和原始管的宏观图像，以证明此处使用的方法可在英尺长的管段上生成均匀一致的水凝胶涂层。  \n\n![](images/7437c1e0a5e988d0f64783d40b90f410e1866ed2135697cd0946790f587ed4b7.jpg)  \n图 2. 水凝胶涂层表面的机械和抗菌特性。a) 原始表面和涂层表面连续剪切 1 小时后的摩擦系数 (COF)。误差条代表 COF 值在 3 分钟内平均值的 SD。 b) 在左图所示装置中连续流动生理盐水溶液（流速 $\\fallingdotseq$ 1.5 升/分钟−1 ）长达 12 小时后的接触角和水凝胶层厚度测量。c) 原始表面和涂覆表面的代表性荧光显微镜图像，GFP 表达的大肠杆菌呈亮绿色。 d) 原始表面和涂覆表面在静态和流动测试条件下的大肠杆菌（面积）覆盖定量。流动条件在与(b) 小节所示类似的仪器中进行。误差条代表多个分析区域的 SD 值。  \n\n$E\\approx\\mathbf{G}$ 兆帕）。含水水凝胶层的存在降低了表面的摩擦系数（COF），[50-53] 如前所述，我们在这里使用钢制平行板几何形状的流变仪进行了测试。  \n\n如图 2a 所示，用 1 牛顿的法向力连续剪切锥形表面和涂层平面，直至 G0 分钟。在整个实验过程中，涂层表面的COF 值始终低于原始表面（0.1-0.15 vs 0.30），这表明涂层表面具有显著的机械坚固性。  \n\n[55]。  \n\n互穿水凝胶层。不坚固的涂层会被持续的剪切力侵蚀，COF 会增加到与无涂层基底相似的值。值得注意的是，这些加载条件超出了实际应用中的最终条件。涂层还能承受生理速率（ $(\\approx1.5~\\mathrm{L~min–^{1}}$ ）和压力（ $({\\approx}100~\\mathrm{mmHg}),$ ）的流体流动。利用图 2b 所示的设置，生理盐水通过涂层管段连续循环长达 12 小时。在选定的时间点，用无柄液滴法测量表面水接触角，并用荧光显微镜评估涂层厚度。由于原始Tygon 表面具有亲水性，因此原始样品的测量接触角高于$80^{\\circ}$ 。引入 ${\\approx}10~\\upmu\\mathrm{m}$ 水凝胶涂层后，测得的接触角有所下降（低于 $40^{\\circ}$ ）。连续流动 12 小时后，接触角或涂层厚度没有变化，这证明了水凝胶涂层的坚固性和完整性。  \n\n以前的出版物表明，水合表面（接枝聚合物和块状水凝胶）可用作防污层，防止不需要的物质附着[7,39,47,48,54]。将涂层表面和原始表面与含有工程大肠杆菌的培养基接触，分别在静态和流动条件下培养 4 小时和 8 小时。大肠埃希氏菌是一种常见的病原体，多见于呼吸道感染和医院内感染[2,4,7,8]，这些实验中使用的菌株被设计为表达 GFP，便于使用荧光显微镜观察。在这两种情况下，涂布表面的细菌粘附和着色都明显减少。  \n\n与原始表面相比，静态和平面测试的结果（p <<0.05），如图 2c 所示。显微镜成像如  \n\n图 2d 显示，即使在没有洗脱抗生素的情况下，水凝胶涂层也能防止细菌粘附。  \n\n34,35] 这样就可以在血液开始在表面凝固时观察到纤维蛋白网络的形成。如图 3a 所示，共聚焦显微镜成像显示，在每个时间点，纤维蛋白沉积和网络形成在原始子基底上都明显多于涂层子基底。值得注意的是，在这些实验中，由于血液经过肝素化处理，所以没有看到宏观凝结现象。图 3b显示了不同代表性区域和样品的定量分析结果，其结果与水凝胶和全氟表面的防污性能相当。[ 34-37,54]预计本研究中展示的水凝胶涂层对其他血液蛋白和凝血级联过程中的因子也具有类似的抗粘附性能，不过还需要更多的工作来验证和量化这一假设。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 4,
+        "chunk": "# 接下来，我们用牛全血来进一步确定  \n\n在比上述试验更接近预期应用的环境中进行表面涂层与血液的相互作用试验。以下测试的目的是比较有涂层和无涂层管材与器械相关的血栓形成、粘附和闭塞情况，这些都是 ISO 标准要求的测试，用于评估医疗器械的血液兼容性由于可以在市场上买到，而且这些实验需要大量血液（大于 50 毫升），因此使用了[3,15,1G,32,5G]。由于瘀血w会w促w.a进dv凝an血ced，s[c3,i1e5,n1cG,e3n2,e5Gw]s.实co验m是在保持血相恒定运动的情况下进行的，以尽量减少这一干扰因素，并更全面地描述血液与表面涂层的相互作用。  \n\n第一个测试是引入血流的简单方法，具体做法是在侧管中来回移动血柱，直到发生凝结，如佐证资料中的视频所示。堵塞时间的定义是，当宏观血栓堵塞管腔，从而在倒转管道时看不到血液流动时的时间。图 3c 显示了多次测试的结果。在没有运动（即瘀滞）的情况下，涂层试管和原始试管的凝血时间与对照组（Eppendorf 试管中的血液）无异。当血液被搅动时，涂层试管中测得的凝血时间长于原始试管。由于测试是在不同的日期进行的，因此数据的差异很可能是所用血样的变化。此外，值得注意的是，最上面的 5 个涂层测试在 $t=25$ 分钟时被任意停止，尽管仍能观察到管内的气流。经仔细观察，试管内仍有未凝固的血液，而且与原始试管测试不同，发现的血栓并没有附着在试管表面。  \n\n总之，这些结果非常有希望，表明涂层有可能被动地改善与血液接触设备的性能，即不需要肝素或柠檬酸盐等抗凝血剂。虽然有人建议使用含肝素的表面来减少血  \n栓形成并发症（如戈尔公司的 CARMEDA 或美敦力公司的  \nCortiva 生物活性涂层），但肝素的引入也会带来负面影  \n响，如出血风险和肝素诱导的血小板减少症。此外，这  \n种局部抗凝特性难以控制，可能会对凝血异常患者产生不  \n可预测的影响。总体而言，这些肝素涂层表面的临床效果  \n并不明显，最多只能维持很短的时间。图 3c 所示结果的一个可能解释是，水凝胶涂层通过细胞裂解、结合或去除关键因子干扰了血液的凝血级联。因此，我们进行了两项实验来排除这些可能性。首先，在轻度搅拌下将全血样本置于原始管材和涂层管材上，然后用离心机收集并造粒。上清液用分光光度计在氧合血红蛋白的最强吸收频率（540 和 57G 纳米）下进行分析。[57] 如图 3d 所示，样品与阴性对照（未处理的牛血）和溶血阳性对照（低渗溶血）进行比较。测量结果证实，与阴性对照（基线）相比，涂层不会引起任何明显的溶血。溶血会导  \n致红细胞胞质中的血红蛋白释放到上清液中，而上清液中的血红蛋白又会被溶解。  \n\n会导致更高的吸光度值。  \n\n其次，进行了光学血栓弹性成像（OTEG），以量化水凝胶涂层对血液凝结过程的影响。 图 3e 是这种方法的示意图，它分析反射激光束的自相关函数并生成Adv.2020, 2001116  \n\n![](images/2f56e967c5badba0c3d6bd64a6d0a703653db195fbf37ed761b440c13ee34d0f.jpg)  \n\n图 3：体外动态和静态血液测试。a) 原始表面和涂层表面纤维蛋白网络形成的代表性图像。b) 纤维蛋白网络在表面上的覆盖面积。c) 在静态或动态（搅拌）条件下，原始管材和涂层管材被凝块堵塞所需的时间。使用的对照是 Eppendorf 管。 d) 原始管和涂层管接触的血液离心后上清液在主要波长下对氧合血红蛋白的吸光率。所用对照为原样血液和裂解血液。e) 改良光学血栓弹性成像（OTEG）实验示意图和量化参数。 f) 与涂层管和原始管接触的血液的归一化活化时间 $(R)$ ）、凝血时间（ $(R+\\kappa)$ ）和最大振幅（MA）的箱形图。归一化处理是与对照样本（分析时未接触管材）一起进行的，以考虑血液样本的可变性。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# 图 3e）[58] 上升曲线表示血液凝结，其中 $R$ 是活化时间（凝结开始前的时间）， $R$  \n\n须避免瘀血，以突出水凝胶涂层的有益作用。  \n\n$+K$ 是总凝血时间。凝块强度由 MA（最大振幅）值来确定。如图 3e、f 所示，我们比较了放置在原始试管和涂层试管中的血液样本的凝血时间和凝血强度。考虑到样本的可变性，我们用对照样本（留在 Ep- pendorf 瓶中的血液）的值对这些值进行了归一化处理，数据以须线图的形式显示。原始试管和涂层试管的 $R$ 值、 $R+K$ 值和 MA 值均无差异（t 检验的 p 值高于 0.05），这表明水凝胶涂层不会干扰凝血本身（与肝素洗脱或肝素涂层表面不同），而且必w验w中w.a，dv创anc建ed了sc封ien闭ce的ne环ws形.co管m回路（Tygon CPB 管），并使用 CPB 机滚筒泵将全血通过回路循环（图 4a）。在这个心脏手术中使用的 CBP 循环的缩小模型中，使用了 0.25 升/分钟的低流速，以避免过压、循环泄漏和溶血。循环回路中的血液一直循环到对照血样（在 Eppendorf 小瓶中静止）完全凝固为止。将凝血剂倒入培养皿中，取出血凝块并称重。用生理盐水轻轻冲洗管道两次，然后称重。如图 4b 所示，在原始管中循环的牛血形成的附壁血块比接触涂层管的血液要多。图 $\\scriptstyle4\\mathrm{c}$ 显示了三次重复实验的量化结果。  \n\n![](images/d0aa59b41055ec1154de94dc6ce6a462c66e3baa9733dc3bb2c312c65d8477fc.jpg)  \n图 4：体外血液循环测试。a) 用于原始管材和涂层管材连续流动测试的仪器图像。b) 原始管材（左）和涂层管材（右）在进行流动测试并用生理盐水轻轻冲洗后的图像。误差条代表三次重复实验的 SD 值。  \n\n原始管材的平均重量增加了 5.03%，而涂层管材的平均重量增加了 0.19%。这一统计学意义上的增加（p < 0.05）表明，血凝块更容易粘附在原始管材上，而不是涂层管材上。接下来，对原始血液中形成血凝块的部分进行了评估（附着在管子上的血凝块和培养皿中的血凝块）。与原始管材接触的血液中约有 $40\\%$ 出现血凝块，而与涂层管材接触的血液中仅有G.2% 出现血凝块。这一差异也很明显， $\\mathrm{P}=0.003$ 。  \n\n这两项结果非常有希望地证明，泰贡管材和其他弹性体基材上的透明凝胶涂层  \n\n血液接触装置显示出解决血栓相关并发症的潜力，而无需肝素或其他抗血栓药物。可以想象，正如之前发表的文章所指出的那样，涂层管道的水合粘性表面减少了血小板或凝血因子的粘附和/或活化。  \n\n为了进一步证明所开发的水凝胶涂层能够在不使用抗凝药物的情况下延缓医疗设备上的凝血，我们进行了一项小型的初步体内研究，将管道用作麻醉巴马猪髂动脉的动脉旁路。没有使用肝素等抗凝药物。示意图见图 ${\\pmb5}{\\bf a}$ 。简而言之，在腹股沟部位做一个切口，然后将一根暴露髂动脉 ${\\approx}7$ 厘米的部分。用止血钳夹住两端，并在夹钳远端约 1 厘米处做小切口。将旁路装置插入切口并缝合，以避免泄漏。然后松开夹钳，使用多普勒超声和超声成像测量通过旁路的血流量和旁路内血栓的形成（图 5c、d）。当超声成像不再显示血流时，实验停止，并记录闭塞时间。  \n\n未涂层和涂有水凝胶的医用级硅胶管（内径 1.2 毫米，长 7 厘米）经过消毒，在本初步研究中用作动脉旁路。使用硅胶管的原因是它比前几节中使用的泰贡管壁厚且更柔韧。每种条件都进行了三次实验。如图 5e 所示，未涂层装置的平均闭塞时间为 3GG.7 秒，标差为 90.7 秒。水凝胶涂层装置的平均闭塞时间为 590.5 秒，标差为 130.9 秒，比未涂层装置的闭塞时间更长（单尾 $t$ 检验 $\\overset{\\cdot}{p}=0.032\\overset{\\cdot}{.}$ ）。在不进行全身抗凝的情况下，在装置上添加水凝胶涂层可使闭塞时间延长 $G0\\%$ 。这项初步体内实验的结果与体外实验的结果相吻合，支持了我们之前的研究结果，即在基于弹性体的医疗设备上引入超薄水凝胶涂层可以延缓血凝块的形成和在设备表面的附着。值得注意的是，这一结果是在不同的（更真实的）血流模式和更窄的管腔尺寸下获得的，这表明只要血液接触表面具有均匀且薄的水凝胶涂层，设备的几何形状并不重要。特别是，本实验中的变量（如动脉旁路而非动脉至静脉瘘和极小的内腔直径）是特意选择的，目的是使流经管道的血流更加顺畅，从而迅速导致血管闭塞。因此，这些在通畅性方面的显著差异非常令人鼓舞。  \n\n我们的结论是，本研究可以作为将水凝胶涂层技术作为一种设计策略的早期概念验证，从而减轻因使用与血液接触的医疗器械而引起的血栓栓塞和感染并发症。  \n\n![](images/eea80bca0e77567b165f887c4d8fdd49c017fcef647cd717a40cc1902cdd2729.jpg)  \n图 5.a) 用于评估恒定血流条件下涂层装置性能的猪模型示意图。  \n\nb) 连接硅胶管的髂动脉图像。c) 实验开始时（左图）和实验结束时（右图）装置的多普勒超声图像。超声波测量结果显示没有血流速度，这表明装置被内表面附着的血块堵塞。误差条代表三次重复实验的 SD 值。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 实验部分  \n\nTygon 表面的水凝胶涂层：除非另有说明，所有化学品均购自Millipore-Sigma，并按收到的原样使用。实验方案如下。将医用级（U.S. Plas- tic Corp.）平面或管材切割成所需尺寸，用异丙醇和去离子水清洗，并用氮气流充分干燥。然后用空气等离子体（PDC-001，Harrick Plasma， $<350$ torr、  \n18 W）1-2 分钟，并浸没在二苯甲酮溶液（ $10\\mathrm{{wt\\%}}$ ）中。  \n乙醇中）3-5 分钟。从溶液中取出装置，用纸巾吸去多余的乙醇，然后将装置放入先前脱气的水凝胶前体溶液（20-30 wt% N,N-二甲基丙烯酰胺，$0.5\\mathrm{wt\\%}$ Irgacure I-2959 水溶液）中。对于平整的表面，表面上方至少应有 5 毫米的前驱体溶液。对于管材，前驱体溶液应完全充满内壁。然后将装置暴露在紫外线（UVP CL-1000， $\\lambda=365$ 纳米）下，时间为 10 分钟。  \n45 分钟，在设备表面形成互穿水凝胶层。  \n聚合溶液被清除并作为废物处理。在测试之前，用去离子水彻底清洗这些器件 3 天（平面器件浸没在水下，放在振动器中，管子连接蠕动 CBP（VWR，可变流量泵））。  \n\n摩擦测量：在法向力控制模式下使用流变仪（AR-G2，TA 仪器公司）测量平面（ $(5\\times5$ 厘米）的摩擦系数，平行钢板的几何尺寸为 20毫米。摩擦系数是根据测量到的扭矩和法向力，按照之前使用的方案计算得出的 $\\pmb{\\hat{\\psi}}^{[39,40]}\\pmb{\\hat{\\psi}}$ 简单地说，将原始样品和涂层样品装入流变仪，对样品施加 1 N 的法向力，并施加 $0.5\\:\\mathsf{s}$ 的稳态剪切速率−1 。法向力和扭矩的测量持续了一个小时。分析并报告了间隔 2.5 分钟的数据。  \n\n抗流动性：图 2b 所示的仪器是通过将内径为 3/4 英寸的管道连接到蠕动泵（Cole Parmer Masterflex L/S）而制成的 。在泵的出口侧连接了一段涂层管，并在下游放置了一个夹子以调节出口压力。流速设定为  \n\n1.5 升/分钟−1 ，在每个时间点取出一段 2 厘米长的涂层管进行分析。接触角是通过无梗水滴法测量的，即在表面滴一滴 3 µL 的水，使用高分辨率相机和背光照明进行成像，然后使用 ImageJ (NIH) 测量接触角。测量水凝胶厚度的方法是对管材进行横截面测量，然后用高分辨率相机和背光源进行成像，并使用 ImageJ (NIH) 测量角度。  \n\n细菌粘附：在 Luria-Bertani 肉汤（LB 肉汤）中 $37^{\\circ}\\mathsf{C}$ 培养表达绿色荧光蛋白（GFP）的大肠杆菌工程菌株[47,48] 过夜。用 $10~\\mathrm{mL}$ 新鲜 LB 肉汤稀释 1 mL 菌体培养液等分，然后将其放置在平面样品（ $1{\\mathsf{c m}}\\times1$ cm）上，在 $37^{\\circ}\\mathsf{C}$ 下培养 4 小时（静态条件）。在流动条件下，使用VWR 蠕动泵和内径为 3/8 英寸的管道安装图 2b 中仪器的缩小版--细菌溶液在 $37^{\\circ}\\mathsf{C}$ 下通过管道流动 8 小时。培养结束后，取出样品，用磷酸盐缓冲盐水（PBS）轻轻冲洗两次以去除自由漂浮的细菌，然后用荧光显微镜（Eclipse LV100ND，尼康）成像。使用 Image J 对样品上的细菌覆盖率进行量化。  \n\n纤维蛋白沉积：按照之前公布的方案，[31,32] ，用 $1\\mathrm{wt\\%}$ 牛血清白蛋白（BSA）在 PBS 中阻塞 24 孔板（康宁公司）的孔 30 分钟，然后用PBS 冲洗。将原始样本和涂布过的扁平样本（ $1\\times1$ 厘米）与添加了荧光标记纤维蛋白原（Alexa Fluor 488 conjugated human fib- rinogen，ThermoFischer Scientific 公司）的肝素化人类全血（ $0.25\\cup\\mathsf{m L}^{-1}$ ，以防止整体凝血）一起放入阻塞孔中。样品在室温下的轨道摇床上孵育的时间点不断增加。将样品从孔中移出后，用生理盐水（ $0.9\\%$ 氯化钠）轻轻冲洗，并用 $0.1\\mathrm{~M~}$ 磷酸盐缓冲液中的 $2.5\\%$ 戊二醛固定 1 小时，然后用直立共聚焦显微镜（SP8，Leica）成像。使用 ImageJ 对图像进行分析和量化。血液溶解：将枸橼酸化的牛血样（ $(\\approx3~\\mathsf{m L}$ ）置于内径为3/8 英寸的原始涂膜管的内腔中，轻轻搅拌 5 分钟。使用两个对照组--接收血液和裂解血液（添加 $20\\%$ 去离子水）。然后将血液倒入Eppendorf 管，离心 2 分钟（VWR 微型离心机）。将上清液置于一次性比色皿中，使用紫外可见分光光度计（BioMate 3S，ThermoScientific）在 540 和 $576\\:\\mathsf{n m}$ 两个波长下进行分析，这两个波长分别对应于氧合血红蛋白的最大吸光度。血红蛋白。  \n\n光学血栓弹性成像：这些实验所使用的设备由 Nadkarni 研究小组的研究人员定制，在其他地方有详细介绍。[51–53]数据收集和分析算法也在这些出版物中有所介绍。将枸橼酸化的人体血液  \n\n的标准差。所有 t 检验的显著性水平设定为 alpha $=0.05$ ，因此，如果 p 值低于 0.05，则表示差异具有统计学意义。  \n\n在原始管材和涂层管材（3/8 英寸内径）内停留 3 分钟，然后用生理盐水中的 $0.2\\ensuremath{\\mathsf{M}}$ 氯化钙溶液（ $60\\upmu\\mathrm{L}\\mathsf{m}\\mathsf{L}^{-1}$ 血液）。将 ${\\approx}100~\\upmu\\upiota$ 的等分血液放入硅胶采血盒中，在 $37^{\\circ}\\mathsf{C}$ 下进行分析，直到测出凝血为止。对照样本中的血液在不接触任何管道的情况下进行再钙化和分析。参数通过使用定制的 MATLAB 算法拟合 OTEG 曲线获得。  \n\n管内血流测试：进行了两种不同类型的测试。第一种试验是用 0.5 毫克氯化钙盐水（每毫升血液 24 微升）重新钙化 3 毫升枸橼酸化牛血，然后将其放入带刺和涂层的导管（≈9′长，3/8″内径）中。管子之前已用乙醇和紫外线消毒，并用生理盐水彻底冲洗。如视频（见佐证资料）所示，来回搅拌管子，直到凝块形成或 25 分钟过去。记录凝血时间，即血柱停止移动时的凝血时间。在第二类试验中，血液搅拌由 CBP 滚筒泵（Cobe Century）提供。在这种情况下，将内径为 3/8 英寸的 20 英寸原始管和涂层管注入重新钙化的血液（ ${\\approx}25$ 毫升），并在两端连接一小段3/4 英寸管，使其闭合成环。在注入血液之前和之后都对管子进行了称重。设定 0.25 升/分钟的−1 流量，直到对照样本（留在 Eppendorf 管中）凝结。将循环内容物倒入培养皿中，将凝块放入称重船中称重。用生理盐水轻轻冲洗管道并称重。  \n\n协议与批准：细菌粘附研究由麻省理工学院生物危害评估和胚胎干细胞研究监督委员会批准，并在适当的 BL-2 设施中进行。人体血液研究根据麻省总医院（MGH）机构审查委员会（IRB）批准的方案进行，并在适当的 BL-2 设施中进行。  \n\n体内装置闭塞：研究在同济医院外科研究室进行。三头雌性关西八马猪（28-30 千克），年龄 6 个月，体重 21-22 千克，购自中国湖北宜之城生物科技有限公司。所有体内动物实验均遵循《湖北省实验动物管理条例》，并经《华中科技大学实验动物伦理委员会章程》审查批准。  \n\n向臀大肌注射氯胺酮（6-8 毫克/千克−1 ）以达到麻醉目的。将留置针插入耳静脉，静脉注射 2 毫升丙泊酚和 2 毫升芬太尼，然后输注生理盐水和阿托品以维持麻醉。置入气管插管并与呼吸机连接，以提供氧气和异氟醚。手术区常规消毒后，切开腹壁、皮下组织和筋膜，小心向上分离股动脉和股静脉，露出髂总动脉和髂静脉。髂动脉直径 ${\\approx}3$ 毫米，髂静脉直径 ${\\approx}8$ 毫米。小心分离并暴露髂动脉 ${\\approx}8$ 厘米的部分。近端用动脉夹夹住，远端用一个小弯血球夹夹住。然后，用眼科剪刀在距离夹钳 1 厘米处做一个 V 形切口。  \n\n用生理盐水润滑已消毒的原始装置和涂层装置，排气，然后小心地插入髂动脉切口。然后小心地关闭切口，以避免血液渗漏。然后松开远端血压计。在腹股沟区域加入足够的生理盐水，使装置完全浸没，并在装置下方放置一块纱布，以便进行超声监测。一旦超声探头定位正确，就松开近端夹钳并启动计时器。通过多普勒超声监测血流和流速。一旦多普勒速度降为零，表明装置内形成血凝块（管腔完全堵塞），实验即停止。计时器停止计时。  \n\n统计分析：数据未经预处理，全部使用 Microsoft Excel 的内置函数进行分析。本文中的所有数据，除非另有说明，否则误差条均代表数据集www对.a于dv摩an擦c试ed验sc（ie图n c2ean）e，ws每.c个o时m间点取六个数据点的平均值。对于接触角测量（图 2b），每个数据点测量六次。在细菌覆盖表征方面（图 2d），对每种条件拍摄六张显微镜图像，并对每对条件（原始与涂层）进行单尾 t 检验。对于纤维蛋白网络覆盖（图 3b），每个数据点拍摄三张显微图像，并在每个时间点进行双尾 t 检验。对于裂解实验（图 3d），对每个条件进行四次吸光度测量，并对试管条件（原始和涂层）与对照进行双尾检验。对于 OTEG 结果（图 3f），分析了六次实验的参数，并以方框图（用 Origin Pro.）这里的误差条（晶须）分别指第 5 个和第 95 个量值。对两种条件下的每个 OTEG 参数进行了双侧 t 检验。对于体外凝血和粘附实验（图 4c），使用了三次测试的结果，并对每个指标进行了双侧 t 检验。对于体内闭塞实验，使用三次实验所测得的时间，并对涂有涂层的和未涂过涂层的进行双尾 t检验。  \n\n原始的管道。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 辅助信息  \n\n辅助信息可从 Wiley 在线图书馆或作者处获取。  \n\n[1] D.J. Kuter, Oncologist 2004, 2, 207.",
+        "category": " References"
+    },
+    {
+        "id": 8,
+        "chunk": "# 致谢  \n\n作者衷心感谢麻省总医院和同济医院所有合作者的宝贵协助和技能。这项工作得到了国家自然科学基金（CMMI-1661627）、海军研究办公室（N00014-17-1-2920）和美国陆军研究办公室通过麻省理工学院士兵纳米技术研究所（W911NF-13-D-0001）提供的支持。",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# 利益冲突  \n\n作者声明没有利益冲突。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 10,
+        "chunk": "# 作者供稿  \n\nG.P.、Y.Y.和C.N.对本研究做出了同等贡献。G.P.、Y.Y.、C.N.和Z.H. 构思并设计了实验。G.P.和Y.Y.制作了涂层装置并进行了大部分体外实验。D.T. 和 S.N. 完成了 OTEG 凝血研究。W.R. 和 S.L. 协助进行了体外血液循环研究。Q.L.、Y.Z.、J.W.和 L.L. 进行了体内实验。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 关键词  \n\n防污水凝胶、抗血栓水凝胶、基于水凝胶的医疗设备、韧性水凝胶设备  \n\n收到：2020 年 7 月 1 日修订：2020 年 8 月 21 日在线发表：  \n\n1159.   \n[3] I.H. Jaffer, J. C. Fredenburgh, J. Hirsh, J. I. Weitz, J . Thromb.Haemostasis 2015, 13, S72.   \n[4] S.S. C. Günther、C. Schwebel、R. Hamidfar-Roy、A. Bonadona、 M. Lu-gosi、C. Ara-Somohano、C. Minet、L. Potton、J.- C.Cartier, A. Vésin、 M.Chautemps, L. Styfalova, S. Ruckly, J.-F.Timsit, Intensive Care Med. 2016, 42, 1753.   \n[5] C.Wall, J. Moore, J. Thachil, J. Intensive Care Soc. 2016, 17, 160.   \n[6] K.K. S. Lavery, C. Rhodes, A. Mcgraw, M. J. Eppihimer, Adv.Drug Delivery Rev. 2017, 112, 2.   \n[7] A.Wallace, H. Albadawi, N. Patel, A. Khademhosseini, Y. S. Zhang, S. Naidu, G. Knuttinen, R. Oklu, Cardiovasc.Diagn.Ther.2017, 7, S246.   \n[8] D.Grau, B. Clarivet, A. Lotthé, S. Bommart, S. Parer, Antimicrob.Resist.Infect.Control 2017, 6, 18.   \n[9] L.N. Tchouta, P. N. Bonde, ASAIO J. 2015, 61, 623.   \n[10] V.Semak, M. B. Fischer, V. Weber, Int.J. Artif.Organs 2017, 40, 22.   \n[11] M.马萨诸塞州韦尔斯利 BCC 研究公司全球导管市场部 Elder 2016.   \n[12] 全球医疗器械市场》，Kalorama 信息公司，弗吉尼亚州阿林顿， 2017 年。   \n[13] J.S. Vanepps, J. G. Younger, Shock 2016, 46, 597.   \n[14] P.P. Parás-Bravo, M. Paz-Zulueta, R. Sarabia-Lavin, F. Jose Amo- Setién, M. Herrero-Montes, E. Olavarría-Beivíde, M. Rodríguez- Rodríguez, B.Torres-Manrique, C. Rodríguez-De La Vega, V. Caso- Álvarez, L. González-Parralo, F. M. Antolín-Juárez, PLoS One 2016, 11, e0162479.   \n[15] B.D. Ratner，《生物材料》，2007，28，5144。   \n[16] B.D. Ratner, J. Biomater.Sci.，Polym.Ed.2012, 11, 1107.   \n[17] T.T. M. Maul, M. P. Massicotte, P. D. Wearden, in Extracorporeal Mem- brane Oxygenation - Advances in therapy (Ed: M.S. Firstenberg), Inte- chOpen, 2016, chp.   \n[18] S.S. M. Hastings、D. N. Ku、S. Wagoner、K. O. Maher、S. Deshpande、 Asaio J. 2017, 63, 86.   \n[19] L.Lucchi, G. Ligabue, M. Marietta, A. Delnevo, M. Malagoli, S. Perrone, L. Stipo, F. Grandi, A. Albertazzi, Artif.Organs 2006, 30, 106.   \n[20] K.P. Sathe、W.-S.Yeo、I. D. Liu、S. Ekambaram、M. Azar、H.- K.Yap, K.-H. Ng, BMC Nephrol.Ng, BMC Nephrol.2015, 16, 3.   \n[21] K.B. Quencer, R. Oklu, Cardiovasc.Diagn.Ther.2017, 7, S299.   \n[22] V.Tchantchaleishvili, F. Sagebin, R. E. Ross, W. Hallinan, K. Q. Schwarz, H. T. Massey, Ann.Surg.Surg. 2014, 3, 490.   \n[23] N.N. M. Lai, N. Chaiyakunapruk, N. A. Lai, E. O'Riordan, W. S. Pau, S. Saint, Cochrane Database Syst.Rev. 2016, 3, CD007878.   \n[24] J.-F.Timsit, Y. Dubois, C. Minet, A. Bonadona, M. Lugosi, C. AraSomohano, R. Hamidfar-Roy, C. Schwebel, Ann.Intensive Care 2011, 1, 34.   \n[25] K.G. Neoh, M. Li, E.-T. Kang, E. Chiong, P. A. Tambyah, J. Mater.Kang, E. Chiong, P. A. Tambyah, J. Mater.Chem.B 2017, 5, 2045.   \n[26] X.Hou, Y. Hu, A. Grinthal, M. Khan, J. Aizenberg, Nature 2015, 512, 70.   \n[27] I.Sotiri, A. Tajik, Y. Lai, C. T. Zhang, Y. Kovalenko, C. R. Nemr, H. Ledoux, J. Alvarenga, E. Johnson, H. S. Patanwala, J. V. I. Timonen, Y. Hu, J. Aizenberg, C. Howell, Biointerphases 2018, 13, 06D401.   \n[28] D.Zhang, Z. Xu, H. Li, C. Fan, C. Cui, T. Wu, M. Xiao, Y. Yang, J. Yang W.Liu, Biomater.2020, 8, 1455.   \n[29] P.P. W. Heyman, C. S. Cho, J. C. Mcrea, D. B. Olsen, S. W. Kim, J. Biomed.Mater.1985，12，419。   \n[30] R.Biran, D. Pond, Adv.Drug Delivery Rev. 2017, 112, 12.   \n[31] M.M. F. Maitz, J. Zitzmann, J. Hanke, C. Renneberg, M. V. Tsurkan, C. Sperling, U. Freudenberg, C. Werner, Biomaterials 2017, 135, 53.   \n[32] I.Reviakine, F. Jung, S. Braune, J. L. Brash, R. Latour, M. Gorbet, W. Van Oeveren, Blood Rev. 2017, 31, 11. //www.fda.gov/media/113951/download. ADVANCED HEALTHCARE   \n[58] M.M. Tripathi、Z. Hajjarian、E. M. Van Cott、S. K. Nadkarni， Biomed.Opt.Express 2014, 5, 817. www.advhealthmat.de   \n[59] M.M. M. Tripathi, S. Egawa, A. G. Wirth, D. M. Tshikudi, E. M. Van Cott S.K. Nadkarni, Sci. Rep. 2017, 7, 9169, https://www.fda.gov/media/ 113951/download.   \n[60] D.D. M. Tshikudi, M. M. Tripathi, Z. Hajjarian, E. M. Van Cott, S. K. Nadkarni, PLoS One 2017, 12, e0182491.   \nGrinthal, J. Aizenberg, Nature 2011, 477, 443.   \n[w34w]w.Aa.dK.vEapnscteidns, cTi.e-Sn.cWeonnegw、s.Rc.oAm. Belisle、E. M. Boggs、J. Aizenberg， Proc.Natl.USA 2012, 102, 13182.   \n[35] D.D. C. 莱斯利、A. 沃特豪斯、J. B. 贝尔特、T. M. 瓦伦丁、A. L. 沃特斯 A.Jain, P. Kim, B. D. Hatton, A. Nedder, K. Donovan, E. H. Super, C. Howell, C. P. Johnson, T. L. Vu, D. E. Bolgen, S. Rifai, A. R. Hansen、 M.Aizenberg、M. Super、J. Aizenberg、D. E. Ingber， Nat.Biotechnol. 2014, 32, 1134.   \n[36] L.Faxälv, T. Ekblad, B.o Liedberg, T. L. Lindahl, Acta Biomater.2010, 6, 2599.   \n[37] T.Ekblad, L. Faxälv, O. Andersson, N. Wallmark, A. Larsson, T. L. Lin- dahl, B. Liedberg, Adv.Funct.Mater.2010, 20, 2396.   \n[38] M.Baghai, N. Tamura, F. Beyersdorf, M. Henze, O. Prucker, J. Rühe、 S.Goto, B. Zieger, C. Heilmann, ASAIO J. 2014, 60, 587. [39] Z.K. Zander, M. L. Becker, ACS Macro Lett.   \n[40] H.H. S. Nanda, A. H. Shah, G. Wicaksono, O. Pokholenko, F. Gao, I. Djordjevic, T. W. J. Steele, Biomacromolecules 2018, 12, 1425.   \n[41] 美国食品和药物管理局，《血管内医疗器械的润滑涂层分离》 ： FDA Safety Communication 2015, safety communication, https://www.fda.gov/media/113951/ download (accessed: August 2020)。   \n[42] R.I. Mehta, R. I. Mehta, Am.J. Med.2017, 130, e287.   \n[43] A.A. M. Chopra 、 M. Mehta 、 J. Bismuth 、 M. Shapiro 、 M. C. Fishbein、A. G. Bridges, H. V. Vinters, Cardiovasc.Pathol.2017, 30, 45.   \n[44] L.Chen, D. Han, L. Jiang, Colloids Surf., B 2011, 85, 2.   \n[45] 美国食品和药物管理局，《带润滑涂层的血管内导管、导线和输 送 系 统 -- 标 签 注 意 事 项 》 ： FDA Guidance 2019, guidance, https://www.fda.gov/media/ 113951/download (accessed: August 2020)。   \n[46] H.Yuk, T. Zhang, G. A. Parada, X. Liu, X. Zhao, Nat.Commun.2016, 7, 12028.   \n[47] G. A. Parada, H. Yuk, X. Liu, A. J. Hsieh, X. Zhao, Adv. Healthcare Mater.2017, 6, 1700520.   \n[48] Y.Yu, H. Yuk, G. A. Parada, Y. Wu, X. Liu, C. S. Nabzdyk, K. YoucefToumi, J. Zang, X. Zhao, Adv. Mater.2019, 31, 1807101.   \n[49] J.Sakamoto, K. Hashimoto, Arch.Toxicol.1985, 57, 282.   \n[50] Z.He, C. Wu, M. Hua, S. Wu, D. Wu, X. Zhu, J. Wang, X. He, Matter 2020, 2, 723.   \n[51] D.Kaneko 、 T. Tada 、 T. Kurokawa 、 J. P. Gong 、 Y. Osada ， Adv. Mater. 2005, 17, 535.   \n[52] J.P. Gong, Y. Katsuyama, T. Kurokawa, Y. Osada, Adv. Mater.2003, 15, 1155.   \n[53] X.Dai, Y. Zhang, L. Gao, T. Bai, W. Wang, Y. Cui, W. Liu, Adv. Mater. 2015, 27, 3566.   \n[54] I.埃舍特、V. 弗雷格、R. 卡舍、M. 赫兹伯格、J. 雷、M. 乌尔布 里希特、 Biomacromolecules 2011, 12, 2681.   \n[55] ISO, 德国标准化研究所，德国柏林，《医疗器械的生物评估--第 4 部分：选择与血液相互作用的测试》，英国标准协会（BSI） ，伦敦，2017 年。   \n[56] L.-C.Xu, J. W. Bauer, C. A. Siedlecki, Colloids Surf., B 2014, 124, 49.   \n[57] E.E. J. van Kampen, W. G. Zijlstra, Adv.Clin.Chem.1966, 8, 141, https ：",
+        "category": " References"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/╤к╦и╨н═м┐╣╛·.json b/task2/task2-chunks/╤к╦и╨н═м┐╣╛·.json
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+[
+    {
+        "id": 1,
+        "chunk": "# Ultrathin and Robust Hydrogel Coatings on Cardiovascular Medical Devices to Mitigate Thromboembolic and Infectious Complications  \n\nGerman Parada, Yan Yu, William Riley, Sarah Lojovich, Diane Tshikudi, Qing Ling, Yefang Zhang, Jiaxin Wang, Lei Ling, Yueying Yang, Seemantini Nadkarni, Christoph Nabzdyk,\\* and Xuanhe Zhao\\*  \n\nThromboembolic and infectious complications stemming from the use of cardiovascular medical devices are still common and result in significant morbidity and mortality. There is no strategy to date that effectively addresses both challenges at the same time. Various surface modification strategies (e.g., silver, heparin, and liquid-impregnated surfaces) are proposed yet each has several limitations and shortcomings. Here, it is shown that the incorporation of an ultrathin and mechanically robust hydrogel layer reduces bacterial adhesion to medical-grade tubing by $95\\%$ . It is additionally demonstrated, through a combination of in vitro and in vivo tests, that the hydrogel layer significantly reduces the formation and adhesion of blood clots to the tubing without affecting the blood’s intrinsic clotting ability. The adhesion of clots to the tubing walls is reduced by over $90\\%$ (in vitro model), which results in an $\\approx60\\%$ increase in the device occlusion time (time before closure due to clot formation) in an in vivo porcine model. The advantageous properties of this passive coating make it a promising surface material candidate for medical devices interfacing with blood.  \n\nCardiovascular devices such as intravascular (IV) catheters are essential for the diagnosis and treatment of many acute and chronic diseases (including cancer, end-stage renal disease, cardiovascular disease, etc.), including the care for critically ill patients in the ICU.[1–10] The US market for these medical devices in 2016 was ${\\approx}\\$9.0$ billion with an expected growth rate of $4.7\\%$ due to the higher incidence of chronic diseases and an overall aging, frailer population.[11,12] Given their widespread use, serious complications such as infections $(5-15\\%$ rate)[4,8,13] and thrombosis $(10-20\\%$ rate)[8,14] are always of concern to clinicians, as they can lead to life-threatening complications such as sepsis, pulmonary embolism and deep-vein thrombosis. These two complications are commonly seen when using indwelling IV catheters such as central venous catheters (CVCs), hemodialysis catheters, and peripherally inserted central catheters (PICCs), as those are often used for longer durations (weeks to months).[1,2,4,5,8,14–16] Moreover, catheter-related complications are costly and challenging to treat as the patients that depend on these catheters are likely frail and/or acutely ill (e.g., in the ICU, patients with severe infections, cancer). Aside from the increased morbidity and mortality associated with, e.g., central venous and urinary catheters, these complications and the associated care costs pose a significant burden on the health care system as a whole.  \n\nThese complications are not unique to catheter devices, as they have also been reported for other blood-contacting devices such as stents, prosthetic bypass grafts, dialysis equipment, ventricular-assisted devices (VADs), artificial heart valves, and extracorporeal membrane oxygenation (ECMO) equipment.[17–22] Despite significant efforts, infectious and thromboembolic complications associated with the use of cardiovascular medical devices continue to represent a significant, unmet clinical challenge, especially given the increasing population of chronically ill patients that depend on these devices.  \n\nThere are currently no commercially available solutions that sufficiently address both thrombosis and infection complications. Most of the commercially available technologies target infectious complications. Those approaches include antiseptic wound dressings, antibiotic-coated catheters and antibioticimpregnated catheters.[7,13,23–28] These technologies show modest reduction of bacteremia but only for select patient populations and short-term catheter usage. None of these approaches yields a device surface that intrinsically decreases bacterial adhesion and thereby mitigates bacterial biofilm formation. Moreover, there is no improvement pertaining to other side effects of catheter usage (including thrombosis), and no proven clinical benefit for longterm applications.[23,24] A separate set of available technologies aims to address thrombosis and the subsequent device occlusion. These approaches rely on attaching bioinert polymers or bioactive molecules such as corn trypsin inhibitor, heparin or thrombomodulin, to the device surface.[6,10,29–32] Despite promising preclinical data, the clinical trial performance has been mixed— only select heparin-coating technologies are able to show clinical benefits.[3,5,6,30]  \n\nThere are very few technologies that aim to address both thrombosis and infections. One approach involves the incorporation of a nanotextured surface that is entrained with perfluorinated liquids.[33–35] This surface repels both bacteria and blood components, however, it has not been translated to clinical use likely due to concerns about the presence of fluorine-containing fluids in bloodstream. A second approach involves the photografting of hydrophilic polymers onto the device surface.[7,36–40] This is a mature technology that was initially developed in the 1980s to reduce the friction and irritation for urinary catheters, and was marketed as a “hydrogel-coating” technology even though it only involves surface polymer grafting and not a 3D polymer network. Most major brands now offer “hydrogelcoated” catheters, with brand names such as Biocath and Lubri-sil (Bard), Flocath (Teleflex), Serpia (Braun), Convey and HydroPlus (Boston Scientific), and HydroPicc (Access Vascular).[41–43] Despite showing clinical performance and being adopted by healthcare professionals, there are concerns about adverse effects stemming from coating failure and delamination, since these grafted coatings are usually tens of nanometers thick.[41,42] The evidence led the FDA to issue a safety communication in 2015 and a labeling guidance in 2019 to address these complications.[44,45] Based on the current clinical data and published literature it is evident that the development of a thrombosis-resistant and bacteria-repellent surface would be a major advancement in the ever growing field of cardiovascular and critical care devices.  \n\nIn this study, we have characterized the mechanical, antibacterial, and thrombosis-resistant properties of ultrathin hydrogel layers introduced on medical device surfaces. The robust adhesion of tough hydrogel materials, a technology recently developed by our group,[46–48] showed the potential to enhance the interfacial properties of elastomer-based medical interfaces. In the experiments discussed here we have used medical-grade Tygon (polyvinyl chloride) tubing, a standard medical device used for blood management in dialysis and cardiopulmonary bypass settings.[12,19] This was done to ensure the blood only contacts a single material, as the blood would be fully contained inside the tubing. Any tests conducted with catheters would require an outer vessel (of a different material) to contain the blood, which is undesired as it may have complicated the analysis. The coated surfaces had low coefficients of friction and withstood fluid flow at physiological rates up to $^{12\\mathrm{h}}$ without any measurable changes. The adhesion of bacteria and fibrin is significantly reduced in comparison to uncoated surfaces. In addition, through a series of in vitro assays and flow loop tests, we showed that the hydrogel coating decreased the formation and adhesion of blood clots to the device surface without compromising the blood’s innate clotting ability. Moreover, we demonstrated in pigs the superior patency rates of hydrogel-coated PVC tubings that were implanted into the systemic circulation (arterial to arterial connection). These initial results indicate that hydrogel coatings of blood-contacting devices may mitigate infection and thrombosisrelated complications of cardiovascular devices and thus could obviate technologies aimed to address these clinical problems individually.  \n\nThe hydrogel coatings were prepared as previously described.[48] This method was chosen as it allowed for the coating of flat surfaces and of the inner and/or outer surface of cylindrical devices (e.g., catheters and tubing). Following published protocols, the coatings in this work were created by first submerging the clean medical surfaces in a benzophenone solution in ethanol. The solution was removed and then an aqueous pregel solution containing N,N-dimethylacrylamide (DMAA) and a biocompatible photoinitiator (Irgacure 2595) was added on the activated surfaces. This monomer was chosen to avoid the toxicity concerns of using acrylamide, the monomer used in previous publications.[49] The surface was then irradiated with UV to polymerize the hydrogel layer. After thorough rinsing of the excess polymers and byproducts, the result was an ultrathin $(\\approx10~\\upmu\\mathrm{m})$ hydrogel layer uniformly coated on the device, as shown schematically in Figure 1a for Tygon CPB tubing. The layer is very thin compared to the typical OD of venous catheters $(5-6\\mathrm{mm})$ or the ID of blood-management tubing $(0.75{-}1.5\\mathrm{cm})$ . Macro images of pristine and coated (inner lumen only) tubing are shown in Figure 1b to demonstrate that the hydrogel coating was uniform and did not affect the overall device dimensions due to its micrometer-sized dimensions. Microscopy images of the cross-section are shown in Figure S1 (Supporting Information). Further details on the chemical composition of the hydrogel coating, the fabrication process and the adhesion mechanism can be found in a previous publication.[48]  \n\nThe elastic modulus of the hydrogel layer was determined previously to be $E\\approx30~\\mathrm{kPa}$ ,[48] value which is two orders of magnitude lower than the pristine Tygon substrate $E\\approx6~\\mathrm{MPa})$ ). The presence of the water-containing hydrogel layer decreased the coefficient of friction (COF) of the surface,[50–53] tested here using a rheometer with a steel parallel plate geometry, as described previously.[47,48] We characterized the COF of both pristine and coated flat surfaces with continuous shearing with a normal force of $1\\mathrm{~N~}$ up to $60~\\mathrm{min}$ , as shown in Figure 2a. The COF of the coated surface was consistently lower than that of the pristine surface throughout the experiment (0.1–0.15 vs 0.30), demonstrating the remarkable mechanical robustness of the interpenetrated hydrogel layer. Coatings with are not robust would have been eroded by the constant shearing and the COF would increase to a similar value as the uncoated substrate. It is important to note that these loading conditions exceeded those eventually seen in actual applications. The coating could also withstand fluid flow at physiologically relevant rates $(\\approx1.5$ $\\mathbf{L}\\operatorname*{min}^{-1}.$ ) and pressures $({\\approx}100\\ \\mathrm{mmHg})$ ). Using the setup shown in Figure 2b, saline was circulated continuously for up to $^{12\\mathrm{~h~}}$ through a coated tubing segment. At selected time points, the surface water contact angle was measured by the sessile drop method, and the coating thickness was assessed using fluorescent microscopy. Since the pristine Tygon surface is hydrophobic, the measured contact angle of the pristine sample was above $80^{\\circ}$ . A decrease in the measured contact angle (under $40^{\\circ}$ ) was observed after the introduction of the ${\\approx}10\\ \\upmu\\mathrm{m}$ hydrogel coating. There was no change in the contact angle or coating thickness after continuous flow up to $12\\mathrm{{h}}$ , evidence of the robustness and integrity of the hydrogel coating.  \n\n![](images/07e4c42444b60ed7fcd2b66f72a7554b4d839676c56ad43354585175d2b04b99.jpg)  \nFigure 1. Hydrogel coatings on medical device surfaces. a) Schematic illustration of the mitigation of bacterial adhesion and thrombosis on vascular medical devices through the use of the proposed ultrathin hydrogel coatings. b) The medical device used in this study is Tygon cardiopulmonary bypass (CPB) tubing, both pristine and hydrogel-coated. The hydrogel coating is shown schematically here highlighting its micrometer-sized thickness. c) Macroscopic images of coated and pristine tubing to demonstrate the methodology used here generates even and uniform hydrogel coatings on feet-long tubing segments.  \n\n![](images/879cc59b7e09fd03ee7ccb19dfd1dadacfb603dc62ea6078f21ed690f6488a34.jpg)  \nFigure 2. Mechanical and antibacterial properties of hydrogel-coated surfaces. a) Coefficient of friction (COF) of pristine and coated surfaces continuously sheared for 1 h. Error bars represent SD of the COF values time-averaged over 3 min. b) Contact angle and hydrogel layer thickness measurements after continuous flow of saline solution (flowrate $\\approx1.5\\mathsf{L}\\mathsf{m i n}^{-1}$ ) for up to $\\mathsf{12h}$ in the apparatus depicted to the left. Error bars represent SD of multiple measurements for each time point. c) Representative fluorescent microscopy images of pristine and coated surfaces with GFP-expressing E. coli in bright green. d) Quantification of E. coli (area) coverage of pristine and coated surfaces for static and flow testing conditions. The flow condition was carried out in an apparatus similar to that shown in subsection (b). Error bars represent SD of multiple areas analyzed.  \n\nPrevious publications have shown that hydrated surfaces (grafted polymers and bulk hydrogels) can serve as antifouling layers to prevent the adhesion of unwanted agents.[7,39,47,48,54] The antifouling performance of the DMAA-based ultrathin hydrogel coatings was assessed with regards to their in vitro efficacy against bacterial and fibrin adhesion. Coated and pristine surfaces were contacted with media containing engineered Escherichia coli and incubated for 4 and $^{8\\mathrm{{h}}}$ in static and flow conditions, respectively. E. coli is a common pathogen seen in ambulatory and nosocomial infections,[2,4,7,8] and the strain used in these experiments was engineered to express GFP for easy visualization using fluorescent microscopy. Bacterial adhesion and colonization of coated surfaces were significantly reduced in both static and flat tests as compared to the pristine surfaces $(\\mathtt{p}<<$ 0.05), as shown in Figure 2c. Microscope imaging as shown in Figure 2d revealed that the hydrogel coating prevented bacterial adhesion even in the absence of eluting antibiotics.  \n\nIn a similar fashion, coated and pristine surfaces were incubated with heparinized human blood containing Alexa Fluor 488- tagged fibrinogen, following published protocols.[34,35] This allowed for visualization of the fibrin network formation as the blood started to coagulate on the surfaces. As shown in Figure 3a, confocal microscopy imaging revealed that fibrin deposition and network formation was significantly greater on the pristine substrates for every time point as compared to the coated ones. It is important to note that no macroscopic clotting was seen in these experiments as the blood was heparinized. The quantification across various representative areas and samples is shown in Figure 3b, and was comparable with the antifouling behavior reported for hydrogels and perfluorinated surfaces.[34–37,54] A similar adhesion-resistant behavior against other blood proteins and factors in the coagulation cascade is expected for the hydrogel coatings presented in this work, although additional work would be needed to verify and quantify this hypothesis.  \n\nNext, bovine whole blood was used to further characterize the interaction of surface coating and blood in a setting closer to the intended applications than the tests described above. The objective of the following tests was to compare device-related thrombus formation, adhesion, and occlusion for coated and uncoated tubing, tests required under the ISO standard to evaluate the blood compatibility of medical devices.[55] Bovine blood was chosen since it is commercially available and large blood volumes $\\scriptstyle\\left(>50{\\mathrm{mL}}\\right)$ were needed for these experiments. As stasis promotes coagulation,[3,15,16,32,56] experiments were conducted while maintaining constant motion of the blood phase in order to minimize this confounder and to characterize the interaction of blood and surface coating more exclusively.  \n\nThe first test was a simple approach to introduce flow, and this was done by moving a column of blood back and forth inside tubing until clotting occurred, as shown in the videos in the Supporting Information. The occlusion time was defined as the time when a macroscopic thrombus occluded the lumen of the tube and thus no blood movement could be seen when inverting the tubing. The results of several tests carried out are shown in Figure 3c. In the absence of movement (i.e., stasis), the clotting time for coated and pristine tubes was no different than that of the control (blood in an Eppendorf tube). When the blood was agitated, the measured clotting time was longer in coated tubing than in pristine tubing. The spread in the data most likely represented variability in the blood samples used, as the tests were run at different days. In addition, it is important to notice that the 5 topmost coated tests were arbitrarily stopped at $t=25$ min even though blow flow within the tubing was still observed. Upon closer inspection there was still uncoagulated blood inside the tubing, and the thrombi noted were not attached to the tubing surface unlike in the pristine tubing tests.  \n\nOverall these were very promising results suggesting that the coating had the potential to improve the performance of bloodcontacting devices passively, i.e., without the presence of an anticoagulant such as heparin or citrate. While the use of heparincontaining surfaces has been proposed to reduce thrombosis complications (such as GORE CARMEDA or Medtronic Cortiva bioactive coatings), the introduction of heparin also carries negative side effects such as the risk of hemorrhage and heparininduced thrombocytopenia. Moreover, this local anticoagulant property is difficult to control and may have unpredictable effects in patients with abnormal coagulation. Overall the clinical effect of these heparin-coated surfaces is modest and short-lived at best.  \n\nOne potential explanation for the results seen in Figure 3c could have been that the hydrogel coating interferes with the blood’s coagulation cascade by either cell lysis, binding or denaturing of key factors. Thus, two experiments were carried out to rule out these scenarios. First, whole blood samples were incubated on top of pristine and coated tubing under mild agitation and subsequently collected and pelleted using a centrifuge. The supernatant was analyzed with a spectrophotometer at the strongest absorption frequencies for oxygenated hemoglobin (540 and $576~\\mathrm{nm}$ ).[57] The samples were compared to a negative control (untreated bovine blood) and a hemolyzed positive control (hypotonic hemolysis), as shown in Figure 3d. The measurements confirmed that the coating did not cause any significant hemolysis when compared to the negative control (baseline). Hemolysis would have resulted in the release of hemoglobin from the red blood cell cytoplasm into the supernatant, which would have resulted in higher absorbance values.  \n\nSecond, optical thromboelastography (OTEG) was performed to quantify the effect of the hydrogel coating on the blood clotting process.[58–60] This method, illustrated schematically in Figure 3e, analyzes the autocorrelation function of a reflected laser beam and generates an OTEG graph (shown at the bottom of  \n\n![](images/19f4742941fc563daa69eccd004bcf37e31a183e945284c6c493f1112cfac9a8.jpg)  \nFigure 3. In vitro dynamic and static blood tests. a) Representative images of fibrin network formation on pristine and coated surfaces. Fluorescently tagged fibrinogen was added to blood for visualization of the network. b) Area coverage of fibrin network on surfaces. Error bars represent SD of multiple areas analyzed. c) Time elapsed until the tubin occluded by clot formation for pristine and coated tubing under static or dynamic (agitation) conditions. Control u ube Abs orb of the rnatant afte entrifugation of bloo ontact with pristine and coated tubing at the main wavelen lobi ntrols blood d lysed blood. Error bars represent SD of 3–4 samples. e) Schematic f dified (OTEG tifie Box plots of normalized activation time (R), clotting time $(R+K)$ (MA) of blo with coated and pristine tubing. The normalization was done with a control sample (analyzed without c nt unt for variability in blood samples  \n\nFigure 3e).[58] The rising curve indicates the clotting of the blood, where $R$ is the activation time (time until clotting starts) and R $+\\ K$ is the total clotting time. The strength of the clot is measured by the MA (max. amplitude) value. We compared the clotting times and clot strength of blood samples that were placed in pristine and coated tubes as shown in Figure 3e,f. The values were normalized by those of a control sample (blood left in Eppendorf vial) to account for sample variability, and the data is presented as whisker plots. Both R, $R+K$ and MA values of pristine and coated tubes were not different from each other (as indicated by $p$ -values above 0.05 from t-tests), indicating that the hydrogel coating does not interfere with coagulation itself (unlike heparineluting or heparin-coated surface) and that stasis must be avoided in order to highlight the beneficial effects of the hydrogel coating.  \n\nIn a separate, clinically relevant in vitro experiment simulating a cardiopulmonary bypass (CPB) circuit, closed circular tube loops (Tygon CPB tubing) were created and whole blood was circulated through the loops using a CPB machine roller pump (Figure 4a). In this scaled-down model of a CBP circuit used during cardiac surgery, low flow rates of $0.25\\mathrm{~L~min^{-1}}$ were used to avoid over-pressurization, leakage from the circuit, and hemolysis. The blood in the loops was circulated until a control blood sample (in stasis in an Eppendorf vial) fully coagulated. The contents were poured into a petri dish and the clot was removed and weighed. The tubing was gently rinsed twice with saline and then weighted. Bovine blood that was circulated through pristine tubing formed larger amounts of wall-adhering clots than blood in contact with coated tubing, as shown in Figure 4b. The quantitative results from three repeat experiments is shown in Figure 4c.  \n\n![](images/5ec9d202e1642461c7fb349e35184901f2bb1ae96b86e4620ce3b2eb4fe71d3d.jpg)  \nFigure 4. In vitro blood loop tests. a) Image of apparatus used for continuous flow testing of pristine and coated tubing. Testing was done in parallel to accurately control the end time point of flow. b) Image of pristine (left) and coated (right) tubing after flow testing and gentle rinsing with saline. c) Quantification of blood clotting and clot adhesion to the tubing walls for blood flow experiments. Error bars represent SD for three repeated experiments.  \n\nThe mean tubing weight increase for the pristine tubing is $5.03\\%$ while that of coated tubing is $0.19\\%$ . This statistically significant increase $(p<0.05)$ indicates that blood clots adhered more readily to the pristine than to the coated tubing. Next, the fraction of the original blood that had formed a blood clot was assessed (clots adhered to the tubing and those in the petri dish). Approximately $40\\%$ of the blood in contact with the pristine tubing clotted, as compared to the $6.2\\%$ of that in contact with the coated tubing. This difference is also significant with $\\mathtt{p}=0.003$ .  \n\nThese two results are very promising evidence that the hydrogel coatings on Tygon tubing and other elastomer-based blood contacting devices show potential to address thrombosisrelated complications without the need of heparin or other antithrombosis medications. It is conceivable that the hydrated, lubricious surface of the coated tubing decreased the adhesion and/or activation of either platelets or coagulation factors, as suggested by previous publications.[9,10,56,44] Additional work is required to fully understand the mechanisms behind the beneficial effects mediated by these hydrogel coatings, and to tailor the hydrogel chemistry and fabrication methods to further improve their performance.  \n\nTo further demonstrate that the developed hydrogel coating can delay clotting on medical devices in the absence of anticoagulation medication, we carried out a small preliminary in vivo study in which tubing was used as an arterial bypass on the iliac artery of anesthetized Bama pigs. No anticoagulation medicine such as heparin was administered. A schematic is shown in Figure 5a. Briefly, an incision was made on the groin area and an ${\\approx}7~\\mathrm{cm}$ section of the iliac artery was exposed. The two ends were clamped with a hemostat and small incisions were made at about $1\\mathrm{cm}$ distal to the clamping. The bypass device was inserted into the incisions and sutured to avoid leakage. The clamps were then released and Doppler ultrasound and ultrasound imaging was used to measure the flow of blood through the bypass and thrombus formation inside the bypass (Figure 5c,d). The experiment was stopped when no more blood flow was observed from the ultrasound imaging, and the occlusion time was recorded.  \n\nUncoated and hydrogel-coated medical-grade silicone tubing ( $\\mathrm{1.2~mm}$ ID, 7 cm length) were sterilized and used as the arterial bypass in this preliminary study. Silicone tubing was used as it is more flexible and has smaller wall thickness than the Tygon tubing used in previous sections. Three experiments were run for each condition. For the uncoated devices, the mean occlusion time was 366.7 s with an SD of $90.7\\mathrm{~s~}$ , as shown in Figure 5e. The mean occlusion time for the hydrogel-coated devices was 590.5 s with an SD of $130.9\\:\\mathrm{s}$ , time that was longer than that of the uncoated device $(p=0.032$ from one-tail t-test). In the absence of systemic anticoagulation, introducing a hydrogel coating to the devices resulted in a $60\\%$ increase in the occlusion time. The result of this preliminary in vivo experiment matches the result obtained in the in vitro experiment, supporting our earlier findings that introducing an ultrathin hydrogel coating on elastomer-based medical devices can delay the formation and adhesion of blood clots to the device surfaces. It is important to note that this result was obtained with a different (and more realistic) blood flow pattern and with narrower lumen dimensions, which suggests the geometry of the device is not relevant as long as the blood-contacting surface has a uniform and thin hydrogel coating. In particular, the variables in this experiment (e.g., arterial bypass instead of arterial to venous fistula and very small inner luminal diameter) were purposely chosen to worsen the flow profile through the tubing and thereby rapidly precipitate vascular occlusion. Therefore, these significant differences in patency are very encouraging.  \n\nWe conclude that the present study could serve as an early proof-of-concept for using the hydrogel-coating technology as a design strategy that may mitigate the thromboembolic and infectious complications that arise from the use of blood-contacting medical devices.  \n\n![](images/6afe4728c1bb5405383c0b615ea6fef66d93752fc0343dbf4379fec966f99a9a.jpg)  \nFigure 5. In vivo device occlusion tests. a) Schematic of porcine model used to assess the performance of the coated devices under constant blood flow. b) Image of iliac artery to which the silicone tubing was attached to. The incision allowed access for direct ultrasound-based flow monitoring within the silicone tubing. c) Doppler ultrasound images of the devices at the start of the experiment (left) and at the end of the experiment (right). The absence of blood flow velocities on ultrasound measurements indicated that the device is occluded by a clot attached to its inner surface. d) Quantification of the occlusion time of the devices in three repeated experiments. Error bars represent the SD for three repeated experiments.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Experimental Section  \n\nHydrogel Coatings on Tygon Surfaces: All chemicals were purchased from Millipore-Sigma and used as received, unless indicated otherwise. The experimental protocol was as follows. The medical-grade (U.S. Plastic Corp.) flat surface or tubing was cut to the desired size, cleaned with isopropanol and DI water, and fully dried with a nitrogen stream. The devices are then air-plasma treated (PDC-001, Harrick Plasma, ${<}350$ torr, 18 W) for $1{-}2\\mathsf{m i n}$ and submerged in a benzophenone solution ( $10\\mathrm{\\Omega}\\mathrm{wt\\%}$ in ethanol) for $3{-}5\\mathsf{m i n}$ . The devices are removed from the solution, the excess ethanol is removed by blotting with tissue, and the devices are submerged in a previously degassed hydrogel precursor solution $(20-30\\mathrm{wt\\%}$ N,N-dimethylacrylamide, $0.5\\ \\mathrm{wt\\%}$ Irgacure I-2959 in water). For flat surfaces, there should be at least $5\\:\\mathsf{m m}$ of precursor solution above the surface. For tubing, the precursor solution should completely fill the inner lumen. The devices were then exposed to UV (UVP CL-1000, $\\lambda=365~\\mathsf{n m}$ ) for $45\\min$ to create the interpenetrating hydrogel layer on the device surface. The polymerized solution was removed and disposed as waste. The devices were thoroughly washed with DI water for 3 days (submerged in water and left in the shaker for flat surfaces, connected to a peristaltic CBP (VWR, variable flow pump) for tubing) before testing.  \n\nFriction Measurements: The Coefficient of Friction was measured for flat surfaces $(5\\times5~{\\mathsf{c m}})$ using a rheometer (AR-G2, TA Instruments) in normal force control mode with a $20~\\mathsf{m m}$ steel parallel plate geometry. The coefficient of friction was calculated from the measured torque and normal force following a protocol used previously.[39,40] Briefly, pristine and coated samples were loaded into the rheometer and a $\\rceil\\textsf{N}$ normal force was applied to the sample, and a steady-state shear rate of $0.5\\ {\\mathsf{s}}^{-1}$ was applied. The normal force and torque were measured for an hour. The data for a 2.5 min interval was analyzed and reported.  \n\nRobustness Against Flow: The apparatus shown in Figure 2b was assembled by connecting $3/4^{\\prime\\prime}$ ID tubing to a peristaltic pump (Cole Parmer Masterflex L/S). A section of coated tubing was connected on the outlet side of the pump, and a clamp was placed downstream to adjust the outlet pressure. A flow rate of $1.5\\ L\\min^{-1}$ was set, and at every time point, a $2c m$ section of the coated tubing was removed for analysis. The contact angle was measured via the sessile drop method, in which a $3\\upmu\\up L$ drop of water was placed on the surface, imaged using a high-resolution camera and back illumination, and the angle was measured using ImageJ (NIH). The hydrogel thickness was measured by cross-sectioning the tubing, contacting it with a fluorescein solution (hydrophilic dye) and imaging it with a fluorescent microscope (Eclipse LV100ND, Nikon). The coating thickness was quantified using built-in tools (NIS-Elements software).  \n\nBacterial Adhesion: An engineered E. coli strain that expresses green fluorescent protein (GFP) used in previous publications[47,48] was cultured in Luria-Bertani broth (LB broth) overnight at $37^{\\circ}C$ A $7m L$ aliquot of bacteria culture was diluted in $70\\mathsf{m L}$ of fresh LB broth and placed on top of flat samples $\\cdot1\\ c m\\times1\\ c m)$ and incubated for $4h$ at $37^{\\circ}\\mathsf{C}$ (static condition). For the flow condition, a scaled-down version of the apparatus in Figure 2b was set up using a VWR peristaltic pump and $3/8^{\\prime\\prime}$ ID tubing—the bacterial solution flowed through the tubing for $8\\ h$ at $37^{\\circ}\\mathsf C$ . After the incubation, the samples were taken out, gently rinsed twice with phosphate buffered saline (PBS) to remove the free-floating bacteria, and imaged with a fluorescence microscope (Eclipse LV100ND, Nikon). The bacterial coverage on the samples was quantified using Image J.  \n\nFibrin Deposition: Following previously published protocols,[31,32] the wells of a 24-well plate (Corning) were blocked with $1\\mathrm{wt\\%}$ bovine serum albumin (BSA) in PBS for 30 min and rinsed with PBS. Pristine and coated flat samples $(1\\times1~\\mathsf{c m})$ were placed in the blocked wells with heparinized whole human blood $0.25\\mathrm{~U~mL^{-1}}$ to prevent overall clotting) spiked with fluorescently labeled fibrinogen (Alexa Fluor 488 conjugated human fibrinogen, ThermoFischer Scientific). The samples were incubated for increasing time points on an orbital shaker at room temperature. After removing them from the well, the samples were gently rinsed with normal saline ( $0.9\\%$ sodium chloride) and fixed for $\\rceil\\boldsymbol{\\mathsf{h}}$ with $2.5\\%$ glutaraldehyde in $0.1~\\mathsf{m}$ phosphate buffer before imaging with an upright confocal microscope (SP8, Leica). The images were analyzed and quantified with ImageJ. Blood Hemolysis: Citrated bovine blood samples $(\\approx3~\\mathsf{m L})$ were placed on the inner lumen of pristine and coated tubing $(3/8^{\\prime\\prime}|\\mathsf{D})$ for 5 min under gentle agitation. Two controls were used—as-received blood and lysed blood ( $20\\%$ DI water added). The blood was then poured on Eppendorf tubes and centrifuged for 2 min (VWR minicentrifuge). The supernatant was placed in disposable cuvettes and analyzed using a UV–vis spectrophotometer (BioMate 3S, Thermo Scientific) at two wavelengths, 540 and $576\\ n m$ , which correspond to the max. absorbance for oxygenated hemoglobin.  \n\nOptical Thromboelastography: The equipment used for these experiments was custom-built by researchers in the Nadkarni group, as described elsewhere.[51–53] The data collection and analysis algorithms are also described in those publications. Citrated human blood was placed inside pristine and coated tubing $(3/8^{\\prime\\prime}|\\mathsf{D})$ for $3\\mathrm{\\min}$ , then recalcified with $0.2\\mathrm{~m~}$ calcium chloride solution in saline $(60\\upmu\\mathrm{L}m\\mathrm{L}^{-1}$ blood). $\\mathsf{A n}\\approx\\mathsf{l o0}\\upmu\\mathsf{L}$ aliquot of blood was placed in a silicone blood collection cartridge and analyzed at $37^{\\circ}\\mathsf{C}$ until coagulation was measured. Control samples were done in which the blood was recalcified and analyzed without contacting any tubing. The parameters were obtained by fitting the OTEG curves using custom-built MATLAB algorithms.  \n\nBlood Flow Inside Tubing Tests: Two different types of tests were carried out. For the first type, $3m L$ citrated bovine blood was recalcified using 0.5 m calcium chloride in saline $(24\\upmu\\up L$ per mL blood) and placed inside pristine and coated tubing ${\\bf\\langle\\approx9^{\\prime}}$ long, $3/8^{\\prime\\prime}$ ID). The tubing had been previously sterilized with ethanol and UV radiation, and thoroughly rinsed with saline solution. The tubing was agitated back and forth as shown in the videos (in the Supporting Information) until a clot was formed or $25\\mathrm{\\:min}$ elapsed. The clotting time, which was determined when the blood column stopped moving, was recorded. For the second type of tests, the blood agitation was provided by a CBP roller pump (Cobe Century). Here, $20^{\\prime\\prime}$ sections of $3/8^{\\prime\\prime}$ ID pristine and coated tubing was filled with recalcified blood $(\\approx25$ $m\\mathsf{L}$ ) and closed into a loop by attaching a small section of $3/4^{\\prime\\prime}$ tubing to the ends. The tubing was weighted before and after filling with blood. $\\mathsf{A}0.25\\mathsf{L}\\mathsf{m i n}^{-1}$ flow was set up until a control sample (left in Eppendorf tube) clotted. The loop contents were poured into a petri dish, the clot was placed in a weigh boat and weighted. The tubing was gently rinsed with normal saline and weighted.  \n\nProtocols and Approvals: The bacterial adhesion studies were approved by MIT’s Committee on Assessment of Biohazards and Embryonic Stem Cell Research Oversight, and carried out in the appropriate BL-2 facilities. The human blood studies were covered under an approved protocol by the institutional review board (IRB) of the Massachusetts General Hospital (MGH), and carried out at the appropriate BL-2 facilities.  \n\nIn Vivo Device Occlusion: The study was carried out at a research animal surgical suite at Tongji Hospital. Three female Guanxi Ba-ma pigs $(28-30\\ k g)$ aged 6 months and weighing $21\\mathrm{-}22\\mathrm{kg}$ , were purchased from of Hubei Yizhicheng Biotechnology Co., Ltd, China. All in vivo animal procedures follow the “Regulations of Hubei Province on the administration of experimental animals,” and were reviewed and approved by “The Charter of Laboratory Animal Ethics Committee of Huazhong University of Science and Technology.”  \n\nKetamine $(6{-}8\\mathrm{~mg~}\\mathsf{k g}^{-1})$ was injected into the gluteus maximus to induce anesthesia. An indwelling needle was placed in the ear vein, IV propofol $2m L$ and fentanyl $2m L$ were injected, followed by infusion of normal saline and atropine to maintain anesthesia. An endotracheal tube was placed and connected to a ventilator to supply oxygen and isoflurane. After routine disinfection of the surgical area, an incision was made, the abdominal wall, subcutaneous tissue and fascia were cut, and the femoral artery and femoral vein carefully separated upward to expose the common iliac artery and the iliac vein. The diameter of the iliac artery was ${\\approx}3~{\\mathsf{m m}}$ , and that of the iliac vein was ${\\approx}8~\\mathsf{m m}$ . An $\\approx8~{\\mathsf{c m}}$ section of the iliac artery was carefully separated and exposed. The proximal end was clamped with an arterial clamp and the distal end was clamped with a small curved hemostat. Then, a v-shaped incision was made with ophthalmic scissors 1 cm away from the clamps.  \n\nThe sterilized pristine and coated devices were lubricated with saline solution, vented, and carefully inserted in the incisions of the iliac artery. The incisions were then carefully closed to avoid blood leaks. The distal hemostat was then released. Enough saline was added the groin area to fully submerge the devices, and a gauze was placed under them for ultrasound monitoring. Once the ultrasound probe was positioned correctly, the proximal clamp was released and a timer was started. Blood flow and velocity were monitored by Doppler ultrasound. The experiment was stopped once the Doppler velocity dropped to zero, indicating the formation of a clot inside the device (and complete occlusion of the lumen). The timer was stopped.  \n\nStatistical Analysis: No preprocessing was done for the data, and it was all analyzed using built-in functions with Microsoft Excel. For all the figures in this article, the error bars represent the SD of the set unless otherwise noted. The significance level for all t-tests was set at alpha $=0.05$ , so statistically significant difference was noted if the $p$ -value was below  \n\n0.05. The $p$ -value is indicated in the figures directly, caption, or discussed in the text.  \n\nFor the friction tests (Figure 2a), six data points were averaged per time point. For the contact angle measurements (Figure 2b), six measurements were done per data point. For the bacterial coverage characterization (Figure 2d), six microscopy images were taken for each condition and a onetailed t-test was carried out for each pair of conditions (pristine vs coated).  \n\nFor the fibrin network coverage (Figure 3b), three microscopy images were taken for each data point and a two-tailed t-test was carried out at each time point. For the lysis experiments (Figure 3d), four absorbance measurements were obtained per condition and two-tailed test were carried out comparing the tubing conditions (pristine and coated) versus the control. For the OTEG results (Figure 3f), the parameters from six experiments normalized by the control for each experiment were analyzed and shows as a boxplot (plotted with Origin Pro. 8.5). Here the error bars (whiskers) refer to the 5th and the 95th quantile, respectively. A two-sided t-test was done comparing the two conditions for each OTEG parameter.  \n\nFor the clotting and adhesion in vitro experiment (Figure 4c), results from three tests were used and a two-tailed t-test was done for each metric. For the occlusion in vivo experiment, the times measured from three experiments were used and a two-tailed was done between the coated and pristine tubing.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 3,
+        "chunk": "# Supporting Information  \n\nSupporting Information is available from the Wiley Online Library or from the author.",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# Acknowledgements  \n\nThe authors gratefully acknowledge all coauthors at the MGH and Tongji hospital for their valuable assistance and skills. This work was supported by the NSF (CMMI-1661627) and the Office of Naval Research (N00014-17-1-2920) and the U.S. Army Research Office through the Institute for Soldier Nanotechnologies at Massachusetts Institute of Technology (W911NF-13-D-0001).",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# Conflict of Interest  \n\nThe authors declare no conflict of interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 6,
+        "chunk": "# Author Contributions  \n\nG.P., Y.Y. and C.N. contributed equally to this work. G.P., Y.Y., C.N., and Z.H. conceived and designed the experiments. G.P. and Y.Y. fabricated the coated devices and carried out most in vitro experiments. D.T. and S.N. enabled the OTEG coagulation studies. W.R. and S.L. assisted with the in vitro blood loop studies. Q.L., Y.Z., J.W., and L.L. carried out the in vivo experiments.",
+        "category": " References"
+    },
+    {
+        "id": 7,
+        "chunk": "# Keywords  \n\nantifouling hydrogels, antithrombotic hydrogels, hydrogel-based medical devices, tough hydrogel devices  \n\nReceived: July 1, 2020 Revised: August 21, 2020 Published online:  \n\n[2] D. G. Maki, D. M. Kluger, C. J. Crnich, Mayo Clin. Proc. 2006, 81, 1159. [3] I. H. Jaffer, J. C. Fredenburgh, J. Hirsh, J. I. Weitz, J. Thromb. Haemostasis 2015, 13, S72. [4] S. C. Günther, C. Schwebel, R. Hamidfar-Roy, A. Bonadona, M. Lugosi, C. Ara-Somohano, C. Minet, L. Potton, J.-C. Cartier, A. Vésin, M. Chautemps, L. Styfalova, S. Ruckly, J.-F. Timsit, Intensive Care Med. 2016, 42, 1753. [5] C. Wall, J. Moore, J. Thachil, J. Intensive Care Soc. 2016, 17, 160. [6] K. S. Lavery, C. Rhodes, A. Mcgraw, M. J. Eppihimer, Adv. Drug Delivery Rev. 2017, 112, 2. [7] A. Wallace, H. Albadawi, N. Patel, A. Khademhosseini, Y. S. Zhang, S. Naidu, G. Knuttinen, R. Oklu, Cardiovasc. Diagn. Ther. 2017, 7, S246. [8] D. Grau, B. Clarivet, A. Lotthé, S. Bommart, S. Parer, Antimicrob. 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Aizenberg, Proc. Natl. Acad. Sci. USA 2012, 109, 13182.   \n[35] D. C. Leslie, A. Waterhouse, J. B. Berthet, T. M. Valentin, A. L. Watters, A. Jain, P. Kim, B. D. Hatton, A. Nedder, K. Donovan, E. H. Super, C. Howell, C. P. Johnson, T. L. Vu, D. E. Bolgen, S. Rifai, A. R. Hansen, M. Aizenberg, M. Super, J. Aizenberg, D. E. Ingber, Nat. Biotechnol. 2014, 32, 1134.   \n[36] L. Faxälv, T. Ekblad, B.o Liedberg, T. L. Lindahl, Acta Biomater. 2010, 6, 2599.   \n[37] T. Ekblad, L. Faxälv, O. Andersson, N. Wallmark, A. Larsson, T. L. Lindahl, B. Liedberg, Adv. Funct. Mater. 2010, 20, 2396.   \n[38] M. Baghai, N. Tamura, F. Beyersdorf, M. Henze, O. Prucker, J. Rühe, S. Goto, B. Zieger, C. Heilmann, ASAIO J. 2014, 60, 587.   \n[39] Z. K. Zander, M. L. Becker, ACS Macro Lett. 2017, 7, 16.   \n[40] H. S. Nanda, A. H. Shah, G. Wicaksono, O. Pokholenko, F. Gao, I. Djordjevic, T. W. J. Steele, Biomacromolecules 2018, 19, 1425.   \n[41] US Food & Drug Administration, Lubricious Coating Separation from Intravascular Medical Devices: FDA Safety Communication 2015, safety communication, https://www.fda.gov/media/113951/ download (accessed: August 2020).   \n[42] R. I. Mehta, R. I. Mehta, Am. J. Med. 2017, 130, e287.   \n[43] A. M. Chopra, M. Mehta, J. Bismuth, M. Shapiro, M. C. Fishbein, A. G. Bridges, H. V. Vinters, Cardiovasc. Pathol. 2017, 30, 45.   \n[44] L. Chen, D. Han, L. Jiang, Colloids Surf., B 2011, 85, 2.   \n[45] US Food & Drug Administration, Intravascular Catheters, Wires, and Delivery Systems with Lubricious Coatings—Labeling Considerations: FDA Guidance 2019, guidance, https://www.fda.gov/media/ 113951/download (accessed: August 2020).   \n[46] H. Yuk, T. Zhang, G. A. Parada, X. Liu, X. Zhao, Nat. Commun. 2016, 7, 12028.   \n[47] G. A. Parada, H. Yuk, X. Liu, A. J. Hsieh, X. Zhao, Adv. Healthcare Mater. 2017, 6, 1700520.   \n[48] Y. Yu, H. Yuk, G. A. Parada, Y. Wu, X. Liu, C. S. Nabzdyk, K. YoucefToumi, J. Zang, X. Zhao, Adv. Mater. 2019, 31, 1807101.   \n[49] J. Sakamoto, K. Hashimoto, Arch. Toxicol. 1985, 57, 282.   \n[50] Z. He, C. Wu, M. Hua, S. Wu, D. Wu, X. Zhu, J. Wang, X. He, Matter 2020, 2, 723.   \n[51] D. Kaneko, T. Tada, T. Kurokawa, J. P. Gong, Y. Osada, Adv. Mater. 2005, 17, 535.   \n[52] J. P. Gong, Y. Katsuyama, T. Kurokawa, Y. Osada, Adv. Mater. 2003, 15, 1155.   \n[53] X. Dai, Y. Zhang, L. Gao, T. Bai, W. Wang, Y. Cui, W. Liu, Adv. Mater. 2015, 27, 3566.   \n[54] I. Eshet, V. Freger, R. Kasher, M. Herzberg, J. Lei, M. Ulbricht, Biomacromolecules 2011, 12, 2681.   \n[55] ISO, German Institute for Standardization, Berlin, Germany Biological Evaluation of Medical Devices—Part 4: Selection of Tests for Interactions with Blood, British Standards Institution (BSI), London 2017.   \n[56] L.-C. Xu, J. W. Bauer, C. A. Siedlecki, Colloids Surf., B 2014, 124, 49.   \n[57] E. J. van Kampen, W. G. Zijlstra, Adv. Clin. Chem. 1966, 8, 141, https: //www.fda.gov/media/113951/download.   \n[58] M. M. Tripathi, Z. Hajjarian, E. M. Van Cott, S. K. Nadkarni, Biomed. Opt. Express 2014, 5, 817.   \n[59] M. M. Tripathi, S. Egawa, A. G. Wirth, D. M. Tshikudi, E. M. Van Cott, S. K. Nadkarni, Sci. Rep. 2017, 7, 9169, https://www.fda.gov/media/ 113951/download.   \n[60] D. M. Tshikudi, M. M. Tripathi, Z. Hajjarian, E. M. Van Cott, S. K. Nadkarni, PLoS One 2017, 12, e0182491.",
+        "category": " References"
+    }
+]
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diff --git a/task2/task2-chunks/╤╨╛┐╣д╫ў╨б╜с.json b/task2/task2-chunks/╤╨╛┐╣д╫ў╨б╜с.json
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+[
+    {
+        "id": 1,
+        "chunk": "透明的超双疏涂层能够在排斥低表面张力液体的同时，在可见光范围内维持较高的透明度，为光学表面如太阳能电池、窗户、电子屏幕、军事设备的自清洁防污提供了潜在的应用。超双疏特性在防水、防冰、防腐蚀、自清洁和抗菌等领域也同样发挥着重要的作用。然而，大多数超双疏材料往往需要依赖于悬垂结构以使低表面张力液滴稳定在 Cassie 状态，而为了获得较高疏液性而制备的微米级粗糙结构往往会造成强烈的可见光散射，使超双疏材料的透明度变低。针对现有超双疏材料透明度低、制备方法复杂和基材适用性差等问题，本文设计了可大规模应用的纳米球模板喷涂法来制备具有分级“类蘑菇形”悬垂结构的透明超双疏材料，研究了材料的表面结构对疏液性和透明度的影响，以及材料在自清洁、防污、液体图案化和辐射制冷等方面的应用。主要研究成果如下：  \n\n1. 制备基于多级纳米悬垂结构的透明超疏油材料。通过喷涂含有原位生长二氧化硅的聚合物纳米球溶胶-凝胶溶液，在固化后除去纳米球模板和低表面能处理即可实现透明超双疏材料的制备。当单分散聚苯乙烯纳米球模板尺寸为 50nm，硅溶胶质量分数为 $30\\mathrm{wt\\%}$ 时，制备得到的材料具有优异的透光性和疏液性，对水具有超过 $165^{\\circ}$ 的静态接触角和低于 $1^{\\circ}$ 的滚动角，水滴很难沉积到材料表面，对表面张力低至 $25\\mathrm{mN/m}$ 的十二烷液滴具有 $155^{\\circ}$ 的静态接触角。同时，可见光区域的平均透光率达 $89\\%$ ，与玻璃基材透光率相当。制备得到的材料不仅表现出亚微米级的分形结构，材料表面还具有起疏液性关键作用的纳米悬垂“蘑菇形”结构，其结构为相互连接的二氧化硅网状骨架，能够在连续沙粒冲击和砂纸磨损下保持超疏油性能，具有良好的耐酸性、耐盐性和热稳定性。  \n\n![](images/e08b8f92a00afedcd493fad775fa5d9a4108d952ed6531d47817a7c7734f7a75.jpg)  \n图1-1 (a) 基于纳米球模板法制备透明超双疏涂层; (b) 经过染色的水滴，乙二醇，橄榄油和十二烷液滴滴在透明超双疏玻璃表面的照片。基底下放置文字图案用于证明涂层的透明性；(c) 不同表面张力液滴在超双疏涂层和普通玻璃表面的接触角；(d) 材料表面微纳米结构对光学性质的影响；(e) 超双疏玻璃与原始玻璃的透射率对比  \n\n![](images/57ad1265ce3d3e854cea7104cbfdd1f1bee13b1883195e705653a36a59955016.jpg)  \n图1-2 不同质量分数溶胶所制备涂层的SEM 图像。(a) $30\\mathrm{wt\\%}$ 。(c) $10\\%$ 。(e) $50\\mathrm{wt\\%}$ 。插图显示了制备的能够超疏低表面张力液体的纳米悬垂结构。比例尺： $200\\mathrm{nm}$ 。溶胶浓度为(b) $30\\mathrm{wt\\%}$ , (d) $10\\mathrm{wt\\%}$ , (f) $50\\%$ 时所制备涂层的结构示意图。d 是两个相邻悬垂结构之间的距离，其中， $\\mathrm{d}3>\\mathrm{d}2>\\mathrm{d}1$  \n\n2. 优化制备工艺，研究超疏油材料在太阳能电池等领域的应用。增加溶剂溶解去除纳米球模板的方式，拓宽了透明超双疏涂层在不同材料如织物、木材、金属、高分子和陶瓷等表面的制备。研究发现，在粗糙表面制备的透明超双疏涂层具有更优异的滚动角性能，在木材上制备的涂层具有低于 $6^{\\circ}$ 的十二烷液滴滚动角，原始粗糙的表面结构对降低涂层表面固液接触面积有促进作用。喷涂法能够将涂层制备在曲形界面上，超双疏改性后的样品瓶表现出和玻璃表面类似的优异疏液性能。在应用方面，通过抗菌测试验证了材料的优异抗细菌粘附性。电池表面的自清洁测试实验表明，涂层改性不会影响电池的光电转换效率，且为电池表面提供了疏油自清洁防护层。通过对超双疏材料进行等离子体的选择性暴露，我们能够制备出具有不同形状的亲疏液体图案化表面，在液体微阵列、微流芯片和防伪方面具有潜在应用前景。  \n\n![](images/4b95a4980d9e09a564ddc1af568d4500260a98bd1edfd1a0ebf59cb6943b393b.jpg)  \n图2-1 (a) 染色水滴组成的亲水性液体图案; (b) 疏水性液体图案; (c) 乙二醇在改性玻璃表 面滚动后形成的微图案; (d) 当液体流过改性玻璃表面时，防伪图案逐步显示示意图  \n\n![](images/5a20d21631eb263dabc21d7f41c34999a4575e8f138863541de4138e3def3d63.jpg)  \n\n图2-2 经过荧光染色的大肠杆菌在涂层和裸玻璃表面生长0, 8, 16, 24 小时后对材料表面的  \n\n粘附性能  \n\n![](images/59e85b1a084a2f79d8283cc73e9e383c3408101756382dcc0132754449fe2910.jpg)  \n\n图2-3 (a) 透明超双疏改性导电玻璃；(b) 透明超双疏改性对导电玻璃ITO 和FTO 透光性的影响；(c) 导电玻璃ITO 和FTO 在涂层改性处理前后润湿性变化；(d) 自组装太阳能电池示意图；(e) 涂层改性处理前后太阳能电池I-V 曲线对比；(f)太阳能电池经过涂层改性处理前后、灰尘污染、去离子水清洁后光电转化效率对比  \n\n3. 制备自清洁型辐射制冷材料。使用 $\\mathrm{Al}_{2}\\mathrm{O}_{3}$ 颗粒对PVDF 膜进行预处理，并在表面覆盖纳米悬垂氧化硅结构，制备了具有超双疏性能的辐射制冷膜（SDRCfilm）。所制备的超双疏辐射制冷膜，具有大于 $155^{\\circ}$ 的十二烷静态接触角和低于 $7^{\\circ}$ 的滚动角。反射率光谱测试表明，SDRC 膜在太阳光能量最高处具有高反射率，平均反射率为 $92.01\\%$ ，大气透明窗口平均发射率为 $96.67\\%$ 。经户外实地测试，在太阳辐照最高的时期，SDRC 膜内凹槽温度比空气温度平均低 $6.45^{\\circ}\\mathrm{C}$ ，最高能低 $7.8^{\\circ}\\mathrm{C}$ ，比对照组隔热铝箔最高可低 $10.5^{\\circ}\\mathrm{C}$ ，具有优良的日间辐射冷却性能。  \n\n![](images/ad710b0e3f21d005d98eb1989b25a99a0954ada459cccdb20cdbd683d3ad2b1f.jpg)  \n图3-1 超双疏日间辐射制冷膜的构建策略  \n\n![](images/cede503ca85372d9b75293a9208fd2579cddbdc84ad72e794af654ff4682f659.jpg)  \n图3-2 超双疏辐射制冷膜在 $0.3\\mathrm{-}18~\\upmu\\mathrm{m}$ 区间内的反射率  \n\n![](images/0847be9da73c99b32d9b35279731a3dfaea7e8c0aeda4b249a602159c36bd5ae.jpg)  \n图3-3 (a) 原始PVDF 膜和超双疏辐射制冷膜的表面润湿性；(b) 不同表面张力液滴在原始PVDF 膜和超双疏辐射制冷膜上的接触角；(c) 不同表面张力液滴在超双疏辐射制冷膜上的滚动角；(d) 水滴在超双疏辐射制冷膜上的弹跳状态；(e) 橄榄油和十六烷在超双疏辐射制冷膜上的粘附性状态  \n\n![](images/3a7146cba95c5f0809297d06996de8a3c18bf37bb2aa573ba13a9b4fbc78c678.jpg)  \n图3-4 SDRC 膜日间制冷效果(a) 实时太阳光功率和日间测得的空气、铝箔和辐射制冷膜的温度数据； (b) 环境温湿度变化；(c) 铝箔和辐射制冷膜与空气的温度差",
+        "category": " Results and discussion"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Molecular design in drug discovery: a comprehensive review of deep generative models  \n\nYu Cheng, Yongshun Gong, Yuansheng Liu, Bosheng Song and Quan Zou  \n\nCorresponding authors: Yuansheng Liu, College of Information Science and Engineering, Hunan University, 2 Lushan S Rd, Yuelu District, 410086 Changsha, China. E-mail: yuanshengliu@hnu.edu.cn; Bosheng Song. E-mail: boshengsong@hnu.edu.cn",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# Abstract  \n\nDeep generative models have been an upsurge in the deep learning community since they were proposed. These models are designed for generating new synthetic data including images, videos and texts by fitting the data approximate distributions. In the last few years, deep generative models have shown superior performance in drug discovery especially de novo molecular design. In this study, deep generative models are reviewed to witness the recent advances of de novo molecular design for drug discovery. In addition, we divide those models into two categories based on molecular representations in silico. Then these two classical types of models are reported in detail and discussed about both pros and cons. We also indicate the current challenges in deep generative models for de novo molecular design. De novo molecular design automatically is promising but a long road to be explored.  \n\nKey words: deep generative model; deep learning; de novo drug design; molecular design",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# Introduction  \n\nIn the long-term struggle between humans and diseases, especially the recent pandemic of coronavirus disease 2019 (COVID19), drugs are playing an increasingly significant role. However, the drug discovery process has been confronted with obstacles, which requires a great deal of manpower, material and financial resource. For example, the drug development cycle from preclinical target screening to final marketing takes an average of at least 13.5 years [1]. And developing a new drug for a pharmaceutical company is a costly tour of about 1.8 billion with a high failure rate. The challenging process of drug discovery is derived from the large and discrete searching space of chemical molecules [2]. Specifically, the scale of possible structures of drug-like compounds is between $10^{23}$ and ${10^{60}}$ , but a small proportion of them about $10^{8}$ are therapeutically relevant [3, 4]. Traditional methods like high-throughput screening [4] are inefficient as the required amounts of resources and small number of hit compounds are not balanced. Big data and high-performance computing capabilities have allowed artificial intelligence to surpass traditional brute strength [5]. With the widespread application of deep learning, it is naturally considered as the potential way for drug discovery. Deep learning has been utilized in drug discovery and development, providing a new direction in pharmaceutical science [6]. Some related applications are shown in Figure 1.  \n\nDeep learning, whose prototype was the perceptron known as neural networks for pattern recognition [7], aimed at learning the latent distribution and representation of data. The concept of deep learning was formally proposed for solving the vanishing gradient problem by Hinton et al. [8] in 2006. Then in the ImageNet image recognition competition, the team led by Hinton used the AlexNet model [9] that made a sensation for eliminating vanishing gradient via the ‘ReLU’ activation function. In 2016, the triumph of AlphaGo [10] proved that deep learning was promising in surpassing humans. Up to now, deep learning has been applied successfully to computer vision [11, 12], natural language processing [13, 14], and some other fields [15, 16]. Deep neural networks are divided into discriminative models and generative models. The discriminative models which reflect the difference between heterogeneous data are to find the optimal classification [7]. The generative models, modeling the prior probability, represent the similarity of congener data.  \n\n![](images/938e707cbe9e39240288845046a79d272f0700e733de3ee532d1239070bcbe95.jpg)  \nFigure 1. The applications of deep learning in drug discovery and development.  \n\nDeep generative models develop rapidly as generating new synthetic data from given samples, including images [17], text [18] and video [19]. The representations of molecules in silico are similar to texts in natural language processing and graphs in social networks. Hence, it is natural to extend such models for de novo molecular design in drug discovery [20]. Different from using discriminative models to screen databases and classify molecules as active or inactive, deep generative models design new molecules with target properties from scratch. The desire for generating molecules automatically has been mentioned in the past by Gómez-Bombarelli et al. [21]. And in recent years, plenty of deep generative models have been devoted to boosting the de novo molecular design, which predominantly has followed two strategies based on the representations of molecules in silico. The first strategy focuses on a sequence representation—simplified molecular input line entry system (SMILES) [22], which utilizes deep generative models and text to generate moleculars. An alternative is to encode molecular into graphs [23] that learn to aggregate information (e.g., bond features and atoms). As a consequence, we categorize these typical models into two categories, i.e. SMILES-based and graph-based models.  \n\nIn this review, we mainly focus on deep generative models for molecular generation in drug discovery. We first introduce the representation methods of molecules and conclude the prevalent databases. We show the pros and cons of different representations. As for generative models, we emphasize the recent advances based on different representations in the de novo molecular design domain. The objective evaluation and the comparison of state-of-the-art models facilitate the selection and improvement for readers. However, there are still some challenges about data and deep learning methods in drug discovery. Therefore, we enumerate current challenges that have been observed in the field to promote the development of new research. Here, the survey is meant to accelerate drug discovery through the sharing and comparison of deep generative models, finally reduce the cost and time with the intervention of silico models.  \n\nrespectively. Specifically, each atom type (carbon, hydrogen, oxygen., etc.) can be encoded into T dimensional one hot vector xi, and the bond type (single, double, triple and aromatic bond) can be represented as $y\\in\\{1,\\ldots,\\Upsilon\\}$ . With the hot research trend of deep learning on the graph [28, 29], training deep generative models based on the molecular graph has emerged in a matter of just a few years and now many works make this be one of the most prominent fields. The more details of graph-based works will be described below.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# Molecular representation and dataset in molecular generation",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# Molecular representations  \n\nThe past few decades have observed the arising of keen interest in computational methods especially with the emergence of deep learning. The appearance of such techniques opened the door to the computer-aided drug design. The major challenges here were how to recognize and store molecules accurately by computers and be acceptable for chemists. A flurry of molecular representations have been designed in the last few years owing to the rapid development of computers [24]. Here we introduce two common representations used in de novo molecular design, including SMILES and graphs.",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# SMILES-based representation  \n\nSequence-based representations mainly use linear strings to express compounds and they can easily be memorized and processed by computer systems. One-dimensional linear representation currently includes SMILES and international chemical identifier (InCHI) [25]. SMILES is an ASCII string that uses a mapping algorithm from molecular graphs to text, where simplifies chemical structure with strict grammars. The example of the SMILES form of a molecule is shown in Figure 2A. The conversion from molecular structure to texts makes SMILES easy to be processed by computers, convenient for chemists and easy to use for training machine learning models [26]. The first strategy for automatic molecular design is to use SMILES-based deep generative models and convert this representation into one-hot vectors. Both the good sides, there are also the disadvantages of SMILES: (1) SMILES fails to capture the molecular structural similarity. A small change between two similar structures may cause the SMILES strings to be greatly different, which the latent space learned from generative models is not smooth. (2) The SMILES string is non-unique, a molecule can be encoded into multiple SMILES representations. These problems have been solved more or less in current work. Aiming at the shortages of canonical SMILES in the generative models, there are many studies in producing the variants of the SMILES notation and improving the models, more will be shown specifically in the section of SMILES-based models..",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# Dataset for drug discovery  \n\nThe training of models in machine learning is based on the data, hence we focus on the datasets involved in de novo molecular design here. Specifically, we divide the datasets involved in the typical molecular generative models into the following categories.  \n\nThe first is the comprehensive databases, which usually contain diverse information such as biological activity, chemical structure and physical properties, including ZINC [30, 31], ChEMBL [32], PubChem [33] and DrugBank [34, 35] appeared in higher frequency. In particular, the data fields of drug in DrugBank can be linked to other databases like PubChem [36]. The second one is the merged databases. These databases are chemical datasets by combining and screening existing databases not only for generating molecules, but also for the validation of various machine learning methods as the benchmark. The MOSES platform [37] screens the ZINC by some rules and divides the final data set into three groups, training set, test set and scaffold set to ensure the diversity of molecules. There are also task-specific databases, which are used in other tasks related to drug discovery, such as L1000 CMap [38] with gene expression profiles, CEPDB [39] for learning potential structures of photovoltaics and so on. The last type, chemical space datasets, contains compounds of specific atom composition in a way similar to enumerating chemical space. For instance, quantum machine (QM) [40, 41] extracted from GDB [42, 43], containing molecules composed of CHONF and their quantum chemical properties. Table 1 shows the specific description of the datasets which are commonly used for de novo molecular design, including the number of compounds contained in these datasets up to now, released years, links, etc.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# Deep molecular generative models  \n\nIn recent years, de novo molecular design, a concept of generating molecules with desired from scratch, can be implemented by either professional experts or machines. Due to the development of generative models, molecular generation not only decreases the searching space of chemical molecules but also time consumption for drug discovery compared with humans. Here, we overview some typical molecular generative models based on two classical representations in the following and summary the timeline of them in Figure 3.",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# Graph-based representation  \n\nSMILES is generated from the graph-based representation of molecules [27]. And structural formulas are often used to represent molecules in chemistry. Thus, a more intuitive way to depict molecular structures is the molecular graph. The example of the graph form of a molecule is shown in Figure 2B. Each molecule can be represented as an undirected graph $\\mathcal{G}$ where the nodes set $\\nu$ and the edge set $\\varepsilon$ are composed of atoms $v_{i}$ , and bonds $\\left({\\boldsymbol{v}}_{\\mathrm{i}},{\\boldsymbol{v}}_{\\mathrm{j}}\\right)$",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# SMILES-based models  \n\nPowerful deep learning techniques have driven the development of generative models. After training on realistic data, generative models are able to produce new synthetic data that are similar to given samples. A central question in deep generative models to be solved is how to capture the unknown data distribution and reveal the internal hidden structures. One of the ways is to learn the data representations which can be easily modeled [45]. In the field of de novo molecular design, a good representation also is capable of being converted back into molecules readily. In terms of the simple characteristics of SMILES, it has been proven easier to learn for deep learning. And the sequence-based methods can be further divided into variational encoder (VAE) [46], generative adversarial networks (GANs) [47] and recurrent neural networks (RNNs) [48] based models.  \n\n![](images/f653c1e9d2a28855ece7e4dc5683639fa0d3520149798b718eb8ec55f38c5a6b.jpg)  \nFigure 2. The process of de novo molecular design for drug discovery.  \n\nTable 1. Datasets of de novo molecular design for drug discovery   \n\n\n<html><body><table><tr><td>Datasets</td><td>Description</td><td>Compound Link</td><td></td><td>Year</td><td>Reference</td></tr><tr><td>ZINC</td><td>A free virtual scanning dataset of</td><td>V</td><td>http://zinc15.docking.org/</td><td>2004</td><td>[30,</td></tr><tr><td>ChEMBL</td><td>commercial compounds Manage and edit biologically active</td><td>750000000 1961462</td><td>http://zinc15.docking.org/</td><td>2009</td><td>31] [32]</td></tr><tr><td></td><td>molecules with drug-like properties</td><td></td><td></td><td></td><td></td></tr><tr><td>QM9</td><td>Small organic molecules with maximum nine atoms in four different types</td><td>134k</td><td>http://quantum-machine.org/datasets/&# x2216;#qm9</td><td>2014</td><td>[40, 41]</td></tr><tr><td>PubChem</td><td>Unique structures with the largest and free chemical information</td><td>103278272</td><td>https://pubchem.ncbi.nlm.nih.gov/</td><td>2004</td><td>[33]</td></tr><tr><td>ExCAPE-DB</td><td> Aggregate PubChem and ChEMBL</td><td>997992</td><td>https://solr.ideaconsult.net/search/excape/</td><td>2016</td><td>[44]</td></tr><tr><td>GDB-13</td><td>Chemical universe database</td><td>977468314</td><td>http://gdb.unibe.ch/downloads/</td><td>2009</td><td>[42]</td></tr><tr><td>GDB-17</td><td>Chemical universe database</td><td>50000000</td><td>http://gdb.unibe.ch/downloads/</td><td>2012</td><td>[43] /</td></tr><tr><td>MEGx</td><td>Natural products from plants and microorganisms</td><td>> 4200</td><td>https://ac-discovery.com/purified-natural- product-screening-compounds/</td><td>2017</td><td></td></tr><tr><td>DrugBank</td><td>With bioinformatics and cheminformatics</td><td>13643</td><td>https://www.drugbank.ca/</td><td>2006</td><td>[34,</td></tr><tr><td>MOSES</td><td>resource A benchmarking dataset</td><td>4591276</td><td>https://github.com/molecularsets/moses</td><td>2018</td><td>35] [32]</td></tr><tr><td>CEPDB</td><td>The Harvard Clean Energy Project Database</td><td>2300000</td><td> http://cepdb.molecularspace.org</td><td>2011</td><td>[37]</td></tr><tr><td>L1000</td><td>Contains mainly induced gene expression</td><td>32855</td><td>https://clue.io/</td><td>2017</td><td>[38]</td></tr></table></body></html>  \n\n![](images/347aacc8f6d5219251a5e34d0983e00d4fcddf299406c2fcb4786f36b6fd1a86.jpg)  \nFigure 3. The timeline of deep generative models for molecular design.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# • VAE-based generative models  \n\nVAE generally contains an encoder and a decoder, which the encoder maps discrete data to a continuous latent space[46]. Further, in order to perform unconstrained optimization for specific properties, the decoder is responsible for reconstructing from the latent vector to SMILES with chemical validity. VAE-based models aim at maximizing the evidence lower bound (ELBO) of the likelihood with Kullback-Leibler divergence. Notably, the latent space of VAE for molecular generation is potentially operated such as controlling the specific properties and the training process is stable. However, reconstructing the training sets limits the ability of exploring in unknown chemical space.  \n\nGómez-Bombarelli et al. [21] first proposed the character VAE composed of encoder, decoder and predictor (refer Figure 2.1). First, the kernel density estimation was used to learn to capture the relevant features of the molecules. Then continuous latent spaces were learned on dimensions, optimizing the specific properties of the molecules, allowed the use of powerful gradient-based to efficiently guide the search. Adding the joint training task of multi-layer perceptron and encoder guaranteed the prediction ability of molecular properties. A trick here was using Gaussian process to reach the points with target attributes. The contribution could be described as a new method for exploring the molecular space in which no prior knowledge was required to manually construct a compound library. Simultaneously, the model captured the character characteristics of the molecule and showed good predictive ability. We take the view that not all the generated one in this model can be converted back to original space owing to the non-uniqueness of SMILES. For this situation, one approach is to give the model explicit restrictions about how to produce valid molecules. For instance, GVAE [49] incorporated the grammar production rules of SMILES into models. It indicated the discrete data could be directly represented as the parse tree by using context-free grammar. The decoder generated valid outputs by learning these rules in order. Taking parse trees into account enabled the model extended to other text representation learning without context. Later, Dai et al. [50] argued that GVAE was lack of semantics and structural information such as the generated ring bonds must be close. However, adding the extra structural constraints in GVAE may cause the unnecessary waste of computing and time. Inspired of the attribute grammar, Dai et al. [50] proposed to introduce the stochastic lazy links into attribute grammars which achieved on-the-fly generated guidance for both syntax and semantics check.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# • GANs-based generative models  \n\nDuring the past 5 years, case studies using GANs towards the generation of novel molecules with specific desired properties have made milestone progress, especially the combination of GAN and reinforcement learning [51]. GAN includes a generator that imitates the real samples and a discriminator that distinguishes the output of the generator from the actual sample to the greatest extent, while the generator is a liar for the discriminator. The ultimate goal of GANs is to make the discriminator unable to judge whether the output of the generator is the fake. Due to the unstable training of GAN, some variants were proposed like wassertein GAN (WGAN) [52]. WGAN incorporates the EarthMover (EM) distance, which reflects the minimum cost under optimal planning to get a smoother gradient. WGAN not only alleviates the problem of unstable training, but also evaluates reliably generative models to avoid mode collapse.  \n\nBuilding on SeqGAN [53], called objective-reinforced generative adversarial networks (ORGAN) [51], was proposed where added the expert-based rewards under the framework of a WGAN [52]. The combined rewards from the discriminator and domain-specific objectives were extended to the training process that the generator was trained as an agent (refer Figure 2.2). There was also a penalized item which avoided mode collapse. ORGANIC [54], a promotion of ORGAN for inversedesign chemistry, implemented the molecular biased generation towards specific properties.  \n\nBesides using GANs associated with reinforcement learning, many studies followed the mix of GANs and autoencoder to alleviate the instability of GANs. For instance, Prykhodko et al. [55] proposed the latentGAN which combined an autoencoder and a GAN. Previous experiments showed that different randomized SMILES representations of the same molecule were encoded into identical latent vectors which moderated the overfitting due to the canonical SMILES. Compared with the proposed GAN-based models, this architecture was comprised of a heteroencoder, that converted pairs of different representations of SMILES into latent vectors, and the decoder, the inputs of which were trained on the generator and discriminator. It is apparent that SMILES is not the input of the generator and discriminator, but instead latent vectors. Another example was the stacked GAN conditioned on the gene expressions signatures that combines with GVAE. Efficient approaches considering the ligand-target interaction to generate molecules with desired biological activity were lacking before. Lucio et al. [56] employed the transcriptomic data as conditions that obtained the active-like molecules for desired targets.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# • RNNs-based generative models  \n\nVAE models with no extra constraint have a high probability to induce invalid molecules. However, language models extract the information automatically at grammar and semantic levels. RNNs are connected models which are able to capture the dynamics of sequences via cycled units in the network of nodes. Consequently, the models can easily process the input and output that consists of sequences. In recent years, some improvement on the network architectures like long-short term memory (LSTM) [57] and gated recurrent unit (GRU) [58] have been proposed due to the difficult training of RNNs. LSTM, adding the memory cell that replaces conventional units, solves difficulties with training encountered by RNNs. And the simplicity of GRU is more suitable for building larger networks due to the smaller amount of parameters.  \n\nSince the sequence representation of SMILES, the analogy of natural language processing tasks and molecular generation is feasible [27]. For RNNs, the features obtained from large molecular datasets can be transferred to produce molecules with activity on demand in small ones, so that Segler et al. [59] generated focused molecule libraries by retraining the model (refer Figure 2.3). Sampling from the large-scale datasets ensured the diversity of molecules and fine-turning increased the focused properties. The drawback of the model was lack of interpretability. Besides, Zheng et al. [60] built a quasi-biogenic compound library including stereo-chemical properties. In addition to adding transfer learning, the computational model proposed by Moret et al. [61] called chemical language model (CLM), was used to design novel molecules in a designated area of the chemical space by combining three preceding optimized methods (data augmentation, temperature sampling and transfer learning). Linking bioactive synthetic compounds with natural products provides source of inspiration for drug discovery and the result expands the application scope of CLM in a small data regime. Notably, conditional generative models have been recommended, which utilized additional information to guide the molecular design. For example, molecular descriptors values were incorporated into the RNNs-based models [62], which were more focused that the traditional methods.  \n\nAs mentioned above, the canonical SMILES form has the lower capacity to create large chemical spaces of valid and semantics structures than randomized SMILES. [63] sampled with replacement 2 billion times and explored three different variants of the SMILES notation (canonical, randomized and deep) from GDB-13 to prove that hypothesis. In addition, different cell architectures (LSTM [57], GRU [58]) and training set sizes (1000000, 10000 and 1000) were the factors that affected the performance. Experiment showed that LSTM on 1 million randomized SMILES achieved state-of-the-art performance. Moreover, traditional RNNs always generate molecules in a forward manner (left to right). Motivated by the bidirectional RNN [64], non-univocity and non-directionality of SMILES, bidirectional molecule designed by alternate learning (BIMODAL) [65] was proposed. BIMODAL referred the neural autoregressive distribution estimator (NADE) [66], which reconstructed missing information by reading the preceding and subsequent tokens in both directions, and synchronous forward backward RNN (FB-RNN) [67] which generated SMILES forward and backward. BIMODAL predicted the sequence alternately by forward at odd positions and backward at even positions. Due to the limitation of two generating directions in BIMODAL, Arós-ous et al. [68] reported a model that generated molecules from a given scaffold without an assigned attachment. Specifically, the model made use of a slicing algorithm to obtain scaffold sets with randomized SMILES representations. And then partially built molecules were decorated in one attachment once or more than one at a time.  \n\nSince SMILES is regarded as string of texts, a large number of models in natural language processing are able to be extended to the field of de novo molecular design. In future research, for example, we can consider the molecular generation for desired properties as a translation, which can translate from the specific target language (protein sequence) to the SMILES language. Notably, despite the surge of SMILES-based models in recent years, there are still some burning problems. Not only is it facing the issues of validity, but the unstructured nature of SMILES makes two similar molecules be quite different with a high probability. And it is expensive to force the validity constraint to incorporate into the decoders, which requires for designing a novel representation with more structural information.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# Graph-based models  \n\nDeep molecular generative models based on graphs have been a hot trend in the graph research with a prospect for drug discovery. In recent three years, there are many surprisingly effective works in the field of molecular graph generation. Considering the success of VAE models on SMILES, architectures based on VAE with molecular graph design were later developed. GómezBombarelli et al. [21] believed that graph-based representation methods should be further explored. Moreover, with the popularity of graph neural networks, graph-based models also play a dominate role in de novo molecular design.",
+        "category": " Introduction"
+    },
+    {
+        "id": 15,
+        "chunk": "# • VAE-based generative models  \n\nOne of the most representative work is junction tree variational autoencoder (JT-VAE) [69]. JT-VAE assembled the building blocks from the substructures of molecules. The substructures included rings, functional groups and atoms by decomposing the molecules from training sets. In contrast to generating graphs node by node before, the entire process was divided into two phases, first represented the valid scaffolds and their arrangement as the trees and then integrated the whole trees into the graph by adding edges between intersecting components. JT-VAE outperformed the proposed models including CVAE [21], GVAE [49], SD-VAE [50] and GraphVAE [70] in molecular reconstruction and the octanol-water partition coefficients logP score, at mean whiles, JT-VAE reached $100\\%$ in generating valid molecules. The results positively advocated the model for graph-based de novo molecular design, with JT-VAE showing superior results to the previous methods for most of the criteria in the tested conditions. However, this design had three critical limitations. First, it was more difficult to grapple in properties optimization with JTVAE because two molecules with identical junction tree might correspond with markedly different attributes. Second, leaving node order permutation out of consideration during generation procedure caused time-consuming. The ultimate sequence under some possible node permutation might be mapped into the same graph. Third, less than 20 atoms in a substructure were not practical due to the complexity of drug molecules in realistic. Later, in [71], the authors regarded the molecular optimization task as graph-to-graph translation which aimed to learn a multi-model mapping between two domains.  \n\nRecently, Jin et al. [72] keeps on the research of molecular generation by employing substructures to enrich the properties of molecules. However, integrating multiple properties into one molecule is a challenge, there are two reasons: (1) lacking of the molecules fits all the constraints such as potency, safety and desired properties in realistic and (2) bad performance of successful ratio and novelty when adding all the property constraints. To address these drawbacks, substructure sets with respect to single property, called molecular rationale, were assembled into multi-rationale vocabularies of interest and completed by graph generation model. Four properties including c-Jun N-terminal kinase 3 (JNK3) and glycogen synthase kinase $3\\beta$ (GSK- $3\\beta_{.}^{\\cdot}$ ), quantitative estimate of drug-likeness (QED) [73] and synthetic accessibility (SA) [74], aiming at generating Alzheimers disease dual inhibitors with drug-likeness and synthetically accessibility, reached a $100\\%$ successful rate.  \n\nCorrelations between edges often are decomposed into discrete sequenced representations during the generation trace. CGVAE [75] was incorporated two types of correlations including some known rules like valency rules as hard one and ring strain (adverse to cycles) as soft one. CGVAE was kept correlative to convert into SMILES with validity semantically. Notably, molecules with similar properties practically differed in the size of nodes and edges while generative models for molecular graphs like GraphVAE [70] did not take this into account. Samanta et al. [76] have proposed NEVAE aggregated features by distinct hops number. Concurrently, graphs generated from NEVAE took on the permutation invariance at node level and meditated the impact of spatial position on properties. Specially, NEVAE was integrated potential energy with the stability of atoms implemented by Gaussian toolbox.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# • GANs-based generative models  \n\nAlbeit wide application of GANs in some areas, the developments of GANs in generating molecular graphs are tender and delicate. To our best knowledge, GANs are inclined to spawn mode collapse [77]. Since averting likelihood-based loss functions, GAN sends molecular optimization hard stable. It is mansized to balance adversarial training and property constraints. De Cao et al. [78] proposed GANs-based graph generative models, called MolGAN, utilized the likelihood free method and avoided the expensive graph matching procedure. Similar to ORGAN, MolGAN applied the policy gradient reward and WGAN with penalty gradient for small molecular graphs.  \n\nCycle-consistent generative adversarial network (CycleGAN) [79] addressed different domains translation without paired input-output examples so that it is potential to optimize molecules from sets without desired properties. Mol-CycleGAN [80] was designed to implement structural transformations and molecular optimization under the embedding of JT-VAE. Datasets were divided into two parts, one was not equipped with target properties (namely halogen moieties, number of aromatic rings, active) for training and the other was opposite for testing. Notably, bioisosteres are groups or substituents that possess similar chemical properties and produce a wide range of similar or opposite biological activities. Bioisosteres replacement like CF3 and CN is one of the methods in modern molecular design. Specifically, the framework of Mol-CycleGAN could be described as follow: (1) datasets: sets X (e.g., with CN group) and Y (e.g., with CF3 group); (2) mapping: $G:X\\rightarrow Y$ and $\\boldsymbol{\\mathrm{F}}:\\boldsymbol{\\mathrm{Y}}\\rightarrow\\boldsymbol{X},$ cycle consistency loss: encouraged $F(G(x))\\approx x$ and $G(F(y))\\approx y)$ metrics: optimized values of a given property, such as logP. MolCycleGAN has shed new light on molecular optimization under the realistic situation of devoid paired samples. Inspired by MolCycleGAN, we can regard molecular optimization as the problem of machine translation or graph translation.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# • RNNs-based generative models  \n\nGenerative networks based on RNNs model the graph generation as a sequential process and make auto-regressive decisions while they generate graphs. GraphNet [81], the first RNNs-based model on arbitrary graph, was on the framework of the messagepassing neural networks (MPNN) [82]. The essence of GraphNet was to add a new atom or bond into the existing graph. More concretely, (1) choosing to add an atom or not, (2) computing the probabilities over the existing graph to determine if adds a new edge, (3) calculating the probabilities which one node in graph to connect. In addition, Li et al. [83] explored MolMP and MolRNN based on graph convolutional networks (GCN) [84] which was similar with the generation of GraphNet, which generated molecules by iteratively adding nodes and edges to the existing subgraphs. Converting the extra constraints into available conditional codes that did not require reinforcement learning provided higher flexibility and outputs the molecules with more diversity.  \n\nGraphRNN [85], a hierarchical model on the graph and edge levels, aimed at capturing the joint probability of nodes and edges. The process of graph generation was regarded as sequences of adjacency vectors under different node orderings. GraphRNN was equipped with the scalability by introducing a breadth-first search (BFS) node ordering. Subsequently, Some works for molecular generation were extended from GraphRNN. For example, MolecularRNN [86] was added nodes and edges feature vectors associated with them based on GraphRNN. The model was inserted valency-based rejection sampling to ensure valid molecular with $100\\%$ rate. It incarnated the traits and advantages of merging pre-training on large datasets and tuning with policy gradient algorithm. MolecularRNN outperformed JTVAE, GCPN and ORGAN in the penalized logP coefficient and QED [73] with reinforcement learning.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# • Flow-based generative models  \n\nAnother series of methods, flow-based generative models [45, 87, 88], have been applied for image generation and have recently begun to obtain attention in the molecular generation community. With the help of normalizing flow, the flow-based generation models explicitly learn the data distribution which are consist of invertible transformations. The flow takes an initial variable as input and converts it into a variable with an isotropic Gaussian by repeatedly using the change of variable rule, which is similar to the inference procedure in an encoder of VAE [89]. Non-linear independent components estimation (NICE) [45] was the first normalizing flow architecture which showed satisfying performance on the mixed national institute of standards and technology (MNIST) database and was applied for inpainting. It just roughly stacked fully connected layers so that flow-based models needed to be explored further. During the follow-up work, RealNVP [87] and Glow [88] yielded unusually brilliant results and became strong performers in the field of generative models.  \n\nAccording to what we know, prior works put forward five models to generate molecular graphs, GraphNVP [90], graph residual flow (GRF) [91], GraphAF [92], MoFlow [93] and MolGrow [94] included (refer Figure 2.4). GraphNVP [90], the first flowbased molecular graph generation model, improved the uniqueness of molecules. Compared with GraphNVP, GRF [91] reached almost equivalent performance while the number of parameters was reduced. Unfortunately, those two one-shot models displayed poor performance in generating valid molecules. Enlightened by the autoregressive and few flow-based models, a flow-based autoregressive sequential model called GraphAF [92] was proposed. GraphAF outperformed the contemporary stateof-art model graph convolutional policy network (GCPN) [36] and generated $100\\%$ valid molecules by incorporating valency checking. As a one-shot manner, MoFlow [93] was broken many state-of-the-art results that generated bonds by a variant of Glow and atoms with a given bond through a new graph conditional flow. Moreover, the author proposed a new validity correction procedure by deleting the bond of the last order recursively that maintained the largest valid components. Recently, MolGrow [94] showed great results constrained optimization of properties by using latent variables of the model. MolGrow recursively splitted a node into two from a single one to generate molecular structures, which could be regarded as plug-and-play modules. And the model achieved better performance while learning on a fixed atom ordering.  \n\nOverall, based on the generation process, the existing graphbased models can roughly classify into two types, one is the sequential iterative process, the other is one-shot generation. Specifically, they can divide into atom-by-atom, subgraph-based (fragment) models. In order to reduce the number of predicting the edge and train under the possible node permutation, some models such as RationaleRL, MolecularRNN was adopted in a BFS manner. Masking in sequence-based models is introduced for maintaining local structural and functional properties like NEVAE, CGVAE. Graph-based generative models now play a dominant role in the molecular design due to the advantages of graphs and the development of graph neural networks, however, some challenges still remain. To our best knowledge, with the increases of nodes size, the total calculation will grow up the square of nodes number at least, which is difficult to acquire the precise likelihood. Hence, the problem of node ordering should be better solved, which is beneficial for generating molecules with high quality.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# Challenges  \n\nData. De novo molecular design is facing the common failing in artificial intelligence, including the representation, quality and scarcity of data. The training of deep neural networks always relies on sufficient data namely data-driven. Therefore, constructing more satisfying datasets in the field of molecular generation is also a hot-potato to solve. In addition, data for some desired targets are scarce. For this, some models [61] choose to pre-train on the large dataset and then fine-tuned to generate molecules for the specific targets. We take the view that incorporating multi-omics data can make up for the insufficiency of data scarcity in the future. Further, designing a representation with enriched information for molecules is also a challenge. No doubt that sequence-based representations are simpler, but they ignore the structure information to some extent. Moreover, graph-based methods have been widely used, nevertheless, incorporating 3D information into graph-based models is still lacking. Combining 3D information with appropriate structurebased models in a simple manner is the Achilles’ heel and it will be an interesting venue for the future work [27]. Last but not least, learning molecules under the representation of images may be a feasible orientation due to the mature of computer vision.  \n\nModels. Most of current models for molecular generation draw lessons from existing methods in computer vision and natural language processing that do not develop novel models from the perspective of this field. While molecules imitate the representation of images and texts, the generation of images and texts is fault-tolerant. And molecules for drug discovery are extremely strict with validity. From this aspect, designing unique models and appropriate representations belongs to molecules are warranted. To some extent, such models can also be able to be extended to the problems in other fields. And in the future, we are also excited about developing a hierarchical model, which can generate molecular with desired properties in a coarseto-fine manner. A hierarchical model is beneficial for extracting different information when incorporating multi-omics data. As early mentioned, some generative models themselves exist some challenges to face. For example, although the flow-based models reconstruct samples perfectly, the cost of computation is still not as friendly as other generative models. In light of that, reducing expensive cost of flow-based models is the next action to optimize. In addition, the explainability of generative models for molecular design is equally worth being researched.  \n\nMetrics. Most of models employ the evaluation metrics from various aspects as following. Bickerton et al. [73] utilized the concept of desirability called the QED to measure drug-likeness. And Fréchet ChemNet Distance (FCD) [95] is a measure of distribution between training sets and generated molecules. That logP is a particular descriptor estimates the octanol–water partition coefficient. A variant of logP, called penalized logP [49], takes synthetic accessibility and ring sizes into account as penalty. MOSES [37], a benchmarking platform, contains a standardized dataset, a set of indicators and multiple baselines for comparing molecular generation models. However, there are several tasks for which these models generate hard synthetic molecules and provide synthetic routes difficultly despite performing well on common benchmarks. And as a matter of fact, these systematic metrics are a far cry from industry to discovery drugs, namely the generated molecules do not meet the requirement for the practical use. How to balance and unify two metrics systems for discovering drug in a faster and effective fashion runs tough at present. And designing the metrics for the practical use and combining with experiments will allow a major step towards molecular generation.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# Conclusion  \n\nIn this review, we have done our utmost to report different stages of molecular generation evolutionary path and highlight recent advances of research. Both of sequence-based and graph-based generative models have their own merits. The way in which molecular generative models are developed plays an important role for drug discovery and mirrors the evolution of deep neural networks in cross realm. Although substantial progress has been made, there is still large room for improving the performance of existing generative models and ameliorating the metrics of synthetic accessibility. These promotions of technologies and computing power promise to further advance the qualities of generating molecules with well-designed drug-like properties and make further efforts to accelerate the de novo drug design in a fully automated fashion. And these advances of molecular generation also herald a promising future of related problems such as retrosynthesis. With the development of friendly and easy-to-use automat tools, collaborative work of chemists and computer technicians will promote drug discovery further in the future.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 21,
+        "chunk": "# Key Points  \n\n• The ability of de novo molecular design based on deep generative models is of great scientific interest and practical importance for drug discovery.   \n• There are several publicly available drug-related datasets for training deep generative models in molecular design.   \n• There are still challenges on generative models for de novo molecular design, including data, model design and evaluation metrics.",
+        "category": " Abstract"
+    },
+    {
+        "id": 22,
+        "chunk": "# Funding  \n\nThe work was supported by National Natural Science Foundation of China (61972138), the Fundamental Research Funds for the Central Universities (531118010355, 531118010626), Hunan Provincial Natural Science Foundation of China (2020JJ4215) and the Key Research and Development Program of Changsha (kq2004016).",
+        "category": " References"
+    },
+    {
+        "id": 23,
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+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,47 @@
+[
+    {
+        "id": 1,
+        "chunk": "# （19）中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# （12）发明专利申请  \n\n（10）申请公布号CN102850924A（43）申请公布日2013.01.02  \n\n（21）申请号201210355296.X CO8F220/54（2006.01）C08F220/38(2006.01)（22）申请日2012.09.21  \n\n（71）申请人中国海洋石油总公司地址100010北京市东城区朝阳门北大街25号中国海油大厦1414室申请人中海油常州涂料化工研究院中海油能源发展股份有限公司中海油常州环保涂料有限公司  \n\n(72)发明人李焕王木立朱东马智俊   \n(51）Int.CI. CO9D175/04（2006.01) CO9D7/12(2006.01) CO9D5/00（2006.01) CO8F220/14（2006.01) CO8F220/18(2006.01) CO8F220/28（2006.01)",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# （54）发明名称  \n\n一种防雾性持久的防雾涂料",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# （57）摘要  \n\n本发明涉及一种防雾性持久的防雾涂料，它是以防雾特性树脂与封闭型异氰酸酯固化剂配合形成的：其防雾特性树脂是以 $10\\sim50\\mathrm{wt\\%}$ 丙烯酸酯单体 $.1\\sim40\\mathrm{wt\\%}$ 含氮原子的乙烯基单体、1～$10\\mathrm{{wt\\%}}$ 改性的表面活性剂、 $0.1\\sim5\\mathrm{wt\\%}$ 引发剂、余量为亲水性溶剂作为原料，在反应容器中加入亲水性溶剂，升温至 $50\\sim140^{\\circ}\\mathrm{C}$ ，将上述原料混合均匀后，匀速滴加到溶剂中，滴加时间为 $2\\sim5$ 小时，滴加结束后，保温反应 $1\\sim3$ 小时制得的；改性的表面活性剂为含磺酸基、硫酸基或羧酸基团的表面活性剂与（甲基）丙烯酸缩水甘油酯单体按摩尔比 $0.5\\sim2{:}1$ 接枝形成的。本发明防雾涂料防雾性持久且耐水、耐老化，综合性能优异。  \n\n1.一种防雾性持久的防雾涂料，其特征在于，以防雾特性树脂作为主要成膜树脂与封闭型异氰酸酯固化剂配合形成防雾涂料；  \n\n所述防雾特性树脂是以 $10\\sim50\\mathrm{w}\\%$ 丙烯酸酯单体、 $1\\sim40\\mathrm{wt\\%}$ 含氮原子的乙烯基单体 $1\\sim10\\mathrm{wt\\%}$ 改性的表面活性剂 $.0.1\\sim5\\mathrm{wt\\%}$ 引发剂、余量为亲水性溶剂作为原料，在反应容器中加入亲水性溶剂，升温至 $50\\sim140^{\\circ}\\mathrm{C}$ ，将上述单体、改性的表面活性剂和引发剂混合均匀后，匀速滴加到溶剂中，滴加时间为 $2\\sim5$ 小时，滴加结束后，保温反应 $1\\sim3$ 小时，制得的；  \n\n其中，改性的表面活性剂为含磺酸基、硫酸基或羧酸基团的表面活性剂与（甲基）丙烯酸缩水甘油酯单体按摩尔比 $0.5\\sim2{:}1$ 混合均匀后，加入催化剂单丁基氧化锡，升温至$80\\sim180^{\\circ}{\\mathrm{C}}$ 并保温 $3\\sim3.5$ 小时接枝形成的。  \n\n2.根据权利要求1所述的防雾涂料，其特征在于，所述防雾涂料由 $20\\sim50\\mathrm{wt\\%}$ 防雾特性树脂， $2\\sim15\\mathrm{wt\\%}$ 封闭型异氰酸酯固化剂， $0.01\\sim2.0\\mathrm{wt\\%}$ 催化剂，余量为稀释剂组成；所述稀释剂为乙二醇丁醚、丙二醇甲醚、乙二醇乙醚、异丙醇、正丁醇、丙酮、丁酮中的一种或几种；所述催化剂为单丁基氧化锡。  \n\n3.根据权利要求1或2所述的防雾涂料，其特征在于，所述封闭型异氰酸酯固化剂为己丙酰胺、苯酚、甲酚、间硝基苯酚、对氯苯酚、邻苯二酚、丙二酸二乙酯、乙酰内酮、乙酰醋酸乙酯或丁酮封闭剂封端的甲苯二异氰酸酯、己二异氰酸酯或异佛尔酮异氰酸酯。  \n\n4.根据权利要求1所述的防雾涂料，其特征在于，用于制备所述防雾特性树脂的含氮原子的乙烯基单体为（甲基）丙烯酰胺、N-甲基丙烯酰胺、N，N-二甲基丙烯酰胺、 $N-$ 乙基丙烯酰胺，N，N-二乙基丙烯酰胺， $N-{\\mathsf{n}}-$ 丙基丙烯酰胺、 $N-$ 异丙基丙烯酰胺、N，N-二甲基吡咯烷酮、N-甲基吡咯烷酮、N，N'-二甲基氨乙基（甲基）丙烯酰胺、N，N'-二甲基氨丙基（甲基）丙烯酰胺和N-乙基 $-2-$ 吡咯烷酮中的一种或几种。  \n\n5.根据权利要求1所述的防雾涂料，其特征在于，用于制备所述防雾特性树脂的丙烯酸酯单体为（甲基）丙烯酸、（甲基）丙烯酸甲酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸羟乙酯、（甲基）丙烯酸羟丙酯、丙烯酸异辛酯、（甲基）丙烯酸乙酯中的至少两种。  \n\n6.根据权利要求1所述的防雾涂料，其特征在于，用于制备所述防雾特性树脂的亲水性溶剂为乙二醇丁醚、丙二醇甲醚、乙二醇乙醚、异丙醇、正丁醇、丙酮、丁酮中的一种或几种；引发剂为过氧化苯甲酰、过氧化月桂酰、异丙苯过氧化氢、叔丁基过氧化氢、过氧化二叔丁基、过氧化二异丙苯、过氧化苯甲酸叔丁酯、过氧化叔戊酸叔丁基酯、过氧化甲乙酮、过氧化环己酮、偶氮二异丁睛、偶氮二异庚睛、过氧化二碳酸二异丙酯、过氧化二碳酸二环已酯中的一种。  \n\n7.根据权利要求1所述的防雾涂料，其特征在于，用于制备所述防雾特性树脂中改性的表面活性剂的含磺酸基表面活性剂为 $\\mathrm{C}_{10^{-20}}$ 链烷基磺酸、芳烃磺酸、烷基芳烃磺酸、烷基磺基琥珀酸或α-烯烃磺酸；所用的含硫酸基表面活性剂为 $\\mathrm{C_{10-20}}$ 链烷基硫酸（酯）， $\\mathrm{C_{10-20}}$ 链烯基硫酸酯或 $\\mathrm{C}_{10-20}$ 链烷基醚硫酸（酯）；所用的羧酸基团的表面活性剂为 $\\mathrm{C_{8-26}}$ 脂肪酸。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 一种防雾性持久的防雾涂料",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001]本发明涉及一种防雾性持久的防雾涂料，特别适用于透明塑料材质和玻璃材质等的防雾。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002]自上世纪70年代开始，国外有大量公司和研究机构进行防雾涂料的开发，特别是日本公司在90年代出现很多专利，发明了各种各样的防雾涂料。在已公开报道的文献和专利中，防雾涂料发挥防雾作用主要是由于表面活性剂在成膜后富集于涂膜表面，形成超亲水的分子层，使水蒸气在漆膜表面具有很大的接触角，水蒸气不会凝结成水珠，从而达到防雾的效果。但是随着时间的推移，其表面活性剂会溶解在涂膜表面的水中，随着水蒸气的擦除，而慢慢的被带走，从而防雾效果会越来越弱，防雾的持久性差。目前国内外的很多产品都很难达到很好的防雾持久性。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0003]本发明的目的是：提供一种持续防雾性改善且耐老化、耐水的防雾性持久的防雾涂料，主要用于透明塑料基材表面，例如聚碳酸酯板（PC板）亚克力板（PMMA板）和玻璃基材表面，例如镜面等。  \n\n[0004]实现本发明目的的技术方案是：一种防雾性持久的防雾涂料，其特征在于，以防雾特性树脂作为主要成膜树脂与封闭型异氰酸酯固化剂配合形成防雾涂料；  \n\n[0005]所述防雾特性树脂是以 $10\\sim50\\mathrm{wt\\%}$ 丙烯酸酯单体、 $1\\sim40\\mathrm{wt\\%}$ 含氮原子的乙烯基单体、 $1\\sim10\\mathrm{wt\\%}$ 改性的表面活性剂 $.0.1\\sim5\\mathrm{wt}\\%$ 引发剂、余量为亲水性溶剂作为原料，在反应容器中加入亲水性溶剂，升温至 $50\\sim140^{\\circ}\\mathrm{C}$ ，将上述单体、改性的表面活性剂和引发剂混合均匀后，匀速滴加到溶剂中，滴加时间为 $2\\sim5$ 小时，滴加结束后，保温反应 $1\\sim3$ 小时，制得的；  \n\n[0006]其中，改性的表面活性剂为含磺酸基、硫酸基或羧酸基团的表面活性剂与（甲基）丙烯酸缩水甘油酯单体按摩尔比 $0.5\\sim2{:}1$ 混合均匀后，加入适量催化剂单丁基氧化锡，升温至 $80\\sim180^{\\circ}\\mathrm{C}$ 并保温 $3\\sim3.5$ 小时接枝形成的。  \n\n[0007］上述防雾涂料由 $20\\sim50\\mathrm{wt\\%}$ 防雾特性树脂， $2\\sim15\\mathrm{wt\\%}$ 封闭型异氰酸酯固化剂，$0.01\\sim2.0\\mathrm{wt\\%}$ 催化剂，余量为稀释剂组成；所述稀释剂为乙二醇丁醚、丙二醇甲醚、乙二醇乙醚、异丙醇、正丁醇、丙酮、丁酮中的一种或几种；所述催化剂为单丁基氧化锡。  \n\n[0008]上述防雾涂料中，所述稀释剂为乙二醇丁醚、丙二醇甲醚、乙二醇乙醚、异丙醇、正丁醇、丙酮、丁酮中的一种或几种。  \n\n[0009]上述防雾涂料中，所述封闭型异氰酸酯固化剂为己内酰胺、苯酚、甲酚、间硝基苯酚、对氯苯酚、邻苯二酚、丙二酸二乙酯、乙酰内酮、乙酰醋酸乙酯或丁酮封闭剂封端的甲苯二异氰酸酯（简称TDI）己二异氰酸酯（简称HDI）或异佛尔酮异氰酸酯（简称IPDI）。  \n\n[0010] 上述防雾涂料中，用于制备所述防雾特性树脂的含氮原子的乙烯基单体为（甲基）  \n\n丙烯酰胺、 $N-$ 甲基丙烯酰胺、N，N-二甲基丙烯酰胺、 $N-$ 乙基丙烯酰胺，N， $N-$ 二乙基丙烯酰胺， $N-\\mathsf{n}-$ 丙基丙烯酰胺、 $N-$ 异丙基丙烯酰胺、N，N-二甲基吡咯烷酮、 $N-$ 甲基吡咯烷酮、N,N'-二甲基氨乙基（甲基）丙烯酰胺、N， $N^{\\prime}-$ 二甲基氨丙基（甲基）丙烯酰胺和N-乙基-2-吡咯烷酮中的一种或几种。  \n\n[0011]上述防雾涂料中，用于制备所述防雾特性树脂的丙烯酸酯单体为（甲基）丙烯酸、（甲基）丙烯酸甲酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸羟乙酯、（甲基）丙烯酸羟丙酯、丙烯酸异辛酯、（甲基）丙烯酸乙酯中的至少两种。  \n\n[0012]上述的防雾涂料中，用于制备所述防雾特性树脂的亲水性溶剂为乙二醇丁醚、丙二醇甲醚、乙二醇乙醚、异丙醇、正丁醇、丙酮、丁酮中的一种或几种；引发剂为过氧化苯甲酰、过氧化月桂酰、异丙苯过氧化氢、叔丁基过氧化氢、过氧化二叔丁基、过氧化二异丙苯、过氧化苯甲酸叔丁酯、过氧化叔戊酸叔丁基酯、过氧化甲乙酮、过氧化环己酮、偶氮二异丁睛、偶氮二异庚睛、过氧化二碳酸二异丙酯、过氧化二碳酸二环己酯中的一种。  \n\n[0013]上述防雾涂料中，用于制备所述防雾特性树脂中改性的表面活性剂的含磺酸基表面活性剂为 $\\mathrm{C}_{10-20}$ 链烷基磺酸、芳烃磺酸、烷基芳烃磺酸、烷基磺基琥珀酸或a-烯烃磺酸；所用的含硫酸基表面活性剂为 $\\mathrm{C}_{10-20}$ 链烷基硫酸（酯）， $\\mathrm{C}_{10-20}$ 链烯基硫酸酯或 $\\mathrm{C}_{10-20}$ 链烷基醚硫酸（酯）；所用的羧酸基团的表面活性剂为 $\\mathrm{C}_{8-26}$ 脂肪酸。  \n\n[0014]本发明的技术效果是：本发明技术方案的防雾涂料，其主要成膜树脂防雾特性树脂是以丙烯酸酯单体、含氮原子乙烯基类单体以及改性的表面活性剂共聚而成，其中，丙烯酸酯类单体为特性树脂的主体结构，含氮原子乙烯基类单体和改性的表面活性剂提供了特性树脂的亲水性结构，这样，更利于提高水蒸气在涂膜表面的接触角，从而使水蒸气不会凝结成水珠，提高防雾效果，而经过接枝改性的表面活性剂在防雾涂料成膜时，改性的表面活性剂能与防雾涂料的主体树脂结构交联固化，使得表面活性剂不溶解在水中，克服了现有技术中因表面活性剂溶解在涂膜表面的水中，随着水蒸气的擦除，而慢慢的被带走的缺点，这样就保持了很好的防雾持久性，同时树脂的耐水性和耐老化性都很优异（见表11）。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 具体实施方式  \n\n[0015] 以下结合实施例对本发明做进一步具体描述，但不局限于此。  \n[0016] 实施例所用原材料除另有说明外均为市售工业用品，可通过商业渠道购得。[0017] （一）改性的表面活性剂的制备  \n[0018] 本发明的改性的表面活性剂为含磺酸基、硫酸基或羧酸基团的表面活性剂与（甲基）丙烯酸缩水甘油酯单体按摩尔比 $0.5\\sim2{:}1$ 混合均匀后，加入适量催化剂单丁基氧化锡，升温至 $80\\sim180^{\\circ}C$ 并保温 $3\\sim3.5$ 小时接枝形成的。  \n\n[0019] 实施例1 [0020] $\\textcircled{1}$ 原料配方见表1。 [0021] 表1  \n\n<html><body><table><tr><td rowspan=\"2\">[0022]</td><td>原料名称</td><td>用量，g</td></tr><tr><td>硬脂酸</td><td>345（相当1.21摩尔）</td></tr></table></body></html>  \n\n<html><body><table><tr><td rowspan=\"2\">[0023]</td><td>甲基丙烯酸缩水甘油酯</td><td>142（相当1摩尔）</td></tr><tr><td>催化剂单丁基氧化锡</td><td>0.5</td></tr></table></body></html>  \n\n[0024] $\\textcircled{2}$ 制备工艺  \n\n[0025]将上述配方中三种原料加入到反应瓶中，升温至 $120^{\\circ}\\mathrm{C}$ ，保温3小时后，制得改性的表面活性剂，保存备用。  \n\n[0026] 实施例2 [0027] $\\textcircled{1}$ 原料配方见表2。 [0028] 表2  \n\n<html><body><table><tr><td rowspan=\"5\">0029]</td><td>原料名称</td><td>用量，g</td></tr><tr><td>十二烷基萘磺酸</td><td>398.6（相当1摩尔）</td></tr><tr><td>甲基丙烯酸缩水甘油酯</td><td>142（相当1摩尔）</td></tr><tr><td>催化剂单丁基氧化锡</td><td>1</td></tr></table></body></html>  \n\n[0030] $\\textcircled{2}$ 制备工艺  \n\n[0031]将上述配方中三种原料加入到反应瓶中，升温至 $130^{\\circ}\\mathrm{C}$ ，保温3小时后，制得改性的表面活性剂，保存备用。  \n\n[0032] 实施例3 [0033] $\\textcircled{1}$ 原料配方见表3。 [0034] 表3  \n\n<html><body><table><tr><td rowspan=\"5\">035]</td><td>原料名称</td><td>用量，g</td></tr><tr><td>月桂酸</td><td>300（相当1.5摩尔）</td></tr><tr><td>甲基丙烯酸缩水甘油酯</td><td>142（相当1摩尔）</td></tr><tr><td>催化剂单丁基氧化锡</td><td>1</td></tr></table></body></html>  \n\n[0036] $\\textcircled{2}$ 制备工艺  \n\n[0037]将上述配方中三种原料加入到反应瓶中，升温至 $\\mathrm{150^{\\circ}C}$ ，保温3小时后，制得改性的表面活性剂，保存备用。  \n\n[0038] （二）制备防雾特性树脂  \n\n[0039]本发明的防雾特性树脂是以 $10\\sim50\\mathrm{wt\\%}$ 丙烯酸酯单体、 $1\\sim40\\mathrm{wt\\%}$ 含氮原子的乙烯基单体、 $1\\sim10\\mathrm{wt\\%}$ 改性的表面活性剂、 $.0.1\\sim5$ wt%引发剂、余量为亲水性溶剂作为原料。  \n\n[0040] 实施例4 [0041] $\\textcircled{1}$ 原料配方见表4。  \n\n[0042] 表4 [0043]  \n\n<html><body><table><tr><td>组分</td><td>原料名称</td><td>用量，g，（%）</td></tr><tr><td>丙烯酸酯单体</td><td>①甲基丙烯酸甲酯 ②丙烯酸丁酯 ③甲基丙烯酸羟乙酯 合计</td><td>20 8 7</td></tr><tr><td>含氮原子的乙烯基单体</td><td>N,N-二甲基甲酰胺</td><td>35(32.4%) 15(13.9%)</td></tr><tr><td>改性表面活性剂</td><td>实施例1制得</td><td>5（4.6%)</td></tr><tr><td>引发剂</td><td>偶氮二异丁基氰</td><td>3（2.8%)</td></tr><tr><td>亲水性溶剂</td><td>①丙二醇甲醚 ②异丙醇 ③丁醇 合计 50（46.3%)</td><td>30 10 10</td></tr></table></body></html>  \n\n[0044] $\\textcircled{2}$ 制备工艺  \n\n[0045]在反应容器中加入亲水性溶剂，升温至 $80^{\\circ}\\mathrm{C}$ ，将单体、改性的表面活性剂和引发剂混合均匀后，匀速滴加到溶剂中，滴加时间为4小时，滴加结束后， $80^{\\circ}\\mathrm{C}$ 保温反应1小时，制得特性防雾树脂A，保存备用。  \n\n[0046] 实施例5   \n[0047] $\\textcircled{1}$ 原料配方见表5。 [0048] 表5   \n[0049]  \n\n<html><body><table><tr><td>组分</td><td>原料名称</td><td>用量，g,(%)</td></tr><tr><td>丙烯酸酯单体</td><td>①甲基丙烯酸甲酯 ②甲基丙烯酸丁酯 ③丙烯酸羟乙酯</td><td>15 20 5</td></tr><tr><td></td><td>合计</td><td>40（38.84%)</td></tr><tr><td>含氮原子的乙烯基单体 改性表面活性剂</td><td>N,N-二甲基丙烯酰胺</td><td>14(13.59%)</td></tr><tr><td>引发剂</td><td>实施例2制得</td><td>6（5.82%)</td></tr><tr><td>亲水性溶剂</td><td>过氧化苯甲酰 ①乙二醇丁醚</td><td>3(2.91%) 30</td></tr></table></body></html>  \n\n[0050] $\\textcircled{2}$ 制备工艺  \n\n[0051]在反应容器中加入亲水性溶剂，升温至 $120^{\\circ}\\mathrm{C}$ ，将单体、改性的表面活性剂和引发剂混合均匀后，匀速滴加到溶剂中，滴加时间为3小时，滴加结束后， $120^{\\circ}\\mathrm{C}$ 保温反应1小时，制得特性防雾树脂B，保存备用。  \n\n[0052] 实施例6   \n[0053] $\\textcircled{1}$ 原料配方见表6。 [0054] 表6   \n[0055]  \n\n<html><body><table><tr><td>组分</td><td>原料名称</td><td>用量，g,(%)</td></tr><tr><td rowspan=\"6\">丙烯酸酯单体</td><td>①甲基丙烯酸甲酯</td><td>12</td></tr><tr><td>②丙烯酸丁酯</td><td>8</td></tr><tr><td>③甲基丙烯酸丁酯</td><td>8</td></tr><tr><td></td><td>5</td></tr><tr><td>④丙烯酸羟丙酯</td><td></td></tr><tr><td>合计</td><td>33（32.04%)</td></tr><tr><td>含氮原子的乙烯基单体</td><td>N,N-二甲基丙烯酰胺</td><td>12(11.65%)</td></tr><tr><td>改性表面活性剂</td><td>实施例3制得</td><td>5（4.86%)</td></tr><tr><td>引发剂</td><td>过氧化苯甲酸叔丁酯</td><td>3(2.91%)</td></tr><tr><td>亲水性溶剂</td><td>①乙二醇丁醚 ②丙二醇甲醚</td><td>5</td></tr></table></body></html>  \n\n[0056] $\\textcircled{2}$ 制备工艺  \n\n[0057]在反应容器中加入亲水性溶剂，升温至 $130^{\\circ}\\mathrm{C}$ ，将单体、改性的表面活性剂和引发剂混合均匀后，匀速滴加到溶剂中，滴加时间为4小时，滴加结束后， $130^{\\circ}\\mathrm{C}$ 保温反应3小时，制得特性防雾树脂C，保存备用。  \n\n[0058] （三）制备防雾涂料及样板  \n\n[0059]本发明防雾涂料由 $20\\sim50\\mathrm{wt\\%}$ 防雾特性树脂， $2\\sim15\\mathrm{wt\\%}$ 封闭型异氰酸酯固化剂， $0.01\\sim2.0\\mathrm{wt\\%}$ 催化剂，余量为稀释剂组成；所述稀释剂为乙二醇丁醚、丙二醇甲醚、乙二醇乙醚、异丙醇、正丁醇、丙酮、丁酮中的一种或几种；所述催化剂为单丁基氧化锡。  \n\n[0060] 实施例7   \n[0061] $\\textcircled{1}$ 防雾涂料配方见表7。 [0062] 表7   \n[0063]  \n\n<html><body><table><tr><td>组分</td><td>原料名称</td><td>用量，g，（%）</td></tr><tr><td>防雾特性树脂</td><td>防雾特性树脂A（实施例4制得）</td><td>30（29.94%)</td></tr><tr><td>封闭型异氰酸酯固化剂</td><td>丁酮封闭剂封端的TDI（市售品）</td><td>8(7.98%)</td></tr><tr><td>催化剂</td><td>单丁基氧化锡</td><td>0.2（0.2%)</td></tr><tr><td>稀释剂</td><td>①乙二醇丁醚 ②异丙醇 合计</td><td>40 22 62（61.88%)</td></tr></table></body></html>  \n\n[0064] $\\textcircled{2}$ 制备防雾涂料及样板[0065] 按照上述配方将各组分混合均匀配制好涂料，然后喷涂于透明聚碳酸酯板（以下简称PC板）上，在 $100^{\\circ}\\mathrm{C}$ 下烘烤20分钟得到的样板保存备检测用。  \n\n[0066] 实施例8  \n[0067] $\\textcircled{1}$ 防雾涂料配方见表8。[0068] 表8  \n[0069][0070] $\\textcircled{2}$ 制备防雾涂料及样板  \n[0071] 按照上述配方将各组分混合均匀配制好涂料，然后喷涂于PC板上，在 $120^{\\circ}\\mathrm{C}$ 下烘烤10分钟得到的样板保存备检测用。  \n[0072] 实施例9  \n[0073] $\\textcircled{1}$ 防雾涂料配方见表9。  \n[0074] 表9  \n[0075][0076] $\\textcircled{2}$ 制备防雾涂料及样板  \n[0077] 按照上述配方将各组分混合均匀配制好涂料，然后喷涂于PC板上，在 $90^{\\circ}\\mathrm{C}$ 下烘烤35分钟，得到的样板保存备检测用。  \n[0078] 实施例10 咪网  \n[0079] $\\textcircled{1}$ 防雾涂料配方见表  \n[0080] 表10  \n[0081][0082] $\\textcircled{2}$ 制备防雾涂料及样板  \n[0083] 按照上述配方将各组分混合均匀配制好涂料，然后喷涂于PC板上，在 $80^{\\circ}\\mathrm{C}$ 下烘烤40分钟，得到的样板保存备检测用。  \n[0084] （四）防雾涂料性能检测  \n[0085] 将实例 $7\\sim10$ 中所制成的涂料样板进行性能测试，具体测试方法如下：  \n[0086] $\\textcircled{1}$ 防雾性能检测：将上述制得的涂有防雾涂料的样板置于 $5^{\\circ}C$ 环境下，向涂膜表面呼气，如无发白现象，视为符合防雾要求；[0087] $\\textcircled{2}$ 耐擦拭性能：在每次进行防雾性能检测后，用干净的棉布或者卷纸将上面的水迹擦拭完，然后继续进行防雾实验，观察在保持涂膜防雾效果不下降的情况下擦拭的次数，擦拭次数越多表明耐擦拭性能越好；  \n[0088] $\\textcircled{3}$ 耐水性检测：室温环境下用水浸渍涂层，以涂层出现发白溶胀现象所用时间的长短来衡量其耐水性；  \n[0089] $\\textcircled{4}$ 附着力：按照国家标准GB/T1720-89采用漆膜附着力测定仪，画格法测定；[0090] $\\textcircled{5}$ 硬度：按照国家标准GB/T6739-2006采用铅笔硬度法测定；  \n[0091] $\\textcircled{6}$ 耐老化性能：按照国家标准GB/T1865-1997进行耐老化性的测定；  \n[0092] 测试结果列在表11。  \n[0093] 表11  \n[0094]  \n\n<html><body><table><tr><td>组分</td><td>原料名称</td><td>用量，g，（%）</td></tr><tr><td>防雾特性树脂</td><td>防雾特性树脂A（实施例4制得）</td><td>35（34.89%)</td></tr><tr><td>封闭型异氰酸酯固化剂</td><td>苯酚封闭剂封端的TDI（市售品）</td><td>10(9.97%)</td></tr><tr><td>催化剂</td><td>单丁基氧化锡</td><td>0.3（0.3%)</td></tr><tr><td>稀释剂</td><td>①乙二醇丁醚 ②异丙醇 合计</td><td>30 25 55（54.84%)</td></tr></table></body></html>  \n\n<html><body><table><tr><td>组分</td><td>原料名称</td><td>用量，g，（%）</td></tr><tr><td>防雾特性树脂</td><td>防雾特性树脂B（实施例5制得）</td><td>40（39.92%)</td></tr><tr><td>封闭型异氰酸酯固化剂</td><td>丁酮封闭剂封端的IPDI（市售品）</td><td>10(9.98%)</td></tr><tr><td>催化剂</td><td>单丁基氧化锡</td><td>0.2（0.2%)</td></tr><tr><td>稀释剂</td><td>①乙二醇丁醚 ②异丙醇 合计</td><td>40 10 50（49.90%)</td></tr></table></body></html>  \n\n<html><body><table><tr><td>组分</td><td>原料名称</td><td>用量，g，（%）</td></tr><tr><td>防雾特性树脂</td><td>防雾特性树脂C（实施例6制得）</td><td>35（34.89%)</td></tr><tr><td>封闭型异氰酸酯固化剂</td><td>丁酮封闭剂封端的HDI（市售品）</td><td>7（6.98%)</td></tr><tr><td>催化剂</td><td>单丁基氧化锡</td><td>0.3（0.3%)</td></tr><tr><td>稀释剂</td><td>①乙二醇丁醚 ②异丙醇 合计</td><td>45 13 58（57.83%)</td></tr></table></body></html>  \n\n<html><body><table><tr><td>检测项目</td><td>实施例7</td><td>实施例8</td><td>实施例9</td><td>实施例10</td><td>对比例</td></tr><tr><td>防雾性</td><td>合格</td><td>合格</td><td>合格</td><td>合格</td><td>合格</td></tr><tr><td>漆膜硬度（H）</td><td>3</td><td>3</td><td>4</td><td>3</td><td>1</td></tr><tr><td>附着力，级</td><td>1</td><td></td><td>1</td><td>1</td><td></td></tr><tr><td>漆膜的耐水性 室温下泡水不溶胀，不脱 240h</td><td>漆膜不发白， 落 防雾性能不 下降</td><td>漆膜不发白， 不溶胀，不脱 落 防雾性能不 下降</td><td>漆膜不发白， 不溶胀，不脱 落 防雾性能不 下降</td><td>漆膜不发白， 不溶胀，不脱 落 防雾性能不 下降</td><td>漆膜不发白， 不溶胀，不脱 落 防雾性能不 下降</td></tr><tr><td>耐老化性， 500h</td><td>不黄变，不粉 化，防雾性能 不下降</td><td>不黄变，不粉 化，防雾性能 不下降</td><td>不黄变，不粉 化，防雾性能 不下降</td><td>不黄变，不粉 化，防雾性能 不下降</td><td>不黄变，不粉 化，防雾性能 不下降</td></tr><tr><td>耐擦拭性能 （次）</td><td>100</td><td>130</td><td>95</td><td>130</td><td>60</td></tr></table></body></html>  \n\n[0095]注：对比例为日本藤仓化成株式会社生产的 $\\mathrm{GAF{-}209A/B}$ 热硬化型防雾涂料，其样板制备方法及检测方法与实施例 $7\\sim10$ 相同。[0096]从表11的测试结果中可以看出，本发明防雾涂料防雾性持久且耐水、耐老化，综合性能优异，特别是耐擦拭性能明显优于对比例的现有防雾涂料产品。",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,52 @@
+[
+    {
+        "id": 1,
+        "chunk": "# （19）中华人民共和国国家知识产权局",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# （12）发明专利申请  \n\n（21）申请号202010650737.3  \n（22）申请日2020.07.08  \n（71）申请人杭州埃比森新材料有限公司地址310000浙江省杭州市余杭区仓前街道文一西路1378号1幢D216室  \n（72）发明人左伟超余钢惠晓宁黄珊  \n（74）专利代理机构杭州天启智汇专利代理事务所（普通合伙）33357代理人周恩慧  \n（51）Int.CI.C09D183/12(2006.01)C08G77/46(2006.01)CO3C17/30（2006.01)",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# （54）发明名称  \n\n一种环保且防雾效果持久的玻璃防雾剂及其制备方法",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# （57）摘要  \n\n本发明涉及一种环保且防雾效果持久的玻璃防雾剂及其制备方法，其特征在于所述玻璃防雾剂为烯丙基聚醚、四甲基环四硅氧烷、八甲基环四硅氧烷、蒸馏水、四乙氧基硅烷按摩尔比4一5:1:10:0.2-0.3:0.2-0.3合成的三乙氧基封端聚醚改性硅油。制备方法采用铂金催化剂和碱胶催化剂，分步反应，分布控制反应条件，制得环保且防雾效果持久的玻璃防雾剂。本发明所得玻璃防雾剂具有使用方便，加水稀释喷涂玻璃表面干燥即可，对环境无污染，防雾效果持久等优点，另外制备工艺简单。  \n\n1.一种环保且防雾效果持久的玻璃防雾剂，其特征在于：所述玻璃防雾剂为烯丙基聚醚、四甲基环四硅氧烷、八甲基环四硅氧烷、蒸馏水、四乙氧基硅烷按摩尔比4一5：1：10：0.2—0.3：0.2—0.3合成的三乙氧基封端聚醚改性硅油。  \n\n2.根据权利要求1所述环保且防雾效果持久的玻璃防雾剂的制备方法，其特征在于采用以下步骤：A、按摩尔比4—5:1:10:0.2—0.3:0.2—0.3称取烯丙基聚醚、四甲基环四硅氧烷、八甲基环四硅氧烷、蒸馏水、四乙氧基硅烷；B、将步骤A称取的烯丙基聚醚、四甲基环四硅氧烷加入到反应釜中，通氮气进行保护，然后加入铂金催化剂，控制釜内温度在60一 $120^{\\circ}\\mathrm{C}$ ，搅拌状态下反应2一3h，得初产物；C、将步骤B所得初产物进行过滤、精馏，然后加入步骤A称取的八甲基环四硅氧烷和蒸馏水；通氮气进行保护，加入碱胶催化剂，控制反应温度在80一 $\\cdot130^{\\circ}\\mathrm{C}$ ，搅拌反应4—5h，得次产物；D、将步骤C的次产物过滤、精馏，然后加入步骤A称取的四乙氧基硅烷；通氮气进行保护，控制反应温度50- $\\cdot70^{\\circ}C$ ，在搅拌状态下反应2一3h；过滤、精馏、冷却，得环保且防雾效果持久的玻璃防雾剂。3.根据权利要求1或2所述的环保且防雾效果持久的玻璃防雾剂，其特征在于：所述丙烯聚醚中环氧乙烷/环氧丙烷为5/6。4.根据权利要求1或2所述的环保且防雾效果持久的玻璃防雾剂，其特征在于：所述四甲基环四硅氧烷纯度为 $98\\%$ 。5.根据权利要求1或2所述的环保且防雾效果持久的玻璃防雾剂，其特征在于：所述八甲基环四硅氧烷纯度为 $98\\%$ 06.根据权利要求1或2所述的环保且防雾效果持久的玻璃防雾剂，其特征在于：所述四乙氧基硅烷纯度为 $98\\%$ 0",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 一种环保且防雾效果持久的玻璃防雾剂及其制备方法",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 技术领域  \n\n[0001]本发明涉及涂层技术领域，特别涉及一种环保且防雾效果持久的玻璃防雾剂及其制备方法。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 背景技术  \n\n[0002]玻璃在我们的生活中十分常见，但由于玻璃表面特殊结构，在温度变化大时，冷环境变到热环境时，空气中的水份会在玻璃表面凝结形成小液珠，从而影响视线，如眼镜玻璃，浴室玻璃等。降低玻璃表面张力，增加液珠在玻璃表面的润湿可有效解决此问题，但是，同时溶剂稀释油性产品会造成环境污染。",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 发明内容  \n\n[0003]本发明要解决的技术问题是，提供一种环保且防雾效果持久的玻璃防雾剂，本发明克服了现有技术中溶剂污染、防雾持久性差的技术问题，且对环境无污染。  \n\n[0004]为解决上述技术问题，本发明采用以下技术方案：一种环保且防雾效果持久的玻璃防雾剂，其特征在于：所述玻璃防雾剂为烯丙基聚醚、四甲基环四硅氧烷、八甲基环四硅氧烷、蒸馏水、四乙氧基硅烷按摩尔比4-5:1:10:0.2-0.3:0.2-0.3合成的三乙氧基封端聚醚改性硅油。  \n\n[0005]一种环保且防雾效果持久的玻璃防雾剂的制备方法，其特征在于采用以下步骤：  \n\n[0006]A、按摩尔比4-5:1:10:0.2-0.3:0.2-0.3称取烯丙基聚醚、四甲基环四硅氧烷、八甲基环四硅氧烷、蒸馏水、四乙氧基硅烷；  \n\n[0007]B、将步骤A称取的烯丙基聚醚、四甲基环四硅氧烷加入到反应釜中，通氮气进行保护，然后加入铂金催化剂，控制釜内温度在 $60{-}120^{\\circ}C$ ，搅拌状态下反应2-3h，得初产物；[0008]C、将步骤B所得初产物进行过滤、精馏，然后加入步骤A称取的八甲基环四硅氧烷和蒸馏水；通氮气进行保护，加入碱胶催化剂，控制反应温度在 $80-130^{\\circ}\\mathrm{C}$ ，搅拌反应4-5h，得次产物；  \n\n[0009]D、将步骤C的次产物过滤、精馏，然后加入步骤A称取的四乙氧基硅烷；通氮气进行保护，控制反应温度 $50-70^{\\circ}C$ ，在搅拌状态下反应2-3h；过滤、精馏、冷却，得环保且防雾效果持久的玻璃防雾剂。  \n\n[0010] 所述丙烯聚醚中环氧乙烷/环氧丙烷为5/6。  \n\n[0011] 所述四甲基环四硅氧烷纯度为 $98\\%$ 6[0012] 所述八甲基环四硅氧烷纯度为 $98\\%$ 。  \n\n[0013] 所述四乙氧基硅烷纯度为 $98\\%$ 0  \n\n[0014]本发明在硅油链节中引入聚醚基团，增加液体润湿基材能力和水溶性，引入乙氧基反应基团，增加了硅油在玻璃基材的持久性。  \n\n[0015]本发明分别以烯丙基聚醚、四甲基环四硅氧烷、八甲基环四硅氧烷、蒸馏水、四乙氧基硅烷为原料，加入适量铂金催化剂和碱胶催化剂，控制反应时长和温度。所的产物收率高，涂布于玻璃表面，降低玻璃表面张力，聚醚亲水，使水珠铺展于玻璃表面，乙氧基与玻璃表面羟基进行反应，增加了防雾剂的持久性。  \n\n[0016]本发明提供的环保持久型玻璃防雾剂及其制备方法，具有工艺步骤简单，使用方便，加水稀释喷涂玻璃表面干燥即可，对环境无污染等优点。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 附图说明  \n\n[0017] 图1为本发明工艺步骤示意图。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 具体实施方式  \n\n[0018] 实施例1：一种环保且防雾效果持久的玻璃防雾剂的制备方法，采用以下步骤：[0019]A、按以下摩尔比4：1:10：0.2:0.2称取烯丙基聚醚、四甲基环四硅氧烷、八甲基环四硅氧烷、蒸馏水、四乙氧基硅烷做为原料备用：  \n[0020]B、将步骤A称取的烯丙基聚醚、四甲基环四硅氧烷加入到反应釜中，通氮气进行保护，加入铂金催化剂，控制温度 $60^{\\circ}\\mathrm{C}$ ，搅拌状态下反应2h，得初产物；  \n[0021]C、将步骤B所得初产物过滤、精馏，然后加入步骤A称取的八甲基环四硅氧烷和蒸馏水，通氮气进行保护，加入碱胶催化剂，控制温度 $80^{\\circ}C$ ，搅拌状态下反应4h，得次产物；[0022]D、将步骤C所得次产物过滤、精馏，然后加入步骤A称取的四乙氧基硅烷，通氮气进行保护，控制温度 $50^{\\circ}\\mathrm{C}$ ，搅拌状态下反应2h；过滤、精馏、冷却，得环保且防雾效果持久的玻璃防雾剂。  \n\n[0023] 所述环保且防雾效果持久的玻璃防雾剂为三乙氧基封端聚醚改性硅油。  \n\n[0024]将本实施例所得环保且防雾效果持久的玻璃防雾剂用蒸馏水稀释到质量浓度为$1\\%$ ，喷涂到玻璃片表面，干燥24h，循环置于室温与热水浴上方，观察玻璃表面起雾情况。测试情况如表1  \n\n[0025] 表1  \n\n<html><body><table><tr><td>天数+次数</td><td>次</td><td>第1天1第1天50第2天 次</td><td></td><td>100次</td><td>第5天 250次</td><td>第10天第20天 500次</td><td>1000次</td></tr><tr><td rowspan=\"2\">玻璃 防雾 效果</td><td>处理过玻璃 片</td><td>无雾</td><td>无雾</td><td>无雾</td><td>轻微</td><td>严重</td><td>失效</td></tr><tr><td>未处理玻璃 片</td><td>无效果</td><td>无效果</td><td>无效果</td><td>无效果</td><td>无效果</td><td>无效果</td></tr></table></body></html>  \n\n[0026]  \n\n[0027] 实施例2：[0028] 一种环保且防雾效果持久的玻璃防雾剂的制备方法，采用以下步骤：  \n\n[0029]A、按以下摩尔比5：1:10:0.3:0.3称取烯丙基聚醚、四甲基环四硅氧烷、八甲基环四硅氧烷、蒸馏水、四乙氧基硅烷做为原料备用；  \n\n[0030]B、将步骤A称取的烯丙基聚醚、四甲基环四硅氧烷加入到反应釜中，通氮气进行保护，加入铂金催化剂，控制温度 $120^{\\circ}\\mathrm{C}$ ，搅拌状态下反应3h，得初产物；[0031]C、将步骤B所得初产物过滤、精馏，然后加入步骤A称取的八甲基环四硅氧烷和蒸馏水，通氮气进行保护，加入碱胶催化剂，控制温度 $130^{\\circ}\\mathrm{C}$ ，搅拌状态下反应5h，得次产物；[0032]D、将步骤C所得次产物过滤、精馏，然后加入步骤A称取的四乙氧基硅烷，通氮气进行保护，控制温度 $70^{\\circ}C$ ，搅拌状态下反应3h；过滤、精馏、冷却，得环保且防雾效果持久的玻璃防雾剂。  \n\n[0033]将本实施例所得环保且防雾效果持久的玻璃防雾剂用蒸馏水稀释到质量浓度为$1\\%$ ，喷涂到玻璃片表面，干燥24h，循环置于室温与热水浴上方，观察玻璃表面起雾情况。测试情况如表2  \n\n[0034] 表2  \n\n[0035]  \n\n<html><body><table><tr><td colspan=\"2\">天数+次数</td><td>第1天第1天</td><td></td><td>第2天</td><td>第5天</td><td>第10天</td><td>第20天</td></tr><tr><td rowspan=\"2\">玻璃防</td><td>处理过</td><td>无雾</td><td>无雾</td><td>轻微</td><td>严重</td><td>失效</td><td>失效</td></tr><tr><td></td><td>无效果</td><td>无效果</td><td>无效果</td><td>无效果</td><td>无效果</td><td>无效果</td></tr></table></body></html>  \n\n[0036] 实施例3：[0037] 一种环保且防雾效果持久的玻璃防雾剂的制备方法，采用以下步骤：  \n\n[0038]A、按以下摩尔比4.6:1:10:0.23:0.24称取烯丙基聚醚、四甲基环四硅氧烷、八甲基环四硅氧烷、蒸馏水、四乙氧基硅烷做为原料备用；B、将步骤A称取的烯丙基聚醚、四甲基环四硅氧烷加入到反应釜中，通氮气进行保护，加入铂金催化剂，控制温度 $102^{\\circ}\\mathrm{C}$ ，搅拌状态下反应2.6h，得初产物；  \n[0039]C、将步骤B所得初产物过滤、精馏，然后加入步骤A称取的八甲基环四硅氧烷和蒸馏水，通氮气进行保护，加入碱胶催化剂，控制温度 $116^{\\circ}C$ ，搅拌状态下反应4.4h，得次产物；[0040]D、将步骤C所得次产物过滤、精馏，然后加入步骤A称取的四乙氧基硅烷，通氮气进行保护，控制温度 $55^{\\circ}\\mathrm{C}$ ，搅拌状态下反应2.7h；过滤、精馏、冷却，得环保且防雾效果持久的玻璃防雾剂。  \n\n[0041]将本实施例所得环保且防雾效果持久的玻璃防雾剂用蒸馏水稀释到质量浓度为$1\\%$ ，喷涂到玻璃片表面，干燥24h，循环置于室温与热水浴上方，观察玻璃表面起雾情况。测试情况如表3。  \n\n[0042] 表3  \n\n[0043]  \n\n<html><body><table><tr><td colspan=\"2\">天数+次数</td><td></td><td>1次50次100次</td><td></td><td></td><td>第1天第1天第2天第5天第10天第20天 250次500次1000次</td><td></td></tr><tr><td rowspan=\"2\"></td><td>处理过 玻璃防玻璃片</td><td>无雾无雾</td><td></td><td>无雾</td><td>无雾</td><td>无雾</td><td>无雾</td></tr><tr><td>雾效果未处理无效 玻璃片果</td><td></td><td>无效果无效果</td><td></td><td></td><td>无效果无效果无效果</td><td></td></tr></table></body></html>\n\n[0044] 经过对比，实施例3的产品效果最好，为最佳方案。  \n\n![](images/f67b94c2fb0ed007bd10a263012dd1191d7089c9791d689ebf477c475d4a534f.jpg)  \n图1",
+        "category": " Materials and methods"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,77 @@
+[
+    {
+        "id": 1,
+        "chunk": "文章编号：  1008-9357(2021)02-0172-10",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# 医用高分子材料抗凝血表面构建策略及研究进展  \n\n栾    轲1,2，  班    雨2，  施德安1，  石恒冲2（1. 湖北大学材料科学与工程学院，高分子材料湖北省重点实验室，武汉 430062；2. 中国科学院长春应用化学研究所，高分子物理与化学国家重点实验室，长春 130022）  \n\n摘    要：  医用高分子材料及医疗器械主要用于疾病的诊断和治疗。此种材料/器械在植/介入人体与血液接触时，血浆蛋白会在几秒钟内吸附到材料/器械表面，并与血小板上的糖蛋白受体结合，导致血小板活化、凝血级联以及补体激活，形成凝血及血栓，严重危及病人的健康及生命安全。为了赋予材料/器械表面抗凝血性能，需有针对性地进行抗凝血表面构建，其方法主要为：生物惰性涂层、生物活性涂层、具有内皮（EC）特异性生长因子的表面涂层和复合抗凝涂层。本文结合国内外该领域研究动态及本课题组近年来在医用高分子材料及医疗器械抗凝血表面构建的研究成果，概述了抗凝血表面构建及其在医疗器械中应用的研究进展。  \n\n关键词：  生物医用高分子材料；医疗器械；抗凝血；生物相容性中图分类号：  O63 文献标志码：  A",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# Construction Strategy and Research Progress of Anticoagulant Surface of Medical Polymeric Materials  \n\nLUAN $\\mathrm{Ke}^{1,2}$ , BAN $\\mathrm{Yu}^{2}$ , SHI Dean1, SHI Hengchong2   \n（1. Hubei Key Laboratory of Polymer Materials, School of Materials Science and Engineering, Hubei University, Wuhan   \n430062, China; 2. State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China）  \n\nAbstract:  Biomedical polymer materials and medical devices are mainly used for the diagnosis and treatment of diseases, and are used by thousands of patients every day. When this material/device is implanted/intervened in the human body and comes into contact with blood, plasma proteins will adsorb to the surface of the material/device within a few seconds and bind to the glycoprotein receptor on the platelet, resulting in platelet activation, coagulation cascade and complement activation, coagulation and thrombus. Human health and life safety are seriously endangered. To impart anticoagulant properties to the surface of materials/devices, it is necessary to construct anticoagulant surfaces in a targeted manner. The main methods are as follows:  biologically  inert  coatings,  biologically  active  coatings,  surface  coatings  with  endothelial  (EC)  specific  growth factors, and composite anti-coagulation coating. Based on the research developments in this field at home and abroad and the research results of our group in recent years in the construction of anticoagulant surface of biomedical polymer material and medical  device,  this  review  summarizes  the  research  progress  of  anticoagulant  surface  construction  and  its  application  in medical devices.  \n\nKey words: biomedical polymer material；   medical device；   anticoagulant；   biocompatibility  \n\n在医学领域中，医用高分子材料及医疗器械主要用于诊断和治疗，每天有成千上万的病人使用血液接触类器械，如血液透析循环管路、中心静脉导管、心脏支架、血管移植物、心脏瓣膜等[1]。该类器械直接与血液接触时会发生一系列反应，血浆蛋白首先会瞬间在材料表面吸附形成血浆蛋白，然后血小板会在血浆蛋白表面黏附、聚集，进而使血小板激活、凝血级联及补体激活，最终导致血栓形成[2]。据美国食品药品管理局（FDA）统计，2016 年美国此类医疗器械的市场销售额约为 90 亿美元，但在心脏支架的使用过程中由于血栓形成导致的死亡率高达 $80\\%$ ，严重威胁着人类的健康及生命安全[3]。临床上，通常需要口服抗血小板药物或抗凝剂来抑制器械表面血栓形成，但同时会增加出血的风险。因此，在材料/器械表面设计及构建安全和有效的抗凝血表面至关重要。  \n\n本文概述了高分子材料/器械表面凝血和血栓形成的过程及相关机制，并总结了目前常见的 4 种抗凝血表面构建策略，主要有生物惰性涂层、生物活性涂层、具有内皮（EC）特异性生长因子的表面涂层和复合抗凝涂层，同时展望了未来材料/器械抗凝血表面构建的发展趋势[4]。",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1    凝血机理及血栓形成  \n\n血液接触类医疗器械接触血液时，血浆蛋白会在几秒钟内吸附到材料/器械表面，并与血小板上的糖蛋白受体结合，导致血小板活化、凝血级联以及补体激活，最终形成血栓[5]，从而导致器械失效。",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 1.1 血浆蛋白吸附  \n\n血浆蛋白是血浆中最主要的成分之一，质量浓度为 $60{\\sim}80~\\mathrm{g/L}$ 。当血液与生物材料相互接触时，会在其表面瞬间形成一层血浆蛋白吸附黏膜。被吸附的血浆蛋白可形成厚度 $2\\sim10\\ \\mathrm{nm}$ 的单层，其表面蛋白浓度比血浆中的浓度高 1 000 倍[3-6]。纤维蛋白原是最早沉积在血液接触类器械上的血浆蛋白之一，其他黏附蛋白吸附在器械表面，并与纤维蛋白原共同作用，引发血小板的黏附与聚集[7]。",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 1.2    血小板的黏附与聚集  \n\n血小板是血栓形成的重要组成部分，在正常血液中血小板是一种质量浓度为 $150{\\times}10^{6}{\\sim}450{\\times}10^{6}\\mathrm{g/mL}$ 的无核血细胞[6, 7]。吸附在血液接触类器械上的纤维蛋白原会进一步激活血小板，导致血小板活化以及形状变化[8, 9]。这些活化的血小板为凝血酶的生成创造了一个巢穴，加快了凝血酶的生成[10]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 1.3 凝血酶的生成  \n\n凝血酶是一种丝氨酸蛋白酶，也是血液凝血级联反应中的主要蛋白酶。血小板在血液接触类器械表面黏附与聚集后，会进一步释放凝血因子 XII（FXII）、高分子量激肽原和前激肽释放酶。被吸附的 FXII 经过自激活成为凝血因子 XIIa（FXIIa），并激活前激肽释放酶[11]。起辅助作用的高分子量激肽原会与器械表面结合，进一步激活 FXII，使得前激肽释放酶激活导致激肽释放酶的产生，从而以相互作用的方式激活更多的 FXII。FXII 的激活引发一系列蛋白水解反应，最终形成凝血酶从而引发了下一步补体系统的激活[12]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 1.4    补体系统的激活  \n\n补体系统是先天免疫系统的一部分，由近 40 种成分组成，多数组分为糖蛋白，主要组分有三碳糖磷酸（C3）、五碳糖磷酸（C5）等，能增强机体对病原体和细胞碎片的清除能力[13]。当血液接触类器械表面形成凝血酶后，产生的前激肽释放酶裂解 FXIIa 生成酶 b-FXIIa，酶 b-FXIIa 会使补体系统初步被激活，导致 C3 和 C5沉积在器械表面。由此产生的磷酸片段可促进白细胞黏附于器械表面并随后激活，从而导致血液接触类器械表面的凝血以及血栓形成[7-9]。",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2    涂层表面构建策略  \n\n为了赋予材料表面抗凝血性能，需有针对性地设计和构建抗凝血表面。目前构建策略主要分为以下  \n\n4 类：生物惰性涂层、生物活性涂层、具有EC 特异性生长因子的表面涂层和复合抗凝涂层。",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.1    生物惰性涂层  \n\n生物惰性涂层可以阻止血液与器械表面之间的相互作用，尤其是非特异性蛋白质吸附。目前主要有两种构建方法：（1）构建聚乙二醇（PEG）或两性离子聚合物等亲水刷或水凝胶，抑制蛋白质、血小板等的吸附。（2）构建滑移表面，抑制水或血液润湿从而阻碍蛋白质、血小板等在材料/器械表面吸附。上述两种方法都能有效减少血浆蛋白和血小板在材料表面的黏附，并减轻材料表面非特异性吸附引起的各种不良反应，有效提高材料表面的生物相容性及抗凝性[3, 4, 14]。  \n\n2.1.1   PEG　 PEG 是安全、无毒、且具有良好生物相容性的聚合物，同时具备较好的生物惰性和优异的亲水性，是常用于构建血液接触类医疗器械抗凝表面的聚合物之一。基于 PEG 的表面改性方法有：物理吸附法、共价接枝法和化学偶联法。共价接枝法由于操作简单、方便且接枝后性能优异、稳定，因此是目前较常见的方法[15-17]。其抗凝机制主要是，在高分子材料表面接枝一定密度和链长的 PEG 后，带中性电荷的亲水性PEG 聚合物链会与水分子结合并在其表面形成水化层，从而抵抗蛋白质和血小板的非特异性黏附，起到抗凝血和抗菌的双重作用[18, 19, 20]。  \n\nKovach 等[21] 通过氧气等离子体预处理和 PEG接枝的方法对聚二甲基硅氧烷（PDMS）微流控网络进行表面抗凝改性，最终得到了修饰后的 PDMS 抗凝表面。实验表明，PEG 接枝物纤维蛋白原的吸附和血小板黏附显著降低，而无涂层的 PDMS 微通道网络可快速吸附血液接触器械中的纤维蛋白原，纤维蛋白原吸附导致血小板活化，并导致凝血现象。结果表明，修饰后的 PDMS 微通道涂层展现出了较好的血液相容性及抗凝性，可望应用到更多的血液接触类器械涂层（如图1 所示）。  \n\n尽管 PEG 涂层在短期应用中展现出了较好的非特异性黏附和抗凝性，但在长期体内实验中，该涂层表面的链段易被氧化分解，且 PEG 层的链长和表面密度逐渐减少[22, 23]，更适合短期使用的血液接触类器械。  \n\n2.1.2   两性离子聚合物　 两性离子聚合物的长链上具有相等数量的阴离子和阳离子基团，这种结构使它们具有高度的亲水性，并可对抗蛋白质和血小板非特异性黏附[24]。两性离子聚合物主要为甜菜碱聚合物，这类聚合物的正负电荷分布在同一单体上，又可分为磷酸盐甜菜碱、磺酸盐甜菜碱和羧酸盐甜菜碱[25]。其抗凝机制与 PEG 一致，两性离子聚合物在与医疗器械接触时会在表面形成致密水化层，该水化层可抑制蛋白、血小板和人体细胞的黏附与聚集，从而使器械表面具有优越的抗蛋白吸附能力和抗凝血性能[26]。  \n\nSmith 等[27] 提出通过氧化-还原聚合反应表面接枝手段将外周静脉导管（PICC）浸入含有两性离  \n\n![](images/b93b2eb208b2f4a0733630670631e48ea274f335dc24607163f451ffb54bdcdd.jpg)  \n图 1    氧等离子体处理过的 PDMS 表面经甲基硅氧烷偶联反应接枝 PEG 示意图[21]  \nFig. 1    Schematic  diagram  of  the  PEG  grafting  reaction  between methoxysilane  molecules  and  the  surface  of  PDMS  treated with oxygen plasma[21]  \n\n子聚合物磺基甜菜碱（PolySB）的溶液中反应 $16\\mathrm{h}$ ，从而对 PICC 的内外表面进行改性，最终得到具有抗凝功能的外周静脉导管。实验表明，与未被修饰的 PICC 相比，经 PolySB 修饰的 PICC 在体外接触人体血液后，血小板、淋巴细胞、单核细胞和中性粒细胞的活性显著降低，其附着性降低 $98\\%$ 。此外，将改性过的 PICC 放置在牛血中 60 d，PICC 周围并无血栓聚集。结果表明，改性后的 PICC 展现出了较好的抗凝性，与 PEG 相比PolySB 具有较好的氧化稳定性和亲水性，更适合长期应用（如图2 所示）。  \n\n2.1.3   滑移表面　 近年来，滑移表面由于其在高分子材料领域中具有良好的抗非特异性黏附和抗凝抗菌多重功能而广受关注[28]。Leslie 等[29] 受猪笼草实验的启发，通过将全氟润滑剂吸到聚四氟乙烯多孔材料中，首次成功制备出“滑移表面”。滑移表面的制备原理主要是通过全氟碳化物渗透多孔或粗糙的基底，形成稳定、光滑的液体覆盖层[30, 31]。由于该表面具有较小的滑移角和接触角滞后值，因此具有优异的滑移性能，能防止水或血液在表面润湿，从而阻碍蛋白质和血小板的吸附，因此滑移表面具有优异的抗凝抗菌性能[32-34]。  \n\n![](images/7e917294c096e90bbd2df68caaff5b033cd71e083b71691fd5ea4351f6f3ab71.jpg)  \n图 2    （a）PICC 表面的 PolySB 亲水改性；（b）将经 PolySB 涂层的 PICC 和未被涂层的 PICC 置于流动血清中，经 60 d 后测得的不同 PICC 中血栓形成情况；（c）PICC 样品在犬血栓模型中的血栓形成情况[27]  \nFig. 2    （a） PolySB hydrophilic modification of PICC surface; （b） Placing the PICC coated with PolySB and the uncoated PICC in the serum, the accumulation of thrombus in different PICCs measured after $60\\mathrm{d}$ ; （c） Evaluation of PICC samples in canine thrombosis model[27]  \n\nLeslie 等[29] 通过化学键接柔性含氟碳链与全氟液体相互作用形成“滑移”液膜，最终得到了滑移表面，该表面能有效抑制血小板和蛋白的黏附。为了评估此种滑移表面对血小板黏附的影响，他们通过 SEM 观察了样品接触人血液 $30\\mathrm{min}$ ，与对照表面相比，涂覆在导管后的滑移表面能有效减少血小板的黏附与聚集。结果表明，此种滑移表面能有效降低血小板的黏附与活化，抑制纤维蛋白原的吸附，具有良好的抗凝性（如图3 所示）。  \n\n殷敬华课题组[35] 通过在聚（苯乙烯- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -异丁烯-苯乙烯）弹性体（SIBS）上采用紫外接枝技术，制备出了一种氟碳褶皱表面（FTWS），在此基础上灌注足量的氟碳液体，最终制备出一种具有褶皱结构、氟化物高分子刷接枝的滑移表面（FLIWS）。该表面能有效“捕获”氟油并形成完整、平滑的氟油液膜，从而赋予材料表面优异的抗凝血和抗菌性，其表面纤维蛋白原吸附量降低了约 $96\\%$ ，血小板黏附量极小、凝血指数增大至 $95\\%$ 左右，且大肠杆菌和金黄色葡萄球菌的黏附量分别降低了约 $98.8\\%$ 和 $96.9\\%$ ，因此该表面具有良好的抗凝性和抗菌性能（如图4 所示）。  \n\n虽然滑移表面涂层抗凝抗菌性能优异，但滑移层表面不稳定、易蒸发，从而导致抗凝持久性欠佳。为了克服这一局限性，在制备滑移表面时需选择稳定、不易挥发的润滑剂注入材料表面[14]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 2.2 生物活性涂层  \n\n在高分子材料表面引入生物活性物质，如肝素、一氧化氮（NO）、抗凝药物等形成生物活性涂层预防凝血和血栓形成，这些活性物质可以选择性吸附或结合特定的生物大分子与血液相互作用及减少凝血酶的产生[5, 6, 21]。目前最常见的生物活性涂层主要有：肝素钠盐涂层、抗凝药物涂层和一氧化氮涂层。  \n\n![](images/d4630bd51eb3ca7b9f91faa43351b8c35eb57d7ca8e6445a0501746fd25a88e3.jpg)  \n图 3    （a）TLP 滑移表面的抑制血液黏附示意图；（b）血液流动 8 h 后，TLP 顶部和底部的聚氨酯套管、聚碳酸酯连接器和 PVC 管血栓流动情况的照片；（c）通入猪血 $2~\\mathrm{min}$ 后的对照样品（左）和 TLP（右）的心脏灌注管照片[29]  \n\nFig. 3    （a） Schematic diagram of blood repelling on TLP sliding surface; （b） After $^{8\\mathrm{~h~}}$ of blood flow, the TLP top and bottom polyurethanecannula,  polycarbonate  connector  and  PVC  tube  thrombus  flow  photos;  （c）  Photos  of  the  control  （left）  and  TLP  （right）  cardiacperfusion tubes after porcine blood was injected for $2\\:\\mathrm{min}^{[29]}$  \n\n![](images/888ad043aa7a22cf58b4eee4799c3fc5eb484fd426507b45305ce5febb540234.jpg)  \n图 4    抗凝功能 SIBS 滑移表面形成过程[35]  \nFig. 4    Formation process of SIBS slip surface with anticoagulation function[35]  \n\n2.2.1   肝素钠盐涂层　 肝素钠（HS）是一种硫酸氨基葡聚糖钠盐，由不同分子量的糖链组成。其抗凝机制主要通过与凝血酶 III（AT-III）结合，增强 AT-III 对凝血因子的抑制作用，阻止血小板聚集及凝血酶原被激活转变为凝血酶，进而阻碍纤维蛋白原被激活转变成纤维蛋白，从而抑制血栓的形成[36, 37]。  \n\nFeng 等[38] 将肝素固定在聚碳酸酯型聚氨酯（PCU）表面，通过在表面接枝 PEG 形成亲水性钝化层作为间隔臂，该间隔臂能有效减少蛋白质和血小板在 PCU 表面的黏附并抑制血栓形成，最终制备出了肝素-PEG 共价接枝的抗凝涂层。实验证明，PCU 薄膜经改性后亲水性和血液相容性显著提高，同时降低了对血小板的黏附。结果表明，生物惰性PEG 和生物活性肝素分子协同作用后显著提高了PCU 的血液相容性和抗凝性。  \n\nCestari 等[39] 通过静电纺丝法制备丝素纳米纤维（FS），并在其表面固定 HS 的方法，使丝素蛋白具有较小的炎症反应和抗凝特性。他们研究了丝素蛋白与肝素之间氢键的形成，证明肝素的固定化是通过丝素蛋白和肝素链之间形成氢键实现的，且能进一步改善血液相容性及抗凝性。  \n\n虽然 HS 抗凝性良好，但由于 HS 在高分子材料表面固定后生物活性会降低，通常在其表面接枝 PEG 亲水性钝化层作为间隔臂来提高肝素活性、减少血浆蛋白和血小板的黏附，从而保证其优异的抗凝性能[38, 40]。  \n\n2.2.2   抗凝药物涂层　 具有抗凝机制的药物也可被涂在血液接触器械上以增强抗血栓能力，这些药物包括玉米胰蛋白酶抑制剂（CTI）、血栓调节蛋白（TM）、直接凝血酶抑制剂水蛭素等[5]。CTI、TM 和水蛭素都可用于血液接触类医疗器械涂层，CTI 是一种从玉米粒中提取的抑制 FXIIa 的蛋白质，可抑制 FXIIa 和 FXII 的自激活，减少血浆蛋白在血液接触类器械表面的沉积。TM 是凝血酶的受体，在内皮细胞表面表达，通过调节蛋白复合物结合凝血酶及促进蛋白活化来抑制凝血。水蛭素则是一种小分子蛋白质，通过抑制凝血酶同血小板的结合及血小板受凝血酶刺激后的释放，可达到在血液接触类器械表面的抗凝功能[7, 18]。  \n\nQu 等[41] 将具有生物活性的 TM 片段包覆在小直径聚氨酯-聚四氟乙烯导管表面，最终得到能有效抑制血栓形成的聚氨酯-聚四氟乙烯涂层。通过用非人灵长类动物模型验证了 TM 修饰导管的生物活性和生物稳定性，得到稳定的 TM 涂层并显著减少血小板黏附和活化。结果表明，改性后的聚氨酯-聚四氟乙烯涂层能有效降低血小板活化及蛋白质黏附，具有优异的血液相容性和抗凝性。  \n\n虽然 TM 涂层表面在体外较稳定且能显著降低血小板黏附、活化和血栓形成，但前期处理与保存 TM 片段及后期合成过程较为繁琐复杂，不易制备[14, 41]。  \n\n2.2.3   NO 涂层　 近 30 年来，NO 作为一种重要的信号分子在许多生物过程中被发现，其中包括作为杀菌剂和抗血栓剂的这两种优异性能[38]。其主要是由一氧化氮合酶（NOS）催化氧化 $L$ -精氨酸末端胍基中的氮而产生，是正常血管内皮细胞释放的一种舒张血管的重要活性物质，可使血管张力得到调节，维持正常的血液流动[14]。其抗凝机制是：NO 经内皮细胞释放后迅速在细胞外液中弥散，并与该受体相结合，激活血小板等靶细胞，促使三磷酸鸟苷环化酶生成环磷酸鸟苷（cGMP），使 cGMP 的量增加并降低血小板激活所需要的钙离子浓度，从而抑制血小板激活和集聚的功能[42]。  \n\n黄楠课题组[43] 通过在等离子体聚丙烯酰胺膜（PPAm）的表面胺基上固定凝血酶抑制剂比卢伐定（BLVD）后，再将 PPAm 浸入甲醇钠的混合溶液同时使用高压反应器通入 NO 气体，最终得到了具有优异抗凝性能的NO-PPAm 涂层。通过体外血小板黏附、纤维蛋白原吸附等一系列实验表明，该涂层显著降低了血小板黏附和活化数量。NO-PPAm 涂层制备手段简单安全，具有优异的抗凝性能（如图5 所示）。  \n\n![](images/af83382a87c96e20c9d3ec573c81fbbd7502e10457b03e04acc0fff867a23e0b.jpg)  \n图 5    （a）通过丙烯酰胺的脉冲等离子体聚合制备 PPAm 涂层的示意图；（b）血液循环 2 h 后样品的横截面图片[45]  \nFig. 5    （a） Schematic diagram of PPAm coating prepared by pulsed plasma polymerization of allylamine； （b） Cross-sectional image of the sample after 2 h of blood circulation[45]  \n\n虽然 NO 作为供体在生物应用中有着良好的抗菌和抗凝性，但其主要缺点就是不稳定易分解且随着时间的推移涂层表面的量逐渐减少。因此，该涂层在长期应用中会失去其抗凝性能[41-43]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 2.3    具有EC 特异性生长因子的表面涂层  \n\n由动脉、静脉和心脏等组成的血液循环系统称为心血管系统，其中，静脉与动脉一般可以根据组成成分的不同分为 3 层：外层由成纤维细胞与胶原基质组成，其功能是组成血管的基底并锚定血管的松散结缔组织；中层由 I 型和 III 型胶原蛋白及一些蛋白聚糖组成；内皮层（EC）由基膜上的内皮细胞（ECs）、胶原纤维以及平滑肌细胞等组成[44]。内皮由单层内皮细胞组成，这些内皮细胞排列在血管管腔上与血液直接接触，EC 在调节炎症和凝块形成中起着至关重要的作用。血管内皮细胞被称为血管的天然内表面，它在各方面都是最好的抗凝表面，其抗凝机制是：带负电荷的 ECs 可以阻止血小板沉积在内皮表面，并能快速降解血小板自身释放的致聚剂，阻止血小板进一步聚集，从而抑制血栓的形成[45]。  \n\nChen 等[46] 设计合成了两性离子磺酰胺与丙烯酸的共聚物，并将血管内皮钙黏蛋白（VECad）细胞以化学接枝的手段固定在两性离子-丙烯酸的共聚物链上，通过简单浸涂工艺使其可以稳定地黏附在支架表面，最终得到了两性共聚物的 EC 抗凝涂层。实验证明，含有 VECad 负载-两性共聚物修饰的涂层显著降低了血小板黏附和活化的数量，该涂层具有较好的血液相容性和抗凝性。  \n\nZheng 等[47] 利用 ECs 对平滑肌细胞（SMCs）的细胞选择性，通过简单浸涂工艺使其可以稳定地黏附在聚四氟乙烯（PTFE）上，最终得到了 EC 抗凝涂层。由贻贝肽、两性多肽和生物活性肽（REDV 和 YIGSR）组成了三嵌段功能蛋白，该三嵌段蛋白可在聚四氟乙烯表面形成涂层，所形成的涂层可有效抵抗蛋白质和血小板的黏附，具有较好的抗凝血性（如图6 所示）。  \n\n![](images/826cfc12d6f4b50e026203b4a343f3ba2f6649e7fd83713f3dbb47f873a3af0d.jpg)  \n图 6    三嵌段功能蛋白-聚四氟乙烯涂层示意图[49]  \nFig. 6    Schematic diagram of triblock functional protein-PTFE coating[49]  \n\n虽然 EC 涂层抗凝效果极佳，但在涂层制备前收集和培养 ECs 的这一过程既昂贵又耗时，因为培养基中产生足够数量的ECs 需要长达8 周的时间，且在此期间还可能存在被污染的风险[45-47]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 2.4    复合抗凝涂层  \n\n复合抗凝涂层是指两种或两种以上不同的物质所构建的涂层[48]，如：PEG-HS、生物活性分子-NO 等抗凝涂层都属于复合抗凝涂层，其抗凝机制主要是通过两种或两种以上材料协同作用，在高分子材料表面形成复合涂层抑制蛋白质和血小板的黏附与活化，从而达到抗凝的作用。该类涂层由多种材料组成同时具备多种功能，因此颇受青睐[49]。  \n\nLin[50] 等将肝素和胶原蛋白通过逐层自组装的方式制备出了肝素-胶原复合膜，该复合膜会紧密包覆在支架内外表面，得到具有抗菌和抗凝双重功能的复合涂层。实验表明，涂层后的支架具有良好的血液相容性且能促进内皮细胞的黏附和增殖。通过肝素-胶原复合膜的改性，可获得具有抗血栓形成性和 EC 偏好性的支架复合涂层且该涂层在促进血液接触材料的内皮化方面具有较大的潜力。  \n\n黄楠课题组[51] 将聚氯乙烯（PVC）导管浸泡在金属离子-酚醛/儿茶酚胺的溶液中，金属离子与酚醛/儿茶酚胺会组装成网络结构包覆在 PVC 导管的内外表面，得到具有抗菌和抗凝双重功能的复合涂层。实验证实，PVC 导管表面血小板和细菌的黏附与聚集数量明显少于无涂层样品，且涂层上残留的酚羟基还赋予了表面抗氧化和抗炎活性。金属-酚醛/儿茶酚胺复合涂层不仅具有类似过氧化物酶的催化活性，同时还具有优异的抗菌性能、抗氧化和抗凝血功能。与其他复杂的接枝方法和涂层技术相比，该方法制备简单易于操作，在血液接触类器械中具有广阔的应用前景（如图7 所示）。  \n\n![](images/564608b6e3ef0ad17c7362a1ca2976e2f509db39e59a60c7b2aa265ba97354bc.jpg)  \n图 7    金属-酚醛/儿茶酚胺表面涂层示意图[51]  \nFig. 7    Schematic illustration of metal-phenolic/catecholamine surface coatings[51]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3    展　望  \n\n医用高分子材料及器械抗凝血表面构建研究虽取得了一定进展，但目前抗凝血策略仍存在一些不足，亟待在以下 3 个方面进行突破：（1）材料/器械抗凝表面改性新方法和新技术的建立；（2）材料/器械表面抗凝性能提高的同时，在表面固定的（肝素钠盐、抗凝药物、NO）等生物活性物质以及涂层的稳定性和耐久性对于器械长期应用也十分重要，需要进一步深入探索；（3）加快开发复合型抗凝涂层，如：兼备抗凝血、抗菌等多功能复合涂层。随着人类在生物学、材料学和医学方面的不断进步，期待未来更加高效、廉价和复合型的抗凝血涂层被开发出来。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 15,
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ZHENG  W  W,  LIU  M,  QI  H  S,  et  al.  Mussel-inspired  triblock  functional  protein  coating  with  endothelial  cell  selectivity  forendothelialization [J]. Journal of Colloid and Interface Science，2020，576：68-78.  \n[48] NOURHAN H, GREVE B, ESPINOZA N A, et al. Mussel-inspired triblock functional protein coating with endothelial cell selectivityfor endothelialization [J]. Cellular Signalling，2021，77：109822.  \n[49] MOVAFAGHI  S,  WANG  W,  BARK  D  L,  et al.  Hemocompatibility  of  super-repellent  surfaces:  Currentand  future  [J].  MaterialsHorizons，2019，6（8）：1596-1610.  \n[50] LIN  Q,  YAN  J,  QIU  F,  et al.  Heparin/collagen  multilayer  as  a  thromboresistant  and  endothelial  favorablecoating  for  intravascularstent [J]. Journal of Biomedical Materials Research Part A，2011，96A（1）：132-141.  \n[51] LI  X,  GAO  P,  TAN  J  Y,  et  al.  Assembly  of  metal-phenolic/catecholamine  networks  for  synergisticallyanti-inflammatory,antimicrobial, and anticoagulant coatings [J]. ACS Applied Materials & Interfaces，2018，10（47）：40844-40853.  \n\n石恒冲，中科院长春应用化学研究所研究员，主要从事医用高分子材料及器械研究工作。发表 SCI 收录论文 50 余篇；申请国家发明专利 33 件，其中已授权 18 件；主持科技部国家重点研发计划课题、国家自然科学基金面上、中科院青促会、山东省重大科技创新工程等项目；入选中国科学院青年创新促进会，获中国科学院院地合作奖优秀产业化项目团队奖。  \n\n![](images/c733ef1c2f9af4d063c1f7bfc4c0b2e2d54eeadccc97143ff2bfeba34b86b410.jpg)",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Article",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Mechanistic formulation of inorganic membranes at the air–liquid interface  \n\nhttps://doi.org/10.1038/s41586-023-05809-y  \n\nReceived: 26 May 2022  \n\nAccepted: 8 February 2023  \n\nPublished online: 29 March 2023 Check for updates  \n\nChen Zhang1, Wanheng Lu1, Yingfeng Xu1, Kaiyang Zeng2 & Ghim Wei Ho1,3,4 ✉  \n\nFreestanding functional inorganic membranes, beyond the limits of their organic and polymeric counterparts1, may unlock the potentials of advanced separation2, catalysis3, sensors4,5, memories6, optical filtering7 and ionic conductors8,9. However, the brittle nature of most inorganic materials, and the lack of surface unsaturated linkages10, mean that it is difficult to form continuous membranes through conventional top-down mouldings and/or bottom-up syntheses11. Up to now, only a few specific inorganic membranes have been fabricated from predeposited films by selective removal of sacrificial substrates4–6,8,9. Here we demonstrate a strategy to switch nucleation preferences in aqueous systems of inorganic precursors, resulting in the formation of various ultrathin inorganic membranes at the air–liquid interface. Mechanistic study shows that membrane growth depends on the kinematic evolution of floating building blocks, which helps to derive the phase diagram based on geometrical connectivity. This insight provides general synthetic guidance towards any unexplored membranes, as well as the principle of tuning membrane thickness and through-hole parameters. Beyond understanding  a complex dynamic system, this study comprehensively expands the traditional notion of membranes in terms of composition, structure and functionality.  \n\nMembrane construction relies on two conditions: constraining the matter distribution in two dimensions and maintaining its geometric continuity. For example, ultrathin polymeric membranes can be prepared through interfacial polymerization (IP)12,13, typically performed at the gas–liquid interface14,15, at which the reactive building blocks are continuously supplied and undergo a systematic aggregation. We sought to take inspiration from the IP and apply the concept to various inorganics to create freestanding inorganic membranes.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# Conversion of nucleation preference  \n\nIn a typical aqueous system for producing inorganic materials, owing to the lowest free energy barrier (Supplementary Fig. 1; see details in Supplementary Section 1.1), solid nuclei formation on the vessel wall is preferred over that on the aqueous surface and homogeneous nucleation within the solution (Fig. 1a,b). Such undesired nucleation affinity, disclosed by exploring the force indentation curve on the interface using underwater atomic force microscopy (AFM), originates from the van der Waals attraction of the solid–liquid interface on adjacent solids, trapping them in a well-defined potential well (Fig. 1c). Regardless of the vessel materials, the interfacial potential well is identified in common aqueous systems (Extended Data Fig. 1). This discovery inspires us to devise a solid–liquid interface shielding (SLIS) strategy to shift the nucleation preference to the air–liquid interface, by simply using a hydrogel coating to raise the energy barrier for nucleation on the vessel wall (Fig. 1b).  \n\nIn this study, partially hydrolysed poly(vinyl acetate) (PVAAc) was used, which has alternating hydrophilic and hydrophobic areas (Supplementary Fig. 2), allowing its rapid swelling into a bulk hydrogel in the aqueous solution with an elastic filament layer facing the fluid (Supplementary Figs. 3 and 4). This hydrogel coat eliminates the potential well on the water–vessel interface and repels any approaching solid (Fig. 1c and Extended Data Fig. 1). Unveiled by the atomic pair distribution function (PDF) technique, the strategy can be described by a simple equation (equation (1)). Any approaching solids will cause a decrease in the conformational entropy $(\\Delta S<0)$ of the coated hydrogel system16,17 (Fig. 1d). This produces a repulsive entropic force $F$ (at the temperature of $T$ and the resulting displacement of $z$ ) to inhibit their adhesion18, which equivalently leads to an extra energy barrier $(\\Delta G_{\\mathrm{SLIS}}>0)$ ) on the solid–liquid interface from an energetic standpoint.  \n\n$$\nT\\frac{\\partial S}{\\partial z}=F=-\\frac{\\partial G_{\\mathrm{SLIS}}}{\\partial z}\n$$",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# From pilot practice to a membrane library  \n\nWe then chose the silver mirror reaction, a well-known aqueous process for producing solid deposits on the vessel surface19, as a pilot practice of the proposed SLIS strategy. When this classic reaction was performed in the PVAAc-coated vessel, a piece of shiny Ag membrane was directly obtained on the solution surface (Fig. 2a), which can be suspended by a varnished wire ring (Fig. 2b). The conductivity mapping (Fig. 2c) indicates its structural homogeneity in morphology,",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# Article  \n\n![](images/e3920991dd683f14df8242f9a1450d7a9d3d0e5b5b710604371a849fb18b3415.jpg)  \nFig. 1 | SLIS-induced conversion of the nucleation preference in aqueous solution. a, Sketch of the free energy change $(\\Delta G)$ normalized to the interfacial tension between the liquid medium and the solid nucleus $(\\gamma_{\\mathrm{ln}})$ through homogeneous nucleation (homo, upper meshed surface) and heterogeneous nucleation (hetero, bottom surface), as a function of the critical nucleus volume and the contact angle with the corresponding interface. The heterogeneous situation corresponds to two nucleation locations, namely, the solid–liquid interface and the air–liquid interface with the contact angles of $\\theta$ and $\\varphi$ respectively. b, Schematic illustration of three possible nucleation locations, with the highlighted nucleation priority in a container-held solution system before and after SLIS treatment. c, AFM force–distance curves for the bare and SLIS-treated glass surfaces measured under water. The two insets zoom in on the force-sensing regions and show the corresponding energy changes for the approach and withdrawal process, respectively. Scale bars are   \n${5}\\mathsf{n m}$ (approach), $20\\mathsf{n m}$ (withdraw) and $25\\mathsf{n N}$ (main plot). d, Microstructure diagrams and PDFs $(G(r))$ of the PVAAc hydrogel coating under free swelling and compressive load. Note that the $_{0^{-}0}$ distance in the hydrogel system results from a superimposed contribution from the relatively short $0_{w}–0_{w}$ (O in water molecule) and the relatively long $0_{w}–0_{\\mathrm{p}}$ (O in the OH group of the PVAAc network) distance. The pair correlation at about $4.8\\mathring\\mathrm{A}$ belongs to $0_{\\mathrm{w}^{-}}\\mathbf{C}_{\\mathrm{P}}$ (C in the PVAAc network) distance. The observed decrease in $_{0^{-}0}$ distances when the hydrogel coating is compressed validates the lower proportion of the $0_{\\mathrm{w}}\\mathrm{-}0_{\\mathrm{p}}$ contribution, which is caused by the decreased density of hydrogen bonds between water and the PVAAc network. This confirms an enhancement in the structural order degree of the hybrid system consisting of the PVAAc network and water molecules, namely, the reduced entropy of mixing $(\\Delta S<0)$ , under a compressive loading.  \n\ndensity and thickness at the macro scale. And the micro-level homogeneity was further confirmed by scanning electron microscopy (SEM; Fig. 2d,e and Supplementary Fig. 5). Moreover, the freestanding Ag membrane, just $189\\mathsf{n m}$ in thickness, is of comparable Young’s modulus (96.3 GPa) to its polycrystalline bulk counterpart20 (Fig. 2f and Supplementary Fig. 6). Meanwhile, the excellent flexibility is evidenced by the absence of fractures in these artificially created wrinkles with a bending radius of several micrometres (Fig. 2d and Supplementary Fig. 7).  \n\nBeyond the initial success, the SLIS technique was further validated to be universal for the direct synthesis of various inorganic membranes at the air–liquid interface (Extended Data Fig. 2a), even for those materials that are conventionally inconceivable, so long as the favourable reaction conditions for ensuring in-plane continuity were identified (Supplementary Table 1). The present membrane library involves 42 elements (Extended Data Fig. 2b) and five representative membranes for each of the eight categories of classic materials (Fig. 2g, Supplementary Figs. 5–46 and Supplementary Section 2), including elementary substances, oxides, sulfides, halides, hydroxides, metallates, nonmetallates and even coordination polymers, based on the three available types of aqueous reaction, that is, precipitation, hydrolysis and redox reaction. These inorganic membranes can reach several centimetres in dimension as determined by the vessel size and are uniform in thickness, typically ranging from tens of nanometres to several micrometres. Some transitional membranes of low-degree compactness have irregular through holes. Compared with their brittle bulk counterparts, most inorganic membranes are sufficiently thin to achieve a good degree of flexibility. In terms of serving as two-dimensional (2D) mediators for various energy couplings and/or conversions (Extended Data Fig. 2c and Supplementary Table 2), these functional membranes promise diverse and intriguing applications oriented to the energy flows (Supplementary Section 3), such as optical filtering and acoustic damping (Supplementary Figs. 47 and 48).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# Kinematic-controlled membrane growth  \n\nThe SLIS technique merely enables the constraint of the building blocks at the air–liquid interface. However, it still lacks the guidance to establish their in-plane continuity, which consequently seeks to gain the insight into the membrane growth mechanism. By exploiting the (FeS, $\\mathsf{C u}_{8}\\mathsf{S}_{5}$ , ZnS, ${\\sf D y}_{2}{\\sf S}_{3}$ and $\\mathsf{W S}_{2})$ , halides $S\\mathsf{m}\\mathsf{F}_{3}$ , $\\mathsf{A g C l}$ , $\\mathsf{B a C l F}_{3}$ , CuBr and $\\mathsf{P b l}_{2})$ , hydroxides $\\boldsymbol{\\left(\\mathbf{Al}(O H)_{3}\\right.}$ , FeOOH, $\\mathsf{C u(O H)}_{2}$ , ${\\mathrm{Cd}}(\\mathrm{OH})_{2}$ and La $\\left(\\mathrm{OH}\\right)_{3})$ , metallates $\\left(Z{\\mathsf{n}}({\\mathsf{A l O}}_{2})_{2}\\right.$ , ${\\tt B i V O}_{4}$ , ${\\bf A g}_{2}{\\bf C r O}_{4}$ , $\\mathbf{CaMoO_{4}}$ and $\\scriptstyle\\mathbf{In}_{2}S\\mathbf{nO}_{5})$ , nonmetallates $({\\bf C a C O}_{3}$ $\\mathrm{Zn}_{2}\\mathrm{SiO}_{4},\\mathrm{Mg}_{3}(\\mathrm{PO}_{4})_{2},\\mathrm{Cu}_{2}\\mathrm{SO}_{3}$ and $\\mathbf{Ag}_{2}\\mathsf{S e O}_{3},$ ) and coordination polymers (KPB, K-containing Prussian blue; Fe-taa, Fe(iii)-polyphenol tannic acid complex; ZIF-67; Ni-dmg, Ni(ii)-dimethylglyoxime complex and Cu-oxa, $\\mathtt{C u(I I)}$ -oxalic acid complex). The micrographs were purposefully focused on the wrinkling membrane areas to highlight their flexibility. The insets are the digital photos of the corresponding membranes suspended on a copper ring with a diameter of $4\\mathrm{{mm}}$ . The symbols in the upper-right corners indicate the reaction types used to prepare the membrane. Scale bars are 1 cm (b), 2 mm (c), $200\\upmu\\mathrm{m}$ (d), ${5}\\upmu\\mathrm{m}$ (d inset), $10\\upmu\\mathrm{m}$ (e), $1\\upmu\\mathrm{m}$ (e inset) and $200\\upmu\\mathrm{m}(\\mathbf{g})$ .  \n\n![](images/233789550ed8e5349795de19fb14127453624f5630f1015006e8c80798a44d28.jpg)  \nFig. 2 | From the pilot Ag membrane to unlocking a colourful membrane library. a, Digital photos of the completed silver mirror reaction performed in the untreated and SLIS-treated vessels. b, Digital photo of the as-prepared Ag membrane suspended by a varnished wire ring. c, Sheet resistance mapping at $20\\times20$ points on the Ag membrane with the test area of $10\\times10\\mathrm{mm}^{2}$ . d,e, Top view (d) and side view (e) SEM images of the Ag membrane. The insets respectively zoom in on a typical membrane wrinkle in d and the membrane edge in e. f, Typical experimental loading curve of the Ag membrane and the curve fitting to the theoretical equation. The inset highlights that the curve between load and deflection approaches cubic behaviour at high loads. g, Optical micrographs of 40 freestanding membranes prepared in the SLIS system, covering eight categories of materials, that is, elementary substances (S, Pd, Ag, Pt and Au), oxides ( $\\mathrm{TiO}_{2}$ , $\\mathbf{M}\\mathbf{n}\\mathbf{O}_{2}$ , $\\mathsf{R u O}_{2}$ , ${\\mathsf{C e O}}_{2}$ and $\\mathsf{W O}_{3};$ ), sulfides  \n\nsize-dependent absorption and reflection of Ag (ref. 21), we developed a fast spectroscopic technique (Supplementary Section 4.1 and Supplementary Figs. 49 and 50) to identify all the critical structural evolutions (Fig. 3a and Supplementary Fig. 51). A successful membrane formation from the floating building blocks depends on two kinematics: Brownian motion22 that dominates the initial aggregation and the capillary attraction, known as the Cheerios effect23 that drives the subsequent self-assembly (Fig. 3b).  \n\n![](images/3f854821b434d5e0c0b37216d744c218854e6f499ae8812cc427ece3f6642fb5.jpg)  \nFig. 3 | Kinematic-controlled membrane growth in the SLIS system.   \nidentify the dimension $f(\\alpha)=\\alpha.\\mathbf{1}$ , Typical high-resolution TEM image of the polycrystalline Ag network with recognizable four regions as highlighted by the lower-right schematic. The fast Fourier transformed images are shown in the respective region-corresponding colours. g, Calculated collision energy against the sizes of the two mutually attracted Brownian clusters driven by the Cheerios effect, which respectively composed of ${\\bf{\\dot{n}}}_{1}$ and $n_{2}\\mathbf{A}\\mathbf{g}$ particles as illustrated in the top diagram. h, Time-course coverage factors and fractal dimensions for different membrane-forming systems (see Supplementary Video 2), involving various building blocks of discal AgCl, hemispherical ${\\tt B i V O}_{4}$ and claviform ${\\bf A g}_{2}{\\bf C r}{\\bf O}_{4}$ particles as shown in the inset SEM images. The bottom pseudo-colour microphotographs depict their corresponding (quasi-) bicontinuous networks, respectively. The arrows indicate the moment when the Cheerios effect starts to work. Scale bars are $.\\upmu\\mathrm{m}$ (c), $500\\mathsf{n m}$ (e inset), ${\\bar{s}}\\mathsf{n m}(\\mathbf{f})$ and ${5\\upmu\\mathrm{m}}$ (h insets). a.u., arbitrary units.  \n\na, Time-resolved reflectance spectra of the solution surface throughout the Ag membrane formation. The numbered arrows indicate the critical structural evolutions and provide index support for subsequent characterizations. b, Schematic of the timeline showing the temporal kinematics of the floating units (particles or clusters) during membrane growth. c, Typical SEM image of the nascent floating Ag particles collected at 0.93 s after initiating the reaction. Their disordered distribution is confirmed by the inset 2D autocorrelation analysis result. d, Autocorrelation analyses for the time series of the attraction between the suspended AFM tip and the air–liquid interface as illustrated in the inset. In contrast to blank water, the intensity fluctuation for the reaction solution collected at 0.93 s indicates the 2D Brownian motion of the floating Ag particles. e, Multifractal spectra of the solid network and the complementary through-hole network in the (quasi-)bicontinuous Ag network as illustrated in the inset pseudo-colour TEM image. The dashed lines help to visually  \n\nAt an early stage after the reaction is initiated, numerous Ag nanoparticles are continuously supplied to the air–liquid interface (Fig. 3c). They are proved to float freely on the aqueous surface with in-plane Brownian motion by a customized AFM technique (Fig. 3d and Supplementary Fig. 52). These isolated particles stick together and create larger particles when random collisions occur. Because the reduced random mobility increases the collision frequency22, the larger particles thus act as the seeds and transform into 2D Brownian clusters as time proceeds (Extended Data Fig. 3a). This stage only lasts a few seconds as indicated by the rapid decrease in the interfacial reflectance.  \n\nThe evolution enters the second stage when the Brownian clusters are large enough, as the attractive capillary force between these solids in floating state (Extended Data Fig. 4 and Supplementary Figs. 53 and 54) overwhelms their random Brownian motion23,24. Driven by the Cheerios curved surfaces Ω, whereas the reaction temperature T, the building unit’s radius r and density $\\rho$ dictate the position of a mobilizable dashed plane $\\psi.$ The region of $\\Omega\\geq\\psi$ represents the desired spontaneous aggregation. These intersecting lines, which predict the critical $n_{1}$ and $n_{2}$ for varied cases of initial distance, are projected to the left plane. Note that, when d is larger than the capillary length of water $\\cdot\\lambda_{\\mathrm{c}}$ (around $2.7\\mathsf{m m}$ at room temperature), the determined curved surface will not intersect the plane. d, Phase diagram based on the density N and radial growth velocity G of the building blocks. The shaded region at the top-right corner is not available owing to the practical constraint of finite reactant supply. The colour bar shows the duration of the feedstocks’ depletion. e, Digital photos of three multiplex membranes derived from simple Ag membrane, including $\\mathsf{A g}_{2}\\mathsf{S}$ •Ag mixed membrane, $\\mathbf{CeO}_{2}$ –Ag bicontinuous membrane and FeOOH/Ag stacked membrane, whose structures are illustrated in the top-left schematics, respectively. Scale bars, 1 cm.  \n\n![](images/67beab96000179bac4753f3aedcaf31a81deb57da090bc1c1b76035bd29e10f7.jpg)  \nFig. 4 | General synthetic methodology and extension of complexity for the SLIS-mediated membrane. a, Phase diagram based on the geometrical description of the patterned floating Ag solids evolving from different reaction temperatures $(T)$ and initial concentrations of $[\\mathsf{A}\\mathbf{g}(\\mathsf{N}\\mathsf{H}_{3})_{2}]^{+}\\left(\\mathsf{l o g}_{2}(c)\\right)$ . GT models for phases, including node islands (NI), clique islands (CI), open network (ON) and closed network (CN), are presented in the same colour as that of the corresponding phase regime. The spheres show the local temperature and concentration-determined membrane thickness indicated by the left colour bar. b, Criterion for the spontaneous formation of Brownian clusters with specific size depending on the particle radius and density. The coloured surface denotes the smallest particle number in a Brownian cluster that may smoothly expand. c, Criterion for the spontaneous aggregation of two Brownian clusters/particles. The space is spanned by their sizes $(n_{1},n_{2})$ and initial distance (d, right colour bar), which collectively determine a family of  \n\neffect, these isolated Brownian clusters mutually attract and move to connect with the adjacent ones (Extended Data Fig. 3a), until they reach a critical state of (quasi-)bicontinuous network (Fig. 3e and Extended Data Fig. 3b). As it satisfies both the 2D matter distribution and the in-plane geometric continuity, this unique structure denotes the least criterion in geometry to define a freestanding membrane (Extended Data Fig. 5). The (quasi-)bicontinuous network is isotropic (Extended Data Fig. 5f–j and Supplementary Video 1) and multifractal (Fig. 3e), shown by transmission electron microscopy (TEM), confirming that it derives from combined Brownian motion and the Cheerios effect rather than a single dynamic mechanism. Thereafter, with the dynamic capture of the nascent particles by the network, these meander-shaped vacant regions are progressively filled and evolved into well-defined closed through holes (Extended Data Fig. 3b). Their circularity and geometrical convexity further increase with gradually reduced size and sharpened size distribution (Extended Data Fig. 3c–e). This process causes a continuous increase in the interfacial reflectance, until the holey membrane becomes compact.  \n\nThe impactful Cheerios-effect-driven collision contributes to the establishment of the physical connections (Supplementary Section 5.1), inferred from the plentiful twist boundaries observed in the polycrystalline Ag membrane (Fig. 3f, Extended Data Fig. 6 and Supplementary Figs. 55 and 56). The collision energy for inducing such mechanical welding25,26 markedly intensifies as the size difference between the floating objects increases (Fig. $3\\mathrm{g}$ and Supplementary Fig. 57). All these findings concerning the dynamic membrane growth are consistently confirmed by the in situ observations on other membrane-forming systems involving various building blocks (Fig. 3h; see also Supplementary Video 2 and Supplementary Section 5.2), regardless of component, size or dimension. Furthermore, experimental quantification of the kinematic parameters (Supplementary Figs. 58–63) validates the theoretical prediction that, during the capillary-attraction-driven acceleration process, the smaller unit of an attractive pair is much more mobile than the bigger one (Extended Data Fig. 7). As a result, the evolution towards a compact membrane that occurs after the (quasi-) bicontinuous network can proceed without any kinetic obstacles",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# Article  \n\n(Supplementary Section 5.3). The outer edge of the network extends epitaxially by attracting the isolated particles/clusters (Extended Data Fig. 8a–c and Supplementary Video 3). Meanwhile, the open vacancies inside the network are continuously separated into closed through holes at the high-curvature locations by the instantaneous capture of nascent particles (Extended Data Figs. 8d–e and 9 and Supplementary Video 4). The smooth evolution of the network provides the practical foundation to continuously adjust the through-hole ratio by simply controlling the reaction time.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# General synthetic methodology  \n\nThe understanding of the membrane growth process motivates our investigation into the synthetic methodology of any unexplored membranes in the complex dynamic system. We experimentally produce all the possible ultimate Ag patterns that emerge from various initial reaction conditions (Supplementary Fig. 64). This helps to construct a phase diagram based on graph theory27,28 (GT; Fig. 4a), a mathematical method that focuses on the geometrical connectivity and organization complexity (Supplementary Section 6). Accordingly, four distinct regimes depending on reaction concentration and temperature can be identified, that is, node islands (NI), clique islands (CI), open network (ON) and closed network (CN) in GT models (Supplementary Table 3). The first two are not membrane-forming phases, which correspond to the isolated particles and Brownian clusters in practice, featuring low graph density and small complexity index. For the other two regimes, successful membrane formation and adjustable thickness across a three-order-of-magnitude range can be achieved. Nevertheless, the CN phase presents a higher complexity index and much smaller thickness compared with the ON phase.  \n\nFor the kinematic-controlled membrane growth (Fig. 3b), the recognizable phase boundaries depict the theoretical obstacles during the dynamic organization of the floating building blocks (Supplementary Sections 7.1 and 7.2 and Supplementary Figs. 65 and 66). Briefly, the floating particles maintain isolated and vigorous Brownian motion when they are tiny with low collision probability, thus forming a primitive NI phase. Only when this initial obstacle is surmounted (Fig. 4b) can these particles organize into growable Brownian clusters. Similarly, the following barrier is whether the clusters’ capillary attraction is strong enough to compete with their random Brownian motion (Fig. 4c). If not, these clusters will remain isolated in the CI phase. If it is, these clusters, with high kinetic energy accumulating from the capillary force acceleration, can spontaneously interconnect into a network, forming the CN phase. Because Brownian motion and the Cheerios effect have inverse relationships with the increasing size of the floating solids, there should be an extreme situation when the initial building blocks are exceptionally large. They may bypass the Brownian motion stage and undergo direct self-assembly driven by capillary attraction, resulting in the ON phase with low graph density. Further kinematic simulation provides an intuitive understanding on the dynamic formation of these GT phases (see Supplementary Video 5).  \n\nAs the phase boundaries are theoretically determined by the size and density of the building blocks (Fig. 4b,c and Supplementary Section 7.3), a qualitative phase diagram can be derived (Fig. 4d and Supplementary Fig. 67) for these GT phases from the perspective of reaction kinetics, which underpins a general guidance for preparing the unexplored inorganic membranes in the SLIS system (Extended Data Fig. 10 and Supplementary Section 8.1). Briefly, for a targeted inorganic production in a mild aqueous reaction, its corresponding membrane synthesis can simply begin with an arbitrary initial concentration and reaction temperature. By evaluating the GT-phase attributes of the floating solids after sufficient time has passed, one can accordingly adjust the reaction conditions of a new synthesis. After a repetition of the prescribed experimental loop (Extended Data Fig. 10a), a well-defined membrane can be readily obtained, whose thickness and through-hole parameters can be further tuned by controlling the building unit size (Extended Data Fig. 10g and Supplementary Fig. 68) and the terminal reaction time (Extended Data Fig. 3b–e and Supplementary Section 8.2), respectively.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# Conclusion  \n\nDifferent from the IP process, the interfacial inorganic membrane emerges from a complex particle system, which involves several dynamics and multibody interactions29,30. Under favourable configuration, these chaotic floating building blocks spontaneously evolve into various elegant and tangible structures. Beyond the presented membrane library, the work broadens the scope of the traditional conception of membrane from several perspectives: in composition, access to any unexplored membrane from the aqueous system is made possible by our general synthetic guidance. Moreover, the membrane variety will further enrich when the SLIS strategy is expanded to organic or melt systems. In structure, the multiplex membranes with diverse topological structures are proposed in contrast to the simplex ones (Fig. 4e and Supplementary Figs. 69–71). In functionality, the concept of the selective 2D barrier to conventional matter flow is extended to energy flow. These newly unlocked dimensions of inorganic membrane design act as a catalyst to rejuvenate the mature membrane technology.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 10,
+        "chunk": "# Online content  \n\nAny methods, additional references, Nature Portfolio reporting summaries, source data, extended data, supplementary information, acknowledgements, peer review information; details of author contributions and competing interests; and statements of data and code availability are available at https://doi.org/10.1038/s41586-023-05809-y.  \n\n1. Ulbricht, M. Advanced functional polymer membranes. Polymer 47, 2217–2262 (2006).   \n2. Cieśla, A. Theoretical consideration for oxygen enrichment from air using high- $T_{c}$ superconducting membrane. Prz. Elektrotech. 88, 40–43 (2012).   \n3. Alvarez, P. J., Chan, C. K., Elimelech, M., Halas, N. J. & Villagrán, D. Emerging opportunitie for nanotechnology to enhance water security. Nat. Nanotechnol. 13, 634–641 (2018).   \n4. Lee, K. C. The fabrication of thin, freestanding, single‐crystal, semiconductor membranes. J. Electrochem. Soc. 137, 2556 (1990).   \n5. Lu, D. et al. Synthesis of freestanding single-crystal perovskite films and heterostructures by etching of sacrificial water-soluble layers. Nat. Mater. 15, 1255 (2016).   \n6. Dong, G. et al. Super-elastic ferroelectric single-crystal membrane with continuous electric dipole rotation. Science 366, 475–479 (2019).   \n7. Genet, C. & Ebbesen, T. W. Light in tiny holes. Nature 445, 39–46 (2007).   \n8. Shi, Y., Bork, A. H., Schweiger, S. & Rupp, J. L. M. The effect of mechanical twisting on oxygen ionic transport in solid-state energy conversion membranes. Nat. Mater. 14,   \n721–727 (2015).   \n9. Nair, J. P., Wachtel, E., Lubomirsky, I., Fleig, J. & Maier, J. Anomalous expansion of $\\mathsf{C e O}_{2}$ nanocrystalline membranes. Adv. Mater. 15, 2077–2081 (2003).   \n10. Liu, Z. et al. Crosslinking ionic oligomers as conformable precursors to calcium carbonate. Nature 574, 394–398 (2019).   \n11. Lalia, B. S., Kochkodan, V., Hashaikeh, R. & Hilal, N. A review on membrane fabrication: structure, properties and performance relationship. Desalination 326, 77–95 (2013).   \n12. Lu, X. & Elimelech, M. Fabrication of desalination membranes by interfacial polymerization: history, current efforts, and future directions. Chem. Soc. Rev. 50,   \n6290–6307 (2021).   \n13. Tan, Z., Chen, S., Peng, X., Zhang, L. & Gao, C. Polyamide membranes with nanoscale Turing structures for water purification. Science 360, 518–521 (2018).   \n14. Wang, Z. et al. On-water surface synthesis of charged two-dimensional polymer single crystals via the irreversible Katritzky reaction. Nat. Synth. 1, 69–76 (2022).   \n15. Ou, Z. et al. Oriented growth of thin films of covalent organic frameworks with large single-crystalline domains on the water surface. J. Am. Chem. Soc. 144, 3233–3241 (2022).   \n16. Haviland, D. B. Quantitative force microscopy from a dynamic point of view. Curr. Opin. Colloid Interface Sci. 27, 74–81 (2017).   \n17. Yang, C. & Suo, Z. Hydrogel ionotronics. Nat. Rev. Mater. 3, 125–142 (2018).   \n18. Gopinath, A. & Mahadevan, L. Elastohydrodynamics of wet bristles, carpets and brushes. Proc. R. Soc. A Math. Phys. Eng. Sci. 467, 1665–1685 (2011).   \n19. Kemp, M. Silver mirror. J. Chem. Educ. 58, 655 (1981).   \n20. Zhu, Y. et al. Size effects on elasticity, yielding, and fracture of silver nanowires: in situ experiments. Phys. Rev. B 85, 045443 (2012).   \n21. Mogensen, K. B. & Kneipp, K. Size-dependent shifts of plasmon resonance in silver nanoparticle films using controlled dissolution: monitoring the onset of surface screening effects. J. Phys. Chem. C 118, 28075–28083 (2014).   \n22. Uhlenbeck, G. E. & Ornstein, L. S. On the theory of the Brownian motion. Phys. Rev. 36, 823 (1930).   \n23.\t Vella, D. & Mahadevan, L. The “Cheerios effect”. Am. J. Phys. 73, 817–825 (2005).   \n24.\t Dixit, H. N. & Homsy, G. Capillary effects on floating cylindrical particles. Phys. Fluids 24, 122102 (2012).   \n25.\t Bai, X.-M. et al. Role of atomic structure on grain boundary-defect interactions in Cu. Phys. Rev. B 85, 214103 (2012).   \n26.\t Hwang, S., Nishimura, C. & McCormick, P. Mechanical milling of magnesium powder. Mater. Sci. Eng. A 318, 22–33 (2001).   \n27.\t Jiang, W. et al. Emergence of complexity in hierarchically organized chiral particles. Science 368, 642–648 (2020).   \n28.\t García-Domenech, R., Gálvez, J., de Julián-Ortiz, J. V. & Pogliani, L. Some new trends in chemical graph theory. Chem. Rev. 108, 1127–1169 (2008).  \n\n29.\t Packard, N. H. & Wolfram, S. Two-dimensional cellular automata. J. Stat. Phys. 38, 901–946 (1985). 30.\t Wolfram, S. Cellular automata as models of complexity. Nature 311, 419–424 (1984).  \n\nPublisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.  \n\nSpringer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.  \n\n$\\circledcirc$ The Author(s), under exclusive licence to Springer Nature Limited 2023",
+        "category": " References"
+    },
+    {
+        "id": 11,
+        "chunk": "# Article Methods",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 12,
+        "chunk": "# Materials and reagents  \n\nPartially acetylated poly(vinyl alcohol) (poly(vinyl alcohol-co-vinyl acetate), PVAAc, $1,750\\pm50,\\ge99.0\\%)$ was purchased from Sinopharm Chemical Reagent Co., Ltd., China. Anhydrous $\\mathsf{D}(+)$ -glucose $\\begin{array}{r}{(\\mathsf{C}_{6}\\mathsf{H}_{12}\\mathsf{O}_{6},}\\end{array}$ $\\geq99.5\\%)$ , ammonium hydroxide $(\\mathsf{N H}_{3}\\bullet\\mathsf{H}_{2}\\mathsf{O},28-30\\%)$ , phosphoric acid $(\\mathsf{H}_{3}\\mathsf{P O}_{4},285\\mathsf{w t}\\%)$ , sodium hydroxide (NaOH, $298.0\\%$ ), ammonium fluoride $(\\mathsf{N H}_{4}\\mathsf{F},\\mathsf{\\ge}99.99\\%)$ , titanium(iv) fluoride $(\\mathrm{TiF}_{4})$ , aluminium chloride $(\\mathsf{A l C l}_{3},99.99\\%)$ , calcium chloride $\\left(\\mathbf{CaCl}_{2}\\right.$ , $299.9\\%$ ), manganese(ii) chloride hydrate $(\\mathsf{M n C l}_{2}\\bullet4\\mathsf{H}_{2}\\mathbf{O}$ , $298.0\\%$ ), iron(iii) chloride $({\\mathrm{FeCl}}_{3},$ $97\\%$ , nickel(ii) chloride $(\\mathsf{N i C l}_{2},98\\%)$ ), copper(ii) chloride $(\\mathsf{C u C l}_{2},99\\%)$ , cadmium chloride $\\mathrm{(CdCl}_{2}$ , $99.99\\%$ , barium chloride $(\\mathsf{B a C l}_{2},99.9\\%)$ , copper(I) bromide (CuBr, $298.0\\%$ ), sodium iodide (NaI, $299.5\\%$ ), gold(iii) chloride trihydrate $(\\mathsf{H A u C l}_{3}{\\bullet}3\\mathsf{H}_{2}\\mathsf{O},\\mathsf{\\ge}99.9\\%)$ , ruthenium(iii) chloride $(\\mathsf{R u C l}_{3})$ , palladium(ii) chloride $(\\mathrm{PdCl}_{2},\\ge99.9\\%)$ ), chloroplatinic acid hydrate $(\\mathsf{H}_{2}\\mathsf{P t C l}_{6}{\\bullet}x\\mathsf{H}_{2}\\mathsf{O},299.9\\%)$ , potassium hexacyanoferrate(iii) $(\\mathsf{K}_{3}\\mathsf{F e}(\\mathsf{C N})_{6},\\mathsf{\\Lambda}_{2}\\mathsf{99}.0\\%)$ , ammonium iron $\\left(\\mathrm{III}\\right)$ citrate $((\\mathsf{N H}_{3})_{x}\\mathsf{F e}_{y}\\mathsf{C}_{6}\\mathsf{H}$ ${\\bf{\\sigma}}_{8}\\bf{O}_{7})$ , cobalt(ii) acetate tetrahydrate $(\\mathbf{Co}(\\mathbf{CH_{3}C O O})_{2}\\bullet4\\mathbf{H_{2}O},$ $299\\%$ ), manganese(ii) acetate tetrahydrate $(\\mathsf{M n}(\\mathbf{CH}_{3}\\mathbf{COO})_{2}\\bullet4\\mathsf{H}_{2}\\mathbf{O},\\mathsf{\\ge}99\\%),$ , sodium aluminate $(\\mathsf{N a A l O}_{2})$ , ammonium metavanadate $\\mathrm{(NH_{4}V O_{3},}$ $299.0\\%$ , potassium chromate $(\\mathsf{K}_{2}\\mathsf{C r O}_{4},\\mathsf{\\ge}99.0\\%)$ , sodium molybdate $(\\mathsf{N a}_{2}\\mathsf{M o O}_{4},\\mathsf{298\\%})$ , ammonium tetrathiotungstate $((\\mathsf{N H}_{4})_{2}\\mathsf{W S}_{4},\\mathsf{\\ge99.9\\%})$ , potassium hydrogen carbonate $\\boldsymbol{\\left(\\mathbf{KHCO}_{3}\\right.}$ , $99.7\\%$ ), sodium metasilicate pentahydrate $(\\mathsf{N a}_{2}\\mathsf{S i O}_{3}{\\bullet}5\\mathsf{H}_{2}\\mathsf{O},295.0\\%)$ , sodium sulfite $(\\mathsf{N a}_{2}\\mathsf{S O}_{3},$ $\\geq98.0\\%)$ , sodium thiosulfate pentahydrate $(\\mathsf{N a}_{2}\\mathsf{S}_{2}\\mathsf{O}_{3}{\\bullet}5\\mathsf{H}_{2}\\mathsf{O},\\mathsf{\\Lambda}_{2}99.5\\%)$ , ammonium persulfate $((\\mathsf{N H}_{4})_{2}\\mathsf{S}_{2}\\mathsf{O}_{8},\\mathsf{\\geq98.0\\%})$ , zinc sulfate heptahydrate $\\mathrm{(ZnSO_{4}{\\bullet}7H_{2}O,299.0\\%)}$ , copper(ii) sulfate pentahydrate $(\\mathrm{CuSO}_{4}{\\bullet}5\\mathsf{H}_{2}0,$ $\\geq98.0\\%)$ , iron(ii) sulfate heptahydrate $(\\mathrm{FeSO}_{4}{\\bullet}7\\mathrm{H}_{2}\\mathrm{O},299.0\\%)$ , sodium phosphate tribasic dodecahydrate $(\\mathsf{N a}_{3}\\mathsf{P O}_{4}\\bullet\\mathsf{1}2\\mathsf{H}_{2}\\mathbf{O},$ $298\\%$ ), magnesium nitrate hexahydrate $\\mathrm{(Mg(NO_{3})_{2}\\bullet6H_{2}O,99^{\\prime}}$ ), silver nitrate $(\\mathsf{A g N O}_{3},\\mathsf{\\ge}99.0\\%)$ , lanthanum(iii) nitrate hexahydrate $\\mathrm{(La(NO_{3})_{3}}{\\bullet}6\\mathsf{H}_{2}\\mathrm{O}_{\\ }$ $99.99\\%)$ , cerium(iii) nitrate hexahydrate $\\left(\\mathbf{Ce}(\\mathsf{N O}_{3})_{3}{\\bullet}6\\mathsf{H}_{2}\\mathbf{O},99.99\\%\\right)$ , dysprosium(iii) nitrate hydrate $\\left(\\mathrm{Dy}(\\mathsf{N O}_{3})_{3}{\\bullet}x\\mathsf{H}_{2}\\mathsf{O},99.9\\%\\right)$ , samarium(iii) nitrate hexahydrate $\\mathrm{(Sm(NO_{3})_{3}{\\bullet6}H_{2}O,99.9\\%)}$ , lead(ii) nitrate $\\left(\\mathrm{Pb}(\\mathsf{N O}_{3})_{2},\\right.$ $299.0\\%$ , bismuth(iii) nitrate pentahydrate $(\\mathtt{B i}(\\mathtt{N O}_{3})_{3}{\\bullet}5\\mathsf{H}_{2}\\mathbf{O},298.0\\%)$ tungsten powder $(\\mathsf{W},99.95\\%)$ ), sodium hypochlorite solution (NaClO, available chlorine $4.00\\substack{-4.99\\%}$ ), hypophosphorous acid solution $(\\mathsf{H}_{3}\\mathsf{P O}_{2},$ $50\\mathrm{wt\\%}$ in ${\\sf H}_{2}{\\sf O}),$ , hydrazine hydrate $(\\mathsf{N}_{2}\\mathsf{H}_{4}{\\bullet}x\\mathsf{H}_{2}\\mathsf{O},50{-}60\\%)$ , L-ascorbic acid $(\\mathbf{C_{6}H_{8}O_{6}},\\ge99.0\\%)$ , tannic acid $(\\mathbf{C}_{76}\\mathbf{H}_{52}\\mathbf{O}_{46})$ , oleamide $(\\mathrm{C_{18}H_{35}N O}$ , $299\\%$ ), hexamethylenetetramine $(\\mathsf C_{6}\\mathsf H_{12}\\mathsf N_{4},\\mathsf{\\ge99.0\\%})$ ), 2-methylimidazole $(\\mathsf{C H}_{3}\\mathsf{C}_{3}\\mathsf{H}_{2}\\mathsf{N}_{2}\\mathsf{H},99\\%)$ and dimethylglyoxime $(\\mathbf{CH}_{3}\\mathbf{C}(=\\mathbf{NOH})\\mathbf{C}(=\\mathbf{NOH})\\mathbf{CH}_{3},$ $299.0\\%$ were purchased from Sigma-Aldrich Inc. Hydrogen peroxide solution $(\\mathsf{H}_{2}\\mathsf{O}_{2},30^{-32\\%})$ was purchased from QReC Chemical Co., Ltd. Hydrochloric acid $(\\mathsf{H C l},37\\%)$ ), sulfuric acid $(\\mathsf{H}_{2}\\mathsf{S}0_{4},\\mathsf{9}8\\%)$ and nitric acid $(\\mathsf{H N O}_{3},67–70\\%)$ were purchased from Thermo Fisher Scientific Inc. Deionized water used was prepared from a TKA water-purification system (Smart-2-Pure).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 13,
+        "chunk": "# Pretreatment on the reaction vessel  \n\nWithout loss of generality, the consumable polystyrene Petri dish (Thermo Scientific, $\\phi=35\\times10\\mathrm{mm},$ ) was used as the reaction vessel for membrane synthesis. The inwall of the Petri dish was manually coated with the PVAAc film of about $1.6\\times10^{-2}\\mathrm{mg}\\mathrm{mm}^{-2}$ , which can rapidly swell into a hydrogel coat once it makes contact with the aqueous solution. Briefly, the Petri dish was waggled sufficiently following the addition of ${500}\\upmu\\upmu\\upmu\\upmu$ of PVAAc aqueous solution $(3.5\\mathrm{wt\\%})$ to guarantee that all of its inwall surface was wetted by the solution. The pretreated Petri dish with PVAAc film coating was then obtained by desiccating it at $70^{\\circ}\\mathrm{C}$ for 2 h, followed by naturally cooling down to room temperature.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 14,
+        "chunk": "# Membrane preparation  \n\nThe Ag membrane was prepared by performing the traditional silver mirror reaction (see the chemical equation in Supplementary Section 2.2) in the SLIS system. Briefly, $1.5\\mathsf{m l}$ of fresh Tollens’ reagent solution $(120\\mathsf{m M})$ ), which was prepared by adding $60\\upmu\\upmu\\upmu$ of ammonium hydroxide solution $(28-30\\mathrm{wt\\%})$ ) into $1.44\\mathrm{ml}$ of ${\\tt A g N O}_{3}$ solution, was first transferred into a pretreated Petri dish. After a subsequent addition of $1.5\\mathrm{ml}$ of mixed solution containing $\\ensuremath{\\mathbf{D}}(+)$ -glucose $(250\\mathsf{m M})$ and NaOH $(50\\mathsf{m M})$ ), the mixture was left to stand at room temperature for $30\\mathrm{min}$ . During this period, the reflective Ag membrane gradually formed on the aqueous solution surface. Finally, the Ag membrane was transferred onto the surface of the deionized water through a glass sheet. As a control, the synthesis was carried out in a clean Petri dish with no surface coating using the same reaction condition. Detailed reactions and procedures for other membrane syntheses in the SLIS system are described in Supplementary Section 2.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# Membrane transfer, suspend and cut  \n\nTo separate the floating membrane from the reaction Petri dish, the solution was first removed using a pipette, followed by adding $\\mathbf{8}\\mathbf{m}\\mathbf{l}$ deionized water to refloat the membrane. The water inside the dish was further replaced three times to fully eliminate residual chemicals. The membrane-held dish was then gently immersed in a large tank (usually a glass container with a diameter of 12 cm and a height of 6 cm) full with deionized water, enabling the transfer of the cleaned membrane to a wider aqueous surface. To cut the membrane into the desired dimensions, it was lifted by a hydrophobic acrylic plate, quickly cut with a razor blade before the water completely evaporated and then released to refloat on the water surface for subsequent transfer. Regardless of substrate composition or surface topology, these water-floating membranes can be conveniently transferred to or suspended by a wide range of substrates, including silicon slice, acrylic plate, glass slide, copper ring, varnished wire ring and conductive carbon tape in facing different characterizations. To adapt to the membranes with varied degrees of hydrophobicity and then prepare the flat membrane for X-ray diffraction (XRD) characterization, an optional hydrophilic surface of the hydrophobic acrylic plate was created by exposing it to 254-nm ultraviolet (UV) light (Novascan PSD-UVT) at room temperature for 15 min. Instead of deionized water, the acetone solution (about $2{-}10\\mathrm{v}0\\%$ in deionized water) was used to clean and float those membranes that were not water resistant.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 16,
+        "chunk": "# Structure characterizations  \n\nSEM images were acquired on a JEOL JSM-7001F with a 15-kV electron beam equipped with a tiltable specimen stage. Energy-dispersive X-ray spectroscopy data were collected using an Oxford X-max 50 detector. One side of the small piece of freestanding membrane was fixed on the conductive carbon tape for cross-sectional SEM observation. For energy-dispersive X-ray spectroscopy analysis, the membrane was transferred onto a flat silicon slice, copper foil or conductive carbon tape according to its chemical composition. TEM images were obtained on a JEM-2100F with a $200{\\cdot}\\mathbf{kV}$ electron beam and the conductive Ag membrane was directly supported on a bare copper grid. Fast Fourier transform (FFT) image processing was performed on DigitalMicrograph. The topography image of the membrane that is supported by a flat silicon slice was obtained on a Bruker JPK NanoWizard Sense AFM equipped with a AC240-PP tip (OPUS, nominal spring force constant of $2\\mathsf{N}\\mathsf{m}^{-1},$ ). The corresponding thickness measurement was performed on the JPKSPAM data-processing software. XRD patterns of membranes at room temperature were collected on a Bruker D8 ADVANCE at Cu $\\mathsf{K}_{\\upalpha}$ radiation $(\\lambda{=}1.54056\\mathring\\mathrm{A})$ at a scanning rate of $4^{\\circ}\\mathsf{m i n}^{-1}$ with the X-ray tube voltage of $40\\up k\\upnu$ and current of $25\\mathsf{m A}$ . The preferred orientation of the membrane was identified by completely indexing the XRD pattern, calculating each of the enhancements in the relative intensities compared with the polycrystalline standard pattern after removing the background and recognizing the $(h k l)$ value that corresponds to maximum enhancement. Fourier-transform infrared spectroscopy spectra were measured on a IRPrestige-21 spectrophotometer by using a Quest SingleReflection ATR Accessory equipped with a standard diamond puck.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 17,
+        "chunk": "# Optical, electrical and wettability characterizations  \n\nThe diffuse reflectance UV–visible–near infrared spectrum was obtained on a Shimadzu UV-3600 spectrophotometer with the wavelength range of 250 to 2,500 nm. Room-temperature sheet resistance of Ag membrane was measured using a Keithley 2602 SourceMeter equipped with a M3TC four-point probe and a Zolix TSM13-1 X-Y mobile station. The sheet resistance mapping was obtained by performing the measurements over an area of $10\\times10\\mathrm{mm}^{2}$ following a square $20\\times20$ grid. Surface wettability test was performed at room temperature by placing ${5}{\\upmu}{\\upmu}$ of sessile deionized water droplet on the substrate surface. On the basis of the side-view picture shot by an H1600 Industrial Camera equipped with S-EYE software, the relevant contact angle was determined using a specific plugin in ImageJ.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 18,
+        "chunk": "# Optical observation of freestanding membranes  \n\nAfter a small piece of membrane with appropriate size ( $3\\mathsf{m m}<$ dimension in each direction $<4\\mathsf{m m}$ ) was cut from a whole one, it was released to refloat onto deionized water surface and then suspended over a copper ring with outer and inner diameters of $4\\mathsf{m m}$ and $2\\mathsf{m m}$ , respectively, to ensure a single-layer membrane. The through-hole membrane was used for optical observation on an Olympus BX53 microscope after natural drying at room temperature.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 19,
+        "chunk": "# Mechanics of the as-prepared freestanding Ag membrane  \n\nOne face of the laser-cut polymethyl methacrylate ring (outer diameter ${\\phi}=11\\mathrm{{mm}}$ , internal diameter $2R=5\\mathsf{m m}$ and thickness $h=3\\mathsf{m m}$ ; Supplementary Fig. 6) was first painted with a thin polydimethylsiloxane coat (mixture of polydimethylsiloxane base and curing reagent in a 10:1 ratio), followed by curing at $80^{\\circ}\\mathsf{C}$ for $2\\mathfrak{h}$ . The coated side of the ring was then used to lift a water-floating Ag membrane with dimensions $12\\times12\\mathrm{mm}$ , which was subsequently dried at $50^{\\circ}\\mathbf{C}$ for $30\\mathrm{min}$ . The indentation measurement was performed at the centre point of the membrane on a MultiTest 1-i tensile and compression test system (Mecmesin) by using a quartz rod (diameter ${\\phi}=1\\mathrm{{mm}}$ ) with a hemispherical head. Before the measurement, the static electricity on the polymethyl-methacrylate-ring-suspended membrane and the quartz rod were fully eliminated using a Milty Zerostat 3. The loading rate was $1\\mathsf{m m}\\mathsf{m}\\mathsf{i n}^{-1}$ . The relation between the force $F$ and the indentation depth $\\delta$ is given by31–33  \n\n$$\nF{=}{\\sigma}^{\\mathrm{mem}}\\uppi R\\bigg(\\frac{\\delta}{R}\\bigg){+}E^{\\mathrm{mem}}q^{3}R\\bigg(\\frac{\\delta}{R}\\bigg)^{3}\n$$  \n\n$$\nq=1.05-0.15\\nu-0.16\\nu^{2}\n$$  \n\nin which $R$ is the radius of the Ag membrane; $E^{\\mathrm{mem}}$ is the membrane Young modulus and defined as $E^{\\mathrm{mem}}=E t$ , with the Young modulus $\\boldsymbol{E}$ and the membrane thickness $t$ ; $\\sigma^{\\mathrm{mem}}$ is the pretension and defined as $\\sigma^{\\mathrm{{mem}}}=\\sigma t$ , with the residual stress $\\sigma;$ and $q$ is a dimensionless constant that is related to the Poisson’s ratio $\\nu$ of silver (taken here as $0.37)^{34}$ . The values of $E^{\\mathrm{mem}}$ and $\\sigma^{\\mathrm{mem}}$ are obtained through curve fitting to the equation.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 20,
+        "chunk": "# In situ reflectance spectra during Ag membrane formation  \n\nThe acquisition of in situ reflectance spectra was carried out in a customized optical system as illustrated in Supplementary Fig. 49. To exclude ambient light, the measurements were performed in a sealed cuboid box $(160\\times100\\times70\\mathrm{mm}^{3})$ with all faces painted black. After a pretreated dish containing $1.5\\mathsf{m l}$ of fresh Tollens’ reagent solution $(120\\mathsf{m}\\mathsf{M})$ ) was placed inside in the central position, an incident light beam (visible fibre-coupled UHP-T-LED, Prizmatix) with a collimator $12\\mathsf{m m}$ in diameter was fixed at $30\\mathrm{mm}$ over the solution surface and set at a $90^{\\circ}$ angle from an opposite fibre detector of the spectrometer (Maya2000, Ocean Optics). To trigger the reaction, $1.5\\mathsf{m l}$ of mixed $\\mathsf{D}(+)$ -glucose $(250\\mathsf{m M})$ and NaOH $(50\\mathrm{mM})$ ) solution prestored in the dropper hanging over the apparatus was instantly introduced into the system and the in situ reflectance spectra of the air–liquid interface were consecutively collected through Spectra­ Suite. The spectra in five minutes before triggering the reaction were collected at a rate of $0.2{\\sf H}z$ to estimate the stability of this customized measurement. The acquisition rates were set at $16.7\\mathsf{H z}$ and $0.032\\mathsf{H z}$ , respectively, for the first 60 s and the remaining 29 min when the reaction was ignited. Critical time nodes were determined by mathematically identifying these moments containing extreme points of the recorded reflection intensity, which is a binary function of time and wavelength.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 21,
+        "chunk": "# Brownian motion of the floating silver particles  \n\nTo determine whether the floating silver particles on the bulk solution surface have been exposed to the gaseous phase or are still completely immersed under the air–liquid interface, we developed an indirect technique based on the collection and analysis of the localized force signal on an Asylum MFP-3D system equipped with a PPP-CONTPt-50 probe (NANOSENSORS; nominal spring force constant $0.2\\ensuremath{\\mathsf{N}}\\ensuremath{\\mathbf{m}}^{-1},$ . As shown in Supplementary Fig. $52\\mathsf{a}\\mathsf{-c}$ , the probe was suspended over the solution with a constant amplitude at which the attraction between the water surface and the probe can be well detected but out of the jump-to-contact distance. As well as the intrinsic noise caused by the fluctuations of water surface, once any floating solid passed through the space between the solution surface and the probe, it would instantly diminish the attracting force that the probe measured. Such a disturbance $D(t)$ would be well contained in the collected time series of force $F(\\mathbf{t})$ (converted from the amplitude signal) and strongly influence its autocorrelation result. At the time node of interest 1 s after initiating the silver mirror reaction in the SLIS system, the reaction was terminated by immediately replacing the reaction solution by equivoluminal deionized water. Besides the deionized water as a blank control, the aforementioned approach was performed on these particle/solution systems for 100 s with the collection frequency of 1 ${,}024\\ H z$ . The subsequent autocorrelation analysis of the time series $F(t)$ was performed by using the MATLAB built-in autocorrelation function (ACF) according to the following:  \n\n$$\n\\mathsf{A C F}(\\tau)=\\sum_{t=\\tau+1}^{n}\\frac{(F_{(t)}-\\overline{{F}})(F_{(t+\\tau)}-\\overline{{F}})}{\\sum_{t=1}^{n}\\left(F_{(t)}-\\overline{{F}}\\right)^{2}}\n$$  \n\nin which $\\overline{{F}}$ is the mean value of the collected time series and $\\tau$ is the time lag. There is a notable difference between the autocorrelation results for the cases of blank water surface and the particles-floated solution surface (Supplementary Fig. 52d–f). The latter case presents oscillatory autocorrelation peaks at different timescales, which were further confirmed to be an intrinsic signal feature instead of originating from noise. These oscillatory autocorrelation peaks are derived from the modulation effect on the detected force by the probe when these air-exposed particles pass through the space between the solution surface and the probe. Evidently, these results confirm that these silver particles generated from the bulk solution have passed through the air–liquid interface and been exposed to the air. Furthermore, these floating particles remain in random 2D Brownian motion on the aqueous surface.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# AFM measurements  \n\nAFM force–distance curves obtained from the indentation experiments were conducted on an Asylum MFP-3D scanning probe microscopy system equipped with a PPP-CONTPt-50 probe (NANOSENSORS; nominal spring force constant of $0.2\\mathsf{N}\\mathsf{m}^{-1})$ . The actual spring force constants in different situations were calibrated by acquiring force–distance curves on a stiff glass surface. To obtain the coated substrate, $10\\upmu\\upmu\\upmu$ of",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 23,
+        "chunk": "# Article  \n\nPVAAc aqueous solution $(3.5\\mathrm{wt\\%})$ ) was applied thoroughly onto the surface of the bare substrate (area $1\\times1\\mathrm{cm}^{2})$ ) at $70^{\\circ}\\mathrm{C}$ in an oven and then desiccated for $2\\mathfrak{h}$ . To measure the surface mechanical properties of various substrates in the aqueous system, the substrate was fixed at the bottom of a Petri dish $(37\\times7~\\mathrm{{mm})}$ , followed by adding $3{\\bmod{\\frac{}{}}}$ of deionized water at room temperature to immerse it. The probe was then completely submerged to perform measurement after the water level was stabilized. All the force curves were recorded under the same loading and unloading rate of $1.5\\upmu\\mathrm{m}\\mathsf{s}^{-1}$ . The displacement $(x)$ -dependent potential energy change $(\\Delta E)$ between $x_{0}$ and $x_{1}$ was obtained by using the recorded force curve $F(x)$ according to the following equation:  \n\n$$\n\\Delta E=-\\int_{x_{0}}^{x_{1}}F(x){\\mathrm{d}}x\n$$  \n\nForce maps of the interfaces of interest, including the control air– deionized water interface and the interface between air and the on-site floating Ag membrane $30\\mathrm{min}$ after igniting the silver mirror reaction in the SLIS system), were performed over an area of $10\\times10~{\\upmu\\mathrm{m}}^{2}$ following a square $5\\times5$ grid. All the measurements were conducted at room temperature, the vertical indentation rate was ${5\\upmu\\mathrm{m}\\mathrm{s}^{-1}}$ and the sampling frequency was 1 kHz. The adhesion force was determined by the lowest point of the retraction curve. The interfacial stiffness was determined by fitting the slope of the repulsive part of the approach curve. The rupture distance was calculated as the difference between the pull-off displacement and the snap-in displacement.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 24,
+        "chunk": "# PDF analysis  \n\nOne millilitre of deionized water was added onto the PVAAc coat (about $5\\times10^{-2}\\mathsf{m g m m}^{-2},$ ) on a square glass plate (area $12\\times12\\mathsf{m m}^{2}$ and thickness $2\\mathsf{m m},$ ), followed by standing at room temperature for 15 min. When the dry PVAAc film fully swelled into the hydrogel coat, the free water was carefully removed by filter paper to prepare the free-swelling hydrogel coating. To obtain the compressive-state hydrogel counterpart, another piece of glass plate was covered on the free-swelling hydrogel coating, followed by applying a compressive load of 21.6 N on a Mecmesin MultiTest 1-i tensile and compression test system. The transudatory water was removed by filter paper during 10-min-retained compressive loading. XRD data of the two-state hydrogel coatings supported by glass substrate was collected on a Bruker D8 ADVANCE at $\\mathtt{C u K\\upalpha}$ radiation $(\\lambda=1.54056\\mathring{\\mathbf{A}})$ with the $2\\theta$ degree range from $5^{\\circ}$ to $145^{\\circ}$ at a scanning rate of $2^{\\circ}\\mathsf{m i n}^{-1}$ . The X-ray tube voltage and current were $40\\up k\\upnu$ and $40\\mathrm{{mA}}$ , respectively. The PDF was directly calculated from the measured total scattering function through Fourier transformation by using PDFgetX3 (ref. 35).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 25,
+        "chunk": "# Fractal and multifractal analysis  \n\nThe Minkowski–Bouligand dimension $D$ of a fractal topological structure was determined through a classic box-counting method, according to the following equation36:  \n\n$$\nD=\\operatorname*{lim}_{\\varepsilon\\to0}{\\frac{\\log N(\\varepsilon)}{\\log_{\\varepsilon}^{\\frac{1}{\\varepsilon}}}}\n$$  \n\nin which $N(\\varepsilon)$ is the number of boxes of side length ε required to cover the geometric structure. $D$ is estimated as the exponent of a power law representing the fractal dimension of a certain structure. Moreover, the multifractal spectrum, also known as the singularity spectrum, namely, the relationship between the Hausdorff dimension f and the average singularity strength $\\alpha$ , was used to identify heterogeneity of the kinetic process and quantify structural complexity, which was determined through a previously reported method according to the following implicit functions of the distorting exponent $q$ (ref. 37):  \n\n$$\n\\alpha(q)=\\underset{\\varepsilon\\rightarrow0}{\\operatorname*{lim}}\\frac{\\sum_{i=1}^{N}\\frac{[P_{i}(\\varepsilon)]^{q}}{\\sum_{j=1}^{N}[P_{i}(\\varepsilon)]^{q}}\\mathsf{l o g}[P_{i}(\\varepsilon)]}{\\mathsf{l o g}\\varepsilon}\n$$  \n\n$$\nf(q)=\\underset{\\varepsilon\\rightarrow0}{\\sum_{i=1}^{N}}\\frac{\\frac{[P_{i}(\\varepsilon)]^{q}}{\\sum_{j=1}^{N}[P_{i}(\\varepsilon)]^{q}}{\\log\\left\\{\\frac{[P_{i}(\\varepsilon)]^{q}}{\\sum_{j=1}^{N}[P_{i}(\\varepsilon)]^{q}}\\right\\}}}{\\log\\varepsilon}\n$$  \n\nin which $P_{i}(\\varepsilon)$ is the probability (integrated measure) in the ith box of longitude $\\varepsilon$ , namely, a fraction of the amount of pixels in each box. The multifractal analyses were performed on both the (quasi-)bicontinuous solid network and the corresponding gaseous network, which were extracted from a typical SEM picture in advance through ImageJ.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 26,
+        "chunk": "# In situ observation of the membrane growth  \n\nThe growth processes of AgCl, ${\\tt B i V O}_{4}$ and ${\\bf A g}_{2}{\\bf C r}{\\bf O}_{4}$ membranes on aqueous surface were recorded using an H1600 Industrial Camera with the S-EYE software. The experiments were performed in a windshield box on a vibration isolator. The temperature was controlled by a bottom electronic heating plate. The reaction temperatures were $35^{\\circ}\\mathsf C$ , $50^{\\circ}\\mathsf{C}$ and $55^{\\circ}\\mathbf{C}$ for AgCl, ${\\tt B i V O}_{4}$ and ${\\bf A g}_{2}{\\bf C r O}_{4}$ membrane synthesis, respectively. A ring light-emitting diode was used in reflection mode as the lighting source. The vertical focal length was fixed in advance by focusing on the aqueous surface of $3{\\bmod{\\frac{}{}}}$ deionized water held in a pretreated Petri dish. After igniting the reaction by a quick addition of all the reactant solution, the kinematic evolution of the floating solids on the aqueous surface was simultaneously recoded at a frame rate of 30 frames per second with the resolution of 1 $^{920\\times1,080}$ pixels. All of the video editing was performed in Shotcut. On the basis of the particle imaging velocimetry algorithm, the velocity field was calculated by performing correlation analysis on the positions of the floating particles between successive video frames using PIVlab written for MATLAB38. The thin-plate spline analysis of differential evolution of the hole was performed using PAST 4.09.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 27,
+        "chunk": "# Data availability  \n\nThe data that support the findings of this study are available from the corresponding author on reasonable request. Source data are provided with this paper.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 28,
+        "chunk": "# Code availability  \n\nThe codes used to solve the kinematic equation, calculate the collision energy and perform dynamic GT-phase simulation are available in the repository at https://github.com/jokerxy624/membrane.  \n\n31.\t Wan, K.-T., Guo, S. & Dillard, D. A. A theoretical and numerical study of a thin clamped circular film under an external load in the presence of a tensile residual stress. Thin Solid Films 425, 150–162 (2003).   \n32.\t Komaragiri, U., Begley, M. & Simmonds, J. The mechanical response of freestanding circular elastic films under point and pressure loads. J. Appl. Mech. 72, 203–212 (2005).   \n33.\t Lee, C., Wei, X., Kysar, J. W. & Hone, J. Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 321, 385–388 (2008).   \n34.\t Cuenot, S., Frétigny, C., Demoustier-Champagne, S. & Nysten, B. Surface tension effect on the mechanical properties of nanomaterials measured by atomic force microscopy. Phys. Rev. B 69, 165410 (2004).   \n35.\t Juhás, P., Davis, T., Farrow, C. L. & Billinge, S. J. PDFgetX3: a rapid and highly automatable program for processing powder diffraction data into total scattering pair distribution functions. J. Appl. Crystallogr. 46, 560–566 (2013).   \n36.\t Liebovitch, L. S. & Toth, T. A fast algorithm to determine fractal dimensions by box counting. Phys. Lett. A 141, 386–390 (1989).   \n37.\t Chhabra, A. & Jensen, R. V. Direct determination of the f(α) singularity spectrum. Phys. Rev. Lett. 62, 1327 (1989).   \n38.\t Thielicke, W., & Stamhuis, E. J. PIVlab – towards user-friendly, affordable and accurate digital particle image velocimetry in MATLAB. J. Open Res. Softw. 2, e30 (2014).  \n\nAcknowledgements This research is supported by A\\*STAR under its 2019 AME IRG & YIRG Grant Calls, A2083c0059, as well as the National Research Foundation Central Gap Fund NRF2020NRF-CG001-023 and National University of Singapore TAP25002021-01-01.  \n\nAuthor contributions C.Z. and G.W.H. conceived the idea. C.Z. designed and performed most of the experiments and theoretical derivations. Y.X. assisted in some membrane characterizations as well as the video editing. W.L. and K.Z. supported the AFM experiments. G.W.H. supervised the project. C.Z. and G.W.H. analysed all the data and wrote the manuscript. All authors commented on the manuscript.  \n\nCompeting interests The authors declare no competing interests.",
+        "category": " References"
+    },
+    {
+        "id": 29,
+        "chunk": "# Additional information  \n\nSupplementary information The online version contains supplementary material available at https://doi.org/10.1038/s41586-023-05809-y.   \nCorrespondence and requests for materials should be addressed to Ghim Wei Ho.   \nPeer review information Nature thanks Edward Gillan and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.   \nReprints and permissions information is available at http://www.nature.com/reprints.  \n\n![](images/65f4b0713771a262317dbb4768444783f992c0fa070d4f7f59c4a0db14bd0d74.jpg)  \nExtended Data Fig. 1 | Universality of the SLIS strategy for diverse types of sessile water droplet on the substrates, visually showing their relative vessel routinely used in the lab to perform aqueous reactions. The polymer- hydrophilicity. $\\mathbf{a}_{3}^{-}-\\mathbf{h}_{3}$ , AFM force–distance curves for bare and PVAAc-coate based substrates include polyethylene (PE) (a), polytetrafluoroethylene (PTFE) substrate surfaces measured in air and under water, respectively. The insets (b), polypropylene (PP) (c), polystyrene (PS) (d) and polyethylene terephthalate zoom in on the force-sensing regions in the force–distance curve for the bar (PET) (e). The ceramic-based substrates include silicon (f) and sapphire (g). The substrate–liquid water interface during approach and withdraw processes metal-based substrate includes platinum (h). Their molecular or crystalline present the related potential energy changes $(\\Delta E)$ . structures are shown in $\\mathbf{a_{1}}\\mathbf{-h_{1}},$ , respectively. $\\mathbf{a}_{2}{-}\\mathbf{h}_{2}$ , Contact-angle images for a  \n\n![](images/ff3f56b7bc25adeeb9dda71e81457fe953aaf84be069073ac82f120e4f7eedfd.jpg)  \n\nExtended Data Fig. 2 | Further information on the inorganic membrane library constructed by the SLIS strategy. a, Digital photos of the reaction systems with freshly prepared membrane floating on the solution surface. b, Chemical elements involved in the inorganic membrane library constructed using the SLIS strategy. The yellow colour indicates that the element has been involved to constitute specific membrane in the presented membrane library. The blue colour denotes all the potential elements that can be theoretically further incorporated into the membrane library because each of them can find the analogue in chemical property in the as-involved ones. The grey colour indicates all the elements that are not available for SLIS synthesis owing to their extremely expensive price, chemical inertness and/or radioactive hazard. c, Chord diagram showing the potential multifield-coupling energy-conversion pathways among these functional membranes presented in the library (for details, see Supplementary Table 2). The available energy forms are mechanical, light, thermal, electric, magnetic and chemical energy.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 30,
+        "chunk": "# Article  \n\nExtended Data Fig. 3 | Critical developments of structural evolution during Ag membrane growth in the SLIS system. a, Voronoi texture-meshed typical SEM images of the floating solid collected at 4.32, 17.1 and 53.5 s. The red dot indicates the centre of each Brownian cluster. The colour of each cell denotes the coordination number, as indicated in the right colour bar. The colour of the boundary highlights the connectivity between the adjacent cells, that is, blue denotes unconnected cells and yellow denotes connected cells that are caused by the cross-domain growth of the Brownian cluster. b, Typical SEM images with pseudo colours of the floating Ag membrane collected at 15, 20.5, 25.5 and 30 min. The numbers above these images (a and b) help to identify the corresponding critical moments as indicated in Fig. 3a. c, Statistical map of the circularity against the logarithmic area for the through holes extracted from the typical SEM images in b. The top and right plots are the density distributions along the axes of the through-hole area and the circularity, respectively.  \n\n![](images/8efe058920969497b71c2553639308c854485c94639a587d66a582b63107dbbc.jpg)  \nd, Violin plots to show the statistical changes in the solidity (left) and the minimum Feret diameter (right) of the through holes after the formation of the (quasi-)bicontinuous framework. The scatter line in right plot shows the corresponding evolution in the coverage factor of the floating Ag membrane. e, Typical structures of the extracted through holes forming at the corresponding critical moments. Starting from the highly connected network structure, the through holes can gradually evolve into a low-circularity closed-hole structure, then to a high-circularity closed-hole structure and an eventual compact structure, accompanied by the continuously sharpened size distribution and increased geometrical convexity. To aid in visual identification, all the scatters, rugs, lines, violins and the extracted hole structures are respectively coloured with the same colours of the corresponding SEM images in b. Scale bars are $1\\upmu\\mathrm{m}$ (a,b and e).  \n\n![](images/1223c126e468f9c96bd18593e6a9f9a5a78ac8cc31e06da0c702867f6f6cc75c.jpg)  \n\nExtended Data Fig. 4 | Confirmation of the actual position of the as-prepared floating Ag membrane on the aqueous surface. a–f, 2D maps of the local adhesion force (a,d), interfacial stiffness (b,e) and rupture distance (c,f) for the interface between air and the on-site floating Ag membrane (d–f, 30 min after igniting the silver mirror reaction in the SLIS system) in comparison with that of the air–deionized water interface (a–c). The maps represent the results of AFM indentation measurements performed at 25 different positions on the two kinds of interface. The colour-coded plots represent variations of the parameters of interest as indicated in the left colour bars. g–i, Statistical variations for the measured adhesion force (g), interfacial stiffness (h) and rupture distance (i) extracted from the corresponding 2D maps. All the points are presented in scatters along with a Gauss function fitting line. The corresponding box plot shows the interquartile range with the marked mean value (open square inside), the median (transverse line inside) and the error bar. The air-floating Ag membrane interface presents a well-defined mechanical characteristic of the typical air–solid interface (Supplementary Fig. 52), featuring a much smaller AFM tip–interface adhesion force, a notably increased interfacial stiffness and a substantially shorter rupture distance in comparison with that of the air–water interface. These evidences confirm that the as-prepared Ag membrane is definitely floating on the aqueous surface with no liquid-water layer above it.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 31,
+        "chunk": "# Article  \n\n![](images/5b50529f5b87d1f5c65e0465fd7832329853a7093bd39acff746f4d83db34edb.jpg)  \n\nExtended Data Fig. 5 | See next page for caption.  \n\nExtended Data Fig. 5 | Structural characterizations of the (quasi-) bicontinuous Ag membrane. a,b, Digital photo (a) and transmission optical microscopic image (b) of the (quasi-)bicontinuous Ag membrane suspended by a varnished wire ring. Under transmission white light, the membrane with sub-visible-wavelength holes exhibits a selective optical transmittance of short-wavelength light, giving it a blue–violet appearance. The consistent colour without any detectable chromatic aberration demonstrates the largescale homogeneity of the (quasi-)bicontinuous structure. c–e, TEM images of the Ag membrane suspended on the TEM copper grid obtained under different magnifications, evidently confirming its multiscale structural homogeneity. The inset in e is the corresponding selected-area electron diffraction pattern, showing the polycrystalline nature. f, Illustration of the image-processing procedure for anisotropic analysis of the (quasi-)bicontinuous structure in a typical TEM image (d). Binary conversion was first performed on the image with the empty portions set to transparent. A copy of the processed image was then stacked on the original one and allowed to undergo a continuous clockwise rotation around the image centre. Through our customized Python image-processing code, the stacked part of the two square images at a specific rotation angle of θ was extracted by using their inscribed circle to calculate the geometric permeability (the ratio of the area of the overlapped through holes to the whole circle area). g, Rotation angle $\\theta$ -dependent geometric  \n\npermeability of the stacked (quasi-)bicontinuous structure. The step size of $\\wp$ is $0.5^{\\circ}$ . The real-time analysis of the geometric permeability with the corresponding stacked configuration is visually presented in Supplementary Video 1. h, Area distribution of the projected through holes of the stacked structure at the selected rotation angles. The density of the strips represents the frequency and the right curve shows the result of the frequency statistic. The dashed red line indicates the peak position of each distribution curve, highlighting the structural isotropy. i, TEM image of the practical stacked two-layer (quasi-)bicontinuous Ag membrane (right) compared with the single-layer counterpart (left). The stacking operation demonstrates a simple strategy to adjust the through-hole sizes in the membrane by using the (quasi-) bicontinuous structure. j, Statistical map of the circularity against the logarithmic area for the through holes in the one-layer and two-layer regions in i. The top plot is the density distribution along the axis of the through-hole area, showing a substantial decrease in both the hole size and the size dispersion after the stacking operation. The right box charts show the statistical result of the circularity of the through holes. The caps indicate the $3\\times$ interquartile range. Every box shows 25th–75th percentiles, with the marked median (transverse line inside) and mean (dot inside). Scale bars are $5\\mathsf{m m}$ (a), $100\\upmu\\mathrm{m}$ (b), $20\\upmu\\mathrm{m}$ (c), $2\\upmu\\mathrm{m}$ (d), $200\\mathsf{n m}$ (e) and $10\\upmu\\mathrm{m}\\left(\\mathbf{i}\\right)$ .",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 32,
+        "chunk": "# Article  \n\n![](images/1590f6fd9ac42840205aa3e02418e4191cf62b644356e9306eeb99a2b631f97c.jpg)  \n\nExtended Data Fig. 6 | Typical twist boundaries in the (quasi-)bicontinuous Ag membrane viewed from a direction parallel to the boundary. a, TEM image of the overall membrane network. b, Size distribution of the grains in the membrane compared with that of the initial floating particles. Two hundred well-defined grains distinguished by the diffraction contrast were counted. The two distributions are nearly identical, evidently confirming that the membrane is derived from the assembly of the initial isolated particles instead of an epitaxial growth based on the sliver atom deposition. c, Magnified TEM image of the marked region in a, visually showing the plentiful grain boundaries in the membrane network. d,e, High-resolution transmission electron microscopy image (d) of the marked region with small curvature in c and its corresponding pseudo-coloured counterpart (e), which highlights the three grains (A, B and C) with two visual grain boundaries $(60^{\\circ}/[0\\cdot11]$ between grains A and B, $60^{\\circ},$ /[-1-10] between grains B and C). The two dashed squares in d mark the well-defined cross-boundary regions (that is, square 1 marks the boundary between grains A and B and square 2 marks that between grains B and C). The black arrows indicate the reactive amorphous surface with about $2\\mathsf{n m}$ thickness. f–i, FFT images (f,h) and the corresponding Fourier-maskfiltered (twin-oval pattern, edge smoothed by five pixels) images (g,i) for the square-marked regions 1 and 2 in d, respectively. The reciprocal vectors in the FFT image were labelled by using the same colours with their mother grains. Note the crystal indices labelled with ‘’ denote that these lattice planes should be absent in the reciprocal space owing to the crystallographic extinction rule, which are identifiable in the direct space in the high-resolution transmission electron microscopy image obtained under an appropriate Scherzer defocus. The white lines in g and i depict the twist boundary plane. Scale bars are $500\\mathsf{n m}$ (a), $50\\mathrm{nm}$ (c) and 5 nm (d).  \n\n![](images/876b3b5a3cb33d0d6668144cb65f8639342674c60091eca4c4232489639ff482.jpg)  \nExtended Data Fig. 7 | Various factors that influence the capillary-attractiondriven kinematics between two floating particles. a–d, Influence of the particle size (variable $R_{1}$ is from 10 to $99.99\\upmu\\mathrm{m},$ ) on the kinematics at $L_{0}=400\\upmu\\mathrm{m},k=3,\\rho=8,000\\upk g\\mathrm{m}^{-3}$ and $\\varepsilon=0.05$ . e–h, Influence of the initial distance (variable $L_{0}$ is from 100 to $1,000\\upmu\\mathrm{m})$ on the kinematics at $R_{1}=20\\upmu\\mathrm{m}$ , $k=3,\\rho=8,000\\mathrm{kg}\\mathrm{m}^{-3}$ and $\\pmb{\\varepsilon=0.05.\\mathbf{i-l}}$ , Influence of the diversity factor (variable $k=R_{2}R_{1}^{-1}$ is from 1 to 10) on the kinematics at $L_{0}=500\\upmu\\mathrm{m},R_{1}=40\\times10^{-6}$ ,   \n$\\rho=8,000\\mathrm{kg}\\mathrm{m}^{-3}$ and $\\varepsilon=0.05$ . a,e,i, Time-dependent distance between the two floating particles in the capillary-attraction-driven acceleration process. b,f,j, Proportion of the displacement of the smaller particle to the initial distance when the two particles mutually collide. c,d,g,h,k,l, Time-dependent velocity for smaller particle $(v_{1};{\\mathbf{c}},{\\mathbf{g}},{\\mathbf{k}})$ and bigger particle $(\\upsilon_{2};{\\bf d},{\\bf h},{\\bf l})$ . Note that $\\pmb{\\nu}_{1}$ and $\\upsilon_{2}$ are in opposite sign, indicating their relative movement under capillary attraction.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 33,
+        "chunk": "# Article  \n\n![](images/5de60e1aee4d2d9c073bff74f224c36724151e59d5e20e4bd4cae4ddef9207e6.jpg)  \nExtended Data Fig. 8 | Further evolution of the membrane after the formation of the bicontinuous 2D network. a, Digital photograph of the aqueous system for AgCl membrane synthesis at the emergence of a whole (quasi-)bicontinuous network. The marked regions 1 and 2 highlight the marginal and internal regions of the floating solid network, respectively. b,c, Representative digital photograph of the marginal region of the (quasi-) bicontinuous AgCl network (b) and the corresponding map from the  \n\nvelocity-field analysis (c) (see the dynamic process in Supplementary Video 3). The colour shows the local vorticity direction and intensity as indicated in the right colour bar. d,e, Digital photographs (d) recording the change of the internal region in the bicontinuous network after continuous particle trapping in 36 s and the time-course spatial distribution of these trapped nascent AgCl particles (e) (see the whole process in Supplementary Video 4). Scale bars are 1 cm (a), ${500\\upmu\\mathrm{m}}$ (b) and $200\\upmu\\mathrm{m}$ (d).  \n\n![](images/4eca4f767c10af457be520876ec8f1c8839b45be2023ce79fdcb3d2b8037a4aa.jpg)  \n\nExtended Data Fig. 9 | Evolution of the through holes in connectivity and geometry during membrane network growth. a, Sequential microscopic images (obtained 6, 10, 26 and 35 min from the beginning of the reaction) recording the evolution of the AgCl membrane from the moment of forming (quasi-)bicontinuous structure (about 6 min). Scale bar, $200\\upmu\\mathrm{m}$ . b, Connectivity analysis of seven selected holes in the corresponding images in a. These selected regions are coloured and numbered as indicated on the right for the convenience of observation on the evolution in the hole’s geometry and connectivity. Note that almost all the holes are interconnected and impartible in the original (quasi-)bicontinuous structure. c, Calculated map obtained from the difference set between the microscopic images taken at 35 and 26 min, showing the locations of these trapped AgCl nascent particles during this period. The image is coloured blue to improve the visual contrast.  \n\nMacroscopically, all of the hole boundaries have a nearly identical rise in thickness, implying that the new AgCl particles are randomly trapped by the solid network and there is little possibility of generating new Brownian clusters in the hole region. d, Spatial evolution mapping of a representative hole (no. 1) during 26 to $35\\mathrm{{min}}$ The length and direction of the black arrows representatively show the maximum shrink rate and orientation of the hole at different boundary regions. The hot colour map highlights the vorticity of the shrink rate caused by the difference in the shrink orientation. The inset is the thin-plate spline analysis of differential evolution of the hole to visualize its shape changes in different areas. e, Distributions of the velocity magnitude and the tangent velocity along the hole boundary in d. These parameters were extracted clockwise along the hole boundary from the start point indicated by the white arrow in d.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 34,
+        "chunk": "# Article  \n\n![](images/0a36219ac3b5fb7abf160d604ddbc97e943f46df0883558f5f7aff235d95cb38.jpg)  \n\nExtended Data Fig. 10 | Foolproof synthetic guidance to an unexplored inorganic membrane in our proposed SLIS system. a, Step-by-step flow chart to guide the synthesis of an inorganic membrane. b, Summary of the initial conditions for creating the membranes in the presented library and the corresponding distributions based on 2D kernel density estimation, offering experiential choice of the initial concentration and temperature for different reaction categories. c–f, Results of the kinematic simulations for the CN (c), ON (d), NI (e) and CI (f) phases (see the dynamic evolutions in Supplementary Video 5). Note that these isolated particles are in grey and turn into blue once they are physically connected. g, 2D kernel density estimation map of the membrane locations in a customized space, which consists of the terminal reaction time-to-critical time ratio and the membrane thickness-to-building unit size (vertical dimension) ratio. All the data were derived from the 40 kinds of membrane in the presented library. The dot density is indicated by the top colour bar. The box chart shows the statistical result of the membrane thickness-to-building unit size (vertical dimension) ratio. The caps indicate the $1.5\\times$ interquartile range. The diamond box shows 10th–90th percentiles, with the marked median (transverse line inside) and mean (dot inside). The empirical deviation coefficient ω, which represents the statistical ratio of the SLIS-mediated membrane thickness to the building unit size (vertical dimension), is determined to be between 1.06 and 5.94 by the box range. The detailed description of the general synthesis of an unexplored inorganic membrane is included in Supplementary Section 8.1.",
+        "category": " Results and discussion"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# A Review of Functional Hydrogels for Flexible Chemical Sensors  \n\nPengcheng Zhou, Zongman Zhang, Fan Mo, and Yan Wang\\*  \n\nHydrogels have drawn considerable attention in the field of flexible chemical sensors due to their unique 3D structure, high permeability, ion-conductivity, and tissue-like mechanical properties. These structures and properties allow them to be functionalized into diverse sensing components and respond to chemical signals in complex environments. Herein, an overview of functional hydrogel-based flexible chemical sensors is provided. First, the representative hydrogel materials are introduced and the operating principles for flexible chemical sensors are discussed. Then, state-of-the-art functional hydrogel-based flexible chemical sensing applications are highlighted including gas sensors, humidity sensors, pH sensors, glucose sensors, wound monitoring, and others. Finally, major challenges and opportunities in this field are provided.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1. Introduction  \n\nAs an important component in health monitoring applications, chemical sensing is essential for real-time monitoring of human physiological information and environmental quality at the molecular level, not only for medical diagnosis, but also for preventive medicine.[1] However, traditional rigid chemical sensors  \n\nThe ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adsr.202300021  \n\n$\\circledcirc$ 2023 The Authors. Advanced Sensor Research published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.  \n\nDOI: 10.1002/adsr.202300021 have restrictions on practical applications, greatly affecting user comfort and mobility, as well as reducing the possibility of integration with emerging interaction approaches (e.g., augmented reality, virtual reality, and personalized medicine) in the future. Flexible chemical sensors change the way that human interacts with the external environment, in the context of “metaverse,”[2] due to their promising properties such as lightness, thinness, excellent stretchability, and clinical-grade accuracy.[3] So far, flexible chemical sensors have seen widespread applications in healthcare,[4] security,[5] environmental monitoring,[6] food safety,[7] and agriculture.[8]  \n\nTremendous efforts have been made to improve the performance of flexible chemical sensors by developing innovative materials and device structures. Advanced materials including carbon-based materials (e.g., carbon nanotubes, graphene, and carbon dots),[1a,9] transition metal compounds (e.g., $\\mathrm{{MnO}}_{2}$ , $\\mathsf{M o S}_{2}$ , and $\\mathrm{Ti}_{3}\\mathrm{C}_{2}\\mathrm{T}_{\\boldsymbol{x}}$ MXene),[10] and hydrogels[11] have been developed to manufacture flexible chemical sensors because of their great mechanical, electrical, and chemical properties. Among them, hydrogels have emerged as one of the most ideal building blocks of flexible chemical sensors, especially in wearable applications due to their excellent biocompatibility as well as tissuelike chemical, mechanical, and biological properties.[12] Hydrogels consist of 3D cross-linking polymer networks whose interstices are filled with abundant water. These networks can swell in water and retain water as well as allow penetration of ions and molecules, while the high-water content of hydrogels can provide a moist and ion-rich environment. On the microcosmic level, the polymer chains are enriched with one or more functional groups, e.g., amine, acylamino, carboxy, and hydroxy.[13] These functional groups can be further modified to endow hydrogels with desirable mechanical strength, conductivity, and stimulus responsivity.[14] On the macroscopical level, hydrogels exhibit favorable soft and flexible nature (withstanding even more than tenfold stretchability).[15]  \n\nAs the materials chemistry improves by leaps and bounds and the understanding of sensing mechanisms deepens, there are increasing efforts in the functionalization of hydrogels to expand the detecting species and enhance the sensing performance. Advanced processing technologies endow hydrogels with new properties (e.g., conductivity, antifreezing, and self-healing).[16] This is mainly done by designing cross-linking structures (e.g., interpenetrating polymer networks),[17] or hosting novel structures (e.g., nanoparticles, nanowires, and nanosheets) of conventional chemical sensing materials.[18] Functional hydrogel-based flexible chemical sensors have experienced extensive development in the last two decades (Figure 1). There are many reviews on hydrogel-based flexible electronics, mainly focusing on materials and properties,[19] and applications such as human–machine interfaces,[12b,20] wound healing,[21] and health monitoring.[14a,22] However, none of them summarizes functional hydrogel-based chemical sensors for environmental and human health monitoring at the molecular level. To this end, this work aims to provide a comprehensive review of functional hydrogel-based flexible chemical sensors and to suggest possibilities for future exciting developments. After a detailed introduction of hydrogel materials and operating principles of functional hydrogel-based chemical sensors, the latest applications such as gas sensors, humidity sensors, pH sensors, glucose sensors, wound monitoring, and others are presented in detail. The report concludes with a critical reflection on the current challenges and pertaining solutions associated with functional hydrogel-based chemical sensors.  \n\n![](images/1cfc3672b970611e8bb0f21e3f9fc54cdb0dc8067c2145d8793c030f70525d15.jpg)  \nFigure 1. Representative examples of functional hydrogel-based flexible chemical sensors over the last two decades. Reproduced with permission.[23,133] Copyright 2004, 2023, Elsevier. Reproduced with permission.[88,99] Copyright 2011, 2022, Royal Society of Chemistry. Reproduced with permission.[15b,69,128b] Copyright 2016, 2020, 2022, American Chemical Society. Reproduced under the terms of CC-BY-NC license.[91a] Copyright 2008, The Authors, published by Multidisciplinary Digital Publishing Institute. Reproduced with permission.[132] Copyright 2018, Wiley-VCH. Reproduced under the terms of CC-BY-NC license.[96b] Copyright 2021, The Authors, published by Walter de Gruyter. Reproduced under the terms of CC-BY-NC license.[131] Copyright 2020, The Authors, published by American Association for the Advancement of Science.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2. Hydrogel Materials  \n\nHydrogels can be classified inseveral ways, e.g., sources of polymer, types of cross-linking, and methods of preparation.[24] Herein, we categorize them by the sources of polymer, namely, natural hydrogels, synthetic hydrogels, and functional hydrogels (Figure 2). Their unique chemical, biological, and physical properties are utilized to enhance sensing capability.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2.1. Natural Hydrogels  \n\nNatural hydrogels, such as cellulose, alginate, chitosan, and their derivatives, are generally extracted from renewable resources.  \n\n![](images/217c75f69d22792f4838273c7c2f59c974fc711ef931ab6ba1be0563620c1227.jpg)  \nFigure 2. Representative hydrogel materials. a–c) Natural hydrogels. a) Cellulose. Reproduced under the terms of the CC-BY-NC license.[25] Copyright 2018, The Authors, published by Multidisciplinary Digital Publishing Institute. b) Alginate. Reproduced with permission.[26] Copyright 2009, American Chemical Society. c) Chitosan. Reproduced under the terms of the CC-BY-NC license.[27] Copyright 2011, The Authors, published by Associacao Brasileira de Polimeros. d–f) Synthetic hydrogels. d) Polyacrylamide. Reproduced with permission.[28] Copyright 2018, Royal Society of Chemistry. e) Polyvinylalcohol. Reproduced with permission.[29] Copyright 2018, Elsevier. f) Polyethylene glycol. Reproduced with permission.[30] Copyright 2020, SpringerLink. g) Functional hydrogels.  \n\nThey have been widely used to fabricate various types of sensors owing to their rich functional groups and unique chemical and/or physical properties, as well as excellent biocompatibility and biodegradability.[19b,c] In addition, they can be modified to meet the needs of specific functions by tuning the mechanical and electrical properties, solubility, and crystal structure, benefiting from the high reactivity of their functional groups.[19a] This section presents natural hydrogels for flexible chemical sensors represented by cellulose, alginate, and chitosan.  \n\nCellulose is the most abundant and ubiquitous polymeric raw material on the earth and is an important green renewable resource of linear polysaccharide material consisting of repeating $\\beta$ -(1,4)-linked D-glucose units (Figure 2a).[31] It is mainly isolated and extracted from plants (e.g., wood, flax, and cotton), or produced by bacteria (e.g., Acetobacter, Sarcina ventriculi, and  \n\nAgrobacterium). Cellulose has desirable mechanical properties, excellent thermal stability, structural stability, biocompatibility, and biodegradability. In addition, its easy-to-process property allows it to be constructed into specific materials with different structures, such as fibers, films, aerogels, and hydrogels.[19c] Among them, cellulose-based hydrogels can be combined with diverse functional materials, including metal or metal oxide nanomaterials, carbon nanomaterials, and conducting polymers, to achieve composite with desired sensing capabilities.[31] For instance, Ruiz-Palomero et al. utilized carboxylated nanocellulose as a carrier for S,N-codoped graphene quantum dots (S,NGQDs) to detect 2,4,5-trichlorophenol. The results showed that the incorporation of GQDs into hydrogels significantly enhanced the fluorescence intensity compared to pristine GQD solutions due to the interactions between the dots and carboxyl groups, where the interactions stabilized the GQDs and prevented their aggregation.[32]  \n\nAlginates are salts refined from brown seaweed, consisting of $\\alpha$ -L-glutamine and 1,4-linked $\\beta$ -D-mannuronic acid (Figure 2b).[26] The gelation process and physical linkage of common alginate-based hydrogels are through the exchange of $\\mathrm{Na^{+}}$ with divalent cations, such as $\\mathrm{Ca^{2+}}$ , ${\\mathrm{Sr}}^{2+}$ , and $\\mathtt{B a}^{2+}$ .[33] The cross-linking mechanisms between different divalent metal ions and sodium alginate vary, which may lead to significant discrepancies in the structures and characteristics of the resulting hydrogels.[34] The rich and tunable physical and chemical properties of alginate-based hydrogels, e.g., biocompatibility, biodegradability, and swellability, make them attractive for wearable and implantable chemical sensors.[35] For instance, Tamayol et al. fabricated alginate-based hydrogel fibers equipped with pHresponsive beads for long-term monitoring of wound pH levels. It should be noted that continuous measurement of wound $\\mathsf{p H}$ is important for wound management because it reflects the current state of healing. Thanks to the excellent flexibility of the asprepared alginate-based hydrogel, the assembled pH-responsive microfibers could maintain conformal contact with the skin. Meanwhile, the hydrogel provided a biocompatible interface with the wound site to prevent adverse effects from pH-responsive beads.[36]  \n\nChitosan is a natural polysaccharide derived from the deacetylation of chitin which is the main component of the exoskeleton of crustacean. It consists of randomly distributed $\\beta$ - (1,4)-linked D-glucosamine and N-acetyl- $D$ -glucosamine units with a degree of polymerization ranging from 500 to 5000 (Figure 2c).[37] Its biodegradability, biocompatibility, and nontoxicity have attracted immense interest in potential medical and sensor applications.[38] Previous studies have demonstrated that chitosan is highly permeable to water and anions, thus easily attaching to negatively charged surfaces and forming clusters with polyanion complexes or binding to metal cations.[19a] In addition, the amine and hydroxyl groups on the chains can be modified to immobilize the sensing materials.[39] Owing to its outstanding adsorption capacity, chitosan-based hydrogels have been widely used for the detection and monitoring of heavy metal ions. For example, Gogoi et al. introduced chitosan-based carbon dot-rooted agarose hydrogel films as a hybrid solid sensing platform for the detection of heavy metal ions. The fabrication of this solid sensing platform focused on simple electrostatic interactions between $\\mathrm{NH_{3}}^{+}$ groups in carbon dots and $\\mathrm{OH^{-}}$ groups in agarose. The strip of hydrogel film was simply immersed in a solution of heavy metal ions, such as ${\\mathrm{Cr}}^{6+}$ , $\\mathsf{P b}^{2+}$ , $\\ensuremath{\\mathrm{Mn}}^{2+}$ , and then displayed a color change upon exposure. The concentration of heavy metal examples can be quantified by the UV–visible reflectance spectrum.[40]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2.2. Synthetic Hydrogels  \n\nThe first observation of synthetic hydrogels dates back to the 1960s, when Otto Wichterle and Drahoslav Lím cross-linked hydroxyethyl methacrylate with ethylene dimethacrylate.[41] This was an incredible discovery, as it meant that people could synthesize polymer with water absorption/retention capabilities and superior biocompatibility even though they do not possess any inherent biological activity.[42] Synthetic hydrogels are becoming increasingly important in various applications, e.g., point-of-care assays, medical products, and biosensors, as they can be manipulated to yield desirable physical and chemical properties, similar to their natural counterparts.[43] They have also attracted extensive interest in flexible chemical sensors, typical examples includ polyacrylamide (PAAm),[44] polyvinyl alcohol (PVA),[18b,45] polyethylene glycol (PEG),[46] and their substituted derivatives.  \n\nPAAm is a water-soluble linear polymer made from acrylamide or a mixture of acrylamide and acrylic acid. Since its structure contains an amide group that readily forms hydrogen bonds with other polymers or functional groups, it can be grafted or cross-linked to obtain a variety of functionalized hydrogels with branched or networked structures (Figure 2d).[28] PAAm hydrogels are highly tunable and can be engineered to possess specific physical and chemical properties, such as mechanical strength, porosity, and biocompatibility, for a wide range of sensing applications.[6a,44b,47] For instance, He et al. constructed a conductive MXene-cellulose nanocrystals-tamarind gum-PAAm hydrogel consisting of ionically cross-linked tamarind gum network and UV photoinitiated cross-linked PAAm network. The asprepared sensor can stably indicate the change of humidity.[47] PAAm hydrogels can also be employed as sensing materials in pH sensors[48] and glucose sensors[49] by ionic intensity tracking. PVA is synthesized by the partial or complete hydrolysis of polyvinyl acetate group, rather than by polymerization of its structural monomer (vinyl alcohol), resulting in a hydrophilic synthetic polymer with semicrystalline, serrated structure, and excellent mechanical properties (Figure 2e).[29] PVA is also a water-soluble polymer that can be physically or chemically crosslinked, and then becomes suitable for special circumstances, such as in water or biological fluid environments.[11a] Due to their unique mechanical properties, biocompatibility, and biodegradability, PVA-based hydrogels have emerged as promising materials to manufacture wearable chemical sensors in recent years.[50] For instance, a bendable/wearable ethanol sensor had been successfully fabricated with a limit of detection (LOD) of 9.17 ppm by using PVA as coating material.[51] In addition, the abundant hydroxyl groups allow them to be modified and combined with diverse compounds to form functional hydrogels for multitude sensing applications, such as $\\mathsf{p H}$ , metal cation, and humidity.[14a,52] For example, Pan et al. reported a conducting PVA-based hydrogel as smart ionic skin for humidity sensing. The sensing mechanism of the ionic skin could be attributed to the hydrolytic ionization and the swelling effect of PVA.[53] PEG is a polar macromolecule consisting of repeating ethylene oxide units (Figure 2f).[30] It is suitable for medical products and sensor applications owing to its unique biological properties such as nontoxicity, biocompatibility, and biodegradability.[54] The cross-linking process of PEG-based hydrogels relies on connecting two or more polymer chains through chemical reactions. It benefits PEG-based hydrogel devices because the 3D structure of the cross-linked network increases the mechanical strength of the material, providing greater durability for applications with complex handling steps or harsh environmental conditions.[55] For example, Yao et al. introduced cellulose nanocrystals into PEG to fabricate flexible and responsive chiral nematic films with uniform helical structures. The resulting sensor exhibited a reversible smooth color change between green and transparent as the humidity varying from $30\\%$ to $100\\%$ , accompanied by a reversible swelling and shrinking. The mechanical strength and thermal stability of the sensors were further enhanced due to the incorporation of PEG.[56]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.3. Functional Hydrogels  \n\nAlthough the key features of virgin hydrogels enable them as promising materials for sensor applications, their drawbacks, such as heterogeneity and network chain termination/entanglement, are also obvious, which can affect their mechanical properties, the diffusion rate of analytes, and the transmission rate of signals.[57] Therefore, their mechanical strength, adsorption/resolution kinetics, and sensitivity still need to be optimized. It has sparked widespread interest in constructing hybrid hydrogels by combining functional materials to improve the properties of sensors and address existing issues.[58] The hybrid hydrogels can both maintain their own features and interact synergistically withother components.[19c,e] Common functional materials include nanoparticles, polymers, biomolecular (e.g., enzyme and DNA), and other additives (Figure 2 g).[21,57c,58c] When exposed to external stimuli, the sensing material undergoes physical/chemical changes that modulate interactions between polymer chains and analytes.[59]  \n\nIn addition, functional hydrogels combined with conductive materials are endowed with high electrical conductivity, a fundamental property of electronics. The conductivity of hydrogels can be enhanced by doping salts, polyelectrolytes, or other conducting compositions,[45,60] including inorganic salts,[16b] gold nanoparticles,[61] silver nanoparticles,[62] magnetic nanoparticles,[63] carbon nanotubes,[64] and conducting polymers.[65] Meanwhile, other monomers can be added to improve the physical-chemical properties of the hydrogels during polymerization. For example, PAAm is one of the most commonly used substrates for tough and stretchable conductive hydrogels, and many vinyl monomers (e.g., 2-hydroxyethyl methacrylate, sodium $p$ -styrenesulfonate, acrylic acid) have been selected to copolymerize with AAm to improve biocompatibility, flexibility, adhesion, and electrical conductivity of PAAm-based hydrogels.[66]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 3. Operating Principles of Hydrogel Chemical Sensors  \n\nHydrogels can exploit their special characteristics, such as hygroscopicity, swellability, and excellent permeability to construct flexible chemical sensors.[67] Typically, hydrogel chemical sensors accept inputs via analytes diffusion and then convert them into quantifiable outputs. The output signals are usually expressed in the form of volumetric,[44b] colorimetric,[17c] chemomechanical,[68] electrical,[69] and optical[70] changes. Based on the visualization of the signals, and the role played by hydrogels in chemical sensors, herein we discuss three operating principles: 1) volume/color change; 2) signal transduction; and 3) bidirectional exchange (Figure 3). For volume/color change and signal transduction, the signal occurs directly within the hydrogel body (Figure 3a,b), while for bidirectional exchange, the hydrogel acts as an interface between the biological system and the chemical sensing components (Figure 3c).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 3.1. Volume/Color Change  \n\nChemical analytes (e.g., ions, biomolecular[68,74]) can induce conformational transitions in polymer chains or networks of hydrogels, such as irregular curling, chain extension, and increase/decrease in cross-link density.[14b,44b] Changes in the composition and structure of polymer chains or networks cause increases/decreases in the volume of hydrogels, which can be visually observed (Figure 3a,I top).[75] For example, polyelectrolyte hydrogels have collapsed or extended polymer chains resulting in a macroscopic expansion or contraction in response to inputs such as pH and ions.[68,76] As another example, Miyata et al. utilized specific binding between antigens and antibodies to construct antigen-sensitive antibody-functionalized hydrogels, in which competitive binding of free antigens triggers a change in the shape of hydrogel.[74a] Hydrogels can also serve as hosts for microorganisms (e.g., Saccharomyces cerevisiae), creating living composites by exploiting genetic networks. Cell proliferation results in a controllable increase in composite volume, allowing sensors or medical devices to respond to the specific analytes, e.g., D-glucose, L-histidine, found in biological environments (Figure 3a,II).[71]  \n\nAnother type is the color change-based hydrogel in which indicators are embedded for the detection of chemical and biochemical signals (Figure 3a,I bottom).[77] Indicators are evenly distributed in hydrogel through reswelling form. Meanwhile, because most hydrogels are transparent and colorless, color changes can be clearly observed without interference.[17c,78] When receiving a chemical signal, the indicator responds rapidly to achieve a smooth transition of color.[56] Koh et al. proposed a mechanically compliant and biocompatible wearable microfluidic patch to collect and analyze sweat during exercise. A cobalt (II) chloride-containing poly(hydroxyethyl methacrylate) hydrogel coating was embedded in the serpentine-shaped channel. Among them, cobalt (II) chloride was responsive to sweat, while the hydrogel coating facilitated sweat sampling and flow. When sweat entered the sensor, the color of channel changed from deep blue to light purple as the chelation of cobalt (II) and water. The color change provides quantitative information on sweat rate and volume.[70] Furthermore, the injection of mixed indicators into hydrogels provides a reliable route to develop multifunctional chemical sensors.[79] Siripongpreda et al. utilized reswelling properties to disperse $\\mathsf{p H}$ indicators, a mixture of GOx, and KI solution in cellulose-based hydrogel. The prepared colorimetric sensor was used for the analysis of epidermal sweat composition (Figure 3a,III).[17b]  \n\nIt can be concluded that volume/color change operation is simple yet effective, but not applicable to high-precision analysis. Many researchers have utilized the potential changes caused by the volume/color changes to further quantify the analysis through apparatuses, such as piezoresistors,[80] smartphone,[70,81] and UV–visible spectrophotometers.[40,52a]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 3.2. Signal Transduction  \n\nThe signal transduction of hydrogel-based chemical sensors is mainly achieved through the conversion of chemical signals into electrical or optical signals and then",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# a Volume/color change  \n\n![](images/6a613d7901080c1157fbabb8c22b50a3d17f88e69d737a44ddab4359a6b31ec3.jpg)  \nFigure 3. Operating principles of functionalized hydrogel in chemical sensors. a) Ambient input for hydrogel detection with volume/color change. Examples include II) living Saccharomyces cerevisiae embedded in PAAm hydrogel as a glucose sensor, and III) carboxymethyl cellulose/bacterial cellulose matrix host pH indicators and glucose oxidase enzyme (GOx) as a sweat sensor. Reproduced under the terms of the CC-BY-NC license.[71] Copyright 2020, The Authors, published by America ciation for the Advancement of Science. R produced with permission.[17b] Copyright 2021, Elsevier. b) Signal transduction. Examples include II x-loaded h polyaniline hydrogel for the detection of glucose, and III) Imprinted asymmetric microlens arrays of PAAm hydro gels ed with permi pyright 2018, Wiley-VCH. Reproduced with permission.[46a] Copyright 2019, Elsevier. c) Hydro terfa e that a eable to emical analytes. Examples include II) glucose-responsive fluorescence dye immobilized with torin g of blood glucos vivo, and III) PAAm hydrogel-based artificial tongue used for astringen ed with permission.[46b Copyright 2021, Wiley-VCH. Reproduced under the terms of the CC-BY-NC license.[73] Copyright 2020, The Authors, published by American Association for the Advancement of Science.  \n\noutputting. The hydrogel can be functionalized with corresponding stimulus-responsive sensing components that are determined by the target analytes (Figure 3b,I).[82] Various active elements (e.g., carbon-based,[83] metal-based,[61,84] and conducting polymer[65,85]) have been integrated with hydrogels to monitor chemical analytes. This is because 1) the abundant functional groups of hydrogels provide the possibility of physical or chemical crosslinking with active materials, allowing them to be orderly arranged along the chains; 2) the high permeability of hydrogels for chemical analytes increases sensing capability.[14a,19e,86]  \n\nFunctional hydrogels exhibit electrical changes upon charge transfer due to chemical reactions induced by the target analytes, which can be achieved by adding specific conductive fillers to the pristine hydrogel.[16b,87] For instance, Bai et al. synthesized graphene oxide/polypyrrole hydrogels by in situ chemical polymerization. The resistance of the as-prepared sensor increases rapidly when exposed to an ammonia atmosphere, which is related to the dedoping of the conductive polymer by ammonia.[88] The electrical changes of functional hydrogelbased chemical sensors can also be manifested in variance of capacitance[89] and dielectric properties.[90] In addition, functional hydrogels are widely used to fabricate electrochemical sensors which is an important branch of chemical sensors. Hydrogel-based electrochemical sensors record the changes of current or potential in electrolytic cells, and analyze their relationships with the concentration of chemical inputs through the interaction between active materials and target analytes.[19a,82,91] For example, Zhong et al. developed a novel nanofibrous hydrogel with remarkable enzyme-like activity that can be used as an “ink” to print flexible electrochemical devices (Figure 3b,II). The as-prepared electrochemical sensor is highly sensitive to glucose.[72]  \n\nConversion of chemical signals to optical signals (e.g., fluorescence, phosphorescence, transmittance/reflectance)[92] typically involves pre-crosslinking the luminescent material, such as porphyrin conjugate, thioflavin, and metal–organic frameworks (MOFs), with hydrogels that emit light of a specific intensity.[93] Alternatively, the sensing components are integrated with the hydrogel to change the transmittance/reflectance intensity in response to stimulation by chemical analytes.[81,94] For instance, Gao et al. reported an agarose hydrogel-based fluorescent sensor composed of ${\\mathsf{Z r}}{\\mathsf{M O F}}$ , $\\mathrm{UiO}{\\cdot}66{\\cdot}\\mathrm{NH}_{2}$ , and rhodamine. This sensor can successfully detect phosphate with a low LOD of $2.0~\\upmu\\mathrm{M}$ . This is due to the high affinity between phosphate and the $\\mathsf{Z r{-}O}$ node affecting the fluorescence intensity of the 2- aminoterephthalic acid ligand.[93c] As another example, Elsherif et al. demonstrated a glucose-responsive hydrogel-based optical fiber via photopolymerization. The as-integrated sensor exhibited high glucose selectivity, rapid response, and high sensitivity $(2.6~\\upmu\\mathrm{W}\\ \\mathrm{m}\\mathrm{{u}^{-1}}$ ) (Figure 3b,III).[46a] Another important application is utilizing diffraction to detect specific analytes.[6a,b] Photonic crystals have a periodic dielectric structure that selectively modulates electromagnetic waves at specific frequencies according to Bragg’s law. When attached to a stimulus-responsive hydrogel, the Bragg diffraction of the sensor varies in response to an external stimulus. The diffraction intensity of the 2D photonic crystal array provides an excellent responsivity to the change of analyte concentration.[95]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3.3. Bidirectional Exchange  \n\nHydrogel is an ideal interface between chemical sensors and biological tissues due to its soft, biocompatibility, permeability, and ionic properties (Figure 3c,I). Functional hydrogels, which are integrated with chemical sensing components, can be directly attached to the human skin and biological tissues with minimum mechanical discomfort.[11b,12c,22b] The high permeability of hydrogels enables efficient bidirectional exchange of target analytes, where the hydrogels serve as substrates of chemical sensors.  \n\nIn the body-to-sensor direction, chemical analytes, such as ions, metabolites, and biomolecules, penetrate from the human body to chemical sensors via the hydrogel matrix.[12b,20] As mentioned previously, this is ascribed to the water-rich 3D crosslinked networks of hydrogels, which facilities the diffusion of analytes. In the sensor-to-body direction, external inputs, such as electricity and light, penetrate through hydrogels and interact with the target analytes.[11a,96] The tunable optical/electrical properties of functionalized hydrogels have significant implications for the development of high-performance implantable/wearable chemical sensors. For example, Sawayama et al. reported a wireless implantable device that incorporated a glucose-responsive fluorescent dye into a four-arm PEG hydrogel for measuring glucose concentrations in rat and pig models (Figure 3c,II). The hydrogel was mounted on top of light-emitting diodes and photodiodes for excitation and fluorescence detection, respectively. The hydrogel effectively mitigated the foreign body response and inhibited the formation of fibrous capsules, thereby minimizing the diffusion hysteresis in sensing. The as-integrated device can continuously measure glucose concentration in a diseased rat model with an accuracy superior to representative commercial glucose monitor.[46b] Another example is that Liu et al. encapsulated genetically engineered bacteria in a hybrid tough, stretchable hydrogel-elastomer. The encapsulated bacteria with programmed genetic circuitry can reflect green fluorescent protein in response to different chemicals. The tough hydrogel matrix allowed the diffusion of water, nutrients, and chemicals into the lumen to be recognized by bacteria and prevented bacteria from leaking into the environment (Figure 3c,III).[73]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 4. Applications  \n\nThe development of flexible chemical sensors is driven by the monitoring of chemical analytes that are crucial indicators of human health and potential hazardous in the environment. Benefiting from their impressive properties, i.e., biocompatibility, high permeability, and tailorable mechanical and electrical properties, functional hydrogels have seen numerous applications as highperformance flexible chemical sensors. In this section, representative examples are discussed and summarized, including gas sensors, humidity sensors, $\\mathsf{p H}$ sensors, glucose sensors, wound monitoring, and others.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 4.1. Gas Sensors  \n\nGas monitoring can be used to determine the levels of specific gases present in the environment, which plays an imperative role in environmental/health monitoring and industrial process gas analysis. For instance, $\\mathsf{N O}_{2}$ is a highly oxidized volatile gas that can affect the human immune, respiratory, and nervous systems. It greatly increases the risk of pneumonia, asthma, and neurological disorders if the concentration exceeds 1 ppm.[97] In addition, gas sensing is essential for monitoring human activities in which respiration involves changes in gas compositions and concentrations (e.g., $\\mathbf{O}_{2}$ , $\\mathrm{CO}_{2}$ , and $\\mathrm{H}_{2}\\mathrm{O})$ .[98] Flexible gas sensors can be employed for respiratory monitoring, industrial production, and other applications requiring deformable structures. Hydrogels are inherently stretchable and therefore have excellent adaptability, making them ideal for the development of flexible gas sensors. In the following part, we review flexible/stretchable hydrogel-based gas sensors for environment monitoring and wearable applications.  \n\nRegarding environmental gas (e.g., $\\mathrm{NO}_{x}$ and $\\mathrm{NH}_{3}$ ) monitoring, an important sensing mechanism is the diffusion of analytes into the hydrogel to participate in the electrode reaction and influence the charge transfer process.[61,99] Then the gas concentration is quantified by measuring changes in electrical signals.[88,91b] For example, a $\\mathrm{CaCl}_{2}$ -functionalized PAAm/carrageenan double network hydrogel was developed as a $\\mathrm{NO}_{2}$ sensor by a salt permeation strategy. Porous PAAm/carrageenan hydrogels were fabricated by a one-pot polymerization method and then immersed in $\\mathrm{CaCl}_{2}$ solutions to allow complete salt penetration (Figure 4a,b). When the sensor was exposed to different concentrations of $\\mathrm{NO}_{2}$ atmosphere, the current recorded by the external source meter changed significantly. In addition, the as-fabricated sensor was able to operate under large mechanical strains. The sensor maintained a relatively stable response (Figure 4c) and excellent linearity (Figure 4d) to $\\mathrm{NO}_{2}$ even with the sensor was stretched to $100\\%$ strain.[87b] To continuously monitor gas concentrations under larger tensile strains, Wu et al. developed a flexible, ultrastretchable, and transparent sensor for simultaneous detection of $\\mathsf{N O}_{2}$ and $\\mathrm{NH}_{3}$ . The increased toughness was achieved by forming a double network of polymer chains. The as-prepared sensor exhibited high selectivity, sensitivity $(78.5\\ \\mathrm{ppm}^{-1})$ ), linearity, and exceptionally low theoretical LOD $(1.2\\ \\mathrm{ppb})$ owing to the interaction between $\\mathsf{N O}_{2}$ and functional groups of the hydrogel (Figure 4e). The signal output was in the form of resistance which caused by the hindering effect of $\\mathsf{N O}_{2}$ on freemoving ions in the hydrogel (Figure 4f). Meanwhile, the asprepared hydrogels can withstand up to $120\\%$ strain, and exhibit a wide range of bending and twisting $(180^{\\circ})$ , allowing it to adapt to the extreme mechanical environment and function normally (Figure $^{4}\\mathrm{g})$ .[15a]  \n\nOther developed functional hydrogel-based flexible gas sensors have been demonstrated for the monitoring of $\\mathrm{NH}_{3}$ ,[6c,88,91a,100] $\\mathrm{CO}_{2}$ ,[101] $\\mathsf{N O}_{2}$ ,[15b,99,102] $\\mathbf{O}_{2}$ ,[91b,98a,c] trimethylamine,[19e,96a] and methanol vapor.[103] The signal output is mainly through colorimetric,[96a,101b] optical,[32,93a] and electrochemical,[91b,98a] forms.  \n\nBeyond monitoring the gases present around the wearer, functional hydrogel-based flexible gas sensors also open up new frontiers in medical diagnostics.[98b] For instance, a flexible/swellable hydrogel-based chemical sensor was fabricated to monitor changes in the concentration of oxygen molecules, based on colorimetric methods. The color-changing hydrogel was formed by rapid cross-linking of the polyamine porphyrin conjugate and the 4-arm star $\\mathrm{PEG}\\mathrm{-NH}_{2}$ polymer/N-hydroxysuccinimide-PEG (SVA-PEG) at room temperature. Herein, the polyamine porphyrin conjugate is the sensing material with a green-dominated fluorescence emission in an oxygen-rich environment and a red-dominated phosphorescence emission in a low oxygenation level, realizing the “traffic light”-like change. The SVA-PEG and the 4-arm PEG dendrimers enable hydrogel to swell and absorb wound exudate (Figure 5a). The as-prepared PEG hydrogel showed a porous structure with a diameter of about $5~{\\upmu\\mathrm{m}}$ after swelling to the maximum volume, enhancing the permeation of oxygen molecules (Figure 5b–d). In addition, the colorchanging hydrogel-based oxygen sensor can maintain sufficient skin-adhesive properties (Figure 5e). The hydrogel exhibited accurate “stoplight” response to oxygen over its dynamic range from green to red, even in the presence of highly disturbed tissue auto-fluorescence (Figure $5\\mathrm{f},\\mathbf{g},$ . In addition, when the asdeveloped hydrogel was directly coated on the wound site, it could swell to $200\\%$ of its original size within one minute and promote wound healing.[93a] Functional hydrogel-based flexible chemical sensors have also found applications in regenerative medicine and respiration monitoring.[98a,c] For example, a stretchable and self-healing PAAm-chitosan double network hydrogel-based oxygen sensor was achieved by utilizing a facile soaking and solvent replacement strategy, which delivered excellent repeatability, low LOD $(5.7\\ \\mathrm{ppm})$ , and high sensitivity $(0.2\\%\\ \\mathrm{ppm^{-1}},$ ).[98a] These results present newmaterial solutions for developing flexible, self-adhesive, and self-healable gas sensors with desirable performance.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 4.2. Humidity Sensors  \n\nHumidity (relative humidity, RH) sensing plays an important role in daily life, as fluctuations in humidity greatly affect the quality of human life and health, ranging from industry, agriculture, and food to respiration.[44a,105] Research on hydrogel-based humidity sensors is flourishing because the conductivity of functional hydrogel is directly related to the water content, while the adsorption/desorption of moisture inevitably leads to a change in conductivity.[53,106] In addition, the intrinsically soft nature of hydrogels provides a natural advantage in the development of wearable humidity sensors.[17a,89]  \n\nThe sensing mechanism of hydrogel-based humidity sensors is mainly attributed to the swelling/deswelling effect in which the hydrophilic groups in the hydrogel matrix are stimulated by water.[47,107] Wu et al. reported a double-network glycol/glycerolbased hydrogel for humidity sensors. With the relative humidity rising from minimum to maximum, the concentration of polymer chains decreases as the ionic solubility of polymer chains increases. Furthermore,the free water molecules weaken the interference of the polymer chains, therefore reducing the resistance and improving the sensing capability.[13] Zeng et al. developed a double network hydrogels with high transparency, viscosity, and flexibility by physical and chemical cross-linking of starch and in situ radical polymerization of acrylamide from the abundant biomass. The starch-based hydrogel had a porous structure after freeze-drying, which is consistent with the fact that the hydrogel can retain a substantial amount of water (Figure 6a). Moreover, the addition of PAAm improved the mechanical performance of the as-prepared hydrogels by creating a covalently cross-linked network and forming extra hydrogen bonds between the $-\\mathrm{OH}$ of the starch and $\\mathrm{-NH}_{2}$ of the polymer chains, which can withstand variedying degrees of compression, stretching, and twisting (Figure 6b). The as-assembled hydrogel-based sensor exhibited remarkable accuracy in detecting ambient humidity fluctuations (between $35\\%$ and $97\\%$ RH) and a broad spectrum of deformations. The device also showed fluctuating conductance curve when exposed to irregular human exhalation (Figure 6c). It is suggested that the as-prepared sensor can effectively track changes in breath length and intensity and help identify respiratory issues.[104]  \n\n![](images/d5babd0f22877b3b862b38f7584068037c593b6d6b8811d5721e0c52870280fe.jpg)  \nFigure 4. Flexible/stretchable gas sensors from functional hydrogels. a) Schematic fabrication process of $\\mathsf{C a C l}_{2}$ -infiltrated hydrogel. b) SEM image of PAAm/carrageenan double network hydrogel. c) Dynamic responses of the $\\mathsf{C a C l}_{2}$ -infiltrated hydrogel to ${\\approx}80{\\-}400\\$ ppb ${\\mathsf{N O}}_{2}$ at $0\\%$ , $50\\%$ , and $100\\%$ strains. d) Quantitative response versus ${\\mathsf{N O}}_{2}$ concentration. Reproduced with permission.[87b] Copyright 2022, Wiley-VCH. e–g) Stretchable ${\\mathsf{N O}}_{2}$ sensor based on PAAm/carrageenan double network hydrogels. Reproduced with permission.[15a] Copyright 2019, American Chemical Society.  \n\n![](images/4a9032bc0944f4a25d39cf8d3b06e06275354169acba31131bdd67c49840ec02.jpg)  \nFigure 5. Flexible/swellable gas sensors from functional hydrogels. a) Schematic of the one-pot synthesis of a swellable oxygensensing hydrogel. Inset are photographs of the as-prepared hydrogel under different oxygen concentrations. b) SEM image of blank hydrogel. c) SEM image of hydrogels containing polyamine porphyrins. d) Pore size distribution of hydrogel with and without polyamine porphyrins $(p<0.0001)$ . e) Photograph of hydrogel adhering to tissue. f) Quantitative luminescence photography of a dual-emissive conjugate. g) Derive normalized oxygen calibration scaled from the Stern–Volmer relationship. Reproduced with permission.[93a] Copyright 2022, Wiley-VCH.  \n\nIn addition, the ultrathin structures can enhance flexibility and sensing performance by increasing the specific surface area.[89,108] For example, a PAAm/carrageenan film with a thickness as low as $54.6~{\\upmu\\mathrm{m}}$ was used to fabricate a highperformance, stretchable, transparent, and low-cost humidity sensor (Figure 6d). As shown in Figure 6e, the responsivity of the hydrogel thin film-based humidity sensor increased with decreasing film thickness over a wide RH range. This is because the specific surface area of the hydrogel was enhanced by filming, which increased the contact area between the hydrogel and the water molecules, thereby improving the responsiveness to humidity (Figure 6f). And there was better sensing performance under high strains due to the exposure of a larger specific surface area (Figure 6g). Finally, the humidity sensor was tightly affixed to the inside of a face mask and applied to track respiratory behavior. It responded quickly to different breath intensity (Figure 6h).[44a]  \n\n![](images/e9ac46aad1f54b063ffd56c92446efd6a5fa80677314c3c50fdb66fefbba8ea2.jpg)  \nFigure 6. Flexible/stretchable humidity sensors from functional hydrogels. a) SEM image of freeze-dried starch hydrogel. b) Photographs of twisting hydrogel. c) Real-time response of the starch hydrogel-based humidity sensor to irregular human exhalation. Reproduced with permission.[104] Copyright 2021, Elsevier. d) Scheme illustration of PAAm/carrageenan hydrogel preparation. e) Time-dependent response of humidity sensors with different film thicknesses when exposed to different RH. f) Relationship between RH and time. g) Dynamic response curves for different RH at different tensile strains. h) Dynamic response curves of the sensor to irregular human exhalation, inset is the photograph of the humidity sensor integrated with a mask. Reproduced according to the terms of the C-CBY license.[44a] Copyright 2022, The authors, published by SpringerOpen.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 4.3. pH Sensors  \n\n$\\mathsf{p H}$ sensors have been investigated extensively over the past few decades because pH is an important parameter that is frequently tracked and regulated in industry and the environment.[110] It is also an important indicator of biological fluids, e.g., sweat, interstitial fluid, and wound exudate, reflecting the changes in the internal environment or the status of wound healing.[17b,111] The number of dissociated functional groups in pH-sensitive polymer network alters in accordance to the $\\mathsf{p H}$ of solution, resulting in fluctuations in the volume and refractive index of the hydrogel.[110c,112] In addition, hydrogels can be functionalized by well-developed pH indicators and conductive materials to improve sensing performance.[71,113]  \n\npH-responsive hydrogels are comprised of main-chain polymers featuring weakly acidic or alkaline groups that become more ionized in acidic or basic surroundings, respectively.[114] Richter et al. published an extensive, comprehensive, and intricate review on this topic in 2008. This review provided fundamental knowledge by describing the behavior of pH-sensitive hydrogel-based sensors and microsensors, as well as development principles and general regulations for such applications.[110b] To date, various cross-linking methods and conductive materials have been utilized to develop functional hydrogel-based pH sensors with high flexibility and conductivity.[79,115] For instance, a pH-sensitive poly(3,4- ethylenedioxythiophene) polystyrene sulfonate/hydrophilic polyurethanes (PEDOT:PSS/HPU) hydrogel was prepared by solution casting. It responded to pH changes in solution by swelling/deswelling, resulting in fluctuating current signal output. PEDOT:PSS dispersions are colloidal particles with a diameter range from 20 to $80\\mathrm{nm}$ and swell when exposed to water. These colloidal particles consist of short chains of PEDOT and long chains of PSS, where the PSS polymer chains are negatively charged and used to balance the positive charge of the PEDOT segments (Figure 7a). The as-prepared PEDOT:PSS/HPU hydrogel exhibited high flexibility and stretchability (Figure 7b). In addition, the resulting hydrogel films exhibit excellent stability and promising pH sensitivity, and can withstand extreme deformations, including twisting, bending, and stretching for 400 cycles, without significant degradation in sensing performance (Figure 7c–e).[109] As another example, Lee et al. demonstrated a wearable pH sensor employing MXene as the conductive agent and polyacrylic acid/PVA hydrogel as the pH-responsive material for muscle fatigue monitoring. The obtained sensor can effectively bind to human skin and firmly maintain its adhesion (Figure 7f). The electromechanical signals during exercise were recorded by a Bluetooth device to determine the pH change in sweat (Figure $\\mathrm{7g)}$ . The results showed that the pH value of sweat decreased as the muscles became exhausted. Hence, the degree of muscle fatigue can be estimated based on the mechanoelectrical response of the as-integrated device.[18b] Moreover, by combining functional hydrogels and smart devices, a variety of thin and flexible chemical sensors have been developed for imperceptible monitoring of the pH of body fluids.[110c,116]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 4.4. Glucose Sensors  \n\nThe measurement of glucose level is critical for diabetes management, such as controlling the conditions and preventing health complications.[46b,92,118] However, traditional sampling methods usually suffer from finger pricking, limiting long-term monitoring application. This issue can be overcome by the application of functional hydrogels, where excellent biocompatibility is ideal for designing subdermal implantable sensors, and outstanding hygroscopicity for constructing noninvasive body fluids collectors.[70,95a,98c,119] To date, functional hydrogels have been extensively exploited for glucose monitoring.[46b,65] The functional hydrogel-based flexible chemical sensors recognize glucose mainly through the following three ways: 1) GOx catalyzes glucose to generate hydrogen peroxide and D-gluconolactone, and then horseradish peroxidase further catalyzes hydrogen peroxide in the presence of hydrogen donor, causing measurable optical/electric signal fluctuations;[11a,17b,72,78b] 2) phenylboronic acid (PBA) binds glucose based on the high specificity of boronic ester group for cis-diols;[81,94] and 3) Concanavalin A combines glucose based on its strong affinity for hydrocarbon molecules.[39b,119a]  \n\nElectrochemical analysis is one of the most widely used methods in functional hydrogel-based flexible chemical sensors for glucose monitoring due to its easy integration, simple operation mode, and wide detection range. For example, Liang et al. fabricated a flexible electrochemical glucose sensor based on quaternized chitosan/oxidized dextran hydrogel. The hydrophilic network of the as-prepared hydrogels enabled the infiltration and enrichment of glucose, thus increasing the contact area between glucose and GOx, and broadening the detection range. The sensor was assembled on a flexible three-electrode screen-printed chip (Figure 8a,b), and the signal output was in the form of current. The anode current increased correspondingly in a stepwise manner when different concentrations of glucose solution were added sequentially to the electrolyte, indicating that the as-assembled functional hydrogel-based flexible chemical sensor has high sensitivity and fast response for glucose (Figure 8c).[117] In addition, PBA and Concanavalin A can reversibly bind to glucose, leading to an increase in the distance of polymer chains, thereby changing the optical/electrical properties of hydrogel.[92] For instance, Yetisen et al. designed a hydrogel optical fiber made of poly(acrylamide-co-polyethylene glycol diacrylate) core and calcium alginate cladding for continuous glucose monitoring. When glucose penetrated the fiber core and reacted with PBA, the osmotic pressure of the hydrogel increased and resulted in a change in the network density (Figure 8d). The asprepared hydrogel fiber is flexible and biocompatible, and can be injected into epidermis (Figure 8e). The glucose content is derived by detecting the refractive index variations of the fiber (Figure 8f).[94]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 4.5. Wound Monitoring  \n\nWound healing is a complex process. Wound monitoring plays a pivotal role in clinical and public health care, especially in patients with diabetes who may suffer from infections due to improper wound management.[122] Traditional gauze bandages are popular in wound healing due to their low cost and excellent air permeability, but they are uncomfortable for a long time wearing because of the need for repetitive uncovering for inspection and dressing replacement.[123] Therefore, many studies are devoted to the development of multifunctional smart integrated wound bandages for long time monitoring, closure, and treatment of skin wounds in recent years.[21a,120] Among them, functional hydrogel based-chemical sensors have attracted extensive attentions due to their intrinsic flexibility, excellent biocompatibility, sensitivity to wound exudate components, and ability to integrate with drug delivery, etc.[36,124] They can respond to the variations of wound exudate compositions in real-time by colorimetric or signal transduction,[47,78b,90] and achieve drug delivery by exploiting the structure changes under stimulation.[125] For instance, a multifunctional wound dressing was established for dynamic monitoring of pH and glucose in the wound area, and for promoting wound healing (Figure 9a). The as-integrated patch was highly transparent to help observe the status of wound, and outputted the accurate pH value and glucose contents in electrochemical signals.[120] As another example, Liang et al. proposed a dual pH and glucose responsive hydrogel based on the dynamic bonding of Schiff bases and phenylboronate for the release of metformin. Here, the Schiff base serves as pH-sensitive material, while the PBA is responsive to glucose. When the as-fabricated sensor was exposed to wound environment with low pH or high glucose content, the hydrogel network would dissociate and the loaded metformin would be released into the wound, promoting wound healing.[125a]  \n\n![](images/d24e83e8c136a7c0d02767d7f6625068b052499a04996815587206b3efe3da84.jpg)  \nFigure 7. Flexible/stretchable pH sensors from functional hydrogels. a) Schematic illustration of the impact of pH on molecular structure of PEDOT:PSS. b) Flexible fully swollen PEDOT:PSS/HPU hydrogels wrapped around a $4\\mathsf{m m}$ glass. c) The swelling behavior of the PEDOT:PSS/HPU hydrogels in Milli-Q water after 1 week and 2 months. d) Correlation between resistance and $\\mathsf{p H}$ of the solution for PEDOT:PSS/HPU hydrogels. e) The electrical response of printed $\\mathsf{p H}$ sensors to both ascending and descending pH changes. Reproduced with permission.[109] Copyright 2018, Wiley-VCH. f) Photograph of squat exercise pose. The inset schematic shows the M-hydrogel sensor exposed to human sweat during exercise. g) Measured pH value during exercise. Reproduced with permission.[18b] Copyright 2021, Wiley-VCH.  \n\nIn addition, taking advantage of the liquid properties of hydrogel, Wang et al. utilized 3D printing technology to prepare smart wound dressing for on-demand treatment. The hydrogels were formed by radical polymerization of quaternary ammonium-type chitosan and acrylamide monomers (HACC-PAAm), obtaining a highly cross-linked 3D network structure (Figure 9b). The asprepared hydrogels had strong adhesion and stretching properties and could follow the motions of human fingers (Figure 9c), which is crucial for long-term usage. Meanwhile, the transparent hydrogel facilitated colorimetric sensing. Figure 9d shows the linear relationship between color intensity of hydrogels and $\\mathrm{\\pH}$ value, and the inset are the corresponding photographs of the as-prepared hydrogel under different pH. The results show that the hydrogels have excellent specificity and sensitivity in response to $\\mathrm{H^{+}}$ while monitoring the wound state. Furthermore, the as-prepared wound monitors promoted wound healing in mice (Figure 9e), attributing to a reduction of underlying inflammation and promotion of nearby tissue growth (Figure $9\\mathrm{f-}$ g).[121] Table 1 provides a summary of recently reported functional hydrogel-based chemical sensors for wound monitoring.  \n\n![](images/7a3297e6b2fb019a2ca59bd8b1d7c86eda20c0e2c433c0255e1cd3669ad96c2f.jpg)  \nFigure 8. Flexible/bendable pH sensors from functional hydrogels. a) Schematic illustration of constructing a glucose sensor on a screen-printed circuit. b) Photograph of the constructed glucose sensor. c) Response of the flexible sensor to the repeated addition of 4 and $8~\\mathsf{m m}$ glucose in the electrolyte at $0.6{\\:}\\mathsf{V}.$ Reproduced with permission.[117] Copyright 2020, Elsevier. d) Structural composition of the glucose-sensitive fiber core cladded with calcium alginate, and quantified the concentration of glucose molecules by measuring the variation in the intensity of the output light. e) The implantation of hydrogel optical fibers in porcine tissue. f) Transmitted light intensity across the hydrogel fiber measured in different glucose concentrations. Reproduced with permission.[94] Copyright 2017, The Authors, published by Wiley-VCH.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# 4.6. Others  \n\nOther applications of flexible chemical sensors for detecting ions (e.g., Na+, K+, Hg2+, Cu2+),[6b,96a,128] alcohol,[69] DNA,[129] pesticide,[130] astringency perception,[131] and living cells[132] have also been developed with functional hydrogels. For example, a skin-like hydrogel elastomer-based electrochemical sensor has been fabricated by employing PAAm/calcium alginate hydrogels as a substrate to achieve conformal contact with skin, while thermoplastic polyurethane (TPU) film as an interlayer to bridge the hydrogels and conductive ink. The hydrogel precursor solution was prepared by crosslinking acrylamide with N, $N^{\\prime}$ - methylenebis-acrylamide and calcium sulfate, which was then carefully casted onto the oxygen plasma-treated side of the TPU film to form stretchable and tough hydrogels. The as-prepared hydrogel-TPU hybrid had a tensile strength of up to $1100\\%$ strain and a Young’s modulus of $0.37\\mathrm{MPa}$ similar to that of skin. In addition, the assembled electrochemical sensor demonstrated high sensitivity $(58.14~\\mathrm{mV^{-1}~p H}$ for $\\mathsf{p H}$ , $58.89\\mathrm{mV}$ decade−1 for $\\mathrm{\\DeltaNa^{+}}$ , and $59.11~\\mathrm{mV}$ decade−1 for $\\mathrm{K^{+}}$ ), excellent specificity and reproducibility for detecting electrolytes in sweat.[133] For chlorpyrifos pesticide monitoring, Yan et al. embedded the fluorescent indicators, namely gold nanoclusters $@$ zeolite-like imidazole framework $(\\mathsf{A u N C s}@\\mathsf{Z I F})$ composites, in double network hydrogels (glutaraldehyde cross-linked bovine serum albumin and Ca(II)- mediated alginate) to fabricate a flexible chemical sensor. Here, the ZIF framework is an ideal structure to achieve aggregationinduced emission through steric confinement effect, while the hydrogels worked as a host to improve the sensitivity by stabilizing the fluorescent signal and providing antifouling properties. Fluorescence images of hydrogels were converted into data information using a homemade portable device consisting of a 3D printed accessory and a smartphone. The device exhibited excellent linearity over the concentration range of ${\\approx}0.5{-}10~000~\\mathrm{ng}$ $\\mathrm{mL}^{-1}$ of chlorpyrifos and a low LOD of $0.2\\ \\mathrm{ng\\mL^{-1}}$ .[130]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 5. Conclusions and Perspectives  \n\nThe advantageous physical and chemical properties of functional hydrogel include intrinsic softness, three-dimensional nanostructure, excellent permeability, swellability, conductivity, and biocompatibility/biodegradability, and large-scale industrial accessibility, all of which provide strong benefits for the development of high-performance flexible chemical sensors. In this review, we first introduce common polymers for functional hydrogel-based chemical sensors, such as natural hydrogels, synthetic hydrogels, and functional hydrogels. Subsequently, we summarize three operating principles of functional hydrogel-based flexible chemical sensors, including 1) volume/color change, 2) signal transduction, and 3) bidirectional exchange according to the role played by hydrogels in chemical sensing process. We then present recent advances in functional hydrogel-based flexible chemical sensors toward environmental and human health monitoring, with a focus on gas sensors, humidity sensors, pH sensors, glucose sensors, wound monitoring, and others. Despite the great progress in this field, there are still challenges. We outline several remaining challenges with pertinent solutions below.  \n\n![](images/9dc58c7d32d8592d453b7b63eda94ffe73748ba0141ab347180b3f29d6e7330e.jpg)  \nFigure 9. Flexible/stretchable wound dressing from functional hydrogel. a) Schematic illustration of constructing multifunctional wound dressing for wound closure, bacteriostasis, and wound infection monitoring. Reproduced with permission.[120] Copyright 2022, Wiley-VCH. b) SEM image of HACCPAAm hydrogels. c) Photograph of HACC-PAAm hydrogels adhere in finger. d) The relationship between color intensity and pH value, inset are the photographs of HACC-PAAm hydrogel under different pH values. e) Photographs of skin wound in different days. f) Wound area in different days. g) Epithelium thickness in different days. Reproduced with permission.[121] Copyright 2022, Elsevier.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 20,
+        "chunk": "# 5.1. Sensing Performance  \n\nNumerous efforts in materials, structures, and synthesis methods have been explored to improve the sensing performance (e.g., selectivity, response time, sensitivity, and linearity) and application scenarios (environmental and health monitoring) of functional hydrogel-based flexible chemical sensors.[31,33,106b] For example, MOFs hydrogels are reliable fluorescent sensing platforms for chemical sensing owing to their solid framework structure, rich porosity, and versatility.[134] As another example, the contact area between the hydrogel and the analyte can be increased by thinning the thickness of the hydrogel, thereby improving sensitivity.[44a] Some macromolecules (e.g., DNA, RNA, enzyme)-functionalized hydrogels are favored for wearable and implantable chemical sensors due to their advantageous bioactivity and biocompatibility.[58c,135] However, hydrogels are not yet ideal candidates for high-performance commercial sensors due to their limited electrical conductivity, mechanical strength, and fatigue resistance. In this case, the introduction of diverse functional components to modulate the physical and chemical properties of hydrogels is a fascinating strategy to improve the measurement capabilities in real-life situations. Nevertheless, this manner still suffers from the Edisonian approach.[12a,b] Further studies should combine experimental analysis, theoretical calculations, and macroscopic modeling to better understand the interactions of hydrogels with other functional components to reduce the burden of development while improving sensor performance. Another important fact is that the existing hydrogels are mostly used as coatings or hosts in a passive manner, rather than in an active, responsive function.[86] Therefore, the development of all-hydrogel flexible chemical sensors, which is possible to truly realize tissue-like devices, can be considered in the future by developing actively responsive hydrogels.  \n\nTable 1. Applications of hydrogel-based flexible chemical sensors for wound monitoring.   \n\n\n<html><body><table><tr><td>Hydrogel materials</td><td>Hydrogel functions</td><td>Stimuli</td><td>Operating principles</td><td>Refs.</td></tr><tr><td>Alginate-based hydrogel</td><td>Substrate</td><td>pH</td><td>Color change</td><td>[36]</td></tr><tr><td>Polycarboxybetai</td><td>Substrate</td><td>Glucose</td><td>Color change, signal transduction</td><td>[78b]</td></tr><tr><td>AAPBAa)</td><td>Sensing materials</td><td>Glucose</td><td>Signal transduction</td><td>[93b]</td></tr><tr><td>Carboxylated agarose</td><td>Sensing materials</td><td>pH</td><td>Volume change</td><td>[124]</td></tr><tr><td>PAAm/chitosan</td><td>Substrate</td><td>pH</td><td>Color change, signal transduction</td><td>[47]</td></tr><tr><td>PAAm-PVA/SFb)</td><td>Sensing materials</td><td>pH and glucose</td><td>Color change</td><td>[108a]</td></tr><tr><td>PEGS-PBA-BA/CS-DA-LAG)</td><td>Sensing materials</td><td>pH and glucose</td><td>Color change</td><td>[125a]</td></tr><tr><td>Xyloglucan-PVA</td><td>Sensing materials</td><td>Moisture</td><td> Signal transduction</td><td>[90,126]</td></tr><tr><td>CMC/PVAd)</td><td>substrate</td><td>pH</td><td>Color change</td><td>[127]</td></tr></table></body></html>\n\na) Poly(3-acrylamide-phenyl boronic acid) b) Silk fibroin c) Polyethylene glycol-co-poly(glycerol sebacic acid)/dihydrocaffeic acid and l-arginine cografted chitosan d) Carboxymethyl cellulose/PVA.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# 5.2. Manufacturing Strategy  \n\nPresent hydrogels are usually fabricated by template method into bulky form factors, which mainly suffer from specific requirements (e.g., UV, high temperature) in the gelation process.[57b] Future flexible chemical sensors require high precision and small size for wearable and implantable applications. However, hydrogels are difficult to be patterned into high-resolution structures by conventional techniques owing to their high-water content. In this end, 3D printing (alias additive manufacturing) and lithography techniques enable rapid and low-cost mass production of functional hydrogel-based flexible chemical sensors.[76b,136] 3D printing has special requirements for the condition of the hydrogel ink, e.g., mechanical strength, gelation mechanism, and rheological properties.[22a] Recent study by Zhong et al. shows that the hydrogels responding to shear stress can rapidly switch between sol and gel states, facile to fabricate different patterns.[72] Lithography, e.g., imprint lithography, photolithography, and flow lithography, is another fascinating strategy for fabricating hydrogel devices at the microscale. However, the pattern obtained by lithography is relatively simple since the crosslinked hydrogel may need to be removed from the mold. In addition, the reactive groups, crosslinking speed, and curing time are important factors for the lithography processability and production efficiency, which requires efforts on the design of molecular structure and precursor solution.[136a,137] 3D printing and lithography techniques, in general, are ideal for fabricating nextgeneration hydrogel-based flexible chemical sensors, benefiting from the selection of multiple additives and the pre-programmed advantages.[24,34b,96a] There is also a need to improve existing processes and develop new manufacturing strategies in synergy with the development of materials.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# 5.3. System Integration  \n\nThe ultimate goal of functional hydrogel-based flexible chemical sensors is to achieve closed-loop sensing systems that can be deployed in real-life situations, where their power supply, data analysis, communication, and management should be considered. Therefore, the robust integration of functional hydrogels with bioelectronic devices and biological tissues is another challenge in this field. Liquid environments and wet substrates prevent hydrogel from adhering to target surfaces and lead to device failure. Recently, progress has been made in the interfacial adhesion properties of hydrogels, such as mussel-inspired selfadhesive hydrogels,[138] Janus hydrogels for bioadhesion to wet surfaces,[139] and hydrogels with strong adhesion in both aqueous and oily environments.[140] Catechol groups are capable of forming covalent and noncovalent bonds with a variety of materials. Therefore, functionalization of hydrogels with catecholcontaining compounds, such as polydopamine, tannic acid, and tea polyphenols, is an important strategy to improve self-adhesive properties.[141] In addition, the establishment of effective interfacial bonding of hydrogels to target surfaces is a promising research direction. This can be achieved by modulating the synergistic interaction between hydrophilic and hydrophobic polymer chains and by removing the interfacial liquid layer.[140] In the future, the enhanced adhesion properties will provide reliable and conformal contact of integrated functional hydrogel-based flexible chemical sensors with tissues, thus enabling high device stability and signal fidelity. In addition, in laboratory research, most hydrogel-based chemical sensors focus on detection of single analyte and require external power source. Therefore, rational design to fabricate multifunctional and self-powered chemical sensing systems with capability of monitoring multiple analytes is expected. To achieve this goal, novel functional materials, transduction mechanisms, and integration methods need to be further explored in the future.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# 5.4. Long-Term Stability  \n\nDespite the great progress in hydrogel-based wearable and implantable electronics, there remains an urgent need for future research to improve the chronic stability and the biocompatibility of hydrogels due to dehydration and the impact of foreign body reactions and damages. Water volatilization caused by high temperatures and dry conditions will affect the mechanical properties of hydrogels, severely limiting their service life and application scenarios. The construction of anti-drying hydrogels by adding hygroscopic salts or water-retaining agents is a promising material solution for applications exposed to air.[13,142] Covering with an elastic material to prevent dehydration is another effective strategy.[108b,133] In addition, the self-healing capability can maintain the structural and functional integrity of hydrogels if compromised by external mechanical force or chemical attack, which is especially important in complex in vivo environments.[2b,143] A promising solution is to construct functional hydrogels with interpenetrating network structures and sufficient dynamic noncovalent bonds by controlling the cross-linking approaches and synthesis steps. The remarkable, tunable mechanical properties of the interpenetrating network structure and the reversible combination of dynamic noncovalent bonds are ideal for simultaneously achieving high mechanical compliance and intriguing self-healing ability.[29,98a] Moreover, the lighter and thinner structural designs should be targeted for better mechanical compliance, which can effectively facilitate long-term, and real-time health monitoring imperceptibly. For the tradeoff of mechanical compliance and robustness, innovative materials design is necessary.[3,144] Last but not least, for on-skin applications, permeable hydrogels enable long-term health monitoring and should be further developed.[145]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# 5.5. Commercialization  \n\nThe advent of hydrogels offers great market prospects for healthcare, pharmaceuticals, etc. At present, many hydrogel-based drugs and wound dressings have been successfully commercialized, such as Advil for fast pain relief, Gaviscon for acid reflux, Kaltostat, and Helix3-cm for wound dressing. A few commercial drugs have utilized the basic chemical sensing ability of hydrogel, which is essentially based on structural expansion caused by glucose level, pH value, and ionic strength, to achieve controlled drug release. For example, Voltaren shrinks in a low pH environment (stomach) and swells in a neutral $\\mathrm{\\tt{pH}}$ environment (intestine) to achieve targeted drug release.[42a] For commercialization of hydrogel chemical sensing and therapeutics, an important direction is the development of smart hydrogels to monitor wound healing status (e.g., glucose levels and pH) in real-time for targeted drug release. This requires the selection of a suitable drug carrier based on the network size and swelling capacity of the hydrogel, as well as an in-depth understanding of wound physiology and lesions.[4c,19d,21b] Advanced flexible hydrogel-based chemical sensors (finely processed, with complex circuitry, capable of transmitting data) are currently in limbo for wearable and implantable commercial applications (e.g., sweat sensors, glucose sensors) due to the issues such as dehydration, ability to pattern and integrate, and weak mechanical strength.[11a,22a] The raw materials, processing methods, biocompatibility, sensing reliability, and cost-effectiveness of hydrogel flexible chemical sensors need to be further validated for their transition from the lab to the factory.  \n\nBesides the aforementioned challenges, there is a great need for extensive interdisciplinary teamwork of experts in mechanics, microelectronics, computing, clinic, and medicine to translate functional hydrogel-based flexible chemical sensors from laboratory prototypes to real-life commodities. It is expected that, after addressing these issues and together with the combined multidisciplinary efforts, functional hydrogel-based chemical sensors will expedite the development of soft bioelectronics toward smart diagnostics and therapeutics.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 25,
+        "chunk": "# Acknowledgements  \n\nThe authors sincerely acknowledged the support from the Li Ka Shing Foundation Cross-disciplinary Research Program (Grant No. 2022LKSFG12A), Young Talent Innovation Project of Guangdong Education Department (Grant No. 2022KQNCX112), Guangdong Science and Technology Department (Grant No. STKJ202209085), Provincial science and technology innovation strategy special project (\"major special project $^+$ task list\") program, the 2022 Key Discipline (KD) fund, the Technion, and the start-up fund from Guangdong Technion. Table of contents image created with BioRender.com",
+        "category": " Acknowledgements"
+    },
+    {
+        "id": 26,
+        "chunk": "# Conflict of Interest  \n\nThe authors declare no conflict of interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 27,
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Nakamata, Y. Kawahara, S. Takeuchi, iScience 2020, 23, 101243; b) Z. Wang, Y. Liu, Z. Wang, X. Huang, W. Huang, VIEW 2021, 2, 20200165; c) F. Li, D. Lyu, S. Liu, W. Guo, Adv. Mater. 2020, 32, 1806538.   \n[136] a) J. Li, C. Wu, P. K. Chu, M. Gelinsky, Mater. Sci. Eng., R. 2020, 140, 100543; b) H. S. Ghazali, E. Askari, Z. S. Ghazali, S. M. Naghib, T. Braschler, Colloid Interface Sci. Commun. 2022, 50, 100667.   \n[137] a) A. C. Daly, L. Riley, T. Segura, J. A. Burdick, Nat. Rev. Mater. 2020, 5, 20; b) A. C. Daly, K. S. Lim, Trends Biotechnol. 2023, 41, 262.   \n[138] Y. Liang, H. Xu, Z. Li, A. Zhangji, B. Guo, Nano-Micro Lett. 2022, 14, 185.   \n[139] H. Wang, X. Yi, T. Liu, J. Liu, Q. Wu, Y. Ding, Z. Liu, Q. Wang, Adv. Mater. 2023, 45, 2300394.   \n[140] C. Fu, L. Shen, L. Liu, P. Tao, L. Zhu, Z. Zeng, T. Ren, G. Wang, Adv. Mater. 2023, 35, 2211237.   \n[141] C. Xie, X. Wang, H. He, Y. Ding, X. Lu, Adv. Funct. Mater. 2020, 30, 1909954.   \n[142] A. López-Díaz, A. Martín-Pacheco, A. M. Rodríguez, M. A. Herrero, A. S. Vázquez, E. Vázquez, Adv. Funct. Mater. 2020, 30, 2004417.   \n[143] Y. Yang, L. Xu, J. Wang, Q. Meng, S. Zhong, Y. Gao, X. Cui, Carbohydr. Polym. 2022, 283, 119161.   \n[144] Y. Wang, S. Lee, T. Yokota, H. Wang, Z. Jiang, J. Wang, M. Koizumi, T. Someya, Sci. Adv. 2020, 6, eabb7043.   \n[145] a) S. Cheng, Z. Lou, L. Zhang, H. Guo, Z. Wang, C. Guo, K. Fukuda, S. Ma, G. Wang, T. Someya, H. M. Cheng, X. Xu, Adv. Mater. 2023, 35, 2206793; b) J. Yang, Z. Zhang, P. Zhou, Y. Zhang, Y. Liu, Y. Xu, Y. Gu, S. Qin, H. Haick, Y. Wang, Nanoscale 2023, 15, 3051.  \n\n![](images/3c2678e3d578066fe420df46c758ad01932547c5688c4b89b3697de8a460246c.jpg)  \n\nDr. Yan Wang joint Technion-Israel Institute of Technology (Guangdong) as an associate professor in November 2021. She received her Ph.D. degree majoring in Chemical Engineering from Monash University in 2018 and completed her postdoc training at the Department of Electrical and Electronic Engineering, The University of Tokyo. At Guangdong Technion, her research group mainly focuses on materials development and the practical implementation of soft wearables in real-life situations toward ambulatory health care and the Internet of Things.",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Hydrogel Paint  \n\nXi Yao, Junjie Liu, Canhui Yang, Xuxu Yang, Jichang Wei, Yin Xia, Xiaoyan Gong, and Zhigang Suo\\*  \n\nFor a hydrogel coating on a substrate to be stable, covalent bonds poly­ merize monomer units into polymer chains, crosslink the polymer chains into a polymer network, and interlink the polymer network to the substrate. The three processes—polymerization, crosslinking, and interlinking—usu­ ally concur. This concurrency hinders widespread applications of hydrogel coatings. Here a principle is described to create hydrogel paints that decouple polymerization from crosslinking and interlinking. Like a common paint, a hydrogel paint divides the labor between the paint maker and the paint user. The paint maker formulates the hydrogel paint by copolymerizing monomer units and coupling agents into polymer chains, but does not crosslink them. The paint user applies the paint on various materials (elastomer, plastic, glass, ceramic, or metal), and by various operations (brush, cast, dip, spin, or spray). During cure, the coupling agents crosslink the polymer chains into a network and interlink the polymer network to the substrate. As an example, hydrogels with thickness in the range of $2-20\\upmu\\mathrm{m}$ are dip coated on medical nitinol wires. The coated wires reduce friction by eightfold, and remain stable over 50 test cycles. Also demonstrated are several proof-of-concept applica­ tions, including stimuli-responsive structures and antifouling model boats.  \n\nA hydrogel-coated substrate unites the superior properties of the substrate (e.g., strength, stiffness, and toughness) and the superior properties of the hydrogel (e.g., hydrophilicity, lubricity, biocompatibility, and drug-release). In principle, any hydrogel can coat any substrate to achieve some functions by their union. This enormous diversity has enabled numerous existing and emerging applications in engineering and medicine.[1] Examples include drug delivery,[2,3] soft robots,[4,5] implants,[6,7] artificial skin,[8,9] sensors and actuators,[10,11] ionotronics,[12,13] and marine antifouling.[14–18]  \n\nFor a hydrogel coating on a substrate to be stable, covalent bonds polymerize monomer units into polymer chains, crosslink the polymer chains into a polymer network, and interlink the polymer network to the substrate. In existing methods of hydrogel coating, the three processes— polymerization, crosslinking, and interlinking—usually concur. This concurrency is unnecessary and hinders the widespread applications. In particular, many hydrogels are made by free-radical polymerization, involving toxic monomers, toxic ­initiators, and oxygen-free environment. For example, in the free-radical polymerization of a covalently crosslinked polyacrylamide hydrogel, when subject to UV light, the vinyl groups of acrylamide monomer and $\\mathbf{\\Psi}_{N,N^{\\prime}}$ -methylenebisacrylamide crosslinker are activated concurrently. The former results in polyacrylamide chains and the latter results in a polyacrylamide network. When the substrate is involved, polymerization of monomers, crosslinking of poly­mer chains, and interlinking between the hydrogel and substrate proceed concurrently. Since free radical polymerization is sensitive to oxygen, molding is usually required. Besides, molding is also used to control the shape and thickness of hydrogel coating. Depending on the geometry of the substrate, coating can be technically challenging for highly curved surfaces (e.g., 1D structures), or even impossible for hollow or cage structures. Furthermore, the monomers (e.g., acrylamide, acrylic acid, etc.) are usually toxic. Consequently, free-radical polymerization is unsuitable for everyday operation.  \n\n![](images/6cbf6d73d51b54b844add076b2105e3f430042280ece1bdcd616d4f550d2a09a.jpg)  \nFigure 1.  Principle of hydrogel paint. a) Formulation: monomer units and coupling agents copolymerize into polymer chains, but do not crosslink into a network, resulting in an aqueous solution. The solution may also contain other compounds for various functions but are not drawn here. b) Substrate preparation: functional groups complementary to the coupling agents are imparted onto the surface of a substrate. c) Paint: The aqueous solution is painted on the substrate by various operations. d) Cure: The coupling agents react with each other to crosslink the polymer chains into network and react with the complementary functional groups to interlink the polymer network to the substrate.  \n\nThis work has the following object: hydrogel coatings for anyone, on various materials (elastomer, plastic, metal, ceramic, or glass), by various operations (brush, cast, dip, spin, or spray). We describe a principle, which we call “hydrogel paint”, that decouples polymerization from crosslinking and interlinking. We are inspired by the economics of common paints: a division of labor between the paint maker and the paint user. To achieve desired functions, the paint maker formulates a paint using various compounds, some of which may be toxic. The paint user is not asked to handle the toxic compounds. We describe the principle of hydrogel paint in four parts: formulation, substrate preparation, paint, and cure (Figure  1). During formulation, monomer and coupling agent are dissolved in water, along with other compounds of various functions, such as initiator, chain transfer agent (CTA), rheological modifier, charge carrier, drug, and toughener. The monomer and the coupling agent react to form uncrosslinked copolymer chains via free-radical polymerization (Figure  1a). During substrate preparation, a functional group complementary to the coupling agent is imparted on the surface of the substrate (Figure 1b). During paint, the paint— the aqueous solution of the uncrosslinked polymer chains and various other compounds—is applied on the prepared substrate (Figure  1c). During cure, the coupling agents react with each other to crosslink the polymer chains into a polymer network, and with the complementary functional groups to interlink the polymer network to the substrate (Figure 1d). In this division of labor, the paint maker is responsible for formulation, whereas the paint user is responsible for substrate preparation, paint, and cure.  \n\nThe principle of hydrogel paint can be illustrated using various chemistries. We will describe a specific embodiment of the principle and study its chemistry and physics. We then show that the hydrogel paint can be applied on medical guidewires to realize sustained lubrication. We further demonstrate ­several proofs-of-concept applications of hydrogel paint, including thermal-responsive pattern, pH-responsive deformation, and antifouling model boats. The hydrogel paint is of immediate importance to broad applications, such as ionotronics, bio­ electronics, surgical instruments, and implants.  \n\nWe illustrate the principle of hydrogel paint using a class of well-established hydrogels synthesized by free-radical poly­ merization, copolymerized with the best-known coupling agents, silanes. We formulate the paint by volume modification developed in our recent papers.[19,20] For example, the monomer acrylamide (AAm) and the coupling agent (3-(trimethoxysilyl) propyl methacrylate) (TMSPMA), both dissolved in water, are copolymerized into p(AAm-co-TMSPMA) chains, and the alkoxy groups on each silane hydrolyze into silanol groups (Figure S1, Supporting Information). During substrate preparation, hydroxyl groups are imparted on the surface of the substrate. During paint, the aqueous solution of uncrosslinked polymer chains is applied on the surface of a substrate. During cure, the silanol groups condense with each other to form siloxane bonds that crosslink the polymer chains into a polymer network, and condense with the hydroxyl groups to form siloxane bonds that interlink the polymer network to the substrate.  \n\nThis embodiment of the principle of hydrogel paint has significant attributes. Polymerization is indeed decoupled from crosslinking and interlinking. Free-radical polymerization involves toxic monomer and initiator, UV light, and oxygenfree environment.[21,22] The toxic monomer and initiator are mostly consumed during copolymerization. The residual unreacted monomers can, if necessary, be removed from the paint through dialysis or distillation. Both the copolymer chains and silane condensation are nontoxic. The hydrogel paint is a viscous liquid and can be applied to a substrate just like a common paint, without mold, UV light, or oxygen-free environment. The rate of condensation is sensitive to $\\mathrm{\\pH}$ and temperature, which can regulate a wide time window for cure, from seconds to days.[23] Many hydrogels are made by free-­radical polymerization and are readily copolymerized with silanes. Inorganic solids, such as glasses,[23] metals,[24] and ceramics,[25] have hydroxyl groups on their clean surfaces exposed in the air. Organic solids such as elastomers and plastics acquire hydroxyl groups through surface treatment such as oxygen plasma and ozone UV. The diversity in hydrogels and substrates, along with the division of labor between the paint maker and the paint user, greatly amplifies the advantage of hydrogel paint for applications.  \n\nThe hydrogel paint can be dried, ground into powders, and stored for a long shelf life. After redissolving in water, the dry powder becomes hydrogel paint again and can form crosslinks and interlinks (Figure S2, Supporting Information). The dry powders extend the shelf life of hydrogel paint, which enables the division of labor between the paint maker and the paint user and further simplifies the practical applications of hydrogel paint.  \n\nRheology of the paint must be tuned to suit each operation of paint. For example, a thick hydrogel paint works for brush and a dilute hydrogel paint works for spray. The rheology of the hydrogel paint can be readily tuned through CTA, silane content, water content as well as rheological modifier. As examples, we study the effects of chain transfer agent and silane on the viscosity of hydrogel paint. CTAs are small molecules with thiol groups, alkanols, or halogen-alkanes.[26] During poly­ merization, a CTA terminates the growth of one chain and initiates a new one. Overall, CTAs shorten polymer chains and reduce the viscosity of hydrogel paint. Higher CTA concentration gives lowers viscosity of hydrogel paint, and the viscosity spans across three orders of magnitude (spanning from 0.5 to $1000\\ \\mathrm{Pa}\\ \\mathrm{s}$ ) (Figure  2a). Such a wide range of tunable viscosity readily meets the requirements of different painting operations. The viscosity decreases as the shear rate increases, which favors most coating techniques that it provides viscous paints with high maneuverability in a fast painting motion. The viscosity of hydrogel paint can also be tuned by changing silane concentration (Figure  2b). After hydrogel paint formation, the silanes are hydrolyzed but do not fully condense. In the presence of silanes, hydrogen bonds are likely to form between silanol groups as well as between silanol and amino groups (from AAm units),[27] which enhances the interchain interaction and results in the increase of viscosity of hydrogel paint. Consequently, higher concentration of silane gives higher viscosity of hydrogel paint.  \n\n![](images/67e78d89bcc6d41b65a64ddab03e8ab8a095de6f1b850e59b46f4a509d3f3492.jpg)  \nFigure 2.  Rheology of uncured paint and adhesion of cured paint. a) Viscosity of the uncured paint decreases as the concentration of CTA increases. The concentration of silane is fixed at $8.0\\times10^{-3}\\ m o l\\ \\mathsf{L}^{-1}$ . $\\mathsf{1.0{C T A}}$ represents $\\dot{5}.4\\times10^{-4}\\sf m o l\\ L^{-1}$ . b) Viscosity of the uncured paint varies with the concentration of silane (with CTA concentration fixed at ${1.0}{\\mathsf{C T A}}.$ ). 1 Silane represents $8.0\\times10^{-3}~\\mathsf{m o l}~\\mathsf{L}^{-1}$ . c) Adhesion energy of the paint cured on nitinol plate decreases as the concentration of silane increases. The amount of CTA is fixed at 1.0 CTA. Inset: $90^{\\circ}$ -peel test. d) Adhesion energy decreases as the concentration of CTA increases. The concentration of silane is fixed at 3 Silane.  \n\nAppreciable adhesion is required for most applications of hydrogel coatings.[1] We study the effects of CTA and silane on adhesion via $90^{\\circ}$ peel test. The siloxane interlinks between the hydrogel and substrate is strong, the crack propagates through the hydrogel, and the bulk toughness of the hydrogel limits the adhesion energy. One can toughen the hydrogel bulk by introducing tougheners, such as covalent networks of short polymer chains or nanoclay. The siloxane interlinks between a hydrogel and a substrate is strong enough to elicit energy dissipation in the bulk of a tough hydrogel, achieving adhesion energy of ${\\approx}900$ J $\\mathrm{m}^{-2}$ .[19] The current work focuses on the concept of hydrogel paint. Toughening the hydrogel bulk to realize tough hydrogel coating with strong adhesion deserves a separate project and is beyond the scope here. The peel force increases as the crack begins to extend then plateaus when the crack propagation reaches a steady state. The ratio of the averaged plateaued peel force over the sample width gives the adhesion energy (Figure S3, Supporting Information). In our experiments, the crack propagates through the hydrogel (Figure S4, Supporting Information), indicating that the interface is tougher than the hydrogel, and that the peel force gives the toughness of the hydrogel. We study the effects of the ­concentration of silane and CTA on the adhesion energy. The effect of two condensed silanes is equivalent to that of one covalent crosslinker. Consequently, a higher concentration of silane results in higher crosslinking density. On the other hand, the CTAs shorten the length of polymer chains, so that a higher concentration of CTA results in a worse network integrity. Both higher crosslinking density and worse network integrity deteriorate the toughness of hydrogel thus the adhesion energy. As expected, the adhesion energy decreases as the concentration of silane increases (Figure 2c), or as the concentration of CTA increases (Figure  2d). The measured adhesion energy ranges from ${\\approx}5$ to $\\approx70\\ \\mathrm{J\\m^{-2}}$ , comparable to the toughness of polyacrylamide hydrogels of various chain lengths.[1]  \n\nAs an example of the applications of hydrogel paint, we dipcoat nitinol guidewires with hydrogels (Movie S1, Supporting Information). Metallic guidewires deliver devices to specific sites inside human bodies.[28] Most human tissues are natural hydrogels. Synthetic hydrogels can mimic human tissues to high fidelity and are ideal materials to coat guidewires for better lubricity, biocompatibility, maneuverability, and patient comforts.[29] However, the implementation of hydrogel coatings in the industry has remained challenging to date. We now demonstrate the use of a hydrogel paint to coat nitinol guidewires. Nitinol is a metallic alloy of titanium and nickel, both of which are rich in hydroxyl groups when the surface is exposed in the air.[30] The native hydroxyl groups on the nitinol guidewires readily condense with the silanol groups in the hydrogel paint. We vary the concentration of CTA and silane to optimize the paint for dip coat (Figure S5a, Supporting Information). The feasible criteria are set as following. After polymerization, the hydrogel paint should remain as a liquid to allow dip-coat. After curing, the hydrogel paint should be able to solidify. Too much silane makes the hydrogel paint too viscous to dip-coat after polymerization, while too much CTA makes the hydrogel paint liquid after cure. Moreover, the feasible formulations are further optimized for the specific application of nitinol guidewires that the resulting hydrogel coating must be firmly adhered to the wire, lubricous and stable over cyclic friction. Eventually, we select a concentration of $5.4\\times10^{-4}$ mol $\\mathrm{L}^{-1}$ for CTA and a concentration of $2.4\\times10^{-2}$ mol $\\mathrm{L}^{-1}$ for silane to formulate the hydrogel paint. The recipe results in hydrogels of appreciable mechanical properties (Figure S5b, Supporting Information). Note that different processing methods require different rheology of hydrogel paint. Depending on the specific applications, the rheology requirements can be different even for the same method. Here we illustrate the idea of tuning rheology for dipcoating nitinol guidewires, but this strategy applies to other processing methods. We have only studied the effects of one type of CTA and one type of silane, Rheology can also be tuned by other types of CTAs, silanes, as well as water content, initiators, rheology modifiers, charge carriers, and tougheners.  \n\nA nitinol guidewire is dipped in a bath of the hydrogel paint and pulled out at a constant velocity of $10\\ \\mathrm{mm\\min^{-1}}$ (Figure 3a). Scanning electron microscopic (SEM) images show that an uncoated wire has texture scars, which are likely generated during manufacturing (Figure 3b), whereas a hydrogelcoated wire has a smooth surface (Figure 3c). The diameter of the wire is ${\\approx}310~\\upmu\\mathrm{m}$ . Viscosity and inertia are the two major factors that determine the thickness of coatings.[31] By changing the pulling velocity, coating thickness ranging between 2 and $20~{\\upmu\\mathrm{m}}$ can be obtained (Figure  3d). After dip coat, the guidewires are cured in a humid container, in an oven at $65~^{\\circ}\\mathrm{C},$ for $24\\mathrm{~h~}$ . When immersed in water, the hydrogel coating swells to equilibrium at ${\\approx}10~\\upmu\\mathrm{m}$ in less than one second (Figure  3e and Movie S2, Supporting Information). The diffusion time of water molecules can be estimated as, $\\tau{\\approx}L^{2}/D$ .[32] Here, $L$ is the diffusion length, which is on the order of $10\\upmu\\mathrm{m}$ in our experiments, and $D$ is the diffusion coefficient of water molecules at room temperature $(\\approx10^{-9}\\mathrm{~m}^{2}\\mathrm{~s}^{-1})$ . Consequently, the time it takes for a $10\\upmu\\mathrm{m}$ thick hydrogel coating to be swollen by water is ${\\approx}0.1$ s, comparable to the experiment observation. No large wrinkles or delamination happens during the swelling process, implying strong adhesion between the hydrogel coating and nitinol guidewire (Figure  3f). By contrast, a hydrogel coating without covalent interlinks easily wrinkles and delaminates (Figure S6, Supporting Information).  \n\nWe test the hydrogel-coated guidewires for lubricity and durability, two major industrial concerns.[33] Due to the lack of a standard for friction tests among different guidewires,[34] one may adopt a test that is close to the scenarios of the guidewire application yet simplified. In an application, a guidewire slides against a soft and curved blood vessel.[35] We set up an apparatus to simulate this process (Figure  3g). An uncoated wire has a highest friction resistance ${\\approx}0.1\\ \\mathrm{N}$ and a coated one has ${\\approx}0.01$ N (Figure 3h). We plot the mean absolute values of friction resistance in each cycle to compare the durability of the wires with and without the hydrogel coating (Figure  3i). The average friction of an uncoated nitinol guidewire increases from 0.045 to ${\\approx}0.08\\mathrm{~N~}$ . By contrast, the average friction of a coated one stabilizes at $0.01\\mathrm{~N~}$ throughout the test.  \n\n![](images/c17c25215195eb7c9d6f52c4931ffa4cf79a52c6e50cc748905ec55f3c815525.jpg)  \nFigure 3.  Hydrogel-coated nitinol guidewires. a) Schematic (left) and image (right) of dip-coating a nitinol guidewire in a p(AAm-co-TMSPMA) hydrogel paint. b,c) SEM images of the rough surface of an uncoated wire (b) and the smooth surface of a coated wire (c). d) Coating thickness varies with withdrawing speed. e) Thickness evolution of the p(AAm-co-TMSPMA) hydrogel coating in deionized water. f) Sequential images showing the swelling process of the hydrogel coating. g) Schematics showing the sliding friction test of guidewire. h) Typical friction resistance-displacement curves of uncoated (blue) and coated (red) wires. The friction resistance of a coated wire is smaller than that of an uncoated wire by eightfold. i) Friction resistance varies with cycle number. Friction resistance of coated wires is low and remains stable over 50 cycles, while the friction resistance of uncoated wires is high and rapidly increases during the first few testing cycles.  \n\nWe demonstrate several proofs-of-concept applications using a variety of hydrogels, substrates, and operations (Figure  4). We prepare a poly(N-isopropyl acrylamide-co-TMSPMA)  \n\n![](images/905e00bde63f7b0aa96a63d181cbc95930b750878a839d54a4b60da44c5e7e15.jpg)  \nFigure 4.  Versatility of hydrogel paint for various hydrogels, substrates, and painting techniques. a) P(NIPAM-co-TMSPMA) hydrogel paint is cast coated on an oxygen-plasma-treated PDMS sheet with a predesigned butterfly pattern. After cure, the butterfly pattern appears (opaque) or disappears (transparent) as the temperature goes above or below the lower critical solution temperature of p(NIPAM-co-TMSPMA) hydrogel. b) P(AAc-coTMSPMA) hydrogel paint is spin coated on an oxygen-plasma-treated PDMS sheet. After curing, the layered structure can undergo rolling/unrolling in response to increasing/decreasing of the ambient pH. c) P(AAm-c -TMSPMA) hydrogel coated on an aluminum boat hull. The hydrogel-coated boat exhibits underwater superoleophobicity to mine oil with of ${\\approx}758^{\\circ}$ and the uncoated boat has a much smaller contact angle of ${\\approx}32^{\\circ}$ . When floating on water covered by a layer of mineral oil (stained in red), the coated boat repels the oil and remains clean, while the uncoated boat is contaminated.  \n\n(p(NIPAm-co-TMSPMA)) hydrogel paint, treat a poly(dimethylsiloxane) (PDMS) elastomer by oxygen plasma, and cast a butterfly pattern of the hydrogel paint on the elastomer (Figure  4a). The surface of treated PDMS contains hydroxyl groups and can react with the silanol groups in the hydrogel paint to form siloxane interlinks between the elastomer and the hydrogel. After cure, a butterfly shaped (p(NIPAM-co-TMSPMA)) hydrogel is formed and adheres to PDMS. Owing to the temperature responsibility of PNIPAm, the butterfly becomes invisible in cold water $(22~^{\\circ}\\mathrm{C})$ and visible in hot water $(46~^{\\circ}\\mathrm{C})$ . The pattern remains stable on PDMS surface as temperature repeatedly alters, indicating a robust bonding between p(NIPAm-co-TMSPMA) hydrogel and PDMS (Movie S3, Supporting Information).  \n\nWe then prepare a poly(acrylic acid-co-TMSPAM) (p(AAcco-TMSPMA)) hydrogel paint and spin-coat a layer of hydrogel on a sheet of PDMS (also pretreated by oxygen plasma) (Figure  4b). After cure, a bilayer composite is formed with interfacial covalent bonding. We cut the bilayer into a slice of area $10\\times50~\\mathrm{mm}^{2}$ and alternatively immerse it into acid $(\\mathrm{pH}=1) $ or alkaline $(\\mathrm{pH}=14^{\\cdot}$ solution. In the bilayer, p(AAc-coTMSPMA) responses to $\\mathrm{\\pH}$ while PDMS does not, which leads to an asymmetric locomotion upon the switching of pH. When $\\mathrm{pH}=14$ , the carboxyl groups are ionized, the hydrogel imbibes water and becomes transparent. The swelling of hydrogel coating causes the slice to roll up (Movie S4, Supporting Information). When $\\mathrm{\\pH}=1$ , the carboxyl groups are deionized (DI), the hydrogel repels water and becomes milk-white. The deswelling of hydrogel coating causes the previously rolled up slice to unwind and regain its original shape (Movie S5, Supporting Information). Both p(NIPAm-co-TMSPMA) hydrogel and p(AAc-co-TMSPMA) hydrogel undergo swelling/deswelling upon stimuli, which exerts internal stress at the hydrogel/ substrate interface. Consequently, such geometrical stimuliresponsive behavior is guaranteed by the strong and stable interfacial bonding.  \n\nWe next demonstrate an anticontamination hydrogel coating (Figure 4c). We prepare a p(AAm-co-TMSPMA) hydrogel paint and brush-paint a model boat hull wrapped with aluminum tape (Movie S6, Supporting Information). After cure, the boat shows superior underwater superoleophobicity with an oil (mineral oil, same below) contact angle ${\\approx}158^{\\circ}$ (Movie S7, Supporting Information), while an uncoated boat shows affinity to oil under water with an oil contact angle ${\\approx}32^{\\circ}$ . We place the boats with and without a hydrogel coating on clean water first. Then, we transfer the boats to mineral-oil-contaminated (the oil is stained red) water surface. The cruising hydrogel painted boat is able to break open the oil layer, repel the oil away from the boat, and reveal the beneath water. Whereas the uncoated boat is cruising on oil the whole time. After $20~\\mathrm{s}$ , we lift both boats out of the bath. The coated boat shows a clean surface, whereas the uncoated boat is contaminated (Movie S8, Supporting Information). This can be explained by the underwater superoleophobicity. Upon contact, the oil tends to bead up and roll away (oil contact angle $\\approx158^{\\circ}$ ) from the hydrogel,[15] resulting in self-cleaning function of the hydrogel-coated boat. Hydrogel paint paves new ways to make hydrogel coatings on ship hull for antifouling performances.[18]  \n\nHydrogel paint strategy applies for diverse substrate materials. Now that we have selected silane chemistry, any substrates can be coated via hydrogel paint, so long as the surface can be imparted with hydroxyl groups. For most inorganic materials with oxidized surface, hydroxyl groups naturally exist. For most organic materials, hydroxyl groups can be generated via surface treatments such as plasma. For inert materials, e.g., Au and Pt, organic compounds containing thiol groups can be used to modify the surfaces.[36] Silanes for many decades have been explored to bond all kinds of materials.[23,37] We have demonstrated the feasibility of hydrogel paint on metals (nitinol, aluminum, steel), polymers (PDMS, polystyrene), and oxides (silica, macor) (Figure S7, Supporting Information). We observe cohesive failure in all cases, implying that siloxane bonds provide strong interlinks. Furthermore, we validate the stability of adhesion by immersing a hydrogel-coated nitinol plate in phosphatebuffered saline (PBS) solution (Figure S8, Supporting Information). The adhesion is stable with no delamination after $7\\mathrm{d}$ .  \n\nWe note that hydrogel paint enables functions such as being highly lubricous, temperature-responsive, pH-responsive, and antifouling. In principle, hydrogel coatings of being lightresponsive, antithrombus/hemocompatible, biodegradable, and self-healing can be achieved by selecting functional polymers or moieties (Table S1, Supporting Information).  \n\nIn summary, we have described a principle of hydrogel paint to coat various hydrogels, on various substrates, by various operations. The principle decouples polymerization from crosslinking and interlinking. A hydrogel paint divides the labor between the paint maker and paint user. The paint maker is free to create new paints to realize functions with sophisticated chemistry. The paint user need not be hampered by this sophistication and is free to apply the paints to substrates of various materials and shapes. The development of hydrogel paints motivates fundamental studies in chemistry and physics. Examples include the kinetics of reaction, the rheology of uncured paints, and the tribology of cured paints. We have illustrated the principle of hydrogel paint by using free-radical polymerization and silane coupling agents, but the principle can be adapted to guide the development of hydrogel paints of other chemistries and characteristics. For instance, we may further decouple crosslinking and interlinking to enable detachable hydrogel coatings, on-demand, in response to a cue, such as a change in $\\mathrm{\\pH}$ or an exposure to a UV light.[38,39] The crosslinks can still be covalent bonds to maintain the integrity of the hydrogel, but the interlinks can be various noncovalent bonds or dynamic covalent bonds to respond to various cues.[40– 43] It is hoped that the principle of hydrogel paint will drastically lower the barrier of entry, motivating many paint makers and paint users to invent hydrogel coatings for industrial and everyday functions. The principle calls for immediate action.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Experimental Section  \n\nMaterials: Monomers for hydrogel paints synthesis were acrylamide (AAm) (Sigma-Aldrich, A8887), N-isopropylacrylamide (NIPAm) (SigmaAldrich, 415324), and acrylic acid (AAc) (Sigma-Aldrich, 147230). The silane coupling agent was 3-(trimethoxysilyl) propyl methacrylate (TMSPMA) (Sigma-Aldrich, 440159). The chain transfer agent was (3-mercaptopropyl) trimethoxysilane (Sigma-Aldrich, 175617). Acetic acid (Sigma-Aldrich, A6283) solution and hydrochloric acid (SigmaAldrich 258148) were used to adjust pH value. Irgacure-2959 (I-2959) (Sigma-Aldrich, 410896) was used as photoinitiator. Tetrahydrofuran (THF) (Sigma-Aldrich, 360589), ethanol (Sigma-Aldrich, 459844), and DI water (Poland Spring) were used as solvents. Isopropyl alcohol (IPA) (BDH, BDH1174, VWR International, LLC) and acetone (Sigma-Aldrich, 650501) were used to wash nitinol plates and guidewires. All chemicals were purchased and used without further purification. PDMS (Sylgard 184) was purchased from Dow Corning. Nitinol plates/guidewires were provided by Innomed Medical Device Co., Ltd. Aluminum plates, steel plates, and macor (8489K241, $4^{\\prime\\prime}\\times4^{\\prime\\prime}$ sheet, $1/{16^{\\prime\\prime}}$ thick) were purchased from McMaster-Carr. Silica glass (Catalog No. 48382-179) and polystyrene plastic were purchased from VWR International, LLC.  \n\nPreparing Hydrogel Paint $p$ (AAm-co-TMSPMA) on Nitinol Guidewire: For 1 mL solution of AAm (2 moles per a liter of DI water, $2\\mathsf{m o l}\\mathsf{L}^{-1}$ ), ${\\sf1\\mu L}$ of CTA ( $10\\%$ volume ratio in THF), ${\\sf10\\upmu L}$ of acetic acid (0.1 moles per a liter of DI water, $0.1\\ m o l\\ \\mathsf{L}^{-1}$ ), and $5.7\\upmu\\up L$ of TMSPMA are added, followed by vortex mixing for $60~\\mathsf{s}$ . Here acetic acid is added to tune the pH value of the precursor, such that the condensation of silane is minimized during the hydrogel paint formulation.[23] After preparation of the hydrogel coating, acetic acid can be removed, if needed, either by distillation or dialysis. Then, $2\\upmu\\upiota$ of I-2959 (0.1 moles per a liter of ethanol, $0.1\\ m o l\\ L^{-1}$ ) is added followed by vortex mixing for $\\boldsymbol{{\\mathsf{10~s}}}$ . The resulting transparent solution is drawn into a plastic syringe and subject to UV irradiation (15W $365\\ \\mathsf{n m}$ ; UVP XX-15L, $5c m$ distance between sample and bulb. For the following mentioned UV curing procedure, the type of the UV lamp and the distance between sample and bulb are kept the same). After $30~\\mathrm{min}$ , the p(AAm-co-TMSPMA) hydrogel paint is obtained. Nitinol guidewire with diameter of ${\\approx}370~\\upmu\\mathrm{m}$ and length of $17c m$ is washed with IPA, acetone, and DI water in sequence twice and then dried by air. The treated guidewire is fixed to Instron (Instron 5966) load cell and immersed in the p(AAm-co-TMSPMA) hydrogel paint. During the dip coating, the guidewire is pulled out of the hydrogel paint vertically with a constant velocity of $\\mathsf{l o m m i n^{-1}}$ . Finally, the coated wire is sealed in a bottle with saturated humidity and stored in oven at $65^{\\circ}C$ for $24\\mathsf{h}$ .  \n\nSEM Characterization: For SEM characterization of nitinol wire with or without the PAAm hydrogel coatings, all samples are exposed in air until water was fully evaporated. Then small sections of wires are cut and sputter-coated with $5\\mathsf{n m}$ thick Pt/Pd before subject to an SEM system (ZEISS Ultra-55).  \n\nViscosity Testing of Uncrosslinked Hydrogel Paint: The viscosity of p(AAm-co-TMSPMA) hydrogel paint is measured using a rheometer (Discovery HR-3, TA Instruments). The shear rate varies from $\\mathsf{10^{-1}}$ to $\\bar{1}0^{3}\\ s^{-1}$ . A cone indenter with $178^{\\circ}$ -apex angle and diameter of $40\\ m\\mathsf m$ is used. The gap is kept at $26\\upmu\\mathrm{m}$ and temperature is fixed at $25^{\\circ}C$ .  \n\nFriction Testing of Guidewire: A silicone tube (inner diameter: $2\\mathsf{m m}$ , outer diameter: $6~\\mathsf{m m}$ ) is fastened in an engraved channel on an acrylic sheet. The silicone tube is slightly curved to ensure a normal force between the inner wall of tube and the guidewire, and the curvature is fixed (30 at a radius of $37~\\mathsf{m m};$ ). In the experiment, the silicone tube is immersed in DI water kept at $37^{\\circ}\\mathsf C$ . One end of the wire $170\\ m m$ long) is clamped by the gripers of Instron and dragged up and down. The friction is recorded by a $\\mathsf{10N}$ load cell. At the initial state, the grip is in its lowest position and the loading displacement is set to be zero. The wire is pulled up forward to $50~\\mathsf{m m}$ at a velocity of $\\mathsf{l o o\\ m m\\ m i n^{-1}}$ and then pushed back the wire to its initial position. This process is repeated for 50 times. The average friction is defined as the area enclosed by the friction-displacement curve in one cycle divided by the loading displacement ( $100~\\mathsf{m m}$ in this case).  \n\nPeel Test: Crosslinked p(AAm-co-TMSPMA) hydrogel coating is formed from hydrogel paint on a nitinol plate and the adhesion energy is tested by the peel test. Nitinol substrate is washed with IPA, acetone, and DI water twice and then dried by air. Hydrogel paint with dimensions of $60~\\mathsf{m m}\\times20~\\mathsf{m m}\\times1.5~\\mathsf{r}$ mm is cast on the nitinol plate. Then the sample is sealed in a humid plastic package and stored in oven at $65^{\\circ}\\mathsf C.$ After curing for $24\\ h$ , the sample is taken out for measurement. The top surface of the hydrogel is glued to a flexible but non-extendable backing film (polyester, $50~{\\upmu\\mathrm{m}}$ thick; McMaster-Carr) by cyanoacrylate glue. The sample is then loaded to the Instron with a $\\mathsf{l o o~N}$ load cell using the $90^{\\circ}$ -peeling fixture (Catalog No. 2820–035). The peeling rate is $\\mathsf{l o m m m i n^{-1}}$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 3,
+        "chunk": "# Supporting Information  \n\nSupporting Information is available from the Wiley Online Library or from the author.",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# Acknowledgements  \n\nX.Y., J.L., and C.Y. contributed equally to this work. Work at Harvard was supported by NSF MRSEC (DMR-14-20570). J.L. and X.Y. are visiting students at Harvard University supported by the China Scholarship Council.",
+        "category": " Acknowledgements"
+    },
+    {
+        "id": 5,
+        "chunk": "# Conflict of Interest  \n\nThe authors declare no conflict of interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 6,
+        "chunk": "# Keywords  \n\nadhesion, friction, hydrogel paint, viscosity  \n\nReceived: May 13, 2019 Revised: June 24, 2019 Published online:  \n\n[1]\t J.  Yang, R.  Bai, B.  Chen, Z.  Suo, Adv. Funct. Mater. 2019, 29, 1901693.   \n[2]\t J. A.  Rowley, G.  Madlambayan, D. J.  Mooney, Biomaterials 1999, 20, 45.   \n[3]\t H.  Cheng, K.  Yue, M.  Kazemzadeh-Narbat, Y.  Liu, A.  Khalilpour, B. Li, Y. S. Zhang, N. Annabi, A. Khademhosseini, ACS Appl. Mater. Interfaces 2017, 9, 11428. [4]\t W. J.  Zheng, N.  An, J. H.  Yang, J.  Zhou, Y. M.  Chen, ACS Appl. Mater. Interfaces 2015, 7, 1758. [5]\t J. Y. Sun, C. Keplinger, G. M. Whitesides, Z. Suo, Adv. Mater. 2014, 26, 7608.   \n[6]\t L. Faxalv, T. Ekblad, B. Liedberg, T. L. Lindahl, Acta Biomater. 2010, 6, 2599.   \n[7]\t B. Butruk, M. Trzaskowski, T. Ciach, Mater. Sci. Eng., C 2012, 32, 1601.   \n[8]\t H.  Yuk, T.  Zhang, G. A.  Parada, X.  Liu, X.  Zhao, Nat. Commun. 2016, 7, 12028.   \n[9]\t Y.  Yu, H.  Yuk, G. A.  Parada, Y.  Wu, X.  Liu, C. S.  Nabzdyk, K. Youcef-Toumi, J. Zang, X. Zhao, Adv. Mater. 2019, 31, 1807101.   \n[10]\t D. Kuckling, Colloid Polym. Sci. 2009, 287, 881.   \n[11]\t C. Keplinger, J.-Y. Sun, C. C. Foo, P. Rothemund, G. M. Whitesides, Z. Suo, Science 2013, 341, 984.   \n[12]\t H. R. Lee, C. C. Kim, J. Y. Sun, Adv. Mater. 2018, 30, 1704403.   \n[13]\t C. Yang, Z. Suo, Nat. Rev. Mater. 2018, 3, 125.   \n[14]\t T.  Ekblad, G.  Bergstrom, T.  Ederth, S. L.  Conlan, R.  Mutton, A. S.  Clare, S.  Wang, Y.  Liu, Q.  Zhao, F.  D’Souza, G. T.  Donnelly, P. R. Willemsen, M. E. Pettitt, M. E. Callow, J. A. Callow, B. Liedberg, Biomacromolecules 2008, 9, 2775.   \n[15]\t M. Liu, S. Wang, Z. Wei, Y. Song, L. Jiang, Adv. Mater. 2009, 21, 665.   \n[16]\t L.  Lin, H.  Yi, X.  Guo, P.  Zhang, L.  Chen, D.  Hao, S.  Wang, M.  Liu, L. Jiang, Sci. China: Chem. 2018, 61, 64.   \n[17]\t R.  Takahashi, K.  Shimano, H.  Okazaki, T.  Kurokawa, T.  Nakajima, T. Nonoyama, D. R. King, J. P. Gong, Adv. Mater. Interfaces 2018, 5, 1801018.   \n[18]\t T. Murosaki, N. Ahmed, J. Gong, Sci. Technol. Adv. Mater. 2011, 12, 064706.   \n[19]\t Q. Liu, G. Nian, C. Yang, S. Qu, Z. Suo, Nat. Commun. 2018, 9, 846.   \n[20]\t P. Le Floch, X. Yao, Q. Liu, Z. Wang, G. Nian, Y. Sun, L. Jia, Z. Suo, ACS Appl. Mater. Interfaces 2017, 9, 25542.   \n[21]\t P. Erkekoglu, T. Baydar, Nutr. Neurosci. 2014, 17, 49.   \n[22]\t D. Biswal, J. Z. Hilt, Macromolecules 2009, 42, 973.   \n[23]\t E. P.  Plueddemann, Silane Coupling Agents, Springer Science+Business Media, New York, USA 1982.   \n[24]\t E. McCafferty, J. P. Wightman, Surf. Interface Anal. 1998, 26, 549.   \n[25]\t C. Y. Lung, J. P. Matinlinna, Dent. Mater. 2012, 28, 467.   \n[26]\t O. Çetinkaya, G. Demirci, P. Mergo, Opt. Mater. 2017, 70, 25.   \n[27]\t I.-S. Chuang, G. E. Maciel, J. Phys. Chem. B 1997, 101, 3052.   \n[28]\t M.  Kipling, A.  Mohammed, R.  Medding, Expert Rev. Med. Devices 2009, 6, 187.   \n[29]\t P.  Wyman, in Coatings for Biomedical Applications (Ed: M. Driver), Woodhead Publishing Limited, Cambridge, UK 2012, pp. 3–42.   \n[30]\t B. Arkles, A. Maddox, M. Singh, J. Zazyczny, J. Matisons, Silane Coupling Agents: Connecting Across Boundaries, Gelest Inc., Morrisville, PA, USA 2014.   \n[31]\t D. Quéré, Annu. Rev. Fluid Mech. 1999, 31, 347.   \n[32]\t K. Harris, L. Woolf, J. Chem. Soc., Faraday Trans. 1 1980, 76, 377.   \n[33]\t D. Burkart, J. Borsa, Endovascular Today, Bryn Mawr Communications II, LLC., Wayne, PA, USA 2008, pp. 69–74.   \n[34]\t J.  Li, J.  Simon, W.  Work, Effects of Testing Parameters on Pinch Test Results for Hydrophilic Coatings, Biocoat Incorporated, Horsham, PA, USA  2012.   \n[35]\t K.  Takashima, A.  Oike, K.  Yoshinaka, K.  Yu, M.  Ohta, K.  Mori, N. Toma, J. Biomech. Sci. Eng. 2017, 12, 17.   \n[36]\t D. G. Castner, Langmuir 1996, 12, 5083.   \n[37]\t G. L. Witucki, J. Coat. Technol. 1993, 65, 57.   \n[38]\t J. Yang, R. Bai, Z. Suo, Adv. Mater. 2018, 30, 1800671.   \n[39]\t Y. Gao, K. Wu, Z. Suo, Adv. Mater. 2018, 31, 1806948.   \n[40]\t Y. Jin, C. Yu, R. J. Denman, W. Zhang, Chem. Soc. Rev. 2013, 42, 6634.   \n[41]\t R.  Nishiyabu, Y.  Kubo, T. D.  James, J. S.  Fossey, Chem. Commun. 2011, 47, 1124.   \n[42]\t B. Gyarmati, Á. Némethy, A. Szilágyi, Eur. Polym. J. 2013, 49, 1268.   \n[43]\t O. Prucker, T. Brandstetter, J. Ruhe, Biointerphases 2018, 13, 010801.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Bioinspired Hydrogel Interferometer for Adaptive Coloration and Chemical Sensing  \n\nMeng Qin, Mo Sun, Ruobing Bai, Yiqi Mao, Xiaoshi Qian, Dipika Sikka, Yuan Zhao, Hang Jerry Qi, Zhigang Suo, and Ximin He\\*  \n\nLiving organisms ubiquitously display colors that adapt to environmental changes, relying on the soft layer of cells or proteins. Adoption of soft materials into an artificial adaptive color system has promoted the development of material systems for environmental and health monitoring, anti-counterfeiting, and stealth technologies. Here, a hydrogel interferometer based on a single hydrogel thin film covalently bonded to a reflective substrate is reported as a simple and universal adaptive color platform. Similar to the cell or protein soft layer of color-changing animals, the soft hydrogel layer rapidly changes its thickness in response to external stimuli, resulting in instant color change. Such interference colors provide a visual and quantifiable means of revealing rich environmental metrics. Computational model is established and captures the key features of hydrogel stimuli-responsive swelling, which elucidates the mechanism and design principle for the broad-based platform. The single material–based platform has advantages of remarkable color uniformity, fast response, high robustness, and facile fabrication. Its versatility is demonstrated by diverse applications: a volatile-vapor sensor with highly accurate quantitative detection, a colorimetric sensor array for multianalyte recognition, breath-controlled information encryption, and a colorimetric humidity indicator. Portable and easy-to-use sensing systems are demonstrated with smartphone-based colorimetric analysis.  \n\nMany animals can change their colors for acclimatization, camouflage, and communication, by tuning the volume or thickness of their cell or protein soft layer. For example, cephalopods (squid, cuttlefish, octopus) rapidly adapt their skin colors to the environment by expanding or contracting the chromatophores. Upon external stimuli, cephalopods would contract or relax radial muscles that are attached to the chromatophores, leading to increased or decreased area of the pigmented sac of a chromatophore.[1,2] Among the cephalopods, some squids (e.g., Euprymna scolopes) possess iridophores that lie underneath the chromatophores. The iridophores can produce iridescent colors, which are generated from the light reflection of reflectin platelet stacks in iridophores and can be tuned with the thickness change of the platelets.[3,4] Besides these soft-bodied animals, longhorn beetle Tmesisternus isabellae (T. isabellae) changes the color of its elytron from green to red when the ambient humidity increases. The elytron contains photonic structures of alternative layers, of which one is a melanoprotein layer, and the other is a mixed layer of melanoprotein and air voids. When the ambient humidity increases, melanoprotein would absorb water molecules and swell, inducing the color change of elytron.[5,6] These typical examples reveal that such adaptive colors are realized by the change in volume or thickness of the cell or protein soft layer in response to environmental cues such as change in humidity, light, temperature, and concentrations of specific molecules. Inspired by this strategy of nature, applying soft materials to advance artificial adaptive coloring could promote the development of various areas such as sensing, displays, optical filters, anti-counterfeiting, and stealth technologies.  \n\nHydrogels are a class of promising soft materials that can change their volume by severalfold in response to a small alteration of environmental cues.[7,8] The polymer network of hydrogels can be readily functionalized to respond to cues like temperature, $\\mathrm{\\DeltapH}$ , and a wide range of specific molecules.[9–13] Furthermore, most hydrogels are transparent and stretchable, as well as low cost and environmentally friendly.[14,15] Hydrogels have been used as stimuli-responsive components in structural color systems commonly in the form of photonic crystals.[16–23] As photonic crystals rely on highly ordered structures and periodically arranged refractive indices, this requires careful coassembling of multiple materials and micro-/nanobuilding blocks to produce uniform color in large scale, limiting their rapid and convenient fabrication.[24] In addition, the multilayer structures prolong the time needed for swelling and hinder their applications for real-time monitoring.[25]  \n\n![](images/0f81a678bee6135bca2b5f553171701c1776c9039b9f0d85405182662d01ee67.jpg)  \nFigure 1.  Color generation of the hydrogel interferometer. a) Animals change color by tuning the volume or thickness of cell or protein soft layer, inspiring the design of soft hydrogel layer–based adaptive color platform. The image of T. isabellae is reproduced from ref. [6] b) Schematic of interference of the two reflected light waves from the air–hydrogel and hydrogel–substrate interfaces. $n_{\\mathrm{1}}$ , $n_{2}$ , $n_{3}$ are the refractive indices of air, hydrogel, and silicon, respectively. $d$ is the thickness of hydrogel. $\\theta$ is the incident angle. c) Photograph of a color palette of hydrogel films with tunable thickness and d) the corresponding reflection spectra at an incident angle of $0^{\\circ}$ . The films show colors determined by reflection peaks $(m=1,2$ ) or complementary colors $m=0.5$ , 1.5, 2.5) determined by reflection valleys.  \n\nHere, we report an adaptive color system of a particularly simple design: a single layer of hydrogel on a reflective substrate. In contrast to the commonly used micro-/nanobuilding blocks, the hydrogel film is featureless and can be readily fabricated with excellent homogeneity, exhibiting uniform color. The colors arise from the interference of the light waves reflected from the air–hydrogel interface and the hydrogel–substrate interface. Similar to the cell or protein soft layer of colorchanging animals, the soft hydrogel layer can rapidly change its thickness in response to external stimuli, resulting in instant color change (Figure 1a). The hydrogel film is covalently bonded to the substrate, with well-controlled thickness at $100\\mathrm{nm}$ scale. The film is thin, enabling fast swelling. A computational model has been established to investigate both the ratio and the rate of the hydrogel-responsive swelling, which validated experimental results and elucidated the mechanism. This adaptive color platform provides a means of unveiling chemical signals by visual and quantifiable color change. Based on this hydrogel interferometer, we have demonstrated a volatile-vapor sensor, presenting highly accurate quantitative detection with response and recovery times to full equilibrium of 140 and $210\\ \\mathrm{ms}$ , respectively, much faster than the previously reported hydrogelbased volatile-vapor sensors (Table S1, Supporting Information).[26–28] By simply arranging the same sensors with different thicknesses into an array, we have further realized multianalyte recognition. Owing to the facile photopatterning of the photo­ curable hydrogel, we have also developed breath-controlled information encryption and humidity indicators. Furthermore, we have established smartphone-based colorimetric analysis to make the hydrogel interferometer a portable and easy-to-use sensing system. This adaptive color system may advance realtime environment monitoring, point-of-care technology, and remote sensing data collection.  \n\nThe hydrogel interferometer was prepared by a one-step method, with spin-coating deposition and in situ polymerization of hydrogel precursor solutions onto a reflective substrate. The whole procedure was completed within minutes. A silicon (Si) wafer modified to allow covalent bonding with the hydrogel was used as the substrate[29] (Figure S1, Supporting Information). The adaptive coloration of such a simple structure that comprises only one homogenous hydrogel layer on a reflective substrate is shown to obey a simple governing equation of thin-film interference physics as follows. The color is generated by interference of the two reflected light waves from the air–hydrogel and hydrogel–substrate interfaces (Figure 1b). The refractive indices of air, hydrogel, and silicon are $n_{1}=1$ , $n_{2}=1.52$ , and $n_{3}=3.8$ , respectively. In the case of $n_{1}<n_{2}<n_{3}$ , the condition for constructive interference is $2n_{2}d\\mathrm{cos}\\theta=m\\lambda$ , and the condition for destructive interference is $2n_{2}d\\mathrm{cos}\\theta=$ $(m-0.5)\\lambda$ , where $d$ is the thickness of hydrogel, $\\theta$ is the angle of incident wave, $\\lambda$ is the wavelength of interference light, and $m$ is an integer.[30] At normal incidence $(\\cos\\theta=1)$ ), the color is mainly determined by the thickness of hydrogel film, where the thickness $d$ is comparable to the wavelength of visible light. As shown in Figure 1c, with an increase in thickness from 89 to $370~\\mathrm{nm}$ , the hydrogel films show a broad color spectrum from violet to yellow-green. The colors correspond to the peaks (constructive interference) and valleys (destructive interference) in the reflection spectra (Figure 1d, see detailed discussion in Figure S3 in the Supporting Information). The reflected light interference–based color is confirmed by good agreement of the experimental values and the theoretical locations of constructive and destructive interference calculated from the equations (Figure S4, Supporting Information).  \n\nTo investigate the response of the hydrogel interferometer, a poly(2-hydroxyethyl methacrylate-co-acrylic acid) (poly(HEMA-co-AAc)) hydrogel interferometer (Fourier transform infrared (FT-IR) spectra shown in Figure S5 in the Supporting Information) was prepared to act as a volatilevapor sensor (ethanol as a model vapor). In the reference state, a poly(HEMA-co-AAc) film of a thickness of $233\\ \\mathrm{nm}$ at ambient condition exhibits an orange color, with the secondorder destructive interference centered at $472\\ \\mathrm{nm}$ (Figure S6, Supporting Information). When exposed to ethanol vapor (saturated with nitrogen gas $\\left(\\mathrm{N}_{2}\\right).$ ), the hydrogel film swells and rapidly changes its color to blue, with a redshift of the valley from 472 to $577~\\mathrm{nm}$ and the occurrence of the second-order constructive interference centered at $441~\\mathrm{nm}$ . We carried out real-time monitoring of the reflectance centered at $472\\ \\mathrm{nm}$ (30 data points in the range of $472\\pm5$ nm were used to avoid inaccuracy) to investigate the response and recovery of the hydrogel film between the reference state and the fully swollen state. As shown in Figure 2a, when the film is exposed to ethanol vapor, the reflectance at $472\\ \\mathrm{nm}$ increases instantly and then decreases immediately after the vapor is removed. The measured response and recovery time for saturated ethanol vapor are 140 and $210~\\mathrm{ms}$ , respectively. For diluted ethanol vapor (diluted by $\\mathrm{N}_{2}$ to $50\\%$ of the saturation pressure, Figure S7, Supporting Information), it still shows the similar fast response, indicating good ethanol sensitivity of the poly(HEMA-coAAc) hydrogel. Compared with current state-of-the-art colorimetric ethanol vapor sensors, which typically exhibit response time of several seconds and even longer recovery time, this hydrogel interferometer responds much faster.[31,32] Such subsecond response time is mainly attributed to two reasons: first, hydrogen bonding and the similarity of the solubility parameters of poly(HEMA-co-AAc) and ethanol result in strong affinity between the polymer network and the vapor, leading to rapid absorption and diffusion of ethanol vapor;[28,33,34] second, the sub-micrometer-scale thickness of the film enables ultrashort diffusion length and thus fast diffusion of analytes to achieve equilibrium of swelling, which also benefits the rapid desorption and leads to a short recovery time. In addition, the sensor shows great robustness, since the response–recovery cycles can be carried out repeatedly with highly consistent performance (Movie S1, Supporting Information).  \n\nThe hydrogel interferometer was then applied to sense various concentrations of ethanol vapor with colorimetric analysis. The effective refractive index of hydrogel changes slightly upon the absorption of ethanol vapor, which is trivial compared with the thickness change of hydrogel and therefore makes negligible effect to interference (Figure S8, Supporting Information). Figure 2b shows the thickness change of a hydrogel film sensor (initial thickness of $224~\\mathrm{nm}$ ) with increased concentration of ethanol vapor mixed by $\\mathrm{N}_{2}$ , with $P$ as the partial pressure of ethanol in the mixture, and $P_{0}$ the saturation pressure of ethanol (corresponding to a concentration of $\\mathrm{\\tilde{\\tau}{\\approx}163\\upmu g m L^{-1}},$ . The experimental data match well with the theoretical prediction obtained by simulation based on a hydrogel swelling model (see details in the Supporting Information).[35,36] With the increase of ethanol vapor concentration, the chemical potential of ethanol in the surrounding increases as well, leading to more ethanol diffusing into the hydrogel. As a result, in the relatively high ethanol vapor concentration range, the hydrogel film exhibits more significant swelling, with faster thickness rise (can also be observed in the simulation results, Figure S18, Supporting Information). The detection limit of the sensor is $1.74~{\\upmu\\mathrm{g}}~\\mathrm{mL}^{-1}$ for ethanol vapor, restricted by the resolution of the fiber optic spectrometer $(1.5~\\mathrm{nm})$ , demonstrating remarkable sensing performance comparable to the reported sensors.[37,38] We then carried out a quantitative colorimetric analysis to detect the ethanol vapor by analyzing red, green, and blue (RGB) color channels. As shown in Figure 2c, with increased vapor concentration from 0 to $P_{0}$ , corresponding to color change of the sensor from yellow to violet (Figure S9, Supporting Information), the $R$ values increase first and then decrease; oppositely, the $G$ values decrease first and then increase; the $B$ values always increase. To investigate the accuracy of the quantitative detection, we divided the acquired data into two groups, one for constructing a calibration curve and the other to be used as unknown analyte samples for validation. By projecting the RGB space onto a 2D hyperplane score plot through principle component analysis, the unknown concentration can be determined by calculating the Euclidean distances between the validation point and its adjacent data (Figure S10, Supporting Information).[39] The estimated concentrations of the two analyte samples are 90.56 and $107.24~\\upmu\\mathrm{g}~\\mathrm{mL}^{-1}$ , respectively. Compared with their actual concentrations as 90.64 and $108.74~\\upmu\\mathrm{g}~\\mathrm{mL}^{-1}$ , the errors are $0.09\\%$ and $1.38\\%$ , respectively, indicating highly accurate estimation. Similar results were obtained by using a sensor with film thickness of $281\\mathrm{nm}$ (Figure S11 and Table S2, Supporting Information).  \n\n![](images/1ab8ee0e3e8e0d9dd8713c35351102541165a15af81a89116c332742a0deac5b.jpg)  \nFigure 2.  Ethanol vapor sensor based on poly(HEMA-co-AAc) hydrogel interferometer. a) Real-time monitoring of ethanol indicated by the reflectance change of the second-order destructive interference centered at $472\\mathsf{n m}$ . The reflectance increases when the sensor is exposed to ethanol vapor (saturated with ${\\sf N}_{2}$ ) and decreases when ethanol vapor is removed. The insets show optical images of the film before and after ethanol response. The scale bar is $500\\upmu\\mathrm{m}$ . b) Experimental and theoretical hydrogel film thickness as a function of the partial pressure of ethanol. c) Quantitative analysis of ethanol vapor concentration based on RGB values. Two analyte samples are used for validation. The arrow indicates increase in the partial pressure of ethanol.  \n\nBy integration of the hydrogel interferometers into a sensor array, multianalyte recognition can be realized, with only one hydrogel material of different thicknesses. Generally, the construction of sensor arrays requires complex synthesis and massive screening of sensing molecules, or cooperation of multiple materials, making it a challenge for facile design with minimum materials.[40–43] Figure 3a shows a sensor array composed of poly(HEMA-co-AAc) of three different film thicknesses ( $234~\\mathrm{nm}$ for S1, $290~\\mathrm{nm}$ for S2, $362~\\mathrm{nm}$ for S3). After being exposed to volatile organic compounds (VOCs, i.e., acetic acid, acetone, ethanol, ethyl acetate, hexane, isopropanol (IPA), methanol, and tetrahydrofuran (THF), all saturated with ${\\bf N}_{2}^{\\prime}$ ), the sensor array shows a distinct color pattern for each VOC, due to the different swelling behaviors of the hydrogel in different vapors (Figure S12 and Table S3, Supporting Information). A single sensor may not give enough colorimetric information to differentiate the VOCs. For example, S1 shows similar violet color after responding to acetone and IPA, but S2 and S3 differentiate the two compounds. Figure 3b shows RGBbased response patterns of the sensor array to the VOCs. Each VOC possesses a specific pattern, even for chemically similar analytes such as alcohols (methanol, ethanol, and IPA). The identification of VOCs was performed by linear discriminant analysis (LDA) on the acquired data $(8{\\mathrm{~VOCs~}}\\times3$ RGB values $\\times3$ sensors $\\times3$ trails) to evaluate the similarity between data clusters (Figure 3c). F1 and $F2$ are the first two functions that describe the greatest spatial separation of the data. As shown in the 2D LDA score plot, clusters of different VOCs are significantly separated, showing $98.3\\%$ correct classification through the first two functions, which suggests successful discrimination. This single response material–based sensor array has provided a facile and effective strategy to differentiate multiple compounds.  \n\nThe sensing elements with different film thicknesses can be realized on a single hydrogel interferometer through ondemand patterning by spatially controlled polymerization. To demonstrate this, we designed a series of patterned devices based on the commonly used poly(acrylamide-co-acrylic acid) hydrogel. As shown in Figure 4a, after spin coating and shorttime ultraviolet (UV) exposure of the precursor solution, partially polymerized film was formed. Subsequently, additional UV exposure on selected regions of the film was conducted with a photomask to enable spatially controlled polymerization. Under this procedure, a freshly made platform appeared a uniform color without observable patterns. After being exposed to moisture, the encoded image area was revealed. Hence, the patterned platform serves as an information encryption device. As shown in Figure 4b, the encrypted letters “UCLA”  \n\n![](images/fecdaa11d50b036fc0b55145f81395cfad79871282c436dde9465b50501dee34.jpg)  \nFigure 3.  Pattern-based recognition of multiple VOCs with single hydrogel material–based sensor array. a) Colorimetric response of the sensor array to 8 VOCs. The three sensing elements are all based on poly(HEMA-co-AAc) hydrogel, with a thickness of $234\\mathsf{n m}$ for S1, $290\\ \\mathsf{n m}$ for S2, $362\\ \\mathsf{n m}$ for S3, respectively. b) RGB value patterns of the sensor array to each VOC. c) The 2D score plot of LDA of 8 VOCs measured three times, showing significant separation of data clusters.  \n\n![](images/779726bd9a3ee62bf978cd7d7d0db1eda4258eb09832098679d60130c2daf6e8.jpg)  \nFigure 4.  Patterning of hydrogel interferometer and smartphone-based sensing. a) Schematic of the patterning process. On-demand patterning can be achieved through spatially controlled polymerization. b) An information encryption device. The decryption is triggered instantly by moisture, while the information is hidden immediately after removing moisture. The scale bar is $2\\mathsf{m m}$ . c) Thickness changes of the image (water droplet pattern) and nonimage (surrounding) areas with increased relative humidity in the surrounding. The insets are the corresponding photographs of water droplet pattern at respective humidity. d) A humidity indicator based on a multicolor image pattern. The scale bar is $2\\mathsf{m m}$ . e) Smartphone-based sensing system for both quantitative estimation and multianalyte identification. The app automatically matches the photograph of samples with the closest records in the database and gives the result of detection. Quantitative sensing of ethanol vapor is demonstrated as an example.  \n\nemerge immediately when the film is exposed to moisture; once the moisture is removed, instantly the letters are hidden again. This reversible encryption and decryption process can be simply triggered by breath (Movie S2, Supporting Information), providing potential for rapid information acquisition and protection in emergency, without any additional equipment (e.g., UV light source for commonly used data encryption devices[44]).  \n\nThe color contrast of the decrypted image and nonimage area is caused by the thickness difference of the hydrogel films, which is proven after removing unreacted monomers. As shown in Figure 4c, a water droplet pattern is achieved after washing the hydrogel interferometer which is fabricated by spatially controlled polymerization. Treated with longer UV exposure time, the hydrogel of the image area (water droplet pattern) is thicker than that of the nonimage area (214 vs $193\\ \\mathrm{nm}$ at ambient relative humidity (RH) of $45\\%$ ). With the increase of RH, the image and nonimage areas simultaneously swell and show shift within their reflection spectra (Figure S13, Supporting Information), exhibiting swelling ratios of $83.6\\%$ and $83.4\\%$ , respectively, at RH of $93\\%$ compared to the ambient RH of $45\\%$ . As a result, the colors of the pattern change along with the humidity. At relatively high RH, the increased chemical potential of surrounding water vapor boosts the swelling ratio of the hydrogel film, resulting in a significant color change even for a small alteration of humidity (e.g., as large as ${\\approx}100$ nm redshift of the reflection valley from RH of $80\\%$ to $85\\%$ ). Such high sensitivity induced by superlinear humidity responsiveness can be further tuned by adjusting the crosslinking density of the hydrogel (Figure S14, Supporting Information). The experimentally measured swelling ratio is consistent with the simulation result based on the theory of hydrogel swelling (Figure S19, Supporting Information). In addition to the monocolor image pattern, multicolor image patterns, such as a half–half star shown in Figure 4d, can be achieved via the same fabrication strategy. Hence, the current adaptive platform can serve as an optical humidity indicator, with fast response (Figure S15 and Movie S3, Supporting Information). These examples demonstrate the potential of intuitive recognition with naked eye as well as accurate measurement by simply incorporating additional color (thickness) areas through on-demand patterning.  \n\nTo realize portable and commercialized detection, we developed a colorimetric analysis application (app) for smartphones. As shown in Figure 4e, two functions are available in the app: measuring the concentration of a single analyte, and differentiating multiple analytes. When the photograph of an unknown sample is taken and analyzed, the app will automatically match the new image with the closest records in the database and give the result of detection (Movies S4 and S5, Supporting Information). The sensing system can be further developed for analysis of more compounds, depending on the design of adaptive sensors for the desired analytes. Through the mobile app, real-time monitoring of environment or bodily condition can be conveniently carried out.  \n\nIn summary, inspired by the color change depending on the cell or protein soft layer of living organisms, we have demonstrated a hydrogel interferometer as an adaptive color platform, based on a thin hydrogel film covalently bonded on a substrate. The simple design avoids the use of photonic structure template or the careful assemblies of micro-/nanobuilding blocks to achieve adaptive coloration, providing a facilely tunable way for achieving broader functionalities. Small environmental alteration causes hydrogel thickness change and thus its interference color change. Hence, interference colors serve as a powerful tool to make very small measurements and reveal rich environmental metrics. We have also established a computational model to systematically investigate the response dynamics, which shows good theory–experiment agreement. This elucidates the mechanism and design principle for the broad functionality. With the simple and covalently bonded structure, the hydrogel interferometer is robust, low cost, and applicable for various hydrogels. Specifically, by employing poly(HEMA-co-AAc) hydrogel, the interferometer can be used as a volatile-vapor sensor for high-accuracy quantitative detection, with fast response and recovery (140 and $210~\\mathrm{ms}$ , respectively). By integrating multiple such interferometers with different thicknesses into an array, the adaptive platform is able to recognize multiple VOCs, providing an approach for multianalyte identification by a single material. Furthermore, patterning can be facilely conducted on the platform, providing the capabilities of breath-controlled information encryption and decryption, as well as multicolor humidity indicator. To benefit its commercial applications, smartphone-based colorimetric analysis is built for portable and easy-to-use sensing systems. Our strategy of constructing adaptive color system provides a simple but general way for achieving diverse functionalities. By simply changing or modifying the hydrogel layer, this hydrogel interferometer can be readily applied in multiple areas such as high-level data security and real-time environment or health monitoring.",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# Supporting Information  \n\nSupporting Information is available from the Wiley Online Library or from the author.",
+        "category": " References"
+    },
+    {
+        "id": 3,
+        "chunk": "# Acknowledgements  \n\nM.Q. and M.S. contributed equally to this work. X.H. acknowledges the UCLA start-up funding and ONR award (N00014-17-1-2117). R.B. and Z.S. acknowledge the support of the NSF MRSEC at the Harvard (DMR-1420570).",
+        "category": " References"
+    },
+    {
+        "id": 4,
+        "chunk": "# Conflict of Interest  \n\nThe authors declare no conflict of interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 5,
+        "chunk": "# Keywords  \n\nchemical sensing, hydrogels, information encryption, interference colors, real-time monitoring  \n\nReceived: January 22, 2018 Revised: February 21, 2018 Published online:  \n\n[7]\t X.  He, M.  Aizenberg, O.  Kuksenok, L. D.  Zarzar, A.  Shastri, A. C. Balazs, J. Aizenberg, Nature 2012, 487, 214. [8]\t A.  Shastri, L. M.  McGregor, Y.  Liu, V.  Harris, H.  Nan, M.  Mujica, Y.  Vasquez, A.  Bhattacharya, Y.  Ma, M.  Aizenberg, O.  Kuksenok, A. C. Balazs, J. Aizenberg, X. He, Nat. Chem. 2015, 7, 447. [9]\t D.  Buenger, F.  Topuz, J.  Groll, Prog. Polym. Sci. 2012, 37, 1678.   \n[10]\t A.  Doring, W.  Birnbaum, D.  Kuckling, Chem. Soc. Rev. 2013, 42, 7391.   \n[11]\t R. Tamate, T. Ueki, R. Yoshida, Adv. Mater. 2015, 27, 837.   \n[12]\t Y. Liu, W. Shen, Q. Li, J. Shu, L. Gao, M. Ma, W. Wang, H. Cui, Nat. Commun. 2017, 8, 1003.   \n[13]\t T.  Masuda, N.  Shimada, T.  Sasaki, A.  Maruyama, A. M.  Akimoto, R. Yoshida, Angew. Chem., Int. Ed. 2017, 56, 9459.   \n[14]\t W.  Li, F.  Gao, X.  Wang, N.  Zhang, M.  Ma, Angew. Chem., Int. Ed. 2016, 55, 9196.   \n[15]\t B.  Sun, Z.  Wang, Q.  He, W.  Fan, S.  Cai, Soft Matter 2017, 13, 6852.   \n[16]\t V. L. Alexeev, A. C. Sharma, A. V. Goponenko, S. Das, I. K. Lednev, C. S.  Wilcox, D. N.  Finegold, S. A.  Asher, Anal. Chem. 2003, 75, 2316.   \n[17]\t Y.  Kang, J. J.  Walish, T.  Gorishnyy, E. L.  Thomas, Nat. Mater. 2007, 6, 957.   \n[18]\t E. Tian, J. Wang, Y. Zheng, Y. Song, L. Jiang, D. Zhu, J. Mater. Chem. 2008, 18, 1116.   \n[19]\t J.-T. Zhang, L. Wang, J. Luo, A. Tikhonov, N. Kornienko, S. A. Asher, J. Am. Chem. Soc. 2011, 133, 9152.   \n[20]\t L. B.  Wang, J. X.  Wang, Y.  Huang, M. J.  Liu, M. X.  Kuang, Y. F.  Li, L. Jiang, Y. L. Song, J. Mater. Chem. 2012, 22, 21405.   \n[21]\t C.  Zhang, M. D.  Losego, P. V.  Braun, Chem. Mater. 2013, 25, 3239.   \n[22]\t C. Zhang, G. G. Cano, P. V. Braun, Adv. Mater. 2014, 26, 5678.   \n[23]\t B. Ye, H. Ding, Y. Cheng, H. Gu, Y. Zhao, Z. Xie, Z. Gu, Adv. Mater. 2014, 26, 3270.   \n[24]\t Z.  Cai, D. H.  Kwak, D.  Punihaole, Z.  Hong, S. S.  Velankar, X.  Liu, S. A. Asher, Angew. Chem., Int. Ed. 2015, 54, 13036.   \n[25]\t Y. Zhang, Q. Fu, J. Ge, Nat. Commun. 2015, 6, 7510.   \n[26]\t R.  Pernice, G.  Adamo, S.  Stivala, A.  Parisi, A. C.  Busacca, D.  Spigolon, M. A.  Sabatino, L.  D’Acquisto, C.  Dispenza, Opt. Mater. Express 2013, 3, 1820.   \n[27]\t Y.-L. Ko, H.-P. Tsai, K.-Y. Lin, Y.-C. Chen, H. Yang, J. Colloid Interface Sci. 2017, 487, 360.   \n[28]\t J.  Liu, Y.  Zhang, R.  Zhou, L.  Gao, J. Mater. Chem. C 2017, 5, 6071.   \n[29]\t S. Lin, H. Yuk, T. Zhang, G. A. Parada, H. Koo, C. Yu, X. Zhao, Adv. Mater. 2016, 28, 4497.   \n[30]\t L. He, M. Janner, Q. Lu, M. Wang, H. Ma, Y. Yin, Adv. Mater. 2015, 27, 86.   \n[31]\t J.-W.  Oh, W.-J.  Chung, K.  Heo, H.-E.  Jin, B. Y.  Lee, E.  Wang, C.  Zueger, W.  Wong, J.  Meyer, C.  Kim, S.-Y.  Lee, W.-G.  Kim, M. Zemla, M. Auer, A. Hexemer, S.-W. Lee, Nat. Commun. 2014, 5, 3043.   \n[32]\t L.  Bai, Z.  Xie, W.  Wang, C.  Yuan, Y.  Zhao, Z.  Mu, Q.  Zhong, Z.  Gu, ACS Nano 2014, 8, 11094.   \n[33]\t T.  Çaykara, C.  Özyürek, Ö.  Kantog˘lu, O.  Güven, J. Polym. Sci., Part B: Polym. Phys. 2002, 40, 1995.   \n[34]\t N. L. Smith, Z. Hong, S. A. Asher, Analyst 2014, 139, 6379.   \n[35]\t W.  Hong, Z. S.  Liu, Z. G.  Suo, Int. J. Solids Struct. 2009, 46, 3282.   \n[36]\t S. A. Chester, L. Anand, J. Mech. Phys. Solids 2011, 59, 1978.   \n[37]\t X. Xu, A. V. Goponenko, S. A. Asher, J. Am. Chem. Soc. 2008, 130, 3113.   \n[38]\t A.  Ranft, F.  Niekiel, I.  Pavlichenko, N.  Stock, B. V.  Lotsch, Chem. Mater. 2015, 27, 1961.   \n[39]\t J. H.  Lee, B.  Fan, T. D.  Samdin, D. A.  Monteiro, M. S.  Desai, O.  Scheideler, H.-E.  Jin, S.  Kim, S.-W.  Lee, ACS Nano 2017, 11, 3632.   \n[40]\t Y.  Huang, F. Y.  Li, M.  Qin, L.  Jiang, Y. L.  Song, Angew. Chem., Int. Ed. 2013, 52, 7296.   \n[41]\t Y.  Liu, T.  Minami, R.  Nishiyabu, Z.  Wang, P.  Anzenbacher, J. Am. Chem. Soc. 2013, 135, 7705.   \n[42]\t M. Qin, F. Y. Li, Y. Huang, W. Ran, D. Han, Y. L. Song, Anal. Chem. 2015, 87, 837.   \n[43]\t M.  Qin, Y.  Huang, Y. N.  Li, M.  Su, B. D.  Chen, H.  Sun, P. Y. Yong, C. Q. Ye, F. Y. Li, Y. L. Song, Angew. Chem., Int. Ed. 2016, 55, 6911.   \n[44]\t X. Li, Y. Xie, B. Song, H.-L. Zhang, H. Chen, H. Cai, W. Liu, Y. Tang, Angew. Chem., Int. Ed. 2017, 56, 2689.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "·综述·",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# 水凝胶在骨组织工程中的应用进展  \n\n曹建泽 张杰 刘永飞 赵海燕  \n\n摘要 骨缺损是骨科的常见疾病之一，随着骨组织工程技术的不断发展与进步，越来越多的骨修复材料被应用于临床，为骨组织修复提供了新型的治疗策略。水凝胶因具有良好的生物相容性和生物降解性，有望成为一种有潜力的骨组织修复材料。近年来，更多有关水凝胶的研究和应用聚焦于对水凝胶进行改性。改性后的水凝胶一方面可以更高效地释放负载因子并发挥作用，另一方面其力学性能也变得更优异，从而更符合组织工程支架的要求。该文就近年来在新型杂化纳米颗粒水凝胶负载细胞因子促进骨修复、水凝胶预防和治疗骨科细菌感染及开发性能更好的骨组织工程支架和3D 打印支架等方面的最新进展进行综述。  \n\n关键词 水凝胶；杂化纳米颗粒水凝胶；骨再生；骨组织修复；DOI: 10.3969/j. issn. 1673-7083. 2023. 05. 010  \n\n骨组织缺损可由多种情况引起，如创伤、关节炎和运动相关损伤[1]。由于骨组织可以自我修复和再生，因而小的缺损无需额外治疗即可正常愈合。但较大面积骨缺损（节段性缺损 ${>}2\\ \\mathrm{cm}$ 或者缺损骨周长 $550\\%$ ）可能会引发骨不连、畸形愈合等情况，此时需要对损伤进行干预，如采取骨移植或置换手术 [2]。然而，自体骨移植和同种异体骨移植均存在供体部位并发症发病率高、潜在感染风险大和宿主组织愈合率不高等不足，在应用方面受到限制 [3-4]。因此，受损骨组织的理想修复方案尚待明确。对于骨缺损患者治疗而言，开发有效的、可持续的受损骨组织修复方法意义重大[5-6]。  \n\n水凝胶具有独特性能优势，不仅可以用作可注射的组织填充剂，以液态形式将负载细胞和（或）  \n\n细胞因子输送到缺损区域并原位固化，从而诱导细胞和组织生长，还可以用作 3D 生物打印的生物墨水或用作细胞或药物输送的纳米级颗粒。在生物医学领域，水凝胶的性能得到了广泛的探索。为改善骨修复，近年来水凝胶设计取得了进展，以提高其效用 [7-8]。",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# 1 水凝胶分类  \n\n水凝胶由具有3D网络结构的亲水聚合物形成。水凝胶通常是由一种或几种单体通过化学反应制备的，通过在聚合物链之间形成缔合键，其水吸收能力可高达其自身干重的成百上千倍 [9]。根据驱动 3D 网络结构的相互作用的不同，水凝胶可分为化学水凝胶和物理水凝胶2 种（见表1）。  \n\n表1 水凝胶的分类  \n\n\n<html><body><table><tr><td></td><td>交联方式</td><td>优势</td><td>劣势</td></tr><tr><td>物理水凝胶</td><td>分子间相互作用</td><td>作用力数量多，相抵黏度低，剪切变稀，快速恢复分子间相互作用力弱，作用强度依赖外部刺激</td><td></td></tr><tr><td>化学水凝胶</td><td>官能团共价作用</td><td>力学性能好，稳定性强，亲水性较好</td><td>会因大孔的形成而发生相分离</td></tr></table></body></html>",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1.1 物理水凝胶  \n\n物理水凝胶是经温度、pH 和离子浓度的变化等物理交联过程生成，并通过分子纠缠和（或）氢键、离子力、疏水力及范德华力连接在一起的网络 [10-12]，主要包括静电相互作用形成的水凝胶、温度或pH 诱导的凝胶化水凝胶、超分子组装水凝胶、剪切稀化水凝胶等 [13]。在上述类型的水凝胶中发生的相互作用虽然很弱，但数量众多，有利于发挥复杂的功能。由于这些相互作用在很大程度上与pH、离子浓度、溶剂组成或温度等外部刺激有关，因此与依靠共价键结合的材料不同，物理水凝胶在环境方面具有高度适应性 [14]。物理水凝胶的可注射或可 3D 打印性能要求其在高剪切速率下黏度相对较低，以便于注射或打印。而在注入和沉积到指定位置后，则需要发生快速的相转变，以防止凝胶流动。换言之，物理水凝胶在剪切应力作用下呈黏性流体状态，而在剪切应力消除后可以快速恢复，即剪切变稀和快速恢复，这是物理水凝胶实现可注射或可打印的关键。",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 1.2 化学水凝胶  \n\n由共价交联的网络组成的水凝胶被称为化学水凝胶，也称永久性水凝胶。它是指由聚合物链中官能团之间的共价相互作用形成的水凝胶，官能团常见的共价偶联反应主要包括迈克尔加成反应、点击反应、席夫碱形成、光交联、酶介导交联等 [13]。与物理水凝胶类似，化学水凝胶也是非均质的，通常是高交联密度和低溶胀度的区域分散在低交联密度和高溶胀度的区域中，这些不同溶胀度区域是受交联剂的疏水聚集影响形成的。在某些情况下，根据凝胶化过程中成分、溶剂、温度和固体浓度不同，化学水凝胶会随着大孔的形成而发生相分离 [15]。与物理水凝胶不同，化学水凝胶具有带有共价键的交联网络结构。这种水凝胶可以通过交联水溶性单体和聚合物，将疏水性单体和聚合物转化为亲水性单体和聚合物来制备。此外，化学水凝胶因成键多为共价键，其力学性能较物理水凝胶更优异，稳定性也更高 [16]。",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2 水凝胶在骨组织工程中的应用  \n\n2.1 作为细胞和（或）生长因子载体促进骨修复  \n\n骨组织工程是一种潜力巨大的骨修复方式，通常是先将细胞和（或）生长因子包裹在水凝胶中，再通过水凝胶将细胞或生长因子定向输送到骨缺损部位，从而可以持续释放细胞和（或）生长因子，以促进缺损部位修复，其修复效果明显。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.1.1 杂化纳米颗粒水凝胶  \n\n金属杂化的纳米颗粒与水凝胶材料结合可以有效改善水凝胶的性质。有研究者设计了一种红外光响应性杂化（UCNP-Au-Alg）水凝胶，即可以在红外光照下快速加热。该水凝胶一方面可以通过非侵入性近红外光有效治疗肿瘤并预防其复发，另一方面则可以使胫骨骨缺损大鼠的胫骨更加光滑，显示该水凝胶可以促进受损骨骼有效愈合，这一策略为治疗由骨肿瘤引起的病理性骨折提供了全新的理论支持[17]。  \n\nWang 等 [18] 报道了一种杂化纳米颗粒（NP）/聚乙二醇水凝胶（PEG）递送系统，他们将包埋在水凝胶中的 siRNA/NP 递送到骨折部位，并使这些颗粒以一定的速度持续定点释放。动物实验证实，在骨折后 1 周 siRNA/NP 水凝胶组钙化愈合组织明显多于对照组。虽然这种方法可能会降低 siRNA在愈合后期的功效，但它对开发负载其他治疗性siRNA 或 miRNA 水凝胶的骨组织工程策略具有重大意义，为未来骨缺损修复提供了一个有潜力的研究方向。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.1.2 调节骨微环境  \n\n骨缺损部位常常因缺氧而出现大量活性氧（ROS）堆积，ROS 的过度产生会阻碍骨折愈合，使骨折部位发生延迟愈合 [19]。因此，改善骨缺损部位的缺氧环境对骨再生具有重大意义。  \n\nSun 等 [20] 设计了可以调控骨微环境的 ROS 清除和响应性延长产氧水凝胶（CPP-L/GelMA），并将其填充在骨缺损部位，该水凝胶可连续释放氧气 2 周以上，在骨缺损部位形成一个富氧环境，从而有效改善缺氧，并抑制 ROS 过度产生 [20]。这在骨组织修复领域属于重大突破。虽然有研究致力于制造释放氧气的支架，但其释放氧气时间过短，无法与骨组织修复过程相匹配，所以仍需进一步改进 [21]。通过调节 ROS 堆积的治疗策略有望成为修复骨缺损的重要手段之一。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.2 作为药物载体预防和治疗骨科细菌感染  \n\n细菌感染可在骨折后或假体置换术后造成严重后果，目前主要的治疗方法是口服抗生素或外科治疗。随着抗生素的过度使用，大量耐药菌株出现，导致抗生素疗效减退 [22]。此外，将抗生素与假体混合后置入受损部位是另一种可行方式，但抗生素易聚集会导致应力集中，且其释放后所留孔隙可能破坏材料结构的完整性。  \n\n水凝胶因其卓越的生物相容性、可控的理化特性和高度的组织适应性，逐渐成为受损骨组织的理想修复材料。Johnson 等 [23] 的研究表明，递送溶葡萄球菌素的可注射 PEG 不但对骨折后的金黄色葡萄球菌感染具有较好的治疗效果，而且在治疗感染的同时亦可促进骨折愈合，表明负载药物的水凝胶在治疗骨科感染性疾病中具有双重作用。Liu 等 [24] 用阳离子季铵盐（QAS）基团改性可光交联的明胶基聚合物（GelMA）制备了一种新型水凝胶系统，该系统可以发挥良好的细胞亲和性和抗菌性的协同作用，在大鼠股骨骨折感染模型中表现出优异的抗菌能力。此外，有研究将 miRNA 拮抗剂负载到细菌敏感性透明质酸基水凝胶中，这类可注射水凝胶被证实有良好的可注射性、组织黏附性和抗菌性，可通过持续释放 miRNA 拮抗剂在抗菌的环境中促进骨折修复[25-26]。上述研究表明，这些水凝胶本身具有抗菌作用，可以直接注射在骨折或骨缺损部位，从而预防或治疗感染，但单纯水凝胶的抗菌作用有限。在水凝胶中负载抗菌物质既能有效抗菌，又可最大程度减轻抗菌物质对骨缺损部位的不良影响。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.3 作为骨再生支架促进骨修复  \n\n组织工程技术是一种具有巨大应用潜力的骨修复新方法，其目标是创建可以模拟细胞外基质并能为新骨形成提供坚固机械支持的支架 [27]，以修复受损骨组织。传统的用于骨修复的支架制造技术已得到广泛研究，但其在模拟生物组织的复杂微环境方面存在局限性 [28]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 2.3.1 明胶和海藻酸肼水凝胶  \n\nWu 等 [29] 使用明胶和海藻酸肼分别用于模拟细胞外基质中胶原蛋白和糖胺聚糖的组成，构建了在生理环境下具有稳定溶胀性能的高强度明胶 -HAlg-DN 水凝胶。在用作组织工程支架时，该水凝胶的抗溶胀能力有利于防止支架术后变形，并可降低支架施加在周围组织的压力。在大鼠骨缺损模型中，负载补骨脂素的明胶 -HAlg-DN 水凝胶可有效促进骨再生，并显示出作为骨组织工程支架的巨大潜力。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 2.3.2 3D 打印复合水凝胶支架  \n\n近年来，3D 打印技术掀起了材料制作的热潮，3D 打印技术可以将一些不易结合的物质联系起来，共同发挥它们的优势，是未来研究的一个重点方向。Liu 等 [30] 设计并开发了一种通过 3D 打印技术制作的纳米凹凸棒石（nano-ATP）/GelMA 复合水凝胶，该水凝胶既保留了水凝胶优良的生物相容性，又通过加入凹凸棒石的改性大大提升了水凝胶的力学性能。他们将小鼠骨髓间充质干细胞（BMSC）和脐静脉内皮细胞负载到该复合水凝胶支架中，结果表明支架内的细胞不仅活力高，而且具有明显促进BMSC 成骨分化的倾向 [30]。  \n\n此外，有大量研究将具有骨诱导活性的天然生物矿物质、新型脱细胞骨细胞外基质、La 离子、miRNA 等通过 3D 打印技术制成复合水凝胶支架，以促进骨缺损修复 [31-34]。上述研究为 3D 打印生物材料提供了良好的例证，即在保证具有明显疗效的同时，也保证了材料尺寸的精确性，为精准化医疗提供了一个新的思路和方向。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3 结语  \n\n水凝胶由于其良好的生物相容性、亲水性和生物降解性而备受瞩目，在生物医药领域具有较大应用潜力，在骨科领域主要于组织工程、药物递送等。由于受到水凝胶材料响应时间太长、力学性能有待改善、可能产生毒理学反应以及可能引发机体免疫排斥反应等问题限制，水凝胶尚未得到广泛的临床应用。  \n\n未来的研究应致力于继续改善水凝胶的性能或发现性能更好的水凝胶种类，并且进一步探究它们的作用机制，使其尽早广泛应用于实际，造福于骨组织损伤患者。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 14,
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Injectable in situ induced robust hydrogel for photothermal therapy and bone fracture repair[J]. Adv Funct Mater, 2021, 31(19).   \n[18] Wang Y, Malcolm DW, Benoit DSW. Controlled and sustained delivery of siRNA/NPs from hydrogels expedites bone fracture healing[J]. Biomaterials, 2017, 139: 127-138.   \n[19] Teh SW, Koh AE, Tong JB, et al. Hypoxia in bone and oxygen releasing biomaterials in fracture treatments using mesenchymal stem cell therapy: a review[J]. Front Cell Dev Biol, 2021, 9: 634131.   \n[20] Sun H, Xu J, Wang Y, et al. Bone microenvironment regulative hydrogels with ROS scavenging and prolonged oxygen-generating for enhancing bone repair[J]. Bioact Mater, 2023, 24: 477-496.   \n[21] Wang Y, Xie C, Zhang Z, et al. 3D printed integrated bionic oxygenated scaffold for bone regeneration[J]. ACS Appl Mater Interfaces, 2022, 14(26): 29506-29520.   \n[22] 张青, 马慧娜. 大肠埃希菌生物膜形成与耐药机制的研究进展[J]. 中国抗生素杂志 , 2018, 43(5): 497-501.   \n[23] Johnson CT, Wroe JA, Agarwal R, et al. Hydrogel delivery of lysostaphin eliminates orthopedic implant infection by Staphylococcus aureus and supports fracture healing[J]. Proc Natl Acad Sci U S A, 2018, 115(22): E4960-E4969.   \n[24] Liu Y, Dong T, Chen Y, et al. Biodegradable and cytocompatible hydrogel coating with antibacterial activity for the prevention of implant-associated infection[J]. ACS Appl Mater Interfaces, 2023, 15(9): 11507-11519.   \n[25] Yu C, Chen L, Zhou W, et al. Injectable bacteria-sensitive hydrogel promotes repair of infected fractures via sustained release of mirna antagonist[J]. ACS Appl Mater Interfaces, 2022, 14(30): 34427- 34442.   \n[26] Liu P, Xiong Y, Chen L, et al. Angiogenesis-based diabetic skin reconstruction through multifunctional hydrogel with sustained releasing of M2 Macrophage-derived exosome[J]. Chem Eng J, 2022, 431.: 132413.   \n[27] Haugen HJ, Lyngstadaas SP, Rossi F, et al. Bone grafts: which is the ideal biomaterial?[J]. J Clin Periodontol, 2019, 46 Suppl 21: 92-102.   \n[28] Ansari MAA, Golebiowska AA, Dash M, et al. Engineering biomaterials to 3D-print scaffolds for bone regeneration: practical and theoretical consideration[J]. Biomater Sci, 2022, 10(11): 2789-2816.   \n[29] Wu T, Liu L, Gao Z, et al. Extracellular matrix (ECM)-inspired highstrength gelatin-alginate based hydrogels for bone repair[J]. Biomater Sci, 2023, 11(8): 2877-2885.   \n[30] Liu C, Dai T, Wu X, et al. 3D bioprinting of cell-laden nanoattapulgite/gelatin methacrylate composite hydrogel scaffolds for bone tissue repair[J]. J Mater Sci Technol, 2023, 135: 111-125.   \n[31] Kara A, Distler T, Polley C, et al. 3D printed gelatin/decellularized bone composite scaffolds for bone tissue engineering: fabrication, characterization and cytocompatibility study[J]. Mater Today Bio, 2022, 15: 100309.   \n[32] Xu Z, Lin B, Zhao C, et al. Lanthanum doped octacalcium phosphate/ polylactic acid scaffold fabricated by 3D printing for bone tissue engineering[J]. J Mater Sci Technol, 2022, 118: 229-242.   \n[33] Pan T, Song W, Xin H, et al. MicroRNA-activated hydrogel scaffold generated by 3D printing accelerates bone regeneration[J]. Bioact Mater, 2022, 10: 1-14.   \n[34] Gang F, Ye W, Ma C, et al. 3D Printing of PLLA/biomineral composite bone tissue engineering scaffolds[J]. Materials (Basel), 2022, 15(12): 4280.  \n\n（收稿日期 ：2023-04-05）  \n\n（本文编辑：富饶）",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Glucose detection with surface plasmon resonance spectroscopy and molecularly imprinted hydrogel coatings  \n\nJing Wang a,  Soame Banerji b,  Nicola Menegazzo a,  Wei Peng b,1,  Qiongjing Zou a,  Karl S.  Booksh a,∗  \n\na Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19711, United States b Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ, 85287, United States",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# a r t i c l e i n f o",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# a b s t r a c t  \n\nArticle history:   \nReceived 12 July 2011   \nReceived in revised form 22 August 2011   \nAccepted 23 August 2011   \nAvailable online 30 August 2011  \n\nKeywords:   \nSurface plasmon resonance   \nMolecular imprinting   \nHydrogel   \nGold nanoparticles   \nGlucose sensing  \n\nMolecularly imprinted hydrogel membranes were developed and evaluated for detection of small analytes via  surface plasmon resonance spectroscopy. Imprinting of glucose phosphate barium  salt into  a poly(allylamine hydrochloride) network covalently bound to  gold surfaces yielded  a  selective  sensor for glucose. Optimization of  relative amounts of chemicals used for  preparation of  the  hydrogel was  performed to obtain  highest sensitivity. Addition of gold  nanoparticles into  the  hydrogel matrix significantly amplified its  response and  sensitivity due  to  the  impact of  gold  nanoparticles on the  refractive index  of the sensing layer.  Evaluation of  its  selectivity showed that  the  sensor displayed preferential recognition to glucose compared to  structurally related sugars in  addition to  being unaffected by phosphate as well as compounds containing amine groups, like  creatinine. The  detection limit  of glucose  in deionized water was calculated to  be $0.02\\mathrm{mg/mL}$ . The  developed sensor was  finally exposed to human urine  spiked with glucose illustrating the  coating’s ability to  re-bind  the  analyte in  complex matrices. While the  working concentration range  in  water  was  determined to  be  suitable for  glucose monitoring in  diabetic individuals at  physiological levels, the  detection in  urine  was  determined to  be $0.12\\mathrm{mg/mL}$ The decreased performance in  urine  provided  an  initial  perspective on  the  difficulties associated with  measurements in complex media.  \n\n$\\mathfrak{C}$ 2011 Elsevier B.V. All rights reserved.",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# 1. Introduction  \n\nMonitoring of small molecules, such as metabolites, drugs, pesticides, and pollutants in complex matrices is of interest to environmental analysis, medical studies, clinical treatment and food science [1–7]. Surface plasmon resonance (SPR) spectroscopy is a versatile approach capable of detecting a wide range of small molecules upon incorporation of appropriate surface modification strategies [8–13]. In the Kretschmann configuration, surface plasmon polaritons (SPPs) are excited by backside-illuminating the plasmon supporting material (typically gold or silver) via total internal reflectance [14–16].  SPR spectroscopic sensing measures changes in the dielectric constant (ultimately, the refractive index, RI) of the sample induced by either chemical (e.g. antibody–antigen binding) or physical (e.g. temperature) events. The analytical signal is derived from the intensity minima of the reflected light (the so-called ‘SPR dip’) which corresponds to photons momentum matched to SPPs, and is measured as a function of in-coupling angle (for monochromatic light sources) or wavelength (for fixed-angle configurations). SPR spectroscopy displays high sensitivity towards biomolecular binding events, as evidenced by low detection limits reported $\\mathrm{\\langleng/mL}$ level [15,17]), as well as capability for real-time monitoring, rendering it an important tool in (bio)chemical analyses [15,16,18,19].  \n\nHowever, RI measurements are not inherently selective, therefore non-specific events originating from interferents present a challenge to SPR sensors. To overcome this limitation, different analyte recognition strategies have been incorporated [20]. Molecularly imprinted polymers (MIPs) and molecularly imprinted hydrogels (MIHs) consist of biomimetic matrices templated with a target analyte, yielding recognition sites capable of selectively rebinding the analyte [21]. Imprinted matrices have been regarded as an attractive approach towards improvement of sensor selectivity [22–25],  due to their versatility, chemical robustness, simple preparation and extended shelf-life compared to biosensing strategies (e.g., enzymes, antibodies). However, adoption of imprinted coatings for SPR sensing has been limited despite initial positive reports from the literature [9,26–28].  \n\nGlucose detection is important for health monitoring in diabetic individuals [29,30].  Furthermore, accurate quantification of glucose in untreated physiological fluids, such as urine, remains challenging due to the complexity of the background matrix. Several examples of commercial glucose sensors are available; however, limitations on the long-term storage, resulting from degradation of the enzymes used for molecular recognition, has fueled investigations in alternative sensing strategies [31], with biomimetic materials, like MIPs, becoming a focus [24,32–34]. Hydrogels consist of a class of hydrophilic polymers capable of absorbing a high fraction of water [35,36], therefore diffusion, and ultimately detection, of polar glucose molecules through these hydrophilic membranes is facilitated. The coatings developed in this work consist of crosslinked poly(allylamine hydrochloride) (PAH) templated with the d-glucose 6-phosphate monobarium salt (GPS-Ba), the hydrogel is then covalently bound to gold-coated glass slides to produce the chemical recognition sites. In addition to health monitoring, the use of glucose as the target analyte also provided a solid baseline to compare the performance of the strategy proposed to other sensing architectures available in the literature and in the market [37].  \n\nBinding site formation in molecular imprinting is largely driven by complexation of the template and monomers in solution via hydrogen bonding and $\\pi{-}\\pi$ stacking [38–40].  Imprinting in solvents that disrupt hydrogen bonding interactions present an additional challenge which can be partially mitigated by employing a template baring a charge. Herein, self-assembly of the positively charged polymer around the template is facilitated by the negatively charged phosphate group. Once the template is removed, detection of glucose (pure, not the barium salt) is achieved following RI changes resulting from physical swelling of the MIH upon binding of the analyte. This sensing platform can be prepared easily, used repeatedly and displays good sensitivity and selectivity towards concentrations lower than $5\\mathrm{mg/mL}$ glucose in aqueous media.  \n\nIn contrast to detection of biomolecules, SPR sensing of small molecules remains largely unexplored due to the low RI changes induced by the analyte [14], ultimately translating into sensors with comparatively poor sensitivity requiring incorporation of a signal amplification method to improve limits of detection [41–43].  One approach used to improve sensor performance relies on incorporating gold nanoparticles into the chemical recognition matrix [44,45]. In this case, the enhancement phenomenon can be attributed to either an increase in bulk RI due to the presence of nanoparticles and/or plasmonic coupling between the nanoparticles and the underlying continuous metal film [45–51].  Addition of nanoparticles to the MIH amplified the response of the sensor to glucose in water approximately 10-fold. The detection limit, sensitivity and selectivity of the sensor over sugars structurally similar to glucose suggests the ability to measure the analyte at physiologically relevant levels, as well as the prospect of applying similar detection strategies to other low molecular weight compounds.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2. Experimental methods",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.1. Instrumental configuration  \n\nSlides used were made from either SF-10 $(n=1.73)$ or BK7 $(n=1.52)$ glass and were coated with $5\\mathrm{nm}$ chromium as an adhesion layer followed by $50\\mathrm{nm}$ of gold by a Cressington 308R DC magnetron sputter coating system (Watford, UK). The SPR system was configured to use the Kretschmann arrangement where the sensor was back-side illuminated with a 5 W Luxeon $\\mathsf{v}$ white light LED (Lumileds Lighting, LLC, San Jose, CA) through a $60^{\\circ}$ equilateral prism of the same material as the slide, and the reflected light was transmitted via a linear array of optical fibers to a Jobin-Yvon SPEX 270M spectrometer (Horiba Jobin-Yvon, Edison New Jersey, NJ) with an $1200\\mathrm{g/mm}$ grating. Spectra were collected with a $1024\\times1024$ pixel TE-cooled CCD camera (Andor Technology, model DV435, South Windsor, CT). The spectrometer allowed light reflected from different positions on the sensor surface being collected separately, therefore allowing both the analytic and reference channels to be probed simultaneously on the same sensor. Each channel consisted of a strip $20\\mathrm{mm}\\mathrm{L}\\times4\\mathrm{mm}\\mathrm{W}$ of the MIH coated sensor, though the spot size probed spectroscopically consisted of a $4\\mathrm{mm}\\times4\\mathrm{mm}$ area in the center of each channel. The SPR shift measured corresponds to the response of the MIH coating to chemical stimuli over the $16\\mathrm{mm}^{2}$ area.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.2. MIH preparation  \n\nTwo different self-assembled monolayers, formed from dithiobis(succinimidyl propionate) (DSP) and N-hydroxysuccinimide ester of 16-mercaptohexadecanoic acid (NHS-MHA) respectively, were evaluated for attachment of the MIH to sensor surfaces. DSP was purchased from Soltec Ventures, Inc. (Beverly, MA), whereas NHS-MHA was synthesized in-house following a previously described procedure [52].  \n\nDSP self-assembled monolayers were prepared by soaking freshly sputtered gold surfaces in 0.001 M DSP in dimethylsulfoxide (DMSO, MP Biomedicals, Solon, OH). Similarly, for the NHS-MHA self-assembled monolayer preparation, sensor surfaces were exposed to 0.005 M NHS-MHA in tetrahydrofuran (THF, Fisher Scientific, Fair Lawn, NJ). Modified gold surfaces were rinsed with DMSO or THF (depending of the SAM used), and then with water before being immediately used in the MIH preparation process.  \n\nThe MIH synthesis employed in this study was modified from Parmpi and Kofinas [53] to yield membranes suitable for SPR analysis. Specifically, a $20\\mathrm{mL}$ aqueous solution containing $0.1\\mathrm{mg/mL}$ aqueous poly(allylamine hydrochloride) (PAH, Sigma–Aldrich, St. Louis, MO), $0.5\\mathrm{mg/mL}$ d-glucose phosphate barium salt (GPS-Ba, Sigma–Aldrich, St. Louis, MO) and sufficient 1 M NaOH (Mallinckrodt, Paris, KY) to raise the solution pH to 9 (in order to partially neutralize the amine sites, rendering them available for subsequent tethering to the gold surface) was stirred for $30\\mathrm{min}$ prior to addition of DSP-modified gold-coated slides. The $30\\mathrm{min}$ delay allows for interaction and re-arrangement of the PAH around the template, initiating the formation of the analyte-recognizing cavities [53,54]. After $3\\mathrm{h}$ , 5 mL  of $0.03\\mathrm{M}$ epichlorohydrin (Acros Organics, Morris Plains, NJ) were added to crosslink the hydrogel and the solution was stirred overnight. The slides were then removed from the solution, rinsed with deionized water and dipped in $4\\mathrm{MNaOH}$ solution overnight to extract the template. Finally, sensors were dipped in stirred deionized water for $30\\mathrm{min}$ to thoroughly rinse off the NaOH. Sensor slides with NHS-MHA were prepared similarly, except that $1\\mathrm{mg/mL}$ GPS-Ba was added to the polymer solution and that $0.2\\ensuremath{\\mathrm{M}}$ NaOH was used to remove the template after imprinting. Finally the slides were dried under a stream of dry nitrogen (Keen Compressed Gas, Wilmington, DE) and stored under atmospheric conditions until used. For FT-IR studies, sensor slides were sputtered with $5\\mathrm{nm}$ chromium followed by $150\\mathrm{nm}$ of gold and prepared as described above. Mid-infrared absorption spectra were acquired with a Vertex 70 FT-IR spectrometer (Bruker Optics, Billerica, MA) equipped with a liquid nitrogen-cooled mercury–cadmium–telluride detector (Infrared Associates, Inc., Stuart, FL) at a $2{\\mathsf{c m}}^{-1}$ resolution. Each spectrum represents an average of 100 scans. An AutoSeagull specular reflectance accessory (Harrick Scientific, Pleasantville, NY) permitted spectral collection at an incident angle of $87^{\\circ}$ . In order to minimize atmospheric contributions, the sample compartment of the FT-IR spectrometer was aggressively purged with dry nitrogen gas. Scanning electron micrographs were acquired using a XL-30 scanning electron microscope (FEI, Hillsboro, OR) equipped with a field emission electron gun and operating in environmental mode.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 2.3. Gold nanoparticle preparation  \n\nGold nanoparticles were synthesized by a modified Turkevitch method [55]. Initially, the pH of a $10\\mathrm{{mL}0.001\\mathrm{{M}H A u C l_{4}}}$ $3\\mathrm{H}_{2}0$ (Acros Organics, Morris Plains, NJ) solution was adjusted to 7.2 with 1 M NaOH. The solution was heated to boiling and $5\\%\\mathrm{(w/w)}$ sodium citrate (Fisher Scientific, Fair Lawn, NJ) was added to achieve a 2:1 ratio between citrate and $\\mathsf{A u C l}_{4}-$ . The boiling solution was continuously stirred for $^{1\\mathrm{h}}$ turning a wine-red color. The colloid solution was allowed to cool to room temperature at which point several drops of a $1\\ensuremath{\\mathsf{M}}$ cysteamine hydrochloride (Sigma–Aldrich, St. Louis, MO) in $1\\mathrm{M}\\ \\mathrm{NaOH}$ solution was added until the colloid solution turned blue, indicating that the gold nanoparticles were modified with the cysteamine capping agent. A $5\\mathrm{mL}$ aliquot of this solution was added to the PAH solution immediately prior to the addition of epichlorohydrin. When gold nanoparticles were used the volume of $0.03\\mathrm{M}$ epichlorohydrin was also adjusted to $6.25\\mathrm{mL}$ to maintain the concentration of cross-linker. Characterization of the synthesized nanoparticles was performed with a JEM-2000fx transmission electron microscope (JEOL, Tokyo, Japan) equipped with a lanthanum hexaboride electron gun using an acceleration voltage of $200\\mathrm{kV}.$ An aliquot of the freshly synthesized colloid solution was drop-casted onto 200-mesh carbon-coated nickel grids purchased from SPI Supplies (West Chester, PA). Size distribution was determined with the DigitalMicrograph software from Gatan Inc. (Pleasanton, CA).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 2.4. Sugar detection in aqueous media  \n\nFor SPR measurements, a custom-made dual channel poly(methyl methacrylate) flow-cell was used to divide the sensor surface into two separate sensing regions and to guide flow of solutions across the sensor surface. One channel was presented with the analyte in solution, while the other served as a reference channel to account for signal drifting from pressure changes, temperature fluctuation or other external factors. The sensor was fixed to the flow-cell with a gasket made from laboratory paraffin film (Parafilm, Pechiney Plastic Packaging, Menasha, WI). The liquid flowing system consisted of a Rainin Dynamax peristaltic pump model RP-1 (Rainin Instrument, LLC, Oakland, CA) and a series of valves connected by 1/16 in. polytetrafluoroethylene tubing and controlled by a custom-written LabView virtual instrument (National Instruments, Austin, TX). Experimental runs began with the collection of s-polarized reflectance spectra used to normalize the light output from the source. Rotating the linear polarizer $90^{\\circ}$ the p-polarized component required for plasmonic coupling. The SPR dip minima was located using automated ‘minimumhunting’ MATLAB (Mathworks, Natick, MA) routines based on polynomial fitting of the parabolic SPR dip, with the roots of the fit corresponding to $\\lambda_{\\mathsf{S P R}}$ .  \n\nEach sensing cycle began with equilibration of the coating in water, followed by exposure to the analyte and then a water washing step to remove non-specifically bound species. At the end of each cycle, 0.1 M NaOH was flushed to regenerate the sensor surface. Each step lasted $10\\mathrm{{min}}$ . The MIHs were evaluated for rebinding affinity towards glucose and structurally related sugars, fructose and sucrose, at various concentrations. Glucose, fructose and sucrose were all obtained from Sigma–Aldrich (St. Louis, MO).",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2.5. Glucose detection in human urine  \n\nUrine sample collected from a healthy (non-diabetic) human male was used to verify the performance of the sensor exposed to physiological fluids. Prior to analysis, the urine was centrifuged to remove any particulate matter and the supernatant was spiked with $0.5{-}5.0\\mathrm{mg/mL}$ glucose. Ammonium phosphate (Fisher Scientific, Fair Lawn, NJ), urea, uric acid and creatinine (all from Sigma–Aldrich, St. Louis, MO) at physiologically relevant concentrations [56] were dissolved in deionized water and used to condition the sensor prior to the SPR measurements. The collection conditions were identical to measurements performed with deionized water.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3. Results and discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3.1. MIH synthesis and characterization  \n\nTwo SAMs with different carbon-chain lengths ( $\\cdot_{\\mathsf{C}_{3}}$ versus $C_{16}$ ) were tested for MIH attachment to the gold SPR surfaces with no discernible difference in coating quality. This is not surprising since in the application described herein, the SAM is utilized merely as a tether site for the MIH, therefore, the length of the carbon chain is inconsequential.  \n\nTwo contrasting processes are responsible for the formation of MIH coatings: the first one involves the availability of primary amines in neutralized PAH for reaction via amide coupling with the succinimidyl end-groups of the immobilized SAM and subsequent cross-linking upon addition of epichlorohydrin. The second process relies on the remaining amine salts in PAH to associate with the negatively charged phosphate groups of the template, forming the analyte binding sites in the MIH. Hence, control of the ratio between protonated and unprotonated amine groups present in solution is necessary, since attachment and cross-linking of the hydrogel network as well as the imprinting process itself are affected.  \n\nThese processes were monitored by FT-IR spectroscopy; Fig. 1(A–C) displays graphically the influence of the relative concentration of protonated to unprotonated amine (as a function of pH) on the attachment of the hydrogel to SAM-modified gold surfaces, while Fig. 1(D–E) highlights the imprinting process of the hydrogel.  \n\nPAH binding to SAM-modified surfaces can be monitored as a function of the decreasing $-C=0$ stretching peak absorbance at $1740\\mathrm{cm}^{-1}$ associated with the NHS end-group. Concomitantly, the increasing symmetric and antisymmetric $\\boldsymbol{-}\\mathsf{N}\\mathsf{H}_{2}$ bands between 1500 and $1700\\mathrm{cm}^{-1}$ further confirms attachment of the hydrogel to the surface [57]. At a pH value of 4 (see Fig. 1(A)) the $-C=0$ peak was still prominent after a reaction time of $420\\mathrm{{min}}$ , whereas it slowly decreases in intensity over $180\\mathrm{{min}}$ at $\\mathsf{p H}9$ (Fig. 1(B)) and completely disappears within $30\\mathrm{min}$ at $\\mathsf{p H}11$ (Fig. 1(C)). Comparison of the spectral time-series collected at the three pH values indicate that the rate of reaction between PAH and SAM concomitantly with the pH. The increase in intensity of the $\\boldsymbol{-}\\boldsymbol{\\mathrm{N}}\\boldsymbol{\\mathrm{H}}_{2}$ band confirms that amide coupling is favored at higher pHs. Estimation of the fraction of unprotonated amine groups in PAH $\\mathsf{p K}_{\\mathsf{a}}\\sim\\mathsf{g}$ [58,59]), yields that at pH values of 4, 9 and 11 the primary amines represent approximately $0.001\\%$ , $50\\%$ and $99\\%$ , respectively, of the total amines present in the hydrogel. Since unprotonated amines are responsible for reaction with the NHS leaving group and covalently bind to the SAM, the pH influences the binding rate of the hydrogel to sensor surfaces. Hydrogel attachment at pH 4 (Fig. 1(A)) was not observed to occur to any appreciable extend, hence further studies focused exclusively on MIHs bound at pH values of 9 and 11.  \n\nImprinting with the template was also evaluated by FT-IR spectroscopy. Using GPS-Ba as the template, instead of glucose, results in the formation of stronger GPS-Ba–hydrogel complex due to the ionic interaction. Because the MIH preparation is carried out in an aqueous environment, hydrogen bonding between glucose and amines cannot be relied on as the sole driving force for the imprinting process due to the interference of water [60,61]. Imprinting of the hydrogel with GPS-Ba yields an absorbance band at approximately $1050\\mathrm{cm}^{-1}$ associated with $-\\mathrm{P}{=}0$ stretching of the phosphate group [57], indicating the incorporation of the template within the hydrogel. The FT-IR spectra in Fig. 1(D) indicate that at $\\mathsf{p H9}$ , where approximately half of the amine groups are protonated, a strong association between the phosphate group and the PAH is achieved, as demonstrated by retention of the phosphate group within the hydrogel even after exposure to DI water for $^{6\\mathrm{h}}$ . At pH 11 (Fig. 1(E)), most of the amine groups are deprotonated, therefore the ionic interaction between the template and the hydrogel is not possible, resulting in a comparatively weak $-\\mathrm{P}{=}0$ absorption peak. These results indicate that at $\\mathsf{p H9}$ a good compromise is achieved between efficient hydrogel attachment to gold surfaces, while maintaining sufficient amine salts capable of interacting with the template. Hence, all hydrogel mixtures used for sensor studies presented below were adjusted to a $\\mathsf{p H9}$ .  \n\n![](images/a732d46698792cf04c92f9e6a85ace92a9632a90852bcf4e3588e27439058444.jpg)  \nFig. 1. The attachment of polymer via the NHS-MHA linker under (A) $\\mathsf{p H4}$ , (B) $\\mathsf{p H9}$ and (C) $\\mathsf{p H}11$ , and the imprinting of GPS-Ba into PAH at (D) $\\mathsf{p H9}$ and (E) $\\mathsf{p H}11$ tracked by mid-IR spectroscopy. Each series of overlaid spectra corresponds to one slide. For (A–C) spectra of slides coated with NHS-MHA were taken after the indicated time in $1\\mathrm{mg/mL}$ polymer solution without template; for (D) and (E) spectra of slides imprinted and cross-linked were taken after the indicated time stirring in DI water. Absorption peaks of interest are highlighted by grey shadows.  \n\nIn addition to PAH binding and extent of complex formation, the relative concentrations of the template, polymer and crosslinker require further tuning to yield a high SPR response. Different MIH synthesis parameters were evaluated with respect to the highest performance (i.e., \u0004RI/\u0004C[glucose]) by exposing the sensor to  \n\n$10\\mathrm{mg/mL}$ aqueous glucose solution. The results are summarized in Table 1.  \n\nHydrogel coatings immobilized in the absence of GPS-Ba serve to establish a baseline ‘control’ response to non-selective diffusion of glucose through the hydrogel. Utilizing PAH concentrations below $1\\mathrm{mg/mL}$ yielded non-reproducible batch-to-batch MIH membranes, therefore no data could be included in Table 1. In contrast, PAH concentrations approaching $2\\mathrm{mg/mL}$ (coating 8) and higher produced broad SPR dips (i.e. SPR coupling occurring at multiple conditions) due to coating heterogeneity within the plasmonically probed volume. Since measuring the response to the analyte is contingent upon precisely locating (in terms of wavelength) the SPR dip minima, broader dips render this procedure challenging. Coatings labeled 1 and 4 both serve as non-imprinted hydrogel (NIH) controls illustrating that non-selective absorption from a $10\\mathrm{mg/mL}$ glucose solution yields a $\\lambda_{S P R}$ shift of approximately $0.15\\mathrm{nm}$ . Addition of $0.05\\mathrm{mg/mL}$ GPS-Ba (coatings 2 and 5) did not improve the response to the analyte beyond levels already attributed to non-specific interactions. Raising the concentration of the template to $0.5\\mathrm{mg/mL}$ (coatings 3 and 6) resulted in the formation of sufficient template binding cavities to yield a statistically relevant $\\lambda_{\\mathsf{S P R}}$ shift. Comparison of MIHs formed with increasing levels of cross-linker (coatings 3, 6 and 7) indicate that structural rigidity of the hydrogel will influence the performance measured. From three epichlorohydrin concentrations investigated, it is evident that “softer” hydrogels obtained at lower concentrations do not exhibit the same level of response to $10\\mathrm{mg/mL}$ glucose as the two ‘more rigid’ counterparts. In part this may be due to the fact that a malleable carbon network is better capable of accommodating enriched analyte molecules within the free volume of the hydrogel, resulting in a lower degree of swelling. In contrast, a more rigid structure is forced to expand upon incorporation of the analyte since the carbon network in unable to re-adjust itself around the analyte.  \n\nTable 1 Measured response to $10\\mathrm{mg/mL}$ glucose in DI water for membranes prepared with different amounts of polymer, template and cross-linker.   \n\n\n<html><body><table><tr><td>Coating</td><td>PAH (mg/mL)</td><td>Epichlorohydrin (mg/mL)</td><td>GPS-Ba (mg/mL)</td><td>△入sPR (nm, μ±1o)</td></tr><tr><td>1</td><td>1.0</td><td>0.2</td><td>0.0</td><td>0.15 ± 0.03</td></tr><tr><td>2</td><td>1.0</td><td>0.2</td><td>0.05</td><td>0.18 ± 0.05</td></tr><tr><td>3</td><td>1.0</td><td>0.2</td><td>0.5</td><td>0.28 ± 0.03</td></tr><tr><td>4</td><td>1.0</td><td>0.5</td><td>0.0</td><td>0.12 ± 0.04</td></tr><tr><td>5</td><td>1.0</td><td>0.5</td><td>0.05</td><td>0.14 ± 0.03</td></tr><tr><td>6</td><td>1.0</td><td>0.5</td><td>0.5</td><td>0.38 ± 0.05</td></tr><tr><td>7</td><td>1.0</td><td>1.0</td><td>0.5</td><td>0.35 ± 0.07</td></tr><tr><td>8</td><td>2.0</td><td>0.5</td><td>0.5</td><td>0.27 ± 0.05</td></tr></table></body></html>  \n\n![](images/644c19536039b68f30377055c585045603642367ec20241ed05bb9c5d9a4f815.jpg)  \nFig. 2. (A) SPR response of imprinted (black circles) and non-imprinted (grey stars) hydrogel sensor to glucose in DI water. Results came from different slides and error bars stand for $95\\%$ confidence interval. Precision of SPR shift is shown by plus/minus standard deviation of the mean (black dots, usually $\\scriptstyle n=3$ ). (B) A TEM image of gold nanoparticles used. (C) SPR response of imprinted (black circles) and non-imprinted (grey stars) hydrogel sensor embedded with gold nanoparticles to glucose in DI water Results came from different slides and error bars stand for $95\\%$ confidence interval. Precision of SPR shift is shown by plus/minus standard deviation of the mean (black dots, usually $n=3$ ).  \n\nCross-linker concentration greater than $1\\mathrm{mg/mL}$ were not pursued in this initial contribution because a structurally rigid coating, less amenable to swelling, and therefore displaying smaller $\\lambda_{\\mathsf{S P R}}$ shifts, is anticipated. For the binding studies presented herein, a cross-linker concentration of $0.5\\mathrm{mg/mL}$ was used since it provided sufficient rigidity for selective cavities to retain their shape after template removal as well as enabling swelling of the MIH upon glucose re-binding.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3.2. Physical characterization  \n\nAs was previously mentioned, RI changes monitored by SPR spectroscopy are non-selective. Therefore, discrimination of $\\lambda_{\\mathsf{S P R}}$ shift induced by bulk RI changes associated with solutions containing different glucose concentrations (e.g. a false positive) from $\\lambda_{\\mathsf{S P R}}$ shifts resulting from selective analyte uptake, is achieved by employing MIH membranes with thicknesses greater than penetration depth $(d_{p})$ of surface plasmons (approximately $200-300\\mathrm{nm}$ [14]).  \n\nScanning electron micrographs acquired along fractured edges provide an approach for evaluating MIH thickness. By this method, MIH thickness ranged from approximately $0.8\\upmu\\mathrm{m}$ to $2.5\\upmu\\mathrm{m}$ . Therefore, \u0003SPR shifts recorded reflect refractive index changes within the MIH rather than in the bulk liquid. The micrograph also reveals superficial accumulations ranging from $1\\upmu\\mathrm{m}$ to $5\\upmu\\mathrm{m}$ in size atop the relatively uniform background. The origin of these features is still unknown though it is likely that they correspond to hydrogel agglomerations formed in solution and bound to the coated sensor during later stages of MIH synthesis.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.3. Glucose detection  \n\nEvaluation of MIH-coated sensors involved measuring glucose solutions with different concentrations. Sensor slides coated with MIH  but without gold nanoparticles reached equilibrium response to the analyte within 2 min and displayed an increasing $\\lambda_{\\mathsf{S P R}}$ shift with glucose concentrations below ${\\sim}5\\mathrm{mg/mL}$ (Fig. 2(A)).  \n\nAs was previously mentioned, control NIHs were prepared in exactly the same way as MIHs but without the template. In all measurements, the response obtained with NIH was lower compared to imprinted hydrogels. Furthermore, NIH sensors required glucose concentrations greater than $5\\mathrm{mg/mL}$ in order to register measurable shifts in $\\lambda_{\\mathsf{S P R}}$ . The difference in response between MIH and NIH suggest the presence of selective binding sites in the imprinted hydrogel, as well as indicating that non-specific interactions, such as surficial adsorption and non-specific diffusion of glucose, do not contribute significantly to the SPR response measured.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3.4. Addition of gold nanoparticles  \n\nThe interaction between metallic nanoparticles, especially gold nanoparticles, and freely propagating plasmons excited at continuous metal films has been previously described as a method for enhancing the SPR sensitivity [45–47,49–51,62]. In order to evaluate the influence of nanoparticles on MIHs, cysteamine-capped gold nanoparticles were embedded into the hydrogel by cross-linking the amine groups of the capping agent with unprotonated primary amines in PAH. An exemplary transmission electron microscopic image of the nanoparticles synthesized is shown in Fig. 2(B). A distribution study of the images recorded indicates that the gold nanoparticles have a diameter of $25\\pm8\\mathrm{nm}$ .  \n\nThe response of MIH-coated sensors containing gold nanoparticles to aqueous glucose solutions of different concentrations is summarized graphically in Fig. 2(C). Comparison with the results shown in Fig. 2(A) demonstrate that addition of gold nanoparticles produces a 10- to 15-fold improvement in the amplitude of the SPR signal as well as increased sensitivity at low glucose concentrations $(<1\\mathrm{mg/mL})$ . In contrast, control experiments with NIH membranes containing gold nanoparticles showed a comparatively small response to non-specific binding of glucose. The linear range of gold nanoparticles-MIH sensors decreased compared to MIH sensors without nanoparticles, as well as reaching saturation levels at lower glucose concentrations: $5\\mathrm{mg/mL}$ versus $10\\mathrm{mg/mL}$ for coatings with and without gold nanoparticles, respectively. A possible explanation for these observations is that the number of binding sites available inside the sensing layer is altered considerably by the incorporation of the nanoparticles. It may also be more difficult for glucose molecules to diffuse into the sensing layer during measurement when the layer is embedded with nanoparticles. Indeed comparison of the response of MIH and Au-MIH membranes to glucose shows that the presence of gold nanoparticles delays the onset of a stable response, as depicted in the sensorgrams shown in Fig. 3.  \n\nThe working concentration range of gold nanoparticles-MIH membranes cover the critical glucose concentrations in plasma tests [63,64] and urine glucose screening [65,66] for diagnosis of diabetes, and its upper limit is comparable to typical nonenzymatic glucose sensors reported [67–71].  From calibration, the limit of detection of the gold nanoparticle-MIH sensor in water was determined to be $0.02\\mathrm{mg/mL}$ $(S/\\mathsf{N}=3$ based on standard deviation of the MIH response in a blank solution) and a limit of quantification of $0.06\\mathrm{mg/mL}$ (based on 10 standard deviations of the MIH response in a blank solution) and a sensitivity of $1.9\\mathrm{nm}$ $\\mathrm{(mg/mL}$ glucose)−1 in deionized water.  \n\n![](images/833fbc634c4e8d651031ec33f8a576383e91a90ff882feff444deec185ec628b.jpg)  \nFig. 3. Exemplary sensorgrams of (A) MIH and (B) Au-MIH coated sensor detecting $1\\mathrm{mg/mL}$ glucose in water. The sensor was rinsed with (i) deionized water, (ii) $0.1\\mathrm{{M}}$ NaOH and (iii) $1\\mathrm{mg/mL}$  \n\nUpon glucose binding and MIH swelling, a red-shift in the resonant wavelength was observed, which is in sharp contrast to the blue-shift expected from the increased distance between the gold nanoparticles and the underlying gold film (so-called “gap-mode” [48,49,72]). SPR responses are enhanced by plasmonic coupling if the distance, d, between the two plasmon active entities is maintained within the radius of the nanoparticle or smaller [73]. For the nanoparticles utilized herein, $r\\sim13\\ensuremath{\\mathrm{nm}}$ . Considering that the MIH synthesis was carried out by mixing all components in one vessel, it is likely that the nanoparticles are randomly distributed within the $0.8\\upmu\\mathrm{m}$ thick membrane, and that most of them reside at $d>13\\mathrm{nm}$ · Therefore, the 10-fold increase in measured signal most likely rises from the increased bulk RI of the composite gold nanoparticles-MIH membrane.  \n\nIt is worth noting that the comparatively large error bars (on average approx. $\\pm0.15\\mathrm{nm}$ ) reported in Fig. 2(C) result from measurements taken with different sensors, providing an estimate of batch-to-batch variability as opposed to variability within the same sensor. Glucose response was observed to decrease during repeated cycles, though this is possibly associated with degradation of the coating by the 0.1 M NaOH washing step used to release the analyte and regenerate the MIH. Finally, Fig. 2(A and C) suggest a Langmuir adsorption behavior. Though at first glance it may appear to appropriately describe the MIH response to glucose, modeling of adsorption processes at imprinted matrices is complicated by the failure to satisfy two of the basic requirements: monolayer adsorption and binding sites homogeneity. The lack of consensus regarding a ‘correct’ isotherm used for imprinted matrices has resulted in a variety of models being invoked to explain the binding event [74–76].  Therefore, at this stage, modeling of glucose re-binding was deferred.  \n\n![](images/c13ab5ac2dd14f9ffda50e625291754c9f1da260dac0dd8f973798d239a411c2.jpg)  \nFig. 4. Sensor performances in presence of interferences. (A) SPR response of MIH sensor to $60\\mathrm{mM}$ aqueous phosphate only. (B) SPR response of MIH sensor to glucose added to $40\\mathrm{mM}$ aqueous phosphate solution in different concentrations (0.1, 0.2 and $0.5\\mathrm{mg/ml}\\cdot$ ). (C) SPR response of Au-MIH sensor to glucose (black circles), fructose (grey triangles) and sucrose (grey stars). Results were obtained from different MIH coatings. Precision of SPR shift is shown by plus/minus standard deviation of the mean (black dots, usually $\\scriptstyle n=3$ for glucose samples). Individual sucrose and fructose samples were not replicated.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 3.5. Interference studies  \n\nThe formation of recognition sites for glucose in the sensing hydrogel is facilitated by ionic bonding of protonated amines in PAH with phosphate groups in GPS-Ba. Since a significant amount of phosphate $(0.03\\substack{-0.06\\mathrm{M}})$ is present in urine [56] it is necessary to evaluate whether the presence of phosphate groups can interfere with the MIH ability to bind to glucose. Initial studies involving MIH coatings exposed to intermittent phosphate plumes did not show a net \u0003SPR shift (i.e., the signal returned to baseline levels immediately upon flushing with deionized water) indicating that phosphate groups do not permanently re-bind to available amines in PAH (Fig. 4(A)). Spiking $0.06\\mathrm{M}$ ammonium phosphate solutions with the analyte showed a response similar in magnitude to the SPR response of glucose in DI water suggesting that physiologically relevant levels of phosphate in urine are unlikely to interfere. Exemplary sensorgrams are depicted in Fig. 4(B), which show a net $\\lambda_{\\mathsf{S P R}}$ shift due to glucose re-binding.  \n\nAnother source of potential interferents for imprinted matrices rises from cross-reactivity with structurally related compounds. Hence, selective glucose recognition was examined by exposing the gold nanoparticles-MIH coatings to similar sugars. Fig. 4(C) summarizes the $\\lambda_{\\mathsf{S P R}}$ shift measured with fructose and sucrose solutions. Fructose is structurally related to glucose, yet induces a significantly smaller response suggesting that although fructose is capable of binding to some of the recognition sites, the MIH preferentially binds to the template. The response measured with sucrose is even smaller than that for fructose. Sucrose is larger than either glucose or fructose, therefore, it can be anticipated that hindered diffusion through the MIH will affected the response level in addition to size incompatibility with most of the recognition sites.  \n\nCross-reactivity between molecularly imprinted materials and compounds structurally related to the template is common and can be minimized by careful choice of synthetic parameters (e.g. solvent, starting monomers) [74,77]; with regards to glucose monitoring, fructose has been previously recognized as a potential interferent [32,53,78].  This presents a challenge for sensing platforms aimed at single-compound detection in complex media. An approach to mitigate cross-reactivity with molecularly imprinted materials involves the use of sensor arrays, wherein coatings with different specificities (analyte and interferents) are utilized and the response obtained is mathematically treated to deconvolute the analytic from the interfering signal [79].  \n\nIn addition to phosphate, urine also contains a number of molecular species with amine groups (urea, uric acid and creatinine). To test their effect on the MIH coatings, a mixture of these compounds at concentrations commonly found in urine [56] was prepared and presented to the sensor similarly to the phosphate experiments described above (except for replacing titrated phosphate solution with the mixture), and it was indicated by the results that these compounds showed no net affect either.  \n\n![](images/39d9c5e7dc03345ff69e5d4242b95d25a3a104742173b7b22723874442a90a73.jpg)  \nFig. 5. Response of (A) MIH and (B) Au-MIH coated glucose sensor in undiluted urine spiked with different concentration of glucose.  \n\nFinally, glucose detection in human urine was explored. The matrix resulted from combining multiple urine collections from a healthy, non-diabetic individual throughout one day, homogenizing any temporal variations in composition. The matrix was centrifuged to remove potential sediment and spiked with glucose at different amount. Fig. 5 shows the response of MIH coatings without and with gold nanoparticle to the spike urine. The measured response decreased significantly compared to sample solutions prepared with DI water. The limit of detection and limit of quantification for urine analysis with Au-MIH were determined to be $0.12\\mathrm{mg/mL}$ and $0.40\\mathrm{mg/mL}$ , respectively, with a sensitivity of approximately $0.34{\\mathrm{nm}}\\ ({\\mathrm{mg/mL~glucose}})^{-1}$ . There are three possible contributing factors, all acting to decrease the MIH sensitivity to glucose. PAA hydrogels undergo contraction when exposed to salt solutions due to increased osmotic pressure [80]. Therefore, it is possible that MIH coatings in urine are prevented from swelling when incorporating glucose to the same extent as in DI water. Similarly, it is likely that some of the binding cavities distort and collapse rending them incapable of interacting with the analyte. Additionally, to the extent that hydrogen bonding between glucose and the amine functional groups in the MIH influence sensitivity, increasing ionic strength decreases the amount of intermolecular hydrogen bonding [81].  \n\nThe limit of detection for the Au-MIH membranes $(0.12\\mathrm{mg/mL})$ is within levels anticipated for glucose content in the urine of healthy individuals $(0.06\\mathrm{-}0.15\\mathrm{mg}/\\mathrm{mL}[78,82\\mathrm{-}84])$ and is comparable to other recent reports [85–89].  The decreased dynamic range, however, renders quantification of glucose at elevated levels difficult. Considering that glucose levels can spike to over $6\\mathrm{{mg/mL}}$ [85] shortly after ingesting a meal and the sensor’s inability to differentiate between glucose concentrations above ${\\sim}1\\mathrm{mg/mL}$ , this first iteration the sensor would only reliably function for threshold sensing, discriminating between glucose levels in healthy or diabetic individuals. If needed, samples could be diluted to expand the dynamic range to higher concentrations. Done in an automated manner this would not significantly increase the variance of analyses at the expense of a greater dynamic range. Regardless, despite the current lack of sensitivity necessary for precise monitoring in urine, these results provide a first approximation of the achievable detection limits as well as highlighting some of the challenges rising from performing measurements in complex solutions.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# 4. Conclusion  \n\nA  SPR sensing system with hydrophilic molecularly imprinted hydrogel as recognition unit was developed for glucose monitoring. Swelling of the hydrogel sensing layer due to combination with glucose was tracked by SPR spectroscopy. While further refinements are necessary to improve sensitivity of the chemical recognition layer, the system displays potential as a specific detection method for glucose monitoring in a complex physiological fluid. Cooperation of gold nanoparticles has significantly enhanced the sensor’s response and sensitivity at low glucose concentrations. The sensor showed selective response to glucose compared to fructose and sucrose, and was capable to detect glucose spiked in deionized water at the $\\upmu\\mathrm{g}/\\mathrm{mL}$ level. Preliminary analysis of glucose in urine indicates that high ionic strength media may be disrupting the re-binding event, decreasing the MIH sensitivity.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 18,
+        "chunk": "# Acknowledgements  \n\nThe authors would like to thank Delaware’s EPSCoR program (grant no. DIBO312214) and the American Heart Association (N.M, grant no. 09POST2120014) for partial funding. W.P. acknowledges the National Natural Science Foundation of China for partial support (grant no. 60977055/61137005).",
+        "category": " References"
+    },
+    {
+        "id": 19,
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+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# 天然及复合海藻酸盐水凝胶改性和构建复合体系修复骨缺损",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# https://doi.org/10.12307/2022.310  \n\n范  谊，刘亚东，崔宇韬，刘  贺，田宇航，李少荣，王  淦，吴丹凯，彭传刚  \n\n投稿日期：2021-03-23  \n采用日期：2021-04-30  \n修回日期：2021-05-16  \n在线日期：2021-07-03  \n\n中图分类号：R459.9；R363；R364  \n\n文章编号：  \n2095-4344(2022)28-04532-07  \n文献标识码：A  \n\n![](images/d4f647374ea4bca2532eafd5a094a63bfbd470d4e456ba2bbf2e046aad31d282.jpg)  \n\n文题释义：  \n\n海藻酸盐：是一种存在于海藻类植物和细菌中的天然聚多糖形成的盐，其钠盐可溶，而与二价金属阳离子形成的螯合物(以海藻酸钙为代表)为不可溶性凝胶。在医药领域，海藻酸盐广泛应用于外科敷料、组织工程等的研究与临床实践中。  \n\n骨缺损：因为先天因素、创伤、感染和肿瘤等原因造成的骨组织缺失，是临床工作中的常见问题，常造成骨不连、骨折的延迟愈合以及局部功能障碍。目前骨缺损的治疗方法主要有植骨、Ilizarov技术(骨搬移技术)及Masquelet技术(膜诱导技术)等。",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 摘要  \n\n背景：作为一种骨组织工程的细胞支架材料，海藻酸盐水凝胶因其良好的生物相容性、可再生的特点受到关注，然而天然海藻酸盐水凝胶因降解缓慢、凝胶不稳定等缺陷使其在机体环境下可能无法实现预期的效果。因此，需要对天然海藻酸盐水凝胶进行改性及构建复合体系，以满足骨缺损修复所需的功能。  \n\n目的：介绍天然海藻酸盐水凝胶的结构及其改性策略，复合海藻酸盐水凝胶的构建策略，强调在不同的骨缺损修复中海藻酸盐水凝胶及其复合体系所需具备的各种功能，并总结当前的研究重点和展望未来的发展趋势。  \n\n方法：作者以“alginate hydrogel、bone defect、bone repair、海藻酸盐、骨缺损、骨修复”为检索词，检索1995-2021年PubMed、Web ofcience、Medline、万方、中国知网和维普数据库中的相关文献，筛选后对69篇文献进行分析。  \n\n结果与结论： $\\textcircled{1}$ 海藻酸盐水凝胶通过氧化及 $\\gamma$ 射线照射等处理，能够获得更快的生物降解性能，而不同的交联方式可以使其具有不同的化学结构。 $\\textcircled{2}$ 通过复合体系的构建，海藻酸盐水凝胶及其复合体系能够作为细胞、生物活性因子及药物的载体，可以单独或者联合其他支架使用。 $\\textcircled{3}$ 因为具备以上复杂的性能，海藻酸盐水凝胶及其复合体系在骨缺损修复中表现出良好的前景，在部分已有的研究报道中，实现了临界性骨缺损的完全骨桥接。海藻酸盐复合体系为骨修复提供了潜在的解决方案，即通过局部生物活性物质的控制性递送，实现骨缺损的加速愈合以及临界性骨缺损的愈合。 $\\textcircled{4}$ 在大节段及承重骨缺损的修复中，可以联合其他高机械强度的支架，在提供机械承重的同时，增强了其他支架的骨整合能力，而这些方案能够适应不同的骨缺损修复的要求。 $\\textcircled{5}$ 总体而言，海藻酸盐水凝胶及其复合体系在动物实验中已经显现出良好的促进骨组织修复效果，为骨组织工程修复骨缺损提供了潜在的途径，但目前尚缺少系统的临床试验，故距离其实际服务于临床工作，还需要更多的临床研究与探索。  \n\n关键词：海藻酸盐水凝胶；海藻酸盐；水凝胶；骨缺损；骨修复；骨组织工程；生物材料；综述",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# Modification of natural and composite alginate hydrogels and repair of bone defect with composite systems  \n\nan Yi, Liu Yadong, Cui Yutao, Liu He, Tian Yuhang, Li Shaorong, Wang Gan, Wu Dankai, Peng Chuangang  \n\nDepartment of Orthopedics, Second Hospital of Jilin University, Changchun 130041, Jilin Province, China   \nFan Yi, Master candidate, Physician, Department of Orthopedics, Second Hospital of Jilin University, Changchun 130041, Jilin Province, China   \nCorresponding author: Wu Dankai, MD, Chief physician, Professor, Doctoral supervisor, Department of Orthopedics, Second Hospital of Jilin University,   \nChangchun 130041, Jilin Province, China   \nCorresponding author: Peng Chuangang, MD, Associate chief physician, Associate professor, Master’s supervisor, Department of Orthopedics, Second Hospital   \nof Jilin University, Changchun 130041, Jilin Province, China  \n\n吉林大学第二医院骨科，吉林省长春市  130041  \n\n第一作者：范谊，男，1998 年生，重庆市人，汉族，吉林大学第二医院骨科在读硕士，医师。  \n通讯作者：吴丹凯，博士，主任医师，教授，博士生导师，主任，吉林大学第二医院骨科，吉林省长春市  130041  \n通讯作者：彭传刚，博士，副主任医师，副教授，硕士生导师，副主任，吉林大学第二医院骨科，吉林省长春市  130041https://orcid.org/0000-0001-7859-6631 ( 吴丹凯 )； https://orcid.org/0000-0001-5596-0285( 彭传刚 )  \n基金资助：吉林省财政厅项目(2019SCZT014)，项目负责人：吴丹凯；吉林省科技厅项目(20200404140YY)，项目负责人：吴丹凯；国家自然科学基金项目(81772456)，项目主要参与人：刘贺  \n引用本文：范谊，刘亚东，崔宇韬，刘贺，田宇航，李少荣，王淦，吴丹凯，彭传刚. 天然及复合海藻酸盐水凝胶改性和构建复合体系修复骨缺损 [J]. 中国组织工程研究，2022，26(28):4532-4538.",
+        "category": " References"
+    },
+    {
+        "id": 5,
+        "chunk": "# Abstract  \n\nBACKGROUND: As a cell scaffold material for bone tissue engineering, alginate hydrogel has attracted attention due to its good biocompatibility and renewable characteristics. However, due to the slow degradation and instability of natural alginate hydrogel, it may not achieve the desired effect in the body environment Therefore, modification of natural alginate hydrogel and construction of its composite system are needed to meet the needs of bone repair.  \n\nOBJECTIVE: To introduce the structure and modification strategy of natural alginate hydrogel, and the construction strategy of composite alginate hydrogel. It emphasizes the various functions of alginate hydrogel and its composite system in different bone defect repair, and summarizes the current research focus and prospects the future development trend.  \n\nMETHODS: With “alginate hydrogel, bone defect, bone repair, alginate, bone defect, bone repair” as the key words, the author searched related articles on PubMed, Web of Science, Medline, Wanfang, CNKI and VIP databases from 1995 to 2021. Totally 69 articles were analyzed after screening.  \n\nRESULTS AND CONCLUSION: (1) Through oxidation, ray irradiation and other treatments, alginate hydrogel can achieve faster biodegradability, and different crosslinking methods can make it have Through the of the comp stem, the alginate hydrogel and the composite system other stents. (3) Due to the above complex propertie esearch reports, complete bone bridging of critic air. Accelerated healing of bone defects an of large segment and load-bearing bon of other scaffolds while providing d its composite system have eering to repair bone defects. However, there tually serves clinical work.  \n\ney words: alginate hydrogel; alginate; hydrogel; bone defect; bone repair; bone tissue engineering; biomaterial; review  \n\nFunding: the Department of Finance Project of Jilin Province, No. 2019SCZT014 (to WDK); the Science and Technology Department Project of Jilin Province, No. 20200404140YY (to WDK); the National Natural Science Foundation of China, No. 81772456 (to LH)   \nHow to cite this article: FAN Y, LIU YD, CUI YT, LIU H, TIAN YH, LI SR, WANG G, WU DK, PENG CG. Modification of natural and composite alginate hydrogels and repair of bone defect with composite systems. Zhongguo Zuzhi Gongcheng Yanjiu. 2022;26(28):4532-4538.",
+        "category": " Abstract"
+    },
+    {
+        "id": 6,
+        "chunk": "# 0   引言   Introduction  \n\n由于创伤、肿瘤、感染及先天性异常造成的骨缺损是现在临床工作中所面临的常见问题[1-2]，并且随着社会老龄化的进展，对于骨缺损治疗的需求也将增加。自体骨移植、同种异体骨移植是常用的骨缺损治疗方法 [3]，但都存在着现阶段难以克服的局限性，例如自体骨移植骨供应来源有限、供区并发症以及需要二次手术 [4-6]，同种异体骨移植可能因免疫排斥反应导致的移植失败、因为不具有细胞成分而表现出低的骨诱导特性以及可能传播疾病等[7-9]。现有骨缺损修复方案不能提供令人满意的修复效果，使得替代途径的开发成为研究热点，骨组织工程因运而生。  \n\n骨组织工程为细胞提供了三维支架，结合生物活性因子以及药物，使其在机体内修复缺损组织，以获得功能性骨重建[10]，在此过程中，支架材料是重要的影响因素。水凝胶常被用作组织工程中的细胞支架材料，其内含有大量的水 [11]，一般来说具有良好的生物相容性。  \n\n水凝胶形成的三维网络状结构为细胞提供了支撑，并允许细胞在其内进行营养物质交换 [12]，起到类似于人体细胞外基质的功能。因为具备成本低廉、产量大及可再生等优点，海藻酸钠是组织工程中应用最广泛的天然水凝胶多糖 [13]。通过海藻酸盐的改性与其他成分的掺入，海藻酸盐水凝胶复合体系能够同时满足骨组织工程“细胞”“支架”及“生物信号”的要求[14-15]。  \n\n在此，文章首先阐述了天然海藻酸盐的主要结构及基本性能，简要说明了天然海藻酸盐运用于骨组织工程中的局限性，并以此为基础，讨论了天然海藻酸盐水凝胶的改性和设计策略，以实现骨组织工程所需求的功能化。复合的材料体系是组织工程材料的常用模式，文章也讨论了基于海藻酸盐水凝胶的复合体系的构建策略，最后简要综述了海藻酸盐水凝胶及其复合凝胶在骨缺损修复中的研究现状，以期为未来研究指明方向。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 1   资料和方法   Data and methods",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 1.1   资料来源  \n\n1.1.1   检索人及检索时间   由第一作者于 2020 年 12 月至 2021年3 月检索。  \n\n1.1.2   检索文献时限   1995-01-01/2021-03-22。  \n\n1.1.3   检索数据库   PubMed、Web of Science、Medline、中国知网、万方和维普数据库。  \n\n1.1.4   检索词   英文检索词：“alginate hydrogel，bone，defect，re-pair，regeneration，fracture，loss，tissue engineering”，中文检索词：“海藻酸盐、藻酸盐、藻酸、骨缺损、骨修复”。  \n\n1.1.5   检索文献类型   研究原著、综述、病例报告、荟萃分析和论著。  \n1.1.6   手工检索情况   无。  \n\n1.1.7   检索策略   在 PubMed、Web of Science、Medline 检索平台或数据库使用英文进行检索，在中国知网、万方、维普检索平台或数据库使用中文进行加检索，在检索过程中根据标题和摘要与文题的匹配情况确定是否筛选文献进行评价；以Web ofScience 为例，使用上述检索词为关键词，限定字段“主题”和“标题”，使用逻辑运算“AND”“OR”“NOT”连接检索词 ( 主要是“AND”)，另外考虑到不同文献中表述与关键词可能不完全相同，加入了通配符“\\*”，如alginate $^{*}\\mathrm{gel}^{*}$ 和 bone defect\\* 等，使用的各部分检索策略式见图1。  \n\n<html><body><table><tr><td>#10</td><td>1,252</td><td>主题：(alginate) AND 主题:(bone) NOT主题:(cartilage) 数据库=WOS，KJD，MEDLINE,RSCI,SCIELO时间跨度=2016-20 检索语言=自动</td></tr><tr><td>#9</td><td>569</td><td>主题: (alginate hydrogel*) AND 主题: (bone tissue engineering*) 数据库=WOS，KJD，MEDLINE,RSCI,SCIELO时间跨度=2016-21 检索语言=自动</td></tr><tr><td>#8</td><td>65</td><td>主题：(\"alginate hydrogel\") 精炼依据：文献类型：（REVIEW） 数据库=WOS,KJD,MEDLINE,RSCI,SCIELO时间跨度=2016-201 检索语言=自动</td></tr><tr><td>#7</td><td>1,130</td><td>主题：(\"alginate hydrogel\") 数据库=WOS,KJD，MEDLINE,RSCI，SCIELO时间跨度=2016-201 检索语言=自动</td></tr><tr><td>#6</td><td>184</td><td>主题：(\"alginate hydrogel\") AND 主题: (bone) 数据库=WOS，KJD，MEDLINE，RSCI，SCIELO时间跨度=2016-21 检索语言=自动</td></tr><tr><td>#5</td><td>146</td><td>主题：（alginate*gel*）AND主题：（fracture*） 数据库=WOS，KJD，MEDLINE，RSCI，SCIELO时间跨度=216- 检索语言=自动</td></tr><tr><td>#4</td><td>37</td><td>主题：(alginate*gel*）AND主题：(bone loss) 数据库=WOS，KJD，MEDLINE,RSCI，SCIELO时间跨度=2016-20 检索语言=自动</td></tr><tr><td>#3</td><td>455</td><td>主题：(alginate*gel*)AND主题：(bone regeneration*) 数据库=WOS,KJD,MEDLINE,RSCI,SCIELO时间跨度=2016-201 检索语言=自动</td></tr><tr><td>#2</td><td>289</td><td>主题：（alginate*gel*）AND主题：(bone repair*） 数据库=WOS，KJD，MEDLINE,RSCI，SCIELO时间跨度=2016-20 检索语言=自动</td></tr><tr><td>#1</td><td>265</td><td>主题：(alginate*gel*)AND主题：(bonedefect*) 数据库=WOS,KJD,MEDLINE,RSCISCIELO时间跨度=2016- 检索语言=自动</td></tr></table></body></html>  \n\n另外少量文献来自于对已经获取的文献进行研究或者质量评估时所涉及到的文中引文，利用文中的参考文献信息进行引文追踪所得，如文章中的Ref[20]。  \n\n1.1.8   检索文献量   各数据库初检得到研究原著、综述、临床研究及论著共237 篇。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 9,
+        "chunk": "# 1.2   入组标准  \n\n1.2.1   纳入标准   根据所得文章题目和摘要进行初步筛选，剔除重复文献，通过文献泛读和精读后得到海藻酸盐水凝胶在骨缺损修复中应用的相关实验研究、综述、临床研究及论著。  \n\n1.2.2  排除标准  发表时间过早的陈旧性文章；非海藻酸盐水凝胶以及海藻酸盐水凝胶的非骨缺损修复相关的研究；文章质量低，证据等级不够以及重复性研究。  \n\n1.3   文献质量评估   首先阅读所有检索文献，并对其主题和质量进行评估。筛除与此次研究无关的文献后，入选文献共 69 篇，见图2。  \n\n![](images/373efa0b2733e0977f56f96c9c87b5e94eac9711a86be57e88b2ab9ba0a13901.jpg)  \n\n文献检索和筛选结果的输出采用文献的引用形式，且保持格式一致性，文献的引用形式包括作者、题名、期刊名称、发表年代、卷数( 期数) 和页码等。  \n\n1.4   数据的提取   共检索到文献237 篇，其中英文216 篇，中文21 篇，经过质量评估排除 168 篇，纳入 69 篇符合标准的文献进行综述 [1-69]，简要介绍天然海藻酸盐水凝胶，讨论海藻酸盐水凝胶及其复合体系的设计策略，重点讨论了目前海藻酸盐水凝胶在不同骨缺损修复中的研究与应用情况。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 2   结果   Results  \n\n2.1   海藻酸盐水凝胶的设计策略  \n\n<html><body><table><tr><td>0天然海藻酸盐水凝胶</td></tr><tr><td>0改良的生物可降解性</td></tr><tr><td>0交联方式</td></tr><tr><td></td></tr><tr><td>O海藻酸盐复合水凝胶</td></tr></table></body></html>  \n\n2.1.1   天然海藻酸盐水凝胶   海藻酸盐是一种由 $a-L-$ 古罗糖醛酸 (G) 和 β-D- 甘露糖醛酸 (M) 两种结构单元依靠 1，4- 糖苷键连接形成主链的嵌段天然聚多糖，主要来源于海藻类植物 ( 褐藻 ) 与细菌 ( 固氮菌和假单胞菌 ) 中，是一种高产量的、可再生的天然生物材料 [16]。海藻酸盐主链由连续的 M 残基、连续的 G残基以及交替的 M 和 G 残基组成。一般来说，海藻酸盐及其水凝胶具有良好的生物相容性，其中海藻酸的钙、钠、铵、钾盐被美国食品药品监督管理局认定为 GRAS[17](Generally Recognizedas Safe，一般认可为安全 )，在伤口愈合、药物输送和细胞移植中的应用被广泛研究。  \n\n在组织工程中，生物材料为细胞提供了三维支架，作为细胞黏附、增殖及分化的环境。细胞支架应该是多孔网络状的结构，其内的细胞在与周围环境进行细胞物质交换的同时，也被提供了必要的空间，以沉积细胞外基质。海藻酸盐形成的水凝胶的三维网络结构与人体生理状态下的细胞外基质相似 [18]，是潜在的骨组织工程细胞支架材料。天然海藻酸盐水凝胶自身存在的缺陷，例如其在机体内表现的缓慢的生物降解，不易被细胞识别和黏附以及传统离子交联凝胶方式下所表现的凝胶结构不稳定等，限制了其在骨组织工程中的应用。因此，为实现其骨缺损治疗的应用，需要设计海藻酸盐水凝胶体系，包括改良的生物可降解性、交联方式的选择及复合水凝胶的构建等。  \n\n2.1.2   改良的生物可降解性   理想的组织工程细胞支架材料应随着组织再生的进程逐渐生物降解，过快的降解将导致细胞支架的崩塌，而过缓的降解将阻碍组织的正常修复，因为细胞只能将矿化基质沉积到其直接的周围环境中 [19]。一般生理情况下，因为缺乏降解海藻酸盐水凝胶的酶，哺乳动物体内的海藻酸盐水凝胶是难以降解的。有研究通过放射性定位实验发现，海藻酸盐进行肾脏清除的分子质量阈值约为 $48~\\mathsf{k D}^{[20]}$ ，市售的海藻酸盐分子质量为 $3.2\\substack{-400.0\\mathsf{k D}}$ ，所以即使完成了植入部位的生物降解，大分子质量的海藻酸盐分子也将汇集在脉管系统中难以酶解或排出，影响其远期安全性。因此，增强其生物降解性以及小分子质量化海藻酸盐是其组织工程应用的重要考虑因素。  \n\n最近的研究指出，海藻酸盐的氧化可以提高其生物降解性，高碘酸盐是其常用的氧化剂[21]。在一项海藻酸钠的氧化研究中，BALAKRISHNAN 等 [22] 通过在水 - 乙醇溶液和水溶液两种介质中使用高碘酸钠氧化海藻酸钠，发现在两种溶液介质中，海藻酸钠水凝胶随着氧化的进行而裂解，并且裂解产物的重均摩尔质量随着氧化体系中高碘酸钠浓度的增加而降低。在此氧化系统中，氧化和低分子质量化是一个协同的过程，是潜在的改性策略。另外，γ 射线照射也能够降低海藻酸盐分子质量，提高其在机体内的降解速率 [23]。以上 2 种提高海藻酸盐水凝胶生物降解性的方法都伴随着海藻酸盐主链的缩短，实现了小分子质量化，有利于海藻酸盐材料在机体内生物降解后的代谢排出，提升了其远期生物安全性。  \n\n2.1.3   交联方式   离子交联和共价交联是海藻酸盐水凝胶主要的两种凝胶方式。一般情况下，离子交联凝胶方式能在安全温和的条件下成胶。海藻酸盐( 主要是海藻酸钠) 与 ${\\mathsf{C a}}^{2+}$ 交联形成离子交联型水凝胶，其机制在于 ${\\mathsf{C a}}^{2+}$ 与海藻酸盐中的 4 个 G 残基进行配位，形成典型的“蛋盒”结构 [24]。除 ${\\mathsf{C a}}^{2+}$ 以外， $Z n^{2+}$ 、${\\mathsf{B}}{\\mathsf{a}}^{2+}$ 、 $\\mathsf{S r}^{2+}$ 和 ${\\mathsf{C u}}^{2+}$ 等二价金属离子也可以与海藻酸盐反应形成水凝胶 [25-27]。在体内液体环境下，离子交联型水凝胶容易因为二价金属阳离子的浸出从而导致水凝胶机械强度降低甚至水凝胶的解体 [28-29]，并且离子交联的凝胶方式容易因为快速地凝胶化而导致不均质水凝胶的产生，所产生凝胶的机械性能也难以控制 [30-31]，而有研究表明，凝胶不同的机械性能会导致不同的细胞谱系分化行为 [32]。一般来说，随着离子浓度的增加，离子交联型水凝胶的机械强度也会增加 [33-35]，但需要注意的是，已有证据表明，过高的离子浓度会表现出细胞毒性 [36]。为解决以上问题，不同的解决方案被提出。DIAZ-RODRIGUEZ 等 [37] 制备了 ${\\mathsf{C a}}^{2+}$ 交联水凝胶，在海藻酸钙水凝胶中加入了 $\\mathsf{C a C O}_{3}$ 晶体，$\\mathsf{C a C O}_{3}$ 的存在可以改善海藻酸盐水凝胶的长期稳定性，因为碳酸钙晶体的部分溶解会导致 ${\\mathsf{C a}}^{2+}$ 离子的释放，从而促进海藻酸盐凝胶的形成。SUN 等 [38] 通过原位缓慢释放 ${\\mathsf{D}}-$ 葡萄糖酸 $-d-$ 内酯水解产生的二价离子，成功交联了多巴胺修饰的海藻酸钠复合水凝胶，缓释的二价阳离子能使海藻酸盐形成均质的水凝胶，其中的羟基磷灰石可以帮助稳定水凝胶网络。基于相同的原理，其他能够提供缓释阳离子的成分，如磷酸钙等，也用于海藻酸盐复合水凝胶的添加材料以保持凝胶结构的稳定性。  \n\n共价交联型海藻酸盐水凝胶是海藻酸盐分子通过共价键结合形成的水凝胶，相比于离子交联型水凝胶，能够减少因离子浸出而导致的凝胶结构问题。共价交联型水凝胶同样存在着局限性，例如在制备共价交联型水凝胶的过程中，应该选择合适的交联剂和交联体系，以避免或减少因为有毒交联剂 ( 如四官能团聚酰胺胺 [39]) 的使用而造成的不良反应。基于仿海底贻贝黏附的设计，LEE 等 [40] 通过共价交联制备形成了海藻酸盐 - 邻苯二酚水凝胶，其细胞毒性小，可忽略，在流变测试下显示出均一的力学性能；相比于海藻酸钙水凝胶，海藻酸盐 - 邻苯二酚水凝胶在水溶液条件下具有更高的稳定性，并且在此凝胶中，通过调节凝胶中的海藻酸盐 - 邻苯二酚的质量分数，可实现对机械强度的调节。  \n\n因此，离子交联与共价交联的凝胶方式各有其优势和局限性，所以在设计构建水凝胶体系时需要结合所需功能进行综合考量。  \n\n2.1.4   海藻酸盐复合水凝胶   人体骨组织由约 $70\\%$ 的无机物和约$30\\%$ 的有机成分组成，从材料的角度考虑，骨为复合材料 [41]。羟基磷灰石是骨组织主要的无机物成分，基于仿生设计，羟基磷灰石常被加入水凝胶材料中以构建复合水凝胶体系，在骨缺损修复的初期，骨组织就能从修复材料中获得所需的钙源。在此体系中，羟基磷灰石浸出的 ${\\mathsf{C a}}^{2+}$ 可以帮助海藻酸盐水凝胶保持结构的稳定，还可以作为其他二价阳离子的载体，例如具有促进细胞成骨活性的 $S r^{2+[42]}$ 。另外，其他组分也被选择性地加入构建海藻酸盐复合水凝胶，以实现其特定的功能，如透明质酸作为细胞识别的位点，可以参与CD44 介导的细胞识别与黏附[43]，弥补天然海藻酸盐水凝胶在细胞识别和黏附中的不足，刺激结缔组织的修复；明胶来源于胶原蛋白，可以用来模拟正常骨组织细胞外有机成分[44]；壳聚糖凝胶带有正电荷，可以构建通过静电相互作用组装分层凝胶 [29]，也可以提供抗菌性能等。  \n\n2.2   海藻酸盐水凝胶修复骨缺损   在临床工作中，骨缺损的修复是一个复杂的问题，例如缺损的大小各异，形状不同，缺损所在的骨的生理功能也不一样。不同的骨缺损修复，需要修复体系具有不同的功能，如细胞、生物活性因子、药物的递送和承重等。  \n\n<html><body><table><tr><td>0细胞、生物活性因子、药物的控制性递送</td></tr><tr><td>O海藻酸盐水凝胶联合高强度支架修复骨缺损</td></tr><tr><td>·金属支架</td></tr><tr><td></td></tr><tr><td>·骨水泥</td></tr></table></body></html>  \n\n2.2.1   细胞、生物活性因子、药物的控制性递送   在一般情况下，骨组织固有的自我修复能力，使得骨组织能够在一定情况下完成缺损的自身修复 [45-46]。但在某些特殊情况下，例如临界性骨缺损时，骨组织难以完成自身修复。骨组织的再生修复是细胞与细胞基质、生物活性因子、药物等环境因素共同作用的结果，控制性地向骨缺损部位输送细胞和药物等生物活性物质以协助骨缺损修复是现阶段骨组织工程的常用策略。运用海藻酸盐水凝胶及其复合水凝胶温和、低机械强度的特点，在植入时能够避免对周围组织的侵入，同时完成目标细胞、生物活性因子以及药物的递送。  \n\n以骨髓间充质干细胞为代表的间充质干细胞是骨缺损治疗中常用的、能够进行成骨分化的细胞 [47]，同时，也被认为是骨缺损细胞疗法的金标准。有研究证据表明，利用简单的海藻酸钙水凝胶作为细胞包裹基质，向骨缺损部位输送间充质干细胞是一种有效的骨缺损修复促进途径[48]，见图3。  \n\n海藻酸盐 / 透明质酸复合水凝胶在细胞输送中以促进骨组织修复过程中体现出与简单海藻酸钙水凝胶类似的性能[43]。有研究利用海藻酸盐甲基丙烯酸甲酯、多巴胺、RGD 短肽和羟基磷图注：图A 为植入间充质干细胞负载的海藻酸钙水凝胶后大鼠肋骨缺损处的X 射线影像，从左到右分别为植入即刻、植入后2 周、4 周、8 周的影像，植入2 周，骨缺损区内无明显变化，植入后 4 周，缺损部位开始出现骨质痕迹，植入后 8 周，缺损部位大部分充满骨质，缺损两端相接；B 为对照组，植入的海藻酸钙水凝胶中不含间充质干细胞，缺损部位始终未见明显骨质修复，缺损两端逐渐封闭并硬化  \n\n![](images/8337a57427201f84c30e9afd7eea9432d411f5e25049e2ad5e87b4164796dd2b.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 11,
+        "chunk": "# 图3 ｜间充质干细胞负载的海藻酸盐水凝胶促进肋骨大节段缺损修复[48]  \n\n灰石合成了光交联的海藻酸基黏合剂水凝胶 [49]，并用其向免疫缺陷小鼠体内输送牙龈间充质干细胞，在异位成骨实验中形成了与天然骨相似的矿化结节。因此，基于细胞输送的治疗是骨缺损修复的有效途径。  \n\n目前，已经有多种生物活性因子，如骨形成蛋白、血管内皮生长因子、血小板衍生生长因子和转化生长因子 β 等，在研究中被用于促进骨组织再生。骨形成蛋白能促进间充质细胞定向分化为成骨细胞，是体内诱导骨和软骨形成的细胞因子，其中在骨缺损修复中最常用的是骨形成蛋白2。在一项大鼠股骨临界性骨缺损的修复实验中，KOLAMBKA 等 [50] 用纳米纤维网状管和海藻酸钠水凝胶构建了一种复合生长因子输送系统，纳米纤维网状管单独或在没有重组人骨形成蛋白 2 的海藻酸盐水凝胶存在下，不足以桥接大鼠股骨 $8\\:\\mathsf{m m}$ 的节段性缺损，而在海藻酸盐水凝胶中输送重组人骨形成蛋白 2 显著增加了骨形成，形成了完全性的骨桥接。另外，CHEN 等 [51] 的研究表明骨形成蛋白 7 能够促进人真皮成纤维细胞的成骨作用，并证实海藻酸盐水凝胶可以用于负载表达骨形成蛋白7 的腺病毒，实现基因治疗。  \n\n氧、微量营养物质等在组织中扩散的距离有限，因此，血管化在成功构建工程组织中起着关键性作用。血管内皮生长因子是一种强有力的血管生成因子，通过刺激内皮细胞的迁移和增殖，在血管网络的形成中起促进作用。KAIGLER 等[52] 研究发现，海藻酸钙水凝胶负载血管内皮生长因子的应用促进了早期的血管生成，而在较晚的时间点，它促进了骨的再生，并且这种结果可能来自于通过血管内皮生长因子的促进血管生成的作用，间接影响骨的愈合和成熟。  \n\n骨组织的再生涉及到多种生物活性因子的作用，这提示了适当递送多种生物活性因子可能是有效组织工程策略的前提。然而，在组织重建过程中，协调的生物“信号”并不是同时进行两种或更多种的活性因子同时递送那么简单[53-54]。例如，骨形成蛋白的作用存在于骨再生的各个阶段中，而血小板衍生生长因子主要作用在骨再生的早期，Bayer 等 [55] 设计了海藻酸盐水凝胶 / 磷酸钙复合支架以控制性释放骨形成蛋白 2 和血小板衍生生长因子 BB，证实，早期的血小板衍生生长因子 BB 递送能够有效地刺激支架的细胞浸润，且并不对延后释放的骨形成蛋白 2 的促进成骨细胞分化的能力产生抑制，证明了顺序释放的血小板衍生生长因子 -BB 和骨形成蛋白 2 有可能协同促进骨再生过程。  \n\n另外，海藻酸盐水凝胶可以作为生物活性物质和细胞相互作用的体系，用于生物活性物质与细胞的反应，并且可以实现生物活性物质与细胞的一起递送。在一项体外实验中，SEVARI等 [56] 在海藻酸盐水凝胶中加入了生物活性玻璃微粒和基质胶，结果表明，生物活性玻璃微粒和基质胶的浓度越高，牙髓干细胞成骨基因骨钙蛋白、矮小相关转录因子 2 和碱性磷酸酶的表达水平越高，矿化程度越高。GE 等 [57] 在海藻酸盐水凝胶中加入了基底膜蛋白、人胎盘Ⅳ型胶原、层粘连蛋白以及硫酸软骨素来模拟细胞外基质，发现，在含有骨形成蛋白 2 和基底膜蛋白的水凝胶微珠中发现了矿物质结节，且基底膜蛋白装载的微珠中的矿化结节更多，而在小鼠颅顶的临界性骨缺损植入中，含有骨形成蛋白 2 和基底膜蛋白的水凝胶微珠负载人间充质干细胞都有新生类骨组织，但无骨形成蛋白2 和基底膜蛋白的水凝胶微珠组则未见。  \n\n因此，海藻酸盐水凝胶在骨组织修复中的应用是因为其能够用作选择性地递送细胞、生物活性因子、药物等的载体。在递送过程中，海藻酸盐水凝胶保持了递送物质的生物活性，并且能够实现细胞、生物活性物质、药物的组合递送，时间顺序缓释等功能，见表1。  \n\n表1 ｜海藻酸盐水凝胶用作细胞、生物活性因子、药物的递送载体  \n\n\n<html><body><table><tr><td>递送体系</td><td>细胞</td><td>生物活性因子</td></tr><tr><td>海藻酸钙</td><td>骨髓间充质干细胞</td><td></td></tr><tr><td>海藻酸钙/明胶</td><td>间充质干细胞</td><td></td></tr><tr><td>海藻酸基黏合剂水凝胶/羟基磷灰石牙龈间充质干细胞-</td><td></td><td></td></tr><tr><td>海藻酸钙／明胶/羟基磷灰石</td><td>前成骨细胞</td><td>一</td></tr><tr><td>海藻酸钙/聚己内酯</td><td></td><td>重组人源骨形成蛋白2</td></tr><tr><td>海藻酸钙</td><td>一</td><td>血管内皮生长因子</td></tr><tr><td>海藻酸钙</td><td>一</td><td>基质细胞衍生因子1α</td></tr><tr><td>海藻酸钙／肝素微粒</td><td></td><td>血管内皮生长因子、骨</td></tr><tr><td>海藻酸钙/磷酸钙</td><td></td><td>形成蛋白2 血小板衍生生长因子</td></tr><tr><td>海藻酸钙/胶原蛋白膜</td><td>骨髓基质细胞</td><td>BB、骨形成蛋白2 骨形成蛋白2</td></tr><tr><td>海藻酸钙</td><td></td><td>骨髓间充质干细胞骨形成蛋白2、转化生</td></tr><tr><td>海藻酸钙/壳聚糖</td><td>人间充质干细胞</td><td>长因子β3 骨形成蛋白2</td></tr><tr><td>海藻酸钙/壳聚糖/磷酸钙</td><td>人真皮成纤维细胞</td><td>一</td></tr><tr><td>海藻酸钠／明胶/羟基磷灰石</td><td></td><td></td></tr><tr><td>海藻酸钠/壳聚糖/硫酸软骨素</td><td></td><td></td></tr></table></body></html>  \n\n海藻酸盐水凝胶的机械强度是凝胶成分、凝胶浓度及交联方式等条件综合的结果，但无论采用哪种途径，目前的海藻酸盐水凝胶都难以满足承重骨缺损修复所需要的机械强度。在修复体系中引入具有高机械强度的支架，例如金属支架、骨水泥、高强度聚合物等，使复合的海藻酸盐水凝胶体系能够表现更优的机械性能，对于大节段骨缺损( 由其是承重骨缺损) 的修复是必需的。  \n\n<html><body><table><tr><td>递送体系</td><td>药物</td><td>作用</td><td>参考文献</td></tr><tr><td>海藻酸钙</td><td></td><td>促进肋骨再生</td><td>[48]</td></tr><tr><td>海藻酸钙/明胶</td><td></td><td>促进骨缺损处的血管形成和[43] 骨再生</td><td></td></tr><tr><td>海藻酸基黏合剂水凝胶/羟基磷- 灰石</td><td></td><td>促进颌面部骨再生</td><td>[49]</td></tr><tr><td>海藻酸钙/明胶/羟基磷灰石</td><td></td><td>增强成骨细胞粘附和增殖</td><td>[58]</td></tr><tr><td>海藻酸钙/聚己内酯</td><td></td><td>形成临界性骨缺损的完全性[50]</td><td></td></tr><tr><td>海藻酸钙</td><td></td><td>骨桥接 增强血管再生和骨再生</td><td>[52]</td></tr><tr><td>海藻酸钙</td><td></td><td>招募内源性细胞进行骨缺损[59]</td><td></td></tr><tr><td>海藻酸钙／肝素微粒</td><td></td><td>修复 促进骨缺损处的血管再生和[53]</td><td></td></tr><tr><td>海藻酸钙/磷酸钙</td><td></td><td>骨再生 促进骨缺损处的骨再生</td><td>[55]</td></tr><tr><td>海藻酸钙/胶原蛋白膜</td><td></td><td>加速骨缺损愈合</td><td>[60]</td></tr><tr><td>海藻酸钙</td><td></td><td>促进骨缺损周围的骨形成</td><td>[54]</td></tr><tr><td>海藻酸钙/壳聚糖</td><td></td><td>加速骨缺损周围矿化及骨缺[57]</td><td></td></tr><tr><td>海藻酸钙/壳聚糖/磷酸钙</td><td></td><td>损修复 多西环素牙龈吓啉单胞菌和金黄色葡[61]</td><td></td></tr><tr><td>海藻酸钠/明胶/羟基磷灰石</td><td></td><td>萄球菌抗菌性 环丙沙星大肠埃希菌和金黄色葡萄球[62]</td><td></td></tr><tr><td>海藻酸钠／壳聚糖／硫酸软骨素 Sr*</td><td></td><td>菌抗菌性 促进骨缺损周围的骨形成</td><td>[63]</td></tr></table></body></html>\n\n表注：“递送体系”栏列举了海藻酸盐及其复合体系的组成情况；“细胞”“生物活性因子”“药物”栏表示在“递送体系”中选择性递送的物质；“作用栏”表示在“递送体系”和选择性递送物质的组合在体外和 ( 或 ) 动物实验中所表现出来的对于骨缺损修复的作用；“-”为不清楚  \n\n一个稳定的机械环境是必要的 [64]，并且承重骨缺损所需的早期承重也是必须考虑的问题。  \n\n金属支架：目前运用于体内的金属植入物主要为钛合金，其与机体能够较好的相容，但是骨整合能力欠缺，可能出现无菌性松动 [65]。裸钛 (Ti) 材料表现出一定的生物惰性，这阻止了生物分子的粘附，基于此问题，MUDERRISOGLU 等 [66] 开发了一种新型的由藻酸盐水凝胶，多孔 $\\mathsf{C a C O}_{3}$ 生物陶瓷和活性酶碱性磷酸酶组成的钛表面纳米结构生物活性涂层，对钛 (Ti) 表面进行改性，以构建骨刺激界面。在此涂层中，释放的碱性磷酸酶和 ${\\mathsf{C a}}^{2+}$ 增强了成骨细胞 MC3T3 的分化和增殖，并使其保持了良好的成骨活性，这表明海藻酸盐水凝胶良好的生物活性分子负载特性是促进界面骨整合的潜在途径。  \n\n2.2.2   海藻酸盐水凝胶联合高强度支架修复骨缺损   为周围组织提供机械支撑及承重是骨的重要生理功能。在骨缺损修复中，  \n\n虽然金属支架能够提供机械支撑，但骨再生不足时，骨缺损也难以愈合，基于此，生物活性分子、细胞等被引入钛合金支架中，以促进骨再生和骨长入。KUMAR 等[58] 在钛合金 $(\\mathrm{Ti}_{6}\\mathsf{A l}_{4}\\mathsf{V})$ 支架中引入负载了前成骨细胞 (MC3T3-E1) 的海藻酸盐 / 明胶 /羟基磷灰石凝胶，在该体系中，细胞具有良好的存活率，并且表现出相比于对照组( 孔板表面) 更高的碱性磷酸酶活性。因此，钛合金以及海藻酸盐水凝胶复合体系在提供良好机械支撑的同时，也是良好的细胞输送载体。  \n\n骨水泥：是骨科临床工作中常用的植入物，具有较高的机械强度，广泛用于骨缺损填充、感染控制和骨科移植物锚定。磷酸钙基骨水泥可以模制和原位注射形成支架，具有良好的骨传导性和生物可降解性 [67-68]。但是其存在着一些缺陷，例如不耐冲洗和较低的生物活性。XU 等 [69] 的研究数据表明，在海藻酸盐水凝胶 / 磷酸钙骨水泥复合支架中，骨水泥体内降解过程中释放的 ${\\mathsf{C a}}^{2+}$ ，为海藻酸盐凝胶结构的保持提供了二价金属阳离子，并且海藻酸盐凝胶的加入提高了骨水泥的耐冲洗性能，在体外细胞相容性实验中，骨水泥 / 海藻酸盐水凝胶组表现出了更高的人骨髓间充质干细胞增殖活性。  \n\n在复合体系中，海藻酸盐水凝胶也可以用于细胞、药物的递送。QIU 等[61] 合成了壳聚糖/ 磷酸钙骨水泥/ 多西环素支架，在体外实验中表现出超过 3 周的抗生素释放，并且呈现出随剂量增长的对牙龈卟啉单胞菌和金黄色葡萄球菌的抑菌性能。掺入复合支架的海藻酸盐水凝胶微珠负载了人牙周膜干细胞，表现出成骨谱系分化，有望应用于颅面、骨科中的感染性骨缺损的修复。  \n\n因此，在大节段骨缺损时，尤其承重骨缺损时，需要具有高机械强度的植入物以提供机械支撑。海藻酸盐水凝胶体系的加入可以提供生物活性因子、细胞等，并且增强了植入体骨整合及促进骨再生的能力，可以帮助加速骨的功能性重建。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3   讨论   Discussion  \n\n3.1   既往他人在该研究领域的贡献和存在的问题   海藻酸盐水凝胶作为一种天然的、可再生的生物材料，被广泛应用于外科敷料、组织工程材料。海藻酸盐水凝胶复合体系拥有合适的机械强度、生物活性及可降解性，在一定程度上能够适应骨组织工程的需要。良好的细胞包裹及生物活性物质输送性能使得各种细胞、药物和生物因子的组合输送得以实现。目前的海藻酸盐水凝胶复合体系尚值得更多的探索，如在凝胶方式中探索中，寻找到更优的骨组织工程材料解决方案，以更多地满足理想的组织工程材料的需求；对于细胞、生物活性因子和药物的更优组合，以获得更好的骨缺损修复结果；对于生物活性因子、药物的剂量进行优化，以减轻不良反应及减少治疗费用问题等。虽然在已有的部分报道中，以海藻酸盐水凝胶为基质的骨组织修复体系实现了骨缺损的完全的骨性修复，取得了令人兴奋的结果，但是目前基于海藻酸盐水凝胶及其复合体系修复骨缺损的实验研究集中在小、中型动物上，尚缺乏更新的足够的大型动物实验结果，基于临床的试验也值得更多的深入研究。总的来说，海藻酸盐为骨组织工程修复骨缺损提供了潜在的途径，但其实际服务于临床前，尚需更多的探索。对于海藻酸盐水凝胶作为一种骨组织工程材料的研究原著较多，且基本表现为海藻酸盐水凝胶体系对骨缺损修复的促进作用，但综述类研究相对较少。  \n\n3.2   作者综述区别于他人他篇的特点   对于海藻酸盐水凝胶修复骨缺损的综述，不论是中文还是英文的相类似的文献都较少，且中文的同题材综述年代久远，资料尚需更新；文章从海藻酸盐水凝胶及其复合凝胶的简单介绍，海藻酸盐水凝胶的设计策略 ( 以适应骨组织工程对骨缺损修复的需求 )，目前海藻酸盐水凝胶修复骨缺损的研究情况等几个大方面对“海藻酸盐水凝胶修复骨缺损”进行了较为系统的综述，能够总结现阶段的发展情况并为以后的研究与应用提供指导，同时也对“海藻酸盐水凝胶修复骨缺损”的证据进行了更新和汇总。  \n\n3.3   综述的局限性   文章发现目前对于海藻酸盐水凝胶用作组织工程材料的研究集中在基础研究领域，缺乏临床试验，故不能为临床工作提供参考。  \n\n3.4   综述的重要意义   更新并汇总了目前关于海藻酸盐材料在骨组织工程研究中的实验证据，较为系统地综述了目前关于海藻酸盐水凝胶促进骨缺损修复的研究及其进展，能够为进一步的实验提供参考，同时为作为一种良好组织工程材料的海藻酸盐水凝胶吸引更多的关注。  \n\n作者贡献：文章设计者为吴丹凯、彭传刚和范谊。资料收集者为范谊。范谊、刘亚东、崔宇韬、刘贺、李少荣、田宇航和王淦撰写论文。吴丹凯和彭传刚审校。  \n\n经费支持：该文章接受了“国家自然科学基金 (81772456)、吉林省财政厅项目 (2019SCZT014) 和吉林省科技厅项目 (20200404140YY)”的资助。所有作者声明，该经费支持没有影响文章观点和对研究数据客观结果的统计分析及其报道。  \n\n利益冲突：文章的全部作者声明，在课题研究和文章撰写过程不存在利益冲突。  \n\n写作指南：该研究遵循《系统综述和荟萃分析报告规范》(PRISMA声明)。  \n\n文章查重：文章出版前已经过专业反剽窃文献检测系统进行3 次查重。  \n\n文章外审：文章经小同行外审专家双盲外审，同行评议认为文章符合期刊发稿宗旨。  \n\n文章版权：文章出版前杂志已与全体作者授权人签署了版权相关协议。  \n\n开放获取声明：这是一篇开放获取文章，根据《知识共享许可协议》“署名- 非商业性使用- 相同方式共享 $4.0^{*}$ 条款，在合理引用的情况下，允许他人以非商业性目的基于原文内容编辑、调整和扩展，同时允许任何用户阅读、下载、拷贝、传递、打印、检索、超级链接该文献，并为之建立索引，用作软件的输入数据或其它任何合法用途。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 4   参考文献   References  \n\n[1] HO-SHUI-LING A, BOLANDER J, RUSTOM LE, et al. Bone regeneration strategies: engineered scaffolds, bioactive molecules and stem cells current stage and future perspectives. Biomaterials. 2018;180: 143-162.  \n\n[2] SHAKYA AK, KANDALAM U. Three-dimensional macroporous materials for tissue engineering of craniofacial bone. Br J Oral Maxillofac Surg. 2017;55(9):875-891.   \n[3] TOURNIER P, GUICHEUX J, PARE A, et al. A partially demineralized allogeneic bone graft: in vitro osteogenic potential and preclinical evaluation in two different intramembranous bone healing models. Sci Rep. 2021;11(1):4907.   \n[4] DIMITRIOU R, MATALIOTAKIS GI, ANGOULES AG, et al. Complications following autologous bone graft harvesting from the iliac crest and using the RIA:A systematic review. 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Biomaterials. 2018; 181:189-198.   \n[29]\t YAN HQ, CHEN XQ, FENG MX, et al. Layer-by-layer assembly of 3D alginate-chitosan-gelatin composite scaffold incorporating bacterial cellulose nanocrystals for bone tissue engineering. Mater Lett. 2017; 209:492-496.   \n[30]\t JEON O, BOUHADIR KH, MANSOUR JM, et al. Photocrosslinked alginate hydrogels with tunable biodegradation rates and mechanical properties. Biomaterials. 2009;30(14):2724-2734.   \n[31]\t JEON O, POWELL C, AHMED SM, et al. Biodegradable, photocrosslinked alginate hydrogels with independently tailorable physical properties and cell adhesivity. Tissue Eng Part A. 2010;16(9):2915-2925.   \n[32]\t HUEBSCH N, ARANY PR, MAO AS, et al. Harnessing traction-mediated manipulation of the cell/matrix interface to control stem-cell fate. Nat Mater. 2010;9(6):518-526.   \n[33]\t 赵德路, 铁朝荣, 王新, 等. 复合锶离子光交联海藻酸盐水凝胶 支架的机械和生物学性能 [J]. 中国组织工程研究 ,2019,23(18): 2880-2887.   \n[34]\t KAYGUSUZ H, EVINGUR GA, PEKCAN O, et al. Surfactant and metal ion effects on the mechanical properties of alginate hydrogels. Int J Biol Macromol. 2016;92:220-224.   \n[35] 张漫, 李昊, 徐婷, 等. 含锶交联藻酸钠凝胶对前成骨细胞黏附和 增殖的影响 [J]. 上海口腔医学 ,2019,28(2):123-127.   \n[36]\t AMIN AK, HUNTLEY JS, BUSH PG, et al. Chondrocyte death in mechanically injured articular cartilage-the influence of extracellular calcium. J Orthop Res. 2009;27(6):778-784.   \n[37]\t DIAZ-RODRIGUEZ P, GARCIA-TRINANES P, LOPEZ MME, et al. Mineralized alginate hydrogels using marine carbonates for bone tissue engineering applications. Carbohydr Polym. 2018;195:235-242.   \n[38]\t SUN XJ, LI ZY, CUI ZD, et al. Preparation and physicochemical properties of an injectable alginate-based hydrogel by the regulated release of divalent ions via the hydrolysis of d-glucono-delta-lactone. J Biomater Appl. 2020;34(7):891-901.   \n[39]\t PATIL SS, NUNE KC, MISRA RDK. Alginate/poly(amidoamine) injectable hybrid hydrogel for cell delivery. J Biomater Appl. 2018;33(2):295-314.   \n[40]\t LEE C, SHIN J, LEE JS, et al. Bioinspired, calcium-free alginate hydrogels with tunable physical and mechanical properties and improved biocompatibility. Biomacromolecules. 2013;14(6):2004-2013.   \n[41]\t SALGADO AJ, COUTINHO OP, REIS RL. Bone tissue engineering: state of the art and future trends. Macromol Biosci. 2004;4(8):743-765.   \n[42]\t LOURENCO AH, NEVES N, RIBEIRO-MACHADO C, et al. Injectable hybrid system for strontium local delivery promotes bone regeneration in a rat criticalsized defect model. Sci Rep. 2017;7(1):15.   \n[43]\t INGAVLE GC, GIONET-GONZALES M, VORWALD CE, et al. Injectable mineralized microsphere-loaded composite hydrogels for bone repair in a sheep bone defect model. Biomaterials. 2019;197:119-128.   \n[44]\t CECOLTAN S, STANCU IC, DRAGUSIN DM, et al. Nanocomposite particles with improved microstructure for 3D culture systems and bone regeneration. J Mater Sci-Mater Med. 2017;28(10):153.   \n[45]\t CUI YT, ZHU TT, LI D, et al. Bisphosphonate-functionalized scaffolds for enhanced bone regeneration. Adv Healthc Mater. 2019;8(23): e1901073.   \n[46]\t LOI F, CORDOVA LA, PAJARINEN J, et al. Inflammation, fracture and bone repair. Bone. 2016;86:119-130.   \n[47]\t ZHOU WY, LIN JX, ZHAO K, et al. Single-cell profiles and clinically useful properties of human mesenchymal stem cells of adipose and bone marrow origin. Am J Sports Med. 2019;47(7):1722-1733.   \n[48]\t 王俊钢, 李聪聪, 毛广显, 等. 骨生物材料复合骨髓间充质干细 胞异位成骨修复肋骨大段缺损[J]. 中国组织工程研究,2017,21(2): 182-186.   \n[49]\t HASANI-SADRABADI MM, SARRION P, POURAGHAEI S, et al. An engineered cell-laden adhesive hydrogel promotes craniofacial bone   \n[50]\t KOLAMBKAR YM, DUPONT KM, BOERCKEL JD, et al. An alginate-based hybrid system for growth factor delivery in the functional repair of large bone defects. Biomaterials. 2011;32(1):65-74.   \n[51]\t CHEN F, BI D, CAO G, et al. Bone morphogenetic protein 7-transduced human dermal-derived fibroblast cells differentiate into osteoblasts and form bone in vivo. Connecti Tissue Res. 2018;59(3):223-232.   \n[52]\t KAIGLER D, SILVA EA, MOONEY DJ. Guided bone regeneration using injectable vascular endothelial growth factor delivery gel. J Periodontol. 2013;84(2):230-238.   \n[53]\t SUBBIAH R, CHENG A, RUEHLE MA, et al. Effects of controlled dual growth factor delivery on bone regeneration following composite bone-muscle injury. Acta Biomaterialia. 2020;114:63-75.   \n[54]\t SIMMONS CA, ALSBERG E, HSIONG S, et al. Dual growth factor delivery and controlled scaffold degradation enhance in vivo bone formation by transplanted bone marrow stromal cells. Bone. 2004;35(2):562-569.   \n[55]\t BAYER EA, JORDAN J, ROY A, et al. Programmed platelet-derived growth factor-bb and bone morphogenetic protein-2 delivery from a hybrid calcium phosphate/alginate scaffold. Tissue Eng Part A. 2017;23(23-24): 1382-1393.   \n[56]\t SEVARI SP, SHAHNAZI F, CHEN C, et al. Bioactive glass-containing hydrogel delivery system for osteogenic differentiation of human dental pulp stem cells. J Biomed Mater Res Part A. 2020;108(3): 557-564.   \n[57]\t GE $\\scriptstyle\\mathbf{Q},$ GREEN DW, LEE DJ, et al. Mineralized polysaccharide transplantation modules supporting human msc conversion into osteogenic cells and osteoid tissue in a non-union defect. Mol Cells. 2018;41(12):1016-1023.   \n[58]\t KUMAR A, NUNE KC, MISRA R DK. Design and biological functionality of a novel hybrid Ti-6Al-4V/hydrogel system for reconstruction of bone defects. J Tissue Eng Regen Med. 2018;12(4):1133-1144.   \n[59]\t CIPITRIA A, BOETTCHER K, SCHOENHALS S, et al. In-situ tissue regeneration through SDF-1 alpha driven cell recruitment and stiffnessmediated bone regeneration in a critical-sized segmental femoral defect. Acta Biomateri. 2017;60:50-63.   \n[60]\t 郑旺, 高丽娜, 李西成, 等. 胶原蛋白膜包裹藻酸钙凝胶/ 骨髓基 质细胞/BMP-2复合体修复兔桡骨缺损[J].中国矫形外科杂志,2012, 20(4):363-366.   \n[61]\t QIU G, HUANG M, LIU J, et al. Antibacterial calcium phosphate cement with human periodontal ligament stem cell-microbeads to enhance bone regeneration and combat infection. J Tissue Eng Regen Med. 2021;15(3):232-243.   \n[62]\t SANGEETHA K, GIRIJA EK. Tailor made alginate hydrogel for local infection prophylaxis in orthopedic applications. Mater Sci Eng C-Mater Biol Appl. 2017;78:1046-1053.   \n[63]\t MA FB, LI SJ, RUIZ-ORTEGA LI, et al. Effects of alginate/chondroitin sulfate-based hydrogels on bone defects healing. Mater Sci Eng C-Mater Biol Appl. 2020;116:11212.   \n[64]\t DIMITRIOU R, JONES E, MCGONAGLE D, et al. Bone regeneration: current concepts and future directions. BMC Med. 2011;9:66.   \n[65]\t RAPHEL J, KARLSSON J, GALLI S, et al. Engineered protein coatings to improve the osseointegration of dental and orthopaedic implants. Biomaterials. 2016;83:269-282.   \n[66]\t MUDERRISOGLU C, SAVELEVA M, ABALYMOV A, et al. Nanostructured biointerfaces based on bioceramic calcium carbonate/hydrogel coatings on titanium with an active enzyme for stimulating osteoblasts growth. Adv Mater Interfaces. 2018;5(19):1800452.   \n[67]\t ZHAO LA, WEIR MD, XU HHK. An injectable calcium phosphate-alginate hydrogel-umbilical cord mesenchymal stem cell paste for bone tissue engineering. Biomaterials. 2010;31(25):6502-6510.   \n[68]\t WEIR MD, XU HHK, SIMON CG. Strong calcium phosphate cementchitosan-mesh construct containing cell-encapsulating hydrogel beads for bone tissue engineering. J Biomed Mater Res Part A. 2006; 77A(3):487-496.   \n[69]\t XU C, WANG XY, ZHOU J, et al. Bioactive tricalcium silicate/alginate composite bone cements with enhanced physicochemical properties. J Biomed Mater Res Part B. 2018;106(1):237-244.  \n\n( 责任编辑：WJ，ZN，ZJP)",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Fiber optic Bragg grating sensor based on hydrogels for measuring salinity  \n\nJun Conga, Xianmin Zhanga,\\*, Kangsheng Chena, Jian Xub  \n\naDepartment of Information and Electronic Engineering, Zhejiang University, Hangzhou 310027, China bPolymer Physics Laboratory, Center for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China  \n\nReceived 25 April 2002; received in revised form 7 July 2002; accepted 22 July 2002",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# Abstract  \n\nWe report a new type of optical salinity sensor with a fiber Bragg grating (FBG) coated with hydrogels. The sensing mechanism in this device is based on mechanical stress that is induced in the chemically sensitive water swellable polymers (hydrogels) coating when the water escapes from it. The stress in the hydrogels coating stretches and shifts the Bragg wavelength of the FBG. Varying the composition of the gel, the sensor can be used to response to different trigger stimulus. Here the sensors for measuring salinity are demonstrated.  \n\n$\\copyright$ 2002 Elsevier Science B.V. All rights reserved.  \n\nKeywords: Optical sensor; Fiber Bragg grating; Hydrogel; Sanility",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# 1. Introduction  \n\nRecently, a considerable research effort has been focused on fiber Bragg gratings (FBGs), particularly on systems using these devices for sensing applications. Because FBG is compact, simple in fabrication, and can be operated in a wavelength-coding manner, it has become an important component for optical sensing devices in measuring temperature and strains [1–4]. Hydrogels are crosslinked polymers which swell to an appreciable extent in water, and are considered as biocompatible materials. The water content depends on the polymer structure, and can be made responsive to environmental factors, such as inorganic salt concentration and $\\mathrm{\\pH}$ value [5,6]. Many research efforts have been done to study volume changes in response to different environmental factors, and develop sensors based on hydrogels for $\\mathrm{\\DeltapH}$ , soil water potentials and other chemical parameters [7,8]. Here we report a fiber Bragg grating sensor for measuring salinity using a water swellable hydrogel as the active sensing component. By modifying the hydrogel chemistry, parameters other than salinity can be detected using the same basic approach.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2. Principles of operation  \n\nThe basic principle of operation commonly used in a FBG based sensor system is to monitor the shift in wavelength of the reflected ‘‘Bragg’’ signal with the changes in the environment, e.g. strain, temperature. The Bragg wavelength, or resonance condition of a grating, is given by the expression:  \n\n$$\n\\lambda_{\\mathrm{B}}=2n_{\\mathrm{eff}}A\n$$  \n\nwhere $\\varLambda$ is the grating pitch and $n_{\\mathrm{eff}}$ is the effective refractive index of the fiber. With such a device, injecting a spectrally broadband source of light into the fiber, a narrowband spectral component at the Bragg wavelength is reflected by the grating.  \n\nHydrogels are a class of hydrophillic polymers which absorb water and swell without dissolution. They can absorb water and swell or emit water and shrink in the presence of a stimulus [5]. The swelling or shrinking actions of the hydrogels are readily converted to a mechanical response in the form of a force or pressure change which is the basis of the detection process in the present sensor.  \n\nThe basic configuration of the sensor is shown in Fig. 1. The device consists of a hydrogel-coated FBG. When the hydrogel absorbs water, mechanical expansion that occurs in the hydrogel pushes the clamps fixed on the FBG. The fiber is physically stretched and the grating period, L, expands which red shifts the Bragg wavelength. When the sensor is immersed in NaCl solution, the hydrogel will shrink and release the water. The Bragg wavelength will be decreased. Due to the fact that the residual stress that is induced depends on the NaCl concentration, the quantity of the Bragg wavelength shift can be directly related to the NaCl concentration.  \n\n![](images/8025b96dc777375253aa3734e862b253473f50b45f3dc6f94ca77d5b2019efb2.jpg)  \nFig. 1. Structure of the hydrogel-coated FBG sensor.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# 3. Sensor fabrication  \n\nA single mode fiber (Corning SMF28) was stripped of the polymer jacked and soaked with hydrogen at $140\\mathrm{MPA}$ and $150^{\\circ}\\mathrm{C}$ for 2 days. FBG was formed on the fiber under $248~\\mathrm{nm}$ KrF laser exposure through a phasemask. The preradiated fiber was subsequently annealed at $150^{\\circ}\\mathrm{C}$ for $24\\mathrm{h}$ to drive out the residual hydrogen. The grating reflectivity was $10\\mathrm{dB}$ at $\\lambda_{\\mathbf{B}}$ and the grating length was $1\\mathrm{cm}$ . Two clamps was adhered on two ends of a fiber grating by the cured epoxy, as shown in Fig. 1. The polyacrylamide hydrogel was prepared by free-radical solution polymerization initiated by a photoinitiator. The monomer, acrylamide (AAm), and the cross-linker, $N\\mathcal{N}^{\\prime}$ -methylene bisacrylamide (MBAAm), were purchased from Xingyi Chemical Cooperation, Beijing, China. AAm was frozen and recrystallized from solution in a mixed solvent of benzene and chloroform three times before use. MBAAm was recrystallized from its alcohol solution twice. The photoinitiator, $\\textsf{\\textsf{q}}$ -ketoglutaric acid (KGA, reagent from Wakolure Chem. Inst. Ltd.) was used without further treatment. The deionized water was redistilled for use as solvents. Before polymerization, the fiber grating was immersed in the mixture solution. Then the solution was polymerized under UV irradiation around $\\lambda=365\\mathrm{nm}$ .  \n\n![](images/18580a9340fbd0422ba4f4360828475c8ed9fe330c0fbea04031d7d48ec31be9.jpg)  \nFig. 2. The transmission spectra of the sensor.  \n\nAfter the hydrogel was polymerized, the sensor was immersed in water. The swelling hydrogel coating pushed the FBG, the Bragg wavelength of the grating was red shifted. Transmission spectra of the sensor are shown in Fig. 2. When the sensor was dipped into a NaCl solution, the shrink of the hydrogel caused the Bragg wavelength of the FBGs to blue shift. As a result, the location of the Bragg wavelength can be used directly to determine the NaCl concentration.  \n\n![](images/b0ae78fd1ba6d5093d0700b0c7d698ebdcc8ebc56901574f11629c41b31c5a8f.jpg)  \nFig. 3. Transmission spectra of the FBG sensor as a function of NaCl concentrations: (a) sensing time is $20\\mathrm{min}$ , (b) sensing time is $40\\mathrm{min}$ .",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 4. Result and discussion  \n\nThe experiments were conducted in dilute NaCl solutions. The sensor was immersed in $\\mathrm{\\DeltaNaCl}$ solution with different concentration $(0.1{-}0.7~\\mathrm{mol/l})$ ). It can be seen that the shifts of the Bragg wavelength were different for each treatment. Transmission spectra of the sensor as a function of $\\mathrm{\\DeltaNaCl}$ concentration are shown in Fig. 3. From the figure, the Bragg wavelengths of the sensors were blue shifted when the sensor was exposed to a higher NaCl concentration. The higher the $\\mathrm{\\DeltaNaCl}$ concentration of the solution is, the larger the Bragg wavelength of the sensor blue shift gets.  \n\nFig. 4 shows the NaCl concentration response of the sensor. When the sensor was immersed in the solution for a longer time $(40\\mathrm{min})$ , the response is improved. The sensitivity can be represented by the slope of the curve of Fig. 4 $:\\Delta(\\Delta\\lambda_{\\mathrm{Bragg}})/\\Delta c(\\mathrm{NaCl})$ . The sensitivity drops when the sensor was exposed to the solution with NaCl concentration higher than $0.5{-}0.7\\ \\mathrm{mol}/1$ .  \n\nResearches have shown that when certain cations, such as $\\mathrm{{Na}^{+}}$ , $\\mathrm{K^{+}}$ , ${\\mathrm{Ca}}^{2+}$ and $\\mathbf{Mg}^{2+}$ are diffused into the hydrogel matrix, they will introduced an anomalous behavior to the shrinking of the hydrogel [5]. The volume change of hydrogel is understood as a phase transition of the system consisting of the charged polymer network, counterions, and fluid [9]. The degree of volume change is based on the positive osmotic pressure of counterions, the negative pressure due to polymer–polymer affinity, and the rubber elasticity of the polymer network [10]. By modifying the hydrogel chemistry, the swelling and shrinking of hydrogel can be designed to be sensitive to other parameters, such as the pH value of aqueous solution [6]. The parameters other than salt concentration can be detected using the same basic approach.  \n\n![](images/9c1139dfe9b6b5847d1d8f3c83cef1f8176ae368fe1027280a8de673b4be7e83.jpg)  \nFig. 4. Bragg wavelengths of the FBG sensor as a function of $\\mathrm{\\DeltaNaCl}$ concentrations.  \n\nIf many Bragg gratings with different Bragg wavelength are located at intervals along a long optical fiber, and each grating coated with hydrogel, the sensor can be used as a quasi-distributed salinity detector, to monitor water quality in coastal areas or salinity level in wells and aquifers.  \n\nTo provide additional protection for glass fiber in aqueous environment, the fiber with FBGs can be coated with a thin gold or carbon film, forming a physical barrier to the diffusion of $\\mathrm{OH^{-}}$ groups to the glass structure [7]. The long-term stability of the crosslinks in the hydrogel matrix can be improved by adding $1\\%$ antioxidant inside the hydrogel matrix to reduce degradation due to radicals formation [7].  \n\nThe minimum detectable resolution of the NaCl concentration of the device is limited by two factors: the resolution of the detecting equipment and the discontinuous and slow volume changes in response to changes in the balance between repulsive intermolecular forces that act to expand the polymer network and attractive forces that act to shrink it. The latter can be reduced by using the hydrogels that can achieve large volume changes in response to the small changes of ion concentration of the solution [11].",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 5. Conclusion  \n\nIn conclusion, we have demonstrated the construction and test of a sensor for detecting salt concentration in water. The technique combines fiber Bragg gratings with chemically sensitive water swellable hydrogel. The mechanism for the sensors is the continuous volume phase transition of PAAm hydrogel when salt concentration is altered. Initial experiments have shown that the sensor is an efficient means of detecting $\\mathrm{\\DeltaNaCl}$ concentration. The sensor design can be readily adapted through modification of the gel chemistry with the same sensor construction to detect other chemical species.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 8,
+        "chunk": "# Acknowledgements  \n\nThis research was supported by National Nature Science Foundation of China (Grant No. 29904007), Zhejiang Provincial Science Foundation of China (Grant No. 699031), and SRF for ROCS, SEM, China.",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# References  \n\n[1] A.D. Kersey, M.A. Davis, H.J. Patrick, M. LeBlanc, K.P. Koo, C.G. Askins, M.A. Putnam, E.J. Friebele, Fiber grating sensors, J. Lightwave Technol. 15 (1997) 1442–1463.  \n\n[2] K.O. Hill, G. Meltz, Fiber Bragg grating technology fundamentals and overview, J. Lightwave Technol. 15 (1997) 1263–1276.   \n[3] M. Xu, H. Geiger, J. Archambault, L. Reekie, J. Pakin, Novel interrogating system for fibre Bragg grating sensors using an acousto-optic tunable filter, Electron Lett. 29 (1993) 1510– 1511.   \n[4] H. Patrick, G. Williams, A. Kersey, J. Pedrozzani, A. Vengsarkar, Hybrid fiber Bragg grating/long period fiber grating sensor for strain/ temperature discrimination, IEEE Photon Technol. Lett. 8 (1996) 1223–1225.   \n[5] T. Tanaka, I. Nishio, S.T. Sun, S.V. Nishio, Collapse of gels in electric field, Science 218 (1982) 467–469.   \n[6] J. Ricka, T. Tanaka, Swelling of ionic gels: quantitative performance of the Donnan theory, Macromolecules 17 (1984) 2916–2921.   \n[7] S. Hadjiloucas, D.A. Keating, M.J. Usher, W.C. Michie, B. Culshaw, M. Konstantaki, N.B. Graham, C.R. Moran, Hydrogel based distributed fibre optic sensor for measuring soil salinity and soil water potentials, Progress in Fibre Optic Sensors and Their Applications, IEE Colloquium on, London, UK, 1995, 9/1–9/6.   \n[8] W.C. Michie, B. Culshaw, M. Konstantaki, I. McKenzie, S. Kelly, N.B. Graham, C. Moran, Distributed pH and water detection using fiber-optic sensors and hydrogels, J. Lightwave Technol. 13 (1995) 1415–1420.   \n[9] T. Tanaka, Dynamics of critical concentration fluctuations in gels, Phys. Rev. A 17 (1978) 763–766.   \n[10] T. Tanaka, Gels, Sci. Am. 244 (1981) 124.   \n[11] E.S. Matsuo, T. Tanaka, Patterns in shrinking gels, Nature 358 (1992) 482–485.",
+        "category": " References"
+    },
+    {
+        "id": 10,
+        "chunk": "# Biographies  \n\nJun Cong was born in Shandong, China, in 1977. He received his BS degree in July 2000 from Department of Information and Electronic Engineering, Zhejiang University. He is currently pursuing his MS degree. His researches are interested in the field of polymer based sensors and fiber gratings.  \n\nXianmin Zhang was born in Zhejiang, China, in 1965. He received the BS and PhD degrees in physical electronics and optoelectronics from Zhejiang University, China, in 1987 and 1992, respectively. He was appointed associate professor of information and electronic engineering at Zhejaing University in 1994 and full professor in 1999. His research interests include optic fiber sensors and optic communication.  \n\nKangsheng Chen was graduated from Zhejiang University, China, in 1962. Since 1962, he has been a member of the faculty of Zhejiang University, where he is now a professor of the Department of Electronic Engineering. He was the Chairman during 1992–1996 of the department. His current interest includes theoretical modeling and numerical simulation of guided wave structures and optical communication.  \n\nJian Xu received the BS, MS and PhD degrees in polymer materials from Department of Chemistry, Chengdu University of Science and Technology, China, in 1982, 1985, and 1994, respectively. During 1985 and 1992, he was a lecturer of Beijing University of Chemical Technology, China. Since 1995, he is working at the Institute of Chemistry, Chinese Academy of Sciences, China. He is currently a professor and deputy director of the institute. His researches are interested in the field of polymer physics.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,102 @@
+[
+    {
+        "id": 1,
+        "chunk": "# Machine Learning-Assisted Design of Advanced Polymeric Materials  \n\nLiang Gao, Jiaping Lin,\\* Liquan Wang, and Lei Du",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# Cite This: Acc. Mater. Res. 2024, 5, 571−584  \n\n![](images/88396e30a8862fdad5ac3754833bd39c621a41cede3c163fe20b01dc47e4a92b.jpg)  \n\nACCESS  \n\nMetrics & More  \n\n![](images/3578bf835abc4a3eaa13a63ad9eea2bbf3667fe710472f7311cc20109bd3a322.jpg)  \nArticle Recommendations  \n\nCONSPECTUS: Polymeric material research is encountering a new paradigm driven by machine learning (ML) and big data. The ML-assisted design has proven to be a successful approach for designing novel high-performance polymeric materials. This goal is mainly achieved through the following procedure: structure representation and database construction, establishment of a ML-based property prediction model, virtual design and high-throughput screening. The key to this approach lies in training ML models that delineate structure−property relationships based on available polymer data (e.g., structure, component, and property data), enabling the screening of promising polymers that satisfy the targeted property requirements. However, the relative scarcity of high-quality polymer data and the complex polymeric multiscale structure−property relationships pose challenges for this ML-assisted design method, such as data and modeling challenges.  \n\nIn this Account, we summarize the state-of-the-art advancements concerning the ML-assisted design of polymeric materials. Regarding structure representation and database construction, the digital representations of polymers are the predominant methods in cheminformatics along with some newly developed methods that integrate the polymeric multiscale structure characteristics. When establishing a ML-based property prediction model, the key is choosing and optimizing ML models to attain high-precision predictions across a vast chemical structure space. Advanced ML algorithms, such as transfer learning and multitask learning, have been utilized to address the data and modeling challenges. During the ML-assisted screening process, by defining and combining polymer genes, virtual polymer candidates are generated, and subsequently, their properties are predicted and high-throughput screened using ML property prediction models. Finally, the promising polymers identified through this approach are verified by computer simulations and experiments.  \n\nWe provide an overview of our recent efforts toward developing ML-assisted design approaches for discovering advanced polymeric materials and emphasize the intricate nature of polymer structural design. To well describe the multiscale structures of polymers, new structure representation methods, such as polymer fingerprint and cross-linking descriptors, were developed. Moreover, a multifidelity learning method was proposed to leverage the multisource isomerous polymer data from experiments and simulations. Additionally, graph neural networks and Bayesian optimization methods have been developed and applied for predicting polymer properties as well as designing polymer structures and compositions.  \n\nFinally, we identify the current challenges and point out the development directions in this emerging field. It is highly desirable to establish new structure representation and advanced ML modeling methods for polymeric materials, particularly when constructing polymer large models based on chemical language. Through this Account, we seek to stimulate further interest and foster active collaborations for developing ML-assisted design approaches and realizing the innovation of advanced polymeric materials.",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# 1. INTRODUCTION  \n\nAdvanced high-performance materials are some of the cornerstones of human civilization development. The rapid progress of technology is closely tied to material innovation. The discovery of advanced high-performance materials primarily relies on labor-intensive trial-and-error methodologies. So far, numerous ground-breaking material innovations have emerged through countless iterations driven by the valuable experience and knowledge from materials scientists.1,2 However, the experience-driven methodology is time consuming, particularly when continuous improvements in the material performance are needed. A new methodology is highly demanded to achieve breakthroughs in material design and fabrication.  \n\n![](images/54d32517d9f96e8e40ccd20b2e0813912e344c77c2878bbbde706b54571f7500.jpg)  \nFigure 1. Development of research paradigms: (A) experimental and empirical, (B) model-based theoretical, (C) computer simulation, and (D) artificial intelligence (AI)-driven paradigms.  \n\n![](images/5ef5c3780d1439226d83a7d45e7b815206ca8a65adc6338e2f2f90455e5a4f02.jpg)  \nFigure 2. ML-assisted design procedure to obtain the desired polymeric materials: (A) structure representation and database construction, (B) establishment of ML-based property prediction model, and (C) virtual design and high-throughput screening.  \n\nThe paradigms of materials research have undergone four stages, known as the four paradigms,3−7 as illustrated in Figure 1. In the early stages, material innovations mainly relied on experiments and empiricism. Researchers intuitively described their experimental observations and summarized valuable experience and knowledge. This is an experimental and empirical paradigm, i.e., the first paradigm. Starting in the 17th century, theoretical models were built to generate more accurate scientific rules, thereby facilitating material development. This paradigm is named the model-based theoretical paradigm, i.e., the second paradigm. However, the theoretical models usually can only be solved analytically under some simplified conditions. Due to the temporal and spatial factors inherent in realistic material systems, some theoretical models have become extremely complex, making analytical solutions no longer feasible. Since the 1950s, the advancement of computer technology has enabled numerical solutions to some complex problems. Therefore, computer simulations of the materials, such as first-principles calculations, molecular dynamics, and Monte Carlo simulations, appeared, and they belong to the third paradigm.8,9 Since the 21st century, with the development of informatics and artificial intelligence (AI), a new research paradigm has emerged, the fourth paradigm, which is centered around the data-intensive science.10−12 Consequently, materials science has entered into the fourth paradigm by leveraging accumulated experimental and computational data. Big data analytics and machine learning (ML) have become indispensable tools within this new paradigm for analyzing massive data and constructing prediction models. So far, various data-driven tools and modeling methods have been employed in the fields of medical science, life science, and chemistry, facilitating the development of interdisciplinary methods such as medical informatics, bioinformatics, and cheminformatics.12−15 For example, by applying the fourth paradigm, various novel drug molecules can be virtually designed and screened out to satisfy the disease treatment requirements.16,17 However, in the material field, especially polymer material design, limited work based on the fourth paradigm has been reported. This Account focuses on the ML-assisted design of polymeric materials and summarizes the advancements and challenges in the emerging field of polymer informatics which is generated from the intersection of polymer science and informatics.  \n\nOver the past century, polymeric materials have been widely utilized in daily life and advanced manufacturing industries.  \n\nTable 1. List of Established Polymer Databases   \n\n\n<html><body><table><tr><td> no.</td><td>database</td><td>URL</td><td> origin of data</td><td> description</td></tr><tr><td>1</td><td>Khazana</td><td>https://khazana.gatech.edu/ dataset/</td><td>computational</td><td>thermoplastic; mechanical, thermal, electrical properties</td></tr><tr><td>2</td><td>PolyInfo</td><td>https://polymer.nims.go.jp/</td><td>empirical</td><td>thermoplastic; mechanical, optical, thermal, rheological properties</td></tr><tr><td>3</td><td>and database</td><td> Polymer property predictorhttps://pppdb.uchicago.edu/</td><td>empirical</td><td>Flory-Huggins parameter, glass transition temperature, binary polymer solution cloud point</td></tr><tr><td>4</td><td></td><td> Material properties database https://www.makeitfrom.com/</td><td>empirical/computational</td><td>thermoplastic, thermoset, rubber; mechanical, thermal, electrical properties</td></tr><tr><td>5</td><td>database</td><td>CROW polymer propertieshttps://polymerdatabase.com/</td><td>empirical/computational</td><td>thermoplastic, rubber, fiber; physical, thermal properties</td></tr><tr><td>6</td><td>PI1M</td><td>https://github.com/ RUIMINMA1996/PI1M</td><td>computational</td><td>virtual polymers; physical, thermal, electrical properties</td></tr><tr><td>7</td><td>Dortmund database</td><td>https://ddbst.com/</td><td>computational</td><td>physical properties, phase equilibrium data</td></tr><tr><td>8</td><td>AI plus Polymers</td><td>https://polymergenome.ecust. edu.cn/</td><td> empirical/computational</td><td>thermoset, thermoplastic; physical, mechanical, thermal, electrical properties</td></tr></table></body></html>  \n\nThe production scale of polymeric materials has surpassed that of the steel industry.18 The polymer properties can be regulated by their chemical structures and morphologies, and almost infinite design spaces are available. Significant efforts have been devoted to improving their performance; however, the existing approaches are time consuming and costly. An efficient new methodology is highly desired. In the emerging field of polymer informatics, the ML-assisted design strategy of polymeric materials can well address the challenge of performance improvement in the vast chemical space by utilizing informatics tools, including big data and ML algorithms.19,20  \n\nThe ML-assisted design of polymeric materials can be achieved through the following process: structure representation and database construction, establishment of a ML-based property prediction model, virtual design and high-throughput screening (Figure 2). The key lies in training ML prediction models that provide a quantitative structure−property relationship (QSPR) based on available polymer data (e.g., structure, component, and property data), enabling the screening of promising polymeric materials that satisfy the specific targeted property requirements. However, compared with metals and inorganic materials, the polymers possess unique multiscale structural characteristics. The polymer performance is determined by polymer structures (e.g., molecular weight and its distribution) and aggregation structures (e.g., crosslinking, crystallization, orientation, and microphase structures). This poses challenges for the data analysis and the ML prediction modeling tasks for polymeric materials.  \n\nIn this Account, we summarize the advancements achieved regarding the ML-assisted design of polymeric materials and emphasize the intricate nature of structure representation, property prediction, and structural design arising from the complex polymeric multiscale structures. Moreover, we discuss the challenges of the ML-assisted materials design approach and the development directions in the polymer informatics field.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2. STRUCTURE REPRESENTATION AND DATABASE CONSTRUCTION  \n\nThe digitization of polymer structures and the construction of a polymer database are the first steps to support the establishment of ML prediction models. After undergoing feature engineering, the digital representations of structures can serve as the inputs for training. Note that simultaneously improving the quality and quantity of the data is essential during the database construction process to ensure adequate consistency and availability. This section discusses the polymer data sources, the digital representation methods of polymer structures, and the database construction methods.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2.1. Polymer Data Sources  \n\nData sources include the literature, public databases, handbooks, theoretical calculations, and computer simulations.20−22 Over the past century, an extensive catalog of polymers was synthesized and their corresponding properties were examined, resulting in a large amount of structure−property data. To date, several databases have been established to compile the existing polymer data. These databases can be utilized as data sources. Table 1 provides an overview of the databases that primarily focus on polymer structure−property data. For example, the PolyInfo database catalogs experimental data for thermoplastic polymers, while Ramprasad et al. utilized computer simulation data to construct the Khazana database. Note that the polymer databases listed in Table 1 are mainly focused on thermoplastics. Recently, we established a platform named AI plus Polymers, which mainly focuses on thermosetting resins and encompasses about 150 000 property data for over 34 000 polymer structures. Such a comprehensive database covers a broader space of polymer structures and properties, providing data for database construction, especially for that of thermosetting resins.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.2. Polymer Structure Representation  \n\nThe polymeric multiscale structures, which encompass repeating unit chemical structures, chain structures, and aggregation structures, necessitate rational and accurate digital representations to ensure the accuracy of the established ML property prediction models.11 Drawing inspiration from the digital representation methods employed for small molecules, various methods have been utilized to digitally represent the structures of polymers. These methods include text-based simplified molecular input line entry systems (SMILES), graph- and fingerprint-based approaches (e.g., Morgan, PubChem, and Daylight fingerprints), as well as 3D geometry-based methods.23−25 The polymer chain structures are generally represented by the chemical structures of their repeating units. After digital representation, descriptors that describe the topological and chemical information of structures are obtained and serve as inputs for training a ML prediction model. In addition, after data preprocessing, the polydispersity information of polymers can also serve as model inputs to improve the accuracy of the ML prediction model.  \n\n![](images/3c72bd7eace2143b60d4c1bd70655f00a1c0c5bf61d475ebdb19559c0c673ee8.jpg)  \nFigure 3. Structure representation methods for polymers: (A) text-based SMILES representation, (B) molecular fingerprint representation, (C) molecular graph representation for the repeating units or monomers of polymers, and (D) newly developed polymer fingerprint representation based on a combination of molecular fingerprints and periodic graphs. (B) Reproduced with permission from ref 23. Copyright 2022 American Chemical Society. (C) Reproduced with permission from ref 25. Copyright 2023 Royal Society of Chemistry.  \n\nFor example, the text-based SMILES representation method encodes chemical structure information into a text form by converting it into SMILES strings (Figure 3A).24 ML models can be trained on these representations to learn the features of molecular structures.26 Molecular fingerprint is a representation method based on chemical structure segments, which converts molecular structure information into binary code.23 The 0 or 1 of each fingerprint indicates whether a certain chemical feature is present in the given molecule, such as atoms and bonds. Recently, the molecular fingerprint method has been extended from a simple 2D model to a 3D representation model. For example, Axelrod et al. first constructed the molecular fingerprint elements $\\vec{h}$ and subsequently embedded them with the statistical weight $p$ to generate a new fingerprint $\\vec{q}$ . Then, they trained deep learning (DL) models with an attention mechanism to yield the final comprehensive fingerprint $\\vec{Q}$ by combining the fingerprints $\\vec{q}$ (Figure 3B).23 This method enables accurate 3D fingerprint representations of molecular structures to be obtained, which is significantly better than 2D methods and holds promise for accurately predicting polymer properties.  \n\nThe molecular graph is a representation method that transforms the chemical structure into a graph, where atoms and bonds are represented as nodes and edges, respectively.23,25 The topological characteristics of a molecular structure are digitized through the connectivity of nodes and edges in the graph. A feature matrix is defined to capture atomic feature information, and an adjacency matrix is defined to reflect chemical bond feature information. For example, we utilized the molecular graph method to represent the monomer of polycyanurate resins.25 After defining atom feature matrices and adjacency matrices, we utilized a graph-based selfsupervised learning framework to learn the low-dimensional representations of monomers and found that the gated attention network performs best among the graph neural network (GNN) models (Figure 3C). Subsequently, we constructed the ML prediction models for hygroscopicity, coefficient of linear thermal expansion (CLTE), and tensile modulus and screened out the high-performance thermosetting polycyanurates.  \n\nHowever, applying these digital representation methods to polymeric structures is subject to certain limitations.23,27−29 For example, SMILES cannot capture the 3D structure and chain information of polymers and may exhibit ambiguity or nonuniqueness when representing complex polymer structures. Molecular fingerprints are unable to adequately capture certain physical information that is inherent in molecular structures and are sensitive to conformation variations, thereby resulting in the instability of representations. Therefore, considering the characteristics of polymer chains and aggregation structures and developing new structure representation methods have become a consensus in the field of polymer informatics. For example, BigSMILES, an extended form of SMILES, offers a more rational representation of polymers, especially for long chain structures and branching structures.28 BigSMILES introduces new symbols and rules, such as using the $^{\\omega}{\\boldsymbol{\\S}}^{\\prime\\prime}$ symbol to represent connections or branch points, thereby partially incorporating the chain structure information into the digital representations.  \n\nRecently, we proposed a representation method based on periodic fingerprints, namely, polymer fingerprints. As illustrated in Figure 3D, this method extracts features, such as chemical bonds, atoms, and molecular substructures from repeating units, and converts them into fixed-length fingerprint vectors. Through a combination and embedding process with an adjacency matrix, the fingerprint vectors are periodically augmented to attain digital representations of the polymer chain structures. This polymer fingerprint method can be integrated with GNN, exhibiting its scalability with the DL models. For example, by incorporating structural chemical information extracted from other representation methods (e.g., the text-based SMILES representation) into the polymer fingerprint vectors, more accurate digital representations at both the molecular scale and the chain scale can be achieved. Additionally, the high-level structural information of polymers is taken into account in our recent work. For example, we proposed a representation method for polymer cross-linking structures in which the cross-linking density is described based on classical gelation theory to capture the cross-linked features.26 By utilizing such a representation method, we obtained the ML models that can predict the moduli, strength, and elongation at break for the cured epoxy thermosets and screened out the high-performance epoxy resins.  \n\nFeature engineering, a crucial step following digital representation, aims to extract meaningful features from the primary representations for training ML prediction models. This process can reduce the dimensions of features and simultaneously improve the efficiency and accuracy of ML modeling.30 There is a series of descriptors and structural features associated with polymer properties. Descriptors are numerical features derived from atoms, molecules, or chain structures, such as molecular weight, charge distribution, and polarity, which can be extracted using RDKit Python tools. The structural features encompass geometric or topological characteristics, including bond lengths, bond angles, torsion angles, and the number of rings. Various statistical methods can be utilized for feature selection and dimensionality reduction, such as principal component analysis (PCA),29 linear discriminant analysis (LDA),31 and least absolute shrinkage and selection operator $(\\mathrm{LASSO})^{26}$ methods. For example, we developed a gate- and attention-augmented graph convolutional network $\\big(\\mathrm{GCN+a+g}\\big)$ to convert 1081 molecular descriptors of epoxy into an 8-dimensional vector.26 This dimensionality reduction method not only significantly incurs a reduced computational cost but also improves the accuracy of ML models for predicting epoxy thermoset properties.  \n\nNew representation methods that take into account the characteristics of polymeric multiscale structures are desirable to be developed. It is necessary to establish the multiscale descriptors to comprehensively describe the multiscale structures of repeated units, polymer chains, crystallization, cross-linking, and other aggregation structures. For example, the performance of organic photovoltaic (OPV) materials is determined by their multiscale structure, such as the crystallization or orientation of donors/acceptors and the morphological structures of crystalline domains. These complex multiscale structures should be rationally and accurately digitized for training the ML models that can precisely predict the properties of OPV materials. Therefore, comprehensively considering the polymeric multiscale structures during the digital representation process is critical to achieving accurate ML prediction for the polymeric materials with complex structure−property relationships.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.3. Polymer Database Construction  \n\nConstructing high-quality data sets is an essential step before conducting data analysis, property prediction, and structural design. However, the structure−property data of polymeric materials exhibit multisource isomerous characteristics in terms of their sources (including experimental and computational data) and types (including numerical values, spectra, and images). These multisource isomerous data sets may contain significant deviations. Therefore, before establishing prediction models, rigorous data cleansing operations should be carried out to improve data availability.31,32 For example, methods such as text similarity testing and entity recognition can be used to standardize data, and $N$ -fold cross-validation (i.e., leave-one-out cross-validation) can be utilized to identify and discard outliers.22,25 By employing the above methods for processing polymer data, the consistency and availability of the constructed polymer database can be ensured.  \n\nTo date, significant advancements have been made in terms of structure representation and database construction for polymeric materials; however, some long-standing issues still require attention. Due to the vast structural diversity of polymers, the amount of currently available data is relatively limited.5,20 Sometimes the polymer property data are of low quality, and the targeted property data are scarce. These issues pose nonnegligible data challenges for the ML-assisted design of polymeric materials. These challenges can be addressed by effectively utilizing computer simulation data or by generating a large amount of high-quality data through high-throughput experiments.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 8,
+        "chunk": "# 3. ESTABLISHMENT OF ML PREDICTION MODELSFOR POLYMER PROPERTIES  \n\nThe establishment of a property prediction model is pivotal for polymer design tasks because it determines the accuracy of virtual design results. Various ML algorithms have been employed to establish property prediction models.33 The key is choosing appropriate algorithms and optimizing the model, aiming to achieve high-precision predictions across a vast chemical structure space. The mainstream modeling approaches include Gaussian process regression (GPR), neural networks, decision trees, support vector machines, etc. For example, GPR is a nonparametric Bayesian regression method that has been widely applied to construct ML models for material structure−property relationships. Random forest algorithm, based on the decision tree model, demonstrates excellent generalizability and can be utilized for classification and regression modeling tasks. The neural network is a modeling method that mimics the human brain. Through the neuron connections and the information transfers in the input layer, hidden layer, and output layer, this modeling method can be utilized for data analysis and prediction.  \n\n![](images/6759b80ee7329efa3686d6401318377379bd8a00d79b51200f6fab3f1937d6ca.jpg)  \nFigure 4. Establishment of the GPR prediction models of polycyanurate resins by a multifidelity learning method on experimental and simulation data. (A) Modeling framework containing the graph-based representation method and multifidelity learning. (B−D) Model performance of the polycyanurate resin properties: (B) hygroscopicity, (C) coefficient of linear thermal expansion (CLTE), and (D) tensile modulus. Reproduced with permission from ref 25. Copyright 2023 Royal Society of Chemistry.  \n\nThe neural networks that contain multiple hidden layers and complex hyperparameters, i.e., deep neural networks, can achieve deep learning (DL) modeling. For example, convolutional neural network (CNN) and graph neural network (GNN) are representative deep neural network models employed to establish DL prediction models of material properties. Recently, various advanced ML algorithms have been successfully applied in the fields of chemical informatics and bioinformatics, especially reinforcement learning and transformer-based chemical language modeling methods. When combining the developed structure representation methods suitable for polymers, e.g., polymer fingerprint and BigSMILES, these advanced modeling methods can be applied to establish the prediction models of polymers.  \n\nMoreover, when dealing with some sparse and low-quality polymer data, it is difficult to construct accurate ML prediction models. To address this issue, advanced ML algorithms, such as transfer learning and multitask learning, have been employed. Transfer learning and multitask learning are indeed powerful modeling methods that can leverage knowledge from related domains or tasks to improve the model performance in a target domain even with limited data. For example, transfer learning involves pretraining a model on a relatively large data set of well-studied polymers and then fine tuning it on a smaller target data set about the desired properties, enabling the model to learn relevant patterns and relationships more efficiently.  \n\nRecently, we utilized GPR to establish the prediction models for polycyanurate properties. During the training process, due to the scarcity of experimental data, we leveraged computer simulations to obtain the polycyanurate properties and developed a multifidelity learning method to effectively map low-quality simulation data to high-quality experimental data (Figure 4A).25 Within this framework, the surrogate function $Y_{\\mathrm{H}}(X)$ of the high-quality data depends on the surrogate function $Y_{\\mathrm{L}}(X)$ of the low-quality data and their difference $Y_{\\mathrm{D}}(X)$ . For thermosetting polycyanurate resins, some property data are limited due to the difficulties of chemical synthesis, for example, hygroscopicity, thermal expansivity, and modulus data of polycyanurates. We calculated the properties of crosslinked polycyanurate structures by simulations and utilized these calculation data (low-quality data) to learn the underlying structure−property relationships via the GPR model. As shown in Figure 4, through graph-based representation and GPR modeling, the trained models of $Y_{\\mathrm{L}}(X)$ demonstrate excellent performance and generalizability. Then, we established the GPR models for the deviations between simulation and experimental data, i.e., $Y_{\\mathrm{D}}(X)$ . By integrating the well-trained models of $Y_{\\mathrm{L}}(X)$ and $Y_{\\mathrm{D}}(X)$ , we obtained the prediction models of $Y_{\\mathrm{H}}(X)$ with high precision. The proposed data mapping strategy can simultaneously improve the quantity and quality of the available data. Compared with the direct ML modeling methods, such a GPR-based multifidelity learning method significantly improves the resulting prediction accuracy and provides a reliable solution for establishing high-precision ML models on limited polymer data.  \n\nUtilizing the deep neural network modeling method, Ramprasad et al. developed a framework containing multitask learning and meta learning algorithms and established the prediction models for copolymer properties.34 Based on a copolymer data set consisting of glass transition $(T_{\\mathrm{g}})$ , melting $\\left(T_{\\mathrm{m}}\\right)$ , and degradation $\\left(T_{\\mathrm{d}}\\right)$ temperatures, they conducted fingerprint representations for copolymers (Figure 5A). These fingerprints served as inputs for training five cross-validation multitask neural networks. The trained multitask learning models were utilized to construct a meta learner as the final prediction model (Figure 5B). The model performance was assessed by metrics, such as the determination coefficient $\\left(R^{2}\\right)$ and root-mean-square error (RMSE). This modeling approach resulted in highly accurate models with an $R^{2}$ value of 0.94 and excellent transferability for both homopolymers and copolymers (Figure 5C−E).  \n\n![](images/f084e485c56084d9aaea788d828a082d66059cab3e8061fddb61a34771290f1e.jpg)  \nFigure 5. Multitask deep neural networks for establishing copolymer property prediction models. (A) Concatenation-based conditioned multitask neural networks. (B) Meta learner that is composed of the five cross-validation models (blue nodes) and neural networks. (C−E) Model performance of meta learner for the (C) glass transition $(T_{\\mathrm{g}})_{\\mathrm{\\ell}}$ , (D) melting $\\left(T_{\\mathrm{m}}\\right)$ , and (E) degradation $\\left(T_{\\mathrm{d}}\\right)$ temperatures. The frequencies of the homopolymer and copolymer data are indicated in black and red, respectively, in the margins of $\\operatorname{C-E}$ . Reproduced with permission from ref 34. Copyright 2021 American Chemical Society.  \n\nWith the advancements in ML algorithms, more intricate prediction modeling tasks can be accomplished. However, the opacity of these black-box models in terms of their prediction and decision-making processes presents challenges in understanding the models and providing physical explanations. Hence, ensuring interpretability is important for ML prediction models. Various model interpretability approaches have been employed to unveil the underlying rules behind black-box models and enhance the transparency and credibility of their decision-making processes.35 Additionally, the existing ML algorithms can be combined with physical mechanisms, such as physics-informed neural network (PINN), to improve model interpretability. During the PINN training process, neural networks with supervised learning tasks are constructed by imposing physical information constraints. Therefore, PINN can not only attain the underlying rules to achieve prediction but also learn and generate physical mechanisms based on the introduced physical constraints, endowing neural networks with interpretability.36  \n\nIn addition to the above considerations, a desirable ML prediction model should also possess robust extrapolation capability for property prediction.35 The capability to precisely extrapolate high-performance spaces is decisive as it impacts whether novel advanced polymeric materials can be efficiently discovered. To endow the model with enough extrapolation capability, the promising strategies include reasonable data preprocessing, integrating domain-specific insights into feature engineering, and employing some advanced modeling methods (e.g., active learning, generative models, and interactive linear regression models).37 Therefore, future ML prediction models for polymeric materials should exhibit enhanced accuracy, interpretability, and generalizability, providing a robust foundation for rational design.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# 4. VIRTUAL DESIGN AND HIGH-THROUGHPUTSCREENING OF POLYMERIC MATERIALS  \n\nML-assisted design usually involves three steps, that is, gene definition and combination, ML-assisted screening, and verification of screened polymers.5,6 The procedure is illustrated in Figure 6A. First, various elements related to material properties are defined as genes, such as structures, components, reaction conditions, and processing parameters. For the polymeric materials, the chemical structures of repeating units or segments along with the length, distribution, and sequence of polymer chains and the morphological features, etc., can be considered to be the genes. We can combine polymer genes according to polymer synthesis routes to generate virtual polymer candidates. Then, using ML models, high-throughput property predictions can be conducted for these candidates, and promising polymers that satisfy the targeted properties can be identified through screening. Finally, computer simulations and experiments are employed to validate the screened polymers.  \n\nRecently, we conducted a ML-assisted design of thermosetting polymer resin and obtained a novel poly(silane arylacetylene) (PSA) resin with enhanced heat resistance and processability.38 The heat-resistant PSA resins, an organic− inorganic hybrid material, have been developed; however, their processability still needs to be improved. First, we defined diyne and silane as the genes of PSA resins according to the synthesis route, collected various genes from the database, and combined them to generate 368 PSA candidates. Then, we established the ML models for predicting the processability and heat resistance of these PSA candidates. Through predicting the candidate properties with these ML models, promising PSA resins with optimal processability and high heat resistance were screened out (see Figure 6B). The black rectangles shown in the heatmap represent the candidates with the top 10 high weighted-average values, i.e., the comprehensive scores of heat resistance and processability. Subsequently, one screened resin containing naphthalene and vinyl groups (PSNP-MV) was synthesized to verify the predictions (Figure 6C). The $T_{\\mathrm{d}5}$ and $T_{\\mathrm{g}}$ values of the PSNP-MV resin are 689 and $608^{\\circ}\\mathrm{C},$ respectively, and its processing window ranges from 110 to $152~^{\\circ}\\mathrm{C}$ . Compared with those of existing PSA resins (e.g., the PSA resin containing 2,7-diethynylnaphthalene, named PSNP-M), the heat resistance and processability of the screened PSNP-MV resins are improved simultaneously, exhibiting enhanced comprehensive performance.  \n\n![](images/14351a855d78104c910b410fc2963acba971336690d675a2d18956d613d255b5.jpg)  \nFigure 6. Virtual design and high-throughput screening of polymeric materials. (A) ML-assisted design procedure including gene definition and combination, ML-assisted screening, and verification of screened polymers. (B) Heatmap of the thermal decomposition temperature and viscosity obtained by ML property prediction for 368 poly(silane arylacetylene) (PSA) resin candidates. (C) Experimental verification for the novel PSNP-MV resin with enhanced comprehensive properties obtained by a ML-assisted design approach. (D) Scatter plot of the modulus, strength, and elongation at break obtained by ML property prediction for 243 942 epoxy resin candidates. (E) Comparison between the experimental values of the screened (red star symbol) and the existing epoxy resin regarding the modulus, strength, and elongation at break. (B and C) Reproduced with permission from ref 38. Copyright 2022 Elsevier. (D and E) Reproduced with permission from ref 26. Copyright 2022 American Chemical Society.  \n\nThe effective screening and design rely on the rational definition and combination of genes to ensure a broader coverage in the target polymer structure space. It is feasible to define genes according to the compositions of polymeric materials and construct gene sets containing diverse structures to generate vast candidates. For example, since epoxy resins generally consist of epoxides and amine curing agents, we defined and collected 746 epoxy genes and 327 amine genes and combined them to generate 243 942 epoxy resin candidates.26 By establishing the ML prediction models for the mechanical properties of epoxy resins and predicting the properties of these candidates, we screened out the epoxy resin thermosets with high strength, high modulus, and high elongation at break from the 243 942 candidates. The mechanical properties of these candidates are shown in Figure 6D. The predicted values of the mechanical properties were standardized and comprehensively scored. The promising resins that meet the multiobjective property targets were screened out according to their comprehensive scores. Finally, one promising high-performance epoxy resin was verified by experiments (see Figure 6E). Its average tensile strength, tensile modulus, and elongation at break are about $89.25\\mathrm{\\:MPa}_{;}$ , $3.85~\\mathrm{GPa},$ , and $6.71\\%$ , respectively, which are close to the predicted values $(99.0~\\mathrm{~\\mp}_{\\mathrm{{a}}}$ , $3.57~\\mathrm{~GPa~}$ , and $6.08\\%$ , respectively). Additionally, compared with other existing epoxy resins, this screened resin exhibits superior mechanical properties, including high modulus, strength, and toughness.  \n\nIn addition to the aforementioned comprehensive score evaluation methods, the multiobjective screening task can be transformed into several single-objective tasks. Through the stepwise screening process one by one, the polymer structures that meet the requirements of superior comprehensive properties are screened out.39 The other possible screening strategies for multiobjective tasks are generally derived from the comprehensive score evaluation method. Sometimes, by defining the approximating function, we can evaluate the approaching degrees of multiple properties to the targets and thereby evaluate whether the candidates meet the requirements of comprehensive properties. Moreover, identifying the Pareto frontier of polymer properties and exploring the promising polymers beyond the Pareto frontier is a feasible screening method.40,41 For the given optimization tasks, the solution that can balance the multiobjective performance is defined as a Pareto-optimal solution, and the set of such solutions is denoted as the Pareto frontier. Therefore, for material properties, in the multiobjective property space, the optimal performance can be obtained at the boundaries of this property space, and these results constitute the Pareto frontier. For example, Li et al. compiled a data set of 2233 existing polyimides (PIs) collected from the PoLyInfo database to identify the Pareto frontier of property space.41 The property space of the glass transition temperature $(T_{\\mathrm{g}})$ , Young’s modulus $(E)$ , and tensile yield strength $(\\sigma_{y})$ of PIs is shown in Figure 7A, where the red squares are the existing PIs with high performance in defining Pareto frontier. Such a Pareto frontier represents an envelope boundary for these three properties $(T_{\\mathrm{g}},\\cal{E},$ and $\\sigma_{y,}^{\\phantom{}}$ . Through gene definition and combination, they obtained 8 million virtual PIs and then established ML models based on the improved Morgan fingerprint representations and the feed-forward neural networks to predict the $T_{\\mathrm{g}},E,$ and $\\sigma_{y}$ values of the candidate PIs.  \n\n![](images/ecf3ab43986ca78889854ee4bd0bdfa85622c936051c06dfb0f871e1f70f443e.jpg)  \nFigure 7. ML-assisted screening of high-performance polyamides (PIs). (A) Comparisons for the properties of PIs to identify the Pareto frontier and screen the promising PIs. The red squares are the existing PIs with high performance in defining a boundary (Pareto frontier). The red stars are the discovered virtual PIs whose properties are beyond the Pareto frontier. The boundaries on each 2D plane are illustrated with the lines passing Pareto frontiers for clarity. (B) ML-assisted screening combined with SAscore for identifying PIs with high $T_{\\mathrm{g}}$ and good synthetic accessibility (SAscore $<3.8$ ). The three typical PI structures are given at the right of Figure 7B. (A) Reproduced with permission from ref 41. Copyright 2023 Elsevier. (B) Reproduced with permission ref 42. Copyright 2023 Royal Society of Chemistry.  \n\n![](images/927db9ca9b111a186a420eb9144e96fea99f649c5f3a746fea89da7b862d3271.jpg)  \nFigure 8. Exploration of compositional space for high-performance copolymers via a Bayesian optimization-guided approach. (A) Illustration of the optimization and exploration in compositional and property spaces. (B) ML-assisted compositional design of the cocured polycyanurates. The variation in the comprehensive score of hygroscopicity, $T_{\\mathrm{g}},$ and Young’s modulus for all measured samples is plotted as a function of iteration. The contour plot displays the distribution of expected improvement (EI) values at the beginning, middle, and end of the iterations, with regions of higher EI values indicated in red. Green circular and red solid square markers represent the measured samples and the best sample at each iteration. Figures are reproduced with permission from ref 44. Copyright 2023 Royal Society of Chemistry.  \n\nBased on these predicted properties of candidate PIs, they screened out three novel PIs beyond the Pareto frontier (see the red stars in Figure 7A). The screened PIs are promising to exhibit superior performance. Finally, they verified the promising PIs through all-atom molecular dynamic simulations and experiments.  \n\nIn addition, synthetic accessibility is another important metric to be considered during the ML-assisted design process of polymeric materials.20,42 For example, Sun et al. predicted the $T_{\\mathrm{g}}$ values of virtual PIs with the GNN model and screened out the promising PIs with $T_{\\mathrm{g}}$ values exceeding $250~^{\\circ}\\mathrm{C}$ . Then, they utilized the synthetic accessibility score (SAscore) to further screen the PIs that can be easily synthesized (e.g., SAscore $<3.8$ ).42 The SAscore represents synthesis accessibility on a scale from 1 (easy) to 10 (difficult) based on the difficulty of synthesizing the corresponding molecules, which is related to molecular segment contributions and molecular complexity. As shown in Figure 7B, 9191 PIs with high $T_{\\mathrm{g}}$ values and good synthetic accessibility were screened out. Although they did not conduct experimental verification, the proposed ML-assisted design strategy combined with synthetic accessibility is commendable, making it helpful for the experimental exploration of high-performance PIs. However, the SAscore evaluation method only considers the synthetic accessibility of small molecules, that is, monomers, and ignores the polymerization ability of these monomers. Thus, developing a new method to evaluate the comprehensive synthetic accessibility of polymeric materials is an important direction.  \n\nIn the industrialization of polymeric materials, formulation and processing parameters play important roles in determining the final performance. For example, when epoxy resins are utilized as the matrix of composites, various multicomponent curing agents, thickeners, and fillers are added to achieve a balance among the mechanical properties, processability, industry costs, and others.43 The trial-and-error approach for formulation exploration is costly and time consuming. Thus, efficiently designing a multicomponent resin formulation is desperately needed. Recently, we developed a Bayesian optimization (BO)-guided method for the compositional design of cocured polycyanurates (see Figure 8A).44 BO is a representative ML approach for solving costly optimization problems. Establishing appropriate optimization frameworks and conducting benchmarking studies are crucial for ensuring the accuracy and efficiency of the BO-based models.  \n\nWe proposed a BO-guided copolymer compositional design workflow in which the compositional space consists of three monomers, i.e., 1,3-bis[2-(4-cyanatophenyl)-2-propyl]benzene (MBCy), 2,5-bis(4-cyanatophenyl)octahydro-1H-4,7-methanoindene (DOCy), and 2,2-bis(4-cyanatophenyl)propane (BADCy). The workflow comprises the following steps: converting the given multiobjective optimization problem into a single-objective optimization problem using a scalarizing function, fitting an underlying function through a Gaussian process-based surrogate, and inferring promising formulas using an acquisition function. Benchmarking studies were conducted by virtue of the knowledge gained from molecular simulations. Then, based on the benchmarking studies, we developed an effective BO-guided design approach. Utilizing this optimization strategy, we discovered several novel cocured copolymers exhibiting low hygroscopicity along with superior $T_{\\mathrm{g}}$ and Young’s modulus after a few iterations (see Figure 8B). Simultaneously improving the multiobjective properties of polymers is challenging due to their contradictory relationships; however, the developed optimization method effectively addresses this challenge. Therefore, data-driven methods, such as Bayesian optimization,45,46 can be employed for the efficient exploration and discovery of advanced polymeric materials, especially for designing their multicomponent formulations.  \n\nMoreover, the reversal design strategy for polymeric materials has attracted considerable attention due to its ability to rapidly discover novel polymers with desirable properties. In contrast to the aforementioned design methods, utilizing the generative algorithms enables the identification and mutation of preferred polymer genes, allowing the design of highperformance polymers in a relatively limited structural space.11,47 By predicting the properties of the first-generation candidates from gene combinations, the differences between candidate performance and target performance can be evaluated. Based on these differences, the combinable polymer genes can be optimized through genetic crossover and mutation. Then, a new generation of polymer genes and candidates can be generated through the structural generative models trained based on self-supervised learning, such as variational autoencoders or generative adversarial networks.  \n\nThe performance of the new-generation candidates can gradually approach the target performance. As a result, through a few iterations, novel polymers that satisfy the multiobjective properties can be identified. Therefore, beyond forward prediction and screening, it is imperative to develop a reversal design approach that can rapidly identify new polymer structures that meet the imposed multiobjective performance requirements.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# 5. SUMMARY AND OUTLOOK  \n\nIn summary, the polymeric material field is entering a new research paradigm driven by ML and big data, promoting advancements in polymer informatics. The QSPR of polymeric materials is predicted by ML models to achieve ML-assisted virtual design and screening, effectively accelerating the discovery of high-performance polymers. However, the relative scarcity of high-quality data and the complex multiscale structure−property relationships of polymeric materials present formidable challenges for such an ML-assisted design method, that is data and modeling challenges, as shown in Figure 9.  \n\n![](images/1af13f657fa9bb95b2f2355c818b4d4254c2834c64a4898e36fcf54f4fc80289.jpg)  \nFigure 9. Schematic summarizing the challenges and development directions of ML-assisted design of polymeric materials.  \n\nTo address these challenges, it is imperative to establish new methods and develop advanced models, especially those inspired by cutting-edge algorithms in the fields of artificial intelligence and cheminformatics. To solve the small data conundrum in polymeric materials, not only the data from the theoretical calculation and computer simulation can be utilized but also advanced ML algorithms can be employed. Directly utilizing the theoretical calculation or simulation data or improving the data quality with the multifidelity surrogate model is effective.25 Additionally, it is essential to account for the multiscale structure characteristics that are inherent in polymeric materials. These development directions are outlined below.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 11,
+        "chunk": "# 5.1. Establishing New Representation Methods for the Polymeric Multiscale Structures  \n\nA series of multiscale descriptors should be established to accurately represent the chemical structures of repeated units, polymer chain structures, and aggregation structures, including crystallization, cross-linking, and phase structures.48 For example, it is advisable to establish a periodic fingerprint or graph representation method that can capture the characteristics of polymer chains by modifying and embedding various digital representations.27 Moreover, the metastable multiscale structures of polymeric materials should also be digitally represented, and the generated descriptors can serve as inputs for ML training. The information of multiscale structures can be obtained from theoretical calculations, computer simulations, and experiments. Then, they are processed using image analysis algorithms to extract relevant features that characterize the crystalline region, orientation degree, phase boundary, etc.49 These features can be directly adopted or further modified to generate polymeric multiscale descriptors for training graph-based prediction models. Furthermore, processing parameters play a crucial role in determining the aggregation structures and ultimately affecting the properties of polymeric materials. Processing parameters such as temperature, pressure, and shear rate significantly impact the crystalline, orientation, and phase structures of polymers during processing. These parameters can be adopted or modified to generate processing descriptors and then serve as the inputs for training models. When these effects are considered during the modeling process, the accuracy of ML models can be further improved.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 5.2. Developing Advanced ML Models To Describe Polymer Structure−Property Relationships  \n\nFor example, ML modeling methods, such as transfer learning and multitask learning, can be adapted and optimized to establish high-precision prediction models, even in cases with limited amounts of reliable data.50 Moreover, the interpretable ML methods can provide insight and guidance for designing polymers and advancing polymer theory. It can give a transparent view into the decision-making process, enabling researchers to understand the underlying relationships between input features and output predictions. On one hand, by using interpretable models or feature importance analysis methods (e.g., SHapley Additive exPlanations, SHAP),51 we can identify the most influential features and correlations that govern polymer properties. On the other hand, by employing the interpretable ML models in combination with genetic algorithms and symbolic regression,35,52 quantitative equations and even new theoretical frameworks for structure−property relationships can be obtained. For example, the sure independence screening and sparsifying operation (SISSO) is a data-driven symbolic regression method. Different from other ML predictive methods, SISSO is a white-box model that can be described as a formula, allowing researchers to analyze and explain the field knowledge. Thus, we believe that such interpretable ML models can promote advancements in polymer theory.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 5.3. Establishing Polymer Large Models Based on Chemical Language  \n\nDrawing inspiration from natural language processing methods, the polymer informatics field is leveraging chemical language to establish large models for polymer structure generation and property prediction.32,53−56 A large model refers to a model with extensive and intricate parameters, such as the large model of Chat Generative Pretrained Transformer (ChatGPT). Several established chemical language models possess the ability to comprehend chemical rules and generate novel chemical substances. Recently, there have been some advancements in polymer chemical language models, such as TransPolymer,53 PolyBERT,54 and PolyNC,56 which aim to address the data and modeling challenges of polymers and predict their various properties in a vast structural space. Polymer large models trained through data parallelism can effectively integrate and utilize the data from different sources and modalities. Moreover, they can also be established by integrating a series of well-trained prediction models through pipeline parallelism training processing. Thus, they can give out the commonality of the structure−property relationships for different properties and inspire researchers to identify important factors influencing the polymer properties and to establish a prediction model for some specific properties. Therefore, the upcoming polymer large models possess immense potential to comprehensively accelerate the development of polymeric materials and revolutionize traditional design methodologies.  \n\nFurthermore, it is coveted to construct high-throughput synthesis and characterization for polymeric materials.57−59 The high-throughput experimental systems can generate highquality data encompassing diverse structures, components, and processing parameters. By combining with ML-assisted design methods, the efficiency of the design and optimization processes for polymeric materials can be further improved. For example, Brabec and Li et al. established a high-throughput experimental platform named AMANDA Line One and realized the automatic fabrication and characterization of organic solar cells.58,59 This platform enables the screening of over 100 processing parameter variations in terms of efficiency and photostability within $^{70\\mathrm{~h~}}$ . Combined with ML methods, they achieved the prediction for both the efficiency and the photostability of OPV materials based on the high-quality experimental data set. However, for polymeric materials, the development of high-throughput experimental systems is still in the nascent stage. The existing relevant equipment is typically adopted from parallel synthesizers but only partially satisfies the requirements for achieving truly high-throughput synthesis and characterization capabilities of polymers. Therefore, developing high-throughput experimental platforms for polymers is anticipated by experimentalists.  \n\nThe integration of ML methods with computer simulations is emerging as an important direction in computational materials science, offering significant enhancements in the accuracy and efficiency of computer simulations. ML algorithms can analyze simulation outputs, identify hidden correlations, and extract meaningful insights. Moreover, by leveraging ML algorithms for feature selection, model optimization, and data preprocessing, researchers can streamline the simulation workflow and reduce computational costs.60 The integration of ML methods with computer simulations can facilitate the development of surrogate models or emulators that can mimic complex computer simulation codes with lower computational costs.  \n\nOverall, the ML-assisted design strategy offers a new methodology for discovering high-performance polymeric materials that are needed for applications in advanced equipment for aerospace, energy storage, communication, and other fields. For example, regarding organic semiconductors, there is a demand for polymeric materials with high electron mobility, high luminescence efficiency, high spin characteristics, and high conductivity. By employing the MLassisted design strategy, it is promising to discover novel polymeric semiconductor materials with good comprehensive properties in a shorter time frame and with reduced costs. Undoubtedly, the emerging paradigm driven by ML and big data can revolutionize the traditional trial-and-error design approach of polymeric materials. As summarized in this Account, state-of-the-art research and achievements have demonstrated both the high efficiency and the advanced nature of this paradigm. Nevertheless, this field is still in its infancy. In future endeavors, developing new methods for data processing, structure representation, ML model establishment, as well as virtual screening is highly desirable for realizing the intelligent design of advanced polymeric materials.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# AUTHOR INFORMATION",
+        "category": " References"
+    },
+    {
+        "id": 15,
+        "chunk": "# Corresponding Author  \n\nJiaping Lin − Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China; $\\circledcirc$ orcid.org/ 0000-0001-9633-4483; Email: jlin@ecust.edu.cn",
+        "category": " References"
+    },
+    {
+        "id": 16,
+        "chunk": "# Authors  \n\nLiang Gao − Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China; $\\textcircled{1}$ orcid.org/ 0000-0001-6852-8301   \nLiquan Wang − Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China; $\\textcircled{6}$ orcid.org/ 0000-0002-5141-8584   \nLei Du − Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China  \n\nComplete contact information is available at: https://pubs.acs.org/10.1021/accountsmr.3c00288",
+        "category": " References"
+    },
+    {
+        "id": 17,
+        "chunk": "# Notes  \n\nThe authors declare no competing financial interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 18,
+        "chunk": "# Biographies  \n\nLiang Gao received his Bachelor’s (2013) and Ph.D. (2019) degrees under the supervision of Jiaping Lin in Materials Science and Engineering from East China University of Science and Technology (ECUST). Now, he is working as an associate professor at ECUST. His research is focused on theoretical simulation of polymers and polymer material genome approach.  \n\nJiaping Lin received his Bachelor’s and Master’s degrees from Shanghai Jiao Tong University and Ph.D. degree from ECUST (1993). After that, he obtained a postdoctoral fellowship from the Japan Society for the Promotion of Science (JSPS), received a LiseMeitner fellowship from Fonds zur Förderung der Wissenschaftlichen Forschung (FWF), and worked as a postdoctoral researcher in the Tokyo Institute of Technology and University of Linz in Austria. He has been in ECUST ever since returning home from abroad in 1997. He became a full professor in 1999. His current research interests include polymer theory and simulation, polymer material genome approach, and polymer self-assembly.  \n\nLiquan Wang received his Ph.D. degree under the supervision of Jiaping Lin in Materials Science and Engineering from ECUST in 2011. Now he is working in the School of Materials Science and Engineering of ECUST. From 2016 to 2017 he worked as a visiting researcher scholar with Zhen-Gang Wang at the California Institute of Technology. His research interests center on theoretical simulation of complex polymer systems and polymer material genome approach.  \n\nLei Du is a professor at the School of Materials Science and Engineering of ECUST. He received his Bachelor’s degree from Nanjing University (1965). From 1985 to 1987, he worked as a visiting researcher scholar in the Polymer Department of Pennsylvania State University. His current research interests include highperformance resin and composites and polymer material genome approach.",
+        "category": " References"
+    },
+    {
+        "id": 19,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nThis work was supported by the National Natural Science Foundation of China (22103025, 52394271, 51833003, and 21975073) and the Shanghai Chenguang Program (22CGA31).",
+        "category": " References"
+    },
+    {
+        "id": 20,
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+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Data-Driven Materials Research and Development for Functional Coatings  \n\nKai Xu, Xuelian Xiao, Linjing Wang, Ming Lou, Fangming Wang, Changheng Li, Hui Ren, Xue Wang, and Keke Chang\\*  \n\nFunctional coatings, including organic and inorganic coatings, play a vital role in various industries by providing a protective layer and introducing unique functionalities. However, its design often involves time-consuming experimentation with multiple materials and processing parameters. To overcome these limitations, data-driven approaches are gaining traction in materials science. In this paper, recent advances in data-driven materials research and development (R&D) for functional coatings, highlighting the importance, data sources, working processes, and applications of this paradigm are summarized. It is begun by discussing the challenges of traditional methods, then introduce typical data-driven processes. It is demonstrated how data-driven approaches enable the identification of correlations between input parameters and coating performance, thus allowing for efficient prediction and design. Furthermore, carefully selected case studies are presented across diverse industries that exemplify the effectiveness of data-driven methods in accelerating the discovery of new functional coatings with tailored properties. Finally, the emerging research directions, involving integrating advanced techniques and data fro.m different sources, are addressed. Overall, this review provides an overview of data-driven materials R&D for functional coatings, shedding light on its potential and future developments.",
+        "category": " Abstract"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1. Introduction  \n\nThe tremendous development of high-tech industry in the last decades has led to the actuality that the modern materials are increasingly served in harsh environments and are always in urgent needs of diversified functionalities. Functional coatings refer to a wide range of materials engineered to provide desirable surface properties, such as thermal barrier,[1,2,3,4] anticorrosion,[5,6,7] wear-resistance,[8,9,10,11] antifouling property,[12,13,14] antimicrobial activity,[15,16] self-healing capability,[17,18,19] superhydrophobicity,[20,21,22] conductivity,[23,24,25,26] color shift,[27,28,29] and etc.[30,31,32,33,34,35] These coatings are an essential component of various industries that can fulfill specific requirements and advance the related material technology, ranging from aerospace and automotive to biomedical and electronics. The choice of customized coating depends on the specific protection or function needs in an industrial application, as show in Figure 1 i. In the aerospace industry, functional coatings, such as thermal/environmental barrier coatings (T/EBCs) can protect aero-engines components from high-temperature exposure, enabling the engine to work  \n\nat higher temperatures with consequently remarkable enhancement in efficiency and safety, bringing breakthrough in thrust-to-weight ratio, and reducing maintenance costs.[1,2,3,4] For the moving parts of spacecrafts operated in the low earth orbit, nanocomposite films such as $\\mathsf{M o S}_{2}$ -based films can achieve high irradiation tolerance to atomic oxygen and self-adaptive lubrication by manipulating the structural transformation of $\\mathbf{MoS}_{2}$ , doping with certain metals or compounds, introducing multilayer, and designing posttreatments.[36,37,38]  \n\nii. In the marine industry, anticorrosion coatings, such as epoxy, polyurethane, and zinc-based coatings, act as a protective barrier on metal surfaces to prevent corrosion and even complex multifactor coupling damage from saltwater or deepsea exposure.[6,39,40] Also, antifouling coatings, include selfpolishing copolymers and controlled depletion paints, prevent the buildup of organisms like algae and barnacles on the hulls of ships.[12,13,14] The build-up of ice on facility surfaces can be prevented by anti-icing coatings, leading to better performance and safety during services.[20,41,42]  \n\n![](images/1839f5b9e500663d7775831d0c4d1b7b7b234b548280566dca3cc77021a0d11b.jpg)  \nFigure 1. Specific protection or function needs of functional coatings in versatile industrial applications.  \n\niii. In the energy industry, the transition to cleaner and lowcarbon energy is high-profile and irresistible. Photocatalytic coatings can be applied to solar panels to enhance their efficiency by converting more sunlight into electricity.[43,44,45] These coatings can also be used to harness solar energy for water splitting, enabling the generation of clean and renewable hydrogen fuel.[46,47] Nuclear energy is also become an increasing crucial alternative for clean electrical power. Different protective coatings designed for accident-tolerant fuel cladding materials can constantly withstand neutron irradiation, as well as high-temperature and frictional wear.[48,49,50]   \niv. In the automotive industry, functional coatings can improve the longevity of different parts and minimize material waste. For example, scratch-resistant coatings protect car surfaces from damage, while coatings that reduce friction assist in the production of more fuel-efficient engines.[51,52] Wear resistant coatings deposited on the surfaces of engine or moving components exhibiting low friction and wear under various operating conditions can help to decrease fuel consumption and prolong service life.[53,54]  \n\nv. In the biomedical industry, surface modification technology is indispensable for the long-term application of medical implants or stents, as well as those nonimplanted medical devices, which can improve the biocompatibility, safety, and efficacy of biomaterials.[23,55,56] Coatings designed to prevent bacterial attachment can reduce the risk of infections, while coatings that promote specific cellular activities can enhance tissue growth and recovery.[57,58,59]  \n\nvi. In the electronics industry, functional coatings can protect delicate circuitry from complex environmental damage and add desirable aesthetic properties. For example, anticorrosion or antidust coatings can reduce the risk of failure in electronic hardware or remove dust and debris on top of interdigitated electrodes,[60,61] while optical or electromagnetic coatings can improve the display quality or inspire specific physical characteristics of electronic devices.[62,63,64] Additionally, with the growing interest in flexible and wearable sensing electronics, versatile functional coatings, including but not limited to electrically conductive coatings, superhydrophobic smart coatings, and low-cost stretchable coatings, are explored and developed to fulfill the innovation demands in modern electronics.[65,66,67]  \n\n![](images/08971fd5ec32953465038e31b66733e246c0810e5b5cff850bbc7d8fb6054e7a.jpg)  \nFigure 2. Workflow of inverse design for functional coatings from the ocean of data to desired materials by data-driven approach.[70]  \n\nThe growing demand for high-performing and sustainable products has led to an increased interest in functional coatings. Despite their widespread applications, the R&D of innovative functional coatings remain a challenging task. Traditional methods used for the discovery of functional coatings with tailored properties rely heavily on trial-and-error, which have proved to be both costly and time-consuming, particularly when dealing with complex coating systems. These systems often involve multiple components, phases, microstructures, properties, and preparation techniques, further exacerbating the challenges faced during the discovery process.  \n\nThe ongoing development and interdisciplinary collaboration of computer technology and other fields, such as materials science in recent years have sparked significant interest in scientific data as the heart of state-of-the-art research, current hardware and software enable the utilization of data at an unprecedented scale.[68,69,70,71] With vast amount of data now available in materials science and engineering, data-driven approach has emerged as a promising choice showing great potential in reducing the time and cost for materials discovery.[72,73,74,75,76] The discovery of highly tailored coatings utilizing machine learning (ML) can be treated as a tool within inverse design strategy, which is unlike the traditional diverse one, as shown in Figure 2.[70] The accumulated data can perform as a foundation for investigation, helping to reduce cost and speed up the development cycle of novel functional coatings by shrinking the search space toward the most promising regions.  \n\nHerein, the purpose of this review paper is to introduce the use of data-driven techniques in the search for promising functional coatings, and to discuss the potential benefits and limitations of this approach. On this basis, we carefully discuss the inevitable challenges in traditional methods and the recent progress in datadriven R&D for functional coatings. Moreover, we prospect the development trend of data-driven approaches in future.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2. Traditional Methods of Coating Material Investigation  \n\nTraditionally, materials to be used in functional coatings have been developed through the trial-and-error method. Different raw materials and chemical compounds are mixed together to make samples through specific processes Their properties are experimentally evaluated, such as thermal stability, hardness, toughness, chemical resistance, and electronic properties. Then, based on the performance, the composition and process are adjusted until the desired performance specifications are achieved. This process is lengthy and expensive, often requiring significant R&D resources. Some classic traditional material development strategies are shown in Figure 3, including trial-and-error, empirical knowledge and experience, nature-inspired, and serendipity. The following section briefly describes these traditional methods of materials investigation.",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2.1. Trial-and-Error  \n\nBefore the development of modern science, trial-and-error methods dominated materials science and chemistry. Researchers typically selected a set of possible material compositions or processing parameters and then tested these choices experimentally, with repeated experiments and refinements to determine the optimal combination of materials and properties. He et al.[77] prepared two types of $\\mathrm{CrSi}$ and $\\mathrm{CrSiN}$ coatings with different Si content ratios by multiarc ion plating. It was found that the friction and wear performance of the CrSi-based coatings with a high Si content was superior to that of the CrSi-based coatings with a low Si content, but inferior to CrSiN coatings. In practice, there is tremendous complexity in the combination of material composition and processing technology. The approach is highly dependent on personal experience and intuition, making it difficult to comprehensively and systematically explore the optimal combination of materials. As a result, it can take a lot of time and resources to find an effective material solution.  \n\n![](images/403aa3308c592893f741c6be37b4c4bd0d65864d292d9b54d4f0b0dd7cc9c8be.jpg)  \nFigure 3. Traditional materials discovery approaches, including a) trial-and-error. Reproduced with permission.[77] Copyright 2020, Elsevier. b) Empirical knowledge and experience. Reproduced with permission.[78] Copyright 2023, Elsevier. c) Nature-inspiration approaches. Reproduced with permission.[79] Copyright 2024, John Wiley and Sons. d) Serendipity. Reproduced under the terms of the CC-BY license.[80] Copyright 2022, the Authors, published by MDPI, Basel, Switzerland.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2.2. Empirical Knowledge and Experience  \n\nMaterials scientists often rely on pre-existing expertise and experience to guide the materials development process. By analyzing existing materials science knowledge and experience, combined with multidisciplinary field crossover, it can help researchers to make the right decisions and thus improve the efficiency of materials science research. Chaouiki et al.[78] combined the knowledge in the fields of electronic modulation and architectural engineering to grow a multifunctional coating with 3D fir tree structure on magnesium alloy matrix, upgrading the structure of the coating and improving the electrochemical efficiency. Although the method of combining experience and knowledge can eliminate a large number of useless attempts in advance, it has higher professional requirements for researchers.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.3. Nature-Inspired Approaches  \n\nThe design and development of biomimetic materials are an important research direction in materials science. There are many high-performance materials in nature with unique structures, and these natural materials have evolved over time to exhibit amazing properties, such as high strength, high toughness, selfhealing, and smart response. Researchers delve into the study of natural material structures and their formation processes, drawing inspiration from nature to develop novel materials through biomimetic design and bio-inspired approaches to meet the needs of modern industrial and technological development. In nature, for example, the complex structure of plant leaves gives them excellent light absorption and wettability. Inspired by the longitudinal gradient characteristics and surface micronanostructures of lotus leaves, the teams of Wang and Tao[79] collaborated in the research to prepare a multifunctional thermoregulatory coating that integrated self-cleaning of superhydrophobic surfaces and automatic adjustable solar reflectivity, and effective utilization of thermal infrared emission through a one-step phase separation process. In this way, radiation refrigeration in high temperature environment and solar heating in low temperature environment were realized, thereby, achieving the Intelligent thermoregulation of “warm in winter and cool in summer.”",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.4. Serendipity  \n\nOccasionally, new materials are discovered by chance during unrelated experiments or observations. A team from ETH Zurich[80] has discovered a polymer coating called polyphenylene propylene methacrylate (PPM) with self-healing. This material is able to repair itself after being damaged, thus restoring its original protective properties. Initially, the researchers only found that the material had good anticorrosion properties, and then accidentally discovered its self-healing properties. The emergence of such new substances or materials could open new horizons for the entire science community, which is of significant value but less likely to be duplicated.  \n\nTraditional experimental approaches for materials discovery have typically relied on trial-and-error methods. While these methods have been effective in the past, they have had some notable limitations, notably in terms of high costs and inefficiencies, especially in novel material systems with multiple components and phases. These methods are usually limited to testing of known materials and do not guarantee the discovery of new materials or properties, which directly limits the development and application optimization of materials science. In addition, these methods of materials development rely heavily on the experience and intuition of researchers, which requires a high level of researchers’ own knowledge base and experience. Moreover, the preparation and testing conditions for each new material may be different, which makes it difficult to standardize the R&D process, and increase the difficulty of translating from the laboratory to real-world applications.  \n\nIn the face of these challenges, data-driven approaches show great potential to significantly accelerate the discovery process of new materials, reducing the number of trials, and improving the accuracy of predictions by utilizing advanced algorithms and big data techniques. These methods can quickly identify and recommend potentially valuable material combinations within large chemical and material databases to optimize material performance and functionality. At the same time, data-driven methods improve theory formation and scientific advancement by modeling more accurate correlations between material composition and properties, which is especially critical for the development of multifunctional coatings and high-performance materials. The data-driven approaches will be cover in detail in the following sections.",
+        "category": " Introduction"
+    },
+    {
+        "id": 8,
+        "chunk": "# 3. Data-Driven Approaches  \n\nData-driven materials research and development is a research approach that involves the analysis of large sets of data from various sources to develop predictive models that can accurately predict the properties of a material before it is synthesized or fabricated in a laboratory. In the 1980s, the rise of ML and artificial intelligence (AI) catalyzed the application of data-driven models to complex problems, leading to the development of early data-driven frameworks. Entering the 21st century, the advent of big data technologies made it possible to process and analyze vast amounts of data, marking humanity’s entry into the Industry 4.0 era. During this period, data-driven approaches rapidly advanced, becoming one of the primary drivers of innovation.[81] Composition and structure design, process modeling and optimization, and performance improvement are critical issues in the field of coating engineering, yet the inherent nonlinear processes within coatings present challenges that conventional research methods struggle to address. ML and deep learning (DL) have proven highly effective in handling these nonlinear problems in a data-driven manner. As early as 2007, Barletta et al. utilized artificial neural network (ANN) technology to model electrostatic fluidized beds (EFB) and screened for the optimal NN model.[82] In 2014, they applied new ML techniques, using support vector machines (SVM) to model the EFB coating process, achieving favorable predictive results.[83] Currently, an increasing number of ML techniques, such as ANN and SVM, alongside Bayesian optimization and genetic algorithms, are being employed in functional coatings, often involving a combination of various methods for comparative use.[84]",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# 3.1. Process Guideline  \n\nLeveraging the capabilities of extensive and diverse datasets, datadriven approaches employ sophisticated modeling techniques to discern significant patterns, which can offer the potential to uncover hidden trends, and predict serving behaviors, and even optimize processes with unprecedented accuracy. The following process outlines the framework of data-driven approaches (Figure 4).  \n\nAt first, collecting extensive materials datasets according to a determined data analysis framework. These datasets can come from various sources, including experimental data, materials databases, and simulations. The collected data needs to ensure its accuracy and completeness. It will be analyzed to identify correlations between the materials properties and potential performance. Correlation analysis can provide a statistical basis for the feature selection and validate whether the highly ranked features are coincident with generally accepted mechanisms, such as Maximum Information Coefficient (MIC), Pearson Correlation Coefficient (PCC). Models will be developed to predict the materials structures and properties based on the analyzed data. Depending on the type of task, these models can be built based on supervised learning, unsupervised learning, or reinforcement learning algorithms.  \n\nThe developed models must be trained using existence data to make models reliable and accurate. Usually, the data are divided into two parts, a training set and a testing set, to train and test the model. There are several commonly used partitioning methods, such as the set aside method, the k-fold cross validation method, and the bootstrap method.  \n\n![](images/afdebf6be4512362e5ba8eed3259ad17ed679e1d6aa443fe7e5d5c5f3f328471.jpg)  \nFigure 4. Framework of data-driven approaches.  \n\nWhile training, the developed models can be optimized by adjusting model parameters or adding additional data. Overfitting is a common issue, which refers to the phenomenon where a model has a small error on the training set data, but a large error on data samples outside the training set. Common solutions include the dropout method, L1 and L2 regularization, and the early stopping method. At last, predictions are made based on the optimized model to either improve existing materials or discover new materials.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# 3.2. Data Collection  \n\nThere are several data sources that can be used for coatings development using data-driven approaches in functional coatings development, commonly used mainly for the following categories: i) Experimental materials databases (Springer Materials, Cambridge Structural Database (CSD), Inorganic Crystal Structure Database (ICSD), National Institute of Standards and Technology (NIST) database, and Crystallography Open Database (COD)); ii) Computational materials databases (Materials Project, Automatic-FLOW, Open Quantum Materials Database (OQMD), and Novel Materials Discovery (NOMAD) project); iii) Research articles and scientific literature;[85,86,87] (iv) Patents and intellectual property databases (United States Patent and Trademark Office (USPTO), European Patent Office (EPO), World Intellectual Property Organization (WIPO)).  \n\nThe integration of large amounts of data from different sources enables assistance in the identification of promising materials and processing parameters, minimizes both time and risk inherent in screening new materials. Consequently, the following section delineates approaches for the concrete implementation of data collation. In accordance with the insights derived from literatures, these data collation methodologies are systematically classified into several categories, namely, high-throughput experimentation, computational modeling, data mining, and big data.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# 3.2.1. High-Throughput Experimentation  \n\nIn recent decades, researchers are working with the principles of multicomponent composition gradient and multiple samples at once, and have gradually proposed and conducted high-throughput preparation or characterization methods in discovering new materials such as alloys, polymers, inorganics, etc.[88,89,90,91,92] In the realm of high-throughput experiments, several critical factors should be considered, including automated instrumentation and processes, parallel processing, as well as data management and analysis. Automation, as applied comprehensively throughout the experimental workflow, spans domains such as sample synthesis and measurement. This pervasive automation serves the pivotal role of minimizing manual intervention, thereby mitigating the potential for inadvertent errors. Parallel processing, an integral component of high-throughput experimentation, expedites research endeavors through the simultaneous execution of multiple experiments. This parallelization significantly accelerates the process of data generation and analysis.  \n\nIn reality, a number of high-throughput experimental preparation methods obeying different principles have been designed in different fields, which include but not limited to the highthroughput diffusion multiples,[93,94,95] high-throughput rapid experimental alloy development (HT-READ) methodology,[96] high-throughput combinatorial printing (HTCP),[97] highthroughput hot-isostatic-pressing based microsynthesis approach (HT-HIP-MSA),[98] high-throughput combinatorial co-sputtering,[99,100,101,102] microfluidic pen lithography (MPL),[103,104,105] scanning-probe block copolymer lithography (SPBCL) mediated synthesis technique,[106,107,108,109] and other high-throughput synthesis approach,[110,111] as summarized in Figure 5. These laboratory techniques have been used successfully in the materials discovery, which can be used to quickly screen a large number of materials for a particular property. By screening a large number of materials simultaneously, researchers can identify promising candidates for further optimization. The researchers have combined design of experiment (DoE) with high-throughput experiments to statistically analyze the effects of different factors on the performance of the materials. The method will further improve the efficiency of high-throughput experiments, thus obtaining more critical experimental data and improving the progress of the screening process.[112,113]  \n\nThe prodigious volume of data generated during these experiments necessitates specialized methodologies for data management and analysis. These approaches are essential for discerning implicit patterns within the data, which, in turn, serve as reference points for subsequent investigations.  \n\n![](images/9fea3c8cba5b30afc2345a2e7c3e08373a2fe336edec918b75e8f6d27502a596.jpg)  \nFigure 5. Summary of typical high-throughput experimental preparation methods. a) Effective alloy design of high-Cr CoNi-based superalloys via multicomponent high-throughput diffusion multiples. Reproduced with permission.[95] Copyright 2023, Elsevier. b) Modifying Alloy 625 based on the integrated high-throughput rapid experimental alloy development (HT-READ) methodology. Reproduced with permission. Copyright 2021, Elsevier. c) The development of combinatorial erials ols by high-throughput combinatorial printing (HTCP). Reproduced under the terms of the CC-BY license.[97] Copyright 2023, the Author published by Spring er Nature. d) The exploration of CoCrFeNi-based high entropy alloys enabled by the newly developed high-throughput hot-is ed microsynthesis approach (HT-HIP-MSA). Reproduced with permission.[98] Copyright 2022, Elsevier. e) Study of thermal stabilit u-Ag/Pd nanocrystalline alloys using high-throughput combinatorial cosputtering. Reproduced with permission.[102] Copyright 2020, Elsevier. f) Femtolitre chemistry of screening new metal-peptide networks assisted by microfluidic pen lithography",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 3.2.2. Computational Modeling  \n\nComputational modeling methods have emerged as powerful tools for materials discovery.[114,115] These computational methods can significantly reduce the need for experimental trial-anderror, and provide insights into the underlying mechanisms that govern materials properties. Each method has its own strengths and limitations, and researchers often utilize a combination of these techniques to gain a comprehensive understanding of material properties and behaviors. Figure 6 displays commonly used computational modeling methods in materials discovery at different scales:  \n\ni. Density functional theory (DFT): DFT is a widely used method for investigating the electronic structure of materials from the viewpoint of atoms and electrons.[124,125] It enables prediction of various properties, such as band structure, defect formation energies, and reaction energies, providing valuable insights into the behavior of materials. DFT provides data for machine learning including electronic structures, band structures, electrochemical, and thermodynamic properties.[87,126]   \nii. Molecular dynamics (MD): MD simulations provide a dynamic view of material behavior under various conditions, such as phase transitions and mechanical stresses, by numerically solving Newton’s equations of motion. These simulations require precise initial specifications, including the types and quantities of molecules, their spatial coordinates, and initial velocities, to generate data on the positions and velocities of atoms at successive time steps. For instance, Xiao et al.[127] used MD simulations to investigate the formation of a biomimetic nanostructured ultrablack coating, revealing how molecular interactions at the nanoscale influence material properties. This study can provide machine learning with time-series data on atomic positions and velocities.  \n\niii. Calculation of phase diagrams (CALPHAD): The CALPHAD approach is a computational method for calculating phase diagrams of multicomponent systems, which allows one to design target microstructure and optimize macro property.[128,129,130,131] These calculations provide machine learning with data on phase stability, transition points, and compositional relationships. For instance, The Chang’s team conducted an in-depth study on the alloy coatings. They calculated the effect of Si addition on the mechanical properties of NbTiZr refractory medium-entropy alloys (RMEA) by the CALPHAD method.[132] This data can train models to predict how alloy hardness, toughness, and strength change with different Si contents. Similarly, the thermodynamic and kinetic data from the study of Lou et al.[133] on the oxidation behavior of TiN system coatings with refractory metal elements can be utilized by machine learning models. The trained model can be used to predict the oxidation behavior and corrosion resistance of coatings under different environmental conditions (such as temperature and oxygen partial pressure).  \n\niv. Phase-field (PF) modeling: It is used to study phase transformations, grain growth phenomenon, fracture behavior, and crack propagation in materials.[134,135] Dynamic equations governing the evolution of PF variables are derived via the variational principle, elucidating how these variables change over time. Initial distribution of PF variables at the inception of the simulation is determined, then, considerations are made regarding the behaviors at boundaries. External driving forces, such as temperature gradients or chemical gradients, are introduced into the model, influencing both the direction and rate of phase field evolution. Gao et al.[122] utilized PF modeling to reveal the mechanisms of grooving and agglomeration in polycrystalline NiSi thin films on monocrystal Si substrates, offering insights into the dewetting phenomena of the polycrystalline thin film. PF modeling results can be used for machine learning models to predict the behavior of materials under different environmental conditions and optimize material design and processing techniques.  \n\nv. Finite element modeling (FEM): FEM is a numerical analysis method that approximates the solution of the whole problem by partitioning a complex continuous problem into simple subregions and performing numerical computations on the subregions in sequence. It is widely used in macroscale structural analysis and various engineering applications.[136] Sajadi et al.[137] used FEM to develop a continuous plastic damage model to understand the damage expansion law of conformal coatings under compressive loads. This approach can provide machine learning with detailed data on structural stresses, deformations, material behaviors, etc. Machine learning models can leverage this data to predict and optimize material and structural performance under complex loading conditions, thereby improving design and material selection.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 3.2.3. Data Mining and Big Data  \n\nThe rise of high-performance computing platforms, cloud computing and IoT sensors infrastructure, has resulted in the generation of vast amounts of data, opening new avenues for materials discovery processes. Data mining and big data technologies play a crucial role in deciphering and utilizing this plethora of information to enhance materials development. Data mining involves the extraction of previously unknown and potentially useful patterns from large datasets and applying computational and statistical technology to data from experiments and simulations. It serves to unveil intricate relationships between material components, experimental conditions, and material properties. By distilling the most relevant features from high-dimensional datasets, identifying errors, anomalies, or unanticipated outcomes within experimental datasets, and utilizing techniques such as classification, clustering, and association rules, data mining provides invaluable guidance to researchers in optimizing research efforts and potentially unearthing unnoticed phenomena. Big data, characterized by its vast volume, multifaceted composition, and real-time attributes, encompasses large and diverse sets of data on materials, which can be used to train ML algorithms to identify critical properties of coating materials. However, big data often arrives in an unfiltered or unprocessed state, laden with noise and anomalies. Specialized tools and methodologies are required to preprocess and refine this data, rendering it amenable for practical utilization. Despite its challenges, big data has emerged as a formidable instrument in the fields of materials design and analysis. Together, the combination of data mining and big data technologies facilitates a deeper understanding of the intricate interplay of variables in materials development and enables the identification of critical properties of materials, thereby optimizing research efforts and leading to the development of new functional coatings. For example, Nikalin et al.[138] reviewed the patent literature of the past 15 years dealing with waterborne coatings used for painting metal surfaces and concluded concerning the most promising and demanded areas in the waterborne paint and varnish sector. Momber et al.[85,86] proposed a concept of a fully data-based procedure for the condition monitoring of protective coating systems of large onshore wind turbines. This data and methodology can provide machine learning with critical information on material characteristics, performance prediction, behavior pattern identification, and new material discovery.  \n\n![](images/8f41a00265200f286b2d9c6393079d96d07ec23ffcc416e252dc5a4be62c7e34.jpg)  \nFigure 6. Illustration of diverse scale of computational modeling. Typical methods from the scale of atoms and electron to macroscale are density functional theory (DFT), molecular dynamics (MD), calculation of phase diagrams (CALPHAD), phase-field (PF) modeling, and finite element modeling (FEM). Reproduced with permission.[116] Copyright 2023, Elsevier. Reproduced under the terms of the CC-BY license.[117] Copyright 2023, the Authors, published by Springer Nature. Reproduced with permission.[118] Copyright 2020, Elsevier. Reproduced with permission.[119] Copyright 2017, Springer Nature. Reproduced under the terms of the CC-BY license.[120] Copyright 2020, the Authors, published by American Association for the Advancement of Science. Reproduced with permission.[121] Copyright 2021, Elsevier. Reproduced with permission.[122] Copyright 2022, Elsevier. Reproduced with permission.[123] Copyright 2014, Elsevier.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 3.3. Data Analysis",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 15,
+        "chunk": "# 3.3.1. Data Preprocessing and Feature Engineering  \n\nIn the process of data analysis and model building, data preprocessing is the first essential step to ensure the quality and consistency of data, which is foundational for subsequent analyses. Data preprocessing mainly includes data cleaning and data transformation. Data cleaning involves handling missing values, anomalies, and obvious erroneous data. Common methods for dealing with missing values include linear and polynomial interpolation. Linear interpolation estimates missing data based on the values of adjacent points and is suitable for cases where data changes are relatively stable; polynomial interpolation is used when data changes are more complex, providing a more accurate interpolation. Anomaly handling often involves identifying and correcting or removing values that significantly differ from others, typically accomplished through statistical methods like box plots or Z-score methods.  \n\nData standardization and normalization are important parts of data transformation. Standardization is achieved by calculating the Z-score of the data, with the formula  \n\n$$\nZ={\\frac{(X-\\mu)}{\\sigma}}\n$$  \n\nwhere $\\mu$ and $\\sigma$ represent the mean and standard deviation of the data, respectively. This method normalizes the data to have zero  \n\nmean and unit variance, helping to eliminate the effects of different scales. Normalization adjusts the data range to [0,1] using the formula  \n\n$$\nX_{\\mathrm{norm}}={\\frac{\\left(\\mathrm{X}-X_{\\mathrm{min}}\\right)}{\\left(X_{\\mathrm{max}}-X_{\\mathrm{min}}\\right)}}\n$$  \n\nwhere X represents the original data points, with $X_{\\operatorname*{min}}$ and $X_{\\mathrm{max}}$ being the minimum and maximum values in the dataset, respectively. It makes the data comparable on the same scale and suitable for input into most machine learning algorithms.  \n\nAfter data preprocessing, feature engineering is conducted to extract and construct features that aid in model prediction. This includes creating new statistical parameters, performing effective variable selection, and necessary data format transformations to meet the model’s needs. For example, calculating the moving average of time series data to smooth the data or constructing composite features (such as interaction terms) to increase the model’s nonlinear capabilities and interpretability. This step not only enhances the model’s predictive power but also aids in improving the model’s understanding and interpretation of the data.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 16,
+        "chunk": "# 3.3.2. Feature Screening  \n\nIn the preparatory phase of model training, comprehensive data analysis is essential to maximize the utility of data and ensure accurate model predictions. The process includes several critical, nonsequential steps that independently contribute to understanding and preparing the data for modeling. Correlation analysis is initiated using statistical methods (PCC and MIC) to evaluate both linear and nonlinear relationships between features and the target variable. The PCC, which measures the linear association between variables, is calculated as  \n\n$$\nP C C=\\frac{\\sum\\left(x_{i}-\\bar{x}\\right)\\left(\\gamma_{i}-\\bar{\\gamma}\\right)}{\\sqrt{\\sum\\left(x_{i}-\\bar{x}\\right)^{2}\\left(\\gamma_{i}-\\bar{\\gamma}\\right)^{2}}}\n$$  \n\nwhere $x_{\\mathrm{i}}$ and $\\gamma_{\\mathrm{i}}$ are the individual sample points, and $\\bar{x}$ and $\\gamma$ are the mean values of the variables.  \n\nAdvanced statistical techniques such as Principal Component Analysis (PCA) and Factor Analysis are employed to delve deeper into the data structure and reduce its dimensionality. PCA, for example, transforms high-dimensional data into a lowerdimensional space by identifying principal components that capture the most variance  \n\n$$\n\\begin{array}{l}{{Z=X-{\\bar{X}}}}\\\\ {{\\ }}\\\\ {{P C A\\left(Z\\right)=Z\\mathrm{W}}}\\end{array}\n$$  \n\nwhere $Z$ represents the data adjusted by subtracting the mean $\\bar{X}$ , and $W$ is the matrix of eigenvectors derived from the covariance matrix of $Z$ .  \n\nFeature importance analysis plays a pivotal role in the development of machine learning models, particularly when employing complex algorithms such as Random Forests (RF) and Gradient  \n\nBoosting (GB). These algorithms come equipped with the ability to assess the contribution of each feature toward the model’s predictive performance, quantifying the specific impact of each feature on model performance.  \n\nIn RF, feature importance is calculated by observing the contribution of each feature to reducing model error during the construction of decision trees. Specifically, it considers the contribution of each feature in reducing impurity (such as Gini impurity or entropy) when used as a split node across all trees. A higher contribution indicates that the feature significantly impacts model prediction accuracy.  \n\nGB assess feature importance slightly differently. They typically consider the contribution of each feature to performance improvement in each iteration. If a feature is frequently used to split nodes across multiple iterations and each split significantly enhances the model’s performance, the feature is considered important. It is a crucial step in ensuring that the model is ready to efficiently handle complex learning tasks. It provides a solid foundation for model training, ensuring the accuracy and reliability of predictions.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 17,
+        "chunk": "# 3.4. Machine Learning (ML)  \n\nThe fundamental tenets of ML entail the discernment of regulations and patterns from specific datasets through computational means. Within this process, automated enhancement stands as a distinguishing feature of ML algorithms, endowing them with the capacity to iteratively refine their performance through critically assessment of datasets without human intervention. Through the iterative optimization of models over multiple cycles, ML algorithms consistently elevate both accuracy and holistic efficacy, thereby encouraging the model within a state of refinement.  \n\nFigure 7 highlights the chronological trajectory of algorithmic discoveries that have wielded a substantial influence within the realm of ML. The genesis of ML traces back to the 1950s and 1960s, embarking on a journey characterized by significant developmental epochs that spanned from the inception of NN algorithms to the emergence of deep learning. Throughout this evolutionary trajectory, foundational algorithms, and concepts have been successively introduced.  \n\nInspired from the timeline of key milestones, we provide a visual representation of commonly employed ML algorithms in Figure 8a. It is always organized into four primary categories: supervised learning, unsupervised learning, reinforcement learning, and deep learning. In supervised learning, algorithms endeavor to discern the relationship between input parameters and corresponding output parameters, with access to labeled output data. Logistic regression, a supervised learning technique, is apt for binary classification and finds utility in fault detection. Gaussian processes not only yield predicted values but also provide confidence intervals for each prediction. Conversely, unsupervised learning operates without the explicit pursuit of predefined objectives, instead aiming to uncover inherent structures within a given dataset, which primarily serves classification and clustering purposes. Reinforcement learning, conversely, serves to optimize process parameters through iterative adjustments guided by feedback from human settings.  \n\n![](images/4526a09db103c15e18ad92bb214ce4b622ef5d5d477259cee9189f63ba704955.jpg)  \nFigure 7. A brief timeline of key milestones for the development of ML.  \n\nDeep learning is especially valuable in image recognition and processing, notably in the context of coatings. Among these, supervised learning finds extensive application in data processing. Figure 8b presents a schematic diagram of four prominent algorithms commonly used in supervised learning for materials discovery, which are K-nearest neighbors (KNN), RF, SVM, and NN.  \n\nKNN is an instance-based learning algorithm that operates by identifying the k nearest data points in proximity to a given sample, leveraging the labels of these nearest neighbors to predict the label of new data points. It addresses both regression and classification problems by computing distances between the samples to be classified and known samples. The distance is defined as follows  \n\n$$\nD\\ \\left(x,x_{i}\\right)={\\sqrt{\\sum_{j}\\left(x_{i}-x_{i j}\\right)^{2}}}\\quad\n$$  \n\nwhere $D(x,x_{i})$ is the distance between data point $x$ and training sample $x_{i}$ . This is called Euclidean distance.  \n\nKNN boasts simplicity and ease of implementation, however, its computational demands become formidable when dealing with extensive datasets. This stems from the necessity to compute distances between each point and all other points, with the computational burden intensifying as data dimensionality increases.  \n\nRF, in contrast, represents an ensemble learning method that derives predictions from a consensus of multiple decision trees. A single decision tree can exhibit excessive branching, leading to poor generalization and overfitting on training data. By aggregating the outputs of multiple decision trees, RF enhances generalization while mitigating overfitting. Its core process involves constructing numerous decision trees and combining their predictions through voting or averaging.  \n\nSVM is a binary classification model, which seeks to find a hyperplane that maximizes the margin between two classes within a dataset. For linearly separable data, the objective is to identify a decision boundary  \n\n$$\n\\boldsymbol{w}^{T}\\boldsymbol{x}_{i}+\\boldsymbol{b}=\\boldsymbol{0}\n$$  \n\nsatisfying the equation  \n\n$$\n\\gamma_{i}\\left(\\boldsymbol{w}^{T}\\boldsymbol{x}_{i}+\\boldsymbol{b}\\right)\\geq1,\\forall i\n$$  \n\nwhere $\\gamma_{i}$ represents the label of $x_{i}$ . When dealing with nonlinearly separable data, a mapping to a higher-dimensional space facilitates the discovery of a linear hyperplane in this expanded context.  \n\nNN, inspired by the human nervous system, comprises interconnected artificial neurons arranged in layered structures, emulating the neural processes in the human brain. The NN’s formulation is as follows  \n\n$$\n\\gamma=f\\left(\\sum_{i}w_{i}x_{i}+b\\right)\n$$  \n\nhere, $w_{i}$ represents the weights, $x_{i}$ signifies the input, $b$ denotes the bias term, and $f$ is the activation function. The NN iteratively adjusts weights through forward and backward propagation to minimize the difference between predicted and actual values, continuing until a suitable convergence criterion is met. This iterative process refines the network’s ability to perform complex recognition tasks.  \n\nFacing nearly ${\\approx}10^{8}$ types of HEAs can be developed from ${\\approx}64$ elements in the periodic table, Singh et al.[139] tested five vanilla algorithms including KNN, SVM, DT, RF, and XGBoost (XGB) concerning HEA fabrication using melting and casting manufacturing methods to predict the phase transitions in HEAs. Vazquez et al.[140] employed a deep neural network (DNN)- based model to identify frequent phases within the elemental system comprising Mn, Ni, Fe, Al, Cr, Nb, and Co. Actually, each algorithm possesses distinct situational strengths and weaknesses. For instance, SVM are predominantly utilized for classification tasks. Similarly, decision trees are well-suited for classification but may exhibit overfitting concerns when the tree structure becomes excessively complex. The implementation of a voting mechanism in RF mitigates the risks associated with overfitting. Table 1 comprehensively outlines the advantages, disadvantages, and application contexts of select algorithms within these four principal categories of ML methodologies.[141]  \n\n![](images/8bdb339bc0b827af0f570852c1dbab22a6fecbd0042c028b665b11e331507ae0.jpg)  \nFigure 8. a) Common machine learning (ML) algorithms organized into four primary categories. b) A concise schematic illustrating four prominent ML algorithms commonly used in supervised learning for materials discovery: K-nearest neighbors (KNN), random forest (RF), support vector machine (SVM), and neural networks (NN).  \n\nIn the development of deep learning, several advanced models have significantly extended the field, including convolutional neural networks (CNNs), recurrent neural networks (RNNs), long short-term memory networks (LSTMs), and transformer models. Each model has a unique structure and purpose, effectively handling various complex data and challenges.  \n\nTable 1. Comparison of machine learning (ML) algorithms used: advantages, disadvantages, and applications.[141]   \n\n\n<html><body><table><tr><td>Category</td><td>Algorithma)</td><td>Advantages</td><td>Disadvantages</td><td>Applications</td></tr><tr><td>Supervised learning</td><td>Logistic regression</td><td>Simple,interpretable</td><td>Suitable for linearly separable problems only</td><td>Classification</td></tr><tr><td></td><td>Support vector machine (SVM)</td><td>Handles linear/nonlinear data, effective in high dimensions</td><td>Long training time, less suitable for large datasets</td><td>Classification,regression</td></tr><tr><td></td><td>Decision trees (DT)</td><td>Interpretability, automatic feature selection</td><td>Prone to overfitting</td><td>Classification, regression</td></tr><tr><td></td><td>Random forests (RF)</td><td>Reduces overfitting, parameter tuning often unnecessary</td><td>Less interpretable</td><td>Classification, regression</td></tr><tr><td></td><td>K-nearest neighbors (KNN)</td><td>Simple</td><td>High storage and computational cost</td><td>Classification,regression</td></tr><tr><td></td><td>Gaussian process</td><td>Highly flexible, no need to specify model form</td><td>Computationally intensive</td><td>Regression, classification</td></tr><tr><td></td><td>Neural networks (NN)</td><td>Handles complex problems, many parameters</td><td>Requires large data,long training times</td><td>Classification,regression,feature extraction</td></tr><tr><td>Unsupervised learning</td><td>K-means</td><td>Easy to understand, fast</td><td>Need to specify number of clusters,sensitive to initial values</td><td>Clustering</td></tr><tr><td></td><td>Hierarchical clustering</td><td>No need to preset number of clusters</td><td>Computationally intensive</td><td>Clustering</td></tr><tr><td></td><td>Principal component analysis (PCA)</td><td>Dimensionality reduction, retains information</td><td>Might lose critical information</td><td>Data analysis, dimensionality reduction</td></tr><tr><td></td><td>Autoencoders</td><td>Feature learning, anomaly detection</td><td> Training can be complex</td><td>Dimensionality reduction, anomaly detection</td></tr><tr><td></td><td>Apriori</td><td>Straightforward</td><td>Might be inefficient on large datasets</td><td>Frequent itemset mining</td></tr><tr><td>Reinforcement</td><td>Eclat</td><td>Efficient, requires a single scan</td><td>May need significant memory</td><td>Frequent itemset mining</td></tr><tr><td>learning</td><td>Q-learning</td><td>Model-free, easy to implement</td><td>Possibly ineficient in large state/action spaces</td><td>Reinforcement learning</td></tr><tr><td></td><td>Deep Q-network (DQN)</td><td>Handles high-dimensional and continuous spaces</td><td>Requires significant computational resources</td><td>Reinforcement learning</td></tr><tr><td></td><td>Policy gradient methods</td><td>Directly optimizes policy</td><td>May suffer from high variance</td><td>Reinforcement learning</td></tr><tr><td>Deep learning</td><td>Deep feedforward networks Convolutional neural network</td><td>Large model capacity</td><td>Needs vast data</td><td>Classification, regression</td></tr><tr><td></td><td>(CNN)</td><td>Efficient for image processing</td><td> Primarily for image data</td><td>Image classfication, object detection</td></tr><tr><td></td><td>Recurrent neural network (RNN)</td><td>Handles sequence data</td><td>Training can be challenging</td><td>Sequence prediction, text generation</td></tr><tr><td></td><td>Long short term memory (LSTM)</td><td>Addresses RNN's long-term dependencies issue</td><td>Training might be slower</td><td>Sequence prediction, text generation</td></tr><tr><td></td><td>Transformer</td><td>Parallel processing, handles long-distance dependencies</td><td>Requires vast data</td><td>NLP, language modeling, machine translation</td></tr></table></body></html>\n\na) Some algorithms can be used in different categories.  \n\nCNNs are specifically designed to process data with a clear grid-like structure, such as images. CNNs use convolutional layers to locally connect and share weights, significantly reducing the model’s parameter count and enhancing the efficiency and accuracy of image processing. For instance, in image recognition and video analysis, CNNs can identify and classify objects within images.  \n\nRNNs excel in processing sequential data, such as text or time series data. Through their recurrent network structure, RNNs retain information from a previous state and use it to influence the output of the current state. This feature makes RNNs exceptionally effective in speech recognition, natural language processing, and other sequence prediction tasks.  \n\nLSTMs are a special form of RNNs that address the issue of vanishing or exploding gradients in traditional RNNs when processing long sequence data. LSTMs introduce three gates (input, forget, and output gates) to regulate the inflow, retention, and outflow of information, thereby maintaining long-term dependencies in tasks, such as machine translation and text generation.  \n\n![](images/599ae5c09e2d248a791c3ea3642c7ead8738325e543446b8de760b81f3c76bc3.jpg)  \nFigure 9. Limitations of current data-driven materials discovery techniques and potential solutions.  \n\nTransformer models, with their unique attention mechanism, can process data independently of its sequential nature. This makes Transformers more efficient in handling large volumes of data and exhibits outstanding performance in natural language processing tasks, such as text translation and sentiment analysis.  \n\nA team from institutions in the USA and China introduced a new machine learning-based protocol—deep potential molecular dynamics (DPMD).[142] DPMD can simulate systems with over 100 million atoms and complete trajectories longer than 1 ns within a single day, a feat unimaginable with traditional molecular dynamics methods. These advanced deep learning models and the application of DPMD demonstrate the immense potential of machine learning in handling large-scale and complex data, opening new possibilities for scientific research and industrial applications. These advanced deep learning models and the application of DPMD demonstrate the immense potential of machine learning in handling large-scale and complex data, opening new possibilities for scientific research and industrial applications.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
+        "chunk": "# 3.5. Limitations of Current Data-Driven Materials Discovery Techniques and Potential Solutions  \n\nData-driven methods analyze large datasets to identify patterns and correlations for making predictions, generating new hypotheses, or uncovering hidden mechanisms. This approach quickly processes vast amounts of data, leading to faster results and more accurate predictions with less reliance on expert knowledge. However, as shown in Figure 9, there are still some limitations that need addressing to fully realize their potential. This section discusses these limitations and suggests potential solutions.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 19,
+        "chunk": "# 3.5.1. Data Quality and Quantity  \n\nThe accuracy and reliability of predictive models depend heavily on the quantity and quality of the data used to train them. The influence of data quality contains three fundamental domains: data accuracy, completeness, and consistency. Data accuracy stands as the linchpin of dataset quality, with inaccuracies potentially yielding erroneous conclusions. The correlation degree of curves fitted by scatter plots should be considered in the data collection process. Data completeness is closely linked to whether the dataset encompasses all requisite information. This entails verifying the inclusion of comprehensive experimental conditions and ensuring a balanced data distribution of specific variables within the dataset. Data consistency pertains to the uniformity of data within each class and across the dataset as a whole, including aspects such as unit conformity and format consistency. Inconsistencies in data pose a significant risk, as they can lead to excessive deviations in model fitting. The quantity of data also wields a profound influence, impacting both model complexity and data reliability. Data reliability holds significance in its ability to mitigate the risks associated with noisy and anomalous data, reinforced by multiple data points. Increasing data volume consequently reduces the influence of distribution variability on accuracy, contributing to a more robust model performance.  \n\nSolution: Data cleaning and preprocessing techniques are used to improve data quality. Additionally, material databases, experimental measurements, and simulations can also be used to increase the amount and diversity of available data. Following the data collection phase, the identification and management of outliers should be carefully handled. In order to maintain the consistency of data, the unified unit can effectively reduce the error caused by unit differences after data collection. For ensuring data completeness, the generation of distribution graphs for specific variables aids in assessing the dataset’s comprehensiveness. A greater degree of uniformity within the distribution signifies enhanced data completeness.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 20,
+        "chunk": "# 3.5.2. Lack of Standardization  \n\nData collected from different sources is difficult to reach a uniform standard. Consequently, the issue of data consistency across multiple sources poses a substantial hurdle. For identical types of experiments, different laboratories may employ distinct methodologies or employ dissimilar instruments for characterization, resulting in disparities within ostensibly identical data categories. These inconsistencies hinder meaningful data comparisons. Moreover, the problem of incomplete data is prevalent among some sources, and data format inconsistencies further complicate data integration and cross-source comparisons. Additionally, differing data representations, such as tables, images, and text, require manual processing or software-driven transformation into a standardized format. Consequently, the development of robust data harmonization and quality assurance strategies remains imperative to mitigate these challenges effectively.  \n\nSolution: Researchers may establish standardized protocols and guidelines for data collection, storage, and sharing in materials research. Implementing data quality control measures, such as rigorous data cleaning and validation processes, can help identify and rectify any inconsistencies or inaccuracies in the collected data. In addition, promoting open and transparent data sharing practices can encourage researchers to openly publish their data and methodologies. This can enable the wider scientific community to assess, validate, and verify the data, thus ensuring its quality and reliability. This concerted effort not only empowers researchers to harness diverse datasets effectively but also serves as a catalyst for advancements and innovations in the field of materials science.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 21,
+        "chunk": "# 3.5.3. Algorithm Selection and Optimization  \n\nA diverse array of ML algorithms exists, each offering unique advantages and constraints, making it essential to choose the appropriate algorithm for the task at hand. Related problems encompass a spectrum, including classification, clustering, and regression. Classification involves the segmentation of data into distinct groups based on provided labels. Clustering, conversely, entails the unsupervised categorization of data into groups without relying on predetermined labels. Regression concerns itself with predicting output values based on input parameters. The choice of algorithm hinges on the nature of the specific problem at hand. The volume of data also plays a pivotal role in algorithm selection. Certain algorithms, like GB, tend to perform optimally when deployed on extensive datasets, in contrast, algorithms such as KNN are adept at handling high-dimensional data, executing classification or regression tasks based on sample distances. Furthermore, the selection process should consider the trade-off between accuracy and computational complexity.  \n\nSolution: It is imperative for the investigator to possess an exhaustive comprehension of the available dataset. To this end, the initial stage necessitates the identification of fundamental elements, namely, the problem classification, the dataset’s intrinsic characteristics, and the intended output parameters. A comprehensive comparative evaluation of diverse algorithms should be conducted to assess their efficacy with respect to specific dataset under consideration. In addition, hyperparameters profoundly influence the performance of most algorithms. Employing hyperparameter optimization techniques becomes instrumental in fine-tuning the algorithms’ behavior. By discerning the optimal hyperparameter configurations for each algorithm, researchers can maximize their efficacy.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 22,
+        "chunk": "# 3.5.4. Narrow Focus on Certain Materials  \n\nData-driven approaches could suffer from the possible bias of being limited to the particular material system under investigation. This limitation could lead to underdeveloped models and limited generalization to unknown materials. Excessive fixation by researchers on specific materials carries the inherent risk of overlooking alternative materials with untapped potential, thereby constraining the scope of material innovation. It is essential to recognize that research outcomes pertaining to a particular material system may not readily translate to diverse materials, which is attributed to the inherent diversity in material properties and behaviors.  \n\nSolution: Researchers must focus on an interdisciplinary approach that includes theoretical insights, experimental data, and the application of the knowledge gained from all material systems. This approach can guarantee the optimization of the models’ reliability and applicability. Primarily, theoretical insights possess an inherent capacity for broader applicability across different material systems, which can help researchers to formulate models characterized by a higher degree of generality. Then the empirical validation through experimental data serves to delineate the scope of models’ applicability. An integrated approach, involving the amalgamation of data originating from disparate material systems into a unified framework through standardized practices, represents an avenue for achieving a more comprehensive understanding of material behavior.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# 3.5.5. Interpretability and Transparency  \n\nThe lack of interpretability and transparency associated with complex algorithms can lead to skepticism regarding their reliability and makes it difficult for researchers to gain insights into the underlying relationships between materials properties. In certain computational tasks, the decision-making process of the model unfolds through a multitude of intricate layers and successive steps. This complexity presents a formidable challenge in terms of elucidating and comprehending the underlying rationale for each decision made. The inherent opacity and absence of transparency within such models pose significant impediments. The deficiency in providing coherent explanations and insights detracts from the model’s credibility, impedes its acceptance, and introduces obfuscation into the interpretation of experimental outcomes and predictions engendered by the model.  \n\nSolution: Researchers can adopt techniques, such as feature importance ranking, that offer an interpretation of the models’ predictions. Additionally, transparent models that prioritize interpretability, such as decision trees and linear regression models, can help researchers gain insights into the underlying mechanisms and relationships. The utilization of model visualization techniques represents a valuable strategy for elucidating the intricacies of the decision-making process inherent to the model. In certain instances, an equilibrium between interpretability and accuracy can be attained by judiciously curtailing the model’s complexity. In addition, it is important to cultivate a profound understanding of the model’s architecture and the physicochemical intension of the input features and output targets from the view of materials science.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# 3.5.6. Computational Cost  \n\nModeling and design of materials using data-driven techniques can be computationally intensive, requiring significant computational resources. Computational resources include hardware resources, such as central processing unit (CPU), graphics processing unit (GPU), memory, hard disk, etc. Different data-driven methods have different demands on hardware resources. Meanwhile, the storage and use of large-scale datasets will have a greater demand for hard disks. Complex models and large-scale datasets can take a lot of time which further increases the computational cost. In addition, in order to evaluate the best model, the model is usually trained and evaluated multiple times, as well as fine-tuning the hyperparameters for optimization, which can lead to additional computational costs. These above factors can limit the speed of model training, evaluation, and optimization.  \n\nSolution: Computational efficiency in material discovery can be improved by developing more optimized and parallelized algorithms. Additionally, leveraging high-performance computing platforms and technologies can help distribute the computational workload and reduce the processing time required. Streamline the data collection and preprocessing stages by minimizing redundant or noisy data and utilizing dimensionality reduction techniques can also tackle the computational cost challenge. As for model design, one effective strategy entails streamlining complexity, notably by reducing the number of layers within NN and optimizing the number of neurons. This approach not only truncates training durations but also preserves performance metrics. At last, the integration of an integration algorithm, particularly the amalgamation of a genetic algorithm into the core model, presents an efficacious approach for hyperparameter optimization, which facilitates an exhaustive search of hyperparameter configurations, executed at a relatively expedited pace.  \n\nIn summary, technical challenges such as data quality, standardization, algorithm selection, narrow focus, interpretability and computational cost can pose significant hurdles to the effectiveness of data-driven approaches. However, researchers can still address these challenges through multiple solutions, which include data cleaning, standardized protocols, comparative algorithm performance analysis, interdisciplinary approaches, data processing streamline, among others.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 25,
+        "chunk": "# 4. Typical Applications of Data-Driven Investigations for Functional Coatings  \n\nEfficient data-driven approaches have gradually permeated modern new materials development strategies. In the development of functional coatings, many researchers are beginning to try to use ML to develop new materials. The follow sections will demonstrate the potential of data-driven approaches in functional coatings development through several case studies. They highlight the advantages of using data-driven approaches, especially ML, to accelerate the discovery of new coatings with improved performance.",
+        "category": " Introduction"
+    },
+    {
+        "id": 26,
+        "chunk": "# 4.1. Anticorrosion Coatings  \n\nCorrosion is a primary failure form for most materials. Since it is inevitable, mitigating corrosion has become a key focus of research to overcome this challenge. Functional coatings serve as protective films, which effectively extend the service life of the materials. Corrosion inhibitors are considered to be one of the most effective anticorrosion functional coatings, whose main functional component is organic molecules. In general, corrosion inhibitors reduce the corrosion by absorbing water and oxygen on the surface of the materials. Therefore, the interfacial adsorption, hydrophilic, and dense properties of corrosion inhibitor molecules directly affect the protection ability of anticorrosion coatings. These characteristics, including chemical structure, charge distribution, film thickness, and roughness, are used as molecular descriptors in data-driven models to establish linear relationships with material property/activity, known as quantitative structure–property/activity relationships (QSPR/QSAR), thereby predicting or designing effective corrosion inhibitor molecules.[143]  \n\nConsidering plentiful candidate organic molecules with potentially useful properties, the traditional trial-and-error method is not only time-consuming and labor-intensive, but also may cause resource waste and environmental pollution. Fortunately, datadriven approaches facilitate rapid exploration of available corrosion inhibitors on the ground of QSPR/QSAR. Among these, ML is the most widely used method. First, ML methods are able to quickly screen functional organic molecules (Figure 10). Galvão et al.[144] used different algorithms to classify 102 organic compounds to distinguish whether they are effective corrosion inhibitors for Al alloys in aviation applications. A large number of descriptors, such as molecular weight, octanol/water partition coefficient, polar surface area, dimerization enthalpy, and Gibbs energy, etc., are used. The linear correlation between these descriptors modeled and inhibition efficiencies can be reflected in Figure 10a, which indicated that identifying molecular structures that can be used as corrosion inhibitors is a highly nonlinear problem. Figure 10b presents the corrosion inhibitor characteristics obtained through training. That is, molecules with one or two aromatic rings, few or no rotational bonds, strong polarity, and more favorable dimerization Gibbs energy are beneficial for corrosion inhibition. Second, ML is also used for designing corrosion inhibitors. For instance, based on structural similarity and kernel ridge regression (KRR), ML models predict the ability of small organic compounds to modulate the corrosion of commercially pure $\\mathbf{\\deltaMg}$ .[145] Similarly, Li et al.[146] utilized support vector regression (SVR) and KRR to acquire the corrosion response of 58 small organic molecules on Mg alloy and encoded their molecular information using the molecular descriptors calculated by their geometry and DFT. Figure 10c shows the training database. First, a pool of 2876 different molecular descriptors were generated as input features of the model, and the features were selected. The most relevant descriptors are then used to train ML models to predict the behavior of untested chemicals. The results were finally tested experimentally.  \n\n![](images/5e20a864a6c4f2b483c6403ca7da6ec171161ea4e5df7fae3416949749eb248f.jpg)  \n\n![](images/2c024dccc5adbae392e196c25562e596ce593f04975a12070e2789485febd97b.jpg)  \n\nIn addition, high-throughput experiments are also one of the ways to rapidly develop corrosion inhibitors. The coupling of ML and high throughput experiment can not only improve the sieving efficiency of corrosion inhibitor molecules and enabling quantitative prediction of material properties, but also accelerate the validation of predictions. In search of effective alternatives to toxic chromate corrosion inhibitors, Winkler et al.[147] combined high-throughput corrosion screening techniques and modern ML methods to obtain the molecular structure-corrosion inhibition relationship for a large number of corrosion inhibitors applied to aerospace Al alloys. Deservedly, metal coatings are another commonly used anticorrosion coating. Álvarez-Zapatero team presented a NN potential capable of predicting the structure of pure and hybrid nanoparticles.[148] The specific training protocol is shown in Figure 10d. In comparison with the values provided by DFT used in the training process, the NN potential able to predict structures with an error in energy and forces of the order of chemical accuracy. Specifically, $\\mathbf{ZnMg}$ nanohalloys with up to 52 atoms were tested and analyzed for structural properties, chemical order, stability and electronic information, to determine whether they could be used as effective corrosion-resistant coating compositions.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 27,
+        "chunk": "# 4.2. Temperature-Resistant Coatings  \n\nHigh-temperature protection coatings are design to provide thermal insulation or withstand extreme heat, which are used to prevent surface oxidation and performance degradation of hightemperature equipment in various fields, such as aerospace, nuclear energy, and manufacturing. The service performance improvement is always accompanied by an increase in working temperature. However, typical heat-resistant materials, such as ceramics or refractory metals, may suffer from phase or structure transformations at high temperatures, leading to a significant accident caused by material damage. The data-driven design of temperature-resistant coatings based on the data ocean has been developing for a long time (Figure 11). Hao et al.[149] adopted ML based on experimental datasets to build a model for predicting the oxidation and ablation resistance of ultra-high-temperature ceramic (UHTC) coatings. 13 factors were considered, and SHapley Additive exPlanations (SHAP) was used to derive each factor’s priority in affecting the coatings’ performance (Figure 11a,b). The mass ablation rates of UHTC coatings increase with melting point $(\\mathrm{Mp}_{\\mathrm{min}})$ , the enthalpy change of oxidation reaction $(\\mathrm{Hfo}_{\\mathrm{ave}})$ , standard enthalpy of formation $\\mathrm{(Hf_{ave})}$ , the temperature of the sample surface (Tem), the powder’s particle size $(\\mathrm{P_{S}})$ , and formation energy $(\\mathrm{Fe_{ave}})$ , but negatively correlate with the density $(\\rho_{\\mathrm{max}}$ and $\\rho_{\\mathrm{ave}})$ and the porosity of the coating $\\left(\\mathrm{P_{o}}\\right)$ (Figure 11a).The factor importance $(|\\mathsf{S}\\mathrm{HAP}|)$ shows that $\\mathrm{{Mp}_{\\mathrm{{min}}}}$ is the most critical factor for predicting mass ablation because of the liquid phase without protection (Figure 11b).  \n\nThermal barrier coatings (TBCs) are important in gas turbine engines, power-generation turbines, and rocket engines. However, the effect of thermal stress on TBCs stability and durability remains difficult to assess, which has puzzled scientists until a new study presented recently by Zhong et al.[150] They developed a cross-scale model that combines DFT calculations, thermodynamic calculations, FEM, and ML to evaluate the thermal stress of TBCs (Figure 11c). Taking rare earth tantalate as an example, the thermal expansion coefficient, heat capacity, thermal conductivity, Young’s modulus, Poisson’s ratio, density, and other properties were obtained by DFT calculation. Then coupled with FEM, the temperature field and stress field distribution were quantified and visualized. Furthermore, the decision tree with thermal stress as the target property was established. The important features affecting thermal stress were ranked to found the features related to low thermal stress, including small Poisson’s ratio, strong electronegativity, small heat capacity, and thermal expansion coefficient. Finally, the rationality and reliability of the low-stress mapping characteristics obtained by ML are verified by using $\\mathrm{YTaO}_{4}$ and double rare earth tantalate $(\\mathrm{Ho}_{0.5}\\mathrm{Er}_{0.5})\\mathrm{TaO}_{4}$ which are not available in the data set.  \n\nAs material genetic engineering develops by leaps and bounds, the prediction of material properties can be achieved based on visual analysis technology. As one of the traditional protective methods, the protective coating has made it difficult to achieve accurate prediction of coating life due to its service process covering many factors and complex failure factors. Liu et al.[151] collected a large number of topography images during the service of the coating and through visual analysis technology to establish image preprocessing screening and standardization. A multilayer convolutional neural network (8–10 layers) was established to automatically identify the characteristic phase of the signal for distinguishing the coating, coating/substrate interface, and corrosion product layer (Figure 11d). Based on the measured results of the coating performance, the neural network was used to establish an effective network correlation between image quantitative and performance quantitative. The image simulation and reconstruction simulation network of coating changes under different service time were established, to realize the simulation of coating service performance image state and life prediction.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 28,
+        "chunk": "# 4.3. Wear-Resistant Coatings  \n\nAmong a variety of properties of functional coatings, wear resistance has been regarded as a critical one, especially for the surface protection of moving components of machineries. Based on data-driven approaches, the role of key microstructural, property, and environmental parameters on the tribological behaviors can be isolated to guide the design of wear-resistant coatings. Xu et al.[152] screened high-entropy coating combining the ML and high-throughput magnetron sputtering experiment (Figure 12a–c). The SHAP suggested that high values of bias voltage, N, Te, and Ta, and low values of Ni and Cr were the key factors of the coatings hardness by training the data of 167 pieces of literature (Figure 12a). Six types of ML algorithms were performed, including linear regression (Lin), linear kernel support vector regression (SVR.l), polynomial kernel support vector regression (SVR.p), radial kernel support vector regression (SVR.r), RF, and gradient boosting regression (GBR) models, to establish the relationship between seventeen variables and hardness. The train error and test error of different ML algorithms showed RF and GBR performed well (Figure 12b). But GBR had an overfitting phenomenon. RF was selected to guide the preparation parameters of coatings.  \n\n![](images/9c852ce0bdb623b809605f991954eb8caee81cedb31ab9fba5ea68514d1c487e.jpg)  \nFigure 11. a) SHAP values and b) |SHAP| values affecting oxidation and ablation to clarify the failure mechanisms of ultrahigh-temperature ceramic coatings. Reproduced with permission.[149] Copyright 2022, Elsevier. c) A multiscale evaluation method coupled with DFT calculations, FEM, and ML, can be used for reverse design for thermal barrier coating. Reproduced with permission.[150] Copyright 2024, Elsevier. d) The architecture of the convolutional neural network for recognizing the characteristic phases of the NiCrAlY coating after oxidation. Reproduced under the terms of the CC-BY license.[151] Copyright 2022, the Authors, published by Springer Nature.  \n\n![](images/32ea5d26f9c26cc7eed51971a589109d33e5d5a05c12ebf49071bef87b9e0874.jpg)  \nFigure 12. a) Global interpretation using SHAP. b) Train error and test error of different machine learning models. c) The optimal hardness and elastic modulus of screened composition by ML and high-throughput experiment compared with other works. Reproduced with permission.[152] Copyright 2022, Elsevier. d) The sketch map of CGCNN transforms the crystal structure into a crystal graph and then outputs the result as a variable input through a series of processes. e) The disordered compound’s predicted and calculated elastic constants are highly consistent. Reproduced under the terms of the CC-BY license.[74] Copyright 2022, the Authors, published by Springer Nature. The algorithm diagram of f) SVM, g) ANN, h) RF, and i) ET. j) Predicting the microhardness of $N i{\\cdot}P{\\cdot}T_{1}0_{2}$ composite coating by ET. Reproduced with permission.[154] Copyright 2023, Elsevier.  \n\nThe high-throughput magnetron sputtering experiments found the hardness of (AlCrNbTaTi)N coating based on the prediction of RF reached $40.1\\mathrm{GPa}$ , which proved the prediction model has great potential in the development of super-hard high-entropy ceramic coatings (Figure 12c). Their team further screened a new composition coating of (AlCrTiMoTa)N with a hardness of $33.4\\mathrm{GPa}$ and modulus of 287.7 GPa through ML and multiobjective optimization from the database of high-entropy ceramic coating.[153] ML can also establish the relationship between 3D structure and performance. Levämäki et al.[74] applied a method that combined DFT calculation and ML to predict elastic properties of hard-coating alloys, such as $\\mathrm{Hf}_{1-x}\\mathrm{Al}_{x}\\mathrm{N}$ and $\\mathrm{Ti}_{1-x}\\mathrm{Al}_{x}\\mathrm{N}$ $\\boldsymbol{\\mathscr{x}}=0$ , 0.25, 0.5, 0.75, 1). They used the database of elastic properties for order compounds in the material project to train the crystal graph convolutional neural network (CGCNN) (Figure 12d). The DFT calculation was performed to calculate the elastic constants of disordered compounds, but was rarely used due to the high cost. Then, the transfer learning (TL) approach established a relationship between the abundance of data for ordered compounds and more minor data for disordered compounds. The predicted bulk (B), shear (G), Young’s (E) modulus, and Poisson’s ratio v of the disorder compound are highly consistent with the calculated value (Figure 12e). Despite using a small amount of data from disordered compounds, it is still possible to accurately predict the data of unknown disordered compounds from the data of large ordered compounds and a few disordered compounds. This method might accelerate the discovery of new hard-alloy coatings with disordered crystal structures. The influence of different treatment methods on the hardness of the coating can be predicted by ML. Shozib et al.[154] applied four ML algorithms, including SVM, ANN, RF, and Extra Trees (ET), to predict the microhardness of the $\\mathrm{Ni-P{\\cdot}T i O}_{2}$ coating (Figure 12f–i) obtained from different compositions and operation conditions of electroless plating bath solutions. The ET was considered a learning model that can minimize the experimental complexities, time, and expense in the manufacture of parts with good surface properties by predicting microhardness (Figure 12j). This method provides a new way to establish a strong relationship between surface modification and coating performance without experimental cost.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 29,
+        "chunk": "# 4.4. Antifouling Coatings  \n\nMaterials can effectively extend their service life by preventing the surface from being attached to biological, inorganic, and organic matter. Early antifouling strategies are embedding metal and/or organometallic fungicides into the polymer matrix of the paint.[155] The toxicity and biological harmfulness of fungicides seriously destroy the environment. Therefore, the modern antifouling policy aims at screening nontoxic and efficient antifouling polymers. The rational design of highly antifouling coatings is essential for fundamental research and applications (Figure 13). The previously mentioned QSAR can be also used to design antifouling coatings. Rasulev et al.[156] synthesized a set of 27 nontoxic, amphiphilic polysiloxane-based polymer coatings by a combinatorial, high-throughput approach. Schematic diagram of the overall steps is shown in Figure 13a. They proposed the variable selection GA and multiple linear regression analysis (MLRA) methods to develop QSAR model to predict foulingrelease activity of relevant marine fouling organisms, including bacteria, microalgae, and adult barnacles. It was found that the polarizability indices, size, mass, and van der Waals volume could significantly affect the antifouling performance of the coatings. In addition to the marine industry, biological antifouling in the medical sector is also crucial. The protein adsorbed on the surface of nanomaterials is an important medium at the bio-nanomaterials interface. Therefore, antiprotein surface coatings can prevent biological contamination. Le et al.[157] used ML methods to extract quantitative relationships between surface chemistry of materials and protein adsorption properties to reliably predict the degree of protein adsorption on the surface of materials, aiming to design effective antifouling coatings. Liu et al.[158] developed a data-driven ML model, combing factor analysis of functional group (FAFG), Pearson analysis, RF, and ANN algorithms as well as Bayesian statistics, to evaluate the antifouling performance of any given or designed self-assembled monolayers. The key molecular descriptors and functional groups for the rational design of antifouling materials were identified. The ANN model was trained and verified by constructing datasets, as shown in Figure 13b,c. Through modeling and prediction, three kinds of antifouling molecules were synthesized and made into self-assembled monolayers (SAMs). The experimental results showed that all three kinds of SAMs could adsorb proteins in undiluted fresh plasma. However, after rinsing with phosphate buffer solution, the proteins all fell off (Figure 13d), and the final adsorption amount was shown in Figure 13e, which indicated that SAMs had weak adsorption capacity for proteins, that is, protein resistance. The difference between SAM-1 and SAM-3 is that the ether group in SAM-1 and the amide group in SAM-3 contribute differently to their respective protein resistance, which is consistent with model predictions.  \n\n![](images/cf0e618b38931bc4cb6918385f308a2975598daab86d8efd166acc9d54d2f58d.jpg)  \nFigure 13. a) Schematic diagram of polymer coating modeling and design. Reproduced with permission.[156] Copyright 2017, American Chemical Society. Validation of the predictivity and reliability of the ANN model: b) Plot of the predicted versus experimental log (RPA) for both training and test sets. c) Application domain analysis of 26 testing samples using the KNN approach. Experimental validation of the protein resistance property of the three designed SAMs: d) Protein adsorption sensing data of the three SAMs in undiluted human blood plasma. e) The final protein adsorption amount of the three SAMs. Reproduced with permission.[158] Copyright 2021, American Chemical Society.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 30,
+        "chunk": "# 4.5. Self-Healing Coatings  \n\nFunctional coatings are used to enhance the sustainability of the materials. However, during harsh conditions, whether they are anticorrosion coatings, wear-resistant coatings, or antifouling coatings, all of them will be subjected to environmental or internal stress resulting in defects. In nature, biological organisms possess repair mechanisms to prevent loss of function, which involves processes of a series of physical/chemical reactions. Similarly, functional coatings on the surface of service materials can be sustainably applied as long as they are allowed to spontaneously heal and repair defects. Self-healing coatings are divided into external self-repair and intrinsic self-repair according to repair types.[159] External self-healing coatings are pre-embedded with additional components, such as microcapsules,[160] carbon nanotubes,[161] fibers,[162] or nanoparticles containing,[163] to realize self-healing function. Under the action of external stimuli (force, pH value, temperature, etc.), the repair agents are released in the damaged region, so as to achieve self-healing. External selfhealing methods are considered to have universal applicability for most coatings. The intrinsic self-healing function is realized by the coating material itself containing special chemical bonds or other physical and chemical properties such as reversible covalent bonds, noncovalent bonds, molecular diffusion, etc. The latter eliminates complex steps such as pre-repair agent embedding technology, and has little impact on substrate properties. The molecular structure design of coating substrate materials is a significant challenge before data-driven methods are widely applied. The multichannel preparation and high-throughput screening methods shorten the experimental time by nearly ten times. Manabe et al.[164] built a ML database based on their experimental research to understand the effects of additives on repair times. By integrating ML with NN and gradient boosting decision tree (GBDT), cross-validation was carried out with the experimental results. Using 14 descriptors as input parameters, they predicted that the horizontal/vertical swelling rate ratio, water absorption rate, and thickness were key factors in reducing self-healing time. The model was then used to predict the $\\scriptstyle{\\mathrm{Zn}}^{2+}$ doped coating, and it was found that the coating did not exhibit self-healing ability, which is consistent with the experimental results. Therefore, it is possible to obtain an initial evaluation of coating properties by inputting the physical and chemical properties of polymers and additives as basic parameters through ML. However, the accuracy of the model needs to be optimized with more available data, otherwise there may be a high risk of overlearning. Fortunately, Anwar Ali et al.[165] proposed a model to predict and understand the evolution of self-healing properties of polymers using energy functional dynamics (SPEED) (Figure 14). Using ML method, the energy function minimization (EFM) model describes the physical mechanisms of self-healing in terms of potential and interfacial energies by extracting an effective underlying dynamical system from a time series of 2D cut images of self-healing polymers of constant thickness. As shown in, the EFM model can predict the healing time of different incision shapes with high prediction accuracy (Figure 14a), and the prediction results of training data (Figure 14b) and test data (Figure 14c) show low healing efficiency errors (Figure 14d,e). The SPEED model, in combination with a static performance prediction model, enables the prediction of macroscopic material properties by training only a small set of experimental measurements evolution.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 31,
+        "chunk": "# 4.6. Electrically Correlated Coatings",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 32,
+        "chunk": "# 4.6.1. Electronic Coatings  \n\nElectronic materials determine the pace of intelligent development, and the widespread adoption of electronic devices has promoted the research into electronic materials. Among them, the application of electronic coatings is particularly extensive, due to their high electrical conductivity, electromagnetic shielding, and antistatic properties. For refining the properties and improving the functionality of coatings, data-driven approaches have been extensively utilized. Flexible electronic materials are a key component in the research of wearable electronic devices and also an important guarantee for the development of high-tech and intelligentization. p-TCMs serve as critical elements within optoelectronic devices such as solar cells, photodetectors, displays, and flexible sensors. Wei et al.[166] demonstrated how ML algorithms, specifically SVR, could efficiently optimize the performance of p-Type transparent conducting materials (p-TCMs) by considering multiple deposition parameters (Figure 15a). The approach involved calculating a figure of merit (FOM) based on coating conductivity and optical transmission, followed by two rounds of optimization to identify optimal areas in the parameter space. Wu et al.[167] introduced a novel ionic conductive hydrogel skin material that exhibited excellent stretchability, strength, toughness, elasticity, transparency, self-healing ability, and stable electrical cycling performance. By integrating a ML module, the hydrogel ionic skin showed tremendous potential in identifying complex human behaviors, such as writing in the air or on paper. The algorithm processed current signals generated from finger movements during writing, achieving high accuracy in predicting and recognizing letters, words, phrases, and short sentences. Certainly, electronic coatings also have extensive applications in electrochemical energy storage. Chen et al.[168] constructed a ML model using 738 sets of data on the relative dielectric constant of polymers, to predict $11\\ 000$ potential polymer candidates. Subsequently, 10 sets of dielectric polymers were investigated. Zhu et al.[169] utilized ML to fine-tune the properties and arrangement of nanofillers, resulting in the creation of a composite material that exhibited high electric breakdown strength and high energy storage density. Kireeva et al.[170] analyzed the existing experimental data of garnet thin coatings in solid-state batteries, focusing on how ionic conductivity was affected by factors such as the lattice mismatch between the coating and the substrate, variations in elastic properties, and inconsistencies in thermal expansion characteristics. Additionally, the impact of the deposition temperature of the coating, the melting point, and the dielectric constant of the substrate on conductivity was investigated. Utilizing the findings from this analysis, a quantitative model for predicting the ionic conductivity of garnet thin coatings was established by using LSTM and Probabilistic Backpropagation (PBP) neural network, as shown in Figure 15b. Interestingly, insulating and separator materials play a vital role in energy storage devices, ensuring their reliable operation.  \n\n![](images/00535099a4e74246a8908b2aa198ccbf32f0bc989cf53a1769deaafe48c93651.jpg)  \nFigure 14. a) Key results of the shape of the cut at different healing times from the EFM model-top row: input cut image data; bottom row: predicted cuts with ML model. The healing efficiency based on a training b) and test c) dataset. The blue line represents the true data and the orange dotted line represents the predicted data. Evolution of healing efficiency error based on training d) and test e) dataset. Orange lines represent the absolute errors between the true and predicted healing efficiency over time. The solid blue line is the average error, and the shadow indicates the standard deviation. Reproduced with permission.[165] Copyright 2022, American Chemical Society.  \n\nSome electronic devices require insulation from external interference to function properly. Salah et al.[171] utilized ML to predict the electromagnetic absorption performance of polycarbonate/carbon nanotube composite materials. By developing a new system, 15 different multilayer perception (MLP) networks were established, each specialized in predicting the absorption value of specific category samples. The research results demonstrated that the system performed exceptionally well in the database, with an average accuracy of $99.7997\\%$ and an overall average calculation time of $0.01295\\mathrm{~s~}$ . Additionally, the composite based on polycarbonate- $5\\mathrm{\\wt\\%}$ carbon nanotube was found to be the ultimate absorber over the microwave range, in line with the requirements of Rozanov formalism. Shi et al.[172] developed a fast predictive ML model for Carbon-based fillers/polymer nanocomposites to shield electromagnetic interference. Relevant features are classified as categorized as categorical or numerical features, as shown in Figure 15c. It was found that the following key features: filler loading, thickness, porosity, and the number of layers, needed to be considered in the design of coatings, and the former should be paid more attention. Such multifunctional electronic coatings using data-driven development have excellent performance, providing strong evidence for data-driven development of more novel and better performance electronic coatings.  \n\n![](images/9e98696a5a55f85b06cc5ee9df143a0ed9c96a99d76556444335d20cbb53ca50.jpg)  \nFigure 15. a) Aims of machine learning optimization. Reproduced with permission.[166] Copyright 2019, American Chemical Society. b) Experimental versus predicted Li-ion -log conductivity values for LSTM (i), PBP (ii) models and their averaged prediction values (iii). Reproduced under the terms of the CC-BY license.[170] Copyright 2023, the Authors, published by MDPI, Basel, Switzerland. c) The composition of data set (i); schematic diagram of one-hot on categorical features (ii); schematic diagram of the model training process, including fivefold cross-validation (iii). Reproduced with permission.[172] Copyright 2019, Elsevier.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 33,
+        "chunk": "# 4.6.2. Solar Cell Coatings  \n\nSolar energy, as a kind of clean energy, has been widely concerned and applied in power generation industry. However, in order to improve the conversion efficiency of solar energy, solar cells are often designed to be large, resulting in expensive manufacturing. Therefore, with the aim of improving the service life, solar cell protective coatings play a key role. The coatings should not only be superhydrophobic, antifouling, and anticorrosion, but also ensure a good light transmittance to ensure the photoelectric conversion efficiency. MacLeod et al.[173] established a selfdriving laboratory named “Ada” to automatically complete the sample preparation, detection, optimization, and screening for the organic hole and electron transport layer or optoelectronics application film. Figure 16a shows the automated workflow of Ada. First, the precursor solutions in different ratios of films are mixed and dropped on the surface of the substrate, which are solidified into coatings under a heated airflow. Second, morphology, spectrum, and conductivity of the thin film will be detected and recorded by a camera, fiber optic, and four-point probe. Finally, the data are automatically inputted into ChemOS using the Phoenics global Bayesian optimization algorithm to analyze and design iterative experiments that guide composition ratio setting in the precursor solutions. After multiple iterations, excellentperformance thin film materials will be selected. Ada takes about $21\\mathrm{min}$ to synthesize, characterize, and plans in one experimental cycle for rapid ingredient screening. An open-source Python software with strong compatibility is used to compile programs for a new experiment in the self-driving laboratory.  \n\nThe metal halide perovskite is a potential material for solar cells to increase efficiency. However, the performance of perovskite solar cells (PSCs) is curtailed due to nonradiative recombination. Passivation coating impedes PSCs’ rapid halide-ion migration and chemical reactions with water, oxygen, and light. Xu et al.[174] addressed the challenges of insufficient defect passivation by previous pseudohalide (PH) anions, which resulted in undesired deep impurity states. To combat this, the study utilized a ML workflow to accelerate the discovery of effective PH anions that could prevent lattice distortion and enhance attachment to the perovskite surface (Figure 16b). First, they screened PH anions from the PubChem database based on six screening tiers, and 168 candidates were selected for surface binding energy calculations including two calculation methods. Gaussian calculations and ML investigated the reason for the molecular structure of PH anions regulating their interaction strength with the perovskite surface. DFT calculations were performed for surface band edge electronic structures and defect formation energy calculations. 24 candidates were confirmed and further verified by experiments. Finally, $15~\\mathrm{PH}$ cations as passivation coating were found to be able to improve power-conversion efficiency. This study combining theoretical calculation and ML provides guidance for the future design of optoelectronic materials.  \n\n![](images/8ef928eb418279701d58e1802d21f5c88562baf53aa4add417624a539c4d3e68.jpg)  \nFigure 16. a) Schematic of Ada’s automated workflow consisting of three main parts: Synthesize, Characterize, and Plan. Reproduced with permission.[173] Copyright 2020, American Association for the Advancement of Science. b) Material screening process workflow with six screening tiers. VBM, valence band maximum; CBM, conduction band minimum. Reproduced with permission.[174] Copyright 2023, Springer Nature.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 34,
+        "chunk": "# 4.6.3. Cathode Coatings for Battery  \n\nLi-ion batteries are currently the most widely energy storage device, benefiting from their advantages of high energy density, high conversion efficiency, and fast response speed. However, users are criticizing the service life of Li-ion batteries declining too fast, especially in mobile phones. At present, there is no good revolutionary technology to replace Li-ion batteries, so that, methods for improvements must be studied. The important reasons for the decline in battery life are the dissolution of the redox-active transition metal ions into the electrolyte, instability against irreversible phase transformations, the dissolution of the cathode, etc. Protective coating, such as Al2O3, MgO, ZnO, etc.,[175,176,177] on the cathode surface, can isolate the cathode and electrolyte and effectively alleviate the occurrence of corrosion. But considering the complex reactions between the cathode, coating, and electrolyte, it is difficult to further select the appropriate multivariate. As mentioned previously, Aykol et al.[87] proposed a strategy for rapid screening of ternary and beyond compounds by high-throughput DFT calculations-based framework to save the trouble of trial-and-error experimentation. The schematic of the method is shown in Figure 17a. The researchers first screened the candidate materials by the criteria of thermodynamic stability for synthesizing experimentally, electrochemical stability for keeping intact in the battery, and nonradioactive & Herfindahl– Hirschman index (HHI) for commercial feasibility analysis from the OQMD. Then, they categorized the candidate materials into three types based on the ability of the materials used as a coating to react with HF: physical barrier for degradation mechanism little related to HF, HF-barrier for protective coating, and HF-scavenger for coating as a sacrificial anode. To balance multiple performance indicators for materials, the best candidate materials were screened by multiobjective optimization with the weighted-sum and rank aggregation. The high similarity of the candidate materials predicted by the weighted sum and rank aggregation indicated the reliability of this work. The functional coatings predicted in this work significantly reduce the cost of materials exploration and aid in battery development. However, there are many factors affecting the performance of battery coatings. Screening by a few important ones could be acceptable, and optimal coatings can be better screened if more factors are considered. Xiao et al.[178] further developed the strategy Aykol et al.[87] proposed by considering whether the coating could be stable with both the cathode and the solid-state electrolyte (SSE) and ionic conductivity for coating performance to screen the cathode coating material for the solid-state batteries (SSBs) from the ICSD and those generated by applying data-mined chemical substitutions. The main difference between the two is that the DFT calculations calculate the chemical stability screening of the latter. In addition, this work considered more reactivity between the fully lithiated cathodes and the coating, as well as the inorganic solid-state electrolytes and the coating (Figure 17b).  \n\n![](images/853efbc2cf6757c4c2cf1056fa36a35e755364cd7490513648e19cae621c2023.jpg)  \nFigure 17. a) The flowchart of designing cathode coatings for Li-ion battery by high-throughput DFT calculation framework. Reproduced under the terms of the CC-BY license.[87] Copyright 2016, the Authors, published by Springer Nature. b) Chemical reaction energy $\\Delta E_{\\mathrm{rxt}}$ with SSEs/coating and fully lithiated cathodes/coating and fully lithiated cathodes/SSEs. Dark green color means low chemical activity and vice versa. Reproduced with permission.[178] Copyright 2019, Elsevier. c) The example of LOTF-MD. The green tetrahedra and trigonal planar geometry is $_{{\\mathsf{B}}-{\\mathsf{O}}}$ bond, Li-ion is sphere, and migrating Li-ions are represented by different colored spheres and locally vibrating ones by green spheres. Reproduced with permission.[179] Copyright 2020, American Chemical Society. d) Heat map of reaction energies at possible solid-state battery interfaces. Reproduced with permission.[180] Copyright 2021, Royal Society of Chemistry.  \n\nAs traditional screening methods, thermal and DFT calculations require considerable computational resources. The researchers are badly in need of a new approach that is economical to screen cathode coating material by theoretical analysis. Wang et al.[179] combined on-the-fly ML and MD simulations to calculate the Li-ion conduction in any crystalline material containing Li that is more efficient than the pure ab initio molecular dynamics (AIMD). A diagram of the LOTF-MD (“learning on the fly”-ML) process is shown in Figure 17c. The methodology is briefly described below. First, the on-the-fly ML provided interatomic potentials trained by AIMD data, and the cost depended on the number of data points. Second, the mean squared displacement (MSD) of Li-ion less than $3\\ \\mathring{\\mathrm{A}}^{2}$ of materials was stripped away to avoid the room temperature Li-ion nonconductors. Third, LOTF-MD calculated the Li-ion mobility in materials at different temperatures. The total mean squared displacement (TMSD) more fabulous than $2000\\mathring{\\mathrm{A}}^{2}$ ensured that the diffusion values of Li-ion had a sufficiently high rate at room temperature. Finally, the data was used to obtain the activation energy $\\left(E_{\\mathrm{a}}\\right)$ and room temperature conductivity related to room-temperature tracer diffusivity (D (300K)) by fitting the Arrhenius function. This method eliminates the hassle of unavailable interatomic potentials, reduces cost dramatically compared to pure AIMD, and could be used to calculate other materials. They recently applied this method to screen for double-layer cathode coatings in allsolid-state batteries.[180] The process of this work is similar to the previous one. First, the Li-containing compounds with a Li content greater than $10\\%$ , nonradioactive, and thermodynamic stability (energy above hull $30{\\leq}\\mathrm{meV}$ were screened for the next step. Second, the interfacial reaction energies set to less than 4 of candidate materials with the thiophosphate electrolyte or cathode NCM/discharged NCM were calculated by AIMD. Finally, $E_{\\mathrm{a}}$ was obtained by the LOTF-MD to determine the final coating materials for the solid electrolyte and cathode (Figure 17d).  \n\n![](images/5c8ba77c48a9e486fb5e7f71820695c5d51a1d256dbb3c06803876c338ed09c9.jpg)  \nFigure 18. Benefits of applying a data-driven approach to functional coatings. a) Improving the accuracy of predicting the microhardness of Ni- ${\\mathsf{.P.T i O}}_{2}$ composite coating by ML. Reproduced with permission.[154] Copyright 2023, Elsevier. b) Effect of the electric potential and distance between the nozzle tip to the substrate on coating thickness. Reproduced with permission.[84] Copyright 2021, Elsevier. c) Prioritizing factors affecting the coefficient of friction and wear rate aids understanding of the friction mechanism by different ML models. Reproduced with permission.[181] Copyright 2023, Elsevier. d) Pearson correlation map importance ranking of features. Reproduced with permission.[152] Copyright 2022, Elsevier. e) The predicted composition of coatings and their performance compared with (AlCrTiNbTa)N. Reproduced with permission.[153] Copyright 2023, Elsevier. f) The Ada self-driving laboratory. Reproduced under the terms of CC-BY license.[173] Copyright 2020, the Authors, pulished by American Association for the Advancement of Science. g) ML to handle data from the production process improves the productivity and quality of battery coatings. Reproduced with permission.[182] Copyright 2022, Elsevier.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 35,
+        "chunk": "# 4.7. Advantages of Data-Driven Approaches in Functional Coatings Development  \n\nData-driven approaches offer numerous advantages in functional coatings development, including improved accuracy, time and cost savings, enhanced understanding of properties, increased productivity and innovation, improved product quality and performance, ability to handle complexity, and adaptability. These benefits make data-driven approaches valuable tools in the formulation and optimization of functional coatings. Figure 18 presents examples of the advantages of the data-driven approach, which will be described in the following sections.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 36,
+        "chunk": "# 4.7.1. Improved Accuracy and Precision  \n\nData-driven approaches use large amounts of data to develop functional coatings, leading to improved accuracy and precision in predicting coating performance. This reduces the need for trial-and-error experimentation. For example, the coating performance can be modeled and optimized based on recorded datasets by ML to improve accuracy and precision. Shozib et al.[154] developed ET model to accurately test the microhardness of the Ni-P$\\mathrm{TiO}_{2}$ coating (Figure 18a) because the experimental detection of microhardness was affected by many factors.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 37,
+        "chunk": "# 4.7.2. Time and Cost Savings  \n\nBy using data-driven approaches, researchers can significantly reduce the time and cost of traditional trial-and-error methods. Data-driven models can quickly analyze and predict coating performance, allowing researchers to optimize formulations in a shorter period. For instance, the preparation process of the coating contains many parameters, such as applied electrical potential, air pressure, substrate distance, flow rate, coating time, and so on. The coatings need to meet the parameters of achievable coating thickness, bonding strength, deposition efficiency, and so on. Paturi et al.[84] applied ML to comprehend the complex parameters and establish the relationship between coating performance and their operational parameters (Figure 18b). The results presented a high prediction capability of electric potential, powder feed pressure, and distance between the nozzle tip to the substrate on coating thickness. Thus, it demonstrates that the ML can endow a precise estimate of coating thickness as well as curtailing time-consuming and expensive electrostatic spray deposition experimental investigations. MacLeod et al.[173] developed a self-driving laboratory to take less than 21 min for an experimental cycle, significantly reducing research costs.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 38,
+        "chunk": "# 4.7.3. Enhanced Understanding of Coating Properties  \n\nData-driven approaches provide insights into the relationships between different variables and coating properties. This deeper understanding allows researchers to identify key factors that influence coating performance and optimize formulations accordingly. For example, Levämäki et al.[74] developed a method that combined ML and DFT calculations to discover the relationship between the disorder nitride coating and ordered nitride coating. Luo et al.[183] summarized the law of the data of multicomponent rare-earth silicide calculated by DFT. They found that the phase structure of multicomponent rare-earth silicide was related to the related to the mean (r̄) and mean square $(\\sigma_{\\mathrm{r}})$ of the rare-earth elements. Further thermodynamic research has found that r̄ and $\\sigma_{\\mathrm{r}}$ affect the conformational entropy, which determines the structure of the coatings (Figure 18c).",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 39,
+        "chunk": "# 4.7.4. Ability to Handle Complex Formulations  \n\nFunctional coatings often involve complex formulations and require a balance between multiple properties. Data-driven approaches can handle the complexity of these formulations and optimize coating performance across various properties simultaneously. Hao et al.[149] used ML to develop a model to describe the oxidation and ablative properties of ultrahigh temperature ceramic coatings. 22 influencing factors were considered, and Pearson correlation map of features and importance ranking were used to derive each factor’s priority in affecting the coatings’ performance (Figure 18d). The approach gives the researchers the ability to quantitatively analyze the effects on the oxidative and ablative properties of a coating, allowing us to quickly identify the most critical indicators from a complex set of factors. Xu et al.[152] also used ML to analyze the effect of multivariate on the properties of high entropy nitride coatings (Figure 18d). The influence of dozens of variables on coating performance is clear at a glance, and the direction of improving coating performance is available.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 40,
+        "chunk": "# 4.7.5. Improved Coating’s Quality and Performance  \n\nResearchers can optimize coating formulations using data-driven approaches to meet specific performance criteria. This leads to improved product quality and performance, resulting in coatings that are more durable, resistant to wear and tear, or possess other desired properties. The multiple elemental variables make highentropy nitride coatings difficult to analyze for getting the optimal product quality and performance. Xu et al.[152] prepared highentropy coating ((AlCrNbTaTi)N) with hardness $9\\%$ higher than the best quinary system through the ML and high-throughput experiment (Figure 12c). Their team further screened a new composition coating of (AlCrTiMoTa)N with a hardness of $33.4\\mathrm{GPa}$ and modulus of 287.7 GPa through ML and multiobjective optimization from the database of high-entropy ceramic coating (Figure 18e).[153]",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 41,
+        "chunk": "# 4.7.6. Adaptability and Scalability  \n\nData-driven approaches can be easily adapted and applied to different coating systems and substrates. This scalability allows researchers to develop functional coatings for various applications, ranging from electronics to automotive and aerospace industries. MacLeod et al.[173] developed a self-driving laboratory to discover organic and inorganic materials relevant to materials sciences and clean energy technologies. (Figure 18f). The software supports Python, making it highly convenient for other researchers to modify the automated laboratory for their needs.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 42,
+        "chunk": "# 4.7.7. Increased Productivity and Innovation  \n\nData-driven approaches enable researchers to screen and evaluate a wide range of formulation options quickly, leading to faster development of new functional coatings. This increased productivity promotes innovation in the field of coating development. Although data on industrial circulation can be collected by monitoring equipment and as a reference for optimizing industrial circulation, several factors affect product quality and production efficiency. A practical method is required for analysis. Liu et al.[182] applied ML to collect data from real industrial circulation to build a model (Figure 18g). This model identifies the information on the coating mass, thickness, and porosity affecting the battery capacity and quantitatively deals with the effect of these three factors. The method directly influences manufacturing parameters’ influence on battery coating performance, which can significantly facilitate engineers to improve production quality and innovation. Kolesnikov et al.[184] combined finite element modeling and ML to optimize the parameters of double-layer coating to design optimal multilayer coatings. Finite element modeling was used to simulate the microhardness of double-layer coating, and ML was used to prepare the coating with a target hardness. This method dramatically improves the efficiency of conducting experiments by adjusting parameters one by one.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 43,
+        "chunk": "# 5. Challenges and Future Outlook  \n\nData-driven approaches offer a promising avenue for functional coatings development, providing researchers with powerful tools to accelerate the materials discovery process, improve the accuracy and reliability of prediction models, and enhance our knowledge of materials properties and performance. They have the potential to revolutionize the field of functional coatings by enabling researchers to discover new materials with exceptional properties in an efficient and systematic way. In this section, challenges of this field and some possible future directions are summarized.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 44,
+        "chunk": "# 5.1. Challenges of Data-Driven Approaches in Functional Coatings Development  \n\nAlthough data-driven materials discovery approaches in functional coatings have great potential, they also have challenges that need to be addressed.",
+        "category": " Introduction"
+    },
+    {
+        "id": 45,
+        "chunk": "# 5.1.1. Limited Availability of High-Quality Data  \n\nThe success of data-driven materials discovery largely depends on the quality of data used to train algorithms. Collecting highquality data can be challenging and expensive, especially for complex systems like functional coatings. It is preferable to obtain data from accredited database and reputable academic journals. Moreover, it is necessary to scrutinize the data in order to establish trust in the data identified, rather than establishing and applying a general quality assessment standard to distinct data sources.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 46,
+        "chunk": "# 5.1.2. Lack of Standardization in Data Collection and Management  \n\nThere is currently no standardized protocol for data collection and management in materials science. This can lead to inconsistencies in data and make it difficult to compare results across different studies. One of the hardest challenges associated with the standardization of data collection and management is overcoming the technological barrier in standardization of collection, aggregation and storage of data in multiple types, including structured data, unstructured data such as plain texts, images and videos. The standardization of data collection and management will guarantee the quality of the data collected as well as implement all relevant data sharing.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 47,
+        "chunk": "# 5.1.3. Unpredictable Factors Affecting the Performance of Coatings  \n\nThe performance of functional coatings can be affected by various factors, such as environmental conditions, manufacturing processes, and substrate properties. It can be challenging to account for all these factors in the development of data-driven models. Since it is difficult to obtain a high-quality dataset, a comprehensive dataset covering a variety of factors that impact performance of functional coatings should be used to improve the accuracy of the data-driven models.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 48,
+        "chunk": "# 5.1.4. Uncertainty in Predicted Results  \n\nThe predictions made by data-driven models have some level of uncertainty associated with them, which can make it difficult to confidently predict the behavior of functional coatings. Uncertainty of predictions due to data-driven models should be quantified, represented and managed. Further, new prediction algorithms with good robustness, reliability and applicability issues should be developed to quantify uncertainty and improve accuracy of estimates, ensuring good prediction performances.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 49,
+        "chunk": "# 5.2. Prospects of Data-Driven Approaches in Functional Coatings R&D  \n\nAs materials scientists, it is essential for us to understand, embrace, and utilize data-driven methods to signal the way forward and maximize the quality, cost-effectiveness, and coverage of our care. We have to jump out of the comfort zone of those commonplace activities and broaden our horizons.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 50,
+        "chunk": "# 5.2.1. Expansion of the Studied Materials Scope  \n\nTraditional coating materials mainly focus on one specific conventional need that is the surface protection of base materials. Currently, many data-driven researches in this field are centered on traditional systems such as metals, ceramics, and polymers. As mentioned hereinbefore, any designed coating will face a complex environment during service in more and more modern applications scenarios, which is dictated by its intrinsic properties and must satisfy some specified requirements. This interaction can drastically limit the coating’s lifetime or even change its properties, thus raising an increasingly demand in expanding research to include advanced functional coating materials such as 2D sheet material and bio-based materials.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 51,
+        "chunk": "# 5.2.2. Collaboration Between Experimentalists and Theorists  \n\nExperimental investigations are often used to study causal relationships, one or more independent variables are usually designed and their effect are measured and recorded. The process may be both costly and time-consuming, particularly when dealing with complex coating systems, and the scientific laws and hidden mechanisms may lack of deep understandings to some extent. From the perspective of theoretical calculations, the above concerns can be handled, while the effectiveness and practicability are eager to be evidenced. As the challenges in materials science increase in scope and interdisciplinarity, collaborations, particularly among experimentalists and theorists, have become increasingly important in dealing with data-driven affairs.  \n\nA closer working relationship between experimental investigators and computational researchers can lead to more accurate predictions of coating behavior and better customization of desirable properties.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 52,
+        "chunk": "# 5.2.3. Development of Database Management Technology for Information Systems  \n\nIn recent years, booming advancements in hardware and software have contributed to the amelioration and emergence of various workflow paradigms for data management from experiments and computational simulations. The improvement of efficiency, reliability, and scalability of collecting, retrieving, storing, processing, and controlling data is and will be an important branch of information systems in data-driven process. A novel distributed database management system are needed for different types data handling and coupling with any material computational software to improve the effectiveness of data-driven materials discovery and better prediction of the coating service behavior.",
+        "category": " Introduction"
+    },
+    {
+        "id": 53,
+        "chunk": "# 5.2.4. Improvement of Machine Learning Algorithms for Advanced AI  \n\nML algorithms can learn and make predictions or decisions from data without being explicitly programmed, which is a key research foundation of advanced AI systems. Improving ML algorithms for advanced AI should pay attention to several approaches and techniques, such as model architecture, optimization algorithms, data augmentation, transfer learning, explainability, and Interpretability, and so on. Constructing a general machine learning model framework that integrates transfer learning and universal descriptors from functional coatings can enhance model’s generalization capabilities and help to accelerate the process of functional coating development by identifying materials with desirable properties quickly and accurately. Study and innovation in these areas will contribute to the development of more powerful and intelligent AI systems for future data-driven materials discovery.",
+        "category": " Introduction"
+    },
+    {
+        "id": 54,
+        "chunk": "# 5.2.5. Integration of Sustainability and Environmental Impact Assessments  \n\nFunctional coatings are normally fabricated on the surface of components in high-tech industrial applications to provide desirable surface properties, which directly contact with human body or surrounding environments. Future research should pay close attention to the sustainability and environmental impact of new coatings developed through data-driven materials discovery. This will help ensure that the materials developed are not only functional but also environmentally sustainable. In addition, sustainability and environmental impact are also important considerations in advanced technology and AI system. Thus, it is important to exploring and implementing strategies, such as improving time-efficient and energy-efficient algorithms, designing environmentally friendly computing systems, developing in situ environmental monitoring system and assessment, and emphasizing knowledge opening and sharing, that promote the development of sustainable and eco-friendly data-driven approaches in functional coatings development.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 55,
+        "chunk": "# 6. Conclusions  \n\nData-driven approaches have emerged as a prominent tool for accelerating the discovery of novel functional coatings. This review paper highlights the potential of data-driven approaches in materials discovery and provides insights into the future of functional coatings research.  \n\ni. Data-driven materials discovery plays a crucial role in the development of functional coatings because it can help identify and optimize the properties of the materials needed for specific applications. Traditional trial-and-error methods can take a long time and may not produce the results needed for a particular application.   \nii. Using data-driven approaches, such as high-throughput experimentation, computational modeling, ML, etc., researchers can quickly screen large numbers of materials and predict their properties before physical testing. These approaches accelerate the discovery process and supports the design of new and improved coatings tailored to specific needs.   \niii. Moreover, data-driven materials discovery allows for the combination of compositions, processes, and components that may have not been considered otherwise, opening up new horizons and possibilities for the development of functional coatings. Ultimately, this interdisciplinary methodology can lead to more efficient and effective coatings with longer lifetimes, higher performance, and even in situ self-adaption in various applications.   \niv. With the growing demand for coatings that exhibit advanced functionalities, such as anticorrosion, antifouling, and selfhealing, data-driven approaches will play a critical role in accelerating the pace of materials discovery and innovation. These approaches have the potential to revolutionize the field of functional coating development and application. Therefore, it is critical for researchers in the field to embrace data-driven approaches and techniques to overcome the limitations of traditional trial-and-error-based approaches and develop high-performance coatings that meet the ever-evolving demands of modern industries. However, despite the promises, it is important to keep in mind that these approaches are still in their early stages of development and we must continue to validate these techniques against experimental data.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 56,
+        "chunk": "# Acknowledgements  \n\nThis work was financially supported by the National Natural Science Foundation of China (Nos. 52222507 and 52101026), the Key Scientific and Technological Programs of Ningbo (No. 2022Z190), and Ningbo 3315 Innovation Team (No. 2019A-18-C). The authors thanked Ms. Y. Liao for her support in graphical abstract.",
+        "category": " Acknowledgements"
+    },
+    {
+        "id": 57,
+        "chunk": "# Conflict of Interest  \n\nThe authors declare no conflict of interest.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 58,
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Wang, Wear 2023, 532–533, 205092.   \n[182] K. Liu, M. F. Niri, G. Apachitei, M. Lain, D. Greenwood, J. Marco, Control Eng. Pract. 2022, 124, 105202.   \n[183] Y. Luo, L. Sun, J. Wang, T. Du, C. Zhou, J. Zhang, J. Wang, Nat. Commun. 2023, 14, 1275.   \n[184] V. I. Kolesnikov, D. M. Pashkov, O. A. Belyak, A. A. Guda, S. A. Danilchenko, D. S. Manturov, E. S. Novikov, O. V. Kudryakov, S. A. Guda, A. V. Soldatov, I. V. Kolesnikov, Acta Astronaut. 2023, 204, 869.  \n\n![](images/3e5dcb4f45749e4c645bd7d4ce8340942a267fec2f76ee308d3ee343ead70372.jpg)  \n\nKai Xu received the B.E. and Ph.D. degrees in Materials Science and Engineering at Central South University, China, in 2012 and 2018, respectively. Since 2022, he has been an associate professor at Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences. His research interests include the study of data-driven materials design, fabrication, and damage mechanism.  \n\n![](images/6d6dab34627eb72fd02ee6cf55a159d530fd17e209adf11edb9e4b0786bf0dd9.jpg)  \n\nKeke Chang received his bachelor and master degrees from Central South University, Changsha, China, in 2008 and 2010, respectively, and Ph.D. degree from RWTH Aachen University, Germany, in 2013. He is now a professor at Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, China. His research interest is theoretical design of coatings, surfaces, and interfaces for serving in harsh environments.",
+        "category": " References"
+    }
+]
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+[
+    {
+        "id": 1,
+        "chunk": "# Self-Powered Machine-Learning-Assisted Material Identification Enabled by a Thermogalvanic Dual-Network Hydrogel with a High Thermopower  \n\nYunsheng Li, Wenxu Wang, Xiaojing Cui, Ning Li, Xueliang Ma, Zhaosu Wang, Yuyou Nie, Zhiquan Huang,\\* and Hulin Zhang\\*  \n\nWearable devices equipped with high-performance flexible sensors that can identify diverse physical information free from batteries are playing an indispensable role in various fields. However, previous studies on flexible sensors have primarily focused on their elasticity and temperature-sensing capability, with few reports on material identification. In this paper, a thermogalvanic dual-network hydrogel is fabricated with $[\\mathsf{F e}(\\mathsf{C N})_{6}]^{3-/4-}$ as a redox couple and lithium magnesium silicate, $\\mathbf{C}\\mathbf{d}\\mathbf{m}^{+}$ and lithium bromide as key electrolytes to optimize the interconnected porous structure of the gel, which shows excellent mechanical and thermoelectric properties with a thermopower as high as $4.01\\mathrm{\\mV}\\mathsf{K}^{-1}$ . A self-powered material identification ring is developed based on the temperature-triggered thermoelectric response of the gel in conjunction with machine learning, which can actively infer materials without an external power connection by analyzing the voltage signals correlated with interfacial heat transfer produced upon contact with different materials. The proposed gel ring has important applications for future areas such as human–computer interaction and haptic-associated artificial intelligence.",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# 1. Introduction  \n\nThe sense of touch is one of the most important ways humans understand the world around them. When humans touch different materials, they can often make general inferences about the type of materials by sensing the temperature.[1] With the advent of the information age, people’s living standards improved with advanced electronics. Expectations for tactile sensors, such as electronic skin, continue to grow with micro and nanofabrication technology advances.  \n\nSuccessful identification of a wide range of physical information through sensing elements, using the principles of piezoresistance,[2] capacitance,[3] piezoelectricity,[4–6] and triboelectricity,[7,8] has been reported and applied in healthcare or artificial intelligence.[9–11] Piezoresistive and capacitive sensors depend on external power supports, which makes them problematic in terms of portability and then limits their application scenarios.[12,13] Additionally, piezoelectric and triboelectric devices lack sufficient applicability due to the indispensableness of contact deformations or interfacial displacements and are complicated to fabricate.[14–16] Thermogalvanic hydrogels have excellent application prospects in physical information recognition by converting arbitrary heat, which is imperceptible to human beings, into electricity, and have the advantages of favorable low cost, biocompatibility, mechanical adaptability, and ease of preparation.[17–19]  \n\nHere, we report a thermogalvanic hydrogel for self-powered material identification with acrylamide as the matrix, gelatin as the reinforcing agent, and $\\mathrm{[Fe(CN)6]^{3-/4-}}$ as the redox couple, respectively. In addition, lithium magnesium silicate (LMS) in the thermogalvanic dual-network hydrogel (TG-DNH) enlarges its pore size, ${\\mathrm{Li^{+}}}$ and $\\mathrm{Br^{-}}$ extend its effective working time and ${\\mathrm{Gdm}}^{+}$ significantly increases its thermopower $(4.01\\mathrm{~mV~K^{-1}};$ ). Based on the temperature-triggered thermogalvanic effect of the TG-DNH in conjunction with machine learning, we have developed a self-powered material identification ring (MIR) that can actively infer the type of materials without an external power connection by analyzing the voltage signals correlated with interfacial heat transfer produced upon contact with different materials. This study shows a great application potential of thermogalvanic hydrogels for human–computer interaction and artificial tactile sensation.  \n\n![](images/6656cb06e60e6657500f6e49123eb34d2cc28ac7d70f257b3fad99e581afb661.jpg)  \nFigure 1. Design of the MIR. a) Schematic representation of the TG-DNH and the MIR. b) Photos show that the TG-DNH can be deformed from external forces and withstand a weight of $\\boldsymbol{\\mathsf{100g}}$ . Scale bar (1 cm). c) Photos of a circular DNH gel, the QR code, and the results obtained after successfully scanning the code using a smartphone. Scale bar (1 cm) d) Comparison of the TG-DNH with existing quasi-solid-state thermogalvanic gel in terms of stretchability, current density, conductivity, thermopower, and maximum power.[30–33]",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 2. Results and Discussion",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# 2.1. Design and Fabrication of the TG-DNH  \n\nThermogalvanic hydrogels have demonstrated outstanding potential in converting temperature stimuli into electrical signals for wearable sensing.[20–23] A general illustration of the TGDNH-based self-powered material identification is sketched in Figure 1a. When one user touches an unknown material with the MIR made of the TG-DNH, a temperature gradient is established across the TG-DNH. At this time, the electrical signal correlated with interfacial heat transfer upon contact with different materials is actively generated by the thermoelectric conversion of the redox couple in the gel, which is then transmitted out for analyzing the interfacial heat transfer characteristics with the aid of machine learning, precisely inferring the type of materials. Polyacrylamide (PAAm) and gelatin are among the best candidates for the preparation of thermogalvanic hydrogels due to their non-toxicity, environmental friendliness, and low price. In the preparation of PAAm/gelatin dual-network hydrogels via an aqueous solution polymerization route, gelatin forms the first network by physical cross-linking, while PAAm forms the second network by chemical cross-linking. It is worth noting that the gelatin chains undergo the coil-helix transition and then aggregate into triple helices when the temperature decreases. However, the unfolding and polymerization of gelatin chains is reversible. Once the temperature increases, the triple helix structure of gelatin chains will unfold, consequently improving its fluidity and hydrogel adhesion.[24] Figure S1 (Supporting Information) demonstrates the excellent adhesion of the TG-DNH to different materials. The FTIR spectra of PAAm, gelatin, and the TG-DNH and the detailed descriptions are shown in Figure S2 and Text S1 (Supporting Information). The absorption associated with the characteristic groups of PAAm and gelatin can be seen, and no significant positional changes or new peaks occur, indicating that PAAm and gelatin are connected by hydrogen bonding.  \n\nConsidering that conventional hydrogels lose water when exposed to the atmosphere and thus affect their performance, we tried to add ${\\mathrm{Li}^{+}}$ and $\\mathrm{Br^{-}}$ to hydrogels. It is evident from Figures S3 and S4 (Supporting Information) that the addition of these two ions at the concentration of $\\mathbf{0.1\\mu_{M}}$ significantly enhanced water retention of the gel. The reason for this change is that the existence of $\\mathrm{Li^{+}}$ and $\\mathrm{Br^{-}}$ diminishes the saturation vapor pressure of water in the hydrogel to a level similar to the partial pressure of atmospheric vapor in the environment, slowing the rate of water loss from the hydrogel.[25] The DTG plots of Figure S5 (Supporting Information) and the explanation in Text S2 (Supporting Information) show that the degradation peak of the TG-DNH weakens after the addition of LiBr, which suggests amelioration in its thermal stability.[26]  \n\nFigure 1b shows that the TG-DNH can withstand various deformations from external forces, including bending, stretching, twisting, cutting, and withstanding a weight of $100\\ \\mathrm{g}$ which reveals that the TG-DNH has favorable mechanical strength and flexibility. Figure 1c exhibits a photograph of a circular DNH gel with a thickness of $5\\mathrm{mm}$ . Due to the excellent transparency, the  \n\n![](images/a9948dc3124b5e02296a72b3f66ab5f0cc9982db58402696624b6920d22a76d3.jpg)  \nFigure 2. Impact of LMS and mechanical property of the TG-DNH. a) SEM image and pore size distribution of the TG-DNH (Hitachi SU8010). Scale bar $(70\\upmu\\mathrm{m})$ . b) Stretching of the TG-DNH with different LMS contents and immersion time (inset). c) The thermopower and current, d) Frequencydependent conductivity, and e) Cyclic voltammetry curves of the TG-DNH with different LMS content (Keithley 2400 and CHI660E). f) The tensile stress– strain curves and g) toughness of the TG-DNH with different gelatin content. h) Cyclic stretching-releasing curves (UTM, Qualitest). The illustration is stretching-recovery images (Scale bar: $\\mathsf{1c m}$ ). i) Cyclic compression-releasing curves with deformation of $50\\%$ . The illustration is compression-recovery images (Scale bar: $\\mathsf{1c m}_{}^{\\mathsf{^{\\prime}}}$ ). The results in (b–i) are represented as the mean (sample size $n=5$ ).  \n\nQR code behind the gel can be clearly seen. We also compared the mechanical and thermoelectric properties of the TG-DNH with those of reported quasi-solid thermogalvanic gels in terms of stretchability, current density, conductivity, thermopower, and maximum power (Figure 1d), and the results show that the TGDNH has an exceptional overall performance, especially in terms of thermoelectricity.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# 2.2. Impact of LMS and Mechanical Property of the TG-DNH  \n\nAs shown in Figure 2a, a scanning electron microscope is utilized to examine the microstructural morphologies of the TG-DNH. The hydrogel has a porous mesh structure that facilitates unimpeded ion transport and exhibits a narrow pore size distribution when it does not contain LMS. However, when the gel includes a certain amount of LMS, its pore size notably enlarges because when LMS mixes with water, it holds up the LMS along its lamellar crystal structure; at this point, the LMS swells rapidly until the lamellae separate.[27] Therefore, the strain of the hydrogel shows a decrease with the increasing LMS content (Figure 2b). In the absence of LMS, the tensile strain of the TG-DNH is as high as $370\\%$ , whereas the tensile length is only $106\\%$ after the addition of $4\\%$ LMS. In the subplot of Figure 2b, we compare the tensile lengths for different times of immersion in electrolyte solutions containing solutes of $\\mathrm{K_{4}[F e(C N)_{6}]/K_{3}[F e(C N)_{6}]}.$ . It can be observed that the TG-DNH immersed for ${\\approx}1\\mathrm{~h~}$ has the best strain property, and the TG-DNH that we have used since then have been obtained by immersing them in electrolytes for $^{1\\mathrm{h}}$ . Not only for the mechanical property, the content of LMS in the gel also affects thermoelectricity. The comparison of the thermopower and current of the TG-DNH containing different concentrations of  \n\nLMS is shown in Figure 2c. Compared to that without LMS, both the thermopower and short-circuit current of the TG-DNH with $1\\%$ LMS show a substantial increase that is up to $4.01\\mathrm{~mV~K^{-1}}$ and $1.18\\mathrm{mA}$ , respectively. With the continuous addition of LMS to the gel, the thermopower of the TG-DNH begins to decrease, and its current also declines accordingly. The conductivity variation with the frequency of the TG-DNH at different LMS contents is depicted in Figure 2d. The trend observed in the EIS data is consistent with that shown in Figure 2c. While LMS is introduced to the gel, the resistance of the TG-DNH decreases and the conductivity increases until the turning point of $1\\%$ LMS content. The inner diagram in Figure 2d plots the frequency-dependent conductivity of the hydrogel at $1\\%$ LMS content. Figure 2e describes the highly symmetric CV curves at different LMS contents. The figure shows the presence of symmetrical peaks, i.e., a reversible reaction exists, where the peak of oxidation occurs upward, while the one of reduction is observed downward. As the LMS content increases from $1\\%$ to $4\\%$ , the peak intensity is gradually weakening, indicating that the conductivity is decreasing, which is in accordance with the conclusion of Figure 2d. The variance in the horizontal positioning of the oxidation and reduction peaks is negligible, suggesting that the polarization phenomenon is basically absent.  \n\nExcellent mechanical performance is crucial for flexible wearable bioelectronics. Hydrogels with good mechanical properties can return to their original shapes when deformed by external forces, significantly improving the applicability of gel-based bioelectronics. We have demonstrated above the remarkable flexibility of the TG-DNH in bending, stretching, twisting, and cutting, as well as the ability to hold a weight of $100\\mathrm{g}$ . Herein, we further investigated the tensile property of the TG-DNH with different gelatin contents. As the gelatin concentration rises from 0 to $10\\mathrm{\\mt.}\\%$ , the tensile strain of the gel increases from $169\\%$ to a maximum of $325\\%$ , and the maximal fracture stress is $0.11\\mathrm{MPa}$ . However, there is a decrease in tensile strain and fracture stress when gelatin concentration is increased to $15\\mathrm{\\wt.\\%}$ (Figure 2f). A proximately positive correlation exists between toughness and gelatin concentration in the gel, as depicted in Figure 2g, where toughness is calculated from the stress–strain curves. Notably, the toughness of PAAm- $10\\%$ Gel attains 164.15 KJ $\\mathbf{m}^{-3}$ , about two times higher than that of PAAm $(74.07\\ \\mathrm{KJ\\m^{-3}},$ ). This trend in Figure $^{2\\mathrm{f},\\mathrm{g}}$ occurs because of the gelatin’s unique triple helix structure, which provides energy dissipation, thus increasing the toughness of the hydrogel. However, if the gelatin concentration is too high, the gelatin chains can stack to form a crystalline structure, leading to a reduction in mechanical performance. Unless otherwise indicated, the TG-DNH with the gelatin concentration of $10\\mathrm{wt.\\%}$ is used in the following experiments. In addition, we further explored the elasticity of the TG-DNH by tensile cycling test. The results of cyclic stretching-recovery processes at different degrees of deformations are depicted in Figures 2h and S6 (Supporting Information), and the built-in inset shows the state of the gel during stretching and recovery. As can be seen from the figure, there is almost no displacement between the curves during the stretching and releasing, indicating that the TG-DNH has excellent fatigue resistance. As summarized in Figure 2i, the TG-DNH is compressed and released for 50 cycles at $50\\%$ deformation, and the insets show a full recovery from $50\\%$ compression. The above results indicate that an appropriate proportion of gelatin in the PAAm network leads to an improved mechanical property of the gel. The optimization of the hydrogel can make it ideally applicable for human wearable applications.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 2.3. Thermoelectric Property of the TG-DNH  \n\nThermopower is one of the most important parameters for assessing thermoelectric conversion, primarily determined by the type of redox pairs, differences in solvation structure entropy, and ion concentration gradients. In order to make the TG-DNH have a desirable thermoelectric conversion efficiency and stable electrical output, we chose $\\mathrm{[Fe(CN)_{6}]^{3-/4-}}$ among p-type redox ions and used ${\\mathrm{Gdm}}^{+}$ to improve its thermopower. We investigated the thermoelectric property of the TG-DNH with a length of ${\\approx}20\\mathrm{mm}$ , a width of ${\\approx}10\\mathrm{mm}$ , and a thickness of ${\\approx}4$ mm using a homemade temperature-controlled platform (Figure S7, Supporting Information). Figure 3a illustrates the operating principle of the TG-DNH concerning the $\\mathrm{[Fe(CN)_{6}]^{3-/4-}}$ redox reaction. At the hot end, the thermodynamic oxidation reaction Equation 1 occurs, with electrons move concurrently toward the anode electrode, accompanied by an electrochemical potential increase and a decrease in electrode potential. The product $\\mathsf{\\Gamma}[\\mathsf{F e}(\\mathsf{C N})_{6}]^{3-}$ obtained from oxidation will return to the cathode by diffusion, convection, and migration. On the contrary, at the cold end, the cathode undergoes a reduction reaction Equation 2. The attraction of electrons from the cold end leads to a reduction in electrochemical potential and a rise in electrode potential. The product $[\\mathrm{Fe}(\\mathrm{CN})_{6}]^{4-}$ obtained from the reduction process is then returned to the anode to continue the redox reaction. Therefore, based on the thermogalvanic effect of the TG-DNH, the temperature stimuli can be transformed into forms that are more intuitive, such as voltage and current signals.  \n\n$$\n\\begin{array}{r l}&{\\mathrm{Hotend:~}\\left[\\mathrm{Fe}(\\mathrm{CN})6\\right]4\\rightarrow\\mathrm{~e-}+[\\mathrm{Fe}(\\mathrm{CN})6]3-}\\\\ &{\\mathrm{Cold}\\mathrm{end:~}\\left[\\mathrm{Fe}(\\mathrm{CN})6\\right]^{3-}+\\mathrm{e^{-}\\rightarrow~}\\left[\\mathrm{Fe}(\\mathrm{CN})6\\right]^{4-}}\\end{array}\n$$  \n\nThe solvation structures of $\\mathrm{[Fe(CN)_{6}]^{3-/4-}}$ and ${\\mathrm{Gdm}}^{+}$ in solution are shown schematically in Figure 3b, where $\\mathrm{[Fe(CN)_{6}]~^{4-}}$ is on the left and $\\mathsf{\\Gamma}[\\mathsf{F e}(\\mathsf{C N})_{6}]^{3-}$ is on the right. It is seen that there is a notable difference between the solvation shells of $\\mathrm{[Fe(CN)_{6}]~^{4-}}$ and $\\mathsf{[F e(C N)_{6}]^{3-}}$ following the introduction of ${\\mathrm{Gdm}}^{+}$ . Compared to slightly affecting the solvation shell of $\\mathrm{[Fe(CN)_{6}]^{3-}}$ , $\\mathrm{Gdm^{+}}$ cations tend to distribute around $\\mathrm{[Fe(CN)_{6}]^{4-}}$ and cause its solvation shell to rearrange, which in turn widens the entropy difference of $\\mathrm{[Fe(CN)_{6}]^{3-/4-}}$ .[28] The thermopower, on the other hand, is mainly affected by the redox reaction entropy difference $\\Delta{\\sf S}$ (Equation 3), where $n$ represents the mole count of electrons transferred, $F$ denotes Faraday’s constant, Vh and Vc denote the open circuit voltages at the hot and cold ends of the sample, respectively, and Th and Tc are the temperatures at the hot and cold ends of the sample, respectively.[29] Thus, while the entropy difference of $\\mathrm{[Fe(CN)_{6}]^{3-/4-}}$ is widened by adding ${\\mathrm{Gdm}}^{+}$ , the thermopower also increases.  \n\n$$\n\\mathrm{S_{e}}=\\Delta\\mathrm{S}/\\mathrm{nF}=\\left(\\mathrm{Vh}-\\mathrm{Vc}\\right)/\\left(\\mathrm{Th}-\\mathrm{Tc}\\right)\n$$  \n\nTo explore the influence of electrolyte ions on the thermoelectric property of the TG-DNH, we varied the concentrations of $[\\mathrm{Fe(CN)}_{6}]^{3-/4-}$ and ${\\mathrm{Gdm}}^{+}$ , respectively (Figures 3c and S8, Supporting Information). The $S_{\\mathrm{e}}$ of the TG-DNH increases with the enhancing concentration of $\\mathrm{[Fe(CN)_{6}]^{3-/4-}}$ and gets maximum at a concentration of $0.4\\textbf{M}$ . Further, when ${\\mathrm{Gdm^{+}}}$ is added to the TG-DNH, there is a significant elevation in the $S_{\\mathrm{e}}$ that increases with the enhancement of the ${\\mathrm{Gdm^{+}}}$ concentration and reaches the maximal value at a concentration of $0.6\\textbf{M}$ . It is evident that ${\\mathrm{Gdm}}^{+}$ plays a vital role in improving the thermopower of electrolyte $\\mathrm{[Fe(CN)_{6}]^{3-/4-}}$ . The symmetrical peaks of CV curves at different $\\mathrm{[Fe(CN)_{6}]^{3-/4-}}$ and ${\\mathrm{Gdm}}^{+}$ concentrations are presented in Figures 3d and S9 (Supporting Information), respectively, showing that $\\mathrm{[Fe(CN)_{6}]^{3-/4-}}$ undergoes a reversible reaction. While the concentration of $\\mathrm{[Fe(CN)_{6}]^{3-/4-}}$ rises from 0.1 to $0.4\\textbf{M}$ , the intensity of the redox peak gradually strengthens, suggesting that the conductivity is elevating. The concentration of ${\\mathrm{Gdm^{+}}}$ has a similar effect on the trend observed from the CV curves. We fixed the temperatures at both the hot and cold ends and thus obtained the current/power-voltage curves at various concentrations of $\\mathrm{[Fe(CN)_{6}]^{3-/4-}}$ .When the $\\mathrm{[Fe(CN)_{6}]^{3-/4-}}$ concentration is  \n\n![](images/d75b54f9804043a8a5bcd397f6f3f2862af126549f11c7122735bb1083cd9270.jpg)  \nFigure 3. Thermoelectric property of the TG-DNH. a) The operating principle of the TG-DNH concerning the $[\\mathsf{F e}(\\mathsf{C N})_{6}]^{3-/4-}$ redox reaction. b) The schematic solvation formations of $[\\mathsf{F e}(\\mathsf{C N})_{6}]^{3-}$ and $[\\mathsf{F e}(\\mathsf{C N})_{6}]^{4-}$ in $\\mathsf{C d m^{+}}$ solution. c) Thermal voltage at varied $\\Delta\\mathsf{T}$ d) Cyclic voltammetry curves, and e) current/power-voltage curves of the TG-DNH with different concentrations of $[\\mathsf{F e}(\\mathsf{C N})_{6}]^{3-/4-}.\\mathsf{f})$ Frequency-dependent conductivity and g) PF and ZT of the TG-DNH with different concentrations of $\\mathsf{G}\\mathsf{d}\\mathsf{m}^{+}$ . h) The maximum specific output power density. i) Short-circuit current curve of the thermogalvanic gel at different temperatures. The results in (c–i) are represented as the mean (sample size ${\\mathsf n}=5$ ).  \n\n$0.1\\textbf{\\ m}$ , the short-circuit current of the TG-DNH is ${\\approx}0.5~\\mathrm{mA}$ , the open-circuit voltage is $25.0~\\mathrm{mV},$ and the maximum power is $3.12\\upmu\\mathrm{W},$ approximately. However, at a concentration of $0.4\\mathrm{~m~}$ $\\mathrm{[Fe(CN)_{6}]^{3-/4-}}$ , the maximal power of the TG-DNH approximately quadruples to $12.98\\upmu\\mathrm{W}$ compared to the concentration of $0.1\\textbf{M}$ (Figure 3e). Next, by varying the temperature of the hot end at the constant cold end temperature of $293\\mathrm{~K~}$ the current/powervoltage curves under different temperature gradients are plotted in Figure S10 (Supporting Information). When the temperature difference $(\\Delta\\mathrm{T})$ increases from 5 to 25 K, the short-circuit current and open-circuit voltage progressively rise from $0.4\\mathrm{mA}$ and $20.0\\mathrm{mV}$ to $2.06\\mathrm{mA}$ and $100.0\\mathrm{mV},$ respectively, with the maximal power increasing from $2.0\\upmu\\mathrm{W}$ to as high as $51.5\\upmu\\mathrm{W}.$  \n\nThe porous structure of the TG-DNH facilitates the free migration of ions, making it suitable as a solid-state electrolyte. The variation of conductivity with frequency at different concentrations of ${\\mathrm{Gdm}}^{+}$ and $\\mathrm{[Fe(CN)_{6}]^{3-/4-}}$ is shown in Figures 3f and S11 (Supporting Information), respectively, indicating the conductivity of the TG-DNH shows a pattern of increasing and then decreasing as the concentrations of $\\mathrm{Gdm^{+}}$ and $[\\mathrm{Fe}(\\mathrm{CN})_{6}]^{3-/4-}$ grow, identical with the trend in Figures 3c and S8 (Supporting Information). It may be because when the ion concentration is too high, the migration of ions in the hydrogel becomes hindered, leading to a decline in conductivity. Both power factor (PF) and figure of merit (ZT), which are essential indicators of the hydrogel thermoelectricity, reach their maximal values at $0.6\\mathrm{~M~Gdm^{+}}$ (Figure 3g), coherent with the trends of ${\\sf S}_{\\mathrm{e}}$ and ionic conductivity in Figure S12 (Supporting Information). Figure $3\\mathrm{h}$ depicts the maximal power density $(\\mathrm{P}_{\\mathrm{max}})$ at different temperature differences, which is approximately proportional to the square of temperature difference and increases substantially from 0.09 to $0.99\\mathrm{~W~m~}^{-2}$ , in agreement with the theoretical results of Equation 4. The specific output power density $(\\mathrm{P_{max}}/\\Delta\\mathrm{T}^{2})$ is also an essential parameter for evaluating the output performance, which is independent of the $\\Delta\\mathrm{T}$ and approximately constant, consistent with Equation 5.  \n\n$$\n\\begin{array}{r}{\\mathrm{P}_{\\mathrm{max}}=\\left(\\sigma\\mathrm{Se}^{2}/4\\mathrm{d}\\right)\\Delta\\mathrm{T}^{2}}\\\\ {\\mathrm{P}_{\\mathrm{max}}/\\Delta\\mathrm{T}^{2}=\\sigma\\mathrm{Se}^{2}/4\\mathrm{d}}\\end{array}\n$$  \n\nwhere $\\sigma$ and d are the conductivity and effective length of the TG-DNH, respectively.  \n\nAs shown in Figure 3i, the output current of the TG-DNH demonstrates a remarkable linear correlation with the temperature difference, indicating high sensitivity and relevance to temperature stimuli. In contrast, the conductivity of the TG-DNH fluctuated slightly between 1.05 and $1.24~\\mathrm{S~m^{-1}}$ as the temperature difference raised from 20 to $60~\\mathrm{K}$ . This suggests that the gel provides relatively stable conductivity even at large temperature differences (Figure S13, Supporting Information). Besides, the TG-DNH maintains a high output current after bending over 800 times, which proves its reliable durability (Figure S14, Supporting Information). Even when a pressure of ${\\approx}5\\mathrm{\\kPa}$ and tensile strain of $\\approx50\\%$ were applied on the TG-DNH, respectively, both the output voltage and current nearly remained constant (Figure S15a,b, Supporting Information), indicating that the TGDNH has a highly excellent thermoelectric reliability and antiinterference performance. To summarize, these results fully illustrate that the TG-DNH developed in this study exhibits an outstanding comprehensive performance based on the thermogalvanic effect.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# 2.4. Machine-Learning-Assisted Self-Powered Material Identification by the MIR  \n\nIdentifying the material by differing between interfacial heat transfer upon contact has the advantages of high accuracy and low cost. We selected seven typical materials and then ranked them according to their capability of interior thermotransport (Figure 4a). To visualize the interfacial heat transfer process of different materials, we preheated the bottoms of seven materials by a heater at the same temperature of $313\\mathrm{~K~}$ (Figure S16, Supporting Information). In the case of the same heating time, the surfaces of different materials have different temperature distributions. The interior thermotransport simulation of three materials, aluminum (i), ceramics (ii), and wood (iii), under this heating condition is shown in Figure 4b. It is observable that accelerated heat transfer and more heat flow within the materials correlate with the superior thermal conductivity. This phenomenon underpins the theoretical basis for employing interfacial heat transfer to distinguish between various materials. Figure 4c,d shows the photograph and the infrared scanning image while wearing the MIR in contact with the top surface of the aluminum. With the interfacial heat transfer triggered during this process, due to the temperature difference between the two ends of the TG-DNH, the MIR generates distinguishable voltage signals when in contact with different materials based on its inherent thermogalvanic effect without an external power supply (Figure 4e,f). In Figure ${4\\mathrm{g}}$ , a detailed analysis of the voltage signal features is provided, where $\\Delta\\mathrm{V_{A}}$ represents the difference between the voltage at the moment of separation and the initial voltage at the beginning of contact, and $\\Delta\\mathrm{V}_{\\mathrm{B}}$ signifies the discrepancy between the peak voltage $V_{\\mathrm{m}}$ and the voltage at the end of measurement. These four characteristics, $\\Delta\\mathrm{V_{A}}$ , $\\Delta\\mathrm{V}_{\\mathrm{B}}$ , $\\Delta\\mathrm{V_{A}}/\\Delta\\mathrm{V_{B}}$ and $\\mathrm{V_{m}}$ , are designated as eigenvalues in machine learning.  \n\nMachine learning has been shown as an efficient tool for achieving material recognition precisely through multiple algorithms. The random forest algorithm integrates multiple decision trees and achieves high identification accuracy through integrated learning, whose core process is described in Figure 4h. In a 2D framework, the distribution of data is characterized by the axes of principal component 1 (PC1) and principal component 2 (PC2), with Principal Component Analysis (PCA). The different colors indexed to different materials indicate most dataset boundaries are clear with favorable intra-class compactness and significant inter-class separability. Figure 4i demonstrates the confusion matrix of the verifying results, where each row is the predicted material and each column is the actual material, with an average recognition accuracy of $97.2\\%$ for seven types of materials. The flowchart of self-powered material identification using the machine-learning-assisted MIR is described in Figure S17 (Supporting Information). Figure 4j presents some of the signal data used for machine learning in the sampling process. During operation with the MIR (Figure 4k), the acquired signal waveforms and final recognition results are visualized (Figures 4l and S18, Supporting Information). The enlarged terminal interface of machine-learning-assisted material identification is exhibited in Figures 4m and S19 (Supporting Information), where the left of the interface shows the real-time voltage signals during measurement and the right depicts material identification results. The whole material identification process is recorded in Movies S1– S3 (Supporting Information). Herein, by discerning differences in the interfacial heat transfer generated upon contact with different materials, the MIR can utilize the intrinsic thermogalvanic effect of the TG-DNH to convert temperature stimulus into a voltage signal and then actively identify the type of materials in conjunction with machine learning, which highlights a great application potential of thermogalvanic hydrogels for human–computer interaction and artificial tactile sensation.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# 3. Conclusion  \n\nIn summary, we reported a thermogalvanic hydrogel for selfpowered material identification with AAm as the matrix, gelatin as the reinforcing agent, and $\\mathrm{[Fe(CN)_{6}]^{3-/4-}}$ as the redox pair, respectively. The dual-network gel has a favorable thermoelectric output performance due to LMS enlarging its pore size and ${\\mathrm{Gdm}}^{+}$ widening the entropy difference of the redox couple, achieving a thermopower of $4.01\\ \\mathrm{mV}\\ \\mathrm{K}^{-1}$ . Meanwhile, ${\\mathrm{Li}^{+}}$ and $\\mathrm{Br^{-}}$ slow down the rate of water loss by adjusting the saturation vapor pressure of water in the hydrogel, which extends its effective working time. Supported by excellent mechanical and thermoelectric properties, we have developed a self-powered MIR based on the temperature-triggered thermoelectric response of the TG-DNH in conjunction with machine learning to accomplish the identification of seven materials with an impressive accuracy of $97.2\\%$ by analyzing the voltage signals correlated with interfacial heat transfer produced upon contact with different materials. This research can be further integrated with human– computer interaction and extended to haptic-associated artificial intelligence in the future.  \n\n![](images/3ffb8b65068a24d3e07be0d92fbe1a6edf3385194711bf29b709ae1c02a4f198.jpg)  \nFigure 4. Machine-learning-assisted material identification with the MIR. a) Ranking of interior thermotransport capability of typical materials. The capability of interior thermotransport enhances from the bottom to the top. b) Temperature distribution of aluminum (i), ceramics (ii), and wood (iii) for the same time of heating by COMSOL software. c) A photo of the tester wearing the MIR and d) the infrared scanning image during the test (FLIR E6-XT) (Scale bar: $10\\:\\mathsf{m m}$ e,f ) Voltag of differ materials mea red by the TG-DNH. g) Analysis of voltage profiles and selection of features. h) Simple flowchart of the RF orith and the distributio 2D pac nd PC2 axes. i) Confusion map of the machine-learnin sult of the arning during the pling process and photos of several test materials $(\\mathsf{n}=270)$ . k) T f the MIR (Scale bar: $\\mathsf{10}\\mathsf{m m}$ ). l) With th of m achine le rning, the aluminum is successfully identified using the MIR, and the results pla ed on the omputer. m) Computer interface for the material identification system when identifying aluminum.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 9,
+        "chunk": "# 4. Experimental Section  \n\nMaterials: Acrylamide (AAm, $\\begin{array}{c c l}{\\mathsf{M}\\mathsf{w}}&{=}&{71.08}\\end{array}$ , $99.0\\%$ , Gelatin $(\\mathsf{M w}=279.66)$ ), Silicic acid, lithium magnesium salt (LMS, $\\mathsf{M w}=$ 290.74, $99.0\\%$ , N, $N^{\\prime}$ -methylene bisacrylamide (MBA, $\\mathsf{M w}=754.77$ , $\\geq98\\%)$ ), Ammonium persulfate (APS, $\\mathsf{M w}=228.2,\\geq98\\%$ ), $\\mathsf{N},\\mathsf{N},\\mathsf{N}^{\\prime},\\mathsf{N}^{\\prime}.$ - Tetramethylethylenediamine (TEMED, $\\mathsf{M w}=776.27,\\geq98\\%)$ , ${\\sf K}_{3}\\sf r e(C N)_{6}.3$ $H_{2}O$ ( $\\mathsf{M w}=422.4$ , $299\\%$ ), ${\\sf K}_{4}\\sf F e(C N)_{6}$ $(\\mathsf{M w}=329.2,\\ge99\\%$ ), Guanidine hydrochloride $(\\mathsf{M w}=95.53$ , $99.0\\%$ , Lithium bromide $(\\mathsf{M w}=86.85$ , $99.0\\%$ were bought from Aladdin Industrial Corporation. If not specified differently, the substances used in this study are employed without additional purification.  \n\nPreparation of the TG-DNH: The TG-DNH is prepared primarily based on an aqueous solution polymerization method. First, acrylamide, LMS, and gelatin were added to $70~\\mathsf{m L}$ of deionized water and stirred at $70~^{\\circ}\\mathsf C$ until wholly dissolved to obtain a mixed solution. After the mixed solution was cooled down, N, $\\mathsf{N}^{\\prime}$ -methylene bisacrylamide, and initiator ammonium persulfate were added sequentially and stirred at room temperature until completely dissolved. Then, catalyst $\\mathsf{N},\\mathsf{N},\\mathsf{N}^{\\prime},\\mathsf{N}^{\\prime}.$ - Tetramethylethylenediamine was added, gently mixed, and quickly poured into the prepared mold for ${\\approx}2\\mathsf{h}$ to obtain DNH. Finally, the prepared DNH was immersed in a mixture of $[\\mathsf{F e}(\\mathsf{C N})_{6}]^{3-/4-}$ , guanidine hydrochloride, and lithium bromide for $2h$ to obtain the TG-DNH.  \n\nThermoelectric Measurement: Each sample used for thermoelectric analysis measured dimensions of $20\\times20\\times4m{\\times}^{3}$ . The samples were placed on a homemade Seebeck coefficient measurement setup, where a DC power source regulated the temperature of both Peltier chips, which was then measured using a thermocouple (NAPUI TR230X). Measurements of the output voltage and current were conducted using a Keithley 2400 source. The temperature difference between the two ends of the sample was controlled by connecting the homemade Seebeck coefficient measurement setup to a controlled DC power supply, and a series of current, voltage and temperature variation data were obtained. A workstation for electrochemistry (CHI660e, Shanghai Chenhua Instrument Co. Limited.) was utilized for assessing the hydrogels’ electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The ionic conductivity of the TG-DNH was calculated according to $\\sigma=\\mathsf{d}/\\mathsf{R A}$ , where d, R, and A represent the thickness, impendence value, and cross-sectional area of the TG-DNH, respectively.[26]  \n\nComposition of the MIR: The TG-DNH, PDMS, PU membrane, graphite electrodes and copper leads. The TG-DNH and the graphite electrodes and copper wires attached to its surface are encapsulated by a PU membrane and use the thermogalvanic effect to generate electrical signals. The PDMS acts as a scaffold in the MIR (Figure 4k).  \n\nMachine Learning-Assisted Data Measurement: To begin with, wires were used to connect the MIR to a data acquisition system (Keithley DAQ6510) and left it in place for $20~\\mathsf{s}$ to acclimatize to the environment and stabilize the voltage signal. Then, the MIR is used to contact the material to be tested with a force of 7N until the signal peaks. Finally, the MIR is allowed to separate from the material until the end of the test to obtain the voltage signal. The obtained signal is modeled to get the prediction result after the process of acquisition, preprocessing and signal extraction.  \n\nMachine Learning-Assisted Data Analysis: First, the tester needs to wear the MIR and expose it to known materials for data acquisition and preprocessing with data acquisition system and prepared Python script (Figure S20, Supporting Information). With data features extracted and selected by the statistical feature extraction, $75\\%$ of the materials was chosen at random from the database for training purposes. The remaining $25\\%$ of the materials are considered test samples. The RF algorithm uses the training samples to build and train a multi-iteration machine learning model. With the expansion of training data, the accuracy of the machine learning model steadily neared the actual truth. In addition, test samples are used to assess whether the model is valid. At the same time, cross-validation and hyperparameter optimization will make the machine learning model more accurate. Finally, the machine learning model predicts the data in real time and identifies the material when the tester wears the MIR in contact with an unknown material, such as aluminum, brass, stainless steel, ceramics, acrylic, wood, and foam.  \n\nCharacterization: At room temperature, Universal Tensile Testing (UTM, Qualitest, USA) was employed to conduct tests for both tensile and compression. Use Keithley 2400 instrument for voltage and current measurements. The morphology of the TG-DNH was characterized using the SEM method (Hitachi SU8010). The electrochemical AC impedance spectra, resistance, and cyclic voltammetry curves of the TG-DNH were measured using an electrochemical workstation (CHI660E, Shanghai Chenhua Instrument Co. Ltd.). The temperature was regulated through a homemade temperature platform, with real-time monitoring of temperature variations using thermocouple (NAPUI TR230X). Thermogravimetric analysis is performed by using TGA-601 thermal analysis instrument with a scan rate of $20^{\\circ}C\\mathsf{m i n}^{-1}$ . Use Keithley DAQ6510 for data acquisition. The temperature distribution of aluminum, ceramics, and wood for the same time of heating is simulated by COMSOL. A FLIR E6-XT infrared camera was utilized to capture infrared photographs.  \n\nStatistical Analysis: The experimental result was subjected to preprocessing procedures such as de-baselining and expressed as mean values. The samples used for the determination of toughness, $S_{\\mathrm{e}}$ , and conductivity at each variation of the TG-DNH were ${\\mathfrak{n}}=5$ . All the statistical analysis was carried out using Microsoft Excel, Origin and COMSOL software. Each data point represents the mean.  \n\nStatements: Ethics approval and informed consent were obtained from all participants, and the protocol was approved by the Ethics Review Committee of Taiyuan University of Technology (Approval No. TYUT2024092301). The study was carried out under the Helsinki Declaration.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 10,
+        "chunk": "# Supporting Information  \n\nSupporting Information is available from the Wiley Online Library or from the author.",
+        "category": " References"
+    },
+    {
+        "id": 11,
+        "chunk": "# Acknowledgements  \n\nThis work was supported by the National Natural Science Foundation of China (52475600), Special Project of Science and Technology Cooperation and Exchange of Shanxi Province (202304041101021) and Shanxi Province Graduate Science and Technology Innovation Project (2023XSY066).",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# Conflict of Interest  \n\nThe authors declare no conflict of interest.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# Data Availability Statement  \n\nThe data that support the findings of this study are available from the corresponding author upon reasonable request.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 14,
+        "chunk": "# Keywords  \n\nmachine learning, material identification, self-powered, thermogalvanic gel, thermopower  \n\nReceived: July 15, 2024   \nRevised: October 18, 2024   \nPublished online: October 31, 2024  \n\n[1] R. S. Johansson, J. R. Flanagan, Nat. Rev. Neurosci. 2009, 10, 345.   \n[2] J. Park, M. Kim, Y. Lee, H. S. Lee, H. Ko, Sci. Adv. 2015, 1, 1500661.   \n[3] L. Beker, N. Matsuhisa, I. You, S. R. A. Ruth, S. Niu, A. Foudeh, J. B.-H. Tok, X. Chen, Z. Bao, Proc. Natl. Acad. Sci. 2020, 117, 11314.   \n[4] Z. Liu, Q. Zheng, Y. Shi, L. Xu, Y. Zou, D. Jiang, B. Shi, X. Qu, H. Li, H. Ouyang, R. Liu, Y. Wu, Y. Fan, Z. Li, J. Mater. Chem. B 2020, 8, 3647.   \n[5] B.-Y. Lee, D. H. Kim, J. Park, K.-I. Park, K. J. Lee, C. K. Jeong, Sci. Technol. Adv. Mater. 2019, 20, 758.   \n[6] H. S. Wang, S. K. Hong, J. H. Han, Y. H. Jung, H. K. Jeong, T. H. Im, C. K. Jeong, B.-Y. Lee, G. Kim, C. D. Yoo, K. J. Lee, Sci. Adv. 2021, 7, eabe5683.   \n[7] T. Chen, Q. Shi, M. Zhu, T. He, L. Sun, L. Yang, C. Lee, ACS Nano 2018, 12, 11561.   \n[8] T. Jin, Z. Sun, L. Li, Q. Zhang, M. Zhu, Z. Zhang, G. Yuan, T. Chen, Y. Tian, X. Hou, C. Lee, Nat. Commun. 2020, 11, 5381.   \n[9] Z. Sun, M. Zhu, Z. Zhang, Z. Chen, Q. Shi, X. Shan, R. C. H. Yeow, C. Lee, Adv. Sci. 2021, 8, 2100230.   \n[10] J. Kim, M. Lee, H. J. Shim, R. Ghaffari, H. R. Cho, D. Son, Y. H. Jung, M. Soh, C. Choi, S. Jung, K. Chu, D. Jeon, S.-T. Lee, J. H. Kim, S. H. Choi, T. Hyeon, D.-H. Kim, Nat. Commun. 2014, 5, 5747.   \n[11] G. Lee, J. H. Son, S. Lee, S. W. Kim, D. Kim, N. N. Nguyen, S. G. Lee, K. Cho, Adv. Sci. 2021, 8, 2002606.   \n[12] S. Wang, J. Xu, W. Wang, G.-J. N. Wang, R. Rastak, F. Molina-Lopez, J. W. Chung, S. Niu, V. R. Feig, J. Lopez, T. Lei, S.-K. Kwon, Y. Kim, A. M. Foudeh, A. Ehrlich, A. Gasperini, Y. Yun, B. Murmann, J. B.-H. Tok, Z. Bao, Nature 2018, 555, 83.   \n[13] S. K. Ravi, N. Paul, L. Suresh, A. T. Salim, T. Wu, Z. Wu, M. R. Jones, S. C. Tan, Mater. Horiz. 2020, 7, 866.   \n[14] L. Zhao, H. Li, J. Meng, A. C. Wang, P. Tan, Y. Zou, Z. Yuan, J. Lu, C. Pan, Y. Fan, Y. Zhang, Y. Zhang, Z. L. Wang, Z. Li, Adv. Funct. Mater. 2020, 30, 1907999.   \n[15] Y. Pang, Y. Cao, M. Derakhshani, Y. Fang, Z. L. Wang, C. Cao, Matter 2021, 4, 116.   \n[16] X. Chen, L. Gao, J. Chen, S. Lu, H. Zhou, T. Wang, A. Wang, Z. Zhang, S. Guo, X. Mu, Z. L. Wang, Y. Yang, Nano Energy 2020, 69, 104440.   \n[17] C. Bai, X. Li, X. Cui, X. Yang, X. Zhang, K. Yang, T. Wang, H. Zhang, Nano Energy 2022, 100, 107449.   \n[18] J. Li, Z. Wang, S. A. Khan, N. Li, Z. Huang, H. Zhang, Nano Energy 2023, 113, 108612.   \n[19] R. Fang, X. Li, S. A. Khan, Z. Wang, X. Cui, H. Zhang, Z.-H. Lin, ACS Appl. Polym. Mater. 2023, 5, 4628.   \n[20] X. Yang, Z. Zhang, S. A. Khan, L. Sun, Z. Wang, X. Cui, Z. Huang, H. Zhang, J. Mater. Chem. C 2024, 12, 3298.   \n[21] C. Tian, C. Bai, T. Wang, Z. Yan, Z. Zhang, K. Zhuo, H. Zhang, Nano Energy 2023, 106, 108077.   \n[22] S. Sang, C. Bai, W. Wang, S. A. Khan, Z. Wang, X. Yang, Z. Zhang, H. Zhang, Nano Energy 2024, 123, 109366.   \n[23] H. Yang, S. A. Khan, N. Li, R. Fang, Z. Huang, H. Zhang, Chem. Eng. J. 2023, 473, 145247.   \n[24] Y. Zhang, Y. Dai, F. Xia, X. Zhang, Nano Energy 2022, 104, 107977.   \n[25] S. Pu, Y. Liao, K. Chen, J. Fu, S. Zhang, L. Ge, G. Conta, S. Bouzarif, T. Cheng, X. Hu, K. Liu, J. Chen, Nano Lett. 2020, 20, 3791.   \n[26] N. Li, S. A. Khan, K. Yang, K. Zhuo, Y. Zhang, H. Zhang, Compos. Sci. Technol. 2023, 239, 110077.   \n[27] Y. Yu, Y. Feng, F. Liu, H. Wang, H. Yu, K. Dai, G. Zheng, W. Feng, Small 2023, 19, 2204365.   \n[28] J. Duan, G. Feng, B. Yu, J. Li, M. Chen, P. Yang, J. Feng, K. Liu, J. Zhou, Nat. Commun. 2018, 9, 5146.   \n[29] L. Liang, H. Lv, X.-L. Shi, Z. Liu, G. Chen, Z.-G. Chen, G. Sun, Mater. Horiz. 2021, 8, 2750.   \n[30] P. Yang, K. Liu, Q. Chen, X. Mo, Y. Zhou, S. Li, G. Feng, J. Zhou, Angew. Chem. Int. Ed. 2016, 55, 12050.   \n[31] Y. Zhou, S. Zhang, M. A. Buckingham, L. Aldous, S. Beirne, C. Wu, Y. Liu, G. Wallace, J. Chen, Chem. Eng. J. 2022, 449, 137775.   \n[32] W. Gao, Z. Lei, C. Zhang, X. Liu, Y. Chen, Adv. Funct. Mater. 2021, 3, 2104071.   \n[33] X. Li, X. Xiao, C. Bai, M. Mayer, X. Cui, K. Lin, Y. Li, H. Zhang, J. Chen, J. Mater. Chem. C 2022, 10, 13789.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Supporting Information",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# Amphiphilic Antifogging/Anti-icing Coatings Containing POSS-PDMAEMA- $b$ -PSBMA  \n\nChuan Li, Xiaohui Li, Chao Tao, Lixia Ren, Yunhui Zhao, Shan Bai, and Xiaoyan Yuan\\*  \n\nSchool of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300072, China  \n\nE-mail: yuanxy $@$ tju.edu.cn; xyuan28 $@$ yahoo.com  \n\nMaterials. Aminopropyllsobutyl POSS (apPOSS) was purchased from Hybrid Plastics, USA, and used as received. 2-(Dimethylamino) ethyl methacrylate (DMAEMA, $598.5\\%$ ), 2-bromoisobutyryl bromide (BIBB, $599\\%$ ) and ethyl-2-bromoisobutanoate (EBIB, $599\\%$ ) were supplied by Beijing Bailingwei Technology Co. Ltd., China. [2-(Methacryloyloxy) ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA, AR), 1,1,4,7,10,10-hexamethyl-triethylenetetramin (HMTETA, $597\\%$ ) , Igracure 2959 (AR), triethylamine (TEA, $599\\%$ ), 2,2,2-trifluoroethanol (AR) and ethyleneglycol dimethacrylate (EGDMA, $59\\%$ ) were obtained from Tianjin Xi'ensi Aupu Technology Co. Ltd., China. DMAEMA and EGDMA were passed through an alumina column to remove inhibitor. BIBB, EBIB, SBMA, HMTETA, TEA and Igracure 2959 were used without further purification. CuBr (AR) was bought from Tianjin Kermel Chemical Reagent Co. Ltd., China, and was dissolved in glacial acetic acid for $24\\mathrm{~h~}$ to remove $\\mathrm{CuBr}_{2}$ , and washed with methanol and glacial acetic acid for three times, and then dried under vacuum. All other reagents were supplied by Tianjin Yuanli Chemical Co. Ltd., China, and used as received without further purification.  \n\nSynthesis of POSS-Br Initiator. POSS-Br as atom transfer radical polymerization (ATRP) initiator was prepared according to the reference.1 ApPOSS $(0.8745~\\mathrm{g},\\ 1\\ \\mathrm{mmol})$ and TEA 1 $\\mathrm{0.1518~g,}1.5\\mathrm{\\mmol}\\mathrm{}\\mathrm{},$ and THF $(20~\\mathrm{mL})$ ) were charged into a three-necked flask and degassed for at least three times. Degassed BiBB $\\mathrm{(0.2759~g,1.2~mmol}$ , dissolved in $10~\\mathrm{ml}$ THF) solution was slowly added into the flask at $0{}^{\\circ}\\mathrm{C}$ . The solution was magnetically stirred for $^{\\textrm{1h}}$ in an ice/water bath and then maintained at room temperature to react for another $12\\mathrm{~h~}$ . The precipitate was removed by filtration, and the filtrate was washed with a saturated aqueous solution of sodium bicarbonate and NaCl. Anhydrous sodium sulfate was added into the organic layer to eliminate residual moisture. Then, macroinitiator POSS-Br was obtained by removing solvent by a rotary evaporator and followed by vacuum drying (yield $75\\%$ ).  \n\nSynthesis of POSS-PDMAEMA. POSS-PDMAEMA was synthesized by using POSS-Br as an ATRP macroinitiator. The mixture of POSS-Br $(0.1024\\ \\mathrm{g},0.1\\ \\mathrm{mmol})$ , DMAEMA $(1.8865\\ {\\mathrm{g}},$ 12 mmol), HMTETA $(0.0277~\\mathrm{g},\\ 0.12~\\mathrm{mmol})$ and THF $(2\\mathrm{~ml})$ ) was injected into the $10\\mathrm{mL}$ standard Schlenk flask. Highly pure nitrogen was filled the flask and then oxygen was removed by three freeze-pump-thaw cycles. Subsequently, CuBr $0.0144\\ \\mathrm{g},0.1\\ \\mathrm{mmol}$ ) was added quickly to the flask. Three freeze-pump-thaw cycles were carried out again to remove residual oxygen. The mixture was reacted at $50^{\\circ}\\mathrm{C}$ for 1.5, 2 and $2.5\\mathrm{h}$ , respectively, and terminated by dropping a few THF droplets into the flask. The solution was passed through a neutral alumina column to intercept ${\\mathrm{Cu}}^{2+}$ and concentrated in a rotary evaporator. Finally, POSS-PDMAEMA polymers with three different polymerization degrees, i.e., POSS-PDMAEMA $50$ , POSS-PDMAEMA70, and POSS-PDMAEMA90, were obtained by precipitating into cold $n$ -hexane and followed by drying in a vacuum oven for $24\\mathrm{h}$ .  \n\nSynthesis of POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\mathbf{b}$ -PSBMA. In order to obtain block copolymer POSS-PDMAEMA- $b$ -PSBMA, ATRP initiator POSS-Br was first synthesized, and followed by POSS-PDMAEMA-Br preparation from ATRP of DMAEMA. Using POSS-PDMAEMA-Br as the macroinitiator, three POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA block copolymers with different polymerization degrees were synthesized via subsequent ATRP of SBMA. Typically, POSS-PDMAEMA-Br (0.01 mmol), SBMA (1 mmol) and HMTETA $(0.2\\mathrm{mmol})$ ) were dissolved in $6~\\mathrm{mL}$ mixed solvent of methanol-water $(1/1,\\mathbf{v}/\\mathbf{v})$ and were injected into the $25~\\mathrm{mL}$ standard Schlenk flask. The solution was degassed by three freeze-pump-thaw cycles under nitrogen atmosphere and then CuBr (0.1 mmol) was added quickly to the flask. Three freeze-pump-thaw cycles subsequently were carried out again to exclude remaining oxygen. The reaction mixture was stirred at $25~^{\\circ}\\mathrm{C}$ for $40\\mathrm{{h}}$ . POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA block copolymers were obtained by dialysis against deionized water for 3 days (MWCO 2000) and recovered by lyophilization. The POSS-PDMAEMA- $b$ -PSBMA block copolymers with different polymerization degrees and similar DMAEMA to PSBMA ratios, POSS- $\\mathrm{\\cdotD}_{50}–b–\\mathrm{S}_{7}$ , POSS- $\\cdot\\mathrm{D}_{70}{-}b{-}\\mathrm{S}_{10}$ , and POSS- $\\mathrm{\\cdotD}_{90}–b–\\ensuremath{\\mathrm{S}}_{13}$ were prepared.  \n\nSynthesis of PDMAEMA- $\\mathbf{\\delta}_{\\mathbf{b}}$ -PSBMA. Similar to the synthesis of POSS-PDMAEMA- $\\cdot b$ - PSBMA, block copolymer PDMAEMA ${.50}$ - $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA7 without POSS was synthesized by using ethyl-2-bromoisobutanoate as the initiator and followed by using PDMAEMA50-Br as the macroinitiator. PDMAE $\\mathrm{MA}_{50}$ -Br (0.01 mmol), SBMA (1 mmol) and HMTETA $(0.2\\mathrm{mmol})$ ) were dissolved in $6~\\mathrm{mL}$ mixed solvent of methanol-water $(1/1,\\mathbf{v}/\\mathbf{v})$ and were injected into the $25~\\mathrm{mL}$ standard Schlenk flask. The solution was degassed by three freeze-pump-thaw cycles under nitrogen atmosphere and then CuBr (0.1 mmol) was added quickly to the flask. Three freeze-pump-thaw cycles subsequently were carried out again to exclude remaining oxygen. The reaction mixture was stirred at $25~^{\\circ}\\mathrm{C}$ for $40\\mathrm{~h~}$ . The PDMAEMA $_{50}$ - $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA7 block copolymer i.e., $\\mathrm{D}_{50}–b–\\mathrm{S}_{7}$ , was obtained by dialysis against deionized water for 3 days (MWCO 2000) and recovered by lyophilization.  \n\nCharacterizations of POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\pmb{b}$ -PSBMA. $\\mathrm{^{1}H\\ N M R}$ spectra were recorded on an INOVA ${500}~\\mathrm{MHz}$ spectrometer (USA) using $\\mathrm{CDCl}_{3}$ and $\\mathrm{D}_{2}\\mathrm{O}$ as solvents. $\\mathrm{^{1}H\\ N M R}$ spectra of apPOSS, POSS-Br, POSS-PDMAE $\\mathrm{\\uA_{70}}$ , POSS-PDMAEMA $70$ - $\\cdot b$ -PSBMA10 are shown in Figure S1. In comparison with the $\\mathrm{^1H}$ NMR spectrum of POSS- $\\cdot\\mathrm{NH}_{2}$ shown in Figure S1(a), there are representative δH (ppm) at 3.26 (f), 1.96 (h), 6.75 (g) in Figure S1(b), verifying that the initiator POSS-Br was successfully synthesized.2 For POSS-PDMAEMA70 (Figure S1(c)), the appearance of signals of DMAEMA δH (ppm) at 0.89-1.05 (a), 1.82-1.96 (b), 2.32 (d), 2.61 (e), 4.07 (f) and typical δH (ppm) at 0.60 (c) of POSS- $\\mathrm{\\cdotNH}_{2}$ could prove the structure of POSS-PDMAEMA70. Compared with POSS-PDMAEMA $70$ (Figure S1(c)), the chemical structure of POSS-PDMAEMA $70$ - $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA10 (Figure S1(d)) could be confirmed by the evident δH (ppm) at S-3  \n\n4.00 (a), 2.61 (b), 2.19 (c, j), 1.70-1.83 (d, l), 0.77-1.00 (e, p), 3.09 (f), 3.50 (g), 4.35 (h), 2.83 (i),   \n3.66 (k).3  \n\n![](images/271dcad5f089ed3b6a8f6fb249884d5745774bf4f12554588de715b7fc2d2bfe.jpg)  \nFigure S1. $\\mathrm{^{1}H\\ N M R}$ spectra of apPOSS (a), POSS-Br (b), POSS-PDMAEMA $^{70}$ in $\\mathrm{CDCl}_{3}$ (c), and POSS- $\\cdot\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ in ${\\bf D}_{2}\\mathrm{O}$ (d).  \n\nFourier-transform infrared (FTIR) spectra of POSS-Br, POSS-PDMAEMA70, $\\mathrm{POSS-D}_{70^{-}}b.$ S10 were obtained on a Perkin-Elmer Spectrum 100 spectrometer (USA) using KBr pellet technique. As shown in Figure S2, the stretching vibration characteristic peak of Si-O-Si at $1112~\\mathrm{{cm}^{-1}}$ is apparent. The peak at $2954~\\mathrm{{cm}^{-1}}$ and $1323~\\mathrm{{cm}^{-1}}$ are attributed to the C-H stretching vibration and the C-H bending vibration, respectively. The signal at $695~\\mathrm{{cm}^{-1}}$ belongs to the C-Br stretching vibration.4,5 The data mentioned above further verify that POSS-Br was synthesized. In the FTIR spectra of POSS-PDMAEMA70, it is easily to find three C-H characteristic peaks at $2950~\\mathrm{cm}^{-1}$ , $2822~\\mathrm{{cm}^{-1}}$ and $2776~\\mathrm{{cm}^{-1}}$ . Meanwhile, the signals at $1723~\\mathrm{{cm}^{-1}}$ , $1457~\\mathrm{{cm}^{-1}}$ , $1270~\\mathrm{{cm}^{-1}}$ and 1112 $\\mathrm{cm}^{-1}$ belong to characteristic absorption bands of $\\scriptstyle\\mathbf{C=O}$ , C-N, $\\mathrm{CH}_{2}$ , and Si-O-Si respectively. All the date above mentioned demonstrates that POSS-PDMAEMA70 was prepared by ATRP. After copolymering with SBMA, we could find there was a new characteristic peak at $1039~\\mathrm{{cm}^{-1}}$ associated to the stretching vibration peak of $\\scriptstyle{\\mathsf{S}}=0$ , indicating the successful introduction of SBMA blocks. The peak appearance of C-O at $1149~\\mathrm{{cm}^{-1}}$ and the weaken strength of peak 1270 $\\mathrm{cm}^{-1}$ also proved the structure of POSS- $\\cdot\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ .6,7  \n\n![](images/a1874b6d00029e3d31c9b72a7f8e1b3e9bb22530edda1cd6b29962d729f7d9a1.jpg)  \nFigure S2. FTIR of POSS-Br, POSS-PDMAEMA70 and POSS- $\\cdot\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ .  \n\nThe molecular weight and polydispersity of the prepared copolymers PDMAEMA50, POSS-PDMAEMA with different polymerization degrees and $\\mathrm{D}_{50}–b–\\mathrm{S}_{7}$ were determined on a Waters 1515-2414 gel permeation chromatography (GPC, USA) with THF as the eluent and polystyrene as calibration. The polydispersity of the prepared polymers POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA were measured using a Viscotek’s GPC system with sodium acetate buffer $(0.5~\\mathrm{M}$ of NaAc and $0.5{\\mathrm{~M~}}$ of HAc, $\\mathrm{pH}=\\sim4.5)\\$ as the eluent at $30~^{\\circ}\\mathrm{C}$ at a flow rate of $1.0~\\mathrm{{mL}\\mathrm{{min}^{-1}}}$ . As shown in Figure S3, the unimodal GPC traces of POSS-PDMAEMA50, POSS-PDMAE $\\mathrm{\\uA_{70}}$ , POSS-PDMAEMA90, $\\mathrm{DMAEMA}_{50}$ , $\\mathrm{POSS-D}_{50^{-}}b{\\cdot}\\mathrm{S}_{7}$ , $\\mathrm{POSS-D}_{70}–b–\\mathrm{S}_{10}.$ , POSS- $\\mathrm{\\bfD}_{90}–b–\\mathrm{\\bfS}_{13}$ and $\\mathrm{D}_{50^{-}}b{-}S_{7}$ represented narrow polydispersity with PDI values of 1.27, 1.26, 1.22, 1.08, 1.07, 1.08, 1.11, and 1.19, respectively, indicating that the controlled polymerization was achieved. Because the molecular weight of zwitterionic polymers was difficult to measure by GPC, so we employed $\\mathrm{^{1}H}$ NMR and GPC to determine the molecular weight of the copolymers in this work. The molecular weight of POSS-PDMAEMA and POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA copolymers were calculated through the $\\mathrm{^{1}H N M R}$ method, but the molecular weight of $\\mathbf{PDMAEMA}_{50}$ and $\\mathrm{D}_{50^{-}}b{-}S_{7}$ were acquired by GPC due to its difficulty to adopt the $\\mathrm{^{1}H N M R}$ spectra by the integration of proton $\\mathrm{^{1}H N M R}$ feature signals.  \n\n![](images/4b53682a5979749255c0f4ae692d113fde9b0cf5bb5a547c7f5054a11ef1bdc3.jpg)  \nFigure S3. GPC curves of POSS-PDMAE $\\mathbf{MA}_{50}$ (a), POSS-PDMAE $\\mathbf{MA}_{70}$ (b), POSSPDMAEMA90 (c), $\\mathrm{DMAEMA_{50}}$ (d) and $\\mathrm{D}_{50^{-}}b{-}S_{7}$ (e) by using THF as the eluent, (A), and POSS- $\\mathbf{\\cdotD_{50}}–b\\mathbf{-S_{7}}$ (f), POSS- $\\cdot\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ (g) and POSS- $\\mathrm{\\cdotD}_{90^{-}}b{-}\\mathrm{S}_{13}$ (h) by using a sodium acetate buffer as the eluent (B).  \n\nThermal gravimetric analysis (TGA) was implemented on a TA Q50 instrument (USA) under nitrogen atmosphere at a heating rate of $10~\\mathrm{{^{\\circ}C/m i n}}$ from 20 to $800~^{\\circ}\\mathrm{C}$ . The TGA tests of POSS-Br, POSS-PDMAEMA70, POSS-PDMAEMA $70$ - $b$ -PSBMA10 were carried out. As shown in Figures S4, the TGA curve of POSS-Br reveals that $T_{\\mathrm{d}}$ at $5\\%$ mass loss is about $223.9\\ ^{\\circ}\\mathrm{C}$ due to its excellent thermodynamic stability, probably resulting from the existence of Si-O-Si bonds. Pure PDMAEMA showed total decomposition at about $500~^{\\circ}\\mathrm{C}$ in the reference.8 In this work, the mass of $\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ decreased to about zero at the end of measurement. For POSS-PDMAE $\\mathbf{MA}_{70}$ and $\\mathrm{POSS-D}_{70}–b–\\ensuremath{\\mathrm{S}}_{10}$ , the mass loss reaches $95.2\\%$ at $500~^{\\circ}\\mathrm{C}$ , and whereafter the mass of polymers remains unchanged, demonstrating the existence of the POSS component in the copolymers.  \n\n![](images/b377cbd859d4b90691c74b825ea562d11bb4c532d029b8ebf1153331e0ad3666.jpg)  \nFigure S4. TGA curves of POSS-Br (a), POSS-PDMAEMA70 (b), POSS- $\\mathrm{\\cdotD}_{70^{-}}b{-}\\mathrm{S}_{10}$ (c), and $\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ (d).  \n\nThermal remediation behavior and stability of the SIPN coatings. The sample C-POSS- $\\cdot\\mathrm{D}_{90}–b–\\mathrm{S}_{13}$ showed self-healing by vapor after scratched by a clean blade. The score disappeared completely after about 3 min as shown in Figure S5.  \n\n![](images/b315366679a4c375e671b421eae27aee3c4853139419911e4a0568690fe226f5.jpg)  \nFigure S5. Photographs of the C-POSS- $\\mathrm{.D}_{90}$ -b-S13 coating with a scratch (a), and the healable coating by vapor (b).  \n\nFigure S6(a) shows the condition of the $\\mathrm{POSS-D}_{70^{-}}b{\\mathrm{-}}\\mathrm{S}_{10}$ coating before immersed in deionized water, suggesting that the coating was as transparent as bare glass. Figure S6(b) shows the condition of the POSS- $\\cdot\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ coating during immersion in deionized water. An enough amount of deionized water was filled in the beaker, in which the coating sample was immersed. Figure S6(c) shows the condition of the $\\mathrm{POSS-D}_{70^{-}}b{\\mathrm{-}}\\mathrm{S}_{10}$ coating after immersion in deionized water for about $30~\\mathrm{min}$ . It can be seen that bare glass was obscure by water droplets, while the coating still kept its good transmittance. Thus, the coatings contain POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA show great stability for long-lasting utilities.  \n\n![](images/3073a8caf340ec30304ff5c23781ec638bcc9382422be089f4fbbadb1aeb41d1.jpg)  \nFigure S6. Photographs of the C-POSS- $\\cdot\\mathrm{D}_{70}{-}b{-}\\mathrm{S}_{10}$ coating before (a), during (b) and after immersed in deionized water (c).  \n\nATR-FTIR analysis of the SIPN coatings. Chemical surface characterization of the prepared SIPN coatings was analyzed by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR, Perkin-Elmer Spectrum100, USA). Figure S7 shows ATR-FTIR spectra of the prepared coatings. The characteristic absorption peaks at $2822~\\mathrm{{cm}^{-1}}$ and $2776\\mathrm{cm}^{-1}$ are attributed to C-H vibration of the $\\J\\mathrm{-N}(\\mathrm{CH}_{3})_{2}$ group from PDMAEMA, while the peak at 2950 $\\mathrm{cm}^{-1}$ belongs to C-H stretching vibration from other groups. Meanwhile, the signals at $1723\\mathrm{cm}^{-1}$ , $1270~\\mathrm{{cm}^{-1}}$ and $1457~\\mathrm{{cm}^{-1}}$ belong to characteristic absorption bands of $\\scriptstyle\\mathbf{C=O}$ , C-N and $\\mathrm{CH}_{2}$ , respectively. Furthermore, the characteristic absorption peak at $1039~\\mathrm{{cm}^{-1}}$ is related to stretching vibration peak of $\\scriptstyle{\\mathsf{S}}=0$ in PSBMA. In addition, the absorbance of the O-H stretching bands of hydrogen bonding was detected at $3414~\\mathrm{{cm}^{-1}}$ . The wavenumber range $1204{\\cdot}1085\\ \\mathrm{cm}^{-1}$ in the curves of Figure S7(a,b,c) include the peaks of $\\mathbf{C}\\mathbf{-}\\mathbf{O}$ at $1149\\mathrm{cm}^{-1}$ and Si-O-Si at $1112\\mathrm{cm}^{-1}$ .4 And, curve Figure S7(d) shows the peak at $1149~\\mathrm{{cm}^{-1}}$ , which is attributed to characteristic absorption band of C-O.4  \n\n![](images/02718d47f0d96d4eb97733a7995e2f9c272373d48b063d20501c2bcd959a381e.jpg)  \nFigure S7. ATR-FTIR spectra of the SIPN coatings of C-POSS- $\\cdot\\mathrm{D}_{50^{-}}b{-}S_{7}$ (a), C-POSS-D70-b-S10 (b), C-POSS- $\\mathrm{\\bfD}_{90^{-}}b.\\mathrm{\\bfS}_{13}$ (c), and $\\mathrm{C}{\\cdot}\\mathrm{D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ (d).  \n\nTEM analysis of the SIPN Coatings. The SIPN coating morphologies were observed under a JEOL JEM100CXII transmission electron microscope (TEM, Japan) at $100\\mathrm{kV}$ . TEM samples were prepared by dropping a droplet of the dilute copolymer solutions ( $1\\mathrm{\\mt{\\%}}$ in trifluoroethanol) on a thin carbon-coated copper grid, and then UV-curing in a XL-1000 ultraviolet cross-linker apparatus (USA) for 30min. As seen from these images (Figure S8), the aggregated POSS clusters are in the size range of $10{\\sim}80~\\mathrm{nm}$ , and well dispersed.  \n\n![](images/22105b4b182b3f7f6933f24c2261d05a5a7bf65488e9d1dbc57e477ae1e711b9.jpg)  \nFigure S8. TEM images of the SIPN coatings of C-POSS-D $50$ -b-S7 (a), C-POSS-D $^{70}$ -b-S10 (b), C-POSS- $\\cdot\\mathrm{D}_{90}–b–\\mathrm{S}_{13}$ (c), and $\\mathrm{C}{\\cdot}\\mathrm{D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ (d).  \n\nDSC analysis of the SIPN Coatings. The SIPN coatings were analyzed by a TA Q2000 differential scanning calorimetry machine (DSC, USA). The samples containing a certain amount of deionized water were prepared by adding water into the SIPN coatings (about $4{\\sim}5~\\mathrm{mg}$ ) scraped from the glass slide, and keeping them in the aluminium pans for 10 days at room temperature. The heating rate had a negligible effect on the content of non-freezable bond water and bond water as shown in Table S1.  \n\nTable S1. Water contents in different states in the samples analyzed by DSC at different heating rates   \n\n\n<html><body><table><tr><td rowspan=\"2\">Sample</td><td rowspan=\"2\">Heating rate</td><td rowspan=\"2\">Wc (mg/mg)</td><td colspan=\"6\">Freezable water Wf (mg/mg)</td><td rowspan=\"2\">Non-freezable Bond bond water water Wb</td></tr><tr><td>Wf</td><td colspan=\"2\">Freezable bond water</td><td colspan=\"2\">Freezable free water</td></tr><tr><td></td><td>(C/min)</td><td></td><td>(mg/mg)</td><td>Wfb (mg/mg)</td><td>Tfbm (℃)</td><td>Wff (mg/mg)</td><td>Tffm (℃)</td><td>Wnfb (mg/mg)</td><td>(mg/mg)</td></tr><tr><td>C-POSS-D50-b-S7</td><td>5</td><td>1.21</td><td>0.76</td><td>0.13</td><td>-14.88</td><td>0.63</td><td>-1.56</td><td>0.45</td><td>0.58</td></tr><tr><td rowspan=\"4\">C-POSS-D7o-b-S10</td><td>10</td><td></td><td>0.76</td><td>0.14</td><td>-14.01</td><td>0.62</td><td>-1.30</td><td>0.45</td><td>0.59</td></tr><tr><td>15</td><td></td><td>0.76</td><td>0.14</td><td>-13.10</td><td>0.62</td><td>-1.07</td><td>0.45</td><td>0.59</td></tr><tr><td>5</td><td>1.20</td><td>0.77</td><td>0.11</td><td>-17.54</td><td>0.66</td><td>-2.06</td><td>0.43</td><td>0.54</td></tr><tr><td>10</td><td></td><td>0.77</td><td>0.16</td><td>-17.42</td><td>0.61</td><td>-1.91</td><td>0.43</td><td>0.59</td></tr><tr><td>C-POSS-D90-b-S13</td><td>15</td><td></td><td>0.77</td><td>0.15</td><td>-14.61</td><td>0.62</td><td>-1.73</td><td>0.43</td><td>0.58</td></tr><tr><td rowspan=\"4\"></td><td>5</td><td>1.22</td><td>0.77</td><td>0.14</td><td>-15.34</td><td>0.63</td><td>-1.96</td><td>0.45</td><td>0.59</td></tr><tr><td>10</td><td></td><td>0.77</td><td>0.14</td><td>-15.01</td><td>0.63</td><td>-1.50</td><td>0.45</td><td>0.59</td></tr><tr><td>15</td><td></td><td>0.77</td><td>0.15</td><td>-14.50</td><td>0.62</td><td>-1.11</td><td>0.45</td><td>0.60</td></tr><tr><td>5</td><td>1.24</td><td>0.72</td><td>0.11</td><td>-16.55</td><td>0.61</td><td>-2.41</td><td>0.52</td><td>0.63</td></tr><tr><td>C-D50-b-S7</td><td>10</td><td></td><td>0.72</td><td>0.09</td><td>-16.34</td><td>0.63</td><td>-2.13</td><td>0.52</td><td>0.61</td></tr><tr><td></td><td>15</td><td></td><td>0.72</td><td>0.12</td><td>-15.13</td><td>0.60</td><td>-1.87</td><td>0.52</td><td>0.64</td></tr></table></body></html>",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 3,
+        "chunk": "# References  \n\n(1) Ma, L.; Geng, H. P.; Song, J. X.; Li, J. Z.; Chen, G. X.; Li, Q. F. Hierarchical Self-Assembly of Polyhedral Oligomeric Silsesquioxane End-Capped Stimuli-Responsive Polymer: From Single Micelle to Complex Micelle. J. Phys. Chem. B 2011, 115, 10586-10591. (2) Shao, Y.; Aizhao, P.; Ling, H. POSS End-Capped Diblock Copolymers: Synthesis, Micelle Self-Assembly and Properties. J. Colloid Interface Sci. 2014, 425, 5-11. (3) Zhang, M. M.; Shen, W.; Xiong, Q. Q.; Wang, H. W.; Zhou, Z. M.; Chen, W. J.; Zhang, Q. Q. Thermo-Responsiveness and Biocompatibility of Star-Shaped Poly[2-(dimethylamino) ethyl methacrylate]- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -Poly(sulfobetaine methacrylate) Grafted on $\\upbeta$ -Cyclodextrin Core. Rsc Adv. 2015, 5, 28133-28140. (4) Li, Y. M.; Xu, B.; Bai, T.; Liu, W. G. Co-Delivery of Doxorubicin and Tumor-Suppressing p53 Gene Using a POSS-Based Star-Shaped Polymer for Cancer Therapy. Biomaterials 2015, 55, 12-23. (5) Liu, Y. H.; Yang, X. T.; Zhang, W. A.; Zheng, S. X. Star-Shaped Poly(ε-caprolactone) with Polyhedral Oligomeric Silsesquioxane Core. Polymer 2006,47, 6814-6825. (6) Chou, Y. N.; Chang, Y.; Wen, T. C. Applying Thermosettable Zwitterionic Copolymers as General Fouling-Resistant and Thermal-Tolerant Biomaterial Interfaces. ACS Appl. Mater. Interfaces 2015, 7, 10096-10107. (7) Dong, Z.; X, Mao, J.; Wang, D. P.; Yang M. Q.; Wang W. C.; Bo S. Q.; Ji X. L. Tunable Dual-Thermoresponsive Phase Behavior of Zwitterionic Polysulfobetaine Copolymers Containing Poly(N,N-dimethylaminoethylmethacrylate)-Grafted Silica Nanoparticles in Aqueous Solution. Macromol. Chem. Phys. 2014, 215, 111-120. (8) Zhang, P.; Yang, J. H.; Li, W. C.; Wang, W.; Liu, C. J.; Griffith, M.; Liu, W. G. Cationic Polymer Brush Grafted-Nanodiamond via Atom Transfer Radical Polymerization for Enhanced Gene Delivery and Bioimaging. J. Mater. Chem. 2011, 21, 7755-7764.",
+        "category": " References"
+    }
+]
\ No newline at end of file
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+[
+    {
+        "id": 1,
+        "chunk": "# Amphiphilic Antifogging/Anti-icing Coatings Containing POSS-PDMAEMA-b-PSBMA  \n\nChuan Li, Xiaohui Li, Chao Tao, Lixia Ren, Yunhui Zhao, Shan Bai, and Xiaoyan Yuan ACS Appl. Mater. Interfaces, Just Accepted Manuscript $\\cdot$ DOI: 10.1021/acsami.7b05286 • Publication Date (Web): 20 Jun 2017 Downloaded from http://pubs.acs.org on June 24, 2017",
+        "category": " References"
+    },
+    {
+        "id": 2,
+        "chunk": "# Just Accepted  \n\n“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier $(\\mathsf{D O}|\\oplus)$ . “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# Amphiphilic Antifogging/Anti-icing Coatings Containing POSS-PDMAEMA-b-PSBMA  \n\nChuan Li, Xiaohui Li, Chao Tao, Lixia Ren, Yunhui Zhao, Shan Bai, and Xiaoyan Yuan School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300072, China  \n\nKEYWORDS: amphiphilic coating, semi-interpenetrating polymer network, POSS, antifogging, anti-icing  \n\nABSTRACT: Highly transparent antifogging/anti-icing coatings were developed from amphiphilic block copolymers of polyhedral oligomeric silsesquioxane-poly[2- (dimethylamino)ethyl methacrylate]-block-poly(sulfobetaine methacrylate) (POSS-PDMAEMA$b$ -PSBMA) with a small amount of ethylene glycol dimethacrylate (EGDMA) via UV-curing. The excellent antifogging properties of the prepared coatings were originated from the hygroscopicity of both PDMAEMA and PSBMA blocks in the semi-interpenetrating polymer network (SIPN) with polymerization of EGDMA, and hydrophobic POSS clusters aggregated on the surface. PDMAEMA with a lower critical solution temperature and PSBMA with an upper critical solution temperature in the block copolymers facilitated dispersion and absorption of water molecules into the SIPN coatings, fulfilling the enhanced antifogging function. Analysis of differential scanning calorimetry further confirmed that there were bond water and non-freezable bond water in the SIPN coatings. The amphiphilic SIPN coatings exhibited the anti-icing ability with a freezing delay time of more than $2~\\mathrm{min}$ , owing to the aggregation of hydrophobic POSS groups and the self-lubricating aqueous layer generated by non-freezable bond water on the surface. The prepared transparent antifogging/anti-icing coatings could have novel potential applications in practice.",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# INTRODUCTION  \n\nFormation of fog is ascribed to condensed water droplets caused by unexpected changes in temperature and humidity, bringing about optical opaque of transparent surfaces such as windshields, periscopes, display devices in the analytical instruments.1-3 To alleviate the trouble of fog, superhydrophilic polymer films have been extensively investigated because their surfaces can quickly absorb and spread condensed water droplets, forming a continuous aqueous layer that allows light to pass through without too much scattering.2-5 Superhydrophobic surfaces were also applied to mitigate fogging problems and impart these surfaces antifogging performance.6,7 Nevertheless, preparation of highly transparent antifogging coatings still remained a challenge, especially for the meticulous preparation process of the superhydrophilic and superhydrophobic surfaces with micro/nano-structures that possibly limited their applications.5-7  \n\nIn the recent years, amphiphilic coatings have been developed to achieve effective antifogging properties via the synergistic strategy of hydrophilic and hydrophobic components.3,8-10 Cohen et al. prepared zwitter-wettable antifogging coatings by layer-by-layer assembly from chitosan and Nafion with a nanoscale thin hydrophobic capping layer, enabling water vapor to diffuse rapidly into the underlying hydrophilic coatings.8 Triggered by the hydrophilic/hydrophobic balance, Ming et al. fabricated a semi-interpenetrating polymer network (SIPN) coating from an acrylate copolymer, namely, poly(2-(dimethylamino)-ethyl methacrylate-co-methyl methacrylate) via polymerization of ethylene glycol dimethacrylate (EGDMA) to achieve the antifogging purpose.9,10 In contrast to superhydrophilic or superhydrophobic antifogging coatings, amphiphilic coatings displayed high initial water contact angles which subsequently decreased to low values within a period of time.8,9 Water or vapor molecules could be rapidly absorbed from the surrounding environment and spread in the coatings by hydrogen-bond interaction in the form of non-freezable water, rather than condensed as drops of liquid water on the surface.2-4,8-10 The hydrophobicity of amphiphilic coatings also facilitated dispersion of water molecules into the coatings.3,8-10  \n\nIn addition to the antifogging capability, the amphiphilic coatings exhibited frost-resisting3,10 or anti-icing properties.11,12 For example, a small amount $(1w t\\%)$ of amphiphilic copolymer polydimethylsiloxane (PDMS)-poly(ethylene glycol) (PEG, $25\\%$ ) was introduced in the smooth PDMS coating, and then a viscous lubricating liquid-like layer could generate at the coating surface which exhibited icephobicity with lower ice adhesion strength.11 Amphiphilic crosslinked hyperbranched fluoropolymers containing water-absorbing PEG chains also demonstrated anti-icing candidates for potential engineering applications.12 Alternatively, the surfaces consisting of cross-linked hygroscopic polymers such as poly(acrylic acid) could be infused with water, bringing about a self-lubricating aqueous layer for the anti-icing purpose.13,14 Moreover, slippery liquid infused nanostructured surfaces could exhibit ice-repellency behaviors,15,16 as well as excellent optical transparency.17 The aqueous layer self-lubricating coatings with distinguished antifogging/anti-icing abilities would exhibit a great advantage in the practical applications.11-14  \n\nAs we know, dual-thermosensitive block copolymers could be prepared from a lower critical solution temperature (LCST) polymer such as poly( $N.$ -isopropylacrylamide) and poly(N,Ndimethylaminoethyl methacrylate) (PDMAEMA), and an upper critical solution temperature (UCST) polymer such as zwitterionic poly(sulfobetaine methacrylate) (PSBMA) or a random copolymer of poly(acrylamide-co-acrylonitrile).18-20 The random or block copolymers could display both LCST and UCST characteristics in the aqueous solution,18-20 even though they were grafted from silica nanoparticles.18 Thus, it can be assumed that antifogging/anti-icing coatings can be developed by combining PDMAEMA with LCST and PSBMA with UCST that could possibly give rise to a self-lubricating aqueous layer when exposed to water or vapor, and synergistically enhance the antifogging and anti-icing performances. Meanwhile, PDMAEMA was chosen as the main part of the amphiphilic polymers because of its good film-forming property on substrates and fine stability. On the other hand, due to strongly electrostatic and hydrogen-bond interactions with water, zwitterionic PSBMA could regulate and control the hydrophilcity of POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA and enhance the antifogging/anti-icing performances of the amphiphilic SIPN coatings. Additionally, the zwitterionic PSBMA component could possibly reduce the freezing point of water as stated in the references.21,22  \n\nAccording to our previous studies on polyhedral oligomeric silsesquioxane (POSS)-containing fluorosilicone block copolymers, POSS groups with low surface energy could migrate and aggregate on the coating surfaces, endowing them with hydrophobicity for anti-icing.23-26 By integrating POSS with both PDMAEMA and PSBMA via atom transfer radical polymerization (ATRP), in this work, we prepared the amphiphilic SIPN coatings from POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ - PSBMA block copolymers with a small amount $(10w t\\%)$ of EGDMA via UV-curing. We supposed that PDMAEMA and PSBMA blocks in the cross-linked PEGDMA network coupled with hydrophobic POSS groups could facilitate absorption of water or vapor molecules into the coatings to enhance the antifogging performance. Also, the amphiphilic SIPN coating was expected to decrease the water freezing-point by forming a self-lubricating aqueous layer at the surface so as to keep high transmittance under foggy conditions and display the anti-icing properties.",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# EXPERIMENTAL SECTION  \n\nSynthesis of POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\mathbf{b}$ -PSBMA.  The POSS-PDMAEMA- $b$ -PSBMA block copolymers were synthesized via ATRP of DMAEMA by using POSS-Br as an initiator according to the reference,27 and followed by ATRP of SBMA by using POSS-PDMAEMA-Br as a macroinitiator (Scheme 1). Three POSS-PDMAEMA- $b$ -PSBMA block copolymers with different polymerization degrees were prepared, while block copolymer PDMAEMA- $b$ -PSBMA without POSS by using ethyl-2-bromoisobutanoate as the initiator was also synthesized as control. According to the references, stronger hydrogen-bonded water molecules can form on the zwitterionic SBMA surfaces rather than on the surface of PEG,28 and a small amount of SBMA in the PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA block copolymers still exhibited dual-thermoresponsive performance.20 Given that PDMAEMA chains played a key role in antifogging,9,10 we further designed the block copolymers with a higher DMAEMA content. In order to obtain similar molar ratios of DMAEMA to SBMA, three block copolymers, i.e., POSS-PDMAEMA ${50}$ -bPSBMA7, POSS-PDMAEMA ${}_{70}$ - $\\boldsymbol{\\cdot}\\boldsymbol{b}$ -PSBMA10 and POSS-PDMAEMA90- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA13 were synthesized. Compositions of the prepared block copolymers, abbreviated as POSS- $\\mathrm{\\cdotD}_{50^{-}}b{-}\\mathrm{S}_{7}$ , POSS- $\\mathrm{\\cdotD}_{70^{-}}b{-}\\mathrm{S}_{10}$ , P $\\mathrm{OSS-D}_{90^{-}}b.$ and $\\mathrm{D}_{50}–b–\\mathrm{S}_{7}$ , respectively, are shown in Table 1. Detailed synthesis of the block copolymers and their characterizations by $\\mathrm{^1H}$ nuclear magnetic resonance ( $\\mathrm{^{1}H}$ NMR), Fourier transform infrared (FTIR), gel permeation chromatography (GPC) and thermogravimetric analysis (TGA) are given in the Supporting Information Figures S1-S4.  \n\nScheme 1.  Schematic illustration of synthesis of POSS-PDMAEMA- $b$ -PSBMA  \n\n![](images/bd421c33bf100bc63ce88cdb066d41a5231659d7e0bb9d632aa5ac0cac5ccd46.jpg)  \n\nTable 1. Compositions of the prepared block copolymers   \n\n\n<html><body><table><tr><td rowspan=\"2\">Sample</td><td>Feeding composition</td><td>Molar composition</td><td rowspan=\"2\">Mna) (×104)</td><td rowspan=\"2\">PDI</td></tr><tr><td>DMAEMA:SBMA (mol:mol)</td><td>DMAEMA:SBMA in the copolymer a) (mol:mol)</td></tr><tr><td>POSS-D50-b-S7</td><td>50:7</td><td>43:7 (6.14:1)</td><td>0.97</td><td>1.07</td></tr><tr><td>POSS-D7o-b-S10</td><td>70:10</td><td>65:11 (5.91:1)</td><td>1.43</td><td>1.08</td></tr><tr><td>POSS-D90-b-S13</td><td>90:13</td><td>95:15 (6.33:1)</td><td>2.02</td><td>1.11</td></tr><tr><td>D50-b-S7</td><td>50:7</td><td>40:11 (3.64:1)</td><td>0.96</td><td>1.19</td></tr></table></body></html>\n\na) The molar composition and the number-average molecular weight of the POSS-PDMAEMA-bPSBMA block copolymers (abbreviated as POSS- $\\mathrm{\\cdotD}_{50}{\\mathrm{-}}b{\\mathrm{-}}\\mathrm{S}_{7}$ , POSS- $\\mathrm{\\cdotD}_{70^{-}}b{\\cdot}\\mathrm{S}_{10}$ and POSS- $\\mathrm{\\bfD}_{90}–b–\\mathrm{S}_{13},$ , respectively) were estimated by $^1\\mathrm{H}$ NMR spectra, and the result of PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA (abbreviated as $\\mathrm{D}_{50}–b–\\mathrm{S}_{7}$ ) was determined by GPC.  \n\nPreparation of the SIPN Coatings.  A given amount of the block copolymer (POSS- $\\cdot\\mathrm{D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ , POSS- $\\cdot\\mathrm{D}_{70}{-}b{-}\\mathrm{S}_{10}$ , $\\mathrm{POSS-D}_{90}–b–\\mathbf{S}_{13}$ , or $\\mathrm{D}_{50}–b–\\mathrm{S}_{7},$ ) was dissolved in 2,2,2-trifluoroethanol to prepare a $25~\\mathrm{mg/mL}$ polymer solution. EGDMA ( $10\\mathrm{{wt\\%}}$ based on the copolymer) and Igracure 2959 UV photoinitiator $(2\\mathrm{wt\\%})$ were also added. The polymer coatings were prepared by casting $0.2~\\mathrm{mL}$ of the polymer solution onto a half of a clean glass slide (both sides), and then placing them under UV conditions $365~\\mathrm{nm}$ , 15 W, 1800 s) in a XL-1000 ultraviolet cross-linker apparatus (USA) for polymerization of EGDMA. The SIPN coatings containing the block copolymer POSS- $\\mathrm{\\cdotD}_{50}–b–\\ensuremath{\\mathrm{S}}_{7}$ , POSS- ${\\bf\\cdot D}_{70}$ -b-S10, POSS- $\\mathrm{\\cdotD}_{90}–b–\\mathrm{S}_{13}$ and $\\mathrm{D}_{50}–b–\\mathrm{S}_{7}$ , denoted as C-POSS- $\\cdot\\mathrm{D}_{50}{-}b{-}\\mathrm{S}_{7}$ , C-POSS- $\\cdot\\mathrm{D}_{70}{-}b{-}\\mathrm{S}_{10}$ , C-POSS- $\\mathrm{D}_{90}–b–\\mathrm{S}_{13}$ and $\\mathrm{C-D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ , respectively, were obtained by further air-drying at room temperature. The thickness of the obtained SIPN coatings was about $10\\upmu\\mathrm{m}$ .  \n\nCharacterizations.  Atomic force microscope (AFM) images were obtained by a CSPM5500A microscope AFM machine (Benyuan Nano-Instruments, China) equipped with an E-type vertically engaged piezoelectric scanner and operated in a tapping-mode at room temperature. X-ray photoelectron spectroscopy (XPS) measurements were performed on a Perkin-Elmer PHI 5000C ECSA system (USA), utilizing an excitation source of Al Kα radiation under a pressure of ${\\sim}6.7\\times10^{-6}$ Pa at $45^{\\circ}$ . Water contact angles of the SIPN coatings and their evolution were recorded by a JC2000D contact angle meter (Shanghai Zhongchen Equipment Co. Ltd., China) to examine the wettability of the samples with deionized water drops $(5\\upmu\\mathrm{L})$ .  \n\nAntifogging Tests.  The antifogging property was tested with the hot-vapor and cold-warm methods, separately. Generally, the glass slide covered by the SIPN coatings on the half was put over hot vapor (above about 5 cm high) on top of a glass beaker which contained hot water $(\\sim80$ $^{\\circ}\\mathrm{C}$ , $100\\%$ relative humidity), and the sample transparency was recorded immediately. In addition, the appearance of the samples was recorded quickly when they were exposed to a warm, humid environment ${\\mathrm{\\sim}}20~^{\\circ}\\mathrm{C},$ , $55\\%$ relative humidity) right after being stored in a ${\\displaystyle-20~^{\\circ}C}$ freezer for $45\\mathrm{\\min}$ . The transmittance of the samples was also measured in a 722s visible spectrophotometer (Shanghai Jinghua Technology Instrument Co. Ltd., China) ranging from 400 to $800\\mathrm{nm}$ for the quantitative measurement.  \n\nAnti-icing Tests.  The freezing delay time $(T_{\\mathrm{D}})$ of water droplets on the SIPN coatings was measured to test the anti-icing performance. The specimen was placed on a cold-plate (Tianjin Jing Yi Industry & Trade Co. Ltd., China) which was controlled at $-15~^{\\circ}\\mathrm{C}$ . Once a deionized water droplet $(5\\upmu\\mathrm{L})$ dropped on the coating surface, its appearance was recorded in every second, and the time when the water droplet became ice completely, i.e., when a sharp tip appeared on the droplet top, was regarded as the freezing delay time.  \n\nDifferential Scanning Calorimetry (DSC) Analysis.   The bond water amount in the SIPN coatings was analyzed by DSC (TA Q2000, USA). The samples for the DSC measurements containing a certain amount of deionized water were prepared by adding water into the SIPN coatings (about $4{\\sim}5\\ \\mathrm{mg}$ ) which were scraped from the glass slide. The sample was kept and stabilized in the aluminium pan for 10 days at room temperature. When no mass changes were confirmed in the several days, the samples were tested in the following a procedure by purging nitrogen gas. The sample was first cooled from 20 to $-70~^{\\circ}\\mathrm{C}$ at a cooling rate of $5~{^\\circ}\\mathrm{C}/\\mathrm{min}$ , and maintained for 3 min. Then, it was heated to $20~^{\\circ}\\mathrm{C}$ at a heating rate of $5~{\\mathrm{{^{\\circ}C/m i n}}}$ , and subsequently held at $20~^{\\circ}\\mathrm{C}$ for around $3~\\mathrm{min}$ . The cooling-heating cycle was also conducted in the same manner at heating/cooling rates of 10 and $15~\\mathrm{{^{\\circ}C/m i n}}$ , respectively. The total water content $(W_{\\mathrm{c}})$ , the freezable water content $(W_{\\mathrm{f}})$ , the non-freezable bond water content $(W_{\\mathrm{nfb}})$ and the bond water content $(W_{\\mathfrak{b}})$ in the samples were calculated according to the following equations.29-33  \n\n$$\n\\begin{array}{r l}&{W_{\\mathrm{c}}=m_{\\mathrm{w}}/m_{\\mathrm{c}}}\\\\ &{W_{\\mathrm{f}}=A_{\\mathrm{c}}/(334\\cdot m_{\\mathrm{c}})}\\\\ &{W_{\\mathrm{nfb}}=W_{\\mathrm{c}}\\cdot W_{\\mathrm{f}}}\\\\ &{W_{\\mathrm{b}}=W_{\\mathrm{fb}}+W_{\\mathrm{nfb}}}\\end{array}\n$$  \n\nwhere, $m_{\\mathrm{w}}$ and $m_{\\mathrm{c}}$ represent the masses of water and the coating, respectively, in the samples, and $A_{\\mathrm{c}}\\left(\\mathrm{J/g}\\right)$ refers to the integral melting peak area in the heating curves. Here, we hypothesize that the enthalpies of both free and freezable water are equal to $334\\ \\mathrm{J/g}$ , the specific heat of water fusion.29 During the analysis, the freezable bond water content $(W_{\\mathrm{fb}})$ was corresponding to the area of the symmetric peak at around $-15^{\\circ}\\mathrm{C}$ in the heating curves, and the free water content $(W_{\\mathrm{ff}})$ (that is freezable) was the difference between Wf and Wfb according to the references.29,30 Therefore, the bond water content $(W_{\\mathfrak{b}})$ was the sum of $W_{\\mathrm{fb}}$ and $W_{\\mathrm{nfb}}$ . The melting temperatures of the freezable bond water $\\left(T_{\\mathrm{fbm}}\\right)$ and the freezable free water $\\left(T_{\\mathrm{ffm}}\\right)$ were designated as the peak temperatures of the fitting symmetric peak and the melting peak, respectively in the heating curves of the samples.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 6,
+        "chunk": "# RESULTS AND DISCUSSION  \n\nAntifogging Properties.  The antifogging performance of the SIPN coatings was demonstrated with the hot-vapor and cold-warm methods. For the hot-vapor method, the glass slides with both sides partially coated by the SIPN coatings were placed 5 cm high above boiling water ${\\mathrm{'}}80{}^{\\circ}\\mathrm{C},$ , $100\\%$ relative humidity). As shown in Figure 1A, it can be seen that the uncoated areas of the bare glass slides were apparently covered by small condensed water droplets of hot vapor, resulting in optical opacity. In contrast, the other halves of the glass slides with the SIPN coatings still remained highly transparent. The excellent antifogging properties of all the samples could be attributed to the hydrophilic PDMAEMA and PSBMA blocks in the copolymers and the cross-linked PEGDMA network, which allowed water molecules to be rapidly absorbed into the SIPN coating and possibly spread over the coating surface, similar with the situation stated in the references.8,34 It was supposed that surface hydration of the prepared coatings could occur owing to the hydrogen-bonded interactions of water molecules with PDMAEMA and PSBMA blocks as well as PEGDMA.28 When water molecules entered into the coatings, hydrogen bonds between water and polymer chains could be formed in the SIPN coatings at a molecular level due to the presence of oxygen atoms of ester and ether groups in PDMAEMA, PSBMA and PEGDMA chains as well as nitrogen atoms in the structure of PDMAEMA, ensuring the excellent optical transparency. Moreover, because of the electrostatic attraction of zwitterionic groups, the hydrogen-bonded interaction between hydrophilic PSBMA and water molecules is stronger than that between water and PDMAEMA or PEGDMA chains in the coatings.28,35  \n\n![](images/b0f89a3e31d15a43327375501360b06d6298ec7fddcb1f7304426c99aa17d942.jpg)  \n\nFigure 1. Photographs of the glass slides partially covered with the SIPN coatings containing POSS- $\\mathrm{\\cdotD}_{50^{-}}b{-}\\mathrm{S}_{7}$ (a), POSS- $\\mathrm{\\cdotD}_{70}$ -b-S10 (b), POSS- $\\mathrm{.D}_{90}$ -b-S13 (c) and $\\mathrm{D}_{50}–b–\\mathrm{S}_{7}$ (d), respectively over boiling water ${\\sim}80~^{\\circ}\\mathrm{C},$ , $100\\%$ relative humidity) (A), and exposed quickly at ambient conditions 1 ${\\sim}20^{\\circ}\\mathrm{C}$ , $55\\%$ relative humidity) right after being stored at ${\\displaystyle-20~^{\\circ}C}$ for 45 min (B).  \n\nIn addition, when the temperature exceeded LCST (about $48~^{\\circ}\\mathrm{C})$ ) of PDMAEMA,20 the random coil conformation of the PDMAEMA chains tended to collapse due to the break of hydrogen-bonded interactions between the polymer and water molecules, resulting in the gathering tendency of PDMAEMA chains.20 The PDMAEMA chains, however, were restricted by the cross-linked network and could not aggregate to some extent. Therefore, the contractive force caused by PDMAEMA chains gathering could give rise to free voids for water molecules dispersion in the SIPN coatings.  \n\nThe antifogging performance of the SIPN coatings was also evaluated with the cold-warm method. The SIPN coatings were first stored in a $-20\\ ^{\\circ}\\mathrm{C}$ freezer for $45\\ \\mathrm{min}$ and then rapidly exposed to a warm, humid environment ( ${\\sim}20~^{\\circ}\\mathrm{C}$ , $55\\%$ relative humidity). As shown in Figure 1B, the uncoated parts of the glass slides were fogged severely and the words and patterns under the container became heavily blurred due to light scattering. In contrast, the coated parts displayed high transparency, indicating the excellent antifogging performance of the SIPN coatings. When water molecules were absorbed in the coatings, hydrogen bonds between water and the polymer molecules were subsequently generated at a molecular level.28 Additionally, when the temperature was inferior to UCST $({\\sim}5^{\\ \\circ}\\mathrm{C})$ of PSBMA,20 the random coil of the PSBMA chains tended to collapse due to the strong inter-chain ionic interactions between PSBMA chains, resulting in gathering tendency of PSBMA chains.18-20 Therefore, water molecules were conducive to well dispersion in the SIPN coatings, which was attributed to the contractive force generated by the trend of gathering of PSBMA blocks under the limitation of the cross-linked PEGDMA structure.  \n\nThe antifogging properties were quantitatively characterized by measuring the transmittance of the bare glass and the coated parts of the glass slides in range of visible light wavelength from 400 to $800\\ \\mathrm{nm}$ (Figure 2). The optical transmittances of C-POSS- $\\mathrm{\\cdotD}_{50^{-}}b{-}\\mathrm{S}_{7}$ , C-POSS- ${\\bf\\cdot D}_{70}$ -b-S10, C-POSS- $\\mathrm{D}_{90}–b–\\ensuremath{\\mathrm{S}}_{13}$ and $\\mathrm{C}{\\cdot}\\mathrm{D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ were $87.2{\\sim}89.2\\%$ , $88.0{\\sim}90.2\\%$ , $89.0{\\sim}91.2\\%$ and $85.9\\sim88.6\\%$ , respectively, which were quite similar to that of the bare glass $(85.1{\\sim}91.0\\%)$ ). The transmittance of the SIPN coatings containing POSS-PDMAEMA-b-PSBMA slightly increased with the rise of the molecular weight of the block copolymers, and all the SIPN coatings with or without POSS exhibited minor differences in the transmittance (Figure 2A). As shown in Figure 2B, during the cold-warm antifogging test, the transmittance of the bare glass decreased sharply to about $61.5{\\sim}63.2\\%$ due to the formation of fog on the surface. The transmittance of the SIPN coatings containing POSS- $\\mathrm{\\cdotD}_{50}–b–\\mathrm{S}_{7}$ , POSS- $\\mathrm{\\cdotD}_{70^{-}}b{-}\\mathrm{S}_{10}$ and POSS- $\\mathrm{\\cdotD}_{90}–b–\\mathrm{S}_{13}$ still remained $87.1{\\sim}89.8\\%$ , $87.1{\\sim}90.0\\%$ and $88.0{\\sim}90.4\\%$ , respectively, with trivial variations compared to the values before tests, showing excellent antifogging performance. The SIPN coating containing $\\mathrm{D}_{50}–b–\\mathrm{S}_{7}$ without POSS became $86.4{\\sim}88.7\\%$ , also exhibiting good antifogging property but inferior to the coatings containing POSS related copolymers. It was suggested that there was an important effect of hydrophobic POSS groups on the antifogging performance of the SIPN coatings.  \n\n![](images/cfcea5cde85f49571ab5b43698c72a74ec489cce27747c040f098fd01e9f81aa.jpg)  \nFigure 2. Transmittance of the SIPN coatings before (A) and after stored at $-20~^{\\circ}\\mathrm{C}$ for $45\\mathrm{min}$ , and exposed quickly to a warm, humid surrounding ${\\sim}20^{\\circ}\\mathrm{C},$ , $55\\%$ relative humidity) (B).  \n\nFor different structures of the polymeric coatings with or without POSS, the $\\mathrm{C}{\\cdot}\\mathrm{D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ coating exhibited low transmittance before and after fogging in comparison with C-POSS- ${\\bf\\cdot D}_{50}$ -b$\\mathbf{S}_{7}$ , indicating that the incorporation of POSS led to an active effect on the transmittance of the coating. It was assumed that the aggregated POSS groups on the SIPN coating surfaces could facilitate water dispersion into the amphiphilic SIPN coatings. However, for the amphiphilic SIPN coatings with similar structures, the transmittance of the coatings slightly increased before and after fogging with the rise of the molecular weight of the POSS block copolymers. It was indicated that the introduction of POSS resulted in a little negative effect on the transmittance which did not decease too much. It was assumed that the POSS-PDMAEMA- $b$ -PSBMA copolymers could regulate and control the wettability of the amphiphilic SIPN coatings.  \n\nAdditionally, the SIPN coatings may possess the ability of “thermal remediation” because the score scratched by a clean blade could be healed by vapor. The score on the C-POSS- ${\\bf\\cdot D}_{70}$ -b-S10 coating disappeared completely when the sample was exposed over the hot vapor for 3 min as shown in the Supporting Information Figure S5. The phenomenon may be explained by the fact that the molecular chains of collapse could be reorganized under the drive of water vapor due to the partially cross-linked network of the SIPN coating as well as the hydrogen-bond interactions between water and the polymeric molecules.3,36 Moreover, the SIPN coatings demonstrated great stability when immersed in water, suggesting their long-lasting utilities as shown in the Supporting Information Figure S6. With the healable antifogging performance and stability, the SIPN coatings of the POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA block copolymers could have versatile potential applications.  \n\nSurface Characteristics of the SIPN Coatings.  AFM was employed to observe the surface morphology of the SIPN coatings. As shown in Figure 3, all C-POSS- $\\mathrm{\\cdotD}_{50^{-}}b{-}\\mathrm{S}_{7}$ , C-POSS- ${\\bf\\cdot D}_{70}$ -b$\\mathrm{S}_{10}$ , C-POSS- $\\mathrm{\\cdotD}_{90}\\mathrm{-}b\\mathrm{-}\\mathrm{S}_{13}$ and $\\mathrm{C}{\\cdot}\\mathrm{D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ samples exhibited smooth coating surfaces. Their root mean square roughness $(R_{\\mathrm{q}})$ values were estimated at ca. 0.6, 0.8, 0.5 and $1.0\\mathrm{nm}$ , respectively. It was proved that an integrated film structure was successfully cross-linked by polymerization of EGDMA, endowing the SIPN coatings with preferable surface morphology.  \n\n![](images/c79a2515a1b5beec3d272085d88a553e15317a8d2e4a204d42f2e40a0dca1a3d.jpg)  \nFigure 3. AFM images over a scope of $10\\upmu\\mathrm{m}\\times10\\upmu\\mathrm{m}$ of the SIPN coatings containing POSS$\\mathrm{D}_{50}–b–\\mathrm{S}_{7}$ (a), POSS- ${\\bf\\cdot D}_{70}$ -b-S10 (b), POSS- $\\mathrm{D}_{90}–b–\\mathrm{S}_{13}$ (c) and $\\mathrm{D}_{50}–b–\\mathrm{S}_{7}$ (d).  \n\nSurface compositions of the SIPN coatings were measured by XPS. All the element percentages on the coating surfaces, i.e., C, N, O, S and Si are shown in Table 2. The theoretical bulk contents of Si element, calculated from the molecular weight of the copolymers and the SIPN coating compositions, are also introduced in Table 2. It can be seen that the surface Si amounts of the amphiphilic SIPN coatings containing POSS-PDMAEMA- $b$ -PSBMA copolymers detected by XPS were all higher than those of their bulk Si contents, respectively. It was suggested that POSS groups could possibly aggregate on the coating surfaces due to their low surface energy and endowed the SIPN surfaces with the hydrophobic property.24-26 ATR-FTIR spectra were also applied in order to analyze and confirm the chemical structure of the SIPN coatings containing $\\mathrm{POSS-D}_{50}–b–\\mathrm{S}_{7}$ , POSS- $\\mathrm{\\cdotD}_{70^{-}}b{-}\\mathrm{S}_{10}$ , $\\mathrm{POSS-D}_{90}–b.\\backslash$ and $\\mathrm{D}_{50}–b–\\mathrm{S}_{7}$ block copolymers, as shown in the Supporting Information Figure S7.  \n\nTable 2. Surface elemental atomic percentages of the SIPN coatings detected by XPS   \n\n\n<html><body><table><tr><td rowspan=\"2\">Sample</td><td>C1s</td><td>O1s</td><td>N1s</td><td>S 2p</td><td>Si 2p</td><td>Bulk Si</td></tr><tr><td>(atomic%)</td><td>(atomic%)</td><td>(atomic%)</td><td>(atomic%)</td><td>(atomic%)</td><td>(atomic%)</td></tr><tr><td>C-POSS-D50-b-S7</td><td>72.3</td><td>20.3</td><td>3.7</td><td>0.7</td><td>3.1</td><td>1.21</td></tr><tr><td>C-POSS-D7o-b-S10</td><td>72.9</td><td>19.9</td><td>3.6</td><td>1.2</td><td>2.5</td><td>0.82</td></tr><tr><td>C-POSS-D90-b-S13</td><td>70.2</td><td>21.2</td><td>3.5</td><td>0.9</td><td>4.2</td><td>0.58</td></tr><tr><td>C-D50-b-S7</td><td>79.1</td><td>17.9</td><td>2.3</td><td>0.5</td><td></td><td></td></tr></table></body></html>  \n\nIn order to further examine the morphology of aggregated POSS clusters in the SIPN coatings, the samples prepared by dropping a droplet of dilute copolymer solutions (1 wt% in trifluoroethanol) on copper grids and UV-curing were observed under a transmission electron microscope (TEM). As shown in the Supporting Information Figure S8, it can be found that the aggregated POSS clusters were well dispersed within the polymer matrix in the size of $10{\\sim}80~\\mathrm{nm}$ , coincided with the reference.37 The size of POSS aggregates tended to decrease with the increase of the relative molecular weight of POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA due to the relative reduction of the POSS proportion in the copolymers. In fact, the size (less than $100\\ \\mathrm{nm},$ ) of the POSS clusters was far smaller than the wavelength of visible light, and hence, the optical properties exhibited trivial discrepancy between samples with and without POSS. Besides, the discrete POSS clusters on the coating surfaces would not affect the absorption of water molecules into the hygroscopic polymers, and play an important role in regulating and controlling the dispersion of water molecules in the coatings. The POSS clusters could be analogous to the outmost layer of hollow silica nanoparticles for antifogging and antireflective thin films as Zhang reported.38 Therefore, the surface structure of $\\mathrm{C}{\\cdot}\\mathrm{D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ coating lack of the POSS function was different from that of the coatings containing POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA copolymers, exhibiting a little lower transmittance (Figure 2B) than the latter.  \n\nWettability of the SIPN Coatings.  Changes of the water contact angle (CA) values of the SIPN coatings with time were recorded carefully under ambient conditions for $150~\\mathrm{s}.$ . As shown in Figure 4A, all C-POSS $\\mathrm{\\cdotD}_{50}–b–\\mathrm{S}_{7}$ , C-POSS- $\\cdot\\mathrm{D}_{70}{-}b{-}\\mathrm{S}_{10}$ and C-POSS- $\\cdot\\mathrm{D}_{90}–b\\ –\\mathrm{S}_{13}$ coatings exhibited high initial CA values of around $105^{\\circ}$ , while the initial CA value of the $\\mathrm{C}{\\cdot}\\mathrm{D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ coating was about $60^{\\circ}$ . The results were coincided with the recent findings in the references that an effective antifogging coating could not be superhydrophilic.3,8-10 Particularly, the C-POSS$\\mathrm{D}_{90}–b–\\ensuremath{\\mathrm{S}}_{13}$ coating had a higher initial CA value $(105.8{\\pm}0.4^{\\circ})$ , followed by a rapid decrease to $43.3{\\pm}1.3^{\\circ}$ in 60 s and $31.4{\\pm}0.7^{\\circ}$ in $150\\mathrm{~s~}$ , which was mainly attributed to the discrete POSS clusters on the coating surface and water-absorbing polymer chains inside. During the measurement, the water CA values on all SIPN surfaces decreased rapidly in 30 s, similar to the situation of the coatings containing strongly hydrophilic polymers such as poly(vinyl alcohol)/poly(acrylic acid) and chitosan/carboxymethyl cellulose as Cohen et al. reported.4,8 The water CA value on all SIPN coatings decreased much more quickly at the early time due to water dispersion than water evaporation. It was suggested that water molecules could diffuse well into the SIPN coatings in a short time, similar to the results in the reference.8  \n\nIn order to further analyze the wettability of the SIPN coatings, the diameter development of the water droplets on the coating surfaces was also calculated as shown in Figure 4B. It can be seen that the diameter of the droplet on the bare glass was almost constant during the measurement period, while the diameter of the water droplet on the $\\mathrm{C}{\\cdot}\\mathrm{D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ coating increased by about $35\\%$ . However, the variation of the droplet diameters on the C-POSS- ${\\bf\\cdot D}_{50}$ -b-S7, C$\\mathrm{POSS-D}_{70}–b–\\mathrm{S}_{10}$ and $\\mathrm{C-POSS-D_{90}-}b{\\mathrm{-}}\\mathrm{S}_{13}$ coatings increased by $70\\%$ , $73\\%$ and $84\\%$ , respectively, demonstrating that the water droplets were fast spread on the coating surfaces containing the POSS related copolymers and well dispersed into the coatings. Moreover, the larger the polymer molecular weight was, the faster the water droplet spread. The C-POSS- $\\mathrm{\\DeltaD}_{90}–b–\\mathrm{S}_{13}$ with the highest molecular weight $(2.02\\times10^{4})$ of the block copolymer exhibited the fastest absorbed water process, whereas the SIPN coatings containing POSS- $\\mathrm{\\cdotD}_{50^{-}}b{-}\\mathrm{S}_{7}$ (with a molecular weight of ${0.97\\times10}^{4}$ ) and $\\mathrm{POSS-D}_{70}–b–\\mathrm{S}_{10}$ (with a molecular weight of $1.43\\times10^{4}$ ) demonstrated similar water-dispersion speeds. Thus, the enhanced antifogging property could be caused by the strong hydrophilic blocks embedded in cross-linked PEGDMA network and the hydrophobic POSS groups on the coating surfaces.  \n\n![](images/e65e6a7dfd16a4e4c6a16e31e1b739670499cd9151ea7c52c9ec3810a6499979.jpg)  \nFigure 4. Variation of the water contact angle (CA) values on the different SIPN coatings with  \n\ntime in 150 s (A), and the diameter evolution $(\\triangle D/D_{0})$ of the droplets on the coating surfaces during the recording period (B), where $\\triangle D{=}D{-}D_{0},{\\cal I}$ $D_{0}$ is the original diameter $\\scriptstyle(t=0\\ s)$ and $D$ is the diameter of the water droplet on the coating surface at a given time.  \n\nAnti-icing Properties.  The freezing delay time of water droplets on the SIPN coatings was recorded at $-15~^{\\circ}\\mathrm{C}$ to evaluate the anti-icing properties. As shown in Figure 5, it can be observed that the SIPN coating containing $\\mathrm{D}_{50}–b–\\mathrm{S}_{7}$ showed a short freezing delay time of $10\\mathrm{~s~}$ , i.e. the water droplet became ice as quickly as it was on the bare glass. In contrast, all the three coatings containing the POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA block copolymers presented a freezing delay time of more than $124{\\mathrm{~s~}}$ , much longer than that of the $\\mathrm{C}{\\cdot}\\mathrm{D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ coating without POSS. Particularly, the C-POSS- $\\mathrm{\\cdotD}_{50^{-}}b{-}\\mathrm{S}_{7}$ coating exhibited a longer freezing delay time of 334 s than C-POSS- ${\\bf D}_{70}$ - ${b\\mathrm{-}}\\mathrm{S}_{10}$ and C-POSS- $\\mathrm{.D}_{90}$ -b-S13 with similar freezing delay times of about 124 s. This phenomenon could be attributed to the following reasons. Firstly, POSS groups with low surface free energy have the ability of improving the surface icephobicity as shown in POSS-containing methacrylate coatings.24,25,39 Secondly, a certain amount of water molecules could be interacted with the hydrophilic PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA copolymers inside the cross-linked coatings as nonfreezable bond water through hydrogen bonds,8-10,28 and the freezing point of water could be decreased by the zwitterionic groups of PSBMA in the coatings.21 Finally, the POSSPDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA coating surfaces, that were comprised of hydrophobic POSS groups on the coating surfaces and hydrophilic components in the SIPN coatings, could motivate the formation of a self-lubricating aqueous layer,11,13,14 and subsequently endow the coatings with the anti-icing properties. In other words, the POSS clusters on the C-POSS- $\\mathrm{\\cdotD}_{50^{-}}b{-}\\mathrm{S}_{7}$ coating surface could give rise to a hydrophobic surface, whereas the hygroscopic PDMAEMA and PSBMA chains were well distributed beneath them. And then, a self-lubricating aqueous layer could form when the coating absorbed water molecules.13,16 The surface structure of the coating is similar with the self-lubricating water layer fabricated by cross-linked hygroscopic polymers inside the micropores of silicon wafer surfaces as Chen et. al. put forward.13 However, the hydrophilic $\\mathrm{C}{\\cdot}\\mathrm{D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ coating surface without hydrophobic components could be a reservoir of water molecules rather than generation of a self-lubricating aqueous layer.13,16  \n\n![](images/e642027f9b8e418f468c0f2f69c24488ab8b9e09830de8da08d9c1a6a4afbc86.jpg)  \n\nFigure 5. Optical images of the water droplets on the bare glass slide and the SIPN coatings containing $\\mathrm{POSS-D}_{50^{-}}b.$ , POSS- $\\mathrm{\\cdotD}_{70^{-}}b{-}\\mathrm{S}_{10}$ , POSS- $\\mathrm{\\cdotD}_{90}\\mathrm{-}b\\mathrm{-}\\mathrm{S}_{13}$ , and $\\mathrm{D}_{50^{-}}b{-}\\mathrm{S}_{7}$ during freezing process. The freezing delay time $(T_{\\mathrm{D}})$ of each sample was observed. The temperature of the coolplate was controlled at $-15^{\\circ}\\mathrm{C}$ .  \n\nIn fact, there were water molecules in the amphiphilic coatings surfaces to maintain the presence of the self-lubricating aqueous layer.11,13 The results of the freezing delay time for each sample exhibited a trend of decrease with the increase of the molecular weight of the copolymers. When the molecular weight of the copolymers was lower than a certain value, the total content of POSS aggregated on the coating surface would be higher, whereas the relative proportion of hydrophilic components dropped. The freezing process of a water droplet on the bare glass and the hydrophilic $\\mathrm{C}{\\cdot}\\mathrm{D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ coating without POSS presented much shorter delay times in about 10 s, very similar to the case of the general polyacrylate coating.40 With the contribution of POSS, the C-POSS- ${\\bf\\delta D}_{50}$ -b-S7, C-POSS- $\\cdot\\mathrm{D}_{70}{-}b{-}\\mathrm{S}_{10}$ and C-POSS- $\\mathrm{\\cdotD}_{90}\\mathrm{-}b\\mathrm{-}\\mathrm{S}_{13}$ coatings exhibited the freezing delay times of more than $2~\\mathrm{min}$ . It could be suggested that POSS groups played an important role in regulating and controlling superior hydrophobic/hydrophilic balance of the coating surface to form a self-lubricating aqueous layer with anti-icing performance.  \n\nTherefore, C-POSS- $\\cdot\\mathrm{D}_{50}{-}b{-}\\mathrm{S}_{7}$ coating, which has the lowest content of hydrophilic units, exhibited the longest freezing delay time, whereas $\\mathrm{C}{\\cdot}\\mathrm{D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ could only prevent water from freezing in a short time.  \n\nNon-freezable Bond Water Amount in the SIPN Coatings.  In order to further understand the antifogging/anti-icing properties of the SIPN coatings, the amounts of bond water, nonfreezable bond water and freezable water in the coatings were analyzed by DSC. Figure 6 shows the DSC thermograms of the samples with the similar water content ( $\\cdot W_{\\mathrm{c}}{\\approx}1.22)$ in the heating process at a rate of $10~\\mathrm{{^{\\circ}C/m i n}}$ , whereas the results of sample C-POSS- $\\mathrm{\\cdotD}_{90}\\mathrm{-}b\\mathrm{-}\\mathrm{S}_{13}$ with different water contents and the pure deionized water were also included. It can be seen that most of the melting peaks in the heating scans of the samples could be fitted into two peaks, a smaller one at around ${\\bf-}20{\\bf-}17\\ ^{\\circ}{\\bf C}$ and a sharp one at ${\\boldsymbol{-8}}{\\boldsymbol{\\sim}}0^{\\circ}\\mathrm{C}$ close to the melting point of pure deionized water. The smaller and the sharp peaks could correspond to the melting enthalpies of freezable bond water $(W_{\\mathrm{fb}})$ and freezable free water $(W_{\\mathrm{ff}})$ , respectively, depending on the different endothermic states in the melting process.29,30 By quantitatively comparing the water contents in different states, we could verify the existence of the non-freezable bond water in the SIPN coatings.29-33  \n\nTable 3 summarizes the water contents in different states determined by DSC. In the C-POSS$\\mathrm{D}_{50}–b–\\mathrm{S}_{7}$ , C-POSS- ${\\bf\\cdot D}_{70}$ -b-S10, C-POSS- $\\mathrm{\\cdotD}_{90}\\mathrm{-}b\\mathrm{-}\\mathrm{S}_{13}$ and $\\mathrm{C-D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ coating/water binary systems, when the total water content $W_{\\mathrm{c}}{\\approx}1.22$ , the measured non-freezable bond water contents $(W_{\\mathrm{nfb}})$ were 0.45, 0.43, 0.45 and $0.52~\\mathrm{mg/mg}$ , respectively, showing similar non-freezable bond water contents in all the SIPN coatings. In addition, the total bond water contents exhibited the similar results about $0.59{\\mathrm{-}}0.61~\\mathrm{mg/mg}$ , indicating that all the SIPN coatings with or without POSS may have the similar situation of polymer-water interactions at a molecular level via hydrogen bonds.28-33  \n\n![](images/a24771f91220144748cbf3e0146808c9bdd346a6743a2314daf7dcbbb43fd509.jpg)  \nFigure 6. DSC heating curves of the SIPN coatings with a total water content $(W_{\\mathrm{c}})$ of approximate 1.22, and the sample C-POSS- ${\\bf\\cdot D}_{90}$ - $b{\\mathrm{-}}\\mathrm{S}_{13}$ with different water contents at a heating rate of $10~{^\\circ}\\mathrm{C}/\\mathrm{min}$ . The DSC heating scan of pure deionized water was also added as control.  \n\nAdditionally, DSC heating curves of C-POSS- $\\mathrm{\\cdotD}_{90}\\mathrm{-}b\\mathrm{-}\\mathrm{S}_{13}$ with different water contents were specially shown in Figure 6. We selected four $W_{\\mathrm{c}}$ values, which are 1.22, 0.83, 0.53 and 0.26 $\\mathrm{{mg/mg}}$ , for comparison. It can be seen that as the water content decreased, the melting points of the free water as well as all the contents of water in different states tended to reduce (Table 3). It was noticed that when $W_{\\mathrm{c}}{=}0.26$ , only one melting peak was detectable in the DSC heating curve, and it was difficult to distinguish the different states of water in this case. It was assumed that the smaller amount of water in the sample could possibly appear only in the state of freezable water because the melting peak was close to the melting peak $T_{\\mathrm{ffm}}$ values $\\mathrm{-}7{\\sim}\\mathrm{-}3^{\\circ}\\mathrm{C}$ of other samples, and higher than the $T_{\\mathrm{fbm}}$ values about ${\\bf-17}\\mathrm{\\sim}{\\bf-14}^{\\circ}\\mathrm{C}$ (Table 3).  \n\nTable 3. Different water contents in the SIPN coatings analyzed by DSC   \n\n\n<html><body><table><tr><td rowspan=\"4\">Sample</td><td rowspan=\"4\">W. (mg/mg)</td><td colspan=\"6\">Freezable water</td><td>Bond</td></tr><tr><td>Wf</td><td colspan=\"2\">Freezable bond water</td><td colspan=\"2\">Freezable Free water</td><td>Non-freezable bond water</td><td>water</td></tr><tr><td>(mg/mg)</td><td>Wfb</td><td>Tfbm</td><td>Wff</td><td>Tffim</td><td>Wnfb (mg/mg)</td><td>Wb</td></tr><tr><td></td><td>(mg/mg)</td><td>(C)</td><td>(mg/mg)</td><td>(℃)</td><td></td><td>(mg/mg)</td></tr><tr><td>C-POSS-D50-b-S7</td><td>1.21</td><td>0.76</td><td>0.14</td><td>-14.01</td><td>0.62</td><td>-1.30</td><td>0.45</td><td>0.59</td></tr><tr><td>C-POSS-D70-b-S10</td><td>1.20</td><td>0.77</td><td>0.16</td><td>-17.42</td><td>0.61</td><td>-1.91</td><td>0.43</td><td>0.59</td></tr><tr><td>C-POSS-D90-b-S13</td><td>1.22</td><td>0.77</td><td>0.14</td><td>-15.01</td><td>0.63</td><td>-1.50</td><td>0.45</td><td>0.59</td></tr><tr><td rowspan=\"4\">C-D5o-b-S7</td><td>0.83</td><td>0.61</td><td>0.15</td><td>-16.14</td><td>0.46</td><td>-3.35</td><td>0.22</td><td>0.37</td></tr><tr><td>0.53</td><td>0.39</td><td>0.10</td><td>-16.79</td><td>0.29</td><td>-7.38</td><td>0.14</td><td>0.24</td></tr><tr><td>0.26</td><td>0.26</td><td></td><td></td><td>0.26</td><td>-8.76</td><td></td><td></td></tr><tr><td>1.24</td><td>0.72</td><td>0.09</td><td>-16.34</td><td>0.63</td><td>-2.13</td><td>0.52</td><td>0.61</td></tr></table></body></html>  \n\nA sufficient amount of the non-freezable bond water in the SIPN coatings played an important role for the excellent antifogging/anti-icing properties. In fact, the non-freezable bond water formed by the polymer-water interactions via hydrogen bonds may vary with hydrophilic polar groups and hydrophobic nonpolar groups.41 Therefore, the similar non-freezable bond water contents in all the SIPN coatings was dominated by the polymeric structure, especially the hydrophilic components. In fact, the C-POSS- $\\mathrm{\\cdotD}_{50}{\\mathrm{-}}b{\\mathrm{-}}\\mathrm{S}_{7}$ , C-POSS- $\\mathrm{\\cdotD}_{70}$ -b-S10, C-POSS- ${\\bf\\cdot D}_{90}$ -b-S13 and $\\mathrm{C}{\\cdot}\\mathrm{D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ coatings exhibited quite close non-freezable bond water contents even when detected at different heating rates of 5, 10 or $15~\\mathrm{{^{\\circ}C/m i n}}$ as shown in the Supporting Information Table S1. The different heating rates exerted no significant influence on non-freezable bond water contents, suggesting well absorption of water in all the SIPN coatings with or without POSS. Containing similar non-freezable water contents, the SIPN coating with or without POSS demonstrated different antifogging/anti-icing properties, further confirming the important role of POSS on the coating surface.  \n\n![](images/dd81f57c65c0efae99bf125b811bd9cff024ebafc4931184b217744ee92be52f.jpg)  \nFigure 7. Illustration of amphiphilic SIPN coatings containing POSS-PDMAEMA- $b$ -PSBMA  \n\n(A) and PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA (B) with cross-linked PEGDMA network. Hydrophobic POSS aggregated on the surface and strongly hydrophilic chains distributed beneath them endowed the amphiphilic SIPN coatings with excellent antifogging/anti-icing performances in comparison with the hydrophilic SIPN coating.  \n\nThe SIPN coatings, which contained POSS-PDMAEMA- $b$ -PSBMA and were comprised of both low surface energy and hydrophilic blocks, endowed the surfaces with the optimum antifogging/anti-icing performances. As illustrated in Figure 7, hydrophobic POSS clusters aggregated on the coating surfaces featured the amphiphilic surface of the SIPN coatings containing POSS-PDMAEMA- $b$ -PSBMA block copolymers. The hygroscopic polymeric components of the coatings manipulated water molecules to well disperse into the hydrophilic matrix via hydrogen bonded interactions. Based on the POSS clusters and the self-lubricating aqueous layer formed by the non-freezable bond water on the surface, the amphiphilic SIPN coating containing POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA block copolymers exhibited excellent antifogging/anti-icing performances over the hydrophilic SIPN coating without POSS.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# CONCLUSIONS  \n\nIn this work, we developed an amphiphilic SIPN coating containing block copolymers of POSS-PDMAEMA- $b$ -PSBMA with cross-linked PEGDMA network. The obtained SIPN coatings that were comprised of both low surface energy and hydrophilic components endowed the coatings with optimal antifogging/anti-icing performances. The excellent antifogging properties were originated primarily from the hygroscopicity of PDMAEMA and PSBMA blocks embedded in cross-linked PEGDMA network, as well as the hydrophobic POSS aggregated on the surface. The amphiphilic SIPN coatings with POSS groups had excellent transparency due to rapid water-absorption in the coatings. PDMAEMA with LCST and PSBMA with UCST facilitated the dispersion of water molecules to enhance the antifogging behaviors. Also, a selflubricating aqueous layer formed by non-freezable bond water at the surface endowed the amphiphilic SIPN coatings with great anti-icing performance which had a freezing delay time of more than $2~\\mathrm{min}$ . The amphiphilic antifogging/anti-icing coatings combining POSS and PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA would contribute to novel potential applications in the future, such as transparent substrates in airplanes and lenses in medical instruments.",
+        "category": " Conclusions"
+    },
+    {
+        "id": 8,
+        "chunk": "# ASSOCIATED CONTENT",
+        "category": " References"
+    },
+    {
+        "id": 9,
+        "chunk": "# Supporting Information  \n\nThe Supporting Information is available including characterizations of the POSSPDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA block copolymers by $\\mathrm{^{1}H N M R}$ , FTIR spectra, GPC and TGA techniques, and the characterizations of the SIPN coatings by TEM and DSC. The “thermal remediation” pictures of the SIPN coating by a digital camera were also presented.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# AUTHOR INFORMATION",
+        "category": " References"
+    },
+    {
+        "id": 11,
+        "chunk": "# Corresponding Author  \n\n\\*E-mail: yuanxy $@$ tju.edu.cn; xyuan28@yahoo.com.",
+        "category": " References"
+    },
+    {
+        "id": 12,
+        "chunk": "# Notes  \n\nThe authors declare no competing financial interest.",
+        "category": " References"
+    },
+    {
+        "id": 13,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nThis work is financially supported by National Natural Science Foundation of China (Nos. 51603143 and 51273146).",
+        "category": " References"
+    },
+    {
+        "id": 14,
+        "chunk": "# REFERENCES  \n\n(1) Mundo, R. D.; D'Agostino, R.; Palumbo, F. Long-Lasting Antifog Plasma Modification of  \n\nTransparent Plastics. ACS Appl. Mater. Interfaces 2014, 6, 17059-17066.   \n(2) Wang, Y.; Li, T. Q.; Li, S. H.; Sun, J. Q. Antifogging and Frost-Resisting Polyelectrolyte Coatings Capable of Healing Scratches and Restoring Transparency. Chem. Mater. 2015, 27, 8058-8065.   \n(3) Li, Y. X.; Fang, X.; Wang, Y.; Ma, B. H.; Sun, J. Q. Highly Transparent and WaterEnabled Healable Antifogging and Frost-resisting Films Based on Poly(vinyl alcohol)-Nafion Complexes. Chem. Mater. 2016, 28, 6975-6984.   \n(4) Lee, H.; Alcaraz, M. L.; Rubner, M. F.; Cohen, R. E. Zwitter-Wettability and Antifogging Coatings with Frost-Resisting Capabilities. ACS Nano 2013, 7, 2172-2183.   \n(5) Zhang, J. L.; Severtson, S. J. Fabrication and Use of Artificial Superhydrophilic Surfaces. J. Adhes. Sci. Technol. 2014, 28, 751-768.   \n(6) Lai, Y. K.; Tang, Y. X.; Gong, J. J.; Gong, D. 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Hydrogen-Bonding-Supported Self-Healing Antifogging Thin   \nFilms. Sci. Rep. 2015, 5, 9227. (37) Ullah, A.; Ullah, S.; Khan, G. S.; Shah, G. M.; Hussain, Z.; Muhammad, S.; Siddiq, M.;   \nHussain, H. Water Soluble Polyhedral Oligomeric Silsesquioxane Based Amphiphilic Hybrid   \nPolymers: Synthesis, Self-Assembly, and Applications. Eur. Polym. J. 2016, 75, 67-92. (38) Zhang, X. J.; He, J. H. Antifogging Antireflective Thin Films: Does the Antifogging   \nLayer Have to Be the Outmost Layer? Chem. Commun. 2015, 51, 12661-12664. (39) Meuler, A. J.; Smith, J. D.; Varanasi, K. K.; Mabry, J. M.; McKinley, G. H.; Cohen. R. E.   \nRelationships between Water Wettability and Ice Adhesion. ACS Appl. Mater. Interfaces 2010, 2,   \n3100-3110. (40) Li, X. H.; Zhao, Y. H.; Li, H.; Yuan, X. Y. Preparation and Icephobic Properties of   \nPolymethyltrifluoropropylsiloxane-Polyacrylate Block Copolymers. Appl. Surf. Sci. 2014, 316:   \n222-231. (41) Varma-Nair, M.; Costello, C. A.; Colle, K. S.; King, H. E. Thermal Analysis of Polymer  \nWater Interactions and Their Relation to Gas Hydrate Inhibition. J. Appl. Polym. Sci. 2007, 103,   \n2642-2653.  \n\n![](images/03ab1750fc3af80ba2b525d4ce0b8f06566f635c81f87b745ad003ec353f58a3.jpg)  \nTable of Contents Graphic",
+        "category": " References"
+    }
+]
\ No newline at end of file
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@@ -0,0 +1,492 @@
+[
+    {
+        "id": 1,
+        "chunk": "# 鼻内镜防雾材料研制及防雾机理探讨 Development Antifogging Agent of Nasal Endoscope and to Explore its Mechanism  \n\n课题来源：新型纳米防雾光学材料的研发，国家高技术研究发展计划（863计划）专题（项目批准号：2007AA021907）  \n\n学位申请人 万良财导师姓名 谢民强专业名称 耳鼻咽喉科学培养类型 委托培养培养层次 博士研究生所在学院 第二临床医学院  \n\n2013年3月31日广州",
+        "category": " Introduction"
+    },
+    {
+        "id": 2,
+        "chunk": "# 鼻内镜防雾剂研制及其防雾机理探讨  \n\n博士研究生：万良财  \n\n指导教师：谢民强教授",
+        "category": " Abstract"
+    },
+    {
+        "id": 3,
+        "chunk": "# 摘要  \n\n研究背景和目的 玻璃、石英、塑料等透明材料在日常生活、工农业及医疗方面有着广泛的用途，如镜子、各种医用内镜镜头、汽车挡风玻璃及农用塑料薄膜，此类材料的应用使我们的生活变得更加便利。但在湿度大或气温较低时这些材料表面容易水汽凝结而起雾影响其透光率或能见度，使其应用受到较大影响。医疗上各种医用内窥镜镜头手术时需反复擦试镜头来保证其清晰度而延长了手术时间，内镜防雾问题已越来越受到学者的关注。鼻内窥镜手术目前已在全国各级医院广泛开展，鼻内镜技术虽日益成熟，但鼻内镜手术并发症尤其是严重并发症仍时有发生，其原因之一是术腔出血，镜面模糊，视野不清所致。临床上大多使用医用碘伏、医用酒精、热水或肥皂液来防雾，但这些材料存在防雾时间短、易烫伤鼻粘膜、刺激性大等缺点，内镜防雾问题实际上仍然没有得到很好地解决。工农业上虽有不少防雾材料的报道，此类防雾材料大多仅要求其有较好的防雾性能，而对其毒性、气味要求较低，但作为临床应用的防雾材料务必要求无毒、无味、刺激性小，因此工农业报导的防雾材料并不适合于临床应用。迄今为止，国内外有关鼻内窥镜防雾材料的研究报道很少，寻求无毒、生物相容性好的防雾剂是与临床密切相关的研究课题。  \n\n目前防雾的途径通常包括：第一：使材料表面亲水，降低其表面能，因亲水材料带有大量亲水基团，可以吸引水分子，雾滴在材料表面可迅速铺展开形成一层水膜减少对光的漫反射而达到防雾目的。亲水性防雾材料通常包括：小分子表面活性剂型防雾剂、有机高分子亲水性防雾涂料、有机/无机杂化亲水性防雾涂料、氧化物、光催化超亲水表面、碳纳米管材料。第二：与亲水材料相反，使材料表面疏水，因疏水材料不能被水浸润，雾滴在材料表面容易滚动，理论上可以达到防雾效果。由于超疏水材料在基础领域及实际应用中具有较大的潜能，超疏水引起了材料学者的广泛兴趣，通常制备方法包括：溶胶-凝胶法、相分离技术、化学气相沉积法(CVD)、刻蚀法、静电纺丝技术、碳纳米管材料及超亲水与超疏水相互转化材料等，其中溶胶-凝胶法是最常用的方法。第三：使材料表面温度高于露点温度，因水汽不能在内镜表面凝结而达到防雾的目的。  \n\n超亲水、超疏水材料理论上可用于鼻内镜防雾，但其在实际应用中却面临以下一系列问题：超亲水材料因雾滴在其表面易形成一层水膜而迅速铺展开来减少光的漫反射而达到防雾的目的，而防雾剂型的液态亲水材料与固体表面通常靠物理吸附即主要靠范德华力结合，因粘附力弱结合不牢固防雾剂容易从固体表面流失而影响其防雾性能。超疏水材料因其表面需要构建粗糙的结构才能达到疏水的状态，且疏水能力与材料表面的粗糙度呈正相关，即材料表面越粗糙其疏水性能就越好，水滴在材料表面的接触角达到180度的理想状态时才能在材料表面自由滚动。但这又带来一个新的问题，即疏水性越好其表面粗糙度就越高，而粗糙度越高其透光率就越差，势必会影响其在光学方面的应用。  \n\n目的：采用表面活性剂、溶剂、分散剂等，通过正交设计，研制一种无刺激性，防雾时间长、镜面清晰度高、经济安全、使用方便的亲水型鼻内镜手术防雾剂；探讨在防雾剂中添加一定质量百分比的不同性质纳米粒子后防雾剂的表面能极性比、防雾剂与鼻内镜镜面的粘附力及防雾时间的变化；同时制备超疏水材料，并对其防雾性能进行初步探讨。",
+        "category": " Abstract"
+    },
+    {
+        "id": 4,
+        "chunk": "# 方法：  \n\n一：亲水型防雾剂制备：表面活性剂、溶剂、分散剂等按一定的配比混合，每种物质重量百分比设有3个水平，本实验采用正交设计，共安排27次试验，使用SPSS13.0进行数据分析。依次将无水乙醇、丙二醇、月桂醇聚氧乙烯醚、十二烷基硫酸钠、聚乙二醇400，余量为去离子水，按不同质量比加入称量瓶中混合，并置于 $50^{\\circ}\\mathrm{C}$ 水浴箱15分钟后即得27种不同浓度配比的无色透明、无刺激性鼻内镜防雾剂。对这27种配方防雾剂的防雾时间及其防雾性能进行测试，通过对不同组分的均值分析得到防雾时间最长的配比，随后即按最佳配比配制防雾剂，并在同一测试环境下对同一受试者进行鼻内镜防雾测试3次，取平均值作为其防雾时间。  \n\n二：纳米粒子改性亲水型鼻内窥镜防雾剂研制：分别取纳米 $\\mathbf{SiO}_{2}0.05$ 克和纳米 $\\mathrm{\\bfSiO}_{2}$ -KH5700.05克加入亲水性鼻内镜防雾剂 $\\mathfrak{s m}$ 中，超声分散30分钟即得两种不同的改性鼻内镜防雾剂。  \n\n三：纳米粒子改性聚乙烯吡咯烷酮（PVP）鼻内窥镜防雾剂研制：将0.05克纳米氧化锌加入 $5\\mathrm{ml}$ 聚乙烯吡咯烷酮溶液中，0.025克自制纳米二氧化钛加入$\\mathsf{5m l}$ 聚乙烯吡咯烷酮溶液中，0.05克自制纳米二氧化硅中空微球加入5ml聚乙烯吡咯烷酮溶液中，超声分散30分钟即得不同鼻内窥镜防雾剂。  \n\n四：对制备的不同防雾剂进行表征，内容包括：防雾时间（鼻内镜防雾测试）、透光率、接触角、粘附功、透射电镜及原子力显微镜观察。  \n\n五：透明超疏水薄膜防雾性能研究：采用溶胶一凝胶法制备超疏水薄膜：酸溶胶制备：将 $8.36\\mathrm{{mL}}$ 正硅酸乙酯（TEOS）加入到 $80\\mathrm{mL}$ 无水乙醇中充分溶解，在磁力搅拌器搅拌下滴加 $36\\%$ 的盐酸4.8mL到上述溶液中，继续搅拌19h。丙烯酸溶液制备：将 $3.0{\\mathrm{g}}{\\mathrm{\\Omega}}$ 纯溶性丙烯酸溶于 $50\\mathrm{mL}$ 无水乙醇中，充分搅拌至完全溶解。碱凝胶制备：将3.1mL正硅酸乙酯（TEOS）加入到 $\\mathrm{80mL}$ 无水乙醇中充分溶解，再加入13.8mL去离子水，在磁力搅拌器搅拌下逐渐滴加4.7mL分析纯氨水到上述溶液中，密封反应1小时。将不同比例的酸溶胶、丙烯酸溶液及碱凝胶加入无水乙醇中，所制备溶液超声振荡1h，制得20 种分散良好的溶胶。将清洁玻璃片浸入以上溶胶中，10s后用提拉涂膜机以3mm/s 的速度提拉出，室温下静置15min，如此反复制备涂有3层及5层的膜。将所制基片放入马弗炉中升温2h至 $400^{\\circ}\\mathrm{~C~}$ ，保温0.5h后自然降温，得到20种透明二氧化硅薄膜样品。将涂膜后的玻璃片放入硅烷偶联剂溶液中浸泡3小时，然后将样品放入 $100^{\\circ}\\mathrm{~C~}$ 烘箱干燥60min，得到透明二氧化硅薄膜。  \n\n疏水薄膜防雾测试：模拟一定温差的情况下，测试具有疏水性能的8号、13号涂膜基片、空白基片及涂硅烷偶联剂溶液基片在遇水汽时的防雾性能。在水浴锅上搭建产生水汽装置，将所制基片静置于其上，疏水二氧化硅薄膜层向水面，基片离水面 $3\\mathsf{c m}$ ，室温为 $13^{\\circ}\\mathrm{C}$ ，水浴温度设置为 $60^{\\circ}\\mathrm{C}$ 。经过5min、 $10\\mathrm{{min}}$ $20\\mathrm{min}$ 、 $30\\mathrm{min}$ 后进行对比，观察其表面起雾情况。  \n\n统计学处理（亲水型防雾剂制备正交试验）因素A：无水乙醇；因素B：丙二醇；因素C：月桂醇聚氧乙烯醚；因素D：十二烷基硫酸钠；因素E：聚乙二醇400，每种物质重量百分比设3个水平（ $a:1=3\\%$ 、 $2=10\\%$ 、 $3{=}20\\%$ ， $\\mathbf{b}:\\mathbf{1}=3$ $\\%$ 、 $2=10\\%$ 、 $3=20\\%$ ； $c:1=3\\%$ 、 $2=10\\%$ 、 $3=20\\%$ ； $d:1=0.6\\%$ 、 $2=2\\%$ 、 $3{=}4\\%$ $e:1=0.6\\%$ 、 $2=2\\%$ 、 $3=4\\%$ ）如要完全试验，需行 $3\\times3\\times3\\times3\\times3=243$ 次试验（Orthogonal），本实验采用正交设计，共安排27次试验，使用SPSS13.0进行数据分析，防雾性能测试结果统计学分析。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 5,
+        "chunk": "# 结果  \n\n一：亲水型防雾剂制备：通过正交实验,得到27种不同浓度配方的防雾剂，对这27种配方防雾剂防雾时间进行测试，通过对不同组分的均值分析得到防雾时间最长配比A3B2C3D3E3。表征不同配比防雾剂其透光率均接近 $100\\%$ ；接触角约为7.6度；扫描电镜示防雾剂在鼻内镜镜头（蓝宝石）表面形成一层平整膜；按最佳配比配制防雾剂并对同一受试者进行测试，其平均防雾时间为15分钟。表征医用碘伏其透光率约 $80\\%$ ；接触角约为10度；扫描电镜示医用碘伏涂在鼻内镜镜面后呈散在岛状分布，表面不规整，未能形成膜状结构。用鼻内镜对同一受试者在相同的环境下进行碘伏及 $95\\%$ 乙醇进行防雾测试，其平均防雾时间分别为 $04^{\\prime}05^{\\prime\\prime}$ 和 $38\"$ ，所研制的防雾剂防雾效果明显优于医用碘伏及 $95\\%$ 乙醇。  \n\n二：防雾剂及其改性剂防雾性能：纳米 $\\mathrm{\\bfSiO}_{2}$ 改性防雾剂鼻内镜防雾时间为$18\\mathrm{{min}}$ ；纳米 $\\mathbf{SiO}_{2}$ -KH570改性防雾剂防雾时间为21min。透光率:在可见光范围内防雾剂的透光率约为 $100\\%$ ；纳米 $\\mathrm{SiO}_{2}$ 改性防雾剂透光率约为 $90\\%$ ；纳米$\\mathbf{SiO}_{2}$ -KH570改性防雾剂透光率约为 $97\\%$ 。接触角：水滴在防雾剂涂膜上的接触角7.8度；水滴在纳米 $\\mathbf{SiO}_{2}$ 改性防雾剂涂膜上的接触角7.0；水滴在纳米$\\mathbf{SiO}_{2}.$ -KH570改性防雾剂涂膜上的接触角6.7度。粘附功：水在蓝宝石镜面的接触角为(56.159.958.0)平均值为58.0度；乙二醇在蓝宝石镜面的接触角为(46.351.648.2)平均值为48.7度；蓝宝石镜面的表面能为 $52.36{\\pm}\\mathrm{mN}/\\mathrm{m}$ ，其中色散分量(Disp$2.92{\\pm}\\mathbf{m}\\mathbf{N}/\\mathbf{m})$ ；极性分量 $(\\mathrm{Polar}49.44{\\pm}\\mathrm{mN}/\\mathrm{m})$ ；研制的鼻内镜防雾剂在蓝宝石镜面的粘附功为 $40.71\\mathrm{mN/m}$ ，纳米二氧化硅改性防雾剂在蓝宝石镜面的粘附功为$49.73\\mathrm{mN/m}$ ，纳米二氧化硅-KH570改性防雾剂在蓝宝石镜面的粘附功为$55.38\\mathrm{mN/m}$ 。透射电镜： $\\mathrm{SiO}_{2}$ 径粒约 $100{\\sim}200\\mathrm{nm},$ 呈球形，纳米 $\\mathbf{SiO}_{2}$ 在防雾剂中分散较差，团聚明显；改性纳米 $\\mathbf{SiO}_{2}$ -KH570在防雾剂中的分散性明显提高，基本呈单个纳米粒子分布。原子力显微镜:鼻内镜防雾剂在蓝宝石镜面形成一均匀的薄膜厚约 $192.30\\mathrm{nm}$ ，膜表面较平整；纳米 $\\mathrm{SiO}_{2}$ 改性防雾剂形成的薄膜最厚处约 $200.09\\mathrm{nm}$ ，膜表面较单纯防雾剂表面粗糙，纳米粒子粒径范围约 $100{\\sim}200\\mathrm{nm}$ 纳米 $\\mathrm{\\bfSiO}_{2}$ -KH570改性防雾剂形成的薄膜最厚处约 $332.38\\mathrm{nm}$ ，膜表面较单纯防雾剂表面粗糙。  \n\n三：PVP及其改性剂防雾性能：PVP鼻内镜防雾时间为 $10\\mathrm{{min}}$ ；纳米氧化锌改性PVP鼻内镜防雾时间为 $15\\mathrm{min}$ ；纳米氧化钛改性PVP鼻内镜防雾时间为$16\\mathrm{{min}}$ ；中空纳米二氧化硅改性PVP鼻内镜防雾时间为 $\\cdot17\\mathrm{{min}}$ 。透光率：在可见光范围内PVP透光率约为 $100\\%$ ；纳米氧化锌改性PVP透光率约为 $90\\%$ ；纳米氧化钛改性PVP透光率约为 $85\\%$ ；中空纳米二氧化硅改性PVP透光率约为 $92\\%$ 碘伏透光率约为 $80\\%$ ；纳米二氧化钛改性碘伏透光率约为 $70\\%$ 。接触角：水滴在PVP 涂膜上的接触角9.6度；水滴在纳米氧化锌改性PVP涂膜上的接触角5.9;水滴在纳米氧化钛改性PVP涂膜上的接触角4.8度；水滴在中空纳米二氧化硅改性 PVP 涂膜上的接触角 6.1 度。粘附功:PVP 在蓝宝石镜面的粘附功为$96.10\\mathrm{mN/m}$ ；纳米氧化锌改性PVP在蓝宝石镜面的粘附功为 $101.02\\mathrm{mN/m}$ ；纳米氧化钛改性PVP在蓝宝石镜面的粘附功为 $100.81\\mathrm{mN/m}.$ ：中空纳米二氧化硅改性PVP 在蓝宝石镜面的粘附功为 $102.92\\mathrm{mN/m}$ 。透射电镜：纳米氧化锌在PVP溶液中分散较好；制备的纳米氧化钛粒径约 $120{\\sim}160\\mathrm{nm}$ 在 PVP溶液中分散较好;制备的中空纳米二氧化硅粒径约 $200\\mathrm{nm},$ 在PVP溶液中分散较好。原子力显微镜：聚乙烯吡咯烷酮鼻内镜防雾剂在蓝宝石镜面形成一均匀的薄膜，最厚处约$78.30\\mathrm{nm}$ ，膜表面较平整，纳米氧化锌改性PVP形成的薄膜最厚处约 $277.97\\mathrm{nm}$ 膜表面较单纯防雾剂表面显粗糙。纳米氧化钛改性PVP 形成的薄膜最厚处约$227.34\\mathrm{nm}$ ，膜表面较单纯聚乙烯吡咯烷酮表面粗糙。中空纳米二氧化硅改性PVP形成的薄膜亦较粗糙，薄膜最厚处约 $34.64\\mathrm{nm}$ D  \n\n四：以玻璃为基底，采用溶胶凝胶法，以丙烯酸诱导正硅酸乙酯(TEOS)相分离并自组装硅烷偶联剂的方法制备的 20种涂膜中具有疏水性质的是 $_{8\\sim13}$ 号，疏水性能最好的是13号，其扫描电镜显示薄膜表面的微观结构呈弹坑状，水滴在此表面上的接触角为 $153^{\\circ}$ ，具有超疏水特性，防雾试验证明其具有一定的防雾性，在可见光区间内其透光率约为 $60\\sim80\\%$ 。  \n\n结论：所制备的亲水型鼻内镜防雾剂透明、无毒、无味，较临床常用的碘伏、酒精的防雾时间长；经纳米二氧化硅粒子改性后的亲水型鼻内镜防雾剂进一步延长了防雾时间，增强了防雾性能；纳米粒子改性聚乙烯吡咯烷酮鼻内窥镜防雾剂透明、无毒、无味，较碘伏、酒精的防雾时间明显延长；超疏水材料具有一定的防雾性能，但因其表面粗糙，透光率受影响，且材料表面很难达到接触角180度的理想状态，应用于临床鼻内镜防雾尚需进一步深入研究。  \n\n关键词：鼻内窥镜、防雾、超亲水、纳米粒子、超疏水",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# Development Antifogging Agent of Nasal Endoscope and to Explore its Mechanism  \n\nName: wanliangcai  \n\nSupervisor:professor xieminqiang",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# ABSTRACT",
+        "category": " Abstract"
+    },
+    {
+        "id": 8,
+        "chunk": "# Background:  \n\nTransparent material has wide application fields in our daily life, in industrial ,agricultural and medical aspects. the application of such materials as mirror, all kinds of medical endoscope, automobile windshield and agricultural plastic film makes our life more convenient. But the above material surface are easy to condense of water vapor , the fog affects the light transmittance or visibility which influence its application in high humidity or in lower temperature ares. In order to keep the good light transmittance or visibility, we must clean our medical endoscope lens again and again during the surgery which will prolong the operation time. Endoscopic antifogging problem has already attracted more and more attentions of scholars. Nasal endoscopic surgery has been widely developed in hospitals at all levels, nasal endoscopic technique is now becoming more mature, but the nasal endoscopic surgery complications, especially serious complications still occur from time to time, the reasons include bleeding, endoscope lens blurred or fog. Nowdays, medical betadine, alcohol, hot water or soap liquid are used to avoid the fogging clinically, but there are many disadvantages for these materials such as short antifog time, easy to burn nasal mucosa ,high irritation, the issue of clinical endoscopic antifog is not resovled up to now. Although there are lots of reports about antifog in industry and agriculture, this kind of antifogging materials only require the high quality of antifog while ingore its toxicity and irritation, so the industrial and agricultural antifog material may not be suitable for clinical application. So far, clinical endoscopic antifog material is rarely reported in literature. Developping a kind of non-toxic, biological compatibility and high quality endoscopic antifog material is closely related with the clinical research.  \n\nUsually antifog methods includes the following ways: first of all: make the material surface hydrophilic and reduce its surface energy, the hydrophilic material contains a large number of hydrophilic group which can attract water molecules,so the droplet in material surface can rapidly spread expands to form a layer of water film which reduce light of diffuse and achieve the purpose of antifog.hydrophilic materials includes: small molecule surfactant, organic polymer hydrophilic antifog coating, organic/inorganic hybrid hydrophilic antifog coating, oxide, photocatalysis hydrophilic surface, carbon nanotube materials. Secondly: contrast to the hydrophilic material, make the material surface hydrophobic, because hydrophobic material cannot be infiltrated by water droplets in its surface and water droplets can roll easily, so the hydrophobic material can avoid fogging theoretically, but the research reports about hydrophobic material antifog are rare. because superhydrophobic material has great potential in the basic fields and practical application , scholars become deeply interested in superhydrophobic material, methods of superhydrophobic material includ: sol - gel method, phase separation, chemical vapor deposition (CVD), etching method, electrostatic spinning technology, carbon nano tube, reciprocal transformation materials between superhydrophilic and superhydrophobic materials, the most commonly used methods is sol-gel method. Thirdly: increase temperature of the material surface and water vapor can't condensate in endoscope surface and can  \n\nachieve the purpose of antifog  \n\nWhen the superhydrophilic and superhydrophobic material are applied in nasal endoscopic antifog ,they will face the following problems: droplets in the super hydrophilic material surface can form a layer of water film easily and unfold rapidly which can reduce light of diffuse and achieve the purpose of antifog, but the adhension between the liquid hydrophilic material of antifog dosage form and solid surface usually is mainly by physical adsorption ,that is , by van der Waals force, the adhesive force is weak and unstable, the liquid hydrophilic antifog material can lose easily from the solid surface which can decrease the antifogging performance of the liquid hydrophilic material. To the superhydrophobic material, a rough structure should be built of its surface to achieve the hydrophobic state, and there is a positive correlation between hydrophobic ability and the material surface roughness,that is, the rougher of the material surface is , the better of hydrophobic performance is. Only when the material surface contact angle is about 180degrees can the water droplets on the material roll freely , however, it is a ideal state.it also brings a new problem, that is, the better the hydrophobic surface is , the rougher of its surface is , which can influence the transmissivity of hydrophobic material and its applications.",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# Objective:  \n\nThe study will develop a kind of antifogging agent for endoscopic sinus surgery with surfactant, solvent, dispersant, etc by orthogonal test, the antifoggant should be colorless, non-irritating, long antifog time, good transmissivity, economic ,security and much easier to manufacture; to explore the changes of surface energy polarity ratio、adhesion between antifoggant and nasal endoscope lens、 anti-fog time by modified antifoggant with different nanoparticles; in addition, to makes a preliminary discussion whether the superhydrophobic material has the function of antifog or not.",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# Methods and materials  \n\nAccording to certain proportion,the hydrophilic antifogging agent was made by surfactant, solvent, dispersant, etc, each material weight percentage has three level, using design of orthogonal test. $\\mathrm{L}27(3^{5})$ of experiments were arranged by SPSS13.0. nasal endoscopy anti-fogging agent were made by adding the ethanol (A), propylene glycol (B), polyoxyethylene lauryl ether (C), sodium dodecyl sulfate (D), polyethylene glycol 40o (E) and deionized water to weighing bottles and mixed According to the order of A、 B 、C、D、 E, then the weighing botles were placed $50\\ \\mathrm{^{\\circ}C}$ water bath for 15 minutes. Each substance has three levels percentage of the total mass (A: $1=3\\%$ 。 $2=10\\%$ ， $3=20\\%$ ; B: $1=3\\%$ $2=10\\%$ 。 $3=20\\%$ ; C: $1=3\\%$ $2=10\\%$ 。 $3=20\\%$ ; D: $1=0.6\\%$ $2=2\\%$ 。 $3=4\\%$ E: $1=0.6\\%,2=2\\%,3=4\\%)$ orthogonal test was designed by SPSS13.0.27 kinds of nasal endoscopy antifogging agents were obtained by the different ratio ,which are colorless, transparent, non-irritating, the $\\mathfrak{p H}$ value is about $\\mathbf{7}{\\sim}{\\mathbf{8}}.$ In accordance with the way of endoscopic surgery, Storz0 nasal endoscopy and its imaging system were used to test the antifogging time of the 27 agents ,each agent was tested 3 times, and the average is antifogging time, while the medical betadine, $95\\%$ ethanol were also tested as control.  \n\nDevelopping a nanoparticles modified hydrophilic antifogging agent of nasal endoscope: adding $0.05\\textbf{g}$ nanoparticles of $\\mathrm{\\bfSiO}_{2}$ into 5ml hydrophilic antifogging agent of nasal endoscope and adding $\\mathbf{0.05\\g}$ nanoparticles of nano sioz-KH570 into 5 ml hydrophilic antifogging agent of nasal endoscope. Then two kinds of nanoparticles modified hydrophilic antifogging agent were made by ultrasonic dispersion for 30 minutes.  \n\nDevelopping a nanoparticles modified polyvinyl pyrrolidone antifogging agent of nasal endoscope: adding $\\mathbf{0.05\\:g}$ of nano zno into $5\\mathrm{ml}$ polyvinylpyrrolidone solution, adding $\\mathbf{0.025g}$ of nano titanium dioxide into $\\mathsf{5m l}$ polyvinyl pyrrolidone solution, adding $\\mathbf{0.05g}$ of hollow microspheres nano silica into $\\mathsf{5m l}$ polyvinylpyrrolidone solution, Then three kinds of nanoparticles modified polyvinyl pyrrolidone antifogging agent were made by ultrasonic dispersion for 30 minutes.  \n\nDifferent antifogging agent were characterized and the content includes: light transmittance, contact angle, antifog time (nasal endoscopic antifog test) , adhesion work and transmission electron microscopy (SEM) and atomic force microscope.  \n\nStudy antifog performance of transparent super hydrophobic film: First super hydrophobic thin film was made by sol-gel method: acid sol preparation: $8.36~\\mathrm{mL}$ ethyl silicate (TEOS) is added into the $\\mathbf{80mL}$ anhydrous ethanol and fully dissolved. $4.8\\mathrm{mL}$ $36\\%$ hydrochloric acid was dropped gradually into the above solution on magnetic stirrer , stirring for 9 hours. Acrylic acid solution preparation: $3.0\\ \\mathsf{g}$ acrylic acid was dissolved in $50\\mathrm{ml}$ anhydrous ethanol, fully stir until completely dissolved. Alkaline gel preparation: $3.1\\mathrm{mL}$ ethyl orthosilicate (TEOS) and $13.8\\mathbf{mL}$ deionized water were added into the $\\mathbf{80mL}$ anhydrous ethanol, and then $4.7\\mathrm{mL}$ ammonia solution was added into the above solution gradually on the working magnetic stirring , the solution was sealed and reaction for 1 hour. Different proportion of acrylic acid solution and alkaline gel were added into the anhydrous ethanol and was dispersed by ultrasonic oscillation for 1h, 20 kinds of dispersive sol were made. clean glass was dipped into above sol for 1Os, then the clean glass was pulled out by coating machine with speed of $3\\mathrm{mm/s}$ , and planced it for about 15 minutes at room temperature, because of the surface adsorption and chemical bonding force, the sol will form a layer of uniform film on the surface of the substrate , 3 layers and 5 layers coating were made. The substrates were put into the muffle furnace and increased the temperature to $400^{\\circ}\\mathrm{Cin}\\ 2$ hours, heat preservation for 0.5h and natural cooling, transparent silica film samples were made .the glass coated with silica film coating were dipped into the silane coupling agent hydrophobic liquid and immersed for 3 hours, then the sample were put into the $100^{\\circ}\\mathrm{C}$ oven drying for sixty minutes and transparent hydrophobic silica film were done.  \n\nThe antifogging performance of the samples No.8 and No.13 which were hydrophobic were tested. methods: simulation certain temperature difference, the antifogging performance of the samples of coating substrate, the blank substrate and silane coupling agent coating substrate were test. The substrate were put on thermostatic water bath and the silica layer face to the surface of the water the distance between the substrate and water surface is $3\\ \\mathrm{cm}$ , room temperature is $13^{\\circ}\\mathrm{C},$ the temperature of water in the Water Bath is set to ${60^{\\circ}}\\mathrm{C}$ After $5\\mathrm{min}$ $10~\\mathrm{{min}}$ , and min, $30\\mathrm{min}$ , the antifogging performance were observed.  \n\nStatistics (chapter 1) factors A: anhydrous ethanol; Factor B: propylene glycol; Factor C: lauryl alcohol polyethylene glycol ether factor D: sodium dodecyl sulfate; Factors E: polyethylene glycol (peg) 400,the weight percentage of each material has three levels (a: $1=3\\%$ $2=10\\%$ . $3=20\\%$ ; b: $1=3\\%$ $2=10\\%$ $3=20\\%$ : c: $1=3\\%$ , 2 $=10\\%$ ， $3=20\\%$ ; d: $1=0.6\\%$ ， $2=2\\%$ $3=4\\%$ ; E: $1=0.6\\%$ $2=2\\%$ 。 $3=4\\%$ if you want todo all the test completely,there need to do 3 by 3 by 3 by 3 by $3=243$ times test (Orthogonal), the Orthogonal test was designed by SPSSi3. the results of antifogging performance were analyzed by variance.",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# Results:  \n\nBy the orthogonal experiment, we made 27 kinds of different concentration of antifogging agent, the antifog time and antifogging performance of all the 27 samples were characterized, the best ratio (A3B2C3D3E3) of weight percentage of each material was got according to the average analysis of the different components. the transmissivity of all the antifogging agent are close to $100\\%$ ; Contact angle is about  \n\n7.6degrees; Scanning electron microscopy (SEM) shows that the antifogging agent form a flat layer on the surface of nasal endoscopic lens (sapphire); another sample was made according to the best ratio and was tested, the average antifog time is 15 minutes. As control, the transmissivity of medical betadine its about $80\\%$ ; Contact angle is about 10degrees; Scanning electron microscopy shows that the medical betadine coating is scattered island and irregular, failure to form a flat layer on the surface of nasal endoscopic lens (sapphire), the average antifog time is $04^{\\prime}05^{\\prime\\prime}$ .the antifogging agent made by ourself was better than $95\\%$ ethanol $(38\"$ ）and medical betadine.  \n\nAntifogging performance of antifogging agent and modified antifogging agent: the average antifog time of antifogging agent modified by $\\mathbf{SiO}_{2}$ is 18 minutes; the average antifog time of antifogging agent modified by nano $\\mathbf{SiO}_{2}$ -KH570 is 21 minutes. Light transmittance: in the visible light range, the light transmittance of antifogging agent is about $100\\%$ ； the light transmittance of antifogging agent modified by $\\mathrm{SiO}_{2}$ is about $90\\%$ ; the light transmittance of antifogging agent modified by nano $\\mathbf{SiO}_{2}$ -KH570 is about $97\\%$ Contact Angle: the contact angle of water droplets on the antifogging agent coating is about 7.8 degrees; the contact angle of water droplets on the antifogging agent modified by $\\mathbf{SiO}_{2}$ coating is about 7.0 degrees; the contact angle of water droplets on the antifogging agent modified by nano $\\mathrm{SiO}_{2}$ -KH570 coating is about 6.7 degrees. Adhesion work: The contact angle between water and the surface of sapphire is about (56.1 59.9 58.0) degrees, the average is 58.0 degrees; The contact angle between ethylene glycol and the surface of sapphire is about (46.3 51.6 48.2), the average is 48.7 degrees; the surface energy of sapphire is $52.36\\pm\\mathrm{mN}/\\mathrm{m},$ the dispersive component is $2.92~\\mathrm{mN/m};$ the polar component is $49.44~\\mathrm{mN/m}$ ； the adhesion work between the antifogging angent of nasal endoscope and the sapphire len is $40.71\\ \\mathrm{mN/m}$ , the adhesion work between the antifogging agent modified by $\\mathbf{SiO}_{2}$ and the sapphire lens is $49.73\\mathrm{mN/m}$ the adhesion work between the antifogging agent modified by nano $\\mathrm{SiO}_{2}$ -KH570 and the sapphire lens is 55.38 $\\mathbf{mN}/\\mathbf{m}$ . Transmission electron microscopy (SEM) : diameter of $\\mathrm{SiO}_{2}$ is about $100\\sim$ $200\\ \\mathrm{nm}$ 。 spherical, the dispersion of nano $\\mathrm{SiO}_{2}$ in the antifoggant is poor ; the dispersion of nano $\\mathrm{SiO}_{2}$ KH570 in the antifoggant is obviously improved, it presents single nanoparticles distribution. Atomic force microscope: the newly developed antifogging agent form a uniform and smooth layer on the surface of nasal endoscope(sapphire) ,the thickness is about $192.30\\ \\mathrm{nm}$ ： antifogging agent modified by $\\mathbf{SiO}_{2}$ form a slightly rough layer on the surface of nasal endoscope(sapphire) ,the thickness is about $200.09\\:\\mathrm{nm}$ ； antifogging agent modified by nano $\\mathrm{SiO}_{2}$ -KH570 form a rough layer on the surface of nasal endoscope(sapphire).  \n\nAntifogging performance of PVP and modified PVP: the average antifog time of PVP is 10 minutes; the average antifog time of PVP modified by nano zno is 15 minutes; the average antifog time of PVP modified by nano titanium oxide is 16 minutes; the average antifog time of PVP modified by hollow nano silica is 17 minutes. Light transmittance: in the visible light range, the light transmittance of PVP is about $100\\%$ the light transmittance of PVP modified by nano zno is about $90\\%$ 。 the light transmittance of PVP modified by nano titanium oxide is about $85\\%$ ：the light transmittance of PVP modified by hollow nano silica is about $92\\%$ The light transmittance of betadine is about $80\\%$ ； The light transmittance of nano titanium dioxide modified betadine is about $70\\%$ . Contact Angle: the contact angle of water droplets on the PVP is about 9.6 degrees; the contact angle of water droplets on the PVP modified by nano zno coating is about 5.9 degrees; the contact angle of water droplets on the PVP modified by nano titanium oxide coating is about 4.8 degrees; the contact angle of water droplets on the PVP modified by hollow nano silica coating is about 6.1 degrees. Adhesion work: the adhesion work between pvp and the sapphire lens is $\\mathbf{96.10mN/m}$ , the adhesion work between the PVP modified by nano zno and the sapphire lens is $101.02\\ \\mathrm{mN/m}$ ， the adhesion work between the PVP modified by nano titanium oxide and the sapphire iens is $100.81~\\mathrm{mN/m}$ ， the adhesion work between the PVP modified by hollow nano silica and the sapphire lens is 102.92 $\\mathbf{mN}/\\mathbf{m}$ . Transmission electron microscopy: the dispersion of nanometer zinc oxide in PVP solution is good; the diameter of nano titanium oxide particle which was made by ourself is about $120\\sim160\\ \\mathrm{nm}$ and well dispersive in PVP solution; the diameter of hollow nano silica particles which was made by ourself is about $200\\mathrm{nm}$ and also well dispersive in PVP solution. Atomic force microscope:the newly developed antifogging agent of pvp form a uniform and smooth layer on the surface of nasal endoscope(sapphire) ,the thickness is about $78.30\\ \\mathrm{nm}$ ： PVP modified by nano zno form a slightly rough layer on the surface of nasal endoscope,the thickness is about $277.97\\ \\mathrm{nm}$ ; PVP modified by nano titanium oxide form a rough layer on the surface of nasal endoscope, the thickness is about $227.34\\:\\mathrm{nm}$ ; PVP modified by hollow nano silica form a rough layer on the surface of nasal endoscope,the thickness is about $34.64\\ \\mathrm{nm}$  \n\nBecause of phase separation and self-assembly silane coupling agent, 20 kinds of coating were made with acrylic induction and ethyl silicate (TEOS) on glass substrate by sol-gel method, the samples of ${\\tt N o}.8\\sim13\\$ were hydrophobic, the best one which has superhydrophobic properties is No.13. Scanning electron microscopy (SEM) shows the microstructure of the film surface is crater form, the contact angle of the surface of the coating is about $153^{\\circ}$ which made the sample has superhydrophobic properties, antifog test shows that it has certain antifog performance, in the visible light range, the light transmittance of the super hydrophobic coating is about $80\\%$ \\*",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# Conclusion:  \n\nThe hydrophilic antifogging agent of nasal endoscope by orthogonal design has some excellent properties such as transparent, non-toxic, tasteless. Its antifog time is much longer than that of the clinical commonly used betadine and alcohol; The nano silica particles modified hydrophilic antifogging agent of nasal endoscope prolong the antifog time evidently and improve the antifogging performance; Nanoparticles modified polyvinyl pyrrolidone antifogging agent of nasal endoscope is transparent, non-toxic, tasteless, its antifog time is also much longer than that of the betadine and alcohol. Superhydrophobic material has certain antifog performance, but its surface is rough and the light transmittance is not so good, it is difficult to make a coating with the surface contact angle of 180 degrees, it need to be further study of transparent super hydrophobic coating to be applied to clinical antifog of nasal endoscope.  \n\nKEYWORDS: nasal endoscope, antifog, super hydrophilic, nanoparticle, super hydrophobic",
+        "category": " Conclusions"
+    },
+    {
+        "id": 13,
+        "chunk": "# 目录  \n\n摘要  \nABSTRACT  \n绪论",
+        "category": " Abstract"
+    },
+    {
+        "id": 14,
+        "chunk": "# 第一章 亲水型鼻内镜防雾剂研制  \n\n1 材料和方法 8  \n2 结果. 11  \n3 讨论 14  \n4 结论 .16  \n参考文献 17  \n附图 .18",
+        "category": " Introduction"
+    },
+    {
+        "id": 15,
+        "chunk": "# 第二章 纳米粒子改性亲水型鼻内镜防雾剂研制 22  \n\n1材料和方法 22   \n2结果. 26   \n3 讨论 .28   \n4 结论 33   \n参考文献 34   \n附图 37",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 16,
+        "chunk": "# 第三章 纳米粒子改性聚乙烯吡咯烷酮鼻内镜防雾剂研制 .42  \n\n1材料和方法 42   \n2 结果 46   \n3讨论 .48   \n4结论 .53   \n参考文献 54   \n附图 56",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 17,
+        "chunk": "# 目录",
+        "category": " References"
+    },
+    {
+        "id": 18,
+        "chunk": "# 第四章 透明超疏水薄膜的防雾性能研究 63  \n\n1 材料和方法 64  \n2 结果 68  \n3 讨论 .70  \n4结论 .78  \n参考文献 .79  \n附图 .81  \n全文总结 89  \n综述一 亲水防雾材料研究进展 91  \n综述二 超疏水材料研究进展 106  \n缩写词简表 .120  \n致谢 121  \n博士研究生期间发表论文情况 122  \n参加国内国际会议 123  \n南方医科大学学位论文原创性声明 124  \n统计学审稿证明 125",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 19,
+        "chunk": "# 绪论",
+        "category": " Introduction"
+    },
+    {
+        "id": 20,
+        "chunk": "# 1．研究鼻内镜防雾剂的意义  \n\n鼻内镜手术因其确切的疗效及损伤小等诸多优势，目前已在全国各级医院广泛开展，与其相关的设备也在不断改进，特别是三晶内镜及其显示系统使手术野更加清晰。但鼻内镜手术并发症尤其是严重并发症仍时有发生，其原因之一是术腔出血，镜面模糊，视野不清所致。迄今国内外有关鼻内窥镜防雾材料的报道罕见，内镜防雾问题仍然没有解决。国内出版的专著多推荐使用医用碘伏、热水、 $95\\%$ 的酒精、 $2.5\\%$ 的新洁尔灭等。但这些材料存在防雾时间短、易烫伤鼻粘膜、刺激性大或发生过敏反应，不能满足临床要求。寻求无毒、生物相容性好的防雾剂是与临床密切相关的研究课题。",
+        "category": " Introduction"
+    },
+    {
+        "id": 21,
+        "chunk": "# 2．鼻内镜表面雾化产生的条件  \n\n人体鼻腔内气体经鼻腔的加温加湿后其温度约为 $33{\\sim}35^{\\circ}\\mathrm{C}$ ，湿度约 $90\\%$ 当呼出的气体遇到冷的内窥镜镜面时，便发生水汽凝结成雾滴，由于雾滴大小、分布不均匀，当平行入射光线射到有雾滴的内镜镜面时，内镜表面会把光线向着四面八方反射，造成反射光线向不同的方向无规则地漫反射而出现镜面模糊，视野不清。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 22,
+        "chunk": "# 3．鼻内镜防雾的机理与途径  \n\n目前日常生活及工农业生产的防雾材料绝大部分是亲水材料，利用材料亲水的特点使材料表面的水汽或雾滴变成一层水膜减少光的漫反射而防雾，疏水材料防雾罕见有研究报道。因此，实验研究鼻内镜防雾材料探讨鼻内镜防雾的机理时也应从亲水或疏水材料入手。在此之前，先要了解接触角、亲水、超亲水、疏水及超疏水几个概念。  \n\n接触角是指在气、液、固三相交点处所作的气-液界面的切线与固-液交界线之间的夹角0，代表液体浸润固体表面的程度，如图0即为接触角：  \n\n若 $\\scriptstyle\\theta<90^{\\circ}$ ，即固体可被液体浸润，表明固体表面是亲水的，接触角越小，液体对固定的浸湿性越好，当 $\\scriptstyle\\Theta=0^{\\circ}$ ，这是一种极端的状态，表明固体表面可被完  \n\n全润湿，水滴面能完全铺展$\\theta{>}90^{\\circ}$ ，表明不易被水滴浸面呈现疏水状固定表面上滚$\\scriptstyle\\theta=180^{\\circ}$ ，这是全浸润相反的状态，水滴完在固体表开来；若固体表面润，固体表态，容易在动，当一种与完另一极端全不润湿  \n\n![](images/7246189da06790638bd2a43a2d5aca86a7260545ce1f91555bc8ef9c4d477a2d.jpg)  \n\n固体表面，即固体表面完全疏水，在此理想状态下水滴可以在固体表面自由滚动。液体浸润固体的过程与体系界面张力有关，当一滴液体滴落在水平固体表面上，其在固体表面有达至平衡趋势，当达到平衡时，固气、固液、气液界面自由能Ysg、Yls、Ygl与接触角θ之间的关系符合界面化学的经典方程杨氏方程即润湿方程， $\\gamma_{\\mathrm{sg}}-\\gamma_{\\mathrm{ls}}{=}\\gamma_{\\mathrm{gl}}C\\cos\\theta^{[2]}$ 。  \n\n目前临床上常用的鼻内镜多以透光率好且耐磨的蓝宝石作镜头，通常防雾的途径包括：第一：内镜表面涂亲水材料，即材料表面带有亲水基团的分子，对水有较大的亲和能力，可以吸引水分子，这类材料在内镜表面形成亲水涂层，易被水所浸湿，雾滴在材料表面可迅速铺展开形成一层水膜减少对光的漫反射而达到防雾的目的，这种分子做成的材料就是亲水材料如医用碘伏、乙醇等，这也是临床上最常用的防雾途径。第二：与亲水材料相反，在鼻内镜表面构建一疏水材料，因疏水材料表面不易被水浸润，雾滴在材料表面容易滚动理论上可以达到防雾效果，但查阅文献至今罕见有此类研究报导。第三：使鼻内窥镜镜面温度升高，当镜面温度高于露点温度时水汽不能在鼻内镜表面凝结而达到防雾的目的，如临床亦常用热水来防雾。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 23,
+        "chunk": "# 4.国内外防雾材料的进展  \n\n自上世纪90年代以来，有关防雾材料的制备方法其实已有报道，主要包括超亲水和超疏水两类。材料表面改性后水滴在其表面的接触角 $<5^{\\circ}$ 称为超亲水表面。1997年，Wang等报导了经紫外光照射的 $\\mathrm{TiO}_{2}$ 半导体薄膜具有超亲水性，即水与 $\\mathrm{TiO}_{2}$ 半导体薄膜表面接触，接触角由几十度迅速变小，最后达到 $\\scriptstyle1\\pm1^{\\circ}$ 。纳米Ti0超亲水表面的形成大多数都是光催化物质存在，受紫外线或可见光的辐射影响后，光催化表面因光激发所产生的氧空位吸附而产生亲水性区域使Ti0薄膜具有超亲水的性能。超亲水表面的形成采用如下几种方法，第一：利用光催化物质，如二氧化钛及氧化锌，它们受紫外线或可见光的辐射影响后，具有超亲水的性能[5]。第二：通过对物质表面化学和几何微结构的改造，微孔表面可以使材料具有超亲水性能，水会被吸附在材料表面的凹缝里，剩下的水滴流在固体和液体的拼凑面上。另外，简便的方法是在材料表面喷涂液态亲水材料即可构成亲水表面，如汽车挡风玻璃喷涂防雾剂，内镜手术时内镜表面涂医用碘伏及乙醇等均属于此类情况，目前文献报导的常用的超亲水性涂料薄膜的制备方法主要有液相沉积法[7、化学气相沉积法[、溶胶-凝胶法[9、浸渍法[、溅射法[0]等，喷涂型防雾剂的研究已有不少报道[[2]。超亲水材料已广泛应用于各种商业、工农业，和生物医药领域，涉及自清洁、防雾、防污性能等方面。  \n\n所谓超疏水性表面一般是指与水的接触角大于 $150^{\\circ}$ 、滚动角小于 $10^{\\circ}$ 的表面。一个真正意义上的超疏水表面既要有较大的接触角，还应具有较小的滚动角[13]。1996年，Kao公司采用造纸施胶剂烷基正乙烯酮二聚体制得分形结构的粗糙表面，其表面与水的接触角达到 $174^{\\circ[14]}$ ，这是利用化学方法构建粗糙表面来制备超疏水表面的著名实验。近年来，随着微纳米科学技术的发展及先进的表面处理技术的应用，以及越来越多行业对超疏水材料的需求，人们对微结构超疏水表面制备的研究也进入了一个全新的阶段。超疏水表面一般可以通过两类技术路线来制备：一类是在低表面能的疏水材料表面上构建微米-纳米级粗糙结构；另一类是用低表面能物质在微米-纳米级粗糙结构上进行修饰处理。其中，制备合适微米-纳米级粗糙结构的方法是相关研究的关键。目前文献报导的主要方法有：模板印刷法[15]、蒸汽诱导相分离法[1]、电纺法[7、溶胶-凝胶法[18]、模板挤压法[9]、激光和等离子体刻蚀法[2]、腐蚀法[]、拉伸法[22]、嵌段聚合物的相分离[23]、溶剂挥发[24]、升华法[25]等。为了得到更有效的超疏水表面，还要予低表面能物质如氟硅烷(FAS)等对粗糙表面进行化学修饰。通常超疏水表面由于表面的粗糙结构而不透明，影响了其应用范围，既有超疏水性又在可见光范围内透明性好的表面在镜片、挡风玻璃等领域具有广阔的应用前景。Nakajima等首次制成同时具有超疏水性、光学透明性和使用耐久性的水软铝石薄膜和二氧化硅薄膜[13]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 24,
+        "chunk": "# 5.超亲水、超疏水材料应用于鼻内镜防雾面临的问题  \n\n超亲水材料因雾滴在其表面易形成一层水膜而迅速铺展开来减少光的漫反射而达到防雾的目的，但亲水材料特别是喷涂型的亲水材料与固体表面结合不牢固而容易从固体表面流失，影响其防雾性能，能否向防雾材料添加纳米粒子增强防雾剂与材料表面的结合力而延长其防雾时间是我们将要研究的科学问题。超疏水材料因其表面需要粗糙的结构才能达到疏水的状态，且疏水能力与材料表面的粗糙度呈正相关，即材料表面越粗糙其疏水性能就越好，但这必将带来一新的问题，即疏水性越好其表面粗糙度就越高，而粗糙度越高其透光率就会越差，影响光学材料的性能。如何在粗糙度、疏水性及透光率之间找到一很好地平衡也是需要亟待解决的问题。另外，超疏水与防雾属于两个不同的概念，水滴在疏水材料表面容易滚动，但水汽因远小于水滴，其在疏水材料表面是否也容易滚动也缺少这方面的研究报导，超疏水材料能否用于防雾还有待于深入研究。",
+        "category": " Introduction"
+    },
+    {
+        "id": 25,
+        "chunk": "#  \n\n疹考又献   \n[1]韩德明．鼻内窥镜外科学．北京：人民卫生出版社,2002，104.   \n[2] Young T, Philos. An Essay on the Cohesion of Fluids[J]. Philos,Trans. R. Soc. London,1805, 95(65):65-87.   \n[3] Wang R, Kazuhito H, Akira F. Light induced amphiphilic surfaccs [J]. Nature, 1997,388(31):431-432.   \n[4] Euvananont C, Junin C, Inpor K, et al. $\\mathrm{TiO}_{2}$ optical coating layers for self-cleaning applications[J].Ceramics International, 2008， 34(4): 1067-1071.   \n[5]Kubo W , Tatsuma T. Photocatalytic remote oxidation with various photocatalysts and enhancement of its activity[J]. Journal of Materials Chemistry， 2005, 15(30):3104-3108.   \n[6]Cebeci C, Wuz, ZhaiL, etal. Nanoporosity-Driven Superhydrophilicity: A Means to Create Multifunctional Antifogging Coatings[J]l.Langmuir, 2006, 22(6): 2856-2862.   \n[7]周磊，赵文宽，方佑龄．液相沉积法制备光催化活性 $\\mathrm{TiO}_{2}$ 薄膜[J]．应用化 学，2002，19(10):919-922.   \n[8] McSporran N, Rico V, Borras A, et al. Synthesis of undoped and Nidoped In TaO4 photoactive  thin  films by metal  organic  chemical  vapor deposition[J]. Surface and Coatings Technology, 2007, 201(22-23): 9365-9368.   \n[9]Lu X, Wang Y B, Liu Y R, et al. Preparation of HA/chitosan composite coatings on alkali treated  titanium surfaces through sol-gel techniques[J].Materials Letters, 2007, 61(18):3970-3973.   \n[10] Ayumi M, Toshiaki Y, Shin-ichi H. Synthesis of porous titania thin films using carbonatation reaction and its hydrophilic property [J]. Thin Solid  \n\nFilms,2008, 56(12):3888-3892.  \n\n[11]王凤平，单金环，刘照斌．长效玻璃防雾剂制备与性能研究[J]．辽宁师范 大学学报(自然科学版)，2007，30（2)：188-190.   \n[12]万屏南，衷友泉，熊丽萍．新型氧化铈玻璃防雾剂的研制[J]．华东交通大 学学报，2006，23（1)：189-172.   \n[13] A.Nakajima, A.Fujishima, K.Hashimoto, et al. Preparation of Transparent Superhydrophobic Boehmite and Silica Films by Sublimation of Aluminum Acetylacetonate Advanced Materials[J]. 1999, 11(l6):1365-1368.   \n[14] OndaT, ShibuichiS, SatohN, et al. Super-water-repellent fractal surfaces [J]. Langmuir,1996,12， 2125-2127.   \n[15] Sun M H, Luo C X, Xu L P, et al . Artificial lotus leaf by nanocasting[J]. Langmuir， 2005， 21,8978-8981.   \n[16] Zhao N, Xie Q D, Weng L H, et al.Superhydrophobic surface from vapor-induced  phase  separation  of  copolymer  micellar  solution[J]. Macromolecules, 2005， 38,8996- 8999.   \n[17] Kang M S, Jung R, kim H S, et al. Preparation of superhydrophobic polystyrene membranes by electrospinning[J]. Colloid Surf A ， 20o8, 313, 411-414.   \n[18] Bhagat S D, Oh C S, Kim Y H , et al.M ethyltrimethoxysilane based monolithic silica aerogels via ambient Dressure drying[J]. Microporous and Mesoporous Mater,2007,100(3):350-355.   \n[19] Feng L, Song Y L, Zhai J, el al. Creation of a superhydrophobic surface from an amphiphilic polymer[J]. Angew Chem Int Ed,2003,42:800-802.   \n[20] Fresnais J, Chapel J P, Poncin-Epaillard F. Synthesis of transparent superhydrophobic polyethylene surfaces[J]. Surf Coatings Tech， 2006, 200,5296-5305.   \n[21]  Li Y, Cai W P, Cao B Q, et al.Two-dimensional hierarchical porous silica film and its tunable superhydrophobicity[J]. Nanotechnology， 2006， 17， 238-243.   \n[22] Zhang J L,Han Y c.superhydrophobic PTFE surfaces by extension [J].Macromol Rapid Commun,2004， 25， 1105-1108.   \n[23] Ma M, Hill RM, Lowery JL, Electrospun poly (styrene block -dimethyisiloxane) block copolymer fibers exhibiting superhydrophobicity[J].Langmuir, 2005, 21(12):5549-5554.   \n[24] Erbil HY, Demirel AL, Avci Y,et al.Transformation of a simple plastic into a superhydrophobic surface[J].Science， 2003， 299(5611): 1377-1380.   \n[25] Zhao.B,Brittain. WJ. Synthesis of Polystyrene Brushes on Silicate Substrates via Carbocationic Polymeriztion from  Self-Assembled  Monolayers[J]. Macromolecules, 2000， 33， 342-348.",
+        "category": " References"
+    },
+    {
+        "id": 26,
+        "chunk": "# 第一章 亲水型鼻内镜防雾剂研制  \n\n前言：目前日常生活及工农业生产所用的防雾剂如汽车玻璃、镜面或农用薄膜的喷涂型防雾剂多属于亲水材料，通常由表面活性剂、溶剂、分散剂等按不同的组分配制而成，此类防雾材料大多仅要求其有较好的防雾性能，而对其毒性、气味要求并不十分严格。但作为能应用临床的防雾材料务必要求其具有无毒、无味、刺激性小等特点，因此，日常生活及工农业报导的防雾材料并不适合于临床内镜防雾。迄今为止，国内各家医院基本上仍使用医用碘伏、医用酒精、热水或肥皂液来防雾，医用碘伏防雾时间相对较长，但因其含碘其透光率受一定的影响；医用酒精也可用于临床内镜防雾，其缺点是易挥发致其防雾时间短且其具有一定的刺激性；肥皂液用作内镜防雾亦有一定的刺激性；热水可使鼻内镜镜面温度升高而具有防雾性能，但因镜头温度高而有烫伤鼻粘膜的风险，且在室内温度较低的情况下鼻内镜镜面的温度可能很快降低，当镜面温度低于露点温度时就不再具有防雾性能，以热水来进行内镜防雾其防雾时间很短，所以临床上鼻内镜防雾问题实际上仍没有得到很好地解决。本实验以无毒、无味、刺激性小的表面活性剂、溶剂、分散剂等原料，拟通过正交设计，按不同的质量配比选配出透光率高且防雾性好的亲水型鼻内镜防雾剂。",
+        "category": " Introduction"
+    },
+    {
+        "id": 27,
+        "chunk": "# 1材料和方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 28,
+        "chunk": "# 1.1 试剂与仪器",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 29,
+        "chunk": "# 实验试剂  \n\n<html><body><table><tr><td>试剂</td><td>规格</td><td>厂家</td><td></td></tr><tr><td>无水乙醇</td><td>ａ</td><td>分析纯</td><td>天津市富宇精细化工有限公司</td></tr><tr><td>丙二醇</td><td>b</td><td>分析纯</td><td>天津市化学试剂—厂</td></tr><tr><td>月桂醇聚氧乙烯醚</td><td>C</td><td>高级纯</td><td>Aladdin Chemistry Co.Ltd</td></tr><tr><td>十二烷基硫酸钠</td><td>d</td><td>化学纯</td><td>广州市化学试剂厂</td></tr></table></body></html>  \n\n聚乙二醇400 e 分析纯 广州市化学试剂厂去离了水 自制",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 30,
+        "chunk": "# 实验仪器  \n\n仪器 型号 厂家  \n数控超声波清洗器 KQ100DB 昆山市超声仪器有限公司  \n超高分辨场发射扫描电镜 NanoSEM430 荷兰  \n紫外-可见分光光度计 Lambda 900 美国Perkin Elmer 公司  \n接触角仪 OCA20LHT 德国Dataphysics 公司  \n扫描电子显微镜 S-3700N 日本日立公司  \nStorz0°鼻内镜及显像系统 德国Storz公司  \nStorz0鼻内镜蓝宝石圆形镜片 德国Storz公司",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 31,
+        "chunk": "# 1.2 实验  \n\n1.2.1实验原理：亲水型防雾剂主要由表面活性剂、溶剂、分散剂等组成。每种物质重量百分比设有3个水平，本实验采用正交设计，共安排27次试验，使用SPSS13.0进行数据分析，具体因素水平设计见表1。  \n\n表1正交因素水平设计表  \n\n\n<html><body><table><tr><td>Table1</td><td></td><td colspan=\"3\">Design of factors and levels of the orthogonal test</td><td></td></tr><tr><td>水平</td><td>因素A</td><td>因素B</td><td>因素C</td><td>因素D</td><td>因素E</td></tr><tr><td></td><td>a与防雾剂质量比</td><td>b与防雾剂质量比</td><td>c与防雾剂质量比</td><td>d与防雾剂质量比</td><td>e与防雾剂质量比</td></tr><tr><td>1</td><td>3:100</td><td>3:100</td><td>3:100</td><td>0.6:100</td><td>0.6:100</td></tr><tr><td>2</td><td>10:100</td><td>10:100</td><td>10:100</td><td>2:100</td><td>2:100</td></tr><tr><td>3</td><td>20:100</td><td>20:100</td><td>20:100</td><td>4:100</td><td>4:100</td></tr></table></body></html>  \n\n本实验有5种物质如表1，因素A：无水乙醇；因素B：丙二醇；因素C：月桂醇聚氧乙烯醚因素D：十二烷基硫酸钠；因素E：聚乙二醇400，每种物质重量百分比设有3个水平（ $\\cdot1=3\\%$ ， $2=10\\%$ 、 $3=20\\%$ ； $6:1=3\\%$ 、 $2=10\\%$ 、 $3=20\\%$ ； $\\mathsf{c}:1=3$  \n\n$9\\%$ ， $2=10\\%$ 、 $3=20\\%$ ． $d:1=0.6\\%$ 、 $2=2\\%$ ， $3{=}4\\%$ ； $e:1=0.6\\%$ 、 $2=2\\%$ ， $3=4\\%$ ）如要完全试验，需行 $3\\times3\\times3\\times3\\times3=243$ 次试验（Orthogonal），  \n\n1.2.2防雾剂的制备按先后顺序将无水乙醇、丙二醇、月桂醇聚氧乙烯醚、十二烷基硫酸钠、聚乙二醇400，余量为去离子水按不同质量比加入称量瓶中混合并置于 $50^{\\circ}\\mathrm{C}$ 水浴箱15分钟后即得无色透明、无刺激性鼻内镜防雾剂。测其pH 值为 $7{\\sim}8$ 。如图1。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 32,
+        "chunk": "# 1.2.3防雾剂表征  \n\n1.2.3.1防雾时间：测试环境：温度 $22.3\\mathrm{^\\circC}$ ，湿度： $74\\%$ ，气压： $1010.2\\mathbf{hPa}$ 。受试者签署知情同意书，剪鼻毛后平躺， $1\\%$ 丁卡因肾上腺素棉片行鼻腔粘膜表面麻醉，Storz0°鼻内镜及显像系统进行测试，鼻内镜镜头涂防雾剂后置于鼻阈处，从鼻内镜进入鼻腔至镜面开始起雾的时间即为防雾时间。通过Storz0°鼻内镜及显像系统对防雾剂性能测试得到最佳配方（28号）见表4并对28号防雾剂进行测试。  \n\n1.2.3.2透光率：本组试验配制的 28种鼻内窥防雾剂均无色透明，利用紫外-可见分光光度计Lambda900测定第28号防雾剂的透光率，并测定防雾时间最短的15号防雾剂的透光率以对照。首先将紫外一可见分光光度计预热15分钟，重新校刻检测仪，设置扫描波长范围 $300{-}800{\\mathrm{nm}}$ ，扫描步长 $2\\mathsf{n m}$ ，对28号、15号防雾剂进行测试，测试结果采用透过率-波长曲线描述。  \n\n1.2.3.3接触角：打开接触角检测仪连接计算机、接触角检测仪电源及接触角仪视频检测后打开检测光源，将制备的Storz0°鼻内镜蓝宝石圆形镜片涂28号防雾剂样品置于检测台上,并用微量注射器缓慢地将 $2.0\\upmu\\mathrm{L}$ 的蒸馏水滴在涂膜上;调整目镜、载玻平台及光源位置，使光源中心、样品表面、蒸馏水滴、目镜在一个水平面上并保持直线；调节焦距至连接计算机视频中出现清晰图像；利用计算机视频截取水滴图像，读出水滴图像的左右两侧的接触角；在该样品上分别选取3个不同的测量点，取其平均值，并分别用接触角测量仪配套设备拍摄液滴在薄膜表面形貌照片，测量水滴在蓝宝石镜片涂28号防雾剂前后的接触角。  \n\n1.2.3.4表面形貌：为了说明涂有本防雾剂的蓝宝石圆形镜片表面形态，将28号防雾剂涂于Storz0°鼻内镜蓝宝石圆形镜片一面,待自然晾干后,用导电胶将涂防雾剂的镜片粘结在样品座上，因涂膜导电性能差，采用小型离子溅射器于其表面喷金，后进行表面形貌观测。检测前先打开场发射扫描电镜电源及连接计算机系统，向冷却阱中加入一定量的液态氮后，打开样品室，装样，关闭样品室后将其抽成真空；当真空指示灯亮时，打开V1阀，将电流加至60 微安，电压加至2万伏;调节亮度和对比度并通过Z轴将工作距离为 $12\\mathrm{mm}$ ;调节X轴及Y轴，寻找到典型的样品区域后调整放大倍数及调好焦距，慢速扫描、拍照并存贮至连接计算机系统。检测完成后将电流和电压值回零并将对比度、亮度值回零，放大倍数降至100，关闭V1阀，打开样品室，取回样品。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 33,
+        "chunk": "# 2结果  \n\n2.1",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 34,
+        "chunk": "# 表二防雾时间及防雾性能测试结果  \n\nTable2 Design of factors and levels of the orthogonal test  \n\n<html><body><table><tr><td colspan=\"5\">因素水平</td><td colspan=\"4\">防雾测试结果</td></tr><tr><td>实 因素A</td><td colspan=\"3\">因素B 因素C 因素D</td><td>因素E</td><td>第一次</td><td>第二次</td><td>第三次</td><td>平均</td></tr><tr><td>验 编</td><td>a与防雾</td><td>b与防雾 c与防雾</td><td>d与防雾</td><td>e与防雾 剂质量</td><td>时间</td><td>时间</td><td>时间</td><td>时间</td></tr><tr><td>号</td><td>剂质量 比</td><td>剂质量 比</td><td>剂质量 比 比</td><td>剂质量 比</td><td>(min)</td><td>(min)</td><td>(min)</td><td>(min)</td></tr><tr><td>一</td><td>20:100</td><td>10:100</td><td>20:100</td><td>4:100 2:100</td><td>12</td><td>13</td><td>11</td><td>12</td></tr><tr><td>2</td><td>3:100</td><td>20:100</td><td>10:100</td><td>4:100</td><td>2:100 8</td><td>10</td><td>9</td><td>9</td></tr><tr><td>3</td><td>3:100</td><td>3:100</td><td>20:100</td><td>4:100 0.6:100</td><td>8</td><td>10</td><td>9</td><td>9</td></tr><tr><td>4</td><td>20:100</td><td>3:100</td><td>3:100</td><td>2:100 4:100</td><td>8</td><td>12</td><td>10</td><td>10</td></tr></table></body></html>  \n\n<html><body><table><tr><td>５</td><td>10:100</td><td>10:100</td><td>3:100</td><td>2:100</td><td>0.6:100</td><td>15</td><td>8</td><td>10</td><td>11</td></tr><tr><td>6</td><td>10:100</td><td>3:100</td><td>3:100</td><td>4:100</td><td>2:100</td><td>11</td><td>８</td><td>８</td><td>９</td></tr><tr><td>７</td><td>3:100</td><td>10:100</td><td>20:100</td><td>2:100</td><td>4:100</td><td>9</td><td>13</td><td>14</td><td>12</td></tr><tr><td>8</td><td>20:100</td><td>20:100</td><td>3:100</td><td>4:100</td><td>0.6:100</td><td>7</td><td>13</td><td>10</td><td>10</td></tr><tr><td>9</td><td>20:100</td><td>10:100</td><td>10:100</td><td>2:100</td><td>2:100</td><td>５</td><td>14</td><td>14</td><td>11</td></tr><tr><td>10</td><td>20:100</td><td>20:100</td><td>20:100</td><td>2:100</td><td>0.6:100</td><td>10</td><td>9</td><td>8</td><td></td></tr><tr><td>11</td><td>20:100</td><td>20:100</td><td>10:100</td><td>0.6:100</td><td>0.6:100</td><td>12</td><td>6</td><td>６</td><td>８</td></tr><tr><td>12</td><td>10:100</td><td>10:100</td><td>10:100</td><td>4:100</td><td>0.6:100</td><td>10</td><td>14</td><td>15</td><td>13</td></tr><tr><td>13</td><td>20:100</td><td>3:100</td><td>10:100</td><td>4:100</td><td>4:100</td><td>11</td><td>12</td><td>13</td><td>12</td></tr><tr><td>14</td><td>20:100</td><td>3:100</td><td>20:100</td><td>0.6:100</td><td>4:100</td><td>15</td><td>11</td><td>16</td><td>14</td></tr><tr><td>15</td><td>3:100</td><td>3:100</td><td>3:100</td><td>0.6:100</td><td>0.6:100</td><td>10</td><td>6</td><td>５</td><td>7</td></tr><tr><td>16</td><td>10:100</td><td>3:100</td><td>10:100</td><td>0.6:100</td><td>2:100</td><td>7</td><td>9</td><td>8</td><td>8</td></tr><tr><td>17</td><td>10:100</td><td>20:100</td><td>20:100</td><td>4:100</td><td>4:100</td><td>11</td><td>13</td><td>15</td><td>13</td></tr><tr><td>18</td><td>3:100</td><td>20:100</td><td>20:100</td><td>0.6:100</td><td>2:100</td><td>10</td><td>7</td><td>7</td><td>８</td></tr><tr><td>19</td><td>10:100</td><td>20:100</td><td>10:100</td><td>2:100</td><td>4:100</td><td>13</td><td>６</td><td>８</td><td>９</td></tr><tr><td>20</td><td>3:100</td><td>10:100</td><td>3:100</td><td>4:100</td><td>4:100</td><td>10</td><td>9</td><td>8</td><td>9</td></tr><tr><td>21</td><td>3:100</td><td>10:100</td><td>10:100</td><td>0.6:100</td><td>4:100</td><td>11</td><td>9</td><td>10</td><td>10</td></tr><tr><td>22</td><td>10:100</td><td>10:100</td><td>20:100</td><td>0.6:100</td><td>0.6:100</td><td>10</td><td>8</td><td>9</td><td>9</td></tr><tr><td>23</td><td>10:100</td><td>3:100</td><td>20:100</td><td>2:100</td><td>2:100</td><td>13</td><td>10</td><td>10</td><td>11</td></tr><tr><td>24</td><td>3:100</td><td>3:100</td><td>10:100</td><td>2:100</td><td>0.6:100</td><td>10</td><td>６</td><td>５</td><td>7</td></tr><tr><td>25</td><td>20:100</td><td>10:100</td><td>3:100</td><td>0.6:100</td><td>2:100</td><td>9</td><td>11</td><td>7</td><td>９</td></tr><tr><td>26</td><td>3:100</td><td>20:100</td><td>3:100</td><td>2:100</td><td>2:100</td><td>10</td><td>５</td><td>６</td><td>7</td></tr><tr><td>27</td><td>10:100</td><td>20:100</td><td>3:100</td><td>0.6:100</td><td>4:100</td><td>10</td><td>６</td><td>8</td><td>8</td></tr></table></body></html>\n\n注：时间精确到分，以 $30^{\\prime\\prime}$ 为界舍入",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 35,
+        "chunk": "# 表3防雾性能测试结果  \n\nTable3  Analyse of propety test result   \n\n\n<html><body><table><tr><td rowspan=\"2\">因素</td><td colspan=\"5\">防雾时间/min</td></tr><tr><td>因素A</td><td>因素B</td><td>因素C</td><td>因素D</td><td>因素E</td></tr><tr><td>均值1</td><td>8.667±0.425</td><td>9.667±0.425</td><td>8.889±0.425</td><td>9.000±0.425</td><td>9.222±0.425</td></tr><tr><td>均值2</td><td>10.111±0.425</td><td>10.667±0.425</td><td>9.667±0.425</td><td>9.667±0.425</td><td>9.333±0.425</td></tr><tr><td>均值3</td><td>10.556±0.425</td><td>9.000±0.425</td><td>10.778±0.425</td><td>10.667±0.425</td><td>10.778±0.425</td></tr><tr><td>Ｆ</td><td>5.402</td><td>3.897</td><td>4.991</td><td>3.897</td><td>4.171</td></tr><tr><td>P</td><td>.016</td><td>.042</td><td>.021</td><td>.042</td><td>.035</td></tr></table></body></html>\n\n（样本量N为 $5\\times3\\times27=405;$  \n\n表4最佳防雾剂配比 $(\\mathbf{w\\%})$ Table 4 best ratio of antifoggant $(\\mathbf{w\\%})$   \n表5正交资料的方差分析表  \n\n\n<html><body><table><tr><td>无水乙醇</td><td>丙二醇</td><td>月桂醇聚氧乙烯醚</td><td>十二烷基硫酸钠</td><td>聚乙二醇400</td><td>去离子水</td></tr><tr><td>20</td><td>10</td><td>20</td><td>4</td><td>4</td><td>余量</td></tr></table></body></html>  \n\nTable 5 Tests of Between-Subjects Effects   \n\n\n<html><body><table><tr><td colspan=\"2\">Type III Sum of</td><td colspan=\"2\"></td><td colspan=\"2\"></td></tr><tr><td>Source</td><td>Squares</td><td>df</td><td> Mean Square</td><td>F</td><td>Sig.</td></tr><tr><td>Corrected Model</td><td>72.667(a)</td><td>10</td><td>7.267</td><td>4.472</td><td>.004</td></tr><tr><td>Intercept</td><td>2581.333</td><td>1</td><td>2581.333</td><td>1588.513</td><td>.000</td></tr><tr><td>a</td><td>17.556</td><td>2</td><td>8.778</td><td>5.402</td><td>.016</td></tr><tr><td>b</td><td>12.667</td><td>2</td><td>6.333</td><td>3.897</td><td>.042</td></tr><tr><td>c</td><td>16.222</td><td>2</td><td>8.111</td><td>4.991</td><td>.021</td></tr><tr><td>d</td><td>12.667</td><td>2</td><td>6.333</td><td>3.897</td><td>.042</td></tr><tr><td>e</td><td>13.556</td><td>2</td><td>6.778</td><td>4.171</td><td>.035</td></tr><tr><td>Error</td><td>26.000</td><td>16</td><td>1.625</td><td></td><td></td></tr><tr><td>Total</td><td>2680.000</td><td>27</td><td></td><td></td><td></td></tr><tr><td>Corrected</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> Total</td><td>98.667</td><td>26</td><td></td><td></td><td></td></tr></table></body></html>\n\na R Squared $\\c=$ .736 (Adjusted R Squared $\\mathbf{\\sigma}=$ .572）Dependent Variable: t  \n\n2．2透光率：28号、15号防雾剂两者透光率均接近 $100\\%$ ,如图2、3。  \n\n2.3接触角：鼻内窥镜镜头蓝宝石表面的接触角为73度，涂防雾剂后鼻内窥镜镜头蓝宝石表面接触角仅为7.6度，如图4、图5。  \n\n2.4表面形貌：防雾剂在鼻内镜镜头蓝宝石表面形成一层均匀膜，如图6、图7。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 36,
+        "chunk": "# 3讨论  \n\n鼻内镜手术时，空气中有一定量水蒸汽存在，一旦具有一定分压的水蒸汽冷却到其露点时，水蒸汽达到饱和，鼻内镜镜头表面就会冷凝析出大量细小的雾滴。由于小雾滴的曲率半径不同，对光产生的漫反射不同，鼻内镜镜头表面就会出现雾化现象。长期以来国内各大医院以医用安尔碘、 $95\\%$ 酒精或肥皂液作为鼻内窥镜防雾剂，但其防雾时间短，需反复擦拭镜头而延误手术时间。目前国内外防雾材料研制主要应用于汽车、建筑玻璃或农用薄膜的防雾上，并且防雾材料大多为亲水材料[-5]，而医用内窥镜防雾剂的研制的报道较少。  \n\n亲水型防雾剂通常由表面活性剂、溶剂、分散剂等组成，配制防雾剂时所选择的表面活性剂必须具备能很好地降低水的表面张力的能力。应用于汽车、建筑玻璃或农用薄膜的防雾剂对气味及毒性要求并不十分严格，但要研究今后能应用于临床内镜的防雾剂，对表面活性剂、溶剂、分散剂等每一组分均要有严格的要求，要求它们必须是无味，无刺激性及无毒的，另外，要求其PH值要为中性或接近中性。本实验鼻内镜防雾剂配方主要成分为阴离子表面活性剂十二烷基硫酸钠、非离子表面活性剂月桂醇聚氧乙烯醚、分散剂丙二醇、溶剂去离子水。十二烷基硫酸钠由于有良好的水溶性，较好的分散和去污性能，不仅表面附着力强，而且有洗涤功能，亲水性也强，是目前洗涤剂配方中使用较多的阴离子表面活性剂，已广泛用于牙膏、洗发膏、及制药行业。月桂醇聚氧乙烯醚具有优良的洗涤、增溶等功能，去污力优异，是表面活性剂中对皮肤、粘膜刺激性最低的品种之一。它能与各种表面活性剂复配，降低它们的刺激性，是化妆品、浴液、婴儿香波和洗面奶的最佳原料，其亲水性是因为月桂醇聚氧乙烯醚分子中氧原子与水形成氢键。丙二醇对人体无毒，具有优异的吸湿性和粘附性，在化妆品、食品和医药行业中广泛用作分散剂、溶剂。聚乙二醇 400为几乎无色的粘稠液体，在水或乙醇中易溶,常用作药用辅料。本防雾剂组分均采用对人体无毒的原料，PH值接近中性，适用于手术时鼻内镜防雾。  \n\n防雾时间是评价防雾剂性能的重要指标之一，防雾时间越长，则防雾剂性能越好。通过正交设计，首先配制出27种不同浓度配方的防雾剂，然后对这27种配方防雾剂的防雾时间及其防雾性能进行测试，结果通过SPSS13.0统计软件分析得出不同组分的不同均值，再通过分析不同的均值得到防雾时间最长的配方为（A3B2C3D3E3），5个因素的水平间均有显著差异，如表五。随后即按（A3B2C3D3E3)配制28号防雾剂并对同一受试者在相同的测试环境下进行防雾测试3次，其平均防雾时间为15分钟。通过与医用安尔碘（平均防雾时间 ${\\bf04^{\\prime}05\"})$ 、$95\\%$ 乙醇（平均防雾时间 $38^{\\prime\\prime}$ ）在相同环境下的防雾时间进行比较发现此防雾剂防雾效果明显优于临床常应用于鼻内镜防雾的 $95\\%$ 乙醇及医用安尔碘。透光率也是鼻内窥镜防雾剂的性能指标之一，好的透光率是材料能作为内镜防雾的首要条件。本试验除所测试的28号、15号防雾剂两者在可见光范围内其透光率均接近 $100\\%$ 外，所配制的其它26种防雾剂亦均为无色透明液体，如图1，这是本试验配制的防雾剂能成为今后理想的鼻内镜防雾剂的前提条件。  \n\n有关超亲水表面防雾、自清洁特性的文献有不少报道[6-0].通常当水滴在某种物质表面形成的接触角小于90度时称该物质亲水，当物质表面被水浸润形成的接触角小于5度时称该物质超亲水1-14l。实验时水滴与鼻内窥镜蓝宝石镜面接触角的大小代表了水滴在镜面的铺展难易程度，接触角越小，表明雾滴或水汽在鼻内镜镜头表面易于铺展。图4和图5分别是蓝宝石镜面涂防雾剂前后水滴的接触角照片，从图4可以看出，未涂防雾剂蓝宝石镜面的接触角大约是73度，水滴在镜头表面几乎呈半球形。图5可以看出,涂防雾剂蓝宝石镜面的接触角明显降低，约7.6度，接近超亲水状态，水滴能够在镜头表面很好的铺展。实验时我们予临床上常用的鼻内镜防雾材料碘伏作为对照发现涂碘伏蓝宝石镜面的接触角约为  \n\n10度，如图8、图9，比实验所配制的鼻内镜防雾剂在蓝宝石镜面的接触角要大，这表明所配制的鼻内镜防雾剂的亲水性能要好于医用碘伏。本防雾剂因表面活性剂能很好地降低水的表面张力可使鼻内镜镜头表面亲水，明显降低镜头表面对水的接触角，使凝聚在表面上的雾滴或水汽不形成微小的水珠而是在内镜表面铺展开而薄膜化，防止鼻内镜镜头表面雾化，减少了对光线的折射和反射，从而保证了鼻内镜镜头的透明度和清晰度。图6、图7是Storz0°鼻内镜蓝宝石圆形镜片表面涂鼻内镜防雾剂前后扫描电镜照片，由图7可以发现,防雾剂涂在鼻内镜镜头表面形成一层平整膜。其防雾原理是由于添加的表面活性剂具有良好的润湿性，降低了水的表面张力，使水滴在薄膜上迅速铺展,而由于膜的形成降低了表面活性剂在使用过程中的流失，由此延长了防雾时间。图10、11是Storz0°鼻内镜镜片表面涂医用碘伏后扫描电镜照片，由图可以发现，医用碘伏涂在鼻内镜镜头表面后呈散在岛状分布，表面不规整，未能形成膜状结构，表明医用碘伏与鼻内镜镜头粘附不够牢固易流失，这也是我们实验得出防雾剂防雾时间明显好于医用碘伏的主要原因。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 37,
+        "chunk": "# 4结论  \n\n1.本实验通过统计软件SPSS13.0正交设计，配制出的28种防雾剂具有无色、无刺激性及镜面清晰度高特点，防雾时间明显较碘伏和医用乙醇长;  \n\n2.配制出的亲水型防雾剂防雾原理是由于防雾剂涂在鼻内镜镜头表面形成一层平整膜，延缓了表面活性剂在使用过程中的流失；其中的表面活性剂可降低水的表面张力，使雾滴在薄膜上迅速铺展开形成一层水膜从而达到防雾目的。  \n\n不足之处：1.防雾时间的测试目前无一统一标准，防雾计时存在人为主观因素；2.每种物质重量百分比设仅有3个水平，根据这3个水平所配制的防雾剂防雾时间也不一定是最好的，当然随着实验原料的重量百分比水平级别越多，所配制最佳配比的防雾剂的机率越大，但存在实验次数明显增多，测试工作更加困难等问题。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 38,
+        "chunk": "# 参考文献  \n\n[1] Hideki ISHOKA. Antifogging Glass for a Vehicle Window,Method for Producing the Same, and Fixing Structure for the same [P]. US Patent:0239017 A1,2009-9-24.   \n[2]Chen Zhao, Cormell Chappell. Silicate-Containing Antifogging Coatings [P]. US Patent:0003160 A1,2011-1-6.   \n[3]Timothy Michael Kneale, Clinton, Iowa. Antifog Composition for Polyolefin Packaging Films[P]. US Patent:6046254,2000-4-4.   \n[4] Seiji Yamazaki, Kensuke Makita, Yasuaki Kai. Hydrophilic Film and Method for Forming Same on Substrate [P]. US Patent:6071606,2000-6-6.   \n[5]Peter Daute, Ernst-Udo Brand. Antifogging Agent for Plastics [P]. US Patent:7488838B2,2009-2-10.   \n[6]Feng, X. Jiang, L. Design and Creation of Superwetting/Antiwetting Surfaces[J].Advnced Materials, 2006, 18,3063-3078.   \n[7]Cebeci, F. C,Wu, Z, Zhai, L,et al.Nanoporosity-Driven Superhydrophilicity:A Means to Create Multifunctional Antifogging Coatings[J].Langmuir, 2006, 22,2856-2862.   \n[8]Xian Ning Xie, Sharon Xiaodai Lim, Yuzhan Wang. A Nanosegregant Approach to Superwettable and Water-Atracting Surfaces[J].Macromol. Chem. Phys, 2010, 211,2187-2192.   \n[9] Jason Fang, Antonios Kelarakis, Luis Estevez, Superhydrophilic and solvent resistant coatings on polypropylene fabrics by a simple deposition process[J].Journal of Materials Chemistry,2010,20, 1651-1653.   \n[10] Feng X, Feng L, Jin M, PJ, et al.Reversible super-hydrophobicity to super-hydrophilicity transition of aligned ZnO nanorod films[J]. J Am Chem  \n\nSoc,2004，126,62-63.  \n\n[11]Hongchen Dong, Penglin Ye, Mingjiang Zhong.Superhydrophilic Surfaces via Polymer-SiO2Nanocomposites[J].Langmuir,2010,26,15567-15573.   \n[12]Han JT, Kim SY, Woo JS, et al.Transparent, conductive,and superhydrophobic films from stabilized carbon nanotube/silane sol mixture solution[J].Adv Mater,2008,20,3724-327.   \n[13] Takeshita N, Paradis LA, Oner D，et al.Simultaneous tailoring of surface topography and chemical structure for controlled wettability[J].Langmuir, 2004,20,8131-8136.   \n[14]Usrey ML, Strano MS.Controlling Single-Walled Carbon Nanotube Surface Adsorption with Covalent and Noncovalent Functionalization[J].Journal of PhysicalChemistryC.2009,113,12443-12453.  \n\n附图  \n\n![](images/515d7e958bac6d07d9e5d8a5d48f353579a66dd439d856c8acae820873e93683.jpg)  \n图1制备的不同配比透明防雾剂  \nFig.1 Different ratio of transparent antifogging agent  \n\n![](images/c12cce696a3fad97b6c4af9fc51513d26c28719a9224f66f357e2bdd6cbdd8f5.jpg)  \n图228号防雾剂透光率  \n\n![](images/e21d0fba6dd10be986553c6bf355dbd12d0f6e8cc7a59d2ef2c6e06088c505a8.jpg)  \nFig.2 light transmittance of the NO.28 antifogging agent   \n图315号防雾剂透光率  \nFig.3 light transmittance of the NO.15 antifogging agent  \n\n![](images/4d8da07342b4ac503e35625dc80f137d85bda1e84f3b30ae5e8e73180c99ffdd.jpg)  \n图4蓝宝石镜片涂防雾剂前接触角 Fig.4 contact angle of sapphire lens without antifogging agent coating  \n\n![](images/a6993ddea24a780706dca5b5b1ab259cbb5d1199245d4699c8ddbfa7d7d5957b.jpg)  \n图5蓝宝石镜片涂防雾剂后接触角 Fig.5 contact angle of sapphire lens with antifogging agent coating  \n\n![](images/28f61608f56f4c2f6b7c02c99780d608bd5c70771d46fc43fff40ff9a88f8f16.jpg)  \n图6：蓝宝石镜片涂防雾剂前电镜（ $\\times2000$ 一Fig.6 SEM of thesapphire lenswithoutantifogging agentcoating(x2000)  \n\n![](images/fca51add22aeedb902ec71aefb987420bf844b2503675b8f39c76412f054e2ad.jpg)  \n图7：蓝宝石镜片涂防雾剂后扫描电镜（ $\\times2000$ ) Fig.7SEMof thesapphirelenswith antifogging agent coating (x2000)  \n\n![](images/db09d43a943cb906169c863438f23769fb428ad602d665a72ab1039724a9e871.jpg)  \n博士学位论文  \n\n![](images/781100036af7daf76ec6c5494d8bd78d73638acb5e179d85630f58ea1833d5b4.jpg)  \n图9蓝宝石镜片涂碘伏表面接触角 Fig.9 contact angle of sapphire lens with betadine coating  \n\n![](images/aa9cd6f28e635ada024ceaeaeea30943aebc09af7e1b5046fd2dcd032d6a444c.jpg)  \n图8蓝宝石镜片涂碘伏表面接触角 Fig.8 contact angle of sapphire lens with betadine coating   \n图10蓝宝石镜片涂碘伏表面 扫描电镜（ $\\times2000$ ？ Fig.10 SEM of the sapphirelens with betadine coating (x 2000)  \n\n![](images/37a16d70fa98663138d8f17b5aa12deaa14ce8b5655205ef2c78a91420b216e4.jpg)  \n图11蓝宝石镜片涂碘伏表面扫描电镜（ $\\times10000^{\\cdot}$ ）Fig.11 SEM of the sapphire lenswithbetadinecoating $(\\mathbf{x}\\ 10000)$",
+        "category": " References"
+    },
+    {
+        "id": 39,
+        "chunk": "# 第二章 纳米粒子改性亲水型鼻内镜防雾剂研制  \n\n前言：喷涂型亲水性防雾剂主要靠物理吸附而粘附于固体表面，这种吸附防雾剂主要靠范德华力和氢键与固体表面结合，这就决定了喷涂型防雾剂与固体表面结合不牢固，容易从固定表面流失而影响其防雾性能。第一章所研制的亲水型鼻内镜防雾剂与临床上用于内镜防雾的医用碘伏、肥皂液与内镜表面同样存在结合不牢固问题。如何能增强液态防雾剂与鼻内镜表面粘附进而增强防雾剂防雾功能呢？目前有文献报道往防雾剂添加纳米粒子或氧化物利用纳米粒子或氧化物的桥接作用可增强防雾剂与固体表面的结合从而延长防雾剂防雾时间。鉴于此观点，本试验拟将自制的纳米二氧化硅按一定的质量百分比添加至第一章所研制的亲水型鼻内镜防雾剂中，探讨改性后的防雾剂防雾性能有何变化并进一步探讨其防雾性能改变的机理。",
+        "category": " Introduction"
+    },
+    {
+        "id": 40,
+        "chunk": "# 1材料和方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 41,
+        "chunk": "# 1.1 试剂与仪器",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 42,
+        "chunk": "# 实验试剂  \n\n<html><body><table><tr><td>试剂</td><td>规格</td><td>厂家</td><td></td></tr><tr><td>无水乙醇</td><td>a</td><td>分析纯</td><td>天津市富宇精细化工有限公司</td></tr><tr><td>丙二醇</td><td>b</td><td>分析纯</td><td>天津市化学试剂一厂</td></tr><tr><td>月桂醇聚氧乙烯醚</td><td>c</td><td>高级纯</td><td>Aladdin Chemistry Co.Ltd</td></tr><tr><td>十二烷基硫酸钠</td><td>d</td><td>化学纯</td><td>广州市化学试剂厂</td></tr><tr><td>聚乙二醇400</td><td>e</td><td>分析纯</td><td>广州市化学试剂厂</td></tr><tr><td>无水乙醇</td><td></td><td>分析纯</td><td>天津市富宇精细化工有限公司</td></tr><tr><td>氨水</td><td></td><td>25%，分析纯</td><td>广州市东红化工厂</td></tr><tr><td>正硅酸乙酯</td><td></td><td>28.4%</td><td>中国五联化工厂</td></tr></table></body></html>  \n\n氢氧化钠 分析纯 天津市福晨化学试剂厂正已烷 分析纯 江苏强盛化学股份有限公司乙二醇 分析纯 天津市红岩化学试剂厂去离子水 自制",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 43,
+        "chunk": "# 实验仪器  \n\n仪器 型号 厂家  \n超高分辨场发射扫描电镜 NanoSEM430 荷兰  \n紫外-可见分光光度计 Lambda 900 美国Perkin Elmer 公司  \n接触角仪 OCA20LHT 德国Dataphysics 公司  \n透射电镜 JEM-100CX II 日本电子公司  \n原子力显微镜 SPM-9500J3 日本SHIMADZU（岛津）公司  \nStorz0°鼻内镜及显像系统 德国Storz公司  \nStorz0°鼻内镜蓝宝石圆形镜片 德国Storz公司",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 44,
+        "chunk": "# 1.2 实验",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 45,
+        "chunk": "# 1.2.1纳米二氧化硅改性亲水型鼻内窥镜防雾剂制备  \n\n1.2.1.1二氧化硅纳米粒子制备：将无水乙醇 $75\\mathrm{ml}$ 、去离子水 $32.0\\mathrm{ml}$ 和 $25\\%$ 氨水$4.0\\mathrm{ml}$ 加入锥形瓶中 $20.0\\mathrm{^{\\circ}C}$ 磁力搅拌器下搅拌30分钟，后在在搅拌过程中缓慢滴加正硅酸乙酯（TEOS） $4.8\\mathrm{ml}$ ，在 $20.0\\mathrm{{^\\circC}}$ 继续搅拌12小时，即得纳米二氧化硅半透明悬浮液。  \n\n1.2.1.2 Nano $\\mathbf{sio}_{2}.$ -KH570制备：将制备的纳米 $\\mathbf{SiO}_{2}$ 离心后，再放入真空干燥箱中在 $100^{\\circ}\\mathrm{C}$ 时干燥24h。取纳米 $\\mathrm{SiO}_{2}1.0$ 克，无水乙醇 $20\\mathrm{ml}$ 和去离了 $20\\mathrm{ml}$ 加入烧杯中配制成溶液，超声分散3h后倒入烧瓶内。取0.05mlKH570溶于 $20\\mathrm{mL}$ 无水乙醇中，充分搅拌30分钟后再加入至上述纳米 $\\mathrm{SiO}_{2}$ 溶液内，在 $70^{\\circ}\\mathrm{C}$ 下恒温搅拌5h。最后将所得乳液进行高速离心（10000r/s）5分钟，去除上层液后加入无水乙醇超声分散10分钟，再离心，如此重复6次去除多余的KH570，干燥后得纳米 $\\mathrm{Si}0_{2}$ -KH570.  \n\n1.2.1.3亲水性鼻内镜防雾剂制备：按先后顺序将无水乙醇 $20\\mathbf{g}$ 、丙二醇 $10\\mathbf{g}$ 、月桂醇聚氧乙烯醚 $20\\mathbf{g}$ 、十二烷基硫酸钠 $4\\mathbf{g}$ 、聚乙二醇 $4004\\mathrm{g}$ ，去离子水 $42\\mathrm{ml}$ 加入烧瓶中混合并置于 $50^{\\circ}\\mathrm{C}$ 水浴箱30分钟后即得亲水性鼻内镜防雾剂。  \n\n1.2.1.4纳米二氧化硅改性亲水性鼻内镜防雾剂配制：取纳米 $\\mathbf{SiO_{2}}\\ 0.025\\mathbf{g}$ ：$0.050{\\bf g}$ 、 $\\mathbf{0.100g}$ 分别加入3试管相同的亲水性鼻内镜防雾剂 $\\mathfrak{s m}$ 中；取纳米$\\mathbf{SiO}_{2}$ -KH5700.025g、0.050g、0.100g分别加入3试管相同的亲水性鼻内镜防雾剂 $5\\mathrm{ml}$ 中,所配制的液体均超声分散30分钟即得六种不同改性的鼻内镜防雾剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 46,
+        "chunk": "# 1.2.2 防雾剂表征  \n\n1.2.2.1防雾时间：测试环境：温度 $20.5\\mathrm{^{\\circ}C}$ ，湿度： $72\\%$ ，气压： $1005.0\\mathrm{{hPa}}$ 。受试者签署知情同意书，剪鼻毛后平躺， $1\\%$ 丁卡因肾上腺素棉片行鼻腔粘膜表面麻醉，Storz0°鼻内镜及显像系统进行测试，鼻内镜镜头涂防雾剂后置于鼻闻处，从鼻内镜进入鼻腔至镜面开始起雾的时间即为防雾时间（选取两种防雾时间最长的配比： $0.050\\mathbf{g}\\ \\mathbf{SiO}_{2}$ 配比及 $0.050{\\bf g}$ 纳米 $\\mathbf{SiO}_{2}–\\mathbf{KH}570$ 配比行进一步表征）。  \n\n1.2.2.2透光率：首先用乙醇将石英比色皿清洗3次，再用待测液体将石英比色Ⅲ 清洗3次，取待测液体 $600\\mathrm{ul}$ 加入石英比色皿，予空白石英比色皿透光率为 $100\\%$ 作对照，测量波长范围 $350{-}800{\\mathrm{nm}}$ 0  \n\n1.2.2.3接触角：首先将上述防雾剂分别在洗净的蓝宝石镜片上涂膜自然晾干，测量水滴在上述样品表面的接触角。打开接触角检测仪连接计算机、接触角检测仪电源及接触角仪视频检测后打开检测光源，将制备好的Storz0°鼻内镜蓝宝石圆形镜片涂防雾剂样品置于检测台上,并用微量注射器缓慢地将 $3.0\\upmu\\mathrm{L}$ 的蒸馏水滴在涂膜上；调整目镜、载玻平台及光源位置，使光源中心、样品表面、蒸馏水滴、目镜在一个水平面上并保持直线；调节焦距至连接计算机视频中出现清晰图像；利用计算机视频截取水滴图像，读出水滴图像的左右两侧的接触角;在该样品上分别选取3个不同的测量点，取其平均值，并分别用接触角测量仪配套设备拍摄液滴在薄膜表面形貌照片。  \n\n1.2.2.4粘附功：1.先用标准水和标准乙二醇测量其在蓝宝石镜片上的接触角，然后利用OWRK(Owens-Wendt-Rabeland-Kaelble)公式计算出蓝宝石镜片表面的自由能，包括色散分量(Disp)、极性分量(Polar)，标准液体可选用（水、乙二醇、二碘甲烷、甲酰胺）。2.测量被测液体的表面张力（用悬滴法）和界面张力（悬滴法，液滴在正已烷中的界面张力）。3.对所测液体的表面张力进行分析包括色散分量(Disp)、极性分量(Polar)；4.接触角仪电脑软件计算出粘附功。  \n\n1.2.2.5透射电镜：将待测防雾剂予蒸馏水稀释3倍后用超声波震荡均匀后滴在微栅上，待其自然干燥后检测。利用日本电子公司JEM-100CXⅡ透射电子显微镜来观察颗粒形貌、分散程度和粒径。首先调好电镜灯丝像，关灯丝后插入样品，在完成电压中心、光栏、聚光镜像散、物镜像散调节后插入物镜光栏，在观察样品的时候调节，在高倍下找到一样品作为参照，改变焦距，观察样品并拍照。  \n\n1.2.2.6原子力显微镜:将蓝宝石镜片放入含有洗洁净溶液中超声清洗1小时，用超纯水反复冲洗镜片表面洗洁净溶液直至洗净，将蓝宝石镜片放于3mol/L的氢氧化钠溶液中浸泡3h，用去离子水反复冲洗，再用酒精清洗蓝宝石镜片吹干从而获得清洁的蓝宝石镜片表面。将蓝宝石镜片完全浸入待检测溶液后再缓缓取出后自然凉干，用日本SHIMADZU（岛津）公司SPM-9500J3原子力显微镜后对样品进行检测。检测时使用接触模式，首先将接触式的探针安装在悬臂夹中，再把涂有防雾剂的镜片粘于样品碟上并放于扫描管的上面，取下激光头，把装有探针的悬臂夹放入激光头中，用激光头后面的锁紧螺丝把悬臂夹锁紧，调整激光点到探针尖端的背面，设置并优化扫描参数，点击engage 按钮，计算机开始自动下针，当针接触到样品并且弯曲量达到预先设定的 setpoint值时，扫描管开始扫描。点击capture 按钮，开始抓取图象并拍照。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 47,
+        "chunk": "# 2结果  \n\n2.1",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 48,
+        "chunk": "# 防雾时间及防雾性能测试结果：  \n\n不同纳米粒子改性防雾剂鼻内窥镜防雾时间（min）Different antifogging time of nanoparticles modified nasal endoscopic antifoggant  \n\n\n<html><body><table><tr><td>类别</td><td>第1次</td><td>第2次</td><td>第3次</td><td>平均</td></tr><tr><td>防雾剂</td><td>14</td><td>16</td><td>14</td><td>15</td></tr><tr><td>防雾剂+0.025g</td><td>Nano SiO2 16</td><td>15</td><td>16</td><td>16</td></tr><tr><td>防雾剂+0.050g</td><td>Nano SiO2 19</td><td>17</td><td>18</td><td>18</td></tr><tr><td>防雾剂+0.100g</td><td>Nano SiO2 14</td><td>15</td><td>15</td><td>15</td></tr><tr><td>防雾剂+0.025g</td><td>Nano SiOz-KH570 17</td><td>19</td><td>18</td><td>18</td></tr><tr><td>防雾剂+0.050g</td><td>Nano SiO-KH570 21</td><td>22</td><td>20</td><td>21</td></tr><tr><td>防雾剂十0.100g</td><td>Nano SiOz-KH570</td><td>16 18</td><td>17</td><td>17</td></tr></table></body></html>\n\n注：时间精确到分，以 $30^{\\prime\\prime}$ 为界舍入。  \n\n2.2透光率：在可见光范围内防雾剂透光率为 $100\\%$ ，如图1；纳米 $\\mathrm{SiO}_{2}$ 改性防雾剂透光率约为 $90\\%$ ，如图3；纳米 $\\mathbf{SiO}_{2}.$ -KH570改性防雾剂透光率约为 $97\\%$ ，如图5。  \n\n2.3接触角：水滴在防雾剂涂膜上接触角7.8度，如图2；水滴在纳米 $\\mathbf{SiO}_{2}$ 改性防雾剂涂膜上接触角7.0度，如图4；水滴在纳米 $\\mathbf{SiO}_{2}$ -KH570改性防雾剂涂膜上的接触角6.7度，如图6。  \n\n2.4粘附功：水在蓝宝石镜面的接触角为(56.159.958.0)平均值为58.0度；乙二醇在蓝宝石镜面的接触角为(46.351.648.2)平均值为48.7度；蓝宝石镜面的表面能为 $52.36{\\pm}\\mathrm{mN}/\\mathrm{m}$ ，其中色散分量 $(\\mathrm{Disp}2.92{\\pm}\\mathrm{mN}/\\mathrm{m})$ ；极性分量 $(\\mathrm{Polar}49.44{\\pm}\\mathrm{mN}/\\mathrm{m})$ 标准水的表面张力为 $72.80{\\pm}0.05\\mathrm{mN/m}$ ，其中色散分量 $(\\mathrm{Disp}29.10\\mathrm{mN/m})$ ，极性分量(Polar $43.70\\ \\mathrm{mN/m})$ ；标准乙二醇的表面张力为 $48.00{\\pm}0\\mathrm{mN/m}$ ，其中色散分量 $(\\mathrm{Disp}29.00\\mathrm{mN/m})$ ，极性分量 $(\\mathrm{Polar~}19.00\\mathrm{\\mN/m})$ 。  \n\n防雾剂在蓝宝石镜面的粘附功测量数值 $\\mathbf{\\left(mN/m\\right)}$   \n\n\n<html><body><table><tr><td colspan=\"10\"> measurement values of the adhesion work between antifoggant and sapphire lens</td></tr><tr><td colspan=\"5\">参数 表面张力</td><td colspan=\"3\">界面张力</td><td rowspan=\"2\">分量 分量</td><td rowspan=\"2\">色散极性粘附</td><td rowspan=\"2\">功</td></tr><tr><td>样品</td><td>第一</td><td>第二</td><td>第三</td><td>平均 第一</td><td>第二</td><td>第三</td><td>平均</td></tr><tr><td></td><td>36.96</td><td>37.12</td><td>36.98 37.01</td><td>4.71</td><td>4.79</td><td>4.70</td><td>4.73</td><td>34.88</td><td>2.13</td><td>40.71</td></tr><tr><td>2</td><td>36.40 36.42</td><td>35.25</td><td>36.02</td><td>6.45</td><td>6.37</td><td>6.48</td><td>6.43</td><td>31.28</td><td>4.74</td><td>49.73</td></tr><tr><td>3</td><td>35.52</td><td>36.84</td><td>35.42</td><td>35.93 7.87</td><td>8.01</td><td>8.45</td><td>8.11</td><td>29.02</td><td>6.91</td><td>55.38</td></tr></table></body></html>\n\n注：样品1指防雾剂；样品2指纳米 $\\mathrm{\\ttSiO}_{2}$ 改性防雾剂；样品3指纳米 $\\mathbf{SiO}_{2}$ -KH570改性防雾剂。  \n\n2.5透射电镜： $\\mathrm{SiO}_{2}$ 径粒约 $100{\\sim}200\\mathrm{nm},$ 呈球形，纳米 $\\mathrm{SiO}_{2}$ 在防雾剂中分散较差，团聚明显，如图9；改性纳米 $\\mathbf{SiO}_{2}$ -KH570在防雾剂中的分散性明显提高，基本呈单个纳米粒子分布，如图10。  \n\n2.6原子力显微镜：研制的鼻内镜防雾剂在蓝宝石镜面形成一均匀的薄膜厚约$192.30\\mathrm{nm}$ ，膜表面较平整，如图11，图12；纳米 $\\mathrm{SiO}_{2}$ 改性防雾剂形成的薄膜最厚处约 $200.09\\mathrm{nm}$ ，膜表面较单纯防雾剂表面粗糙，纳米粒子明显团聚，粒径范围约 $100{\\sim}200\\mathrm{nm}$ ，如图13；纳米 $\\mathbf{SiO}_{2}$ -KH570改性防雾剂形成的薄膜最厚处约$332.38\\mathrm{nm}$ ，膜表面较单纯防雾剂表面粗糙，纳米粒子分散较均匀，如图14。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 49,
+        "chunk": "# 3讨论  \n\n光学材料已广泛应用于工农业及医疗行业，如汽车建筑玻璃、医用内镜，但光学材料表面容易起雾可导致光的散射而影响其功能[。雾化是由于温度、湿度的改变导致水汽凝结而引起的，当材料表面的温度低于露点温度，随着湿度增加，环境中的水汽会在材料表面凝结[2。防雾问题已引起学者的广泛关注。自上世纪90年代以来，防雾材料的制备陆续已有不少报道，所报道的防雾材料绝大多数为亲水材料[-5。因雾滴可在亲水材料表面形成一层水膜或近似水膜，减少对光的散射，保证材料的透光率[6][7]。通常认为防雾性能与亲水性能成正相关，但目前对防雾性能评价尚无统一的标准。实验所研制的鼻内镜防雾剂中的表面活性剂因同时含有亲水和亲油基团，具有良好的界面活性，其防雾性能主要与以下两种因素有关，第一：防雾剂在鼻内镜表面形成薄膜的表面张力大小，当水汽与防雾剂在内镜表面形成膜的表面张力越接近时，水汽对防雾剂形成薄膜面越易浸润，水汽或雾滴在防雾剂薄膜上的接触角就会越小甚至趋于0度，水汽或雾滴越易在防雾剂薄膜表面铺展开形成一层水膜进而减少对光的漫反射达到防雾的目的，防雾剂防雾性能就越好。反之，当水汽与防雾剂形成膜面的表面张力相差越大，水汽对防雾剂形成薄膜面浸润就越差，水汽或雾滴在防雾剂形成薄膜面越难铺展开形成水膜，其防雾性能就越差。第二：防雾剂与鼻内镜表面的粘附强度有关，当防雾剂与鼻内镜表面的粘附越强时，防雾剂在内镜表面形成的薄膜越不易流失从而延长其防雾功能，反之防雾性能则越差。  \n\n上章已提到碘伏在鼻内镜蓝宝石表面实际难以形成一层均匀的膜，而呈岛状结构表明其与内镜表面的粘附强度不够，在鼻内镜表面易流失影响其防雾性能。酒精因其易挥发的特点影响其防雾性能。与碘伏、酒精等相比，虽上章所研制的亲水性鼻内镜防雾剂防雾时间明显延长，但同样存在与鼻内镜表面存在结合力不够强易流失而影响其防雾性能的缺点。如何进一步增强亲水性防雾剂与内镜表面的结合力从而延长防雾剂防雾时间是本章重点研究的内容。目前有文献报道往防雾剂添加纳米粒子或氧化物可增强防雾剂与固体表面的结合从而延长防雾剂防雾时间[9-11l。基于此观点，本章利用自制的纳米二氧化硅对所研制的亲水性鼻内镜防雾剂进行改性探讨了防雾剂防雾性能有何变化及变化机理。  \n\n纳米二氧化硅是一种无色、无味、无毒的白色粉末状材料，在工业及医药领域用途十分广泛[2]。纳米二氧化硅具有特殊的表面结构和电子能级结构，这使之具有普通粒子所不具有的小尺寸效应、表面效应，使其在热、光和表面稳定性等方面不同于常规粒子[13]。纳米二氧化硅因其粒径小，比表面积很大，表面能高，处于热力学非稳定状态，极易聚集成团，将其直接添加至防雾剂中势必影响防雾剂的透光率，而作为好的防雾剂所具备的首要条件就是要有好的透光率。要解决上述纳米二氧化硅在防雾剂中分散性问题，有必要对其表面进行改性，降低表面能以提高纳米粒子的分散性[14][15]。目前已有作者往纳米二氧化硅中加入硅烷偶联剂对其进行改性，因硅烷偶联剂水解产物极易吸附在 $\\mathbf{SiO}_{2}$ 微粒表面与二氧化硅网络结构的表面羟基脱水缩合，阻碍了微粒间氢键的作用，达到了阻止纳米二氧化硅团聚的目的，得到单分散 $\\mathbf{SiO}_{2}$ 微粒[16][17]。  \n\n实验中采用的硅烷偶联剂KH-570，化学名称：-（甲基内烯酰氧）内基三甲氧基硅烷，分子式： $\\mathrm{CH2}{=}\\mathrm{C}(\\mathrm{CH3})\\mathrm{COOC3}\\mathrm{H6}\\mathrm{Si}(\\mathrm{OCH3})3$ ，是一种有机官能团硅烷偶联剂。硅烷偶联剂与二氧化硅表面羟基之间很容易发生脱水缩合作用，连接在 $\\mathrm{SiO}_{2}$ 表面的偶联剂可以阻碍颗粒之间的团聚，使得纳米 $\\mathbf{SiO}_{2}$ 在防雾剂中具有良好的分散性。利用硅烷偶联剂KH-570对纳米 $\\mathbf{SiO}_{2}$ 粉体表面进行改性后二氧化硅分散性明显提高有不少文献报道[18-21]。本实验予硅烷偶联剂KH-570对自制的纳米 $\\mathrm{SiO}_{2}$ 表面进行了改性。通过电子显微镜检测，改性后纳米二氧化硅在防雾剂中达到纳米级的分散，分散性明显提高，呈单个粒子分布，如图10，而在未改性纳米二氧化硅在防雾剂中团聚现象较明显，如图9，这势必会在一定程度上影响其透光率。在可见光范围内所研制防雾剂的透光率约为$100\\%$ ;纳米 $_{\\mathsf{S i O}_{2}-\\mathsf{K H}570}$ 改性防雾剂因纳米粒子分散较好其透光率也接近 $100\\%$ 约为 $97\\%$ ；纳米 $\\mathbf{SiO}_{2}$ 改性防雾剂因纳米粒子有团聚现象其透光率受一定的影响约为 $90\\%$ 但都达到了作为防雾剂透光率要求。  \n\n液态喷涂型防雾剂能延缓从鼻内镜镜面的流失是其具有良好防性能的必要条件。为了解防雾剂与鼻内镜镜面的粘附就必须对其两者之间的界面进行了解。目前表征固液界面的相互作用还较困难[22]。但已有学者通过热力学自由能及湿润来阐述固液界面的相互作用[23]。在所有相互作用的系统中，表面自由能起着至关重要的作用[24]。在探讨固液界面的相互作用时粘附功可一定程度体现液体与固体之间的粘附强度[25]。本实验重点从粘附功角度探讨了所制备的防雾剂与鼻内镜之间的粘附强度从而可一定程度解释不同防雾剂的防雾性能为何不同。在固液接触体系中，其界面因受到固液表面两相的分子力作用而存在吸附，要分离固液界面两相的吸附所作的功即为粘附功Wa，它是液、固粘附时，体系对外所做的最大功，如下图示。  \n\n![](images/2ec10d13ae9105240079f207a46267ca4de533e614c2900f4ee4d58288f23278.jpg)  \n\n$$\n\\mathrm{W_{2}=\\gamma_{_{g-1}}+\\gamma_{_{g-s}}-\\gamma_{_{l-s}}}\n$$  \n\n从示意图可以看出，Wa值越大，液体愈容易润湿固体，液、固界面结合得愈牢固。理论粘附功与表面相貌、极性表面自由能及表面的物理化学均质性有关[26]。为得到有意义的粘附功值，要在相同的环境下测量两种或以上标准液体（水、乙二醇、二碘甲烷、甲酰胺等）在待测固体表面的接触角，计算出固体的表面能，包括极性分量及色散分量，还要测待测液体的表面张力及界面张力，表面张力指液气界面时液体的表面张力，通常用悬滴法测量，实验时表面张力数值较易测出，如图7。界面张力指液液界面时待测液体的表面张力，亦用悬滴法，通常测量液滴在正已烷中的界面张力，如图8。但可能因防雾剂表面能与正已烷表面能接近，界面张力太小， $4.70{\\sim}4.79\\mathrm{mN/m}$ ，平均也仅 $4.73\\mathrm{mN/m}$ ，界面张力数值较难测出，改性后的防雾剂因纳米粒子的添加，在正已烷中的界面张力有所增加，但也仅为 $6.43\\ \\mathrm{mN/m}\\mathcal{F}||8.11\\ \\mathrm{mN/m}$ ，界面张力数值亦较难测出。另外，测量粘附功时要考虑影响液固相相互作用的相关因素[27]。液体与固体之间的粘附强度与固体表面能极性比及液体表面能极性比有关，通常两者表面能极性比越接近，表明液体越容易浸润固体，其粘附功值会越大。本实验中，防雾剂与鼻内镜蓝宝石镜面的粘附功为 $40.71\\mathrm{mN/m}$ ，而添加了纳米粒子的防雾剂与鼻内镜蓝宝石镜面的粘附功均有增加，纳米 $\\mathbf{SiO}_{2}$ 改性防雾剂与鼻内镜蓝宝石镜面的粘附功 $49.73\\mathrm{\\mN/m}$ ，纳米 $\\mathrm{SiO}_{2}$ -KH570改性防雾剂与鼻内镜蓝宝石镜面的粘附功$55.38~\\mathrm{mN/m}.$ 这可能一方面由于纳米粒子的存在，因其桥接作用对液态防雾剂有一定的固定作用，另外，从实验数据可以看出，鼻内镜蓝宝石镜面表面能色散分量 $2.92\\mathrm{mN/m}$ ，极性分量 $49.44\\mathrm{mN/m},$ 极性比为94：100，极性比较大，而未经改性的防雾剂色散分量 $34.88~\\mathrm{mN/m}$ ，极性分量 $2.13~\\mathrm{mN/m}$ ，极性比仅为6：100，两者极性比相差较大，粘附功值也相对较小。而纳米粒子的添加改变了防雾剂的极性，纳米 $\\mathbf{SiO}_{2}$ 改性防雾剂色散分量 $31.28~\\mathrm{mN/m}.$ ，极性分量 $4.74~\\mathrm{mN/m}$ ，极性比为13:100；纳米 $\\mathrm{SiO}_{2}$ -KH570改性防雾剂色散分量 $29.02\\ \\mathrm{mN/m},$ ，极性分量6.91$\\bf{m N}/\\bar{m}$ ，极性比为19:100；经纳米二氧化硅改性后的亲水性防雾剂极性均有提高，其表面能极性比更接近鼻内镜蓝宝石表面能极性比，与鼻内镜蓝宝石基体之间可能出现化学键结合，增强了防雾剂与鼻内镜蓝宝石镜面的粘附，延缓了防雾剂在鼻内镜镜面的流失，提高了防雾性能。通常对同一固体表面，液体的极性越大，粘附功一般也越大。翟兰兰等在研究低密度聚乙烯涂料与钢铁之间的粘附强度时，往聚乙烯涂料中添加一定质量百分比的纳米Si0颗粒、纳米氧化铝颗粒及纳米碳酸钙颗粒后，由于聚乙烯涂料极性发生改变，导致含有纳米颗粒的聚乙烯涂料与金属基体之间出现化学键的结合而增强了聚乙烯涂料与金属基体之间的结合[28]。但潘慧铭等认为：理论粘附功不完全等同于实际粘接强度，影响实际粘接强度的存在众多因素，而粘附功仅是主要影响因素之一[29]。  \n\n不少学者用原子力显微镜来研究固液界面[30][31]。原子力显微镜是一种可用于对有机/无机薄膜和生物材料表面形貌产生高分辨率图像的的技术。本实验原子力显微镜图表明研制的鼻内镜防雾剂在蓝宝石镜面形成一均匀的薄膜厚约$192.30\\mathrm{nm}$ ，膜表面较平整；防雾剂中添加 $\\mathrm{SiO}_{2}$ 纳米粒子后，膜表面变厚且较单纯防雾剂表面要粗糙，突点明显增多，尺寸约在 $200{\\sim}330\\mathrm{nm}$ ，这些突点为纳米粒子所在处，由于纳米粒子的固定作用增强了防雾剂与玻璃基片的粘附，从而延缓防雾剂在玻璃基片表面的流失，延长了防雾时间，提高防雾剂的防雾性能。罗茂鲜等通过实验认为向防雾剂添加 $\\mathrm{SiO_{x}}$ 纳米粒子后因纳米粒子桥接作用可使防雾剂防雾时间延长9]。  \n\n另外，从实验数据可以看出添加了纳米粒子的防雾材料其亲水性比单纯防雾剂亲水性要好。接触角测量示水滴在防雾剂涂膜上接触角7.8度；水滴在纳米$\\mathrm{SiO}_{2}$ 改性防雾剂涂膜上接触角7.0度；水滴在纳米 $\\mathrm{SiO}_{2}$ -KH570改性防雾剂涂膜上的接触角6.7度。改性后的防雾材料亲水性能改善与材料表面要粗糙度增加有关，这是解释添加纳米粒子的亲水材料比单纯防雾剂的防雾性能要好的另一重要原因。Wenzel认为对于亲水材料而言，随着材料表面的粗糙度增加，其亲水性能亦增加，这可以由Wenzel's方程来解释[32]。对于粗糙亲水材料表面而言，因二维毛细管效应，液体可浸润固体表面从而形成一液固复合表面，增加固液接触面积，水滴可几乎牢固地粘附于亲水材料表面增强了亲水材料的亲水性能[33]。  \n\n![](images/c06d0d105edb6ce47450c727d5e22bd61dc88973eee9b9730f671196ea6ab325.jpg)  \n\n但在实验时并不是纳米粒子质量百分比越大防雾性能就越好，5ml防雾剂中加入0.050g $\\mathbf{SiO}_{2}$ 及 $\\mathbf{0.050g}$ 纳米 $\\mathbf{SiO}_{2}.$ -KH570的配比防雾时间最长，随着纳米粒子质量百分比的增加其防雾性能有所下降，可能由于纳米粒子含量增加，防雾剂表面微纳米级的粗糙结构反而不典型所致，另外，当 $\\mathsf{5m l}$ 防雾剂中加入 $0.100\\mathbf{g}\\ \\mathbf{SiO}_{2}$ 及$0.100{\\bf g}$ 纳米 $\\mathrm{\\bfSiO}_{2}$ -KH570的配比时，防雾剂透光率明显下降。故认为 $\\mathrm{5ml}$ 防雾剂中加入0.050g $\\mathbf{SiO}_{2}$ 及 $0.050{\\bf g}$ 纳米 $\\mathrm{SiO}_{2}$ -KH570的配比为最佳配比。本试验通过纳米二氧化硅对亲水性鼻内镜防雾剂改性，其与鼻内镜蓝宝石镜面的粘附增强，亲水性能进一步增强，防雾性能也进一步提高，从鼻内镜防雾测试试验可以看出，单纯防雾剂组平均防雾时间为 $15\\mathrm{{min}}$ ，纳米 $\\mathbf{SiO}_{2}$ 改性防雾剂剂组平均防雾时间为$18\\mathrm{{min}}$ ，纳米 $\\mathrm{SiO}_{2}$ -KH570改性防雾剂平均防雾时间为21min，而改性后的防雾剂透光率并未受太大影响。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 50,
+        "chunk": "# 4结论  \n\n1.本实验通过添加一定质量百分比的纳米二氧化硅及纳米 $\\mathbf{SiO}_{2}$ -KH570对亲水型防雾剂进行改性，通过防雾试验得出改性后的防雾剂防雾时间延长，通过粘附功及表面形态解释了改性后的鼻内镜防雾剂其性能要好于改性前防雾剂的主要原因是：提高了防雾剂表面能极性比；因涂膜后表面粗糙度增加增强了亲水性能。  \n\n2.纳米二氧化硅因比表面积大易发性团聚，经硅烷偶联剂KH-570改性后其分散性能有所提高。  \n\n不足之处：1.缺少X射线光电子能谱（X-rayPhotoelectron Spectroscopy）XPS对化学位移及化学键的检测。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 51,
+        "chunk": "# 参考文献  \n\n[1] Cebeci FC, Wu Z, Zhai L, Nanoporosity-driven superhydrophilicity: a means to create multifunctional antifogging coatings[J].Langmuir, 2006,22(6):2856-2862.   \n[2] Margrain TH, Owen C. The misting characteristics of spectacle lenses [J].Ophthalmic Physiol Opt.1996,16(2):108-14.   \n[3] Timothy Michael Kneale, Clinton, Iowa. Antifog Composition for Polyolefin Packaging Films[P]. US Patent:6046254,2000-4-4.   \n[4]  Seiji Yamazaki, Kensuke Makita, Yasuaki Kai. Hydrophilic Film and Method for Forming Same on Substrate [P]. US Patent 6071606, 2000-6-6.   \n[5]Peter Daute, Ernst-Udo Brand. Antifogging Agent for Plastics [P]. US Patent 7488838B2,2009-2-10.   \n[6]B. J. Briscoe, K. P. Galvin.The effect of surface fog on the transmittance of light[J].Solar Energy, 1991,46(4):191197.   \n[7] H. Zhao, D. Beysens.From droplet growth to film growth on a heterogeneous surface:condensation associated with a wettability gradient[J]. 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Chem. B 2002,106,12594-12599.   \n[23] Kwok D Y, Neumann A W. Contact angle measurement and contact angle inter  \n\n-pretation [J].Advances in Colloid and Interface Science , 1999 , 81,167-249.  \n\n[24] Doyle JD, Oldring K, Churchley J,et al. Struvite formation and the fouling propensity of different materials[J].Water Res, 2002 , 36(16): 3971-3978.  \n\n[25] Aldo Handojo , Yumei Zhai , Gerald Frankel , et al.Measurement of adhesion strengths between various milk products on glass surfaces using contact angle measurement  and atomic  force  microscopy[J].  Journal  of  Food Engineering,2009,92,305-311.  \n\n[26] Bargir S, Dunn S,Jefferson B.The use of contact angle measurements to estimate the adhesion propensity of calcium carbonate to solid substrates in water[J].Applied Surface Science, 2009,255(9): 4873-4879.  \n\n[27] N. Eustathopoulos, N. Sobczak, A. Passerone,et al. Measurement of contact angleand work of adhesion at high temperature[J].Journal of Materials Science,2005,40,2271-2280.  \n\n[28]翟兰兰，凌国平，郦剑.纳米颗粒改性聚乙烯与钢铁的附着机理[J].材料科学 与工程学报,2007,25(5):676-679  \n\n[29]潘慧铭，黄素娟.表面、界面的作用与粘接机理[J].粘接,2003,24(2):40-45.  \n\n[30] A. Roters, M. Schimmel, J. Ruhe,et al. Collapse of a polymer brush in poor solvent probed by noise analysis of a scanning force microscope cantilever[J].Langmuir,1998 ,14, 3999-4004.  \n\n[31] M. Gelbert, A. Roters, M. Schimmel,et al. Viscoelastic spectra of soft polymer interfaces obtained by noise analysis of AFM cantilevers[J]. Surf.Interface Anal, 1999,27,572-577.  \n\n[32] Wenzel, RN. Resistance of Solid Surfaces to Wetting by Water[J].Ind. Eng. Chem.,1936,28:988-994.  \n\n[33]  Bico J, Thiele U, Quere D. Wetting of textured surfaces[J].Colloids and Surfaces A, 2002, 206,41-46.  \n\n![](images/f683a940484454fdc457ee4517d6188a3fa14fe852369a44c431ff087bda209c.jpg)  \n附图  \n\n![](images/47eac20216fada810b4c3baf8ca925c4db238bdd0bb2fb99bd1010d1f380fe02.jpg)  \n图2防雾剂接触角7.8度 Fig.2 contact angle of 7.8 degrees  \n\n![](images/57559bcb0c516e3b1a80fdf040f0af7e1a5ad12b9ae8d9a11154baa0afb452d8.jpg)  \n图1防雾剂透光率  \n图3纳米 $\\mathrm{Si0_{2}}$ 改性防雾剂  \nFig.3 light transmittance of antifoggant modifiedbynano $\\mathrm{SiO_{2}}$  \n\n![](images/1c2367fa1961e93be61662431208bf72cafb4d326a1f647320c47d6f9571dcbf.jpg)  \nFig.1 light transmittance of antifoggant   \n图4纳米 $\\mathrm{Si}0_{\\mathrm{2}}$ 改性防雾剂接触角7.0度  \nFig.4 contact angle of 7.0 degrees  \n\n![](images/a19e131dbcb4e3e687a9283c2dd2a92131057e2d2b7d9a71e572f62da4280bcd.jpg)  \n图5纳米 $S_{i}0_{:}-\\mathsf{K H}570$ 改性防雾剂 Fig.5 light transmittance of antifoggant modifiedbynano $\\mathrm{SiO}_{2}$ -KH570  \n\n![](images/fff5c85c6347554dad871136f27149fcfaede737587da4191a72bef785fef20c.jpg)  \n图6纳米Si0-KH570改性防雾剂接触角6.7度  \n\n![](images/642eccc87b4f2e2e0b57f2ebe80f1230d10c88a46c3b60c762520dfb2c824c83.jpg)  \n图7在空气中测界面张力 Fig.7measuring interfacial tensionin air  \n\n![](images/7ec0e60943670ba12dd109bb3101fa8662ad2fbda2cc908926ef3d981f3f7a4e.jpg)  \nFig.6 contact angleof 6.7 degrees   \n图8在正已烷中测界面张力 Fig.8 measuring interfacial tensionin n-hexane  \n\n![](images/4bacc83f8ec0ced29c2baee3638a668728da3295f324059080d66c5cf7f39a55.jpg)  \n图9透射电镜检测纳米 $\\mathrm{SiO}_{2}$ 改性防雾剂结果（ $\\times50000$ D  \n\n![](images/4a721448ee0e26b6074c47c2f1f1a5c70d32fb612db9b4bececcaea42ef0393c.jpg)  \nFig.9 TEM of of antifoggant modified by nano $\\mathbf{SiO}_{2}$   \n图10透射电镜检测纳米 $\\mathbf{SiO}_{2}$ -KH570改性防雾剂结果（ $\\times50000$ ） Fig.10 TEM of antifoggant modified by nano $\\mathrm{SiO}_{2}$ KH570  \n\n![](images/83702d3653de0169b37f67e5dd0ed91a0e4acd0eef0e8d05b8e92b17253ab65d.jpg)  \n图11原子力显微镜检测防雾剂结果 Fig.11 AFM of antifogging agent  \n\n![](images/2edb9318839c583577423f49248f4e38b6ce8551accd850358c5fdff1ade8535.jpg)  \n图12原子力显微镜检测防雾剂结果 Fig.12 AFM of antifogging agent  \n\n![](images/2a7319f481e4db0eba632c44f09a16ad62a6688afe0819639367c9640e6bfd6d.jpg)  \n图13原子力显微镜检测纳米二氧化硅改性防雾剂结果  \n\n![](images/e7452eb2b7a648eb0187b2c890560207dee190589d7d07c7e501ca7a026d178a.jpg)  \nFig.13AFM of $\\mathrm{SiO}_{2}$ modified antifogging agent   \n图14原子力显微镜检测纳米二氧化硅-KH570改性防雾剂结果Fig.14AFM of Nano $\\mathrm{SiO}_{2}$ -KH570modifiedantifogging agent",
+        "category": " References"
+    },
+    {
+        "id": 52,
+        "chunk": "# 第三章 纳米粒子改性聚乙烯吡咯烷酮鼻内镜防雾剂研制  \n\n前言：医用碘伏是目前临床较常用的鼻内镜防雾剂，碘伏通用名为聚维酮碘，是碘与表面活性剂聚乙烯吡咯烷酮相结合而成的松散络合物，碘伏作为鼻内镜防雾的主要原理是其组分聚乙烯吡咯烷酮具有表面活性剂的功能而使得其具有一定的防雾性能。在第一部分的研究中发现碘伏作为鼻内镜防雾剂也存在如下缺点：防雾时间不够长，在鼻内窥镜上呈岛状分面很难形成一较均匀的膜，另外碘伏因含有碘也影响了其透光率，经检测，在可见光范围内碘伏透光率仅约为 $80\\%$ 。为了克服上述缺点。能否以一定浓度的聚乙烯吡咯烷酮溶液作用鼻内镜防雾剂，因不含碘，所制备的聚乙烯吡咯烷酮应是无色透明的；另外，基于往防雾剂添加纳米粒或氧化物利用纳米粒或氧化物的桥接作用可增强防雾剂与固体表面的结合从而延长防雾剂防雾时间的观点，对聚乙烯吡咯烷酮进行改性，往聚乙烯吡咯烷酮溶液中添加一定的质量百分比的纳米氧化锌、纳米氧化钛及中空纳米二氧化硅，探讨改性后的防雾剂防雾性能有何变化并进一步探讨其防雾性能改变的机理。",
+        "category": " Introduction"
+    },
+    {
+        "id": 53,
+        "chunk": "# 1材料和方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 54,
+        "chunk": "# 1.1 试剂与仪器",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 55,
+        "chunk": "# 实验试剂  \n\n<html><body><table><tr><td>试剂</td><td>规格</td><td>厂家</td></tr><tr><td>PVP K88-96</td><td>Mw 1300000</td><td>Aladdin Chemistry Co.Ltd</td></tr><tr><td>纳米氧化锌</td><td>90±10nm</td><td>Aladdin Chemistry Co.Ltd</td></tr><tr><td>钛酸丁酯</td><td>≥99.0% (GC)</td><td>Aladdin Chemistry Co.Ltd</td></tr><tr><td>盐酸</td><td>ACS, 37%</td><td>Aladdin Chemistry Co.Ltd</td></tr><tr><td>正硅酸乙酯</td><td>28.4%，分析纯</td><td>中国五联化工厂</td></tr></table></body></html>  \n\n聚丙烯酸 Mw 3000 Aladdin Chemistry Co.Ltd氢氧化钠 分析纯 天津市福晨化学试剂厂无水乙醇 分析纯 天津富宇精细化工有限公司",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 56,
+        "chunk": "# 实验仪器  \n\n仪器 型号 厂家  \n数控超声波清洗器 KQ100DB 昆山市超声仪器有限公司  \n超高分辨场发射扫描电镜 NanoSEM430 荷兰  \n紫外-可见分光光度计 Lambda 900 美国Perkin Elmer 公司  \n接触角仪 OCA20LHT 德国Dataphysics 公司  \n恒温磁力搅拌器 GB-3 上海雷磁创益仪器有限公司  \n透射电镜 JEM-100CX II 日本电子公司  \n原子力显微镜 SPM-9500J3 日本SHIMADZU公司  \nStorz0°鼻内镜及显像系统 德国Storz公司  \nStorz $\\boldsymbol{\\mathrm{0}}^{0}$ 鼻内镜蓝宝石圆形镜片 德国Storz公司",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 57,
+        "chunk": "# 1.2 实验",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 58,
+        "chunk": "# 1.2.1纳米氧化锌、纳米二氧化钛、纳米二氧化硅中空微球改性亲水型鼻内窥镜防雾剂制备  \n\n1.2.1.1纳米二氧化钛制备：取钛酸丁酯 $10\\mathrm{ml}$ 加入至 $\\mathbf{40ml}$ 无水乙醇中，充分搅拌1小时，盐酸 $2\\mathrm{ml}$ 及去离子水3ml加入至 $\\mathbf{8ml}$ 无水乙醇中，充分搅拌10分钟后磁力搅拌器下缓慢滴入至上述钛酸丁酯乙醇溶液，调节 $\\mathrm{PH}{=}5$ ，并在 $30^{\\circ}\\mathrm{C}$ 下反应24小时。将反应物质（转速 $6000\\mathrm{rpm}$ ）离心分离后，在 $100^{\\circ}\\mathrm{C}$ 的烘箱中放置10小时后将烘干的物质放入马弗炉中升温2h至 $500^{\\circ}\\mathrm{C}$ ，保温0.5h后自然降温，得到纳米二氧化钛。  \n\n1.2.1.2纳米二氧化硅中空微球制备：将0.50g聚丙烯酸溶于 $\\mathsf{5.60m l}$ 氨水中至充分溶解，加入 $100\\mathrm{ml}$ 无水乙醇，磁力搅拌器快速搅拌下缓慢滴加正硅酸乙酯 $2.00\\mathbf{m},$ 室温下搅拌12小时，将反应物质（转速 ${\\bf6000r p m}$ ）离心分离5分钟后，去除上层，加入去离子水，超声分散15分钟，再离心，如此予去离子水洗4次，将离心物在$100^{\\circ}\\mathrm{C}$ 的烘箱中放置6小时干燥后得到纳米二氧化硅中空微球。  \n\n1.2.1.3聚乙烯吡咯烷酮溶液制备：将9克聚乙烯吡咯烷酮溶于80ml去离子水中，在 $60^{\\circ}\\mathrm{C}$ 水浴恒温下搅拌4小时充分溶解。  \n\n1.2.1.4纳米粒子改性聚乙烯吡咯烷酮亲水型鼻内窥镜防雾剂制备：将0.025g、$0.050{\\bf g}$ 、 $\\mathbf{0.100g}$ 纳米二氧化锌分别加入3试管相同的 $\\mathsf{5m l}$ 聚乙烯吡咯烷酮溶液;0.025g、0.050g、 $\\mathbf{0.100g}$ 纳米氧化钛分别加入3试管相同的 $5\\mathrm{ml}$ 聚乙烯吡咯烷酮溶液; $0.025\\mathbf{g}\\cdot0.050\\mathbf{g}\\cdot\\mathbf{0.100g}$ 纳米二氧化硅中空微球分别加入3试管相同的 $5\\mathrm{ml}$ 聚乙烯吡咯烷酮溶液，所有液体均超声分散30分钟即得不同鼻内窥镜防雾剂。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 59,
+        "chunk": "# 1.2.2 防雾剂表征  \n\n1.2.2.1防雾时间:鼻内窥防雾试验：测试环境：温度 $13.0^{\\circ}\\mathrm{C}$ ，湿度： $65\\%$ ，气压：1020.0hPa。受试者签署知情同意书，剪鼻毛后平躺，1%丁卡因肾上腺素棉片行鼻腔粘膜表面麻醉，Storz0°鼻内镜及显像系统进行测试，鼻内镜镜头涂防雾剂后置于鼻闻处，从鼻内镜进入鼻腔至镜面开始起雾的时间即为防雾时间。（选取防雾时间最长的配比：0.050g纳米氧化锌配比、0.025g二氧化钛配比、及0.050g纳米二氧化硅中空微球配比行进一步表征）。  \n\n1.2.2.2透光率:对PVP、改性PVP及碘伏的透光率进行检测，先用乙醇将石英比 色皿清洗3次，再用待测液体将石英比色Ⅲ清洗3次，将待测液体600ul加入石 英比色Ⅲ，予空白石英比色皿透光率为 $100\\%$ 作对照，测量波长范围 $350{-}800\\mathrm{nm}$  \n\n1.2.2.3接触角：首先将上述防雾剂分别在洗净的蓝宝石镜片上涂膜自然晾干，测量水滴在上述样品表面的接触角。打开接触角检测仪连接计算机、接触角检测仪电源及接触角仪视频检测后打开检测光源，将制备好的Storz0°鼻内镜蓝宝石圆形镜片涂防雾剂样品置于检测台上,并用微量注射器缓慢地将 ${3.0\\upmu\\mathrm{L}}$ 的蒸馏水滴在涂膜上；调整目镜、载玻平台及光源位置，使光源中心、样品表面、蒸馏水滴、自镜在一个水平面上并保持直线；调节焦距至连接计算机视频中出现清晰图像；利用计算机视频截取水滴图像，读出水滴图像的左右两侧的接触角;在该样品上分别选取3个不同的测量点，取其平均值，并分别用接触角测量仪配套设备拍摄液滴在薄膜表面形貌照片。  \n\n1.2.2.4粘附功:1.先用标准水和标准乙二醇测量其在蓝宝石镜片上的接触角，然后利用OWRK(Owens-Wendt-Rabeland-Kaelble)公式计算出蓝宝石镜片表面的自由能，包括色散分量(Disp)、极性分量(Polar)，标准液体可选用（水、乙二醇、二碘甲烷、甲酰胺）。2.测量被测液体的表面张力（用悬滴法）和界面张力（悬滴法，液滴在正已烷中的界面张力）。3.对所测液体的表面张力进行分析包括色散分量(Disp)、极性分量(Polar)；4.接触角仪电脑软件计算出粘附功。  \n\n1.2.2.5透射电镜：将待测防雾剂予蒸馏水稀释3倍后用超声波震荡均匀后滴在微栅上，待其自然干燥后检测。利用日本电子公司JEM-100CXI透射电子显微镜来观察颗粒形貌、分散程度和粒径。首先调好电镜灯丝像，关灯丝后插入样品，在完成电压中心、光栏、聚光镜像散、物镜像散调节后插入物镜光栏，在观察样品的时候调节，在高倍下找到一样品作为参照，改变焦距，观察样品并拍照。  \n\n1.2.2.6原子力显微镜：将蓝宝石镜片放入含有洗洁净溶液中超声清洗1小时，用超纯水反复冲洗镜片表面洗洁净溶液直至洗净，将蓝宝石镜片放于3mol/L的氢氧化钠溶液中浸泡3h，用去离子水反复冲洗，再用酒精清洗蓝宝石镜片吹干从而获得清洁的蓝宝石镜片表面。将蓝宝石镜片完全浸入待检测溶液后再缓缓取出后自然凉干，用日本SHIMADZU（岛津）公司SPM-9500J3原子力显微镜后对样品进行检测。检测时使用接触模式，首先将接触式的探针安装在悬臂夹中，再把涂有防雾剂的镜片粘于样品碟上并放于扫描管的上面，取下激光头，把装有探针的悬臂夹放入激光头中，用激光头后面的锁紧螺丝把悬臂夹锁紧，调整经激光点到探针尖端的背面，设置并优化扫描参数，点击engage按钮，计算机开始自动下针，当针接触到样品并且弯曲量达到预先设定的setpoint值时，扫描管开始扫描。点击capture 按钮，开始抓取图象并拍照。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 60,
+        "chunk": "# 2结果",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 61,
+        "chunk": "# 2.1防雾时间及防雾性能测试结果  \n\n不同纳米粒子改性防雾剂鼻内窥镜防雾时间（min）Different antifogging time of nanoparticles modified nasal endoscopic antifoggant  \n\n\n<html><body><table><tr><td>类别</td><td>第1次</td><td>第2次</td><td>第3次</td><td>平均</td></tr><tr><td>PVP</td><td>10</td><td>12</td><td>8</td><td>10</td></tr><tr><td>PVP+0.025g 纳米氧化锌</td><td>10</td><td>13</td><td>13</td><td>12</td></tr><tr><td>PVP+0.050g 纳米氧化锌</td><td>13</td><td>16</td><td>16</td><td>15</td></tr><tr><td>PVP+0.100g 纳米氧化锌</td><td>10</td><td>14</td><td>15</td><td>13</td></tr><tr><td>PVP+0.025g 纳米氧化钛</td><td>15</td><td>17</td><td>16</td><td>16</td></tr><tr><td>PVP+0.050g 纳米氧化钛</td><td>13</td><td>11</td><td>15</td><td>13</td></tr><tr><td>PVP+0.100g 纳米氧化钛</td><td>13</td><td>9</td><td>14</td><td>12</td></tr><tr><td>PVP+0.025g 中空纳米二氧化硅</td><td>14</td><td>11</td><td>14</td><td>13</td></tr><tr><td>PVP+0.050g 中空纳米二氧化硅</td><td>17</td><td>15</td><td>19</td><td>17</td></tr><tr><td>PVP+0.100g 中空纳米二氧化硅</td><td>16</td><td>15</td><td>12</td><td>14</td></tr></table></body></html>\n\n注：时间精确到分，以 $30^{\\prime\\prime}$ 为界舍入  \n\n2.2透光率：在可见光范围内PVP的透光率约为 $100\\%$ ，如图1；纳米氧化锌改性PVP透光率约为 $90\\%$ ，如图2；纳米氧化钛改性PVP透光率约为 $85\\%$ ，如图3；  \n\n中空纳米二氧化硅改性PVP透光率约为 $92\\%$ ，如图4；碘伏透光率约为 $80\\%$ 如图5；碘伏 $+$ 纳米二氧化钛透光率约为 $70\\%$ ，如图6。  \n\n2.3接触角：水滴在PVP涂膜上的接触角度9.6度，如图7；水滴在纳米氧化锌改性PVP涂膜上的接触角5.9度，如图8；水滴在纳米氧化钛改性PVP涂膜上的接触角4.8度，如图9；水滴在中空纳米二氧化硅改性PVP涂膜上的接触角6.1度，如图10。  \n\n2.4粘附功：水在蓝宝石镜面的接触角为(56.159.958.0)平均值为58.0度；乙二醇在蓝宝石镜面的接触角为(46.351.648.2)平均值为48.7度；蓝宝石镜面的表面能为 $52.36{\\pm}\\mathrm{mN}/\\mathrm{m}$ ，其中色散分量 $(\\mathrm{Disp}2.91\\pm\\mathrm{mN}/\\mathrm{m})$ ；极性分量 $(\\mathrm{Polar}49.44{\\pm}\\mathrm{mN}/\\mathrm{m})$ 标准水的表面张力为 $72.80{\\pm}0.05\\mathrm{mN/m}$ ，其中色散分量 $(\\mathrm{Disp}29.10\\mathrm{mN/m})$ ，极性分量 $\\left(\\mathrm{Polar~}43.70~\\mathrm{mN/m}\\right)$ ；标准乙二醇的表面张力为 $48.00{\\pm}0\\mathrm{mN/m}$ ，其中色散分量 $(\\mathrm{Disp}29.00\\mathrm{mN/m})$ ，极性分量 $\\mathrm{(Polar~19.00~mN/m)}$ 。  \n\n防雾剂在蓝宝石镜面的粘附功测量数值 $\\left(\\mathbf{mN}/\\mathbf{m}\\right)$   \n\n\n<html><body><table><tr><td colspan=\"8\"> measurement values of the adhesion work between antifoggant and sapphire lens</td></tr><tr><td>参数</td><td colspan=\"4\">表面张力 界面张力</td><td colspan=\"4\">色散极性粘附</td></tr><tr><td>样品 第一</td><td>第一</td><td>第三 平均</td><td>第一</td><td>第二</td><td>第三 平均</td><td>分量</td><td>分量</td><td>功</td></tr><tr><td>1</td><td>68.64 68.86</td><td>68.68 68.73</td><td>32.57</td><td>31.98</td><td>32.29 32.28</td><td>40.85</td><td>27.88</td><td>96.10</td></tr><tr><td>2</td><td>66.52 66.43</td><td>67.26 66.74</td><td>35.36</td><td>35.44 36.04</td><td>35.61</td><td>33.32</td><td>33.42</td><td>101.02</td></tr><tr><td>3</td><td>67.58 68.04</td><td>67.45 67.69</td><td>35.16</td><td>35.42 35.83</td><td>35.47</td><td>34.80</td><td>32.89</td><td>100.81</td></tr><tr><td>4</td><td>66.17 66.10</td><td>66.26 66.18</td><td>37.30</td><td>37.34</td><td>37.04</td><td>37.23 30.45</td><td>35.73</td><td>102.92</td></tr></table></body></html>\n\n注：样品1指PVP溶液；样品2指纳米氧化锌改性PVP；样品3指纳米氧化钛改性PVP;样品4指中空纳米二氧化硅改性PVP。  \n\n2.5透射电镜：纳米氧化锌在PVP溶液中分散较好，如图11，制备的纳米氧化钛粒径约 $120{\\sim}160\\mathrm{nm}.$ 在 PVP溶液中分散较好,如图12，如图13，制备的中空纳米二氧化硅粒径约 $200\\mathrm{nm},$ 在 PVP溶液中分散较好,如图14。  \n\n2.6原子力显微镜：聚乙烯吡咯烷酮鼻内镜防雾剂在蓝宝石镜面形成一均匀的薄膜，最厚处约 $78.30\\mathrm{nm}$ ，膜表面较平整，如图15，图16；纳米氧化锌改性PVP形成的薄膜最厚处约 $277.97\\mathrm{nm}$ ，膜表面较单纯防雾剂表面粗糙，如图17，图18；纳米氧化钛改性PVP形成的薄膜最厚处约 $227.34\\mathrm{nm}$ ，膜表面较单纯聚乙烯吡咯烷酮表面显粗糙，如图19，图20。中空纳米二氧化硅改性PVP形成的薄膜亦较粗糙，薄膜最厚处约 $34.64\\mathrm{nm}$ ，如图21，图22。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 62,
+        "chunk": "# 3讨论  \n\n目前国内各医院通常予碘伏、乙醇、皂液作为鼻内镜手术时内镜防雾剂。碘伏通用名为聚维酮碘，是碘与表面活性剂聚乙烯吡咯烷酮相结合而成的松散络合物。碘伏除了作鼻内镜防雾剂外，同时还具有广谱的抗微生物作用，毒性低、对粘膜无刺激，作为鼻内镜的主要原理是其组分聚乙烯吡咯烷酮具有表面活性剂的功能而使得其具有一定的防雾性能。但在第一部分的研究中发现碘伏作为鼻内镜防雾剂也存在如下缺点：防雾时间不够长，在鼻内镜上很难形成一较均匀的膜，另外碘伏因含有碘也影响了其透光率，经检测，在可见光范围内碘伏透光率仅约为 $80\\%$ 。为了克服上述缺点，实验以一定质量百分比不含碘的聚乙烯吡咯烷酮水溶液作为鼻内镜防雾剂。所制备的聚乙烯吡咯烷酮溶液几乎是无色透明的，透光率接近 $100\\%$ 。聚乙烯吡咯烷酮 Polyvinylpyrrolidone（PVP）,分子式： $(\\mathbf{C6H9NO})\\mathbf{n}$ ，是一种非离子型高分子化合物，PVP 是由N-乙烯吡咯烷酮(NVP)聚合而成的，其中的亚甲基可形成桥和吡咯烷酮环，是非极性基团，具有亲油性，PVP 分子中具有亲水作用的是内酰胺，属于强极性基团。PVP 是高分子化合物，本身就具有吸附作用的特点，通过吸附作用可使其吸附在许多界面上并显著降低界面的表面张力。通常平均分子量越大，其粘度越大，吸附性越强，本试验选用Mw为1300000的聚乙烯吡咯烷酮溶液作鼻内镜防雾剂，通过检测，其在鼻内镜蓝宝石镜面的粘附功为 $96.10(\\mathrm{mN/m})$ 。PVP无色、无味且无毒，对人体皮肤、粘膜等不形成任何刺激。另外，它具有良好的生理相容性、溶解性、优良的生理惰性及较好地洗涤性能，因此PVP在医药、食品、化妆品等相关的领域有广泛的应用。以一定浓度的PVP水溶液作为鼻内镜防雾剂一方面利用其较强的吸附作用使其在鼻内镜镜面上能较好地粘附；另外，聚乙烯吡咯烷酮虽是一种高分子聚合物,但也因其含有亲水作用的强极性内酰胺基团可表现出阴离子表面活性剂的性质[2]。利用PVP分子中的强极性基团内酰胺的亲水作用，则能吸附环境中的水汽使其能在PVP成膜的表面形成一水膜减少对光的漫反射而达到防雾目的，上述原因是本试验选用PVP作为鼻内镜防雾的主要原因。同样，基于往防雾剂添加纳米粒子或氧化物可增强防雾剂与固体表面的粘附这一观点[3]4]。本实验向 PVP 水溶液添加纳米粒子对其进行改性而增强其与鼻内镜蓝宝石镜面的粘附。纳米粒子因其具有的多种优异性能，可明显改善高分子材料的各项力学特性[5。实验时向PVP水溶液添加了一定质量比的对人体无毒的纳米氧化锌、纳米氧化钛及中空纳米二氧化硅。  \n\n纳米氧化锌具有抗菌抑菌、高效生物学活性、安全无毒且稳定性好等特性，已广泛应用于化妆品抗紫外线，抗菌、光催化剂、卫浴洁具及医疗卫生等领域。纳米氧化锌颗粒特殊的体积效应及表面效应，决定了其具有特殊的化学性质及功能，如增强表面吸附力，表现出很高的化学反应活性，光照射时，不仅有催化功能，且会产生亲水性[7-9]。因此向防雾剂中添加纳米氧化锌颗粒，一是可以增强防雾剂的表面吸附力；其次可以光催化内镜表面上的有机污物，增强防雾剂的清洁和防雾作用；另外，PVP加纳米氧化锌的透光率仍较高，达到 $90\\%$ 0  \n\n纳米 $\\mathrm{TiO}_{2}$ 具有极好的光学特性，具有较高的化学稳定、热稳定、超亲水、抗菌、价廉、对人体安全无毒，对皮肤无刺激性等独特性能，所以被广泛应用于食品加工、光催化、玻璃自洁、化妆品等领域[10-12]。纳米二氧化钛颗粒表面含有大量羟基，在水中会发生部分电离，使颗粒表面带负电荷，所以在 PVP水溶液中加入纳米二氧化钛颗粒后，纳米二氧化钛微粒吸附聚乙烯吡咯烷酮后，纳米微粒之间产生新的排斥能，即空间阻力势能，减少纳米粒子的团聚，可提高防雾剂的稳定性。秦伟庭曾报导在纳二氧化钛 $\\mathrm{TiO}_{2}$ 溶胶分散体系中加人聚乙烯吡咯烷酮后溶胶的稳定性会得到提高[13]。本实验将一定质量百分比二氧化钛加入PVP溶液中通过透射电镜可以看出，纳米粒子有较好的分散。加入纳米氧化钛后对透光率有一定的影响，约为 $85\\%$ ，但也较临床常用的鼻内镜防雾剂碘伏的透光率要好，碘伏透光率仅约为 $80\\%$ 。  \n\n实验添加中空纳米二氧化硅主要是利用纳米二氧化硅的中空不会对所配制的防雾溶液的透光率造成太大影响。本实验在可见光范围内PVP的透光率约为$100\\%$ ；PVP加中空纳米二氧化硅的透光率达到 $92\\%$ 8  \n\n虽然近年来国内外在高分子的固液界面吸附理论研究方面取得了一定的进展[4][15]。但实验表征固液界面吸附往往较困难。通常液体与固体之间的粘附主要是由分子间的作用力，包括氢键力和范德华力所决定，另外也有可能出现化学键结合。影响高分子吸附的主要因素包括高分子与固体表面的自身因素，当固体表面或高分子具有可以强化两者相互作用的结合点或基团时高分子的吸附量增加，相反则减少[16。固液两相都有将表面能降到最低趋势，液体因粒子能自由运动，常呈球形而将表面能降至最低，固体则不同，由于表面的粒子不能自由移动，其表面总是呈高表面能区域。当固液接触后，固液界面通常会发生两种吸附：即物理吸附和化学吸附，物理吸附主要为分子间吸引力，即范德华力;另外，也可由于固体表面表面与液体间发生化学反应而产生化学吸附，这是由于固体表面的原子化学结合力未完全被相邻原子所饱和，还有剩余的形成化学键的能力，则在固液之间可以发生电子转移形成化学键[17[18]。当液体吸附在固体表面后，由于固体界面的结构与原界面明显不同，使得固体表面由较高的表面能降低为较低的表面能。  \n\n仕鼻内镜与防务剂衣面就属于上还情况，鼻内镜监玉石镜面属于相对高衣面能区域，当接触到高分子PVP溶液时，其有吸附高分子PVP将表面能降到最低趋势，这即是鼻内镜表面吸附防雾剂的原理，其中包括由范德华力引起的物理吸附作用，还包括由于鼻内镜蓝宝石表面的原子化学结合力未完全被相邻原子所饱和，有剩余的形成化学键的能力，可与高分子PVP与间而产生化学吸附。实验时向防雾剂添加了不同组分的纳米粒子（纳米氧化锌、纳米氧化钛、 $\\mathbf{SiO}_{2}$ 中空微球），这几种物质均无毒，无味，对皮肤粘膜刺激小，因其比表面积大，表面存在大量不饱和键和羟基及丰富的极性基团，而用作防雾剂的PVP含有大量的氧、氮等原子，这些原子容易与纳米粒子表面存在的羟基形成大量氢键，增强了纳米粒子对防雾剂的吸附，同时由于纳米粒子的高表面活性也可对鼻内镜蓝宝石表面产生较强的吸附，这样由于纳米粒子的桥接作用增强了防雾剂与鼻内镜蓝宝石表面的吸附，延长了防雾剂的流失，从而达到延长防雾时间的效果。AldoHandojo研究牛奶产品与玻璃表面的粘附时指出牛奶因含有大量的悬浮的固体颗粒，固体颗粒不但与牛奶液体间存在分子吸引力，同时也与玻璃表面存在分子吸引力9。我们所研制的纳米粒子改性的亲水型鼻内镜防雾剂也存在类似情况，其中的纳米粒子不但与液体间存在分子吸引力，同时也与鼻内镜镜面存在分子吸引力。PVP与鼻内镜蓝宝石镜面的粘附力主要是由分子间的作用力，包括氢键力和范德华力所决定。在上一章已提到固液之间的粘附作用通常以粘附功大小来反应。粘附功即在等温等压条件下，单位面积的液面与固体表面粘附时对外所作的最大功，它是液体能否润湿固体的一种量度。粘附功越大，液体越能润湿固体，液-固结合得越牢。在粘附过程中，消失了单位液体表面和固体表面，产生了单位液-固界面。粘附功就等于这个过程表面吉布斯自由能变化值的负值。粘附功表征不同液体或液体与固体间的吸引强度，与相互作用液固材料的表面自由能及界面张力有关[2%。随着PVP中加入不同的纳米粒子纳米$\\mathrm{TiO}_{2}$ 、纳米ZnO、中空纳米二氧化硅后，一方面由于纳米粒子的存在，因其桥接作用对液态防雾剂有一定的固定作用，另外，因纳米粒子的添加改变了防雾剂的极性，从上章已知鼻内镜蓝宝石镜面表面能色散分量 $2.92\\mathrm{mN/m}$ ，极性分量$49.44\\mathrm{mN/m}$ 极性比为94：100，未经改性的聚乙烯吡咯烷酮溶液表面能色散分量$40.85\\ \\mathrm{mN/m}.$ ，极性分量 $27.88\\mathrm{mN/m}$ ，极性比为41：100，粘附功值 $96.10\\mathrm{mN/m}$ 9而纳米粒子的添加改变了聚乙烯吡咯烷酮溶液的极性，纳米氧化锌改性PVP防雾剂色散分量 $33.32\\mathrm{\\mN/m}.$ ，极性分量 $33.42\\mathrm{mN/m}$ ，极性比为50:100，粘附功值$101.02\\mathrm{mN/m}$ ；纳米氧化钛改性PVP防雾剂色散分量 $34.80\\mathrm{mN/m}$ ，极性分量32.89$\\bf{m N/m}$ ，极性比为49:100，粘附功值 $100.81\\mathrm{mN/m}$ ；中空纳米二氧化硅改性PVP防雾剂色散分量 $30.45~\\mathrm{mN/m}$ ，极性分量 $35.73~\\mathrm{mN/m}$ ，极性比为54:100，粘附功值 $102.92\\mathrm{mN/m}$ ，经纳米氧化锌、纳米氧化钛及中空纳米二氧化硅改性后的聚乙烯吡咯烷酮溶液极性均有提高，其表面能极性比更接近鼻内镜蓝宝石表面能极性比，更易浸润鼻内镜蓝宝石镜面，与蓝宝石镜面的粘附增强，进而延缓了防雾剂在鼻内镜镜面的流失，提高了防雾剂防雾性能。  \n\n透射电镜可以看出纳米氧化锌在PVP溶液中分散较好；制备的纳米氧化钛在 PVP溶液中分散较好;制备的中空纳米二氧化硅在PVP溶液中分散较好,但可能因实验时水洗次数不够，聚丙烯酸存留导致了大部分纳米粒子还呈实心，如图14.  \n\n原子力显微镜（Atomic ForceMicroscope，AFM)，—种可用来研究包括固体材料表面结构的分析仪器，是一种可用于对有机/无机薄膜和生物材料表面形貌产生高分辨率图像的的技术,它利用原子、分子间的相互作用力来观察物体表面微观形貌。它通过纳米级的探针检测样品表面和一个微型力敏感元件之间的极微弱的原子间相互作用力来研究物质的表面结构及性质。当探针靠近样品时，其顶端的原子与样品表面原子间的作用力会使悬臂弯曲，偏离原来的位置。根据扫描样品时探针的偏离量或振动频率重建三维图像，就能间接获得样品表面纳米级分辨率的形貌图像用于物体表面分析。另外，原子力显微镜也可用来研究固液界面的粘附，AldoHandojo曾用原子力显微镜来表征溶解并悬浮在牛奶样品中的固体颗粒和玻璃表面的粘附强度[9]。通过AFM可以看出我们所研制的  \n\nPVP鼻内镜防雾剂在蓝宝石镜面形成一均匀的薄膜厚约 $78.30\\mathrm{nm}$ ，膜表面较平整;PVP鼻内镜防雾剂中添加纳米氧化锌、纳米氧化钛及中空纳米二氧化硅后，膜表面较单纯PVP鼻内镜防雾剂表面粗糙，突点明显增多，尺寸约在 $34{\\sim}277\\mathrm{nm}$ ，这些突点为纳米粒子所在处。另外，上章已提到对于亲水材料而言，表面粗糙度增加其表面亲水性亦增加，因材料亲水，微观结构下液体可完全浸润固体亲水材料表面，形成一液固复合表面，固液接触面积明显增加，水滴可牢固地粘附于亲水材料表面，即亲水性能增加，这可以从接触角检测结果可以看出，水滴在聚乙烯吡咯烷酮涂膜上的接触角度9.6；水滴在纳米氧化锌改性PVP涂膜上的接触角5.9；水滴在纳米氧化钛改性PVP涂膜上的接触角4.8度；水滴在中空纳米二氧化硅改性PVP涂膜上的接触角6.1度。这样一方面因纳米粒子的添加改变了防雾剂的亲水性能，另一方面这些纳米粒子的固定作用及因纳米粒子的添加使防雾剂极性比提高，与鼻内镜蓝宝石表面粘附增强，延缓了防雾剂在鼻内镜镜面的流失，延长了防雾时间，使水汽或雾滴更易在防雾剂涂膜表面浸润从而提高防雾剂的防雾性能。从鼻内镜防雾试验可以看出，聚乙烯吡咯烷酮溶液的防雾时间为10分钟，而经纳米粒子改性后防雾时间均延长，约为15\\~17分钟。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 63,
+        "chunk": "# 4结论  \n\n1.研究表明以在医药、食品等相关的领域有广泛应用的一定浓度的PVP水溶液作为鼻内镜防雾剂是可行的，通过氧化锌、氧化钛及纳米 $\\mathrm{SiO}_{2}$ 中空微球对其进行改性使其防雾性能进一步增强。  \n\n2.通过粘附功、表面形貌对改性后的防雾机理进行阐述得出：一方面因纳米粒子添加使防雾溶液的极性比提高使改性后的防雾剂与鼻内镜表面的粘附增强，另一方面因改性后防雾剂涂膜表面粗糙度增强防雾材料的亲水性能。  \n\n不足之处：1.缺少不同分子量、不同浓度PVP防雾性能比较；2.缺少X射线光电子能谱（X-ray Photoelectron Spectroscopy）XPS对化学位移及化学键的检测。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 64,
+        "chunk": "# 参考文献  \n\n[1]马婷芳，史铁钧．聚乙烯吡咯烷酮的性能、合成及应用[J]应用化 工,2002,31(3):16-18.   \n[2]M.C.R.Symons, J.M.Harvey, S.E.Jackson.Spectroscopic studies of water aprotic solvent interactions in the water-rich region[J].Chem.Soc.,Faraday. Tram. 1980, 76,256-265.   \n[3]罗茂鲜，刘东辉术，孟丽丰，纳米 SiOx改性喷涂型防雾剂的研制[]广东 化工,2009,192(38):148-152.   \n[4]万屏南，衷友泉，熊丽萍．新型氧化铈玻璃防雾剂的研制[J].华东交通大学 学报，2006,23 (1):169-172.   \n[5]   Shantalii T A, Karpova I L, Dragan K S, et al. Synthesis and thermomechanical characterization of poyiides reinforced with the sol-gel derived nanoparticles [J].Science and Technlolgy of Advanced Materials 2003,4,115-119.   \n[6] Chisholm N, Mahfuz H, Rangari V K, et al. Fabrication and ecanical characterization of caron/SiC-epoxy Nanocomposites [J].Composite Structures, 2005, 67(1): 115-124.   \n[7] YE Chang Hui, BANDO Y, SHEN Guo Zhen, et al. Thickness dependent photocatalytic performance of $z_{\\mathrm{nO}}$ nanoplateletsl [J]. J Phys Chem B, 2006, 110(31): 15146-15151.   \n[8]GUO I, YANG C I,YANG S H. et al. Highly monodisperse polymer-capped ZnO nanoparticles: Preparation and optical properties [J].Appl Phys Lett, 2000, 76(20): 2901-2903.   \n[9]冯怡,袁忠勇.ZnO 纳米结构制备及其器件研究[].中国科技论文在线,2009, 4，157-168.   \n[10] Prasher R S, Phelan P E. Non-dimensional size effect on the thermodynamic properties of solids[J]. Intemation Journal of Heat and Mass Transfer, 1998,  \n\n42(11): 1991-2001.  \n\n[11] Sekiya T,Ohta S,Kamei S. Raman spectroscopy and phase transition of anatase $\\mathrm{TiO}_{2}$ under high pressure[J].Phys Chem Solids, 2001, 62,717-721.  \n\n[12] Jung S M,Dupont O, Grange P. Photocatalytic degradation of phthalic acid on $\\mathrm{TiO}_{2}$ nanoparticles[J]. Appl Catal A,2001,208,393-401.  \n\n[13]秦伟庭，沈勇，张惠芳．纳米 $\\mathrm{Ti}0_{2}$ 在水分散体系中的稳定性[J].印染，2006,32(7):4-6.  \n\n[14] Roach P, Farrar D, Perry CC.Interpretation of protein adsorption: surface induced conformational changes[J].J Am Chem Soc. 2005, 127(22): 8168-8173.  \n\n[15]李浩，杨海洋，朱平平,等．利用Poiseuille方程确定聚乙烯醇在粘度计毛细管管壁上吸附层的厚度[J]功能高分子学报，2002，15(3):319-323.  \n[16]李海普，李星，张莎莎,等．高分子在固液界面吸附构象的研究方法及手段[J].化学通报,2011,74(5):417-423.  \n\n[17]崔燕．第七章减少微颗粒与界面间粘附力措施的实验研究.中南大学博士学位论文,2011,111-112.  \n\n[18]李明.第二章固体表面粘附微颗粒的原因及方式研究.中南大学博士学位论文,2009,14-35.  \n\n[19]  Aldo Handojo , Yumei Zhai , Gerald Frankel , et al.Measurement of adhesion strengths between various milk products on glass surfaces using contact anglemeasurement and atomic force microscopy [J]. Journal of Food Engineering,2009,92,305-311.  \n\n[20] A. Ola'h, M. A. Hempenius, S. Zou, et al. Adhesion studies of latex film surfaces on the meso and anoscale[J].Applied Surface Science ,2006, 252, 3714-3728.  \n\n![](images/dbe80cdc57f3578fa417c34df797f176267bb1a9ffc4d5b55e8b665f1d3c522c.jpg)  \n附图  \n\n![](images/386d7023f70c38793c3769fc427cb9350834866d2fdebd0c60c77ccb04b0c6b3.jpg)  \n图2纳米氧化锌改性PVP透光率Fig.2 light transmittance of PVP modified bynanozno  \n\n![](images/e10c53fecbdb037f98ad3c63a1a98668150f64d813eb8f893224c96356ebba9f.jpg)  \n图1PVP透光率  \n\n![](images/92ed4cd5a5c8715fefc5319919888be1d051938e157caa6b1be5221876974c65.jpg)  \nFig.1 light transmittance of PVP  \n\n![](images/c6e6fd93e9c2735518553fa7b6421407735a29ae766e2d9b9b7c7cad6c0a03a6.jpg)  \n图3纳米氧化钛改性PVP透光率 Fig.3light transmittance ofPVP modified by nano titanium oxide   \n图5碘伏透光率  \nFig.5 light transmittance of Betadine  \n\n![](images/5fdf61036e99791eef2d3aa25fe24a7b4177346dac31bc9ff0615b89e9a10a88.jpg)  \n图4中空纳米二氧化硅改性PVP透光率Fig.4 light transmittance of PVPmodifiedbynano hollownanosilica  \n图6纳米二氧化钛改性碘伏透光率 Fig.6 light transmittance of Betadine modified by nano titanium oxide  \n\n![](images/778fe7bbf712c598d9a87f11630476df94b33f8918844dbc3ead3b3b72dee3ec.jpg)  \n博士学位论文  \n\n![](images/e2e7e4ab16b1308fde5c60f532e3fdf29e7dfd33fd5f055ca4e881cc9859084f.jpg)  \n图7PVP接触角9.6度 Fig.7 contact angle of 9.6 degrees of PVP  \n\n![](images/167b66afbadb7123d31cee6b457464bc7fbb5cda8046060399b822662bd9dd90.jpg)  \n图9纳米氧化钛改性PVP接触角4.8度 Fig. 9 contact angle of 4.8 degrees of PVPmodifiedby nano titaniumoxide  \n\n![](images/d6d06b3693e1ebadfe4afbd3285c4a5058a873c099c3bcf19401c1c287f49b05.jpg)  \n图8纳米氧化锌改性PVP接触角5.9度Fig.8 contact angle of 5.9 degreesofPVPmodifiedbynanozno  \n图10中空纳米二氧化硅PVP接触角6.1度 Fig.10 contact angle of 6.1 degrees of PVPmodifiedbyhollownano silica  \n\n![](images/cef8d3916d636714b7e488efe3c4948234cfbad7282ace3e500810f60d428fc3.jpg)  \n图11纳米氧化锌改性PVP 透射电镜结果（ $\\times50000\\$ ? Fig.11TEM of of of PVP modifiedbynanozno  \n\n![](images/47011f49119690ba3cc7a32d0f22da5592d9bae31ba66d428ebbb54ab31b63c8.jpg)  \n图12纳米氧化钛改性PVP透射电镜结果 $(\\times50000^{\\cdot}$ 0Fig.12TEM of of of PVPModified bynano titanium oxide  \n\n![](images/4c1f7477ee69d35cfa6f1ec098f4acaf512854d446eff297d4d44aaeacffa904.jpg)  \n图13纳米氧化钛改性PVP透射电镜结果（ $\\times100000\\$ Fig.13TEM of of of PVPmodifiedbynanotitanium oxide  \n\n![](images/37659899f225b24fedf2408d4c86d8c4f276b673886eb1e30f4f2a6e9189b692.jpg)  \n图14纳米中空二氧化硅改性PVP透射电镜结果 $(\\times50000)$ Fig.14TEMof of of PVPmodifiedbyhollownanosilica  \n\n![](images/13028d4ac6061e438e97052ba36d74190cde4cf309bf4e7e19faf335ee463ea9.jpg)  \n图15原子力显微镜检测PVP结果  \n\n![](images/1d88dc1515791008e625145616ac504d8961ebdea349de703047c49bf5e014b5.jpg)  \nFig.15AFMofPVP   \n图16原子力显微镜检测PVP结果  \nFig.16AFMofPVP  \n\n![](images/463446ae18ba0232be3d6fca4ef008a93aa8b171aa5002b5124938682405b16c.jpg)  \n图17原子力显微镜检测纳米氧化锌改性PVP结果  \n\n![](images/d78f1ce7c9a769c599c0daeb5176013c474bc5139d5bb3f311d858ad9d072df6.jpg)  \nFig.17 AFM of PVP modified by nano zno   \n图18原子力显微镜检测纳米氧化锌改性PVP结果  \nFig.18 AFM of PVPmodified by nano zno  \n\n![](images/8d35bc7fefec06d298b1ae2a5f180d40c848534ee100279182814c74c22d749a.jpg)  \n图19原子力显微镜检测纳米氧化钛改性PVP结果 Fig.19 AFM of PVPmodified by nano titanium oxide  \n\n![](images/cd7184853a4e22b2a1f52a820468b545c72d29d92d560e9019646784bd1edf47.jpg)  \n图20原子力显微镜检测纳米氧化钛改性PVP结果Fig.20AFMofPVPmodifiedbynano titaniumoxide  \n\n![](images/022055d60c510c678e7018c3c0f3c32f4e73ac283ffdb0c550953b3168f8cd63.jpg)  \n图21原子力显微镜检测中空纳米二氧化硅改性PVP结果  \n\n![](images/6140dc4c023743d15cf4cf4d78453b704715bcf32bf6d6a48db04eafe8fc301d.jpg)  \nFig.21 AFMof PVP modified byhollow nano silica   \n图22原子力显微镜检测中空纳米二氧化硅改性PVP结果  \nFig.22 AFM ofPVPmodified by hollow nano silica",
+        "category": " References"
+    },
+    {
+        "id": 65,
+        "chunk": "# 第四章 透明超疏水薄膜防雾性能研究  \n\n前言：在前面三个部分探讨了亲水性鼻内镜的研制及防雾性能研究，亲水物质包括阴离子表面活性剂、阳离子表面活性剂及非离子表面活性剂，其中阴离子表面活性剂的亲水基团有羧酸基、硫酸基；阳离子表面活性剂的亲水基团有氨基、季铵基等；非离子表面活性剂的亲水基团有由含氧基团组成的醚基与羧酸酯。亲水物质能吸引水分子，这类分子形成的固体表面易被水浸润，水汽在亲水物质表面容易形成一层水膜减少对光的漫反射而达到防雾的目的。亲水防雾的研究国内外有已较多报道[-。内镜手术时亲水防雾特别是喷涂型防雾材料最大缺点是材料与内镜接合不够牢固，防雾剂易流失导致防雾时间较短。相反，疏水材料因制备过程的特殊性常能与其它材料结合牢固，水滴在其表面容易滚动理论上可以达到防雾效果。超疏水材料是指对于水的浸润角超过 $150^{\\circ}$ ，而水滴在其表面的滚动角小于 $10^{\\circ}$ 的材料，在基于经典的Wenzel和Cassie 模型的理论指导下，超疏水材料成为全球广大材料科研工作者的研究热点，超疏水材料表面的自洁净效应已在工农业及日常生活中广泛应用，但其应用于防雾的研究报导罕见，主要由于疏水材料的疏水性能与材料表面的粗糙度呈正相关，即材料表面的粗糙度越高其疏水性能越好，而粗糙度越高其透光率势必就越受影响，实际上很难在疏水性与透光率之间找到一较好地平衡。另外，水滴要能在材料表面自由滚动，这就要求水滴在材料表面的接触角要达到180度，这其实是一种理想的状态。另外，材料疏水性好其防雾效果是否也会更好呢？理论上分析材料疏水性越好水滴在其表面越容易滚动，防雾效果理应更好些，但疏水与防雾是不同的概念，因为水滴与水汽或雾滴大小完全不同，材料对水滴的疏水效果好是否对小雾滴的疏水性也更好呢？目前国内外缺少这方面的报道。疏水材料的制备方法已有大量的文献报道，但溶胶凝胶法(sol-gelmethod)是最常用的制备超疏水表面的方法[3-。本章通过制备超疏水表面来对其防雾性能进行初步研究，从超疏水理论方面探讨疏水材料有无进行内镜防雾的可能。",
+        "category": " Introduction"
+    },
+    {
+        "id": 66,
+        "chunk": "# 1材料和方法",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 67,
+        "chunk": "# 1.1试剂与仪器",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 68,
+        "chunk": "# 实验试剂  \n\n试剂 规格 厂家无水乙醇 分析纯 天津市富宇精细化工有限公司盐酸 $36\\%$ ，分析纯 广州市东红化工厂氨水 分析纯 广州市东红化工厂氢氧化钠 分析纯 天津市百世化工有限公司正硅酸乙酯 $28.4\\%$ ，分析纯 中国上海五联化工厂丙稀酸 分析纯 广州市化学试剂厂硅烷偶联剂 分子量290 武大有机硅新材料股份有限公司",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 69,
+        "chunk": "# 实验仪器  \n\n仪器 型号 厂家  \n可调温式磁力搅拌仪 CL-3 巩义市英峪予华仪器厂  \nNabertherm 马弗炉 Mod LH 15/13S 德国  \n台式匀胶机 KW-4A 中国科学院微电子研究所  \n水浴锅 HSG IB-2 上海仪表供销公司  \n超声波清洗器 KQ-100DB 昆山市超声仪器有限公司  \n干燥箱 PH0307 上海实验仪器总厂  \n超高分辨场发射扫描电镜 NanoSEM430 荷兰  \n紫外-可见分光光度计 Lambda 900 美国Perkin Elmer 公司  \n接触角仪 OCA20LHT 德国Dataphysics 公司",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 70,
+        "chunk": "# 1.2实验过程  \n\n载玻片的预处理：将载玻片切成约 $2.0\\mathrm{cm}\\times2.0\\mathrm{cm}$ 大小；用洗洁净适量溶于水中配置成溶液，将切好载玻片放入含有洗洁净溶液中超声清洗30min，用超纯水反复冲洗载玻片表面洗洁净溶液直至洗净，将载玻片放于3mol/L的氢氧化钠溶液中浸泡3h，用去离子水冲洗，直到载玻片上没有水珠成线性流下即可，再用酒精清洗载玻片吹干从而获得清洁的载玻片表面。为避免清洁后的载玻表面再受污染，应尽量缩短从清洗到提拉成膜的时间。  \n\n酸溶胶制备：将8.36mL正硅酸乙酯（TE0S）加入到80mL无水乙醇中充分溶解，在磁力搅拌器搅拌下滴加36%的盐酸4.8mL到上述溶液中，继续搅拌19h。  \n\n碱凝胶制备：将3.1mL正硅酸乙酯（TE0S）加入到80mL无水乙醇中充分溶解，再加入13.8mL去离子水，在磁力搅拌器搅拌下逐渐滴加4.7mL分析纯氨水到上述溶液中，密封反应1小时。  \n\n丙烯酸溶液制备：将4种不同批次的丙稀酸（A396、A842、A53、BM-51）各 $3.0{\\tt g}$ 分别溶于 $\\mathsf{50m L}$ 无水乙醇中，磁力搅拌器上充分搅拌至完全溶解  \n\n按下表中所示将酸溶胶、丙烯酸溶液、碱凝胶加入无水乙醇中，所制备溶液超声振荡1h，使溶胶良好分散。  \n\n表一：不同的试剂配比实验（ml）  \nFig.1 Different experiment of different reagent ratio(ml)   \n\n\n<html><body><table><tr><td>序号</td><td>酸溶胶</td><td>碱凝胶</td><td>无水乙醇</td><td>丙稀酸</td><td></td></tr><tr><td>1</td><td>1.6</td><td rowspan=\"6\">3.6</td><td>2.6</td><td>4</td><td>(A396)</td></tr><tr><td>2</td><td>1.3</td><td>2.6</td><td>6</td><td></td></tr><tr><td>3</td><td>1.6</td><td>2.6</td><td>4</td><td></td></tr><tr><td>4</td><td>1.5</td><td>2.6</td><td>6</td><td></td></tr><tr><td>5</td><td>1.8</td><td>2.6</td><td>6</td><td>(A842)</td></tr><tr><td>6</td><td>1.3</td><td>2.6</td><td>6</td><td></td></tr><tr><td>7</td><td>1.8</td><td>3.6</td><td>2.6</td><td>6</td><td></td></tr><tr><td>8</td><td>1.5</td><td></td><td>2.6</td><td>6</td><td></td></tr><tr><td>9</td><td>1.5</td><td></td><td>2.6</td><td>4</td><td>(A-53)</td></tr><tr><td>10</td><td>1.3</td><td></td><td>2.6</td><td>6</td><td></td></tr></table></body></html>  \n\n<html><body><table><tr><td>11</td><td>1.5 3.6</td><td rowspan=\"7\"></td><td>2.6 4</td></tr><tr><td>12</td><td>1.8</td><td>2.6 6</td></tr><tr><td>13</td><td>1.4</td><td>2.6 4 (BM-51)</td></tr><tr><td>14</td><td>1.5</td><td>2.6 6</td></tr><tr><td>15</td><td>1.4 3.6</td><td>2.6 4</td></tr><tr><td>16</td><td>1.5</td><td>2.6 4</td></tr><tr><td>17</td><td>1.2</td><td>2.6 2</td></tr><tr><td>18</td><td>1.2</td><td>2.6 3</td></tr><tr><td>19</td><td>2.0</td><td>2.6 4</td></tr><tr><td>20</td><td>2.4</td><td>2.6 5</td></tr></table></body></html>  \n\n硅烷偶联剂溶液的配制：将去离子水3ml，硅烷偶联剂2ml加入无水乙醇$50.0\\mathrm{ml}$ 中搅拌均匀即得硅烷偶联剂溶液。本实验中采用武大有机硅新材料股份有限公司出品的一种硅烷偶联剂进行低表面能处理，其分子式为 $\\mathrm{CH}_{3}$ （ $\\mathrm{CH}_{2}$ ） $_{11}\\mathrm{Si}$ （OCH）3，分子量 $290\\mathrm{g}\\cdot\\mathrm{mol}^{-1}$ 9  \n\n将清洁玻璃片浸入以上溶胶中，10s后用提拉涂膜机以 $3\\mathrm{mm/s}$ 的速度拉出，室温下静置 $15\\mathrm{{min}}$ ，由于表面吸附及化学结合力，可使溶胶在基片上形成一层均匀的薄膜，如此反复制备涂有3层及5层的膜，自然晾干后将所制基片放入马弗炉中升温2h至 $400^{\\circ}\\mathrm{C}$ ，保温0.5h后自然降温，得到透明二氧化硅薄膜样品。将涂敷有二氧化硅薄膜涂层的玻璃片放入硅烷偶联剂溶液中浸泡3小时，然后将样品放入 $100^{\\circ}\\mathrm{C}$ 烘箱干燥 $60\\mathrm{{min}}$ ，得到透明二氧化硅薄膜。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 71,
+        "chunk": "# 1.3样品表征  \n\n1.3.1接触角(CA)测试：首先予微量注射器对每一样品进行粗测，将 $5.0\\upmu$ L水滴滴在涂有薄膜的载玻片上看水滴在涂膜表面的滚动情况，如水滴容易滚动证明其具有疏水性能，否则不具有疏水性。经过初筛得出8、9、10、11、12、13号样品水滴在涂膜表面容易滚动而具有一定的疏水性能，遂对上述6种试样行接触角检测。打开接触角检测仪连接计算机、接触角检测仪电源及接触角仪视频检测后打开检测光源，将制备的不同涂膜样品放置在样品台上，并用微量注射器缓慢地将 ${\\ 5.0\\upmu\\mathrm{L}}$ 的蒸馏水滴在涂膜上；调整目镜、载玻平台及光源位置，使光源中心、样品表面、蒸馏水滴、目镜在一个水平面上并保持直线；调节焦距至连接计算机视频中出现清晰图像；利用计算机视频截取水滴图像，读出水滴图像的左右两侧的接触角；在该样品上分别选取3个不同的测量点，取其平均值，并分别用接触角测量仪配套设备拍摄液滴在薄膜表面的形貌照片。  \n\n1.3.2防雾性能测试：模拟一定温差的情况下，以空白基片及涂硅烷偶联剂溶液基片作对照，测试疏水性能最好的13号涂膜基片、空白基片及涂硅烷偶联剂基片在遇水汽时的防雾性能；另外，测试疏水性能一般的8号样品，将其3层及5层涂膜进行防雾测试比较。在水浴锅上搭建产生水汽装置，将所制基片静置于其上，疏水二氧化硅薄膜层向水面，基片离水面3cm，室温为 $13^{\\circ}\\mathrm{~C~}$ ，水浴温度设置为 $60^{\\circ}\\mathrm{~C~}$ 。经过5min、10min、20min、30min 后进行对比，观察其表面随时间变化起雾情况，并拍摄数码照片以便进行对比分析。  \n\n1.3.3紫外一可见分光光度计（UV-Vis）表征:对疏水性能最好的13号涂层进行紫外一可见分光光度检测，首先将紫外一可见分光光度计预热15分钟，重新校刻检测仪，设置扫描波长范围 $300{-}800{\\mathrm{nm}}$ ，扫描步长2nm，对3层、5层涂膜进行测试，测试结果采用透过率-波长曲线描述。同样方法测量空白载玻片，与样品进行对比。  \n\n1.3.4场发射扫描电镜（SEM）表征：将予微量注射器往涂膜表面滴水初筛得出的具有疏水性能的8、9、10、11、12、13号样品进行场发射扫描电镜扫描，疏水涂膜载玻片切割成约 $4\\mathrm{mm}\\times5\\mathrm{mm}$ 大小，切割时尽量勿破坏涂膜，用导电胶将切割好的疏水涂膜样品粘结在样品座上，因疏水涂膜导电性能差，采用小型离子溅射器于其表面喷金，后进行表面形貌观测。检测前先打开场发射扫描电镜电源及连接计算机系统，向冷却阱中加入一定量的液态氮后，打开样品室，装样，关闭样品室后将其抽成真空；当真空指示灯亮时，打开V1阀，将电流加至60微安，电压加至2万伏；调节亮度和对比度并通过Z轴将工作距离为 $12\\mathrm{mm}$ ;调节X轴及Y轴，寻找到典型的样品区域后调整放大倍数及调好焦距，慢速扫描、拍照并存贮至连接计算机系统。检测完成后将电流和电压值回零并将对比度、亮度值回零，放大倍数降至100，关闭V1阀，打开样品室，取回样品。",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 72,
+        "chunk": "# 2结果  \n\n2.1",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 73,
+        "chunk": "# 表二：接触角(CA)测试结果  \n\nFig.2 Results of contact angle   \n\n\n<html><body><table><tr><td rowspan=\"2\">序号</td><td colspan=\"2\">接触角测量值(度)</td><td rowspan=\"2\">接触角平均值 (度)</td></tr><tr><td>左侧</td><td>右侧</td></tr><tr><td>空白对照</td><td>73.4</td><td>74.7</td><td rowspan=\"3\">73.4</td></tr><tr><td>空白对照</td><td>74.1</td><td>74.8</td></tr><tr><td>空白对照</td><td>71.2</td><td>72.4</td></tr><tr><td>涂涂硅烷偶联剂</td><td>83.5</td><td>84.7</td><td rowspan=\"3\">83.0</td></tr><tr><td>涂涂硅烷偶联剂</td><td>81.3</td><td>82.8</td></tr><tr><td>涂涂硅烷偶联剂</td><td>82.5</td><td>83.2</td></tr><tr><td>8号3层</td><td>91.2</td><td>91.3</td><td rowspan=\"3\">91.1</td></tr><tr><td>8号3层</td><td>90.5</td><td>91.4</td></tr><tr><td>8号3层</td><td>91.7</td><td>90.8</td></tr><tr><td>8号5层</td><td>109.0</td><td>109.3</td><td rowspan=\"3\">111.0</td></tr><tr><td>8号5层</td><td>108.4</td><td>108.9</td></tr><tr><td>8号5层</td><td>114.2</td><td>114.8</td></tr><tr><td>9号3层</td><td>109.5</td><td>110.2</td><td rowspan=\"3\">109.5</td></tr><tr><td>9号3层</td><td>108.6</td><td>109.8</td></tr><tr><td>9号3层</td><td>109.8</td><td>109.4</td></tr></table></body></html>  \n\n<html><body><table><tr><td>9号5层</td><td>123.3</td><td>122.3</td><td rowspan=\"4\">126.7</td></tr><tr><td>9号5层</td><td>127.9</td><td>127.6</td></tr><tr><td>9号5层</td><td>129.4</td><td>128.8</td></tr><tr><td>10号3层</td><td>114.5</td><td>115.3</td></tr><tr><td>10号3层</td><td>115.2</td><td>115.1</td><td rowspan=\"3\">114.9</td></tr><tr><td>10号3层</td><td>114.9</td><td>114.8</td></tr><tr><td>10号5层</td><td>128.7</td><td>128.9</td></tr><tr><td>10号5层</td><td>129.1</td><td>128.3</td><td rowspan=\"3\">129.1</td></tr><tr><td>10号5层</td><td>129.9</td><td>129.4</td></tr><tr><td>11号3层</td><td>132.4</td><td>131.6</td></tr><tr><td>11号3层</td><td>133.5</td><td>133.8</td><td rowspan=\"3\">132.6</td></tr><tr><td>11号3层</td><td>131.6</td><td>132.7</td></tr><tr><td>11号5层</td><td>150.3</td><td>150.3</td></tr><tr><td>11号5层</td><td>150.1</td><td>150.2</td><td rowspan=\"3\">150.6</td></tr><tr><td>11号5层</td><td>151.4</td><td>151.5</td></tr><tr><td>12号3层</td><td>135.6</td><td>134.2</td></tr><tr><td>12号3层</td><td>134.8</td><td>135.8</td><td rowspan=\"4\">135.3</td></tr><tr><td>12号3层</td><td>135.1</td><td>136.2</td></tr><tr><td>12号5层</td><td>152.8</td><td>153.1</td></tr><tr><td>12号5层</td><td>153.1</td><td>153.1</td></tr><tr><td>12号5层</td><td>151.9</td><td>151.9</td><td rowspan=\"4\">131.3</td></tr><tr><td>13号3层</td><td>131.7</td><td>131.2</td></tr><tr><td>13号3层</td><td>130.9</td><td>131.6</td></tr><tr><td>13号3层</td><td>131.1</td><td>131.4</td></tr><tr><td>13号5层</td><td>153.6</td><td>153.7</td><td rowspan=\"3\">153.5</td></tr><tr><td>13号5层</td><td>153.2</td><td>153.8</td></tr><tr><td>13号5层</td><td>154.3</td><td>152.6</td></tr></table></body></html>  \n\n2.2防雾性能：空白基片放置于水浴锅上即刻起雾，5分钟时空白基片表面已经生成了细密的小水珠，此时水珠已影响到字迹的观察，随着时间的推移，水珠生成越来越大，至30分钟时部分区域的水珠已连成片状；涂硅烷偶联剂溶液基片5分钟时表面起雾，但尚不影响字迹的观察，至10分钟表面也形成了细密的小水珠，随着时间的推移，水珠生成越来越大，至30分钟时水珠未连成片状。而疏水涂膜材料至10分钟时才起雾，但此时雾滴对于透光率的影响有限，仍可以透过涂层看清楚下面的文字，20分钟时表面才生成了细密的小水珠，且水珠较涂硅烷偶联剂溶液基片细小。随着时间的延长，表面水珠越来越大，透光率也受到很大影响。继续延长时间，水滴继续长大，并在重力作用下坠落，而原位再次凝结水滴，如图10。8号样品通过5分钟、10分钟、20分钟、30分钟防雾试验拍照对比可以发现5层涂膜的防雾性能要好于3层涂膜，如图11。  \n\n2.3紫外—可见分光光度计（UV-Vis）：可见光区间内空白基片的透光率约为 $90\\%$ ，经疏水材料涂膜处理后，由于表面粗糙度增加，光线在涂层传播过程中散射导致透光率下降，3层涂层的透光率约为 $75\\%$ ，5层涂层的透光率约为 $65\\%$ ，如图1。  \n\n2.4场发射扫描电镜：在溶胶一凝胶法制备过程中加碱溶胶的11号样品电镜下出现了大量大小不等的结晶，有些区域结晶团聚明显，如图22、图22。未加碱溶胶实验样品电镜下未出现大的结晶，9号、10号样品出现了弹坑状结构，但不典型，特别是10号，弹坑状结构分布很不均匀。12号及13号样品都出现了较多的弹坑状结构，但12号仍有少量团聚现象，弹坑状结构分布仍不够均匀。13号样品出现了较多的且分布均匀的弹坑状结构，弹坑状结构直径约 $200\\mathrm{nm}\\mathrm{\\sim}2\\upmu\\mathrm{m}$ 口其表面粗糙结构均匀，基本未有结晶团聚的现象。随着涂层的层数增加其表面粗糙度随之增加，上述不同样品5层均比3层涂膜表面结构明显粗糙。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 74,
+        "chunk": "# 3讨论  \n\n润湿性是固体的表面的一重要特性，通常描述固体表面润湿性能的指标是水滴在其表面的接触角大小。改变材料表面的浸润性是防雾的常用方法，通常两种极端情况被重点关注：超亲水性与超疏水性。使基材表面高度亲水化，材料表面与水的接触角趋近于零，让水蒸气在基材表面凝结后快速铺展形成透明水膜的亲水性防雾方法已经得到了深入研究[7-10]。临床内镜手术时通常以 $95\\%$ 乙醇、医用安尔碘、肥皂液或其它亲水材料来防雾，但这些亲水防雾材料均存在防雾时间较短缺点，手术时为保证清晰的术野，术者需将鼻内镜镜头反复涂覆防雾剂，从而影响操作延长手术时间。在前三章基于亲水原理已研制出了防雾时间相对较长的防雾剂，防雾时间约为 $10{\\sim}20$ 分钟，较目前临床应用的乙醇、医用安尔碘、肥皂液防雾时间明显延长。超亲水材料利用材料吸引水分子使水汽在材料表面形成一层水膜可防雾。与超亲水材料相对应的是超疏水材料，超疏水是指水滴与材料表面的接触角大于 $150^{\\circ}$ 且滚动角小于 $10^{\\circ}$ 的情况[1-14]。判断某种材料表面是否具有超疏水特性主要依据以下两点：1.水滴在材料表面是否有足够高的接触角 $\\left(>150^{\\mathrm{~o~}}\\right)$ ）；2.水滴在材料表面是否有足够小的滚动角(即液滴开始滚动时，平面所倾斜的角度 ${<}10^{\\circ})$ 。虽然自上世纪50年代以来，人们就开始了对超疏水表面的理论研究，但直到1997年德国波恩大学的植物家WilhelmBarthlott受到荷叶自清洁现象启发，对荷叶的超疏水现象进行了一系列的实验并第一次揭示了荷叶的疏水性能与自洁净之间的关系以来，超疏水材料的研究成为全球广大材料科研工作者的研究热点。在基于经典的Wenzel和Cassie模型的理论指导下，超疏水表面研究进入了一个全新的发展阶段。超疏水材料表面的自洁净效应在工农业生产及日常生活中具有十分广阔的应用前景，涌现出了各种各样的制备方法。常用的有溶胶-凝胶法、相分离技术、化学气相沉积法(CVD)刻蚀法、静电纺丝技术、碳纳米管材料及超亲水与超疏水相互转化材料等。相对于超亲水表面，超疏水表面的构筑要复杂的多。理论上讲，与材料表面超疏水性能密切相关的因素主要有：表面粗糙度、表面粗糙形貌及其化学成分。从表面粗糙度及粗糙形貌而言，要实现超疏水，必须增加材料表面的粗糙度，最好是能形成与天然植物荷叶表面类似的微/纳米级结构。正如 Wenzel方程所述粗糙度增加可使本身疏水材料表面越疏水。从化学组分而言，要使表面超疏水应当使材料表面与水分子的相互作用尽可能降低。大量的研究一致认为，要构建一超疏水表面的两个必要条件为：材料表面要具有一定的粗糙度，要予低表面自由能物质对材料表面进行修饰。  \n\n超疏水材料表面呈微观的微纳米粗糙结构，水滴因材料表面微观的“空气垫”的存在使水滴实际很难浸润材料表面粘附不强，故容易在材料表面滚动而滑落。超疏水材料有天然的及人工合的两大类，自然界动植物界均存在天然超疏水材料，典型植物超疏水材料有荷叶，荷叶表面因天然超疏水，水滴难以浸润其表面，很容易从荷叶表面滑落并带走其表面的污物通常称之为自清洁。动物超疏水现象典型代表的是水蝇，水的腿也是很好的天然超疏水材料，因超疏水水尾能在水面承受自身15倍的重量而不下沉。经研究，荷叶表面、水龟腿表面均存在微观的微纳米结构。学者因受自然界天然超疏水现象的启发，利用不同方法制备了各种不同的超疏水材料，其原理也与自然界超疏水材料超疏原理一样，即材料表面构建微观粗糙的微纳米结构，再予低表面能物质修饰即可构建出超疏水材料，因制作过程特殊决定疏水材料通常能与其它物质表面牢固接合，超疏水材料在工农业生产及白常生活的自清洁、防水等方面己广泛应用，但在防雾方面的报道罕见。显然，防水与防雾属于两个不同概念的范畴，雾是由水汽或雾滴在露点温度下凝结而形成的，水汽或雾滴体积大小明显小于水滴，水滴在超疏水表面容易滚动，然而雾滴在超疏水材料是否也容易滚动尚无法确定。因材料表面超疏水性质，水汽在材料表面凝结形成的雾滴理应能从超疏水材料表面滚动滑落，从而具有防雾性能。目前国内外有关超疏水表面的研究主要集中在以下几方面：1.超疏水表面理论研究；2.超疏水材料制备及其性能研究；3.超疏水材料的应用研究。虽然Gao等认为超疏水表面的一个应用方向是防雾。但迄今为止国内外从超疏水方面进行系统防雾研究的报道少见。  \n\n为了探讨超疏水材料能否防雾，实验时利用构建超疏水材料的基本原理，首先构建了一微观粗糙的表面结构，再予低表面能物质硅烷偶联剂对其表面修饰。实验时采用溶胶一凝胶法制备疏水薄膜。溶胶一凝胶法首先要选用合适的化合物作前驱体，这种化合物要含高化学活性组分，在液相条件下将反应试剂混合，搅拌均匀使之充分进行水解、缩合化学反应，这样可在溶液中形成透明稳定的溶胶体系，然后再溶胶经过一段时间陈化，在陈化过程中胶粒间可缓慢聚合，溶剂则因充满凝胶网络间从而失去流动性，可形成具有三维空间网络结构的凝胶，最后将凝胶于燥并烧结固化即可制备出微米纳米亚结构的材料。在利用溶胶一凝胶法制备疏水材料实验时因加碱溶胶后溶液变得十分混浊，提拉涂膜后表面变得不光整，部分未加碱凝胶实验样品，提拉涂膜后其表面较均匀。  \n\n为进一步深入了解制备的涂层表面的微观结构，对疏水性相对较好的 $9{\\sim}13$ 号行扫描电镜检查。因疏水涂膜导电性能差，为防止电镜检查时电荷积累影响图像质量及破坏疏水涂层。检查前先采用小型离子溅射器在其表面喷金镀膜处理，这样可在疏水涂膜表面可形成一层导电膜，以避免电荷积累进而影响图像质量，并可防止样品的破坏。离子溅射镀膜是在低气压系统中，气体分子在相距一定距离的阴极与阳极之间的强电场作用下电离成正离子和电子，电子飞向阳极，正离子飞向阴极，在阴阳极辉光放电过程中，具有一定动量的正离子撞击阴极，使阴极表面的原子被逐出。疏水涂膜镀膜时，涂层样品放在作为阳极的样品台上，金作为镀膜的材料作为阴极，被正离子轰击而溅射出来的金原子则沉积在疏水涂膜止，形成一定厚度的镀金层。镀膜有真空镀膜及离子溅射镀膜，实验时我们采用离子溅射镀膜主要是检测的样品量较多，而离子溅射镀膜速度快，一次镀膜仅需几分钟，装置结构也简单，每次消耗贵重金属仅约几毫克，且形成的镀膜更均匀、致密及附着力更强。  \n\n从扫描电镜结果可以看出溶胶一凝胶法制备疏水材料实验时加碱溶胶涂膜后的11号样出现了大量大小不等的结晶，如图，图22、图23。而部分未加碱溶胶实验样品电镜下未出现大的结晶，相分离较好，样品涂膜表面出现了相对较均匀的弹坑状结构，如9号、10号、12号及13号样品，9号、10号样品虽然出现了弹坑状结构，但结构均不典型，特别是10号涂层，弹坑状结构分布不均匀。12号及13号样品都出现了较多的弹坑状结构，但12号仍有团聚现象，13号样品检测结果是最好的，出现了较多的且分布均匀的弹坑状结构，其表面粗糙结构均匀，基本未见有团聚的现象，满足了制备疏水材料的首先条件即构建合适的粗糙面。另外，从扫描电镜图可以看出， $_{9\\sim13}$ 号样品表面结构相对较粗糙，且样品随着涂层增多，其表面的粗糙亦明显增加，5层的粗糙度要好于3层涂膜的粗糙度。材料表面形成的弹坑状微观结构是由于向组分中添加丙烯酸酯而得到的。在显微结构和膜生成过程的基础上，这种由丙烯酸酯添加引起的结构性变化有助于相分离，在烧过程中丙烯酸被破坏后留下的孔隙从而形成弹坑状的粗糙结构，这是涂膜具有疏水性能的前提条件。Nakajima等曾推测扫描电子显微镜照片中观察弹坑内部是在烧之前丙烯酸酯存在的地方，并认为弹坑大小与相分离程度有关[16]。实验时采用了4种不同批次的丙稀酸（A396、A842、A53、BM-51)，结果发现，10号12号（加丙稀酸A53）出现了弹坑状的粗糙结构，而13号（加丙稀酸BM-51）出现了典型的弹坑状的粗糙结构，均分布较均匀，而添加丙稀酸（A396、A842）的所有试样均未出现弹坑状的粗糙结构。11号加碱溶胶涂层电镜图可以看出，材料表面有较多大小不等的颗粒，可能是加碱凝胶后溶胶中二氧化硅出现明显团聚致丙烯酸无法完全在溶胶中均匀分散开来，在涂膜表面丙烯酸也不均匀，烧过程中纯溶性丙烯酸未挥发故而形成上述不规则含有大小不等颗粒的表面结构，而未能形成弹坑结构。  \n\n通常认为，合适的微纳米粗糙结构是表面具有超疏水特性的关键[]。本实验清洁光滑玻璃与水滴的接触角为 $73^{\\circ}$ ，含硅烷偶联剂疏水液修饰的光滑玻璃与水滴的接触角要大些，但也仅为 $83^{\\circ}$ 。通过扫描电镜及接触角检测结果对比分析我们发现表面微观结构相似的涂层其接触角亦相近。如9号3层及10号3层表面微观结构相似，其接触角也相近分别为 $109^{\\circ}$ 和 $114^{\\circ}$ ；9号5层及10号5层表面微观结构相似，其接触角也相近分别为 $126^{\\circ}$ 和 $129^{\\circ}$ 。另外，12号3层及13号3层表面微观结构相似，其接触角也相近分别为 $135^{\\circ}$ 和 $131^{\\circ}$ ；12号5层及13号5层表面微观结构相似，其接触角也相近分别为 $152^{\\circ}$ 和 $153^{\\circ}$ 。11号因实验时碱溶胶的添加使得其表面有较多大小不等结晶，但由于结晶颗粒之间互相形成空隙，亦具有较高的粗糙度，涂膜亦具有良好的疏水性能，其接触角3层132.6度，5层150.6度，这也进一步证明，只要能在材料表面构建一定微观结构的粗糙度，而不论粗糙面的构成如何，就具备了疏水性能的前提条件。我们所制备的样品中疏水性能最好的是13 号样品，电镜扫描可以看出13 号样品出现了较多的且分布均匀的弹坑状结构，弹坑状结构直径约 $200\\mathrm{nm}{\\sim}2\\upmu\\mathrm{m}$ ，弹坑状结构直径具有纳米级及微米级二级结构，这与植物界的荷叶及动物界的水腿表面的微纳米级二级结构相似，经低表面能修饰后其表面理应具有超疏水性能。在行接触角检测前予微量泵注射3.0微升蒸馏水滴在涂膜表面，水滴即刻在材料表面在滚动，证明其疏水性能较好，接触角检测也进一步证实其是疏水性能最好的样品。13号样品3层涂膜水滴在表面上接触角为 $131^{\\circ}$ ，具有疏水特性，而5层涂膜水滴在其表面上基本为球形，接触角高达 $153^{\\circ}$ ，已具有超疏水特性，接触角的增加是由于表面的粗糙结构引起的。另外，构建一理想的疏水材料，不仅要强调材料表面的粗糙度，还要强调粗糙度的均匀性，否则即使表面粗糙度再高，如粗糙不够均匀，其疏水性能势必会受较大影响。  \n\n对于粗糙表面,Wenzel认为水滴在其表面可完全浸润,水滴在其表面的接触角为:cosor-rcosθ，式中的r为表面粗糙度,即实际表面积与其投影面积之比值,0为光滑表面的接触角[8]。在第二章及第三章已讨论过，对于亲水材料表面,增加表面粗糙度,材料表面的亲水性能就越好，液滴在其表面的接触角会反而减小。但通过Wenzel方程可以得出：对于疏水材料而言，增加材料表面的粗糙度,液滴的接触角会随之增大。Cassie9 认为水滴在其表面的接触角为:cos0r-flcos0-f2式中,f1、f2分别为接触面中液固界面的面积分数与气固界面的面积分数。从Cassie模型可以得出提高材料表面的粗糙可以提高水滴在基材表面的接触角。Wenzel状态和Cassie 状态都可以实现接触角大于 $150^{\\circ}$ 的超疏水状态。然而材料研究工作者更希望制备的材料符合Cassie 状态，因为在Cassie 状态下材料表面不仅接触角很高，而且由于空气垫的存在，材料表面的滚动角可很小，液滴很容易从材料表面滑落，而很难附着在这种表面上，实现真正意义的不沾水。通过多种试剂配比的实验，我们选出了以酸溶液1.4毫升，无水乙醇2.6毫升，丙稀酸(BM-51)4毫升及不添加碱凝胶的试剂反应可制备出疏水性能较好的材料。制备的涂层表面的接触角可以用Cassie提出的复合表面接触角的计算公式计算：cosor$=\\textrm{f}\\cos\\theta+\\mathbf{f}-1$ 式中，0r和0分别表示粗糙表面的表观接触角和光滑表面的本征接触角,f 为复合接触面中固体的面积分数。我们所制备的超疏水薄膜，通过计算得出涂层表面的复合接触面中固体的面积分数f为0.083。在材料表面疏水的情况下，水滴不能进入到表面的孔隙中，于是空气被截留于孔中，因此，这种表面可以看作是固体与空气的复合表面。液滴被认为是\"坐\"在这种固体表面上。  \n\n透光率是材料光学应用的前提条件，实验时利用物质对不同波长光的选择吸收现象来进行分析的分光光度法来对疏水性最好的13号涂膜进行检测，并对空白玻璃基片进行对比。从透光率曲线可以看出，在可见光区间内，玻璃基片的透光率为 $89\\sim91\\%$ ，而经涂膜处理后，由于表面粗糙度增加，光线在涂层传播过程中散射导致透光率下降，在可见光区间内透光率约为 $60\\sim80\\%$ 。由于可见光的波长范围在 $400{\\sim}800\\ \\mathrm{nm}$ 之间，NakajimaA认为要保证涂层的透明性，涂层的表面粗糙度应控制在 $100\\mathrm{{nm}}$ 以下[20]。事实上，如果不能在保证透光率的情况下，一味通过增加涂层次数改变材料表面粗糙度以求获得更好疏水性能的方式已无意义了。  \n\n由于实验所制备的具有一定的透明度二氧化硅薄膜具有超疏水特性，因此可以用于超疏水表面的防雾性能研究，为今后予疏水材料行内镜防雾研究奠定基础。实验时先对疏水性能最好的13号样品进行防雾试验，首先予空白基片作对照，当空白基片放置于水浴锅上即刻起雾证明其不具有防雾性能，至5分钟时空白基片表面已经生成了细密的小水珠，此时水珠已影响到字迹的观察，随着时间的推移，水珠生成越来越大，至20分钟时开始有水珠连成片状，至30分钟时较多区域的水珠已连成片状。其次，予涂硅烷偶联剂溶液基片作对照，当涂硅烷偶联剂溶液基片放置于水浴锅上，水汽对其表面无明显影响，雾气在其表面上凝结有限，透光率未受明显影响；其表面5分钟后也起雾开始影响到字迹的观察,至10分钟其表面也形成了细密的小水珠，随着时间的推移，水珠生成越来越大，但至30分钟时水珠并未连成片状。而疏水涂膜材料至10分钟时才起雾，细小雾滴凝结于疏水涂膜表面，肉眼难以分辨，此时雾滴对于透光率的影响有限，仍可以透过涂层看清楚下面的文字，20分钟时表面才生成了细密的小水珠，且水珠较涂硅烷偶联剂溶液基片细小，水滴在疏水涂层表面上的凝结速度也比空白基片上及涂硅烷偶联剂溶液基片慢得多，随着时间的延长，表面水珠越来越大，透光率也受到很大影响。继续延长时间，水滴继续长大，但水滴未互相融合成片状，在重力作用下成滴坠落，而原位再次凝结水滴。之后也对具有疏水性的8号样品进行了防雾试验，从接触角检测可以看出5层涂膜的疏水性能要好于3层涂膜疏水性能，防雾测试实验中，在相同的条件下，5层涂膜的防雾性能要好于3层涂膜，从实验拍照的图像对比可以证实，如图11。通过疏水涂层的防雾试验可初步得出相对于空白基片及涂硅烷偶联剂溶液基片而言，制备的疏水薄膜具一定的防雾性能；随着接触角增大，疏水性能越好，防雾效果也越好。本实验时涂膜正背面的温差大，水汽更易在涂膜表面凝聚起雾，而在实际内镜手术时温差要较此实验时小，所以可能更不易起雾。与超亲水防雾不同，超疏水材料在一定程度上使水汽能在其表面上凝结，形成的雾滴对于透光度有一定的影响；而超亲水材料可使水汽在其表面上瞬间凝结并使水汽快速在其表面形成一层水膜，减少光的散射或漫反射从而防雾。所以在光学材料防雾时，亲水材料应为首选。  \n\n在超疏水表面，水滴在表面的滚动角与其重量有关，尺寸越小，滚动角越大。微升量级的水滴形成毫米量级的大小的水滴，其滚动角只有几度，但对于微米尺寸的水滴则不一定容易滚动。另外，水汽在超疏水表面可以凝结，当雾滴凝结成水滴的大小超过一定尺度，比如微米量级，就会对透明度有影响，而此时水滴可能还未能滚动。Zheng等报道了水滴在荷叶表面的动态凝结过程[1]。水汽首先在荷叶表面上的乳突之间形成的\"谷\"中凝结，当其尺寸与\"谷\"的尺寸相当时，水滴再生长会受到周围乳突的挤压。由于水滴在乳突的上下部分的接触角不同，这使得乳突对水滴有一个向上的推动力，推动水滴移动到乳突的顶部，然后水滴继续生长，最终可以形成较大的水滴，从而可以在表面上自由滚动，水滴的大小应大于 $\\gamma30~{\\upmu\\mathrm{m}}.$ 才可能在表面上滚动。空气中的雾滴尺寸通常为 $30\\sim$ $40\\upmu\\mathrm{m}$ ，即此尺寸大小或大于此尺寸的微小液滴对光线的折射与反射会使人视觉感觉模糊，产生所谓的\"雾化\"效果。对大液滴（微升量级，即毫米尺寸量级）而言，我们所制备表面是超疏水表面，而对于微小液滴而言，因对于同一疏水面小液滴的滚动角要较大液滴滚动角大，则不一定具备超疏水特征。虽然我们所制备的超疏水表面接触角为 $153^{\\circ}$ ，也具有一定的防雾性，但防雾效果仍不够满意，其主要原因可能是水汽在此表面上凝结形成的微小液滴较难滚动所致。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 75,
+        "chunk": "# 4结论  \n\n本文以玻璃为基底，采用溶胶凝胶法，以丙烯酸诱导正硅酸乙酯(TEOS)相分离并自组装硅烷偶联剂的方法制备透明二氧化硅涂层，部分具有疏水性能。疏水性能最好的涂层表面微观结构呈具有微纳米级的弹坑状结构。水滴在其表面上的接触角为 $153^{\\circ}$ ，具有超疏水特性及较好的透光性，防雾试验证明其具有一定的防雾性，但如何使超疏水材料获得较满意的防雾效果有待于进一步研究。  \n\n不足之处：1.样品有接触角数据，但缺少滚动角数据；2.只进行了同一材料不同接触角表面的防雾实验，缺少有相同或相近接触角的不同疏水材料其防雾性能之间的比较。3.缺少环境扫描电子显微镜动态表征水汽在疏水涂膜表面的凝结过程进而深入探讨防雾机理。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 76,
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+        "category": " References"
+    },
+    {
+        "id": 77,
+        "chunk": "# 附图  \n\n![](images/acb998332ea2f42ce1bfcc5ef025e7a67059336a85de80fa544688b71c6d4f63.jpg)  \n图1紫外一可见分光光度计（UV-Vis）表征  \nFig.1 Ultraviolet-visible spectrophotometer(UV-Vis) characterization  \n\n接触角(CA）测试结果Results of contact angle  \n\n![](images/8ec0d973dbf1ca7ad5b3c07dd575bd9f76302a1ca55f94fd2d9993614369897b.jpg)  \n图2空白基片接触角 $72^{\\circ}$ Fig.2 contact Angle of $72^{\\circ}$ ofblanksubstrate  \n\n![](images/d5f61e75b132c30815277d24287b75d3aea2c7df5b24814a5d159119219c0f5f.jpg)  \n图3硅烷偶联剂溶液基片接触角 $83^{\\circ}$ Fig.3 contact Angle of $83^{\\circ}$ ofsubstrate coated silane coupling agent  \n\n![](images/5afa81eb03fce153395b83c79419b10953fa93a7c158472f30286c9650eb3f83.jpg)  \n图413号样3层涂膜基片接触角 $131^{\\circ}$ Fig.4contactAngleof131°of substrate with3 layer ofhydrophobiccoating of NO.13  \n\n![](images/27700c523082a47034f0a48d19e0e7351365840c5a4687d36893688132116e83.jpg)  \n图513号样5层涂膜基片接触角 $153^{\\circ}$ Fig.5contactAngleof153°ofsubstrate with5 layer ofhydrophobiccoating ofNO.13  \n\n接触角(CA）测试结果Results of contact angle  \n\n![](images/6fa0d82713ac909d1f3a36931ad458886a4fa13c90d73f2260f3a78c8bdcbcff.jpg)  \n图68号5层接触角111° Fig.6 contact Angle of $111^{\\circ}$ ofsubstrate with5layer of hydrophobiccoating ofNO.8  \n\n![](images/722052650e1a19ed636717a800ab4e09e5709856220d71e33fd275092418c7a3.jpg)  \n图79号5层接触角 $126^{\\circ}$ Fig.7contact Angleof $126^{\\circ}$ ofsubstrate with5layer of hydrophobiccoating of NO.9  \n\n![](images/fb51b71a969403fd5c4852e04e903822b9de44da58c3b22466df3d5727d5705e.jpg)  \n图810号样5层涂膜基片接触角 $129^{\\circ}$ Fig.8contact Angleof $129^{\\circ}$ ofsubstrate with 5layer ofhydrophobic coating of NO.10  \n\n![](images/a49f0f975ed545a123b14a1ed984eb055a6e9da1e1b61be9e17e9cc9d5f3e59d.jpg)  \n图911号样5层涂膜基片接触角 $150^{\\circ}$ Fig.9contactAngleof $150^{\\circ}$ ofsubstrate with5layer of hydrophobiccoatingof NO.11  \n\n![](images/8eee8c9e0e33e76532c6e0d59a58401144466357be1c8c778d20f5cd82657893.jpg)  \n图1013号样品防雾性能(时间min）Fig.10 Anti-fog performance（min）of NO.13  \n\n![](images/bf7315ae938fb89e7768e62ec129d28a13c225d5953d4e152cd78c5edfa513a5.jpg)  \n\n13号样品场发射扫描电镜结果 ScanningElectronMicroscopy ofNO.13  \n\n![](images/9ca9987218899dbb571ae5921940533bc22282f2ca3011df1ed7fe371ff34fd9.jpg)  \n图123层涂膜表面结构 $(\\times2000$ j Fig.12 SEM of substratewith 3layer of hydrophobic coating  \n\n![](images/bc73bf9ebe033131698ecc34da3dd96230d7140cb6426402f4ab6d033ee9169f.jpg)  \n图133层涂膜表面结构（ $\\times10000$ Fig.13SEMof substratewith 3layer of hydrophobic coating  \n\n![](images/eea57357f22749bc29dbb17d9aee63793418ff9a79ae1e32238e5a5f49adf7df.jpg)  \n图145层涂膜表面结构（ $\\times2000$ ）Fig.14 SEMof substratewith5layer of hydrophobic coating  \n\n![](images/1a59066d6e7ba2f9f84ab08cdbef853aeef4bfa3da87300a525a4de161f5330b.jpg)  \n图155层涂膜表面结构 $(\\times10000$ jFig.15SEM of substratewith5 layer of hydrophobic coating  \n\n$9\\sim12$ 号样品场发射扫描电镜结果 Scanning Electron Microscopy of $_{\\mathrm{NO}.9\\sim12}$  \n\n![](images/476b3a19ec47ae941321276abeb1a4770a09049b2898cc46d13470137d5e0c6b.jpg)  \n图169号3层涂膜表面结构 $(\\times2000$ ） Fig.16 SEM of substratewith3 layer of hydrophobic coating of NO.9  \n\n![](images/e41b69057d77a5e1de76e9e39c3f3926d665f5568d9b32e675d9dec8ea80ebbc.jpg)  \n\n![](images/811e4ec764b801604af6b53e44c8f262cb0788221d286e34420a5e881e7f8f32.jpg)  \n图2010号5层涂膜表面结构 $(\\times2000$ ） Fig.20 SEM of substratewith5 layer of hydrophobic coating of NO.10  \n\n![](images/e2ba8d19ae727070d8e3992539870bc2e9eb54dbbe5563e7d145f8587d34b660.jpg)  \n图179号5层涂膜表面结构 $(\\times2000)$ Fig.17SEM of substratewith5 layer of hydrophobic coating of NO.9  \n\n![](images/90d8652bc1c84e4f378dd403446334ecf5c0a79b9368ad2358847251af839c51.jpg)  \n\n![](images/e07ae9cf9bc459946afe70c0572432862efb58e3ff7689b223d8b84c8fa8cbdb.jpg)  \n图1810号3层涂膜表面结构 $(\\times2000$ ） Fig.18 SEM of substratewith3 layer of hydrophobic coating of NO.10   \n图1910号3层涂膜表面结构 $(\\times10000)$ Fig.19 SEM of substrate with3 layer of hydrophobic coating of NO.10   \n图2110号5层涂膜表面结构 $(\\times10000$ ） Fig.21 SEM of substrate with5 layer of hydrophobic coating of NO.10  \n\n$9\\sim12$ 号样品场发射扫描电镜结果 ScanningElectron Microscopy of $_{\\mathrm{NO}.9\\sim12}$  \n\n![](images/71eec654aa4095c87e9c258106031a09bf4bda936d568cebfcfb9c848edb6585.jpg)  \n\n![](images/47b43a7745913ed70bdc77b758224d3a3acc6b7a03c9cbbb3775950c06d453b2.jpg)  \n图2211号3层涂膜表面结构 $(\\times2000$ ）Fig.22 SEMof substratewith3 layerof hydrophobic coating of NO.11  \n\n![](images/4d14af1d3e73ebb8706298f9003819c599b1a20c53e90df1da0ca418c85681a0.jpg)  \n图2412号3层涂膜表面结构 $(\\times2000$ ）Fig.24SEMof substratewith3layerof hydrophobiccoatingof NO.12  \n图2612号5层涂膜表面结构 $(\\times2000$ >Fig.26SEM of substratewith5layerof hydrophobic coating ofNO.12  \n\n![](images/6c9b08405d6fcd1aab5b989df7504cb7616e8f5c985539ad91ecf98ae1a50557.jpg)  \n\n![](images/a0a5c3eb19d630f8ac9174659163a3f1208a7c465afbd59a03b1dc4bc17b0941.jpg)  \n图2311号5层涂膜表面结构 $(\\times2000)$ Fig.23SEM of substratewith5layerofhydrophobiccoatingofNO.11  \n\n![](images/f3800ff805a096cd50ce55f986f79ff6f7f83a1d434379deb715f60c948ee4b9.jpg)  \n图2512号3层涂膜表面结构 $(\\times10000)$ Fig.25SEMof substratewith3layerof hydrophobic coating of NO.12  \n图2712号5层涂膜表面结构 $(\\times10000^{\\cdot}$ jFig.27 SEM of substratewith5 layerof hydrophobic coating of NO.12",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 78,
+        "chunk": "# 全文总结  \n\n本实验依据亲水型防雾剂通常由表面活性剂、溶剂、分散剂等组成原理，选用在医药领域及日常生活应用广泛的丙二醇、月桂醇聚氧乙烯醚、十二烷基硫酸钠、聚乙二醇等原料通过正交设计配制出28种亲水型防雾剂，其具有无色、无刺激性及镜面清晰度高的特点，防雾时间明显较临床常用的医用碘伏和医用乙醇长。防雾原理是由于防雾剂涂在鼻内镜镜头表面可形成一层平整膜，从而延缓了表面活性剂在使用过程中的流失；其中的表面活性剂可降低水的表面张力，使雾滴在薄膜上迅速铺展开形成一层水膜从而达到防雾目的。实验第二部分通过添加一定质量百分比自制的纳米二氧化硅及纳米 $_{\\mathrm{SiO}_{2}-\\mathrm{KH}570}$ 对亲水型防雾剂进行改性，鼻内镜防雾试验得出改性后的防雾剂防雾时间延长，通过粘附功及原子力显微镜表面形态解释了改性后的鼻内镜防雾剂性能要好于改性前防雾剂的主要原因是：提高了防雾剂极性比增强了与鼻内镜镜面的粘附；因涂膜后表面微观粗糙度增加增强了改性后防雾剂的亲水性能。  \n\n实验第三部分是由于受碘伏常用于临床内镜防雾但又存在防雾时间不够长及透光率还不够好的启发，采用在医药、食品等相关领域有广泛应用制碘伏的原料聚乙烯吡咯烷酮水溶液作为鼻内镜防雾剂,并通过纳米氧化锌、氧化钛及纳米 $\\mathbf{SiO}_{2}$ 中空微球对其进行改性使其防雾性能进一步增强。通过粘附功、表面形貌对改性后的防雾机理进行阐述得出与第二部分相似的结论即：一方面因纳米粒子添加使防雾溶液的极性比提高，改性后的防雾剂与鼻内镜表面的粘附增强；另一方面因防雾涂膜后表面微观粗糙度增加进而增强了防雾材料的亲水性能。研究证明以聚乙烯吡咯烷酮水溶液作为鼻内镜防雾剂是可行的。  \n\n实验第四部分通过以玻璃为基底，采用溶胶凝胶法，以丙烯酸诱导正硅酸乙酯相分离并自组装硅烷偶联剂的方法制备二氧化硅薄膜，部分具有疏水性能，对疏水性能最好的涂膜电镜表征得出涂膜表面的疏水性质是由于表面微纳米大小呈弹坑状微观结构造成的。通过与空白玻璃基片及与涂硅烷偶联剂基片对比的防雾试验发现其具有一定的防雾性能，但因表面粗糙结构使其透光率受较大影响。目前通过超疏水材料进行防雾的研究报道少见，如何使超疏水材料获得较满意的防雾效果有待于深入地研究。  \n\n实验的不足之处：目前防雾时间的测试尚无一统一标准，防雾计时存在人为主观因素；正交设计每种物质质量百分比设仅有3个水平，根据这3个水平所配制的防雾剂防雾时间也不一定是最好的，当然随着实验原料的质量百分比水平级别越多，配制最佳配比的防雾剂机率就越大，但存在实验次数明显增多，测试工作更加困难等问题。在第二、三部分通过粘附功大小来判定改性后防雾剂与内镜表面粘附增强，如能加上X射线光电子能谱（X-rayPhotoelectronSpectroscopy）XPS对化学位移及化学键的检测则更具有说服力。另外，制备防雾剂时虽然尽最大可能选用医药应用广泛对人体无毒的试剂，但实验缺少防雾剂毒性试验，其安全性及应用于临床还需要进一步证实。实验四制备的部分涂层虽然表面接触角已达到超疏水条件，但缺少滚动角数据，所以说制备的涂层为超疏水涂层还不够严谨；实验只进行了同一材料不同接触角表面的防雾实验，缺少有相同或相近接触角的不同疏水材料其防雾性能之间的比较；另外，缺少环境扫描电子显微镜动态表征水汽在疏水涂膜表面的凝结过程进而深入探讨防雾机理。  \n\n总之，进行防雾材料研制并对其防雾机理进行深入探讨涉及材料学、有机化学、界面化学、高等物理学及高等数学等多门学科，由于本人知识水平有限，对防雾机理的探讨还不够深入，有些地方可能还不够严谨。今后要加强相关学科学习，加深对防雾机理的认识；要进一步对所制备的防雾材料进行动物毒性试验以证明其安全性。另外，对超疏水防雾，可多制备几种具有不同的接触角、滚动角的超疏水涂层，深入探讨超疏水防雾与接触角、滚动角及涂层本身有何关系。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 79,
+        "chunk": "# 综述一亲水防雾材料研究进展  \n\n玻璃、石英、塑料等透明材料在日常生活、工农业及医疗方面有着广泛的用途，如镜子、各种医用内镜镜头、汽车挡风玻璃及农用塑料薄膜，此类材料的应用使我们的生活变得更加便利。但在湿度大或气温较低时这些材料表面容易水汽凝结而起雾影响其透光率或能见度，其应用受到较大影响，如各种医用内镜镜头手术时需反复擦试镜头来保证其清晰度而延长了手术时间，农用薄膜因透光率降低会降低其光合作用，汽车起雾严重时可导致交通事故的发生。透明材料的雾化问题已给人们的日常生活带来诸多不变，防雾问题已越来越受到学者的关注。所谓起雾是当空气中有一定量或具有一定分压的的水汽存在，在其冷却到露点时，水汽会达到饱和，冷凝析出小雾滴，小雾滴粘附于透明材料表面进而形成大量细小的水珠，由于小水珠曲率半径不同而对光产生的漫反射，最终会导致雾化现象发生。为了防止透明材料表面起雾，目前通常的作法是使材料表面超亲水，超亲水的概念通常是指水滴在材料表面能迅速铺展开来所形成的接触角接近于 $0^{0}$ 。如此可使凝聚在材料表面上的雾滴不形成细小的水珠而可在材料表面铺展开形成薄层水层，减少对光线的漫射，进而保证了材料的透明度。从Young氏方程来看，要达到超亲水的效果，只需要减小固体和液体间的界面张力即可。实际上，实现这一点并不困难，洗液清洗过的玻璃、硅表面以及一些干净的金属氧化物表面就可以表现出很小的接触角，水滴在表面会铺展成水膜。这是由于这些固体表面的分子与水分子有很强的相互作用，以至于水与固体的界面变得接近于水和水之间\"界面”，也就是趋向于消失的界面，此时固体和水之间的界面张力降到接近零。对于某些聚合物的\"软表面”，水和固体之间的界面张力甚至可以变成负值，此时水会渗透入高分子界面以降低表面能[。从亲水性防雾材料的发展史看来，亲水性防雾方法主要包括：小分子表面活性剂型防雾剂、有机高分子亲水性防雾涂料、有机/无机杂化亲水性防雾涂料、氧化物、光催化超亲水表面、碳纳米管材料。",
+        "category": " Introduction"
+    },
+    {
+        "id": 80,
+        "chunk": "# 小分子防雾剂  \n\n小分子防雾剂又称防雾滴剂。早在上世纪50年代，人们发现在镜面上涂上肥皂水就可以防止镜面起雾，这便是最早的予表面活性剂防雾的方法。表面活性剂是指具有固定的亲水亲油基团的一类物质，它在溶液的表面能定向排列，在加入量很少时即能改变体系的表面状态，大幅度降低溶液的表面张力。表面活性剂的分子结构具有两亲性：一端为亲水基团，另一端为憎水基团；亲水基团常为极性的基团，如羧酸、硫酸、氨基或胺基及其盐，也可是羟基、酰胺基、醚键等；而憎水基团常为非极性烃桥。常用的防雾剂是小分子表面活性剂型。主要有木糖醇酯、山梨醇单棕榈酸酯、月桂酸或硬树脂酸甘油单酯等。小分子防雾剂防雾剂因制备过程简单，原料价廉，防雾效果良好，国内外至今还有广泛的用途[3][4]。但因其各组分均为小分子物质，因此不能形成真正意义的膜，故其防雾时间较短，其应用也受到一定的限。",
+        "category": " Introduction"
+    },
+    {
+        "id": 81,
+        "chunk": "# 高分子型防雾剂  \n\n高分子防雾材料是能显著降低液体表面张力的高分子量物质，它是近期才发展起来的一种新型防雾技术。因其含有大量亲水性基团(-OH、-NH,等)而具有较好的亲水性能，其防雾效果好、防雾时间较长且较耐磨。最常用的是丙烯酸酯类、甲基丙烯酸酯类、聚氧乙烯多元醇类防雾剂、硅树脂类防雾剂。Karvinen等制备的丙烯酸和聚丙烯酰胺-硅酸钠膜层形成稳定、均匀的结构后，水滴接触膜层时会迅速分散，实现了膜层很好地亲水性[5。于洁等将一定比例的甲基丙烯酸、甲基丙烯酸羟乙酯、过氧化苯甲酰和乙二醇单甲醚的混合液等在一定条件下反应制得的防雾涂料，其涂膜透明，防雾性、耐擦伤性和耐水性良好。李坚等将聚丙烯酸、阳离子聚丙烯酰胺和硅酸钠通过逐层涂膜法构建丙烯酸/聚丙烯酰胺-硅酸钠亲水防雾膜，烘干后得到稳定的纳米膜层结构，防雾性及稳定性好[7]。RahimiA 等利用有机硅树脂制备了亲水防雾薄膜其防雾性能好]。亲水型高分子涂层的优点为:防雾时间明显较小分子型防雾剂防雾时间长,原料品种多,合成过程亦较容易。但其缺点亦较突出即：水溶性高分子涂料因水的表面张力较高.形成防雾层表面不均匀从而影响透明材料的透光率，油溶性的高分子材料需大量使用有机溶剂,危害人体健康甚至可能造成严重的环境污染。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 82,
+        "chunk": "# 高分子/无机杂化复合防雾涂层  \n\n高分子/无机杂化复合防雾涂层主要由亲水性的有机高分子与少量的硅酸盐或有机硅溶胶组成，其亲水性能由有机高分子涂层和无机涂层决定，而耐磨性能及机械性能则由无机涂层所决定。Fang通过简单的涂层方法将 $\\mathbf{SiO}_{2}$ 纳米粒涂覆于经等离了体处理后高分子聚丙烯聚合物基板上制备了一种超亲水薄膜，认为经等离子体处理后的高分子聚丙烯材料因其形态各异，可作为理想的防雾涂层基板材料。由于表面纳米粒子和带电基板之间静电相互作用，从而制得较稳定和抗溶性多层涂料。其超亲水原因主要是由于材料表面的形貌特点和粗糙度增加引起的[9。Hong 等通过高分子材料聚甲基丙烯酸二甲氨基乙酯(PDMAEMA),甲基丙烯酸3-(三甲氧基硅基)丙酯（PTMOSPMA）与溶胶硅纳米粒、制氧化硅粉、制氧化硅纳米粒混合制备了超亲水表面，高分子材料 $\\mathbf{SiO}_{2}$ 复合涂层能很好地固定在玻璃基片上，二氧化硅纳米粒能固定的在聚合物桥和交联的聚合物薄膜。涂层中二氧化硅纳米粒能形成微/纳米结构，涂层中由于制氧化硅纳米粒和高分子聚合物制氧化硅纳米粒的存在使之表现出超亲水特性。所制备的纳米复合材料涂层性质稳定，具有较好地防雾及自清洁特性。认为高分子材料中加入硅纳米可增加其表面的粗糙度进而导致三维毛细管现象亲水性，硅纳米的比例及其分散程度也是影响复合涂层的重要因素，硅纳米的比例越大、分散度越好其亲水性能越好[10]。有机无机复合防雾涂层在保留涂层亲水性能的基础上，使涂层其他各项性能大大提高，因而这类防雾技术应用前景广泛，已成为防雾领域研究热点。沙鹏宇等以带有环氧基官能团的有机硅氧烷、带有亲水基团的胺基化合物、水解催化剂、固化催化剂等作为反应物，用溶胶-凝胶法制备了有机无机杂化复合防雾耐磨涂料。由于有机组分通过化学键键合到无机网络中，在固化过程中形成缩聚体与共聚体互穿的均一网络型膜层。有机硅氧烷提供了膜层的强度,亲水性胺基化合物提供了良好的防雾性[]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 83,
+        "chunk": "# 氧化物类  \n\n$\\mathbf{TiO}_{2}$ ： $\\mathbf{TiO}_{2}$ 俗称铁白或铁白粉，是一种化学性质稳定的两性氧化物。在自然界中 $\\mathrm{TiO}_{2}$ 以金红石(Rutile)、锐铁矿(Anatase)和板铁矿(Brookite)三种矿物形式存在，纳米 $\\mathrm{TiO}_{2}$ 特别是锐钛型多形体被视为是理想的光催化材料，所以被广泛应用于各种光催化材料。当紫外线照射时二氧化钛薄膜可呈现一个具有非常小的接触角的亲水性表面 $(\\leq5^{0}$ ）[12-15]。自1997年Wang等发现在紫外光诱导下$\\mathrm{TiO}_{2}$ 表现出极好地表面浸润性以来，活性 $\\mathrm{TiO}_{2}$ 薄膜应用研究受到世人瞩目， $\\mathrm{TiO}_{2}$ 材料在防雾、自清洁方面具有广泛的应用，将该薄膜涂覆在玻璃、陶瓷、聚合物和金属表面具有很好的除污防雾效果。通常情况下， $\\mathbf{TiO}_{2}$ 薄膜表面与水有较大的接触角，但是当 $\\mathrm{TiO}_{2}$ 表面受到紫外线照射时，其表面即具有极强的亲水性能，水的接触角减小到 $5^{\\circ}$ 以下，并且还可以渗入到 $\\mathrm{TiO}_{2}$ 颗粒的界面间，由于超亲水性特性使得原本在 $\\mathrm{TiO}_{2}$ 表面上的水滴甚至可在 $\\mathbf{TiO}_{2}$ 薄膜表面完全铺展开来而形成均一的水膜。当 $\\mathrm{TiO}_{2}$ 受紫外光（波长 $<380\\mathrm{nm}$ ）照射时,传导和价带分别产生电子和空穴，电子和空穴向半导体材料表面迁移，其表面因电子降低了钛阳离子（IV）到钛（I）状态，孔穴氧化 $0^{-2}$ 离子。在这个过程中，氧原子释放出，氧空位形成，水分子则占据氧空位产生吸附的OH基团从而使其表面亲水性[6][17]。而在实际生活中，由于需在紫外光照射下才表现其亲水性能，如果把$\\mathrm{TiO}_{2}$ 薄膜置于黑暗中，其表面会转为疏水状态。其原因可能是由于表面吸覆了有机污染物或由于氧分子的吸覆使水分子的释放[。这极大地限制了 $\\mathrm{TiO}_{2}$ 在玻璃防雾及自清洁方面的应用。Gao等认为 $\\mathrm{TiO}_{2}$ 亲水材料除了受紫外光及表面修饰外，还受环境 $\\mathfrak{p H}$ 值的影响，并认为迄今为止还没有哪种 $\\mathrm{TiO}_{2}$ 亲水材料在没有任何高自由能物质修饰或无紫外光照射的情况下其亲水性能不受环境环境pH值的影响[19]。另外因 $\\mathrm{TiO}_{2}$ 具有较大的拆散率，其透光率也在一定程度上限制了其应用。所以制备一种无需光诱导而长期保持亲水性能且透光率的 $\\mathrm{TiO}_{2}$ 材料成为近年来的研究热点。为了克服 $\\mathrm{TiO}_{2}$ 薄膜的缺点，研究人员开始在保证其化学成分和表面层的表面形貌的条件下不少学者对 $\\mathrm{TiO}_{2}$ 结构进行了改性，引入较低的反射率、高亲水性的 $\\mathrm{\\bfSiO}_{2}$ 材料或者制备特殊结构来增加亲水性或研究复合涂层及其它复合半导体[20-23]。Gan 等报道聚乙烯乙二醇与 $\\mathrm{TiO}_{2}$ 纳米通过多层组装制备了一种亲水材料，在无紫外光照射下亦表现出较好的亲水性能[24]。Huang 等通过聚乙二醇2000改性 $\\mathrm{TiO}_{2}$ 后可使其形成多孔的多孔的微结构而呈亲水性[25]。Vassilia 通过溶胶凝胶法在玻璃基片上制备了一种多孔的超亲水的 $\\mathrm{TiO}_{2}$ 薄膜，该薄膜具有数百、数十及数个纳米级别的粗糙结构。认为因 $\\mathrm{TiO}_{2}$ 固有的亲水性加之不同级别的多孔纳米粗糙结构使其具有了极好的浸润性。这种 $\\mathrm{TiO}_{2}$ 薄膜透光率高，及在无传统的光催化作用下亦表现出极好的亲水性能，使其在自清洁及防雾方面应用成为可能[2。Qing 等报道利用四氯化钛、氨水等为原料，在经高温处理过的玻璃基片上制备了一种掺杂氮的超亲水的钛薄膜，这种钛薄膜透明，可见光就可催化呈现超亲水特性，其光催化强度是普通商业自清洁玻璃的14倍[27]。半导体氧化物复合：利用具有不同能带结构的半导体微粒进行半导体复合，可以使窄带隙半导体敏化宽带隙半导体，从而实现宽带隙半导体的可见光激发，同时由于两种半导体之间的能级差能使光生载流子由一种半导体微粒的能级注入到另一种半导体的能级上，导致了有效和长期的光生电子一空穴对的有效分离，因此这将是一种提高纳米 $\\mathrm{TiO}_{2}$ 薄膜可见光激发超亲水性的有效手段。其实质是一种颗粒对另一种颗粒的修饰。通过半导体的复合可提高系统的电荷分离效果，很容易地调节半导体的带隙和光谱吸收范围，使光吸收呈带边型，通过粒子的表面改性可增加其光稳定性和超亲水性。采用带隙较窄的半导体来修饰$\\mathrm{TiO}_{2}$ ，因混晶效应，提高催化活性和改变晶体结构，从而使其超亲水性能得到提高[28]。Machida 等报道往二氧化钛内添加二氧化硅（10～30mol%）形成 TiOz-SiO2复合膜可改善 TiOz的亲水性，特别是在黑暗处[29]。Permpoon 待制备的 SiOz-TiOz薄膜在没有紫外光照射的情况下在很长时间内能保持接触角接近零度的超亲水状态[30]。 $\\mathbf{SiO}_{2}–\\mathrm{TiO}_{2}$ 薄膜的制备包括如下诸多方法：物理气相沉积法、化学溶液沉积法、化学气相沉积、电化学法、溶胶凝胶法，在以上诸多方法中，溶胶凝胶法是最受青睐的[31l。由于大规模制备 $\\mathbf{SiO}_{2}\\mathbf{-}\\mathbf{TiO}_{2}$ 薄膜较困难限制了了其在实际生活中的应用。射频电子磁控溅射法也是一种制备 $\\mathrm{SiO}_{2}{\\cdot}\\mathrm{TiO}_{2}$ 薄膜的常用方法，Liu等通过射频电子磁控溅射法制备 $\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ 薄膜在没有紫外光照射的情况下能达至超亲水状态。该方法使得Ti和Si原子更容易进入 $\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ 薄膜的点阵结构并有利于 Si-O-Ti化学键的形成。TiO $\\mathbf{\\sigma}_{2}/\\mathbf{SiO}\\mathbf{\\sigma}_{2}$ 复合膜制备可以以多种材料为基片，如：玻璃、石英或铝表面。制备的 $\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ 复合膜呈多孔的形态其原因可能是由于在 $\\mathrm{TiO}_{2}$ 中加 $\\mathrm{SiO}_{2}$ 阻碍了 $\\mathrm{TiO}_{2}$ 结晶化。由于 $\\mathrm{TiO}_{2}/\\mathrm{SiO}_{2}$ 界面酸度的提高导致其在自然条件下表现出超亲水特性[32]。S.Permpoon 等则认为：由于界面 Si-O-Ti 联结可促使 $\\mathrm{TiO}_{6}{}^{2.}$ 和 $\\sin^{4+/3}$ 的形成，而这又导致了 $\\mathrm{SiO}_{2}\\mathrm{-TiO}_{2}$ 颗粒界面的电子不平衡，复合膜表面由于去质子化的 $\\mathrm{TiO}_{6}{}^{2.}$ 单位和质子化的 $\\mathrm{SiO}_{4}^{4+/3}$ 单位存在使得其更易吸附 $\\mathrm{H}_{3}\\mathrm{O}^{+}$ 和 OH离子,这使得 TiO $\\mathbf{\\sigma}_{2}/\\mathbf{SiO}\\mathbf{\\sigma}_{2}$ 复合膜表面更易吸附水分子而表现出超亲水特性3。据报道，加了二氧化硅的二氧化钛薄膜增强了光诱导超亲水性能，并且在没有紫外线照射的情况下还可在一定时间内保持超亲水性能[34]。Poznyak 和 Sviridov 报道通过溶胶凝胶法往 $\\mathrm{TiO}_{2}$ 内添加 $\\mathrm{In}_{2}\\mathrm{O}_{3}$ 形成 $\\mathrm{TiO}_{2}\\mathrm{-}\\mathrm{In}\\ _{2}\\mathrm{O}_{3}$ 薄膜可明显改善 $\\mathrm{TiO}_{2}$ 的光学性及亲水性[35]。Eshaghi 等通过溶胶凝胶法往 $\\mathrm{TiO}_{2}$ 内添加 $\\mathrm{In}_{2}\\mathrm{O}_{3}$ 、 $\\mathbf{SiO}_{2}$ 形成 $\\mathrm{TiO}_{2^{-}}\\mathrm{SiO}_{2^{-}}\\mathrm{In}_{2}\\mathrm{O}_{3}$ 薄膜可明显改善其透光率及亲水性。原因是由于电荷不平衡羟基大量吸覆于薄膜表面，另外，表面酸度增加也是其即使在没有光照的情况下亦具有超亲水特性。K.Guan 等亦认为薄膜表面大量羟基吸覆及表面酸度增加也是 $\\mathrm{TiO}_{2}$ 即使在没有光照的情况下亦具有超亲水特性的主要原因。  \n\nZnO：纳米ZnO属于纳米级金属氧化物，呈针状或球状结构，是一种新型高功能精细无机产品，纳米ZnO由于其尺寸介于原子簇和宏观微粒之间，因具有光吸收、光催化等特性使具有广泛的应用前景[38-39]。Sun 等认为 $z_{\\mathrm{nO}}$ 和 $\\mathrm{TiO}_{2}$ 具有类似的浸润性转化机理.紫外光照射以后，薄膜中的电子和空穴分离，产生电子一空穴对，产生的电子一空穴对可以移动到表面.通常，空穴可以和表面晶格中的氧反应在表面形成氧空位;而电子可以和晶格中的金属离子反应生成 $Z_{\\mathfrak{n}^{+}}$ 缺陷点，如此，水分子可能配位进氧空位，发生表面游离水分子的吸收而在材料表面形成亲水点进而使其呈超亲水特性[40]。化学气相沉积法（CVD）能较好地控制系统形态的发生，在纳米材料制备方面亦有广泛的应用[41-42l。其中的光诱导超亲水（PSH）和光催化氧化（PCO）是化学气相沉积法（CVD）制备纳米ZnO 材料的重要的光化学过程[43。这两者均是由于光诱导产生了电子空穴对进而使之具有半导体光学特性。其原因是光诱导产生了电子空穴对能与 $z_{\\mathrm{nO}}$ 金属离子点阵相互作用并且它们各自又能与材料表面氧离子形成桥接，从而形成Zn与氧缺失位点[44]。材料表面羟基形成使其表面具有起亲水特性。而在黑暗处由于表面羟基数量的减少从而其从超亲水状态转为超疏水[45-46]。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 84,
+        "chunk": "# 碳纳米管  \n\n自1991年Iijima报道以来，碳纳米管因其优越的物理化学性能而广泛应用于许多领域[47]。碳纳米管的紫外吸收特性，在紫外激光照射下吸收光子能量，并将其传递给样品分子使其电离。另外，碳纳米管还具有一定程度亲水性能的特殊材料，其表面浸润特性易控[48-49]。表面浸润性是碳纳米管材料的一重要特性[50]。Erbil等认为碳纳米管材料表面的接触角是由其表面的化学组成和粗糙度决定的[51l。电子显微镜下由于纳米尺寸大小的不同，碳纳米管材料表面本身就表现出一定程度的粗糙度，因此，对碳纳米管材料的修饰主要集中在改进化学组成上[52]。根据Wenzel's理论cosθw $=r$ cosOy可知，材料表面的粗糙度可增强其浸润的特性，即粗糙度增加可材料亲水性能增加。w是粗糙表面的接触角，是该材料在理想状态下光滑面的接触角， $r$ 是材料表面的粗糙度。所以在没有紫外光照射的情况下获得一稳定的超亲水表面是予高自由然化学物质来修饰[53]。Gao等认为使用高表面化学物质修饰同样存在诸多问题如：修饰过程需要多步才能完成，可能含有污染物，严格的修饰条件，环境污染，最大的缺陷是其亲水性能不够稳定[9]。通常由化学气相沉积法制备的碳纳米管材料不能溶于大多数溶剂，这使得其应用受到很大限制。目前文献报道了多种方法诱导碳纳米管材料从超疏水或疏水向超亲水或亲水性能转变，如酸化法、微波处理法、氧等离子蚀刻法、碳纳米管材料表面溶入杂环原子法[5456]。Jin等报道了通过简单喷涂而无需任何化学修饰的方法制备的超疏水碳纳米管薄膜，其重要的特性是通过紫外线照射和置于黑暗处时其表面可由超亲水向超疏水转换，薄膜表面吸覆水分子光化学反应使得其呈超亲水，在黑暗中由于水分子被氧置换后薄膜呈超疏水性。这项研究表明，在紫外线光照射下所制备的碳纳米管材料具有可调谐的表面润湿性[57]。Sun等报道通过聚N-异丙基丙稀酰胺组装的碳纳米管材料具有温敏的浸润性[58]。Han等报道用一种碳纳米管材料通过易控的方法制备了一种透明的、超亲水和超疏水可转换的薄膜[59。Pillai等制备了一种碳纳米管材料，通过改变电场可使其表面从超疏水向超亲水转变，但这种转变并不可逆转[。Miyauchi等报道通过酸处理在钛钠米管上合成了一种单晶金红石纳米棒，这些金红石纳米棒在水溶液能很好地分散开来形成稳定的胶体溶液，然后将铜离子联接到金红石纳米棒上。由于金红石 $\\mathrm{TiO}_{2}$ 价带与表面修饰的铜离子之间界面的电荷转移，与铜离子联接后金红石纳米棒能吸收可见光。通过涂层法在基片上形成透明的与铜离子联接的金红石纳米棒薄膜，其在可见光下呈超亲水性[6]。Wang等报道了在在干燥条件50℃紫外线照射下，臭氧（O）和它的分解成分（O，O)与碳纳米管材料反应，碳纳米管材料表面可迅速从超疏水状态转变为超亲水状态。而在真空高温下通过加热碳纳米管可使其反向转变，即从超疏亲状态转变为超疏水状态。据此可认为，碳纳米管粗糙程度在其表面润湿性转变中起到至关重要的作用[]。  \n\n总之，随着工农业、医疗卫生事业的发展及人们生活水平的不断提高,人们对防雾产品需求越来越大,防雾材料的制备已发展成为一个重要的产业。制备一种透光率高和防雾时间持久性但制备方法简单,原料成本低廉,无毒辣且耐磨性好的防雾材料一直是广大科研工作者们努力的方向。目前市场上应用比较多的还是各种防雾剂类的产品，光催化的TiO防雾膜在一定范围内也得到了应用。制备一种无需光诱导而长期保持亲水性能且透光率的TiO材料成为近年来的研究热点。碳纳米管亲水防雾材料在基础研究方面取得了很大的进展,但要应用到实际生活中还仍有待于进一步的深入研究。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 85,
+        "chunk": "# 参考文献  \n\n[1] Feng X, JiangL. Design and Creation of Superweting/Aniwetting Surfaces[J].Adv. Mater,2006,18,3063-3078.   \n[2] Wang R, Hashimoto K, Fujishima A,et al.Light-induced amphiphilic surfaces[J].Nature, 1997. 388(6641): 431-432.   \n[3] Hideki ISHOKA. Antifogging Glass for a Vehicle Window,Method for Producing the Same, and Fixing Structure for the same[P].US Patent:0239017 A1,2009-9-24.   \n[4]Chen Zhao, Cormell Chappell.Silicate-Containing Antifogging Coatings[P].US Patent:0003160 A1,2011-1-6.   \n[5]  Karvinen SM. The Effects of Trace Element Doping on the Optical Properties and Photocatalytic Activity of Nanostructured Titanium Dioxide[J]Ind Eng Chem Res,2003,42 (5):1035-1043.   \n[6]于洁，王大勇，程俊．聚丙烯酸酯透明防雾涂料的研制[]．涂料工 业,2002,32(9):7-8.   \n[7]李 坚,刘佳一，张阳德.表面改性对光学眼镜膜增透防雾效果的影响[J]·中 国组织工程研究与临床康复,2010,14(8):1418-1421.   \n[8] RahimiA, Gharazi S, Ershad-Langroudi, et al.Synthesis and characterization of hydrophilic nanocomposite coating on glass substrate[J].Journal of Applied Polymer Science,2006,102(6): 5322-5329.   \n[9]Jason Fang, Antonios Kelarakis, Luis Estevez. Superhydrophilic and solvent resistant coatings on polypropylene fabrics by a simple deposition process[J]. J  \n\nMater. 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+        "category": " References"
+    },
+    {
+        "id": 86,
+        "chunk": "# 综述二 超疏水材料研究进展  \n\n自1997年德国波恩大学的植物家第一次揭示了荷叶的疏水性能与自洁净之间的关系以来，超疏水材料的研究成为全球广大材料科研工作者的研究热点。现综述如下。",
+        "category": " Introduction"
+    },
+    {
+        "id": 87,
+        "chunk": "# 超疏水表面理论研究  \n\n润湿性是固体的表面的一重要特性,通常描述固体表面润湿性能的指标是水滴在其表面的接触角大小，当接触角大于 $90^{\\circ}$ 时称之为疏水表面,而当接触角大于$150^{\\circ}$ 则称为超疏水表面。对于粗糙表面,Wenzel认为水滴在其表面可完全浸润，水滴在其表面的接触角为:cosor-rcosθ,式中的 $\\textbf{r}$ 为表面粗糙度,0为光滑表面的接触角[2]。Cassie 等认为水滴在其表面的接触角为:cos0r=flcosθ-f2 式中,fl、f2 分别为接触面中液固界面的面积分数与气固界面的面积分数3]。Wenzel 状态和Cassie状态都可以实现接触角大于 $150^{\\circ}$ 的超疏水状态。  \n\n此后，学者对于粗糙固体表面的超疏水性能机理，进行了大量的理论研究。Johnson等构造出一理想正弦曲率平面，测量水滴在其表面上的接触角并通过反复试验得出当固体表面形貌为Wenzel模型时，水滴在具有疏水性的粗糙固体表面的接触角以及滚动角均随粗糙因子r的增加而增大，而r等于1.7时为临界值，当r大于1.7以后，由于水滴和固体表面接触界面空气含量增加，使得粗糙具有疏水性能的固体表面由Wenzel模型转变为Cassie模型，此时再继续增大r，水的接触角可继续增大，而滚动角反而减小[4。Drelich从分子水平讨论了固体表面的不均匀性，结合气-固-液三相接触的线张力和滚动角修正了Cassie方程[5。此后Drelich等又在亲水、疏水区构成的平整表面上发现，材料表面的浸润性与其化学组成明显相关。Yamauchi等运用Wenzel方程和Cassie方程，探讨了聚四氟乙烯材料体系中聚四氟乙烯粒子的形状、大小、分散性等因素与材料表面的疏水性能密切相关。Wei 等人研究了表面颗粒形状、排列方式和间距对疏水性的影响[7。金美花等制备了高接触角和高粘滞力的阵列聚苯乙烯纳米管膜，水滴在其表面的接触角达到 $162^{0}$ ，而滚动角却大于 $23^{0}$ ，并指出要制备一性能良好的动态超疏水表面，除了水滴在其表面的接触角大于 $150^{0}$ ，还要求水滴在表面的滚动角小于 $10^{0}$ 更为科学[。Sakai等研究了重力与粗糙液-固界面的相互关系，并指出气体被吸附于粗糙固体表面的微孔中后，其界面张力可因重力作用而增大[9]。Yoshida等通过对含氟甲基丙烯酸甲酯及光滑的甲基丙烯酸甲酯的表面浸润性进行了研究，通过调节共聚物表面的氟含量，发现其表面的接触角随氟含量的增加而增大，而滚动角的却先增加后减小[]。禹营等通过化学气相沉积的方法，在具有规则微形貌的硅片表面沉积硅的有机物制备出了超疏水表面，并发现不同的成膜时间和微形貌的结构尺寸直接影响着表面的润湿性；表面的接触角随着时间的增长而增大；当微形貌深度一定，随着形貌宽度的增加接触角无明显变化，但超过某一临界值时，接触角下降明显，不再形成超疏水表面[。Richard等认为：三相接触线是对超疏水表面液滴最重要的影响因素，液滴接触面可随着接触角的增大而缩小,接触线变得更不易变形,滚动角即前进角和后退角之间的滞后作用随之减低[2]。研究一致认为，要构建一超疏水表面的两个必要条件为：材料表面要具有一定的粗糙度，要予低表面自由能物质对材料表面进行修饰。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 88,
+        "chunk": "# 超疏水材料制备及其性能研究  \n\n在基于经典的Wenzel和Cassie模型的理论指导下，超疏水表面研究进入了一个全新的发展阶段。涌现出了各种各样的制备方法，常用的有溶胶-凝胶法、相分离技术、化学气相沉积法(CVD)、刻蚀法、静电纺丝技术、碳纳米管材料及超亲水与超疏水相互转化材料等。  \n\n溶胶一凝胶法：是用含高化学活性组分的化合物作前驱体，在液相下将这些原料均匀混合，并进行水解、缩合化学反应，在溶液中形成稳定的透明溶胶体系，溶胶经陈化胶粒间缓慢聚合，凝胶网络间充满了失去流动性的溶剂，形成三维空间网络结构的凝胶。凝胶经过干燥、烧结固化制备出微米纳米亚结构的材料。Venkateswara等以甲基三甲氧基硅氧烷(MTMS)、甲醇为原料，通过溶胶-凝胶法制备了透明薄膜，以三甲基氯硅烷进行修饰，水在其表面的接触角高达 $166^{\\circ}$ ，该硅气凝胶表面富含大量的 $\\mathrm{CH}_{3}$ 基团和粗糙的纳米级孔洞结构使之具有超疏水性能[13]。Shirtcliffe等通过溶胶-凝胶法使用甲基三乙氧基硅烷制备了多孔泡沫具有超疏水性能材料，该材料并能够在不同的温度下实现超疏水到超亲水的转变[4]。Michele 等以三乙氧基甲基硅烷原料，通过溶胶-凝胶法制备了一减反射且透明的超疏水薄膜，水在其表面的接触角高达 $168^{0}$ ，且稳定性极好，将其置于室外2000小时后仍超疏水特性[15]。Sunetra 等以丁基三甲氧基硅烷和正硅酸乙酯为前驱体，通过溶胶-凝胶法，以玻璃为基片，通过浸渍涂膜制备了透明的超疏水薄膜[]。Satish 等以三乙氧基甲基硅烷、三甲基甲氧基硅制备了一透明粗糙表面结构，电镜下观察其为直径1-10微米大小的球形粒子组成，以低表面能物质氯化三甲基硅烷修饰后其表面具有超疏水特性，水在表面的接触角高达$172^{\\circ}$ ，最小滚动角仅为 $2^{0[17]}$ 。Sanjay等以甲基三乙氧基硅烷、四乙氧基硅烷、甲醇为原料，以氟化铵为催化剂，通过溶胶凝胶法在室温下制备了一透明的多孔薄膜，电镜观察孔径约 $250\\mathrm{-}300\\mathrm{nm}$ 大小，水滴在其表面的接触角为 $160^{\\circ}$ ，滚动角为 $3^{\\circ[18]}$ 。  \n\n相分离技术：是指将一些室温下难溶的高聚合物在升温条件下溶解于合适的溶剂中,然后降温分相和脱除稀释剂,形成微孔结构的技术。Xu等利用相分离的原理，成功制备了类似荷叶微米/纳米双重结构的超疏水材料，水在其表面的接触角高达 $166^{\\circ}$ ，滚动角仅为 $3.4^{\\circ[19]}$ 。Joong 等通过相分离技术合成了2-[3-（三乙烷氧基硅烷基）丙基氨甲酰胺基]-6-甲基-4氢吡啶酮，该物质在乙酸乙酯中通过氢键形成两端具有三乙烷氧基团的棒状二聚体分子，通过水解形成Si-O-Si 键交联的粗糙结构，经低表面能物质修饰后其表面具有了超疏水性能[0]。Yabu等通过相分离技术，使用带有氟化丙烯酸酯和甲基丙烯酸甲酯结构的共聚物溶解于氟化溶剂中。将玻璃璃基片浸润在氟硅烷溶液中做氟化处理后干燥，得到一种孔径约 $100\\mathrm{nm}$ 的多孔状结构薄膜，水滴在其表面的接触角可达到 $170^{\\circ[21]}$ 。Nakajima等通过正硅酸乙酯（TEOS）中添加丙烯酸聚合物，采用相分离技术，得到弹坑状结构粗糙表面，经过氟硅烷(FAS)化修饰处理后其表面呈超疏水[22]。  \n\n化学气相沉积法(CVD)：是半导体工业中应用最为广泛的用来沉积多种材料的技术，包括大多数绝缘材料，金属材料和金属合金材料。其基本原理是两种或两种以上的气态原材料导入到一个反应室内，然后他们相互之间发生化学反应，形成一种新的材料，沉积到晶片表面上。江雷等以金为催化剂，利用化学气相沉积法制备了具有微米/纳米双重结构的氧化锌薄膜，水在其表面接触角可达 $164.3^{\\circ}$ ，另外，经紫外光照射后由材料表面可由超疏水性能向超亲水转变，水的接触角小于 $5^{\\circ\\left[23\\right]}$ 。Lau 等通过化学气相沉积法制备了垂直阵列碳纳米薄膜，并用聚四氟乙烯对其进行修饰,得到超疏水表面[24]。Zhao 等将ITO导电玻璃浸入聚二丙烯二甲基氯化铵水溶液和聚对苯乙烯磺酸盐的水溶液各 $5\\mathrm{{min}}$ ，干燥后以处理过的ITO导电玻璃作为阴极在Ag/AgNO3电镀液中进行电沉积处理，因离子键发生自组装行为，镀在ITO 玻璃上的两种聚电解质使得银在ITO 表面选择性生长，最终得到类树枝结构的粗糙结构，其表面经十二烷基硫醇修饰后具有超疏水特性[25]。  \n\n刻蚀法：刻蚀法是一种较为简单且直接的方法。根据刻蚀的能量来源不同分为等离子体刻蚀、激光刻蚀及化学刻蚀法。McCathy等采用刻蚀法在硅片上刻蚀出不同形状、不同尺寸、不同深度的柱形列阵,并分别采用含碳氢长桥、碳氟长桥、碳硅长桥的低表面能物质修饰表面,结果表明当刻蚀深度大于 $20\\upmu\\mathrm{m}$ 时,刻蚀深度与接触角无关,当列柱间距小于 $32\\upmu\\mathrm{m}$ 时,上述低表面能物质修饰后接触角均大于 $160^{\\circ\\left[26\\right]}$ 。Jiang等人用激光刻蚀的方法在硅片表面刻蚀间距为微米级的小柱子来增加表面的粗糙度，和平滑的硅片相比，粗糙度大大增加，制备的表面具有显著的超疏水性[]。金美花等采用激光刻蚀方法制备了具有柱子的形貌类似于类\"菜花\"状粗糙度的聚二甲基硅氧烷(PDMS)膜，由于其表面具有微米-亚微米-纳米复合的多级结构而呈现较好的超疏水性能，水滴的接触角高达 $165^{0}$ [28] 。Baldacchlni等采用激光加工技术制作粗糙表面，不但能使表面化学性质保持不变，还能在表面形成密集的微结构粗糙表面，从而大幅度提高表面的疏水性能，与水接触角高达 $170^{\\circ}$ [29]。Khorasani等在室温环境下用CO 脉冲激光处理聚二甲基硅氧烷(PDMS),其表面的接触可高达 $175^{\\circ}$ 。电镜观察可见在激光处理后，PDMS表面产生多孔结构，PDMS的分子桥排列规整[30]。  \n\n静电纺丝技术：静电纺丝技术是一种较常用的制备微米、纳米纤维的方法，通过静电力可将高分子溶液从喷嘴中喷出而在表面植入超细纤维，形成立体网状结构，通过调整喷嘴的直径、溶液的电导率、溶液表面张力和粘度来调整纤维直径大小。Ma 等利用电纺技术制备了一种聚己内酯粗糙表面，予全氟烷基乙基甲基丙烯酸甲酯对薄膜进行修饰后水滴在其表面的接触角高达 $175^{\\circ}$ ，滞后角仅约 $2.5^{\\circ}$ ，具有极好的超疏水特性〖31。江雷课题组利用聚苯乙烯为原料，采用电纺技术制备了一种新颖的具有多孔微球与纳米纤维复合结构的超疏水薄膜，其中多孔微球对薄膜的超疏水性起主要作用，而纳米纤维则交织成一个三维的网络支架，固定住多孔微球，增强了薄膜的稳定性。水滴在其表面的接触角高达$160^{\\circ}$ [32]。王丽芳等采用静电纺丝技术制备了一粗糙表面，并予低表面能物质硅油在烧过程中进行同步修饰，制备出接触角大于 $150^{0}$ ，滚动角小于 ${\\boldsymbol{5}}^{0}$ 的TiO超疏水表面。该超疏水表面是由于 $\\mathrm{TiO}_{2}$ 纳米纤维和微米尺寸颗粒状硅油经高温分解后而形成了纳米纤维网膜结构，此微纳米二级粗糙结构经疏水性硅油分解产物的修饰后而具有超疏水性能[33]。  \n\n碳纳米管材料：早在1991年，日本NEc的Iijima教授在用电弧法制备富勒烯时通过高分辨透射电镜分析放电后阴极上的沉淀物，发现了具有纳米尺寸的碳的多层管状物-碳纳米管[34]。碳纳米管自被发现以来，因其多种优良性能引起了人们广泛兴趣。碳纳米管是在一定条件下由大量碳原子聚集在一起形成的同轴空心管状的纳米级材料，它的径向尺寸为纳米数量级，轴向尺寸为微米数量级。碳纳米管可以是单壁碳纳米管,也可以是多壁碳纳米管。单壁碳纳米管由单层石墨卷绕而成，多壁碳纳米管由多层同心石墨卷绕而成，也可看作是同轴心的单壁碳纳米管组成。碳纳米管材料因其硬质的纳米圆柱形结构，直径约1至几十纳米不等，长度约数百至微米结构大小，这使其成米构建纳米粗糙结构的理想材料。并在超疏水领域里有广泛的应用[35]。Huang等通过化学气相沉积法制备的碳纳米管材料在其表面修饰氟硅烷后其表面接触角高达160度以上[3。Xu等认为碳纳米管材料制备的超疏水结构最显著的特点是其轮廓分明的结构，但由于制备过程特殊，应用碳纳米管制备大规模超疏水材料受到限制[37。Wu等通过商业碳纳米管和防水生物材料及硬脂酸制备了一种仿生超疏水多壁碳纳米管材料[38]。Georgakilas 等采用具有长桥全氟烷烃桥的硅烷偶联剂接枝到碳管表面上，并将此改性碳管共混到高分子基体中获得了疏水表面[9。张超等基于ATRP聚合方法在碳纳米管的管壁接枝了低表面能的含氟聚合物，进而利用含氟聚合物共价包裹的碳纳米管来取代羟基化的碳纳米管来降低所制备聚合物复合膜的表面自由能．同时，采用溶剂蒸气刻蚀法使掩理或分散在聚合物基体中的碳纳米管端部或部分管体裸露在复合膜表面，制备了一种表面粗糙度高以及表面目由能低的具有良好疏水性能的复合材料表面[4]。  \n\n超亲水与超疏水相互转化材料：为了拓宽对材料的应用，超亲与超疏性能互相转换的材料应用研究引起了学者的极大兴趣，制备表面浸润性可逆转的材料各种各样的方法相继报道出来如：热处理法[41、电场法[、溶剂处理法[43、光催化法[44]。Chang 等认为因大量羟基存在，离解溶液中的H和OH离子或与之相互作用，金属氧化物表面常呈亲水状态，增加其表面粗糙度后可呈现超亲水特性。他在空气中通过加热铜基板制备了纳米线状的 $\\mathtt{C u O}$ 薄膜，其表面呈超亲水状态，然而将其置于室温或将其低温退火处理后CuO纳米线状薄膜可从超亲水状态向超疏水状态转变。其超疏水性是由于材料表层的 ${\\tt C u O}$ 还原成 $\\mathtt{C u_{2}O}$ 结构造成的，当将这种材料经高温处理后，其表面又可成超亲水性45]。Feng 等报道制备的ZnO纳米棒薄膜经紫外光照射或置于黑暗中后可从超亲水向超疏水转变[46]。Pei 等报道利用铜板在K2S2O8(0.1M）及 KOH(3M）浸渍后制备了一种无而化学物质修饰可超亲与超疏性能互相转换的表面，该表面呈微/纳米级结构，呈疏水性能时其接触角可达 $158^{0}$ ，其主要原因是该表面呈荷叶状的微/纳米级结构和呈亲水性的羟基消失造成的。当予紫外光照射或置于黑暗中时呈亲水性能，其接触角 $<10^{0[47]}$ 。Hou 等将 $\\mathrm{TiO}_{2}$ 纳米粒浸于高分子聚本乙烯材料后于玻璃基片上涂膜，不同温度下干燥形成PS/TiO $_2$ 薄膜，随着干燥温度的升高其表面接触角也随之增大，通过调整干燥温度其表面可超亲与超疏性能互相转化，在紫外光照射下其表面接触可低于 ${\\boldsymbol{5}}^{0}$ 。经加热后又呈现超疏性能[48]。",
+        "category": " Introduction"
+    },
+    {
+        "id": 89,
+        "chunk": "# 超疏水材料的应用研究  \n\n超疏水性透明涂层由于具有独特的表面性能，在建筑玻璃、汽车挡风玻璃、卫星天线等方面具有重要的应用前景。由于涂层的超疏水特性，水滴及冰雪等不易其表面附着，这在防止空调和冰箱等电器结霜、天线结冰等方面有重要的作用。另外，如果在船只、潜艇等水上工具的外层涂上一层具有超疏水特性的薄膜，基于Cassie模型原理，由于涂层表面具有一定的粗糙度，涂层结构的微孔与水之间的表面层中存在一空气垫，这将大大降低船只在运行过程中与水之间的阻力。Feng 等将不锈钢网及聚四氟乙烯、聚乙酸乙烯酯、聚乙烯醇制备了一超疏水网，由于其表面超疏水、亲油性能而用于分离油水混合物分离[49]。  \n\n生物医学领域：生物材料是其与生命科学之间相互渗透而产生的一个重要领域,在设计生物医用材料时,首先遇到的是体内植入材料的生物相容性问题由于有机质和界面之间多种不同的相互作用，基材表面的生物粘附是一个十分复杂的现象。具有强疏水性和强亲水性表面的材料都具有较好的血液相容性。当高分子材料的疏水性很强时,由于对血液成分的吸附能力下降而具有较好的血液相容性。例如聚四氟乙烯(PTFE),它的疏水性很强而血液相容性也很好。超疏水材料具有很低的表面自由能和很好的抗粘附性能，因此，超疏水的材料也显示了良好的生物相容性。Wang等将制备的亲水/超疏水的表面浸入蛋白质溶液中时，在超疏水部分形成一空气层,这个空气层可有效地阻止了细胞与表面的接触,形成了一独特的分离区域,这使得活细胞可以在亲水性表面自由生长[50]。Sun等人在阵列型的碳纳米管基材上涂附含氟聚氨酯，得到了接触角大于 $160^{0}$ 的超疏水材料表面，予一种部分氟化且具有生物兼容性的聚氨基甲酸乙酯表面来对血小板的粘附性能进行测试,发现超疏水表面因具有明显抗细胞粘附的特性从而使得其具有非常优异的血液相容性，这为制备新的血液相容性材料，如人工血管，提供了一条新的途径[5。Khorasani等人研究发现超疏水聚PDMS比普通PDMS有更好的血液相容性，另外他通过血小板粘附实验证实了经二氧化碳脉冲激光处理后具有超疏水特性有机硅表面具有较好的血液相容性，可用作人体植入材料的表面涂层[52]。袁志庆通过血液相容性实验表明,具有低滚动角的超疏水聚丙烯表面抗凝血性能优于高滚动角的超疏水表面和光滑薄膜;超疏水聚丙烯和光滑聚丙烯表面的溶血率都低于 $5\\%$ 并且具有低滚动角的超疏水聚丙烯表面的溶血率最低;超疏水聚丙烯表面没有血小板吸附,而光滑的聚丙烯薄膜表面则有大量的血小板吸附[53]。曹宗顺等指出当高分子材料的疏水性增强时，由于对血液成分的吸附能力下降而具有较好的血液相容性，聚四氟乙烯等就是如此，它们的疏水性很强，血液相容性也很好。因而，增强高分子材料的疏水性是研制生物医用高分子材料的方法之一[54]。  \n\n超疏水材料因其的独特的超疏水及自清洁性能使其在工农业生产及日常生活中具有广阔的应用前景,近年来已成为广大材料科研工作者的研究热点。不同的超疏水材料及其制备方法也相继报道出来,但是超疏水表面的在实际生活中应用还不够广泛,许多问题尚需解决，超疏水材料能否防雾还未见有系统报道，防水与防雾机理是否一致还未能阐述清楚。为最终实现超疏水材料在的工农领域的广泛应用,仅仅注重超疏水材料的制备技术还远不够的，超疏水强理论研究还要加强，而对这一系列问题的深入研究必将为最终实现超疏水表面的广泛应用提供可能。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 90,
+        "chunk": "# 参考文献  \n\n[1] Barthlott W, Neinhuis C. Purity of the sacred lotus or escape from contamination in biological surfaces[J].Planta, 1997, 202(1):1-8.   \n[2] Wenzel, RN. Resistance of Solid Surfaces to Wetting by Water[J].Ind. Eng. Chem.,1936,28:988-994.   \n[3] A B D Cassie, S Baxter. Wettability of porous surfaces[J]. Transactions of the Faraday Society,1944,40,546-551.   \n[4] Rulon E. Johnson Jr., Robert H. Dettre. An evaluation of Neumann's \"surface equation of state\"[J].Langmuir,1989, 5(1):293-295.   \n[5] Jaroslaw Drelich ， Jan D. Miller. Modification of the Cassie equation [J].Langmuir,1993,9(2):619-621.   \n[6] Yamauchi G, Miller J D, Saito H. The wetting characteristics of PTFE particulate composites [J].Materials Transactions,1996,37 (4):721--728.   \n[7] Wei Chen, Alexander Y. Fadeev, Meng Che Hsieh,et al. McCarthy Ultrahydrophobic and Ultralyophobic Surfaces: Some Comments and Examples[J] Langmuir,1999,15(10):3395-3399.   \n[8] 金美花．超疏水性纳米界面材料的制备及研究．吉林大学博士学位论文， 2004，第37页.   \n[9] Hideki sakai, Tomiko Fujii.The Dependence of the Apparent Contact Angles on Gravity[J].Journal of Colloid and Interface Science 1999,210(1):152-156.   \n[10] Yoshida N, Abe Y, Shigeta H,, etal. Sliding behavior of water droplets on flat polymer surface[J].J Am Chem Soc. 2006,128(3):743-747.  \n\n[11]禹营,汪家道,陈大融.超疏水表面膜的制备[J].润滑与密封,2007,32(8):37-38.  \n\n[12] Richard D., Clanet C., Quere, D..Contact time of a bouncing drop[J].Nature, 2002, 417:811-811.  \n\n[13] A.Venkateswara Rao, Sanjay S. Latthe, Digambar Y. Nadargi. Preparation of MTMS based  transparent  superhydrophobic  silica  films by  sol-gel method[J].Journal of Colloid and Interface Science, 2009, 332,484-490.  \n\n[14] Shirtcliffe N J, Mchale G, Newton M I, et al.Porous materials show superhydrophobic to superamphiphilic switching[J].Chem Commun, 2005， 15: 3135-3137.  \n\n[15] Michele Manca, Alessandro Cannavale, Luisa De Marco. Durable Superhydrophobic and Antireflective Surfaces by Trimethylsilanized Silica Nanoparticles-Based Sol-Gel Processing[J].Langmuir,2009, 25(11):6357-6362.  \n\n[16] Sunetra L. Dhere, Sanjay S. Latthe, Charles Kappenstein .Transparent water repellent silica films by sol-gel process[J].Applied Surface Science, 2010, 256, 3624-3629.  \n\n[17] Satish A. Mahadik,Mahendra S. Kavale,S.K. Mukherjee. Transparent Super hydrophobic silica coatings on glass by sol-gel method[J].Applied Surface Science 2010,257,333-339.  \n\n[18] Sanjay S. Latthe a, Hiroaki Imai b, V. Ganesan. Porous superhydrophobic silica films by sol-gel process[J].Microporous and Mesoporous Materials 2010, 130,115-121.  \n\n[19]  Xu J, Jiang L, Xie Q D, et al. Facile creation of a super-amphiphobic coating surface with bionic microstructure[J].Adv.Mater., 2004, 16,302-305.  \n\n[20] Han JT, Lee DH, Ryu CY, Fabrication of superhydrophobic surface from a supramolecular organosilane with quadruple hydrogen bonding. J Am Chem  \n\nSoc. 2004,126(15):4796-4797.  \n\n[21]  Yabu H, Shimomura M.Single step fabrication of transparent superhydrophobic porous polymer films[J]. Chem Mater, 2005,17, 5231-5234.  \n\n[22]A.Nakajima, K Abe, K Hashimoto.PreParation of hard super-hydroPhobic films with visible light transmssion[J].Thin Solid Films, 2000, 376(122):140-143.  \n\n[23]  Jiang L., Liu H., Feng L., et al. Reversible wettability of a chemical vapor deposition prepared ZnO film between superhydrophobicity and superhydrophilicity[J]. Langmiur, 2004, 20,5659-5661.  \n\n[24] Lau K KS, Bico J, Teo K B K, et al. Superhydrophobic carbon nanotube forests[J].Nano letters, 2003, 3(12):1701-1705.  \n\n[25] N Zhao, F Shi, L Jiang, et al. Combining layer-by-layer assembly with electrodeposition of silver aggregates for fabricating superhydrophobic surfaces[J].Langmuir 2005,21(10):4713-4716.  \n\n[26] T J McCathy. Ultrahydrophobic Surfaces. Effects of Topography Length Scales on Wettability[J].Langmuir, 2000,16(20):7777-7782.  \n\n[27] Sun T， Wang G, Feng L, et al.Reversibie Switching between Superhydrophilicity and Superhydrophobicity[J]. Angew.Chem.. Int.Ed.,2004, 43(3): 357-360.  \n\n[28]金美花，廖明义,江雷.超疏水性聚二甲基硅氧烷膜的制备及其表面吸附性研究[J].高等学校化学学报,2008,28(5):996-998  \n\n[29] BALDACCHINI, Craey T ,Zhou JE. Superhydrophobic Surfaces Prepared by Micro-structuring of Silicon Using a Femtosecond Laser. Langmuir(Letter), 2006,22,4917-4919.  \n\n[30] Khorasani M T , Mirzadeh H , Kermani Z.Wettability of porous polydimethylsiloxane surface: Morphology study[J]. Appl Surf Sci, 2005, 242,239-245.  \n\n[31] Ma M,Mao Y, Gupta M, et al. Superhydrophobic fabric produced by electrospingning and chemical vapor deposition[J].Macromolecules, 2005,38 (23):9742-9748.  \n\n[32]  Zhao Y,Zhai J, Jiang L. A lotus-leaf -like superhydrophobic surface:a porous microsphere/nanofiber composite film prepared by electrohydrodynamics[J] Angew Chem Int Ed. 2004,43,4338-4l.  \n\n[33]王丽芳，赵勇，江雷，等．静电纺丝制备超疏水 $\\mathrm{TiO}_{2}$ 纳米纤维网膜[]]高等学校化学学报，2009，30（4)：731-734.  \n\n[34]Iijima S. Helical microtubes of graphite carbon[J].Nature, 1991,354:56-58.  \n\n[35]  Paul Roach, Neil J. Shirtcliffe, Michael I. Newton.Progess in superhydrophobic surface development[J].Soft Matter, 2008, 4, 224-240.  \n\n[36] Huang L, Lau SP, Yang HY,et al.Stable superhydrophobic surface via carbon nanotubes coated with a ZnO thin film[J].2005, 109(16): 7746-7748.  \n\n[37] D. Xu, H. Liu, L. Yang,et al.Fabrication of superhydrophobic surfaces with non-aligned alkyl-modified multi-wall carbon nanotubes[J]. Carbon, 2006, 44, 3226-3231.  \n\n[38] Tongfei Wu, Yongzheng Pan, Lin Li. Study on superhydrophobic hybrids fabricated from multiwalled carbon nanotubes and stearic acid[J].Journal of Colloid and Interface Science,2010,348,265-270.  \n\n[39] Georoakilas, V., Bourlinos, A. B., Zboril, R.,et al. Synthesis, Characterization and Aspects of Superhydrophobic Functionalized Carbon Nanotubes[J].Chem. Mater., 2008,20,2884-2886.  \n\n[40]张 超，郭述忠，汪伟志，等．含氟聚合物修饰碳纳米管及其聚氨酯复合疏水膜的研究[J].化学学报,2009,67（9）:1001-1007.  \n\n[41] Shirtcliffe, N. J., McHale, G.,Newton, M. I.,et al.Porous materials show superhydrophobic to superhydrophilic switching[J].Chem. Commun., 2005,25, 3135-3136.  \n\n[42] Krupenkin, T. N.,Taylor, J. A., Wang, E. N., et al. Reversible Wetting Dewetting Transitions on  Electrically Tunable  Superhydrophobic Nanostructured Surfaces (letter).Langmuir, 2007, 23(18):9128-9133.  \n\n[43] Zhu Y, Feng L, Xia F,et al. Chemical Dual-Responsive Wettability of Superhydrophobic PANI-PAN Coaxial  Nanofibers[J].Macromol.  Rapid Commun , 2007,28, 1135-1141.  \n\n[44] Ho Sun Lim, Joong Tark Han, Donghoon Kwak,et al. Photoreversibly Switchable Superhydrophobic Surface with Erasable and Rewritable Pattern [J].Am.Chem. Soc. 2006, 128, 14458-14459.  \n\n[45] FengMing Chang, ShaoLiang Cheng, SiangJie Hong. Superhydrophilicity to superhydrophobicity transition of CuO nanowire films[J].Applied Physics Letters,96,114101-2010.  \n\n[46] Feng,X., Feng,L., Jin,M.,et al. Reversible superhydrophobicity to super hydrophilicity transition of aligned ZnO nanorod films[J].Am. Chem. Soc. 2003,126(1):62-63.  \n\n[47] MingDe Pei, Bo Wang, Er Li, Xuehong Zhang.The fabrication of superhydrophobic copper films by a low pressure oxidation Method[J]. Applied Surface Science, 2010,256,5824-5827.  \n\n[48] Weixin  Hou,Qihua  Wang.  UV-Driven  Reversible Switching  of a  \n\nPolystyrene/Titania Nanocomposite Coating between Super hydrophobicity and Superhydrophilicity[J]. Langmuir, 2009, 25(12): 6875-6879.  \n\n[49] Lin Feng,Zhongyi Zhang,Zhenhong Mai, et al. A Super-Hydrophobic and Super-Oleophilic Coating Mesh Film for the Separation of Oil and Water[J]. Angewandte Chemie,2004,116(15):2046-2048.  \n\n[50]  Wang Y ,Sims CE,Marc P, et, al. Allbritton NL. Micropatterning of living cells on a heterogeneously wetted surface[J].Langmuir, 2006, 22,8257-8262.  \n\n[51] Aoley Sun, Hong Tan, Dong Han, et al.No platelet can adhere-largely improved blood compatibility on nanostructured supergydrophobic surfaces [J]. Small，2005，1 (10): 959-963.  \n\n[52]  Khorasani M, Mirzadeh H. In Vitro blood compatibility of modified PDMS surfaces as superhydrophobic and superhydrophilic materials[J]. Joumal of applied polymer science， 2004， 91: 2042-2047.  \n\n[53]袁志庆，陈洪，汤建新．超疏水聚丙烯表面的制备及血液相容性研究[J]功能材料．2007,8(38):1359-1361.  \n\n[54]曹宗顺，卢凤琦.界面现象与材料的生物相容性[J].化学通报.1994，7，15-20.",
+        "category": " References"
+    },
+    {
+        "id": 91,
+        "chunk": "# 缩写词简表  \n\n<html><body><table><tr><td>英文缩写</td><td>英文全称</td><td>中文名称</td></tr><tr><td rowspan=\"9\">SDS PEG</td><td>Nasal Endoscope</td><td>鼻内窥镜</td></tr><tr><td>Antifogging Agent</td><td>防雾剂</td></tr><tr><td>Ethyl alcohol absolute</td><td>无水乙醇</td></tr><tr><td>1,2-Propylene glycol</td><td>丙二醇</td></tr><tr><td>Polyoxyethylene lauryl ether</td><td>月桂醇聚氧乙烯醚</td></tr><tr><td> Sodium dodecyl sulfate</td><td>十二烷基硫酸钠</td></tr><tr><td>Polyethylene Glycol</td><td>聚乙二醇</td></tr><tr><td>Ammonia water</td><td>氨水</td></tr><tr><td>caustic soda</td><td>氢氧化钠</td></tr><tr><td>Hydrophile</td><td></td><td>亲水性</td></tr><tr><td></td><td>Hydrophobe</td><td>疏水性</td></tr><tr><td>CA</td><td>Contact angle</td><td>接触角</td></tr><tr><td>TEOS</td><td>Tetraethyl orthosilicate</td><td>正硅酸乙酯</td></tr><tr><td></td><td>n-hexane</td><td>正已烷</td></tr><tr><td>MEG</td><td>Mono ethylene glycol</td><td>乙二醇</td></tr><tr><td>PVP</td><td> Polyvinylpyrrolidone</td><td>聚乙烯吡咯烷酮</td></tr><tr><td>PAA</td><td> Polyacrylic Acid</td><td>聚丙烯酸</td></tr><tr><td></td><td> Tetra-n-butyl Titanate</td><td>钛酸丁酯</td></tr><tr><td>Wa</td><td>Work of adhension</td><td>粘附功</td></tr><tr><td>AFM</td><td>Atomic force microscope</td><td>原子力显微镜</td></tr><tr><td>SEM</td><td> scanning electron microscope</td><td>扫描电镜</td></tr><tr><td>TEM</td><td> transmission electron microscope</td><td>透射电镜</td></tr><tr><td></td><td> sol-gel method</td><td>溶胶凝胶法</td></tr></table></body></html>",
+        "category": " References"
+    },
+    {
+        "id": 92,
+        "chunk": "# 致谢  \n\n本论文从选题、设计到实验实施和论文的撰写是在我的导师谢民强教授悉心指导下完成的。感谢谢老师多年来在学业上给予我极大的指导和帮助，在工作和生活上给予我无微不至的关怀和照顾并且对我今后的发展道路提出了许多宝贵意见。恩师严谨求实的治学态度、精湛的医术以及诲人不倦严于律己的高尚品德都将是我一生做人、从医的楷模。  \n\n感谢珠江医院耳鼻咽喉-头颈外科郭梦和教授、龙孝斌教授、李永贺教授、黄金中教授、谢南屏教授、文忠教授、徐宏胜副教授、江刚副教授、张宏征副主任医师、龚剑医师多年来在临床工作中的关心和帮助，使我受益匪浅。  \n\n感谢华南理工大学材料科学与工程学院符小艺副研究员在课题设计、实验实施及样品表征方面的指导与帮助。  \n\n感谢珠江医院耳鼻咽喉科姜雯频护士长及全体护士给予我的支持和帮助。  \n\n感谢陈帅君、陈浩、许煜铭、张涛、江珊珊、洗献清、王瑾瑜等师兄妹给予我的支持与帮助。  \n\n感谢南方医科大学研究生学院及珠江医院教务处的领导与老师给予学业上的大力支持和帮助。  \n\n最后，我要衷心感谢我的妻子和女儿及在远方的父母给我的默默鼓励和支持，让我顺利的走完人生中这段最难忘的路程。",
+        "category": " Conclusions"
+    },
+    {
+        "id": 93,
+        "chunk": "# 博士研究生期间发表论文情况  \n\n[1]万良财，谢民强，符小艺,等.透明超疏水薄膜的防雾性能研究.中国现代医学杂志，2011;21(35):4375-4379.  \n[2]万良财，谢民强，符小艺,等.亲水型鼻内窥镜防雾剂的研制.南方医科大学学报,2011;31(9):1521-1525.",
+        "category": " References"
+    },
+    {
+        "id": 94,
+        "chunk": "# 参加国内国际会议  \n\n1.2012.03.16～2012.03.18参加第44期全国鼻内镜手术培训班暨慢性鼻窦炎国际研讨会。  \n2.2012.05.26～2012.05.27参加广东省第11期题骨解剖及耳显微外科手术培训班。  \n3.2012.10.16～2012.10.17参加国际头颈肿瘤联盟全球巡讲（IFHNOS）暨东亚头颈肿瘤论坛学术会议。",
+        "category": " References"
+    },
+    {
+        "id": 95,
+        "chunk": "# 南方医科大学学位论文原创性声明  \n\n本人郑重声明：所呈交的论文是本人在导师的指导下独立进行研究所取得的研究成果。除了文中特别加以标注引用的内容外，本论文不包含任何其他个人或集体已经发表或撰写的成果作品。对本文的研究做出重要贡献的个人和集体，均已在文中以明确方式标明。除与外单位合作项目将予以明确方式规定外，本研究已发表与未发表成果的知识产权均归属南方医科大学。  \n\n本人承诺承担本声明的法律效果。  \n\n作者签名：万良财 日期：2013年5月30日",
+        "category": " Abstract"
+    },
+    {
+        "id": 96,
+        "chunk": "# 学位论文版权使用授权书  \n\n本学位论文作者完全了解学校有关保留、使用学位论文的规定，同意学校保留并向国家有关部门或机构送交论文的复印件和电子版，允许论文被查阅和借阅。本人授权第一军医大学可以将本学位论文的全部或部分内容编入有关数据库进行检索，可以采用影印、缩印或扫描等复制手段保存和汇编本学位论文。  \n\n本学位论文属于（请在以下相应方框内打“√\")：  \n\n1、保密口，在年解密后适用本授权书。  \n2、不保密。  \n\n![](images/da34f282b3ce975d878ac77a1abafa09b59f5f327e18c6da910abbdd35fe8b17.jpg)",
+        "category": " Conclusions"
+    },
+    {
+        "id": 97,
+        "chunk": "# 统计学审稿证明  \n\n编号：D13-0189",
+        "category": " References"
+    },
+    {
+        "id": 98,
+        "chunk": "# 研究生毕业论文统计学审稿证明  \n\n兹有博士研究生万良财的论文（编号：D13-0189）《鼻内镜防雾材料研制及防雾机理探讨》中有关统计学方面的内容，经我系审定合格，特此证明。",
+        "category": " References"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/▓у▓у╫╘╫щ╫░ Science ╓╨╬─.json b/task2/task2-chunks/▓у▓у╫╘╫щ╫░ Science ╓╨╬─.json
new file mode 100644
index 0000000..cecfa43
--- /dev/null
+++ b/task2/task2-chunks/▓у▓у╫╘╫щ╫░ Science ╓╨╬─.json	
@@ -0,0 +1,122 @@
+[
+    {
+        "id": 1,
+        "chunk": "这些技术仍是新技术，目前正在积极探索中，研究将揭示沉积技术和基本驱动力如何影响薄膜的形成、特性和性能，以及加工的难易程度、产量和规模。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 2,
+        "chunk": "# 以技术为驱动逐层组装纳米薄膜  \n\n展望未来：在过去的二十年里，逐层组装技术已被证明具有显著的功能，并对科学研究产生了深远的跨学科影响。扩大该工艺的规模对于进一步提高  \n\n约瑟夫-J-理查森、马蒂亚斯-比约恩马姆、弗兰克-卡鲁索\\*背景：在过去的几十年里，逐层（LbL）组装薄膜一直备受关注，因为它能够对薄膜厚度进行纳米级的控制，并有多种选择。",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# 在我们的网站上  \n\n阅读全文请访问： http://dx.doi. org/10.1126/ science.aaa2491  \n\n进展：与经典 LbL 组装的扩散驱动动力学相比，LbL 组装技术的最新进展探索了组装过程的不同驱动力。  \n\n在现实世界的应用中，了解如何精心选择组装方法以利用不同技术的具体优势有可能带来变革。比较  \n\n可用于平面和颗粒基底涂层的材料。通过对材料的选择，可为各种应用设计出具有赞助性和功能性的薄膜、  \n\n包括催化、光学、能源、薄膜和生物医学。此外，现在越来越多的人认识到，组装技术会极大地影响薄膜的物理化学特性，并最终影响薄膜的性能。  \n\n将基材浸入聚合物溶液中。目前已有的不同组装技术包括：浸渍、去湿、卷对卷、离心、乳化、计算饱和、固定、旋转、高重力、喷涂、雾化、电沉积、磁性组装、电泳、电泳、电泳、电泳、电泳、电泳、电泳、电泳、电泳、电泳、电泳、电泳、电泳、电泳、电泳、电泳、电泳、电泳、电泳、电泳、电泳、电泳、电泳等。耦合、过滤、微流体和流化床。这些技术可归纳为五大类，其中也可应用自动化或机器人技术，即：  \n\n(i) 沉浸式、(ii) 旋转式、(iii) 喷雾式、(iv)电磁式和 (v) 流体装配式。许多  \n\n这些技术之间的比较仍有待进行，特别是在颗粒基底涂层方面，虽然比较有限，但对促进基础研究和实际应用至关重要。",
+        "category": " Introduction"
+    },
+    {
+        "id": 4,
+        "chunk": "#  \n\n<html><body><table><tr><td colspan=\"4\"></td></tr><tr><td></td><td colspan=\"3\">旋转</td></tr><tr><td>评论摘要</td><td colspan=\"2\"></td><td>作为功能材 料的独特应</td></tr><tr><td>层材料</td><td>电磁喷雾</td><td></td><td>用</td></tr><tr><td colspan=\"4\">流体</td></tr><tr><td rowspan=\"6\"></td><td rowspan=\"6\"></td><td></td><td></td></tr><tr><td></td><td></td></tr><tr><td></td><td></td></tr><tr><td>逐层组装纳米薄膜以制备功能材料。所得薄膜的特性和性能取决于基底和层材料的选择以及组装技术。</td><td></td></tr><tr><td></td><td></td></tr><tr><td></td><td></td></tr><tr><td colspan=\"3\"></td><td></td></tr></table></body></html>  \n\n![](images/362ed256e354f4b7e2947d7fbdcd7b3f8fa53d3375e6c9f403464f93eca6c2cf.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 5,
+        "chunk": "# 评论  \n\n多层装配",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 6,
+        "chunk": "# 以技术为驱动逐层组装纳米薄膜  \n\n约瑟夫-J-理查森、马蒂亚斯-比约恩马姆、弗兰克-卡鲁索\\*由于多层薄膜在催化、光学、能源、薄膜和生物医学等不同领域的潜在应用，它们引起了科学界的浓厚兴趣。  \n\n在此，我们回顾了目前采用以下方法进行多层薄膜沉积的技术我们讨论了这些技术的不同特性和应用。我们重点介绍了五种不同的组装方法--浸入式、旋转式、喷射式、电磁式和流体组装式--每种方法都具有逐层组装薄膜的材料和加工优势。每种技术都有许多创新，可用于自动分层和改进分层，这对研究和工业应用都很重要。此外，我们还讨论了如何通过明智地选择组装技术来设计具有定制物理化学特性的薄膜，如独特的层状分层、可控粗糙度和高度有序堆积。  \n\n用于制作此类影片的技术形成了五个不同的类别，即：(i) 沉浸式；(ii) 旋转式；(iii) 浮雕式；(iv) 浮雕式、  \n\n(iii) 喷涂、(iv) 电磁和 (v) 流体组装（图 2）。这些组装技术既影响工艺性能，也影响材料的最终性能（表 1），因此，谨慎选择组装方法对于成功应用组装薄膜至关重要。此外，装配技术目前的发展有两大主题：首先是层沉积不再采用随机扩散驱动动力学，其次是从手工组装向自动化系统发展。  \n\n身临其境的装配  \n\n沉浸式 LbL 组装（有时也称为 \"浸渍组装\"）是应用最广泛的方法，也是新技术经常比较的标准。浸入式组装通常是通过人工将平面基底浸入所需材料的溶液中（2、24、25），然后经过三个清洗步骤去除未结合的材料（26）。微粒基底也可使用浸没法进行分层；但是，清洗和沉积步骤用于 LbL 组装，以各种材料（如聚合物、蛋白质、脂质、核酸、纳米颗粒、超结构）作为薄膜成分  \n\n功能材料的性能取决于它们以明确定义和可控的方式与周围环境相互作用的能力。无论是利用光子或电子，分离气体  \n\n环境-材料界面是决定材料在各种应用中性能的关键。涂层技术提供了控制材料表面的手段，从而创造出复合材料，在这种材料中，界面和材料的主体在很大程度上可以独立设计和控制。  \n\n逐层（LbL）组装是在基底上涂覆功能薄膜的一种普遍方法。继早期的多层组装研究报告（1、2）之后，该领域在过去二十年中才有了长足的发展（3）。一般来说，LbL 组装是一个循环过程，在这一过程中，带电材料被吸附在基底上，经过洗涤后，带相反电荷的材料被吸附在第一层之上。这样就形成了厚度一般在纳米级的 单层双电层，然后可以重复沉积过程，直到形成所需厚度的多层薄膜为止 (3)。在某些应用中，可以移除基底，形成独立的宏观薄膜，如膜（4），或独立的微观或纳米薄膜，如空心胶囊（5、6）。尽管静电作用仍被广泛用于促进薄膜的形成，但其他分子相互作用（如共价作用、氢键作用、主客作用等）也已得到充分证实。  \n\n澳大利亚研究理事会（ARC）聚合生物纳米科学与技术卓越中心和墨尔本大学化学与生物分子工程系，澳大利亚维多利亚州帕克维尔 $3010_{\\circ}$ \\*通讯作者。电子邮件：fcaruso@unimelb.edu.au  \n\n(7).LbL 组装所具有的简便性、多功能性和纳米级控制能力，使其成为在光学、能源、催化、分离和生物医学等多个领域最广泛使用的平面和颗粒基底涂层技术之一（图 1A）。  \n\n由于 LbL 组装广泛应用于具有不同标准工具和程序的领域，以及与多孔膜、颗粒和生物物质等基底相关的不同加工要求，因此开发出了许多 LbL 组装技术。例如浸渍 (2)、  \n\n脱湿 (8)、卷对卷 (9)、离心 (10)、起泡 (11)、计算饱和度 (12)、浸渍 (13)、起泡(14)双化 (13)、旋转 (14)、高重力 (15)、喷雾(16)、雾化 (17)、电沉积 (18)、磁性组件 (19)、电耦合 (20)、过滤 (21)、流体学 (22) 和流化床  \n\n(23).这些不同的方法通常被视为 \"黑箱\"，主要关注的是使用什么材料（输入）来组装薄膜（输出），而很少关注实际的组装方法。然而，现在越来越多的人认识到，组装方法不仅决定了工艺特性（如时间、可扩展性和人工干预），还直接影响薄膜的物理化学特性（如厚度、均匀性、层间和层内薄膜组织），而这两组特性都与特定应用的性能有关（图 1B）。",
+        "category": " Introduction"
+    },
+    {
+        "id": 7,
+        "chunk": "# 打开 \"黑盒子\"  \n\nLbL 组装的基础是依次将基底暴露于构成多层薄膜的材料中。组装技术  \n\n一般通过离心将颗粒分离成颗粒（5、6、10）。关于使用颗粒沉积平面多层膜的早期研究指出，从理论上讲，只要条件合适，任何能产生表面电荷的材料（如金属、非金属、有机物和无机物）都可用于生长多层膜（2、24、27）。另据报道，每层的厚度与被吸附颗粒的厚度一致（24、28）。与气体沉积和成核沉积等非 LbL 组装技术相比，Im-mersive 组装技术（使用颗粒多层膜 (27)或聚合物多层膜 (3)）可形成更均匀的薄膜，因此 LbL 组装技术被广泛用于薄膜形成0  \n\n浸入式组装的改进包括通过将沉积动力学从随机扩散转向更快的动力学（如露湿产生的动力学）（8），以及通过使用机器人浸入机将劳动密集型步骤自动化（24、26、29、30）来加快工艺流程。早期研究中用于平面组装的胶体，每个吸附步骤只需浸泡 1分钟（31）；然而，使用聚合物进行浸泡组装时，基底最好浸泡约 15 分钟才能充分沉积（25、26）。为了缩短聚合物的组装时间，并允许低表面电荷和/或小接触面积材料的沉积，可使用掺杂有机溶剂（如二甲基甲酰胺）的溶液，通过脱湿过程消除漂洗和干燥步骤（8）。由于吸附过程不再受扩散控制，而是受蒸发和脱水控制，因此脱水可使组装时间缩短约 30 倍。另一种摆脱随机扩散的有趣方法是利用磁力搅拌棒对聚合物溶液进行持续搅拌，这样就能使聚合物层沉积在  \n\n浸泡后几十秒（32）。与其通过使用不同的吸附动力学来加快吸附过程，不如通过自动化处理过程来缩短处理时间（9、24、26、27、29、30、33）。一种自动化方法是使用石英晶体微天平（QCM）作为基底，通过计算机监控的反馈回路来控制分层（30）。QCM 使分层过程基于固定的吸附材料质量，而不是固定的浸泡时间。此外，反馈回路还能对薄膜生长进行精确和可重复的控制，并能利用固定时间从非线性薄膜生长的聚合物组合中设计出线性薄膜生长（30）。对于固定时间的浸入式组装，可将计算机编程的自动载玻片染色机改装为自动多层组装，以便在清洗步骤中进行搅拌和溶液交换（24，29）。类似的计算机编程机器虽然是定制的，但也能沉积多层膜。  \n\n\\~将 ${\\sim}1000$ 层带电胶体沉积到微粒基底上（基底直径约 100 毫米）（27）。虽然自动化减少了人工操作，但并不能大幅缩短整体组装时间，这就是为什么有些人致力于将更快的沉积动力学与自动化系统相结合。例如，一种市售的机器人使用旋转载玻片支架来加(26).这种旋转可将吸附时间缩短 3 到 10 倍，并可使用更高的旋转速度制备更厚的薄膜。通过使用柔性基底，辊对辊组装还能使分层速度更快（5 到 10 倍）（9）。轧制过程的浸泡时间和速度在决定薄膜性能方面起着重要作用，而且干燥条件、润湿性和基底移动速度也需要优化，以便生产出与标准浸泡装配性能相似的薄膜（9）。对辊对辊组装的进一步改进是使用压辊技术来防止多余的溶液交叉污染系统，从而获得比浸入式组装更均匀的涂层（34）。  \n\n沉浸式组装可在微粒基底上进行，因为微粒基底太小，无法在溶液间快速沉淀或物理移动，如微型和纳米颗粒。在微粒基底上进行沉浸式组装的最常 见 技术是将聚合物溶液添加到分散的致密微粒基底上，用离心机将微粒造粒，去除上清液，用类似的造粒过程多次清洗，然后重复这些步骤进行多层生长（5、6、10）。由于需要离心步骤，这通常既耗时又耗力，而且还需要密度足够大的颗粒才能造粒。不过，通过使用比水轻的微粒子层（如乳液），可以实现起皱和脱脂循环  \n\n能在几分钟而不是几小时内起泡（36）。与使用固体模板相比，使用乳液作为模板可获得更厚的薄膜，这可能是由于  \n\n用于稳定乳液的表面活性剂（36）。洗涤步骤 (11)，但离心也可用于加快浮选和起泡过程 (35)，乳化程度较轻的乳液  \n\n图 1.逐层组装的多功能性。(A) 逐层组装示意图概述；(B) 显示组装技术影响薄膜和工艺性能以及应  \n\n![](images/b2b810d3ab2d322b6088aaefc2186768106adca4e72170b9b7693417151ecf60.jpg)  \n\n微粒基质的制备需要避免离心处理，因为离心处理会导致聚集，耗费大量人力，而且一般难以自动配对。避免离心的一个简单方法是取消洗涤步骤。要做到这一点，可以通过添加精确量的聚合物来实现。  \n\n而不是通常使用的高浓度过量聚合物溶液（5、6、10）。起初，在颗粒开始聚合之前只能沉积两到三层（12），但可以沉积更多层。  \n\n通过在组装过程中逐步测量 zeta 电位（37）来沉积。此外，对于软颗粒基质，如乳液（38），可使用持续搅拌；对于硬颗粒基质，如药物晶体（39），可在层沉积过程中使用声波，从而减少聚集。通过优化方案，饱和法可获得与离心法相似的壳厚，但速度快三倍（37、39）。这种技术需要持续监测和计算表面积，以避免添加过量聚合物，因此无法减少人工参与。一种技术的重点是减少人工参与和降低离心需要，它使用琼脂糖中固定的微粒基质，将微粒基质集合转化为宏观基质。  \n\n(33).这种固定颗粒的宏观集合可以像平面基底一样处理，并使用滚动浸渍机将其浸入聚合物溶液中，从而在分层过程中实现完全自动化。可能由于聚合物在琼脂糖水凝胶中的扩散受阻，这种技术生成的薄膜厚度仅为传统离心法制备的薄膜厚度的一半左右。  \n\n据报道，在层数较高的情况下，基于离心分离的装配会造成 ${\\sim}90\\%$ 的损失（21，33）。  \n\n由于配料和模板选择的易用性和多样性，沉浸式组装已被广泛应用。例如，可通过沉浸式组装在平面基底上制备发光二极管（LED），聚合物的选择和多层厚度可控制亮度和开启电压（29）。自动卷对卷沉浸式组装可用于沉积导电和阻燃涂层（34）。涂有颗粒多层膜的平面基底可用于通过多层膜的颜色变化检测肉眼不可见的小颗粒（2）。玻璃载玻片也可以涂上颗粒多层膜，用于制备抗反射、防雾和自清洁表面（24）。涂有颗粒的融合微反应器更有利于反应（27）。某些颗粒基质很容易去除模板颗粒，留下空心多层胶囊。同样，药物本身也可用作微粒模板，两种类型都适用于药物输送（5、6、33、38-40）。  \n\n总之，沉浸式组装是最常用的长尺寸层组装技术，也是比较其他技术的实际标准。将几乎任何形状或尺寸的基底浸入装有分层溶液的容器中非常简单，因此这种技术  \n\n很容易获得。生产出的薄膜具有相互渗透 的结构，并形成 \" 模糊 \" 的纳米装配，几乎图 2.逐层组装技术。(A至E）逐层组装的五大技术类别示意图。[插图来源：Alison E. Burke 和 CassioLynm］  \n\n是同步的。 研究审查  \n与 LbL 组装 (3)。最近的许多工作都围绕着缩  \n短组装时间展开",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# A Immersive  \n\n![](images/c28d37d5642ae1a7992663c7c71629813a10f79cd56ae570ee24b173e70491ac.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 9,
+        "chunk": "# B Spin  \n\n![](images/3d3b5398b0f9e816ed1ac616b55213336129aaf23e010c5b03ee23cf8bcb92f3.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 10,
+        "chunk": "# CSspray  \n\n![](images/31779912017a95835b65bc9388b2e5578762cbeb6b0c0f3c3cd82a7540f848d6.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# D Electromagnetic  \n\n![](images/95346fd2eff1ca72fd0dcd33f043a69c34e7721e53e56985d101f6fbd44f41a1.jpg)  \n\nE Fluidic  \n\n![](images/5a7a95ff2116addac9d4f3889f77e76a5b245d4d1fa6df41ea91a337deed2599.jpg)  \n\n以及减少人工干预的自动化系统。对于颗粒基底的涂层，适用于较小、低密度颗粒（如纳米二氧化硅颗粒）涂层的技术也引起了相当大的兴趣，传统的离心装配很难处理这些颗粒。由于浸没式涂层通常比其他技术需要更多的材料，特别是在工业规模上浸没大型基底时，废料可能是一个问题。  \n\n尽管只要交叉污染保持在较低水平，解决方案就可以重复使用。沉浸式组装一直是 LbL组装的主力军，毫无疑问，它将继续在新型和改进型薄膜的开发中发挥不可或缺的作用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# 旋转组件  \n\n使用旋涂技术逐层组装（即：\"旋转组件\"）利用普通涂层旋转基底以促进材料沉积的技术（14）。虽然浸入式 LbL 组装后基底的干燥可以通过旋转来实现（41），但大多数旋转组装都是通过将溶液浇注到旋转基底上（42）或将溶液浇注到静止基底上，然后进行旋转（43）。旋转大大加快了组装过程，由于旋转基底上有各种不同的旋转方式，因此可在 ${\\sim}30$ 秒内沉积层状物。  \n\n表 1.选定的 LbL 组装技术和使用每种技术产生的特性。本表旨在提供总体概述，并非详尽无遗。NR 表示未在选定的参考文献中报告。[插图来源：Alison E.  \n\n\n<html><body><table><tr><td colspan=\"2\">Burke 和 Cassio Lynm]</td><td colspan=\"2\">BUILDING BLOCKS</td><td colspan=\"2\">PROCESSPROPERTIES</td><td colspan=\"3\">NANOFILM PROPERTIES</td></tr><tr><td>LbLASSEMBLY TECHNOLOGY</td><td>Substrates</td><td>Substrate sizes*</td><td>Layer materials</td><td>Time per layer</td><td>Automated</td><td>Layer (current status) thickness, nmt nm</td><td>Roughness, Layer</td><td></td></tr><tr><td colspan=\"2\">Immersive</td><td>10 nm-1 m</td><td></td><td>10 s-12 h</td><td></td><td><1-15</td><td>1-20</td><td>structure Interpenetrated</td></tr><tr><td colspan=\"2\">Dipping (2,25)</td><td>Planar 1-100 mm</td><td>Polymers, colloids</td><td>10-30 s (32) or 10-20 min (26)</td><td>Yes</td><td>1-2 (25, 26)</td><td>1-10 (44, 49)</td><td></td></tr><tr><td colspan=\"2\">Dewetting (8)</td><td>Planar 1-10 mm</td><td></td><td>Polymers, colloids 30-60 s (8)</td><td>No</td><td>1-2 (8)</td><td>NR</td><td></td></tr><tr><td colspan=\"2\">Roll-to-roll (9)</td><td>Flexible planar 100 mm-1 m</td><td>Polymers</td><td>2-5 min (9,34)</td><td>Yes</td><td>1-15 (9, 34)</td><td>15-20 (9,34)</td><td></td></tr><tr><td rowspan=\"3\">Centrifugation (5, 6) Calculated saturation</td><td>Particulate</td><td>10 nm-10 μm</td><td>Polymers, colloids</td><td>20+ minl (5, 6)</td><td>No</td><td>1-2 (5, 10)</td><td>3-10 (23, 94)</td><td></td></tr><tr><td>Particulate</td><td>100 nm-1 μm</td><td>Charged polymers</td><td>5-10 min (39)</td><td>No</td><td>1-2 (39)</td><td>NR</td><td></td></tr><tr><td>Immersiveimmobilization Particulate</td><td>100 nm-1 μm</td><td>Polymers</td><td>40-50 min (33)</td><td>Yes</td><td><1 (33)</td><td>NR</td><td></td></tr><tr><td>(33) Creaming (11)</td><td>Emulsion</td><td>10 nm-1μm</td><td>Polymers, colloids</td><td>0.5-12 h (11, 36)</td><td>No</td><td>1-7 (36, 38)</td><td>NR</td><td></td></tr><tr><td colspan=\"2\">Spin</td><td>1-100mm</td><td></td><td>10 s-5 min</td><td></td><td><1-2</td><td>1-10</td><td>Stratified</td></tr><tr><td colspan=\"2\">Spin (14, 42, 43)</td><td>Planar 1-100 mm Planar</td><td></td><td>Polymers, colloids 10-60 s (43)</td><td>Yes</td><td><1-2 (42)</td><td>1-10 (44, 46)</td><td></td></tr><tr><td colspan=\"2\">High gravity (15)</td><td>1-10 mm</td><td>Polymers, colloids</td><td>20 s-5 min (15, 49)</td><td>No</td><td>NR</td><td>1-2 (49)</td><td></td></tr><tr><td colspan=\"2\">Spray</td><td>10 nm-10 m</td><td></td><td><1 s-24 h</td><td></td><td><1-15</td><td>1-10</td><td>Stratified</td></tr><tr><td colspan=\"2\">Spray (16,52)</td><td>Planar</td><td>1 mm-10 m Polymers</td><td><1-30 s (59)</td><td>Yes</td><td></td><td><1-5 (16, 51) 1-10 (51)</td><td></td></tr><tr><td colspan=\"2\">Atomization (17)</td><td>None 10-100 nm</td><td>Charged polymers</td><td>12-24 h (17)</td><td>No</td><td>5-15 (17)</td><td>NR</td><td></td></tr><tr><td colspan=\"2\">Spray immobilization (63)</td><td>Particulate 10-100nm</td><td>Polymers</td><td>5-10 s (63)</td><td>Yes</td><td>2-4 (63)</td><td>NR</td><td></td></tr><tr><td>Electromagnetic</td><td></td><td>10 nm-100 mm</td><td></td><td>1 s-20 min</td><td></td><td>1-20,000</td><td>10-30</td><td>Stratified</td></tr><tr><td>67,73) Magnetic (19,76)</td><td>Electrodeposition(18,20, Planar</td><td>1-100 mm</td><td>Polymers, colloids</td><td>1 s-20 minI (65, 71)</td><td>No</td><td>2-20,000 (20,67,71)</td><td>10-30 (66, 70)</td><td></td></tr><tr><td colspan=\"2\">Electro-immobilization(13)</td><td>Planar and Particulate</td><td>10 nm-100 mm</td><td>Polymers, colloids 15-20 min (19, 76)</td><td>No</td><td>1-2 (19, 75)</td><td>NR</td><td></td></tr><tr><td colspan=\"2\">Fluidic</td><td>Particulate</td><td>10 nm-1μm</td><td>Charged polymers</td><td>15-20 min (13) No</td><td>2-3 (13)</td><td>NR</td><td></td></tr><tr><td colspan=\"2\">Microfluidic planar (22)</td><td>100 nm-100mm</td><td></td><td>10 s-45 min</td><td></td><td><1-3</td><td>1-11</td><td>NR</td></tr><tr><td>Microfluidic particulate</td><td>Planar Particulate</td><td>10 μm-100 mm</td><td>Polymers Polymers</td><td>1-15 min (80, 81) 10-60 s (96-98)</td><td>Yes Yes</td><td>1-3 (96, 97)</td><td><1-3 (83,84) 1-10 (80, 84)</td><td></td></tr><tr><td>(96-98)</td><td></td><td>100 nm-10 μm</td><td></td><td></td><td></td><td></td><td>NR</td><td></td></tr><tr><td>Fluidized bed (23) Fluidic immobilization (86,</td><td>Particulate Particulate</td><td>1-10 μm</td><td>Polymers</td><td>3-5 min (23)</td><td>No No</td><td>2-3 (23) 1-2 (87)</td><td>9-11 (23) NR</td><td></td></tr><tr><td>87)</td><td></td><td>100 nm-1 μm</td><td>Polymers, colloids</td><td>5-45 min (86,87)</td><td></td><td></td><td></td><td></td></tr><tr><td>Vacuum/filtration (21)</td><td>Particulate and fragile**</td><td>100 nm-1μm</td><td>Polymers</td><td>10-20 min (95)</td><td>Yes</td><td>1-2 (94)</td><td>5-10 (94)</td><td></td></tr></table></body></html>  \n\n\\* 标出了典型的数量级基底尺寸。衬底尺寸可大可小。所示为线性生长薄膜的典型每层厚度。考虑到非线性生长曲线，指数生长研薄究膜审的查每 层厚度变化很大。分别表示搅拌或不搅拌的时间。§脱湿可以利用通常难以分层的材料（如低电荷或低表面接触的材料）。离心处理时间因手动移液和再悬浮步骤而变化很大。厚度取决于时间。\\*\\*哺乳动物细胞等易碎基质可通过流体过滤分层。  \n\n力的作用（43）。此外，自旋装配可实现自动化，使用市售的自旋涂布机可对直径达 10厘米的基底进行涂布（44、45）。然而，标准旋涂机通常是为平面而设计的，不适于浸入式装配所能达到的复杂形状。  \n\n与浸入式组装相比，旋转式组装通常会产生更均匀的薄膜。这是因为组装是由一系列力驱动的，包括静电相互作用力（导致聚合物的吸附和重新排列）、离心力、空气剪切力和粘性力（导致弱结合聚合物的解吸和薄膜的脱水）（43）。这些力也是自旋组装比浸入式组装快几个数量级的原因。聚合物溶液的盐浓度在较高的旋转速度下影响更大，这意味着在低离子强度下静电力的作用更大，而在高离子强度下剪切力占主导地位（46）。这些剪切力  \n\n与产生较厚穿透膜的浸入式组装相比，旋转力产生的具有特定层界面的薄膜更薄、更有序（47）。具体来说，旋转组装聚合物薄膜的厚度通常与旋转速度有关，速度越高，薄膜越薄（42）。在沉积胶体时，旋转过程中的作用力会导致胶体形成单层，而标准浸入式组装通常会导致基底未完全涂覆的假单层（43、48）。一项关于自动浸入式组装和自动旋转式组装之间差异的比较研究发现，浸入式组装制备的薄膜更厚、更粗糙，而旋转式组装制备的薄膜更薄、更光滑（44）。这些薄膜在视觉上也有所不同，旋转组装的薄膜由于层间分层明显而具有透光性，而浸入式组装的薄膜由于 层间不均匀、相互渗透而不透明（图 3）。接触角和相对  \n\n自旋组装薄膜的聚合物浓度在所有双层膜中都是一致的，而浸入组装薄膜则随着时间的推移变得粗糙，从而产生不同的接触角和两个组成层之间的相对浓度比（44）。另一项研究比较了自旋组装和浸入组装，结果表明自旋组装薄膜中的粘土纳米复合材料具有更高的取向度（45）。不过，旋转组装可能产生的一个问题是，在聚合物溶液离子强度较高和旋转速度较低的情况下，与子层边缘相比，溶液浇注处的薄膜可能更厚（42，46）。  \n\n在自旋装配的一种特殊情况下，可以将子晶体与聚合物溶液或胶体分散液一起放置在一个与旋转轴平行（而不是垂直）的封闭容器中。旋转时，离心力会将层材料直接推到基底上，而不是穿过基底，因此被称为 \"高重力装配\"（15）。这可以改善薄膜沉积和均匀性，尤其是在聚合物浓度较低的情况下，因为旋转和增加的湍流可以降低层状层和基底周围扩散层的厚度。达到吸附平衡的速度至少比无损装配快五倍，并且可以通过旋转速度进行控制。此外，使用浸入式装配时呈指数增长的聚合物组合，使用这种技术也能呈线性增长。同样，以这种方式组装的 LbL 薄膜的粗糙度要低得多（约为 2 至 10 倍）（49）。  \n\n自旋装配通常比浸入式装配产生更有组织的薄膜和多层膜，这使其成为制备颜色可控且均匀的光学涂层（14）和制备透明薄膜（44）的有用工具。同样，与浸入式组装相比，自旋组装可用于制备亮度更高的发光二极管（41）。旋涂装配在应用方面的一个主要限制是，它仅限于涂覆小的平面子基片，因为增加基片尺寸需要更高的旋涂速度。此外，非平面表面的旋涂也很复杂。  \n\n总之，旋转组装使用旋转的子板来沉积层并去除多余的涂层材料。与浸入式组装相比，自旋组装通常能产生更薄、更有序、更分层的多层膜，而且过程更快。在许多研究环境中，甚至在一些工业环境中，  \n\n如半导体行业中常见的机器人晶片加工中 这有助于从实验室转化到实际应用中。此，通常都能使用装配所需的旋转涂布机， 外，在非平面上沉积多层薄膜图 3.浸入式装配与自旋装配的比较。(A) 不同材料层的示意比较。(B) 比较浸入式组装薄膜（左）和旋转式组装薄膜（右）。薄膜由疏水改性聚（环氧乙烷）和聚（丙烯酸）制成。[经许可改编自 (44)。2008 美国化学学会版权所有]。[插图来源：Alison E. Burke 和 Cassio Lynm  \n\n由于薄膜组装过程中会产生剪切力，因此，要在平整但粗糙的表面或甚至是平坦的表面上组装薄膜是一项挑战。然而，旋压组装所产生的薄膜和加工特性，包括在相对较短的时间内组装出光滑的薄膜。  \n\nA Creating different nanofilm properties using immersive vs spin LbL assembly  \n\n![](images/38f15f86b3c51a34bf8b650b59e0455266199e1bc7e072dd4f3740f69382798a.jpg)  \n\nBExamples of polymer-polymer nanofilms using immersive vs spin LbL assembly时间，继续使这种方法成为一种有吸引力的选择。  \n\n![](images/f45ec2118f0810177cd1d444f11a79057380b34a77cecedaae91dd1cbecc4c03.jpg)  \n\n![](images/90a870198a06a65614c3a187874a1e2532a1ac06756a51242a0f17bbe59ccf91.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# 喷雾组件  \n\n喷涂 LbL 组装是另一种组装类型，通过气溶胶化聚合物溶液并将其依次喷涂到基底上组装薄膜（16）。虽然在 LbL 组装过程中，喷射空气可用于干燥薄膜以减少污染（并对齐纳米碳管）（50），但在此我们仅在层沉积的背景下讨论喷射组装。标准喷射组装比浸入式组装快得多（每层可快至 \\~6 秒）（51），其工业水平远远超过旋压组装（52,53）。真空也可用于进一步加快工艺流程，最大限度地减少喷涂和清洗之间的滞后时间，反之亦然，还可用于促进三维（3D）物体（如存储器）的喷涂（54）。  \n\n在喷雾组装过程中，薄膜的特性--如形态、均匀性、化学成分和选择性膜特性--可以调整到与浸入式组装制备的薄膜相似，薄膜厚度受悬浮液浓度、喷雾流速、喷雾持续时间、静止持续时间、是否清洗基底和清洗时间长短以及溶液是垂直还是水平喷雾等因素的影响（16、51、55-57）。这种控制源于喷涂组装过程中的两种主要作用力，即实际喷涂中的大量运动和液膜中的随机运动 (56)。液膜中的随机运动可使聚合物重新排列，并在靠近子结构处产生更强的对流，从而改善沉积效果。这是因为基底界面上的液膜厚度为亚微米级，而且喷雾接触基底的速度很快（16，56）。清洗基底通常比不清洗基底产生更厚的薄膜，这是因为聚合物在清洗过程中发生了重排。$(5I)$ ).与自旋装配一样，喷雾装配产生的薄膜与浸入式装配相比，层次更加分明（16，53）。  \n\n喷涂组装还与其他技术相结合，以充分利用特定技术的优势并实现组装过程自动化。例如，喷涂 LbL 组装的一个缺点是，由于重力排水的影响，在溶液滴漏附近的沉积增加，以及喷嘴在一定距离上造成的不规则图案，获得的薄膜可能不均匀（51，57）。为解决这一问题，在喷涂组装过程中旋转基底可制备出更均匀的薄膜，每层的喷涂时间可达到亚秒级（56、58、59）。通过喷涂旋转基底，添加到基底上的大部分聚合物都会被吸附。相比之下，绝大部分聚合物在浸入式组装后会重新留在涂层溶液中。因此，喷涂时的适用浓度可比浸入式组装所需的浓度低 10 到 50 倍。  \n\n在旋转基底上组装（55、59）。较大的三维基底，如管状膜，也可在喷涂过程中通过旋转基底进行喷涂（60）。计算机辅助自动化喷涂组装是进一步的改进，可减少人工处理（58、60）。与在 QCM 芯片上使用自动沉浸式装配类似，使用 QCM 芯片进行自动喷涂装配可实现反馈回路控制和实时薄膜生长跟踪（61）。自动匹配喷涂装配还与卷对卷加工相结合，用于涂覆工业尺寸基底（即数十米长的基底）（62）。通过对固定在可溶解表面上的微粒基底进行喷涂组装，卷对卷喷涂组装也可用于在微粒基底上涂覆多层薄膜（63）。  \n\n一种用于微粒基底涂层的独立喷雾装配技术使用振幅为 1 到 10 纳米的表面声波来雾化聚合物和货物（17）。当雾化液滴在空气中移动时，溶剂蒸发，聚合物凝结成颗粒状，从而使第一种雾化溶液成为后续涂层的模板，每微升溶液可产生约 1000 个颗粒。将颗粒透析以去除多余的聚合物，然后加入带相反电荷的聚合物溶液中，再重新雾化以涂覆颗粒。此过程可重复进行多层组装；不过，透析过程会将此技术的处理时间增加到每层约 24 小时。  \n\n喷涂装配的应用范围很广，因为它可以相对容易地涂覆工业规模的基底（62），而且不局限于平面基底（54、60、63）。喷涂组装已被用于制备棉布上的阻燃薄膜，结果表明，与在水平方向的基底上喷涂或浸渍相比，在垂直方向的基底上喷涂能产生更好的阻燃薄膜（57）。服装材料也使用喷涂组件进行涂层，以控制空气流动并提供化学保护，有可能用于军服  \n\n(54).与其他组装技术一样，喷涂技术也可用于制备抗反射涂层（61），同样，汽车着色也可通过结构化着色来减少红外线的加热（62）。膜管也可以通过涂层来改善有机染料与水的分离（60）。由于薄膜的结构可通过喷涂时间控制在纳米级，因此喷涂组装可用于控制薄膜的导电性，这是其他组装技术所不具备的（59）。喷雾组装已被用于制备颗粒，以研究细胞对不同涂层和颗粒长宽比的吸收（63）以及体外基因递送（17）。由于喷雾组装组装时间短，易于实现自动化和规模化，因此已被广泛应用于各种应用和工业领域。  \n\n总之，喷涂装配是通过将涂层溶液气溶胶化来生产多层薄膜的。  \n\n将它们喷涂到基底上。生成的薄膜通常组织良好，层次分明。喷涂组装是一种快速简便的方法，可为大型或非平面基底涂膜，但浸入式组装仍是为复杂三维基底涂膜的首选方法。喷涂组装是与工业应用最密切相关的技术之一，因为它已在工业中得到广泛应用。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# 电磁组件  \n\n电磁装配的基础是利用外加电场或磁场来实现分层，例如在聚合物溶液中涂覆电极，或在涂覆溶液中移动磁性微粒（18、19）。前者通常称为电沉积，是在电解槽中使用外加电压对材料进行涂层的成熟技术。在标准的电沉积设置中，两个电极浸入聚合物溶液中，然后施加电流。然后清洗电极并将其放入带相反电荷的聚合物溶液中；电极的极性反转，过程重新开始 $(64)$ 。电沉积可用于快速组装离子、聚合物和胶体，所需的时间远远少于浸入式组装（18）。例如，可通过电沉积制备双金属介孔LbL 薄膜，电沉积时间决定层厚度，速度约为 $1.5~\\mathrm{{nm/s}}$ （65）。在另一种设置中，可将基底置于两个电极之间，这样就能在平面基底上进行涂层（ $(66)$ ），甚至固定颗粒（13）。这种技术产生的薄膜厚度大约是离心法的两倍。电沉积还可以使用更高的电压，最高可达 $30\\mathrm{V}$ （13、66）；然而，固定颗粒的组装过程每层可能需要 15 分钟（13）。  \n\n电沉积薄膜的厚度与组装过程中使用的电压直接相关，获得最厚薄膜的最佳电压取决于聚合物溶液的 $\\mathsf{p H}$ 值（ $(\\delta7)$ ）。较高的电压会导致薄膜解吸，因为电极（即基底）开始排斥之前沉积的薄膜层。一般来说， $\\mathsf{p H}$ 值低于聚合物的 ${p K}_{\\mathrm{a}}$ （其中 $K_{\\mathrm{a}}$ 是酸的解离常数）时，需要较低的电压才能达到峰值厚度，而且峰值厚度也比 $\\mathsf{p H}$ 值较高时的峰值厚度大，更接近或高于聚合物的 ${p K_{\\mathrm{a}}}$ 。不过，如果电压升得足够高，就能达到第二厚度峰值，从而在其他技术难以生长的 pH 值下组装薄膜（67）。造成这种厚度 \"低谷 \"的原因是，在高电压下，电极上水的电解在研阻究碍审聚查合 物吸附方面发挥了更大的作用；然而，在更高的电压下$(>3\\mathrm{~V~}}$ ），聚合物与电极之间的静电作用超过了电解造成的任何影响（67）。例如，聚合物-酶薄膜在最佳电压为  \n\n$1.2{\\mathrm{V}}$ ，而使用较低或较高的电压（低于 3V）（68）。这些研究表明，电沉积与其他LbL 组装技术类似，聚合物溶液的 pH 值以及聚合物本身的构型是控制薄膜厚度的关键。  \n\n在较高电压下，电磁沉积薄膜比浸入式沉积薄膜更加相互渗透，这与在较低电压下制备的高度分层薄膜形成了鲜明对比（66）。当形成聚合物-聚合物薄膜时，在电流作用下，薄膜在流动池中生长过程中折射率不会发生静态变化，这表明沉积过程比浸入式组装过程更加均匀。  \n\n(69).同样，聚合物胶体薄膜也显示出较高的组织性，因为在较高电压下组装薄膜时，折射率会降低，透射率会增加（70）。相应地，电沉积酶-聚合物薄膜比浸入式组装薄膜更均匀，对基底的覆盖率分别为 $90\\%$ 和${\\sim}50\\%$ （68）。由于这种分层和高表面覆盖率，电沉积可以控制层与层之间的间距（68）。  \n\n电沉积也可以通过电极的局部效应来实现，例如引起氧化还原反应或改变 pH 值。阳极和阴极附近溶液的 pH 值会发生明显变化，分别从大量溶液变为较低和较高的pH 值（71）。阳极附近的低 pH 值可诱导聚合物沉积。不过，这种 pH 值诱导的电沉积效果相当有限，因为只能形成少量双电层（使用海藻酸盐和壳聚糖等材料），因为电层太厚（几十微米），电流无法穿透，导致 pH 值没有变化，因此也就没有沉积。利用类似的原理，可在电极（即基底）上就地由铜（II）生成铜（I），通过铜催化的 \"点击 \"反应交联含叠氮化物和炔烃的聚合物，制备共价稳定薄膜（20）。含有电敏感点击基团的聚合物也可进行电耦合，从而可在以下条件下制备出 500 纳米厚的透明薄膜，从而实现分层和均质。  \n\n${\\sim}30$ 分钟（72）。使用相同的基本原理，通过交变电压在氧化反应和还原反应之间进行切换，就可以进行单锅合成，从而利用电聚合实现免清洗组装（73）。  \n\n磁铁而不是电流可用于在敏感的微粒模板（如乳液 (74) 或难以通过离心法制粒的小模板（如 10 纳米以下的氧化铁纳米粒子）上组装 LbL 薄膜。  \n\n(19).含有磁性纳米颗粒的模板颗粒可以用磁铁从聚合物溶液中分离出来，这种方法与过滤法类似，可以在无离心的 LbL 组装过程中回收几乎 $100\\%$ 的颗粒（75）。磁铁或外部磁场也可用于定向层状  \n\n平面基底上的磁性纳米粒子，使随后的纳米粒子层能够以定向方式更快地去定位(76).该技术使用标准浸入式组装法沉积带正电和负电的磁性纳米粒子，并在沉积步骤之间施加磁场。因此，与标准浸入式组装相比，厚度不会增加；但是，薄膜的吸光度会随着磁铁的应用而增加，这表明填料增加了（76）。  \n\n电磁装配可用于多种不同的应用，因为它可用于形成具有其他技术难以装配的成分的 LbL 薄膜。铂层和钯层的双金属薄膜具有约 $40\\mathrm{m}^{2}\\mathrm{g}^{-1}$ 的布鲁纳-艾美特-泰勒表面积，因此与单层薄膜相比，在甲醇氧化反应中表现出更强的 电化学活性（65）。通过在不同电压下组装薄膜，调整薄膜的反射率，可以制备出抗反射涂层（70）。生物应用也在探索之中，因为生物相容性涂层可通过电磁组装形成，体外测试证实其细胞毒性可忽略不计（71）。与传统制备的薄膜相比，具有生物电溶解特性的生物酶薄膜具有更高的表面覆盖率和活性（68）。组装薄膜的分层也有利于制造高性能光电设备（72）和分离膜（66）。固定颗粒上的电沉积也可制备中空聚合物胶囊（直径从微米到 100 纳米以下）（13）。  \n\n总之，电磁组装利用电场或磁场，通常是以聚合物溶液中的电极或磁性微粒基底的形式来沉积薄膜。电磁组装可以利用电流引起的 pH 值变化或氧化还原反应来实现薄膜组装，因此使用的驱动力与其他主要组装类别的驱动力大不相同。一般来说，电磁组装的薄膜比使用其他 LbL 组装方法制备的薄膜更厚、更致密（13，68）。电磁组装仍不如其他一些技术普遍，尽管它需要特殊的设备和专业知识，但它确实为多层薄膜组装提供了一种不同的方法（例如，通过磁力处理基底和材料或通过电感应组装），从而为组装薄膜提供了其他机会。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# 流体组件  \n\n流体组装可用于通过流体通道沉积多层，既可以在通道壁上涂布，也可以在放置或固定在流体通道中的基底上涂布（77）。一般的方法是利用压力或真空使聚合物和洗涤溶液依次通过通道，通道可以是流体元件，如管道或毛细管，也可以是设计好的微流体网络（78、79）。流动  \n\n室基 QCM 是一种常见的流体组装技术，可提供关键的实时信息，用于研究薄膜特性和多层生长（22）。较高浓度的聚合物溶液通常会产生较厚的薄膜 (79)，而决定流动下吸附聚合物量的关键因素是接触时间而不是流速 (80)。  \n\n流体组装通常使用泵、毛细管力或旋转使液体通过通道，当然也可以使用移液和静态孵育。不过，当聚合物溶液与基底保持静态接触超过 10 分钟时，流体组装与浸入式组装非常相似（81、82）。用泵或真空将聚合物和洗涤溶液装入通道，可在 5 到10 分钟内沉积 ${\\sim}1.5$ 纳米厚的层 (83)。毛细力也可用于将聚合物溶液拉过微流体通道，方法是将溶液液滴置于流体入口处，然后旋转基底以移除溶液，这样就能将聚合物溶液拉过微流体通道。  \n\n\\~1.2 纳米厚的层可在 2 分钟内沉积完成（84）。基于毛细作用力的流体分层很容易实现，因为毛细作用不需要外部活性成分，但不适合体积较大或需要动态控制流速的情况。  \n\n流体设备和灌注室还可用于实现特定区域的流体分层，或在更复杂的三维结构上进行流体组装。例如，复杂的自动化微流体设备可用于并行流化数百个层，利用帽状流动和真空来填充和排空多个通道（85）。这样就能使用少量材料对薄膜库进行高通量筛选，因为只需要一个液滴就能填满一个微通道。通过在基底上粘贴一个几何腔室，然后将溶液流过腔室和基底，可在基底上涂布特定区域的薄膜（80）。灌注室可用于在复杂的三维基底上进行流体分层，如敏感的生物基底（如动脉），这些基底在分层过程中必须始终保持水合状态（86）。同样，灌注室也可用于容纳含有固定颗粒的琼脂糖，以进行流体组装（87）。这种技术不仅能沉积聚合物，还能沉积较大的货物，如金纳米颗粒或脂质体，并能产生与标准离心组装法预制的薄膜厚度几乎相同的薄膜（87）。  \n\n真空通常与其他组装技术（如喷雾组装）一起使用，或用于将溶液从流体通道中重新移出，但也可用研于究在审宏查 观流体型组装中形成多层，尤其是在气凝胶等非普通基质上。气凝胶可通过真空装配进行功能化，方法是将导电聚合物、生物分子或碳纳米管溶液从顶部浇入气凝胶，然后用真空将这些溶液向下抽吸。  \n\n88）。真空组装还可用于沉积材料，如还原氧化石墨烯，否则会对形成均匀的多层造成挑战（89）。对于微粒基底，可使用孔径小至 200 纳米的分离过滤器进行无离心分层（21，90）。真空并不适用于所有敏感模板；然而，对于包括乳液（91）、细胞小体（92）或碳酸钙纳米线（93）在内的模板颗粒，轻微真空（约 100 毫巴）可促进分层过程（21）。使用优化程序在组装过程中损失的颗粒不到 $3\\%$ ，远远低于基于计算饱和度的方法（可能损失约 $50\\%$ ）或基于离心的方法（在层数较高时可能损失超过$80\\%$ ）（21）。这种过滤-真空组合装配技术产生的膜层厚度约为 1.3 纳米，表面粗糙度约为 5 至 10 纳米，与通过离心装配制备的膜层相似（94）。细胞胰岛涂层的过滤装置也实现了自动化，使用回馈回路将液体从再作用室抽空，从而将人工处理时间减少了约 $60\\%$ （95）。  \n\n与真空装配一样，流体装配并不局限于平面基底，它是在颗粒基底上进行无离心装配的可行替代方法（96-98）。许多流体组装方法都是对乳液或液晶进行涂层，因为这些材料在流体学领域研究得很透彻。一般来说，涂层和洗涤溶液通过使用小于颗粒的物理间隙偏离颗粒流，使流体垂直（96）或平行于颗粒流（97）进入。在平行流系统中进行流体组装时，需要使用较大的模板颗粒（直径约 50 毫米），因为可以使用固体柱以约 $45^{\\circ}$ 角将它们偏转到三股平行层流流（溶液 A、洗涤液和溶液 B）中，形成约 2 到 3 纳米的层厚（97）。类似的技术也可用于在 15 毫米的珠子上涂覆阿维丁和生物素，较高的偏转角度与失效率有很大的相关性，最佳角度为 $1^{\\circ}$ ，失效率几乎为零（99）。可以使用特定的几何形状来捕捉乳状液，而不是柱状液，以实现脂质层的流体组装  \n\n(98).在用聚合物涂覆脂质颗粒时，切向流过滤可用作一种快速透析，以去除多余的聚合物溶液（100）。为了给足够大和/或足够致密的颗粒涂层，可以使用基于流化床的装置。这样的组装速度比离心组装快八倍，生产的薄膜厚度也是离心组装的两倍（23）。在这种情况下，洗涤液或聚合物溶液提升颗粒的力量与重力沉积颗粒的力量相平衡，从而形成了一个流化床，洗涤液和聚合物溶液可以被推过颗粒。类似的装置也可用于在填料柱中对较大（大于100 毫米）的颗粒进行包衣，不过这些流化床需要  \n\n由于粒度较大，无需流化，而且可以利用重力而不是真空或泵驱动的流体力学原理将涂层和洗涤溶液拉过色谱柱 (1)。  \n\n在开发流体装配技术的过程中，引入了许多应用。许多应用，如改进的毛细管电泳，都是在毛细管内实现的（81）。流体组装技术还可用于设计复杂的流动模式，例如，只需改变毛细管壁的外涂层并通过电流产生流动，即可在同一毛细管中实现反向流动（82）。流体组装并不局限于平面基底：例如，可以在气凝胶上制备多层涂层，从而提高抗压强度、湿态超弹性、荧光和机械响应阻力，同时还能产生高电荷存储能力（88）。受损老化的猪主动脉可通过流体组件进行体外修复，以保护动脉免受不必要的血液凝固，并促进愈合（86）。同样，导管管道也可以涂上抗真菌多层膜，以防止堵塞（78）。涂有多层颗粒的层析珠可增加珠子的表面积，从而改善层析效果（1）。虽然流体组装通常是在较大的颗粒（直径数十或数百微米）上进行的，但较小的颗粒（直径约 5 毫米以下）也可以涂覆和装载功能性货物，通过将微流控技术与固定化技术相结合，实现潜在的药物输送应用（87）。乳液等脆弱的微粒基质也可以涂上脂质，利用流体组装技术生成合成细胞（98）。神经细胞可通过流体组装进行图案化（83），细胞胰岛可通过涂覆提高稳健性，从而实现体内移植（92、95）。流体组装是涂覆哺乳动物细胞等敏感颗粒基质的重要工具，使用其他技术可能会损坏这些基质，例如在离心组装处理过程中。  \n\n总之，流体组装提供了在其他方法不易触及的表面（如盖子内部）组装多层膜的方法，提供了特定区域图案化的新途径（如通过流体通道遮蔽表面），并提高了多层膜组装的工业能力（如通过薄膜组装并行化和减少试剂消耗）。虽然建立（微）流体系统所需的专用设备和专业知识会使流体组装的使用复杂化，但这些优势使其在许多应用中具有牵引力。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# 大大小小的挑战  \n\n在过去的二十年里，LbL 组装在可用材料和基底方面经历了爆炸式的增长。如果将所有可用的不同装配技术结合在一起，我们就会明白为什么 LbL 装配技术在众多学科中都很普遍。尽管  \n\n尽管多层薄膜的工具箱非常丰富，但在研究环境之外产生广泛影响的多层薄膜却相对较少。工业应用的一个重点是确定可靠、可扩展和资源节约型的组装工艺，尽管这可能需要针对宏观基底和微观颗粒基底采取不同的方法。  \n\n对于宏观基底，改进的高产能保形涂料装配方法将发挥关键作用。浸入式和喷涂卷对卷装配具有工业相关性，但仅适用于柔性平面基底；因此，需要在可轻松扩展以涂覆大型或大量三维宏观基底的系统方面进行创新。同样，减少涂层过程中的材料浪费也非常重要，尤其是对于生物分子和定制聚合物等有价值的涂层材料。用于体内生物医学应用（如药物输送和组织工程）的薄膜面临的另一个挑战是确保产品的无菌性。通常是在使用前进行无菌处理（加热、紫外线照射、化学处理等），这会影响薄膜的特性和性能。最后，提高薄膜的可靠性和可重复性--例如，通过提高自动化程度和减少人工干预--对于扩展有关薄膜特性和组装技术的知识以及在实际应用中应用多层薄膜至关重要。  \n\n微粒子材料也面临着类似的挑战。一个关键的区别是，有几种微粒组装方法依赖于离心分离法，而离心分离法仍然难以扩大规模，也难以与干预最少的高通量组装相结合。此外，还需要对各种技术的产量和尺寸范围进行规定，因为这些细节往往无法确定。还需要研究主要在平面基底上研究的详细薄膜特性（如层间穿插、层密度、薄膜稳定性或响应性以及渗透性），以便进一步比较平面基底和微粒基底。总之，这些挑战都非同小可，需要集中力量加以克服；它们也并非 LbL 领域所独有。应对这些挑战的方法之一是继续保持开放的态度，在邻近领域和更遥远领域的新领域（有时甚至是意想不到的领域）寻找解决方案；这是 LbL 组装技术创新的基础。  \n\n机会：突破思维定式逐层组装是一项成熟的技术，在多个不同领域大有可为。迄今为止，这项技术的发展主要集中在利用研新究的审分查子 驱动力进行薄膜组装，从而能够使用一系列基底和层材料。然而，这一巨大潜力在很大程度上仍局限于小规模研究环境，需要技术和方法上的创新。尽管新技术层出不穷、  \n\n虽然许多技术都是最新发展的，但在利用不同技术的特殊优势进行特定应用以及开发新的和改进的技术方面，仍然存在尚未解决的难题。  \n\n尽管在建立新的组装技术方面已经开展了大量工作，但只有少数研究是针对所产生的材料特性（如分层、密度、粗糙度）而不是所使用的加工特性（如易于使用、节省材料和时间、降低参与度、批量更大）来选择特定的组装技术。例如，对于电导率非常重要的应用领域（如燃料电池和电池），浸入式组装薄膜的电导率可能优于喷射式组装薄膜，这可以用组成导电层材料的层间组织差异（互渗与分层）来解释（59）。相反，对于光学清晰度和/或润湿行为非常重要的应用，旋压组装可形成光滑、分层的薄膜，从而组装出具有良好水接触角的光学透明薄膜，而沉浸组装的薄膜可能是半透明的，并且由于形成粗糙、相互渗透的层，其接触角会随沉积层数的变化而急剧变化（图 3）（44）。然而，层结构只是为特定应用设计薄膜时需要考虑的关键薄膜特性之一。例如，与电磁组装相关的较高表面覆盖率和层密度可使电沉积酶薄膜具有比同类浸入式组装薄膜更高的酶活性（68）。当然，如果所需的薄膜成分不能分层，那么层结构和密度就无关紧要了，例如，在使用电荷密度低的材料（如还原氧化石墨烯）或接触表面积低的材料（如支化纳米线）时，这可能是一个问题。在这种情况下，脱墨和真空装配等技术可以使用其他技术难以分层的成分形成薄膜（8，89）。这些例子表明，明智地选择组装技术可以组装出新的和改进的薄膜。随着我们对不同技术及其相互比较的了解不断加深，我们也有机会利用这种洞察力来指导下一代 LbL 装配薄膜的开发。  \n\n值得注意的是，本文讨论的组装技术最初并不是为 LbL 组装而开发的，其他领域的交叉技术将继续在新的，甚至可能是革命性的发展中发挥重要作用。一个涉及工业规模分层的有趣例子是使用改装的洗车机在一辆全尺寸汽车上进行喷雾装配（101）。制药业长期使用的技术，如处理、提纯和浓缩药物的方法，可能会对生物医学产生变革性的影响。  \n\n同样，利用喷漆罐这样的日常用品也可以彻底改变装配方法。同样，利用喷漆罐等日常用品也能彻底改变装配方法，因为它们基本上结合了脱脂和喷涂装配技术，可快速完成特定区域的装配，几乎没有材料浪费，也没有清洗步骤。现有装配技术之间的其他组合也有助于加快装配过程并使之自动化。按照这种思路，颗粒基底上的组装技术预计将继续整合固定化方法，因为它们可以像处理平面基底一样处理低浓度的颗粒，从而使本文讨论的许多平面组装技术成为可能。另一种很有前景的颗粒基底方法是使用一种 \"海绵 \"从溶液中吸附多余的聚合物，从而无需将颗粒造粒。就未来的应用发展而言，了解多层薄膜与复杂自然环境（如人体（40）、户外或海水中的环境）之间的相互作用至关重要。其中一个重要方面可能是使用能够以协同方式复合不同多层膜优点的功能性基底。总之，LbL组装的前景是光明的，随着组装技术的黑匣子慢慢被揭开，创新和应用的巨大潜力将会被发现。",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
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Shiratori, 基于原位 QCM 监测的自动喷射铅机。Kyung, K. Fujimoto, S. Shiratori, 基于原位 QCM 监测的自动喷涂-LbL 机。doi: 10.1021/ ma200024w   \n62. K.K. C. Krogman、R. E. Cohen、P. T. Hammond、M. F. Rubner B.N. Wang，用于生产仿生光子系统的工业规模逐层喷雾装配。 Bioinspir.Biomim.doi: 10.1088/1748-3182/8/4/ 045005; PMID: 24263056   \n63. S.S. W. Morton等人，\"按订单生产的纳米药物的可扩展制造\" ：PRINT 纳米颗粒的喷涂辅助逐层功能化。Adv.25, 4707-4713 (2013). doi: 10.1002/adma.201302025; pmid: 23813892   \n64. P.R. Van Tassel, Polyelectrolyte adsorption and layer-by layer assembly：电化学控制。Curr.Colloid Interface Sci.17, 106- 113 (2012). doi: 10.1016/j. cocis.2011.08.008   \n65. H.Wang, S. Ishihara, K. Ariga, Y. Yamauchi, All-metal layer-by-layer films：双金属交替层与 可进入的介孔以增强电催化。J. Am.134, 10819-10821 (2012).134, 10819-10821 (2012). JA303773Z; PMID: 22715877   \n66. G. Zhang, L. Dai, L. Zhang, S. Ji, 外部电场对绝缘基底上聚电 解质和纳米杂化多层膜的薄膜生长、形貌和纳米结构的影 响。doi: 10.1021/ LA104120B; PMID: 21280593   \n67. Y.Y. H. Ko 等人，弱带电聚电解质多层膜的电场辅助逐 层组装。doi: 10.1021/ ma102112a   \n68. 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Asakawa, Stable cationiccapillary coating with successive multiple ionic polymerlayers for capillary electrophoresis.Anal.Chem.70, 5272-5277 (1998). doi: 10.1021/ac980522l; pmid: 9868917  \n82. S.S.L.Barker、D.Ross、M.J.Tarlov、M.Gaitan、L.E.Locascio，用聚电解质多层膜控制微流体装置中的流动方向。Anal.Anal.72, 5925-5929(2000). DOI: 10.1021/AC0008690; PMID: 11140758  \n83. D.R. Reyes、E. M. Perruccio、S. P. Becerra、L. E. Locascio、M.Gaitan, Micropatterning neuronal cells on polyelectrolytemultilayers.doi: 10.1021/LA049249A; PMID: 15379510  \n84. H.Jang, S. Kim, K. Char, 利用微流体通道中的对流自组装实现多层线微图案化。Langmuir 19, 3094-3097 (2003).doi: 10.1021/la026788b  \n85. S.S. A. Castleberry, W. Li, D. Deng, S. Mayner, P. T.Hammond, Capillary flow layer-by-layer：用于高通量组装和筛选纳米层薄膜库的微流体平台。doi: 10.1021/NN501963Q; PMID: 24836460  \n86. B.Thierry, F. M. Winnik, Y. Merhi, M. Tabrizian, 通过逐层沉积在动脉上的纳米涂层：实现受损血管的体内修复。J.Am.J. Am.125, 7494-7495 (2003). doi:10.1021/ja034321x; pmid: 12812471  \n87. J.J. Richardson等人，固定颗粒上沉积纳米结构和聚合物薄膜的对流聚合物组装。Nanoscale 6, 13416-13420(2014). doi: 10.1039/C4NR04348K; pmid: 25273509  \n88. M.Hamedi 等人，通过快速逐层组装实现功能化的纳米纤维素气凝胶，用于高电荷存储及其他。Angew.Chem.Int.Ed.52, 12038-12042 (2013). doi:10.1002/anie.201305137; pmid: 24573788  \n89. B.-S.Kong, J. Geng, H.-T. Jung, Layer-by layer assemblyof graphene and gold nanoparticles by vacuum filrationand spontaneous reduction gold ion.Jeng, H.-T. Jung,Layer-by-layer assembly of graphene and goldnanoparticles by vacuum filtration and spontaneousreduction of gold ion.Chem.Chem.2009, 2174-2176(2009). doi: 10.1039/b821920f; pmid: 19360184  \n90. S.Hirsjärvi、L. Peltonen、J. Hirvonen，低分子量聚（乳酸）纳米粒子的逐层聚电解质涂层。Colloids Surf.B生物界面 49、93-99 (2006). doi: 10.1016/j.colsurfb.2006.03.009；  \n\npmid: 16616460",
+        "category": " References"
+    },
+    {
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+        "chunk": "# 研究审查  \n\n91. A.V. Sadovoy, M. V. Kiryukhin, G. B. Sukhorukov、M.N. Antipina，包裹在聚电解质多层外壳中的水分散油滴的动力学稳定性。Phys.13, 4005-4012 (Phys.Chem.13, 4005-4012 (2011). doi: 10.1039/c0cp01762k;pmid: 21240391  \n92. J.T. Wilson等人，《多电解质多层薄膜的细胞表面工程》。J.Am.133, 7054-7064 (2011).133, 7054-7064 (2011). doi:10.1021/ja110926s; pmid: 21491937  \n93. T.T.Sasaki、M.Shimizu、Y.Wu、K.Sakurai，逐层沉积法制备壳聚糖衍生物/碳酸钙复合胶囊。J. Nanomater.2008, 1-8 (2008). Doi: 10.1155/2008/185632  \n94. S.Leporatti 等人，聚电解质纳米和微胶囊壁纹理的扫描力显微镜研究。doi: 10.1021/la991429a  \n95. J.J. M. Mets、J. T. Wilson、W. Cui、E. L. Chaikof，在可存活细胞聚集体上逐层组装聚电解质多层薄膜的自动化流程。Adv. Healthcare Mater.2, 266-270 (2013). doi:10.1002/adhm.201200148；PMID: 23184761  \n96. C.Priest 等人，用于微胶囊合成的液晶液滴上的微流体聚合物多层吸附。Lab Chip 8, 2182-2187 (2008). doi: 10.1039/b808826h；pmid: 19023485  \n97. C.Kantak, S. Beyer, L. Yobas, T. Bansal, D. Trau, 片上生成逐层聚电解质的 \"微流体弹球  \n\n微胶囊。Lab Chip 11, 1030-1035 (2011). C0LC00381F; PMID: 21218225  \n\n98. S.Matosevic, B. M. Paegel, 逐层细胞膜组装。 Nat.Chem.doi: 10.1038/ nchem.1765; pmid: 24153375  \n\n99. R.D. Sochol 等人，\"通过微柱阵列栏杆系统实现连续流逐层微珠功能化\"，《第 16 届国际微波会议论文集》，第 16卷，第 1 期，第 2 页。固态传感器、执行器和微系统（传感器 2011），北京，2011年 6 月 5 日至 9 日（美国电气与电子工程师学会）。和电子工程师协会，新泽西州皮斯卡塔韦，2011 年）、pp.1761-1764.  \n100. S.Hirsjärvi, Y. Qiao, A. Royere, J. Bibette, J.-P. Benoit,Layer-by-layer surface modification of lipid nanocapsules.  \n\nEur.J. Pharm.Biopharm.76, 200-207 (2010). doi: 10.1016/j.ejpb.2010.07.010; pmid: 20656028101. K.Ariga 等人，逐层纳米结构学：发明、创新和进化。Chem.Lett.DOI: 10.1246/CL.130987",
+        "category": " References"
+    },
+    {
+        "id": 19,
+        "chunk": "# 致谢  \n\n这项工作得到了澳大利亚研究理事会澳大利亚桂冠奖学金（FL120100030，授予 F.C.）和澳大利亚政府澳大利亚研究生奖（授予 M.B.）的支持。本研究还得到了澳大利亚研究理事会聚合生物纳米科学与技术卓越中心（项目编号：CE140100036）的支持。  \n\n10.1126/science.aaa2491",
+        "category": " References"
+    },
+    {
+        "id": 20,
+        "chunk": "# Science",
+        "category": " Introduction"
+    },
+    {
+        "id": 21,
+        "chunk": "# 以技术为驱动逐层组装纳米薄膜  \n\n约瑟夫-J-理查森、马蒂亚斯-比约恩马姆和弗兰克-卡鲁索  \n\nScience 348 (6233), aaa2491. DOI: 10.1126/science.aaa2491",
+        "category": " References"
+    },
+    {
+        "id": 22,
+        "chunk": "# 薄膜制造  \n\n多种材料薄膜的沉积对一系列材料制造工艺至关重要。逐层沉积工艺是将两种或两种以上的材料按顺序沉积在一起，使其物理结合在一起。Richardson 等人回顾了用于制造薄膜的一些技术和材料，包括连续浸涂、喷涂和电化学沉积。尽管这些方法用途广泛，可沉积的材料范围也很广，但由于工业规模的挑战，这些技术仍主要局限于实验室。但是，由于微调多层膜结构和性能的空间巨大，人们对扩大这些技术的使用范围很感兴趣。  \n\n科学》，本期 10.1126/science.aaa2491  \n\n文章工具  \n\nhttp://science.sciencemag.org/content/348/6233/aaa2491",
+        "category": " Introduction"
+    },
+    {
+        "id": 23,
+        "chunk": "# 参考文献  \n\n许可",
+        "category": " References"
+    },
+    {
+        "id": 24,
+        "chunk": "# 使用本文须遵守服务条款",
+        "category": " References"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-chunks/▓у▓у╫╘╫щ╫░ Science.json b/task2/task2-chunks/▓у▓у╫╘╫щ╫░ Science.json
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@@ -0,0 +1,112 @@
+[
+    {
+        "id": 1,
+        "chunk": "# MULTILAYER ASSEMBLY",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 2,
+        "chunk": "# Technology-driven layer-by-layer assembly of nanofilms  \n\nJoseph J. Richardson, Mattias Björnmalm, Frank Caruso\\*  \n\nBACKGROUND: Over the past few decades, layer-by-layer (LbL) assembly of thin films has been of considerable interest because of its ability to exert nanometer control over film thickness and its extensive choice of",
+        "category": " Introduction"
+    },
+    {
+        "id": 3,
+        "chunk": "# ON OUR WEB SITE  \n\nRead the full article at http: /dx.doi. org/10.1126/ science.aaa2491  \n\nusable materials for coating planar and particulate substrates. The choice of materials allows for responsive and functional thin films to be engineered for various applications, including catalysis, optics, energy, membranes, and biomedicine. Furthermore, there is now a growing realization that the assembly technologies substantially affect the physicochemical properties and, ultimately, the performance of the thin films.  \n\nADVANCES: Recent advances in LbL assembly technologies have explored different driving forces for the assembly process when compared with the diffusion-driven kinetics of classical LbL assembly, where a substrate is immersed in a polymer solution. Examples of different assembly technologies that are now available include: dipping, dewetting, roll-to-roll, centrifugation, creaming, calculated-saturation, immobilization, spinning, high gravity, spraying, atomization, electrodeposition, magnetic assembly, electrocoupling, filtration, microfluidics, and fluidized beds. These technologies can be condensed into five broad categories to which automation or robotics can also be applied—namely, (i) immersive, (ii) spin, (iii) spray, (iv) electromagnetic, and (v) fluidic assembly. Many of these technologies are still new and are actively being explored, with research shedding light on how the deposition technologies and the underlying driving forces affect the formation, properties, and performance of the films, as well as the ease, yield, and scale of the processing.  \n\nOUTLOOK: Layer-by-layer assembly has proven markedly powerful over the past two decades and has had a profound interdisciplinary effect on scientific research. Scaling up the process is crucial for furthering real-world applications, and moving forward, an understanding of how to carefully select assembly methods to harness the specific strengths of different technologies has the potential to be transformative. Comprehensive comparisons between the technologies still need to be conducted, especially in regard to coating particulate substrates, where comparisons are limited but crucial for advancing fundamental research and practical applications. ▪  \n\n![](images/e5bcacff9ea1aa13130abe4250fae947111184a82ddf8c1b4ea96684a9f7beac.jpg)  \nLayer-by-layer assembly of nanofilms for preparing functional materials. The properties and performance of the resulting films depend on the substrate and layer material choices, as well as the assembly technology.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 4,
+        "chunk": "# MULTILAYER ASSEMBLY",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 5,
+        "chunk": "# Technology-driven layer-by-layer assembly of nanofilms  \n\nJoseph J. Richardson, Mattias Björnmalm, Frank Caruso\\*  \n\nMultilayer thin films have garnered intense scientific interest due to their potential application in diverse fields such as catalysis, optics, energy, membranes, and biomedicine. Here we review the current technologies for multilayer thin-film deposition using layer-by-layer assembly, and we discuss the different properties and applications arising from the technologies. We highlight five distinct routes of assembly—immersive, spin, spray, electromagnetic, and fluidic assembly—each of which offers material and processing advantages for assembling layer-by-layer films. Each technology encompasses numerous innovations for automating and improving layering, which is important for research and industrial applications. Furthermore, we discuss how judicious choice of the assembly technology enables the engineering of thin films with tailor-made physicochemical properties, such as distinct-layer stratification, controlled roughness, and highly ordered packing.  \n\nT ghoeveprenrfeodrmbyantche ior afbuinlicttyiotnoalintmeartaecrtialws ihs surrounding environments in a well-defined and controlled manner. Whether harnessing photons or electrons, separating out gas molecules or solutes, or responding to biomolecules or organisms, the environment-material interface is essential in determining the performance of the materials in various applications. Coating technologies provide the means to control the surface of a material, thus creating composite materials where the interface and the bulk of the material can, to a large extent, be engineered and controlled independently.  \n\nLayer-by-layer (LbL) assembly is a prevalent method for coating substrates with functional thin films. Following early studies that reported multilayer assembly (1, 2), it is only in the past two decades that the field has witnessed considerable growth (3). Generally, LbL assembly is a cyclical process in which a charged material is adsorbed onto a substrate, and after washing, an oppositely charged material is adsorbed on top of the first layer. This constitutes a single bilayer with a thickness generally on the order of nanometers, and the deposition process can then be repeated until a multilayer film of desired thickness has been assembled (3). For certain applications the substrate can then be removed, yielding freestanding macroscopic films, such as membranes (4), or freestanding micro- or nanoscopic films, such as hollow capsules (5, 6). Although electrostatic interactions remain widely used in facilitating formation of the films, other molecular interactions (e.g., covalent, hydrogenbonding, host-guest) are now well established for LbL assembly, with diverse materials (e.g., polymers, proteins, lipids, nucleic acids, nanoparticles, suprastructures) used as film constituents (7). The simplicity, versatility, and nanoscale control that LbL assembly provides make it one of the most widely used technologies for coating both planar and particulate substrates in a diverse range of fields, including optics, energy, catalysis, separations, and biomedicine (Fig. 1A).  \n\nThe widespread use of LbL assembly in fields with different standard tools and procedures— as well as the different processing requirements associated with substrates such as porous membranes, particles, and biological matter—has led to the development of a number of LbL assembly technologies. Examples include dipping (2), dewetting $(\\delta)_{;}$ , roll-to-roll $(\\boldsymbol{g})$ , centrifugation (10), creaming $(I I)$ , calculated saturation (12), immobilization (13), spinning $(I4)$ , high gravity (15), spraying (16), atomization $(I7)$ , electrodeposition (18), magnetic assembly (19), electrocoupling (20), filtration (21), fluidics (22), and fluidized beds (23). These different methods have often been treated as “black boxes,” where the main focus has been on what materials are used (the input) for assembling the thin films (the output), with little focus placed on the actual assembly method. However, there is now a growing realization that the assembly method not only determines the process properties (such as the time, scalability, and manual intervention) but also directly affects the physicochemical properties of the films (such as the thickness, homogeneity, and interand intralayer film organization), with both sets of properties linked to application-specific performance (Fig. 1B).",
+        "category": " Introduction"
+    },
+    {
+        "id": 6,
+        "chunk": "# Unpacking the “black box”  \n\nThe basis of LbL assembly is the sequential exposure of a substrate to the materials that will compose the multilayer films. The assembly technologies used to assemble such films form five distinct categories, namely: (i) immersive, (ii) spin, (iii) spray, (iv) electromagnetic, and (v) fluidic assembly (Fig. 2). These assembly technologies affect both the process properties and the resultant material properties (Table 1), and therefore careful choice of the assembly method can be crucial for successful application of the assembled films. Furthermore, two main themes can be identified for current developments in assembly technologies: The first is the move away from random diffusion-driven kinetics for layer deposition, and the second is the advancement from manual assembly toward automated systems.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 7,
+        "chunk": "# Immersive assembly  \n\nImmersive LbL assembly, sometimes referred to as “dip assembly,” is the most widely used method and the standard that newer technologies are often compared against. Immersive assembly is typically performed by manually immersing a planar substrate into a solution of the desired material (2, 24, 25), followed by three washing steps to remove unbound material (26). Particulate substrates can also be layered using immersion; however, the washing and deposition steps are generally broken up by centrifugation to pellet the particles (5, 6, 10). Early studies on using particles for depositing planar multilayers noted that, theoretically, any material capable of having a surface charge (such as metals, nonmetals, organics, and inorganics) could be applied for growing multilayers if suitable conditions are used (2, 24, 27). Further, it was also reported that the thickness of each layer corresponds to the thickness of the particles being adsorbed (24, 28). Immersive assembly allows for more homogenous films [when using either particle (27) or polymer multilayers (3)] in comparison with non-LbL assembly technologies such as gas deposition and nucleation deposition, making LbL assembly widely used for thin-film formation.  \n\nImprovements in immersive assembly include speeding up the process by shifting the deposition kinetics away from random diffusion toward faster kinetics, such as those arising from dewetting $(\\delta)$ , and by automating labor-intensive steps with robotic immersion machines (24, 26, 29, 30). The colloids used for planar assembly in early studies required only 1 min of immersion for each adsorption step (31); however, for immersive assembly using polymers, the substrate is ideally immersed for ${\\sim}15$ min for sufficient layer deposition (25, 26). To reduce the assembly time for polymers and to allow for the deposition of low– surface charge and/or small–contact area materials, solutions doped with organic solvents (e.g., dimethylformamide) can be used to eliminate the need for rinsing and drying steps through the process of dewetting (8). Dewetting leads to a ${\\sim}30$ -fold reduction in assembly time because the adsorption process is no longer governed by diffusion but by evaporation and dewetting. Another interesting move away from random diffusion utilizes polymer solutions that are constantly stirred by magnetic stirrer bars, which allows for robust layers to be deposited within tens of seconds after immersion (32). Instead of speeding up the adsorption process by using different adsorption kinetics, handling times can be decreased by automating the process (9, 24, 26, 27, 29, 30, 33). One approach to automation uses a quartz crystal microbalance (QCM) as a substrate, allowing for layering to be controlled with a computer-monitored feedback loop (30). QCM enables the layering process to be based on a fixed mass of adsorbed material rather than fixed immersion times. Furthermore, the feedback loop allows for precise and reproducible control over the film growth and allows for linear film growth to be engineered from polymer combinations that give nonlinear film growth using fixed times (30). For fixedtime immersive assembly, computer-programmed automated slide stainers can be retrofitted for automated multilayer assembly, allowing for agitation and solution exchange during washing steps (24, 29). A similar, although custom-built, computer-programmed machine can deposit \\~1000 layers of charged colloids onto particulate substrates (substrates ${\\sim}100~\\upmu\\mathrm{m}$ in diameter) (27).  \n\nAlthough automation decreases manual involvement, it does not substantially reduce the overall assembly time, which is why some efforts have focused on combining faster deposition kinetics with automated systems. For example, one commercially available robot uses a rotating slide holder to speed up the assembly process (26). This rotation allows for a 3- to 10-fold reduction in adsorption times and allows for thicker films to be prepared using higher rotation speeds. Roll-to-roll assembly also allows for layering to be performed faster (by 5- to 10-fold), through the use of flexible substrates (9). The immersion time and speed of the rolling process play a large role in determining the film properties, and the drying conditions, wettability, and substrate movement speed require optimization to produce films with similar properties to standard immersive assembly (9). A further improvement to roll-toroll assembly uses a nip-roll technique to prevent excess solution from cross-contaminating the system, resulting in more homogenous coatings than immersive assembly (34).  \n\nImmersive assembly can be performed on particulate substrates that are too small to sediment quickly or physically move between solutions, such as micro- and nanoparticles. The most common technology for immersive assembly on particulate substrates is performed by adding polymer solution to dispersed dense particulate substrates, pelleting the particles with centrifugation, removing the supernatant, washing multiple times with a similar pelleting process, and then repeating the steps for multilayer growth (5, 6, 10). This is generally time-consuming and labor-intensive due to the centrifugation steps, and particles dense and large enough to be pelleted are required. However, by using particulate substrates lighter than water (e.g., emulsions), creaming and skimming cycles can be applied for washing steps $(I I)$ , although centrifugation can also be used to speed up the flotation and creaming process (35), with lighter emulsions capable of creaming in a matter of minutes rather than hours (36). The use of emulsions the surfactants used for emulsion stabilization (36).  \n\n![](images/b7a9ce7ea9198ca3372723cb19c2e1c25fc327cd69823e19235114a6372907be.jpg)  \nFig. 1. Versatility of layer-by-layer assembly. (A) Schematic overview of LbL assembly and (B) an overview showing that the assembly technology influences film and process properties, as well as application areas. [Illustration credit: Alison E. Burke and Cassio Lynm]  \n\nparticulate substrates is the attempt to avoid centrifugation, as it can lead to aggregation, is labor intensive, and is generally difficult to automate. A simple way to avoid centrifugation is to remove the need for washing steps. This can be achieved by adding exact amounts of polymer",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 8,
+        "chunk": "# AImmersive  \n\ncalculated to saturate the surface of the particulate substrates (12, 37), rather than the high concentrations of excess polymer solution generally used $(5,6,70)$ . Initially, only two to three layers could be deposited before the particles start to aggregate (12), but more layers can be  \n\n![](images/db49d6a8b2aa4dcd35b85ddf86eb582a1c7a4c9ea08ad01759a77f7816eb2d0e.jpg)",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 9,
+        "chunk": "# B Spin  \n\n![](images/fff766b39dedea6385454d126875f6e3a4596ee8e5ae5f192b8cee882e771352.jpg)",
+        "category": " Introduction"
+    },
+    {
+        "id": 10,
+        "chunk": "# CSpray  \n\n![](images/7d743aa88d75ad5b6c751b9f409ea8c2a2bb828105f4805a657c29d97dad42cc.jpg)",
+        "category": " Materials and methods"
+    },
+    {
+        "id": 11,
+        "chunk": "# D Electromagnetic  \n\n![](images/73748c7bdc555ca4d6cf1b1e2891039f216336ee81b3803df46ff3cc2d3472d0.jpg)  \n\nE Fluidic  \n\n![](images/2f4a9ca2112bb59a97af9c51da5c9c3a288df4951d0119bccd71b1a03de13855.jpg)  \nFig. 2. Layer-by-layer assembly technologies. (A to E) Schematics of the five major technology categories for LbL assembly. [Illustration credit: Alison E. Burke and Cassio Lynm]  \n\ndeposited by incrementally measuring the zeta potential during assembly (37). Additionally, the use of constant mixing for soft particulate substrates such as emulsions (38) or sonication during layer deposition for hard particulate substrates like drug crystals (39) reduces aggregation. By optimizing the protocol, the saturation method gives a similar shell thickness to centrifugation-based assembly but is about three times faster (37, 39). This technology requires constant monitoring and surface area calculations to avoid adding excess polymer and therefore does not reduce manual involvement. A technology that focuses on decreasing manual involvement and reducing the need for centrifugation uses particulate substrates immobilized in agarose to convert collections of particulate substrates into a macroscopic substrate (33). This macroscopic collection of immobilized particles can be treated like a planar substrate and immersed in polymer solutions using a robotic dipping machine, allowing for full automation during the layering process. Although this technology generates films roughly half the thickness of those prepared by conventional centrifugation-based assembly, probably due to the impeded diffusion of polymers through the agarose hydrogel, ${\\sim}80\\%$ of the particles can be recovered, which is an improvement over the ${\\sim}90\\%$ loss that has been reported for centrifugation-based assembly at high layer numbers (21, 33).  \n\nDue to the ease of use and versatility of material and template choice, immersive assembly has been applied for numerous applications. For example, light-emitting diodes (LEDs) can be prepared from immersive assembly on planar substrates, with the polymer choice and multilayer thickness giving control over luminance and the turn-on voltage (29). Automated roll-toroll immersive assembly can be used for depositing conductive and flame-retardant coatings (34). Planar substrates coated with particle multilayers can be used for the detection of small particles invisible to the naked eye through color shifts in the multilayer films (2). Glass slides can also be coated with particle multilayers for the preparation of antireflective, antifogging, and self-cleaning surfaces (24). Fusion microreactors coated with particles are more conducive toward reaction (27). Certain particulate substrates easily allow for the removal of the template particle, leaving behind hollow multilayer capsules. Similarly, drugs themselves can be used as the particulate templates, with both types suitable for drug delivery, (5, 6, 33, 38–40).  \n\nIn summary, immersive assembly is the most commonly used LbL assembly technology and the de facto standard against which other technologies are compared. The simplicity of immersing substrates of almost any shape or size into containers with layering solution makes this technology easily accessible. The films produced have an interpenetrated structure and form “fuzzy” nanoassemblies that are almost synonymous with LbL assembly (3). Much recent work has been focused around shorter assembly times and automated systems with less manual intervention. For coating particulate substrates, there has also been considerable interest in technologies applicable to coating smaller, low-density particles (such as silica nanoparticles), which can be difficult to handle with the conventional centrifugation-based assembly. As immersive assembly typically requires more material than other technologies, especially to submerge large substrates on industrial scales, waste can be an issue, although solutions can be reused as long as cross-contamination remains low. Immersive assembly has been the workhorse of LbL assembly and will undoubtedly continue to play an integral part in the development of new and improved thin films.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 12,
+        "chunk": "# Spin assembly  \n\nLayer-by-layer assembly using spin coating (i.e., “spin assembly”) utilizes the common coating technology of spinning a substrate to facilitate the deposition of materials $(I4)$ . Although drying a substrate after immersive LbL assembly can be achieved through spinning (41), the majority of spin assembly is performed by either casting the solution onto a spinning substrate (42) or casting the solution onto a stationary substrate that is then spun (43). Spinning quickens the assembly process considerably, allowing for layers to be deposited in $\\sim30~\\mathrm{s}$ due to the various  \n\nTable 1. Selected LbL assembly technologies and properties arising from using each technology.The table is intended to provide a general overview and is not exhaustive. NR indicates not reported in selected references. [Illustration credit: Alison E. Burke and Cassio Lynm]   \n\n\n<html><body><table><tr><td colspan=\"2\"></td><td colspan=\"2\">BUILDING BLOCKS</td><td colspan=\"2\">PROCESS PROPERTIES</td><td colspan=\"3\">NANOFILM PROPERTIES</td></tr><tr><td>LbLASSEMBLY TECHNOLOGY</td><td>Substrates</td><td>Substrate sizes*</td><td>Layer materials</td><td>Time per</td><td>Automated</td><td>Layer (current status) thickness, nmt nm</td><td>Roughness, Layer</td><td>structure</td></tr><tr><td colspan=\"2\">Immersive Dipping (2,25)</td><td>Planar</td><td>10 nm-1 m</td><td>layer 10 s-12 h</td><td></td><td><1-15</td><td>1-20</td><td>Interpenetrated</td></tr><tr><td colspan=\"3\">Calculated saturation (12,37)</td><td>1-100 mm</td><td>Polymers, colloids</td><td>10-30 s (32) or 10-20 min (26)</td><td>Yes</td><td>1-2 (25, 26)</td><td>1-10 (44, 49)</td></tr><tr><td rowspan=\"6\">Roll-to-roll (9) Centrifugation (5, 6)</td><td rowspan=\"5\">Dewetting (8)</td><td>Planar</td><td>1-10 mm</td><td>Polymers, colloidss 30-60 s (8)</td><td></td><td>No</td><td>NR</td><td></td></tr><tr><td></td><td>Flexible planar 100 mm-1 m</td><td>Polymers</td><td>2-5 min (9, 34)</td><td>Yes</td><td>1-2 (8) 1-15 (9,34)</td><td>15-20 (9,34)</td></tr><tr><td>Particulate</td><td>10 nm-10 μm</td><td>Polymers, colloids</td><td>20+ minl (5, 6)</td><td>No</td><td>1-2 (5,10)</td><td>3-10 (23, 94)</td></tr><tr><td>Particulate</td><td>100 nm-1 μm</td><td>Charged polymers</td><td>5-10 min (39)</td><td>No</td><td>1-2 (39)</td><td>NR</td></tr><tr><td>Immersive immobilization Particulate</td><td>100 nm-1μm</td><td>Polymers</td><td>40-50 min (33)</td><td>Yes</td><td><1 (33) NR</td><td></td></tr><tr><td>(33) Creaming (11)</td><td>Emulsion</td><td>10 nm-1μm</td><td>Polymers, colloids</td><td>0.5-12 h (11, 36)</td><td>No</td><td>1-7 (36, 38) NR</td><td></td></tr><tr><td colspan=\"2\">Spin</td><td>1-100 mm</td><td></td><td>10 s-5 min</td><td></td><td><1-2</td><td>1-10</td><td>Stratified</td></tr><tr><td colspan=\"2\">Spin (14, 42, 43)</td><td>1-100 mm</td><td>Polymers, colloids</td><td>10-60 s (43)</td><td>Yes</td><td><1-2 (42)</td><td>1-10 (44, 46)</td><td></td></tr><tr><td colspan=\"2\">Planar High gravity (15) Planar</td><td>1-10 mm</td><td>Polymers, colloids</td><td>20 s-5 min (15, 49)</td><td>No</td><td>NR</td><td>1-2 (49)</td><td></td></tr><tr><td colspan=\"2\">Spray</td><td>10 nm-10 m</td><td></td><td><1 s-24 h</td><td></td><td><1-15</td><td>1-10</td><td>Stratified</td></tr><tr><td rowspan=\"4\"></td><td>Spray (16, 52)</td><td>Planar</td><td>1 mm-10 m</td><td><1-30 s (59)</td><td></td><td>Yes</td><td><1-5 (16,51) 1-10 (51)</td><td></td></tr><tr><td>Atomization (17)</td><td>None</td><td>Polymers 10-100 nm Charged polymers</td><td>12-24 h (17)</td><td>No</td><td>5-15 (17)</td><td>NR</td><td></td></tr><tr><td>Spray immobilization (63)</td><td>Particulate</td><td>10-100 nm Polymers</td><td>5-10 s (63)</td><td>Yes</td><td>2-4 (63)</td><td>NR</td><td></td></tr><tr><td>Electromagnetic</td><td></td><td>10 nm-100 mm</td><td>1 s-20 min</td><td></td><td>1-20,000</td><td>10-30</td><td>Stratified</td></tr><tr><td>Electrodeposition (18, 20, 67,73)</td><td>Planar</td><td>1-100 mm</td><td>Polymers, colloids</td><td>1 s-20 min1 (65, 71)</td><td>No</td><td>2-20,0001 (20,67, 71)</td><td>10-30 (66, 70)</td><td></td></tr><tr><td>Magnetic (19, 76)</td><td>Planar and Particulate</td><td>10 nm-100 mm</td><td>Polymers, colloids</td><td>15-20 min (19, 76)</td><td>No</td><td>1-2 (19, 75)</td><td>NR</td><td></td></tr><tr><td colspan=\"2\">Electro-immobilization (13)</td><td>Particulate 10 nm-1μm</td><td>Charged polymers</td><td>15-20 min (13)</td><td>No</td><td>2-3 (13)</td><td>NR</td><td></td></tr><tr><td colspan=\"2\">Fluidic Planar</td><td>100nm-100mm</td><td></td><td>10 s-45 min</td><td></td><td><1-3</td><td>1-11</td><td>NR</td></tr><tr><td colspan=\"2\">Microfluidicplanar(22)</td><td>10 μm-100 mm</td><td>Polymers</td><td>1-15 min (80, 81)</td><td>Yes</td><td></td><td><1-3 (83,84) 1-10 (80, 84)</td><td></td></tr><tr><td colspan=\"2\">Microfluidicparticulate (96-98)</td><td>Particulate 100 nm-10μm</td><td>Polymers</td><td>10-60 s (96-98)</td><td>Yes</td><td>1-3 (96, 97)</td><td>NR</td><td></td></tr><tr><td>Fluidized bed (23)</td><td>Particulate</td><td>1-10 μm</td><td>Polymers</td><td>3-5 min (23)</td><td>No</td><td>2-3 (23)</td><td>9-11 (23)</td><td></td></tr><tr><td>Fluidic immobilization（86, 87)</td><td>Particulate</td><td>100 nm-1μm</td><td>Polymers, colloids</td><td>5-45 min (86, 87)</td><td>No</td><td>1-2 (87)</td><td>NR</td><td></td></tr><tr><td>Vacuum/filtration(21)</td><td>Particulate and fragile**</td><td>100 nm-1 μm</td><td>Polymers</td><td>10-20 min (95)</td><td>Yes</td><td>1-2 (94)</td><td>5-10 (94)</td><td></td></tr></table></body></html>  \n\n\\*Typical order of magnitude substrate sizes are indicated. Larger or smaller substrate sizes are possible. †Typical thicknesses per layer for linearly growing films are indicated. Per-layer thicknesses for exponentially growing films vary widely, given the nonlinear growth profile. ‡Time with or without agitation, respectively. §Dewetting can make use of materials that are usually difficult to layer (e.g., materials with low charge or with low surface contact). ‖Centrifugation processing time is highly variable due to manual pipetting and resuspension steps. ¶Thickness is dependent on time. \\*\\*Fragile substrates, such as mammalian cells, can be layered using fluidic filtration.  \n\nforces governing the process (43). Furthermore, spin assembly allows for automation and the coating of substrates up to $10\\ \\mathrm{cm}$ in diameter using commercially available spin coaters (44, 45). However, standard spin coaters are generally designed for flat surfaces and are not amenable to the complex shapes accessible to immersive assembly.  \n\nSpin assembly typically results in more homogenous films compared with immersive assembly. This is because assembly is driven by a collection of forces including electrostatic interactions, which cause the adsorption and rearrangement of polymers, and centrifugal, air shear, and viscous forces, which cause desorption of weakly bound polymers and dehydration of the films (43). These forces are also the reason why spin assembly can be orders of magnitude faster than immersive assembly. The salt concentration of the polymer solution has a larger effect at higher spin speeds, meaning that electrostatic forces play a greater role at low ionic strength, and shear forces dominate at high ionic strength (46). These shear forces produce thinner, highly ordered films with specific layer interfaces when compared with immersive assembly, which produces thicker interpenetrated films (47). Specifically, the thickness for spin-assembled polymer films is generally linked to the spin speed, with higher speeds leading to thinner films (42). When depositing colloids, the forces experienced during spinning lead to a monolayer of colloids, whereas standard immersive assembly often leads to a pseudomonolayer in which the substrate is not fully coated (43, 48). A comparison study of the differences between automated immersive assembly and automated spin assembly found that immersive-assembly prepared thicker, rougher films, whereas spinning resulted in thinner, smoother films (44). The films differed visually, as the spin-assembled films were transparent because of their distinct-layer stratification, and the immersive-assembled films were opaque due to their inhomogeneous, interpenetrated layers (Fig. 3). The contact angle and the relative concentration of polymers were consistent across all bilayers for spin-assembled films, whereas immersive-assembled films became rougher with time, giving varying contact angle and relative concentration ratios between the two constituent layers $(44)$ . Another study, which compared spin assembly and immersive assembly, showed that clay nanocomposites in spin-assembled films have a higher degree of orientation (45). However, one issue that can result from spin assembly, which is not a concern for other assembly technologies, is that at higher ionic strengths of polymer solution, and also at lower spin speeds, the films can be thicker where the solution was cast when compared with the edges of the substrate (42, 46).  \n\n![](images/62a1cdaf212f9b0e4e5123f2560a71655d2f1d5ae49dd65bad9551e9136b3543.jpg)  \nCreating different nanofilm properties using immersive vs spin LbL assembly   \nFig. 3. Comparison between immersive and spin assembly. (A) Schematic comparison with layers of different materials. (B) Comparison between an immersive-assembled film (left) and a spinassembled film (right). Films are made of hydrophobically modified poly(ethylene oxide) and poly(acrylic acid). [Adapted with permission from (44). Copyright 2008 American Chemical Society.] [Illustration credit: Alison E. Burke and Cassio Lynm]  \n\nIn a special case of spin assembly, the substrate can be placed in a closed container with a polymer solution or a colloidal dispersion parallel to the axis of rotation (rather than perpendicular). Upon spinning, centrifugal force pushes the layer material directly onto the substrate rather than across the substrate, hence the name “highgravity assembly” (15). This allows for improved film deposition and uniformity, especially at low polymer concentrations, because the rotation and increased turbulence lower the thicknesses of both the laminar layer and the diffusing layer around the substrate. The adsorption equilibrium can be reached at least five times faster than immersive assembly and is controllable by the spin speed. Furthermore, polymer combinations that grow exponentially using immersive assembly also grow linearly using this technology. Similarly, the roughness is much lower (\\~2- to 10-fold) for LbL films assembled in this way (49).  \n\nSpin assembly typically produces substantially more organized films and multilayers than immersive assembly, which has made it a useful tool in preparing optical coatings with controllable and homogenous color (14) and for preparing transparent films (44). Similarly, spin assembly is useful for preparing LEDs with higher luminance than immersive assembly (41). A primary limitation for spin assembly in terms of application is that it is limited to coating small planar substrates, as increasing the substrate size requires higher spin speeds. Furthermore, spin coating of nonplanar surfaces is complicated.  \n\nIn summary, spin assembly uses rotating substrates to deposit layers and remove excess coating material. Spin assembly typically produces thinner, more organized, and more stratified multilayers than does immersive assembly, and the process can be much faster. The spin coater needed for assembly is commonly accessible in many research environments and even some industrial settings, such as with the robotic wafer processing common in the semiconductor industry, which could facilitate translation from the laboratory to real-world applications. Furthermore, depositing multilayer films on nonflat surfaces, or even flat but rough surfaces, can be challenging due to the shear forces involved with film assembly. Nevertheless, the film and process properties arising from spin assembly, including smooth films assembled in a relatively short time, continue to make this method an attractive choice.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 13,
+        "chunk": "# Spray assembly  \n\nSpray LbL assembly is another assembly category, where films are assembled by aerosolizing polymer solutions and sequentially spraying them onto substrates (16). Although spraying air has been used to dry films during LbL assembly to reduce contamination (and align carbon nanotubes) (50), here we discuss spray assembly solely in the context of layer deposition. Standard spray assembly is much faster (as quick as ${\\sim}6\\mathrm{s}$ per layer) than immersive assembly $(5I)$ and approaches an industrial level far surpassing that of spin assembly (52, 53). Vacuum can also be used to further speed up the process by minimizing the lag time between spraying and washing, and vice versa, and to facilitate the spray coating of three-dimensional (3D) objects like membranes $(54)$ .  \n\nIn spray assembly, the film properties—such as the morphology, uniformity, chemical composition, and selective membrane properties—can be tailored to be similar to those prepared by immersive assembly, with the film thickness influenced by suspension concentration, spray flow rate, spray duration, resting duration, whether or not the substrate is washed and for how long, and whether the solution is sprayed vertically or horizontally (16, 51, 55–57). This control arises from the two main forces governing the spray assembly process, namely, bulk movement in the actual spray and random movement in the liquid film $\\left(56\\right)$ . The random movement in the liquid film allows for polymer rearrangement and generates much higher convection close to the substrate, allowing for improved deposition. This is because of the submicron thickness of the liquid film at the substrate interface and because of the speed at which the spray contacts the substrate (16, 56). Washing the substrate generally produces thicker films than leaving the substrate unwashed, due to polymer rearrangements during washing $(5I)$ . Like spin assembly, the films resulting from spray assembly have more distinct layers in comparison to immersive assembly (16, 53).  \n\nSpray assembly has also been combined with other technologies to leverage technology-specific advantages and automate the assembly process. For example, a disadvantage of spray LbL assembly is that the obtained films may not be homogeneous due to the effects of gravity draining, causing increased deposition in the vicinity of the solution drips, and because of irregular patterns caused by the spray nozzles at certain distances (51, 57). To address this problem, rotating the substrate during spray assembly allows for the preparation of more homogeneous films and subsecond spray times for each layer (56, 58, 59). By spraying rotating substrates, a majority of the polymer added to the substrate is adsorbed. In comparison, the vast majority of polymer remains in the coating solutions after immersive assembly. Therefore, applicable concentrations roughly 10 to 50 times less than those required for immersive assembly can be used for spray assembly on rotating substrates (55, 59). Larger 3D substrates, such as tubular membranes, can also be coated by rotating the substrate during spraying (60). A further improvement has been the computer-aided automation of spray assembly to reduce manual processing (58, 60). Similar to the use of automated immersive assembly on QCM chips, the use of QCM chips for automated spray assembly enables feedback loop control and tracking of real-time film growth (61). Automated spray assembly has also been combined with roll-to-roll processing for coating industrialsize substrates (i.e., substrates that are tens of meters long) (62). Roll-to-roll spray assembly can also be used to coat particulate substrates with multilayer films by performing spray assembly on particulate substrates immobilized on top of a dissolvable surface (63).  \n\nA stand-alone spray assembly technology for coating particulate substrates uses surface acoustic waves of 1 to $10\\ \\mathrm{nm}$ in amplitude to atomize polymers and cargo $(I7)$ . As the atomized droplets move through the air, the solvent evaporates and the polymer condenses into particle form, resulting in the first atomized solution becoming the template for subsequent coatings, with \\~1000 carriers produced from each microliter of solution. The particles are dialyzed to remove excess polymer, added to a solution of oppositely charged polymer, and then re-atomized to coat the particles. This process can be repeated for multilayer assembly; however, the dialysis process increases the processing time of this technology to ${\\sim}24$ hours for each layer.  \n\nSpray assembly has found use for a wide variety of applications because it can be used to coat industrial-scale substrates with relative ease (62) and is not limited to planar substrates $(54,60,63)$ . Spray assembly has been used to prepare flameretardant films over cotton cloth, where it was shown that spraying on vertically oriented substrates produced superior flame-retardant films compared with both spraying on horizontally oriented substrates or dipping $(57)$ . Clothing material was also coated with spray assembly to control air flux and provide chemical protection, potentially for use with military uniforms $(54)$ . Like other assembly technologies, spray assembly has been used to prepare antireflective coatings $(6\\bar{{I}})$ , and similarly, car tinting with structured coloring to reduce heating from infrared light $(\\theta2)$ . Membrane tubes could also be coated to improve the separation of organic dyes from water (60). Because the structure of the films can be controlled at the nanometer-level by the spray time, spray assembly can be used to control conductance in thin films in ways that are not available to other assembly technologies $(59)$ . Spray assembly has been used to prepare particles to examine cellular uptake of different coatings and aspect ratios of particles $(63)$ and for gene delivery in vitro $(I7)$ . Spray assembly has found use in diverse applications and industry because it offers rapid assembly times and is amenable to both automation and scale-up.  \n\nIn summary, spray assembly produces multilayer films by aerosolizing coating solutions and spraying them onto the substrate. The resulting films are typically well organized with distinct layers. Spray assembly is a quick and easy method to coat large or nonplanar substrates, although immersive assembly remains the method of choice for coating complex 3D substrates. Spray assembly is one of the most highly relevant technologies for industrial applications, as it is already widely used in industry.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 14,
+        "chunk": "# Electromagnetic assembly  \n\nElectromagnetic assembly is based on the use of an applied electric or magnetic field to effect layering, such as by coating electrodes in polymer solutions or by moving magnetic particulate substrates in and out of coating solutions (18, 19). The former, commonly referred to as electrodeposition, is a well-established technology for coating materials using an applied voltage in electrolytic cells. In the standard electrodeposition setup, two electrodes are immersed in polymer solution, then an electric current is applied. The electrodes are then washed and placed into solution of an oppositely charged polymer; the polarities of the electrodes are reversed, and the process is repeated (64). Electrodeposition can be used to rapidly assemble ions, polymers, and colloids in much less time than in immersive assembly (18). For example, bimetallic mesoporous LbL films can be prepared by electrodeposition, with the electrodeposition time determining the layer thickness at ${\\sim}1.5\\ \\mathrm{nm/s}$ $(65)$ . In another setup, the substrate can be placed between the two electrodes, allowing for planar substrates to be coated $(66),$ or even immobilized particles (13). This technology results in films roughly twice the thickness of those resulting from centrifugation-based assembly. Electrodeposition can also use higher voltages, upwards of 30 V (13, 66); however, the assembly process for immobilized particles can take as long as $15~\\mathrm{min}$ per layer (13).  \n\nThe thicknesses of the electrodeposited films are directly related to the voltage used during assembly, with the optimum voltage for achieving the thickest films dependent on the pH of the polymer solution $(67)$ . Higher voltages can cause desorption of the film as the electrode (i.e., the substrate) begins to repel the previously deposited layer. Generally, pH values lower than the $\\mathrm{p}K_{\\mathrm{a}}$ (where $K_{\\mathrm{a}}$ is the acid dissociation constant) of the polymers need lower voltages to reach peak thickness, and that peak thickness is also larger than the peak thickness at higher $\\mathrm{pH}$ , closer to or above the $\\mathrm{p}K_{\\mathrm{a}}$ of the polymers. However, if the voltage is raised high enough, a secondary peak thickness can be reached, allowing for the assembly of films at pH values otherwise difficult to grow using other technologies $(67)$ . The reason for this “valley” in thickness is that at high voltages, the electrolysis of water at the electrode plays a bigger role in hindering polymer adsorption; however, at even higher voltages $\\mathrm{({>}3~V)}$ the electrostatic interaction between the polymer and electrode exceeds any hindrance due to electrolysis (67). For example, polymer-enzyme films are roughly twice as thick when assembled at an optimal voltage of  \n\n$1.2\\:\\mathrm{V}$ , compared with using lower or higher voltages (below 3 V) (68). These studies show that electrodeposition is similar to other LbL assembly technologies in the sense that the pH of the polymer solution, and therefore the configuration of the polymer itself, is crucial in controlling film thickness.  \n\nAt higher voltages, electromagnetically assembled films are more interpenetrated than immersive-assembled films, which is in contrast to the highly stratified films prepared at lower voltages (66). When forming polymer-polymer films, the refractive index does not change substantially during film growth in a flow cell under an electric current, suggesting a more homogenous deposition than in immersive assembly (69). Similarly, polymer-colloid films show high organization, as the refractive index decreases and transmittance increases when assembling films under higher voltages (70). Correspondingly, electrodeposited enzyme-polymer films are more uniform than immersive-assembled films, with $90\\%$ coverage of the substrate versus $\\sim50\\%$ coverage, respectively $(\\boldsymbol{68})$ . Because of this stratification and high surface coverage, electrodeposition allows for control over the spacing between layers (68).  \n\nElectrodeposition can also be achieved by using local effects at the electrodes, such as inducing redox reactions or changes in pH. The $\\mathrm{pH}$ of the solution near the anode and cathode changes markedly from bulk solution to lower and higher pH values, respectively $(7\\bar{1})$ . The low pH near the anode can induce polymer deposition. However, this pH-induced electrodeposition is fairly limited, as only a few bilayers can be deposited (using materials such as alginate and chitosan) because the layers become too thick (tens of micrometers) for the electric current to penetrate, resulting in no pH change and therefore no deposition. Using a similar principle, covalently stabilized films can be prepared by generating copper(I) from copper(II) in situ at the electrode (i.e., the substrate) for crosslinking azide- and alkyne-containing polymers with copper-catalyzed “click” reactions (20). Polymers containing electrically sensitive click groups can also be electrocoupled, allowing for 500-nm-thick transparent, and therefore stratified and homogenous, films to be prepared in ${\\sim}30\\ \\mathrm{min}$ $(72)$ . One-pot synthesis can be performed using the same basic principles by switching between oxidative and reductive reactions by alternating the voltage, allowing for washfree assembly using electropolymerization $(73)$ .  \n\nMagnets, rather than electric currents, can be used to assemble LbL films on sensitive particulate templates, such as emulsions (74), or small templates difficult to pellet through centrifugation, such as sub–10-nm iron oxide nanoparticles (19). Template particles containing magnetic nanoparticles can be separated from the polymer solution using a magnet, which, similar to the filtration method, allows for nearly $100\\%$ of the particles to be recovered in a centrifugationfree LbL assembly process $(75)$ . Magnets or an external field can also be used to orient layered magnetic nanoparticles on a planar substrate so that a subsequent layer of nanoparticles can deposit more rapidly and in an oriented fashion $(76)$ . This technology uses standard immersive assembly for the deposition of positively and negatively charged magnetic nanoparticles with application of a magnetic field between deposition steps. Therefore, the thickness does not increase in relation to standard immersive assembly; however, the absorbance of the film increases with application of the magnet, suggesting increased packing $\\left(76\\right)$ .  \n\nElectromagnetic assembly has found use in several different applications, as it can be used to form LbL films with compositions that are not readily assembled using other technologies. Bimetallic films of Pt and Pd layers have BrunauerEmmett-Teller surface areas of $\\sim40\\ \\mathrm{m^{2}\\ g^{-1}}$ and therefore exhibit enhanced electrochemical activity in the methanol oxidation reaction, compared with single-layer films $(\\boldsymbol{65})$ . Antireflective coatings can be prepared by adjusting the refractive index of the films by assembling the films at different voltages $(70)$ . Biological applications have also been explored, as biocompatible coatings can be formed using electromagnetic assembly, with in vitro tests confirming negligible cytotoxicity $(\\pi)$ . Bienzyme films with bioelectric catalytic properties have higher surface coverage, and therefore activity, when compared with traditionally prepared films $^{\\prime}68)$ . The stratification of the assembled films is also conducive toward high-performance photoelectric devices $(72)$ and separation membranes ${(\\delta\\delta)}$ . Hollow polymer capsules (from micrometers to sub– $\\cdot100\\ \\mathrm{nm}$ in diameter) can also be prepared using electrodeposition on immobilized particles $(I3)$ .  \n\nIn summary, electromagnetic assembly uses electric or magnetic fields, typically in the form of electrodes in polymer solutions or magnetic particulate substrates, to deposit films. Electromagnetic assembly can exploit current-induced changes in pH or redox-reactions to effect film assembly, thus using a driving force substantially different from that of the other main assembly categories. Generally, electromagnetic-assembled films are thicker and more densely packed than films prepared using other LbL assembly methods (13, 68). Electromagnetic assembly is still not as common as some of the other technologies, and even though it requires special equipment and expertise, it does offer a different approach to multilayer film assembly (e.g., through magnetic handling of substrates and materials or through electrically induced assembly), thereby providing alternative opportunities for assembling films.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 15,
+        "chunk": "# Fluidic assembly  \n\nFluidic assembly can be used to deposit multilayers with fluidic channels, both by coating the channel walls and by coating a substrate placed or immobilized in a fluidic channel $(77)$ . The general method involves using pressure or vacuum to sequentially move polymer and washing solutions through the channels, which can be fluidic components, such as tubing or capillaries, or designed microfluidic networks (78, 79). Flowchamber–based QCM is a common fluidic assembly technology used for investigating thin-film properties and multilayer growth by providing crucial real-time information (22). Higher concentrations of polymer solution typically yield thicker films $(79)_{:}$ , with the contact time rather than the flow rate as the crucial factor determining the amount of adsorbed polymer under flow (80).  \n\nFluidic assembly is typically implemented using a pump, capillary forces, or spinning to transport the liquid through the channels, although pipetting and static incubation can also be used. However, fluidic assembly strongly resembles immersive assembly when polymer solutions are allowed to remain in static contact with the substrate for more than 10 min (81, 82). Polymer and washing solutions loaded into channels with a pump or vacuum can deposit \\~1.5-nm-thick layers in 5 to $10~\\mathrm{min}$ (83). Capillary forces can also be used to pull polymer solutions through microfluidic channels by placing droplets of solution at fluidic inlets, followed by spinning the substrate to remove the solution, allowing for \\~1.2-nm-thick layers to be deposited in less than $2\\ \\mathrm{min}$ $(\\boldsymbol{84})$ . Fluidic layering based on capillary forces is easy to implement, as capillary action does not require external active components, but it is not suitable for larger volumes or when dynamic control over the flow rate is needed.  \n\nFluidic devices and perfusion chambers can also be used to achieve region-specific fluidic assembly or to perform fluidic assembly on more complicated 3D structures. For example, complex automated microfluidic devices can be used to assemble hundreds of layers in parallel using capillary flow and vacuum to fill and empty multiple channels $(85)$ . This enables the high-throughput screening of film libraries using small quantities of materials, as only a droplet is needed to fill a single microchannel. Region-specific films can be coated on substrates by affixing a geometric chamber over the substrate and then flowing the solution through the chamber and over the substrate (80). Perfusion chambers can be used for fluidic layering on complex 3D substrates such as sensitive biological substrates (like arteries), which must remain constantly hydrated during layering (86). Similarly, perfusion chambers can be used to hold agarose that contains immobilized particles for fluidic assembly $({\\boldsymbol{87}})$ . This technology not only allows for the deposition of polymers but also for the deposition of larger cargo, such as gold nanoparticles or liposomes, and produces films with nearly identical thickness to those prepared by standard centrifugation-based assembly $({\\boldsymbol{87}})$ .  \n\nVacuum is typically used with other assembly technologies, such as spray assembly, or to remove the solution from channels in fluidic assembly, but it can also be used to form multilayers in a macrofluidic-type assembly, especially on unusual substrates like aerogels. Aerogels can be functionalized using vacuum assembly by pouring solutions of conducting polymers, biomolecules, or carbon nanotubes from the top and applying vacuum to pull these solutions down through the aerogel (88). Vacuum assembly can also be used to deposit materials, such as reduced-graphene oxide, that would otherwise pose a challenge to the creation of uniform multilayers (89). For particulate substrates, vacuum assembly can be performed using separating filters, down to $200~\\mathrm{nm}$ in pore size, for centrifugationfree layering (21, 90). Vacuum is not applicable for all sensitive templates; however, for template particles including emulsions (91), cell islets (92), or calcium carbonate nanowires $(93)$ , a slight vacuum $(\\sim100~\\mathrm{mbar})$ can facilitate the layering process (21). Less than $3\\%$ of the particles are lost during assembly using an optimized procedure, far less than with the calculated saturationbased method, where $\\sim50\\%$ can be lost, or the centrifugation-based method, where more than $80\\%$ can be lost at high layer numbers (21). This combined filter-and-vacuum assembly technology yields a layer thickness of ${\\sim}1.3\\ \\mathrm{nm}$ and a surface roughness of ${\\sim}5$ to $10\\mathrm{nm}$ , which are both similar to those prepared via centrifugation-based assembly $(94)$ . A filtration setup has also been automated for coating cell islets, using a feedback loop for evacuating the fluid from the reaction chamber, thereby reducing the manual handling time by $\\sim60\\%$ (95).  \n\nLike vacuum assembly, fluidic assembly is not restricted to planar substrates and is a viable alternative for centrifugation-free assembly on particulate substrates (96–98). Many fluidic assembly approaches coat emulsions or liquid crystals, as these materials are well studied in the fluidics field. Generally, the coating and washing solutions are deflected past the flow of particles by using physical gaps smaller than the particles so that the flow can enter perpendicular (96) or parallel to the particle flow stream $(97)$ . For fluidic assembly in parallel flow systems, larger template particles ${\\sim}50~\\upmu\\mathrm{m}$ in diameter) are necessary, as they can be deflected in a zig-zag pattern using solid pillars at a ${\\sim}45^{\\circ}$ angle to three parallel laminar flow streams: solution $\\mathbf{A},$ washing, and solution B. This gives a layer thickness of ${\\sim}2$ to $3\\ \\mathrm{nm}$ $(g\\gamma)$ . A similar technology can be used to coat $15\\mathrm{\\cdot}\\upmu\\mathrm{m}$ beads with avidin and biotin, where higher deflection angles have a high correlation to failure rates, with angles of $1^{\\circ}$ optimal for a failure rate of virtually zero (99). Instead of pillars, specific geometries can be used to catch emulsions for the fluidic assembly of lipid layers $(98)$ . For coating lipid particles with polymers, tangential flow filtration can be used as a type of expedited dialysis for removing excess polymer solution (100). To coat sufficiently large and/or dense particles, a setup based on fluidized beds can be used. This allows for assembly that is \\~eight times faster when compared with centrifugation-based assembly and produces films twice as thick (23). In this instance, the force of the washing or polymer solution lifting the particles is balanced against the force of gravity sedimenting the particles, resulting in a fluidized bed where washing and polymer solutions can be pushed past the particles. A similar setup can be used to coat larger ${\\scriptstyle\\left(>100-||{\\mathrm{{m}}}\\right)}$ particles in packed columns, although these beds do not need to be fluidized due to the large particle size, and gravity rather than a vacuum or pumpdriven fluidics can be used to pull the coating and washing solutions through the column $(I)$ .  \n\nNumerous applications have been introduced during the process of developing technologies for fluidic assembly. Many applications, such as improved capillary electrophoresis, are realized inside capillaries (81). Fluidic assembly can also be used to engineer complex flow patterns, such as having flow in opposite directions in the same capillary, simply by changing the outer coating of the capillary walls and generating flow with an electric current (82). Fluidic assembly is not limited to planar substrates: For example, multilayer coatings can be prepared on aerogels, resulting in improved compressive strength, wet-state super elasticity, fluorescence, and mechano responsive resistance, while also creating high charge-storage capacity (88). Damaged aortic porcine arteries can be repaired ex vivo with fluidic assembly, to protect the artery against unwanted blood coagulation, as well as to facilitate healing $(86)$ . Similarly, catheter tubing can be coated with antifungal multilayers to reduce fouling $(78)$ . Chromatography beads coated with multilayers of particles increase the surface area of the beads, thereby improving chromatography $(I)$ . Although fluidic assembly is typically performed on larger particles (tens or hundreds of micrometers in diameter), smaller particles (below ${\\sim}5~\\upmu\\mathrm{m}$ in diameter) can be coated and loaded with functional cargo for potential drug delivery applications by combining microfluidics with immobilization $(87)$ . Fragile particulate substrates like emulsions can also be coated with lipids, using fluidic assembly for the generation of synthetic cells (98). Neuronal cells can be patterned with fluidic assembly (83), and cell islets can be coated to improve robustness, allowing for in vivo transplantation (92, 95). Fluidic assembly functions as a valuable tool for coating sensitive particulate substrates, like mammalian cells, that may be damaged using other technologies, such as during handling in centrifugationbased assembly.  \n\nIn summary, fluidic assembly provides the means to assemble multilayers on surfaces not easily accessible to other methods (e.g., inside capillaries), provides new ways for region-specific patterning (e.g., by masking a surface with a fluidic channel), and increases the industrial capacity of multilayer assemblies (e.g., through parallelization of film assembly and decrease of reagent consumption). Although the specialized equipment and expertise required to set up (micro)fluidic systems can complicate the use of fluidic assembly, these advantages make it attractive for many applications.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 16,
+        "chunk": "# Challenges both big and small  \n\nOver the past two decades, LbL assembly has undergone an explosive growth in usable materials and substrates. When taken together with all of the different assembly technologies available, it becomes obvious why LbL assembly is prevalent across a broad spectrum of disciplines. Despite this extensive toolbox, relatively few multilayer films have had widespread impact outside of research environments. One focus for industrial applications is the identification of reliable, scalable, and resource-effective assembly processes, although this may require different approaches for macroscopic substrates and for microscopic particulate substrates.  \n\nFor macroscopic substrates, improved highthroughput assembly methods for conformal coatings will play a key role. Immersive and spray roll-to-roll assembly are industrially relevant but only readily applicable to flexible planar substrates; therefore, innovation is needed in systems that can be easily scaled for coating large or numerous 3D macroscopic substrates. Similarly, reducing material waste during the coating process remains important, especially for valuable coating materials like biomolecules and custom polymers. Another challenge for films intended for in vivo biomedical application, such as drug delivery and tissue engineering, is ensuring sterility of the product. This is typically achieved through sterilization (heat, ultraviolet light, chemical treatment, etc.) just before use, which can affect film properties and performance. Finally, increasing the reliability and reproducibility of the films— for example, by increasing automation and reducing manual intervention—is crucial for extending knowledge about film properties and assembly technologies and also for applying the multilayer films in real-life applications.  \n\nSimilar challenges exist for particulate substrates. One crucial difference is that several particulate assembly methods depend on centrifugation, which remains difficult to scale or combine with minimal-intervention high-throughput assembly. Furthermore, yield and size ranges need to be specified for the various technologies, as these details are often not determined. Detailed film properties (such as layer interpenetration, layer density, film stability or responsiveness, and permeability) that have primarily been studied on planar substrates also need to be investigated so that further comparisons between planar and particulate substrates can be drawn. Altogether, these challenges are not trivial and require focused efforts to overcome; they are also not unique to the field of LbL assembly. One way to address these challenges is to continue to be open and look for solutions in new and sometimes unexpected areas, both in neighboring and more distant fields; this has underpinned much of the technological innovation in LbL assembly.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 17,
+        "chunk": "# Opportunities: Thinking outside the box  \n\nLayer-by-layer assembly is a firmly established technology and shows great promise in multiple, diverse fields. Much of the development up until now has focused on using new molecular driving forces for film assembly, thus enabling the use of a suite of substrates and layer materials. However, this enormous potential still remains largely limited to small-scale research settings and requires technological and methodological innovation. Despite a surge of new technologies, many being recent developments, unmet challenges still remain, both for harnessing the specific strengths of different technologies for particular applications and also for developing new and improved technologies.  \n\nAlthough much work has been undertaken on establishing new assembly technologies, only a few studies have chosen a specific assembly technology for the material properties generated (e.g., stratification, density, roughness) rather than the processing properties used (e.g., ease-of-use, material and time savings, lowered involvement, larger batches). For example, for applications where electrical conductivity is important (such as fuel cells and batteries), the conductivity of an immersive-assembled film can be superior to that of spray-assembled films, which can be explained by differences in the interlayer organization of the constituent conductive layer materials (interpenetration versus stratification) (59). Conversely, for applications where optical clarity and/or wetting behavior is important, spinassembly can allow for an optically transparent film with well-controlled water-contact angles to be assembled due to the smooth, stratified layers formed, whereas an immersive-assembled film can be translucent and with a contact angle that drastically changes depending on the number of layers deposited due to the rough, interpenetrated layers formed (Fig. 3) (44). However, layer structure is only one of the critical film properties to be taken into account when designing films for specific applications. For example, the higher surface coverage and layer density associated with electromagnetic assembly can allow for electrodeposited enzyme films to have higher enzymatic activity than comparable immersive-assembled films ( $^{\\prime}\\mathit{68})$ . Of course, the layer structure and density are not relevant if the desired film components cannot be layered, which can be an issue, for example, when using materials with low charge density (e.g., reducedgraphene oxide) or with a low surface area of contact (e.g., branched nanowires). In such cases, technologies such as dewetting and vacuum assembly enable film formation using constituents that cannot be easily layered using other technologies (8, 89). These examples demonstrate how the judicious choice of assembly technology can enable the assembly of new and improved thin films. As our understanding of the different technologies and how they compare to each other increases, so does the opportunity to let this insight help guide the development of the next generation of LbL assembled thin films.  \n\nIt is noteworthy that the assembly technologies discussed herein were not originally developed for LbL assembly, and crossover technologies from other fields will continue to play an important part for new, and perhaps even revolutionary, developments. One interesting example involving industrial-scale layering was performed using a modified car wash for spray assembly on a full-sized car (101). Technologies long used in the pharmaceutical industry, such as methods used to treat, purify, and concentrate pharmaceuticals, may prove transformative for biomedical applications. Similarly, using everyday objects like spray-paint cans could revolutionize assembly methods by essentially combining dewetting and spray assembly for rapid region-specific assembly with little to no material waste and no washing steps. Other combinations between existing assembly technologies should also help to expedite and automate the assembly process. Along these lines, technologies for assembly on particulate substrates are expected to continue to integrate immobilization methods, as they allow collections of particles to be treated like planar substrates, making accessible many of the planar assembly technologies discussed herein. Another promising approach for particulate substrates could be to use a type of “sponge” to adsorb excess polymer from solution, thus removing the need to pellet the particles. In terms of future developments for applications, it will be important to understand the interaction between multilayer films and complex and natural environments, such as those found in the human body (40), outdoors, or in seawater. An important aspect of this could be the use of functional substrates capable of compounding the benefits of different multilayers in a synergistic fashion. Overall, the future of LbL assembly is bright, and as the black box of assembly technologies is slowly illuminated, great potential for innovation and application will be found.",
+        "category": " Results and discussion"
+    },
+    {
+        "id": 18,
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Sochol et al., “Continuous flow layer-by-layer microbead functionalization via a micropost array railing system,” in Proceedings of the 16th International Conference on Solid-State Sensors, Actuators and Microsystems (Transducers 2011), Beijing, 5 to 9 June 2011 (Institute of Electrical and Electronics Engineers, Piscataway, NJ, 2011), pp. 1761–1764.   \n100. S. Hirsjärvi, Y. Qiao, A. Royere, J. Bibette, J.-P. Benoit, Layer-by-layer surface modification of lipid nanocapsules.  \n\nEur. J. Pharm. Biopharm. 76, 200–207 (2010). doi: 10.1016/ j.ejpb.2010.07.010; pmid: 20656028 101. K. Ariga et al., Layer-by-layer nanorchitectectonics: Invention, innovation, and evolution. Chem. Lett. 43, 36–68 (2014). doi: 10.1246/cl.130987",
+        "category": " References"
+    },
+    {
+        "id": 19,
+        "chunk": "# ACKNOWLEDGMENTS  \n\nThis work was supported by the ARC under the Australian Laureate Fellowship (FL120100030 to F.C.) and the Australian government through an Australian Postgraduate Award (to M.B.). This work was also supported by the ARC Centre of Excellence in Convergent Bio-Nano Science and Technology (project number CE140100036).  \n\n10.1126/science.aaa2491",
+        "category": " References"
+    },
+    {
+        "id": 20,
+        "chunk": "# Science",
+        "category": " Introduction"
+    },
+    {
+        "id": 21,
+        "chunk": "# Technology-driven layer-by-layer assembly of nanofilms  \n\nJoseph J. Richardson, Mattias Björnmalm and Frank Caruso  \n\nScience 348 (6233), aaa2491. DOI: 10.1126/science.aaa2491",
+        "category": " References"
+    },
+    {
+        "id": 22,
+        "chunk": "# Thin-film fabrication  \n\nThe deposition of thin films from multiple materials is essential to a range of materials fabrication processes. Layer-by-layer processes involve the sequential deposition of two or more materials that physically bond together. Richardson et al. review some of the techniques and materials that are used to make thin films, including sequential dip coating, spraying, and electrochemical deposition. Despite the versatility of the methods and the range of materials that can be deposited, the techniques remain mostly confined to the lab because of challenges in industrial scaling. But because there is tremendous scope for fine-tuning the structure and properties of the multilayers, there is interest in broadening the use of these techniques.  \n\nScience, this issue 10.1126/science.aaa2491  \n\nREFERENCES  \n\nPERMISSIONS  \n\nUse of this article is subject to the Terms of Service",
+        "category": " Introduction"
+    }
+]
\ No newline at end of file
diff --git a/task2/task2-paper-info/1-s2.0-S0040609020301334-main.json b/task2/task2-paper-info/1-s2.0-S0040609020301334-main.json
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--- /dev/null
+++ b/task2/task2-paper-info/1-s2.0-S0040609020301334-main.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The membranes were synthesized using Plasma Enhanced Chemical Vapor Deposition (PECVD) at an optimal plasma input power of 100 W. The synthesis involved investigating the nature of the plasma discharge, either continuous or pulsed. Characterization of the membranes included Scanning Electron Microscopy (SEM) for morphology and thickness, X-ray photoelectron spectroscopy (XPS) for chemical composition, and contact angle method for surface hydrophily/hydrophoby. For evaluating the water sorption behavior, ellipsometry and Cahn microbalance were used, while water permeability was assessed through diffusion measurements using a permeation cell.1. Clean substrates (boron-doped p-type silicon wafer and Nafion® 212) by applying a continuous plasma pre-treatment for 15 minutes at 100 W to improve adherence. 2. Set up the PECVD device with a capacitively coupled plasma reactor operating at 13.56 MHz and a discharge power fixed at 100 W. 3. Use dimethyl allylphosphonate as the precursor and argon as the gas carrier. 4. Perform the membrane deposition either in continuous or pulsed configuration, with pulsed configuration alternating between T_on (5 ms on) and T_off (5 ms off) at a frequency of 100 Hz, resulting in a duty cycle of 50%.To synthesize hydrophilic polymers with functional groups, the following experimental procedure is employed: Begin by preparing a dry sample of the polymer (50 mg for PECVD membranes or 5 mg for Nafion® 212), and place it in the measuring nacelle within a thermoregulated chamber. Prior to water sorption measurements, perform a conditioning step by passing dry nitrogen (Technical Nitrogen, Air Product) at a flow rate of 200 cm³.min⁻¹ to eliminate any moisture. Record the mass of the sample as the dry mass M₀. Subsequently, program a sequence of water vapor activity from 0.05 to 0.95, allowing the sample to reach sorption equilibrium at each level. Record the mass variation as a function of time to determine the intrinsic diffusion coefficient and sorption equilibrium using a Cahn D200 microbalance with electromagnetic compensation. The interaction between the penetrant and substrate can be analyzed through sorption isotherms using models such as DualMode or the Park model to characterize the sorption behavior."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/1-s2.0-S030094402400482X-main.json b/task2/task2-paper-info/1-s2.0-S030094402400482X-main.json
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--- /dev/null
+++ b/task2/task2-paper-info/1-s2.0-S030094402400482X-main.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The hydrophilic polymer network was synthesized by copolymerization of triethoxyvinylsilane (A151) and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) followed by complexation with poly(vinyl alcohol) (PVA).Poly (vinyl alcohol) (PVA-1799) and triethoxyvinylsilane (A151) are mixed with 3-methacryloxypropyltrimethoxysilane (KH570) and 2-acrylamide-2-methylpropane sulfonic acid (AMPS) in a suitable solvent. An initiator, ammonium persulfate (APS), is added to the mixture to initiate the polymerization process. The reaction is carried out under controlled conditions to ensure the formation of hydrophilic polymers with functional groups.Antifogging coating was prepared by thermal polymerization. PVA (10 wt%) aqueous solution was prepared by dissolving 1.0 g PVA in 10 g distilled water and stirred for 2 h at 95°C. 5 wt% AMPS was added to the above PVA solution at 60 °C, and silane coupling agent (A151, 2 wt%) and the initiator APS were added sequentially after AMPS dissolved. The reaction was continued for 2 h at 60 °C. The polymer solution obtained was spread uniformly on the glass surface using drip coating to obtain a coating film. The layer was further dried at 50°C for 2 h to obtain a dried polymer layer (abbr. as PVA/P(A151_n·coAMPS)), where n was the amount of A151. The preparation of PVA/(KH570_n-co-AMPS) layer was the same as that of PVA/P(A151_n-co-AMPS), just by substituting A151 with KH570."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/1-s2.0-S0927775719302274-main.json b/task2/task2-paper-info/1-s2.0-S0927775719302274-main.json
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--- /dev/null
+++ b/task2/task2-paper-info/1-s2.0-S0927775719302274-main.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of hydrophilic polymers with functional groups was achieved using gas-phase processing through Chemical Vapor Deposition (CVD). Specifically, surfaces rich in residual silanol groups were treated by immersion in HMDS (hexamethyldisilazane) in hexane, with concentrations varying from 0% to 100% HMDS for immersion times ranging from 0 to 1400 minutes at room temperature. The goal was to reduce the number of reactive silanol groups on the glass surface to enhance surface wettability. The modifications resulted in an increase in the static contact angle from 25° to 105° after treatment with 100% HMDS for more than 60 minutes.Expose rigid flat samples of glass microscope slides, silicon pieces, SU-8 2005 coatings, and PDMS membranes to HMDS vapor and FDTS vapor at room temperature. After chemical vapor deposition (CVD) exposure, measure the contact angle of liquid drops of deionised water or water-based phosphate-buffered saline solution on the solid surface.Samples of glass and silicon have been washed with Alconox® anionic detergent for 3 hours, rinsed with isopropanol (>99.8%, Labchem) followed by DI water, and blow dried. PDMS membranes have been prepared by manually mixing 3 dimethyl siloxane and 184 silicone elastomer (cross linking agent) in a 10:1 ratio, left for 1 hour on the vacuum desiccator (1-800-4Bel-Art, Bel-Art Products) to remove any bubbles present in the mixture, and cured at 70°C for 1 hour (Memmert GmbH+Co. KG 100–800 oven). SU-8 20055µm thickness homogeneous coating has been defined by a 2-step spin coating on previously dehydrated silicon pieces (step 1: 500 rpm for 10 s at 100 rpm.s^{-1}, step 2: 3056 rpm for 30 s at 300 rpm.s^{-1}; Modular spin coater ws-650-23NPP, Laurell Technologies Inc.). After a soft baking step on a hot plate (95°C for 2 min, SD160 hotplate, Stuart), the SU-8 2005 has been exposed to UV light (17 s, 5.95 W.cm^{-2}, UH-H 254, UV Light Technology LTD; black filter: 320-405 nm), followed by another soft bake step at 95°C for 3 min and finally left to cool to room temperature. All steps have been prepared inside a laminar flow hood (Faster-BSC-EN) to avoid surface contamination.Expose the surface to a volume of 6μL HMDS or FDTS vapor on a vacuum desiccator for 2, 10, 20, 30 or 50 minutes at ambient temperature (22°C) and pressure -0.78 ± 0.09 atm.Contact angle analysis was performed by dispensing 6μL liquid drops of DI water or PBS solution on the surface using a controllable syringe pump (NE 4000, New Era) and a 1mL syringe (CODAN) with polyethylene tubing BTPE-90 863.3μm inner diameter. CA measurements were taken in cleaned, non-exposed control sample surfaces for an exposure time of 0min. Images of each droplet on the surface were captured under ambient conditions within 5min after CVD exposure. The effectiveness and stability of SWM over time were evaluated through CA measurements over 65h after CVD. Droplet images were recorded with a CMOS camera (5.1μm pixel size, 12 Mpixel), coupled with a macro lens with 0.33 maximum magnification. Each combination of experimental conditions (substrate – liquid – CVD fluid – exposure time) was repeated three times. CA evaluation was conducted using Image J software with LBADSA plugin."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/1-s2.0-S0927775719311537-main.json b/task2/task2-paper-info/1-s2.0-S0927775719311537-main.json
new file mode 100644
index 0000000..fef2088
--- /dev/null
+++ b/task2/task2-paper-info/1-s2.0-S0927775719311537-main.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "A one-step thermally initiated crosslinking reaction is employed for the synthesis of antifogging/frost-resisting cross-linked acrylic coatings. The monomers used are 2-acrylamido-2-methyl propane sulfonic acid (AMPS) for hydrophilicity and methyl methacrylate (MMA) for hydrophobicity. Cross-linkers ethylene glycol dimethacrylate (EGDMA) and 3-Trimethoxysilylpropyl methacrylate (TMSMA) are added to adjust the cross-linking density and coating adhesion.Dissolve 2-Acrylamido-2-methyl propane sulfonic acid (AMPS) in N,N-dimethylformamide (DMF) to form a reaction mixture. Add ethylene glycol dimethacrylate (EGDMA) as a crosslinker, followed by the thermal initiator 2,2'-azobis (2-methylpropionitrile) (AIBN). Incorporate the silane coupling agent 3-trimethoxysilylpropyl methacrylate (TMSMA) into the mixture. Stir the reaction mixture under an inert atmosphere at a specified temperature until polymerization occurs, forming the hydrophilic polymer with functional groups.Glass slides (2.5x2.5cm2) were sonicated in acetone for 30 min, dried by argon flow, and exposed to an air plasma cleaner for 180 s. A series of mixtures (1.00g) with varying AMPS/MMA molar ratios (20/80, 40/60, 50/50, 60/40, 80/20), EGDMA contents (0.1-2 wt% relative to monomers), TMSMA (0.1 wt% relative to monomers), AIBN (1 wt% relative to monomers), and NH3·H2O (1 wt% relative to TMSMA) were dissolved in 10 ml DMF, purged by argon, mixed, and spin-coated on the plasma-treated glass slides at different rates (500, 1000, 1500, 2000 rpm) for 4s. The spun-coated films were heated in an oven at 80°C for 12h to complete copolymerization and dried in a vacuum oven overnight (80°C) to remove unreacted impurities. Resultant coatings were labeled according to AMPS/MMA ratios and EGDMA contents.Fogging/frosting tests were conducted as follows: For the fogging test, samples were held 5 cm above a water bath at 80°C for different durations (15, 30, 45, and 60 seconds), using a control glass as a reference. The frosting test involved placing samples in a freezer at -20°C for 30 minutes, after which photographs were taken following exposure to ambient conditions (20°C, 50% relative humidity) for 5 seconds. Light transmission in the range of 400-700 nm was measured using a UV–vis spectrophotometer during the fogging/frosting test.Prepare antifogging/frost-resisting coatings by combining hydrophilic AMPS and hydrophobic MMA with EGDMA and TMSMA as cross-linkers via thermal curing. Adjust the contents of AMPS and MMA to tune the water-absorbing ability, while varying EGDMA and TMSMA amounts influences the balance between water-swellability and cross-linking density. Treat glass slides with air plasma to generate active groups, enhancing interfacial interaction with TMSMA and facilitating uniform coating formation. Control the coating thickness by adjusting spin-coating speed. Measure the coating thickness and surface roughness using Atomic Force Microscope (AFM). Vary the AMPS/MMA molar ratio (20/80, 40/60, 50/50, 60/40, and 80/20) to optimize antifogging/frost-resisting performance. Prepare coatings with EGDMA contents ranging from 0.1 to 2 wt% to study the impact of cross-linking density on performance."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/1-s2.0-S0960852424013415-main.json b/task2/task2-paper-info/1-s2.0-S0960852424013415-main.json
new file mode 100644
index 0000000..8f0919e
--- /dev/null
+++ b/task2/task2-paper-info/1-s2.0-S0960852424013415-main.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The palm oil waste is grounded and screened to obtain uniform particle size, afterward dried in a Force Air Convention Oven (Venticell Oven) at 105°C for 24 hours to ensure moisture escaped from the palm oil waste.1. Cut a silicon wafer disc to 1 cm x 1 cm using a diamond cutter. 2. Clean each silicon wafer and dry in a Forced Air Convention Oven for 1 hour. 3. Prepare a ZnCl2 solution with a molarity of approximately 0.4 M. 4. Airbrush the 0.4 M ZnCl2 solution onto the cleaned silicon wafer from a distance of 15 cm. 5. Dry the silicon wafer coated with ZnCl2 in a Drying Oven at 105°C for 1 hour to produce the ZnCl2 - Silicon Wafer, ready for use as a graphene growth template.A tubular quartz tube with a length of 124 cm, an internal diameter of 6.9 cm, and an outer diameter of 7.5 cm is placed in a Heating Furnace. The biochar produced and ZnSw is placed in an alumina boat with a length of 10.0 cm, a height of 1.8 cm, and a width of 4.0 cm, along with two different alumina boats (i) with dimensions 5.0 cm x 2.0 cm x 2.0 cm and (ii) with dimensions 5.0 cm x 0.5 cm x 1.0 cm positioned to cover the biochar and ZnSw. The furnace temperature is raised to 900°C at a heating rate of 10°C/min, maintaining a residence time of 35 min. Nitrogen gas is used as an inert gas to purge air from the pyrolizer at 500 mL/min until the pyrolizer cools down. In a continuation of the experiment, biochar and ZnSw are placed in another alumina boat of dimensions 9.0 cm x 1.5 cm x 1.0 cm, with a similar-sized alumina boat placed on top. The same heating parameters are applied in this second configuration."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/1-s2.0-S1385894722033654-main.json b/task2/task2-paper-info/1-s2.0-S1385894722033654-main.json
new file mode 100644
index 0000000..6282cf3
--- /dev/null
+++ b/task2/task2-paper-info/1-s2.0-S1385894722033654-main.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "To synthesize the hydrophilic PSTG coating, mix polyvinyl alcohol (PVA), sodium alginate (SA), titanium dioxide (TiO2), and glycerin. The coating can be applied using the dipping method, knife coating, or spin coating. A specific example involves using 5 cycles of acid and alkali treatment followed by sodium percarbonate deposition for 150 minutes, with hot and cold treatments for 120 minutes each. Ensure to maintain the structural integrity of the coating throughout the process.PVA and TiO2 (anatase) were used as the primary materials for synthesis. TiO2 particles were sourced with various sizes (20 nm, 40 nm, 60 nm, 100 nm) and were of 99.8% purity. Other reagents included SA, n-hexane, hexadecane, absolute ethanol, isopropanol, and glycerin. All materials were utilized without purification.The synthesis of hydrophilic polymers involved selecting the mass concentrations of PVA (2.78%), SA (0.83%), and TiO2 (0.025%) based on the results of an orthogonal experimental design L25(5^3). The criteria for evaluation included antifogging grade and light transmission, where light transmittance was measured against a blank film in the range of 400-720 nm, with a scoring system based on deviations from the blank film. The antifogging level was evaluated on a scale with adjustments made based on the improvement or decline in levels.Dissolve 2.78 wt% PVA and 0.83 wt% SA in 35 mL distilled water/glycerol solution (volume ratio of 6:1) at 95 °C for 2 hours to obtain a homogeneous and transparent solution. Suspend 0.025 wt% TiO2 particles in the solution. Treat PE membranes with oxygen plasma for 20 seconds to enhance superhydrophilic ability. Scrape an appropriate amount of the obtained solution onto the PE substrate. Dry the coated PE at 60 °C for 2 hours."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/1-s2.0-S2468023024008459-main.json b/task2/task2-paper-info/1-s2.0-S2468023024008459-main.json
new file mode 100644
index 0000000..70000fb
--- /dev/null
+++ b/task2/task2-paper-info/1-s2.0-S2468023024008459-main.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Amphiphilic polymeric thin films were produced by copolymerization of 2,2,2,3,4,4,4,4 hexafluorobutyl acrylate (HFBA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) monomers using the initiated chemical vapor deposition (iCVD) technique. Different chemical compositions of the copolymer films were achieved by varying the flow rate ratios of the monomers.The monomers HFBA (95%), DMAEMA (98%) and the initiator di‑tert butyl peroxide (TBPO, 98%) were acquired from Sigma–Aldrich and utilized as received without any additional modifications or post-purification procedures.The iCVD process for amphiphilic film coatings was conducted within a stainless-steel chamber. The substrates were kept at a constant temperature by placing them on the reactor floor with a heat exchanger connected to a recirculating chiller. The energy for polymerization was provided by a tungsten filament array placed 22 mm above the reactor floor. The filament's temperature was monitored using a K type thermocouple and manually adjusted by a variac. Precursors DMAEMA, HFBA, and TBPO were placed in stainless-steel jars and their vapors were fed into the reactor using needle valves. The temperatures were kept constant at 55°C for DMAEMA, 25°C for HFBA, and 25°C for TBPO. A vacuum environment was created using a rotary vacuum pump and pressure was monitored with a capacitance-type manometer. A PID-controlled butterfly valve was used to maintain desired pressure. The flow rates of HFBA/DMAEMA were adjusted to fabricate amphiphilic polymers with different chemical compositions, using three different DMAEMA flow rates while keeping TBPO and HFBA flow rates constant at 1.0 sccm. The amphiphilic polymers were designated as AP1, AP2, and AP3 with flow rate ratios of HFBA/DMAEMA being 1/0.3, 1/0.7, and 1/1, respectively.The synthesis of hydrophilic polymers was conducted using the initiated chemical vapor deposition (iCVD) method. The specific experimental conditions for the deposition of amphiphilic thin films with the functional groups HFBA and DMAEMA are outlined as follows: For AP1, the flow rates were set to 1.0 sccm for HFBA, 0.3 sccm for DMAEMA, and 1.0 sccm for TBPO, with a reactor pressure of 600 mTorr, filament temperature at 245 °C, and substrate temperature at 25 °C. For AP2, the flow rates were 1.0 sccm for HFBA, 0.7 sccm for DMAEMA, and 1.0 sccm for TBPO, maintaining the same reactor pressure, filament temperature, and substrate temperature as AP1. For AP3, the flow rates were 1.0 sccm for HFBA, 1.0 sccm for DMAEMA, and 1.0 sccm for TBPO, with identical reactor, filament, and substrate conditions as the previous experiments."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/10.1002@adfm.201903419.json b/task2/task2-paper-info/10.1002@adfm.201903419.json
new file mode 100644
index 0000000..1d024d8
--- /dev/null
+++ b/task2/task2-paper-info/10.1002@adfm.201903419.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of hydrophilic polymers with functional groups involves the use of pulse laser deposition (PLD) where a distance of 4 cm is set between the bulk BP target and the substrate. The chamber is evacuated to around 1.5 x 10^-7 Torr before deposition. The substrate is maintained at a temperature of 150 °C. The BP target is evaporated using a KrF pulse laser at a wavelength of 248 nm at a cycle of 5 Hz. During the deposition, both the BP and the substrate are rotated to ensure uniform film growth. After deposition, the film is cooled to room temperature in a high vacuum chamber.This method is one of the bottom-up approaches for preparing 2D materials, and it comprises solvothermal, hydrothermal, template synthesis, and self-assembly of particles. Hydrothermal synthesis was carried out for functionalized phosphate carbon, which consists of composite carbon with porous support material via a model of hydrothermal approach, preceded by heat treatment."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/10.1002@advs.202000439.json b/task2/task2-paper-info/10.1002@advs.202000439.json
new file mode 100644
index 0000000..3f557eb
--- /dev/null
+++ b/task2/task2-paper-info/10.1002@advs.202000439.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The BP sheets are synthesized by a modified liquid exfoliation technique, where 20 ppm BP sheets are dispersed in aqueous solution and exposed to an NIR laser (808 nm, 1.0 W cm^-2) for 10 minutes.The micro-sized BP flakes were prepared by mechanical exfoliation from the bulk crystal using scotch tape and transferred to a Si/SiO2 wafer. The BP sheets were prepared by a modified liquid exfoliation technique. Briefly, the BP crystals were dispersed in NMP with an initial concentration of 1 mg/mL and ground to fine powders. The dispersion was sonicated in an ice bath for 70 hours using a power of 300 W and centrifuged at 4000 rpm for 10 minutes. The supernatant containing the BP sheets was decanted gently and centrifuged for another 10 minutes at 7000 rpm. The precipitate was collected and resuspended for subsequent experiments. A certain amount of agarose powders (4 wt%) was dispersed in deionized water under mechanical stirring at 90°C for 30 minutes and stored in a 4°C refrigerator for 30 minutes to obtain the agarose hydrogels. BP Hydrogel was prepared by mixing the agarose solution with BP sheets (20 ppm). B P&C A P Hydrogel was obtained by dispersing 2 mg CAP nanoparticles (approximately 200 nm in diameter) into the BP Hydrogel solution and prepared by the same method as described above."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/10.1007@s11998-020-00338-z.json b/task2/task2-paper-info/10.1007@s11998-020-00338-z.json
new file mode 100644
index 0000000..5610455
--- /dev/null
+++ b/task2/task2-paper-info/10.1007@s11998-020-00338-z.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The hydrophilic nano-SiO2/PVA coating was fabricated by the solution blending method and deposited on PE film using a dip coating technique. The addition of nano-SiO2 into PVA was aimed at improving the network structure, mechanical properties, thermal stability, and water resistance of the film.1. Prepare a PVA solution at 5 wt% in water. 2. Mix the PVA solution with Ludox (N2010, SS3010) via mechanical stirring for 1 hour. 3. Dilute the resulting solution with deionized water. 4. Add fluorocarbon surfactant at a concentration of one thousandth to the diluted solution to reduce surface tension. 5. Immerse the PE film in the hybrid solution for 5 seconds. 6. Perform thermal treatment of the PE film at 80°C for 5 minutes to evaporate the solvent."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/10.1016@j.porgcoat.2019.01.061.json b/task2/task2-paper-info/10.1016@j.porgcoat.2019.01.061.json
new file mode 100644
index 0000000..bbc1f14
--- /dev/null
+++ b/task2/task2-paper-info/10.1016@j.porgcoat.2019.01.061.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "PUA is synthesized from polyurethane by introducing double bonds of acrylates into the molecular chain terminal. Oligomers are then utilized to initiate a double-crosslinking reaction using photoinitiators.To synthesize hydrophilic polymers with functional groups, select diisocyanates (such as TDI, IPDI, MDI, HMDI, or HDI) as urethane segments and use chain extenders like polyethylene glycol (PEG) or polytetrahydrofuran (PTMEG). Employ hydroxyethyl acrylate (HEA) as the end-capper to introduce unsaturated bonds. For enhanced functionality and mechanical properties, consider incorporating trimethylolpropane diallyl ether (TMPDE) or pentaerythritol triacrylate (PETA) as end-capping reagents. For a greener approach, utilize non-isocyanate polyurethane (NIPU) synthesis through transurethanization polycondensation involving cyclic carbonate and diamine, or explore renewable resources such as vegetable oils as raw materials."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/1980-kao soap-anti-fog.json b/task2/task2-paper-info/1980-kao soap-anti-fog.json
new file mode 100644
index 0000000..61c75f4
--- /dev/null
+++ b/task2/task2-paper-info/1980-kao soap-anti-fog.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "The sulfonic acid type amphoteric surface active agent is prepared by reacting an alpha-hydroxyalkyldialkylamine derived from a tertiary alkylamine or alpha, beta-alkylene epoxide with an alkane sultone or by reacting the alpha-hydroxyalkyldialkylamine with benzyl chloride or epichlorohydrin and sulfating the resulting product. This agent is incorporated in the anti-fogging agent in an amount of 0.05 to 30% by weight. Additionally, an inorganic salt or acetate is used as a second component in the amount of 0.01 to 20% by weight, selected from inorganic salts and acetates such as NaSCN, NaNO3, KCl, LiBr, NH4Cl, KI, MgCl2, CaCl2, and CH3COONa.To synthesize hydrophilic polymers with functional groups, incorporate a nonionic surface active agent represented by the formula R O(C H2C H2O)n, where R is an alkyl group (10 to 16 carbon atoms), an alkenyl group (14 to 18 carbon atoms), or a phenyl group. The amount of this agent should be 0.01 to 30% by weight, preferably 0.1 to 10% by weight. Additionally, incorporate a water-soluble polymer composed of a maleic anhydride-vinyl monomer copolymer, such as a maleic anhydride-acetalized vinyl alcohol copolymer, in an amount of 0.005 to 10% by weight, preferably 0.01 to 5% by weight. The average degree of polymerization of the water-soluble polymer should be in the range of 500 to 1500. To enhance low temperature stability, include up to 30% by weight of an alcohol with two or three carbon atoms (e.g., ethanol, propanol).A durable anti-fogging composition consists essentially of 0.05 to 30% by weight of at least one sulfonic acid type amphoteric surface active agent having the formula (I) wherein R1, R2 and R3 each is alkyl, hydroxyalkyl or benzyl, the sum of the number of carbon atoms of R1, R2 and R3 is in the range of from 16 to 38 and one of R1, R2 and R3 is alkyl or hydroxyalkyl having at least 14 carbon atoms, and R4 is alkylene or hydroxyalkylene having 2 to 4 carbon atoms; 0.01 to 20% by weight of at least one member selected from the group consisting of inorganic salts and acetates having the formulae MeSCN, MeNO3, MeX and MeOOCCH3 in which Me is a cation selected from the group consisting of Na, K, Li, NH4, Ca and Mg and X is halogen; up to 30% by weight of alkanol having 2 or 3 carbon atoms; and the balance is water."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/2001-US-anti-fog.json b/task2/task2-paper-info/2001-US-anti-fog.json
new file mode 100644
index 0000000..61ee1da
--- /dev/null
+++ b/task2/task2-paper-info/2001-US-anti-fog.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of hydrophilic polymers involves a polycondensation reaction of a hydrolysate of an inorganic alkoxide in the presence of polyacrylic and polyvinyl alcohol. Additional components may include hydrosilicofluoric acid and a silane coupling agent having an epoxy group, or a specific benzophenone compound.Synthesize hydrophilic polymers by using alkoxides as precursors. Select an inorganic alkoxide compound from the formula M(OR)n(X)α-n, where M is an element such as Si, Al, Ti, or Zr, and R and X are appropriate alkyl groups or functional groups. For example, use Si(OR1)4 with R1 being a lower alkyl group (1 to 4 carbon atoms). Prepare mixtures using aluminum, titanium, or zirconium alkoxides in varying proportions to enhance properties such as light transmission, heat resistance, and toughness. Specifically, combine aluminum alkoxides in a ratio of 1 to 10 parts by weight per 100 parts by weight of alkoxysilane, titanium alkoxides in a ratio of 0.1 to 3 parts by weight, and zirconium alkoxides in a ratio of 0.5 to 5 parts by weight per 100 parts by weight of alkoxysilane. The use of functional groups in the X position, such as vinyl, carboxyl, carbonyl, amino, or epoxy, can enhance anti-fogging properties. Example compounds include vinyltrichlorosilane and γ-methacryloxypropyltrimethoxysilane. Employ polyacrylic and polyvinyl alcohol with specified saponification degrees to further modify the properties of the polymers.To synthesize hydrophilic polymers with functional groups, prepare a reaction solution containing at least one inorganic alkoxide, a hydrolysate of the inorganic alkoxide, and a low molecular weight polycondensate of the hydrolysate, along with a polyacrylic, polyvinyl alcohol, and a catalyst for accelerating the polycondensation reaction. The inorganic alkoxide can undergo hydrolysis and polycondensation either before or after the preparation of the reaction solution. Use an acid catalyst, preferably a mineral acid (e.g., hydrochloric acid, sulfuric acid, nitric acid) or organic acids, in an amount of 0.01 to 0.5 parts by weight per 100 parts by weight of the alkoxide. Add hydrosilicofluoric acid (0.005 to 0.5 parts by weight) and a silane coupling agent (0.05 to 10 parts by weight) such as γ-glycidoxypropyltrimethoxysilane to the mixture. Optionally, incorporate a benzophenone compound known for weather resistance properties. Mix the components to form a transparent coating fluid, apply it to a substrate, and dry under heating at 80°C or higher, preferably between 120°C to 200°C, to form an anti-fogging coating film with hydrophilic properties.A coating fluid was prepared by adding a 10% aqueous solution of polyvinyl alcohol (average polymerization degree: 2,000, saponification degree: about 82 mol%) to a 2.5% water-methanol solution of a 20 mol% saponified product of polymethyl acrylate. The saponified product was obtained by adding methanol to a 25% aqueous solution of polyacrylic acid (average molecular weight: 150,000), stirring the mixture at ordinary temperature (25°C) for 30 minutes to produce polymethyl acrylate, adding sodium hydroxide to achieve a saponification degree of 20%, and stirring for an additional 30 minutes to saponify the methyl ester. The resulting mixture was stirred at 25°C for 10 minutes, and then a solution of γ-glycidoxypropyl-trimethoxysilane, a solution of a hydrolysate of aluminum isopropoxide (5% by weight in terms of Al2O3), and a 0.47% methanol solution of hydrosilicofluoric acid were added. The mixture was stirred at 25°C for 15 minutes. A glass sheet was dip coated with the fluid at a lifting rate of 50 mm/min using a dip coating device, heated and dried at 150°C for 10 minutes to obtain a colorless, transparent coating film with a thickness of 3.0 μm. The coated glass sheet was placed in a refrigerator (about 0°C) for 5 minutes and then left at 25°C and 81% RH, with no fogging observed on the coated surface.A coating fluid was prepared by adding methanol and a 10% aqueous solution of polyvinyl alcohol (average polymerization degree: 2,000; saponification degree: about 82 mol%) to a 25% aqueous solution of polyacrylic acid (average molecular weight: 150,000), stirring the resulting mixture at ordinary temperature (25°C) for 10 minutes. Then, a solution of γ-glycidoxypropyltrimethoxysilane, a solution of a hydrolysate of aluminum isopropoxide (obtained by hydrolyzing aluminum isopropoxide using an acid catalyst in ethanol; 5% by weight in terms of Al2O3), and a 0.47% methanol solution of hydrosilicofluoric acid were added. The resulting mixture was stirred at ordinary temperature (25°C) for 15 minutes.Prepare a $10\\\\%$ methanol solution of $^{2,2^{\\prime},4,4^{\\prime}}$ -tetrahydroxybenzophenone and a $10\\\\%$ methanol solution of bis-[N-formyl-(2,2,6,6-tetramethyl-4- piperidyl)imino]hexamethylene. Add both solutions to a coating fluid prepared in accordance with the formulation shown in Table 3. Stir the mixture at ordinary temperature $(25^{\\\\circ}\\\\mathrm{C})$ for 15 minutes to obtain a yellow coating fluid. Apply the coating fluid to a glass sheet and dry as specified. The thickness of the coating film should be ${3.0\\\\ \\\\mu\\\\mathrm{m}}$. Expose the coated glass sheet to ultraviolet light $(250\\\\ \\\\mathrm{nm}, 4\\\\ \\\\mathrm{kW})$ for 20 hours from a distance of about 24 cm. Test the coated surface for anti-fogging properties after exposure.A composition is obtained by a polycondensation reaction of a hydrolysate of an inorganic alkoxide in the presence of a polyacrylic, polyvinyl alcohol, and either hydrosilicofluoric acid or a benzophenone compound. The resulting composition should include functional groups selected from hydrogen, hydroxyl, sulfonic acid, carboxyl, acyl, ester, ether, hydrocarbon groups, alkoxyl groups having 1 to 6 carbon atoms, amino, hydroxyalkyl, and hydroxyalkoxyl groups, ensuring at least one group is a hydroxyl or sulfonic acid group."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/2002-╚¤┴т-anti-fog.json b/task2/task2-paper-info/2002-╚¤┴т-anti-fog.json
new file mode 100644
index 0000000..4dddb51
--- /dev/null
+++ b/task2/task2-paper-info/2002-╚¤┴т-anti-fog.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of hydrophilic polymers with functional groups involves using a water soluble copolyester, preferably made up of about 90 mol percent isophthalic acid, about 10 mol percent of the sodium salt of 5-sulfoisophthalic acid, and about 100 mol percent ethylene glycol. The preferred percentage ranges in the context of this synthesis are 50 to about 98 mol percent isophthalic acid, 0 to about 50 mol percent aliphatic dicarboxylic acid, and 2 to about 20 mol percent sulfomonomer. The copolyester may be created as the condensation product of a maderfogi sulfonate group attached to a dicarboxylic aromatic nucleus and an alkylene glycol with about 2 to about 11 carbon atoms. A preferred method of incorporating the binder into the solution is by maintaining it at about 1 to about 30 percent by weight in the coating solution. The binder components are mixed with surfactants including anionic surfactants such as sodium dodecyl benzenesulfonate, as well as fluorosurfactants containing fluoroaliphatic oxyethylenes. The resulting mixture should be formulated as a dispersion in water or a water-containing solvent, reaching a solids level up to about 50 weight percent and enabling the final dry coating thickness to yield between about 0.02 to 0.1 microns. Coating is preferably applied to a polymer film substrate after corona treatment and prior to stretch orientation in a process that may be in-line or off-line, ensuring adherence of the functionalized copolyester binder.The synthesis of hydrophilic polymers involves incorporating about 20 mol percent of at least one sulfomonomer that contains a sulfonate group attached to a dicarboxylic nucleus and about 100 mol percent of at least one copolymerizable glycol with 2 to 11 carbon atoms. The resulting polymer can comprise polyester with various binders present in specific weight percentages for applications like anti-fog coatings. The process may include coating a surface with an anti-fog coating containing a water-soluble hydrophilic copolyester binder and a surfactant, while ensuring the surfactant's weight percent of fluorosurfactant is less than 0.5. The final coating must have a wetting tension greater than 60 dynes/cm and be fog-free after exposure to a warm air humidifier."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/2003-JP-anti-fog.json b/task2/task2-paper-info/2003-JP-anti-fog.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/2003-JP-anti-fog.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/2011-DE-anti-fog.json b/task2/task2-paper-info/2011-DE-anti-fog.json
new file mode 100644
index 0000000..d9c6e79
--- /dev/null
+++ b/task2/task2-paper-info/2011-DE-anti-fog.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "S1) provision of a reaction mixture comprising as reaction components S1a) a polyglycerol comprising at least two glycerol units; S1b) an oil based on a natural oil; S2) reaction of the reaction mixture by a transesterification in the presence of a basic catalyst to give the ester product.255.6g of rape oil, 74.4g of Polyglycerol-3 (Solvay Chemicals) and 0.03g of LiOH*H2O were initially introduced into a glass flask and heated to 235°C, while stirring. After 1 hour, a vacuum of 300 mbar was applied, and after a reaction time of 2 hours, the mixture was cooled.The components were mixed together and the mixture was rolled on a laboratory roll mill at 185°C for 5 min. The rolled sheets were investigated by the 'hot fogging test' at 60°C."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/2020-US-anti-fog.json b/task2/task2-paper-info/2020-US-anti-fog.json
new file mode 100644
index 0000000..efd72be
--- /dev/null
+++ b/task2/task2-paper-info/2020-US-anti-fog.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "1. Prepare an aqueous coating composition containing water-soluble organic polymers, such as Bermocoll E230FQ (ethyl hydroxyethyl cellulose). The cellulose should be present in an amount of between 0.1 and 0.5 wt%, preferably about 0.2 wt%. 2. Include colloidal silica nanoparticles (e.g., Nalco 2326, 5 nanometers mean particle size, pH 10.5, 15% solid content) in the coating composition at an amount between 5 and 20 wt%, desired at about 15 wt%. 3. Add a surfactant such as Masil SF-19 or Surfactant 10G at a concentration of 0.05 to 0.15 wt%, preferably about 0.1 wt%. 4. Ensure the aqueous solution contains at least 75 wt% water, preferably de-ionized (DI) water, with some embodiments containing at least 90 wt% or 96 wt% water. 5. Oxidize the PET film prior to applying the aqueous coating using corona or plasma glow discharge at 2 to 10 watt/((ft²/min)/side) to enhance coating receptivity. 6. Apply the coating composition to the PET surface using bar, roll, knife, curtain, print, spray, slot-die, or dip-coating techniques. 7. Dry the coated substrate in an oven at a temperature of from about 20°C to about 150°C, preferably from about 50°C to 120°C, or from about 100°C to 110°C. 8. Aim for an average coating thickness between 90 to 140 nanometers to minimize glare and achieve desired optical properties. 9. The final coating should consist of at least 50 wt% water-soluble organic polymers, ideally at least 75 wt% or 90 wt%.The coating compositions were applied to clear polyester film by initially dispersing the ingredients in deionized water. The resulting dispersion was thoroughly mixed at a temperature of less than 45 degrees C. (or ambient temperature) until a clear solution was obtained. The coating was applied sequentially, one side at a time, with drying conducted in a hot air convection oven at about 110 degrees C. for typically about 1 minute or until constant weight."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/2_UV╖└╬э╥║╩╣╙├╦╡├ў╩щ.json b/task2/task2-paper-info/2_UV╖└╬э╥║╩╣╙├╦╡├ў╩щ.json
new file mode 100644
index 0000000..08d5fce
--- /dev/null
+++ b/task2/task2-paper-info/2_UV╖└╬э╥║╩╣╙├╦╡├ў╩щ.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "本产品可以直接进行淋涂，根据需要进行适当稀释，稀释比例不得超过 30%。涂层厚度为5-8μm，流平烘烤温度应设定在50~60℃，UV固化能量为480-550 J/cm²。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/A novel organic-inorganic zwitterionic acrylate polymer for high-performance anti-fog coating.json b/task2/task2-paper-info/A novel organic-inorganic zwitterionic acrylate polymer for high-performance anti-fog coating.json
new file mode 100644
index 0000000..4116760
--- /dev/null
+++ b/task2/task2-paper-info/A novel organic-inorganic zwitterionic acrylate polymer for high-performance anti-fog coating.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "The self-designed silicone modified acrylic zwitterionic polymer is copolymerized by acrylic monomers as acrylic macromolecular skeleton, sulfonic acid quaternary ammonium salt as hydrophilic monomer, and the silane as a stabilization component.Synthesize 3-(bis(hydroxymethyl)amino)-2-hydroxypropyl methacrylate (D-GMA) by mixing diethanolamine (DEA) and glycidylmethacrylate (GMA) in a molar ratio of 1:1 in tetrahydrofuran solvent. Stir the mixture for 3 hours at 60°C under refluxing conditions until the solution is transparent. Wash the mixture repeatedly with 5-7 ml of dichloromethane and water to remove unreacted DEA and GMA, retaining the aqueous supernatant. Remove residual water from the aqueous supernatant fraction via rotary evaporation to obtain D-GMA with a yield of 30%.To synthesize the silicone modified acrylic resin hydrophilic polymer (SMA-H), five monomers including D-GMA, AMPS, HEMA, MMA, and BA were used. The synthesis involved two steps: First, 10 ml DMF was heated to 60°C in a 250 ml three-neck flask, and MMA, BA, and KH-570 were added in a molar ratio of 3:1:2. AIBN was added at approximately 0.3%. After reacting for 1 hour, a low molecular weight copolymer was obtained. Second, the low molecular weight copolymer was reacted with HEMA, AMPS, and D-GMA in a molar ratio of 3:1:3 at 60°C for 4 hours.1. Configure the silicone modified acrylic resin hydrophilic polymer (SMA-H), solvent, hydrolysis catalyst, and leveling agent to form a mixture. 2. Prepare the solvent by mixing iso-propyl alcohol (IPO) and ethylene glycol monomethylether (EE) in a volume ratio of 1:1. 3. Mix the silicone modified acrylic resin hydrophilic polymer and the solvent in a volume ratio of 2:3, stirring to obtain a diluted solution. 4. React the diluted solution with an acetic acid solution (pH=4, mass fraction 0.04%) and BYK-300 leveling agent (mass fraction 0.1%) at 40°C for 0.5 hours to obtain the silicone modified acrylic resin hydrophilic coating mixture. 5. Graft the hydrophilic polymer of SMA-H onto a pretreated PC board (5cm x 5cm). 6. Immerse the PC board into a solution containing PVB and ethanol (with PVB mass fraction between 0.05%-0.1%) for 3 minutes. 7. Dry the surface-treated PC board at 80°C for 10 minutes. 8. Deposit the silicone modified acrylic hydrophilic coating with approximately 20μm thickness onto the pretreated PC board using a bar applicator at a heat treatment temperature of 110°C for 2 hours."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/AI╙├╙┌╙╨╗·-╛█║╧╬я║╧│╔.json b/task2/task2-paper-info/AI╙├╙┌╙╨╗·-╛█║╧╬я║╧│╔.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/AI╙├╙┌╙╨╗·-╛█║╧╬я║╧│╔.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/AI╝╝╩ї╘┌╗п╣д╨╨╥╡╔ш╝╞╣д╫ў╓╨╡─╙ж╙├╒╣═√_╜к╥╦╛¤.json b/task2/task2-paper-info/AI╝╝╩ї╘┌╗п╣д╨╨╥╡╔ш╝╞╣д╫ў╓╨╡─╙ж╙├╒╣═√_╜к╥╦╛¤.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/AI╝╝╩ї╘┌╗п╣д╨╨╥╡╔ш╝╞╣д╫ў╓╨╡─╙ж╙├╒╣═√_╜к╥╦╛¤.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/ANTI-FOG    US10241237B2.json b/task2/task2-paper-info/ANTI-FOG    US10241237B2.json
new file mode 100644
index 0000000..86b17fe
--- /dev/null
+++ b/task2/task2-paper-info/ANTI-FOG    US10241237B2.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "The coating compositions are prepared by reacting isocyanates with polyfunctional polyols to obtain a polyurethane. Subsequently, the prepared polyurethane is contacted with a hydrophilic surface-active agent to diffuse molecules of the surface-active agent into the interior of the coating. Additionally, the addition of sulfonated resins is suggested by reacting diols or diamines with di-carboxylic acid esters, followed by sulfonation of double bonds or quaternization of amines. Reactive non-ionic surfactants containing functional groups are incorporated into polyurethanes using polyvinylpyrrolidone as a hydrophilic agent, followed by reacting the isocyanate prepolymer with polyvinylpyrrolidone and the non-ionic surfactant having reactive groups, such as hydroxyl reactive groups.To synthesize hydrophilic polymers with functional groups, prepare a reaction mixture that includes a diisocyanate, short-chain diols (chain extenders), and long-chain difunctional diols (polyols), ensuring the presence of an internal emulsifier. The internal emulsifier can be a diol with an ionic group (such as carboxylate or sulfonate) or a non-ionic group like polyethylene oxide. When preparing an aqueous polyurethane dispersion, utilize dimethylol propionic acid (DMPA) to provide anionic stabilization and curing sites. The final polymer should be dispersed in a volatile liquid diluent, predominantly water, before coating application.No specific experimental protocol for the synthesis of hydrophilic polymers with functional groups was provided in the text excerpt.The synthesis of hydrophilic polymers with functional groups involves using a polyalkylene oxide backbone that may be formed into acid or salt forms. The process typically includes reacting a polyalkylene oxide amine with a succinic anhydride to form a diacid, and then converting the acid group to an ammonium salt group using an alkyl amine. The resulting compound features a divalent linking group which may vary depending on the reactants used. Additionally, the synthesis may incorporate aziridine crosslinkers that react with carboxylate segments in the polymer backbone, where the concentration of the crosslinker should typically be at least 5 wt-% of the coating composition, and potentially higher concentrations may be explored.To synthesize hydrophilic polymers with functional groups, begin by preparing a coating composition using liquid polyurethane. This can be accomplished either by providing the composition in a pourable or sprayable form, or by impregnating it into an applicator substrate such as a sponge or nonwoven fabric. The application of the coating can be performed through conventional methods such as spraying or spin coating. It is critical to cure the coating with crosslinkers, for instance, aziridine, at elevated temperatures ranging from about 90 to 120°C for approximately 20 minutes. Adjust the curing time depending on temperature; lower temperatures may require longer curing periods. The resulting dried and cured polymer should ideally exhibit high transparency (greater than 90%) and minimal haze (less than 5%). Additionally, ensure that the cured coatings demonstrate good anti-fog properties and mechanical durability under various soaking conditions in water at different temperatures for specified durations.Prepare silica nanoparticles by dispersing them in a suitable solvent. Slowly add a desired amount of functional silane to the nanoparticle dispersion based on the desired equivalent surface coverage. Stir the dispersion for 4 hours at room temperature. Heat the mixture to 65°C and maintain it in an oven overnight. This process modifies the silica nanoparticles with functional silanes, resulting in dispersions with different particle sizes and surface coverages.Prepare trifunctional aziridine crosslinkers PZ-2382 and PZ-502 via a Michael addition of EM2382 (MW=692) or SR-502 (MW=692) with 2-methylaziridine. Use 9.1 grams (0.1385 mol) of 2-methylaziridine in the reaction.1. Dissolve succinic anhydride (10 grams) in THF and heat to 50°C. 2. Add ED-900 (50 grams) or ED-2003 (100 grams) to the solution. 3. Allow the reaction to proceed for 24 hours at 50°C. 4. Remove THF under vacuum to obtain a yellow viscous liquid or yellowish wax. 5. Dissolve the resulting PEG-based diacid in water to create a 30% aqueous solution. 6. Add 10 grams of triethylamine to the aqueous solution and stir at room temperature for 30 minutes. 7. The product is now PEG-based dicarboxylic acid ammonium salts with 30 wt% solid.The components were mixed together and stirred for 20 minutes at room temperature. The resulting coating solutions with a solid content of about 30% were coated on polyester (PET), polycarbonate (PC) or glass substrates using a #15 Mayer bar or by dip coating. The resulting coatings were then cured at a temperature from 110-120°C for 20-30 minutes, to form coatings with the desired properties.Place clip with freshly prepared polycarbonate lens slide on metal bar of Velmax Unislide dip coater. Align slide so sides are perpendicular to lab bench top and bottom is parallel to lab bench top. Secure binder clips with tape. The substrates were immersed in coating solutions and were gradually pulled out at an appropriate pulling speed of about 1 mm/second.The polyurethane dispersion W835/140 (32 wt %, 79.7 grams) was mixed with 4.5 grams of PZ-2382 (neat) and 15.8 grams of water, and then stirred for 20 minutes until a homogenous dispersion was obtained. The solution (30 wt% solids) was applied on a PC film with a #14 Mayer Bar and then cured at 110°C for 20 minutes.Mix 75.0 grams of polyurethane dispersion W835/140 (32 wt%) with 6.0 grams of PZ-2382 (neat) and 9.0 grams of water. Stir the mixture for 20 minutes until a homogeneous dispersion is obtained. Apply the solution (30 wt% solids) on a PC film using a #14 Mayer Bar. Cure the coated film at 110°C for 20 minutes. After curing, soak the film in room temperature water for 1 hour and then in water at 50°C for 24 hours to assess performance.The polyurethane dispersion W835/360 (33 wt %, 63.6 grams) was mixed with 9.0 grams of PZ-2382 (neat) and 27.4 grams of water, and then stirred for 20 minutes until a homogenous dispersion was obtained. The solution (30 wt% solids) was applied on a PC film with a #14 Mayer Bar and then cured at 110°C for 20 minutes.The polyurethane dispersion U9800 (34 wt %, 61.8 grams) was mixed with 9.0 grams of PZ-2382 (neat) and 29.2 grams of water, and then stirred for 20 minutes until a homogeneous dispersion was obtained. The solution (30 wt% solids) was applied on a PC film with a #14 Mayer Bar and then cured at 110°C for 20 minutes.The polyurethane dispersion R961 (34wt%, 61.8 grams) was mixed with 9.0 grams of PZ-2382 (neat) and 29.2 grams of water, and then stirred for 20 minutes until a homogenous dispersion was obtained. The solution (30wt% solids) was applied on a PC film with a #14 Mayer Bar and then cured at 110°C for 20 minutes.The polyurethane dispersion W835/140 (32 wt %, 74.1 grams) was mixed with 6.0 grams of PZ-502 (neat), 1.0 g BYK-346, and 18.9 grams of water, and then stirred for 20 minutes until a homogenous dispersion was obtained. The solution (30 wt % solids) was applied on a PC film with a #14 Mayer Bar and then cured at 110°C for 20 minutes.The polyurethane dispersion W835/140 (32 wt %, 74.1 grams) was mixed with 6.0 grams of PZ-502 (neat), 1.0 gram BRIJ 30 and 18.9 grams of water, and then stirred for 20 minutes until a homogenous dispersion was obtained. The solution (30 wt% solids) was applied on a PC film with a #14 Mayer Bar and then cured at 110°C for 20 minutes.The polyurethane dispersion W835/140 (32 wt %, 75.0 grams) was mixed with 4.5 grams of PZ-2382 (neat), 5.0 grams PEG-modified DVSZN004 (50% coverage and 30 wt% solid) and 15.5 grams water, and then stirred for 20 minutes until a homogenous dispersion was obtained. The solution (30 wt% solids) was applied on a PC film with a #14 Mayer Bar and then cured at 110°C for 20 minutes.The polyurethane dispersion W835/140 (32 wt %, 65.6 grams) was mixed with 7.5 grams of PZ-2382 (neat), 5.0 grams PEG-modified DVSZN004 (50% coverage and 30 wt%) and 21.9 grams of water, and then stirred for 20 minutes until a homogenous dispersion was obtained. The solution (30 wt % solids) was applied on a PC plate with a #14 Mayer Bar and then cured at 110°C for 20 minutes. After soaking in room temperature water for 1 hour and then for 24 hours at 50°C water, the coated PET film still exhibited good anti-fog performance.The polyurethane dispersion W835/140 (32 wt %, 65.6 grams) was mixed with 7.5 grams of PZ-2382 (neat), 5.0 grams PEG-modified DVSZN004 (100% coverage and 30 wt%) and 21.9 grams of water, and then stirred for 20 minutes until a homogenous dispersion was obtained. The solution (30 wt % solids) was applied on a PC film with a #14 Mayer Bar and then cured at 110°C for 20 minutes.The polyurethane dispersion W835/140 (32 wt %, 65.6 grams) was mixed with 7.5 grams of PZ-2382 (neat), 5.0 grams PEG-modified DVSZN004 (50% coverage and 30 wt%) and 21.9 grams of water, and then stirred for 20 minutes until a homogeneous dispersion was obtained. Then, 0.6 gram of poly(ethylene glycol) (200) monomethacrylate was added to the above dispersion under stirring until a homogeneous dispersion was formed. The solution (30 wt % solids) was applied on a PC film with a #14 Mayer Bar and then cured at 110°C for 20 minutes.The polyurethane dispersion W835/140 (32 wt %, 65.6 grams) was mixed with 7.5 grams of PZ-2382 (neat), 5.0 grams PEG-modified DVSZN004 (Preparative Example 2, 50% coverage and 30 wt %) and 21.9 grams of water, and then stirred for 20 minutes until a homogenous dispersion was obtained. Then, 1.0 gram of BYK-346 was added to the above dispersion under stirring until a homogenous dispersion was formed. The solution (30 wt % solids) was applied on a PC film with a #14 Mayer Bar and then cured at 110°C for 20 minutes.The polyurethane dispersion W835/140 (32 wt %, 65.64 grams) was mixed with 7.5 grams of PZ-2382 (neat), 5.0 grams PEG-based modified DVSZN004 (50% coverage and 30 wt %) and 21.9 grams of water, and then stirred for 20 minutes until a homogenous dispersion was obtained. Then, 1.0 gram of BRIJ 30 was added to the above dispersion under stirring until a homogenous dispersion was formed. The solution (30 wt % solids) was applied on a PC film with a #14 Mayer Bar and then cured at 110°C for 20 minutes.The polyurethane dispersion W835/140 (32 wt %, 8.43 grams) was mixed with 0.94 gram R-961 (32%), 1.15 grams of PZ-2382 (neat) and 2.5 grams PEG-based modified l0 DVSZNo04 (Preparative Example 2, 50% coverage and 10 wt %) and stirred for 20 minutes until a homogeneous dispersion was obtained. Then, 0.4 gram of A-18 and 0.2 gram BC-10 were respectively added to the above dispersion under stirring until a homogeneous dispersion was formed. The solution was applied on a PC film with a #14 Mayer Bar and then cured at 110°C for 20 minutes.Mix 65.6 grams of polyurethane dispersion W835/140 (32 wt%) with 6.0 grams of PZ-2382 (neat), 10.0 grams of PEG-based modified DVSZN004 (5% coverage and 30 wt%), and 18.4 grams of water. Stir the mixture for 20 minutes until a homogenous dispersion is obtained. Apply the resulting solution (30 wt% solids) on a PC film using a #14 Mayer Bar. Cure the applied film at 110°C for 20 minutes. After curing, soak the coated PC film in room temperature water for 1 hour and then for 24 hours at 50°C water.The polyurethane dispersion W835/140 (32 wt %, 56.3 grams) was mixed with 6.0 grams of PZ-2382 (neat), 20.0 grams PEG-based modified DVSZN004 (5% coverage and 30 wt%) and 17.7 grams of water. The mixture was stirred for 20 minutes until a homogeneous dispersion was obtained. The solution (30 wt% solids) was applied on a PC film with a #14 Mayer Bar and then cured at 110°C for 20 minutes.The polyurethane dispersion W835/140 (32 wt %, 65.6 grams) was mixed with 7.5 grams of PZ-2382 (neat), 1.5 grams AL-2450, and 22.9 grams water. The mixture was stirred for 20 minutes until a homogenous dispersion was obtained. The solution (30 wt % solids) was applied on a PC film with a #14 Mayer Bar and then cured at 110°C for 20 minutes.Mix 28.1 grams of polyurethane dispersion W835/140 (32 wt %) with 6.0 grams of PZ-2382 (neat), 50.0 grams of PEG-based modified DVSZN004 (5% coverage and 30 wt %) and 15.9 grams of water. Stir the mixture for 20 minutes until a homogenous dispersion is obtained. Apply the solution (30 wt% solids) on a PC film using a #14 Mayer Bar and cure at 110°C for 20 minutes.Mix 60.9 grams of polyurethane dispersion W835/140 (32 wt %) with 15 grams of 900-DA (30 wt %) under stirring to form a homogenous dispersion. Then add 6.0 grams of PZ-2382 (neat) and 18.1 grams of water, and stir for 20 minutes until a homogenous dispersion is obtained. Apply the solution (30 wt % solids) on a PC plate using a Velmax Unislide dip coater and cure at 110°C for 20 minutes. After curing, soak in room temperature water for 240 hours, or at 80°C for 96 hours, or at 65°C for 120 hours.The polyurethane dispersion W835/140 (32 wt %, 60.2 grams) was mixed with 29.2 grams of 900-DA (30 wt %) under stirring to form a homogenous dispersion, then 7.0 grams of PZ-2382 (neat) and 3.6 grams of water were added and stirred for 20 minutes until a homogenous dispersion was obtained. The solution (35 wt% solids) was applied on a PC plate by a Velmax Unislide dip coater and then cured at 110 °C for 20 minutes. The resulting coated PC film exhibited anti-fog performance and good light transmittance (>90). After soaking in room temperature water for 240 hours, as well as 96 hours at 80 °C water or 120 hours at 65 °C, the coated PET film still exhibited excellent anti-fog performance and durability.The polyurethane dispersion W835/140 (32 wt %, 54.7 grams) was mixed with 35.0 grams of 900-DA (30 wt %) under stirring to form a homogenous dispersion. Then, 7.0 grams of PZ-2382 (neat), 1 gram of BYK-346, and 4 grams of water were added and stirred for 20 minutes until a homogenous dispersion was obtained. The solution (35 wt% solids) was applied on a PC plate with a #14 Mayer Bar and cured at 110 °C for 20 minutes. The coated PC film exhibited excellent anti-fog performance when exposed to 50 °C vapor and good light transmittance (>90). After soaking in room temperature water for 240 hours, as well as in 96 hours at 80 °C water or 120 hours at 65 °C, the coated PC film still exhibited excellent anti-fog performance and was very durable. Additionally, a glass plate and a PC lens were coated with the same coating solution using casting and dip coating methods, followed by curing at 110 °C for 20 minutes.The polyurethane dispersion W835/140 (32 wt %, 56.325 grams) was mixed with 15.0 grams of 900-DA (30 wt %) under stirring to form a homogeneous dispersion. Then, 6.0 grams of PZ-2382 (neat), 5.0 grams PEG-modified DVSZN004 (Preparative Example 2, 50% coverage and 30 wt %) and 17.7 grams of water were added and stirred for 30 minutes until a homogeneous dispersion was obtained. The solution (30 wt % solids) was applied on a PC plate by a Velmax Unislide dip coater and then cured at 110°C for 20 minutes. After coating, it was soaked in room temperature water for 240 hours, as well as 96 hours at 80°C water or 120 hours at 65°C, to test for the durability of the coated film.Mix 60.9 grams of polyurethane dispersion W835/140 (32 wt %) with 15 grams of 2003-DA (30 wt %) under stirring to form a homogenous dispersion. Add 6.0 grams of PZ-2382 (neat) and 18.1 grams of water, and stir for 20 minutes until a homogenous dispersion is obtained. Apply the solution (30 wt% solids) on a PC plate using a Velmax Unislide dip coater and cure at 110°C for 20 minutes. Soak the coated PC plates in room temperature water for 240 hours, or in water at 80°C for 96 hours, or at 65°C for 120 hours.Add 28 grams of PZ-502 (neat) and 11.1 grams of water, and stir for 20 minutes until a homogenous dispersion is obtained. Apply the resulting solution (30 wt% solids) on a PC film using a #14 Mayer Bar. Cure the film at 110°C for 5 minutes. Soak the coated PC film in room temperature water for 240 hours, or 96 hours at 80°C, or 120 hours at 65°C.The polyurethane dispersion W835/140 (32 wt %, 60.9 grams) was mixed with 25 grams of 900-DA (30 wt %) under stirring to form a homogenous dispersion. Then, 3.0 grams of PZ-502 (neat) and 11.1 grams of water were added and stirred for 20 minutes until a homogenous dispersion was obtained. The solution (30 wt% solids) was applied on a PC plate with a #14 Mayer Bar and then cured at 110°C for 20 minutes. After curing, the coated PC film was soaked in room temperature water for 240 hours, as well as at 80°C for 96 hours, or at 65°C for 120 hours.Mix 60.9 grams of polyurethane dispersion W835/140 (32 wt %) with 25 grams of 900-DA (30 wt %) under stirring to form a homogenous dispersion. Add 3.0 grams of XL-706 (neat) and 11.1 grams of water, then stir for 20 minutes until a homogenous dispersion is obtained. Apply the solution (30 wt % solids) on a PC film using a #14 Mayer Bar and cure at 110°C for 20 minutes. The coated PC film should then be soaked in room temperature water for 240 hours, or for 96 hours at 80°C water, or for 120 hours at 65°C. The final product should exhibit excellent anti-fog performance and good light transmittance (>90).The polyurethane dispersion W835/140 (32 wt %, 60.9 grams) was mixed with 25 grams of 900-DA (30 wt %) under stirring to form a homogenous dispersion. Then, 3.0 grams of CX-100 (neat) and 11.1 grams of water were added and stirred for 20 minutes until a homogenous dispersion was obtained. The solution (30 wt% solids) was applied on a PC 5 film with a #14 Mayer Bar and then cured at 110°C for 20 minutes.The polyurethane dispersion W835/140 (32 wt %, 54.7 grams) was mixed with 35.0 grams of 900-DA (30 wt %) under stirring to form a homogenous dispersion. Then, 7.0 grams of PZ-2382 (neat), 1 gram BRIJ 30, and 4 grams of water were added and stirred for 20 minutes until a homogenous dispersion was obtained. The solution (35 wt % solids) was applied on a PC plate with a #14 Mayer Bar or by dip coating and then cured at 110°C for 20 minutes. Coated PC films were soaked in room temperature water for 240 hours, and also tested in hot water (96 hours at 80°C and 120 hours at 65°C). The coated PC film exhibited excellent anti-fog performance and good light transmittance (>90). A glass plate and a PC lens were coated with the same coating solution by casting and dip coating methods, followed by curing at 110°C for 20 minutes.The polyurethane dispersion W835/140 (32 wt %, 65.6 grams) was mixed with 23.3 grams of 900-DA (30 wt %) under stirring to form a homogeneous dispersion. Then, 7.0 grams of PZ-2382 (neat), 1 gram BRIJ 30 and 3 grams of water were added and stirred for 20 min until a homogeneous dispersion was obtained. The solution (35 wt% solids) was applied on a PC plate with a #14 Mayer Bar or by dip coating and then cured at 110°C for 20 minutes. The resulting coated PC film exhibited 'excellent' anti-fog performance and good light transmittance (>90). After soaking in room temperature water for 240 hours as well as 96 hours at 80°C or 120 hours at 65°C, the coated PC film still exhibited 'excellent' anti-fog performance and was very durable. A glass plate and a PC lens were coated with the above coating solution by casting and dip coating methods followed by curing at 110°C for 20 minutes.An acrylic latex (40.5 wt %, 43.5 grams) was mixed with 900-DA (30 wt % D 30 grams) under stirring to form a homogeneous dispersion. Then PZ-2382 (7.0 grams, neat) and 19.5 grams of water were added respectively, and the resulting solution was stirred for 20 minutes. The final dispersion solution (35 wt % solids) was applied on a PC film with a #14 Mayer. The resulting coating was cured at 110 °C for 20 minutes.A polyurethane/acrylic hybrid latex (40 wt %, 43.5 grams) was mixed with 900-D (30 wt %, 30.0 grams) under stirring to form a homogenous dispersion. Then, PZ-2382 (7.0 grams, neat) and 19.5 grams of water were added, and the resulting solution was stirred for 20 minutes until a homogenous dispersion was obtained. The final dispersion solution (35 wt % solids) was applied on a PC film using a #14 Mayer. The resulting coating was cured at 110°C for 20 minutes. The coated PC film exhibited excellent anti-fog performance and good optical properties, with light transmittance up to 90%. Samples were subjected to water soak tests, one at room temperature for 120 hours and one at 65°C for 120 hours.Silica nanoparticles comprising an epoxy silane surface treatment were prepared by combining Nalco 105O silica nanoparticles sol (180 grams, 10\\mathrm{\\mt\\\\%}) with concentrated 50 \\mathrm{H}_{2}\\mathrm{SO}_{4}$ to a \\mathfrak{p H} value :=2\\mathord{\\sim}3 under stirring condition. Then \\upgamma-Glycidoxypropyl-trimethoxysilane (1.31 grams, 50 mole \\% coverage) was added to the acidified sol dispersion by drop wise. After addition, the solution was heated at 60^{\\circ}\\mathrm{C} overnight. After reaction, the solution \\mathfrak{p H} was adjusted to a neutral condition by adding NaOH aqueous solution (5 wt \\%). A polyurethane dispersion (4.0 grams, 10\\mathrm{wt\\%}), available from DSM NeoResins Company under the trade designation 'NeoResin \\ensuremath{\\mathrm{R960^{\\circ}}}' was mixed with a hydroxyl-containing acrylic latex (2.0 grams, 10 wt \\%) obtained from Bayer Company under the trade designation 'VPLS2058'. To the solution was sequentially added polyisocyanate, available from Bayer under the trade designation 'Bayhdur 2665^{\\mathrm{,}\\mathrm{,}}' (0.04 gram, neat), PZ-2382 (0.15 gram, neat) and epoxy silane modified nanoparticles (50 mole \\% coverage, 2.0 grams, 10\\ \\mathrm{\\mt}\\ \\%). The final solution was stirred for 10 minutes."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/ANTI-FOG  US10048408B2.json b/task2/task2-paper-info/ANTI-FOG  US10048408B2.json
new file mode 100644
index 0000000..e6e3933
--- /dev/null
+++ b/task2/task2-paper-info/ANTI-FOG  US10048408B2.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of hydrophilic polymers with functional groups involves reacting isocyanates with polyfunctional polyols to obtain a polyurethane. Subsequently, a hydrophilic surface-active agent is contacted with the prepared polyurethane to allow diffusion of the agent into the coating's interior. Additionally, sulfonated resins can be prepared from diols or diamines reacted with di-carboxylic acid esters and then sulfonated or quarternized. These resins are reacted into the polyurethane backbone in an end-to-end fashion to increase hydrophilicity. Furthermore, a non-ionic surfactant with reactive functional groups can be incorporated by reacting it with an isocyanate prepolymer that has been reacted with polyvinylpyrrolidone to improve antifog properties while integrating hydroxyl reactive groups.To synthesize hydrophilic polymers with functional groups, use thermoplastic polyurethane compositions formed from the reaction of a diisocyanate with short-chain diols (chain extenders) and diisocyanates with long-chain difunctional diols (polyols). Ensure that the resulting polymeric dispersion maintains an alkaline pH and can be prepared as a latex.To synthesize hydrophilic polymers with functional groups, begin with the polyesterification of an organic polycarboxylic acid or anhydride thereof with organic polyols and/or an epoxide. Utilize aliphatic or aromatic dibasic acids and diols, including acyclic alkylene glycols such as ethylene glycol, and cyclic glycols like hydrogenated Bisphenol A. For polyol components, consider using hydroxy-containing acrylic polymers or acrylic polyols, and examples of polyether polyols with specific formulas. Following the formation of polyester polyols, proceed by reacting these polyols with diisocyanates or polyisocyanates, ensuring a molar excess for complete reaction. Incorporate an internal emulsifier during the reaction, which can be a diol with ionic or non-ionic groups, such as polyethylene oxide. For anionic polyurethane dispersions, include dimethylol propionic acid (DMPA) to enhance dispersibility and provide curing sites. The resulting polymer structure can exhibit a combination of soft and hard segments, forming a stable aqueous dispersion, which is then processed to achieve desired properties.The synthesis of hydrophilic polymers with functional groups involves creating a coating composition that typically contains one or more polymers, such as polyurethane and/or acrylic polymers, in an amount totaling at least 40 wt% solids. The crosslinker concentration is generally at least 2 wt% and can go up to 25 wt% of the solids. A hydrophilic additive that is non-reactive with the polymer yet can be crosslinked is included, typically at a concentration of at least 5 wt%. This additive comprises a polyalkylene oxide backbone with terminal acid or salt groups. The hydrophpilic additive can be formed from a polyalkylene oxide amine reacted with succinic anhydride, then with an alkyl amine to convert acid groups into ammonium salt groups. The polymeric dispersion may also include various commercial polyurethanes and acrylic emulsions as needed. The crosslinking occurs when the composition is cured, typically under ambient conditions or when the pH drops below 6.Silica nanoparticles modified with functional silanes were prepared by slowly adding a desired amount of a functional silane to selected silica nanoparticle dispersion. The relative amounts of the silica nanoparticle dispersion to the functional silane were determined based on equivalent surface coverage desired. The resulting dispersions were stirred for 4 hours at room temperature and then heated to 65°C in an oven overnight.To synthesize PEG-based ammonium salts, begin with the appropriate molecular weight polyethylene glycol (PEG) as the base polymer. React the PEG with a suitable amine source to introduce ammonium functional groups. The reaction conditions should include appropriate temperatures and solvent systems conducive to the formation of ionic bonds. After completion of the reaction, purify the synthesized polymer through dialysis or precipitation methods to remove unreacted monomers and by-products. Finally, characterize the resulting hydrophilic polymer using techniques such as NMR and FTIR to confirm the presence of the ammonium functional groups.Trifunctional aziridine crosslinkers PZ-2382 and PZ-502 were prepared via a Michael addition of EM 2382 (6) with 2-methylaziridine. 2-methylaziridine (9.1 grams, 0.1385 mol) was added drop-wise to the EM 2382 or SR-502 (30 grams, 0.0434 mol) at room temperature. The resulting mixture was stirred for 1 hour at room temperature and then refluxed at 60°C for 24 hours. Next, succinic anhydride (10 grams) was dissolved into THF at 50°C, and ED-900 (50 grams) or ED-2003 (100 grams) was added. After 24 hours of reaction at 50°C, the product yellow viscous liquid or yellowish wax was obtained after removal of THF under vacuum. The resulting PEG-based diacid was dissolved into water to obtain a 30% aqueous solution, to which 10 grams of triethylamine was added and stirred at room temperature for 30 minutes to obtain PEG-based dicarboxylic acid ammonium salts with 30 wt% solid.The polyurethane dispersion W835/140 (32 wt %, 60.9 grams) was mixed with 15 grams of 900-DA (30 wt %), prepared as described in Preparative Example 5, under stirring to form a homogenous dispersion. Then, 6.0 grams of PZ-2382 (neat, prepared as described in Preparative Example 4) and 18.1 grams of water were added and stirred for 20 minutes until a homogenous dispersion was obtained. The solution (30 wt% solids) was applied on a PC plate by a Velmax Unislide dip coater and then cured at 110°C for 20 minutes.The polyurethane dispersion W835/140 (32 wt %, 60.26 grams) was mixed with 29.2 grams of 900-DA (30 wt % prepared as described above in Preparative Example 5) under stirring to form a homogenous dispersion, then 7.0 grams of PZ-2382 (neat) and 3.6 grams of water were added and stirred for 20 min until a homogenous dispersion was obtained. The solution (35 wt% solids) was applied on a PC plate by a Velmax Unislide dip coater and then cured at 110°C for 20 minutes.The polyurethane dispersion W835/140 (32 wt %, 54.7 grams) was mixed with 35 grams of 900-DA (30 wt % D prepared as described above in Preparative Example 5) under stirring to form a homogenous dispersion. Then 45 grams of PZ-2382 (neat) and 3 grams of water were added and stirred for 20 minutes until a homogenous dispersion was obtained. The solution (35 wt% solids) was applied on a PC plate by a Velmax Unislide dip coater and then cured at 110°C for 20 minutes.The polyurethane dispersion W835/140 (32 wt %, 65.6 grams) was mixed with 23.3 grams of 900-DA (30 wt % prepared as described above in Preparative Example 5) under stirring to form a homogenous dispersion. Then, 7.0 grams of PZ-2382 (neat), 1 gram BYK-346, and 3 grams of water were added and stirred for 20 minutes until a homogenous dispersion was obtained. The solution (35 wt % solids) was applied on a PC plate by a Velmax Unislide dip coater and then cured at 110°C for 20 minutes.The polyurethane dispersion W835/140 (32 wt %, 54.7 grams) was mixed with 35.0 grams of 900-DA (30 wt % prepared as described above in Preparative Example 5) under stirring to form a homogenous dispersion. Then 7.0 grams of PZ-2382 (neat), 1 gram BYK-346, and 4 grams of water were added and stirred for 20 minutes until a homogenous dispersion was obtained. The solution (35 wt% solids) was applied on a PC plate with a # 14 Mayer Bar and then cured at 110°C for 20 minutes. Coating solutions were applied to a glass plate and a PC lens by casting and dip coating methods followed by curing at 110°C for 20 minutes.The polyurethane dispersion W835/140 (32 wt %, 56.3 grams) was mixed with 15.0 grams of 900-DA (30 wt %, 4C) under stirring to form a homogenous dispersion. Then, 6.0 grams of PZ-2382 (neat), 5.0 grams PEG-modified DVSZN004 (50% coverage and 30 wt %) and 17.7 grams of water were added and stirred for 45 minutes until a homogenous dispersion was obtained. The solution (30 wt % solids) was applied on a PC plate by a Velmax Unislide dip coater and then cured at 110°C for 20 minutes. After soaking in room temperature water for 240 hours, as well as 96 hours at 80°C water or 120 hours at 65°C, the coated PC film still exhibited excellent anti-fog performance and durability.Mix 60.9 grams of polyurethane dispersion W835/140 (32 wt %) with 15 grams of 2003-DA (30 wt % prepared as described in Preparative Example 5) under stirring to form a homogeneous dispersion. Then, add 6.0 grams of PZ-2382 (neat) and 18.1 grams of water, and stir for 20 minutes until a homogeneous dispersion is obtained. Apply the solution (30 wt % solids) on a PC plate using a Velmax Unislide dip coater and cure at 110°C for 20 minutes. Soak the coated PC plates in room temperature water for 240 hours, or in water at 80°C for 96 hours, or at 65°C for 120 hours.The polyurethane dispersion W835/140 (32 wt %, 60.9 grams) was mixed with 25 grams of 900-DA (30 wt % D) under stirring to form a homogenous dispersion. Then, 3.0 grams of PZ-28 (neat) and 11.1 grams of water were added and stirred for 20 minutes until a homogenous dispersion was obtained. The solution (30 wt% solids) was applied on a PC film with a # 14 Mayer Bar and then cured at 110°C for 20 minutes. The coated PC film was soaked in room temperature water for 240 hours, and 96 hours at 80°C or 120 hours at 65°C.The polyurethane dispersion W835/140 (32 wt %, 60.9 grams) was mixed with 25 grams of 900-DA (30 wt % D prepared as described above in Preparative Example 5) under stirring to form a homogenous dispersion. Then, 3.0 grams of PZ-33 (neat) and 11.1 grams of water were added and stirred for 20 min until a homogenous dispersion was obtained. The solution (30 wt% solids) was applied on a PC plate with a #14 Mayer Bar and then cured at 110°C for 20 minutes. The resulting coated PC film exhibited 'excellent' anti-fog performance and good light transmittance (>90). After soaking in room temperature water for 240 hours, as well as 96 hours at 80°C water or 120 hours at 65°C, the coated PC film still exhibited 'excellent' anti-fog performance and was very durable.Mix 60.9 grams of polyurethane dispersion W835/140 (32 wt %) with 25 grams of 900-DA (30 wt % D) under stirring to form a homogenous dispersion. Add 3.0 grams of XL-706 (neat) and 11.1 grams of water, stirring for 20 minutes until a homogenous dispersion is obtained. Apply the solution (30 wt % solids) onto a PC film using a #14 Mayer Bar and cure at 110°C for 20 minutes. After curing, soak the coated PC film in room temperature water for 240 hours, or at 80°C for 96 hours, or at 65°C for 120 hours.The polyurethane dispersion W835/140 (32 wt %) was mixed with 25 grams of 900-DA (30 wt % D).Prepare a homogenous dispersion under stirring. Add 3.0 grams of CX-100 (neat) and 11.1 grams of water, and stir for 20 minutes until a homogenous dispersion is obtained. Apply the solution (30 wt% solids) on a PC film using a #14 Mayer Bar. Cure the coated film at 110°C for 20 minutes. To test the performance, expose the film to 50°C vapor and assess anti-fog performance and light transmittance. Soak the coated film in room temperature water for 240 hours, or 96 hours at 80°C, or 120 hours at 65°C to evaluate durability and anti-fog performance.The polyurethane dispersion W835/140 (32 wt %, 54.7 grams) was mixed with 35.0 grams of 900-DA (30 wt % prepared as described in Preparative Example 5) under stirring to form a homogenous dispersion. Then, 7.0 grams of PZ-502 (neat), 1 gram BRIJ 30, and 4 grams of water were added and stirred for 20 min until a homogenous dispersion was obtained. The solution (35 wt% solids) was applied on a PC plate with a # 14 Mayer Bar or by dipping coating and then cured at 110°C for 20 minutes. The coated films were subjected to soaking in room temperature water for 240 hours, 96 hours at 80°C water, or 120 hours at 65°C. The resulting films were tested for anti-fog performance and light transmittance.Mix 65.6 grams of polyurethane dispersion W835/140 (32 wt %) with 23.3 grams of 900-DA (30 wt %) under stirring to form a homogenous dispersion. Add 7.0 grams of PZ-502 (neat), 1 gram of BRIJ 30, and 3 grams of water, and stir for 20 minutes until a homogenous dispersion is obtained. Apply the solution (35 wt % solids) on a PC plate using a #14 Mayer Bar or by dip coating, and cure at 110°C for 20 minutes. The coated PC film exhibits 'excellent' anti-fog performance. Additionally, the solution can be used to coat a glass plate and a PC lens using casting and dip coating methods, followed by curing at 110°C for 20 minutes. After soaking in room temperature water for 240 hours, as well as 96 hours at 80°C or 120 hours at 65°C, the coated surfaces maintain 'excellent' anti-fog performance.An acrylic latex (40.5 wt %, 43.5 grams) was mixed with 900-DA (30 wt %, 30 grams) under stirring to form a homogenous dispersion. PZ-2382 (7.0 grams, neat) and 19.5 grams of water were then added, and the solution was stirred for 20 minutes. The final dispersion solution (35 wt% solids) was applied on a PC film with a #14 Mayer. The coated PC film was cured at 110°C for 20 minutes.A polyurethane/acrylic hybrid latex (40 wt %, 43.5 grams) was mixed with 900-DA (30 wt %, 30.0 grams) under stirring to form a homogenous dispersion. Then, PZ-2382 (7.0 grams, neat) and 19.5 grams of water were added respectively, and the resulting solution was stirred for 20 minutes until a homogenous dispersion was achieved.1. Combine 94.38 grams of polyurethane dispersion W835/140 (32 wt %) with 61.17 grams of 900-DA (30 wt %). Stir for 15 minutes to form a homogenous dispersion. 2. Add 1.75 grams of BYK-346 with stirring, and stir for an additional 15 minutes to achieve a homogenous dispersion. 3. Combine the specified crosslinker type and amount with 0.4 grams of water and 9 grams of the polyurethane blend to create the anti-fog coating composition. 4. Coat the compositions onto PC film using Meyer bar #15. 5. Cure the coatings at 120°C for 20 minutes.The polyurethane dispersion W835/140 (32 wt %, 32.8 grams) was mixed with 11.5 grams of 900-DA (30 wt %) under stirring to form a homogenous dispersion. Then, 3.0 grams of PZ-502 (neat), 0.75 grams Jeecol LA-7 (C12E0_7 from Jeen International Co.) and 1.0 gram BYK-346 were added and stirred for 20 minutes until a homogenous dispersion was obtained. The solution was cast on the substrates, such as stainless steel, PVC, and fiberboard, then cured at room temperature.Mix 32.8 grams of polyurethane dispersion W835/140 (32 wt %) with 11.5 grams of 900-DA (30 wt %) under stirring to form a homogenous dispersion. Add 1.0 gram of Bacote 20 (20% by weight in water), 0.75 grams of Jeecol LA-7 (C12E0_7), and 1.0 gram of BYK346. Stir for 20 minutes until a homogenous dispersion is obtained. Cast the solution on substrates such as stainless steel, PVC, and fiberboard, then cure at room temperature.A method of providing an anti-fog coating on a surface of a substrate, the method comprising providing the coating composition according to claim 1; applying the coating composition to a substrate; and drying and curing the coating composition."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/ANTI-FOG  US9346974B2.json b/task2/task2-paper-info/ANTI-FOG  US9346974B2.json
new file mode 100644
index 0000000..5a2adc6
--- /dev/null
+++ b/task2/task2-paper-info/ANTI-FOG  US9346974B2.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "The hydrophilic polymer for the anti-fog layer can be synthesized by choosing a polymer such as polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate, polyvinylpyrrolidone, polyethylene oxide, polyacrylamide, polyester, polyurethane, cellulose acetate, hydroxyethyl cellulose, hydroxymethyl cellulose, or gelatin, or blends or copolymers thereof. The hydrophilic polymer can be a polymer having a backbone and hydrophilic segments covalently bonded to the backbone. The synthesis can include introducing hydrophilic segments which may comprise alkylene oxides, lactones, lactams, silanes, acrylamides, alcohols, or combinations thereof. The polymer should be formed such that the hydrophilic segments comprise at least about 1 wt% to about 95 wt% by weight of the hydrophilic polymer. The resulting hydrophilic polymer can be incorporated into an anti-fog layer that might also contain an adhesive polymer and a hard polymer, ensuring that all polymers in the composition are different.Coating compositions for the adhesive layer were coated onto C-treated FEP substrates and dried at 93 degrees Celsius for 10 minutes. Each adhesive coated FEP sheet was laminated to a PVC sheet with the adhesive layer in between. Lamination was done at a foot press at 40 psi at 121 degrees Celsius or with a hand roller at room temperature. Some composites were additionally cured at 107 degrees Celsius for various time periods. Peel strength between the FEP and PVC sheets was determined using an Instron following ASTM D1876.Two FEP sheets, C-treated on both sides, are coated on both sides with Adhesive 4 and dried at 93 degrees Celsius for 10 minutes. Each adhesive coated FEP sheet is laminated between two PVC sheets with a hand roller at room temperature, followed by 5 minutes of curing at 107 degrees Celsius. Anti-fog coating compositions as detailed in Table 3 are then coated on Composites B1 and B2 over the surface of one of the PVC layers, and also applied directly to a stand-alone C-treated FEP sheet.The synthesis of hydrophilic polymers involves creating a polymer with a backbone and hydrophilic segments covalently bonded to it. Specifically, the hydrophilic polymer may be a hydrophilic polyurethane which includes hydrophilic segments such as alkylene oxides, lactones, lactams, or combinations thereof. The hydrophilic polymer should be present in the composition in an amount within a range of about 10 wt% to about 90 wt% based on the total dry weight of the anti-fog coating composition.The hydrophilic polymer comprises a polymer having a polyurethane backbone and hydrophilic segments covalently bonded to the polyurethane backbone wherein the hydrophilic segments comprise alkylene oxides, lactones, lactams, or combinations thereof."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/Advanced Materials - 2024 - Ng - Progress and Opportunities for Machine Learning in Materials and Processes of Additive.json b/task2/task2-paper-info/Advanced Materials - 2024 - Ng - Progress and Opportunities for Machine Learning in Materials and Processes of Additive.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/Advanced Materials - 2024 - Ng - Progress and Opportunities for Machine Learning in Materials and Processes of Additive.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/Advanced Science - 2022 - Shi - Effective Antifogging Coating from Hydrophilic Hydrophobic Polymer Heteronetwork.json b/task2/task2-paper-info/Advanced Science - 2022 - Shi - Effective Antifogging Coating from Hydrophilic Hydrophobic Polymer Heteronetwork.json
new file mode 100644
index 0000000..d72774c
--- /dev/null
+++ b/task2/task2-paper-info/Advanced Science - 2022 - Shi - Effective Antifogging Coating from Hydrophilic Hydrophobic Polymer Heteronetwork.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "To synthesize the hydrophilic/hydrophobic polymer heteronetwork (PVA/PTPM HN), begin with the mixing of hydrophilic poly(vinyl alcohol) (PVA) and hydrophobic poly 3-(trimethoxysilyl) propyl methacrylate (PTPM). Ensure strong bonding by implementing either covalent bonding or topological entanglements with the substrate surfaces. Increase the thickness of the PVA/PTPM HN coating to enhance water absorption capacity, while monitoring for high optical transmittance and integrity against wrinkling and peeling during drying-swelling cycles.1. Dissolve hydrophilic PVA and hydrophobic 3-(Trimethoxysilyl) propyl methacrylate (TPM) monomer in dimethyl sulfoxide (DMSO). 2. Photopolymerize TPM in situ using 365 nm ultraviolet light, confirmed by FTIR through the disappearance of C=C double bond at 1635 cm−1 and the increase in viscosity. 3. Set the mass ratio of PVA to TPM as 7:1. 4. Displace DMSO with water to restore interpolymer hydrogen bonding, forming the hydrophilic PVA network. 5. Allow siloxane moieties on PTPM to hydrolyze and condense, forming the hydrophobic PTPM network that interpenetrates with the hydrophilic PVA network.The synthesis of hydrophilic polymers with functional groups involves the following steps: Dissolve 3.6 g of PVA in 75 mL of DMSO and stir for 2 hours at 95 °C. Add a mixture of 0.5 mL of TPM and 75 mg of DMPA to the solution and stir for 20 minutes in the dark. After defoaming, spread the solution onto glass slides to create a uniform liquid layer with thicknesses of 25, 100, or 200 micrometers using a wet film coater. Irradiate the layer with UV light at a wavelength of 365 nm and power of 0.8 W/cm² for a designated time. Perform solvent exchange in water for an additional 0.5 hours. Finally, dry the PVA/PTPM HN coated substrates at 25 °C for 24 hours."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/Application of machine learning in polymer additive manufacturing_ A review.json b/task2/task2-paper-info/Application of machine learning in polymer additive manufacturing_ A review.json
new file mode 100644
index 0000000..862a633
--- /dev/null
+++ b/task2/task2-paper-info/Application of machine learning in polymer additive manufacturing_ A review.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "VP consists of selective curing of liquid photo-sensitive material using light/radiation. Light is projected onto the photopolymer, following a pattern defined by a CAD file. The process selectively cures the photopolymer, resulting in the formation of the final part. Typical material systems consist of acrylate or epoxy-based monomers, photoinitiators, diluents, light absorbers, and radical inhibitors. Low viscosity resins (0.25-10 Pa.s) are recommended to avoid damaging printed features during the recoating process. Factors influencing the properties of VP parts include layer height, build orientation, exposure time, light source intensity, resin viscosity, reactivity, and photoinitiator concentration."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/Bio-inspired antifogging PDMS coupled micro-pillared superhydrophobic arrays and SiO2 coatings.json b/task2/task2-paper-info/Bio-inspired antifogging PDMS coupled micro-pillared superhydrophobic arrays and SiO2 coatings.json
new file mode 100644
index 0000000..57ee038
--- /dev/null
+++ b/task2/task2-paper-info/Bio-inspired antifogging PDMS coupled micro-pillared superhydrophobic arrays and SiO2 coatings.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "A regular micro-pillared array (MPA) was designed using a PDMS film (PF) in combination with silicon dioxide (SiO2) modification. An SU-8 mold of negative well arrays was obtained using traditional UV lithography. A soft replication method was adopted to obtain a PF with MPA as the substrate. SiO2 nanometer coatings were then sprayed on the surface of the PF with the MPA. The dimensional uniformity and quality of the prepared PF were characterized using field emission scanning electronic microscopy (FESEM). Fourier transform infrared spectroscopy (FTIR) indicated the presence of functional groups -CH2 and -CH3 on the surfaces of the bioinspired PF samples.First, clean glass slides (approximately 4x3 cm^2) for 10 min. Dry the substrate at 200°C for 30 min. Dispense SU-8 photoresist on the glass slide through a spin-coating program at 500 rpm for 10 s and 3000 rpm for 30 s. Soft bake the substrate on a level hotplate at 103°C for 6 min. Perform traditional UV lithography with UV exposure (exposure energy at 158 mJ cm^-2 for 10 s) perpendicularly to a photomask of circle-shaped array patterns. Carry out a post exposure bake step at 98°C for 5 min to harden the SU-8 layer. The thickness of the resulting film is approximately 6 μm. Lastly, immerse the substrate in the developer for 30 s and agitate the solution using a tweezer to obtain the uniform SU-8 CMHA on the glass substrate.First, the prepolymer and the curing agent were mixed uniformly and stirred in a glass beaker to synthesize the PDMS. Second, the PDMS was poured over the photoresist layer gently and the assembly was moved into the vacuum chamber for 40 min to remove air bubbles, next it was heated in a drying oven at 80 °C for 1 h to completely cure the PDMS. Last, the solidified PDMS was peeled off from the glass substrate and the MPA was transferred to the PF.A commercial SiO2 coating agent was sprayed on top of the as-prepared PDMS using a spray coating setup at a distance of approximately 15 cm from the nozzle head. The samples were then baked in a drying oven at 80 °C for 20 min. The spray coating and heating processes were repeated twice."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/CN102666753B╖└╬э═┐┴╧╫щ║╧╬я.json b/task2/task2-paper-info/CN102666753B╖└╬э═┐┴╧╫щ║╧╬я.json
new file mode 100644
index 0000000..51adaac
--- /dev/null
+++ b/task2/task2-paper-info/CN102666753B╖└╬э═┐┴╧╫щ║╧╬я.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of hydrophilic polymers involves the use of a copolymer (A) formed from a mixture of monomers A1, A2, and A3. Monomer A1 is a vinyl monomer with N-hydroxymethyl or N-alkoxy hydroxymethyl groups; monomer A2 is a vinyl monomer with a sulfonic acid group; and monomer A3 is an alkyl (meth)acrylate monomer. The total amount of monomers A1, A2, and A3 is 100 parts by mass, where A1 comprises 3-20 parts, A2 comprises 3-20 parts, and A3 comprises 60-94 parts, with the total of A1 and A2 being 6-40 parts. The base compound (B), which includes single or multiple amines such as monoethanolamine or diethanolamine, is used in an amount of 50-95 mol% relative to the sulfonic acid group of monomer A2. Surfactant (C) is included at 0.5-30 parts by mass relative to 100 parts of copolymer (A). Additionally, N,N-dialkyl (meth)acrylamide monomer (A4) can be included in the mixture, comprising 5-50 parts for a total of 100 parts with monomer A3. The copolymer A is shown to possess crosslinked structures formed through condensation reactions of monomer A1, while the neutralized and non-neutralized sulfonic acid groups in monomer A2 enhance the hydrophilicity of the copolymer.该加热固化型防雾涂料组合物含有嵌段共聚物或接枝共聚物，所述嵌段共聚物或接枝共聚物由亲水性聚合物部分与疏水性聚合物部分构成，所述亲水性聚合物部分由具有N-羟甲基、N-羟甲基醚基、羟基中的任一种交联官能团的单体、亲水性单体及（甲基）丙烯酸低级烷基酯形成，所述疏水性聚合物部分由具有磺酸基、羧基或磷酸基的乙烯基类单体及（甲基）丙烯酸低级烷基酯形成。在具有搅拌装置、氮气导入管及冷凝管的反应容器中加入聚合溶剂的正丙醇（240g），以及单体（A1）N-羟甲基丙烯酰胺（10g），单体（A2）2-丙烯酰胺-2-甲基丙磺酸（10g），单体（A3）甲基丙烯酸甲酯（60g）和丙烯酸正丁酯（20g），单体（A4）N,N-二甲基丙烯酰胺（20g），以及碱性化合物（B）三乙醇胺（5.04g）。边吹入氮气边加热至65°C。将自由基聚合引发剂的过氧化新戊酸叔己酯的烃稀释品（1g）溶于40g正丙醇中，然后在3小时内滴入反应容器中。聚合5小时后，将反应容液升温至80°C，在该温度下聚合1小时，得到共聚物浓度为30质量%的溶液。然后在该共聚物溶液中加入NPA和丙二醇单甲醚（400g），使共聚物浓度调整至10质量%；接着加入表面活性剂（C）2-乙基己基磺化琥珀酸钠（10g）和流平剂（0.1g），混合得到防雾涂料组合物。涂饰时，将防雾涂料组合物涂布于基材上，干燥后在60-150°C条件下加热固化5-60分钟，形成涂膜。"
+}
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diff --git a/task2/task2-paper-info/CN104080861B╦с╗Є╤╬╡─╖└╬э═┐▓у░№└и╦о╨╘╛█║╧╬я╖╓╔в╠хбв╜╗┴к╝┴║═╛█╗╖╤ї═щ.json b/task2/task2-paper-info/CN104080861B╦с╗Є╤╬╡─╖└╬э═┐▓у░№└и╦о╨╘╛█║╧╬я╖╓╔в╠хбв╜╗┴к╝┴║═╛█╗╖╤ї═щ.json
new file mode 100644
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+++ b/task2/task2-paper-info/CN104080861B╦с╗Є╤╬╡─╖└╬э═┐▓у░№└и╦о╨╘╛█║╧╬я╖╓╔в╠хбв╜╗┴к╝┴║═╛█╗╖╤ї═щ.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "提供根据权利要求1-18中任一项的涂料组合物;将所述涂料组合物施涂到基底；以及干燥并固化所述涂料组合物。使异氰酸酯与多官能多元醇反应以获得聚氨酯，并且随后使因而制得的聚氨酯与亲水性表面活性剂接触以便使表面活性剂的分子扩散到涂料的内部中。在水性聚氨酯聚合物的制备中，通常通过合适的二醇或多元醇与摩尔过量的二异氰酸酯或聚异氰酸酯在内部乳化剂的存在下反应而形成中等分子量的聚合物（例如预聚物）。内部乳化剂通常为具有离子基团（羧酸盐、磺酸盐或季铵盐）或非离子基团的二醇，诸如聚环氧乙烯。根据聚氨酯主链中所存在的亲水性链段的类型，水性聚氨酯分散体通常为三种类型（即非离子、阳离子和阴离子）之一。就阴离子聚氨酯而言，通常向聚氨酯主链中掺入二羟甲基丙酸（DMPA）。聚合物中DMPA的羧酸根离子为亲水的并用作阴离子中心以及内部乳化剂。水性丙烯酸聚合物还通常用内部乳化剂制备，通常也包含羧酸根离子以稳定分散体并提供固化位点。The synthesis of hydrophilic polymers involves the use of various functional group-containing compounds and crosslinking agents. Specific chemicals such as PZ-28 and PZ-33, which are trifunctional aziridines, are sourced from PolyAziridine, LLC, Medford, NJ. Crosslinking agents are also employed, including XL-706 (a VOC-free trifunctional aziridine from Picassian Polymers), CX-100 (a multifunctional aziridine from Royal DSM, Harleen, Netherlands), and other agents like succinic anhydride from Alfa Aesar, Ward Hill, MA, and ERL-4221 (an alicyclic epoxy resin from Dow Chemicals, Midland, MI). The process may further include the use of various other crosslinking agents such as V-04 (from Nisshinbo Industries, Japan) and BH-305 (from Bayer Materials Science, Leverkusen, Germany), along with tertiary amine from Sigma Aldrich Chemical Company, St. Louis, MO, as a catalyst.1. 将官能硅烷慢慢添加到所选的二氧化硅纳米粒子分散体中，以制备官能硅烷改性的二氧化硅纳米粒子。 2. 确定二氧化硅纳米粒子分散体与官能硅烷的相对量，以确定所需的等同表面覆盖。 3. 在室温下搅拌所得的分散体4小时。 4. 在烘箱中加热至最高65°C，过夜。 5. 在合成多官能氮丙啶交联剂的过程中，在室温下将2-甲基氮丙啶逐滴添加到EM2382或SR-502中并搅拌1小时，然后在60°C下回流24小时。 6. 在真空下移除过量的甲基氮丙啶，得到的产物为浅黄色液体。 7. 在50°C下，将琥珀酸酐加入THF中，反应24小时后在真空下移除THF，得基于PEG的二酸。 8. 将基于PEG的二酸溶解于水中并添加三乙胺搅拌30分钟以形成基于PEG的二羧酸铵盐。 9. 用聚氨酯分散体与900-DA混合，添加交联剂，搅拌并涂覆于基底。 10. 在110-120°C固化20-30分钟。"
+}
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diff --git a/task2/task2-paper-info/CN104926988B.json b/task2/task2-paper-info/CN104926988B.json
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+++ b/task2/task2-paper-info/CN104926988B.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "(1)称取质量比为2:1∼9:1的甲基丙烯酸二甲氨基乙酯和1,3-丙磺酸内酯，向甲基丙烯酸二甲氨基乙酯中加入1,3-丙磺酸内酯，在10∼60°C反应0.5∼4h，经过滤、抽提、干燥制得甲基丙烯酰氧乙基-N, N^-二甲基丙磺酸盐；(2)称取摩尔比为1:1.1∼1:1.3的4-乙烯基吡啶和1,3-丙磺酸内酯，准备有机溶剂和助剂，反应中有机溶剂与4-乙烯基吡啶和1,3-丙磺酸内酯的总质量比为2:1∼8:1，加入助剂后将溶剂分成三份与上述物质混合，得到的三种混合溶液依次加入反应器，在20∼90°C下反应1∼10h，经过滤、洗涤、干燥制得4-乙烯基吡啶丙磺酸内盐；(3)将步骤(1)的甲基丙烯酰氧乙基-N, N^-二甲基丙磺酸盐、丙烯酰胺和步骤(2)的4-乙烯基吡啶丙磺酸盐，按照1.5∼3:6∼7:0.5∼1.5的摩尔比加入溶剂溶解后通入N2除氧0.5∼1h，并升温至50∼70°C，恒温5∼10min后加入引发剂反应4∼6h，得到凝胶状固体，用丙酮沉淀得白色沉淀物；(4)将步骤(3)得到的沉淀物在100∼120°C下干燥16∼24h后粉碎，最终得两性离子共聚物。The text excerpt does not provide any experimental protocol for the synthesis of hydrophilic polymers with functional groups.杨小华采用MAOPS,AM和AA合成两性离子磺酸盐聚合物CPS-2000。杨金荣以氧化还原体系为引发剂,采用水溶液聚合合成了两性离子四元共聚物：聚丙烯酰胺-二甲基二烯丙基氯化铵-2-丙烯酰胺基-2-甲基丙磺酸钠-甲基丙烯酸(PADAM)，郑海洪以丙烯酰胺(AM)、2-丙烯酰胺-2-甲基丙磺酸(AMPS)、二甲基二烯丙基氯化铵(DMDAAC)和顺丁烯二酸酐(MA）为单体，采用水溶液聚合方法，以过硫酸铵/亚硫酸氢钠为引发剂合成了两性离子聚合物降滤失剂PA-1。杨文以二甲基二烯丙基氯化铵(DMDAAC)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、马来酐(MA)、丙烯酰胺(AM）为单体，氧化还原体系为引发剂，利用水溶液聚合法合成了两性离子聚合物降滤失剂PMADA。贺爱民采用水溶液聚合方法合成的AEDMAC/AM/AA两性共聚物降滤失剂。中国专利CN2008100472416以丙烯酰胺2-丙烯酰胺基-2-甲基丙磺酸为单体，采用水溶液聚合合成了一种两性离子聚合物降滤失剂。(1)称取质量比为 2:1∼9:1 的甲基丙烯酸二甲氨基乙酯和1,3-丙磺酸内酯，并向甲基丙烯酸二甲氨基乙酯中加入1,3-丙磺酸内酯，反应在 10∼60°C 的温度下进行 0.5∼4h，最后经过滤、抽提、干燥得到甲基丙烯酰氧乙基-N,N-二甲基丙磺酸盐; (2)按照摩尔比为 1:1.1∼1:1.3 称取4-乙烯基吡啶和1,3-丙磺酸内酯，加入有机溶剂和助剂，有机溶剂与4-乙烯基吡啶和1,3-丙磺酸内酯的质量比为2:1∼8:1，助剂与总质量的比例为 0.001∼0.01，平均分三次混合后，在20°C∼90°C反应 1∼10h，经过滤、洗涤、干燥得到4-乙烯基吡啶丙磺酸内盐; (3)按 1.5∼3:6∼7:0.5∼1.5 的摩尔比称取步骤(1)的产物、丙烯酰胺和步骤(2)得到的4-乙烯基吡啶丙磺酸盐，溶解后通入N2除氧 0.5∼1h，升温至 50∼70°C，恒温 5∼10min 后加入引发剂反应 4∼6h，得到凝胶状固体，丙酮沉淀得白色沉淀; (4)将步骤(3)得到的沉淀物在 100∼120°C 下干燥 16∼24h 后粉碎，最终得到DMAPS-AM-VPPS两性离子共聚物。1. Preparation of DMAPS: Weigh 630g of DMA and place it in a reactor. Heat in a constant temperature water bath and begin stirring. Weigh 122g of PS and directly add it to DMA. The reaction temperature is 35°C, and stir for 1.5 hours to obtain the crude product of DMAPS. Transfer the crude product to filter paper, wrap it, and place it in a Soxhlet extractor using ethanol as the solvent for extraction for 1 hour. After extraction, dry the wrapped filter paper in an oven at 40°C to obtain pure DMAPS monomer with a yield of 92.8%.  \\n\\n2. Preparation of VPPS: Weigh 105g of 4-VP, 125g of PS, 500g of organic solvent (benzene), and 0.75g of diethyl hydroxylamine. Divide the benzene into three equal parts, dissolving each with 4-VP, PS, and diethyl hydroxylamine respectively. Sequentially add the three solutions into the reactor and react at 70°C for 2 hours. After that, perform vacuum filtration, wash with benzene 2-3 times, and dry at 50°C for 15 hours to obtain a pale yellow solid powder product weighing 2136g.  \\n\\n3. Synthesis of DMAPS/AM/VPPS copolymer: Weigh 50g of DMAPS, 60g of AM, and 40g of VPPS; dissolve in a certain amount of deionized water and transfer to a reactor with a total monomer concentration of 35%. Bubble N2 to remove oxygen for 1 hour, heat to 60°C for 30 minutes, then add 0.9g of potassium persulfate. After 6 hours, a gel-like solid is obtained, which is precipitated with acetone to yield a white precipitate. Dry at 110°C for 24 hours, then crush to obtain the DMAPS/AM/VPPS zwitterionic copolymer.  \\n\\n4. Synthesis of DMAPS/AM/VPPS copolymer with NaCl: Weigh 120g of DMAPS, 60g of AM, 34g of VPPS, and 15g of NaCl; dissolve in a certain amount of deionized water and transfer to the reactor with a total monomer concentration of 30%. Bubble N2 to remove oxygen for 1 hour, heat to 55°C for 30 minutes, then add 1.4g of sodium persulfate. After 5 hours, a gel-like solid is obtained, which is precipitated with acetone to yield a white precipitate. Dry at 110°C for 24 hours, then crush to obtain the DMAPS/AM/VPPS zwitterionic copolymer."
+}
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diff --git a/task2/task2-paper-info/CN106574167B╖└╬э╝┴╫щ║╧╬я╝░╩╣╙├╕├╖└╬э╝┴╫щ║╧╬я╡─╖└╬э╨╘▓·╞╖.json b/task2/task2-paper-info/CN106574167B╖└╬э╝┴╫щ║╧╬я╝░╩╣╙├╕├╖└╬э╝┴╫щ║╧╬я╡─╖└╬э╨╘▓·╞╖.json
new file mode 100644
index 0000000..e84bb61
--- /dev/null
+++ b/task2/task2-paper-info/CN106574167B╖└╬э╝┴╫щ║╧╬я╝░╩╣╙├╕├╖└╬э╝┴╫щ║╧╬я╡─╖└╬э╨╘▓·╞╖.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "所述共聚物(A)由相对于100重量份的所述共聚物(A)为 $35{\\sim}90$ 重量份的单体（A-1） $5\\sim60$ 重量份的单体(A-2） $5\\sim30$ 重量份的单体(A-3)构成。所述多官能嵌段异氰酸酯化合物(B)的异氰酸酯基含量NCO与所述共聚物(A)的羟基含量OH之比NCO/OH比为 $0.1{\\sim}1.5$ 的范围。相对于100重量份的所述共聚物(A)，所述表面活性剂(C)含有 $1.00{\\sim}10.0\\$ 重量份的阴离子表面活性剂(C-1)和 $0.01{\\sim}3.00$ 重量份的阳离子表面活性剂(C-2)。The synthesis of hydrophilic polymers involves the following steps: 1) Combine a water-soluble vinyl monomer (monomer A), a non-water-soluble vinyl monomer (monomer B), and a hydroxyl-containing vinyl monomer (monomer C). 2) Introduce a crosslinking agent with isocyanate groups (crosslinking agent D) to facilitate the formation of a network structure. 3) Add a surfactant (surfactant E) to improve anti-fog performance. The proportions and specific conditions for each component should be determined according to the desired properties of the final polymer.使用装有温度计、搅拌装置、氮气导入管及冷却管的反应容器，对作为有机溶剂的213重量份的叔戊醇进行吹氮的同时，加热至80°C。在此反应容器中，经时2小时滴加下列溶液(a)及溶液(b)；溶液(a)为混合有50重量份的N,N-二甲基丙烯酰胺、35重量份的丙烯酸丁酯及15重量份的2-羟基丙烯酸酯的溶液；溶液(b)为在20重量份的叔戊醇中溶解有相当于0.5重量份的过氧化特戊酸叔己酯的溶液。通过直接对滴加溶液(a)及溶液(b)后的反应容器中的溶液搅拌1小时,得到共聚物(A)的溶液。随后，在与可获得防雾膜的持久性相结合的情况下，向100重量份的共聚物(A)中添加100重量份的聚丙二醇单甲基醚、200重量份的双丙酮醇、100重量份的甲基异丁基酮和267重量份的正丁醇，将固含量调增至10.0重量%。作为多官能嵌段异氰酸酯化合物(B)，使用了NCO/OH比相当于1.0的83.5重量份的六亚甲基二异氰酸酯的丙二酸嵌段异氰酸酯体。然后混合上述共聚物(A)、多官能嵌段异氰酸酯化合物(B)、阴离子表面活性剂(C-1)、阳离子表面活性剂(C-2)及流平剂，得到防雾剂组合物。最后，利用喷涂法将防雾剂组合物涂布于聚碳酸酯树脂板并在130°C下保持30分钟加热固化以获得防雾膜。"
+}
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diff --git a/task2/task2-paper-info/CN106977688A-neo-ssq.json b/task2/task2-paper-info/CN106977688A-neo-ssq.json
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+++ b/task2/task2-paper-info/CN106977688A-neo-ssq.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "使用溶胶-凝胶技术以分子作为前驱体，将有机部分和无机部分通过化学键的方式键合在一起制备有机-无机杂化高分子复合材料。选择合适的活性功能型硅倍半氧烷，其中含有乙烯基、烯丙基或(甲基)丙烯酸酯基等活性取代基，与反应对象进行自由基聚合反应，或引入氨基、环氧基、羧基等基团以形成新的杂化分子或实现特定功能。根据反应条件优化水解反应和缩合反应的控制，并确保反应完全，以提高产物的热稳定性和水解稳定性。1) 以有机硅烷和水作为反应物，进行水解和缩合反应，获得作为第一中间体; 2) 选择或者制备第二中间体，所述第二中间体含有能与硅羟基进行封端反应的官能团，并同时具有可聚合或可交联活性有机官能团; 3) 第二中间体对第一中间体进行硅羟基封端反应，生成可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物。第一步：以有机硅烷和水作为反应物，进行水解和缩合反应，所得产物(MASSQ)作为第一中间体; 第二步:等摩尔的丙烯酸羟乙酯(HEA)与异佛尔酮二异氰酸酯(IPDI)发生加合反应,得到单异氰酸酯基的化合物异佛尔酮二异氰酸酯-丙烯酸羟乙酯(IPDI-HEA),即带有能和硅羟基反应的NCO基团以及可聚合的丙烯酸酯基团的第二中间体; 第三步：IPDI-HEA中的NCO基团与MASSQ中的硅羟基的加合反应，获得可聚合或可交联的硅倍半氧烷-聚氨酯及其衍生物(MASSQ-UA)。1) 在一个100mL的三口烧瓶中，称取 40.0g (0.161mol) 3-甲基丙烯酰氧基丙基三甲氧基硅烷(MAPTMS)，安装温度计、机械搅拌器和恒压滴液漏斗；2) 在另一个50mL的烧杯中，称取 8.792g 的0.1mol/L稀盐酸和 14.8g 乙醇，搅拌均匀后转移至恒压滴液漏斗中；3) 在室温下，开始滴加反应物溶液于MAPTMS中，控制滴加速度使其在30分钟内滴加完成；4) 滴加完成后，更换为回流冷凝管，保持机械搅拌，加热至 60°C 并保持4小时，得到无色溶液；5) 将所得溶液倒入一个100mL圆底烧瓶中，减压旋转蒸发，水浴加热至 80°C，真空度达到 0.095MPa，保持4小时，得到第一中间体甲基丙烯酰氧基丙基硅倍半氧烷(MASSQ)。"
+}
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diff --git a/task2/task2-paper-info/CN111303746B_╥╗╓╓╖└╬э═┐┴╧╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json b/task2/task2-paper-info/CN111303746B_╥╗╓╓╖└╬э═┐┴╧╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json
new file mode 100644
index 0000000..cc56376
--- /dev/null
+++ b/task2/task2-paper-info/CN111303746B_╥╗╓╓╖└╬э═┐┴╧╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "将1-20份金纳米粒子、1-40份亲水纳米颗粒、10-30份有机粘合剂和40-90份溶剂依次加入混合，搅拌均匀，即可得到防雾涂料。金纳米粒子的制备方法先将甲基丙烯酸叔丁酯与逆加成-断裂链转移剂在催化剂下反应，生成含二硫酯键的聚合物，然后通过还原反应得到末端含硫醇基团的聚合物，最后加入HAuCl和NaBH，使其还原为Au粒子，聚合物包裹Au粒子形成金纳米粒子。有机粘合剂中应包含环氧基、氨基和羟基中的一种或多种。一种防雾涂料的制备方法，将亲水纳米颗粒、有机粘合剂和金纳米粒子依次加入溶剂中，混合搅拌均匀，即可得到防雾涂料。金纳米粒子的制备方法如下：S1：甲基丙烯酸叔丁酯单体或甲基丙烯酸叔丁酯单体/苯乙烯与逆加成‑断裂链转移剂在催化剂的作用下反应，生成末端含二硫酯键的聚甲基丙烯酸叔丁酯或聚基丙烯酸叔丁酯/聚苯乙烯共聚物；S2：对步骤S1的产物进行还原反应，制备末端含硫醇基团的聚甲基丙烯酸或聚基丙烯酸/聚苯乙烯共聚物；S3：将HAuCl和NaBH放入步骤S1的产物水溶液中，HAuCl被NaBH还原为Au粒子，末端含硫醇基团的聚甲基丙烯酸或聚基丙烯酸/聚苯乙烯共聚物将Au粒子包裹，形成金纳米粒子。1. 将0.5份偶氮二异丁腈、2份2‑(甲氧基碳酰基)‑乙基双硫苯酯和70份甲基丙烯酸叔丁酯单体加入反应釜中，在氮气保护环境下，在70°C温度下反应24h，然后冷却至5°C，得到混合物A；2. 将步骤1中的混合物A溶解在三氯甲烷中，向其中加入0°C的乙醚，搅拌均匀，收集混合溶液中的固体沉淀得到沉淀物B，沉淀物B为末端含二硫酯键的聚甲基丙烯酸叔丁酯；3. 将步骤2中得到的沉淀物B与200份1,4‑二氧六环和20份质量分数为37%的浓盐酸混合，在85°C温度下反应72h，得到混合液；旋蒸去除混合液中的1,4‑二氧六环，然后加入乙醚，搅拌均匀，收集混合液中的固体沉淀得到沉淀物C，沉淀物C为末端含硫醇基团的聚甲基丙烯酸；4. 将步骤3得到的沉淀物C溶于水，配置成质量浓度为1%的溶液，在其中加入10份HAuCl4，搅拌6h后，再加入0.5份NaBH4，在室温下反应0.5h，收集混合液中的沉淀物，即获得金纳米粒子。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/CN113372807B_╥╗╓╓│╓╨°─═─ж▓┴╡─╫╧═т╣т╣╠╗п╖└╬э═┐┴╧╫щ║╧╬я╝░╞ф═┐▓у╡─╓╞▒╕.json b/task2/task2-paper-info/CN113372807B_╥╗╓╓│╓╨°─═─ж▓┴╡─╫╧═т╣т╣╠╗п╖└╬э═┐┴╧╫щ║╧╬я╝░╞ф═┐▓у╡─╓╞▒╕.json
new file mode 100644
index 0000000..c831f9e
--- /dev/null
+++ b/task2/task2-paper-info/CN113372807B_╥╗╓╓│╓╨°─═─ж▓┴╡─╫╧═т╣т╣╠╗п╖└╬э═┐┴╧╫щ║╧╬я╝░╞ф═┐▓у╡─╓╞▒╕.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "将二异氰酸酯和丙烯酸酯混合，溶剂为乙酸乙酯；在 40-60ºC 反应1-2小时后加入脂肪醇聚氧乙烯醚(AEO)继续反应3-4小时后制得；二异氰酸酯、丙烯酸酯及脂肪醇聚氧乙烯醚(AEO)三者投料摩尔比为1-1.3：2-2.4：2-2.2。该涂层通过反复沉积聚二烯丙基二甲基氯化铵和聚苯乙烯磺酸钠制备 $5\\sim20$ 层的双层结构，再通过反复沉积聚二烯丙基二甲基氯化铵和含有粒径为 $10{\\sim}40\\mathrm{nm}$ 的 $\\mathrm{Si0_{2}}$ 球形纳米粒子的悬浮液制备 $3{\\sim}8$ 层的双层结构，再通过 $100{\\sim}140^{\\circ}\\mathrm{C}$ 的水热处理和在 $600{\\sim}800^{\\circ}\\mathrm{C}$ 的马弗炉中淬火 $100{\\sim}300\\mathrm{s}$ 制得所需涂层。将二异氰酸酯和丙烯酸酯混合，溶剂为乙酸乙酯。在 40-60°C 反应1-2小时后加入脂肪醇聚氧乙烯醚(AEO)继续反应3-4小时后制得可光固化丙烯酸亲水树脂。二异氰酸酯、丙烯酸酯及脂肪醇聚氧乙烯醚(AEO)三者投料摩尔比约为1-1.3:2-2.4:2-2.2。将紫外光固化防雾组合物原液涂覆在板材上， 60-80°C 预烘 2-3 min，紫外LED灯光固化30-60s，能量为 500-1000 mJ/cm²，涂覆方式为喷涂、淋涂、滴涂、刮涂或滚涂中的一种。将0.1mol异佛尔酮二异氰酸酯(IPDI)与0.2mol丙烯酸羟乙酯(HEA)混合，溶剂为乙酸乙酯。在40°C反应2小时后加入0.2mol十二醇聚氧乙烯醚继续反应3小时后制得。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/CN113416473A_╥╗╓╓╦л▓у╫╧═т╣т╣╠╗п─═─ж▓┴╖└╬э═┐▓у╝░╓╞▒╕.json b/task2/task2-paper-info/CN113416473A_╥╗╓╓╦л▓у╫╧═т╣т╣╠╗п─═─ж▓┴╖└╬э═┐▓у╝░╓╞▒╕.json
new file mode 100644
index 0000000..8c3a2a2
--- /dev/null
+++ b/task2/task2-paper-info/CN113416473A_╥╗╓╓╦л▓у╫╧═т╣т╣╠╗п─═─ж▓┴╖└╬э═┐▓у╝░╓╞▒╕.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "1. Preparation of original solution A: Accurately weigh each component, mix epoxy acrylate resin and acrylate with solvent, and then add the photoinitiator to obtain the mixture. 2. Preparation of original solution B: Accurately weigh each component, mix photopolymerizable hydrophilic resin, photopolymerizable hydrophilic small molecules, and photopolymerizable hydrophilic salts with solvent for 10-20 minutes, then add the photoinitiator and mix for 0.5-1 hour to obtain the mixture. 3. Applying original solution A on the substrate: pre-bake at 60-80°C for 1-3 minutes, then cure with UV LED light for 20-30 seconds with energy of 400-800 mJ/cm2. 4. Applying original solution B on the substrate: pre-bake at 60-80°C for 1-3 minutes, then cure with UV LED light for 60-120 seconds with energy of 400-800 mJ/cm2.原液A的制备方法为：准确称取各组分，将环氧丙烯酸酯树脂，丙烯酸酯，加入溶剂混合搅拌，再加入光引发剂，混合后制得。原液A的涂覆方式为喷涂、淋涂、滴涂、刮涂或滚涂中的一种。原液A涂层的制备方法为将原液A涂覆在板材上，60-80℃预烘1-3分钟，紫外LED灯光固化20-30s，能量为400-800 mJ/cm²。原液B的制备方法为：准确称取各组分，将光固化亲水树脂，光固化亲水小分子，光固化亲水盐加入溶剂混合搅拌10-20分钟，再加入光引发剂，混合0.5-1h后制得。原液B的涂覆方式和原液A一样，为喷涂、淋涂、滴涂、刮涂或滚涂中的一种。原液B涂层的制备方法为将原液B涂覆在板材上，60-80℃预烘1-3分钟，紫外LED灯光固化60-120s，能量为400-800 mJ/cm²。将1mol甲基丙烯酸缩水甘油酯(GMA)与1.1mol己二酸溶于乙酸乙酯中， $0.05\\mathrm{mol}$ 四丁基溴化铵作为催化剂，加热至 $80^{\\circ}\\mathrm{C}$ 反应6h制得。\\n制备原液A: 一坏氧内烯酸酯树脂70份、0EPA作为内烯酸酯25份和1173作为元引发剂5份；溶剂米用乙酸丁酯：异丙醇：乙醇 $=4:3:3$ (体积比)，总重量是其它组分总重量的0.3倍。准确称取上述组分，将环氧丙烯酸酯树脂和OEPA，加入溶剂混合搅拌10min，再加入光引发剂，混合0.5h后制得。\\n制备原液B: PEG400DA作为光固化亲水树脂60份、丙烯酸作为光固化亲水小分子20份、DNS86作为光固化亲水盐15份、1173作为光引发剂5份；溶剂采用乙酸丁酯：异丙醇：乙醇 $=4:3:3$ (体积比)，总重量是其它组分总重量的1倍。准确称取各组分，将PEG400DA，丙烯酸，DNS86加入溶剂混合搅拌10min，再加入1173，混合0.5h后制得。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/CN113603850B_╥╗╓╓╕▀─═─е╟╫╦о╩ў╓мбв╥╗╓╓╕▀─═─е╬▐╚▄╝┴╖└╬э═┐┴╧╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json b/task2/task2-paper-info/CN113603850B_╥╗╓╓╕▀─═─е╟╫╦о╩ў╓мбв╥╗╓╓╕▀─═─е╬▐╚▄╝┴╖└╬э═┐┴╧╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json
new file mode 100644
index 0000000..f33f5a7
--- /dev/null
+++ b/task2/task2-paper-info/CN113603850B_╥╗╓╓╕▀─═─е╟╫╦о╩ў╓мбв╥╗╓╓╕▀─═─е╬▐╚▄╝┴╖└╬э═┐┴╧╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "1. 将高硬度单体与二乙醇胺按照摩尔比1：1‑1：8反应得到亲水改性的预聚体1。2. 将含羟基的混合物与二异氰酸酯按照羟基(‑OH)与异氰酸酯(‑NCO)摩尔比1：1反应得到部分封端的预聚体2。3. 将预聚体1和预聚体2按照摩尔比1：1‑1：24混合反应生成高耐磨亲水树脂。高硬度单体包括异氰脲酸三丙烯酸酯、双季戊四醇六丙烯酸酯、丙烯酰氧丙基笼型聚倍半硅氧烷、八环氧环己基乙基笼状聚倍半硅氧烷、缩水甘油醚氧丙基笼状聚倍半硅氧烷中的至少一种。含羟基的混合物由亲水表面活性剂和羟基丙烯酸酯单体按照1:1‑1:4的比例混合而成。亲水表面活性剂为非离子的具有聚氧乙烯片段的单羟基聚合物，包括分子量400‑1000的聚乙二醇单甲醚、壬基酚聚氧乙烯醚、辛基酚聚氧乙烯醚中的至少一种。羟基丙烯酸酯单体包括甲基丙烯酸羟乙酯(HEMA)、丙烯酸羟乙酯(HEA)、丙烯酸羟丙酯(HPA)、4‑羟基丁基丙烯酸酯(4HBA)、季戊四醇三丙烯酸酯(PETA)中的至少一种。二异氰酸酯包括异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、六亚甲基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(HMDI)、改性二苯基甲烷二异氰酸酯(液化MDI)中的至少一种。在合成亲水型防雾涂料时，首先选择具有亲水基团的高分子材料作为主要成分。配制包括硬质耐磨材料（如硅烷偶联剂、甲基丙烯酸缩水甘油酯和磺酸基亲水单体）的混合物，随后添加相应比例的助剂和有机溶剂以调节粘度和增强稳定性。使用如正硅酸乙酯和三乙烯四胺作为固化剂，与主链的硅氧烷基及环氧基团反应，以提高交联密度和耐磨性。注意控制各成分的混合与涂布时间，以确保涂层在透明玻璃或塑料基材上的应用效果，同时需关注溶剂的使用对环境的影响，力求无溶剂制备方法以实现绿色可持续发展。首先将高硬度单体与二乙醇胺按照摩尔比1：1‑1：8反应得到亲水改性的预聚体1，然后将含羟基的混合物与二异氰酸酯按照羟基(‑OH)与异氰酸酯(‑NCO)摩尔比1：1反应得到部分封端的预聚体2，最后将预聚体1和预聚体2按照摩尔比1：1‑1：24混合反应而成。实施例1 一、高耐磨亲水树脂的制备： (a) 100mL 的三口烧瓶中加入 8.46g(0.02mol)异氰脲酸三丙烯酸酯和 4.2g (0.04mol)二乙醇胺，开启搅拌并升温至 65°C 反应2h得到亲水改性的预聚体1； (b) 另取100mL的三口烧瓶，加入 17.78g(0.08mol)异佛尔酮二异氰酸酯和 0.021g (0.05wt%)二月桂酸二丁基锡，开启搅拌；再依次称取 0.11g(0.262wt%)对羟基苯甲醚，0.22g(0.525wt%)2,6-二叔丁基-4-甲基苯酚以及 24.0g(0.04mol)聚乙二醇单甲醚600和11.92g(0.04mol)季戊四醇三丙烯酸酯(PETA)，充分混合至完全溶解，转移至恒压滴液漏斗中，在室温下慢慢滴加至上述三口烧瓶中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 60°C 反应直至混合物的异氰酸酯基(-NCO)的含量达到理论值(通过盐酸二正丁胺法测定)，降温得到部分封端的预聚体2，干燥密封保存； (c) 将预聚体1和预聚体2混合，升温至 70°C 反应3h得到官能度为7的高耐磨的亲水性树脂。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/CN113637345B_╥╗╓╓╦о╨╘╗╖▒г─═─е╨═╙╨╗·╬▐╗·╘╙╗п╖└╬э═┐┴╧╝░╞ф╓╞▒╕.json b/task2/task2-paper-info/CN113637345B_╥╗╓╓╦о╨╘╗╖▒г─═─е╨═╙╨╗·╬▐╗·╘╙╗п╖└╬э═┐┴╧╝░╞ф╓╞▒╕.json
new file mode 100644
index 0000000..708c9d6
--- /dev/null
+++ b/task2/task2-paper-info/CN113637345B_╥╗╓╓╦о╨╘╗╖▒г─═─е╨═╙╨╗·╬▐╗·╘╙╗п╖└╬э═┐┴╧╝░╞ф╓╞▒╕.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "本发明提供的水性环保耐磨型有机无机杂化防雾涂料的制备方法包括以下步骤：将水性聚氨酯丙烯酸树脂、TiO2/SiO2杂化微球、活性稀释剂、聚丙烯酰胺、光引发剂、流平剂、助剂、去离子水、乙醇或异丙醇依次加入到容器中进行混合，水浴超声分散，待溶液澄清后用机械搅拌进行二次分散。水性聚氨酯丙烯酸树脂由三步反应制备：第一步是聚丙烯酸酯的制备，第二步是聚氨酯树脂预聚体的制备，第三步是水性聚氨酯丙烯酸树脂的制备。聚丙烯酸酯的制备采用不同比例的甲基丙烯酸甲酯、丙烯酸、苯乙烯、丙烯酸羟乙酯作为单体，以及偶氮二异丁腈作为引发剂，在60~80°C条件下反应8~10小时。聚氨酯树脂预聚体的制备采用聚醚多元醇和异佛尔酮二异氰酸酯。水性聚氨酯丙烯酸树脂的制备是在聚氨酯树脂预聚体中加入聚丙烯酸酯，并在60~80°C继续反应5~6小时。将水性聚氨酯丙烯酸树脂、TiO2/SiO2杂化微球、活性稀释剂、聚丙烯酰胺、光引发剂、流平剂、助剂、去离子水、乙醇或异丙醇依次加入到容器中进行混合，水浴超声分散，待溶液澄清后再二次分散。聚丙烯酸酯(PAA)的制备，采用不同比例的单体(MMA，AA，St，HEA)以及引发剂偶氮二异丁腈(AIBN)，在60~80°C条件下反应8~10小时。聚氨酯树脂预聚体(PUA)的制备，采用聚醚多元醇和异佛尔酮二异氰酸酯制得，二者官能团摩尔比为(-NCO：-OH为2：1)。将一定量的PAA加入到PUA中，在60~80°C条件下继续反应5~6小时。TiO2/SiO2杂化微球的制备，首先将TBT/TEOS：H2O：Et‑OH的质量比为1~2:3~8:3~8，反应条件为温度50~80°C，反应时间3~5小时，随后加入KH‑570、KH‑560、HEA或MTMS进行搅拌3~5小时。调节pH值于6.8~7.2之间进行保存。光引发剂为184D，MBF，TPO，1173D中的至少一种。预烘温度为75~85°C，预烘时间为5~15分钟，固化能量为40000~60000mJ/cm²。将上述原料依次加入 200ml 的烧杯中，在 50°C 水浴中超声15min，待溶液澄清后继续用机械搅拌进行二次分散，待分散均匀后转移到棕色遮光瓶中进行储存。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/CN113667393B_╥╗╓╓╖└╤г╣т╨═╙╨╗·╬▐╗·╘╙╗п╖└╬э═┐┴╧╝░╞ф╓╞▒╕.json b/task2/task2-paper-info/CN113667393B_╥╗╓╓╖└╤г╣т╨═╙╨╗·╬▐╗·╘╙╗п╖└╬э═┐┴╧╝░╞ф╓╞▒╕.json
new file mode 100644
index 0000000..4ee5610
--- /dev/null
+++ b/task2/task2-paper-info/CN113667393B_╥╗╓╓╖└╤г╣т╨═╙╨╗·╬▐╗·╘╙╗п╖└╬э═┐┴╧╝░╞ф╓╞▒╕.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "将水性聚氨酯丙烯酸树脂、Ti02@Si02杂化/PS微球或TiO2@SiO2杂化/PMMA微球、活性稀释剂、光引发剂、流平剂、助剂、以及乙醇或异丙醇依次加入到容器中进行混合，水浴超声分散，待溶液澄清后再二次分散。所述Ti02@Si02杂化/PS微球或TiO2@SiO2杂化/PMMA微球采用原位聚合法制备，具体步骤如下：1) 钛酸四丁酯(TBT)/正硅酸乙 ester(TEOS)：H2O：无水乙醇的质量比为1:3:3； 2) 采用表面活性剂十二烷基苯磺酸钠(SDBS)、十二烷基磺酸钠(SDS)或十六烷基三甲基溴化铵(CTAB)进行预乳化； 3) 边搅拌边滴加反应单体及丙烯酸的混合物，反应单体与丙烯酸的物质的量比为8:1； 4) 在60-80°C下继续反应1-2h，得到TiO2@SiO2杂化/PS微球或TiO2@SiO2杂化/PMMA微球。1) 钛酸四丁酯(TBT)/正硅酸乙酯(TEOS)：H2O:Et-OH (无水乙醇)的质量比为 1~2 : 3~8:3~8，其中TBT/TEOS摩尔比为 0.98~0.8，pH值为 2~3.5，搅拌速率为 2000~3000rpm，反应温度为 50~80°C，反应时间为 3~5h，得到 TiO2@SiO2 杂化纳米微球；2) 采用表面活性剂十二烷基苯磺酸钠(SDBS)、十二烷基磺酸钠(SDS)或十六烷基三甲基溴化铵(CTAB)对TiO2@SiO2杂化纳米微球进行预乳化；3) 边搅拌边滴加反应单体苯乙烯、丙烯酸及其衍生物和引发剂过硫酸铵的混合物，其中苯乙烯与丙烯酸及其衍生物质量比为 8~12:1；4) 滴加完后在 60~80°C 下继续反应 1~2h 后结束反应，得到 TiO2@SiO2 杂化/PS微球，所述丙烯酸及其衍生物为丙烯酸或甲基丙烯酸或丙烯酰胺中的至少一种。1) TBT/TEOS: H2O:Et‑OH (无水乙醇) 的质量比为1:3:3，其中TBT/TEOS摩尔比为0.98，pH值为2，搅拌速率为 2000rpm，反应温度为 50°C，反应时间为 3∼5h; 2) 采用表面活性剂 5% 的十二烷基苯磺酸钠(SDBS)对 TiO2/SiO2 杂化纳米微球进行预乳化; 3) 边搅拌边滴加反应单体苯乙烯、丙烯酸和占总质量 2% 的催化剂过硫酸铵的混合物，其中甲基丙烯酸甲酯与丙烯酸物质的量比为8:1; 4) 滴加完后在 60°C 下继续反应2h后结束反应，得到 TiO2/SiO2 杂化/PS纳米微球。在固化膜表面滴2.5uL的超纯水，在室温下采用接触角测量仪进行测试。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/CN113930121B╗∙╙┌┴╜╟╫╨╘╣▓╛█╬я╡─╖└╬э═┐▓у╫щ║╧╬я╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json b/task2/task2-paper-info/CN113930121B╗∙╙┌┴╜╟╫╨╘╣▓╛█╬я╡─╖└╬э═┐▓у╫щ║╧╬я╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json
new file mode 100644
index 0000000..08a9d13
--- /dev/null
+++ b/task2/task2-paper-info/CN113930121B╗∙╙┌┴╜╟╫╨╘╣▓╛█╬я╡─╖└╬э═┐▓у╫щ║╧╬я╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "将单体 A1、单体 A2、单体 A3、单体 A4、单体 A5、引发剂、碱性化合物加入到溶剂中，在温度为 50~95°C 的条件下反应 3~24h 得到两亲性共聚物；将交联剂、表面活性剂、流平剂、溶剂加入到制得的两亲性共聚物中，在室温条件下搅拌混合，制得基于两亲性共聚物的防雾涂层组合物。按照上述的基于两亲性共聚物的防雾涂层组合物组分进行备料，将单体 A1、单体 A2、单体 A3、单体 A4、单体 A5、引发剂、碱性化合物加入到溶剂中，在温度为 50∼95°C 的条件下反应 3∼24h 得到两亲性共聚物；将交联剂、表面活性剂、流平剂加入到制得的两亲性共聚物中，在室温条件下搅拌混合，制得基于两亲性共聚物的防雾涂层组合物。步骤一，两亲性共聚物的制备，向500mL玻璃三口烧瓶反应容器中加入作为溶剂的100g异丙醇、作为单体A的30g的N‑乙烯基‑2‑吡咯烷酮、作为单体A2的20g丙烯酸羟乙 Ester、作为单体A3的30g甲基丙烯酸甲酯、作为单体A4的18g的N,N-二甲基丙烯酸胺、作为单体A5的1g的2‑丙烯酰胺‑2‑甲基丙磺酸、作为碱性化合物的0.2g吡啶，在磁力搅拌下升温加热至55°C，然后将作为溶液自由基聚合引发剂的1g偶氮二异丁腈加入三口瓶反应器中，将水浴锅温度升高至75°C继续反应10小时，得到200.2g质量浓度为50%的两亲性共聚物溶液。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/CN114213963B_╥╗╓╓╣т-╚╚╦л╓╪╣╠╗п╬▐╚▄╝┴─═─е╖└╬э═┐┴╧╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json b/task2/task2-paper-info/CN114213963B_╥╗╓╓╣т-╚╚╦л╓╪╣╠╗п╬▐╚▄╝┴─═─е╖└╬э═┐┴╧╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json
new file mode 100644
index 0000000..cae5ee4
--- /dev/null
+++ b/task2/task2-paper-info/CN114213963B_╥╗╓╓╣т-╚╚╦л╓╪╣╠╗п╬▐╚▄╝┴─═─е╖└╬э═┐┴╧╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "在容器内加入所述稀释单体，在搅拌状态下依次加入光引发剂、光‑热双固化树脂并搅拌溶解，再依次加入流平剂并搅拌，加入固化剂并搅拌均匀即得所述防雾涂料；其中，所述光‑热双固化树脂由二异氰酸酯与醇1反应得到预聚体1，再与醇2反应得到超支化树脂，将羟基丙烯酸酯单体与二异氰酸酯反应得到部分封端的预聚体2，最后将超支化树脂与预聚体2混合反应，得到光‑热双固化树脂；所述固化剂为热固型异氰酸酯固化剂，能够与光‑热双固化树脂中的羟基发生交联反应。亲水防雾涂料的合成包括以下步骤：首先，以具有亲水基团的高分子材料为主要成分，按相应比例添加稀释剂和其他助剂进行调配。根据固化方式，可以选择热固化或UV光固化。在热固化法中，需要将涂料体系加热至超过100℃以实现固化；而在UV光固化法中，涂料在紫外光照射下进行瞬间固化。为提高防雾和耐磨性，可以采用光‑热双重固化方法，结合使用亲水无机纳米粒子。将光‑热双固化树脂30‑70份、稀释单体20‑40份、固化剂5‑15份、光引发剂3‑5份，流平剂0.5‑1.0份分散混合，即可得到所述防雾涂料；具体包括以下步骤：在容器内加入所述活性稀释剂，在搅拌状态下依次加入光引发剂、光‑热双固化树脂并搅拌溶解，流平剂并搅拌，固化剂并搅拌均匀即得所述防雾涂料。250mL的三口烧瓶中加入44.46g (0.2mol) 异佛尔酮二异氰酸酯和0.09g (0.1wt%) 二月桂酸二丁基锡开启搅拌；另称取2.36g (0.02mol) 1,6-己二醇和32.0g (0.08mol) 聚乙二醇400，充分混合至完全溶解，转移至恒压滴液漏斗中，在室温下缓慢滴加至上述三口烧瓶中，滴完继续室温反应30min后，升温至70°C反应直至混合物的异氰酸酯基(-NCO)的含量达到理论值，得到亲水改性的预聚体1；然后加入26.83g (0.2mol) 三羟甲基丙烷继续反应直至异氰酸酯基(-NCO)的含量为零，得到超支化树脂。另取250mL三口烧瓶，向其加入11.11g (0.05mol) 异佛尔酮二异氰酸酯和0.016g (0.1wt%) 二月桂酸二丁基锡开启搅拌；另依次称取0.044g (0.262wt%) 对羟基苯甲醚，0.088g (0.525wt%) 2,6-二叔丁基-4-甲基苯酚以及5.8g (0.05mol) 丙烯酸羟乙酯，充分混合至完全溶解，转移至恒压滴液漏斗中，在室温下缓慢滴加至上述三口烧瓶中，滴完继续室温反应30min后，升温至70°C反应直至混合物的异氰酸酯基(-NCO)的含量达到理论值，降温得到预聚体2，加入上述超支化树脂继续反应直至异氰酸酯基(-NCO)的含量为零，得到光-热双固化树脂，干燥密封保存。"
+}
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diff --git a/task2/task2-paper-info/CN114829509A╚╒▒╛-╖└╬э═┐▓у╫щ║╧╬ябв╖└╬э═┐─д╝░╖└╬э╓╞╞╖.json b/task2/task2-paper-info/CN114829509A╚╒▒╛-╖└╬э═┐▓у╫щ║╧╬ябв╖└╬э═┐─д╝░╖└╬э╓╞╞╖.json
new file mode 100644
index 0000000..feab858
--- /dev/null
+++ b/task2/task2-paper-info/CN114829509A╚╒▒╛-╖└╬э═┐▓у╫щ║╧╬ябв╖└╬э═┐─д╝░╖└╬э╓╞╞╖.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "首先准备酸性长条状胶体氧化硅(ST-OUP，固体成分15%，水分散液)48.93重量份、碱性长条状胶体氧化硅(ST-UP，固体成分20%，水分散液)12.23重量份、碱性球状胶体氧化硅(ST-N，固体成分20%，水分散液)10.49重量份、碱性球状胶体氧化硅(ST-NXS，固体成分15%，水分散液)13.98重量份、表面活性剂(FT-150，氟系阴离子系表面活性剂)0.03重量份、及有机溶剂(丙二醇单甲醚)14.34重量份，加以混合而制作防雾涂料组合物。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/CN114957645B_╥╗╓╓╙├╙┌ABS╗∙▓─╡─╣т╣╠╗п│м╟╫╦о═┐┴╧╫щ║╧╬я╝░╞ф═┐▓у╡─╓╞▒╕╖╜╖и.json b/task2/task2-paper-info/CN114957645B_╥╗╓╓╙├╙┌ABS╗∙▓─╡─╣т╣╠╗п│м╟╫╦о═┐┴╧╫щ║╧╬я╝░╞ф═┐▓у╡─╓╞▒╕╖╜╖и.json
new file mode 100644
index 0000000..4e54751
--- /dev/null
+++ b/task2/task2-paper-info/CN114957645B_╥╗╓╓╙├╙┌ABS╗∙▓─╡─╣т╣╠╗п│м╟╫╦о═┐┴╧╫щ║╧╬я╝░╞ф═┐▓у╡─╓╞▒╕╖╜╖и.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "1) 三羟甲基丙烷在强碱作用下与环氧丙烷开环加成，80~120°C 下反应 3~6h，三羟基甲基丙烷与环氧丙烷的摩尔比为 1:3~1:7; 2) 将步骤1)的产物与丙烯酸在 60~80°C 下进行酯化反应 3~6h，对甲苯磺酸作为催化剂，二者摩尔比为 1:1~1:1.5，得到含聚乙二醇链段的乙氧化三羟甲基丙烯酸酯; 3) 将光固化超亲水涂料组合物涂覆在ABS基材上，60-80°C 预烘 2-3min，紫外LED灯光固化30-60s，能量为 500-1000mJ/cm²。该制备方法包括以下步骤：1. 准备所需的ABS基材；2. 将光固化树脂与增稠剂混合，形成均匀的涂料；3. 添加功能团改性剂，提升涂料的超亲水性；4. 将混合物均匀涂布于ABS基材表面；5. 通过紫外光照射固化涂层，得到超亲水涂层。The article does not provide a specific experimental protocol for the synthesis of hydrophilic polymers with functional groups.1) 三羟甲基丙烷在强碱作用下与环氧丙烷开环加成， $80\\sim120^{\\circ}\\mathrm{C}$ 下反应 $3\\sim6\\mathrm{h}$ ，三羟基甲基丙烷与环氧丙烷的摩尔比为 $1{:}3\\sim1{:}7$ ； 2) 将步骤1)的产物与丙烯酸在 $60\\sim80^{\\circ}\\mathrm{C}$ 下进行酯化反应 $3\\sim6\\mathrm{h}$ ，对甲苯磺酸作为催化剂，二者摩尔比为1 $:1\\sim1:1.5$ ，得到含聚乙二醇链段的乙氧化三羟甲基丙烷三丙烯酸酯。1) 聚醚胺(ED2003)与三(2‑羟乙基)异氰脲酸三丙烯酸酯(THEICTA)在 $60-80^{\\circ}\\mathrm{C}$ 下进行加成反应，二者摩尔比为1：2； 2) 羟乙基丙烯酸酯(HEA)与异佛尔酮二异氰酸酯(IPDI)在 $30-50^{\\circ}\\mathrm{C}$ 下反应 $0.5\\sim$ 1h，二者摩尔比为1：1； 3) 将步骤1)和步骤2)所得产物在 $30-50^{\\circ}\\mathrm{C}$ 下进行聚合反应，反应 $0.5\\sim1\\mathrm{h}$ 。在150ml反应瓶中投入1mol三羟甲基丙烷与3mol环氧丙烷，加入0.05mol NaOH，80°C下反应3h后加入1mol丙烯酸以及0.01mol对甲苯磺酸，60°C下反应3h。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/CN115028830B_╥╗╓╓╙├╙┌╖└╬э═┐▓у╡─╟╫╦о╩ў╓м╝░╞ф╓╞▒╕╖╜╖и.json b/task2/task2-paper-info/CN115028830B_╥╗╓╓╙├╙┌╖└╬э═┐▓у╡─╟╫╦о╩ў╓м╝░╞ф╓╞▒╕╖╜╖и.json
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index 0000000..ddec3d6
--- /dev/null
+++ b/task2/task2-paper-info/CN115028830B_╥╗╓╓╙├╙┌╖└╬э═┐▓у╡─╟╫╦о╩ў╓м╝░╞ф╓╞▒╕╖╜╖и.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "制备多官能度亲水性紫外光固化树脂，通过迈克尔加成接枝甲氧基聚乙二醇丙烯酸酯，结合低聚物亲水树脂以实现防雾功能衰退速度较慢的超亲水涂层。使用亲水树脂和单体中的PEG(EO)n，乙氧化双酚A(EO)n二丙烯酸酯及三羟甲基丙烷(EO)n三丙烯酸酯，和附着力树脂及单体如DSMAgiSynTM 2421、1,6‑己二醇二丙烯酸酯(HDDA)。如果混合后的黏度较大，添加单组份溶剂或混合溶剂进行稀释。1) Dissolve 2-acrylamido-2-methylpropanesulfonic acid in a liquid monomer with active double bonds and neutralize it with organic tertiary amine to obtain intermediate product 1; 2) Add linear hydrophilic polyether amine to intermediate product 1 and react at 40-80°C for 2-8 hours to obtain intermediate product 2; 3) Add multifunctional monomer to intermediate product 2 and react at 40-80°C for 2-8 hours to obtain the hydrophilic resin for anti-fog coating.1) 2‑丙烯酰胺基‑2‑甲基丙磺酸(AMPS)溶解于等摩尔的丙烯酰吗啉(ACMO)中，并用等摩尔量的三乙胺中和，得到中间产物1； 2) 选用直链亲水聚醚胺ED2003，按照摩尔比为聚醚胺：中间产物1=1：2的比例投料，在40°C下反应8h，得到中间产物2； 3) 中间产物2再与1，6‑己二醇二丙烯酸酯(HDDA)、季戊四醇三丙烯酸酯(PETA)、聚乙二醇200二丙烯酸酯(PEG200DA)三种的混合物，按照摩尔比为中间产物2：多官能单体=1：2的比例投料，在80°C下反应8h，得到用于防雾的亲水树脂。"
+}
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diff --git a/task2/task2-paper-info/CN115044008B_╥╗╓╓╟╫╦о╨═╤Ї└ы╫╙╣т╣╠╗п╩ў╓м╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json b/task2/task2-paper-info/CN115044008B_╥╗╓╓╟╫╦о╨═╤Ї└ы╫╙╣т╣╠╗п╩ў╓м╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json
new file mode 100644
index 0000000..0f02f3e
--- /dev/null
+++ b/task2/task2-paper-info/CN115044008B_╥╗╓╓╟╫╦о╨═╤Ї└ы╫╙╣т╣╠╗п╩ў╓м╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "1) 二异氰酸酯与带羟基的氧杂环丁烷反应得到端NCO的半封端预聚体，其中二异氰酸酯的异氰酸酯基(‑NCO)和氧杂环丁烷的羟基(‑OH)的摩尔比2:1；2) 二元聚醚胺与聚乙二醇二丙烯酸酯在室温下进行迈克尔加成反应，得到丙烯酸酯基封端的亲水聚合物中间体1，其中二元聚醚胺与聚乙二醇二丙烯酸酯的摩尔比为1:2‑4:5；3) 氨基磺酸盐与中间体1中的丙烯酸酯基在室温下进行迈克尔加成反应得到中间体2，其中氨基磺酸盐与中间体1的摩尔比为2:1，氨基磺酸盐事先用去离子水配置成溶液，质量分数为50%-80%；4) 将步骤1中端NCO的半封端预聚体和中间体2按照异氰酸酯基(‑NCO)与仲胺(‑NH‑)摩尔比1:1反应得到亲水型阳离子光固化树脂。The synthesis of hydrophilic cationic photocurable resin involves the following steps: 1. Combine a hydrophilic monomer with functional groups, such as hydroxyl or amino groups, with a suitable photoinitiator and a reactive diluent. 2. Heat the mixture to a specified temperature to ensure complete dissolution and mixing of the components. 3. Allow the mixture to cool down to room temperature. 4. Conduct photopolymerization under UV light irradiation for a designated period to achieve crosslinking and solidify the resin. 5. Finally, characterize the resultant polymer using spectroscopy and mechanical testing to evaluate its properties.The document does not provide a specific experimental protocol for the synthesis of hydrophilic polymers with functional groups.阳离子光固化树脂的合成方法包括引入功能基团以提高耐水性和附着力。合成过程中，采用UV光照射以促进自由基的生成，引发聚合反应，形成具有超亲水性能的树脂。在实验中，应控制光固化的时间与引发剂的用量，以优化固化效果和树脂性能，同时注意避免氧阻聚对反应的影响。此外，确保原料的配比和反应条件，以实现良好的机械性能和长期的亲水性。1) 二异氰酸酯与带羟基的氧杂环丁烷反应得到端NCO的半封端预聚体，其中二异氰酸酯的异氰酸酯基(‑NCO)和氧杂环丁烷的羟基(‑OH)的摩尔比2:1； 2) 二元聚醚胺与聚乙二醇二丙烯酸酯在室温下进行迈克尔加成反应，得到丙烯酸酯基封端的亲水聚合物中间体1，其中二元聚醚胺与聚乙二醇二丙烯酸酯的摩尔比为1:24:5； 3) 氨基磺酸盐与中间体1中的丙烯酸酯基在室温下进行迈克尔加成反应得到中间体2，其中氨基磺酸盐与中间体1的摩尔比为2:1，氨基磺酸盐事先用去离子水配置成溶液，质量分数为50%-80%； 4) 将步骤1中端NCO的半封端预聚体和中间体2按照异氰酸酯基(‑NCO)与仲胺(‑NH‑)摩尔比1:1反应得到亲水型阳离子光固化树脂。步骤1) 向反应釜a 中加入 444.6g(2.0mol) 异佛尔酮二异氰酸酯和 0.06g(0.01wt%)二月桂酸二丁基锡开启搅拌；将 204.2g(2.0mol)3·-甲基‑3‑羟甲基氧杂环丁烷加入恒压滴液槽中，在室温下缓慢滴加至上述反应釜中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至 70{^\\circC}反应直至混合物的异氰酸酯基(-NCO)的含量达到理论值(通过盐酸二正丁胺法测定)，得到半封端的预聚体； 步骤2)向反应釜b中加入 450g(0.5mol) 聚醚胺ED900开启搅拌，将 381g(0.75mol)PEG400DA加入恒压滴液槽中，室温条件下缓慢滴加至上述反应釜中，滴完维持室温继续反应2h得到丙烯酸酯基封端的亲水聚合物中间体1，其中二元聚醚胺与聚乙二醇二丙烯酸酯的摩尔比为2:3； 步骤3)用 70g 去离子水将 95.0g(0.5mol) 乙二胺基乙磺酸钠溶解均匀后转移至恒压滴液槽中，室温条件下缓慢滴加至反应釜b中，滴完维持室温继续反应2h后，升温至 50^{\\circ}C反应2h得到中间体2； 步骤4)将步骤1中的预聚体转移到反应釜b的恒压滴液槽中，冰水浴条件下缓慢滴加至反应釜b中，滴完继续室温反应30min后，升至室温反应直至混合物的异氰酸酯基(-NCO)的含量为零，得到亲水型阳离子光固化树脂，避光保存。"
+}
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diff --git a/task2/task2-paper-info/CN115044012B_╥╗╓╓╟╫╦о╨═╣т╣╠╗п╩ў╓м╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json b/task2/task2-paper-info/CN115044012B_╥╗╓╓╟╫╦о╨═╣т╣╠╗п╩ў╓м╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json
new file mode 100644
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--- /dev/null
+++ b/task2/task2-paper-info/CN115044012B_╥╗╓╓╟╫╦о╨═╣т╣╠╗п╩ў╓м╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "1) 反应二异氰酸酯与羟基丙烯酸酯，摩尔比2:1，得到端NCO的半封端预聚体； 2) 在室温下进行迈克尔加成反应，将二元聚醚胺与聚乙二醇二丙烯酸酯（摩尔比1:2-4:5）混合，得到丙烯酸酯基封端的亲水聚合物中间体1； 3) 将氨基磺酸盐溶解在去离子水中（质量分数50%-80%），慢慢滴加至中间体1（摩尔比2:1），在室温下反应2-3小时，升温至40-50°C反应2小时，得到中间体2； 4) 将步骤1的半封端预聚体与中间体2（摩尔比1:1）反应，得到亲水型光固化树脂，避光保存。The specific experimental protocol for the synthesis of hydrophilic polymers with functional groups was not provided in the text excerpt.UV光固化型亲水树脂的合成采用紫外光固化方法，能够实现瞬间固化，非常适合连续工业化生产。1) 二异氰酸酯与羟基丙烯酸酯反应得到端NCO的半封端预聚体，其中二异氰酸酯的异氰酸酯基(‑NCO)和丙烯酸酯的羟基(‑OH)的摩尔比2:1； 2) 二元聚醚胺与聚乙二醇二丙烯酸酯在室温下进行迈克尔加成反应，得到丙烯酸酯基封端的亲水聚合物中间体1，其中二元聚醚胺与聚乙二醇二丙烯酸酯的摩尔比为1:24:5； 3) 氨基磺酸盐与中间体1中的丙烯酸酯基在室温下进行迈克尔加成反应得到中间体2，其中氨基磺酸盐与中间体1的摩尔比为2:1，氨基磺酸盐事先用去离子水配置成溶液，质量分数为50%-80%； 4) 将步骤1中端NCO的半封端预聚体和中间体2按照异氰酸酯基(‑NCO)与仲胺(‑NH‑)摩尔比1:1反应得到亲水型光固化树脂。制备亲水型光固化树脂的过程中还额外添加了二月桂酸二丁基锡DBTDL，该反应使用异佛尔酮二异氰酸酯和丙烯酸羟乙酯进行反应。步骤1: 加入异佛尔酮二异氰酸酯和催化剂，随后慢速加入丙烯酸羟乙酯并在室温反应30分钟，升温至70°C反应；步骤2: 向反应釜b中加入聚醚胺，慢速加入PEG400DA，室温反应2小时，得到亲水聚合物中间体1；步骤3: 溶解乙二胺基乙磺酸钠于去离子水中，并加入反应釜b，室温反应2小时后升温至50°C反应2小时，得到中间体2；步骤4: 将预聚体转移到反应釜b并在冰水浴条件下添加，继续在室温反应直至异氰酸酯基含量为零，得到亲水型光固化树脂，避光保存。"
+}
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diff --git a/task2/task2-paper-info/CN115521452B_╥╗╓╓╣т╣╠╗п╡═╛█╬ябв╞ф╓╞▒╕╖╜╖и╝░║м╙╨╕├╡═╛█╬я╡─╣т╣╠╗п═┐┴╧.json b/task2/task2-paper-info/CN115521452B_╥╗╓╓╣т╣╠╗п╡═╛█╬ябв╞ф╓╞▒╕╖╜╖и╝░║м╙╨╕├╡═╛█╬я╡─╣т╣╠╗п═┐┴╧.json
new file mode 100644
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+++ b/task2/task2-paper-info/CN115521452B_╥╗╓╓╣т╣╠╗п╡═╛█╬ябв╞ф╓╞▒╕╖╜╖и╝░║м╙╨╕├╡═╛█╬я╡─╣т╣╠╗п═┐┴╧.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "(1) 聚醚胺与三(2‑羟乙基)异氰脲酸三丙烯酸酯在 60-80°C 下进行加成反应，得到异氰尿酸聚醚胺丙烯酸酯；(2) 羟乙基丙烯酸酯与异佛尔酮二异氰酸酯在 30-50°C 下反应0.5‑1h，得到脲基丙烯酸酯；(3) 将步骤(1)和步骤(2)所得产物在 30-50°C 下进行聚合反应，反应0.5‑1h，即得到所述光固化低聚物，命名为异氰尿酸聚氧乙烯醚丙烯酸酯。(1) 聚醚胺(ED2003)与三(2‑羟乙基)异氰脲酸三丙烯酸酯(THEICTA)在 60-80°C 下进行加成反应，得到聚氧乙烯醚异氰尿酸丙烯酸酯；(2) 羟乙基丙烯酸酯(HEA)与异佛尔酮二异氰酸酯(IPDI)在 30-50°C 下反应0.5‑1h，得到脲基丙烯酸酯；(3) 将步骤(1)和步骤(2)所得产物在 30-50°C 下进行聚合反应，反应0.5‑1h，即得到所述光固化低聚物。将1mol聚醚胺(ED2003)与2mol三(2‑羟乙基)异氰脲酸三丙烯酸酯(THEICTA)在60℃下反应4h，将1mol羟乙基丙烯酸酯(HEA)与1mol异佛尔酮二异氰酸酯(IPDI)在30℃下反应0.5h，将两步反应所得产物在30℃下反应0.5h得到光固化低聚物B。"
+}
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diff --git a/task2/task2-paper-info/CN116023849B_╥╗╓╓╖└╬э═┐┴╧╝░╞ф╓╞▒╕╖╜╖ибв╖└╬э═┐▓у.json b/task2/task2-paper-info/CN116023849B_╥╗╓╓╖└╬э═┐┴╧╝░╞ф╓╞▒╕╖╜╖ибв╖└╬э═┐▓у.json
new file mode 100644
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--- /dev/null
+++ b/task2/task2-paper-info/CN116023849B_╥╗╓╓╖└╬э═┐┴╧╝░╞ф╓╞▒╕╖╜╖ибв╖└╬э═┐▓у.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "将多元醇A和二异氰酸酯混合，加入溶剂，加热反应，得到亲水聚合物，向亲水聚合物中加入多元醇B混合均匀，得到亲水组分A；所述多元醇A选用异山梨醇、吐温20、吐温60、吐温80、甘油、甘油聚醚‑18、甘油聚醚‑26中的任一种或多种的混合；所述多元醇B选用吐温20、吐温60、吐温80、甘油、甘油聚醚‑18、甘油聚醚‑26中的任一种或两种的混合；将聚醚胺与甲基丙烯酰胺类化合物混合进行加成反应，得到含有多个活泼N‑异丁氧基和/或N‑正丁氧基的亲水组分B；所述甲基丙烯酰胺类化合物选用N‑(异丁氧基)甲基丙烯酰胺或N‑(正丁氧基)甲基丙烯酰胺中的任一种或两种的混合；将亲水组分A和亲水组分B混合，即得到防雾涂料；所述亲水组分A中的羟基与亲水组分B中的N‑异丁氧基和/或N‑正丁氧基的摩尔比为1.2:1.5; 其中，亲水组分A中的羟基含量为亲水聚合物中的羟基含量和多元醇B中的羟基含量的总和。The hydrophilic polymer is prepared using monomers with crosslinking functional groups. The polymer should have a large molecular weight and lower reactivity of functional groups on the molecular chain. The polymer must be cured at a temperature between 100 to 120 degrees Celsius for 1 to 2 hours.步骤S101，将多元醇A和二异氰酸酯混合，加入溶剂，加热反应，得到亲水聚合物，待亲水聚合物的温度降至小于 40^{\\circ}C 后，向亲水聚合物中加入多元醇B混合均匀，得到亲水组分A；步骤S102，将聚醚胺与甲基丙烯酰胺类化合物混合进行加成反应，得到含有多个活泼N‑异丁氧基和/或N‑正丁氧基的亲水组分B；步骤S103，将亲水组分A和亲水组分B混合，即得到防雾涂料。步骤S101，将多元醇A和二异氰酸酯按照摩尔比2:1混合，加入二丙酮醇，于80~85 °C反应4~8h至NCO完全被消耗，得到亲水聚合物，待亲水聚合物的温度降至小于40 °C后，向亲水聚合物中加入多元醇B混合均匀，得到亲水组分A；步骤S102，将聚醚胺与甲基丙烯酰胺类化合物按照摩尔比1:4混合，在30~80 °C下进行迈克尔加成反应2~8h，得到含有多个活泼N‑异丁氧基和/或N‑正丁氧基的亲水组分B；步骤S103，将亲水组分A和亲水组分B混合，即得到防雾涂料；亲水组分A中的羟基与亲水组分B中的丁氧基的摩尔比为1.2~1.5:1。"
+}
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diff --git a/task2/task2-paper-info/CN116023854B_╥╗╓╓╕▀╙▓╢╚─═─ж▓┴╖└╬э═┐┴╧╝░╓╞▒╕╖╜╖и.json b/task2/task2-paper-info/CN116023854B_╥╗╓╓╕▀╙▓╢╚─═─ж▓┴╖└╬э═┐┴╧╝░╓╞▒╕╖╜╖и.json
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+++ b/task2/task2-paper-info/CN116023854B_╥╗╓╓╕▀╙▓╢╚─═─ж▓┴╖└╬э═┐┴╧╝░╓╞▒╕╖╜╖и.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "步骤一，按质量份称取亲水环状聚硅氧烷、聚硅氮烷、固化剂、流平剂、溶剂；步骤二，在容器中加入溶剂，然后在搅拌状态下依次加入亲水环状聚硅氧烷、聚硅氮烷、流平剂和固化剂混合均匀即得所述防雾涂料。步骤一，按质量组分称取亲水环状聚硅氧烷、聚硅氮烷、固化剂、流平剂、溶剂；步骤二，在容器中加入溶剂，然后在搅拌状态下依次加入亲水环状聚硅氧烷、聚硅氮烷、流平剂和固化剂混合均匀即得所述防雾涂料。(a) Hydrophilic cyclic polysiloxane synthesis: In a 250 mL three-necked flask, add 69.7 g (0.1 mol) of glycerol ether propylene cyclic siloxane and start stirring; then add 21.0 g (0.2 mol) of diethanolamine to the above flask, and react at 80 degrees for 3 hours until the pH is neutral, yielding prepolymer 1. Another 1000 mL three-necked flask is taken, and 133.3 g (0.6 mol) of isophorone diisocyanate and 0.2 g (0.05 wt%) of dibutyltin dilaurate are added while stirring; then, mix 300.0 g (0.6 mol) of polyethylene glycol monomethyl ether 500 until fully dissolved, transfer to a constant pressure drop funnel, and slowly add to the flask at room temperature (the reaction is highly exothermic, control the drop rate to avoid local overheating). After the addition is complete, continue reacting at room temperature for 30 minutes, then raise to 70 degrees Celsius and react until the isocyanate (-NCO) content of the mixture reaches the theoretical value (measured by hydrochloric acid dibutylamine method) to obtain prepolymer 2. Add prepolymer 1 and continue the reaction until the isocyanate (-NCO) content is zero to obtain hydrophilic cyclic polysiloxane, then cool, dry, and store sealed."
+}
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diff --git a/task2/task2-paper-info/CN116554477B_POSS╕─╨╘╛█║╧╬я╝░╞ф╓╞▒╕╖╜╖ибв░№║м╞ф╡─│м╟╫╦о═┐┴╧.json b/task2/task2-paper-info/CN116554477B_POSS╕─╨╘╛█║╧╬я╝░╞ф╓╞▒╕╖╜╖ибв░№║м╞ф╡─│м╟╫╦о═┐┴╧.json
new file mode 100644
index 0000000..7132b0e
--- /dev/null
+++ b/task2/task2-paper-info/CN116554477B_POSS╕─╨╘╛█║╧╬я╝░╞ф╓╞▒╕╖╜╖ибв░№║м╞ф╡─│м╟╫╦о═┐┴╧.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "将巯基丙酸与八环氧环己基乙基笼状聚倍半硅氧烷混合，加入第一催化剂进行加热反应，得到中间体；向中间体中加入乙氧化三羟甲基丙烷三丙烯酸酯和第二催化剂在室温下进行点击反应，即得到POSS改性聚合物；其中，八环氧环己基乙基笼状聚倍半硅氧烷与巯基丙酸的摩尔比为1：2～1：8；乙氧化三羟甲基丙烷三丙烯酸酯与中间体的摩尔比为1:1∼1:3。The text excerpt does not provide specific details regarding the experimental protocol for the synthesis of hydrophilic polymers with functional groups. Therefore, I am unable to extract the requested information.The text excerpt does not provide specific experimental protocols for the synthesis of hydrophilic polymers with functional groups.利用表面接枝有烯键和磺酸基的改性硅溶胶、UV树脂低聚物、活性稀释剂、表面活性剂和光引发剂等成分制备得到紫外光固化涂料。将巯基丙酸与八环氧环己基乙基笼状聚倍半硅氧烷混合，加入第一催化剂进行加热反应，得到中间体；向中间体中加入乙氧化三羟甲基丙烯酸酯和第二催化剂在室温下进行点击反应，即得到POSS改性聚合物。第一催化剂为三乙胺，加热反应的温度为95至110°C，反应时间为3至6小时，八环氧环己基乙基笼状聚倍半硅氧烷与巯基丙酸的摩尔比为1：2至1：8，第二催化剂为碳酸钠，乙氧化三羟甲基丙烯酸酯与中间体的摩尔比为1：1至1：3。步骤S101，将巯基丙酸与八环氧环己基乙基笼状聚倍半硅氧烷混合，加入三乙胺在 $95\\sim110^{\\circ}\\mathrm{C}$ 的条件下反应 $3\\sim6\\mathrm{h}$ ，得到中间体；八环氧环己基乙基笼状聚倍半硅氧烷与巯基丙酸的摩尔比为 $1{:}2\\sim1{:}8$；步骤S102，向中间体中加入乙氧化三羟甲基丙烯酸酯和碳酸钠在室温下进行点击反应，即得到POSS改性聚合物；乙氧化三羟甲基丙烯酸酯与中间体的摩尔比为 $1{:}1\\sim1{:}3$ 。"
+}
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diff --git a/task2/task2-paper-info/CN200910236651-╥╗╓╓╗╞╘н╜║╜╙╓ж╣▓╛█╬я╟¤╙═╝┴╝░╞ф╓╞╖и║═╙ж╙├-╔ъ╟ы╣л┐к.json b/task2/task2-paper-info/CN200910236651-╥╗╓╓╗╞╘н╜║╜╙╓ж╣▓╛█╬я╟¤╙═╝┴╝░╞ф╓╞╖и║═╙ж╙├-╔ъ╟ы╣л┐к.json
new file mode 100644
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--- /dev/null
+++ b/task2/task2-paper-info/CN200910236651-╥╗╓╓╗╞╘н╜║╜╙╓ж╣▓╛█╬я╟¤╙═╝┴╝░╞ф╓╞╖и║═╙ж╙├-╔ъ╟ы╣л┐к.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "在250mL三口烧瓶中，加入1g黄原胶和100mL蒸馏水，放置过夜，充分搅拌使黄原胶完全溶解。将三口烧瓶放在恒温水浴锅中，在反应温度下搅拌并通氮气保护，加入一定量的过硫酸铵和丙烯酰胺，反应至预定时间后，中止反应，冷却。将产物用过量丙酮沉淀，50°C下完全干燥，得到接枝共聚粗产物。将粗产品用体积比为80:20的甲醇-水混合溶剂在索氏提取器中萃取12h以上，以除去PAM均聚物，抽提剩余物用蒸馏水反复洗涤，得到XG-g-AM接枝共聚物。第1步，将100 份黄原胶在反应容器中完全溶解于 300 到 30000 份去离子水中，通入高纯氮气鼓泡除氧；第2步，将所述单体中的反应活性低的一种或两种 10 到 1500 份加入到反应容器中，搅拌至完全溶解；第3步，向反应容器中继续通入高纯氮气鼓泡除氧20分钟以上；第4步，在氮气保护下，向反应容器中加入 0.1 到 10 份硝酸铈铵，在 20°C 到 70°C 下反应 5 到 15分钟；第5步，在氮气保护下，向反应容器中加入 0.1 到 1000 份过硫酸盐， 0.1 到 3000 份亚硫酸氢钠，将所述单体中反应活性高的另一种单体 190 到 2990 份配成水溶液，在 0.5小时内以均匀速率加到反应容器中，在 20°C 到 70°C 下反应 2 到 6小时；第6步，将上步产物用过量丙酮沉淀， 50°C 下完全干燥，得到接枝共聚粗产物；第7步，将粗产物用体积比为 80:20 的甲醇 - 水混合溶剂在索氏提取器中萃取12小时，抽提剩余物用蒸馏水反复洗涤，得到接枝共聚物，进行干燥，得到产品。在 $250\\mathrm{ mL}$ 三口烧瓶中，加入 1g 黄原胶和 $100\\mathrm{g}$ 蒸馏水，充分搅拌使黄原胶完全溶解，通入高纯氮气鼓泡除氧。将 $6.43\\mathrm{g}$ 的 $2^{-}$ 丙烯酰胺基 $-2-$ 甲基丙磺酸 (AMPS) 加入到反应容器中，搅拌至完全溶解；向反应容器中继续通入高纯氮气鼓泡除氧 20 分钟以上。将三口烧瓶放在 $55^{\\circ}\\mathrm{C}$ 恒温水浴锅中，在氮气保护下，加入 $0.02\\mathrm{g}$ 硝酸铈铵， $55^{\\circ}\\mathrm{C}$ 下反应5 分钟后，加入 $0.2\\mathrm{g}$ 过硫酸铵， $0.6\\mathrm{g}$ 亚硫酸氢钠，将 $\\mathrm{2g}$ 丙烯酰胺 (AM) 配成 $50\\%$ 的水溶液缓慢滴加入到反应容器中， $55^{\\circ}\\mathrm{C}$ 下反应 3 小时，将产物用过量丙酮沉淀， $50^{\\circ}\\mathrm{C}$ 下完全干燥，得到接枝共聚粗产物。将粗产品用体积比为 $80:20$ 的甲醇- 水混合溶剂在索氏提取器中萃取12 小时以上，以除去均聚物，抽提剩余物用蒸馏水反复洗涤，得到接枝共聚物，于 $50^{\\circ}\\mathrm{C}$ 下完全干燥，称重，得到黄原胶接枝共聚物 $\\mathrm{XG^{-}g^{-}}(AM-co-AMPS)$。"
+}
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diff --git a/task2/task2-paper-info/CN201080052429.5 - ╖└╬э═┐┴╧╫щ║╧╬я - ░█╠┌═°.json b/task2/task2-paper-info/CN201080052429.5 - ╖└╬э═┐┴╧╫щ║╧╬я - ░█╠┌═°.json
new file mode 100644
index 0000000..ceda1f7
--- /dev/null
+++ b/task2/task2-paper-info/CN201080052429.5 - ╖└╬э═┐┴╧╫щ║╧╬я - ░█╠┌═°.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "1. Prepare a mixture of monomers consisting of (A1) vinyl monomers with N-hydroxymethyl or N-alkoxy hydroxymethyl groups, (A2) vinyl monomers with sulfonic acid groups, and (A3) (methacrylic) alkyl ester monomers. 2. Use a weight ratio where the total weight of (A1), (A2), and (A3) is 100 parts by weight, with (A1) in the range of 3 to 20 parts, (A2) in the range of 3 to 20 parts, and (A3) in the range of 60 to 94 parts, such that the total of (A1) and (A2) is between 6 and 40 parts. 3. For every 100 parts of the copolymer (A), include a surfactant (C) in the range of 0.5 to 30 parts by weight. 4. The basic compound (B) should be included in an amount corresponding to 50 to 95 mol% relative to the sulfonic acid group of (A2). 5. Optionally, include N,N-dialkyl(methacrylamide) monomer (A4) in the mixture, with 5 to 50 parts by weight for (A4) when accounting for the total of (A3) and (A4) being 100 parts by weight. 6. Ensure the basic compound (B) has a dissociation constant in aqueous solution at 25 degrees Celsius between 3 and 14 and a boiling point between 130 and 150 degrees Celsius. 7. The copolymer (A) should exhibit a crosslinked structure formed by a condensation reaction of the N-hydroxymethyl or N-alkoxy hydroxymethyl groups from (A1) and include both neutralized and unneutralized sulfonic acid groups from (A2) to enhance hydrophilicity and promote the condensation reaction.所述亲水性聚合物部分由具有N-羟甲基、N-羟甲基醚基、羟基中的任一种交联官能团的单体、亲水性单体及（甲基）丙烯酸低级烷基酯形成，所述疏水性聚合物部分由具有磺酸基、羧基或磷酸基的乙烯基类单体及（甲基）丙烯酸低级烷基酯形成。共聚物（A)的合成步骤：首先，准备包含单体（A1，N-羟甲基或N-烷氧基羟甲基的乙烯基类单体）、单体（A2，具有磺酸基的乙烯基类单体）和单体（A3，（甲基）丙烯酸烷基酯类单体）的单体混合物。按比例将单体（A1）和单体（A2）各3至20质量份，单体（A3）60至94质量份混合，使得单体（A1）和（A2）的总量为6至40质量份。加入N，N-二烷基（甲基）丙烯酰胺类单体（A4），比例为5至50质量份。然后，将碱性化合物（B）与磺酸基比例设为50至95mol%。最后，加入表面活性剂（C），比例为0.5至30质量份。混合物在适宜的条件下进行聚合反应，得到的共聚物（A）具有良好的亲水性和耐热性，且能够在高湿度和低温条件下固化。1. 在具有搅拌装置、氮气导入管及冷凝管的反应容器中加入聚合溶剂（如正丙醇）、单体（A1）N-羟甲基丙烯酰胺、单体（A2）2-丙烯酰胺-2-甲基丙磺酸、单体（A3）甲基丙烯酸烷基酯类单体以及可选的单体（A4）N,N-二甲基丙烯酰胺。2. 加入碱性化合物（B），如三乙醇胺，其用量为单体（A2）的磺酸基的50-95 mol%。3. 将自由基聚合引发剂加入反应容器中，进行聚合反应，聚合时间为5小时，升温至80°C聚合1小时，以获得共聚物溶液。4. 调节共聚物的浓度，加入表面活性剂，并混合以制备防雾涂料组合物。5. 使用喷涂法将防雾涂料组合物涂布于基材上，随后进行干燥及加热固化。"
+}
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diff --git a/task2/task2-paper-info/CN201410852633-│м╟╫╦о═╕├ў╖└╬э═┐▓у╡─╓╞▒╕╖╜╖и-╔ъ╟ы╣л┐к.json b/task2/task2-paper-info/CN201410852633-│м╟╫╦о═╕├ў╖└╬э═┐▓у╡─╓╞▒╕╖╜╖и-╔ъ╟ы╣л┐к.json
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+++ b/task2/task2-paper-info/CN201410852633-│м╟╫╦о═╕├ў╖└╬э═┐▓у╡─╓╞▒╕╖╜╖и-╔ъ╟ы╣л┐к.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "制备聚氨酯预聚体：将二异氰酸单体、丙烯酸羟酯和有机溶剂 A 加入反应容器中，其中二异氰酸单体与丙烯酸羟酯的摩尔比为 0.7:1-1:1，丙烯酸羟酯与有机溶剂 A 的摩尔比为 3:7-1:1，然后加入二月桂酸二丁基锡作为催化剂，催化剂的用量为二异氰酸单体质量的 0.1%，将以上的混合物在 50–70°C 反应 2-4h，得到聚氨酯预聚体；制备聚山梨酯改性的超亲水预聚体：将聚山梨酯用有机溶剂 B 溶解并添加到上述制备的聚氨酯预聚体中，其中，在聚山梨酯与有机溶剂 B 的混合溶解液中，聚山梨酯的质量浓度为 50‰，聚山梨酯与二异氰酸的单体的摩尔比0.5:1-1:1，将以上混合物在 50–70°C 反应2-4h，得到聚山梨酯改性的超亲水预聚体；制备超亲水透明抗雾涂层：将上述制备的聚山梨酯改性的超亲水预聚体与活性稀释剂、光引发剂均匀混合；光引发剂为聚山梨酯改性的超亲水预聚体质量的 1-2%，混合均匀后涂覆在基材上烘干，经紫外线辐射交联固化5-10s，即得到超亲水透明抗雾涂层。1. Prepare polyurethane prepolymer: Add diisocyanate monomer, hydroxy acrylate, and organic solvent A into a reaction vessel, with a molar ratio of diisocyanate monomer to hydroxy acrylate of 0.7:1-1:1, and a molar ratio of hydroxy acrylate to organic solvent A of 3:7-1:1. Then add dibutyltin dilaurate as a catalyst at a dosage of 0.1% by mass of the diisocyanate monomer. React the mixture at 50-70°C for 2-4 hours to obtain the polyurethane prepolymer. 2. Prepare polysorbate-modified super hydrophilic prepolymer: Dissolve polysorbate in organic solvent B and add it to the prepared polyurethane prepolymer, with a concentration of polysorbate at 50% in the mixed solution. The molar ratio of polysorbate to diisocyanate monomer is 0.5:1-1:1. React this mixture at 50-70°C for 2-4 hours to obtain the polysorbate-modified super hydrophilic prepolymer. 3. Prepare super hydrophilic transparent anti-fog coating: Mix the polysorbate-modified super hydrophilic prepolymer with reactive diluents and photoinitiators uniformly, where the photoinitiator accounts for 1-2% of the mass of the super hydrophilic prepolymer. Add an appropriate amount of reactive diluent to maintain the viscosity between 3000-6000 cps at 25°C. After uniform mixing, coat this on the substrate and dry it, then UV cure for 5-10 seconds to obtain the super hydrophilic transparent anti-fog coating.聚山梨酯改性的超亲水预聚体的制备方程式1. 制备聚氨酯预聚体：将二异氰酸单体、丙烯酸羟酯和有机溶剂 A 加入反应容器中，二异氰酸单体与丙烯酸羟酯的摩尔比为 0.7:1，丙烯酸羟酯与有机溶剂 A 的摩尔比为 3:7，加入二月桂酸二丁基锡作为催化剂，催化剂用量为二异氰酸单体质量的 0.1%，在 50-70°C 反应 2-4h，得到聚氨酯预聚体；2. 制备聚山梨酯改性的超亲水预聚体：将聚山梨酯用有机溶剂 B 溶解并添加到聚氨酯预聚体中，聚山梨酯的质量浓度为 50%，聚山梨酯与二异氰酸的单体摩尔比 0.5:1-1:1，在 50-70°C 反应 2-4h，得到聚山梨酯改性的超亲水预聚体；3. 制备超亲水透明抗雾涂层：将聚山梨酯改性的超亲水预聚体与活性稀释剂、光引发剂均匀混合，光引发剂为聚山梨酯改性的超亲水预聚体质量的 1-2%，添加适量的活性稀释剂使体系粘度在 25°C 下为 3000-6000 cps，涂覆在基材上烘干，经紫外线辐射交联固化 5-10s，得到超亲水透明抗雾涂层。"
+}
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diff --git a/task2/task2-paper-info/CN201580040385-░№║м╗╟╦с╧╡╣▓╛█╬я║═░▒╗∙╩ў╓м╡─╟╫╦о╨╘▓─┴╧-╔ъ╟ы╣л┐к.json b/task2/task2-paper-info/CN201580040385-░№║м╗╟╦с╧╡╣▓╛█╬я║═░▒╗∙╩ў╓м╡─╟╫╦о╨╘▓─┴╧-╔ъ╟ы╣л┐к.json
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+++ b/task2/task2-paper-info/CN201580040385-░№║м╗╟╦с╧╡╣▓╛█╬я║═░▒╗∙╩ў╓м╡─╟╫╦о╨╘▓─┴╧-╔ъ╟ы╣л┐к.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "将包含共聚物(i)和氨基树脂(ii)的组合物固化，从而制作固化物。共聚物(i)包含下述通式(1)、(2)及(3)所示的结构单元，氨基树脂(ii)为下述通式(7)所示的氨基树脂。氨基树脂的重量比(i)/(ii)在99/1至1/99的范围内。共聚物(i)的重均分子量为500至3,000,000，宜利用凝胶渗透色谱(GPC)测得。固化物中可以还包含无机粒子(iii)，其中共聚物(i)、氨基树脂(ii)及无机粒子(iii)的总重量设为100重量份，具体包含5至98重量份共聚物(i)、1至70重量份氨基树脂(ii)及1至90重量份无机粒子(iii)。The synthesis of hydrophilic polymers with functional groups involves the use of sulfonated copolymers and amino resins, ensuring a balanced incorporation of functional groups to enhance hydrophilicity and other desired properties.向羟基硅烷中配合三聚氰胺树脂和具有环氧基的硅化合物，或向羟基硅烷中配合环氧化合物和铝络合物，或向羟基硅烷中配合具有羟基的丙烯酸系聚合物进行乳液聚合。另有向烷氧基硅烷中配合苯乙烯磺酸系聚合物，或使具有磺酸基及烷氧基甲硅烷基的共聚物与烷氧基硅烷反应，或使具有磺酸基及环氧基的共聚物与烷氧基硅烷反应，以获得高亲水性的固化物形成的膜。本发明的聚合物合成包括以下步骤：1. 准备用于合成的共聚物(i)，该共聚物应在分子内至少包含磺酸基和环氧基、磺酸基和烷氧基甲硅烷基，或磺酸基和环氧基和烷氧基甲硅烷基。2. 结合氨基树脂(ii)，选择与共聚物(i)的重量比为99/1至1/99的范围。3. 如果需要，可以加入无机粒子(iii)，其中共聚物(i)、氨基树脂(ii)与无机粒子(iii)的总重量设为100重量份，并保持共聚物(i)与氨基树脂(ii)的恒定比例。4. 通过固化这些组分得到固化物，形成膜，膜的厚度应控制在0.01至300微米内。将在减压下脱气的483.3g甲醇装入反应烧瓶中，一边搅拌一边缓缓添加28.0g（0.424摩尔）纯度85wt%的KOH小片并使其完全溶解。接下来，分批装入89.9g（0.424摩尔）丙烯酰胺基-叔丁基磺酸进行中和（pH=7.2），制作含有丙烯酰胺基-叔丁基磺酸钾盐的中和混合物。然后，分别制备7.54g（0.0530摩尔）甲基丙烯酸缩水甘油酯、15.40g（0.0530摩尔）甲基丙烯酰氧基丙基三乙氧基硅烷和22.8g甲醇的混合液，以及1.15g作为聚合引发剂的过氧化-2-乙基己酸叔丁酯和11.5g甲醇的混合液。将它们经2小时分批装入得到的中和混合物中，在加热回流条件下反应（内温66°C），每次三分之一，装入结束后，继续在加热回流及搅拌条件下聚合8小时。冷却至室温后，过滤结晶析出的共聚物，再用300ml甲醇洗涤2次，然后在减压下（低于100mmHg）、50°C条件下充分干燥，得到86.0g白色的共聚物（收率67%）。将535.5g甲醇装入反应烧瓶中，边搅拌边缓慢添加23.6g (0.357摩尔)纯度85wt%的KOH小片，使其完全溶解。分批装入75.7g (0.357摩尔)ATBS，进行中和(pH=7.5)，制作含有ATBS-K的中和混合物。该中和混合物加热回流(内温63°C)，分批装入5.14g (0.036摩尔)GMA与0.13g作为聚合引发剂的过丁基-O的混合液，在加热回流下混合搅拌4.5小时进行聚合。冷却至室温后，过滤结晶析出的聚合物，用甲醇洗涤后，在减压下(低于100mmHg)及50°C的条件下干燥，直至不发生重量变化，得到88.8g白色的共聚聚合物'CH110901' (收率94%)。"
+}
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diff --git a/task2/task2-paper-info/CN201710055059-╝╛яз╤╬╨═╟╫╦о╨╘╫╧═т╣т╣╠╗п╩ў╓м╡─╓╞▒╕╖╜╖и-╔ъ╟ы╣л┐к.json b/task2/task2-paper-info/CN201710055059-╝╛яз╤╬╨═╟╫╦о╨╘╫╧═т╣т╣╠╗п╩ў╓м╡─╓╞▒╕╖╜╖и-╔ъ╟ы╣л┐к.json
new file mode 100644
index 0000000..4dfc8a0
--- /dev/null
+++ b/task2/task2-paper-info/CN201710055059-╝╛яз╤╬╨═╟╫╦о╨╘╫╧═т╣т╣╠╗п╩ў╓м╡─╓╞▒╕╖╜╖и-╔ъ╟ы╣л┐к.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The experimental protocol for the synthesis of hydrophilic polymers with functional groups is not provided in the text excerpt.将二元聚醚胺与丙烯酰氧乙基三甲基氯化铵在室温下进行迈克尔加成反应，得到双末端仲氨基化合物中间体；将所述双末端仲氨基化合物中间体与多官能度丙烯酸酯在 40~45°C 下进行迈克尔加成反应，得到所述季铵盐型亲水性紫外光固化树脂。The synthesis of quaternary ammonium salt-type hydrophilic UV-curable resin involves the following steps: 1. Mix the selected monomers and oligomers to achieve the desired viscosity and reactivity. 2. Add a photoinitiator to the mixture in an appropriate concentration to facilitate UV curing. 3. Introduce functional groups such as quaternary ammonium salts into the polymer backbone by selecting suitable reagents and controlling the reaction conditions. 4. Place the mixture in a UV curing chamber and expose it to UV light for a specified duration to initiate the polymerization process. 5. After curing, the resulting resin can be characterized for its hydrophilicity and functional properties.本发明涉及一种季铵盐型亲水性紫外光固化树脂的制备方法该涂料的主体亲水性树脂是由可聚合非离子表面活性剂烯丙氧基壬基苯氧基丙醇聚氧乙烯醚、丙烯酸酯及丙烯酸经自由基聚合得到侧链含有羧基的聚丙烯酸酯，然后侧链羧基进行开环甲基丙烯酸缩水甘油酯的环氧基而得到侧链含有双键的光固化亲水性聚丙烯酸酯。将二元聚醚胺与丙烯酰氧乙基三甲基氯化铵在室温下进行迈克尔加成反应，得到双末端仲氨基化合物中间体；将所述双末端仲氨基化合物中间体与多官能度丙烯酸酯在 40到45摄氏度 下进行迈克尔加成反应，得到季铵盐型亲水性紫外光固化树脂。在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(70克)，阻聚剂对羟基苯甲醚(0.14克)，聚醚胺D400(2.30克，5mmol)和80%丙烯酰氧乙基三甲基氯化铵水溶液(24.2克，10mmol)，室温反应1.5小时，FT-IR检测不到810cm^{-1}处双键的吸收峰，第一步反应结束。然后加入乙氧基双季戊四醇六丙烯酸酯(EO96mol)(48.02克，10mmol)，升温至45°C反应3小时，FT-IR检测不到3400{-}3300cm^{-1}处仲胺的吸收峰，结束反应，得到浅黄色透明液体。然后用正己烷进行沉淀，再经50°C真空干燥12小时得到官能度为10的季铵盐型亲水性紫外光固化树脂。"
+}
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diff --git a/task2/task2-paper-info/CN201710055097-╢р╣┘─▄╢╚╟╫╦о╨╘╫╧═т╣т╣╠╗п╩ў╓м╡─╓╞▒╕╖╜╖и╝░╞ф╙ж╙├-╔ъ╟ы╣л┐к (1).json b/task2/task2-paper-info/CN201710055097-╢р╣┘─▄╢╚╟╫╦о╨╘╫╧═т╣т╣╠╗п╩ў╓м╡─╓╞▒╕╖╜╖и╝░╞ф╙ж╙├-╔ъ╟ы╣л┐к (1).json
new file mode 100644
index 0000000..ad2d911
--- /dev/null
+++ b/task2/task2-paper-info/CN201710055097-╢р╣┘─▄╢╚╟╫╦о╨╘╫╧═т╣т╣╠╗п╩ў╓м╡─╓╞▒╕╖╜╖и╝░╞ф╙ж╙├-╔ъ╟ы╣л┐к (1).json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "1.室温条件下，将二元聚醚胺与两倍当量的甲氧基聚乙二醇丙烯酸酯在乙醇溶剂中进行迈克尔加成反应1-2小时，得到双末端仲氨基化合物中间体；2.将双末端仲氨基化合物中间体与两倍当量的多官能度丙烯酸酯在40–45°C条件下进行迈克尔加成反应2-3小时，即得到多官能度亲水性紫外光固化树脂。在制备亲水性树脂时，可采用可聚合的非离子表面活性剂烯丙氧基壬基苯氧基丙醇聚氧乙烯醚、丙烯酸酯及丙烯酸为主要成分，通过自由基聚合反应实现侧链含有羧基的聚丙烯酸酯的合成。随后，对该聚丙烯酸酯的侧链羧基进行开环反应，使用甲基丙烯酸缩水甘油酯的环氧基，以得到侧链含有双键的光固化亲水性聚丙烯酸酯。同时，需注意控制聚合反应，以减少未反应的单体残留，确保其参与固化反应形成交联网络。室温条件下，将二元聚醚胺与两倍当量的甲氧基聚乙二醇丙烯酸酯在乙醇溶剂中进行迈克尔加成反应1-2小时，得到双末端仲氨基化合物中间体；然后，该双末端仲氨基化合物中间体再与两倍当量的多官能度丙烯酸酯在 $40–45^{\\circ}\\mathrm{C}$ 条件下，进行迈克尔加成反应2-3小时，得到多官能度亲水性紫外光固化树脂。在配有机械搅拌、温度计、氮气导入装置的250毫升四口瓶中，加入乙醇(61克)，阻聚剂对羟基苯甲醚(0.18克)，聚醚胺D-400(2.30克，5mmol)和甲氧基聚乙二醇(1000)丙烯酸酯(10.54克，10mmol)，室温反应1.5小时，FT-IR检测不到$810\\mathrm{cm}^{-1}$处双键的吸收峰，第一步反应结束。然后加入乙氧基双季戊四醇六丙烯酸酯(EO96mol)(48.02克，10mmol)，升温至45度反应3小时，FT-IR检测不到$3400{-}3300{\\mathrm{cm}}^{-1}$处仲胺的吸收峰，结束反应，得到浅黄色透明液体，为$50\\%$固含量的10官亲水性紫外光固化树脂。"
+}
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diff --git a/task2/task2-paper-info/CN201810154740-╥╗╓╓║м╗╟╦с╤╬╡─╛█▒√╧й╦сїе╦о╖╓╔в╠х╝░╞ф╓╞▒╕╖╜╖и╙ы╙ж╙├-╔ъ╟ы╣л┐к.json b/task2/task2-paper-info/CN201810154740-╥╗╓╓║м╗╟╦с╤╬╡─╛█▒√╧й╦сїе╦о╖╓╔в╠х╝░╞ф╓╞▒╕╖╜╖и╙ы╙ж╙├-╔ъ╟ы╣л┐к.json
new file mode 100644
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--- /dev/null
+++ b/task2/task2-paper-info/CN201810154740-╥╗╓╓║м╗╟╦с╤╬╡─╛█▒√╧й╦сїе╦о╖╓╔в╠х╝░╞ф╓╞▒╕╖╜╖и╙ы╙ж╙├-╔ъ╟ы╣л┐к.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "(1) Synthesis of sulfonate-containing polyacrylate: Mix all acrylic monomers with chain transfer agents to prepare mixture I. Dissolve vinyl sulfonate monomers, initiators, and organic solvents to prepare mixture II. Add 10-30% mixture I and 10‰ mixture II to the reaction vessel, stir and heat to 80-95°C for 30-60 minutes. Gradually add the remaining mixture I and mixture II into the reaction vessel over 4-6 hours. Maintain temperature for 0.5-2 hours, cool down to below 40-70°C, and add a neutralizing agent to obtain sulfonate-containing polyacrylate. (2) Preparation of aqueous dispersion: Add 1-3 times the mass of the obtained sulfonate-containing polyacrylate in water for emulsification until the solid content is 20%, thus obtaining the sulfonate-containing polyacrylate aqueous dispersion.本发明涉及一种聚丙烯酸酯水分散体及其制备方法，特别是含磺酸盐的聚丙烯酸酯水分散体的合成。亲水性防雾涂料的合成包含两层涂料：底层涂料和面层涂料。底漆和面漆均为聚丙烯酸酯乳液。面层涂料通过使用极性亲水基团如羟基、羧基等以提供亲水性。对基材的附着力通过两层涂料的组合来提高，但需注意二层涂料会影响涂膜的透明性和增加施工成本。(1) Preparation of sulfonate-containing polyacrylate: Mix all acrylic monomers with chain transfer agents to prepare mixture I. Dissolve vinyl sulfonate monomers, initiators, and organic solvents to prepare mixture II. Add 10-30% of mixture I and 10‰ of mixture II into the reactor, stir and heat to 80-95°C for 30-60 minutes. Add the remaining mixture I and mixture II into the reactor over 4-6 hours, then maintain the temperature for 0.5-2 hours. Cool down to below 40-70°C, add neutralizing agent to neutralize, obtaining sulfonate-containing polyacrylate; (2) Preparation of water dispersion: Add 1-3 times the mass of sulfonate-containing polyacrylate in water, emulsify to a solid content of 20%, yielding sulfonate-containing polyacrylate water dispersion.含磺酸盐的聚丙烯酸酯水分散体的制备：按照质量份计，将相应质量份的甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸羟乙酯、丙烯酸、链转移剂巯基乙醇混合制备混合液I；将相应质量份的2-丙烯酰胺-2-甲基丙磺酸、引发剂偶氮二异丁腈加入至N,N-二甲基甲酰胺和丙酮溶剂中，搅拌至完全溶解制备混合液II；向反应釜中加入10%质量的混合液I和10%质量的混合液II，搅拌，升温至80°C保温30分钟，控制剩余混合液I和II在6小时内滴加完成，保温2小时，降温至40°C后加入3.6份的2-氨基-2-甲基丙醇中和，得到含磺酸盐的聚丙烯酸酯。(1) Synthesis of hydrophilic polymer: First, prepare the raw material formulation with the following composition by weight: Solvent: acetone 25 parts; Acrylate monomers: Butyl methacrylate 15 parts, Methyl methacrylate 15 parts, Octyl acrylate 25 parts, Itaconic acid 1.0 parts, Hydroxypropyl methacrylate 11.5 parts, Allyl ether sulfate 4 parts; Initiator: azobisisobutyronitrile hydrochloride 1.0 parts; Neutralizing agent: triethylamine 1.5 parts; Chain transfer agents: dodecyl mercaptan 0.5 parts, thioglycol 0.5 parts; Total: 100 parts. (2) Prepare the sulfonate-containing polyacrylate by mixing the appropriate amounts of butyl methacrylate, methyl methacrylate, octyl acrylate, hydroxypropyl methacrylate, itaconic acid, thioglycol, and dodecyl mercaptan to make mixture I; In another container, dissolve the appropriate amounts of ally ether sulfate and azobisisobutyronitrile hydrochloride in acetone to make mixture II; Add 10% by weight of mixture I and 20% by weight of mixture II into the reaction kettle, stir, heat to 90°C and maintain for 60 min, then control the remaining mixtures I and II to be added dropwise within 4 hours, hold for 1.5 hours, cool to 50°C, and add 1.5 parts of triethylamine for neutralization to obtain sulfonate-containing polyacrylate. (3) Prepare the aqueous dispersion: Add 1.3 times the weight of deionized water to the obtained sulfonate-containing polyacrylate to emulsify, resulting in sulfonate-containing polyacrylate aqueous dispersion with a white, translucent appearance, solid content of 35%, average particle size of 176 nm, and viscosity at 25°C of 5000 CP."
+}
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diff --git a/task2/task2-paper-info/CN201910237001-╥╗╓╓╦л╔·╜с╣╣╛█├╤╣ш╤ї═щ╝░╓╞▒╕╖╜╖и-╔ъ╟ы╣л┐к.json b/task2/task2-paper-info/CN201910237001-╥╗╓╓╦л╔·╜с╣╣╛█├╤╣ш╤ї═щ╝░╓╞▒╕╖╜╖и-╔ъ╟ы╣л┐к.json
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@@ -0,0 +1,3 @@
+{
+    "protocol": "将化合物A与化合物B混合搅拌均匀，通惰性气体保护，升温至50-100°C, 加入催化剂，在100°C-140°C反应2-8h，在真空有惰性气体保护条件下，脱除低分子即得所述双生结构聚醚硅氧烷。化合物B与化合物A的摩尔比例为0.8-1.5:1，优选为1.2；加入催化剂温度50-100°C，优选为60-80°C；反应温度为100-150°C，优选为110-140°C；反应时间为2-8h，优选为4-6h。催化剂为铂、铑、钯或它们的化合物，催化剂用量为5-300ppm，优选为10-200ppm。惰性气体为氮气。将化合物A与化合物B混合搅拌均匀，通惰性气体保护，升温至50-100°C, 加入催化剂，在100°C-140°C反应2-8小时，在真空有惰性气体保护条件下，脱除低分子即得所述双生结构聚醚硅氧烷。化合物B与化合物A的摩尔比例为0.8-1.5:1，优选为1.2；加入催化剂的温度为50-100°C，优选为60-80°C；反应温度为100-150°C，优选为110-140°C；反应时间为2-8小时，优选为4-6小时；催化剂为铂、铑、钯或它们的化合物，催化剂用量为5-300ppm，优选为10-200ppm；惰性气体为氮气。在装有电动搅拌器、温度计的250ml干燥三口瓶中，分别加入46克七甲基三硅氧烷、100克2,4,7,9-四甲基-5-癸炔-4,7-二醇四乙氧基醚搅拌均匀，通N2，然后升温，当温度升至60°C，加入氯铂酸催化剂0.2克，继续升温至110°C，反应4h，在N2保护下，抽真空脱除低组分，即得一种浅黄色液体RA。在实施例2至实施例5中，通过调节七甲基三硅氧烷和二醇醚的比例、添加不同的催化剂量以及改变反应温度和时间，合成各具特性的聚合物RB、RC、RD和RE。"
+}
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diff --git a/task2/task2-paper-info/CN202011067473-╦о╨╘╖└╬э═┐┴╧╝░╞ф╓╞▒╕╖╜╖и-╔ъ╟ы╣л┐к.json b/task2/task2-paper-info/CN202011067473-╦о╨╘╖└╬э═┐┴╧╝░╞ф╓╞▒╕╖╜╖и-╔ъ╟ы╣л┐к.json
new file mode 100644
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@@ -0,0 +1,3 @@
+{
+    "protocol": "1. Combine 80-100 g of water-based resin emulsion, 10-30 g of crosslinking agent, and 10-30 g of anti-fog modifier. 2. Synthesize the anti-fog modifier by performing an addition reaction between the octavinyl polyhedral oligomeric silsesquioxane (as shown in formula (1)) and a polyether containing epoxy propylene and epoxy ethylene chains (as shown in formula (2)). 3. Conduct the addition reaction in a solvent selected from one or more of benzene, toluene, butyl glycol ether, ethyl acetate, and tetrahydrofuran. 4. Use a catalyst such as platinum, nickel, or gold, preferably chloroplatinic acid, with an amount of 1-3 wt% of the octavinyl polyhedral oligomeric silsesquioxane. 5. Maintain a molar ratio of 1:(8-10) for the reactants in the addition reaction, at a reaction temperature of 60-100°C, for a reaction time of 3-6 hours.将八乙烯基聚倍半硅氧烷与含有环氧丙烷链和环氧乙烷链的聚醚以1:（8-10）的摩尔比混合，进行加成反应。反应在60{-}100^{\\circ}\\mathrm{C}的温度下进行，反应时间为3{-}6小时，使用催化剂氯铂酸，其用量为八乙烯基聚倍半硅氧烷的1-3\\mathrm{wt\\%}。反应在苯、甲苯、乙二醇单丁醚、乙酸乙酯、四氢呋喃等溶剂中进行。取式（1）所示的八乙烯基聚倍半硅氧烷1mol，配制成1mol/L的溶液；取式（2）所示的聚醚8mol（或9mol、10mol）、配制成相应浓度的溶液。在1L的八乙烯基聚倍半硅氧烷的溶液中加入氯铂酸，随后与聚醚溶液混合，搅拌，并在特定温度下（80°C、90°C、100°C）进行加成反应（4h、5h、3h），以得到防雾改性剂。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/CN202180007560-╖└╬э═┐┴╧╫щ║╧╬я╝░╖└╬э═┐─д╥╘╝░╖└╬э╬я╞╖-╔ъ╟ы╣л┐к.json b/task2/task2-paper-info/CN202180007560-╖└╬э═┐┴╧╫щ║╧╬я╝░╖└╬э═┐─д╥╘╝░╖└╬э╬я╞╖-╔ъ╟ы╣л┐к.json
new file mode 100644
index 0000000..55cf12a
--- /dev/null
+++ b/task2/task2-paper-info/CN202180007560-╖└╬э═┐┴╧╫щ║╧╬я╝░╖└╬э═┐─д╥╘╝░╖└╬э╬я╞╖-╔ъ╟ы╣л┐к.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of the hydrophilic polymer involves mixing elongated colloidal silica with a mixture of silane derivative compounds. This silane derivative mixture must include at least one compound with a polyethylene glycol chain and one compound with an epoxy group. Additionally, the silane derivative compounds may contain acyl or carbamate groups. The optimal amount of the silane derivative mixture, relative to 100 parts by weight of the solid component of elongated colloidal silica, should be between 0.1 and 10.0 parts by weight. The synthesis may include spherical colloidal silica and the elongated colloidal silica can be a mix of acidic and basic types.本发明的实施方式中的防雾涂料组合物的特征在于含有：长条状胶体氧化硅；及硅烷衍生物化合物混合物，其至少包含分子内具有聚乙二醇链的硅烷衍生物化合物及分子内具有环氧基的硅烷衍生物化合物。将酸性长条状胶体氧化硅、碱性长条状胶体氧化硅、分子内具有聚乙二醇链的硅烷衍生物化合物、分子内具有环氧基的硅烷衍生物化合物、表面活性剂及有机溶剂加以混合而制作防雾涂料组合物。合成氨基甲酸酯硅烷A的步骤包括向茄型烧瓶中加入3‑异氰酸基丙基三甲氧基硅烷和Uniox M-400，在75°C下搅拌10小时，通过1H-NMR确认源自异氰酸基的峰消失，得到氨基甲酸酯硅烷A。其余氨基甲酸酯硅烷B、C、D的合成步骤类似，以不同的原料和氧化硅混合物的调配量为基础。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/CN97126279-╙├╙┌╣╠╗п╗╖╤ї╩ў╓м╡─╕─╜°╡─╣╠╗п┤▀╗п╝┴-╔ъ╟ы╣л┐к.json b/task2/task2-paper-info/CN97126279-╙├╙┌╣╠╗п╗╖╤ї╩ў╓м╡─╕─╜°╡─╣╠╗п┤▀╗п╝┴-╔ъ╟ы╣л┐к.json
new file mode 100644
index 0000000..a3cd5a1
--- /dev/null
+++ b/task2/task2-paper-info/CN97126279-╙├╙┌╣╠╗п╗╖╤ї╩ў╓м╡─╕─╜°╡─╣╠╗п┤▀╗п╝┴-╔ъ╟ы╣л┐к.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "1. 使咪唑与含有至少一个活化的双键的不饱和化合物反应，生成每一分子含有一个以上咪唑片断的亲核加成加合物; 2. 制备含有该亲核的加成加合物和一种环氧树脂的配方，该方法的特征在于，在亲核的加成加合物中，少于50% （当量)的咪唑片断在步骤(2)以前被酸中和.制备可固化配方的方法包括以下步骤：\\n(1) 咪唑与含有至少一个活化双键的不饱和化合物反应，制成亲核的加成加合物;\\n(2) 在亲核的加成加合物中有小于50% (当量)的咪唑片断用酸中和，之后将亲核的加成加合物与环氧树脂混合，以形成配方。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/ChemDFMг║╗п╤з┴ь╙Є╡─┤є╨═╙я╤╘╗∙┤б─г╨═.json b/task2/task2-paper-info/ChemDFMг║╗п╤з┴ь╙Є╡─┤є╨═╙я╤╘╗∙┤б─г╨═.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/ChemDFMг║╗п╤з┴ь╙Є╡─┤є╨═╙я╤╘╗∙┤б─г╨═.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/Corkuna Introduction.json b/task2/task2-paper-info/Corkuna Introduction.json
new file mode 100644
index 0000000..df4805a
--- /dev/null
+++ b/task2/task2-paper-info/Corkuna Introduction.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "Very thin layer of specially designed molecules coated on PCB. Applied with glue dispenser/PVD/CVD, etc.Two steps to apply VCN L1-B and L2 on the surface.PCB or FPC fixed in clips then put in the convey belt. Plasma surface cleaning and pretreatment. Coating. Curing in tunnel oven under certain condition. Finished product. Can be checked under UV light."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/FSI-CN110546212A╖└╬э═┐┴╧╫щ║╧╬я╝░╩╣╙├╞ф═┐┴╧╫щ║╧╬я╡─╖└╬э╨╘═╕├ў╞м▓─.json b/task2/task2-paper-info/FSI-CN110546212A╖└╬э═┐┴╧╫щ║╧╬я╝░╩╣╙├╞ф═┐┴╧╫щ║╧╬я╡─╖└╬э╨╘═╕├ў╞м▓─.json
new file mode 100644
index 0000000..72e0a16
--- /dev/null
+++ b/task2/task2-paper-info/FSI-CN110546212A╖└╬э═┐┴╧╫щ║╧╬я╝░╩╣╙├╞ф═┐┴╧╫щ║╧╬я╡─╖└╬э╨╘═╕├ў╞м▓─.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "本发明的第一方式涉及的防雾涂料组合物含有：(A)亲水性双酚A型(甲基)丙烯酸酯、(B)反应性非离子表面活性剂、(C)反应性离子液体和(D)聚合性引发剂。本实施方式涉及的防雾涂料组合物含有：(A)亲水性双酚A型(甲基)丙烯酸酯、(B)反应性非离子表面活性剂、(C)反应性离子液体和(D)聚合性引发剂。其中，(A)成分优选含量为50质量份以上至90质量份，(B)成分含量应为超过2质量份且20质量份以下，(C)成分含量应为1质量份以上5质量份以下，(D)聚合引发剂含量优选为5质量份以上30质量份以下。组合物中的(B)和(C)成分的质量比应为1以上10以下。反应性非离子表面活性剂中的反应性官能团为乙烯基或(甲基)丙烯酰基。聚合性引发剂推荐使用光聚合引发剂。在甲基乙基酮(MEK)等溶剂中添加(A)亲水性双酚A型(甲基)丙烯酸酯、(B)反应性非离子表面活性剂、(C)反应性离子液体、(D)聚合引发剂、(E)环氧乙烯改性二季戊四醇六丙烯酸酯、(F)尿烷(甲基)丙烯酸酯类树脂、均化剂以及其它必要成分，并投入到搅拌机中搅拌。然后将所获得的防雾涂料组合物涂布在聚对苯二甲酸乙二酯(PET)的透明片材上，进行干燥，形成膜。接着，可通过紫外线照射固化涂膜，形成防雾被膜。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/HDI╚¤╛█╠х╡─╙ж╙├US9676895B2.json b/task2/task2-paper-info/HDI╚¤╛█╠х╡─╙ж╙├US9676895B2.json
new file mode 100644
index 0000000..7c670d7
--- /dev/null
+++ b/task2/task2-paper-info/HDI╚¤╛█╠х╡─╙ж╙├US9676895B2.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "To synthesize hydrophilic polymers with functional groups, prepare a polyfunctional oligomer featuring at least two epoxy urethane functional groups and integrate it with a hydroxylated polyalkylene oxide chain. Optionally, include a surfactant to aid dispersion. Combine these components in water to create a dispersion without volatile organic solvents. The resulting dispersed polymer can undergo self-crosslinking and can further crosslink with multifunctional amine compounds to achieve a hard, glossy, solvent-resistant coating.Epoxy urethane (glycidyl carbamate) functional polymers are synthesized from the reaction of an isocyanate with glycidol.To synthesize hydrophilic polymers with functional groups, mix isocyanate monomers with polyols in a two-component system, using a ratio of isocyanates to alcohol of 2:1, keeping isocyanate in excess. Increase the molecular weight by building a prepolymer to mitigate isocyanate reactivity with water.The synthesis of hydrophilic polymers with functional groups involves the preparation of an aqueous coating composition comprising a polyfunctional oligomer that has at least two epoxy urethane functional groups and a polyalkylene oxide chain. Optional components can include a surfactant and water. The process ensures that the resulting composition is completely solvent-free, with no co-solvents used, thereby maintaining a zero VOC content while ensuring the copolymer remains dispersible in water.The polyfunctional oligomer is prepared from the reaction of hydrophilic modified polyfunctional isocyanates resin with glycidol. The polyfunctional resin is derived from the controlled polymerization or oligomerization of difunctional isocyanates. Free isocyanate is reacted with glycidol to form an epoxy urethane functional resin. The polyfunctional resin also includes a polyfunctional biuret or isocyanurate.The method for making an aqueous coating composition comprises the steps of mixing a polyfunctional oligomer having at least two epoxy urethane functional groups and a hydroxylated polyalkylene oxide chain, an optional surfactant, and water. The method may further comprise the step of adding a curing agent to the mixture of the polyfunctional oligomer, the surfactant, and water after the dispersion.The hydrophilic polymer synthesis protocol involves the use of hydrophilic materials like mPEG and glycidol, along with polyfunctional isocyanate resin (isocyanurate trimer of HDI with polyethylene oxide). Amines such as bis(para-aminocyclohexyl)methane (PACM) and Anquamine 419 are used as hardeners. The preparation may also involve anionic surfactants and defoamers to modulate the properties of the final product.A 1000 ml four neck round bottom flask with condenser, nitrogen inlet and Model 21O J-KEM temperature controller, 45 mechanical stirrer, with heating mantle were used for synthesis. The reaction vessel was charged with 225.21 grams glycidol and 700 grams of Bayhydur XP 7165 polyfunctional isocyanate resin and 0.112 grams K-KAT XC-6212 (0.0025 weight percent). The temperature was held at 60°C and the reaction was monitored and controlled within +/- two degrees Celsius. Infrared analysis was performed to determine reaction completion by monitoring the disappearance of the isocyanate peak at 2270 cm−1. Epoxy equivalent weights were determined by titration with HBr (ASTM 55 D1652). Theoretical epoxide equivalent weight of the product was 304, which compares with 303 grams/equivalent determined by titration. Aqueous coating compositions were formulated using the epoxy urethane resin, an amine curing agent, and water without addition of organic co-solvent. Coatings were formulated using 70% epoxy urethane resin and 30% water without addition of cosolvent. After mixing the resin and water, 1-drop Triton GR-7M surfactant was added for dispersion and diluting 1/6 of a drop of BYK 028 was used as a flow aid. After the resin was dispersed in water, the amine curing agent, PACM or Anquamine 419, was added. Film preparation involved applying the aqueous coating formulations onto iron phosphated steel panels using a drawdown bar for a final dry film thickness of approximately 64 microns for the PACM addition and approximately 71 microns for the Anquamine 419 addition. The coated panels were then air cured or placed in an oven at 80°C for 60 minutes for crosslinking.A 500 ml four neck reaction vessel with a condenser, nitrogen inlet, mechanical stirrer, and water bath was used for synthesis. The synthesis occurred in two steps. In the first step, the hydroxyl group of mPEG was reacted with a portion of isocyanate groups of the HDI polyisocyanate. The molecular weight and mole % of mPEG reacted varied from 350, 550, and 750 at 5%, 10%, and 15%, respectively. In the second step, the hydroxyl group of glycidol was reacted with the remaining isocyanate groups of the HDI isocyanate. The overall stoichiometric equivalent amount of isocyanate, mPEG, and glycidol based on —NCO and —OH groups used for the synthesis of GC resins was maintained at 1:1. The catalyst K-KAT XC-6212, in the form of a solution in tertiary butyl acetate (1-2% by wt.), was used for the reaction of isocyanates and hydroxyl groups. The reaction vessel was charged with Desmodur N3600 followed by the addition of the required amount of mPEG, stirring at 50-60 °C for 45-60 min. The catalyst was added after this mixing time at 0.03% by wt. (of the total reaction mass), and the reaction continued for 4-5 hrs at 60-70 °C before the addition of glycidol, which was divided into 3-4 increments added over 4-5 hrs. The first increment was added at 45 °C, followed by subsequent additions at 55-60 °C, maintained until the isocyanate peak at 2271 cm^-1 was gone in FTIR.Waterborne coating formulations of GC resins were made by mixing the components in deionized water by hand. The required amount of resin was dispersed in water using a tongue depressor. After dispersing the GC resins in water, the necessary amount of amine crosslinker was added. The formulations were kept at ambient for about 5 minutes to stabilize. Following stabilization, the coating formulations containing crosslinker were mixed by hand for about 5 minutes and kept at ambient for 10-20 minutes (induction time) before drawdowns. Films were drawn down at 8 mils wet thickness on cleaned steel panels and then cured at ambient conditions for about two weeks.A method for making a polyfunctional oligomer having at least two epoxy urethane functional groups and a C1-C15 alkyl terminated polyalkylene oxide chain comprising the steps of reacting (a) methoxy poly(ethylene glycol) with a polyfunctional isocyanate resin derived from an isocyanurate or a biuret compound; and (b) glycidol with said polyfunctional isocyanate resin.The synthesis of hydrophilic polymers with functional groups involves the use of polyfunctional resins such as hexamethylene diisocyanate isocyanurate or hexamethylene diisocyanate biuret. The alkyl terminated polyalkylene oxide used in the synthesis should be a C1-C10 alkyl terminated polyalkylene oxide, which can include an ethylene oxide chain, a propylene oxide chain, or an ethylene propylene oxide chain. Furthermore, an amine curing agent, which can be bis(para-aminocyclohexyl)methane, diethylene triamine, or 4,4'-methylene dianiline, may be employed in the process."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/HTA╥╗┐ю╙├╙┌╖╓┼ф╕║╘Ё╚╦║═╛█║╧╖┤╙ж╓╨SMILES╡─╬▓▓┐.json b/task2/task2-paper-info/HTA╥╗┐ю╙├╙┌╖╓┼ф╕║╘Ё╚╦║═╛█║╧╖┤╙ж╓╨SMILES╡─╬▓▓┐.json
new file mode 100644
index 0000000..137a793
--- /dev/null
+++ b/task2/task2-paper-info/HTA╥╗┐ю╙├╙┌╖╓┼ф╕║╘Ё╚╦║═╛█║╧╖┤╙ж╓╨SMILES╡─╬▓▓┐.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The HeadTailAssign (HTA) algorithm quantifies the reactivity of the functional groups of the monomer structure and assigns special characters to those positions in the output SMILES.1. Input a csv file containing the polymer name and either a reaction SMILES or a monomer SMILES. 2. If a reaction SMILES is provided, use HTA to identify the monomer by evaluating Chemical Similarity. 3. Separate molecular entities and calculate fingerprints using RDKFingerprint. 4. Compare fingerprints using Tanimoto Similarity and select the reactant SMILES with the highest similarity score as monomer SMILES. 5. Use the Assigner module to perform classification tasks and tag head and tail atoms. 6. For identifying the polymer class, compare the monomer SMILES with SMARTS of common functional groups. 7. For polyamide, ensure a primary amine and a carboxylic acid or a secondary amide and a heterocycle monomer are present. 8. For polyester, ensure an aliphatic alcohol group and a carboxylic acid group or a heterocycle group and a carboxylic acid group are present. 9. For polyether, ensure an ether group and perform ring-opening. 10. For polyurethane, include one monomer with an alcohol group and another with a cyanate group. 11. Calculate the nucleophilicity index using the STO-3G basis set and Mulliken’s population analysis method. 12. Generate the GAMESS input file by converting the SMILES string into a 3D coordinate file with OpenBabel and geometry optimization. 13. Extract HOMO population data from the GAMESS output file to calculate R_X for each atom. 14. Rank R_X in descending order to identify the functional group with the highest reactivity as the polymerization site. 15. Assign the polymer to its class based on the highest R_X functional group. 16. Use the Get Class routine to obtain the polymerization mechanism. 17. Assign the head and tail atoms in the monomer SMILES according to the defined polymerization rules. 18. Compile the results in csv format, including polymer name, reaction SMILES, assignment results for monomer, polymer class, polymerization mechanism, head, and tail atoms."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/High performance pressure-sensitive adhesive polymers-1989.json b/task2/task2-paper-info/High performance pressure-sensitive adhesive polymers-1989.json
new file mode 100644
index 0000000..c3ff94b
--- /dev/null
+++ b/task2/task2-paper-info/High performance pressure-sensitive adhesive polymers-1989.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of hydrophilic polymers with functional groups is conducted by copolymerizing a glycidyl monomer with an N-vinyl lactam. Specific details include the use of 35-75% by weight of at least one glycidyl monomer, in combination with 10-30% by weight of the N-vinyl lactam. Additional functional groups can be introduced by including an ethylenically unsaturated carboxylic acid in percentages ranging from 0.1-10% by weight. The molecular weight of the copolymers is optimized to be within the range of 10,000-500,000. Catalysts or curing agents such as 1,3-bis(dimethylamino)-2-hydroxypropane may be utilized to facilitate the curing of the epoxy groups. The resulting polymer should demonstrate high adhesion properties and suitable mechanical characteristics under varying temperatures and humidity conditions.Copolymers are prepared by copolymerizing a mixture of 15 monomers comprising: 55 to 85% by weight of an alkyl acrylate and/or methacrylate ester containing 4 to 12 carbon atoms in the alkyl group; 0.01 to 2% by weight of a glycidyl monomer; 1 to 20% by weight of an N-vinyl lactam monomer; 0 to 15% by weight of an unsaturated carboxylic acid; 0 to 35% by weight of an alkyl acrylate and/or methacrylate ester containing less than 4 carbon atoms in the alkyl group; optionally 0 to 33% by weight of one or more other comonomers. The precise ratio of the monomers is selected to give a polymer with a glass transition temperature lower than -15° C. The weight average molecular weight of the polymers should be at least 200,000, preferably from 200,000 to 500,000, determined by size exclusion chromatography using polystyrene as the calibrator. The copolymers may be synthesized using solution, emulsion, and batch polymerization techniques.The synthesis of hydrophilic polymers is performed via solution polymerization using a mixture of solvents, preferably a blend of ethyl acetate and hexane or ethyl acetate and acetone. The solvent ratio is adjusted to achieve a reflux temperature between 68° C. and 78° C. A solids content of approximately 40% to 60% is maintained during polymerization to achieve the desired weight average molecular weight and manageable viscosities. Free-radical initiators, preferably azo-type such as 2,2'-azobis(isobutyronitrile), are used to initiate the reaction. The glycidyl monomer is limited to 2% by weight of the total monomers to avoid cross-linking. Post-polymerization cross-linking may be performed using heat, actinic or electron beam radiation. The presence of glycidyl and lactam monomers is essential for superior adhesion to high energy surfaces.A monomer mixture was prepared by mixing 423 g of 5 2-ethyl hexyl acrylate, 145 g of methyl acrylate, 3.15 g of glycidyl methacrylate, 12.6 g of N-vinyl pyrrolidone, and 44.1 g of acrylic acid. 157 g of this mixture was introduced into a 2-liter reactor equipped with a pitched turbine agitator, a reflux condenser, and a thermistor. Additionally, 73.5 g of ethyl acetate and 78.76 g of hexane were added. The reactor contents were heated to reflux, and 0.238 g of Vazo 64 was added in 5 g of ethyl acetate. The contents were held under vigorous reflux for 23 minutes. The remaining monomers, mixed with 37.2 g of ethyl acetate, 5.2 g of hexane, and 0.707 g of Vazo 64, were added as a single feed mixture over 3.5 hours, maintaining the temperature to keep the reactor contents under reflux. One hour after the end of the feed, an additional 0.17 g of Vazo 64 was added in 5 g of ethyl acetate, and the mixture was held for an additional hour. The final solids content was 46.4% and the viscosity was 23 Pa.s using #4@12 on a Brookfield viscometer.A monomer mixture was made up by mixing 453.6 g of Isooctyl acrylate, 100.8 g of methyl acrylate, 6.3 g of glycidyl methacrylate, 25.2 g of N-vinyl caprolactam, 4.1 g of acrylic acid and 0.945 g of Vazo 64. 157.5 g of this mixture was introduced to the reactor with 78.76 g of hexane, 78.76 g of ethyl acetate and heated to reflux. Once vigorous reflux initiated, the contents were held for about 12 minutes and the remaining monomers added along with 537.24 g of ethyl acetate and 75.24 g of hexane as a single feed over 3 hours. Two hours after the end of feed, the contents were cooled.To synthesize hydrophilic polymers with functional groups, combine the following monomers in specified weight percentages: For Control 1, use 65.7% 2-ethyl hexyl acrylate, 27.3% methyl acrylate, and 7% acrylic acid. For Control 2, use 67% 2-ethyl hexyl acrylate, 24% methyl acrylate, 7% acrylic acid, and 2% N-vinyl pyrrolidone. For Control 3, use 65.7% 2-ethyl hexyl acrylate, 27.2% methyl acrylate, 7% acrylic acid, and 0.1% glycidyl methacrylate. For Control 4, use 65% 2-ethyl hexyl acrylate, 27% methyl acrylate, 7% acrylic acid, and 1% glycidyl methacrylate. Add 0.2 parts by weight of aluminum acetyl acetonate as a cross-linker. The polymers are then subjected to a rivet tenting test using an adhesive transfer coating method on a cast vinyl facestock at a coat weight of 30 g/m2."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/Highly transparent superhydrophilic graphene oxide coating for antifogging.json b/task2/task2-paper-info/Highly transparent superhydrophilic graphene oxide coating for antifogging.json
new file mode 100644
index 0000000..925c16f
--- /dev/null
+++ b/task2/task2-paper-info/Highly transparent superhydrophilic graphene oxide coating for antifogging.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "A simple and low-cost method for preparing high performance GO coating on glass substrate is described. The synthesis involves using graphene oxide (GO) which has various oxygen-containing functional groups that contribute to its hydrophilic properties. The process aims to achieve high optical transmittance and superhydrophilic characteristics without the complex steps of reduction and bridization commonly associated with other preparation methods.GO was prepared using the modified Hummers method. To remove the oxidant and other inorganic impurities, the GO slurry was washed with deionized water by repeated vacuum filtration through a 100 nm cellulose acetate membrane. Then the suspension was centrifuged at 13,000 rpm for 80 minutes, and the supernatant was kept. Finally, the supernatant was diluted with deionized water to a total volume of 200 ml in a 500 ml flask to make a homogeneous GO suspension at 0.2 mg/l for storage.GO coating was deposited on the glass substrate by a spin coating process. Initially, the substrate was ultrasonically cleaned in ethanol and deionized water. After cleaning, the substrate was dried at 60°C for 1h. Then, the above-mentioned GO suspension was dropped on the glass substrate and spun at 500rpm for 10s and dried at 60°C for 3h to enhance the mechanical property of the coating. The other side of the glass substrate was operated by the same procedure. Finally, both sides of the glass substrate were covered with GO coating."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/Hydrophilic and superhydrophilic surfaces and materials.json b/task2/task2-paper-info/Hydrophilic and superhydrophilic surfaces and materials.json
new file mode 100644
index 0000000..739c2b5
--- /dev/null
+++ b/task2/task2-paper-info/Hydrophilic and superhydrophilic surfaces and materials.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "The excerpt does not contain any specific experimental protocol for the synthesis of hydrophilic polymers with functional groups."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/IPDI╘┌╛█░▒їе╖┤╙ж╓╨╢╘╤б╘ё╨╘╬┬╢╚бв┤▀╗п╣¤│╠║═╖┤╙ж╢╘╧є╡─╙░╧ь.json b/task2/task2-paper-info/IPDI╘┌╛█░▒їе╖┤╙ж╓╨╢╘╤б╘ё╨╘╬┬╢╚бв┤▀╗п╣¤│╠║═╖┤╙ж╢╘╧є╡─╙░╧ь.json
new file mode 100644
index 0000000..dc2e940
--- /dev/null
+++ b/task2/task2-paper-info/IPDI╘┌╛█░▒їе╖┤╙ж╓╨╢╘╤б╘ё╨╘╬┬╢╚бв┤▀╗п╣¤│╠║═╖┤╙ж╢╘╧є╡─╙░╧ь.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "本项研究中的内容包括：在氨基甲酸酯反应中各种催化剂、温度、位阻和/或醇类的反应活性对模型反应的选择性影响以及其对工业中可予实践体系的适用性。假设：单氨基甲酸酯单异氰酸酯的氨基甲酸酯官能团对残余异氰酸酯基的反应活性既无催化剂性质、也无阻遇性质的影响；顺式和反式IPDI具有可比的反应活性。根据以上假设，构建简化动力学模型，研究异氰酸酯在过量状态下的转化率。在一个有搅拌的反应器中，在氮气保护下恒温进行，将赫斯公司（Huels AG）的VESTANATIPDI和催化剂加人反应器中，将醇在5h内滴加完。反应持续进行到转化完全为止。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/PUA.json b/task2/task2-paper-info/PUA.json
new file mode 100644
index 0000000..55a7beb
--- /dev/null
+++ b/task2/task2-paper-info/PUA.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of hydrophilic polymers with functional groups involves incorporating polar groups or rigid groups into the molecular chains of the polymer to enhance crystallinity or rigidity. This can be executed by blocking or grafting techniques at the molecular level, which allows for the adjustment of the mechanical properties of the resulting polymer.PUA is synthesized by introducing double bonds of acrylates into the terminal molecular chain of polyurethane. Oligomers are then used to initiate a double-crosslinking reaction in the presence of photoinitiators.To synthesize hydrophilic polymers, select diisocyanates such as toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), or hexamethylene diisocyanate (HDI) as urethane segments, and chain extenders like ethylene diamine (EDA) or ethane glycol (EG). Use polyols or polyamines such as polyethylene glycols (PEG), polytetrahydrofuran (PTMEG), poly(caprolactone glycol) (PCL), or polycarbonate diols (PCDL) with hydroxyl or amino groups to react with the diisocyanates by semi-adduct reaction. For acrylate segments, include hydroxyethyl acrylate (HEA) as an end-capper. To increase functionality, introduce trimethylolpropane diallyl ether (TMPDE) or pentaerythritol triacrylate (PETA) into the system. Explore greener raw materials for non-isocyanate polyurethane (NIPU) synthesis, such as cyclic carbonate and diamine, and consider vegetable oils as sustainable polyol substitutes. Optionally, add reactive diluents like tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), or pentaerythritol tetraacrylate (PETTA) to enhance crosslinking and lower viscosity during UV curing."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/Photoinitiator pendanted on hydrophilic oligomer.json b/task2/task2-paper-info/Photoinitiator pendanted on hydrophilic oligomer.json
new file mode 100644
index 0000000..cc68e14
--- /dev/null
+++ b/task2/task2-paper-info/Photoinitiator pendanted on hydrophilic oligomer.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "The hydrophilic polymer is synthesized using a two-component system comprising a first oligomer and a second oligomer. The first component oligomer includes: (a) 20 to 99 parts by weight of polymerized monomer units derived from an ethylenically-unsaturated monomer possessing a poly(alkylene oxide) group, (b) 0.1 to 35 parts by weight of polymerized monomer units derived from an ethylenically-unsaturated monomer with a pendent polymerizable group, (c) 0 to 50 parts by weight of polar monomer units, and (d) 0 to 20 parts by weight of hydrophobic monomer units. The second component oligomer consists of: (a) 0.01 to 99.99 parts by weight of free radically polymerizable monomer units and (b) 99.99 to 0.01 parts by weight of polymerized monomer units derived from an ethylenically-unsaturated monomer having a pendent photoinitiator group. The two components should be combined such that the second component provides greater than two crosslinks per first component oligomer chain upon curing. Polymerization can be conducted through thermal or photochemical methods using appropriate solvents and initiators. For photoinitiation, a variety of UV light sources and photoinitiators, as well as their optimal concentrations, are specified to achieve desired crosslinking and material properties.A series of hydrophilic copolymers were synthesized by charging 5 amber glass bottles with different weight proportions of hydrophilic monomers and alpha-methyl styrene. Sufficient ethyl acetate was added to each bottle so that the total monomer concentration was 50 weight percent. VAZO 52 (0.4 g) was added to each bottle. The contents of each bottle were purged with nitrogen gas for 20 minutes and the bottle was capped using poly(tetrafluoroethylene) thread tape. Each bottle was placed in a Model LLF LAUNDER-O-METER, with the water bath temperature set at 60°C, for 16 hours. After 24 hours, each sample disk was removed from the solution and the excess liquid was allowed to drip off for 1 minute. The sample disk was weighed and this weight was recorded as \"wet weight.\" The absorbency of each sample disk was calculated as the increase in sample weight, expressed as a percentage of the dry weight.A hydrophilic copolymer with photoinitiator pendant groups was synthesized by charging an amber glass bottle with 99.0 g of MPEG, 1.0 g of DAROCUR ZLI-3331, 0.1 g of α-methyl styrene, 0.4 g of VAZO 52 and 100 g of ethyl acetate. The contents of the bottle were purged with N2 for 20 minutes and the bottle was capped, using poly(tetrafluoroethylene) thread tape between the cap and the threads of the bottle. The bottle was placed in a Model LLF LAUNDER-OMETER, with the water bath temperature set at 60°C, for 16 hours. The resulting polymer had a Mn of 36,900 as determined by GPC.Charge an amber glass bottle with 65.0 g of MPEG, 35.0 g of HEMA, 1.0 g of DAROCURE ZLI-3331, 4.0 g of alpha-methylstyrene, 0.4 g of AIBN, and 90 g of ethyl acetate. Purge the contents with nitrogen gas for 20 minutes and cap the bottle using poly(tetrafluoroethylene) thread tape. Place the bottle in a water bath shaker at 65°C for 24 hours. The resulting polymer has a Mn of 15,700 as determined by GPC.Each solution of the products from Preparatory Examples 3-7 was combined with VDM and a catalytic amount of DBU in an amber bottle. The bottle was agitated in a heated shaker water bath at 60°C for 16 hours.Each solution of the products from Preparatory Examples 3-5 was combined with IEM and a catalytic amount of dibutyltin dilaurate in an amber bottle. The bottle was agitated in a heated shaker water bath at 60 degrees C for 16 hours.A series of hydrophilic copolymers were synthesized by charging 4 amber glass bottles with different weight proportions of hydrophilic monomers and alpha-methyl styrene, and VAZO 52 (0.4 g). Sufficient ethyl acetate was added to each bottle so that the total monomer concentration was 50 weight percent. The contents of each bottle were purged with nitrogen gas for 20 minutes and the bottles were capped using poly(tetrafluoroethylene) thread tape. Each bottle was placed in a Model LLF LAUNDER-O-METER, with the water bath temperature set at 60 degrees Celsius, for 16 hours. This step was performed by agitating the mixture at room temperature for 48 hours.Combine solutions of products from Preparatory Examples 16-19 with different proportions of HEMA, BHT (100 ppm), and a catalytic amount of DBU in an amber bottle. Agitate the bottle in a heated shaker water bath at 60°C for 16 hours.A hydrophilic copolymer was synthesized by charging an amber glass bottle with 65.1 g of MPEG, 35.0 g of HEMA, 4.0 g of a-methyl styrene, 0.4 g of AIBN and 90 g of ethyl acetate. The contents of the bottle were purged with nitrogen gas for 20 minutes and the bottle was capped, using poly(tetrafluoroethylene) thread tape. The polymerization bottle was placed in a water bath shaker at 65°C for 24 hours. The resultant polymer had a M_n of 12,200 as determined by GPC. A series of copolymers with pendent ethylenic unsaturation were prepared by reacting portions of this copolymer with different weight proportions of IEM and a catalytic amount of dibutyltin dilaurate.A series of films were prepared by mixing either IG184 or different proportions of the solution of the product of Preparative Example 1 (referred to as Component C) with different proportions of each solution of the product of Preparative Examples 20-23 (referred to as Component D). The mixed solutions were separately coated onto poly(ethylene terephthalate) (PET) release liner and the solvent was evaporated by heating the coatings in an oven at 50°C for 4 hours. Another layer of PET release liner was then placed on top of the film, providing a coated film between two sections of PET release liner. This was irradiated as described in previous examples.A series of films were made by mixing equal weights of a solution of each of the products from Preparative Example 24-29 (identified as Component E in Table 9) with a solution of the product of Preparative Example 2. The resultant solutions were separately coated onto poly(ethylene terephthalate) (PET) release liner, and the solvent was evaporated by heating the coatings in an oven at 50°C for 4 hours. Another layer of PET release liner was then placed on top of the film, providing a coated film between two sections of PET release liner. This was irradiated as described in Examples 30-61."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/Preparation of water-resistant antifog hard coatings on plastic substrate.json b/task2/task2-paper-info/Preparation of water-resistant antifog hard coatings on plastic substrate.json
new file mode 100644
index 0000000..3a7e570
--- /dev/null
+++ b/task2/task2-paper-info/Preparation of water-resistant antifog hard coatings on plastic substrate.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "The antifog coating is prepared using a bilayer configuration. The bottom layer (primer) is created by forming a cross-linked network of poly(acrylate) embedded with nanosized silica to provide mechanical strength and adhesiveness. The top layer, an antifog (AF) layer, has a surface active agent, Tween 20, that is modified and covalently incorporated into the polymer host. The two layers are interlinked by UV-cured poly(acrylate), making them mechanically inseparable while maintaining a uniform transparent appearance. The coating is designed to withstand rinsing in water and remain intact after drying, due to the hydrophobic feature of the primer, which prevents water penetration and detachment from the substrate.To synthesize hydrophilic polymers with functional groups, follow these steps: First, prepare the coating sol for the antifog (AF) layer by modifying hydrophilic agents. Stir equal moles of 2-hydroxyethyl methacrylate (2-HEMA) and isophorone diisocyanate (IPDI) in a glass reactor under temperature control. When the temperature reaches 50 °C, add dibutyltin dilaurate (0.1% of the total weight of 2-HEMA and IPDI) as the catalyst and allow the reaction to proceed for 2 hours at this temperature. Next, add the hydrophilic agent (Tween 20) and react for another 2 hours. The molar ratio of IPDI to Tween 20 should be set to 1. This produces a modified hydrophilic agent referred to as T20. Subsequently, prepare the AF coating sols by mixing T20 with the coating sol for the bottom layer, adjusting the dipentaerythritol hexaacrylate (DPHA) content to ensure 30 wt% silica in the sol. Finally, spin-coat this sol on a partly cured bottom layer, predry at 80 °C for 40 seconds, and UV-cure at 500 mJ/cm² to obtain an AF layer approximately 1 μm thick."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/RSC-terminated polysilicon.json b/task2/task2-paper-info/RSC-terminated polysilicon.json
new file mode 100644
index 0000000..0d45bbd
--- /dev/null
+++ b/task2/task2-paper-info/RSC-terminated polysilicon.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of hydrophilic polymers involves the use of (meth)acrylate groups for photopolymerization. Proper selection of acrylic/methacrylic monomers and curing agents is essential to tailor the performance characteristics of the polymers. The process aims to improve the hydrophobicity of the materials for applications by combining these monomers with additives or modifications to achieve the desired properties.Minor amount of hydroxyethylmethacrylate were added to promote adherence property. Glycidyl methacrylate was used to introduce epoxy groups to react with methacrylate (MA) in the following reaction step. A series of organosiloxane modified polyacrylate (OSPAs) at different organosilicone concentration ratios were prepared by mixing PA with MATSi. In the presence of photoinitiator, OSPAs were crosslinked by the radical polymerization of the carbon-carbon double bonds in UV irradiation. The obtained polymers were characterized by gel permeation chromatography (GPC), fourier transform infrared (FT-IR) spectroscopy and nuclear magnetic resonance (NMR). Additionally, surface hydrophobic, optical, and thermal properties of the cross-linked coatings were investigated by gel content test, flexibility test, pencil hardness test, contact angle (CA) analysis, refraction index test, scanning electron microscope, energy dispersive spectrometer, differential scanning calorimetry thermograms, and thermogravimetric analyzer.Octaphenylpolyoxyethylene (OPE) was obtained from Quzhoumingfeng chemical company. Irgacure 1173 was obtained from Ciba Specialty Chemicals.Dodecylbenzene sulfonic acid (DBSA), glycidyl methacrylate (GMA), hydroxyethylmethacrylate (HEMA), 6-methylheptyl methacrylate (MHMA), methacrylic acid (MA), and methacryloxy propyl trimethoxylsilane (KH570) were utilized for the synthesis of hydrophilic polymers. The synthesis involves mixing these components without purification and can include other solvents and initiators such as methanol, triethanolamine, and azobisisobutyronitrile (AIBN) under specified reaction conditions to obtain the desired hydrophilic polymer with functional groups.The polyacrylate was prepared using a 1:1:8 weight ratio of GMA, HEMA, and MHMA in the presence of 4 wt% AIBN as initiator and butanone as solvent at a temperature of 80°C. The reaction was performed in a four-neck reaction kettle equipped with mechanical stirring, nitrogen inlet, water condenser, and thermometer for 8 hours. After the reaction, butanone was removed by reduced pressure distillation, and the product was labeled as GHM. This was then transferred to another four-neck kettle where a certain amount of MA was added in the presence of 0.8 wt% TBAB. The reaction continued at 102°C until 99.5% conversion was achieved, determined by standard acid value. Remaining butanone and unreacted MA were removed by reduced pressure distillation, and the final product was obtained and labeled as PA.MATSi was synthesized by emulsion polymerization. Distilled water, surfactants (DBSA and OPE), and monomers (D4) were added into a four-necked flask equipped with a thermometer, a reflux condenser, a mechanical stirrer, and a nitrogen inlet. Nitrogen was introduced to remove oxygen initially. The reaction was carried out for 8 hours at 80°C with stirring at about 500 rpm. After neutralizing with NaOH solution to stop the reaction, the final latex of PDMS was obtained. A specific quantity of KH570 was added into PDMS latex, and the condensation reaction of PDMS and KH570 was performed at 80°C for 3 hours. The copolymers were precipitated in ethanol and dried in a vacuum drying oven. The product was purified in ethanol and hexane several times to remove unreacted monomers and surfactants, resulting in the product designated as MATSi.Mix PA and MATSi in relative mass ratios ranging from 100:0 to 90:10. Add 5 wt% photoinitiator (Irgacure 1173/triethanolamine at a 2:3 w/w ratio) to each formulation while stirring for 10 minutes. Use triethanolamine to prevent oxygen inhibition during the UV-curing process. Cast the films onto a glass plate using 5% w/v solutions.Copolymers are synthesized in methanol using a wire-wound applicator. The coated films are allowed to sit at room temperature for at least 5 minutes until the solvent evaporates. After evaporation, the films are irradiated with a high-pressure mercury lamp (500W) for 30 seconds, maintaining a distance of 20 cm from the lamp to the surface of the samples in air atmosphere. The final thickness of the coating is approximately 100 micrometers.The molecular weight and distributions of PA and MATSi oligomer samples were measured at 25°C by gel permeation chromatography (GPC) on Waters 2410 instrument with THF as the solvent (1.0 ml/min) and polystyrene as the calibration standards. The FT-IR spectra were recorded with TENSOR27, Bruker, Germany spectrometer over the range 400 to 4000 cm^-1. 1H NMR and 29Si NMR were recorded with a 400MHz Bruker NMR spectrometer using CDCl3 as solvent and tetramethylsilane as the internal reference. The gel content method was performed on the cured films by measuring the weight loss after a 48-h extraction at 80°C, according to the standard test method ASTM D2665-84. Gel content was calculated as: Gel content = (W_t / W_0) × 100%, where W_0 is the initial weight of the film, and W_t is the final weight after extraction.Five UV-curable organosiloxane modified polyacrylates, OSPA1, OSPA2, OSPA3, OSPA4, OSPA5, were first prepared in this work in order to study the effects of silicon on the properties of UV-curable composite coatings.The synthesis of hydrophilic polymers involves the reaction of epoxide groups with methacrylic acid (MA) via a ring-opening addition reaction. Monitor the reaction by recording FT-IR spectra to confirm the disappearance of the characteristic absorption peak of the epoxide group at 910 cm^{-1}, which indicates the completion of the reaction. The formation of hydroxyl groups is indicated by the peaks at 1640 cm^{-1} (methacrylate double bond) and 700 cm^{-1} (C-O-H bending). Additionally, confirm the introduction of C=C groups and the presence of acrylate characteristics by observing carbonyl stretch at 1720 cm^{-1} and C-O stretches between 1140 cm^{-1} to 1280 cm^{-1}.The coating formulation was coated on a KBr window and then exposed to UV radiation for 30 s. The degree of conversion was determined using FT-IR spectroscopy by monitoring the absorption band at 1640 cm^{-1} due to C=C vibration. The degree of conversion was calculated using the equation Degree of conversion = (1 - (A_t / A_o)) x 100, where A_o is the absorption before UV exposure and A_t is the absorption after UV exposure."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/Rheology_-_2015.json b/task2/task2-paper-info/Rheology_-_2015.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/Rheology_-_2015.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/SDC-FSI CN109070134B.json b/task2/task2-paper-info/SDC-FSI CN109070134B.json
new file mode 100644
index 0000000..e4f1cc0
--- /dev/null
+++ b/task2/task2-paper-info/SDC-FSI CN109070134B.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "1. Prepare a coating composition with one or more radiation-curable acrylates that have a hydrophilic region containing one or more reactive hydrophilic alkylene oxide moieties characterized by the formula: Ω(CH2)Ωn(0-)Σm-, where n is between 1 and 3, and m is between 1 and 10. 2. Include a reactive surfactant with a reactive portion in an amount of 0.5 wt% to 4.3 wt% based on the weight of the coating composition. 3. Add a photoinitiator to the composition. 4. Expose the photoinitiator to light energy, which will cure the radiation-curable acrylates to form a hydrophilic network by binding the reactive portion of the surfactant moiety to one or more acrylate groups in the hydrophilic region of the acrylates. 5. Apply the coating to a substrate and cure it to achieve a transparent, washable, anti-fog coating. 6. Soak the coating in room temperature water for 1 hour, then dry at 25°C and 50% relative humidity for 12 hours. 7. Expose the coating to water vapor from a heated water bath at 50°C for 1 minute, ensuring the coating remains fog-free.将涂料组合物中的亲水网络与一种或多种可辐射固化的丙烯酸酯结合，所述丙烯酸酯包含一个或多个亲水烷氧基化物基团，所述基团的化学式为$\\big(\\mathrm{(CH_{2})^{}_{n}0-}\\big)_{\\mathrm{~m~}^{-}}$，其中n的范围为1至3，m的范围为1至10。将涂料组合物中反应性表面活性剂的添加量控制在0.5重量%-4.3重量%并将其反应性部分结合到所述亲水区域中的丙烯酸酯基团。将涂层在室温水中浸泡1小时，随后在25°C且50%相对湿度下干燥12小时，最后暴露于来自加热至50°C的水的水蒸气中1分钟以实现防雾效果。提供涂料组合物，其中包含(a)具有亲水区和在亲水区中的反应性基团的可辐射固化树脂，和(b)包含可与在聚合物的亲水区中的反应性基团反应的一个或多个反应性基团的反应性表面活性剂。在固化后，由于树脂的反应性基团和反应性表面活性剂之间的结合形成亲水网络。该涂料组合物在施加到基材并固化时提供光学透明的可洗涤的防雾涂层。反应性表面活性剂的反应性部分可与可交联树脂的反应性基团反应，且可以在将反应产物加入到丙烯酸酯混合物之前使表面活性剂与反应性部分反应，或可以同时将表面活性剂和反应性部分加入到丙烯酸酯混合物中。在一些实施方案中，组合物可以包含分散在整个亲水可交联树脂例如丙烯酸酯的网络中的金属氧化物颗粒。金属氧化物颗粒的合适实例包括但不限于二氧化硅颗粒、氧化钛、氧化铝、氧化锌、氧化锑、氧化锡、锆氧化物及其组合。组合物中的丙烯酸酯的浓度可以为约4%至95%重量。反应性表面活性剂的浓度可以为液体涂料的0.5%至30%重量。在一些实施方案中，组合物还可以包含具有烯基反应性基团的反应性表面活性剂，且可选自阴离子表面活性剂。组合物可以通过将涂覆的基材暴露到UV灯提供的UV辐射、由可见光灯提供的可见光辐射，或在一些实施方案中，由电子束促进剂提供的EB辐射来进行固化。将135.01克SR9035加入到含有24.65g配备有磁力搅拌棒的3‑EGA的圆底烧瓶。将内容物在室温下连续搅拌30分钟。在搅拌30分钟后，在室温下在不断搅拌下缓慢加入850.65克MEK‑AC‑2140Z，且将混合物搅拌过夜。然后使用Buschi Rotovap在40°C和730 mTorr下真空蒸馏混合物。然后将浓缩的树脂用192g的PM二醇醚稀释。然后将混合物转移到适合于包装可UV固化涂料的加盖棕色容器中并使其冷却至室温。将94.7克预混物1、1.47克预混物2、1.50克预混物3和2.29克Darocur 1173加入到容器，并使用磁力搅拌棒在室温下搅拌30分钟。然后使涂料混合物静置1小时。根据施加方式，通过用PM稀释进一步调节固体的涂料混合物。经由浸涂、刮涂棒、流涂和旋涂以各种方式施加涂料。涂覆的部分在Fusion UV固化单元中用H灯泡在2.0 J/cm²下固化。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/SDC-FSI╖└╬э-CN109070134B.json b/task2/task2-paper-info/SDC-FSI╖└╬э-CN109070134B.json
new file mode 100644
index 0000000..0d64e63
--- /dev/null
+++ b/task2/task2-paper-info/SDC-FSI╖└╬э-CN109070134B.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "将亲水网络制作成包含一种或多种可辐射固化的丙烯酸酯，所述丙烯酸酯具有包含一个或多个亲水烷氧基化物基团的亲水区域，亲水烷氧基化物基团满足公式-(CH_{2})_{n}0-，其中n在1到3之间，且结合包含反应性部分的反应性表面活性剂到亲水区域中的丙烯酸酯基团，反应性表面活性剂的用量为涂料组合物重量的0.5%到4.3%。然后，将涂层在室温水中浸泡1小时，随后在25°C和50%相对湿度下干燥12小时，最后暴露于从加热至50°C的烧杯中蒸发出的水蒸气中1分钟，最终形成不雾化的涂层。本公开提供涂料组合物，其包含(a)具有亲水区和在亲水区中的反应性基团的可辐射固化树脂，和(b)包含可与在聚合物的亲水区中的反应性基团反应的一个或多个反应性基团的反应性表面活性剂。在一些实施方案中，组合物是液体且在暴露到辐射后固化。在固化后，由于树脂的反应性基团和反应性表面活性剂之间的结合形成亲水网络，其中所述反应性表面活性剂结合到网络。在一些实施方案中，当施加到基材并固化时，这种涂料组合物提供光学透明的可洗涤的防雾涂层。反应性表面活性剂的反应性链段在固化过程期间与丙烯酸酯的亲水区反应，从而在固化后保持在原位，以提供具有持久的防雾性质的涂层。组合物可以通过常规方法例如流涂、喷涂、幕涂、浸涂、旋涂、缝模涂覆、辊涂等施加到固体基材以形成基材上的连续表面膜。然后涂料组合物通过将涂覆的基材暴露到由UV灯提供的UV辐射、由可见光灯提供的可见光辐射，或在一些实施方案中，由EB促进剂提供的EB辐射，或这些的组合来固化。将69.88克预混物1、1.09克预混物2、1.11克REASOAP SR-10、1.69克Darocur 1173、0.37克Tergitol 15-s-7和25.86克PM混合30分钟。在混合后，在施加到基材之前使制剂静置1小时。经由浸涂和旋涂以各种方式施加涂料。涂覆的部分在Fusion UV固化单元中用H灯泡在2.0 J/cm²下固化。"
+}
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diff --git a/task2/task2-paper-info/SMiPoly┐╔║╧│╔╛█║╧╬я╨щ─т┐т╡─╔·│╔╩╣╙├╗∙╙┌╣ц╘Є╡─╛█║╧╖┤╙ж.json b/task2/task2-paper-info/SMiPoly┐╔║╧│╔╛█║╧╬я╨щ─т┐т╡─╔·│╔╩╣╙├╗∙╙┌╣ц╘Є╡─╛█║╧╖┤╙ж.json
new file mode 100644
index 0000000..5e018ea
--- /dev/null
+++ b/task2/task2-paper-info/SMiPoly┐╔║╧│╔╛█║╧╬я╨щ─т┐т╡─╔·│╔╩╣╙├╗∙╙┌╣ц╘Є╡─╛█║╧╖┤╙ж.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Using 1083 input monomers carefully selected based on availability, cost, safety, and legal compliance, polymerize seven classes of polymers, specifically polyolefins, polyesters, polyethers, polyamides, polyimides, polyurethanes, and polyoxazolidones, in silico. Implement a comprehensive rule set consisting of 22 reaction rules, which includes six chain polymerization reactions and 16 step-growth polymerization reactions.To synthesize hydrophilic polymers with functional groups, first classify starting molecules to identify those capable of forming monomers as per the polymerization rule set, which involves checking for specific functional groups. Utilize the submodule 'monc.py' to categorize the extracted starting molecules into 19 different monomer classes based on the presence or absence of polymerizable functional groups. Then, apply the submodule 'polg.py' to map the identified monomers to applicable polymerization reactions based on the specified functional group transformations. For step-growth polymerization, select pairs of monomers that each contain at least two polymerizable functional groups, or opt for a single monomer with two different functional groups. Ensure that the occurrences of polymerizable functional groups in monomers are within the default limits of 2 to 4 for the reaction to proceed efficiently. Finally, generate the polymer library using the combination of selected monomers and the designated polymerization reactions, committing to either bipolymer or homopolymer formation as dictated by the functional group compatibility."
+}
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diff --git a/task2/task2-paper-info/Solvents_-_2015.json b/task2/task2-paper-info/Solvents_-_2015.json
new file mode 100644
index 0000000..dfecdb6
--- /dev/null
+++ b/task2/task2-paper-info/Solvents_-_2015.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Determine solubility parameters by trying various known solvents to find the most compatible one for the unknown polymer. Measure the viscosity of the polymer solution in relation to the solubility parameter of the solvent, identifying the solvent that yields the highest viscosity as the most suitable for swelling the polymer."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/Synthesis and characterization of UV curable urethane acrylate oligomers containing ammonium salts for anti-fog coatings.json b/task2/task2-paper-info/Synthesis and characterization of UV curable urethane acrylate oligomers containing ammonium salts for anti-fog coatings.json
new file mode 100644
index 0000000..227a38f
--- /dev/null
+++ b/task2/task2-paper-info/Synthesis and characterization of UV curable urethane acrylate oligomers containing ammonium salts for anti-fog coatings.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "UV curable urethane acrylate oligomer containing ammonium salts for anti-fog coating was developed.Monomers, including ethanolamine and 2-butanone, are purified by vacuum distillation before use. SY-40M is used without purification. Dimethyl sulfate is purified by vacuum distillation prior to use. Isophorone diisocyanate (IPDI) and dibutyltin dilaurate (DBTDL) are sourced from reputable suppliers. TLC analysis is performed using TLC Silica gel $60\\mathsf{F}_{254}$ for monitoring the reactions.Ethanolamine (10.16 g, 0.166 mol) was added to a 250 mL three-neck flask equipped with water bath, thermometer, refluxing condenser, dropping funnel, and magnetic stirring bar, and heated to 60°C with stirring. 86.55 g of alkyl glycidyl ether (Sy 40M) was slowly added and the mixture was maintained for 2 h at 70°C. Dimethyl sulfate (20.99 g, 0.166 mol) and methyl ethyl ketone (MEK, 29.8 g) were added dropwise to the stirred mixture over 3 h, while maintaining the temperature at 60°C. The salt group of the final product was identified by titration of the remaining amine group with 0.1 N HCl solution, indicating that 80% of the total amine group was converted into quaternary ammonium group. The reaction product was identified with 1H NMR (CDCl3, 300 MHz): 4.17 ppm (N+-CH2C(H)(-OH)-CH2), 4.01 ppm (N+-CH2C(H)2OH), 3.52 ppm (CH2CH(-OH)-C(H2)O), 3.43 ppm (N+-CH2C(H)2OH), 3.39 ppm (N+-CH2C(H)(OH)CH2), 3.29 ppm (N+-CH3), 1.22 ppm O(CH2)C(H)3.To a solution of IPDI (34.5g, 0.16mol) and PETA (100g) in MEK (100mL), DBTDL (0.25g) was added dropwise at 10°C with stirring. After complete addition, the mixture was stirred at 10°C for 4h. The reaction progress was analyzed by TLC using ethyl acetate: hexane = 1:2 (v/v). The AS monomer (96.2g) in MEK (20mL) was added to the above reaction product over 4h, while maintaining the temperature at 20°C. The reaction product was identified with 1H NMR (CDCl3, 300MHz) and FT-IR.UV curable anti-fog (AF) compositions were prepared by mixing homogenously UV-UAO with reactive diluents (PETA:DPHA = 8.5:1.5 by weight) and the photoinitiator (1- Hydrophenyl ketone, Irgacure 184 from Ciba Specialty Chemicals, maximum peak of absorption: 245-330 nm). Different amounts of UV-UAO (55-70 wt.%) were added into the above composition and the photoinitiator concentration was kept constant at 5 wt.% all on the basis of final formulation. A 20-μm thick coating of the resin composition was applied on the polycarbonate (PC) using bar applicator and then cured with 80 W/cm light a medium pressure mercury lamp of conventional UV equipment."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/Synthesis of UV-curable acrylate polymer containing sulfonic groups for anti-fog coatings.json b/task2/task2-paper-info/Synthesis of UV-curable acrylate polymer containing sulfonic groups for anti-fog coatings.json
new file mode 100644
index 0000000..1e1b40e
--- /dev/null
+++ b/task2/task2-paper-info/Synthesis of UV-curable acrylate polymer containing sulfonic groups for anti-fog coatings.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis involves the preparation of UV-curable acrylate polymers that contain sulfonic groups specifically designed for anti-fog coatings.The hydrophilic polymer was prepared via free radical copolymerization using 2-acrylamido-2-methyl propane sulfonic acid (AMPS) as the hydrophilic monomer. The subsequent UV-curing of the copolymer led to the formation of a coating with good anti-fog and mechanical properties.An isocyanate-containing unsaturated monomer named HIp was prepared via nucleophilic addition of IPDI and HEMA at a molar ratio of 1:1, maintaining the temperature at 40°C. A series of sulfo-group-containing acrylate copolymers (PHEMA) were synthesized through free radical copolymerization of AMPS, HEMA, EHA, and MMA using AIBN as an initiator. The bulk copolymerizations were conducted at 90°C with a fixed concentration of AIBN at 2x10^-3 mol per mol of all monomers. The prepared PHEMA was then reacted with Hip to introduce urethane groups and cross-linkable double bonds, resulting in a UV-curable copolymer named U-PHEMA. IU-PHEMA, as a prepolymer for antifog coating, was obtained by ionization of U-PHEMA with a KOH–methanol solution.The IU-PHEMA was mixed with photoinitiator and reactive diluents to obtain formulas. HDDA and EOTMPTA were chosen as the reactive diluents to increase the double bond content, and CD9051 and w190 were used to improve the adhesion of the formula on glass. The formula was then coated on clean substrates to obtain a transparent film.Coatings are prepared on one side of clean substrates and cured under UV lamp. One part of each substrate is coated and the other part is uncoated. Samples are held above hot water at 80 degrees Celsius for 15 seconds for the anti warm fog test. For the anti cold fog test, coatings are prepared on both sides of clean substrates and cured under UV lamp, then samples are placed in a -15 degrees Celsius refrigerator for 10 minutes and taken out in a 50% humidity environment. Coated panels are immersed in oleic acid at room temperature to evaluate oil resistance. For chemical resistance, samples are immersed in 0.5 mol L-1 H2SO4, 1 mol L-1 NaOH and 50% ethanol."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/US10377933-Antifog coating composition and method of making thereof.json b/task2/task2-paper-info/US10377933-Antifog coating composition and method of making thereof.json
new file mode 100644
index 0000000..04aae75
--- /dev/null
+++ b/task2/task2-paper-info/US10377933-Antifog coating composition and method of making thereof.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "Prepare an antifog coating composition by combining at least one thermoplastic or polymer matrix, at least one hydrophilic component, and at least one surfactant. Optionally, include a thermal initiator or a photo-initiator in the formulation. Apply the composition to a substrate to create a durable antifog coating.The synthesis of hydrophilic polymers involves selecting components for the matrix and functional groups as follows: the matrix is an acrylate matrix, and can include poly (methylmethacrylate) (PMMA), polycarbonate (PC), polyether ether ketone (PEEK), or polyimide (PI). Functional groups should be selected from a list that includes H, substituted or unsubstituted linear alkyl groups (1 to 20 carbon atoms), substituted or unsubstituted cycloalkyl groups (1 to 20 carbon atoms), substituted or unsubstituted divalent aromatic groups (6 to 20 carbon atoms), and substituted or unsubstituted divalent heterocyclic groups (5 to 20 carbon atoms). The polymer may also incorporate methacrylate and acrylate groups, with the possibility of including bisphenol A units.The synthesis of hydrophilic polymers with functional groups involves selecting hydrophilic mono- or multifunctional acrylates such as poly(ethyleneoxy)methacrylate, poly(ethyleneoxy)acrylate, or glycerol dimethacrylate. The selected acrylate is then added to a thermoplastic matrix, which may include poly(methylmethacrylate) (PMMA), along with a surfactant such as poly(ethylene glycol) monolaurate or Tween 20. The mixture also includes a photo-initiator, which can be either a thermal initiator like benzoyl peroxide or a specific photo-initiator such as Irgacure 184. The components are mixed in specific weight percentages, where the acrylate comprises about 10-70 wt % of the formulation, alongside 10-40 wt % of glycerol dimethacrylate, about 10-40 wt % of a surfactant, and about 2-5 wt % of the photo-initiator.To synthesize hydrophilic polymers with functional groups, the protocol includes creating an antifog composition that involves a polymer matrix and a hydrophilic component, wherein the hydrophilic component includes at least one hydrophilic acrylate. The polymer matrix should be composed of suitable thermoplastic elastomers such as PMMA or PC, and contain at least 45 wt% of the total antifog composition, preferably ranging from 45 wt% to 70 wt%. The hydrophilic acrylate may be selected based on specific formulas, where substituents such as R1, R2, R3, A, A', and B can vary to incorporate desired functional groups. Cross-linking occurs during the curing process of the polymer matrix with a thermal or photo-initiator, enhancing adhesion and antifog properties.To synthesize hydrophilic polymers with functional groups, start with glycerol dimethacrylate, glycerol diacrylate, bisphenol-A-glycerol tetraacrylate, bisphenol-A-glycerol diacrylate, or bisphenol-A-ethyleneoxy diacrylate, either individually or in combinations. Incorporate at least one hydrophilic epoxy compound from the specified formula.To synthesize hydrophilic polymers with functional groups, begin by selecting an appropriate hydrophilic epoxy compound, such as a bisphenol-A substituted epoxy. Incorporate surfactants such as non-ionic surfactants, including sorbitan esters, in varying amounts from 10 to 40 wt%. Ensure the hydrophilic component is included at a concentration between 15 wt% to 30 wt%, adjusting as necessary based on the specific embodiment (20 wt% to 30 wt%, or 25 wt% to 30 wt%, for example). Additionally, a photo-initiator (e.g., Irgacure 184 or Darocur 1173) may be included to facilitate free radical polymerization upon exposure to suitable light wavelengths. Alternatively, a thermal initiator such as AIBN or benzoyl peroxide can be used for heat-triggered polymerization. The combinations and specific ratios of these components can vary based on the desired properties of the resulting hydrophilic polymer.The synthesis of hydrophilic polymers involves the following components: a thermoplastic matrix (e.g., poly(methylmethacrylate) (PMMA)), hydrophilic mono or multifunctional acrylates (e.g., glycerol dimethacrylate, bisphenol A glycerolate diacrylate, bisphenol A ethoxylate diacrylate), and a surfactant (e.g., Finafog PET, poly(ethyleneglycol) monolaurate). The mixture is prepared in amounts ranging from about 10 wt % to about 70 wt % thermoplastic matrix, 10 wt % to about 40 wt % hydrophilic acrylates, and 10 wt % to about 40 wt % surfactant. Additionally, a thermal or photo-initiator (e.g., benzoyl peroxide or AIBN) can be added in the range of 1 wt % to about 5 wt % based on the total weight. The resulting composition can then be applied to suitable polymeric substrates.The antifog composition may be thermal or UV cured after applying the formulation onto a suitable polymeric substrate (e.g., polycarbonate substrates) thereby covalently cross-linking the hydrophilic diacrylates into the polymer matrix. The hydrophilic component and the photo-initiator undergo covalent crosslinking and are then incorporated into the thermoplastic matrix (e.g., PMMA).The PC substrates were cleaned with isopropanol and dried at room temperature for 20 minutes. The filtered solutions of antifog resin formulation were flow coated onto the PC substrate using a squeeze bottle. The coated substrates were air-dried at room temperature for 5 minutes and subsequently at 75 degree Celsius for 5 minutes in an air-oven. The substrates were then cured in a UV curing machine with UVA intensity of 30-150 mW/cm^2.Formulations were made with PMMA (52 wt %), Finafog PET (22 wt %), and one of the three hydrophilic acrylates namely, Glycerol dimethacrylate (or) Bisphenol-A-ethoxylate diacrylate (or) Bisphenol-A-glycerolate diacrylate (22 wt %) and 4 wt % photoinitiator. Polycarbonate substrates (PC substrates) were cleaned with deionized water and isopropanol and dried at room temperature for 20 min prior to coating. Each flow was coated on a PC substrate and then the optical properties were measured. The coated panels were subjected to Fog Test Studies at 60°C.The synthesis of hydrophilic polymers with functional groups involves the selection of various functional groups: R2 can be H or CH3; R3 can be H, an alkyl group (1-6 carbon atoms), a hydroxy group, an alkoxy group (1-3 carbon atoms), methacrylate, or acrylate; A can be O, a linear alkyl group (1-20 carbon atoms), a cycloalkyl group (1-20 carbon atoms), divalent aromatic group (6-20 carbon atoms), alkylene oxide, or divalent heterocyclic group (5-20 carbon atoms); A' can also be selected similarly as A; B can be O, a linear alkyl group (1-20 carbon atoms), a cycloalkyl group (1-20 carbon atoms), a divalent aromatic group (6-20 carbon atoms), a divalent heterocyclic group (5-20 carbon atoms), or a bisphenol A unit; where n is from 1-5, m is from 0-5, and R4, R5, R6 can vary within specified groups; Q can be a linear alkylene, cycloalkylene, divalent aromatic, or divalent heterocyclic group; and at least one non-ionic surfactant should be included. In addition, the hydrophilic acrylate might include components such as poly(ethyleneoxy)methacrylate, poly(ethyleneoxy)acrylate, and others. Components should be added based on a weight percentage specification concerning the total weight of the composition."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/US20030148113A1.json b/task2/task2-paper-info/US20030148113A1.json
new file mode 100644
index 0000000..ecd84f3
--- /dev/null
+++ b/task2/task2-paper-info/US20030148113A1.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Combine a silicone compound having a hydrophilic functional group with a water dispersible polyurethane compound. The silicone polymer or oligomer should be present in the formulation at about 0.1 to about 20 parts by weight, preferably about 1 to about 10 parts by weight, and more preferably about 1 to about 5 parts by weight. The water dispersible polyurethane polymer or oligomer should be included at about 5 to about 50 parts by weight, preferably about 10 to about 40 parts by weight, and more preferably about 20 to about 30 parts by weight. The remainder of the formulation should be an aqueous solvent, primarily water, with the optional addition of a co-solvent at about 1 to about 10 parts by weight, preferably about 5 to 10 parts by weight. The total weight of the compounds in the formulation should sum to 100 parts by weight. Functional groups may include —CO2H, —OH, —NH, —SH, ester, urethane, and isocyanate groups, but should exclude strong acids such as sulfonic acid functional groups. The silicone polymer or oligomer is to be carefully selected to maintain film integrity and prevent degradation.The synthesis of hydrophilic polymers with functional groups involves the following steps: Charge polypropylene glycol diol, dimethylol propionic acid (dissolved in percentage of N-methyl-pyrrolidinone), and dibutyltin dilaurate into a reactor under a nitrogen environment at approximately 80°C. Slowly add hydrogenated diphenyl methane diisocyanate to the reactor, maintaining the reaction for 3 hours until the theoretical NCO% is reached. Cool the reaction mixture to 60°C, then add triethylamine to neutralize the acid functionalities. Introduce water with vigorous agitation to form the dispersion, followed by adding a solution of diethylene triamine in N-methyl-pyrrolidinone and water to complete chain extension, continuing the reaction for an additional 2 hours. The resulting polyurethane dispersion should have a solids content of about 35 to 40 weight percent. Apply the dispersion to a substrate and dry at elevated temperature to achieve a crosslinked film."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/US20080076851A1.json b/task2/task2-paper-info/US20080076851A1.json
new file mode 100644
index 0000000..a8511e3
--- /dev/null
+++ b/task2/task2-paper-info/US20080076851A1.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of hydrophilic polymers involves the following steps: 1. Utilize gamma or electron beam irradiation to initiate the polymerization process; 2. Employ N-vinylpyrrolidone (NVP) or copolymerize NVP with 2-hydroxyethyl-methacrylate (HEMA) to form coatings; 3. Apply the polymerized and chemically grafted coating on the surfaces of articles intended for contact with living tissue; 4. Ensure that appropriate process conditions and parameters are maintained to achieve thin, hydrophilic layers on various polymeric materials.1. Prepare a mixture of pre-polymerized hydrophilic polymers and monomers suitable for surface modification, such as PVP, PHEMA, NVP, and HEMA. 2. Subject the mixture to high energy radiation to induce graft polymerization on surfaces of articles such as contact lenses. 3. Ensure that the resulting graft coating entraps or enmeshes the pre-polymerized polymer as it forms. 4. Maintain the grafting solution with osmolarity similar to that of normal saline (iso-osmolar) to keep contact lenses in the grafting solution after irradiation until use.Place silicone copolymer contact lenses in tubes containing 10 ml of a deionized water (DI) solution of polyvinylpyrrolidone (PVP/K-90) and N-vinylpyrrolidone (NVP) in a w/w ratio of 4:1 and a total concentration of 10 wt %. Use a carousel holder to rotate the tubes around a gamma source at a distance of approximately 4 inches. Irradiate the samples to a total dose of 0.1 Mrad at a dose rate of approximately 480 rads/min. Wash the contact lenses in DI water.1. Conduct gamma- or electron beam-irradiation induced graft polymerization in an aqueous solution containing a hydrophilic polymer. 2. Ensure that the hydrophilic polymer is at least partially entrapped in the graft polymerized coating. 3. Use a hydrophilic polymer selected from a diverse group including polyalkylene oxides, polyols, and other hydrophilic or hydrophobic materials. 4. Utilize a hydrophilic monomer from a range of ethylenically unsaturated C3–C6 carboxylic acids, allylamines, and other specified monomers with at least one hydrophilic functionality. 5. Optionally, incorporate an ionic monomer, salt of an ionic monomer, or mixture thereof in the total monomer weight. 6. The polymer-monomer mix ratio is varied from 1:4 to >4:1 with total solution concentrations ranging from 1% to 25%. 7. Conduct the process under a pH of high aqueous solution (2% KOH or NaOH)."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/US20220106497A1.json b/task2/task2-paper-info/US20220106497A1.json
new file mode 100644
index 0000000..5eea88f
--- /dev/null
+++ b/task2/task2-paper-info/US20220106497A1.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Free radical polymerization is utilized for synthesizing hydrophilic polymers. The coating composition involves a mixture comprising an initiator, a radical curable polyurethane with ethylenically unsaturated functional groups, and a liquid phase. The polyurethane is derived from the reaction products of a polyol component, a polyisocyanate component, an isocyanate-reactive surfactant, and an isocyanate-reactive component with ethylenically unsaturated functional groups. The curing process can be initiated through exposure to UV radiation, thermal radiation, or both, to impart desired anti-fog and wear resistance properties.1. Prepare a mixture comprising an initiator, a radical curable polyurethane with ethylenically unsaturated functional groups, and a liquid phase. 2. The polyurethane must include the reaction products of: A) a polyol component, B) a polyisocyanate component, C) an isocyanate-reactive surfactant, and D) an isocyanate-reactive component containing ethylenically unsaturated functional groups. 3. Utilize thermal or radiation-induced free radical polymerization to cure the coating composition, forming a hydrophilic polymeric polyurethane network. 4. Ensure the reactive surfactant binds to the network during the curing process. 5. Optionally, incorporate hydrophilic alkoxylated acrylate as part of the isocyanate-reactive component to enhance hydrophilicity and maintain permanent anti-fog properties. 6. Optionally, add metal oxide nanoparticles to improve abrasion resistance while ensuring optical transparency. 7. Apply the resulting coatings onto optically transparent substrates, such as lenses for eyeglasses.The coating compositions comprise an initiator, a radical curable polyurethane with ethylenically unsaturated functional groups, and a liquid phase. Suitable liquid phases include water, organic solvents, and combinations thereof. Select organic solvents based on the constituent components for polyurethane synthesis, ensuring they can dissolve the selected polyols and do not readily react with the polyisocyanates. Examples of suitable organic solvents include ketones (methylethylketone, methylisobutyl ketone, diacetone alcohol, 3,3-dimethyl-2-butanone, pentanedione), N-methyl pyrrolidone, acetonitrile, esters, glycol esters, and tertiary alcohols (tertiary-butyl alcohol, tertiary-amyl alcohol).The coating compositions of the present disclosure comprise an initiator selected from thermal radical initiators, photoinitiators, or a combination of both. Suitable thermal radical initiators include azo initiators like 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) and peroxide initiators such as benzoyl peroxide. Photoinitiators may include UV-sensitive compounds like benzoin or 2-hydroxy-2-methyl-1-phenyl-propan-1-one. The initiators are used in amounts ranging from 0.3 to 6 wt%, based on the total weight of the solid coating composition.The synthesis of hydrophilic polymers with functional groups involves the preparation of a radical curable polyurethane. This polyurethane is created through a reaction that includes the following components: (A) a polyol, (B) a polyisocyanate, (C) an isocyanate-reactive surfactant, and (D) an isocyanate-reactive component that possesses ethylenically unsaturated functional groups. The isocyanate-reactive component can be substituted with any compound having unsaturated reactive functionality, such as isocyanate-reactive alkenyl compounds that contain reactive vinyl, reactive acrylate, reactive methacrylate, or reactive allyl groups. The resulting radical curable polyurethane should be included in the final composition at a concentration ranging from 85 to 97.5 wt%, based on the total weight solids of the coating composition.The synthesis of hydrophilic polymers involves the use of polyols, specifically at least one polyol that is either a diol or a triol with main chain segments selected from polyethylene oxide, polypropylene oxide, or combinations thereof. Suitable diols can include polyethylene oxide side chain segments, alkyl diols, alkyl triols, polycarbonate diols, and polycarbonate triols. It is preferred to use a polypropylene oxide and polyethylene oxide block copolymer diol in an amount of approximately 10% to 25% polyethylene oxide by weight of the polyol. Similarly, for triols, a polypropylene oxide and polyethylene oxide copolymer triol with 60% to 95% polyethylene oxide is preferred. The polyols should have one or more hydrophilic regions due to the presence of the formula: —((CH2)nO-)m, where n is between 1 and 3, and m is between 1 and 10. The coating compositions should comprise one or more polyol in amounts ranging from 10-60 wt%, based on the total weight solids of the radical curable polyurethane.The synthesis involves using one or more multifunctional polyisocyanates, specifically diisocyanates or triisocyanates, to form polyurethane linkages. The components should be selected based on their isocyanate functionalities and include examples such as isophorone diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate. For optimal light stability, aliphatic polyisocyanates such as IPDI-type and HDI-type diisocyanates are preferred. The coating compositions should consist of polyisocyanates in amounts ranging from 5.60 wt% to 58 wt%, which can vary across specified ranges based on the total weight solids of the radical curable polyurethane.The synthesis of hydrophilic polymers involves the following steps: 1. Use isocyanate-reactive surfactants containing reactive groups such as hydroxyl, thiol, or amine in amounts ranging from 1-50 wt % based on the total weight solids of the radical curable polyurethane. 2. Incorporate an isocyanate-reactive component with ethylenically unsaturated functional groups, adhering to the formula Y—R—X, where Y is an ethylenically unsaturated group and X is an isocyanate reactive group, in amounts ranging from 1-25 wt %. 3. Optionally include radical reactive surfactants containing groups like alkenyl, acrylate, or thiol at 0-20 wt %. 4. Combine these components with a polyol and a polyisocyanate to form the radical curable polyurethane, ensuring reactive functionalities from all components interact during the curing process. 5. Use multifunctional ethoxylated acrylate monomers to form the network. 6. Optionally add metal oxide particles to enhance properties, maintaining their concentrations between 0 and 70 wt %. 7. Apply the mixture to the desired substrate, followed by curing to form the final hydrophilic polymer.The coating compositions described can be applied to substrates using methods such as flow coating, spray coating, curtain coating, dip coating, spin coating, slot-die coating, roll coating, etc., to form a continuous surface film. The coated substrate is cured by exposing it to UV radiation, visible light radiation, or EB radiation, with cumulative UV radiation exposure needed for curing being between 1.5 to 3.0 J/cm² when using a Fusion H bulb. When using LED light, curing occurs in 1 to 30 minutes with a peak emission wavelength of 460±20 nm and intensity from 200 to 300 mW/cm² at a distance of 1 to 20 cm. Heat curing can be applied at temperatures between 50 to 150°C for 1 minute to 4 hours, preferably from 100 to 125°C for 2 minutes to 1 hour, or in combination with another radical cure mechanism such as UV curing. The final coatings exhibit anti-fog, wear-resistant, and water-washable properties.In a round-bottom flask, mix 19.74 g of trimethylolethane, 9.87 g of ethylene glycol, 78.97 g of POLY-G 83-34, and 276.41 g of DAA at 50°C until dissolved. Add 195.85 g of isophorone diisocyanate, 9.87 g of ETERNACOLL UH200, and 63.18 g of TEGOMER D3403 to the flask. Then, add 0.18 g of FOMREZ UL-22 and mix at 70°C for 30 minutes. Next, add 188.35 g of DAA, 15.07 g of Aerosol OT-75, 6.46 g of SCHERCOQUAT IAS-PG, 59.23 g of CIRRASOL G-265, 1.97 g of TERGITOL 15-s-7, and another 0.18 g of FOMREZ UL-22 and mix at 70°C for 1 hour. Afterward, introduce 63.18 g of 4-hydroxybutyl acrylate and 0.18 g of FOMREZ UL-22 and mix for 30 minutes at 70°C. Next, add 11.85 g of trimethylolethane and 0.18 g of UL-22, mixing for 2 hours at 70°C. Once mixing is complete, cool the flask to room temperature. After cooling, add 726 g of 1-methoxy propanol and 18.73 g of IRGACURE 1173 and mix at room temperature for 1 hour. Finally, dip-coat the sample onto a polycarbonate lens and cure using a Vela 3D (UV) cure unit at 2.0 J/cm².25.00 g of trimethylolethane, 10.00 g of ethylene glycol, 100.00 g of POLY-G 83-34, and 276.41 g of DAA were loaded into a round-bottom flask and mixed at 50°C until dissolved. 215.00 g isophorone diisocyanate, 10.00 g of ETERNACOLL UH200, and 60.00 g of TEGOMERD3403 were added to the flask. 0.18 g of FOMREZ UL-22 was then added to the flask and mixed at 70°C for 30 minutes. 125.00 g SURFCON 94 and 0.18 g FOMREZ UL-22 were added to the round-bottom flask and allowed to mix at 70°C for 1 hour. After mixing, 75.00 g 4-hydroxybutyl acrylate and 0.18 g FOMREZ UL-22 were added to the mixture and allowed to mix for 30 minutes at 70°C. 15.00 g trimethylolethane and 0.18 g UL-22 were added to the round-bottom flask and mixed for 2 hours at 70°C. After mixing, the flask was cooled to room temperature. After the mixture is cooled, 725 g 1-methoxy propanol and 20.22 g of IRGACURE 1173 were added and mixed at room temperature for 1 hour. The sample was dipcoated onto a polycarbonate lens and cured using a Vela 3D (UV) cure unit at 2.0 J/cm².7.79 g of trimethylolethane, 4.54 g of ethylene glycol, 37.63 g of POLY-G 83-34, and 181.68 g of DAA were loaded into a round-bottom flask and mixed at 50°C until dissolved. 77.86 g isophorone diisocyanate, 6.49 g of ETERNACOLL UH200, and 31.14 g of TEGOMER D3403 were added to the flask. 0.08 g of FOMREZ UL-22 was then added to the flask and mixed at 70°C for 30 minutes. 90.84 g DAA, 7.26 g Aerosol OT-75, 3.11 g SCHERCOQUAT IAS-PG, 28.55 g CIRRASOL G-265, 1.04 g TERGITOL 15-s-7, and 0.18 g FOMREZ UL-22 were added to the round-bottom flask and allowed to mix at 70°C for 1 hour. After mixing, 16.87 g 4-hydroxybutyl acrylate and 0.08 g FOMREZ UL-22 were added to the mixture and allowed to mix for 30 minutes at 70°C. 5.19 g trimethylolethane and 0.08 g UL-22 were added to the round-bottom flask and mixed for 2 hours at 70°C. After mixing, the flask was cooled to room temperature. After the mixture is cooled, 363 g 1-methoxy propanol and 9.37 g of IRGACURE 1173 were added and mixed at room temperature for 1 hour. The sample was dip-coated onto a polycarbonate lens and cured using a Vela 3D (UV) cure unit at 2.0 J/cm^2.$1.78 g of trimethylolethane, $1.75 g of ethylene glycol, $41.26 g of POLY-G 83-34, and $79.10 g of DAA were mixed together.$100\\\\mathrm{g}$ of Example 1 was mixed with $0.4\\\\ \\mathrm{g}$ of 3-EGA for 1 hour at room temperature conditions. The sample was dipcoated onto a polycarbonate lens and cured using a Vela 3D (UV) cure unit at $\\\\mathsf{2.0~J}/\\\\mathrm{cm}^{2}$.$100\\mathrm{g}$ of Example 3 was mixed with $0.4\\ \\mathrm{g}$ of 3-EGA for 1 hour at room temperature conditions. The sample was dipcoated onto a polycarbonate lens and cured using a Vela 3D (UV) cure unit at $2.0\\mathrm{J}/\\mathrm{cm}^{2}$.$100\\\\ \\mathrm{g}$ of Example 1 was mixed with $0.2\\\\ \\mathrm{g}$ of 3-EGA for 1 hour at room temperature. The sample was dip-coated onto a polycarbonate lens and cured using a Vela 3D (UV) cure unit at $2.0\\\\mathrm{J}/\\\\mathrm{cm}^{2}$.100 g of Example 3 was mixed with 0.2 g of 3-EGA for 1 hour at room temperature. The sample was dipcoated onto a polycarbonate lens and cured using a Vela 3D (UV) cure unit at 2.0 J/cm^2. Additionally, 16.50 g of IPDI, 15.20 g of 4-hydroxybutylacrylate, and 0.08 g of FOMREZ UL-22 were mixed in a round-bottom flask at 70°C for 1 hour. After cooling, 114.40 g of 1-methoxy propanol and 3.87 g of IRGACURE 1173 were added and mixed at room temperature for 1 hour. Another protocol involved loading 19.74 g of trimethylolethane, 9.87 g of ethylene glycol, 78.97 g of POLY-G 83-34, and 276.41 g of DAA into a round-bottom flask and mixed at 50°C until dissolved, followed by adding 195.85 g of isophorone diisocyanate, 9.87 g of ETERNACOLL UH200, and 63.18 g of TEGOMER D3403, then adding 0.18 g of FOMREZ UL-22 and mixing at 70°C for 30 minutes. Finally, 152.0 g of SURFCON 94 and 0.18 g of FOMREZ UL-22 were added to the round-bottom flask and mixed at 70°C for 1 hour, followed by adding 63.18 g of 4-hydroxybutyl acrylate and mixing for 30 minutes at the same temperature.To 7.00 g of the Example 9, 1.75 g of PGM-AC2140Y was added while stirring. After mixing for 15 minutes, 3.00 g of PM glycol ether was added while stirring. This was followed by the addition of 0.05 g thermal radical initiator (AIBN). Also, 0.10 g of 10% BYK 356 in PM and 0.04 g of a mixture of CAPSTONE FS35 and SCHERCOQUAT IAS-PG in the ratio 1:25 were added. The coating solution was mixed for 30 minutes. Coated parts were prepared by flow coating the liquid formulations on polycarbonate substrate. All the parts were air dried for 1 minute. Thermal curing was then initiated at 90°C for 3 minutes and completed at 90°C for 4 hours.To 7.00 g of the Example 9, 1.75 g of PGM-AC2140Y was added while stirring. After mixing for 15 minutes, 3.00 g of PM glycol ether was added while stirring. This was followed by addition of 0.05 g thermal radical initiator (VAM-110). 0.10 g of 10% BYK 356 in PM, and 0.04 g of mixture of CAPSTONE FS35 and SCHERCOQUAT IAS-PG in the ratio 1:25, were added. The coating solution was mixed for 30 min. Coated parts were prepared by flow coating the liquid formulations on polycarbonate substrate. All the parts were air dried for 1 min. Thermal curing was then initiated at 90°C for 3 min and completed at 115°C for 2h.Another set of coated parts using the same liquid formulation of Example 11 were prepared by flow coating on polycarbonate substrates. Parts were air dried for 1 min. Thermal curing was then initiated at 90°C for 3 min and completed at 110°C for 45 min.To 7.00 g of the Example 9, 1.75 g of PGM-AC2140Y was added while stirring. After mixing for 15 minutes, 3.00 g of PM glycol ether was added while stirring. This was followed by addition of 0.05 g thermal radical initiator (VA-086). 0.10 g of 10% BYK 356 in PM, and 0.04 g of mixture of CAPSTONE FS35 and SCHERCOQUAT IAS-PG in the ratio 1:25, were added. The coating solution was mixed for 30 minutes. Coated parts were prepared by flow coating the liquid formulations on polycarbonate substrate. All the parts were air dried for 1 minute. Thermal curing was then initiated at 90°C for 3 minutes and completed at 100°C for 4 hours.To 50.00 g of Example 9, 0.74 g of IRGACURE 184 and 30.00 g of a 10% mix of SOKALAN K17 in PM were added. The mixture was agitated for at least 20 minutes prior to coating. Coated parts were prepared by flow coating the liquid formulations on polycarbonate substrate. All the parts were air dried for 1 min and initially thermally cured at 90°C for 3 min. The cure was completed using a Vela 3D (UV) Cure Unit at 2.0 J/cm².To 50.00 g of Example 9, 0.74 g of IRGACURE 184 and 10.00 g of a 30% K60 in water were added. After mixing for 2 minutes, 20.00 g of PM was added to the beaker. The mixture was agitated for at least 20 minutes prior to coating. Coated parts were prepared by flow coating the liquid formulations on polycarbonate substrate. All the parts were air dried for 1 minute, and initially thermally cured at 90°C for 3 minutes. The cure was completed using a Vela 3D (UV) cure unit at 2.0 J/cm².1. Mix anhydrous citric acid (34.6 g), polyethylene glycol diglycidyl ether (200) (207.6 g) at 90°C. 2. Add dimethylamine hydrochloride (3 g) and stir for 3 hours. 3. Incorporate acrylic acid (57.9 g). 4. Add hydroquinone (0.3 g). 5. Prepare formulations using Synthesis II products as specified in Table 10. 6. Apply to polycarbonate substrate. 7. Cure with Fusion Conveyor (UV) cure unit.100 g of Example 2 was mixed with 0.25 g of azobisisobutyronitrile (AIBN) overnight at room temperature. The sample was dipcoated onto a polycarbonate lens. Samples were initially cured at 90°C for at least 5 minutes and cure was completed using a Vela 3D (UV) cure unit at 2.0 J/cm².100 g of Example 2 was mixed with 0.38 g of AIBN overnight at room temperature. The sample was dipcoated onto a polycarbonate lens. Samples were initially cured at 90°C for at least 5 minutes and cure was completed using a Vela 3D (UV) cure unit at 2.0 J/cm²."
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+    "protocol": "The anti-fog polyurethane coating compositions are applied directly to a substrate or directly to a primer-coated substrate and cured, or the coating compositions are cast into unsupported films for later attachment to the substrate.Surfactants can be mixed into the polyurethane coating composition before application to a substrate. This allows the surfactant to become physically trapped within the polyurethane polymer structure during the curing process.1. Prepare a first polyurethane using a diol with polyethylene oxide side chain segments, an additional polyol component, a first polyisocyanate, and a dihydroxy-carboxylic acid neutralized with a carboxylic-reactive amphoteric surfactant to form a salt. 2. Mix the first polyurethane with a liquid phase (water, organic solvent, or a combination). 3. Prepare a second polyurethane from a second polyol and an additional polyol component, a partially blocked tri-functional polyisocyanate, an isocyanate-reactive salt of a surfactant, and an isocyanate-reactive cationic surfactant. 4. Incorporate hydrophilic main chain or side chain segments in the polyurethanes at a concentration of 0.01% to 40% by weight of the solids. 5. Adjust the composition as needed for the desired properties.The synthesis of the third polyurethane involves the reaction of a third polyol component, which includes a diol with polyethylene oxide side chain segments and an additional different polyol, with a third polyisocyanate component. The third polyisocyanate comprises at least one polyisocyanate from the group of diisocyanates, triisocyanates, or their derivatives, and at least one partially blocked tri-functional polyisocyanate. The resulting polyurethane should contain hydrophilic main chain segments or hydrophilic side chain segments in an amount ranging from about 0.01% to about 40% by weight of the solids of the polyurethane.The synthesis of hydrophilic polymers with functional groups involves the following steps: 1. Combine a diol containing polyethylene oxide side chain segments with at least one other different polyol in a reaction mix. 2. Introduce a polyisocyanate into the reaction mix, ensuring the ratio of isocyanate functional groups to hydroxyl functional groups is greater than or equal to about 1.1:1. 3. Incorporate a dihydroxy-carboxylic acid into the reaction mix. 4. Allow the reaction to occur in a suitable organic solvent at high temperatures, leading to the formation of a polyurethane with carboxylic acid functional groups. 5. Introduce a carboxylic-reactive amphoteric surfactant to the reaction mixture to neutralize the carboxylic acid functional groups, resulting in a salt of the amphoteric surfactant chemically bonded to the polyurethane. 6. The final polyurethane structure will have hydrophilic segments that contribute to its dispersibility and anti-fog properties.To synthesize hydrophilic polymers with functional groups, the following steps should be taken: 1) Combine a liquid phase consisting of either water, an organic solvent, or combinations thereof with a polyurethane. 2) The polyurethane is formed from the reaction of polyols such as: (a) diols with main chain segments from polyethylene oxide and/or polypropylene oxide, (b) triols with similar segments, and (c) at least one additional different polyol. Ensure the polyol used has hydrophilic main chain segments, preferably comprising polyethylene oxide or polypropylene oxide, in amounts between 0.01% and 40% by weight of the solids of polyurethane. 3) Incorporate at least one partially blocked tri-functional polyisocyanate into the system. The polyisocyanates should comprise between 5% and 60% of the weight of the solids of the polyurethane. 4) Introduce an isocyanate-reactive salt of a surfactant, preferably mono-functional, accounting for 0.1% to 7% by weight of solids. 5) Add an isocyanate-reactive cationic surfactant, which should constitute 0.1% to 20% by weight of the solids and should contain at least one isocyanate-reactive functional group. 6) Catalysts, such as metal carboxylates, can be introduced to aid the reaction. 7) Once the mixture is prepared, agitate mechanically to disperse the prepolymer into the liquid phase, aiding the formation of a stable colloidal dispersion. 8) Perform a final polymerization step where the isocyanate-terminated prepolymer reacts with chain extenders to yield a higher molecular weight polyurethane. These extenders may include multifunctional amines or polyols. 9) The final product can then be applied to various substrates using methods such as flow coating or spray coating.The synthesis of hydrophilic polymers with functional groups is performed by applying an aqueous polyurethane dispersion to polycarbonate lenses. Specifically, five or six polycarbonate lenses are dip-coated in the aqueous polyurethane dispersion at a draw speed of 12 inches per minute. After dip-coating, the lenses are allowed to dry and may undergo pre-curing conditions before the final curing step. The curing is conducted by treating the coated lenses with heat at a designated temperature for a specified duration. The selection of polyurethane coated lenses varies based on the tests to be performed, ensuring that different coated lenses are utilized for adhesion and anti-fogging assessments.To synthesize the PEO side-chained diol, a two-step reaction is conducted. In the first step, hexamethylene diioscyanate is reacted with a mono-methyoxy-polyethylene glycol with an average molecular weight (Mn) of about 1,000. After the mono-functional mono-methyoxy-polyethylene glycol reacts with one isocyanate functional group of the diisocyanate, the remaining isocyanate functional group is then reacted with diethanolamine to yield the final diol product. This diol compound possesses polyethylene oxide side chains.21.1 grams (g) of IPDI, 28.2 g of PC 2000, 2.1 g of trimethylolpropane, 3.2 g of dimethylolpropionic acid, 8.1 g of Tegomer D3403, and 35 g of methylethylketone are mixed together. The mixture is heated to 70°C, and 0.01 g of tin 6: catalyst is added. The mixture is then reacted for 3 hours in a nitrogen environment. After the reaction finishes, the resulting polyurethane prepolymer mixture is cooled to 40°C. 40.3 g of polyurethane prepolymer mixture is then dispersed into 51.2 g of water and 7.0 g of aqueous betaine surfactant solution with a high shear disperser. 0.25 g of hydrazine-monohydrate and 0.58 g of 1,6-hexanediamine are also added during dispersion with the high shear disperser, resulting in an aqueous polyurethane dispersion having about 27% solids by weight of the dispersion. The resulting polyurethane comprises about 10% polyethylene oxide side chains by weight of the solids of the polyurethane and about 10% neutralized amines by weight of the solids of the polyurethane.Mix $24.7\\mathrm{g}$ of IPDI, $14.7\\mathrm{g}$ of PC 2000, $3.2\\mathrm{g}$ of trimethylolpropane, $3.0\\mathrm{g}$ of dimethylolpropionic acid, $15.3\\mathrm{g}$ of PEO-side chained diol, $1.9\\mathrm{g}$ of PTF 1000, and $35\\mathrm{g}$ of acetonitrile. Heat the mixture to $70^{\\circ}\\mathrm{C}$ and add $0.01\\mathrm{g}$ of tin catalyst. React for 3 hours in a nitrogen environment. After the reaction, cool the resulting polyurethane prepolymer mixture to $40^{\\circ}\\mathrm{C}$. Disperse $40.9\\mathrm{g}$ of the polyurethane prepolymer mixture into $51.2\\mathrm{g}$ of water and $7.4\\mathrm{g}$ of aqueous amine oxide surfactant solution using a high shear disperser. Add $0.55\\mathrm{g}$ of hydrazinemonohydrate during dispersion. Resulting in an aqueous polyurethane dispersion having about $28\\%$ solids by weight. The resulting polyurethane comprises about $17\\%$ polyethylene oxide side chains by weight and about $8\\%$ neutralized amines by weight of the solids. Measure viscosity at $25^{\\circ}\\mathrm{C}$, which is 39 cps. Dip-coat a polycarbonate lens in the aqueous polyurethane dispersion at a 12 inch/min draw speed. Dry for $30\\mathrm{min}$ at room temperature, resulting in a tack-free coating. Cure the coated lens at $90^{\\circ}\\mathrm{C}$ for 2 hours. The resulting coating thickness is about $11.5\\upmu\\mathrm{m}$.Dissolve 22.0 g of IPDI, 20.2 g of PC 2000, 2.1 g of trimethylolpropane, 3.2 g of dimethylolpropionic acid, and 9.1 g of PEO-side in an appropriate solvent. Stir the mixture until completely homogeneous to prepare the aqueous polyurethane dispersion containing functional groups.Mix 5.9 g of PEG 1000 and 35 g of methylethylketone, then heat the mixture to 70°C. Add 0.01 g of tin catalyst and react for 3 hours in a nitrogen environment. Allow the reaction to cool to 40°C. Disperse 37.2 g of the polyurethane prepolymer mixture into 53.3 g of water and 7.3 g of aqueous amine oxide surfactant solution using a high shear disperser. During dispersion, add 0.25 g of hydrazine-monohydrate and 0.59 g of 1,6-hexanediamine. This will result in an aqueous polyurethane dispersion with about 27% solids by weight. The dispersion contains approximately 10% polyethylene oxide side chains, 10% polyethylene oxide main chains, and 8% neutralized amines by weight of the solids. The measured viscosity of the dispersion should be 63 cps at 25°C. Dip-coat a polycarbonate lens in the dispersion at a 12 inch/min draw speed. Dry the dip-coated lens for 30 minutes at room temperature, resulting in a tack-free coating. Cure the coated lens at 90°C for 2 hours, achieving a coating thickness of about 11.0 μm.To synthesize hydrophilic polymers with functional groups, mix 21.8 g of IPDI, 19.0 g of PC 2000, 2.1 g of trimethylolpropane, 3.2 g of dimethylolpropionic acid, 9.1 g of PEO-side chained diol, 5.9 g of PEG 1000, and 35 g of methylethylketone. Heat the mixture to 70°C and add 0.01 g of tin catalyst. React for 3 hours in a nitrogen environment. Cool the mixture to 40°C and add 1.4 g of Trixene BI 7961. Disperse 37.1 g of the resulting polyurethane prepolymer mixture into 53.4 g of water and 7.3 g of aqueous amine oxide surfactant solution using a high shear disperser. Add 0.25 g of hydrazine-monohydrate and 0.59 g of 1,6-hexanediamine during dispersion. The final dispersion should contain about 25% solids by weight. For the polycarbonate lens application, dip-coat at a 12 inch/min draw speed, dry at room temperature for 30 minutes, and cure at 90°C for 2 hours. Alternatively, for the polyurethane mixture with an isocyanate-reactive salt, mix 24.7 g of Trixene DP9C/012, 4.2 g of Poly G 83-34, 1.1 g of Pluronic L-62, 0.5 g of trimethylolethane, 0.6 g of triethanolamine, and 5.0 g of DMAMP DBS solution with 4.1 g of N-methyl pyrrolidone, 4.5 g of tertiary amyl alcohol, 7.9 g of methylethylketone, and 0.9 g of 2-pentanedione. Heat to 60°C and react for 8 hours in a nitrogen environment, then cool to 30°C.35 g Trixene DP9C/012, 1.2 g PEG 1000, 4.6 g PC 2000, 0.6 g trimethylolpropane, 3.8 g Tegomer D3403, 1.2 g Cirrasol G-265, and 0.002 g tin catalyst are added to 4.0 g methylethylketone and 2.8 g diacetone alcohol and are mixed together. The mixture is heated to 60°C and then reacted for 6 hours in a nitrogen environment. Following the reaction, the resulting polyurethane prepolymer mixture is cooled to 30°C. The polyurethane prepolymer mixture is then dispersed in 63.0 g of distilled water, 0.34 g 1,6-hexanediamine, and 0.15 g 30% aqueous hydrazine with a high shear disperser, resulting in a stable aqueous polyurethane dispersion having about 24% solids by weight of the dispersion.Add 4.6 g IPDI, 5.5 g DP9C/012, 7.8 g PC 2000, 0.7 g trimethylolpropane, 3.2 g PEO-side chained diol, 2.1 g Cirrasol G-265, and 0.011 g tin catalyst to 10.3 g N-methyl pyrrolidone and 2.2 g diacetone alcohol. Mix and heat to 65°C, then react for 3 hours in an inert atmosphere. Cool the mixture to 40°C, then disperse in 66.6 g distilled water and 0.65 g (2-aminoethyl) aminoethanol using a high shear disperser, obtaining a stable aqueous polyurethane dispersion with about 24% solids. Resulting polyurethane comprises about 11% polyethylene oxide side chains, about 2% polyethylene oxide main chains, and about 11.7% blocked polyisocyanates by weight of solids. For dip-coating, use a draw speed of 12 inch/min and cure at 120°C for 1 hour, aiming for a thickness of about 8.1 µm.To prepare the hydrophilic polymer, mix 3.1 g of IPDI, 3.6 g of DP9C/012, 3.0 g of PC 2000, 0.3 g of trimethylolpropane, 2.3 g of PEO side-chained diol, 1.0 g of Poly G 83-34, 1.3 g of Cirrasol G-265, 0.7 g of DMAMP DBS solution, 0.9 g of sodium dioctylsulfosuccinate, and 0.011 g of tin catalyst in 5.1 g of N-methyl pyrrolidone and 2.2 g of diacetone alcohol. Heat this mixture to 65°C and react for 3 hours in an inert atmosphere. After the reaction, cool the resulting polyurethane prepolymer mixture to 40°C. Then, disperse the cooled mixture in 75.7 g of distilled water and 0.4 g of 2-(2-aminoethyl)aminoethanol using a high shear disperser, resulting in a stable aqueous polyurethane dispersion with about 16% solids by weight. The final polymer composition includes about 12% polyethylene oxide side chains, 6% polyethylene oxide main chains, and 11% blocked polyisocyanates by weight of the solids.100 g of the aqueous polyurethane dispersion from Example 8 is mixed with 100 g of the aqueous polyurethane dispersion from Example 3.To synthesize the hydrophilic polyurethane, prepare an aqueous polyurethane dispersion containing 25% solids by weight. To reduce viscosity, add 100 g of water with agitation until a stable, hazy dispersion with about 17% solids by weight is achieved. The resulting polyurethane should consist of 6.7% polyethylene oxide side chains, 10.9% polyethylene oxide main chains, 4.2% neutralized amines, and 22.6% blocked polyisocyanates by weight of the solids. Next, dip-coat a polycarbonate lens in the dispersion at a draw speed of 12 inches/min. Dry the dip-coated lens at room temperature for 5 minutes, then at 85°C for an additional 10 minutes until tack-free. Cure the tack-free coated lens at 120°C for 1 hour, resulting in a coating thickness of about 8.1 µm.50 g of the prepolymer of Example 3 and 50 g of the prepolymer of Example 8 are mixed together and added to 185.5 g 1-methoxy-2-propanol with agitation, resulting in a homogenous, clear polyurethane solution. The polyurethane solution comprises essentially all non-aqueous solvents and has about 20% solids by weight. The resulting polyurethane comprises about 9.0% polyethylene oxide side chains, about 11.5% polyethylene oxide main chains, and about 22.6% blocked polyisocyanates by weight of the solids. The viscosity of the solution is about 25 cps at 25°C. A polycarbonate lens is dip-coated in the polyurethane solution at a 12 inch/min draw speed, dried at room temperature for 5 minutes, then at 85°C for an additional 10 minutes. The coated lens is cured at 120°C for 1 hour, resulting in a coating with a thickness of about 5.8 μm.50 g of the prepolymer of Example 3 and 50 g of the prepolymer of Example 8 are mixed together and added to a mixture of 93 g 1-methoxy-2-propanol and 93 g water. 5.8 g aqueous amine oxide surfactant solution, 0.20 g hydrazine monohydrate, and 0.47 g hexanediamine chain extenders are added to the prepolymer mixture with agitation, resulting in a hazy aqueous polyurethane dispersion and an organic solvent polyurethane solution mixture. The resulting polyurethane mixture has a solid content of about 20% by weight of the polyurethane mixture. A polycarbonate lens is dip-coated in the aqueous polyurethane dispersion at a 12 inch/min draw speed. The dip-coated lens is dried at room temperature for 5 minutes and then dried at 85°C for an additional 10 minutes. The tack-free coated lens is cured at 120°C for 1 hour.Mix 23.3 g of IPDI, 7.1 g of PC 2000, 2.1 g of trimethylolpropane, 29.6 g of Tegomer D3403, 2.8 g of 1,6-hexanediol, and 35 g of acetonitrile together. Heat the mixture to 70°C, then add 0.01 g of tin catalyst. React the mixture for 3 hours in a nitrogen environment. After the reaction, cool the resulting polyurethane prepolymer mixture to 40°C. Disperse 45.2 g of the cooled polyurethane prepolymer mixture in 51.7 g of water using a high shear disperser. Add 0.62 g of hydrazine-monohydrate during dispersion. The resulting aqueous polyurethane dispersion will have about 30% solids by weight and comprise about 40% polyethylene oxide side chains by weight of the solids. Measure the viscosity of the dispersion, which is 70 cps at 25°C. Dip-coat a polycarbonate lens in the dispersion at a draw speed of 12 inches/min. Dry the dip-coated lens for 30 minutes at room temperature and cure at 90°C for 2 hours, resulting in a coating thickness of about 18.0 µm.$22.9\\mathrm{g}$ of IPDI, $14.5\\mathrm{g}$ of PC 2000, $2.2\\mathrm{g}$ of trimethylolpropane, $22.6\\mathrm{g}$ of Tegomer D3403, $2.9\\:\\mathrm{g}$ of 1,6-hexanediol, and $35\\mathrm{g}$ of acetonitrile are mixed together. The mixture is heated to $70^{\\circ}\\mathrm{C}.$ $_{0.01\\mathrm{~g~}}$ of tin catalyst is added. The mixture is then reacted for 3 hours in a nitrogen environment. After the reaction finishes, the resulting polyurethane prepolymer mixture is cooled to $40^{\\circ}$ C. $_{45.2\\mathrm{~g~}}$ of the cooled polyurethane prepolymer mixture is dispersed in $51.7\\mathrm{g}$ of water with a high shear disperser. $\\mathbf{0.62\\g}$ of hydrazine-monohydrate is also added during dispersion with the high shear disperser, resulting in an aqueous polyurethane dispersion having about $30\\%$ solids by weight of the dispersion.$21.6\\ \\mathrm{g}$ of IPDI, $31.0\\mathrm{g}$ of PC 2000, $2.1\\ \\mathrm{g}$ of trimethylolpropane, $7.4\\ \\mathrm{g}$ of Tegomer D3403, $2.8\\ \\mathrm{g}$ of 1,6-hexanediol, and $35\\mathrm{g}$ of acetonitrile are mixed together. The mixture is heated to $70^{\\circ}\\mathrm{C}$, and $0.01\\ \\mathrm{g}$ of tin catalyst is added. The mixture is then reacted for 3 hours in a nitrogen environment. After the reaction finishes, the resulting polyurethane mixture is cooled to $40^{\\circ}\\mathrm{C}$. $_{45.2\\mathrm{~g~}}$ of the cooled polyurethane mixture fails to disperse in $51.8\\ \\mathrm{g}$ of water with a high shear disperser. The resulting polyurethane comprises about $10\\%$ polyethylene oxide side chains by weight of the solids of the polyurethane.$25.4 g of IPDI, $24.8 g of PC 2000, $0.5 g of trimethylolpropane, $4.0 g of dimethylolpropionic acid, $9.9 g of Tegomer D3403, $2.5 g of 1,6-hexanediol, and $30 g of acetonitrile are mixed together. The mixture is heated to $70^{\\circ}C$, and $0.01 g$ of tin catalyst is added. The mixture is then reacted for 3 hours in a nitrogen environment. After the reaction finishes, the resulting polyurethane mixture is cooled to $40^{\\circ} C$. $27.9 g$ of the cooled polyurethane mixture fails to disperse into a mixture of $47.4 g$ of water and $24.8 g$ of quaternary amine surfactant solution with high shear disperser. The resulting polyurethane comprises about $12\\%$ polyethylene oxide side chains by weight of the solids of the polyurethane and about $10\\%$ neutralized amine by weight of the solids of the polyurethane.Mix 22.2 g of IPDI, 22.8 g of PC 2000, 2.1 g of trimethylolpropane, 15.0 g of Tegomer D3403, 2.8 g of 1,6-hexanediol, and 35 g of acetonitrile together. Heat the mixture to 70°C and add 0.01 g of tin catalyst. React for 3 hours in a nitrogen environment. After the reaction, cool the resulting polyurethane prepolymer mixture to 40°C. disperse 45.2 g of the cooled polyurethane prepolymer mixture in 51.8 g of water using a high shear disperser. Add 0.60 g of hydrazine-monohydrate during dispersion. The result will be an aqueous polyurethane dispersion with about 30% solids by weight. This polyurethane will comprise about 20% polyethylene oxide side chains by weight of the solids.The synthesis involves the composition of a first polyisocyanate component that may include a blocked polyisocyanate, and a second polyisocyanate component selected from diisocyanates and triisocyanates. Additionally, the synthesis uses a partially blocked tri-functional polyisocyanate with 1 free isocyanate functional group and 2 blocked isocyanate functional groups. An isocyanate-reactive salt of a surfactant is created through a neutralization reaction between an anionic surfactant's acid and a base containing an isocyanate-reactive functional group. Specific examples include a quaternary ammonium surfactant with 2 hydrophilic isocyanate-reactive functional groups and a hydrocarbon chain of at least 18 carbon atoms. The organic solvent utilized can comprise a variety of substances such as ketones, esters, or glycol ethers. Moreover, the process involves applying the coating composition to a substrate and curing it to create a durable coating."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/UV-curable anti-fog coatings.json b/task2/task2-paper-info/UV-curable anti-fog coatings.json
new file mode 100644
index 0000000..362c993
--- /dev/null
+++ b/task2/task2-paper-info/UV-curable anti-fog coatings.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "Silica nanoparticles, of size 10-15 nm, were used in a 30% dispersion in methanol, either directly without modification or modified by polyethylene glycol-modified silane and acrylate/methacrylate-modified silanes.Monomethyl ether polyethylene glycol (mPEG) (Mw=1100) was dissolved in toluene and the mixture was dried. At room temperature and under nitrogen, a molar equivalent (with respect to the mPEG) of 3-isocyantopropyl trimethoxysilane was added dropwise to the reaction mixture. A few drops of dibutyl tin dilaurate were added as a catalyst. The reaction mixture was then stirred continuously for 24h at 50°C. The reaction was monitored by infrared spectroscopy; the isocyanate signal is at 2271cm^-1. Upon completion, approximately two thirds of the toluene was removed by rotary evaporation and the mPEG trimethoxysilane was precipitated into hexane and washed several times. The resulting solid was dried and characterized by 1H NMR. Reaction yields of >90% were obtained.The surface of silica nanoparticles was functionalized with mPEG triethoxysilane and 3-(trimethoxysilyl)propyl acrylate or 3-(trimethoxysilyl)propyl methacrylate. The mixtures were stirred at room temperature overnight to finish the reaction.Formulations were prepared by mixing modified or unmodified silicon oxide nanoparticles with reactive diluents, polyethylene glycol diacrylate (Mw=575 g mol^{-1}), sulfopropyl acrylate potassium salt, and a photoinitiator, 1-hydroxycyclohexyl benzophenone. The sulfopropyl acrylate potassium salt was added as a solution in water. All the liquid coatings have a solid content of about 12%. Coatings were applied on PET or polycarbonate sheets using #16 wire wound rod. The coatings were dried for half a minute, and then cured under a 300 W per inch mercury vapor lamp at a dose of 1 J/cm^2 in a nitrogen atmosphere. The thicknesses of the cured coatings were about 5 micrometers."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/Verma2019_Article_AReviewOnProtectivePolymericCo.json b/task2/task2-paper-info/Verma2019_Article_AReviewOnProtectivePolymericCo.json
new file mode 100644
index 0000000..77140ce
--- /dev/null
+++ b/task2/task2-paper-info/Verma2019_Article_AReviewOnProtectivePolymericCo.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of hydrophilic polymers with functional groups involves the use of various precursor materials and potentially the incorporation of foreign materials like superhydrophobic particles. The methodology may involve the modification of polymer surfaces and/or bulk properties through wet chemistry, physical modifications, or biological modifications. Specific polymers that can be synthesized for coatings include polysaccharides, zwitterionic polymers, polycationic coatings, and others which are designed for antifouling applications. The process emphasizes incorporating surface-active additives during polymer fabrication to enhance functional properties."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/Zhao et al.json b/task2/task2-paper-info/Zhao et al.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/Zhao et al.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/a facile approach to UV-curable super-hydrophilic polyacrylate coating film grafted on glass substrate.json b/task2/task2-paper-info/a facile approach to UV-curable super-hydrophilic polyacrylate coating film grafted on glass substrate.json
new file mode 100644
index 0000000..f5d7d4b
--- /dev/null
+++ b/task2/task2-paper-info/a facile approach to UV-curable super-hydrophilic polyacrylate coating film grafted on glass substrate.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "First, treat the glass substrate with a piranha solution to increase the number of hydroxyl groups. Next, modify the substrate with gamma-methacryloxypropyltrimethoxysilane (MPS) to introduce C=C double bonds. Prepare the superhydrophilic polyacrylate coating films by utilizing 2-methacrylatoethyl trimethyl ammonium chloride (DMC) as the hydrophilic monomer and trimethylolpropane triacrylate (TMPTA) as the crosslinker through UV-initiated polymerization.Glass slides were treated by submerging in a freshly prepared piranha solution containing 70% H2SO4 and 30% H2O2 at 90°C for 1h, then rinsed with copious amounts of deionized water to obtain hydroxylated glass substrates. 10 g MPS was added into 190 g ethanol solution (Vethanol/Vwater=2) in a 500 mL beaker and stirred for 1h at room temperature. The solution was heated to 70°C, the hydroxylated glass substrates were immersed for 45min, then taken out and placed in a vacuum oven at 110°C for 1h for further reaction. Finally, the glass substrates were rinsed thoroughly with ethanol by ultrasonic three times at room temperature, then dried in a vacuum oven at 40°C for 24h to prepare MPS-modified glass substrates.Appropriate amount of DMC solution, TMPTA, Darocur 1173, and ethanol were uniformly mixed. The obtained solution was dripped and scraped onto the MPS-modified glass substrate using a flat-plate knife coater. The samples were then exposed to UV light (INTELLIRAY 400, Uvitron International, Inc., USA) for 400 seconds, with the distance between the samples and the center of the UV light lamp being 15 cm. After ethanol evaporation and the occurrence of the UV-curing reaction, films with an average thickness of 13±1 μm were obtained.To synthesize UV-curable super-hydrophilic polyacrylate coating films, the following formulations (with mass ratios of DMC to TMPTA) and corresponding amounts of each component are used: S1 (9/1) - 4.0 g DMC, 0.32 g TMPTA, 0.16 g Darocur 1173, 20.0 g Ethanol; S2 (8/2) - 4.0 g DMC, 0.72 g TMPTA, 0.16 g Darocur 1173, 20.0 g Ethanol; S3 (7/3) - 4.0 g DMC, 1.23 g TMPTA, 0.16 g Darocur 1173, 20.0 g Ethanol; S4 (6/4) - 4.0 g DMC, 1.92 g TMPTA, 0.16 g Darocur 1173, 20.0 g Ethanol; S5 (5/5) - 4.0 g DMC, 2.88 g TMPTA, 0.16 g Darocur 1173, 20.0 g Ethanol. The films are then applied as a coating on a glass substrate."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/adma.201807101.json b/task2/task2-paper-info/adma.201807101.json
new file mode 100644
index 0000000..225ecc1
--- /dev/null
+++ b/task2/task2-paper-info/adma.201807101.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "To synthesize hydrophilic polymers with functional groups, first treat the polymer substrates with a 10 wt% solution of hydrophobic photo- or thermoinitiators (e.g., benzophenone, 4-methyl benzophenone, benzoyl peroxide, azobisisobutyronitrile) in an organic solvent (e.g., ethanol, isopropanol, acetone) via swelling-driven surface absorption to form a surface-bound diffusion layer of hydrophobic initiators. Next, immerse the treated polymer substrates in a hydrogel pregel solution bath containing hydrophilic photo- or thermoinitiators (e.g., Irgacure-2959, α-ketoglutaric acid, ammonium persulfate, potassium persulfate) and hydrogel monomers (e.g., acrylamide (AAm), acrylic acid (AA), N,N-dimethylacrylamide (DMAA), N-vinylpyrrolidone (VP), hydroxyethyl methacrylate (HEMA)) in aqueous solution. Polymerize the hydrogel pregel solution using UV light or heat, allowing the hydrophobic initiators to act as grafting agents and oxygen scavengers, while the hydrophilic initiators facilitate the polymerization of the hydrogel monomers. After polymerization, wash the non-crosslinked hydrogel polymer solution away with water to obtain the polymer substrates with hydrogel skins.The polymer substrates were first cleaned with isopropanol and deionized water followed by drying under nitrogen flow. To enhance wettability of the polymer substrates, the substrates were treated by atmospheric plasma by a plasma cleaner for 3 min. The plasma treated polymer substrates were then immersed into a hydrophobic initiator organic solution for 3-5 min. After gently rinsing with isopropanol followed by drying under nitrogen flow, the substrates were immersed into a hydrogel monomer aqueous solution containing hydrophilic initiator. To form hydrogel skins, the monomer solution bath was subjected to either UV irradiation or an 80°C oven for 30–90 min. After formation of hydrogel skins, unreacted regents were thoroughly rinsed with a large amount of deionized water for 24 h."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/adma202002710-sup-0001-suppmat.json b/task2/task2-paper-info/adma202002710-sup-0001-suppmat.json
new file mode 100644
index 0000000..ad368c9
--- /dev/null
+++ b/task2/task2-paper-info/adma202002710-sup-0001-suppmat.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "1. Prepare dipping solutions with the following concentrations: CHI and CMC at 1 mg/ml, positive charged SiO2 at 0.03% (w/w), and negative charged SiO2 at 0.03% (w/w). 2. For CHI, add 0.3% (v/v) acetic acid and dissolve the polymer. 3. Filter the solution with a 5 μm pore filter after stirring overnight. 4. Use deionized water (18.2 MΩ·cm at 25 °C) for all aqueous solutions. 5. Perform sequential stacking of polymer and nanoparticle layers using a StratoSequence 8 spin dipper. 6. Immerse the substrate in each dipping solution for 10 minutes followed by three rinsing steps (2, 1, and 1 min) in deionized water. 7. Create the polymeric reservoir (CHI/CMC)n by alternately dipping in CHI and CMC solutions with rinsing steps in between. 8. Prepare the polymer-silica nanocomposite by depositing two complementary interacting nanoparticles on the polymeric reservoir.To synthesize hydrophilic polymers with functional groups, follow these steps: First, fabricate a SU-8 pillar array using typical lithography with a negative photoresist (SU-8 50). Then, pour PDMS onto the master and cure it in an oven at 70°C for 3 hours. After that, pour a photocurable PFPE polymer precursor containing 4% (w/w) Darocur 1173 into the PDMS microwell and remove the excess using a razorblade. Prior to attachment and curing, infuse the polymer-silica nanocomposite with silicone oil to prevent PFPE film formation on the polymer-silica nanocomposite. Finally, irradiate with UV light at an intensity of 20 mW cm^-2 for 5 minutes to induce photocuring of the PFPE pillars, and wash off any residue with acetone."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/admi.201801018.json b/task2/task2-paper-info/admi.201801018.json
new file mode 100644
index 0000000..a566d39
--- /dev/null
+++ b/task2/task2-paper-info/admi.201801018.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "1. Prepare a primer layer by pretreating the solid surface with a solution containing poly(vinyl acetate) (PVAc) and a radical initiator. 2. Allow the primer layer to dry, forming a strong physical coating with the embedded initiator. 3. Prepare a pre-gel solution that contains brittle first network gel particles and second network monomer, acrylamide (AAm), and poly(2-acrylamido-2-methylpropane sulfonic acid sodium salt) (PNaAMPS). 4. Apply the pre-gel solution to the surface covered with a glass plate and spacer to prevent drying and control thickness. 5. Initiate polymerization of the second network from the initiator embedded in the primer layer. 6. The second network will strongly bond to the surface via covalent bonding to the primer layer, forming a tough hydrogel coating.P-DN gel films were synthesized using a two-step sequential free-radical polymerization method. In the first step, for the first network particle preparation, MBAA (0.5-6 mol%) and α-keto (0.1 mol%) were added to a 1 M NaAMPS solution. The mixture was poured into reaction cells consisting of a pair of glass plates with a 1 mm silicone spacer. Photoinduced free radical polymerization was conducted under argon atmosphere with a UV lamp for 10 h (UV light intensity was 3.9 mW/cm²). The resulting PNaAMPS gels were ground into particles, dried in a vacuum oven for 24 h, and then finely ground with a multibead shocker to achieve particles ranging from 10 to 200 μm. For the second network, the dried PNaAMPS particles were added into a 4 M AAm aqueous solution containing MBAA (0.01 mol%) and α-keto (0.01 mol%), with the concentration of PNaAMPS particles to AAm solution varied from 0.005 to 0.030 mg/mL. This precursor mixture was poured into reaction cells and the AAm monomers were photopolymerized with a UV lamp for 8 h to obtain P-DN gel sheets. The P-DN gels exhibited an equilibrium thickness of 1.5 mm when swollen in pure water."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/advs3770-sup-0001-suppmat.json b/task2/task2-paper-info/advs3770-sup-0001-suppmat.json
new file mode 100644
index 0000000..775d0b8
--- /dev/null
+++ b/task2/task2-paper-info/advs3770-sup-0001-suppmat.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Preparation of PVA-WI coating: PVA with the mass of 3.6 g was dissolved in 15 ml water and stirred for 2 h at 95°C. After defoaming, the resultant solution was spread on the glass slides to produce a uniform liquid layer with different thickness (25, 100, 200 µm) using a wet film coater. To obtain dry PVA-WI coated substrates, the samples were dried at 25°C for 24 h. Preparation of PVA-SI coating: Oxygen plasma-treated glass slides were immersed in a mixture of 90 ml ethanol, 10 ml water, 5 ml 3-glycidoxypropyltrimethoxysilane, and 100 µl acetic acid at room temperature for 12 h. After cleaning, the epoxy-functionalized glass slides were prepared. PVA with the mass of 3.6 g was dissolved in 15 ml water (pH=2) and stirred for 2 h at 95°C. After defoaming, the resultant solution was spread on the epoxy-functionalized glass slides to produce a uniform liquid layer with different thickness (25, 100, 200 µm) using a wet film coater. The samples were placed in a 60°C oven for 12 hours to complete chemical grafting of PVA. To obtain dry PVA-SI coated substrates, the samples were dried at 25°C for 24 h."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/am3c17117_si_001.json b/task2/task2-paper-info/am3c17117_si_001.json
new file mode 100644
index 0000000..a18d470
--- /dev/null
+++ b/task2/task2-paper-info/am3c17117_si_001.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "1. Prepare a solution of PVP at a concentration of 0.053 g/ml using a mixture of 1-propanol, water, and 30% H2O2 in volume ratios of 0.931:0.029:0.040. 2. Develop PETRA/1-Propanol solutions and add to the PVP solution in a volume of 2 ml, adjusting according to the desired mass ratio of PETRA/PVP. 3. Dispense 5 ml of the final PVP-based solution into a silicone mold (76.2 x 50.8 x 1.2 mm) and allow to dry for 2 days. 4. Cure the dried film and mold under UVC for 30 minutes. 5. Cut the cured polymer sheet to approximately 7.5-8 mm widths and lengths of approximately 76 mm. 6. Sandwich the cut samples between two glass plates and allow to dry uniformly for more than 10 hours in an environment with relative humidity less than 20%.Hansen solubility parameters were measured by dissolving a small amount (3-5 drops) of surfactant into 10 ml of solvent. The solvents consisted of DI water, Methanol, Ethanol, 1-Propanol, 2-Propanol, Dimethyl Formamide, 1-Hexanol, Dimethyl Sulfoxide, Ethyl Acetate, Toluene, Benzene, Cyclohexane, Decane, Pentane, n-Heptane, O-Xylene, Perfluorohexane, Formamide, Acetonitrile, Acetic Acid, Propylene Carbonate, Methyl Acetate, Chloroform, and 30% Hydrogen Peroxide. Once added to the solvent, the solutions were mixed briefly in a vortexer. The solutions were visually inspected to determine their solubility within each solvent and noted. The data was plugged into the HSPiP version 5.3.09 and Hansen solubility parameters and sphere radii were generated."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/am7b05286_si_001.json b/task2/task2-paper-info/am7b05286_si_001.json
new file mode 100644
index 0000000..38dfcee
--- /dev/null
+++ b/task2/task2-paper-info/am7b05286_si_001.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Synthesis of POSS-PDMAEMA. POSS-PDMAEMA was synthesized by using POSS-Br as an ATRP macroinitiator. The mixture of POSS-Br (0.1024 g, 0.1 mmol), DMAEMA (1.8865 g, 12 mmol), HMTETA (0.0277 g, 0.12 mmol) and THF (2 ml) was injected into the 10 mL standard Schlenk flask. Highly pure nitrogen was filled the flask and then oxygen was removed by three freeze-pump-thaw cycles. Subsequently, CuBr (0.0144 g, 0.1 mmol) was added quickly to the flask. Three freeze-pump-thaw cycles were carried out again to remove residual oxygen. The mixture was reacted at 50°C for 1.5, 2 and 2.5 h, respectively, and terminated by dropping a few THF droplets into the flask. The solution was passed through a neutral alumina column to intercept Cu^{2+} and concentrated in a rotary evaporator. Finally, POSS-PDMAEMA polymers with three different polymerization degrees, i.e., POSS-PDMAEMA 50, POSS-PDMAEMA 70, and POSS-PDMAEMA 90, were obtained by precipitating into cold n-hexane and followed by drying in a vacuum oven for 24 h."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/am9b09610_si_001.json b/task2/task2-paper-info/am9b09610_si_001.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/am9b09610_si_001.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/am9b21871_si_001.json b/task2/task2-paper-info/am9b21871_si_001.json
new file mode 100644
index 0000000..75864b3
--- /dev/null
+++ b/task2/task2-paper-info/am9b21871_si_001.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of hydrophilic polymers involves the use of N-Hydroxyethylacrylamide as a monomer. The reaction typically requires the addition of a suitable initiator and may include functional groups through copolymerization with other acrylates or methacrylates. The mixture is then subjected to a controlled temperature to initiate polymerization, followed by purification processes such as dialysis or precipitation to obtain the final polymer product.Synthesis of POSS-P(QAC-co-AEMA): QAC (588.0 mg, 2 mmol), AEMA (82.8 mg, 0.5 mmol), POSS-CPADB (11.4 mg, 0.01 mmol) and AIBN (0.4 mg, 0.0025 mmol) dissolved in EtOH (1 mL) were added into a 10 mL Schlenk flask. The flask was deoxygenated by three consecutive freeze-pump-thaw cycles before the polymerization was conducted at 70°C for 10 h, and then quenched by rapid cooling immersion of the flask into iced water. The synthesized copolymer of POSS-P(QAC-co-AEMA) was precipitated into n-hexane for five times and subsequently dialyzed for 3 days to lyophilize."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/ao4c03563_si_001.json b/task2/task2-paper-info/ao4c03563_si_001.json
new file mode 100644
index 0000000..5e592f4
--- /dev/null
+++ b/task2/task2-paper-info/ao4c03563_si_001.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis involves using CarboxyFunctionalized Polyhedral Oligomeric Silsesquioxane (POSS-C) and Oligo(ethylene glycol) (OEG) in varying molar ratios. The mixtures are prepared with different ratios as follows: COOH:OH (POSS-C):(OEG) ratios of 5:1, 2:1, and 1:1, and for each ratio, different numbers of ethylene glycol repeating units (n=1 to n=6) can be utilized. The coatings are then applied to a glass substrate for further characterization."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/ap4c00912_si_001.json b/task2/task2-paper-info/ap4c00912_si_001.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/ap4c00912_si_001.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/bai-et-al-2020-antifogging-antibacterial-coatings-constructed-by-n-hydroxyethylacrylamide-and-quaternary-ammonium.json b/task2/task2-paper-info/bai-et-al-2020-antifogging-antibacterial-coatings-constructed-by-n-hydroxyethylacrylamide-and-quaternary-ammonium.json
new file mode 100644
index 0000000..19e6e1e
--- /dev/null
+++ b/task2/task2-paper-info/bai-et-al-2020-antifogging-antibacterial-coatings-constructed-by-n-hydroxyethylacrylamide-and-quaternary-ammonium.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of hydrophilic polymers with functional groups involves the blending of polyhedral oligomeric silsesquioxane-poly(N-(2-(methacryloyloxy)ethyl)-N,N-dimethylbutan ammonium bromide-co-2-aminoethyl methacrylate hydrochloride) [POSS-P(QAC-co-AEMA)] and poly(N-hydroxyethyl acrylamide-co-glycidyl methacrylate) [P(HEAA-co-GMA)]. Incorporation of AEMA and GMA is performed to crosslink the two random copolymers. A small quantity of 1,3,5-triformylbenzene (TFB) is added as a co-crosslinker to further react with the amino and hydroxyl groups in the copolymers, as well as amino-modified glass substrates, forming a chemically crosslinked stable system. The specific compositions for the coatings include varying amounts of POSS-P(QAC-co-AEMA), P(HEAA-co-GMA), and TFB with specified mass ratios to achieve optimal blending for antifogging and antibacterial properties.Synthesis of POSS-P(QAC-co-AEMA) and P(HEAA-co-GMA) Copolymers involves the following steps: 1. Prepare QAC by quaternizing 2-(dimethylamino)ethyl methacrylate (DMAEMA) with 1-bromobutane. 2. Modify the RAFT agent CPADB with aminopropylisobutyl polyhedral oligomeric silsesquioxane (POSS-NH2) to obtain POSS-CPADB. 3. Synthesize POSS-P(QAC-co-AEMA) copolymers via reversible addition−fragmentation chain transfer (RAFT) polymerization. 4. Synthesize P(HEAA-co-GMA) copolymers using free radical polymerization. The copolymers are characterized by proton nuclear magnetic resonance (1H NMR) spectroscopy and gel permeation chromatography (GPC).Materials and synthesis procedures of QAC, POSS-CPADB, POSS-P(QAC-co-AEMA), and P(HEAA-co-GMA) are discussed along with characterizations by $^{1}\\mathrm{H}$ NMR and GPC."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/bai2020.json b/task2/task2-paper-info/bai2020.json
new file mode 100644
index 0000000..772eeb1
--- /dev/null
+++ b/task2/task2-paper-info/bai2020.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "1. Synthesize POSS-P(QAC-co-AEMA) and P(HEAA-co-GMA) copolymers. 2. Incorporate AEMA and GMA to crosslink the two random copolymers. 3. Add a small quantity of 1,3,5-triformylbenzene (TFB) as a co-crosslinker to react with amino and hydroxyl groups in the copolymers and amino-modified glass substrates. 4. Blend copolymers with varying ratios: For one-component coatings, use POSS-P(QAC-co-AEMA) or P(HEAA-co-GMA) only. For blending coatings, utilize different mass ratios as follows: PPQA (POSS-P(QAC-co-AEMA) 18 mg, TFB 0.54 mg), PPQA/PHG (12 mg POSS-P(QAC-co-AEMA), 6 mg P(HEAA-co-GMA), TFB 0.54 mg), PPQA/PHG (9 mg POSS-P(QAC-co-AEMA), 9 mg P(HEAA-co-GMA), TFB 0.54 mg), PPQA/PHG (6 mg POSS-P(QAC-co-AEMA), 12 mg P(HEAA-co-GMA), TFB 0.54 mg), PHG (18 mg P(HEAA-co-GMA), TFB 0.54 mg). 5. Evaluate antifogging and antibacterial properties using hot-vapor and cold-warm antifogging tests, standard plate count method, bacterial antiadhesive assays, and growth inhibition.Synthesis of POSS-P(QAC-co-AEMA) and P(HEAA-co-GMA) Copolymers was carried out using reversible addition−fragmentation chain transfer (RAFT) polymerization for POSS-P(QAC-co-AEMA) and free radical polymerization for P(HEAA-co-GMA). QAC was prepared by quaternization of 2-(dimethylamino)ethyl methacrylate (DMAEMA) with 1-bromobutane. The hydrophobic component was incorporated by modifying the RAFT agent of CPADB with aminopropylisobutyl polyhedral oligomeric silsesquioxane (POSS-NH2) to obtain POSS-CPADB. For blending coatings, bare glass was treated with oxygen plasma (18 W, 60 s) and immersed in (3-aminopropyl)-trimethoxysilane/methanol solution (5%, v/v) for 4 h. After sonicating with methanol and ethanol, copolymers with varying POSS-P(QAC-co-AEMA)/P(HEAA-co-GMA) blending ratios were dissolved in 200 µL of ethanol. A determined volume of the mixture was drop-coated onto the modified glass slides to allow crosslinking for antifogging tests. Coated samples were dried at room temperature and thermal cured at 40 °C overnight.Synthesis procedures of QAC, POSS-CPADB, POSS-P(QAC-co-AEMA), and P(HEAA-co-GMA) with functional groups are detailed in the Supporting Information, including their characterizations by $^{1}\\mathrm{H}$ NMR and GPC."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/bayer2655-US6767958.json b/task2/task2-paper-info/bayer2655-US6767958.json
new file mode 100644
index 0000000..8346958
--- /dev/null
+++ b/task2/task2-paper-info/bayer2655-US6767958.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The article provides a detailed experimental procedure for the synthesis of hydrophilic polymers with functional groups using modified polyisocyanates. First, the polyisocyanate is reacted with a suitable polyol or amine compound under controlled temperature conditions to achieve the desired functionalization. The reaction is carried out in a solvent that enhances solubility and ensures thorough mixing. The modified product is then precipitated out, washed, and dried to obtain the final hydrophilic polymer. Specific ratios of reactants and the reaction time are crucial for optimizing the functional groups on the polymer backbone.The synthesis of hydrophilic polymers with functional groups, specifically water-dispersible polyisocyanates, involves the modification of polyisocyanates with polyethers to increase hydrophilicity. Additionally, the incorporation of ionic groups, such as chemically bonded carboxyl groups, is explored to enhance dispersibility in aqueous systems. The process includes neutralization of carboxyl groups to allow for easier stirring into aqueous systems without requiring high shear forces. Emulsifiers are formed from the reaction of polyisocyanates with hydroxy-, mercapto-, or amino-functional compounds that possess at least one sulfuric acid group or its anion. Preferred emulsifiers include hydroxysulfonic acids or their sodium salts, which are prepared in forms suitable for industrial scaling. The final products aim for compatibility with conventional paint binders while avoiding undesirable characteristics such as excessive yellowing or permanent hydrophilicity from sodium ions.2-(cyclohexylamino)-ethanesulfonic acid or 3-(cyclohexylamino)-propanesulfonic acid is reacted with polyisocyanates under mild reaction conditions in the presence of a suitable neutralization amine to obtain storage-stable, light-coloured products that can be emulsified in water.A) A polyisocyanate component with an average functionality of 2.0 to 5.0 and a content of aliphatically, cycloaliphatically, araliphatically and/or aromatically bonded isocyanate groups of 8.0 to 27.0 wt. %. B) 0.3 to 25.0 wt. %, based on the total weight of components A) and B), of 2-(cyclohexylamino)-ethanesulfonic acid and/or 3-(cyclohexylamino)-propanesulfonic acid. C) Up to 25 wt. %, based on the total weight of components A), B) and C), of a monohydric polyalkylene oxide polyether alcohol containing a statistical average of 5 to 35 ethylene oxide units. D) 0.2 to 2.0 equivalents, based on the sulfonic acid groups of component B), of a tertiary amine. These components are reacted while observing an equivalent ratio of isocyanate (NCO) groups to groups which are reactive towards NCO groups of 2:1 to 400:1.To synthesize hydrophilic polymers with functional groups, follow these steps: 1. Use polyisocyanates (Component A) that have exclusively aliphatically and/or cycloaliphatically bonded isocyanate groups, preferably those with an isocyanurate structure based on HDI, IPDI, or 4,4'-diisocyanatodicyclohexylmethane. 2. Optionally, include polyisocyanates modified hydrophilically with ethylene oxide polyethers. 3. Choose aminosulfonic acids (Component B), such as 2-(cyclohexylamino)-ethanesulfonic acid (CHES) or 3-(cyclohexylamino)-propanesulfonic acid (CAPS), in amounts ranging from 0.3 to 25 wt.%, preferably 0.5 to 25 wt.%, based on the total weight of components A and B. 4. Optionally, incorporate monohydric polyalkylene oxide polyether alcohols (Component C), containing a statistical average of 5 to 35 ethylene oxide units, in amounts of up to 25 wt.%, preferably up to 20 wt.%, based on the total weight of components A, B, and C. 5. Introduce tertiary amines (Component D) for neutralizing the sulfonic acid groups, in amounts that maintain an equivalent ratio of tertiary amino groups to sulfonic acid groups of 0.2 to 2.0, preferably 0.5 to 1.5. 6. React components A, B, and optionally C, in the presence of amine D at temperatures between 40 to 150 °C, observing an equivalent ratio of NCO groups to reactive groups of 2:1 to 400:1, preferably 4:1 to 250:1, until the theoretically calculated NCO content is reached. 7. Additional catalysts may be used to accelerate the reaction.The synthesis of hydrophilic polymers with functional groups involves the use of polyisocyanates characterized by an average NCO functionality preferably between 2.0 to 4.8, an NCO content of 7.0 to 23.0 wt. %, a sulfonate group content (calculated as SO3-) preferably within 0.2 to 6.3 wt. %, and a content of ethylene oxide units in the polyether chains preferably up to 17 wt. %. The process is carried out in a suitable solvent that is inert to isocyanate groups, such as ethyl acetate, butyl acetate, acetone, and N-methylpyrrolidone among others. The resulting polyisocyanates should be converted into sedimentation-stable dispersions by stirring into water. The polyisocyanates can then be used to prepare polyisocyanate plastics through the isocyanate polyaddition process, preferably in the form of aqueous emulsions reacted with polyhydroxy compounds that contain groups reactive with isocyanate, such as alcoholic hydroxyl groups.900 g (4.97 eq) of a polyisocyanate which contains isocyanurate groups and is based on HDI, with an NCO content of 23.2%, an average NCO functionality of 3.2, a content of monomeric HDI of 0.1%, and a viscosity of 1,200 mPas (23°C) are stirred together with 100 g (0.45 eq) CAPS and 57 g (0.45 mol) dimethylcyclohexylamine under dry nitrogen for 10 hours at 80°C. After cooling to room temperature, a practically colourless clear polyisocyanate mixture according to the invention with the following characteristic data is present.$950\\\\mathrm{~g~}$ (4.90 eq) of a polyisocyanate which contains isocyanurate groups and is based on 1,6-diisocyanatohexane (HDI), with an NCO content of $21.7\\\\%$, an average NCO functionality of 3.5 (according to GPC), a content of monomeric HDI of $0.1\\\\%$ and a viscosity of $3,000\\\\mathrm{mPas}$ $(23^{\\\\circ}\\\\mathrm{C})$, are stirred together with $50\\\\mathrm{g}(0.23\\\\mathrm{eq})$ 3-(cyclohexylamino)- propanesulfonic acid (CAPS), $29\\\\mathrm{g}\\\\left(0.23\\\\mathrm{mol}\\\\right)$ dimethylcyclohexylamine and $257\\\\mathrm{g}1$ -methoxyprop-2-yl acetate under dry nitrogen for 5 hours at $80^{\\\\circ}\\\\mathrm{~C~}$. After cooling to room temperature, a practically colourless clear solution of a polyisocyanate mixture according to the invention with the following characteristic data is present:$950\\ \\mathrm{~g~}$ (4.90 eq) of the polyisocyanate containing isocyanurate groups based on HDI is stirred with $50\\ \\mathrm{~g~}$ (0.36 eq) 2-methylaminoethanesulfonic acid, $\\boldsymbol{46}_{\\mathrm{~\\scriptsize~g~}}$ (0.36~\\mathrm{~mol}) dimethylcyclohexylamine, and $262\\ \\mathrm{~g~}$ 1-methoxyprop-2-yl acetate under dry nitrogen at $80^{\\circ}\\mathrm{~C~}$. The reaction is carried out for a total of 12 hours, with the temperature increased to $120^{\\circ}\\mathrm{~C~}$ after 8 hours. The reaction mixture remains cloudy and inhomogeneous, and methyltaurine settles as a crystalline sediment.100 g deionized water were added to a conical flask with 35 g of polyisocyanate mixtures, including 15 g of an 80% solution from examples 1, 2, and 4, 40 g of a 70% solution from example 5, and 25 g of the polyisocyanate mixture from example 3, resulting in a solids content of approximately 20 wt%. The mixtures were stirred for 1 min with a magnetic stirrer at 900 rpm. The emulsions obtained were stable for 5 hours without visible CO2 evolution, precipitates, or sediment.Combine 950 g (4.90 eq) of polyisocyanate containing isocyanurate groups based on HDI with 50 g (0.40 eq) of 2-aminoethanesulfonic acid (taurine), 51 g (0.40 mol) of dimethylcyclohexylamine, and 263 g of 1-methoxyprop-2-yl acetate. Stir the mixture under dry nitrogen at 80°C for 8 hours. If the reaction mixture remains cloudy, increase the temperature to 120°C and continue stirring for an additional 6 hours. Observe that methyltaurine may settle as a crystalline sediment in the reaction mixture.Initially introduce 350 g of the polyisocyanate mixture into the reaction vessel at 70°C. Add 126 g of 3,5-dimethylpyrazole in portions over 30 min while maintaining the temperature of the reaction mixture below 80°C. Stir the mixture for approximately 2 hours at 70°C until free isocyanate groups are no longer detectable by IR spectroscopy. Cool the mixture to 40°C, then allow 539 g of deionized water to run in with vigorous stirring over 30 min.Combine up to 20 wt. % of a monohydric polyalkylene oxide polyether alcohol, containing an average of 5 to 35 ethylene oxide units, with 0.5 to 1.5 equivalents of a tertiary amine based on the sulfonic acid groups of the other components. Use a polyisocyanate prepared from at least two molecules of specified isocyanates such as 1,6-diisocyanatohexane or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/binder2014.json b/task2/task2-paper-info/binder2014.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/binder2014.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/biomimetics-07-00162-v2.json b/task2/task2-paper-info/biomimetics-07-00162-v2.json
new file mode 100644
index 0000000..7ba49a8
--- /dev/null
+++ b/task2/task2-paper-info/biomimetics-07-00162-v2.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "A series of copolymers consisting of hydrophilic hydroxyethyl methacrylate (HEA), hydrophobic methyl methacrylate (MMA), and benzophenone-based acrylate (BP-Acrylate) units were synthesized by thermally triggered radical polymerization. The hydrophilic-hydrophobic balance of the copolymers can be adjusted by varying the molar ratio of HEA to MMA. After synthesis, the copolymers were coated on the surface of PC plates, followed by exposure to UV light to achieve covalently bonded anti-fogging coatings.A series of acrylate copolymers were synthesized via free radical copolymerization containing HEA (3.0g), MMA (7.0g), and 4-BP acrylate (0.5g) with AIBN (0.21g, ~2% of total mass weight of monomers). The monomers were dissolved in 10 mL DMF to form a homogeneous solution. The mixture was maintained at 60°C for 12 hours and then dialyzed against distilled water using 5 kDa MWCO dialysis tubing with a regenerated cellulose membrane for 24 hours with 3 water changes to remove the organic solvent and unreacted monomer. The sample was labeled as P-30% according to the mass percentage of HEA (30 wt.%) to the total mass weight of HEA and MMA. Other products with different mass percentages of HEA (50, 70, and 90 wt.%) were prepared and labeled as P-50%, P-70%, and P-90% accordingly. The purified copolymers (P-30%, P-50%, P-70%, P-90%) were dissolved in D6-DMSO to form a uniform solution. 1H-NMR measurements were conducted on a 400 MHz NMR spectrometer, with ~100 mg of polymer dissolved in 1 mL D6-DMSO solvent. The chemical structures were characterized by the 1H NMR spectra, and the monomer unit ratios were calculated from the peak integration values of the spectra. Number-average molecular weights (Mn) and molecular weight distributions (PDI = Mw/Mn) were determined by gel permeation chromatography (GPC) using linear Tskgel Super columns (AW3000 and AW5000), with OPTILAB DSP Interferometric Refractometer as the detector. The eluent was DMF at a flow rate of 1.0 mL min-1. Monodispersed polystyrene standards were used to generate the calibration curve, yielding Mn of the copolymers in the range of 63.4 to 79.1 kDa and PDI ranging from 1.3 to 1.6.Cut PC plates into rectangular pieces (2.5x7.5 cm), sonicate in ethanol and water, and dry completely in a vacuum oven. Dissolve resultant copolymers in acetone to create 10 wt.% solutions. Immerse PC plates into the copolymer solution for 60 s, then suspend in air for 20 s. Illuminate the copolymer coated PC plates with a UV lamp for 3 minutes (300 W, 360 nm) to obtain UV curable coatings. Wash prepared coatings with acetone and dry in a vacuum oven at 80 °C, naming them C-30%, C-50%, C-70%, C-90% respectively.The copolymers were synthesized through a thermally triggered free-radical polymerization reaction using hydrophilic HEA, hydrophobic MMA, and 4-BP-acrylate units. The 4-BP-acrylate groups function as a UV photo-initiator to immobilize the copolymer on the PC substrate surface. Under UV irradiation, the BP-based groups are excited to a singlet state, then jump to a triplet state, undergoing a hydrogen-abstracting reaction from the substrates, followed by a coupling reaction that covalently bonds the copolymers to the substrate surface. The mass percentages of HEA and MMA can be adjusted to control the surface zwitter-wettable behaviors. The desired molar ratios of HEA/MMA/4-BP acrylate in copolymers are monitored and confirmed through 1H NMR analysis. Post-UV treatment, the coatings are cleaned to remove unbonded copolymers and are evaluated by ATR-FTIR spectroscopy for characterization."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/c5ra21399a.json b/task2/task2-paper-info/c5ra21399a.json
new file mode 100644
index 0000000..377e63b
--- /dev/null
+++ b/task2/task2-paper-info/c5ra21399a.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Prepare a semi-interpenetrating polymer network (SIPN) using a linear terpolymer poly(2-(dimethylamino)ethyl methacrylate-co-N-vinylpyrrolidone-co-methyl methacrylate) at an optimal molar ratio of 40/30/30 for DMAEMA/NVP/MMA, combined with a network of poly(ethylene glycol dimethacrylate) (PEGDMA).Monomers including DMAEMA (98%), N-vinylpyrrolidone (NVP, 99%), EGDMA (99%), and MMA (99%) are dissolved in a suitable solvent such as DMF, toluene, or chloroform. Free radical initiators, HHMP (98%) or AIBN (99%), are added to the solution to initiate the polymerization. The reaction mixture is stirred at an appropriate temperature and for a specific duration to allow the formation of the hydrophilic polymers with desired functional groups.Three monomers, DMAEMA (4.8 g), NVP (4.5 g) and MMA (3.0 g) (molar percentage: 30% DMAEMA, 40% NVP, and 30% MMA) were added into DMF in a 100 mL flask to obtain 10 wt% solution; then, the thermal initiator AIBN (0.5 wt% with respect to the total monomer mass) was added. After being purged by argon for 20 min, the polymerization was carried out at 70°C for 24 h under magnetic stirring (200 rpm). The final terpolymer, designated as T-30 according to the DMAEMA molar percentage, was purified by dissolution in chloroform and precipitation in cyclohexane (twice), and dried in a vacuum oven.Glass slides (1.5 × 1.5 cm²) were sonicated consecutively in acetone and ethanol for 30 min, followed by blow-drying with air. A terpolymer (2.0 g), EGDMA (0.5 wt% with respect to the terpolymer), and HHMP (2.0 wt% relative to EGDMA) were dissolved in toluene (20.0 mL) to obtain a homogeneous solution. The mixture was then spun-coated on clean glass slides at various rates (400, 800, 1500 and 3000 rpm) for 15 s. The spun-coated film was then cured under UV irradiation in a UVP CL-1000 ultraviolet cross-linker apparatus (365 nm, 15 W) for 45 min, and dried in a vacuum oven at 70 °C for 24 h.Synthesize terpolymers using three monomers: DMAEMA, NVP, and MMA through conventional free radical polymerization. The molar ratio of the monomers should be adjusted to achieve a balanced hydrophobicity and hydrophilicity in the final terpolymer. After synthesis, form a SIPN coating comprising the terpolymer and a network of polymerized EGDMA at a concentration of 0.5 wt% relative to the copolymer. Monitor the molecular weight of the terpolymers using GPC, aiming for an Mn of approximately 30,000, and confirm the molar ratio of the monomeric units using 1H-NMR. Adjust the Tg of the terpolymer by varying the composition, particularly increasing the NVP content while keeping MMA fixed at about 30 mol%."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/chang2012.json b/task2/task2-paper-info/chang2012.json
new file mode 100644
index 0000000..72706a3
--- /dev/null
+++ b/task2/task2-paper-info/chang2012.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The antifog coating is prepared using a bilayer configuration. The bottom layer (primer) consists of a cross-linked network of poly(acrylate) embedded with nanosized silica for mechanical strength and adhesiveness. On top of this primer, the antifog (AF) layer is formed by incorporating a modified surface-active agent, Tween 20, covalently into the polymer host. The two layers are interlinked using UV-curing of the poly(acrylate), ensuring they are mechanically inseparable and transparent. The coating can be rinsed in water without detaching from the substrate, facilitated by the hydrophobic nature of the primer.The silica sol for the bottom layer was synthesized by mixing an appropriate amount of TEOS with 2-propanol to form a homogeneous solution. HCl (aq) with a pH of 1.2 was added to induce hydrolysis-condensation of TEOS, setting the molar ratio of H2O/TEOS to four. The mixture was stirred for 3 hours at room temperature to yield a silica sol. Then, additional HCl (aq) and MSMA were slowly added, maintaining a molar ratio of H2O/MSMA equal to 3 and TEOS/MSMA to 4.5. After another reaction for 3 hours, surface-modified silica (MSiO2) was obtained. To prepare the antifog coating, 10 g of DPHA, 0.59 g of Darocure 1173, and 17.68 g of 2-propanol were added to 20 g of the MSiO2 sol, adjusting to a total solid content of 30 wt%. The mixture was spin-coated on a PMMA substrate, prebaked at 80 °C for 40 seconds, and then UV-irradiated (250 mJ/cm²) to form a cured film of approximately 1.2 μm thickness. For the AF coating, an equal number of moles of 2-HEMA and IPDI were stirred at 50 °C, with 0.1% dibutyltin dilaurate added as a catalyst. The reaction was allowed to proceed for 2 hours, after which Tween 20 was introduced and reacted for another 2 hours. The molar ratio of IPDI/Tween 20 was set to 1, with the modified Tween 20 termed T20. The AF coating sols were formed by mixing T20 with the bottom layer sol and adjusting DPHA content to maintain 30 wt% silica. The sol was spin-coated on the pre-cured bottom layer, followed by predrying at 80 °C for 40 seconds and UV-curing at 500 mJ/cm²."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/f4873e73d5de21b101f3e4875ca97069.json b/task2/task2-paper-info/f4873e73d5de21b101f3e4875ca97069.json
new file mode 100644
index 0000000..e6346c7
--- /dev/null
+++ b/task2/task2-paper-info/f4873e73d5de21b101f3e4875ca97069.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Acrylic ester was used as the main chain. Hydrophilic monomer 2-acrylamide-2-methylpropane sulfonic acid (AMPS) was introduced to enhance the hydrophilicity of the film. The main chain of acrylic resin was modified with 3-(trimethoxysilyl)propyl-2-methyl-2-methacrylate (MPS), and tetraethylorthosilicate (TEOS) was used as the curing agent. Hydroxyl groups from MPS and TEOS undergo dehydration condensation reactions to form Si–O–Si bonds under alkaline conditions. The film is cured by adding a photoinitiator and reactive diluents through the double bonds introduced into the main chain from half-blocked polyurethane.A series of acrylate copolymers (PAAMH) were synthesized via free-radical copolymerization. AA and HEA were pretreated to remove polymerization inhibitor. A mixture of AA, AMPS, HEA, MPS, and DMF was added into a dried 250-mL four-necked flask equipped with mechanical stirrer, condenser, N2 catheters, and pressure-equalizing dropping funnel. The mixture was stirred at room temperature under N2 protection and gradually heated to 80°C. AIBN (3% of total monomer weight) was dissolved in a small amount of DMF, half added into the flask dropwise via the constant-pressure dropping funnel for 1 hour at 80°C, and reacted for another 3 hours at 80°C. The remaining initiator was then added at the same dripping speed, and reacted for another 3 hours. To prepare an isocyanate-containing unsaturated monomer (IPHE), a mixture of IPDI, HEA, MEHQ, ACE, and DBTDL was added into a dried 250-mL four-necked flask equipped with mechanical stirrer, condenser, N2 catheters, and pressure-equalizing dropping funnel, then gradually heated to 55°C and allowed to react for 2 hours. The isocyanate (NCO) content was monitored during the reaction using the standard dibutylamine backtitration method. Upon reaching the theoretical NCO value, the product was cooled to room temperature, transferred to another pressure-equalizing dropping funnel, then added dropwise to the PAAMH. At the same time, additional catalyst DBTDL was added and reacted at 80°C for about 3 hours until the NCO content reached another theoretical value. Reaction completion was confirmed by the disappearance of the FTIR absorption peak at 2270 cm-1 corresponding to the stretching vibration of the NCO group. During the above process, acetone was added to adjust the viscosity of the IPHE prepolymer. Finally, the acetone was removed to afford PAAMH-IH with 30 wt% solid content.Mix PAAMH-IH with 3-4 wt% photoinitiator (Irgacure 1173), 0.3 wt% leveling agent 3288, and 25 wt% reactive diluents 15EO-TMPTA. Introduce a certain amount of TEOS based on Table 2. Adjust the pH to approximately 13 using aqueous ammonia (concentration approximately 25%), followed by quick stirring at room temperature. Coat the solution on clean glass slides by dipping, then slowly dry at 50°C for 5 hours. Heat the resulting films in an oven at 70°C for another 2 hours. Finally, irradiate the films using a 1200-W UV (200-400 nm) lamp for 30 seconds at room temperature.Purified product was dissolved in deuterated DMSO with tetramethylsilane (TMS) as internal standard. Then, 1H and 13C NMR spectra were recorded using a Bruker 500 MHz NMR (Avance III) to confirm the structure of PAAMH. Samples were diluted to 15 wt% solid content with DMF, dripped onto a silicon wafer, and cured."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/fuctional polymer.json b/task2/task2-paper-info/fuctional polymer.json
new file mode 100644
index 0000000..fa41a4f
--- /dev/null
+++ b/task2/task2-paper-info/fuctional polymer.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of hydrophilic polymers involves utilizing unsaturated monomers such as acrylates and methacrylates, which can be cross-linked by ultraviolet light (UV) radiation. The process may employ a Michael addition reaction, using acetoacetate donors with multifunctional acrylate receptor compounds to yield polyesters with reactive pendent acrylate groups. These pendent groups facilitate cross-linking in a subsequent curing reaction, eliminating the need for added photoinitiators. Upon exposure to UV radiation, an acyl radical is formed, which acts as an internal photoinitiator, leading to the polymerization of the system.Polymers are synthesized by polymerizing ethylenically or acetylenically unsaturated polymerizable monomers or oligomers that have alpha, beta-unsaturation. The polymers must have an average molecular weight of at least 1000 daltons. The polymer backbone is terminated with at least one free unsaturated group at either end. Additionally, one or more monomers or oligomers used to create the polymer backbone should contain groups that can react with other compounds to form pendent functional groups. These pendent functional groups may either end in free unsaturated functional groups or other types of functional groups.Functional polymers may be prepared by first functionalizing one or more monomers or oligomers followed by free radical polymerization of the functionalized monomers or oligomers. Monomers with free hydroxyl (-OH), carboxyl (-COOH), or ester (—COO—R) groups are reacted with compounds having hydroxyl, carboxyl, ester, aminyl (-NH2 or —NHR), or isocyanate (—NCO) groups to form pendent functional groups. The polymerization process can occur in suspension solution (60°C to 80°C) or emulsion (−20°C to 60°C) form, typically at near or at 1 atmosphere pressure. Initiators like peroxide (e.g., dibenzoyl peroxide) or azo initiators (e.g., 2,2'-azobis(2-methylpropane nitrile)) may be used. Alternative methods like anionic polymerization or post polymerization functionalization may also be applied, which entails separately preparing the polymer backbone and pendant functional groups and subsequently joining them together. A free isocyanate can be reacted with a hydroxyl, carboxyl, or aminyl group on the polymer backbone at temperatures below 80°C for 1 to 8 hours to form linkages such as R—NH—C(O)—P or R—NH—C(O)—NR'-G-P.  The presence of inert solvents and catalysts can be employed to accelerate reactions, and stabilizers or polymerization inhibitors may be added to prevent premature cross-linking.To synthesize hydrophilic polymers with functional groups, use polymerizable groups such as isocyanates, alkenes, and carboxylic acid derivatives for components A' and B. Base cleavable groups and optional spacer groups should be included in component Z, where suitable spacer groups can be alkyleneoxy or aryleneoxy types. The composition of Z may follow the formula S_x4(BCG)_y4, with S being a spacer group and BCG being a base cleavable group. Preferred base cleavable groups include anhydrides, esters, and carbonates. Aim for multiple base cleavable groups in the polymer structure, preferably at least two, with an emphasis on using four or more for enhanced functionality.1. Use difunctional branch-point monomers with polymerizable end groups that include base cleavable functional groups, such as (meth)acrylate esters. 2. Choose suitable difunctional monomers including acrylic anhydride, methacrylic anhydride, or ester linkages with (meth)acrylate end groups. 3. Mix multiple difunctional branch-point monomers in the range of 0.1 to 100 wt% based on the total weight of monomers. 4. Ensure that polymers contain acid functionality capable of forming a salt upon contact with alkaline developers, aiming for an acid number up to 250, preferably between 50 to 250. 5. Incorporate ester links in the backbone and/or side chains, targeting 2 to 50 ester links, ideally between 20 to 40. 6. Utilize isocyanate compounds with at least one free isocyanate group to react with hydroxyl-containing compounds. 7. Conduct the reaction at a 1:1 mole ratio of hydroxyl group to isocyanate group. 8. If desired, use free-radical generating compounds capable of promoting polymerization upon exposure to actinic radiation. 9. Incorporate hydrophilic components that provide water solubility or dispersibility, preferably with light absorbance at or above 300nm.To synthesize hydrophilic polymers with functional groups, use the following steps: 1. Functionalize photoinitiators (e.g., benzophenones, acetophenones) with reactive groups such as hydroxyl, carboxyl, or amine by reacting them with isocyanate groups on a carrier component to create urethane, amide, or urea bonds. 2. Alternatively, react an isocyanate group from the photoinitiator with a hydroxyl, carboxyl, or amine group on the carrier. 3. Form ester bonds by reacting an acid group with an alcohol group. 4. Optionally, incorporate aromatic chromophores that have light sensitivity in the range of 320 to 450 nm, joining these via similar methods used for photoinitiators. 5. For polymer backbone functionalization, ensure an average molecular weight of at least 1000 daltons, typically between 10,000 to 500,000 daltons. 6. Maintain reactive groups such as hydroxyl and carboxyl on the polymer backbone for solubility in alkaline solutions. 7. Optionally functionalize the polymer with 1.0 to 100 mole percent of reactive sites, preferably between 2 and 20 mole percent. 8. The synthesized polymer is then processed into liquid photoresists by dissolving in an organic diluent or water, followed by cross-linking upon exposure to radiation.A homogeneous solution containing 62.0 grams of methacrylic acid and 265.0 grams of methyl methacrylate was prepared. 75% by weight of the homogeneous solution were transferred into a second flask. The homogeneous solution of the first flask was diluted to 26.0% by weight solids and the homogeneous solution of the second flask was diluted to 86.50% by weight solids by adding sufficient methyl ethyl ketone. The first flask was mixed and heated to reflux under atmospheric conditions. 2.0 grams of 2,2'-azobis (2-methylbutyronitrile) was added to the reaction mixture, mixed and held at reflux for about 30 minutes. 6.25 grams of 2,2'-azobis (2-methylbutyronitrile) was mixed with 38.0 grams of methyl ethyl ketone and fed into the first flask along with the contents of the second flask over 4 hours while maintaining reflux. An additional amount of 9.0 grams of methyl ethyl ketone was then added to the first flask and the mixture was refluxed for an additional hour.In a separate clean dry air sparged addition funnel, 193.0 grams of polypropoxylated hydroxypropylmethacrylate (hydroxyl number $^{-158}$) was weighed out. The polypropoxylated hydroxypropylmethacrylate was added to a flask containing 1,6-hexamethylene diisocyanate biuret over about 1 hour with mixing while maintaining a temperature of $35^{\\circ}\\mathrm{C}$. The addition funnel was rinsed with 118.0 grams of methyl ethyl ketone, which was added to the flask containing the biuret, and the temperature was increased to $60^{\\circ}\\mathrm{C}$. The reaction was maintained for 3 hours at $60^{\\circ}\\mathrm{C}$ and monitored for completion using known analytical methods. The functionalized polymer was prepared by weighing out 763.0 grams of the acrylic polymer (47% solids) and 55.0 grams of methyl ethyl ketone in a clean, dry air-sparged flask, mixing, and heating to $45^{\\circ}\\mathrm{C}$. The urethane/acrylate moiety was added to the acrylic polymer over about 1 hour. Then, 0.50 grams of Irganox 1076 and 28.0 grams of methyl ethyl ketone were added to the reaction mixture, which was held at $45^{\\circ}\\mathrm{C}$ for 3 hours with constant mixing. The polymer main chain was functionalized with 6 mole percent of the moiety. 4.55 grams of 2,2'-azobis (2-methylbutyronitrile) were dissolved in 48.0 grams of methyl ethyl ketone and mixed, then added to the first flask over a period of 90 minutes while maintaining reflux. An additional 8.5 grams of 2,2'-azobis (2-methylbutyronitrile) mixed with 48.0 grams of methyl ethyl ketone was fed into the reaction mixture over about 150 minutes while maintaining reflux, followed by 23.0 grams of methyl ethyl ketone. At the end of the reaction, 2,2'-azobis (2-methylbutyronitrile) was thermally killed off to below parts per million concentrations. 150.0 grams of 1,6-hexamethylene diisocyanate biuret (23.0% NCO) were added to a clean dry, nitrogen-sparged flask along with 0.06 grams of dibutylin dilaurate, 0.05 grams of Irganox 1076, and 160.0 grams of methyl ethyl ketone. The flask was sparged with dry air, stoppered, mixed, and heated at about $35^{\\circ}\\mathrm{C}$.To prepare the acrylic polymer backbone, 70.0 grams of 2-hydroxyethyl methacrylate was added to a mixture of methacrylic acid and methyl methacrylate. For the functionalized pendent groups, 1 mole of isophorone diisocyanate was reacted with about one mole of hydroxy methacrylate to form an isophorone diisocyanate hydroxy methacrylate moiety.The isocyanate groups of isophorone diisocyanate hydroxy methacrylate were reacted with the hydroxyl groups of 2-hydroxyethyl methacrylate to form a functionalized polymer with 6 mole percent functionalization.One mole of 1,6-hexamethylene diisocyanate trimer is added to a clean dry, nitrogen sparged flask. 0.06 grams of dibutylin dilaurate, 0.05 grams of Irganox (antioxidant) 15 and 160.0 grams of methyl ethyl ketone are also added to the flask. The flask is sparged with dry air and stoppered. The components are mixed and heated at 35°C. Two moles of a polyalkoxylated hydroxyalkyl (meth)acrylate, or two moles of hydroxyalkyl (meth)acrylate are added to the flask, mixed with the trimer, and heated at 35°C for one hour. The reaction temperature is increased to 60°C and the reaction is maintained for 3 hours.$60\\\\textrm{g}$ of a diacrylate acceptor compound and $0.5\\\\mathrm{~g~}$ of diazabicyclo-undecene (DBU) are weighed into a $500~\\\\mathrm{ml}~3$ -neck round bottom flask equipped with a mechanical stirrer and addition funnel. $15.0~\\\\mathrm{g}$ of an acetoacetate derived donor compound is weighed into the addition funnel. The acceptor compound and DBU are mixed for 5 minutes prior to the addition of the donor compound. The donor compound is then added dropwise to the stirred acceptor/DBU mixture over a 15 minute period. The solution is warmed to 54 degrees Celsius after the addition of the donor compound is complete. After the 1s exotherm subsided in 100 minutes, a viscous yellow liquid is obtained which does not gel upon standing.To 1.1 parts of the prepared imidazole dissolved in 100 parts of ethanol containing 12 parts of potassium hydroxide, add 450 parts of a 1% by weight water solution of potassium ferricyanide at a rate of 5 parts per minute for 1.5 hours with continuous stirring. After the reaction, isolate the oxidation product in an amount of 1.0 parts by filtration and wash with water until free from ferricyanide. Dry the product at 56°C for eight hours under 0.1 mm mercury pressure after predrying overnight in a vacuum oven at 50°C. Solvate the product with two moles of ethanol for every three moles of biimidazole. Dry a portion of the ethanol-solvated product azeotropically with cyclohexane or recrystallize from ether to produce non-solvated material. Furthermore, prepare an oligomer composed of methylmethacrylate and acrylic acid by free radical polymerization in an aqueous acidic environment at reflux between 90°C to 100°C for a water-soluble photoinitiator yield of 85% to 90% by weight.Prepare a homogeneous solution containing 197 grams of methacrylic acid, 512 grams of methyl methacrylate, and 79 grams of poly(ethoxylated) monomethacrylate. Transfer 75% by weight of the homogeneous solution into a second flask.1. Dilute the first flask to 25% by weight solids. Dilute the homogeneous solution of the second flask to 60% by weight solids by adding sufficient methyl ethyl ketone. 2. Mix the first flask and heat to reflux under atmospheric conditions. Add 2.0 grams of 2,2'-azobis (2-methylbutyronitrile) to the reaction mixture, mix, and hold at reflux for 30 minutes. 3. Mix 6.0 grams of 2,2'-azobis (2-methylbutyronitrile) with about 40 grams of methyl ethyl ketone. Feed this into the first flask along with the contents of the second flask over 4 hours while maintaining reflux. 4. Add an additional 9.0 grams of methyl ethyl ketone to the first flask and reflux for an additional hour. 5. Dissolve 5.0 grams of 2,2'-azobis (2-methylbutyronitrile) in 50.0 grams of methyl ethyl ketone. Add this mixture to the first flask over a period of 90 minutes while maintaining reflux. 6. Mix 9.0 grams of 2,2'-azobis (2-methylbutyronitrile) with 50.0 grams of methyl ethyl ketone and feed into the reaction mixture over 150 minutes while maintaining reflux. 7. Add an additional 25.0 grams of methyl ethyl ketone to the reaction mixture. 8. At the end of the reaction, thermally kill off 2,2'-azobis (2-methylbutyronitrile) to below parts per million concentrations. Set aside the acrylic copolymer main chain or backbone.5.31 grams of 1,6-hexamethylene diisocyanate biuret (23.% free-NCO) were added to a clean dry, nitrogen sparged flask. 0.06 grams of dibutylin dilaurate, 0.05 grams of Irganox 1076 (antioxidant) and 160.0 grams of methyl ethyl ketone were also added to the flask. The flask was sparged with dry air and stoppered. The components were mixed and heated at 35°C. In a separate clean dry air sparged addition funnel, 15.97 grams of poly(ethoxylate-b-caprolactone) monomethacrylate oligomer was weighed out. The oligomer was added to the flask containing the 1,6-hexamethylene diisocyanate biuret over 1 hour with mixing and maintaining a temperature of 35°C. The addition funnel was then rinsed with 118.0 grams of methyl ethyl ketone to remove any remaining oligomer. The rinse was added to the flask containing the biuret with a temperature increased to 60°C. The reaction was maintained for 3 hours at 60°C. The reaction was monitored to determine completion of the synthesis of a urethane acrylate moiety by high pressure liquid chromatography (HPLC). The functionalized polymer was prepared by weighing out 763.0 grams of the acrylic copolymer (47% solids) and 50.0 grams of methyl ethyl ketone to a clean, dry air sparged flask. The combination was mixed and heated to 45°C. The urethane/acrylate moiety was then added to the acrylic polymer over 1 hour. 0.50 grams of Irganox 1076 and 30.0 grams of methyl ethyl ketone was added to the reaction mixture. The reaction contents were held at 45°C for 3 hours with constant mixing. The resulting copolymer was composed of 25 mole % of methyacrylic acid, 65 mole % of methyl methacrylate and 10 mole % of poly(ethoxylated) monomethacrylate residues. The copolymer main chain was 6 mole % functionalized with the moiety.A homogeneous solution containing 77.5 grams of 2-hydroxyethyl methacrylate, 194 grams of methacrylic acid, and 504 grams of methyl methacrylate was prepared. 75% by weight of the homogeneous solution was transferred to a second flask. The homogeneous solution of the first flask was diluted to 25% by weight solids and the homogeneous solution of the second flask was diluted to 60% by weight solids by adding sufficient methyl ethyl ketone. The first flask was mixed and heated to reflux under atmospheric conditions. 2.0 grams of 2,2'-azobis (2-methylbutyronitrile) was added to the reaction mixture, mixed and held at reflux for 30 minutes. 6.25 grams of 2,2'-azobis (2-methylbutyronitrile) was mixed with 40.0 grams of methyl ethyl ketone and fed into the first flask along with the contents of the second flask over 4 hours while maintaining reflux. An additional amount of 9.0 grams of methyl ethyl ketone was then added to the first flask and the mixture was refluxed for an additional hour. 5.0 grams of 2,2'-azobis (2-methylbutyronitrile) were dissolved in 50.0 grams of methyl ethyl ketone and mixed. The mixture was then added to the first flask over a period of 90 minutes while maintaining reflux. 9.0 grams of 2,2'-azobis (2-methylbutyronitrile) were mixed with 50.0 grams of methyl ethyl ketone and then fed into the reaction mixture over 150 minutes while maintaining reflux. An additional amount of 23.0 grams of methyl ethyl ketone was added to the reaction mixture. At the end of the reaction, 2,2'-azobis (2-methylbutyronitrile) was thermally killed off to below parts per million concentrations. The acrylic polymer main chain or backbone product was set aside. 150.0 grams of 1,6-hexamethylene diisocyanate biuret (23.0% -NCO) were added to a clean dry, nitrogen sparged flask. 0.06 grams of dibutylin dilaurate, 0.05 grams of Irganox 1076 (antioxidant) and 160.0 grams of methyl ethyl ketone were also added to the flask. The flask was sparged with dry air and stoppered. The components were mixed and heated at 35°C. In a separate clean dry air sparged addition funnel, 190.0 grams of poly(ethoxylate-b-caprolactone) monomethacrylate oligomer was weighed out. The oligomer was added to the flask containing the 1,6-hexamethylene diisocyanate biuret over 1 hour with mixing and maintaining a temperature of 35°C. The addition funnel was then rinsed with 120.0 grams of methyl ethyl ketone to remove any remaining oligomer. The rinse was added to the flask containing the biuret with a temperature increased to 60°C. The reaction was maintained for 3 hours at 60°C. The reaction was monitored to determine completion of the synthesis of the urethane acrylate moiety. 750.0 grams of the acrylic copolymer and 55.0 grams of methyl ethyl ketone were weighed out in a clean, dry air sparged flask. The combination was mixed and heated to 45°C. The urethane/acrylate moiety was then added to the acrylic copolymer over 1 hour. 0.50 grams of Irganox 1076 and 30.0 grams of methyl ethyl ketone was added to the reaction mixture. The reaction contents were held at 45°C for 3 hours with constant mixing. The polymer main chain was 6 mole percent functionalized with the moiety.Select a photoinitiator from the following options: imidazole dimer, anthraquinone, naphthaquinone, ketal, triazine compound, or combinations thereof. Ensure the polymer has an average molecular weight of at least 1000 daltons. For enhanced properties, incorporate multiple ester links, specifically greater than 2. Consider including one or more side chains with greater than 2 ester links. Optionally, use hexaarylbiimidazole as the imidazole dimer and include additional components such as a stripping agent, plasticizer, surfactant, aromatic chromophore, dye, or combinations thereof to modify the polymer."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/functionalized polymer.json b/task2/task2-paper-info/functionalized polymer.json
new file mode 100644
index 0000000..3db92d9
--- /dev/null
+++ b/task2/task2-paper-info/functionalized polymer.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "1. Provide a photopolymerizable composition which includes a compound having a formula: (A)_{u}(B)_{v}(C)_{w}(D)_{x}(E)_{y}(F)_{z}, where A is derived from one or more hydroxyalkyl (meth)acrylate, B is derived from one or more hydroxy polyalkyleneoxide (meth)acrylate, C is derived from one or more alkyl(meth)acrylate, D is derived from one or more (meth)acrylic acid, E is derived from one or more vinyl aromatic monomer, nitrogen containing compound or thioanalog of a nitrogen containing compound, silicon containing monomer, substituted ethylene monomer, or cyclic olefin monomer, and F is derived from one or more hydroxy poly opened-ring lactone polyalkylene oxide (meth)acrylate. Ensure that u, v, w, x, y, and z are weight percentages of the monomers in the backbone, with u being 0 to 30%, v being 0 to 30%, w being 5 to 70%, x being 5 to 40%, y being 0 to 20%, and z being 0 to 30%, ensuring at least one of u, v, or z is greater than 0, and at least one of A, B, C, D, E, and F has at least one pendent functional group. 2. Optionally, include at least one ethylenically unsaturated monomer as a cross-linking agent and a photoinitiator. 3. Apply the photopolymerizable composition to a substrate. 4. Imagewise expose the photopolymerizable composition to actinic radiation to form a polymerized composition. 5. Develop the imagewise exposed photopolymerized composition to form an image on the substrate.The polymer backbone may be made by dissolving chosen monomers into an appropriate solvent and heating in a reaction vessel with a thermal free radical initiator to initiate polymerization. Suitable initiators include peroxide compounds and azo compounds. The functionalized polymers may be prepared using a post polymerization functionalization process, where the main chain and functional pendent components are prepared separately and then joined together. After polymerization, free hydroxyl groups or amino groups on the polymer are reacted with a compound having unsaturated groups to form functional groups. The reaction may occur with isocyanate compounds at mild temperatures (20°C to 60°C) for 1 to 8 hours, preferably 4 to 6 hours. A catalyst can be added to accelerate the reaction. The reaction completion is determined using standard analytical instruments. The overall method includes using various monomers such as hydroxyalkyl (meth)acrylate, hydroxy polyalkylene oxide (meth)acrylate, alkyl (meth)acrylate, (meth)acrylic acid, vinyl aromatic monomers, nitrogen-containing compounds, silicon-containing monomers, and cyclic olefins.A homogeneous solution containing 250 grams of methacrylic acid, 100 grams of poly(ethoxylate-b-caprolactone) monomethacrylate with 6 ethoxylations, and 650 grams of methyl methacrylate was prepared. 75% by weight of this solution was transferred into a second flask. The solution in the first flask was diluted to 26.0% by weight solids, while the second flask was diluted to 60% by weight solids with methyl ethyl ketone. The first flask was heated to reflux under atmospheric conditions, and 11 grams of 2,2'-azobis (2-methylbutyronitrile) was added, mixed, and held at reflux for about 30 minutes. Over 4 hours, a mixture of 18 grams of 2,2'-azobis (2-methylbutyronitrile) and 38.0 grams of methyl ethyl ketone was added to the first flask along with the contents of the second flask while maintaining reflux. Afterward, an additional 9.0 grams of methyl ethyl ketone was added, and the mixture was refluxed for an additional hour. A solution of 15 grams of 2,2'-azobis (2-methylbutyronitrile) in 48.0 grams of methyl ethyl ketone was added to the first flask over 90 minutes while maintaining reflux. Then, 24 grams of 2,2'-azobis (2-methylbutyronitrile) mixed with 48.0 grams of methyl ethyl ketone was added to the reaction mixture over 150 minutes while maintaining reflux. Another 23.0 grams of methyl ethyl ketone was added, and at the end of the reaction, 2,2'-azobis (2-methylbutyronitrile) was thermally killed off to below parts per million concentrations. The resulting copolymer contained 68.1 mole % of methyl methacrylate, 30.5 mole % of methacrylic acid, and 1.4 mole % of poly(ethoxylate-b-caprolactone) monomethacrylate residues, with 95.0% hydroxyl capping.A homogeneous solution containing 250 grams of methacrylic acid, 650 grams of methyl methacrylate and 100 grams of 2-hydroxyethyl methacrylate was prepared. 75% by weight of the homogeneous solution were transferred into a second flask. The homogeneous solution of the first flask was diluted to 25% by weight solids and the homogeneous solution of the second flask was diluted to 60% by weight solids by adding sufficient methyl ethyl ketone. The first flask was mixed and heated to reflux under atmospheric conditions. 11 grams of 2,2'-azobis (2-methylbutyronitrile) was added to the reaction mixture, mixed and held at reflux for 30 minutes. 18 grams of 2,2'-azobis (2-methylbutyronitirle) was mixed with 40.0 grams of methyl ethyl ketone and fed into the first flask along with the contents of the second flask over 4 hours while maintaining reflux. An additional amount of 10.0 grams of methyl ethyl ketone was then added to the first flask and the mixture was refluxed for an additional hour. 15 grams of 2,2'-azobis (2-methylbutyronitirle) were dissolved in 50.0 grams of methyl ethyl ketone and mixed. The mixture was then added to the first flask over a period of 90 minutes while maintaining reflux. 24 grams of 2,2'-azobis (2-methylbutyronitrile) were mixed with 50.0 grams of methyl ethyl ketone and then fed into the reaction mixture over 150 minutes while maintaining reflux. An additional amount of 20.0 grams of methyl ethyl ketone were added to the reaction mixture. At the end of the reaction, 2,2'-azobis (2-methylbutyronitirle) was thermally killed off to below parts per million concentration. The copolymer formed contained 63.8 mole % of methyl methacrylate, 28.6 mole % of methacrylic acid and 7.6 mole % of 2-hydroxyethyl methacrylate residues. The copolymer was 17.6% hydroxyl capped.A homogeneous solution containing 250 grams of methacrylic acid, 650 grams of methyl methacrylate, and 100 grams of poly(ethoxylated) monomethacrylate with 6 ethoxylations was prepared. 75% by weight of the homogeneous solution were transferred into a second flask. The homogeneous solution of the first flask was diluted to 25% by weight solids and the homogeneous solution of the second flask was diluted to 60% by weight solids by adding sufficient methyl ethyl ketone. The first flask was mixed and heated to reflux under atmospheric conditions. 11 grams of 2,2'-azobis (2-methylbutyronitrile) was added to the reaction mixture, mixed and held at reflux for 30 minutes. 18 grams of 2,2'-azobis (2-methylbutyronitrile) was mixed with 40 grams of methyl ethyl ketone and fed into the first flask along with the contents of the second flask over 4 hours while maintaining reflux. An additional 10.0 grams of methyl ethyl ketone was then added to the first flask and the mixture was refluxed for an additional hour. 15 grams of 2,2'-azobis (2-methylbutyronitrile) were dissolved in 50 grams of methyl ethyl ketone and mixed. The mixture was then added to the first flask over a period of 90 minutes while maintaining reflux. 24 grams of 2,2'-azobis (2-methylbutyronitrile) were mixed with 50.0 grams of methyl ethyl ketone and then fed into the reaction mixture over 150 minutes while maintaining reflux. An additional 25.0 grams of methyl ethyl ketone were added to the reaction mixture. At the end of the reaction, 2,2'-azobis (2-methylbutyronitrile) was thermally killed off to below parts per million concentrations.A homogeneous solution containing 250 grams of methacrylic acid, 650 grams of methyl methacrylate, 100 grams of 2-hydroxyethyl methacrylate, and 2.0 grams of n-butyl acrylate was prepared. 75% by weight of the homogeneous solution were transferred into a second flask. The homogeneous solution of the first flask was diluted to 26.0% by weight solids and the homogeneous solution of the second flask was diluted to 60% by weight solids by adding sufficient methyl ethyl ketone. The first flask was mixed and heated to reflux under atmospheric conditions. 11 grams of 2,2'-azobis (2-methylbutyronitrile) was added to the reaction mixture, mixed and held at reflux for 30 minutes. 18 grams of 2,2'-azobis (2-methylbutyronitrile) was mixed with 40.0 grams of methyl ethyl ketone and fed into the first flask along with the contents of the second flask over 4 hours while maintaining reflux. An additional amount of 9.0 grams of methyl ethyl ketone was then added to the first flask and the mixture was refluxed for an additional hour. 15 grams of 2,2'-azobis (2-methylbutyronitrile) were dissolved in 50.0 grams of methyl ethyl ketone and mixed. The mixture was then added to the first flask over a period of 90 minutes while maintaining reflux. 24 grams of 2,2'-azobis (2-methylbutyronitrile) were mixed with 50.0 grams of methyl ethyl ketone and then fed into the reaction mixture over 150 minutes while maintaining reflux. An additional amount of 23.0 grams of methyl ethyl ketone was added to the reaction mixture. At the end of the reaction, 2,2'-azobis (2-methylbutyronitrile) was thermally killed off to below parts per million concentrations. The copolymer was composed of 59.6 mole % of methyl methacrylate, 28.9 mole % of methacrylic acid, 7.6 mole % of 2-hydroxyethyl methacrylate and 3.9 mole % of n-butyl acrylate. The copolymer was 17.4% hydroxyl capped.Two photopolymerizable compositions were prepared using copolymers 2 or 4. Each composition contained the following components: 66.75 wt% of copolymer 2 or 4 as the polymer binder, 13.67 wt% of Bis A ethoxylate dimethacrylate as the photopolymerizable oligomer, 10.80 wt% of alkylene oxide, mono methacrylate as the photopolymerizable monomer, 0.05 wt% of Michler's ethyl ketone as a UV absorber, 3.50 wt% of Lophine dimmer as a color activator/photoinitiator, 0.40 wt% of Leuco crystal violet as a color formor, 0.05 wt% of Malachite green as a dye, 4.48 wt% of phthalate as a plasticizer, 3.0 wt% of benzophenone as a photoinitiator, and 0.10 wt% of Modaflow as a flow control agent. Each composition was prepared in a 7:1 mixture of 2-butanone to 2-propanol at 50% solids. The solution was coated onto biaxially orientated 80 gauge polyester films and dried to 1% or less retained solvent. The coated mixtures were laminated onto mechanically scrubbed 1 oz/FR 4/1 oz clad copper composite using a hot roll laminator at 110°C, at 2 meters/minute and 3 bar pressure.A homogeneous solution containing 197 grams of methacrylic acid, 512 grams of methyl methacrylate, and 79 grams of poly(ethoxylated) monomethacrylate was prepared. 75% by weight of the homogeneous solution was transferred into a second flask. The first flask's solution was diluted to 25% by weight solids, and the second flask's solution was diluted to 60% by weight solids by adding methyl ethyl ketone. The first flask was mixed and heated to reflux under atmospheric conditions. 2.0 grams of 2,2'-azobis (2-methylbutyronitrile) was added to the reaction mixture and held at reflux for 30 minutes. 6.0 grams of 2,2'-azobis (2-methylbutyronitrile) was mixed with 40 grams of methyl ethyl ketone and added to the first flask along with the second flask's contents over 4 hours while maintaining reflux. An additional 9.0 grams of methyl ethyl ketone was added to the first flask, and the mixture refluxed for another hour. 5.0 grams of 2,2'-azobis (2-methylbutyronitrile) were dissolved in 50.0 grams of methyl ethyl ketone and added to the first flask over 90 minutes while maintaining reflux. 9.0 grams of 2,2'-azobis (2-methylbutyronitrile) were mixed with 50.0 grams of methyl ethyl ketone and added to the reaction mixture over 150 minutes while maintaining reflux, followed by the addition of 25.0 grams of methyl ethyl ketone. 5.31 grams of 1,6-hexamethylene diisocyanate biuret (23% free-NCO) were added to a clean dry, nitrogen sparged flask along with 0.06 grams of dibutylin dilaurate, 0.05 grams of Irganox 1076, and 160.0 grams of methyl ethyl ketone. The flask was sparged with dry air and stoppered. The components were mixed and heated at 35°C. In a separate air-sparged addition funnel, 15.97 grams of poly(ethoxylate-b-caprolactone) monomethacrylate oligomer were added over 1 hour while maintaining a temperature of 35°C. After rinsing with 118.0 grams of methyl ethyl ketone, the temperature was increased to 60°C and maintained for 3 hours. 763.0 grams of the acrylic copolymer (47% solids) and 50.0 grams of methyl ethyl ketone were mixed in another flask and heated to 45°C. The urethane/acrylate moiety was added over 1 hour, followed by 0.50 grams of Irganox 1076 and 30.0 grams of methyl ethyl ketone. The mixture was held at 45°C for 3 hours with constant mixing, resulting in a copolymer composed of 25 mole % methacrylic acid, 65 mole % methyl methacrylate, and 10 mole % poly(ethoxylated) monomethacrylate residues, with 6 mole % functionalization.A homogeneous solution containing 77.5 grams of 2-hydroxyethyl methacrylate, 194 grams of methacrylic acid, and 504 grams of methyl methacrylate was prepared. 75% by weight of the homogeneous solution was transferred to a second flask. The homogeneous solution of the first flask was diluted to 25% by weight solids and the homogeneous solution of the second flask was diluted to 60% by weight solids by adding sufficient methyl ethyl ketone. The first flask was mixed and heated to reflux under atmospheric conditions. 2.0 grams of 2,2'-azobis (2-methylbutyronitrile) was added to the reaction mixture, mixed and held at reflux for 30 minutes. 6.25 grams of 2,2'-azobis (2-methylbutyronitrile) was mixed with 40.0 grams of methyl ethyl ketone and fed into the first flask along with the contents of the second flask over 4 hours while maintaining reflux. An additional amount of 9.0 grams of methyl ethyl ketone was then added to the first flask and the mixture was refluxed for an additional hour. 5.0 grams of 2,2'-azobis (2-methylbutyronitrile) were dissolved in 50.0 grams of methyl ethyl ketone and mixed. The mixture was then added to the first flask over a period of 90 minutes while maintaining reflux. 9.0 grams of 2,2'-azobis (2-methylbutyronitrile) were mixed with 50.0 grams of methyl ethyl ketone and then fed into the reaction mixture over 150 minutes while maintaining reflux. An additional amount of 23.0 grams of methyl ethyl ketone were added to the reaction mixture. At the end of the reaction, 2,2'-azobis (2-methylbutyronitrile) was thermally killed off to below parts per million concentrations. 150.0 grams of 1,6-hexamethylene diisocyanate biuret (23.0% -NCO) were added to a clean dry, nitrogen sparged flask along with 0.06 grams of dibutyltin dilaurate, 0.05 grams of Irganox 1076, and 160.0 grams of methyl ethyl ketone. The flask was sparged with dry air and stoppered. The components were mixed and heated at 35°C. In a separate clean dry air sparged addition funnel, 190.0 grams of poly(ethoxylate-b-caprolactone) monomethacrylate oligomer was weighed out and added to the flask containing the 1,6-hexamethylene diisocyanate biuret over 1 hour while maintaining a temperature of 35°C. The addition funnel was rinsed with 120.0 grams of methyl ethyl ketone and added to the flask. The temperature was then increased to 60°C and the reaction was maintained for 3 hours at that temperature. The functionalized polymer was prepared by weighing out 750.0 grams of the acrylic copolymer and 55.0 grams of methyl ethyl ketone to a clean, dry air sparged flask. The combination was mixed and heated to 45°C. The urethane/acrylate moiety was added to the acrylic copolymer over 1 hour. 0.50 grams of Irganox 1076 and 30.0 grams of methyl ethyl ketone was added to the reaction mixture. The reaction contents were held at 45°C for 3 hours with constant mixing. The polymer main chain was 6 mole percent functionalized with the moiety.Functionalized copolymers are prepared by combining components in the specified proportions. Each photopolymerizable composition is created using a solvent mixture of 2-butanone and 2-propanol at a 7:1 ratio, achieving 50% solids. The resulting solutions are then applied to biaxially oriented 80 gauge polyester films and dried to retain 1% or less solvent. Following this, the coated films are laminated onto FR-4 copper clad composites with a hot roll laminator set at 110°C, a speed of 2 meters/minute, and a pressure of 3 bar. The laminated materials are imaged on a UV printer and developed in a 1% sodium carbonate monohydrate solution at 30°C, using a conveyorized spray developer at 26 psi, followed by rinses with tap water and deionized water. The final steps include etching with a 2N cupric chloride/hydrochloric acid solution at 50°C and stripping the developed photopolymerized composition using a 3% sodium hydroxide solution at 55°C, also in a conveyorized unit with multiple spray nozzles, finishing with a rinse of tap water."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/gui2020.json b/task2/task2-paper-info/gui2020.json
new file mode 100644
index 0000000..6a85eec
--- /dev/null
+++ b/task2/task2-paper-info/gui2020.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "We immobilize either polymerase or DNA on the BP surface to replicate DNA."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/herkert-et-al-2022-characterization-of-per-and-polyfluorinated-alkyl-substances-present-in-commercial-anti-fog-products.json b/task2/task2-paper-info/herkert-et-al-2022-characterization-of-per-and-polyfluorinated-alkyl-substances-present-in-commercial-anti-fog-products.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/herkert-et-al-2022-characterization-of-per-and-polyfluorinated-alkyl-substances-present-in-commercial-anti-fog-products.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/j.tribology.2022016.json b/task2/task2-paper-info/j.tribology.2022016.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/j.tribology.2022016.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/lee2013.json b/task2/task2-paper-info/lee2013.json
new file mode 100644
index 0000000..586ac81
--- /dev/null
+++ b/task2/task2-paper-info/lee2013.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of hydrophilic polymers with functional groups involves several steps: First, degrease the glass substrates by sonication in a 4% (v/v) solution of Micro-90 for 15 min, followed by two rinses in deionized water for 15 min, and then dry with compressed air. Treat the cleaned glass with oxygen plasma for 2 min at 150 mTorr. Build layer-by-layer (LbL) assemblies of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) using a spin dipper with 10 min dipping times in 1 mg/mL polymer solutions at pH 2.0, rinsing three times (2, 1, and 1 min). The PVA/PAA multilayer film is cross-linked thermally for 5 min at 140°C. For PEG functionalization, immerse the PVA/PAA multilayer in a 10 mg/mL PEG solution (pH 2.0) for 20 min, then soak in 0.13% (w/w) glutaraldehyde in phosphate buffer saline for 10 min, followed by rinsing with deionized water and drying. For PMMA coating, dissolve PMMA in Asahiklin at 10 mg/mL, dip-coat on the pretreated glass for 1 h, and heat at approximately 60°C for 1 h to evaporate the solvent."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/li-et-al-2017-amphiphilic-antifogging-anti-icing-coatings-containing-poss-pdmaema-b-psbma.json b/task2/task2-paper-info/li-et-al-2017-amphiphilic-antifogging-anti-icing-coatings-containing-poss-pdmaema-b-psbma.json
new file mode 100644
index 0000000..403c031
--- /dev/null
+++ b/task2/task2-paper-info/li-et-al-2017-amphiphilic-antifogging-anti-icing-coatings-containing-poss-pdmaema-b-psbma.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "To prepare amphiphilic SIPN coatings from POSS-PDMAEMA-b-PSBMA block copolymers, integrate POSS with both PDMAEMA and PSBMA via atom transfer radical polymerization (ATRP). Use a small amount (10 wt%) of EGDMA and subject the mixture to UV-curing. The PDMAEMA and PSBMA blocks should be coupled with hydrophobic POSS groups to enhance water or vapor absorption in the coatings.The POSS-PDMAEMA-b-PSBMA block copolymers were synthesized via ATRP of DMAEMA using POSS-Br as an initiator, followed by ATRP of SBMA using POSS-PDMAEMA−Br as a macroinitiator. Three block copolymers with different polymerization degrees were prepared. Control block copolymer PDMAEMA-b-PSBMA was synthesized using ethyl-2-bromoisobutanoate as the initiator. Each block copolymer was prepared by dissolving in 2,2,2-trifluoroethanol at 25 mg/mL, with EGDMA (10 wt%) and Igracure 2959 UV photoinitiator (2 wt%) added. 0.2 mL of the polymer solution was cast on a glass slide and polymerized under UV (365 nm, 15 W, 1800 s). The thickness of the SIPN coatings was approximately 10 µm."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/liang-et-al-2019-transparent-and-scratch-resistant-antifogging-coatings-with-rapid-self-healing-capability.json b/task2/task2-paper-info/liang-et-al-2019-transparent-and-scratch-resistant-antifogging-coatings-with-rapid-self-healing-capability.json
new file mode 100644
index 0000000..d1ac187
--- /dev/null
+++ b/task2/task2-paper-info/liang-et-al-2019-transparent-and-scratch-resistant-antifogging-coatings-with-rapid-self-healing-capability.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "A self-healing antifogging coating based on polyzwitterion copolymer reinforced by silica nanoparticles is prepared in a one-pot synthesis. The interactions among the polymer components and silica nanoparticles can be tuned by varying the co-monomer ratio, which helps produce a coating that maintains transparency, resists scratching and abrasion, and repairs damages quickly.To synthesize hydrophilic polymers with functional groups, silica nanoparticles were first modified by dissolving 5.0 g (24 mmol) of DMASi and 3.0 g (25 mmol) of 1,3-propane sultone in 25 mL of anhydrous acetone under nitrogen, stirring for 6 h, collecting the white precipitate, and drying at room temperature. Then, 50 mg of silica nanoparticles were sonicated in 5 mL of water for 30 min, after which 9.5 mg of SBS were added, and the mixture was stirred for 6 h at 80 °C. The mixture was centrifuged at 5000 rpm for 30 min, and the centrifugate was washed three times with deionized water, dried at 80 °C, and stored under vacuum. For the fabrication of the P(SBMA7-co-HEMA3) coating, the substrates were cleaned with boiling piranha solution for 1 h, rinsed with water, and dried under nitrogen. Freshly cleaned substrates were immersed in an MPSi solution in anhydrous toluene (1:60, v/v) at 80 °C for 2 h, rinsed with toluene, and dried with nitrogen. Silica nanoparticles (2.5 or 5.0 wt% relative to the total mass of SBMA and HEMA) were sonicated in 2.5 mL of water for 20 min, a mixture of SBMA/HEMA (7/3 mole ratio), ammonium persulfate (1.0 mol%), and sodium metasulfite (0.5 mol%) was added, and the solution was stirred at 25 °C for 20 min. This solution was then spin-cast on the pretreated substrate and heated at 80 °C for 2 h to complete the polymerization and bonding."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/macdonald-et-al-2024-design-of-abrasion-resistant-long-lasting-antifog-coatings.json b/task2/task2-paper-info/macdonald-et-al-2024-design-of-abrasion-resistant-long-lasting-antifog-coatings.json
new file mode 100644
index 0000000..f64c132
--- /dev/null
+++ b/task2/task2-paper-info/macdonald-et-al-2024-design-of-abrasion-resistant-long-lasting-antifog-coatings.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The antifogging coatings are fabricated by utilizing a cross-linked polyvinylpyrrolidone (PVP) matrix that is modified with two critical additives. The coatings are applied using a facile two-step spray-coating process onto various plastic surfaces.A 0.0265 g/mL solution of 1300 kDa PVP and 0.001 g/mL benzophenone was prepared by dissolving these components in a solution containing 1-propanol, distilled water, and 15% Hydrogen peroxide with a volumetric ratio of 0.931:0.029:0.040. Surfactants (such as Polysorbate 20, Polysorbate 80, Polysorbate 85, Span 20, or Span 80) and Pentaerythritol tetraacrylate (PETRA) were dissolved in 1-propanol in varying concentrations. These were then added to the solvent mixture to achieve a final volume ratio of 0.895 1-propanol: 0.027 DI water: 0.03915% H2O2: 0.019 PETRA/1-propanol solution: 0.019 surfactant/1-propanol solution. The combined solution was stirred in a glass septa-jar for over 2 hours until fully dissolved. For coating fabrication, polycarbonate strips were cleaned with isopropyl alcohol and exposed to 30 W oxygen plasma for 10 minutes. A homebuilt automated spray coating apparatus was used to coat the plasma-treated strips from a distance of 20 cm, with parameters set to a linear speed of approximately 20 cm/s, 2 spray passes, and a spray pressure of 20 psi. After spraying, the coatings were exposed to UVA and UVC light at a distance of 12 cm for 10 minutes."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/martin-audus-2023-emerging-trends-in-machine-learning-a-polymer-perspective.json b/task2/task2-paper-info/martin-audus-2023-emerging-trends-in-machine-learning-a-polymer-perspective.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/martin-audus-2023-emerging-trends-in-machine-learning-a-polymer-perspective.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/nakagawa-et-al-2024-preparation-of-antifog-hard-coatings-based-on-carboxy-functionalized-polyhedral-oligomeric.json b/task2/task2-paper-info/nakagawa-et-al-2024-preparation-of-antifog-hard-coatings-based-on-carboxy-functionalized-polyhedral-oligomeric.json
new file mode 100644
index 0000000..26211e5
--- /dev/null
+++ b/task2/task2-paper-info/nakagawa-et-al-2024-preparation-of-antifog-hard-coatings-based-on-carboxy-functionalized-polyhedral-oligomeric.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The preparation of antifog hard coatings involved the polycondensation of silane coupling agents bearing amino or glycidyl groups under hydrolytic conditions (sol-gel reaction). The development of antifog hard coatings based on polyamides was done using POSS with amino and carboxy groups on side chains, employing a condensation agent, 1-(3-(dimethylamino)propyl)-3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS). The reaction was conducted by heating at 80 °C in dehydrated dimethyl sulfoxide (DMSO) for 12 hours.Preparation of Carboxy-Functionalized Rod-like PolySQ: Add 60 mL of 2.0 mol L^{-1} NaOH aqueous solution to 8.871 g of CETES while stirring at room temperature for 15 hours. Heat the mixture at ca. 50 °C in an open system until the solvent completely evaporates. Maintain the crude product at 100 °C in an oven for 2 hours. Add 120 mL of 1.0 mol L^{-1} HCl aqueous solution at room temperature and heat at ca. 50 °C until the solvent evaporates (ca. 6 hours). Add 25 mL of water to the resulting solid, stir for 1 minute, and perform immediate suction filtration to eliminate generated sodium chloride. Repeat this suction filtration three times. Dry the resulting solid under reduced pressure at room temperature to yield a white powdered product (5.304 g, quantitative yield). Preparation of POSS-C: Add 100 mL of 0.50 mol L^{-1} HOTf aqueous solution to 4.171 g of carboxy-functionalized rod-like polySQ. Heat the solution at ca. 60 °C for 20 minutes, then stir at room temperature for 2 hours. Heat at ca. 50 °C in an open system until the solvent completely evaporates (ca. 5.5 hours). Hold the liquid in an oven at 100 °C for 2 hours. After cooling, add 8.4 mL of acetone and pour the solution into 416 mL of a mixed solvent of acetone and chloroform (1:9 v/v) and stir at room temperature for 15 hours. Separate the insoluble part by filtration and wash 5 times with acetonitrile (ca. 25 mL). Dissolve the insoluble part in ca. 25 mL of acetone, separate the acetone-soluble part using filtration, evaporate acetone, and dry under reduced pressure at room temperature to yield a white powdered product (0.707 g, yield 17%)."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/olveira2015.json b/task2/task2-paper-info/olveira2015.json
new file mode 100644
index 0000000..863a5da
--- /dev/null
+++ b/task2/task2-paper-info/olveira2015.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "To synthesize hydrophilic polymers using the sol–gel method, prepare a precursor solution containing tetraethyl orthosilicate (TEOS) and a poloxamer (Pluronic F-127) with added nitric acid. Stir the solution at room temperature for 2 hours to form the sol. Then, spin-coat glass substrates with the sol and perform drying steps to create a mesoporous silica coating. Introduce mesopores on the surface to achieve superamphiphilicity without UV illumination, ensuring high surface energy and roughness due to Si–O–Si and Si–OH groups. For further optimization, similar procedures can be applied using indium nitrate and niobium ethoxide mixed in ethanol for UV-induced superamphiphilicity."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/optically transparent super-hydrophobic thin film fabricated by reusable polyurethane-acrylate(PUA) mold.json b/task2/task2-paper-info/optically transparent super-hydrophobic thin film fabricated by reusable polyurethane-acrylate(PUA) mold.json
new file mode 100644
index 0000000..d38f844
--- /dev/null
+++ b/task2/task2-paper-info/optically transparent super-hydrophobic thin film fabricated by reusable polyurethane-acrylate(PUA) mold.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "Thick PR molds with reversed hierarchical structures were prepared using a modified photolithography process. The unique structure of the PR molds is replicated on the PDMS surface. The structure is then re-replicated to the photocurable polymer layer for the purpose of reusing the mold.The PDMS monomer (base) and curing agent are mixed in a 10:1 ratio and placed in a desiccator to de-gas in a vacuum. The degassed PDMS solution is gently poured onto an under-baked PR mold and placed in a vacuum oven. The PDMS sample is degassed until trapped bubbles are removed from the interface with the PR mold. The thickness of the cured PDMS layer is controlled by adjusting the spin speed and number of coatings. The PDMS layer is cured at >80°C for 4h. The PR mold is removed using an acetone solution to replicate the super-hydrophobic PDMS film. For synthesis of UV-curable PUA, mix 85% 4-hydroxybutyl acrylate, 11% acrylic acid, 1% ethylene glycol dimethacrylate, and 3% 2'-dimethoxy-2-phenylacetone phenone. Pour this mixture on the replicated PDMS film and solidify with UV light for 20s at an optical power of 5mW."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/passaglia2018.json b/task2/task2-paper-info/passaglia2018.json
new file mode 100644
index 0000000..cab99aa
--- /dev/null
+++ b/task2/task2-paper-info/passaglia2018.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "bP has been directly exfoliated in the liquid vinyl monomer, methyl methacrylate (MMA), without solvents, and after the addition of a radical initiator, the hybrid material has been obtained by in situ radical polymerization. For comparison purposes, PMMA-based composites have also been prepared by the direct bP exfoliation in polymer solution or by starting from bPn previously exfoliated by LPE with DMSO and successively dispersed in the PMMA matrix.In Situ Radical Polymerization. A Schlenk tube (10 mL) equipped with a magnetic stirrer and previously degassed, backfilled three times with nitrogen, was loaded with the MMA_bPn or Sty_bPn or NVP_bPn suspensions (previously prepared). A weighted amount of AIBN (2 wt % with respect to the monomer) was added, and the tube was placed in an oil bath (temperature and time of polymerization depending on the vinyl monomer used). The product was then dissolved in CHCl3 and precipitated in an appropriate solvent to remove unreacted monomer and polymerization byproducts: MeOH was used for PMMA and PS, while Et2O was used for PNVP. After recovering via filtration, the resulting powder was dried under vacuum until a constant weight was achieved."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/preparation of antifog and antibacterial coatings by photopolymerization.json b/task2/task2-paper-info/preparation of antifog and antibacterial coatings by photopolymerization.json
new file mode 100644
index 0000000..7494b1b
--- /dev/null
+++ b/task2/task2-paper-info/preparation of antifog and antibacterial coatings by photopolymerization.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "In this study, a quaternary ammonium salt (14QAS) was synthesized in the lab for use in ultraviolet-cured antifog coatings. The QAS-containing polymers were applied to create durable antifog coatings, which demonstrated long-lasting antifogging properties and antibacterial effects.The synthesis route of 14QAS was list in Scheme 1.Dimethylaminoethyl methacrylate (0.25 mol), BTD (0.2 mol), and tetrahydrofuran (30 ml) were added into a 250 ml three-neck round-bottomed flask equipped with a condenser, desiccator, and mechanical stirrer. The mixture was stirred at 37°C for 24 hr. After the reaction, unreacted BTD and DMAEMA were removed by repeated washing for 1-2 min with 5-7 ml ether aliquots, discarding the ether supernatant after each wash. Residual ether was removed via gentle nitrogen stream, and the final product was dried for 24 hr under vacuum in the dark. The yield of 14QAS under 37°C could be 33.7%.Dissolve 14QAS and 1173 in HEA, then mix with PEGDA 600, CN929, and leveling agent. Use a wire bar coater (20 µm) to prepare the film on glass slides and irradiate for 3 min with a medium-pressure mercury lamp. Light intensity should be set to 20 mW/cm² as measured by an ultraviolet light radiometer.14QAS was prepared by the reaction of tertiary amine and bromoalkane. The synthesis was optimized by varying temperatures between 35°C and 40°C, with the maximum yield of 35.4% obtained at 37°C."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/s41467-020-14807-x.json b/task2/task2-paper-info/s41467-020-14807-x.json
new file mode 100644
index 0000000..cb2574d
--- /dev/null
+++ b/task2/task2-paper-info/s41467-020-14807-x.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "To synthesize hydrophilic polymers with functional groups, employ a photoinduced strategy involving the coupling of photolysis, photopolymerization, and transesterification. First, use photolysis to generate dissociable ionic groups which enhance the swelling ability of the substrate. This swelling allows nutrient solutions containing polymerizable components to be absorbed into the irradiated region. Next, utilize photopolymerization to convert these polymerizable components into polymers. Finally, perform transesterification to incorporate the newly formed polymers into the original polymer network structure. This method enables spatial control, dose-dependency, and modulation of the size, composition, and mechanical properties of the synthesized structures.To fabricate seeds, mix HBA (80 mol%) and NBA (20 mol%). Add HDDA (crosslinker, 1 wt%) and I-819 (photoinitiator, 1 wt%) to obtain the precursor. Coat the precursor solution on Teflon substrates and cure under blue light (intensity: 0.6 mW cm^-2) for 20 min. Immerse the obtained substrate in ethanol, changing the solution every 8 hours (3 times) to remove unreacted specimens. Dry to afford seed-20%. For light-induced growth, immerse seed-20% in a nutrient solution containing HBA (96 wt%), HDDA (1 wt%), I-819 (1 wt%), and BZSA (2 wt%) for 12 hours to obtain swollen samples. Subject swollen samples to UV light (intensity: 10 mW cm^-2) with a suitable photomask for growth."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/s41524-023-01000-z.json b/task2/task2-paper-info/s41524-023-01000-z.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/s41524-023-01000-z.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/s41529-024-00427-z.json b/task2/task2-paper-info/s41529-024-00427-z.json
new file mode 100644
index 0000000..bebddb7
--- /dev/null
+++ b/task2/task2-paper-info/s41529-024-00427-z.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The self-healing coating formulation consists of an EP resin, polyetheramines, amino-terminated urea-pyrimidinone monomers (UPy-D400), and ZIF-8@Ca microfillers. The EP resin mixed with polyetheramine reacts to form an EP-based polymer, while UPy-D400 acts as a quadruple hydrogen bonding unit that is grafted into the EP network. The parameter variables include the molecular weights of polyetheramine, the molar ratio of polyetheramine to EP, UPy-D400 content, and ZIF-8@Ca content. The initial dataset for the machine learning model was obtained from preliminary experiments, and the self-healing and corrosion protective properties of the optimal coating were verified by electrochemical impedance spectroscopy (EIS) and salt spray testing.Polyetheramine curing agents with different molecular weights (230, 400, 2000, and 4000 g mol^{-1}) are used along with E51 EP resin as the base material. ZIF-8@Ca microfillers and UPy-D400 monomers are incorporated into the formulation. The Q235 mild steel serves as the substrate for the polymer application.The ZIF-8@Ca microfillers were mixed with E51 EP resin under magnetic stirring. Then, a polyetheramine curing agent and UPy-D400 were added to the mixture using a mechanical agitator at 500 rpm for 10 min. Steel specimens were wet-polished with 150-, 240-, and 400-grit sandpapers, washed with ethanol, and blow-dried in a nitrogen atmosphere. The resulting mixture was applied to a steel piece using a bar coater, and the coated samples were dried at room temperature for 48 hours. The final thickness of each dry film was approximately 85 μm."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/synthesis of acrylate-based UV thermal dual-cure coatings for antifogging.json b/task2/task2-paper-info/synthesis of acrylate-based UV thermal dual-cure coatings for antifogging.json
new file mode 100644
index 0000000..91274ba
--- /dev/null
+++ b/task2/task2-paper-info/synthesis of acrylate-based UV thermal dual-cure coatings for antifogging.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "1. Use acrylic ester as the main chain for the polymer synthesis. 2. Introduce hydrophilic monomer 2-acrylamide-2-methylpropane sulfonic acid (AMPS) to enhance the hydrophilicity. 3. Modify the acrylic resin main chain with 3-(trimethoxysilyl)propyl-2-methyl-2-methacrylate (MPS). 4. Use tetraethylorthosilicate (TEOS) as a curing agent. 5. Conduct a dehydration condensation reaction under alkaline conditions to generate Si–O–Si bonds from the hydroxyl groups of MPS and TEOS. 6. Ensure that Si–O–Si bonds migrate to the coating surface during curing to form a dense Si–O–Si network structure. 7. Cure the film by adding a photoinitiator and reactive diluents through the double bonds from half-blocked polyurethane. 8. Measure properties of the films with varying TEOS contents using contact angle measurements, atomic force microscopy (AFM), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM).AA and HEA were pretreated to remove polymerization inhibitor. A mixture of AA, AMPS, HEA, MPS, and DMF was added into a dried 250 mL four-necked flask equipped with mechanical stirrer, condenser, N2 catheters, and pressure-equalizing dropping funnel. The mixture was stirred at room temperature under N2 protection and gradually heated to 80°C. AIBN (3% of total monomer weight) was dissolved in a small amount of DMF, half of which was added into the flask dropwise via the constant-pressure dropping funnel for 1 hour at 80°C, and reacted for another 3 hours at 80°C. The remaining initiator was then added to the flask at the same dripping speed and reacted for another 3 hours. Nucleophilic addition of IPDI and HEA was employed to prepare isocyanate-containing unsaturated monomer, IPHE. A mixture of IPDI, HEA, MEHQ, ACE, and DBTDL was added into a dried 250 mL four-necked flask equipped with mechanical stirrer, condenser, N2 catheters, and pressure-equalizing dropping funnel, then gradually heated to 55°C and allowed to react for 2 hours. The NCO content was monitored during the reaction using the standard dibutylamine backtitration method. Upon reaching the theoretical NCO value, the product was cooled to room temperature, transferred to another pressure-equalizing dropping funnel, then added dropwise to the PAAMH. At the same time, additional catalyst DBTDL was added and reacted at 80°C for about 3 hours until the NCO content reached another theoretical value. Reaction completion was confirmed by disappearance of the FTIR absorption peak at 2270 cm-1 corresponding to stretching vibration of NCO group. Acetone was added to adjust the viscosity of the IPHE prepolymer, which was later removed to afford PAAMH-IH with 30 wt% solid content.Combine PAAMH-IH with 3-4 wt% photoinitiator (Irgacure 1173), 0.3 wt% leveling agent 3288, 25 wt% reactive diluents 15EO-TMPTA, and an appropriate amount of TEOS as per Table 2. Adjust the pH to approximately 13 using 25% aqueous ammonia, then stir quickly at room temperature. Coat the solution onto clean glass slides by dipping, and allow to dry slowly at 50°C for 5 hours. Heat the films in an oven at 70°C for 2 hours. Finally, irradiate the films using a 1200-W UV lamp (200-400 nm) for 30 seconds at room temperature."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/uchiyama2015.json b/task2/task2-paper-info/uchiyama2015.json
new file mode 100644
index 0000000..a2364a0
--- /dev/null
+++ b/task2/task2-paper-info/uchiyama2015.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Prepare sol-gel-derived titania films by dip coating from Ti(OC3H7i)4 solutions containing 2-propanol (2-Pr) as the major solvent and propylene glycol (PG) and dipropylene glycol (DPG) as the co-solvents. Vary the contents of PG and DPG to control the surface tension gradient in the coating layer. The effect of the co-solvents on the spontaneous pattern formation induced by Bénard−Marangoni convection should be systematically discussed.The preparation of hydrophilic polymers with functional groups follows the outlined steps: First, starting solutions with molar compositions of Ti(OC3H7^i)4/H2O/HNO3/2-Pr/PG or DPG were prepared in the ratio 1:2:0.2:40:x or y (where x or y ranges from 0 to 1.50). Begin by adding Ti(OC3H7^i)4 to half of the prescribed amount of 2-Pr. Mix the remaining 2-Pr with H2O and HNO3, and then add this solution dropwise to the Ti(OC3H7^i)4 solution while stirring. Allow the combined solution to stand at room temperature in a sealed glass container for 30 minutes, then add PG or DPG under stirring. Let the solution stand for an additional 3 hours to serve as a coating solution. Titania gel films are then deposited on Si(100) substrates using a dip coater, where substrates are withdrawn at a rate of 50.0 cm/min in a thermostatic oven maintained at 60°C, with solutions and substrates preheated for 30 minutes before dip coating. After gel film deposition, keep at 60°C for 3 minutes, then heat the films at 200 or 600°C for 10 minutes in air."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/water drop-surface interactions as the basis for the design of anti-fogging surfaces.json b/task2/task2-paper-info/water drop-surface interactions as the basis for the design of anti-fogging surfaces.json
new file mode 100644
index 0000000..01bfea9
--- /dev/null
+++ b/task2/task2-paper-info/water drop-surface interactions as the basis for the design of anti-fogging surfaces.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of hydrophilic polymers with functional groups is not explicitly detailed in the provided text excerpt. The excerpt primarily discusses the concepts of fogging, the drawbacks of condensation, anti-fogging strategies, and the classification of wetting behaviors of surfaces without providing specific experimental protocols or detailed methods related to polymer synthesis."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/xu2012.json b/task2/task2-paper-info/xu2012.json
new file mode 100644
index 0000000..fcc6b25
--- /dev/null
+++ b/task2/task2-paper-info/xu2012.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The UV-PUA oligomer was prepared with isophorone diisocyanate (IPDI), polyether polyol (NJ-210), dimethylol propionic acid (DMPA), hydroxyethyl methyl acrylate (HEMA) via in situ and anionic self-emulsifying method; and the UV-PUA system was composed of the oligomer, photoinitiator Darocur 1173 and monomers (BA-TPGDA). The effects of the ratio of the BA/TPGDA, Darocur 1173 and the curing time on the performance of the UV-PUA films were investigated.Polyether polyols (NJ-210) were mixed with dimethylpropionic acid (DMPA) and isophorone diisocyanate (IPDI) under controlled conditions. Additionally, hydroxyethyl methyl acrylate (HEMA) and butyl acrylate (BA) were incorporated into the mixture. The reaction was catalyzed with triethylamine (TEA) and monitored with the use of acetone and dibutylbis (lauroyloxy) tin (DBLT). The resulting blend was then further processed by adding N-methyl -2-pyrrolidone (NMP) and tripropyleneglycol diacrylate (TPGDA). The polymerization was initiated using Darocur 1173, allowing the formation of hydrophilic polymers with desired functional groups.A certain amounts of NJ-210 (10.802 g) and IPDI (8.325 g) were added into a four-necked flask equipped with a mechanical stirrer, thermometer and reflux condenser. Then, DBLT was added as catalyst and the mixture was heated to 60°C and kept at this temperature for 2 hours to prepare the –NCO terminated prepolymer. Next, the prepolymer was reacted with 1.221 g of DMPA dissolved in a small amount of NMP at 80-85°C for another 2 hours, resulting in the –NCO terminated prepolymer containing a carboxyl group. The reactant was cooled down to 60°C, then 4.875 g of HEMA was added and the mixture was reacted at 60°C for 5 hours. When the temperature cooled down to 40°C, TEA was added into the flask and reacted at 40°C for 30 minutes. The mixture was then dispersed into deionized water under vigorous stirring for 30 minutes.UV-PUA films were prepared by casting the newly synthesized oligomer, BA and TPGDA onto a poly (tetrafluoroethylene) drying at 65°C for 3 h. Water was used as a diluent in this system, requiring a flash-off step to evaporate the water before UV curing. Physical entanglement occurred due to the large molecular weight of the prepolymer during water removal. The samples were then irradiated with UV light from a lamp with a main wavelength of 365 nm, power of 1000 W, UV energy per second of 1000 J/s, and at a distance of 20 cm from the UV lamp. This activated Darocur 1173, producing radicals that broke the acrylate double bond of the monomers and oligomers, resulting in crosslinking and the formation of the UV-PUA film.The PU or PUA films were cut into the size of 30mm x 30mm and put into water, 5% NaOH and ethanol at 25°C after being weighted. 24 hours later, the film was taken out, rubbed dry by wiping off the surface water with a piece of filter paper, and then weighted again. The water absorption (or swelling degree) was calculated using the formula: omega = (W2 - W1) / W1 x 100%, where W1 is the mass of the film before being put into the solution and W2 is the mass of the film after.The UV-PUA films were cut into the size of 2 cm x 2 cm, then the sample was put into a solvent (acetone) for 48 hours, and dried for 72 hours at 30°C to give a constant weight. The gel content was calculated using the formula G = (W/W0) x 100%, where W0 is the mass of the film before being put into the toluene, and W is the mass of the film after being put into the toluene.Put the UV-curable emulsion (the water had been evaporated) under the UV lamp irradiating for a certain amount of time, then gently pressed the UV-curable film with finger. If there is no trace on the film, the time of the UV lamp irradiating was the surface drying time of UV-PUA films.FT-IR spectrum of the UV-PUA film was obtained between 4000 and 400 cm-1 with an FTIR spectrometer (AVATAR 360, Madison, Nicolet). A minimum of 32 scans was signal-averaged with a resolution of 2 cm-1 in the 4000-400 cm-1 ranges.The synthesis of hydrophilic polymers with functional groups involves using a UV-PUA oligomer. The specific steps are not detailed in the provided text excerpt.Prepare a series of UV-PUA films by fixing the content of Darocur 1173 at 3%, maintaining an NCO:OH ratio of 2.0, and using a constant weight of the PUA oligomer at 10.8 g while varying the ratio of BA/TPGDA (R).Prepare UV-PUA films by fixing the ratio of BA/TPGDA to 5/5, adding 4% of Darocur 1173, and using 10.8 g of PUA oligomer. Change the curing time to prepare a series of films."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/zhang-et-al-2024-robust-uv-curable-dual-cross-linked-coating-with-increased-transparency-long-term-antifogging-and.json b/task2/task2-paper-info/zhang-et-al-2024-robust-uv-curable-dual-cross-linked-coating-with-increased-transparency-long-term-antifogging-and.json
new file mode 100644
index 0000000..2d1ecb9
--- /dev/null
+++ b/task2/task2-paper-info/zhang-et-al-2024-robust-uv-curable-dual-cross-linked-coating-with-increased-transparency-long-term-antifogging-and.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Synthesis of hydrophilic polymers with functional groups was achieved through a UV-assisted cross-linking method, incorporating quaternary ammonium groups into the polymer network. The process involved creating a dual-cross-linked structure using pMDHAB−AA−aziridine and PEGDA networks.Synthesis of the Prepolymer pDMAEMA−AA Copolymer: A total of 40 g of DMAEMA and 4 g of AA were added to a 250 mL flask, followed by the addition of 44 g of o-xylene and 0.44 g of AIBN (1 wt % with respect to the total monomer mass) as the thermal initiator. The polymerization was conducted at 80 °C in an oil bath with magnetic stirring for 12 h. After the reaction, the final copolymer was precipitated by hexane, and the pure pDMAEMA−AA copolymer was obtained by washing three times with hexane and drying in a vacuum oven for 24 h at 60 °C. Preparation of Quaternary Ammonium Salt: 4 g of pDMAEMA−AA copolymer and 6.24 g of 1-bromoheptane were introduced to 30 mL of acetonitrile, followed by stirring at 80 °C for 12 h. Solid residues were collected through vacuum rotary evaporation after cooling to room temperature. The products were purified and washed with hexane three times, then dried in a vacuum oven at 60 °C for 24 h to obtain the pure quaternary ammonium copolymer (pMDHAB−AA). Preparation of the Dual-Cross-Linked pMDHAB−AA/PEGDA Coating: 1.2 g of quaternary ammonium copolymer was dissolved in 8 g of deionized water with stirring for 12 h. Added 0.236 g of APA and stirred for 2 h, then added 0.024 g of PEGDA and 0.0024 g of 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone, stirring for 1 h. The solution was drop-coated on a clean PET film treated with oxygen plasma, followed by UV curing at 365 nm for 30 min. Single PEGDA coatings were prepared using the same UV-curing method without pMDHAB−AA and APA, while the single APA coating was cured at room temperature for 24 h."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/zhang2021.json b/task2/task2-paper-info/zhang2021.json
new file mode 100644
index 0000000..f6db26a
--- /dev/null
+++ b/task2/task2-paper-info/zhang2021.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The most adopted methods to prepare BP/polymers comprise solution casting (SC), polymerization methods (PMs), and spinning technology (ST) methods.1. Dissolve specific amounts of polymers and BP in solvents to form homogeneous solutions, using sonication or vigorous stirring. 2. For PEG-\\\\cdotNH2 modification, dissolve the modified BP QDs in deionized water and sonicate for 30 minutes. 3. Treat the resulting BP/PEG-\\\\cdotNH2 nanocomposite with repeated centrifugation and water rinsing. 4. For emulsion solvent evaporation method, disperse materials in organic solvents to create a homogeneous solution, then add this to an aqueous solution and sonicate to obtain an emulsion. 5. Centrifuge the emulsion to obtain solid BP/polymer nanocomposites. In specific examples, BP QDs and PLGA can be dissolved in dichloromethane and added to a PVA aqueous solution, stirring overnight to remove residual DCM.1. Mix BP with the chosen polymer (e.g., PDLLA, agarose, PPMS, or MF) to form a composite. 2. For agarose, heat the mixture to enable reversible hydrolysis and softening. 3. For PPMS, disperse PPMS and BP NSs in a DCM solution via ultrasound. 4. Drop the mixture onto the surface of polished Ti-OH to fabricate a film. 5. Cure the mixture thermally in a vacuum oven. 6. For MF, mix BP-MF and DDM in acetone and stir for 10 min, then add EP and stir for an additional 30 min. 7. Place the final mixture in a vacuum oven at 60 °C for 2 hours to remove acetone, then cure at 100 and 150 °C for 2 hours. 8. Characterize the resulting nanocomposite for specific properties (e.g., antibacterial rate or char yield).The synthesis of hydrophilic polymers with functional groups involves the use of various methods. For example, the electrochemical deposition method is utilized to prepare BP/PPy films, while freeze drying is employed to obtain BP/PVA nanocomposites connected through strong hydrogen bonding. Additionally, BP/Pluronic F127 can also be prepared using the freeze drying technique. It is important that the BP and polymers exhibit excellent fluidity, homogeneity, and large cohesion to ensure continuous spinning flow when using spinning technology."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/zhao-et-al-2016-dual-functional-antifogging-antimicrobial-polymer-coating.json b/task2/task2-paper-info/zhao-et-al-2016-dual-functional-antifogging-antimicrobial-polymer-coating.json
new file mode 100644
index 0000000..0fc7348
--- /dev/null
+++ b/task2/task2-paper-info/zhao-et-al-2016-dual-functional-antifogging-antimicrobial-polymer-coating.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Prepare a smooth antifogging coating using a semi-interpenetrating polymer network (SIPN) that comprises either a binary copolymer poly(2-(dimethylamino)ethyl methacrylate-co-methyl methacrylate) [poly(DMAEMA-co-MMA)] or a terpolymer containing DMAEMA segments along with a network from polymerized ethylene glycol dimethacrylate (EGDMA). Ensure to balance hydrophilicity and hydrophobicity in the formulation. This coating should rapidly absorb water from the environment to prevent the formation of discrete water droplets on the surface.The synthesis of hydrophilic polymers with functional groups was conducted via a free radical solution polymerization method. Specifically, the copolymer poly(DMAEMA-co-MMA) was synthesized by adding 9.6 g of DMAEMA and 2.0 g of MMA into a 250 mL flask, then dissolving in toluene to achieve a 10 wt % solution. Following the addition of 0.058 g of AIBN as a thermal initiator, the mixture was purged with argon for 20 minutes and subjected to polymerization at 70 °C for 24 hours. The resulting poly(DMAEMA-co-MMA), referred to as B-75 with 75 mol% of DMAEMA segments, was purified by dissolution in chloroform followed by precipitation in hexane. For partial quaternization, 1.0 g of B-75 was dissolved with 0.063 g of 1-bromoundecane in 15 mL of acetonitrile in a 50 mL flask, followed by a 24-hour reaction at 70 °C. The resulting product was likewise purified and dried in a vacuum oven at 45 °C for 24 hours. The yield from the quaternization process was 95%."
+}
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diff --git a/task2/task2-paper-info/г╒г╓ ╣╠╗п╡е╠х╝░╡═╛█╬я╘┌╦▄╜║╗∙▓─╔╧╡─╕╜╫┼┴ж╙ы╗п╤з╜с╣╣╓о╝ф╣╪╧╡╡─╤╨╛┐.json b/task2/task2-paper-info/г╒г╓ ╣╠╗п╡е╠х╝░╡═╛█╬я╘┌╦▄╜║╗∙▓─╔╧╡─╕╜╫┼┴ж╙ы╗п╤з╜с╣╣╓о╝ф╣╪╧╡╡─╤╨╛┐.json
new file mode 100644
index 0000000..83b7e86
--- /dev/null
+++ b/task2/task2-paper-info/г╒г╓ ╣╠╗п╡е╠х╝░╡═╛█╬я╘┌╦▄╜║╗∙▓─╔╧╡─╕╜╫┼┴ж╙ы╗п╤з╜с╣╣╓о╝ф╣╪╧╡╡─╤╨╛┐.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "To synthesize hydrophilic polymers with functional groups, the following materials are used: TPGDA, NPG(PO)2DA, TMPTA, TMP(EO)3TA, GP(PO)3TA, PE-TIA, DPHA, EBECRYL series of di-, tri-, tetra-, and hexafunctional urethane and polyester acrylates, and SR502. The process involves high-speed stirring using an SFJ-400 mixer. UV curing is performed using a conveyor UV curing machine from IST, followed by measuring the coating thickness with a Qnix 4500 device. A photo initiator, IRGACURE 184, is utilized during the synthesis.按照表 1 依次配料， 然后用高速搅拌机在800~r/min 的条件下搅拌 15~min， 密封避光存放。将配好的涂料依次喷于 ABS 板上，置于烘箱闪干，然后通过履带式 UV 固化机固化。漆膜厚度控制在 $10\\sim15~{\\upmu\\mathrm{m}}$。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/│╠╥л╗╘-╧╦╬м╦╪└ы╫╙╥║╠х╤Ї└ы╫╙╨═╤▄╔·╬я╖└╬э.json b/task2/task2-paper-info/│╠╥л╗╘-╧╦╬м╦╪└ы╫╙╥║╠х╤Ї└ы╫╙╨═╤▄╔·╬я╖└╬э.json
new file mode 100644
index 0000000..989a0a6
--- /dev/null
+++ b/task2/task2-paper-info/│╠╥л╗╘-╧╦╬м╦╪└ы╫╙╥║╠х╤Ї└ы╫╙╨═╤▄╔·╬я╖└╬э.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "2.2.2.1 多种不同阳离子纤维素衍生物的合成, 2.2.2.2 阻燃性水溶性纤维素衍生物合成人工合成纤维素的合成主要有酶催化和葡萄糖衍生物的开环聚合两种方法。纤维素的化学改性提供了基础，可以使纤维素衍生化制备得到各功能化材料。首先处理含有酸和氨的植物组织，随后用水、乙醇和乙醚萃取得到残留的抗性纤维状固体。两种方向性不同的末端基，即C4-OH和C1-OH分别提出仲醇羟基和半缩醛结构，提供了进一步反应的基础。衍生化过程中，可能采用离子液体或离子液体和有机溶剂共溶剂体系直接将纤维素溶解，以进行后续的分子量和分布的测定。To synthesize hydrophilic polymers with functional groups, utilize non-derivatizing solvents that physically dissolve cellulose without altering its chemical structure. Key solvent systems include aqueous solutions of proton acids such as HCl (40-43%), HNO3 (84%), H2SO4 (65-80%), and H3PO4 (73-83%) which protonate cellulose and allow it to dissolve. Additionally, Lewis acid solutions, particularly zinc chloride at 64% concentration, effectively dissolve cellulose. For derivatization reactions, which include esterification and etherification, inorganic metal salt hydrates can be employed post dissolution. A notable system is NaOH/H2O, where cellulose disintegration occurs best at -20 to 4 °C with NaOH concentrations between 6% and 18%. This method is more effective for microcrystalline cellulose with a polymerization degree below 200. Incorporating thiourea or urea can enhance the solubility of higher polymerization cellulose at lower temperatures.To synthesize hydrophilic polymers with functional groups using a non-aqueous solvent system, first prepare a multicomponent solution of N,N-dimethylacetamide (DMAc) and LiCl, which effectively dissolves higher molecular weight cellulose resulting in a homogenous transparent solution. This solution can be utilized for various analytical techniques such as NMR, mass spectrometry (MS), gel permeation chromatography (GPC), and dynamic light scattering (DLS). Ensure the chemical stability of the DMAc/LiCl system by using it as a reaction solvent for the reaction of anhydrides or acyl chlorides with cellulose. For the esterification reaction, catalysts like DMAP (4-dimethylaminopyridine), DCC (1,3-dicyclohexylcarbodiimide), or CDI (N,N'-carbonyl diimidazole) can be introduced into the reaction mixture.纤维素的衍生化反应可以是非均相和均相反应，例如纤维素纤维、纤维素纳米晶的表面修饰。均相反应例如离子液体体系、DMAc/LiCI体系中的酯化反应。通常来说，均相反应的反应效率更高，反应更为均一，产物也更为均一。纤维素醚的合成主要有三种方法：1. Williamson醚化反应; 2. 碱催化环氧加成反应; 3. 碱催化加成反应。使用Williamson醚化反应时，将纤维素与对应取代基的卤化物在碱性条件下反应，获得诸如羧甲基纤维素、甲基纤维素、乙基纤维素、丙基纤维素等产物。对于羟乙基纤维素、羟丙基纤维素，通过碱催化环氧加成反应实现。此外，纤维素与丙烯酰胺等含吸电子基团的分子通过Michael加成反应得到含氨基或氰基的纤维素醚。Yan通过原位光聚合得到咪唑型 PILs，随后将两种氨基酸（L-脯氨酸（Pro）和L-色氨酸（Trp)）通过阴离子置换，得到两种氨基酸阴离子型PILs膜。通过均相酯化反应和后续的亲核取代反应，利用纤维素材料多羟基的特点合成具有功能的阳离子纤维素衍生物。在离子液体溶液中进行均相酯化反应。首先通过酯化反应将氯引入到纤维素中，随后将其和三丁基麟、吡啶、1-甲基咪唑和1-乙烯基咪唑等反应制备了多种阳离子纤维素衍生物，然后考察了取代度对其溶解性影响。随后，通过离子交换的方式，得到可被有机溶剂溶解的疏水型纤维素衍生物。1. Dry cotton pulp in a vacuum oven at 70°C for 48 hours before use. 2. Use 2-Chloropropionylchloride directly with a purity of 97%. 3. Synthesize 1-Allyl-3-methylimidazole chloride in the laboratory with a moisture content not exceeding 0.3%. 4. Use Tributyl phosphine, pyridine, 1-Methylimidazole, and 1-Allylimidazole directly with a purity of 98%. 5. Use montmorillonite with a specific surface area of 240 m2/g directly. 6. Use bistrifluoromethanesulfonimidelithium salt, Lithium Hexafluorophosphate, and Lithium Tetrafluoroborate directly with a purity of 98%. 7. Use Sudan II and Isatin directly with a purity of 98%. 8. Utilize Milli-Q ultra-pure water and DMSO-d6 directly with a purity of 99.8%. 9. All other chemical reagents should be obtained from Beijing Guoyao Chemical Reagent Company with analytical purity, no further purification required.该实验涉及合成阳离子型纤维素衍生物。首先，准备纤维素粉末并将其溶解在适当的溶剂中。接着，加入阳离子试剂，如三甲基氯化铵，并进行反应，通常在加热条件下进行，以促进反应的进行。这些步骤需要在惰性气氛下操作，并控制反应时间和温度。最后，通过沉淀、离心和洗涤等过程纯化产物，得到目标阳离子型纤维素衍生物。1g棉浆粕加入到 49 g 离子液体AmimCl中，于 80°C油浴中剧烈搅拌溶解1h，得到浓度为 5%的纤维素/离子液体溶液。将纤维素溶液置于 0%的冰水浴中，等温度稳定后，加入含有 2.4 g 的2-氯丙酰氯，充分混合。随后，将其转移到 40°C油浴中反应 3 h。反应结束后加入乙醇和水使样品沉淀，使用砂芯漏斗抽滤，干燥。将干燥后的样品重新溶于二甲基亚矾中，使用 0.45μm滤膜过滤，再次使用乙醇沉淀，抽滤、洗涤三次后，置于 80°C的真空烘箱中干燥，得到取代度为3.0的纤维素2-氯丙酸酯。取一定量上述纤维素2-氯丙酸酯，溶解于N,N-二甲基甲酰胺（DMF）中，加入一定量三丁基麟、吡啶、1-甲基咪唑、1-乙烯基咪唑，置于 80°C油浴中回流反应 24h，待反应结束后，加入丙酮使样品沉淀，使用砂芯漏斗抽滤三遍以上，真空干燥。将干燥后的样品重新溶于二甲基亚矾中，使用 0.45μm滤膜过滤，再次使用丙酮沉淀，砂芯漏斗抽滤、洗涤三次后，置于 80°C的真空烘箱中干燥。将上述中咪唑型阳离子衍生物（2.5 mmol）溶于水中，滴加LiTfN、LiBF4或LiPF6的饱和水溶液（2.3 mmol），将反应体系在室温搅拌 24h，出现白色沉淀。过滤沉淀物，用去离子水洗涤三次，并在 80°C下真空干燥 24h，以获得不同阴离子型咪唑阳离子纤维素衍生物。1. Synthesis of cellulose 2-chloropropionate: Dissolve 49 g of ionic liquid AmimCl in cotton pulp at 80°C with vigorous stirring for 1 hour to prepare a 5% cellulose/ionic liquid solution. Place the cellulose solution in an ice bath at 0°C until the temperature stabilizes, then add 2.4 g of 2-chloropropionyl chloride and mix thoroughly. Transfer the mixture to a 40°C oil bath and react for 3 hours. After the reaction, add ethanol to precipitate the sample, perform suction filtration, and dry. Redissolve the dried sample in dimethyl sulfoxide, filter using a 0.45 μm filter membrane, and precipitate again using ethanol. Perform suction filtration, wash three times, and dry in a vacuum oven at 80°C to obtain cellulose 2-chloropropionate with a substitution degree of 3.0. Follow the same procedure for step 2 to prepare water-soluble cellulose derivatives. 2. Preparation of flame-retardant water-soluble cellulose membranes: All membranes are prepared using the solvent evaporation method by dispersing the obtained water-soluble cellulose ester in water at 10 wt%. Add varying amounts of montmorillonite and sonicate for 40 minutes with a cell crusher, then pour the mixture into a mold and place it on a hot plate at 80°C. After 2 hours, transfer the membrane and continue drying in a vacuum oven for 24 hours.第一步，将纤维素溶解在AmimCI离子液体中，进行均相衍生化以合成不同取代度的纤维素2-氯丙酸酯（DS分别为1.5和3.0）。第二步，向反应体系中加入三丁基麟、吡啶、1-甲基咪唑和1-乙烯基咪唑，通过控制投料比和反应时间，合成三种阳离子型纤维素衍生物。在表2.1和表2.2中，记录不同反应条件（如基础试剂的摩尔比、反应温度和反应时间）对纤维素衍生物取代度的影响，具体如下：对于DS=3.0的样品，使用6:1的投料比，反应时间为24小时时，取代度可达到2.51，而对于DS=1.5的样品，使用6:1的投料比，反应时间为24小时时，取代度可达到1.4。首先，将1-丁基咪唑阳离子（[Bim]*）引入到CA中，得到两种新型的阳离子化纤维素酯，醋酸纤维素1-丁基咪唑氯盐(CA-BimCI)和醋酸纤维素1-丁基咪唑双(三氟甲烷磺酰基)酰亚胺(CA-BimTfN)。然后，阳离子化纤维素酯通过强静电相互作用可以有效地固定各种游离ILs，从而制得均匀，高透明的具有高 CO2 透过性，高热稳定性和高机械性能的纤维素酯/ ILs复合膜。醋酸纤维素（CA）在 $80^{\\circ}\\mathrm{C}$ 真空烘箱干燥 $24\\mathrm{h}$，然后将2-氯丙烯酰氯（2-Chloropropionylchloride）、N-丁基咪唑（1-butylimidazole）和双三氟甲磺酰亚胺锂盐（LiTfN）以纯度为 $97\\%$ 和 $98\\%$ 的原料直接使用。其余其他化学药品均为分析纯，使用前无需进一步提纯。Dissolve CA (4.1 mmol) in N,N-dimethylformamide (DMF). Add 13.7 mmol of 2-chloro propionyl chloride to the CA/DMF solution at 0°C. Transfer to a 40°C oil bath and react for 3 hours. Add the resulting homogeneous solution to ethanol to terminate the reaction, filter the precipitate with ethanol, wash three times with ethanol, and dry in a vacuum oven at 80°C for 24 hours to obtain CA-Cl.将 CA-Cl（3.1mmol）溶解在DMF 中。随后，添加14.0mmol的1-丁基咪唑，并且反应在 80°C 油浴中进行 24h。将所得溶液加入乙醇中以终止反应。过滤沉淀物，用乙醇洗涤三次， 80°C 真空干燥 24h，得到CA-BimCl。将CA-BimCl（2.5mmol）溶于水中。然后，滴加LiTfN的饱和水溶液（2.3mmol）。将反应体系在室温搅拌 24h。出现白色沉淀。过滤沉淀物，用去离子水洗涤三次，并在 80°C 下真空干燥 24h，以获得CA-BimTfN。将1.5g 的CA或CA-BimTfN溶解在 13.5 g 的DMF中，以获得浓度为 10‰ 的CA/DMF或CA-BimTfN/DMF溶液。然后，加入一定量的所需IL。将所得溶液流延到玻璃板上。在 65°C 的热台上蒸发溶剂。随后，成膜后将其从玻璃基板剥离。在真空下于 80°C 进一步干燥 24h，获得 CA-BimTfN/ILs 和 CA/ILs膜。通过均匀且可控的酯化过程合成醋酸纤维素2-氯丙酸酯（CA-Cl）。随后，与1-丁基咪唑进行亲核取代反应，获得阳离子化纤维素衍生物CA-BimCl。最后，通过阴离子交换步骤制备CA-BimTfN。在亲水性物质纤维素上引入亲水性阳离子基团，通过离子交换将阴离子交换为疏水性离子，得到一种新型离子化纤维素衍生物材料。纤维素链上有多个羟基，可以通过控制取代度调节亲水基团和疏水基团比例，以达到调节界面水目的，从而实现调节冰成核温度及冰粘附力。在80°C真空烘箱中将聚合度DP=650的棉浆粕烘干24小时。使用2-氯丙烯酰氯（纯度97%）、N-丁基咪唑（纯度98%）和全氟辛酸钠（纯度97%）作为反应试剂。离子液体1-烯丙基-3-甲基咪唑氯盐（含水量小于0.3%）由实验室合成。反应过程中使用超纯水（Milli-Q，Millipore 0.22μm）和牛血清蛋白（AR，纯度98%）。培养普通小球藻（Chlorella sp）时，使用BG11培养基，并在120°C高压灭菌锅中灭菌25分钟，待冷却后备用。其他化学药品均应为分析纯，使用前无需进一步提纯。(1) Synthesis of Cellulose-C1: Dissolve 1 g of cotton pulp in 24 g of AmimCl at 80°C, then add 2.4 g of 2-chloropropionyl chloride while stirring at an ice-water bath. After uniform mixing, transfer to a 40°C oil bath for 2 hours. Upon completion, add ethanol to terminate the reaction and precipitate the sample using ethanol. Filter using a sand core funnel, wash three times, and dry in an 80°C vacuum oven. Dissolve the dried sample in DMSO, precipitate again with ethanol, filter, wash three times, and finally dry in an 80°C vacuum oven to obtain Cellulose-C1 with varying degrees of substitution. (2) Synthesis of Cellulose-BimCl: Dissolve 1 g of Cellulose-Cl in DMF, add 2.5 g of N-butylimidazole, and reflux at 80°C for 24 hours. After reaction completion, precipitate with acetone, filter using a sand core funnel, wash three times, and dry in an 80°C vacuum oven. Dissolve the dried sample in DMSO, precipitate again with acetone, filter, wash three times, and dry in an 80°C vacuum oven to obtain Cellulose-BimCl with varying degrees of substitution. (3) Synthesis of Cellulose-BimPFO: Dissolve 1 g of Cellulose-BimCl in water, add 2.7 g of sodium perfluorooctanoate for anionic exchange. After 12 hours, wash with ultrapure water at least three times and dry in an 80°C vacuum oven. Dissolve the dried sample in DMSO, precipitate again with ultrapure water, filter, wash three times, and dry in an 80°C vacuum oven to obtain Cellulose-BimPFO with varying degrees of substitution.将Cellulose-BimPFO溶解于DMF中，得到 $5-10~\\mathrm{wt}\\%$ 的溶液，然后将其倒入聚四氟乙烯模具中，放置在 ${80}^{\\circ}{\\bf C}$ 热台上4h，用水辅助将膜揭下。随后放置到 ${\\bf80}^{\\circ}{\\bf C}$ 真空烘箱中 $24\\mathrm{h}$ ，烘干以备测试。本章中通过均相衍生法，制备了一种醋酸纤维素1-丁基咪唑氯盐，将氯化铁、氯化铜、氯化钴和氯化镍等通过络合的方式引入到醋酸纤维素上制备了一种对紫外屏蔽和蓝光具有屏蔽作用的材料。醋酸纤维素（CA）在 $80^{\\circ}C$ 真空烘箱干燥 $24$ 小时。使用的其他试剂包括 2-氯丙烯酰氯（纯度 $97\\%$ 直接使用）、N-丁基咪唑（纯度 $98\\%$ 直接使用）、双三氟甲磺酰亚胺锂盐（纯度 $98\\%$ 直接使用）、以及多种氯化盐（均为纯度 $98\\%$ 直接使用）和超纯水（Milli-Q，Millipore $0.22\\upmu\\mathrm{m}$）。其他化学药品均从北京国药化学试剂公司获得，使用前无需进一步提纯。1. 合成醋酸纤维素2-氯丙酸酯（CA-CI）：将CA（4.1mmol）溶解在N,N-二甲基甲酰胺（DMF）中，在0°C下将13.7mmol的2-氯丙酰氯添加到CA/DMF溶液中，随后转移到40°C油浴中，反应3h；将所得均匀溶液加入乙醇中以终止反应，并用乙醇过滤沉淀物，洗涤三次，最后在真空烘箱中80°C干燥24h以获得CA-Cl。  \\n2. 合成醋酸纤维素1-丁基咪唑氯盐（CA-BimCI）：将CA-Cl（3.1mmol）溶解在DMF中，添加14.0mmol的1-丁基咪唑，反应在80°C油浴中进行24h；将所得溶液加入乙醇中以终止反应，过滤沉淀物，洗涤三次，最后在80°C真空干燥24h，以获得CA-BimCl。  \\n3. 合成醋酸纤维素1-丁基咪唑氯化金属盐（CA-BimX）：将CA-BimCI（2.5mmol）溶于水中，滴加所需金属氯化盐的水溶液，反应体系在室温搅拌12h；用超纯水透析2天，冻干后在80°C下真空干燥24h，以获得CA-BimX。合成CA-C1的步骤如下：利用可设计的纤维素结构，首先进行均匀且可控的酯化过程，合成纤维素醋酸纤维素2-氯丙酸酯（CA-C1）。接着，通过亲核取代反应，将CA-CI与1-丁基咪唑反应，获得阳离子化纤维素衍生物CA-BimCl。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/└н┬№.json b/task2/task2-paper-info/└н┬№.json
new file mode 100644
index 0000000..36a1e9d
--- /dev/null
+++ b/task2/task2-paper-info/└н┬№.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The study aims to characterize the kinetics of thermoplastic polyurethane (TPU) polymerization in situ using Raman spectroscopy. Specifically, the focus is on acquiring conversion versus time data from an uncatalyzed polyester-based TPU formulation. The data obtained through Raman spectroscopy will be compared with kinetics parameters from differential scanning calorimetry (DSC) experiments.The synthesis of hydrophilic polymers involves the use of a hydroxyl terminated poly(butylene adipate) (PBA) oligomer with a number average molecular weight of approximately 2000 g/mol as the soft segment. The hard segments are derived from 4,4'-diphenylmethane diisocyanate (MDI) and 1,4-butanediol (BDO), with MDI being supplied by Bayer and BDO supplied by ARCO chemical company.In preparation for TPU synthesis, PBA was melted and dried under a vacuum at 100°C for a minimum of 4h while BDO was dried over type 3A molecular sieves at room temperature for at least 2 weeks prior to synthesis. MDI was used as received but stored under a vacuum at 0°C until required for synthesis. The TPU was synthesized with a stoichiometric ratio of hydroxyl to isocyanate functionality at unity, using equimolar quantities of PBA and BDO. The TPU contained 76.84% PBA, 3.536% BDO, and 19.62% MDI by mass. The polymerization was performed using a 'one-shot' process, where dewatered PBA (heated to 100°C), BDO (at room temperature), and MDI (at room temperature) were gravimetrically metered into a 500ml polypropylene beaker and vigorously hand mixed for 15s. Upon thorough mixing of all TPU reactants, samples were removed and prepared for immediate kinetic analysis.To synthesize hydrophilic polymers with functional groups, prepare a TPU reactant mixture and place it between fused quartz cover slips to form samples approximately 1.0 mm in thickness. Use a hot stage preheated to isothermal polymerization temperatures of 100, 120, 140, and 160°C. Align the sample with the focused Raman laser beam and measure the kinetics of polymerization using a Kaiser Optical Systems Series 5000 Holoprobe Raman spectrometer equipped with a 785 nm GaAlAs diode laser. Conduct measurements with a 30-second exposure time every 30 seconds for a total duration of 60 minutes. Process all Raman spectra with chemometric techniques using Grams/386 software for quantitative analysis, including baseline subtraction and normalization using an internal standard related to the MDI aromatic ring breathing/stretching modes.TPU reactant mixture samples were carefully weighed to 10±2 mg and sealed in aluminum hermetic pans and lids. Samples were placed into a DSC preheated to a specific isothermal temperature. Heat flow resulting from the exothermic TPU polymerization reaction was measured as a function of time for 60 minutes. After isothermal polymerization, samples were quenched to 0°C at a cooling rate of -100°C/min and subjected to a temperature scan from 0 to 200°C at a heating rate of 20°C/min. Isothermal polymerization temperatures of 100, 120, 140, and 160°C were used to evaluate all kinetic parameters.The synthesis of hydrophilic polymers with functional groups involves the following steps: 1. Prepare a reactant mixture that includes diisocyanates, such as MDI, and polyols at a ratio conducive to urethane formation. 2. Conduct polymerization at a controlled temperature of 120°C. 3. Monitor the reaction progress using Raman spectroscopy by measuring the peak intensities of characteristic functional groups at specific Raman shifts, particularly focusing on isocyanate and urethane bands. 4. Record Raman spectra at time intervals, specifically at 1 minute, 30 minutes, and 12 hours to observe changes in band intensities. 5. Utilize the peak height of the MDI band at 1530 cm-1 as an indicator of unreacted isocyanate groups for quantitative analysis of polymer conversion. 6. Calculate the conversion of the polymer using the formula α(t) = (I0 - I(t)) / I0, where I(t) denotes the peak height at time t and I0 represents the peak height at zero conversion.The synthesis of hydrophilic polymers involves following a step growth polyaddition reaction. Initially, the isocyanate (NCO) functional groups in the TPU reactant mixture are prepared and mixed. The temperature of the reaction is monitored, and the enthalpic heat of reaction is calculated using a differential scanning calorimetry (DSC) to determine the conversion over time. The enthalpic heat lost during sample preparation and loading is considered to ensure accurate measurement. The initial conditions of the reaction are set, ensuring a homogeneous mixture, and the polymerization progresses under controlled heating conditions. The heat capacity is calculated as a linear function of temperature to yield the necessary thermal data during polymerization. Maximum temperature rise correlates with the conversion of the reaction and is combined with heat flow measurements from attenuated total reflectance (ATR) experiments to derive the overall reaction heat. This process allows for the quantitative assessment of conversion as a function of both time and temperature during the synthesis of hydrophilic polymers with functional groups."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/└√╙├PubChem╜°╨╨╨щ─т╔╕╤б.json b/task2/task2-paper-info/└√╙├PubChem╜°╨╨╨щ─т╔╕╤б.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/└√╙├PubChem╜°╨╨╨щ─т╔╕╤б.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/└√╙├╔ю╢╚╤з╧░╥¤╡╝╡─╥┼┤л╦у╖и╠╜╦ў▓─┴╧╔ш╝╞┐╒╝ф.json b/task2/task2-paper-info/└√╙├╔ю╢╚╤з╧░╥¤╡╝╡─╥┼┤л╦у╖и╠╜╦ў▓─┴╧╔ш╝╞┐╒╝ф.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/└√╙├╔ю╢╚╤з╧░╥¤╡╝╡─╥┼┤л╦у╖и╠╜╦ў▓─┴╧╔ш╝╞┐╒╝ф.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/┤·▒э│╔╣√5-nanomaterials.json b/task2/task2-paper-info/┤·▒э│╔╣√5-nanomaterials.json
new file mode 100644
index 0000000..fef9efe
--- /dev/null
+++ b/task2/task2-paper-info/┤·▒э│╔╣√5-nanomaterials.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Prepare a hybrid super-hydrophilic polymer hetero-network (HN) by combining acrylic resin and polyurethane acrylate. Utilize UV curing to construct P-C bonds through a UV-initiated free radical reaction, ensuring a covalent linkage between BP nanosheets (BPs) and the polymer matrix, thereby embedding BPs firmly into the polymer structure.The synthesis of hydrophilic polymers with functional groups involves the following steps: First, prepare the monomer solution by dissolving the desired hydrophilic monomers in a suitable solvent. Next, introduce functional groups by incorporating specific functionalized monomers or reactants into the solution. Maintain the reaction conditions under controlled temperature and stirring for a specified duration to allow polymerization. After polymerization, purify the resulting polymer by dialysis or precipitation to remove unreacted monomers and solvents. Finally, characterize the functionalized hydrophilic polymers using techniques such as NMR, FTIR, or GPC to confirm the presence and functionality of the desired groups.Hydrophilic polymers with functional groups were synthesized using polyethylene glycol 2000 (PEG 2000), isophorone diisocyanate (IPDI), and pentaerythritol triacrylate (PETA) as the main components. The synthesis involved the use of dibutyltin dilaurate (DBTDL) as a catalyst. Acrylic acid (AA), 2-hydroxyethyl methacrylate (HEMA), and sulfobetaine methacrylate (SBMA) were integrated as functional group sources. The reaction was initiated using azodiisobutyronitrile (AIBN) or diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide (TPO) as photoinitiators. All chemicals were used without further purification.Synthesis of polyurethane acrylate (PUA): Dissolve 2 g PEG 2000, 6 mg MeHQ, 3 mg BHT, and 3 mg DBTDL in 20 ml ethyl acetate to obtain the dropping solution. Add 444 mg of IPDI into a three-port flask, and then add the dropping solution to the three-port flask for 2 h at room temperature with stirring at 200 rpm. Carry out the reaction at 40 °C for 6 h. Then add 500 mg PETA and continue the reaction for 3 h at 80 °C. After filtration and solvent evaporation, dry the residue in a vacuum to yield a colorless oil. Synthesis of P(AA-HEMA-SBMA) acrylic resin (PAHS): In a three-port flask, dissolve 3.6 g AA, 6.5 g HEMA, 14 g SBMA, and 24 mg AIBN in 30 ml ethyl acetate and carry out the reaction at 80 °C for 6 h. After filtration and solvent evaporation, dry the residue in a vacuum to yield a white powder. Synthesis of super-hydrophilic polymer hetero-network coating (PUA/PAHS HN): Prepare the UV-curable solution by dissolving the photo initiator TPO and the obtained PUA, PAHS in 2-propanol with about 40% total solid content. Spin-coat the UV-curable solution on a plastic substrate and then follow by UV irradiation (broadband, 400 mj/cm²) to obtain a cured PUA/PAHS/BPs HN coating.The preparation method for samples involved dispersing the UV-cured coating in ethanol (EtOH) and dropping it onto silicon (Si) substrates for investigation. For cross-section samples, the samples were pasted onto the cross-section sample table after freezing extraction.The polymer HN was synthesized by combining polyurethane acrylate (PUA) and acrylic resin (poly (acrylic acid (AA)-2-hydroxyethyl methacrylate (HEMA)-sulfobetaine methacrylate (SBMA), denoted as PAHS), using UV-initiated cross-linking. The PUA was prepared through the polymerization of polyethylene glycol (PEG) with diisocyanate and was end-capped with pentaerythritol triacrylate (PETA). PAHS was synthesized via radical polymerization of three hydrophilic monomers: AA, HEMA, and SBMA. A UV-curable solution was then created by dissolving the obtained PUA, PAHS, and BP nanosheets in a solvent."
+}
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diff --git a/task2/task2-paper-info/┤є╣ц─г╗п╤з╙я╤╘▒э╩╛▓╢╫╜╖╓╫╙╜с╣╣╙ы╨╘╓╩ zh.json b/task2/task2-paper-info/┤є╣ц─г╗п╤з╙я╤╘▒э╩╛▓╢╫╜╖╓╫╙╜с╣╣╙ы╨╘╓╩ zh.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/┤є╣ц─г╗п╤з╙я╤╘▒э╩╛▓╢╫╜╖╓╫╙╜с╣╣╙ы╨╘╓╩ zh.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/┤є╣ц─г╗п╤з╙я╤╘▒э╩╛▓╢╫╜╖╓╫╙╜с╣╣╙ы╨╘╓╩.json b/task2/task2-paper-info/┤є╣ц─г╗п╤з╙я╤╘▒э╩╛▓╢╫╜╖╓╫╙╜с╣╣╙ы╨╘╓╩.json
new file mode 100644
index 0000000..b965afb
--- /dev/null
+++ b/task2/task2-paper-info/┤є╣ц─г╗п╤з╙я╤╘▒э╩╛▓╢╫╜╖╓╫╙╜с╣╣╙ы╨╘╓╩.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The article does not provide a specific experimental protocol for the synthesis of hydrophilic polymers with functional groups."
+}
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diff --git a/task2/task2-paper-info/┤╙═и╙├╨═╡╜╫и╝╥╨═г║╗п╤з┴ь╙Є┤є╨═╙я╤╘─г╨═╡─╫█╩Ў.json b/task2/task2-paper-info/┤╙═и╙├╨═╡╜╫и╝╥╨═г║╗п╤з┴ь╙Є┤є╨═╙я╤╘─г╨═╡─╫█╩Ў.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/┤╙═и╙├╨═╡╜╫и╝╥╨═г║╗п╤з┴ь╙Є┤є╨═╙я╤╘─г╨═╡─╫█╩Ў.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/═и═∙╧┬╥╗┤·╢р╧р┤▀╗п╝┴г║╗·╞ў...╓·┴ж▒э├ц╖┤╙ж╨╘╘д▓тги╙в╬─гй_┴ї╨╛╤╘.json b/task2/task2-paper-info/═и═∙╧┬╥╗┤·╢р╧р┤▀╗п╝┴г║╗·╞ў...╓·┴ж▒э├ц╖┤╙ж╨╘╘д▓тги╙в╬─гй_┴ї╨╛╤╘.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/═и═∙╧┬╥╗┤·╢р╧р┤▀╗п╝┴г║╗·╞ў...╓·┴ж▒э├ц╖┤╙ж╨╘╘д▓тги╙в╬─гй_┴ї╨╛╤╘.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/═и╣¤╗·╞ў╤з╧░╘д▓т╛█╡ч╜т╓╩╢р▓у─д╡─═┐▓у║ё╢╚.json b/task2/task2-paper-info/═и╣¤╗·╞ў╤з╧░╘д▓т╛█╡ч╜т╓╩╢р▓у─д╡─═┐▓у║ё╢╚.json
new file mode 100644
index 0000000..84d8b3f
--- /dev/null
+++ b/task2/task2-paper-info/═и╣¤╗·╞ў╤з╧░╘д▓т╛█╡ч╜т╓╩╢р▓у─д╡─═┐▓у║ё╢╚.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Layer-by-layer (LbL) deposition method of polyelectrolytes involves successive deposition of polycations and polyanions onto the surface of a material, with a rinsing step after each deposition. Various methods can be employed for the build-up of LbL coatings, including dip-coating, spin-coating, and spraying, with dip-coating being the most commonly used but also time-consuming. To develop coatings, different parameters such as temperature, pH, and ionic strength must be controlled. The formation of coatings requires careful selection of polyelectrolytes to ensure desired properties, and evaluation methods such as quartz crystal microbalance with dissipation monitoring (QCM-D), atomic force microscopy (AFM), confocal microscopy, or ellipsometry may be used to assess film thickness.To synthesize hydrophilic polymers with functional groups, prepare polycations (PAR30 and chitosan variants) and polyanions (28 different polymers) at 0.5 mg/mL in either Tris/NaCl buffer (10 mM Tris, 0.15 M NaCl, pH 7.4) for PAR30 or sodium acetate buffer (70 mM sodium acetate, 80 mM NaCl, pH 5) for chitosan. Clean a SiO2 coated crystal for 30 min with 2% Hellmanex, rinse with water, and perform final cleaning with 1 M HCl for 10 min, followed by rinsing with water. Deposit the chosen polycation onto the crystal for 5 min, then rinse with the respective buffer for 5 min. Repeat the deposition and rinsing steps for a total of 8 bilayers at a flow rate of 250 µL/min."
+}
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diff --git a/task2/task2-paper-info/═и╣¤╗п╤з╠╪╨╘╔ш╝╞╫╘╫щ╫░╢■ы─╦о─¤╜║╝░╞ф╗·╞ў╤з╧░╤╨╛┐.json b/task2/task2-paper-info/═и╣¤╗п╤з╠╪╨╘╔ш╝╞╫╘╫щ╫░╢■ы─╦о─¤╜║╝░╞ф╗·╞ў╤з╧░╤╨╛┐.json
new file mode 100644
index 0000000..63ca7ae
--- /dev/null
+++ b/task2/task2-paper-info/═и╣¤╗п╤з╠╪╨╘╔ш╝╞╫╘╫щ╫░╢■ы─╦о─¤╜║╝░╞ф╗·╞ў╤з╧░╤╨╛┐.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Develop a peptidelike chemical library based on a Ugi four-component reaction for screening compounds that can form hydrogels. Select hydrogels for characterization using a rheometer and transmission electron microscopy (TEM). Culture selected hydrogels with an adherent cell line. Generate the chemical features of the chemical library and develop a machine learning method to link these features to self-assembly properties, predicting gel formation ability at neutral pH without divalent or trivalent metal ions."
+}
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diff --git a/task2/task2-paper-info/═┐┴╧╚▄╝┴╡─╜щ╔▄.json b/task2/task2-paper-info/═┐┴╧╚▄╝┴╡─╜щ╔▄.json
new file mode 100644
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+++ b/task2/task2-paper-info/═┐┴╧╚▄╝┴╡─╜щ╔▄.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
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diff --git a/task2/task2-paper-info/═┐┴╧╣д╥╒ги╡┌╦─░цгй╔╧▓с.json b/task2/task2-paper-info/═┐┴╧╣д╥╒ги╡┌╦─░цгй╔╧▓с.json
new file mode 100644
index 0000000..90a2f18
--- /dev/null
+++ b/task2/task2-paper-info/═┐┴╧╣д╥╒ги╡┌╦─░цгй╔╧▓с.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "通常将它们溶解在适当溶剂体系中配成树脂溶液制备涂料，通过溶剂蒸发后固化成膜。对于热固性或交联型树脂，在成膜过程中与外加固化剂反应交联成膜，生成的涂层不溶、不熔。为了制备单组分热固性涂料，可以将树脂和固化剂做成互不相溶的两个相，在成膜时借助加热或其他方式使二者混溶反应成膜。牛口性树脂乳液及其他水分散型树脂一般需在聚合后用水稀释，并确保其化学结构中引入亲水基团。在开发水性丙烯酸自交联型乳液和涂料过程中，采用羟甲基丙烯酰胺、含羰基丙烯酸单体、不饱和硅氧烷等功能单体改性等多种手段。以不饱和聚酯、丙烯酸或烯丙基化的环氧、聚氨酯、聚酯低聚物及环氧化合物与活性稀释剂等组成的成膜物在自由基引发剂作用下，或者紫外线、电子束等高能光束引发光敏剂分解产生的自由基或活性离子作用下发生聚合交联成膜。松香主要由各种树脂酸组成，树脂酸含有三环骨架结构，含有两个双键和一个羧基两种活性中心，通过与羧基的酯化、中和及与双键的加成、氢化、歧化、聚合等，可改变松香的理化性能，拓展其应用领域，这些经过改性的产物，统称为改性松香树脂。使用松香作为主要原料，结合多元醇（如甘油或季戊四醇）、醛类（如甲醛）、多元酸（如顺丁烯二酸酐）、和酚类（如苯酚、双酚A或对叔丁酚），以及催化剂（如次磷酸、乌洛托品、氧化锌）进行改性。生产设备应根据所生产松香树脂的类型来建设。采用不锈钢制作的反应釜，使用浆式搅拌（附刮沫器)。用高位槽滴加丙烯酸单体和分水器来维持回流。改性松香树脂的合成需在高温和适当的催化剂条件下进行，以便顺利实现羧基的酯化反应。将树脂酸与金属氧化物或氢氧化物在高温下中和，生成树脂酸的金属盐（如松香钙皂）。在生产时加入少量碳酸锂以改善成品的透明度。注意事项包括：加石灰前应开启防爆管，防止加石灰时突然溢锅；维持温度不宜超过230°C，过高容易造成树脂胶结，若发现树脂有结锅的趋势，可立即投入少量松香来避免结锅；尽量使用新制得的熟石灰。吸人熔化后的松香，开动搅拌；在160℃以下，均匀地加入熟石灰，加完后维持1h。维持结束，升温到约220℃后维持1h。取样，进行终点控制（软化点、酸值)；若酸值未到则继续维持反应。合格后，放料、冷却、包装。1. Prepare a reaction vessel for esterification by adding polyols to rosin. 2. Use commonly used polyols such as glycerol or pentaerythritol. 3. For glycerol esters, control the addition rate to avoid foam overflow. For pentaerythritol, add slowly and evenly to avoid caking on vessel walls. 4. Heat the mixture to a specified temperature and maintain reduced pressure to remove impurities like oxidized rosin and turpentine. 5. Once purified, cool the mixture and proceed with esterification using the polyols. 6. Use appropriate catalysts to ensure the reaction proceeds smoothly. 7. Monitor acid value and supplement with additional polyol if necessary.1. 吸进松香、开动搅拌，投入甘油（加料时应注意泡沫上升情况，防止溢锅)，同时开启横、直冷凝器冷却水。在140℃以下，加人300与168抗氧剂。 2. 维持15min，升温至200℃后，维持1h。 3. 维持结束，升温到270℃后维持6h，关闭直冷凝器冷却水，在维持温度下抽真空2h。 4. 取样，进行终点控制（软化点、酸值)；若酸值未到则继续维持反应。 5. 合格后，放料、冷却、包装。甲醛和酚类的缩合产物与松香加成后，并与多元醇酯化改性而成的合成树脂。1. 吸进松香、开动搅拌，在 150°C 以下，迅速加入顺酐，温度会自升，并维持1.0h；打开直冷凝器、横冷凝器冷却水，缓慢加入甘油；加料时应注意泡沫上升情况，防止溢锅。\\n2. 加入甘油，不要升温，在 140°C 以下，加入次磷酸和300抗氧剂；然后升温至200°C，并在200°C维持2.0h。\\n3. 维持结束，升温到270°C维持4.0h，关闭直冷凝器冷却水，然后抽真空2h。\\n4. 取样，进行终点控制（软化点、酸值）。\\n5. 合格后，放料、冷却、包装。松香、顺酐、乙二醇在一定温度与条件下进行酯化反应，然后在引发剂的作用下与丙烯酸单体进行共聚反应。为提高产品的性能，反应后期需将未反应的多元醇从产物中除去，选择能够与后加入的二甲苯形成共沸的多元醇，如乙二醇或1,3-丙二醇。在进行酯化反应时采用溶剂法，并加入酯化催化剂以加快反应。滴加乙二醇和丙烯酸单体时需控制好滴加速度及温度，确保水和残余乙二醇顺利脱尽。生产固体成品前需消耗掉补加的引发剂，并在降温后减压脱溶剂。1. 投入熔化后的松香，开动搅拌；在150℃以下，迅速加入顺酐、TNPP和二甲苯；等温度稳定后维持在180~185℃。 2. 滴加乙二醇，控制滴加温度180~185℃，滴加时间2~3小时。 3. 滴加完成后，在180~185℃维持反应，并取样测酸值，等酸值≤50后，结束维持。 4. 加人二甲苯，回流，脱出酯化反应生成水和残留的乙二醇。 5. 滴加混合好的甲甲酯、苯乙烯、过氧化二叔丁基，控制滴加温度135~140℃，滴加时间8~10小时。 6. 滴加完成后，在135~140℃维持2~4小时，补加过氧化二叔丁基，继续维持反应并取样，直至反应到规定的黏度为止。 7. 减压脱尽溶剂后，冷却后造粒包装或加人适当的溶剂，稀释到规定的浓度后包装。采用苯酚的酚醛树脂，采用的缩合反应催化剂有六亚甲基四胺和熟石灰。使用六亚甲基四胺的酚醛树脂用于生产酚醛胶黏剂时，胶黏剂性能要好。采用双酚A、叔丁基苯酚的酚醛树脂主要用于生产胶印油墨，进一步提高树脂性能需使用辛基酚、壬基酚、十二烷基酚等碳链较长的烷基酚以改善树脂的溶解性、黏度和分子量。配方实例包含多种原料和用量，酚醛漆料由210酚醛树脂与桐油等干性油熬炼而成。将松香和顺酐混合，进行加成反应以消失共轭双键，确保化学性质稳定，降低氧化变色倾向；然后采用多元醇进行酯化，调整酯化产物的酸值和软化点。根据所选多元醇和顺酐加成量的不同，调节产品的性能以适应不同应用领域。进行醇解反应，将油（甘油三脂肪酸酯）与醇共热，选择合适的多元醇如甘油或季戊四醇，可选择加入催化剂（如黄丹或氢氧化锂）或不加入。反应在较高的温度下进行，利用羧基重新分配现象生成包含不同数量比的油、甘油一酸酯、甘油二酸酯的混合物。该步骤是醇酸树脂制造的重要部分，确保生成的不完全酯能够溶解于苯二甲酸酐与甘油的混合物，形成均相反应。油和其他的有机酸共热反应，与醇解相似，有过量的羧基存在，将产生羟基重分配现象。酸解法多在间苯二甲酸制造醇酸树脂时使用。进行醚化反应，将两个含羟基的化合物在200至250摄氏度的温度下反应，过程中需要有酸或碱的存在，以促进醚键的形成。反应中两个羟基缩合脱除一个水分子，形成醚化产物。酯化反应在常温下进行缓慢，通常醇酸树脂酯化温度在 180∼240°C 之间，酯化速率和程度与酸和醇的结构有关。伯醇反应快且有最高的平衡值；仲醇较慢；叔醇反应最慢、产率也低。催化剂可以加快酯化速率，但不能改变酯化程度。选择合适的酸，如苯二甲酸酐，与多元醇反应形成半酯，在较低温度下进行反应。调整偏苯三甲酸在醇酸树脂中的用量，可制得含有剩余羧基的醇酸树脂，并进行中和成铵盐以制成水性醇酸树脂。The synthesis of hydrophilic polymers containing functional groups involves a condensation reaction between at least two monomers, each with functional groups, resulting in a polymer and a low molecular weight byproduct, typically water. The reaction is characterized by the use of polyols and polyacids that undergo co-condensation, often modified by fatty acids. The functional groups relevant to this process may include —COOH, -OH, —NCO, and —C—C—. It is important for the reacting monomers to have the same number of reactive functional groups, e.g., a dicarboxylic acid reacting with a diol, resulting in an ester linkage while retaining reactive carboxyl and hydroxyl groups for further reactions. This process leads to the stepwise formation of polymer chains, with molecular weight increasing over time.The experimental protocol for the synthesis of hydrophilic polymers with functional groups involves the following steps: 1. Determine the type of oil and its oil content, as well as the kappa value, which can be calculated using the formula K = m0/eA. 2. Specify the amount of polyol (such as glycerol or pentaerythritol) to use in excess. 3. Calculate the total equivalent number of acids (eA) and the equivalent numbers for any additional components (for example, eA1 for the oil and eA2 for benzenedicarboxylic anhydride) using the specified ratios. 4. Adjust the formula by considering the constants for the chosen raw materials, ensuring the reaction doesn't lead to gelation while achieving the desired esterification degree and hydroxyl value. 5. Perform the reaction under appropriate conditions to maintain the stoichiometry and avoid excessive loss of reactants. 6. Monitor the acid value, aiming for a target value around 8 mg KOH/g for typical alkyd resins.醇酸树脂的主要原料是多元醇、多元酸、植物油（脂肪酸），在生产过程中还需加少量助剂，并用适当溶剂兑稀成液体树脂。多元醇的合成可以通过将饱和烃类分子上的氢原子用羟基（-OH）取代而实现。根据羟基连接的碳原子上的氢原子数量，可以合成伯醇、仲醇和叔醇。具体的操作包括：选择适当的烷烃原料，采用适合的化学反应方法（如酯化反应）引入羟基，进而制备需要的多元醇。常规法将全部反应物同时加入反应釜内，在不断揽拌下升温，在规定温度(200∼250°C)下保持酯化，中间不断地定期测定酸值与黏度，直至达到规定要求时停止加热，将树脂溶解成溶液、过滤净化。高聚物法中，先将全部多元醇、苯二甲酸酐与一部分脂肪酸反应至低酸值，制成高分子量链状成分；然后加入其余量的脂肪酸再反应成为低酸值树脂。醇解在油与甘油的混溶相中进行，油、甘油和催化剂的比例为 1:(0.2~0.4):(0.04~0.2)，首先将油加入反应釜中，然后加入甘油和催化剂。加热至 200~250°C 进行醇解，反应在气体保护下进行，直到达到平衡点。醇解后稍微降温，添加苯二甲酸酐进行酯化。将季戊四醇与油以摩尔比1:1混合，加入催化剂，温度升高至醇解温度230至250℃，在惰性气体保护下不断搅拌，分批加入季戊四醇，搅拌均匀，避免空气进入。反应过程中观察形成的‘壳’和其熔化情况，保持反应至达到透明阶段。可通过测醇容忍度和电导率变化监控醇解进程。醇解完成后降温至180至200℃，加入苯二甲酸酐，升温至200至250℃进行酯化反应，定时取样测定酸值与黏度，达到要求后降温、兑稀、调整黏度、过滤、包装。将脂肪酸、油、多元醇、多元酸（苯二甲酸酐）一同加入反应釜中，升温至 $210\\sim$ $280^{\\circ}\\mathrm{C}$ 保持酯化至达到规定要求。试验表明，在以不同比例的亚麻油/亚麻油酸混合物与甘油在不同的催化条件下，进行醇解反应，把油的酯交换和脂肪酸的酯化结合起来，才能更好地完成O/F体系的醇解。$z_{\\mathrm{nO}}$ 不是酯交换的良好催化剂，但对酯化有良好催化作用；LiOH是典型的酯交换催化剂，对酯化没有明显的作用。对 $\\mathrm{{_{O/F}}}$ 体系来说， $z_{\\mathrm{nO}}$ 和LiOH的配合，才能取得最佳效果。在醇酸树脂的酯化工艺中，采用溶剂法进行脱水，使用3%至5%的二甲苯作为溶剂。脂肪酸法与多元酸、多元醇、脂肪酸同时投料升温进行酯化，进行共沸脱水。醇解法在完成醇解反应后，加回流二甲苯。反应釜上装有蒸汽加热的分馏柱，便于低沸点成分的分离和水的排出。需控回流的二甲苯温度在25℃至40℃之间，确保酯化反应的有效进行，并通过收集生成的水计量反应进程。改进工艺则使用填料塔、回流冷凝器和分水器，以更高的温度（110℃至125℃）返回反应釜，降低含水量并节省能源。1. 将豆油加人反应釜中，升温，通人 CO2 ，搅拌，在 45~55 min 内升温到 120℃，停止搅拌，加人氧化铅，开始搅拌。 2. 升温到220℃分批加入季戊四醇，再继续升温到240℃，保温醇解，至取样测定95%乙醇容忍度（25℃）为5作为醇解终点。在醇解时准备好油水分离器中垫底二甲苯及回流二甲苯。 3. 降温到220℃加入苯二甲酸酐，加完停止通人CO2，立即加入总加料量5%的二甲苯（约 108kg）。 4. 继续升温到200℃保温1h，升温到220℃保温2h，测酸值、黏度（黏度测定：样品：200#油漆溶剂油=10:7.3，以加氏管测定）。接近终点时每隔0.5h测一次。当黏度达到7s，酸值达到 18mgKOH/g 以下时，立即停止加热，抽入或放人稀释罐进行冷却。当温度降到 150℃ 以下，加人 200#油漆溶剂油 1567kg溶解成醇酸树脂溶液，再冷却至 60℃ 以下过滤。将豆油脚脂肪酸、松香、苯酐、顺丁烯二酸酐、甘油及回流二甲苯加入酯化釜中，升温至 150°C ，开动搅拌，升温至 175~180°C ，恒温回流1h。继续升温到 200~230°C ，回流酯化，待黏度、酸值合格后，抽人反应釜中。降温到 160°C 兑稀，在 80°C 过滤。顺丁烯二酸酐作为催化剂，用量为投料的 0.5%。将配方中原材料都加入反应釜中；在情性气体的保护下升温、搅拌；在 230∼250℃ 回流酯化反应；酸值达到 5∼10 mgKOH/g ，黏度（25℃ ，60% 固体分于 200# 油漆溶剂油中）达到加氏 J∼L 时停止反应，以油漆溶剂油溶解，制成66%固体分溶液。将配方中原料加入反应釜中，升温至回流温度 (173\\mathrm{\\sim}175^{\\circ}\\mathrm{C}) 并共沸分水。反应至加氏黏度 (60%固体分于油漆溶剂油中) 达到V～X时停止反应，用油漆溶剂油溶解，制成固体分为 60% 的溶液。先混合悬浮助剂和 30% 有机硅改性醇酸树脂A；再加入二氧化钛、炭黑、石棉粉、卵磷脂混合并分散至细度在 30μm 以下；加上述配方的其余原料混合，包装。将配方中全部原料装入溶剂法反应釜，在共沸脱水下升温至 250°C 。反应至固体树脂酸值达到 9~12 mgKOH/g ，加氏黏度（ 60% 于二甲苯中）为 Z_{1}~Z_{3} ，并在 200°C 热盘上胶化，时间为 19~22 s 。以二甲苯溶解成 68%~69% 溶液。在溶剂法反应釜中加入配方中硅醇和醇酸树脂并加热至回流以共沸脱水。于 200^{\\circ}C 热盘上反应至固化时间为11s，加氏黏度（60%二甲苯中）为 Z_{1}∼Z_{2} 。以二甲苯溶解，制成60%溶液。将豆油醇酸树脂、有机硅中间体及甲基丙烯酸-2-羟乙酯（HEMA）混合合成聚合物。使用未经任何提纯的HEMA、端羟基硅氧烷（Z-6018）、钛酸四异丙酯（TPT）等作为原材料。合成过程分为硅丙单体（SAM）的合成、豆油醇酸树脂的合成及硅丙豆油醇酸树脂的合成。将SAM通过化学反应加入豆油醇酸树脂中。通过C-NMR分析和FTIR测量确认反应形成SAM并与豆油醇酸树脂反应。最佳合成比例为30% SAM，以获得最佳的耐候性和力学性能。QM-657的合成是先由乙二醇与环戊二烯在强酸下反应，然后与甲基丙烯酸甲酯进行酯交换制得。酚醛树脂是由醛类和酚类在酸性或碱性条件下，通过缩合反应得到的合成树脂。醛与酚的摩尔比对于酚醛树脂的形成非常关键，一般酚醛树脂所采用的醛与酚摩尔比在1至2之间。如醛与酚的摩尔比小于1，则无法形成热固性酚醛树脂；若摩尔比大于1，则有利于形成羟甲基，促使缩合反应持续进行。合成酚醛树脂的原料包括醛和酚，若涉及萃取步骤需使用能够溶解酚醛树脂的溶剂，生产改性酚醛树脂时需使用相关的改性原料。酚醛树脂的合成是由酚与醛在酸性或碱性条件下进行，使用的催化剂包括熟石灰（氢氧化钙）、液碱（30%氢氧化钠）、乌洛托品（六亚甲基四胺）等作为碱性催化剂，或使用盐酸（30%）、草酸等作为酸性催化剂。生产改性酚醛树脂时，需要使用改性剂。对于松香改性酚醛树脂，需进行松香与酚醛产物的加成反应，并与多元醇（如甘油、季戊四醇）进行酯化。对于酚醛醚化浆，根据需要使用丁醇或乙醇与酚醛产物进行醚化反应。酚醛树脂的合成包括以下步骤：(1) 选择官能度至少为3的单体，如苯酚类和甲醛类，苯酚一般需具备三个可反应的官能团。甲醛作为二官能度单体参与反应。(2) 确保体系的平均官能度在反应中达到要求，通常控制为低分子量聚合物，通过进一步交联处理以形成三维网状结构的高强度聚合物。(3) 控制反应条件以防止凝胶化，特别是在碱催化条件下，需谨慎操作以避免黏度突然增加，导致反应达到凝胶点。根据Carothers方程式预测凝胶点，并根据官能团数量准确计算平均官能度。(4) 反应介质的酸碱性应适宜，pH值低于3或高于3均可触发反应，使用酸或碱催化以促进反应进行.在合成热塑性酚醛树脂时，首先在酸催化的条件下，甲醛和水分子反应生成主要的羟基化合物(CH2OH)-。随后，通过苯酚的对位亲电取代反应，生成对位的羟甲基苯酚。接着，这些羟基化合物快速与游离苯酚（主要在对位）缩合，生成二酚基甲烷。最后，在酚基邻位继续加成，形成线型聚合产物。在强酸性条件(pH<3)下，缩聚反应速率与氢质子（酸）的浓度成正比。需要注意的是，甲醛和苯酚的配比对最终产物的结构有显著影响，若甲醛过量可能导致支化结构的出现。使用锰、钴、镉、铬等金属碱盐作为催化剂，反应历程包括：甲醛 (水分子)→甲二醇 + 二阶金属离子 (催化剂)→与苯酚氧原子整合，并在邻位亲电取代→生成邻羟甲基苯酚 + 二阶金属离子 (催化剂)→继续与游离苯酚氧原子整合，并在邻位亲电取代→形成o,o'-二羟基二苯基甲烷→高邻位线型聚合产物。固化剂为15%六亚甲基四胺，固化温度为160℃。在催化剂的作用下，通过酚（常用的是对叔丁酚、苯酚等）与醛（最常用的是甲醛）的缩合反应，合成纯酚醛树脂；对于改性酚醛树脂，采用化学反应引入除酚、醛之外的其他成分，通过松香改性、醇改性、环氧改性、醇酸改性等方法，接入到酚醛树脂的分子链上。在碱性或酸性条件下，烃基取代酚与甲醛缩合反应达到一定程度后，终止反应，缩合产物经水洗后，采用先常压、后减压的方法脱去反应水，中控合格后出料。在碱性条件下，使用乌洛托品作为催化剂，采用一步法生产松香酚醛树脂，同时在酸性条件下，通过水洗并添加丁醇进行回流脱水反应，再进行酚醛醚化。生产酚醛树脂的主要设备为反应釜。松香改性酚醛树脂的制备需在高温下执行，反应温度达到270℃，一般采用高温导热油循环加热，反应釜的内置盘管与夹套通导热油，采用不锈钢制作，使用浆式搅拌器（附刮沫器），并配备直冷凝器、横冷凝器（附分水器）、真空泵等，底部出料。相较于松香改性酚醛树脂，纯酚醛树脂的反应温度不高，回收溶剂的最高温度不超过130℃，采用饱和蒸汽加热，不需要内置盘管，夹套可通蒸汽与冷却水，两个反应釜分别用于酚醛缩合与溶剂回收，均应采用不锈钢材料，并配备横冷凝器（附分水器）。酚醛醚化浆的制备在缩合反应后，需调整酸性并加入丁醇进行醚化反应，最终产出一定固体分的酚醛丁醇溶液，整个过程可在单釜内完成。吸进松香，放去真空，开动搅拌，加人苯酚、氧化锌、氧化镁、H促进剂，加料时应均匀地加人，防止溢锅。当温度下降至110℃以下时，打开直冷凝器冷却水，可逐渐加入甲醛，加人速度以不溢锅为原则；加完甲醛后在温度98~102℃维持3.5h。维持毕，关闭直冷凝器冷却水，开横冷凝器冷却水；同时升温脱水（升温时注意液面情况，防止溢锅），温度逐渐上升。当温度升至约220℃时，打开直冷凝器冷却水，逐渐加入甘油，加完后升温；升温至265℃，并保温维持4h。关闭直冷凝器冷却水，保持原温度并抽真空1h。取样，进行终点控制（软化点、酸值)；若终点未到则继续维持减压反应，若维持过程中酸值下降慢，难以达到产品的酸值，则应补加一定量甘油后继续维持，至酸值达到为止。合格后，放料冷却后包装。氨基树脂的合成涉及氨基化合物（含有-NH2官能团）与醛类（主要为甲醛）经缩聚反应，产物含有-CH2OH官能团。然后与脂肪族一元醇进行部分或全部醚化，获得氨基树脂。合成氨基树脂，最基本的原料是氨基化合物（主要为尿素、三聚氰胺、苯代三聚氰胺等)、醛类（主要为各种规格的甲醛)、醇类（主要为脂肪族一元醇，如甲醇、丁醇、异丁醇、乙醇、异丙醇等)。为使反应生成水顺利脱除，通常采用二甲苯作为带水剂来帮助脱水。合成氨基树脂的各种反应要在酸性或碱性条件下进行，需调整反应时的 pH。为降低和保证树脂的色泽，有时需要轻质碳酸镁来脱色。在碱性（氢氧化钾）条件下，以丁醇或丙二醇甲醚作溶剂，采用双氰胺和苯甲睛合成，经洗涤和干燥后得到苯代三聚氰胺成品。合成使用的苯甲睛国内采用甲苯胺氧化工艺来生产。在碱性条件下，以丁醇作溶剂，采用双氰胺和乙睛合成，经过洗涤和干燥后得到甲代三聚氰胺成品。将氨基化合物与甲醛反应，得到含有羟甲基的产物。使用脂肪族一元醇进行醚化改性，推荐使用甲醇、正丁醇、异丁醇等。反应过程中，使用二甲苯作为带水剂，利用其与水分层的特性，通过冷凝器将水分带出反应釜。1. 将甲醛投入反应器，使用10% NaOH调整pH至8，然后加入尿素，再调整pH至8。2. 升温至40-50°C维持，待溶液透明后，加入丁醇，升温至回流，全回流约0.5小时。3. 加入二甲苯与溶剂，再加入苯酐，继续升温至回流，全回流1.5小时。4. 关闭蒸汽，停止搅拌，静置1小时后，从反应锅底去废水。5. 开搅拌并升温至回流，开始脱水；水分逐渐脱去，温度会逐渐上升并在102-103°C时取样测试（容忍度、黏度）。6. 不断脱出溶剂，并进行终点控制，要求达到T-4黏度(25°C) 70-90秒，苯中清，容忍度1:(3-8)浑，7. 达到要求后，冷却到80°C以下，若树脂颜色偏深，可加入适量轻质碳酸镁脱色，最后过滤包装。a.先投入异丁醇、二甲苯、溶剂（无溶剂时不投)，然后加三聚氰胺和轻质碳酸镁，再投入甲醛；逐渐升温，当温度达到 80°C 时，停止加热，维持1.0h，再升温至回流。 b.全回流反应（约 92% ）3.0h后，关闭蒸汽，等回流停止后关搅拌。 c.加苯酐后开搅拌加热，并继续保持全回流反应2.0h。 d.关闭蒸汽、停止搅拌，静止1h后，从反应锅底部分去废水。 e.开搅拌，升温至回流，开始脱水，注意控制脱水速度；随着水分逐渐脱去，温度会逐渐上升，约 100~101°C 时取样第一次中控，整个回流脱水阶段一般控制在 4~5h 。 f.中控测试（容忍度、黏度)。此时测试结果一般为（25℃）： T-4黏度 30~40s 容忍度 1:(2~3）浑g.不断脱出溶剂，并进行终点控制，要求达到： T-4黏度（25C) 110~140s 苯中清 容忍度 11(4~9)浑 清 h.达到要求后，冷却到 80°C 以下（若树脂颜色偏深，可加入适量轻质碳酸镁脱色，一般加人量在 300~500g)，过滤包装。1. 合成六羟甲基三聚氰胺（HMM）: \\n   a. 先投入甲醛、去离子水，调节pH为8.8~9.0（使用10% NaOH）。 \\n   b. 加入三聚氰胺，逐步升温至约50℃，控制在60~65℃维持反应。 \\n   c. 当反应体系透明后，第二次调节pH为8.8~9.0，再维持60~65℃直到结晶析出。 \\n   d. 冷却，去除水分和未反应的甲醛，低温干燥至固体分390%。 \\n\\n2. 合成六甲氧基甲基三聚氰胺（HMMM）： \\n   a. 先投入甲醇，调节pH为1.8~2.0（使用盐酸）。 \\n   b. 加入HMM后升温至约40℃，维持40~45℃，第二次调节pH为2.5~2.8。 \\n   c. 维持醚化反应1小时，第三次调节pH为8.8~9.0。 \\n   d. 在减压条件下脱出过量甲醇和水分，控制温度不超过60℃。 \\n   e. 脱到甲醇完全被脱出为止。 \\n   f. 必要时，可加入丁醇稀释后进行过滤除盐。a. 先投入甲醛、甲醇，第一次调节 pH，用液碱调节要求控制 pH 为 8.8~9.0; b. 加入多聚甲醛后升温，升温度到约 70℃ 时停止升温，放热自升，并维持温度75～80℃，多聚甲醛溶解透明后，维持1.0h；维持结束后，冷却降温至 35℃ 以下; c. 第二次调节 pH，用液碱调节，控制釜内物料 pH 为 8.5~8.8; d. 加入三聚氰胺，逐步升温至约 50℃ 停止升温，温度因放热而自升，要勤取样，认真观察反应变化状况，维持反应控制在 58~63℃ 时进行; e. 反应物全部溶解后，继续维持 30~45 min，加入甲醇，第三次调节 pH，用盐酸调节，控制釜内物料 pH 为 4.8~5.0，同时控制温度 45~50℃; f. 反应物在盐酸作用下，物料逐渐透明，待完全透明后，维持 30 min，第四次调节 pH 用液碱调节，要求控制 8.8~9.0; g. 打开真空泵，在减压条件下将过量的甲醇和反应生成水脱出，要适当控制锅内温度（不超过 75℃); h. 当将过量的甲醇和反应生成水脱完后，加人丁醇，搅拌均匀后过滤包装.1. Add n-butanol, isobutanol, xylene, and solvent (omit solvent if not present), then add melamine and light magnesium carbonate, followed by formaldehyde. Gradually increase the temperature, and when it reaches 80°C, stop heating and maintain for 1.0 hour, then raise the temperature to reflux. 2. Conduct a complete reflux reaction (approximately 92°C) for 2.5 hours, close the steam, and stop stirring after reflux ceases. 3. After adding phthalic anhydride, start stirring and heating, and continue to maintain a full reflux reaction for 1.5 hours. 4. Close the steam, stop stirring, and let it stand for 1 hour, then drain the wastewater from the bottom of the reaction vessel. 5. Stir, increase to reflux temperature, and start dehydration, controlling the dehydration rate; as water gradually evaporates, the temperature will increase. Sample for the first time when the temperature reaches 100~101°C. The entire reflux dehydration stage is generally controlled within 4~5 hours. 6. Conduct mid-control testing (tolerance, viscosity). The typical test results are (25T) T-4 viscosity 30~40s tolerance 1:(2~3) cloudy. 7. Continuously remove solvent and conduct endpoint control, requiring T-4 viscosity (25°C) of 110~140s, clear in benzene, and tolerance of 1 (6~9) cloudy. If the tolerance is too high, increase the solvent removal speed (if excessively high, consider reducing pressure for solvent removal). 8. After meeting the requirements, cool down to below 80°C (if the resin color is too dark, an appropriate amount of light magnesium carbonate can be added to decolorize, generally 300~500g), then filter and package.氨基树脂反应过程中，有需要加热的工序，也有需要冷却的工序，反应进行到某一阶段，需要降温来快速减缓反应速度，以便进入另一阶段操作。氨基树脂反应温度，一般最高不超过120°C，采用饱和蒸汽加热的方式可满足生产工艺的要求。反应釜内搅拌的作用是保证参与反应的物料充分混合，使反应体系成为均相，氨基树脂在生产时黏度不大，通常采用桨式搅拌器或锚式搅拌器。氨基树脂生产过程中产生盐分，还有原料中可能带人的机械杂质，这些都要通过过滤去除，采用垂直网板式过滤机过滤，反应釜和过滤机之间安装袋式过滤装置以分离掉较大的固体颗粒。冷凝器收集冷凝下来的反应水和溶剂共沸物，上层溶剂经过回流管重新进入反应釜，水则从分水器底部排出。将氨基树脂与基体树脂进行共缩聚反应，主要依靠羟基、羧基、酰氨基等功能团的交联。羧基催化交联反应，同时氨基树脂的羟甲基、烷氧基甲基与基体树脂的羟基交联，羟甲基和亚氨基间发生自缩聚。提高交联温度和增大酸催化剂用量，可促进与羧基的反应。可选择合适的酸催化剂，如对甲苯磺酸吡啶盐，该酸催化剂在储存条件下不释放酸性，在交联固化条件下迅速释放酸性以促进反应。也可采用封闭型酸催化剂，如双肾基萘磺酸的衍生物，以适应不同的解封温度。采用部分甲醚化氨基树脂配合水性醇酸树脂，可生产水性氨基-醇酸烤漆。1. 将豆油、甘油投人反应釜，开揽拌加入氢氧化锂，加热升温，并在240～250℃醇解维持。 2. 醇解1h后，取样测试醇解是否完成，测试方法（样品：无水甲醇 =1:3 清/室温)，一般醇解时间不超过3h。 3. 醇解到终点后，冷却到 180°C 以下，加入苯酐、顺酐、次磷酸（与少量甘油混匀后加人）及回流二甲苯，打开直冷凝器及横冷凝器冷却水，升温至回流，进行酯化反应。 4. 酯化1h后，关闭直冷凝器冷却水，注意控制脱水及升温速度，最高酯化温度 ≤220°C。 5. 酯化反应2h后，开始取样测黏度、酸值。中控取样11. τg样品 +8,3g二甲苯要求控制加氏黏度 (25U) 15~19s酸值/(mgKOH/g) ≤11。 6. 酯化反应达到规定要求后，冷却到 180°C 以下放料到对稀锅中（对稀锅中先加入部分对稀二甲苯）；反应锅中加入剩余对稀二甲苯，洗锅后放入对稀锅中，揽拌均匀、复测调整黏度。符合要求后过滤包装。1.先将麻油、甘油投入反应锅，开搅拌加入苯酐、顺酐、次磷酸（与少量甘油混匀后加人）；加热升温并在 150~165°C 维持1h。\\n2.升温到 195~205°C 维持反应，维持到取样合格后冷却（取样在玻璃上，冷至室温后要达到透明，一般要 1~2h)，同时分去分水器中水。\\n3.冷却到 160°C 以下，加回流二甲苯，打开直冷凝器及横冷凝器冷却水，升温至回流；酯化反应1h后，关闭直冷凝器冷却水。\\n4.注意控制脱水及升温速度，最高酯化温度 ≤205°C。在实际控制时，当酸值符合要求时，黏度接近下限最理想，控制时应根据黏度上升情况，来放分水器中水，以免温度过高，黏度上升过快。\\n5.酯化反应2h后，开始取样测黏度、酸值。\\n6.酯化反应达到规定要求后，冷却到 180°C 以下放料到对稀锅中（对稀锅中先加入部分对稀二甲苯)；反应锅中加入剩余对稀二甲苯，洗锅后放入对稀锅中，搅拌均匀、复测调整黏度。符合要求后过滤包装。将桐油、亚麻油、甘油投入反应釜，开搅拌加入氢氧化锂，加热升温，并在 240~250℃ 醇解维持。醇解1h后，取样测试醇解是否完成，测试方法（样品：无水甲醇 =1:3 清/室温)，一般醇解时间不超过 3h。醇解到终点后，冷却到 180°C 以下，加人苯酐及回流二甲苯，打开直冷凝器及横冷凝器冷却水，升温至回流，进行酯化反应。酯化1h后，关闭直冷凝器冷却水，注意控制脱水及升温速度，最高酯化温度≤200℃。酯化反应2h后，开始取样测黏度、酸值。中控取样 11.0g 样品 +9.0g 二甲苯，要求控制加氏黏度（25℃） 10~11s，酸值 ≤ 11。酯化反应达到规定要求后，冷却到 180°C 以下放料到对稀锅中（对稀锅中先加入部分对稀二甲苯)；反应锅中加入剩余对稀二甲苯，洗锅后放入对稀锅中，搅拌均匀、复测调整黏度。符合要求后过滤包装。将十六酸、甘油、苯酐、三羟、苯甲酸、次磷酸、回流二甲苯投入反应锅，加热到能揽拌时开揽拌；同时打开直冷凝器及横冷凝器冷却水。逐步升温至回流，进行酯化反应；注意液面情况，泡沫可能较高，要防止溢锅，放出回流出水。注意控制脱水及升温速度，酯化反应1h后，关闭直冷凝器冷却水，并继续进行反应，最高酯化温度 ≤200 T。维持酯化反应3h后，开始取样测固体酸值（不兑稀）；控制酸值 25~30。冷却到 170 U 下面；打开倒门，快速投入偏苯三酸酐，升温，控制回流温度 ≤180 U。酯化反应0.5h后，开始取样测黏度、酸值。中控取样 11. 0g 样品 +9.0 g 二甲苯。要求控制加氏黏度（25℃） 15~19s酸值 20~25。酯化反应达到规定要求后，冷却到 180 ‰ 以下放料到对稀锅中（对稀锅中先加人部分对稀二甲苯)；反应锅中加入剩余对稀二甲苯，洗锅后放入对稀锅中，搅拌均匀、复测调整黏度。符合要求后过滤包装。将月桂酸、苯酐、三羟、顺酐、次磷酸、回流二甲苯投入反应锅，加热到能搅拌时开搅拌；同时打开直冷凝器及横冷凝器冷却水。逐步升温至回流，进行酯化反应；注意液面情况，泡沫可能较高，要防止溢锅，放出回流出水。注意控制脱水及升温速度，酯化反应1h后，关闭直冷凝器冷却水，并继续进行反应，最高酯化温度≤220°C。维持酯化反应3h后，开始取样测固体酸值（不对稀）；酸值7~10。达到规定要求后，冷却到180°C以下放料到对稀锅中（对稀锅中先加人部分对稀二甲苯)；反应锅中加入剩余对稀二甲苯，洗锅后放入对稀锅中，搅拌均匀、复测调整黏度。符合要求后过滤包装。将丙烯酸丁酯、甲甲酯、羟丙酯、BPO、α-甲基苯乙烯投入滴加槽，搅拌均匀后，待滴加用。将预聚物投人反应釜，升温至约130°C开始滴加单体，同时打开直冷凝器冷却水，控制滴加温度(130±2)°C；滴加时间控制为(75±15)min，不可过快或过慢。滴加完毕，在(130±2)°C维持1.0h，补加BPO。加完BPO后，升温至回流；回流1h后开始取样黏度。要求控制加氏黏度（25°C）20~25s。反应达到要求后，冷却到100°C以下放料到对稀锅中；揽拌均匀后复测黏度，符合要求后过滤包装。1. 投入新戊二醇、间苯二甲酸、对苯二甲酸、偏苯三酸酐、己二酸到反应釜，通氮气并升温。 2. 加热到能搅拌时，开动搅拌，投入单丁基氧化锡，打开直冷凝与横冷凝冷却水，反应出水后，停止通氮气。 3. 逐步升温，控制气相温度 ≤ 105°C，釜内温度最高 ≤ 235°C。 4. 当釜内温度达到 230°C 后，取样在玻璃上，冷却到室温后，要达到透明，透明后维持 30~45分钟。冷却到 180°C 以下，加人二甲苯。 5. 关闭直冷凝冷却水，边脱水边升温进行回流酯化反应，控制反应温度 ≤ 220°C。 6. 回流反应 1小时后，进行中控，检验黏度、酸值（注意反应后阶段黏度上升趋势）。取样比例 12: τg 样品 + 7.38稀释溶剂，要求控制加氏黏度 (25°C) 15~20秒，酸值/ (mgKOH/g) 2~5。 7. 中控符合要求后，冷却到 180°C 以下，放料到对稀釜中（对稀釜中先加入部分对稀溶剂）；反应釜中加入剩余的对稀溶剂，回流一段时间后放入对稀釜中，搅拌均匀后复测黏度，达到要求后过滤包装。丙烯酸树脂的合成包括使用丙烯酸酯类、甲基丙烯酸酯类及其他烯类单体进行共聚，确保树脂结构中含有羟基和羧基官能团，以便与氨基树脂交联形成膜。具体应用于汽车、摩托车、卷铝和油墨等行业。1. Add all monomers into the dropping funnel, then add BPO, stir evenly, and prepare for dropping. 2. Place xylene into the reaction kettle, heat to 85°C, turn on the cooling water of the direct condenser, and start adding the monomer at a controlled uniform rate. The dropping time is about 4.0 to 4.5 hours, with a dropping temperature of 85 to 90°C. 3. After completing the addition, maintain the temperature at 85 to 90°C for 2.0 hours; supplement with BPO and maintain at the same temperature for 1.0 hour. 4. Further supplement with BPO and maintain the same temperature for 1.0 hour, then take samples to observe the viscosity. 5. Turn off the cooling water of the direct condenser, turn on the cooling water of the horizontal condenser, heat to reflux, and maintain reflux for 1.0 hour. 6. Perform viscosity control, using a sample ratio of 5g sample + 2.5g xylene, to ensure that the kinematic viscosity (at 25°C) is greater than 20 to 25 seconds. 7. Once viscosity control meets the requirements, cool below 100°C, add xylene, stir evenly, re-measure viscosity, and filter and package when the requirements are met.氨基-环氧树脂的合成涉及将环氧树脂与羟甲基和烷氧基交联。使用下列原料进行配方：50%609环氧溶液441kg、锌黄粉89kg、锡铬黄粉18kg、锐钛型钛白粉224kg、超细滑石粉34kg，配漆时使用环氧底漆浆1000kg、醋酸丁酯74kg、乙二醇丁醚86kg、丁醚化脲醛树脂79kg、环已酮29kg、15%磷酸丁醇7kg。采用多元醇与多元酸经酯化反应合成涂料用聚酯树脂，开发特殊多元醇、多元酸及功能性树脂以满足不同应用领域的性能要求。合成饱和聚酯树脂的原料包括多元醇与多元酸。在合成过程中，使用溶剂以帮助脱水和稀释。为了加快反应速度，工业生产中通常加入催化剂。为了改善树脂的色泽，需加入抗氧剂。此外，生产改性饱和聚酯需要采用相应的改性剂，如合成脂肪酸、环氧树脂、有机硅材料、丙烯酸单体或树脂等。在合成亲水性聚合物时，选用含有伯羟基的多元醇，并依据性能要求选择适当的多元醇组合，以达到所需的聚酯树脂性能。常用的多元醇包括新戊二醇、季戊四醇、三羟甲基丙烷、1,4-环已烷二甲醇、1,6-已二醇等。这些多元醇具有不同的分子量、熔点和羟基含量，根据聚合物的应用需求设计配方，确保适当的柔韧性、硬度和耐水性。聚酯树脂通常由二元醇、三元醇和二元酸、三元酸等混合物通过缩聚反应制得。多元醇过量得到端羟基的聚酯树脂，可以用氨基树脂或多异氰酸酯进行交联。To synthesize hydrophilic polymers with functional groups via esterification, select an appropriate acylating agent such as carboxylic acids, acid anhydrides, or acyl chlorides based on the required reactivity. Use primary alcohols or phenols as the starting materials. Ensure to use tri-functional polyol like trimethylolpropane to maintain high reactivity and uniformity of hydroxyl groups. The general reaction scheme for the esterification process is R'OH + RCOZ → RCOOR' + H2O, where RCOZ represents the chosen acylating agent.通过酯化反应，利用各个单体（简单单元、小分子试剂）上固有的多个官能团（例如羟基和羧基）进行反应，连接成高分子聚合物（聚酯树脂)。聚合实施方法包括三种主要的反应方式：1) 熔融聚合，在单体和聚合物熔点温度以上进行，要求产品具有较高的热稳定性，并注意脱羧等副反应；2) 溶液聚合，称为回流聚合，在适当的溶剂中进行，能够平稳反应并减少副反应，但需考虑溶剂引起的污染和成本；3) 界面聚合，在两种溶剂的界面进行，要求单体具有极高的反应活性，且对官能团摩尔比没有要求。1. 投料：首先，根据工艺要求的顺序准确投料。将容易熔化的多元醇分为两份，分别投放到反应釜底部和上部，多元酸投放在物料的中间。2. 熔融反应：在无溶剂状态下进行酯化反应与缩聚反应。投料后，加热使多元醇熔化，形成均相，反应进行到一定阶段后，再加入回流溶剂，进入回流反应阶段。3. 回流反应：在有二甲苯等回流溶剂的情况下进行酯化反应与缩聚反应。溶剂沸腾使反应生成的水从反应物中分离，提高反应进程。4. 中控：取样检验反应是否达到规定要求，使用与生产时相同的稀释溶剂进行测试，以保证测试准确。5. 稀释：反应达到终点后，放料到稀釜中稀释，并加入强溶剂清洗反应釜内壁。6. 压滤：使用过滤方法将树脂中的杂质滤掉，保证聚酯树脂产品清澈透明。1. Prepare a reaction vessel and charge with polyols, polyacids, and a catalyst in a solvent-free condition. 2. Gradually increase the temperature to melt the substances while stirring slowly, then increase the stirring speed as melting progresses to achieve a homogeneous mixture. 3. Control the gas phase temperature during the melting reaction by dividing it into three segments: 99-102°C, 102-105°C, and 105-108°C to reduce sublimation losses. 4. Establish a maximum allowable temperature for the molten reaction and balance conditions through preliminary testing. 5. Introduce inert gases (such as CO2 or N2) into the reaction environment before the melting process begins to prevent oxidation by creating a barrier with the atmosphere. 6. After a certain degree of reaction, add a non-aqueous solvent to facilitate the removal of generated water during the backflow esterification phase, which helps control viscosity. 7. Monitor the temperature and maintain it below a set maximum during the backflow reaction, adjusting based on solvent addition and reaction parameters. 8. After the reaction, take a sample, add solvent according to the type and dilution ratio, mix well, and test for viscosity and acid value to ensure process control targets are met.To synthesize hydrophilic polymers with functional groups, use two-component systems involving diols and dicarboxylic acids for linear structures, or polyols and polyacids for branched structures. For linear saturated polyester resins, employ linear diols such as neopentyl glycol or 1,6-hexanediol, and dicarboxylic acids like isophthalic acid or adipic acid. For branched structures, utilize tri-functional or multi-functional acids or alcohols, such as trimethylolpropane or trimellitic anhydride, to create cross-linked networks. Further, to modify properties, introduce other chemical components through reactions outside of typical polyols or polyacids.1. 设计依据: 理解树脂所应用的涂料场合、性能要求以及成本要求，进行基础配方设计。 2. 原料选择: 选择含端羟基官能团的多元醇和多元酸，关键因素为多元醇和多元酸的特性，包括官能度、硬度、柔韧性、成本等。 选择原料时应考虑含苯环的原料以增加硬度，以及三官能团及以上的多元醇或多元酸促进网状结构的形成。 3. 配方设计时，考虑二元醇的升华损耗，确保反应后过量羟基封端以保留交联固化的活性基团。 4. 典型树脂参数: 羟值一般控制在60-80 mgKOH/g（面漆），及根据用途调整醇超量（面漆醇超量约1.15-1.25，底漆约1.05-1.10）。 5. 配方实例: 针对卷材涂料面漆设计的聚酯树脂，确定所需原料后，按性能需求进行比例测算，并微调理想的羟值和官能度，确保最终树脂的综合性能。1. 新戊二醇、间苯二甲酸、三羟甲基丙烷、1,6-己二醇、BEPD投入反应釜，通氮气、升温。 2. 加热到能搅拌时，开动搅拌，投入单丁基氧化锡，打开直冷凝与横冷凝冷却水，反应出水后，停止通氮气。 3. 继续缓慢升温，气相温度控制：第1小时，气相温度 102~105°C；第2~3小时，气相温度 108~112°C；第4小时，气相温度 105~108°C。釜内温度前1.5小时，釜内温度 ≤ 190°C；后2.5小时，釜内温度 190~210°C。 4. 熔融酯化反应4小时后，取样在玻璃上，冷却到室温后达到透明，维持透明状态 30~45分钟。冷却到 170°C 以下，加入已二酸和二甲苯。 5. 关闭直冷凝冷却水，边脱水边升温，进行回流酯化反应，控制反应温度 ≤ 220°C。 6. 回流反应2小时后，进行中控，检验黏度、酸值。取样比例 12.7g样品 + 7.3g稀释溶剂，控制加氏黏度 (25°C) 25~35s，酸值 2~6 mgKOH/g。 7. 中控合格后，冷却到 180°C 以下，放料到对稀釜中；反应釜中加入剩余对稀溶剂，回流一段时间后放入对稀釜中，搅拌均匀后复测黏度，达到要求后过滤包装。将饱和聚酯树脂、固化剂、颜填料按比例混合后，由研磨设备粉碎后，经熔融挤出、粉碎过筛，可得到聚酯粉末涂料。配方设计为多元酸过量，生产中为避免胶化，将部分多元酸后投，先合成端羟基聚酯树脂，等反应到一定程度后，再加入起始投料时留出来的多元酸，继续反应一段时间，达到规定的指标后，结束反应，并加入添加剂，搅拌均匀，在熔融状态下由切片机制成聚酯薄片。聚酯树脂酸值控制在50~80mgKOH/g较为合适。采用熔融酯化的工艺，以助反应终止后的成型，需通入惰性气体以帮助脱水。本实验使用的单体包括丙烯酸、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸甲酯等，同时可选用含羟基（如丙烯酸羟丙酯），含羧基，含环氧基，含叔氨基等功能性单体。引发剂常用的有偶氮二异丁腈和过氧化苯甲酰等，需根据其不同的分解温度和半衰期进行选择。使用时，应注意溶剂应选用与丙烯酸树脂相似溶解度参数的化合物(如甲苯、二甲苯等)，并添加链转移剂如十二烷基硫醇以调节分子量分布。具体操作包括：将选定的单体与引发剂混合，加热至设定温度下进行聚合，最终通过冷却与脱气处理得到所需的功能性聚合物。1. Prepare a solution containing monomers, initiators, and solvents. Maintain the temperature between 80°C to 160°C, adjusting as per the boiling point of the solvent and the decomposition temperature of the initiator. 2. Control the addition of monomers using a slow dripping method over a timeframe of 2 to 4 hours to prevent excessive heat generation and ensure a uniform polymerization speed. 3. Introduce functional groups in the monomers to create polymers with desired functionalities. 4. Monitor the reaction temperature and use nitrogen gas to displace oxygen and prevent inhibition of the polymerization reaction. 5. After most of the monomer is consumed, add more initiators to achieve a higher conversion rate. 6. Use a chain transfer agent when necessary to control the molecular weight of the resulting polymer. 7. Terminate the reaction once the desired properties of the polymer are met.1. 按工艺配方，将规定数量的单体通过不锈钢过滤器过滤后，加入单体配置器中，待混合均匀后，放置待用。2. 将引发剂投入引发剂配制器中，用少量聚合溶剂溶解，过滤待用。如系BPO等含水过氧化物，则应除去水分。3. 空釜时，先打开氮气（或二氧化碳）通管，赶走釜内空气。然后按配方规定加入溶剂。有时，可先加人部分单体和引发剂。4. 继续通情性气体，开动搅拌，打开蒸汽阀加热，并打开回流加热和冷却两个冷凝器的冷却水，待升到离规定的反应温度前20~30℃时（可视具体情况而定）即可关闭蒸汽，待其慢慢自升到反应温度。5. 开始加入单体和引发剂溶液，一般在2~4h内加完，但应视反应热的除去情况而稍加调整。单体和引发剂的加入速度应均衡，在此期间温度也要保持恒定。6. 加完单体和引发剂后，保温1.5~2h，追加第一次引发剂（可溶于溶剂中一次投人)，再追加第二次引发剂，继续保温到转化率和黏度达到规定指标。整个反应时间约在6~15h完成，视品种配方不同而异。7. 反应完成后，可加热升温蒸出少部分溶剂，借以脱除自由单体。然后，补加新鲜溶剂以调整固体含量。8. 冷却后，出料。1. 确定树脂的类型是热塑性的还是热固性的。\\n2. 确定树脂用来制造何种涂料。\\n3. 确定树脂聚合方法。\\n4. 确定设计的树脂和涂料应达到的主要技术指标及施工性能。\\n5. 根据涂料产品特性选择单体。\\n6. 对选择的单体互相间反应性论证，选择有利于共聚反应的单体。\\n7. 确定聚合工艺条件。\\n8. 模拟单体配比，进行树脂合成。\\n9. 根据模拟单体配比合成的结果，对单体配比进行反复调整。\\n10. 确定合成树脂工艺规程，包括聚合方法、树脂配方、聚合工艺、树脂质量指标等。原料甲基丙烯酸甲酯、甲基丙烯酸丁酯、苯乙烯、甲基丙烯酸、丙烯酸丁酯、CPP等，过氧化苯甲酰，甲苯，甲基异丁基酮。合成方法在反应釜内加人CPP及 70% 溶剂加热至 100^{\\circ}C ，搅拌至完全溶解。将100%的混合单体及 70% 的BPO事先混合好，用4h均匀加到反应系统进行聚合反应。滴加完毕后，保温1h，然后将剩余 30% 的溶剂与 30% 的BPO事先混合好，分别补加三次，每次保温 2h 。整个反应温度保持在 100{\\sim}110^{\\circ}C 之间。将全部单体、链转移剂和配方中 70% 的BPO在高位槽中混合均匀。在反应釜内，投人溶剂和 30% 的混合单体，搅拌升温至回流温度（约 120°C），保温 30min，滴加混合单体，于3h左右滴完，并保温1h，补加剩余的BPO，继续回流保温2h，测定树脂的技术指标合格后，降温出料备用。将部分1放人反应釜，搅拌，氮气保护，加热至165°C。部分2在6h内均匀滴加，温度保持165℃，搅拌，氮气保护，滴加完毕后加入部分3继续反应1h，冷却至100%，用醋酸丁酯调整固体分至50%。水可稀释型丙烯酸树脂的制备通过溶液聚合实现。在制备时，选择含有羧基、磺酸基、醚键等官能团的不饱和单体与丙烯酸酯单体共聚。然后，用有机胺或氨水中和成盐，再溶解于水以获得水溶性丙烯酸树脂。若在体系中引入含羟基单体，则可以制成水性热固性丙烯酸树脂。与氨基树脂、多异氰酸酯配合，可分别制备水性单组分丙烯酸氨基树脂涂料和水性双组分丙烯酸聚氨酯涂料。水可稀释性丙烯酸树脂的合成需在助溶剂中进行聚合反应，水在成盐时加入。聚合物主链上含的羧基或氨基通过与碱或酸的中和反应形成盐类，从而获得水溶性。该方法被称为成盐方法，通常用于合成水性丙烯酸树脂。另外，醇解法可应用于丙烯酸树脂在溶液中共聚后进行水解以获得水溶性。1.称取配方量（质量份）混合单体，加人单体量2% 的偶氮二异丁晴引发剂，在氮气保护下将混合单体于2.5h内慢慢滴入丙二醇醚类溶剂（单体：溶剂的质量比为2:1). 2.继续在101℃左右保温1h，再加入总质量20%的丙二醇醚类溶剂，然后升温蒸出过量的溶剂，至固体分浓缩至75%，树脂的酸值为62，降温、过滤、出料。 3.水性丙烯酸树脂的合成在1000mL的四口瓶中，分别装有冷凝管，温度计，机械搅拌器，按具体配方量加入丙烯酸树脂溶液和环氧树脂溶液，在搅拌条件下，用甘油浴加热到95℃，1~2min内加入配方量的N，N-二甲基乙醇胺，恒温反应，经1.5h后，黏度保持恒定，取样测环氧值为零，结束反应。使用丙烯酸酯共聚物乳液合成含功能基团的亲水性聚合物，单体选择丙烯酸甲酯、丙烯酸乙酯等，并加入功能单体例如(甲基)丙烯酸、马来酸等以及交联单体，如(甲基)丙烯酸羟乙酯。功能单体及交联单体的添加量一般为单体总量的1.5%\\sim5%。引发剂选择水溶性过硫酸钾或过氧化氢，浓度范围为0.01%\\sim0.2%。乳化剂使用阴离子型与非离子型结合，添加量为单体总量的2%\\sim5%。中和剂根据树脂不同类型选择相应碱性或有机酸类中和剂。无皂乳液聚合是指不加乳化剂或加入微量乳化剂的乳液聚合过程，即以水溶性低聚物为乳化剂，使用的低聚物可包括顺丁烯二酸化聚丁二烯、顺丁烯二酸化醇酸、顺丁烯二酸化油。可用聚合性表面活性剂进行共聚，例如丙烯酸磺基丙醇酯、对苯乙烯磺酸钠等。在水性介质中先加少量亲水的丙烯酸或甲基丙烯酸酯单体进行聚合，形成粒径为100至200 nm的聚合物粒子。然后再加入憎水性单体进行聚合，憎水性单体在前述聚合物粒子表面上选择吸附，聚合就在这里发生。成核单体相对于憎水单体量约为0.5%至2%。此法可制得粒度为0.08至0.4 μm、分布窄、不含乳化剂和稳定剂的乳液。上述配方中，按照如下比例进行反应：甲基丙烯酸甲酯 5，硫酸钢 (0.01 mol/L) 7.5，水 250，苯乙烯 120，过硫酸钾 (0.005 mol/L) 0.4，硫代硫酸钠 (0.005 mol/L) 0.37。在60°C和pH 3至4的条件下，数分钟内聚合完成，生成的聚合物粒径为104 nm。随后添加苯乙烯，大约用5小时完成聚合，得到单体：水相为1:2的乳液，粒度为287 nm。在合成丙烯酸乳液时，首先选择适合的生产工艺，如半连续工艺。将计量过的水加入混合物配料罐中，并加入分散剂、湿润剂、增稠剂、消泡剂、杀菌剂等助剂，低速下搅拌均匀后加入颜料和填料，待润湿后提高搅拌速度。将混合均匀的浆料送入砂磨机研磨至细度符合要求。然后将乳液送入基料配制罐，边搅拌加入成膜助剂、消泡剂、杀菌剂等助剂，充分混合后过滤并送入调漆罐。调漆罐中边搅拌边加入研磨色浆，搅拌15至30分钟后调色，最后加入剩余增稠剂和配方水，确认合格后进行出料和包装。将乳化剂溶解于水中，加入混合单体，在激烈搅拌下进行乳化。然后把乳化液的1/5投人反应釜中，加入1/2的引发剂，升温到70~72℃，保温至物料呈蓝色，此时会出现一个放热高峰，温度可能升至80℃以上。待温度下降后开始滴加混合乳化液，滴加速度以控制釜内温度稳定为准，单体乳液滴加完后，升温至95℃，保温30min，再抽真空除去未反应单体，最后冷却，加入氨水调pH至8~9，出料。The synthesis of hydrophilic polymers with functional groups involves the following steps: First, prepare a prepolymer consisting of low molecular weight resin with C=C unsaturated bonds, typically using acrylated or methacrylated resins such as epoxy acrylate, polyurethane acrylate, and others. Second, incorporate an active diluent, which may be a monofunctional or multifunctional reactive diluent, to adjust viscosity and improve application performance. The choice of active diluent should consider factors such as viscosity, solubility, dilution capacity, volatility, odor, toxicity, and the presence of functional groups. Use photoinitiators suitable for UV radiation which absorb light and generate reactive intermediates to initiate polymerization. Select photoinitiators based on their absorption efficiency, radical quantum efficiency, solubility in the resin, stability, and non-reactive nature with the cured resin. Finally, add necessary additives to enhance the stability and performance of the curing system. Ensure that the curing process is optimized by controlling factors such as temperature, humidity, light intensity, and the presence of oxygen.在带有搅拌、回流冷凝器和加热系统的反应釜中加入环氧树脂，缓慢升温到100摄氏度，以三乙胺为催化剂，缓慢滴加丙烯酸，并控制反应温度在120摄氏度以下，滴加完毕以后，反应2至4小时，取样测定至酸值10以下，降温、出料、包装待用。环氧树脂的合成分为两种主要类型：1)缩水甘油类，通过环氧氯丙烷与多元酚或多元醇反应获得；2)非缩水甘油类，通过氧化剂（如过醋酸）与碳-碳双键反应获得。对于缩水甘油树脂，常见的有缩水甘油醚、缩水甘油酯和缩水甘油胺。而非缩水甘油类树脂主要用于辐射固化的阳离子聚合涂料。 具体合成实例包括由二酚基丙烷（双酚A）与环氧氯丙烷缩合而成的树脂。将环氧基与羧酸反应，通常在\"混合型\"粉末涂料中广泛应用。配方中含有少量碱性的咪唑，如2-苯基咪唑，催化羧基与环氧基反应。强亲核试剂RCOO-可用于反应。其他催化剂如二甲基苄胺也常用。环氧基与羟基反应在常温下进行较慢，可以使用路易斯酸如三氟化硼乙醚配合物催化开环。环氧基与碱或叔胺在加热下会自行缩聚成醚，并胶结。使用DMP-30催化剂可促进环氧基与硫基反应。环氧树脂与酚羟基反应等用于制造管道粉末涂料。环氧基与异氰酸酯反应可生成唑烷酮，用于制备耐高温产品。将双酚A和环氧氯丙烷按1:(3~5)质量比的比例加入反应釜中，升温至50~80°C溶解，控制釜温为60~70°C，分几次加入约为酚羟基当量0.08~0.1当量的液碱，常压反应4~6小时，控制釜内真空度为0.075~0.085MPa，温度60~70°C，于3~5小时内滴加完约为酚羟基当量0.8~0.9的碱，维持回流反应3~6小时，回收过量的环氧氯丙烷，加入溶剂溶解，再加入约为酚羟基当量0.08~0.1的液碱进行精制反应，通过水洗、回流、脱溶剂等一系列后处理工序得到成品树脂。将双酚A和NaOH溶液投入溶解釜中，搅拌加热至70°C使双酚A完全溶解，趁热过滤，滤液放人反应釜中冷却至47°C时一次加入环氧氯丙烷，然后缓缓升温至80°C。在80~85°C反应1h，然后在85~95°C维持至软化点合格为止。加水降温，将废液水放掉，再用热水洗涤多次，至中性和无盐，最后用去离子水洗涤。先在常压脱水，液温升至115%以上时，减压至21.33kPa，逐步升温至135~140°C。脱水完毕，出料冷却，即得固体环氧树脂。将低分子量环氧树脂（预含催化剂）及双酚A投入反应釜，通氮气，加热至110~120°C，此时放热反应开始，控制釜温至177℃左右。注意用冷却水控制反应，使之不超过193°C以免催化剂失效。在177°C所需保温的时间，取决于制得的环氧树脂的分子量：环氧当量在1500以下保持45min，环氧当量在1500以上保持90~120min。双酚A用量计算公式：W=(Ev1-Ev2)/(0.8771+Ev2)Q，其中W是双酚A用量，kg；Q是液体环氧树脂投料，kg；Ev1是基础树脂环氧值；Ev2是成品树脂环氧值。E-51环氧树脂 248.6g, 双酚A 94.4g, 乙基三苯基磷碘化物 0.21g, 渐渐升温至 170^{\\circ}C 发生反应，保温。制成的环氧树脂的环氧当量为693。先将二酚基丙烷、环氧氯丙烷溶解于乙醇中，滴加第一份氢氧化钠溶液，室温搅拌16h，再加第二份氢氧化钠，升温回流，在80°C反应半小时，加5kg混合溶剂。每隔半小时加混合溶剂2.5kg1次，共加3次。回流4h后，加苯酚，再加混合溶剂5kg，继续回流1.5h，再加冷水10kg。弃去下层废液。树脂用热水洗涤，洗到pH=7~7.5为止。加入余量的混合溶剂。真空回流脱水，水脱尽后加环已酮。过滤，即为成品。诺伏勒克环氧树脂是由苯酚或邻甲酚与甲醛反应制得诺伏勒克，再与环氧氯丙烷反应而成。将脂肪族多元胺与少量环氧树脂反应，使用例如乙二胺与低（或中）分子量环氧树脂进行反应。与此同时，可以运用二亚乙基三胺与液体低分子量环氧树脂反应来制得加成物。酰氨基胺是用植物油脂肪酸（或塔油）与多元胺缩合而成。在制造时，若升高温度则脱水成为咪唑啉，黏度降低。氨基聚酰胺树脂的合成步骤包括：首先，将不饱和脂肪酸加热聚合得到二聚酸；然后，将二聚酸与多元胺进行缩合反应，形成氨基聚酰胺树脂。The article does not provide a specific experimental protocol for the synthesis of hydrophilic polymers with functional groups. It mainly discusses the characteristics of various curing agents such as aliphatic amines and their properties.使用4,4'-二氨基二苯甲烷和间苯二胺制备低共熔混合物，按比例6:4混合，形成液态固化剂。芳脂胺类有间苯二亚甲基二胺（xylylenediamine，XDA)的合成过程使用了作为固化剂的芳脂胺，具体实验步骤和条件未在文本中详细说明。Mannich碱类固化剂的合成是通过酚（或酮）、甲醛和胺的缩合反应进行的。对于合成叔胺，使用相同的反应条件，但不添加多元胺，而是加入单官能的二甲胺。在此过程中，酚羟基促进固化，缩聚反应产生的产品具有催化作用。将双氰胺充分粉碎成极细粉末，分散在液体树脂内，使用量为100份E-12树脂用2.5至4份双氰胺。固化条件为在145至180摄氏度下烘烤半小时。The text provided does not contain any specific experimental protocol for the synthesis of hydrophilic polymers with functional groups.Not applicable as the text excerpt does not provide specific experimental protocol for the synthesis of hydrophilic polymers with functional groups.环氧树脂E-20 32.6g, 正丁醇 30.0g, 二乙烯三胺 7.4g, 二甲苯 30.0g。将环氧树脂和胺分别溶解于溶剂中，在胺溶液中在揽拌下逐渐加入环氧树脂溶液，加毕搅拌3h。此产物的固体分为 $40\\\\%$。配漆的配比，（固体分）：环氧树脂E-20 100g, 加成物（固体计） 30~35g将乙二胺、丁醇、二甲苯置入反应釜，搅拌，慢慢地加入环氧树脂，加毕后，密闭反应釜，加热回流反应2至3小时，然后减压蒸出溶剂和过量的乙二胺，达到终点（产物的软化点约96%）降温出釜。聚酰胺树脂的合成通过将二聚酸（如二聚酸Dimer acid）与多元胺（如二乙烯三胺）缩合反应而成。反应方程式为：HOOC-E~~-COOH + 2HNCH—N—-CHNH—。聚酰胺树脂采用的胺值根据产品的技术要求选择对应牌号的固化剂（如Versamid100、115、125），其配比通常为环氧树脂与聚酰胺树脂按3:1比例。注意在聚合过程中，避免过高的温度以防止脱羧反应。将环氧树脂E-20(75%溶液) 17.8g与双酚A/F液体环氧树脂 13.4g混合，加入磷酸锌系防锈颜料7.3g及滑石粉 24.5g，消泡剂BYK057 0.5g和FeO 4.9g，最后加入固化剂450 11.1g。确保混合均匀，涂料的PVC约29%，混合后涂料的固体含量约85%（质量分数），涂料的VOC约250g/L。To synthesize hydrophilic polymers with functional groups, mix epoxy resin E-42 (283.5g) and gas phase silicon dioxide (6.7g) as part A. Part B consists of xylene (436.0g) and dibutyl phthalate (57.68g). Add a curing agent such as triethylene tetramine with a specified ratio. Mix these components thoroughly and maintain the mixture for several weeks to monitor viscosity changes, indicating possible reactions. Adjust the solid content and mixing ratios according to performance requirements.高分子量的环氧树脂的仲羟基与多异氰酸酯的交联反应，在室温或较低温度下进行，制成常温干型涂料。固化剂为二异氰酸酯和多元醇的加成物。配方中环氧树脂（E-03）需要分子量1400以上。选择适宜的环氧树脂作为原料，常用的环氧树脂包括E-20、E-12和E-06，具体规格见表2-1-140。对于酯化反应，通常选择E-12树脂，因为其在耐化学品性能和操作控制上表现优异。根据用途不同，选择适当的脂肪酸，例如，对于常温干型环氧酯，使用干性油脂肪酸（如亚麻油酸和桐油酸）；对于烘干型环氧酯，使用脱水麻油酸和椰子油酸。在合成具有功能基团的亲水性聚合物时，首先选择适当的脂肪酸，并确定其酯化程度，通常为60%至90%。应加入催干剂以促进涂膜的氧化聚合干燥，一般选择环烷酸钴，催干剂用量约为环氧酯不挥发部分的0.04%左右。对于烘干型漆，通常使用不干性油脂肪酸，酯化当量在0.5以下，催干剂用量可以减少，金属钴的用量为清漆不挥发分的0.005%至0.01%。在计算配方时，应考虑到各组分的摩尔比和实际质量，以确保最终产品的性能符合预期要求。将树脂、脱水麻油酸、回流二甲苯，催化剂 z_{nO} （为环氧酯量的 0.1% 投人釜中，升温至 150^{\\circ}\\mathrm{C} 树脂熔化后，开动搅拌，升温至 200\\sim205\\mathrm{^\\circC} ，保温酯化约 2\\mathrm{h} ，开始取样，测黏度和酸值。当酸值降到5以下时，停止加热，立即冷却降温，将酯化物抽入对稀罐中降温至 130^{\\circ}\\mathrm{C} 以下，加入二甲苯稀释，至 60^{\\circ}\\mathrm{C} 以下，过滤，贮存备用。1. Select high molecular weight epoxy resin (2900-4000) to ensure a high content of hydroxyl groups for effective curing with phenolic resin. 2. Use butanol etherified phenolic resin, preferably those that can mix with epoxy resin for curing. The amount of phenolic resin should be 25%-35% of the total non-volatile content of the coating. 3. Add a leveling agent, such as 2%-3% urea-formaldehyde resin solution, or small amounts of 1% silicone oil solution or 1% polyvinyl butyral. 4. For increased curing rate, include 1%-2% phosphoric acid as a catalyst, or 0.5% of latent catalyst like toluenesulfonic acid salt if using lower temperature curing. 5. Employ multi-stage drying: Intermediate layer drying at 90-150°C for 10-30 minutes, followed by final drying at 180°C for 60 minutes.甲醛与双酚A在 NaOH 存在下于 40℃ 反应，产物以 H2SO4 中和水洗，加入苯酐、丁醇使之醚化，再经脱水（终点控制沸点 120℃）过滤即得成品，其不挥发分为 50%±2% 黏度 (25℃ ，涂-4杯）为 60∼75s。将乙组分混入甲组分中，搅拌 $3\\mathrm{min}$ 以上。将Casamid 362通过 $\\mathrm{CO_{2}}$ 形成碳酸盐，搅拌甲组分（Casamid 362 20.8g, TiO 10.5g, 异丙醇 6.3g, 水 25.0g, 消泡剂BYK 031 0.4g）和乙组分（液体环氧树脂 16.0g），施工时限（20℃）为3.5h。将环氧分散体EPI-REZ3520-WY-551、固化剂EPI-CURE8537-WY-60、消泡剂、乙二醇丁醚和TiO依次加入，分别为510.5g、155.4g、4.0g、7.5g和250.0g，然后将以上投料高速分散并加水149.8g。将甲、乙组分充分搅拌混合后，配比可按需调整，加入多官能度环氧树脂和固化剂。首先将EPI-REZ 5522-WY-55与消泡剂、二丙酮醇、水混合，再加入硅灰石、硅酸铝、FeOs、BaSO等。将所有成分高速分散后，再加入EPI-REZ 5522-WY-55和水，得到双组分混合物。最终微调黏度至60-70KU。The text excerpt does not provide any specific experimental protocol for the synthesis of hydrophilic polymers with functional groups.聚氨酯漆的树脂是由多异氰酸酯与多元醇结合而成。制备氨基甲酸酯的方法包括：1. 氯甲酸酯与胺反应；2. 氨基甲酰氯与醇反应；3. 醇与脲加热反应。将甲苯二胺溶解于二氯化苯中，将光气通入此液相溶液中，前期是低温光气化，后期再升温光气化。多异氰酸酯与多元醇反应形成聚氨酯。操作过程中需注意：1) 原料中不应含水分，因水分会导致胶凝；2) 检查原料及中间体的纯度；3) 投料应准确，遵守操作规程，避免因顺序错误或温度不当引发副反应；4) 监控反应温度，通常控制在100℃以下，以防止生成不必要的副产物。反应过程中，一旦有故障导致反应过热，需要立即采取措施如夹套冷却以减少局部过热。选择酯类溶剂（例如醋酸乙酯、醋酸丁酯）和酮类溶剂（如甲基异丁基酮、甲基戊基酮）。确保所用溶剂不含能够与NCO基反应的物质，如醇和醚醇类溶剂，同时控制水分含量以避免胶凝。使用高纯度的氨酯级溶剂，以尽量减少对NCO基反应性的影响，并在制造过程中监测残留的异氰酸酯量以评估溶剂的合用性。制造方法是将干性油、多元醇、催化剂（$4\\\\%$ 环烷酸钙，加入量为油量的 $0.1\\\\%\\\\sim 0.3\\\\%$ ，不宜用黄丹，否则黏度上升太快）加入反应釜，在 $230\\\\sim250^{\\\\circ}C$ 间醇解 $1\\\\sim2h$ ，待醇解符合指标后（以甲醇容忍度测定之)，加入溶剂共沸脱水，在 $50^{\\\\circ}C$ 滴加入二异氰酸酯，搅拌半小时后，升温至 $80\\\\sim90^{\\\\circ}C$ ，并加入催化剂（二月桂酸二丁基锡，为不挥发分总量的$0.02\\\\%$），待充分反应，异氰酸酯基完全消失（以二丁胺法测定）后，加入少量醇（作为稳定剂，以防残留NCO基，在贮存时引起胶凝）及溶剂，过滤，加入抗结皮剂及催干剂。将3分子TDI与1分子三羟甲基丙烷的加成物制备。将TDI投人反应釜，搅拌升温至60°C，将熔融的三羟甲基丙烷或添加醋酸乙酯等溶剂，渐渐加入，使其充分反应，在60~70°C保温3小时，加入其余溶剂，保温均匀，冷却出料装罐。对废弃的游离TDI采用薄膜蒸发法或溶剂萃取法处理。具体操作中，应注意维持温度，使反应温度不超过50°C，避免生成脲基甲酸酯。将苯酐及 27.1kg 三羟甲基丙烷投入反应釜，在 180~200°C 酯化，通入二氧化碳以带除水分，待酸值降到220左右，加入第二批三羟甲基丙烷 54.2kg 及月桂酸，继续酯化至酸值达3.5左右。产品是浅黄色固体，软化点 37~42℃，羟基当量为310。将2mol的二甲苯与2mol的叙碳酸缩水甘油酯加热至142°C，再将单体混合物均匀加入到该溶液中，反应3小时。在135°C下聚合4至5小时，产品的固体含量约为70%。随后，将丙烯酸树脂与HDI缩二脲按照固体含量比例64.68g与35.48g混合，加入颜料可制得优良汽车修补漆，喷涂至干膜厚度45至50μm，常温干燥时间为40分钟。将聚氨酯涂料的羟基组分与固化剂混合，保证NCO/OH比例为1:1，配制所需的聚氨酯漆时，首先准备丙烯酸树脂A870（70%固体）48.38g，然后加入固化剂Desmodur N 3390 18.14g，搅拌均匀。接着加入消泡剂BYK331（50%溶液）0.30g和光稳定剂Tinuvin292（50%溶液）1.00g及Tinuvin1130（50%溶液）2.01g，这些成分混合后细致搅拌，以确保均匀分散。随后，添加DBTDL（1%溶液）1.51g作为催化剂与溶剂（MPA + Xylene : BuAc=1 : 1 ）28.66g，再次混合均匀。最后，理想的干膜厚度控制在45μm，待涂膜在7天后测试摆干硬度（konig）为198s，完成聚氨酯漆的合成。预聚物制备时，将葛麻油（26.88kg）、环烷酸钙（0.05kg）和甘油（1.97kg）在240℃下醇解2小时，随后降温至40℃以下，加入TDI（21.0kg）、二甲苯（43.7kg和6.3kg）在80℃下充分反应，直至粘度达到加氏管2至3秒。催化剂溶液由甲基二乙醇胺（0.5kg）和二甲苯（9.5kg）组成，施工前两部分混合，预聚物（1000g）与催化剂溶液（26g）按NCO/OH比例1.7/1配制。制造双组分聚氨酯漆时，将颜料分散在含羟基组分中作为一个组分，将多异氰酸酯作为另一组分，使用时互相配合。制造潮气固化型色漆时，因树脂中含有游离的异氰酸酯基，能与颜料的水分反应，采用异氰酸酯除水法，即用单体的异氰酸酯预先与颜料及溶剂反应，脱除其所含水分，然后加入含NCO基的预聚物树脂充分研磨分散。具体操作为：将多异氰酸酯、云母氧化铁、冲稀铝粉浆、消泡剂、膨润土浆、滑石粉等投入高速分散机搅匀5分钟后，加PCE，用13m/s线速度搅拌15分钟，确保充分分散，随后加入云母氧化铁以较低速度搅拌5分钟，最终停止搅拌，加入芳烃溶剂和原甲酸三乙酯，静置过夜，次日搅拌均匀装罐。先溶解硝化棉片于部分溶剂中；硬脂酸锌及P104分散于聚酯中；混合硝化棉溶液和聚酯溶液。(1) Prepare the prepolymer by reacting rosin oil with glycerol in a molar ratio of 1:0.48 using calcium naphthenate as a catalyst. Add 0.04 kg of calcium (calculated as metal) per kilogram of oil and perform alcoholysis at 240°C for 2 hours. Measure the tolerance using an 84% ethanol-water solution until it exceeds 25, then cool to 60°C. Add xylene to remove water by azeotropic distillation and adjust the non-volatile content to 70%, yielding a solution with a hydroxyl value of 150-165. Additionally, perform azeotropic dehydration on polyether (hydroxyl value 460-470) using toluene and adjust the non-volatile content to 80% to obtain a solution with a hydroxyl value of 360-380. Introduce toluene diisocyanate 24kB into the reaction vessel, start stirring, and heat to 50°C. Then add the above alcoholysis solution 32kB and raise the temperature to 60-65°C, followed by adding the previously prepared polyether solution 6.75 kg. Subsequently, add toluene 24 kg, raise the temperature to 70°C, and maintain the temperature until the NCO content is between 6.0-6.8% and the viscosity reaches 17-22 seconds on a Gardener tube. Finally, add 22g of diluted phosphoric acid solution (2% phosphoric acid in cyclohexanone), mix thoroughly, and cool to below 50°C for discharge. The addition of phosphoric acid enhances storage stability and offsets the catalytic action of calcium naphthenate during alcoholysis. (2) Prepare the asphalt solution by placing 400 kg of coal tar asphalt (softening point 45-55°C) into a kettle, heat until melted, and start stirring. Raise the temperature to 130-150°C and maintain it. Sample hourly to measure softening point, and when it reaches within 57°C ± 3°C, cool down to 110-120°C. Add 266 kg of dehydrated mixed solvent (cyclohexanone:toluene:xylene = 40:35:25), mix thoroughly, and cool below 50°C for discharge. The volatile content should be maintained at 60% ± 2%.制造聚氨酯沥青漆：1. 选择聚醚作为原料，因其含有较多的仲羟基，反应性较慢。2. 如需延长施工时限，挑选较强的溶剂。3. 对一些煤焦沥青可加入少量的单官能异氰酸酯处理（如甲苯磺酸异氰酸酯或少量MDI），以缩短施工时限。第一步：先制备聚酯。 使用葵二酸、己二酸、癸二酸与一缩乙二醇、三羟甲基丙烷进行反应，配比为葵二酸 59.4kg、己二酸 38.6kg、癸二酸 46.1kg、己二酸 53.9kg、三羟甲基丙烷 2.0kg。 第二步：制备预聚物。 将聚酯与TDI（或其他二异氰酸酯）在反应烧瓶中反应，加入TiO和二甲苯等助剂，得到预聚物色浆时，保持比例为聚酯-氨酯-二元醇（35%溶液）、TiO（17.5g）、丁醚化三聚氰胺树脂（50%溶液）和XDI/TMP加成物（75%）。干燥条件为120℃烘10分钟，即可获得涂膜。将乙组分中1300号聚酯（75%溶液）28.3g、甲基异丁基酮10.2g、VAGH氯醋共聚体（20%溶液）10.0g、甲苯6.0g、硅油（1%溶液）0.6g、MPA溶剂3.4g及醋酸乙酯27.2g混合。根据所需的NCO/OH比例进行计算和调整。聚脲树脂的合成是通过异氰酸基-NCO的单体或预聚物与氨基-NH2或-NRH的单体或预聚物进行加成缩合反应。反应速率上，氨基与-NCO的反应快于-OH与-NCO的反应。可以通过特种喷枪混合喷涂的方法，将氨基聚醚与MDI反应，材料在几秒至十几秒内胶化，并在几分钟内完成交联反应。调整胺或-NCO的反应活性，可以在几分钟至几十分钟内固化聚脲材料。还可以使用含-OH的多元醇或环氧改性聚脲材料，以制备不同性能的聚脲聚氨酯及环氧改性聚脲成膜体系。In the synthesis of hydrophilic polymers, the raw materials used consist of three main categories: amine-terminated polyether, isocyanates, and chain extenders. In addition, various additives such as thinners, flame retardants, antioxidants, antiblocking agents, pigments, and silane coupling agents may be included to enhance properties like viscosity, flame resistance, aging resistance, antistatic properties, appearance, and adhesion. In the SPUA technology, the component formed by the reaction of isocyanates with polyether polyols to produce a quasi-prepolymer is referred to as component A; the component containing amine-terminated polyether, liquid amine chain extenders, and other additives is referred to as component B or R.a. 加热690g（1.38当量）的分子量为1000的聚醚，在90℃下，真空揽拌1～2h，除去所存在的湿气。 b. 氮气保护下冷却至70℃。 c. 加入435g（3.5当量）的纯MDI。反应热将使温度升高至(80±4)℃，保持这个温度1~2h，确保反应完全。整个反应要求在氮气保护下进行，生成的预聚物也必须充入氮气进行保护，用这种技术生产的预聚物，在室温下可贮存数月，甚至一年。HDI is synthesized by the reaction of hexamethylenediamine with phosgene. IPDI is synthesized through the reaction of isophorone with hydrogen cyanide to generate isocyanurate, followed by hydrogenation and phosgenation. XDI is produced by reacting dimethylbenzenes with ammonia oxidation to form benzyl cyanide, which is then reduced to benzyl amine and ultimately phosgenated. The hydrogenated form of XDI (HXDI) and hydrogenated MDI (HMDI) are produced through the hydrogenation of their respective amines followed by phosgenation. TMXDI is obtained by modifying the hydrogens on the methylene groups of XDI with methyl groups, enhancing its properties.使用芳香族A料合成的端羟基聚醚和脂肪族A料合成以及B料制备的端氨基聚醚进行合成。1. 聚氧化丙烯醚多元醇在起始剂和催化剂存在下，由环氧丙烷开环聚合制得。主要使用二元醇起始剂，如丙二醇，也可以掺混部分三官能团多元醇。聚醚的官能度由起始剂的官能度或活泼氢个数决定。2. 聚四氢呋喃多元醇通过四氢呋喃的开环聚合制得。需添加抗氧剂（如抗氧剂264），添加量约为200mg/kg。3. 聚己内酯多元醇由γ-己内酯开环聚合合成，常用的催化剂有四丁基钛酸酯、四异丙基钛酸酯、辛酸亚锡等。4. 芳香族端氨基聚醚的合成: a. 用对硝基苯异氰酸酯封端聚醚二元醇，然后通过加氢反应转化为氨基；b. 聚醚双氯甲酯与苯二胺反应得到端氨基聚醚；c. 异氰酸酯预聚体经水解反应得到端氨基聚醚。5. 脂肪族端氨基聚醚的合成: a. 将醇、氨和氢气混合在高温和压力下通过Cu-Ni催化作用反应；b. 结合含有离去基团的聚醚与胺反应。将二异氰酸酯和低聚物多元醇或氨基聚醚反应先合成半预聚物。一般的二胺类扩链剂在实际使用中，除了起扩链作用外，还可在过量一NCO基存在下，在大分子之间产生缩二脲交联。将适量的胺类扩链剂与氨基聚醚混合加热至105°C，熔化后使用。使用平均分子量为2000的聚己二酸乙二醇酯与TDI制备预聚物，再分别与TX-2、DADMT、MOCA扩链生成聚氨酯弹性体。合成半预聚物的过程中，采用芳香族异氰酸酯同端羟基聚醚的反应。常用的羟基化合物包括聚氧化丙烯醚多元醇、聚四氢呋喔多元醇（PTMEG）、聚e-已内酯多元醇和端羟基聚丁二烯。为了确保预聚物质量，需严格控制原料中的水分含量，低于0.05%。若使用二苯基甲烷二异氰酸酯（MDI），在合成时应保持温度在60至80°C，同时需在冷冻条件下贮运以防止自聚反应。半预聚物同氨基聚醚与液体胺类扩链剂的反应可在没有催化剂的情况下进行，形成聚脲材料。反应需要在高温下进行，同时，还需考虑脲基的副反应。在实验过程中，使用官能度大于2的多异氰酸酯合成的半预聚物，并与官能度大于2的氨基聚醚反应。同时，可以利用过量的异氰酸酯与脲基反应生成缩二脲交联。为了提高SPUA材料性能，也可加入邻氨基扩链剂以延长凝胶时间，改善涂层的流平性及附着力。对于聚脲或聚氨酯的合成，需要计算当量以确保反应的正确进行。端异氰酸酯组成物的当量可以通过NCO基含量的分析计算，具体公式为根据每种化合物的特性。端羟基组成物的当量则可以通过羟值的定义进行计算，使用公式为端羟基组成物的当量粒子=56.1×1000。胺当量是所有端异氰酸酯基化合物的实际当量，通过与二正丁胺反应分析得到。胺值用于反映每克端氨基聚醚等的含氨基物质的量，并可评估二胺的纯度或含量。水相法氯化橡胶的制备就是采用天然橡胶乳液作为原料，加入适量助剂，排除蛋白质、脂肪酸和糖分等杂质，然后用浓盐酸水溶液进行酸化处理至一定 pH 值，20∼40°C 下通人氯气进行氯化反应一定时间，再在催化剂作用下，40∼70°C 深度氯化，通氯气直到产物含氯量达到 60% 以上。将反应产物溶液经过水洗脱酸。将沉淀物（氯化橡胶）送人离心机用清水洗涤数次，以除净其残剩的氯化氢至中性时再离心脱水，经过烘廊干燥，压缩、包装、入库。氯磺化聚乙烯是由分子量20000左右的高压聚乙烯溶解于四氯化碳，在偶氮二异丁睛的作用下与氯、二氧化硫进行氯化和磺化制得。采用适当分子量和粒度的聚乙烯粉末，分散剂和水或稀盐酸-与PE比例为 1:(8∼10)，均匀分散在塘瓷反应罐中，加入引发剂并在UV光照射下，搅拌下通氯气反应，控制温度程序和时间、压力，计量通氯量至氯含量 >60% 并停止反应。反应副产物氯化氢回收制备稀盐酸。HCPE沉降后用水和碳酸钠漂洗至中性，离心脱水至气流干燥工段，检验包装入库。氯醚树脂由20世纪70年代德国BASF公司开发，采用氯乙烯和乙烯异丁基醚进行悬浮乳液聚合，以获得含有功能基团的共聚物。具体步骤包括：将75%的氯乙烯和25%的乙烯异丁基醚按比例混合，进行聚合反应。聚合反应产物为LAROFLEXMP树脂，具有不同的粘度规格。纤维素与硝酸和硫酸的混合酸进行酯化反应1. 纤维素的精制：以优质短绒棉形式的纤维素在加入湿润剂（如松香皂）的苛性碱中隔离空气煮沸，以除去脂肪、蜡、表皮质等脏物和不纯物。然后经漂洗、漂白、机械碾压和热空气烘干处理，得到含有98%以上α纤维素的精制脱脂棉。2. 硝酸纤维素的生产：在间歇式生产中，以脱脂棉为原料，用硝酸和硫酸混合酸进行酯化，反应需仔细和精确地控制，以达到预想的硝化度。硫酸用于带走反应中形成的水。然后经过驱酸、安定处理和加压降黏，脱水，再加湿润剂（乙醇、异丙醇或丁醇）以驱水及混合、离心，得到的产品为硝化棉。市场上销售的硝化棉一般为70%硝化棉和30%醇湿润剂的混合。溶解硝酸纤维素的溶剂包括活性溶剂、非活性溶剂和助溶剂。活性溶剂有酯类（如乙酸乙酯、乙酸丁酯、乙酸异丁酯等）、酮类（如丙酮、甲乙酮、甲基异丁酮）、醚醇类（如丙二醇乙醚、丙二醇丁醚和二丙酮醇等）。助溶剂一般为醇类，如丁醇、异丁醇、异丙醇和乙醇。稀释剂通常为甲苯和二甲苯，但也可用一些环保的脂肪烃。1. 先用非活性溶剂进行搅拌，打碎厚实的结块以形成均匀的糊状浆。2. 搅拌糊状浆并缓慢地加入活性溶剂，以便快速地溶解硝酸纤维素。3. 为了得到有效的预湿润，1份（质量）的硝酸纤维素需要至少1.5～2份（质量）的非活性稀释剂。4. 如果混合溶液中有高比例的稀释剂，建议留下多余的稀释剂，先加入真溶剂和助溶剂，让硝酸纤维素完全溶解后，再慢慢加入剩余的稀释剂，并加以充分搅拌。5. 在溶解的过程中，硝酸纤维素必须完全浸泡在溶剂中，以保证高剪切力下溶解的安全。6. 加入的顺序和所用液体成分的量对溶解速率有重要关系。7. 特别有效的是，硝酸纤维素先与助溶剂或者稀释剂相混合，再加入剩余的活性溶剂。整出某一中间黏度的硝化棉液：X_{\\star}=\\frac{\\log t_{\\sf t}=-\\log t_{\\sf\\ A}}{\\log t_{\\star}-\\log t_{\\sf\\ A}}; X_{\\curlywedge}=1-X_{\\star}; 其中，x_{\\star} 是黏度大的硝化棉分数；t_{\\mp}，I_{\\mathsf{B}^{t}\\star}，lg t_{\\hbar} 是落球经过中间黏度、大小黏度的同溶剂配方的硝化棉液所用秒数的对数。将甲基丙烯酸羟基乙基酯作为反应中产生的HCl的捕获剂，加入三乙基胺和正已烷作为溶剂到反应瓶中。在冷却状态下，滴加三甲基氯硅烷。过滤去除所得铵盐，进行减压蒸馏，得到甲基丙烯酸三甲基硅氧乙基酯（TMSEMA），这是含有封闭羟基的甲基丙烯酸酯单体，可以与其他丙烯酸酯或乙烯基单体共聚，制成丙烯酸酯低聚物。将丙烯酸和其他单体按照表2-1-262中的配方配制，分别置于两个滴加器中。在 $140^{\\circ}\\mathrm{C}/6\\mathrm{h}$ 搅拌下，滴加到预先放置有二甲苯的反应釜中（总投料量 $75\\%$ ）。物料滴加完后，在 $140^{\\circ}\\mathrm{C}$ 下保持 $5\\mathrm{h}$ ，然后减压蒸去二甲苯。得出不同功能基的丙烯酸低聚物R-1到R-6。1. Use dichlorodimethylsilane monomer and hydroxyethyl methacrylate to perform hydrolysis and condensation under basic catalysis, introducing acryloxy as the end group to the polysiloxane chain. 2. Conduct an ester exchange reaction between dialkoxysilane and hydroxy methacrylate, also introducing acryloxy as the end group. 3. Utilize hydroxyl-containing silane and methacrylate for esterification to introduce acryloxy. 4. React terminal hydroxyl silane with diisocyanate, followed by a reaction between NCO group and hydroxy methacrylate, or react terminal hydroxyl silane with diisocyanate-methacrylate semi-addition product to introduce acryloxy. These methods lead to UV-curable organic silicon-polyurethane-methacrylate oligomers, which are still acryloxy terminated.辐射固化有机-无机杂化涂料的成膜物结构溶胶-凝胶法的原理是利用Si、Ti、A1、$z_{\\mathrm{r}}$等烷氧化物作为无机前驱体，经水解、缩合形成无机网络溶胶，和加入的有机单体或低聚物聚合，形成有机-无机杂化凝胶体。根据有机-无机杂化体系中引入的基团性质，采用阴离子或阳离子UV固化工艺；如果是丙烯酰氧基为主，用阴离子的UV固化工艺；如果是环氧基封端为主，则采用阳离子的UV固化工艺。此外，采用气溶胶促进等离子体工艺（AAAP）固化有机-无机杂化涂料，具有不用光敏剂，不受氧阻聚，可以固化UV不能固化和热不能固化的涂料，所得涂膜致密性强，性能良好，工艺成本低。在装有冷凝器、搅拌器的三口烧瓶中加入水和保护胶，升温，搅拌。待温度达到82℃时，加1/2的引发剂过硫酸铵，保温10分钟后，加1/10混合单体和1/10乳化剂，10分钟后开始滴加剩余混合单体和剩余引发剂、缓冲剂ΔNaHCO3和抑制剂G的混合溶液，在82~84℃用3小时滴加完，保温1小时，降温，过滤出料。为安全起见，通常在四氟乙烯单体中加入一定量的三乙胺以阻止发生自聚。实验室采取聚四氟乙烯热分解的方法制取六氟丙烯单体，而工业上则采取六氟一氯丙烷的热分解来制取。三氟氯乙烯单体可以通过三氟三氯乙烷脱氯、三氟二氯乙烷脱氯、氟氯代羧酸的碱金属盐脱二氧化碳、二氟一氯甲烷与一氟二氯甲烷的共热分解和聚三氟氯乙烯的热分解五种方法合成。氟乙烯（VF）单体可以通过乙炔与氟化氢加成、氟（氯）乙炔脱卤化氢、氯乙烯或氯乙烷与氟化氢反应和乙炔与氟乙烷共热分解合成。工业上制备氟乙烯单体最常用的方法是乙炔的气相氢氟化。溶剂型氟碳树脂主要由三氟氯乙烯/四氟乙烯、烷基乙烯基醚/烷基乙烯基酯、羟烷基烯醚、烯酸等单体共聚而成。多元共聚的氟烯烃-乙烯基醚/酯共聚物氟碳树脂需关注氟烯烃单体、烷基乙烯基醚、羟烷基乙烯基醚及烯酸单体的合适配比，以保证树脂具备良好的耐候性、耐化学药品性及优良的附着力和润湿性。聚偏二氟乙烯氟碳树脂可通过乳液聚合和悬浮聚合合成。在乳液聚合中，使用含氟表面活性剂、引发剂和链终止剂，反应结束后去除残余引发剂和表面活性剂，然后将乳胶干燥并研磨成平均粒径为2至4μm的细粉末。悬浮聚合在水介质中进行，使用引发剂、胶体分散剂（不一定都需要）和链转移剂以控制分子量，获得颗粒状聚合物。溶剂可溶常温固化氟烯烃-乙烯基醚/酯共聚物的生产采用溶液聚合工艺，聚合反应为高压聚合反应，常用引发剂包括偶氮二异丁睛、过氧化二苯甲酰和有机过氧化酯类。溶剂型含氟丙烯酸酯类氟碳树脂则采用常压溶液聚合工艺。在2L带有电磁搅拌的高压釜中加入200g乙酸丁酯、2.5g偶氮二异丁腈，将高压釜抽空，充氮，然后用计量泵加入126g环己基乙烯基醚、17.2g醋酸乙烯酯、147.2g叔碳酸乙烯酯、116g羟丁基乙烯基醚、300g丙酮，然后通入四氟乙烯至反应釜压力为0.5MPa，将高压釜逐渐加温至70℃，通入四氟乙烯至反应釜压力为1.5MPa，维持压力，保持温度在70℃。反应时间为4.5小时。降温出料，得到清澈透明的无色或浅黄色黏稠液体。取部分该黏稠液体，用石油醚作为沉淀剂进行沉淀，然后将沉淀物在60℃下真空干燥24小时得到样品。1. Select fluorinated monomers such as trifluorochloroethylene (CTFE), and consider mixing with other fluoromonomers like VDF and TFE if desirable. 2. Introduce hydrophilic non-fluorinated monomers which may include vinyl alkyl ethers, allyl alkyl ethers, or unsaturated carboxylic acids, such as hydroxyl butyl vinyl ether (HBVE), ethyl vinyl ether (EVE), and various acrylates. 3. For enhancing performance, add functional monomers, such as vinyl alkoxysilanes for increased adhesion and crosslinking monomers for improved solvent resistance. 4. Utilize an appropriate emulsifier, preferably fluorinated emulsifiers like perfluorooctanoic acid, or conventional emulsifiers to ensure stability. 5. For polymerization, utilize initiators; azo-type initiators like azobisisobutyronitrile for solution polymerization, or water-soluble persulfate-type initiators like potassium persulfate for emulsion polymerization. Optionally, use a redox initiation system. 6. Maintain the pH of the polymerization system using sodium carbonate or disodium hydrogen phosphate.水性氟碳树脂制备的方法可以分为溶液聚合-相反转法和乳液聚合法。溶液聚合-相反转法需设计合适的羧基值和分子量，在一定温度下蒸除大部分溶剂，使用氨化成盐法以及适量乳化剂，使得氟碳树脂在水相中稳定分散。乳液聚合法则通过将单体、乳化剂、调节剂混合在水相中控制工艺条件。在分散（悬浮）聚合法中，以过硫酸盐为引发剂，在不锈钢压力容器中加入全氟羧酸盐分散剂，通入四氟乙烯气体，加入活化剂并在一定温度下引发聚合，制作聚四氟乙烯水分散液。使用三氟氯乙烯为主要含氟单体，在压力状态下进行聚合反应，控制生产工艺以获得稳定的水性氟碳树脂。在高压反应釜中加入定量去离子水、部分乳化剂及碳酸氢钠，搅拌溶解均匀后，加入按一定预乳化工艺进行乳化的单体预乳化液 4%~6%，开动搅拌混合均匀后，开始升温，当温度达到 (60±2)℃，加入 20% 引发剂溶液，因反应放热温度自行升高，控制温度在75～85℃，当温度平稳时，滴加单体预乳化液和引发剂溶液，在2～4h内加完，当系统压力逐步下降直至平衡时，反应结束。冷却到40℃以下。加入中和剂，调节pH为7～8，过滤，包装。若在聚合过程中引入双丙酮丙烯酰胺（DAAM）功能单体，先制成含有活泼羰基的水性氟碳树脂，然后加入适量多元酰肼，在干燥成膜过程中进行反应，得到可交联的单组分氟碳树脂涂料。选择合适的氟烯烃单体（如四氟乙烯、三氟氯乙烯、乙烯等）进行均聚或共聚，通过选择聚合工艺、引发剂（过硫酸盐和有机过氧化物）与引发体系，控制分子量以及聚合反应参数。不忘在热塑性粉末氟碳树脂的合成中加入链转移剂（如含氟化合物）以优化特性。对于热固性粉末氟碳树脂，主要是指含羟基官能团的氟烯烃-乙烯基醚/酯共聚物，在自由基引发剂存在条件下， $30\\mathrm{\\sim}100\\mathrm{\\textperthousand}$ 之间，可通过溶液聚合、乳液聚合或悬浮聚合进行共聚反应。采用溶液聚合工艺时，制得共聚物树脂溶解在溶液中，通过沉淀剂进行沉淀，树脂从溶液中分离、干燥。采用乳液聚合或悬浮聚合时，制得共聚物氟碳树脂从乳液或悬浮液中分离、水洗、干燥。1. 乙烯-三氟氯乙烯共聚物热塑性粉末氟碳树脂的制备过程：使用2L高压反应釜，抽真空脱氧，氧气浓度为42μL/L。加入混合溶剂（1240B三氟三氯乙烷、20g脱氧去离子水），搅拌加热至50℃。用高压计量泵打入1.0g过氧化二碳酸环己酯，同时停止进料。反应温度控制在50~60°C，反应压力1.55MPa，聚合时间1.0h。第二步反应中加入180g脱氧去离子水，反应温度在60~85°C，时间3.0h，补加混合反应单体共加入31.2g。最后，聚合产物溶液投入蒸馏釜，加1000g去离子水，蒸馏回收有机溶剂，冷却、放料、干燥，得到粉状聚合物158g。  \\n\\n2. 三氟氯乙烯-乙烯基酯共聚物粉末氟碳树脂的制备过程：在2L不锈钢高压反应釜中加入270g醋酸乙烯酯、82g羟乙基烯丙基醚、8g乙烯基乙酸、4.6g正丙基过氧化二碳酸酯、506g乙酸丁酯，氮气置换。加入576g三氟氯乙烯，温度升至40°C，聚合反应持续24h。反应结束后排出未反应三氟氯乙烯，取反应溶液入正已烷中沉淀，干燥得到氟碳树脂共聚物768g。The text excerpt does not provide a specific experimental protocol for the synthesis of hydrophilic polymers with functional groups.高分子聚合物的溶解度参数通常是通过物质的化学结构计算获得。此外，可以使用反相色谱法或通过与已知溶解度参数的溶剂相溶的方法获得。特性黏度法中，将一定量的聚合物溶解于具有不同溶解度参数的溶剂中，并在特定温度下测定其特性黏度；最大特性黏度对应的溶剂体系的溶解度参数即为聚合物的溶解度参数。平衡溶胀法是在特定温度下将交联的高分子聚合物放入具有不同溶解度参数的溶剂中进行溶胀，达到平衡后测定溶胀度，最大溶胀度对应的溶剂体系的溶解度参数即为该高聚物的溶解度参数。将100g贝壳松脂溶于500g丁醇中配制成标准溶液，温度在25°C±2°C，取20g贝壳松脂·丁醇溶液滴加烃类溶剂至出现浑浊时，记录所需烃类溶剂的毫升数，试验平均误差为±0.1mL。1. Utilize trimethylolpropane triglycidyl ether with the molecular formula C15H26O6 and a molecular weight of 398. Ensure the density is 1.16 g/cm³ and the epoxy equivalent is in the range of 135 to 160. This compound contains three hydroxyl groups and three epoxy groups, which enhance its performance as a diluent for epoxy resin, particularly in improving the thermal resistance of the epoxy system.新戊二醇与环氧氯丙烷进行脱水反应将正丁醇与环氧氯丙烷进行脱水反应，以合成4-丁二醇二缩水甘油醚。在反应过程中，确保温度保持在150°C以上，以促进环氧基团的形成。在固化过程中，这些环氧基团将参与反应，形成链状及网状结构。乙二醇与环氧氯丙烷脱水反应苄基缩水甘油醚由苯甲醇与环氧氯丙烷脱水反应而成，制得无色透明液体，含有功能性环氧基团，以用于高要求应用。The hydrophilic polymer is synthesized using 1-butanol and epichlorohydrin through an etherification process followed by an epoxidation step to obtain a glycerol-type active epoxy diluent containing ether bonds and epoxy groups.使用脂肪缩水甘油醚作为单官能基稀释剂，以降低树脂体系的黏度，添加至最适比例以达到理想的降黏效果。The synthesis of hydrophilic polymers can involve the use of allyl glycidyl ether, which has the molecular formula C6H10O2 and a relative molecular mass of 114. It has a density of 0.97 g/cm3 and an epoxy equivalent of 98 to 102. This monofunctional diluent can be utilized to reduce the viscosity of resin systems when mixed with epoxy resins, allowing for the incorporation of a higher proportion of fillers and enhancing permeability.苯酚与环氧氯丙烷经开环醚化，再经环氧化合成含有功能基团的亲水性聚合物，使用丙烯酸羟乙酯（HEA）、丙烯酸羟丙酯（HPA）、甲基丙烯酸羟乙酯（HEMA）和甲基丙烯酸羟丙酯（HPMA）作为活性稀释剂，这些稀释剂具有高沸点、低黏度和低玻璃化温度。反应中，应保证这些活性稀释剂与异氰酸基反应以增强聚合物的特性。The synthesis of hydrophilic polymers with functional groups involves using various monomers such as GMA (glycidyl methacrylate), IBOA (isobornyl acrylate), THFFA (tetrahydrofuran methacrylate), and POEA (phenoxyethyl acrylate). Each of these monomers is characterized by specific properties such as molecular weight, boiling point, and density that influence the polymerization process. For instance, GMA has a molecular weight of 142, low viscosity, and high adhesion properties due to the epoxy group, while IBOA, with a molecular weight of 208, offers low shrinkage and low skin irritation. THFFA incorporates a polar tetrahydrofuran ring enhancing adhesion, and POEA is noted for its high reactivity and low skin irritation despite having a phenolic odor. The specific conditions for polymerization, such as temperature and initiation method, are dependent on the chosen monomers and their inherent properties.双官能团活性稀释剂的合成涉及使用具有两个可参与光固化反应的活性基团的分子。可以从二元醇结构出发，合成乙二醇类二丙烯酸酯、丙二醇类二丙烯酸酯以及其他二醇类二丙烯酸酯。聚乙二醇二丙烯酸酯系列的合成方法涉及选择相应摩尔质量的聚乙二醇（例如PEG（200）、PEG（400）、PEG（600）），与丙烯酸酯进行反应，通过聚合导致反应物形成具有特定功能基团的聚合物。反应条件调整以控制黏度和其他物理性质，如光固化速率。二丙二醇类二丙烯酸酯（DPGDA）与三丙二醇类二丙烯酸酯（TPGDA）可以作为光固化涂料的稀释剂，通过一定比例配比后，利用光固化技术进行合成。1，4-丁二醇二丙烯酸酯（BDDA）相对分子质量为198，沸点为275^{\\circ}C，密度为1.0578/{\\mathrm{cm}}^{3}，低黏度，对低聚物溶解性好、稀释能力强，但对皮肤刺激性较大。1，6-己二醇二丙烯酸酯（HDDA）相对分子质量为226，沸点为295\\mathrm{^{\\circ}C}，密度为1.038/\\mathrm{cm}^{3}，具有低黏度、稀释能力强、对塑料附着力好的特点，可改善固化膜的柔韧性，但对皮肤刺激性较大，价格较高，是光固化涂料常用的活性稀释剂之一。新戊二醇二丙烯酸酯（NPGDA）相对分子质量为212，密度为1.03g/cm，具有低黏度、稀释能力强、高活性、光固化速率快的特点，对塑料附着力好，玻璃化温度较高，但对皮肤刺激性较大，是光固化涂料常用的活性稀释剂之一。邻苯二甲酸乙二醇二丙烯酸酯（PDDA）价格便宜，光固化速率快，是我国自行开发的活性稀释剂，效果稍差。多官能团活性稀释剂每个分子中含有三个或三个以上可参与光固化反应的活性基团，因此不仅光固化速率快，而且交联密度大。常用的多官能团活性稀释剂包括三羟甲基丙烯酸酯（TMPTA）、季戊四醇三丙烯酸酯（PETA）、季戊四醇四丙烯酸酯（PETTA）、二缩三羟甲基丙烷四丙烯酸酯（DTMPTTA）、二季戊四醇五丙烯酸酯（DPPA）和二季戊四醇六丙烯酸酯（DPHA）。使用时应考虑其分子量、密度、黏度、光固化速率、交联密度、固化膜的硬度和低皮肤刺激性等特性。N,N-Dimethylacetamide (DMA) is used for dissolving a variety of resins and polymers. It is compatible with water and organic solvents, and is employed in the production of acrylic fibers, films, sheets, and coatings. Additionally, DMA serves as a reaction medium and intermediate in organic synthesis.合成亲水性聚合物的过程包括：1. 选择合适的纤维素衍生物，如羟乙基纤维素（HEC）、甲基羟乙基纤维素（MHEC）、或聚阴离子纤维素（PAC）。2. 在反应体系中引入功能性长链疏水烷基进行改性，形成疏水改性纤维素（HMHEC）。3. 在碱性条件下，与不饱和共聚单体和羧酸进行共聚反应，以合成非缔合型碱溶胀增稠剂（ASE）。4. 在聚合过程中，加入交联剂以提高聚合物的稳定性。5. 控制pH以调节合成过程中羧基的电离程度，从而影响聚合物的粘度特性。6. 最后，根据特定的应用需求，通过调节疏水基团的类型和含量，优化聚合物的增稠效果和相应的物理化学性质。成膜助剂的用量主要应根据乳液的MFT、乳胶漆的MFT和成膜助剂的助成膜效能，通过试验确定。确定成膜助剂用量时，不仅要考虑乳液的低温成膜性，更应注意乳胶漆的低温成膜性，如在 5℃ 或较低温度下的成膜性，通常在调漆阶段加入成膜助剂，并在乳液加入后，一边慢速加人一边不停地混合。成膜助剂一般是单独使用的，但也可搭配使用，以便取得更好结果。对每个批号的进货，通常还要进行验收检验，测试内容如折射率、馏程、密度、外观和气味等。聚合型乳化剂的合成在乳液聚合中使用，需选择含有可聚合基团的乳化剂，并在反应中应用自由基聚合的条件。在此过程中，这些乳化剂不仅参与乳化，还作为共聚单体直接融入聚合反应，使乳化剂分子通过共价键结合到乳液聚合物分子上，从而增强成膜聚合物的耐水性、黏结性和涂膜性。合理选择乳化剂，优化其用量，并确定适宜加人方式，是获得优质乳液的前提条件之一。所选乳化剂的HLB值应和乳液聚合体系相匹配。对于乳液共聚体系，所要求的HLB值可将各组分的HLB值按质量分数进行加权平均求取。用于乳液聚合的乳化剂通常为阴离子型乳化剂和非离子型乳化剂的复配物，所选用的离子型乳化剂的三相点应低于反应温度，非离子型乳化剂的浊点应高于反应温度。应选用临界胶束浓度尽量小和增溶度大的乳化剂，且所选用的乳化剂不应干扰聚合反应。合成树脂乳液是由乳液聚合法制取的合成树脂在水中的稳定分散体。用于乳胶漆的乳胶粒径一般为 0.05至0.5微米。高分子量赋予涂膜优良性能，低黏度给乳胶漆的生产、施工应用带来便利。将乳液涂布在玻璃板上，如在 (50±2)τ 放置4h，观察乳液膜的透明度，越透明越好。将上述玻璃板浸泡在蒸馏水中，观察其出现泛白所需的时间，时间越长说明耐水性越子。可在纤维水泥板上涂布白石试验乳胶漆进行试验。根据经验和调查了解，选定原材料。确定配方参数，乳胶漆的体积固含量为 33%，颜料体积浓度PVC为 63%。在100L乳胶漆中，固体为33L，颜料和填料总体积为33×63%=20.79（L)。配方中乳液用量12.21÷53.09%×1.08=24.84（kg）。初始配方包括水、羟甲基纤维素Celflow S-100、pH调节剂AMP-95、丙二醇、成膜助剂Texanol、防腐剂AMA480、消泡剂Colloid 643、湿润剂Triton N 101、分散剂Colloid 226(35%)、钛白粉、粗碳酸钙、烧高岭土等。配比根据体积和质量固含量计算。在生产硅酸盐乳胶涂料时，乳液的耐碱性、耐水解性以及和水玻璃的相容性是十分重要的。相容性可通过试验确定，即将乳液和等量的水玻璃用调墨刀搅拌混合，当乳液和水玻璃都没有凝聚和结块时，认为相容性合格。生产硅酸盐乳胶涂料的加料次序是水玻璃必须在最后加入，以防强碱使乳液凝聚和结块。The synthesis of hydrophilic polymers involves using a blend of solvents to adjust drying time and control fluidity. The formulations typically include thermoplastic acrylic resin solutions and acrylic ester-polyester resin solutions as film-forming substances. Plasticizers are added at approximately 2% of the resin weight to enhance flexibility, and organic silicons are used as defoamers due to the limited usage of surfactants. Organic clay serves as a rheological thickener to improve thickening and anti-sedimentation effects, although it may adversely affect the leveling of the coating.在引发剂存在的条件下，将含氟丙烯酸酯单体、甲基丙烯酸酯类单体和丙烯酸酯类单体进行引发聚合，以获得具有较强憎水性能的含氟丙烯酸酯改性的丙烯酸酯树脂。在料浆制备时，先将分散介质投入涂料罐中，按照设计的配方投入各种助剂，搅拌均匀后再投入颜料和填料，充分搅拌并使之均匀，得到预分散料浆。作为分散介质的溶剂一般不止一种，大多是使用混合溶剂。根据情况可以将各种溶剂全部投入，也可以预留一部分溶剂留待涂料调制程序中加入。在助剂的投料过程中一般是先投入消泡剂、润湿剂、分散剂等，搅拌均匀后再投入流变增稠剂。为了使料浆具有一定黏度以利于研磨操作，并方便其后的涂料调配操作，在料浆制备时常常加入一定量的树脂溶液。将磨细的料浆转移至混料罐中，在混料罐中的磨细料浆处于搅拌的状态下，将基料缓慢地投入混料罐中，搅拌均匀，制成涂料混合料。在水玻璃涂料中加入固化剂来加速固化和提高耐水性，固化剂的用量为水玻璃重量的12%至15%为宜。常用的固化剂包括氟硅酸钠（Na2SiF6）和缩合磷酸盐，前者促进蜕出硅酸凝胶加速析出。缩合磷酸盐在涂料中缓慢水解，释放出H+与水玻璃反应，形成以—Si—O—Si为主链的无机网状薄膜。The excerpt does not provide a specific experimental protocol for the synthesis of hydrophilic polymers with functional groups.把水和硅溶胶投人反应釜中混合均匀，再投入分散剂搅拌均匀后，投入颜料和填料，充分搅拌均匀。然后，将混合料浆通过砂磨机或胶体磨进行磨细/研磨后进行调漆操作，即投入乳液和助剂，充分搅拌混合均匀，过滤包装，得到成品无机外墙建筑涂料。将硅酸钾溶液投入搅拌罐中，加水搅拌均匀。然后向搅拌罐中投入分散剂，接着加入各种颜料和填料，搅拌均匀后，再加入成膜助剂和部分消泡剂，采用高速(800~1000r/min)搅拌0.5小时以得到料浆。随后通过砂磨机研磨至细度小于60μm，并将磨细的混合料浆转移至搅拌罐中。在低速(300~500r/min)搅拌状态下，缓慢加入SBR乳液，加入后再搅拌约20分钟使之均匀。根据泡沫的多少酌加适量消泡剂以消泡。如果需要配制彩色涂料，可以根据色卡经试验确定加入色浆的种类和数量，然后搅拌均匀以调配所需要的颜色。To synthesize hydrophilic polymers with functional groups, start with a linear long-chain macromolecule to achieve high elasticity. Use short rigid segments generated from diols to form polyurethane chain segments. Incorporate isocyanates and chain extenders to control the rigid and flexible segments. Adjust the type of terminal hydroxyl compounds and their molecular weights to influence the flexibility and curling of macromolecular chains. Control the reaction conditions to balance the opposing properties of both segments, achieving a block structure that meets performance requirements for the elastic polyurethane resin.预聚体的合成工艺按配方称取聚醚多元醇（N220、N330），置于反应釜中加热脱水。当温度升至 80°C 左右时，开动真空泵进行抽真空脱水，抽真空的压力保持为 66.66∼ 93.33kPa且始终搅拌。再加热至 110°C，继续脱水2h。然后关闭蒸汽阀和真空泵，同时开启冷却水，使反应釜内的物料冷却，降温至 50°C 以下。按配方称取TDI和PAPI，在该过程中勿使温度超过 85°C。当TDI和PAPI加完后，关闭冷却水。继续用蒸汽加热升温。升至85℃后，保温2h。将聚醚N303投入反应釜中，加入5%苯脱水，冷却至35{^circ}C，加入TDI，通氮气，搅拌，升温至60~70^{\\circ}C反应，加入10%甲苯以调节黏度，然后加入二元聚醚N204（预先用苯脱水），升温至80~90^{\\circ}C，保温2~3小时，取样以二丁胺测定—NCO含量决定终点。将粉料各个组分投入混料机中混合均匀，作为粉料组分包装；液料组分分开包装，使用时混合均匀。粉料和液料的配合比粉料：液料 = (1.5至3.0):1。将粉料各个组分投入混料机中混合均匀，作为粉料组分包装；液料组分分开包装，使用时混合均匀。将涂料各个组分材料投入圆锥形螺旋混料机中混合均匀。为了保证各组分能够充分混合均匀，可将用量小的消泡剂、分散剂和甲基纤维素先和少量的石英粉混合均匀，然后再和涂料其他组分混合，作为粉料组分包装。该类涂料的生产技术较为简单，和一般粉状建筑涂料的生产过程极为相似，主要是一般的粉状物料的物理混合过程。具体步骤包括将以下原材料按照质量分数进行混合：水泥（87%）、渗透结晶母料（4%）、粉状硅酸钠（3%）、石英砂（5%）和糖（1%）。涂料配方为：水 18至24 份；润湿分散剂 0.4至1.0 份；复合纳米材料 0.1至0.3 份；纳米硅基氧化物 1.0至3.0 份；二氧化钛 10至20 份；填料 25至35 份；消泡剂 0.1至0.2 份；丙烯酸醋乳液 25至35 份；增稠剂 0.3至0.4 份；流平剂 0.2至0.3 份。日光热反射绝热涂料的制备同普通涂料相似，都是物理混合过程，但在生产程序的设计上应注意空心玻璃微珠不能够受到研磨，否则会使其破碎而失去反射性能。将异丁醇加人到反应釜中，升温至回流，保持稳定 10min；将丙烯酸丁酯、苯乙烯、丙烯酸羟丙酯、丙烯酸、BPO混合，搅拌至完全混溶，在搅拌下滴加到大约4/5的混合物（耗时约2h）后暂停，保温2h，然后继续滴加，耗时约30min，继续保温 3h；降温至 110°C，加入乙醇胺，搅拌约 30min；降温至 60°C，过滤、出料。将低分子量聚丁二烯树脂与不饱和脂肪酸（如顺酐或反丁烯二酸酐）进行加成反应，引入羧基，反应条件为190至200°C，持续6至10小时，确保顺酐的加成率达到98%以上。反应中添加阻聚剂以控制反应粘度，提高稳定性。随后，使用水溶性胺类中和反应产物以获得可水稀释的聚合物。首先在环氧树脂上引入含N、P、S等元素的可成盐基团（一般采用有机胺类)，再用有机酸中和成盐使之分散在去离子水中。对阳离子树脂的合成采用仲胺或亚胺酮胺化的方法。然后，用酸中和成铵盐赋予树脂以阳离子特性。接着，扩链反应中合并了低分子量环氧树脂与各类链扩展剂。固化剂可以使用封闭型异氰酸酯类化合物，反应温度设置在60至80°C，反应持续2至3小时。最后，反应后的高分子量环氧树脂中间体与胺反应，得到阳离子化的树脂，再与交联剂和助剂一同分散在水-酸溶液中。1. 将新戊二醇、三羟甲基丙烷、四氢苯酐、苯二甲酸酐、己二酸以及回流二甲苯等原料投入反应釜中，分水器中加好二甲苯。 2. 升温到固体物料全部熔融后再开启搅拌。在 175°C 反应1.5h，保持正常回流。升温到 190°C，反应2h，然后继续升温至 200°C，保温回流。 3. 在 200°C 下，保温回流至酸值为 9~13，测黏度。 4. 如果酸值合格，而黏度偏低，则可升温至 210°C，保温回流直至黏度合格。 5. 待黏度合格后将物料抽至兑稀罐中。降温至 130°C 以下，加入兑稀的二甲苯，搅拌均匀，然后降温至 70% 以下，过滤、包装。1. 制造浓色浆工艺:\\n   a. 在配料缸中加入配方中所列溶剂及主成膜物质，搅拌均匀。\\n   b. 在搅拌下慢慢加入颜料，加完后再搅拌一定时间。\\n   c. 在搅拌下慢慢加入氨基树脂，加完后再高速分散一定时间使之完成预分散。\\n   d. 在砂磨机上研磨至细度小于10μm，过滤、出料。\\n\\n2. 冲淡工艺:\\n   a. 在调漆缸中先加入制备的浓色浆。\\n   b. 根据浓浆黏度的具体情况，在搅拌下分批逐步加入冲淡用调和漆料。\\n   c. 第一批投入后，慢搅10分钟直至浓浆变成均匀、流动性较好的糊状物。\\n   d. 继续加入后几批冲淡用调和漆料，最后加溶剂，再搅拌至少10分钟。将分散蜡液 $(6\\%$ ）添加到配漆缸中，搅拌 $10\\mathrm{{min}}$ 左右，检查细度（如 ${\\leqslant}20\\mu\\mathrm{m})$ 。然后在搅拌下慢慢加人热固性丙烯酸树脂，再继续搅拌至少 $30\\mathrm{{min}}$ ，检查细度应合格（如${\\leqslant}20\\mu\\mathbf{m})$ 。依次加入聚酯膨润土胶液 $(10\\%)$ 、聚酯树脂、Setal90173SS50、CAB381-0.5溶液$(20\\%)$ 、CAB381-2溶液 $(20\\%)$ 、MF650氨基树脂、BYK300、松节油，然后在揽拌下慢慢加入PMA、Alpate816AR（铝粉浆）、Alpate8820（铝粉浆）、二甲苯，继续搅拌 $30\\mathrm{{min}}$ 。至少熟化10h以上，方可用于配制底色漆。将棕榈油和甘油投入到反应釜中，在 N2 保护下升温至 150°C；将LiOH（预先将其与部分棕榈油混合成浆状物）加入到反应釜中，升温至 230°C 保持温度至 1:5 清 (甲醇)；降温至 150℃，加入回流二甲苯和苯二甲酸酐，升温至 180°C，回流至 AV 约为 30；继续升温至 200°C，保温至 AV ≤ 15，粘度为 15~20 s；降温，加入兑稀二甲苯，过滤、出料。反应釜应清洁、干燥，在分水器中加满回流溶剂，通 ${\\bf N}_{2}$ @ 按顺序加人异壬酸、三羟甲基丙烷、季戊四醇、苯酐、亚麟酸三苯酯、二丁基氧化锡（注：亚麟酸三苯酯和二丁基氧化锡需称量精确)，关闭反应釜，最后加人二甲苯（1）。在 ${\\bf N}_{2}$ 保护下升温至 $200\\Upsilon$ ，当釜内温度达到 $100^{\\circ}\\mathrm{C}$ 时，停通 ${\\bf N}_{2}$ ，关闭部分热媒油管，此时有放热反应发生，故釜内温度上升到 $135\\mathrm{^{\\circ}C}$ 垂 再次开启热媒油管，继续升温至回流、脱水。待出水量达到总投料量的 $5.5\\%$ 时，加入二甲苯(二)，继续回流至黏度 $\\mathbf{\\Delta}=\\mathbf{V}\\sim\\mathbf{W}$ $\\scriptstyle\\mathbf{A}\\mathbf{V}=5\\sim7$ 。取样配比如下：样品 50.0 二甲苯 丙二醇丁醚 15.0。当抽样合格后，停加热，加人丙二醇丁醚，搅拌均匀后，将物料转移至加有二甲苯（四）的兑稀釜中。反应釜用二甲苯（五）清洗，放人兑稀釜。降温至 $80^{\\circ}\\mathrm{C}$ 左右，过滤、包装。In the synthesis of hydrophilic polymers, combine thermosetting acrylic resins and polyester resins with SCA-modified polyester resins, amino resins, and CAB. Maintain the ratio of polyester resin at 16% to 26%, acrylic resin at 27% to 32%, SCA-modified polyester resin at 3% to 15%, and CAB at approximately 10%. It is recommended to balance the ratio of polyester and acrylic resins at around 1:1. Use a combination of different CABs to adjust the solid content during application, prevent re-dissolution during glossing, and achieve suitable physical drying times. SCA-modified polyester resin serves as a control for flow and prevents the lacquer film from running, providing thixotropic properties, which is particularly important for light metallic glitter paints to effectively prevent color spots and local color differences.1. Add 10% dispersing wax liquid (part one) to the mixing tank, stir, and check the fineness, which should be ≤20μm. Then, add thermosetting acrylic resin and polyester resin while stirring for 30 minutes, checking the fineness to be ≤20μm. 2. Sequentially add Setal 90173 SS 50, CAB 381-0.5 (20%) (part one), CAB 381-2 (20%), etherified melamine formaldehyde resin, BYK 306, 100° aromatic, and butyl soluble fiber (part one) into the tank. Slowly add 101 black under stirring and disperse at high speed for 1 hour. Filter the mixture using a bag filter equipped with a double-layer filter bag. 3. In a separate tank, add Alpate 8160 AR and Alpate 8820 AR, then add 10% dispersing wax liquid (part two), and disperse at high speed for 1 hour. Under stirring, add CAB 381-0.5 (20%) (part two) and continue stirring for 30 minutes, checking the fineness to be ≤20μm. 4. After the aluminum powder slurry is prepared, it should mature for 10 hours, and stir for another 30 minutes before use. 5. Slowly add the prepared varnish solution to the aluminum powder slurry under stirring, dispersing for 30 minutes. Filter using a sieve, and then stir for 2 hours.a.将甲苯和丁醇加人到反应釜中，在 N2 保护下升温到 80°C 。b.将苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸丁酯、-甲基丙烯酸氧丙基三甲氧基硅烷、顺丁烯二酸单丁酯、过氧化2-乙基己酸叔丁酯、偶氮二异丁晴、甲苯混合均匀，然后抽入高位槽中。c.滴加混合物，耗时3h左右。d.继续保温 15h 后，降温、出料。将上述物料全数投入到反应釜中，N2保护下升温至 180∼240℃。待 AV≤10 时，降温至 120Ω。将物料放至加有100#芳烃、醋酸甲氧基丁酯（3：1）的兑稀釜中，使之兑稀成固含量大约为 61% 的制品。过滤、包装。在流动缸中加入配方中所列溶剂及润湿分散剂，搅拌均匀。接着在搅拌下加入研磨树脂，加完后再搅拌30分钟。在搅拌下慢慢加入颜料，加完后再高速分散30分钟。最后在砂磨机上研磨至细度小于10μm。To synthesize hydrophilic polymers with functional groups, cross-linking agents such as hexamethylene diisocyanate (HDI) and its derivatives (e.g., HDI trimer, IPDI trimer) are typically utilized. When using HDI trimer, ensure compatibility with hydroxyl-containing acrylic polymers and hydroxyl polyester resins. The mixture of HDI and IPDI trimer can be recommended at a weight ratio of 3:1 to enhance properties such as drying time, film hardness, and weather resistance. Additionally, the total non-volatile content after dilution with non-reactive solvents should be kept above 35%-40%. It is crucial to select solvents free from active hydrogen-containing groups and maintain low humidity levels during the process to prevent hydrolysis and ensure optimal performance.将聚乙烯醇缩丁醛树脂、异丙醇、碱式铬酸锌、丁醇等组分按质量份混合，采取研磨、分散处理后使用。使用时，将甲组分与乙组分混合均匀后，静置至少10秒，再薄薄喷涂一层，控制涂层厚度在10μm左右。a.将醇酸树脂（70%）、醋酸丁酯、丁醇、环己酮、二甲苯、硅油投入到调漆缸中，搅拌均匀。b.在搅拌下慢慢投人滑石粉、重晶石粉、超细轻质碳酸钙、锐太型钛白粉、氧化铁黄、炭黑，再高速分散至少30s。c.在三辊机上研磨至细度 <30μm。d.在搅拌下慢慢加人有机膨润土胶（8%）和硝基纤维素溶液（35%），搅拌均匀。e.用二甲苯和醋酸丁酯调黏。不饱和聚酯树脂的合成采用多元醇、多元酸与不饱和多元酸进行酯化和缩聚反应，添加特种改性剂如环戊二烯、双环戊二烯等以提高性能。引发剂选择低温引发剂如过氧化环己酮或过氧化甲乙酮，促进剂为环烷酸钴或合成脂肪酸钴，添加比例为树脂量的2%-4%。加入活性稀释剂如苯乙烯、环戊二烯以调整黏度，并作为交联剂。为防止流挂，需加入触变剂如气相白炭黑。颜料和填料如钛白粉、滑石粉等需根据需求选择，加阻聚剂如取代酚类以延长贮存期。此外，添加封闭剂如石蜡以隔断氧气，改进厌氧性问题。将所有反应物全部投入到反应釜中，升温至 160~190℃ 进行酯化反应3h。再在195℃下反应3h。打开回流冷凝器开关，蒸出二甲苯，大约需1h。加入苯乙烯兑稀成 65% 的树脂溶液，此时的黏度大约为1.0～1.2Pa·s(20℃)。降温、过滤、出料。1. 清洗: 在电泳槽等设备中加满自来水，然后加 0.5% 的氨水和 1% 的溶剂，循环清洗 12至24小时。2. 洗涤: 排放所有的碱液至废水处理站，用高压水冲洗内壁，并手动清除残留的污垢。3. 酸洗: 加入0.1%的有机酸进行中和及清洗，循环时间为12至24小时，酸洗后水溶液的pH应为5至6。4. 二次水洗: 排放酸洗液后，用高压水冲洗设备。5. DI水洗: 用DI水冲洗并排空，循环清洗至少12小时。6. 投槽: DI水的质量应≤10μS/cm，pH 6至7。7. 加入CED乳液: 可按0.0005%的比例加入乳酸或其他酸性物质，确保循环系统正常工作。8. 监测: 定期检查pH值及电导率，并根据情况调整参数。9. 确保槽液的固含量控制在适合范围内，避免过量。本实验旨在测定CED涂料的MEQ值，方法综述如下：精称样品于一个干净的小烧杯中，加入四氢呋喃和丙二醇的混合溶液（容积比80:20）进行溶解，然后通过电位滴定测定终点，以计算样品中的总酸或碱含量。具体步骤包括：（1）将样品吸入5mL的塑料指示器中并称重，（2）将2g样品注射于150mL烧杯中，并再次称重，（3）加入70mL混合溶液于烧杯中，使用磁力搅拌器搅拌至样品溶解，（4）插入电极并使用0.1mol/L的滴定液进行滴定直至终点，（5）进行空白实验以校正，记录并计算样品的MEQ值。"
+}
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+{
+    "protocol": "第一步：自聚反应第二步：交联聚合Synthesize hydrophilic polymers with functional groups by selecting appropriate epoxy resins (such as Bisphenol A epoxy and phenolic epoxy), curing agents (such as amine curing agents including aliphatic amines and cycloaliphatic amines) and active diluents. Combine liquid or solid epoxy resins with amine curing agents that may be water-soluble or emulsifiable. Use active diluents to adjust viscosity and improve performance, ensuring that single-functional active diluents do not exceed 15% of the epoxy resin content, while multi-functional active diluents may comprise 20-25%. Select solvents that positively influence curing rate and ensure compatibility with the epoxy resin components.The synthesis of hydrophilic polymers with functional groups involves preparing a two-component system, comprising low molecular weight liquid epoxy resin (90.0%), an active diluent (10.0%), along with component B which includes a water-based epoxy curing agent (30.0%) and water. The formulation may be adjusted based on user requirements and cost to produce primers and topcoats. The ratio of component A to component B is set at (1.0 to 1.2):1, ensuring the proper amount of epoxy groups reacts with an equivalent amount of active hydrogen in the curing agent. Additionally, modifiers such as wetting and dispersing agents (45.0%), defoamers (0.6%), leveling agents (0.3%), and thickeners (0.3%) are used to achieve desired performance characteristics.To synthesize hydrophilic polymers with functional groups, a dual-component polyurethane system is employed where one component contains hydroxyl groups and the other contains isocyanate groups. These components are stored separately and mixed prior to application to allow for the reaction of isocyanate groups with hydroxyl groups, forming a polyurethane polymer. For single-component humidity-curing polyurethane coatings, a prepolymer terminated with -NCO groups reacts with moisture from the air, generating amines that subsequently react with isocyanate to crosslink and form a cured film. In preparation for unsaturated polyester resin coatings, polyols and polyacid are condensed, then diluted with monomers (like styrene) and cured into an insoluble film with the aid of initiators and accelerators. Vinyl ester resins are synthesized from epoxy resins and unsaturated monocarboxylic acids in a ring-opening reaction. Finally, for polyurea elastomer coatings, a two-component system consisting of an amino-terminated polyether and liquid amine chain extender is mixed with an isocyanate component, facilitating a rapid reaction without the need for catalysts at room temperature.在硅酸乙酯水解物中加入醇溶性聚乙烯醇缩丁醛或乙基纤维素，用硅酸乙酯水解物与多元酸在酸存在下进行酯交换生成聚醚硅酸酯，硅酸乙酯水解物和含乙氧基、甲氧基、羟基的硅中间体，在酸催化下进一步水解引入部分有机硅组分；通过与有机高分子接枝共聚或加入硅烷偶联剂、悬浮剂、碱金属氢氧化物、磷酸盐、有机树脂乳液等方法改进硅溶胶漆膜性能等方法。环氧改性有机硅树脂的方法有两种：一是冷拼法（物理法)，即以相容性好的有机硅树脂与环氧树脂冷拼混合而成；二是热缩聚法（化学法)，即以环氧树脂的活性官能团（即羟基）与适当的有机硅中间体的烷氧基或羟基在一定条件下进行缩聚反应。改性用的环氧树脂一般采用中等分子量的环氧如E-35、E-20、E-12等，反应在溶剂中进行，常用的溶剂有环已酮、异佛尔酮、甲基环己酮等。树脂合成中主要是硅中间体中的乙氧基或羟基与环氧树脂中的羟基反应，含乙氧基的硅中间物与环氧树脂反应生成乙醇，而含羟基的硅中间物则生成水。将40%的正硅酸乙酯、醇放入罐内，搅拌均匀，然后慢慢滴加入酸化水，此反应是放热反应，一般控制在0.5~1h内滴加完成，然后放置过夜，测试水解程度用碱性溶液，如时间超过控制范围，可以追加补人酸化水，然后再放置4~8h进行测试。The synthesis of hydrophilic polymers with functional groups involves the polymerization of acrylic acid copper type, which generates a polymer-Cu-COO complex. The reaction proceeds with the formation of a soluble polymer species containing COO- and Cu species.有机硅改性醇酸涂料的制备包括将有机硅树脂直接加入达到终点的醇酸树脂反应釜中进行混合，以及制备反应性的有机硅低聚物，与醇酸树脂上的自由羟基进行反应，或将有机硅低聚物用作多元醇与醇酸树脂进行共缩聚。具体方法包括采用羟基封端醇酸预聚体与有机硅预聚体进行缩聚反应，合成出(A-B)n型结构的有机硅-醇酸嵌段共聚物，并以此为基料制成清漆。该清漆具有优秀的耐热、耐大气老化和抗水介质腐蚀性能。首先设置模拟实船钢质水柜两个，内壁按饮水舱条件分别涂刷环氧聚酰胺饮水舱漆、环氧酮亚胺饮水舱漆两个品种，室温干燥一周后在无污染的卫生监督下装人一批自来水1t，供水质分析及毒性试验用。同时要存放同一批自来水一并作为化学分析对照用水。涂漆的水柜在贮存自来水90天内定期做常规水质分析及涂料溶出物分析。表面调整处理通常采用含有胶质钛盐的溶液浸渍基板，随即进行化学转化处理。表面调整液的 pH 要保持稳定，可以加入适量的碳酸盐，起缓冲作用。例如，采用含 5 mg/L 钛离子、 184 mg/L 磷酸根离子、 49 mg/L 焦磷酸根离子和 50 mg/L 碳酸根离子的表面调整处理液对冷轧钢板进行处理后，再进行磷化处理。对电镀锌表面，可用含有络合剂和钛离子或锆离子的， pH 为 12.0~13.5 的碱性表面调整液活化处理，例如用含 70 g/L 氟钛酸（浓度为 40%）， 60 g/L 乙二胺四乙酸四钠盐、 140 g/L 氢氧化钠和 730 g/L 水的溶液喷淋电镀锌钢板后，再用铬酸盐处理。对热镀锌钢板，采用酸性的含镍离子的溶液对表面进行活化调整处理，得一个较粗糙、活性较高的表面。选用氧化铁-磷酸盐型转化液处理冷轧钢板，含磷酸、碱金属磷酸盐及氧化剂，处理温度40~75°C，成膜时间5~20s，膜厚约0.3g/m²；镀锌钢板使用磷酸盐、铬酸盐和复合金属氧化物型转化液，处理温度65°C，成膜时间5~20s，膜厚约2.0g/m²；复合氧化物型转化液处理，温度40~70°C，时间5~20s，膜厚0.1~0.3g/m²；反应型铬酸盐-复合氧化物型转化液处理温度20~60°C，处理时间3~15s；辊涂法对镀锌和合金化镀锌钢板使用铬酸盐类转化液，加入树脂和二氧化硅粒子以提高膜的强度和致密性。取100份聚烯烃聚合物和43份环氧树脂混合均匀；加入21份环氧稀释剂，混合均匀得到玻璃状熔融体；冷却至90°C，继续捏合混合，待冷却至聚烯烃熔融温度以下以出现相分离，聚烯烃沉淀于树脂稀释溶液中；加入21份环氧稀释剂，在90°C捏合并继续冷却，得到软浆状分散体；将186份聚烯烃分散体与108份己二醇二缩水甘油醚和单缩水甘油醚、74份己二醇二缩水甘油醚、29份邻苯二甲酸二异壬酯、80份滑石粉、6份N,N-(4-甲基-间亚苯基)双(N',N'-二甲基脲)、17份双氰胺与0.08份黑色颜料在60°C混合均匀，得到熔融温度不超过70°C的玻璃浆状产物。在带有温度计、搅拌和回流冷凝器的反应容器中加人 $297.5\\mathrm{g}$ 环己烷二甲酸、 $50.5\\dot{\\mathbf{g}}$ 己二酸、 $207.48$ 新戊二醇、 $44.5\\mathrm{g}$ 三羟甲基丙烷、 $0.6\\dot{\\mathrm{g}}$ 二月桂酸二丁基锡和 $\\widehat{\\mathfrak{f}}\\widehat{\\mathfrak{f}}_{\\mathbf{\\Xi}}$ 二甲苯，以 $3\\sim5\\mathrm{h}$ 升温至 $220^{\\circ}C$ 并保温回流脱水反应至酸值 ${<}3\\mathrm{mg}~\\mathrm{KOH/g}$ 脱水量约 $74.6g$ ，降温至 $<160^{\\circ}C$ ，加人兑稀溶剂 $282.9\\underline{{\\sigma}}$ ，得到耐久型聚酯树脂。在带有温度计、搅拌和回流冷凝器的反应容器中加人212.4g间苯二甲酸、220.1g环已烷二甲酸、31.1g己二酸、277.0g新戊二醇、58.4g三羟甲基丙烷、0.4g二月桂酸二丁基锡和80g二甲苯，以3~5小时升温至220°C并保温回流脱水反应至酸值<3mg KOH/g，降温至<160°C，加入混合溶剂（S-150#:DBE:丙二醇甲醚醋酸酯=6:2:2, 609.3g兑稀）；加入硅氧烷中间体DC3074（道康宁）213.9g、钛酸四异丙酯0.5g，升温至160~180°C脱醇反应1~2小时，取样观察至树脂透明为终点。The protocol for synthesizing hydrophilic polymers with functional groups involves using EPIKOTE 1009 epoxy as a base, which is a 50% solution used at 37.8 g. A blocked isocyanate curing agent, also in a 50% solution, is utilized at 12.6 g. Additional components include 17.6 g of R-902 (titanium white), 2.5 g of zinc chrome yellow, 5.0 g of aluminum tripolyphosphate, 0.5 g of organic bentonite, 0.5 g of Efka-8512 (dispersant), 0.8 g of Syloid C-807 (extinction powder), 0.3 g of Efka-3777 (leveling agent), 11.2 g of xylene, and 11.2 g of cyclohexanone, summing up to 100.0 g total.The surface treatment composition for metal materials contains a water-based medium and the following components: 1) Metal ions selected from M̄n ions, CO ions, Zπ ions, M_E ions, Ni ions, Ti ions, V ions, and z_r ions; 2) Fluorinated acids containing at least 4 fluorine atoms and elements selected from Ti, Zr, Si, Hf, Al, and B; 3) Silane coupling agents having reactive functional groups selected from amino, epoxy, vinyl, thiol, and methacryloxy groups, which contain active hydrogen; 4) Water-based emulsified resins selected from cationic or non-ionic polyurethane resins, acrylic resins, epoxy resins, polyester resins, and polyamide resins as the resin component.合成端羟基或端羧基的聚酯树脂，端羧基聚酯树脂酸值 $20\\sim$ $40\\mathrm{mg\\KOH/g}$，端羟基聚酯树脂羟值 $40{\\sim}100\\mathrm{mg}\\mathrm{KOH/g}$，聚酯树脂可以是线型的，也可以部分支链化。固化剂一般选用常温下为固态的类型。对端羟基聚酯树脂，固化剂选用氨基树脂和封闭异氰酸酯树脂；对端羧基聚酯树脂，固化剂可选用含环氧官能团的环氧树脂和丙烯酸树脂，以及多环氧化合物如三缩水甘油基异氰脲酸酯（TGIC）等。粉末浆涂料组成物中的粉末树脂（包括固态的固化剂）的玻璃化温度或软化点为 $40\\sim60^{\\circ}C$。粉末涂料制备时，将树脂和固化剂干研磨至粒径 $20\\mathrm{\\sim}30\\mu\\mathrm{m}$ 后加入水性介质中，如需要还可加入颜料或填料。在水性介质中除了水，还可以预先加入分散剂、流变助剂、催化剂、消泡剂等助剂。然后将此粉末浆料以合适的分散设备研磨得到平均粒径 $3\\sim6\\mu\\mathrm{m}$ 的粉末浆涂料。聚酰胺的合成方法多为两种单体的缩合反应。酚醛树脂的合成是通过苯酚与甲醛进行缩聚反应，添加各种助剂以得到酚醛塑料。合成过程中涉及控制反应条件，如温度与货架期，以确保树脂性能。苯酚和甲醛的混合比应根据所需的功能化特性进行调整。聚氨酯（PU) 是由异氰酸酯（单体)与羟基化合物聚合而成。For the treatment of ABS plastic, soak in a solution of chromic acid (H2CrO4) at a concentration of 420 g/L and sulfuric acid (relative density 1.83) at a dilution ratio of 1 mL/L for 4 to 12 minutes at a temperature of 60 to 70°C. Subsequently, rinse with water and dry. For polyester and polycarbonate, treatment can be done with 1,6-hexanediamine or N,N-dimethylpropylamine to introduce -OH and R-NH- groups, improving surface polarity and wettability. For polyoxymethylene, treatment involves strong acids or oxidizing agents such as p-toluenesulfonic acid, phosphoric acid, ammonium persulfate, and chromic acid to introduce hydroxyl and carboxyl groups, improving wettability and adhesion. Polyamide products can be soaked in a 40% phosphoric acid solution at 30°C for 1 hour, followed by rinsing and drying.聚乙烯的紫外线处理将市售的聚乙烯或聚丙烯板用洗涤剂水溶液清洗 5至10分钟，水洗 5分钟，丙酮清洗 2至5分钟，苯洗 2至5分钟后干燥 5小时，保存在充氮气容器中待处理。紫外光处理用的光源为石英汞灯，其最大强度波长为 253.7nm，聚乙烯实验板离光源 20cm 照射过程中聚乙烯表面温度保持在 80至90°C，照射时间为 3分钟至3小时。聚酯薄膜先用 0.2% 洗涤剂水溶液、清水、蒸馏水依次洗过干燥后备用。用170W的低压汞灯处理，表面距离为 8cm，照射时间为 5分钟。同时进行 80°C，37% NaOH 溶液处理和有机钛烷酯的偶联剂处理做对比实验。表面处理的主要目的是活化情性的塑料（PP、PE、PTFE等），以产生可与涂料成膜物相结合的官能团。表面分析的作用在于确定活性官能团的存在及其分布。采用元素和官能团的表面分析方法，如Auger电子分光光度法（AES）、光电子分光法（ES-CA）、X射线分析法（XMA）、二次离子质量分析法（SIMS）和离子散射光谱法（ISS）来进行表面元素分析及官能团种类确认。润湿性的评价主要通过测定表面对液体的接触角和表面的临界表面张力Y来进行，方法包括液滴形状法、气泡形状法和前进与后退润湿板法等。最后，通过推算接触角和液体在固体上的润湿功来确定处理表面的临界表面张力。将200：100：700（单体配料比）的甲基丙烯酸特丁酯-甲基丙烯酸十二烷基酯-甲基丙烯酸甲酯共聚物（50.3%的不挥发分，分子量25000）100质量份与铝粉浆（65%的不挥发分）10质量份混合，稀释，喷涂在聚苯乙烯上，并在60℃下烘烤30min。使用含活性基团的水分散性交联剂的丙烯酸聚合物乳胶制备合成。配方为：甲基丙烯酸甲酯59质量份、甲基丙烯酸丁酯33质量份、甲基丙烯酸羟乙酯6质量份和甲基丙烯酸2质量份，配置 $20\\%$ 聚合物乳胶，并加入 $1\\%$ 三羟甲基丙烷聚缩水甘油醚（I）交联剂。用该乳液涂覆 $0.\\dot{0}15\\mathrm{mm}$ 厚的增塑氯乙烯薄膜，涂层厚 $5\\mu\\mathrm{m}$，在 $130^{\\circ}C$ 下烘干 $50\\mathbf{s}$。滴加 $600\\mathbf{g}31\\%$ 的水性胶体二氧化硅分散体于 $500\\mathbf{g}$ 甲基三甲氧基硅烷中，并在 $\\mathrm{\\ttPH}=3\\sim\\hat{6}$ 下搅拌 $4\\ h$ ，然后用 $100g$ Ⅱ兑稀。这种面漆在 $100^{\\circ}C$ 下烘烤$60\\mathrm{min}$。将甲基丙烯酸月桂酯、甲基丙烯酸、苯乙烯和过氧化苯甲酰按比例混合。将上述单体混合物于80～100℃滴加到氯化聚烯烃的甲苯溶液中，CI含量27%的氯化聚丙烯的30%甲苯液44质量份，高氯化聚乙烯（CI含量67%）的30%申苯液20质量份。反应并稀释至40%固体分，该树脂液可制备清漆、色漆。涂装于聚酯表面后于80℃干燥10分钟，可得附着力100/100（划格法）的涂层。将主剂和固化剂按涂料制造厂家要求的比例混合，加入适量的稀释剂调整施工黏度，进行涂装。主剂采用含羟基基团的各类树脂，固化剂含有异氰酸酯的预聚物树脂。选择新鲜猪血作为原料，立即处理以避免腐败。使用400至800目的滑石粉作为填料。现场加水配置氧化钙，制备高浓度的石灰水溶液\\[\\mathrm{Ca(OH)_{2}}\\]，避免长时间放置导致反应生成无效的碳酸钙溶液[\\mathrm{CaCO_{3}}]。根据用途调整滑石粉的用量，作为嵌补腻子时用量多，稠厚；作为填孔腻子时用量少，稀薄。猪血与石灰水的比例是关键，调节可控制腻子的硬度，理想状态下腻子应呈青绿色。1. Prepare a nitrocellulose solution by mixing butyl acetate, butanol, xylene, and nitrocellulose in the ratio of 44:11:11:34 to a total mass fraction of 50%. 2. Add 15% of alkyd resin (60%) into the mixture. 3. Gradually introduce 10% of maleic anhydride resin solution (50%) and 1% of DOP plasticizer, stirring continuously. 4. Slowly add 2% of zinc stearate PLB, ensuring uniform dispersion. 5. Incorporate 22% of talcum powder (1250 mesh), mixing slowly for uniform dispersion. Then, high-speed disperse for 10-15 minutes, maintaining temperature below 50°C until achieving the required fineness, then package using 40 mesh filter cloth.选择原料包括硝化棉、短油度豆油醇酸树脂、硬脂酸锌和填料（如滑石粉）。硝化棉需预先溶解成30%。增塑剂推荐使用邻苯二甲酸盐（如DBP、DOP）或环保型增塑剂（如环氧大豆油）。确保粉料的含水量在0.2%以下。硝化棉与醇酸树脂的比例为1:(0.8至1)，有助于调节腻子的技术指标。加入422马来酸酐树脂以降低黏度并改善刮涂性能，确保在加入量上控制，以免影响涂膜性能。添加硬脂酸锌以改善打磨性，添加量需根据实验确定。膨润土的添加量约为配方量的1%至1.5%。生产过程中采用夹套缸，物料温度控制在50°C以下以防变色。施工时采用刮涂法，避免一次性厚涂，并确保干燥后表面打磨干净。将气干型UPE树脂（70%）、防绿化剂、苯乙烯、阻聚剂以及蓝水和分散剂按比例依次投人，先进行中速分散均匀；然后加入滑石粉（800目）和硬脂酸锌PLB，进行高速分散10～15分钟，检测细度，并通过40目滤网过滤。选择市售的UPE树脂，根据吸氧单体的不同分为烯丙基醚类和双环戊二烯类，前者表干性能好，后者硬度较高。使用苯乙烯作为活性稀释剂，降低黏度并参与最后交联。添加阻聚剂如对苯二酚提升生产和贮存稳定性。使用SiOz作为防沉剂，注意苯乙烯的含水量测试以保持贮存稳定性。对于滑石粉，选择400目或800目。生产过程中采用捏合机，避免物料温度过高，使用高速分散机时建议使用夹套缸进行水循环冷却，温度不超过50°C，并避免光线直射苯乙烯。1. Prepare the following materials: bifunctional acrylic monomer epoxy acrylate resin (75%), defoamer (0.2%), dispersant (0.5%), talcum powder (20%), photoinitiator (2%). 2. Add the bifunctional acrylic monomer and epoxy acrylate resin sequentially to a mixing vessel and stir at medium speed until uniform. 3. Add the defoamer and dispersant, and continue stirring at medium speed to ensure uniform distribution. 4. Introduce talcum powder and disperse it using high-speed stirring until the particle size is within acceptable limits (≤100μm). 5. Finally, add the photoinitiator and mix thoroughly. Filter through a 30 mesh screen and package.选择低聚物，如环氧丙烯酸酯、聚氨酯丙烯酸酯、聚酯丙烯酸酯、聚醚丙烯酸酯等；选择单官能度、双官能度或多官能度丙烯酸单体，根据低聚物的性能进行搭配，确保优势互补；使用自由基光引发剂，如裂解型（汽巴的1173）和夺氢型（如二苯甲酮）的组合，搭配活性胺类光敏剂；避免光线直射，控制物料分散时的温度；注意不在PU和NC涂料中加入硬脂酸锌，以免影响施工性能。水性腻子的合成包括以下步骤：1. 以18.6%的水为基础，加进0.8%至3.5%的氨水（胺中和剂），搅拌均匀直至pH值达到8-9；2. 加入0.3%防腐防霉剂和0.8%防沉剂（重质碳酸钙），慢慢加入并搅拌至完全溶解；3. 添加45%重质碳酸钙，分散均匀；4. 加入15%滑石粉，用于改善腻子的打磨性，缓慢加人并确保分散均匀；5. 调整pH、加入其他添加剂如丙二醇以提高低温冻融稳定性，完成整个配方。依次投人，低速搅拌均匀，200目过滤包装。生产工艺为依次加人，搅拌均匀。选择常用的树脂有椰子油酸短油度醇酸树脂、豆油酸短油度醇酸树脂、合成脂肪酸醇酸树脂、羟基丙烯酸树脂。固化剂一般选用TDI加成物和三聚体。主漆与固化剂的配比控制在4:1。PU封闭底漆的固含量控制在15%以下，固化剂的固含控制在45%至50%。混合后最好在4小时内用完，若混合物黏度超过原始黏度的两倍则不宜再使用。配方调整树脂一般选用羟基丙烯酸树脂，封闭性能较好。加人染料溶液调色。硝基底漆的生产通常分四个工序进行：硝化棉及硬树脂的溶解；颜填料的研磨分散；调漆及配色；过滤包装。常用的生产设备为高速分散机，颜料的研磨分散需用到球磨机、砂磨机、三辊机。颜料做成色浆后在调漆及配色过程中加入，填料则可在调漆过程中用高速分散机直接分散，两个过程均需注意漆料的黏度，黏度太稀可能会导致分散不均匀而有颗粒。调配好的产品用120~150目的滤网过滤包装。不饱和聚酯底漆的生产通常分三个工序进行：颜料、填料的研磨分散；调漆及配色；过滤包装。常用的生产设备为双轴高速分散机，不饱和聚酯底漆的整个生产过程必须控制好漆液的温度，一般控制在 50℃ 左右，温度太高会影响涂料的贮存稳定性。调配好的产品用 120~150 目的滤网过滤包装。按序投人，中速分散8～10min，搅拌均匀；称量二甲苯，投人分散缸；加入422马来酸酐树脂溶液，中速搅拌15～20min，待溶解完全，200目过滤，备用。1. 原料选择：硝化棉、增塑剂（如邻苯二甲酸二丁酯或邻苯二甲酸二辛酯）、短油度豆油酸醇酸树脂、422马来酸酐树脂、混合溶剂（如二甲苯、醋酸丁酯、丁醇）等。 2. 硝化棉溶液制备：选择1/4s或高黏度的硝化棉，制成25%~30%的溶液。 3. 组分比例：将硝化棉溶液、邻苯二甲酸二丁酯、短油度豆油酸醇酸树脂（70%）、422马来酸酐树脂溶液（50%）、分散剂、混合溶剂、消光粉聚乙烯蜡、流平剂按照质量分数配制，加入表3-7-27中所列具体比率。 4. 生产工艺：以上原料依次加人，中速搅拌均匀后，缓慢加入溶剂，并高速分散15~18分钟。 5. 注意事项：硝化棉和醇酸树脂混合时要边搅拌边慢慢加人，以免析出；选用的溶剂应具有适当的挥发性过高的溶剂可能导致缺陷。原料选择树脂一般选用豆油酸短油度醇酸树脂、椰子油短油度醇酸树脂、饱和聚酯树脂、羟基丙烯酸树脂。改性树脂主要是氯醋树脂、CAB。粘度和固化剂的比例应根据所使用的树脂进行调整，以保持异氰酸根与羟基的当量比为1:1。生产工艺为按序加入原料，中速搅拌均匀，200目过滤包装。Production of the hydrophilic polymers involves the following steps: 1. Add raw materials in a specific order, starting with short oil fatty acid resin (60%) with a proportion of 43%, xylene at 1.4%, butyl acetate at 6%, and dispersant. Mix at medium speed until uniform. 2. Introduce polyethylene wax at 0.2%, matting powder at 1.5%, and short oil fatty acid resin (60%) at 5.5%, then disperse at high speed for 10-15 minutes until the fineness is qualified. 3. Add a sediment-resistant agent (30%) at 1.5% and nitrocellulose solution (0.5s, 30%) at 11%, followed by a leveling agent at 0.3% and defoamer at 0.3%. Mix at medium speed until uniform and filter before packaging.混合固化剂的主要组分包括异氰酸酯组分、混合溶剂、催干剂和吸水剂。生产工艺为将几种组分物料混合搅拌均匀，需防止水的副作用，确保设备清洁。设备清洗采用醋酸丁酯搅拌清洗，判定标准为清洗后的溶剂不发白、清澈透明。如使用1:10比例的清洗溶剂与固化剂混合后出现发白、浑浊则表明清洗不达标。为防止水污染，推荐进行溶剂脱水、通入氮气保护，以及加入吸水剂，吸水剂优先与水反应以降低水分对固化剂的影响。稀释剂的生产一般采用可调速的搅拌机，容器最好采用密闭的，以避免生产过程中溶剂的挥发。生产过程中确保各组分搅拌均匀，调配好的产品用 120~150 目的滤网过滤包装。引发剂（白水）分解产生高度活性的自由基，自由基攻击聚酯分子链中的不饱和双键和交联单体（如苯乙烯)，使之活化，从而发生交联反应。促进剂（蓝水）通过氧化还原反应，使引发剂分解产生高度活性的游离基。选择适合的引发剂，如过氧化甲乙酮或过氧化环己酮，其用量为1%至2%（质量分数），根据气温调整使用量。在聚酯固化过程中选择促进剂，如金属化合物或叔胺类促进剂，主要根据其与引发剂的相容性进行选择。具体配比及用量根据涂装环境温度调整，并参考相关表格进行引发剂和促进剂用量的调整。在实际操作中，判断反应是否完成可通过漆膜颜色变化确认。称取 25∼35g 试样于 250mL 磨口瓶中，加入 20∼30mL 刚用氢氧化钾标准溶液中和好的乙醇，加入 2∼3 滴酚酞指示剂，盖好后摇匀，立即用 0.02∼0.04mol/L 的氢氧化钾标准溶液滴定至试液呈粉红色，且在 10s 内不消失为终点。称取试样 1~3g (准确至 0.001g, NCO含量大于 20% 时称样 1E 左右) 于 250mL 的三角瓶中，加人 20mL 乙酸乙酯，充分溶解，用瓶颈加液器(或移液管)准确加入 10ml. 二丁胺-甲苯溶液，充分摇匀，不需放置(仲裁时放置 20min)，加人3滴溴甲酚绿-乙醇指示剂(如用电位滴定仪滴定时不需加指示剂，由仪器直接判断滴定终点)，用 0.5mol/L 的盐酸-乙醇标准溶液滴定至颜色由纯蓝色变成黄色为终点，同时做空白试验。（1）底材的准备在至少 \\mathfrak{f m m} 厚的平玻璃板上，滴几点 200^{\\#} 溶剂汽油，将聚酯膜铺展在上面。 200^{\\#} 溶剂汽油的表面张力使聚酯膜紧贴在玻璃板上面。不能弄湿聚酯膜的上表面，在聚酯膜与玻璃板之间不能存留气泡。必要时可用洁净白绸布指拭聚酯膜表面将聚酯膜与玻璃板之间的气泡消除。 （2）试板制备将亚光清漆产品按规定的施工配比配制，并将其黏度调整到： (20\\pm1)\\:s （岩田2号杯，温度 25^{\\circ}\\mathrm{C})。配好产品后，用 400\\mu\\mathrm{m} 的涂膜涂布器在聚酯膜上均匀涂布一遍，并将涂过漆的聚酯膜固定在平整的表面上，在水平条件下干燥。 （3）干燥条件试板应在温度 (23\\pm2)^{\\circ}C 和相对湿度（ (65\\pm5)\\% 的条件下至少干燥 24\\mathrm{h} 才可进行反射率测定。 （4）首涂对比率的测定在反射率测定仪的黑、白陶瓷板上，滴上几滴 200^{\\#} 溶剂汽油，从玻璃板上取下干燥好的试板，使其紧贴在黑、白陶瓷板上，不能弄湿测试样板的上表面，在试板与黑、白陶瓷板之间不能存留气泡。然后分别在紧贴黑、白陶瓷板的试板上至少6个位置上测量试板的反射率，记为 R_{\\mathrm{B}} (黑板）、 R_{\\mathbb{W}} （白板)，分别去除所录数据的最大值和最小值后，取余下四个数值的平均值，再计算每张试板的首涂对比率 R_{\\mathrm{B}}/R_{\\mathrm{W}}。 （5）重涂对比率的测定按 （1）~（2）的方式在测完对比率的试板上，重涂一次，再按 （3）~（4）的要求进行试板的干燥和对比率的测试。 （6）结论分别计算首涂和重涂的对比率，评价自身的透明度；计算首涂和重涂的对比率之差，并取绝对值，评价重涂性，并得出结论。将聚乙烯或聚丙烯与含有羧酸基团的附着力改性剂进行简单混合，以改善聚烯烃的附着力。粉末涂料用环氧树脂的生产分为\"两步法\"和\"一步法\"。\"两步法\"的环氧树脂即先将环氧氯丙烷和双酚A通过滴加氢氧化钠溶液制成小分子量的环氧树脂，再与双酚A进行二次反应制成所需要的中等分子量环氧树脂。\"一步法\"环氧树脂又分为\"溶剂一步法\"和\"水洗一步法\"，\"溶剂一步法\"是首先将双酚A和氢氧化钠溶液以及部分溶剂溶解后加人环氧氯丙烷进行反应制成中等分子量的环氧树脂，加入溶剂溶解环氧树脂使之成为低黏度溶液，再进行水洗脱除无机杂质，最后进行真空脱溶剂。使用双氰胺作为固化剂，计算方案为：双氰胺的分子量（84.08）乘以环氧值，再乘以100g的环氧树脂，得出双氰胺的用量，其中双氰胺的活泼氢数量为21.02。在实际应用中，双氰胺的用量需比理论计算量多15%左右，固化条件为160°C/60min或180°C/30min。此外，可以使用加速双氰胺和改性双氰胺，此过程中混合咪唑或咪唑衍生物以降低固化温度及改善涂膜的机械强度。也可采用2-苯基-2-咪唑啉与多元酸盐反应生成单胺盐，以作为固化促进剂，同时需要注意控制环氧树脂中的羟值以确保配方的有效性。合成过程：先将多元醇和一部分多元酸反应生成端羟基聚酯，再与剩余的多元酸反应成为端羧基聚酯树脂。可根据需要合成出不同羧基含量的聚酯树脂，与环氧树脂采用不同的质量比进行搭配使用。使用其他的交联剂固化聚酯树脂，使体系的涂膜能够在很大程度上增加对紫外线的耐受性，聚酯树脂可制成端羧基的聚酯树脂，也可以制成端羟基的聚酯树脂。不饱和聚酯树脂的合成是通过不饱和二元酸和饱和二元酸与饱和二元醇进行酯化缩聚而制成的。使用的主要原料包括不饱和二元酸（如顺丁烯二酸或富马酸）和饱和二元醇。为了促进固化反应，可以使用有机胺或有机金属钻盐作为引发剂，同时加入过氧化物催化剂（如过氧化苯甲酰或过氧化酮）以实现快速固化。在紫外线固化的应用中，需加入光引发剂，而无需有害的过氧化物催化剂，以提高贮存稳定性并确保良好的低温固化效果。为了解决不饱和体系的厌氧固化问题，可以在不饱和聚酯树脂中引入烯丙基的功能团。将颜料、填料和醇酸树脂混合，搅拌均匀，经研磨至细度合格，再加入环氧树脂液和三聚氰胺甲醛树脂、环氧漆稀释剂，充分调匀，过滤包装。The text provided does not include a specific experimental protocol for the synthesis of hydrophilic polymers with functional groups. It primarily describes formulations and performance indicators related to epoxy polyurethane primers, which do not pertain to the synthesis of hydrophilic polymers.将选定的氟碳树脂、钛白粉、炭黑、绢云母、滑石粉、助剂、消光粉、混合溶剂按一定比例混合均匀，砂磨到细度小于 10μm 后出料，用混合溶剂调配成固含量 50%±2%，即为淡灰色氟碳飞机蒙皮涂料色浆。将上述色浆与固化剂按 4:1 混合均匀，制板，室温固化7d后检测。先制备线型的预聚物，再用芳香族二胺如4，4-二氨基-3，3-二chlor二苯甲烷或间二胺等来固化。硅橡胶的合成分为双组分和单组分室温固化硅橡胶。双组分硅橡胶由含硅醇端基的聚合物组分和交联剂如硅酸乙酯或烷基三烷氧基硅烷及催化剂如辛酸亚锡、二丁基二月桂酸锡等组成。固化时两个组分混合后发生，固化时间室温下为数小时至数天，较高温度下固化加快。单组分硅橡胶则使用可水解的多官能度硅酮或硅氧烷交联，交联反应在湿气中进行。固化速率受相对湿度和温度影响，通常在较高的温度和湿度下可在10分钟内表面膜形成。在160至180℃下反应4至8小时可获得硅亚芳基聚合物，其玻璃转化温度可达-72℃，热稳定性超过500℃。丙烯酸树脂的合成涉及将丙烯酸酯或甲基丙烯酸酯与其他不饱和单体进行加成聚合，形成具有不同物性和用途的共聚树脂。The text does not provide a specific experimental protocol for the synthesis of hydrophilic polymers with functional groups. It discusses the properties and general characteristics of epoxy resins, including their advantages and disadvantages, but does not outline the steps or methods for their synthesis.The text does not provide a specific experimental protocol for the synthesis of hydrophilic polymers with functional groups.将目标树脂（杂化树脂）溶解在丙烯酸单体中，经过预乳化至微乳（平均粒径500nm左右），再采用乳液聚合工艺得到成膜性能优良、稳定的杂化乳液。使用高速分散机将颜料、填料和树脂、溶剂混合均匀，然后用砂磨机进一步混合研磨。预先将防沉淀剂制成预凝胶，参考配方为10%有机膨润土，3%工业酒精，87%甲苯，0.3%分散剂。生产过程主要是用高速分散机，把乳液、颜料、填料、助剂等充分搅拌分散均匀。投料的顺序是在搅拌的状态下，先加人乳液、水、表面活性剂及消泡剂，随后再加颜料、填料等，使之充分搅拌分散均匀。在调漆过程中，缓慢加人成膜助剂、增稠剂、防霉防腐剂、乙醇等，最后加氨水调整涂料的 pH 中。A组分和B组分的比例是1:1。施工前，B组分需添加4%固化剂过氧化二苯甲酰（BPO）。喷涂的标线厚度约0.6mm（干膜）。1. Gather required materials and equipment including liquid anhydride measuring tank, liquid raw material measuring tank, condenser, water separator, dilution tank, reaction kettle, high-temperature gear pump, internal gear pump, temperature recording devices, vacuum equipment, and filtration system. 2. For alkyd resin synthesis, initiate the process by performing alcoholysis and esterification above 200°C (typically around 250°C), ensuring that about 4% of water generated during the reaction is removed via reflux. 3. For amino resin synthesis, operate at approximately 100°C, applying vacuum to remove excess water and butanol during methylation and etherification processes. 4. For acrylic resin synthesis, emulsify water and add the mixed acrylic monomers to the reaction kettle, using a batch addition method for initiators and maintaining temperature control, stirring until the reaction is complete. 5. After reaching the endpoint, allow samples to cool, and then proceed with purification steps like filtration and storage.蒸汽加热是低温树脂最常用的加热方法。将蒸汽从上部通入反应釜的夹套或反应釜内盘管中，然后将冷凝水从夹套或盘管下方通过疏水器排出。加热至约 $150^{\\circ}C$ 时，需使用 $0.6\\sim 0.7\\mathrm{MPa}$ 压力的蒸汽。操作过程中，应注意排尽夹套的空气、及时排除冷凝水、控制蒸汽压力不得超过设备许可的工作压力。冷却时，关掉蒸汽，在冷凝水出口处通入冷却水。加压热水（过热水）加热，其温度视压力的大小可提高很多。如用表压0.7MPa的蒸汽通过一个高效换热器可将水加热到 $150^{\\circ}C$ 左右，加压热水（约0.4MPa）经离心泵密闭循环，向反应釜供热。反应釜可采用半管夹套结构，对温度可进行自动调节，加热均匀，操作方便。加压热水加热可用于低温树脂生产，如丙烯酸树脂和乳液等。The experimental protocol for the synthesis of hydrophilic polymers with functional groups is not present in the provided text excerpt.将试板2/3面积浸入3%氯化钠溶液中，按产品标准规定的时间浸泡后取出并检查。可采用常温浸盐水法或加温耐盐水法，后者试验温度为 (40±1)°C，使用恒温设备控制。将铝及铝合金置于含碳酸钠、铬酸盐等碱性溶液中，在高温下处理 5∼20min，使表面生成一层氧化膜。氧化后的工件要进行钝化处理，其目的是使氧化膜稳定，并中和残留在工件表面的碱性溶液，可进一步提高耐腐蚀能力。钝化溶液为含铬酐 20g/L 的水溶液，处理时间为 5∼15s，冲洗干净后，再放到 50°C 的烘箱中烘干，烘干后即可涂装。1. Prepare a treatment solution containing phosphoric acid, chromic acid, and fluoride as a corrosive agent, adjusting the pH to 1.5-3.0. 2. In an acidic environment, aluminum reacts with hydrofluoric acid, resulting in aluminum fluoride and releasing hydrogen gas. 3. The chromate ions dissociate, reacting with hydrogen to produce chromium hydroxide and hydroxide ions. 4. At a specified pH, trivalent chromium reacts with phosphoric acid to precipitate chromium phosphate. 5. The aluminum ions in solution subsequently react with phosphoric acid to create aluminum phosphate. 6. To precipitate aluminum hydroxide, increase pH leading to the formation of aluminum oxide. 7. Control the aluminum ion concentration to prevent color changes in the treatment solution using alkali metal fluorides as precipitating agents. The treatment can be applied using immersion or spray methods, with specific formulations and processing times outlined in the provided table.铬酸盐处理工艺规程如下：铬酸/（g/L): 3.5~4, pH 1.5; 重铬酸钠/（g/L): 3.0～3.5, 温度/C: 30; 氟化钠/（g/L): 0.8, 时间/min: 31. Remove surface contaminants by cleaning with soap water or detergents for plastics like ABS, polystyrene, and acrylic that have good coating adhesion. For solvent-resistant plastics such as polyolefins and thermosetting plastics, perform vapor cleaning with chlorinated solvents like trichloroethane or trichloroethylene and aromatic solvents like toluene for 1-3 minutes.\\n\\n2. Treat the surface using plasma flow, which includes infrared, ultraviolet, ions, and free radicals. Utilize the high-energy reactivity to engage in various reactions with the surface of plastics and rubber to remove contaminants and generate double bonds and other functional groups.对聚乙烯、聚丙烯等结晶性高的非极性塑料，使用强酸强氧化物组合的酸性液进行处理以导入基、羧基等官能团。酸液配方包括重铬酸钾 4.5%；水 8.0%；浓硫酸 87.5%。首先将重铬酸钾和水配成溶液，然后缓缓加入浓硫酸混合均匀。处理参数为：铬酸钾 质量份 75，浓硫酸 质量份 1500，水 质量份 120，温度 70~75℃，时间 5~10分钟。用缠于棒上棉球，蘸取甲酰胺和乙二醇乙醚的混合液，在被处理过的薄膜上涂布约6.5cm（直径约2.9cm)，若此薄膜上的液膜保持2s以上不破时，再用表面张力高的混合液试验；若薄膜在2s内破裂成小液滴时，则再用张力低的混合液实验，从而获得适当的表面张力值。将经过火焰处理的塑料表面，浸入清洁的冷水或3质量份乙醇和1质量份水组成的溶液中，若水膜能保持30s，则认为处理合适。用染料（如纯色淀蓝）的硝基乙烷溶液（4g/L）涂刷，若润湿的表面不形成液滴，则为合格。1. Remove resin-rich areas by excavating them and replace with wood of the same size, ensuring fiber direction consistency. 2. Use an organic solvent to dissolve the resin and apply 1 to 2 coats of shellac as a barrier layer to prevent resin seepage. Common organic solvents include ethanol, turpentine, gasoline, toluene, and acetone. 3. Wash with an alkaline solution using a 5% to 8% sodium carbonate solution or a 4% to 5% caustic soda solution to saponify the resin, then rinse with hot water and after drying, apply 1 to 2 coats of shellac. 4. Clean with a mixture of alkaline solution and acetone. Mix 80 g of a 5% to 6% sodium carbonate solution with 200 g of an acetone-water solution (50 g of acetone and 150 g of water), apply to the resin areas, then rinse with water, and after drying, apply 1 to 2 coats of shellac.浸涂最合适的涂装膜厚是30μm，膜厚的控制可以通过黏度进行调节。涂料黏度越大，膜厚越厚；反之，黏度越小，膜厚越薄。浸涂时应该根据具体的涂装要求确定合适的涂料黏度，并进行严格的控制。涂料的黏度和温度密切相关，黏度随温度的升高而降低，因此浸涂槽内的温度必须严格控制，使其保持稳定。被涂物出槽的速率要适宜。出槽速率过快将造成浸涂槽内涂料剧烈运动，从而产生气泡，影响浸涂的质量。反之，如果出槽速率慢，而溶剂挥发速率快，则在垂直平面的漆膜厚度不均，一般出槽速率控制在 10cm/min 左右。在施工过程中需进行适当的搅拌，保持浸涂槽内涂料的均匀，防止涂料沉淀。施工过程中要加强通风，保持操作环境空气的流通，从而减少有机溶剂对操作工人的危害。工件 $\\cdot+$ 预脱脂 $\\blacktriangleleft$ 脱脂 $\\twoheadrightarrow$ 水洗 $\\nrightarrow$ 热水洗 $\\rightarrow$ 表面调整 $\\cdots$ 磷化 $\\cdot^{-}$ 水洗 $-\\mathbf{\\delta}$ 去离子水洗 $\\twoheadrightarrow$ 热风烘干 $\\twoheadrightarrow$ 电泳沉积 $\\nrightarrow$ 超滤循环水洗 $\\nrightarrow$ 烘烤成膜 $\\blacktriangleright$ 冷却 $\\nrightarrow$ 涂装面漆"
+}
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diff --git a/task2/task2-paper-info/║г╤є╗╖╛│╓╟─▄╖└╕п═┐▓уг║╜с╣╣╔ш╝╞╙ы╧ь╙ж╗·╓╞_╦я╙н╧ш.json b/task2/task2-paper-info/║г╤є╗╖╛│╓╟─▄╖└╕п═┐▓уг║╜с╣╣╔ш╝╞╙ы╧ь╙ж╗·╓╞_╦я╙н╧ш.json
new file mode 100644
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--- /dev/null
+++ b/task2/task2-paper-info/║г╤є╗╖╛│╓╟─▄╖└╕п═┐▓уг║╜с╣╣╔ш╝╞╙ы╧ь╙ж╗·╓╞_╦я╙н╧ш.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
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diff --git a/task2/task2-paper-info/╒│╨╘╞Ё╩╝▓у ═и╙├╦о─¤╜║AM.json b/task2/task2-paper-info/╒│╨╘╞Ё╩╝▓у ═и╙├╦о─¤╜║AM.json
new file mode 100644
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+++ b/task2/task2-paper-info/╒│╨╘╞Ё╩╝▓у ═и╙├╦о─¤╜║AM.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "1) Deposit a sticky polydopamine/ $\\mathsf{\\Pi}_{\\mathsf{F e}^{3+}}$ coating on the surface of the substrates to create a sticky initiation layer (SIL). 2) Reduce $\\mathsf{F e}^{3+}$ ions to $\\mathsf{F e}^{2+}$ ions as active catalysts by UV illumination with the assistance of citric acid. 3) Conduct surface catalytically initiated radical polymerization (SCIRP) in a monomer solution at room temperature to grow hydrogel coatings.The synthesis of hydrophilic polymers involves several key steps: First, graft coupling molecules with specific functional groups onto the substrate. Depending on the method chosen, such as the hydrogel painting method, a polymer layer is grafted using silane before the curing process. In the SCIRP method, an iron catalyst is doped into the substrates beforehand. For the UV-SCIRP method, a sticky initiation layer (SIL) is formed, providing an anchoring site for radical initiation. Following this, radical initiators are introduced and a monomer solution is applied. The photoinitiation or thermal initiation is then conducted, facilitating the radical polymerization process under UV or heat for a duration of 30-90 minutes."
+}
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diff --git a/task2/task2-paper-info/╒│╨╘╞Ё╩╝▓у ═и╙├╦о─¤╜║AM╕╜╝■.json b/task2/task2-paper-info/╒│╨╘╞Ё╩╝▓у ═и╙├╦о─¤╜║AM╕╜╝■.json
new file mode 100644
index 0000000..7292acd
--- /dev/null
+++ b/task2/task2-paper-info/╒│╨╘╞Ё╩╝▓у ═и╙├╦о─¤╜║AM╕╜╝■.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "Preparation of HPAA-PAM coating: The substrates after UV irradiation were immersed into the PAA-PAM monomer solution (4.26 g AM, 1.08 g AA, 0.02 g APS and 0.05 g MBAA, 30 mL H2O) for SCIRP to grow a hydrogel coating. After removal from the monomer solution, the substrates aged for 5 min at room temperature, followed by rinsing with deionized water five times. Preparation of HPNIPAM-PAA coating: The substrates after UV irradiation were immersed into the monomer solution (6.78 g NIPAM, 0.864 g AA, 0.02 g APS and 0.05 g MBAA, 40 mL H2O) for SCIRP for 25 min. Following removal from the monomer solution, the substrates were allowed to age for 5 min at room temperature and then rinsed with deionized water five times. Preparation of HPVA-PHEMA coating: 6.5 g HEMA, 0.01 g MBAA, 0.02 g APS and 0.1 g AA were dissolved in 50 mL H2O (solution A), while 20 g PVA was dissolved in 100 mL H2O (solution B). Solution A was mixed with solution B at a ratio of 1.5:1. The substrates after UV irradiation were immersed in the mixed monomer solution for SCIRP for 25 min, followed by a freeze-thaw process (-40 °C to 20 °C for 3 cycles) and rinsed with deionized water five times. Preparation of HPOEGMA-PAA coating: The substrates after UV irradiation were immersed into the POEGMA-PAA monomer solution (6.5 g OEGMA, 1.08 g AA, 0.01 g MBAA, 0.02 g APS, 40 mL H2O) for SCIRP for 25 min, then aged for 5 min at room temperature and rinsed with deionized water five times. Preparation of HPOEGMA-PAA-PHEMA coating: The substrates after UV irradiation were immersed in the POEGMA-PAA monomer solution (3.75 g OEGMA, 3.25 g HEMA, 1.08 g AA, 0.01 g MBAA, 0.02 g APS, 20 mL H2O) for SCIRP for 25 min, aged for 5 min at room temperature, then rinsed with deionized water five times.Preparation of HPVA-PAA-PAM coating on Ti substrate: First, 4.26 g AM, 1.08 g AA, 0.02 g APS and 0.05 g MBAA were dissolved in 30 mL H2O (solution C), 20 g PVA was dissolved in 100 mL H2O and heated to 100°C until complete dissolution (solution B); then, solution C was mixed with solution B at a volume ratio of 1:1; finally, the substrates after UV irradiation were immersed in the above mixed monomer solution to perform SCIRP for 2 min and put into the freeze-dryer to experience freezing (-40°C) and thawing (20°C) for 3 cycles. After the cyclic freezing-thawing process, the Ti substrate with the HPVA-PAA-PAM coating was rinsed with deionized water five times to remove unreacted monomers.  Preparation of HPHEMA-SA-Ca coating on Ti substrate: First, 6.5 g HEMA, 0.01 g MBAA, 0.02 g APS and 1 g SA were dissolved in 50 mL H2O and stirred until complete dissolution; then, the substrates after UV irradiation were immersed into the above monomer solution to perform SCIRP for 2 min; finally, the Ti substrate with HPHEMA-SA coating was immersed into CaCl2 solution (2%) for 2 h. Preparation of patterned hydrogel coating on Ti substrate: First, 5.91 g CA and 5.09 g FeCl3·6H2O were dissolved in 150 mL deionized water, and 1 mol/L NaOH solution was added to the above solution until the pH reached 4.0. Then, the substrate deposited with the PDA coating was immersed into the above mixed solution for 3 h. Subsequently, the treated substrate was placed under the programmable UV light source of a 3D printer for 5 min to reduce Fe3+. Next, the substrate after irradiation with UV light was immersed in monomer solution A to grow a patterned hydrogel coating for a certain time. Correspondingly, the Ti substrate with the growed patterned PAA-PAM hydrogel coating after removal from the monomer solution was allowed to naturally age for 5 min at room temperature. Finally, the sample after aging was rinsed with deionized water five times to further remove unreacted monomers.1. Immerse PDA-decorated medical devices in an aqueous solution of dopamine (2 mg/mL, in 10 mM Tris buffer, pH 8.5) under stirring for 24 h to decorate the PDA layer. 2. Rinse the PDA-decorated devices with deionized water and alcohol to remove unreacted chemicals. 3. Dissolve 5.91 g CA and 5.09 g FeCl3·6H2O in 150 mL deionized water. 4. Add 1 mol/L NaOH solution until the pH reaches 4.0. 5. Immerse the PDA-decorated devices in the mixed solution for 3 h. 6. Expose the devices to UV light (365 nm, 15 mW/cm2) for 2 min to produce Fe2+ in situ. 7. Immerse the devices in solution A to grow hydrogel coatings for a specified time. 8. Allow the devices with grown PAA-PAM hydrogel coating to naturally age for 5 min at room temperature. 9. Rinse the aged devices with deionized water five times to further remove unreacted monomers."
+}
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diff --git a/task2/task2-paper-info/╔ю╢╚╤з╧░╦о─¤╜║.json b/task2/task2-paper-info/╔ю╢╚╤з╧░╦о─¤╜║.json
new file mode 100644
index 0000000..0be0abd
--- /dev/null
+++ b/task2/task2-paper-info/╔ю╢╚╤з╧░╦о─¤╜║.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "To synthesize hydrophilic polymers with functional groups, a unique triple interlocking network composed of polyvinyl alcohol (PVA), polyacrylamide (PAAm), and CNFs•Zn2+ is utilized. The molecular chains are oriented and aligned through a mechanical training process, enhancing both strength and toughness. Additionally, polyaniline (PANI) is anchored to CNFs to create conductive pathways, improving conductivity post-orientation. Template structures are introduced into the system to mitigate negative interactions between the gel matrix and the conductive filler. The post-synthesis properties such as self-healing, antifreezing, and moisturizing capabilities are incorporated to ensure long-term functionality.A dual-network hydrogel composed of PVA and PAAm is synthesized with borax as a crosslinker. Subsequently, CNFs and Zn^{2+} ions are introduced to modify the hydrogel, enhancing its mechanical properties. Mechanical training is applied to the interlocked-network structure to align molecular chains and improve toughness and fatigue resistance.Synthesis of $P_{B}A C_{A}.Z n^{2+}$ Hydrogels: Briefly, a certain quantity of PVA, AAm, Borax and the synthesized CNFs-PANI were placed in a three-necked flask and thoroughly mixed. Subsequently, KPS and MBAA were added to the mixture and stirred until a homogeneous solution was obtained. The polymerization solution was injected into a specific mold and placed at $65~^{\\circ}C$ to initiate polymerization. After five hours, a PVA $_{\\mathsf{B o r a x}}/\\mathsf{A A m/C N F}.$ PANI hydrogel, abbreviated as $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}$ hydrogel, was obtained. The prepared hydrogel was immersed in the $Z\\mathsf{n}(\\mathsf{B F}_{4})_{2}$ solution for $6\\mathfrak{h}$ , and the final product was obtained and noted as $\\mathsf{P}_{\\mathsf{B}}\\mathsf{A C}_{\\mathsf{A}}.\\mathsf{Z n}^{2+}$ hydrogel."
+}
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diff --git a/task2/task2-paper-info/╔┘╤∙▒╛SI.json b/task2/task2-paper-info/╔┘╤∙▒╛SI.json
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index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/╔┘╤∙▒╛SI.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
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diff --git a/task2/task2-paper-info/╕┤╨╘╦о─¤╜║═┐┴╧ Sci. Adv.json b/task2/task2-paper-info/╕┤╨╘╦о─¤╜║═┐┴╧ Sci. Adv.json
new file mode 100644
index 0000000..f411167
--- /dev/null
+++ b/task2/task2-paper-info/╕┤╨╘╦о─¤╜║═┐┴╧ Sci. Adv.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "The renatured hydrogel painting (RHP) method involves a two-step technology for synthesizing hydrophilic polymers with functional groups. First, dehydrated xerogel particles are adhered to solid surfaces using a special adhesive. Next, these xerogel particles are rehydrated in an aqueous medium, resulting in a uniform hydrogel coating layer on the intended surface.First, spread or spray an uncured fluidic adhesive (e.g., diluted epoxy resin with acetone) on the surface of the substrate. Next, immediately cover the adhesive layer with xerogel particles made from a polyacrylamide-alginate-Ca2+ double-network hydrogel. Allow the adhesive to cure, bonding the xerogel particles to the substrate. Subsequently, rehydrate the xerogel particles in the presence of water to initiate the renaturation process, forming a hydrogel layer.The synthesis of hydrophilic polymers involved the use of sodium alginate (SA) as the primary material, which is extracted from brown algae. Acrylamide (AM) and N,N'-methylenebisacrylamide (MBAM) were incorporated as crosslinking agents to modify the polymer network. The process also utilized calcium chloride (CaCl2) and N,N,N',N'-tetramethyl-ethylenediamine (TEMED) as catalysts to facilitate the polymerization reaction. The precise mixing ratios and conditions such as temperature and time were not specified in the provided text.The epoxy resin components A and B were added to acetone with a ratio of 1:1, and they were fully stirred to form a uniform solution. The linker solution was freshly prepared just before use, but the component A or B solution could be stored separately for the long term. The viscosity of epoxy resin solution was measured by a rheometer (MCR 302, Anton Paar). The shear rate varied from 10^{-1} to 10^{3} s^{-1}. A steel parallel rotor with a diameter of 20 mm was used. The gap was kept at 50 µm, and the temperature was fixed at 25°C.PAM-alginate-${\\mathrm{Ca}}^{2+}$ hydrogel was prepared by curing a precursor solution containing 20 wt % AM, 0.05 wt % MBAM, 2 wt % SA, 0.05 wt % $(\\mathrm{NH}_{4})_{2}\\mathrm{S}_{2}\\mathrm{O}_{8}$, 0.34 wt % $\\mathrm{CaSO}_{4}{\\cdot}2\\mathrm{H}_{2}\\mathrm{O}$, and 0.1 wt % TEMED for 12 hours at room temperature. The double-network xerogel was made by vacuum freeze-drying and then triturated into multisize xerogel microparticles by ball milling. The multisize xerogel microparticles were filtered by size using ethanol as the solution. After evaporation of the ethanol, SP (30 to 40 μm), MP (60 to 80 μm), and LP (100 to 150 μm) were obtained. The substrates were cleaned with deionized water and ethanol, followed by drying at room temperature. The linker solution was coated on the surface of dry substrates, and then the xerogel powder was sprayed on the intermediate layer prepolymer. After polymerization of the linker, a uniform hydrogel coating was obtained, which was then immersed in deionized water for 24 hours.The PAM-Alginate hydrogel labeled with Rhodamine B was prepared by curing a pregel solution, containing 20 wt % AM, 0.05 wt % MBAM, 2 wt % SA, 0.05 wt % (NH4)2S2O8, 0.34 wt % CaSO4·2H2O, 0.1 wt % TEMED, and Rhodamine B (10^-5 g/ml) for 12 hours at room temperature. The xerogel containing Rhodamine B was punched into xerogel microparticles by ball milling. The microparticles with size approximately at 30 μm were screened out via rational filtration. The glass substrates were cleaned with deionized water and ethanol followed by drying under room temperature. A linker solution containing epoxy resin prepolymer (1.0 g/ml) and petroleum fluorescent tracing dye (10^-5 g/ml) in acetone was coated on the surface of cleaned glass slide. Afterward, the xerogel powder was sprayed on the adhesive layer after its precuring for 15 min at 75°C. The sandwich-like sample was further placed in an oven with a temperature of 75°C for another 3 hours and then immersed in Rhodamine B solution (10^-5 g/ml) for 24 hours to allow the rehydration of xerogel particles.The RHP coated on a metal panel was immersed in silicone oil for full impregnation. Upon placement into deionized water, the oil skin in the hydrogel coating was gradually removed. This demonstrated the completeness and continuity of the hydrogel coating. The RHP coated panel was then subjected to a high-pressure water jet impingement test. Finally, the panel that endured the impact went through an oil skin delamination experiment to verify the hydrogel coating's completeness.Spraying the epoxy solution on the PVC substrate for about 5 minutes. Allowing the epoxy resin to precure for 30 minutes at room temperature. Spraying xerogel powders on the surface of the partially cured epoxy resin for about 15 minutes. Further curing the epoxy resin for 3 hours at room temperature. Rinsing the xerogel layer with water to form the RHP coating."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╕▀═и┴┐║╧│╔╖╓╬Ў║═╙┼╗п╙├╙┌╡░░╫╓╩╡▌╦═╡─┐╔╫в╔ф╦о─¤╜║.json b/task2/task2-paper-info/╕▀═и┴┐║╧│╔╖╓╬Ў║═╙┼╗п╙├╙┌╡░░╫╓╩╡▌╦═╡─┐╔╫в╔ф╦о─¤╜║.json
new file mode 100644
index 0000000..fc7dee0
--- /dev/null
+++ b/task2/task2-paper-info/╕▀═и┴┐║╧│╔╖╓╬Ў║═╙┼╗п╙├╙┌╡░░╫╓╩╡▌╦═╡─┐╔╫в╔ф╦о─¤╜║.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "To synthesize hydrophilic polymers with functional groups, mix 12 precursor polymers functionalized with hydrazide groups and 2 functionalized with aldehyde groups in various ratios. Utilize a high-content robotics system for automated mixing to fabricate 126 different hydrogels within 25 minutes. Ensure the selected precursor polymers exhibit various charges (anionic, cationic, neutral), degradabilities (naturally sourced vs synthetic), and thermoresponsiveness (utilizing PNIPAM and POEGMA with different LCST values).1. Synthesize hydrazide functionalized POEGMA by mixing diethylene glycol methacrylate, oligo ethylene glycol methacrylate, acrylic acid, AIBMe, TGA, and 20 mL of dioxane in a 50 mL Schlenk three-neck flask. Purge with nitrogen for 30 min. Place the flask in a 75 °C oil bath and stir for 4 hours. 2. Remove excess dioxane by rotary evaporation and redissolve poly(OEGMA-co-AA) in 100 mL of distilled deionized water (DIW). 3. Functionalize acrylic acid residues with hydrazide groups using 5-fold excess of adipic acid dihydrazide and 2.5-fold excess of EDC at pH 4.75. 4. Dialyze for purification (6 hours for 6 cycles, MWCO = 3.5 kDa). 5. Characterize polymers using 1H NMR and conductometric titration to determine net cationic and anionic charge content."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╕▀╖╓╫╙═┐▓у▓─┴╧╝░╞ф╖└╬█╩═╖┼╗ю╨╘╥╗╓╓╙├╙┌╘д▓т╨╘╓╩╡─╗п╤з╨┼╧в╤з╖╜╖и.json b/task2/task2-paper-info/╕▀╖╓╫╙═┐▓у▓─┴╧╝░╞ф╖└╬█╩═╖┼╗ю╨╘╥╗╓╓╙├╙┌╘д▓т╨╘╓╩╡─╗п╤з╨┼╧в╤з╖╜╖и.json
new file mode 100644
index 0000000..73f6658
--- /dev/null
+++ b/task2/task2-paper-info/╕▀╖╓╫╙═┐▓у▓─┴╧╝░╞ф╖└╬█╩═╖┼╗ю╨╘╥╗╓╓╙├╙┌╘д▓т╨╘╓╩╡─╗п╤з╨┼╧в╤з╖╜╖и.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Silica was dispersed in butyl acetate (BA) at a 20:80 silica/BA wt./wt. ratio for preparation of the coating materials. Tetrabutylammonium fluoride (TBAF) was diluted with 4-methyl-2-pentanone (MIBK) to produce a 50 mM solution for catalysis. Coating compositions were prepared by encoding them as xPEG/yCF3, where x is the TMS-PEG content expressed as a weight percentage relative to the total weight of PDMS, CF3-PDMS, silica, TMS-PEG, and MeTAcSi, and y is the CF3-PDMS content expressed as a weight percentage relative to the total weight of CF3-PDMS and PDMS.A set of 27 polymer coatings was produced using a combinatorial approach with a focus on synthesizing hydrophilic polymers with various functional groups. Polymer coatings were prepared in multiwell plates employing an automated water-jet method to assess adhesion to marine bacteria and microalgae. The specific components used included CF3-PDMS and TMS-PEG. These components were under varying concentrations, forming mixture systems for further QSAR modeling, which was executed using Genetic Algorithm (GA) and Multiple Linear Regression Analysis (MLRA) techniques to establish a correlation between their structural properties and biological activities. Descriptors encoding chemical structure were generated and utilized for mixture models, leading to the prediction of biological activities based on the component properties within polymer coatings."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╕▀╖╓╫╙▓─┴╧╗∙╥Є╫щ╤╨╛┐╜°╒╣_╙жь│╢∙.json b/task2/task2-paper-info/╕▀╖╓╫╙▓─┴╧╗∙╥Є╫щ╤╨╛┐╜°╒╣_╙жь│╢∙.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/╕▀╖╓╫╙▓─┴╧╗∙╥Є╫щ╤╨╛┐╜°╒╣_╙жь│╢∙.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╖█─й═┐┴╧╛▓╡ч┼ч═┐╡──¤╣╠╣¤│╠╖╓╬Ў╙ы▓╬╩¤╙┼╗п.json b/task2/task2-paper-info/╖█─й═┐┴╧╛▓╡ч┼ч═┐╡──¤╣╠╣¤│╠╖╓╬Ў╙ы▓╬╩¤╙┼╗п.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/╖█─й═┐┴╧╛▓╡ч┼ч═┐╡──¤╣╠╣¤│╠╖╓╬Ў╙ы▓╬╩¤╙┼╗п.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╗∙╙┌├ш╩Ў╖√╠ї╝■╤н╗╖╔ё╛н═°┬ч╡─┤╙═╖╖╓╫╙╔·│╔╓▒╜╙╥¤╡╝.json b/task2/task2-paper-info/╗∙╙┌├ш╩Ў╖√╠ї╝■╤н╗╖╔ё╛н═°┬ч╡─┤╙═╖╖╓╫╙╔·│╔╓▒╜╙╥¤╡╝.json
new file mode 100644
index 0000000..130c066
--- /dev/null
+++ b/task2/task2-paper-info/╗∙╙┌├ш╩Ў╖√╠ї╝■╤н╗╖╔ё╛н═°┬ч╡─┤╙═╖╖╓╫╙╔·│╔╓▒╜╙╥¤╡╝.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of hydrophilic polymers with functional groups involves constructing conditional recurrent neural networks (cRNNs) by setting the internal states of long short-term memory cells (LSTMs) after input conditions. The process utilizes molecular descriptors, which can include physicochemical properties derived from the molecular structure using software tools like the RDKit Python library. For example, the physchem-based (PCB) model incorporates six scalar properties: logP, TPSA, molecular weight, drug-likeness (QED), number of hydrogen-bond acceptors (HBA), and donors (HBD), concatenated with bioactivity predictions from QSAR models. The model is trained using randomized SMILES strings as targets, with inference triggered by a specific starting character and stopping upon the generation of a designated character."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╗∙╙┌╗·╞ў╤з╧░╡─╥■╔э═┐┴╧╔ш╝╞╖╜╖и╙ы╤╨╛┐╜°╒╣_┴ї╨ё.json b/task2/task2-paper-info/╗∙╙┌╗·╞ў╤з╧░╡─╥■╔э═┐┴╧╔ш╝╞╖╜╖и╙ы╤╨╛┐╜°╒╣_┴ї╨ё.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/╗∙╙┌╗·╞ў╤з╧░╡─╥■╔э═┐┴╧╔ш╝╞╖╜╖и╙ы╤╨╛┐╜°╒╣_┴ї╨ё.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╘┌╚э╗·╞ў╚╦╓╨╩╡╧╓┤л╕╨╘╦╢п╣ж─▄╡─╚э▓─┴╧║═╫░╓├.json b/task2/task2-paper-info/╘┌╚э╗·╞ў╚╦╓╨╩╡╧╓┤л╕╨╘╦╢п╣ж─▄╡─╚э▓─┴╧║═╫░╓├.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/╘┌╚э╗·╞ў╚╦╓╨╩╡╧╓┤л╕╨╘╦╢п╣ж─▄╡─╚э▓─┴╧║═╫░╓├.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╙├╙┌▓─┴╧╖в╧╓╡─╔·│╔╩╜╚╦╣д╓╟─▄ги╙в╬─гй_Jianjun Hu.json b/task2/task2-paper-info/╙├╙┌▓─┴╧╖в╧╓╡─╔·│╔╩╜╚╦╣д╓╟─▄ги╙в╬─гй_Jianjun Hu.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/╙├╙┌▓─┴╧╖в╧╓╡─╔·│╔╩╜╚╦╣д╓╟─▄ги╙в╬─гй_Jianjun Hu.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╙═╦о╖╓└ыAFM.json b/task2/task2-paper-info/╙═╦о╖╓└ыAFM.json
new file mode 100644
index 0000000..919ac3a
--- /dev/null
+++ b/task2/task2-paper-info/╙═╦о╖╓└ыAFM.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Prepare an ethanol/water solvent system to regulate hydrogen bond cross-linking between polyvinyl alcohol (PVA) and tannic acid (TA). Create a 'hydrogel paint' using a one-pot method. Apply the hydrogel paint onto the surface of stainless-steel mesh (SSM) using a common paint application method. Allow the ethanol in the hydrogel paint to evaporate gradually, enabling the reestablishment of hydrogen bond cross-linking between PVA and TA, resulting in a stable hydrogel coating layer.Dissolve poly(vinyl alcohol) (PVA) and the crosslinking agent, tannic acid (TA), in a solvent system consisting of ethanol and water. The final optimized volume ratio of water to ethanol should be 5:5 to ensure uniform fluidity and good processability. Mix the components until a stable and homogeneous hydrogel paint is obtained. Apply the hydrogel paint to the surface of the porous substrate (SSM) using one of the following methods: dipping, spraying, brushing, or shearing. Remove the ethanol from the coating by volatilization to re-establish the hydrogen bond between PVA and TA, forming a 3D network structure. Optionally, integrate an appropriate amount of nano-sized SiO2 to enhance the surface roughness and stability of the PVA-TA gel.PVA (3.0 g) and TA (3.0 g) were dissolved in 94.0 g mixed solvent (deionized water/ethanol = 1:1 v/v) with stirring at approximately 90°C for 6 hours to obtain PVA-TA hydrogel paint. For PVA-TA@SiO2 hydrogel paint, 0.6 g SiO2 was added to the water/ethanol solvent under ultra-sonication for 30 minutes before adding PVA and TA. The SSM (average pore diameter of approximately 50 μm) was immersed in the pre-gel solution for 2 minutes, then taken out and dried at room temperature to obtain the hydrogel-coated mesh."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╙╛╛╡╖└╬э╥й╦о╕─╔╞╩ф╚ы-20191028.json b/task2/task2-paper-info/╙╛╛╡╖└╬э╥й╦о╕─╔╞╩ф╚ы-20191028.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/╙╛╛╡╖└╬э╥й╦о╕─╔╞╩ф╚ы-20191028.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╚э╨╘║═╥║╠м╖╓╫╙▓─┴╧╡─╗·╞ў╤з╧░.json b/task2/task2-paper-info/╚э╨╘║═╥║╠м╖╓╫╙▓─┴╧╡─╗·╞ў╤з╧░.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/╚э╨╘║═╥║╠м╖╓╫╙▓─┴╧╡─╗·╞ў╤з╧░.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╚╦╣д╓╟─▄+╨┬▓─┴╧╤╨╖вг║┬ї╧Є...╘д▓т╨╘╔ш╝╞б▒║═б░╛л╫╝┤┤╓╞б▒_╣∙╫╙╖╝.json b/task2/task2-paper-info/╚╦╣д╓╟─▄+╨┬▓─┴╧╤╨╖вг║┬ї╧Є...╘д▓т╨╘╔ш╝╞б▒║═б░╛л╫╝┤┤╓╞б▒_╣∙╫╙╖╝.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/╚╦╣д╓╟─▄+╨┬▓─┴╧╤╨╖вг║┬ї╧Є...╘д▓т╨╘╔ш╝╞б▒║═б░╛л╫╝┤┤╓╞б▒_╣∙╫╙╖╝.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╚╦╣д╓╟─▄╕и╓·╔ш╝╞╣ж─▄╨╘║═┐╔│╓╨°╛█║╧╬я.json b/task2/task2-paper-info/╚╦╣д╓╟─▄╕и╓·╔ш╝╞╣ж─▄╨╘║═┐╔│╓╨°╛█║╧╬я.json
new file mode 100644
index 0000000..c2f1201
--- /dev/null
+++ b/task2/task2-paper-info/╚╦╣д╓╟─▄╕и╓·╔ш╝╞╣ж─▄╨╘║═┐╔│╓╨°╛█║╧╬я.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Develop a candidate list of polymers using 'virtual forward synthesis' (VFS). Start with commercially available monomer molecules and use known polymerization reaction templates to create polymers."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╚╦╣д╓╟─▄╕и╓·╨┬╗п╤з╞╖╔ш╝╞╩╙╜╟.json b/task2/task2-paper-info/╚╦╣д╓╟─▄╕и╓·╨┬╗п╤з╞╖╔ш╝╞╩╙╜╟.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/╚╦╣д╓╟─▄╕и╓·╨┬╗п╤з╞╖╔ш╝╞╩╙╜╟.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╚╦╣д╓╟─▄╘┌╗п╤з╣д│╠╓╨╡─╙ж╙├бкбк┤┤╨┬╡─╨┬╞к╒┬ги╙в╬─гй_╚╬╞ф┴·.json b/task2/task2-paper-info/╚╦╣д╓╟─▄╘┌╗п╤з╣д│╠╓╨╡─╙ж╙├бкбк┤┤╨┬╡─╨┬╞к╒┬ги╙в╬─гй_╚╬╞ф┴·.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/╚╦╣д╓╟─▄╘┌╗п╤з╣д│╠╓╨╡─╙ж╙├бкбк┤┤╨┬╡─╨┬╞к╒┬ги╙в╬─гй_╚╬╞ф┴·.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╚╦╣д╓╟─▄╘┌╤к╥║╝▓▓б╒я┴╞╓╨╡─╙ж╙├╤╨╛┐╜°╒╣_╒┼└ё╟▒.json b/task2/task2-paper-info/╚╦╣д╓╟─▄╘┌╤к╥║╝▓▓б╒я┴╞╓╨╡─╙ж╙├╤╨╛┐╜°╒╣_╒┼└ё╟▒.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/╚╦╣д╓╟─▄╘┌╤к╥║╝▓▓б╒я┴╞╓╨╡─╙ж╙├╤╨╛┐╜°╒╣_╒┼└ё╟▒.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╚╦╣д╓╟─▄╟¤╢п╡─╦о─¤╜║╔ш╝╞бв╙┼╗п╝░╞ф╘┌╔·╬я╥╜╤з╓╨╡─╙ж╙├.json b/task2/task2-paper-info/╚╦╣д╓╟─▄╟¤╢п╡─╦о─¤╜║╔ш╝╞бв╙┼╗п╝░╞ф╘┌╔·╬я╥╜╤з╓╨╡─╙ж╙├.json
new file mode 100644
index 0000000..c5b3669
--- /dev/null
+++ b/task2/task2-paper-info/╚╦╣д╓╟─▄╟¤╢п╡─╦о─¤╜║╔ш╝╞бв╙┼╗п╝░╞ф╘┌╔·╬я╥╜╤з╓╨╡─╙ж╙├.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of hydrophilic polymers with functional groups can be achieved through various methods including physical cross-linking, dynamic cross-linking, and chemical cross-linking. These methods allow for the engineering of the gelation process to meet specific needs. Advanced chemical approaches can be utilized to manipulate the shape, structure, and architecture of hydrogels, enabling the incorporation of desirable functionalities such as adjustable properties, excellent biocompatibility, controllable degradability, and mechanical compatibility with biological tissues."
+}
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diff --git a/task2/task2-paper-info/╚╦╣д╓╟─▄╥¤╡╝╡─╔┘╤∙▒╛─ц╧Є╔ш╝╞╙├╙┌┐╣╥й╨╘╧╕╛·╡─╕▀├▄╢╚╛█║╧╬я─г─т╛█║╧╬я.json b/task2/task2-paper-info/╚╦╣д╓╟─▄╥¤╡╝╡─╔┘╤∙▒╛─ц╧Є╔ш╝╞╙├╙┌┐╣╥й╨╘╧╕╛·╡─╕▀├▄╢╚╛█║╧╬я─г─т╛█║╧╬я.json
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+{
+    "protocol": "The synthesis of hydrophilic polymers was achieved by implementing a comprehensive multi-step AI-guided framework. First, the polymer structures were transformed into multimodal polymer representations to enhance the model performance by capturing comprehensive multi-scale polymer information. Then, a graph grammar distillation method was developed, which decomposed the chemical structure of collected beta-amino acid polymers and homologous natural alpha-amino acids into various molecular graph grammar fragments. These fragments were recombined to form new molecules. The resolution-recombination process was iterated to pre-train a generative model focused on generating beta-amino acid polymer structures that adhere to rational chemical principles. The pre-trained predictive and generative models were combined using reinforcement learning to form a polymer inverse design framework. This framework allowed the generative model to create a set of novel polymers, while the predictive model evaluated their bioactivity and structures, providing rewards that updated the generative model's parameters for subsequent iterations. The final outcome was the identification of candidate polymers exhibiting the desired bioactivity.The synthesis of hydrophilic polymers involves two main stages. Firstly, a GRU-based molecular scaffold-decorator is pre-trained to generate valid subunits. Secondly, a reinforcement learning fine-tuning stage is implemented to explore the chemical space for optimal polymers. During fine-tuning, each reasonable molecule generated is recorded for final analysis and evaluation.1. Mix 15.0 g (0.1 mol) of 3,3-Dimethylallyl bromide and 20.4 g (0.11 mol) of potassium phthalimide in 300 mL DMF. Stir vigorously at room temperature for 16 h. 2. Pour the reaction mixture into 800 mL ice water with vigorous stirring to precipitate the product. Collect the precipitate by filtration and wash with ethanol. The crude product is used without purification (20.0 g, 93.0%). 3. In a solution of the intermediate compound (20.0 g, 0.093 mol) in 50 mL dichloromethane, add 10.4 mL of chlorosulfonyl isocyanate (0.11 mol) under N2 atmosphere. Stir for 30 min at 0°C, then warm up to room temperature for 72 h. 4. Pour the reaction mixture into a suspension of 41.6 g (0.33 mol) of Na2SO3 and 46.9 g (0.33 mol) of Na2HPO4 in 800 mL water and stir for 12 h. 5. Extract the aqueous phase with dichloromethane (3 x 500 mL). Combine the organic phase, dry over anhydrous magnesium sulfate, and concentrate under vacuum to obtain the crude product. 6. Purify the crude product by recrystallization from ethyl acetate and hexane to isolate maleimide-protected DM (14.6 g, 60.8%). 7. Dissolve 14.6 g (56.5 mmol) of compound 2 in 200 mL methanol. Add 14 mL of 80% hydrazine hydrate solution in water. Stir at 70°C for 12 h to precipitate. 8. Filter out the precipitate and coevaporate the filtrate with toluene (3 x 200 mL) to remove residual hydrazine hydrate. 9. Mix 24.6 g (113.0 mmol) of di-tertbutyl dicarbonate and 15.3 mL (113.0 mmol) of triethylamine in 500 mL methanol. Reflux for 6 h. 10. After filtration, concentrate the solvent under vacuum to obtain the residue. 11. Dissolve the residue in 200 mL dichloromethane, and wash sequentially with 1 N hydrochloric acid, 1 N sodium hydroxide, and 200 mL brine. 12. Dry the organic phase over anhydrous magnesium sulfate and concentrate under vacuum to yield the crude product. Purify directly by column chromatography to obtain β-Lactam DM (9.7 g, 75.2%).All polymerizations of β-lactams were carried in nitrogen-regulated glove box at room temperature. Initiator (tBuBzCl), β-lactams (DM and iPen) and the base catalyst LiHMDS were dissolved in dry THF to a concentration of 0.2 M respectively. The positive charge and hydrophobic composition of β-amino acid polymers was controlled by the initial feed ratio of tBuBzCl: DM: iPen. Briefly, 2 mL β-lactams with different volume ratios of DM: iPen were mixed, after adding 100 µL tBuBzCl solution in THF and 300 µL LiHMDS in THF into the mixture sequentially, the reaction mixture was stirred for 12 h. When the polymerization reaction was completed, the reaction mixture was poured into cold petroleum ether (PE, 45 mL) to precipitate out the crude product as a white solid, followed by centrifugation (2810 g) to remove the solvent. The crude product was dissolved in 2 mL THF followed by pouring cold petroleum ether (45 mL) to precipitate out the crude product. The N-Boc protected polymers were purified by dissolution-precipitation process using THF/PE (2 mL/45 mL) three times and vacuum drying for overnight to give a white solid. The number-average molecular weight (Mn) and polydispersity index (D) were characterized by GPC using N,N-dimethylformamide (DMF) as the mobile phase. N-Boc protected polymers were dissolved in trifluoroacetic acid (2 mL). Then the mixture was under shaking for 2 h at room temperature. After removing the solvent under a nitrogen flow, the residue was dissolved in methanol (1 mL), followed by addition of cold MTBE (45 mL) to precipitate out the crude polymers. The crude polymers were purified by three times of dissolution-precipitation process using methanol/MTBE (1 mL/45 mL) and vacuum drying for overnight. The purified polymers were dissolved in Milli-Q water and lyophilized to obtain a white powder in the form of TFA salt (>80.0% yield), which was further characterized by 1H NMR and used for antibacterial assay.The dye-labeled beta-amino acid polymer (DM_{0.8}iPen_{0.2})_{20} was synthesized by dissolving the initiator Dye-NHS ester, co-initiator LiHMDS, DM monomer, and iPen monomer in dried tetrahydrofuran (THF) at a final concentration of 0.2M inside a glove box. 1.6 mL of DM, 0.4 mL of iPen, and 0.1 mL of Dye-NHS ester were mixed and stirred. 0.3 mL of LiHMDS was quickly added to the mixture. The reaction was stirred for 6 hours at room temperature and quenched with 5 drops of MeOH. The solvent was removed under N2 flow, and the residue was dissolved in 1 mL of THF, then transferred to a centrifuge tube. Cold PE (45 mL) was added to precipitate a yellow product. The N-Boc protected polymer was purified via three dissolution-precipitation processes using THF/PE (1 mL/45 mL), vacuum dried, and characterized by GPC using DMF containing 10 mM LiBr as the mobile phase. The polymer was dissolved in 2 mL TFA and stirred at room temperature for 2 hours to remove the Boc protection. After TFA removal under N2 flow, the residue was dissolved in 1 mL MeOH, and cold MTBE (45 mL) was added to precipitate a yellow product. The N-Boc deprotected polymer was purified via three dissolution-precipitation processes using MeOH/MTBE (1 mL/45 mL), vacuum dried, and dissolved in MilliQ water. Finally, the solution was lyophilized to obtain the final dye-labeled polymer (DM_{0.8}iPen_{0.2})_{20}, suitable for confocal imaging.The outer membrane permeabilization assay for drug-resistant E. coli was conducted according to the protocol in our previous study. Briefly, the bacteria were cultured in LB medium at 37°C for 6 hours to obtain the bacterial suspension. The bacterial suspension was washed by PBS buffer and then diluted in HEPES medium (5 mM HEPES, 20 mM glucose, pH=7.4) to achieve a working suspension with a cell density of 3×10^8 CFU mL^{-1}. Following this, 1-N-phenyl-naphthylamine (NPN) dye was added at a final concentration of 10 μM. An aliquot of the working suspension containing NPN was added to each well of a 384-well plate. The fluorescence changes (excitation λ=350 nm, emission λ=420 nm) were recorded on a SpectraMax M2 plate reader (Molecular Devices, USA). Once the fluorescence intensity remained stable, 10 μL of (DM0.8iPen0.2)20 was added to the bacterial solution, and the fluorescence intensity was recorded continuously."
+}
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diff --git a/task2/task2-paper-info/╛╓▓┐╡▌╦═└╫┼┴├╣╦╪═и╣¤╡ў┐╪╣╟...┐╫╝┘╠х╜ч├ц╣╟╒√║╧╡─╗·╓╞╤╨╛┐_└ю╫ц║╞.json b/task2/task2-paper-info/╛╓▓┐╡▌╦═└╫┼┴├╣╦╪═и╣¤╡ў┐╪╣╟...┐╫╝┘╠х╜ч├ц╣╟╒√║╧╡─╗·╓╞╤╨╛┐_└ю╫ц║╞.json
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+{
+    "protocol": "The text excerpt does not provide specific details on the experimental protocol for the synthesis of hydrophilic polymers with functional groups.本研究拟通过构建经皮超声介导雷帕霉素递送和功能化水凝胶介导的雷帕霉素局部递送两种策略，上调 OP-BMSCs 的自噬水平，以恢复下降的细胞活性（包括细胞活力、增殖、迁移和成骨）和抑制成脂分化，从而促进 3D打印微孔假体界面在骨质疏松状态下的骨整合。取 9.14~\\\\upmu\\\\mathrm{g} 雷帕霉素充分溶解于 10~\\\\mathrm{ml} 低糖DMEM 中，配置出浓度为 1000~\\\\mathrm{{nM}} 雷帕霉素溶液。将明胶海绵裁剪为直径为 1cm 的圆片状，并将 200~\\\\upmu\\\\mathrm{l} 雷帕霉素溶液添加到明胶海绵块中。将明胶海绵与超声发射探头紧密贴合，然后用新鲜兔皮外层包裹明胶海绵与探头，兔皮内层朝向含有 2~\\\\mathrm{ml} 溶液的孔板。设置超声电导仪的频率为 30~\\\\mathrm{kHz} ，强度为 45\\\\mathrm{W/cm}^{2} ，每隔 2\\\\mathrm{min} 收集孔板中的液体，并用新鲜溶液等量替换，导药结束后用高效液相色谱-串联质谱仪检测各时间点孔板中雷帕霉素的浓度。然后将 3D 打印微孔钛合金支架植入兔左侧股骨远端外侧髁，配制浓度为 1000~\\\\mathrm{{nM}} 的FITC-雷帕霉素。将浸有 200~\\\\upmu\\\\mathrm{l} 药液的明胶海绵稳定放置在左侧股骨远端外侧髁皮肤与超声发射器头之间进行药物递送，设置超声电导仪的频率为 30\\\\mathrm{kHz} ，强度为 45\\\\mathrm{W/cm}^{2} ，时间为 10\\\\mathrm{min} 。将细胞以 $1{\\times}10^{4}/$ 孔的密度种植在 12 孔板中，待细胞贴壁后换液，使用成脂诱导培养基，给与超声介导的雷帕霉素递送处理。待细胞贴壁后更换成脂诱导培养基 A 液进行培养，3 天后换用成脂诱导培养基B 液进行培养 $24\\mathrm{h}$，如此A、B 培养基交替使用培养至第 21 天； $10\\%$ 多聚甲醛固定细胞 $10\\mathrm{min}$，弃去固定液，PBS 洗涤，加入油红 O 染色液 $400~\\upmu\\mathrm{l}$ 孵育 $30~\\mathrm{min}$，移除油红 O 染液，并用 PBS 洗涤 2 次，光镜下观察；使用甲醇洗脱染色 $30\\mathrm{min}$，并使用酶标仪在 $510\\mathrm{nm}$ 处测量吸光度进行定量。1) 制备 N-羧乙基壳聚糖（CEC）：将壳聚糖（2g，12.4mmol）与丙烯酸（2.9mL，42.6mmol）溶解于100mL去离子水中，在50°C水浴中磁力搅拌72h。随后，滴加NaOH溶液调节体系pH值至10–12。将所得溶液置于去离子水中透析（MWCO 14000）3天，将产品冷冻干燥，获得CEC粉末备用；\\n\\n2) 制备纳米银线（AgNW）：在磁力搅拌下（260rpm）将无水乙二醇（5ml）加热至151.5°C 1小时。向体系中加入含CuCl2的乙二醇溶液（(4mmol L^{-1}, 0.9ml)）。继续搅拌15min，然后加入溶于乙二醇中的聚乙烯基吡咯烷酮（PVPON）溶液（(0.1g, 2.5ml)），再注射溶有AgNO3的乙二醇溶液（(0.05g, 2.5ml)），继续搅拌30min，待反应结束体系冷却至室温后，进行2000rpm，5min乙醇离心洗涤多次，获得AgNW待用；\\n\\n3) 合成CEC-PVA-AgNW水凝胶：将0.5g聚乙烯醇（PVA），CEC（(0.025g)），琼脂糖（0.025g）和甘油（0.2ml）溶解在10ml去离子水中，在90°C磁搅拌下油浴2h，然后向上述溶液中加入AgNW(0.2mgml^{-1})，继续搅拌15min。最后，将10ml Na2B4O7溶液（0.04mol L^{-1}）加入上述混合物中，通过搅拌约10min即可获得CEC-PVA-AgNW水凝胶。将获得的 CEC-PVA-AgNW 水凝胶冻干、脱模，在样本表面进行喷金处理后在扫描电子显微镜下进行观察水凝胶表面微观结构。将 $100~\\mathrm{{mg}}$ 冻干水凝胶放入体外生理模拟液中（ $37^{\\mathrm{{\\circ}}}\\mathrm{C}$ ，PBS 缓冲液），并在溶液中加入 $0.02\\mathrm{wt\\%}$ 叠氮化钠，抑制细菌生长。在预先设定的时间点收集PBS 中残存的水凝胶，冻干后计算质量损失。将 Na2B4O7 溶液添加到 PVA、CEC、琼脂糖、甘油和 AgNW 的混合溶液中，均匀搅拌后即可获得透明的导电超分子水凝胶。To synthesize hydrophilic polymers with functional groups, begin with a prepolymer solution prepared by dissolving a chosen monomer in a suitable solvent. Add a crosslinking agent to this solution in a predetermined molar ratio. Then, incorporate any desired functional groups into the polymer chain by introducing functionalized monomers or reagents during the polymerization process. Initiate polymerization by heating the solution or adding an appropriate catalyst. Maintain the reaction conditions, including temperature and time, according to the specific polymerization method selected, such as free radical polymerization or condensation reactions. After the reaction is complete, precipitate the polymer by adding a non-solvent, followed by washing and drying to remove unreacted materials and solvents. Finally, characterize the functionalized hydrophilic polymer using techniques such as NMR, FTIR, or gel permeation chromatography to confirm successful synthesis.在凝胶溶液混合前，将 $10\\mathrm{mlNa}_{2}\\mathrm{B}_{4}\\mathrm{O}_{7}$ 溶液（ $0.04\\mathrm{mol}\\mathrm{L}^{-1}$ ）溶液中预先加入放有3D 打印微孔假体的模具中，再往模具中加入含有雷帕霉素（ $54.85~\\mathrm{mg}$ ）的PVA（ $(0.5\\mathrm{g})$ ）、CEC（ $(0.025\\mathrm{g})$ ）、琼脂糖（ $(0.025\\mathrm{g})$ ）、甘油（ $0.2{\\mathrm{ml}}$ ）和 AgNW（ $0.2\\mathrm{mg}$ $\\mathrm{ml}^{-1}$ ）混合溶液，搅拌 $15\\mathrm{min}$ ，使溶胶充分混合并浸入微孔内部并成胶，最终获得雷帕霉素终浓度为 $3~{\\upmu\\mathrm{M}}$ 的3D 打印生物活性界面。取 1~ml 初始菌液加入细菌培养试管，再加入 LB 液体培养基 5~ml，将试管放入恒温震荡箱中，设置温度为 37^{\\circ}C，转速为 100r/min。培养 20h 后收集试管中培养液 100μl，进行细菌活死染色，具体步骤如下：1）将1 体积的 DMAO 和2 体积的EthD-Ⅲ在离心管中充分混合均匀，加入8 体积的 0.85%NaCl 得到 100×染色工作液；2）100μl 菌液中加入 1μl 的 100×染色工作液，混合均匀，室温下避光孵育15min；3）取 10~μl 染色后的菌液滴加在载玻片上，并盖上盖玻片；4）荧光显微镜下观察细菌活死情况。将 OP-BMSCs 以 $1\\times10^{4}/$ 每孔种植在 12 孔板中，OP-BMSCs 不接受任何处理（NC 组）、与微孔支架共培养（pTi 组）、与填充 CEC-PVA-AgNW 水凝胶的微孔支架共培养（$\\left(\\mathfrak{p}\\mathrm{Ti}\\ @\\mathrm{Gel}\\right.$ 组）和与填充负载雷帕霉素的 CEC-PVA-AgNW 水凝胶的微孔支架共培养（pTi-Rap $\\ @\\mathrm{Gel}$ 组）；将接受不同处理3 天后的细胞收集并提取蛋白，BCA 法测定总蛋白浓度，Western Blot 检测；使用 Image J 软件计算各条带灰度值，以 $\\upbeta$ -actin 为内参计算各组蛋白的表达量。The specific experimental protocol for the synthesis of hydrophilic polymers with functional groups is not provided in the text excerpt.在 $20~\\mathrm{ml}$ PBS 中加入 $0.2{\\mathrm{~g~BSA}}$ ，置于水平摇床室温摇 $20~\\mathrm{min}$ ，再加入 200ul 山羊血清封闭液并混匀， $4^{\\circ}\\mathrm{C}$ 保存。使用双侧卵巢切除术制备骨质疏松动物模型。植入 3 种不同的 3D 打印微孔假体：1) 3D 打印微孔支架（pTi 组）；2) 填充 CEC-PVA-AgNW 水凝胶的 3D 打印微孔支架（pTi@Gel 组）；3) 填充负载雷帕霉素的 CEC-PVA-AgNW 水凝胶的 3D 打印微孔支架（pTi-Rap@Gel 组）。所有动物在处死前第 14 天和第 4 天肌肉注射钙黄绿素（8 mg/kg）。术后第 12 周，过量麻醉法处死实验动物，收集左侧股骨样本，并将其固定在 4% 多聚甲醛中或储存在-80°C 冰箱中，用于进一步研究。收集股骨远端样本，制备未脱钙硬组织切片，马松染色观察再生骨组织与假体微孔界面整合情况，具体步骤如下：样本固定脱水及硬切片制备同章节 2.5.2.4；有机溶剂脱去有机树脂，无菌水冲洗，Weigert 氏苏木素染液染 $20\\mathrm{min}$ ，并流水冲洗 $10\\mathrm{min}$ ；使用Masson 代丽春红-复红染料染色 $10\\mathrm{min}$ ；滤纸吸干染液，将切片置于 $0.5\\%$ 冰醋酸分色处理 $1~\\mathrm{min}$ ，蒸馏水洗涤后用亮绿-冰醋酸染色 $5\\mathrm{min}$ ；放入二甲苯中两次，其浓度为 $10\\%$ ，透明后置于载玻片上用加拿大胶封固。"
+}
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@@ -0,0 +1,3 @@
+{
+    "protocol": "The raw materials used for the synthesis of hydrophilic polymers include octavinyl-POSS from Suzhou Sisu New Materials Co., Ltd., ethanedithiol from Shanghai Titan Technology Co., Ltd., 2-methyl-4-methylthio-2-morpholinobenzophenone (I907), polyethylene glycol mono-methacrylate (PEGMA, $M_{\\mathrm{n}}{\\sim}475$), polyethylene glycol diacrylate (PEGDMA, $M_{\\mathrm{n}}{\\sim}600$), pentaerythritol tetrathioglycolate (PTMP) from Shanghai Aladdin Biochemical Technology Co., Ltd., and pentaerythritol triacrylate (PETA) from Shanghai Miklin Biochemical Technology Co., Ltd. Anhydrous ethanol, tetrahydrofuran (THF), and anhydrous ether were obtained from Sinopharm Group Chemical Reagent Co., Ltd.1.2 PTMP、八乙烯基 POSS 的亲水改性称取 5 g (0.0079 mol) 纯化八乙烯基 POSS 溶于50 mL THF 中，制得A 液。另将 14.8734 g (0.158 mol) 乙二硫醇溶于 30 mL THF 中，并向其中加入 0.15 g I907，制得 B 液。在 600 W 汞灯的照射下，将 A 液以 100 mL/h 的流速滴加至 B 液中，滴加完毕后，再继续反应 30 min。将反应后的溶液倒入离心管中，并向其中加入一定量的无水乙醇作为沉淀剂使产物析出，在 8000 r/min 的离心转速下，离心 10 min。倒去上层清液，再用无水乙醇反复洗涤粗产物 8~10 次，除去未反应的乙二硫醇以及少量 I907，得到白色黏稠状粗产物。接着在索氏提取器中用无水乙醇回流处理3 天，进一步除去未反应的乙二硫醇和 I907。最后在70 °C 真空烘箱中放置 24 h，除去产物中的无水乙醇。最终得到无色透明黏稠状液体。称取 4.1185g (~0.00867 mol) PEGMA 溶于 20 mL THF 中，制得 A 液。另将 6 g (0.00434 mol) POSS-·sH8 溶于 15 mL THF 中，并向其中加入 0.06g I907，制得 B 液。将 A 液以 10 mL/h 的流速滴加至 B 液中，滴加完毕后，再继续反应 30 min。用聚四氟乙烯注射器滤膜滤去反应后溶液中的不溶物，再在 35°C 的温度下，旋蒸除去部分溶剂，然后将剩余溶液转移至离心管中，并向其中加入一定量的无水乙醚作为沉淀剂使产物析出，在 8000 r/min 的离心转速下，离心 10 min。白色蜡状物质（聚乙二醇单丙烯酸酯聚合物）沉淀在最底层，中间层为产物层，上层为乙醚/THF 混合溶剂层。将产物提取出，用无水乙醚反复洗涤 5~8 次，除去 I907。最后在 30 °C 真空烘箱中放置 24h，除去乙醚。最终得到无色透明黏稠状液体。称取 2.196~g (0.0046~mol) PEGMA 溶于 20~mL THF 中，制得 A 液。另将 2~g (0.0046~mol) PTMP 溶于 3~mL THF 中，并向其中加入 0.02~g I907，制得 B 液。将 A 液以 10~mL/h 的流速滴加至 B 液中，滴加完毕后，再继续反应 30~min。然后按照合成 POSS- SH6 -PEGMA2 的后处理过程进行后处理，最终得到无色透明液体。Prepare hydrophilic anti-fog resin according to the composition ratios listed in Table 1. Add a total mass of 1% I907 to each group of resin and mix thoroughly. Use a blade coater to apply the mixture onto the surface of a polycarbonate (PC) plate with a coating thickness of 10 µm. Cure the coating under a 3000 W mercury lamp for 30 seconds to obtain a series of hydrophilic coatings.涂层耐水性表征：将 PC 基材裁剪为 5 cm x 5 cm 大小，并对其称量，记作 m0。刮涂涂层并 UV 固化后，称取涂层与基材的总质量，记作 m1。将涂层在水中浸泡 24 h 后，擦干涂层表面，称取总质量，记作 m2。涂层的吸水率计算公式如下：m = (m2 - m1) / (m1 - m0) x 100%。涂层防雾性能测试：将 PC 基材裁剪为 6 cm x 5 cm 大小，刮涂涂层并 UV 固化。向 200 mL 烧杯中加入 90 °C 以上的热水 100 mL，将涂层面向下盖在烧杯上，15 s 后观察涂层起雾情况。"
+}
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diff --git a/task2/task2-paper-info/╛█║╧╬я╡─░┤╨ш─ц╧Є╔ш╝╞╙ыPolyTAO║╧╫ў.json b/task2/task2-paper-info/╛█║╧╬я╡─░┤╨ш─ц╧Є╔ш╝╞╙ыPolyTAO║╧╫ў.json
new file mode 100644
index 0000000..a7f1e75
--- /dev/null
+++ b/task2/task2-paper-info/╛█║╧╬я╡─░┤╨ш─ц╧Є╔ш╝╞╙ыPolyTAO║╧╫ў.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The polymer synthesis is conducted using a generative pre-trained large language model (PolyTAO) based on a curated polymer structure-property dataset containing nearly 1,000,000 entries. The model operates through supervised learning to generate polymers with user-defined properties, including fine-tuning on three publicly available small polymer datasets. The approach includes evaluations of polymer generation under both semi-template and template-free generation paradigms, demonstrating capabilities for on-demand polymer generation."
+}
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diff --git a/task2/task2-paper-info/╛█║╧╬я╦о─¤╜║╡─╕▀╢╚╚▄╒═.json b/task2/task2-paper-info/╛█║╧╬я╦о─¤╜║╡─╕▀╢╚╚▄╒═.json
new file mode 100644
index 0000000..05fe819
--- /dev/null
+++ b/task2/task2-paper-info/╛█║╧╬я╦о─¤╜║╡─╕▀╢╚╚▄╒═.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of hydrophilic polymers with functional groups involves the consideration of a new reference state for the gel, assuming it is in a state of free expansion and in equilibrium with a solvent of chemical potential μ_ref. The deformation gradient F can be multiplied to decompose it into F' and F0, where the value of λ0 is calculated by solving a boundary value problem simplified to an algebraic equation: G(1/λ0 - 1/λ0^3) + K_mix[log(1 - 1/λ0^3) + 1/λ0^3 + χ/λ0^6] - μ_ref = 0. After determining λ0, the free energy density and mobility tensor in the new reference configuration can be obtained through Piola transformation. Two expressions for the elastic free energy and mixing free energy are derived, along with the expression for the mobility tensor relative to the expansion reference configuration.在模型开发器窗口的组件 1 (comp1) 节点下，单击达西定律 (dl)。选择\"域\" 2。在达西定律的设置窗口中，单击以展开因变量栏。在压力 (Pa) 文本框中键入 \"mu\"。在模型开发器窗口的组件 1 (comp1) | 达西定律 Π(dI)> 多孔介质 1 节点下，单击流体 1。在流体的设置窗口中，定位到流体属性栏。从流体类型列表中选择不可压缩。从 ρ_ref 列表中选择用户定义。在关联文本框中键入 \"rhof\"。从 μ 列表中选择用户定义。在关联文本框中键入 \"muf\"。在模型开发器窗口中，单击多孔基体 1。在多孔基体的设置窗口中，定位到基体属性栏。从 ε_p 列表中选择用户定义。在关联文本框中键入 \"poro0\"。从 κ 列表中选择用户定义。从列表中选择对称。在 κ 表中，输入以下设置：KRR KRZ；KRZ KZZ。在模型开发器窗口的组件 1 (comp1) | 达西定律 (dl) 节点下，单击初始值 1。在初始值的设置窗口中，定位到初始值栏。在 mu 文本框中键入 \"mu_ref\"。在模型开发器窗口中，单击连续性 1。在连续性的设置窗口中，定位到高级栏。选中断开连接对复选框。The text excerpt does not contain any specific experimental protocol for the synthesis of hydrophilic polymers with functional groups."
+}
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diff --git a/task2/task2-paper-info/╝╫╗∙▒√╧йїг╢р░═░╖.json b/task2/task2-paper-info/╝╫╗∙▒√╧йїг╢р░═░╖.json
new file mode 100644
index 0000000..63f4b75
--- /dev/null
+++ b/task2/task2-paper-info/╝╫╗∙▒√╧йїг╢р░═░╖.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "In a three-neck round-bottom flask, add 6.0 g of Na2B4O7·10H2O and 3.0 g of Na2CO3 to 250.0 mL of deionized water. Stir and degas the solution with high purity argon (99.999%) for 2 hours. Under an argon atmosphere, add 1.5 g of dopamine hydrochloride to the solution and stir for an additional 30 minutes. Drop-wise add 3.0 mL of acryloyl chloride to the flask at 0 °C, then add 4.5 g of Na2CO3 to maintain the pH above 9 during the reaction. Stir the mixture for 12 hours at room temperature. Adjust the pH to 1-2 using a 6 mol/L HCl solution. Extract the solution with ethyl acetate, wash the organic layer with a 0.1 mol/L diluted HCl solution, and dry over MgSO4. Remove the solvent in vacuum to obtain the crude product, which is then purified by flash silica gel column chromatography using ethyl acetate and petroleum ether, yielding a white solid with an 80% yield."
+}
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diff --git a/task2/task2-paper-info/╡ч│┴╗¤Janus▓─┴╧.json b/task2/task2-paper-info/╡ч│┴╗¤Janus▓─┴╧.json
new file mode 100644
index 0000000..d61ad89
--- /dev/null
+++ b/task2/task2-paper-info/╡ч│┴╗¤Janus▓─┴╧.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "1. Prepare a chitosan solution for electrodeposition. 2. Set the temperature to a range of 0-5 °C to influence the deposition process. 3. Perform the first step of electrodeposition without salt to create the dense face of the Janus film. 4. Proceed with the second step of electrodeposition in the presence of salt to generate the porous face. 5. Control deposition conditions such as time and current density to adjust structural parameters (pore size, porosity, layer thicknesses) of the deposited hydrogel.Chitosan (7% w/v) was dissolved in 2M hydrochloric acid (pH range from 4.5–5.0), followed by the addition of 0.1 M H2O2. The temperatures of electrolytes were controlled at 27 and 5°C during the film’s electro-fabrication. Electro-fabrication was performed with a constant current density (0.83 to 20.01 mA cm^-2) and potential ranging from 3 to 8 V for designated times (from 100 to 1000 s). After electro-deposition, the chitosan-coated electrode was washed with ultra-pure water three times, and the deposited chitosan was peeled from the cathode to obtain a free-standing film."
+}
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diff --git a/task2/task2-paper-info/╡═─ж▓┴╧╡╩¤╦о─¤╜║═┐▓у JACS.json b/task2/task2-paper-info/╡═─ж▓┴╧╡╩¤╦о─¤╜║═┐▓у JACS.json
new file mode 100644
index 0000000..8aa2dd5
--- /dev/null
+++ b/task2/task2-paper-info/╡═─ж▓┴╧╡╩¤╦о─¤╜║═┐▓у JACS.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "The PAMPS gel was synthesized by radical polymerization. An aqueous solution of 1.0 M 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), 5.0 mol% cross-linking agent, N,N'-methylenebisacrylamide (MBAA), and 0.1 mol% initiator, 2-oxoglutaric acid, was prepared in the reaction cell, purged with nitrogen gas for 30-45 min, and irradiated with UV light for 5 h at 20 °C. The reaction was conducted between a pair of polystyrene substrates or glass substrates, separated by a 2 mm thick spacer. After polymerization, the gel was immersed in a large amount of water for 1 week to equilibrate and wash away residual chemicals. The swollen PAMPS gels were cut into square shapes of 1.0 x 1.0 cm² for friction measurement using a rheometer with a coaxial two parallel planar geometry. The average frictional force was calculated from the torque detected as the lower platen rotated in water at 25 °C."
+}
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diff --git a/task2/task2-paper-info/╢р╣ж─▄─¤╜║╨▐╩╬╠╝╧╦╬м╘Ў╟┐╛█...╚ы╬я╡─╓╞▒╕╝░╣╟╒√║╧╨╘─▄╤╨╛┐_╢н╬─╙в.json b/task2/task2-paper-info/╢р╣ж─▄─¤╜║╨▐╩╬╠╝╧╦╬м╘Ў╟┐╛█...╚ы╬я╡─╓╞▒╕╝░╣╟╒√║╧╨╘─▄╤╨╛┐_╢н╬─╙в.json
new file mode 100644
index 0000000..d170a88
--- /dev/null
+++ b/task2/task2-paper-info/╢р╣ж─▄─¤╜║╨▐╩╬╠╝╧╦╬м╘Ў╟┐╛█...╚ы╬я╡─╓╞▒╕╝░╣╟╒√║╧╨╘─▄╤╨╛┐_╢н╬─╙в.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "采用磺化处理和紫外接枝的表面改性方法将负载地塞米松（Dex）的甲基丙烯酰化明胶/聚丙烯酰胺（GelMA/PAAM）修饰到CFRPEEK植入物的表面上。采用原位键合法制备GO-HAP纳米复合材料，然后采用磺化处理和基于自由基光聚合的冷冻凝胶方法将负载GO-HAP的冷冻凝胶接枝到CFRPEEK植入物表面上。通过磺化处理和紫外接枝的方法将负载HAP@Mg-GA MOF纳米颗粒的甲基丙烯酰化壳聚糖（CSMA）凝胶接枝到CFRPEEK植入物表面。Methacryloyl gelatin/polyacrylamide (GelMA/PAAM) loaded with dexamethasone (Dex) was modified onto the surface of the CFRPEEK implant by sulfonation treatment and ultraviolet grafting. For the GO-HAP cryogel, the GO-HAP nanocomposites were prepared using in situ bonding method, and then the cryogel loaded with GO-HAP was grafted onto the surface of the CFRPEEK implant by sulfonation and the cryogelation technique based on free radical photopolymerization. For the pH-responsive metal-organic framework (MOF) hydrogel, hydroxyapatite @$ magnesium-gallic acid (HAP@Mg-GA) nanoparticles were prepared, and then methacryloyl chitosan (CSMA) hydrogel loaded with HAP@$Mg-GA was grafted onto the surface of the CFRPEEK implant by sulfonation and ultraviolet grafting.合成聚合物可以通过适当设计聚合物官能团，以呈现定制的结构来满足生物材料所需的功能。采用磺化处理和紫外接枝的表面改性方法将负载地塞米松（Dex）的甲基丙烯酰化明胶/聚丙烯酰胺复合水凝胶（GelMA/PAAM）修饰到CFRPEEK植入物上，首先通过原位键合的方法制备氧化石墨烯-羟基磷灰石（GO-HAP）纳米复合材料，再采用磺化处理和基于自由基光聚合的冷冻凝胶方法将负载氧化石墨烯-羟基磷灰石的冷冻凝胶接枝到CFRPEEK植入物表面上，最后通过磺化处理和紫外接枝的方法对CFRPEEK植入物进行表面改性，构建出负载HAP@Mg-GA MOF纳米颗粒的水凝胶层，水凝胶基质使用具有pH响应性的甲基丙烯酰化壳聚糖。The text excerpt does not provide specific details or an experimental protocol for the synthesis of hydrophilic polymers with functional groups.通过浓硫酸的磺化处理和紫外（UV）照射将GelMA/PAAM复合水凝胶接枝在CFRPEEK植入物的多孔表面上，随后通过浸泡Dex溶液将Dex负载在CFRPEEK表面的GelMA/PAAM复合水凝胶上。(1) Mix long PEEK fibers (70 wt%, 40 mm length) and carbon fibers (30 wt%, 40 mm length) to prepare a 3D CFRPEEK composite needle-punched felt through carding, laying, and needle punching; (2) Trim the needle-punched felt to the size of a specific mold, and place it in a vacuum hot press for molding. Set the hot pressing parameters as follows: molding temperature at 400°C, molding time for 20 min, cooling rate at 20°C/min, and molding pressure at 4 MPa; (3) Obtain black plate-like CFRPEEK composite by demolding; (4) To remove surface contaminants from CFRPEEK composites, clean the samples using an ultrasonic cleaner with acetone, ethanol, and ultra-pure water sequentially, each for 10 min; (5) Stir the CFRPEEK samples in concentrated sulfuric acid at room temperature for 5 min to achieve a uniform porous surface; (6) Immerse the reacted CFRPEEK samples in ultra-pure water and acetone, and clean them in an ultrasonic cleaner; (7) Dry the obtained sulfonated CFRPEEK composite at 60°C in a vacuum drying oven for 24 hours for subsequent use; (8) Use sulfonated CFRPEEK samples with dimensions of Φ14x1.5 mm for surface characterization and in vitro cell experiments, and samples with dimensions of Φ5x1.5 mm for in vivo animal experiments.在 60°C ，5 克明胶于50 毫升磷酸盐缓冲溶液（PBS，CELLCOOK，中国）中溶解；向明胶溶液中缓慢滴入 4 毫升甲基丙烯酸酐， 50°C 磁力搅拌 3 小时进行酰化反应；在 50°C 下，将反应完的溶液用 200 毫升的PBS 稀释，装入透析袋中用去离子水透析3 天，以除去未反应的甲基丙烯酸酐；将透析后的反应液在真空冷冻干燥机中冻干，获得白色泡沫状的甲基丙烯酰化明胶（GelMA）。在常温条件下，将少量的明胶和甲基丙烯酸酰化明胶分别溶解于氘代重水（D2O），通过 400MHz 核磁共振波谱仪来测试样品的 1H NMR 光谱，以确定所制备的甲基丙烯酸酰化明胶（GelMA）的分子结构。在避光条件下，将 GelMA 和 AM 按照 $10{:}5\\mathrm{\\wt\\%}$ 的比例溶解到去离子水中，得到无色透明的 GelMA/AM 凝胶前体液；将按照 2.2.2 制备的磺化 CFRPEEK 浸入到 GelMA/AM 凝胶前体液中；将含有磺化 CFRPEEK 的混合溶液置于波长为$365~\\mathrm{nm}$ 、光强度为 $10\\mathrm{\\mW/cm}^{2}$ 的紫外灯下 45 分钟；为了去除未反应的 GelMA和AM，将接枝后的样品浸入到去离子水中；将紫外接枝后的样品在浓度为 250$\\upmu\\mathrm{g/mL}$ 的Dex 溶液中孵育24 小时；最后，在真空冷冻干燥机中冻干孵育后的样品。将复合水凝胶修饰CFRPEEK置于4mL浓度为250~μg/mL的Dex溶液中，放在25°C的恒温摇床上以50rpm的速度匀速振荡，孵育24h后取出载药的复合水凝胶修饰CFRPEEK，使用紫外-可见分光光度计测量剩余Dex溶液在240nm处的吸光度。计算Dex负载率（%）= (M0-MT)/M0×100%，其中MT为剩余Dex溶液的药物质量，M0为总的药物质量。对于体外Dex释放实验，将SCP/GP/Dex样品浸入2 mL PBS的离心管中，在37°C的恒温摇床以100rpm的速度振荡，预定时间收集含有释放Dex的PBS，并加入等体积的新鲜PBS，通过紫外-可见分光光度计测量释放的Dex浓度，计算Dex的释放效率（%）= Rt/R0×100%，其中Rt为释放的Dex的质量，R0为复合水凝胶修饰CFRPEEK负载的Dex的总质量。将 CP、SCP、SCP/GP 和 SCP/GP/Dex 浸入到 $2\\\\mathrm{mL}$ 的 SBF 溶液中，置于 $37^{\\\\circ}\\\\mathrm{C}$ 恒温摇床中，以 $100\\\\mathrm{rpm}$ 的速度匀速振荡；每两天更换等量新鲜的 SBF 溶液，在14 天后，将试样取出，在真空冷冻干燥机中冷冻干燥；利用 SEM 及能量色散光谱仪（EDS）测量试样的微观形貌和化学构成。将明胶与甲基丙烯酸进行共聚合，生成甲基丙烯酰化明胶（GelMA）。在紫外线照射下，二苯甲酮单元产生自由基，后续聚合反应使得GelMA与CFRPEEK表面处形成C-C共价键。此外，GelMA/PAAM复合水凝胶层的制备亦通过自由基聚合实现，并且用于载药地塞米松（Dex）。首先利用原位键合法制备了 GO-HAP 纳米复合材料，然后通过基于自由基光聚合的冷冻凝胶技术在惰性磺化 CFRPEEK 植入物表面上制备了多功能 3D 海绵状大孔 GelMA/PEGDA/GO-HAP 冷冻凝胶层。1. Dissolve 185 mg of anhydrous calcium chloride (CaCl2) in 15 mL of deionized water. 2. Prepare a 13.2 mL suspension of 3.8 mg/mL GO and sonicate for 30 minutes. 3. Slowly add the GO suspension to the CaCl2 solution while stirring magnetically for 30 minutes. 4. Prepare 1.7 mL of 0.6 M sodium phosphate (Na2HPO4) solution and slowly add it to the mixture. 5. Adjust the pH to between 9 and 11 using 1 M NaOH solution and stir in a 45°C water bath for 12 hours. 6. Wash the GO-HAP precipitate with deionized water, centrifuge at 8000 rpm for 3 times, and dry in a vacuum oven at 60°C for 24 hours.（1）（2）（3）（4）与第二章 2.2.2 的实验步骤相同；（5）在室温下，CFRPEEK 复合材料在浓硫酸中磁力搅拌 $3\\mathrm{min}$ ，以获得均匀的多孔表面；（6）反应后的 CFRPEEK 复合材料依次浸入超纯水和丙酮中，并在超声波清洗器中清洗；（7）将得到的磺化CFRPEEK 复合材料在真空干燥箱中 $60^{\\circ}\\mathrm{C}$ 干燥24 小时，以备后续使用；（8）尺寸为 $\\Phi8{\\times}1.5~\\mathrm{mm}$ 的磺化 CFRPEEK 用于表面表征和体外细胞实验，尺寸为 $\\Phi5{\\times}1.5\\ \\mathrm{mm}$ 的磺化 CFRPEEK 用于动物体内实验。在避光条件下，按 $10{:}5\\mathrm{wt\\%}$ 配制 GelMA/PEGDA 溶液；将 $0.5\\mathrm{mg/mL}$ GO-HAP悬液超声分散1 小时，然后以 $25,50,100(\\upmu\\mathrm{g/mL})$ 的浓度添加到 GelMA/PEGDA溶液中；将混合溶液 $37^{\\circ}\\mathrm{C}$ 磁力搅拌 8 小时，得到不同浓度的 GelMA/PEGDA/GO-HAP 凝胶前体液。在避光条件下，将磺化 CFRPEEK 按 $60~{\\upmu\\mathrm{L}}/{\\upmathrm{c m}}^{2}$ 的比例浸没到 GelMA/PEGDA/GO-HAP 凝胶前体液中；静置 10-15 分钟，让凝胶前体液均匀覆盖在磺化CFRPEEK 表面；浸泡在前体液中的磺化CFRPEEK 先 $4^{\\circ}\\mathrm{C}$ 冷藏1 小时，再 -20^{\\circ}\\mathrm{C}$ 冷冻 12 小时；冷冻后，将磺化 CFRPEEK 置于波长 $365~\\mathrm{nm}$ 、光强 10$\\mathrm{mW}/\\mathrm{cm}^{2}$ 的紫外灯下 15 分钟；光照后，将改性的磺化 CFRPEEK 浸入蒸馏水中，以去除未反应的前体液，得到 GelMA/PEGDA/GO-HAP 冷冻凝胶修饰 CFRPEEK。将锭子用环氧胶垂直粘在尺寸为 50mm×50mm×1.5mm 的 GP_{10-5} 样品上，静置24小时等待环氧胶完全干透；沿着锭子的边缘用切割器切划冷冻凝胶层，清除切划过程中产生的碎屑；将附着力测试仪的套筒套在锭子上，然后打开仪器进行测试；测试完成后，观察锭子和被测表面的状况并记录附着力。将 GH_{25}，GH_{50} 和 GH_{100} 分别浸泡在 2 mL PBS 中，并在 37^{\\circ}C 恒温摇床上以100 rpm 匀速振荡；在规定的时间点，收集含有释放 Ca^{2+} 的PBS 并加入等体积的新鲜 PBS；通过 ICP-OES 检测 Ca^{2+} 的浓度。SCP, GP10-5, GH25, GH50, and GH100 in vitro mineralization research experimental steps are the same as in Chapter 2, refer to section 2.2.7 in vitro mineralization behavior study.1. Sterilize different samples using Cobalt 60 irradiation (15KGy, 20 hours) and place them in a 24-well plate, wash each well with PBS, and add 1 mL of DMEM medium containing 1% FBS to each well; collect the medium after 24 hours. 2. Prepare a cell suspension of logarithmic phase HUVEC cells using the collected medium at a density of 1×10^5 cell/ml. 3. Apply Matrigel evenly in the 24-well plate and incubate at 37°C to allow it to solidify. 4. After 1 hour, inoculate 1 mL of the HUVEC cell suspension onto the surface of the Matrigel. 5. Incubate in a 37°C incubator for 6 hours and observe the formation of vascular-like networks using a microscope.采用原位键合法制备 GO-HAP 纳米复合材料，促进磺化 CFRPEEK 表面的成骨和血管生成能力。通过紫外辐照的方法在磺化 CRPEEK 表面上制备羟基磷灰石 @$\\mathrm{Mg-GA}$ /甲基丙烯酰化壳聚糖（HAP@Mg-GA/CSMA）MOF 水凝胶层。CSMA 是可以通过光引发聚合且对pH 高度敏感，能够将核壳结构的 MOF 纳米颗粒负载到磺化CFRPEEK 的表面，并在低 pH 条件下控制 $\\mathrm{HAP}@\\mathrm{Mg-GA~MOF}$ 纳米颗粒中生物活性物质的持续释放。将1g 的纳米羟基磷灰石超声分散到 100mL 的去离子水中，随后用 10M 的KOH 水溶液调节 pH 在 8-9 之间；将 0.19g 没食子酸和 0.05g 氯化镁分别加入到纳米羟基磷灰石分散液中，将此混合液放入三颈烧瓶中，于 120^{\\circ}C 回流搅拌，反应 24h ，冷却至室温，然后进行高速离心处理，取 HAP@Mg-GA 沉淀物；沉淀物用蒸馏水和无水乙醇分别洗涤三次，并以 10000rpm 高速离心回收；将回收的沉淀物在 60^{\\circ}C 的真空烘箱中干燥 24h ，得到棕褐色的核壳结构的羟基磷灰石 @ 镁-没食子酸MOF 纳米颗粒（ HAP@Mg-GA）。配制 200mL 1.5% 壳聚糖溶液，溶剂为 4% (v/v) 醋酸溶液，40℃ 磁力搅拌直至壳聚糖溶解；向上述溶液中缓慢滴加 16 mL 的甲基丙烯酸酐，40℃ 避光磁力搅拌反应 3 小时；反应完成后，将反应液置于透析袋中，用蒸馏水透析 7 天，除去未反应的甲基丙烯酸酐；将透析液在真空冷冻干燥机中干燥，得到甲基丙烯酰化壳聚糖（CSMA）。在常温条件下，将少量的壳聚糖和甲基丙烯酰化壳聚糖（CSMA）分别溶解于含 2% 酰代乙酸的氘代水 (ΔD2O) 中，通过 400MHz 核磁共振波谱仪测定它们的 1H NMR 谱，以判断甲基丙烯酰化壳聚糖（CSMA）的分子结构。磺化 CFRPEEK 复合材料的制备步骤与第三章相同，详见 3.2.3 磺化CFRPEEK 复合材料的制备，其中尺寸为 Φ 8×1.5 mm 的磺化 CFRPEEK 用于表面表征、体外细胞实验和大鼠的皮下植入实验，尺寸为 Φ 5×6 mm 的磺化 CFRPEEK 用于兔的胫骨缺损实验。(1) Preparation of CSMA/HAP@Mg-GA gel precursor solution: In a dark environment, add HAP@Mg-GA at a concentration of 0.5 wt% to a prepared 3 wt% CSMA aqueous solution. To achieve a uniform mix, ultrasonically disperse the mixture for 30 minutes, followed by magnetic stirring at room temperature for 8 hours to obtain the CSMA/HAP@Mg-GA gel precursor solution. (2) Preparation of MOF hydrogel modified CFRPEEK: In a dark environment, immerse the sulfonated CFRPEEK composite material in a ratio of 100 μL/cm² into the HAP@Mg-GA/CSMA gel precursor solution (HAP@Mg-GA:0.5 wt%, CSMA:3 wt%) and let it sit at room temperature for 15-30 minutes for sufficient contact. Under inert atmosphere, irradiate the CFRPEEK immersed in the solution with a UV lamp at a wavelength of 365 nm and an intensity of 10 mW/cm² for 60 minutes. After completion, soak the CFRPEEK in distilled water to remove unreacted gel precursor solution, and finally dry it using a freeze dryer for later use.将不同的CFRPEEK样品裁切成 $35\\times15\\times1.5~\\mathrm{mm}^{3}$ 大小，以 $0.001\\mathrm{~M~}$ 氯化钾（KCl）溶液作为流动电解液，电解液的 $\\mathsf{p H}$ 使用 $0.1\\mathrm{~M~HCl}$ 和 $0.1\\mathrm{~M~NaOH}$ 溶液进行调整，范围为5.0-8.0，探究样品表面的 zeta 电位和pH 的关系曲线。将HAP 和 MGH 两组样品分别浸没到 $2\\mathrm{mL}$ 的 $\\mathrm{pH}{=}5.5$ 、6.5 和 7.4 的 PBS 溶液中，置于恒温 $37^{\\circ}\\mathrm{C}$ 、转速为 $100\\mathrm{rpm}$ 的摇床；在 1、3、5、7、14、21 天吸出缓释液并重新加入 $2{\\mathrm{~mL~}}$ 的新鲜的 PBS 溶液；用电感耦合等离子体光谱仪测定 $\\mathrm{Ca}^{2+}$ 和 $\\mathrm{Mg^{2+}}$ 的缓释效率，用紫外分光光度计测定 GA 的缓释效率。"
+}
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diff --git a/task2/task2-paper-info/╢р░═░╖═┐▓у.json b/task2/task2-paper-info/╢р░═░╖═┐▓у.json
new file mode 100644
index 0000000..7cbae5f
--- /dev/null
+++ b/task2/task2-paper-info/╢р░═░╖═┐▓у.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "To synthesize hydrophilic polymers with functional groups, prepare tannic acid by utilizing its hydroxyl groups. For functionalization, create complexes with proteins or zwitterionic polymers like poly(sulfobetaine methacrylate) (PSBMA). For surface modifications, apply tannic acid onto substrates such as metal oxides or hydrophobic polymers to achieve a thickness of approximately 20 nm. Generate metal−phenolic networks (MPNs) by coordinating metal ions with tannic acid, resulting in thin adherent films suitable for various substrates. For functionalizing surfaces, use techniques such as vacuum filtration to create superoleophobicity. Explore complexes by lyophilizing catechin with poly(ethylene glycol) (PEG) to enhance water solubility for therapeutic uses. Consider using laccase for oxidative cross-linking in urushiol-based coatings to develop protective layers on surfaces."
+}
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diff --git a/task2/task2-paper-info/╣ж─▄╗п╦о─¤╜║═┐▓у ╫█╩Ў.json b/task2/task2-paper-info/╣ж─▄╗п╦о─¤╜║═┐▓у ╫█╩Ў.json
new file mode 100644
index 0000000..c039cd5
--- /dev/null
+++ b/task2/task2-paper-info/╣ж─▄╗п╦о─¤╜║═┐▓у ╫█╩Ў.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "Free-radical polymerization of hydrogel precursors, which consist of monomers, crosslinkers, and initiators, is used for hydrogel preparation. After curing, incubate the hydrogel in excess deionized (DI) water for several hours to days, regularly replenishing the DI water, to remove unreacted monomers and initiators.To synthesize hydrophilic polymers with functional groups, cyanoacrylate monomers are used. These monomers diffuse into the hydrogel polymer network and polymerize through anionic polymerization, forming polycyanoacrylate chains within the network. This process involves topological entanglement with the existing hydrogel polymer matrix. It is essential to ensure that the thickness of the hydrogel coating is significantly greater than the diffusion depth of cyanoacrylates, which has been observed to reach approximately 10 micrometers, to maintain the integrity of the hydrogel during the bonding process."
+}
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diff --git a/task2/task2-paper-info/╣т╕и╓·3D┤Є╙б╦о─¤╜║╙├╙┌┐╣╛·╙ж╙├.json b/task2/task2-paper-info/╣т╕и╓·3D┤Є╙б╦о─¤╜║╙├╙┌┐╣╛·╙ж╙├.json
new file mode 100644
index 0000000..9eaf56d
--- /dev/null
+++ b/task2/task2-paper-info/╣т╕и╓·3D┤Є╙б╦о─¤╜║╙├╙┌┐╣╛·╙ж╙├.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Light-assisted 3D printing technology is used to solidify a photopolymerizable prepolymer solution. The process involves integrating inorganic nanomaterials, antibiotics, and functional polymers into 3D-printed hydrogels to enhance antibacterial effects. Attention must be given to the customization of structures and the specific functionalities required for applications in tissue engineering, regenerative medicine, wound healing, and implants.Mugnaini et al. synthesized photocrosslinkable methacrylic pullulan, utilizing it as a bioink. The aqueous dispersions of methacrylated pullulan served as the substrate for inkjet printing.Ouyang et al. developed a generalizable in situ-crosslinking strategy in which the light was introduced immediately before the deposition to achieve high encapsulated cell viability (approximately 95%).The synthesis of hydrophilic polymers involves the crosslinking of one or more monomers, where the number of monomers and functional groups attached to the polymer backbone determines the degree of crosslinking. The functional groups can be introduced through natural polymers such as collagen, gelatine, hyaluronic acid, or alginate, or synthetic polymers like poly(ethylene glycol) and poly(acrylamide).The article does not provide a specific experimental protocol for the synthesis of hydrophilic polymers with functional groups."
+}
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diff --git a/task2/task2-paper-info/╣т╜╗┴к╗·└э╖╓╬Ў-AFM.json b/task2/task2-paper-info/╣т╜╗┴к╗·└э╖╓╬Ў-AFM.json
new file mode 100644
index 0000000..0a45fd2
--- /dev/null
+++ b/task2/task2-paper-info/╣т╜╗┴к╗·└э╖╓╬Ў-AFM.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The article does not provide a specific experimental protocol for the synthesis of hydrophilic polymers with functional groups.Photocurable hydrogels are synthesized by chemically reacting biomaterials with methacrylic anhydride or acryloyl chloride to introduce functional groups such as MA or DA. The process involves using a photoactivatable radical initiator like lithium pheny (2,4,6-trimethylbenzoyl) phosphinate (LAP) under light exposure of a certain wavelength. The unsaturated double bonds of these photosensitive groups polymerize with each other to form a crosslinking network.To synthesize hydrophilic polymers with functional groups, the following steps should be followed: 1. Prepare GelMA by hydrating gelatin and functionalizing it with methacrylic anhydride (MA). 2. Calculate the mass of GelMA after curing (x) and the double bond conversion (DBC). 3. Determine the degree of functionalization (DoF) using the ratio of amino acids containing amino groups in gelatin and the substitution rate of MA group. 4. Calculate the average molecular weight (M_ave) of the basic unit in GelMA using the proportions and molecular weights of amino acids. 5. Measure the concentration of P element using inductively coupled plasma mass spectrometry (ICP-MS) to find the number of initiator residues (N_ini-res). 6. Finally, calculate the Average Crosslinking Steps (ACS) using the formula: ACS = 2 * (N_DB / N_ini-res) - 1, where N_DB is derived from the values provided. Ensure thorough mixing and proper handling of all reactants and reagents throughout the process.The synthesis of hydrophilic polymers with functional groups involves crosslinking a liquid substance, which can be achieved by using reagents such as GelMA. To analyze the degree of crosslinking, the double bond content (DBC) is calculated using NMR spectrometry before and after crosslinking. Degradation of the crosslinked hydrogel can be performed with collagenase to obtain a liquid for measurement. The integral areas of characteristic peaks of carbon–carbon double bond in NMR spectra before and after crosslinking are used to evaluate the DBC, which is then used to calculate the degree of crosslinking (DGC) using the formulas provided: DBC = (1 - (A(after) / A(before))) x 100% and DGC = DBC x EDBC x 100%.The synthesis of hydrophilic polymers with functional groups involves the utilization of GelMA as an example. The main chain of GelMA is a peptide chain wherein crosslinking occurs through the interconnection of MA groups on the side chains. The degree of crosslinking (DSC) can be calculated using the formula: DSC = (N_(crosslinked bond) / (N_(peptide bond) + N_(crosslinked bond))) × 100%. The calculation of N_(peptide bond)* is given by N_(peptide bond)* = (ACS + 1) * (1 / DoF), and N_(crosslinked bond)* is calculated as N_(crosslinked bond)* = ACS. The final DSC formula is DSC = (DoF * ACS) / ((DoF + 1) * ACS + 1) × 100%."
+}
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diff --git a/task2/task2-paper-info/╣т╜╗┴к╦о─¤╜║╫█╩Ў.json b/task2/task2-paper-info/╣т╜╗┴к╦о─¤╜║╫█╩Ў.json
new file mode 100644
index 0000000..6146c35
--- /dev/null
+++ b/task2/task2-paper-info/╣т╜╗┴к╦о─¤╜║╫█╩Ў.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis method for hydrophilic polymers with functional groups, such as poly(ethylene glycol) diacrylate (PEGDA), gelatin methacryloyl (GelMA), and methacrylated hyaluronic acid (MeHA), involves photo-crosslinking techniques. These materials are subjected to light stimuli, including ultraviolet (UV) light and visible light, to induce crosslinking under mild conditions. This approach allows for tunable mechanical properties, biocompatibility, and biodegradability, making them suitable for applications in tissue engineering, drug delivery, and cancer therapy.Photo-crosslinkable hydrogels are synthesized by incorporating a photoreactive moiety, typically a photochromic chromophore, into a polymeric network. The synthesis process involves capturing an optical signal through the photochromic chromophore, which subsequently converts this signal into a chemical signal via photoreactions such as isomerization, cleavage, or dimerization. This chemical signal is then transferred to the functional groups of the hydrogel, modifying its properties such as elasticity, degree of swelling, and degradation. These modifications derive from the hydrogel's molecular structures and the setup used for photo-irradiation.To synthesize PEGDA, begin with PEG (molecular weight above 400 Da) and substitute the terminal hydroxyl groups with acrylates to create a PEG derivative with double-bond acrylate groups at each end. This enables the polymer to undergo free radical initiated chain photopolymerization in the presence of a photoinitiator, such as Irgacure 2959. The photopolymerization process is carried out under a UV or visible light source to form a 3D polymer network. Adjust the concentration or molecular weight of PEGDA to tune the mechanical properties of the hydrogel.To synthesize PEGDA, PEG diol is first dissolved in benzene, followed by the removal of water through azeotropic distillation in toluene using a Dean-Stark trap. The PEG acrylation is then carried out under argon by dissolving PEG in dichloromethane solution with acryloyl chloride and triethylamine at a molar ratio of 1:1.5:1.5 of OH-groups of PEG: acryloyl chloride: triethylamine, respectively. The mixture is stirred in the dark at room temperature overnight. The product is then precipitated by the addition of diethyl ether and chilled to 4°C to eliminate toluene and subsequently recovered using filtration. Finally, the recovered PEGDA product is dried in a vacuum oven overnight.To synthesize GelMA hydrogel, gelatin is first obtained, as it is a biodegradable and biocompatible material. The gelatin is then functionalized with methacrylic anhydride (MA) through a methacrylation process. This process enhances the degradation rate control and improves the mechanical strength of the gelatin. The resultant GelMA hydrogel is suitable for various biomedical applications.To synthesize GelMA, methacrylate gelatin in PBS (pH=7.4) at 50°C to produce the GelMA pre-polymer solution. Terminate the methacrylation reaction by adding phosphate buffer solution and dialyze against deionized water using dialysis tubing with MW cut-offs of 12 to 14 kDa for 5 to 7 days to remove impurities. Freeze-dry the dialyzed solution to obtain GelMA pre-polymers. For a novel method, methacrylate gelatin in a carbonate–bicarbonate buffer at pH 9 and 35-50°C to lower MA to gelatin ratio and achieve a higher degree of methacrylation (96%). To form GelMA hydrogels, polymerize pre-polymers (1 to 15% w/v) in the presence of an energy source (UV or visible light) and a photoinitiator like Irgacure 2959. Adjust photoinitiator concentration and light exposure duration to tune mechanical properties.The hydrophilic polymers were synthesized by first combining gelatin methacryloyl (GelMA) with specific functional groups under controlled conditions. The mixture was then subjected to photopolymerization using a photoinitiator and exposed to UV light to initiate crosslinking. The resulting hydrogels were then washed and characterized for their structural integrity and functional properties.To synthesize methacrylated hyaluronic acid (MeHA), begin by preparing a solution of hyaluronic acid (HA) in a suitable buffer. Add methacrylic anhydride to the HA solution while stirring continuously. The reaction should be allowed to proceed for a specified time under controlled conditions to achieve complete methacrylation of HA. After the reaction, purify the modified product by dialysis or precipitation to remove excess reagents. Finally, characterize the synthesized MeHA through spectroscopic techniques to confirm the presence of methacrylate functional groups.To synthesize MeHA, methacrylate HA by substituting methacryloyl groups on the hydroxyl and reactive amine groups of HA in deionized water at pH 8.0-8.5 and 4°C to produce the MeHA pre-polymer solution. Next, dialysis should be performed using dialysis tubing with MW cut-offs from 6 to 8 kDa for 2-3 days to remove MA byproducts and unreacted MA. Finally, produce the MeHA pre-polymers by freeze-drying the dialyzed solution. Pre-polymers should be at concentrations of 0.25 to 4.0% (w/v) for fabricating MeHA hydrogel constructs in the presence of UV light and Irgacure 2959.Synthesize photo-crosslinkable hydrogels such as poly(ethylene glycol) diacrylate (PEGDA), gelatin methacryloyl (GelMA), and methacrylated hyaluronic acid (MeHA) through free radical initiated chain-growth polymerization.The synthesis of PEGDA hydrogel involves using polyethylene glycol diacrylate (PEGDA) as the main monomer. The hydrogel is formed through photopolymerization or thermal polymerization methods. The specific conditions for polymerization, such as the concentration of PEGDA, the presence of a photoinitiator or thermal initiator, and the exposure time to UV light or heat, are crucial for obtaining the desired polymer properties.The synthesis of GelMA hydrogel involves incorporating functional arginine, glycine, and aspartate peptides into the polymer structure."
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+    "protocol": "活性稀释剂的合成主要通过直接酯化法进行。使用对甲苯磺酸作为催化剂进行酯化反应，反应结束后容易分离催化剂和产物。在反应过程中，使用甲苯作为脱水剂去除生成的水。为了防止原料丙烯酸和产物丙烯酸酯的聚合，需要加入阻聚剂，如对苯二酚、叔丁基对苯二酚或其他酚类和胺类化合物。对丙烯酸高级酯也可以通过熔融酯化法，不必使用脱水剂，在110-120℃回流反应后进行脱水，最后通过减压蒸馏除去未反应的丙烯酸和残余水。酯交换法制备丙烯酸高级醇或官能性丙烯酸酯时，低级酯大多用丙烯酸甲酯，在较低的温度下进行反应，产物甲醇与丙烯酸甲酯形成共沸物，反应时间延长，需使用更多的阻聚剂。将丙烯酸与二氯亚矾反应制得丙烯酰氯，再与醇发生酯化反应。反应条件为低温，无需催化剂和脱水剂，酯化反应几乎定量进行，产品纯度高。反应中产生大量HCl和SO2，需要用多级稀碱液和水进行吸收。使用相转移催化剂合成甲基丙烯酸钠基的亲水性聚合物，选择十六烷基三甲基溴化铵、苄基三甲基氯化铵或四甲基氯化铵作为催化剂，确保反应体系中的原料和系统保持干燥无水，以提高产率。将环氧乙烷或环氧丙烷直接通入（甲基）丙烯酸，在催化剂存在下发生开环加成酯化反应，制得（甲基）丙烯酸羟基酯。根据文献中的描述，合成亲水性聚合物的具体实验步骤如下：使用缩醛热分解法，反应物为 R1 R2 CHCY(OR3) 利用液相分解设备进行反应，催化剂为 85% H3PO4或 98% H2SO4或者 H3C-⊕-SO3H。反应条件应为温和，以便于控制。最终的目标产物为 R1 R2 C - CY-OR3。单官能团活性稀释剂的合成包括选择分子量较低的活性基团，确保每个分子中仅含有一个可参与光固化反应的活性基团。合成过程中，需要控制反应条件以确保光固化速率和交联密度适当，采取措施提高转化率并减少体积收缩。此外，在选择活性稀释剂时考虑其挥发性和闪点，以确保安全使用。常见的单官能团活性稀释剂包括丙烯酸烷基酯、（甲基）丙烯酸羟基酯，以及带有环状结构或苯环的（甲基）丙烯酸酯和乙烯基活性稀释剂。The synthesis involves the use of various alkyl acrylates including butyl acrylate (BA), 2-ethylhexyl acrylate (2-EHA), isodecyl acrylate (IDA), lauryl acrylate (LA), and ethoxy ethoxyethyl acrylate (EOEOEA). Each of these alkyl acrylates has specific properties such as low viscosity, good dilution effects, and low glass transition temperatures (Tg) which contribute to their use in creating hydrophilic polymers with functional groups. The general procedure is to mix the chosen acrylate with appropriate solvents and additives to achieve the desired viscosity and functional characteristics.丙烯酸羟乙酯（HEA）和丙烯酸羟丙酯（HPA）与异氰酸基反应，制备PUA的原料。甲基丙烯酸羟乙酯（HEMA）和甲基丙烯酸羟丙酯（HPMA）由于含有羟基，能够提高对极性基材的附着力。1. Select the appropriate (meth)acrylate monomer based on desired properties, such as GMA, IBOA, THFA, or POEA, which contain functional groups that enhance adhesion. 2. Prepare the monomer by ensuring it is in a suitable state (e.g., low viscosity, high boiling point). 3. Mix the monomer with any necessary additives or initiators to facilitate polymerization. 4. Conduct a polymerization reaction under controlled conditions, monitoring parameters such as temperature and time to achieve the desired polymerization rate. 5. After polymerization, characterize the resulting hydrophilic polymer to confirm functional groups and assess properties such as adhesion, viscosity, and thermal behavior.The synthesis of hydrophilic polymers with functional groups involves using N-vinylpyrrolidone (NVP) as a primary component. The recommended usage level of NVP is between 10% to 20%, as concentrations above this can adversely affect the water resistance of the polymers due to their water-soluble nature.双官能团活性稀释剂每个分子中含有两个可参与光固化反应的活性基团，成膜时发生交联。常用的双官能团活性稀释剂包括BDDA、HDDA、NPGDA、DEGDA、TEGDA、PEG(200)DA和PEG(400)DA，分子量范围从198到508。1. Obtain diethylene glycol diacrylate (DEGDA) or triethylene glycol diacrylate (TEGDA) or polyethylene glycol diacrylate (PEGDA) series with varying molecular weights (e.g., PEG(200)DA, PEG(400)DA, PEG(600)DA). 2. Mix the polymer components in appropriate ratios to form the desired formulation. 3. Ensure the formulation has low viscosity and is suitable for fast photopolymerization. 4. Note that DEGDA and TEGDA have significant skin irritation and are less preferable. 5. For PEGDA, adjust the variable 'n' such that for PEG(200)DA n=4, for PEG(400)DA n=8-9, and for PEG(600)DA n=13. 6. Monitor the viscosity and glass transition temperature (Tg) during the synthesis, and adjust as needed to optimize hydrophilicity and flexibility of the resulting hydrophilic polymers.二丙二醇二丙烯酸酯（DPGDA)和三丙二醇二丙烯酸酯（TPGDA)为主要反应物，利用其低粘度、稀释能力强、光固化速率快的特性进行合成。选择合适的比例与条件以降低皮肤刺激性，确保合成的高效与安全。Synthesize hydrophilic polymers by reacting diacrylate esters of various glycols such as 1,4-butanediol diacrylate (BDDA), 1,6-hexanediol diacrylate (HDDA), neopentyl glycol diacrylate (NPGDA), and phthalic acid diethylene glycol diacrylate (PDDA). Ensure low viscosity and strong dilution capability during the polymerization process, while considering the properties including skin irritation and adhesion to plastics. Use appropriate activation methods such as photopolymerization for rapid curing when needed.阳离子光引发体系使用的活性稀释剂主要为乙烯基醚类和环氧类稀释剂。活性稀释剂包括1-丙烯基醚类、1-丁烯基醚类、1-戊烯基醚类、乙烯酮缩二乙醇类、环氧类、环氧化三甘油酯、氧杂环丁烷类，以及含有环氧基和烯醇醚基团的混合型活性稀释剂。通过环氧化植物种子中不饱和三甘油酯可以获得环氧化单体，进行阳离子光聚合。在带有分水器的三口烧瓶中加人0.1mol十八醇和适量环已烷、1.5%对苯二酚，搅拌升温至60°C，加入0.12mol丙烯酸和1.5%对甲苯磺酸，加热至80~86°C，使反应液处于微沸状态，待分水器分出水量达到理论值时（约6h）停止反应。反应液先用5%硝酸钠洗涤，去除下层，再用10%碳酸钠或氢氧化钠洗至微碱性，最后用饱和氯化钠溶液和蒸馏水洗至中性。用无水硫酸镁干燥过夜、过滤减压蒸馏除去环已烷和微量丙烯酸，得到黏稠液体，冷却后即为丙烯酸十八酯蜡状固体，酯化产率89%，提纯收率95%以上。将二元酸、二元醇和适量阻聚剂（如对苯二酚）加人到反应器中，通入氮气，搅拌升温到 160°C 回流，测酸值至 200 mg K O H/g 左右，开始出水，升温至 175∼200°C，当酸值达到设定值时，停止反应，降温至 80°C 左右，加人 20%∼30% 的活性稀释剂（苯乙烯或丙烯酸酯类活性稀释剂）和适量阻聚剂出料。反应中通氮气，可促进脱水，也能防止树脂在反应中因高温而颜色变深。反应程度通过测定反应体系的酸值来监控；反应结束可以通过测定产物的碘值了解产物的双键含量。环氧丙烯酸酯是由环氧树脂和（甲基）丙烯酸酯化而制得。将环氧树脂升温至80~90°C，滴加丙烯酸、催化剂和阻聚剂混合物，控制反应温度100°C，同时取样测定酸值。到反应后期升温至110~120°C，使酸值降至小于5 mg KOH/g停止反应（一般反应时间需要4~6h），冷却到80°C出料。为防止丙烯酸和环氧丙烯酸酯的聚合，加入0.01%~1%（质量分数）的阻聚剂。丙烯酸与环氧树脂投料比控制在1:1~1:1.05。聚氨酯丙烯酸酯的合成是利用异氰酸酯中异氰酸根—NCO与长链二醇和丙烯酸羟基酯中羟基—OH反应，形成氨酯键—NHCOO—（氨基甲酸酯）而制得。使用的多异氰酸酯可选用甲苯二异氰酸酯（TDI）、二苯基甲烷二异氰酸酯（MDI）、苯二亚甲基二异氰酸酯（XDI）、六亚甲基二异氰酸酯（HDI）、异佛尔酮二异氰酸酯（IPDI）、二环已基甲烷二异氰酸酯（HMDI）。长链二醇的来源包括聚醚二醇和聚酯二醇，其中聚醚二醇有聚乙二醇、聚丙二醇等，聚酯二醇通常由二元酸和二元醇缩聚所得。反应所需的（甲基）丙烯酸羟基酯包括丙烯酸羟乙酯（HEA）、丙烯酸羟丙酯（HPA）、甲基丙烯酸羟乙酯（HEMA）、甲基丙烯酸羟丙酯（HPMA）、三羟甲基丙烷二丙烯酸酯（TMP-DA）、季戊四醇三丙烯酸酯（PETA）。反应中需使用催化剂以缩短反应时间和提高反应速率。常用催化剂包括叔胺类、金属化合物和有机磷，实际应用时，月桂酸二丁基锡为常用催化剂。将2mol二异氰酸酯和月桂酸二丁基锡加人反应器中，升温到40～50℃，慢慢滴加1mol二醇，反应1h后，升温到60℃，测定—NCO值到计算值，加入2mol丙烯酸羟基酯和阻聚剂对苯二酚，升温至70～80℃，直至—NCO值为零。反应完毕，可加入适量的丙烯酸酯活性稀释剂，如用三丙二醇二丙烯酸酯进行稀释，搅拌均匀出料。聚酯丙烯酸酯（PEA）的合成方法包括以下步骤：1. 二元酸、二元醇、丙烯酸一步酯化；2. 二元酸与二元醇反应形成聚酯二醇，再与丙烯酸酯化；3. 二元酸与环氧乙烷加成后，再与丙烯酸酯化；4. 丙烯酸羟基酯与酸酐反应制得酸酐半加成物，再与聚酯二醇酯化；5. 聚酯二元酸与（甲基)丙烯酸缩水甘油酯反应；6. 用少量三元醇或三元羧酸代替部分二元醇或二元酸，制得支化的多官能度聚酯。3.6 聚醚丙烯酸酯聚醚丙烯酸酯的合成通过以下步骤进行：首先，在强碱条件下，将环氧乙烷或环氧丙烷与二元醇或多元醇进行阴离子开环聚合，得到端羟基聚醚。接着，将端羟基聚醚与过量的丙烯酸乙酯及阻聚剂混合，进行加热。在催化剂（如钛酸三异丙酯）的作用下，发生酯交换反应，产生的乙醇和丙烯酸乙酯形成共沸物而蒸馏出来。通过分馏塔，丙烯酸乙酯馏分会重新回到反应釜，而乙醇将被分馏出来，以确保酯交换反应彻底进行。最后，过量的丙烯酸乙酯需要通过真空蒸馏去除。纯丙烯酸树脂的合成使用带有官能基的聚丙烯酸酯共聚物与丙烯酸缩水甘油酯、丙烯酸羟基酯或丙烯酸反应。在反应中，丙烯酸、丙烯酸甲酯、丙烯酸丁酯和苯乙烯共聚物与丙烯酸缩水甘油酯反应，丙烯酸的羧基与丙烯酸缩水甘油酯中的环氧基开环加成酯化，形成丙烯酰氧基以构成光固化树脂。此外，苯乙烯和马来酸酐共聚物与丙烯酸羟乙酯反应，丙烯酸羟乙酯中的羟基与马来酸酐作用，引入丙烯酰氧基，也能生成光固化树脂。1. Use dichlorodimethylsilane monomer and hydroxyethyl acrylate under base catalysis for hydrolysis condensation, introducing HEA as a terminal group to the polyorganosiloxane chain. 2. Introduce acrylate functional groups through an ester exchange reaction between diethoxysilane and hydroxyethyl acrylate. 3. Utilize terminal hydroxy silane to react with acrylic acid for esterification, introducing acrylate functional groups. 4. React terminal hydroxy silane with diisocyanate, then with hydroxyethyl acrylate, or react terminal hydroxy silane with a partial adduct of diisocyanate-hydroxyethyl acrylate to introduce acrylate functional groups.在三口烧瓶中加人一定量环氧大豆油（环氧值0.42)，升温至85℃，滴加含1.5%的三苯基磷、0.1%的对甲氧基苯酚和一定量AA（环氧基：羧基=1.1：1，摩尔比）混合液，加毕升温至110℃，反应至酸值<8mg KOH/g，停止反应得到环氧大豆油丙烯酸酯，得率95%。在三口烧瓶中加入1.05mol 828环氧树脂（环氧值0.548）和0.02%的阻聚剂，加热搅拌，升温至一定温度，滴加1mol丙烯酸和1%的环氧树脂量的催化剂混合液，1h滴完，控制反应温度，定时取样测酸值，当反应体系酸值<3mg KOH/g时停止反应，得到环氧丙烯酸酯。在三口烧瓶中加人25g环氧树脂（E-44)，加人适量甲苯溶解，加热至85℃，滴加溶有0.15g对苯二酚、0.6g二甲苯胺和7.8g丙烯酸的混合溶液，反应1h，升温至95℃反应4h，体系酸值<3mg KOH/g，减压蒸馏，除去甲苯和未反应的丙烯酸得到环氧丙烯酸酯。在三口烧瓶中加入计算量环氧树脂（E-44)、对甲氧基苯酚，升温，缓慢滴加计算量的丙烯酸（羧基与环氧基摩尔比为1：1）和0.6～0.9份催化剂三甲基苄基溴化铵，100～105℃反应2h，酸值<5mg KOH/g，停止反应，得环氧丙烯酸酯，反应转化率≥95%。在三口烧瓶中加入酚醛环氧树脂（F-51）和适量对甲氧基苯酚，升温至90℃搅匀，滴加丙烯酸（羧基与环氧基等摩尔比）和适量N,N′-二甲基苄胺，维持反应温度100℃反应5h左右，至酸值≤5mg KOH/g，趁热出料，或降温至60℃，加入适量稀释剂甲基丙烯酸羟乙酯搅匀后出料。在三口烧瓶中加人50g甲基酚醛环氧树脂JE43、22g醋酸丁氧基乙酯，加热至80℃搅匀，加人0.2g对甲氧基苯酚、15.58丙烯酸以及催化剂(0.25mmol四丁基溴化铵、0.25mmol三乙酰丙酮铬)，搅匀后升温至120℃反应6h得到甲基酚醛环氧丙烯酸树脂。在三口烧瓶中加人1mol聚乙二醇200、2mol双酚A环氧树脂、0.1%的三乙胺，100℃反应5h。降温至80℃加入计算量的丙烯酸（与环氧基等摩尔比)、0.1%的对甲氧基苯酚，升温至100~110℃，反应至酸值≤5mg KOH/g得到低黏度环氧丙烯酸酯。在三口烧瓶中加入1mol双酚A环氧树脂、0.2mol聚醚多元醇、0.25%的催化剂三乙胺，升温至110℃，反应2.5h，测环氧值，降温加人0.1%的对羟基苯甲醚，缓慢滴加1.2mol丙烯酸（与测定环氧等值）并缓慢升温至115℃，反应3h，测酸值KOH/g，停止反应，趁热放料，得低黏度环氧丙烯酸酯。在三口烧瓶中加人100g828环氧树脂、20g二缩三乙二醇（扩链剂）和0.5g三乙胺(催化剂)，升温(70±5)℃反应，每隔30min测环氧值至所需时停止反应。按环氧值：丙烯酸为1:1加人丙烯酸、三乙胺（改性环氧与丙烯酸量的1%），对苯二酚（改性环氧的0.02%）升温至(100±5)℃，反应至酸值<5mg KOH/g得到低黏度环氧丙烯酸酯。在三口烧瓶中加人一缩二乙二醇与环氧树脂E-44（摩尔比为1：10）和催化剂四丁基溴化铵（或四甲基氯化铵、三乙基苄基氯化铵)，100℃反应2h，得改性环氧树脂，黏度低于原环氧树脂，降温至80℃缓慢滴加计算量丙烯酸（羧基与环氧基摩尔比为1：1）和0.6～0.9份催化剂，100～105℃反应2h，当酸值<5mg KOH/g时停止反应，得低黏度环氧丙烯酸酯。在三口烧瓶中加人一定量的环氧树脂（E-51)、已二酸（E-51：已二酸=1：0.3，质量比）和四甲基氯化铵，升温至 $90\\%$ ，反应至酸值接近零时，滴加计量的丙烯酸和2,6-二叔丁基对甲酚混合物， $30\\mathrm{\\sim}40\\mathrm{min}$ 加毕，升温至 $95\\sim100\\mathrm{^{\\circ}C}$ ，反应至酸值 $\\leq5\\mathrm{mg}\\ \\mathrm{KOH/g}$ ，降温过滤出料，得己二酸改性环氧丙烯酸酯，无色或接近无色透明黏稠体，黏度（ $50^{\\circ}\\mathrm{C}$ ）为$3{\\sim}4\\mathrm{Pa}\\cdot\\mathbf{s} $ .在三口烧瓶中加人 50g 甲基酚醛环氧树脂JF43、22g 醋酸丁氧乙酯，加热至 80^{\\circ}C，搅拌至树脂全溶，加入 0.2g 对甲氧基苯酚、15.5g 丙烯酸及 1.25mmol 催化剂，升温至 120^{\\circ}C，反应至体系酸值基本不变为止，得甲基酚醛环氧丙烯酸树脂JFA溶液。将 40g JFA树脂溶液、适量醋酸丁氧乙酯及 0.05g 对甲氧基苯酚加人三口烧瓶中，搅拌升温至 80\\sim90^{\\circ}C，加入 0.098mol 多元羧酸酐，于 120^{\\circ}C 反应至酸值基本不变为止。在三口烧瓶中加入0.5mol聚醚二元醇（PPO210）、1mol甲苯二异氰酸酯（TDI)、0.1%的二月桂酸二丁基锡、0.05%的对甲氧基苯酚，60℃反应至—NCO值到计算值，再加入1mol丙烯酸羟乙酯（HEA)，升温至70～75℃，反应至—NCO值接近于0，得到聚醚型聚氨酯丙烯酸酯。在三口烧瓶中加人410g已二酸、40g马来酸酐、80g三羟甲基丙烷、312g新戊二醇、lg30%的磷酸（催化剂)，加热至110℃，搅拌，通Nz，升温至150～160℃开始出水时，加人80g二甲苯和0.2g抗氧剂，180℃反应4～6h，反应至酸值<5mgKOH/g，停止通N，抽真空，当抽出的二甲苯与加入的二甲苯相当时，停止反应，降温出料，测羟值和酸值，得端羟基聚酯。将600g端羟基聚酯（羟值以100计）加入三口烧瓶中，升温至90℃，加人对甲苯磺酸0.8g、丙烯酸85g对苯二酚0.2g和甲苯80g，0.5h内加完，升温至110～115℃，回流反应4h，测酸值<10mgKOH/g，真空蒸馏除去甲苯，得到黄色的透明树脂，黏度（25℃）1000～3000mPa·s，固含量≥95%，为双官能团聚酯丙烯酸酯。1. Synthesize the organosilicon oligomer by adding octamethylcyclotetrasiloxane and catalyst FeCl·6H2O (0.1% to 0.3%) into a three-neck flask. Stir and add dimethyl dichlorosilane, then heat to 80°C and react for 6 hours. Distill under reduced pressure at 80°C/1333.2Pa, and then centrifuge at 8000r/min to separate residues, resulting in a light yellow transparent liquid α,ω-dichloropolydimethylsiloxane. 2. In the three-neck flask, add pentaerythritol triacrylate, triethylamine (HCl absorbent), solvent toluene, and polymerization inhibitor p-methoxyphenol. Stir in a cold water bath and gradually add α,ω-dichlorodimethylsiloxane while slowly heating to 40°C, reacting for 1 hour. Distill toluene and unreacted triethylamine under reduced pressure at 40°C/1333.2Pa, and then perform a second centrifugation at 8000r/min to separate the precipitate, resulting in a milky to colorless transparent liquid which is the polymethylsiloxane acrylate oligomer.在三口烧瓶中加人计算量的含氢硅油（H-20端氢硅油)、三丙二醇二丙烯酸酯和甲苯/二甲苯溶剂，搅匀通Nz保护，加（35～50)×10-6氯铂酸的异丙醇溶液、1%的对羟基苯甲醚，升温至90～120℃，反应4h，停止反应，减压蒸馏除去溶剂，即得有机硅丙烯酸酯低聚物。在三口烧瓶中加入1mol甲基硅氧烷、2mol丙烯酸羟乙酯、适量的催化剂（二辛酸锡）、阻聚剂（对甲氧基苯酚)，通干燥空气，90℃反应5h，得到UV固化有机硅低聚物。将2mol-甲基丙烯酰氧丙基三甲氧基硅烷、1mol二端羟基二甲基聚硅氧烷和适量二月桂酸二丁基锡催化剂加入到装有回流冷凝器、减压泵的三口烧瓶中，于80～100℃反应8h。反应过程中要及时排走副产物甲醇，以利反应顺利进行，最后减压蒸馏，除去剩下的甲醇和其他烷基醇，得到淡黄色的丙烯酸酯改性的聚硅氧烷低聚物。在三口烧瓶中加入计算量的甲基丙烯酸烯丙酯、反应物总重0.04%的三苯基麟氯化佬（催化剂）、反应物总重50%的甲苯（溶剂）和适量阻聚剂对甲氧基苯酚，通Nz保护，升温至65～70℃，滴加等物质的量的甲基含氢硅油（含量为0.35%)，反应过程中测定含氢硅油的含氢量至转化率达100%时，停止反应，得到光敏有机硅丙烯酸酯低聚物。在三口烧瓶中加人17.4g（0.1mol）甲苯二异氰酸酯以及质量分数0.1%的二月桂酸二丁基锡，升温至40℃，滴加含有阻聚剂对羟基苯甲醚的29.8g（0.1mol）季戊四醇三丙烯酸酯（—NCO：—OH=2：1，摩尔比)，加毕，40℃继续反应4h，当—NCO含量达到预定值后，滴加双烷羟基硅油85g（0.05mol）（—NCO：—OH=1：1，摩尔比)，升温至70～75℃，反应至一NCO含量为零时，停止反应，得到光固化有机硅丙烯酸酯。在三口烧瓶中，将环氧聚硅氧烷与等当量的丙烯酸于100～110℃反应6h，测定酸值和环氧转化率为90%左右，减压蒸馏除去溶剂和未反应的丙烯酸，得环氧聚硅氧烷丙烯酸酯(AEPS)。在三口烧瓶中加人一定量的环氧基硅油和丙烯酸（环氧基与羧基的摩尔比为1：0.95)、总量0.6%的催化剂三乙胺和适量的对甲氧基苯酚，搅匀后升温至100～110℃反应，当酸值<5mgKOH/g时，停止反应，得到环氧有机硅丙烯酸酯(PSAE)。将3份光敏有机硅树脂PSUA和2份三丙二醇二丙烯酸酯以及3%的光引发剂1173加人三口烧瓶中搅拌均匀，滴加1份硅溶胶剧烈搅拌至体系均匀透明，得到光固化有机硅/SiO2杂化材料。在三口瓶中加入一定量的双酚A环氧树脂E-51和适量的对甲氧基苯酚，搅拌加热升温至60℃，慢慢滴加丙烯酸（与E-51环氧基摩尔比为1：1）和适量的苄基三甲基氯化铵，1h滴完，升温至（100士5)℃，反应至酸值<5mgKOH/g，停止反应制得环氧丙烯酸树脂EA。降温至50℃，再加人一定量的偏苯三酸酐B（与EA中羟基摩尔比为0.4～0.5）和适量丙酮，升温至80℃，反应至酸值为理论值时，停止反应，得到酸酐改性EA（B-EA)。常温下加人三乙醇胺搅匀中和，在剧烈搅拌下加水稀释，得到UV水性EA。在三口烧瓶中加入一定量的甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、琉基乙酸、甲苯和偶氮二异丁腈，依次抽真空，充氮气重复3次，升温至85℃，反应10h，制得分子链一端带有羧基官能团的低聚物P，用甲醇沉淀，再用甲苯重新溶解，重复3次，红外干燥真空干燥至恒重。将低聚物P和甲基丙烯酸缩水甘油酯（摩尔比为1：1.5)、催化剂1.5%苄基氯化三乙胺及高温阻聚剂混合，氮气保护下，升温到138℃，反应9～12h，制得聚丙烯酸酯低聚物，精制方法同P。在三口烧瓶中加人 0.050 mol 三氯氧磷和 200 mL 乙醚，置于冰浴中，缓慢滴加 22.80 g (0.050 mol) 全氟烃基乙醇和 5.10 g (0.050 mol) 三乙胺混合物，在 25°C 搅拌反应 8 h。再滴加 5.81 g (0.050 mol) 丙烯酸羟乙酯、5.10 g (0.050 mol) 三乙胺和适量乙醚混合物，在 25°C 搅拌反应 12 h。然后再慢慢滴加 2.43 g (0.027 mol) 1,4-丁二醇、5.5 g (0.054 mol) 三乙胺和适量乙醚混合物，在 25°C 搅拌反应 12 h。反应产物经过滤，滤饼经中和、洗涤和干燥，蒸去溶剂，得到淡黄色固体B，为光固化含氟丙烯酸磷酸酯。在三口烧瓶中加入1mol季戊四醇、4mol偏苯三酸酐和溶剂二甲基甲酰胺，在氮气保护下，搅拌升温至110至115°C，每半小时取样测酸值至恒定。加入计算量的环氧丙烷，反应至酸值恒定；加入计算量的偏苯三酸酐，反应至酸值恒定，如此重复反应至设计要求，得到超支化聚酯树脂。在上述反应所得超支化聚酯树脂冷却至60°C以下，加入配方量二甲基甲酰胺、计算量的甲基丙烯酸缩水甘油酯及适量的以羟基苯甲醚，升温至90至95°C反应至酸值恒定，得到超支化聚酯甲基丙烯酸树脂。PPA是一种双官能度的哌嗪基苯乙酮引发剂，为无味的浅黄色液体，在 λ=332 nm 处有较强吸收，能增强或拓宽夺氢型光引发剂的紫外线吸收，提供更高效的固化性能。在装有 200g 、 50% 的乙醇的三口烧瓶中加人 197g 苯甲醛、 40g 四乙基溴化铵和 80g 氰化钠，升温至 90°C ，回流搅拌2h。冷却过滤，得淡黄色结晶，用乙醇重结晶得产品 184g .熔点 134~135°C ，收率 92%。将 50mmol 新蒸苯甲醛、 12mmol 氰化钠、 12.5mL 95% 的乙醇和 0.8mol 氢氧化钠（5%）加入 100mL 锥形瓶中，置于超声波清洗器中超声辐射3h，冷却后抽滤，用乙醇重结晶得到产物苯偶姻，产率 85%。在三口烧瓶中加人 100g 安息香、 250g 冰醋酸和 250g 浓硝酸，加热至 85~95°C ，回流4h，冷却，过滤，用甲醇重结晶得黄色结晶 132g ，熔点 94~95°C ，收率 97%。在三口烧瓶中加入1mol安息香双甲醚和1mol一缩二乙二醇及催化剂对甲苯磺酸（总量的2%），升温至100℃反应5h，中和反应液，水洗至中性，干燥，得到一缩二乙二醇安息香双甲醚，可溶于80℃的蒸馏水中(0.1g/50mL)。在三口烧瓶中加入1mol安息香双甲醚、4mol三羟甲基丙烷及催化剂对甲苯磺酸（总量的2%），升温至100℃，溶解反应5h，中和反应液，水洗至中性，干燥得三羟甲基丙烷改性安息香双甲醚，可溶于80℃的蒸馏水中(0.18/50mL)。在三口烧瓶中加入128g羟甲基安息香甲醚、49g马来酸酐、200mL二氧六环和催化剂2mL三乙胺，搅拌升温，回流30min减压蒸馏除去溶剂，用热水洗两次，在烘箱中60℃干燥5h，得到淡黄色粉末168g，为马来酸酐改性羟甲基安息香甲醚，产率95%。在三口烧瓶中加人144g乙苯和296g无水三氯化铝，维持在20~30°C下，分批加人150g苯酐，控制温度<40°C，反应2h，至无氯化氢逸出，反应完毕，得橘红色溶液。冷却后慢慢滴加10%的盐酸溶液进行水解，快速搅拌，控制温度<40°C，物料变为乳白色油状，分离，油状物在55~60°C/4kPa减压蒸馏，得A。将A置于三口烧瓶中，加热至110~120°C，搅拌下慢慢滴加20%的发烟硫酸，使反应温度<120°C。反应完毕得深黄色液体，倾入冰水混合物中，析出黄色的2-乙基葱粗品，经过滤、碱洗、水洗得浅黄色固体，熔点104~106°C，产率89%。粗品加入硫代硫酸钠和10%的NaOH溶液，中和至pH=11，于95°C反应20min，得无色2-乙基氢，通空气氧化，得2-乙基。用500mL95%的乙醇萃取，再于79~85°C蒸去乙醇，再80°C恒温干燥得浅黄色固体即为2-乙基葱结晶，熔点110~111°C。在三口烧瓶中加人2.20g硫酚、5.64g3-硝基-N-对甲苯基-邻苯二甲酰亚胺和50mL二甲基甲酰胺，搅拌溶解，在氮气保护下慢慢加入2.8mL三乙胺，混合物迅即转黄，颜色加深，待再转成淡黄色后，搅拌20min，把混合物倒人稀盐酸/冰水中，经过滤、干燥，得6.86g A，熔点 187~188℃，收率 95%。将3.5g A加到35mL、20%的氢氧化钠溶液中，在100℃搅拌30min，冷却，用浓盐酸酸化，过滤，将滤饼转至30mL浓盐酸中回流1h，冷却、过滤，真空干燥得2.2g B，熔点 >270℃，收率 81%。将6.9g B和70mL多聚磷酸在200℃下搅拌100min，冷却至室温，倒人200mL冷水中，过滤，干燥，再溶于二甲基甲酰胺中，加活性炭升温脱色，加水重新析出产品，过滤、干燥，用冰醋酸重结晶得6.2g黄色的硫杂葱酮-1-羧酸，熔点260~262℃，收率96%。在三口烧瓶中加入5.22g（0.03mol）甲苯二异氰酸酯（TDI）、3滴二月桂酸二丁基锡和无水乙酸乙酯，通氮气，升温至45℃，缓慢滴加丙烯酸羟乙酯（HEA）3.48g（0.03mol），升温至50℃，反应2h，得HEA-TDI半加成物。将18g（0.03mol）聚乙二醇加入到HAPK-TDI反应容器中，通氮气加热至70℃，反应3~4h，再加入HEA-TDI，70℃反应3~4h，真空蒸馏除去乙酸乙酯，得到可聚合大分子光引发剂HAPK-TDI-PEG600-TDI-HEA。将甲基丙烯酸甲酯 $12.50\\mathbf{g}$ （ $125\\mathrm{mmol})$ 、丙烯酸 $25.00\\mathbf{g}$ （347.2mmol）、丙烯酸丁酯$12.50\\mathbf{g}$ （97.7mmol）混合，加人 $0.75{\\bf g}$ 偶氮二异丁腈使之溶解，倒入滴液漏斗中。在三口烧瓶中加入 $70\\mathbf{g}$ 乙二醇单甲醚，升温到 $80^{\\circ}\\mathrm{C}$ ，通氮气0.5h，慢慢滴加混合单体， $85^{\\circ}\\mathrm{C}$ 反应$5\\mathord{\\sim}6\\mathbf{h}$ ，冷却，反应物倒人水中使聚合物析出，反复洗涤，真空干燥 $50^{\\circ}\\mathrm{C}\\times24\\mathrm{h}$ ，得高分子酸，数均分子量6956，重均分子量13223，多分散性1.90；酸值 $436.88\\mathrm{mg}\\mathrm{KOH/g}.$ 在三口烧瓶中加人高分子酸 $5.00\\mathbf{g}$ 、 $60\\mathrm{mL}$ 四氢呋喃，超声振荡 $15\\mathrm{min}$ ，得清澈溶液，升温至 $60^{\\circ}\\mathrm{C}$ ，慢慢滴加二氯亚矾，使其保持微沸反应 ${\\mathfrak{6}}\\sim7{\\mathrm{h}}$ ，停止加热，旋蒸除去溶剂，用正己烷多次洗涤，真空干燥 $30^{\\circ}\\mathrm{C}$ ， $24\\mathbf{h}$ ，得高分子酰氯。将高分子酰氯 $2.80\\mathbf{g}$ 完全溶于 $60\\mathrm{mL}$ 四氢呋喃中，倒人用铝箔包裹的三口烧瓶中，加人三乙胺 $\\phantom{-}3.\\phantom{-}03g$ C $\\mathbf{\\left(30.0mmol\\right)}$ ，升温到 $60^{\\circ}\\mathrm{C}$ ，慢慢滴加光引发剂1173（2-羟基-2-甲基苯基丙酮） $0.432g$ ? $\\left(2.63\\mathrm{mmol}\\right)$ ）回流反应 $6\\mathrm{h}$ 。再慢慢滴加丙烯酸羟乙酯 $2.697_{8}$ （23.3mmol)，保温 $40^{\\circ}\\mathrm{C}$ ，反应 $6\\mathrm{h}$ ，避光旋转蒸除溶剂，用正已烷洗涤，真空干燥 $48\\mathrm{h}$ 制得带光引发基的低聚物。在三口烧瓶中加人 5.2g 甲苯二异氰酸酯、1arg L 二月桂酸二丁基锡和 150mL 乙酸乙酯，加热至 50°C，搅拌下滴加 68~4Å -羟基二苯甲酮和 60mL 乙酸乙酯混合液，加毕升温至 60°C，保温反应 3h。再滴加 2,78 N,N-二甲基乙醇胺和 60mL 乙酸乙酯混合液，加毕升温至 78%，反应 3h，将反应后的有机层分别用 10% 的 NaOH 和蒸馏水洗2次，再用无水 Na2SO4 干燥，用旋转蒸发除去乙酸乙酯，得到浅黄色的产品—带叔胺基的大分子光引发剂。在三口烧瓶中加入 4.5 g (0.03 mol) 对二甲氨基苯甲醛、30 mL 无水乙醇，待全部溶解后，再加入 3.6 g (0.03 mol) 苯乙酮，混匀，在快速搅拌下，慢慢滴加 6 mL 的 15% 的氢氧化钠水溶液，开始滴加时，溶液逐渐变为橘红色，然后析出大量黄色固体，室温下反应4小时后停止，抽滤，样品以无水甲醇重结晶两次，得黄色晶形固体为4-二甲氨基亚苄基苯乙酮，熔点 109.5°C。在三口烧瓶中加入 40g 三甲胺盐酸盐和 80mL 无水乙醇，加热至 30^{\\circ}C，搅拌滴加 42.58g 环氧氯丙烷，反应 3～4h，有大量白色晶体产生，过滤，用无水乙醇洗涤，干燥后得粗品，用乙醇重结晶，得纯品A（3-氯-2-羟基丙基三甲氯化铵)，熔点186～188℃，收率 38.4%。在干燥的三口烧瓶中加入 0.27g 金属钠和 27mL 无水乙醇，待钠反应完全后，加入 2.28g 2-羟基硫杂葱酮，搅拌加热至回流，加入 2.14g A 回流反应 20h。加几滴 2mol/L 盐酸异丙醇溶液，调pH=4，趁热过滤，滤液用冰水冷却得黄色晶体，甲醇洗涤，干燥得黄色固体，熔点245～246.5℃，用乙醇与甲醇混合溶剂重结晶，再用乙醇洗涤，真空干燥，得亮黄色晶体B[2-羟基-3-(2'-硫杂葱酮氧基)-N，N,N-三甲基-1-丙胺氯化物]，收率 62.8%。在三口烧瓶中加入浓硫酸、邻琉基苯甲酸，搅拌下分批加入2,5-二甲基苯酚，室温搅拌1h，升温至85℃，反应2h静置过夜，反应液倒入冰水中，过滤，用100g/L氢氧化钠水溶液洗涤滤饼，过滤，用稀盐酸中和，得粗品，用冰醋酸重结晶，得浅绿色晶体A（2-羟基-1,4-二甲基硫杂葱酮)，熔点220.3～220.8℃，产率63.2%。随后在三口烧瓶中加入A、3-氯-2-羟基丙基三甲基氯化铵和二甲基甲酰胺，搅拌5min升温至100℃，加入乙醇钠乙醇溶液（30g/L），调pH值至9，反应24h后滴加2mol/L盐酸异丙醇溶液调pH值至4，过滤，冷却得黄绿色晶体，过滤，真空干燥，用乙醇与水（20:1体积比）混合溶剂重结晶，得到B［2-羟基·3–(1′,4′)二甲基·2′-硫杂葱酮氧基)-N,N,N-三甲基-1-丙胺氯化物]，熔点254.6~255.8℃，收率76.8%。在三口烧瓶中加入 32.4g 亚硫酸氢钠、 12.6g 亚硫酸钠和 52.58L 去离子水，边搅拌边滴加 25g 环氧丙烷，温度控制在 18∼30°C ，反应 1∼1.5h ，沉降，过滤、水洗、干燥，得高纯度白色结晶A，熔点 262∼263°C ，得率 95% 。在三口烧瓶中加入 2.15g 2·-羟基硫杂葱酮的钠盐、 1.7g A和 38mL 二甲苯甲酰胺及少量四丁基溴化铵，搅拌、加热至回流反应 2h ，冷却倒入 200mL 丙酮中，有大量固体析出，过滤，用丙酮多次洗涤，烘干，粗品用甲醇重结晶，得化合物B。在三口烧瓶中加入2-羟基-1,4-二甲基硫杂葱酮的钠盐、3-氯-2-羟基丙基磺酸钠、二甲基甲酰胺和少量三乙基苄基氯化铵，搅拌5min，升温至回流，反应2h，冷至室温，反应液用大量丙酮洗涤，过滤、烘干得粗品，用无水甲醇重结晶得A［2-羟基-(1',4'-二甲基-2'-硫杂葱酮氧基)-丙基磺酸钠，熔点 ${>}300^{\\circ}\\mathrm{C}$ ，产率 $26.1\\%$。将对二甲氨基苯甲酸分别与硫酸二甲酯、硫酸二乙酯或溴丁烷、溴戊烷、溴己烷、溴辛烷在相转移催化剂存在下反应，分别得到不同的对二甲氨基苯甲酸酯。不同对二甲氨基苯甲酸酯的收率和性能见表4-43。在三口烧瓶中加人 $83.81g$ 甲基丙烯酸羟乙酯、 $105\\mathrm{mL}$ 三乙胺和 $250\\mathrm{mL}$ 无水甲苯，搅匀，在冰浴中控制温度 $0\\sim5\\mathrm{{\\ttC}}$，4h内慢慢滴加 $79.79g$ 丙烯酰氯和 $\\mathfrak{s o}_{\\mathbf{g}}$ 无水甲苯混合物，加毕，静置过夜，抽滤除去生成的季铵盐，用 $\\scriptstyle40\\mathrm{mL}$ 甲苯洗2遍，滤液依次用 ${75}\\mathrm{mL}$ 蒸馏水、$\\mathtt{50m L1m o l/L}$ 盐酸、 $\\mathrm{50mL~1mol/L}$ 碳酸氢钠洗涤，然后用无水硫酸钠干燥。过滤、旋转蒸发除去甲苯，得浅黄色A(乙二醇丙烯酸酯甲基丙烯酸酯)。在三口烧瓶中加人 $0.05\\mathrm{mol}$ A和 $25\\mathrm{mL}$ 无水甲醇，搅匀，冰浴中、氮气保护下慢慢滴加0.05mol吗啡啉和25mL无水甲醇混合物，红外监控反应至N—H峰（330cm-1）消失，旋转蒸发除去甲醇。The synthesis protocol involves the use of high functionality bifunctional aliphatic polyurethane acrylate with varying content percentages (e.g., CN8000 with 75%, CN8001 with 77%, etc.) which exhibits rapid curing rates and excellent adhesion to plastics and metals. Additionally, it includes modified epoxy acrylates and modified polyester acrylates for desirable properties such as toughness, gloss, adhesion, and resistance to yellowing, among others. Specific products recommended include ETERCURE6233 and ETERCURE6145-100 for their outstanding performance in UV vacuum coatings.一般的UV真空镀涂料施工工艺如下。工件的前处理 → 喷涂UV底漆 → 室温流平 → 红外线流平（60∼70℃ /约 3min）→ UV固化 → 工件冷却 → 真空镀膜 → 喷涂UV面漆 → 室温流平 → 红外线流平（60∼70℃ /约 3min）→ UV固化。氟代烷烃改性的丙烯酸酯通过丙烯酸含氟烷基酯自聚或与丙烯酸酯共聚来合成。共聚物还可通过三氟氯乙烯和烷基乙烯基醚的共聚形成，接着经过丙烯酰基合成含氟丙烯酸酯树脂。配方中含氟丙烯酸酯树脂的含量一般为350%。使用的活性稀释剂是TMPTA和TPGDA的丙烯酸官能单体。光引发剂采用耐黄变性好、光引发活性高的TPO和184等。UV粉末涂料的制备方法是将物料（树脂、光引发剂、颜料、填料和助剂等）经预混后在挤出机中熔融混炼、挤出、然后冷冻、粉碎、过筛。1. Prepare a mixture of low viscosity EA TPGDA at a ratio of 30 parts. 2. Add propoxylated glycerol triacrylate at 23 parts. 3. Incorporate N,N-Dimethylethanolamine at 4 parts. 4. Include DPPA at 2 parts. 5. Add leveling agent at 1 part. 6. Mix thoroughly until a homogeneous solution is obtained.Mix EA, PUA, and TPGDA in the following ratios: 55 parts EA, 10 parts PUA, and 8 parts TPGDA. Add 651 parts of an active amine and 15 parts of a polysiloxane lubricant, followed by 1 part of another component.Mix the following components to synthesize hydrophilic polymers with functional groups: EA (CN10420 containing 20% NPG (PO) DA) 44.0 parts, active amine (CN366) 9.9 parts, NPG(PO)2DA 30.9 parts, DTMPTA 3.2 parts, Bentone 27 2.0 parts, and zinc oxide 0.4 parts.The synthesis involves using aliphatic PUA (CN970E60) and DPPA in specific ratios: 57.5 parts of CN970E60, 10.0 parts of DPPA, and 3.5 parts of KIP100F TZT, with an additional 3.0 parts added for further specifications.Combine the following components: EA (34.5), TMP(EO)TA (20.0), DPTTA (25.0), BP (2.0), KIP150 (3.0), ITX (0.5), 活性胺 (12.0), 有机硅丙烯酸酯 (3.0).To synthesize hydrophilic polymers with functional groups, mix the following components: EA (36 parts), GPTA (25 parts), TPGDA (184 parts), and BP (10 parts). Additionally, include 20 parts of reactive amine and 6 parts of silicone leveling agent.The synthesis involves using a combination of ethyl acrylate (EA) at a concentration of 22.8 g, trimethylolpropane triacrylate (TMPTA) at 23.0 g, and tripropyleneglycol diacrylate (TPGDA) at 45.0 g, along with 3.0 g of a curing agent. An amine flow agent such as N-methyldiethanolamine is added at 3.0 g, with an additional 0.2 g of a leveling agent.The synthesis of hydrophilic polymers involves the use of EA containing 20% NPG(PO)DA, with a proportion of 44.0 g of EA and 9.9 g of active amine. Additionally, NPG(PO)DA DTMPTA is included at 30.9 g and 3.2 g, along with 184 g of a thixotropic agent. The process continues with the addition of 3.6 g of another component and optional increments of 1.0 g and 0.2 g, respectively.Prepare a mixture containing 46.0 parts EA, 16.5 parts TPGDA, and 10.0 parts TMP(E)(O)TA. Add 1.0 part of BP as a photoinitiator and 5.0 parts of leveling agent. Incorporate 21.0 parts of active amine into the mixture. Adjust the mixture viscosity with additional components if necessary, aiming for a final volume of 100 parts, ensuring uniform mixing throughout.改性EA（623，A-80，含20%TPGDA） (PO)NPGDA BP 184 活性胺（Etercure6420） 二官能度脂肪族PUA（611A-85，含15%TPGDA） 60 消泡剂（FoamerxN） 20 平滑剂（Eyerslip70） 20低黏度EA（CN124A80） TPGDA 52 24 1173 2 活性胺 15低黏度EA（CN141） PEG（400)DA的配比为13.5和15.0; 非迁移光引发剂（SR1111）和流平剂（SR011）的配比为30.0和0.5。低黏度EA（CN124C60） HDDA 39 26 BP 6 活性胺 12To synthesize hydrophilic polymers with functional groups, combine the following components in specified amounts: EA (30.0), amine modified polyether acrylate (10.0), GPTA (30.0), polyether acrylate (5.0), LE-HK (6.0), and TPGDA (24.0).Combine 38 parts of EA, 10 parts of TPGDA, 5 parts of HEA. Add 10 parts of SiO2, 4 parts of BP, and 1 part of active amine. Use 0.01 parts of a suitable catalyst.Synthesize four-functional group PEA (CN920) by mixing PEG(400)DA (20.0g), TEA (3.0g), talcum powder (25.0g), and leveling agent (SR011) (0.3g).Synthesize a hydrophilic polymer using a mixture of four-functional group polyethylene amine (PEA, CN920) and PEG(400)DA in the proportions of 35.0 g and 55.2 g respectively. Add 651 g of TEA and 5.0 g of a suitable curing agent.升温至70～90℃，趁热喷涂到开孔木基材上，经流平，再UV固化。To synthesize hydrophilic polymers with functional groups, combine the following components: 26.5 parts of EA(EB3720), 30.00 parts of tri-functional aliphatic PUA (EB264), 1.00 part of organosilicon diacrylate (EB350), 4.00 parts of BP, 2.00 parts of amine accelerator (FirstcureAS), 0.30 parts of fluorosurfactant (FC4430), and 0.02 parts of MEHQ. Ensure proper mixing and curing conditions as required.芳香酸丙烯酸酯半酯（SB520E35） 45 NPG（EO)DA 38, EOEOEA 7, 非迁移光引发剂（SR1112） 10Combine EA (85), PEA (40.0), TPGDA (30.0), and BP (5.0) in a suitable reaction vessel. Then add 1173 (1.0), an active amine (10.0), SiO2 (5.0), and a leveling agent (0.5). Stir the mixture under appropriate conditions to ensure complete mixing and activation of functional groups.Combine 40.0 parts of EA, 40.0 parts of TPGDA with 0.1 parts of BYK307, 10.0 parts of HDDA with 0.1 parts of 2,6-di-tert-butyl-p-cresol, and 10.0 parts of TMPTA.The synthesis of hydrophilic polymers involves the use of the following components: EA (Ethyl Acrylate) and TMPTA (Trimethylolpropane Triacrylate) in a ratio of 18.0 to 24.0. Additionally, active amine groups can be incorporated with SiO2 (Silicon Dioxide) in quantities ranging from 5.0 to 7.0. Furthermore, TPGDA (Tripropylene Glycol Diacrylate) and BP (Benzoyl Peroxide) are included in amounts of 32.0 and 3.0 respectively. For the formulation, a leveling and defoaming agent along with ethyl acetate is added at 0.5. Lastly, another component labeled as 651 is used at a concentration of 4.0.Mix low viscosity EA (CN140) at 35.0 g, non-migratory photoinitiator (SR1112) at 10.0 g, PEG(400)DA at 54.7 g, and leveling agent (SR011) at 0.3 g.The synthesis of hydrophilic polymers with functional groups involves combining various components in specified ratios. The following steps can be adapted for a specific formulation: 1. Combine low viscosity EA (CN141), SiO (OK412) at ratios of 12.0 each. 2. Use TMP (EO) TA, in a range of 27.5 - 37.0 - 7.0 over three formulations; include a wetting agent (SR021) at 1.0. 3. Introduce NPG (EO) DA with a leveling agent (SR011) at 0.5. 4. Optionally, include other components like modified EA three-functional PUA at 10.0 - 30.0 with TMPTA at 13.0, TPGDA at 15.0, and EHA at 8.0, incorporating EFKA additives and dispersants as needed. The resulting blend should achieve desired properties for targeted applications.To synthesize hydrophilic polymers with functional groups, combine the following components: PEA (6315) 45 parts, six-functional group aliphatic PUA (6145-100) 10 parts, HDDA 15 parts, TMPTA 10 parts, and 4 parts of BP initiator (EC645) along with 0.1 parts of abrasive powder Elerslip70.To synthesize hydrophilic polymers with functional groups, combine the following components: PEA (EB800) at 32.5 g, DPGDA at 48.0 g, Syloid161 at 8.0 g, amine-modified acrylate (EB7100) at 5.0 g, TS100 at 2.0 g, and EB350 at 0.5 g. The total mixture should be stirred for 500 seconds.Synthesize four-functional PEA (EB800), DPGDA, and amine-modified acrylate (EB7100) in the following ratios: 42 parts of four-functional PEA, 1173 parts of DPGDA, and 40 parts of amine-modified acrylate. Include 3 parts of the silica extender SiO (Syloid161) and additional silica extender SiO (TS100) as needed.The synthesis of hydrophilic polymers with functional groups includes the following components: 27.5 g of four-functional PEA (EB810), 27.5 g of aliphatic PUA containing 25% TPGDA (EB265), 36.6 g of HDDA, 1.0 g of matting powder (LO-VOIHSF), 3.0 g of reactive amine (EB7100), and 0.4 g of non-silicone defoamer (BYK055).1. Sequentially add the following components in the specified order: ① Amino-modified polyether acrylate (Laromer LR8997) 59.0 g, ③ Silicon coupling agent (Dynasilan MEMO), ④ Defoamer (TEGO Ainex 920), ③ Water, Nano SiO (Cab-O-Sil MS, particle size 1-14 nm) 3.1 g, ② Polytetrafluoroethylene micro powder wax (Ceraflour 996) 12.2 g, ⑧500 g. 2.0 g of Nano AlO (Alodur ZWSKF 1200) 5.1 g, SiO (Syloid ED80) 18.6 g, TPGDA 31.4 g. 3. Ensure to add the materials in the specified order, and finally add SO shear slowly until the mixture reaches a paste-like consistency.1. Mix modified EA PEA (5429), aliphatic PUA (EB270), TMPTA, TPGDA, and HDDA in the following proportions: 15g EA PEA, 20g aliphatic PUA, 20g TMPTA, 10g TPGDA, and 15g HDDA. 2. Add BP 1173 active amine and adhesion promoter EFKA3777 to the mixture. 3. Use a solvent mixture of ethyl acetate and butyl acetate in a ratio of 6:4.根据文中描述，合成亲水性聚合物的实验步骤未直接阐述，但涉及的单体包括：EA, PUA, TMPTA, DPGDA, HEMA、附着力促进型PUA、三丙烯酸酯等。此外，各种聚合物的配比和助剂（如TPO、云母）也在表中列出。需要选择适当的单体和配比，配制成涂料，经稀释后进行喷涂，并在特定条件下固化以形成具有功能基团的亲水性聚合物。使用自引发低聚物（DrewRad150），EO-TMPTA，DPGDA和BP进行合成。具体比例为：DrewRad150 43.4, EO-TMPTA 1173, DPGDA 10.8, BP 0.5。使用消光自引发低聚物（DrewRadm-15）比例为：3.0，DrewFax860 1.0，添加共聚物总量为31。总粘度为250 mPa·S，采用Fusion300WH灯进行固化，速率为100 ft/min，耐摩擦为圈数。Synthesis of hydrophilic polymers with functional groups involves mixing the following components: 21.0 parts of six-functional group aliphatic PUA (PRO30000), 10.0 parts of three-functional group acrylate (SR9012), 7.0 parts of three-functional group ester (CD9051), 1.0 parts of three-functional group aliphatic PUA (CN970A60), 20.0 parts of ethyl acetate, 23.0 parts of butyl acetate, and 17.0 parts of n-butanol. Additionally, include 0.1 parts of leveling agent (Tego450) and other functional additives as needed.合成三官能团脂肪族PUA (U100) PEG(200)DA，配方包含67.8g U100，1173g PEG(200)DA，29.1g助剂（BYKUV3500），2.9g黏度（23C）/mPa·s。通过UV辊涂技术进行施涂，涂层量为10g/m²，固化速率为>20m/min，固化条件使用1盏80W/cm的汞灯，固化能量为200mJ/cm²。脂肪族二官能团PUA（ECX-6025）与EO-NPGDA(Photomer4039)和环氧大豆油丙烯酸酯（Photomer3005）混合，按照LA 8, EHA 4的比例进行合成。To synthesize hydrophilic polymers with functional groups, mix 40.0 parts of三官能度脂肪族PUA (6130B-80) with 30.0 parts of PETA PEG(200)DA, adding 5.0 parts and 25.0 parts respectively. Incorporate 0.3 parts of ES70.Synthesize a hydrophilic polymer by combining 50.0 parts of a tri-functional aliphatic polyurethane acrylate (911B-85), 30.0 parts of HDDA, and 10.0 parts of TMPTA. Add 2.0 parts of BP as a photoinitiator, 4.0 parts of an active amine (Etercure 6410), and 0.2 parts of Eterslip 70 as a slip agent.用138份丙烯酸羟乙酯/已内酯的加成产与39份六羟甲基蜜胺，加人0.05份MEHQ在90℃，反应6h制得。将脂肪族PUA（LPWDS4060）和POEA按照比例49.41:16.47:1.65混合。加入颜料和添加剂，总量达到28.91。然后加人乙酸乙酯，使黏度（25°C，涂-4杯）为35s。加人乙酸乙酯，使黏度 $25^{\\circ}C$ ，涂-4杯）为35s。合成六官能度脂肪族PUA（EB5129）与乙氧基季戊四醇四丙烯酸酯（SR494）和TPO，比例为80:120:6，加入乙酸丁酯，然后加入受阻胺（TINUVIN292）3和有机硅助剂BYK306 1，最终总量为20。The synthesis of hydrophilic polymers with functional groups involves using a formulation that includes a di-functional aliphatic polyurethane acrylate (EB4858) at a concentration of 58.0, and a silicone additive (BYK306). For a UV spray coating, a blend of aliphatic PUAs (LPWDJ4060 and XP2513) is combined with PETA in a ratio of 184:TPO (3:1), alongside the hindered amine (Sanduvor 3058) at 14.00, an additive (BYK331) at 10.70, and ethyl acetate. Additionally, UV absorbers (Sanduvor 3206) are incorporated, adding 2.14, 1.07, and 0.10 at 20.00 for viscosity control. The viscosity measured at 25℃ using a涂-4 cup was 20, with a solid content of 69%. The curing condition specified is at 50℃ under a 900W mercury lamp for a rate of 5 m/min.脂肪族PUA（VPLS2308） 脂肪族PUA（XP2513） HDDA 184:819（7:1） 44.30 (BYK306) 2.20 紫外吸收剂（TinUVin400） 48.45 受阻胺（TinUVin292） 2.85 0.60 1.00 0.60 1。黏度（23C）/mPa·s 150。喷涂量/（g/m²） 50。固化条件/（mJ/cm²） 2800。汞灯（80W/cm）/盏 1。灯（80W/cm）/盏 2.5。脂肪族PUA 甲氧基聚乙二醇（550）单丙烯酸酯（LD552） 聚乙二醇（200）二丙烯酸酯（SR259） HDDA 70 PETA 10 1173 8 硅烷偶联剂（KH-570） 2 6 2 0.5脂肪族PUA 48 EO-TMPTA 9; EOEOEA 40 1173 3The synthesis involves mixing EA (30 parts), PUA TPGDA (10.34 parts), a coupling agent (KH-560, 2 parts), and gas-phase SiO2 (5 parts).脂肪族PUA（CN988） 42; POEA 40; 低黏度单丙烯酸酯低聚物（CN131） 10; 非迁移光引发剂（SR1112） 8脂肪族PUA 20.0, 氨基（甲基）丙烯酸酯 24.0, TPGDA 30.0, $({\\mathrm{PO}})_{3}$ TMPTA 20.0, 添加助剂 BYK306 0.5, BYK333 0.5, BYK920 1.0To synthesize hydrophilic polymers with functional groups, combine the following components: 10.0 parts of aliphatic PUA, 10.0 parts of low viscosity EA, 70.0 parts of (PO)NPGDA, 5.0 parts of (EO)TMPTA, 0.5 parts of adhesion promoter, and 0.5 parts of leveling agent. Mix thoroughly and proceed with polymerization under appropriate conditions.The text excerpt does not provide a specific experimental protocol for the synthesis of hydrophilic polymers with functional groups. It mainly outlines various formulations for UV water-based coatings and does not include detailed synthesis steps or procedures.将水性PEA（PE22WIN）与亲水性聚醚丙烯酸酯（LR8982）按比例混合，水性PEA用量为70，亲水性聚醚丙烯酸酯用量为30。将PEA/脂肪族PUA分散体（UAVPLS2229）与HEA以90:10的比例混合。将混合物在$45^{\\circ}C$下干燥10分钟，然后进行UV曝光。显影时使用水/乙醇的比例为28/1。UV固化4s， $120^{\\circ}\\mathrm{C}\\times30\\mathrm{min}$A组分准备：混合DesmophenAVPLS2099/1（30%BA）21.1g、RoskydalUAVPLS2308(20%BA)32.3g、184/819(911)3.7g与Sanduvor3206 1.3g。加入Sanduvor3058助剂MPA。B组分准备：使用RoskydalUAVPLS2337。A组分： 多羟基丙烯酸酯AcryflowAl40（70%丙酮） 16.10g; 多羟基丙烯酸酯AcryflowP120 3.75g; IBOA 2.50g; TMPTA 2.50g; HEA 2.50g. B组分： HDI三聚体（80%丙酮） 819; 锡催化剂（1%DBTDL）; UV吸收剂（50%Tinuvin400）; 光稳定剂（50%Tinunin292）; 流平剂（BYK358）。UV固化4s，$60^{\\circ}\\mathrm{C}\\times30\\mathrm{min}$ 烘烤。A组分： 烯丙基醚改性PUA 45.0; B组分： EO-TMPTA 20.0; 三甘醇二乙烯基醚（DVE-3） 10.0 20.0; 1173 5.01. Prepare A and B components in a 1:1 ratio. A组分 includes 脂肪族PUA (15.0), TMPTA (30.0), HDDA (40.0), HEMA (10.0), 1173 (3.0), and 环烷酸钻 (1.0). B组分 includes 脂肪族PUA (15.0), TMPTA (30.0), HDDA (40.0), HEMA (10.0), 1173 (3.0), 过氧化叔丁酸 (1.0), 硅表面活性剂 (0.2), and 氟表面活性剂 (0.2). 2. Mix components within 8 hours. 3. Ensure the inclusion of functional groups such as -OH from HEMA.A组分与B组分混合均匀，具体包括三重固化PUA PO-TMTA 49.0g，羟基聚酯树脂（181X）10.0g，环烷酸钻 4% 27.0g，过氧化环已酮 3.0g，乙酸丁酯 1.5g，且TPGDA 11.0g及其余成分按比例加入和搅拌。脂环族环氧树脂与乙烯基醚、三芳基硫盐及硅流平剂的混合用以合成含功能基团的亲水性聚合物3，4-环氧已烷甲酸-3，4-环氧环己烷 甲酯（ECC） 2-乙基-2-羟甲基氧杂丙烷 57.1 10.0 联苯基硫杂葱酮，六氟磷酸硫盐 BPITX-PF（23%碳酸丙酯） 黄颜料（Y13） 流平剂BYK361 17.4 15.0四官能度PEA 52.5 PEGDMA 22.5, 二氧化钛 25.0The synthesis of hydrophilic polymers with functional groups involves the addition of monomers containing hydroxyl or carboxyl groups to the formulation. Common functional groups used include methacrylic acid and other acrylic derivatives. The process typically requires a suitable reaction environment, such as the presence of a photoinitiator to facilitate polymerization under UV light. Conditions such as temperature and time should be carefully controlled to optimize the polymer integrity and functional group availability. After the synthesis, the polymers may be further characterized and modified to enhance hydrophilicity and compatibility with the desired application.To synthesize hydrophilic polymers with functional groups, mix 20 parts of multi-functional PUA, 10 parts of EA, and 22 parts of GPTA.四官能团PEA（CN294）: 30.0, 颜料: 19.0, 滑石粉: 5.0; 六官能团PEA（CN293）: 18.6, 活性胺（CN373）: 2.0, 颜料: 5.0.双官能度PEA（PRO7978） PEA(CN2203) GPTA 907 TZT 35.0 KS300 23.0 ITX 8.0 3.5 滑石粉 3.0 0.5 品颜料（CibaMagentaSMA） 20.0 4.0The synthesis of hydrophilic polymers involves the use of the following components in specified ratios: FA (PRO8008A) 28, PEA (CN2203) 20, Di-TMPTA 11, (EO)TMPTA 5, 907 3, KBI 5, active amine (CN373) 2, red pigment (P.R.57:1) 20, talcum powder 2, polyethylene wax 2. The total formulation also includes other PEA variants: PEA (PRO30037) 27, PEA (CN2282) 20, Di-TMPTA 11, (EO)TMPTA 2, and TZT 2.四官能度PEA 25.0, 四官能度EA 37.0, 四官能度GPTA 4.0, 稳定剂 1.0, 填料 0.5, 蓝颜料PB15:3 17.0, 光引发剂 6.0, 蜡 10.0.The synthesis of hydrophilic polymers with functional groups involves the following components: Tri-functional PEA (38.1), PE(EO)TA (30.5), pigment dispersant stabilizer (2), ITX (0.5), and an active amine (5.0). Additional components include DPGDA (17), and Esacure1001 (3.5). The mixing ratios and sequence of addition are critical for achieving the desired polymer characteristics.Combine the following components: PEA (39.3), Esacure 1001 (3.5), PE(EO)TA (31.0), KT55 (3.0), carbon black (23.3), 651 (3.0), and additives (6.4), including active amine (4.0) for the synthesis of hydrophilic polymers with functional groups.Use a mixture of four-functional acrylate (EB40) at 26.8 parts, TPO at 2.0 parts, PEA (EB2958) at 13.0 parts, ITX at 0.5 parts, amine-modified acrylate (EB7100) at 5.0 parts, EDAB at 5.0 parts, DPGDA at 5.5 parts, Tego Rad2300 at 1.5 parts, Kronos 2063S at 40.0 parts, and Tego Dispers 655 at 0.7 parts for synthesis.多官能度PEA 13.0 ITX 0.5, 四官能度聚丙烯酸酯 26.8 EDAB 5.0, 胺改性聚丙烯酸酯 5.0, 胺改性聚丙烯酸酯 5.0, DPGDA 25.5 Rad2300 1.5, $T_{1}0_{2}$ 20.0 TEGODispers655 0.7, TPO 2.0The synthesis of hydrophilic polymers with functional groups involves mixing the following components: EA (20 g), epoxy methacrylate (15 g), diacrylate of bisphenol A (20 g), propylene glycol triacrylate (10 g), BP (8 g), TEA (3 g), ultrafine PTFE wax (2 g), and White EX-102 (22 g).聚酯四丙烯酸酯（EB657）与苯乙烯-马来酸酐共聚物（SMA1440F）以比例合成，其中采用(EO)4PETA(SR494)作为交联剂，添加巴西棕榈蜡作为增塑剂，表面活性剂、磺化麻油、癸二酸二丁酯及UV稳定剂以功能化。具体配方为：EB657 30.0g, SMA1440F 10.0g, (EO)4PETA(SR494) 17.0g, 巴西棕榈蜡 3.0g, 表面活性剂 4.0g, 磺化麻油 2.0g, 癸二酸二丁酯 3.0g及UV稳定剂 1.0g。The synthesis involves mixing TPGDA (30.0 g), acrylic resin (Elvacite2013) (5.0 g), active amine (15.0 g), polysiloxane (2.5 g), TMP(EO)TA (1.0 g), N-vinylcaprolactam (20.0 g), and pigment (7.0 g) in appropriate proportions.脂肪族PUA TPGDA NVP 4.5 50.0 16.5 8.5 1.0 EDAB 颜料 填料 硅消泡剂 1.5 7.0 10.0 1.5二官能度脂肪族PUA（611A-85，含15%TPGDA） (PO)NPGDA PETA 80 10 10 2 磨砂料（5378）活性胺（Etercure6420） 5 消泡剂（FoamexN）等 4 平滑剂（Eterslip70） 0.2(PO)NPGDA 10二官能度脂肪族PUA（611B-85，含15%HDDA）改性EA（6231A-80，含20%TPGDA），加入50，184，1，20 BP 2，以及活性胺（EterCure6420）5。To synthesize hydrophilic polymers with functional groups, combine the following components in specified amounts: 25 parts of di-functional aliphatic PUA (611A-85, containing 15% TPGDA), 20 parts of (622A-80, 20% TPGDA), 15 parts of TMPTMA, 20 parts of (EO)TMPTA, and 10 parts of HDDA. Then, add 4 parts of BP, 10 parts of active amine (Etercure6420), 5 parts of defoamer (FoamexN), and 0.2 parts of smooth agent (Eterslip70).先研磨A得到色浆，再加人B组分，继续研磨均匀即为UV蓝色印刷油墨。Mix the following components to prepare the hydrophilic polymer: EA (30.0), TPGDA (15.0), EO-TMPTA (15.0), N-乙烯基己内酰胺 (20.0), and 丙烯酸树脂（Elvacite2013） (5.0). Add the active amine pigment in the ratio of 2.5, 2.0, 1.0, and 7.0 for optimal performance.To synthesize hydrophilic polymers with functional groups, combine the following components: PUA 20.0, TPGDA 30.0, Elvaclte2031 (acrylic resin) 16.0, N-vinylhexylamine 10.0, ITX 1.0, 651 3.0, DMEA 1.5, pigments 7.0, fillers 10.0, and silicone defoamer 1.5. Mix thoroughly to create the desired polymeric ink.Synthesize hydrophilic polymers by combining the following components: 35 parts EA (Ethyl Acrylate) Chlorinated PEA, 20 parts TMPTA (Trimethylolpropane Triacrylate), 10 parts TPGDA (Tripropylene Glycol Diacrylate), and 2 parts 184 (photo initiator). Stir and mix the components thoroughly to ensure uniformity in the formulation.To synthesize hydrophilic polymers with functional groups, use the following components in the specified quantities: 27.75 parts of low-viscosity PUA (CN987), 10.00 parts of low-viscosity monoacrylate oligomer (CN131), 6.00 parts of non-migrating, non-yellowing photoinitiator (SR1113), and 0.25 parts of wetting agent (SR022).芳香酸丙烯酸酯半酯（SB520E35） 46.0 低黏度单丙烯酸酯低聚物（CN131） 22.0 POEA 20.0 907 4.5; ITX 0.5 BP 2.0 炭黑（Raven450） 4.0; 低黏度脂肪族PUA（CN987） 低黏度单丙烯酸酯低聚物（CN131） 三官能团丙烯酸树脂（SR9051） 非迁移无黄变光引发剂（SR1113） 27.75 10.00 30.00 TiO2(R-900) 25.00 润湿剂（SR022） 0.25 非硅流平剂（SR012） 1.00.No specific experimental protocol for the synthesis of hydrophilic polymers with functional groups is provided in the text excerpt.使用端环氧基硅氧烷（SM-A）和脂肪族单体（AM-D）以比例38.0:38.0混合，加入BYK30（0.2）和白颜料（Kronos2020，10.0）.合成光固化胶黏剂的步骤包括使用低聚物、活性稀释剂和光引发剂。确保选用的原料中含有能够产生化学反应的活性基团，以促进胶黏剂与被粘连材料之间的粘接性能。在必要时，利用偶联剂促进胶黏剂与被粘物的表面之间形成化学键结合。对被粘物表面进行处理，使之产生活性基团（例如 -OH、-ONO2等），以提高粘接力和润湿性。最后，通过光源固化胶黏剂，确保固化过程没有环境污染并维持材料性能的稳定性。将有机硅丙烯酸酯低聚物与光引发剂配成的涂布液涂覆在基材（纸基或塑料薄膜）上并经UV固化，以制得UV离型材料。涂布量 60g/m2 ，固化时间30s，粘接强度 25N/2.5cm ，附着力 85N/6.25cm 。将脂肪族PUA（CN966） 50 四乙氧基壬基酚丙烯酸酯（CD504） 40 二乙醇胺 KIP100F 3与光敏剂混合，涂布于PET膜上，UV固化，得到胶膜。Mix the components: 78 parts BA, 0.5 parts double acetone acrylamide, 20 parts MMA, 0.25 parts hexanedioic acid dihydrazide, 2 parts AA, and 0.6 parts 2BP. The reaction should be performed under appropriate conditions to ensure the formation of the hydrophilic polymer with functional groups.用过硫酸盐引发乳液聚合，用其乳液粘聚丙烯薄膜与纸板，UV固化。配方中含有PETA、三乙二醇二乙烯基醚（DVE-3）作为主要成分，用于聚酯与聚酯层压。脂肪族聚醚型PUA EO-TMPTA 40 20 HDDA NPGDA; 脂肪族聚醚型PUA 40 EO-TMPTA 35 HDDA 20 1173 5; 脂肪族PUA 40 PEG(400)DMA 35 PETA 20 184 5; EA 15 IBOA 40 12 脂肪族PUA 1173 5 TPGDA BYK307 0.2; HEA 6 BMA 25 1,4-BDDMA 68 651 1.由TDI、聚乙二醇、甲基丙烯酸羟乙酯合成的聚氨酯甲基丙烯酸酯。用于LCD封口和TN-LCD金属管脚固定的聚合物合成中，使用的原料配方为：EA 50.0, HEMA 17.6, BA 5.2, PETA 1.8, KH-550 0.6。Prepare a mixture containing 100.0 parts of EA (ethyl acrylate), 17.5 parts of active amine, and 1.0 part of silane coupling agent. Add to this, 17.5 parts of allyl bisphenol A acrylate and 1.0 part of MMA (methyl methacrylate) 1173. Stir the mixture to obtain a homogeneous solution.The synthesis involves mixing the following components: 70 parts of EA (Ethyl Acrylate), 20 parts of TMPTA (Trimethylolpropane triacrylate), 4 parts of triphenyl phosphine, 4 parts of tertiary amine, 2 parts of 651 (a specific amine compound), and 2 parts of n-butylamine.EA(CYD128) 100, Coupling Agent Titanate 35, Dipropylene Glycol Dibenzoate 5, Butyl Phthalate 4, HQ 0.15HEMA C16~C20二元羧酸二缩水甘油醚丙烯酸酯 85 UP 35 651 90 100 2聚酯芳香族PUA PEA(EB524) 20.0 1173 5.0 184, TPGDA 12.0 3.0, TMPTA, 大分子表面活性剂 0.5 0.6.芳香族PUA: 45g, IBOA: 50.5g, 1700 增塑剂: 1g丙烯酸共聚物（MMA：BA：VAc：AA：MAA= 85 50:40:5:3:1.5) 二甲基丙烯酸乙二醇酯 2 BEE 1 增塑剂邻苯二甲酸二辛酯 10 硅烷偶联剂（A-171） 2; 固化速率/s 3~5; 耐热性（100℃水煮2h） 无气泡及缺陷; 透射率/% 88.7; 耐光老化/% 97.4; 抗穿透性（钢球2.26kg，4m冲击） 不穿透; 抗冲击性（40C钢球227g，12m落下） 不穿透.The synthesis of hydrophilic polymers involves the use of PUA EHA at a ratio of 45.0 to 20.0, the addition of a tackifier at 5.0, and BEE at 0.5.在丙酮-丙醇混合溶剂中自由基聚合，除去溶剂，混合 $0.5\\%$ 的907，制得UV热熔胶。脂肪族PUA 45.0, TPO 5.0, IBOMA HDDA 22.0 23.0, 附着力促进剂 2.0, 助剂 2.5铜粉预处理在铜粉中加人无水乙醇为介质，氮气保护下用行星式球磨机球磨20h，除去无水乙醇，得珠光色粒径1～10μm片状铜粉。用浓度5%的稀硫酸溶液洗两次，再用无水乙醇洗两次，加入质量分数4%的偶联剂KH-570快速放人真空干燥箱干燥备用。将8.51g AgNO3溶于去离子水中，搅拌下慢慢放入氨水，至溶液呈透明无沉淀状态。再加去离子水至 100mL，配成银氨溶液。将1.81g 38%的甲醛加入到120mL无水乙醇中，搅拌混匀，配成还原液。将10g 200目铜粉在真空球磨机中球磨10h，取出用5%的稀 H2SO4 和无水乙醇分别洗涤两次，滤去清液，放置于250mL三口烧瓶中，加入还原液，搅拌均匀，升温至50℃，边搅拌边滴加银氨溶液，滴加完继续反应1.5h，过滤，将得到的粉末用5%的稀 H2SO4 和无水乙醇分别洗涤两次，滤去清液后再重复上述步骤两次，将最后得到的粉末洗涤干燥后。真空球磨处理 $^{10\\mathbf{h}}$ ，得到片状镀银铜粉。The synthesis of hydrophilic polymers is carried out using the following components: EA N-VP (3.00 g), BP (0.08 g), and a mixture of photopolymerizable resin (100 g), silver-coated copper powder (70 g), azobisisobutyronitrile (2 g), and silane coupling agent KH-570 (3 g). The final electrical resistivity achieved is approximately 1.5×10^-Ω.cm.涂覆感光性树脂→正面和背面同时UV曝光→显影→干燥后曝光→印刷。在制版机玻璃板上安放阴图底片，覆盖聚酯薄膜，浇注液体感光性树脂至一定厚度，放上聚酯片基，然后用紫外灯上下同时曝光。下侧正面曝光，使见光部分树脂交联固化形成图文部分，上侧背面曝光，使图片部分黏附于聚酯片基上。曝光完毕，回收未曝光树脂，取出版材，经显影、干燥，再次UV充分曝光，使细小的图文部分彻底固化，制成印版。将饱和聚合物、交联剂和光引发剂混合均匀后，涂布到带有防光晕层的聚酯片基或铝基上，干燥后即制成固体感光性树脂凸版。也有将固体树脂版组分共混后，经挤出成型而制得。随后，覆盖阴图底片，进行UV曝光，显影，干燥，后曝光，以提高印版硬度，最终制成印版。The synthesis protocol involves using elastic synthetic rubber resins such as polybutadiene, polyisoprene, polybutadiene-styrene copolymer, polyurethane, and polyethylene-vinyl acetate copolymer. The crosslinking agent is a multifunctional acrylic monomer, such as pentaerythritol tri/teacrylate or trimethylolpropane triacrylate. A photoinitiator such as benzoin ethers, acyloximes, or benzoyl compounds is used. The resin layer is formed by blending the rubber resin, crosslinking monomer, photoinitiator, and thermally resistant additives and then extruding the mixture. The process includes back exposure with UV light to increase the thickness of the base; followed by placement of a photographic negative, front exposure with UV light to induce crosslinking in exposed areas; developing to wash away unexposed areas; drying; and final post-exposure with UV light for complete curing, followed by anti-adhesion treatment to complete the printing plate.在曝光成型机中，在下玻璃板上铺上阴图底片，覆盖聚酯薄膜，涂覆液体感光树脂到所需厚度，覆盖聚酯片基，压好上玻璃板。再背面UV曝光，然后正面UV曝光，见光部分发生光交联固化，与背面曝光固化部分连接一起形成图文，接着背面全面UV曝光，形成版基，回收未固化的感光树脂后，再经显影、水洗、干燥，最后用紫外灯对版面全面曝光。在铝基材上涂布感光树脂层，并在干燥后进行紫外光照射以使重氮基分解，产生氮气并通过分子内重排形成烯酮。烯酮在水存在下水解生成羧基。用碱性显影液处理去除感光部分，露出铝基材。将阳图底片与阳图型PS.版真空贴合，紫外曝光，一般采用金属卤素灯（如碘灯）或中压汞灯。显影一般采用硅酸钠、磷酸钠、碳酸钠或有机胺等碱性水溶液。版面经除脏、修补、干燥后，即成印版。有时为了提高耐印力，还可采用高温烤版。将阴图底片与阴图型PS版真空贴合，紫外曝光，一般采用金属卤素灯（碘灯）或中压汞灯。显影一部分是用稀碱液如碳酸钠，还有一部分是要用溶剂。版面经除脏、修补、干燥后，即成印版。选择一定目数的丝网（有尼龙、聚酯、不锈钢、铜、镍丝网等）在木框或铝框上绷紧，用绷网胶粘在网框上，使其具有一定的张力。再涂覆感光胶，在40℃士5℃烘箱中干燥。一般要涂两遍，最多三遍。放上底片，真空吸片；因网印感光胶吸收400nm左右的紫外光。采用制版荧光灯或金属卤素灯曝光。经用水显影后，干燥，修版，制成印版。丝网印版使用完后，还可以脱膜回收，使用脱膜液，除去感光胶后，丝网可重复使用。绷网 → 粘贴感光膜 → 晒版曝光 → 显影 → 干燥 → 印版将18.4g（0.1mol）对氨基二苯胺溶于5%的盐酸溶液，冷至0℃，搅拌下慢慢滴加6.9g（0.1mol）亚硝酸钠的浓水溶液，保持0～5℃，加毕，继续搅拌0.5h。加人6.8g理论量稍过量的氯化锌结晶，充分振荡后放置，析出对重氮二苯胺氯化锌复盐结晶，过滤后自然晾干，产率90%以上。将9.4g（0.05mol）2-氯-5-硝基苯甲醚和11.5g（0.13mol）吗啉充分混合，升温至155℃，搅拌反应，减压蒸馏除去未反应的吗啉，冷却加人40mL水，析出固体，捣碎、抽滤，滤渣用40mL 6mol/L硫酸加热溶解，冷却，在<15℃放置过夜，此时未反应完全的原料2-氯-5-硝基苯甲醚以固相析出，过滤，滤渣回收，滤液用浓氨水中和至pH=7-8，析出黄色沉淀，冷却抽滤，水洗两次，真空干燥，得黄色固体产品2-N-(2-甲氧基-4-硝基苯基）吗啉（A）8.8g，产率82.2%，熔点102.5~103.5℃。将13.7g二氯化锡（SnCl2·2H2O）溶于35mL浓盐酸中，在剧烈搅拌下加人3.57g A，用冷水浴冷却，控制反应温度<70℃，约几分钟后，硝基化合物全部溶解，反应温度开始下降，同时析出大量白色不溶物，70℃反应2.5h，冷至室温，置冰水水浴中静置1.5h，充分沉淀，抽滤，白色滤渣用20mL水溶解，用30%的氢氧化钠溶液中和，直至所生成Sn(OH)4全部溶解，冷却抽滤，水洗至弱碱性，真空干燥，用1:3.5的乙醇水溶液重结晶，得白色产品3-甲氧基-4-吗啉基苯胺(B)2.85g，收率88.8%，熔点130~130.5℃。将2.088g B溶于10mL 6mol/L盐酸中，用冰水浴冷至0℃后滴加0.85g (0.012mol）亚硝酸钠和2mL水配成的溶液，控制滴加速率，使反应温度在2~4℃，加毕搅拌15min，用淀粉KI试纸检验显蓝色，剧烈搅拌，滴加由2.5g(0.007mol) SnCl4·5H2O和35mL水所配成的溶液，很快析出黄色沉淀，在0℃放置15min充分沉淀，迅速抽滤，立即真空干燥，得产品3-甲氧基-4-吗啉基苯基重氮四氯化锡复盐（C）3.8g，收率99%，该重氮盐紫外光谱吸收波长为320~480nm，λmax=408nm。在三口烧瓶中加入 10g 聚乙烯醇（05-88)、5g对二甲氨基苯甲醛、100g 冰醋酸和 0.3g 催化剂对甲苯磺酸，升温至 80~100℃ ，反应2h，加人 5g 马来酸酐、0.01g 对苯二酚，升温至 100~115℃ 反应 2h ，减压蒸馏除去溶剂，提纯，得到产物为聚乙烯醇环缩二甲基苯甲醛的马来酸酯，具有感光性。在三口烧瓶中加人 10g 聚乙烯醇 (05-88)、 2g 对二甲氨基苯甲醛、 100g 冰醋酸、 0.38 对甲苯磺酸，升温至 80~100°C 反应 2h，加人 10g 羟甲基丙烯酰胺，在 90~100°C 反应2h，减压蒸馏除去溶剂，提纯，得到黄色固体，为聚乙烯醇环缩二甲氨基苯甲醛的丙烯酰胺缩合物，具有感光性，产率 85%。将6.3g (0,05mol) 连苯三酚溶于 10.5mL (0.1mol) 30% 的盐酸溶液中，搅拌，加热到 80℃，使连苯三酚全部溶解，再降温至 55℃，缓慢滴加 6.58g (0,05mol) 乙酰乙酸乙酯，滴加完缓慢升温至有棕黄色物质析出，停止反应，抽滤水洗，再用乙酸乙酯洗，抽滤，50×干燥，用乙醇重结晶，得A（7,8-二羟基-4-甲基香豆素）。将2,1,5-重氮萘磺酰氯（或2,1,4-重氮萘磺酰氯）与A以摩尔比 2:1 溶解在丙酮中，恒温 40℃，搅拌下2h内滴加2mol三乙胺，加毕再反应2~3h，将反应液倒入十倍蒸馏水中洗涤，过滤水洗，40℃干燥至恒重，得到B，为重氮萘感光剂，整个过程避光。将6.3g（0.05mol）连苯三酚溶解在31.5mL（0.3mol）盐酸溶液中，加热至65℃，全部溶解为黑色透明液体，降温至55℃，加人11.4g（0.05mol）二苯基羟基乙酸，升温至78℃，搅拌混合均匀，滴加40mol无水乙醇，在78℃反应5h，冷却旋蒸除去乙醇，用甲苯重结晶抽滤，50℃干燥，得无色结晶体A（6,7-二羟基-3,3-二苯基-3H-苯并呋喃-2-酮)，熔点 $186^{\\circ}\\mathrm{C}$ ，产率 $44.65\\%$。将2mol2,1,5-重氮萘磺酰氯（或2,1,4-重氮萘磺酰氯）与1molA溶解于丙酮中，恒温40℃，搅拌下于2h内滴加2mL三乙胺，加毕再反应2～3h，将反应液倒人十倍蒸馏水中洗涤，过滤、水洗，40℃干燥至恒重，得到B为重氮萘感光剂(整个过程需避光)。在三口烧瓶中加人11.0g（0.10mol）对苯二酚、60mL丙酮搅拌溶解，升温，滴加8.0g（0.045mol）甲苯二异氰酸，回流反应2.5h。冷却，倒入适量去离子水中，析出白色沉淀，抽滤，固体真空干燥，得产物A16g，产率88.9%。在三口烧瓶中加人16gA和30mL二氧六环，搅拌溶解，滴加5.4g1,2-蒸二叠氮-5-磺酰氯和20mL二氧六环混合液，再加人2.5g碳酸钠固体和5mL去离子水，搅拌、升温至60℃反应1.5h，65℃反应1h，冷却后倒入盐酸水溶液中析出黄色沉淀，抽滤，用去离子水洗至中性，真空干燥，得产物为聚氨酯叠氮萘鼠磺酸酯。将（4-N，N-二苯氨基）-苯甲醛和磷叶立德试剂（摩尔比为1.5：1）和适量二甲基甲酰胺加人三口烧瓶中，通氮气，冰浴冷至0℃，加入等物质的量的甲醇钠，0℃搅拌30min，室温搅拌24h，用甲醇沉淀，过滤，用二氯甲烷/乙醇重结晶，得黄色固体A为4-[4-(甲硫基)苯乙烯基]-N,N-二苯基苯胺，产率70%，熔点185.4～187.2℃。将A溶解在80mL干燥的二氯甲烷中，加入三氟磺酸甲酯（摩尔比为5.1：6.1)。室温避光搅拌反应4h，蒸出溶剂后，用乙醇沉淀，得黄绿色固体B，产率70%，熔点151.2～159.5℃，为硫盐光产酸剂。1. Dissolve 4-diethylaminobenzaldehyde and phosphorus ylide reagent (molar ratio 1.5:1) in dimethylformamide in a three-neck flask, purging with nitrogen, and cool to 0°C. 2. Add an equimolar amount of sodium methoxide, stir for 30 minutes at 0°C, and then stir at room temperature for 24 hours. 3. Precipitate with methanol, filter, and recrystallize the filter cake using dichloromethane/ethanol to obtain yellow-green solid A, which is 4-[4-(methylthio)styryl]-N,N-diethylphenamine, with a yield of 30% and a melting point of 143.5–144.7°C. 4. Dissolve A in 80 mL of dry dichloromethane, add trifluoromethanesulfonic anhydride (molar ratio 5.1:6.1), and stir in the dark at room temperature for 4 hours. 5. Evaporate the solvent, precipitate in ethanol, and recrystallize from acetonitrile/ether to yield light yellow solid B with a yield of 40%.将改性不饱和聚酯与安息香异丁醚、HEA、2,6-二叔丁基对甲苯酚混合，配比为：改性不饱和聚酯 100.0，HEA 30.0，2,6-二叔丁基对甲苯酚 30.0。使用双丙酮丙烯酰胺、安息香乙醚、对甲氧基苯酚以及HEMA，具体配比为：不饱和聚酯 HEMA 100.0，双丙酮丙烯酰胺 20.0，安息香乙醚 20.0，对甲氧基苯酚 10.0。将不饱和聚氨酯与BP及2,6-二叔丁基对甲苯酚混合，具体配比为：不饱和聚氨酯 120.3，BP 7.3，2,6-二叔丁基对甲苯酚 1.5，0.1。对于醇溶性聚酰胺与TEGDA、间-二甲苯双丙烯酰胺、N-羧甲基丙烯酰胺-双乙二醇醚，配比为：醇溶性聚酰胺 70.0，安息香甲醚 7.0，对甲氧基苯酚 14.0，甲醇 8.2。此外，使用醇溶性聚酰胺、对-苯二亚甲基双丙烯酰胺、六次甲基双丙烯酰胺、TEGDA与丙烯酸丁二醇酯进行合成，配比为：醇溶性聚酰胺 100，顺丁烯二酸酐 32，安息香甲醚 21，对苯二酚 10，甲醇 1，1，0.002，500。最后，组合不饱和聚酯、DEGDA与丙烯酰胺，配比为：不饱和聚酯 70.0，安息香甲醚 15.0，对-叔丁基邻苯二酚 15.0，2.0，0.1。1. Prepare a mixture containing polyvinyl alcohol with a saponification degree of 80.5% and a degree of polymerization of 500 (70.0 g) and polyvinyl alcohol with a saponification degree of 88.5% and a degree of polymerization of 500 (30.0 g). 2. Add HEMA (100 g) to the mixture. 3. Include benzyl isopropyl ether (2.5 g), p-methoxyphenol (0.2 g), and a 5% aqueous solution of diiodofluorescein (0.5 mL) to the mixture. 4. Finally, incorporate ethylene glycol dimethacrylate (5.0 g) and water as necessary for the synthesis.四种溶液混合搅拌 $30\\mathrm{\\sim}40\\mathrm{min}$ ，抽滤置于棕色瓶中，避光、避潮湿待用。混合上述化学品：重氮树脂、乙二醇单甲醚、丙烯酸共聚树脂、二甲基甲酰胺以及醇溶蓝。按照配方将其在混合溶剂中溶解。使用的混合溶剂为甲乙酮和水的混合物。将甲基丙烯酸烯丙酯与甲基丙烯酸以50.0的比例共聚，加入油性蓝603 1.0，TMPTA 20.0，二十二碳酸 1.5，4-重氮二苯胺-甲醛缩合物六氟化磷盐 3.0，乙二醇独甲醚 500.0，2，4-二甲基-硫杂葱酮 2.0，甲醇 150.0，2,4-二（三氯甲基）-6-（4-甲氧基）1，3，5均三嗪 2.0，甲基乙基酮 300.0。甲基丙烯酸甲酯-甲基丙烯酸共聚物（摩尔比9：1） PETA 特丁基慈 2.0 53.8 乙基紫 43.7 丁酮 对甲氧基苯酚 300.0 0.4 0.1; 甲基丙烯酸丙酯-甲基丙烯酸共聚物 3.2 结晶紫 0.1 PETA 1.7 甲基乙基酮 20.0 2，4-二甲基-硫杂葱酮 0.1 丙二醇单甲醚乙酸酯 20.0 2,4，6-三（三氯甲基）-1，3，5-均三嗪 0.1 含氟阴离子表面活性剂 0.031. Prepare a mixture of styrene-maleic anhydride copolymer, ethyl acrylate/methyl methacrylate/acrylic acid copolymer, and TEGDMA in the specified proportions. 2. Use a mixture of chloroform and methanol as solvents. 3. For light-sensitive resin formulation, combine methyl methacrylate, acrylic acid, and styrene in a 1:2:0.5 ratio with a crosslinking agent. 4. Add a photoacid generator dissolved in tetrahydrofuran. 5. Utilize a mixed solvent of n-butanol, water, and pentanone at a ratio of 60:20:20, and heat to 70°C, followed by drying for 75 seconds. 6. For additional formulations, use similar proportions and solvents as described, making sure to incorporate the functional groups and crosslinkers as required.重铬酸盐-胶体聚合物系光刻胶主要由重铬酸盐和胶体聚合物组成。重铬酸盐多采用重铬酸铵，而常用的天然胶体聚合物有明胶、蛋白质、淀粉等；合成聚合物则有聚乙烯醇、聚乙烯吡咯烷酮、聚乙烯醇缩丁醛等。在使用前现配现用，避免存放导致暗反应。The synthesis of hydrophilic polymers involves using cyclized rubber with double bond groups as the film-forming resin and aromatic diazide compounds as crosslinking agents. The film-forming resin, cyclized rubber, is obtained by polymerizing isoprene into polyisoprene and then undergoing cyclization in the presence of an acidic catalyst. The crosslinking agent decomposes under UV light to form aziridines, which abstract hydrogen from the polymer backbone, generating free radicals that promote crosslinking between different polymer molecules, resulting in an insoluble polymer.215邻重氮萘磺酸酯或214邻重氮萘磺酸酯的合成采用相应的邻重氮萘磺酰氯与多羟基化合物进行酯化反应，所用的多羟基化合物包括2,3,4-三羟基二苯甲酮和$^{2,3,4,4^{\\prime}}$ -四羟基二苯甲酮。酯化度一般在60%～80%。成膜树脂是由甲醇和甲醛水溶液在酸催化下缩聚而成的线型酚醛树脂。(1) 聚乙烯醇肉桂酸酯的合成（一）：将 11g 聚乙烯醇放到 100mL 吡啶中，在水浴上加热使其溶解，补加 100mL 吡啶，温度降到 50°C 以下，滴加 50g 肉桂酸酰氯，在 50°C 继续反应4h，生成的黏稠块状物溶于四倍丙酮中，过滤后注入水中析出聚乙烯醇肉桂酸酯，过滤，水洗，暗处晾干，得 31g 聚乙烯醇肉桂酸酯。(2) 聚乙烯醇肉桂酸酯的合成（二）：将精制的聚乙烯醇放人 95~100°C 溶剂吡啶中膨润，在 50°C 时，滴加肉桂酰氯，聚乙烯醇：肉桂酰氯摩尔比为1:（1.2～1.3），加毕继续反应5h，再加丙酮稀释，在水中沉淀、洗净，干燥得到聚乙烯醇肉桂酸酯。(3) 聚乙烯醇肉桂酸酯的合成（三）：将精制的聚乙烯醇溶于温水中，加入氢氧化钠水溶液，冷却至 0°C，成为碱溶液。在 0°C 剧烈搅拌下滴加溶解在丁酮中的肉桂酰氯，聚乙烯醇摩尔比为 1.3:1，继续在 0°C 反应1.5h，反应完毕，在 0°C 下静置，生成的聚乙烯醇肉桂酸酯溶于上层溶液中，分出上层溶液在汽油中沉析，过滤、脱水、干燥得到聚乙烯醇肉桂酸酯。(4) 聚乙烯醇肉桂酸酯的合成（四）：将100mL浓度1mol/L的聚乙烯醇溶液和100mL4mol/L的氢氧化钾溶液混合，加人100mL丁酮，在搅拌下加人24mL甲苯和116mL溶有1.2mol肉桂酰氯的丁酮溶液，在0~5℃反应2h，反应结束静置，将上层有机层滴入甲醇中，析出聚乙烯醇肉桂酸酯，产率几乎是100%。(5) 聚乙烯醇肉桂酸酯的合成（五）：在三口烧瓶中加入精制的聚乙烯醇44g（1mol)、无水吡啶400mL，隔绝水汽下100℃溶胀24h。再加人3.5mL二氧六环，冷到45℃，滴加200g（1.2mol）肉桂酰氯和50mL二氧六环混合液，在50~55°C用1~1.5h加毕，继续揽拌 3h，再加人少量乙酸酐继续反应1h。冷却加丙酮稀释，过滤除去吡啶盐后，滤液沉析于大量去离子水中，过滤洗至无氯根，再用乙醇浸泡过夜，过滤产物在60°C下干燥，得到固体产物为聚乙烯醇肉桂酸酯，得率约90%。(6) 聚乙烯氧乙醇肉桂酸酯的合成：将两分子氯乙醇在浓硫酸作用下脱水生成2，2'-二氯二乙基醚。(7) 2,2'-二氯二乙基醚在氢氧化钠作用下，加热至200~220℃，制得2-氯乙基乙烯基醚。用2-氯乙基乙烯基醚和肉桂酸钠在四甲基碘化铵存在下，回流反应4h，得到单体乙烯氧基肉桂酸乙酯。经精制后，在三氟化硼-乙醚催化剂作用下，于低温178℃进行阳离子聚合，得到聚乙烯氧乙醇肉桂酸酯。在避光条件下，将 \\\\(\\\\alpha\\\\) 澳代-2-蔡乙酮 \\\\(20\\\\mathrm{g}\\\\) 、 \\\\(100\\\\mathrm{mL}\\\\) 丙酮加入三口烧瓶中，在 \\\\(0^{\\\\circ}\\\\mathrm{C}\\\\) 时加入 \\\\(4.8\\\\mathrm{mL}\\\\) 水，搅拌下慢慢滴加四氢噻吩 \\\\(14\\\\mathrm{mL}\\\\)，加毕 \\\\(0\\\\%\\\\) 搅拌1h，产生沉淀后，室温下继续搅拌1h，滤出固体，用无水乙醇重结晶两次，得淡粉色晶体 S-(2-蔡甲酰)甲基四氢噻吩溴化物 \\\\(21.1\\\\mathrm{g}\\\\) ，产率 \\\\(78\\\\%\\\\)，熔点 \\\\(136\\\\sim137^{\\\\circ}\\\\mathrm{C}\\\\)。将 \\\\(3.6\\\\mathrm{g}\\\\) 上述溴化物、 \\\\(150\\\\mathrm{mL}\\\\) 乙晴加入三口烧瓶中，避光操作，搅拌下慢慢滴加 \\\\(3\\\\mathrm{g}\\\\) 对甲苯磺酸银的 \\\\(70\\\\mathrm{mL}\\\\) 乙腈溶液，室温反应 \\\\(24\\\\mathrm{h}\\\\)，滤出不溶物，浓缩滤液，将浓缩滤液倾入大量无水乙醚中，滤出固体用乙晴溶解，重复上述操作三次，得到纯的白色晶体 S-(-2-萘甲酰)甲基四氢噻吩对甲苯磺酸盐 \\\\(4.3\\\\mathrm{g}\\\\) ，产率 \\\\(94\\\\%\\\\)，熔点 \\\\(146\\\\sim147^{\\\\circ}\\\\mathrm{C}\\\\)。将 \\\\(8.6\\\\mathrm{g}\\\\) 对甲苯磺酸、5.1g氧化银加入三口烧瓶中，加 \\\\(120\\\\mathrm{mL}\\\\) 乙晴，避光操作，搅拌 \\\\(5\\\\sim8\\\\mathrm{h}\\\\)，滤出不溶物，滤液旋蒸至干得到白色固体，用丙酮洗三次，得白色对甲苯磺酸银固体 \\\\(12.3\\\\mathrm{g}\\\\)，产率 \\\\(97\\\\%\\\\) 。将3.36g对乙酰氨基苯甲醛溶于50mL乙醇中，滴加到3.74g间乙酰氨基苯乙酮、20mL乙醇、20mL4%的氢氧化钠水溶液的混合液中，在冰浴下搅拌3h，抽滤得到黄色固体（I）6.12g，产率为86.2%。将3.3g（I）加到150mL5%的盐酸溶液中，加热回流3h，冷却抽滤得到红色固体，用去离子水重结晶得到红色固体（Ⅱ）1.85g，产率为71.9%。将0.476g（Ⅱ）加人到三口烧瓶中，在氮气保护下，滴人6mL经蒸馏并用分子筛处理后的二甲基乙酰胺，搅拌溶解后加入0.436g均苯四甲酸二酐，室温搅拌48h，再加入3mL等摩尔比的乙酸酐和吡啶混合液，80℃下保温5h，随反应进行，体系黏度明显增大，搅拌变得困难，说明聚酰亚胺高分子形成。将反应液倒人大量冰水中，聚酰亚胺以丝状沉淀析出，抽滤后得深黄色固体，用乙醇洗涤，70℃下真空干燥8h，得黄色固体粉末即为光敏聚酰亚胺（Ⅲ）耐热400℃以上，紫外吸收λmax=365nm。配方A: 高分子量聚乙烯醇 2, 低分子量聚乙烯醇 10, 染料 适量; 配方B: 重铬酸铵 20; 按 A:B=3:1 (质量比)混合后立即使用。聚乙烯醇肉桂酸酯光刻胶参考配方: 聚乙烯醇肉桂酸酯 10g, 5-硝基 0.07g, 环己酮 100g, 添加剂 适量。聚乙烯氧乙醇肉桂酸酯光刻胶参考配方: 聚乙烯氧乙醇肉桂酸酯 15g, 环已酮 5-硝基 0.75g, 乙二醇乙醚醋酸酯。聚肉桂亚丙二酸乙二醇酯: 12g; 环已酮: 5-硝基 0.3g; 光刻胶感光区波长: 350~470nm; 分辨率: 1~2μm; 环化聚异戊二烯: 15.0g; 2,6-双（4-叠氮亚苄基）-4-甲基环已酮: 0.4g; 2，6-二叔丁基对甲苯酚: 适量; N-苯基-a-萘胺: 适量; 光刻胶感光区波长: 300~450nm; 负型水性化学增幅抗蚀剂: 邻甲酚醛树脂: 100g; 六甲氧基甲基三聚氰胺: 32g; 对甲苯磺酸二苯基碘盐: 10g单面板制作都用网印法，要网印三道油墨。制作工艺为：覆铜板 → 前处理 ★ 网印UV抗蚀油墨 ~ 紫外固化 → 腐蚀（有时需电镀） → 去膜→网印UV阻焊油墨 → 紫外固化 → 网印UV字符油墨 → 紫外固化 → 检验 → 成品。UV抗蚀油墨一般都选用酸酐改性的环氧丙烯酸酯、高酸值的聚酯丙烯酸酯或改性的马来酸酐树脂等碱溶性感光树脂作为主体树脂，与丙烯酸官能单体配合，光引发剂常用651或葱酿类如2-乙基葱酮，颜料大多用酞菁蓝，一般1%即可，还需加人较大量的填料如滑石粉；为提高触变性能，需加入气相二氧化硅等。含有一定数量羧基的碱溶性感光树脂，交联固化成膜后，必须要能溶于3%左右氢氧化钠溶液中，以便去除。UV阻焊油墨低聚物的合成主要选择耐热性好、绝缘性好、与铜黏附性好的树脂，如双酚A-环氧丙烯酸酯、酚醛环氧丙烯酸酯和聚氨酯丙烯酸酯。常用的是酚醛环氧丙烯酸酯。活性稀释剂选择多官能度丙烯酸酯配以单官能团羟基酯。光引发剂主要使用651或2-乙基葱。颜料一般以菁绿为主，用量不超过1%，可加入较多的填料以提高耐热性和减少体积收缩。为提高油墨与铜的附着力，需加人1%-2%的附着力促进剂，如甲基丙烯酸磷酯单酯或双酯。针对感光胶膜的制备，首先配制感光涂布液，该液体由胶黏剂、光聚合单体、光引发剂及其他添加剂组成。胶黏剂应选用高分子物质，通常经酯化或酰胺化改性的苯乙烯-马来酸酐共聚物。光聚合单体选择多官能团的丙烯酸酯，如PETA、TMPTA、TPGDA。光引发剂则可以使用651、1173、184等。随后，用丙酮、丁酮或无水乙醇等溶剂将感光涂布液涂覆在聚酯片基上，并进行干燥以制得感光胶膜。阻焊干膜的感光胶膜必须采用耐热性良好的感光性树脂，如环氧丙烯酸树脂或酚醛环氧丙烯酸树脂，水溶性阻焊干膜需要使用带有羧基的环氧丙烯酸树脂或酚醛环氧丙烯酸树脂。前处理包括去油、酸洗、水洗、刷板和干燥，以去除覆铜板铜箔上的油污、灰尘。油墨涂覆方法包括丝网满版漏印、帘涂、辊涂和静电喷涂。预干燥温度 80±5°C，时间一般为15至20分钟，远红外烘道5至6分钟，高红外烘道1至1.2分钟。UV曝光采用银盐片或重氮片作掩膜，以中压汞灯或金属卤素灯为光源，接触曝光。显影使用1.0%至1.5%的碳酸钠溶液，温度30±2°C，喷射显影30至120秒；可选择手工显影。水洗以洗去显影液，热风干燥50至60°C 1分钟，或烘箱干燥100°C 1至2分钟。检查抗蚀图像质量，修补缺陷。蚀刻使用酸性氯化铜蚀刻液，温度约50°C。去墨时使用5%的氢氧化钠水溶液，温度50至60°C，喷淋1分钟，或手工浸人后去墨。经热水洗、循环水洗、自来水冲洗，干燥后检查合格，转入后序工艺。光成像阻焊油墨的制作工艺流程为：经蚀刻、电镀的覆铜板→前处理→涂布油墨→烘干→第二面涂油墨→烘干→UV曝光→显影→热固化。油墨涂布可采用80~150目丝网满板漏印，油墨厚度（干后）20~25μm。干燥多采用热风干燥，单面板70~75°C，10~15分钟；双面板、多层板第一面70~75°C，8分钟，第二面70~75°C，10~20分钟。UV曝光用银盐片或重氮片作掩膜，以中压汞灯或金属卤素灯为光源接触曝光。显影用1.0%的碳酸钠溶液，20~30°C，喷射显影60~120秒，再水洗除去显影液，热固化在140~150°C下30分钟，以使油墨进一步发生热交联。主体树脂为碱溶性感光树脂和热固化树脂。活性稀释剂如TMPTA和PETA，一般使用二氰二胺、咪唑等高温固化剂。The synthesis of hydrophilic polymers involves mixing the following components: EA (10.30), ITX (1.40), a specific type of acrylate (3.40) which is made from n-nonylphenoxethyl acrylate and (ethylene glycol) bis(2-hydroxyethyl) dimethacrylate (1.00), and (PO)NPGDA (5.10). Additional components include LiNO3 (0.30), FC-430 (0.05), methoxyphenol (0.04), carboxylated acrylate (14.80), methanol (52.96), Rad Cure (5.10), and butanone (2.55). The mixing ratios and order of addition are critical for achieving the desired functional groups in the polymer.To synthesize hydrophilic polymers, use the following formulation: EA (Ethyl Acrylate) 25.0 g, TMPTA (Trimethylolpropane Triacrylate) 30.0 g, HEMA (Hydroxyethyl Methacrylate) 10.0 g, along with additives such as talc powder 30.0 g, SiO2 (Silicon Dioxide) 1.0 g, and an adhesion promoter at 0.5 g.The experimental protocol involves combining specific components to achieve hydrophilic polymers with functional groups. Use the following ratios: 24.0 parts of EA (CN144), 14.0 parts of ITX, 10.0 parts of BP, 7.0 parts of 菁绿, 0.5 parts of TMPTA, 2.0 parts of (EO)TMPTA, 0.5 parts of IBOA, 19.0 parts of HEMA, 3.0 parts of SiO (Aerosil200), and 1.0 part of non-silicone leveling agent (SR012). Ensure to maintain the correct order of mixing and reaction conditions as per standard polymer synthesis protocols.The synthesis of hydrophilic polymers involves the following components: FA (20), EA TMPTA (10-13), DPHA (3), HEMA (18), and BaSO4 (2).The synthesis of hydrophilic polymers with functional groups involves combining various components in specified ratios. Key compounds include 2-Ethylhexyl acrylate (2-EA), trimethylolpropane triacrylate (TMPTA), ethylene oxide (EO), isobornyl acrylate (IBOA), and hydroxyethyl methacrylate (HEMA). Additional materials such as SiO2, phthalocyanine green, and flow leveling defoamer are also incorporated in the synthesis. The specific amounts for each component are indicated in the provided data.To synthesize hydrophilic polymers with functional groups, combine 40 parts of aliphatic PUA, 28 parts of HEMA, and 18 parts of ethoxylated bisphenol A diacrylate. Additionally, include 5 parts each of PETA 651 and TMPTA.The synthesis involves mixing PUA, TMPTA, and HEMA in the following ratios: PUA - 25.0, TMPTA - 35.0, HEMA - 10.0. Additionally, pigments such as phthalocyanine green, talc powder, and SiO2 should be incorporated in the amounts of 0.5, 22.5, and 3.0 respectively.使用FA、TMPTA、HEMA和TPO 184混合物合成含官能团的亲水性聚合物。具体比例为：FA 10，TMPTA 10，HEMA 11，TPO 184 2。同时加入30的TiO2、30的滑石粉、10的SiO2、1的流平剂和3的其他成分。1. Combine the following components in specified amounts: Tri-functional aliphatic PUA (CN945B85) 20.0, HDDA 15.0, (EO)PETA 19.0, TiO2 20.0, THFA 10.0, BYK-LPN7057 1.0, Bi-functional amine initiator (CN386) 2.0, BYK333 0.5. 2. Mix thoroughly to ensure homogeneity. 3. Follow appropriate curing or polymerization steps as per standard procedures for crosslinking.马来酸酐聚合物 DPHA HEMA synthesis using a formulation of 40 parts maleic anhydride polymer, 6 parts HEMA, 10 parts ITX, 25 parts blue dye, and 1 part additives.The synthesis of hydrophilic polymers involves using high acid value reactive agents such as PEA or styrene-maleic anhydride resin. The specific formulation includes components like alkali-soluble hyperbranched polyester methacrylate and phenolic epoxy resin along with agents like melamine, 2,4-diamino-6-(1-methyl-1H-imidazolin-2-yl)-s-triazine, and other additives forming a mixture with specified ratios for effective cross-linking and function.The synthesis involves the use of high acid value photosensitive resin TMPTA 651 in combination with the following components: 35 parts high acid value resin, 5 parts talc, 7 parts SiO2, 1 part leveling agent, along with 30.0 parts anhydride modified FA, DPHA, HEMA, and other additives such as 15.0 parts SiO2, 10.0 parts ITX, 20.0 parts 907, 3.0 parts leveling agent (BYK405), and 1.0 part defoamer (acrylic silicone ester), followed by solvent addition, totaling 12.0 parts solvent. Additionally, 2.0, 1.5, 4.5, and 0.5 parts of other specified components are included.To synthesize hydrophilic polymers with functional groups, prepare the following components: 32.0 g of maleic anhydride-modified FA, 6.0 g of 651 ITX, 2.0 g of epoxy resin TMPTA, 8.0 g of 907, 10.0 g of HEMA, and 1.0 g of EDAB. Additionally, include 10.0 g of solvent with 20.0 g, 0.5 g of phthalo green, 5.0 g of talc as a defoaming agent and leveling agent, and 0.5 g of SiO2. Finally, add 1.5 g of imidazole as a catalyst.将组分A（六氢苯酐改性EA 55.0, SiO2 14.0, TPGDA 12.0, 菁绿 0.5-1.0, 三羟甲基丙烷二烯丙基醚 15.0, 消泡剂BYK361, 双氰胺 2.0, 流平剂BYK346 0.5）与组分B（甲酚醛环氧树脂 55.0, 双甲基丙烯酸丁二酯 25.0, 184, 三羟甲基丙烷二烯丙基醚 6.0, 8.5, 0.5）的比例为3:1混合，搅匀后使用。1. Mix 5.4 g of aromatic acid methacrylic half ester (SB500-E50) with 40.8 g of DPET/PA (SR-399). 2. Add 15.2 g of (EO)6TMPTA (SR-499) to the mixture. 3. Incorporate 1.0 g of I1850. 4. Include 2.3 g of Irganox1035 and 0.3 g of CPTX. 5. Add 11.5 g of blue pigment (LionelBlueES) and 3.5 g of dispersant BYK161 (30% SR399) to the solution. 6. Ensure uniform mixing of the components to form the hydrophilic polymer.芳香酸甲基丙烯酸半酯（SR500E50） 14.0, DPET/PA（SR399) 45.1, (EO)6TMPTA(SR-499) 13.7, Irganox1035 2.15; CPTX 绿颜料（HoliogenGreenL9361） 0.7, 黄颜料（PolioTolYellowDl819） 15.2, 分散剂BYK161（30%SR399） 3.5超支化聚酯通过偏苯三酸和环氧氯丙烷反应制得，最终用苯甲酰氯封端。所用的材料包括丙烯酸四氟丙酯、TPGDA、二氯甲烷和光引发剂784，反应的比例为20.0/1.2/100.0。The synthesis of hydrophilic polymers with functional groups involves the use of UV-curable coatings, specifically including polyurethane acrylic resins, modified epoxy acrylic resins, organosilicon acrylic resins, and polyester acrylic resins. The inner coating requires a low glass transition temperature (Tg) (below room temperature), high flexibility, low modulus over a wide temperature range (-60 to 100 °C), antioxidant properties, and a high refractive index. The outer coating necessitates a higher Tg and modulus for adequate mechanical strength and resistance to aging, acids, bases, solvents, and saline solutions. The use of reactive diluents such as hydroxyethyl acrylate and lauryl acrylate helps lower viscosity and enhance flexibility. The choice of photoinitiators is critical, with high-efficiency options being used to ensure full curing at high speeds (2000 to 3000 m/min).在实验中，将颜料与部分低聚物、活性稀释剂和分散剂在高效研磨设备中制备色浆，确保色浆的颗粒大小为≤1μm。然后，将色浆与剩余的低聚物、活性稀释剂、光引发剂和助剂（如消泡剂、流平剂、润湿剂和阻聚剂）一起研磨，制得光纤着色油墨。光引发聚合采用紫外光作为引发剂，适合于透明或半透明体系，如水溶液、微乳液、反相微乳液及分散体系。聚合反应利用光引发剂对紫外光的吸收，结合反应介质的散射效应进行，形成活性中心，并导致聚合速率在不同介质层的分布不均匀。For the surface graft polymerization of hydrophilic polymers with functional groups, three methods are outlined: 1) Gas-phase method: Place the polymer, monomer, and photoinitiator in a sealed glass container and heat to evaporate the solution, allowing surface grafting in the gaseous atmosphere of the monomer and photoinitiator. 2) Liquid-phase method: Dissolve the photoinitiator, monomer, and other additives in a solution, then immerse the polymer sample directly in the solution for grafting; alternatively, pre-coat the polymer sample with photoinitiator before immersion. 3) Continuous liquid-phase method: Feed the polymer substrate into a nitrogen-purged reaction chamber, treating it with a solution containing the photoinitiator and monomer, then expose to UV light through a quartz window. After grafting, remove excess monomer and photoinitiator with a suitable solvent, clean with acetone, and dry in air.将聚乙烯膜浸入二苯甲酮/氯仿溶液中（5~10分钟），取出晾干，再真空干燥至恒重。将该聚乙烯膜置于丙烯酸（含0.1%阻聚剂）的石英容器中，压实，用40W紫外光源照射接枝反应。反应后，用温水和氯仿充分洗涤并干燥至恒重。对于低密度聚乙烯膜，浸泡于含有二苯甲酮的丙烯酸溶液中，盖上聚丙烯膜，夹住氮气保护，在紫外灯下光照一定时间，反应完毕后用沸水清洗。对于低密度聚乙烯膜光接枝醋酸乙烯酯，注入光引发剂/醋酸乙烯酯溶液后进行紫外光照射，反应结束后清洗并干燥。各实验条件包括反应时间、溶剂浓度和温度等。The synthesis of hydrophilic polymers with functional groups involves selecting oligomers, photoinitiators, and reactive diluents. For free radical curing systems, common oligomers include epoxy (meth)acrylate, polyurethane (meth)acrylate, and polyester (meth)acrylate. Reactive diluents are chosen primarily to adjust viscosity and curing rate, with multifunctional acrylates preferred for their high reactivity and low viscosity. Photoinitiators must match the wavelength of the laser source used (e.g., He-Cd laser or Ar laser) and have high initiation activity. Additionally, additives such as defoamers, leveling agents, and stabilizers should be included in the formulation.1. Prepare the resin matrix using oligomers and reactive diluents. Use bis-GMA (bisphenol A diglycidyl methacrylate) as the primary oligomer to lower the double bond concentration to reduce volumetric shrinkage during polymerization. 2. Introduce UDMA (urethanedimethacrylate) to decrease viscosity and increase polymerization degree. 3. Add TEGDMA (triethylene glycol dimethacrylate) as a reactive diluent to enhance clinical operability and increase filler loading. 4. Use camphorquinone (CQ) as the visible light initiator, in combination with DMAEM (dimethylaminoethyl methacrylate) as an amine co-initiator for efficient polymerization upon exposure to visible light (470 nm). 5. Incorporate inorganic fillers, ensuring they are treated with a coupling agent such as KH570 (y-methacryloxypropyl trimethoxysilane) to enhance compatibility and bonding between the resin matrix and fillers. Solidify the composite under room temperature and visible light exposure.光聚合法制备水凝胶通常采用本体光聚合和界面光聚合。本体光聚合步骤为：将光引发剂溶于水凝胶前驱体溶液中，在适当的光照条件下，前驱体溶液经聚合、交联转化为水凝胶状态。界面光聚合步骤为：将光引发剂附着于细胞或组织表面，然后与水凝胶前驱体溶液接触，在适当波长的光照射下，在光引发剂和溶液界面形成水凝胶薄膜。光聚合水凝胶的合成可通过以下步骤进行：使用水溶性的高分子单体，如聚乙二醇丙烯酸酯和透明质酸衍生物，这些单体应包含两个或多个反应基团，并具有良好的生物相容性。化学合成的大分子单体可在UV光照下进行聚合反应，形成水凝胶。同时，天然高分子单体则通过酰化反应得到相应的丙烯酸酯或丙烯酰胺衍生物，并随后通过光交联反应形成水凝胶。可通过调整共聚物中链段的长度、单体浓度和聚乙二醇链段的长度来控制水凝胶的性能。The hydrophilic polymer is synthesized by accurately weighing a specific amount of the sample to be tested, dissolving it in ethanol or acetone (for more difficult to dissolve samples, it can be heated in a water bath), and adding 2-4 drops of phenolphthalein indicator. While stirring continuously, the solution is titrated with approximately 0.1 mol/L potassium hydroxide solution until a noticeable color change of the indicator occurs. The acid value is calculated using the formula A = (56.1V N/m), where A is the acid value in mg/g, V is the volume of KOH used in mL, N is the molarity of KOH in mol/L, and 56.1 is the molar mass of KOH in g/mol.1. 维氏溶液制备：将13g碘溶于1000mL冰醋酸中，稍加热至溶解，冷却后取200mL，通入纯干燥氯气，至橘红色消失为止。 2. 制备氯气的反应：MnO2 + 2NaCl + 2H2SO4 -> Cl2 + MnSO4 + Na2SO4 + 2H2O。 3. 准备0.1mol/L K2Cr2O7溶液。 4. 准备0.1mol/L Na2S2O3溶液。 5. 制备1%淀粉指示剂：将10g淀粉溶于蒸馏水形成糊状，迅速倒入1000mL煮沸的蒸馏水中，冷却并可加1.25g水杨酸防腐。 6. 准备15% KI溶液。 7. 准备氯仿(CHCl3)。 8. 准备碘。 9. 冰醋酸需无还原性杂质，若有则用8-10g高锰酸钾于800mL醋酸中精制，进行蒸馏收集118-119°C馏出物。称取样品于锥形瓶中，加入10mL氯仿，摇动使其溶解。用滴定管加入维氏液25mL，封口后在暗处于20°C存放30至60分钟。再加入KI液15～20mL，蒸馏水100mL，使用0.1mol/L Na2S2O3溶液滴定未被吸收的多余碘，至黄色褪尽，加入淀粉指示剂1mL，再以0.1mol/L Na2S2O3溶液滴至蓝色完全消失。同时进行空白试验，所有步骤相同但不加样品。1. 苯酐吡啶法\\n（1）试剂：\\n- 苯酐吡啶液：42g 苯酐溶于 300mL 无水吡啶中。\\n- 指示剂：1% 酚酸吡啶溶液。\\n- 滴定液：0.5mol/L 氢氧化钾乙醇溶液。\\n- 无水吡啶：含水量少于 0.1%。\\n\\n（2）测试方法：精确称取约 2g 样品，加入带有回流冷凝器的磨口锥形瓶内，用移液管加入 10mL 苯酐吡啶液，并用吡啶将瓶塞润湿，接上冷凝器置于油浴加热，在 115°C 下回流，间歇地摇荡，保持1.5h左右，冷却到室温，加 15mL 吡啶冲洗冷凝器，加 15mL 蒸馏水以使多余的苯酐水解，加5滴指示剂，以 0.5mol/L 氢氧化钾滴定至终点保持15s不褪色，同样条件做空白试验。\\n\\n按下列计算羟值：\\n羟值 = {(V - V0)C × 56.1}/m + 酸值羟基含量 = {(V - V0)C × 1.7}/m × 100%\\n其中 V0 - 空白滴定消耗氢氧化钾的体积，V - 样品滴定消耗氢氧化钾的体积，C - 氢氧化钾的浓度 (mol/L)，m - 样品质量 (g)。称取4.0g对甲苯磺酸于100mL醋酸乙酯中，搅拌至溶解，在搅拌下慢慢加入33mL醋酐。取5mL该液消耗氢氧化钾滴定液(0.5mol/L)。准确称取样品，加入5mL醋酸乙酯溶解样品，随后准确加入(5.00士0.02)mL乙酰化试剂，在50℃水浴上加热回流20min。反应后加入2mL水，振摇，再加入10mL吡啶与水(3:1)的混合液，振摇并室温放置10min。根据样品溶液的浑浊情况，加入一定量的甲苯/丁醇混合液，再加数滴酚肽指示剂，使用0.5mol/L氢氧化钾乙醇标准溶液滴定至溶液呈粉红色作为终点。试剂所有试剂的配制应在通风橱中进行，并戴防护眼镜或面罩。 (1) 高氯酸溶液的制备：在烧杯中依次缓慢加入250mL冰醋酸（AR）、13mL浓度为60%的高氯酸（分析纯）和50mL醋酸酐（分析纯），混匀后转移至1L的容量瓶中，以冰醋酸稀释至刻度，充分混合后静置8h以上，使醋酸酐与水充分反应。 (2) 样品测试：准确称取一定量的环氧树脂至三角烧瓶中，加入10~15mL二氯甲烷，在磁力搅拌下加入100mL溴化四乙基铵及6~8滴结晶紫指示剂，用高氯酸滴定，颜色由蓝变绿并持续2min为终点。1. Reagents: 1 mL of hydrochloric acid with a relative density of 1.19 dissolved in 40 mL of acetone, mixed well and prepared fresh. Methyl red indicator and 0.1 mol/L standard sodium hydroxide solution are also needed. 2. Method: Accurately weigh 0.5 to 1.5 g of resin and place it into a stoppered Erlenmeyer flask. Add 20 mL of hydrochloric acid-acetone solution using a pipette. Stopper the flask and shake to ensure complete dissolution of the resin, then let it sit in a cool place (around 15°C) for 1 hour. Add 3 drops of methyl red indicator, and titrate with approximately 0.1 mol/L standard sodium hydroxide solution until the color changes from red to yellow. Conduct a blank test in the same manner without adding resin. 3. Calculation: Calculate the epoxy value (EV) using the formula: EV = ((V1 - V2) * c) / (10 * m), where V1 is the volume of sodium hydroxide consumed in the blank test (mL), V2 is the volume for the sample (mL), C is the concentration of the sodium hydroxide solution (mol/L), and m is the sample weight (g).1. Prepare hydrochloric acid-pyridine solution by mixing 17 mL of hydrochloric acid (relative density 1.19) with 984 mL of pyridine. 2. Accurately weigh approximately 5 g of the sample and place it in a 250 mL round-bottom flask. 3. Add 25 mL of hydrochloric acid-pyridine solution using a pipette. 4. Attach a reflux condenser to the flask and heat slowly, refluxing for 40 minutes. 5. Allow the flask to cool to room temperature, then rinse the condenser with 20 mL of acetone. 6. Remove the flask and add 3 drops of phenolphthalein indicator. 7. Titrate with the 0.1 mol/L standard sodium hydroxide solution until a faint pink color persists for at least 30 seconds. 8. Perform a blank test without adding resin to ensure accuracy.1. Prepare the following reagents: a) Bromocresol green (0.1%): Dissolve 0.100 g of bromocresol green indicator in 1.5 mL of 0.1 mol/L sodium hydroxide solution, then dilute with water to a final volume of 100 mL. b) Dibutylamine solution (258 g/L): Dissolve 258 g of anhydrous dibutylamine in anhydrous toluene to a final volume of 1 L, achieving a concentration of 2 mol/L, and store in a brown bottle. c) Hydrochloric acid solution: 1 mol/L. d) Anhydrous toluene: dried. e) Ethanol (analytical grade).  \\n\\n2. Determine the isocyanate content: Add 40 mL of anhydrous toluene to a clean and dry 500 mL iodine flask, then use a pipette to add 50 mL of the dibutylamine solution. Next, add 6.5 to 7.0 g of toluene diisocyanate (TDI) sample into the flask (accurate to ±0.0018 g). Carefully swirl the flask, wash the neck with 10 mL of anhydrous toluene, seal the flask, and let it sit at room temperature for 15 minutes. After the reaction is complete, add 225 mL of ethanol and 0.8 mL of the bromocresol green indicator; titrate with the 1 mol/L hydrochloric acid solution until the color changes from blue to yellow and stays for 15 seconds. Conduct a blank test using the same method without adding the sample. \\n\\nCalculate the isocyanate group content using the following formula: -NCO(%) = ((V0 - v)N × 4.2) / m, where V0 = volume of hydrochloric acid used in the blank test (mL), v = volume of hydrochloric acid used for titrating the sample (mL), N = accurate concentration of hydrochloric acid (mol/L), m = sample mass (g). \\n\\n3. For determining the isocyanate group (-NCO) content in oligomers: Accurately weigh 1 g of the oligomer sample and place it in a 25 mL iodine flask; add 25 mL of anhydrous toluene and dissolve the sample (heating might be necessary). Then, use a pipette to add 25 mL of 0.1 mol/L dibutylamine solution, seal the flask, and mix well. After 15 minutes, add 100 mL of isopropanol and 4 to 6 drops of bromocresol green indicator. Titrate with hydrochloric acid to the yellow endpoint and also conduct a blank test. Calculate the isocyanate group (-NCO) content using the formula: -NCO(%) = ((V0 - V)N × 4.2) / m, where V0 = volume of hydrochloric acid used in the blank test (mL), v = volume of hydrochloric acid used for titration (mL), N = accurate concentration of hydrochloric acid (mol/L), m = sample mass (g).The text does not provide a specific experimental protocol for the synthesis of hydrophilic polymers with functional groups.试板的制作包括取玻璃板 $100\\mathrm{mm}\\times100\\mathrm{mm}\\times(3\\sim5)\\mathrm{mm}$，按照GB1727—1979《漆膜一般制备法》的规定进行表面处理和制备漆膜。试板的干燥根据GB1727—1979规定进行，干涂层的厚度使用GB1764一1979（杠杆千分尺法）测定，结果以\"μm\"表示。所有测试应在温度（25士1)℃，相对湿度 $(60\\sim70)\\%$ 条件下进行。1. Materials and Instruments: Prepare a set of high-grade drawing pencils from 6H to 6B, a pencil sharpener, a pencil scratch hardness tester, and 400# sandpaper. 2. Sample Preparation: Prepare three pieces according to GB1727-1979 or cut representative samples from coated items. 3. Tool Preparation: Sharpen the pencil to expose a 5-6 mm cylindrical core. Hold the pencil at a 90-degree angle to the sandpaper and continuously rub it in circles to obtain a flat and sharp pencil tip. Rotate the pencil 180 degrees after each use. 4. Manual Operation: Secure the coated sample on a horizontal surface. Hold the sharpened pencil at a 45-degree angle and apply force to scrape the coating at a speed of approximately 1 mm/s, starting with the hardest pencil and scraping five marks until finding a pencil that does not damage the coating. This pencil's hardness represents the coating's pencil hardness. 5. Instrument Testing: Place the coated item on the testing apparatus with the coated side up. Adjust the vertical line of the apparatus to intersect at the point of contact between the pencil tip and the coating. Insert the sharpened pencil into the holder at a 45-degree angle and apply a load sufficient to touch the sample. Add a silicon weight of (1.00±0.05) kB to the magnetic weight platform and allow contact with the coating. Move the sample and pencil against each other by 3 mm at a speed of 0.5 mm/s, scrape five marks, and rotate the pencil 180 degrees to ensure no damage to the tip, then change the sample position. Repeat with different hardness pencils to determine the pencil hardness of the coating.1. 试件处理：试板为马口铁板或钢板或铝板，处理和涂漆按GB9271进行。干燥在恒温23±2°C，湿度50±5%下，通常放置16小时。 2. 浸泡法：测试用液体材料应按产品标准，测试温度为23±2°C。程序A使用单相液体，容器加盖，鼓入空气时用脱除油脂的缓慢空气流，以保持原体积或浓度。浸泡后用水或已知溶剂清洗试件，检查涂层变化。 3. 使用吸收性介质：吸湿盘不受测试液影响，浸入试液，使盘均匀分布，并至少离试板边缘12mm，放置在无风环境中。移去盘子后清洗并检查涂层变化。 4. 点滴法：试板置于水平位置，滴加试液，每滴液体约0.1mL，中心至少间隔20mm，离边缘12mm，保持温度在23±2°C。达到规定期后清洗并检查涂层变化。将试样装入洁净干燥的试管中，在（25士1)℃下于暗箱的透射光下与铁钴比色计进行比较，选出两个与试样颜色最接近的，或一个与试样颜色相同的标准色阶溶液。试样颜色的等级直接以标准色阶的号表示。如色相不同时，可比较其颜色的深浅。在测试时试样若由于低温而引起浑浊，可在水浴上加热到50～55℃，保持5min，然后冷却至 (25±1)℃ ，再保持 5min 后进行测定。1. Use a palette knife to take approximately 5g of both the standard sample and the test sample, placing them onto a glass plate and mixing them uniformly. 2. Take about 0.5g of the mixed standard sample and apply it to the top left corner of a scraping paper, then take about 0.5g of the test sample and apply it to the top right corner, ensuring that they are adjacent but not connected. 3. Position the scraping blade above the applied ink samples, keeping the main part of the scraper at a 90-degree angle to the scraping paper. Apply force from top to bottom to spread the ink onto the scraping paper until reaching 15mm below the black horizontal line, then reduce the force so that the inside angle of the scraping blade is approximately 25 degrees, creating a thicker layer of ink on the paper. The final scraping shape should resemble the indicated sketch. 4. The thin layer of ink on the scraping paper is called the surface color, and the thick layer at the bottom of the scraping paper is referred to as the ink color; the thin layer of ink on the paper, viewed in light, is referred to as the bottom color. 5. After inspecting the color of the ink, cover the thick ink layer with glass paper.1. 使用调墨刀将受检油墨放置于道林纸中上方，持刮墨刀自上而下用力刮于刮样纸上，形成均匀的刮样。让刮样在常温条件下干燥24小时（个别品种可适当延长）。 2. 将干燥后刮样剪下面色部分小块，分别置于规定浓度的酸、碱、醇、水各试管内浸泡。 3. 浸泡24小时后，用镊子取出刮样，并与未经浸泡的刮样对比，检视刮样变色情况，依据附表4-2评定受检油墨耐酸、碱、醇、水的级别。 注意：耐乙醇试验需在密封条件下进行，做空白实验以观察纸张在溶液中变化情况，定级时应减除纸张变化因素。测定时室温应在20～25℃之间。取15～30mL医用注射器一支，装满胶黏剂，排掉气泡，将胶黏剂注入已经称量过的带磨口锥形瓶中精确称重，算出胶黏剂的质量。同样，用注射器向锥形瓶注人同体积的蒸馏水，精确称重，得到同体积蒸馏水的质量，即可用公式计算胶黏剂的相对密度。称取1～1.5g试样，置于干燥洁净的称量瓶中。将称量瓶置于通风橱中，用250W红外灯加热，干燥至试样不流动后，放入已按实验温度调好的鼓风恒温箱内加热1.5h。以丙酮、乙醇、乙酸乙酯等作溶剂时，加热温度为80±2℃；以甲苯、汽油等作溶剂时，加热温度为110±2℃。取出后放入干燥器中，冷却至室温，称重。再次将试样放入鼓风恒温箱内加热0.5h，取出，放入干燥器中冷却至室温，称重。实验至两次称量的质量差不大于0.01g为止。全部称量准确至0.001g。不挥发物含量按公式计算，取两次平行实验数值的平均值，两次平行实验数值之差不大于1%。精确称取一定质量的胶黏剂，放在坩埚中小心地灼烧，直至灼烧完全。可先用喷灯灼烧，再放人高温炉中；为了加速灼烧，并使灼烧完全，可滴入少量硝酸或 30% 的过氧化氢，但氧化剂的加人应在主要成分燃尽、坩埚冷却后加入。灼烧后，冷至室温称量，按下式计算灰分的百分含量：X{=}\\frac{d_{1}}{d}{\\times}100%。Prepare a metal plate with dimensions of 70mm x 20mm x 1.5 (or 2) mm including a groove. Accurately weigh the test plate. Apply the adhesive to the groove of the plate and dry it in an 80℃ oven for 2 hours. Once dried, allow the plate to reach room temperature and weigh until a constant weight is achieved. Immerse the plate in the medium for a specified time at the predetermined temperature (which may be defined by product standards or set independently). After immersion, wash the plate with ethanol if the medium is water or with petroleum ether if the medium is oil. Dry the plate again in an 80℃ oven for 2 hours and allow it to cool to room temperature. Weigh the plate until a constant weight is reached. The mass change rate (K) is calculated using the formula K = ((w2 - w3) / (w2 - w1)) × 100%, where w1 is the weight of the test plate, w2 is the weight before immersion, and w3 is the weight after immersion.盐雾实验可在各种盐雾试验箱内进行。所用试片的处理与大气老化相同，按有关标准配制含 NaCl, MgCl（无水）, CaCl（无水）/KCl等一定浓度的盐水溶液，控制 pH 值为 6.5{\\sim}7.2。试片从试验箱取出后，用少量棉花蘸水，去除试片上的盐粒，存放 24 h 后测定各种性能，将其与空白试验比较，判断该种胶黏剂的耐盐雾腐蚀性能。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╤к╦и╨н═м┐╣╛· ╓╨╬─.json b/task2/task2-paper-info/╤к╦и╨н═м┐╣╛· ╓╨╬─.json
new file mode 100644
index 0000000..1b767c4
--- /dev/null
+++ b/task2/task2-paper-info/╤к╦и╨н═м┐╣╛· ╓╨╬─.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "在这项研究中，我们使用了医用级聚氯乙烯（Ty-gon）管，涂层表面的摩擦系数很低，可承受生理流速下的流体流动长达12小时，且无任何可测量的变化。我们展示了植入全身循环（水凝胶涂层PVC管）的良好通畅率，并通过一系列体外试验和流动循环测试，发现透明凝胶涂层可减少血凝块的形成和对设备表面的粘附，同时不影响血液的正常凝结能力。首先将洁净的医疗表面浸没在乙醇中的二苯甲酮溶液中。除去溶液后，在活化表面加入含有 N,N-二甲基丙烯酰胺（DMAA）和生物相容性光引发剂（Irgacure 2595）的预凝胶水溶液。然后用紫外线照射表面，使水凝胶层聚合。彻底冲洗多余的聚合物和副产品后，在设备上均匀涂上一层超薄的水凝胶。将医用级平面或管材切割成所需尺寸，用异丙醇和去离子水清洗，并用氮气流充分干燥。然后用空气等离子体处理1-2分钟，并浸没在二苯甲酮溶液（10wt%乙醇中）3-5分钟。从溶液中取出装置，用纸巾吸去多余的乙醇，然后将装置放入脱气的水凝胶前体溶液（20-30 wt% N,N-二甲基丙烯酰胺，0.5wt% Irgacure I-2959水溶液）中。确保平面表面上方至少有5毫米的前驱体溶液，对于管材，前驱体溶液应完全充满内壁。将装置暴露在紫外线（UVP CL-1000，λ=365纳米）下，时间为10分钟。随后在设备表面形成互穿水凝胶层，聚合溶液被清除并作为废物处理，并在测试之前用去离子水彻底清洗这些器件3天。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╤к╦и╨н═м┐╣╛·.json b/task2/task2-paper-info/╤к╦и╨н═м┐╣╛·.json
new file mode 100644
index 0000000..6a81531
--- /dev/null
+++ b/task2/task2-paper-info/╤к╦и╨н═м┐╣╛·.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Hydrogel coatings were prepared by first submerging clean medical surfaces in a benzophenone solution in ethanol. After removal of the solution, an aqueous pregel solution containing N,N-dimethylacrylamide (DMAA) and a biocompatible photoinitiator (Irgacure 2595) was added to the activated surfaces. UV irradiation was then applied to polymerize the hydrogel layer. Excess polymers and byproducts were thoroughly rinsed away, resulting in an ultrathin (approximately 10 µm) hydrogel layer uniformly coated on the device.The medical-grade flat surface or tubing was cut to the desired size, cleaned with isopropanol and DI water, and fully dried with a nitrogen stream. The devices were air-plasma treated for 1-2 min and submerged in a benzophenone solution (10 wt% in ethanol) for 3-5 min. The devices were then removed from the solution, and excess ethanol was removed by blotting with tissue. The devices were submerged in a hydrogel precursor solution (20-30 wt% N,N-dimethylacrylamide, 0.5 wt% Irgacure I-2959 in water). For flat surfaces, there should be at least 5 mm of precursor solution above the surface. For tubing, the precursor solution should completely fill the inner lumen. The devices were then exposed to UV (UVP CL-1000, λ=365 nm) for 45 min to create the interpenetrating hydrogel layer on the device surface. The polymerized solution was removed and disposed as waste. The devices were thoroughly washed with DI water for 3 days before testing."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╤╨╛┐╣д╫ў╨б╜с.json b/task2/task2-paper-info/╤╨╛┐╣д╫ў╨б╜с.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/╤╨╛┐╣д╫ў╨б╜с.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╥й╬я╖в╧╓╓╨╡─╖╓╫╙╔ш╝╞╔ю╢╚╔·│╔─г╨═╡─╫█╩Ў.json b/task2/task2-paper-info/╥й╬я╖в╧╓╓╨╡─╖╓╫╙╔ш╝╞╔ю╢╚╔·│╔─г╨═╡─╫█╩Ў.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/╥й╬я╖в╧╓╓╨╡─╖╓╫╙╔ш╝╞╔ю╢╚╔·│╔─г╨═╡─╫█╩Ў.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╥╗╓╓╖└╬э│╓╛├╡─╖└╬э═┐┴╧.json b/task2/task2-paper-info/╥╗╓╓╖└╬э│╓╛├╡─╖└╬э═┐┴╧.json
new file mode 100644
index 0000000..44b3160
--- /dev/null
+++ b/task2/task2-paper-info/╥╗╓╓╖└╬э│╓╛├╡─╖└╬э═┐┴╧.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "在反应容器中加入亲水性溶剂，升温至 50∼140℃，将上述单体、改性的表面活性剂和引发剂混合均匀后，匀速滴加到溶剂中，滴加时间为 2∼5 小时，滴加结束后，保温反应 1∼3 小时制得。改性的表面活性剂为含磺酸基、硫酸基或羧酸基团的表面活性剂与（甲基）丙烯酸缩水甘油酯单体按摩尔比 0.5∼2:1 混合均匀后，加入催化剂单丁基氧化锡，升温至 80∼180℃并保温 3∼3.5 小时接枝形成的。以防雾特性树脂作为主要成膜树脂与封闭型异氰酸酯固化剂配合形成防雾涂料；所述防雾特性树脂是以 10至50wt% 丙烯酸酯单体、 1至40wt% 含氮原子的乙烯基单体、 1至10wt% 改性的表面活性剂、 0.1至5wt% 引发剂、余量为亲水性溶剂作为原料，在反应容器中加入亲水性溶剂，升温至 50至140°C，将上述单体、改性的表面活性剂和引发剂混合均匀后，匀速滴加到溶剂中，滴加时间为 2至5小时，滴加结束后，保温反应 1至3小时，制得的；改性的表面活性剂为含磺酸基、硫酸基或羧酸基团的表面活性剂与（甲基）丙烯酸缩水甘油酯单体按摩尔比 0.5至2:1 混合均匀后，加入适量催化剂单丁基氧化锡，升温至 80至180°C 并保温 3至3.5小时接枝形成的。将含磺酸基、硫酸基或羧酸基团的表面活性剂与（甲基）丙烯酸缩水甘油酯单体按摩尔比 $0.5\\sim2{:}1$ 混合均匀后，加入适量催化剂单丁基氧化锡，升温至 $80\\sim180^{\\circ}C$ 并保温 $3\\sim3.5$ 小时接枝形成改性的表面活性剂。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╥╗╓╓╗╖▒г╟╥╖└╬э╨з╣√│╓╛├╡─▓г┴з╖└╬э╝┴╝░╞ф╓╞▒╕╖╜╖и.json b/task2/task2-paper-info/╥╗╓╓╗╖▒г╟╥╖└╬э╨з╣√│╓╛├╡─▓г┴з╖└╬э╝┴╝░╞ф╓╞▒╕╖╜╖и.json
new file mode 100644
index 0000000..42cdc79
--- /dev/null
+++ b/task2/task2-paper-info/╥╗╓╓╗╖▒г╟╥╖└╬э╨з╣√│╓╛├╡─▓г┴з╖└╬э╝┴╝░╞ф╓╞▒╕╖╜╖и.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "A、按摩尔比4—5:1:10:0.2—0.3:0.2—0.3称取烯丙基聚醚、四甲基环四硅氧烷、八甲基环四硅氧烷、蒸馏水、四乙氧基硅烷；B、将步骤A称取的烯丙基聚醚、四甲基环四硅氧烷加入到反应釜中，通氮气进行保护，然后加入铂金催化剂，控制釜内温度在60一120°C，搅拌状态下反应2一3h，得初产物；C、将步骤B所得初产物进行过滤、精馏，然后加入步骤A称取的八甲基环四硅氧烷和蒸馏水；通氮气进行保护，加入碱胶催化剂，控制反应温度在80一130°C，搅拌反应4—5h，得次产物；D、将步骤C的次产物过滤、精馏，然后加入步骤A称取的四乙氧基硅烷；通氮气进行保护，控制反应温度50-70°C，在搅拌状态下反应2一3h；过滤、精馏、冷却，得环保且防雾效果持久的玻璃防雾剂。A、按摩尔比4-5:1:10:0.2-0.3称取烯丙基聚醚、四甲基环四硅氧烷、八甲基环四硅氧烷、蒸馏水、四乙氧基硅烷；B、将步骤A称取的烯丙基聚醚、四甲基环四硅氧烷加入到反应釜中，通氮气进行保护，然后加入铂金催化剂，控制釜内温度在 60{-}120^{\\circ}C ，搅拌状态下反应2-3h，得初产物；C、将步骤B所得初产物进行过滤、精馏，然后加入步骤A称取的八甲基环四硅氧烷和蒸馏水；通氮气进行保护，加入碱胶催化剂，控制反应温度在 80-130^{\\circ}C ，搅拌反应4-5h，得次产物；D、将步骤C的次产物过滤、精馏，然后加入步骤A称取的四乙氧基硅烷；通氮气进行保护，控制反应温度 50-70^{\\circ}C ，在搅拌状态下反应2-3h；过滤、精馏、冷却，得环保且防雾效果持久的玻璃防雾剂。A、按以下摩尔比4：1:10：0.2:0.2称取烯丙基聚醚、四甲基环四硅氧烷、八甲基环四硅氧烷、蒸馏水、四乙氧基硅烷做为原料备用；B、将步骤A称取的烯丙基聚醚、四甲基环四硅氧烷加入到反应釜中，通氮气进行保护，加入铂金催化剂，控制温度 $60^{\\circ}\\mathrm{C}$ ，搅拌状态下反应2h，得初产物；C、将步骤B所得初产物过滤、精馏，然后加入步骤A称取的八甲基环四硅氧烷和蒸馏水，通氮气进行保护，加入碱胶催化剂，控制温度 $80^{\\circ}C$ ，搅拌状态下反应4h，得次产物；D、将步骤C所得次产物过滤、精馏，然后加入步骤A称取的四乙氧基硅烷，通氮气进行保护，控制温度 $50^{\\circ}\\mathrm{C}$ ，搅拌状态下反应2h；过滤、精馏、冷却，得环保且防雾效果持久的玻璃防雾剂。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╥╜╙├╕▀╖╓╫╙▓─┴╧┐╣─¤╤к▒э├ц╣╣╜и▓▀┬╘╝░╤╨╛┐╜°╒╣.json b/task2/task2-paper-info/╥╜╙├╕▀╖╓╫╙▓─┴╧┐╣─¤╤к▒э├ц╣╣╜и▓▀┬╘╝░╤╨╛┐╜°╒╣.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/╥╜╙├╕▀╖╓╫╙▓─┴╧┐╣─¤╤к▒э├ц╣╣╜и▓▀┬╘╝░╤╨╛┐╜°╒╣.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╦о─¤╜║ Nature.json b/task2/task2-paper-info/╦о─¤╜║ Nature.json
new file mode 100644
index 0000000..a981c6c
--- /dev/null
+++ b/task2/task2-paper-info/╦о─¤╜║ Nature.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "Ultrathin polymeric membranes can be prepared through interfacial polymerization (IP), typically performed at the gas–liquid interface, where the reactive building blocks are continuously supplied and undergo systematic aggregation.For targeted inorganic production in a mild aqueous reaction, membrane synthesis begins with an arbitrary initial concentration and reaction temperature. After sufficient time, evaluate the GT-phase attributes of the floating solids and adjust the reaction conditions for new synthesis. Repeat the experimental loop to obtain a well-defined membrane, adjusting thickness and through-hole parameters by controlling building unit size and terminal reaction time.The consumable polystyrene Petri dish was used as the reaction vessel for membrane synthesis. The inwall of the Petri dish was manually coated with the PVAAc film of about 1.6x10^{-2} mg mm^{-2}, which can rapidly swell into a hydrogel coat once it makes contact with the aqueous solution. Briefly, the Petri dish was waggled sufficiently following the addition of 500 microliters of PVAAc aqueous solution (3.5 wt%) to guarantee that all of its inwall surface was wetted by the solution. The pretreated Petri dish with PVAAc film coating was then obtained by desiccating it at 70 degrees Celsius for 2 hours, followed by naturally cooling down to room temperature.1. Prepare Tollens’ reagent by mixing 60μl of ammonium hydroxide solution (28-30wt%) with 1.44ml of AgNO3 solution to yield a 120mM solution. 2. Transfer 1.5ml of the fresh Tollens’ reagent solution into a pretreated Petri dish. 3. Add 1.5ml of a mixed solution containing D(+)-glucose (250mM) and NaOH (50mM) to the Petri dish. 4. Allow the mixture to stand at room temperature for 30 minutes to enable the Ag membrane formation on the aqueous solution surface. 5. Transfer the formed Ag membrane onto the surface of deionized water using a glass sheet. 6. Perform a control synthesis in a clean Petri dish with no surface coating under the same conditions.To separate the floating membrane from the reaction Petri dish, first remove the solution using a pipette. Then, add 8 ml deionized water to refloat the membrane. Replace the water inside the dish three times to fully eliminate residual chemicals. Immerse the membrane-held dish in a larger tank full of deionized water to transfer the cleaned membrane to a wider surface. To cut the membrane, lift it using a hydrophobic acrylic plate, cut with a razor blade before the water completely evaporates, and release it to refloat on the water surface for subsequent transfer. For characterization, the membrane can be transferred to various substrates. To prepare a flat membrane for X-ray diffraction (XRD) characterization, create a hydrophilic surface on the hydrophobic acrylic plate by exposing it to 254-nm ultraviolet (UV) light for 15 minutes at room temperature. For membranes that are not water resistant, clean and float them using an acetone solution (about 2-10% in deionized water).Cut a small piece of membrane with dimensions larger than 3 mm and smaller than 4 mm in each direction. Release the membrane to refloat on the surface of deionized water. Suspend the membrane over a copper ring with outer diameter of 4 mm and inner diameter of 2 mm to ensure a single-layer configuration. Use the through-hole membrane for optical observation on an Olympus BX53 microscope after natural drying at room temperature.In a sealed cuboid box (160×100×70 mm³) painted black, place a pretreated dish with 1.5 ml of fresh Tollens' reagent solution (120 mM) at the center. Position a visible fibre-coupled UHP-T-LED light source with a 12 mm diameter collimator 30 mm above the solution surface at a 90° angle from the opposite fibre detector of a spectrometer (Maya2000, Ocean Optics). To start the reaction, introduce 1.5 ml of a mixed D(+)-glucose (250 mM) and NaOH (50 mM) solution from a dropper hanging over the apparatus. Collect in situ reflectance spectra of the air-liquid interface consecutively using Spectra Suite. Collect spectra for five minutes prior to reaction initiation at a rate of 0.2 Hz to estimate measurement stability. For the first 60 seconds after the reaction starts, set acquisition rate at 16.7 Hz; for the remaining 29 minutes, set it at 0.032 Hz.PVAAc aqueous solution (3.5wt%) was applied onto the surface of the bare substrate (area 1x1cm2) at 70°C in an oven and then desiccated for 2h.One millilitre of deionized water was added onto the PVAAc coat on a square glass plate, followed by standing at room temperature for 15 min. The dry PVAAc film swelled into a hydrogel coat, and free water was removed by filter paper to prepare the free-swelling hydrogel coating. A second piece of glass plate was placed on the free-swelling hydrogel coating, and a compressive load of 21.6 N was applied using a Mecmesin MultiTest 1-i tensile and compression test system. Transudatory water was removed by filter paper during 10-min-retained compressive loading."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╦о─¤╜║┤л╕╨╫█╩Ў.json b/task2/task2-paper-info/╦о─¤╜║┤л╕╨╫█╩Ў.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/╦о─¤╜║┤л╕╨╫█╩Ў.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╦о─¤╜║═┐┴╧ AM.json b/task2/task2-paper-info/╦о─¤╜║═┐┴╧ AM.json
new file mode 100644
index 0000000..e464217
--- /dev/null
+++ b/task2/task2-paper-info/╦о─¤╜║═┐┴╧ AM.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "1. Formulation: Dissolve monomer (acrylamide, AAm) and coupling agent (3-(trimethoxysilyl)propyl methacrylate, TMSPMA) in water to create an aqueous solution. Include other compounds as necessary (initiators, chain transfer agents, rheological modifiers, etc.). 2. Polymerization: The monomer and the coupling agent copolymerize into uncrosslinked p(AAm-co-TMSPMA) chains via free-radical polymerization. 3. Substrate preparation: Impart hydroxyl groups onto the surface of the substrate to ensure complementary functional groups to the silanols. 4. Application: Apply the uncrosslinked polymer chain solution onto the prepared substrate using methods such as brush, cast, dip, spin, or spray. 5. Cure: Allow the paint to cure by enabling the silanol groups to condense and crosslink the polymer chains into a polymer network, while simultaneously bonding the polymer network to the substrate through the formation of siloxane bonds.For 1 mL solution of AAm (2 moles per a liter of DI water, 2 mol L^{-1} ), 1 μL of CTA (10% volume ratio in THF), 10 μL of acetic acid (0.1 moles per a liter of DI water, 0.1 mol L^{-1} ), and 5.7 μL of TMSPMA are added, followed by vortex mixing for 60 s. Then, 2 μL of I-2959 (0.1 moles per a liter of ethanol, 0.1 mol L^{-1} ) is added followed by vortex mixing for 10 s. The resulting transparent solution is drawn into a plastic syringe and subjected to UV irradiation (15W 365 nm; UVP XX-15L, 5 cm distance between sample and bulb). After 30 min, the p(AAm-co-TMSPMA) hydrogel paint is obtained. Nitinol guidewire is washed with IPA, acetone, and DI water in sequence twice and then dried by air. The guidewire is immersed in the p(AAm-co-TMSPMA) hydrogel paint and pulled out vertically with a constant velocity of 10 mm min^{-1}. The coated wire is sealed in a bottle with saturated humidity and stored in an oven at 65°C for 24 h."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╦о─¤╜║╗п╤з┤л╕╨.json b/task2/task2-paper-info/╦о─¤╜║╗п╤з┤л╕╨.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/╦о─¤╜║╗п╤з┤л╕╨.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╦о─¤╜║╘┌╣╟╫щ╓п╣д│╠╓╨╡─╙ж╙├╜°╒╣_▓▄╜и╘є.json b/task2/task2-paper-info/╦о─¤╜║╘┌╣╟╫щ╓п╣д│╠╓╨╡─╙ж╙├╜°╒╣_▓▄╜и╘є.json
new file mode 100644
index 0000000..b044908
--- /dev/null
+++ b/task2/task2-paper-info/╦о─¤╜║╘┌╣╟╫щ╓п╣д│╠╓╨╡─╙ж╙├╜°╒╣_▓▄╜и╘є.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "水凝胶通常是由一种或几种单体通过化学反应制备的，通过在聚合物链之间形成缔合键物理水凝胶的合成过程通过温度、pH和离子浓度的变化等物理交联过程生成，具体步骤未详细列出.化学水凝胶的合成涉及通过共价交联的网络形成。主要采用的共价偶联反应包括迈克尔加成反应、点击反应、席夫碱形成、光交联和酶介导交联。可通过交联水溶性单体和聚合物，以及将疏水性单体和聚合物转化为亲水性单体和聚合物来制备。"
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╦о─¤╜║╞╧╠╤╠╟╝ь▓т.json b/task2/task2-paper-info/╦о─¤╜║╞╧╠╤╠╟╝ь▓т.json
new file mode 100644
index 0000000..cb7915a
--- /dev/null
+++ b/task2/task2-paper-info/╦о─¤╜║╞╧╠╤╠╟╝ь▓т.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "To synthesize hydrophilic polymers with functional groups, start with crosslinking poly(allylamine hydrochloride) (PAH) and template the polymer with d-glucose 6-phosphate monobarium salt (GPS-Ba). The hydrogel should then be covalently bonded to gold-coated glass slides to create the chemical recognition sites. This will involve utilizing the hydrogen bonding and π-π stacking interactions between the template and monomers in solution. Ensure to facilitate self-assembly of the positively charged polymer around the negatively charged phosphate group of the template. After the template is removed, the hydrogel will allow for the detection of glucose based on refractive index changes due to physical swelling upon analyte binding.To prepare the MIH, a 20 mL aqueous solution containing 0.1 mg/mL poly(allylamine hydrochloride) (PAH), 0.5 mg/mL d-glucose phosphate barium salt (GPS-Ba), and sufficient 1 M NaOH to raise the solution pH to 9 was stirred for 30 min prior to adding DSP-modified gold-coated slides. After 3 h, 5 mL of 0.03 M epichlorohydrin was added to crosslink the hydrogel and the solution was stirred overnight. The slides were then rinsed with deionized water and dipped in 4 M NaOH solution overnight to extract the template, followed by dipping in stirred deionized water for 30 min to thoroughly rinse off the NaOH. For slides with NHS-MHA, 1 mg/mL GPS-Ba was added to the polymer solution and 0.2 M NaOH was used to remove the template after imprinting. Finally, the slides were dried under a stream of dry nitrogen and stored under atmospheric conditions until used.Gold nanoparticles were synthesized by a modified Turkevitch method. The pH of a 10 mL 0.001 M HAuCl4 3H2O solution was adjusted to 7.2 with 1 M NaOH. The solution was heated to boiling and 5% (w/w) sodium citrate was added to achieve a 2:1 ratio between citrate and HAuCl4. The boiling solution was continuously stirred for 1 hour until it turned a wine-red color. The colloid solution was allowed to cool to room temperature, and then several drops of a 1 M cysteamine hydrochloride in 1 M NaOH solution were added until the colloid turned blue, indicating modification with the cysteamine capping agent. A 5 mL aliquot of this solution was added to the PAH solution immediately prior to the addition of epichlorohydrin. The volume of the 0.03 M epichlorohydrin was adjusted to 6.25 mL to maintain the concentration of the cross-linker.Each sensing cycle began with equilibration of the coating in water, followed by exposure to the analyte and then a water washing step to remove non-specifically bound species. At the end of each cycle, 0.1 M NaOH was flushed to regenerate the sensor surface. Each step lasted for 10 min."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╦о─¤╜║╨▐╕┤╣╟╚▒╦Ё.json b/task2/task2-paper-info/╦о─¤╜║╨▐╕┤╣╟╚▒╦Ё.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/╦о─¤╜║╨▐╕┤╣╟╚▒╦Ё.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╦о─¤╜║▓т╤╬╢╚.json b/task2/task2-paper-info/╦о─¤╜║▓т╤╬╢╚.json
new file mode 100644
index 0000000..1fcda4f
--- /dev/null
+++ b/task2/task2-paper-info/╦о─¤╜║▓т╤╬╢╚.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The polyacrylamide hydrogel was prepared by free-radical solution polymerization initiated by a photoinitiator. The monomer, acrylamide (AAm), and the cross-linker, N,N'-methylene bisacrylamide (MBAAm), were purchased and treated as follows: AAm was frozen and recrystallized from a mixed solvent of benzene and chloroform three times before use, while MBAAm was recrystallized from its alcohol solution twice. The photoinitiator, q-ketoglutaric acid (KGA), was used without further treatment. Deionized water was redistilled for use as solvents. Before polymerization, the fiber grating was immersed in the mixture solution. The solution was then polymerized under UV irradiation around λ=365 nm."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╧╚╜°╛█║╧╬я▓─┴╧╡─╗·╞ў╤з╧░╕и╓·╔ш╝╞.json b/task2/task2-paper-info/╧╚╜°╛█║╧╬я▓─┴╧╡─╗·╞ў╤з╧░╕и╓·╔ш╝╞.json
new file mode 100644
index 0000000..ab03505
--- /dev/null
+++ b/task2/task2-paper-info/╧╚╜°╛█║╧╬я▓─┴╧╡─╗·╞ў╤з╧░╕и╓·╔ш╝╞.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "No specific experimental protocol for the synthesis of hydrophilic polymers with functional groups is provided in the text excerpt."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╩¤╛▌╟¤╢п▓─┴╧╤╨╖в╣ж─▄╨╘═┐┴╧.json b/task2/task2-paper-info/╩¤╛▌╟¤╢п▓─┴╧╤╨╖в╣ж─▄╨╘═┐┴╧.json
new file mode 100644
index 0000000..ff997f0
--- /dev/null
+++ b/task2/task2-paper-info/╩¤╛▌╟¤╢п▓─┴╧╤╨╖в╣ж─▄╨╘═┐┴╧.json
@@ -0,0 +1,3 @@
+{
+    "protocol": ""
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/╫╘╣й─▄╡─╗·╞ў╤з╧░╕и╓·▓─┴╧╩╢▒Ёгм╥└═╨╙┌╕▀╚╚╡ч╩╞╡─╚╚╡ч╦л═°┬ч╦о─¤╜║.json b/task2/task2-paper-info/╫╘╣й─▄╡─╗·╞ў╤з╧░╕и╓·▓─┴╧╩╢▒Ёгм╥└═╨╙┌╕▀╚╚╡ч╩╞╡─╚╚╡ч╦л═°┬ч╦о─¤╜║.json
new file mode 100644
index 0000000..914eb06
--- /dev/null
+++ b/task2/task2-paper-info/╫╘╣й─▄╡─╗·╞ў╤з╧░╕и╓·▓─┴╧╩╢▒Ёгм╥└═╨╙┌╕▀╚╚╡ч╩╞╡─╚╚╡ч╦л═°┬ч╦о─¤╜║.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "A thermogalvanic dual-network hydrogel is fabricated using [Fe(CN)6]^{3-/4-} as a redox couple along with lithium magnesium silicate, Cdm^{+}, and lithium bromide as key electrolytes. These components are combined to optimize the interconnected porous structure of the gel, which is designed to exhibit excellent mechanical and thermoelectric properties.Synthesize a thermogalvanic hydrogel using acrylamide as the matrix, gelatin as the reinforcing agent, and [Fe(CN)6]^{3-/4-} as the redox couple. Incorporate lithium magnesium silicate (LMS) to enlarge pore size and include Li+ and Br- to extend effective working time, while adding Gdm+ to significantly increase thermopower to 4.01 mV K^{-1}.The TG-DNH is prepared primarily based on an aqueous solution polymerization method. First, acrylamide, LMS, and gelatin were added to 70 mL of deionized water and stirred at 70 °C until wholly dissolved to obtain a mixed solution. After the mixed solution was cooled down, N,N'-methylene bisacrylamide and initiator ammonium persulfate were added sequentially and stirred at room temperature until completely dissolved. Then, catalyst N,N,N',N'-Tetramethylethylenediamine was added, gently mixed, and quickly poured into the prepared mold for approximately 2 hours to obtain DNH. Finally, the prepared DNH was immersed in a mixture of [Fe(CN)6]3-/4-, guanidine hydrochloride, and lithium bromide for 2 hours to obtain the TG-DNH."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/▒√╧й╦с╩ў╓м.json b/task2/task2-paper-info/▒√╧й╦с╩ў╓м.json
new file mode 100644
index 0000000..8c9cca1
--- /dev/null
+++ b/task2/task2-paper-info/▒√╧й╦с╩ў╓м.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "The synthesis of POSS-PDMAEMA involves using POSS-Br as an ATRP macroinitiator. The mixture of POSS-Br (0.1024 g, 0.1 mmol), DMAEMA (1.8865 g, 12 mmol), HMTETA (0.0277 g, 0.12 mmol), and THF (2 ml) is injected into a 10 mL standard Schlenk flask. The flask is filled with highly pure nitrogen, and residual oxygen is removed by three freeze-pump-thaw cycles. CuBr (0.0144 g, 0.1 mmol) is added quickly to the flask, followed by another three freeze-pump-thaw cycles. The mixture is reacted at 50°C for 1.5, 2, and 2.5 hours, respectively, and the reaction is terminated by adding a few drops of THF into the flask. The solution is passed through a neutral alumina column to intercept Cu2+ and concentrated using a rotary evaporator. Finally, the resulting POSS-PDMAEMA polymers with different polymerization degrees are obtained by precipitating in cold n-hexane and drying in a vacuum oven for 24 hours."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/▒√╧й╦с╩ў╓м2.json b/task2/task2-paper-info/▒√╧й╦с╩ў╓м2.json
new file mode 100644
index 0000000..7602807
--- /dev/null
+++ b/task2/task2-paper-info/▒√╧й╦с╩ў╓м2.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "Prepare amphiphilic SIPN coatings from POSS-PDMAEMA-PSBMA block copolymers by integrating POSS with both PDMAEMA and PSBMA via atom transfer radical polymerization (ATRP). Add a small amount (10 wt%) of EGDMA and perform UV-curing.The POSS-PDMAEMA-b-PSBMA block copolymers were synthesized via ATRP of DMAEMA using POSS-Br as an initiator, followed by ATRP of SBMA using POSS-PDMAEMA-Br as a macroinitiator. Three block copolymers with different polymerization degrees (POSS-PDMAEMA50-b-PSBMA7, POSS-PDMAEMA70-b-PSBMA10, and POSS-PDMAEMA90-b-PSBMA13) were prepared. For control, PDMAEMA-b-PSBMA was synthesized using ethyl-2-bromoisobutanoate as the initiator. The block copolymers were characterized by 1H NMR, FTIR, GPC, and TGA. The SIPN coatings were prepared by dissolving the block copolymer in 2,2,2-trifluoroethanol to create a 25 mg/mL solution, adding EGDMA (10 wt% based on copolymer) and Igracure 2959 UV photoinitiator (2 wt%). The solution was cast onto a glass slide and cured under UV light (365 nm, 15 W, 1800 s). The coatings were air-dried at room temperature."
+}
\ No newline at end of file
diff --git a/task2/task2-paper-info/▒╟─┌╛╡╖└╬э▓─┴╧╤╨╓╞╝░╖└╬э╗·└э╠╜╠╓.json b/task2/task2-paper-info/▒╟─┌╛╡╖└╬э▓─┴╧╤╨╓╞╝░╖└╬э╗·└э╠╜╠╓.json
new file mode 100644
index 0000000..88af3e1
--- /dev/null
+++ b/task2/task2-paper-info/▒╟─┌╛╡╖└╬э▓─┴╧╤╨╓╞╝░╖└╬э╗·└э╠╜╠╓.json
@@ -0,0 +1,3 @@
+{
+    "protocol": "一：亲水型防雾剂制备：表面活性剂、溶剂、分散剂等按一定的配比混合，依次将无水乙醇、丙二醇、月桂醇聚氧乙烯醚、十二烷基硫酸钠、聚乙二醇400，余量为去离子水，按不同质量比加入称量瓶中混合，并置于 50^{\\circ}C 水浴箱15分钟得27种无色透明、无刺激性的鼻内镜防雾剂。对27种配方的防雾时间及性能进行测试，得到最佳配比。纳米粒子改性亲水型鼻内窥镜防雾剂的制备为：将纳米 SiO_{2} 0.05克和纳米 SiO_{2}-KH5700.05克加入亲水性鼻内镜防雾剂中，超声分散30分钟。纳米粒子改性聚乙烯吡咯烷酮（PVP）鼻内窥镜防雾剂：0.05克纳米氧化锌、0.025克自制纳米二氧化钛和0.05克自制纳米二氧化硅中空微球分别加入5ml聚乙烯吡咯烷酮溶液中，超声分散30分钟。The synthesis of hydrophilic polymers with functional groups involves inducing hydrophilicity on the material surface by incorporating a large number of hydrophilic groups. This can be achieved through various methods including the use of small molecule surfactants or organic polymer coatings. Techniques such as sol-gel method, phase separation, and chemical vapor deposition (CVD) can also be utilized in the process. The goal is to create a surface that attracts water molecules, allowing droplets to spread and form a continuous water film, enhancing antifogging properties.Hydrophilic antifogging agent was synthesized by mixing the following components in a weighing bottle: ethanol (0.6-20%), propylene glycol (0.6-20%), polyoxyethylene lauryl ether (0.6-20%), sodium dodecyl sulfate (0.6-4%), polyethylene glycol 400 (0.6-4%), and deionized water. The mixture was placed in a water bath at 50 °C for 15 minutes. 27 different formulations were prepared based on an orthogonal test design (L27(3^5)). For nanoparticles modification, 0.05 g of SiO2 and 0.05 g of nano sioz-KH570 were added to 5 ml of the hydrophilic antifogging agent and mixed via ultrasonic dispersion for 30 minutes. Another modification involved adding 0.05 g of nano ZnO, 0.025 g of nano titanium dioxide, and 0.05 g of hollow microspheres nano silica into 5 ml of polyvinylpyrrolidone solution followed by ultrasonic dispersion for 30 minutes. Light transmittance, contact angle, antifog time, adhesion work, transmission electron microscopy, and atomic force microscopy were used for characterization of the antifogging agents.本实验以无毒、无味、刺激性小的表面活性剂、溶剂、分散剂等原料，拟通过正交设计，按不同的质量配比选配出透光率高且防雾性好的亲水型鼻内镜防雾剂。The experimental protocol for synthesizing hydrophilic polymers with functional groups includes the use of specific reagents: Anhydrous ethanol (specifications 'a', analytical pure, from Tianjin Fuyu Fine Chemical Co., Ltd.), propylene glycol (specifications 'b', analytical pure, from Tianjin Chemical Reagents Factory), lauryl alcohol polyethylene ether (specifications 'C', high purity, from Aladdin Chemistry Co. Ltd.), and sodium dodecyl sulfate (specifications 'd', chemical pure, from Guangzhou Chemical Reagents Factory). Additionally, polyethylene glycol 400 (specifications 'e', analytical pure, from Guangzhou Chemical Reagents Factory) is dehydrated for use. 防雾剂的制备按先后顺序将无水乙醇、丙二醇、月桂醇聚氧乙烯醚、十二烷基硫酸钠、聚乙二醇400，余量为去离子水按不同质量比加入称量瓶中混合并置于 50^{\\circ}C 水浴箱15分钟后即得无色透明、无刺激性鼻内镜防雾剂。测其pH 值为 7{\\sim}8 。本试验拟将自制的纳米二氧化硅按一定的质量百分比添加至第一章所研制的亲水型鼻内镜防雾剂中，探讨改性后的防雾剂防雾性能有何变化并进一步探讨其防雾性能改变的机理。1.2.1.1 Preparation of silica nanoparticles: Mix 75ml of anhydrous ethanol, 32.0ml of deionized water, and 4.0ml of 25% ammonia water in a conical flask and stir for 30 minutes at 20.0°C. Slowly add 4.8ml of tetraethyl orthosilicate (TEOS) during stirring and continue stirring for 12 hours at 20.0°C to obtain a translucent suspension of nano silica. 1.2.1.2 Preparation of nano SiO2-KH570: Centrifuge the prepared nano SiO2, then dry in a vacuum oven at 100°C for 24 hours. Mix 1.0g of nano SiO2, 20ml of anhydrous ethanol, and 20ml of deionized water in a beaker to form a solution. Ultrasonically disperse for 3 hours and transfer to a flask. Dissolve 0.05ml of KH570 in 20ml of anhydrous ethanol, stir for 30 minutes, then add to the nano SiO2 solution, maintaining stirring at 70°C for 5 hours. Finally, centrifuge the obtained emulsion at high speed (10,000r/s) for 5 minutes, remove the supernatant, and disperse in anhydrous ethanol for 10 minutes, repeating this step 6 times to remove excess KH570, and dry to obtain nano SiO2-KH570. 1.2.1.3 Preparation of hydrophilic nasal endoscope anti-fog agent: Mix 20g of anhydrous ethanol, 10g of propylene glycol, 20g of lauryl alcohol polyoxyethylene ether, 4g of sodium dodecyl sulfate, 4004g of polyethylene glycol, and 42ml of deionized water in a flask and place in a water bath at 50°C for 30 minutes to obtain the hydrophilic nasal endoscope anti-fog agent. 1.2.1.4 Preparation of nano silica modified hydrophilic nasal endoscope anti-fog agent: Add 0.025g, 0.050g, and 0.100g of nano SiO2 respectively to three test tubes containing the same hydrophilic nasal endoscope anti-fog agent; then add 0.025g, 0.050g, and 0.100g of nano SiO2-KH570 respectively to three test tubes with 5ml of the same hydrophilic nasal endoscope anti-fog agent. The mixed solutions are ultrasonically dispersed for 30 minutes to obtain six different modified anti-fog agents.To synthesize hydrophilic polymers with functional groups, prepare a solution of polyvinylpyrrolidone (PVP) at a desired concentration. Modify the PVP by adding a specific mass percentage of nanoparticles, such as nano zinc oxide, nano titanium dioxide, and hollow nano silica, into the PVP solution. Investigate the changes in anti-fog performance of the modified anti-fog agent and explore the mechanism behind the alterations in its anti-fog properties.将10ml钛酸丁酯加入至40ml无水乙醇中，充分搅拌1小时，随后将2ml盐酸及3ml去离子水加入至8ml无水乙醇中，充分搅拌10分钟后缓慢滴入至上述钛酸丁酯乙醇溶液中，调节pH为5，并在30°C下反应24小时。离心分离反应物质（转速6000rpm），在100°C的烘箱中放置10小时后将物质放入马弗炉中升温2小时至500°C，保温0.5小时后自然降温，得到纳米二氧化钛。将0.50g聚丙烯酸溶于5.60ml氨水中至充分溶解，加入100ml无水乙醇，快速搅拌下缓慢滴加2.00ml正硅酸乙酯，在室温下搅拌12小时。离心分离反应物质（转速6000rpm）5分钟后，去除上层，加入去离子水，超声分散15分钟，再离心，清洗去离子水4次，将离心物在100°C的烘箱中干燥6小时，得到纳米二氧化硅中空微球。将9克聚乙烯吡咯烷酮溶于80ml去离子水中，在60°C水浴恒温下搅拌4小时充分溶解。将不同量的纳米二氧化锌、纳米氧化钛和纳米二氧化硅中空微球加入至各自的5ml聚乙烯吡咯烷酮溶液中，所有液体均超声分散30分钟，即得不同鼻内窥镜防雾剂。无水乙醇、盐酸（36%）、氨水、氢氧化钠、正硅酸乙酯（28.4%）、丙稀酸及硅烷偶联剂（分子量290）被用作实验试剂。1. Prepare clean glass slides by cutting them to approximately 2.0 cm x 2.0 cm size. Clean the slides in a solution of detergent in water using ultrasonic cleaning for 30 minutes, then rinse with ultrapure water until clean. Soak the slides in 3 mol/L sodium hydroxide solution for 3 hours, rinse with deionized water until no water beads remain on the surface, then clean with alcohol and dry to obtain a clean surface. Minimize time between cleaning and film formation to avoid contamination.\\n\\n2. Prepare acid sol by adding 8.36 mL tetraethyl orthosilicate (TEOS) to 80 mL anhydrous ethanol and dissolve fully. Under magnetic stirring, drop in 4.8 mL of 36% hydrochloric acid and stir for 19 hours.\\n\\n3. Prepare alkaline gel by adding 3.1 mL TEOS to 80 mL anhydrous ethanol and dissolve fully. Then add 13.8 mL deionized water and, under magnetic stirring, gradually drop in 4.7 mL analytical grade ammonia solution. Seal and react for 1 hour.\\n\\n4. Prepare acrylic acid solution by dissolving 3.0 g of four different batches of acrylic acid (A396, A842, A53, BM-51) in 50 mL anhydrous ethanol, stirring until completely dissolved.\\n\\n5. Combine acid sol, acrylic acid solution, and alkaline gel in anhydrous ethanol as per the specified ratios in the accompanying table, and sonicate for 1 hour to ensure proper dispersion.\\n\\n6. Prepare silane coupling agent solution by adding 3 mL deionized water and 2 mL silane coupling agent to 50.0 mL anhydrous ethanol and mix thoroughly.\\n\\n7. Immerse the cleaned glass slides in the sol for 10 seconds, then pull out at a speed of 3 mm/s using a film-coating machine. Let the coated slides sit at room temperature for 15 minutes to form a uniform film due to surface adsorption and chemical bonding. Repeat this process to prepare 3-layer and 5-layer films.\\n\\n8. Allow the films to air dry, then place the coated slides in a muffle furnace, heat to 400°C for 2 hours, and maintain for 0.5 hours before allowing to cool naturally to obtain transparent silica film samples.\\n\\n9. Finally, immerse the silica-coated glass slides in the silane coupling agent solution for 3 hours, then dry in an oven at 100°C for 60 minutes to obtain the final transparent silica film.In the sol-gel method, high chemical activity components are used as precursors. These raw materials are uniformly mixed in the liquid phase, followed by hydrolysis and condensation chemical reactions to form a stable transparent sol system in the solution. The sol undergoes slow polymerization of gel particles and forms a gel with a three-dimensional spatial network structure filled with solvent that has lost its fluidity. The gel is then dried and sintered to prepare micro-nano structures. For example, Venkateswara et al. used methyl trimethoxysilane (MTMS) and methanol to prepare a transparent film, which was modified with trimethyl chlorosilane. The contact angle of water on its surface reached $166^{\\circ}$. Furthermore, various other studies are mentioned where similar methods using different precursors lead to hydrophilic polymers with functional groups and desired contact angles."
+}
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diff --git a/task2/task2-paper-info/▓у▓у╫╘╫щ╫░ Science ╓╨╬─.json b/task2/task2-paper-info/▓у▓у╫╘╫щ╫░ Science ╓╨╬─.json
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+{
+    "protocol": "LbL 组装是一个循环过程，在这一过程中，带电材料被吸附在基底上，经过洗涤后，带相反电荷的材料被吸附在第一层之上。这样就形成了厚度一般在纳米级的单层双电层，然后可以重复沉积过程，直到形成所需厚度的多层薄膜为止。"
+}
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diff --git a/task2/task2-paper-info/▓у▓у╫╘╫щ╫░ Science.json b/task2/task2-paper-info/▓у▓у╫╘╫щ╫░ Science.json
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+++ b/task2/task2-paper-info/▓у▓у╫╘╫щ╫░ Science.json	
@@ -0,0 +1,3 @@
+{
+    "protocol": "Layer-by-layer (LbL) assembly is a cyclical process in which a charged material is adsorbed onto a substrate, and after washing, an oppositely charged material is adsorbed on top of the first layer. This constitutes a single bilayer with a thickness generally on the order of nanometers, and the deposition process can then be repeated until a multilayer film of desired thickness has been assembled. Various interactions can be utilized for LbL assembly, including electrostatic interactions, covalent bonds, hydrogen bonding, and host-guest interactions, using diverse materials such as polymers, proteins, lipids, nucleic acids, nanoparticles, and suprastructures."
+}
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diff --git a/task2/task2-qa/1-s2.0-S0040609020301334-main.json b/task2/task2-qa/1-s2.0-S0040609020301334-main.json
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+{
+  "design_question": "Considering dimethyl allylphosphonate, explain how you would optimize the PECVD process parameters, such as plasma power and pulsed versus continuous plasma configuration, to achieve uniform surface modification of the polymer.",
+  "design_answer": "To answer your question systematically and comprehensively, I will first analyze the query and derive key points, followed by detailing the process of optimizing the Plasma Enhanced Chemical Vapor Deposition (PECVD) process parameters for uniform surface modification of polymers using dimethyl allylphosphonate. By taking a logical and scientific approach, I will aim to provide specific experimental parameters to help you achieve your objective in the laboratory.\n\n---\n\n### **Key Points Analysis**\nThe key aspects of your question are:\n1. **Material of Interest**: Dimethyl allylphosphonate (DMAP), a molecule with polar functional groups, which suggests potential for imparting hydrophilic properties upon the polymer surface.\n2. **Goal**: Achieving uniform surface functionalization with the help of the PECVD process to enhance hydrophilicity.\n3. **Optimization Factors in PECVD**:\n   - **Plasma Power**: Balancing fragmentation and deposition to achieve the desired surface modification.\n   - **Pulsed vs. Continuous Plasma Configurations**: Examining the impact of each mode on deposition uniformity, crosslinking density, and preservation of the desired functional groups.\n4. **Outcome**: Uniform, controlled incorporation of dimethyl allylphosphonate onto the polymer surface to increase hydrophilicity while preserving the chemical integrity of functional groups.\n\nWith these points in mind, let us proceed step by step with the PECVD optimization process.\n\n---\n\n### **Systematic Explanation of PECVD Optimization Using Dimethyl Allylphosphonate**\n\n#### **Step 1: Understanding the Molecular Properties of Dimethyl Allylphosphonate**\nDimethyl allylphosphonate contains:\n- A polar phosphonate group (-PO3R2), which enhances surface wettability through hydrogen bonding or dipole interactions with water molecules.\n- An allyl group (-CH2CH=CH2), which allows potential crosslinking or copolymerization in the PECVD plasma environment.\n- Moderate thermal and chemical stability, which influences the choice of process conditions (e.g., plasma energy and substrate temperature).\n\nThis combination makes DMAP a suitable precursor for hydrophilic modification via PECVD.\n\n---\n\n#### **Step 2: Selection of Precursor Delivery System**\n1. Utilize a **vapor delivery system** to introduce dimethyl allylphosphonate (DMAP) into the PECVD chamber as a vapor-phase precursor. \n   - DMAP can be vaporized by heating mildly above room temperature (35–50°C) depending on its vapor pressure while avoiding decomposition.\n   - A carrier gas such as argon (Ar) or nitrogen (N2) can help transport the precursor into the chamber.\n\n#### **Step 3: Plasma Power Optimization**\nThe plasma power (or RF power) parameter controls the energy imparted to the precursor, influencing its fragmentation and reactivity:\n1. **Low Plasma Power (20–50 W)**:\n   - Promotes gentle fragmentation, preserving polar phosphonate groups.\n   - Results in longer deposition times but maintains functional group integrity and hydrophilicity.\n   - Suitable if minimal chemical alteration of DMAP is desired.\n   \n2. **Moderate Plasma Power (50–150 W)**:\n   - Achieves a balance between precursor fragmentation and recombination.\n   - Increases deposition rate and enhances crosslinking, while still retaining polar functionalities under optimal conditions.\n   - Likely an ideal range for your experiment to ensure uniform surface coverage and effective functionalization.\n\n3. **High Plasma Power (>150 W)**:\n   - Causes excessive precursor fragmentation, leading to loss of functional groups and formation of non-hydrophilic crosslinked films (graphitic or carbon-rich layers).\n   - Avoid at high power if preservation of hydrophilic properties is critical.\n\n---\n\n#### **Step 4: Pulsed vs. Continuous Plasma Configuration**\nThe choice between pulsed and continuous plasma significantly affects surface uniformity and functional group preservation:\n\n1. **Pulsed Plasma**:\n   - Involves alternating \"on\" and \"off\" cycles of plasma generation.\n   - Benefits:\n     - Reduces excessive fragmentation by allowing functional group-containing fragments to deposit during the \"off\" periods.\n     - Better control over crosslinking density, reducing polymer damage or over-deposition.\n   - Parameters to consider:\n     - Duty Cycle (on/off ratio): Start with around 50% duty cycle (e.g., 500 ms \"on\", 500 ms \"off\").\n     - Frequency: Use typical ranges such as 1–10 kHz for controlled energy delivery.\n\n2. **Continuous Plasma**:\n   - Plasma remains \"on\" through the entire process.\n   - Benefits:\n     - Higher deposition rates and simpler process control.\n   - Drawbacks:\n     - Potential for over-fragmentation of DMAP, reducing hydrophilic group density.\n   - Suitable only if optimization of other parameters (low plasma power, short deposition time) prevents overreaction.\n\n**Recommendation**: Start with pulsed plasma to achieve higher uniformity and better functional group retention. Optimize duty cycle and frequency for your specific setup.\n\n---\n\n#### **Step 5: Deposition Temperature**\nThe substrate temperature during PECVD also affects deposition quality:\n- Maintain moderate substrate temperatures (40–80°C) to avoid premature polymer degradation or over-fragmentation of DMAP.\n- Higher temperatures may enhance crosslinking but can also result in the loss of polar functional groups.\n\n---\n\n#### **Step 6: Reaction Chamber Pressure**\nThe chamber pressure directly influences the mean free path of ions and radicals in the plasma:\n- Start with standard PECVD pressures (50–200 mTorr) and ensure uniform precursor distribution.\n- Lower pressures favor higher energy collisions, whereas higher pressures reduce ion energy but enhance layer uniformity.\n\nExperiment with 100 mTorr as a baseline pressure for your trials.\n\n---\n\n#### **Step 7: Experimental Trials and Optimization**\nConduct a systematic evaluation of the combinations of key parameters:\n1. Plasma Power: Start with 50 W and incrementally increase up to 150 W.\n2. Pulsed Plasma Duty Cycle: Experiment with 30–70% duty cycles.\n3. Chamber Pressure: Test 100 mTorr ± 50 mTorr.\n4. Temperature: Keep 60°C constant initially, then adjust if necessary.\n\n---\n\n#### **Step 8: Characterization and Evaluation**\nAfter surface modification, evaluate the polymer surface to confirm successful deposition of hydrophilic DMAP:\n1. **Contact Angle Measurement**:\n   - Quantify hydrophilicity by measuring water contact angles. Lower angles indicate increased hydrophilic modification.\n2. **Fourier Transform Infrared Spectroscopy (FTIR)**:\n   - Confirm the presence of phosphonate functional groups on the surface.\n3. **X-ray Photoelectron Spectroscopy (XPS)**:\n   - Detect elemental composition and confirm the incorporation of phosphorus (from DMAP) on the surface.\n4. **Surface Morphology**:\n   - Use Scanning Electron Microscopy (SEM) or Atomic Force Microscopy (AFM) to check for uniformity.\n5. **Adhesion Testing**:\n   - Verify the durability of the modified surface layer.\n\n---\n\n### **Conclusion**\nTo achieve uniform surface functionalization while preserving hydrophilicity, I recommend the following optimized process:\n1. **Plasma Configuration**: Pulsed plasma with a duty cycle around 50%.\n2. **Plasma Power**: Moderate power of ~100 W (adjust as necessary).\n3. **Temperature**: Substrate temperature of 60°C.\n4. **Pressure**: Chamber pressure of 100 mTorr.\n5. **Precursor Introduction**: Vaporized DMAP with N2 or Ar as carrier gas.\n\nConduct systematic variations in these parameters while evaluating the results through appropriate characterization techniques. By carefully balancing plasma power and deposition conditions, you should achieve a uniform, hydrophilic polymer surface.\n\nI hope this detailed explanation provides clarity. If you have further questions, don’t hesitate to ask!"
+}
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diff --git a/task2/task2-qa/1-s2.0-S030094402400482X-main.json b/task2/task2-qa/1-s2.0-S030094402400482X-main.json
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+{
+  "design_question": "Explain how you would use triethoxyvinylsilane (A151) in the synthesis of a hydrophilic polymer. Specify the conditions and steps required for this molecule to effectively contribute to the polymerization process.",
+  "design_answer": "Thank you for your question. I appreciate your curiosity in the synthesis of hydrophilic polymers and your interest in triethoxyvinylsilane (A151) as a precursor. Let’s examine this systematically, step-by-step, in detail.\n\n---\n\n### **Analysis and Key Points**\n\nTriethoxyvinylsilane (A151) is a silane coupling agent containing a vinyl group that facilitates participation in polymerization reactions, while its triethoxy functional group enables hydrolysis and condensation to generate silanol groups. Its versatility makes it an ideal component for enhancing the hydrophilicity of polymer systems.\n\nTo use A151 effectively in the synthesis of a hydrophilic polymer, the strategy typically involves:\n1. **Incorporating the vinyl group into the polymer backbone** via radical polymerization.\n2. **Introducing hydrophilic functional groups** through strategies like co-polymerization or post-modification.\n3. **Exploiting the triethoxy functionalities** for hydrolysis and cross-linking to introduce silanol (-SiOH) functionalities that enhance hydrophilicity.\n\nWe will design a practical synthesis scheme involving A151 based on these properties.\n\n---\n\n### **Experimental Preparation Scheme for the Synthesis of a Hydrophilic Polymer Using Triethoxyvinylsilane (A151)**\n\n#### **Step 1: Selection of Co-Monomer or Hydrophilic Modifier**\nSince A151 does not inherently contribute significant hydrophilicity, it is essential to co-polymerize A151 with a hydrophilic monomer such as:\n- **Acrylic acid (AA)**: A monomer with carboxylic acid groups that ensure hydrophilicity.\n- **Hydroxyethyl methacrylate (HEMA)**: Provides hydroxyl groups for enhanced hydrophilicity.\n\nFor this example, we will co-polymerize A151 with acrylic acid (AA).\n\n---\n\n#### **Step 2: Preparation of the Reaction Mixture**\n- **Reagents:**\n  - Triethoxyvinylsilane (A151): 0.2–0.5 mol\n  - Acrylic acid (AA): 1 mol\n  - Solvent: Ethanol or water (ethanol aids in solubilizing A151; water facilitates hydrolysis of the triethoxy groups later).\n  - Initiator: Azobisisobutyronitrile (AIBN), commonly used for radical polymerization; ~0.01 mol% relative to monomer concentrations.\n  - Catalyst (optional): Acidic catalysts such as HCl or H2SO4 for hydrolysis of the triethoxy group.\n\n---\n\n#### **Step 3: Radical Co-Polymerization**\nRadical polymerization introduces vinyl groups (from A151 and AA) into the polymer backbone.\n\n1. **Reaction Setup:**\n   - Use a three-neck flask equipped with a stirrer, condenser, and nitrogen inlet.\n   - Charge the flask with A151, acrylic acid, the solvent (ethanol or ethanol-water mixture), and AIBN.\n   - Purge the reaction mixture with nitrogen for ~30 minutes to eliminate oxygen, which can inhibit polymerization.\n\n2. **Reaction Conditions:**\n   - Maintain a temperature of **65–75°C** for 4–6 hours (this is the optimal range for AIBN decomposition and radical initiation).\n   - Stir continuously to ensure homogeneity of the reaction mixture.\n\n3. **Polymer Formation:**\n   - Co-polymerization proceeds, where vinyl groups polymerize to form the hydrophilic polymer backbone, incorporating silane groups.\n\n---\n\n#### **Step 4: Hydrolysis of Triethoxy Groups**\nPost-polymerization, the triethoxy groups on A151 are hydrolyzed to generate hydrophilic silanol groups. This step significantly enhances the hydrophilicity of the polymer.\n\n1. **Hydrolysis Conditions:**\n   - Add a small amount of acidic catalyst (e.g., dilute HCl, pH ~3–4) to the reaction mixture.\n   - Use water or a water-ethanol mixture as a solvent medium.\n   - Stir at room temperature (~20–25°C) for 6–12 hours to allow hydrolysis of the ethoxy groups (-OEt) into hydroxyl (-OH) groups, forming silanol (-SiOH).\n\n2. **Condensation (Optional):**\n   - Catalyze condensation between silanol groups to form cross-linked domains in the polymer structure. This creates a gel-like or network structure, further enhancing hydrophilicity and mechanical stability.\n\n---\n\n#### **Step 5: Purification**\nAfter the polymerization and hydrolysis reactions, purification ensures the removal of unreacted monomers, initiators, and by-products.\n1. **Precipitation:**\n   - Precipitate the polymer by adding the reaction solution to a non-solvent such as acetone or diethyl ether.\n2. **Washing:**\n   - Wash the polymer with water to remove soluble impurities.\n3. **Drying:**\n   - Dry the purified polymer in a vacuum oven at ~40–60°C.\n\n---\n\n#### **Step 6: Characterization**\nThe synthesized polymer may be characterized to confirm structure and hydrophilicity enhancement.\n1. **Structural Analysis:**\n   - Use Fourier-transform infrared (FTIR) spectroscopy to identify hydroxyl (-OH), carboxyl (-COOH), and silanol (-SiOH) groups in the polymer.\n2. **Thermal Properties:**\n   - Perform thermogravimetric analysis (TGA) or differential scanning calorimetry (DSC) to evaluate the polymer's thermal stability.\n3. **Hydrophilicity Test:**\n   - Measure water contact angle to confirm improved hydrophilicity.\n\n---\n\n### **Conclusion**\nThrough this experimental scheme, triethoxyvinylsilane (A151) plays a dual role:\n1. **Polymer Backbone Incorporation:** The vinyl group participates in radical co-polymerization, forming part of the backbone.\n2. **Hydrophilicity Enhancement:** The hydrolysis of triethoxy groups introduces silanol (-SiOH) functionalities, amplifying the hydrophilic character of the polymer.\n\nBy carefully following reaction conditions—such as correct temperature, reagent ratios, hydrolysis conditions, and purification steps—you should be able to synthesize a hydrophilic polymer that leverages the unique properties of A151 effectively.\n\nIf you have additional questions or need further clarification, don’t hesitate to ask—synthesizing high-performance hydrophilic polymers is a fascinating and rewarding process!"
+}
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diff --git a/task2/task2-qa/1-s2.0-S0927775719302274-main.json b/task2/task2-qa/1-s2.0-S0927775719302274-main.json
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+{
+  "design_question": "Design an experimental procedure using HMDS to evaluate how its exposure time affects the contact angle of water on a polymer surface. Include steps for surface cleaning, treatment, and analysis.",
+  "design_answer": "This is an interesting and insightful question, as analyzing the effect of hexamethyldisilazane (HMDS) exposure time on the wettability of a polymer surface can provide valuable insights into surface modification chemistry and its influence on hydrophilicity. To answer this systematically and in detail, let's break it down step by step while emphasizing surface cleaning, treatment, experimental design, and analysis.\n\n---\n\n### Key Points from the Question:\n1. **Objective**: Evaluate how the exposure time of HMDS affects the contact angle of water on a polymer surface. \n2. **Key Steps**: Surface cleaning (to remove contaminants), surface HMDS treatment (to modify surface properties), and analysis (to measure water contact angle and assess changes in hydrophilicity).\n3. **Critical Parameters**: Exposure time to HMDS, contact angle measurement, and reproducibility.\n\n---\n\n### Detailed Experimental Procedure:\n\n#### Step 1: **Material Preparation and Surface Cleaning**\n1. **Materials Required**:\n   - Polymer samples (e.g., polymethyl methacrylate (PMMA), polyethylene (PE), or polydimethylsiloxane (PDMS)).\n   - Hexamethyldisilazane (HMDS) – analytical grade.\n   - Solvents for cleaning: ethanol, acetone, deionized (DI) water.\n   - Clean glassware and a desiccator.\n   - Nitrogen (N₂) gas or compressed dry air for drying.\n\n2. **Surface Cleaning Protocol**:\n   - Clean the polymer surfaces thoroughly to remove dust, oils, and any organic contaminants. Follow this procedure:\n     - Sonicate the polymer samples in ethanol for 10 minutes.\n     - Rinse them with acetone to remove residual organic contaminants.\n     - Wash the surfaces with DI water to eliminate any residual impurities.\n     - Dry the samples with nitrogen gas or place them in a vacuum desiccator for 30 minutes to ensure a dry, clean surface.\n   - **Note**: Surface cleaning is crucial to ensure that observed changes in wettability are solely due to HMDS treatment and not residual contamination.\n\n---\n\n#### Step 2: **HMDS Treatment**\n1. **Reaction Vessel Setup**:\n   - Use a vacuum desiccator or a sealed reaction chamber that can be evacuated and refilled with HMDS vapor. Ensure cleanliness of the chamber prior to introducing the polymer samples.\n   - Place the polymer samples evenly spaced on a clean glass tray or holder, ensuring uniform exposure to HMDS vapor.\n\n2. **Introducing HMDS**:\n   - Add approximately 1–2 mL of HMDS to a small Petri dish or watch glass and place it at the bottom of the desiccator/chamber.\n   - Seal the chamber and evacuate the air within to reduce ambient humidity and create a low-pressure environment (optional but recommended).\n\n3. **Exposure Process**:\n   - Allow HMDS to vaporize and interact with the polymer surfaces for specific exposure times. Design the experiment to test different exposure times to study their effect on the contact angle. Suggested time intervals: 5 minutes, 15 minutes, 30 minutes, 1 hour, and 2 hours.\n   - After each exposure time, remove the polymer sample carefully from the chamber and proceed to characterization (detailed in Step 4 below).\n\n4. **Post-Treatment Drying (Optional)**:\n   - After exposure, polymer samples can be baked at 60–80 °C for 15 minutes in a hot-air oven or placed in a vacuum desiccator for 30 minutes to ensure evaporation of unreacted HMDS.\n\n5. **Reaction Mechanism**:\n   - HMDS reacts with surface hydroxyl (-OH) groups, replacing them with methyl (-CH₃) groups. This results in changes to surface wettability and potentially increases hydrophobicity (reduces hydrophilicity). By varying exposure time, the extent of surface modification can be controlled.\n\n---\n\n#### Step 3: **Characterization and Analysis**\n1. **Contact Angle Measurement**:\n   - Use a contact angle goniometer to measure the static water contact angle on the HMDS-treated polymer surfaces. Follow these steps:\n     - Place a polymer sample on the goniometer stage.\n     - Deposit a ~2 µL droplet of DI water on the polymer surface using a microsyringe.\n     - Measure the contact angle between the baseline of the droplet and the tangent at the contact point with the surface.\n   - Record the contact angle for each exposure time.\n   - Perform 3–5 measurements on different locations of each sample to ensure reproducibility and report the average contact angle.\n\n2. **Surface Chemistry Analysis (Optional)**:\n   - Use Fourier-transform infrared spectroscopy (FTIR) to confirm the surface chemical modification (e.g., disappearance of -OH groups and appearance of -CH₃ functional groups).\n   - Conduct X-ray photoelectron spectroscopy (XPS) to quantify the elemental composition and extent of HMDS interaction.\n\n3. **Control Experiment**:\n   - Measure the contact angle of untreated polymer surfaces as a control for comparison with HMDS-treated samples.\n   - Also consider treating the polymer with shorter (1–2 minute) and longer exposure times (e.g., 4–6 hours) for better understanding of saturation behavior.\n\n---\n\n#### Step 4: **Data Analysis**\n1. **Plot the Results**:\n   - Plot contact angle versus HMDS exposure time. This will help visualize trends (e.g., a potential increase in the contact angle due to surface modification).\n   - Analyze whether the contact angle plateaus after a certain exposure time, indicating saturation of surface modification.\n\n2. **Interpretation**:\n   - Compare the treated samples to the untreated control to evaluate the effect of HMDS treatment.\n   - Discuss surface wettability changes in terms of surface energy and the extent of surface modification.\n\n---\n\n### Safety Considerations:\n1. HMDS is volatile and flammable, so work in a fume hood and avoid open flames.\n2. Wear proper personal protective equipment (PPE), including gloves, goggles, and a lab coat.\n3. Dispose of HMDS and other chemical waste according to institutional safety guidelines.\n\n---\n\n### Conclusion:\nThis experimental procedure addresses your question in a structured manner. By cleaning the surface, treating it with HMDS vapor under controlled conditions, and analyzing the water contact angle, you can systematically evaluate how HMDS exposure time affects the hydrophilicity of the polymer. This approach ensures reproducibility, reliability, and scientific rigor, providing meaningful results for your study."
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+{
+  "design_question": "Explain how you would utilize 3-Trimethoxysilylpropyl methacrylate (TMSMA) in the experiment to improve adhesion of the polymer to a glass substrate. What specific steps would you take to activate the substrate prior to applying the polymer coating?",
+  "design_answer": "To answer your question regarding the use of **3-Trimethoxysilylpropyl methacrylate (TMSMA)** to improve the adhesion of a polymer to a glass substrate, I will first analyze the key points of the question and then systematically present an experimental procedure with all the necessary details.\n\n---\n\n### **Key Points of the Question:**\n1. **Role of TMSMA**: TMSMA is a silane coupling agent containing both silane functionality (trimethoxysilyl) and a polymerizable methacrylate group. The dual functionality can form strong covalent bonds with the silanol groups on the glass surface and participate in polymerization reactions, thereby improving adhesion.\n2. **Activation of the Glass Substrate**: Glass substrates need to be cleaned and activated (typically through chemical or plasma methods) to ensure that the hydroxyl groups on the surface are accessible for reaction with the silane coupling agent.\n3. **Synthesis and Application Process**: Applying the polymer coating involves substrate pretreatment, TMSMA surface functionalization, and subsequent polymer deposition using appropriate conditions.\n\n---\n\n### **Detailed Experimental Scheme:**\n\n#### **Step 1: Glass Substrate Cleaning and Activation**\nThe first step is to prepare the glass surface to ensure high surface energy, cleanliness, and the presence of reactive hydroxyl (-OH) groups.\n1. **Materials Required**:\n   - Glass slides or substrates.\n   - Cleaning agents: Deionized (DI) water, ethanol (or isopropanol), and piranha solution (or equivalent cleaning method).\n   - Sodium hydroxide (NaOH) or hydrochloric acid (HCl) for surface activation.\n2. **Procedure**:\n   a. **Physical Cleaning**:\n      - Rinse the glass thoroughly with a 50:50 mixture of ethanol and DI water to remove dust and grease.\n      - Sonicate the glass slides in ethanol for 15 minutes for better cleaning.\n   b. **Chemical Cleaning** (if higher cleanliness is required):\n      - Prepare a piranha solution (3:1 mixture of H₂SO₄ and H₂O₂). Warning: Handle with extreme caution in a fume hood, as this reaction is highly exothermic.\n      - Immerse the glass slides in the piranha solution for 10-15 minutes to remove organic contaminants.\n      - Rinse thoroughly with DI water multiple times to remove all residual acid.\n   c. **Surface Hydroxylation**:\n      - Prepare an alkaline solution (0.1 M NaOH) or acidic solution (0.1 M HCl).\n      - Immerse the clean glass substrate in the NaOH (or HCl) solution for 30 minutes at room temperature.\n      - Rinse the glass substrate with DI water and dry with nitrogen gas.\n   d. **Final Drying**:\n      - Dry the glass substrates in a clean oven at 110–120 °C for 30 minutes to completely remove moisture but ensure reactive -OH groups remain intact.\n      - Cool the substrates to room temperature in a desiccator before proceeding.\n\n---\n\n#### **Step 2: Functionalization with TMSMA**\nThe next step is to treat the activated glass substrate with TMSMA to create a silanized surface that enhances polymer adhesion.\n1. **Materials Required**:\n   - TMSMA.\n   - Ethanol or an ethanol-water mixture (95:5 ratio).\n   - Acetic acid (as a catalyst for hydrolysis).\n   - Glass substrates from Step 1.\n   - Glovebox or clean environment to minimize contamination.\n2. **Procedure**:\n   a. **Prepare the Silane Solution**:\n      - In a clean glass vial, mix ethanol and DI water in a 95:5 ratio (v/v).\n      - Add acetic acid dropwise to adjust the pH to ~4.5 (slightly acidic).\n      - Slowly add TMSMA to achieve a concentration of 2–5% (v/v) in the solution.\n      - Stir the solution at room temperature for 10–15 minutes to promote hydrolysis of the methoxysilyl groups to silanols (Si–OH).\n   b. **Coating Process**:\n      - Immerse the cleaned and activated glass substrates in the TMSMA solution.\n      - Allow the substrates to sit in the solution for 15–30 minutes to enable sufficient binding of the silane to the glass surface through condensation reactions between TMSMA’s Si–OH groups and the glass’s surface hydroxyl groups.\n   c. **Post-Treatment**:\n      - Remove the substrates from the solution and rinse them gently with ethanol to remove excess unreacted silane.\n      - Allow the substrates to dry at room temperature in a nitrogen atmosphere for 10–15 minutes.\n      - Cure the silanized substrates in a vacuum oven at 110–120 °C for 1–2 hours to drive the condensation reaction to completion, forming a covalent Si–O–Si network.\n\n---\n\n#### **Step 3: Polymer Coating Application**\nWith the TMSMA-functionalized glass substrate prepared, the polymer (containing hydrophilic components) can now be coated. In this step, the methacrylate group in TMSMA can covalently bond with the polymer, ensuring strong adhesion.\n1. **Materials Required**:\n   - Polymer solution or monomer(s) for polymerization (compatible with the targeted application).\n   - Additional solvent (if needed) to adjust coating viscosity.\n   - Initiator for polymerization (e.g., thermal, UV, or redox initiators, depending on monomer choice).\n   - Spin coater (optional) or dip-coating setup.\n2. **Procedure**:\n   a. **Preparation of Polymer or Monomer Solution**:\n      - Dissolve the polymer in a suitable solvent if applying an existing polymer. Alternatively, prepare a monomer solution with the desired molar ratios for copolymerization.\n      - Add the initiator in the required proportion (commonly 1–5% w/w of the monomers).\n   b. **Coating onto the Substrate**:\n      - Place the TMSMA-functionalized glass substrate in a spin-coater or dip-coating setup.\n      - Deposit the polymer or monomer solution onto the substrate.\n      - Spread the solution evenly over the surface (e.g., spin-coating can use 1500–3000 rpm for 30–60 seconds, depending on viscosity).\n   c. **Polymerization** (if monomers are used):\n      - Expose the coated substrate to appropriate conditions (e.g., heat to 60–80 °C for thermal polymerization or UV lamp for photopolymerization, depending on initiator).\n   d. **Curing and Finalization**:\n      - Allow the polymer-coated substrate to cure and cool to room temperature.\n      - Rinse and dry the substrate if necessary to remove unreacted monomers or solvents.\n\n---\n\n### **Reaction Details and Mechanism:**\n1. **Glass Functionalization (Step 2)**:\n   - Hydrolyzed TMSMA silanol groups react with the surface hydroxyl groups on the glass, forming strong Si–O–Si covalent bonds while the methacrylate group remains exposed for further polymerization.\n   - Reaction mechanism:\n     \\[\n     \\text{Si-OCH}_3 + \\text{H}_2\\text{O} \\rightarrow \\text{Si-OH} + \\text{CH}_3\\text{OH}\n     \\]\n     \\[\n     \\text{Si-OH (TMSMA)} + \\text{Si-OH (glass)} \\rightarrow \\text{Si-O-Si (covalent bond)} + \\text{H}_2\\text{O}\n     \\]\n2. **Polymer-Coating Step**:\n   - The methacrylate groups on TMSMA copolymerize with monomers or cross-link with polymers, forming a durable interfacial bond.\n\n---\n\nBy following the steps outlined above, the adhesion of hydrophilic polymers to glass substrates will be greatly enhanced due to the dual functionality of TMSMA. Be sure to carefully monitor reaction conditions and maintain a clean working environment to ensure reproducibility of results."
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+{
+  "design_question": "In the preparation of hydrophilic polymers, what factors should be considered when applying ZnCl2 to a substrate? Suggest specific parameters such as concentration, application method, and environmental conditions to achieve optimal results.",
+  "design_answer": "Certainly! Let’s analyze your question step by step to provide a systematic and detailed answer.\n\n---\n\n### **Analysis of the Question**\nYour question focuses on the application of ZnCl₂ to a substrate in the context of hydrophilic polymer preparation. ZnCl₂ (zinc chloride) is a versatile reagent, often used in polymer science due to its hygroscopic properties, catalytic activity, and ability to enhance hydrophilicity by modifying surface chemistry. To achieve optimal performance, the following key considerations need to be addressed:\n\n1. **ZnCl₂ concentration**: The concentration of ZnCl₂ affects its ability to activate the substrate surface or participate in the polymerization process.\n2. **Application method**: How ZnCl₂ is applied to the substrate (e.g., solution immersion, spin coating, dip-coating, spray coating, etc.) can determine uniformity and reaction efficiency.\n3. **Environmental conditions**: Parameters such as temperature, pH, humidity, and reaction time have a significant influence on the functionalization of the substrate and the successful incorporation into a hydrophilic polymer system.\n\n---\n\n### **Step-by-Step Detailed Answer**\n\nBelow, I outline an experimental preparation scheme for applying ZnCl₂ to a substrate with optimal parameters for hydrophilic polymer synthesis.\n\n#### **Step 1: Preparation of ZnCl₂ Solution**\n1. **Concentration**: Prepare a ZnCl₂ aqueous solution with a typical concentration range of **0.1 M to 0.5 M**, depending on the substrate's surface area, compatibility, and the desired surface modification.\n   - For highly porous or absorptive substrates, use a lower concentration (e.g., 0.1 M) to prevent excessive deposition, which might limit polymer interaction.\n   - For non-porous substrates or when stronger surface modification is desired, 0.3–0.5 M is appropriate.\n2. **Solvent Selection**: Use distilled water as the solvent for ZnCl₂, unless the substrate is water-sensitive. In such cases, ethanol, methanol, or a water-ethanol blend may be used to dissolve ZnCl₂.\n\n#### **Step 2: Surface Preparation of the Substrate**\nBefore applying the ZnCl₂ solution, ensure the substrate is clean and prepared:\n1. **Cleaning**: Remove any surface impurities by washing the substrate with ethanol or isopropanol, followed by deionized water. Dry the substrate in air or in an oven at **80–100°C**.\n2. **Activation (if applicable)**: For stronger ZnCl₂ adherence, activate the substrate surface using plasma treatment, UV-ozone treatment, or mild etching with a dilute acid (e.g., 1 M HCl) to remove oxides and impurities.\n\n#### **Step 3: Application of ZnCl₂ to the Substrate**\nChoose an application method tailored to the substrate and experimental goals:\n1. **Dip Coating**:\n   - Immerse the substrate in the ZnCl₂ solution for **5–30 minutes** to allow sufficient interaction and coverage.\n   - Use gentle stirring of the ZnCl₂ solution to ensure even contact.\n   - After immersion, remove the substrate and drain excess solution to achieve a uniform layer. Optionally, rinse briefly with the solvent to remove excess ZnCl₂ crystals.\n2. **Spin Coating** (for smooth, uniform layers):\n   - Place the substrate on a spin-coater and deposit a controlled amount of ZnCl₂ solution (e.g., 100–500 µL, depending on substrate size).\n   - Use a two-step spin program: typically, **500 rpm for 10 seconds** followed by **2000 rpm for 30 seconds** to spread the solution and achieve uniform coverage.\n3. **Spray Coating** (for large or uneven surfaces):\n   - Use a fine mist spray to apply the ZnCl₂ solution evenly over the substrate. Optimize the nozzle distance (10–20 cm) and application pressure to avoid droplet formation.\n4. **Drying**:\n   - After application, dry the substrate under controlled conditions (see Step 5) to solidify the ZnCl₂ layer.\n\n#### **Step 4: Environmental Conditions**\nDuring and after ZnCl₂ application, control the environmental factors to enhance reaction performance:\n1. **Temperature**: Perform the application process at **room temperature (20–25°C)** to prevent thermal decomposition of ZnCl₂. Higher temperatures may lead to ZnCl₂ crystallization instead of forming a uniform surface layer.\n2. **Humidity**: Avoid high humidity during the application process (keep it below **50% RH**) to prevent premature hydrolysis of ZnCl₂ and delamination.\n3. **pH Control (if applicable)**: ZnCl₂ is highly hygroscopic and can hydrolyze in aqueous media. Keep the solution mildly acidic (pH ~5–6) by adding a buffer (e.g., acetic acid) if necessary.\n\n#### **Step 5: Post-Application Treatment**\n1. **Thermal Treatment** (optional but beneficial):\n   - After ZnCl₂ application, cure the substrate at **80–120°C** for **30–60 minutes** in an oven or a vacuum chamber. This step ensures better bonding to the substrate and removes residual solvent.\n2. **Rinsing (if needed)**:\n   - For applications requiring a clean but hydrophilically modified surface (e.g., before polymer grafting), briefly rinse the substrate with a dilute ethanol/water solution and air-dry to remove loosely bound ZnCl₂.\n\n#### **Step 6: Integration with Hydrophilic Polymer Preparation**\n1. If ZnCl₂ is used as a catalytic or functional layer for subsequent polymerization (e.g., free radical or graft polymerization of hydrophilic monomers like acrylamide, hydroxyethyl methacrylate, or polyethylene glycol):\n   - Introduce the monomer solution directly over the ZnCl₂-coated substrate.\n   - Adjust the reaction conditions (e.g., temperature, initiator concentration) to ensure uniform polymer growth.\n\n2. For applications where ZnCl₂ enhances surface wettability prior to functionalization:\n   - Assess surface wettability by measuring the water contact angle. A reduction in the angle compared to the untreated substrate indicates successful hydrophilicity enhancement.\n\n---\n\n### **Key Experimental Parameters Summary**\n| **Parameter**            | **Recommended Range/Value**                  |\n|---------------------------|----------------------------------------------|\n| ZnCl₂ Concentration       | 0.1–0.5 M                                   |\n| Application Method        | Dip coating, spin coating, or spray coating |\n| Drying Temperature        | 80–120°C                                    |\n| Application Temperature   | 20–25°C (room temperature)                  |\n| Relative Humidity         | <50% RH                                     |\n| Reaction pH (if aqueous)  | Mildly acidic (pH ~5–6)                     |\n| Drying/Curing Time        | 30–60 minutes                               |\n\n---\n\nThis systematic approach should allow you to successfully apply ZnCl₂ to a substrate and progress toward hydrophilic polymer synthesis. Let me know if you’d like to discuss specific polymer systems or reaction mechanisms!"
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+{
+  "design_question": "Outline a detailed approach to dissolve polyvinyl alcohol (PVA) in a solvent mixture to prepare a solution that promotes hydrophilic properties in the final polymer. Highlight factors such as temperature and solvent ratios.",
+  "design_answer": "When preparing a hydrophilic polymer solution using polyvinyl alcohol (PVA), the goal is to optimize the solution conditions such that the hydrophilic properties of PVA are fully exploited while ensuring a uniform and stable solution for subsequent processing. Let's analyze and answer this question step by step.\n\n---\n\n### **Key Points to Address:**\n1. **Nature of Polyvinyl Alcohol (PVA):**  \n   PVA is inherently hydrophilic due to its hydroxyl (-OH) groups along the polymer backbone, which can form hydrogen bonds with water and other polar solvents.\n   \n2. **Factors Affecting Dissolution:**  \n   Successful dissolution of PVA involves careful attention to the following factors:\n   - Molecular weight and degree of hydrolysis of the PVA (fully or partially hydrolyzed forms).\n   - Solvent or solvent mixture compatibility with PVA (e.g., water or water with co-solvents like ethanol).\n   - Temperature, solvent ratios, and stirring conditions to ensure uniform dissolution.\n\n3. **Objective of the Solution Preparation:**  \n   Prepare a PVA solution with hydrophilic characteristics, suitable for processing into hydrophilic polymer formulations or blends.\n\n---\n\n### **Step-by-Step Detailed Approach:**\n\n#### **Step 1: Select the Appropriate PVA Grade**\n- **Molecular Weight and Degree of Hydrolysis:**  \n   Choose a PVA grade based on the application. Both fully hydrolyzed (~98-99% hydrolysis) and partially hydrolyzed (~87-89% hydrolysis) grades can be used, but fully hydrolyzed PVA tends to be more hydrophilic due to the higher hydroxyl content.\n   - Typical weight-average molecular weights: 9,000–125,000 g/mol.\n   - For this experiment, assume we are using fully hydrolyzed PVA with a molecular weight of 88,000 g/mol.\n\n#### **Step 2: Prepare the Solvent System**\n- **Solvent Selection:**  \n   - Primary solvent: Water is typically used for PVA dissolution because it forms strong hydrogen bonds with the polymer.\n   - Co-solvent (optional): A small amount of ethanol (e.g., 5-20% w/w) may be added to improve solubility, reduce viscosity, or control crystallization in certain applications.\n- **Solvent Ratio:**  \n   For a basic PVA solution, start with 100% water. If incorporating ethanol, use a 90:10 or 80:20 (water:ethanol) ratio by weight.\n\n#### **Step 3: Weigh and Mix Reagents**\n1. **Weigh the PVA Powder:**  \n   Measure the desired amount of PVA. For a typical solution:\n   - Prepare a 5-10 wt% polymer solution (i.e., 5-10 g PVA per 100 mL of solvent).\n   - Example: For a 5 wt% solution, weigh 5 g of PVA powder.\n\n2. **Measure the Solvent:**  \n   Based on the desired polymer concentration and solvent ratio, measure the water (and ethanol, if used).  \n   Example for a 5 wt% solution (100 mL total):\n   - If using 100% water: Measure 100 mL of deionized (DI) water.\n   - If using a 90:10 water:ethanol mixture: Measure 90 mL of DI water and 10 mL of ethanol.\n\n#### **Step 4: Heat and Stir the Solution**\n1. **Gradual Heating:**  \n   - Transfer the solvent (or solvent mixture) into a round-bottom flask or beaker and begin gentle heating using a hot plate with a magnetic stirrer.\n   - Heat the solvent to **80-95°C**—this is the temperature range where PVA dissolves effectively.\n   - Avoid excessive heating (>100°C), as this may degrade the polymer or evaporate volatile solvents.\n\n2. **Add PVA Gradually:**  \n   - Slowly sprinkle the weighed PVA powder into the heated solvent while stirring continuously to prevent clumping.\n\n3. **Control Stirring and Dissolution Time:**  \n   - Increase the stirring speed to ensure uniform mixing. Use a magnetic stir bar or mechanical stirrer.\n   - Continue stirring for **30-60 minutes** until the solution becomes clear and viscous, indicating full dissolution.\n\n#### **Step 5: Cool the Solution**\n- Once the PVA is fully dissolved, remove the solution from heat and allow it to cool to room temperature while continuing to stir to prevent gel formation.\n- If the solution is too viscous, additional water (or ethanol-water mixture) can be added to dilute the polymer solution while maintaining stirring.\n\n#### **Step 6: Filter the Solution (Optional)**\n- To remove undissolved particles or impurities, filter the cooled solution using a fine mesh sieve or a filter paper (e.g., Whatman filter paper).\n\n#### **Step 7: Store the Solution**\n- Transfer the prepared solution into a clean, airtight container.\n- Store at room temperature or in the refrigerator if stability and microbial growth are concerns.\n- Label the container with the concentration, date of preparation, and any special instructions.\n\n---\n\n### **Additional Notes:**\n- **Impact of Solvent Ratios on Hydrophilicity:**  \n   The inclusion of small amounts of ethanol can improve processability but slightly reduces the hydrophilicity compared to pure water solutions. Use pure water if maximizing hydrophilicity is critical.\n   \n- **Viscosity Considerations:**  \n   Higher concentrations of PVA or higher molecular weight grades will produce more viscous solutions. Adjust polymer concentration and stirring conditions accordingly.\n\n- **Application to Hydrophilic Polymers:**  \n   The prepared PVA solution can be used directly for casting hydrophilic films, as a component in hydrogels, or as a blending agent with other hydrophilic monomers/polymers (e.g., acrylamide or polyethylene glycol) to enhance water affinity.\n\n---\n\nBy following these detailed steps, you will successfully prepare a solution of polyvinyl alcohol tailored for hydrophilic properties. If any equipment or procedural questions arise in the lab, remember to consult me or the relevant materials safety data sheets (MSDS) for the reagents. Happy experimenting!"
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+{
+  "design_question": "Considering 2-(dimethylamino)ethyl methacrylate (DMAEMA) as one of the monomers, how would you vary its flow rate during initiated chemical vapor deposition to influence the chemical composition of the copolymer for improved hydrophilicity? Justify your reasoning.",
+  "design_answer": "To answer your question about how to vary the flow rate of 2-(dimethylamino)ethyl methacrylate (DMAEMA) during initiated chemical vapor deposition (iCVD) to influence the chemical composition of the copolymer and enhance hydrophilicity, let's analyze the question step by step and design an experimental approach systematically. I will also provide justification for each decision and detailed experimental parameters.\n\n---\n\n### 1. **Analyze the Question and Summarize Key Points**\nAt the core of your question is DMAEMA, a monomer with an amine-containing side group, which introduces certain hydrophilic characteristics via hydrogen bonding or ionic interactions when protonated. However, the degree to which it contributes to the hydrophilicity of the resultant copolymer depends on its incorporation in the final polymer structure. Your query specifically asks:\n   - How varying the flow rate of DMAEMA during iCVD can influence the copolymer’s chemical composition.\n   - How this can be used strategically to enhance the hydrophilicity of the polymer.\n\nKey considerations here include:\n   - The relationship between flow rate of DMAEMA, its partial pressure in the reactor, and its incorporation into the copolymer.\n   - The choice of a co-monomer (if any) and how the relative amount of DMAEMA in the polymer backbone affects the hydrophilicity.\n   - Optimizing the copolymer's overall composition to ensure maximum hydrophilicity while maintaining process control.\n\n---\n\n### 2. **Understanding the Principles Behind iCVD**\nBefore proceeding to the synthesis, understanding the mechanics of iCVD is crucial:\n   - iCVD relies on the adsorption of monomer vapors onto a substrate in the presence of an initiator species (e.g., a thermal initiator like tert-butyl peroxide or TBPO).\n   - The relative rates of adsorption and subsequent polymerization of each monomer correlate with the monomer's vapor pressure and flow rate, affecting the final copolymer composition.\n   - Controlling individual monomer flow rates allows us to tune the composition of the copolymer in situ.\n\nIn the context of DMAEMA, its relatively hydrophilic nature can be contrasted with a more hydrophobic co-monomer (e.g., methyl methacrylate or ethyl methacrylate). By modulating its flow rate, we can increase or decrease its incorporation into the copolymer to favor hydrophilicity.\n\n---\n\n### 3. **Experimental Preparation Scheme**\n\n#### **Step 1: Selection of Monomers**\n- **Monomer A:** DMAEMA (hydrophilic). Its flow rate will be varied to control the hydrophilic content.\n- **Monomer B (co-monomer):** Choose a complementary hydrophobic monomer (e.g., methyl methacrylate, MMA, or butyl acrylate, BA) to form a balanced copolymer structure. The purpose of the co-monomer is to help polymer chain propagation while introducing structural stability to the copolymer.\n\n---\n\n#### **Step 2: Reactor Setup for iCVD**\n1. Use a stainless steel iCVD reactor with precise flow controllers for each gas input.\n2. Equip the system with:\n   - A vaporizer for DMAEMA monomer.\n   - A separate vaporizer for the co-monomer.\n   - A thermal initiator vaporizer (e.g., tert-butyl peroxide).\n3. Maintain substrate temperature at ~30–40°C to promote physical adsorption of the monomers without initiating unwanted side reactions.\n\n---\n\n#### **Step 3: Optimization of Process Parameters**\nTo evaluate the effect of DMAEMA's flow rate, start with a baseline condition and systematically vary DMAEMA flow while keeping other parameters constant.\n\n**Baseline Conditions:**\n- **Monomer A (DMAEMA):** Flow rate = 2 sccm (standard cubic centimeters per minute).\n- **Monomer B (co-monomer):** Flow rate = 2 sccm.\n- **Initiator (TBPO):** Flow rate = 1 sccm.\n- **Reaction Pressure:** Maintain at ~0.5–1 Torr. Optimize pressure to ensure uniform adsorption of monomer vapors.\n- **Substrate Temperature:** 30°C.\n- **Filament Temperature:** 250–280°C to thermally decompose the initiator into free radicals for polymerization.\n- **Reaction Time:** 30 minutes.\n\n---\n\n#### **Step 4: Systematic Variation of DMAEMA Flow Rate**\nTo study its effect on copolymer composition:\n1. Vary DMAEMA flow rate between 1–5 sccm in increments of 1 sccm while keeping other flow rates stable.\n2. For each increment:\n   - Record the total monomer incorporation using Fourier-transform infrared spectroscopy (FTIR) or X-ray photoelectron spectroscopy (XPS).\n   - Measure the resultant surface hydrophilicity using contact angle measurements: lower contact angle correlates to higher hydrophilicity.\n   - Analyze the final copolymer composition using nuclear magnetic resonance spectroscopy (NMR) or gel permeation chromatography (GPC).\n\n---\n\n#### **Step 5: Parameter Justification for Enhanced Hydrophilicity**\n- **Low DMAEMA Flow Rate (1–2 sccm):** Produces a copolymer with a lower DMAEMA content, favoring hydrophobic character.\n- **Moderate DMAEMA Flow Rate (3 sccm):** Balances hydrophilic and hydrophobic content, leading to moderate hydrophilicity.\n- **High DMAEMA Flow Rate (4–5 sccm):** Maximizes DMAEMA incorporation, increasing hydrophilicity but may compromise film uniformity if the monomer over-adsorbs.\n  - Consider protonating DMAEMA post-polymerization (e.g., with dilute HCl) to form positively charged ammonium groups, further enhancing hydrophilicity through ionic effects.\n\n---\n\n#### **Step 6: Post-Synthesis Characterization**\n1. Analyze copolymer structure via FTIR and XPS to confirm incorporation.\n   - Peaks at ~1730 cm⁻¹ (carbonyl stretch) indicate successful polymerization.\n   - Peaks related to amine groups (~2800–2900 cm⁻¹) confirm DMAEMA presence.\n2. Perform water contact angle measurements to quantify hydrophilicity:\n   - Ideal hydrophilic polymers exhibit contact angles <30°.\n3. Evaluate thermal stability (TGA) and molecular weight distribution (GPC).\n\n---\n\n### 4. **Justification for Approach**\n1. **Why flow rate matters:** In iCVD, the monomer’s partial pressure directly affects its incorporation into the polymer. Increasing DMAEMA flow boosts its adsorption rate on the substrate, modifying the copolymer composition.\n2. **Optimizing hydrophilicity:** Higher DMAEMA fractions enhance polar moieties but must be balanced with co-monomers to maintain structural and process stability.\n3. **Post-polymerization treatment:** Protonation or further functionalization ensures maximal hydrophilicity and application-specific functionality.\n\n---\n\n### 5. **Summary**\nBy systematically varying the DMAEMA flow rate during iCVD and monitoring the copolymer's composition and hydrophilicity, a tailor-made polymer can be fabricated with enhanced hydrophilic properties. This approach provides precise control over chemical composition and surface characteristics, offering a robust design strategy for hydrophilic polymer synthesis."
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+{
+  "design_question": "What experimental parameters, such as temperature and chamber pressure, would you consider critical when utilizing functionalized phosphate carbon to modify the surface properties of a polymer?",
+  "design_answer": "Certainly, let us analyze your question and address it in a systematic and detailed manner to ensure clarity and practical understanding of the experimental procedure.\n\n---\n\n**Step 1: Analyze the Question and Identify Key Points**\n\nThe central topic of your question is: *What experimental parameters are critical (e.g., temperature, pressure) when using functionalized phosphate carbon (FPC) to modify the surface properties of a polymer?*\n\nKey points:\n1. The goal is surface modification of a polymer to enhance its properties (e.g., hydrophilicity).\n2. The functionalizing agent is *functionalized phosphate carbon (FPC)*, a material known for its reactive phosphate groups that can engage with polymer surfaces.\n3. The critical conditions (such as temperature and pressure) for this modification process must be optimized to ensure successful grafting or interaction of the FPC with the polymer.\n\n---\n\n**Step 2: Systematic Answer—Explanation of Parameters and Suggested Experimental Scheme**\n\nTo modify a polymer’s surface using FPC, the process often relies on a chemical interaction between the phosphate groups and functional groups on the polymer surface (such as hydroxyl, carboxyl, or amine groups). Here is a step-by-step experimental preparation scheme, detailing critical parameters for successful modification.\n\n### **1. Polymer Surface Pre-treatment**\n\nBefore any surface modification, the polymer surface must typically be pre-treated to activate it. This might involve:\n- **Cleaning**: Use solvents (e.g., ethanol or acetone) to remove grease or contaminants.\n- **Plasma treatment**: Expose the polymer to oxygen or argon plasma to increase surface energy and introduce reactive groups.\n\n#### Critical Parameters:\n- Plasma chamber pressure: 10–100 Pa (low pressure ensures ionized gas flow).\n- Treatment time: 5–10 minutes.\n- Temperature: Room temperature (to prevent thermal degradation of the polymer).\n\n---\n\n### **2. Preparation of Functionalized Phosphate Carbon (FPC)**\n\nThe FPC, often synthesized by grafting phosphate groups onto carbon (e.g., graphene oxide or activated carbon), should be dispersed in a solvent to facilitate interaction with the polymer. \n\n- Prepare an aqueous or alcohol-based dispersion of FPC.\n- Typical concentration: 0.1–0.5% w/v (sufficient for uniform coating without aggregation).\n\n#### Critical Parameters:\n- **Temperature of dispersion preparation**: 25–40 °C (to maintain stability of FPC).\n- **Sonication time**: 30–60 minutes (to achieve a uniform dispersion of FPC).\n- **pH adjustment**: Adjust pH using dilute NaOH or HCl if needed, ideally between 6 and 8, as phosphate groups are stable under neutral/near-neutral conditions.\n\n---\n\n### **3. Surface Functionalization Reaction**\n\nNow comes the critical step: modification of the polymer using FPC. Typically, this is achieved by immersing the polymer in the FPC dispersion or applying FPC via a coating method. Depending on the nature of your polymer, the reaction may involve physical adsorption, chemical bonding, or both.\n\n#### Reaction Procedure:\n- Immerse or coat the polymer with the FPC dispersion.\n- Use mild agitation (e.g., magnetic stirring) to ensure uniform coverage.\n\n#### Critical Parameters:\n1. **Temperature**: 50–80 °C. This range prevents degradation of the polymer while providing sufficient energy for interaction between the polymer surface and FPC. For thermally sensitive polymers, work at lower temperatures (30–50 °C).\n2. **Duration**: 1–4 hours. Longer times allow stronger interactions but must be optimized to prevent undesirable surface reactions.\n3. **Pressure (if using a sealed chamber)**: Atmospheric pressure is typically sufficient. However, if working in a controlled atmosphere (e.g., nitrogen or vacuum), maintain chamber pressure at 0.9–1 atm.\n\n---\n\n### **4. Post-treatment: Removal of Excess FPC**\n\nAfter surface modification, any unreacted or excess FPC must be removed to avoid affecting the polymer's functionality.\n\n#### Procedure:\n- Wash the polymer thoroughly with deionized water or a mild phosphate-buffered solution (PBS) to remove unattached FPC.\n- Dry the polymer at low temperature (30–50 °C) in an oven or under a vacuum for 12–24 hours.\n\n#### Critical Parameters:\n1. Washing solvent: Deionized water or PBS, pH 6–7.5.\n2. Drying temperature: 30–50 °C to prevent thermal damage to the polymer or decomposition of chemically bonded phosphate groups.\n\n---\n\n### **5. Characterization of Modified Polymer Surface**\n\nTo confirm successful modification, various characterization techniques should be employed:\n- **Contact Angle Measurement**: Determine the hydrophilicity of the modified surface (expect a decrease in water contact angle if hydrophilic phosphate groups are successfully attached).\n- **FTIR or XPS Analysis**: Analyze the chemical composition of the surface and confirm the presence of phosphate functional groups.\n- **SEM or AFM**: Examine the surface morphology to check for uniform coverage of FPC.\n\n---\n\n**Final Notes on Critical Parameters**\n- Maintain precise control of temperature during all steps to preserve the integrity of the polymer and phosphate groups.\n- Work under clean and controlled conditions to prevent contamination, which can interfere with surface interactions.\n- Optimize the time, temperature, and concentration of FPC experimentally, focusing on your specific polymer type.\n\nBy following this scheme and carefully tailoring the parameters to your specific materials, you should achieve excellent surface modification, enhancing the hydrophilicity of the polymer. Let me know if you'd like further assistance with this or any related topic!"
+}
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diff --git a/task2/task2-qa/10.1002@advs.202000439.json b/task2/task2-qa/10.1002@advs.202000439.json
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+{
+  "design_question": "When preparing a hydrogel using agarose as the polymer matrix, describe how black phosphorus (BP) sheets can be added to the system to enhance the hydrophilicity of the final material. Include the conditions needed for successful dispersion and integration.",
+  "design_answer": "Certainly! When preparing a hydrogel using agarose as the polymer matrix and incorporating black phosphorus (BP) sheets to enhance the hydrophilicity of the final material, we must carefully consider the dispersion of BP sheets in the polymer matrix and the interactions needed to create a stable, hydrophilic system. Let's proceed step by step:\n\n---\n\n### **Step 1: Key Points and Analysis**\n1. **Objective:** To enhance the hydrophilicity of an agarose-based hydrogel by integrating black phosphorus (BP) sheets.\n2. **Challenges:**\n   - Black phosphorus sheets are hydrophobic in their native form and can aggregate in aqueous environments, so dispersing them uniformly is critical.\n   - BP sheets are sensitive to oxidation in aqueous solutions, so careful handling and stabilization are needed to preserve their properties.\n   - Compatibility between BP sheets and the agarose matrix requires establishing physical or chemical interactions.\n3. **Strategies:**\n   - Functionalizing BP sheets to improve their solubility and dispersion in aqueous solutions.\n   - Processing the agarose in conditions that allow uniform integration of BP sheets without degrading either component.\n\n---\n\n### **Step 2: Experimental Preparation Scheme**\n\n#### **Step 2.1: Materials Required**\n1. **Agarose:** High-purity agarose as the polymer matrix.\n2. **Black Phosphorus (BP) Sheets:** Exfoliated BP sheets with controlled thickness (e.g., nanoscale sheets).\n3. **Dispersing Agent:** A suitable surfactant or stabilizer such as polyvinylpyrrolidone (PVP) or sodium cholate to improve BP dispersion.\n4. **Deionized (DI) Water:** As a solvent for agarose preparation.\n5. **Optional Functionalizing Agents:** For example, dopamine or polyethylene glycol (PEG) to modify BP sheets chemically for enhanced hydrophilicity and compatibility.\n6. **Crosslinkers (if required):** If agarose requires additional crosslinking for mechanical stability.\n\n---\n\n#### **Step 2.2: Preparation of Black Phosphorus (BP) Dispersion**\n1. **Exfoliation of BP Sheets:**\n   - Weigh a specific amount of black phosphorus crystals (e.g., 100 mg).\n   - Prepare a solution of surfactant or stabilizer in deionized water (e.g., use 0.1–0.5 wt% PVP or 1% sodium cholate).\n   - Add the BP crystals to the solution and sonicate using a probe-tip ultrasonicator for 2–3 hours at 4 °C (to prevent overheating and oxidation). Set the sonicator to a pulsed mode (e.g., 10 s on, 10 s off) to avoid degradation of BP sheets.\n   - After sonication, centrifuge the solution at 5000 rpm for 15 minutes to remove larger aggregates, leaving a stable dispersion of BP sheets in the supernatant.\n\n2. **Optional Functionalization:**\n   - If additional hydrophilicity or stability is needed:\n     - Functionalize BP sheets with molecular modifiers such as dopamine or PEG by adding them to the BP dispersion. \n     - For example, add dopamine (10 mg/mL) under mildly basic conditions (e.g., pH ~8 using tris buffer) to graft it onto the BP surface.\n   - Stir the mixture for 12 hours at room temperature under an inert atmosphere (e.g., nitrogen or argon).\n\n---\n\n#### **Step 2.3: Preparation of Agarose Hydrogel Matrix**\n1. **Agarose Solution Preparation:**\n   - Weigh the desired amount of agarose (e.g., 1–3 wt% depending on the desired stiffness of the hydrogel).\n   - Dissolve the agarose in deionized water by heating the solution to 90–95 °C with constant stirring. Ensure the agarose completely dissolves to form a clear solution.\n\n2. **Integration of BP Sheets:**\n   - Cool the agarose solution to approximately 50–60 °C (still in the liquid state but not too hot to degrade BP sheets).\n   - Slowly add the prepared BP dispersion dropwise under constant stirring to the agarose solution. Maintain the BP-to-agarose weight ratio as desired (e.g., 0.2–0.5 wt% BP relative to the agarose).\n   - Stir the mixture for 10–15 minutes to ensure uniform distribution of BP sheets within the agarose matrix.\n\n---\n\n#### **Step 2.4: Gelation and Crosslinking**\n1. **Gelation:**\n   - Pour the BP-agarose solution into a mold or container of desired shape.\n   - Allow the solution to cool to room temperature, promoting the physical gelation of agarose.\n\n2. **Optional Crosslinking (If Required):**\n   - If mechanical strength or stability enhancement is needed, introduce a chemical crosslinker (e.g., genipin or glutaraldehyde) at this stage. Ensure that the crosslinking reaction conditions (e.g., pH, reaction time) are mild enough to preserve BP integrity.\n\n---\n\n### **Step 3: Final Steps and Considerations**\n1. **Oxidation Mitigation:**\n   - Store the prepared hydrogel under an inert environment (e.g., nitrogen or argon) during experiments to minimize BP oxidation. \n   - Alternatively, incorporate antioxidants such as ascorbic acid or sodium ascorbate into the system to prolong BP stability.\n\n2. **Characterization:**\n   - Verify the uniform dispersion of BP sheets and their interaction with the agarose matrix using techniques such as optical microscopy, scanning electron microscopy (SEM), or transmission electron microscopy (TEM).\n   - Assess the hydrophilicity of the prepared hydrogel using water contact angle measurements.\n\n3. **Applications Testing:**\n   - Test the performance of the hydrogel in its intended application (e.g., biomedical, environmental, or sensing applications). \n\n---\n\n### **Summary**\nIncorporating BP sheets into an agarose-based hydrogel requires optimizing both the exfoliation and dispersion of BP sheets and their integration into the agarose matrix. Key steps include the preparation of a stable BP dispersion, functionalization (if needed), and careful mixing with the agarose solution under controlled conditions to prevent aggregation or degradation. The resulting hydrogel benefits from the enhanced hydrophilicity and potential functional properties imparted by the BP sheets.\n\nBy following this preparation scheme, you can reliably produce a high-quality BP-agarose hydrogel for further experimentation. Let me know if you have any additional questions or require clarification!"
+}
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diff --git a/task2/task2-qa/10.1007@s11998-020-00338-z.json b/task2/task2-qa/10.1007@s11998-020-00338-z.json
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+{
+  "design_question": "How would you incorporate nano-SiO2 into a polymer solution to ensure uniform dispersion and effective integration into the polymer matrix? Detail the steps you would follow.",
+  "design_answer": "To address your question systematically, we need to carefully analyze the problem and provide a detailed experimental preparation scheme that enables the incorporation of nano-SiO₂ into a polymer solution, ensuring uniform dispersion and effective integration into the polymer matrix. Here is a step-by-step method to achieve this, along with the reasoning and conditions for each step.\n\n---\n\n### **1. Key Analysis and Summary of the Problem**\n#### Key Concepts:\n- **Nano-SiO₂** is a hydrophilic nanoparticle that often aggregates due to its high surface energy and hydrogen bonding among hydroxyl groups on the surface.\n- **Effective incorporation**: It is critical to ensure the uniform dispersion of nano-SiO₂ into the polymer matrix to avoid agglomerated nanoparticles and to maintain the desired properties (e.g., hydrophilicity, transparency, and mechanical properties) of the final polymer composite.\n- **Polymer compatibility**: Depending on the polymer system, the dispersion can be either via covalent bonding, physical entrapment, or surface modification.\n\n#### Approach:  \nWe will use a combination of surface modification of nano-SiO₂ and sonication-assisted dispersion methods, followed by uniform mixing into the polymer solution.\n\n---\n\n### **2. Detailed, Step-by-Step Experimental Preparation Scheme**\n\n#### **Step 1: Surface Modification of Nano-SiO₂ (Optional but Recommended)**\nPurpose: Nano-SiO₂ particles are prone to aggregation; therefore, surface modification (via silanization) with hydrophilic or polymer-compatible groups improves dispersion and compatibility with the polymer matrix.\n\n1. **Reagents:**\n   - Nano-SiO₂\n   - Silane coupling agent (e.g., 3-aminopropyltriethoxysilane (APTES) or methacryloxypropyltrimethoxysilane (MPTMS), depending on the polymer system)\n   - Ethanol or toluene (as solvent)\n   - Water (deionized)\n   - Acetic acid (to adjust pH for silanization)\n\n2. **Procedure:**\n   a. In a glass beaker, prepare a solution of ethanol and deionized water in a 95:5 volume ratio.\n   b. Adjust the pH of this solution to ~4.5 using acetic acid (acidity promotes hydrolysis of the silane agent).\n   c. Add the silane coupling agent to the ethanol-water mixture under magnetic stirring (e.g., 2 wt% of silane based on the weight of nano-SiO₂).\n   d. Gradually add nano-SiO₂ to the solution and sonicate for 1 hour to break any agglomerates.\n   e. Stir the reaction at 60–80°C for 4 hours to complete the silanization reaction.\n   f. After the reaction, collect the modified nano-SiO₂ by centrifugation and wash thoroughly with ethanol to remove unreacted silane.\n   g. Dry the modified nano-SiO₂ in a vacuum oven at 60°C for 12 hours.\n\n#### **Step 2: Preparation of the Polymer Solution**\nPurpose: Dissolve the polymer in an appropriate solvent to ensure a homogeneous medium for introducing nano-SiO₂.\n\n1. **Reagents:**\n   - Desired polymer (e.g., PVA, PVP, or a hydrophilic polymer of your interest)\n   - Solvent (depending on polymer solubility; common solvents include water, ethanol, or DMF)\n\n2. **Procedure:**\n   a. Weigh the required amount of polymer (e.g., 5 g for a 10 wt% polymer solution).\n   b. Dissolve the polymer in the solvent under constant stirring at the appropriate temperature (e.g., 80°C for PVA in water) to ensure complete dissolution.\n   c. Allow the polymer solution to cool to room temperature, ensuring it is homogeneous and free from undissolved particles.\n\n#### **Step 3: Dispersion of Nano-SiO₂**\nPurpose: Achieve a uniform distribution of nano-SiO₂ in the polymer solution using sonication and stirring.\n\n1. **Reagents:**\n   - Modified nano-SiO₂ (prepared in Step 1 or unmodified nano-SiO₂ if skipping Step 1)\n   - Polymer solution (prepared in Step 2)\n\n2. **Procedure:**\n   a. Calculate the desired amount of nano-SiO₂ to incorporate into the polymer solution (e.g., 1–5 wt% relative to the weight of the polymer).\n   b. Pre-disperse nano-SiO₂ in a small volume of the same solvent used for the polymer solution using a probe sonicator. Use short bursts (10–30 seconds) to avoid overheating the solvent.\n   c. Gradually add the pre-dispersed nano-SiO₂ into the polymer solution under continuous stirring.\n   d. Use a probe sonicator to ensure uniform dispersion. Sonicate for 5–10 minutes in pulse mode (e.g., 5 seconds on, 5 seconds off) while maintaining the solution temperature below 40°C.\n\n#### **Step 4: Integration and Final Mixing**\nPurpose: Ensure stable and uniform integration of nano-SiO₂ into the polymer matrix.\n\n1. Continue stirring the polymer-nano-SiO₂ mixture for 1–2 hours at room temperature.\n2. Check the dispersion visually or using analytical techniques such as dynamic light scattering (DLS) or scanning electron microscopy (SEM).\n3. If visible aggregates are still present, apply additional sonication or filtration through a mesh to remove large agglomerates.\n\n#### **Step 5: Polymer Processing or Film Casting**\nPurpose: Process the polymer-nano-SiO₂ mixture into the desired form (e.g., film, gel, or coating).\n\n1. Pour the homogeneous solution onto a substrate (e.g., glass or PTFE molds) for film casting.\n2. Dry the film slowly at room temperature to avoid defects, followed by thermal treatment (e.g., 60°C for several hours) to remove residual solvent.\n\n---\n\n### **3. Notes on Reaction Conditions and Considerations**\n- **Safety:** Nano-SiO₂ is an inhalation hazard; always handle it in a fume hood while wearing appropriate PPE.\n- **Sonication:** Prolonged sonication can degrade some polymers. Use optimized parameters to avoid this.\n- **Surface Modification:** If your polymer has specific functional groups (e.g., hydroxyls or amines), consider using silanes with complementary groups to enhance bonding between nano-SiO₂ and the polymer matrix.\n- **Verification:** Use analytical techniques (e.g., SEM for morphology, FTIR for chemical interaction, TGA for thermal stability) to confirm successful integration of nano-SiO₂.\n\n---\n\nBy following this systematic approach, you should achieve uniform dispersion and effective integration of nano-SiO₂ into the polymer matrix, resulting in a high-performance composite material with enhanced hydrophilicity."
+}
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diff --git a/task2/task2-qa/10.1016@j.porgcoat.2019.01.061.json b/task2/task2-qa/10.1016@j.porgcoat.2019.01.061.json
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+{
+  "design_question": "Explain how hydroxyethyl acrylate (HEA) can be used to introduce unsaturated bonds into the molecular structure of a polymer and discuss how these bonds can enhance the hydrophilicity of the final material.",
+  "design_answer": "Certainly! Thank you for your thoughtful question. Let us carefully address this topic step by step, ensuring clarity and precise understanding, particularly focusing on how hydroxyethyl acrylate (HEA) can be harnessed within a hydrophilic polymer synthesis process. We will cover its role in introducing unsaturated bonds and how these bonds contribute to hydrophilicity enhancement.\n\n---\n\n### **Key Points of the Question**\n1. **Significance of Hydroxyethyl Acrylate (HEA):** We are tasked with exploring how HEA can introduce unsaturated bonds into the molecular structure of a polymer.\n2. **Hydrophilicity Enhancement:** Understand how incorporating HEA contributes to the hydrophilicity of the resulting polymer.\n3. **Experimental Process Design:** Develop detailed, step-by-step synthetic procedures using HEA within a polymerization context.\n\n---\n\n### **Step-by-Step Explanation and Experimental Design**\nWe will now undertake the design of an experiment using HEA to synthesize a hydrophilic polymer, integrate it into the polymer chain, and explain how this improves hydrophilicity.\n\n---\n\n#### **1. Overview of Hydroxyethyl Acrylate (HEA)**\nHEA is a monomer containing two key functional groups:\n   - **The acrylate group (-CH=CHCOO-):** Contains an unsaturated double bond, which enables its participation in polymerization reactions, such as free radical polymerization, to form the backbone of a polymer.\n   - **The hydroxyl group (-OH):** Hydrophilic in nature, which increases water affinity in the resulting polymer.\n\nThis bifunctionality allows HEA to be copolymerized with other monomers while simultaneously introducing hydrophilic and reactive sites into the polymer structure.\n\n---\n\n#### **2. Reaction Strategy: Introducing HEA into a Polymer**\nTo incorporate HEA into a polymer, we will employ **free radical polymerization**, which is a robust and versatile technique for acrylate-based monomers. The steps are as follows:\n\n---\n\n#### **Step 1: Selection of Copolymerizable Monomers**\n- Identify the desired copolymer structure and its intended hydrophilicity. Copolymerization with HEA ensures two outcomes:\n  1. Introduction of hydrophilic hydroxyl groups.\n  2. Incorporation of the unsaturated acrylate group.\n\nCommon comonomers for HEA in hydrophilic polymer synthesis include:\n   - **Methyl methacrylate (MMA):** For thermomechanical stability.\n   - **Acrylic acid (AA):** To further enhance hydrophilicity through its carboxylic acid functionality.\n   - **N-vinylpyrrolidone (NVP):** Provides additional hydrophilic sites.\n\n---\n\n#### **Step 2: Experimental Conditions for Polymerization**\nWe propose a free radical solution polymerization using the following:\n- **Monomers:** HEA (hydroxyethyl acrylate) and a comonomer (e.g., acrylic acid).\n- **Initiator:** Azo-based initiators such as azobisisobutyronitrile (AIBN) are ideal. Use at 1.0 mol% relative to total monomers for efficient initiation.\n- **Solvent:** A polar aprotic solvent like dimethylformamide (DMF), as it can dissolve both the monomers and the resulting hydrophilic polymer.\n- **Reaction Temperature:** 60-75 °C, as AIBN decomposes into free radicals at these temperatures.\n- **Reagent Ratios:** HEA to comonomer molar ratio should be tailored to achieve the desired level of hydrophilicity. Typically:\n  - HEA: 70 mol% (higher proportion for greater hydrophilicity).\n  - Comonomer (e.g., acrylic acid): 30 mol%.\n\n---\n\n#### **Step 3: Experimental Procedure**\n1. **Prepare the Reaction Mixture:**\n   - Dissolve HEA (e.g., 7 g, ~60 mmol) and comonomer acrylic acid (e.g., 2.5 g, ~35 mmol) in DMF (50 mL) in a 100 mL round-bottom flask equipped with a magnetic stir bar.\n   - Add AIBN (0.05 g, ~0.3 mmol) as the initiator.\n\n2. **Degas the Mixture:**\n   - Purge the solution with nitrogen or argon gas for 20-30 minutes to remove oxygen, which inhibits radical polymerization.\n\n3. **Polymerization Reaction:**\n   - Heat the reaction mixture at 65 °C under nitrogen atmosphere with constant stirring.\n   - Allow the reaction to proceed for 6-8 hours to achieve complete polymerization.\n\n4. **Precipitation and Recovery:**\n   - After cooling the reaction to room temperature, precipitate the polymer by adding the reaction mixture dropwise into diethyl ether, a nonsolvent for the polymer.\n   - Collect the polymer by filtration and dry under vacuum at 40 °C to obtain a hydrophilic polymer.\n\n---\n\n#### **3. Hydrophilicity Enhancement in the Final Material**\nIncorporating HEA into the polymer structure contributes to hydrophilicity in two ways:\n1. **Hydroxyl Groups (-OH):**\n   The hydroxyl groups on HEA provide strong hydrogen bonding with water molecules, enhancing the polymer's affinity for water.\n\n2. **Controlled Hydrophilic-Hydrophobic Balance:**\n   By adjusting the molar ratio of HEA to the comonomer during polymerization, one can finely tune the hydrophilic/hydrophobic balance of the polymer surface.\n\n---\n\n### **4. Crosslinking with HEA**\nIf desired, the unsaturated acrylate group in HEA retains its reactivity post-polymerization and can be further used for crosslinking reactions with additional monomers or oligomers:\n- **Example:** UV curing with photoinitiators to form crosslinked hydrophilic networks.\n- Crosslinking enhances mechanical strength while maintaining hydrophilicity.\n\n---\n\n#### **Final Remarks**\nYou now have a comprehensive, step-by-step synthetic strategy to use HEA for the preparation of hydrophilic polymers. By leveraging HEA's dual functionality (acrylate and hydroxyl groups), you can achieve tailored levels of hydrophilicity in the polymer. Adjusting monomer ratios, reaction conditions, and crosslinking will allow additional fine-tuning for diverse applications such as hydrogels, coatings, and biomedical materials. \n\nLet me know if you have further questions!"
+}
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diff --git a/task2/task2-qa/1980-kao soap-anti-fog.json b/task2/task2-qa/1980-kao soap-anti-fog.json
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+{
+  "design_question": "Describe how you would incorporate a sulfonic acid type amphoteric surface active agent, derived from alpha-hydroxyalkyldialkylamine reacted with benzyl chloride, into a polymer system to enhance its hydrophilicity. Be specific about the reaction steps and the resulting molecular interactions.",
+  "design_answer": "Certainly! Let us approach your question step by step, breaking it into its parts while focusing on the desired goal: incorporating a sulfonic acid-type amphoteric surfactant, derived from the reaction of alpha-hydroxyalkyldialkylamine with benzyl chloride, into a polymer system to enhance its hydrophilicity.\n\n### **Key Points**\n1. **Objective:** Enhance the hydrophilicity of a polymer system using a specifically derived sulfonic acid-type amphoteric surfactant.\n   - This surfactant is synthesized by reacting alpha-hydroxyalkyldialkylamine with benzyl chloride.\n\n2. **Requirements:**\n    - Detailed synthesis process for the sulfonic acid-type surfactant.\n    - Method for incorporating the surfactant into the polymer system.\n    - Clear instructions on experimental conditions, reagent proportions, reaction mechanisms, and molecular interactions.\n\n---\n\n### **Detailed Experimental Preparation Scheme**\n\n#### **Part I: Synthesis of Sulfonic Acid-Type Amphoteric Surfactant**\nWe first need to synthesize the surfactant, which involves the reaction of alpha-hydroxyalkyldialkylamine with benzyl chloride.\n\n##### **Step 1: Preparation of Alpha-Hydroxyalkyldialkylamine**\n1. **Reagents Required:**\n   - Dialkylamine (e.g., dimethylamine or diethylamine).\n   - Alpha-hydroxyalkyl halide (e.g., 2-chloroethanol).\n   - Solvent: Tetrahydrofuran (THF) or ethanol.\n\n2. **Reaction Conditions:**\n   - Perform the reaction in a round-bottom flask under an inert nitrogen atmosphere to prevent oxidation.\n   - Combine dialkylamine and alpha-hydroxyalkyl halide in a 1:1 molar ratio.\n   - Add THF as a solvent to maintain homogeneity.\n   - Stir the mixture at **room temperature** for 8–12 hours.\n   - Monitor the reaction progress using thin-layer chromatography (TLC).\n\n3. **Reaction Mechanism:**\n   A nucleophilic substitution occurs, where the alpha-hydroxyalkyl halide reacts with the amine to produce alpha-hydroxyalkyldialkylamine and a byproduct (e.g., HCl or NaCl).\n\n4. **Purification:**\n   - Neutralize the reaction solution with a base (if acidic byproducts form).\n   - Use distillation or recrystallization to obtain the alpha-hydroxyalkyldialkylamine.\n\n---\n\n##### **Step 2: Reaction with Benzyl Chloride**\n1. **Reagents Required:**\n   - Alpha-hydroxyalkyldialkylamine (from **Step 1**).\n   - Benzyl chloride (functionalization agent).\n   - Solvent: Dimethylformamide (DMF).\n\n2. **Reaction Conditions:**\n   - Add benzyl chloride to the alpha-hydroxyalkyldialkylamine in a **2:1 molar ratio**.\n   - Use DMF as a solvent and perform the reaction at **40–60°C** for 8–10 hours under stirring.\n   - Include a catalytic amount of potassium carbonate (K2CO3) or another weak base to facilitate the reaction and neutralize liberated HCl.\n\n3. **Reaction Mechanism:**\n   - Benzyl chloride reacts with the hydroxy and amine groups of alpha-hydroxyalkyldialkylamine, forming a structure with benzyl substitution.\n   - This molecule serves as the precursor **(intermediate)** for the sulfonic acid-containing surfactant.\n\n4. **Purification:**\n   - Wash the crude product with ethyl acetate to remove unreacted benzyl chloride.\n   - Purify using column chromatography, employing a methanol/water solvent mixture.\n\n---\n\n##### **Step 3: Functionalization to Incorporate Sulfonic Acid**\n1. **Reagents Required:**\n   - Intermediary product (benzyl-functionalized alpha-hydroxyalkyldialkylamine).\n   - Sulfonating agent: Chlorosulfonic acid or sodium bisulfite.\n\n2. **Reaction Conditions:**\n   - Use a well-ventilated fume hood, as sulfonating agents release acidic vapors.\n   - Add the sulfonating agent dropwise to the benzyl-functionalized compound at **0–5°C**.\n   - Let the reaction proceed at room temperature for **6–12 hours** under stirring.\n\n3. **Reaction Mechanism:**\n   - The sulfonating agent introduces sulfonic acid (-SO3H) groups onto the benzyl-functionalized molecule, forming a sulfonic acid-type amphoteric surfactant.\n\n4. **Purification:**\n   - Neutralize excess sulfonating agent with dilute NaOH.\n   - Dialyze the product to remove impurities, followed by lyophilization.\n\n---\n\n#### **Part II: Incorporation into Polymer System**\nWith the surfactant ready, the next step involves introducing it into the polymer system to enhance hydrophilicity.\n\n##### **Step 4: Polymer System Selection**\n1. The polymer must be compatible with the surfactant. Examples include:\n   - Polyvinyl alcohol (PVA).\n   - Polyacrylamide (PAM).\n   - Polyethylene glycol (PEG).\n\n2. Polymer characteristics to modify:\n   - Hydrophilicity, wettability, or biocompatibility.\n\n---\n\n##### **Step 5: Blending Method**\nThe surfactant can be introduced into the polymer system using either **grafting** or **physical blending**.\n\n1. **Grafting Approach:**\n   - Use radical polymerization to covalently bind the surfactant to the polymer backbone.\n   - Initiators: Potassium persulfate or benzoyl peroxide.\n   - Reaction Conditions:\n     - Dissolve the polymer in an aqueous solution.\n     - Add the surfactant (in 10–20% w/w ratio).\n     - Initiate the reaction at **70–80°C** under nitrogen for 6 hours.\n\n2. **Physical Blending Approach:**\n   - Dissolve the polymer and surfactant in a common solvent (e.g., water, ethanol).\n   - Use sonication or mechanical stirring to homogeneously mix the two.\n   - Cast the solution onto a substrate (glass or Teflon) and dry at **room temperature** to remove the solvent.\n\n---\n\n##### **Step 6: Characterization**\nTo confirm enhanced hydrophilicity:\n1. **Contact Angle Measurement:** Verify reduced water contact angle on surfaces.\n2. **FTIR Analysis:** Confirm sulfonic acid functional groups (-SO3H) in the polymer structure.\n3. **Tensile Strength Tests:** Ensure mechanical integrity of the polymer post-modification.\n\n---\n\n### **Molecular Interactions**\n1. **Hydrophilic Effect:**\n   - Sulfonic acid (-SO3H) groups form hydrogen bonds with water, increasing surface hydrophilicity.\n   - Benzyl groups help improve polymer-surfactant compatibility by introducing aromatic interactions.\n\n2. **Amphoteric Behavior:**\n   - The structure allows interactions with both acidic and basic solvents, further enhancing wettability.\n\n---\n\n### **Conclusion**\nBy systematically synthesizing the sulfonic acid-type amphoteric surfactant and effectively incorporating it into a polymer matrix, the hydrophilicity of the polymer can be enhanced through increased water affinity, amphoteric character, and hydrogen-bonding capabilities. This approach ensures optimal polymer performance in applications requiring high wettability or biocompatibility.\n\n"
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+{
+  "design_question": "Design an experimental procedure to incorporate γ-glycidoxypropyltrimethoxysilane into a polymer modification process. Explain its role in enhancing the hydrophilicity of the resulting material.",
+  "design_answer": "### Analysis of the Question:\nThe student is asking for an experimental procedure to incorporate **γ-glycidoxypropyltrimethoxysilane (GPTMS)** into the polymer modification process, along with an explanation of how it contributes to enhancing the hydrophilicity of the resulting material. \n\n#### Key Points:\n1. **GPTMS Structure**: GPTMS is an organosilane compound with both epoxy functional groups and silane groups. The epoxy group can undergo ring-opening reactions, and the silane group can participate in hydrolysis and condensation reactions.\n2. **Role in Hydrophilicity**: GPTMS can enhance hydrophilicity because the hydrolyzed silane groups form silanol groups (-Si-OH) during polymer modification. These silanol groups can interact strongly with water, increasing hydrophilic properties.\n3. **Objective**: Develop a systematic, detailed synthesis procedure integrating GPTMS into a polymer to ensure controlled hydrophilicity enhancement.\n\n---\n\n### Experimental Procedure for Incorporating GPTMS:\n#### Materials and Reagents:\n- γ-Glycidoxypropyltrimethoxysilane (GPTMS)\n- Base polymer (e.g., polyethylene glycol diacrylate – PEGDA or polyurethane elastomer)\n- Water (preferably deionized for silane hydrolysis)\n- Catalyst (e.g., hydrochloric acid or acetic acid for acid-catalyzed hydrolysis of silane)\n- Solvent (e.g., ethanol or isopropanol for silane dissolution)\n- Stirring apparatus, glass reactor equipped with temperature control\n- Optional crosslinker or secondary monomers with hydrophilic properties\n\n---\n\n#### Stepwise Experimental Procedure:\n**Step 1: Preparation of the GPTMS Solution**  \n1. Dissolve GPTMS in ethanol to form a homogeneous solution.  \n    - Typical concentration: Use 5–10 wt% GPTMS relative to the polymer matrix for moderate hydrophilicity.\n    - Example: For 50 g polymer, dissolve 2.5 g GPTMS in 20 mL ethanol.\n2. Gradually add deionized water (~5–10% volume of the GPTMS solution) to initiate hydrolysis of the methoxy groups to silanol groups (-Si-OH).  \n    - Reaction: GPTMS + H2O → Hydrolyzed silanol-containing intermediate.\n3. Add a small amount of acid catalyst (e.g., 0.1–0.5% of solution volume) to accelerate the hydrolysis reaction.  \n    - Maintain a mild temperature (~25–40°C) for 30–60 minutes while stirring.\n\n---\n\n**Step 2: Polymer Base Preparation**  \n1. Select a suitable polymer base for modification. If the polymer has hydroxyl (-OH), carboxyl (-COOH), or amine (-NH2) groups, they can react with the epoxy group in GPTMS.\n2. For a polymer like PEGDA, dissolve it in ethanol or other compatible solvents depending on the polymer solubility.  \n\n---\n\n**Step 3: Grafting of GPTMS onto the Polymer**  \n1. Slowly add the hydrolyzed GPTMS solution prepared in Step 1 to the polymer solution under constant stirring.  \n    - Use a polymer-to-GPTMS ratio tailored for desired hydrophilicity, e.g., 1:1 molar ratio of epoxy groups to hydroxyl groups in the polymer. Adjust based on experimental trials.\n2. Allow the epoxy group of GPTMS to undergo a ring-opening reaction with functional groups on the polymer backbone (e.g., -OH from PEG or polyurethane).  \n    - Reaction Conditions: Stir at 60–80°C for 2–8 hours, depending on the reactivity and viscosity of the mixture.\n    - Ensure the reaction proceeds in an inert atmosphere (e.g., nitrogen purging) to prevent oxygen-induced degradation.\n\n---\n\n**Step 4: Crosslinking/Condensation of Silane Groups**  \n1. After grafting GPTMS, allow the hydrolyzed silanol groups to undergo condensation reactions to form a crosslinked network within the polymer matrix.  \n    - Reaction: 2 Si-OH → Si-O-Si + H2O (polycondensation reaction).\n    - Maintain mild heating (40–60°C) with gentle stirring for an additional 4–6 hours to facilitate crosslinking.\n2. Add additional water (5–10 wt% of total materials) if condensation slows down.\n\n---\n\n**Step 5: Post-treatment and Curing**  \n1. After the reaction, remove excess ethanol and water by vacuum drying or solvent evaporation at a controlled temperature (~50°C).\n2. If needed, cure the polymer at elevated temperatures (e.g., 80–120°C) to finalize crosslinking and stabilize the network.\n\n---\n\n**Step 6: Analysis of Modified Polymer**  \n1. Confirm success using characterization techniques:\n   - **FTIR**: Look for characteristic epoxy ring-opened signals (~900–1000 cm⁻¹) and Si-O-Si stretching (~1000–1100 cm⁻¹).\n   - **Contact Angle Measurement**: Assess enhanced hydrophilicity – smaller contact angles indicate improved hydrophilicity.\n   - **Thermal Analysis (TGA/DSC)**: Verify thermal stability and crosslinking density.\n   - **SEM/TEM**: Observe morphology changes post-modification.\n\n---\n\n### GPTMS Role in Enhancing Hydrophilicity:\n1. **Silanol Groups**: The hydrolyzed silane groups (-Si-OH) can form hydrogen bonds with water molecules, significantly increasing the material's ability to interact with water.\n2. **Epoxy Reactivity**: The epoxy group ensures covalent bonding of GPTMS to the polymer matrix, improving durability and compatibility of the hydrophilic segments.\n3. **Crosslinked Structure**: GPTMS can create a crosslinked network with silanol condensation, further increasing the polymer's water absorption capacity and improving hydrophilicity.\n\nBy following these detailed steps and understanding GPTMS's dual functionality, you can successfully integrate the material into a hydrophilic polymer system."
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+{
+  "design_question": "Design an experiment to incorporate the sodium salt of 5-sulfoisophthalic acid into a copolyester structure. What would be the role of this molecule in enhancing the hydrophilicity of the polymer material, and how would you ensure it is properly integrated during the condensation reaction?",
+  "design_answer": "This is an excellent question, and I appreciate your interest in understanding how to enhance the hydrophilicity of polymer materials through structural modification. Let me guide you through the design and analysis step by step.\n\n---\n\n### ANALYSIS OF THE QUESTION AND KEY POINTS:\n1. **Goal**: To incorporate the sodium salt of 5-sulfoisophthalic acid (5-SSIPA) into a copolyester structure via a condensation reaction.\n2. **Purpose**: To enhance the hydrophilicity of the polymer material.\n3. **Key considerations**:\n   - The sodium salt of 5-SSIPA introduces sulfonic acid (-SO₃⁻Na⁺) groups into the polymer, which increases hydrophilicity due to the ionic, polar nature of the sulfonate group.\n   - The integration of 5-SSIPA into the copolyester backbone must be carefully controlled to ensure proper condensation without undesired side reactions (e.g., hydrolysis, incomplete incorporation).\n   - Proper stoichiometric balance and reaction conditions are crucial for copolymerization.\n\n---\n\n### SYSTEMATIC EXPERIMENTAL PREPARATION SCHEME:\n\n#### **Step 1: Selection of Monomers**\nTo prepare a copolyester containing 5-SSIPA, we need the following monomers:\n1. **Diacid component**: A combination of terephthalic acid (or its dimethyl ester, dimethyl terephthalate - DMT) with the sodium salt of 5-sulfoisophthalic acid (5-SSIPA).\n   - 5-SSIPA provides ionic hydrophilicity, while terephthalic acid forms the bulk of the aromatic backbone, ensuring mechanical integrity.\n2. **Diol component**: Ethylene glycol (EG) is most commonly used due to its reactivity and compatibility with aromatic polyesters.\n\nThese components will form the copolyester backbone, with 5-SSIPA serving as a hydrophilic modifier.\n\n---\n\n#### **Step 2: Experimental Design**\n\n**Reaction Mechanism**: The synthesis involves a polycondensation reaction. If using terephthalic acid, an esterification reaction precedes the condensation step. If using DMT, it will directly transesterify with ethylene glycol to produce the oligomers before polycondensation.\n\n---\n\n**Step 2.1: Reaction Setup**\n1. **Reactor Preparation**:\n   - Use a 3-neck round-bottom flask equipped with a mechanical stirrer, nitrogen inlet (to prevent oxidation), and a condenser (to collect by-products like methanol or water).\n   - A thermometer and heating mantle will provide accurate temperature control.\n\n2. **Reagents**:\n   - 5-Sulfoisophthalic acid sodium salt (5-SSIPA): 5–15 mol% of the total acid content (for sufficient hydrophilicity without drastically reducing crystallinity).\n   - Terephthalic acid (or dimethyl terephthalate - DMT): Remaining mol% of the aromatic diacid content.\n   - Ethylene glycol (EG): A stoichiometric excess is typically used (2–3 moles of EG per mole of total diacid) to drive the esterification/condensation equilibrium forward.\n\n---\n\n**Step 2.2: Reaction Sequence**\nThe reaction proceeds in two stages: (1) Formation of oligomers, and (2) Polycondensation.\n\n---\n\n### **Stage 1: Oligomer Formation**\n1. **Reagent Addition**:\n   - Charge the reactor with terephthalic acid (or DMT), 5-SSIPA, and ethylene glycol.\n   - Ensure thorough mixing of 5-SSIPA and terephthalic acid/DMT to achieve uniform distribution.\n\n2. **Catalyst**:\n   - Add 0.01–0.05 mol% of a transesterification catalyst, such as titanium(IV) isopropoxide (Ti(O-iPr)₄) or antimony trioxide (Sb₂O₃), for DMT. \n   - Alternatively, if terephthalic acid is used, a carboxyl-esterification catalyst like p-toluenesulfonic acid (p-TSA) may be used.\n\n3. **Temperature Control**:\n   - For DMT: Heat to 180–200°C to drive the transesterification reaction. Methanol will be collected as a condensate (by-product).\n   - For terephthalic acid: Heat to 220–240°C to facilitate esterification, with water as a by-product.\n\n4. **Monitoring**:\n   - Stir constantly and monitor the release of methanol or water to ensure the reaction progresses toward oligomer formation.\n   - Reaction time: Typically 2–4 hours to ensure full conversion.\n\n---\n\n### **Stage 2: Polycondensation**\n1. **Vacuum Application**:\n   - Once oligomers are formed, decrease the pressure gradually to <1 mmHg (high vacuum). This prevents side reactions and removes volatile by-products efficiently.\n\n2. **Temperature Control**:\n   - Increase the temperature to 250–280°C in this step to achieve the required viscosity. Maintain stirring to ensure uniform mixing.\n\n3. **Duration**:\n   - The polycondensation reaction typically takes 2–6 hours, depending on the viscosity target (related to molecular weight).\n\n4. **Integration of 5-SSIPA**:\n   - The sulfonate groups of 5-SSIPA are already incorporated into the polyester backbone during Stage 1. To ensure proper integration, avoid using excessive 5-SSIPA levels that could lead to phase separation or poor polymerization.\n\n---\n\n#### **Step 3: Polymer Recovery and Analysis**\n1. Cool the reaction mixture and collect solidified polyester.\n   - The final product should be a copolyester with an ionic hydrophilic functionality due to the sulfonate groups from 5-SSIPA.\n\n2. **Purification**:\n   - Wash thoroughly with distilled water to remove unreacted monomers or residual sodium salts.\n\n3. **Characterization**:\n   - Conduct **Fourier-transform infrared spectroscopy (FTIR)** to confirm the incorporation of sulfonate groups (-SO₃⁻).\n   - Use **Nuclear Magnetic Resonance (NMR)** spectroscopy to verify the molecular structure.\n   - Measure intrinsic viscosity and molecular weight using gel-permeation chromatography (GPC).\n   - Perform water contact angle measurements to confirm enhanced hydrophilicity.\n\n---\n\n### ROLE OF 5-SSIPA IN HYDROPHILICITY:\n1. The sulfonate (-SO₃⁻Na⁺) groups on 5-SSIPA are highly hydrophilic and enhance the water absorption capacity of the polymer, making it more suitable for applications such as water filtration membranes or hydrophilic coatings.\n2. The ionic nature of the sulfonate groups enables stronger interactions with water molecules, ensuring better wetting properties and potential ion-exchange functionality.\n\n---\n\n### TROUBLESHOOTING AND TIPS:\n1. Excessive use of 5-SSIPA (>15 mol%) may lead to phase separation, brittle polymers, or poor processability due to the disruption of crystallinity.\n2. Avoid hydrolysis of ester bonds by maintaining an anhydrous environment (once water by-products have been removed) and controlling vacuum application rates.\n3. Use high-purity reagents and prevent contamination to avoid side reactions.\n\n---\n\nBy following these steps meticulously, you can successfully incorporate 5-SSIPA into a copolyester and achieve a hydrophilic material tailored for your target application. Let me know if you have any further questions!"
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+{
+  "design_question": "Design an experimental scheme using rape oil as a key reagent to modify a polymer for increased hydrophilicity, and outline all necessary steps and conditions.",
+  "design_answer": "Thank you for posing the question regarding the use of rape oil to modify a polymeric system for enhanced hydrophilicity. As your professor, I will analyze the problem, summarize the critical points, and carefully design a methodical and detailed experimental preparation scheme. This response aligns with your needs and laboratory practice requirements.\n\n---\n\n### **Key Points of the Question:**\n1. **Objective:** Increase the hydrophilicity of a polymer system using rape oil as a key reagent.\n2. **Primary Considerations:** Design the experimental procedure systematically, focusing on the functionalization chemistry that employs rape oil.\n3. **Essential Details:** Include necessary steps such as reaction conditions, reagent ratios, molar quantities, temperatures, catalysts, and purification.\n\n---\n\n### **Scientific Approach and Analysis:**\nRape oil (commonly known as rapeseed oil) is composed mainly of triglycerides, where long-chain fatty acids are esterified with glycerol. To enhance hydrophilicity, it will be necessary to modify its hydrophobic aliphatic chains with hydrophilic functional groups. The polymer itself must be selected or synthesized to permit such functionalization. The key mechanism here involves exploiting the reactivity of rape oil (such as its unsaturated bonds or ester group) to improve the hydrophilicity of the resulting polymer.\n\n---\n\n### **Experimental Preparation Scheme:**\nBelow is a systematic formulation of the experimental procedure:\n\n---\n\n#### **Step 1: Polymer Selection and Pretreatment**\n1. **Polymer Choice:** Select a polymer capable of functionalization, such as polyethylene, polypropylene, or polyacrylate. For enhanced hydrophilicity, a base polymer containing reactive groups (e.g., hydroxyl or carboxyl) or capable of grafting is ideal.\n   - Example: Poly(acrylic acid) or poly(vinyl alcohol) can serve as an excellent starting point.\n2. **Pre-treatment (if necessary):**\n   - If starting with a hydrophobic polymer (e.g., polyethylene), perform surface activation via plasma treatment or chemical oxidation to introduce functional groups such as hydroxyl groups.\n   - **Reagents and Conditions:**\n     - Plasma treatment: Treat polymer with oxygen plasma for 2–5 minutes at low pressure (~10–20 Pa).\n     - Chemical oxidation: Soak polymer in an aqueous solution of a strong oxidant (e.g., KMnO₄ in acidic medium) at room temperature for 1–2 hours.\n\n---\n\n#### **Step 2: Modification of Rapeseed Oil**\n1. **Objective:** Introduce hydrophilic functionality into rapeseed oil by functionalizing its fatty acid chains with polar groups (e.g., hydroxyl, carboxyl).\n   \n2. **Reaction Pathway: Epoxidation, followed by hydrolysis**\n   - **Epoxidation of Unsaturated Bonds:** Use rapeseed oil's unsaturated fatty acids (e.g., oleic acid) to introduce epoxy groups, which can then be hydrolyzed to form hydroxyl groups.\n   - **Reaction Setup and Conditions:**\n     - In a 3-neck flask, add 100 g of rapeseed oil.\n     - Add 0.05 mol of hydrogen peroxide (H₂O₂, 30%) and catalytic acetic acid (0.01 mol).\n     - Stir at 60°C for 4–6 hours under mild reflux.\n   - Post-epoxidation, perform hydrolysis:\n     - Add dilute sulfuric acid (0.1 mol H₂SO₄) to the reaction mixture.\n     - Heat to 80–85°C for 3 hours until hydroxyl groups are introduced on the fatty acid chains.\n   - Purify the hydroxylated rape oil product via solvent extraction, e.g., diethyl ether, followed by drying.\n\n---\n\n#### **Step 3: Polymer Functionalization via Grafting**\n1. **Objective:** Use hydroxylated rapeseed oil as a hydrophilic modifier to graft onto the polymer backbone.\n   \n2. **Reaction Pathway: Esterification or amidation**\n   - If the polymer contains carboxyl or hydroxyl groups (e.g., poly(acrylic acid)), esterification or amidation can bond the hydrophilic segments.\n   - **Reaction Procedure:**\n     - Dissolve 10 g of the base polymer in 100 mL of dimethylformamide (DMF) or another suitable solvent.\n     - Add 0.5 mol hydroxylated rape oil and 0.1 mol of coupling agent (e.g., dicyclohexylcarbodiimide, DCC) along with 0.01 mol of catalyst (e.g., 4-dimethylaminopyridine, DMAP).\n     - Stir at 80–90°C for 6–8 hours.\n   - Ensure reflux and proper stirring throughout the reaction.\n   - Monitor functionalization progress using FTIR spectroscopy (look for emergence of ester carbonyl peaks).\n\n---\n\n#### **Step 4: Purification of Hydrophilic Polymer**\n1. Precipitate the modified polymer by adding the reaction mixture dropwise into an excess of non-solvent (e.g., water or ethanol).\n2. Wash the precipitated polymer repeatedly with fresh solvent to remove uncoupled rape oil and reaction byproducts.\n3. Dry the washed polymer under vacuum at 60–70°C overnight.\n\n---\n\n#### **Step 5: Characterization**\n1. **Hydrophilicity Testing:**\n   - Perform water contact angle measurements to compare the hydrophilicity of the original polymer and the modified polymer.\n   - Expect a significant decrease in the water contact angle if functionalization is successful.\n2. **Structural Characterization:**\n   - Use FTIR to confirm the introduction of hydrophilic groups.\n   - Run NMR to verify the structural modification of rape oil and its grafting onto the polymer.\n3. **Thermal Analysis:**\n   - Use DSC/TGA to ensure the thermal stability of the modified polymer.\n\n---\n\n### **Final Notes:**\n- Carefully note all molar ratios and quantities during the experiment.\n- Perform reactions involving peroxide or acids in a well-ventilated fume hood with appropriate protective equipment.\n\nThis experimental scheme outlines the modification of a polymer using rape oil through logical steps, ensuring enhanced hydrophilicity. Let me know if further clarification or adjustments are required, and good luck with your laboratory work!"
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+{
+  "design_question": "Based on the molecule ethyl hydroxyethyl cellulose, explain how you would utilize it in the preparation of a hydrophilic polymer coating to enhance the polymer's wettability. Include the rationale behind its inclusion in the composition.",
+  "design_answer": "Certainly! Let’s break down your question systematically to ensure thorough understanding and practical application for the preparation of a hydrophilic polymer coating using ethyl hydroxyethyl cellulose (EHEC). \n\n---\n\n### **Step 1: Analyze the Question – Key Points**\nThe molecule mentioned, **ethyl hydroxyethyl cellulose (EHEC)**, is a cellulose derivative. It contains both hydrophobic ethyl groups and hydrophilic hydroxyethyl groups, making it a surface-active agent. Its structure makes it highly valuable in improving hydrophilicity due to its excellent water retention and film-forming properties. Your question is to design a synthesis scheme for a **hydrophilic polymer coating**, aimed at enhancing the polymer's wettability.\n\nThus, the focus is:\n- Incorporating EHEC into the coating composition.\n- Optimizing the reaction to maximize hydrophilic properties.\n- Ensuring clear steps, conditions, and rationale for achieving a successful hydrophilic polymer film.\n\n---\n\n### **Step 2: Detailed Experimental Preparation Scheme**\nHere is a systematic approach for preparing a hydrophilic polymer coating using ethyl hydroxyethyl cellulose:\n\n---\n\n#### **Step 2.1: Gather Materials and Reagents**\nBefore starting, gather the following:\n1. **Ethyl Hydroxyethyl Cellulose (EHEC)** – hydrophilic component.\n2. **Acrylic Monomer** – such as acrylic acid (AA), acrylamide (AM), or hydroxyethyl methacrylate (HEMA) for polymer backbone formation.\n3. **Crosslinker** – such as N,N'-methylenebisacrylamide (MBA) to provide structural stability to the polymer network.\n4. **Initiator** – such as ammonium persulfate (APS) or potassium persulfate (KPS) for radical polymerization.\n5. **Deionized Water** – used as the reaction medium to aid hydrophilic interaction.\n6. **Neutralization Agent** – e.g., sodium hydroxide (NaOH), to adjust the pH of acrylic acid to improve solubility.\n\n---\n\n#### **Step 2.2: Design the Reaction Procedure**\nNow, let us synthesize the hydrophilic polymer coating step by step.\n\n---\n\n##### **Step 2.2.1: Prepare the EHEC Solution**\n- **Purpose**: Dissolve EHEC to distribute it homogeneously in the reaction matrix.\n- **Procedure**:\n   1. Measure **2-5 wt% of EHEC** relative to the final polymer solution’s weight. The exact percentage can vary based on the hydrophilicity required.\n   2. Add EHEC slowly to **deionized water** under continuous stirring (around 300 rpm).\n   3. Heat the solution to **50-60°C** to promote complete dissolution, as EHEC dissolves more readily at elevated temperatures.\n   4. Stir until a clear viscous solution is obtained.\n- **Rationale**: EHEC acts as a film-former and hydrophilicity enhancer; a homogeneous solution ensures uniform properties throughout the film.\n\n---\n\n##### **Step 2.2.2: Prepare the Monomer Solution**\n- **Purpose**: Mix acrylic monomers and adjust the pH for solubility and polymerization readiness.\n- **Procedure**:\n   1. Add **acrylic acid (10 wt%)** to a separate container of water under stirring. Acrylic acid imparts hydrophilic carboxylic groups to the polymer.\n   2. **Neutralize the acrylic acid** by slowly adding 2 M NaOH until the solution pH reaches around **6.5–7.5**. This avoids excess acidity that might disrupt polymerization.\n   3. Add **1–2 wt% hydroxyethyl methacrylate (HEMA)** or acrylamide (AM), which contribute additional hydrophilic functional groups. Adjust the ratio if you wish to vary hydrophilic and mechanical properties.\n   4. Mix thoroughly to ensure all monomers are well-dispersed.\n\n---\n\n##### **Step 2.2.3: Combine Solutions**\n- **Purpose**: Blend EHEC into the monomer solution for copolymerization.\n- **Procedure**:\n   1. Slowly pour the prepared **EHEC solution** into the monomer solution while stirring continuously at 300-400 rpm.\n   2. Ensure no clumping occurs, and the mixture forms a uniform, viscous solution.\n- **Rationale**: EHEC integrates into the polymer matrix during polymerization, contributing hydroxyl groups and hydrophilic features.\n\n---\n\n##### **Step 2.2.4: Initiate Polymerization**\n- **Purpose**: Start radical polymerization to form the hydrophilic polymer.\n- **Procedure**:\n   1. Cool the solution to **25-30°C**, then add the initiator (e.g., 0.5 wt% APS) under gentle stirring.\n   2. Optionally, add **crosslinker** (e.g., 1 wt% MBA) to create a 3D network for more robustness.\n   3. Degas the solution by bubbling nitrogen gas through it for 30 minutes to prevent oxygen inhibition.\n   4. Heat the reaction vessel to **60-70°C** and maintain it for 2–3 hours to allow polymerization to proceed.\n- **Rationale**: Radical polymerization promotes the copolymerization of acrylic monomers with EHEC, forming a hydrophilic copolymer.\n\n---\n\n##### **Step 2.2.5: Coat the Substrate**\n- **Purpose**: Apply the polymer solution as a coating for testing hydrophilicity.\n- **Procedure**:\n   1. Once the polymerization is complete, cool the viscous polymer solution to room temperature.\n   2. Spin-coat or dip-coat the solution onto the desired substrate (e.g., glass, plastic) to form a thin film.\n   3. Dry the coated substrate at **40-50°C** in a vacuum oven for 24 hours to remove residual moisture and stabilize the film.\n- **Rationale**: Coating the substrate allows for testing of the hydrophilic properties imparted by the EHEC-polymer matrix.\n\n---\n\n#### **Step 2.3: Evaluate the Hydrophilic Polymer Coating**\n- **Contact Angle Measurement**: Measure the water contact angle of the coated surface to assess wettability. A smaller contact angle (<30°) indicates good hydrophilicity.\n- **Film Uniformity**: Inspect the film for transparency and defects to ensure quality.\n- **Water Retention**: Perform a water absorption or retention test to quantify hydrophilicity.\n\n---\n\n### **Step 3: Rationale for Using EHEC**\n- **Enhances Hydrophilicity**: EHEC contains abundant hydroxyl (-OH) groups that attract water molecules, reducing the water contact angle.\n- **Improves Film-Forming Ability**: Its cellulose backbone contributes to the uniformity and stability of the coating.\n- **Prevents Aggregation**: EHEC provides steric stabilization, ensuring even distribution of hydrophilic properties in the final polymer matrix.\n- **Environment-Friendly**: As a cellulose derivative, EHEC is biodegradable and non-toxic, making the process sustainable.\n\n---\n\n### **Conclusion**\nIn this process, EHEC serves as a vital component for enhancing the hydrophilicity of the polymer coating by introducing hydroxyl groups and water-compatible structures. By following the detailed protocol above, you should be able to successfully prepare a hydrophilic polymer coating with improved wettability."
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diff --git a/task2/task2-qa/2_UV╖└╬э╥║╩╣╙├╦╡├ў╩щ.json b/task2/task2-qa/2_UV╖└╬э╥║╩╣╙├╦╡├ў╩щ.json
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+{
+  "design_question": "Explain the reasoning behind setting specific temperature and UV curing energy parameters during the molecule application process, and how these factors contribute to achieving enhanced hydrophilicity in the modified polymer.",
+  "design_answer": "Certainly! Let us approach your question step-by-step to fully explore the reasoning behind setting specific *temperature* and *UV curing energy* parameters during the modification of the polymer to enhance its hydrophilicity. Please follow along sequentially as we analyze the key factors at play, establish the practical rationale for these parameters, and relate them to the molecular mechanisms driving hydrophilicity.\n\n---\n\n### **1. Analysis of the Question and Key Points**\nThe question focuses on two critical process factors during the polymer modification for enhanced hydrophilicity:\n- **Temperature:** Why is a specific temperature range chosen during the synthesis or application of the polymer?\n- **UV Curing Energy:** How does the intensity and duration of UV exposure improve hydrophilicity?\n\nTo properly answer this, we need to:\n- Examine the molecular interactions between the functional species (e.g., hydrophilic monomers, oligomers, or additives) and the parent polymer.\n- Consider how temperature affects reaction kinetics, polymer cross-linking, and functional group mobility.\n- Understand the role of UV curing in initiating chemical reactions, stabilizing hydrophilic functionalities, polymerizing or cross-linking species, and minimizing undesired side reactions.\n\n---\n\n### **2. Step-by-Step Explanation**\n\n#### **Step 1: Setting the Specific Temperature Range**\n**Why is temperature important?**  \nIn the preparation of hydrophilic polymers, temperature directly impacts:\n1. **Reaction Kinetics:** Higher temperatures accelerate the polymerization or grafting reaction of hydrophilic monomers onto the polymer backbone by:\n   - Increasing the energy of molecular collisions.\n   - Reducing the activation energy needed for bond formation.\n2. **Diffusion and Incorporation:** Many hydrophilic functional groups (e.g., -OH, -NH2, -COOH) are relatively polar. At elevated temperatures, monomers or reagents have improved diffusion into the polymer matrix, promoting better surface wetting and incorporation.\n3. **Avoiding Degradation:** The temperature must not be so high as to cause the degradation or thermal decomposition of either the polymer backbone or functional groups.\n\n**Typical temperature considerations:**\n- Common hydrophilic monomers such as acrylic acid (AA), hydroxyethyl methacrylate (HEMA), or polyethylene glycol (PEG) derivatives polymerize effectively in the range of **60–80°C** in the presence of free-radical initiators (e.g., azobisisobutyronitrile, AIBN) or **40–60°C** with redox initiator systems.\n- For polymers susceptible to temperature degradation (e.g., hydrogels, proteins, or naturally derived polymers like gelatin), lower temperatures (even as low as 30–40°C) may be used.\n- Temperatures in the curing stage ensure effective volatilization of water or solvents, promoting strong adherence and uniform functionalization.\n\n**Optimal temperature settings:**\n- Determine experimentally by thermal analysis (e.g., thermogravimetric analysis, TGA) to pinpoint the range where the polymer remains stable and hydrophilic functionalization proceeds efficiently.\n\n---\n\n#### **Step 2: Setting the UV Curing Energy Parameters**\n**How does UV curing promote hydrophilicity?**  \nUV curing introduces functionality into the polymer matrix by initiating specific photochemical reactions. This process depends on UV wavelength, intensity, and exposure duration. Key mechanisms are:\n\n1. **Photoinitiation of Polymerization:**\n   - UV light triggers the decomposition of photoinitiators (e.g., benzophenone, Irgacure species) into reactive radicals.\n   - These radicals initiate chain reactions, leading to polymerization of hydrophilic precursor monomers or grafting of functional species onto the polymer backbone.\n   - For optimal curing, wavelengths of **300–365 nm (near UV-A region)** are typical for activating most photoinitiators.\n\n2. **Formation of Hydrophilic Structures:**\n   - UV-generated radicals can directly form hydrophilic moieties such as -COOH (carboxyl) or -OH (hydroxyl) groups on the polymer surface by photooxidation reactions.\n   - This enhances surface energy, boosting the affinity for water molecules.\n\n3. **Cross-linking of Hydrophilic Components:**\n   - UV curing can stabilize hydrophilic functionality by forming a 3D network of cross-linked polymer chains, locking the hydrophilic groups into place and ensuring chemical stability in aqueous environments.\n\n4. **Optimizing UV Energy Parameters:**\n   - **Low UV energy (insufficient):** May lead to incomplete curing, leaving residual unreacted species or unbound hydrophilic groups.\n   - **Excess UV energy/intensity:** Can cause chain scission and degrade either the hydrophilic components or the polymer backbone, reducing performance.\n   - **Controlled Parameters:**\n     - Wavelength: ~300–365 nm (activation of most typical photoinitiators).\n     - Intensity: ~100–150 mW/cm² (commonly sufficient for monomer cross-linking without degradation).\n     - Exposure time: Often optimized by experimentation, e.g., **30–120 seconds**.\n\n---\n\n#### **Step 3: How These Factors Work Together to Enhance Hydrophilicity**\nThe interplay of temperature and UV curing determines the final hydrophilic properties of the polymer. Their mechanisms and contributions are summarized below:\n\n1. **Enhanced Incorporation of Hydrophilic Groups:**\n   - Temperature improves the diffusion and reaction kinetics of the hydrophilic monomers and functional groups, increasing the density of hydrophilic moieties on the polymer surface.\n   - UV curing ensures stable chemical bonding of these groups within the polymer matrix by initiating polymerization or photo-cross-linking.\n\n2. **Optimal Surface Modification:**\n   - Temperature promotes uniform interaction between the hydrophilic reagents and the polymer substrate.\n   - UV energy drives surface-specific reactions, ensuring the hydrophilic modification is localized near the polymer-water interface, enhancing water wettability and compatibility.\n\n3. **Long-Term Stability of Hydrophilic Surface:**\n   - Cross-linking at appropriate UV curing energy prevents leaching of hydrophilic agents in aqueous media, maintaining the hydrophilicity over time.\n\n---\n\n### **3. Summary**\nTo enhance hydrophilicity in a modified polymer:\n1. Set a specific **temperature range** suitable for hydrophilic monomer reactions, balancing reaction kinetics and polymer stability (e.g., **60–80°C** for free-radical polymerization or lower for sensitive systems).\n2. Optimize **UV curing energy parameters** to polymerize and/or cross-link hydrophilic functionalities without causing degradation (e.g., **300–365 nm wavelength**, **100–150 mW/cm² intensity**, **30–120 s exposure time**).\n3. Ensure these conditions promote uniform diffusion, bonding, and stabilization of hydrophilic groups, enabling both enhanced hydrophilicity and long-term stability.\n\nBy properly tuning both factors, you can control the functionality and performance of the final hydrophilic polymer in real-world applications.\n\nWould you like me to draft a specific experimental procedure for applying these principles?"
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diff --git a/task2/task2-qa/A novel organic-inorganic zwitterionic acrylate polymer for high-performance anti-fog coating.json b/task2/task2-qa/A novel organic-inorganic zwitterionic acrylate polymer for high-performance anti-fog coating.json
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+{
+  "design_question": "Describe the steps you would take to synthesize 3-(bis(hydroxymethyl)amino)-2-hydroxypropyl methacrylate (D-GMA) and explain why this molecule is significant for enhancing the hydrophilicity of the polymer material.",
+  "design_answer": "Let us carefully approach your question step by step and systematically design a synthesis scheme for the molecule **3-(bis(hydroxymethyl)amino)-2-hydroxypropyl methacrylate (D-GMA)** while also explaining its significance. First, I will analyze the problem, summarize the key chemistry involved, and then provide a stepwise protocol for performing the synthesis in the laboratory.\n\n---\n\n### **Step 1: Analyze the Question and Summarize Key Points**\n\n**Aims of the Question:**\n1. To design a synthetic route for preparing **3-(bis(hydroxymethyl)amino)-2-hydroxypropyl methacrylate (D-GMA)**.\n2. To explain why incorporating D-GMA into a polymer structure improves the hydrophilicity of the material.\n\n**Important Observations:**\n- D-GMA contains a **methacrylate (vinyl ester)** moiety for polymerization, combined with functional groups that enhance hydrophilicity, such as:\n  - A central hydroxy group (-OH).\n  - Bis(hydroxymethyl)amino functionality (-CH2OH groups attached to an amine nitrogen).\n- These highly polar hydroxyl (-OH) groups and the amine's interaction with water contribute to its hydrophilic nature.\n- We will need to pay close attention to reaction conditions, as D-GMA contains highly reactive functional groups that require careful handling to avoid side reactions.\n\n---\n\n### **Step 2: Experimental Synthesis of D-GMA**\n\nI will now detail the synthesis process with a complete explanation of each step, the reagents required, conditions, and molar quantities to aid your understanding and performance in a laboratory setting.\n\n---\n\n#### **Step A: Synthesis of Hydroxymethylamines**\n\nThe first objective is to introduce bis(hydroxymethyl) functionality into an amine group. The precursor is **ammonia (NH3)** or a primary amine, reacted with **formaldehyde (CH2O)**.\n\n1. **Reactant Preparation:**\n   - React formaldehyde with ammonia solution (or methylamine) in an aqueous medium.\n   - Employ a molar ratio of **3:1 (formaldehyde:ammonia/methylamine)** to maximize the formation of bis(hydroxymethyl)amine.\n\n2. **Reaction Conditions:**\n   - Conduct the reaction in water as the solvent at a controlled **temperature of 50–60°C** for 4–6 hours with gentle stirring to ensure uniform mixing.\n   - The reaction scheme:\n     \\[\n     NH_3 + 2CH_2O \\rightarrow NH(CH_2OH)_2\n     \\]\n\n3. **Product Outcome:**\n   - The resulting intermediate is **bis(hydroxymethyl)amine (NH-CH2OH)2)** in aqueous solution.\n\n4. **Workup:**\n   - Cool the reaction mixture to room temperature.\n   - Extract and purify the product by crystallization or evaporation of water to concentrate it.\n\n---\n\n#### **Step B: Addition of Epichlorohydrin**\n\nNext, we introduce a secondary hydroxy group (-OH) using **epichlorohydrin**, an epoxide-containing compound, which reacts with the amine derivative from Step A.\n\n1. **Reactant Preparation:**\n   - Use **1 mol equivalent of bis(hydroxymethyl)amine** and **1.2 mol equivalents of epichlorohydrin** in an aqueous or organic solvent, such as methanol.\n\n2. **Reaction Conditions:**\n   - React the mixture at **35–50°C** for approximately 12–16 hours with stirring.\n\n3. **Reaction Mechanism:**\n   - Epichlorohydrin undergoes nucleophilic ring-opening by the amine, forming a hydroxypropyl-amine intermediate:\n     \\[\n     NH(CH_2OH)_2 + \\text{Epichlorohydrin} \\rightarrow \\text{3-(bis(hydroxymethyl)amino)-2-hydroxypropyl derivative.}\n     \\]\n\n4. **Workup:**\n   - Purify the product by extracting the reaction mixture with an organic solvent (e.g., ethyl acetate).\n   - Wash with brine to remove impurities, dry over anhydrous sodium sulfate, and evaporate the solvent under reduced pressure.\n\n---\n\n#### **Step C: Esterification with Methacrylic Acid**\n\nFinally, the **methacrylate moiety** is introduced by esterification of the hydroxypropyl-amine derivative.\n\n1. **Reactant Preparation:**\n   - Combine **1 mol equivalent of the hydroxypropyl-amine product** from Step B with **1.1 mol equivalents of methacrylic acid**.\n   - Include a **catalyst** such as **p-toluenesulfonic acid (PTSA)** or dicyclohexyl carbodiimide (DCC) if required.\n\n2. **Reaction Conditions:**\n   - Conduct the reaction in a dry organic solvent such as **toluene** at **60–70°C** under nitrogen atmosphere for 6–8 hours.\n   - Continuously remove the water (a by-product of esterification) using a Dean-Stark trap to drive the reaction forward.\n\n3. **Reaction Scheme:**\n   \\[\n   3-(\\text{bis(hydroxymethyl)amino)}-2-hydroxypropyl) + \\text{Methacrylic acid} \\rightarrow \\text{D-GMA}\n   \\]\n\n4. **Workup:**\n   - Allow the reaction mixture to cool to room temperature.\n   - Extract the crude product with an organic solvent (e.g., dichloromethane), wash with water, dry over anhydrous sodium sulfate, and evaporate the solvent under reduced pressure.\n\n5. **Purification:**\n   - Purify the product using column chromatography or recrystallization.\n\n---\n\n### **Step 3: Why D-GMA Enhances Hydrophilicity**\n\nThe hydrophilic nature of D-GMA arises due to its structural features:\n- The presence of three highly polar groups: a central **hydroxy (OH)** group and two **hydroxymethyl (-CH2OH)** groups attached to the amino group. These groups form hydrogen bonds with water, improving the polymer’s wettability and water retention.\n- When copolymerized with other monomers, D-GMA structures remain exposed on the polymer surface, ensuring hydrophilic properties in applications like biomaterials, coatings, and hydrogels.\n\n---\n\n### **Step 4: Summarized Notes for Lab Execution**\n\n1. Strictly control the molar ratios of reactants to minimize by-products.\n2. Optimize temperatures to avoid degradation of reactive groups.\n3. Use inert atmospheres during esterifications to prevent side reactions (e.g., oxygen inhibiting methacrylate polymerization).\n4. Purify intermediates to ensure high product quality.\n\nBy carefully following these steps, you will obtain pure D-GMA suitable for use as a polymerizable hydrophilic monomer."
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diff --git a/task2/task2-qa/ANTI-FOG    US10241237B2.json b/task2/task2-qa/ANTI-FOG    US10241237B2.json
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+{
+  "design_question": "How would you use the molecule dimethylol propionic acid (DMPA) to prepare a hydrophilic polymer with enhanced water dispersibility and anionic stabilization properties? Describe the steps and the role of this molecule in the synthesis process.",
+  "design_answer": "Certainly! Enhancing the hydrophilicity and water dispersibility of polymers is a critical area in materials science, particularly in applications such as coatings, adhesives, and biomedical materials. Dimethylol propionic acid (DMPA) is a versatile monomer for introducing hydrophilic groups into polymer structures due to its unique structure—it contains hydroxyl groups for polymerization and a carboxylic acid group that can impart anionic stabilization properties. Let’s analyze your question step by step and provide a systematic experimental preparation scheme.\n\n---\n\n### Key Points from Your Question:\n1. **Target Polymer Properties**:\n   - Enhanced water dispersibility.\n   - Anionic stabilization properties.\n\n2. **Role of DMPA**:\n   - Hydrophilic hydroxyl groups for improved water affinity.\n   - Carboxylic acid groups for introducing ionic stabilization.\n\n3. **Preparation Method**:\n   - Choosing appropriate co-monomers or pre-polymers.\n   - Incorporating DMPA into the polymer backbone or as a pendant group.\n\nNow let’s proceed with the detailed experimental design.\n\n---\n\n### Experimental Preparation Scheme for Hydrophilic Polymer Using DMPA:\n\n#### Step 1: Polymer Design and Selection of Co-monomers\nStart by selecting monomers or pre-polymers that can polymerize with DMPA to form a polymer matrix. Examples include diols (e.g., neopentyl glycol or ethylene glycol), diisocyanates (e.g., hexamethylene diisocyanate, HDI), or pre-polymers such as polyesters or polyethers. Given the goal of hydrophilicity, you should prioritize aliphatic diols or other flexible molecules with minimal steric hindrance.\n\n#### Step 2: Reaction Type\nIncorporate DMPA using a step-growth polymerization process, such as polyurethane or polyester synthesis, where its hydroxyl groups participate in esterification or urethane formation, and its carboxylic acid group is retained for ionic stabilization. An alternative approach is using free radical polymerization where DMPA is a co-monomer with vinyl-functionalized molecules.\n\n#### Step 3: Experimental Details\nLet us focus on the preparation of a polyurethane polymer with enhanced hydrophilic properties using DMPA.\n\n---\n\n### Experimental Procedure: Synthesis of Hydrophilic Polyurethane Using DMPA\n\n#### **Materials**:\n- **Dimethylol propionic acid (DMPA)**: Key hydrophilic monomer.\n- **Diisocyanate**: Hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI) for urethane linkage.\n- **Diols**: Ethylene glycol (EG) or neopentyl glycol (NPG) for additional polymer backbone properties.\n- **Neutralizing agent**: Triethylamine (TEA) or sodium hydroxide for ionic stabilization.\n- **Catalyst**: Dibutyltin dilaurate (DBTDL).\n- **Solvent**: N,N-dimethylformamide (DMF) or acetone (optional, for reaction medium).\n\n---\n\n#### **Steps in Synthesis**:\n\n##### **1. Pre-Polymer Formation (Isocyanate Reaction Stage)**:\n- Weigh the diisocyanate according to a stoichiometric ratio (NCO/OH ratio slightly above 1.05 to produce an NCO-terminated pre-polymer).\n- Add DMPA to the reaction vessel in stoichiometric proportions with OH functionality accounted for.\n- Introduce the diol (e.g., ethylene glycol) as the co-reagent.\n- Heat the reaction vessel to 60–80°C under nitrogen atmosphere while stirring.\n- Add the catalyst (DBTDL, typically 0.05–0.1% w/w) to enhance urethane linkage formation.\n\nReaction Pathway:\n\\[ \\text{R}{-}\\text{NCO} + \\text{HO}{-}\\text{R} \\rightarrow \\text{R}{-}\\text{NHCOO−R} \\]\n\nRole of DMPA: The hydroxyl groups react to form urethane linkages, while the carboxylic acid groups remain unreacted.\n\n---\n\n##### **2. Neutralization (Carboxylate Formation via Ionization)**:\n- After forming the pre-polymer, introduce triethylamine (TEA) or sodium hydroxide to neutralize the carboxylic acid groups of DMPA.\n- Stir at room temperature for 30 minutes to ensure full neutralization.\n\nReaction Pathway:\n\\[ \\text{COOH} + \\text{NaOH (or TEA)} \\rightarrow \\text{COO}^- \\text{(anionic stabilization group)} \\]\n\nEffect of Neutralization: Enhances ionic stabilizing properties and increases water dispersibility due to the formation of carboxylate groups.\n\n---\n\n##### **3. Final Polymerization and Chain Extension**:\n- Introduce excess diol (optional for chain extension) or crosslinking agent to react with any remaining NCO groups.\n- Heat the mixture to 80–90°C for the completion of polymerization while monitoring viscosity changes.\n- Ensure complete conversion of NCO groups using an FTIR analysis (absence of peak at ~2270 cm⁻¹).\n- The resulting product will be a water-dispersible polyurethane with hydrophilic properties imparted by DMPA.\n\n---\n\n##### **4. Post-Treatment and Characterization**:\n- Dissolve the polymer in an aqueous medium to test for water dispersibility.\n- Characterize the polymer using techniques like FTIR (functional group confirmation), DSC/TGA (thermal stability), and DLS (particle size in dispersion).\n- Adjust pH and ionic strength as needed to optimize water dispersibility.\n\n---\n\n### Role of DMPA in the Polymer:\n1. **Hydrophilicity**: The hydroxyl groups of DMPA integrate into the polymer backbone, promoting water affinity.\n2. **Anionic Stabilization**: The carboxylic acid groups (after neutralization) form charged carboxylate groups that stabilize the polymer in aqueous systems and prevent aggregation.\n3. **Dispersion Enhancement**: The resulting polymer exhibits excellent water dispersibility, making it suitable for applications like coatings or adhesives.\n\n---\n\n### Final Notes:\nBy carefully controlling the reagent ratios, reaction conditions, and neutralization process, you can successfully synthesize a hydrophilic polymer with enhanced water dispersibility and stabilization properties using DMPA. Its unique structure is essential for achieving these properties.\n\nIf you have additional questions or wish to tweak the formulation for specific applications, feel free to ask!"
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diff --git a/task2/task2-qa/ANTI-FOG  US10048408B2.json b/task2/task2-qa/ANTI-FOG  US10048408B2.json
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+{
+  "design_question": "Using the molecule polyethylene glycol (PEG), design an experimental procedure to synthesize a PEG-based ammonium salt. Specify the reaction conditions required, including temperature, solvent system, and purification methods to obtain a hydrophilic polymer.",
+  "design_answer": "Certainly! Let’s break this down systematically to address your question about synthesizing a PEG-based ammonium salt to enhance hydrophilicity. I will ensure that my response provides a clear understanding of the experimental framework while discussing each step in detail as per the established requirements.\n\n---\n\n### **Analysis of the Question**\n1. **Objective**: To synthesize a hydrophilic polymer by functionalizing polyethylene glycol (PEG) with ammonium salt groups.\n2. **Key Consideration**: PEG, a hydrophilic polymer due to its ether (-CH2-CH2-O-) repeat units, can be further modified by introducing ionic functionalities, such as quaternary ammonium salts, to improve hydrophilicity and impart additional properties like ion exchange potential.\n3. **Primary Task**: To design a systematic experimental procedure, specifying:\n    - Reagents for functionalization of PEG.\n    - Reaction conditions like temperature, time, and solvent(s).\n    - Purification and characterization steps.\n\n---\n\n### **Detailed Experimental Procedure**\nBelow is a step-by-step description of the synthesis process for modifying PEG into a PEG-based ammonium salt polymer using a well-documented quaternization reaction:\n\n---\n\n#### **1. Activation of Polyethylene Glycol (Preparation of PEG-Tosylate)**\nIn this step, PEG is functionalized with a tosyl group (p-toluenesulfonyl group) as a leaving group to facilitate quaternization.\n\n1. **Reagents**:\n    - Polyethylene Glycol (average molecular weight: e.g., 4,000 g/mol, PEG-4000) → 1 equivalent.\n    - p-Toluenesulfonyl chloride (TsCl) → 2 equivalents.\n    - Triethylamine (TEA) → 2 equivalents (acts as a base to neutralize HCl byproduct).\n    - Dry Dichloromethane (DCM) → Solvent.\n    - Dry Ice Bath (for maintaining low reaction temperature).\n\n2. **Procedure**:\n    - Dissolve PEG in dry dichloromethane (DCM) in a round-bottom flask under nitrogen atmosphere to prevent moisture contamination.\n    - Add triethylamine (TEA) dropwise to the reaction flask to act as a base.\n    - Cool the mixture to 0°C using an ice bath or dry ice-chilled bath.\n    - Slowly add a solution of tosyl chloride (TsCl) dissolved in dry DCM to the reaction mixture while continuously stirring.\n    - Continue stirring for 12-16 hours at room temperature to ensure complete tosylation.\n\n3. **Reaction Scheme**:\n    ```reaction\n    HO-(CH2CH2O)n-H + TsCl → Tosyl-O-(CH2CH2O)n-H + HCl\n    ```\n\n4. **Purification**:\n    - Extract the tosylated PEG product by washing with water (to remove TEA hydrochloride) and brine (to remove excess DCM).\n    - Dry the organic layer over anhydrous magnesium sulfate (MgSO4) and evaporate the solvent under reduced pressure.\n    - The pure PEG-tosylate appears as a viscous liquid or solid, depending on the molecular weight of the PEG used.\n\n---\n\n#### **2. Quaternization Reaction (Formation of PEG-Based Ammonium Salt)**\nThe tosyl group on PEG is replaced with a quaternary ammonium group using a tertiary amine.\n\n1. **Reagents**:\n    - Tosylated PEG (from Step 1) → 1 equivalent.\n    - Trimethylamine (TMA) → 3-5 equivalents.\n    - Acetonitrile (CH3CN) → Dry solvent.\n    - Nitrogen Atmosphere → To avoid moisture from the air.\n\n2. **Procedure**:\n    - Dissolve the tosylated PEG in dry acetonitrile in a round-bottom flask.\n    - Cool the reaction mixture to 0°C using an ice bath.\n    - Slowly bubble an excess of gaseous trimethylamine (TMA) into the solution or add TMA as a solution in dry acetonitrile.\n    - Cap the flask and allow the reaction mixture to stir at room temperature for 24-48 hours (alternatively, heat the reaction to 40°C for faster conversion).\n    - Monitor the progress using thin-layer chromatography (TLC), tracking the displacement of the tosyl group by TMA.\n\n3. **Reaction Scheme**:\n    ```reaction\n    Tosyl-O-(CH2CH2O)n-H + (CH3)3N → (CH3)3N+-O-(CH2CH2O)n-H + Tos-\n    ```\n\n4. **Purification**:\n    - Evaporate excess TMA and acetonitrile under reduced pressure.\n    - Dissolve the crude product in water to precipitate out any unreacted reagents or byproducts.\n    - Dialyze the product against distilled water for 24-48 hours to remove residual salts or reactants (using a dialysis membrane with an appropriate molecular weight cutoff).\n\n5. **Final Product**:\n    - The resulting PEG-based ammonium salt is highly hydrophilic and readily soluble in water.\n    - Its structure is characterized by quaternary ammonium groups (-N+(CH3)3) grafted onto the PEG backbone.\n\n---\n\n### **Reaction Conditions Summary**\n- **Step 1 (Tosylation)**:\n    - Solvent: Dry DCM.\n    - Temperature: 0°C initially, then room temperature.\n    - Time: 12-16 hours.\n    - Atmosphere: Nitrogen (dry conditions).\n\n- **Step 2 (Quaternization)**:\n    - Solvent: Dry acetonitrile.\n    - Temperature: 0°C initially, then room temperature (or 40°C for faster reaction).\n    - Time: 24-48 hours.\n    - Atmosphere: Nitrogen (to prevent moisture contamination).\n\n---\n\n### **Characterization Methods**\nTo confirm successful synthesis and elucidate the structure of the PEG-based ammonium salt:\n1. **NMR Spectroscopy**:\n    - Use Proton NMR (1H-NMR) to confirm the presence of quaternary ammonium groups (signal at ~3.2 ppm for -N+(CH3)3 protons).\n    - Carbons in PEG backbone and attached groups can be verified by 13C-NMR.\n2. **FTIR Spectroscopy**:\n    - Monitor characteristic peaks for the ether group (-C-O-C) and ammonium group (-N+(CH3)3).\n3. **Gel Permeation Chromatography (GPC)**:\n    - Determine the molecular weight distribution of the modified PEG.\n4. **Ion Exchange Capacity (IEC)**:\n    - Assess the presence of the quaternary ammonium groups by measuring the ion-exchange capacity.\n\n---\n\n### **Conclusion**\nThis systematic procedure outlines the synthesis of a PEG-based ammonium salt via a two-step functionalization process: (1) tosylation of PEG and (2) quaternization with trimethylamine. By optimizing reaction conditions, including solvent systems, temperature, and molar ratios, you can effectively prepare a highly hydrophilic PEG-based polymer. Careful purification and characterization will ensure high-quality polymer for subsequent applications."
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+{
+  "design_question": "Explain how you would incorporate alkylene oxides into the backbone of a polyurethane polymer to enhance its hydrophilicity. Include specific steps in the synthesis process.",
+  "design_answer": "Incorporating alkylene oxides into the backbone of a polyurethane polymer is an effective strategy to enhance its hydrophilicity. I will systematically address your question by analyzing the key points and providing a detailed experimental preparation scheme, including reaction conditions, reagent ratios, molar quantities, and other relevant details to ensure a clear understanding and practical implementation.\n\n---\n\n### **Key Points to Consider**\n1. **Objective**: To enhance the hydrophilicity of a polyurethane polymer by introducing alkylene oxides, such as polyethylene glycol (PEG) or polypropylene glycol (PPG), as soft segments into the polymer backbone.\n2. **Polyurethane Basics**: Polyurethane synthesis involves the reaction between polyols and di- or multi-functional isocyanates. Alkylene oxides serve as hydrophilic polyols due to their ether linkages.\n3. **Primary Requirements**: \n   - Selection of hydrophilic alkylene oxides as polyol precursors.\n   - Control of molar ratios to achieve the desired hydrophilicity and mechanical properties.\n   - Prevention of phase separation during polymerization.\n\n---\n\n### **Experimental Preparation Scheme**\n\n#### **Step 1: Selection of Raw Materials**\n1. **Polyols (Hydrophilic Component)**:  \n   Use polyethylene glycol (PEG) with controlled molecular weights, e.g., PEG-400 or PEG-1000, depending on the desired degree of hydrophilicity. PEG is a copolymer of ethylene oxide, making it particularly suitable for introducing hydrophilic properties.\n   - For lower hydrophilicity: You might consider polypropylene glycol (PPG), a copolymer of propylene oxide, as its hydrophilic nature is less pronounced than PEG.\n2. **Isocyanates**:  \n   Select aromatic or aliphatic di-isocyanates, such as:\n   - Aromatic: Methylene diphenyl diisocyanate (MDI).\n   - Aliphatic: Hexamethylene diisocyanate (HDI).  \n   Aliphatic di-isocyanates are less likely to yellow with time and exposure, suitable for applications in coatings and biomedical devices.\n3. **Chain Extender (Optional)**:  \n   Use a small diol such as 1,4-butanediol (BDO) or ethylene glycol to tune mechanical properties.\n\n---\n\n#### **Step 2: Pre-experiment Setup**\n1. **Equipment**:\n   - A glass reactor equipped with stirring, temperature control, and nitrogen purging.\n2. **Safety Precautions**:\n   - Isocyanates are highly reactive and toxic. Work in a fume hood with gloves and proper protective equipment.\n3. **Solvents** (if required for miscibility): Use dry solvents such as dimethylformamide (DMF) or tetrahydrofuran (THF). Ensure solvents are anhydrous to prevent side reactions with water.\n\n---\n\n#### **Step 3: Synthesis Process**\n1. **Molar Ratios**:  \n   - Maintain a 1:1 isocyanate-to-hydroxyl ratio for a stoichiometric reaction.\n   - If PEG is the soft segment, select molecular weights and adjust ratios based on desired hydrophilicity. For example:\n     - For enhanced hydrophilicity: Use PEG-1000 and target 50% by weight in the final polymer.\n     - For reduced hydrophilicity: Use PEG-400 and target 30% by weight in the final polymer.\n\n2. **Reaction Conditions**:\n   - Dry all materials before use to avoid water interfering with the isocyanate reaction.\n   - Degas PEG and solvents by purging with dry nitrogen for 30 minutes.\n   - Tropsch the isocyanates under inert gas (e.g., nitrogen).\n\n3. **Step-by-Step Polymerization**:\n   **Step 3.1: Formation of Prepolymer**  \n   - Add the calculated amount of PEG to a reactor with anhydrous solvent (if required).\n   - Heat the reactor to 60–80°C under gentle stirring.\n   - Introduce the di-isocyanate slowly in the stoichiometric ratio (NCO:OH = 1:1). Monitor the progress with FTIR spectroscopy—hydroxyl depletion and NCO peaks should be tracked.\n   - Allow the reaction between PEG and di-isocyanate to form the prepolymer. This typically takes **2–4 hours**.\n\n   **Step 3.2: Polymer Formation**  \n   - Cool the reaction mixture to 40–60°C.\n   - If a chain extender is used (e.g., BDO), add it slowly in the calculated stoichiometric ratio (NCO:OH = 1:1). Chain extenders help tune mechanical properties.\n   - Continue stirring at 40–60°C for an additional **3–6 hours**.\n\n4. **Post-reaction Monitoring**:\n   - Analyze the polymer structure using **FTIR**: Ensure complete reaction of isocyanate and hydroxyl groups.\n   - Gel permeation chromatography (GPC) can be used to analyze molecular weight distribution.\n\n---\n\n#### **Step 4: Purification and Post-processing**\n- Allow the polymer to cure if necessary (e.g., for coatings).\n- Optionally wash with ethanol or other solvents to remove unreacted reactants or side products.\n- Dry the polymer in a vacuum oven at 40–60°C to remove residual solvents.\n\n---\n\n#### **Step 5: Testing Hydrophilicity**\n- Perform water contact angle measurements. Hydrophilic polymers typically exhibit a low contact angle (<90°).\n- Optional: Measure swelling properties in water, as PEG-incorporated polyurethane will absorb water due to its hydrophilic nature.\n\n---\n\n### **Notes on Optimization**\n1. **Balancing Hydrophilicity**: Excess PEG can reduce mechanical properties like tensile strength and elasticity. Carefully optimize its weight fraction in the polymer backbone.\n2. **Curing Agents** (if necessary): Select curing agents depending on the application, such as water for polyurethane foams or UV-activated agents for coatings.\n3. **Environmental Considerations**: Use greener alternatives if possible, such as bio-based isocyanates.\n\n---\n\nBy following these steps, you should be able to successfully synthesize a polyurethane polymer with enhanced hydrophilicity, customized to your experimental requirements. Let me know if you'd like further assistance with detailed calculations or any specific adjustments!"
+}
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diff --git a/task2/task2-qa/Advanced Science - 2022 - Shi - Effective Antifogging Coating from Hydrophilic Hydrophobic Polymer Heteronetwork.json b/task2/task2-qa/Advanced Science - 2022 - Shi - Effective Antifogging Coating from Hydrophilic Hydrophobic Polymer Heteronetwork.json
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+{
+  "design_question": "How would you confirm the successful photopolymerization of 3-(Trimethoxysilyl) propyl methacrylate (TPM) in your experiment, and what spectral features would you monitor to ensure this process has occurred?",
+  "design_answer": "Certainly! Let's systematically address your question to ensure comprehension and laboratory success.\n\n### Analysis and Summary of Key Points\nYour inquiry focuses specifically on the confirmation of successful **photopolymerization** of 3-(Trimethoxysilyl) propyl methacrylate (TPM) and identifying the **spectral features** that must be monitored to verify this transformation. Key aspects include:\n1. **Photopolymerization process**: The TPM monomer undergoes photopolymerization under the influence of light (typically UV or visible light) and a photoinitiator, converting the monomer into a polymer.\n2. **Spectral confirmation**: The degree of polymerization and the chemical changes must be verified, primarily using spectral techniques such as Fourier-transform infrared spectroscopy (FTIR) or nuclear magnetic resonance spectroscopy (NMR).\n\n### Detailed Steps to Confirm Photopolymerization and Monitoring Spectral Features\n\n#### **Step 1: Preparation of the Reaction System**\n1. **Set up the polymerization process**:\n   - Utilize TPM as the monomer.\n   - Dissolve the TPM monomer in a suitable solvent, such as ethanol or acetone, to ensure homogeneity.\n   - Add a photoinitiator (e.g., Irgacure 2959 or 2,2-Dimethoxy-2-phenylacetophenone) at an appropriate concentration (commonly 0.1–2 wt% of the monomer). The photoinitiator is crucial for generating radicals upon exposure to UV light.\n   - Purge the system with nitrogen or argon to eliminate oxygen, which can inhibit radical polymerization.\n\n2. **Photopolymerization process**:\n   - Subject the solution to UV irradiation (typically 365–405 nm wavelength) at controlled conditions. Monitor the duration and intensity of UV exposure (e.g., 5–20 minutes, depending on the light source power).\n   - Stir the reaction gently to maintain uniform polymerization.\n\n#### **Step 2: Characterization of TPM Before and After Polymerization**\nTo confirm the success of polymerization, spectral techniques should be employed to detect the structural changes occurring during the reaction.\n\n---\n\n#### **Spectral Features to Monitor**\n1. **Fourier-Transform Infrared (FTIR) Spectroscopy**:\n   - Prior to polymerization:\n     - Monitor the **C=C stretching vibration** of the methacrylate group, which typically exhibits absorption near **1635–1645 cm⁻¹**.\n     - Observe symmetric and asymmetric **OCH3 (methoxy group)** stretches related to trimethoxysilane functionality (~2800–3000 cm⁻¹).\n   - After polymerization:\n     - A significant **reduction or disappearance** in the intensity of the **C=C stretching vibration** (~1635–1645 cm⁻¹) indicates successful polymerization.\n     - New bands may appear or intensify due to the formation of polymeric **C-O** bonds (~1000–1200 cm⁻¹) that arise from ester linkages in the polymer backbone.\n     - The trimethoxysilane group may remain intact, retaining its spectral signature, unless hydrolysis/condensation reactions are deliberately performed.\n\n2. **Nuclear Magnetic Resonance (NMR) Spectroscopy** (¹H NMR or ¹³C NMR):\n   - Before polymerization:\n     - Observe characteristic peaks for the vinyl protons at ~5.6 and ~6.1 ppm (¹H NMR). These peaks correspond to the methacrylate's **C=CH₂** group.\n   - After polymerization:\n     - The disappearance of the vinyl proton peaks (~5.6 and ~6.1 ppm) and the emergence of broad **aliphatic proton signals** (e.g., ~0.5–2 ppm) indicate that the C=C bonds have polymerized into aliphatic chains.\n     - For the trimethoxysilyl group, inspect the chemical shift attributed to **O-SiCH3**, which generally remains consistent (unless hydrolysis occurs).\n\n3. **Gel Permeation Chromatography (GPC)**:\n   - Conduct GPC analysis to measure the molecular weight distribution of the polymerized TPM. A shift toward higher molecular weights (Mn and Mw) versus the starting monomer confirms polymerization.\n\n4. **Additional Techniques (if available)**:\n   - **Dynamic Mechanical Analysis (DMA)** or thermal analysis can corroborate increased cross-linking density in the resulting polymer.\n   - **Contact angle measurements** may quantify the increased hydrophilicity of the polymer (trimethoxysilane functionality contributes to surface hydroxylation under aqueous conditions).\n\n---\n\n#### **Step 3: Practical Notes for Laboratory Success**\n- Ensure the reaction chamber is light-tight to avoid unintended polymerization before initiating UV exposure.\n- Track reaction progress periodically using FTIR to observe the disappearance of the C=C bond and emergence of polymer peaks.\n- Handle TPM with care, as it is reactive and sensitive to moisture (due to hydrolysis of the silane groups).\n\n---\n\n### Concluding Remarks\nTo confirm successful photopolymerization of TPM:\n1. Use FTIR spectroscopy to verify the disappearance of the C=C group (~1635–1645 cm⁻¹) and the emergence of ester-related polymeric C-O bonds.\n2. Use NMR spectroscopy to monitor the loss of vinyl protons (~5.6–6.1 ppm) and observe the aliphatic polymer backbone signals.\n3. Complement these analyses with molecular weight measurements and/or thermal characterization to ensure polymerization is complete.\n\nThis step-by-step approach provides robust confirmation of your photopolymerization experiment, equipping you with the necessary insights to successfully execute and validate your findings in the lab!"
+}
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diff --git a/task2/task2-qa/Application of machine learning in polymer additive manufacturing_ A review.json b/task2/task2-qa/Application of machine learning in polymer additive manufacturing_ A review.json
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+{
+  "design_question": "Evaluate the effect of varying photoinitiator concentration on achieving hydrophilicity in the polymer. How would you optimize this parameter to ensure successful hydrophilic modification?",
+  "design_answer": "To systematically approach your question, let's break it into manageable components and address them step by step to ensure a robust understanding of the relationship between photoinitiator concentration and hydrophilicity in polymer synthesis. The photoinitiator concentration is critical in photopolymerization reactions because it impacts both the polymer structure and its hydrophilicity. \n\n---\n\n### **Step 1: Analyze the Question and Key Points**\n1. **Key Points**:\n   - The effect of photoinitiator concentration on hydrophilicity in the resulting polymer.\n   - The optimization of photoinitiator concentration for successful hydrophilic modification.\n\n2. **Understanding the Problem**:\n   - Photoinitiators generate free radicals under light exposure to initiate polymerization.\n   - Varying the photoinitiator concentration influences the polymer's crosslink density, molecular weight, chain structure, and ultimately the distribution of hydrophilic functional groups within the polymer.\n\n---\n\n### **Step 2: Systematic Answer and Experimental Guidelines**\nTo evaluate and optimize photoinitiator concentration for enhancing hydrophilicity, one must design and implement a photopolymerization experiment. Below, I will outline the approach in detail:\n\n---\n\n#### **Step 2.1: Define the Experimental System**\n- **Polymer Composition**: Identify the monomer(s) used for hydrophilic polymer synthesis. Examples include:\n  - Monomers such as acrylamide, hydroxyethyl methacrylate (HEMA), or acrylic acid, which naturally impart hydrophilicity. \n  - Comonomers for additional functionality, e.g., N-vinyl pyrrolidone (NVP).\n\n- **Photoinitiator**: A commonly used photoinitiator, such as Irgacure 2959 or 2,2-dimethoxy-2-phenylacetophenone (DMPA), will be analyzed for its effect.\n\n- **Reaction Conditions**:\n  - Light wavelength: Match the spectrum to the absorption range of the photoinitiator, typically UV light around 365 nm.\n  - Reaction medium: Aqueous or hydroorganic systems to support hydrophilic polymerization.\n\n#### **Step 2.2: Experimental Procedure**\n1. **Preparation of Monomer Solution**:\n   - Dissolve hydrophilic monomer(s), such as HEMA (1 M), in deionized water or an appropriate solvent, depending on solubility.\n   - (Optional) Add comonomers in desired mole ratios if copolymerization is required.\n\n2. **Photoinitiator Addition**:\n   - Prepare a series of monomer solutions with varying photoinitiator concentrations. For example:\n     - Concentrations at 0.1%, 0.25%, 0.5%, 1.0%, and 2.0% (w/v) relative to the monomer weight.\n   - Ensure complete dissolution of the photoinitiator by stirring thoroughly in a dark environment to avoid premature initiation.\n\n3. **Polymerization Setup**:\n   - Transfer the solutions into mold chambers (e.g., glass Petri dishes or vials) for uniform light exposure.\n   - Degas the monomer solution under nitrogen or argon to remove dissolved oxygen, which inhibits free radical polymerization.\n\n4. **Photopolymerization**:\n   - Illuminate the samples uniformly with UV light (365 nm) at a controlled intensity.\n   - Polymerization time can range from 10 minutes to 1 hour, depending on the system and photoinitiator efficiency. Monitor the reaction.\n\n---\n\n#### **Step 2.3: Characterization and Evaluation of Hydrophilicity**\nPost-polymerization, evaluate the hydrophilicity of the resulting polymers. The hydrophilicity depends on factors such as surface functional groups, swelling behavior, and water absorption, which are influenced by photoinitiator concentration.\n\n1. **Key Characterization Techniques**:\n   - **Contact Angle Measurement**:\n     - Hydrophilicity is inversely related to the water contact angle. Lower contact angles indicate higher hydrophilicity.\n   - **Swelling Ratio**:\n     - Immerse the polymer in water and measure the mass change over time. Higher swelling ratios reflect better hydrophilic behavior.\n   - **Fourier Transform Infrared Spectroscopy (FTIR)**:\n     - Confirm the incorporation of hydrophilic functional groups (e.g., hydroxyl or carboxyl peaks).\n\n2. **Expected Trends**:\n   - At low photoinitiator concentrations: Polymerization may be incomplete, resulting in reduced crosslink density and poor hydrophilicity due to insufficient chain propagation.\n   - At high photoinitiator concentrations: Excessive free radicals can lead to rapid termination reactions, forming a dense, highly crosslinked network that may restrict the hydration capacity or functional group accessibility.\n\n---\n\n#### **Step 2.4: Optimization of the Photoinitiator Concentration**\nBased on the experimental results, optimize the photoinitiator concentration:\n1. **Determine the Optimal Range**:\n   - Identify the concentration that achieves a balance between adequate polymerization and sufficient hydrophilic functional group exposure.\n   - Typically, this might fall within a moderate concentration range (e.g., 0.5%–1.0% w/v), depending on the specific system.\n\n2. **Reiterate Synthesis**:\n   - Fine-tune the photoinitiator concentration within the identified range to confirm reproducibility and enhance polymer hydrophilicity further.\n\n3. **Consider Additives or Secondary Modifications**:\n   - If optimal photoinitiator concentration alone does not yield desired hydrophilicity, consider post-polymerization modification or blending of hydrophilic monomers.\n\n---\n\n### **Summary**\nTo study the effect of photoinitiator concentration on hydrophilicity, conduct a systematic photopolymerization experiment by preparing polymer formulations with varying photoinitiator levels and characterizing hydrophilicity using contact angles, swelling behavior, and chemical analysis. The optimal concentration balances efficient polymerization with accessibility to hydrophilic functional groups, likely in the moderate range of photoinitiator. Through careful optimization, you can ensure successful hydrophilic modification of the polymer while maintaining reproducibility and efficiency.\n\n"
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diff --git a/task2/task2-qa/Bio-inspired antifogging PDMS coupled micro-pillared superhydrophobic arrays and SiO2 coatings.json b/task2/task2-qa/Bio-inspired antifogging PDMS coupled micro-pillared superhydrophobic arrays and SiO2 coatings.json
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+{
+  "design_question": "When applying the silicon dioxide (SiO2) coating to a polymer substrate, why is it necessary to repeat the spray coating and heating processes multiple times? Discuss the potential impact on the surface properties.",
+  "design_answer": "Ah, this is an excellent question regarding the functionalization of a polymer substrate with a silicon dioxide (SiO₂) coating. Let us carefully analyze the question and address it systematically by thinking step by step, delving into the underlying principles of material science and surface engineering.\n\n---\n\n### 1. **Question Analysis and Key Points**\n\nIn this problem:\n- We are concerned with the process of applying a SiO₂ coating to a polymer substrate via successive steps of **spray coating** followed by **heating.**\n- You are asking specifically why it is necessary to **repeat these steps multiple times**.\n- Additionally, we should examine how repeating these steps influences the **surface properties** of the coated polymer.\n\nThe key points to explore are:\n1. The physical and chemical rationale for repeating the cycles of coating and heating,\n2. The role of each step (spray coating and heating),\n3. The influence on surface properties, with a focus on aspects like thickness, uniformity, adhesion, hydrophilicity, and surface durability.\n\n---\n\n### 2. **Systematic Answer and Step-by-Step Explanation**\n\n#### **Step 1: Spray Coating Process**\nSpray coating is used to deposit a thin film of SiO₂ precursor solution (e.g., a silica sol or tetraethyl orthosilicate, TEOS solution) onto the polymer substrate. When a single layer of any coating is applied, some challenges commonly arise:\n- A single layer is often insufficient for achieving **complete surface coverage,** especially on substrates with imperfections, porous structures, or irregular geometries.\n- Uneven spraying or surface tension effects can result in a thin coating layer that is non-uniform.\n- A single layer may exhibit poor film thickness, which limits its desired functional properties (e.g., hydrophilicity, robustness, or thermal stability).\n\n#### **Step 2: Heating Process**\n- Heating is required primarily to **condense and densify the SiO₂ coating.**\n- Sol-gel precursors like TEOS undergo hydrolysis and condensation reactions to form a silica network, but these reactions need thermal activation to proceed fully.\n- Heating also promotes adhesion of the SiO₂ layer to the polymer substrate by improving intermolecular interactions and potentially enhancing chemical bonding at the interface.\n- However, a single heating step may not achieve full densification of the material or optimal cross-linking, leaving voids or defects in the silica film.\n\n---\n\n#### **Why Is Repetition Necessary?**\nRepeating the spray coating and heating processes builds successive layers of the SiO₂ coating. Each iteration addresses the limitations of the previous layer by adding **thickness, uniformity, and durability**. Specifically:\n\n1. **Improved Surface Coverage:**\n   - A single spray may leave some areas of the polymer substrate exposed due to surface irregularities or spray inconsistencies.\n   - By repeating the process, subsequent layers cover these imperfections, ensuring a uniform and complete SiO₂ film.\n\n2. **Increased Coating Thickness:**\n   - A thicker SiO₂ layer is required to achieve functional surface properties such as high hydrophilicity, mechanical strength, and better thermal or UV resistance.\n   - The thickness of SiO₂ coatings follows an additive principle: each spray-and-heat cycle results in additional material deposition.\n\n3. **Enhanced Uniformity:**\n   - Repeated cycles smooth out inconsistencies in the film that may arise after a single spray-and-heat step, leading to a more homogeneous coating.\n\n4. **Improved Adhesion:**\n   - Successive heating steps enhance the interactions between SiO₂ and the polymer surface, promoting stronger adhesion. This is particularly critical for polymers, which are generally hydrophobic and may initially exhibit poor bonding affinity to hydrophilic SiO₂ layers.\n\n5. **Optimization of Surface Properties:**\n   - Each layer contributes to the evolution of desirable surface characteristics. For instance:\n     - Surface **hydrophilicity** increases as the SiO₂ layer becomes thicker and more uniform, exposing many hydroxyl (-OH) groups on the surface.\n     - Surface durability improves as the silica network becomes more cross-linked and compact with each heating step.\n     - Optical or mechanical properties may stabilize with the formation of a defect-free, continuous film.\n\n---\n\n### **Step 3: Potential Impact on Surface Properties**\nAfter several cycles of coating and heating, the surface properties of the polymer substrate are profoundly enhanced. Let us explore these enhancements in detail:\n\n1. **Hydrophilicity:**\n   - SiO₂ is inherently hydrophilic due to surface silanol groups (-Si-OH), which attract water molecules through hydrogen bonding.\n   - Repeated applications ensure that these groups are exposed over the entire surface, imparting strong hydrophilic properties.\n\n2. **Coating Uniformity and Smoothness:**\n   - Repetition addresses thickness variations or gaps in the initial layers, yielding a smoother, more uniform film. Surface uniformity is essential for applications such as optical coatings or wettability control.\n\n3. **Mechanical and Chemical Durability:**\n   - Multi-layer coatings are more resistant to abrasion, peeling, or chemical attack because they are thicker, more cross-linked, and better adhered to the substrate.\n   - The heating step in each cycle ensures that each new layer adds strength without compromising the integrity of the previous layers.\n\n4. **Barrier Properties:**\n   - SiO₂ is an effective barrier against oxygen, moisture, and other environmental contaminants. A thicker, denser film achieved via multiple cycles enhances these barrier properties.\n\n---\n\n### **Experimental Recommendations**\n- Based on the above explanation, I recommend the following general experimental scheme to optimize the SiO₂ application:\n  1. **Prepare a Sol-Gel Solution:** If using TEOS as the SiO₂ precursor, prepare a solution with a catalyst (e.g., acidic or basic) to initiate hydrolysis. You may also use pre-synthesized silica nanoparticles in a suitable dispersion medium.\n  2. **Spray Coating Step:** Apply a fine mist of the SiO₂ solution onto the polymer substrate, ensuring even coverage.\n  3. **Heating Step:** Heat the coated substrate to 60–120 °C (or higher, depending on the polymer’s thermal stability) to promote condensation and adhesion of SiO₂.\n  4. **Repeat Cycles:** Perform at least 3–5 cycles for complete coverage, uniformity, and durability.\n  5. **Post-Treatment:** For specific applications, you may consider curing the coating further at higher temperatures or under specific environmental conditions.\n\n---\n\nIn conclusion, repeating the spray coating and heating processes is essential for achieving uniform, thick, and durable SiO₂ layers on a polymer substrate. Each cycle improves the surface coverage, adhesion, and surface properties such as hydrophilicity, ultimately resulting in a functionalized surface suitable for a wide variety of applications.\n\n"
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diff --git a/task2/task2-qa/CN102666753B╖└╬э═┐┴╧╫щ║╧╬я.json b/task2/task2-qa/CN102666753B╖└╬э═┐┴╧╫щ║╧╬я.json
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+{
+  "design_question": "Describe the role of N-hydroxymethylacrylamide in the synthesis of hydrophilic polymers and explain how its inclusion in the polymer mixture might contribute to enhancing hydrophilicity.",
+  "design_answer": "Let us address this question systematically and in detail. \n\n---\n\n### Step 1: **Analyze the Question**\n\nThe question asks about the role of **N-hydroxymethylacrylamide (NHMA)** in the synthesis of hydrophilic polymers and how it contributes to enhancing the hydrophilicity of the resulting polymer. To answer this effectively, I will:\n1. Explain the chemical properties of NHMA relevant to hydrophilicity.\n2. Describe how NHMA behaves when included in polymer systems.\n3. Discuss its specific contribution to hydrophilicity and the broader implications for polymer design.\n\n---\n\n### Step 2: **Basic Understanding of N-hydroxymethylacrylamide**\n\n**N-hydroxymethylacrylamide (NHMA)** is a bifunctional monomer consisting of:\n1. A reactive **acrylamide group (-CH=CH-CONH2)** capable of free-radical polymerization.\n2. A **hydroxymethyl (-CH2OH) side group**, which introduces hydrophilic functionality.\n\n**Key Properties of NHMA with Relevance to Hydrophilicity:**\n- The hydroxyl (-OH) group in the molecule is highly polar, enabling hydrogen bonding with water, which enhances the hydrophilicity of the polymer.\n- NHMA can copolymerize with other monomers, introducing hydrophilic segments into otherwise hydrophobic polymers.\n- Upon polymerization, it offers a secondary potential functionalization (via the hydroxyl group), such as cross-linking or post-polymerization modification, enhancing structural properties while maintaining water affinity.\n\n---\n\n### Step 3: **Role of NHMA in Synthesis of Hydrophilic Polymers**\n\nWe now outline the role of NHMA in hydrophilic polymer systems and its experimental relevance.\n\n---\n\n#### **I. As a Monomer in Free-Radical Polymerization**\nWhen synthesizing hydrophilic polymers, NHMA serves as one of the monomeric precursors in a **free-radical polymerization reaction**. Its role can be summarized as follows:\n1. **Polymer Backbone Formation:** NHMA participates in chain propagation via its acrylamide functional group. This forms the backbone polymer, either as a homopolymer (poly-NHMA) or as part of a copolymer system.\n2. **Hydrophilic Side Chains:** The hydroxymethyl (-CH2OH) moiety provides polar groups distributed along the polymer chain, increasing its affinity for water.\n\n#### **II. Copolymerization with Hydrophobic Monomers**\nNHMA is commonly copolymerized with hydrophobic monomers (e.g., methyl methacrylate or styrene) to modify their properties for specific applications. By including NHMA, the resultant copolymer gains:\n- Improved hydrophilic properties (e.g., water-wettability, water absorption, etc.).\n- Compatibility with aqueous environments.\n\nFor instance, incorporating 10–30 mol% of NHMA into a predominantly hydrophobic polymer can dramatically increase its hydrophilicity without severely compromising its mechanical integrity.\n\n#### **III. Crosslinking and Post-Synthesis Functionalization**\nThe hydroxymethyl (-CH2OH) groups can also act as crosslinking sites:\n1. NHMA can undergo crosslinking reactions with dialdehydes, epoxides, or other crosslinkers, enhancing water retention in hydrogels or membranes.\n2. The pendant hydroxyl groups are reactive post-synthesis, enabling chemical modifications (e.g., phosphorylation or sulfation) to further enhance hydrophilicity or impart additional functionalities.\n\n---\n\n### Step 4: **Experimental Scheme for Preparing Hydrophilic Polymer Using NHMA**\n\nLet me now provide a specific experimental preparation scheme for synthesizing a hydrophilic copolymer containing NHMA.\n\n---\n\n**Objective:** To prepare a hydrophilic copolymer of N-hydroxymethylacrylamide (NHMA) and methyl methacrylate (MMA) by free-radical polymerization.\n\n#### **Materials:**\n1. **Monomers:** NHMA and MMA.\n2. **Solvent:** Ethanol-water mixture (70:30 v/v, to enhance NHMA solubility).\n3. **Initiator:** Azobisisobutyronitrile (AIBN, 1 wt% of total monomer mass).\n4. **Reaction Vessel:** Round-bottom flask with magnetic stirrer, reflux condenser, nitrogen gas, and oil bath for temperature control.\n\n#### **Procedure:**\n1. **Solution Preparation:**\n   - Dissolve the desired amount of NHMA and MMA in the ethanol-water mixture. Typically, use a 70:30 mole ratio of MMA:NHMA for moderate hydrophilicity.\n   - Stir the solution to ensure homogenization.\n\n2. **Degassing:**\n   - Purge the reaction vessel with nitrogen gas for 20 minutes to remove dissolved oxygen, which could inhibit free-radical polymerization.\n\n3. **Initiation:**\n   - Add the AIBN initiator into the reaction mixture under a nitrogen atmosphere. A typical initiator concentration is 1 wt% of the total monomer mass.\n\n4. **Polymerization:**\n   - Heat the reaction vessel to 65–75 °C in an oil bath for 4–6 hours with continuous stirring. This temperature initiates and sustains free-radical propagation.\n\n5. **Precipitation and Purification:**\n   - After polymerization, cool the reaction mixture to room temperature and precipitate the polymer in diethyl ether or acetone.\n   - Wash the precipitate multiple times to remove unreacted monomers and initiators.\n\n6. **Drying:**\n   - Dry the purified polymer under vacuum at 40 °C until a constant weight is achieved.\n\n---\n\n#### **Reaction Conditions and Ratios:**\n- **NHMA Mole Fraction:** The mole percentage of NHMA determines the hydrophilicity. Use 10–30 mol% NHMA for moderate hydrophilicity or increase to 50 mol% for highly water-absorbent materials.\n- **Initiator Concentration:** 1 wt% of monomer mass ensures efficient chain initiation.\n- **Solvent System:** Ethanol-water ensures solubility of NHMA and MMA while creating a reaction medium conducive to homogeneous polymerization.\n\n---\n\n### Step 5: **How NHMA Enhances Hydrophilicity**\nThe inclusion of NHMA in the polymer system enhances hydrophilicity due to:\n1. **Hydrogen Bonding:** The hydroxymethyl (-CH2OH) groups form hydrogen bonds with water, improving water uptake and swelling behavior.\n2. **Increased Surface Wettability:** NHMA-derived segments improve the surface properties of the polymer, allowing it to resist water repellency.\n3. **Water Retention Stability:** In hydrogels or coatings, NHMA contributes to stable water retention, vital for biomedical or environmental applications.\n\n---\n\n### Conclusion\n\nBy incorporating N-hydroxymethylacrylamide (NHMA) into a polymer, the hydrophilic character of the material is significantly enhanced. NHMA achieves this both directly—through its hydroxymethyl group—and indirectly, by enabling crosslinking or functionalization. Experimentally, polymerization using NHMA requires careful consideration of reaction conditions, solvent choice, and monomer ratios to achieve the desired hydrophilicity.\n\nBy following the experimental scheme provided above, you should be well-equipped to synthesize and study hydrophilic polymers based on NHMA. Let me know if you have further questions!"
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+  "design_question": "Describe how you would use multifactorial aziridines, such as CX-100, as crosslinking agents during the preparation of a hydrophilic polymer. What role do these crosslinking agents play in improving the hydrophilicity of the polymer material?",
+  "design_answer": "To answer your question systematically and with thorough scientific rigor, let us carefully analyze the problem and break it down into its essential aspects, followed by providing a comprehensive experimental preparation approach for using multifactorial aziridines such as CX-100 as a crosslinking agent in hydrophilic polymer synthesis.\n\n---\n\n### Analysis of Key Points in the Question:\n1. **Focus on Hydrophilic Polymer Preparation**: You are asking about how to incorporate CX-100 (a multifactorial aziridine compound) as a crosslinking agent to prepare a hydrophilic polymer.\n2. **Role of Crosslinking Agents in Hydrophilicity**:\n   - Crosslinking agents help form a stable three-dimensional network within the polymer, which can contribute to enhanced water compatibility and mechanical properties.\n   - In the case of aziridines, their reactive aziridine functional groups can react with other polar or hydrophilic groups, improving water wettability and hydrophilicity.\n\nNow, let's delve into the detailed experimental preparation scheme, ensuring clarity for laboratory practice.\n\n---\n\n### Experimental Preparation Scheme for Using CX-100 as a Crosslinking Agent:\n\n#### Materials:\n1. **CX-100 (Multifunctional Aziridine)**: A commonly used trifunctional aziridine compound with excellent reactivity.\n2. **Hydrophilic Polymer Precursor**: Examples could include poly(acrylic acid), poly(vinyl alcohol), or other systems containing carboxyl (-COOH), hydroxyl (-OH), or amine (-NH2) functional groups.\n3. **Solvent**: Deionized water or aqueous alcohol mixtures (e.g., ethanol-water) for solubilizing the polymer precursor.\n4. **Catalyst (if needed)**: Acidic or basic catalysts to facilitate ring-opening reactions of aziridine groups.\n5. **Additives (optional)**: pH buffers, stabilizers, or surfactants if required for uniform dispersion.\n\n#### Step-by-Step Procedure:\n---\n\n**Step 1: Preparation of the Hydrophilic Polymer Precursor Solution**\n- Weigh out the required amount of the hydrophilic polymer precursor (e.g., poly(acrylic acid)).\n- Dissolve the polymer in deionized water or a compatible aqueous solvent system at room temperature (~25°C) under stirring. Use a magnetic stir bar to ensure complete dissolution.\n    - For example:\n      - Use 5 wt% poly(acrylic acid) in water for optimal solubility.\n- Add pH buffers if necessary to maintain neutrality (pH 7), to avoid undesired secondary reactions during crosslinking.\n\n---\n\n**Step 2: Addition of CX-100 Crosslinker**\n- Slowly add CX-100 (trifunctional aziridine) to the polymer solution under constant stirring. \n    - **Key Stoichiometry**: Maintain a functional group molar ratio of approximately 1:1 between aziridine groups (CX-100) and reactive groups (e.g., carboxyl groups of poly(acrylic acid)).\n    - For instance:\n      - Calculate the moles of –COOH groups in the polymer precursor.\n      - Add an equimolar amount of CX-100 based on its molecular weight and assay.\n\n- Example: For a 5 wt% poly(acrylic acid) solution, using an average molecular weight of ~76 g/mol per –COOH group, add the crosslinker proportionately.\n\n---\n\n**Step 3: Initiate Crosslinking Reaction**\n- Heat the solution gently to around 40–60°C while stirring to allow the aziridine functional groups to undergo ring-opening reactions with the polymer (e.g., carboxylic acid groups form amide linkages).\n    - **Note**: Aziridine groups react in a pH range of 6–9. If the pH is too low (<5), protonation could hinder the reactivity of the aziridine groups.\n    - In the presence of amines or hydroxyl groups, aziridine groups may form secondary amines or ether linkages. Adjust reaction conditions (e.g., temperature or catalyst) to selectively promote desired linkages.\n\n- Reaction Time: Allow the reaction to proceed for 4–6 hours to ensure complete crosslinking.\n\n---\n\n**Step 4: Stabilization and Washing of the Crosslinked Hydrophilic Polymer**\n- After the reaction is complete, cool the polymer solution to room temperature and precipitate the polymer network (if needed) by adding a nonsolvent, such as ethanol.\n- Wash the crosslinked polymer thoroughly with deionized water to remove unreacted CX-100 or other byproducts.\n\n---\n\n**Step 5: Drying the Crosslinked Polymer**\n- Dry the crosslinked hydrophilic polymer under vacuum at 50–60°C until a constant weight is achieved.\n\n---\n\n#### Role of CX-100 in Enhancing Hydrophilicity:\n1. **Crosslinking Effect**: CX-100 creates covalent bonds between polymer chains, resulting in a three-dimensional network that improves water retention and stability in aqueous environments.\n2. **Maintaining Polarity**: The hydrophilic domains of the polymer (e.g., -COOH, -OH, or -NH2 groups) remain accessible, ensuring good compatibility with water.\n3. **Hydrophilization via Aziridine Groups**: The aziridine groups promote reactions that introduce polar amide or hydroxyl groups, further enhancing hydrophilicity.\n\n---\n\n### Key Notes and Precautions for Success:\n1. **Reactivity Control**: The aziridine ring-opening mechanism is highly reactive. Control the pH and temperature to avoid premature side reactions.\n2. **Environmental Considerations**: Aziridines can sometimes exhibit toxicity. Work in a fume hood and use appropriate personal protective equipment (PPE).\n3. **Optimization**: The functional group molar ratio (e.g., aziridine to –COOH groups) and reaction conditions should be fine-tuned based on the specific polymer system used.\n\n---\n\nBy systematically following this approach, you will achieve a hydrophilic polymer network with enhanced water affinity. Let me know if you need additional guidance during your experimental practice."
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+  "design_question": "In an experiment aimed at enhancing polymer hydrophilicity, how would you utilize methylacryloyloxyethyl-N,N-dimethylpropanesulfonate (DMAPS) as a monomer during the synthesis process? Please outline the preparation steps and reaction conditions.",
+  "design_answer": "Certainly! Let's analyze your question and systematically outline a detailed experimental synthesis process using methylacryloyloxyethyl-N,N-dimethylpropanesulfonate (DMAPS) as a monomer to enhance polymer hydrophilicity.\n\n---\n\n### 1. **Key Points in the Question**\n- **Objective**: To use DMAPS as a functional hydrophilic monomer in the experimental synthesis of a polymer with enhanced hydrophilicity. This will leverage the zwitterionic nature of DMAPS, which has sulfonate (-SO₃⁻) and quaternary ammonium groups (-N⁺(CH₃)₂).\n- **Approach**: Incorporate DMAPS into a polymer backbone via free-radical polymerization to ensure its hydrophilic moieties are part of the resulting polymer chain.\n- **Deliverables**: The preparation steps, detailed reaction conditions, and reagent requirements.\n\nBased on this information, the target synthesis likely involves copolymerization or homopolymerization of DMAPS to prepare a water-soluble or hydrophilic polymer. Let me now outline the necessary steps.\n\n---\n\n### 2. **Experimental Preparation Scheme for Hydrophilic Polymer Using DMAPS**\n\n#### (A) **Materials and Reagents**\n1. **Monomer**: Methylacryloyloxyethyl-N,N-dimethylpropanesulfonate (DMAPS).\n2. **Co-monomers** (optional): Depending on the desired polymer composition, hydrophobic monomers such as methyl methacrylate (MMA) or hydrophilic co-monomers like acrylic acid (AA) or acrylamide (AM) can be used.\n3. **Solvent**: Deionized water (for aqueous polymerization) or a mixture of water and ethanol.\n4. **Initiator**: A water-soluble free-radical initiator (e.g., ammonium persulfate (APS), or potassium persulfate (KPS)).\n5. **Cross-linker** (optional): For gel formation, cross-linkers like N,N'-methylenebisacrylamide (MBAA) can be used.\n6. **pH Adjusting Agents**: Sodium hydroxide (NaOH) or hydrochloric acid (HCl), if needed.\n\n---\n\n#### (B) **Experimental Steps**\n\n**Step 1: Reaction Setup**\n- Use a clean, dry round-bottom flask or a reaction vessel equipped with a magnetic stirrer and nitrogen purging system.\n- Add the required amount of DMAPS and other desired monomers (if performing copolymerization) to the reaction flask.\n- Depending on the solubility of DMAPS and co-monomers, dissolve them in deionized water or a water-ethanol solvent mixture. The concentration of the monomers should usually be around **10–20% (w/v)**.\n\n**Step 2: Degassing**\n- **Why?** Oxygen inhibits free radical polymerization, so purging the reaction mixture with nitrogen (or argon) is essential.\n- Bubble nitrogen through the reaction solution for **15–30 minutes** while stirring.\n\n**Step 3: Initiator Preparation**\n- Prepare a fresh solution of the free-radical initiator, such as **ammonium persulfate (APS)** or **potassium persulfate (KPS)**, in a small amount of deionized water.\n- The typical initiator-to-monomer molar ratio is **1:100 to 1:200**, depending on the desired polymer molecular weight. For example:\n  - If using 1 g of DMAPS (MW = 295.34 g/mol), this is approximately **3.38 mmol**. The initiator amount would be **0.0169–0.0338 mmol** (e.g., 4–8 mg of APS or KPS).\n\n**Step 4: Polymerization Reaction**\n- Heat the reaction mixture to **60–70°C** while maintaining stirring and continuous nitrogen flow.\n- Slowly add the initiator solution dropwise to the reaction mixture to initiate polymerization.\n- Allow the polymerization to proceed for **4–6 hours** under constant temperature and stirring. Over time, the mixture will become more viscous, indicating polymer formation.\n\n**Step 5: Termination**\n- After completing the polymerization, cool the reaction mixture to room temperature and expose it to air to terminate the reaction. Antioxidants (e.g., hydroquinone) can also be added to quench free radicals if necessary.\n\n**Step 6: Purification**\n- Precipitate the polymer by adding the reaction mixture into a non-solvent like acetone or ethanol for hydrophilic polymers.\n- Collect the precipitated polymer via filtration or centrifugation, and wash it several times with the non-solvent to remove unreacted monomers and by-products.\n- Dry the purified polymer under vacuum at **40–50°C** until constant weight is achieved.\n\n---\n\n#### (C) **Optimization Tips**\n1. **Solvent Selection**: DMAPS is hydrophilic, so aqueous systems are generally preferred. However, for copolymerization with hydrophobic monomers, incorporate a water-miscible organic solvent like ethanol.\n2. **Cross-Linking (Optional)**: If you want a hydrogel, add a small amount (<1 mol%) of MBAA as the cross-linker.\n3. **Polymer Composition**: Vary the ratio of DMAPS to co-monomers to tune the hydrophilicity of the final polymer.\n4. **Reaction pH**: Keep the pH neutral (around 6–7) to prevent premature decomposition of the persulfate initiator or hydrolysis of the sulfonate groups.\n\n---\n\n#### (D) **Characterization**\nAfter synthesis, you must confirm the successful incorporation of DMAPS and verify the polymer's hydrophilicity. Suggested methods:\n1. **FTIR Spectroscopy**: Confirm functional groups, especially sulfonate (-SO₃⁻) at ~1040–1080 cm⁻¹.\n2. **NMR Spectroscopy**: Identify the chemical structure and verify the presence of DMAPS' zwitterionic moieties.\n3. **Water Contact Angle Measurements**: Evaluate surface hydrophilicity.\n4. **Swelling Tests** (for hydrogels): Quantify water absorption to assess hydrophilic performance.\n\n---\n\n### 3. **Summary**\nBy effectively utilizing DMAPS as a monomer in polymerization, we introduce zwitterionic moieties that significantly enhance the hydrophilicity of the resulting polymer. The outlined procedure includes crucial steps, reaction conditions, and optimization tips to ensure reproducibility and success in the lab. This synthesis can be easily tailored for homopolymerization or copolymerization, depending on the specific application.\n\nFeel free to discuss any step in further detail if you have questions!"
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+  "design_question": "Describe how you would use a multi-functional isocyanate compound such as hexamethylene diisocyanate to crosslink the polymer and explain its significance in achieving the desired hydrophilic properties.",
+  "design_answer": "Certainly, let's break down your inquiry regarding using hexamethylene diisocyanate (HDI), a multifunctional isocyanate, to crosslink polymers for improving hydrophilic properties. I will analyze your question first, summarize the key points, and provide a systematic and detailed experimental preparation scheme.\n\n---\n\n### **1. Analysis of the Question and Key Points**\nTo approach your question logically:\n- You inquire about crosslinking polymers using HDI and the significance of its role in achieving hydrophilic properties.\n- The primary focus is on utilizing HDI, an aliphatic diisocyanate compound, as a crosslinking agent.\n- HDI must react with functional groups in the polymer to form crosslinks that enhance hydrophilicity.\n\nKey considerations:\n1. HDI's bifunctionality allows it to react with nucleophilic functional groups (e.g., hydroxyl, amine) on the polymer backbone or side chains.\n2. Crosslinking needs to be controlled to minimize insolubility or brittleness while promoting hydrophilic features.\n3. Hydrophilic properties can be engineered with suitable functional additives and modification during the polymer crosslinking process.\n\n---\n\n### **2. Systematic Preparation Scheme for Crosslinking Using HDI**\n\nHere is the detailed step-by-step synthesis protocol to crosslink polymers with HDI. I will include reaction conditions, reagent quantities, and how they contribute to hydrophilicity.\n\n#### **Step 1: Preparation of Polymer Base**\nThe starting polymer should contain reactive functional groups capable of engaging in a reaction with the isocyanate groups (-NCO) of HDI. Common functional groups include:\n- Hydroxyl groups (-OH) in poly(vinyl alcohol) or polyethylene glycol (PEG).\n- Amine groups (-NH2) in poly(amidoamine) or other polymers with primary/secondary amines.\n\nIn this example, we will assume the base polymer is polyethylene glycol (PEG), chosen for its inherent hydrophilicity due to the ether (-O-) linkages along its backbone.\n\n1. **Materials Needed**:\n   - Polyethylene glycol (PEG, molecular weight ~2000 g/mol).\n   - Hexamethylene diisocyanate (HDI).\n   - Catalyst: Stannous octoate or dibutyltin dilaurate (to accelerate urethane bond formation).\n\n2. **Reagent Ratios**:\n   - Mole ratio of HDI to functional groups in the polymer: Adjust to maintain slight molar excess of HDI (1.1:1).\n   - For 10 g of PEG (approx. 5 mmol hydroxyl groups): Use **5.5 mmol of HDI**.\n\n3. **Significance of Polymer Choice**:\n   PEG itself is hydrophilic due to its ether functionalities, but crosslinking will stabilize this structure and reduce solubility without compromising hydrophilic behavior. This ensures water compatibility and an extended hydrophilic network.\n\n---\n\n#### **Step 2: Dissolution and Mixing**\n1. **Procedure**:\n   - Dissolve PEG in anhydrous toluene or dimethylformamide (DMF). Use solvent volume sufficient for complete homogeneity (e.g., 50 mL for 10 g PEG).\n   - Add HDI into the solution dropwise to prevent localized excess, which could lead to uneven crosslinking.\n   - Stir the solution at room temperature (or slightly elevated to ~40 °C) under nitrogen gas to prevent moisture interference with the isocyanate groups (moisture may lead to urea formation).\n\n2. **Reaction Conditions**:\n   - Maintain stirring for 1-2 hours.\n   - Introduce a catalyst such as stannous octoate (~0.1% w/v relative to polymer) after initial mixing to accelerate crosslinking.\n\n---\n\n#### **Step 3: Crosslinking Reaction**\n1. **Mechanism**:\n   - The HDI molecule reacts via its isocyanate (-NCO) groups with hydroxyl (-OH) groups from PEG to form urethane linkages (-NH-CO-O-).\n   - HDI's bifunctionality allows it to form a stable network of crosslinks between multiple polymer chains.\n\n2. **Control Parameters**:\n   - Temperature: Ideally 40–60 °C. Excess heat must be avoided to prevent polymer degradation or rapid gelation.\n   - Reaction time: 6–12 hours, depending on the concentration of reagents and desired degree of crosslinking.\n\n---\n\n#### **Step 4: Post-Reaction Processing**\n1. **Purification**:\n   - The resulting crosslinked polymer will be insoluble in the reaction solvent but may swell in water or other polar solvents.\n   - Wash the product with anhydrous acetone or ethanol to remove unreacted HDI and residual catalyst.\n   - Dry under vacuum at 40 °C for 24 hours.\n\n2. **Characterization**:\n   - Verify successful crosslinking and hydrophilic enhancement using:\n     - FTIR spectroscopy: Check for urethane peaks (characteristic C=O stretch at ~1690 cm⁻¹ and N-H stretch at ~3300 cm⁻¹).\n     - Swelling tests in water: Assess hydrophilic behavior by measuring water uptake or swelling percentage.\n     - Contact angle measurements: Demonstrate reduced hydrophobicity of the crosslinked polymer.\n\n---\n\n### **3. The Significance of HDI Crosslinking in Enhancing Hydrophilicity**\n1. **Formation of Crosslinked Networks**:\n   - HDI forms stable urethane bonds, creating a robust three-dimensional network. This structure improves the polymer's mechanical strength without compromising its ability to interact with water through hydrogen bonding.\n\n2. **Hydrophilic Nature**:\n   - Hydrophilic polymers like PEG retain their ability to swell or absorb water, thanks to the polar nature of urethane linkages and PEG's ether-based structure.\n\n3. **Applications**:\n   - Used in hydrogel formation, coatings, or biomedical devices requiring water compatibility.\n   - Crosslinking limits polymer dissolution in water while maximizing hydrophilic interaction, making it suitable for moist environments.\n\n---\n\n### **Conclusion**\nBy using HDI to crosslink a polymer such as PEG, you can create a hydrophilic network that balances structural stability with water compatibility. The detailed preparation protocol provided should guide you through the synthesis process systematically, enabling successful implementation in the laboratory."
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+  "design_question": "Describe how the molecule '3-methacryloxypropyltrimethoxysilane (MAPTMS)' can be utilized in a sol-gel process to modify a polymer for enhanced hydrophilicity. Specifically, outline the steps needed to hydrolyze and condense this molecule to create a suitable intermediate for further polymerization.",
+  "design_answer": "Certainly, let us thoughtfully analyze and systematically address your question regarding the use of 3-methacryloxypropyltrimethoxysilane (MAPTMS) in a sol-gel process to modify a polymer for enhanced hydrophilicity. Following this, I will provide a detailed, step-by-step experimental scheme to accomplish this synthetic goal in the laboratory.\n\n---\n\n### **Step 1: Key Points of the Question**\nTo accurately address your question:\n1. **Objective:** Enhance the hydrophilicity of a polymer by modifying it with MAPTMS through a sol-gel process.\n2. **Main Reactant:** MAPTMS, which is an organosilane compound featuring both methacryloyl functionality (for later polymerization) and silane groups (for hydrolysis and condensation).\n3. **Preparation Strategy:** Use the sol-gel process to hydrolyze and condense MAPTMS into a suitable intermediate (organosilica network or oligomers) that can subsequently graft to or be incorporated into the target polymer.\n4. **Experimental Details:** Design a systematic approach that considers the precise reaction conditions (e.g., catalyst, pH, solvent, temperature, reagent ratios) for controlling hydrolysis and condensation.\n\n---\n\n### **Step 2: Detailed Experimental Procedure**\n\nHere is a systematic experimental preparation scheme for the hydrolysis and condensation of MAPTMS in the sol-gel process:\n\n#### **2.1 Materials Required**\n- **Reagent:** 3-methacryloxypropyltrimethoxysilane (MAPTMS, ≥98% purity).\n- **Hydrolysis Catalyst:** Acidic catalyst (e.g., hydrochloric acid, acetic acid) at a dilute concentration (typically pH ~3-5).\n- **Solvent:** Aqueous-alcohol mixture (e.g., ethanol/water system).\n- **Deionized Water:** For facilitating hydrolysis.\n- **Optional Additives:** Small amounts of surfactants or stabilizers (e.g., Triton X-100) to enhance dispersion, if required.\n\n#### **2.2 Outline of the Reaction Steps**\n\n1. **Preparation of Reaction Mixture:**\n   - **Volume Ratios:** Prepare an ethanol-water solution with an **ethanol:water molar ratio of 4:1**. Write down the desired volume based on your required scale. Ethanol acts as a co-solvent to dissolve hydrophobic MAPTMS, while water provides the source for hydrolysis.\n   - **pH Adjustment:** Use dilute HCl solution to adjust the pH of the ethanol-water mixture to approximately 3-4. This mildly acidic pH is optimal for silane hydrolysis without promoting excessive condensation at this stage.\n\n2. **Hydrolysis of MAPTMS:**\n   - Dissolve MAPTMS into the acidic ethanol-water solution with stirring at room temperature (~25°C).\n   - Recommended **MAPTMS:water molar ratio:** 1:3. This ensures each methoxy group (-OCH3) on the silane is sufficiently hydrolyzed into a silanol (-Si-OH). For instance, if you use 10 mmol MAPTMS, you should add 30 mmol water.\n   - **Stirring and Time:** Stir the reaction mixture continuously for **1-2 hours** to allow hydrolysis to proceed. During this time, you may observe the formation of a clearer solution, indicating the conversion of MAPTMS to silanol groups.\n\n3. **Condensation of Silanols:**\n   - Adjust the hydrolysis step to transition to silanol condensation by slightly raising the temperature to ~50°C under **gentle stirring**. This promotes the formation of Si-O-Si bonds between hydrolyzed silanol groups, leading to the formation of a partially condensed organosilica network (oligomeric siloxane intermediates).\n   - Monitor viscosity changes in the reaction mixture, which indicate that partial condensation is occurring. Do not allow full gelation, as the product should remain in a soluble or colloidal state.\n\n4. **Optional Stabilization/Homogenization:**\n   - If your intermediate forms aggregates or larger particles during condensation, use a sonicator or mild surfactant to redisperse and stabilize the solution.\n\n5. **Storage:** Store the condensed MAPTMS intermediate at low temperature (~4°C) if it is not used immediately, as further crosslinking may proceed over time.\n\n#### **2.3 Key Observations:**\n- During hydrolysis, methanol (by-product) can be detected as the methoxy (-OCH3) groups are replaced with hydroxyl (-OH).\n- During condensation, the formation of Si-O-Si linkages can be confirmed using FTIR spectroscopy by observing characteristic peaks at ~1000 cm⁻¹ (Si-O-Si stretching).\n\n---\n\n### **Step 3: Subsequent Polymerization Step**\nAfter preparing the MAPTMS-derived organosilica network:\n1. It can be incorporated into or grafted onto your target polymer matrix through the methacryloyl (-C=C-) functionality on MAPTMS, which enables polymerization with other vinyl monomers.\n2. Use free radical polymerization (e.g., with an initiator like AIBN or potassium persulfate) to covalently anchor MAPTMS-derived hydrophilic moieties into the polymer.\n\n---\n\n### **Step 4: Consideration for Enhancing Hydrophilicity**\nThe resulting polymer will be made hydrophilic due to the following:\n1. **Si-OH Surface Groups:** The hydrolysis and partial condensation of MAPTMS leave residual silanol (-Si-OH) groups, which enhance hydrophilicity via hydrogen bonding with water.\n2. **Post-Polymerization Functionalization:** If desired, additional functional hydrophilic groups (e.g., by reacting amino or carboxylic acids) can be introduced through post-grafting techniques to further increase water affinity.\n\n---\n\n### **Step 5: Notes on Laboratory Practice**\n- Perform the sol-gel process in a moisture-controlled environment to avoid uncontrolled gelation or crosslinking.\n- Always ensure the stoichiometry of MAPTMS, water, and catalysts is properly calculated to guide the progression of hydrolysis and condensation.\n\n---\n\nThis step-by-step protocol should now enable you to successfully use MAPTMS in a sol-gel process to create intermediates suitable for modifying polymers with enhanced hydrophilicity."
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+  "design_question": "Explain the mechanism by which NaBH4 (sodium borohydride) interacts with HAuCl4 during the preparation process. How does this reaction contribute to the hydrophilicity of the final polymer?",
+  "design_answer": "Excellent question! Let's carefully analyze the problem and systematically unpack every detail to ensure clarity and comprehensiveness.\n\n---\n\n### **Key Question Analysis:**\n1. **Reagents Involved:**\n   - **NaBH₄ (Sodium Borohydride):** A powerful reducing agent commonly used in both organic and inorganic synthesis.\n   - **HAuCl₄ (Gold Chloride or Chloroauric Acid):** A gold-containing precursor that can reduce into nanoparticles or different gold states depending on the reducing agent and reaction conditions.\n\n2. **Synthesis Context:**\n   - The interaction between NaBH₄ and HAuCl₄ likely pertains to some reduction mechanism where NaBH₄ reduces HAuCl₄ to metallic gold nanoparticles (AuNPs) or other metallic gold forms.\n   - The gold nanoparticles or species formed may play a role in modifying the hydrophilicity of the final polymer.\n\n3. **Hydrophilicity Enhancement:**\n   - The formation of AuNPs or some intermediates could contribute to improving the hydrophilicity of the polymer when surface-functionalized with hydrophilic moieties.\n   - Understanding the mechanism will reveal how this reaction fits into the broader context of hydrophilic polymer synthesis.\n\n---\n\n### **Step-by-Step Answer:**\n\n#### **Step 1: The Mechanism of NaBH₄ and HAuCl₄ Interaction**\nWhen NaBH₄ interacts with HAuCl₄, it reduces the Au³⁺ ions (from the HAuCl₄) to metallic gold (Au⁰), typically producing gold nanoparticles (AuNPs) in the process. Let us break this mechanism down:\n\n- **Reduction Reaction:**\n  - HAuCl₄ in water dissociates into Au³⁺ ions and Cl⁻ ions:\n    \\[\n    HAuCl_4 \\longrightarrow Au^{3+} + 4Cl^{-} + H^{+}.\n    \\]\n\n  - Sodium borohydride (NaBH₄) donates electrons to the gold cation (Au³⁺), reducing it to metallic gold (Au⁰), which often nucleates to form nanoparticles. The reaction follows:\n    \\[\n    NaBH_4 + 3H_2O + 4Au^{3+} \\longrightarrow 4Au^{0} + NaB(OH)_4 + 3H^{+}.\n    \\]\n\n- **Formation of Nanoparticles:**\n  - Au⁰ atoms aggregate to form colloidal gold nanoparticles (AuNPs) in the aqueous solution. The size and distribution of these nanoparticles depend on factors such as the NaBH₄ concentration, temperature, reaction time, and stabilizers (if present).\n\n- **Reaction Conditions:**\n  - The reduction is fast and occurs at ambient temperature. Stirring is usually required to ensure uniform mixing of the reducing agent and the gold precursor.\n  - A freshly prepared sodium borohydride solution is typically used since it decomposes rapidly in water, releasing hydrogen gas.\n\n#### **Step 2: Linking This to the Hydrophilicity of the Final Polymer**\nHow exactly does this reaction contribute to the hydrophilicity of the polymer? The answer lies in the **role of the gold nanoparticles and subsequent surface functionalization**.\n\n1. **Surface Interaction with the Polymer:**\n   - Gold nanoparticles have a high surface energy, which allows them to interact with various functional groups on the polymer. This creates an **attachment point for hydrophilic groups**.\n\n2. **Surface Functionalization:**\n   - Often, AuNPs are surface-functionalized with hydrophilic ligands or molecules, such as thiols, carboxylic acids, or polyethylene glycols (PEG). These hydrophilic moieties, once integrated with the polymer, dramatically enhance the hydrophilicity of the overall material.\n\n3. **Uniform Dispersion & Compatibility:**\n   - Due to their colloidal nature, AuNPs can uniformly disperse throughout the polymer matrix. This ensures an even distribution of hydrophilic groups, leading to a highly hydrophilic material.\n\n4. **Crosslinking or Anchoring with the Polymer:**\n   - If the polymer is designed with reactive sites (e.g., amine, thiol, hydroxyl, or carboxylic groups), gold nanoparticles can act as a cross-linker or anchor by forming stable chemical interactions (e.g., Au-S bonds, Au-NR₂ complexes). These cross-linked or anchored regions may also expose hydrophilic functional groups, further improving the material's water affinity.\n\n#### **Step 3: Overall Role in Polymer Hydrophilicity**\nThe reduction of HAuCl₄ by NaBH₄ to form AuNPs plays a critical role in the hydrophilicity of the polymer for the following reasons:\n- AuNPs provide a high-surface-area platform for the attachment of hydrophilic functional groups.\n- Surface-functionalized AuNPs can be embedded within the polymer matrix, ensuring that hydrophilic regions are uniformly present throughout the material.\n- If the polymer structure itself incorporates hydrophilic groups, the presence of AuNPs can enhance the exposure and accessibility of these groups, thereby increasing overall hydrophilicity.\n\n---\n\n### **Comprehensive Summary:**\nIn summary:\n1. NaBH₄ reduces HAuCl₄ to form metallic gold nanoparticles (AuNPs) via a redox reaction. During this process, Au³⁺ ions from HAuCl₄ are reduced to Au⁰, with NaBH₄ being oxidized.\n2. AuNPs can then act as scaffolding or anchoring sites for hydrophilic functional groups, either through direct functionalization of the nanoparticle surface or by interacting with the polymer matrix.\n3. The incorporation of hydrophilic AuNPs into the polymer enhances its hydrophilicity by providing water-attracting moieties and creating a more hydrophilic polymer structure.\n\nThis reaction demonstrates the versatility of AuNPs in improving material properties via strategic chemical modifications. Be sure to maintain precise control over reaction parameters—such as reagent concentrations and mixing conditions—to achieve highly uniform and functional nanoparticles for the targeted hydrophilic polymer synthesis."
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+{
+  "design_question": "Design a step-by-step experimental scheme for synthesizing a hydrophilic polymer by reacting isophorone diisocyanate (IPDI) with appropriate reagents. Specify reaction conditions, solvents, and the role of IPDI in enhancing hydrophilicity.",
+  "design_answer": "### Question Analysis and Key Points\n\nThe objective is to design an experimental scheme for synthesizing a hydrophilic polymer using **isophorone diisocyanate (IPDI)**. The core challenges here include:\n1. Understanding the chemistry of IPDI, a commonly used diisocyanate with two reactive isocyanate (-NCO) groups that can form urethane or urea linkages.\n2. Selecting appropriate reagents that can react with IPDI to yield a hydrophilic polymer. Typically, incorporation of hydrophilic functionality (e.g., polyethers, amines, or hydroxyl-containing groups) is required to enhance water affinity.\n3. Providing systematic experimental details, including reaction conditions, solvent choices, molar ratios, and any catalysts if needed, for each step of the proposed synthesis.\n\nNow, let’s proceed step-by-step to design a detailed experimental preparation scheme.\n\n---\n\n### Step-by-Step Experimental Scheme for Synthesizing a Hydrophilic Polymer Using IPDI\n\n#### Step 1: Selection of Reagents and Reaction Strategy\nTo enhance hydrophilicity, we aim to introduce hydrophilic functional groups into the polymer backbone. For this, we will:\n1. **Use a diol or polyether polyol** with hydrophilic characteristics, such as **polyethylene glycol (PEG)**, which has ether linkages (-CH2-CH2-O-) that significantly improve water compatibility.\n2. Optionally, introduce ionic or zwitterionic groups that further enhance water solubility. For example, adding a tertiary amine group (later quaternized) or carboxylic acid can be effective.\n\nIPDI will act as the key diisocyanate component to react with these reagents, forming urethane linkages that hold the polymer structure together. Its unique asymmetric structure provides an additional advantage in controlling the polymer’s physical properties.\n\n---\n\n#### Step 2: Reaction 1 – Preparation of Prepolymer\nWe will synthesize a prepolymer by reacting IPDI with polyethylene glycol (PEG).\n\n**Materials:**\n- Isophorone diisocyanate (IPDI)\n- Polyethylene glycol (PEG, molecular weight 400–1000, depending on desired polymer properties)\n- Organic solvent: **anhydrous dimethylformamide (DMF)** or **toluene**\n- Catalyst: Dibutyltin dilaurate (DBTDL)\n\n**Procedure:**\n1. Dry all glassware and reagents (anhydrous conditions are critical to avoid unwanted water reactions with isocyanate groups).\n2. Dissolve a calculated amount of PEG in 50 mL of anhydrous DMF or toluene. The PEG should be used in slight stoichiometric excess relative to one isocyanate group of IPDI. For example, for 1 mole of IPDI, use ~1.05 moles of PEG.\n3. Add a catalytic amount of DBTDL (e.g., 0.05–0.1 wt% of the reaction mixture) to accelerate the reaction.\n4. Add IPDI slowly to the PEG solution under a nitrogen blanket with continuous stirring to ensure proper mixing. The reaction temperature should be maintained at 50–60°C for 3–4 hours (optimize this based on monitoring).\n5. Monitor the reaction progress by tracking the disappearance of the NCO stretch (~2275 cm⁻¹) in FTIR spectroscopy.\n\n**Outcome:** A urethane-linked prepolymer with terminal isocyanate groups (-NCO) is formed.\n\n---\n\n#### Step 3: Reaction 2 – End-Capping with a Hydrophilic Chain Extender\nTo further enhance hydrophilicity, react the prepolymer’s terminal -NCO groups with a **hydrophilic chain extender**, such as a diol containing ionic or polar groups. \n\n**Materials:**\n- Chain extender: Amino alcohol like **2-aminoethanol** or a diol like **dimethylolpropionic acid (DMPA)**\n- Organic solvent: Water-miscible solvents like acetone\n- Neutralizing agent (if DMPA is used): **Triethylamine (TEA)** or NaOH\n\n**Procedure:**\n1. Dissolve the prepolymer obtained from Step 2 in a suitable solvent like acetone, ensuring complete solubility.\n2. Dissolve the chain extender (e.g., 0.9–1.0 moles of DMPA or amino alcohol per mole of IPDI used in Step 1) separately in a small volume of solvent.\n   - If DMPA is used: Neutralize DMPA with TEA to form a carboxylate salt, which enhances solubility in the reaction medium.\n3. Add the chain extender solution dropwise into the prepolymer solution under nitrogen at room temperature. Allow the reaction to proceed for 4–6 hours, monitoring the -NCO stretch in FTIR.\n4. Terminate the reaction when no free -NCO groups are observed in FTIR.\n\n**Outcome:** The final product is a hydrophilic polymer containing urethane linkages and polar/ionic side groups from the chain extender.\n\n---\n\n#### Step 4: Purification and Characterization\n1. **Purification:**\n   - Precipitate the polymer into a non-solvent like hexane (if acetone is used as the reaction medium) to remove impurities.\n   - Alternatively, dialyze the polymer solution (if water-soluble) against distilled water to eliminate unreacted species.\n2. **Characterization:**\n   - Use **FTIR spectroscopy** to confirm the absence of -NCO groups and the presence of urethane (-NH-CO-) linkages.\n   - Determine the molecular weight using **GPC (gel permeation chromatography)**.\n   - Check hydrophilicity and water interaction using contact angle measurements or solubility tests.\n\n---\n\n#### Reaction Conditions Summary\n| Step               | Reagents/Materials                              | Solvent   | Catalyst | Temperature | Time    |\n|--------------------|------------------------------------------------|-----------|----------|-------------|---------|\n| Prepolymerization  | IPDI + PEG (1:1.05 mol)                        | DMF/Toluene | DBTDL    | 50–60°C     | 3–4 hrs |\n| Chain Extension    | Prepolymer + DMPA/2-Aminoethanol               | Acetone   | None     | RT          | 4–6 hrs |\n\n---\n\n### Role of IPDI in Enhancing Hydrophilicity\nAlthough IPDI itself is hydrophobic, its role is pivotal in this synthesis:\n1. It provides the reactive isocyanate groups needed to form urethane linkages with hydrophilic reagents.\n2. Its bulky, asymmetric structure contributes to the polymer’s solubility and physical flexibility, improving hydrophilic group accessibility.\n\n---\n\nBy following these steps, a hydrophilic polymer with urethane linkages and excellent water compatibility can be successfully synthesized. Let me know if you need help tailoring this approach further for specific experimental requirements!"
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+{
+  "design_question": "Design a procedure for incorporating GMA into a polymer matrix to form a hydrophilic coating. Specify the steps required, including any necessary pre-treatment, reaction parameters, and curing conditions.",
+  "design_answer": "Certainly! Incorporating glycidyl methacrylate (GMA) into a polymer matrix to form a hydrophilic coating is a common strategy to enhance the polymer's hydrophilicity due to GMA’s reactive epoxy group and methacrylate functionality. Let us proceed step by step while analyzing your question and systematically addressing all details.\n\n---\n\n### Step 1: **Analyze the Key Points**\n1. **Objective**: To modify a polymer matrix with GMA to create a hydrophilic coating.\n2. **Significance of GMA**: \n   - It serves as the key building block, offering:\n     - A methacrylate group for polymerization.\n     - An epoxy group for subsequent hydrophilic functionalization.\n3. **Requirements**:\n   - Pre-treatment of the polymer matrix to enable functionalization.\n   - Incorporation of GMA into the polymer structure.\n   - Curing and further reaction of the epoxy groups to introduce hydrophilic functionalities.\n\n---\n\n### Step 2: **Experimental Scheme**\nHere is the detailed procedure for incorporating GMA into a polymer matrix and forming a hydrophilic coating.\n\n---\n\n#### **A. Pre-treatment of the Polymer Matrix**\nBefore functionalizing any polymer surface with GMA, ensure that the surface is ready for effective adhesion and reaction.\n\n1. **Surface Cleaning**:\n   - Clean the polymer surface (if solid or film-based) to remove dirt, grease, or any contaminants.\n   - Use solvents such as ethanol or isopropyl alcohol (IPA) for thorough cleaning.\n   - Dry the surface using nitrogen gas or in a vacuum oven at 40–50°C to remove residual moisture.\n   \n2. **Surface Activation (if needed)**:\n   - If the polymer matrix is inert or hydrophobic, activate the surface to introduce functional groups (e.g., hydroxyl or carboxyl groups) for better reactivity:\n     - **Plasma Treatment**: Expose the polymer to oxygen plasma at low pressure (~0.3–0.8 Torr) for 1–3 minutes.\n     - **Chemical Etching**: Treat with a solution like chromic acid or potassium permanganate (5–10% w/v) for 10–30 minutes, followed by thorough rinsing and drying.\n\n---\n\n#### **B. Incorporation of GMA**\nThe incorporation of GMA into the polymer matrix can be achieved using free-radical polymerization or grafting techniques.\n\n1. **Preparation of the Reaction Mixture**:\n   - Dissolve **GMA** in a suitable solvent (e.g., acetone, ethanol) to ensure compatibility with the polymer matrix.\n   - Add a free-radical initiator such as **benzoyl peroxide (BPO)** or **azobisisobutyronitrile (AIBN)** at 1–2% molar equivalent of the GMA monomer. This will initiate polymer grafting.\n   - Optionally, include a co-monomer (e.g., acrylic acid or methacrylic acid at a 50:50 molar ratio with GMA) to introduce additional hydrophilic groups.\n\n   Example ratio of reagents:\n   - GMA: 0.2–0.5 M final concentration in solvent.\n   - Initiator (AIBN): 0.005 M (ensure 1–2% of GMA molar equivalent).\n   - Co-monomer (if used): Same molar concentration as GMA.\n\n2. **Polymer Grafting**:\n   - Immerse the polymer matrix (or substrate) into the reaction mixture.\n   - Degas the reaction system by purging with nitrogen or argon for 15–20 minutes to eliminate oxygen (oxygen can inhibit free-radical polymerization).\n   - Heat the reaction system to 50–70°C for 2–4 hours with constant stirring.\n\n3. **Post-reaction Washing**:\n   - After the reaction, rinse the modified polymer thoroughly with ethanol or acetone to remove any unreacted GMA or by-products.\n   - Dry the polymer matrix under a mild vacuum at ~50°C.\n\n---\n\n#### **C. Curing and Introduction of Hydrophilic Groups**\nThe next step is to utilize the epoxy groups of GMA for hydrophilization.\n\n1. **Epoxy Ring-Opening Reaction**:\n   - React the epoxy groups of GMA with a hydrophilic reagent, such as amines (e.g., ethanolamine, diethanolamine) or acids (e.g., citric acid).\n   - Prepare an aqueous or alcohol-based solution (10–20% w/v) of the hydrophilic reagent.\n   - Immerse the GMA-modified polymer surface in the solution and adjust pH to 7–9 (for amines) or mildly acidic (pH 5–6, for acids).\n   - Heat the system to ~40°C and allow the reaction to proceed for 1–2 hours, depending on the reagent used.\n\n2. **Curing**:\n   - After the reaction, rinse the polymer matrix with deionized water to remove unreacted reagents.\n   - Cure the polymer at 50–70°C for 1–2 hours to stabilize the hydrophilic layer.\n\n---\n\n### Step 3: **Reaction Conditions and Parameters Summary**\nHere is a concise summary for the parameter setup:\n\n1. **GMA Incorporation**:\n   - Initiation: Free-radical polymerization using AIBN or BPO.\n   - Solvent: Acetone or ethanol.\n   - Temperature: 50–70°C.\n   - Time: 2–4 hours.\n   - Molar Ratio: 2–5% initiator to GMA.\n\n2. **Epoxy Ring-Opening**:\n   - Reagent: Ethanolamine (or similar).\n   - pH: Basic (7–9) for amines; slightly acidic for acids.\n   - Time: 1–2 hours.\n   - Temperature: 40°C.\n   \n3. **Curing**:\n   - Time: 1–2 hours.\n   - Temperature: 50–70°C.\n\n---\n\n### Step 4: Additional Considerations\n- **Characterization**:\n  - Confirm hydrophilicity using contact angle measurements (smaller angles indicate higher hydrophilicity).\n  - Analyze the chemical structure using techniques like Fourier-transform infrared spectroscopy (FTIR) to verify the incorporation of GMA and subsequent modifications.\n- **Safety**:\n  - Work in a well-ventilated fume hood when handling volatile solvents like acetone or ethanol.\n  - Use gloves, safety goggles, and other appropriate protective equipment.\n\n---\n\nBy following the outlined procedure, you should be able to successfully incorporate GMA into the polymer matrix and create a hydrophilic coating. Let me know if additional clarifications or adjustments are needed!"
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+{
+  "design_question": "Describe how you would use polyethylene glycol monomethyl ether (PEGME600) in a preparation scheme to modify a polymer to enhance its hydrophilicity. Specify the key reaction steps and conditions.",
+  "design_answer": "Certainly! To systematically describe how polyethylene glycol monomethyl ether (PEGME600) can be used to modify a polymer and enhance its hydrophilicity, let us proceed step-by-step:\n\n---\n\n### **Step 1: Analyze the Problem and Summarize Key Points**\n- **Objective**: Improve the hydrophilicity of a polymer by attaching polyethylene glycol monomethyl ether (PEGME600) chains to its structure. PEGME600 is hydrophilic due to its polyethylene glycol backbone, which is rich in ether groups (-CH₂-O-) capable of forming hydrogen bonds with water.\n- **Key Considerations**:\n  1. Choose a modification strategy based on the functional groups of the polymer backbone.\n  2. Ensure chemical compatibility between PEGME600 and the polymer.\n  3. Optimize reaction conditions to achieve an effective attachment of PEGME600.\n- **Approach**: Functionalize the polymer so it can react with PEGME600, using a coupling reaction (e.g., esterification, amidation, or click chemistry, depending on the polymer structure).\n\n---\n\n### **Step 2: Detailed Experimental Preparation Scheme**\nWe will assume the base polymer is a carboxylic acid-functionalized polymer (e.g., polymethacrylic acid or a polymer with pendent -COOH groups). If your polymer does not have carboxylic acid groups but has other reactive groups like hydroxyl (-OH), an amine (-NH₂), or others, minor adjustments can be provided.\n\n#### **2.1. Materials and Reagents**\n1. **Polymer with carboxylic acid (-COOH) groups**: For example, polymethacrylic acid (PMAA) as a model polymer.\n2. **Polyethylene glycol monomethyl ether (PEGME600)**: Molecular weight ~600 g/mol, provided as a liquid at room temperature.\n3. **Coupling Agent**: N,N'-Dicyclohexylcarbodiimide (DCC) or 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC·HCl) as a coupling agent to activate the -COOH group of the polymer.\n4. **Catalyst**: 4-Dimethylaminopyridine (DMAP) as a co-catalyst to facilitate esterification.\n5. **Solvent**: Anhydrous dichloromethane (DCM) or dimethylformamide (DMF) as an aprotic solvent.\n6. **Purification materials**: Methanol, diethyl ether, and deionized water.\n\n---\n\n### **2.2. Reaction Steps**\n\n#### **Step 2.2.1: Preparation of the Reaction Mixture**\n1. **Activation of Carboxylic Acid Groups**:\n   - Dissolve the carboxylic acid-functionalized polymer (PMAA) in DCM or DMF. Concentration: ~10-20 mg/mL.\n   - Add a molar equivalent (1:1 molar ratio to carboxylic acid groups) of DCC or EDC·HCl to the polymer solution. DCC/EDC activates the carboxylic acid groups to form reactive O-acylisourea intermediates.\n   - Optionally, add 0.1 molar equivalents of DMAP as a catalyst to improve reaction kinetics.\n   - Stir the mixture under inert gas (argon or nitrogen) for 30-60 minutes at room temperature.\n\n2. **Addition of PEGME600**:\n   - Slowly add PEGME600 to the activated polymer solution. Use a slight molar excess of PEGME600 (e.g., 1.1-1.2 molar equivalents relative to -COOH groups) to ensure complete reaction.\n   - Maintain stirring and allow the reaction to proceed at room temperature or slightly elevated temperatures (e.g., 35-40°C) under inert conditions for 12-24 hours.\n\n---\n\n#### **Step 2.2.2: Filtration and Work-Up**\n1. **Removal of By-Products**:\n   - Precipitate the reaction product by adding the reaction mixture into a large volume of cold methanol. Unreacted PEGME600 and small-molecule by-products (e.g., dicyclohexylurea from DCC) will remain soluble in methanol, while the polymer will precipitate.\n   - Filter the precipitated polymer using a vacuum filtration setup. Wash the polymer thoroughly with cold methanol to remove unreacted reagents.\n\n2. **Drying**:\n   - Dry the polymer precipitate under vacuum at room temperature for 24-48 hours or until a constant weight is achieved.\n\n---\n\n#### **Step 2.2.3: Characterization**\n1. **Fourier Transform Infrared Spectroscopy (FTIR)**:\n   - Check for the disappearance of the -COOH group peak (typically ~1700 cm⁻¹ for carbonyl) and the presence of -C-O-C- ether peaks (~1100 cm⁻¹) characteristic of PEG chains.\n2. **Nuclear Magnetic Resonance (NMR) Spectroscopy**:\n   - Use 1H NMR to confirm the presence of PEGME600 in the polymer. Characteristic PEG peaks include a singlet around δ ~3.5 ppm (for -OCH₂CH₂O- protons).\n3. **Contact Angle Measurements**:\n   - Measure the water contact angle on a film of the modified polymer to confirm improved hydrophilicity. A lower contact angle indicates greater hydrophilicity.\n4. **Gel Permeation Chromatography (GPC)**:\n   - Determine the molecular weight distribution of the modified polymer.\n\n---\n\n### **Step 3: Expected Outcomes**\n- By covalently attaching PEGME600 to the polymer backbone, the hydrophilicity of the polymer is significantly enhanced. This is due to the presence of hydrated ethylene oxide groups in PEG, which interact strongly with water molecules.\n- The resulting material is expected to exhibit better water dispersion or solubility and reduced fouling, making it suitable for applications such as hydrophilic coatings, biomedical devices, and drug delivery systems.\n\n---\n\n### **Alternative Strategies**\nIf the polymer lacks carboxylic acid groups:\n- For polymers with hydroxyl (-OH) groups: Convert -OH to tosylate groups using tosyl chloride, which can then react with PEGME600 under basic conditions (e.g., NaH).\n- For polymers with amine (-NH₂) groups: Directly react with PEGME600 activated with a carbonate group (e.g., PEGME600 carbonate derivative).\n\nLet me know if you need further guidance or adjustments for your specific polymer!"
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+{
+  "design_question": "Explain the role of hydroxyethyl acrylate (HEA) as a monomer in the preparation of hydrophilic polymers and how it can be integrated into the experimental process.",
+  "design_answer": "Certainly, let’s analyze your question and break it down systematically to ensure we cover the role of hydroxyethyl acrylate (HEA) comprehensively and provide a detailed step-by-step experimental preparation scheme.\n\n---\n\n### **Analysis of the Question:**\n\n1. You are interested in understanding the role of **hydroxyethyl acrylate (HEA)** as a monomer in imparting hydrophilic properties to polymers.\n2. You also want guidance on how HEA can be incorporated into an experimental process for synthesizing hydrophilic polymers.\n\nKey aspects that we need to address:\n- Chemical properties of HEA that make it hydrophilic.\n- How HEA can be polymerized or co-polymerized.\n- Detailed experimental steps, including reaction conditions, molar ratios, reagents needed, and other critical factors.\n\n---\n\n### **Understanding the Role of Hydroxyethyl Acrylate (HEA):**\n\nHydroxyethyl acrylate (HEA) is an acrylic monomer with a hydroxyl (-OH) group on the ethyl substituent. Its key properties that contribute to hydrophilicity are:\n1. **Hydrophilic Hydroxyl Group**: The –OH group is polar and can form hydrogen bonds with water molecules, increasing the polymer’s affinity for water.\n2. **Acrylate Functional Group**: The acrylate group allows HEA to undergo free radical polymerization, enabling it to form linear or crosslinked polymer networks.\n\nAs a monomer, HEA is often used in formulations to enhance hydrophilicity in biomedical applications (e.g., hydrogels), coatings, adhesives, and membranes.\n\n---\n\n### **Experimental Process for Synthesizing Hydrophilic Polymer Using HEA:**\n\nBelow is a systematic preparation scheme for synthesizing a hydrophilic polymer incorporating HEA, through **free radical polymerization**:\n\n#### **Step 1: Preparation of Materials and Equipment**\n**Materials Needed:**\n- Hydroxyethyl acrylate (HEA).\n- Co-monomers (optional, such as acrylamide or methacrylic acid for tailored properties).\n- Initiator (e.g., azobisisobutyronitrile, AIBN, or potassium persulfate).\n- Solvent (e.g., water, ethanol, or dimethylformamide (DMF) depending on solubility and desired polymer properties).\n- Crosslinker (optional, e.g., ethylene glycol dimethacrylate (EGDMA) for hydrogels).\n- pH-adjusting agent (if acidic or basic conditions are required).\n\n**Equipment Needed:**\n- Reaction flask (glass vessel with stirring mechanism).\n- Nitrogen gas source (to avoid oxygen interference during polymerization).\n- Thermostat or oil bath for temperature control.\n- Stirrer (magnetic or mechanical).\n\n---\n\n#### **Step 2: Reaction Setup**\n1. **Solution Preparation**:\n   - Dissolve the HEA monomer in a suitable solvent (e.g., ethanol for moderate polarity or water for full hydrophilic polymer synthesis).\n   - For co-polymerization, add additional monomers like acrylamide or methacrylic acid (adjust the ratio depending on desired hydrophilic and mechanical properties).\n   - If crosslinking is needed, incorporate the crosslinker (e.g., EGDMA) at a concentration of 1–5 mol% relative to the total monomer content.\n\n2. **Initiator Addition**:\n   - Add the initiator (e.g., AIBN at 0.5–2.0 wt% relative to monomer weight) to the solution.\n   - Dissolve the initiator completely to ensure uniform catalysis during polymerization.\n\n---\n\n#### **Step 3: Polymerization Reaction Conditions**\n1. **Degassing**:\n   - Purge the reaction flask with nitrogen for 15–30 minutes to remove dissolved oxygen, which can inhibit free radical polymerization.\n   \n2. **Temperature Control**:\n   - Heat the solution to the optimal temperature for the chosen initiator:\n     - For AIBN, ~70–80°C is ideal.\n     - For potassium persulfate, ~50–60°C may be used.\n\n3. **Reaction Duration**:\n   - Maintain the reaction at the set temperature for 4–6 hours, depending on the system. Monitor the viscosity of the solution as the polymer forms.\n\n4. **Neutralization (if pH-sensitive monomers are used)**:\n   - If acidic co-monomers like methacrylic acid were used, adjust the pH with a neutralizing agent post-reaction to ensure stability.\n\n---\n\n#### **Step 4: Post-Polymerization Processing**\n1. **Precipitation** (if in non-aqueous solution):\n   - Precipitate the polymer by pouring the reaction mixture into a non-solvent (e.g., ethyl acetate or acetone).\n   - Filter and wash the precipitate to remove unreacted monomers.\n\n2. **Drying**:\n   - Dry the polymer at 40–60°C in a vacuum oven to remove residual solvent.\n\n---\n\n#### **Step 5: Characterization**\nTo confirm the hydrophilic properties of the synthesized polymer, perform the following tests:\n1. **Water Contact Angle Measurement**:\n   - Assess the hydrophilicity by measuring the contact angle on a flat polymer surface.\n2. **Swelling Ratio Test** (for hydrogels):\n   - Immerse the polymer in water and measure its swelling capacity.\n3. **Fourier Transform Infrared Spectroscopy (FTIR)**:\n   - Analyze the presence of hydroxyl (-OH) groups and confirm polymer structure.\n4. **Solubility Test**:\n   - Evaluate the polymer’s solubility in water or polar solvents.\n\n---\n\n### **Notes and Adjustments for HEA Incorporation**\n1. Carefully adjust the HEA content in the monomer feed to tune the hydrophilicity:\n   - Higher HEA ratios will generally yield higher hydrophilicity, but may reduce mechanical strength.\n   - Typical feed composition ranges may be HEA: 50%–100%, with 0–50% co-monomers.\n2. If crosslinking is involved, ensure the crosslinker concentration is optimized to prevent over-crosslinking, which may cause reduced swelling or altered hydrophilicity.\n\n---\n\n### **Conclusion:**\n\nHydroxyethyl acrylate (HEA) serves as an excellent monomer to enhance hydrophilicity in polymers due to its hydroxyl group. Its integration into the polymerization process requires careful selection of reaction conditions, initiators, and solvent systems to achieve desired properties. By systematically following the outlined experimental scheme, the student should be able to successfully synthesize hydrophilic polymers and characterize their hydrophilic behaviors.\n\nDo not hesitate to bring up any nuances or ask further questions if clarification is needed—science thrives on rigorous pursuit!"
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+  "design_question": "Explain the role of surfactants, such as sodium dodecyl benzene sulfonate (SDBS), in improving the distribution and stability of TiO2 particles during polymer modification for hydrophilicity enhancement.",
+  "design_answer": "Certainly, let's dive into your question thoughtfully and step by step, integrating both theoretical insights and practical considerations to strengthen your understanding of the role surfactants, like sodium dodecyl benzene sulfonate (SDBS), play in the context of improving the dispersion and stability of TiO₂ particles during polymer modification for enhanced hydrophilicity.\n\n---\n\n### 1. **Analyzing the Question and Summarizing Key Points**\n\n- **Question Focus:** Understanding the mechanism by which surfactants like SDBS assist in improving TiO₂ particle distribution and stability in the polymer matrix to enhance hydrophilicity.\n- **Context:** TiO₂ is often employed as a functional additive in hydrophilic polymer preparation due to its photocatalytic activity, surface properties, and ability to enhance hydrophilicity. However, proper dispersion and stability of TiO₂ within the polymer are critical for achieving desired properties.\n- **Key Role of Surfactant (SDBS):** To enhance distribution and stability by addressing challenges such as particle aggregation and poor interfacial interaction between TiO₂ and the polymer matrix.\n\n---\n\n### 2. **Systematic and Detailed Explanation**\n\nLet me now break this down systematically, focusing on surfactant function, interaction mechanisms, and experimental considerations.\n\n---\n\n#### **(A) Challenges with TiO₂ in Polymer Modification**:\n1. **Agglomeration of TiO₂ Nanoparticles**:\n   - TiO₂ nanoparticles possess high surface energy, which drives their tendency to aggregate.\n   - Aggregation reduces the effective surface area of TiO₂ available for interaction and diminishes its beneficial properties (e.g., hydrophilicity enhancement and photocatalytic activity).\n\n2. **Hydrophobic Incompatibility**:\n   - TiO₂ particles often have a surface chemistry that may not distribute well in polymeric matrices with differing hydrophilic/hydrophobic balance.\n\n---\n\n#### **(B) Role of SDBS as a Surfactant**:\nSodium dodecyl benzene sulfonate (SDBS) is an anionic surfactant, and its amphiphilic structure makes it an excellent dispersing agent. Its role can be detailed as follows:\n\n1. **Adsorption onto TiO₂ Nanoparticle Surfaces**:\n   - The sulfonate head group (-SO₃⁻) in SDBS has strong electrostatic affinity for the TiO₂ surface.\n   - The adsorption of SDBS introduces a negative charge layer around each TiO₂ nanoparticle, imparting electrostatic repulsion.\n   - This prevents aggregation by overcoming the attractive Van der Waals forces between particles.\n\n2. **Enhanced Hydrophilicity via Amphiphilicity**:\n   - The hydrophilic sulfonate head ensures compatibility with hydrophilic components in the polymer or aqueous reaction medium.\n   - The hydrophobic tail of SDBS can interact with nonpolar domains, facilitating better dispersion within the hydrophilic polymer matrix.\n\n3. **Stabilization in Suspension**:\n   - SDBS forms a stable colloidal suspension of TiO₂ particles in aqueous media, which is crucial for uniform incorporation into the polymerization process.\n\n4. **Improved Interfacial Interaction**:\n   - Even after incorporation into the polymer matrix, SDBS helps maintain the spatial separation of TiO₂ particles.\n   - Additionally, the hydrophilic sulfonate groups on the surface of TiO₂ create active sites for hydrophilic polymer chains to interact, thereby enhancing overall polymer hydrophilicity.\n\n---\n\n#### **(C) Step-by-Step Experimental Scheme**\n\n1. **Preparation of TiO₂ Suspension Using SDBS**:\n   - **Materials**: TiO₂ nanoparticles, SDBS, deionized water.\n   - **Process**:\n     1. Dissolve an appropriate amount of SDBS in deionized water (e.g., 1–2% w/v surfactant solution).\n     2. Add TiO₂ nanoparticles gradually to the SDBS solution under stirring.\n     3. Sonicate the solution for 30–60 minutes to break up agglomerates and achieve fine dispersion.\n   - **Key Considerations**:\n     - The concentration of SDBS should be sufficient to cover the entire surface of TiO₂ particles without leading to micelle formation.\n     - Ultrasonication helps disintegrate existing agglomerates, and vigorous stirring ensures homogeneous dispersion.\n\n2. **Incorporation into Polymerization or Polymer Matrix**:\n   - **For in situ polymerization**:\n     1. After preparing the stable TiO₂–SDBS suspension, introduce it into the polymerization reaction medium.\n     2. Ensure compatibility between the polymerization conditions and TiO₂ dispersion (e.g., pH, ionic strength).\n   - **For blending with pre-synthesized polymer**:\n     1. Mix the TiO₂–SDBS suspension with the polymer solution or melt under strong shear forces to achieve uniform distribution.\n\n3. **Polymer Crosslinking and Hydrophilicity Enhancement**:\n   - The incorporated TiO₂ particles, stabilized by SDBS, enhance hydrophilicity because:\n     - They increase the water-attracting properties of the polymer due to their surface hydrophilic functionality.\n     - The sulfonate groups of SDBS on the surface of TiO₂ participate in further hydrogen bonding or electrostatic interactions with water.\n\n4. **Post-treatment**:\n   - Remove excess unbound SDBS by washing the polymer (if non-covalently bound SDBS could impact final properties).\n   - Conduct curing or thermal treatments as required for polymerization completion.\n\n---\n\n#### **(D) Reaction Conditions and Ratios**\n\n1. **SDBS to TiO₂ Ratio**:\n   - An SDBS-to-TiO₂ weight ratio of approximately 1:10 to 1:5 often works optimally, depending on the TiO₂ particle size and specific surface area.\n\n2. **Dispersion Medium**:\n   - Use deionized water or a compatible aqueous media to prepare the TiO₂ suspension.\n\n3. **Sonication Conditions**:\n   - Ultrasonic frequency: ~20–40 kHz.\n   - Duration depends on the degree of dispersion observed visually (typically 30–60 min).\n\n4. **Polymerization Compatibility**:\n   - Adjust pH to prevent destabilization of TiO₂ suspension during polymerization (neutral to slightly acidic pH works well for SDBS-stabilized TiO₂).\n\n---\n\n### 3. **Summary**\n\nThe use of sodium dodecyl benzene sulfonate (SDBS) plays a pivotal role in achieving effective dispersion and stabilization of TiO₂ nanoparticles during polymer modification. By adsorbing onto the TiO₂ surface, SDBS prevents aggregation and promotes compatibility with the polymer matrix, ensuring that the hydrophilic properties of both the TiO₂ and the surfactant synergistically enhance the hydrophilicity of the final polymer.\n\nThrough proper experimental design, including optimized SDBS-to-TiO₂ ratios, dispersion techniques, and integration into the polymer system, one can successfully prepare hydrophilic polymers with uniformly distributed TiO₂ particles that exhibit improved performance and stability."
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+  "design_question": "What precautions would you take to ensure successful free-radical polymerization when using N,N-二甲基丙烯酸胺 as a monomer in a hydrophilic polymer synthesis? Include considerations for reaction temperature and initiators in your explanation.",
+  "design_answer": "To answer your question systematically and comprehensively, we will identify the key points regarding the use of **N,N-dimethylacrylamide (DMAA, N,N-二甲基丙烯酸胺)** as a monomer in the context of free-radical polymerization for synthesizing a hydrophilic polymer. I will walk you through the details of the synthesis process, including critical precautions to ensure the success of the reaction.\n\n---\n\n### **Key Points for Analysis**\n1. **Monomer background**: DMAA is hydrophilic due to its amide group, which can engage in hydrogen bonding. It is an excellent choice when designing hydrophilic polymers.\n2. **Polymerization method**: Free-radical polymerization is widely used for DMAA because it allows easy control over reaction conditions and is compatible with various initiators.\n3. **Critical considerations**:\n   - Temperature regulation (a crucial factor in the rate of reaction, polymer quality, and prevention of undesirable side reactions).\n   - Choice of initiators (specific initiators and concentrations significantly influence the polymerization process).\n   - Oxygen inhibition (oxygen scavenges free-radicals and can inhibit polymerization efficiency).\n   - Reaction solvent/medium (for consistent monomer solubility and controllable mixing).\n   \nHaving identified these, let us proceed step by step in developing a detailed experimental approach that covers all the necessary precautions.\n\n---\n\n### **Detailed Steps and Precautions for Free-Radical Polymerization**\n\n#### **1. Selection of the Initiator**\nFree-radical polymerization requires an initiator to generate free radicals that start the polymerization chain reaction. Common initiators for polymerizing DMAA include:\n   \n- **Thermal initiators**:\n  - **Azobisisobutyronitrile (AIBN)**: A widely used free-radical initiator that decomposes thermally to generate radicals. It requires temperatures in the range of **60–80°C** (initiator half-life depends on temperature).\n  - **Potassium persulfate (KPS)**: Also effective for water-based polymerization, especially if the solvent is aqueous.\n\n- **Redox initiator systems**:\n  - In cases where low temperatures (e.g., room temperature) are desired, a redox system such as **ammonium persulfate (APS)** combined with a reducing agent like **N,N,N',N'-tetramethylethylenediamine (TEMED)** can be used to initiate polymerization.\n\n##### **Precaution 1**: Initiator concentration must be optimized:\nUse initiator concentrations in the range of **0.1–1.0 wt% of the total monomer weight**, depending on the desired molecular weight of the polymer (lower initiator concentrations generally yield higher molecular weights).\n\n##### **Precaution 2**: Avoid premature decomposition of the initiator:\nAdd the initiator to the reaction mixture **after all other components (monomer, solvent, chain transfer agents, etc.) are fully dissolved and mixed**. For thermal initiators like AIBN, ensure the reaction vessel has reached the desired polymerization temperature before introducing the initiator.\n\n---\n\n#### **2. Reaction Temperature Control**\nTemperature is a critical factor in free-radical polymerization for DMAA:\n- **AIBN**: Requires **60–80°C**, typically 70°C is optimal for generating radicals at a sustainable rate.\n- **KPS**: Functions effectively in the range of **60–80°C**, with decomposition accelerated by higher temperature.\n- **Redox initiators (e.g., APS/TEMED)**: Operate at **room temperature to around 40°C**, advantageous for thermally sensitive applications.\n\n##### **Precaution 3**: Use a controlled heating mechanism:\nEmploy a thermostated water bath or oil bath with precise temperature control to keep the reaction mixture at the target temperature. Temperature fluctuations can affect the polymerization rate and molecular weight distribution.\n\n##### **Precaution 4**: Avoid excessive heat:\nOverheating can lead to radical termination reactions, undesirable crosslinking, or side reactions, leading to polymer degradation or gelation.\n\n---\n\n#### **3. Purging with Inert Gas (Removing Oxygen)**\nOxygen in the reaction environment interferes with free-radical polymerization by scavenging radicals and forming peroxides, resulting in reduced polymerization efficiency or premature termination.\n\n##### **Precaution 5**: Degas the reaction mixture:\n- Purge the reaction system (flask, solvent, monomer, etc.) with **inert gas (e.g., nitrogen or argon)** for at least **15–30 minutes** before initiating polymerization. Use a gas inlet system connected to the reaction vessel.\n- Perform the reaction under a nitrogen or argon blanket to maintain an oxygen-free atmosphere throughout the reaction.\n\n---\n\n#### **4. Choice of Solvent**\nDMAA is water-soluble, making it well-suited for **aqueous or mixed solvent polymerizations**. However, other polar solvents such as **methanol, ethanol, or dimethyl sulfoxide (DMSO)** can also be used depending on the specific application.\n\n##### **Precaution 6**: Choose a solvent that:\n- Ensures complete solubility of the monomer and initiator.\n- Does not interfere with the reaction or generate side reactions.\n- Can stabilize the resulting polymer (e.g., aqueous solutions often aid in maintaining hydrophilic polymer properties).\n\n##### **Precaution 7**: Maintain solvent proportions:\nExcess solvent may dilute the reaction mixture and reduce polymerization kinetics. Typically, **30–50 wt% monomer concentration** is used for polymerization in solution. Adjust based on the target polymer and reactor type.\n\n---\n\n#### **5. Reaction Time and Monitoring**\nPolymerization time should be optimized to allow complete monomer conversion while minimizing degradation or chain termination from prolonged reaction.\n\n##### **Precaution 8**: Monitor the reaction:\n- Check the mixture's viscosity and perform monomer conversion analysis using tools such as **NMR spectroscopy** or **gas chromatography**.\n- Terminate the reaction promptly when desired conversion (usually >95%) is achieved by rapid cooling or addition of a radical inhibitor (e.g., hydroquinone).\n\n---\n\n#### **6. Post-Polymerization Purification**\nAfter polymerization, the polymer must be purified to remove unreacted monomer, initiator residues, or side products.\n\n##### **Precaution 9**: Choose a suitable purification process:\n- **Precipitation method**: Precipitate the polymer into a nonsolvent (e.g., precipitate DMAA polymer using diethyl ether or acetone). Collect the polymer via filtration and dry under vacuum.\n- **Dialysis**: For water-soluble polymers (e.g., where a hydrophilic polymer is intended), use dialysis to remove low molecular weight impurities.\n\n---\n\n### **Summary**\nTo ensure a successful free-radical polymerization of N,N-dimethylacrylamide for a hydrophilic polymer:\n1. Choose an appropriate initiator (e.g., AIBN for thermal, APS/TEMED for redox).\n2. Carefully control reaction temperature within the optimal ranges and avoid overheating.\n3. Purge the system with nitrogen or argon to exclude oxygen.\n4. Use a proper solvent to ensure solubility and avoid side reactions.\n5. Monitor reaction progress and terminate at the desired conversion.\n6. Purify the polymer thoroughly to remove traces of impurities.\n\nBy following these steps and precautions, you will enhance the hydrophilicity of the resulting polymer while achieving a high-purity product with controlled molecular weight characteristics. Let me know if you need clarification or further discussion!"
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+  "design_question": "In the preparation of Prepolymer 2, hydroxyethyl acrylate is added during synthesis. Explain the purpose of using this molecule, including its functional groups, and how it aids in modifying the polymer to enhance hydrophilicity.",
+  "design_answer": "Alright, let's break the question into its components and systematically address each aspect to ensure clarity.\n\n### 1. **Analysis of the Question and Key Points**\nThe question pertains to the use of **hydroxyethyl acrylate (HEA)** in the synthesis of a polymer (specifically a prepolymer labeled \"Prepolymer 2\"). You want to understand:\n- The **purpose of HEA** in the reaction.\n- The **functional groups** in HEA and their roles.\n- How HEA contributes to the **enhancement of hydrophilicity** in the synthesized polymer.\n\nTo address these key points, we need to explore:\n- The molecular structure and properties of hydroxyethyl acrylate.\n- The chemistry underlying its role in polymer synthesis.\n- The specific enhancement of polymer hydrophilicity using HEA.\n\n---\n\n### 2. **Understanding Hydroxyethyl Acrylate: Functional Groups and Properties**\n\n#### (a) **Molecular Structure of HEA**:\n   - Hydroxyethyl acrylate (HEA) is a bifunctional molecule with the following structure:\n     ```\n     CH2=CH-COO-CH2-CH2-OH\n     ```\n     It contains two key functional groups:\n     1. **Acrylic group (-CH=CH2)**: This vinyl group can undergo **radical polymerization** or other chain-growth polymerization mechanisms when forming the polymer backbone. It serves as the **reactive site** for incorporation into the polymer chain.\n     2. **Hydroxyl group (-OH)**: This group is hydrophilic in nature, meaning it can form hydrogen bonds with water. It also allows for secondary chemical modifications, such as crosslinking or additional functionalization. \n\n#### (b) **Reactivity of HEA**:\nThe dual functionality of HEA (acrylic group for polymerization and hydroxyl group for hydrophilicity or further reactions) makes it a versatile monomer in polymer synthesis. Its structure allows it to:\n   - Participate in **copolymerization** with other monomers.\n   - Enhance the polymer's compatibility with water (owing to its hydrophilic nature).\n   - Provide functional groups for tailoring the polymer's mechanical or chemical properties.\n\n---\n\n### 3. **Purpose of Using Hydroxyethyl Acrylate in Prepolymer 2**\n\nDuring the synthesis of **Prepolymer 2**, HEA is introduced to achieve the following objectives:\n\n#### (a) **Incorporation of Hydrophilic Functional Groups**:\n- By including HEA in the monomer mixture during polymerization, the hydroxyl (-OH) groups from HEA are chemically bound to the polymer backbone. This incorporation leads to an increase in the overall **hydrophilicity** of the polymer.\n- The hydroxyl groups can form **hydrogen bonds** with water molecules, improving the polymer's ability to absorb water, swell, or dissolve in polar solvents. This is highly desirable for applications where water interaction is critical, such as in hydrogels, coatings, or biomaterials.\n\n#### (b) **Improving Polymer Versatility**:\n- The presence of hydroxyl groups from HEA introduces sites for **post-polymerization modification**. For example, hydroxyl groups can react with isocyanates to form urethane linkages or can be crosslinked to improve mechanical properties while retaining hydrophilicity.\n- This functionality provides flexibility in polymer design, allowing downstream tailoring of material properties.\n\n#### (c) **Modifying Surface Properties**:\n- When incorporated, HEA can facilitate **surface hydrophilization** of the polymer. If the polymer is used in coatings or membranes, the hydroxyl groups exposed at the surface reduce interfacial tension with water, thereby improving wettability and biocompatibility.\n\n#### (d) **Introducing Stability Against Phase Separation**:\n- The hydrophilic nature of HEA contributes to improved **compatibility** between hydrophilic and hydrophobic domains in copolymers. This reduces phase separation and ensures better dispersion of hydrophilic segments throughout the material.\n\n---\n\n### 4. **Experimental Preparation Scheme for Prepolymer 2**\n\nBelow is a generalized experimental scheme for incorporating HEA into a polymer while discussing the key details. While this is a guided outline, specific parameters (like temperatures or time) should align with the larger context provided for Prepolymer 2.\n\n#### **Step 1: Selection of Monomers**\n- HEA is added as part of the monomer mixture during polymerization.\n- Typical molar ratios would be determined based on the desired level of hydrophilicity. For instance, if the target hydrophilic content is moderate, HEA might comprise 10–30% of the total monomers by molar ratio.\n- Additional monomers with complementary properties (e.g., hydrophobic acrylates, crosslinkers, etc.) are selected to balance the polymer’s hydrophilicity and structural integrity.\n\n#### **Step 2: Polymerization Mechanism**\n- HEA is often used in **free-radical polymerization**, though other mechanisms like controlled radical polymerization (e.g., RAFT or ATRP) may also be used.\n- A typical reaction mixture would contain:\n  - HEA: 10–30% molar fraction.\n  - Other acrylate monomers (e.g., methyl methacrylate, butyl acrylate): 70–90% molar fraction.\n  - Initiator (e.g., azobisisobutyronitrile, AIBN): 1–2 wt% relative to total monomers.\n  - Solvent: An inert solvent like ethanol or dimethylformamide (DMF) may be used to dissolve the monomers and improve miscibility.\n  - Optional additives: A chain-transfer agent (e.g., mercaptans) may be added to control molecular weight.\n\n#### **Step 3: Reaction Conditions**\n- The polymerization is initiated at elevated temperatures (e.g., 60–80°C for AIBN) in a nitrogen-purged environment to prevent inhibition by oxygen.\n- The reaction is allowed to proceed for several hours (e.g., 4–12 hours) with stirring to ensure uniform polymerization.\n\n#### **Step 4: Post-Polymerization Processing**\n- The resulting prepolymer is purified via:\n  - Precipitation into a non-solvent (e.g., diethyl ether).\n  - Filtration or dialysis to remove unreacted monomers and byproducts.\n\n#### **Step 5: Characterization**\n- The functional incorporation of HEA can be confirmed through techniques such as:\n  - **FTIR spectroscopy**: Identification of hydroxyl (-OH) groups and acrylic backbone.\n  - **NMR spectroscopy**: Verification of HEA’s incorporation ratio.\n  - **Contact angle measurement**: Determination of surface hydrophilicity.\n\n---\n\n### 5. **How HEA Enhances Hydrophilicity**\n\n- The hydroxyl groups from HEA act as points of interaction with water, enabling the polymer to form **hydrogen bonds**. This greatly improves water compatibility and wettability.\n- Incorporation of HEA increases the polymer’s **polar content**, reducing surface energy and enhancing **water absorption capacity**.\n- For biomedical or environmentally sensitive applications, this hydrophilicity can improve biocompatibility, reduce biofouling, or improve degradability.\n\n---\n\n### Final Summary\n\nHydroxyethyl acrylate is a bifunctional molecule with an acrylic group for chain polymerization and a hydroxyl group for enhancing polymer hydrophilicity. Its incorporation into Prepolymer 2 provides hydrophilic functionality, facilitates water interaction, and introduces sites for functional modification. By systematically controlling its concentration and reaction conditions, HEA enables precise tuning of polymer properties for a wide range of applications. If you need specific numeric calculations for this synthesis, feel free to ask!"
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+{
+  "design_question": "When using '丙二醇单甲醚' (propylene glycol monomethyl ether) in the modification of a polymer, what considerations should be taken regarding its solubility and compatibility with other components? Outline how this might affect the overall hydrophilicity.",
+  "design_answer": "Certainly! As a seasoned professor with expertise in polymer science, let us approach your question systematically, step by step.\n\n---\n\n### **1. Analyzing the Question and Summarizing Key Points**\nThe question pertains to the use of propylene glycol monomethyl ether (PGME, 丙二醇单甲醚) as a modifying agent in the synthesis of hydrophilic polymers. Specifically, we need to delve into:\n- The solubility and compatibility of PGME with other components in the polymerization system.\n- How these factors affect the hydrophilicity enhancement of the polymer.\n- The experimental preparation scheme that incorporates PGME into the polymer while ensuring hydrophilicity improvement.\n\n### **2. Detailed Answer: Polymer Modification Scheme with PGME**\nTo address this question thoroughly, I will provide a systematic process to synthesize and functionalize a hydrophilic polymer with PGME while considering solubility, compatibility, and hydrophilicity enhancement.\n\n---\n\n#### **Step 1: Understanding PGME's Fundamental Properties**\nPropylene glycol monomethyl ether (PGME) has characteristics critical to its role as a modifier:\n- **Chemical structure**: PGME contains both a hydrophilic hydroxyl (-OH) group and a hydrophobic methyl ether functionality (-CH3).\n- **Solubility**: It is partially hydrophilic due to the hydroxyl group, capable of dissolving in aqueous and organic systems depending on the solvent polarity.\n- **Compatibility**: PGME can interact with hydrophilic or moderately hydrophobic components via hydrogen bonding or van der Waals interactions.\n\nKey considerations:\n1. PGME tends to form hydrogen bonds with water or hydrophilic polymers, enhancing compatibility in aqueous or polar environments.\n2. For hydrophobic systems, care must be taken to ensure miscibility or compatibility through proper adjustments in solvent or formulation.\n\n---\n\n#### **Step 2: Selecting the Polymer Substrate**\nTo incorporate PGME, choose a polymer substrate that:\n- Has functional groups (such as carboxyl, hydroxyl, or amine) for chemical coupling or physical blending with PGME.\n- Requires enhanced hydrophilicity for improved performance in aqueous environments.\nCommon candidates include:\n- Polyacrylic acid (PAA) or polyvinyl alcohol (PVA) for their hydrophilic backbone.\n- Copolymers of styrene derivatives modified to include polar groups.\n- Polyurethane with hydroxyl or amine functional groups.\n\n---\n\n#### **Step 3: Reaction Pathways and Mechanisms**\nPGME can be introduced into the polymer matrix via two main pathways:\n\n**A. Chemical Grafting or Crosslinking:**\nPGME can be chemically grafted to the polymer backbone through reactions involving hydroxyl or ether groups. Below is a typical experimental scheme:\n\n1. **Choose a coupling agent**:\n   - Select a coupling agent that reacts with the -OH group of PGME and the polymer's functional groups (e.g., carboxylic acid or amine).\n   - Commonly used coupling agents: diisocyanates (for urethanes), carbodiimides (for carboxylic acids), or epoxides.\n\n2. **Reaction setup**:\n   - Dissolve PGME in a polar solvent (such as acetone or methanol) to ensure uniform dispersion. For aqueous polymers, water can be used as a co-solvent.\n   - Add the polymer substrate in the same solvent system to ensure compatibility.\n   - Introduce the coupling agent at a stoichiometric ratio. For example:\n     - PGME:polymer:functional agent in a molar ratio of **1:1:0.8–1** ensures sufficient reaction while minimizing excess reagents.\n\n3. **Reaction conditions**:\n   - Maintain the temperature at ~60–80°C to activate functional groups without decomposing PGME.\n   - pH control (near neutral to slightly basic, pH ~7–8) may be necessary for hydroxyl group reactivity.\n\n4. **Post-reaction purification**:\n   - Precipitate the product if needed by adding a non-solvent (e.g., hexane or ethanol).\n   - Wash and dry the polymer to remove unreacted PGME or coupling agent.\n\n---\n\n**B. Physical Blending:**\nAlternatively, PGME can be blended physically into the polymer matrix if chemical bonding is unnecessary, provided that solubility and phase compatibility are sufficient.\n\n1. **Polymer preparation**:\n   - Dissolve the polymer in an appropriate solvent for blending (e.g., water or DMSO for hydrophilic polymers).\n   - Introduce PGME gradually under stirring, ensuring homogeneous mixing.\n\n2. **Compatibility considerations**:\n   - Ensure no phase separation occurs during mixing. The solvent should promote miscibility to avoid PGME aggregation.\n   - Optionally, introduce a surfactant or co-solvent to improve solubility.\n\n3. **Final product formation**:\n   - Evaporate/precipitate the solvent after blending, yielding a modified polymer matrix with enhanced hydrophilicity.\n\n---\n\n#### **Step 4: How PGME Enhances Hydrophilicity**\nBy integrating PGME into the polymer structure:\n1. The hydroxyl group interacts with water molecules, enhancing water affinity (hydrophilicity).\n2. The methyl ether group balances hydrophilic absorption and prevents excessive swelling for improved mechanical stability.\n3. Functional grafting further introduces hydrophilic domains, uniformly dispersing PGME as part of the polymer matrix.\n\n---\n\n### **Conclusion**\nIncorporating PGME to modify a polymer requires careful consideration of its solubility and compatibility:\n- Match PGME’s reactivity and miscibility with the polymer and other reaction components.\n- Adjust molar ratios, solvent systems, and reaction conditions methodically to optimize hydrophilicity improvement.\n\nThis systematic approach ensures your experimental scheme succeeds in synthesizing a hydrophilic polymer effectively, ready for laboratory application. Should you pose a specific polymer system, I can tailor the preparation scheme further."
+}
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diff --git a/task2/task2-qa/CN114957645B_╥╗╓╓╙├╙┌ABS╗∙▓─╡─╣т╣╠╗п│м╟╫╦о═┐┴╧╫щ║╧╬я╝░╞ф═┐▓у╡─╓╞▒╕╖╜╖и.json b/task2/task2-qa/CN114957645B_╥╗╓╓╙├╙┌ABS╗∙▓─╡─╣т╣╠╗п│м╟╫╦о═┐┴╧╫щ║╧╬я╝░╞ф═┐▓у╡─╓╞▒╕╖╜╖и.json
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+{
+  "design_question": "Describe an experimental procedure to synthesize a hydrophilic polymer using trimethylolpropane (tri-hydroxy methyl propane), including details on how to enhance the hydrophilicity of the final polymer product.",
+  "design_answer": "### Thought Process:\nTo synthesize a hydrophilic polymer based on the provided molecule, trimethylolpropane (TMP), we need to leverage its tri-functional hydroxyl groups (-OH) as reactive sites. These hydroxyl groups make TMP an excellent precursor for forming a range of polymers, especially those designed for hydrophilicity due to the ability to introduce polar and hydrogen-bonding functional groups. To enhance the hydrophilicity of the final polymer product, we can introduce additional hydrophilic groups such as carboxyl (-COOH), hydroxyl (-OH), or ionic groups, such as sulfonic acid (-SO3H).\n\nTaking these aspects into consideration, I will provide a step-by-step systematic experimental procedure below for the synthesis of a hydrophilic polymer based on TMP, which includes techniques to increase hydrophilicity.\n\n---\n\n### Key Points for Planning the Synthesis:\n1. **Reactant Selection**: Trimethylolpropane (tri-hydroxy methyl propane) is the core monomer. Other monomers/reagents should be chosen to introduce hydrophilic functional groups.\n2. **Polymerization Route**: Select either a step-growth polymerization (e.g., esterification) or other functionalization using hydrophilic reactants.\n3. **Enhancing Hydrophilicity**: Use reagents containing groups like -COOH, -OH, or -SO3H. These groups increase hydrophilicity and water solubility.\n4. **Reaction Parameters**: Determine the ideal reaction conditions (temperature, catalysts, and solvent) to optimize polymerization and hydrophilicity.\n\n---\n\n### Detailed Experimental Procedure:\n#### **Synthesis of Hydrophilic Polymer from Trimethylolpropane**:\nWe will prepare a hydrophilic polyester by reacting trimethylolpropane (TMP) with a dicarboxylic acid (e.g., citric acid) followed by end-functionalization to enhance hydrophilicity.\n\n---\n\n#### **Step 1. Esterification Polymerization (Base Polymer Synthesis):**\n**Objective**: Cross-link TMP with citric acid to form a three-dimensional hydrophilic polyester network.\n\n- **Materials Needed**:\n  - Trimethylolpropane (TMP): 10 g (0.075 mol)\n  - Citric acid (CA): 14.02 g (0.073 mol, slight stoichiometric excess to favor ester bond formation and ensure residual unreacted carboxylic acid groups contribute to hydrophilicity)\n  - Catalyst: p-Toluenesulfonic acid (PTSA), 0.2 g (approx. 2 wt% of total reactants)\n  - Solvent: None (reaction performed in bulk to avoid solvent contamination for hydrophilic performance enhancement).\n  - Reaction vessel: 250-mL round-bottom flask with a reflux condenser.\n\n**Procedure**:\n1. Place TMP and citric acid in a round-bottom flask equipped with a magnetic stirrer, and add PTSA as a catalyst.\n2. Gradually heat the mixture to **140–160°C** under inert nitrogen gas to prevent oxidation.\n3. Stir and maintain temperature for **4–5 hours**. Initially, the system will appear molten as ester bonds begin forming.\n4. Monitor the reaction progress by observing water evolution (a by-product of esterification) using a Dean-Stark trap if necessary.\n5. Monitor polymer formation using FT-IR spectroscopy. Look for diminishing O-H stretching (~3300 cm⁻¹) and increasing ester carbonyl band (~1730 cm⁻¹).\n6. Once complete, allow the reaction mixture to cool to room temperature.\n\n**Expected Product**:\nA hydrophilic polyester with terminal -COOH groups (from excess citric acid), as well as some unreacted -OH groups (from TMP).\n\n---\n\n#### **Step 2. Enhancing Hydrophilicity via Post-Functionalization**:\n**Objective**: Introduce additional hydrophilic ionic groups (e.g., sulfonic acid) to the polymer.\n\n- **Materials Needed**:\n  - Chlorosulfonic acid (HSO3Cl): 5 mL (be cautious with its high reactivity)\n  - Pyridine: 10 mL (acts as a scavenger for HCl formed by the reaction)\n  - Solvent: Dry dichloromethane (DCM), 50 mL.\n  - Product from Step 1: 5 g.\n\n**Procedure**:\n1. Dissolve the polyester from Step 1 in 50 mL of dry DCM in a 250-mL round-bottom flask under nitrogen atmosphere.\n2. Slowly add chlorosulfonic acid dropwise (over 30 minutes) to prevent localized overheating, stirring continuously at **0°C** (ice bath).\n3. After the addition, allow the mixture to gradually warm to room temperature and stir for another **4 hours**.\n4. Quench the reaction by carefully adding ice-cold water while stirring (beware of vigorous HCl release).\n5. Separate the aqueous phase containing the sulfonated polymer and dialyze it against water for 48 hours to remove residual salts and impurities.\n6. Lyophilize (freeze dry) the polymer solution to obtain the sulfonated hydrophilic polymer as a powder.\n\n**Expected Product**:\nThe final polymer now contains sulfonic acid (-SO3H) groups and residual -OH or -COOH groups, rendering it highly water-absorbent and hydrophilic.\n\n---\n\n#### **Step 3. Characterization and Confirmation**:\nPerform the following tests to verify the structure and hydrophilicity of the synthesized polymer:\n1. **FT-IR Spectroscopy**: Look for:\n   - Ester carbonyl (C=O) peaks around 1730 cm⁻¹.\n   - Sulfonic acid (S=O) doublet peaks around 1190–1260 cm⁻¹.\n2. **Contact Angle Measurement**: Drop water on the polymer film to observe its hydrophobicity; a lower contact angle indicates higher hydrophilicity.\n3. **Water Absorption Test**: Measure the water uptake (swelling ratio) by immersing the polymer in water.\n4. **Thermogravimetric Analysis (TGA)**: Check for thermal stability of the hydrophilic polymer.\n5. **NMR Spectroscopy**: Analyze the backbone structure and quantify functional group incorporation.\n\n---\n\n### Notes and Safety Considerations:\n1. **Stoichiometry Control**: Ensure a slight excess of citric acid in Step 1 to promote hydrophilicity through residual functional groups.\n2. **Reaction Environment**: Keep the system moisture-free during the sulfonation reaction to prevent side reactions.\n3. **Safety**:\n   - Handle chlorosulfonic acid in a fume hood due to its corrosive nature and potential HCl release.\n   - Ensure proper personal protective equipment (PPE), including gloves, goggles, and a lab coat.\n\n---\n\n### Conclusion:\nThis experimental protocol details the synthesis of a hydrophilic polymer using trimethylolpropane via esterification with citric acid followed by sulfonation. The resulting polymer is rich in hydrophilic functional groups (-OH, -COOH, and -SO3H), making it suitable for applications such as hydrophilic coatings, biomedical devices, or absorbent materials."
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+{
+  "design_question": "Explain how you would utilize 2-acrylamido-2-methylpropanesulfonic acid (AMPS) to synthesize an intermediate product for a hydrophilic polymer. Include details of any neutralization steps and justify their role in the reaction.",
+  "design_answer": "Sure! Let us proceed step by step to analyze your question, summarize the key points, and design a detailed experimental preparation scheme for the synthesis of an intermediate product using 2-acrylamido-2-methylpropanesulfonic acid (AMPS). \n\n---\n\n### **Step 1: Analyze the Question and Summarize Key Points**\nThe goal of this question is to utilize AMPS, a hydrophilic and highly charged monomer due to its sulfonic acid functional group, to synthesize an intermediate product for a hydrophilic polymer. Key points to be addressed include:\n1. Reaction steps involving AMPS.\n2. Consideration of the sulfonic acid group, including its acidic nature, and whether it needs to be neutralized in the reaction process.\n3. Reaction conditions (solvent, temperature, pH, etc.), reagent quantities, and specific outcomes.\n\n---\n\n### **Step 2: Systematic Answer – Experimental Preparation Scheme**\n\n#### **Introduction to AMPS Chemistry**\nAMPS (2-acrylamido-2-methylpropanesulfonic acid) is a popular hydrophilic monomer because of its sulfonic acid group, which imparts strong ionic interactions and water affinity. In its unneutralized form, the sulfonic acid group (–SO₃H) is an acidic proton donor. Depending on the reaction requirements, we can leave this group protonated or neutralize it to a sulfonate anion (–SO₃⁻). For most polymerization processes or intermediate synthesis, the neutralization step is critical to control pH, improve reactivity, and avoid potential acid-catalyzed side reactions like hydrolysis.\n\n#### **Proposed Scheme: Neutralization and Preparation of a Hydrophilic Intermediate**\n\nHere’s a stepwise scheme to synthesize an intermediate using AMPS:\n\n---\n\n### **Step 1: Neutralization of AMPS**\n1. **Objective**:\n   Neutralize the sulfonic acid group (–SO₃H) of AMPS to form its sodium salt (sodium AMPS, Na-AMPS). This ensures:\n    - Adjusted pH for subsequent reactions (around neutral or slightly basic).\n    - Improved solubility and reactivity of AMPS in aqueous systems.\n\n2. **Reagents**:\n   - 2-Acrylamido-2-methylpropanesulfonic acid (AMPS).\n   - Sodium hydroxide (NaOH) solution or another suitable base (like KOH).\n\n3. **Experimental Procedure**:\n   - Dissolve the required amount of AMPS (e.g., **10 g, 0.048 mol**) in distilled water (100 mL with stirring). AMPS is highly water-soluble.\n   - Prepare an equimolar aqueous solution of NaOH. For **0.048 mol** AMPS, use **0.048 mol of NaOH, which corresponds to about 1.92 g NaOH**.\n   - Add the NaOH solution dropwise to the AMPS solution under vigorous stirring while monitoring the pH using a pH meter.\n   - Stop addition when a pH of **6.8–7.5** is reached (indicating complete conversion of –SO₃H to –SO₃⁻, without over-neutralizing to alkalinity).\n   - The reaction is as follows:\n     \\[\n     \\text{AMPS} + \\text{NaOH} \\rightarrow \\text{Sodium-AMPS (Na-AMPS)}\n     \\]\n\n4. **Important Notes**:\n   - Do not exceed pH 7.5; strong alkalinity could affect the acrylamide group, causing unwanted side reactions (e.g., hydrolysis to acrylic acid derivatives).\n   - The solution should remain transparent and homogeneous.\n\n---\n\n### **Step 2: Creation of the Intermediate Product**\n1. **Objective**:\n   Use sodium AMPS (Na-AMPS) in a polymerization or conjugation reaction to synthesize the desired hydrophilic intermediate.\n\n2. **Choice of Polymerization Technique**:\n   - For this step, we can opt for a **free-radical polymerization**, as it’s a common and efficient route for hydrophilic polymer synthesis.\n   - The intermediate could be a homopolymer of AMPS or a copolymer with other hydrophilic/acrylic monomers (depending on the target properties).\n\n3. **Reagents**:\n   - Sodium-AMPS (prepared above).\n   - Water-soluble radical initiator (e.g., **ammonium persulfate (APS)**, potassium persulfate, or azobisisobutyronitrile (AIBN) in certain solvents).\n   - Optional comonomers if copolymerization is desired (e.g., acrylamide, acrylic acid, etc.).\n   - Deionized water as a solvent.\n\n4. **Experimental Procedure**:\n   - Prepare an aqueous solution with the desired concentration of Na-AMPS. For a typical reaction:\n     - Use **10 g (0.048 mol)** of Na-AMPS in 100 mL of deionized water.\n   - If using a comonomer, add it at the desired feed ratio. For example:\n     - Add **4.26 g (0.06 mol)** of acrylamide for a 50:50 molar copolymerization.\n   - Purge the solution with nitrogen gas for **30 minutes** to remove dissolved oxygen, which could inhibit polymerization.\n   - Add 0.1–1 wt% APS (relative to the total monomer mass) as the radical initiator. For example:\n     - Use approximately **0.01 g APS**.\n   - Maintain the reaction temperature at **60–70°C** for 2–4 hours with constant stirring.\n   - After the reaction, precipitate the intermediate polymer product by adding the solution dropwise into a nonsolvent (e.g., ethanol).\n   - Collect the intermediate by filtration, washing with ethanol, and drying under vacuum at 60°C.\n\n---\n\n### **Step 3: Justification of Neutralization**\nNeutralization of AMPS is critical for the following reasons:\n1. Prevents unwanted side reactions due to the acidic –SO₃H group (e.g., hydrolysis of the acrylamide group or acid catalysis).\n2. Facilitates better control of reaction conditions (pH, ionic strength), essential for achieving high polymerization efficiency.\n3. Improves water solubility of the monomer and its compatibility with comonomers or initiators, enabling a more homogenous reaction mixture.\n\n---\n\nBy following the above process, you can successfully synthesize an intermediate product based on AMPS. Let me know if you'd like assistance with specific variations in comonomers or reaction techniques!"
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diff --git a/task2/task2-qa/CN115044008B_╥╗╓╓╟╫╦о╨═╤Ї└ы╫╙╣т╣╠╗п╩ў╓м╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json b/task2/task2-qa/CN115044008B_╥╗╓╓╟╫╦о╨═╤Ї└ы╫╙╣т╣╠╗п╩ў╓м╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json
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+{
+  "design_question": "In a Michael addition reaction, polyethylene glycol diacrylate (PEG400DA) reacts with a diamine to form an intermediate hydrophilic polymer. Outline a detailed experimental procedure for preparing this intermediate, focusing on how the molar ratio of the two reactants influences the hydrophilicity of the intermediate.",
+  "design_answer": "Certainly! I'll guide you systematically through the process of answering your question, focusing on analysis, experimental procedure, and key aspects such as the molar ratio's influence on hydrophilicity.\n\n---\n\n### **Step 1: Analyze the Question**\nThe reaction described involves a **Michael addition** reaction between **polyethylene glycol diacrylate (PEG400DA)** and a **diamine** to synthesize an intermediate hydrophilic polymer. The goal is not only to understand the preparation procedure but also to examine how the molar ratio of PEG400DA and diamine influences the hydrophilicity of the intermediate.\n\nKey Points:\n1. **Reactants**:\n   - PEG400DA: A difunctional acrylate-based reagent with hydrophilic properties due to the PEG chain (average molar mass ~400 g/mol per PEG chain).\n   - Diamine: A molecule containing primary amine groups (-NH2), capable of undergoing nucleophilic addition during the Michael addition reaction.\n2. **Reaction Conditions**: The Michael addition is a base-catalyzed nucleophilic reaction generally conducted in the presence of mild base and/or solvent.\n3. **Molar Ratio Effect**: The degree of functionality achieved in the product (extent of crosslinking and chain formation) depends on the molar ratio of the two reactants. This balance regulates:\n   - The density of amino and acrylate groups available for the reaction.\n   - The hydrophilicity of the product: A higher PEG content will enhance hydrophilicity, while excessive crosslinking via diamine could reduce it.\n\n---\n\n### **Step 2: Experimental Design for Polymer Preparation**\n\nHere is a detailed experimental scheme for synthesizing the intermediate hydrophilic polymer.\n\n---\n\n#### **Materials Required**\n1. **Polyethylene glycol diacrylate (PEG400DA)**: Commercially available; ensure purity >98%.\n2. **Diamine**: Choose a suitable hydrophilic diamine (e.g., ethylenediamine or 1,6-hexanediamine).\n3. **Solvent**: Deionized water or a polar aprotic solvent like dimethyl sulfoxide (DMSO). Avoid nonpolar solvents to maintain hydrophilicity.\n4. **Base Catalyst**: Triethylamine (TEA) or sodium bicarbonate (~0.1 equivalent to diamine) for mildly basic conditions.\n5. **pH Adjuster (Optional)**: Small amounts of dilute solutions of HCl or NaOH for fine-tuning.\n6. **Stirrer Setup**: Magnetic stirrer and sealed flask to prevent contamination.\n\n---\n\n#### **Step 1: Define Molar Ratios**\n\nThe molar ratio of PEG400DA to diamine is critical. The interaction of ratios with hydrophilicity is as follows:\n- **Molar Ratio**: PEG400DA:Diamine.\n   1. **Low Diamine (2:1 or higher)**: Excess PEG400DA results in incomplete crosslinking and introduces free hydrophilic PEG acrylate groups, enhancing hydrophilicity.\n   2. **Equimolar Ratio (1:1)**: A balanced reaction results in full reaction of all functional acrylate and amine groups, yielding a network with moderate hydrophilicity.\n   3. **High Diamine (1:2 or higher)**: Excess diamine introduces additional amino groups, which could slightly reduce the polymer's hydrophilicity due to reduced free PEG content.\n\nDecide on the desired hydrophilicity for your product and adjust the molar ratio accordingly. For example, if high hydrophilicity is desired, a PEG-rich environment (e.g., 2:1 molar ratio) is preferred.\n\n---\n\n#### **Step 2: Reaction Setup**\n\n1. **Prepare Reaction Mixture**:\n   - Dissolve PEG400DA (e.g., **2 mmol, 0.8 g for PEG400**) in 10 mL of the chosen solvent (water or DMSO) under mild stirring to form a homogenous solution.\n   - Add the diamine (e.g., **1 mmol, 0.06 g for ethylenediamine**) slowly, ensuring the desired molar ratio. Stir continuously.\n   - Add the base catalyst (e.g., **0.1 mmol of triethylamine**, ~0.01 mL).\n\n2. **Control Reaction Parameters**:\n   - **Temperature**: Maintain mild conditions (~25–40°C) to prevent side reactions or premature polymerization.\n   - **Stirring**: Stir gently (~500 RPM) but uniformly for effective mixing.\n   - **pH Monitoring**: Ensure the pH stays between 8–10 to facilitate the Michael addition reaction without degrading reactants.\n   - **Reaction Time**: Allow 2–4 hours for the reaction to complete. Monitor the reaction progress using infrared spectroscopy (IR peaks for acrylate at ~810 cm⁻¹ will disappear as the acrylate groups react).\n\n---\n\n#### **Step 3: Post-Reaction Steps**\n\n1. **Isolation**:\n   - After the reaction completes, remove the solvent using mild vacuum evaporation or dialysis (in case of water-based reactions) to purify the intermediate polymer.\n   - Adjust pH if necessary and wash the polymer with deionized water to remove unreacted diamine or PEG.\n\n2. **Characterization**:\n   - Use **Fourier-transform infrared spectroscopy (FTIR)** to confirm the disappearance of acrylate groups and appearance of new bonds (e.g., C-N stretching at ~1250 cm⁻¹).\n   - Check molecular weight distribution using **gel permeation chromatography (GPC)**.\n   - Confirm hydrophilicity by checking the water contact angle or swelling behavior in an aqueous environment.\n\n---\n\n### **Step 3: Discuss Influence of Molar Ratio on Hydrophilicity**\n\n- **PEG400DA-Rich Polymers**: High hydrophilicity due to excess free PEG chains. These materials swell significantly in water and are ideal for applications like hydrogels or bio-compatible materials.\n- **Balanced Ratios**: Moderate hydrophilicity with well-balanced crosslinked networks.\n- **Diamine-Rich Polymers**: Reduced hydrophilicity due to higher amine content, which could affect the degree of swelling or solubility in water.\n\nTailor the molar ratio based on the application. For hydrogels, PEG-rich conditions (e.g., 2:1) would be ideal. For structural purposes, a balanced (1:1) ratio provides mechanical stability without compromising water compatibility.\n\n---\n\n### **Conclusion**\n\nTo prepare a hydrophilic polymer via the Michael addition of PEG400DA and diamine:\n1. Choose a molar ratio suitable for your hydrophilicity requirements.\n2. Control reaction conditions (e.g., mild temperature, stirring, pH).\n3. Characterize the product to ensure hydrophilicity and chemical structure meet expectations.\n4. Adjust experimental parameters iteratively as needed for refinement.\n\nGood luck in the lab—let me know if you want any additional clarifications!"
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diff --git a/task2/task2-qa/CN115044012B_╥╗╓╓╟╫╦о╨═╣т╣╠╗п╩ў╓м╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json b/task2/task2-qa/CN115044012B_╥╗╓╓╟╫╦о╨═╣т╣╠╗п╩ў╓м╝░╞ф╓╞▒╕╖╜╖и║═╙ж╙├.json
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+{
+  "design_question": "Describe how you would utilize isophorone diisocyanate (IPDI) in a reaction with hydroxyethyl acrylate (HEA) to obtain a reactive prepolymer functionalized with isocyanate groups. Specify the mole ratio and key conditions for the reaction.",
+  "design_answer": "Certainly! Let us systematically tackle your question about reacting isophorone diisocyanate (IPDI) with hydroxyethyl acrylate (HEA) to obtain a reactive prepolymer functionalized with isocyanate groups.\n\n---\n\n### **Step 1: Analysis of the Reaction and Goal**\n- **Reaction Overview**: The goal is to synthesize a reactive prepolymer by reacting isophorone diisocyanate (IPDI), an aliphatic diisocyanate, with hydroxyethyl acrylate (HEA), which contains both an acrylate group and a hydroxyl (-OH) group.\n- **Underlying Chemistry**: The hydroxyl group of HEA reacts selectively with one of the isocyanate (-NCO) groups of IPDI to form a urethane linkage, leaving the second isocyanate group unreacted. The resulting product is a functionalized molecule with both acrylate and isocyanate reactivities.\n- **Key Considerations**:\n  - Reaction selectivity is crucial: we aim for a monoaddition reaction where only *one* -NCO group reacts.\n  - Excess IPDI is used to prevent unintended side reactions, such as diacrylate formation or crosslinking.\n\n---\n\n### **Step 2: Reaction Equation**\n\\[\\text{IPDI} + \\text{HEA} \\xrightarrow{\\text{Catalyst, Solvent}} \\text{IPDI-HEA adduct (isocyanate-functionalized)}\\]\n\n---\n\n### **Step 3: Detailed Experimental Scheme**\nNow, let us outline the step-by-step process for synthesizing the reactive prepolymer. I will specify stoichiometric ratios, reaction conditions, and practical considerations.\n\n#### **i. Determining Reaction Molar Ratio**\n- Use a molar ratio of **1.1:1 (IPDI:HEA)**.\n  - Slight excess of IPDI ensures complete reaction of HEA's hydroxyl group with an -NCO group, preventing secondary reactions.\n  - For example, if 1 mole of HEA is used, add 1.1 moles of IPDI.\n\n#### **ii. Selection of Solvent**\n- Use an anhydrous, aprotic solvent such as **dry toluene**, **dry acetonitrile**, or **methyl ethyl ketone (MEK)**:\n  - These solvents dissolve both IPDI and HEA well.\n  - The solvent must be water-free to avoid hydrolysis of isocyanate groups.\n  - Add enough solvent to produce a 10–20% (w/v) reaction mixture for ease of control.\n\n#### **iii. Catalyst and Additives**\n- Add a catalytic amount (0.1–0.5 wt% relative to HEA) of a mild urethane formation catalyst, such as **dibutyltin dilaurate (DBTDL)** or **1,4-diazabicyclo[2.2.2]octane (DABCO)**, to facilitate the reaction without promoting side reactions.\n- Alternatively, a tertiary amine catalyst may also work effectively.\n\n#### **iv. Experimental Procedure**\n1. **Preparation of Materials**:\n   - Dry the HEA under reduced pressure to ensure it is free of moisture, as water will react with the isocyanate groups.\n   - Store IPDI in a sealed container to avoid exposure to atmospheric moisture.\n\n2. **Reaction Setup**:\n   - Set up a **3-necked round-bottom flask** under a nitrogen or argon atmosphere to prevent atmospheric moisture and oxygen from interfering.\n   - Add the dry solvent to the reaction vessel, followed by the required amount of IPDI (e.g., 1.1 moles for 1 mole of HEA).\n   - Add the catalyst to initiate the reaction.\n\n3. **Controlled Addition of HEA**:\n   - Using a dropping funnel, slowly add HEA into the reaction mixture over 30–60 minutes while stirring. The slow addition ensures selective reaction of the hydroxyl group with an -NCO group without unwanted side reactions.\n   - Maintain a controlled temperature during the addition: **20–40°C** is typically optimal. Higher temperatures increase the risk of side reactions, while lower temperatures may slow the reaction.\n\n4. **Monitoring the Reaction**:\n   - Stir the reaction mixture and monitor it using **FTIR spectroscopy**. The disappearance of the O–H stretching band of hydroxyl (~3300 cm⁻¹) and reduction in the -NCO stretching band (~2270 cm⁻¹) indicate the formation of the urethane bond.\n   - Avoid complete disappearance of the -NCO band, as one isocyanate group should remain unreacted.\n\n5. **Post-Reaction Workup**:\n   - After the reaction completes (typically 2–3 hours), remove unreacted IPDI by vacuum distillation or precipitation in a non-solvent like hexane if needed.\n   - Store the product under inert conditions to prevent reaction of residual isocyanate groups with moisture.\n\n---\n\n### **Step 4: Reaction Conditions Summary**\n| Parameter                  | Value                                |\n|----------------------------|--------------------------------------|\n| Mole Ratio (IPDI:HEA)      | 1.1:1                               |\n| Catalyst                   | DBTDL or DABCO (0.1–0.5 wt% HEA)    |\n| Solvent                    | Dry toluene, acetonitrile, or MEK   |\n| Temperature                | 20–40°C                             |\n| Reaction Time              | 2–3 hours                           |\n| Atmosphere                 | Inert (nitrogen or argon)           |\n\nThe final product is a urethane prepolymer with an acrylate group and a remaining isocyanate group. This material can subsequently serve as a useful intermediate in hydrophilic polymer synthesis, for example, by reacting it further with amines, alcohols, or water to create functional hydrophilic polymers.\n\n---\n\n### **Step 5: Further Use and Applications**\nThis reactive prepolymer can be crosslinked or copolymerized with other vinyl compounds (e.g., acrylates, methacrylates) to generate hydrophilic polymer matrices. Additionally, the residual isocyanate group can be used to introduce other hydrophilic moieties or reactive sites to tailor material properties.\n\n---\n\nShould you need clarification or additional details about any specific step, feel free to ask!"
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+  "design_question": "When integrating polyethylene glycol-based amines (such as ED2003) into a polymer network, what functional group interactions are critical for ensuring the resulting polymer exhibits increased hydrophilicity? Propose experimental conditions to optimize this reaction.",
+  "design_answer": "Certainly! Let's break this question into key components to ensure a thorough analysis and a systematic answer.\n\n---\n\n### **Key Analysis of the Question**\n1. **Polyethylene glycol-based amines (e.g., ED2003)**:\n   - ED2003 is a polyethylene glycol (PEG)-based amine, known for its hydrophilic nature due to its repeating ethylene glycol (EG) units. The amine termini add potential reactivity for covalent incorporation into polymer networks.\n   - The challenge lies in properly grafting or crosslinking ED2003 into the polymer to enhance hydrophilicity without compromising structural integrity.\n\n2. **Functional group interactions**:\n   - The specific chemical interactions (e.g., reactions of the terminal amine groups, interactions with other network moieties, or incorporation via crosslinking) dictate the success of the functionalization.\n\n3. **Experimental conditions**:\n   - Providing detailed experimental parameters (reagents, molar ratios, reaction conditions) is critical to ensuring successful synthesis and optimization in a laboratory setting.\n\n---\n\n### **Critical Functional Group Interactions for Hydrophilicity**\nTo ensure increased hydrophilicity of the resulting polymer, the following functional group interactions should be considered:\n- **Amine Functionality of ED2003**: The primary or secondary amines (-NH2/-NH) in ED2003 can react with functional groups such as carboxylic acids (-COOH), epoxy groups, or isocyanates (-NCO) via condensation, addition, or crosslinking reactions.\n- **PEG Backbone in ED2003**: The poly(ethylene glycol) chain itself provides inherent hydrophilic properties due to its high affinity to water (via hydrogen bonding). Its presence in the polymer enhances water-solubility, wettability, and overall hydrophilicity.\n\n---\n\n### **Proposed Experimental Scheme**\nBelow I outline a systematic experimental procedure for integrating ED2003 into a polymer matrix. I'll include a specific reaction, reaction conditions, and optimization steps.\n\n#### **Reaction Mechanism**: Crosslinking ED2003 with a multi-functional Epoxy Resin\nThis process leverages the reactivity between the terminal amine groups (-NH2) of ED2003 and the epoxy groups (-CH(O)CH2).\n\n---\n\n### **Step 1: Selection of Starting Materials and Reagents**\n- **Base Polymer**: Select a multi-functional epoxy resin with high epoxy equivalent weight (e.g., polyethylene glycol diglycidyl ether for biocompatibility or a diglycidyl ether of bisphenol A (DGEBA) for rigidity).\n- **Hydrophilic Modifier**: ED2003 (a PEG-based diamine with molecular weight ~2000 g/mol).\n- **Curing Agent**: To ensure effective network formation, include a co-monomer (e.g., triethylenetetramine (TETA)).\n\n#### **Preparation Conditions**\n1. **Reagent Ratios**:\n   - Epoxy Resin: Hydrophilic diamine (ED2003): Curing Agent = 1:0.5:0.25 (molar ratio).\n   - Example Calculations for 10 g of polymer network:\n     - Epoxy resin: ~5.0 g.\n     - ED2003: ~3.5 g.\n     - TETA: ~1.5 g.\n2. **Solvent**:\n   - Optional: Use a small amount of polar aprotic solvent (e.g., dimethylformamide, DMF) to improve miscibility if the reagents are not soluble in a common medium.\n\n#### **Procedure**:\n1. Dissolve the epoxy resin in DMF at room temperature under continuous stirring until a homogeneous solution forms.\n2. Gradually add ED2003 to the resin, ensuring complete mixing. Stir the mixture at 50–60°C (to reduce viscosity) for 1–2 hours.\n3. Add the curing agent (TETA) dropwise at ~50°C under stirring. Continue stirring for an additional 30 minutes to ensure uniform mixing.\n   - **Note**: Excess ED2003 can lead to a more hydrophilic product but may compromise the mechanical properties.\n4. Pour the formulation into a mold or flat casting surface. Allow the mixture to thermally cure at 80°C for 4 hours, then post-cure at 120°C for an additional 6 hours.\n\n#### **Optimization**:\n- Screen different molar ratios (e.g., ED2003:Epoxy ratios of 1:1, 1:0.75, and 1:0.5) to determine the optimal balance between hydrophilicity and mechanical properties.\n- Assess the effect of curing time and temperature ramp rate—gradual heating often produces better crosslinked networks.\n\n---\n\n### **Step 2: Characterization of Hydrophilicity**\n- Perform water contact angle measurements for surface hydrophilicity. Expect angles < 30° with a high ED2003 content.\n- Conduct swelling ratio tests in water to assess the polymer's ability to absorb water.\n- FTIR spectroscopy:\n   - Look for characteristic absorption peaks for ether groups (PEG, ~1100–1200 cm⁻¹) and secondary amine groups (NH bending, ~1600 cm⁻¹).\n   - Confirm the reduction of hydroxyl peaks (~3400 cm⁻¹), indicating successful amine-epoxy reactions.\n\n---\n\n### **Final Notes for Laboratory Practice**\n1. Ensure precise weighing of reagents with an analytical balance.\n2. Work in a well-ventilated fume hood when handling solvents and curing agents.\n3. Conduct small-scale trials to identify optimal reaction parameters before scaling up.\n\nThis detailed experimental pathway should allow for the successful integration of ED2003 into a hydrophilic polymer network, balancing both hydrophilicity and material properties."
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+  "design_question": "You are tasked with utilizing N-(isobutoxy)methylacrylamide in the preparation of a hydrophilic polymer. Describe the chemical reaction mechanism this molecule participates in and its contribution to the overall hydrophilicity of the final polymer.",
+  "design_answer": "### Step 1: Analyze the Question and Summarize Key Points\nTo answer the question comprehensively, it is important to understand the functional characteristics of **N-(isobutoxy)methylacrylamide**, its reactivity, and how it can be incorporated into a polymer structure to enhance hydrophilicity. Key considerations include:\n1. **Chemical Reactivity**:\n   - The acrylamide group allows the molecule to participate in addition polymerization reactions via the double bond.\n   - The N-(isobutoxy)methyl group can be hydrolyzed under suitable conditions to yield functional groups that improve hydrophilicity.\n2. **Mechanism**:\n   - The molecule participates in radical polymerization or other chain-growth polymerization mechanisms involving the acrylamide moiety.\n   - Post-reaction hydrolysis can introduce hydrophilic groups to enhance water affinity.\n3. **Overall Contribution**:\n   - The hydrophilicity arises from functional groups (such as hydroxyl groups) introduced by hydrolysis after polymerization.\n\nThe experimental plan must outline a polymerization scheme and post-synthesis modification to maximize hydrophilicity.\n\n---\n\n### Step 2: Detailed and Systematic Description of the Preparation Scheme\nBelow is the detailed preparation scheme for synthesizing the hydrophilic polymer using **N-(isobutoxy)methylacrylamide**.\n\n#### **Step 2.1: Materials and Reagents**\n- **Monomer**: N-(isobutoxy)methylacrylamide\n- **Initiator**: Common radical polymerization initiators, such as azobisisobutyronitrile (AIBN) or potassium persulfate (KPS).\n- **Solvent**: Water or an organic solvent (acetone, ethanol, or dimethylformamide [DMF]) for controlling the reaction environment.\n- **Crosslinker (optional)**: N,N’-methylenebisacrylamide (MBA) to improve mechanical properties of the polymer.\n- **Acid catalyst**: Hydrochloric acid (HCl) or sulfuric acid (H2SO4) for hydrolysis in post-polymerization stages.\n\n---\n\n#### **Step 2.2: Experimental Preparation Scheme**\nThe synthesis will be divided into two phases:\n1. **Polymerization Reaction Phase**: Formation of the polymer backbone.\n2. **Post-Polymerization Hydrolysis Phase**: Enhancing hydrophilicity by converting hydrophobic groups to hydrophilic ones.\n\n---\n\n### **Phase 1: Radical Polymerization**\n#### **Step 1: Preparation of the Reaction Mixture**\n1. **Reagent Quantities**:\n   - Monomer (N-(isobutoxy)methylacrylamide): Depending on the desired degree of polymerization, use approximately **10 mmol** for smaller scale reactions.\n   - Solvent: Ensure a solvent volume sufficient to fully dissolve the monomer. For aqueous polymerizations, use 50 mL deionized water.\n   - Initiator (e.g., AIBN): Add 1 mol% relative to the monomer concentration (e.g., 0.1 mmol).\n   - Crosslinker (optional): Add N,N’-methylenebisacrylamide in amounts ranging from 0.5–2 mol% of the monomer concentration for gel-like polymers.\n\n2. **Mixing**:\n   Dissolve the monomer, initiator, and optional crosslinker in the solvent under nitrogen or argon to prevent oxygen inhibition of radical initiated polymerization.\n\n#### **Step 2: Polymerization Reaction**\n1. The reaction mixture is placed in a reaction vessel equipped with a stirrer and thermometer.\n2. **Reaction Conditions**:\n   - Temperature: Heat to 60–70°C (specific to the initiator decomposition temperature; for AIBN, 65°C is suitable).\n   - Duration: Allow polymerization to proceed for 4–6 hours to ensure high monomer conversion.\n3. **Monitoring**:\n   - Monitor viscosity changes in the reaction mixture, indicative of polymer formation.\n   - Optionally, take aliquots for spectroscopic analysis (e.g., FTIR) to confirm double bond consumption.\n\n4. **Isolation**:\n   - Precipitation Method: Precipitate the polymer by adding the reaction mixture to a non-solvent (e.g., cold methanol or acetone).\n   - Filtration and Washing: Wash with methanol to remove impurities and unreacted monomer.\n\n---\n\n### **Phase 2: Hydrolysis**\n#### **Step 1: Hydrolysis Setup**\nTo enhance hydrophilicity, the N-(isobutoxy)methyl group can be hydrolyzed to introduce hydrophilic functionalities (e.g., hydroxyl or amide groups).\n\n1. **Reagent Quantities**:\n   - Acid catalyst (e.g., HCl): Prepare a 0.1–0.5 M solution. Use 20–50 mL per 10 mmol of polymer.\n2. **Reaction Medium**:\n   - Dissolve the isolated polymer in water or a polar solvent capable of facilitating hydrolysis.\n\n#### **Step 2: Hydrolysis Reaction**\n1. Heat the solution to 80–95°C under acidic conditions.\n2. Reaction Time: Maintain for 12–24 hours for complete hydrolysis.\n3. Monitor Progress:\n   - Use FTIR spectroscopy (monitor disappearance of isobutoxy absorption bands and appearance of hydroxyl or amide bands).\n   - pH titration may be used to confirm acid consumption.\n\n#### **Step 3: Neutralization and Purification**\n1. Neutralize the solution using a mild base (e.g., sodium bicarbonate) if the polymer is acid-sensitive.\n2. Dialysis: Purify the hydrophilic polymer by dialysis against deionized water for 2–3 days to remove salts and residual acid.\n3. Drying: Lyophilize or air-dry the purified polymer.\n\n---\n\n### **Step 3: Mechanistic Insights**\n#### **Polymerization Mechanism**\nThe acrylamide moiety undergoes free radical polymerization initiated by AIBN. Radicals generated by initiators attack the double bond, forming a propagating chain that incorporates the monomer into the polymer backbone.\n\n#### **Hydrolysis Mechanism**\nUnder acidic conditions, the isobutoxy group undergoes hydrolysis:\n1. Cleavage of the N-(isobutoxy)methyl group.\n2. Formation of primary amide and/or hydroxyl groups, which can form hydrogen bonds with water.\n\n---\n\n### Summary\nThe overall hydrophilicity of the polymer arises from the conversion of hydrophobic isobutoxy functional groups into hydrophilic ones during the post-polymerization hydrolysis phase. This design leverages the reactivity of acrylamide and the functional group's transformability, resulting in a highly water-friendly polymer ideal for hydrophilic applications. Ensure careful monitoring and purification to obtain optimal results."
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+{
+  "design_question": "Describe how you would utilize diethanolamine in the synthesis of a hydrophilic polymer, considering its structural properties and potential reactivity. How does this molecule contribute to enhancing hydrophilicity?",
+  "design_answer": "### Analysis of the Question and Key Points:\n\nThe focus of the question is on using **diethanolamine** (DEA, a molecule with two hydroxyl groups and one secondary amine group) in the synthesis of a **hydrophilic polymer**. To answer, we must:\n1. Analyze the structural properties and reactivity of diethanolamine.\n2. Propose an experimental scheme where diethanolamine is utilized as a monomer or co-monomer.\n3. Highlight how diethanolamine contributes to hydrophilicity.\n4. Provide systematic details of the synthesis steps, including reaction conditions, reagents, and quantitative aspects.\n\n### Detailed and Systematic Experimental Preparation Scheme:\n\n#### Step 1: Understanding the Role of Diethanolamine (DEA)\n**Structural Properties of Diethanolamine (DEA):**\n- Diethanolamine contains:\n  - Two hydroxyl groups (–OH) that are hydrophilic and reactive.\n  - One secondary amine group (–NH) that can participate in nucleophilic reactions, such as amidation or ring-opening polymerizations.\n- DEA's structure makes it a versatile molecule for introducing both **hydrophilic functional groups** (hydroxyls) and potential crosslinking points (secondary amine).\n\n**Contribution to Hydrophilicity:**\n- The hydroxyl groups increase **hydrophilicity** by forming hydrogen bonds with water.\n- The secondary amine can add sites for further chemical modifications, which can also influence water affinity, depending on the derivative.\n\n#### Step 2: Experimental Scheme for Synthesizing a Hydrophilic Polymer Using DEA\n\nDiethanolamine can be incorporated into a hydrophilic polymer in various ways. Here, I will provide a stepwise synthesis of a **polyurethane hydrogel**, a common class of hydrophilic polymers where DEA can play a key role.\n\n---\n\n### ***Synthesis of a Polyurethane-Based Hydrophilic Polymer Using Diethanolamine***\n\n#### **Overview of the Synthetic Pathway:**\nThe polymer will be prepared by the reaction of:\n1. Diethanolamine (a tri-functional monomer).\n2. A diisocyanate (e.g., hexamethylene diisocyanate, HDI) as the coupling/chain-extending agent.\n3. Polyethylene glycol (PEG, molecular weight 400–2000 Da) as a soft, hydrophilic segment to improve water interaction.\n4. A crosslinker or optional additives (if forming a 3D network).\n\n---\n\n#### **Step 1: Preparation of the Reaction Mixture**\n- **Reagents Required**:\n  - Diethanolamine (DEA): 0.01 moles.\n  - Polyethylene glycol (PEG, MW 1000): 0.005 moles.\n  - Hexamethylene diisocyanate (HDI): 0.015 moles (stoichiometric excess to ensure complete reaction with hydroxyl and amine groups).\n  - Catalyst: Dibutyltin dilaurate (0.1 wt% of the reaction mixture).\n  - Solvent: Anhydrous dimethylformamide (DMF, 15–20 mL).\n\n#### **Step 2: Reaction Setup**\n1. **Pre-mixing DEA and PEG**:\n   - Dissolve DEA and PEG in anhydrous DMF (10 mL).\n   - Stir at room temperature under an inert nitrogen atmosphere to prevent moisture contamination (isocyanates react with water to form ureas).\n   - DEA and PEG provide the hydroxyl functionality to react with HDI.\n\n2. **Addition of Hexamethylene Diisocyanate (HDI)**:\n   - Slowly add HDI to the reaction mixture at 60–70°C while stirring continuously.\n   - Maintain a **stoichiometric ratio** where the molar sum of hydroxyl groups (from DEA and PEG) and amine groups (from DEA) equals the number of isocyanate groups in HDI.\n   - The reaction involves the formation of urethane linkages (-NH-CO-O-) between hydroxyls and isocyanates and urea linkages (-NH-CO-NH-) between amines and isocyanates.\n\n3. **Catalysis**:\n   - Add dibutyltin dilaurate (0.1 wt%) as a catalyst to increase the reaction rate and enhance polymerization.\n\n4. **Reaction Monitoring**:\n   - Monitor the progress of the reaction using Fourier Transform Infrared Spectroscopy (FTIR). The disappearance of the –NCO peak (~2270 cm⁻¹) indicates complete reaction with the hydroxyl and amine groups.\n\n---\n\n#### **Step 3: Formation of the Hydrogel (Optional Cross-Linking)**\n- To form a 3D hydrophilic network (a hydrogel), you can use an additional di- or tri-functional crosslinker (e.g., glycerol or trimethylolpropane). \n- Add the crosslinker in small amounts (0.001–0.002 moles) before introducing HDI to ensure homogeneous network formation.\n\n---\n\n#### **Step 4: Purification of the Polymer**\n1. Precipitate the polymer by pouring the reaction mixture into excess cold diethyl ether.\n2. Wash the precipitate with diethyl ether to remove unreacted monomers and catalyst residues.\n3. Dry the purified polymer in a vacuum oven at 50°C overnight.\n\n---\n\n#### **Step 5: Characterization of the Polymer**\n1. Confirm the structure using **FTIR**:\n   - Look for characteristic urethane (-NH-CO-O-) peaks (~1700 cm⁻¹).\n   - Absence of –NCO peaks (~2270 cm⁻¹) indicates complete reaction.\n2. Investigate hydrophilicity:\n   - Measure the **water absorption/swelling ratio** to assess hydrophilicity.\n   - Conduct **contact angle measurements** to quantify surface hydrophilicity.\n3. Test the thermal properties (optional):\n   - Use **Thermogravimetric Analysis (TGA)** or **Differential Scanning Calorimetry (DSC)** to investigate thermal stability.\n\n---\n\n### Key Features of This Polymer:\n1. **Hydrophilicity**: The hydroxyl groups from DEA and PEG provide sites for hydrogen bonding, improving water affinity.\n2. **Biocompatibility** (optional): The polymer can be tailored for biomedical applications by selecting medical-grade PEG and diisocyanates.\n3. **Customizability**: Varying the PEG molecular weight or DEA-HD ratio tailors the polymer's hydrophilicity and mechanical properties.\n\n---\n\n### Conclusion\nIn this synthesis, **diethanolamine** plays a dual role:\n- Its hydroxyl groups enhance **hydrophilicity** by facilitating hydrogen bonding with water.\n- Its secondary amine group participates in reactions to form urea linkages, which contribute to the structural integrity of the polymer.\n\nBy following the steps above, a hydrophilic polyurethane polymer can be systematically prepared, ensuring precise control over the polymer's chemical and physical properties."
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+{
+  "design_question": "Describe how you would use mercaptopropionic acid as a reactant to modify a polymer in an experiment designed to enhance its hydrophilicity. Specify the necessary reaction conditions based on your understanding of hydrophilic polymer synthesis.",
+  "design_answer": "### Step 1: Analyze the Question and Summarize the Key Points\n\nThe question involves **modifying a polymer using mercaptopropionic acid (MPA)** to enhance its hydrophilicity. Mercaptopropionic acid possesses two functional groups: a **thiol (-SH)** group and a **carboxylic acid (-COOH)** group. The **thiol group** can participate in reactions such as thiol-ene reactions or thiol-disulfide exchange, while the **carboxylic acid group** contributes hydrophilic properties, which aligns with the goal to increase the polymer’s hydrophilicity.\n\nWe aim to:\n1. Identify a suitable method to attach mercaptopropionic acid to the polymer.\n2. Specify the reaction conditions (e.g., catalyst, temperature, solvent) and reagent ratios.\n3. Systematically detail the entire experimental process to ensure this functionalization can be achieved practically in the lab.\n\n---\n\n### Step 2: Detailed and Systematic Reaction Design\n\n#### **Approach: Grafting Mercaptopropionic Acid onto the Polymer Backbone**\nTo attach mercaptopropionic acid to a polymer, two commonly used reactions can be utilized, depending on the polymer's structure and available functional groups:\n- **Thiol-ene Reaction** if the polymer contains unsaturated bonds (C=C).\n- **Thiol-disulfide Exchange Reaction** if the polymer already has disulfide linkages.\n\nFor this analysis, I will assume we are modifying a polymer featuring **vinyl groups (C=C bonds)** through a **thiol-ene click chemistry approach**. This choice is widely applicable and allows controlled, efficient grafting with good functional group tolerance.\n\n---\n\n#### **Experimental Procedure**\n\n**Step 1: Materials and Equipment**\nYou will need:\n- Mercaptopropionic acid (MPA): The key reactant.\n- Polymer with vinyl functionality (e.g., poly(butyl acrylate-co-glycidyl methacrylate) or similar).\n- Photoinitiator: 2,2-Dimethoxy-2-phenylacetophenone (DMPA) or Irgacure 651, commonly used in thiol-ene reactions.\n- Solvent: Ethanol or a similar polar, hydrophilic solvent.\n- UV light source (e.g., a UV lamp emitting at 365 nm).\n- Nitrogen gas for inert atmosphere.\n- Glassware: Reaction flask, stirrer, and UV-transparent quartz cell.\n\n---\n\n**Step 2: Reaction Setup and Conditions**\n1. **Prepare the Reaction Mixture:**\n   - In a reaction flask, dissolve the polymer with vinyl groups (amount depends on desired functionalization, typically 1–2 g) in ethanol (20–30 mL).\n   - Add mercaptopropionic acid in molar excess (2:1 molar ratio of MPA to vinyl groups). This ensures all available vinyl groups react with MPA for maximum hydrophilicity.\n   - Introduce the photoinitiator, e.g., DMPA, at around 1 wt% of the total reaction mixture.\n\n2. **Degas the Reaction Mixture:**\n   - Bubble nitrogen gas through the reaction mixture for 15–20 minutes to remove dissolved oxygen. Oxygen can interfere with the photochemical reaction.\n\n3. **Expose to UV Light:**\n   - Place the reaction vessel under UV light (365 nm) at room temperature.\n   - Stir the reaction continuously to ensure uniform exposure and prevent localized overheating.\n   - Allow the reaction to proceed for 30–60 minutes. Monitor the reaction's progress using FTIR spectroscopy by observing the reduction in the vinyl group peak (1600–1660 cm⁻¹) and the appearance of thiol-modified peaks near 1700 cm⁻¹ (C=O stretching from the incorporated MPA).\n\n---\n\n**Step 3: Purification**\n1. After completing the reaction, remove the solvent using a rotary evaporator.\n2. Dissolve the polymer in a suitable solvent (e.g., ethanol or water) and precipitate it into an antisolvent (commonly diethyl ether or hexane).\n3. Wash the precipitated polymer thoroughly to remove unreacted mercaptopropionic acid and photoinitiator residues.\n4. Dry the purified polymer under vacuum at 40–50°C until constant weight is achieved.\n\n---\n\n**Step 4: Characterization**\n1. **FTIR Spectroscopy:** Verify successful grafting by checking the reduction of vinyl peaks (1600–1660 cm⁻¹) and appearance of carboxylic acid peaks (1700 cm⁻¹).\n2. **Contact Angle Measurement:** Test the hydrophilicity of the modified polymer by performing a water contact angle test. A lower water contact angle compared to the unmodified polymer indicates enhanced hydrophilicity.\n3. **Thermal Analysis (TGA/DSC):** Confirm thermal stability after modification.\n4. **NMR Spectroscopy:** Use ¹H NMR to confirm the successful attachment of mercaptopropionic acid onto the polymer backbone (look for thiol and vinyl proton disappearance).\n\n---\n\n### Final Notes on Optimization and Scaling Up\n\n- **Reaction Time Optimization:** If time allows, conduct small-scale trials varying UV exposure time to maximize grafting efficiency without degradation.\n- **Stoichiometry Adjustments:** Optimize the MPA/polymer ratio for functionalization balance and material performance.\n- **Scaling Up:** For larger-scale synthesis, ensure that UV light exposure is uniform by using a controlled photoreactor. Monitor the reaction temperature more closely to avoid local heating.\n\nThis systematic approach ensures successful modification of the polymer, enhancing its hydrophilicity via the attachment of mercaptopropionic acid. If you have additional details about the polymer involved, we can refine this scheme further."
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+{
+  "design_question": "Considering the use of 2-acrylamide-2-methylpropanesulfonic acid (AMPS) as a hydrophilic monomer, describe how you would incorporate it into a polymer matrix to enhance the hydrophilicity of the final material. Specify the steps and conditions you would follow for the modification process.",
+  "design_answer": "To address your question systematically and in detail, let us work through the experimental preparation scheme step by step, focusing on incorporating 2-acrylamide-2-methylpropanesulfonic acid (AMPS) into a polymer matrix to enhance hydrophilicity. Incorporating AMPS, a highly hydrophilic monomer, into a polymer is a widely adopted strategy due to its functional sulfonic acid groups that summon exceptional water-affinity and ion-exchange properties to the final material. I will outline the relevant experimental details, reaction conditions, reagent ratios, and additional considerations to assist you in successfully executing this experiment in the lab. \n\n---\n\n### Step 1: Analyze the Key Aspects of the Question\n1. **Objective**: To incorporate AMPS into a polymer matrix to enhance the hydrophilicity.\n2. **Key challenge**: Ensuring efficient polymerization of AMPS while maintaining its water-solubility and functional properties.\n3. **Method**: Copolymerization of AMPS or grafting AMPS onto an existing polymer backbone via free-radical polymerization or other suitable methods, depending on the application.\n\nWe will focus on free-radical copolymerization, as it allows the introduction of AMPS into the polymer chain with good control and accessibility.\n\n---\n\n### Step 2: Design of the Experimental Preparation Scheme\n### Materials Required (Reagents and Solvents):\n1. **2-acrylamide-2-methylpropanesulfonic acid (AMPS)**: Hydrophilic monomer.\n2. **Other comonomers** (if copolymerization is intended):: For example, N,N-dimethylacrylamide (DMA), acrylic acid (AA), or acrylamide (AM), depending on the final polymer properties desired.\n3. **Crosslinker (optional)**: N,N'-methylenebisacrylamide (MBAA) or other similar crosslinkers if a network structure or hydrogel formation is required.\n4. **Initiator**: Potassium persulfate (KPS) or ammonium persulfate (APS) for free-radical initiation.\n5. **Chain transfer agent** (optional): Such as thiols, to control polymer molecular weight if a precise molecular weight distribution is desired.\n6. **Solvent**: Ultrapure water or a compatible solvent system for AMPS and co-monomers.\n7. **pH Adjuster**: Sodium hydroxide or hydrochloric acid for pH adjustment.\n\n---\n\n### Step 3: Copolymerization Reaction Process\n#### 3.1 Preparation of Reaction Solution\n1. **Dissolve the Monomers**:\n   - Dissolve AMPS in ultrapure water under stirring. Typical concentration ranges from 10–30 wt% of the total reaction solution, depending on the desired properties of the final polymer.\n   - If using comonomers (e.g., DMA, AA, AM), dissolve them in water as well, maintaining a target molar ratio of AMPS-to-comonomer. For example, a 70:30 AMPS-to-comonomer molar ratio will yield a hydrophilic polymer while maintaining some tunable structural properties.\n2. **Optional Crosslinking**:\n   - Include a small amount of crosslinker (e.g., 0.05–1 mol% MBAA relative to total monomer concentration) if the formation of a hydrogel or network structure is desired.\n3. **Adjust the pH**:\n   - Adjust the pH of the monomer solution to around 6–8 using sodium hydroxide or hydrochloric acid. AMPS contains a sulfonic acid group, so pH regulation is crucial to minimize side reactions and maintain monomer solubility.\n\n#### 3.2 Deoxygenation of the Solution\n- Degas the reaction mixture by purging nitrogen gas for 20–30 minutes to remove dissolved oxygen, which can inhibit free-radical polymerization.\n\n#### 3.3 Initiation of Polymerization\n1. **Dissolve the Initiator**:\n   - Dissolve potassium persulfate (KPS) or ammonium persulfate (APS) in water (0.1–1 wt% relative to total monomer weight) and add it to the reaction mixture.\n2. **Thermal or UV Initiation**:\n   - For thermal initiation: Heat the reaction mixture to around 60–70°C (depending on the decomposition temperature of the initiator). This step will generate radicals and start the polymerization.\n   - For photoinitiation: If integrating UV-sensitive initiators like Irgacure 2959, expose the solution to UV light to initiate free-radical formation.\n\n#### 3.4 Reaction Time and Stirring\n- Allow the reaction to proceed for 4–6 hours under constant stirring at the set temperature. Monitor viscosity changes during the reaction to observe polymer growth.\n\n#### 3.5 Quenching the Reaction\n- After the reaction is complete, cool the solution to room temperature and quench by diluting with additional water or by cooling rapidly. Note: The polymer may precipitate depending on its solubility.\n\n---\n\n### Step 4: Purification of the Hydrophilic Polymer\n1. **Precipitation**:\n   - If the polymer is water-miscible, precipitate the polymer by pouring the reaction mixture into a non-solvent (e.g., acetone or ethanol) under stirring.\n   - Filter and wash with the same non-solvent to remove unreacted monomers or side products.\n2. **Dialysis (optional)**:\n   - For completely dissolvable hydrophilic polymers, purify by dialysis using a membrane with an appropriate molecular weight cutoff to remove impurities.\n3. **Drying**:\n   - Dry the purified polymer under vacuum at 40–50°C to avoid decomposition of functional groups, especially the sulfonic acid group of AMPS.\n\n---\n\n### Step 5: Characterization of the Prepared Hydrophilic Polymer\n1. **Fourier-Transform Infrared Spectroscopy (FTIR)**:\n   - Confirm the incorporation of AMPS by detecting characteristic peaks such as sulfonic acid (S=O, ~1040–1080 cm⁻¹).\n2. **Nuclear Magnetic Resonance (NMR)**:\n   - Use ¹H-NMR and ¹³C-NMR to verify the presence of AMPS in the polymer matrix.\n3. **Gel Permeation Chromatography (GPC)**:\n   - Assess molecular weight distribution and verify chain transfer control (if applicable).\n4. **Hydrophilicity Testing**:\n   - Conduct water absorption studies or contact angle measurements to quantify the improvement in hydrophilicity.\n\n---\n\n### Key Notes and Precautions:\n1. **Storage of AMPS**: Ensure AMPS is stored in a cool, dry place, as it may clump or degrade when exposed to high humidity.\n2. **Side Reactions**: Minimize side reactions by maintaining proper pH and avoiding prolonged exposure to high temperatures during polymerization.\n3. **Safety**: Wear appropriate PPE, as persulfate initiators and AMPS can cause irritation upon contact.\n\nBy following the above preparation scheme, you will successfully synthesize a hydrophilic polymer with AMPS incorporated into the matrix, ensuring enhanced water affinity and desired physical properties. Let me know if you have any further questions!"
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+{
+  "design_question": "Using N-hydroxymethylacrylamide as a monomer, design a step-by-step polymerization process to create a hydrophilic polymer. Include details on the role of this molecule in the crosslinking structure.",
+  "design_answer": "Certainly! Let's carefully break the question down and provide a systematic, detailed explanation for the synthesis of a hydrophilic polymer utilizing **N-hydroxymethylacrylamide (NHMA)** as the monomer. We will also incorporate details on how NHMA contributes to the crosslinking structure.\n\n---\n\n### **Key Points**\n1. **N-hydroxymethylacrylamide (NHMA)** is a functional monomer that is hydrophilic due to its hydroxyl (-OH) and amide (-CONH2) groups. These enhance water solubility and hydrophilicity.\n2. NHMA possesses reactive hydroxymethyl (-CH2OH) groups that can participate in crosslinking through condensation reactions or covalent linkage.\n3. The goal is to polymerize NHMA into a hydrophilic polymer while exploiting the crosslinking ability of NHMA to enhance structural rigidity and hydrophilic properties.\n\nOur approach involves **radical polymerization**, a widely used method for synthesizing hydrophilic polymers, coupled with post-polymerization crosslinking to strengthen the structure.\n\n---\n\n### **Step-by-Step Polymerization Process Using NHMA**\n\n#### **Step 1: Preparation of Monomer Solution**\n1. **Reagents**: \n    - N-hydroxymethylacrylamide (NHMA) (monomer)\n    - Distilled deionized water (solvent, hydrophilic medium)\n    - Potassium persulfate (KPS) (initiator)\n    - N,N'-methylenebisacrylamide (MBA) (optional crosslinker, if enhanced structural rigidity is desired)\n2. **Steps**:\n    - Dissolve **NHMA** monomer (e.g., 10 g) in distilled deionized water (e.g., 50 mL) to form a clear solution. Stir gently to ensure uniform dissolution.\n    - If desired, add **N,N'-methylenebisacrylamide** (~0.2 g) as an external crosslinking agent. For this experiment, NHMA’s hydroxymethyl (-CH2OH) group will also act as an intrinsic crosslinker.\n    - Prepare a separate solution of **potassium persulfate** (1 g in 10 mL water).\n\n#### **Step 2: Creation of Reaction Medium**\n1. **Reaction Vessel**: A clean glass reactor or flask equipped with magnetic stirring, a nitrogen inlet, a thermometer, and a heating mantle.\n2. **Nitrogen Purging**:\n    - Purge the monomer solution with nitrogen gas (10-15 min) to eliminate dissolved oxygen, as oxygen inhibits radical polymerization.\n\n#### **Step 3: Initiation of Radical Polymerization**\n1. **Reaction Conditions**:\n    - **Temperature**: Heat the reactor to ~70°C (optimal for potassium persulfate decomposition).\n    - **pH**: NHMA is stable in slightly acidic to neutral conditions (pH ~6-7), allowing ideal polymerization.\n2. **Procedure**:\n    - Gradually add the potassium persulfate solution to the monomer solution under constant stirring.\n    - Maintain stirring to ensure uniform mixing of initiator with monomer.\n    - Monitor the viscosity of the solution; the viscosity will increase as polymerization progresses (indicative of polymer formation).\n\n#### **Step 4: Polymerization Monitoring**\n1. **Reaction Duration**: Allow the polymerization reaction to proceed for 3-4 hours at 70°C.\n2. **Observations**:\n    - Gel formation or solution thickening indicates increasing molecular weight.\n    - Hydrophilic properties can be tested by sampling the polymer and dissolving it in water.\n\n---\n\n### **Step 5: Crosslinking**\nThe hydroxymethyl (-CH2OH) group of NHMA provides intrinsic crosslinking functionality. During polymerization, NHMA monomers can react via condensation reactions (elimination of water) or covalent bonding between hydroxymethyl groups, forming crosslinked structures.\n\n1. **Heating Step**:\n    - Post-polymerization, heat the polymer solution gently (~90°C) to encourage crosslinking via the hydroxymethyl (-CH2OH) groups. This forms a stronger network.\n    - Optionally, increase pH slightly (~8-9 using sodium carbonate) to enhance hydroxymethyl reactivity.\n\n2. **Optional Crosslinker Addition**:\n    - If additional crosslinking agents like **MBA** were added earlier, ensure controlled heating and stirring to promote uniform crosslink formation.\n\n---\n\n### **Step 6: Polymer Purification**\n1. **Dilution and Washing**:\n    - Dilute the polymerized solution with excess water to enhance hydration and dissolve any unreacted NHMA monomers.\n    - Wash the polymer thoroughly with water or ethanol (if soluble contaminants exist) to remove residual chemicals (e.g., initiator, unreacted monomers).\n2. **Precipitation**:\n    - Precipitate the polymer by adding it to a non-solvent (e.g., acetone or ethanol) if the polymer is insoluble in these solvents.\n3. **Drying**:\n    - Wash the polymer further and air dry it at room temperature or under mild vacuum at a slightly elevated temperature (~40-50°C).\n\n---\n\n### **Step 7: Characterization**\nTo confirm successful polymerization and crosslinking:\n1. **Solubility Test**: Evaluate the hydrophilicity of the polymer by testing its solubility in water.\n2. **FTIR Analysis**:\n    - Validate the presence of hydroxyl (-OH) and amide (-CONH2) functional groups, as well as evidence of crosslinking.\n3. **Thermal Analysis**: \n    - Differential Scanning Calorimetry (DSC) or Thermogravimetric Analysis (TGA) can confirm structural stability and crosslinking density.\n\n---\n\n### **Role of NHMA in Crosslinking**\n1. The hydroxymethyl (-CH2OH) group in NHMA acts as an intrinsic crosslinking site. During polymerization, adjacent NHMA units can form covalent or hydrogen bonds between their hydroxymethyl groups.\n2. Such crosslinking enhances the polymer's structural integrity, reduces solubility (in excessive crosslinking cases), and contributes to a three-dimensional network that retains high hydrophilicity due to remaining hydroxyl and amide groups.\n\n---\n\n### **Conclusion**\nBy this step-by-step approach, students can synthesize a hydrophilic polymer using NHMA while understanding its dual role as a monomer and a crosslinking agent. Following systematic laboratory practices—careful control over reaction conditions, monomer ratios, and crosslinking—ensures reproducibility and successful polymer generation.\n\nIf any step requires clarification, feel free to ask!"
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+{
+  "design_question": "Describe the role of polysorbate in modifying a polymer to enhance its hydrophilicity and propose a method for incorporating it into a polyurethane-based prepolymer system.",
+  "design_answer": "Certainly! Let us break down your question systematically and address it in detail so that you can understand the role of polysorbate in enhancing polymer hydrophilicity and learn how to successfully incorporate it into a polyurethane-based prepolymer system.\n\n---\n\n### **Question Analysis and Key Points**\nYour question focuses on:\n1. **The role of polysorbate** in modifying a polymer to enhance hydrophilicity. Polysorbates are widely used non-ionic surfactants with amphiphilic properties, which can improve the hydrophilicity of a polymer system.\n2. **A method for incorporating polysorbate into a polyurethane (PU)-based prepolymer system**, which means an experimental approach to physically or chemically integrate polysorbate into the polymer during synthesis.\n\n---\n\n### **Step 1: Role of Polysorbate in Enhancing Hydrophilicity**\n**Polysorbate (e.g., Polysorbate-20, Polysorbate-80)** is a surfactant containing hydrophilic polyoxyethylene groups and hydrophobic fatty acid ester groups. These characteristics allow polysorbates to interact with both hydrophilic and hydrophobic components in polymer matrices. Here is its specific role in enhancing polymer hydrophilicity:\n\n1. **Introduction of Hydrophilic Groups:** The polyoxyethylene moieties (-CH₂CH₂O-) in polysorbate are highly hydrophilic and can interact with water or other polar environments. Incorporating polysorbate into a polymer matrix adds functional groups capable of forming hydrogen bonds with water, thereby increasing the polymer's affinity for water (hydrophilicity).\n   \n2. **Improved Surface Properties:** Polysorbate tends to migrate toward the polymer surface, where its hydrophilic groups can improve wettability and create a water-compatible outer layer. This effect is particularly desirable in biomedical applications (hydrogels, coatings) where contact with aqueous media is required.\n\n3. **Compatibility with Polyurethane Systems:** Polysorbates are miscible with polyurethane prepolymers and can be covalently or physically incorporated during synthesis without significantly disturbing the polymer's mechanical properties.\n\n---\n\n### **Step 2: Proposed Method for Incorporating Polysorbate into a Polyurethane-Based Prepolymer System**\n\nTo systematically incorporate polysorbate into a polyurethane-based system, here is a detailed preparative scheme:\n\n#### Overview of the Process:\nIn polyurethane synthesis, polymers are typically prepared by the reaction between a diisocyanate and a polyol in the presence of catalysts. Polysorbate can be incorporated **either as a hydrophilic polyol** or as an additive blended into the polymer matrix.\n\n---\n\n### **Experimental Scheme – Incorporation of Polysorbate**\n\n#### **Materials Required:**\n1. **Polyisocyanate:** e.g., methylene diphenyl diisocyanate (MDI) or toluene diisocyanate (TDI).\n2. **Polyols:** A conventional polyether or polyester polyol (base polyol for polyurethane synthesis).\n3. **Polysorbate (e.g., Polysorbate-20 or Polysorbate-80):** To introduce hydrophilicity into the polymer.\n4. **Catalyst:** Dibutyltin dilaurate (DBTL) or other organotin catalysts to accelerate the reaction.\n5. **Solvent (if required):** Tetrahydrofuran (THF) or dimethylformamide (DMF) as the reaction medium.\n6. **Chain Extender or Crosslinker (Optional):** Such as ethylene glycol or 1,4-butanediol, to enhance polymer properties.\n\n---\n\n#### **Step 1: Preparation of the Polyurethane Prepolymer**\n1. **Set-Up:**\n   - Use a round-bottom flask equipped with a mechanical stirrer, thermometer, and nitrogen inlet to prevent moisture contamination.\n   - Add the required polyisocyanate (e.g., MDI) and polyol in a molar ratio (usually 2:1 for diisocyanate to polyol).\n\n2. **Reaction Conditions:**\n   - Carry out the reaction at 70–80 °C under a nitrogen atmosphere.\n   - Stir the mixture until the reaction is complete (typically 1–2 hours), as indicated by the disappearance of the NCO absorption peak in IR spectroscopy (~2270 cm⁻¹).\n\n---\n\n#### **Step 2: Incorporation of Polysorbate**\n1. **Determine the Amount of Polysorbate:**\n   - To enhance hydrophilicity without sacrificing mechanical integrity, polysorbate can replace 5–20 wt% of the primary polyol used in the synthesis.\n   - Example: For 50 g of a polyol, incorporate 5–10 g of polysorbate.\n\n2. **Blend Polysorbate:**\n   - Add the pre-determined quantity of polysorbate slowly into the prepolymer mixture prepared in Step 1 while stirring at 70–75 °C.\n   - Ensure homogeneous mixing for approximately 30 minutes. The hydrophilic polyoxyethylene groups in the polysorbate will interact with the polyurethane network.\n\n---\n\n#### **Step 3: Chain Extension and Crosslinking**\n1. **Introduce a Chain Extender:**\n   - Add a small-molecule chain extender (e.g., ethylene glycol or 1,4-butanediol) to react with any remaining NCO groups in the prepolymer. This step increases molecular weight and forms a crosslinked polymer network.\n\n2. **Reaction Conditions:**\n   - Maintain the temperature at 70–80 °C for an additional 1–2 hours under stirring.\n   - Monitor the reaction by tracking the disappearance of the NCO group in IR spectroscopy.\n\n---\n\n#### **Step 4: Cure the Polymer**\n1. Allow the polymer to cool and set in a mold or solution-cast it, depending on the application.\n2. If a solvent was used (e.g., THF), remove the solvent by evaporation or precipitation in non-solvent (e.g., methanol).\n\n---\n\n### **Key Reaction Notes:**\n1. **Polysorbate Stability:** Ensure polysorbate is compatible at reaction temperatures. Overheating may degrade the polyoxyethylene chain, reducing effectiveness.\n2. **Optimize Ratios:** Excess polysorbate can weaken the mechanical properties of the polymer network (e.g., tensile strength).\n3. **Hydrophilic Balance:** The amount of polysorbate directly affects water uptake/swelling of the polymer. Optimize based on desired application (e.g., biomedical hydrogels or coatings).\n\n---\n\n### **Expected Results and Benefits**\n1. **Enhanced Hydrophilicity:** The incorporation of polysorbate introduces polyoxyethylene chains that significantly increase the water affinity of the polyurethane.\n2. **Improved Wettability:** The polymer surface becomes more hydrophilic, which can be confirmed using contact angle measurements (decreased water contact angle).\n3. **Versatility:** The modified polymer is suitable for use in water-compatible applications, such as drug delivery systems, tissue engineering scaffolds, or anti-fouling coatings.\n\n---\n\n### **Conclusion**\nThrough the experimental strategy outlined above, polysorbate can be successfully incorporated into a polyurethane-based prepolymer system, enhancing its hydrophilicity while maintaining structural and mechanical integrity. By optimizing polysorbate content during prepolymer synthesis, you can fine-tune the properties of your hydrophilic polymer for specific applications."
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+{
+  "design_question": "Design an experimental procedure to use '丙烯酰胺基-叔丁基磺酸钾盐' in the preparation of a hydrophilic polymer. Include details on how this molecule contributes to the overall hydrophilicity enhancement.",
+  "design_answer": "Certainly! Thank you for bringing up this intriguing question regarding the use of '丙烯酰胺基-叔丁基磺酸钾盐' (potassium acrylamide-based tert-butyl sulfonate) in the synthesis of a hydrophilic polymer. This molecule, with its distinctive structural design, has great potential for enhancing hydrophilicity due to the strong ionic character of the sulfonate group and the amide functionalities. Let us approach this systematically.\n\n---\n\n### Key Points Analysis\n1. **Objective**: Develop an experimental procedure to synthesize a hydrophilic polymer using '丙烯酰胺基-叔丁基磺酸钾盐.'\n2. **Hydrophilicity Contributions from the Monomer**:\n   - **Amide Functional Groups**: Promote hydrogen bonding with water molecules.\n   - **Sulfonate Group (-SO₃⁻)**: Strongly ionic and contributes significantly to water solubility and electrostatic interactions with water.\n3. **Synthetic Approach**: Design a polymerization scheme using this monomer, likely via free radical polymerization due to the presence of the acrylamide functional group. Consider supplemental monomers for copolymer formation if further structural or functional tuning is desired.\n\n---\n\n### Detailed and Systematic Experimental Procedure: Free Radical Polymerization\n\n#### 1. **Materials and Equipment**\n   - **Key Monomer**: 丙烯酰胺基-叔丁基磺酸钾盐 (provided by student).\n   - **Initiator**: Potassium persulfate (K₂S₂O₈) for aqueous polymerization or azobisisobutyronitrile (AIBN) for organic solvent-based polymerization.\n   - **Crosslinker**: N,N'-methylenebisacrylamide (to create hydrophilic gels, optional).\n   - **Solvent**: Deionized water (preferred for hydrophilic polymerization, unless the monomer requires organic solvents like dimethyl sulfoxide (DMSO)).\n   - **pH Adjusting Agent**: Dilute sodium hydroxide or sulfuric acid.\n   - **Nitrogen Gas**: For purge to remove oxygen during the reaction.\n   - Additional support equipment: Magnetic stirrer, reaction vessel with lid, UV/IR lamp (if photopolymerization is chosen), thermo-regulated water bath (for controlled temperature).\n\n---\n\n#### 2. **Experimental Design**\n\n##### **Step 1: Reaction Setup**\n   - Prepare a reaction vessel and ensure it is clean and oxygen-free.\n   - Add deionized water (50–100 mL per gram of monomer) to the flask as the solvent. Adjust parameters depending on required polymer concentration.\n\n##### **Step 2: Monomer Preparation**\n   - Accurately weigh the monomer: typically, 0.5–2 g of 丙烯酰胺基-叔丁基磺酸钾盐 depending on desired polymer yield.\n   - Dissolve the monomer in the solvent under constant stirring to ensure complete dissolution. The strong ionic nature will typically allow for easy solubility in water.\n\n##### **Step 3: Initiator Addition**\n   - Prepare the initiator solution: Dissolve an appropriate amount of potassium persulfate (~0.01–0.1 g per gram of monomer) in deionized water.\n   - Add the initiator solution dropwise to the reaction solution under stirring to ensure uniform distribution.\n\n##### **Step 4: pH Adjustment (Optional based on monomer chemistry)**\n   - If necessary, adjust the pH of the reaction to optimize polymerization kinetics. The optimal pH for acrylamide-based systems is typically neutral to slightly acidic (pH 6–7). Use dilute NaOH or HCl to achieve this.\n\n##### **Step 5: Oxygen Purge**\n   - Purge the system with nitrogen gas for 10–15 minutes. Oxygen can inhibit free radical polymerization reactions.\n\n---\n\n##### **Step 6: Reaction Conditions**\n   - **Temperatures**: 60–75°C for potassium persulfate, or ~65°C for AIBN if using organic solvents.\n   - Stirring Rate: Approximately 300–500 rpm for homogeneous mixing.\n   - Reaction Duration: 4–6 hours, or until polymerization is complete (monitor viscosity or turbidity increases).\n\n##### **Step 7: Crosslinking (Optional)**\n   - If forming crosslinked hydrogels, add N,N'-methylenebisacrylamide (~0.1–0.5% of total monomer mass) during the reaction. Ensure thorough mixing.\n\n---\n\n##### **Step 8: Polymer Purification**\n   - After completion of polymerization, remove non-reacted monomers and impurities via dialysis or repeated washing with deionized water.\n   - To precipitate and isolate the polymer, perform solvent exchange (e.g., precipitate in ethanol or acetone if needed).\n\n---\n\n#### 3. **Characterization of the Synthesized Polymer**\n   - **Hydrophilicity Testing**: Measure water contact angle of polymer films to confirm enhanced hydrophilicity.\n   - **Molecular Weight Analysis**: Conduct gel permeation chromatography (GPC).\n   - **Functional Group Verification**: FTIR spectroscopy to confirm retention of sulfonate and amide groups.\n   - **Thermal Stability**: Perform thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC).\n\n---\n\n### Hydrophilicity Enhancement via 丙烯酰胺基-叔丁基磺酸钾盐\nThe molecule provides hydrophilicity primarily through:\n1. **Amide Groups**: Contribute to hydrogen bonding, increasing water affinity.\n2. **Sulfonate Ionic Groups**: Strong electrostatic interactions with water molecules, making the polymer highly water-absorptive and hydrophilic.\n\nDepending on the application, this polymer can be ideal for water-retentive membranes, superabsorbent hydrogels, or coatings for biomedical devices.\n\n---\n\n### Conclusion\nBy following the above systematic procedure, students can successfully synthesize the hydrophilic polymer using 丙烯酰胺基-叔丁基磺酸钾盐. The detailed stepwise account ensures the experiment's reproducibility and facilitates the understanding of key mechanisms involved in hydrophilicity enhancement. Let me know if you need any additional clarification or adjustments for specific applications!"
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+  "design_question": "Explain how you would incorporate 'acryloyloxyethyltrimethylammonium chloride' into a polymer backbone to introduce hydrophilic properties, and describe the subsequent steps required to prepare the final polymer material.",
+  "design_answer": "Absolutely, let us systematically analyze and address your question. To incorporate the hydrophilic monomer **acryloyloxyethyltrimethylammonium chloride** (AETMAC) into a polymer backbone and achieve a hydrophilic polymer while meeting your needs for clarity and practicality in the laboratory, we will need to design a controlled polymerization experiment. Here's how we proceed:\n\n---\n\n### Step 1: Analyze the Problem\n1. **Key Objective:** Incorporating the hydrophilic monomer **AETMAC** into the polymer backbone to impart hydrophilic properties.\n2. **Suitable Polymerization Method:** Since AETMAC contains a polymerizable acrylate group (-C=C-), it can undergo radical polymerization with other monomers. **Solution polymerization** or **emulsion polymerization** are commonly used methods for water-soluble hydrophilic polymers.\n3. **Polymer Design:** We can create a homopolymer (all AETMAC polymerized together) or a copolymer (AETMAC polymerized with other monomers like acrylamide or acrylic acid).\n\n---\n\n### Step 2: Experimental Preparation Scheme\nBelow is the detailed synthesis protocol with reagents, reaction conditions, and procedural steps to guide you through laboratory implementation.\n\n---\n\n#### **Preparation Method: Radical Copolymerization**\n\n##### **Materials and Chemicals Required:**\n1. **Monomers:**\n   - **Acryloyloxyethyltrimethylammonium chloride (AETMAC):** Hydrophilic monomer.\n   - **Optional co-monomer (e.g., acrylamide or acrylic acid):** Enhances other physical properties such as viscosity and mechanical strength.\n2. **Solvent:**\n   - **Deionized water (or a water/ethanol mixture):** Ideal solvent for water-soluble hydrophilic polymers.\n3. **Initiator:**\n   - **Ammonium persulfate (APS):** A radical initiator for water-based reactions.\n4. **Crosslinker (optional):**\n   - For a lightly crosslinked polymer, add **N,N'-methylene bisacrylamide** in small quantities.\n\n##### **Procedure:**\n\n**Step 1: Preparation of the Reaction Solution**\n1. **Dissolve Monomers:** In an Erlenmeyer flask or a reaction vessel, dissolve the desired amount of **AETMAC** (typically 0.5–1.0 mol equivalent relative to total monomers) in **deionized water**.\n2. **Add Optional Co-monomer:** For a copolymer, weigh and add the co-monomer to the solution (e.g., acrylamide in 1:1 molar ratio with AETMAC or differing ratios to tune properties).\n3. **Maintain Neutral pH:** Adjust the pH of the solution to 6–7 using NaOH or HCl as needed to optimize the solubility and polymerization kinetics.\n4. **Introduce Crosslinker:** If desired, dissolve **N,N'-methylene bisacrylamide** (typically ≤1 mol% of total monomers) for partial crosslinking.\n\n**Step 2: Dissolve Polymerization Initiator**\n1. **Prepare Initiator Solution Separately:** Dissolve **ammonium persulfate (APS)** in deionized water (e.g., 0.5–1.0 wt% relative to total monomers).\n2. **Keep Initiator Fresh:** Only add APS to the reaction mixture immediately before polymerization to avoid premature initiation.\n\n**Step 3: Polymerization Reaction**\n1. **Degas the Solution:** Oxygen inhibits radical polymerization, so sparge the monomer solution with nitrogen gas for 20–30 minutes to remove dissolved oxygen.\n2. **Mix Polymerization Components:** Gradually add the APS solution to the monomer under stirring.\n3. **Control Temperature:** Increase the reaction temperature to 50–70°C to initiate radical polymerization. Maintain the solution at this temperature for 4–6 hours with continuous stirring.\n4. **Monitor Viscosity Change:** As the polymerization occurs, the viscosity of the solution will increase. Ensure the reaction remains homogeneous by adjusting stirring speed if necessary.\n\n---\n\n**Step 4: Purification of the Polymer**\n1. **Precipitation (Optional):** If the final polymer is soluble but needs further purification, precipitate the polymer by dripping the mixture into a nonsolvent like cold methanol while stirring.\n2. **Dialysis:** For water-soluble polymers, dialyze the reaction mixture against deionized water to remove unreacted monomers, impurities, and low molecular weight byproducts.\n3. **Drying:** Freeze-dry or dry the purified product in a vacuum oven at ≤40°C to preserve its hydrophilic qualities.\n\n**Step 5: Characterization**\n1. **Molecular Weight:** Use gel permeation chromatography (GPC) or viscometry to analyze the molecular weight distribution of the final polymer.\n2. **Hydrophilicity Testing:** Test surface hydrophilicity by measuring the water contact angle or conducting swelling studies in aqueous media.\n3. **FTIR:** Confirm the presence of characteristic functional groups (such as quaternary ammonium peaks) to ensure AETMAC integration into the polymer.\n\n---\n\n### Step 3: Notes and Reaction Tips\n1. **Reagent Ratios:** Adjust the ratio of **AETMAC** to co-monomers depending on the desired hydrophilicity and polymer properties. Higher AETMAC content results in greater hydrophilicity.\n2. **Safety Considerations:** AETMAC is generally stable but handle radical initiators like APS with care due to their oxidative nature.\n3. **Reaction Optimization:** Perform small-scale preliminary reactions to optimize reagent concentrations and polymerization conditions before scaling up.\n\n---\n\nThis systematic protocol incorporates **AETMAC** into the polymer backbone and enhances hydrophilicity. By following these steps, you should be able to successfully synthesize hydrophilic polymers suitable for various applications, such as water treatment, biomedical materials, or surface modification.\n\nLet me know if you have specific concerns about polymer design or application!"
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+  "design_question": "Given the molecule 'methoxy polyethylene glycol acrylate', outline a detailed experimental procedure for its use in forming an amine-terminated intermediate that can be further modified to enhance the hydrophilicity of a polymer material.",
+  "design_answer": "To address your question regarding the preparation of an amine-terminated intermediate from the molecule **methoxy polyethylene glycol acrylate (MPEG-A)**, I will design a detailed experimental procedure. By following these steps systematically, we can achieve the formation of the amine-functionalized intermediate, which can further be used for enhancing the hydrophilicity of a polymer material. Let us first analyze and break down the problem:\n\n---\n\n### **1. Question Analysis and Key Points**\n- **Molecule of focus:** Methoxy polyethylene glycol acrylate (MPEG-A). This molecule contains:\n  - A polyethylene glycol (PEG) segment, which imparts inherent hydrophilicity.\n  - A methoxy group (-OCH3) at one terminal, providing end termination and stability.\n  - An acrylate functional group (-CH=CHCO-) at the other end, which is reactive and can be used for polymer synthesis or further functionalization.\n\n- **Objective:** Synthesize an **amine-terminated intermediate** starting from MPEG-A, as a precursor to modify and enhance the hydrophilicity of polymer materials.\n  \n- **General Approach:** This involves modifying the acrylate group of MPEG-A into an amine-functionalized group. Acrylate groups are highly reactive and can undergo nucleophilic addition reactions with an appropriate amine-containing reagent, forming an amine-functionalized product.\n\n---\n\n### **2. Detailed Experimental Procedure**\n\nBelow, I outline a step-by-step preparation of the amine-terminated intermediate **methoxy polyethylene glycol amine (MPEG-NH2):**\n\n---\n\n#### **Step 1: Materials and Reagents**\n- **Methoxy polyethylene glycol acrylate (MPEG-A)** (molecular weight tuned—commonly ~500 to 4000 Da, depending on the desired flexibility/hydrophilicity).\n- **Ethanolamine** or **diethanolamine** (nucleophilic amine to react with the acrylate group).\n- **Solvent:** Tetrahydrofuran (THF), anhydrous (if required, dimethylformamide (DMF) can also be used as an alternative polar aprotic solvent).\n- **Catalyst:** Triethylamine (TEA) to optimize the reaction by neutralizing side-products (optional, depending on the conditions).\n- **Purification materials:** Silica gel, rotary evaporator.\n- **Nitrogen or Argon:** For inert atmosphere if necessary.\n\n---\n\n#### **Step 2: Reaction Setup**\n\n- Prepare a **dry round-bottom flask** equipped with a magnetic stir bar.\n- If needed, ensure the reaction is conducted under an **inert atmosphere** (e.g., by purging with nitrogen) to avoid contamination or oxidation.\n\n---\n\n#### **Step 3: Reaction Mechanism**\n\nThe functionalization occurs via **Michael addition**, where the nucleophilic nitrogen in ethanolamine or diethanolamine attacks the electrophilic β-carbon of the acrylate group in MPEG-A, resulting in the formation of an amine-functionalized product.\n\n1. **Reagent Ratios**: \n   - For each mole of MPEG-A acrylate, use 1.2–1.5 moles of ethanolamine to ensure complete reaction (the slight excess helps drive the reaction to completion).\n   - TEA as a catalyst can be added in catalytic quantities (e.g., ~5 mol% relative to MPEG-A).\n\n---\n\n#### **Step 4: Reaction Conditions**\n1. Dissolve **methoxy polyethylene glycol acrylate (MPEG-A)** in an anhydrous solvent, such as THF or DMF, at a concentration of ~10 wt%.\n2. Gradually add ethanolamine (1.2–1.5 eq.) dropwise to the solution under constant stirring.\n3. Maintain the reaction temperature at **50–60°C** for 6–12 hours. The temperature facilitates the nucleophilic attack while avoiding product degradation.\n4. Monitor the reaction progress via **thin-layer chromatography (TLC)** or nuclear magnetic resonance (NMR) by observing the disappearance of the acrylate proton signals (typically ~6 ppm in NMR).\n\n---\n\n#### **Step 5: Quenching and Work-Up**\n\n1. After the reaction is complete, cool the mixture to room temperature.\n2. If necessary, neutralize excess ethanolamine by adding a small amount of dilute HCl, followed by washing with water.\n3. Evaporate the solvent (e.g., THF) under reduced pressure using a rotary evaporator.\n4. Purify the product via **column chromatography** if needed (silica gel with a polar eluent such as ethyl acetate:hexane or methanol:chloroform).\n5. Characterize the final product (**MPEG-NH2**) using techniques such as:\n   - **1H NMR spectroscopy:** Confirm the disappearance of acrylate peaks and the appearance of amine-associated peaks.\n   - **Mass spectrometry (MS):** Verify the product mass matches the expected structure.\n\n---\n\n#### **Step 6: Storage**\n- Store the purified MPEG-NH2 in a desiccator or under inert conditions (argon environment) at low temperatures (e.g., 4°C) to avoid degradation.\n\n---\n\n### **3. Final Notes and Reaction Scheme**\n\n---\n\n1. **Reaction Scheme:**\n   Methoxy polyethylene glycol acrylate (MPEG-A) + Ethanolamine → Methoxy polyethylene glycol amine (MPEG-NH2)\n\n2. **Key Considerations:**\n   - Carefully control reaction conditions to prevent side reactions such as acrylate polymerization.\n   - Optimize ethanolamine quantity to achieve efficient Michael addition while minimizing unreacted starting material.\n\n3. **Potential Applications:**\n   Once the amine-terminated MPEG-NH2 is prepared, it can be further functionalized (e.g., via reaction with carboxylic acids, isocyanates, or other hydrophilic groups) to prepare advanced hydrophilic polymers with tailored properties.\n\n---\n\nThis method provides a clear and reliable route to prepare the required amine-functionalized intermediate for further use in hydrophilic polymer modification. If you have further questions, feel free to ask!"
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+{
+  "design_question": "Design an experiment using allyl ether sulfate to modify a polymer. Outline the quantities and conditions you would use, specifying the stages where allyl ether sulfate is added.",
+  "design_answer": "### Step-by-Step Answer:\n\nTo design an experimental procedure for modifying a polymer with **allyl ether sulfate (AES)**, we aim to introduce hydrophilic characteristics into the polymer structure. This modification typically exploits the reactive **allyl group (-CH2-CH=CH2)** and the **sulfate groups (-OSO3H)** present in AES. The following outlines the steps for a systematic approach.\n\n---\n\n### **Step 1: Analyze the Objective and Key Reaction Points**\n\n1. **Objective:** \n   Enhance a given polymer's hydrophilicity by chemically modifying it using allyl ether sulfate (AES). The hydrophilic sulfate groups can impart polar or ionic characteristics to otherwise relatively hydrophobic polymers, improving their performance in applications like water absorption, adhesion, or emulsification.\n   \n2. **Key Reaction Considerations:**\n   - Allyl ether sulfate is amphiphilic, with an electrophilic nature around its sulfate group and a reactive allyl functionality. It can undergo copolymerization or surface grafting via free-radical or other coupling mechanisms.\n   - Suitable initiation methods include **free-radical polymerization** (if the polymer has unsaturated bonds) or **grafting reactions** (if the polymer has active hydroxyl, amine, or carboxylic acid groups).\n   - Reaction conditions must preserve the integrity of the sulfate group while ensuring high efficiency in the allyl group’s reactivity.\n\n3. **Polymer Type:**\n   Let’s assume the polymer contains hydroxyl (-OH) or carboxyl (-COOH) functional groups. (This procedure can be adapted to other functionalized polymers as discussed below.)\n\n---\n\n### **Step 2: Design the Experimental Scheme**\n\n#### **Materials Required:**\n1. **Polymer substrate:** Assume we use Polyvinyl Alcohol (PVA) or a hydroxyl-functional acrylic polymer.\n2. **Allyl ether sulfate (AES):** Commercially available as a sodium salt (e.g., sodium allyl ether sulfate).\n3. **Initiator:** Water-soluble radical initiator (e.g., potassium persulfate (KPS) or ammonium persulfate (APS)) for graft polymerization.\n4. **Solvent:** Deionized water or a compatible aqueous medium.\n5. **Reaction aids:** Acid/base for pH adjustment (if needed).\n6. **Other reagents:** Sodium chloride (optional, to adjust ionic properties).\n\n#### **Step-by-Step Instructions:**\n\n---\n\n#### **Step 2.1: Polymer Dissolution (Pre-treatment)**\n1. **Weigh polymer substrate:**\n   - For example, PVA: 5 g. (This is scalable depending on intended application.)\n2. **Dissolve polymer:**\n   - Dissolve the weighed PVA in **deionized water** (~100 mL) under stirring and heating (80–90°C) until fully dissolved.\n\n---\n\n#### **Step 2.2: Preparation of the Allyl Ether Sulfate Solution**\n1. **Weigh allyl ether sulfate (AES):**\n   - Use a specific ratio with respect to the polymer (example: molar ratio of AES functional groups: polymer OH groups is 1.5:1). Calculate AES needed from its molecular weight and concentration:\n     - If using AES sodium salt, weigh approximately **6 g AES powder** (assuming polymer molecular weight of ~100 kDa for 5 g).\n2. **Dissolve AES in water or reaction medium:**\n   - Dissolve AES in **15 mL deionized water.**\n\n---\n\n#### **Step 2.3: Graft Polymerization Reaction**\n\n1. **Combine polymer solution and AES solution:**\n   - Lower the temperature of the dissolved PVA to 70°C.\n   - Add the prepared AES solution dropwise with continuous stirring at 70°C to ensure uniform interaction.\n\n2. **Add initiator (free-radical generation):**\n   - Dissolve **0.1 g potassium persulfate (KPS)** or ammonium persulfate (APS) in ~5 mL deionized water.\n   - Add the initiator to the reaction mixture in a dropwise fashion.\n   - Maintain stirring and heating at 70°C–75°C for 2–4 hours to allow sufficient time for graft polymerization.\n\n---\n\n#### **Step 2.4: pH Adjustment and Purification**\n1. **Adjust pH:** \n   - Check pH of the reaction mixture. If it becomes too acidic (due to sulfate group interactions), carefully neutralize to pH ~7 using a dilute sodium hydroxide (NaOH) solution.\n2. **Cool the mixture:** \n   - Allow the polymerized product to cool to room temperature.\n3. **Precipitate the product (if needed):**\n   - Add the mixture dropwise into excess 95% ethanol to precipitate the modified polymer. Filter and wash with ethanol to remove unreacted AES and other impurities.\n4. **Dry the polymer:**\n   - Dry the precipitated polymer in a vacuum oven at **50°C** for ~24 hours.\n\n---\n\n#### **Step 2.5: Characterization**\n1. Verify the successful modification of the polymer using:\n   - **Fourier Transform Infrared Spectroscopy (FTIR):** Look for characteristic sulfate peaks (~1220–1270 cm⁻¹).\n   - **Thermogravimetric Analysis (TGA):** Evaluate thermal stability changes.\n   - **Contact Angle Measurement/Aqueous Swelling Studies:** Assess hydrophilicity.\n   - **Elemental analysis or ion chromatography:** Confirm sulfate ion incorporation.\n\n---\n\n### **Quantities Chart for a 5 g Polymer Batch**\n\n| Component            | Quantity          |\n|----------------------|-------------------|\n| Polymer (PVA)        | 5 g              |\n| Deionized Water      | 100 mL (for polymer) + 15 mL (AES solution) |\n| Sodium Allyl Ether Sulfate (AES) | ~6 g |\n| Potassium Persulfate | 0.1 g            |\n| NaOH (for pH adjustment) | As required |\n| Ethanol (for precipitation)| ~200 mL     |\n\n---\n\n### **Step 3: Summarize Key Learnings**\n1. Allyl ether sulfate introduces hydrophilic sulfate groups into the polymer, enhancing water-solubility or swelling properties.\n2. Graft polymerization requires careful stoichiometric calculations, controlled heating, and correctly chosen initiators to balance efficiency and sulfate group integrity.\n3. Purification by ethanol precipitation and characterization methods validate the hydrophilic nature and structural integration of AES.\n\nThis detailed, stepwise procedure ensures a systematic approach to modifying polymers with hydrophilic allyl ether sulfate. Would you like me to clarify any specific step or reaction condition?"
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+{
+  "design_question": "When incorporating the molecule 2,4,7,9-tetramethyl-5-decyne-4,7-diol tetraethoxy ether into a reaction to synthesize a hydrophilic polymer, what parameters would you optimize (e.g., molar ratios, reaction time, or catalyst concentration) to achieve a controllable and uniform modification?",
+  "design_answer": "Certainly! Let us analyze and systematically address your question regarding the incorporation of **2,4,7,9-tetramethyl-5-decyne-4,7-diol tetraethoxy ether** into a reaction to synthesize a hydrophilic polymer. We will also explore the optimization of reaction parameters to ensure a controllable and uniform modification. This step-by-step response will cover the key aspects of the process, including molar ratios, reaction time, catalyst concentration, and other relevant factors important for successful synthesis.\n\n---\n\n### **Step 1: Analyze the structure and function of 2,4,7,9-tetramethyl-5-decyne-4,7-diol tetraethoxy ether**\nFirst, examine the role and features of the molecule you have provided:\n- **Structure**: The compound contains both **hydrophobic aliphatic chains** (methyl and decyne functionality) and **hydrophilic ethoxy ether groups** (-CH2-O-CH2). This makes it an amphiphilic molecule that can act as a surface-active agent or stabilizing moiety in polymer systems.\n- **Role in modification**: Its ethoxy ether groups provide a potential route for enhancing hydrophilicity when incorporated into a polymer chain. Adding this molecule could impart desirable water affinity and surface-wetting properties to the resulting polymer.\n- **Challenges**: The hydrophilic modification process must balance the distribution of hydrophilic and hydrophobic elements to ensure uniform and controlled integration.\n\n---\n\n### **Step 2: Key parameters to optimize the synthesis**\nTo achieve a controllable and uniform hydrophilic modification of the polymer while incorporating **2,4,7,9-tetramethyl-5-decyne-4,7-diol tetraethoxy ether**, the following reaction parameters require careful optimization:\n\n1. **Molar ratio of monomers/reagents**:\n   - The ratio between the polymerizable base monomer(s) (e.g., acrylic acid, acrylamide, or polyethylene glycol methacrylate) and the modifying agent (your provided molecule) must be carefully controlled.\n   - Excess modifying agent leads to phase separation or irregular incorporation, while insufficient amounts will not achieve the desired hydrophilicity.\n   - A typical starting molar ratio for functional monomer: modifying agent is **10:1 to 20:1**. Depending on solubility and reactivity, you may need to adjust the ratio slightly for optimal results.\n\n2. **Catalyst concentration**:\n   - If the synthesis involves radical polymerization, catalysts such as **azobisisobutyronitrile (AIBN)** or **persulfates** (e.g., potassium persulfate) are commonly used.\n   - Catalyst concentration typically ranges from **0.5-1 wt%** of the total monomer weight. Lower concentrations may result in incomplete reaction, while higher concentrations can lead to uncontrolled polymerization or the formation of side products.\n\n3. **Reaction solvent**:\n   - A polar solvent (e.g., water, dimethyl sulfoxide (DMSO), or ethanol) that solubilizes both the base monomers/oligomers and the hydrophilic ether moiety on the modifying agent is preferred.\n   - Water-ethanol mixtures are often an excellent choice for balancing hydrophilicity and hydrophobicity.\n\n4. **Reaction temperature**:\n   - Polymerization temperature significantly impacts the reaction rate and uniformity of incorporation.\n   - For free radical polymerization with AIBN, reaction temperatures of **60–80°C** are typical. For certain water-soluble initiators (e.g., ammonium persulfate), operating between **50–70°C** often yields better control.\n\n5. **Reaction time**:\n   - The polymerization time influences the degree of incorporation and completeness of hydrophilic modification.\n   - Start with a **2–4-hour reaction window**, monitoring the conversion and molar mass evolution (via gel permeation chromatography or FTIR if feasible). Extension beyond this point may result in undesirable crosslinking.\n\n6. **pH conditions**:\n   - If the polymerization involves ionizable groups, such as acrylic acid, pH control is necessary to ensure proper reaction. For example:\n     - A pH of **7–9** works well with neutral or mildly alkaline conditions to avoid premature ester or ether hydrolysis.\n\n---\n\n### **Step 3: Detailed synthesis scheme**\nUsing the above parameters, the following is a proposed experimental synthesis scheme:\n\n1. **Preparation of Reaction Mixture**:\n   - Dissolve the base monomer (e.g., acrylamide or acrylic acid) in a solvent mixture (e.g., water/ethanol).\n   - Add a measured amount of **2,4,7,9-tetramethyl-5-decyne-4,7-diol tetraethoxy ether** to the reaction flask, ensuring the molar ratio to the monomer lies between **10:1 to 20:1**.\n   - Stir the solution until fully homogenized.\n\n2. **Catalyst Addition**:\n   - Prepare a separate stock solution of the initiator (e.g., AIBN in ethanol or ammonium persulfate in water).\n   - Add this solution dropwise to the reaction flask under constant stirring, maintaining the final concentration of the catalyst at **0.8 wt%** of the total monomer weight.\n\n3. **Purging and Polymerization**:\n   - Purge the reaction flask with nitrogen or argon for **30 minutes** to eliminate oxygen, which can inhibit radical polymerization.\n   - Heat the reaction mixture to **70°C** while stirring continuously for **3 hours**.\n\n4. **Post-reaction Workup**:\n   - After the reaction, cool the mixture to room temperature.\n   - Precipitate the polymer by adding the reaction mixture into a large excess of a non-solvent (e.g., acetone or diethyl ether).\n   - Filter and wash the polymer thoroughly to remove unreacted components.\n   - Dry the resulting polymer in a vacuum oven at **40°C** overnight.\n\n---\n\n### **Step 4: Characterization and Evaluation**\nAfter synthesis, evaluate the polymer's hydrophilicity and modification uniformity:\n- **Contact angle measurements**: To determine surface hydrophilicity.\n- **FTIR spectroscopy**: To verify the incorporation of the ethoxy ether groups by identifying specific C-O-C stretch signals.\n- **Gel permeation chromatography (GPC)**: To assess the molecular weight distribution and uniformity.\n- **Water absorption/swelling studies**: To confirm hydrophilic property improvements.\n\n---\n\n### **Conclusion**\n- By carefully optimizing the molar ratios, catalyst concentration, reaction time, and temperature, you can achieve a controllable and uniform modification of the polymer with **2,4,7,9-tetramethyl-5-decyne-4,7-diol tetraethoxy ether**.\n- Employing rigorous characterization methods allows you to ensure the hydrophilic properties of the resulting polymer align with the intended application.\n\nIf you have further questions about adjustments to these parameters or additional characterization techniques, don't hesitate to ask!"
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+{
+  "design_question": "Describe the steps required to synthesize an anti-fog modifier using octavinyl polyhedral oligomeric silsesquioxane and a polyether containing epoxy propylene and epoxy ethylene chains. Highlight the key reaction conditions you would implement to ensure a successful addition reaction.",
+  "design_answer": "### Question Analysis and Key Points\nThe student's question concerns the synthesis of an anti-fog modifier using two distinct components: **octavinyl polyhedral oligomeric silsesquioxane (OV-POSS)** and **a polyether containing epoxy propylene and epoxy ethylene chains**. The goal is to carry out a chemical addition reaction that ensures the functionalization of OV-POSS with hydrophilic polyether chains, ultimately enhancing its hydrophilicity for anti-fogging applications.\n\nThe key reaction involves:\n1. **Addition of the epoxy groups in the polyether chain to the vinyl groups on OV-POSS** (likely through a thiol-ene click reaction, radical addition reaction, or Michael addition).\n2. Optimization of the reaction conditions to maximize yield and minimize side reactions.\n\nHere’s the detailed, step-by-step protocol for synthesizing the anti-fog modifier.\n\n---\n\n### Experimental Preparation Scheme\n\n#### Step 1: Materials and Reagents\n- **Octavinyl polyhedral oligomeric silsesquioxane (OV-POSS)**: The starting material containing vinyl groups.\n- **Polyether (with epoxy propylene and epoxy ethylene chains)**: Provides hydrophilic epoxy groups.\n- **Catalyst**: A platinum catalyst (e.g., Karstedt’s catalyst) is highly effective for facilitating the selective addition reaction between the vinyl and epoxy groups.\n- **Solvent**: Toluene or tetrahydrofuran (THF) as the reaction medium. Choose based on reagent compatibility.\n- **Inert gas (e.g., nitrogen)**: To create a non-oxidizing atmosphere and avoid side reactions.\n\n---\n\n#### Step 2: Experimental Setup and Safety Precautions\n1. **Equipment Setup**:\n   - Use a three-neck round-bottom flask equipped with:\n     - A magnetic stirrer.\n     - A reflux condenser (to avoid evaporation of volatile reactants).\n     - A septum for sampling.\n     - A thermometer to monitor reaction temperature.\n\n2. **Safety Precautions**:\n   - Ensure the reaction is conducted under an inert atmosphere (nitrogen or argon) to prevent polymer degradation or unwanted oxidation.\n   - Use protective gloves and lab goggles, as both OV-POSS and the polyether can irritate skin and mucous membranes.\n\n---\n\n#### Step 3: Reaction Mechanism\nThe vinyl groups on OV-POSS react with the epoxy groups in the polyether via a **hydrosilylation reaction** (if using silane derivatives) or alternatively a **radical addition reaction** under catalytic or thermal conditions. We’ll assume a platinum-catalyzed hydrosilylation pathway since it is highly specific for functionalizing vinyl groups.\n\n---\n\n#### Step 4: Detailed Procedure for Synthesis\n\n##### A. Catalyst Preparation\n1. Prepare an ultra-dilute solution of **Karstedt’s catalyst** (Pt catalyst) in dry toluene or THF. Typical concentration: **10–20 ppm of platinum** relative to the total reactants. \n2. Store the catalyst solution in an amber vial away from light.\n\n---\n\n##### B. Reactant Mixture\n1. **Weigh OV-POSS**: Scale approximately **2.5 g (around 3.4 mmol)** of OV-POSS into the reaction flask.\n2. **Prepare polyether solution**:\n   - Dissolve **polyether epoxy chains** in dry toluene (e.g., 10 mL, concentration ~20 wt%) for easy mixing.\n   - Add a slight excess of the polyether epoxy chains (e.g., **1.2:1 molar ratio relative to OV-POSS**) to ensure complete vinyl group conversion.\n3. Add the catalyst solution: Typically, add **0.1 mL of the Karstedt catalyst solution**.\n\n---\n\n##### C. Reaction Conditions\n1. **Inert Atmosphere**:\n   - Purge the flask with nitrogen gas for 10 minutes before heating the reaction mixture.\n   - Maintain a slight nitrogen flow throughout the reaction.\n\n2. **Heating**:\n   - Heat to **90–110°C** for **8–12 hours**. This temperature range is optimal for the platinum-catalyzed hydrosilylation of vinyl groups.\n   - Stir the solution continuously to ensure homogeneous mixing and avoid local over-heating.\n\n3. **Monitoring**:\n   - Monitor the reaction progress using **FTIR spectroscopy**. Disappearance of the vinyl C=C stretching band (~1600 cm⁻¹) and emergence of C-O-C bonds (~1100 cm⁻¹ for epoxide reaction products) confirm the successful addition.\n\n---\n\n#### Step 5: Purification\n1. Cool the reaction mixture to room temperature and dilute further with an inert solvent like THF.\n2. Precipitate the polymerized product by slowly dripping the reaction mixture into cold diethyl ether or methanol under stirring. This step removes unreacted polyether or low-molecular weight byproducts.\n3. Collect the precipitate via vacuum filtration and wash thoroughly with methanol.\n\n---\n\n#### Step 6: Characterization\n1. **Confirm the structure**:\n   - Use **NMR spectroscopy** (¹H and ¹³C):\n     - Verify the absence of vinyl peaks (~5–6 ppm for C=C in OV-POSS).\n     - Appearance of peaks corresponding to epoxy-derived functionalities (~3–4 ppm for CH-O).\n   - Perform **FTIR** spectroscopy to ensure conversion.\n2. **Molecular weight**:\n   - Measure the molecular weight using **Gel Permeation Chromatography (GPC)** to confirm successful grafting of polyether chains onto OV-POSS.\n3. **Hydrophilicity testing**:\n   - Conduct contact angle measurements on a thin coating of the synthesized polymer to confirm its anti-fogging properties.\n\n---\n\n### Notes on Optimizing Hydrophilicity\n1. **Polyether Selection**:\n   - Choose a polyether with a higher proportion of **ethylene oxide** vs. propylene oxide units to maximize hydrophilicity.\n2. **Epoxy-to-Vinyl Ratio**:\n   - An excess of polyether is recommended to ensure complete functionalization.\n3. **Reaction Time**:\n   - Extend reaction time if FTIR shows incomplete vinyl group conversion after 12 hours.\n\n---\n\n### Final Remarks\nBy following this systematic protocol, students should be able to prepare a hydrophilic anti-fog modifier successfully in the lab. The controlled functionalization of OV-POSS with hydrophilic polyether chains enhances its anti-fogging capabilities, making it a suitable candidate for optical, automotive, or coating applications. Always prioritize precise molar ratios, reaction temperature control, and inert conditions for optimal results!"
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diff --git a/task2/task2-qa/CN202180007560-╖└╬э═┐┴╧╫щ║╧╬я╝░╖└╬э═┐─д╥╘╝░╖└╬э╬я╞╖-╔ъ╟ы╣л┐к.json b/task2/task2-qa/CN202180007560-╖└╬э═┐┴╧╫щ║╧╬я╝░╖└╬э═┐─д╥╘╝░╖└╬э╬я╞╖-╔ъ╟ы╣л┐к.json
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+{
+  "design_question": "When incorporating silane derivatives containing an epoxy group and polyethylene glycol chains into a polymeric network, what factors would you consider to ensure optimal hydrophilicity? Include how 3-isocyanatopropyltrimethoxysilane can influence these factors.",
+  "design_answer": "To address your question regarding incorporating silane derivatives containing an epoxy group and polyethylene glycol (PEG) chains into a polymeric network to enhance hydrophilicity, let us systematically break it down step-by-step while considering all relevant factors, including the role of 3-isocyanatopropyltrimethoxysilane. Here's a detailed analysis and an experimental framework:\n\n---\n\n### **Step 1: Analyze the Question**\n- **Goal:** To enhance the hydrophilicity of a polymeric network using silane derivatives with epoxy and PEG chains.\n- **Key Consideration:** Silane chemistry, PEG hydrophilicity, crosslinking mechanisms, and surface characteristics of the polymer networks.\n- **Role of 3-Isocyanatopropyltrimethoxysilane:** A trifunctional silane compound with an isocyanate (-NCO) group for covalent bonding and trimethoxysilane (-Si(OCH3)3) groups for hydrolysis/condensation to form a siloxane network.\n\n---\n\n### **Step 2: Factors Influencing Hydrophilicity**\n1. **Incorporation of PEG Chains:**\n   - PEG is inherently hydrophilic due to its repeating ether oxygen atoms that interact with water molecules via hydrogen bonding.\n   - The molecular weight and chain length of PEG influence hydrophilicity. Higher molecular weight PEG derivatives yield better water affinity but can reduce crosslinking density.\n\n2. **Functionalization via Silane Derivatives:**\n   - Silane derivatives (such as those containing epoxy and PEG chains) can act as crosslinkers, imparting hydrophilicity while also ensuring compatibility with the polymer matrix.\n   - Hydrolysis and condensation reactions of silane moieties allow network formation, anchoring hydrophilic domains effectively into the polymer.\n\n3. **Role of Epoxy Groups:**\n   - Epoxy groups facilitate nucleophilic addition reactions with primary amines, alcohols, or thiols (present in the polymer matrix) to establish covalent bonds within the material.\n\n4. **Role of 3-Isocyanatopropyltrimethoxysilane:**\n   - The isocyanate group reacts with nucleophilic groups in the polymer (e.g., hydroxyl or amines) to form strong urethane bonds, ensuring anchoring.\n   - After attachment, the trimethoxysilane group undergoes hydrolysis (in the presence of water or moisture) into silanol groups (-SiOH), followed by condensation into polysiloxane bonds, leading to network integrity.\n\n5. **Hydrophobic/Hydrophilic Balance:**\n   - Proper balancing is required to ensure that the PEG hydrophilicity is not overshadowed by residual hydrophobic siloxane domains or other non-polar groups in the polymer.\n\n---\n\n### **Step 3: Experimental Preparation Scheme**\nThe following step-by-step synthesis procedure incorporates silane derivatives with epoxy and PEG chains for a hydrophilic polymeric network: \n\n#### **Materials:**\n- Silane derivative with an epoxy group and PEG chain (e.g., epoxy-PEG-silane).\n- 3-Isocyanatopropyltrimethoxysilane.\n- Polymer matrix with reactive groups (e.g., hydroxyl-terminated or amino-terminated polymer).\n- Solvent: Anhydrous toluene or ethanol, depending on the solubility of components.\n- Catalyst for silane hydrolysis/condensation, such as acetic acid or ammonium hydroxide (for pH control).\n- Water (controlled for hydrolysis of silane functionalities).\n\n---\n\n#### **Step 1: Functionalization with 3-Isocyanatopropyltrimethoxysilane**\n1. **Reaction Design**:\n   - React 3-isocyanatopropyltrimethoxysilane with the polymer's reactive groups (e.g., –OH or –NH2).\n   - Allow urethane bond formation (amine or hydroxyl group attacking the –NCO group).\n\n2. **Procedure**:\n   - Dissolve the polymer (5 mmol hydroxyl or amino groups) in 50 mL of anhydrous toluene under inert conditions (e.g., nitrogen).\n   - Add 3-isocyanatopropyltrimethoxysilane (5.5 mmol, slightly excess to ensure complete reaction) dropwise.\n   - Heat the solution to 50–60°C for 4–6 hours with continuous stirring to allow the nucleophilic reaction to occur.\n   - Confirm reaction completion using FTIR (disappearance of the isocyanate peak at ~2270 cm⁻¹ and appearance of urethane peaks ~1680 cm⁻¹).\n\n---\n\n#### **Step 2: Incorporation of Epoxy-PEG-Silane**\n1. **Reaction Design**:\n   - Incorporate the silane derivative with an epoxy-PEG group into the functionalized polymer network to introduce hydrophilic PEG domains.\n   - Utilize the trimethoxysilane groups for hydrolysis and condensation to form siloxane linkages.\n\n2. **Procedure**:\n   - Dissolve the functionalized polymer (from Step 1) in 50 mL of ethanol or a similar polar solvent.\n   - Add the epoxy-PEG-silane (molar ratio of PEG-silane to polymer hydroxyl/amine groups = 1:1).\n   - Add catalytic amounts of acetic acid (~0.1 mL) to the mixture to initiate silane hydrolysis at ambient temperature.\n   - Stir the solution at room temperature for 12–24 hours to allow for silane hydrolysis into silanol groups (-SiOH) and subsequent condensation into a stable network.\n   - Monitor the reaction via FTIR (appearance of Si–O–Si bonds at ~1100 cm⁻¹ and disappearance of Si–OCH3 peaks).\n\n---\n\n#### **Step 3: Network Formation and Curing**\n1. **Crosslinking Reaction**:\n   - To enhance network stability, cure the polymer in a humid environment, facilitating further condensation of silanol groups into polysiloxanes.\n   - Optional heat treatment (e.g., 70–100°C) may help accelerate curing without degrading the PEG components.\n\n2. **Post-treatment:**\n   - Wash the polymer network with ethanol and distilled water to remove residual unreacted components.\n   - Dry the polymer network under vacuum at 40–50°C to constant weight.\n\n---\n\n### **Step 4: Characterization**\n- Confirm the incorporation of PEG and silane derivatives using:\n  - **FTIR:** Characteristic peaks for PEG (C–O at ~1100 cm⁻¹), siloxanes (Si–O–Si at ~1100 cm⁻¹), and urethane groups (~1680 cm⁻¹).\n  - **NMR (¹H or ²⁹Si):** To detect polymer backbone modifications and silane species.\n  - **Contact Angle Measurements:** Assess surface hydrophilicity (values near or below 30° indicate high hydrophilicity).\n  - **Water Swelling Test:** Quantify the hydrophilic character by absorption/swelling behavior.\n\n---\n\n### **Conclusion**\nIncorporating silane derivatives containing epoxy and PEG chains into a polymeric network enhances hydrophilicity via PEG's water affinity and silane's functional versatility. 3-Isocyanatopropyltrimethoxysilane contributes by forming stable covalent linkages and integrating siloxane domains into the polymer. Precise control over reaction conditions (e.g., molar ratios, hydrolysis pH, and curing process) ensures optimal hydrophilicity and structural stability."
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diff --git a/task2/task2-qa/CN97126279-╙├╙┌╣╠╗п╗╖╤ї╩ў╓м╡─╕─╜°╡─╣╠╗п┤▀╗п╝┴-╔ъ╟ы╣л┐к.json b/task2/task2-qa/CN97126279-╙├╙┌╣╠╗п╗╖╤ї╩ў╓м╡─╕─╜°╡─╣╠╗п┤▀╗п╝┴-╔ъ╟ы╣л┐к.json
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+{
+  "design_question": "Describe the steps you would take to integrate imidazole into a formulation containing a nucleophilic addition product and an epoxy resin. How would you adjust the formulation to ensure proper functionality and hydrophilicity enhancement?",
+  "design_answer": "Certainly! Thank you for your thoughtful question. To proceed systematically and logically, let's work step by step through the integration of **imidazole** into your formulation to achieve functionality enhancement, hydrophilicity, and performance optimization. I will provide a detailed experimental preparation scheme as you requested.\n\n---\n\n### **Step 1: Analyze the Question and Key Points**\n1. **Components**: You are working with a **nucleophilic addition product, an epoxy resin, and imidazole**. These components suggest a formulation likely involving epoxy curing or modification.\n2. **Objective**: The goal is twofold:\n    - **To integrate imidazole into the epoxy resin system**, possibly as a curing agent or modifier.\n    - **To enhance hydrophilicity** of the polymer product, which may involve hydrophilic functional groups or further chemical grafting/modification.\n3. **Challenges**:\n    - Controlling reaction conditions to prevent over-curing or undesirable crosslinking.\n    - Balancing hydrophilicity addition with maintaining the physical and mechanical properties of the polymer.\n\n---\n\n### **Step 2: Experimental Preparation Scheme**\n\nHere is the detailed scheme for preparing a hydrophilic polymer based on epoxy resin, nucleophilic addition products, and imidazole integration:\n\n---\n\n#### **Step 2.1: Materials and Reagents**\n- **Epoxy Resin**: Typically, a diglycidyl ether of bisphenol A (DGEBA) or another suitable epoxy compound.\n- **Imidazole**: Used as a curing agent or nucleophilic catalyst.\n- **Hydrophilic Nucleophilic Addition Product**: Depending on the specific substrate, this could include polyols, amino alcohols, or carboxyl-functionalized compounds that react with epoxy groups.\n- **Solvent (if needed)**: Water-miscible solvents such as dimethylformamide (DMF) or ethanol to improve homogeneity.\n- **Optional Hydrophilic Modifiers**: Molecules like polyethylene glycol (PEG) or hydroxyl-/amine-functionalized compounds to boost hydrophilicity.\n\n---\n\n#### **Step 2.2: Reaction Scheme**\nWe will perform the synthesis in two stages: (a) Pre-functionalization of the epoxy resin with hydrophilic groups via nucleophilic addition, and (b) Imidazole integration.\n\n---\n\n### **Stage I: Pre-functionalization of Epoxy Resin**\nThe first step is to react the epoxy resin with the nucleophilic addition product to introduce hydrophilic functional groups. This process increases the water compatibility and polar character of the final polymer.\n\n1. **Reaction Setup**:\n   - Place the epoxy resin into a clean, dry reaction flask equipped with a mechanical stirrer, nitrogen inlet, and a temperature control system.\n   - Add a small amount of solvent (if the resin viscosity is high) to improve stirring.\n\n2. **Addition of Nucleophilic Addition Product**:\n   - Slowly add the hydrophilic nucleophilic addition product to the flask. \n   - Ratio: Maintain an **equimolar ratio of epoxide groups to nucleophilic functional groups** of your addition product. Adjust depending on whether you desire partial or full reaction (e.g., a 1:1 molar ratio for complete functionalization).\n\n3. **Reaction Conditions**:\n   - **Temperature**: Maintain between **50–80°C** to activate the epoxy rings without thermal degradation.\n   - **Time**: Reaction proceeds for **3–6 hours** under stirring, depending on reactivity.\n   - Monitor progress using Fourier-transform infrared spectroscopy (FTIR), looking for the disappearance of the epoxide band (~915 cm⁻¹).\n\n4. **Optional Purification**:\n   - If necessary, remove excess nucleophilic addition product via solvent washing or vacuum distillation.\n\n---\n\n### **Stage II: Integration of Imidazole**\nNext, we incorporate imidazole into the pre-functionalized epoxy system. Imidazole is a strong nucleophile and base, and in this context, it can act as both:\n- A curing agent to generate a crosslinked network.\n- A hydrophilicity enhancer due to its heterocyclic nature.\n\n1. **Reaction Setup**:\n   - Transfer the pre-functionalized epoxy resin (from Stage I) into a reaction flask.\n   - Add imidazole gradually under continuous stirring to ensure homogeneous mixing.\n\n2. **Molar Ratio**:\n   - The imidazole-to-epoxide ratio depends on its role in the formulation:\n     - If imidazole serves as the **sole curing agent**, a ratio of **0.1–0.2 moles of imidazole per mole of residual epoxide groups** is typically sufficient.\n     - If imidazole is used in synergy with other curing agents, the ratio might be lowered (~0.05 moles of imidazole per mole of epoxide groups).\n\n3. **Reaction Conditions**:\n   - **Temperature**: Heat the mixture to **100–150°C** to promote the reaction between imidazole and remaining epoxide groups.\n   - **Time**: Allow the reaction to proceed for **1–2 hours** under a nitrogen blanket to avoid moisture interference and epoxy degradation.\n   - Monitor progress by FTIR and Differential Scanning Calorimetry (DSC) to ensure curing is near completion.\n\n4. **Crosslinking and Hydrophilicity Enhancement**:\n   - Imidazole may initiate curing and simultaneously introduce hydrophilic amine groups into the polymer, due to its high polar functionality.\n   - Additional small hydrophilic compounds (e.g., low-molecular-weight PEG or amine-functionalized molecules) can be added at this stage if further hydrophilicity is desired.\n\n---\n\n### **Post-Reaction Processing**\n1. **Cool and Collect**:\n   - After curing or modification is complete, cool the system to room temperature.\n   - The product may precipitate as a solid or form a gel, depending on the degree of crosslinking.\n\n2. **Characterization**:\n   - Conduct characterization to confirm enhanced hydrophilicity:\n     - **Water Contact Angle Measurement**: Lower contact angles indicate improved hydrophilicity.\n     - **FTIR Analysis**: Verify the reduction of epoxide peaks and the appearance of imidazole-related peaks.\n     - **Solubility Test**: Evaluate water compatibility of the modified polymer.\n     - **Thermal Analysis (DSC/TGA)**: Ensure the thermal stability of the final polymer.\n\n3. **Final Adjustments**:\n   - If additional hydrophilicity is needed, post-polymerization grafting with hydrophilic groups (e.g., carboxylic acids, sulfonates) can be performed.\n\n---\n\n### **Experimental Notes and Tips**:\n- Ensure precise temperature and reactant control to avoid over-curing or epoxide ring scission.\n- Keep all solvents and reagents anhydrous to prevent side reactions with water.\n- The hydrophilicity of the final product should always be assessed relative to the application (e.g., biomedical coatings, hydrogels, etc.).\n\n---\n\n### Conclusion\nBy following this step-by-step methodology, you can successfully integrate imidazole into the epoxy-basded formulation and achieve hydrophilicity enhancement. This approach allows for systematic tuning of both the curing process and the hydrophilic properties of the final polymer.\n\nIf you have additional details about your nucleophilic addition product or desired applications, I’d be happy to refine these protocols even further. Good luck with your experiment, and let me know how it progresses!"
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+{
+  "design_question": "If plasma surface cleaning is required before applying the molecule VCN L1-B, explain the role and importance of the plasma cleaning process in ensuring effective hydrophilic modification of the polymer material.",
+  "design_answer": "Let's think through your question step by step to provide a thorough and detailed explanation of the role and importance of plasma surface cleaning before applying the molecule VCN L1-B as part of a hydrophilic polymer synthesis process. Throughout this process, I'll also explain its relevance to ensuring effective hydrophilic modification of the polymer material.\n\n---\n\n### Step 1: Analyze the Question and Summarize Key Points\nFrom your question, we need to focus on the following:\n1. **The role of plasma surface cleaning:** Why it is used as a preparatory step before applying VCN L1-B.\n2. **The importance of plasma surface cleaning in hydrophilic modification:** How it enhances the polymer surface's ability to undergo hydrophilic modification effectively.\n\nThese points suggest that the key issue is the preparation of the polymer surface to ensure optimal interaction or bonding with the hydrophilic molecule VCN L1-B for effective modification.\n\n---\n\n### Step 2: Answer the Question in Detail and Systematically\n\n#### **2.1. Overview of Plasma Cleaning in Surface Preparation**\nPlasma surface cleaning is a physical and chemical technique that uses a low-pressure gas plasma to modify the surface properties of materials. It is particularly effective for polymers because it:\n- Removes surface contaminants, such as oils, dust, organic residues, and weakly bound materials.\n- Physically activates the surface by introducing functional groups (e.g., hydroxyl -OH, carboxyl -COOH, or amine -NH2 groups) that improve surface reactivity.\n- Enhances the wettability and adhesion properties of the surface. This is critical for hydrophilic modifications.\n\nTypically, plasma cleaning is performed under vacuum conditions using a selected inert, oxygen, or argon gas. The plasma is generated by applying a high-frequency electric field, which ionizes the gas and creates a high-energy plasma environment.\n\n#### **2.2. Role of Plasma Surface Cleaning for VCN L1-B Application**\nBefore applying VCN L1-B to modify a polymer material for hydrophilicity, the plasma cleaning process plays several critical roles:\n\n1. **Surface Contaminant Removal:**\n   - Organic pollutants (e.g., oils or residual monomers) and atmospheric contaminants can block the binding sites on the polymer surface.\n   - Plasma cleaning removes these contaminants effectively, exposing a clean polymer surface for subsequent reactions with VCN L1-B.\n\n2. **Surface Activation:**\n   - Plasma treatment chemically activates the polymer surface by embedding hydrophilic functional groups (e.g., -OH or COOH), boosting reactivity with the functional groups on VCN L1-B.\n   - For example, certain polymers such as polypropylene or polyethylene that are inherently hydrophobic can be functionalized with oxygen-bearing groups during plasma treatment using oxygen plasma.\n\n3. **Improved Adhesion and Bonding:**\n   - The cleaning process improves molecular-level adhesion by creating an ideal interfacing environment. Hydrophilic molecules like VCN L1-B often require clean, active surfaces to anchor effectively through covalent or non-covalent interactions.\n   - A poorly prepared surface may result in weak or uneven attachment of VCN L1-B, drastically affecting the hydrophilic properties of the final product.\n\n4. **Even Distribution and Wettability Enhancement:**\n   - Plasma treatment increases surface energy, ensuring that VCN L1-B can spread and form a uniform coating on the polymer. This uniformity translates to consistent hydrophilic properties across the material surface.\n\n#### **2.3. Experimental Protocol for Plasma Cleaning**\nTo assist in successfully performing this step in the laboratory, let me outline a detailed experimental protocol for plasma surface cleaning before applying VCN L1-B:\n\n1. **Equipment Required:**\n   - Plasma cleaner (depending on lab availability, you might use low-pressure plasma or atmospheric-pressure plasma systems).\n   - Inert or reactive gas supply (e.g., Ar for inert cleaning, O₂ for oxidative cleaning).\n\n2. **Procedure:**\n   - **Step 1: Polymer Sample Placement:**\n     - Cut the polymer sample to the desired dimensions and ensure it is free from any visible macroscopic contaminants (e.g., dust or large particles). Place it in the plasma chamber.\n   - **Step 2: Chamber Evacuation:**\n     - Evacuate the chamber to a base pressure of 0.1–1 Torr to ensure minimal contamination during treatment.\n   - **Step 3: Gas Introduction:**\n     - Introduce the chosen plasma gas (e.g., oxygen gas for oxidative cleaning) at a steady flow rate. Maintain pressure in the range of ~0.2–0.5 Torr.\n   - **Step 4: Plasma Generation:**\n     - Activate the plasma by applying RF power (e.g., 13.56 MHz) at an appropriate power level (~50–200 W, depending on sample size and desired cleaning intensity).\n     - Treat the polymer surface for approximately 5–15 minutes. The exact time depends on the polymer type and the level of contamination.\n\n3. **Post-Treatment Verification:**\n   - After plasma cleaning, verify the surface modification using techniques such as:\n     - **Contact Angle Measurement:** Ensure the treated surface has improved wettability (lower contact angle indicates greater hydrophilicity).\n     - **Fourier Transform Infrared Spectroscopy (FTIR):** Detect newly formed oxygen-containing groups on the polymer.\n     - **Surface Energy Analysis:** Quantify the increase in surface energy due to plasma treatment.\n\n4. **Storage Before Application of VCN L1-B:**\n   - If VCN L1-B application is not immediate, store the cleaned polymer material in a vacuum or inert atmosphere. Exposure to air can result in contamination or aging of the activated surface.\n\n#### **2.4. Importance of Plasma Cleaning in Hydrophilic Modification**\nWithout plasma surface cleaning, the effectiveness of hydrophilic modification using VCN L1-B may be significantly compromised. Problems that could arise include:\n- Inconsistent or poor bonding of VCN L1-B to the polymer substrate.\n- Non-uniform distribution of hydrophilic properties across the polymer surface.\n- Reduced durability and stability of the hydrophilic coating in aqueous environments.\n\nIn contrast, by using plasma cleaning to prepare the polymer surface, the reaction kinetics between VCN L1-B and the surface are greatly enhanced. This step leads to a more robust hydrophilic layer with improved functionality and longevity, ensuring the desired performance of the hydrophilic polymer.\n\n---\n\n### Final Thoughts:\nPlasma surface cleaning is an indispensable preparatory step when producing hydrophilic polymers with VCN L1-B. Its role in removing contaminants, activating the polymer surface, and preparing the substrate for seamless interaction with the hydrophilic molecule is pivotal. By following the detailed procedure and understanding the science behind this process, you will ensure a successful outcome in hydrophilic polymer synthesis experiments in the lab."
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+{
+  "design_question": "Suggest a suitable polymerization strategy to cure a hydrophilic bisphenol A-based (meth)acrylate modification of a polymer, ensuring that its hydrophilic properties are preserved. Why would you choose this particular polymerization method?",
+  "design_answer": "Certainly! Let us carefully analyze the problem and provide a step-by-step explanation to help you understand the process and ensure successful implementation in the laboratory.\n\n---\n\n### Question Analysis:\n\nYou are seeking a suitable polymerization strategy to cure a *hydrophilic bisphenol A-based (meth)acrylate* while preserving its hydrophilic properties. The key aspects here are:\n\n1. **The monomer structure:** The bisphenol A-based (meth)acrylate likely includes both hydrophilic functional groups and acrylate/methacrylate moieties for polymerization.\n2. **Hydrophilicity preservation:** The polymerization method must avoid processes that could compromise the hydrophilic functional groups.\n3. **Polymerization approach:** The most appropriate strategy must ensure uniform curing with high efficiency to achieve the desired hydrophilic polymer.\n\nLet us now develop a detailed experimental scheme to address your request.\n\n---\n\n### Proposed Polymerization Strategy:\nThe most suitable approach for curing hydrophilic bisphenol A-based (meth)acrylates is **photopolymerization** via free radical initiation, specifically using UV light in the presence of a hydrophilic photoinitiator. This method ensures efficient curing under mild conditions, avoiding thermal degradation or reaction with hydrophilic functional groups.\n\n---\n\n### Step-by-Step Experimental Preparation Scheme:\n\n#### **Step 1: Materials and Reagents Selection**\n- **Monomer:** Hydrophilic bisphenol A-based (meth)acrylate.\n  - Verify the presence of hydrophilic functional groups such as hydroxyl (-OH) or ether (-C-O-C-) groups.\n  - Ensure the acrylate/methacrylate groups are available for free radical polymerization.\n- **Photoinitiator (PI):** A water-compatible, hydrophilic photoinitiator such as *Irgacure 2959* (2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone).\n  - This initiator is widely used in aqueous systems and is non-toxic.\n- **Diluent Solvent (if necessary):**\n  - If the bisphenol A derivative is highly viscous, use a hydrophilic solvent (e.g., ethanol, water, or a water-methanol mixture) to control viscosity.\n- **Other Additives:** Consider adding crosslinkers (e.g., ethylene glycol dimethacrylate) if a crosslinked polymer is required.\n\n---\n\n#### **Step 2: Preparing the Reaction Mixture**\n1. **Monomer Dissolution:**\n   - Dissolve the hydrophilic bisphenol A-based (meth)acrylate monomer in the chosen solvent if it is solid or viscous.\n   - Use a concentration of 10–50% monomer (w/v) depending on the desired polymer density.\n\n2. **Photoinitiator Incorporation:**\n   - Add the hydrophilic photoinitiator (e.g., Irgacure 2959) to the monomer solution.\n   - Typical photoinitiator concentrations range from 0.5% to 1.5% (w/w) relative to the total monomer weight.\n   - Ensure thorough mixing by stirring under moderate conditions.\n\n3. **Optional Additives:**\n   - If crosslinking is desired, add a small quantity of a bifunctional crosslinker (e.g., ethylene glycol dimethacrylate) at 1–5% molar concentration relative to the monomer.\n\n---\n\n#### **Step 3: Photopolymerization Process**\n1. **Sample Preparation:**\n   - Transfer the reaction mixture to a mold or substrate (e.g., a glass slide or petri dish).\n   - Ensure a uniform layer to enable consistent curing.\n\n2. **UV Light Exposure:**\n   - Use a UV lamp with a wavelength of 365 nm (appropriate for photoinitiator activation) and an intensity between 5–20 mW/cm².\n   - Cure the monomer mixture by exposing it to UV light for 10–20 minutes. The curing time varies based on layer thickness and photoinitiator concentration.\n\n3. **Environmental Control:**\n   - Maintain ambient temperature (20–25 °C) during polymerization to prevent thermal effects that could degrade hydrophilic functionalities.\n   - Exclude oxygen during polymerization (e.g., by purging with nitrogen gas) to avoid inhibition of free radical polymerization.\n\n---\n\n#### **Step 4: Post-Polymerization Handling**\n1. **Polymer Washing:**\n   - Wash the cured polymer with distilled water or ethanol to remove unreacted monomer or photoinitiator residues.\n   - This step ensures the final polymer is free of impurities and safe for application.\n\n2. **Drying:**\n   - Dry the polymer under vacuum or at room temperature to preserve its hydrophilic properties.\n\n---\n\n### Why Choose Photopolymerization?\n\n1. **Preservation of Hydrophilicity:**\n   - Photopolymerization occurs under mild conditions that minimize the risk of side reactions, preserving the hydrophilic functional groups.\n   - Hydrophilic photoinitiators like Irgacure 2959 are compatible with aqueous systems and do not interfere with the hydrophilic nature of the polymer.\n\n2. **Efficient Curing:**\n   - UV-induced polymerization is fast and highly efficient, ensuring uniform curing of the bisphenol A-based (meth)acrylate.\n\n3. **Temperature Control:**\n   - Unlike thermal polymerization, UV curing is carried out at room temperature, avoiding the degradation of temperature-sensitive groups.\n\n4. **Process Simplicity:**\n   - Photopolymerization does not require complex equipment, making it a practical and economical choice for hydrophilic polymer preparation.\n\n---\n\n### Final Remarks:\nThe above procedure provides a systematic approach to cure hydrophilic bisphenol A-based (meth)acrylates while ensuring that the hydrophilic properties are preserved. UV photopolymerization with hydrophilic photoinitiators is a robust and versatile method, suitable for creating hydrophilic polymers tailored to a wide range of applications such as coatings, hydrogels, and biomedical materials.\n\nFeel free to follow up if you have any further questions!"
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diff --git a/task2/task2-qa/HDI╚¤╛█╠х╡─╙ж╙├US9676895B2.json b/task2/task2-qa/HDI╚¤╛█╠х╡─╙ж╙├US9676895B2.json
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+{
+  "design_question": "Formulate an aqueous coating preparation using an oligomer synthesized from glycidol and polyfunctional isocyanate resin. Specify how you would disperse the polymer in water and incorporate a curing agent, taking into account a solvent-free system.",
+  "design_answer": "Thank you for the detailed description of your question! Let us carefully think through your problem step by step to design a systematic experimental preparation scheme for an aqueous coating based on a hydrophilic polymer derived from glycidol and a polyfunctional isocyanate resin. To meet the requirements of a solvent-free system and to achieve excellent dispersion in water, we must break this problem into logical stages. \n\n### Key Points of the Question:\n1. **Polymer Synthesis**:\n   - Use glycidol as one reactive monomer (highly hydrophilic).\n   - Combine it with a polyfunctional isocyanate resin to form a hydrophilic oligomer or prepolymer with tunable molecular architecture.\n2. **Aqueous Dispersion of Polymer**:\n   - Post-synthesis, the polymer must be made water-dispersible.\n   - Design must involve methods to introduce hydrophilic segments, allowing effective water compatibility.\n3. **Incorporation of a Curing Agent**:\n   - Developing a crosslinked network during cure, taking care to adjust reactivity.\n   - Use of solvent-free strategies compatible with the prepolymer/coating formulation.\n\n### Detailed Experimental Preparation Scheme:\nLet us now work through the experiment systematically.\n\n---\n\n#### Step 1: **Synthesis of Hydrophilic Oligomer**\n##### Reaction:\nThe reaction involves **glycidol** (a highly reactive epoxide) and the **polyfunctional isocyanate resin**. Glycidol's hydroxyl and epoxide groups are reactive and will readily react with the isocyanate groups (-N=C=O), forming urethane and secondary hydroxyl functional groups. The secondary hydroxyl groups enhance water dispersibility while maintaining hydrophilicity.\n\n##### Reagents and Molar Ratios:\n- **Polyfunctional isocyanate resin** (e.g., hexamethylene diisocyanate (HDI) trimer or toluene diisocyanate (TDI) trimer): 1 mole (starting material).\n- **Glycidol**: Use a slight molar excess (1.1–1.2 moles) relative to -NCO groups in the resin to ensure all isocyanates are fully reacted and optimize hydrophilicity.\n- **Catalyst**: Dibutyltin dilaurate (DBTDL) or triethylamine (concentration: ~0.1% w/w of total reaction mixture) to promote reaction.\n\n##### Procedure:\n1. Set up a three-neck round-bottom flask equipped with a thermometer, stirrer, and reflux condenser under nitrogen atmosphere to prevent moisture interference.\n2. Add the polyfunctional isocyanate resin (e.g., HDI trimer) to the flask. Heat to 50–60 °C under stirring.\n3. Slowly add glycidol dropwise over 1–2 hours using an addition funnel, maintaining the temperature at 50–60 °C to avoid excessive exothermicity.\n4. Add a trace amount of DBTDL catalyst to accelerate the reaction.\n5. Allow the reaction to proceed for 4–6 hours at 50–60 °C until FTIR spectroscopy confirms the disappearance of the isocyanate peak (~2270 cm⁻¹).\n6. The resulting product will be a hydrophilic oligomer containing secondary hydroxyl and urethane linkages.\n\n##### Key Notes:\n- Ensure a nitrogen blanket to prevent interaction with atmospheric moisture during the reaction.\n- Avoid overheating, as this may lead to side reactions such as oligomer gelation or crosslinking.\n\n---\n\n#### Step 2: **Dispersing the Hydrophilic Oligomer in Water**\nTo create a solvent-free aqueous coating, we will modify the synthesized oligomer to make it dispersible in water. The free hydroxyl groups on the oligomer allow neutralization and ionic stabilization in water.\n\n##### Procedure:\n1. **Neutralization with Acid**:\n   - Add a small amount of neutralizing acid (e.g., dilute acetic acid or lactic acid) to the oligomer, converting some hydroxyl groups into carboxylate salts for improved dispersibility.\n   - Acid addition should be done at room temperature with continuous stirring.\n   - Recommended neutralization ratio: ~10–15% of hydroxyl groups.\n2. **Water Addition**:\n   - Slowly add deionized water to the neutralized oligomer under vigorous stirring at room temperature to form a stable aqueous dispersion.\n   - Continue stirring for 30 minutes to ensure uniform dispersion.\n\n---\n\n#### Step 3: **Incorporating the Curing Agent**\nNow that we have a stable water-dispersible polymer system, a curing agent is added to allow crosslinking during coating formation. An ideal curing agent will crosslink the hydroxyl groups of the oligomer while being compatible with the solvent-free, aqueous system.\n\n##### Choice of Curing Agent:\n- **Polycarbodiimide** or **blocked isocyanate** derivatives are excellent curing agents for hydroxyl-functional systems, as they promote urethane crosslinking upon curing at elevated temperatures (e.g., 120–150 °C).\n- Molar ratio: Use curing agent at ~0.8–1.0 equivalents per hydroxyl group.\n\n##### Procedure:\n1. Add the chosen curing agent directly to the aqueous dispersion of the oligomer under stirring.\n2. Mix thoroughly for 15–20 minutes at room temperature to ensure homogeneity.\n3. The final coating formulation is now ready for application.\n\n---\n\n#### Step 4: **Thermal Curing of the Coating**\nAfter coating application, curing is essential to achieve full crosslinking and develop robust film properties.\n\n##### Procedure:\n1. Apply the prepared aqueous coating onto the substrate (e.g., steel, plastic, or glass) using standard methods like dip coating or spraying.\n2. Bake the coated substrate in an oven at 120–150 °C for 30–60 minutes, depending on the curing agent and substrate tolerance.\n3. Allow the coating to cool to room temperature.\n\n---\n\n### Final Notes:\n1. The hydrophilicity of the final coating can be tuned by adjusting the glycidol-to-isocyanate ratio during synthesis.\n2. The choice of curing agent and baking conditions depend on the substrate and desired coating properties.\n3. Test the coating for adhesion, water resistance, and appearance to validate application goals.\n\nBy following this experimental scheme, you will successfully prepare a hydrophilic aqueous coating system that meets the requirements of solvent-free processing. Let me know if there are additional aspects to clarify!"
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diff --git a/task2/task2-qa/HTA╥╗┐ю╙├╙┌╖╓┼ф╕║╘Ё╚╦║═╛█║╧╖┤╙ж╓╨SMILES╡─╬▓▓┐.json b/task2/task2-qa/HTA╥╗┐ю╙├╙┌╖╓┼ф╕║╘Ё╚╦║═╛█║╧╖┤╙ж╓╨SMILES╡─╬▓▓┐.json
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+{
+  "design_question": "Using a molecule with a primary amine and a carboxylic acid group, propose how you would identify the head and tail atoms and classify the polymerization mechanism to create a hydrophilic polymer. Explain the rationale behind your choices.",
+  "design_answer": "To address your question step by step, let us carefully analyze the given scenario and my approach to designing an experimental preparation scheme for a hydrophilic polymer based on your given molecule with a primary amine (-NH2) and a carboxylic acid (-COOH) group.\n\n---\n\n### **Step 1: Analyze the Question**\n\nThe key points from your question are:\n1. **Molecule provided**: The molecule contains a primary amine (-NH2) group and a carboxylic acid (-COOH) group.\n2. **Goal**: Identify the \"head\" and \"tail\" atoms in the molecule to enable polymerization and subsequently classify the polymerization mechanism.\n3. **Objective**: Synthesize a hydrophilic polymer, enhancing its hydrophilicity based on the structure and functionality of the given molecule.\n\nThe hydrophilic nature of the polymer likely stems from the presence of hydrophilic groups (e.g., -NH2, -COOH, or derivatives such as amides, if introduced through polymerization). This requires careful consideration of chemical reactivity and how these groups will be preserved or modified during polymerization.\n\n---\n\n### **Step 2: Understanding the Head, Tail, and Polymerization Mechanism**\n\nIn polymer chemistry:\n- The **head** refers to the reactive site in the monomer that initiates or propagates chain growth through covalent bonding.\n- The **tail** refers to another complementary site in the monomer that connects to the head of the next monomer molecule.\n- **Polymerization mechanism** depends on the functional groups available in the monomer; in this case, we will consider a condensation polymerization mechanism due to the presence of -NH2 and -COOH groups.\n\nFor your molecule:\n- The **primary amine (-NH2)** can act as the nucleophile, donating electrons to form bonds.\n- The **carboxylic acid (-COOH)** can act as the electrophile, accepting nucleophilic attack and enabling condensation.\n\nBased on this, the primary amine can be designated as the \"head\" of the monomer (responsible for initiating bonding), while the carboxyl group serves as its \"tail\" (allowing chain propagation with subsequent monomer molecules).\n\n---\n\n### **Step 3: Classify the Polymerization Mechanism**\n\nThe polymerization mechanism that naturally fits for such a setup is **step-growth polymerization via condensation reactions**, where the removal of a small molecule (e.g., water) accompanies the formation of covalent bonds between the monomer units.\n\n- In this case, the polymerization occurs between the -NH2 and -COOH groups of the molecule through **amide bond formation** (-CONH-).\n- As a result, the polymer will consist of repeating units containing amide linkages, which are polar and contribute significantly to the hydrophilicity of the final polymer.\n\n---\n\n### **Step 4: Detailed Experimental Design of the Polymerization Scheme**\n\nHere, I provide a step-by-step protocol to synthesize a hydrophilic polymer based on the monomer you described.\n\n---\n\n#### **Materials Required**\n1. Monomer with primary amine (-NH2) and carboxylic acid (-COOH) group\n2. Catalyst: Condensation catalysts like dicyclohexylcarbodiimide (DCC) or a carbodiimide derivative can be used to facilitate amide bond formation.\n3. Solvent: Dimethylformamide (DMF) or tetrahydrofuran (THF) to dissolve the monomer and enable proper mixing.\n4. Dehydrating agent: To promote the condensation reaction by scavenging water (e.g., molecular sieves or an agent like thionyl chloride, if necessary).\n\n---\n\n#### **Step 1: Pre-Treatment of Monomer Solution**\n- Dissolve the monomer in a suitable aprotic polar solvent like DMF or THF. The concentration of the solution can typically be in the range of 0.5–1.0 M to ensure sufficient reactivity without excessive viscosity.\n- Add a small amount of base (e.g., triethylamine, ~5 mol% relative to the monomer) to neutralize any acidic impurities, maintaining the amine functionality.\n\n---\n\n#### **Step 2: Addition of Catalyst**\n- Introduce the catalyst (e.g., DCC) to the reaction mixture in equimolar proportion to the monomer or slightly in excess (~1.1 equivalents).\n- If high dehydration efficiency is needed, include a drying agent to remove water produced during the condensation process.\n\n---\n\n#### **Step 3: Reaction Conditions**\n- Heat the reaction mixture gently (e.g., 50–80°C) for 12–24 hours under an inert atmosphere (e.g., nitrogen or argon) to prevent unwanted side reactions.\n- Monitor the reaction progression using spectroscopic techniques such as FTIR (to track the disappearance of -NH2 and -COOH bands) or NMR.\n\n---\n\n#### **Step 4: Purification of the Polymer**\n- After polymerization, cool the solution and precipitate the polymer by pouring the reaction mixture into a large volume of a non-solvent (e.g., cold methanol or diethyl ether).\n- Filter or centrifuge the precipitated polymer, then wash thoroughly with the non-solvent to remove excess reagent and by-products.\n- Dry the purified polymer under vacuum at room temperature or slightly elevated temperature (~40–50°C) until constant weight is achieved.\n\n---\n\n### **Outcome and Observations**\n- The resulting polymer will contain repeating amide linkages (-CONH-) in its backbone. The polar nature of these bonds ensures that the polymer has significant hydrophilicity.\n- The degree of polymerization and molecular weight can be adjusted by controlling the reaction conditions, reagent ratios, or introduction of chain stoppers (e.g., monofunctional amines or carboxylic acids).\n\n---\n\n### **Step 5: Enhancing Hydrophilicity**\nDepending on the application, additional functionalization can enhance hydrophilicity, such as:\n1. Grafting onto the polymer with hydrophilic side chains (e.g., PEGylation).\n2. Increasing the density of hydrophilic groups by copolymerization with monomers containing hydroxyl (-OH) groups or sulfonic acid (-SO3H) groups.\n\n---\n\n### **Summary**\n\n1. **Head-Tail Assignment**: The -NH2 group acts as the nucleophilic \"head,\" while the -COOH group is the electrophilic \"tail.\"\n2. **Polymerization Mechanism**: Step-growth condensation polymerization forms amide bonds (-CONH-) between monomers.\n3. **Protocol**: The synthesis involves dissolving the monomer, activating polymerization with a carbodiimide catalyst, and purifying the product post-reaction.\n4. **Enhancing Hydrophilicity**: Functional groups in the polymer backbone, such as amide bonds, inherently contribute hydrophilicity, while grafting or copolymerization offers additional pathways.\n\nBy following this systematic method, you can successfully prepare hydrophilic polymers from the given bifunctional monomer."
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diff --git a/task2/task2-qa/High performance pressure-sensitive adhesive polymers-1989.json b/task2/task2-qa/High performance pressure-sensitive adhesive polymers-1989.json
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+{
+  "design_question": "Design a polymerization experiment that utilizes glycidyl methacrylate as a monomer to prepare a hydrophilic polymer with functional groups. Specify the polymerization technique you would choose and why.",
+  "design_answer": "### Detailed Explanation and Polymerization Experiment Design:\n\n#### **Step 1: Analyze the Problem**\n\nYou are asking to design an experiment to prepare a hydrophilic polymer using glycidyl methacrylate (GMA) as the base monomer. GMA is a widely used monomer due to its reactive **epoxide groups** and the methacrylate **vinyl group**, which makes it amenable to radical polymerization. However, GMA itself is hydrophobic or insufficiently hydrophilic in its native state, so the goal is to introduce functional groups that enhance hydrophilicity.\n\nTo prepare a hydrophilic polymer, we have two key components in the process:\n1. **Polymerization mechanism:** The main polymerization method to form the polymer backbone.\n2. **Post-functionalization strategy** (optional): A chemical modification step to react with the epoxide groups on GMA and introduce hydrophilic functional groups.\n\nGiven this context and the need for hydrophilicity, I propose choosing free radical polymerization for its simplicity and effectiveness with vinyl monomers. Additionally, the epoxide ring on GMA provides an opportunity for a secondary functionalization step to add highly hydrophilic functionalities such as hydroxyl groups, amines, or carboxylic acid groups.\n\n#### **Step 2: Proposed Polymerization Technique**\n- **Polymerization Type:** Free Radical Polymerization (FRP).\n- **Justification for FRP:** \n  - FRP is compatible with methacrylate monomers like GMA.\n  - It is an efficient, widely used, and scalable technique.\n  - The method allows for the incorporation of comonomers to tune the polymer properties.\n  - Post-polymerization modification of epoxide groups can be achieved without interfering with the polymer backbone.\n\n#### **Step 3: Experimental Scheme**\nI propose a two-step approach:\n1. **Step 1:** Synthesize poly(glycidyl methacrylate) (PGMA) via free radical polymerization.\n2. **Step 2:** Introduce hydrophilic functional groups by post-polymerization modification of reactive epoxide rings.\n\n---\n\n### **Step 1: Polymerization of Glycidyl Methacrylate (PGMA)**\n\n#### **Materials Required**\n1. **Glycidyl methacrylate (GMA):** Monomer\n2. **Azobisisobutyronitrile (AIBN):** Thermal initiator\n3. **Solvent:** Toluene or dimethylformamide (DMF) (soluble GMA monomers); alternatively, polymerize in bulk.\n4. **Reaction apparatus:** Round-bottom flask with thermal stirrer, thermometer, reflux condenser, inert gas (nitrogen/argon).\n\n#### **Procedure**\n1. **Cleaning & Setup:**\n   - Clean and dry the round-bottom flask.\n   - Assemble stirring apparatus and attach a reflux condenser (to prevent solvent evaporation).\n   - Purge the system with an inert gas (e.g., argon or nitrogen) for about 30 minutes to remove oxygen, which inhibits radical polymerization.\n\n2. **Reagent Preparation:**\n   - Dissolve a predetermined amount of GMA in toluene or DMF. Typical concentrations are **10-30% by weight** in the solvent.\n   - Add AIBN as an initiator. Common usage is 1-2 mol% of the monomer. For instance, if 10 mmol (~1.42 g) of GMA is used, add 0.1-0.2 mmol (~0.016-0.032 g) of AIBN.\n   - Ensure all reagents are thoroughly mixed.\n\n3. **Reaction Conditions:**\n   - Degas the solution by gentle bubbling/purging with an inert gas.\n   - Heat the mixture under constant stirring at 65-70°C for 4-6 hours. This is the typical decomposition range for AIBN.\n   - Monitor the solution viscosity as polymerization progresses. The reaction is complete when there is no further change in viscosity or when the desired conversion is achieved.\n\n4. **Precipitation & Purification:**\n   - Cool the reaction to room temperature.\n   - Precipitate the polymer by dripping the reaction mixture into a non-solvent such as hexane or methanol, depending on solvent compatibility.\n   - Filter and wash the polymer. Dry in a vacuum oven at around 50°C to remove residual solvent.\n\n#### **Key Parameters**\n- Monomer-to-initiator ratio affects polymer chain length and molecular weight.\n- Free radical polymerization may result in some branching or slight cross-linking, especially under high monomer concentrations.\n\n---\n\n### **Step 2: Functionalization of PGMA to Enhance Hydrophilicity**\n\nThe synthesized PGMA contains reactive epoxide rings on its side chains. These rings can undergo nucleophilic substitution or ring-opening reactions to introduce hydrophilic functional groups, such as hydroxyl groups, amine groups, or zwitterionic moieties.\n\n#### **Materials Required**\n1. **Hydrophilic reagents:**\n   - Ethanolamine (to introduce hydroxyl and amine groups).\n   - Water (*if simple hydrolysis is preferred for hydroxylation*).\n   - Amines, e.g., 2-(dimethylamino)ethanol, for zwitterionic properties.\n2. **Catalyst:**\n   - Sulfuric acid or triethylamine (depending on the reaction type).\n3. **Solvent:** Methanol, ethanol, or water.\n4. **pH Adjuster:** Sodium hydroxide if a base-catalyzed reaction is chosen.\n\n#### **Procedure**\n1. **Epoxide Ring Opening:**\n   - Dissolve the PGMA polymer in a suitable solvent such as methanol or ethanol at a concentration of 5-10% w/v.\n   - Slowly add the hydrophilic reagent (e.g., ethanolamine) to the reaction mixture. Maintain a molar ratio of **1:1 or 1:2** (reagent to epoxide groups).\n   - Add a small quantity of a catalyst like sulfuric acid or triethylamine to initiate ring-opening.\n\n2. **Reaction Conditions:**\n   - Heat the solution gently at 50-60°C with stirring for 4-8 hours. Ensure complete solubilization.\n   - Monitor progress using techniques like FTIR (appearance of –OH or amine-related bands) or NMR spectroscopy (disappearance of epoxide signals).\n\n3. **Neutralization and Precipitation:**\n   - Cool the reaction and neutralize the medium (if acidic) with sodium hydroxide or another neutralizing agent.\n   - Precipitate the modified polymer from a non-solvent (as described in Step 1), then clean and dry the product.\n\n---\n\n### **Final Product:**\nThe resulting polymer, functionalized PGMA, possesses hydrophilic groups such as hydroxyl or amine groups, making it significantly more hydrophilic than unmodified PGMA. The hydrophilicity can be tuned by varying the extent of functionalization or selecting reagents with high water affinity.\n\n#### **Characterization:**\n- **Fourier-transform infrared spectroscopy (FTIR):** To confirm the presence of hydrophilic groups (e.g., OH, NH).\n- **NMR spectroscopy:** To monitor epoxide conversion.\n- **Contact Angle Measurement:** To quantify hydrophilicity.\n\n---\n\n### **Conclusion:**\nThis two-step strategy (polymerization followed by functionalization) offers a robust and versatile method for producing functionalized hydrophilic polymers using glycidyl methacrylate. The approach allows for significant control over polymer properties and is compatible with various functionalization agents to meet diverse application needs (biomedical coatings, hydrogels, etc.)."
+}
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+{
+  "design_question": "Describe a method to deposit a graphene oxide (GO)-modified polymer coating on a substrate, ensuring both high hydrophilicity and good mechanical stability of the coating.",
+  "design_answer": "To design a method for depositing a **graphene oxide (GO)-modified polymer coating** on a substrate with high hydrophilicity and good mechanical stability, let us proceed step by step while adhering to the scientific and detail-oriented guidelines.\n\n---\n\n### Step 1: **Analyze the Question and Summarize the Key Points**\nThe critical requirements of the question are as follows:\n1. The desired coating must exhibit **high hydrophilicity**, which implies the need for hydrophilic functional groups and compatibility between GO and the polymer.\n2. The coating must have **good mechanical stability**, ensuring it adheres well to the substrate and exhibits robust physical properties.\n3. A graphene oxide (GO)-modified polymer needs to be incorporated into the coating.\n\nKey approach: GO is a functional nanomaterial with numerous hydrophilic groups such as carboxyl (–COOH), hydroxyl (–OH), and epoxy (–C–O–C), making it inherently hydrophilic. Its incorporation into a hydrophilic polymer matrix will enhance both the hydrophilicity and mechanical resilience of the coating. The preparation must involve systematic steps of substrate preparation, polymer-GO functionalization, and coating deposition.\n\n---\n\n### Step 2: **Design the Preparation Scheme**\nBelow is a systematic preparation scheme that addresses the requirements of high hydrophilicity and mechanical stability in detail.\n\n#### **A. Materials and Reagents**\n1. **Graphene Oxide (GO):** Commercially available or synthesized via the Hummers’ method.\n2. **Hydrophilic Polymer Precursor:** Candidates could include:\n   - Poly(vinyl alcohol) (PVA)\n   - Polyethylene glycol diacrylate (PEG-DA)\n   - Polyacrylamide (PAM)\n3. **Crosslinker:** For mechanical stability, use crosslinking agents like glutaraldehyde (for PVA), N,N'-methylenebisacrylamide (for PAM), or UV light (for PEG-DA).\n4. **Solvent:** Water or aqueous ethanol for dissolving the polymer precursor.\n5. **Substrate:** Glass, metal, silicon wafer, or polymer.\n\n---\n\n#### **B. Experimental Procedure**\n\n##### **Step 1: Substrate Preparation**\n1. Choose a smooth, clean substrate (e.g., glass or silicon wafer).\n2. Wash the substrate thoroughly with:\n   - Distilled water and ethanol to remove organic contaminants.\n   - Optional: Perform plasma treatment to enhance surface activation, increasing adhesion of the polymer coating.\n3. Air-dry the substrate or dry in an oven at 70 °C.\n\n---\n\n##### **Step 2: Preparation of the GO-Modified Polymer Solution**\n1. **Disperse Graphene Oxide:**\n   - Disperse GO in deionized water (concentration ~2-5 mg/mL) using ultrasonication for 1 hour to create a stable colloidal suspension.\n   - Integrating GO: Higher GO loading enhances hydrophilicity, but excessive GO can reduce the flexibility of the polymer matrix. Typical GO mass fraction: ~0.5-5% relative to the polymer precursor.\n   \n2. **Prepare the Polymer Precursor Solution:**\n   - For **PVA:** Dissolve 10 g of PVA in 90 mL deionized water while gently heating (~80–90 °C) and stirring until completely dissolved.\n   - For **PEG-DA:** Use 10 wt% PEG-DA dissolved in water as the precursor solution.\n   - For **PAM:** Prepare a solution of acrylamide monomer (10–15 wt%) in water.\n   \n3. **Combine GO with the Polymer Precursor:**\n   - Gradually add the GO suspension into the polymer precursor under continuous stirring to form a homogeneous GO-polymer mixture.\n   - Optional chemical grafting: If stronger interactions between GO and the polymer are desired, modify GO with coupling agents (e.g., silanes or carbodiimides) to attach to the polymer chains.\n\n---\n\n##### **Step 3: Deposition of the Coating**\n1. **Spin Coating:** This is suitable for uniform coatings.\n   - Drop ~100 µL of the GO-polymer mixture onto the substrate.\n   - Spin the substrate at ~1000–3000 rpm for 30–60 seconds to spread the coating evenly.\n2. **Dip Coating:** Submerge the substrate into the GO-polymer solution, then withdraw it at a controlled rate (e.g., 10 mm/min) to form a uniform film.\n3. **Spray Coating (Optional):** Use for irregular or large-scale surfaces.\n   - Use a fine mist sprayer to evenly deposit the GO-polymer solution onto the substrate.\n\n---\n\n##### **Step 4: Crosslinking (Enhancing Mechanical Stability)**\n1. Select a crosslinking strategy based on the chosen polymer:\n   - **For PVA:** Immerse the coated substrate in a 1 wt% glutaraldehyde aqueous solution for 1 hour, followed by washing thoroughly with water.\n   - **For PEG-DA:** Cure the coating under UV light (365 nm) for 5–10 minutes.\n   - **For PAM:** Add N,N'-methylenebisacrylamide as a crosslinker during polymer precursor preparation and initiate crosslinking with a radical initiator like ammonium persulfate (APS) and TEMED.\n2. After crosslinking, wash the coating with water to remove unreacted reagents.\n\n---\n\n##### **Step 5: Drying and Post-Treatment**\n1. Dry the substrate under ambient conditions or in an oven at ~60 °C for 1–2 hours.\n2. (Optional) Conduct additional plasma treatment or annealing (~120 °C) to improve coating stability and adhesion, if needed.\n\n---\n\n#### **C. Characterization of the Coating**\n1. **Hydrophilicity Test:** Measure water contact angle. A contact angle <30° indicates excellent hydrophilicity.\n2. **Mechanical Stability Test:** Perform adhesion tests (tape test or nano-scratch test) and monitor wear resistance under mechanical stress.\n3. **Morphology and Uniformity:** Use scanning electron microscopy (SEM) or atomic force microscopy (AFM) to analyze surface structure.\n4. **Chemical Composition:** Confirm successful incorporation of GO using Fourier-transform infrared spectroscopy (FTIR) or Raman spectroscopy.\n\n---\n\n### Final Notes:\nThis procedure ensures a hydrophilic polymer coating modified with GO, fulfilling the requirements for both enhanced hydrophilic properties and mechanical stability. The key to success lies in proper dispersion of GO without aggregation, appropriate polymer-GO compatibility, and effective crosslinking for stability."
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+{
+  "design_question": "Given a specific molecule of your choice that enhances hydrophilicity, propose a mechanism for incorporating it into a polymer material to increase water affinity. What type of functional groups on the polymer backbone would facilitate this modification?",
+  "design_answer": "Certainly! Let's break this down step by step and propose a detailed experimental strategy for synthesizing a hydrophilic polymer by incorporating a specific functionality into a polymer backbone to increase its water affinity.\n\n---\n\n### **Step 1: Analyze the Question**\n#### Key Points:\n1. **Objective**: To enhance polymer hydrophilicity by chemically modifying the polymer backbone with a hydrophilic molecule.\n2. **Key Deliverable**: A detailed experimental preparation scheme, including:\n   - The choice of a specific hydrophilic molecule.\n   - A method or mechanism to chemically incorporate the molecule into the polymer material.\n   - Consideration of functional groups on the polymer backbone that facilitate this modification.\n\n---\n\n### **Step 2: Selection of Hydrophilic Molecule**\nTo increase hydrophilicity, we need a molecule or functionality that exhibits strong interactions with water, such as:\n- Hydroxyl (-OH) groups\n- Amine (-NH₂) groups\n- Carboxylic acid (-COOH) groups\n- Sulfonic acid (-SO₃H) groups\n- Polyethylene glycol (PEG)-based chains (ethylene oxide units).\n\nFor this scheme, I will choose **polyethylene glycol (PEG)** as the hydrophilic molecule. PEG provides excellent hydrophilicity due to its rich ether oxygen atoms capable of hydrogen bonding with water molecules.\n\n---\n\n### **Step 3: Selection of Polymer Backbone and Functional Groups**\nPotential polymer backbones for modification include those that contain reactive functional groups or can be suitably functionalized to include:\n- Hydroxyl (-OH)\n- Amino (-NH₂)\n- Epoxy groups\n- Double bonds for radical reactions\n\nFor this scheme, let’s use **poly(methyl methacrylate) (PMMA)** as the polymer backbone because:\n1. It has good compatibility with modification chemistry.\n2. Its ester groups can be hydrolyzed to introduce carboxylic acids (-COOH) or reacted with suitable hydrophilic molecules such as PEG.\n\n---\n\n### **Step 4: Experimental Preparation Scheme**\nNow, I will outline a systematic scheme for the modification of PMMA with PEG to create a hydrophilic polymer.\n\n---\n\n#### **Step 4.1: Materials and Reagents**\n1. **Poly(methyl methacrylate) (PMMA)** – backbone polymer.\n2. **Hydrophilic molecule**: Polyethylene glycol monomethacrylate (PEG-MA) (or PEG with appropriate terminal functionality).\n3. **Solvent**: Dimethylformamide (DMF) or tetrahydrofuran (THF).\n4. **Initiator**: Azobisisobutyronitrile (AIBN) for free radical polymerization.\n5. **Catalysts/Additional Reagents**: Depending on the specific modification route (e.g., DCC/NHS for ester bond formation, or NaOH for hydrolysis).\n\n---\n\n#### **Step 4.2: Reaction Mechanisms and Steps**\n##### **Option 1: Grafting PEG on the PMMA Backbone via Free Radical Polymerization**\n1. **Dissolve PMMA and PEG Monomer**: \n   - Dissolve PMMA and PEG-monomethacrylate in DMF at a concentration of approximately 0.5–1.0 M (molecular weight ratios can be chosen to control the degree of modification).\n   \n2. **Introduce Initiator**:\n   - Add AIBN at 1–3 wt% of the total monomer weight and purge the reaction flask with nitrogen to remove oxygen that inhibits free radical polymerization.\n\n3. **Polymerization**:\n   - Heat the mixture to 60–70°C under constant stirring for 6–8 hours.\n   - Monitor the reaction progress using ^1H NMR to observe the consumption of C=C double bonds in the monomers.\n\n4. **Purification**:\n   - Precipitate the modified polymer (PMMA-g-PEG) in an anti-solvent such as cold methanol or acetone.\n   - Filter and dry under vacuum.\n\n##### **Option 2: Hydrolysis of PMMA and Coupling with PEG**\n1. **Hydrolyze PMMA**:\n   - Dissolve PMMA in a mixture of methanol and NaOH at reflux conditions (approximately 60°C) for 6 hours. This converts a portion of the ester groups into carboxylic acid groups (-COOH).\n\n2. **Activate the Carboxylic Acid Groups**:\n   - Add dicyclohexylcarbodiimide (DCC) and N-hydroxysuccinimide (NHS) in stoichiometric amounts relative to the carboxylic acid groups, stirring the solution at 0°C for 30 minutes.\n   - This forms active ester intermediates.\n\n3. **Couple PEG Chains**:\n   - Add PEG with terminal amine (-NH₂) or hydroxyl (-OH) groups.\n   - Allow the reaction to proceed for 12–24 hours at room temperature to couple PEG onto the PMMA backbone via amide or ester linkages.\n\n4. **Purification**:\n   - Remove unreacted PEG and byproducts by dialysis or precipitation in an anti-solvent (e.g., ether).\n   - Dry the modified polymer under vacuum.\n\n---\n\n### **Step 5: Characterization and Confirmation**\n1. **Fourier Transform Infrared Spectroscopy (FTIR)**:\n   - Confirm the introduction of PEG by detecting characteristic C-O-C (ether) and O-H stretches.\n   \n2. **Nuclear Magnetic Resonance (NMR)**:\n   - ^1H NMR to identify PEG-specific resonances and quantify the degree of modification.\n\n3. **Contact Angle Measurements**:\n   - Measure the water contact angle to verify enhanced hydrophilicity (lower angles indicate higher hydrophilicity).\n\n4. **Thermogravimetric Analysis (TGA)**:\n   - Assess thermal stability of the modified polymer.\n\n---\n\n### **Step 6: Conclusion**\nUsing the above approach, PEG can be systematically and chemically incorporated into the PMMA backbone to enhance its hydrophilicity. The proposed grafting or coupling methodology ensures site-specific modification, maintains the structural integrity of the polymer, and significantly increases its water affinity. Both methods outlined are widely used and can be tailored depending on the specific application or properties desired in the final material.\n\nWould you like me to further elaborate on any step or consider a different hydrophilic molecule/polymer system?"
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+{
+  "design_question": "Explain how you would control the addition of alcohol over time during the synthesis process when IPDI is used as a reactant, and detail how this step contributes to enhancing the hydrophilicity of the polymer material.",
+  "design_answer": "To address your question comprehensively and systematically, let's break the problem into its core components: the role of IPDI (isophorone diisocyanate) in the polymer synthesis, the controlled addition of alcohol as a reactant, the contribution of alcohol addition to enhancing polymer hydrophilicity, and the key parameters necessary for experimental success.\n\n---\n\n### **Step 1: Analyzing the Problem**\n- **Key Reactant:** IPDI is a diisocyanate compound commonly used in the synthesis of urethane polymers. It has two reactive isocyanate functional groups (-NCO), which allow it to react with hydroxyl (-OH) groups in alcohols or other molecules to form urethane linkages.\n- **Main Objective:** The controlled addition of alcohol during the reaction with IPDI, with the intention of modifying the polymer structure to enhance hydrophilicity.\n- **Enhancing Hydrophilicity:** To make the polymer hydrophilic, hydroxyl-functional alcohols or polyols can be used that introduce hydrophilic groups such as hydroxyl (-OH), ether (-O-), or carboxylic acid (-COOH) groups into the polymer backbone or side chains.\n\nThe success of this step depends on controlling reagent addition and reaction kinetics, ensuring an adequate ratio of reactants and achieving a uniform distribution of hydrophilic groups in the polymer matrix.\n\n---\n\n### **Step 2: Detailed Experimental Preparation Scheme**\n\n#### **Materials Required**\n1. **IPDI (Isophorone Diisocyanate):** The diisocyanate reactant.\n2. **Hydrophilic Alcohol or Polyol:** Choose an alcohol with hydrophilic groups (e.g., polyethylene glycol (PEG), glycerol, or 2-hydroxyethyl methacrylate (HEMA)) to enhance hydrophilicity.\n3. **Solvent:** Dimethylformamide (DMF) or acetone may be used as an inert solvent to facilitate mixing and control viscosity.\n4. **Catalyst:** Dibutyltin dilaurate (DBTDL) or another suitable catalyst to accelerate urethane formation.\n5. **Deionized Water:** For post-synthesis purification.\n6. **Nitrogen Gas:** To provide an inert atmosphere and minimize moisture interference, as -NCO groups are reactive toward water.\n\n---\n\n#### **Step 3: Experimental Procedure**\n\n##### **Part A: Pre-Reaction Setup**\n1. **Prepare the Reaction Vessel:** Use a clean, dry, three-necked flask equipped with a mechanical stirrer, thermometer, and addition funnel. Ensure the setup is moisture-free because IPDI reacts with water.\n2. **Inert Atmosphere:** Purge the reaction vessel with nitrogen gas to create an inert environment, preventing unwanted side reactions (e.g., formation of urea due to moisture).\n3. **Prepare Solutions:**\n   - Dissolve IPDI in DMF (or desired solvent) to create a 10–20% (w/v) solution.\n   - Prepare the alcohol or polyol solution separately, ensuring accurate concentration (e.g., 20–25% w/v), depending on the target molar ratio relative to IPDI.\n\n---\n\n##### **Part B: Controlled Addition of Alcohol**\n1. **Set Reaction Temperature:** Heat the reaction vessel to 60–70°C, maintaining constant stirring (600–800 rpm). This temperature range is optimal for urethane bond formation without spontaneous side reactions.\n2. **Initiate Reaction:** Introduce the catalyst (DBTDL at 0.1–0.5 wt%) into the IPDI solution. This step activates the isocyanate groups for reaction with hydroxyl groups.\n3. **Alcohol Addition (Key Step):**\n   - Use an addition funnel to add the alcohol solution dropwise over **3–5 hours**. This slow addition is critical to controlling reaction kinetics, preventing local saturation of alcohol, and ensuring uniform polymer chain formation.\n   - Monitor the molar ratio: Target an IPDI-to-alcohol ratio between **1:1 and 1:1.2**, depending on the final hydrophilic polymer design. A slight excess of alcohol guarantees complete reaction of all isocyanate groups and incorporation of hydrophilic functionality.\n   - Maintain stirring during addition to prevent localized concentration spikes and ensure homogeneous polymer formation.\n\n---\n\n##### **Part C: Post-Reaction and Purification**\n1. **Reaction Completion:** After alcohol addition, continue stirring at 60–70°C for an additional 1–2 hours to ensure all -NCO groups are fully reacted.\n2. **Neutralization Step:** Carefully add deionized water dropwise if necessary to quench any unreacted -NCO groups without introducing defects.\n3. **Purification:** Precipitate the polymer by pouring the reaction mixture into a nonsolvent (e.g., diethyl ether or hexane). Filter and wash the precipitate with deionized water to remove impurities and unreacted reagents.\n4. **Drying:** Dry the purified polymer under vacuum at 40–50°C to remove residual solvent.\n\n---\n\n### **Step 4: Role of Controlled Addition of Alcohol**\n- **Uniform Distribution:** Slow addition prevents uncontrolled crosslinking or excessive chain termination, resulting in a well-defined polymer structure with hydrophilic segments distributed uniformly.\n- **Hydrophilicity Enhancement:** Alcohol contributes hydrophilic groups (-OH, -O-) that improve water absorption, wetting properties, and overall hydrophilicity of the polymer.\n- **Improved Mechanical Properties:** Controlled addition enhances polymer chain regularity, improving mechanical strength and minimizing defects.\n\n---\n\n### **Step 5: Notes on Reaction Controls**\n1. **Monitoring:** Use FTIR spectroscopy during the reaction to monitor the disappearance of the -NCO peak (around 2270 cm⁻¹) and the appearance of a urethane peak (around 1680 cm⁻¹), confirming reaction progress.\n2. **Safety:** Handle IPDI with care in a fume hood and wear appropriate PPE, as it is toxic and moisture-sensitive.\n3. **Optimization:** Lab trials can fine-tune alcohol addition rates to balance hydrophilicity, reaction kinetics, and product yield.\n\n---\n\n### **Conclusion**\nThe controlled addition of alcohol during polymer synthesis with IPDI ensures successful reaction progress and the incorporation of hydrophilic groups, enhancing the hydrophilicity of the final polymer material. By adhering to the outlined methodology — including reagent preparation, reaction conditions, and purification steps — students can carry out the synthesis confidently and achieve high-quality materials."
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diff --git a/task2/task2-qa/PUA.json b/task2/task2-qa/PUA.json
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+{
+  "design_question": "If polyethylene glycol (PEG) is chosen as the polyol component, outline the steps needed to introduce this molecule into the polymer chain. How does the structure of PEG contribute to the hydrophilicity of the final polymer material?",
+  "design_answer": "Certainly! Let’s break this question into two parts: first, outlining the step-by-step experimental preparation scheme for incorporating polyethylene glycol (PEG) into the polymer chain, and second, discussing how the structure of PEG enhances the hydrophilicity of the resulting polymer.\n\n---\n\n### Part 1: Experimental Preparation Scheme for Incorporating PEG into a Polymer Chain\n**Key Points of the Question:**\n- PEG is the chosen polyol component.\n- The goal is to integrate PEG into the polymer chain to enhance hydrophilicity.\n- A detailed preparation scheme is required, covering each step, including reaction conditions and reagent amounts.\n\nHere is the step-by-step synthesis process:\n\n#### Step 1: Select the Polymerization Type\nPolyethylene glycol (PEG), with its hydroxyl (-OH) end groups, is ideal for reactions that rely on hydroxyl functionality. Common polymerization methods to incorporate PEG into the chain include:\n1. **Condensation Polymerization** (e.g., with diacid chlorides or isocyanates to form polyesters or polyurethanes).\n2. **Free Radical Polymerization** (if PEG is first functionalized with acrylate or methacrylate groups).\n\nFor this example, we’ll design a scheme based on **condensation polymerization**, creating a polyester by reacting PEG with a diacid or diacid chloride.\n\n---\n\n#### Step 2: Prepare Reagents\n**Key Materials:**\n- Polyethylene glycol (PEG): Select the desired molecular weight (e.g., PEG-400, PEG-600, etc.) depending on the desired flexibility and hydrophilicity in the final polymer.\n- Diacid or Diacid Chloride: Terephthaloyl chloride, succinic acid, or adipoyl chloride are commonly used.\n- Catalyst: Use a catalyst such as p-toluenesulfonic acid (PTSA) or dibutyltin dilaurate (DBTDL) to enhance the reaction rate.\n- Solvent: An inert solvent like toluene (optional for azeotropic removal of byproduct water in esterifications).\n\n---\n\n#### Step 3: Reaction Conditions and Experimental Procedures\nHere is the experimental procedure for incorporating PEG into a polyester polymer chain:\n\n1. **Pre-reaction Preparation:**\n   - Dry PEG under vacuum at 50-60°C to remove any residual moisture, as water interferes with condensation reactions.\n   - Prepare the diacid or diacid chloride in the desired molar ratio to PEG, typically a 1:1 molar ratio for linear polymers.\n\n2. **Reaction Setup:**\n   - In a three-neck round-bottom flask fitted with a stirrer, nitrogen inlet, and reflux condenser, combine PEG and the diacid/diacid chloride in the specified ratio.\n   - Add the catalyst (typically 0.5-1 wt% relative to the total monomer weight).\n\n3. **Reaction Conditions:**\n   - If using a diacid:\n     - Heat the reaction mixture gradually to 150-180°C under nitrogen to initiate esterification. Use azeotropic distillation (if a solvent like toluene is used) to continuously remove water byproduct.\n     - Maintain stirring until the reaction reaches completion, as indicated by cessation of water evolution or FTIR analysis (absence of -OH stretching).\n   - If using a diacid chloride:\n     - Keep the reaction temperature lower (50-80°C) to prevent side reactions. The reaction proceeds more rapidly, and instead of water, HCl gas is the byproduct.\n     - Provide adequate scavenging for HCl gas (e.g., add an HCl trap or conduct the reaction in a basic medium like pyridine).\n\n4. **Completion and Material Isolation:**\n   - After the reaction, cool the mixture to room temperature.\n   - Precipitate the polymer by pouring the reaction mixture into a nonsolvent (e.g., cold methanol or ethanol).\n   - Filter the precipitated polymer and wash with fresh methanol to remove any residual catalyst or unreacted monomers.\n   - Dry the polymer under vacuum at 40-50°C.\n\n5. **Structural Analysis of the Polymer:**\n   - Confirm the successful incorporation of PEG into the polymer chain using:\n     - Nuclear Magnetic Resonance (NMR) spectroscopy (look for characteristic PEG peaks at δ ~3.5 ppm).\n     - Fourier Transform Infrared (FTIR) spectroscopy (identify ester carbonyl peaks at ~1720 cm⁻¹ and absence of unreacted -OH stretches).\n\n---\n\n### Part 2: The Role of PEG in Enhancing Hydrophilicity\nPolyethylene glycol (PEG) has a unique structure that directly contributes to exceptional hydrophilicity. Here is how:\n\n1. **Molecular Structure of PEG:**\n   - PEG consists of a repeating unit: -(CH₂-CH₂-O)-. This hydrophilic backbone contains both hydrophobic (CH₂ groups) and hydrophilic (ether oxygen) components.\n   - The ether oxygens engage in water hydrogen bonding, while the flexible, linear chains allow for solvation and extensive interaction with water molecules.\n\n2. **Hydrophilicity Enhancement:**\n   - When incorporated into a polymer matrix, PEG acts as a hydrophilic domain. It forms pathways within the polymer that enable water absorption, resulting in increased wettability and hydrophilicity.\n   - Greater PEG content typically yields higher water uptake or water solubility, improving the polymer's performance in aqueous environments.\n   - The molecular weight of PEG also affects its hydrophilic character; shorter chains enhance hydrophilicity, while longer chains contribute more to flexibility and mechanical properties.\n\n3. **Applications:**\n   - PEG-based hydrophilic polymers are widely used in biomedical applications (e.g., hydrogels, drug delivery systems) because they resist protein adsorption and have high water retention capacity.\n   - They are also useful in coatings, membranes, and adhesives for environments requiring superior wettability.\n\n---\n\n### Summary\nTo incorporate PEG into the polymer chain, the experimental preparation involves condensation polymerization with a diacid or diacid chloride, carefully controlling the stoichiometry and reaction conditions. PEG’s ether-rich structure enhances hydrophilicity by forming hydrogen bonds with water, making it crucial for biomedical, coating, and water-compatible polymer applications. Understanding PEG's chemistry and processing is essential in designing hydrophilic materials."
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diff --git a/task2/task2-qa/Photoinitiator pendanted on hydrophilic oligomer.json b/task2/task2-qa/Photoinitiator pendanted on hydrophilic oligomer.json
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+{
+  "design_question": "The molecule MPEG is mentioned as a component in the experiment involving hydrophilic polymer preparation. Describe a detailed procedure for incorporating MPEG into a polymer synthesis process to enhance its hydrophilicity, ensuring you address monomer proportions and polymerization conditions.",
+  "design_answer": "Alright, let us carefully address your question and design an experimental preparation scheme for incorporating MPEG (Methoxy-polyethylene glycol) into a hydrophilic polymer synthesis process. Our goal is to enhance the hydrophilicity of the final polymer. I will approach this step by step as per your requirements.\n\n---\n\n### **Step 1: Analyze the Problem**\nThe target is to incorporate MPEG into a polymer to improve its hydrophilicity. MPEG is known for its excellent hydrophilic properties due to the presence of polyethylene glycol segments, which introduce polar ether groups capable of hydrogen bonding with water molecules. Incorporation of MPEG into a polymer backbone or polymer matrix can significantly increase water affinity.\n\nKey considerations for this experiment:\n- MPEG typically has a terminal methoxy group on one end and a hydroxyl (-OH) functional group on the other, making it suited for reactions such as esterification, urethane formation, or radical polymerization.\n- The chosen polymerization scheme must ensure uniform incorporation of MPEG without compromising the hydrophilicity of the polymer.\n- Reaction conditions, monomer ratios, and reagents must be carefully controlled for reproducibility.\n\n---\n\n### **Step 2: Selection of Polymerization Strategy**\nFor incorporating MPEG, two main strategies are commonly employed:\n1. **Grafting MPEG onto an existing polymer backbone.**\n2. **Copolymerizing MPEG with other monomers to form a hydrophilic polymer.**\n\nHere, we will focus on designing a **copolymerization experiment**, as MPEG can be effectively utilized as a macromonomer due to the presence of its hydroxyl group. Specifically, we will utilize free-radical polymerization and functionalize MPEG with a reactive group, such as acrylate or methacrylate, to incorporate it into a growing polymer chain.\n\n---\n\n### **Step 3: Experimental Synthesis of Hydrophilic Polymer**\nBelow, I describe a detailed procedure for synthesizing a hydrophilic polymer using MPEG.\n\n---\n\n#### **3.1 Functionalization of MPEG with Methacrylate**\nBefore MPEG can take part in radical polymerization, it must be functionalized with a methacrylate group. This allows MPEG to act as a macromonomer in the free-radical polymerization process.\n\n1. **Reagents:**\n   - MPEG (Molecular weight: 1000–5000 g/mol, commercially available as a waxy solid or viscous liquid).\n   - Methacrylic anhydride (MAA) or methacryloyl chloride (used to introduce the methacrylate group).\n   - Triethylamine (TEA) as a base.\n   - Solvent: Dry tetrahydrofuran (THF) or dimethylformamide (DMF).\n   - 4-dimethylaminopyridine (DMAP) as a catalyst.\n\n2. **Procedure:**\n   - In a dry reaction vessel under an inert nitrogen atmosphere, dissolve MPEG (1 mol equivalent) in dry THF or DMF.\n   - Add TEA (1.2 mol equivalents) slowly to neutralize the acid generated during the reaction.\n   - Slowly add methacryloyl chloride (1.1 mol equivalents) dropwise to the stirred solution at 0°C to prevent side reactions.\n   - Introduce a catalytic amount of DMAP to accelerate the esterification reaction.\n   - Allow the reaction mixture to warm to room temperature and stir continuously for 8–12 hours to ensure complete conversion of the hydroxyl group to a methacrylate ester.\n   - Purify the methacrylated MPEG by precipitating the product in cold diethyl ether and drying under vacuum.\n\n3. **Confirmation:**\n   - Use nuclear magnetic resonance (NMR) spectroscopy to confirm the successful methacrylation of MPEG:\n     - Look for characteristic peaks corresponding to the methacrylate vinyl protons (~5.6 and ~6.2 ppm) and the MPEG methylene protons (~3.5 ppm).\n\n---\n\n#### **3.2 Free-Radical Copolymerization**\nWith methacrylated MPEG (MPEG-MA) prepared, we perform free-radical polymerization with a comonomer to synthesize the hydrophilic polymer.\n\n1. **Reagents:**\n   - Methacrylated MPEG (MPEG-MA) as the hydrophilic macromonomer (1 mol equivalent).\n   - A hydrophobic or hydrophilic comonomer (e.g., methyl methacrylate (MMA) or hydroxyethyl methacrylate (HEMA)). Select HEMA for enhanced hydrophilicity.\n   - Azobisisobutyronitrile (AIBN) as a radical initiator (1 wt% relative to total monomers).\n   - Solvent: Ethanol, methanol, or a water-alcohol mixture (depending on the solubility of the reaction components).\n\n2. **Procedure:**\n   - In a round-bottom flask, dissolve MPEG-MA and the comonomer (MMA or HEMA) in the chosen solvent. Maintain a total monomer concentration of 20–40 wt% for controlled polymerization.\n   - Add AIBN as the radical initiator to the solution.\n   - Purge the reaction mixture with nitrogen gas for 30 minutes to remove dissolved oxygen, which can inhibit the radical polymerization.\n   - Heat the reaction mixture to 65–70°C and stir for 6–8 hours. Monitor the reaction progress using gel permeation chromatography (GPC) or viscosity measurements.\n   - Once the polymerization is complete, precipitate the polymer by pouring the reaction mixture into excess cold diethyl ether or acetone.\n   - Wash the precipitate several times with the nonsolvent to remove unreacted monomers and oligomers. Dry the polymer under vacuum.\n\n3. **Molar Ratios:**\n   - For a hydrophilic polymer with balanced hydrophilicity, use an MPEG-MA:comonomer ratio of 1:2 to 1:5, depending on the molecular weight of MPEG.\n   - Example: For MPEG-MA (MPEG MW = 2000 g/mol) and HEMA, use 5 mmol MPEG-MA and 10–20 mmol HEMA.\n\n---\n\n#### **3.3 Characterization of the Final Polymer**\n1. **Solubility Test:**\n   - Assess the solubility of the polymer in water to confirm improved hydrophilicity.\n\n2. **Thermal Characterization:**\n   - Use differential scanning calorimetry (DSC) or thermogravimetric analysis (TGA) to evaluate the thermal properties of the polymer.\n\n3. **Structural Analysis:**\n   - Use Fourier-transform infrared spectroscopy (FTIR) or NMR to confirm the incorporation of MPEG in the polymer. Look for characteristic ether peaks from MPEG (~1100 cm⁻¹ in FTIR) and vinyl proton disappearance in NMR.\n\n---\n\n### **Step 4: Summarized Recommendations for Laboratory Practice**\n1. Maintain strict inert conditions during MPEG functionalization to avoid hydrolysis of methacryloyl chloride.\n2. Use freshly distilled solvents and purified reagents to minimize side reactions.\n3. Control the polymerization temperature and reaction time precisely for consistent molecular weight distribution.\n\nBy following this procedure, the synthesized polymer should exhibit significantly enhanced hydrophilicity due to the presence of MPEG segments, making it suitable for biomedical, coating, or water-compatible applications.\n\nI hope this systematically addresses your question. Please let me know if you’d like further clarification on any step!"
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diff --git a/task2/task2-qa/Preparation of water-resistant antifog hard coatings on plastic substrate.json b/task2/task2-qa/Preparation of water-resistant antifog hard coatings on plastic substrate.json
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+{
+  "design_question": "How would you modify Tween 20 to ensure its molecular structure improves the hydrophilicity of a polymer matrix during preparation?",
+  "design_answer": "Certainly, let’s systematically address your question regarding how to modify Tween 20 to improve its contribution to the hydrophilicity of a polymer matrix.\n\n---\n\n### **Step 1: Analyze the Question and Key Points**\n\n1. **Tween 20**: It is a polysorbate-based nonionic surfactant often used for its amphiphilic nature, with a hydrophilic head group (polyoxyethylene chains) and a hydrophobic tail derived from fatty acid esters (commonly derived from lauric acid).\n2. **Hydrophilicity**: To enhance hydrophilicity, the focus should be on increasing the hydrophilic portions of the molecule, such as extending the polyoxyethylene chain, introducing hydrophilic functional groups, or modifying the fatty acid-derived region to include hydrophilic substitutions.\n3. **Integration with a polymer matrix**: Tween 20 must be modified or crosslinked in a way that it becomes chemically grafted or physically bound within the polymer structure, ensuring a stable improvement in hydrophilicity.\n\nThus, the objective is to design a preparation scheme where Tween 20 is chemically or physically modified and incorporated into a polymer matrix to enhance the matrix's hydrophilic properties.\n\n---\n\n### **Step 2: Experimental Preparation Scheme**\n\nLet us now detail a systematic experimental plan addressing this objective.\n\n---\n\n#### **Step 2.1: Modification of Tween 20 to Enhance Hydrophilicity**\n\nTo improve the hydrophilicity of Tween 20 and facilitate its incorporation into a polymer matrix, the primary strategy involves introducing additional hydrophilic or reactive moieties (e.g., carboxyl, hydroxyl, or acrylate groups). A suitable modification scheme is as follows:\n\n---\n\n##### **Step 2.1.1: Carboxylation of Tween 20**\n- **Reagents**: Succinic anhydride (for carboxyl group introduction).\n- **Reaction**: The hydroxyl groups in Tween 20's polyoxyethylene chain react with succinic anhydride to form ester linkages with terminal carboxylic acid groups.\n\n**Procedure**:\n1. Dissolve Tween 20 in dry toluene (as the solvent) under an inert atmosphere (e.g., nitrogen or argon) to prevent oxidative degradation.\n2. Add succinic anhydride at a molar ratio of Tween 20:succinic anhydride = 1:2 to ensure sufficient carboxylation.\n3. Include a catalytic amount of 4-dimethylaminopyridine (DMAP) to assist the esterification reaction.\n4. Heat the reaction mixture to **60–80°C** with stirring for 6–8 hours.\n5. Cool the reaction mixture, wash it with aqueous NaHCO₃ (to neutralize unreacted succinic anhydride), and extract the carboxylated Tween 20 into an organic solvent (e.g., dichloromethane).\n6. Precipitate the product by adding the organic solution dropwise into cold diethyl ether, then dry the modified Tween 20 under vacuum.\n\n**Outcome**: The resulting Tween 20 derivative will contain hydrophilic carboxylic acid groups, boosting hydrophilicity and providing functional sites for subsequent covalent bonding to a polymer matrix.\n\n---\n\n##### **Step 2.1.2: Acrylation of Tween 20**\nFor incorporation into hydrophilic polymers formed by free-radical polymerization, acrylation is an alternative modification.\n\n- **Reagents**: Acryloyl chloride, triethylamine (TEA) as a base.\n- **Reaction**: Terminal hydroxyl groups in Tween 20 react with acryloyl chloride to introduce acrylate groups.\n\n**Procedure**:\n1. Dissolve Tween 20 in dry dichloromethane.\n2. Slowly add acryloyl chloride (molar ratio Tween 20:acryloyl chloride = 1:1.2) and TEA (molar ratio Tween 20:TEA = 1:2) dropwise while keeping the reaction mixture on an ice bath.\n3. Stir the reaction for 6 hours at room temperature.\n4. Filter out triethylammonium chloride (a byproduct of the reaction) and wash the product solution with water.\n5. Purify the acrylated Tween 20 using silica gel column chromatography, if necessary.\n\n**Outcome**: Acrylated Tween 20 can co-polymerize with vinyl monomers (e.g., acrylamide, acrylic acid), facilitating incorporation into hydrophilic polymers.\n\n---\n\n#### **Step 2.2: Incorporation into a Polymer Matrix**\n\nOnce Tween 20 has been chemically modified to introduce hydrophilic or reactive groups, the next step is to incorporate it into a polymer matrix. Two common methods—physical blending and chemical grafting—are discussed below:\n\n---\n\n##### **Step 2.2.1: Physical Blending**\nUse this method if the modified Tween 20 does not need to be covalently bonded to the polymer.\n\n1. Dissolve the hydrophilic polymer matrix precursor (e.g., polyvinyl alcohol or polyacrylamide) in water.\n2. Add the modified Tween 20 (carboxylated or acrylated) to the polymer solution under vigorous stirring.\n3. Cast the solution into a mold and allow it to dry by solvent evaporation at **40–50°C**.\n4. Crosslink the polymer matrix (e.g., using glutaraldehyde for polyvinyl alcohol or thermal crosslinking for polyacrylamide) to stabilize the structure while locking Tween 20 in place.\n\n---\n\n##### **Step 2.2.2: Chemical Grafting**\nThis method creates stable covalent bonds between the modified Tween 20 and the polymer matrix.\n\n**Example for Acrylated Tween 20**:\n- **Reaction**: Co-polymerization with hydrophilic monomers such as acrylic acid or acrylamide.\n- **Procedure**:\n  1. Prepare an aqueous solution of acrylated Tween 20 and the hydrophilic monomer (e.g., acrylamide).\n  2. Add a redox initiator system (e.g., ammonium persulfate and N,N,N',N'-tetramethylethylenediamine) or use UV light to initiate polymerization.\n  3. Stir the reaction at room temperature or irradiate the mixture if UV is used.\n  4. Recover the hydrophilic polymer by precipitation in ethanol, if necessary, or by drying under reduced pressure.\n\n**Outcome**: The modified Tween 20 becomes covalently grafted to the polymer backbone, ensuring long-term hydrophilicity enhancement.\n\n---\n\n### **Step 3: Reaction Conditions and Practical Notes**\n1. **Molar Ratios**: Ensure sufficient reagent stoichiometry. For example:\n   - Tween 20:succinic anhydride = 1:2\n   - Tween 20:acryloyl chloride = 1:1.2\n2. **Solvents**: Use dry, inert solvents to prevent side reactions involving moisture.\n3. **Reaction Environment**: Conduct esterification or acrylation under an inert atmosphere (e.g., nitrogen or argon) to prevent oxidative degradation of Tween 20.\n4. **Purification**: Remove unreacted reagents and by-products to ensure high purity of the modified Tween 20 prior to incorporation.\n\n---\n\n### **Conclusion**\nIn summary, to improve the hydrophilicity of a polymer matrix using Tween 20, you can:\n1. Modify Tween 20 by introducing hydrophilic functional groups (e.g., carboxylic acid or acrylate groups).\n2. Incorporate the modified Tween 20 into the polymer matrix via physical blending or chemical grafting.\nThese steps, when carefully followed with attention to reaction conditions and stoichiometry, will allow you to create a hydrophilic polymer with enhanced performance.\n\nLet me know if you have any further questions or require clarification on specific steps of this process."
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+{
+  "design_question": "Describe how glycidyl methacrylate (GMA) can be used to modify a polymer to introduce hydrophilic properties. Include the reaction mechanism and the functional groups formed during the process.",
+  "design_answer": "Certainly! Let us proceed step by step in tackling this question systematically, based on your request.\n\n---\n\n### **Step 1: Analyze the Question and Summarize Key Points**\n1. **What is being modified?**\n   A polymer (generic or existing polymer) is the starting substrate.\n   \n2. **What is introduced?**\n   Hydrophilic properties need to be incorporated into the polymer.\n\n3. **What reagent is used?**\n   Glycidyl methacrylate (GMA) is the modifying reagent of interest.\n\n4. **Mechanism and functional groups?**\n   A detailed explanation of how modification occurs, including the reaction mechanism and the hydrophilic functional groups formed, is required.\n\nKey takeaways: We need a comprehensive synthesis scheme where Glycidyl Methacrylate (GMA) modifies a polymer to improve hydrophilicity, detailing reaction pathways, functional groups formed, and experimental conditions.\n\n---\n\n### **Step 2: Explanation of the Synthesis Process**\n\nGlycidyl methacrylate (GMA) is a versatile monomer commonly used to functionalize polymers. Its molecular structure includes a methacrylate group and an epoxide group. By leveraging the chemical reactivity of these groups, GMA introduces hydrophilic functional groups, such as hydroxyl (-OH) or additional polar functionalities, into the polymer backbone. Here's a detailed step-by-step experimental design:\n\n---\n\n#### **Step 2.1: Select the Base Polymer**\nThe choice of the base polymer depends on the intended application. Common examples include:\n   - **Polyethylene (PE)** or **Polypropylene (PP)** (non-functionalized polymers).\n   - **Poly(methyl methacrylate) (PMMA)**, which already has functionalized methacrylate groups.\n   - **Poly(vinyl alcohol) (PVA)** or similar hydrophilic polymers that might benefit from further functionalization.\n\nFor simplicity, I'll assume the polymer contains reactive groups such as hydroxyl (-OH), amine (-NH\\(_2\\)), or carboxyl (-COOH) groups. \n\n---\n\n#### **Step 2.2: Proposed Reaction**\nWhen modifying a polymer using GMA, the two main functionalities of GMA (the **epoxide group** and **methacrylate group**) play distinct roles based on the polymer involved.\n\n1. **Epoxide Ring Opening Reaction**\n   - The epoxide group of GMA can react with nucleophilic groups on the surface of the polymer.\n   - Common nucleophilic groups include hydroxyl (-OH), amine (-NH\\(_2\\)), and carboxyl (-COO\\(^-\\)).\n   - Upon reaction, the epoxide ring opens to form **hydroxyether** linkages, resulting in new hydroxyl (-OH) groups that enhance the polymer's hydrophilicity.\n\n2. **Methacrylate Polymerization**\n   - If free-radical polymerization or copolymerization is desired, the methacrylate group of GMA can undergo polymerization to link with other monomers, creating a network that includes GMA units.\n\n---\n\n#### **Step 2.3: Reaction Mechanism**\n\nHere we focus on the **epoxide ring-opening reaction**, the most common scenario for hydrophilicity enhancement:\n\n1. **Activation of Nucleophile and Ring Opening:**\n   - A nucleophile (e.g., -OH, -NH\\(_2\\), or COO\\(^-\\)) attacks the less sterically hindered carbon in the epoxide ring of GMA.\n   - This results in ring opening and the formation of one hydroxyl group and one ether group. (For amine nucleophiles, the product is a β-amino alcohol.)\n\n2. **Example Reaction with a Hydroxyl Group (-OH):**\n   \\[\n   R-OH + \\text{[CH}_2\\text{-O-CH-CH}_2\\text{]} \\rightarrow R-O-CH_2CH(OH)CH_2 \\, \n   \\]\n\n---\n\n#### **Step 2.4: Experimental Procedure**\n\nBelow is a systematic approach for modifying a polymer using GMA.\n\n**Materials Needed:**\n   - Glycidyl methacrylate (GMA).\n   - A polymer substrate (e.g., polyvinyl alcohol, polyethylene glycol, etc.).\n   - Solvent: Use an inert, non-reactive solvent such as dimethylformamide (DMF) or toluene, depending on polymer solubility.\n   - Catalyst: Typically, a base such as triethylamine (TEA) or potassium hydroxide (KOH) facilitates epoxide ring opening.\n   - Optional radical initiator (for methacrylate polymerization): Azobisisobutyronitrile (AIBN).\n\n**Reaction Steps:**\n1. **Dissolution of Polymer:**\n   - Dissolve the polymer in a suitable solvent (e.g., PVA in water, PMMA in DMF).\n   - Polymer concentration: 1–5 wt.%.\n   \n2. **Addition of GMA:**\n   - Add glycidyl methacrylate to the reaction system. The GMA concentration is typically 5–10 mol-% with respect to the polymer repeat unit.\n\n3. **Catalyst Addition:**\n   - Add TEA or KOH (catalyst) to facilitate the epoxide ring opening.\n   - The typical molar ratio of catalyst to GMA is ~1:10.\n\n4. **Reaction Conditions:**\n   - Stir the mixture at 50–70 °C to promote reaction.\n   - Maintain the reaction for 6–12 hours to ensure complete functionalization.\n\n5. **Neutralization (Optional):**\n   - If a base catalyst is used (e.g., KOH), neutralize the solution using dilute acid (e.g., acetic acid) after reaction.\n\n6. **Purification:**\n   - Precipitate and isolate the modified polymer by adding the reaction mixture to a non-solvent (e.g., ethanol for PVA) to remove unreacted GMA.\n   - Dry the polymer under vacuum at 50–60 °C to constant weight.\n\n---\n\n### **Step 3: Hydrophilic Functional Groups Introduced**\n\nAfter the modification, the polymer surface gains hydroxyl (-OH) groups or secondary hydrophilic linkages arising from the opened epoxide. These groups:\n1. Improve wettability due to hydrogen-bond donating and accepting capacity.\n2. Allow for further functionalization or compatibility with aqueous systems.\n\n---\n\n### **Step 4: Additional Insights**\n1. **Copolymerization Option:**\n   - If using the methacrylate functionality of GMA, copolymerization with monomers like acrylamide or acrylic acid can result in a polymer with both hydrophilic and cross-linked properties.\n   - Radical initiators (e.g., AIBN) and thermal curing (65–80 °C) are typically required for this approach.\n\n2. **Applications:**\n   - Biomedical polymers (e.g., hydrogels, drug delivery systems).\n   - Coatings with anti-fouling or water-compatible properties.\n   - Adhesion promoters or surface-active agents.\n\n---\n\n### **Conclusion**\nTo modify a polymer and enhance its hydrophilicity, glycidyl methacrylate (GMA) can be used effectively due to its epoxide ring, which reacts with nucleophiles in the polymer, introducing hydroxyl groups. This process requires a suitable solvent, a catalytic base (KOH or TEA), and optimized reaction conditions (50–70 °C, 6–12 hours). The resulting hydrophilic polymer shows improved interaction with aqueous environments, expanding its application scope.\n\nIf you have further questions about implementing this method in the lab, do not hesitate to ask!"
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diff --git a/task2/task2-qa/SDC-FSI CN109070134B.json b/task2/task2-qa/SDC-FSI CN109070134B.json
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+{
+  "design_question": "Describe how you would incorporate a radiation-curable acrylate containing hydrophilic alkylene oxide moieties (characterized by the formula Ω(CH2)Ωn(0-)Σm-, where n is between 1 and 3, and m is between 1 and 10) into a polymer system to enhance its hydrophilicity. Include any relevant steps for curing and network formation in your explanation.",
+  "design_answer": "### Question Analysis:\nTo address your question, let us break it into its critical components:\n1. **Understanding the molecule**: The target molecule is a radiation-curable acrylate containing hydrophilic alkylene oxide moieties, which takes the general form of \\( \\Omega(\\text{CH}_2)\\Omega_n(\\text{O}-)\\Sigma_m- \\) where \\( n \\) (number of alkylene oxides) ranges from 1–3 and \\( m \\) (number of hydrophilic EO/PO units) from 1–10. Such hydrophilic functional groups enhance water compatibility through hydrogen-bonding interactions.\n2. **Objective**: To effectively incorporate this species into a polymer to make the overall material hydrophilic while developing a cross-linked network through radiation curing.\n3. **Steps**: This involves systematically integrating the reagents, selecting appropriate curing methodologies (likely UV or electron beam radiation), optimizing reaction conditions, and achieving final properties in the polymer system.\n\nWe must focus on specific details, including polymer system preparation, radiation-curing methods, and the formation of cross-linked hydrophilic networks. Now, let us systematically design your experimental preparation scheme.\n\n---\n\n### Experimental Preparation Scheme\n\n#### Step 1: Selection of base polymer system\nFirst, choose the polymer or prepolymer system to which you will add the hydrophilic acrylate. Depending on the final application's requirements:\n- For **soft, flexible materials**, use oligomers or prepolymers such as a urethane acrylate or polyester acrylate.\n- For **rigid materials**, select epoxy acrylates or highly cross-linked methacrylate formulations.\n\nThis choice should ensure compatibility with the targeted acrylate co-monomer and the desired mechanical and water-absorbing properties.\n\n#### Step 2: Monomer preparation\nThe hydrophilic acrylate monomer structure provides the basis for the addition of hydrophilic functional groups into the polymer network. Examples include acrylates functionalized with ethylene oxide (EO) or propylene oxide (PO) groups. Typical examples include:\n- Poly(ethylene glycol) diacrylate (PEGDA) or poly(propylene glycol) acrylate.\n- Structures where EO/PO chains are linear or branched.\n\nBefore proceeding, calculate the molar quantities based on the ratio of hydrophilic monomer to hydrophobic components. Typical formulas:\n- Incorporate **10-30 wt% of hydrophilic acrylate** relative to the total monomer weight for moderate hydrophilicity.\n- For higher hydrophilicity, increase to **40-60 wt% hydrophilic monomer**.\n\n#### Step 3: Preparation of the polymer mixture\nThoroughly mix **hydrophilic acrylate** with the base polymer (or oligomer). Use stimulating agents if viscosity issues arise:\n1. Add **hydrophilic acrylate** gradually to prevent phase separation.\n2. Include a photoinitiator (around **1–3 wt%** of total monomers), such as:\n   - Irgacure 2959 (water-compatible UV initiator).\n   - Darocur 1173 or benzophenone-based initiators, depending on acrylate compatibility.\n\nStir under nitrogen or vacuum to avoid oxygen inhibition (which can inhibit polymerization of acrylates).\n\n#### Step 4: Substrate preparation and coating\nIf forming films, evenly spread the polymer mixture over a clean substrate (e.g., glass, polyethylene, or a mold). Control the thickness of the desired film using a blade applicator or spin-coating.\n\n- Typical film thickness: 50–300 μm.\n\n#### Step 5: Radiation curing\nRadiation curing is critical for polymer network formation:\n1. **UV curing**:\n   - Use a UV lamp emitting wavelengths between 280–400 nm.\n   - Apply fluence of **2–4 J/cm²**. The intensity and exposure time depend on film thickness and photoinitiator used.\n   - Cure under a **nitrogen atmosphere** to prevent oxygen inhibition.\n   - Result: Formation of a cross-linked hydrophilic network.\n\n2. **Electron beam curing (optional)**:\n   - Use electron beam irradiation for solvent-free processing or highly cross-linked systems.\n   - Typical parameters: \\( 50-300 \\, \\text{keV} \\) energy and \\( 2-10 \\, \\text{kGy} \\) dose.\n   - Benefit: Does not require photoinitiators and eliminates concerns with oxygen inhibition.\n\n#### Step 6: Post-treatment and characterization\n1. **Swelling behavior**:\n   - Immerse cured polymer in deionized water to assess water uptake.\n   - Measure the equilibrium swelling ratio \\( Q \\) to quantify hydrophilicity:  \n     \\[\n     Q = \\frac{\\text{Weight of swollen polymer} - \\text{Weight of dry polymer}}{\\text{Weight of dry polymer}}\n     \\]\n   \n2. **Mechanical testing**:\n   - Use tensile testing to analyze elasticity and strength if flexibility is critical.\n   \n3. **Surface hydrophilicity**:\n   - Measure water contact angle to confirm hydrophilicity enhancement. Typical hydrophilic surfaces show contact angles \\( < 45^\\circ \\).\n\n4. **Network structure**:\n   - Use FTIR spectroscopy to confirm acrylate polymerization (C=C peak disappearance) and presence of hydrophilic groups.\n\n---\n\n### Summary of Key Reaction Conditions\n| **Step**                 | **Parameter**                  | **Typical Value/Range**   |\n|--------------------------|---------------------------------|---------------------------|\n| Hydrophilic monomer ratio| % Hydrophilic acrylate         | 10–60 wt%                |\n| Photoinitiator           | wt% of total                   | 1–3 %                    |\n| UV radiation dose         | Energy density                 | 2–4 J/cm²                |\n| Film thickness           | μm                              | 50–300 μm                |\n| Swelling test condition  | Temperature                    | 25–37°C                  |\n| Water contact angle       | For hydrophilic surface        | \\( < 45^\\circ \\)         |\n\nBy following this carefully designed experimental procedure, you should achieve a hydrophilic polymer system with water-absorbing properties and a stable, cross-linked network! Always confirm through testing after each stage of synthesis."
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diff --git a/task2/task2-qa/SDC-FSI╖└╬э-CN109070134B.json b/task2/task2-qa/SDC-FSI╖└╬э-CN109070134B.json
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+{
+  "design_question": "Explain the role of the molecule REASOAP SR-10 in the synthesis of a hydrophilic polymer. Specifically, discuss how its reactive group contributes to the formation of a hydrophilic network during the curing process.",
+  "design_answer": "To systematically answer your question about the role of the molecule REASOAP SR-10 in the synthesis of a hydrophilic polymer and its contributions through its reactive groups, let us proceed step by step. This breakdown will help you fully understand the relevance of the molecule and guide you on how to use it effectively during the polymer synthesis.\n\n---\n\n### Step 1: **Analyze the Question and Summarize Key Points**\n\nKey aspects of your question:\n1. Identify the role of **REASOAP SR-10** within the synthesis of a hydrophilic polymer.\n2. Understand how its **reactive group** contributes to the curing process.\n3. Explain how the reactive group plays a role in developing the **hydrophilic network** within the polymer matrix.\n\nThus, we need to investigate:\n- The structure of REASOAP SR-10 and its functional groups.\n- The chemistry of its reactive group and how it participates in curing.\n- The contribution of its molecular structure to overall hydrophilicity.\n\n---\n\n### Step 2: **Detailed, Systematic Explanation**\n\n#### (i) **Chemical Nature of REASOAP SR-10**\n\nWhile the precise molecular structure and exact reactive groups of REASOAP SR-10 must be verified from its datasheet or literature, let us assume for this explanation that it includes key reactive functional groups such as **epoxy, hydroxyl, or acrylic** moieties. These functional groups are typically involved in covalent crosslinking reactions during curing processes, which are common in polymer synthesis.\n\nAdditionally, REASOAP SR-10 likely incorporates **hydrophilic side groups** such as -OH, -COOH, or ether (-C-O-C-) linkages, which enhance water affinity and contribute to the polymer's hydrophilicity.\n\n#### (ii) **Role of REASOAP SR-10 in Polymer Synthesis**\n\nREASOAP SR-10 serves as a **functional crosslinker or comonomer** in the synthesis of the hydrophilic polymer. It contributes in the following ways:\n\n1. **Introduction of Reactive Sites:**\n   Its reactive groups (e.g., epoxy, hydroxyl, or acrylic) can enable:\n   - Covalent bonding with other monomers.\n   - Formation of a crosslinked polymeric network during curing.\n\n2. **Enhancement of Hydrophilicity:**\n   The presence of polar or hydrophilic groups in REASOAP SR-10 (e.g., hydroxyl or ether units) increases the water-attracting ability of the final polymer. These groups can form hydrogen bonds with water and improve polymer wettability.\n\n3. **Formation of a Crosslinked Hydrophilic Network:**\n   During curing, the reactive groups in REASOAP SR-10 chemically link chains into a 3D network. This crosslinked structure improves water uptake without dissolving, a key feature for certain hydrophilic polymers like hydrogels.\n\n#### (iii) **Curing Process and Reactive Group Chemistry**\n\n- The reactive group in REASOAP SR-10 determines the specific curing reaction.\n  - For **epoxy groups**, crosslinking typically involves an amine-based curing agent that reacts with the epoxy ring.\n  - For **acrylic groups**, curing involves free-radical polymerization initiated by a thermal or photochemical initiator (e.g., benzoyl peroxide or UV light).\n  - For **hydroxyl groups**, curing may occur via esterification with diacids or urethane formation with isocyanates.\n\n- Optimal curing conditions (e.g., temperature, catalysts, and molar ratios) should be chosen based on the reactive group.\n\n---\n\n### Step 3: **Experimental Preparation Scheme for the Synthesis**\n\nHere is a generalized preparation scheme for a hydrophilic polymer incorporating REASOAP SR-10:\n\n1. **Materials Required:**\n   - Monomers (e.g., acrylic acid, N-vinylpyrrolidone, or other hydrophilic monomers).\n   - REASOAP SR-10 as the reactive hydrophilic crosslinker.\n   - Curing agent or initiator (depending on reactive group: e.g., a free-radical initiator for acrylic groups or an amine-based curing agent for epoxies).\n   - Solvent (if required for homogeneity, e.g., water or ethanol).\n\n2. **Step-by-Step Procedure:**\n   - **Step 1: Monomer Mixing:**\n     In a clean reaction flask, mix a selected hydrophilic monomer (e.g., acrylic acid) with the desired amount of REASOAP SR-10. Maintain a molar ratio such that REASOAP SR-10 contributes ~10-20 mol% to promote crosslinking without excessive rigidity.\n\n   - **Step 2: Addition of Initiator/Curing Agent:**\n     Add the curing agent or initiator based on the reactive group in REASOAP SR-10. For example:\n       - If REASOAP SR-10 has acrylic groups, dissolve a free-radical initiator like benzoyl peroxide (0.5 wt%) in the monomer mixture.\n       - If REASOAP SR-10 has epoxy groups, introduce a stoichiometric quantity of an amine curing agent such as triethylenetetramine.\n\n   - **Step 3: Polymerization/Curing:**\n     Heat the reaction mixture to the required temperature (e.g., 60–80°C for free-radical polymerization or room temperature for epoxy curing). For UV-curable systems, expose the mixture to a UV lamp under nitrogen to avoid oxygen inhibition.\n\n   - **Step 4: Post-Curing (If Necessary):**\n     Cure the polymer for additional time (e.g., 2–4 hours) at a slightly elevated temperature (e.g., 100°C) to ensure complete crosslinking.\n\n   - **Step 5: Washing and Drying:**\n     Wash the resultant polymer product to remove any unreacted monomers or byproducts. Use distilled water or a suitable solvent. Dry the polymer in a vacuum oven at 50–60°C.\n\n3. **Precautions:**\n   - Ensure the REASOAP SR-10 and other monomers are fully dissolved/mixed to avoid phase separation.\n   - Control temperature accurately, as overheating can lead to side reactions or degradation.\n\n4. **Characterization:**\n   - Confirm the hydrophilicity of the polymer using contact angle measurements or swelling tests in water.\n   - Verify the crosslinked structure via FTIR spectroscopy (to detect functional groups) or thermal analysis (DSC/TGA).\n\n---\n\n### Step 4: **Specific Contribution of REASOAP SR-10’s Reactive Group**\n\nThe reactive group of REASOAP SR-10 plays a dual role:\n1. It directly participates in the covalent crosslinking reaction to form a stable 3D polymer network.\n2. It introduces hydrophilic functionality to the network, allowing the polymer to exhibit water-swelling or water-retention behavior, crucial for hydrophilic applications like coatings, membranes, or hydrogels.\n\n---\n\n### Conclusion\n\nIn summary, REASOAP SR-10 is a valuable component in hydrophilic polymer synthesis due to its dual functionality: crosslinking via reactive groups and enhancing hydrophilicity through polar side groups. By carefully optimizing reaction conditions and polymerization parameters, you can exploit its properties to produce a robust and hydrophilic polymer network capable of absorbing water or interacting with aqueous environments. Following the above experimental scheme should allow you to successfully synthesize and characterize the desired hydrophilic polymer product."
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+  "design_question": "Using ethylene glycol, propose a step-growth polymerization reaction that would allow the formation of a polymer with enhanced hydrophilicity. Ensure the monomer selection complies with the prerequisites for polymerizable functional groups.",
+  "design_answer": "Certainly! Let’s systematically break down your question regarding the formation of a hydrophilic polymer using ethylene glycol and propose a comprehensive experimental preparation scheme based on step-growth polymerization principles. To meet your objectives, we will aim to enhance the polymer's hydrophilicity and provide detailed instructions for the synthesis.\n\n---\n\n### 1. **Analyze the question and summarize the key points:**\n   - **Objective:** Design a step-growth polymerization reaction using ethylene glycol to produce a hydrophilic polymer.\n   - **Key considerations:**\n     - Ethylene glycol is a diol (contains two hydroxyl groups, –OH), making it suitable for step-growth polymerization.\n     - For step-growth polymerization, we need complementary monomers with functional groups that react with hydroxyl groups, such as diacids, diacyl chlorides, or their derivatives.\n     - The final polymer should exhibit enhanced hydrophilicity. Hydrophilicity can be improved by increasing the density of hydrophilic groups (-OH, -COOH, -C=O, amides, etc.) in the polymer backbone.\n   - **Chemistry involved:** Typical step-growth polymerization routes involve esterification or amidation reactions between diols and diacids (or diacid derivatives), or urethane reactions between diols and isocyanates.\n   - **Approach:** We will use ethylene glycol as the diol and pair it with a diacid containing hydrophilic groups.\n\n---\n\n### 2. **Propose the detailed synthesis process:**\n   We will design a copolymer of poly(ethylene glycol-co-succinate) using **ethylene glycol** and **succinic acid** as the monomers. Succinic acid (HOOC-(CH2)2-COOH) is chosen for its hydrophilic carboxylic acid groups and straightforward reactivity.\n\n---\n\n#### Step 1: Materials and reagent preparation\n   - **Monomer 1 (Diol):** Ethylene glycol (HOCH2CH2OH).\n   - **Monomer 2 (Diacid):** Succinic acid (HOOC-(CH2)2-COOH).\n   - **Catalyst:** Typically, a strong acid catalyst such as **p-toluenesulfonic acid (p-TSA)** or **sulfuric acid** is used for esterification.\n   - **Solvent (optional):** Xylene or toluene can be added to aid in azeotropic removal of water during the reaction.\n   - **Other equipment:** Dean-Stark apparatus (if using azeotropic water removal), reflux setup.\n\n---\n\n#### Step 2: Reaction schematic\nThe reaction involves the **esterification** of ethylene glycol and succinic acid to form an aliphatic polyester with hydrophilic ester linkages:\n\\[\nHOCH_2CH_2OH + HOOC-(CH_2)_2-COOH \\rightarrow [-CH_2CH_2-O-C(O)-(CH_2)_2-C(O)-]_n + nH_2O\n\\]\n\n---\n\n#### Step 3: Experimental setup and procedure\n1. **Reaction setup:**\n   - Assemble a round-bottom flask with a reflux condenser and a Dean-Stark trap (if using azeotropic water removal) to eliminate the water formed during the reaction.\n   - Add a magnetic stir bar to the flask for mixing.\n   - Preheat the flask in an oil bath to maintain a temperature of 140–180 °C throughout the reaction.\n\n2. **Molar ratios of reactants:**\n   - Take ethylene glycol and succinic acid in a 1.1:1 molar ratio. For example:\n     - Ethylene glycol: 110 mmol (6.8 g, MW = 62.07 g/mol).\n     - Succinic acid: 100 mmol (11.8 g, MW = 118.09 g/mol).\n   - The slight excess of ethylene glycol ensures the complete reaction of the diacid, minimizing unreacted acid groups.\n\n3. **Catalyst addition:**\n   - Add 0.5–1 wt% (relative to the total mass of reactants) of p-toluenesulfonic acid (p-TSA) as the catalyst. Alternatively, a few drops of concentrated sulfuric acid can be used.\n\n4. **Heating and monitoring:**\n   - Heat the reaction mixture to 140–180 °C under reflux with vigorous stirring.\n   - As the reaction proceeds, water is produced as a byproduct. Using a Dean-Stark apparatus, collect and remove water from the system to shift the equilibrium toward polyester formation.\n\n5. **Reaction duration:**\n   - Continue heating for 4–6 hours or until water formation ceases, indicating the completion of esterification.\n\n6. **Optional purification:**\n   - Cool the reaction mixture to room temperature. Dissolve the crude polymer in a minimal amount of dichloromethane (CH2Cl2) and precipitate it into cold methanol to purify the polymer. Collect the polymer by filtration and allow it to dry under vacuum.\n\n---\n\n#### Step 4: Expected results and hydrophilicity enhancement\n- **Polymer formed:** Poly(ethylene glycol-co-succinate), an aliphatic polyester containing hydrophilic ester groups (-C=O and -O).\n- **Hydrophilic character:** The incorporation of multiple ester linkages significantly enhances the hydrophilicity of the polymer compared to a purely aliphatic hydrocarbon chain polymer.\n\n---\n\n#### Step 5: Safety considerations\n1. Ensure proper ventilation when heating (e.g., using a fume hood) to prevent exposure to toxic vapors.\n2. Handle acids and organic solvents with care to avoid burns or inhalation hazards—use nitrile gloves and safety goggles.\n\n---\n\n### Final Summary of the Experimental Scheme\n- **Reactants:** Ethylene glycol and succinic acid in a 1.1:1 molar ratio.\n- **Catalyst:** p-TSA (0.5–1 wt%) or sulfuric acid.\n- **Temperature:** 140–180 °C under reflux.\n- **Reaction time:** 4–6 hours with water removal.\n- **Purification:** Precipitation into methanol.\n- **Product:** A hydrophilic polyester with ester linkages.\n\nThis systematic approach ensures that you achieve a polymer with enhanced hydrophilicity while providing a reliable experimental scheme for laboratory practice. Let me know if you have further questions or need a refinement of this scheme!"
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diff --git a/task2/task2-qa/Solvents_-_2015.json b/task2/task2-qa/Solvents_-_2015.json
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+{
+  "design_question": "Identify a suitable solvent to swell the polymer that will allow effective interaction with the provided molecule and explain the criteria you used to select this solvent.",
+  "design_answer": "Certainly! Let me systematically guide you through the question, providing the criteria and method used to identify the most suitable solvent for swelling the polymer. Let us think step by step.\n\n---\n\n### Step 1: Analyze the Question and Summarize Key Points\nThe goal is to identify a solvent that can:\n1. Adequately swell the polymer, allowing its chains to become accessible to the provided molecule.\n2. Facilitate effective interaction between the polymer and the provided molecule for subsequent chemical modifications or adsorption.\n3. Meet practical experimental considerations, such as polymer solubility, compatibility with functional groups, and safety in the laboratory.\n\nThe selection of this solvent depends on:\n- The nature of the polymer (e.g., hydrophobic, hydrophilic, polar, nonpolar).\n- The properties of the molecule provided by the student.\n- The solvent’s ability to interact with both the polymer and the molecule, particularly in the context of hydrophilic polymer preparation.\n\n---\n\n### Step 2: Criteria for Solvent Selection\nTo make a systematic and logical choice, consider the following criteria:\n\n1. **Polymer-Solvent Interaction**:\n   - The solvent must interact well with the polymer to cause swelling. This depends on the polymer's polarity, functional groups, and molecular structure.\n   - Use the principle of \"like dissolves like.\" For hydrophilic polymers, polar and hydrophilic solvents are typically more effective.\n\n2. **Solvent-Molecule Interaction**:\n   - The solvent should also provide a medium in which the molecule remains soluble or sufficiently miscible to interact with the polymer. Consider the polarity, hydrogen bonding capability, or ionic nature of the molecule.\n\n3. **Chemical Compatibility**:\n   - The solvent must not react with the polymer's functional groups or the provided molecule, ensuring the intended interaction or modification is preserved.\n\n4. **Swelling Power and Safety**:\n   - The solvent must swell the polymer without dissolving it entirely.\n   - Factors like boiling point, toxicity, ease of removal, and environmental considerations should also guide your choice.\n\n---\n\n### Step 3: Common Solvent Classes and Selection Guidelines\nFor hydrophilic polymers, some typical solvent categories to consider include:\n1. **Water and Aqueous Solutions:**\n   - If the polymer is strongly hydrophilic, pure water or water with added salts (e.g., NaCl for ionic strength adjustment) may work well to swell the polymer.\n\n2. **Alcohols:**\n   - Short-chain alcohols, such as methanol or ethanol, can enhance swelling if the polymer has moderate hydrophilicity. Alcohol-water mixtures are also a good choice.\n\n3. **Polar Aprotic Solvents:**\n   - Solvents like dimethyl sulfoxide (DMSO) or N,N-dimethylformamide (DMF) are excellent for some polar polymers, as they have strong solvating power.\n\n4. **Acidic or Basic Solvents:**\n   - If the polymer or molecule has acid-base interactions, acidic (e.g., acetic acid) or basic (e.g., triethylamine) solvents could promote swelling or activation.\n\n---\n\n### Step 4: Specific Recommendations\nWithout the exact polymer and molecule details, it appears you are preparing a hydrophilic polymer. Therefore:\n1. Start by testing **water or water-alcohol mixtures.**\n   - Use water if the polymer is highly hydrophilic (e.g., poly(acrylic acid)).\n   - Use ethanol-water mixtures (e.g., 70% ethanol) for moderately hydrophilic polymers.\n\n2. If water-based systems do not work, test **DMSO or DMF.**\n   - They are compatible with a wide variety of hydrophilic and polar polymers.\n\n3. Check for sensitivity to pH or ionic strength:\n   - For charged polymers (e.g., poly(amines) or polyelectrolytes), adjust the pH or add salts (e.g., NaCl) to control electrostatic interactions and enhance swelling.\n\n4. Perform trial experiments with small amounts to optimize solvent-polymer ratios.\n\n---\n\n### Step 5: Justification and Experimental Plan\n#### Justification:\nThe selection of the solvent is driven by:\n- Hydrophilic interactions (based on polymer polarity).\n- Accessibility of polymer functional groups for reaction or interaction with the molecule.\n- Solubility and miscibility considerations.\n\n#### Experimental Plan:\n1. **Material Preparation**:\n   - Measure 100 mg of the polymer into a glass vial.\n\n2. **Solvent Addition**:\n   - Add 10 mL of the selected solvent (e.g., water, ethanol, water-ethanol mixture, or DMSO).\n\n3. **Swelling Observation**:\n   - Allow the system to equilibrate for 24 hours at room temperature (or elevated temperatures, e.g., 40°C, if needed).\n   - Measure the degree of swelling or dissolution visually or gravimetrically.\n\n4. **Further Testing**:\n   - If swelling does not occur, systematically change the solvent ratio or test additional solvents.\n\n5. **Safety Precautions**:\n   - Always handle organic solvents (e.g., DMSO or ethanol) with proper ventilation and PPE.\n\n---\n\n**Conclusion**:\nStart with the simplest and least toxic solvents, prioritizing water or water-alcohol mixtures for hydrophilic systems. Adjust solvent composition as needed based on observed swelling behavior. By carefully considering polarity, compatibility, and safety, you will identify the optimal solvent for enabling interactions between the polymer and the provided molecule."
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diff --git a/task2/task2-qa/Synthesis and characterization of UV curable urethane acrylate oligomers containing ammonium salts for anti-fog coatings.json b/task2/task2-qa/Synthesis and characterization of UV curable urethane acrylate oligomers containing ammonium salts for anti-fog coatings.json
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+{
+  "design_question": "Ethanolamine is one of the starting materials used in polymer modification. Propose how ethanolamine's structure and reactivity play a vital role in introducing hydrophilic functional groups into the polymer material.",
+  "design_answer": "To answer your question and explain how ethanolamine can be utilized in introducing hydrophilic functional groups into polymer materials, let us carefully approach this step by step, analyzing its structure and reactivity. We will then outline an experimental strategy for modifying a polymer, ensuring we cover all relevant details methodically, as per your request.\n\n---\n\n### Step 1: Key Points in the Question\n1. **Ethanolamine’s Structure and Reactivity:**\n   - Ethanolamine (HOCH₂CH₂NH₂) has both hydroxyl (-OH) and amine (-NH₂) functional groups.\n   - These groups make ethanolamine reactive towards various chemical transformations, allowing it to graft hydrophilic groups onto polymers.\n   - Importantly, the hydroxyl group introduces hydrogen-bonding capacity, while the amine group can participate in nucleophilic reactions or protonation under acidic conditions.\n\n2. **Objective:**\n   - To design an experimental approach to modify a polymer using ethanolamine as a reagent to enhance its hydrophilicity.\n\n---\n\n### Step 2: Role of Ethanolamine in Enhancing Hydrophilicity\n- The **hydroxyl (-OH)** and **amine (-NH₂)** moieties of ethanolamine are highly hydrophilic. When these groups are covalently incorporated into a polymer backbone or grafted onto the surface, they:\n  1. Improve the polymer's *wetting properties* by interacting with water molecules via hydrogen bonding.\n  2. Increase solubility or water absorption (depending on the degree of functionalization).\n  \nAs an amphiphilic molecule, ethanolamine is particularly useful because it is small and reactive, enabling selective functionalization without drastically altering the polymer’s mechanical properties.\n\n---\n\n### Step 3: Experimental Preparation Scheme for Polymer Modification with Ethanolamine\nHere, I propose a synthetic strategy where ethanolamine is chemically attached to an existing polymer backbone to enhance its hydrophilicity. The polymer system will depend on the functional groups present, but common strategies involve reacting ethanolamine with polymers bearing **reactive electrophilic groups** (e.g., anhydride, epoxide, or halide).\n\nLet us consider using **poly(maleic anhydride)** as the starting polymer, as it is a common material for functional modification.\n\n---\n\n#### **Reaction Schematic**\nPoly(maleic anhydride) (PMA) + Ethanolamine → Poly(maleic acid ethanolamine) (Modified PMA with hydrophilic groups)\n\n---\n\n### Experimental Steps for Synthesizing Hydrophilic Polymer\n\n#### **Materials:**\n1. **Poly(maleic anhydride)** (PMA) - Source of reactive anhydride groups.\n2. **Ethanolamine** - Hydrophilic reagent.\n3. **Solvent:** Dimethylformamide (DMF) or tetrahydrofuran (THF) - Polar, aprotic solvent for dissolution.\n4. **Catalyst (optional):** Triethylamine (TEA) or a few drops of pyridine to neutralize excess acidity.\n\n---\n\n#### **Step-by-Step Procedure:**\n\n##### 1. **Polymer Dissolution:**\n   - Dissolve **1 g of poly(maleic anhydride)** in **20 mL of dry DMF** under an inert atmosphere (e.g., nitrogen or argon) at room temperature. \n   - Stir continuously until the polymer is fully dissolved (1–2 hours).\n\n   *Note:* Ensure complete solubilization for a uniform reaction.\n\n##### 2. **Preparation of Ethanolamine Solution:**\n   - In a separate container, dissolve **0.1 mL of ethanolamine (1.5 mmol)** in **5 mL DMF.**\n   - This ensures accurate dispersion and avoids localized overreaction in the polymer solution.\n\n##### 3. **Controlled Addition:**\n   - Add the ethanolamine solution dropwise to the polymer solution with constant stirring at **room temperature.**\n   - Allow the reaction to proceed for **4–6 hours.**\n\n   *Key Reaction:* Ethanolamine reacts with the anhydride group of PMA, opening the cyclic anhydride and forming an amide bond (via the amine group) and a carboxylic acid group (from the hydroxyl group).\n\n##### 4. **Monitoring the Reaction:**\n   - Monitor the reaction progression using **FTIR spectroscopy.**\n     - Absorption peaks at ~1850 cm⁻¹ and ~1780 cm⁻¹ (characteristic of maleic anhydride) will diminish.\n     - New peaks around ~3300 cm⁻¹ (O-H stretch) and ~1650 cm⁻¹ (C=O stretch for amide) will appear.\n\n##### 5. **Precipitation and Purification:**\n   - Precipitate the modified polymer by adding the reaction mixture dropwise into **100 mL of cold diethyl ether** while stirring.\n   - Filter the precipitate using a vacuum filtration setup and wash with ether to remove residual ethanolamine and unreacted starting materials.\n\n##### 6. **Drying:**\n   - Dry the polymer under vacuum at **40–50°C** overnight.\n\n---\n\n### Reaction Stoichiometry and Yield Estimation:\n- For a 1 g sample of poly(maleic anhydride) (approx. 10 mmol of anhydride groups) and 1.5 mmol ethanolamine, this is a sub-stoichiometric reaction. Hence, only partial modification is expected (10–15% functionalization) to retain the polymer chain’s physical integrity.\n\n---\n\n### Step 4: Post-Reaction Characterization\n\n1. **FTIR Analysis:**\n   - Confirm the disappearance of anhydride peaks and the appearance of O-H and N-H stretches.\n\n2. **Contact Angle Measurement:**\n   - Measure the water contact angle of the modified polymer film to assess the improvement in hydrophilicity. A decreased contact angle indicates better hydrophilicity.\n\n3. **Thermal Stability:**\n   - Perform thermogravimetric analysis (TGA) to ensure the modification does not compromise the polymer’s thermal properties.\n\n---\n\n### Step 5: Conclusion\nEthanolamine’s bifunctional nature (hydroxyl and amine) plays a pivotal role in enhancing polymer hydrophilicity by introducing hydrogen-bonding-capable groups. When properly reacted with polymers such as poly(maleic anhydride), ethanolamine introduces carboxylic acids and amides, enhancing hydrophilicity while maintaining the polymer matrix’s structural integrity.\n\nBy following the outlined experimental scheme, you should be able to successfully utilize ethanolamine for producing hydrophilic polymers with applications in water-based coatings, biomedical materials, or membrane technologies.\n\nIf you have further questions or need clarification, feel free to ask!"
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diff --git a/task2/task2-qa/Synthesis of UV-curable acrylate polymer containing sulfonic groups for anti-fog coatings.json b/task2/task2-qa/Synthesis of UV-curable acrylate polymer containing sulfonic groups for anti-fog coatings.json
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+{
+  "design_question": "Explain the role of 2-acrylamido-2-methyl propane sulfonic acid (AMPS) in enhancing the hydrophilicity of the polymer during its copolymerization process.",
+  "design_answer": "Certainly! Let's address your question systematically while following the outlined requirements for clarity and depth. The focus here is understanding the role of 2-acrylamido-2-methyl propane sulfonic acid (AMPS) in enhancing the hydrophilicity of a polymer during its copolymerization process.\n\n---\n\n### **Key Points from the Question**\n1. **Analyzing the molecule**: AMPS is a highly functional monomer with both amide and sulfonic acid groups. These groups contribute significantly to the hydrophilicity of the polymer.\n2. **Core topic**: We aim to determine and explain how AMPS enhances hydrophilicity during copolymerization and the mechanisms that underlie its behavior.\n\nNow, I will answer systematically step by step:\n\n---\n\n### **Detailed Explanation and Experimental Preparation for Copolymerization Involving AMPS**\n\n#### **I. Properties of AMPS Relevant to Hydrophilicity**\nAMPS is a hydrophilic monomer for several reasons:\n1. **Sulfonic Acid Group (-SO₃H)**:\n   - The sulfonic acid functional group is highly polar and ionizable. This polarity enables AMPS-containing polymers to interact strongly with water molecules through hydrogen bonding and ionic interactions, thereby enhancing hydrophilicity.\n   - The sulfonic group also provides excellent water solubility and anti-fouling properties, making AMPS ideal for polymers in aqueous environments.\n   \n2. **Amide Group (-CONH₂)**:\n   - The amide group can form hydrogen bonds, further contributing to hydrophilicity.\n   - It assists in stabilizing the polymer structure with dual hydrophilic capabilities from both the amide and sulfonic acid functionalities.\n\nTogether, these groups make AMPS a building block for hydrophilic polymers, enabling applications such as water-absorbent materials, medical hydrogels, and ion-exchange membranes.\n\n---\n\n#### **II. Copolymerization Process Using AMPS**\n\n**Objective**: To introduce AMPS as a co-monomer during the synthesis of a hydrophilic polymer, enhancing the polymer's interaction with water.\n\n##### **1. Selection of Co-Monomers**\nWhen designing the copolymerization scheme:\n- Select co-monomers that are compatible with AMPS. Examples include non-ionic hydrophilic monomers (e.g., acrylamide, N-vinyl pyrrolidone) or ionic monomers (e.g., acrylic acid).\n  \n- The choice of co-monomers depends on the targeted polymer properties. For hydrophilic polymers, acrylamide (AM) or acrylic acid (AA) are common partners in copolymerization with AMPS.\n\n##### **2. Reaction Conditions**\n- **Reaction Type**: Free-radical copolymerization is the preferred method for incorporating AMPS due to its efficiency.\n- **Initiator**: Use a water-soluble initiator such as potassium persulfate (KPS) or ammonium persulfate (APS), as AMPS is highly hydrophilic.\n- **Solvent**: An aqueous system is suitable since AMPS and most co-monomers dissolve well in water.\n- **Temperature**: Set the reaction temperature within 60–80°C, which is typical for persulfate initiators.\n- **pH Control**: Important to maintain pH between 5–7 to ensure the sulfonic acid group remains ionized, maximizing hydrophilic properties.\n\n##### **3. Proportions and Molar Ratios**\n- The molar ratio of AMPS to co-monomer (e.g., acrylamide) depends on the desired hydrophilicity. Typical ratios are 1:1 or 1:2 (AMPS:co-monomer).\n- Example: For 10 g total monomer weight:\n  - AMPS: 5 g\n  - Acrylamide (AM): 5 g\n\n##### **4. Reaction Monitoring**\n- Stir the solution continuously to ensure homogeneous mixing of AMPS during polymerization.\n- Monitor viscosity as the reaction progresses, indicating polymer formation.\n\n---\n\n#### **III. Role of AMPS in Enhancing Hydrophilicity**\nDuring copolymerization, AMPS contributes to hydrophilicity in several ways:\n1. **Ionic Nature**:\n   - The sulfonic acid group dissociates in water, creating negative charges on the polymer chain. These charges attract water molecules and repel contaminants, maximizing hydrophilic behavior.\n   \n2. **Hydrogen Bonding**:\n   - Both the sulfonic group and amide group enable the polymer to form strong hydrogen bonds with water molecules, further enhancing water retention.\n\n3. **Copolymer Formation**:\n   - AMPS forms covalent bonds with co-monomers (e.g., acrylamide) during free-radical polymerization. The resulting polymer chain integrates AMPS units uniformly, ensuring hydrophilicity throughout the polymer.\n\n4. **Structural Impact**:\n   - The bulkiness of the AMPS molecule contributes to chain separation within the polymer, preventing aggregation. This structural feature increases surface area exposure to water, boosting hydrophilicity.\n\n---\n\n#### **IV. Example Protocol for Copolymerization of AMPS and Acrylamide**\n1. **Materials**:\n   - AMPS: 5 g\n   - Acrylamide: 5 g\n   - Distilled water: 100 mL\n   - Potassium persulfate (KPS): 0.1 g (initiator)\n\n2. **Procedure**:\n   1. Dissolve acrylamide and AMPS in distilled water to form a homogeneous solution.\n   2. Add KPS to the solution while stirring under nitrogen purge to eliminate oxygen (oxygen inhibits free-radical polymerization).\n   3. Heat the solution to 70°C and maintain constant stirring for 2 hours.\n   4. After polymerization, cool the mixture and precipitate the polymer by adding it dropwise into acetone (non-solvent).\n\n3. **Characterization**:\n   - Test hydrophilicity using water absorption studies, contact angle measurements, or swelling ratio analysis.\n\n---\n\n#### **Key Takeaways**\n- AMPS plays a critical role in enhancing hydrophilicity through its sulfonic acid and amide groups, providing ionic and hydrogen-bonding capabilities.\n- During copolymerization, careful control of molar ratios, reaction conditions, and solvent systems ensures successful incorporation of AMPS into the polymer chain.\n- AMPS-based hydrophilic polymers can be tailored for diverse applications, including water treatment, superabsorbent materials, and biomedical devices.\n\nBy following this systematic approach, you can fully leverage AMPS's properties to synthesize a polymer with enhanced hydrophilicity.\n\n--- \n\nLet me know if you'd like further clarification on any step or additional insights!"
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+{
+  "design_question": "How would you incorporate glycerol dimethacrylate into a thermoplastic polymer matrix to enhance its hydrophilicity? Detail the steps for blending it with other components and describe the curing process.",
+  "design_answer": "### Analysis of the Question:\n\nThe central idea of your question concerns the incorporation of **glycerol dimethacrylate (GDMA)** into a thermoplastic polymer matrix to enhance its hydrophilicity. GDMA has multiple hydroxyl (-OH) groups that contribute to hydrophilicity, and its methacrylate groups allow it to chemically bond or polymerize within a matrix.\n\nKey considerations:\n1. **Chemical Characteristics**: GDMA is a hydrophilic monomer with two methacrylate groups, which makes it ideal for copolymerization to enhance the hydrophilicity of thermoplastic polymers.\n2. **Polymer Compatibility**: Choosing a compatible thermoplastic polymer with free functional groups or open chains for blending and crosslinking.\n3. **Preparation Method**: Achieving homogeneous mixing, polymerization, and curing within the thermoplastic matrix.\n4. **Reaction Conditions**: Ensuring the methacrylate groups polymerize effectively without damaging the polymer matrix.\n\n### Experimental Preparation Scheme:\n\nHere’s the step-by-step, systematic procedure to incorporate GDMA into a thermoplastic polymer matrix and enhance the hydrophilicity:\n\n---\n\n#### **Step 1: Selection of Thermoplastic Polymer Matrix**\nChoose a thermoplastic polymer that can physically or chemically blend with GDMA. Suitable candidates include:\n- Polyvinyl chloride (PVC)\n- Poly(methyl methacrylate) (PMMA)\n- Polystyrene (PS)\n- Polyethylene glycol (PEG) blends\n\nEnsure the polymer has sufficient thermal stability to withstand the curing process and can interact with methacrylate groups and hydroxyl functionalities.\n\n---\n\n#### **Step 2: Preparation of Materials**\n**Materials Needed:**\n- **GDMA**: Monomer to enhance hydrophilicity.\n- **Thermoplastic polymer**: Base matrix (e.g., PMMA).\n- **Crosslinking agent**: Ethylene glycol dimethacrylate (EGDMA) or other crosslinkers (optional).\n- **Thermal initiator**: Benzoyl peroxide (BPO) or azobisisobutyronitrile (AIBN) to initiate free radical polymerization.\n- **Solvent**: Tetrahydrofuran (THF), to facilitate mixing if the polymer matrix is not molten.\n- **Heat Source**: Oven or water bath to control curing temperature.\n\n---\n\n#### **Step 3: Formulate the Polymer Blend**\n1. **Weigh the Components**:\n   - GDMA (10–50 wt% relative to the polymer matrix, depending on desired hydrophilicity).\n   - Thermoplastic polymer (remaining weight percentage).\n   - Crosslinking agent (if used): 1–5 wt% based on GDMA content.\n   - Thermal initiator: 0.5–1 wt%.\n\n2. **Dissolve in a Solvent** (if necessary):\n   - Dissolve the thermoplastic polymer in THF. Ensure the solvent fully solubilizes the polymer to create a homogeneous solution.\n   - Separately, dissolve GDMA and the initiator in the same solvent, then mix this solution with the above polymer solution.\n\n---\n\n#### **Step 4: Mixing and Homogenization**\n- Use a mechanical mixer or ultrasonic stirring apparatus to create a homogeneous blend of GDMA and the thermoplastic polymer matrix. Maintain stirring for 30–60 minutes at room temperature for a uniform mixture.\n\n---\n\n#### **Step 5: Polymerization and Curing**\n1. **Transfer the Blend**:\n   - Pour the homogenized mixture into molds or onto a flat surface lined with a non-stick layer (e.g., Teflon-coated sheets).\n\n2. **Set the Reaction Temperature**:\n   - Gradually heat the material to the polymerization temperature (e.g., 60–80°C for BPO or AIBN systems).\n   - Ensure even heating throughout the polymer layer. This activates the thermal polymerization of the methacrylate groups.\n\n3. **Control Curing Time**:\n   - Allow curing to proceed for 2–6 hours, depending on the matrix’s thickness and crosslink density. Longer curing ensures complete polymerization and bonding.\n\n---\n\n#### **Step 6: Post-Curing Treatment**\n1. **Remove Residual Solvent**:\n   - Dry the cured polymer at 50–70°C for 3–6 hours in a vacuum oven to eliminate any leftover solvent.\n\n2. **Enhanced Network Formation** (if required):\n   - Use UV curing or additional thermal treatment to strengthen bonding further.\n\n---\n\n#### **Step 7: Characterization**\nOnce the polymers are formed:\n1. **Hydrophilicity Testing**:\n   - Test the water contact angle (WCA) on the cured polymer surface.\n   - A decrease in the WCA indicates improved hydrophilicity.\n\n2. **Mechanical Testing**:\n   - Confirm that the addition of GDMA did not compromise the structural integrity of the polymer matrix.\n3. **Fourier Transform Infrared Spectroscopy (FTIR)**:\n   - Verify the successful incorporation of GDMA by identifying the characteristic hydroxyl and methacrylate functional group signals.\n\n---\n\n### Additional Notes:\n1. **Safety Precautions**:\n   - Handle GDMA and initiators (like BPO or AIBN) with care as they can be reactive and harmful.\n2. **Optimization**:\n   - The wt% ratio of GDMA and polymer matrix can be adjusted through preliminary trials to balance hydrophilicity and mechanical properties.\n\n---\n\nThis approach provides clear guidelines for incorporating glycerol dimethacrylate into a thermoplastic polymer matrix for enhanced hydrophilicity."
+}
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+{
+  "design_question": "A water dispersible polyurethane compound is to be modified using a silicone compound containing —OH groups. How would you determine the appropriate ratio of the silicone compound to the polyurethane compound to ensure uniform dispersion while maintaining film integrity?",
+  "design_answer": "### Analyzing the Question and Summarizing Key Points\n\nYour question pertains to the modification of a **water-dispersible polyurethane** with a **silicone compound containing —OH groups.** Specifically, you are looking to determine the appropriate **ratio** of the silicone compound to the polyurethane to achieve:\n1. **Uniform dispersion** of the modified polymer in water.\n2. **Good film-forming properties** (film integrity) while maintaining hydrophilicity.\n\nThis problem requires understanding both chemistry fundamentals (polyurethane modification and silicone reactivity) and considerations of physical properties (film-forming, dispersibility).\n\nKey points of the question:\n- Polyurethane is the base polymer, and it is water-dispersible. This implies it likely contains hydrophilic ionic or non-ionic groups (e.g., sulfonates, carboxylates, or ethylene oxide/PEG chains) that facilitate dispersion in water.\n- Silicone compound has —OH groups, suggesting it may participate in chemical bonding (via reaction with isocyanates in polyurethane) or physical interaction, potentially introducing hydrophobicity or altering the polymer's surface activity.\n- The challenge is optimizing the **silicone-to-polyurethane ratio** to balance uniform dispersion and good film integrity without compromising hydrophilicity. Incorrect ratios might lead to phase separation, poor dispersibility, or brittle/incompatible films.\n\nTo address this systematically, we need a detailed experimental scheme for synthesizing and evaluating the modified polymer.\n\n---\n\n### Detailed and Systematic Preparation Scheme\n\n#### Step 1: Define the Reaction Mechanism\nThe modification typically occurs through **grafting or blending**:\n1. If isocyanate groups (—NCO) are still available in your prepolymer, the silicone compound (containing —OH) can react with them to form urethane linkages (R—N—CO—O—Si). This creates a covalent bond, incorporating silicone into the polyurethane backbone.\n2. If no —NCO is available, the silicone compound may mix physically with the polyurethane, assisted by hydrogen bonding or secondary interactions. In this case, phase compatibility becomes critical to prevent separation.\n\n---\n\n#### Step 2: Experimental Strategy to Determine Silicone-to-Polyurethane Ratio\n\n1. **Start with a theoretical calculation** based on molecular weights:\n   - Determine the molecular weight of the silicone compound (M_s) and the polyurethane (M_p).\n   - Calculate the number of —OH groups in the silicone compound and the number of reactive sites (e.g., —NCO or ionic sites) in the polyurethane.\n\n2. **Establish an initial range of silicone-to-polyurethane ratios:**\n   - Start with **silicone-to-polyurethane weight ratios** (0.5:100, 1:100, 2:100, 5:100, etc.).\n   - Too much silicone can compromise dispersion or overplasticize the film, while too little may not produce significant modification.\n\n3. **Reaction Stoichiometry (if grafting is used):**\n   - For a covalent reaction with —NCO, ensure a moderate stoichiometric excess of —NCO groups (e.g., [NCO]/[OH] ≥ 1.2) for complete reaction.\n   - Example: If your prepolymer contains 2 mmol of —NCO groups per gram, and your silicone compound has 1 mmol of —OH groups per gram, start with a 1:3 or 1:2 molar ratio of —OH to —NCO.\n\n4. **Solvent and Catalyst Selection:**\n   - Use a polar aprotic solvent (like DMF or acetone) for uniform mixing and control of viscosity.\n   - Incorporate a catalyst like dibutyltin dilaurate (DBTDL) if curing or grafting the silicone compound via reaction with —NCO.\n\n---\n\n#### Step 3: Reaction Process\n1. **Stepwise Addition of Silicone:**\n   - Dissolve the water-dispersible polyurethane in a suitable solvent.\n   - Slowly add the silicone compound under stirring to prevent localized oversaturation, which can lead to phase separation. A mechanical stirrer or homogenizer is recommended for uniform dispersion.\n\n2. **Temperature and Reaction Time:**\n   - If a chemical reaction is expected (bonding silicone to polyurethane through —NCO groups), maintain the temperature at 50–80°C for 2–6 hours, avoiding premature gelation.\n   - For physical blending, ensure thorough emulsification for 30–60 minutes at room temperature.\n\n3. **Water Dispersion Testing:**\n   - Gradually add water (pH ~7) to the reaction mixture under high-speed stirring to produce an aqueous dispersion. Test the stability of dispersion (check for sedimentation or agglomeration over time).\n\n---\n\n#### Step 4: Evaluate Film Integrity and Hydrophilicity\n1. **Prepare Thin Films:**\n   - Cast films of the modified polymer on a glass substrate and dry at 50–80°C for 24 hours.\n\n2. **Characterize the Films:**\n   - **Film integrity:** Test mechanical properties (tensile strength, elongation at break) using a universal testing machine. Optimize the silicone content to achieve films that are flexible and continuous.\n   - **Hydrophilicity:** Measure the water contact angle. Lower angles indicate higher hydrophilicity (~30–50° is optimal).\n\n---\n\n#### Step 5: Optimize Ratio Based on Results\n1. Compare results for different silicone-to-polyurethane ratios.\n2. Select the lowest silicone ratio that maintains good film integrity and hydrophilicity, ensuring uniform dispersion in water.\n\n---\n\n### Final Notes\n- Typical starting ratios are in the range of **1–5% (w/w) silicone compound relative to polyurethane.** Increase gradually if needed.\n- Excess silicone might reduce hydrophilicity and cause phase separation, so balance is critical.\n\nBy following this systematic experimental protocol, you will be able to determine the optimal silicone-to-polyurethane ratio while ensuring uniform dispersion and maintaining film integrity."
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+{
+  "design_question": "Explain the role of polyvinylpyrrolidone (PVP), specifically when used in combination with other compounds, in creating graft polymerized coatings to enhance hydrophilicity. How would you ensure that PVP becomes effectively entrapped within the polymer matrix?",
+  "design_answer": "To address your question, we will systematically approach the role of polyvinylpyrrolidone (PVP) in enhancing hydrophilicity when combined with other compounds, particularly in graft polymerizations to produce hydrophilic coatings. I will also provide an experimental preparation scheme that ensures PVP becomes effectively entrapped within the polymer matrix.\n\n---\n\n### **Key Points to Consider**\n1. **Polyvinylpyrrolidone's Properties**:\n   - PVP is a hydrophilic polymer due to its amide functional groups that can form hydrogen bonds with water molecules. It is non-toxic, biocompatible, and highly soluble in water, making it ideal for creating hydrophilic materials.\n   - When used in polymer coatings, PVP improves water absorption, antifouling properties, and biocompatibility of the substrate.\n\n2. **Graft Polymerization Technique**:\n   - Graft polymerization creates a covalent bond between the polymer backbone and side chains (like PVP), ensuring the coating is durable and strongly adhered to the substrate.\n\n3. **Challenges in Entrapping PVP**:\n   - PVP must become covalently linked or physically entrapped in the polymer matrix to prevent it from washing away or leaching out during use.\n   - Designing reaction conditions that promote grafting of PVP onto the polymer backbone is critical.\n\n---\n\n### Step-by-Step Experimental Preparation Scheme\n\n#### **Step 1: Surface Preparation**\n- Before initiating graft polymerization, prepare the substrate (e.g., glass, polymeric film, ceramic surface) to ensure proper adhesion.\n- **Procedure**:\n  - Clean the surface using ethanol or acetone, followed by water to remove impurities.\n  - Apply an oxygen plasma or UV treatment to introduce reactive functional groups (e.g., hydroxyl or carboxyl groups) onto the surface, increasing its reactivity for subsequent polymerization.\n\n---\n\n#### **Step 2: Selection of Base Polymer**\n- Select a hydrophobic or semi-hydrophilic base polymer (e.g., poly(acrylic acid), polyethylene glycol, or polystyrene) for grafting.\n- Choose a polymer that can interact with PVP chemically or physically by forming covalent bonds.\n\n- **Key Reaction Principle**: \n  Incorporation of PVP occurs through radical or ionic mechanisms, depending on the desired polymerization method.\n\n---\n\n#### **Step 3: Reaction System Design**\nChoose **graft polymerization conditions** that enhance the covalent grafting of PVP onto the polymer backbone. Here, we use *radical graft polymerization* as a general method.\n\n##### **Reaction Details**:\n1. **Initiator System**:\n   - Use an appropriate radical initiator (commonly, **potassium persulfate (KPS)** or **benzoyl peroxide**) to generate free radicals on the base polymer backbone, promoting the addition of PVP.\n\n2. **Solvent**:\n   - Use a polar, aprotic solvent (e.g., DMF or water) to dissolve PVP and the base polymer and allow proper interactions between the reactants.\n\n3. **Molar Ratios and Concentrations**:\n   - Base polymer: Adjust base polymer concentration between 5–15 wt%.\n   - PVP: Use PVP at 20–40 wt% to ensure an excess of the hydrophilic component.\n   - Initiator: Typically use 0.5–1 wt% based on the total weight of the solution.\n\n---\n\n#### **Step 4: Grafting Reaction Procedure**\n- **Experimental Setup**:\n   - Dissolve base polymer, PVP, and the radical initiator in the solvent under stirring at constant temperature.\n   - Maintain the reaction temperature between 60–80°C (optimal for radical reactions) under a nitrogen or argon atmosphere to prevent oxygen quenching.\n\n- **Reaction Mechanism**:\n   - The initiator generates free radicals on the backbone, which promote the grafting of PVP molecules. This forms covalent bonds between PVP and the polymer network, ensuring PVP is entrapped and permanently integrated.\n\n- **Reaction Time**:\n   - Allow the reaction to proceed for 4–6 hours to ensure complete grafting.\n\n---\n\n#### **Step 5: Post-Reaction Processing**\n- After the reaction:\n   - Cool the reaction mixture to room temperature.\n   - Wash the resulting polymer coating thoroughly with ethanol or water to remove unreacted PVP and initiators.\n   - Dry the coating under vacuum to eliminate residual solvents.\n\n---\n\n#### **Step 6: Characterization**\nTo confirm successful grafting and entrapment of PVP:\n1. **Contact Angle Measurement**:\n   - Measure the water contact angle of the coated surface. A lower contact angle (<30°) confirms enhanced hydrophilicity.\n\n2. **Fourier Transform Infrared Spectroscopy (FTIR)**:\n   - Identify the characteristic amide peak at ~1650 cm⁻¹, indicative of PVP grafting.\n\n3. **Scanning Electron Microscopy (SEM)**:\n   - Observe the coating morphology to ensure uniform distribution of PVP.\n\n4. **Leaching Test**:\n   - Test for stability by immersing the coated substrate in water and verifying that PVP does not leach out significantly.\n\n---\n\n### Additional Considerations\n1. **Crosslinkers**:\n   - To further secure PVP within the polymer matrix, add a crosslinker (e.g., glutaraldehyde or ethylene glycol dimethacrylate), which bridges PVP and the base polymer.\n   - Introduce ~5 wt% crosslinker during polymerization to form a denser network.\n\n2. **Scaling Up**:\n   - Optimize the reagent ratios during small-scale experiments to ensure consistent results before scaling up to larger batches.\n\n---\n\n### Summary\nPolyvinylpyrrolidone (PVP) enhances hydrophilicity when covalently grafted onto a polymer matrix. Using radical graft polymerization with the correct initiator, solvent system, and reaction conditions, PVP can be effectively entrapped within the polymer matrix. This ensures the hydrophilic properties are stable and durable under operational conditions. By systematically following the described experimental steps, your lab experiment should yield success in synthesizing hydrophilic coatings with entrapped PVP.\n\nLet me know if you need clarification on any step or further details on experimental variations!"
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+  "design_question": "During free radical polymerization, you need to add IRGACURE 1173 as an initiator. Explain how you would incorporate this molecule in the reaction mixture and why it is critical to the curing process of the polymer network.",
+  "design_answer": "To address your question systematically, we will analyze the molecular context and discuss the role and integration of IRGACURE 1173 as an initiator during free-radical polymerization. This explanation will help you understand its importance and guide you toward performing the synthesis accurately in the laboratory.\n\n---\n\n**Analysis of the Questions' Key Points:**\n\n1. **IRGACURE 1173**: IRGACURE 1173 (1-Hydroxycyclohexyl phenyl ketone) is a photoinitiator commonly used in free-radical polymerization processes. It absorbs UV light and creates free radicals necessary to initiate polymerization.\n2. **Critical Role in Curing**: The photoinitiator is essential in triggering the polymerization reaction and ensuring the curing process forms a polymer network efficiently and uniformly.\n3. **Incorporation into the Reaction Mixture**: Understanding how to safely and precisely introduce IRGACURE 1173 into the system is vital for the stability of the reaction mixture and achieving the desired polymer properties.\n\n---\n\n**Detailed Experimental Procedure: Incorporating IRGACURE 1173 in the Polymerization Reaction**\n\nBelow is a step-by-step guide for incorporating IRGACURE 1173 in free-radical polymerization experiments. Follow this methodology carefully for laboratory success:\n\n---\n\n### **Step 1: Selection of Reactants and Materials**\nPrepare the following materials based on the designed polymer network:\n- **Monomer mixture**: Decide on the hydrophilic monomers to be polymerized. For example, hydroxyethyl methacrylate (HEMA), N-vinylpyrrolidone (NVP), or polyethylene glycol methacrylate (PEGMA) are commonly used for hydrophilic polymers.\n- **Cross-linker** (optional): If a network structure is desired, include a bifunctional or multifunctional monomer such as ethylene glycol dimethacrylate (EGDMA).\n- **Solvent** (optional): Select a solvent if dilution is needed for controlling viscosity (e.g., ethanol or water for hydrophilic systems).\n- **IRGACURE 1173**: The photoinitiator (1-Hydroxycyclohexyl phenyl ketone).\n- **Other additives**: Consider stabilizers or co-initiators (if applicable).\n\n---\n\n### **Step 2: Weighing and Ratio Calculation**\nAccurate weighing and molar ratios are critical for reproducibility. Example reaction ratios may be:\n- Monomers: Typically 95–98 wt% of the total composition.\n- Cross-linker: 2–5 wt%, depending on the desired network structure.\n- IRGACURE 1173: Added at 1–5 wt% of the total monomer weight. A typical starting point is around 2 wt%.\n  \n**Example Calculation**:\nIf preparing a 100 g reaction mixture:\n- Monomer: 95 g (e.g., HEMA).\n- Cross-linker (if used): 4 g (e.g., EGDMA for cross-linked hydrophilic polymers).\n- IRGACURE 1173: 1 g (2 wt%).\n\n---\n\n### **Step 3: Preparation of the Mixture**\n1. **Dissolve the Components**:\n   - Use a clean, glass reaction vessel. Start by dissolving the monomers and cross-linkers into the chosen solvent (if applicable). Stir gently to avoid introducing air bubbles.\n   - Add the IRGACURE 1173 after the monomers and cross-linkers are fully solubilized. Ensure uniform mixing for homogeneity. IRGACURE 1173 is soluble in many organic solvents but may precipitate in water. Select solvents accordingly if water is used.\n   \n2. **Reaction Mixture Observations**:\n   - Check for any cloudiness or precipitation in the solution. Adjust solvent or ratios as needed for complete solubility.\n\n---\n\n### **Step 4: UV Irradiation Setup**\n1. **UV Lamp Selection**:\n   - IRGACURE 1173 absorbs UV light within the wavelength range of 300–400 nm. Ensure your UV lamp operates in this range. A typical choice is a medium-pressure mercury vapor lamp or LEDs emitting ~365 nm.\n2. **Intensity Calibration**:\n   - Calibrate the energy density of the UV light source. A standard protocol involves applying 2–5 mW/cm² intensity, depending on the formulation's photoreactivity. Too low intensity may delay curing, while too high intensity may overheat the mixture or induce unwanted side reactions.\n\n---\n\n### **Step 5: Polymerization and Curing**\n1. **Initiation**:\n   - Illuminate the reaction mixture with the UV source. IRGACURE 1173 absorbs UV light and undergoes photochemical cleavage to generate free radicals. These radicals initiate chain polymerization and cross-linking (if applicable) of the monomers.\n   \n2. **Curing Duration**:\n   - Typical curing times range between 5–15 minutes, depending on the mixture's thickness and UV intensity. Monitor the reaction to avoid under- or over-curing.\n\n3. **Temperature Maintenance**:\n   - Keep the reaction vessel temperature constant during curing. Excessively high temperatures can accelerate degradation. A temperature range of 20–40°C is generally sufficient for hydrophilic polymer synthesis.\n\n---\n\n### **Step 6: Post-Curing and Analysis**\n1. **Post-Curing**:\n   - Expose the cured polymer to UV light for an additional 2–5 minutes, if necessary, to ensure complete polymerization and elimination of residual monomers.\n   \n2. **Characterization**:\n   - Perform tests to confirm success:\n     - FTIR spectroscopy to verify functional groups.\n     - Swelling tests for hydrophilicity (in water or similar solvents).\n     - Mechanical testing (if relevant).\n\n---\n\n**Importance of IRGACURE 1173 in the Curing Process:**\n\n- **Initiator Efficiency**: IRGACURE 1173 achieves high radical generation efficiency under UV light, ensuring rapid and uniform initiation of polymerization across the mixture.\n- **Control of the Network**: By controlling the quantity of IRGACURE 1173, you can regulate the kinetics and degree of curing to achieve desired polymer properties (e.g., mechanical strength, degree of swelling, or water affinity).\n- **Reduced Side Reactions**: IRGACURE 1173 typically decomposes cleanly under UV light, minimizing the generation of undesired byproducts.\n\n---\n\nBy following this step-by-step scheme, you will be able to incorporate IRGACURE 1173 into the reaction mixture effectively and ensure its critical role in forming the hydrophilic polymer network. Feel free to ask any follow-up questions or discuss potential optimizations for your specific polymer system!"
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+  "design_question": "How would you incorporate the diol with polyethylene oxide side chains into the polymer synthesis to enhance hydrophilicity? Describe the reaction steps and the impact of this molecule on the final properties of the polymer.",
+  "design_answer": "Certainly. To incorporate a diol with polyethylene oxide side chains (let’s call it PEO-diol) into a polymer to enhance hydrophilicity, we need to systematically develop a preparation scheme for your desired hydrophilic polymer. This involves analyzing the functionality of our starting materials, determining a suitable polymerization method, and carefully controlling the reaction conditions. Let us proceed step by step:\n\n---\n\n### **Analysis of the Problem and Key Points**\n1. **Objective**: To incorporate the PEO-diol into a polymer structure to increase its hydrophilicity.\n2. **Reactant Characteristics**:\n   - The PEO-diol contains hydroxyl (-OH) functional groups which are reactive and can participate in condensation or addition polymerization.\n   - The polyethylene oxide side chains are hydrophilic due to the ether linkages and their ability to form hydrogen bonds with water.\n3. **Desired Outcome**: A hydrophilic polymer where the PEO segment enhances water compatibility, wettability, and the polymer's water-uptake behavior.\n4. **Method**: We must select a polymerization strategy that incorporates the PEO-diol while ensuring control over the molecular architecture of the final product.\n\n---\n\n### **Experimental Preparation Scheme**\nLet us outline a step-by-step synthesis method to incorporate the PEO-diol into a polymer chain. A common and effective strategy is **step-growth polymerization** via a urethane or polyester backbone, as this allows us to link diols with other functional groups. For this example, we will design a scheme to prepare a **urethane-based hydrophilic polymer**.\n\n---\n\n#### **Step 1: Selection of Co-monomers**\nTo prepare a urethane polymer, the two main building blocks are:\n1. **PEO-Diol**: Acts as the hydrophilic segment. For example, choose a PEO-diol with a molecular weight between 400–2000 g/mol to provide adequate side-chain length for hydrophilicity.\n   - Example structure: HO-(CH₂CH₂O)ₙ-CH₂CH₂-OH.\n2. **Diisocyanate**: Acts as the coupling agent with diols to form urethane linkages (-NHCOO-). A widely used choice is **hexamethylene diisocyanate (HDI)** for flexibility or **toluene diisocyanate (TDI)** for rigidity, depending on the desired mechanical properties.\n\nOptional: A **chain extender (small diol)**, such as 1,4-butanediol, may be included to adjust the polymer's molecular weight and mechanical properties.\n\n---\n\n#### **Step 2: Precursor and Reagent Quantities**\n- **PEO-Diol**: Calculate the molar quantity based on the desired polymer weight and PEO content. For example, for a 5 g batch with 50% PEO content by mass, choose 5 g × 50% = 2.5 g of PEO-diol.\n   - If the PEO-diol has a molecular weight of 1000 g/mol, calculate the moles: \\( \\text{Moles of PEO-diol} = \\frac{2.5 \\text{ g}}{1000 \\text{ g/mol}} = 0.0025 \\text{ mol} \\).\n- **Diisocyanate**: Use an equimolar or slightly excess amount (1.05:1 ratio) to ensure complete reaction with diol groups. For 0.0025 mol PEO-diol, use 0.0025–0.002625 mol HDI.\n   - Convert this to mass: \\( \\text{Mass} = \\text{moles} \\times \\text{molar mass of HDI (168.2 g/mol)} \\).\n   - Example: \\( 0.002625 \\times 168.2 = 0.441 \\text{ g HDI} \\).\n- **Catalyst**: Radical scavengers or dibutyltin dilaurate (DBTDL, ~0.1 wt% of total reactants) may be added to facilitate urethane formation.\n\n---\n\n#### **Step 3: Reaction Setup and Polymer Synthesis**\n1. **Preparation**:\n   - Dry all reagents and solvents (e.g., toluene or dimethylformamide, DMF) to avoid moisture interference, as water reacts with isocyanates, forming urea byproducts.\n   - Set up a nitrogen-purged reaction flask to ensure an inert, dry atmosphere.\n\n2. **Reaction Steps**:\n   - **Step 3.1: Pre-polymer Formation**:\n     - In a reaction flask, dissolve PEO-diol in a dry solvent (e.g., anhydrous DMF or toluene) under stirring at 60–80°C.\n     - Slowly add the diisocyanate dropwise to control heat evolution, ensuring continuous mixing.\n     - Allow the reaction to proceed at 60–80°C for 1–2 hours to form the urethane pre-polymer. Monitor via FTIR (isocyanate peak ~2270 cm⁻¹ starts disappearing).\n   - **Step 3.2: Chain Extension (Optional)**:\n     - If using a chain extender, add the small diol (e.g., 1,4-butanediol) in the appropriate stoichiometric ratio, and continue stirring for another 1–2 hours at 80°C.\n   - Continue monitoring FTIR to confirm isocyanate group disappearance and urethane bond formation (-NH stretch at ~3300 cm⁻¹; -C=O stretch at ~1700 cm⁻¹).\n\n3. **Finalize the Product**:\n   - Recover the polymer by precipitation into a non-solvent (e.g., cold diethyl ether) or direct solvent removal under vacuum (if soluble).\n   - Dry the polymer thoroughly in a vacuum oven at 40–60°C.\n\n---\n\n### **Step 4: Characterization**\n1. **Hydrophilicity Testing**:\n   - Measure water contact angle to confirm improved hydrophilicity due to the PEO incorporation.\n   - Use swelling experiments to determine the polymer's water uptake capacity.\n2. **Molecular Characterization**:\n   - Confirm the polymer structure using FTIR and/or NMR.\n   - Measure molecular weight and distribution via GPC if necessary.\n\n---\n\n### **Step 5: Impact on Final Properties**\n1. **Hydrophilicity**:\n   - The incorporated PEO chains provide excellent hydrophilic behavior as they attract and retain water through hydrogen bonding.\n   - This can lead to applications in hydrogels, biomedical coatings, or membranes.\n2. **Flexibility**:\n   - The flexibility of the PEO-diol and its ether linkages improves polymer elasticity and reduces brittleness.\n3. **Applications**:\n   - The hydrophilic polymer can be used in drug delivery, anti-fouling coatings, and other applications where water interaction is critical.\n\n---\n\nThis systematic approach ensures a successful experiment and helps you design hydrophilic polymers for diverse applications. Do you have any specific details of your molecule or application that you'd like us to refine further?"
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+++ b/task2/task2-qa/UV-curable anti-fog coatings.json	
@@ -0,0 +1,4 @@
+{
+  "design_question": "Explain the role of monomethyl ether polyethylene glycol (mPEG, Mw = 1100) in improving the hydrophilicity of the polymer material and describe how you would modify it using 3-isocyanatopropyl trimethoxysilane.",
+  "design_answer": "To address your question systematically and help you thoroughly understand how monomethyl ether polyethylene glycol (mPEG, Mw = 1100) improves the hydrophilicity of polymers and how to use it in a modification process involving 3-isocyanatopropyl trimethoxysilane, let us analyze your query step by step. I will also provide detailed experimental steps to ensure reproducibility in the lab.\n\n---\n\n### **Step 1: Analyze the Question and Summarize Its Key Points**\n\n1. **What is mPEG (Mw = 1100)?**\n   - mPEG is a hydrophilic polymer with a single hydroxyl (-OH) group at one end. Its hydrophilicity arises from its ethylene oxide backbone, which enables strong hydrogen bonding with water molecules.\n\n2. **Why is mPEG useful for hydrophilicity enhancement?**\n   - Incorporating mPEG into polymer matrices enhances water compatibility, wettability, and biocompatibility due to the high hydrophilicity of the polyethylene glycol (PEG) chain.\n\n3. **What is 3-Isocyanatopropyl Trimethoxysilane?**\n   - This molecule contains reactive isocyanate (-NCO) and silane functional groups. The isocyanate group reacts with nucleophiles such as hydroxyl (-OH) groups, while the silane group can form siloxane (Si–O–Si) bonds with other surfaces or networks.\n\n4. **How do the two reagents interact?**\n   - mPEG's terminal hydroxyl (-OH) group can react with the isocyanate group of 3-isocyanatopropyl trimethoxysilane to form a urethane linkage, resulting in a functionalized compound that retains PEG’s hydrophilic property while introducing silane chemistry.\n\n5. **Objective:**\n   - Provide a systematic experimental preparation scheme for modifying mPEG with 3-isocyanatopropyl trimethoxysilane to enhance its utility for improving polymer hydrophilicity.\n\n---\n\n### **Step 2: Experimental Scheme for the Modification**\n\n#### **Materials Required:**\n1. Monomethyl ether polyethylene glycol (mPEG, Mw = 1100)\n2. 3-Isocyanatopropyl trimethoxysilane\n3. Anhydrous toluene (solvent)\n4. Catalyst: Dibutyltin dilaurate (DBTDL) or Stannous octoate (catalyst for urethane formation)\n5. Nitrogen or argon gas (to create an inert atmosphere)\n6. Magnetic stirrer and hot plate\n7. Reaction vessel (round bottom flask with a reflux condenser)\n8. Drying oven (to dry the final product)\n\n---\n\n#### **Detailed Synthesis Procedure:**\n\n##### **Step 1: Preparation of Reaction System**\n1. **Dehydration of mPEG:**\n   - Dry mPEG under vacuum at 60–80°C for 3–4 hours to remove any trace water. This step is crucial because water can react with the isocyanate (-NCO) group, forming unwanted by-products.\n\n2. **Prepare the Reaction Setup:**\n   - Use a clean, dry reaction flask equipped with a reflux condenser, magnetic stirrer, and nitrogen/argon inlet. Ensure the system is purged with nitrogen or argon to provide an inert atmosphere, as isocyanates are moisture-sensitive.\n\n##### **Step 2: Reaction of mPEG and 3-Isocyanatopropyl Trimethoxysilane**\n1. **Reagent Loading:**\n   - Add the dehydrated mPEG (1 equivalent) to the reaction flask.\n   - Add anhydrous toluene as a solvent; use a sufficient amount to dissolve mPEG completely (usually about 5 mL of toluene per 1 gram of mPEG).\n\n2. **Addition of Isocyanate Reagent:**\n   - Add 3-isocyanatopropyl trimethoxysilane (1.1–1.2 equivalents relative to mPEG) dropwise to the reaction mixture under a nitrogen atmosphere.\n\n3. **Catalyst Introduction:**\n   - Add a catalytic amount (0.01–0.05 equivalents) of DBTDL to the reaction mixture. This is essential for promoting the reaction between the hydroxyl group of mPEG and the isocyanate group of the silane.\n\n4. **Reaction Conditions:**\n   - Heat the reaction mixture to 60–80°C while stirring continuously.\n   - Maintain these conditions for 4–6 hours while monitoring the reaction's progress. You can monitor the disappearance of the isocyanate (-NCO) group using Fourier-transform infrared (FTIR) spectroscopy; the characteristic peak at ~2270 cm⁻¹ (from -NCO) will diminish as the reaction proceeds.\n\n##### **Step 3: Isolation and Purification**\n1. **Cooling and Precipitation:**\n   - After the reaction is complete, allow the reaction mixture to cool to room temperature.\n   - Precipitate the modified mPEG by slowly adding the reaction mixture to a large volume of cold diethyl ether or hexane under stirring. The urethane-functionalized mPEG will separate as a solid.\n\n2. **Washing:**\n   - Wash the precipitate several times with diethyl ether or hexane to remove unreacted reagents and by-products.\n\n3. **Drying:**\n   - Dry the purified product under vacuum at 40–50°C for 12–24 hours to obtain the silane-functionalized mPEG as a white or off-white powder.\n\n---\n\n#### **Step 4: Characterization of the Product**\n1. **FTIR Spectroscopy:**\n   - Confirm the formation of urethane linkages by observing a new peak at ~1700 cm⁻¹ (C=O stretching of the urethane bond).\n   - Verify the absence of the -NCO peak around 2270 cm⁻¹.\n\n2. **Nuclear Magnetic Resonance (NMR):**\n   - Use ¹H-NMR to confirm the presence of mPEG and the trimethoxysilane group (look for trimethoxy peaks and PEG chain peaks).\n\n3. **Thermogravimetric Analysis (TGA):**\n   - Evaluate thermal stability, which may be needed for further processing.\n\n---\n\n### **Step 3: Explanation of Hydrophilicity Improvement**\n\n1. **PEG Backbone:**\n   - The mPEG backbone is highly hydrophilic due to its ability to form hydrogen bonds with water. By incorporating mPEG into a polymer structure, water affinity improves significantly.\n\n2. **Surface Functionalization with Silane:**\n   - The trimethoxysilane group in the synthesized product permits covalent bonding to silica surfaces or incorporation into inorganic-organic hybrid systems. This further enhances the surface hydrophilicity and enables stable attachment to other materials.\n\n3. **Applications:**\n   - The modified polymer can be used in biomaterials, coatings, and membranes where improved water compatibility and adhesion to substrates are required.\n\n---\n\n### Summary:\n\nYou can improve the hydrophilicity of a polymer system by modifying mPEG (Mw = 1100) with 3-isocyanatopropyl trimethoxysilane. The resulting compound combines the hydrophilic nature of PEG with the reactivity of silane chemistry, enabling its use in diverse hydrophilic polymer-based applications.\n\nBy following the systematic procedure above, you will be able to synthesize and characterize the desired product effectively. If you have any further questions or uncertainties about implementing this protocol, feel free to ask!"
+}
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diff --git a/task2/task2-qa/Verma2019_Article_AReviewOnProtectivePolymericCo.json b/task2/task2-qa/Verma2019_Article_AReviewOnProtectivePolymericCo.json
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+{
+  "design_question": "Polysaccharides are often used to prepare hydrophilic polymer coatings. How would you modify a polymer surface with polysaccharides, and what factors would you evaluate to confirm the improvement in hydrophilicity?",
+  "design_answer": "### Analysis of the Question:\n\nPolysaccharides are a class of hydrophilic macromolecules commonly used in biomedical and material applications due to their inherent hydrophilicity, biocompatibility, and versatility in chemical modification. Your question pertains to modifying a polymer surface with polysaccharides to enhance hydrophilicity and determining the successful improvement of hydrophilicity via evaluation methods.\n\nThe process requires:\n1. **Surface modification strategy:** Covalent or non-covalent attachment of polysaccharides to the polymer surface.\n2. **Factors to confirm hydrophilicity improvement:** Experimental evaluation using techniques such as water contact angle measurement and surface characterization tools.\n\n### Step-by-Step Experimental Preparation Scheme:\n\n#### Step 1: Selection of Polysaccharide\nChoose a hydrophilic polysaccharide that can adhere or bond to the polymer surface. Examples include:\n- **Chitosan** (due to its amine groups for chemical reactivity)\n- **Alginate** (carboxyl groups can form ionic or covalent bonds)\n- **Dextran** (hydroxyl groups for functionalization)\n- **Hyaluronic acid** (useful in biomedical applications due to biocompatibility)\n\n#### Step 2: Surface Functionalization of Polymer\nTo facilitate polysaccharide attachment, the polymer must be functionalized via various methods:\n1. **Plasma or UV/Ozone Treatment**:\n   - Use plasma treatment or UV/ozone oxidation to introduce reactive hydroxyl (-OH), carboxyl (-COOH), or carbonyl (-C=O) groups on the surface if the polymer is chemically inert (e.g., polyethylene or polystyrene).\n   - Example protocol: Treat polymer surfaces with oxygen plasma at 20–50 W for 3–5 minutes.\n2. **Activation with Chemical Coupling Agents**:\n   - Use coupling agents (such as EDC/NHS for carboxyl groups or silanes for hydroxyl groups) for surface activation.\n\n#### Step 3: Covalent Attachment of Polysaccharide\nAfter activation, polysaccharides can be covalently bonded to the polymer surface using established chemistry:\n1. **Carbodiimide Chemistry for Carboxyl Groups**:\n   - Use a solution of EDC (1-ethyl-3-(3-dimethylaminopropyl) carbodiimide) and NHS (N-hydroxysuccinimide) in water or buffer (e.g., MES buffer) to activate carboxyl groups on the surface.\n   - Dissolve polysaccharide in water or buffer at 1–10 mg/mL.\n   - React the functionalized surface with the polysaccharide solution at room temperature for 4–8 hours.\n2. **Epoxy Crosslinking**:\n   - If epoxy groups are introduced on the polymer surface during functionalization, polysaccharides with hydroxyl or amine groups can directly react under mild conditions (in buffers at pH 7–9).\n3. **Ionic Bonding or Adsorption**:\n   - For polymers with ionic charges after functionalization (e.g., quaternized surfaces), use oppositely charged polysaccharides (such as alginate or chitosan).\n\n#### Step 4: Washing and Post-Curing\n- Wash the modified polymer surface thoroughly with distilled water or buffer to remove unbound reagents and polysaccharide residues.\n- Perform mild drying under vacuum or ambient conditions, ensuring no thermal damage occurs to the polysaccharide layer.\n\n#### Step 5: Confirmation of Hydrophilicity Improvement\nEvaluate hydrophilicity enhancement using the following methods:\n1. **Water Contact Angle Measurement**:\n   - Measure the contact angles before and after modification using a contact angle goniometer.\n   - A reduction in water contact angle (e.g., from over 90° to below 30°) indicates increased hydrophilicity.\n2. **Surface Characterization**:\n   - Perform **Fourier-Transform Infrared (FTIR) Spectroscopy** to confirm the presence of polysaccharide-specific functional groups (e.g., hydroxyl, amine, and carboxyl groups).\n   - Conduct **X-ray Photoelectron Spectroscopy (XPS)** to confirm the chemical composition changes.\n3. **Atomic Force Microscopy (AFM)**:\n   - Evaluate surface roughness after modification, as smoother surfaces often correlate with improved hydrophilicity due to uniform coatings.\n4. **Protein and Water Adsorption Tests** (if applicable):\n   - Measure protein adsorption or the water retention capacity of the surface to confirm hydrophilic behavior (typically, hydrophilic surfaces exhibit lower protein adsorption and higher water affinity).\n\n#### Step 6: Optimization for Application-Specific Properties\nEvaluate additional parameters based on application requirements:\n- **Durability and Stability:** Test the polysaccharide coating under various pH or temperature conditions to ensure adherence and stability.\n- **Biocompatibility:** If using the modified surface in biomedical applications, perform cell adhesion and proliferation studies to confirm application suitability.\n\n---\n\n### Recap of Factors to Evaluate Hydrophilicity Improvement:\n- Reduction in water contact angle.\n- Changes in surface chemistry indicative of polysaccharide attachment (FTIR, XPS, etc.).\n- Improved water adsorption/capacity or lower protein adhesion.\n- Enhanced biocompatibility or specific functional properties (application-dependent).\n\nBy employing these systematic steps, you can successfully modify a polymer surface with polysaccharides to enhance hydrophilicity and evaluate its improvement rigorously."
+}
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diff --git a/task2/task2-qa/a facile approach to UV-curable super-hydrophilic polyacrylate coating film grafted on glass substrate.json b/task2/task2-qa/a facile approach to UV-curable super-hydrophilic polyacrylate coating film grafted on glass substrate.json
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+{
+  "design_question": "How can gamma-methacryloxypropyltrimethoxysilane (MPS) be utilized to introduce functional double bonds onto a substrate, and why is this step critical for preparing hydrophilic polymer coatings?",
+  "design_answer": "To thoroughly answer your question, we will systematically analyze the problem and design a detailed experimental preparation scheme based on the requirements and context provided. Here's how gamma-methacryloxypropyltrimethoxysilane (MPS) can be utilized to introduce functional double bonds onto a substrate, and why this step is critical for preparing hydrophilic polymer coatings.\n\n---\n\n### **Step 1: Analyze the Question**\n- **Key molecule**: Gamma-methacryloxypropyltrimethoxysilane (MPS).\n- **Goal**: Introduce functional double bonds onto a substrate surface using MPS.\n- **Purpose**: The double bonds serve as reactive sites for preparing hydrophilic polymer coatings.\n- **Importance of double bonds**: These double bonds enable subsequent polymerization or surface grafting to form hydrophilic polymer networks, improving the substrate's wettability and compatibility with aqueous environments.\n\n---\n\n### **Step 2: Systematic Explanation and Experimental Design**\nHere is the detailed preparation scheme step-by-step:\n\n#### 2.1 **Substrate Pretreatment**\nBefore functionalizing the substrate with MPS, it is important to ensure the surface is clean and reactive:\n- **Importance**: Any contamination (organic or inorganic debris) will hinder adhesion of MPS and reduce the availability of silanol groups required for silane bond formation.\n- **Procedure**:\n  1. **Cleaning**: Immerse the substrate (e.g., glass, metal oxide, polymer film, etc.) in a solution of ethanol and deionized water (1:1 v/v) containing 1% (v/v) acetic acid. Sonicate the substrate for 20–30 minutes to remove debris.\n  2. **Activation**: If the substrate is non-reactive like glass or silicon wafer, use a plasma treatment or immerse the substrate in 1 M NaOH or piranha solution (a mixture of sulfuric acid and hydrogen peroxide) for 10 minutes to generate hydroxyl groups (-OH) for silane coupling.\n\n#### 2.2 **Preparation of MPS Solution**\n- **Reagents**:\n  - Gamma-methacryloxypropyltrimethoxysilane (MPS).\n  - Ethanol (solvent).\n  - Deionized water.\n  - Acetic acid or hydrochloric acid (catalyst for hydrolysis).\n- **Procedure**:\n  1. Prepare a solution with 5% (v/v) MPS in ethanol and deionized water mixture (90:10 ethanol/water by volume).\n  2. Add 0.1–0.5% (v/v) acetic acid or hydrochloric acid to the mixture to catalyze hydrolysis of the trimethoxysilane groups.\n  3. Stir the solution at room temperature for 30–60 minutes to form silanol (-Si-OH) groups through hydrolysis.\n\n---\n\n#### 2.3 **Functionalization of Substrate**\n- **Procedure**:\n  1. Immerse the cleaned and activated substrate in the prepared MPS solution. Ensure complete immersion for uniform functionalization.\n  2. Allow the substrate to react with MPS for 1–2 hours at room temperature or slightly elevated temperatures (~50 °C) to promote condensation reactions between silanol groups on the substrate and MPS molecules.\n  3. After functionalization, remove the substrate and rinse thoroughly with ethanol to remove non-reacted MPS molecules.\n  4. Dry the substrate under vacuum or by gentle heating (~70–80 °C) to ensure complete crosslinking and condensation.\n\n---\n\n#### 2.4 **Characterization of Double Bonds**\n- **Purpose**: Verify the successful modification of the substrate surface with double bonds from the MPS molecule.\n- **Techniques**:\n  - **FTIR Analysis**: Look for characteristic C=C stretching vibrations (~1635 cm⁻¹) and Si-O-Si vibrations (~1100 cm⁻¹) confirming the presence of double bonds and silane coupling.\n  - **Contact Angle Measurements**: A reduction in the contact angle after functionalization indicates the introduction of reactive groups.\n  - **XPS Analysis**: Detect the chemical changes confirming the incorporation of MPS onto the surface.\n\n---\n\n#### 2.5 **Polymerization of Hydrophilic Polymer**\nWith the substrate now bearing double bonds, hydrophilic polymers can be grafted or polymerized onto the surface:\n- **Importance of Double Bonds**: The methacrylate double bonds (-CH=CH₂) present on the surface serve as reactive sites for free-radical polymerization or covalent bonding of hydrophilic monomers, such as acrylamide, acrylic acid, or polyethylene glycol methacrylate (PEGMA).\n- **Procedure**:\n  1. Prepare an aqueous solution containing the hydrophilic monomer (e.g., 10–20% by mass acrylamide) and a radical initiator like ammonium persulfate (APS) or photoinitiator.\n  2. Place the MPS-functionalized substrate into the solution and initiate polymerization through heat (~60 °C) or UV irradiation, depending on the initiator.\n  3. After the polymerization is complete, rinse and dry the coated substrate.\n\n---\n\n### **Step 3: Why Is This Step Critical for Hydrophilic Polymer Coatings?**\n1. **Anchoring Sites**: The MPS introduces double bonds, which act as anchoring sites for grafting hydrophilic polymers. Without these bonds, polymerization would not occur uniformly or strongly on the surface.\n2. **Strong Adhesion**: The silanol groups formed during MPS coupling create robust covalent bonds with hydroxyl groups on the substrate, preventing delamination or weak adhesion.\n3. **Uniform Polymerization**: The presence of double bonds ensures a consistent reaction interface for hydrophilic polymers to grow, yielding homogeneous coatings.\n4. **Enhanced Hydrophilicity**: The resulting hydrophilic polymer layer lowers the surface energy of the substrate, increasing wettability by water.\n\n---\n\n### Final Notes:\nThe inclusion of MPS in the process is foundational for hydrophilic polymer coating preparation. As you practice this in the lab, ensure precision in contamination removal, reagent concentrations, and reaction conditions to achieve reliable and reproducible results. Don't forget to thoroughly characterize the intermediate and final products to validate each step."
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diff --git a/task2/task2-qa/adma.201807101.json b/task2/task2-qa/adma.201807101.json
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+{
+  "design_question": "If Irgacure-2959 is selected as the photoinitiator for this experiment, outline the steps required to utilize this molecule in polymerizing hydrophilic monomers and explain its specific role in initiating the reaction under UV light.",
+  "design_answer": "Great question, and thank you for your inquiry! Irgacure-2959 is indeed a commonly used photoinitiator, especially in experiments involving the UV-induced polymerization of hydrophilic monomers. Let me guide you through the details systematically, breaking it down into clear steps with an explanation of its specific role in initiating the reaction.\n\n---\n\n### 1. **Analysis of the Question and Summary of Key Points**\n- **Objective**: To outline the experimental steps required to polymerize hydrophilic monomers using Irgacure-2959.\n- **Core Concepts**: \n  - Polymerization of hydrophilic monomers.\n  - Role of Irgacure-2959 as a photoinitiator.\n  - Importance of UV light in initiating and propagating free radical polymerization.\n\n---\n\n### 2. **Detailed and Systematic Experimental Preparation Scheme**\n\nHere is a systematic procedure for this experiment:\n\n#### **Step 1: Obtain Materials and Reagents**\n- **Hydrophilic Monomer**: Examples include acrylamide, N-isopropylacrylamide, hydroxyethyl methacrylate (HEMA), or polyethylene glycol diacrylate (PEGDA), depending on the desired polymer.\n- **Photoinitiator**: Irgacure-2959 (chemical name: (1-Hydroxycyclohexyl) phenyl ketone).\n- **Solvent**: Deionized (DI) water, ethanol, or a water/ethanol mixture—depends on the solubility of the monomer.\n- **Crosslinker (Optional)**: If required, use a diacrylate-based crosslinker such as ethylene glycol dimethacrylate (EGDMA) to form a 3D network structure.\n- **Equipment**: UV lamp (wavelength: ~365 nm), nitrogen gas source (optional to deoxygenate for efficient free radical polymerization), magnetic stirrer, reaction flask, and quartz mold or Petri dish.\n\n---\n\n#### **Step 2: Prepare the Reaction Mixture**\n1. **Weigh Reagents**:\n   - Select and weigh the required amount of your hydrophilic monomer(s). For instance, if using acrylamide, typically 5–20 wt% of the total solution weight is used.\n   - Add Irgacure-2959. A common ratio is 0.5–1 wt% of the monomer concentration (e.g., 0.5 g Irgacure-2959 for 100 g of monomer solution). This ensures sufficient radical initiation without premature degradation of the monomer.\n   - Optional: If a crosslinked polymer is desired, add crosslinker to the solution—typically 1–5 mol% relative to the monomer.\n\n2. **Dissolve in a Solvent**:\n   - Dissolve the monomer and photoinitiator in the solvent (e.g., DI water). For instance, use around 10 mL of DI water for every 1 g of the monomer for a typical aqueous polymerization.\n   - Ensure complete dissolution by stirring the mixture at room temperature (~25°C) until all components (monomer, crosslinker, and photoinitiator) are fully dissolved. It might take ~30–60 minutes.\n\n3. **Deoxygenate (Optional)**:\n   - Degassing the solution with nitrogen gas helps to remove oxygen, which can quench free radicals and inhibit the polymerization process. Bubble nitrogen into the reaction mixture for ~15–20 minutes.\n\n---\n\n#### **Step 3: UV-Induced Polymerization**\n1. **Transfer to Mold**:\n   - Pour the reaction mixture into a suitable mold. Use a quartz mold or a UV-transparent Petri dish to allow proper exposure to UV light.\n\n2. **UV Light Irradiation**:\n   - Place the mold under a UV lamp emitting light at ~365 nm (UVA range). Ensure uniform exposure to all parts of the mixture.\n   - **Duration**: The polymerization reaction typically takes 5–30 minutes, depending on the UV intensity and monomer concentration.\n   - **Intensity Setting**: Use UV light with an intensity of ~5–10 mW/cm² for controlled polymerization.\n\n3. **Initiation Mechanism with Irgacure-2959**:\n   - **Photoactivation**: Under UV light, Irgacure-2959 absorbs photons, undergoing photolysis to generate free radicals:\n     \\[\n     \\text{Irgacure-2959} \\stackrel{UV}{\\longrightarrow} \\text{Radicals (R•)}\n     \\] \n     These free radicals are then available to initiate the polymerization of the hydrophilic monomers.\n   - **Radical Addition**: The free radicals react with the double bonds of the hydrophilic monomer (e.g., acrylamide, HEMA), forming reactive sites that propagate the polymer chain:\n     \\[\n     \\text{R•} + \\text{Monomer} \\rightarrow \\text{Polymer Chain}\n     \\]\n   - The polymerization proceeds via radical propagation until chain termination.\n\n---\n\n#### **Step 4: Post-Polymerization Processing**\n1. **Curing**: After the estimated reaction time, the polymer should be fully cured (solidified or gelled).\n2. **Washing**:\n   - Rinse the polymer with DI water or ethanol to remove any unreacted monomer, photoinitiator, or solvent. Washing is especially critical for biomedical applications where residual chemicals must be minimized.\n3. **Drying (Optional)**:\n   - If a dried film or hydrogel is required, dry the polymer in a vacuum oven at ~40–50°C (low enough to avoid degradation).\n\n---\n\n### 3. **Role of Irgacure-2959 as a Photoinitiator**\n- **Photolytic Behavior**:\n   - Irgacure-2959 is highly efficient in absorbing UV light at ~365 nm due to its chemical structure. Upon absorption, it breaks down into free radicals.\n- **Hydrophilic Compatibility**: Irgacure-2959 is water-soluble, making it highly compatible with aqueous systems and hydrophilic monomers.\n- **Controlled Radical Generation**: The free radicals generated by Irgacure-2959 initiate polymerization at specific rates, enabling uniform polymer formation even in heterogeneous systems.\n\n---\n\n### 4. **Key Reaction Considerations**\n- **UV Exposure Control**: Overexposure to UV can lead to gelation or degradation, so monitor the exposure time carefully.\n- **Concentration of Photoinitiator**: Excess Irgacure-2959 can cause premature termination of chains, while too little will slow polymerization.\n\n---\n\nBy following the procedure and maintaining proper conditions, you should achieve a high-quality hydrophilic polymer. Please let me know if you have additional questions or need specific guidance on your selected monomer system!"
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diff --git a/task2/task2-qa/adma202002710-sup-0001-suppmat.json b/task2/task2-qa/adma202002710-sup-0001-suppmat.json
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+{
+  "design_question": "Describe the steps you would follow to create a layered structure using CMC (carboxymethyl cellulose) and CHI. How does the alternating deposition of these molecules influence the overall hydrophilicity of the polymer?",
+  "design_answer": "Certainly! Let’s thoughtfully and systematically address your question about creating a layered structure using carboxymethyl cellulose (CMC) and chitosan (CHI). Additionally, we will explore how the alternating deposition of these molecules affects the hydrophilicity of the resulting polymer.\n\n---\n\n### **Step 1: Analyze the Question and Summarize the Key Points**\n\n1. **Key Molecules**  \n   - CMC: A hydrophilic, negatively charged, water-soluble derivative of cellulose with carboxyl (-COO⁻) functional groups.  \n   - CHI: Chitosan, a polysaccharide derived from chitin that is positively charged under acidic conditions due to primary amine groups (-NH₃⁺).\n\n2. **Problem Objective**  \n   - To form layered structures (thin films) using these two molecules, likely through an approach such as Layer-by-Layer (LbL) self-assembly.\n   - To understand how alternating layers of negatively charged CMC and positively charged CHI influence the final material’s hydrophilicity.\n\n3. **Underlying Concept**  \n   - The alternating deposition of oppositely charged polymers exploits electrostatic interactions to form stable layered films.\n   - The hydrophilicity of the system depends on the chemical nature and exposure of functional groups, especially polar groups like -COOH, -OH, and -NH₂.\n\n---\n\n### **Step 2: Detailed and Systematic Experimental Scheme**\n\nHere is a complete step-by-step guide to design and execute the experiment:\n\n---\n\n#### **Step 2.1: Prepare CMC and CHI Solutions**\n\n- **CMC Solution Preparation**:\n  1. Dissolve CMC powder in deionized (DI) water to create a solution (recommended concentration: 0.5–1.0 wt%).\n  2. Adjust the pH to ~7.0 using a dilute NaOH solution, ensuring complete dissolution and carboxyl group ionization (-COO⁻ formation).  \n  3. Stir the solution for 1–2 hours at room temperature until homogeneous.\n\n- **CHI Solution Preparation**:\n  1. Dissolve CHI in 0.1–1.0 wt% acetic acid solution (adjust pH to ~4.0 for protonation of -NH₂ groups to -NH₃⁺).\n     - **Note:** Chitosan dissolves better in acidic conditions due to protonation.\n  2. Stir the solution for 1–2 hours at room temperature or slightly warm (~40–50 °C) for better solubility, if needed.\n\n---\n\n#### **Step 2.2: Surface Preparation for Layer-by-Layer Assembly**\n\n1. **Substrate Selection**:  \n   Choose a flat substrate (e.g., glass slide, quartz, or a polymeric surface). This will act as the base for film formation.\n\n2. **Substrate Cleaning**:  \n   - Soak the substrate in piranha solution (3:1 mixture of sulfuric acid and hydrogen peroxide) for ~15 minutes [CAUTION: Handle with extreme care under a fume hood].  \n   - Rinse thoroughly with DI water, and dry with filtered nitrogen gas.\n   - For hydrophobic surfaces, consider plasma treatment to increase initial hydrophilicity.\n\n---\n\n#### **Step 2.3: Multilayer Film Assembly**\n\nThis step involves the sequential deposition of CMC and CHI using the Layer-by-Layer (LbL) technique:\n\n1. **Dip Coating Process**:  \n   - Immerse the cleaned substrate into the CMC solution for 5–10 minutes to allow for adsorption of the negatively charged polymer.\n   - Rinse the substrate thoroughly with DI water to remove loosely bound/unadsorbed molecules.\n   - Dry the substrate gently using nitrogen gas or by air-drying.\n\n2. Repeat Using CHI Solution:  \n   - Immerse the CMC-coated substrate into the CHI solution for 5–10 minutes, allowing electrostatic interaction between CHI (-NH₃⁺) and the CMC (-COO⁻).\n   - Rinse thoroughly with DI water to remove unbound CHI.\n   - Dry the substrate gently.\n\n3. **Repeat Alternating Layers**:  \n   - Repeat this deposition process alternately with CMC and CHI for the desired number of layers (e.g., 10–20 bilayers).  \n   - Typical thickness per bilayer is in the range of 5–10 nm, depending on deposition conditions and solution concentrations.\n\n---\n\n#### **Step 2.4: Post-Processing and Characterization**\n\n1. **Drying**:  \n   - After completing the desired number of layers, dry the multilayer structure at room temperature or under a vacuum.\n\n2. **Confirmation of Layer Formation**:  \n   - Use techniques like **UV-Vis spectroscopy** (for optically active polymers), **Fourier Transform Infrared Spectroscopy (FTIR)** for functional group analysis, or **Atomic Force Microscopy (AFM)**/**Scanning Electron Microscopy (SEM)** for surface imaging.\n\n3. **Hydrophilicity Testing**:  \n   - Measure the hydrophilicity of the film using **static water contact angle measurements.**\n     - A lower contact angle (<90°) indicates higher hydrophilicity.\n\n---\n\n### **Step 3: Explanation of Hydrophilicity Changes**\n\n1. **Influence of Alternating Deposition**:\n   - Alternating layers introduce both hydrophilic functional groups (-COOH/-COO⁻ from CMC and -NH₂/-NH₃⁺ from CHI).\n   - Electrostatic interactions between CMC and CHI increase the stability of the system, but exposed residual groups (e.g., -OH, -COOH) further enhance water affinity.\n\n2. **Hydrophilicity of the Composite**:\n   - The layered structure creates a highly hydrophilic film due to the abundance of polar functional groups from both polymers. CMC, as a highly hydrophilic polymer, contributes significantly to water absorption.  \n   - The addition of CHI also enhances hydrophilicity via its amino groups, which can hydrogen bond with water molecules.\n\n---\n\n### **Summary**\n\nTo prepare a layered structure of CMC and CHI, we use Layer-by-Layer (LbL) assembly, alternating between solutions of CMC (at pH 7.0) and CHI (at pH ~4.0). Electrostatic attraction forms stable multilayers, and the overall hydrophilicity increases due to the exposed polar functional groups. The combination of CMC and CHI imparts not just hydrophilicity but also versatility for applications such as drug delivery, wound dressings, and hydrophilic coatings.\n\nLet me know if there’s a specific aspect of the procedure you'd like me to elaborate on!"
+}
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+{
+  "design_question": "During the synthesis of a hydrophilic polymer, poly(vinyl acetate) (PVAc) is often used in the preparation process. How would you prepare a substrate layer using PVAc, and why is this step important for enhancing hydrophilicity?",
+  "design_answer": "To address your question systematically, we will examine the requirements for preparing a substrate layer using poly(vinyl acetate) (PVAc) and its importance in enhancing hydrophilicity during hydrophilic polymer synthesis. Let us proceed step-by-step, keeping in mind the logical rigor and detail you require.\n\n---\n\n### 1. **Key Points Analysis of the Question:**\n   - **Goal of the experiment:** To synthesize a hydrophilic polymer.\n   - **Role of PVAc:** PVAc is used in the preparation of a substrate layer during the synthesis process.\n   - **Task:** Devise an experimental procedure to prepare a substrate layer of PVAc.\n   - **Objective:** Explain the importance of this step in enhancing the hydrophilicity of the polymer.\n\n   The preparation and role of the PVAc substrate layer must be clearly explained, ensuring that it contributes to the hydrophilicity of the overall polymer system.\n\n---\n\n### 2. **Systematic Procedure for PVAc Substrate Preparation:**\n\nTo prepare a PVAc substrate layer, the following experimental steps can be followed. These steps involve the synthesis, deposition, and modification of PVAc for use as a base layer for the final hydrophilic polymer.\n\n#### **Step 1: Sourcing Poly(vinyl acetate) (PVAc)**\n   You can either use commercially available PVAc (available in pellet or powder form with known molecular weights) or synthesize PVAc in the laboratory via the free-radical polymerization of vinyl acetate (VAc) monomers.\n   \n   **Synthesis of PVAc (if needed):**\n   - Use vinyl acetate monomers with an appropriate free-radical initiator such as benzoyl peroxide (BPO) or azobisisobutyronitrile (AIBN).\n   - Dissolve the initiator (0.5–1% by weight of VAc) in a suitable solvent (ethanol or toluene).\n   - Polymerize under inert conditions (nitrogen atmosphere) at 60–70°C for several hours until polymerization is complete.\n\n   Ensure that the synthesized PVAc is purified by precipitation in methanol or ethanol, followed by drying in vacuum.\n\n#### **Step 2: Preparation of PVAc Solution for Substrate Layer**\n   - Dissolve PVAc powder (or use pre-synthesized PVAc) in a solvent such as ethanol, acetone, or tetrahydrofuran (THF). The choice of solvent depends on the molecular weight of PVAc and the desired viscosity of the solution.\n   - Typical concentration: Prepare a solution with **5–20 wt% PVAc** depending on substrate thickness requirements.\n   - Stir the solution thoroughly (at room temperature or slightly elevated temperatures) until the PVAc is fully dissolved.\n\n#### **Step 3: Substrate Layer Deposition**\n   - Use a substrate material such as a glass slide, silicon wafer, or polymer film as the base layer.\n   - Clean the substrate thoroughly using sequential sonication in solvents (e.g., acetone, isopropanol, and deionized water) and dry it with nitrogen gas to remove residual contaminants.\n\n   **Deposition techniques for PVAc:**\n   - **Spin Coating (recommended for uniform thickness):**\n     - Deposit the PVAc solution onto the substrate surface.\n     - Spin the substrate at 2000–4000 rpm for 30–60 seconds until a thin and uniform PVAc layer forms.\n     - Dry thoroughly (allow the solvent to evaporate) at room temperature or in an oven at 40–50°C.\n   - **Dip Coating:**\n     - Dip the substrate into the PVAc solution and slowly withdraw it at a controlled speed (~1–5 mm/s).\n     - Air dry the coated substrate and cure it in an oven at 50°C for several hours.\n   - **Drop Casting:**\n     - Deposit a controlled volume of the PVAc solution onto the substrate and allow it to spread evenly.\n     - Let the solvent evaporate slowly in ambient conditions or in an oven.\n\n   The final PVAc substrate layer thickness can be controlled by adjusting the solution concentration, coating speed, and deposition technique. Typical layer thickness ranges from **100 nm to a few microns**.\n\n#### **Step 4: Modification of PVAc Layer – Hydrolysis**\n   After forming the substrate layer, PVAc can be converted into poly(vinyl alcohol) (PVA) through hydrolytic treatment to introduce hydrophilic hydroxyl (-OH) groups. This step enhances the hydrophilicity of the PVAc layer.\n\n   - **Hydrolysis Reaction:**\n     - Immerse the PVAc-coated substrate in a solution of **sodium hydroxide (NaOH)** or potassium hydroxide (KOH) in ethanol or water. A typical concentration is **0.1–0.5 M NaOH in ethanol/water (80:20)**.\n     - Allow the hydrolysis reaction to proceed at **room temperature for 30–60 minutes**.\n   - Monitor the degree of hydrolysis carefully. Partial hydrolysis results in a balance of hydrophilicity and structural stability, while complete hydrolysis maximizes hydrophilicity.\n\n   - **Washing and Drying:**\n     - Wash the substrate gently with deionized water to remove residual NaOH/KOH and byproducts (e.g., sodium acetate or potassium acetate).\n     - Dry the modified PVAc (PVA) layer under nitrogen gas or in a low-temperature oven (50°C).\n\n---\n\n### 3. **Why is the PVAc Substrate Important?**\n\nThe PVAc substrate layer plays a critical role in enhancing hydrophilicity for subsequent polymer synthesis:\n1. **Adhesion and Compatibility:**\n   - PVAc acts as a uniform, adhesive base for the growth or deposition of a secondary hydrophilic polymer layer. This ensures strong interfacial bonding and prevents delamination.\n2. **Hydrophilic Transformation via Hydrolysis:**\n   - Hydrolyzing PVAc into PVA introduces a high density of hydrophilic hydroxyl (-OH) groups, which increases the overall water affinity of the system.\n3. **Template for Advanced Functionalization:**\n   - The presence of hydroxyl groups on PVA serves as reactive sites for further chemical modifications, such as graft polymerization using hydrophilic monomers (e.g., acrylic acid, acrylamide, or polyethylene glycol methacrylate).\n4. **Enhanced Wettability:**\n   - A partially or fully hydrolyzed PVAc layer improves the wettability of the substrate, crucial for applications such as coatings, membranes, and biomaterials.\n\n---\n\n### 4. **Experimental Considerations**\n   - *Safety Precautions:* Handle solvents and alkali solutions in a fume hood with proper PPE (gloves, goggles, lab coat).\n   - *Reaction Control:* Monitor the hydrolysis reaction to optimize the degree of hydrophilicity without over-degradation of the polymer.\n   - *Characterization:* Analyze the surface properties of the PVAc substrate through techniques such as water contact angle measurement, Fourier-transform infrared spectroscopy (FTIR, to confirm hydrolysis), and atomic force microscopy (AFM, for surface topography).\n\n---\n\n### Final Conclusion:\nTo prepare a PVAc substrate layer for enhancing hydrophilicity, dissolve and deposit PVAc using appropriate coating techniques. Modify the PVAc layer via hydrolysis to introduce hydrophilic hydroxyl groups, creating a PVA base that promotes adhesion, wettability, and further functionalization. This procedural framework allows a successful experiment and serves as a stepping stone for synthesizing advanced hydrophilic polymers."
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+{
+  "design_question": "Describe how you would utilize 3-glycidoxypropyltrimethoxysilane in a procedure to functionalize glass slides before coating a hydrophilic polymer. Specify the purpose of this treatment and how it contributes to enhancing the hydrophilicity of the final polymer material.",
+  "design_answer": "Certainly! As a materials science professor with expertise in hydrophilic polymers, I’ll guide you step-by-step through the process of functionalizing glass slides with 3-glycidoxypropyltrimethoxysilane (GPTMS) as part of a preparation scheme for enhancing the hydrophilicity of the final polymer material. I will also explain the purpose of each step to enrich your understanding.\n\n---\n\n### **Step 1: Analyze the Question and Summarize Key Points**\n\n**Key Question Goals:**\n1. Design a procedure to functionalize glass slides using GPTMS.\n2. Specify the purpose of this surface treatment.\n3. Explain how the treatment enhances hydrophilicity of the final polymer material.\n\n---\n\n### **Step 2: Systematic Experimental Procedure**\n\nBelow is a detailed, systematic procedure for functionalizing glass slides with GPTMS and subsequently coating them with a hydrophilic polymer:\n\n---\n\n#### **Materials Required**\n1. Glass slides (cleaned thoroughly, as described in Step 3).\n2. 3-Glycidoxypropyltrimethoxysilane (GPTMS).\n3. Absolute ethanol or isopropanol (as the solvent).\n4. Deionized (DI) water.\n5. Glacial acetic acid (or another acid catalyst, e.g., HCl, if needed).\n6. Nitrogen (N\\(_2\\)) or argon gas (for inert environment, if used).\n7. Hydrophilic polymer precursor (specific to your experiment, such as poly(ethylene glycol)-based polymer, polyacrylamide, etc.).\n8. Oven or hot plate (for curing).\n9. Desired buffer/reagents for hydrophilic polymer synthesis and application.\n\n---\n\n#### **Step 3: Cleaning and Preparing Glass Slides**\nThe first step ensures the glass surface is free of contaminants like grease, dust, or residual organics that can inhibit silanization.\n\n1. **Initial Cleaning:** Immerse the glass slides in a piranha solution (3:1 concentrated sulfuric acid: 30% hydrogen peroxide) to remove organic residues. *(Caution: Handle piranha solution with extreme care! Always add H\\(_2\\)O\\(_2\\) to acid, not vice versa.)*\n   \n2. **Rinse:** After cleaning, rinse the slides thoroughly with copious amounts of deionized water.\n   \n3. **Ethanol/Isopropanol Wash:** Submerge the slides in ethanol or isopropanol to remove water from the surface. Allow them to air dry or gently dry them in a nitrogen/argon stream.\n   \n4. **Plasma Cleaning (Optional):** For further activation, expose the slides to oxygen plasma or UV-ozone treatment. This step increases surface hydroxyl groups, creating reactive sites for bonding with the silane.\n\n---\n\n#### **Step 4: Preparation of GPTMS Silanization Solution**\n1. Mix the silane solution by combining the following:\n   - 1% to 2% (v/v) GPTMS in absolute ethanol or isopropanol.\n   - Introduce a small amount (e.g., 0.1–0.2% v/v) of glacial acetic acid or any other acid catalyst to promote hydrolysis of the methoxy groups in GPTMS.\n   - Add DI water to the mixture in a molar ratio of approximately 1:3 molar equivalents of water to silane to initiate partial hydrolysis.\n   \n2. Allow the mixture to hydrolyze at room temperature for 15–30 minutes under constant stirring. The hydrolysis transforms the silane methoxy groups into reactive silanol groups (\\(-SiOH\\)), which will later condense with hydroxyl groups on the glass slide surface.\n\n---\n\n#### **Step 5: Functionalizing the Glass Slides**\n1. Immerse the cleaned glass slides in the silane solution completely, ensuring full coverage. Allow them to remain in the solution for 1–4 hours at room temperature or slightly elevated temperatures (e.g., 40–60°C).\n   \n2. After incubation, remove the slides from the solution and rinse gently with ethanol to remove loosely bound or excess silane.\n\n3. Cure the silane layer:\n   - Bake the coated slides in an oven at 100–120°C for 1–2 hours. This step induces condensation reactions between the silanol groups of GPTMS and hydroxyl groups on the glass slide surface, forming covalent \\(-Si-O-Si-\\) linkages.\n   - This curing step stabilizes the silane layer and ensures strong attachment to the glass substrate.\n\n4. After curing, allow the slides to cool to room temperature in a clean and dust-free environment. At this stage, the glass slide is successfully functionalized with GPTMS.\n\n---\n\n#### **Step 6: Coating or Grafting the Hydrophilic Polymer**\n1. **Activation of Epoxide Groups:** The functionalized surface now contains terminal glycidoxy (epoxide) groups that can react chemically with hydrophilic polymer precursors or crosslinkers. These epoxide groups are highly reactive toward nucleophiles such as amines, hydroxyls, or thiols.\n\n2. Prepare the hydrophilic polymer:\n   - For example, if using a poly(ethylene glycol) (PEG)-based polymer, mix the PEG polymer or precursor with a coupling agent and initiator to react with the epoxide group.\n   - Another example is coating polyacrylamide or acrylate-based hydrogels by initiating free-radical polymerization on the reactive surface.\n\n3. Apply the polymer or precursor to the silanized slide:\n   - Spread or dip-coat the functionalized slides in the polymer solution.\n   - Allow the reaction between the epoxide groups on the GPTMS and the functional groups of the polymer to proceed for the required time, typically under ambient or slightly elevated temperatures (e.g., 40–60°C).\n   - Ensure proper curing/grafting steps, based on the polymer used.\n\n4. Rinse off any unreacted polymer with a compatible solvent, such as water or ethanol.\n\n---\n\n#### **Step 7: Evaluation of Surface Hydrophilicity**\n1. To confirm enhancement of hydrophilicity, conduct surface characterization:\n   - Perform water contact angle measurements before and after polymer coating. A significant decrease in the contact angle confirms higher hydrophilicity.\n   - Use techniques like FTIR or XPS to confirm successful silanization and polymer attachment.\n\n---\n\n### **Purpose of GPTMS Functionalization**\n\nFunctionalization with GPTMS serves the following purposes:\n1. **Enhanced Surface Adhesion:** The covalent \\(-Si-O-Si-\\) bonds between the GPTMS and the glass surface ensure strong adhesion of the polymer to the substrate.\n2. **Chemical Reactivity:** The epoxide group in GPTMS serves as a versatile anchor that forms covalent bonds with nucleophilic groups in hydrophilic polymers. This tailored reactivity facilitates uniform and strong polymer attachment.\n3. **Improved Hydrophilicity:** GPTMS-treated surfaces provide a functional interface that allows robust binding of hydrophilic polymers, which significantly increases the overall hydrophilicity of the material.\n\n---\n\n### **How This Treatment Enhances Hydrophilicity**\n\n1. **Stable Polymer Attachment:** By functionalizing glass with a reactive silane like GPTMS, the hydrophilic polymer can be stably grafted or attached to the surface. This prevents polymer delamination or degradation over time.\n2. **Uniform Hydrophilic Coating:** A robust interface promotes uniform polymer dispersion, minimizing hydrophobic regions and maximizing water attraction.\n3. **Water-Wicking Behavior:** Hydrophilic polymers, when attached to such functionalized surfaces, promote hydrogen bonding and capillary action, further enhancing hydrophilicity.\n\n---\n\n### **Conclusion**\n\nThe functionalization of glass slides with GPTMS is an essential preparatory step for grafting hydrophilic polymers. Through precise silanization and polymer coating, the hydrophilicity of the final material is greatly improved, allowing for applications in biomedical devices, antifouling surfaces, and hydrophilic coatings."
+}
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diff --git a/task2/task2-qa/am3c17117_si_001.json b/task2/task2-qa/am3c17117_si_001.json
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+{
+  "design_question": "Explain how the combination of 1-propanol with water during the solution preparation phase might affect the interactions between the polymer and the added molecule. How is this relevant to increasing the hydrophilicity of the final polymer product?",
+  "design_answer": "Certainly, let’s systematically analyze your question and break it down step by step.\n\n---\n\n### **1. Key Points Analysis**\nYour question revolves around:\n- How the combination of **1-propanol with water** in the solution preparation phase influences the interactions between the polymer and the added molecule.\n- How this combination is relevant to enhancing the hydrophilicity of the final polymer product.\n\nThe essence of the question ties chemical solvent choices to polymer hydration and reactions that ultimately alter hydrophilicity.\n\n### **2. Detailed and Systematic Answer**\nTo answer this question fully, we need to address the following:\n1. **Role of solvents (1-propanol and water) in controlling polymer-molecule interactions**.\n2. How solvent polarity and hydrogen bonding mechanisms enable hydrophilicity modulation during synthesis.\n3. A proposed experimental preparation scheme that includes 1-propanol and water for hydrophilic polymer synthesis.\n\n---\n\n#### **Step-by-Step Explanation**\n\n### **2.1 The Interaction Between 1-Propanol, Water, and the Polymer**\nWhen preparing a solution of 1-propanol combined with water, the solvent mixture functions as a medium for modulating hydrogen bonding and hydrophobic interactions. Here’s why:\n\n- **Solvent Polarity**:\n  - Water is a **highly polar** solvent, capable of forming extensive hydrogen bonds. It promotes the hydration and hydrophilicity of chemical groups like –OH, –COOH, or –NH2 on the polymer molecule.\n  - 1-Propanol is moderately polar and includes both a hydrophilic hydroxyl (-OH group) and a hydrophobic alkane section. By combining these complementary solvents, you can tailor the solvent environment to balance polar and nonpolar interactions.\n\n- **Hydrogen Bonding**:\n  - 1-propanol can form weaker hydrogen bonds compared to water because the –OH is attached to an alkyl group. However, its hydrophilic properties ensure compatibility with water.\n  - The presence of both water and 1-propanol allows optimization of hydrogen bond donation and acceptance in the system, facilitating interactions between the polymer backbone and any hydrophilic functional groups introduced.\n\n### **2.2 Relevance to Hydrophilicity**\nThe addition of 1-propanol to water significantly impacts polymer hydrophilicity for multiple reasons:\n\n1. **Improved Solvent Dynamics**:\n   The presence of 1-propanol ensures that hydrophilic functional groups (e.g., hydroxyl or amine groups) in the polymer precursor or the added molecule have access to water molecules, enhancing hydration.\n\n2. **Control Over Functional Group Orientation**:\n   The combined solvent mixture creates a favorable environment for the polymer structure to adopt a conformation that maximizes exposure of hydrophilic groups to water. 1-propanol can help solubilize and evenly distribute added molecules that might otherwise resist water solvation.\n\n3. **Enhanced Reaction Efficiency**:\n   During synthesis, intermediates or monomers containing hydrophilic groups may dissolve more uniformly in the water-1-propanol solution, improving reactivity and ensuring uniform incorporation of hydrophilic groups into the final polymer matrix.\n\n---\n\n### **Proposed Experimental Preparation Scheme**\n\n#### **Step 1: Prepare Solvent Mixture**\n- Combine **1-propanol and water** in a ratio of **30:70 vol/vol** (adjustable based on solubility requirements and polymer chemistry).\n  - This ratio balances moderate solvation power from 1-propanol with strong hydrogen bonding from water.\n\n#### **Step 2: Dissolve Polymer Precursor**\n- Add the polymer precursor (e.g., a hydrophilic monomer such as acrylamide or a combination of monomers like polyethylene glycol (PEG), acrylonitrile, etc.) to the solvent mixture at a concentration of **0.5–2 mol/L**.\n  - Stir the solution vigorously to ensure homogeneity.\n\n#### **Step 3: Introduce Hydrophilic Additives**\n- Introduce hydrophilic molecules or functionalization agents (e.g., hydroxyl-rich molecules, carboxylic acids, ammonium salts) to the solvent mixture. These can include molecules like glycerol, acrylic acid, or other modifiers.\n  - Maintain a **molar ratio** of additive to polymer precursor between **1:1–1:2** to ensure sufficient hydrophilic functional group incorporation.\n\n#### **Step 4: Polymerization Reaction**\nDepending on the type of polymer, perform one of the following polymerization techniques:\n- **Free Radical Polymerization**:\n  - Initiator: Use a radical initiator like ammonium persulfate (APS) or azobisisobutyronitrile (AIBN).\n  - Reaction Conditions: Conduct the polymerization at **60–70 °C** for 6–12 hours with continuous stirring.\n- **Condensation Reaction**:\n  - Catalyst: Use a condensation catalyst such as sulfuric acid or phosphoric acid.\n  - Reaction Conditions: Heat the reaction vessel under reflux at **80–100 °C** for a suitable time (~12 hours).\n\n#### **Step 5: Purification**\n- Precipitate the polymer by adding a non-solvent (e.g., methanol or acetone) to isolate the hydrophilic polymer.\n- Wash the polymer thoroughly with water to remove unreacted monomers and residual solvent.\n\n#### **Step 6: Characterization**\n- Use techniques like **FTIR spectroscopy** to confirm the incorporation of hydrophilic groups into the polymer matrix.\n- Perform water contact angle measurements to evaluate hydrophilicity.\n\n---\n\n### **Conclusion**\nThe combination of 1-propanol with water during the solution preparation phase enhances polymer hydrophilicity by optimizing solvent dynamics, hydrogen bonding capabilities, and functional group orientations. This enables the added hydrophilic molecules or groups to interact effectively with the polymer precursor. Following the outlined preparation scheme, you can ensure successful synthesis of a hydrophilic polymer while maintaining rigorous experimental standards.\n\n"
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diff --git a/task2/task2-qa/am7b05286_si_001.json b/task2/task2-qa/am7b05286_si_001.json
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+{
+  "design_question": "Describe the key experimental steps you would follow to ensure the reaction involving POSS-Br proceeds efficiently under oxygen-free conditions.",
+  "design_answer": "To address your question scientifically and systematically, we will first analyze the problem, identify the key points, and then provide a detailed step-by-step experimental protocol to ensure an efficient reaction of POSS-Br under oxygen-free conditions.\n\n---\n\n### Step 1: **Analyze the Problem**\nThe key points you’ve raised are:\n1. **Substrate**: POSS-Br is the compound in focus here.\n2. **Efficiency**: The goal is to maximize the reaction efficiency.\n3. **Reaction Conditions**: The reaction must be carried out under oxygen-free (inert) conditions, which often signifies safeguarding the reaction against oxygen interference, typically for sensitive reagents or catalysts.\n\n### Step 2: **Rationale for Oxygen-Free Conditions**\nOxygen, even in trace amounts, can inhibit reactions—particularly those involving radicals, moisture-sensitive catalysts, or materials prone to oxidative damage (such as POSS derivatives). Therefore, specific strategies, such as inert gas purging or using a glovebox, are critical to maintaining an oxygen-free environment.\n\n---\n\n### Step 3: **Detailed Experimental Protocol**\nBelow is a systematic procedure to ensure the reaction proceeds efficiently under oxygen-free conditions:\n\n---\n\n#### **Step 3.1: Preparing the Setup**\n1. **Glassware Preparation**:\n   - Use Schlenk tubes, flasks, or a sealed reactor compatible with inert gas handling.\n   - Dry the glassware thoroughly in a vacuum oven (110 °C for at least 2 hours) before the experiment to ensure no residual moisture exists.\n\n2. **Assembly Under Inert Atmosphere**:\n   - Move the glassware into a glovebox (preferred) or connect it to a Schlenk line capable of argon or nitrogen purging.\n   - Ensure all joints are airtight by lubricating them with vacuum grease and securing them with clamps.\n\n3. **Selection of Solvent**:\n   - Use an anhydrous, oxygen-free solvent suitable for the reaction. Possible solvents are tetrahydrofuran (THF), dimethylformamide (DMF), or toluene.\n   - Before use, distill the solvent under inert gas if necessary, or use commercially available anhydrous solvents from sealed bottles.\n\n---\n\n#### **Step 3.2: Reaction Setup and Execution**\n1. **Introducing POSS-Br and Reagents**:\n   - Weigh POSS-Br under ambient conditions (if stable in air), or inside a glovebox if it is air sensitive.\n   - Introduce a stoichiometric or slightly excess amount of POSS-Br into the reactor based on the reaction requirement (e.g., 1 mmol for preliminary scale testing).\n   - Add any required co-reagents (e.g., a nucleophile, catalyst, or other reactive species), ensuring accurate molar ratios as dictated by your specific reaction.\n\n2. **Purging Oxygen**:\n   - If using a Schlenk line, perform **three cycles of evacuation and refilling** with argon or nitrogen to displace air completely.\n   - If using a glovebox, transfer all materials and seal the glassware tightly before removing it from the box.\n\n3. **Addition of Solvent**:\n   - Add the anhydrous solvent inside the inert atmosphere (e.g., through a septum using a syringe) to ensure no atmospheric exposure.\n   - Use approximately 10–15 mL of solvent for every mmol of POSS-Br, depending on the reaction scale and solubility of the compounds.\n\n4. **Stirring and Reaction Conditions**:\n   - Seal the reaction vessel and heat or cool it to the desired conditions (e.g., 60–80 °C for nucleophilic substitutions reactions if no incompatibilities arise).\n   - Ensure vigorous stirring to maintain homogeneity.\n   - If air-sensitive catalysts (e.g., transition metal complexes) or thermal initiators are involved, ensure their storage and handling under inert conditions before use.\n\n---\n\n#### **Step 3.3: Monitoring Reaction Progress**\n1. **Sampling**:\n   - Periodically withdraw small aliquots of the reaction mixture using a gas-tight syringe and analyze using gas chromatography (GC), high-performance liquid chromatography (HPLC), or nuclear magnetic resonance (NMR) spectroscopy to ensure reaction progression.\n   - Continue purging the reactor during sampling (if applicable).\n\n2. **Duration**:\n   - Allow the reaction to run for a pre-determined time (e.g., 8–24 hours), depending on the kinetic studies for POSS-Br reactions.\n\n---\n\n#### **Step 3.4: Workup**\n1. **Quenching the Reaction**:\n   - If applicable, the reaction may require quenching by adding a non-reactive diluent (e.g., ethanol) under inert conditions.\n   - Follow the quenching protocol as dictated by reagent incompatibilities or reaction type.\n\n2. **Removing Solvent**:\n   - Remove the solvent under reduced pressure (using a rotary evaporator) after purging the system once more with inert gas.\n\n3. **Purification**:\n   - Purify the product, if necessary, via recrystallization, column chromatography, or precipitation techniques.\n   - Store purified products in sealed containers under inert conditions.\n\n---\n\n### Step 4: **Reaction-Specific Optimizations**\nConsider the following for higher reaction specificity:\n- Catalyst concentration: If a catalyst (e.g., palladium or copper) is used, optimize its concentration (start with 5 mol% relative to POSS-Br).\n- Additives: In certain cases, a reductant (e.g., sodium ascorbate) or ligand might be required to accelerate the reaction.\n- Temperature or Pressure: Adjust based on initial yields; for example, radical reactions sometimes benefit from UV or controlled heating under pressure.\n\n---\n\n### Closing Remarks\nBy carefully following this process, you can ensure the reaction involving POSS-Br proceeds efficiently under oxygen-free conditions. The critical aspects include the proper establishment and maintenance of the inert atmosphere, precise measurements of reagents, and consistent monitoring of reaction progress. If there are any ambiguities specific to your experiment, feel free to share more details or consult particular reaction protocols for POSS-based compounds."
+}
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diff --git a/task2/task2-qa/am9b21871_si_001.json b/task2/task2-qa/am9b21871_si_001.json
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+{
+  "design_question": "Design an experimental scheme for polymerization using N-Hydroxyethylacrylamide, specifying the type of initiator you would use, the solvent, and the conditions required to ensure optimal reaction.",
+  "design_answer": "Certainly! Let us tackle this problem step by step to design a well-thought-out experimental scheme for the polymerization of **N-Hydroxyethylacrylamide (NHEA)**, a molecule commonly used to prepare hydrophilic polymers. Here's how we will proceed:\n\n---\n\n### **Step 1: Analyze the question and summarize the key points**\nTo polymerize **N-Hydroxyethylacrylamide (NHEA)**, the following parameters need to be considered:\n1. **Polymerization Type:** The method of polymerization best suited for NHEA.\n2. **Initiator System:** Selection of an efficient initiator that ensures controlled polymerization.\n3. **Solvent Selection:** Determining an appropriate solvent to dissolve NHEA and promote hydrophilicity in the reaction medium.\n4. **Reaction Conditions:** Optimizing key variables such as temperature, time, concentration of reagents, and atmosphere (e.g., inert gas to prevent oxygen inhibition).\n5. **Polymer Characterization:** How to verify the success of the polymerization.\n\n---\n\n### **Step 2: Experimental Scheme for Polymerization**\n\nThe polymerization of **N-Hydroxyethylacrylamide (NHEA)** can be efficiently carried out using **free-radical polymerization**. Below is a detailed and systematic scheme to achieve this:\n\n#### **Reagents and Materials:**\n- **Monomer:** N-Hydroxyethylacrylamide (NHEA)\n- **Initiator:** Azobisisobutyronitrile (AIBN) – a thermal initiator commonly used for free-radical polymerizations\n- **Solvent:** Deionized water or a water/ethanol mixture for hydrophilic polymerization\n- **Inert Gas:** Nitrogen or argon for purging to remove oxygen\n- **Reaction Flask:** A round-bottom flask equipped with a magnetic stirrer, reflux condenser, and thermometer\n\n#### **Reaction Conditions:**\n1. **Monomer Concentration:** 10–20% (w/v) NHEA in the selected solvent.\n2. **Initiator Concentration:** AIBN at 0.5–1.0 weight percent relative to the weight of the monomer.\n3. **Temperature:** 60–75 °C (based on the thermal decomposition range of AIBN).\n4. **Time:** 4–8 hours for complete polymerization.\n\n---\n\n### **Step 3: Step-by-Step Procedure**\n\n#### **(1) Preparation of the Reaction Mixture**\n1. **Dissolving the Monomer:**\n   - Accurately weigh the required amount of **NHEA** (e.g., 10 g).\n   - Dissolve it in 90 mL of deionized water or a water/ethanol mixture (e.g., 80/20 v/v) under gentle magnetic stirring.\n   - Ensure the monomer is completely dissolved, as this is key for homogeneous polymerization.\n\n2. **Adding the Initiator:**\n   - Weigh and add **AIBN** (e.g., 0.1 g) to the monomer solution.\n   - Stir until the initiator is dissolved. AIBN is only slightly soluble in water, so a water/ethanol mixture may improve its solubility.\n\n#### **(2) Degassing the Reaction Mixture**\n- Transfer the reaction mixture to a round-bottom flask equipped with a reflux condenser.\n- Bubble **nitrogen gas** (or argon) through the reaction mixture for **30 minutes** to eliminate dissolved oxygen, which can inhibit the free-radical polymerization process.\n\n#### **(3) Thermal Polymerization**\n1. **Heating and Reaction:**\n   - Place the flask in an oil bath or water bath controlled at **65 °C**.\n   - Stir constantly using a magnetic stir bar to ensure even heating and mixing.\n   - Maintain the temperature for **4–8 hours**. You may observe an increase in viscosity as the reaction progresses, indicating polymer formation.\n\n2. **Monitoring the Reaction:**\n   - If needed, withdraw small aliquots of the reaction mixture at regular intervals to monitor the conversion of monomer to polymer using **NMR spectroscopy**, **FTIR**, or **GPC** (Gel Permeation Chromatography).\n\n#### **(4) Post-Polymerization Workup**\n1. **Precipitation (if desired):**\n   - After the reaction is complete, cool the mixture to room temperature.\n   - Precipitate the polymer by adding the reaction mixture into an excess of cold ethanol under vigorous stirring.\n   - Collect the polymer by filtration and wash with ethanol several times to remove unreacted monomer and impurities.\n\n2. **Drying the Polymer:**\n   - Dry the resulting polymer under vacuum at 40–50 °C until a constant weight is achieved.\n\n---\n\n### **Step 4: Polymer Characterization**\n\nThe synthesized polymer can be characterized using the following techniques:\n- **FTIR Spectroscopy:** To confirm the polymer structure, look for characteristic amide absorption bands (~1650 cm⁻¹) and hydroxyl groups (~3400 cm⁻¹).\n- **NMR Spectroscopy:** To verify monomer conversion and polymer integration.\n- **Gel Permeation Chromatography (GPC):** To determine the molecular weight (Mn, Mw) and polydispersity index (PDI).\n- **Contact Angle Measurements:** To evaluate the hydrophilicity of the polymer surface.\n\n---\n\n### **Step 5: Notes and Recommendations**\n- **Safety Precautions:**\n  - Handle AIBN carefully, as it is a thermal explosive. Store it in a cool and dry place and weigh it in a fume hood.\n  - Always work with proper personal protective equipment (PPE) and ensure good ventilation in the laboratory.\n- **Optimization Tips:**\n  - The reaction conditions (e.g., initiator concentration, temperature) can be adjusted depending on the molecular weight and PDI required for the polymer.\n  - For improved control over the polymer structure (e.g., block or graft copolymers), consider using another polymerization approach like RAFT (Reversible Addition-Fragmentation chain Transfer) polymerization.\n  \n---\n\n### Final Words\nThis experimental scheme provides a reliable and systematic approach to synthesizing hydrophilic polymers using **N-Hydroxyethylacrylamide**. By following these steps and maintaining rigorous control over the reaction conditions, the desired polymer with excellent hydrophilicity can be achieved. Let me know if you have any additional questions or need assistance with advanced polymerization techniques!"
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+{
+  "design_question": "When using Carboxy-Functionalized Polyhedral Oligomeric Silsesquioxane (POSS-C), explain how changing the number of ethylene glycol (e.g., n=1 to n=6) repeating units could affect the hydrophilicity of the modified polymer.",
+  "design_answer": "Let us carefully analyze and systematically address your question.\n\n### **1. Analysis of the Question and Key Points**\nYour query seeks to explore the relationship between **ethylene glycol (EG) chain length** (i.e., number of repeating EG units, denoted as \\( n \\)) and the **hydrophilicity of a modified polymer** synthesized using Carboxy-Functionalized Polyhedral Oligomeric Silsesquioxane (POSS-C). Specifically, you are asking how varying \\( n \\) (from 1 to 6) influences the hydrophilic properties of the resulting polymer.\n\nTo fully address this question, we need to:\n- Provide a systematic explanation for why ethylene glycol contributes to hydrophilicity.\n- Examine trends in hydrophilicity as \\( n \\) increases (from \\( n=1 \\) to \\( n=6 \\)).\n- Tie these effects specifically to the POSS-C-based polymer.\n\n---\n\n### **2. Answer: Detailed and Systematic Explanation**\n\n#### **Step-by-step Synthesis Process of the Hydrophilic Polymer**\nTo study the effect of ethylene glycol chain length on the hydrophilicity of POSS-C-derived polymers, we propose a synthetic approach that incorporates ethylene glycol of varying lengths (e.g., \\( HO-(CH_2CH_2O)_n-H \\)) into the POSS-C framework. Here is a step-by-step experimental scheme:\n\n---\n\n#### **Step 1: Preparation of Methacrylate-Terminated POSS (Intermediate)**\n**Rationale:** To enhance compatibility and reactivity with ethylene glycol derivatives, POSS-C is often functionalized with polymerizable methacrylate groups. This step involves esterification of the carboxylic acid groups in POSS-C.\n\n**Reaction:**\n\\[ \\text{POSS-C} + \\text{Methacrylic Anhydride} \\xrightarrow{\\text{Catalyst (DMAP)}} \\text{Methacrylate-POSS (POSS-MA)} \\]\n\n- **Reagents:**\n  - Starting material: POSS-C (1.0 equivalent, typically in dry THF for solubility).\n  - Methacrylic anhydride (around 1.2 equivalents to ensure complete esterification).\n  - Catalyst: 4-Dimethylaminopyridine (DMAP, ~0.1 equivalent) to promote esterification.\n  - Solvent: Tetrahydrofuran (THF, anhydrous).\n\n- **Conditions:**\n  - Reaction temperature: 50–60°C.\n  - Reaction time: ~12–16 hours under stirring.\n  - Nitrogen atmosphere: To prevent polymerization of methacrylate under oxygen.\n\n- **Workup:**\n  - Purify the product via solvent evaporation and precipitation in methanol.\n  - Characterize the POSS-MA using FTIR or NMR (ensure disappearance of carboxylic acid signal and appearance of ester bonds).\n\n---\n\n#### **Step 2: Grafting Ethylene Glycol Chains of Varying Length**\n**Rationale:** Incorporation of ethylene glycol derivatives into the polymer enhances hydrophilicity due to the excellent water affinity of the EG moieties (via hydrogen bonding). The oligomers \\( HO-(CH_2CH_2O)_n-H \\) are reacted with POSS-MA to form polymerizable macromonomers.\n\n**Reaction:**\n\\[ \\text{POSS-MA} + HO-(CH_2CH_2O)_n-H \\xrightarrow{\\text{Catalyst (e.g., acid or base)}} \\text{POSS-grafted-EG} \\]\n\n- **Reagents:**\n  - POSS-MA (1.0 equivalent).\n  - Ethylene glycol oligomer (\\( HO-(CH_2CH_2O)_n-H \\), n varies from 1 to 6, 1.2 equivalents depending on desired grafting density).\n  - Catalyst: Acid (e.g., p-toluenesulfonic acid) if using esterification, or base (e.g., TBD or DBU) if using transesterification.\n\n- **Conditions:**\n  - Solvent: Typically use toluene or THF (ensure anhydrous conditions).\n  - Reaction temperature: 40–60°C.\n  - Reaction time: ~6 hours.\n\n- **Workup:**\n  - Remove unreacted ethylene glycol oligomer by dialysis or precipitation in hexane.\n  - Confirm grafting by characterizing via FTIR (EG signature peaks) and GPC (verify molecular weight increase).\n\n---\n\n#### **Step 3: Polymerization to Form Hydrophilic Polymer**\n**Rationale:** The POSS-grafted macromonomer obtained in Step 2 (with \\( n=1 \\) to \\( n=6 \\)) is polymerized to produce the final hydrophilic polymer.\n\n**Reaction:**\n\\[ n[\\text{POSS-grafted-EG}] \\xrightarrow{\\text{Free Radical Polymerization (Initiator)}} \\text{Hydrophilic POSS-Polymer.} \\]\n\n- **Reagents:**\n  - POSS-grafted macromonomer (variable molecular weight depending on \\( n \\)).\n  - Initiator: Azobisisobutyronitrile (AIBN, ~1 wt.%).\n  - Solvent: Anhydrous DMSO (for solubility of both hydrophobic and hydrophilic components).\n\n- **Conditions:**\n  - Polymerization temperature: ~70°C under nitrogen.\n  - Reaction time: ~24 hours.\n\n- **Workup:**\n  - Precipitate the polymer in cold diethyl ether.\n  - Dry under vacuum.\n\n---\n\n### **3. Relationship Between Ethylene Glycol Chain Length and Hydrophilicity**\nOnce the polymer is synthesized, the chain length of ethylene glycol (\\( n \\)) significantly influences the hydrophilicity of the resulting material. Here's how:\n\n1. **Hydrogen Bonding Capacity:**\n   - As \\( n \\) increases, the number of ether oxygen atoms (-O-) and hydroxyl terminals contributing to hydrogen bonding with water molecules also increases.\n   - This enhances the hydration layer around the polymer in aqueous systems, improving hydrophilicity.\n\n2. **Water Solubility:**\n   - Short EG chains (\\( n=1 \\) or 2) may not provide sufficient hydrophilicity for full water solubility. As \\( n \\) increases, the polymer becomes increasingly water-soluble due to a greater density of hydrophilic groups.\n\n3. **Hydrophilic-Hydrophobic Balance:**\n   - At smaller \\( n \\), the POSS structure (which is relatively hydrophobic) dominates in terms of physical behavior.\n   - Larger \\( n \\) ensures that the ethylene glycol units counterbalance POSS’s hydrophobicity, yielding a more hydrophilic material.\n\n4. **Applications Tuning:**\n   - **Short EG Chains (\\( n=1–2 \\)):** Better for applications requiring amphiphilic behavior (e.g., emulsion stabilization or coatings).\n   - **Long EG Chains (\\( n=4–6 \\)):** Better for highly hydrophilic applications (e.g., hydrogels, water purification membranes, drug delivery vehicles).\n\n---\n\n### **4. Experimental Validation**\nTo experimentally confirm the hydrophilicity as a function of \\( n \\):\n- **Contact Angle Measurement:** Lower values indicate higher hydrophilicity.\n- **Water Absorption Test:** Measure the water uptake percentage for films or crosslinked samples.\n- **Swelling Behavior:** Monitor equilibrium swelling ratio in water for crosslinked materials.\n- **Thermogravimetric Analysis (TGA):** Thermal stability may slightly decrease with increasing \\( n \\) due to the higher organic content (EG chains).\n\n---\n\n### **5. Conclusion**\nBy increasing the number of EG repeating units (\\( n \\)), the hydrophilicity of the POSS-C-based polymer is systematically enhanced due to increased hydrogen bonding and water affinity. This tunable hydrophilicity is key for designing materials tailored for specific applications like hydrogels, coatings, or biomaterials."
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+{
+  "design_question": "When synthesizing a hydrophilic polymer system, how would you incorporate 1,3,5-triformylbenzene (TFB) to enhance the stability of the crosslinked network? Outline the specific functional groups this molecule reacts with during the process.",
+  "design_answer": "Certainly, let us systematically address your question on how to incorporate **1,3,5-triformylbenzene (TFB)** into the synthesis of a hydrophilic polymer system to enhance the stability of the crosslinked network. First, we will analyze the question, identify the key points, and provide a comprehensive experimental preparation scheme. Let us proceed step by step:\n\n---\n\n### Key Considerations in the Question:\n1. **The role of TFB:** You wish to employ TFB as a crosslinking agent to enhance the stability of the polymer network. To do so, we must focus on its functional groups (**formyl groups, -CHO**) and identify functional groups in the polymer network that can react with these.\n2. **Hydrophilicity requirements:** Maintaining or enhancing the hydrophilic nature of the polymer system during the process is essential.\n3. **Reaction mechanism:** The interaction of TFB’s formyl groups with complementary reactive groups is necessary to form the chemical bonds responsible for network crosslinking.\n\n--- \n\n### **Step-by-Step Synthesis Process:**\nBelow, I outline the experimental preparation scheme:\n\n#### Step 1: Selection of Polymer Precursor\n- Choose a hydrophilic monomer or polymer precursor that contains reactive functional groups capable of reacting with TFB’s formyl groups. Examples of useful reactive groups include:\n  - **Amine groups (-NH2):** For Schiff base condensation to form imine bonds (-C=N).\n  - **Hydroxyl groups (-OH):** For acetal or hemiacetal formation in acidic conditions.\n- A suitable candidate could be a hydrophilic polymer such as poly(ethyleneimine) (PEI) or a functionalized poly(vinyl alcohol) (PVA) that has ample hydroxyl or amino groups.\n\n---\n\n#### Step 2: Preparation of Reaction Solution\n**Materials Required:**\n1. **1,3,5-Triformylbenzene (TFB):** Acts as a trifunctional aldehyde-based crosslinker.\n2. **Polymer precursor (e.g., PEI or PVA):** Provides the backbone with reactive groups (-NH2 or -OH).\n3. **Solvent:** Ensure a hydrophilic solvent to support solubility of reactants. Frequently used solvents include water, ethanol, or DMSO.\n4. **Catalyst (if applicable):**\n   - For Schiff base reactions: Acidic catalysts (e.g., acetic acid) to promote condensation.\n   - For hydroxyl-based crosslinking: Mild acids like p-toluenesulfonic acid.\n\n**Experimental Setup:**\n1. Dissolve the hydrophilic polymer precursor in the solvent. For instance:\n   - Dissolve PEI in water (e.g., at 10 wt% concentration).\n2. Separately dissolve TFB in the same solvent. Since TFB is sparingly soluble in water, use moderate stirring, heating (~40–50 °C), or employ DMSO if solubility challenges arise.\n\n---\n\n#### Step 3: Stoichiometric Ratios\n- The ratio of **TFB to reactive groups** on the polymer backbone is crucial for uniform crosslinking.\n- Calculate the stoichiometric ratio based on the molar amount of functional groups. For example:\n  - If PEI has ~5 mmol of amino groups, use ~1.6 mmol of TFB (1:3 ratio of amine groups to TFB’s formyl groups ensures all sites are engaged).\n\n---\n\n#### Step 4: Reaction Conditions\n- Gradually combine the TFB solution with the polymer solution under constant stirring.\n- Maintain the reaction temperature between 40–50 °C to foster crosslinking. Avoid overheating as it can degrade sensitive groups and reduce hydrophilicity.\n- Allow the reaction to proceed for **6–12 hours** to ensure complete network formation.\n- Monitor progress using techniques such as:\n  - FTIR spectroscopy to verify the formation of imine bonds (-C=N) or acetal/ether linkages.\n\n---\n\n#### Step 5: Post-Processing\n1. **Purification:** If necessary, remove unreacted TFB or polymer by precipitation (e.g., using acetone) and dialysis in water to enhance purity.\n2. **Drying and Curing:** Dry the crosslinked polymer at ambient temperature or under vacuum at 40–50 °C to avoid disrupting the hydrophilic structure.\n\n---\n\n#### Step 6: Characterization of the Hydrophilic Polymer\n- Confirm the formation of the crosslinked network:\n  1. **FTIR Spectroscopy:** Look for characteristic peaks corresponding to imine (C=N, ~1640 cm⁻¹) or acetal bonds.\n  2. **Swelling Test:** Assess the hydrophilicity by studying the swelling behavior of the new polymer network in water or buffer solutions.\n  3. **Thermal Stability Tests (TGA/DSC):** Confirm that the crosslinking imparts the desired stability.\n  4. **Mechanical Tests:** Evaluate the strength of the crosslinked network using tensile/compression tests if applicable.\n\n---\n\n### **Functional Groups Involved:**\n**1,3,5-Triformylbenzene (TFB)** reacts with:\n1. **Amino groups (-NH2):** Via Schiff base condensation to form **imine bonds** (-C=N), which provide robust and stable crosslinks.\n2. **Hydroxyl groups (-OH):** Under acidic conditions, TFB can form acetals (R-CH(OR’)₂) or hemiacetals (R-CH(OH)(OR')) with alcohol groups, leading to hydrophilic and chemically stable crosslinked structures.\n\n---\n\n### **Summary**\nIncorporating TFB into a hydrophilic polymer system enhances the stability of the crosslinked network through Schiff base condensation (imine bond formation) or acetal linkages, depending on the reactive groups of the polymer precursor. By systematically controlling the reaction stoichiometry, temperature, and catalysts, you can successfully synthesize a hydrophilic polymer with improved network stability, suitable for applications such as hydrogel formation, water-resistant coatings, and biomedical devices.\n\nBy following this protocol step by step, you should have no trouble incorporating TFB into your hydrophilic polymer system. Let me know if there are any additional questions!"
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+{
+  "design_question": "Given that 1,3,5-triformylbenzene (TFB) can react with both amino and hydroxyl groups, detail an experimental approach to incorporate TFB into a polymer coating for hydrophilic surface modification.",
+  "design_answer": "Certainly! Let us analyze your question systematically and design an experimental preparation scheme for incorporating 1,3,5-triformylbenzene (TFB) into a polymer coating for hydrophilic surface modification.\n\n### **Step 1: Analyze the key points in the question**\n1. **Target molecule properties**: TFB has reactive formyl (–CHO) groups capable of undergoing condensation reactions with amino (–NH₂) or hydroxyl (–OH) groups.\n2. **Objective**: Incorporate TFB into a polymer coating to enhance hydrophilicity.\n3. **Reaction pathways**: Given TFB’s chemical properties, the primary reactions likely involve Schiff base formation (reaction with amines) or acetal formation (reaction with hydroxyl groups).\n4. **Experimental goal**: Develop a hydrophilic polymer coating with surface modification that leverages TFB's functionality to improve hydrophilicity and performance.\n\n### **Step 2: Design the experimental scheme**\nWe will develop a step-by-step synthesis methodology, including reagent choices, reaction conditions, molar ratios, and equipment requirements.\n\n---\n\n#### **Step 2.1: Selection of polymer backbone**\nTo design a hydrophilic polymer coating, we select a polymer featuring either amino groups (e.g., polyethyleneimine) or hydroxyl groups (e.g., polyvinyl alcohol, PVA). Both polymers are inherently hydrophilic and thus provide a foundation for improving surface hydrophilicity.\n\nFor this synthesis, we will use **polyethyleneimine (PEI)** due to its abundant amino groups available for Schiff base condensation with TFB.\n\n#### **Step 2.2: Preparation of the polymer solution**\nPrepare an aqueous solution of PEI for the reaction:\n- **Reagents**:\n  - Branched polyethyleneimine (PEI) with a molecular weight of ~25,000.\n  - Deionized water.\n- **Procedure**:\n  - Dissolve PEI in deionized water at a concentration of 10 wt% (e.g., 10 g PEI in 100 mL water).\n  - Stir the solution at room temperature for 30 minutes until fully dissolved.\n- **Notes**: The resulting PEI solution serves as the base polymer for surface modification.\n\n---\n\n#### **Step 2.3: Adding TFB to the reaction**\nIntroduce TFB into the PEI solution to begin the Schiff base formation reaction:\n- **Reagents**:\n  - 1,3,5-Triformylbenzene (TFB; molecular weight = 192.14 g/mol).\n- **Procedure**:\n  - For every 10 g of PEI, add TFB in a molar ratio of **1:3** (TFB-to-primary amines).\n  - Approximate calculation:\n    - PEI has ~7 mmol primary amines per gram. For 10 g PEI, the total amines = 70 mmol.\n    - Add 23.33 mmol TFB (equivalent to ~4.48 g TFB).\n  - Dissolve TFB in ethanol or dimethyl sulfoxide (DMSO) to achieve complete solubility, then add this solution dropwise into the stirring PEI solution.\n\n---\n\n#### **Step 2.4: Reaction conditions**\nPerform the Schiff base condensation reaction under optimized conditions:\n- **Reaction environment**:\n  - Maintain the reaction at **50–60 °C** to promote condensation between formyl groups (TFB) and amino groups (PEI).\n  - Adjust the pH to ~8 using triethylamine or dilute NaOH to facilitate the reaction but avoid hydrolysis of the Schiff base.\n- **Time**:\n  - Stir the reaction mixture for 6–12 hours under nitrogen atmosphere to prevent oxidation.\n- **Mixing apparatus**:\n  - Use a magnetic stirrer for homogeneous mixing and a sealed reaction vessel for reducing contamination.\n\n---\n\n#### **Step 2.5: Purification of the polymer**\nIsolate and purify the modified polymer to remove unreacted TFB:\n- **Procedure**:\n  - Dialyze the reaction product against deionized water (using dialysis tubing, molecular weight cutoff ~12–14 kDa).\n  - Perform dialysis for up to 48 hours with frequent water changes to remove small molecule impurities.\n\n---\n\n#### **Step 2.6: Formation of hydrophilic polymer coating**\nApply the purified polymer onto the desired substrate to create a hydrophilic coating:\n- **Coating procedure**:\n  - Dissolve 1–5 wt% of the purified polymer in water or ethanol.\n  - Clean the substrate (e.g., glass, silicon wafer, or metal) with ethanol and deionized water, then dry thoroughly.\n  - Use spin coating, dip coating, or spray coating to apply the polymer solution evenly on the surface.\n  - Dry the coated substrate at **60–80 °C** in a vacuum oven for 2–3 hours to remove residual solvents and enhance adhesion.\n\n---\n\n### **Reaction scheme:**\nThe reaction between TFB and PEI follows this simplified chemical pathway:\n#### TFB + Amino groups (PEI) → Schiff base-modified PEI\nThe Schiff base structure (–C=N–) enhances surface hydrophilicity by introducing polar functional groups while maintaining polymer stability.\n\n---\n\n### **Step 3: Summary of the experiment**\n1. Dissolve PEI in deionized water to prepare the polymer base.\n2. Add TFB to the PEI solution in a controlled molar ratio of 1:3 (TFB-to-primary amine groups).\n3. Perform the reaction under mild temperature (50–60 °C) and optimized pH (~8) for 6–12 hours.\n4. Purify the modified polymer by dialysis to remove unreacted TFB.\n5. Coat the substrate with the polymer and cure at elevated temperatures to finalize the hydrophilic coating.\n\n### **Scientific rationale and expected outcome:**\nThe incorporation of TFB via Schiff base formation introduces polar groups into the polymer matrix, enhancing water affinity and hydrophilicity. This functionalized polymer coating should provide improved wettability and adhesion properties for surface modification applications.\n\nIf you have further questions, feel free to ask, and I’ll gladly assist in refining any step or explaining the underlying chemistry!"
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+{
+  "design_question": "Describe the procedure for reacting 2-(cyclohexylamino)-ethanesulfonic acid with polyisocyanate under controlled temperature conditions to enhance the hydrophilicity of the polymer. What key parameters require monitoring during the reaction?",
+  "design_answer": "Certainly! I appreciate your question, as it highlights a significant approach to tuning the hydrophilicity of a polymer through chemical modification. Let’s methodically break this task down and develop a detailed experimental preparation scheme.\n\n---\n\n### Step 1: **Question Review and Key Points Summarized**\nThe problem involves reacting 2-(cyclohexylamino)-ethanesulfonic acid (commonly referred to as CHES) with a polyisocyanate to create a polymer with enhanced hydrophilicity. CHES is hydrophilic due to both its sulfonic acid group and secondary amine, and introducing it into a polyisocyanate structure would impart hydrophilicity to the resulting polymer. Key parameters to consider during this process include:\n1. Maintaining controlled temperature conditions (to avoid side reactions or premature crosslinking).\n2. Ensuring proper molar ratios of CHES to isocyanate groups for an optimized reaction.\n3. Proper solvent selection to ensure complete dissolution and adequate mixing of reactants.\n4. Monitoring reaction variables, such as the reaction time, temperature, and degree of polymerization.\n\n---\n\n### Step 2: **Reagent and Material Preparation**\n#### Required materials:\n1. **2-(Cyclohexylamino)-ethanesulfonic acid (CHES)**: Hydrophilic reactant.\n2. **Polyisocyanate** (e.g., hexamethylene diisocyanate [HDI], or a polyisocyanate oligomer): Base polymer reagent.\n3. **Solvent**: N,N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) is recommended for dissolving CHES and the polyisocyanate.\n4. **Catalyst (optional)**: Dibutyltin dilaurate (DBTDL) or triethylamine to promote urethane bond formation.\n5. **Desiccant or drying agent**: To remove water, since water reacts with isocyanates.\n6. **Nitrogen or argon gas**: To create an inert atmosphere and prevent reaction of the isocyanates with ambient moisture.\n\n#### Reaction overview:\nThe key reaction mechanism involves:\n- Reaction of the isocyanate (-N=C=O) groups from the polyisocyanate with the secondary amine (-NH-) group of CHES to form a urea linkage (-NH-CO-NH-).\n- The resultant polymer will have hydrophilic sulfonic acid (-SO₃H) side groups, enhancing the overall hydrophilicity.\n\n---\n\n### Step 3: **Experimental Procedure**\n#### (1) **Preparation of CHES Solution**:\n   - **Weigh CHES**: Based on the desired molar ratio (e.g., 1:1 ratio between CHES and isocyanate groups on the polyisocyanate), determine the number of moles of CHES required relative to the isocyanate functionality. For example, if 1 g of a polyisocyanate contains 4 mmol of -NCO groups, weigh 4 mmol (approximately 1.03 g) of CHES.\n   - **Dissolve CHES**: Dissolve CHES in DMF or DMSO in a dry reaction flask. Use enough solvent to create a homogenous solution (10-20 mL per gram of CHES). If necessary, gentle heating (~40–50°C) can assist dissolution.\n   - **Neutralize pH (optional)**: If the sulfonic acid group interferes with reactivity, consider neutralizing it with a base like triethylamine to its sulfonate (R-SO₃⁻) form before reaction.\n\n#### (2) **Preparation of Polyisocyanate Solution**:\n   - **Dry the polyisocyanate**: Remove any moisture from the polyisocyanate by vacuum drying or storing it over desiccant in a dry container.\n   - **Weigh the polyisocyanate**: Quantify the amount needed based on the molar ratio desired.\n   - **Dissolve in solvent**: Add the polyisocyanate to DMF or DMSO to form a solution. Stir gently under an inert nitrogen atmosphere to prevent moisture absorption.\n\n#### (3) **Reaction Setup**:\n   - Combine the CHES and polyisocyanate solutions in a round-bottom flask equipped with a magnetic stir bar. Ensure the reaction is performed under an inert atmosphere (e.g., nitrogen or argon) to avoid isocyanate degradation.\n   - Add a catalytic amount of DBTDL or triethylamine (0.1–0.5% molar relative to isocyanate groups) if necessary to enhance reaction rates.\n   - Stir the mixture continuously.\n\n#### (4) **Reaction Conditions**:\n   - **Temperature Control**: Slowly raise the temperature to 50–70°C (optimal range). Ensure the reaction temperature does not exceed 80°C to prevent side reactions (e.g., isocyanate dimerization or trimerization, or thermal breakdown of CHES).\n   - **Reaction Time**: Allow the reaction to proceed for 8–12 hours. Continuously monitor the progress using Fourier-transform infrared spectroscopy (FTIR) to track the disappearance of the -N=C=O stretching band at ~2270 cm⁻¹ and the appearance of urea carbonyl (-C=O) stretching near 1640–1660 cm⁻¹.\n\n#### (5) **Post-Reaction Workup**:\n   - Cool the reaction mixture to room temperature.\n   - Precipitate the polymer by adding the reaction mixture into a large excess of a nonsolvent like diethyl ether or methanol.\n   - Wash the precipitated polymer thoroughly to remove residual solvent and unreacted CHES.\n   - Dry the polymer under vacuum at 40–50°C to remove any remaining solvent.\n\n---\n\n### Step 4: **Monitoring and Optimization**\n#### Key parameters to monitor:\n1. **Molar Ratios**: Ensure stoichiometry between CHES and polyisocyanate is balanced. Under-stoichiometric CHES leads to incomplete hydrophilicity; excess CHES can impede crosslinking.\n2. **Temperature**: Keep the reaction temperature stable to avoid side reactions or isocyanate degradation.\n3. **Moisture Control**: Isocyanates are highly reactive with water, leading to undesirable urea formation or foaming.\n4. **Reaction Progress**: Track the disappearance of isocyanate groups using FTIR.\n5. **Polymer Properties**: Analyze the final polymer (e.g., hydrophilicity via contact angle measurement, molecular weight via gel permeation chromatography [GPC], and chemical structure via NMR or FTIR).\n\n---\n\n### Step 5: **Final Remarks**\nThis experimental procedure ensures that the hydrophilic CHES is covalently attached to the polyisocyanate backbone to enhance the polymer's water affinity. By carefully controlling the reaction conditions and monitoring key parameters, you should be able to prepare a functionalized polymer with excellent hydrophilicity tailored to your application.\n\nWould you like me to explain the underlying reaction mechanisms (e.g., urea formation) or assist with troubleshooting potential challenges during this synthesis?"
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+{
+  "design_question": "How would you incorporate hydroxyethyl methacrylate (HEA) into a copolymer synthesis process to achieve enhanced hydrophilicity in the final polymer material? Specify any variables you would adjust and explain their role in the experiment.",
+  "design_answer": "Ah, a thought-provoking and essential inquiry! Incorporating hydroxyethyl methacrylate (HEMA) into a copolymer synthesis process to enhance hydrophilicity is a classic and practical approach in the field of hydrophilic polymers. Let's approach this systematically and step by step to ensure you can confidently replicate this in the laboratory.\n\n---\n\n### **Step 1: Analyze the Key Points of Your Question**\n1. **Objective**: To synthesize a hydrophilic copolymer with enhanced hydrophilicity by incorporating HEMA into the polymer composition.\n2. **Monomer Details**:\n   - HEMA is a hydrophilic monomer due to its hydroxyethyl group (-CH₂CH₂OH), making it suitable for increasing polymer-water interactions.\n   - We need to copolymerize HEMA with one or more comonomers to fine-tune the physical, chemical, or mechanical properties of the final material.\n3. **Variables to Adjust**:\n   - HEMA content in the copolymer (molar or weight fraction).\n   - Type of comonomer(s) used (e.g., hydrophobic or amphiphilic monomers for balance).\n   - Initiator type and concentration.\n   - Reaction conditions, including solvent selection, reaction temperature, and time.\n\n---\n\n### **Step 2: Step-by-Step Synthesis Process for a HEMA-Based Hydrophilic Copolymer**\n\n#### **Step 2.1: Materials and Equipment**\n- **Monomers**: \n  - **Hydrophilic monomer**: Hydroxyethyl methacrylate (HEMA).\n  - **Comonomer options** (depending on application): Methyl methacrylate (MMA) for biocompatibility or ethyl methacrylate (EMA) for increased flexibility.\n- **Solvent**: Use a water-miscible solvent such as ethanol or isopropanol for hydrophilic systems. Alternatively, consider a mixed solvent system (e.g., ethanol and water) for controlled solubility.\n- **Initiator**: Azobisisobutyronitrile (**AIBN**) for free-radical polymerization in organic solvents, or ammonium persulfate (**APS**) for aqueous polymerization.\n- **Reaction Vessel**: Round-bottom flask with a reflux condenser for temperature control.\n\n#### **Step 2.2: Reaction Conditions and Setup**\n1. **Monomer Feed Ratio**:\n   - Adjust the molar ratio of HEMA to the comonomer(s). For high hydrophilicity:\n     - Use 50–80% HEMA in the monomer mixture (by mole).\n   - For balanced hydrophilicity and mechanical properties:\n     - Use 30–50% HEMA with 50–70% hydrophobic or amphiphilic comonomers.\n\n2. **Preparation**:\n   - In a round-bottom flask, dissolve the monomers (e.g., HEMA and MMA) in the selected solvent under stirring.\n   - Add the initiator (typically 1–2% by weight of the total monomers) and dissolve thoroughly.\n     - **For AIBN**: Pre-dissolve in the chosen solvent. Ensure the mixture is purged with nitrogen to remove oxygen, which can inhibit radical generation.\n     - **For APS**: Mix directly if using water as the solvent and ensure proper dissolution.\n   - Optional: Use chain transfer agents such as mercaptopropionic acid if molecular weight control is required.\n\n3. **Reaction Temperature and Time**:\n   - For AIBN: Set the reaction temperature to 60–70°C for efficient thermal decomposition of the initiator.\n   - For APS: Conduct the reaction at 60°C for aqueous systems.\n   - Typical reaction time: 4–6 hours, until the reaction achieves near-complete conversion. Monitor the reaction's progress using techniques such as ^1H-NMR or FTIR.\n\n4. **Solvent and Mixing Considerations**:\n   - Ensure thorough mixing to maintain homogeneity, as HEMA is prone to phase separation during copolymerization if the composition or solvent system is poorly matched.\n\n#### **Step 2.3: Reaction Workup**\n1. **Precipitation of the Polymer**:\n   - Transfer the reaction mixture into a nonsolvent such as diethyl ether or methanol to precipitate the polymer.\n   - Filter and wash the polymer thoroughly with a nonsolvent to remove residual unreacted monomers or solvent.\n\n2. **Drying**:\n   - Air-dry the precipitated polymer. Further dry it under vacuum at 40–50°C to remove any trapped solvent.\n\n3. **Characterization of the Polymer**:\n   - **Hydrophilicity Test**: Measure water contact angle (lower contact angle = higher hydrophilicity).\n   - **Molecular Weight**: Use gel permeation chromatography (GPC) to confirm molecular weight and distribution.\n   - **Chemical Structure**: Use ^1H-NMR or FTIR to confirm successful incorporation of HEMA into the copolymer.\n\n---\n\n### **Variables to Optimize and Their Role**\n1. **HEMA Content**:\n   - Higher HEMA content generally increases water uptake and hydrophilicity due to the presence of hydroxyl groups. However, excessively high HEMA may compromise the mechanical properties and processability of the polymer.\n   - Suggestion: Start with a 50:50 molar ratio of HEMA to a hydrophobic comonomer like MMA, and adjust based on desired properties.\n\n2. **Solvent System**:\n   - Select a solvent system that ensures both HEMA and the comonomer remain dissolved during the polymerization to promote uniformity.\n   - Mixed solvents (e.g., ethanol-water) can modulate polymer properties.\n\n3. **Initiator Concentration**:\n   - Low initiator concentrations favor higher molecular weights but may slow reaction kinetics.\n   - Higher concentrations speed up polymerization but yield lower molecular weight polymers.\n\n4. **Reaction Temperature**:\n   - Ensure control of temperature within a few degrees, as over-heating can cause side reactions or degrading of the polymer ends.\n\n---\n\n### **Final Notes for Laboratory Practice**\n- The approach I've described is primarily for free-radical solution polymerization. If you aim for a different architecture, such as block or graft copolymers, adjustments will be necessary.\n- Always consider the specific end-use application of the polymer to balance hydrophilicity with other desirable properties, such as mechanical strength or biocompatibility.\n  \nBy carefully adjusting HEMA content, reaction conditions, and comonomer selection, you should be able to achieve a copolymer with enhanced hydrophilicity tailored to your application.\n\nGo ahead and implement this thoughtfully in the lab — I look forward to hearing about your experimental results!"
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+{
+  "design_question": "Describe the role of 2,2'-azobis(2-methylpropionitrile) (AIBN) in the polymerization process and how the amount of AIBN influences the formation of hydrophilic polymers.",
+  "design_answer": "Certainly! Let's break the question into key components and systematically address it:\n\n---\n\n### **Question Analysis and Key Points:**\n1. **Role of 2,2'-azobis(2-methylpropionitrile) (AIBN):**\n   - AIBN is a commonly used free radical initiator in polymerization.\n   - The specific role of AIBN during polymerization needs to be clarified in terms of initiating the reaction and its impact on the resulting polymer properties.\n\n2. **Influence of AIBN Amount on Polymer Formation:**\n   - Investigate how the concentration of AIBN affects the polymerization rate, molecular weight, and hydrophilic nature of the final polymer.\n   - Explore the balance between initiator concentration and reaction control in achieving the desired hydrophilicity.\n\n---\n\n### **Systematic Answer to the Question:**\n\n#### **Step 1: Role of 2,2'-Azobis(2-methylpropionitrile) (AIBN) in Polymerization**\n   1. **Initiation of Polymerization:**\n      - AIBN is a thermal initiator that decomposes upon heating to release free radicals, which are essential for initiating chain polymerization reactions. Upon heating (generally between 60–90°C), AIBN undergoes homolytic cleavage to form two 2-cyanoprop-2-yl radicals:\n        \\[\n        \\text{R-N=N-R} \\xrightarrow{\\Delta} 2R^\\bullet\n        \\]\n        Here, \\(R^\\bullet\\) represents the free radical species.\n\n      - These radicals react with monomer molecules, forming reactive centers that propagate polymer chains.\n\n   2. **Control of Polymerization Kinetics:**\n      - The rate of polymerization depends on the concentration of free radicals generated by AIBN. A higher concentration of radicals accelerates the chain-initiation step but also increases the rate of chain-termination reactions, ultimately influencing the polymer's molecular weight.\n\n   3. **Impact on Hydrophilicity:**\n      - For hydrophilic polymer synthesis, AIBN facilitates polymerization of hydrophilic monomers (e.g., acrylamide, hydroxyethyl methacrylate) or ensures copolymerization with hydrophilic segments.\n      - The uniformity of radical formation by AIBN is critical to achieving a controlled polymer architecture, minimizing defects, and reliably incorporating hydrophilic functional groups.\n\n---\n\n#### **Step 2: Influence of AIBN Amount on Polymer Formation**\n   1. **Optimal AIBN Concentration:**\n      - **Low Concentration of AIBN:** \n        - Generates fewer radicals, leading to slower polymerization and longer polymer chains. This results in higher molecular-weight polymers with reduced termination events.\n        - For hydrophilic polymers, fewer radicals may allow better incorporation of hydrophilic monomers, enhancing solubility and water affinity.\n        - However, excessively low concentration can result in incomplete polymerization or uneven hydrophilic segment distribution.\n\n      - **High Concentration of AIBN:**\n        - Produces a higher number of free radicals, which accelerates initiation and polymerization.\n        - Leads to shorter polymer chains due to the increased likelihood of chain termination (e.g., radical recombination).\n        - At very high concentrations, hydrophilicity may be reduced, as the polymerization may favor formation of shorter hydrophobic blocks or inefficient incorporation of hydrophilic monomers.\n\n   2. **Determining the Right Balance:**\n      - The amount of AIBN should be optimized to achieve the desired hydrophilic properties without comprising chain uniformity or molecular weight distribution. This typically involves experimental trials with varying concentrations.\n      - A guideline for AIBN is to use 0.5–2.0 mol% relative to monomer concentration, though specific optimization depends on the nature of the monomers and reaction medium.\n\n---\n\n#### **Step 3: Experimental Scheme for Optimizing AIBN in Hydrophilic Polymer Synthesis**\n   We’ll outline a general experiment where the influence of AIBN is studied systematically to find the optimal conditions:\n\n   1. **Materials:**\n      - Monomer: A hydrophilic monomer such as acrylamide or hydroxyethyl methacrylate (HEMA).\n      - Solvent: Deionized water or a suitable solvent compatible with the monomer (e.g., ethanol for HEMA).\n      - Initiator: AIBN (start with 1.0 mol% relative to total monomer).\n      - Additional reagents: Crosslinker (if needed) or a chain transfer agent (to modulate chain length).\n\n   2. **Procedure:**\n      - **Step 1: Preparation of Reaction Mixture**\n        - Dissolve the hydrophilic monomer in the chosen solvent at the desired concentration (e.g., 10–20% w/v).\n        - Add AIBN at an initial amount (e.g., 1.0 mol% of monomer) and mix thoroughly.\n      - **Step 2: Degassing**\n        - Purge the reaction mixture with nitrogen or argon gas for 15–30 minutes to remove dissolved oxygen, which can inhibit radical polymerization.\n      - **Step 3: Polymerization**\n        - Heat the mixture to 70°C (or the recommended temperature for AIBN) and maintain under constant stirring. Monitor the reaction for 1–6 hours, depending on the desired conversion and polymerization rate.\n      - **Step 4: Quenching and Isolation**\n        - Stop the reaction by cooling to room temperature and diluting with water (if needed). Precipitate the polymer using an anti-solvent (e.g., acetone for HEMA) or dialyze to remove unreacted species.\n\n   3. **Analysis of Results:**\n      - Measure molecular weight and distribution (e.g., using GPC or SEC).\n      - Evaluate hydrophilicity via water contact angle measurements, swelling tests, or solubility in water.\n      - Compare the results for multiple AIBN concentrations (e.g., 0.5, 1.0, and 2.0 mol%) to identify trends and optimize conditions.\n\n---\n\n### **Conclusion:**\n2,2′-Azobis(2-methylpropionitrile) (AIBN) plays a critical role as a thermal initiator by generating free radicals that drive polymerization. The amount of AIBN significantly impacts the polymerization kinetics, molecular weight, chain architecture, and ultimately the hydrophilic properties of the polymer. A balance must be struck in choosing the appropriate AIBN concentration to achieve high polymerization efficiency while maximizing hydrophilicity. Systematic experimental trials are essential to determine optimal conditions, tailored to the specific monomers used and their reactivity.\n\n"
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+{
+  "design_question": "Describe how the molecule Tween 20 can be chemically modified and incorporated into a polymer matrix to enhance its hydrophilicity. Include details of any reactions or catalysts that might be required.",
+  "design_answer": "Certainly! Thank you for your question. Let’s systematically approach the task of chemically modifying Tween 20 and incorporating it into a polymer matrix to enhance hydrophilicity. Here's how we proceed, step by step.\n\n---\n\n### **1. Analysis of the Question and Key Points**\n#### Key Points:\n- **Tween 20**: Tween 20 is a surfactant with a polyoxyethylene chain, which gives it inherent hydrophilicity. It contains hydroxyl groups in its polyether structure.\n- **Enhancing Hydrophilicity**: The goal is to chemically modify Tween 20 so that it becomes more hydrophilic when integrated into a polymer matrix.\n- **Incorporation into a Polymer Matrix**: Chemical modification and integration into a polymer network must occur under controlled conditions to ensure compatibility with the matrix and stability of the final material.\n\n#### Summary of the Approach:\nTo enhance hydrophilicity using Tween 20, we will:\n1. Modify its structure by functionalizing the hydroxyl groups to create reactive sites for polymerization.\n2. Couple it to a polymer backbone through covalent linkage, utilizing appropriate catalysts and reaction conditions.\n3. Optimize the polymerization reaction and validate the hydrophilicity of the resulting material.\n\nNow, let’s delve into the experimental preparation scheme step by step.\n\n---\n\n### **2. Detailed Experimental Preparation Scheme**\n\n#### **Step 1: Functionalizing Tween 20**\nTo integrate Tween 20 into a polymer matrix, the hydroxyl groups in its structure must be activated to allow polymer attachment. A common strategy is using acryloyl chloride or glycidyl methacrylate to introduce polymerizable functional groups.\n\n**Reaction:**\nHydroxyl groups on Tween 20 react with acryloyl chloride to form acrylate-functionalized Tween 20.\n\n- **Reagents**: Tween 20, Acryloyl chloride, Triethylamine (TEA).\n- **Solvent**: Dichloromethane (DCM) or anhydrous toluene.\n- **Reaction Conditions**:\n  - Dissolve Tween 20 in DCM or toluene under inert conditions (argon or nitrogen atmosphere).\n  - Slowly add acryloyl chloride dropwise in the presence of TEA to neutralize HCl produced during the reaction.\n  - Maintain the temperature at 0–5°C during addition, then stir at room temperature for 6–12 hours.\n\n**Key Parameters**:\n- Molar ratio of Tween 20:acryloyl chloride:TEA = 1:2:2 to ensure complete activation of hydroxyl groups.\n- Monitor reaction progress using thin-layer chromatography (TLC) or FTIR spectroscopy (look for the formation of ester bonds by observing C=O stretching at ~1720 cm⁻¹).\n\n---\n\n#### **Step 2: Copolymerization of Tween 20**\nOnce Tween 20 is functionalized, it can be grafted onto a hydrophilic polymer matrix, such as poly(acrylamide) or poly(acrylic acid), by free radical polymerization.\n\n**Reaction:**\nCopolymerization of acrylate-functionalized Tween 20 with acrylamide or acrylic acid.\n\n- **Reagents**: Acrylate-functionalized Tween 20, acrylamide or acrylic acid, initiator (e.g., potassium persulfate (KPS)), crosslinker (N,N'-methylenebisacrylamide).\n- **Solvent**: Water or a water/ethanol mixture.\n- **Reaction Conditions**:\n  - Prepare an aqueous solution of acrylamide, functionalized Tween 20, and the crosslinker.\n  - Add KPS as a radical initiator and gently heat the solution to 40–60°C.\n  - Stir under nitrogen atmosphere or vacuum to remove oxygen, which inhibits polymerization.\n  - Allow the reaction to proceed for 4–6 hours.\n\n**Key Parameters**:\n- Ratios:\n  - Functionalized Tween 20: acrylamide = 1:10–1:50 (optimize hydrophilicity without compromising the integrity of the polymer).\n  - Crosslinker ~1–2 mol% relative to monomer units.\n- Polymerization temperature: 40–60°C.\n\n**Outcome**:\nThe resulting polymer matrix incorporates Tween 20 as a hydrophilic segment, providing amphiphilic characteristics and enhanced water absorption.\n\n---\n\n#### **Step 3: Validation of the Hydrophilic Polymer**\nAfter polymer synthesis, the material’s hydrophilicity can be characterized through water contact angle measurements and swelling tests.\n\n- **Contact Angle**: Measure the contact angle of a water droplet on the polymer surface to determine hydrophilicity. Lower contact angles indicate higher hydrophilicity.\n- **Swelling Ratio**: Immerse polymer samples in water and calculate the swelling degree to evaluate water uptake.\n- **Spectroscopic Analysis**: Use FTIR to confirm the presence of Tween 20 in the matrix (polyoxyethylene stretching bands at ~1100 cm⁻¹) and ensure successful covalent bonding.\n\n---\n\n### **3. Summarizing Benefits of This Approach**\nBy functionalizing Tween 20 and incorporating it into a polymer matrix, the hydrophilicity is enhanced due to the increased density of hydrophilic groups (polyoxyethylene chains and hydroxyl groups) within the network. Additionally, covalent bonding ensures it remains stably integrated, unlike physical blending methods.\n\nIn the lab, following this scheme will allow precise control over the polymer composition, enabling better optimization for hydrophilic properties tailored to specific applications.\n\nIf you have further questions or need clarification on any step, feel free to ask!"
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+{
+  "design_question": "When using tetraethylorthosilicate (TEOS) in the experimental process, explain how its role affects the structure and hydrophilicity of the polymer material, and outline a step-by-step approach for incorporating it effectively.",
+  "design_answer": "Of course. Let’s analyze your question step by step and design a detailed experimental preparation scheme for incorporating tetraethylorthosilicate (TEOS) into a hydrophilic polymer to achieve enhanced hydrophilicity.\n\n---\n\n### **Analysis of the Question**\nThe key points in your question are:\n1. **Role of TEOS**: Understanding the chemical function of tetraethylorthosilicate (TEOS) in the polymer synthesis and how it influences the structure and hydrophilicity of the polymer.\n2. **Experimental Process for Incorporation**: A systematic approach to integrating TEOS into the polymer synthesis, with a focus on achieving improved hydrophilicity.\n3. **Reaction Details**: Consideration of reaction conditions, reagent ratios, and molar quantities to optimize the process.\n\nTo address these, we’ll first discuss the underlying principles and role of TEOS in enhancing polymer hydrophilicity, followed by a detailed, step-by-step synthesis procedure.\n\n---\n\n### **Role of TEOS in Polymer Materials**\nTEOS, a silicon-based alkoxide, is a precursor commonly used in sol-gel chemistry and hybrid organic-inorganic material synthesis. Its hydrolysis and condensation reactions produce polysiloxane or silica networks. TEOS contributes to hydrophilicity in two ways:\n1. **Silica Network Formation**: Hydrolysis of TEOS in the presence of water generates silanol (–Si–OH) groups. These hydroxyl groups are intrinsically hydrophilic and can form hydrogen bonds with water. As a result, incorporating TEOS into a polymer matrix increases the density of hydrophilic sites.\n2. **Crosslinking and Hybrid Structures**: TEOS can form covalent or physical interactions with organic polymer chains, creating a hybrid material with enhanced mechanical properties while retaining high hydrophilicity due to the silica’s surface chemistry.\n\nThus, TEOS essentially serves as a hydrophilic crosslinking agent and a structural modifier for the polymer material.\n\n---\n\n### **Step-by-Step Experimental Process**\n\nBelow is a comprehensive experimental preparation scheme for synthesizing a TEOS-modified hydrophilic polymer:\n\n---\n\n#### **Step 1: Materials Preparation**\n**Chemicals Required:**\n1. Tetraethylorthosilicate (TEOS) – the precursor for silica formation.\n2. Precursor polymer – select a hydrophilic monomer such as poly(ethylene glycol) (PEG), poly(vinyl alcohol) (PVA), or poly(acrylamide) (PAM).\n3. Deionized water – for hydrolysis of TEOS.\n4. Ethanol – as a solvent for TEOS to improve miscibility.\n5. Catalysts:\n   - Acidic catalyst (e.g., HCl) for hydrolysis.\n   - Basic catalyst (e.g., NH₄OH) for condensation.\n6. Crosslinker (optional) – such as glutaraldehyde if additional network formation is required.\n\n---\n\n#### **Step 2: Hydrolysis of TEOS**\n1. **Reaction Setup**:\n   - Mix TEOS and ethanol in a molar ratio of 1:5 (TEOS:Ethanol) in a stirred beaker or reaction flask.\n   - Gradually add the catalyst (acidic, typically dilute HCl) dropwise into the solution. \n   - Use deionized water at a molar ratio of 1:4 (TEOS:H₂O) to ensure effective hydrolysis.\n\n2. **Conditions**:\n   - Maintain constant stirring at room temperature (20–25°C) for 2–4 hours to fully hydrolyze TEOS into silanol intermediates (Si–(OH)₄).\n\n3. **Mechanism**:\n   - Hydrolysis reaction (acidic conditions):\n     \\[\n     Si(OC₂H₅)₄ + 4H₂O \\xrightarrow{\\text{HCl}} Si(OH)₄ + 4C₂H₅OH\n     \\]\n   - This step replaces ethoxy groups with hydroxyl groups, making the system hydrophilic.\n\n---\n\n#### **Step 3: Condensation and Polymer Matrix Incorporation**\n1. **Mixing with Polymer Precursor**:\n   - In a separate vessel, prepare the polymer precursor solution (e.g., dissolve PEG, PVA, or PAM in deionized water or ethanol). The polymer-to-TEOS ratio should be approximately 1:1–1:2 (w/w).\n   - Combine the hydrolyzed TEOS solution with the polymer precursor under stirring to ensure homogeneous mixing.\n\n2. **Condensation Reaction**:\n   - Add a basic catalyst (e.g., NH₄OH) dropwise to initiate the condensation of silanol groups.\n   - Reaction conditions: temperature 40–60°C, constant stirring for 4–6 hours.\n   - Condensation reaction:\n     \\[\n     Si(OH)₄ + Si(OH)₄ \\xrightarrow{\\text{NH₄OH}} Si–O–Si + 2H₂O\n     \\]\n\n3. **Hybrid Formation**:\n   - Silica particles or crosslinked silica structures form in situ within the polymer matrix, physically or chemically linking to polymer chains.\n   - These silica regions provide enhanced hydrophilicity due to their surface hydroxyl groups.\n\n---\n\n#### **Step 4: Gelation and Curing**\n1. Transfer the mixture into molds or appropriate substrates if forming a specific polymer shape is required.\n2. Cure the sample by heating at 60–80°C for 6–12 hours to solidify the polymer network and promote complete condensation.\n\n---\n\n#### **Step 5: Post-Treatment and Washing**\n1. Wash the cured material with deionized water and ethanol to remove unreacted precursors, ethanol byproducts, and weakly bonded silica particles.\n2. Dry the sample in a vacuum oven at 50–60°C until a constant weight is achieved.\n\n---\n\n### **Key Notes on Reaction Ratios and Optimization**\n1. **TEOS-to-polymer ratio**: A higher TEOS ratio increases hydrophilicity but could compromise flexibility. Experiment with ratios like 1:1 or 1:2 for optimization.\n2. **Catalyst Concentration**: Acidic or basic catalyst concentration should be optimized to ensure controlled hydrolysis and condensation without excessive gelation.\n3. **Hydrolysis Time**: Ensure TEOS is fully hydrolyzed before proceeding to prevent poor silica distribution within the polymer matrix.\n\n---\n\n### **Additional Remarks**\n- To further enhance hydrophilicity, you may consider incorporating other co-monomers, such as acrylic acid or hydrophilic functional groups, into the polymer matrix during synthesis.\n- TEOS-modified hydrophilic polymers are ideal for applications like hydrogels, membranes, and biomedical coatings.\n\n---\n\nBy following this systematic synthesis approach, you should be able to successfully incorporate TEOS into your polymer to increase hydrophilicity while maintaining a robust material structure. Let me know if you have further questions!"
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diff --git a/task2/task2-qa/fuctional polymer.json b/task2/task2-qa/fuctional polymer.json
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+{
+  "design_question": "How would you incorporate poly(ethoxylate-b-caprolactone) monomethacrylate oligomer as a functionalizing agent to create a hydrophilic polymer? Describe the step-by-step process and the expected structural changes to the polymer backbone.",
+  "design_answer": "Certainly! Let us break down your question systematically and design a detailed experimental preparation scheme for incorporating **poly(ethoxylate-b-caprolactone) monomethacrylate oligomer** as a functionalizing agent to synthesize a hydrophilic polymer. This step-by-step process also includes the expected structural changes to the polymer backbone.\n\n---\n\n### **Key Points of the Question:**\n\n1. **Objective:** Functionalize a polymer to enhance its hydrophilicity.\n2. **Given Functionalizing Agent:** The provided molecule is **poly(ethoxylate-b-caprolactone) monomethacrylate oligomer**. This is a block oligomer with hydrophilic ethoxylate (EO) segments, hydrophobic caprolactone (CL) moieties, and a reactive methacrylate group at one terminus.\n3. **Strategy:** Use the methacrylate group for **radical copolymerization** to integrate the oligomer into the polymer backbone.\n4. **Functionalization Target:** Generate a hydrophilic polymer backbone containing poly(ethoxylate-b-caprolactone) side chains to improve hydrophilicity and potentially tune amphiphilicity.\n\n---\n\n### **Step-by-Step Experimental Synthesis:**\n\n#### **Step 1: Selection of the Polymer Backbone**\nTo incorporate **poly(ethoxylate-b-caprolactone) monomethacrylate (PEG-b-PCL)** into a hydrophilic polymer, we need to copolymerize it with a compatible monomer through radical polymerization. Suitable hydrophilic monomers include:\n   - Acrylic acid (AA)\n   - Hydroxyethyl methacrylate (HEMA)\n   - N-vinylpyrrolidone (NVP)\n\nFor this synthesis, let's use **acrylic acid (AA)** as the primary monomer due to its strong hydrophilic nature and ability to form carboxylic functionalities in the resulting polymer.\n\n---\n\n#### **Step 2: Reaction Scheme Overview**\nThe process involves **free-radical copolymerization** of:\n   - Acrylic acid **(AA)** (hydrophilic base monomer).\n   - **Poly(ethoxylate-b-caprolactone) monomethacrylate (PEG-b-PCL)** oligomer (the functionalizing monomer).\n\nThe polarized methacrylate group in PEG-b-PCL enables its copolymerization with acrylic acid, while the ethoxylate and caprolactone blocks become part of the hydrophilic side chains.\n\n---\n\n#### **Step 3: Materials Required**\n1. **Monomers**:\n   - Acrylic acid (AA) - Base hydrophilic monomer.\n   - Poly(ethoxylate-b-caprolactone) monomethacrylate (PEG-b-PCL) - Functionalizing agent.\n2. **Initiator**:\n   - Azobisisobutyronitrile (**AIBN**), a commonly used radical initiator.\n3. **Solvent**:\n   - Anhydrous dioxane or dimethylformamide (DMF), which can dissolve both AA and PEG-b-PCL.\n4. **Chain Transfer Agent (Optional)**:\n   - Mercaptoethanol or dodecanethiol to control molecular weight.\n\n---\n\n#### **Step 4: Reaction Procedure**\n##### **Step 4.1: Preparation of the Reaction Mixture**\n1. **Calculate reagent quantities:**\n   - **Acrylic acid (AA)**: Determine the required molar amount (e.g., target MW: ~50,000 g/mol). Commonly, ratios of AA:PEG-b-PCL around **90:10 (molar)** provide good hydrophilicity.\n   - **PEG-b-PCL oligomer**: Measure a known mass based on its molecular weight (typically 2–5 kDa) and desired feed ratio.\n   - **Initiator (AIBN)**: Use ~1–2% molar of the total monomer concentration.\n   - **Solvent**: Add solvent (dioxane/DMF) to achieve 20–30 wt% monomer concentration for proper polymerization control.\n\n2. Add AA and PEG-b-PCL together in a clean, dry round-bottom flask containing the solvent. Ensure homogeneous dissolution (stirring, mild heating if needed).\n\n3. Add the AIBN initiator last to the monomer mixture under inert gas (nitrogen or argon flow) to prevent premature radical formation.\n\n##### **Step 4.2: Purge the System with Inert Gas**\n4. Degas the mixture by bubbling nitrogen/argon gas for ~30 minutes to eliminate dissolved oxygen, as free radicals are susceptible to oxygen quenching.\n\n##### **Step 4.3: Radical Polymerization**\n5. Place the reaction flask in an oil bath or a heating block and maintain the temperature at **60–70°C** for ~4–6 hours under constant stirring. The elevated temperature triggers the dissociation of AIBN, generating radicals for polymerization.\n\n6. During the copolymerization, the methacrylate group on PEG-b-PCL reacts with the double bond in AA, incorporating the PEG-b-PCL units into the polymer backbone with ethoxylate and caprolactone blocks forming the **hydrophilic pendant groups**.\n\n---\n\n#### **Step 5: Purification of the Polymer**\n1. After the reaction is complete, cool the mixture to room temperature and precipitate the polymer by adding the reaction mixture dropwise into a large volume of non-solvent (e.g., diethyl ether or ethanol).\n\n2. Filter and wash the precipitate with the non-solvent to remove unreacted monomers or oligomers.\n\n3. Dry the purified polymer under vacuum at 40–50°C until constant weight is achieved.\n\n---\n\n#### **Step 6: Characterization**\n1. **Fourier-transform infrared spectroscopy (FTIR):**\n   - To confirm the incorporation of PEG-b-PCL. Look for characteristic peaks of ethoxylate (-C-O-C-) and caprolactone groups.\n2. **Gel permeation chromatography (GPC):**\n   - To analyze molecular weight and distribution.\n3. **Contact angle measurement:**\n   - To evaluate the hydrophilicity of the resulting polymer.\n4. **Nuclear magnetic resonance (NMR):**\n   - To determine the composition and quantify the molar ratio of AA to PEG-b-PCL in the copolymer.\n\n---\n\n### **Expected Structural Changes**\n1. The methacrylate group of **PEG-b-PCL** copolymerizes with acrylic acid, integrating **PEG-b-PCL as hydrophilic pendant side chains** onto the polymer backbone.\n2. The resulting polymer has repeating units of acrylic acid and **side-chain blocks** of ethoxylate-caprolactone, which increase hydrophilicity due to:\n   - **Poly(ethoxylate) moieties** (highly hydrophilic and water-soluble).\n   - Moderate amphiphilicity from **poly(caprolactone)** units, which provide tunable hydrophobicity.\n\n---\n\n### **Conclusion**\nThe described free-radical copolymerization process effectively integrates **poly(ethoxylate-b-caprolactone) monomethacrylate oligomer** into a hydrophilic polymer backbone. By controlling the feed ratio and reaction conditions, the resulting polymer will exhibit enhanced hydrophilicity due to the ethoxylate groups, with potential amphiphilic behavior from the caprolactone moieties.\n\nThis step-by-step process should enable you to perform the experiment successfully in the lab! Let me know if you need further clarification."
+}
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diff --git a/task2/task2-qa/functionalized polymer.json b/task2/task2-qa/functionalized polymer.json
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+{
+  "design_question": "Methacrylic acid is used in the preparation of hydrophilic polymers. How would the carboxylic acid groups in methacrylic acid contribute to the hydrophilic nature of the final polymer, and what strategies can you use to ensure proper polymerization and uniform incorporation of this monomer into the polymer structure?",
+  "design_answer": "Certainly. Let’s analyze your question systematically and develop a detailed experimental preparation scheme for hydrophilic polymers based on methacrylic acid as a monomer.\n\n### **Analysis and Summarization**\nYour question involves:\n1. Understanding how the carboxylic acid groups in methacrylic acid contribute to the hydrophilicity of the final polymer.\n2. Strategies to ensure the proper polymerization and uniform incorporation of methacrylic acid into the polymer structure.\n\nThis requires a detailed explanation of the polymerization mechanism involving methacrylic acid and the optimization of experimental conditions to achieve an evenly distributed hydrophilic polymer.\n\n---\n\n### **Detailed Answer**\n\n#### **Step 1: Contribution of Carboxylic Acid Groups to Hydrophilicity**\nMethacrylic acid (MAA) contains a functional carboxylic acid group (-COOH), which plays a pivotal role in enhancing the hydrophilic nature of the polymer. The -COOH group:\n- **Hydrogen Bonding:** Can form strong hydrogen bonds with water molecules, increasing affinity for water.\n- **Ionization in Aqueous Media:** In slightly alkaline or neutral conditions, carboxylic acid groups can ionize to carboxylate anions (-COO⁻), further improving water solubility and hydrophilicity.\n- **Functional Site for Further Modification:** Carboxylic acid groups can serve as anchor points for additional functionalization (e.g., grafting hydrophilic chains or biomolecules).\n\nIn a polymer structure, the presence of the -COOH group ensures that the resulting polymer has strong hydrophilic domains suitable for applications like biomaterials, water purification, or responsive hydrogels.\n\n---\n\n#### **Step 2: Strategies for Polymerization and Incorporation**\nTo ensure proper polymerization and uniform incorporation of MAA into the polymer structure, an optimized approach is required. Below is a step-by-step experimental preparation scheme:\n\n---\n\n### **Experimental Preparation Scheme**\n\n#### **Materials and Reagents**\n1. **Monomers:**\n   - Methacrylic acid (MAA): Primary hydrophilic monomer.\n   - Hydrophobic or neutral co-monomer (e.g., methyl methacrylate or acrylamide) for tuning hydrophilicity, if desired.\n2. **Initiator:**\n   - Azobisisobutyronitrile (AIBN) (for free radical polymerization) or potassium persulfate (KPS), depending on the polymerization method.\n3. **Solvent:**\n   - Water or polar solvent (e.g., ethanol-water mixture) to ensure the dissolution of methacrylic acid and enable hydrophilic interaction during polymerization.\n4. **Crosslinker (optional):**\n   - Bisacrylamide, if a crosslinked polymer/hydrogel is desired.\n5. **pH Modifiers:**\n   - Sodium hydroxide or ammonium hydroxide to adjust the pH and ionize carboxyl groups for increased hydrophilicity.\n\n---\n\n#### **Step 1: Monomer Selection and Composition**\n1. Decide the ratio of methacrylic acid to the co-monomer (if present) based on the desired hydrophilicity. A typical ratio could be:\n   - Pure MAA polymer (100% monomer).\n   - Copolymer with 70% MAA and 30% methyl methacrylate (MMM) or acrylamide.\n\n#### **Step 2: Solvent Preparation**\n1. Prepare an ethanol-water solution (50:50) to dissolve MAA. This solvent reduces viscosity and stabilizes radicals during polymerization.\n2. Adjust pH to ~7 using a weak base (e.g., NaOH) if carboxylic groups are to be ionized for enhanced hydrophilicity.\n\n#### **Step 3: Initiator Selection**\n1. Dissolve AIBN (0.5 mol% relative to total monomer content) in the solvent. Alternatively, if using potassium persulfate (KPS), dissolve in a dilute aqueous solution at 60°C.\n\n#### **Step 4: Reaction Parameters**\nEstablish favorable reaction conditions for radical polymerization:\n1. **Temperature:** Polymerization occurs at ~60–80°C. Heating provides the activation energy necessary for initiator decomposition.\n2. **Duration:** Allow polymerization for 2–6 hours under a nitrogen or inert gas blanket to prevent oxygen inhibition.\n\n#### **Step 5: Start Polymerization**\n1. Combine MAA monomer and co-monomer in the solvent.\n2. Add initiator solution (AIBN or KPS) to the reaction vessel.\n3. Maintain stirring at 200–400 RPM to ensure uniform mixing and consistency in polymer composition.\n\n#### **Step 6: Control Molecular Architecture**\n1. To ensure uniform incorporation, maintain a constant feed of monomer and initiator. A semi-batch approach can avoid the early depletion of MAA, ensuring consistency in polymer composition.\n2. Adjust crosslinker concentration (0–0.1 mol%) if you’re creating a hydrogel.\n\n#### **Step 7: Quenching Polymerization**\nOnce polymerization is complete, cool the reaction mixture to room temperature. Deactivate radicals by purging excess initiator with butanol or ethanol.\n\n---\n\n### **Step 3: Purification of Hydrophilic Polymer**\n1. Precipitate the polymer by adding the reaction mixture into chilled non-solvent, such as acetone or diethyl ether.\n2. Wash the polymer several times with water and ethanol to remove unreacted monomers and initiators.\n3. Dry at 50°C under vacuum until obtaining a solid polymer.\n\n---\n\n### **Step 4: Characterization**\n1. Perform Fourier-transform infrared spectroscopy (FTIR) to confirm the presence of carboxylic acid (-COOH) functional groups.\n2. Measure hydrophilicity via water contact angle or swelling studies (for hydrogels).\n\n---\n\n### **Conclusion**\nFollowing the above strategy, methacrylic acid can be effectively polymerized into hydrophilic polymers with uniform distribution of carboxylic acid groups. By optimizing monomer ratios, reaction conditions, and purification steps, you can ensure high-quality hydrophilic polymers suitable for diverse applications. If further functionality is required, post-polymerization modifications can be explored.\n\n"
+}
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diff --git a/task2/task2-qa/gui2020.json b/task2/task2-qa/gui2020.json
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+{
+  "design_question": "Design a step-by-step procedure to immobilize DNA onto the polymer surface, ensuring that the modification increases the hydrophilic characteristics of the polymer.",
+  "design_answer": "Certainly, immobilizing DNA onto a polymer surface is an excellent method to enhance the polymer's hydrophilicity due to DNA's inherent hydrophilic properties arising from its sugar-phosphate backbone. Let’s tackle this systematically and design a robust experimental procedure for this modification.\n\n### Step 1: Analyze the Question\nThe goal is to immobilize DNA onto a polymer surface to enhance the polymer's hydrophilicity. To achieve this:\n- The polymer surface must be activated or functionalized to offer reactive sites for DNA immobilization.\n- DNA immobilization should be done under conditions that preserve its structural and functional integrity.\n- Select a coupling chemistry suitable for covalent attachment to ensure stable immobilization of DNA on the polymer.\n\n### Step 2: Experimental Preparation Scheme\nBelow is a detailed step-by-step procedure to modify the polymer and immobilize DNA:\n\n---\n\n#### **Step 1: Surface Activation (Introduce Reactive Functional Groups)**\nTo immobilize DNA, the polymer surface (e.g., a hydrophobic polymer like polyethylene or a partially hydrophilic polymer like polyacrylamide) needs to be activated. One common method is oxidation or functionalization with specific groups like -COOH, -NH2, or -OH that can react with DNA.\n\n1. **Clean the Polymer Surface:**\n   - Wash the polymer surface with ethanol and distilled water thoroughly to remove any impurities or residues.\n   - Dry the polymer with nitrogen gas.\n\n2. **Introduce Carboxyl Groups (if not already present):**\n   If the polymer is inert or hydrophobic (e.g., polyethylene, polystyrene), oxidative methods like plasma treatment or chemical oxidation can be used:\n   - **Plasma Treatment:** Expose the polymer to oxygen plasma to introduce surface carboxyl and hydroxyl groups.\n     - Conditions: Oxygen plasma, 200 W, 10 minutes, room temperature.\n   - Alternatively, use potassium permanganate or a chromic acid solution to oxidize the polymer surface:\n     - **Chromic Acid:** Immerse the polymer in an aqueous solution containing 10% w/v sodium dichromate and 1M sulfuric acid. Incubate at 60 °C for 1 hour.\n     - After oxidation, rinse with copious amounts of deionized water to remove residual chemicals.\n\n---\n\n#### **Step 2: Crosslinker Coupling for DNA Immobilization**\nFunctionalizing the surface with a crosslinker ensures effective binding between the polymer and DNA. One effective choice for DNA immobilization is the use of carbodiimide chemistry (e.g., EDC/NHS coupling) to attach the DNA via its amine or phosphate groups.\n\n1. **Activation of Carboxyl Groups:**\n   - Prepare a fresh solution of EDC (1-ethyl-3-(3-dimethylaminopropyl) carbodiimide) and NHS (N-hydroxysuccinimide).\n     - Dissolve 0.1 M EDC and 0.05 M NHS in a buffer solution at a pH of 5.5 (e.g., MES buffer).\n   - Immerse the polymer surface in the EDC-NHS solution and incubate for 2 hours at room temperature under mild agitation.\n   - This step activates the carboxyl groups on the polymer, creating reactive esters that can covalently bind amino groups in DNA.\n\n2. **DNA Solution Preparation:**\n   - Dissolve the DNA (single-stranded or double-stranded, depending on your application) in phosphate-buffered saline (PBS) at a concentration of 50–100 µM.\n   - Ensure the DNA is free from contaminants like salts or organic solvents; purify if necessary.\n\n3. **Covalent Coupling of DNA:**\n   - Add the DNA solution onto the EDC/NHS-activated polymer surface.\n   - Incubate at room temperature for 4–6 hours or at 4 °C overnight to allow efficient binding.\n   - During this step, the amino group in DNA (e.g., from nucleobases or chemically modified DNA with terminal -NH2 groups) reacts with the ester group on the polymer surface, forming a stable amide bond.\n\n---\n\n#### **Step 3: Post-Immobilization Washing and Confirmation**\nAfter coupling, unbound DNA and reagents must be removed, and the degree of DNA modification needs to be verified.\n\n1. **Washing:**\n   - Wash the polymer surface thoroughly with PBS buffer to remove unreacted DNA and any residual EDC/NHS.\n   - Perform additional washing with deionized water to ensure the removal of salts.\n\n2. **Blocking Remaining Active Sites:**\n   - To avoid nonspecific interactions, block any unreacted carboxyl groups on the polymer surface by treating with 1M ethanolamine (pH 8.0) for 30 minutes.\n   - Wash again with PBS buffer.\n\n3. **Characterization:**\n   - Confirm DNA immobilization using techniques like:\n     - UV-Vis spectroscopy to measure DNA absorbance at 260 nm on the surface.\n     - X-ray photoelectron spectroscopy (XPS) or Fourier-transform infrared spectroscopy (FTIR) to detect characteristic phosphate or amide bond peaks.\n     - Contact angle measurements to confirm increased hydrophilicity (a decrease in water contact angle indicates successful surface modification and enhanced hydrophilicity).\n\n---\n\n### Summary of Key Reaction Conditions and Reagent Ratios:\n- **Surface Oxidation (if needed):** Chromic acid treatment or oxygen plasma.\n- **Carbodiimide Coupling:** 0.1 M EDC, 0.05 M NHS in MES buffer (pH 5.5).\n- **DNA Concentration:** 50–100 µM in PBS buffer.\n- **Reaction Time:** 4–6 hours at room temperature or overnight at 4 °C.\n- **Blocking Agent:** 1M ethanolamine (pH 8.0).\n\nThis detailed and systematic scheme should enable the successful immobilization of DNA onto your polymer surface, significantly enhancing its hydrophilicity. Feel free to consult me for further clarifications or scaling adjustments for your specific setup."
+}
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diff --git a/task2/task2-qa/lee2013.json b/task2/task2-qa/lee2013.json
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+{
+  "design_question": "When using poly(ethylene glycol) (PEG) as a functionalizing molecule to enhance the hydrophilicity of a polymer, what steps would you take to ensure proper attachment onto the polymer matrix? Outline and justify each step in the process.",
+  "design_answer": "Certainly. Let us approach this question systematically to ensure your understanding, while providing a detailed, step-by-step outline of the synthesis process for functionalizing a polymer with a hydrophilic poly(ethylene glycol) (PEG) molecule.\n\n---\n\n### Key Points in the Problem\n\n1. **Objective**: Enhance the hydrophilicity of a polymer by attaching poly(ethylene glycol) (PEG) onto its matrix.\n2. **Challenges**: \n   - Ensuring proper chemical attachment of PEG to the polymer.\n   - Maintaining control over reaction conditions to achieve efficient grafting.\n   - Preserving the hydrophilic properties of PEG during the functionalization process.\n\n---\n\n### Step-by-Step Synthesis Process Using Poly(ethylene glycol) (PEG)\n\nBelow is a detailed plan of action to attach PEG molecules onto a polymer matrix, including comments on each step to ensure scientific rigor.\n\n---\n\n#### **Step 1: Analyze the Polymer Matrix**\n   - **Purpose**: Understanding the functional groups present on the polymer's surface determines the appropriate strategy for PEG attachment.\n   - **Actions**:\n     - Assess the chemistry of the polymer matrix (e.g., backbone functionality, surface reactivity). For instance:\n       - If the polymer contains hydroxyl (-OH), carboxylic acid (-COOH), or amine (-NH2) groups, these can serve as reactive handles for PEG attachment.\n       - If the polymer lacks such functional groups, surface modification (e.g., plasma treatment or chemical activation) may be required to introduce reactive sites.\n     - Determine whether you are grafting PEG along the polymer backbone (grafting-to method) or onto a pre-activated polymer chain end (grafting-from method).\n\n---\n\n#### **Step 2: Choose the Appropriate PEG Derivative**\n   - **Purpose**: Unmodified PEG is inert in most reactions, so a functionalized PEG derivative is required for efficient covalent bonding onto the polymer.\n   - **Actions**:\n     - Select a PEG derivative based on the polymer surface functionality:\n       - For coupling with -COOH (e.g., in poly(acrylic acid)): Use a PEG containing an amine (-NH2) or hydroxyl (-OH) group.\n       - For coupling with -OH, consider PEG terminated with a carboxylic acid or isocyanate (-N=C=O) functional group.\n       - For a more versatile approach, methoxy-PEG-succinimidyl carbonate (mPEG-SC) or PEG-diisocyanate can facilitate covalent attachment through reactive activated ends.\n     - Choose an appropriate molecular weight (common PEG molecular weights range from 200 to 20,000 Da) to balance hydrophilicity and polymer flexibility. Lower molecular weight provides better penetration into the matrix but less bulk hydrophilicity, while higher molecular weight PEG enhances hydration but reduces polymer mobility.\n\n---\n\n#### **Step 3: Surface Activation of the Polymer Matrix**\n   - **Purpose**: Enhance the polymer reactivity toward PEG.\n   - **Actions**:\n     - If the polymer lacks reactive functional groups, activate its surface by:\n       1. **Plasma Treatment**: Employ oxygen or ammonia plasma to introduce reactive oxygen-containing groups (e.g., -OH, -COOH) or amines (-NH2).\n       2. **Chemical Activation**: Use mild oxidation (e.g., sodium periodate for polysaccharides) or graft reactive monomers onto the polymer backbone.\n     - If reactive groups already exist on the polymer (e.g., -COOH on poly(acrylic acid)), proceed directly to coupling chemistry.\n\n---\n\n#### **Step 4: Reaction Setup for PEG Grafting**\n   - **Purpose**: Covalently attach PEG to the polymer matrix.\n   - **Reaction Pathways**:\n     1. **Amide Bond Formation** (if polymer possesses -COOH groups):\n        - **Chemistry**: React carboxylic acid groups on the polymer with amine-terminated PEG.\n        - **Activation**: Activate the -COOH groups with a coupling reagent like carbodiimides (e.g., EDC, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide) along with NHS (N-hydroxysuccinimide) to form a stable ester intermediate.\n        - **Conditions**:\n          - Solvent: Use a water-miscible solvent (e.g., DMF, DMSO, or PBS buffer, pH ~7).\n          - Molar ratio: Maintain a 1:1.1 molar ratio of polymer -COOH groups to PEG amine groups.\n          - Temperature: Perform reaction at room temperature (~25°C) or slightly elevated (e.g., 37°C) for 4–12 hours.\n        - **Expected Outcome**: Amide bonds form, covalently attaching the PEG molecule to the polymer matrix.\n     2. **Urethane Bond Formation** (if polymer possesses -OH groups):\n        - **Chemistry**: Isocyanate-terminated PEG reacts with hydroxyl groups on the polymer.\n        - **Conditions**:\n          - Solvent: Use an anhydrous solvent (e.g., tetrahydrofuran or DMF) to prevent isocyanate hydrolysis.\n          - Catalyst: Include dibutyltin dilaurate (DBTDL) as a catalyst to accelerate reaction kinetics.\n          - Temperature: Reaction should occur at 50–70°C under inert atmosphere (e.g., nitrogen) for 6–8 hours.\n        - **Expected Outcome**: Urethane linkages form, binding PEG to the polymer.\n\n---\n\n#### **Step 5: Purification of the Functionalized Polymer**\n   - **Purpose**: Remove unreacted reagents and excess PEG.\n   - **Actions**:\n     - Perform extensive washing of the polymer using water, ethanol, or suitable solvents to remove unreacted PEG and byproducts.\n     - Dialysis (if in solution) or Soxhlet extraction (if solid polymer) may also be employed for purification.\n     - Dry under vacuum to remove residual solvents and stabilize the polymer.\n\n---\n\n#### **Step 6: Characterization of the Modified Polymer**\n   - **Purpose**: Confirm the success of PEG grafting and measure the degree of hydrophilicity.\n   - **Analytical Techniques**:\n     1. **Fourier Transform Infrared Spectroscopy (FTIR)**:\n        - Observe characteristic peaks for PEG (C–O–C stretching near 1100 cm⁻¹) and newly formed functional groups (amide or urethane).\n     2. **Nuclear Magnetic Resonance (NMR)**:\n        - Use 1H NMR to detect PEG protons (chemical shifts around 3.4–3.7 ppm correspond to the ethylene oxide units in PEG).\n     3. **Contact Angle Measurements**:\n        - Measure the water contact angle to evaluate the improved hydrophilicity.\n     4. **Gravimetric Analysis**:\n        - Determine the degree of PEG grafting by comparing the polymer mass before and after functionalization.\n\n---\n\n### Justification of the Process\n\n1. **Surface Modification**: Ensures availability of reactive sites for PEG attachment, even for inert polymers.\n2. **Choice of Chemistry**: Selecting specific reagents and reaction conditions ensures high grafting efficiency with minimal PEG degradation.\n3. **Control of Reaction Parameters**: Optimizing molar ratios and temperature helps achieve reproducible results.\n4. **Characterization**: Essential to verify successful functionalization and quantify hydrophilicity improvements.\n\n---\n\nBy following the above systematic approach, you should be able to successfully graft PEG onto your polymer matrix and significantly enhance its hydrophilicity. Let me know if you need further clarification or assistance!"
+}
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diff --git a/task2/task2-qa/li-et-al-2017-amphiphilic-antifogging-anti-icing-coatings-containing-poss-pdmaema-b-psbma.json b/task2/task2-qa/li-et-al-2017-amphiphilic-antifogging-anti-icing-coatings-containing-poss-pdmaema-b-psbma.json
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+{
+  "design_question": "If you were to use POSS-Br in an ATRP-based reaction, how would you control the polymerization to achieve the desired balance between hydrophilic and hydrophobic properties in the resulting polymer? Include any factors you would consider in your design.",
+  "design_answer": "To design an ATRP (Atom Transfer Radical Polymerization) reaction using POSS-Br (Polyhedral Oligomeric Silsesquioxane functionalized with bromine) as an initiator, the goal is to control the polymerization such that the resulting polymer achieves an optimized balance between hydrophilic and hydrophobic properties. Below, I will analyze your question systematically and provide a comprehensive experimental preparation scheme.\n\n---\n\n### **Step 1: Analyze the Question**\nThe key points to consider in this synthesis are:\n1. **Use of POSS-Br as the initiating site**: POSS is inherently hydrophobic due to its silicon-oxygen cage structure, but the functionalization with bromine allows POSS to act as an ATRP initiator. This combination of hydrophobic POSS with compatible hydrophilic polymer chains can lead to a balanced amphiphilic polymer matrix.\n2. **Control of the polymerization conditions**: ATRP provides excellent control over molecular weight and chain architecture, which is critical for achieving the desired balance of hydrophobic and hydrophilic properties.\n3. **Selection of monomers**: By incorporating specific hydrophilic and hydrophobic monomers, the hydrophilicity/hydrophobicity of the resulting polymer can be tuned.\n4. **Reaction conditions**: Factors such as the catalyst, solvent, temperature, monomer ratios, and reaction time need optimization for balanced polymer characteristics.\n\n---\n\n### **Step 2: Systematic Preparation Scheme Using POSS-Br**\nThe following outlines all steps of the experimental design:\n\n---\n\n#### **Step 2.1: Materials Required**\n**Reagents:**\n1. POSS-Br as ATRP initiator.\n2. Hydrophilic monomers (e.g., poly(ethylene glycol) methyl ether methacrylate (PEGMA), 2-hydroxyethyl methacrylate (HEMA)).\n3. Optionally, hydrophobic monomers (e.g., styrene or methyl methacrylate (MMA)).\n4. Catalyst system (e.g., Cu(I) halide and ligand such as N,N,N',N\",N\"-pentamethyldiethylenetriamine (PMDETA) or bipyridine).\n5. Solvent (e.g., anisole, DMF, or toluene).\n6. Reducing agent (e.g., Cu(0) powder if an activator regeneration process is used).\n7. Purification agents (e.g., methanol or water for precipitation; activated carbon for copper removal).\n\n**Equipment:**\n- Schlenk flask or inert-atmosphere glovebox for oxygen-free conditions.\n- Magnetic stirrer, oil bath/heating mantle.\n- NMR spectrometer for monomer conversion tracking.\n- Gel permeation chromatography (GPC) for molecular weight analysis.\n\n---\n\n#### **Step 2.2: Reaction Design**\n1. **Initiator Setup**:\n   - POSS-Br serves as the bromine-functional initiator for ATRP, which actively supports controlled polymer growth. The hydrophobic POSS structure will remain central and will anchor grafted polymer chains.\n\n2. **Monomer Selection**:\n   - Hydrophilic monomers such as PEGMA or HEMA are incorporated to enhance hydrophilicity.\n   - Adding a hydrophobic monomer like MMA or styrene in varying ratios enables fine control over the polymer's amphiphilicity.\n   - The ratio between hydrophilic and hydrophobic monomers should be adjusted depending on the desired property. A typical range could be 70:30 (hydrophilic to hydrophobic).\n\n3. **Catalyst and Ligand**:\n   - Use Cu(I) halide (e.g., CuCl or CuBr) as the catalyst.\n   - Typically, a ligand like PMDETA or bipyridine is chosen to stabilize the Cu(I) species.\n   - Maintain a typical catalyst-to-initiator molar ratio of 1:1.\n\n4. **Solvent**:\n   - Solvent polarity affects polymerization. Use anisole or DMF for hydrophilic monomers.\n   - For better control, solvent must dissolve POSS-Br, and facilitate the solubility of Cu catalyst and ligand.\n\n5. **Reaction Temperature**:\n   - Control the reaction temperature between 50–90 °C, as higher temperatures generally speed up the polymerization but may reduce control over molecular weight and dispersity.\n\n---\n\n#### **Step 2.3: Experimental Procedure**\n1. **Prepare Reaction Mixture**:\n   - In a Schlenk flask under nitrogen atmosphere or vacuum, add POSS-Br (initiator), Cu(I) halide (catalyst), ligand, and selected monomers (hydrophilic and hydrophobic).\n   - Dilute the mixture with pre-cooled solvent (e.g., anisole or DMF).\n   - Add reducing agent (if necessary) to ensure activation of the catalyst.\n\n2. **Polymerization**:\n   - Begin polymerization at the controlled temperature (e.g., 70 °C).\n   - Monitor reaction progress by withdrawing aliquots periodically for NMR or GPC analysis.\n   - Depending on the degree of polymerization, the reaction typically runs for 6–24 hours.\n\n3. **End the Reaction**:\n   - To terminate the polymerization, expose the reaction mixture to air to deactivate the Cu species.\n   - Add an antioxidant (e.g., hydroquinone) if necessary to prevent side reactions.\n\n4. **Purification of Polymer**:\n   - Precipitate the polymer by adding the reaction mixture to a non-solvent (e.g., methanol or water).\n   - Recover polymer by filtration and dry under vacuum.\n   - If copper residuals are present, treat the polymer with activated carbon or use dialysis in aqueous solution.\n\n---\n\n#### **Step 2.4: Characterization**\n1. **Molecular Weight and Dispersity**:\n   - Use GPC analysis to confirm the molecular weight and dispersity (target dispersity = 1.1–1.3 for controlled AT).\n   - Ensure that the molecular weight falls within the range necessary for your intended application.\n\n2. **Hydrophilicity Assessment**:\n   - Measure the hydrophilicity/hydrophobicity via contact angle measurement or water absorption tests.\n\n3. **Structural Analysis**:\n   - Confirm the successful incorporation of hydrophilic/hydrophobic monomers by FTIR spectroscopy.\n\n---\n\n#### **Step 2.5: Factors to Optimize Balance Between Hydrophilic and Hydrophobic Properties**\n1. **Monomer Ratio**:\n   - Adjust hydrophilic-to-hydrophobic monomer ratio carefully. A higher percentage of PEGMA or HEMA will enhance hydrophilicity, while increasing MMA will boost hydrophobicity.\n\n2. **Chain Architecture**:\n   - Consider synthesizing block copolymers or graft polymers, as the arrangement of hydrophilic and hydrophobic segments affects overall properties.\n\n3. **Molecular Weight**:\n   - Higher molecular weights generally reduce the mobility of chains, which can affect surface properties.\n\n4. **End Group Functionalization**:\n   - Post-polymerization modification can be done to introduce ionic or polar groups at chain ends to further tune hydrophilicity.\n\n---\n\n### **Conclusion**\nUsing POSS-Br in an ATRP reaction provides excellent control over polymer architecture. By carefully selecting hydrophilic and hydrophobic monomers, optimizing reaction conditions, and tailoring molecular weight and structure, you can precisely control the amphiphilic balance in the resulting polymer. Follow these steps systematically, and ensure each parameter is adjusted based on experimental data for successful synthesis.\n\nIf you have more information (e.g., intended application or specific surface property requirements), I can further refine this scheme to optimize your outcome."
+}
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diff --git a/task2/task2-qa/liang-et-al-2019-transparent-and-scratch-resistant-antifogging-coatings-with-rapid-self-healing-capability.json b/task2/task2-qa/liang-et-al-2019-transparent-and-scratch-resistant-antifogging-coatings-with-rapid-self-healing-capability.json
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+{
+  "design_question": "Explain how silica nanoparticles can be functionalized using 1,3-propane sultone during a polymer modification experiment. What steps would you take to ensure this reaction is both effective and complete?",
+  "design_answer": "### Analyzing the Question:\n\nThe question involves the functionalization of silica nanoparticles using 1,3-propane sultone, particularly in the context of a polymer modification experiment. To address this question systematically:\n1. **Objective**: The goal is to functionalize silica nanoparticles to introduce new hydrophilic groups, likely to enhance the surface hydrophilicity of the silica while potentially enabling further polymer modifications (e.g., incorporation of hydrophilic polymers).\n2. **Reagent**: 1,3-propane sultone is a small organic molecule used to add sulfonic acid or sulfonate groups onto surfaces through a ring-opening reaction.\n3. **Challenges**: Ensuring uniform and complete functionalization of the silica nanoparticles requires optimizing the reaction conditions (e.g., solvent choice, reaction temperature, ratio of reagents) and proper characterization to confirm the success of the functionalization.\n4. **Key Points to Address**:\n   - Preparation of silica nanoparticles (if necessary).\n   - Surface preparation and activation of silica nanoparticles (e.g., hydroxylation or silanization if required).\n   - Detailed reaction protocol for functionalization using 1,3-propane sultone.\n   - Post-reaction workup and characterization procedures.\n\n---\n\n### Detailed and Systematic Steps:\n\n#### **Step 1: Preparation of Silica Nanoparticles**\nIf not obtained in a pre-functionalized form, silica nanoparticles should first be synthesized, e.g., via the Stöber process:\n1. **Reagents**: Tetraethyl orthosilicate (TEOS), ethanol, ammonia (catalyst), and deionized water.\n2. **Procedure**:\n   - Prepare a reaction mixture in ethanol containing ammonia as a catalyst.\n   - Slowly add TEOS dropwise to the mixture (e.g., molar ratio TEOS:ethanol:water:ammonia = 1:50:7:6).\n   - Stir vigorously at room temperature for 12–24 hours until uniform nanoparticles form.\n   - Centrifuge to collect the nanoparticles, wash with ethanol, and dry at 60 °C.\n3. **Key Conditions**: Control the size of nanoparticles by adjusting ammonia concentration and reaction time.\n\n#### **Step 2: Surface Activation of Silica Nanoparticles**\nTo ensure effective functionalization, the silica surface must have hydroxyl (-OH) groups for subsequent reactions with 1,3-propane sultone:\n1. **Hydroxylation (if required)**: \n   - Treat silica nanoparticles with a mixture of sodium hydroxide (0.1 M) and water at 80 °C for 2 hours.\n   - Wash thoroughly with deionized water to remove any residual base and dry under vacuum at 60 °C.\n   - **Note**: Silica typically already has -OH groups on the surface, particularly with freshly prepared silica nanoparticles.\n2. **Optional Silanization**: \n   - Alternatively, introduce amine groups onto the silica surface prior to the 1,3-propane sultone reaction.\n   - Aminosilane (e.g., 3-aminopropyltriethoxysilane, APTES) can be used, as these amine groups can nucleophilically attack 1,3-propane sultone in the subsequent step.\n   - Procedure:\n     - Disperse silica nanoparticles in toluene and add 5% (v/v) APTES.\n     - Heat under reflux for 4–6 hours.\n     - Wash particles with ethanol and dry at 60 °C.\n\n#### **Step 3: Functionalization with 1,3-Propane Sultone**\nThe ring-opening reaction between 1,3-propane sultone and surface hydroxyl (or amine) groups introduces sulfonic acid (-SO3H) groups, enhancing the hydrophilicity of the silica nanoparticles.\n1. **Reagents**:\n   - Activated silica nanoparticles with surface -OH or -NH2 groups.\n   - 1,3-Propane sultone (typically used in slight excess to ensure complete reaction).\n   - An anhydrous polar solvent such as toluene, DMF, or chloroform.\n2. **Procedure**:\n   - Disperse ~500 mg silica nanoparticles in 10 mL anhydrous toluene or DMF under an inert atmosphere (e.g., nitrogen or argon) to prevent moisture interference.\n   - Add 1,3-propane sultone dropwise to the dispersion, maintaining a molar ratio of at least 1.2:1 (propane sultone:surface hydroxyl or amine groups).\n   - Stir the mixture at 60–80 °C for 12 hours to allow complete ring-opening functionalization.\n   - Cool the reaction to room temperature and centrifuge the reaction mixture to separate the functionalized nanoparticles.\n   - Wash the nanoparticles with anhydrous solvents (e.g., ethanol or acetone) to remove unreacted species.\n   - Dry the functionalized nanoparticles under vacuum at 60 °C.\n\n---\n\n#### **Step 4: Post-Reaction Workup and Characterization**\nAfter functionalization, the success of the reaction must be confirmed using appropriate methods:\n1. **Washing**:\n   - Perform multiple washes with ethanol or water to ensure removal of unreacted starting materials or side products.\n   - Check for pH neutrality of the washing solvent to confirm complete removal of acidic or basic residuals.\n2. **Drying**:\n   - Dry under vacuum at 60 °C for 6–12 hours.\n3. **Characterization**:\n   - **FTIR**: Confirm the presence of -SO3H functionalities through characteristic bands in the IR spectrum (e.g., ~1200–1000 cm⁻¹ for -SO3 stretching vibration).\n   - **Thermogravimetric Analysis (TGA)**: Assess functional group loading by determining organic weight loss.\n   - **Zeta Potential or Contact Angle**: Measure surface hydrophilicity and charge characteristics.\n   - **Elemental Analysis (e.g., XPS)**: Confirm sulfur incorporation and quantify sulfonic acid groups.\n4. **Storage**: Store silica nanoparticles in a desiccator or inert atmosphere to prevent contamination or moisture absorption.\n\n---\n\n### Key Considerations for Effectiveness and Completeness:\n1. **Reaction Atmosphere**: Use an anhydrous solvent and inert atmosphere to avoid competitive side reactions involving moisture.\n2. **Excess 1,3-Propane Sultone**: Maintain a slight molar excess of 1,3-propane sultone to ensure high surface coverage of functional groups.\n3. **Reaction Duration and Temperature**: Ensure sufficiently high temperature and long enough reaction duration for complete surface functionalization while avoiding thermal decomposition.\n4. **Thorough Washing and Characterization**: Consistently wash the product and rigorously verify incorporation of sulfonic acid groups to confirm complete functionalization.\n5. **Monitoring Dispersion**: Maintain adequate dispersion of silica particles during reaction to avoid aggregation, which might reduce the surface area available for functionalization.\n\nBy following these steps and considerations, you should achieve effective and uniform functionalization of silica nanoparticles with 1,3-propane sultone, producing a hydrophilic material suitable for further polymer modification experiments."
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diff --git a/task2/task2-qa/macdonald-et-al-2024-design-of-abrasion-resistant-long-lasting-antifog-coatings.json b/task2/task2-qa/macdonald-et-al-2024-design-of-abrasion-resistant-long-lasting-antifog-coatings.json
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+{
+  "design_question": "Design a procedure to uniformly dissolve benzophenone in a solvent mixture prior to its use in preparing a hydrophilic polymer coating. Specify the type of solvents you might choose and their potential effects on the final coating.",
+  "design_answer": "Certainly! The process of dissolving benzophenone uniformly in a solvent mixture to be used in preparing a hydrophilic polymer coating involves a number of considerations. Allow me to break this down step by step to provide a detailed and systematic experimental protocol, while discussing the choice of solvents and their impact on the final polymer coating.\n\n---\n\n### **1. Analyze the question and summarize the key points:**\n- **Objective:** Dissolve benzophenone uniformly in a solvent mixture as part of the preparation step for a hydrophilic polymer coating.\n- **Key considerations:**\n   - Benzophenone's solubility depends on the solvent polarity.\n   - The solvent must be compatible with the monomers and/or polymers used in the hydrophilic coating preparation.\n   - The solvent system should not interfere with hydrophilicity or polymerization reactions.\n   - Uniform dissolution is critical to ensure consistent coating performance.\n\n---\n\n### **2. Detailed procedure for dissolving benzophenone in a solvent mixture:**\n\n#### **Step 1: Solvent selection**\nTo dissolve benzophenone efficiently, a combination of polar and nonpolar solvents may be required. Benzophenone has moderate polarity due to the carbonyl functional group, so solvents of intermediate polarity are ideal. For a hydrophilic polymer formulation, the following solvent options are commonly used:\n\n1. **Ethanol (polar solvent):**\n   - It has good solubility for benzophenone.\n   - Enhances the hydrophilicity of the system.\n   - Evaporates relatively quickly, minimizing interference in subsequent polymerization.\n\n2. **Acetone (polar aprotic solvent):**\n   - Solubilizes benzophenone effectively.\n   - Compatible with many hydrophilic polymers' synthesis processes.\n\n3. **Tetrahydrofuran (THF, moderately polar):**\n   - Excellent solvent for benzophenone.\n   - Miscible with water, which may be useful for hydrophilic polymer coatings.\n\n4. **Isopropanol (IPA, polar):**\n   - Acts as a good miscible solvent and complements benzophenone's dissolution.\n\nAlternatively, for a two-solvent system:\n- Ethanol (polar) and THF (intermediate polarity) can be combined to tune solvent polarity.\n- Water can also be introduced in small amounts in specific cases to promote greater hydrophilicity.\n\n#### **Step 2: Determine reagent quantities**\n- Decide on the quantity of benzophenone to dissolve based on your hydrophilic polymer formulation. For example, if the coating mixture requires 10 g of benzophenone:\n  - Use a 1:10 (w/v) ratio initially as a starting point, i.e., 100 mL of solvent mixture per 10 g of benzophenone.\n  - Adjust solvent quantities based on solubility tests to ensure complete dissolution.\n\n#### **Step 3: Prepare the solvent mixture**\n1. Choose the primary solvent (e.g., THF) and secondary solvent (e.g., ethanol), ensuring they are miscible.\n2. Mix the solvents in appropriate proportions (common mixtures are 70:30, 50:50, or 30:70 by volume) to achieve the desired polarity for benzophenone dissolution.\n3. Stir the solvent mixture thoroughly for 5 minutes to ensure homogeneity.\n\n#### **Step 4: Dissolve benzophenone**\n1. Gradually add benzophenone to the solvent mixture under continuous stirring.\n   - Use a magnetic stirrer set at moderate speed (e.g., 300–500 rpm).\n   - Maintain room temperature (20–25°C) initially, as benzophenone dissolves readily at this temperature.\n2. Monitor dissolution visually. If complete dissolution is not achieved:\n   - Slightly warm the solvent mixture to about 40–50°C using a water bath. Avoid overheating, which may degrade benzophenone.\n\n#### **Step 5: Filtration (if necessary)**\n- If undissolved particles remain, filter the solution through a fine-pore membrane (e.g., 0.45 µm) to obtain a clear, uniform solution.\n\n#### **Step 6: Storage of the solution**\n- Store the benzophenone solution in an amber glass container to protect it from light (benzophenone is light-sensitive).\n- Keep the solution at room temperature if used within 24 hours; otherwise, refrigerate to prevent solvent evaporation.\n\n---\n\n### **3. Potential effects of selected solvents on the final coating:**\n\n1. **Hydrophilicity impact:**\n   - Using polar solvents like ethanol or water can enhance the hydrophilicity of the final polymer coating.\n   - Nonpolar solvents should be minimized to avoid compromising hydrophilicity.\n\n2. **Polymerization compatibility:**\n   - Ensure the solvent system does not interfere with the polymerization reaction (e.g., radical initiators may react with some solvents).\n   - For hydrophilic polymer coatings, ethanol and THF are preferred due to their inert behavior in common polymerization systems (like free-radical or photoinitiated reactions).\n\n3. **Uniformity of coating:**\n   - The choice of solvent affects coating uniformity and surface morphology.\n   - High volatility of solvents like acetone and ethanol aids in quick evaporation but requires controlled drying conditions to prevent uneven coating.\n\n---\n\n### **Final Notes for Lab Execution:**\n- Perform a small-scale solubility test before preparing the full solution.\n- Document all quantities and observations for reproducibility.\n- Use proper safety measures when handling volatile solvents (work in a fume hood, avoid open flames, use PPE).\n\nBy following these steps and considerations, you should obtain a uniform benzophenone solution compatible with hydrophilic polymer synthesis, ensuring high-quality coating preparation. Let me know if you have further questions!"
+}
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diff --git a/task2/task2-qa/nakagawa-et-al-2024-preparation-of-antifog-hard-coatings-based-on-carboxy-functionalized-polyhedral-oligomeric.json b/task2/task2-qa/nakagawa-et-al-2024-preparation-of-antifog-hard-coatings-based-on-carboxy-functionalized-polyhedral-oligomeric.json
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+{
+  "design_question": "Imagine you are provided with carboxy-functionalized rod-like polySQ and asked to utilize it as a precursor in sol-gel chemistry to create hydrophilic polymer coatings. What experimental conditions (e.g., temperature, solvents) would you optimize and why?",
+  "design_answer": "To address your question regarding the utilization of carboxy-functionalized rod-like polySQ as a precursor in sol-gel chemistry to create hydrophilic polymer coatings, let's proceed systematically, as guided by the outlined requirements:\n\n---\n\n### **Step 1: Identifying the Key Aspects of the Problem**\n1. **Precursor Material**: Carboxy-functionalized rod-like polySQ.\n   - Understanding its critical functional groups (carboxylic acid groups) and its structural implications (rod-like polySQ backbone) is essential.\n   - The carboxylic acid groups provide reactive sites for chemical modification or processing in sol-gel chemistry to form hydrophilic coatings.\n\n2. **Target Objective**: Prepare a hydrophilic polymer coating.\n   - Hydrophilicity implies enhancing the polymer's affinity for water by incorporating functional groups (e.g., hydroxyl, amine, or other hydrophilic moieties) or optimizing the reaction morphology to expose hydrophilic sites.\n   - Sol-gel chemistry should be tailored to achieve a uniform, stable, hydrophilic coating on the substrate.\n\n3. **Experimental Parameters to Optimize**:\n   - Reaction conditions, including temperature, solvent selection, pH, catalyst concentration, and reaction duration, should be analyzed and justified.\n   - Control of hydrolysis and condensation steps typical of sol-gel chemistry is critical for uniform and defect-free coatings.\n\n---\n\n### **Step 2: Detailed Experimental Process for Synthesizing Hydrophilic Polymer Coating**\n\n#### **Step 2.1: Precursor and Solvent Preparation**\n- **Precursor (carboxy-functionalized polySQ)**:\n  - We assume that the precursor contains a carboxylic acid (-COOH) functionality along the polySQ rod-like backbone. This can act as a reactive site for sol-gel branching or a self-assembly moiety.\n  - Use 0.1–0.2 g of carboxy-functionalized polySQ (varied depending on the coating area required).\n\n- **Selection of Solvent**:\n  - Sol-gel reactions involve hydrolysis and condensation steps that are solvent-sensitive.\n  - Suggested solvents: Polar protic solvents like ethanol or isopropanol (88–99% pure) are recommended due to their ability to facilitate hydrolysis of precursors while maintaining uniform mixing.\n  - Ratio of solvent to precursor by mass: ~5:1 to ensure complete dissolution of polySQ.\n\n#### **Step 2.2: Optimizing Sol-Gel Reaction Conditions**\n1. **Hydrolysis**:\n   - Add **deionized water** (DI water) to the polySQ solution to induce hydrolysis of carboxylic sites and promote sol-gel reactions. The molar ratio of water to precursor is critical:\n     - Use approximately 10:1 molar ratio of water to precursor to ensure sufficient hydrolysis, as the carboxy-functionalized sites are hydrophilic and can accommodate excess water.\n   - Maintain pH around 3.5–5.0 using **acetic acid** as a weak acid catalyst.\n     - Acetic acid facilitates the hydrolysis step without over-accelerating condensation, which can lead to gelation inconsistencies.\n\n2. **Temperature**:\n   - Perform the hydrolysis at **40–45 °C** with constant stirring (500–700 rpm) for 2–3 hours.\n   - This moderate temperature range ensures sufficient reaction rates while preserving the structural integrity of the polySQ backbone.\n\n3. **Condensation**:\n   - After hydrolysis is complete, increase the reaction temperature to **60–70 °C** to initiate the condensation step.\n   - Stirring should be maintained to avoid localized gelation, which could lead to non-uniform coatings.\n   - Add a small amount of **tetraethoxysilane (TEOS)** or another alkoxysilane (if added crosslinking is required) in a 1:1 molar ratio with carboxy-functionalized sites to promote silica-based network formation. The silanol intermediates will attach to the carboxy-functionalized polySQ, enhancing hydrophilicity and introducing structural robustness.\n\n#### **Step 2.3: Application as Coating**\n- Once the sol-gel material achieves the desired viscosity and homogeneity, it can be coated onto the desired substrate (e.g., glass, ceramics, or metals).\n  - Coating method: Use **dip-coating** or **spin-coating** depending on the substrate and desired layer thickness.\n  - Dip-coating protocol: Immerse the substrate, hold it for 1 minute to allow uniform polymer adhesion, then withdraw it at a rate of 1–2 mm/s.\n\n- Post-deposition curing:\n  - Cure the coated substrate in an oven at **80–100 °C** for 12–24 hours to remove residual solvents and stabilize the polymer network.\n  - This step crosslinks the polymeric sol-gel and ensures a stable, hydrophilic coating.\n\n---\n\n### **Step 3: Theoretical Justification for Conditions**\n1. **Hydrolysis and Condensation Control**:\n   - Controlled pH (mildly acidic, 3.5–5) allows a balance between hydrolysis and condensation, avoiding premature gelation.\n   - Moderate temperature aids in molecular mobility, ensuring uniform reactions.\n\n2. **Solvent Choice**:\n   - Polar protic solvents like ethanol dissolve polySQ effectively and aid in hydrolysis of any added alkoxysilanes.\n   - A high solvent-to-precursor ratio facilitates homogeneity.\n\n3. **Enhancing Hydrophilicity**:\n   - Incorporating silanol [Si–OH] groups from TEOS or functionalizing the carboxylic groups with hydrophilic moieties (e.g., hydroxyl or amine groups) enhances water affinity.\n\n4. **Coating Methodology**:\n   - Dip-coating provides reproducible thickness and defect-free surfaces in sol-gel processing.\n   - Post-deposition curing eliminates trapped solvents and solidifies the polymer networks.\n\n---\n\n### **Step 4: Notes for Experimental Practice**\n- **Safety Considerations**:\n  - Use a fume hood for handling solvents like ethanol.\n  - Wear gloves and goggles for handling acids and TEOS, which can be corrosive.\n\n- **Reproducibility**:\n  - Maintain consistent stirring speed and deposition conditions for reproducible results.\n\n- **Characterization**:\n  - Assess hydrophilicity through techniques like water contact angle measurement (<15° is ideal for hydrophilic coatings).\n  - Use spectroscopic methods (e.g., FTIR) to confirm the presence of silanol and carboxylic acid groups after deposition.\n\n---\n\nBy following this methodology, you will obtain a well-controlled, hydrophilic polymer coating derived from carboxy-functionalized rod-like polySQ using sol-gel chemistry. Let me know if further clarification is needed!"
+}
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diff --git a/task2/task2-qa/olveira2015.json b/task2/task2-qa/olveira2015.json
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+{
+  "design_question": "Propose a method to optimize the introduction of Si–OH groups on the surface of a polymer coating using tetraethyl orthosilicate (TEOS) and explain how the presence of these groups contributes to hydrophilicity.",
+  "design_answer": "To optimize the introduction of Si–OH groups using tetraethyl orthosilicate (TEOS) on the surface of a polymer coating, we need to analyze your question systematically, determine how TEOS can be hydrolyzed and polymerized to deposit Si–OH-functionalized silica coatings, and investigate the linkage between Si–OH groups and improved hydrophilicity. Below, I will guide you step by step through the synthesis approach, ensuring we meet your detailed requirements for understanding and laboratory practice.\n\n---\n\n### **Step 1: Key points of the question**\n- The goal is to introduce Si–OH groups onto a polymer surface to enhance hydrophilicity.\n- TEOS (tetraethyl orthosilicate) is the precursor chosen for this functionalization.\n- Strong emphasis is placed on the optimization of reaction conditions, reagent ratios, and experimental details.\n\n### **Step 2: Systematic method for Si–OH group introduction using TEOS**\nThis process relies on the hydrolysis and condensation of TEOS to form silica-based coatings functionalized with Si-OH groups. Below is an optimized experimental scheme for achieving this goal:\n\n---\n\n#### **Step 2.1: Materials and reagents**\n1. **Polymer substrate**: Choose a polymer with surface chemistry compatible with silica adhesion (e.g., polyurethane or polycarbonate).\n2. **Tetraethyl orthosilicate (TEOS)**: Silica precursor.\n3. **Solvent**: Ethanol (as a common solvent for hydrolysis).\n4. **Catalyst**: Acidic or basic catalyst for hydrolysis. Typically, dilute hydrochloric acid (HCl) is used.\n5. **Deionized water**: Hydrolysis agent.\n6. **pH-adjusting reagents**: For controlling the reaction medium.\n7. **Optional surface modifier**: If needed, base polymer surface pretreatment (e.g., UV/ozone treatment).\n\n---\n\n#### **Step 2.2: Reaction scheme**\nHydrolysis and polymerization of TEOS take place under controlled conditions to deposit silica coatings. The goal is to create Si–OH group-rich surfaces. The process typically involves the sol-gel method.\n\n---\n\n### **Step 3: Experimental procedure**\n#### **Step 3.1: Surface pretreatment of the polymer substrate**\nPrepare the polymer surface to enhance the binding of the silica coating:\n1. **Surface cleaning**: Clean the polymer substrate thoroughly using ethanol or methanol and deionized water to remove impurities.\n2. **Activation**: Treat the polymer surface to improve adhesion, such as:\n   - UV ozone treatment for 15–30 minutes to increase surface energy.\n   - Plasma treatment, if available.\n\n#### **Step 3.2: Preparation of the TEOS solution**\nPrepare a sol-gel solution as follows:\n1. **Step 1: Hydrolysis**\n   - In a clean beaker, mix tetraethyl orthosilicate (TEOS), ethanol, and deionized water in a molar ratio **TEOS : H2O : ethanol ≈ 1 : 4 : 4.**\n   - Add a catalytic amount of dilute hydrochloric acid (HCl). For instance, use **0.01 M HCl** to bring the solution pH to around 3–4 (acidic conditions promote better hydrolysis rates).\n   - Stir the mixture at room temperature for **2 hours** to ensure complete hydrolysis of TEOS into silicic acid monomers, which contains Si–OH groups.\n\n2. **Step 2: Condensation**\n   - Allow the solution to undergo condensation reactions for a further **2–4 hours** under slow stirring. This leads to the formation of silica particles or networks rich in Si–OH groups.\n\n#### **Step 3.3: Polymer coating**\nDeposit the silica layer containing Si–OH groups onto the polymer surface using one of the following methods:\n1. **Dip-coating**:\n   - Immerse the treated polymer substrate into the prepared TEOS solution for **30 minutes** to enable adsorption of the Si–OH-functionalized silica.\n   - Withdraw the sample at a controlled rate (e.g., **5–10 mm/s**) to ensure uniform coating.\n2. **Spin-coating**:\n   - Deposit a few drops of the TEOS solution onto the polymer and spin-coat the surface at **1000–3000 rpm** for **30–60 seconds**.\n\n#### **Step 3.4: Heat treatment**\n1. Heat the coated substrate to cure the silica layer:\n   - Gradually heat to **60–120°C** for **2–4 hours** to evaporate residual solvents and ensure the silica network forms.\n   - Gradual heating prevents cracking or delamination of the silica coating.\n2. Optionally, increase the temperature to **150–200°C** to further densify the silica, if the polymer substrate's thermal stability allows.\n\n#### **Step 3.5: Characterization**\nEvaluate the success of the functionalization:\n1. **Contact angle measurement**:\n   - Use a goniometer to assess hydrophilicity by measuring the contact angle of water droplets on the silica-coated polymer surface. Lower angles (<45°) indicate enhanced hydrophilicity.\n2. **Fourier-transform infrared spectroscopy (FTIR)**:\n   - Confirm the presence of Si–OH groups by detecting characteristic absorption peaks at **~3200–3400 cm⁻¹** (O–H stretching) and **~1000–1200 cm⁻¹** (Si–O–Si vibrations).\n3. **Scanning electron microscopy (SEM)**:\n   - Examine the surface morphology to ensure uniform coating.\n\n---\n\n### **Step 4: Why Si–OH groups enhance hydrophilicity**\n- **Hydrophilic functionality**: Si–OH groups are polar and interact strongly with water molecules through hydrogen bonding. This improves wettability, as water is attracted to and spreads across the functional surface.\n- **Water adsorption**: The hydrophilic Si–OH groups create a high-density site for water binding and retention.\n- **Application benefits**: Hydrophilic surfaces prepared through this method can enhance anti-fogging, improve lubrication in aqueous environments, and aid applications like water purification and biomedical surfaces.\n\n---\n\n### Conclusion\nThe optimized method involves hydrolyzing TEOS in the presence of ethanol, water, and acid, depositing the silica layer via dip- or spin-coating, followed by heat curing to functionalize the polymer surface with Si–OH groups. Characterizing the hydrophilic properties ensures experimental success. This process is rigorous yet feasible for laboratory practice and should yield a hydrophilic coating optimal for various applications.\n\n"
+}
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diff --git a/task2/task2-qa/optically transparent super-hydrophobic thin film fabricated by reusable polyurethane-acrylate(PUA) mold.json b/task2/task2-qa/optically transparent super-hydrophobic thin film fabricated by reusable polyurethane-acrylate(PUA) mold.json
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+{
+  "design_question": "Propose a polymerization setup using ethylene glycol dimethacrylate as a crosslinking agent, and discuss how the choice of this molecule affects the mechanical and hydrophilic properties of the polymer.",
+  "design_answer": "Absolutely, let's approach this step by step.\n\n---\n\n### **Step 1: Analyze the question and summarize the key points.**\n\n#### Key Points:\n1. **Monomer system and crosslinking agent**: The question specifies the use of **ethylene glycol dimethacrylate (EGDMA)** as a crosslinking agent.\n2. **Objective**: You need to design a polymerization setup, detailing the synthesis process and reaction conditions.\n3. **Properties to discuss**: \n   - Influence of **EGDMA** on the **mechanical properties**, such as rigidity and toughness, of the resulting polymer.\n   - Influence of **EGDMA** on the **hydrophilic properties** of the polymer.\n\n---\n\n### **Step 2: Answer the question in detail and systematically.**\n\n#### **Experimental Preparation Scheme for a Hydrophilic Polymer Crosslinked with EGDMA**\n\n---\n\n#### **1. Monomer Selection**\nTo design a hydrophilic polymer, we'll start by selecting a hydrophilic monomer — for example, **2-hydroxyethyl methacrylate (HEMA)**. HEMA is widely used in biomaterial applications (like hydrogels) due to its hydrophilic hydroxyl (-OH) group, which interacts with water.\n\n- **EGDMA** will serve as the crosslinking agent. Its two methacrylate groups can form covalent crosslinks between polymer chains, enhancing the mechanical strength while retaining hydrophilicity because of the ethylene glycol backbone of EGDMA.\n\n---\n\n#### **2. Reaction Setup**\nPolymerization of HEMA in the presence of EGDMA involves a free-radical polymerization process. Below are the experimental details:\n\n---\n\n**a) Apparatus and materials:**\n- **Monomers**: HEMA as the base monomer and EGDMA as the crosslinking agent.\n- **Solvent**: Use **water** or **ethanol** as solvents to ensure a homogeneous reaction phase.\n- **Initiator**: Azobisisobutyronitrile (**AIBN**) or potassium persulfate (**KPS**) can be used as free-radical initiators.\n- **Inert atmosphere**: Nitrogen (N₂) will be used to purge the system to remove oxygen, which inhibits radical polymerization.\n\n---\n\n**b) Reaction steps:**\n\n1. **Preparation of Reaction Mixture**:\n   - Weigh the monomer **HEMA** and the crosslinking agent **EGDMA**. \n     - Example molar ratio: **HEMA:EGDMA** = 95:5 (to maintain a hydrophilic network while providing sufficient crosslinking for mechanical strength).\n     - For 10 g total monomer mixture:\n       - HEMA = 9.5 g (approx. 80 mmol)\n       - EGDMA = 0.5 g (approx. 2.5 mmol)\n   - Dissolve the monomer and crosslinker in 20 mL ethanol or water to form a homogeneous solution.\n\n2. **Initiation**:\n   - Dissolve **AIBN** (approx. 1 wt% of total monomer weight, e.g., 0.1 g) in the monomer solution.\n   - Sonicate the solution for a few minutes to ensure proper dispersion.\n\n3. **Deoxygenation**:\n   - Transfer the solution to a round-bottom flask or reaction vessel.\n   - Purge the reaction mixture with nitrogen gas for 20–30 minutes to remove dissolved oxygen, which can quench free-radical polymerization.\n\n4. **Polymerization**:\n   - Heat the reaction mixture to **65–70°C** while stirring (AIBN decomposes to generate radicals at this temperature).\n   - Allow the reaction to proceed for **4–6 hours** to ensure complete polymerization. The time will depend on the desired crosslink density and molecular weight.\n\n5. **Post-Polymerization and Purification**:\n   - After polymerization, the resulting hydrogel or polymer matrix will form.\n   - Wash the polymer thoroughly with ethanol and deionized water to remove unreacted monomer and impurities.\n   - Dry the polymer in a vacuum oven at 40–50°C.\n\n---\n\n**c) Optimization Notes**:\n- **Crosslinker concentration**: Increasing EGDMA concentration above 5 wt% will result in higher crosslink density, which enhances mechanical properties but may reduce swelling (and hence hydrophilicity). A careful balance between these parameters is essential.\n- **Solvent polarity**: Water as a solvent can enhance hydrophilicity, but ethanol can sometimes improve chain mobility during polymerization.\n\n---\n\n#### **3. Effects of EGDMA on Polymer Properties**\n\n**a) Hydrophilicity**:\n- The hydrophilic nature of the polymer primarily arises from the HEMA monomer’s hydroxyl (-OH) group, which forms hydrogen bonds with water. \n- **Impact of EGDMA**: EGDMA contributes a polyethylene glycol-based hydrophilic segment, which further enhances hydrophilicity. However, an excessive amount of EGDMA may reduce overall water-absorbing capacity due to increased crosslinked density, limiting the polymer chain’s ability to stretch and absorb water.\n\n**b) Mechanical Strength**:\n- EGDMA introduces crosslinks between polymer chains, forming a 3D network structure.\n - **Low EGDMA concentration (<5 wt%)**: Polymer will form a flexible hydrogel with high water swelling.\n - **Higher EGDMA concentration (5–10 wt%)**: Crosslink density increases, leading to a stiffer, stronger polymer with reduced swelling. This is useful where mechanical robustness is critical (e.g., biomaterial scaffolds or coatings).\n - **Excessive EGDMA (>10 wt%)**: Can lead to brittleness due to overly rigid crosslinking.\n\n**c) Tunability**:\n- The ratio of HEMA to EGDMA can be adjusted to tailor the hydrogel or polymer’s water absorption capacity, toughness, and elasticity, making this system versatile for various applications.\n\n---\n\n### **Step 3: Final Notes and Recommendations**\n\n- **Safety Precautions**: Always handle methacrylate monomers with gloves and work in a fume hood due to their volatility and potential skin sensitizing properties. EGDMA is also a potential irritant.\n- **Characterization**: After synthesis, confirm the polymer's properties:\n  - Use **Fourier-transform infrared spectroscopy (FTIR)** to check for functional group incorporation (e.g., hydroxyl and ester groups).\n  - Measure swelling degree in water to evaluate hydrophilicity.\n  - Conduct tensile tests to assess mechanical properties.\n\nBy following this preparation scheme and systematically varying the HEMA:EGDMA ratio, you can produce hydrophilic polymers with tunable mechanical properties, suitable for diverse applications such as biomedical devices, hydrogels, and coatings.\n\n--- \n\nWould you like further guidance on specific characterization techniques or potential modifications to this procedure?"
+}
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+{
+  "design_question": "Describe the procedure for purifying the polymer product obtained after using methyl methacrylate (MMA) to modify the polymer. What would be the rationale for choosing specific solvents during the precipitation process?",
+  "design_answer": "### Question Analysis and Key Points\nYour question focuses on the **purification of a polymer modified by methyl methacrylate (MMA)** and the choice of solvents during the **precipitation process**. Both aspects are essential for isolating the polymer product in a pure, high-quality form. To answer this question in a systematic manner, let us:\n1. Break down the steps of polymer purification after MMA modification.\n2. Discuss the rationale for solvent selection during precipitation in detail.\n\nThe underlying principles guiding the purification process are:\n- Separation of unreacted monomers or initiators, residual MMA, by-products, and solvents from the polymer.\n- Ensuring the polymer's integrity, hydrophilicity, and molecular structure remain unaltered.\n\n### Systematic Answer: Purification Procedure\n\n#### **Step 1: Dissolution of the Crude Polymer**\nAfter the MMA modification reaction is complete, the reaction mixture typically contains the following components:\n- The synthesized polymer (a blend of original polymer and MMA-based copolymer).\n- Unreacted monomers (MMA).\n- Initiators, additives, or catalysts (optional, depending on the conditions of the MMA modification reaction).\n- Reaction solvents.\n\n1. **Selection of a Solvent for Dissolution**:\n   - Choose a solvent in which the polymer is highly soluble.\n   - Common choices include **tetrahydrofuran (THF)**, **acetone**, or a similar organic solvent compatible with MMA-modified hydrophilic polymers.\n   - Ensure the solvent can dissolve not just the polymer but also smaller molecular impurities and residuals, which will facilitate separation in later steps.\n\n2. **Procedure**:\n   - Transfer the reaction mixture to a flask.\n   - Add the selected solvent gradually (approximately 10–15 mL per gram of crude polymer) while stirring gently.\n   - Heat the mixture slightly (e.g., to 30–50°C) to assist dissolution if required. Avoid temperatures that can degrade the polymer.\n\n#### **Step 2: Precipitation of the Purified Polymer**\nPrecipitation is a key isolation method in polymer purification. The goal is to selectively precipitate the polymer while leaving soluble by-products and impurities in the liquid phase.\n\n1. **Selection of a Precipitation Solvent**:\n   - Choose a nonsolvent, i.e., a solvent in which the polymer is **insoluble**, but one that can dissolve impurities and residual reactants effectively.\n   - The nonsolvent must also enable the precipitation of the polymer into a collectable solid without deforming its structure or molecular conformation.\n\n   **Common solvent pairings**:\n   - **Polymer-solvent (e.g., THF) and nonsolvent (e.g., methanol)**.\n   - **Acetone-chilled diethyl ether**.\n   - Other common nonsolvents: ethanol, isopropanol, water (depends on polymer solubility and hydrophilicity).\n\n2. **Precipitation Procedure**:\n   - Gradually add the reaction solution (dissolved polymer in solvent) dropwise into a large volume of cold nonsolvent (ratio of 1:5 or 1:10, polymer solution to nonsolvent, is typical). E.g., 10 mL of dissolved polymer solution is added to 100 mL of cold methanol.\n   - Stir continuously during the addition to ensure uniform mixing and efficient precipitation.\n   - Maintain the precipitation system at low temperatures (0–5°C using an ice bath) to increase polymer yield and enhance purity.\n\n3. **Observations**:\n   - The polymer will precipitate as a solid or gel-like phase, while the impurities remain dissolved in the nonsolvent.\n\n#### **Step 3: Collection of the Precipitated Polymer**\n1. Use vacuum filtration to separate the polymer precipitate from the liquid phase (mother liquor).\n   - Filter using a Buchner funnel lined with qualitative filter paper.\n   - Wash the precipitate with additional cold nonsolvent (e.g., cold methanol) to remove any residual impurities on the polymer surface.\n\n2. Dry the polymer under vacuum at a moderate temperature (e.g., 40–50°C) until constant weight is achieved.\n   - Avoid overheating, as this may degrade or modify the polymer.\n\n#### **Step 4: Verification of Purity**\n1. Check the polymer for purity using analytical techniques such as:\n   - **Fourier-transform infrared spectroscopy (FTIR)**: Ensure functional groups characteristic of MMA-modified hydrophilic polymers are present and impurities (e.g., unreacted MMA) are absent.\n   - **Nuclear magnetic resonance (NMR)**: Quantify how much MMA has been incorporated and confirm that no monomer residue remains.\n   - **Gel permeation chromatography (GPC)**: Analyze molecular weight distribution to confirm polymer integrity.\n\n---\n\n### Rationale for Solvent Selection in Precipitation\nChoosing the appropriate nonsolvent is critical for the success of the precipitation process.\n\n1. **Solubility Difference**:\n   - The polymer must be insoluble in the nonsolvent to allow efficient precipitation. This depends on the polymer's chemical structure and the solubility parameters (e.g., Hansen solubility parameters).\n   - The nonsolvent must be miscible with the initial solvent to promote even mixing.\n\n2. **Enhancing Hydrophilicity**:\n   - Since the polymer is hydrophilic (MMA-modified), water or polar organic solvents (e.g., ethanol, methanol) are often used as nonsolvents.\n\n3. **Temperature Effects**:\n   - Using a cold nonsolvent reduces polymer aggregation and enhances particle separation, ensuring uniform precipitation.\n\n4. **Impurity Removal**:\n   - The nonsolvent should be able to dissolve small-molecule impurities (unreacted MMA, catalyst residues, etc.) while leaving the high-molecular-weight polymer to precipitate cleanly.\n\n---\n\n### Final Notes\nBy following the outlined purification steps and carefully selecting the combination of solvent and nonsolvent, you will be able to obtain a high-purity MMA-modified hydrophilic polymer. The methodology is robust, scalable, and adaptable to various polymer systems. If you have specific constraints or additional details on the polymer system, such as its molecular weight or functional groups, I can further refine the approach. Always ensure safety protocols are in place when handling volatile and hazardous solvents."
+}
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diff --git a/task2/task2-qa/preparation of antifog and antibacterial coatings by photopolymerization.json b/task2/task2-qa/preparation of antifog and antibacterial coatings by photopolymerization.json
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+{
+  "design_question": "Describe the synthetic procedure you would use to prepare a quaternary ammonium salt (14QAS) starting from a tertiary amine and a bromoalkane. Include the reaction conditions and steps required to ensure high product yield.",
+  "design_answer": "Certainly! I will provide you with a systematic and detailed experimental scheme for the preparation of a quaternary ammonium salt (14QAS) starting from a tertiary amine and a bromoalkane. Quaternary ammonium salts are widely used in hydrophilic polymer systems to enhance ionic and hydrophilic characteristics.\n\n---\n\n### Key Points in the Question:\n1. **Substrates**:\n   - The starting materials are a **tertiary amine** (R₃N) and a **bromoalkane** (R′-Br).\n   - The tertiary amine provides the basic nitrogen atom, while the bromoalkane introduces the alkyl group to generate the quaternary ammonium structure.\n\n2. **Reaction Goal**:\n   - The reaction is a **nucleophilic substitution reaction (SN2)**, where the nucleophilic nitrogen in the tertiary amine attacks the electrophilic carbon in the bromoalkane to form the quaternary ammonium salt, R₃N⁺R′-Br⁻.\n\n3. **Optimizing Product Yield**:\n   - The presence of unwanted side reactions or incomplete conversions should be minimized.\n   - Reaction parameters, such as solvent, stoichiometry, temperature, and reaction duration, must be optimized for high yield.\n\n---\n\n### Synthetic Procedure for Preparing 14QAS:\n\n#### **Step 1: Preparation and Reagent Ratio Setup**\n1. **Reagents Required**:\n   - Tertiary amine: Choose an appropriate tertiary amine (e.g., trimethylamine, triethylamine, or other trialkylamines depending on the desired final structure).\n   - Bromoalkane: Select the desired bromoalkane (e.g., 1-bromotetradecane if preparing a tetradecyl quaternary salt).\n   - Solvent: Use a polar aprotic solvent such as **acetonitrile (CH₃CN)** or a nonpolar solvent like **toluene**. Acetonitrile is often preferred because it promotes the SN2 reaction mechanism.\n\n2. **Molar Ratio**:\n   - Use a slight **excess of bromoalkane** (1.1–1.2 equivalents with respect to the tertiary amine) to drive the reaction to completion.\n\n3. **Reaction Vessel**:\n   - Utilize a **round-bottom flask** equipped with a reflux condenser to maintain a constant temperature.\n\n---\n\n#### **Step 2: Reaction Procedure**\n1. **Dissolution**:\n   - Dissolve the tertiary amine in acetonitrile in the round-bottom flask. For example, if using 10 mmol of the tertiary amine, dissolve it in approximately 20–30 mL of acetonitrile.\n\n2. **Addition of Bromoalkane**:\n   - Slowly add the bromoalkane to the solution of tertiary amine while stirring at room temperature. Add it dropwise if needed to ensure controlled mixing.\n   - Example: For 10 mmol of tertiary amine, add approximately 11–12 mmol (1.1–1.2 equivalents) of bromoalkane.\n\n3. **Heating**:\n   - Heat the reaction mixture under reflux (70–90 °C, depending on the solvent used). The exact temperature may vary depending on the reactivity of the specific tertiary amine and bromoalkane, typically optimized within this range.\n   - Allow the reaction to proceed for 12–24 hours to ensure complete conversion.\n\n4. **Monitoring Progress**:\n   - Use **thin-layer chromatography (TLC)** or **NMR spectroscopy** to monitor the reaction’s progression. \n\n---\n\n#### **Step 3: Workup and Purification**\n1. **Precipitation of the Product**:\n   - After completion, cool the reaction mixture to room temperature. The quaternary ammonium salt may precipitate in the reaction solvent (depending on the solubility).\n   - If precipitation occurs, filter the solid product using a Büchner funnel and wash it with a small amount of cold solvent (e.g., diethyl ether) to remove unreacted bromoalkane or impurities.\n\n2. **Recrystallization (if necessary)**:\n   - If the quaternary ammonium salt is not pure, recrystallize it from a suitable solvent mixture. A common choice is a mixture of **ethanol and diethyl ether** or **methanol and ether**, depending on the salt’s solubility.\n\n3. **Drying**:\n   - Dry the purified quaternary ammonium salt under vacuum at 40–50 °C to remove any residual solvent.\n\n---\n\n### Additional Notes:\n- **Yield Considerations**:\n   - Using a polar aprotic solvent like acetonitrile is critical to enhance the nucleophilicity of the nitrogen and to promote the SN2 mechanism, which improves yield.\n   - Employing an excess of bromoalkane helps to drive the reaction forward.\n   - Prolonged heating under reflux ensures complete conversion of reactants.\n  \n- **Safety Precautions**:\n   - Handle bromoalkanes with care, as they are irritants and potentially toxic.\n   - Work in a well-ventilated fume hood and wear proper personal protective equipment.\n\n- **Example Calculation**:\n   - If using 10 mmol of trimethylamine (MW = 59.11 g/mol) and 12 mmol of 1-bromotetradecane (C14H29Br, MW = 273.3 g/mol), the required masses of the reagents are:\n     - Trimethylamine: \\( 0.01 \\, \\text{mol} \\times 59.11 \\, \\text{g/mol} = 0.591 \\, \\text{g} \\)\n     - 1-Bromotetradecane: \\( 0.012 \\, \\text{mol} \\times 273.3 \\, \\text{g/mol} = 3.28 \\, \\text{g} \\)\n\n---\n\nBy following this systematic procedure, you should be able to successfully prepare a quaternary ammonium salt with a high yield. Feel free to ask if you have further questions or require modifications for specific tertiary amines or bromoalkanes!"
+}
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diff --git a/task2/task2-qa/s41467-020-14807-x.json b/task2/task2-qa/s41467-020-14807-x.json
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+{
+  "design_question": "Explain how the molecule I-819 can be used to facilitate the synthesis of a hydrophilic polymer and what its specific function is during the experimental process.",
+  "design_answer": "To answer your question step-by-step, let us carefully analyze your question, identify the key points, and systematically explore how the molecule I-819 can be utilized to synthesize a hydrophilic polymer while discussing its specific function in the experimental process. Since we aim for a methodical explanation that you can practically apply in the laboratory, let me follow the rigorous scientific approach required as per your request.\n\n---\n\n### **Step 1: Analyzing the Question**\n- **Key Points to Understand:**\n  1. **Molecule I-819** and its functional role in facilitating the synthesis of a hydrophilic polymer.\n  2. The focus on **enhancing hydrophilicity** of the synthesized polymer.\n  3. Understanding the **reaction mechanism** or pathway by which I-819 contributes to the polymerization process.\n\n- **Important Contextual Considerations:**\n  - Once I-819's chemical nature is clear (likely a photoinitiator or crosslinking agent based on its molecular designation), we can determine how it participates in the experimental preparation. \n  - Hydrophilic polymers often involve incorporation of hydrophilic functional groups either into the monomer(s) or through modification of the polymer backbone.\n\n---\n\n### **Step 2: Understanding Molecule I-819**\n- Molecule I-819 is known as a **highly efficient photoinitiator**. This means it can absorb light and produce reactive species (e.g., free radicals) to initiate polymerization.\n- In the context of hydrophilic polymer synthesis, I-819 likely serves to initiate **free radical polymerization** of hydrophilic monomers (like acrylamide, acrylic acid, or polyethylene glycol derivatives). These monomers polymerize to form chains with hydrophilic properties.\n\n---\n\n### **Step 3: Designing the Experimental Preparation Sequence**\n\nLet us construct a detailed experimental protocol for synthesizing a hydrophilic polymer using I-819 to initiate polymerization. For clarity, I will break this down into steps.\n\n---\n\n#### **Step 3.1: Selection of Hydrophilic Monomers**\n- Choose appropriate monomers that contain **hydrophilic pendant groups**. Common choices include:\n  1. **Acrylamide (AM):** Offers -CONH2 groups for strong hydrophilicity.\n  2. **Acrylic Acid (AA):** Provides -COOH groups, enhancing water solubility.\n  3. **Polyethylene glycol methacrylate (PEG-MA):** Introduces hydroxyl (-OH) functionality, excellent for biocompatibility.\n- The choice of monomers can be tailored depending on whether you aim for nonionic, anionic, or neutral hydrophilicity.\n\n---\n\n#### **Step 3.2: Preparing the Reaction Mixture**\n1. **Weighing the Monomers:**\n   - Decide on specific molar ratios of monomers to achieve the desired hydrophilic balance. For example, blend **Acrylamide (5 g, 70 mol%)** with **Acrylic Acid (2.2 g, 30 mol%)** for copolymer synthesis.\n   \n2. **Dissolving Monomers:**\n   - Dissolve the monomers in **deoxygenated water** or a suitable solvent (e.g., DMSO if water solubility of some components is an issue). Ensure thorough mixing.\n\n3. **Adding Crosslinker (if required):**\n   - Add a crosslinking agent, e.g., **N,N'-methylenebisacrylamide (MBA)**, if you aim for a 3D network structure (e.g., hydrogels). Use ~0.5–1 wt% relative to the total monomer weight. \n\n4. **Incorporating the Initiator:**\n   - Add **I-819** into the reaction mixture. Optimal concentration is ~0.1–1 wt% relative to the monomer content.\n   - Ensure uniform mixing, as I-819 must be homogeneously distributed to ensure consistent radical generation during polymerization.\n\n---\n\n#### **Step 3.3: Polymerization Process**\n1. **Photopolymerization Setup:**\n   - Transfer the reaction mixture to a clean polymerization vessel (quartz or UV-transparent glass is ideal). Nitrogen purging is essential to remove residual oxygen during free-radical polymerization.\n\n2. **Light Source Selection:**\n   - Choose a UV lamp or LED source emitting at a wavelength compatible with the absorption range of I-819 (~365 nm for typical use). Adjust the light intensity to ~5–10 mW/cm².\n\n3. **Reaction Conditions:**\n   - Expose the mixture to UV light for **10–30 minutes**. Maintain constant temperature (~25–40°C, depending on the monomers) to avoid thermal side reactions.\n\n4. **Polymer Formation:**\n   - I-819 absorbs UV light, generating radicals that attack the double bonds of the monomers, initiating chain propagation. The reaction continues until most monomers are consumed, yielding the desired hydrophilic polymer.\n\n---\n\n#### **Step 3.4: Post-Processing**\n1. **Purification:**\n   - Wash the polymer with water or ethanol to remove unreacted monomers and photoinitiator residues.\n   \n2. **Drying:**\n   - Dry the purified polymer under vacuum at ~40–50°C to avoid degradation of hydrophilic segments.\n\n3. **Characterization:**\n   - Characterize the polymer’s hydrophilicity using tests such as:\n     - **Water absorption capacity** or swelling ratio (for hydrogels).\n     - **Contact angle measurement** to quantify surface hydrophilicity.\n     - **FTIR analysis** to confirm the presence of hydrophilic functional groups.\n\n---\n\n### **Step 4: Specific Role of I-819 in the Experimental Process**\n- As a **photoinitiator**, I-819 facilitates:\n  1. **Radical Generation Under UV Light:** Absorbs UV radiation and decomposes to produce radicals that initiate polymerization.\n  2. **Control of Polymerization Rate:** Allows precise control by adjusting UV exposure time and intensity.\n  3. **Minimized Thermal Side Effects:** Being a photoinitiator, it avoids harsh thermal conditions that could degrade hydrophilic groups.\n\nI-819 is particularly advantageous due to its **low light absorption threshold, excellent radical efficiency**, and ability to function well in aqueous/largely hydrophilic systems.\n\n---\n\n### **Step 5: Final Remarks and Suggestions**\n- I-819 is a versatile and efficient tool for synthesizing hydrophilic polymers under mild conditions. However, consistent handling of UV exposure and maintaining a deoxygenated atmosphere are critical to ensure efficiency.\n- When scaling this to the lab, ensure meticulous adherence to reagent ratios and reaction conditions. This will result in polymers with reproducible and robust hydrophilic properties.\n\n--- \n\nIf you have further questions regarding this approach, alternative monomers, or post-functionalization to enhance hydrophilicity, feel free to ask!"
+}
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diff --git a/task2/task2-qa/s41529-024-00427-z.json b/task2/task2-qa/s41529-024-00427-z.json
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+{
+  "design_question": "What steps would you take to ensure effective mixing of UPy-D400 into a polymer formulation, and how would you verify its successful incorporation into the final polymer structure?",
+  "design_answer": "To address your question and help you understand the experimental process thoroughly, let us first break it down into key components, so we can approach the task systematically. Based on your question, we aim to figure out:\n\n1. **Key Points to Analyze:**\n   - What is UPy-D400, and why is it being incorporated into the polymer formulation?\n   - How can effective mixing of UPy-D400 (a hydrophilic or functional additive) into the polymer matrix be ensured?\n   - What experimental steps and parameters are critical during the incorporation process to maintain homogeneity and preserve the integrity of the UPy-D400 structure and functionality?\n   - How do we verify or confirm that UPy-D400 has been successfully incorporated into the polymer structure?\n\n2. **Step-by-Step Experimental Strategy:**\n   I will now provide a detailed and systematic approach, specifying each step in the preparation process, along with important reaction conditions, equipment, and analytical techniques for successful execution in the lab.\n\n---\n\n### **Step 1: Understanding UPy-D400 and Its Significance**\n- **UPy-D400 description**: UPy (ureido-pyrimidinone) is a functional group known for its hydrogen-bonding interactions, making it valuable for improving a polymer’s hydrophilicity, self-healing, or supramolecular properties. D400 is typically a hydrophilic chain attached to the UPy group, likely based on polyethylene glycol (PEG) or another water-compatible structure.\n- **Incorporation Goal**: The goal is to mix UPy-D400 effectively into the polymer formulation in a uniform manner to retain its hydrophilicity or supramolecular assembly properties.\n\n---\n\n### **Step 2: Pre-treatment and Preparation of UPy-D400**\n1. **Purity Verification**: Before use, ensure that UPy-D400 is free of moisture and impurities since these can impact its reactivity and dispersion. Dry the material under vacuum at ~40–50 °C for 3–4 hours.\n    - **Equipment**: Vacuum oven or desiccator.\n    - **Control Parameter**: Ensure no thermal degradation occurs by limiting temperature.\n\n2. **Optional Solubilization**: If UPy-D400 has limited dispersibility in the polymer matrix at high viscosities, prepare a stock solution:\n    - Solubilize UPy-D400 in a hydrophilic solvent such as ethanol, methanol, or dimethyl sulfoxide (DMSO) if the polymer formulation can tolerate the solvent.\n    - Typical concentration: 10–30 wt%, depending on the target ratio in the formulation.\n    - Stir the solution at room temperature (25–30 °C) to ensure complete dissolution.\n\n---\n\n### **Step 3: Preparation of the Polymer and Mixing with UPy-D400**\n3. **Selection of Base Polymer**:\n   - Choose the polymer type that aligns with the hydrophilic design goal. For example, polyacrylamides, hydroxyl-functionalized polymers, or PEG-based networks work well.\n   - If the polymer is being synthesized in situ (e.g., via polymerization of monomers), UPy-D400 can be incorporated directly into the reaction system.\n\n4. **Mixing Parameters**:\n    - **Method**: Use a mechanical stirrer, twin-screw extruder (for molten polymers), or magnetic stirrer (for liquid/slurry systems).\n    - **Process**: Gradually add UPy-D400 (solid or solution form) to the polymer formulation under consistent stirring. \n        - Stirring Speed: Generally between 300–1000 rpm for liquid systems.\n        - Mixing Time: 30–60 minutes depending on the viscosity of the polymer solution.\n\n5. **Reaction/Polymerization with UPy-D400** (If the polymer is synthesized in situ):\n    - **Chemical Considerations**:\n      - If UPy-D400 contains reactive functional groups (e.g., hydroxyl, amine, or urethane), ensure it participates in the polymerization or crosslinking reaction. Adjust monomer and crosslinker ratios accordingly.\n    - **Reaction Conditions**:\n      - Typical temperatures for hydrophilic polymer synthesis are ~40–70 °C to maintain UPy functional integrity.\n      - Maintain the reaction in inert conditions (e.g., nitrogen or argon atmosphere) to avoid unwanted side reactions.\n      - Example: If using acrylamide-based monomers, UPy-D400 can be incorporated as a co-monomer, with molar ratios tailored to achieve ~2–10 mol% UPy-D400 in the final structure.\n\n---\n\n### **Step 4: Post-Processing and Verification**\n6. **Post-Mixing Homogenization**: After incorporating UPy-D400 into the polymer blend, ensure proper homogenization:\n    - Utilize shear mixing or sonication for liquid-state formulations or melt-blending for molten polymers.\n\n7. **Formulation Stabilization**: If the polymer is crosslinked, cure the formulation under suitable conditions (e.g., UV light for photocurable systems or mild heating for thermally activated cure).\n\n---\n\n### **Step 5: Verification of Successful Incorporation**\n8. **Visual/Physical Inspection**:\n    - Inspect for macroscopic uniformity (e.g., absence of phase separation, visible aggregates).\n    - Measure viscosity changes in the formulation (increased viscosity often indicates successful hydrogen-bonding interactions).\n\n9. **Chemical and Structural Analysis**:\n    - **FTIR Spectroscopy**:\n        - Look for characteristic peaks of UPy groups (e.g., N–H at ~3200–3500 cm⁻¹, C=O at ~1700 cm⁻¹) in the final polymer. Compare it with the pristine spectra of UPy-D400.\n    - **NMR Spectroscopy**:\n        - Confirm the presence of UPy-D400 by detecting signature chemical shifts (e.g. pyrimidinone protons) in the final polymer.\n    - **X-ray Diffraction (XRD)** (if crystalline domains are present):\n        - Check for new crystalline peaks from UPy interactions, which indicate successful interaction and self-assembly in the polymer matrix.\n\n10. **Water Absorption/Contact Angle Testing**:\n    - Validate the enhanced hydrophilicity by measuring water contact angle (should decrease after UPy-D400 incorporation).\n    - Alternatively, perform swelling experiments to test water uptake in hydrophilic environments.\n\n---\n\n### **Conclusion**\nBy following these steps, you can ensure the successful incorporation of UPy-D400 into the polymer formulation. The detailed checks and balances ensure uniform mixing during preparation and adequate verification for successful integration into the polymer structure. This approach provides a systematic synthesis pathway while ensuring reproducibility for experimental success. ✧"
+}
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diff --git a/task2/task2-qa/synthesis of acrylate-based UV thermal dual-cure coatings for antifogging.json b/task2/task2-qa/synthesis of acrylate-based UV thermal dual-cure coatings for antifogging.json
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+{
+  "design_question": "Describe the importance of tetraethylorthosilicate (TEOS) in achieving a hydrophilic polymer film. What specific reaction does TEOS participate in, and how does this contribute to the surface properties of the material?",
+  "design_answer": "To answer your question systematically, let's break it down into clear and logical steps: \n\n---\n\n### **1. Analyzing the Question and Key Points**\n\nThe focus of your question lies on understanding:\n- The **importance of tetraethylorthosilicate (TEOS)** in hydrophilic polymer film preparation.\n- The **specific reaction TEOS undergoes** and its role in modifying surface properties.\n- How these reactions ultimately contribute to the **hydrophilicity of the polymer material's surface**.\n\nUnderstanding the chemistry of TEOS and its ability to interact with polymers to introduce hydrophilicity requires delving into its molecular structure as well as the process of hydrolysis and condensation, core steps in sol-gel chemistry.\n\n---\n\n### **2. Systematic and Detailed Answer**\n\n#### **2.1 The Role and Importance of TEOS**\n\nTetraethylorthosilicate (TEOS, Si(OC₂H₅)₄) is an organosilicate compound widely used in sol-gel processes to introduce silica-based functionalities to materials. Its role in the preparation of hydrophilic polymer films is essential for the following reasons:\n\n1. **Hydrophilic Functional Group Introduction**:\n   TEOS reacts to produce silanol groups (-SiOH) on hydrolysis, which are inherently hydrophilic. These silanol groups can interact with water molecules through hydrogen bonding, enhancing surface hydrophilicity.\n\n2. **Improving Uniformity and Cross-Linking**:\n   TEOS undergoes condensation reactions, leading to silica network formation. This silica layer provides a stable, interconnected architecture on the polymer surface, thereby enhancing its physical properties and distributing hydrophilicity uniformly.\n\n3. **Customizable Surface Functionalization**:\n   By controlling TEOS reaction parameters (e.g., pH, temperature, time, solvent), the density of silanol groups and their spatial distribution can be fine-tuned to achieve desired hydrophilicity.\n\n#### **2.2 The Specific Reaction TEOS Participates In**\n\nTEOS participates in a **two-step reaction process** characteristic of sol-gel chemistry:\n\n1. **Hydrolysis**:\n   TEOS reacts with water in the presence of an acid or base catalyst to generate silanol groups (-SiOH). This step typically occurs as follows:\n   \\[\n   Si(OC₂H₅)₄ + 4H₂O → Si(OH)₄ + 4C₂H₅OH\n   \\]\n   Here, hydrolysis replaces ethoxy groups (-OC₂H₅) on the TEOS molecule with hydroxyl groups (-OH), resulting in the formation of silicic acid (Si(OH)₄) and ethanol (C₂H₅OH) as a by-product.\n\n2. **Condensation**:\n   The silanol groups formed in the hydrolysis step undergo condensation reactions, resulting in the formation of siloxane bonds (-Si-O-Si-), which create a solid silica network:\n   \\[\n   Si(OH)₄ + Si(OH)₄ → Si-O-Si + H₂O\n   \\]\n   Alternatively:\n   \\[\n   Si(OH)₄ + Si(OC₂H₅)₄ → Si-O-Si + C₂H₅OH\n   \\]\n   These reactions lead to the development of a three-dimensional silica matrix.\n\n#### **2.3 Contribution to Hydrophilic Surface Properties**\n\nOnce the silica layer forms, the material surface gains desirable hydrophilic properties due to:\n- The presence of **free silanol groups (-SiOH)** on the exposed surface. These groups engage in hydrogen bonding with water, significantly increasing surface wettability.\n- The intrinsic **porosity** of the silica network, which supports water absorption and adhesion at the interface.\n  \nIn polymer films, this process facilitates enhanced interaction with aqueous environments, making them suitable for applications in fields like separation membranes, biomedical devices, and coatings that require hydrophilic properties.\n\n---\n\n### **3. Experimental Preparation Scheme for a TEOS-Based Hydrophilic Polymer Film**\n\nHere is a step-by-step guide to synthesizing a hydrophilic polymer film using TEOS via sol-gel chemistry:\n\n#### **Step 1: Materials Required**\n- Tetraethylorthosilicate (TEOS): 98% purity or higher.\n- Polymer substrate: A suitable hydrophobic polymer (e.g., poly(dimethylsiloxane) (PDMS), polystyrene, etc.).\n- Solvents: Ethanol (C₂H₅OH) as a co-solvent to ensure miscibility.\n- Deionized water (H₂O): For hydrolysis.\n- Acidic Catalyst: Hydrochloric acid (HCl) or acetic acid as a catalyst (preferred pH: 2–3).\n- Optional: Organosilanes such as 3-aminopropyltrimethoxysilane (APTMS) for further functionalization.\n\n#### **Step 2: Preparation of Sol Solution**\n1. Dissolve TEOS in ethanol at a TEOS-to-ethanol molar ratio of approximately **1:4**.\n2. Add deionized water to achieve a water-to-TEOS molar ratio of **4:1**, sufficient for full hydrolysis.\n3. Introduce a small amount of acid (HCl) to the solution. Begin with 0.01 M and adjust as necessary to maintain pH at 2–3. This acidic environment catalyzes the hydrolysis reaction.\n4. Stir the solution continuously at room temperature for 1–2 hours to allow hydrolysis to occur.\n\n#### **Step 3: Coating Polymer Substrate**\n1. Clean the surface of the hydrophobic polymer substrate (e.g., PDMS) thoroughly to remove dust, grease, or oils.\n   - Use isopropanol and deionized water for cleaning.\n2. Apply the sol solution to the polymer substrate using one of the following techniques:\n   - **Dip Coating**: Immerse the substrate into the sol solution and withdraw it at a controlled speed to create a uniform film.\n   - **Spin Coating**: Deposit a small amount of sol solution onto the substrate and spin it at ~2000–3000 rpm to achieve a uniform coat.\n\n#### **Step 4: Gelation and Aging**\n1. Allow the coated substrate to rest at room temperature or slightly elevated temperature (e.g., 40°C) for several hours to facilitate gelation.\n2. During this step, condensation reactions will densify the silica layer and establish siloxane bonds.\n\n#### **Step 5: Curing**\n1. Cure the sample by heating it at a temperature range of **60–120°C** for 4–8 hours. This step removes any remaining solvent and consolidates the silica network.\n2. Optionally, higher curing temperatures (~200°C) may be used if the polymer substrate can tolerate it for better condensation of siloxane bonds.\n\n#### **Step 6: Characterization of Surface Hydrophilicity**\n- **Contact Angle Measurement**: Evaluate the success of the process by measuring the water contact angle on the polymer film. A reduction in the angle (e.g., <30°) confirms hydrophilicity.\n- **Fourier Transform Infrared Spectroscopy (FTIR)**: To verify the presence of silanol (-SiOH) and siloxane (-Si-O-Si-) groups, highlighting successful hydrolysis and condensation.\n\n---\n\n### **4. Summary**\n\nTEOS plays a pivotal role in creating hydrophilic polymer films through its hydrolysis and condensation reactions in sol-gel chemistry. The introduction of silanol groups and a silica network significantly enhances the surface's hydrophilicity. By customizing processing parameters (e.g., pH, water content, curing time), you can optimize the coating process to achieve desired properties. The outlined experimental scheme provides a reliable approach to achieving this goal in the laboratory.\n\nThis comprehensive understanding and experimental outline should equip you with the knowledge and confidence to conduct the experiment successfully."
+}
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diff --git a/task2/task2-qa/uchiyama2015.json b/task2/task2-qa/uchiyama2015.json
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+{
+  "design_question": "Given a molecule like propylene glycol (PG), explain how varying its concentration could impact both the spontaneity of pattern formation on the polymer surface and the resulting hydrophilicity of the material.",
+  "design_answer": "Certainly! This is an excellent question that delves into the interplay between molecular design, reaction conditions, and the resulting polymer surface properties such as hydrophilicity and pattern formation. Let us analyze and systematically address your inquiry step by step.\n\n---\n\n### **Step 1: Analyzing the Question and Identifying Key Points**\n1. **Molecule of Interest:** The molecule provided is **propylene glycol (PG)**, which is a small bifunctional molecule containing two hydroxyl (-OH) groups. These hydroxyl groups are hydrophilic in nature and will play a significant role in both surface hydrophilicity and polymerization.\n  \n2. **Factors Under Study:**\n   - **Varying Concentration of PG:** The concentration of PG during the polymerization process is a variable to be examined.\n   - **Spontaneity of Pattern Formation:** PG concentration may impact the self-assembly process or microphase/macrophase separation during polymerization, which could lead to surface pattern formation.\n   - **Hydrophilicity of the Material:** Surface hydrophilicity depends on the distribution and availability of hydrophilic functional groups (e.g., hydroxyl groups) exposed on the polymer surface.\n\n3. **Goal:** To explain the relationship between **PG concentration** and its effect on **pattern formation** as well as on the **hydrophilicity** of the resulting polymer.\n\n---\n\n### **Step 2: Systematic Explanation**\n#### **Background Concepts**\nBefore diving into the synthesis scheme, it is essential to understand how PG contributes to polymerization and surface hydrophilicity:\n- PG is often used as a co-monomer or chain extender in polymer systems. Its primary action is to introduce hydroxyl groups into the polymer matrix.\n- Higher concentrations of PG can lead to an increase in hydrophilic functional groups, which improves the surface hydrophilicity.\n- Surface pattern formation can arise spontaneously due to phase separation (hydrophilic vs. hydrophobic domains) during polymerization or post-polymerization annealing.\n\n---\n\n### **Step 3: Experimental Preparation Scheme**\nTo study the effect of PG concentration, we will outline a typical polymerization reaction using a base polymer (such as polyethylene glycol diacrylate (PEGDA)) with PG incorporated. The experimental steps are as follows:\n\n---\n\n#### **Step 3.1: Materials and Reagents**\n1. **Base Polymer Precursor:** Polyethylene glycol diacrylate (PEGDA).\n2. **Hydrophilic Modifier:** Propylene glycol (PG).\n3. **Crosslinker (if needed):** Ethylene glycol diacrylate (EGDA) or similar.\n4. **Photoinitiator (if UV-polymerizable):** 2-hydroxy-2-methylpropiophenone.\n5. **Solvent (if applicable):** Dimethyl sulfoxide (DMSO) or deionized water.\n6. **Other Required Equipment:** UV light source (if photopolymerization), mold/template, mixers, etc.\n\n---\n\n#### **Step 3.2: Reaction Scheme and Process**\nThis scheme assumes a UV-curable system using PEGDA as the base polymer.\n\n1. **Solution Preparation:**\n   - Weigh out PEGDA (e.g., 1 mmol, based on your target polymer chain length and density).\n   - Dissolve PEGDA in a suitable solvent (e.g., DMSO or water) to a fixed total volume (e.g., 10 mL).\n   - Gradually add **propylene glycol** (PG) to the solution. Vary its concentration across different batches for comparison. Suggested PG concentrations: 0.1 mmol (low), 0.5 mmol (medium), and 1 mmol (high).\n\n2. **Crosslinking and Initiation:**\n   - Add a crosslinking agent (e.g., EGDA, 0.1 mmol if used) to control polymer network density.\n   - Add a photoinitiator (e.g., 0.05 mmol) into the mixture.\n   - Ensure the solution is homogeneously mixed before polymerization.\n\n3. **Polymerization (Reaction):**\n   - Pour the solution into a mold or onto a flat surface for thin-film preparation.\n   - Expose the mixture to UV light (wavelength: 365 nm) for 5–15 minutes, depending on the thickness of the sample and intensity of the UV source. Crosslinking will be triggered by the initiator.\n\n4. **Post-Processing:**\n   - Rinse the resulting polymer in deionized water to remove unreacted monomers or initiators.\n   - Dry the polymer under vacuum or room temperature, depending on the volatility of the solvent.\n\n---\n\n#### **Step 3.3: Characterization of Results**\n1. **Surface Pattern Formation:**\n   - Use AFM (Atomic Force Microscopy) or SEM (Scanning Electron Microscopy) to observe the formation of micro/nano-patterns on the polymer surface. Monitor how the PG concentration affects phase separation and the resulting patterns.\n\n2. **Hydrophilicity Measurements:**\n   - Measure the **contact angle** of water droplets on the polymer surface. Lower contact angles indicate higher hydrophilicity.\n   - Perform water absorption or swelling studies, which are strongly influenced by the concentration of hydroxyl-rich PG.\n\n---\n\n### **Step 4: Expected Results and Analysis**\n#### **Effect of PG on Pattern Formation:**\n- **Low PG Concentration:** At lower concentrations, PG may not significantly contribute to hydrophilic phase domains. Hence, pattern formation on the surface may be absent or negligible.\n- **Medium PG Concentration:** With moderate PG levels, phase separation may occur, leading to microstructured patterns due to competing hydrophilic and hydrophobic interactions.\n- **High PG Concentration:** Excess PG promotes more hydrophilic interactions, which could result in finer patterns or even homogeneous hydrophilic surfaces.\n\n#### **Effect of PG on Hydrophilicity:**\n- Higher concentrations of PG should lead to an increase in surface hydrophilicity due to the availability of hydroxyl groups. \n- However, excessive PG may sometimes lead to poorer crosslinking or reduce mechanical properties, so careful optimization is required.\n\n---\n\n### **Step 5: Conclusion**\nBy systematically varying the concentration of propylene glycol in the reaction mixture, you can study its influence on surface micro/nano-pattern formation and hydrophilicity. Ensure that the polymerization reaction is well-controlled and that post-synthesis characterization is thorough to understand the trends in detail.\n\nDetailed execution of the steps outlined will allow you to successfully complete the experiment and gain insight into the interplay between PG concentration, surface morphology, and hydrophilicity."
+}
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diff --git a/task2/task2-qa/water drop-surface interactions as the basis for the design of anti-fogging surfaces.json b/task2/task2-qa/water drop-surface interactions as the basis for the design of anti-fogging surfaces.json
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+{
+  "design_question": "Explain how you would evaluate the effectiveness of a molecule in reducing condensation and fogging on the surface of the polymer after modifying it. What tests or measurements would you implement to confirm the hydrophilicity enhancement?",
+  "design_answer": "Certainly, let's approach this question step by step, analyzing it thoroughly to ensure clarity and completeness. To evaluate the effectiveness of a molecule in reducing condensation and fogging on the surface of a polymer after modification, and subsequently confirm hydrophilicity enhancement, several systematic tests and measurements can be implemented. I'll provide a detailed procedure below.\n\n---\n\n### Step 1: **Key Considerations and Context Analysis**\nBefore designing the experimental evaluation scheme, the following aspects must be clarified and emphasized:\n1. **Objective**: Assess whether the modification enhances the hydrophilicity of the polymer and effectively reduces condensation and fogging.\n2. **Target Property**: Hydrophilicity should be quantified through measurable parameters, such as water contact angle, surface energy, or anti-fogging performance.\n3. **Practical Applicability**: The polymer's performance must be tested under realistic conditions (e.g., environments that mimic condensation or fogging scenarios).\n4. **Test Methods**: A combination of qualitative (visual) and quantitative (scientific) methods should be used.\n\n---\n\n### Step 2: **Experimental Design for Evaluation**\nTo systematically evaluate the effectiveness of the modified polymer, follow these experimental steps:\n\n#### A. **Surface Hydrophilicity Measurement**\nThe hydrophilicity of the polymer surface can be quantitatively assessed using the water contact angle test.\n\n1. **Apparatus**: Use a **goniometer** to measure the water contact angle on the polymer surface.\n2. **Procedure**:\n    - Place a water droplet (typically ~3–5 μL) on the polymer surface.\n    - Measure the contact angle formed between the baseline of the droplet and the tangent at the droplet contour using the goniometer.\n3. **Expected Results**:\n    - A reduction in the water contact angle indicates improved hydrophilicity. For hydrophilic polymers, the contact angle should ideally be <50°, with values closer to ~10° denoting excellent hydrophilicity.\n4. **Repetition**:\n    - Perform measurements at multiple points on the polymer surface to confirm uniform hydrophilicity after modification.\n    - Average the gathered contact angle data to reduce variability.\n\n#### B. **Anti-Fogging Performance Test**\nEvaluate the polymer’s effectiveness in reducing fogging under controlled environmental conditions.\n\n1. **Apparatus**:\n    - **Fog chamber** or a controlled humidity chamber that simulates condensation conditions.\n    - Heating and cooling equipment to alternate between temperature gradients.\n2. **Procedure**:\n    - Place the polymer sample inside the fog chamber.\n    - Introduce humid air or water vapor to stimulate fog formation.\n    - Cycle the temperature to create a condensation scenario (e.g., cooling the surface rapidly under high humidity).\n    - Observe fog formation visually.\n3. **Qualitative Criteria**:\n    - Observe if the modified polymer remains clear or becomes foggy during condensation. Hydrophilic surfaces spread water droplets into thin films, preventing fogging.\n4. **Quantitative Measurement**:\n    - Use **transmittance spectroscopy** to compare light transmission before and after condensation. A highly hydrophilic surface should maintain high transmittance (close to ~90%) even under fogging conditions.\n\n#### C. **Surface Energy Analysis**\nQuantify the surface energy to corroborate hydrophilicity enhancement.\n\n1. **Methods**:\n    - Employ **contact angle measurements** of multiple liquids with varying polarities (e.g., water, ethylene glycol, diiodomethane).\n    - Use the equations from the **sessile drop method** or the **Owens-Wendt model** to calculate the surface energy.\n2. **Expected Results**:\n    - Hydrophilic surfaces exhibit higher polar surface energy (dominated by high polarity components), which indicates improved interaction with water molecules.\n\n#### D. **Durability Testing of Hydrophilicity**\nEvaluate the longevity of the hydrophilic properties to ensure stable performance.\n\n1. **Tests**:\n    - Subject the polymer to repeated fog formation and wiping cycles (mechanical durability).\n    - Expose the polymer to UV light or temperature fluctuations to test chemical stability.\n2. **Criteria**:\n    - Consistent performance in condensation/fogging tests and unchanged water contact angle post-testing indicates durable hydrophilicity.\n\n#### E. **Chemical Characterization**\nIf surface modifications involve molecular or structural changes, confirm the presence of functional groups responsible for hydrophilicity enhancement.\n\n1. **Methods**:\n    - **FTIR spectroscopy**: Confirm characteristic functional groups such as hydroxyl (-OH) or amine (-NH2) groups added during modification.\n    - **XPS (X-ray photoelectron spectroscopy)**: Analyze surface elemental composition and confirm incorporation of hydrophilic components.\n2. **Criteria**:\n    - The appearance of hydrophilic functional groups (e.g., -OH peaks at ~3300 cm⁻¹ in FTIR) demonstrates successful modification.\n\n---\n\n### Step 3: **Systematic Data Analysis**\nAfter conducting the outlined experiments, analyze the gathered data for clear insights:\n1. **Compare Pre- and Post-Modification Results**: Determine the reduction in contact angle, improvement in anti-fogging performance, and increase in surface energy.\n2. **Correlate Observations**: Relate visual results (e.g., fog formation) with quantitative metrics (contact angle, transmittance percentage).\n3. **Confirm Consistency**: Ensure all metrics point toward improved hydrophilicity. Any discrepancies should be investigated (e.g., uneven modification distribution).\n\n---\n\n### Step 4: **Conclusion and Practical Recommendations**\nIf the polymer successfully meets the criteria above:\n- **Hydrophilicity Confirmation**: Reduced contact angle, higher surface energy, and effective anti-fogging behavior validate the molecule’s effectiveness.\n- **Application Advice**: Recommend optimized synthesis and surface modification techniques for scaling production in future applications.\n\nIf the results show insufficient enhancement:\n- Suggest further optimization of the surface modification process, such as increasing the functional group density, altering reaction conditions, or trying additional hydrophilic compounds.\n\n---\n\nBy following this systematic experimental plan, both qualitative and quantitative evaluations will provide robust proof of hydrophilicity enhancement and anti-fogging effectiveness. This ensures a scientific, logical, and precise approach for assessing the polymer’s performance."
+}
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diff --git a/task2/task2-qa/xu2012.json b/task2/task2-qa/xu2012.json
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+{
+  "design_question": "In your synthesis of hydrophilic polymers, if isophorone diisocyanate (IPDI) is used to form a prepolymer, how would you ensure that the functional groups required for increased hydrophilicity are introduced into the polymer structure?",
+  "design_answer": "To address your question systematically, let's analyze the problem and summarize key points:\n\n### Key Points:\n1. **Objective**: The synthesis involves using isophorone diisocyanate (IPDI) as a key reagent to form a prepolymer, and the goal is to introduce functional groups into the polymer structure that enhance hydrophilicity.\n2. **Challenge**: Isophorone diisocyanate contains isocyanate (-NCO) groups which offer reactivity for further modification. To achieve hydrophilicity, we need hydrophilic functional groups like hydroxyl (-OH), carboxylic (-COOH), sulfonic (-SO3H), or amine (-NH2).\n3. **Approach**: The experimental scheme should include:\n   - Reaction conditions to form the initial prepolymer with IPDI.\n   - Introduction of hydrophilic functional groups through precise chemical reactions.\n   - Control of reagent ratios, reaction conditions, and steps for purification.\n\nHere’s the detailed experimental preparation scheme:\n\n---\n\n### Step-by-Step Synthesis Scheme:\n\n#### **Step 1: Formation of the Prepolymer**\n- **Objective**: React IPDI with a polyol to form the prepolymer containing pendant functional groups.\n- **Reagents**:\n  - IPDI: Acts as the diisocyanate source.\n  - Polyol: Choose a hydrophilic polyol such as polyethylene glycol (PEG) or glycerol to introduce intrinsic hydrophilicity. PEG with molecular weight 400-1000 g/mol is recommended for moderate chain length.\n- **Procedure**:\n  1. Dissolve PEG (or the polyol of choice) in anhydrous dimethylformamide (DMF) or tetrahydrofuran (THF).\n  2. Add a catalytic amount (0.2–0.5% w/w) of dibutyltin dilaurate (DBTDL) as the catalyst.\n  3. Gradually add IPDI to the stirred solution under nitrogen atmosphere or inert conditions to prevent moisture interference.\n  4. Maintain reaction at 70–80°C for 3–4 hours while stirring continuously to allow efficient reaction of -NCO groups with hydroxyl (-OH) groups of PEG.\n  5. Monitor the reaction using FTIR spectroscopy to ensure disappearance of the excess -NCO peak (~2260 cm⁻¹) corresponding to unreacted isocyanate.\n\n---\n\n#### **Step 2: Introduction of Hydrophilic Functional Groups**\n- **Objective**: Incorporate specific terminal hydrophilic groups that enhance water affinity beyond the hydrophilicity from PEG.\n- **Reagents**:\n  - Amino acids (e.g., lysine for -NH2 groups or glutamic acid for -COOH groups).\n  - Chain extenders with hydrophilic groups, such as diethanolamine (provides hydroxyl and amine groups).\n- **Procedure**:\n  1. After forming the IPDI-polyol prepolymer, cool the reaction mixture to room temperature.\n  2. Prepare an aqueous or alcoholic solution of the chosen hydrophilic reagent (e.g., lysine or glutamic acid).\n  3. Slowly add the solution to the prepolymer mixture under stirring. Monitor stoichiometric ratios carefully:\n     - For lysine: Use 1 mol equivalent of lysine per unreacted -NCO group.\n     - For diethanolamine: Use 1.2–1.3 mol equivalents per -NCO group to ensure full reaction.\n  4. Resume stirring at 50–70°C for 6–8 hours, ensuring complete grafting of functional groups.\n  5. Verify the incorporation by FTIR or NMR spectroscopy:\n     - FTIR: Appearance of peaks ~3300 cm⁻¹ (NH2 stretching) or ~1720 cm⁻¹ (-COOH stretching).\n     - NMR: Chemical shifts corresponding to the hydrophilic groups.\n\n---\n\n#### **Step 3: Finalization of the Polymer**\n- **Objective**: Purify the hydrophilic polymer and process it into usable form.\n- **Procedure**: \n  1. Precipitate the polymer by slowly adding the reaction mixture into excess cold water or ethanol, depending on solvent solubility.\n  2. Filter the precipitate and wash thoroughly to remove unreacted reagents or by-products.\n  3. Dry under vacuum at 50–60°C for 12–24 hours until moisture content is eliminated.\n  4. Characterize the final polymer for hydrophilicity:\n     - Test water contact angle (expected to be < 60° for highly hydrophilic polymers).\n     - Measure swelling behavior in water or other polar solvents.\n\n---\n\n### Notes for Reaction Optimization:\n1. **Molar Ratios**: Ensure tight control of the molar ratios of IPDI, polyol, and hydrophilic chain extenders to avoid issues of cross-linking or incomplete functionalization.\n2. **Catalyst Use**: Avoid excessive catalyst concentrations as this may lead to side reactions and degrade product quality.\n3. **Reaction Atmosphere**: Isocyanates are moisture-sensitive; use a dry nitrogen atmosphere throughout the experiment.\n4. **Solvent Choice**: DMF is highly effective for dissolving reagents but toxic. Ensure proper ventilation or consider THF for safer handling.\n\n---\n\n### Conclusion:\nThe synthesis involves forming an IPDI-based hydrophilic prepolymer using PEG or glycerol, followed by functionalization with amino acids or hydrophilic extenders like diethanolamine. Reaction conditions (temperature, molar ratios, and atmosphere) should be finely tuned, and purification processes optimized for high-yield, hydrophilic polymer production.\n\nFeel free to discuss any further modifications or inquire if you're unclear about any steps!"
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diff --git a/task2/task2-qa/zhang-et-al-2024-robust-uv-curable-dual-cross-linked-coating-with-increased-transparency-long-term-antifogging-and.json b/task2/task2-qa/zhang-et-al-2024-robust-uv-curable-dual-cross-linked-coating-with-increased-transparency-long-term-antifogging-and.json
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+{
+  "design_question": "Describe the steps you would take to prepare a dual-cross-linked hydrophilic polymer coating using quaternary ammonium groups. Why do you think these groups are important in modifying the surface properties of the polymer?",
+  "design_answer": "To answer your question regarding the preparation of a dual-cross-linked hydrophilic polymer coating using quaternary ammonium groups, I will analyze the key aspects of the question, systematically provide the preparation steps, and delve into the details necessary for experimental implementation. Additionally, I will explain why quaternary ammonium groups are important for modifying the surface properties of the polymer.\n\n---\n\n**Analysis of the Question:**\n\n1. **Key Objectives:**\n   - To design a dual-cross-linked hydrophilic polymer coating.\n   - Incorporate quaternary ammonium groups into the polymer structure.\n   - Enhance surface hydrophilicity and functionality.\n\n2. **Quaternary Ammonium Groups:**\n   These positively charged groups can impart antibacterial properties, improve ionic conductivity, enhance hydrophilicity, and contribute to electrostatic interactions.\n\n3. **Dual-cross-linked Polymer:**\n   Dual cross-linking typically involves two distinct cross-linking strategies, such as covalent bonds and ionic interactions, to improve mechanical stability, durability, and functionality.\n\n---\n\n**Step-by-Step Preparation of Dual-Cross-Linked Hydrophilic Polymer Coating:**\n\n### Step 1: **Selection of Base Polymer**\nChoose a base polymer capable of functionalization with quaternary ammonium groups and suitable for cross-linking. For this experiment, polyvinyl alcohol (PVA) is an excellent candidate due to its hydrophilicity, ease of functionalization, and compatibility with cross-linking strategies.\n\n- **Materials Needed:** PVA (with molecular weight ~85,000–124,000 g/mol), deionized water, stirring apparatus.\n- **Procedure:**\n  - Dissolve PVA in deionized water at 80°C under constant stirring to prepare a 10 wt.% aqueous solution. Ensure complete dissolution to form a homogeneous polymer solution.\n\n---\n\n### Step 2: **Functionalization with Quaternary Ammonium Groups**\nIntroduce quaternary ammonium groups into the polymer structure via chemical reactions or grafting.\n\n- **Reagents:**\n  - Epichlorohydrin (cross-linking agent).\n  - Trimethylamine or a similar tertiary amine (to form quaternary ammonium groups).\n- **Procedure:**\n  1. Add epichlorohydrin dropwise (molar ratio: PVA:epichlorohydrin = 1:1) to the cooled PVA solution (~30°C) while maintaining stirring.\n  2. After homogenization, introduce trimethylamine (molar ratio trimethylamine:epichlorohydrin = 1:1) to the solution.\n  3. Allow the reaction to proceed for 4–6 hours at 50°C under mild stirring.\n  4. Monitor the reaction using FTIR or ^1H NMR to verify the formation of quaternary ammonium groups.\n  5. Dilute the solution to adjust viscosity, if required.\n\n---\n\n### Step 3: **Covalent Cross-Linking**\nEstablish the first cross-linking network through covalent bonding.\n\n- **Reagents:**\n  - Glutaraldehyde (as a secondary cross-linker).\n- **Procedure:**\n  1. Add glutaraldehyde to the final quaternized polymer solution (molar ratio glutaraldehyde:PVA = 1:2).\n  2. Maintain stirring at room temperature (~25°C) for 4–8 hours.\n  3. Ensure covalent cross-linking occurs through aldehyde groups reacting with hydroxyl groups on PVA.\n  4. Confirm the cross-linking using gel formation tests or swelling ratio analysis.\n\n---\n\n### Step 4: **Ionic Cross-Linking**\nIntroduce a secondary ionic cross-linking network using divalent or trivalent cations to create additional stability.\n\n- **Reagents:**\n  - Metal ions such as calcium chloride (CaCl₂) or magnesium sulfate (MgSO₄) (ionic cross-linkers).\n- **Procedure:**\n  1. Add an aqueous solution of CaCl₂ (molar ratio CaCl₂:PVA = 1:5) to the polymer coating mixture.\n  2. Allow ionic cross-linking interactions to occur for 1–2 hours with gentle stirring.\n  3. Evaluate ionic cross-linking stability using mechanical tests.\n\n---\n\n### Step 5: **Polymer Coating Application**\nApply the prepared polymer to the target substrate (e.g., glass, metal, or polymer surface).\n\n- **Procedure:**\n  1. Clean the substrate thoroughly (e.g., with ethanol or acetone).\n  2. Dip-coat or spray-coat the polymer solution onto the substrate.\n  3. Dry the coated substrate at 50–70°C for several hours to ensure film formation.\n  4. Characterize the coating's uniformity and adhesion using SEM or AFM.\n\n---\n\n### Step 6: **Characterization**\nAssess the hydrophilic polymer coating for desired properties.\n\n- **Characterization Techniques:**\n  - **Hydrophilicity Test:** Water contact angle measurement to confirm enhanced hydrophilicity.\n  - **Antibacterial Activity:** Zone of inhibition tests to verify the efficacy of quaternary ammonium groups.\n  - **Mechanical Properties:** Tensile testing for polymer strength.\n  - **Chemical Analysis:** FTIR or XPS to confirm the presence of quaternary ammonium groups.\n\n---\n\n**Why Quaternary Ammonium Groups are Important:**\n\n1. **Hydrophilicity:** Quaternary ammonium groups improve water affinity due to their ionic nature, leading to enhanced wetting on the surface.\n2. **Antibacterial Properties:** The positively charged ammonium groups can disrupt bacterial membranes, reducing microbial contamination on the surface.\n3. **Electrostatic Interactions:** These groups enable ionic interaction, which can be exploited for secondary cross-linking or surface functionalization.\n4. **Functional Versatility:** Apart from hydrophilicity, they can also enhance chemical resistance and introduce ionic conductivity, making the coating suitable for diverse applications like biomedical devices or filtration membranes.\n\n---\n\nBy following these steps systematically and precisely, you can successfully prepare a dual-cross-linked hydrophilic polymer coating integrated with quaternary ammonium groups. This process not only optimizes surface hydrophilicity and functionality but also ensures durability and applicability in advanced material systems."
+}
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+{
+  "design_question": "When preparing a hydrophilic polymer using BP and PLGA, explain how you would utilize dichloromethane to dissolve the components and what steps you would take to remove any residual solvent from your material.",
+  "design_answer": "To address your question systematically, I will break down the approach for preparing a hydrophilic polymer using BP (likely referring to Bisphenol or its derivative) and PLGA (Poly(lactic-co-glycolic acid)), specifically focusing on the use of dichloromethane as a solvent while ensuring removal of any residual solvent from the final material. Here is a detailed experimental scheme:\n\n---\n\n### **Analysis of the Question**\n1. **Components:** The reaction involves BP and PLGA as the key reagents. BP is hydrophobic in nature, and PLGA is biodegradable and has tunable hydrophobic-to-hydrophilic ratios depending on its lactide-to-glycolide ratio. To enhance hydrophilicity, blending, modification, or copolymerization will likely be carried out.\n   \n2. **Role of Dichloromethane:** Dichloromethane (DCM) is commonly used in polymer synthesis due to its ability to dissolve a wide range of hydrophobic compounds.\n\n3. **Objective:** Not only to achieve homogeneous mixing and interaction between BP and PLGA using DCM, but also to ensure complete removal of DCM, which is toxic and harmful in the final product.\n\n---\n\n### **Experimental Preparation Scheme**\n#### **Step 1: Materials and Setup**\n1. **Chemicals Required:**\n   - BP (Bisphenol or specified derivative of BP)\n   - PLGA (Poly(lactic-co-glycolic acid))\n   - Dichloromethane (DCM, >99% pure, HPLC grade)\n   - Purified water or ethanol for washing (for later steps).\n\n2. **Equipment:**\n   - Magnetic stirrer\n   - Clean round-bottom flask\n   - Nitrogen or inert gas supply (to avoid interaction with water during dissolution)\n   - Rotary evaporator\n   - Vacuum oven\n   - Precision analytical balance (for stoichiometry)\n   - Vacuum pump\n\n#### **Step 2: Dissolution of Components**\n1. **Ratio Selection (BP and PLGA):**\n   - Consult relevant polymer literature to determine the optimal molar ratio between BP and PLGA. For example:\n     - If BP is to act as a crosslinking agent or functional group modifier, its ratio might range between 5–20 mol% relative to PLGA.\n   - For practicality:\n     Example: Dissolve **1.0 g of PLGA** and **0.1–0.2 g of BP** by weight in DCM.\n\n2. **Dichloromethane as Solvent:**\n   - Transfer **50–100 mL DCM** into a clean, dry round-bottom flask.\n   - Add BP and PLGA to the DCM and seal the flask tightly.\n   - Bubble nitrogen gas into the solution briefly to purge oxygen and moisture.\n\n3. **Homogeneous Mixing:**\n   - Place the round-bottom flask on a magnetic stirrer under ambient conditions.\n   - Stir at **300–500 rpm** for **1–3 hours**, ensuring complete dissolution of both components. The solution should be clear, indicating proper solvation.\n\n---\n\n#### **Step 3: Polymerization or Crosslinking**\n(To enhance hydrophilicity, BP may interact covalently with PLGA chains or function as a surface modifier.)\n\n1. **Reaction Conditions:**\n   - Add any catalyst or co-solvent required for the desired interaction (if needed). For instance:\n     - If a hydroxyl group reaction occurs, catalysts like **triethylamine** may be required.\n   - Maintain room temperature or temperatures slightly above DCM boiling point (**40–50°C**) for reactivity.\n\n2. **Completion:**\n   - Stir for an additional **2–6 hours**, ensuring complete reaction.\n\n---\n\n#### **Step 4: Removal of Residual DCM**\nSince dichloromethane is volatile and toxic, carefully removing it is critical.\n\n1. **Rotary Evaporation:**\n   - Transfer the polymer solution into a rotary evaporator. Adjust the following settings:\n     - Temperature: **40–50°C**\n     - Vacuum pressure: **200–300 mbar**\n   - Gradually evaporate DCM while spinning the flask, ensuring the flask contents do not overheat (PLGA degrades above 60°C).\n\n2. **Vacuum Drying:**\n   - Transfer the dried polymer to a vacuum oven to remove trace amounts of DCM:\n     - Temperature: **40–45°C** (below PLGA's glass transition temperature).\n     - Vacuum pressure: Absolute pressure **<50 mbar**.\n     - Time: **8–12 hours** to ensure complete solvent removal.\n\n3. **Testing for Residual Solvent:**\n   - Confirm absence of DCM using techniques such as:\n     - **Gas Chromatography-Mass Spectrometry (GC-MS)**\n     - **Thermogravimetric Analysis (TGA)**\n\n---\n\n#### **Step 5: Post-Treatment to Enhance Hydrophilicity**\nOnce BP and PLGA have interacted or polymerized:\n1. **Hydrophilic Functionalization:**\n   - To further enhance hydrophilicity, consider introducing hydroxyl (-OH) or carboxylic (-COOH) groups onto the polymer surface.\n   - This can be achieved via post-polymerization treatments (e.g., hydrolysis, amidation).\n\n2. **Final Purification:**\n   - Wash the polymer thoroughly with ethanol or water to remove unreacted monomers or impurities.\n   - Dry the washed polymer in a vacuum oven (**30–40°C**, minimum **4 hours**) to regain a solid, purified product.\n\n---\n\n### **Summary of Key Steps**\n1. Dissolve BP and PLGA in DCM using a round-bottom flask under stirring.\n2. Ensure uniform mixing and allow necessary chemical interaction.\n3. Evaporate DCM using a rotary evaporator and vacuum drying.\n4. Characterize the material to confirm solvent removal and hydrophilicity enhancement.\n\nThis systematic approach ensures the preparation of a hydrophilic polymer from BP and PLGA while adhering to laboratory practices and safety precautions."
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+{
+  "design_question": "Describe a detailed procedure for synthesizing a hydrophilic polymer using 2-(dimethylamino)ethyl methacrylate (DMAEMA) as a primary monomer through free radical polymerization. Include steps for purification and any post-modification, if applicable.",
+  "design_answer": "Certainly! To synthesize a hydrophilic polymer using **2-(dimethylamino)ethyl methacrylate (DMAEMA)** as the primary monomer via free radical polymerization, I'll provide a detailed and systematic experimental procedure. Let's analyze the question and move step by step for clarity.\n\n---\n\n### **Key Points of the Question**\n1. **Monomer information**: The main monomer is DMAEMA. This is an amphiphilic monomer and under appropriate conditions, it can be used to synthesize hydrophilic polymers.\n2. **Polymerization technique**: The synthesis should use free radical polymerization, a widely used and versatile method for polymerization.\n3. **Final product**: A hydrophilic polymer, with possible post-modification to increase or enhance hydrophilicity, if required.\n4. **Key steps required**: Detailed description of the **synthesis process**, **purification**, and **post-modification** with reaction specifics.\n\n---\n\n### **Detailed Procedure**\n\n#### **I. Materials and Reagents**\n- **2-(Dimethylamino)ethyl methacrylate (DMAEMA)** (monomer) - ensure it is inhibitor-free.\n- **Azoisobutyronitrile (AIBN)** - a thermal free radical initiator.\n- Solvent: Ethanol or a water-ethanol mixture (acts as the reaction medium and enhances hydrophilicity).\n- Deionized (DI) water.\n- Methanol (for purification by precipitation).\n- Optional post-modification reagents:\n  - **Hydrochloric acid (HCl)** (to quaternize amines and increase charge/hydrophilicity).\n\n---\n\n#### **II. Instrumentation**\n- Round-bottom flask with **magnetic stirrer** and reflux condenser.\n- Oil bath or water bath for controlled heating.\n- Nitrogen gas source for creating an inert atmosphere.\n- Rotary evaporator.\n- Ultrafiltration or dialysis membrane (for purification).\n\n---\n\n#### **III. Experimental Scheme**\n\n---\n\n### **Step 1: Monomer Preparation**\n1. **Remove inhibitors**: Commercial DMAEMA monomers usually contain inhibitors like hydroquinone or MEHQ (to prevent premature polymerization). You must remove them before polymerization. \n   - Pass the monomer through a **basic alumina column** to adsorb the inhibitors.\n   - Alternatively, you can perform a **distillation under reduced pressure** to purify the monomer.\n\n2. Store the purified monomer in a dry, nitrogen-filled sealed container to prevent degradation.\n\n---\n\n### **Step 2: Polymerization Reaction**\n\n**1. Preparation of Reaction Solution:**\n- Add monomer (DMAEMA) and solvent (ethanol or ethanol-water mixture) into a clean, dry 250 mL round-bottom flask.\n  - **Example composition**: For a 1:100 (initiator:monomer) ratio:\n    - DMAEMA: ~10 mL (~66 mmol; density = 0.942 g/mL, molecular weight = 157.2 g/mol).\n    - AIBN: ~0.108 g (0.66 mmol; molecular weight = 164.21 g/mol, as 1% molar ratio to monomer).\n    - Solvent: Add ~40 mL of ethanol or ethanol-water mixture (60:40) to dilute the mixture.\n\n- Ensure the mixture has good stirring to completely dissolve all reagents.\n\n**2. Degassing:**\n- Purge the reaction mixture with nitrogen gas to remove oxygen for ~30 minutes. Oxygen inhibits free radical polymerization by scavenging radicals.\n\n**3. Polymerization:**\n- Attach a reflux condenser to the flask and place the setup in an oil bath preheated to ~65°C.\n- Heat and stir the reaction mixture at this temperature for 8–12 hours.\n  - The specific temperature should be close to the decomposition temperature of AIBN (~65–70°C). Avoid overheating to prevent premature termination.\n  - Monitor the viscosity of the solution over time — increased viscosity indicates polymerization.\n\n---\n\n### **Step 3: Precipitation and Purification**\n1. **Precipitation**:\n   - After completing the reaction, cool the solution to room temperature.\n   - Slowly pour the reaction mixture into a large volume (~300 mL) of cold methanol or diethyl ether with vigorous stirring. This will precipitate the polymer product.\n   - Collect the precipitated polymer by filtration or centrifugation.\n\n2. **Reprecipitation**:\n   - Dissolve the polymer in a minimum amount of ethanol or DI water (depending on polymer solubility), then reprecipitate in cold methanol or diethyl ether. Repeat this process twice to remove unreacted monomers, initiator, and byproducts.\n\n3. **Drying**:\n   - Transfer the purified polymer to a vacuum oven or desiccator and dry at ~40–50°C (or ambient temperature) under reduced pressure for 24 hours to obtain the final polymer.\n\n---\n\n### **Step 4: Post-Modification (Optional)**\nTo enhance hydrophilicity, DMAEMA polymers can be chemically modified:\n\n- **Quaternization**:\n  - Dissolve the polymer in an ethanol-water mixture and add a few drops of concentrated HCl (or other acids like CH3I for methylation).\n  - Stir the mixture at room temperature for ~12 hours. The tertiary amines in DMAEMA will quaternize to form positively charged ammonium salts, significantly enhancing hydrophilicity.\n  - Purify the quaternized polymer by dialysis (using DI water) or precipitation, as described earlier.\n\n---\n\n### **Step 5: Characterization**\nOnce the final polymer is prepared, conduct the following characterization techniques:\n1. **Gel Permeation Chromatography (GPC)**: To determine molecular weight distribution (e.g., weight-average and number-average molecular weights, \\( Mw \\) and \\( Mn \\)).\n2. **Fourier Transform Infrared (FTIR) spectroscopy**: Confirm the chemical structure and identify functional groups (e.g., quaternized ammonium groups, C=O stretching from methacrylate backbone).\n3. **Dynamic Light Scattering (DLS)**: If using in aqueous solution, measure solubility, hydrodynamic diameter, or zeta potential.\n4. **Contact angle measurements**: Assess surface hydrophilicity.\n5. **Nuclear Magnetic Resonance (NMR)**: Verify polymerization efficiency and quantify chemical modification.\n\n---\n\n### **Summary**\nBy following this detailed free radical polymerization procedure, you will synthesize a hydrophilic polymer from DMAEMA. Optional quaternization further enhances hydrophilicity by introducing charged groups. Ensure proper purification and characterization for high-quality polymer products.\n\nFeel free to clarify any step or request further specific details!"
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+{
+  "design_question": "Describe a detailed experimental scheme for incorporating TMP(EO)3TA into a polymer matrix to enhance hydrophilicity. Outline the mixing, curing, and thickness measurement steps clearly.",
+  "design_answer": "To design a detailed experimental scheme for incorporating TMP(EO)₃TA (Trimethylolpropane triethoxylated triacrylate) into a polymer matrix to enhance hydrophilicity, we must carefully analyze the question, break it down into its essential components, and address each step of the synthetic process systematically. The preparation scheme will include mixing, curing, and thickness measurement. Let’s proceed step by step:\n\n---\n\n### **Step 1: Analyzing the Task**\n**Key Points of the Question**:\n1. **Incorporating TMP(EO)₃TA** into a polymer matrix to enhance hydrophilicity.\n2. Systematic detailing of **mixing**, **curing**, and **thickness measurement** steps.\n3. Emphasis on reaction conditions, reagent ratios, molar quantities, and clear experimental instructions.\n\nTMP(EO)₃TA is a hydrophilic acrylate monomer with ethylene oxide groups that improve water affinity. Introducing it into a polymer matrix typically involves free radical polymerization, where it serves as a crosslinker or co-monomer. By appropriately tailoring the formulation, curing, and processing conditions, this compound can significantly enhance the polymer's hydrophilicity.\n\n---\n\n### **Step 2: Materials Required**\n1. **TMP(EO)₃TA** (hydrophilic monomer).\n2. **Base polymer matrix** (e.g., polyethylene glycol dimethacrylate (PEGDMA) or other acrylate-based matrix).\n3. Initiator: **2,2’-Azobis(2-methylpropionitrile) (AIBN)** or **Irgacure-2959** for UV-initiated curing.\n4. Solvent: **Ethanol** or **DI water** (to enhance mixing and dissolve reactants).\n5. Substrate: Glass or silicon wafer for thin film deposition.\n6. Lab equipment: Spin coater (optional), UV curing station, precision micrometer or profilometer.\n\n---\n\n### **Step 3: Experimental Scheme**\n#### **A. Mixing Step**\nThe goal is to prepare a homogeneous solution containing TMP(EO)₃TA and the polymer matrix.\n\n1. **Reaction Mixture Preparation**:\n   - **Base Polymer Solution**: Dissolve 10 g of PEGDMA or another target polymer matrix in 50 mL of ethanol to create a 20% (w/v) solution. Stir at room temperature until complete dissolution (approximately 30 minutes).\n   - **TMP(EO)₃TA Addition**: Add TMP(EO)₃TA to the polymer solution. Typically, use TMP(EO)₃TA at **10-30 wt%** relative to the base polymer to ensure enhanced hydrophilicity. For example:\n     - For 10 g of PEGDMA, add 3 g of TMP(EO)₃TA.\n   - **Initiator Addition**: Add the polymerization initiator (e.g., 0.05 g of AIBN per 10 g of the polymer matrix).\n   - Mix the solution thoroughly under mechanical stirring at 300–500 rpm for 1 hour to ensure homogeneity.\n\n2. **Degassing**:\n   - Place the reaction mixture in a vacuum desiccator for ~15 minutes to remove oxygen and avoid inhibition of free radical polymerization.\n\n---\n\n#### **B. Curing Step**\nCuring will involve polymerization of the TMP(EO)₃TA into the polymer matrix to create a crosslinked hydrophilic network.\n\n1. **Film Preparation**:\n   - Use a spin coater to spread the reaction mixture onto the substrate (e.g., a glass slide or silicon wafer). Spin at **2500 RPM** for 60 seconds to ensure uniform coating. Alternatively, apply the mixture using a drop-casting method for thicker films.\n   - Target initial thickness: **200–500 μm**, depending on application.\n\n2. **Polymerization/Curing**:\n   - **Thermal Curing**:\n     - Place the coated substrate in an oven preheated to 70–80°C for 2 hours. Ensure constant temperature and uniform heat distribution in the oven.\n   - **UV Curing (Preferred for TMP(EO)₃TA)**:\n     - Use a UV curing station with a wavelength range of 365–405 nm.\n     - Irradiate for 5 minutes at **10 mW/cm²** intensity. Extend curing time to 10 minutes if a higher crosslink density is desired.\n\n3. **Post-Curing Treatment**:\n   - After curing, rinse the film gently with DI water to remove unreacted monomers or initiator residues.\n   - Dry the cured polymer samples in an oven at 40°C for 30 minutes.\n\n---\n\n#### **C. Thickness Measurement Step**\n1. **Tools**:\n   - Use a precision micrometer or a profilometer to measure the final thickness of the cured polymer films.\n\n2. **Procedure**:\n   - Select three different regions of the cured film across the substrate to ensure uniformity.\n   - Measure thickness using the profilometer in **nanometer (nm)** or **micrometer (μm)** scales.\n   - Record and average the readings to determine the final thickness. Ensure it aligns with the desired range (e.g., 200–500 μm).\n\n---\n\n### **Step 4: Enhancing Hydrophilicity**\nTo confirm enhanced hydrophilicity:\n1. Perform **contact angle measurements**. A reduced contact angle (<40°) on the cured film indicates hydrophilic behavior.\n2. Conduct **swelling studies**:\n   - Immerse the polymer in DI water and measure weight changes over time to assess water uptake and hydrophilicity.\n\n---\n\n### **Step 5: Notes on Experimental Conditions**\n1. **Safety Considerations**:\n   - Handle TMP(EO)₃TA and initiators with care in a fume hood.\n   - Wear gloves and safety goggles.\n\n2. **Optimization**:\n   - Adjust TMP(EO)₃TA concentration based on desired hydrophilicity. Higher wt% increases hydrophilicity but might reduce mechanical strength.\n\n3. **Storage**:\n   - Store the polymer films in sealed containers to prevent contamination and degradation.\n\n---\n\nThis detailed experimental scheme should enable successful incorporation of TMP(EO)₃TA into the polymer matrix for enhanced hydrophilicity. Let me know if you have further questions or need clarification on specific steps!"
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+{
+  "design_question": "Describe how you would utilize N-butylimidazole to introduce a cationic functional group into a polymer. Include the reaction conditions you would implement to achieve a homogenous product.",
+  "design_answer": "Certainly! Introducing a cationic functional group into a polymer using N-butylimidazole is an excellent way to increase hydrophilicity, as the resulting cationic charges will promote water attraction and solubility. Let’s systematically address your question by analyzing and providing a detailed experimental scheme.\n\n---\n\n### **1. Problem Analysis and Key Points Identification**\nThe goal is to introduce a cationic functional group into a polymer using N-butylimidazole. Here's what we need to focus on:\n- Selection of a polymer backbone that can react with N-butylimidazole to form covalent bonds.\n- Functionalization via a reaction that grafts or incorporates N-butylimidazole-derived cationic groups onto the polymer.\n- Reaction conditions that avoid side reactions and ensure a homogenous product.\n- Specific details on reaction time, temperature, solvents, and mole ratios of reagents.\n\n---\n\n### **2. Experimental Design**\n\n#### **Step 1: Choosing a Suitable Polymer Backbone**\nTo react with N-butylimidazole, the polymer must contain electrophilic groups (e.g., alkyl halides, epoxides, or unsaturated groups). A common example is **poly(ethylene glycol)-bromoalkane** (PEG-Br), where the terminal bromine acts as an electrophile enabling a nucleophilic substitution reaction with the imidazole molecule.\n\nWhy PEG-Br?\n- It's water-compatible, providing inherent hydrophilicity.\n- The bromine on the polymer chain allows for efficient substitution by N-butylimidazole to introduce cationic imidazolium groups.\n\n#### **Step 2: Chemical Reaction Overview**\nThe targeted reaction is **nucleophilic substitution (SN2)** between the alkyl bromide group of the polymer (PEG-Br) and N-butylimidazole:\n\n\\[\nPEG-Br + N\\text{-}butylimidazole \\xrightarrow{\\text{SN2 Conditions}} PEG\\text{-}imidazolium-Bu^+Br^-\n\\]\n\nThe product is a cationic polymer functionalized with butylimidazolium groups, with the bromide acting as the counterion.\n\n#### **Step 3: Detailing the Experimental Procedure**\n\n---\n\n**a) Materials Required:**\n- Poly(ethylene glycol)-bromoalkane (PEG-Br) (molecular weight tailored to your needs, e.g., PEG Mw ~2000 or 4000, functionalized with terminal bromide).\n- N-butylimidazole.\n- Solvent: Acetonitrile (anhydrous, polar aprotic solvent to facilitate the SN2 mechanism).\n- Reaction flask (round-bottom flask with magnetic stirrer or overhead stirrer).\n- Nitrogen or argon gas for an inert atmosphere.\n- Reagents for post-synthesis purification: e.g., diethyl ether for polymer precipitation.\n- Analytical tools: FTIR or NMR for structural confirmation, TGA or DSC for thermal property verification.\n\n---\n\n**b) Reaction Setup:**\n1. **Polymer Dissolution**:\n   - Weigh out a known amount of PEG-Br (e.g., **2 g, ~1 mmol of terminal Br groups**).\n   - Dissolve PEG-Br in 20 mL of anhydrous acetonitrile under inert gas (e.g., nitrogen) with continuous stirring.\n\n2. **Addition of N-butylimidazole**:\n   - Use an equimolar or slight molar excess of N-butylimidazole (1.5 mmol, ~175 mg) to ensure all bromide groups are functionalized. The slight excess minimizes unreacted bromine sites on the polymer.\n   - Add the N-butylimidazole dropwise to the stirred PEG-Br solution under inert conditions.\n\n3. **Reaction Conditions**:\n   - Conduct the reaction at an elevated temperature (~70–80 °C) for optimal SN2 kinetics. Use an oil bath to control the temperature accurately.\n   - Stir the reaction mixture for 12–24 hours to ensure complete substitution. Monitor the reaction progress using thin-layer chromatography (TLC) or by taking aliquots for NMR analysis.\n\n4. **Work-Up**:\n   - Cool the reaction mixture to room temperature.\n   - Precipitate the polymer by slowly adding it to a large volume of cold hydrophobic solvent (e.g., diethyl ether). The cationic polymer will separate as a solid.\n   - Wash the resulting polymer precipitate with diethyl ether multiple times to remove unreacted N-butylimidazole and solvent.\n\n5. **Drying and Storage**:\n   - Dry the purified polymer in a vacuum oven at 40 °C for ~12 hours to remove residual solvent.\n   - Store the dried polymer in a desiccator to preserve its purity.\n\n---\n\n#### **Step 4: Characterization of the Product**\n1. **Structural Confirmation**:\n   - Use **NMR spectroscopy (1H-NMR)** to confirm the presence of cationic imidazolium groups. Peaks corresponding to the imidazole ring and attached butyl group should appear. The integration of these peaks against the PEG backbone provides quantitative confirmation of substitution.\n   - **FTIR analysis**: Look for characteristic peaks around 3100–3300 cm⁻¹ for the imidazole C–H stretch and confirm the absence of any residual C–Br bonds (should disappear at ~500–600 cm⁻¹ in PEG-Br).\n\n2. **Molecular Weight Analysis**:\n   - Determine molecular weight shifts (e.g., using gel permeation chromatography—GPC) as imidazole substitution will slightly increase the polymer's molar mass.\n\n3. **Thermal Properties**:\n   - Perform **DSC (Differential Scanning Calorimetry)** to study any changes in thermal transitions (e.g., glass transition or melting point shifts).\n   - **TGA (Thermogravimetric Analysis)** to examine stability and decomposition temperatures, ensuring polymer integrity.\n\n4. **Evaluation of Hydrophilicity**:\n   - **Contact Angle Measurements**:\n     Harvest the functionalized polymer as a coating or film and measure its water contact angle to confirm enhanced hydrophilicity due to the introduction of cationic groups.\n   - **Water Solubility Test**: Assess the degree of solubility in water or aqueous buffers.\n\n---\n\n### **3. Key Reaction Parameters and Suggestions for Homogeneity**\n- **Stoichiometry**: Use slightly excess N-butylimidazole (1.5 equiv.) to ensure complete substitution.\n- **Solvent Choice**: Polar aprotic solvent (acetonitrile) ensures good solvation for the polymer and promotes the SN2 mechanism.\n- **Temperature Control**: Elevated temperature (70–80 °C) speeds up the reaction, but don’t exceed 90 °C to avoid polymer degradation.\n- **Inert Atmosphere**: Oxygen-free conditions (nitrogen or argon) prevent side reactions that may degrade imidazole or oxidize the polymer backbone.\n\n---\n\n### **4. Conclusion**\nBy reacting PEG-Br with N-butylimidazole under SN2 reaction conditions, we successfully introduce cationic butylimidazolium groups into the polymer. Careful control of reaction conditions ensures a homogenous polymer product, which can significantly enhance hydrophilicity. With this detailed experimental scheme, you should be able to execute the synthesis in a laboratory and validate your results through appropriate characterization techniques.\n\nIf you need clarifications during the synthesis or characterization process, don’t hesitate to ask! Good luck!"
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+{
+  "design_question": "Explain how you would monitor the progress of the polymerization reaction involving MDI using Raman spectroscopy. Identify which spectral feature of MDI you would focus on and how you would use this information to determine the conversion of the reaction.",
+  "design_answer": "Certainly! Let’s systematically approach your question about monitoring the progress of a polymerization reaction involving MDI (methylene diphenyl diisocyanate) using Raman spectroscopy. I’ll break down the process step by step to ensure clarity.\n\n---\n\n### **Step 1: Analyze the Question and Summarize Key Points**\nYour question pertains to monitoring a polymerization reaction involving MDI. Specifically, you are asking:\n- How Raman spectroscopy can be used for this purpose.\n- Which spectral feature of MDI should be monitored.\n- How to determine the reaction's progress (conversion) using the information from Raman spectroscopy.\n\nTo answer comprehensively, I will:\n1. Briefly explain the chemistry of MDI and its relevance to the reaction.\n2. Identify the key Raman-active functional group in MDI to monitor.\n3. Provide step-by-step guidance on using Raman spectroscopy to track conversion during polymerization.\n\n---\n\n### **Step 2: Overview of MDI Chemistry**\nMDI is a diisocyanate widely used in polymerization reactions, particularly in forming polyurethanes. A typical polymerization reaction involving MDI occurs between the –N=C=O (isocyanate groups) of MDI and hydroxyl-containing compounds (such as polyols). During this process:\n- The isocyanate groups react with hydroxyl groups to form urethane linkages (-NH-CO-O-).\n- The consumption of the isocyanate group is a direct indicator of reaction progress.\n\nBecause MDI contains two isocyanate groups per molecule, monitoring the disappearance of the –N=C=O functional group during the reaction is critical for determining the reaction's progress.\n\n---\n\n### **Step 3: Key Raman Spectral Feature of MDI**\nRaman spectroscopy is ideally suited for monitoring isocyanate functionality due to its sensitivity to certain vibrational modes. The key feature for MDI is:\n- The **Raman-active symmetric stretching vibration of the isocyanate group (–N=C=O)**, which typically appears as a strong band in the Raman spectrum around **2230–2270 cm⁻¹**.\n\nThis distinct band is well-separated from other vibrational features, making it ideal for monitoring the consumption of –N=C=O during the reaction.\n\n---\n\n### **Step 4: Experimental Monitoring Procedure with Raman Spectroscopy**\n\n#### **4.1. Initial Setup**\n1. **Instrumentation**: Use a Raman spectrometer equipped with a laser source (commonly 532 nm, 785 nm, or 1064 nm) suitable for your sample. Choose a laser wavelength to minimize fluorescence, especially for aromatic compounds like MDI.\n2. **Sample Preparation**: \n   - Prepare the polymerization reaction mixture by combining MDI with the co-monomer/polyol under controlled stoichiometry.\n   - Ensure the reaction is run in a sealed vessel (if necessary) to prevent moisture from interfering, as isocyanate groups are highly reactive with water.\n3. **Baseline Spectrum of MDI**:\n   - Before starting the reaction, record the Raman spectrum of pure MDI as a reference.\n   - Note the intensity of the isocyanate peak (~2230–2270 cm⁻¹).\n\n#### **4.2. Real-Time Reaction Monitoring**\n1. **Time-Resolved Spectroscopy**:\n   - Collect Raman spectra of the reaction mixture at regular intervals (e.g., every 5–10 minutes) during the polymerization reaction.\n   - Focus on the spectral region around 2100–2300 cm⁻¹ for tracking the isocyanate peak.\n\n2. **Monitoring the Intensity**:\n   - Observe the gradual decrease in the intensity of the isocyanate peak (~2230–2270 cm⁻¹) over time. The decrease indicates the consumption of isocyanate groups as the reaction progresses.\n\n#### **4.3. Quantifying Conversion of MDI**\n1. **Peak Intensity Ratio Method**:\n   - Use the intensity of the isocyanate peak at a specific time, \\( I_t \\), relative to its initial intensity, \\( I_0 \\).\n   - The conversion, \\( X \\), of MDI can be calculated as:\n     \\[\n     X = \\frac{I_0 - I_t}{I_0} \\times 100\\%\n     \\]\n     where \\( I_t \\) is the peak intensity of –N=C=O at time \\( t \\) and \\( I_0 \\) is the initial peak intensity before the reaction starts.\n\n2. **Internal Standard (Optional)**:\n   - To improve accuracy, you can compare the isocyanate peak intensity to an internal standard (a non-reactive spectral feature in the same sample) rather than relying solely on the absolute intensity.\n\n#### **4.4. End-Point Determination**\n- The reaction is considered complete when the isocyanate peak at 2230–2270 cm⁻¹ is no longer detectable, indicating complete consumption of –N=C=O groups.\n- If the intensity plateaus but does not reach zero, it may indicate incomplete reaction due to stoichiometric mismatch, side reactions, or reagent impurities.\n\n---\n\n### **Step 5: Important Considerations**\n1. **Controlling Reaction Conditions**:\n   - Perform the reaction under controlled temperature (typically 50–80°C for urethane formation) and exclude moisture to prevent side reactions.\n2. **Calibration**:\n   - Validate the Raman-based conversion determination by performing parallel experiments with a quantitative chemical analysis method (e.g., FTIR or NMR spectroscopy).\n3. **Interference**:\n   - Ensure no other components in the reaction mixture (e.g., solvents or additives) produce Raman bands overlapping with the –N=C=O region.\n\n---\n\n### **Step 6: Summary**\nTo monitor the polymerization reaction of MDI using Raman spectroscopy, you focus on the isocyanate group’s symmetric stretching band (~2230–2270 cm⁻¹). By tracking the intensity decrease of this band over time, you can determine the reaction conversion. This method is straightforward, non-destructive, and highly sensitive to changes in isocyanate concentration, allowing real-time reaction monitoring in the lab.\n\nWith careful execution of the outlined procedure and attention to details such as calibration and temperature control, you should be able to successfully track your polymerization reaction and evaluate its progress quantitatively.\n\nLet me know if you have further questions or need assistance with experimental design specifics!"
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+{
+  "design_question": "Outline an experimental approach for utilizing acrylic acid (AA) in the synthesis of a hydrophilic polymer. What reactions need to occur to ensure the incorporation of this molecule into the polymer structure?",
+  "design_answer": "Certainly. Let us now address your question methodically, considering the use of acrylic acid (AA) for synthesizing a hydrophilic polymer.\n\n---\n\n### 1. **Analysis of the Question and Key Points**:\n- The primary goal is to prepare a hydrophilic polymer using acrylic acid (AA) as one of the main building blocks.\n- Acrylic acid is a versatile molecule often used in the synthesis of hydrophilic polymers because of its carboxylic acid group (-COOH), which imparts hydrophilicity.\n- To achieve this, we need to strategically polymerize acrylic acid into a more hydrophilic macromolecular structure, ensuring the -COOH groups are preserved or functionalized to enhance hydrophilicity.\n- The two most common approaches include **homopolymerization** (polyacrylic acid) or **copolymerization** with other monomers to introduce additional functionality.\n\nNow, I will outline a step-by-step experimental scheme to create a hydrophilic polymer from acrylic acid, including all relevant reaction conditions and process details.\n\n---\n\n### 2. *Experimental Scheme for Synthesizing a Hydrophilic Polymer Using Acrylic Acid*\n\n#### **Step 1: Selection of Polymerization Method**\nAcrylic acid can be polymerized via free radical polymerization, which is widely used for producing hydrophilic polymers efficiently and reproducibly.\n\n- **Polymerization Strategy**:\n  - **Homopolymerization:** If the goal is to produce poly(acrylic acid) (PAA), acrylic acid is polymerized as the sole monomer.\n  - **Copolymerization:** To further enhance hydrophilicity or introduce specialized properties, AA can be copolymerized with other hydrophilic monomers (e.g., acrylamide, hydroxyethyl methacrylate).\n\nFor simplicity, I will describe both approaches.\n\n---\n\n#### **Step 2: Materials and Reagents**\n- **Monomers**:\n  - Acrylic acid (AA): Ensure it is of high purity (>99% to minimize impurities).\n  - Co-monomers (if needed): Acrylamide (AM) or other vinyl monomers.\n- **Initiator**:\n  - A water-soluble, free radical initiator such as ammonium persulfate (APS).\n- **Crosslinking Agent (if desired)**:\n  - N,N'-methylenebisacrylamide (MBA) can be added to form a crosslinked hydrogel structure.\n- **Solvent**:\n  - Deionized water or a water-organic mixture.\n- **pH Adjuster**:\n  - Sodium hydroxide (NaOH) or other bases if neutralization of acrylic acid is desired for specific properties.\n\n---\n\n#### **Step 3: Reaction Procedure (Homopolymerization of AA)**\n\n1. **Preparation of Reaction Mixture**:\n   - Dissolve acrylic acid monomer in deionized water to prepare a 10–30% (w/v) aqueous solution (depending on desired polymerization density).\n   - Optionally adjust the pH to ~7 by neutralizing a portion of the AA with NaOH, converting -COOH groups into sodium acrylate (-COONa); this will lead to a slightly hydrophilic, charged polymer.\n\n2. **Initiator Solution**:\n   - Dissolve 0.1–0.5% (w/v) ammonium persulfate (APS) in water and add the solution to the AA mixture under gentle stirring.\n\n3. **Polymerization Setup**:\n   - Transfer the solution to a nitrogen-purged reaction vessel (to eliminate oxygen, which inhibits radical polymerization).\n   - Heat the mixture to ~60–70°C while stirring gently; this will activate the persulfate initiator and initiate polymerization through the formation of free radicals on the double bonds of acrylic acid.\n\n4. **Completion**:\n   - Allow the polymerization to continue for 4–6 hours, maintaining a constant temperature.\n   - A viscous solution of poly(acrylic acid) (PAA) will result, with hydrophilic carboxylic acid groups (-COOH) distributed throughout the polymer backbone.\n\n---\n\n#### **Step 4: Reaction Procedure (Copolymerization Example)**\n\nIf copolymerization is desired (e.g., with acrylamide):\n\n1. **Preparation of Monomer Mixture**:\n   - Use a molar ratio of acrylic acid:acrylamide (AA:AM) = 70:30 or adjust based on the desired balance between carboxyl and amide functional groups.\n   - Dissolve the monomers in water similarly as described above, ensuring a total monomer concentration of ~10–20% (w/v).\n\n2. **Initiator and Polymerization Conditions**:\n   - Add ammonium persulfate (0.1–0.5% w/v) along with a crosslinker like MBA (0.1–0.3 mol% of total monomers for hydrogel formation).\n   - Carry out free radical polymerization as outlined in Step 3 under nitrogen atmosphere, heating at 60–70°C.\n\n3. **Resultant Polymer**:\n   - A copolymer of AA and AM (e.g., poly(AA-co-AM)) will be formed, containing both carboxylic acid (-COOH) and amide (-CONH2) groups. This structure is more hydrophilic and can form highly swellable hydrogels.\n\n---\n\n#### **Step 5: Purification of the Polymer**\n- Dialyze the resulting polymer solution against deionized water for 2–3 days to remove unreacted monomers and initiator residues.\n- Alternatively, precipitate the polymer by adding the reaction mixture to a non-solvent (e.g., acetone or ethanol), then filter and dry the polymer under vacuum.\n\n---\n\n### 3. *Ensuring Incorporation of Acrylic Acid into the Polymer Structure*\n\nThe incorporation of acrylic acid into the polymer backbone relies on free radical polymerization, wherein the vinyl double bond (-C=C-) of AA participates in chain growth. Key considerations are:\n- **Initiator Efficiency**: APS ensures rapid formation of free radicals to activate the acrylic acid monomers.\n- **Reaction Control**: Proper temperature and oxygen removal prevent side reactions.\n- **Crosslinking (Optional)**: Incorporating crosslinkers like MBA during synthesis enhances structural stability, especially for hydrogels, by attaching AA units through covalent bonding.\n\n---\n\n### 4. Notes for Experiment\n- **Hydrophilicity Enhancement**:\n  - Ensuring high molar content of AA in the polymer or copolymer will promote good water solubility or swellability, as the -COOH groups significantly interact with water.\n- **Alternative Functionalization**:\n  - The carboxylic groups (-COOH) can be further modified post-polymerization by converting them to carboxylate (-COO⁻) via neutralization.\n\nWith this detailed plan, you should be able to synthesize a hydrophilic polymer efficiently while ensuring controlled reaction conditions and reproducible results.\n\nIf additional clarification or an alternative route is needed, feel free to ask!"
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+{
+  "design_question": "Describe the steps you would take to incorporate the given molecule into the polymer structure to enhance its hydrophilicity, ensuring you include any required reaction conditions or solvents.",
+  "design_answer": "Certainly! Let’s carefully analyze your question and systematically outline an experimental preparation scheme for incorporating your given molecule into a polymer structure to enhance its hydrophilicity.\n\n---\n\n#### **Step 1: Analyze the Problem and Identify the Goals**\nYour goal is to enhance the hydrophilicity of a polymer by integrating a molecule you’ve provided. To achieve this, we need to do two things:\n1. Identify the functional groups on your molecule that can be used to either directly participate in polymerization or attach as side groups to a polymer backbone.\n2. Choose an appropriate polymerization or grafting method (e.g., free radical polymerization, condensation polymerization, or post-polymerization modification) that facilitates efficient incorporation while maintaining or improving hydrophilic properties.\n\nLet’s proceed by designing the experimental protocol step-by-step, ensuring each step contains precise reaction conditions and details for laboratory execution.\n\n---\n\n#### **Step 2: Experimental Design for Hydrophilic Polymer Synthesis**\n\n##### **(Step 2.1) Analyze the Given Molecule**\n- Examine the chemical structure of the molecule. Look for:\n  - **Hydrophilic functional groups** such as hydroxyl (-OH), amino (-NH2), carboxyl (-COOH), sulfonic acid (-SO3H), or polyhydric alcohols (e.g., poly(ethylene glycol), PEG) that will impart hydrophilicity.\n  - **Polymerizable groups** like vinyl (-C=C-) or epoxide rings, which can be used directly in polymerization.\n  - **Reactive groups** that can engage in post-polymerization modifications, such as -OH, -NH2, or acid anhydrides.\n\nLet me assume your molecule contains a vinyl group and a strongly hydrophilic group like a hydroxyl or sulfonic acid. We can then employ free radical polymerization for direct incorporation during polymer synthesis.\n\n---\n\n##### **(Step 2.2) Select the Polymerization Method**\nTo directly polymerize the hydrophilic molecule, the **free radical polymerization** method is well-suited because it:\n- Works with most vinyl monomers.\n- Is robust, straightforward, and widely adaptable.\n\nHere, we can use the provided molecule as a comonomer, alongside another hydrophilic monomer (e.g., acrylic acid or N-vinylpyrrolidone), to prepare a copolymer with enhanced hydrophilicity.\n\n---\n\n##### **(Step 2.3) Materials and Reagents**\n1. **Monomers**:\n   - The given molecule, which we shall call the \"functional monomer.\"\n   - Another hydrophilic comonomer (e.g., acrylic acid, acrylamide, or hydroxyethyl methacrylate, HEMA) to boost hydrophilicity further.\n2. **Initiator**:\n   - A radical initiator, typically **azobisisobutyronitrile (AIBN)** or **ammonium persulfate (APS)**.\n3. **Solvent**:\n   - A compatible polar solvent, such as water, ethanol, or a water-ethanol mixture.\n4. **Crosslinker** (optional):\n   - If a networked hydrogel structure is required, consider adding a bifunctional crosslinker like **ethylene glycol dimethacrylate (EGDMA)**.\n5. **pH Adjuster**:\n   - Sodium hydroxide (NaOH) or hydrochloric acid (HCl) to tune the pH of the reaction medium if required for specific monomers.\n\n---\n\n##### **(Step 2.4) Reaction Protocol**\n1. **Preparation of the Reaction Mixture**:\n   - Dissolve the hydrophilic monomer (e.g., acrylic acid) and the given functional monomer in the chosen solvent. These can be mixed at a molar ratio such as **1:1** or adjusted depending on the desired hydrophilicity and monomer reactivities.\n   - Add the radical initiator (e.g., AIBN) at a concentration of **0.5–1.0 wt% relative to the total monomer content**.\n   - If a crosslinking agent is required, add it at a low molar fraction (e.g., **1–2 mol% of the total monomers**).\n   - Ensure the solution is well-mixed and degas the reaction mixture by bubbling nitrogen or argon gas to remove oxygen, which can inhibit radical polymerization.\n\n2. **Polymerization Reaction**:\n   - Transfer the reaction mixture into a three-necked round-bottom flask equipped with a magnetic stirrer, reflux condenser, and thermometer.\n   - Initiate the reaction by heating the mixture to **60–80°C** under an inert nitrogen atmosphere. Maintain stirring throughout the reaction.\n   - Allow the polymerization to proceed for **4–6 hours**, depending on the reactivity of the monomers chosen.\n\n3. **Post-Reaction Processing**:\n   - After completion, cool the reaction mixture to room temperature.\n   - Precipitate the polymer by adding the reaction mixture dropwise into a nonsolvent (e.g., diethyl ether or acetone for aqueous polymerizations).\n   - Filter and wash the polymer thoroughly to remove unreacted monomers and impurities.\n\n4. **Drying and Storage**:\n   - Dry the purified polymer under vacuum at **40–50°C** until a constant weight is achieved.\n   - Store the polymer in a desiccator to prevent moisture absorption.\n\n---\n\n#### **Step 3: Characterization of the Synthesized Polymer**\nTo confirm the successful incorporation of your molecule and assess hydrophilicity:\n1. **FTIR Spectroscopy**: To identify characteristic functional group peaks in the polymer structure.\n2. **Contact Angle Measurement**: To measure the water contact angle and evaluate surface hydrophilicity.\n3. **NMR Spectroscopy**: To verify the incorporation of the hydrophilic groups and the functional monomer into the polymer backbone.\n4. **Swelling Studies (for hydrogels)**: Immerse the polymer in water and measure its swelling ratio as an indicator of hydrophilicity.\n\n---\n\n#### **Conclusion**\nBy following the outlined procedure, you’ll successfully synthesize a hydrophilic polymer incorporating your molecule. The chosen method, free radical polymerization, is versatile for handling a wide range of vinyl-functionalized hydrophilic molecules. Always monitor the reaction conditions (temperature, pH, solvent system) for optimal results and ensure proper purification to obtain high-quality polymers.\n\nLet me know if you'd like a further refinement of this protocol or assistance with an alternative reaction pathway!"
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+{
+  "design_question": "How would you utilize chitosan variants as polycations within the experimental setup to modify a polymer for enhanced hydrophilicity? Specify the buffer conditions required.",
+  "design_answer": "Certainly, thank you for your question. Let us carefully analyze the problem, step by step, to systematically propose a sound experimental preparation scheme. \n\n### **Analysis of Your Question**\n\nThe main goal of your question is to use *chitosan variants as polycations* to modify a polymer in order to enhance its hydrophilicity. Breaking this down into key points:\n\n1. **Chitosan Variants**: Chitosan is a naturally derived polysaccharide composed of β-(1→4)-linked D-glucosamine and some N-acetyl-D-glucosamine units. Since chitosan has primary amine groups (-NH2), it can act as a polycation in appropriate pH conditions. Variants may include different degrees of deacetylation (DD) and molecular weights, which will affect their solubility and reactivity.\n\n2. **Hydrophilicity Modulation**: The hydrophilic character of polymers can be enhanced either by introducing charged functional groups, polar groups, or chemically/physically grafting hydrophilic moieties. Using a polycationic chitosan structure is a promising approach as it increases polar functionality.\n\n3. **Experimental Setup & Buffer Conditions**: Since chitosan is only soluble under acidic or mildly acidic pH due to protonation of the amine groups, precise buffer conditions are critical for its preparation and subsequent functionalization steps.\n\nWith this understanding, let me now provide a step-by-step experimental preparation scheme in detail.\n\n---\n\n### **Detailed Experimental Preparation Scheme**\n\n#### **1. Materials Required**\n1. **Chitosan Variant**:\n   - Select a chitosan variant with a degree of deacetylation (DD) ≥ 80% for higher amino group content.\n   - Use a medium molecular weight (~100–300 kDa) chitosan for a balance of solubility and mechanical properties.\n   \n2. **Target Polymer**: Choose a polymer with reactive functional groups that can interact with chitosan (e.g., carboxylic groups, epoxides, or halides).\n\n3. **Reagents**:\n   - Acetic acid (weak acid for chitosan dissolution)\n   - Reaction coupling agents (carbodiimides like EDC/NHS for amine-carboxyl reactions, or glutaraldehyde for Schiff base crosslinking)\n   - Buffer systems (phosphate buffer or acetate buffer depending on target polymer chemistry)\n\n4. **Solvents**:\n   - Deionized (DI) water for dissolving hydrophilic components.\n   - Ethanol or other organic solvents for polymer processing, if required.\n\nNow, let us move on to the experimental design.\n\n---\n\n#### **2. Preparation of the Chitosan Solution**\n1. **Dissolution of Chitosan**:\n   - Weigh out the required amount of chitosan (typically 1% w/v solution).\n   - Dissolve chitosan in 1% (v/v) acetic acid solution at room temperature (~25°C) under constant stirring for 2–4 hours until a clear, homogenous solution forms.\n   - Adjust the pH to 5–6 using dilute NaOH to ensure protonation of amino groups, making chitosan positively charged. This is critical for hydrophilic modification reactions.\n\n2. **Buffer Preparation** (Optional for Downstream Steps):\n   - Prepare a weak phosphate buffer (pH 6–7) or acetate buffer (pH 5–6) as required for subsequent coupling or grafting.\n\n#### **3. Activation of the Target Polymer**\n   (Specific to the functional groups present on the polymer)\n1. **If the Polymer Contains Carboxylic Groups**:\n   - Treat the polymer with 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) (10–50 mM) and N-hydroxysuccinimide (NHS) (10–20 mM) in a buffer (e.g., MES buffer, pH 6.0) to activate the carboxylic groups.\n   - Incubate the polymer solution at room temperature for 15–30 minutes with gentle stirring.\n\n2. **If the Polymer Contains Epoxide or Chloride Groups**:\n   - Directly react these groups with chitosan at slightly elevated temperatures (e.g., 40–50°C) to enable a substitution or crosslinking reaction.\n\n#### **4. Coupling Chitosan to the Polymer**\n1. Add the chitosan solution dropwise to the activated polymer solution (in EDC/NHS-activated carboxylic polymers) while stirring.\n2. Maintain reaction conditions for coupling:\n   - pH: Adjust to a mildly acidic range (5–6) to retain amino group protonation.\n   - Temperature: ~25–30°C.\n   - Reaction Time: Stir for 4–6 hours to ensure efficient coupling.\n\n3. **Control Reaction Stoichiometry**:\n   - Molar ratio of polymer carboxylic groups to chitosan NH2 groups: 1:2 to maximize hydrophilic functionalization.\n\n#### **5. Post-Modification Purification**\n1. Dialyze the reaction mixture (if water-soluble) using a membrane (MWCO ~10–30 kDa) to remove unreacted reagents, coupling catalysts, and by-products.\n2. If the polymer is insoluble, wash thoroughly with DI water followed by ethanol to remove impurities.\n\n#### **6. Characterization of Modified Polymer**\n1. Perform Fourier-transform infrared spectroscopy (FTIR) to confirm new bonding (e.g., amide bonds at ~1650 cm⁻¹, Schiff base formation at ~1630–1640 cm⁻¹).\n2. Use contact angle measurements to evaluate hydrophilicity improvements (contact angle should decrease after modification).\n3. Thermogravimetric analysis (TGA) or scanning electron microscopy (SEM) can also be used to evaluate bulk properties or structural changes.\n\n---\n\n### **Buffer Conditions**\n1. **During Chitosan Dissolution**: Use 1% acetic acid (v/v) to protonate chitosan's amino groups, ensuring solubility.\n2. **During Coupling Reactions**:\n   - Use a pH ~5.5 acetate buffer or a mild phosphate buffer (pH ~6.0) to maintain charge balance and enhance crosslinking stability.\n\n---\n\n### **Key Points for Laboratory Success**\n1. Always confirm the compatibility of your chosen buffer with the target polymer and chitosan.\n2. Avoid excessively high or low pH values to prevent chitosan precipitation (optimum: pH 5–6).\n3. Carefully control the molar ratios of functional groups to ensure efficient coupling.\n\nBy following this systematic approach, you should obtain a hydrophilic polymer modified with chitosan variants, significantly enhancing its hydrophilicity. If you encounter any challenges during the experiment, feel free to reach out.\n\nGood luck with your laboratory work!"
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+{
+  "design_question": "Describe how you would use the Ugi four-component reaction to synthesize a molecule capable of enhancing the hydrophilicity of a polymer. Include the specific roles of each component in the reaction.",
+  "design_answer": "### Question Analysis and Key Points\n\nThe student is asking how to use the **Ugi four-component reaction (Ugi-4CR)** to synthesize a molecule that can enhance the hydrophilicity of a polymer. To address this question systematically, we need to:\n\n1. **Understand the Ugi reaction:** The Ugi-4CR is a versatile reaction where an aldehyde (or ketone), an amine, a carboxylic acid, and an isocyanide combine to form a single product—the output contains an amide functional group and typically multiple functional groups that can be leveraged for further modifications.\n\n2. **Design a molecule that enhances hydrophilicity:** Hydrophilic polymers often rely on functional groups such as hydroxyl (-OH), amide (-CONH-), carboxyl (-COOH), or sulfated groups to interact favorably with water. Incorporating such groups during or after the Ugi reaction is key.\n\n3. **Identify roles of the components:** Each of the four components in the Ugi reaction serves a specific purpose (structural building block or functional group provider).\n\n4. **Provide detailed experimental steps:** The synthesis process must include reagent ratios, reaction times, purification methods, and options to attach the synthesized product to the target polymer for enhanced hydrophilicity.\n\n---\n\n### Detailed Experimental Scheme for Hydrophilic Polymer Enhancement Using Ugi-4CR\n\n#### Objective:\nTo design and synthesize a hydrophilic molecule via the Ugi four-component reaction (Ugi-4CR) that can be incorporated into a polymer to enhance hydrophilicity.\n\n---\n\n#### Components to Use:\n1. **Aldehyde/Ketone:** Choose an aldehyde or ketone that offers no hydrophobic steric hindrance. For instance:\n    - **Formaldehyde (HCHO)**: A small molecule capable of adding functional flexibility and simplicity.\n    - Alternatively: Use **glyoxal** (HOCHCHO) to add more hydrophilic moieties directly.\n\n2. **Amine:** Select an amine containing hydrophilic groups such as hydroxyl (-OH), sulfonic acid (-SO3H), or amino (-NH2). For example:\n    - **Ethanolamine (HOCH2CH2NH2)**: Provides a hydroxyl group for hydrophilicity and potentially polymer compatibility.\n\n3. **Carboxylic Acid:** Use a carboxylic acid with water-soluble characteristics. For instance:\n    - **Glycine (H2NCH2COOH)**: Contains both amine and carboxylic acid functionalities to increase hydrophilicity. Glycine is simple and widely available.\n    - Alternatively: **Acryloyl acid derivatives** to introduce polymerizable double bonds.\n\n4. **Isocyanide:** Select an isocyanide that retains compatibility with water and does not introduce hydrophobic groups.\n    - Example: **Tert-butyl isocyanide (t-BuNC)**: Facilitates efficient reaction kinetics without hindering hydrophilicity.\n\n---\n\n#### Reaction Scheme:\nThe synthesis proceeds as follows:\n\n1. **Reaction Setup:**\n   - **Molar ratio:** Aldehyde:Amine:Carboxylic acid:Isocyanide should be **1:1:1:1**. This ensures maximum yield of the Ugi adduct.\n   - **Solvent:** Conduct the reaction in methanol or ethanol, as they are polar solvents that facilitate mixing and solvation for hydrophilic components.\n   - **Reaction temperature:** Typically at room temperature (20–25°C).\n   - **Reaction time:** Stir for 12–24 hours for complete conversion.\n\n2. **Procedure:**\n   - Dissolve the aldehyde (formaldehyde/glyoxal) in the solvent.\n   - Add the amine dropwise while stirring.\n   - Introduce the carboxylic acid while maintaining gentle stirring.\n   - Add the isocyanide last, observing a slight exothermic reaction (if the mixture warms up, cool it back to room temperature).\n   - Continue stirring until no starting materials remain (monitor progress via TLC or NMR spectroscopy).\n\n3. **Purification:**\n   - Isolate the Ugi adduct using vacuum filtration or rotary evaporation if the solvent cannot be recovered.\n   - Further purify by recrystallization from ethanol or methanol.\n\n---\n\n#### Example Hydrophilic Product Design:\nUsing **glyoxal, ethanolamine, glycine**, and **tert-butyl isocyanide**, the Ugi reaction yields a highly functionalized molecule with the following characteristics:\n   - **Hydroxyl groups** (from glyoxal and ethanolamine).\n   - **Amide linkage** (formed during the Ugi reaction).\n   - **Carboxylic acid group** (retained from glycine).\n\nThis product will be inherently hydrophilic due to the presence of hydroxyl and carboxylic groups.\n\n---\n\n#### Reaction Details (Example):\nReagent Quantities (for 1 mmol scale):\n- **Glyoxal (40% aqueous solution)**: 67 µL (provides 1 mmol of active CHO groups).\n- **Ethanolamine:** 61 µL (1 mmol).\n- **Glycine:** 75 mg (1 mmol).\n- **Tert-butyl isocyanide:** 107 µL (1 mmol).\n- Solvent: Use 5 mL methanol.\n\n---\n\n#### Incorporation into Polymer:\nOnce the Ugi adduct is synthesized, you can:\n1. Attach it to a polymer via covalent bonding if the polymer backbone contains active sites (e.g., -OH or -COOH groups).\n2. Directly polymerize the Ugi adduct if it contains functional groups (e.g., unsaturated bonds) that allow radical or addition polymerization.\n\n---\n\n### Summary:\nUsing the Ugi four-component reaction allows you to synthesize a hydrophilic functional molecule with precise control over functional groups. Each component serves a clear role:\n1. **Aldehyde/Ketone**: Facilitates condensation to yield the central scaffold.\n2. **Amine**: Adds nitrogen-containing hydrophilic groups for function and reactivity.\n3. **Carboxylic Acid**: Enhances hydrophilicity directly and stabilizes the product.\n4. **Isocyanide**: Finalizes the reaction by forming the amide backbone.\n\nThis methodology provides an efficient pathway to produce hydrophilic additives for materials applications and can be tuned further for specific polymer systems."
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+{
+  "design_question": "How would you utilize glycerol as a key reactant to synthesize a hydrophilic polymer through an esterification reaction? Provide a detailed experimental scheme, including necessary reaction conditions and any precautions you would take during the process.",
+  "design_answer": "Certainly! To synthesize a hydrophilic polymer using glycerol as a key reactant through an esterification reaction, one can leverage glycerol’s trifunctional nature (it has three hydroxyl groups) to create a polymer with hydrophilic pendant groups or a hydrophilic backbone. Let us carefully analyze and design an experimental scheme to carry out this process, adhering to the systematic approach you requested.\n\n---\n\n### **1. Analysis of the question and key points**\nThe question requires a detailed and systematic synthesis of a hydrophilic polymer using glycerol in an esterification reaction. Key points to address include:\n- Leveraging glycerol's multiple reactive hydroxyl groups as sites for polymer formation.\n- Achieving esterification while introducing hydrophilicity into the polymer chain.\n- Providing precise reaction conditions, reagent quantities, molar proportions, and necessary precautions for a successful experiment.\n\nGiven the question, it is ideal to combine glycerol with a diacid (or anhydride) and potentially copolymerize it with other hydrophilic monomers to tailor the polymer's properties. A widely-used hydrophilic polymer synthesis strategy involves polycondensation or step-growth polymerization.\n\n---\n\n### **2. Experimental preparation scheme**\nBelow, I provide a step-by-step experimental scheme for synthesizing a hydrophilic polymer using glycerol via an esterification reaction.\n\n---\n\n#### **Materials and equipment**\n- **Reagents:**\n  1. Glycerol (C₃H₈O₃) – the core reactant.\n  2. Adipic acid (C₆H₁₀O₄) – the diacid for esterification (you may substitute this with other diacids/anhydrides, such as maleic anhydride, for enhanced hydrophilicity).\n  3. Catalysts: Sulfuric acid (H₂SO₄) or p-toluenesulfonic acid (PTSA) – commonly used acid catalysts.\n  4. Solvent (optional): Toluene or xylene – sometimes used to form a water azeotrope for removing byproduct water.\n  5. Additional hydrophilic monomers (optional): Hydroxyethyl methacrylate (HEMA) or polyethylene glycol (PEG) if desired for further hydrophilic modification.\n\n- **Equipment:**\n  1. Three-neck round-bottom flask.\n  2. Condenser for reflux and water collection.\n  3. Magnetic stirrer and heating mantle.\n  4. Nitrogen gas for inert atmosphere (if required).\n  5. Thermocouple or thermometer.\n\n---\n\n#### **Step-by-step reaction procedure**\n\n##### **Step 1: Reaction setup**\n1. Prepare a **three-neck round-bottom flask** equipped with a magnetic stirrer.\n2. Connect a **condenser** to the flask to perform the reaction under reflux and collect the water generated during esterification.\n3. Optionally, run the reaction under an **inert nitrogen atmosphere** to prevent oxidative degradation.\n\n---\n\n##### **Step 2: Initial reactant loading**\n1. Add **glycerol** (1.00 mol) into the round-bottom flask. For instance, 92 g of glycerol (molecular weight = 92.09 g/mol) will be sufficient for 1.00 mol.\n2. Add **adipic acid** (1.00 mol) into the same flask. For instance, 146.14 g of adipic acid (molecular weight = 146.14 g/mol) will be sufficient for 1.00 mol.\n3. Add a catalytic amount of **sulfuric acid**: approximately 1–2 wt% of the reaction mass. For example, if the total mass of glycerol and adipic acid is ~238 g, add ~2 g (0.01 mol) of sulfuric acid.\n\n---\n\n##### **Step 3: Reaction conditions**\n1. Heat the system to 160–200 °C using a heating mantle. Ensure vigorous stirring to maintain homogeneity.\n2. Maintain the reflux temperature so that the esterification proceeds effectively. You will visibly observe water collecting in the condenser receiver due to the condensation reaction.\n3. Monitor the reaction progress by observing the reduction in the hydroxyl group intensity via FTIR spectroscopy.\n\n---\n\n##### **Step 4: Removal of byproduct water**\n1. Collect the water byproduct during the reaction to shift equilibrium toward polymer formation.\n   - If water generation slows, you may use an azeotropic solvent (e.g., toluene or xylene) to assist in water removal.\n\n---\n\n##### **Step 5: Reaction time**\n1. Allow the reaction to proceed for **6–12 hours**, depending on the reactivity of the monomers and desired molecular weight. \n   - Longer reaction times tend to yield higher molecular weights but could risk side reactions.\n\n---\n\n##### **Step 6: Post-polymerization**\n1. Once the desired viscosity and hydrophilicity are achieved:\n   - Cool the reaction mixture to room temperature.\n   - Precipitate the polymer by adding the reaction mixture to excess cold alcohol (e.g., methanol or ethanol).\n2. Wash the polymer thoroughly with alcohol to remove unreacted monomers and catalyst residues.\n3. Dry the polymer under vacuum at 60–80 °C.\n\n---\n\n#### **Precautions during the experiment**\n1. Ensure the catalyst concentration is controlled to prevent excessive side reactions such as crosslinking.\n2. Prevent overheating above 200 °C, as glycerol may decompose or lead to unwanted oligomer formation.\n3. Use an inert atmosphere to minimize oxidative degradation of the polymer backbone if running long reaction times.\n4. Regularly monitor the reaction by FTIR or NMR spectroscopy to confirm ester bond formation and molecular structure.\n\n---\n\n#### **Optional hydrophilic enhancement**\nIf further hydrophilicity is required:\n1. Copolymerize **glycerol** and **adipic acid** with hydrophilic monomers such as **polyethylene glycol (PEG)** or **hydroxyethyl methacrylate (HEMA)**. For example:\n   - Use PEG with molecular weights of 400 or 1000 (adjust mole ratios accordingly).\n   - Maintain similar reaction conditions with controlled molar ratios (~30% hydrophilic monomer by weight).\n\n---\n\n#### **Conclusion**\nThe described polycondensation reaction between glycerol and adipic acid creates a hydrophilic polyester backbone. The ester groups contribute hydrophilicity while retaining mechanical stability. Additional copolymerization with PEG or HEMA can further enhance hydrophilicity, making this polymer ideal for applications such as hydrogels, biocompatible coatings, or water treatment membranes.\n\nBy following this carefully designed experimental scheme, students should successfully achieve the synthesis of a hydrophilic polymer using glycerol in the laboratory."
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diff --git a/task2/task2-qa/═┐┴╧╣д╥╒ги╡┌╦─░цгй╧┬▓с.json b/task2/task2-qa/═┐┴╧╣д╥╒ги╡┌╦─░цгй╧┬▓с.json
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+{
+  "design_question": "Design a complete experimental setup using phenolic epoxy as the starting polymer and describe how you would incorporate a functional group using triethanolamine to make the polymer hydrophilic. Include the necessary reactants, solvents, and environmental conditions (e.g., temperature, pH) for the synthesis.",
+  "design_answer": "Certainly! Let us carefully dissect your question and systematically create an experimental plan to synthesize a hydrophilic polymer using phenolic epoxy as the starting material and incorporating triethanolamine to enhance hydrophilicity. I shall break this process into a thoughtful, step-by-step experimental preparation scheme and ensure the details are intuitive and practical, focusing on the mechanistic considerations, experimental conditions, and rationale behind each step.\n\n---\n\n### **I. Key Analysis of the Question:**\n\n1. **Starting Polymer:** Phenolic epoxy polymer. It has reactive epoxide groups and phenolic moieties, which are amendable to reaction.\n   \n2. **Goal:** To introduce hydrophilic functional groups into the polymer structure to enhance its hydrophilicity.\n\n3. **Key Reactant:** Triethanolamine is a small molecule bearing three hydroxyl groups (-OH) and an amine (-NH) group. These groups can react with the epoxide in phenolic epoxy and provide hydrophilic functionality.\n\n4. **Chemical Strategy:** A **nucleophilic ring-opening reaction** where triethanolamine reacts with the epoxide rings in the phenolic epoxy backbone is the most appropriate pathway. This forms covalent bonds between triethanolamine and the polymer, while also increasing hydroxyl content.\n\n5. **Experimental Setup:** The scheme must include:\n   - Controlled reaction conditions for selective epoxide ring opening.\n   - A suitable solvent for uniform mixing of phenolic epoxy and triethanolamine.\n   - Post-reaction workup for purification and characterization.\n\n---\n\n### **II. Complete Experimental Preparation Scheme:**\n\nThe preparation scheme involves the following distinct steps:\n\n---\n\n#### **Step 1: Materials and Reagents**\n1. **Materials Needed:**\n   - Phenolic epoxy polymer (commercially available or synthesized as oligomers with controllable molecular weight).\n   - Triethanolamine (TEA, reagent grade, >99% purity).\n   - Solvent: Dimethylformamide (DMF, anhydrous, polar aprotic solvent).\n   - Catalyst (optional): Tertiary amine (e.g., N,N-dimethylbenzylamine (BDMA)) or heat.\n   - Deionized water (for post-reaction clean-up).\n   - Ethanol (for polymer washing and precipitation).\n\n2. **Apparatus:**\n   - A three-neck round-bottom flask (for temperature control and stirring).\n   - Magnetic stirrer with heating capabilities.\n   - Thermometer.\n   - Inert nitrogen gas setup.\n   - Condenser (if performing longer reactions).\n\n---\n\n#### **Step 2: Reaction Conditions and Functionalization Protocol**\n\n1. **Dissolution of Polymer:**\n   - Weigh 5 g of phenolic epoxy polymer and dissolve it in 50 mL of DMF in the three-neck flask under constant stirring at room temperature.\n   - Ensure complete dissolution of the polymer in DMF, as this provides a homogenous medium for reaction.\n   - Remove residual oxygen by purging with nitrogen gas for 10–15 minutes, as oxygen could interfere (e.g., through unwanted side reactions with radicals).\n\n2. **Addition of Triethanolamine:**\n   - Measure the molar equivalent amount of triethanolamine based on the number of epoxy groups in the starting polymer. Assume theoretical calculations: one mole of triethanolamine per mole of epoxide functionalities.\n   - Typically, use **1.05 mol** of TEA per mol of the epoxy groups to ensure complete reaction.\n   - Add the triethanolamine dropwise into the reaction solution to avoid exothermic overheating from the nucleophilic reaction.\n\n3. **Reaction Conditions:**\n   - Heat the reaction mixture to **80–90°C**, the optimal range for the epoxide ring-opening reaction.\n   - Stir constantly to maintain homogeneity.\n   - Maintain the heat and stirring for approximately **6–8 hours**, ensuring complete conversion of the epoxide groups.\n   - Monitor the reaction periodically using an appropriate method, such as FTIR spectroscopy (look for disappearance of the epoxy peak near 915 cm⁻¹ and appearance of hydroxyl groups at ~3200–3500 cm⁻¹).\n\n4. **Optional Catalyst:** To accelerate the process, you may add 0.5 wt% BDMA to the reaction mixture as a catalyst for epoxide ring opening.\n\n---\n\n#### **Step 3: Post-Reaction Workup**\n\n1. **Precipitation of Functionalized Polymer:**\n   - After completion of the reaction, cool the mixture to room temperature.\n   - Slowly add the reaction solution into a large excess (500 mL) of ethanol under stirring. This step precipitates the functionalized polymer.\n\n2. **Washing and Purification:**\n   - Wash the precipitated polymer with ethanol and deionized water to remove any unreacted triethanolamine and DMF residues.\n   - Dry the purified polymer in a vacuum oven at **40–50°C** until constant weight is achieved.\n\n---\n\n#### **Step 4: Characterization of the Hydrophilic Polymer**\n\n1. **Hydrophilicity Measurement:**\n   - Evaluate the hydrophilicity of the functionalized polymer using water contact angle measurements. A decrease in the contact angle compared to the starting material confirms improved hydrophilicity.\n   \n2. **Structural Characterization:**\n   - Use FTIR spectroscopy to confirm the successful ring-opening reaction (e.g., disappearance of epoxy group signal and appearance of O-H stretching from hydroxyl groups).\n   - Use NMR spectroscopy to confirm the covalent bonding between triethanolamine and the polymer backbone.\n   \n3. **Thermal and Mechanical Property Analysis:**\n   - Test properties such as thermal stability (TGA analysis) or mechanical integrity of the hydrophilic polymer using DMA.\n\n---\n\n### **III. Summary of the Experimental Setup**\n\n- **Reaction Type:** Nucleophilic epoxide ring-opening with triethanolamine.\n- **Polymer Functionalization:** Formation of hydroxyl-rich functionalized phenolic epoxy polymer.\n- **Solvent:** DMF (polar aprotic) for efficient reaction.\n- **Reaction Conditions:** 80–90°C for 6–8 hours under stirring, in the presence of inert nitrogen gas.\n- **Post-Reaction Workup:** Precipitate in ethanol, wash, and dry.\n- **Characterization Tools:** FTIR, NMR, contact angle measurement.\n\n---\n\nBy reacting phenolic epoxy with triethanolamine under the above conditions, hydrophilic hydroxyl and secondary amine functionalities will be incorporated into your polymer backbone, making it significantly more hydrophilic.\n\nGood luck with your experiments, and feel free to return with any further questions about synthesis or characterization!"
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diff --git a/task2/task2-qa/╒│╨╘╞Ё╩╝▓у ═и╙├╦о─¤╜║AM.json b/task2/task2-qa/╒│╨╘╞Ё╩╝▓у ═и╙├╦о─¤╜║AM.json
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+{
+  "design_question": "How would you utilize the molecule polydopamine in your experimental design to create an initiation layer that facilitates the synthesis of hydrophilic polymers?",
+  "design_answer": "To address your question using polydopamine as an initiation layer for the synthesis of hydrophilic polymers, let us proceed systematically and thoughtfully. Here are the critical steps to follow:\n\n---\n\n### **Step 1: Analyze the Question and Summarize Key Points**\nYou intend to use polydopamine (PDA) as the basis for creating an initiation layer to facilitate the synthesis of hydrophilic polymers. Polydopamine is a versatile material that exhibits strong adhesion to virtually any surface due to its catechol and amine groups. These functional groups can serve as reactive sites to anchor hydrophilic polymer chains either through grafting or polymerization strategies. The key goal is to build a surface-functionalized polymer layer with enhanced hydrophilicity by leveraging PDA's unique properties.\n\nConsequently, the experimental scheme must:\n1. Deposit PDA onto a substrate as the initiation layer.\n2. Identify mechanisms (grafting or polymerization) and hydrophilic monomers to create the polymer layer.\n3. Ensure the hydrophilic polymer is synthesized systematically, with precise reaction conditions, reagent ratios, and techniques.\n\n---\n\n### **Step 2: Systematic Answer**\nHere is the detailed experimental preparation scheme for synthesizing a hydrophilic polymer layer using PDA.\n\n---\n\n#### **Step A: Polydopamine Deposition on the Substrate**\n1. **Substrate Preparation**: Choose an appropriate substrate, such as glass, metals (e.g., titanium, stainless steel), or polymers (e.g., polyethylene, polystyrene). Clean the substrate to remove contaminants (if applicable):\n   - Wash substrate thoroughly with deionized (DI) water.\n   - Sonicate in ethanol followed by DI water for 15 minutes each.\n   - Dry substrate with nitrogen.\n\n2. **Polydopamine Coating**:\n   - Prepare a dopamine solution (2 mg/mL) in Tris buffer (10 mM, pH 8.5).\n   - Place the clean substrate into the dopamine solution and allow it to polymerize at room temperature for 12–24 hours under gentle stirring. Dopamine self-polymerizes into polydopamine under mildly alkaline conditions.\n   - After deposition, rinse the substrate thoroughly with DI water to remove any unreacted dopamine or loosely bound PDA particles.\n   - Dry the polydopamine-coated substrate under nitrogen or air.\n\n   **Mechanism and Role**: During polymerization, dopamine forms a PDA layer through covalent and π−π interactions. The catechol and amino groups on PDA provide a reactive initiation layer for further functionalization.\n\n---\n\n#### **Step B: Selection of Hydrophilic Monomers and Polymerization Method**\nChoose a hydrophilic monomer capable of forming the desired polymer layer. Common hydrophilic monomers include:\n   - Acrylamide (AM) for polyacrylamide.\n   - Polyethylene glycol methacrylate (PEGMA) for PEG-based hydrophilic polymers.\n   - N-vinylpyrrolidone (NVP) for polyvinylpyrrolidone.\n\nA suitable polymerization method must also be selected:\n   - **Grafting-to**: Attach preformed hydrophilic polymer chains to PDA.\n   - **Grafting-from**: Initiate polymerization directly from PDA.\n   - **Surface-initiated polymerization (SIP)**: Use PDA’s reactive groups to create polymer chains directly.\n\n---\n\n#### **Step C: Experimental Design for Hydrophilic Polymerization**\nWe will use surface-initiated atom transfer radical polymerization (SI-ATRP) as an example due to its controllability. Let’s synthesize polyacrylamide (PAAm) for enhanced hydrophilicity.\n\n1. **Step 1: Activate PDA Layer for ATRP initiation**\n   - Prepare a bromoisobutyryl bromide (BIBB) solution in dry dichloromethane (DCM).\n   - Immerse the PDA-coated substrate into the solution for 4–6 hours, ensuring covalent binding of ATRP initiator (BIBB) to PDA's amine groups.\n   - Wash substrate with DCM and ethanol to remove excess BIBB.\n   - Dry the substrate under inert gas.\n\n2. **Step 2: Prepare the Polymerization Solution**\n   - Dissolve acrylamide monomer (1 M concentration) in DI water.\n   - Add a catalyst system (CuBr/CuBr2 complex) and ligand (e.g., N,N,N′,N′′-tetramethylethylenediamine, TMEDA) to the solution, ensuring a monomer:catalyst ratio of **100:1**.\n   - Degas the solution using nitrogen bubbling for 10 minutes to remove oxygen (oxygen inhibits ATRP).\n\n3. **Step 3: Initiate Polymerization on PDA Layer**\n   - Immerse the PDA-bound substrate into the polymerization solution.\n   - Maintain the reaction at room temperature or slightly elevated temperature (e.g., 25–35°C) for 2–4 hours, depending on the desired polymer thickness.\n   - After polymerization, remove the substrate and rinse thoroughly with DI water and ethanol to eliminate unreacted monomers and residual reagents.\n\n4. **Step 4: Post-Treatment (Optional)**\n   - Purify the polymer layer further if needed, such as soaking the substrate in ethanol or acetone.\n   - Dry the final polymer-coated substrate under nitrogen.\n\n---\n\n#### **Step D: Confirmation of Hydrophilic Polymer Coating**\nTo confirm successful polymer synthesis and hydrophilicity enhancement:\n1. **Surface Characterization**:\n   - Use Fourier-transform infrared spectroscopy (FTIR) to identify functional groups indicative of the hydrophilic polymer.\n   - Use scanning electron microscopy (SEM) or atomic force microscopy (AFM) to visualize the coating's morphology.\n\n2. **Hydrophilicity Tests**:\n   - Measure the water contact angle using a goniometer: A significantly reduced angle (e.g., <30°) indicates hydrophilic enhancements.\n   - Conduct dynamic water absorption tests.\n\n---\n\n### **Step 3: Wrap-Up**\nUsing polydopamine as an initiation layer not only provides a robust base for polymerization but also ensures excellent adhesion of hydrophilic polymer chains to the substrate. By selecting ATRP as the polymerization method and acrylamide as the hydrophilic monomer, we achieved a controllable synthesis of polyacrylamide on a PDA-coated substrate. Every reaction step, from polydopamine deposition to polymer layer confirmation, is critical for successful experimental implementation in the lab.\n\nLet me know if further clarification or customization is needed!"
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+{
+  "design_question": "Design an experimental scheme to prepare a hydrophilic polymer coating using acrylamide (AM) as the primary monomer. Ensure you include key steps such as polymerization initiation, cross-linking, and any necessary post-treatment processes.",
+  "design_answer": "Certainly, thank you for the detailed context and specific question. Let us now design a systematic experimental scheme for synthesizing a hydrophilic polymer coating using acrylamide (AM) as the primary monomer. I will adhere to the outlined requirements, breaking down the synthesis into essential steps and providing detailed information on reaction conditions, reagent ratios, and other critical parameters to facilitate the experiment's successful execution in the laboratory.\n\n---\n\n### **Step 1: Analysis of Key Points**\nYour objective is to synthesize a hydrophilic polymer coating using acrylamide (AM) as the primary monomer. The polymer must exhibit high hydrophilicity, making it suitable for applications such as biocompatible coatings or anti-fouling surfaces. \n\nFor this, we'll focus on:\n1. **Polymerization initiation** – Efficiently initiating polymerization using a free-radical approach.\n2. **Cross-linking** – Introducing a cross-linking agent to ensure that the coating exhibits the desired mechanical properties and stability.\n3. **Post-treatment** – If applicable, further processing to enhance the hydrophilic performance or functional properties of the polymer.\n\nThe process will rely on aqueous polymerization to align with the hydrophilic property requirements. Let us proceed step by step.\n\n---\n\n### **Step 2: Detailed Experimental Scheme**\n\n#### **2.1 Materials Required**\n1. **Monomer**: Acrylamide (AM) – A hydrophilic monomer with water-soluble properties.\n2. **Cross-linker**: N,N′-methylenebisacrylamide (MBAA) – A commonly used cross-linker for acrylamide-based systems to introduce network structures.\n3. **Initiator**: Ammonium persulfate (APS) – A water-soluble initiator to generate radicals.\n4. **Accelerator**: N,N,N′,N′-Tetramethylethylenediamine (TEMED) – To speed up the radical formation process initiated by APS.\n5. **Solvent**: Deionized water.\n6. **Substrate for Coating**: Glass slides, polymer films, or other support surfaces requiring hydrophilic coatings.\n\n---\n\n#### **2.2 Synthesis Steps**\n\n**Step 1: Surface Preparation (Substrate Pre-treatment)**\n1. **Purpose**: Ensure strong adhesion of the hydrophilic polymer coating to the substrate.\n2. **Procedure**:\n   - Clean the substrate (e.g., glass slides) thoroughly with a detergent solution.\n   - Immerse in a mixture of ethanol and water (1:1 ratio) to remove organic contaminants.\n   - Rinse with deionized water and dry under a stream of nitrogen.\n   - For glass substrates, further activate the surface by treating with an oxygen plasma or 1 M NaOH for 10 minutes to improve adhesion.\n\n---\n\n**Step 2: Preparation of the Monomer Solution**\n1. **Purpose**: Synthesize an aqueous precursor solution containing all necessary reagents.\n2. **Procedure**:\n   - Weigh **5.0 g of acrylamide (AM)** and dissolve it in **40 mL of deionized water** in a glass beaker. Stir at room temperature until fully dissolved.\n   - Add **0.05 g of N,N′-methylenebisacrylamide (MBAA)** as the cross-linking agent while continuing to stir.\n   - Prepare a solution of **0.02 g of ammonium persulfate (APS)** in **1 mL of deionized water**, and add it to the reaction mixture. This acts as the radical initiator.\n   - Add **5 μL of TEMED** to the reaction mixture while stirring. TEMED acts as an accelerator, facilitating the decomposition of APS and generating free radicals for polymerization.\n   - Degas the solution under a flow of nitrogen or argon for 5–10 minutes to remove dissolved oxygen, which can inhibit free-radical polymerization.\n\n---\n\n**Step 3: Coating Application**\n1. **Purpose**: Uniformly apply the monomer solution to the substrate.\n2. **Procedure**:\n   - Place the pretreated substrate on a clean, leveled surface.\n   - Apply a thin layer of the monomer solution (ca. 50–100 μm thickness) using a spin-coating technique or dip-coating method for uniform coating. Control the speed and withdrawal rate for optimal thickness.\n   - If spin-coating, spin at **1000 rpm for 30 seconds**.\n\n---\n\n**Step 4: Polymerization**\n1. **Purpose**: Induce free-radical polymerization to form the hydrophilic polymer network.\n2. **Procedure**:\n   - Transfer the coated substrate to a covered humidified chamber maintained at **50–60°C**.\n   - Allow polymerization to proceed for **2 hours**.\n   - The heat will decompose APS, initiating polymerization, while TEMED accelerates the process. MBAA will introduce cross-links into the polymer, stabilizing it as a coating.\n\n---\n\n**Step 5: Post-treatment**\n1. **Purpose**: Remove unreacted monomers and enhance hydrophilicity.\n2. **Procedure**:\n   - Immerse the coated substrate in deionized water and gently agitate it for **24 hours** to remove any unreacted monomer or unbound polymer.\n   - Replace the water every 6 hours for effective purging.\n   - Optionally, treat the coating with dilute ethanol (10% v/v) for surface restructuring to improve uniformity.\n\n---\n\n**Step 6: Characterization and Analysis**\n1. **Surface Hydrophilicity**:\n   - Measure the **water contact angle** on the coated substrate to confirm hydrophilicity. Values below 30° indicate high hydrophilicity.\n2. **Chemical Structure**:\n   - Use **FTIR spectroscopy** to verify the successful incorporation of acrylamide and cross-links.\n3. **Adhesion Test**:\n   - Conduct an adhesion test (e.g., tape peeling) to confirm the robustness of the coating on the substrate.\n\n---\n\n### **Step 3: Notes and Additional Tips**\n1. The concentration of cross-linker (MBAA) should be carefully tuned. If too high, the polymer may become overly rigid and lose its hydrophilicity. If too low, the polymer may lack mechanical stability.\n2. TEMED must be handled carefully in small amounts, as excessive TEMED can cause uncontrolled polymerization.\n3. Ensure the polymerization chamber has consistent temperature control to obtain uniform cross-linking and polymer growth.\n\n---\n\nThis systematic procedure should enable the successful preparation of a thin, uniform, and mechanically stable hydrophilic polymer coating. Feel free to ask additional clarifying questions if needed, and I encourage you to carefully plan and document the steps during the experiment."
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+{
+  "design_question": "Incorporating polyaniline (PANI) into a polymer network involves addressing potential interactions between PANI and the gel matrix. How would you design an experiment to minimize any negative interactions while retaining the hydrophilicity enhancement provided by PANI?",
+  "design_answer": "Thank you for your thoughtful question. Incorporating polyaniline (PANI) into a polymer network to enhance hydrophilicity while minimizing potential negative interactions requires an understanding of both the chemical interactions between PANI and the polymer gel matrix, and the strategies needed to optimize compatibility. Let us approach this problem step by step, specifying a detailed experimental design you could follow:\n\n---\n\n### **Step 1: Analyze the Key Points of the Problem**\n1. **Objective:** Incorporate PANI into a hydrophilic polymer network to enhance hydrophilicity.\n2. **Challenge:** Prevent negative interactions between PANI and the polymer gel matrix, which might result in phase separation, reduced mechanical strength, or loss of hydrophilicity.\n3. **Main Considerations:**\n   - PANI is inherently hydrophobic in its emeraldine base form, meaning initial modifications will be required.\n   - PANI's compatibility with the matrix can be influenced by factors such as surface interactions, dispersion stability, and crosslinking.\n   - The gel matrix should preserve its hydrophilicity while integrating PANI without compromise.\n\n---\n\n### **Step 2: Proposed Experimental Preparation Scheme**\n\n#### **Part A: Functionalization of PANI**\nThe first step involves chemically modifying PANI to increase its hydrophilicity and compatibility with the hydrophilic polymer matrix.\n   \n1. **Oxidative Polymerization of PANI:**\n    1. **Materials:**\n        - Aniline monomer (1.0 M aqueous solution)\n        - Ammonium persulfate (APS) as oxidant\n        - Hydrochloric acid (HCl, 1.0 M aqueous solution)\n        - Deionized water\n    2. **Procedure:**\n        - Dissolve the aniline monomer in 1.0 M HCl to prepare a 0.1 M solution.\n        - Separately, dissolve APS in 1.0 M HCl to prepare a 0.1 M solution. Maintain a molar ratio of APS to aniline at 1.25:1.\n        - Slowly add the APS solution dropwise to the aniline solution under constant stirring (300 rpm) at 0-5°C to maintain a controlled polymerization rate.\n        - Allow the reaction to proceed for 4 hours. Collect the resulting PANI precipitate and wash it with deionized water until neutral pH is achieved.\n        - Dry the PANI at 60°C under vacuum.\n\n2. **Introduction of Sulfonic Acid Groups (Sulfonation):**\n    1. **Purpose:** Sulfonation increases hydrophilicity and introduces functional groups (-SO3H) to improve compatibility with the hydrophilic matrix.\n    2. **Materials:**\n        - Sulfuric acid (H2SO4, concentrated)\n        - PANI prepared above\n    3. **Procedure:**\n        - Disperse PANI in concentrated H2SO4 (10 mL H2SO4 per gram of PANI) under vigorous stirring.\n        - Heat the mixture at 80°C for 6 hours to achieve sulfonation.\n        - Precipitate the sulfonated PANI (SPANI) by adding the dispersion to a large volume of deionized water with stirring.\n        - Collect the SPANI by filtration, wash extensively until pH neutral, and dry at 60°C.\n\n---\n\n#### **Part B: Preparation of the Hydrophilic Polymer Matrix**\nThe second step involves synthesizing the hydrophilic polymer gel and integrating the functionalized PANI into the network.\n\n1. **Hydrogel Synthesis:**\n    1. **Monomers and Crosslinkers:**\n        - Select a hydrophilic monomer such as acrylamide (AAm) or 2-hydroxyethyl methacrylate (HEMA).\n        - Use a crosslinker such as N,N'-methylenebisacrylamide (MBAA) to stabilize the polymer network.\n    2. **Initiators:**\n        - Use ammonium persulfate (APS) and tetramethylethylenediamine (TEMED) as the redox pair for polymer initiation.\n    3. **Procedure:**\n        - Prepare an aqueous solution of AAm (10 wt%) and MBAA (1.0 mol% of AAm concentration).\n        - Add APS (0.5 wt% relative to monomer content) and TEMED (0.1 wt%) to the solution.\n        - Mix thoroughly and pour into a mold to form a uniform gel.\n\n---\n\n#### **Part C: Integration of SPANI**\nNow incorporate SPANI into the polymer matrix during gel synthesis to avoid phase separation and enhance compatibility.\n\n1. **Preparation of SPANI-Polymer Mixture:**\n    1. Disperse SPANI in deionized water using ultrasonication to ensure uniform dispersion. Use 1-5 wt% of SPANI based on the total weight of the gel.\n    2. Add this SPANI dispersion to the monomer-crosslinker solution prepared in Part B. Stir thoroughly to ensure homogeneity.\n\n2. **Polymerization in the Presence of SPANI:**\n    1. Add the APS and TEMED initiator system to the SPANI-polymer solution.\n    2. Pour the mixture into the mold and allow polymerization to proceed at room temperature for 24 hours.\n    3. Wash the resulting hydrogel to remove unreacted monomers and initiator.\n\n---\n\n### **Step 3: Post-Synthesis Modifications**\nAfter polymerization, you may need to conduct further modifications to optimize the material properties.\n\n1. **Swelling Test:**\n   Immerse the hydrogel in deionized water to test its swelling behavior. A high swelling ratio indicates successful integration of hydrophilic properties.\n\n2. **Characterization:**\n   - **FTIR Spectroscopy:** Confirm the presence of sulfonic acid groups in SPANI and the hydrogel matrix.\n   - **Scanning Electron Microscopy (SEM):** Investigate the dispersion of SPANI within the polymer matrix.\n   - **Contact Angle Measurement:** Evaluate the hydrophilicity enhancement.\n   - **Mechanical Testing:** Assess the impact of SPANI inclusion on gel strength.\n\n---\n\n### **Step 4: Optimization and Troubleshooting**\nIf the synthesized material shows phase separation or poor mechanical strength:\n1. Reduce the SPANI content to improve compatibility.\n2. Increase the crosslinking density by adding more MBAA.\n3. Test alternative surface functionalization methods for PANI, such as carboxylation or grafting with polyethylene glycol (PEG), to improve its affinity for the hydrogel.\n\n---\n\n### **Conclusion**\nThe approach outlined above systematically addresses the incorporation of PANI into a hydrophilic polymer network while minimizing negative interactions. By functionalizing PANI (e.g., sulfonation) and ensuring uniform dispersion during polymer synthesis, we retain the hydrophilicity enhancement potential of PANI in the polymer gel. Follow these step-by-step procedures carefully, and with diligent practice in the lab, you should achieve a stable and hydrophilic PANI-integrated hydrogel. If you encounter any further issues, feel free to ask for additional clarification or guidance!"
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+{
+  "design_question": "Describe a step-by-step procedure to include calcium chloride (CaCl2) in the polymerization process to enhance the hydrophilicity of the resulting material. What is the significance of adding this molecule, and how might it interact with other components during synthesis?",
+  "design_answer": "Certainly! To address your question regarding the inclusion of calcium chloride (CaCl₂) in the polymerization process for improving the hydrophilicity of the resulting material, let us analyze the problem first, then proceed to systematically describe the step-by-step procedure, and finally discuss the significance and potential interaction of CaCl₂ with other components.\n\n---\n\n### **Step 1: Analyzing the Question**\n\nThe goal is to:\n1. Incorporate calcium chloride (CaCl₂) into the polymerization process.\n2. Enhance the hydrophilicity of the resulting polymer material.\n \nCaCl₂ is a hygroscopic salt known for its excellent water-attracting and dissolving properties. Adding CaCl₂ may increase the affinity of the polymer for water (hydrophilicity) either directly through ionic interactions with charged groups on the polymer or indirectly by influencing the polymerization process itself, such as affecting crosslinking or chain interactions.\n\nTo systematically prepare a polymer with improved hydrophilicity enhanced by CaCl₂, we need to carefully control all reaction parameters and understand the role that CaCl₂ plays during the polymerization process.\n\n---\n\n### **Step 2: Experimental Preparation Scheme**\n\nBelow is the detailed, step-by-step approach to designing an experimental polymerization process incorporating CaCl₂:\n\n---\n\n#### **Step 2.1: Selection of Monomers**\n- Choose monomers or comonomers that allow polymerization and have functional groups capable of interacting with CaCl₂. For instance:\n    - Acrylamide (AM) is a common monomer for hydrophilic polymer synthesis.\n    - Acrylic acid (AA) or methacrylic acid (MAA) can be used for introducing carboxylic acid groups, which interact with Ca²⁺ ions.\n- Optionally, copolymerization with hydrophilic monomers like hydroxyethyl methacrylate (HEMA) or polyethylene glycol methacrylate (PEGMA) might further augment the polymer's water-attracting properties.\n\n---\n\n#### **Step 2.2: Preparation of Reaction Solution**\n- **Solvent:** Prepare an aqueous medium as water facilitates the solubilization of CaCl₂ and is ideal for hydrophilic polymer synthesis.\n- **Calcium Chloride Pre-Dissolution:** Dissolve CaCl₂ in water before introducing it to the polymer reaction solution. The concentration of CaCl₂ typically ranges from 0.05 M to 0.5 M, depending on the desired enhancement in hydrophilicity.\n    - Example: For 0.2 M CaCl₂ concentration in 100 mL water, dissolve 2.2 g of CaCl₂ in water.\n\n---\n\n#### **Step 2.3: Polymerization Setup**\n- **Reaction Vessel:** Use a glass reactor equipped with a magnetic stirrer, nitrogen inlet (for inert atmosphere), and a temperature-controlled heating mantle.\n- **Initiator System:** Choose a suitable radical initiator (e.g., ammonium persulfate (APS), potassium persulfate (KPS), or azobisisobutyronitrile (AIBN) depending on solvent and conditions).\n\n---\n\n#### **Step 2.4: Reaction Conditions**\n1. **Initiator Activation:**\n   - Dissolve the initiator in the CaCl₂-containing aqueous solution. A typical initiator amount is 0.1–0.5 wt% of the total monomer content.\n   - For APS, dissolve 0.2 g APS in 50 mL water containing CaCl₂.\n   - Degas the solution by bubbling nitrogen through for 30 minutes to create an inert atmosphere.\n   - Heat the solution to ~70 °C to activate APS under controlled stirring conditions.\n\n2. **Addition of Monomers:**\n   - Add monomers (e.g., 10 g AM, 5 g AA, and optionally 1 g PEGMA) into the reactor slowly while stirring to ensure homogeneous mixing.\n   - Monitor the pH of the solution and adjust with NaOH or HCl if required. The optimal range is slightly acidic to neutral (pH ~6–7).\n\n3. **Crosslinking Agent:**\n   - If a crosslinked hydrogel is desired, add a crosslinker such as N,N′-methylenebisacrylamide (MBA). Typical quantities are 0.1–0.5 wt% of monomer content.\n   - Example: Add 0.1 g MBA to the monomer mixture.\n\n4. **Role of CaCl₂:**\n   - During polymerization, CaCl₂ enhances ionic interactions with the polymer chains, potentially influencing chain orientation as well as hydration properties. Ca²⁺ ions can interact electrostatically with carboxyl groups on acrylic acid or hydroxyl groups in PEGMA or AM, creating ionic clusters that increase polymer hydrophilicity.\n\n5. **Polymerization Reaction:**\n   - Allow the polymerization to proceed for 2–4 hours under constant stirring and controlled temperature (~70–75 °C).\n   - Monitor the reaction's viscosity and appearance (gelation may occur if crosslinked).\n\n---\n\n#### **Step 2.5: Polymer Washing and Purification**\n- **Washing:**\n   - After polymerization, remove unreacted CaCl₂ and other impurities by washing the polymer thoroughly with distilled water.\n   - For hydrogels, immerse them in large volumes of water and replace the water daily for 2–3 days.\n\n- **Drying:**\n   - Dry the polymer for further characterization, e.g., in a vacuum drying oven at 50 °C. Alternatively, leave hydrogels hydrated for direct use.\n\n---\n\n### **Step 3: Significance of Adding CaCl₂**\n\n#### 3.1: **Enhancement of Hydrophilicity**\n- Calcium chloride is hygroscopic and readily attracts water, which translates to a polymer system with increased water-binding capacity.\n- The interaction between Ca²⁺ ions and functional groups on the polymer chains introduces ionic exchanges that promote enhanced water diffusion and retention, thus increasing hydrophilicity.\n\n#### 3.2: **Impact on Polymer Structure**\n- CaCl₂ may influence the polymer network by ionic crosslinking or modifying polymer chain conformations. These effects might result in a softer, more porous structure, which is ideal for applications like hydrogels, tissue scaffolds, and superabsorbent polymers.\n\n#### 3.3: **Applications**\n- CaCl₂-modified hydrophilic polymers may find applications in biomedical fields (e.g., drug delivery), agriculture (e.g., soil conditioners), water purification, and personal care (e.g., hydrating gels).\n\n---\n\n### **Step 4: Interaction with Other Components**\n- **Monomers and Ca²⁺:** Ionic interactions between Ca²⁺ ions and acidic functional groups strengthen polymer-water bonding.\n- **Crosslinker and CaCl₂:** Ca²⁺ ions may compete with covalent crosslinking, leading to altered mechanical properties in crosslinked hydrogels.\n\n---\n\nBy following these detailed steps and understanding the significance and interactions during synthesis, your experiment should yield a successful hydrophilic polymer with enhanced properties attributed to the addition of calcium chloride. Let me know if you need further clarification or assistance!"
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+{
+  "design_question": "Describe how you would verify that adipic acid dihydrazide has been successfully incorporated into a polymer to enhance its hydrophilicity. What specific analytical techniques would you use, and what results would you expect?",
+  "design_answer": "Certainly, let’s carefully analyze and systematically address your question.\n\n---\n\n### **Key Points to Analyze:**\n1. **Objective**: Verify the incorporation of adipic acid dihydrazide (AADH) into a polymer.\n2. **Rationale**: AADH is a hydrophilic functional group, and its successful incorporation into the polymer backbone or side chain is expected to enhance the hydrophilicity of the polymer.\n3. **Focus**: Use appropriate analytical techniques to confirm the successful incorporation of AADH into the polymer matrix.\n4. **Expected Outcome**: Identify key signatures (structural confirmation, compositional data, and hydrophilicity measurements) that verify AADH's presence and its impact on polymer properties.\n\n---\n\n### **Systematic Approach to Verification Using Analytical Techniques**\n\n#### **Step 1: Structural Confirmation (Chemical Bond Analysis)**\n**Objective**: Identify characteristic chemical groups of AADH (e.g., hydrazide groups, amide-like bonds) in the polymer structure.\n\n1. **FTIR (Fourier Transform Infrared Spectroscopy)**:\n   - **Purpose**: Confirm the presence of functional groups characteristic of AADH in the polymer.\n   - **Key Features to Look For**:\n     - **N–H stretching vibrations**: A broad peak around 3200–3500 cm⁻¹ (characteristic of amine groups).\n     - **C=O stretching vibrations**: Carbonyl peaks near 1640–1700 cm⁻¹ in the amide region, indicative of the hydrazide group.\n     - **N–N stretching**: Hydrazide-specific peaks in the range of 1000–1150 cm⁻¹.\n   - **Comparison**: Compare the FTIR spectrum of the modified polymer with the spectra of the base polymer and pure AADH. The emergence of new absorption bands corresponding to AADH groups indicates successful incorporation.\n\n2. **NMR (Nuclear Magnetic Resonance Spectroscopy)**:\n   - **Purpose**: Identify chemical shifts corresponding to the hydrogen and carbon atoms in the AADH structure.\n   - **Key Regions in ¹H NMR**:\n     - Proton peaks of the N–H group (broad signal around 7–8 ppm, depending on hydrogen bonding).\n     - Incorporation of aliphatic protons from the AADH chain can give rise to peaks around 1.2–2.4 ppm.\n   - **Key Regions in ¹³C NMR**:\n     - Carbonyl carbons of AADH would appear in the range of 160–180 ppm.\n   - **Expected Outcome**: Clear signals in both spectra corresponding to AADH indicate its presence in the polymer matrix.\n\n3. **XPS (X-ray Photoelectron Spectroscopy)**:\n   - **Purpose**: Provide elemental and bonding information on the polymer surface.\n   - **Analysis**: Look for nitrogen content (N 1s peak) from the hydrazide group. Deconvolution of N 1s and C 1s peaks can reveal the presence of specific bonding environments (e.g., C–N, N–N).\n\n---\n\n#### **Step 2: Quantification of Incorporation**\n**Objective**: Estimate the extent of AADH incorporation into the polymer.\n\n1. **Elemental Analysis (EA)**:\n   - **Purpose**: Quantify nitrogen and other elemental contents in the polymer (indicating AADH incorporation).\n   - **Comparison**: Compare nitrogen content before and after AADH modification. A significant increase in nitrogen indicates AADH incorporation.\n\n2. **Titration Method** (if applicable):\n   - If reactive hydrazide end-groups remain in the polymer, these can be quantified through titrimetric analysis using aldehydes (e.g., formaldehyde).\n\n3. **GPC (Gel Permeation Chromatography)**:\n   - **Purpose**: Assess changes in molecular weight distribution after polymer functionalization.\n   - **Expected Outcome**: An increase in molecular weight or polydispersity index (PDI) indicates successful modification. However, ensure that the reaction conditions do not lead to polymer degradation or crosslinking.\n\n---\n\n#### **Step 3: Verification of Enhanced Hydrophilicity**\n**Objective**: Confirm that AADH’s incorporation improves the polymer's hydrophilic nature.\n\n1. **Water Contact Angle (WCA)**:\n   - **Purpose**: Measure the surface wettability of the polymer.\n   - **Expected Outcome**: A lower water contact angle after modification indicates improved hydrophilicity due to the incorporation of polar AADH groups.\n\n2. **Swelling Behavior**:\n   - **Experiment**: Immerse the polymer in water or a hydrophilic solvent and measure the swelling ratio.\n   - **Expected Outcome**: Increased swelling capacity of the polymer due to improved water absorption.\n\n3. **Zeta Potential (if relevant)**:\n   - **Purpose**: Measure the polymer surface charge in aqueous solution.\n   - **Expected Outcome**: A more negative surface potential may indicate the presence of polar groups (from AADH) enhancing hydrophilicity.\n\n4. **DSC (Differential Scanning Calorimetry)**:\n   - **Purpose**: Assess changes in thermal properties due to AADH incorporation.\n   - **Expected Outcome**: An increase in the glass transition temperature (Tg) may result from the introduction of hydrogen-bonding groups, which restrict polymer chain mobility.\n\n---\n\n### **Integration of Results**\n\nBy combining the results from the above techniques, systematic confirmation of AADH incorporation can be achieved:\n- **Structural Evidence**: FTIR, NMR, and XPS provide direct evidence of AADH linkage in the polymer.\n- **Compositional Evidence**: Elemental analysis and GPC quantify the extent of functionalization.\n- **Property Enhancement**: Hydrophilicity tests (e.g., WCA, swelling) validate functional improvement.\n\n---\n\n### **Expected Results and Discussion**\n1. **FTIR/NMR/XPS Analysis**: New peaks corresponding to AADH functional groups.\n2. **EA/GPC/Quantification**: Increased nitrogen content and possibly higher molecular weight after modification.\n3. **Hydrophilicity Tests**: Lower contact angle, increased swelling ratio, confirming improved hydrophilicity.\n\nBy systematically leveraging these methods, we can conclusively verify AADH incorporation and its effects on polymer hydrophilicity.\n\n"
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+{
+  "design_question": "In an experimental setup, how would you systematically vary the concentration of TMS-PEG to study its effect on the hydrophilicity of the modified polymer? Suggest a methodology to evaluate and quantify the change in hydrophilicity across different samples.",
+  "design_answer": "Certainly! Thank you for asking such a thoughtful question. Let's approach this systematically to design your experimental setup and methodology for varying the concentration of TMS-PEG (trimethylsilane-polyethylene glycol) to study its effect on enhancing the hydrophilicity of the modified polymer.\n\n---\n\n### **Step 1: Analyzing the Question**\n\n- **Key Objective**: The goal is to systematically vary the TMS-PEG concentration and evaluate its effect on the hydrophilicity of the polymer.\n- **Specific Tasks**:\n  1. Prepare a series of modified polymer samples with varying concentrations of TMS-PEG.\n  2. Characterize and quantify the hydrophilicity of these polymers.\n- **Evaluation Criteria**: Quantify changes in hydrophilicity using appropriate analytical techniques, such as contact angle measurements or water absorption capacity testing.\n- **Critical Variables**:\n  - Concentration of TMS-PEG used in synthesis.\n  - Consistency in other synthetic parameters to isolate the effect of TMS-PEG.\n\n---\n\n### **Step 2: Experimental Design**\n\n---\n\n#### **A. Synthesis of Modified Polymer**\n\n1. **Polymer Platform**: Start with the base polymer that is to be modified with TMS-PEG. For example, let's assume the base polymer contains reactive hydroxyl or carboxyl groups suitable for chemical grafting or modification.\n\n2. **Reagents and Chemicals**:\n   - Base polymer (e.g., poly(vinyl alcohol), poly(acrylic acid), etc.).\n   - TMS-PEG (functionalized polyethylene glycol with reactive end groups, such as methoxysilyl groups).\n   - An appropriate coupling agent (if necessary) to link TMS-PEG to the base polymer.\n   - Solvent (e.g., ethanol, water, or an appropriate buffer, depending on the solubility of reactants).\n   - Catalyst (e.g., acids, bases, or silanization activators if using methoxysilyl groups).\n\n3. **Procedure**:\n   - Prepare a series of reaction solutions with varying concentrations of TMS-PEG (e.g., 0.1%, 0.5%, 1%, 2%, 5% by weight relative to the base polymer).\n   - Dissolve the base polymer in the solvent at a suitable concentration (e.g., 5–10 wt%).\n   - Gradually add TMS-PEG to the polymer solution while stirring to promote homogeneous mixing.\n   - Adjust the pH or add a coupling agent/catalyst as required to initiate the reaction (e.g., in the case of silanization, acidic or basic conditions may be required).\n   - Allow the reaction to proceed at a controlled temperature (e.g., 50–70°C) while stirring for the recommended reaction time (e.g., 24–48 hours for silanization reactions).\n\n4. **Post-Reaction Curing and Purification**:\n   - After the reaction is complete, remove unreacted TMS-PEG by dialyzing the solution against pure solvent or precipitating the polymer from the solution, followed by thorough washing.\n   - Dry the polymer under vacuum at a low temperature to avoid degradation of grafted TMS-PEG.\n\n---\n\n#### **B. Systematic Variation**\n\n- To study the effect of TMS-PEG concentration:\n  - Prepare a **set of samples** where the TMS-PEG concentration differs (e.g., 0.1%, 0.5%, 1%, 2%, 5% by weight relative to the base polymer).\n  - Ensure all other reaction parameters—such as temperature, time, base polymer concentration, and solvent—remain **constant** to isolate the effect of TMS-PEG concentration.\n  - Label the samples clearly and store them under consistent conditions.\n\n---\n\n### **Step 3: Hydrophilicity Evaluation**\n\nHydrophilicity can be evaluated using the following techniques. Systematic characterization is essential to extract reliable and quantitative data.\n\n#### **A. Contact Angle Measurements**\n1. **Principle**: Contact angle measures the wettability of a solid surface. Lower contact angles indicate higher hydrophilicity.\n2. **Equipment**: Contact angle goniometer.\n3. **Procedure**:\n   - Prepare thin polymer films or coatings on a flat substrate.\n   - Measure the static contact angle of a water droplet (2–5 µL) placed on the surface of each sample.\n   - Take multiple measurements on different areas of each sample to ensure reproducibility.\n4. **Analysis**: Compare the contact angles across different samples. Plot TMS-PEG concentration vs. contact angle to understand the correlation.\n\n#### **B. Water Absorption Studies**\n1. **Principle**: Hydrophilic polymers absorb more water than hydrophobic ones.\n2. **Procedure**:\n   - Immerse dry polymer samples (of known weight) in deionized water for a fixed duration (e.g., 24 hours).\n   - Remove excess water gently and weigh the swollen samples to calculate water uptake.\n   - Water absorption (%) = [(Wet Weight − Dry Weight) / Dry Weight] × 100.\n3. **Analysis**: Compare water absorption as a function of TMS-PEG concentration.\n\n#### **C. FTIR Spectroscopy**\n1. **Principle**: Confirm the extent of TMS-PEG incorporation by identifying characteristic PEG peaks (e.g., C–O–C stretching at ~1100 cm⁻¹).\n2. **Procedure**:\n   - Record FTIR spectra of all samples and the base polymer.\n   - Use the relative intensity of PEG characteristic peaks to assess modification levels.\n\n#### **D. Swelling Behavior**\n- Hydrophilicity can also be inferred from the swelling ratio in an aqueous environment. This involves immersing the polymer in water, measuring its dimensions or weight over time, and comparing swelling behavior across samples.\n\n---\n\n### **Step 4: Data Analysis and Interpretation**\n\n1. Plot the concentration of TMS-PEG (x-axis) against:\n   - Contact angle (y-axis, inversely proportional to hydrophilicity).\n   - Water absorption (%) or swelling ratio (y-axis, directly proportional to hydrophilicity).\n\n2. Analyze trends:\n   - Increased TMS-PEG concentration is expected to enhance hydrophilicity (lower contact angle, higher water absorption) up to a saturation point. Beyond this, additional TMS-PEG may have diminishing returns due to steric hindrance or aggregation.\n\n3. Statistical Analysis:\n   - Use statistical tools (e.g., ANOVA) to confirm the significance of observed trends.\n\n---\n\n### **Conclusion**\n\nBy systematically varying TMS-PEG concentration and employing the outlined evaluation methods, you can reliably quantify its effect on polymer hydrophilicity. This approach not only provides valuable insights but also establishes a robust framework for optimizing the synthesis process.\n\n---\n\nFeel free to ask additional questions or seek clarification on any step of the procedure!"
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+{
+  "design_question": "Propose an approach to assess the influence of the topological polar surface area (TPSA) of the chosen molecule on the hydrophilicity of the modified polymer after the experiment.",
+  "design_answer": "To assess the influence of the topological polar surface area (TPSA) of the chosen molecule on the hydrophilicity of the modified polymer after the experiment, we need to systematically outline a detailed experimental protocol that incorporates measurement tools and analytical methods. Here's my detailed answer, broken down step by step:\n\n---\n\n### **Step 1: Analyze the Question**\nThe question requires us to evaluate the relationship between TPSA, a molecular descriptor that correlates strongly with hydrophilicity, and the hydrophilicity of the final polymer. The experiment involves:\n1. Modifying a polymer with a chosen molecule (with its TPSA as a key feature).\n2. Measuring the hydrophilicity of the resulting polymer.\n3. Linking the observed hydrophilicity to the molecule’s TPSA.\n\nTPSA can serve as a helpful theoretical parameter when selecting or designing molecules for hydrophilic modification. A larger TPSA indicates greater polar functional group content, which is often associated with higher hydrophilicity.\n\n---\n\n### **Step 2: Design an Experimental Plan**\nTo assess the influence of TPSA on polymer hydrophilicity, the experiment can be broken down into four main phases: **polymer modification**, **hydrophilicity characterization**, **TPSA calculation**, and **correlation analysis**.\n\n---\n\n### **Phase 1: Polymer Modification**\nIn this phase, you will use the molecule provided to modify the base polymer, preparing a series of modified polymers.\n\n#### **Step 1.1: Base Polymer Selection**\n- Choose a polymer with tunable modification sites, such as **polyvinyl alcohol (PVA)** or **polyacrylamide (PAAM)**, which are hydrophilic but can be further modified.\n- Ensure hydroxyl, amine, or carboxylic groups are available for functionalization.\n\n#### **Step 1.2: Reaction Conditions**\n1. **Reagents**: Use the chosen molecule containing polar functional groups (TPSA known or calculable). Ensure it has reactive groups (e.g., hydroxyl, carboxyl, or amine).\n2. **Reaction Type**:\n   - If the molecule has carboxyl groups, employ **amide formation** or **esterification** (e.g., use N,N'-dicyclohexylcarbodiimide (DCC) or EDC in aqueous or organic solvents).\n   - If hydroxyl groups are present, use **etherification** or similar reactions with sodium hydroxide as a base.\n3. **Solvent**: Choose a solvent suitable for both the polymer and the chosen molecule. For hydrophilic polymers, water or dimethyl sulfoxide (DMSO) is often suitable.\n4. **Reaction Conditions**:\n   - Maintain temperature between **60–80°C** for esterification or amide formation.\n   - Adjust the reaction time to **4–6 hours** based on the reactivity of the molecule.\n   - Use a molar ratio of molecule to polymer functional groups as **2:1** to achieve sufficient modification.\n\n#### **Step 1.3: Purification**\n- Dialyze the solution against water for 48 hours to remove unreacted molecules and byproducts.\n- Freeze-dry the polymer to obtain a modified polymer sample.\n\n---\n\n### **Phase 2: Hydrophilicity Characterization**\nTo determine the hydrophilicity of the modified polymer, perform the following experiments:\n\n#### **Step 2.1: Contact Angle Measurement**\n- Prepare thin films of the modified polymer on a glass substrate.\n- Measure the water contact angle using a goniometer. Lower contact angles indicate higher hydrophilicity.\n- Ensure consistent experimental conditions (e.g., drop volume of 5 μL, temperature 25°C).\n\n#### **Step 2.2: Swelling Behavior**\n- Immerse the polymer sample in water at room temperature and measure the swelling ratio over time (e.g., equilibrium swelling after 48 hours). Hydrophilic polymers will absorb more water, leading to higher swelling ratios.\n  \n#### **Step 2.3: Surface Energy Analysis**\n- Perform surface energy characterization using an advanced tensiometer or surface analysis tool. Hydrophilic surfaces have higher polar component contributions.\n\n### **Phase 3: TPSA Calculation**\nThe TPSA values of the chosen molecule influence the hydrophilicity. To accurately measure TPSA:\n1. Use computational software like **ChemBioDraw, MarvinSketch**, or **SwissADME**.\n2. Input the structure of the chosen molecule and calculate its TPSA.\n3. For molecules already tested, TPSA values are readily available in the literature.\n\n### **Phase 4: Correlation Analysis**\nOnce hydrophilicity data and TPSA values are available:\n1. Plot the TPSA of the different molecules used for modification against the hydrophilicity metrics (e.g., contact angle, swelling ratio).\n2. Use statistical tools such as **linear regression analysis** to establish the relationship between TPSA and hydrophilicity. A positive trend (e.g., higher TPSA correlates to increased hydrophilicity) supports the hypothesis.\n\n---\n\n### **Additional Considerations**\n1. **Reproducibility**: Perform each step of synthesis and characterization in triplicate to minimize experimental error.\n2. **Controls**: Include unmodified polymer as a control sample.\n3. **Functional Group Characterization**:\n   - Use Fourier-transform infrared (FTIR) spectroscopy to confirm successful attachment of the molecule to the polymer.\n   - Use nuclear magnetic resonance (NMR) spectroscopy to quantify the degree of functionalization.\n\n---\n\n### **Summary**\nThis experimental scheme systematically explores the influence of TPSA on polymer hydrophilicity. By linking TPSA values to hydrophilicity measurements (contact angle, swelling, surface energy), you can evaluate the extent to which polar functional groups and TPSA contribute to hydrophilic behavior in the final polymer. This approach is both rigorous and comprehensive, providing the ability to scientifically validate the relationship between TPSA and hydrophilicity.\n\n---\nThis scheme should allow you to successfully complete the experiment and provide insight into the molecular design principles for enhanced hydrophilicity in polymers!"
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+{
+  "design_question": "When preparing a hydrophilic polymer using tannic acid (TA) and polyvinyl alcohol (PVA), what solvent system would you recommend to achieve good processability and stability of the mixture? Justify your choice.",
+  "design_answer": "Certainly! This is an excellent question regarding the synthesis of hydrophilic polymers, especially using tannic acid (TA) and polyvinyl alcohol (PVA). Let's systematically analyze your question and provide a detailed and scientifically rigorous response.\n\n---\n\n### **Step 1: Analysis of the Question**\nThe question centers on selecting a solvent system for the preparation of a hydrophilic polymer using tannic acid (TA) and polyvinyl alcohol (PVA). The key considerations here are:\n\n1. **Solubility Compatibility**:\n   Both tannic acid and polyvinyl alcohol must be dissolved or dispersed effectively in the solvent to ensure homogeneous blending.\n\n2. **Processability**:\n   The solvent system should facilitate smooth preparation, avoid aggregation or precipitation of components, and allow consistent polymer formation.\n\n3. **Stability**:\n   The solvent medium should maintain the stability of the components (chemically and thermodynamically) during reaction and polymer processing.\n\n4. **Hydrophilicity Enhancement**:\n   The solvent choice must align with the goal of maximizing hydrophilicity in the resulting polymer, as TA and PVA are both hydrophilic in nature.\n\n---\n\n### **Step 2: Recommended Solvent System**\nAn ideal solvent system for the synthesis of a hydrophilic polymer using tannic acid (TA) and polyvinyl alcohol (PVA) would be **water-based**, specifically:\n\n1. **Distilled Water**:\n   - Tannic acid is highly soluble in water due to its polyphenolic structure with hydroxyl groups, which readily form hydrogen bonds with water.\n   - Polyvinyl alcohol is also soluble in water, particularly at elevated temperatures, as its hydroxyl groups interact strongly with water molecules.\n\n2. **Addition of Ethanol (Optional)**:\n   - If necessary to enhance processability (such as to reduce viscosity or facilitate mixing), a small percentage (5–20%) of ethanol can be added to the system. Ethanol improves miscibility and can slightly reduce the polarity of the solvent, aiding in uniform blending of the components.\n\n---\n\n### **Step 3: Justification of the Solvent Choice**\nThe selection of distilled water (with optional ethanol) is justified as follows:\n\n1. **Compatibility**:\n   - Tannic acid (TA) is inherently highly hydrophilic due to its phenol groups, and polyvinyl alcohol (PVA) has hydroxyl-rich chains. Water effectively solubilizes both components while supporting hydrogen bonding interactions.\n   - Ethanol can help stabilize the mixture by reducing viscosity and enhancing mixing, without compromising the hydrophilic characteristics.\n\n2. **Processability**:\n   - Water is a green solvent, easy to handle, and readily evaporates during the drying or curing process of polymer preparation. Ethanol evaporates even more quickly, ensuring clean processing.\n\n3. **Stability**:\n   - At room temperature and mild reaction conditions, both tannic acid and polyvinyl alcohol remain chemically stable in water. Upon heating (e.g., 70–90°C), PVA dissolves completely, and TA remains intact, forming a homogeneous mixture ideal for polymer crosslinking.\n\n4. **Promotion of Hydrophilicity**:\n   - The use of water ensures the hydrophilic functionality of TA and PVA is retained and further emphasized in the polymer network, as no nonpolar solvents are introduced that could interfere with hydrophilicity.\n\n---\n\n### **Step 4: Detailed Experimental Preparation Scheme**\nHere is a step-by-step synthesis procedure for preparing the hydrophilic polymer using tannic acid (TA) and polyvinyl alcohol (PVA), utilizing the selected solvent system:\n\n1. **Materials Required**:\n   - Tannic acid (TA)\n   - Polyvinyl alcohol (PVA) (molecular weight 85,000–124,000, 99+% hydrolyzed preferred)\n   - Distilled water\n   - Ethanol (optional, for processability)\n   - Magnetic stirrer and heating plate\n   - Beaker, thermometer, and other standard laboratory equipment\n\n2. **Step 1: Preparation of PVA Solution**:\n   - Add **5–10 g of PVA** to **100 mL of distilled water** in a beaker.\n   - Heat the mixture to **70–90°C** with stirring to dissolve the PVA completely. Monitor the temperature carefully to avoid overheating, which may degrade the polymer.\n\n3. **Step 2: Preparation of TA Solution**:\n   - Dissolve **1–3 g of tannic acid** into **20–50 mL of distilled water** in a separate container. Stir the solution to ensure complete dissolution. If ethanol is being used, add it to this solution in a **10–15 vol% ratio**.\n\n4. **Step 3: Mixing**:\n   - Slowly add the TA solution to the PVA solution while stirring continuously to ensure homogeneous blending.\n   - If necessary, maintain a mild heating condition (around **50–60°C**) to facilitate uniform mixing.\n\n5. **Step 4: Crosslinking (Optional)**:\n   - To form a crosslinked hydrophilic polymer network, introduce a crosslinking agent (e.g., boric acid or glutaraldehyde) in controlled quantities. Typically, use **1–3 wt% of the crosslinker** based on the total weight of PVA present.\n   - Continue stirring for an additional 30–60 minutes.\n\n6. **Step 5: Casting and Drying**:\n   - Pour the mixture onto a flat substrate (glass or Teflon mold) and allow it to cure or evaporate at room temperature or mild heating (~40–60°C) overnight.\n   - Peel off the resulting polymer film, and confirm hydrophilicity via contact angle measurement or water absorption studies.\n\n---\n\n### **Step 5: Concluding Remarks**\nThe solvent system consisting of distilled water (with optional ethanol) provides the optimal balance of compatibility, processability, and stability for synthesizing hydrophilic polymers based on tannic acid and polyvinyl alcohol. Additionally, it promotes the desired hydrophilicity due to the absence of nonpolar solvents.\n\nThis comprehensive approach ensures that you can successfully synthesize a high-quality hydrophilic polymer in the laboratory while maintaining environmental considerations and scientific rigor.\n\nIf you have further questions or need clarification on experimental details, feel free to ask!"
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+{
+  "design_question": "Describe the process of using a polymerization reaction template to incorporate the molecule into a polymer structure in order to improve its hydrophilicity. Highlight any considerations specific to this molecule.",
+  "design_answer": "To systematically address your question regarding incorporating the molecule into a polymer structure via a polymerization reaction template to enhance hydrophilicity, allow me first to analyze the key aspects of your question and then design an experimental preparation scheme accordingly.\n\n---\n\n### **Analysis of Your Question**\n1. **Goal:**  \n   The objective is to integrate the provided molecule into a polymer structure to improve hydrophilicity. This involves leveraging functional groups in the molecule that contribute to hydrophilicity, such as hydroxyl (-OH), amine (-NH2), carboxyl (-COOH), or other polar groups.\n\n2. **Polymerization Reaction Template:**  \n   We need to select an appropriate polymerization method (e.g., free radical polymerization, condensation polymerization, or controlled/living polymerization) suited to the molecule and its functional groups.\n\n3. **Key Considerations:**  \n   Specific strategies will depend on the chemical structure of the molecule you provided, including:\n   - Whether the molecule serves as a monomer or requires functionalization.\n   - The compatibility of its functional groups with the polymer backbone.\n   - Reaction conditions to preserve the integrity of hydrophilic groups.\n\n4. **Output:**  \n   The synthesized polymer must exhibit enhanced hydrophilicity, which may be tested by water absorption, contact angle measurements, or dissolution behavior in aqueous environments.\n\n---\n\n### **Experimental Synthesis Scheme**\n\nBelow, I'll outline a detailed and systematic synthesis protocol for preparing a hydrophilic polymer while incorporating your molecule into the polymer structure. This procedure can be tailored depending on the exact chemical structure of the molecule you provided.\n\n#### **Step 1: Selection of Polymerization Method**\nBased on the functional groups in the molecule:\n- **Free Radical Polymerization** is suitable if the molecule contains unsaturation like a vinyl group (-CH=CH2).\n- **Condensation Polymerization** works well for molecules with carboxylic acids (-COOH), hydroxyl groups (-OH), or amines (-NH2).\n- **Ring-Opening Polymerization** may be chosen for cyclic molecules capable of hydrolysis.\n\nGiven the emphasis on hydrophilicity, monomers like acrylic acid, acrylamide, or their derivatives might be used.\n\n---\n\n#### **Step 2: Molecular Incorporation**\nIf the provided molecule does not possess reactive polymerizable groups, we may need to functionalize it, preparing it as a co-monomer. For instance:\n- **Functionalization Strategy:** Add polymerizable groups like methacrylate or acrylate by esterification or amidation reactions.\nExample:\n   - To functionalize a molecule with a hydroxyl (-OH) group:\n     - React it with methacrylic acid via esterification using a catalyst like dicyclohexylcarbodiimide (DCC) or 4-dimethylaminopyridine (DMAP).\n\n---\n\n#### **Step 3: Polymerization Reaction**\n**Reaction Type:**  \nLet’s proceed step-by-step for free radical polymerization:\n\n1. **Reagents:**\n   - Monomer: Acrylic acid (hydrophilic base polymer).\n   - Co-monomer: Functionalized molecule.\n   - Initiator: Azobisisobutyronitrile (AIBN) or potassium persulfate (KPS).\n   - Solvent: Water or ethanol (to favor hydrophilicity).\n\n2. **Preparation:**\n   - **Molar Ratios:**  \n     A typical ratio for a copolymer is 1 mole of acrylic acid to 0.1–0.3 mole of functionalized co-monomer. Adjust based on desired hydrophilicity and molecular weight.\n\n3. **Reaction Conditions:**\n   - Temperature: 60–70 °C (optimal for AIBN decomposition).\n   - Atmosphere: Nitrogen to prevent oxidative deterioration.\n   - Time: 4–6 hours (ensures high conversion).\n\n4. **Procedure:**\n   - Dissolve the monomer and co-monomer in the solvent.\n   - Add the initiator under stirring.\n   - Heat the reaction mixture while maintaining nitrogen flow.\n   - Monitor viscosity changes as polymerization progresses.\n\n---\n\n#### **Step 4: Post-Polymerization Processing**\n1. **Purification:**\n   - Precipitate the polymer in a non-solvent like methanol or acetone.\n   - Filter and wash thoroughly to remove unreacted monomers.\n\n2. **Drying:**\n   - Dry the polymer under vacuum at 40–50 °C to avoid thermal degradation.\n\n---\n\n#### **Step 5: Characterization of Hydrophilicity**\n1. **Water Absorption:**\n   - Soak the polymer in water and measure the percentage increase in mass.\n2. **Contact Angle Measurement:**\n   - Analyze the angle formed between water droplets and the polymer surface.\n3. **Fourier Transform Infrared (FTIR) Spectroscopy:**\n   - Verify incorporation of hydrophilic functional groups.\n\n---\n\n### **Specific Considerations for the Provided Molecule**\nDepending on your molecule:\n1. **Functional Groups:** Pay attention to primary functional groups (e.g., hydroxyl, amine, carboxyl) for reactivity and hydrophilicity enhancement.\n2. **Steric Hindrance:** If bulky groups are present, ensure they do not impede polymerization or reduce hydrophilicity.\n3. **Hydrophilic Enhancement:** Incorporating additional hydrophilic monomers (e.g., ethylene glycol derivatives) alongside your molecule may improve water affinity.\n\n---\n\n### **Concluding Remarks**\nBy following this protocol, you can:\n1. Systematically integrate your molecule into a hydrophilic polymer structure.\n2. Achieve a material with enhanced water affinity suited for biomedical, coating, or other applications.\n\nLet me know if you can share the exact chemical structure of the molecule you provided for further tailoring!"
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+{
+  "design_question": "Explain how you can design an experiment using a molecule capable of forming dynamic cross-links to prepare a hydrophilic polymer with controllable degradability. What factors would you consider to ensure the stability and functionality of the final material?",
+  "design_answer": "To answer your question, we will develop a systematic experimental preparation scheme based on the principles of hydrophilic polymer synthesis and the design of materials with dynamic cross-links. This approach will allow us to engineer a hydrophilic polymer with controllable degradability, suitable for various applications such as drug delivery, tissue engineering, or bio-inspired materials.\n\n---\n\n### **Step-by-Step Approach**\n\n#### **Step 1: Key Points of the Question**\n- **Objective:** Design an experiment to synthesize a hydrophilic polymer that incorporates dynamic cross-links for controllable degradability.\n- **Key Considerations:**\n  1. Selection of hydrophilic monomers/polymers to enhance water affinity.\n  2. Incorporation of reversible or dynamic cross-links to introduce degradability.\n  3. Optimization of reaction conditions (solvent, temperature, pH, catalyst, etc.).\n  4. Factors to ensure stability and functionality, such as avoiding premature degradation and maintaining hydrophilic properties.\n\n#### **Step 2: Experimental Scheme Overview**\nTo prepare a hydrophilic polymer with controllable degradability, the experiment will involve:\n1. Selection of base polymer or monomers (hydrophilic).\n2. Functionalization or grafting with dynamic cross-linking groups.\n3. Polymerization process or cross-linking step, followed by purification.\n4. Characterization and testing of hydrophilicity, degradability, and stability.\n\n---\n\n### **Detailed Experimental Preparation Scheme**\n\n#### **Step 3: Selection of Materials**\n1. **Hydrophilic Monomers/Polymers:**\n   - Choose well-known hydrophilic monomers such as acrylamide, polyethylene glycol (PEG), or poly(ethylene oxide) (PEO).\n   - Alternatively, select functionalized hydrophilic molecules like hydroxyl or carboxyl-containing acrylates (e.g., acrylic acid or hydroxyethyl methacrylate).\n\n2. **Dynamic Cross-linking Groups:**\n   - Use molecules capable of forming reversible bonds:\n     - Schiff base chemistry (aldehyde + primary amine).\n     - Disulfide bonds.\n     - Boronic ester bonds (diol + boronic acid).\n     - Hydrogen bonding or ionic interactions (e.g., calcium alginate).\n   - Consider the application conditions: For physiological environments, dynamic bonds that respond to pH or reducing agents are ideal.\n\n---\n\n#### **Step 4: Experimental Procedure**\n##### **A. Preparation of Hydrophilic Polymer Solution**\n1. **Step:** Dissolve the hydrophilic monomer or polymer in a suitable solvent.\n   - Common solvents: Water, ethanol, or an aqueous buffer (pH ~7).\n   - Example ratio: For PEG, prepare a 20 wt% solution.\n2. **Consideration:** Adjust pH to maintain stable cross-linking functionality (e.g., ~pH 7–8 for Schiff base reactions).\n\n##### **B. Functionalization of Polymer with Dynamic Cross-linking Groups**\n3. **Step:** Add functional group precursors into the hydrophilic polymer solution to graft dynamic cross-linking moieties. \n   - Example: For aldehyde-amine Schiff base formation, PEG-dialdehyde can be prepared by oxidizing PEG with periodate. Dialdehyde groups can then react with primary amines during cross-linking.\n   - Ratios: Ensure the molar ratio of reactive groups matches the desired cross-linking density (e.g., aldehyde-to-amine molar ratio ~1.2:1 to ensure complete cross-linking).\n\n##### **C. Polymerization or Cross-link Formation**\n4. **Step:** Initiate polymerization or cross-linking under controlled conditions.\n   - Example: For Schiff base cross-linking:\n     - Mix the dialdehyde-grafted hydrophilic polymer with an amine-containing crosslinker (e.g., lysine or polyethyleneimine).\n     - Adjust the molar ratio to control the resulting polymer network density.\n     - Allow the reaction to proceed at room temperature (~20–25°C) for several hours.\n5. **Consideration:** For dynamic bonds, ensure reversibility under target degradation conditions (e.g., Schiff base stability depends on pH; rapid degradation occurs in acidic environments <pH 6).\n\n##### **D. Purification**\n6. **Step:** Remove unreacted reagents via techniques like dialysis or precipitation.\n   - Example: Dialyze the polymer gel in water or buffer for 24–48 hours to remove small molecule impurities.\n7. **Consideration:** Verify that dynamic cross-links remain intact after purification.\n\n---\n\n#### **Step 5: Characterization**\nAfter synthesizing the hydrophilic polymer, conduct the following tests:\n1. **Hydrophilicity:**\n   - Evaluate water absorption or swelling properties (e.g., swelling ratio in water).\n   - Measure contact angle (lower values indicate higher hydrophilicity).\n\n2. **Dynamic Cross-linking and Degradability:**\n   - Test the polymer under degradable conditions (e.g., acidic pH for Schiff bases, reducing environments for disulfide bonds).\n   - Measure mass loss over time to quantify degradability.\n\n3. **Stability:**\n   - Confirm that the polymer remains functional under storage conditions (e.g., stability in water at room temperature over weeks).\n   - Use FTIR or NMR spectroscopy to confirm retention of dynamic cross-linking groups.\n\n---\n\n#### **Step 6: Factors to Ensure Stability and Functionality**\nFinally, consider the following factors:\n1. **Reaction Environment:** Maintain favorable solvent, pH, and temperature to ensure proper cross-link formation without premature degradation.\n2. **Control of Cross-link Density:** Optimize the molar ratios to balance hydrophilicity, mechanical properties, and degradability (e.g., excessive cross-linking can hinder degradation).\n3. **Postprocessing:** Store the polymer in a hydrated environment to retain hydrophilic features.\n4. **Application-Specific Design:** Tune degradability based on intended use (e.g., rapid degradation for drug delivery vs. slow degradation for scaffolds).\n\n---\n\n#### **Summary**\nBy combining hydrophilic monomers/polymers with dynamic cross-linking groups, you can design a hydrophilic polymer with controlled degradability. Careful adjustment of reaction conditions (pH, molar ratios, solvent selection) and characterization techniques will help ensure the stability and functionality of the final material. This systematic approach will allow you to successfully prepare the material in a laboratory setting.\n\n"
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+{
+  "design_question": "Design an experimental sequence to synthesize a hydrophilic polymer using Dye-NHS ester as an initiator. Justify how this molecule contributes to the hydrophilicity of the resulting polymer without referencing proprietary information.",
+  "design_answer": "### Analysis of the Question\n\nYour question revolves around designing an experimental scheme for synthesizing a hydrophilic polymer using Dye-NHS ester as an initiator, while explaining the role of this molecule in improving hydrophilicity. Based on the given question, the following key points need to be addressed systematically:\n\n1. **Experimental framework:** Provide a detailed, step-by-step preparation sequence for polymer synthesis using Dye-NHS ester as the initiator. Specification of reaction conditions, quantities, and key synthetic procedures is required.\n2. **Hydrophilicity enhancement:** Scientifically justify why the Dye-NHS ester contributes to hydrophilicity and how its molecular structure influences the properties of the polymer.\n\nLet us proceed step by step, ensuring all scientific aspects are covered.\n\n---\n\n### Part 1: Experimental Sequence for Synthesizing a Hydrophilic Polymer\n\n**Objective:** To prepare a hydrophilic polymer initiated by Dye-NHS ester to ensure optimal hydrophilicity, while considering the functional reactivity of NHS esters and their incorporation into the polymer backbone.\n\n#### Step 1: Materials and Reagents Collection\n\n- **Dye-NHS ester:** Initiator molecule. NHS esters react efficiently with nucleophilic amines or hydroxyl-containing monomers.\n- **Hydrophilic monomer(s):** Choose monomers such as acrylamide (AM), polyethylene glycol (PEG) acrylate, N-vinylpyrrolidone (NVP), or hydroxyethyl methacrylate (HEMA), which form hydrophilic polymer chains.\n- **Solvent:** Prefer aqueous or mixed organic-aqueous solvents like DMSO-water or ethanol-water to promote solubility and maintain hydrophilicity during polymerization.\n- **Catalyst (optional):** Depending on the monomer, include catalysts such as ammonium persulfate (APS) for radical polymerization or use a thermal or photoinitiation pathway.\n- **Crosslinker (if needed):** For films or networks, optional hydrophilic crosslinkers like N,N′-methylenebisacrylamide (MBA) may be added.\n\n---\n\n#### Step 2: Synthetic Procedure\n\n1. **Activation of Dye-NHS Ester:**\n   - Molecular dye components containing NHS esters act as coupling agents that facilitate polymer initiation. Dissolve Dye-NHS ester in an appropriate solvent (e.g., DMSO or ethanol) to activate the ester functionality.\n   - Place Dye-NHS ester (e.g., 0.01 mole) in a reaction vessel and stir at room temperature to ensure dissolution.\n\n2. **Preparation of Monomer Solution:**\n   - Prepare the hydrophilic monomer solution. Dissolve acrylamide (AM) or PEG acrylate in the solvent to create a mixture. Use a molar ratio of monomer to Dye-NHS ester in the range of **20:1–50:1**, depending on the desired molecular weight of the polymer.\n   - For example:\n     - Acrylamide (AM): Weigh ~2 g (0.03 mole).\n     - DMSO mixed with water (50:50 v/v) to maintain miscibility and control hydrophilicity.\n\n3. **Reaction Initiation (Coupling or Radical):**\n   - Slowly add Dye-NHS ester to the monomer solution under stirring. Allow the NHS ester to react with hydroxyl or amine groups of the monomers.\n   - If no natural nucleophiles are available, trigger radical polymerization using APS (0.01 mole) and heat (~60°C) in oxygen-free conditions (purge with nitrogen). Alternatively, UV irradiation could initiate polymerization using photoinitiators.\n\n4. **Polymer Chain Propagation:**\n   - Maintain the reaction temperature at 60°C for approximately 3–4 hours. If radical conditions are used, ensure uniform stirring under N2 atmosphere to prevent chain termination.\n\n5. **Polymer Purification:**\n   - Precipitate the polymer by pouring the reaction mixture into cold ethanol or acetone. Collect the precipitate by centrifugation or filtration.\n   - Wash the polymer thoroughly with ethanol and water to remove unreacted Dye-NHS ester or unreacted monomer traces.\n\n6. **Drying:**\n   - Dry the purified polymer in a vacuum oven at ~40°C to obtain the final hydrophilic polymer.\n\n---\n\n### Part 2: Justification of Hydrophilicity Improvement\n\n**Role of Dye-NHS Ester:**\n- **Reactive functionality:** The NHS ester group in Dye-NHS ester readily reacts with hydroxyl or amine-containing monomers, ensuring that the dye is covalently incorporated into the polymer backbone. This incorporation enhances the polarity and hydrophilicity of the polymer as NHS esters are compatible with hydrophilic monomers.\n  \n- **Dye contribution:** The molecular dye incorporated into the polymer backbone could contain hydrophilic substituents like sulfonic groups (-SO3H), carboxylic groups (-COOH), or hydroxyl groups (-OH). These substituents significantly increase the water solubility and wettability of the polymer surface.\n\n- **Hydrophilic scaffold:** As polymer chains grow, the NHS ester ensures functional grafting and compatibility with hydrophilic monomers, leading to an evenly distributed hydrophilic profile and preventing aggregation.\n\n---\n\n### Final Notes\n\nThe experiment outlined provides a clear, reproducible pathway for the synthesis of Dye-NHS ester-based hydrophilic polymers. The use of hydrophilic monomers in aqueous or mixed solvents complements the inherent polar properties introduced by Dye-NHS ester. By carefully controlling reagent ratios, reaction conditions, and purification steps, the student will achieve a hydrophilic polymer suitable for biomedical coatings, water purification, or other applications."
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diff --git a/task2/task2-qa/╛╓▓┐╡▌╦═└╫┼┴├╣╦╪═и╣¤╡ў┐╪╣╟...┐╫╝┘╠х╜ч├ц╣╟╒√║╧╡─╗·╓╞╤╨╛┐_└ю╫ц║╞.json b/task2/task2-qa/╛╓▓┐╡▌╦═└╫┼┴├╣╦╪═и╣¤╡ў┐╪╣╟...┐╫╝┘╠х╜ч├ц╣╟╒√║╧╡─╗·╓╞╤╨╛┐_└ю╫ц║╞.json
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+{
+  "design_question": "Design an experimental protocol to incorporate N-carboxyethyl chitosan (CEC) into a polymer hydrogel system, ensuring the final material has improved hydrophilic properties. Describe the role of CEC in the resulting hydrogel's hydrophilicity.",
+  "design_answer": "Certainly. Let us carefully think through the question and break it down for clarity.\n\n### **Step 1: Analysis of the Question and Key Points**\nYour question centers on incorporating **N-carboxyethyl chitosan (CEC)**, a functionalized derivative of chitosan, into a polymer hydrogel system to enhance its **hydrophilic properties**. My task is to design a complete, step-by-step experimental protocol while justifying the choice of reagents and conditions, and explaining how CEC contributes to increased hydrophilicity in the resulting hydrogel.\n\n#### Key Points:\n1. The functional CEC (a derivative of chitosan) needs to be integrated into a polymer hydrogel matrix.\n2. The goal is to achieve greater hydrophilicity in the hydrogel, likely owing to CEC’s inherent hydrophilic groups (e.g., carboxyl (-COOH) and amine (-NH2)).\n3. The experimental protocol must detail each step of the synthesis process, including reaction conditions, reagents, and their roles.\n\n---  \n\n### **Step 2: Systematic Experimental Protocol**\nBelow, I outline a suggested experimental protocol for incorporating CEC into a polymer hydrogel system. For simplicity, we assume the base hydrogel system is poly(vinyl alcohol) (PVA), known for its biocompatibility and film-forming properties. We will crosslink the CEC with PVA to form a composite hydrogel.\n\n#### **Materials Required:**\n- **N-carboxyethyl chitosan (CEC)**: The hydrophilic functional component.\n- **Poly(vinyl alcohol) (PVA)**: A base polymer for hydrogel synthesis.\n- **Glutaraldehyde** (50 wt% aqueous solution): A crosslinking agent.\n- **Distilled water**: Solvent.\n- **Hydrochloric acid (HCl)**: pH adjustment for crosslinking activation.\n- **Phosphate buffer solution (PBS)** (pH 7.4): Used to wash and neutralize the hydrogel.\n- **Glycerol** (optional): A plasticizer to enhance flexibility of the final hydrogel.\n\n---\n\n#### **Step-by-Step Protocol**\n\n1. **Preparation of PVA Solution (10 wt%):**\n   - Dissolve **10 g PVA** in **90 mL distilled water**.\n   - Heat at **90°C** with constant stirring to ensure complete dissolution.\n   - Cool the solution to room temperature before proceeding to the next step.\n\n2. **Preparation of CEC Solution (2.5 wt%):**\n   - Dissolve **2.5 g CEC** in **97.5 mL distilled water** under gentle stirring.\n   - The pH of the solution may need to be adjusted if CEC does not dissolve easily due to electrostatic interactions. Adjust the pH to **4-6 using 0.1 N HCl**, ensuring solubility.\n\n3. **Mixing PVA and CEC:**\n   - Gradually mix the CEC solution with the prepared PVA solution.\n   - For example, use a PVA-to-CEC ratio of **80:20 by mass** (e.g., 8 g PVA solution and 2 g CEC solution). \n   - Stir the combined solution thoroughly to ensure uniform dispersion of CEC in the PVA matrix. Monitor the mixture visually for homogeneity.\n\n4. **Addition of Crosslinking Agent:**\n   - Add **glutaraldehyde (GA)** dropwise to the PVA-CEC mixture. Typical GA concentrations range from **0.5-1 wt% based on the total polymer weight**.\n   - Stir the mixture continuously at **room temperature**. The crosslinking reaction between the primary amine groups of CEC and aldehyde groups of GA helps create a covalent network structure between PVA and CEC.\n\n5. **pH Adjustment for Crosslinking Reaction:**\n   - Using **0.1 M HCl**, adjust the pH of the mixture to **4-5** to optimize the reactivity of glutaraldehyde, which is most effective at slightly acidic conditions.\n\n6. **Casting the Hydrogel:**\n   - Pour the resulting viscous solution into a clean glass mold or Petri dish to ensure even distribution.\n   - Allow the hydrogel to cure at **room temperature for 12-24 hours**, ensuring proper crosslinking and network formation.\n\n7. **Post-Treatment and Washing:**\n   - After curing, immerse the hydrogel in **phosphate buffer solution (PBS, pH 7.4)** for 24 hours to remove residual glutaraldehyde and any unreacted components. This step ensures biocompatibility and neutrality of the hydrogel.\n   - Optionally, introduce **glycerol (e.g., 1 wt% of total polymer weight)** into the washing process to enhance flexibility.\n\n8. **Drying or Storage (Optional):**\n   - (If a dry hydrogel is needed) Dry the hydrogel in a vacuum oven at **40-50°C** until a constant weight is achieved.\n   - If maintaining hydrated conditions, store in PBS solution at **4°C** until use.\n\n---\n\n#### **Step 3: Role of CEC in the Hydrogel’s Hydrophilicity**\nN-carboxyethyl chitosan (CEC) contributes significantly to the hydrophilicity of the resulting hydrogel:\n1. **Presence of Carboxyl Groups (-COOH):** The carboxyl groups of CEC are highly hydrophilic and can hydrogen bond with water, increasing the overall water-retention capacity of the hydrogel.\n2. **Amino Groups (-NH2):** The functional amine groups add additional sites for hydrogen bonding with water, further enhancing hydrophilicity.\n3. **Ionic Interactions:** The carboxyl groups (in their ionized form) can also increase ionic interactions, improving water adsorption and swelling behavior.\n4. **Homogeneous Dispersion:** When well-dispersed in the PVA matrix, CEC forms a network that promotes both physical and covalent bonding, increasing the integrity of the hydrogel while enhancing hydrophilicity.\n\n---\n\n### **Final Notes**\nThis protocol can be adjusted to the specific needs of your hydrogel application (e.g., biomedical, environmental, etc.) by tweaking the polymer blend ratios, crosslinker concentration, or reaction conditions. Additionally, to further analyze the hydrogel’s hydrophilicity after preparation, characterization techniques such as **contact angle measurement**, **swelling ratio tests**, or **Fourier-transform infrared spectroscopy (FTIR)** can be utilized.\n\nIf you have further questions or need assistance during your experiment, feel free to ask. It is important to plan, prepare reagents carefully, and prioritize safety in the laboratory.\n\n"
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diff --git a/task2/task2-qa/╛█├╤╕─╨╘╢р├ц╠х╡═╛█▒╢░ы╣ш╤ї═щ╣╣╓■─═╦о╨╘╟╫╦о╖└╬э═┐▓у.json b/task2/task2-qa/╛█├╤╕─╨╘╢р├ц╠х╡═╛█▒╢░ы╣ш╤ї═щ╣╣╓■─═╦о╨╘╟╫╦о╖└╬э═┐▓у.json
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+{
+  "design_question": "How would you utilize pentaerythritol tetrathioglycolate (PTMP) in a polymer modification experiment to enhance hydrophilicity? Elaborate on the steps to ensure a consistent product and high reaction yield.",
+  "design_answer": "Certainly! Let us analyze your question and systematically construct a detailed response to ensure clarity and rigor for your experiment. The goal is to utilize pentaerythritol tetrathioglycolate (PTMP) in a polymer modification experiment to enhance hydrophilicity. With a hydrophilic end goal in mind, we can approach this by leveraging PTMP's thiol functional groups to graft hydrophilic functional groups onto the polymer matrix. I will break this down step by step, covering each step in detail.\n\n---\n\n### 1. Analysis of the Question\n\n- **Key molecule**: Pentaerythritol tetrathioglycolate (PTMP). This molecule possesses 4 thiol (-SH) groups, making it a highly reactive branching agent in polymer chemistry.\n- **Objective**: Enhance hydrophilicity of a polymer.\n- **Approach**: Modify the polymer using PTMP through chemical grafting.\n- **Desired outcome**: A hydrophilic polymer with consistent product quality and a high reaction yield.\n\n---\n\n### 2. Experimental Preparation Scheme for Hydrophilic Polymer Modification Using PTMP\n\n#### Step 1: Selection of the Polymer Substrate\nChoose a polymer substrate that readily undergoes functional group modification. Polymers such as polyethylene glycol (PEG), polyacrylamides, or polyvinyl alcohol (PVA) are good candidates. If the polymer lacks reactive sites, it may require pre-treatment, such as introducing double bonds or reactive pendant groups into its structure.\n\n#### Step 2: Solvent System\nUse an appropriate solvent that ensures efficient solubility of PTMP and the polymer. Possible solvents include polar organic solvents such as dimethyl sulfoxide (DMSO) or tetrahydrofuran (THF). DMSO is preferred for reactions targeting hydrophilic polymers due to its polar nature and compatibility with thiol chemistry.\n\n#### Step 3: Functionalization Reaction\nTo graft PTMP onto the polymer backbone, utilize a thiol-ene or thiol-Michael addition chemistry approach—both are ideal to exploit PTMP’s thiol groups in a controlled environment.\n\n- **Reaction conditions:**\n  - **Mechanism 1 - Thiol-Ene Click Reaction**:\n    - Requires unsaturated (C=C double bond) groups on the polymer.\n    - These can be naturally present or introduced via pre-modification. A free-radical initiator (e.g., azobisisobutyronitrile, AIBN) or photoinitiator (e.g., Irgacure) can be used under UV light or thermal conditions.\n    - Reaction temperature: 60-80°C (mild heating ensures reactivity and avoids side reactions).\n    - Reaction time: 4-6 hours under inert conditions (e.g., nitrogen or argon blanket to prevent thiol oxidation).\n\n  - **Mechanism 2 - Thiol-Michael Addition**:\n    - Requires electron-deficient alkene groups on the polymer (e.g., acrylates or maleimides).\n    - Reaction catalyst: Tertiary amines like triethylamine (TEA) or sodium hydroxide (NaOH) at 0.1 to 0.5 M concentration.\n    - Reaction temperature: 30-50°C (near ambient temperature avoids degradation).\n    - Reaction time: 3-4 hours with stirring.\n\n- **Reagent Ratios:**\n  - PTMP:Polymer = 1:2 molar ratio (excess polymer ensures complete utilization of PTMP’s reactive sites while avoiding crosslinking-induced gelation).\n\n#### Step 4: Introduction of Hydrophilic Groups\nThe hydrophilicity of the modified polymer will be increased by appending polar functional groups. Some strategies include:\n- **Hydrolysis**: Post-reaction hydrolysis of ester groups on PTMP (if applicable) can generate hydroxyl (-OH) groups.\n- **Use of Polar Monomers or Crosslinkers**: You may alternatively consider coupling PTMP with hydrophilic crosslinkers such as acrylic acid, methacrylic acid, or sulfonic acid derivatives.\n\n#### Step 5: Purification\nTo ensure a consistent product, remove unreacted PTMP and polymer impurities using the following methods:\n- Dilute the reaction medium with excess water or alcohol, inducing precipitation of excess reagent.\n- Perform dialysis using a membrane with an appropriate molecular weight cutoff (MWCO). For instance, polyethylene glycol dialysis tubing works well for hydrophilic polymers.\n- Dry the purified polymer under vacuum or lyophilize to avoid thermal degradation.\n\n#### Step 6: Characterization of the Final Hydrophilic Polymer\nOnce the modified polymer is prepared, confirm the success of hydrophilic functionalization using the following techniques:\n- **Fourier-transform infrared spectroscopy (FTIR)**: Look for characteristic thiol peaks (2550 cm⁻¹) interactions and emergence of polar group peaks (-OH stretch ~3400 cm⁻¹ or sulfate peaks ~1200 cm⁻¹).\n- **Contact angle measurements**: Measure water contact angle to quantify surface hydrophilicity enhancement; a lower angle indicates higher hydrophilicity.\n- **NMR spectroscopy**: Proton-NMR can identify changes in the polymer backbone and confirm successful grafting of PTMP moieties.\n- **Thermal analysis**: Use Differential Scanning Calorimetry (DSC) or Thermogravimetric Analysis (TGA) to confirm thermal stability after modification.\n\n---\n\n### 3. Notes for Optimization and Troubleshooting\n1. **Prevent Oxidation of Thiols**: Work under inert conditions (N₂ or Argon) throughout the reaction to prevent thiol oxidation to disulfides, which would reduce yield.\n2. **Minimize Cross-Linking**:\n   - Adjust molar ratios of PTMP and polymer carefully. Excess PTMP may lead to undesired cross-linking and gelation, complicating purification.\n   - Graft hydrophilic side chains uniformly rather than allowing random polymer branching.\n3. **Yield Improvement**:\n   - Use high-purity reagents and solvents to avoid side reactions.\n   - Optimize reaction temperature and time to maximize utilization of PTMP.\n\n---\n\nBy systematically following this preparation scheme, you should achieve a high yield of a consistently hydrophilic polymer modified with PTMP, suitable for applications such as biomedical coatings, water purification membranes, or hydrophilic adhesives. Make sure to test the material under relevant application conditions to verify its enhanced hydrophilicity."
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diff --git a/task2/task2-qa/╛█║╧╬я╡─░┤╨ш─ц╧Є╔ш╝╞╙ыPolyTAO║╧╫ў.json b/task2/task2-qa/╛█║╧╬я╡─░┤╨ш─ц╧Є╔ш╝╞╙ыPolyTAO║╧╫ў.json
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+{
+  "design_question": "Design an experimental scheme that incorporates the molecule generated by PolyTAO into the backbone or side chain of the target polymer. How would you ensure the successful integration of this hydrophilic molecule during the synthesis process?",
+  "design_answer": "Certainly! To help you navigate this complex topic, let’s break it down step by step — analyzing the question, summarizing the key points, and finally, designing a detailed experimental scheme for the incorporation of the hydrophilic molecule generated by PolyTAO into the polymer backbone or side chain.\n\n---\n\n### **Analysis of the Question**\n\nYour question focuses on the experimental preparation of a hydrophilic polymer, specifically targeting the integration of a molecule (generated by PolyTAO) into the polymer structure. The goal is to:\n1. Select appropriate polymerization techniques for incorporating the hydrophilic molecule into either the backbone or side chain.\n2. Ensure successful integration through precise reaction conditions, reagent ratios, and molar quantities.\n3. Enhance the hydrophilicity of the resulting polymer while maintaining process scalability and reproducibility in the lab.\n\n---\n\n### **Key Considerations**\n1. **Nature of the molecule generated by PolyTAO**: Is it reactive (e.g., does it have functional groups like hydroxyl, amine, carboxyl) or inert? Does it act as a monomer, macromer, or a reactive additive?\n2. **Target polymer backbone or structure**: Are we working with an established polymer chain where we need to graft the molecule? Or are we incorporating it through direct polymerization into a novel polymer network?\n3. **Polymerization route**: Evaluate different polymerization methods, such as free radical polymerization, step-growth polymerization, atom transfer radical polymerization (ATRP), or ring-opening polymerization (ROP), depending on the functionality of the PolyTAO molecule.\n4. **Reaction conditions**: Optimize the temperature, solvents, catalysts, and other experimental parameters for successful incorporation without degradation.\n5. **Characterization**: Sufficient characterization at each step of the synthesis should be performed (e.g., FTIR, NMR, GPC) to confirm successful integration of the molecule.\n\n---\n\n### **Experimental Scheme**\nBelow is the step-by-step experimental synthesis scheme for incorporating the hydrophilic molecule generated by PolyTAO into the polymer backbone or side chain:\n\n#### **Step 1: Identify Reactivity of the PolyTAO Molecule**\n- Analyze the chemical structure of the molecule generated by PolyTAO — specifically, its functional groups (e.g., -OH, -NH2, -COOH, or double bonds). These functional groups will dictate its reactivity and polymerization pathways (backbone or side-chain incorporation).\n- If the molecule contains reactive groups (e.g., hydroxyl or carboxyl), it can serve as a comonomer in step-growth polymerization, a chain-transfer agent in free-radical polymerization, or a macromer in graft polymerization.\n\n#### **Step 2: Selection of Polymerization Route**\nBased on the reactivity of the PolyTAO molecule, choose an appropriate polymerization route:\n1. **Free Radical Polymerization** (if PolyTAO contains vinyl groups or unsaturated bonds):\n   - PolyTAO molecule will co-polymerize with hydrophilic monomers like acrylamide or acrylic acid.\n2. **Ring-Opening Polymerization** (if PolyTAO contains cyclic moieties):\n   - PolyTAO molecule can be incorporated into a polyether or polyester backbone.\n3. **Grafting or Post-Polymerization Modification** (if PolyTAO contains functional groups for side-chain modification):\n   - The molecule is chemically grafted onto a pre-synthesized hydrophilic polymer backbone, such as hydroxyethyl cellulose or polyvinyl alcohol.\n\n#### **Step 3: Prepare Reagents and Reaction Setup**\n- **Monomers**: Obtain hydrophilic monomers such as acrylamide, acrylic acid, or methacrylic acid, depending on your target polymer.\n- **PolyTAO Molecule**: Ensure its purity and characterize it using NMR, FTIR, or mass spectroscopy.\n- **Initiators**: Use thermal or photochemical initiators (e.g., potassium persulfate, AIBN, or photoinitiators for UV-polymerization).\n- **Solvent**: Use water or water-miscible solvents (ethanol, methanol) to promote hydrophilic interactions.\n- **Catalyst**: If required, use catalysts like tin octoate (in ROP) or copper-based catalysts (in ATRP).\n\n#### **Step 4: Optimize Reaction Conditions**\nLet’s outline the detailed experimental conditions based on the polymerization route chosen:\n\n1. **For Free Radical Polymerization**:\n   - **Reaction Setup**: Dissolve the hydrophilic monomer (e.g., acrylamide) and PolyTAO molecule at the desired molar ratio in distilled water.\n   - **Initiator Addition**: Add potassium persulfate as the initiator (typically 0.5–2% wt. of total monomer content).\n   - **Temperature**: Heat the reaction mixture to 65–75°C under nitrogen or argon to minimize oxygen inhibition.\n   - **Polymerization Time**: Allow the reaction to proceed for 4–6 hours.\n   - **Post-Polymerization**: Purify the product by dialysis to remove unreacted monomers and PolyTAO residues.\n\n2. **For Post-Polymerization Grafting (Side-Chain Incorporation)**:\n   - **Reaction Setup**: Prepare a hydrophilic base polymer (e.g., polyvinyl alcohol or hydroxyethyl cellulose) with reactive side chains.\n   - **PolyTAO Activation**: If the PolyTAO molecule contains carboxylic acid groups, activate them using coupling agents like EDC/NHS for amide bond formation.\n   - **Reaction Conditions**: Mix the activated PolyTAO molecule and the base polymer in water or DMSO at room temperature.\n   - **Time**: Stir the reaction for 12–24 hours.\n   - **Purification**: Precipitate the polymer in acetone or ethanol to remove coupling agents and byproducts.\n\n3. **For Ring-Opening Polymerization**:\n   - **PolyTAO Molecule**: React cyclic monomers with PolyTAO in the presence of a catalyst (e.g., tin octoate) and an initiator (e.g., alcohol).\n   - **Temperature**: Conduct the reaction at elevated temperatures (90–120°C) under vacuum or inert gas.\n   - **Time**: Proceed for 6–12 hours until the conversion is complete.\n   - **Post-Reaction**: Dissolve the product in water and dialyze against water to remove unreacted species.\n\n#### **Step 5: Characterization**\n- **FTIR Spectroscopy**: Confirm functional group incorporation (e.g., appearance of PolyTAO-specific peaks).\n- **NMR Spectroscopy**: Verify the covalent addition of PolyTAO molecules into the polymer structure.\n- **Gel Permeation Chromatography (GPC)**: Determine molecular weight and distribution.\n- **Contact Angle Measurements**: Measure the hydrophilicity of the polymer surface.\n\n---\n\n### **Final Remarks**\nThis experimental scheme is highly flexible and can be adapted based on the unique chemical properties of the molecule generated by PolyTAO. The key is to ensure that reaction conditions are mild enough to preserve the integrity of the hydrophilic functional groups while selecting a polymerization method that maximizes the incorporation efficiency. \n\nFeel free to reach out if the PolyTAO molecule's specific characteristics require adjustments to this schematic!"
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+{
+  "design_question": "Describe the steps you would take to calculate the value of λ0 when modifying the polymer with 'μ_ref'. How does solving this boundary value problem contribute to determining the hydrophilic properties of the modified polymer?",
+  "design_answer": "To address your question systematically, let's break it down and develop a logical and detailed approach. I'll provide a comprehensive explanation within the framework you've outlined, including analysis, experimental details, and how solving the boundary value problem contributes to determining the hydrophilic properties of the modified polymer.\n\n---\n\n### Part 1: **Analysis of the Question**\n\n#### Key Points:\n1. **Polymer Modification**: The question revolves around the modification of a polymer to enhance hydrophilicity, specifically using a parameter denoted as 'μ_ref'.\n2. **Value of λ₀**: The goal is to calculate the value of a parameter λ₀ while considering its dependence on 'μ_ref'.\n3. **Boundary Value Problem**: This suggests we are solving a mathematical or physical equation that governs the system's behavior, such as a differential equation with specific boundary conditions.\n4. **Relevance to Hydrophilicity**: Solving this problem has implications for understanding and predicting the hydrophilic properties of the modified polymer, which we must connect in our final explanation.\n\nWith these points clarified, we’ll now devise a step-by-step methodology to calculate λ₀ and explain its impact on the polymer’s hydrophilicity.\n\n---\n\n### Part 2: **Detailed and Systematic Answer**\n\n#### **Step 1: Background on λ₀ and μ_ref**\nFor many hydrophilic polymers, λ₀ represents a key parameter related to the system's equilibrium or characteristic property, such as water affinity, hydration dynamics, or solvation. μ_ref presumably refers to a reference chemical potential associated with a specific solvent (e.g., water). By modifying the polymer with μ_ref, we are altering its interaction with polar molecules like water.\n\nThe determination of λ₀ therefore involves describing this interaction mathematically, which may be based on thermodynamic, kinetic, or transport properties of the system.\n\n#### **Step 2: Mathematical Framework**\nAssume the hydrophilic modification introduces a functional relationship involving λ₀. Often, the relationship is governed by a differential equation involving mass transport, chemical potential, or free energy. For example:\n\n\\[\n\\frac{d^2\\lambda}{dx^2} - f(\\lambda, x, \\mu_{\\text{ref}}) = 0\n\\]\n\nHere:\n- \\(x\\): Spatial coordinate (e.g., polymer depth or solvent concentration gradient).\n- \\(f(\\lambda, x, \\mu_{\\text{ref}})\\): A function coupling λ with the polymer-solution environment.\n- Boundary conditions: To solve this, we must specify boundary conditions such as:\n  - \\(λ(x=0) = λ_{\\text{surface}}\\) (surface hydrophilicity).\n  - \\(λ(x=L) = λ_{\\text{bulk}}\\) (bulk hydrophilicity at distance \\(L\\)).\n\nBoundary values ensure the problem reflects the physical system's constraints.\n\n#### **Step 3: Setting up the Experiment**\n1. **Polymer Pre-Treatment**:\n   - Select a base polymer and ensure it is ready for hydrophilic modification through surface activation techniques (e.g., plasma treatment, oxidation, or grafting).\n   - Ensure uniformity in the initial polymer properties to minimize experimental variability.\n\n2. **Modification with μ_ref**:\n   - Introduce hydrophilic functional groups (e.g., –OH, –COOH, or poly(ethylene glycol) chains) through a coupling reaction influenced by μ_ref.\n   - This may involve:\n     - A grafting agent (e.g., hydroxyethyl methacrylate (HEMA) or polyethylene glycol methacrylate).\n     - A controlled reaction environment (solvent, catalysts, etc.).\n\n3. **Parameter Setup for λ₀ Determination**:\n   - Vary the applied μ_ref during polymer modification using a range of controlled conditions.\n   - Each modification corresponds to a unique μ_ref-induced structure.\n\n4. **Boundary Data Collection**:\n   - Measure relevant properties such as surface energy, water contact angles, or hydration levels across polymer depth.\n   - These measurements define our boundary conditions.\n\n#### **Step 4: Solving the Boundary Value Problem**\n1. Substitute experimental parameters and boundary conditions into the chosen governing equation (specific to your context, e.g., diffusion equation or chemical potential gradient).\n2. Use numerical methods (e.g., finite element analysis) for solutions if the equation is non-analytic. Software like MATLAB or COMSOL can perform this computation.\n3. Determine λ₀ as a parameter that satisfies the equation under the given constraints.\n\n#### **Step 5: Validation and Interpretation**\n1. Correlate λ₀ with experimentally observed hydrophilic properties:\n   - For example, as λ₀ increases, water contact angle decreases, indicating greater hydrophilicity.\n2. If necessary, run additional experiments for polymers modified with different μ_ref values to validate trends.\n\n---\n\n### Part 3: **How Solving the Boundary Value Problem Relates to Hydrophilicity**\n1. **Quantitative Understanding**: By calculating λ₀, we can quantitatively describe the polymer's modified hydrophilicity. For instance, λ₀ might define free energy at the water-polymer interface or solvent diffusion rate into the polymer network.\n2. **Optimization**: Solving the problem allows optimization of μ_ref to achieve the desired hydrophilicity, assisting in fine-tuning the polymer properties for specific applications (e.g., biomedical hydrogels or membranes).\n3. **Predictability**: Theoretical solutions provide predictive power for how future modifications (via changes in μ_ref) affect hydrophilic behavior, saving materials and time during experimental trials.\n\n---\n\n### Final Notes:\nUnderstanding and calculating λ₀ involves careful synthesis, accurate experimental data, and robust mathematical solutions. Treat each step as iterative, where experimental observations refine model parameters. If you have additional context or polymer-specific data (e.g., chemical structure), I can help tailor the experimental and mathematical framework more precisely."
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+{
+  "design_question": "Propose a purification method to isolate the final product after modifying a polymer with dopamine hydrochloride. How would you ensure the product’s hydrophilicity is preserved during purification?",
+  "design_answer": "To design an effective purification method to isolate a polymer modified with dopamine hydrochloride, while ensuring the polymer’s hydrophilicity is preserved, we need to approach this systematically. Below is the step-by-step analysis and detailed experimental procedure.\n\n---\n\n### **1. Key Points Analysis**\n- **Objective:** Isolate the dopamine-modified polymer after synthesis and ensure the hydrophilicity imparted by dopamine hydrochloride is retained during purification.\n- **Challenges:** Dopamine hydrochloride is hydrophilic and prone to oxidation during purification. Preservation of the polymer's hydrophilic features and avoidance of degradation or loss during purification must be considered.\n- **Focus:** Selection of purification techniques suited to hydrophilic polymers, avoiding exposure to conditions (e.g., high temperature, oxidative atmospheres) that might affect the dopamine structure.\n\n---\n\n### **2. Proposed Purification Method**\nThe purification process involves the removal of unreacted reagents, by-products, and residual solvents while retaining the hydrophilic properties of the modified polymer. Here's a systematic approach:\n\n#### Step 1: **Dilution and Solubilization**\n- **Objective:** Prevent aggregation or loss of hydrophilicity during purification.\n- **Procedure:**\n  - Dissolve the polymer solution in a hydrophilic solvent or solvent mixture that enhances solubility. For dopamine-modified polymers, aqueous media is ideal. Use water, ethanol, or a buffer solution with a neutral pH (e.g., phosphate-buffered saline at pH 7.4) to maintain dopamine's stability.\n  - Confirm solubility using gentle stirring or sonication (avoid high agitation to prevent heat buildup).\n\n#### Step 2: **Dialysis**\n- **Objective:** Remove low molecular weight impurities, unreacted dopamine hydrochloride, and small by-products.\n- **Procedure:**\n  - Select a dialysis membrane with a molecular weight cut-off (MWCO) appropriate for the polymer size (e.g., MWCO of 10,000 Da for smaller polymers or 50,000 Da for larger ones).\n  - Immerse the dialysis bag in deionized water or buffer solution maintained at neutral pH to avoid oxidation of dopamine functional groups.\n  - Exchange the dialysis water or buffer every 3–4 hours for the first 12 hours, then every 6–8 hours thereafter. Perform dialysis for 24–48 hours, depending on purity requirements.\n  - Ensure the dialysis system remains in a low-temperature environment (typically at ~4°C) to prevent polymer degradation or dopamine oxidation.\n\n#### Step 3: **Precipitation (if needed)**\n- **Objective:** Isolate the polymer by precipitation without compromising its hydrophilic character.\n- **Procedure:**\n  - Gradually add a non-solvent (e.g., acetone or ethanol) into the polymer solution with stirring to precipitate the polymer selectively.\n  - Avoid excessive non-solvent addition since it may cause collapse of hydrophilic chains or loss of dopamine functional groups.\n  - Collect the precipitate via centrifugation or filtration.\n\n#### Step 4: **Ultrafiltration or Size-Exclusion Chromatography**\n- **Objective:** Further purify the polymer by removing higher and lower molecular weight contaminants.\n- **Procedure:**\n  - Use ultrafiltration techniques employing hydrophilic membranes to selectively retain the polymer while removing impurities.\n  - Alternatively, pass the solution through size-exclusion chromatography (SEC) using a hydrophilic column (e.g., Sephadex or Superdex columns) to ensure separation while retaining the polymer’s hydrophilicity.\n\n#### Step 5: **Final Drying**\n- **Objective:** Obtain the purified polymer in solid form without compromising its structure or hydrophilicity.\n- **Procedure:**\n  - Lyophilize (freeze-dry) the purified solution rather than subjecting it to oven drying. Lyophilization avoids exposure to heat and preserves hydrophilic features.\n  - Confirm the drying chamber is flushed with inert gas (e.g., nitrogen) to reduce oxidative stress on dopamine groups.\n\n---\n\n### **3. Ensuring Product Hydrophilicity During Purification**\nTo preserve the hydrophilic properties:\n1. **Control pH:** Keep the pH neutral throughout dialysis and filtration steps (e.g., ~pH 7–7.5). Dopamine hydrochloride can degrade or oxidize in acidic or basic conditions.\n2. **Protect from Oxidation:** Perform all handling in low-temperature environments and, where possible, under an inert atmosphere (e.g., nitrogen or argon). Dopamine is prone to oxidative degradation.\n3. **Maintain Solubility:** Use hydrophilic solvents or buffers to ensure polymer chains remain hydrated and functional groups (e.g., amine and hydroxyl groups) do not collapse or aggregate.\n4. **Avoid Heat:** Prefer cold methods such as lyophilization, dialysis, or ultrafiltration to eliminate heat exposure, which could damage functional groups.\n\n---\n\n### **4. Verification of Purification**\nAfter purification, verify the polymer’s hydrophilicity through:\n- **Water Contact Angle Measurement:** A decrease in the contact angle compared to the unmodified polymer indicates enhanced hydrophilicity.\n- **Fourier-Transform Infrared (FTIR) Spectroscopy:** Check for characteristic peaks (e.g., O-H and N-H stretching) to confirm the presence of hydrophilic groups.\n- **Nuclear Magnetic Resonance (NMR):** Verify that dopamine groups remain intact post-purification.\n- **Thermogravimetric Analysis (TGA):** Confirm no degradation occurred during purification steps.\n\n---\n\nWith this detailed purification approach, your polymer modified with dopamine hydrochloride can be isolated while retaining its hydrophilic properties. Let me know if you require further clarification or guidance!"
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+{
+  "design_question": "Describe how the addition of hydrogen peroxide (H2O2) might interact with the electrodeposition process of chitosan and influence the structural parameters such as pore size, porosity, and overall hydrophilicity of the resulting polymer.",
+  "design_answer": "To adequately address your question on how the addition of hydrogen peroxide (H₂O₂) might interact with the electrodeposition process of chitosan and influence the structural parameters, including pore size, porosity, and overall hydrophilicity of the resulting polymer, let us proceed step by step, adhering to the outlined requirements for a systematic, detailed, and rigorous explanation. \n\n---\n\n### **Step 1: Analyze the Question and Key Points**\n1. **Understanding the Role of Hydrogen Peroxide (H₂O₂):**\n   Hydrogen peroxide is a mild oxidative agent. Its addition can introduce hydroxyl radicals (•OH) and alter the ionic environment during electrodeposition processes. Therefore, it can impact the cross-linking density, pore formation, and surface chemistry of polymers like chitosan.\n   \n2. **Electrodeposition of Chitosan:**\n   Chitosan is a pH-responsive polysaccharide that can be electrodeposited on a substrate by taking advantage of its solubility at low pH. Under an applied electric field, chitosan undergoes deprotonation, gelation, and deposition on the electrode.\n\n3. **Structural Parameters of Interest:**\n   - **Pore Size:** Controlled by reaction kinetics and the interplay between coagulants and solvents.\n   - **Porosity:** Dictated by the deposition dynamics and potential cross-linking interactions between hydrogen peroxide and chitosan.\n   - **Hydrophilicity:** Dependent on the surface chemistry, oxidation states, and introduction of functional groups (e.g., hydroxyl groups).\n\n### **Step 2: Systematic Answer with Detailed Experimental Preparation Scheme**\n\nTo better understand the effects of adding H₂O₂, I will outline a step-by-step experimental preparation scheme for the electrodeposition of chitosan with hydrogen peroxide. Each step includes relevant conditions and expected outcomes.\n\n---\n\n### **Experimental Scheme: Electrodeposition of Chitosan in the Presence of Hydrogen Peroxide**\n\n#### Step 1: **Preparation of Chitosan Solution**\n1. **Reagents:**\n   - Chitosan: High molecular weight (>70% deacetylation) is preferred.\n   - Acetic acid (glacial): 1% (v/v) solution used as a solvent to dissolve chitosan.\n   - Hydrogen peroxide (H₂O₂): 30% stock solution.\n\n2. **Procedure:**\n   - Dissolve chitosan in a 1% acetic acid solution to obtain a 1-2% (w/v) solution. Stir the solution for 12 hours to ensure complete dissolution.\n   - After complete dissolution, adjust the pH to ~5.0 using sodium hydroxide (NaOH), as chitosan is soluble at acidic pH but precipitates at higher pH values.\n   - Add 1-10 mM hydrogen peroxide to the chitosan solution and mix gently for another 30 minutes. The exact concentration of H₂O₂ can be varied to study its effects on the polymer structure (discussed below).\n\n---\n\n#### Step 2: **Electrodeposition of Chitosan**\n1. **Setup:**\n   - Use a two-electrode configuration:\n     - Cathode: Conducting substrate (e.g., stainless steel or indium tin oxide, ITO glass).\n     - Anode: Platinum or graphite electrode.\n   - Power Supply: Constant voltage or current source, capable of applying voltages in the range of 1-3 V.\n\n2. **Procedure:**\n   - Submerge the electrodes in the chitosan solution (prepared above) with hydrogen peroxide.\n   - Apply a constant voltage (e.g., 2 V) for 5-10 minutes to precipitate chitosan on the cathode. During electrodeposition, chitosan is locally deprotonated near the electrode surface, forming a hydrogel-based film.\n\n   **Expected Role of Hydrogen Peroxide:**\n   - The presence of H₂O₂ introduces mild oxidative stress, which can:\n     - Generate hydroxyl radicals (•OH) that react with the amino and hydroxyl groups of chitosan.\n     - Modify the gelation process, potentially resulting in looser cross-linking and enhanced porosity.\n     - Promote interactions between chitosan chains, introducing new hydroxyl-rich groups that enhance hydrophilicity.\n\n---\n\n#### Step 3: **Post-Treatment and Cross-Linking**\n1. **Reagents:**\n   - Sodium tripolyphosphate (TPP) as a cross-linking agent (optional), used to further stabilize the chitosan film.\n   - PBS (phosphate-buffered saline) to wash the deposited polymer.\n\n2. **Procedure:** \n   - After electrodeposition, carefully rinse the substrate with PBS to remove unbound chitosan and residual acetic acid.\n   - Optionally, immerse the substrate in a 1-2% (w/v) TPP solution for 10 minutes to cross-link the deposited chitosan. This step can enhance mechanical stability but could reduce porosity slightly.\n\n   **Expected Role of Hydrogen Peroxide:**\n   - Hydrogen peroxide can oxidize certain functional groups, which may lead to the introduction of carbonyl and carboxyl groups, further increasing hydrophilicity.\n\n---\n\n#### Step 4: **Characterization of the Polymer Film**\nConduct a detailed examination of the structural and hydrophilic properties of the resulting film.\n\n1. **Pore Size and Porosity:**\n   - Use scanning electron microscopy (SEM) or atomic force microscopy (AFM) to analyze the surface morphology and determine the pore size and porosity.\n   - Hydrogen peroxide's oxidative interactions with chitosan and its influence on hydrodynamic deposition rates are expected to increase pore size and porosity.\n\n2. **Hydrophilicity:**\n   - Measure the water contact angle (WCA). A lower WCA indicates higher hydrophilicity.\n   - Hydrogen peroxide is anticipated to introduce hydroxyl-rich oxidized functional groups, reducing the WCA and increasing compatibility with aqueous environments.\n\n3. **Chemical Composition:**\n   - Conduct Fourier-transform infrared spectroscopy (FTIR) to identify new functional groups formed due to H₂O₂ interaction.\n   - Peaks corresponding to hydroxyl (-OH) and carbonyl (-C=O) groups should become more prominent in the presence of H₂O₂.\n\n4. **Mechanical Stability and Swelling Behavior:**\n   - Perform swelling studies in aqueous media to assess the hydrophilicity and porosity.\n   - Films prepared with higher H₂O₂ concentrations may show increased swelling due to reduced cross-linking density.\n\n---\n\n### **Step 3: Analysis of Effects**\n\n1. **Pore Size:** In the presence of H₂O₂, pore size is expected to increase due to altered gelation dynamics and reduced ion-driven cohesion between chitosan chains.\n\n2. **Porosity:** Porosity will also increase because H₂O₂ generates hydroxyl radicals that disrupt the compactness of the deposited polymer network.\n\n3. **Hydrophilicity:** Hydrophilicity is enhanced due to the oxidative modification of chitosan chains, with the formation of hydroxyl and carboxyl groups contributing to water affinity.\n\n### **Step 4: Variations and Optimization**\n\nYou can vary the concentration of H₂O₂ (1–10 mM) to observe its impact systematically. At lower concentrations (e.g., 2 mM), structural changes may be less pronounced, while higher concentrations (e.g., 10 mM) may result in excessive oxidation and weaker mechanical integrity.\n\n---\n\n### **Conclusion**\nThe addition of hydrogen peroxide to the electrodeposition process of chitosan plays a crucial role in tuning the pore structure, porosity, and hydrophilicity of the resulting polymer. By optimizing the experimental parameters (e.g., H₂O₂ concentration, voltage, and deposition time), you can create a highly hydrophilic, porous polymer film tailored for applications such as drug delivery, biosensors, or tissue engineering scaffolds."
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diff --git a/task2/task2-qa/╡═─ж▓┴╧╡╩¤╦о─¤╜║═┐▓у JACS.json b/task2/task2-qa/╡═─ж▓┴╧╡╩¤╦о─¤╜║═┐▓у JACS.json
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+{
+  "design_question": "Describe the role of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) in the synthesis process and explain how its incorporation enhances the hydrophilicity of the resulting polymer.",
+  "design_answer": "Certainly! Let’s analyze your question and address it step-by-step, thoroughly discussing the role of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) in the synthesis of hydrophilic polymers.\n\n---\n\n### **Step 1: Analyze the Question and Key Points**\nThe question targets two aspects:\n1. The role of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) in the synthesis process.\n2. How AMPS improves the hydrophilicity of the resulting polymer.\n\nTo answer this, we need to:\n- Understand the chemical structure and properties of AMPS.\n- Explain its function during polymerization.\n- Illustrate how its structural features contribute to hydrophilicity.\n\n---\n\n### **Step 2: Describe AMPS and Its Role in Synthesis**\n\n#### **1. Chemical Properties of AMPS**\nAMPS is a monomer with the structural formula CH₂=CH-CONH-C(CH₃)₂-CH₂-SO₃H. The key functional groups are:\n- A **vinyl group (-CH=CH₂)**: Enables chain propagation in polymerization by undergoing free radical addition polymerization.\n- A **sulfonic acid group (-SO₃H)**: Highly hydrophilic due to its ionic nature and ability to hydrogen bond with water molecules.\n- An **amide group (-CONH-)**: Enhances hydrogen bonding interactions and affects polymer stability.\n\nThese functional groups collectively make AMPS a versatile and highly polar monomer.\n\n#### **2. Role of AMPS in the Polymerization Process**\nAMPS typically participates in **free radical polymerization** or **copolymerization** with other monomers such as acrylamide, acrylic acid, or other methacrylate derivatives. Here's how AMPS operates in the reaction:\n\n- **Initiation**: In the presence of an initiator (such as potassium persulfate, APS, or azobisisobutyronitrile, AIBN), AMPS’s vinyl group forms a reactive radical.\n- **Propagation**: The radical reacts with other monomeric units (either AMPS itself or a comonomer), forming extended polymer chains.\n- **Termination**: Radical termination occurs when two growing chains terminate with combined radicals or other deactivators, completing polymer growth.\n\n#### **Experimental Parameters to Consider**:\n- **Solvent Medium**: Due to its ionic nature, water or mixed solvent systems (water-methanol) are ideal for dissolving AMPS.\n- **pH Regulation**: The -SO₃H groups in AMPS are pH-sensitive; near-neutral pH (6-7) prevents excessive protonation or deprotonation that may destabilize the reaction.\n- **Reaction Temperature**: Generally, 40–70°C for free radical polymerization is used to decompose the initiator and maintain efficient chain growth.\n- **Molar Ratios**: The proportion of AMPS in the comonomer feed controls the degree of hydrophilicity. For highly water-soluble polymers, higher AMPS content, ~30–50 mol%, is often used.\n\n---\n\n### **Step 3: Enhancement of Hydrophilicity by AMPS**\n\nThe incorporation of AMPS significantly enhances the hydrophilicity of the resulting polymer. Here’s how:\n\n#### **1. Sulfonic Acid Groups (-SO₃H)**\n- The **sulfonic acid group** is extremely hydrophilic due to its strong ionic character. When incorporated into a polymer, these groups are highly effective at attracting and binding water molecules through ion-dipole interactions and hydrogen bonding.\n- Even under harsh conditions like saline or high-temperature environments (e.g., oil field applications), the -SO₃H groups retain their hydrophilic properties, making AMPS-based polymers highly water-compatible and stable.\n\n#### **2. Hydrogen Bonding Contributions**\nThe amide group (-CONH-) in AMPS can establish hydrogen bonds with water molecules, increasing the water retention ability of the polymer.\n\n#### **3. Increased Solubility**\nPolymers containing AMPS dissolve better in aqueous systems because their ionic groups lower the surface energy and reduce hydrophobic interactions. This makes these polymers suitable for hydrogel formation, coatings, or drug delivery systems.\n\n#### **4. Ionic Charge Density**\nCopolymerizing AMPS with neutral or slightly hydrophobic monomers introduces charged groups that enhance water compatibility. This is especially useful in tailoring water-absorbing polymers or superabsorbents.\n\n---\n\n### **Step 4: A Synthesis Plan for an AMPS-Based Hydrophilic Polymer**\nBelow is a stepwise protocol for the preparation of a hydrophilic polymer containing AMPS:\n\n#### **Materials:**\n- AMPS monomer\n- Comonomer (e.g., acrylamide or acrylic acid)\n- Initiator (e.g., APS for aqueous initiation or AIBN for organic solvent systems)\n- Solvent (deionized water or water-methanol)\n- pH buffer (e.g., phosphate buffer for neutral pH control)\n- Nitrogen gas (to create an inert atmosphere)\n\n#### **Procedure:**\n1. **Preparation of Monomer Solution:**\n   - Dissolve AMPS in deionized water (e.g., 10–20 wt% concentration).\n   - Add desired comonomer (e.g., acrylamide) in a specific molar ratio (e.g., AMPS:acrylamide = 30:70 for moderate hydrophilicity, or 50:50 for more hydrophilic polymers). Stir thoroughly.\n\n2. **Adjust pH:**\n   - Use a pH meter to adjust the pH of the solution to ~6.5-7.0 using NaOH or HCl as needed.\n\n3. **Deoxygenation:**\n   - Bubble nitrogen gas through the reaction mixture for 30 minutes to remove dissolved oxygen, which can inhibit radical polymerization.\n\n4. **Initiation:**\n   - Dissolve the initiator (e.g., potassium persulfate) in a small amount of water and add it to the monomer solution. Typical initiator concentration is 0.1–1 wt% based on the total monomer weight.\n   - Raise the reaction temperature to ~60°C to activate the initiator.\n\n5. **Polymerization:**\n   - Allow the reaction to proceed under constant stirring (300–500 rpm) for 4–6 hours. Maintain an inert nitrogen atmosphere throughout.\n\n6. **Termination and Purification:**\n   - Cool the reaction mixture to room temperature to terminate the polymerization.\n   - Precipitate the polymer in ethanol or acetone to remove unreacted monomers.\n   - Wash the precipitate and dry under vacuum at 50°C.\n\n#### **Expected Results**:\nThe resulting polymer will exhibit enhanced hydrophilicity, as evidenced by its high water absorption capacity, swelling behavior in aqueous media, or solubility in water. Characterization using methods such as FTIR (to confirm sulfonic group incorporation), TGA (to assess thermal stability), and contact angle measurement (to evaluate hydrophilicity) can verify the polymer's properties.\n\n---\n\n### **Conclusion**\nAMPS plays a dual role in polymer synthesis:\n1. It acts as a hydrophilic monomer that incorporates ionic and hydrogen-bonding groups into the polymer backbone.\n2. It enhances polymer hydrophilicity due to its sulfonic acid and amide groups.\n\nThrough careful control of reaction parameters, AMPS-containing polymers can be tailored for applications ranging from hydrogels to water treatment and biomedical systems."
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+{
+  "design_question": "Describe the process of modifying a polymer using methacryloyl gelatin (GelMA). Specifically, outline how you would ensure the successful grafting of GelMA onto the polymer surface while maintaining its hydrophilic properties.",
+  "design_answer": "Certainly! Let's tackle this step by step to design a systematic preparation scheme for the modification of a polymer using methacryloyl gelatin (GelMA) while ensuring its hydrophilic properties are maintained. We'll analyze the question first and then delve into the detailed experimental steps, following the guidelines provided.\n\n---\n\n### **1. Analysis of the Question and Key Points**\nThe question revolves around the incorporation of methacryloyl gelatin (GelMA) onto a polymer surface. GelMA has hydrophilic properties due to the presence of gelatin and methacryloyl functional groups, and its grafting onto the polymer can enhance surface hydrophilicity. To ensure successful modification:\n- We need to confirm grafting occurs efficiently and preserves functionality.\n- We should optimize reaction conditions to ensure hydrophilic properties are enhanced.\n- A systematic experimental scheme must be developed with attention to reagent ratios, reaction conditions, and characterization.\n\n---\n\n### **2. Detailed Experimental Preparation Scheme**\n\nBelow is a step-by-step preparation method for grafting GelMA onto the polymer surface while maintaining its hydrophilic properties.\n\n---\n\n#### **Step 1: Preparation of Methacryloyl Gelatin (GelMA)**\nBefore we proceed to grafting, GelMA itself must be synthesized if not already available. Follow these steps:\n1. **Materials**: Gelatin, methacrylic anhydride (MA), phosphate-buffered saline (PBS), and reagents for purification (e.g., dialysis tubing).\n2. **Procedure**:\n   - Dissolve **gelatin** (e.g., Type A gelatin) in PBS at pH 7.4 under stirring at 50°C until fully dissolved (1–10 wt.% solution recommended).\n   - Slowly add **methacrylic anhydride** drop-wise (e.g., 10% volume/volume of methacrylic anhydride relative to the gelatin solution) under continuous stirring. Maintain the pH at 8.0 with NaOH (to avoid acidification of the gelatin solution).\n   - Stir at 50°C for 2 hours; the methacrylic anhydride reacts with amine groups on gelatin to form GelMA.\n   - Purify GelMA by dialysis against distilled water for 5–7 days to remove unreacted methacrylic anhydride and other impurities. Freeze-dry the solution to obtain GelMA powder.\n3. **Characterization**:\n   - Confirm the synthesis of GelMA using **proton nuclear magnetic resonance (¹H NMR)** or **Fourier-transform infrared spectroscopy (FTIR)** to verify the presence of methacryloyl groups.\n\n---\n\n#### **Step 2: Activation of Polymer Surface**\nTo ensure GelMA can graft onto the polymer, the polymer surface must contain reactive groups (e.g., amine, carboxylic, or hydroxyl groups). Depending on the polymer type:\n1. **Materials**: Surface-activating agent (e.g., plasma treatment, UV activation, or chemical activation using carbodiimide chemistry).\n2. **Procedure**:\n   - If using a plasma treatment setup, expose the polymer surface to **oxygen plasma** for 1–5 minutes to introduce hydrophilic functional groups such as hydroxyl (-OH) or carboxylic (-COOH) groups.\n   - Alternatively, if using carbodiimide activation:\n     - Treat the surface with **1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC)** and **N-hydroxysuccinimide (NHS)** in aqueous conditions (pH 5.5–7.5). EDC will activate carboxylic groups on the polymer to create reactive esters for GelMA attachment.\n\n---\n\n#### **Step 3: Grafting GelMA Onto Polymer Surface**\nOnce the polymer surface is activated, GelMA can be grafted efficiently.\n1. **Materials**: GelMA solution, activated polymer, photoinitiator (e.g., Irgacure 2959 for UV curing or ammonium persulfate for redox curing).\n2. **Procedure**:\n   - Dissolve GelMA in deionized water or PBS to create a 10–20 wt.% solution at 37°C.\n   - Combine the polymer with the GelMA solution, immerse it in the GelMA solution, ensuring uniform coverage of the polymer surface.\n   - Add the appropriate **photoinitiator** (e.g., 0.1–0.5 wt.%) to the GelMA solution; this is necessary for photo-crosslinking at the methacryloyl groups.\n   - Subject the mixture to UV light (around 365 nm wavelength, 5–10 mW/cm² intensity) or a thermal curing method (e.g., 60°C for 30 minutes) to initiate polymerization. This forms covalent bonds between GelMA and the surface.\n\n---\n\n#### **Step 4: Washing and Post-Treatment**\nRemove unbound GelMA and ensure quality grafting.\n1. **Procedure**:\n   - Wash the modified polymer thoroughly with distilled water or PBS to remove loosely bound GelMA or impurities that may affect hydrophilicity.\n   - Optionally, use gentle ultrasonic cleaning to enhance the washing process and prevent physical damage to the surface.\n\n---\n\n#### **Step 5: Characterization of Modified Polymer**\nAfter grafting, confirm GelMA attachment and evaluate hydrophilicity.\n1. **Surface Analysis**:\n   - Use **FTIR spectroscopy** to identify functional groups of GelMA on the polymer.\n   - Use **X-ray photoelectron spectroscopy (XPS)** or **atomic force microscopy (AFM)** for a detailed surface chemical analysis.\n2. **Hydrophilicity Assessment**:\n   - Measure the water contact angle of the polymer surface before and after modification. A lower water contact angle indicates improved hydrophilicity.\n   - Perform **swelling tests** in water or PBS to evaluate the hydrophilic nature.\n\n---\n\n### **3. Notes and Optimization Suggestions**\n1. Reaction **pH**, temperature, and initiator concentration must be optimized for successful GelMA grafting and polymerization.\n2. Ensure **sterility** if the modified polymer will be used for biological applications.\n3. Consider environmental factors like oxygen inhibition during photopolymerization and mitigate it by working in inert atmospheres (e.g., argon or nitrogen).\n\n---\n\n### **4. Summary**\nTo modify a polymer using GelMA:\n- Synthesize or procure GelMA with methacryloyl groups.\n- Activate the polymer surface to introduce reactive groups.\n- Utilize a crosslinking method (UV or chemical) to covalently bond GelMA to the polymer.\n- Characterize the grafted polymer, confirming functionality and hydrophilicity enhancements.\n\nThis systematic approach ensures successful grafting while retaining or enhancing the hydrophilic properties of the polymer.\n\n--- \n\nFeel free to discuss any points in detail!"
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+{
+  "design_question": "Describe a procedure for functionalizing an inert polymer surface using tannic acid in combination with metal ions. How would this approach improve the hydrophilicity of the polymer?",
+  "design_answer": "Ah, this is an excellent and timely question, touching upon the functionalization of an inert polymer surface to improve hydrophilicity! Let's break it down step by step, analyze the key points, and systematically provide an experimental preparation scheme for the functionalization process.\n\n---\n\n### **Key Points in the Question:**\n1. **Objective:** Functionalization of an inert polymer surface to improve hydrophilicity.\n2. **Methodology:** Utilization of tannic acid (TA) in combination with metal ions.\n3. **Desired Outcome:** Enhanced hydrophilicity of the polymer surface, likely by modifying its physical or chemical surface properties, including introducing hydrophilic functional groups or hydrophilic coordination structures.\n\nNow, I will design a precise preparation procedure employing tannic acid and metal ions to achieve this goal.\n\n---\n\n### **Experimental Procedure for Functionalization Using Tannic Acid and Metal Ions**\nFunctionalizing a polymer surface with tannic acid (TA) and metal ions involves creating a hydrophilic coating that strongly adheres to the polymer while imparting hydrophilic functional groups like hydroxyl (-OH). The tannic acid works as a polyphenolic molecule, forming coordination complexes with metal ions, which enhance crosslinking and stability.\n\n#### **Materials Needed:**\n1. **Polymer Substrate:** An inert polymer (e.g., polyethylene, polypropylene, or polystyrene). Ensure the sample has a smooth, clean surface.\n2. **Tannic Acid (TA):** Pharmaceutical-grade or analytical-grade powder.\n3. **Metal Ions Solution:** Transition metal ions (e.g., Fe³⁺ or Cu²⁺). Ferric chloride (FeCl₃·6H₂O) is an excellent starting choice.\n4. **Solvent for TA Solution:** Deionized water or ethanol-water mixture (preferred: deionized water to avoid interference).\n5. **Cleaning Agents:** Ethanol, acetone, and deionized water.\n6. **Buffer Solution (Optional):** pH-sensitive polymers may benefit from a phosphate buffer to control pH for tannic acid deposition.\n7. **Glassware and Reaction Vessels:** Clean, hydrophilic containers (glass Petri dishes or beakers).\n\n#### **Step 1: Pre-Treatment of the Polymer Surface**\n1. **Purpose:** Clean and activate the polymer surface, improving adhesion of the hydrophilic coating.\n2. Procedure:\n   - Rinse the polymer substrate thoroughly in ethanol or acetone to remove grease or contaminants.\n   - Subject the substrate to oxygen plasma treatment or a UV-ozone treatment for 10–15 minutes to increase surface energy and create active sites (e.g., carboxyl or hydroxyl groups). This step is crucial for inert, low-surface-energy polymers.\n\n#### **Step 2: Preparation of Tannic Acid Solution**\n1. **Purpose:** Create a tannic acid solution for polymer deposition.\n2. Procedure:\n   - Dissolve tannic acid (e.g., 2 g) in 100 mL deionized water to achieve a 2% (w/v) solution.\n   - Stir the solution at room temperature until fully dissolved. The solution may appear slightly brown.\n\n#### **Step 3: Preparation of Metal Ion Solution**\n1. **Purpose:** Provide a source of metal ions for complexation with tannic acid.\n2. Procedure:\n   - Prepare a 0.1 M ferric chloride solution by dissolving 1.35 g of FeCl₃·6H₂O in 50 mL of deionized water.\n   - Mix thoroughly and keep the solution away from light to avoid photolysis.\n\n#### **Step 4: Coating the Polymer with Tannic Acid-Metal Complex**\n1. **Purpose:** Functionalize the polymer surface via TA-metal complexes, forming a hydrophilic, adherent coating.\n2. Procedure:\n   - Immerse the pre-treated polymer substrate in the tannic acid solution for 10–20 minutes at room temperature. This ensures adsorption of TA onto the polymer surface via interactions such as hydrogen bonding.\n   - Without removing the substrate, immediately add the metal ion solution dropwise into the tannic acid solution. Use a pipette to add the metal solution in a 1:3 molar ratio (Fe³⁺:tannic acid units), achieving a stable metal-polyphenol network.\n   - Allow the polymer substrate to remain immersed in this mixed solution for 20–30 minutes, ensuring the surface is covered evenly with the TA-metal complex.\n\n#### **Step 5: Post-Treatment and Rinsing**\n1. **Purpose:** Remove loosely adhered molecules and unreacted components.\n2. Procedure:\n   - Carefully remove the polymer substrate from the coating solution.\n   - Rinse the substrate with deionized water three times to remove unbound tannic acid and residual salts.\n   - Allow the substrate to dry in a clean environment at room temperature or under a nitrogen stream.\n\n#### **Step 6: Final Heating or Crosslinking (Optional)**\n1. **Purpose:** Improve mechanical stability and adhesion of the coating layer.\n2. Procedure:\n   - Place the coated polymer in an oven at 50–60°C for 1–2 hours to enhance crosslinking and evaporation of any solvent.\n\n---\n\n### **Key Reaction Chemistry and Mechanism:**\n1. **Tannic Acid Adsorption:** Tannic acid, with its multiple phenol groups (-OH), adsorbs onto the polymer surface through hydrogen bonding or hydrophobic interactions.\n2. **Metal-Polyphenol Network Formation:** Metal ions (Fe³⁺ or Cu²⁺) coordinate with the phenolic -OH groups of TA, forming stable complexes. This forms a strongly adherent hydrophilic network.\n3. **Hydrophilicity Enhancement:** The resulting surface contains hydrophilic hydroxyl (-OH) groups from tannic acid, which improve water wetting and reduce the polymer's contact angle with water.\n\n---\n\n### **Expected Results:**\n- **Improved Hydrophilicity:** The functionalized polymer should exhibit water contact angles below 40° (depending on the polymer type), indicating significant improvement in hydrophilicity.\n- **Durable Coating:** The TA-metal complex layer should resist mild mechanical or solvent stresses, ideal for biological or aqueous applications.\n\n---\n\n### **Experimental Notes:**\n1. **Reaction Conditions:** Room temperature is sufficient. Avoid excessively high temperatures, as tannic acid may degrade.\n2. **Choice of Metal Ions:** Fe³⁺ is preferred due to its strong interactions with phenolics, but Cu²⁺ or Al³⁺ can be options for different applications.\n3. **Polymer Variability:** This method is best applied to hydrophobic polymers such as polyethylene or polypropylene but requires surface pre-treatment for effective results.\n\n---\n\n### **Conclusion:**\nThis procedure demonstrates a systematic approach to functionalizing an inert polymer surface with a tannic acid-metal ion complex. By following each step carefully, you will achieve a hydrophilic polymer surface with improved wettability, suitable for applications in biomedical devices, membranes, or coatings.\n\n"
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+{
+  "design_question": "Explain how cyanoacrylate monomers can be utilized to modify a polymer network to enhance its hydrophilicity. Include details about the type of polymerization involved and any necessary considerations during preparation.",
+  "design_answer": "### Analysis of the Question:\n\nYour question asks how cyanoacrylate monomers can be used to *modify a polymer network* to enhance its hydrophilicity. Key aspects to focus on include:\n\n1. **Cyanoacrylate Monomers**: A class of monomers featuring a highly reactive electron-deficient double bond due to the electron-withdrawing groups (e.g., -CN and -COOR substituents). These monomers are known for their rapid polymerization and adhesive properties.\n2. **Hydrophilicity Enhancement**: The end goal is to introduce functionalities into the polymer network that interact favorably with water, such as polar or hydrophilic groups.\n3. **Polymerization Methodology**: Insights into the type of polymerization (e.g., free-radical, anionic) that can be employed. This includes specifying reaction conditions, initiators, and any supporting reagents.\n4. **Modification of Existing Networks**: Whether the existing polymer is crosslinked, linear, or branched, you'll need to consider how functional cyanoacrylate domains can be successfully integrated.\n\nWith these points in mind, let us systematically design an experimental preparation scheme:\n\n---\n\n### Preparation Scheme for Enhancing Hydrophilicity of a Polymer Network Using Cyanoacrylate Monomers:\n\n#### Step 1: Understanding the Parent Polymer Network\n- **Assess the Polymer Network**: Start by identifying the structure and functional groups of the existing polymer to determine how cyanoacrylate monomers can react with it. Common networks (e.g., polyacrylamide gels, polyethylene glycol matrices, or other water-compatible polymers) can be tailored for this purpose.\n- **Crosslinking**: If the network is crosslinked, care should be taken to ensure that the introduction of cyanoacrylate does not compromise the network’s integrity.\n- **Surface Modification or Bulk Incorporation**: Decide whether the cyanoacrylate will coat the surface or be incorporated into the bulk structure.\n\n---\n\n#### Step 2: Reaction Chemistry of Cyanoacrylate Monomers\nCyanoacrylate monomers (e.g., methyl-2-cyanoacrylate or ethyl-2-cyanoacrylate) polymerize via **anionic polymerization** in aqueous or slightly alkaline environments. Key steps:\n1. **Initiation**: The reaction is initiated by nucleophiles (e.g., OH⁻, amines, or the water environment itself). This nucleophilic attack opens the cyanoacrylate’s C=C bond, generating an anionic propagating species.\n2. **Propagation**: The chain grows rapidly by addition of further cyanoacrylate molecules until terminated.\n\nBy leveraging this rapid polymerization mechanism, the cyanoacrylate can be covalently grafted or integrally polymerized onto/into the hydrogel or polymer matrix.\n\n---\n\n#### Step 3: Materials and Reagents\n- **Cyanoacrylate Monomer**: Select a commercially available monomer like ethyl-2-cyanoacrylate.\n- **Polymer Substrate**: Depending on the application, start with a readily available hydrophilic substrate such as poly(vinyl alcohol) (PVA), poly(acrylic acid) (PAA), or poly(ethylene glycol) (PEG). If enhancing an existing polymer gel, assess its chemical compatibility.\n- **Initiator**: Use deionized (DI) water as the initiator if the polymerization is grafted onto a hydrogel surface. Alternatively, add weak bases (e.g., ammonium hydroxide) to accelerate the reaction.\n- **Solvent**: If conducting this in bulk or solution, use a water-miscible organic solvent such as ethanol or acetone.\n\n---\n\n#### Step 4: Experimental Procedure\nHere we outline the preparation pathway for modifying the hydrophilicity of a polymer with cyanoacrylate:\n\n1. **Preparation of Polymer Substrate**:\n   - If the polymer is a solid surface or hydrogel, clean and equilibrate it in DI water to ensure wetting and remove impurities.\n   - For surface grafting, slightly roughen the substrate to increase adhesion (if applicable).\n\n2. **Preparing the Reaction Mixture**:\n   - Dissolve the cyanoacrylate monomer (e.g., 0.1–0.5 g) in an organic solvent (10 mL acetone or ethanol).\n   - Optionally, add a trace amount of water (∼0.1 mL) or weak base to initiate controlled polymerization.\n\n3. **Applying the Cyanoacrylate**:\n   - **Surface Modification**: Apply the cyanoacrylate solution to the polymer surface using drop-casting, dip-coating, or spin-coating techniques. Allow polymerization to proceed for 1–5 minutes at room temperature.\n   - **Bulk Modification**: To incorporate cyanoacrylate into a gel network, allow the monomer solution to diffuse into the gel matrix for 10–30 minutes before initiating polymerization using environmental conditions (e.g., applying water vapors or increasing pH).\n\n4. **Polymerization Reaction**:\n   - Allow the cyanoacrylate to polymerize fully in an oxygen-free environment, as oxygen may inhibit polymerization.\n   - Conduct the reaction at room temperature or slightly elevated temperatures (e.g., 30–40°C) to ensure complete propagation.\n\n5. **Post-Polymerization Treatment**:\n   - Wash the polymer with water or ethanol to remove unreacted monomers and oligomers.\n   - Immerse in DI water for 24 hours to fully hydrate the structure and assess hydrophilicity.\n\n---\n\n#### Step 5: Evaluation of Hydrophilicity\nTo confirm enhancement of hydrophilicity, perform the following tests:\n1. **Contact Angle Measurement**: Test the water contact angle on the surface. A lower angle indicates higher hydrophilicity.\n2. **Swelling Behavior**: For gels, measure water uptake by determining the swelling ratio before and after modification.\n3. **FTIR Analysis**: Verify the incorporation of cyanoacrylate by identifying characteristic absorption peaks at ∼1730 cm⁻¹ (C=O stretch) and ∼2200 cm⁻¹ (C≡N stretch).\n\n---\n\n### Key Considerations During Preparation\n1. **Side Reactions**: Prevent unwanted polymerization in bulk solution by controlling the environmental conditions (e.g., reducing exposure to humid air).\n2. **Homogeneity**: If possible, use mechanical stirring or ultrasonication to increase mixing and uniformity of the modification.\n3. **Biocompatibility or Toxicity**: If the final polymer is to be used in biomedical applications, ensure cytotoxic components are thoroughly removed.\n\n---\n\nBy coupling the highly reactive polymerization tendencies of cyanoacrylate monomers with the existing polymer network, this approach systematically enhances hydrophilicity in a controlled, reproducible manner."
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+{
+  "design_question": "Design an experimental scheme for synthesizing a hydrophilic polymer using photocrosslinkable methacrylic pullulan, ensuring the polymer is suitable for applications requiring high water retention. Include the methods for crosslinking and any functional group modifications.",
+  "design_answer": "Certainly! Let's approach this question step by step to systematically develop an experimental scheme for synthesizing a hydrophilic polymer using photocrosslinkable methacrylic pullulan. The goal is to create a hydrogel-like material with high water retention properties, ensuring it is ideal for applications requiring superior hydrophilicity (e.g., bioengineering scaffolds or wound dressings). I'll break down the process as follows:\n\n---\n\n### **Step 1: Analyze the Question and Summarize Key Points**\n\nThe key aspects of the question include:\n1. **Polymer Base Material:** Photocrosslinkable methacrylic pullulan (a polysaccharide derivative that can be functionalized to include methacrylate groups for crosslinking).\n2. **Desired Property:** High hydrophilicity with excellent water retention.\n3. **Experimental Requirements:**\n   - Synthesis of the hydrophilic polymer using methacrylic pullulan.\n   - Introduction of any necessary functional group modifications to enhance hydrophilicity.\n   - Use of photocrosslinking (via UV irradiation and photoinitiator) to form a well-structured polymer network.\n\nThe objective is thus to functionalize pullulan, photocrosslink it into a hydrogel, and optimize its water retention properties by controlling the degree of crosslinking and incorporating hydrophilic functional groups where necessary.\n\n---\n\n### **Step 2: Develop the Experimental Scheme**\n\n#### **(A) Materials Required**\n1. **Methacrylic Pullulan:**\n   - Prepared by modifying pullulan with methacrylate groups. If unavailable, this functionalization can be done in-house (see details in Step 2B).\n2. **Photoinitiator:** Irgacure 2959 (2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone) is commonly used due to water solubility and suitability for UV curing.\n3. **Solvent for Dissolution:** Deionized water or a water/ethanol mixture.\n4. **Optional Co-monomer for Hydrophilicity Enhancement** (if needed):\n   - Acrylic acid, N-vinylpyrrolidone, or polyethylene glycol diacrylate (PEGDA) can be included to increase hydrophilic properties.\n\n#### **(B) Preparation of Methacrylic Pullulan (if pre-synthesized methacrylic pullulan is not available)**\n\n1. **Reagents Needed:**\n   - Pullulan (a polysaccharide polymer).\n   - Methacrylic anhydride (functionalizing agent with methacrylate groups).\n   - Base catalyst (e.g., triethylamine).\n   - Solvent: Deionized water or phosphate-buffered saline.\n\n2. **Synthesis Procedure:**\n   - Dissolve pullulan in deionized water (5–10 wt% concentration) under agitation at 25–50 °C.\n   - Slowly add methacrylic anhydride to the pullulan solution while maintaining the pH between 8 and 9 using a base (triethylamine or NaOH). Ensure dropwise addition to avoid rapid hydrolysis.\n   - Allow the reaction to proceed for 3–6 hours at room temperature, constantly monitoring the pH and stirring.\n   - The methacrylation of hydroxyl groups in pullulan results in methacrylic pullulan.\n   - Purify the product by dialyzing against deionized water for 48–72 hours to remove unreacted methacrylic anhydride and byproducts.\n   - Lyophilize the purified product to obtain methacrylic pullulan as a dry powder.\n\n---\n\n#### **(C) Photo-Crosslinking and Hydrogel Formation**\n\n1. **Reagents Needed:**\n   - Methacrylic pullulan (prepared or pre-synthesized).\n   - Photoinitiator: Irgacure 2959 (recommended concentration: 0.5 wt% relative to polymer).\n   - Water or an aqueous solvent.\n\n2. **Procedure:**\n   - Dissolve methacrylic pullulan (10–15 wt%) in deionized water at room temperature to form a clear solution.\n   - Add the photoinitiator (Irgacure 2959) to the solution and stir until completely dissolved. Ensure uniform mixing.\n   - Pour the solution into molds (e.g., Teflon molds or glass molds) to achieve the desired hydrogel shape/geometry.\n   - Expose the solution to UV light (typically 365 nm wavelength) for crosslinking. Use a UV lamp with an intensity of ~5–10 mW/cm².\n   - UV irradiation time may vary (5–15 minutes), depending on the desired crosslinking density and mechanical strength of the final hydrogel.\n\n   **Notes on UV Crosslinking Conditions:**\n   - A longer exposure time generally increases crosslinking density but reduces swelling capacity. Optimize based on water retention requirements.\n   - Avoid overheating during UV curing to preserve polymer properties.\n\n---\n\n#### **(D) Enhancing Hydrophilicity**\nIf additional hydrophilicity is required, incorporate hydrophilic co-monomers into the formulation prior to crosslinking. For example:\n- Add acrylic acid to the polymer solution to introduce carboxylic groups.\n- Include PEGDA if increased elasticity and water absorption are desired.\nOptimize the ratio of methacrylic pullulan to hydrophilic co-monomer (e.g., 90:10 or 80:20) to improve final properties.\n\n---\n\n#### **(E) Characterization of the Hydrophilic Polymer**\n1. **Swelling Ratio:**\n   - Immerse the hydrogel in deionized water and measure its swelling behavior over time.\n   - Calculate the swelling capacity using the formula:\n     \\[\n     \\text{Swelling Ratio} = \\frac{\\text{Weight of swollen hydrogel} - \\text{Weight of dry hydrogel}}{\\text{Weight of dry hydrogel}}\n     \\]\n2. **Water Retention Test:**\n   - Monitor the water content retained by the hydrogel after exposure to different environmental conditions.\n3. **Mechanical Testing:**\n   - Assess the hydrogel’s mechanical properties (e.g., elasticity, compressive strength) if required for load-bearing applications.\n4. **Fourier Transform Infrared Spectroscopy (FTIR):**\n   - Confirm the presence of methacrylate groups and successful crosslinking.\n\n---\n\n### **Step 3: Summary**\nThis experimental scheme provides a detailed methodology for synthesizing a hydrophilic polymer with excellent water retention properties, using methacrylic pullulan as a base. The process includes:\n1. Functionalization of pullulan with methacrylate groups.\n2. Photocrosslinking methacrylic pullulan under UV irradiation to form a hydrogel.\n3. Optional incorporation of hydrophilic co-monomers to enhance hydrophilicity.\n4. Evaluation of the polymer's water absorption and retention properties.\n\nBy carefully adjusting the degree of crosslinking and evaluating the role of hydrophilic additives, this approach allows tuning of the polymer’s properties to meet the desired application. Let me know if you need help with protocol adjustments or further discussion!"
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+{
+  "design_question": "How would you determine the degree of functionalization (DoF) after functionalizing a polymer with methacrylic anhydride (MA)? Describe this process and the calculations involved.",
+  "design_answer": "To determine the **degree of functionalization (DoF)** after functionalizing a polymer with methacrylic anhydride (MA), we need to consider a systematic approach that analyzes the chemical structure of the polymer before and after modification to quantify the extent of functionalization. Below, I’ll walk you through the process, covering experimental techniques, calculation methods, and supporting details to help you successfully evaluate the DoF.\n\n---\n\n### **Key Points to Analyze**\n1. **What does Degree of Functionalization (DoF) mean?**\n   - DoF refers to the fraction (or percentage) of reactive functional groups on the polymer backbone that are successfully modified with the desired functional group—in this case, the methacrylic group from MA.\n\n2. **Main experimental objective:**\n   - Quantitatively determine how many functional sites on the polymer (e.g., hydroxyl, amine, or other reactive groups) have reacted with methacrylic anhydride.\n\n---\n\n### **Step-by-Step Process with Detailed Procedures**\n\n#### **Step 1: Characterization Techniques to Measure DoF**\nThere are several analytical techniques that can be used to quantify DoF, depending on the composition and molecular structure of the polymer. Below are the most common methods:\n\n##### **A. Nuclear Magnetic Resonance (NMR) Spectroscopy**\n   - **Objective:** Use NMR (typically 1H-NMR or 13C-NMR) to compare the chemical shifts and integration values representing the modified groups and the unmodified functional groups.\n   - **Experimental Process:**\n     1. Prepare polymer samples before and after functionalization.\n     2. Dissolve the samples in an appropriate solvent (e.g., deuterated chloroform, DMSO-d6, or water, depending on polymer solubility).\n     3. Run an NMR spectrum and identify peaks corresponding to the methacrylic group's protons (e.g., vinyl protons or ester protons) and those of the unmodified polymer.\n     4. Integrate the peak areas associated with the functionalized groups (such as methacrylic vinyl (-CH=CH2) or ester groups (-COO-)).\n   - **Calculation:**\n     - Degree of functionalization (DoF) is calculated as:\n       \\[\n       \\text{DoF} = \\frac{\\text{Integration of functionalized groups}}{\\text{Total polymer group integration (before/after modification)}} \\times 100\n       \\]\n       For example, if the hydroxyl or amine group on the polymer backbone was targeted, a reduction in hydroxyl/amine signals and an increase in methacrylate signals can be correlated.\n\n##### **B. Fourier Transform Infrared (FTIR) Spectroscopy**\n   - **Objective:** Identify functional groups that appear (e.g., ester groups from MA) or disappear (e.g., hydroxyl groups modified during the reaction) by comparing IR spectra of the unmodified and modified polymer.\n   - **Experimental Process:**\n     1. Prepare polymer samples before and after functionalization.\n     2. Record FTIR spectra in the appropriate range (e.g., 4000–400 cm⁻¹).\n     3. Identify new bands corresponding to methacrylic functional groups (characteristic C=O stretching around 1720 cm⁻¹, C=C stretching around 1650 cm⁻¹) and track the depletion of unmodified groups like hydroxyl stretching (O-H at ∼3300 cm⁻¹).\n   - **Calculation:**\n     - Use peak intensities to semi-quantitatively estimate the degree of functionalization. FTIR is less accurate for detailed DoF calculations but can serve as a good complementary tool.\n\n##### **C. Mass Spectrometry (if necessary)**\n   - Measure the molecular weight change before and after functionalization using tools such as MALDI-TOF or ESI-MS.\n   - This is most useful for low molecular weight polymers or oligomers.\n\n---\n\n#### **Step 2: Direct Titration Method**\nIf the polymer contains reactive functional groups such as hydroxyl or amine groups, titration can provide direct quantitative data on DoF.\n\n##### **Experimental Procedure:**\n1. **Unmodified Polymer Titration**:\n   - Dissolve the unmodified polymer in a solvent (e.g., water or ethanol, depending on solubility).\n   - React the polymer with a titrant that reacts with the functional group (e.g., strong acid for hydroxyl or amine groups) and measure the consumption of titrant.\n\n2. **Modified Polymer Titration**:\n   - Repeat the titration with the modified polymer to measure how many residual functional groups remain unreacted.\n\n##### **Calculation:**\n   - Assuming methacrylic anhydride reacts in a 1:1 molar ratio with the functional group, the DoF is determined as:\n     \\[\n     \\text{DoF} = \\frac{\\text{Moles of modified functional groups}}{\\text{Moles of total functional groups (initially present)}} \\times 100\n     \\]\n     Here, \"moles of modified functional groups\" can be calculated by the difference in titration results before and after functionalization.\n\n---\n\n#### **Step 3: Experimental Controls**\n1. **Run blank experiments with unmodified polymer** to validate baseline characterization data.\n2. Ensure reaction completion by optimizing reaction parameters such as time, temperature, solvent, and catalyst (e.g., pyridine for MA-functionalization of hydroxyl-containing polymers).\n\n---\n\n### **Detailed Example Calculation**\nAssume the polymer starts with 1.00 mmol hydroxyl groups and after reaction with methacrylic anhydride, NMR analysis shows integration values corresponding to 0.80 mmol modified methacrylic groups.\n\n- **DoF Calculation:**\n  \\[\n  \\text{DoF} = \\frac{\\text{0.80 mmol}}{\\text{1.00 mmol}} \\times 100 = 80\\%\n  \\]\n\n---\n\n### **Practical Notes and Additional Tips**\n1. **Optimize reaction conditions**: Methacrylic anhydride functionalization might require mild conditions to avoid polymer degradation (e.g., reaction temperatures of 25–50°C, mild catalysts like pyridine, and solvents like DMSO or dichloromethane).\n2. **Monitor the reaction progress**: Use real-time NMR or FTIR spectroscopy data to confirm when the reaction reaches completion.\n3. **Repeat trials** for reproducibility and statistically evaluate surface or bulk functionalization (if applicable).\n\nBy following these steps, the student should be able to determine the DoF with adequate precision and understand the various dynamics involved in polymer functionalization."
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diff --git a/task2/task2-qa/╣т╜╗┴к╦о─¤╜║╫█╩Ў.json b/task2/task2-qa/╣т╜╗┴к╦о─¤╜║╫█╩Ў.json
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+{
+  "design_question": "You are tasked with synthesizing poly(ethylene glycol) diacrylate (PEGDA). Based on the molecule provided, describe the procedure to functionalize polyethylene glycol (PEG) with acrylate groups and identify the key reaction steps involved in the acrylation process.",
+  "design_answer": "To synthesize poly(ethylene glycol) diacrylate (PEGDA), we need to functionalize a polyethylene glycol (PEG) molecule with acrylate groups. Before diving into the experimental details of the procedure, let’s first analyze the question, summarize the critical points, and plan the process step-by-step.\n\n---\n\n### **1. Analyze the Question and Summarize Key Points**\n- **Objective**: To synthesize poly(ethylene glycol) diacrylate (PEGDA) by introducing acrylate functional groups to both hydroxyl (-OH) groups at the ends of a polyethylene glycol chain.\n- **Key Requirements**: \n  - A polyethylene glycol (PEG) molecule as the starting material.\n  - Acrylation reagents to react with the hydroxyl groups.\n  - Specific reaction conditions to ensure proper functionalization, avoiding side reactions or incomplete conversion.\n  - Reaction byproducts (e.g., water or acid byproducts) must be removed carefully to purify PEGDA.\n\n**Critical steps to achieve this**:\n1. Activation of acrylate functionality.\n2. Controlled reaction between PEG and acrylate precursor to obtain PEGDA.\n3. Purification of the final product to isolate pure PEGDA.\n\n---\n\n### **2. Step-by-Step Detailed Synthesis of PEGDA**\nBelow is a systematic synthesis procedure with details on reagents, conditions, and practical laboratory considerations for preparing PEGDA.\n\n---\n\n#### **Step 1: Select the Starting Materials and Reagents**\n1. **Polyethylene Glycol (PEG):**\n   - Use a dihydroxyl-terminated polyethylene glycol (HO-PEG-OH). The molecular weight of PEG can vary (e.g., PEG of Mw = 400 or 1000 g/mol) depending on the intended application of the PEGDA product.\n\n2. **Acryloyl Chloride**: \n   - Acryloyl chloride is used as the acrylate precursor. It reacts readily with hydroxyl groups to introduce acrylate moieties.\n\n3. **Base:**\n   - A base (e.g., triethylamine, TEA) is used to neutralize the HCl byproduct formed during the reaction and prevent side reactions involving the acid.\n\n4. **Solvent:**\n   - Use a dry, inert organic solvent such as dichloromethane (DCM) or tetrahydrofuran (THF).\n\n5. **Inhibitors:**\n   - Add a polymerization inhibitor (e.g., hydroquinone or 4-methoxyphenol, MEHQ) to prevent premature polymerization of the acrylate groups.\n\n---\n\n#### **Step 2: Reaction Setup**\n1. **Apparatus**: \n   - A reaction flask equipped with a magnetic stirrer, a dropping funnel (for controlled addition of reagents), and a reflux condenser.\n   - Maintain an inert atmosphere using nitrogen or argon gas if necessary to avoid moisture or oxygen contamination.\n   - A thermometer to monitor the reaction temperature.\n\n2. **Preparation of PEG Solution**:\n   - Dissolve the PEG in dry dichloromethane (DCM) or THF in the reaction flask. Use approximately 1 equivalent of PEG (dihydroxyl groups).\n\n3. **Addition of Base**:\n   - Add triethylamine (TEA) at a molar ratio of 2 equivalents per hydroxyl group of PEG to the reaction mixture. TEA will neutralize HCl generated during the acrylation reaction.\n\n---\n\n#### **Step 3: Acrylation Reaction**\n1. **Prepare Acryloyl Chloride Solution**:\n   - In a separate container, dilute acryloyl chloride in dry DCM or THF. The molar ratio of acryloyl chloride to PEG hydroxyl groups should be slightly higher (>1:1, typically 1.1–1.2 equivalents per hydroxyl group) to ensure full functionalization.\n\n2. **Controlled Addition**:\n   - Using the dropping funnel, add the acryloyl chloride solution slowly to the stirred PEG solution over ~30 minutes. This helps maintain a stable reaction and minimizes side reactions.\n\n3. **Reaction Conditions**:\n   - Maintain the reaction mixture at 0–5°C during the addition of acryloyl chloride to reduce the exothermic nature of the reaction.\n   - After the addition is complete, allow the reaction to stir at room temperature (~25°C) for 4–6 hours to ensure complete conversion to PEGDA.\n\n4. **Inhibitor Addition** (if not already added):\n   - Add a small amount of hydroquinone or MEHQ (e.g., ~100 ppm) to prevent premature polymerization of the acrylate-functionalized product.\n\n---\n\n#### **Step 4: Workup and Purification**\n1. **Neutralize Byproducts**:\n   - Filter the reaction mixture to remove the triethylamine hydrochloride salt precipitate.\n\n2. **Washing**:\n   - Wash the organic phase with deionized water or dilute sodium bicarbonate solution to neutralize and remove any unreacted acid (e.g., HCl).\n\n3. **Drying**:\n   - Dry the organic phase over anhydrous sodium sulfate to remove residual moisture.\n\n4. **Evaporation**:\n   - Use a rotary evaporator to remove the solvent under reduced pressure, isolating the crude PEGDA product.\n\n5. **Purification**:\n   - If needed, the product can be purified further by precipitation in cold diethyl ether or through column chromatography.\n\n---\n\n#### **Step 5: Product Characterization**\n1. **Nuclear Magnetic Resonance (NMR)**:\n   - Use 1H NMR spectroscopy to confirm successful acrylation. The vinyl protons of the acrylate group (-CH=CH2) should appear as distinctive peaks (~5.8–6.5 ppm).\n\n2. **Fourier Transform Infrared Spectroscopy (FTIR)**:\n   - Verify the presence of acrylate groups by observing the stretching vibration of the carbonyl groups (C=O) near 1720 cm⁻¹.\n\n3. **Gel Permeation Chromatography (GPC)**:\n   - Confirm the molecular weight of the PEGDA product and assess the polydispersity index (PDI).\n\n---\n\n### **Summary of Reaction**\nThe reaction can be summarized as:\n\\[ HO-PEG-OH + 2 \\, \\text{CH}_2=CH-\\text{COCl} \\xrightarrow[\\text{TEA}]{\\text{DCM or THF}} \\text{CH}_2=CH-\\text{COO}-PEG-\\text{OCO}-CH=CH_2 + 2 \\, \\text{HCl} \\]\n\nIn this synthetic scheme, PEG is di-functionalized with acrylate groups to yield PEGDA, which is widely used in hydrogel synthesis, bioconjugation, and tissue engineering.\n\n---\n\nBy following this carefully designed protocol, you will obtain high-purity PEGDA ready for further applications. Good luck, and remember to take necessary laboratory precautions, especially when handling acryloyl chloride and organic solvents! 😊"
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diff --git a/task2/task2-qa/╣т╣╠╗п▓─┴╧╨╘─▄╝░╙ж╙├╩╓▓с ╜Ё╤°╓╟.json b/task2/task2-qa/╣т╣╠╗п▓─┴╧╨╘─▄╝░╙ж╙├╩╓▓с ╜Ё╤°╓╟.json
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+{
+  "design_question": "Using diethylene glycol diacrylate (DEGDA) as the chosen molecule, outline the steps for synthesizing a crosslinked polymer network. How would this structure contribute to improved hydrophilicity, and what methods would you use to assess the polymer's water-absorption capacity?",
+  "design_answer": "To synthesize a crosslinked polymer network using diethylene glycol diacrylate (DEGDA) and assess its hydrophilicity and water absorption capacity, we will break this process into a detailed, systematic experimental preparation scheme. By following exact steps and describing relevant conditions, reagent ratios, and methods, you will be adequately prepared to complete the experiment successfully in the laboratory.\n\n---\n\n### **Step 1: Analyze the Question and Summarize Key Points**\n\n1. **Objective:** Synthesize a crosslinked polymer network from diethylene glycol diacrylate (DEGDA).\n2. **Challenges to Address:** Enhance hydrophilicity of the polymer and examine its water-absorption capacity.\n3. **Approach:**\n   - Leverage the diacrylate structure of DEGDA to form a crosslinked polymer network.\n   - Highlight how the ether linkages in DEGDA contribute to water affinity.\n   - Specify methods to assess water absorption, such as gravimetric analysis or swelling studies.\n\n### **Step 2: Experimental Plan for Synthesizing the Crosslinked Polymer**\n\n#### **Step 2.1: Materials and Reagents**\n- **Diethylene Glycol Diacrylate (DEGDA):** Monomer with two acrylic functional groups for crosslinking.\n- **Initiator:** Use a radical initiator such as azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO), depending on experimental setup (thermal or photoinitiated polymerization).\n- **Crosslinking Agent (Optional):** Although DEGDA already contains diacrylate groups that promote crosslinking, small amounts of a third monomer like acrylic acid (AA) may be introduced to further improve hydrophilicity.\n- **Solvent (if needed):** Ethanol or deionized water to dissolve monomers and ensure homogeneity.\n- **Deionized Water:** For later washing and testing.\n- **Nitrogen or Argon:** To create an inert atmosphere for polymerization and prevent oxygen inhibition.\n\n---\n\n#### **Step 2.2: Polymerization Method**\n\n##### **Option 1: Thermal Radical Polymerization**\n1. **Preparation of Reaction Mixture:**\n   - Dissolve DEGDA in a solvent (e.g., ethanol) at a desired concentration (e.g., 10–20 wt% relative to solvent).\n   - Add AIBN at a concentration of ~1–2 mol% relative to DEGDA monomer.\n   - Optional: If a comonomer such as acrylic acid is used, mix at a molar ratio of 90:10 (DEGDA:AA) to further boost hydrophilicity.\n\n2. **Degassing the Solution:**\n   - Place the reaction mixture in a reaction flask.\n   - Bubble nitrogen gas (or argon) through the solution for 10–15 minutes to remove dissolved oxygen that may inhibit free-radical polymerization.\n\n3. **Thermal Polymerization:**\n   - Heat the degassed reaction mixture to **60–70°C** under a nitrogen atmosphere.\n   - Polymerization will proceed via the initiation, propagation, and termination steps of free-radical mechanisms, forming a crosslinked network as DEGDA's two acrylate groups react with one another.\n   - Allow the reaction to proceed for **4–8 hours** to ensure full polymerization.\n\n---\n\n##### **Option 2: Photopolymerization (UV-Curing)**\n1. **Preparation of Reaction Mixture:**\n   - Dissolve DEGDA in ethanol at the desired concentration.\n   - Add a photoinitiator, such as Irgacure-2959, at ~1 wt% relative to the DEGDA.\n   - Optional: Add a comonomer such as a polyethylene glycol (PEG)-acrylate derivative for enhanced hydrophilicity.\n\n2. **Degassing Step:**\n   - Degas the reaction mixture with nitrogen/argon prior to UV exposure to avoid oxygen inhibition.\n\n3. **UV Irradiation:**\n   - Place the reaction mixture in a UV-curing chamber.\n   - Irradiate with UV light (wavelength ~365 nm) for **10–30 minutes**. The UV energy will activate the photoinitiator, initiating radical polymerization and creating the crosslinked network.\n\n---\n\n#### **Step 2.3: Purification of the Polymer**\n- After the polymerization reaction is complete:\n  - Wash the polymer thoroughly with ethanol and deionized water to remove unreacted monomers and other impurities.\n  - Dry the polymer in a vacuum oven or desiccator at 40–50°C until a constant weight is achieved.\n\n---\n\n### **Step 3: Assess How the Structure Improves Hydrophilicity**\n\nThe structure of the synthesized polymer network contributes to improved hydrophilicity in the following ways:\n1. **Ether Linkages in DEGDA Backbone:** The ether (-CH2-O-CH2-) groups in the diethylene glycol segment of DEGDA are inherently polar and capable of hydrogen bonding with water molecules, enhancing water affinity.\n2. **Crosslinked Network:** The polymer network's crosslinking density determines water uptake, as lower-density crosslinks create larger pores that enhance swelling and water absorption.\n3. **Optional Acrylic Acid (AA) Comonomer:** If incorporated, carboxylic acid groups (-COOH) in AA add ionizable groups that increase hydrophilicity by promoting osmotic swelling in water.\n\n---\n\n### **Step 4: Methods to Assess Water-Absorption Capacity**\n\nEvaluate the hydrophilicity and water-absorption properties of the synthesized polymer using the following methods:\n\n#### **4.1: Water-Swelling Capacity (Gravimetric Analysis)**\n1. **Procedure:**\n   - Dry the polymer to a constant weight (**W_d**) in a vacuum oven.\n   - Immerse the dried polymer sample in deionized water at room temperature and allow it to swell for 24 hours.\n   - Remove the swollen polymer, blot the surface with filter paper, and weigh it immediately (**W_s**).\n2. **Calculate Water Absorption:**\n   - Use the formula:\n     \\[\n     \\text{Water Absorption (%) = } \\frac{W_s - W_d}{W_d} \\times 100\n     \\]\n   - This gives the mass percentage of water absorbed by the polymer.\n\n---\n\n#### **4.2: Contact Angle Measurement**\n1. **Procedure:**\n   - Place the synthesized polymer as a thin film or disk in a contact angle goniometer.\n   - Drop a small droplet of water on the polymer surface and measure the contact angle.\n2. **Analysis:**\n   - A smaller contact angle (<90°) indicates higher hydrophilicity, while a larger angle (>90°) suggests hydrophobicity.\n\n---\n\n#### **4.3: Swelling Kinetics**\n1. **Procedure:**\n   - Measure polymer weight at different time intervals (e.g., every 10, 20, 30 minutes) during water immersion.\n   - Observe how rapidly the polymer absorbs water, indicating the speed of swelling.\n2. **Analysis:**\n   - Plot swelling ratio vs. time to determine the equilibrium swelling time and saturation behavior.\n\n---\n\n### **Conclusion**\n\nBy following the described experimental procedure, you can successfully prepare a hydrophilic, crosslinked polymer network using diethylene glycol diacrylate (DEGDA). The structural features of DEGDA, including hydrophilic ether linkages, and the potential use of hydrophilic comonomers, enhance water affinity. Use the outlined evaluation techniques, such as water-swelling capacity and contact angle measurement, to confirm the polymer's hydrophilicity and quantify its water absorption. This hands-on approach ensures a complete understanding of hydrophilic polymer preparation and testing methods."
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+{
+  "design_question": "Design an experimental scheme where N,N-dimethylacrylamide (DMAA) is included to form a hydrophilic coating on a medical-grade polymer surface. Be specific about the steps and conditions required.",
+  "design_answer": "To design an experimental scheme incorporating **N,N-dimethylacrylamide (DMAA)** to create a **hydrophilic coating** on a medical-grade polymer surface, we will step through the process meticulously. The hydrophilic polymer coating must be stable, biocompatible, and offer sustained hydrophilicity, all of which are critical for medical applications.\n\n---\n\n### **Step 1: Key Question Analysis**\n\n**Primary Goal:**\n1. To utilize DMAA to form a hydrophilic coating on a medical-grade polymer surface.\n\n**Considerations:**\n1. The polymer surface must be modified to ensure the coating strongly adheres, as untreated polymer surfaces typically lack reactive groups for polymerization. \n2. The polymerization of DMAA will likely proceed via free-radical polymerization, a well-established method for hydrophilic polymer synthesis.\n3. Surface-induced polymerization or grafting may be used for coating stability.\n4. The hydrophilicity will stem from the DMAA side-chain's ability to form hydrogen bonds with water molecules.\n\nKey steps will include:\n1. Surface preparation of the medical-grade polymer.\n2. Initiating or facilitating graft polymerization of DMAA.\n3. Optimization of reaction conditions to achieve a uniform and functional hydrophilic coating.\n\n---\n\n### **Step 2: Experimental Scheme**\n\n#### **Step 2.1: Materials and Reagents**\n- **Substrate:** Medical-grade polymer (e.g., Polyurethane, Silicone, or Polyethylene).\n- **Monomer:** N,N-Dimethylacrylamide (DMAA).\n- **Photoinitiator:** Benzophenone (surface-attached or dissolved for UV-initiated polymerization), or similar radical initiators (e.g., Irgacure 2959 for aqueous photopolymerization).\n- **Solvent:** Ethanol or isopropanol, if needed, to clean the surface.\n- **Oxidizing agent:** Hydrogen peroxide (H₂O₂), for pretreating the polymer surface in cases where no reactive groups are present.\n- **Crosslinker (optional):** N,N′-methylenebisacrylamide, if some degree of crosslinking is needed for coating durability.\n- **Buffers and additives** (if needed): To ensure biocompatibility and stability.\n\n---\n\n### **Step 2.2: Procedure**\n\n#### **A. Surface Preparation of the Medical-Grade Polymer**\n1. **Cleaning:** Rinse the medical-grade polymer in ethanol or isopropanol and ultrasonicate for 5–10 minutes to remove surface contaminants.\n2. **Oxidation/Activation:** \n   - Immerse the substrate in a solution of **30% hydrogen peroxide** at room temperature for 1–2 hours to create hydroxyl or peroxide groups on the surface. \n   - Alternately, plasma treatment (e.g., oxygen plasma for 5 minutes) can be used to increase surface wettability and introduce surface functionalities.\n3. **Functionalization with a Photoinitiator (if applicable):**\n   - Immerse the substrate in a solution of **Benzophenone (2% w/v)** dissolved in ethanol or acetone for 30 minutes at room temperature. This step enables photoinitiated radical grafting of DMAA onto the surface.\n\n#### **B. Preparation of the DMAA Polymerization Mixture**\n1. **Prepare the Monomer Solution:**\n   - Dissolve **N,N-dimethylacrylamide (DMAA)** monomer in distilled water or an alcohol-water mixture to create a 5–10% (v/v) solution.\n   - If durability is critical, add **0.01–0.05% N,N′-methylenebisacrylamide** as a mild crosslinker.\n   - Adjust the solution to neutral pH using a buffer (e.g., phosphate-buffered saline) to ensure compatibility with medical surfaces.\n\n2. **Photoinitiator Activation (if not surface-tethered):**\n   - Add **Irgacure 2959 (0.2–0.5% w/v)** or a water-soluble photoinitiator to the solution for radical initiation under UV light.\n   - If thermal polymerization is preferred, **ammonium persulfate (0.5% w/v)** with **N,N,N′,N′-tetramethylethylenediamine (TEMED)** can substitute the photoinitiator.\n\n#### **C. Polymerization Process**\n1. Place the pre-treated medical-grade polymer substrate into the monomer solution, ensuring complete surface contact.\n2. Initiate polymerization:\n   - For **UV-initiated polymerization**, irradiate the substrate with a UV lamp (e.g., 365 nm wavelength) at an intensity of ~5 mW/cm² for 15–30 minutes.\n   - For **thermal polymerization**, incubate at 40–60 °C for 2–4 hours.\n\n#### **D. Post-Polymerization Washing and Drying**\n1. Remove the substrate from the solution and rinse thoroughly with **water or weak ethanol solution** to remove unreacted monomers.\n2. Immerse the substrate in distilled water overnight at room temperature to leach out any remaining initiators or non-bonded polymer byproducts.\n3. Dry the coated substrate under vacuum or air-dry it in a dust-free environment.\n\n---\n\n### **Step 3: Reaction Parameters & Optimization**\n\n- **Monomer Concentration:** 5–10% w/v is optimal for forming a uniform, hydrophilic coating without excessive swelling.\n- **UV Curing Time:** Monitor for uniform polymerization, optimizing exposure time depending on lamp intensity and polymer surface geometry.\n- **Hydrophilic Test:** Assess surface hydrophilicity via **water contact angle measurement (target: <30°)** and confirm via XPS (for nitrogen incorporation from DMAA).\n\n---\n\n### **Step 4: Quality Control and Validation**\n1. Perform **water retention and stability tests** (e.g., immersion in saline solution at 37 °C for 24 hours) to verify coating durability.\n2. Conduct **biocompatibility tests** to confirm that the coated surface meets medical standards.\n\n---\n\n### **Concluding Remarks**\n\nThis process ensures a stable, covalently grafted hydrophilic coating incorporating N,N-Dimethylacrylamide. The use of photoinitiators and surface pretreatment maximizes adhesion, while the detailed reaction conditions ensure reproducibility for medical applications. Feel free to discuss specific materials or reaction constraints if adaption is needed to different substrates!\n\n"
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+{
+  "design_question": "Describe how you would ensure that N,N-dimethylacrylamide (DMAA) is effectively polymerized onto a polymer surface to enhance hydrophilicity. Include any necessary steps to prepare the surface before polymerization.",
+  "design_answer": "To ensure that N,N-dimethylacrylamide (DMAA) is effectively polymerized onto a polymer surface to enhance hydrophilicity, it is essential to consider both the surface preparation and the polymerization process itself. Below, I will systematically and comprehensively outline the procedure, incorporating detailed reaction conditions, reagent ratios, and practical laboratory considerations.\n\n---\n\n### **Step-by-Step Experimental Preparation Scheme**\n\n---\n\n#### **Step 1: Analyze the Question and Define the Key Points**\n\nThe main objective is to graft a hydrophilic polymer, specifically poly(N,N-dimethylacrylamide) (PDMAA), onto the surface of a base polymer to enhance the hydrophilicity of the material. Two critical aspects need to be addressed:\n1. **Surface preparation**: Modify the polymer surface to introduce reactive functional groups for subsequent DMAA polymerization.\n2. **Polymerization process**: Ensure that DMAA polymerizes effectively onto the functionalized surface in a controlled manner to create a uniform hydrophilic coating.\n\n---\n\n#### **Step 2: Surface Preparation**\n\nBefore DMAA can be polymerized onto the polymer surface, the surface must be treated to introduce functional groups (e.g., hydroxyl, carboxyl, or amine groups) that can act as initiation points for the polymerization process.\n\n1. **Cleaning the Base Polymer Surface:**\n    - Wash the polymer substrate thoroughly with a series of solvents to remove surface contaminants (e.g., organic residues, oils, or dust).\n    - Suggested protocol: rinse in deionized water, followed by immersion in ethanol or isopropanol, and then air-dry.\n\n2. **Activation via Oxidation (if applicable):**\n    - For non-reactive polymer surfaces (e.g., polyethylene or polypropylene), plasma treatment or oxidative treatment (e.g., using ozone or chromic acid) can introduce carboxyl or hydroxyl groups.\n    - Example: Plasma treatment with oxygen gas for 5–10 minutes at low pressure (~200 mTorr). Alternatively, immerse the polymer in 0.1 M chromic acid for 15–20 minutes, followed by rinsing thoroughly with deionized water.\n\n3. **Coupling Agent Application (Optional for Improved Attachment):**\n    - Apply a silane coupling agent if the polymer surface is inherently poor in chemical reactivity.\n    - Example: Treat the polymer surface with 0.1% (v/v) solution of 3-aminopropyltriethoxysilane (APTES) in ethanol for 30 minutes at room temperature, followed by rinsing and curing at 100 °C for 1 hour.\n\nThe resulting surface should contain active functional groups (e.g., hydroxyl, carboxyl, or amine moieties) to enable subsequent reaction with DMAA and initiators.\n\n---\n\n#### **Step 3: Polymerization of DMAA**\n\nDMAA will be grafted onto the prepared surface by free radical polymerization. This process involves the use of an initiator (e.g., a peroxide-based compound) and reaction conditions conducive to DMAA polymerization.\n\n1. **Preparation of Reaction Mixture:**\n    - Dissolve N,N-dimethylacrylamide (DMAA) in deionized water or an aqueous ethanol solution at a concentration of ~10–20% (w/v).\n    - Add an initiator, such as ammonium persulfate (APS), at 0.5–1.0% (w/v) relative to the DMAA monomer concentration.\n    - Include a catalyst or co-initiator for enhanced polymerization rates. For APS, N,N,N',N'-tetramethylethylenediamine (TEMED) can be used at 0.1% (w/v).\n    - Adjust the pH of the solution to ~7–8 using NaOH to ensure a stable reaction environment.\n\n2. **Immobilization of Initiator onto the Surface:**\n    - Coat the surface with a thin layer of APS solution (~0.1 M) and allow it to dry. This step ensures localized polymerization at the surface rather than in bulk solution.\n\n3. **Grafting of DMAA via Radical Polymerization:**\n    - Submerge the treated polymer surface into the DMAA reaction mixture.\n    - Maintain the reaction at ~40–60 °C for 4–8 hours (depending on monomer concentration and desired graft density). Ensure consistent stirring or gentle agitation of the solution to maintain uniform contact with the substrate.\n    - Optional: For UV-mediated polymerization, incorporate a photoinitiator (e.g., benzophenone) at ~1% (w/v) and expose the system to UV light (wavelength: 365 nm) for 1–2 hours.\n\n4. **Post-Polymerization Washing:**\n    - Thoroughly rinse the polymer substrate with deionized water to remove unreacted monomer and initiator residues.\n    - Use mild sonication (~40 kHz) in water for 10–15 minutes to ensure the removal of loosely bound polymer chains.\n\n---\n\n#### **Step 4: Characterization and Validation**\n\nTo confirm successful polymerization, employ the following characterization techniques:\n1. **Contact Angle Measurement:**\n    - Evaluate the hydrophilicity of the polymer surface by measuring the water contact angle. A significant reduction (e.g., <40°) compared to the untreated polymer indicates successful grafting of PDMAA.\n\n2. **Fourier Transform Infrared Spectroscopy (FTIR):**\n    - Look for characteristic amide peaks in the IR spectrum (e.g., C=O stretching at ~1650 cm⁻¹ and N-H bending at ~1540 cm⁻¹) as confirmation of DMAA polymerization.\n\n3. **Scanning Electron Microscopy (SEM):**\n    - Observe the surface morphology of the treated polymer. Uniform coating with polymerized PDMAA should appear smooth and continuous.\n\n4. **X-ray Photoelectron Spectroscopy (XPS):**\n    - Analyze surface elemental composition to confirm the presence of nitrogen from the DMAA structure.\n\n---\n\n#### **Step 5: Optimization of Grafting Density**\n\nThe grafting density of PDMAA can be optimized by altering the DMAA concentration, initiator ratio, or reaction time. Higher DMAA concentration or longer reaction times typically yield thicker hydrophilic coatings but may pose risks of delamination or brittleness. Iterative testing with the above characterization techniques will help refine the experimental parameters.\n\n---\n\n### **Conclusion**\n\nBy carefully preparing the polymer surface and conducting controlled radical polymerization of DMAA, you can achieve a robust hydrophilic coating that enhances surface wettability. This experimental scheme can be modified based on the specific polymer substrate or application requirements."
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+{
+  "design_question": "Describe the steps you would take to use sulfonic acid group-containing surfactants to prepare a modified hydrophilic polymer. Include the reaction conditions and catalysts required for the process.",
+  "design_answer": "Alright, let’s systematically develop an experimental preparation scheme for synthesizing a sulfonic acid group-modified hydrophilic polymer using a sulfonic acid group-containing surfactant. I'll analyze the problem first and then outline each step clearly.\n\n---\n\n### **Step 1: Problem Analysis**\nThe challenge is to prepare a hydrophilic polymer modified with sulfonic acid groups. Sulfonic acid groups (-SO₃H) are strongly hydrophilic due to their high polarity and ability to attract water. Incorporating these groups into a polymer will greatly enhance its hydrophilicity.\n\nWe will achieve this by:\n1. Choosing an appropriate polymer backbone that can react with the sulfonic acid group-containing surfactant.\n2. Ensuring the sulfonic acid groups can chemically attach (often through grafting or copolymerization methods) or become stably incorporated into the polymer matrix.\n3. Optimizing reaction conditions (temperature, pH, catalysts) for efficient grafting/modification.\n\n---\n\n### **Step 2: Experimental Design**\nHere is a systematic synthesis process. The approach will use free radical copolymerization to attach a sulfonic acid group-containing surfactant onto a vinyl monomer or polymer backbone.\n\n#### **Materials Required:**\n1. **Base Polymer**: A suitable vinyl monomer such as acrylamide, methacrylic acid, or vinyl acetate.\n2. **Sulfonic Acid Group-Containing Surfactant**: Sodium dodecylbenzenesulfonate (SDBS), known for its strong sulfonic acid group (-SO₃Na).\n3. **Initiator (Radical Source)**: Potassium persulfate (KPS) or ammonium persulfate (APS).\n4. **Solvent/Medium**: Deionized water or an aqueous ethanol solution (depending on polymer solubility).\n5. **Crosslinking Agent (if needed)**: N,N'-methylenebis(acrylamide) for structural integrity.\n6. **Catalyst**: Sodium metabisulfite, which facilitates decomposition of the persulfate initiator for rapid radical formation.\n\n---\n\n### **Step 3: Reaction Mechanism and Steps**\n\n#### **1. Pre-Treatment and Solution Preparation**\n1. **Preparation of Reaction Medium**:\n   - Dissolve the base monomer (e.g., acrylamide) in deionized water, keeping the concentration around 15-25 wt%. \n   - Add a small amount of crosslinker (if mechanical strength is desired), e.g., N,N'-methylenebis(acrylamide), at 0.1-0.5 wt%.\n\n2. **Preparation of Sulfonic Acid Surfactant Solution**:\n   - Dissolve the sulfonic acid surfactant (e.g., SDBS) in water. Maintain a surfactant concentration of ~1-5 wt%, optimizing based on the desired degree of sulfonation. \n   - Adjust the pH to ~6-7 if needed, ensuring all reactants stay in a suitable ionic state.\n\n3. **Initiator Solution**:\n   - Dissolve potassium persulfate (KPS) in deionized water (at ~0.5-1 wt%). Optionally, prepare sodium metabisulfite (0.5 wt%) in a separate container to accelerate initiation.\n\n---\n\n#### **2. Polymerization Reaction: Radical Copolymerization**\n1. **Reaction Setup**:\n   - Use a three-neck round-bottom flask with a reflux condenser, magnetic stirrer, thermometer, and nitrogen inlet (to maintain an inert nitrogen atmosphere).\n   - Add the prepared monomer solution and sulfonic acid group-containing surfactant solution to the flask.\n\n2. **Degassing**:\n   - Purge the flask with nitrogen gas for 20-30 minutes to remove dissolved oxygen, which can inhibit radical polymerization.\n\n3. **Initiation**:\n   - Heat the reaction mixture to 60-70°C under a nitrogen atmosphere.\n   - Slowly add the persulfate initiator solution dropwise into the reaction flask. If using sodium metabisulfite, add it simultaneously.\n   - Stir the mixture constantly to ensure uniform distribution of radicals.\n\n4. **Polymerization**:\n   - Maintain the reaction temperature at 65-70°C for 4-6 hours. Monitor the viscosity of the reaction mixture as polymerization progresses.\n\n---\n\n#### **3. Post-Polymerization and Purification**\n1. **Precipitation**:\n   - Once polymerization is complete, cool the reaction mixture to room temperature. Precipitate the polymer by adding the mixture dropwise into a large volume of a non-solvent (e.g., ethanol or acetone) with stirring.\n\n2. **Washing**:\n   - Wash the precipitated polymer thoroughly to remove unreacted monomers, surfactant residues, and salts. Use ethanol and deionized water alternately.\n\n3. **Drying**:\n   - Dry the purified polymer in a vacuum oven at 40-50°C until constant weight is achieved.\n\n---\n\n### **Step 4: Characterization**\n1. **FTIR Analysis**:\n   - Confirm the presence of sulfonic acid groups on the polymer backbone by identifying the characteristic -SO₃ stretching vibration peak (~1035–1080 cm⁻¹) in the FTIR spectrum.\n\n2. **Contact Angle Measurement**:\n   - Evaluate the hydrophilicity of the modified polymer surface using contact angle goniometry. A lower contact angle indicates enhanced hydrophilicity.\n\n3. **Thermogravimetric Analysis (TGA)**:\n   - Assess the thermal stability of the modified polymer.\n\n4. **Water Absorption Test**:\n   - Quantify the increase in water absorption (swelling ratio) after sulfonation as a measure of hydrophilicity.\n\n---\n\n### **Key Reaction Equation**\nIf acrylamide (CH₂=CHCONH₂) is used as the base monomer, the reaction involves free radical copolymerization with SDBS:\n\n\\[ \\text{CH}_{2}=\\text{CHCONH}_{2} + \\text{C}_{12}\\text{H}_{25}\\text{C}_{6}\\text{H}_{4}\\text{SO}_{3}^{-} \\longrightarrow \\text{[Polymer-SO}_{3}\\text{H]} \\]\n\n---\n\n### **Important Notes**\n1. **Temperature Control**: Ensure the temperature does not exceed 70°C to avoid decomposition of reactants.\n2. **Molar Ratios**:\n   - Monomer (vinyl monomer): 1 mmol.\n   - Sulfonic acid surfactant: 0.1-0.3 mmol.\n   - Initiator (KPS): 0.01-0.05 mmol.\n3. **Safety**: Work with sulfonic acid surfactants in a well-ventilated fume hood, as they can release fumes during dissolution.\n\nBy following this method step by step, you should successfully prepare a sulfonic acid-modified hydrophilic polymer and understand its chemistry thoroughly.\n\n---\n\nWould you like further clarification on any part of the process?"
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+{
+  "design_question": "Describe the role of allyl polyether in improving the hydrophilicity of a polymer. How would you ensure that its functional groups are effectively incorporated into the polymer structure?",
+  "design_answer": "Certainly, let’s carefully analyze, think logically, and address your question step by step. To begin with:\n\n---\n\n### **Step 1: Analyze the Question and Summarize the Key Points**\nYour question consists of two distinct but interrelated aspects:\n1. **Understanding the Role of Allyl Polyether.**\n   - How allyl polyether contributes to the improvement of hydrophilicity in the polymer structure.\n2. **Ensuring Functional Group Incorporation.**\n   - How to ensure that the functional groups of allyl polyether are effectively integrated during polymer synthesis.\n\nThese two parts form the foundation for designing a comprehensive and practical experimental scheme for synthesizing a hydrophilic polymer. Let us now discuss them systematically.\n\n---\n\n### **Step 2: Allyl Polyether and Its Role in Enhancing Hydrophilicity**\n1. **Chemical Nature of Allyl Polyethers:**\n   - Allyl polyethers are macromolecules containing **alkoxide chains** (e.g., ethylene oxide units -CH2CH2O-) with a terminal allyl group (-CH2=CH-CH2-).\n   - The alkoxide (-CH2CH2O-) chains are hydrophilic due to their polar nature, capable of forming hydrogen bonds with water molecules, thereby imparting significant hydrophilicity.\n\n2. **Incorporating Hydrophilicity into a Polymer:**\n   - When allyl polyether is incorporated into a polymer backbone or as a side chain, the hydrophilic alkoxide functionalities increase the polymer's ability to interact with water.\n   - This can improve properties such as water solubility, wettability, or biocompatibility, depending on the application.\n   - Ideal applications include hydrogels, coatings, or drug delivery systems where hydrophilicity is critical.\n\n---\n\n### **Step 3: Ensuring Functional Group Incorporation**\nThe allyl group (-CH2=CH-) attached to the polyether chain plays a key role in the polymerization process. It can participate in **radical polymerization** or **copolymerization**, ensuring that the polyether structure is effectively grafted onto or integrated into the polymer chain.\n\n---\n\n### **Step 4: Experimental Preparation Scheme for Incorporation of Allyl Polyether**\nThe specific approach to synthesizing a hydrophilic polymer with allyl polyether depends on the polymerization technique used. Below, I lay out a detailed example using **free-radical copolymerization**, which is a commonly adopted method.\n\n#### **Materials Required:**\n- **Monomer:** Allyl polyether (functional hydrophilic component).\n- **Co-monomer:** A hydrophobic/hydrophilic base monomer (e.g., acrylamide, methyl methacrylate, or styrene) to form the polymer backbone.\n- **Initiator:** Azobisisobutyronitrile (AIBN) for radical initiation.\n- **Solvent:** A suitable solvent such as ethanol, dimethylformamide (DMF), or water, depending on the solubility of the reactants.\n- **Crosslinking Agent (if needed):** Ethylene glycol dimethacrylate (EGDMA) to introduce structural stability.\n\n---\n\n#### **Step-by-Step Procedure:**\n1. **Preparation of Reaction Mixture:**\n   1. Accurately weigh out the allyl polyether and base monomer in the desired molar ratio (e.g., 10–30 mol% allyl polyether, depending on the desired hydrophilicity).\n   2. Add the reactants to a solvent (e.g., ethanol) to ensure proper solubility of both reactants.\n   3. Optionally, add a crosslinking agent if a three-dimensional network polymer is needed (e.g., for hydrogel formation).\n\n2. **Addition of Radical Initiator:**\n   - Dissolve 1–2 mol% of AIBN (based on total monomers) in the reaction mixture. AIBN decomposes under heat to generate free radicals which initiate polymerization.\n\n3. **Polymerization Reaction:**\n   1. Transfer the reaction mixture into a nitrogen-purged, sealed glass reactor to exclude oxygen, which can quench free radicals.\n   2. Heat the mixture to 60–70°C (the decomposition temperature of AIBN) and stir it continuously for 4–8 hours to allow polymerization. Monitor the viscosity increase, as this indicates polymer chain growth.\n\n4. **Post-Reaction Processing:**\n   - After polymerization, the reaction product is precipitated into a non-solvent (e.g., diethyl ether or cold water) to separate the polymer. The hydrophilic polymer is then washed and dried under vacuum at room temperature.\n\n---\n\n### **Step 5: Ensuring Effective Incorporation**\n1. **Reaction Conditions:**\n   - Carefully control molar ratios: The percentage of allyl polyether relative to the co-monomer must be optimized to balance hydrophilicity and mechanical properties.\n   - Maintain rigorously controlled temperatures to prevent side reactions.\n   - Use appropriate solvent systems to ensure both monomers are soluble.\n\n2. **Analysis of Grafting Efficiency:**\n   - **Fourier Transform Infrared Spectroscopy (FTIR):** To confirm the presence of characteristic allyl polyether peaks (e.g., -CH2CH2O- bands).\n   - **Nuclear Magnetic Resonance (NMR):** To quantify the composition and confirm integration of allyl polyether into the polymer backbone.\n   - **Thermal Gravimetric Analysis (TGA):** To measure thermal stability consistent with the grafted polymer.\n\n3. **Optimization Through Repetition:**\n   - Iterative experiments may be necessary to optimize the hydrophilicity of the resulting polymer by varying monomer ratios and crosslinking concentrations.\n\n---\n\n### **Conclusion:**\nIn summary, allyl polyethers contribute to the hydrophilicity of a polymer by introducing polar alkoxide chains capable of hydrogen bonding. Their allyl group enables radical or copolymerization processes for effective integration into a polymer structure. By employing free-radical polymerization with controlled reaction conditions, you can synthesize a hydrophilic polymer with well-incorporated allyl polyether functionalities. Analytical techniques are essential to confirm successful incorporation and adjust the synthesis parameters as needed. \n\nWith proper lab technique, you should be able to prepare hydrophilic polymers efficiently and tailor their properties to the desired application. Happy experimenting!"
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diff --git a/task2/task2-qa/╦о─¤╜║ Nature.json b/task2/task2-qa/╦о─¤╜║ Nature.json
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+{
+  "design_question": "When preparing hydrophilic polymers, explain how Tollens' reagent interacts with the polymer material during the experimental procedure. What characteristics of this reagent make it suitable for this synthesis?",
+  "design_answer": "To address your question about how Tollens' reagent interacts with the polymer material during the experimental procedure, and why this reagent is suitable for this synthesis, let us proceed step by step. We will carefully follow the outlined requirements to provide a systematic explanation conducive to both theoretical understanding and practical application in the laboratory.\n\n---\n\n### **Step 1: Analyze the Key Points of the Question**\n1. The question pertains specifically to the role of *Tollens' reagent* in the synthesis of hydrophilic polymers.\n2. We need to clarify:\n   - How Tollens' reagent chemically interacts with the polymer material.\n   - The functional groups that enable this interaction.\n   - The suitability of Tollens' reagent for such reactions, focusing on its properties and reactivity.\n3. The explanation should cover:\n   - Reaction mechanism details.\n   - Conditions under which Tollens' reagent is used.\n   - Sufficient experimental parameters (concentrations, temperature, pH, etc.) that influence the success of the reaction.\n\n---\n\n### **Step 2: Introduction and Context**\nTollens' reagent is an ammoniacal silver nitrate solution, represented as [Ag(NH₃)₂]⁺, and is best known for its ability to oxidize aldehydes into carboxylic acids while itself being reduced to metallic silver (Ag⁰). The reagent is mild and selective and is commonly used to introduce functional modifications to substrates containing reducible functional groups like aldehydes or other specific oxidizable groups.\n\nIn the context of hydrophilic polymer preparation, Tollens' reagent can be employed to:\n1. Modify a polymer that possesses aldehyde functional groups (e.g., polysaccharides like oxidized cellulose or partially oxidized polymers).\n2. Facilitate the introduction of **silver nanoparticles** (AgNPs) onto the polymer chain, which can further enhance hydrophilicity.\n\nThese interactions can lead to the formation of a functional polymer with enhanced hydrophilicity due to the introduction of carboxyl groups (from aldehyde oxidation) or improved surface functionality through the incorporation of silver, known for its hydrophilic nature.\n\n---\n\n### **Step 3: Systematic Explanation of the Experimental Procedure**\n\n#### **(1) Step 1: Preparation of Tollens' Reagent**\nTollens' reagent must be freshly prepared due to its instability. The procedure is as follows:\n1. Dissolve 1.0 g of silver nitrate (\\(AgNO₃\\)) in approximately 10 mL of distilled water in a clean glass container.\n2. Gradually add aqueous ammonia (\\(NH₃\\) solution, ~25% concentration) dropwise to this solution while stirring. Initially, a brown precipitate of silver oxide (\\(Ag₂O\\)) will form.\n3. Continue adding the ammonia solution until the brown precipitate dissolves completely, yielding a clear, colorless solution of [Ag(NH₃)₂]⁺.\n4. The freshly prepared Tollens' reagent is now ready for use.\n\nTo prevent side reactions or decomposition, prepare the reagent in small quantities.\n\n---\n\n#### **(2) Step 2: Interaction of Tollens' Reagent with the Polymer**\nTollens' reagent primarily interacts with aldehyde groups present in the polymer backbone. The detailed reaction mechanism and experimental protocol are described below:\n\n**a. Mechanism of Interaction:**\n- The aldehyde functional groups (\\(-CHO\\)) on the polymer oxidize to carboxylic acids (\\(-COOH\\)) when treated with Tollens' reagent. During this oxidation:\n  - The silver ion (\\(Ag^+\\)) in Tollens' reagent is reduced to metallic silver (\\(Ag^0\\)), which can deposit on the polymer surface.\n\n  The chemical reaction can be represented as:\n  \\[\n  RCHO + 2[Ag(NH₃)₂]^+ + 3OH^- \\rightarrow RCOO^- + 2Ag^0 \\ (↓) + 4NH₃ + 2H_2O\n  \\]\n\n  - The newly introduced carboxylic groups (\\(-COOH\\)) significantly improve the hydrophilicity of the polymer by increasing its ability to interact with water through hydrogen bonding.\n\n**b. Experimental Conditions:**\n  Key reaction parameters to ensure the success of this step:\n  1. **pH Control**: The reaction is typically carried out under slightly basic conditions (pH ~8-9), which can be maintained using dilute sodium hydroxide (\\(NaOH\\)).\n  2. **Temperature**: Perform the reaction at room temperature (~25°C) to avoid decomposition of the Tollens' reagent or excessive side reactions.\n  3. **Reaction Time**: Allow the reaction to proceed for 1–2 hours with stirring to ensure complete interaction between the polymer and the reagent.\n\n---\n\n#### **(3) Step 3: Post-Reaction Treatment**\nOnce the reaction is complete:\n1. **Purification**:\n   - Wash the modified polymer thoroughly with distilled water to remove any residual silver ammonia complex or unreacted reagents.\n   - If metallic silver (\\(Ag^0\\)) has deposited on the polymer, it can either be left as-is, or excessive surface silver can be removed by gentle polishing or washing with dilute acid.\n\n2. **Characterization**:\n   - Use Fourier-transform infrared (FTIR) spectroscopy to confirm the successful oxidation of aldehyde groups to carboxylic acids. Look for characteristic peaks near 1720–1750 cm⁻¹ for \\(-COOH\\).\n   - Scanning electron microscopy (SEM) or energy-dispersive X-ray spectroscopy (EDX) can be used to confirm the presence of metallic silver on the polymer surface.\n\n---\n\n### **Step 4: Suitability of Tollens' Reagent for Hydrophilic Polymer Preparation**\nThe suitability of Tollens' reagent for this process arises from its unique chemical properties:\n1. **Selective Oxidant**: Tollens' reagent selectively oxidizes aldehyde groups without affecting other functional groups like hydroxyls, ensuring targeted modification of the polymer.\n2. **Mild Reaction Conditions**: The reagent operates effectively under mild, aqueous, and slightly basic conditions, which are compatible with sensitive polymeric materials.\n3. **Dual Functionality**: In addition to oxidation, the reagent enables the deposition of silver nanoparticles, which can further improve surface properties, including hydrophilicity and antimicrobial functionalities.\n4. **Hydrophilicity Enhancement**: The incorporation of carboxyl groups and/or silver results in greater water compatibility, rendering the polymer highly hydrophilic.\n\n---\n\n### **Step 5: Practical Tips for Laboratory Success**\n1. Always use freshly prepared Tollens' reagent to prevent decomposition or reduced efficiency.\n2. Avoid working with large quantities of Tollens' reagent, as it can form explosive silver fulminate residues upon drying.\n3. Perform a small-scale trial reaction to optimize the reagent-to-polymer ratio and minimize waste.\n\n---\n\nBy following this methodical approach, you can successfully modify your polymer to enhance its hydrophilicity using Tollens' reagent. Please ensure meticulous handling of the reagents and adherence to safety protocols when carrying out the experiment in the lab."
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diff --git a/task2/task2-qa/╦о─¤╜║═┐┴╧ AM.json b/task2/task2-qa/╦о─¤╜║═┐┴╧ AM.json
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+{
+  "design_question": "Describe how you would utilize 3-(trimethoxysilyl)propyl methacrylate (TMSPMA) to create a polymer solution suitable for application onto a substrate, while maintaining its ability to crosslink during curing.",
+  "design_answer": "To address your question and to construct a well-prepared experimental preparation scheme for using 3-(trimethoxysilyl)propyl methacrylate (TMSPMA) to create a polymer solution suitable for application onto a substrate, while maintaining its ability to crosslink during curing, let us systematically break it down step by step. TMSPMA is an organosilane monomer with both methacrylate functionality (capable of free radical polymerization) and silane groups (capable of hydrolysis and subsequent condensation reactions). By leveraging these functionalities, we can prepare a hydrophilic, crosslinkable polymer solution.\n\n---\n\n### Key Points to Address:\n1. **Use of TMSPMA**: It contains a methacrylate group for free-radical polymerization and hydrolyzable trimethoxysilane groups that allow crosslinking.\n2. **Preparation of Solution**: The solution should be prepared to optimize its hydrophilic properties for application onto a substrate.\n3. **Crosslinking Capability**: Ensure the silane groups retain their reactivity for hydrolysis and condensation, which will enable crosslinking post-application and curing.\n\n---\n\n### Experimental Preparation Scheme:\n\n#### **Step 1: Selection of Solvent (Preparation of the Polymer Solution)**\nA suitable solvent must be selected to dissolve TMSPMA and maintain reaction stability. Commonly used solvents are ethanol, methanol, or a mixture of ethanol/water. Ethanol is a preferred choice since it improves solubility of TMSPMA and is compatible with hydrolysis of the silane groups.\n\n- **Reagents**:\n  - TMSPMA: 10 g (example weight, can be adjusted depending on intended polymer concentration).\n  - Ethanol: Enough to prepare a 10-20% (w/v) solution of TMSPMA in ethanol.\n  - DI Water: 3-5% by volume relative to the ethanol to enable controlled hydrolysis of the silane groups.\n\n- **Procedure**:\n  1. Add ethanol to a clean reaction vessel.\n  2. Gradually add TMSPMA to ethanol with gentle stirring to dissolve completely.\n  3. Add DI water dropwise to initiate partial hydrolysis of the trimethoxysilane groups.\n\n---\n\n#### **Step 2: Catalyst Addition for Controlled Hydrolysis**\nSince the trimethoxysilane groups of TMSPMA undergo hydrolysis (producing silanol groups) before condensation, a small amount of acid catalyst is necessary to promote this step.\n\n- **Reagents**:\n  - Glacial acetic acid (or dilute HCl): ~0.1-0.5 wt% relative to TMSPMA.\n\n- **Procedure**:\n  1. Add glacial acetic acid dropwise to the prepared TMSPMA-ethanol-water solution under mild stirring.\n  2. Continue stirring the mixture at room temperature for 30–60 minutes. The resulting solution contains hydrolyzed silanol groups, ensuring the TMSPMA remains in a crosslinkable state.\n\n**Notes**: Avoid prolonged hydrolysis or high water content, which might prematurely polymerize or gel the system.\n\n---\n\n#### **Step 3: Polymerization (Optional Step, if Pre-polymer Desired)**\nIf a partially polymerized (oligomeric) structure is desired before applying to the substrate, radical polymerization can be initiated.\n\n- **Reagents**:\n  - TMSPMA solution (prepared in Step 2).\n  - Azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO): ~0.5–1.0 wt% relative to TMSPMA.\n  - Appropriate solvent (ethanol works well).\n\n- **Procedure**:\n  1. Transfer the TMSPMA solution to a sealed glass reactor.\n  2. Add the initiator (AIBN or BPO) to the solution and stir gently.\n  3. Heat the solution to 60–70°C under an inert nitrogen atmosphere to initiate polymerization.\n  4. Monitor viscosity to stop the reaction at a desired oligomerization stage (to avoid fully polymerized gel formation).\n\n---\n\n#### **Step 4: Application onto a Substrate**\nAfter preparing the polymer solution or oligomer, it is applied onto the desired substrate.\n\n- **Procedure**: \n  1. Clean the substrate thoroughly using solvents (e.g., ethanol) to remove contaminants.\n  2. Coat the substrate with the TMSPMA solution using spin coating, dip coating, or spray coating, depending on the application.\n  3. Allow the solvent to evaporate at room temperature, forming a thin film.\n\n---\n\n#### **Step 5: Curing (Crosslinking Step)**\nThe final curing step ensures crosslinking between hydrolyzed silanol groups, forming a robust siloxane network.\n\n- **Conditions**:\n  - Humidity: Maintain a relative humidity of 50–70% during curing to promote condensation.\n  - Temperature: Cure at ~100–120°C for 2–3 hours to facilitate complete siloxane bonding.\n\n---\n\n#### **Step 6: Characterization and Hydrophilicity Testing**\nOnce cured, the hydrophilicity of the film can be determined using contact angle measurements (lower contact angles indicate higher hydrophilicity). Additional characterization using FTIR can confirm crosslinking (siloxane bonds).\n\n---\n\n### Important Notes:\n1. The level of hydrolysis must be controlled to avoid premature gelling of the solution.\n2. Proper storage of the polymer solution (if not used immediately) is critical, ideally under an inert atmosphere to prevent unwanted reactions.\n3. Adjust solvent ratios or reaction conditions as per specific requirements for hydrophilicity and substrate compatibility.\n\nBy following these steps, you will have a TMSPMA-derived polymer solution that is hydrophilic, suitable for substrate application, and capable of crosslinking during curing."
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+{
+  "design_question": "Explain how you would employ a molecule capable of undergoing a Michael addition reaction to chemically crosslink a polymer system. Describe the role of the molecule in forming a hydrophilic network and justify why this method enhances hydrophilicity.",
+  "design_answer": "To answer your question thoroughly, let us proceed step by step, analyzing the problem and delving into an experimental preparation scheme grounded in rigorous materials science principles.\n\n---\n\n### **Step 1: Analyze the Question and Summarize Key Points**\nThe core of this question revolves around:\n1. Utilizing a molecule capable of participating in a **Michael addition reaction** for chemically crosslinking a polymer system.\n2. Designing a network that forms a hydrophilic polymer.\n3. Justifying how this method enhances hydrophilicity.\n\nThe **Michael addition reaction**, a well-known nucleophilic conjugate addition, typically involves the addition of a nucleophile (often an amine, thiol, or active methylene compound) to an α,β-unsaturated carbonyl compound or derivative, such as an acrylate or acrylamide group.\n\nKey roles of such reactions in a hydrophilic polymer system:\n- The molecule involved in the Michael addition serves as a **crosslinking agent**, which chemically links polymer chains to form a network.\n- Such crosslinking results in the formation of hydrophilic 3D networks, where functional groups, hydrogen bonding sites, and hydrophilic moieties (such as amides, hydroxyls, or carboxyls) are retained, contributing to water absorption or swelling.\n\n---\n\n### **Step 2: Design the Reaction Scheme & Experimental Process**\n\nWe will design **a two-step experimental process** to synthesize a hydrophilic polymer using the Michael addition reaction with a suitable crosslinking agent. For this example, we will create a **hydrogel system** by crosslinking a poly(ethylene glycol) (PEG)-based prepolymer functionalized with acrylate groups. The crosslinking agent introduced will be **triethanolamine**, which brings hydrophilic properties due to its hydroxyl groups and acts as a nucleophile.\n\n#### 2.1 **Step 1: Selection of Starting Materials**\n- **Prepolymer**: Poly(ethylene glycol) diacrylate (PEGDA)  \n  (Provides the α,β-unsaturated carbonyl for Michael addition).\n  - Functional groups: Acrylate (–C=C–CO–).\n  - Molecular weight: 700-10,000 g/mol (choice depends on the desired mechanical properties).\n  - Role: Forms the backbone of the crosslinked hydrophilic polymer.\n  \n- **Crosslinker/Reactant**: Triethanolamine  \n  (Tri-functional nucleophile that can react with acrylate groups to form a crosslinked network).\n  - Functional groups: Hydroxyl (–OH) and amine (–NH).\n  - Role: Chemical crosslinker and hydrophilic promoter due to polar hydroxyl groups, enhancing water affinity.\n\n- **Solvent**: Deionized water (to maintain high polarity and support hydrophilicity).\n\n- **Initiator (if polymerization is needed)**: For UV-induced polymerization, use **Irgacure 2959** (2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone), while for thermal polymerization, use **hydroquinone**.\n\n#### 2.2 **Step 2: Experimental Procedure**\n\n**Step 2.2.1: Preparation of Reaction Mixture**  \n1. Dissolve the PEGDA prepolymer in deionized water (concentration: ~10%-20% by weight, depending on the desired network density). Stir until fully dissolved.\n2. Add triethanolamine to the PEGDA solution in a molar ratio of **1:2** (amine/acrylate), ensuring that the amount of amine is in slight excess to maximize the reaction with all acrylate groups.  \n   - Example: For a PEGDA prepolymer with a molecular weight of 700 g/mol:\n     - Use 2 mmol of PEGDA and 4 mmol of triethanolamine.\n\n---\n\n**Step 2.2.2: Michael Addition Crosslinking Reaction**  \n1. Adjust the pH of the reaction medium to **pH ~8-9** using a mild base like NaOH. This ensures that the amine groups in triethanolamine are in their nucleophilic form.  \n2. Heat the solution mildly to ~40–50°C to enhance the reaction kinetics while avoiding polymer degradation.  \n3. Stir the mixture under inert conditions (e.g., nitrogen atmosphere) to prevent unwanted oxygen inhibition of any subsequent acrylate polymerization.\n4. Allow the reaction to proceed for 2–4 hours. During this time:\n   - Triethanolamine nucleophiles attack the β-carbons of the acrylate groups in a Michael addition reaction.\n   - This results in covalent bonds forming between the PEG backbone and crosslinker, generating a 3D hydrogel network.\n\n---\n\n**Step 2.2.3: Optional UV/Free-Radical Polymerization for Fully Curing**  \n1. If necessary, add 0.1%-0.5% (w/w) of a free-radical photoinitiator such as Irgacure 2959.  \n2. Expose the mixture to 365 nm UV light for ~5–10 minutes to polymerize any unreacted acrylate groups further, ensuring a highly crosslinked and stable network structure.\n\n---\n\n**Step 2.2.4: Post-Processing**  \n1. Neutralize the reaction mixture and wash the resulting hydrogel thoroughly with deionized water to remove any unreacted triethanolamine or PEGDA.  \n2. Store the hydrogel in a hydrated state at ambient temperature.\n\n---\n\n### **Step 3: Justification of the Strategy**\n\nThe Michael addition-mediated crosslinking serves as an ideal method to enhance hydrophilicity for multiple reasons:\n1. **Incorporation of Hydrophilic Groups**: Triethanolamine introduces hydroxyl (–OH) groups throughout the network, which can form hydrogen bonds with water, significantly boosting hydrophilicity.\n2. **Controlled Crosslinking**: Michael addition provides precise control over the degree of crosslinking, allowing tuning of water uptake, swelling ratio, and mechanical properties.\n3. **Superior Network Formation**: The 3D network traps water due to capillary forces, hydrogen bonding, and hydroxyl/amino groups, making the material ideal for hydrogel or biomedical applications.\n\nBy using an excess of triethanolamine, any remaining —OH groups also contribute to hydrophilicity without compromising network integrity.\n\n---\n\n### **Conclusion**\n\nTo chemically crosslink a polymer system via Michael addition, the selected molecule (triethanolamine, in this case) acts as a nucleophile reacting with acrylate groups on PEG-based prepolymers to form a hydrophilic, crosslinked hydrogel network. This precise process introduces hydrophilic functional groups and provides robust network properties, enhancing the material's ability to absorb and retain water."
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+{
+  "design_question": "Describe how d-glucose 6-phosphate monobarium salt (GPS-Ba) can be utilized as a template in the synthesis of a hydrophilic polymer. What is the significance of its interaction with the polymer precursor during the preparation process?",
+  "design_answer": "Great question! Let's break down the problem methodically and tackle it step by step.\n\n---\n\n### **Step 1: Analyzing the question**\n**Key points:**\n- The molecule in question is **D-glucose 6-phosphate monobarium salt (GPS-Ba)**.\n- It needs to be used as a **template** in the synthesis of a **hydrophilic polymer**.\n- You are asking for details about both the synthesis process (experimental preparation scheme) and the significance of its interaction with the polymer precursor during the preparation.\n\n**Hydrophilic polymers** are materials that attract water due to their high affinity for polar molecules such as water. In this case, GPS-Ba offers unique advantages because:\n1. **Hydrophilicity of D-glucose 6-phosphate**: The molecule has highly hydrophilic functional groups (-OH, -COOH, and -PO4), which can significantly enhance the hydrophilicity of the polymer matrix.\n2. **Template role**: Because GPS-Ba has coordination sites through its phosphate group, it can interact with precursors (monomers or crosslinking agents) to create a structured or functionalized polymer with controlled architecture.\n3. **Significance of Ba2+ ion**: The presence of barium adds ionic strength and may influence the polymerization environment (e.g., by stabilizing certain intermediates or by controlling precursor interactions).\n\n---\n\n### **Step 2: Detailed experimental preparation scheme**\nI'll describe a systematic experiment in which GPS-Ba acts as a template. Additionally, I'll delve into each step of the polymer synthesis, discussing reaction conditions, reagents, and their molar ratios.\n\n---\n\n#### **Materials and reagents**\n1. **D-glucose 6-phosphate monobarium salt (GPS-Ba)**\n2. **Monomer** (e.g., acrylamide, acrylic acid, or hydroxyethyl methacrylate)\n3. **Crosslinking agent** (e.g., N,N’-methylenebisacrylamide or ethylene glycol dimethacrylate)\n4. **Initiator** for free-radical polymerization (e.g., ammonium persulfate (APS) or azobisisobutyronitrile (AIBN))\n5. **Solvent**: Water or a water-miscible organic solvent (e.g., ethanol)\n6. **Additional catalyst or stabilizer** (if necessary)\n7. **Neutralizing agent** (e.g., NaOH or HCl solution to adjust pH)\n\n---\n\n#### **Synthetic strategy**\nPreparation of hydrophilic polymer with GPS-Ba involvement proceeds in these systematic stages:\n\n---\n\n#### **Step 2.1: Preparation of the reaction system**\n1. Dissolve **GPS-Ba** in deionized water to create a homogeneous solution. The phosphate groups of GPS-Ba will ionize, providing a hydrophilic environment and ionic strength to enhance precursor interactions.\n   - Concentration: Aim for 0.1–0.2 M GPS-Ba solution.\n   - pH: Adjust pH to 7–8 using a dilute NaOH/HCl solution since phosphate groups perform optimally in near-neutral conditions.\n2. To this solution, add the chosen **monomer** (e.g., acrylamide) at a molar ratio suited for polymerization:\n   - Suggested monomer-to-template ratio: 10:1 to ensure sufficient interaction while maintaining a polymerizable volume.\n3. Add the **crosslinking agent** at a small fraction (typically 1–5 mol% of the monomer) to control the polymer's physical structure while retaining hydrophilicity.\n\n---\n\n#### **Step 2.2: Free radical polymerization with GPS-Ba as the template**\n1. Introduce the **initiator** (e.g., APS or AIBN) to the reaction system to generate radicals for polymerization:\n   - Initiator concentration: 0.5–2 wt% relative to the monomer. Ensure complete dissolution for an optimal reaction.\n   - Temperature: 50–70°C for thermal initiators like AIBN or APS. Maintain gentle stirring to ensure uniform heat distribution and thorough mixing.\n2. Allow polymerization to proceed for 4–12 hours. During this time, GPS-Ba templates the polymer by facilitating localized monomer interactions via its phosphate groups.\n\n**Mechanism of interaction:**\n- The phosphate groups in GPS-Ba act as functional sites, interacting with the amide or carboxylic acid groups in the monomer through hydrogen bonding and ionic coordination.\n- The barium ions (Ba2+) stabilize polar intermediates and potentially catalyze some chain-transfer reactions. This improves the polymerization rate and yields a hydrophilic polymer with tailored architecture.\n\n---\n\n#### **Step 2.3: Finalization and purification**\n1. After polymerization, quench the reaction by adding ice-cold deionized water or ethanol.\n2. Purify the synthesized polymer by dialysis to remove unreacted GPS-Ba. Alternatively, extraction via ultrafiltration may be used.\n3. Dry the polymer under a vacuum at ~40°C to avoid thermal degradation.\n\n---\n\n#### **Step 2.4: Characterization**\nTo confirm the presence of hydrophilic functional groups and polymer structure:\n1. Perform **Fourier-transform infrared spectroscopy (FTIR)** to verify interaction between GPS-Ba phosphate groups and polymer backbone.\n2. Conduct **contact angle measurements** to evaluate hydrophilicity.\n3. Use **gel permeation chromatography (GPC)** to analyze molecular weight distribution.\n\n---\n\n### **Step 3: Significance of GPS-Ba in the process**\nThe role of GPS-Ba is pivotal and multidimensional:\n1. **Template structuring**: GPS-Ba organizes monomers via its hydrophilic and ionic phosphate groups, leading to localized polymer growth and enhanced functional group dispersion.\n2. **Hydrophilicity enhancement**: Incorporating GPS-Ba ensures integration of polar regions (phosphate and hydroxyl groups) into the polymer matrix, increasing water affinity.\n3. **Controlled polymerization**: Ba2+ ions stabilize polar intermediates, minimizing undesirable side reactions and ensuring predictable polymer architecture.\n4. **Functionalization**: GPS-Ba leaves behind structural imprints on the polymer, enhancing specific functionalities (e.g., ion-exchange capacity or reactivity), depending on the intended application.\n\n---\n\n### **Step 4: Practical tips for success**\n1. Ensure thorough dissolution of GPS-Ba before adding any monomer.\n2. Maintain precise temperature control during polymerization to avoid runaway reactions.\n3. Use appropriate purification techniques to remove excess GPS-Ba, as residual salt may influence the physical properties of the polymer.\n\n---\n\n### **Conclusion**\nUsing **D-glucose 6-phosphate monobarium salt (GPS-Ba)** as a template provides both structural and functional advantages in synthesizing hydrophilic polymers. Its hydrophilic nature enhances water affinity, while its ionic phosphate groups facilitate organized polymerization. This method is scientifically robust and practically feasible for designing hydrophilic polymers tailored to various applications, such as biomedical materials, water purification membranes, or functional coatings.\n\nLet me know if you have further questions—I'd be happy to elaborate!"
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+{
+  "design_question": "How would you utilize acrylamide (AAm) in a polymer synthesis experiment to prepare a hydrophilic polymer? Describe the steps you would take to ensure the monomer is in a purified state before use.",
+  "design_answer": "To prepare a hydrophilic polymer using acrylamide (AAm) and ensure its suitability through purification, let us approach the problem systematically. Here's the step-by-step procedure:\n\n---\n\n### **Step 1: Analyze the Problem and Summarize Key Points**\nThis question can be separated into two main components:\n1. **Synthesis of a hydrophilic polymer using acrylamide (AAm):** Acrylamide is a popular monomer used to prepare polyacrylamide, which is highly hydrophilic due to the amide (-CONH2) groups in its structure. The polymer synthesis could be achieved by free-radical polymerization, and specific reaction conditions must be controlled to optimize the polymer's properties.\n2. **Purification of acrylamide prior to polymerization:** Since monomer purity is crucial for ensuring reproducibility and avoiding side reactions, acrylamide must be purified before polymerization to remove any inhibitors, impurities, or storage byproducts.\n\nNow, I'll provide a detailed experimental scheme covering both aspects.\n\n---\n\n### **Step 2: Polymer Synthesis Using Acrylamide (AAm)**\n\nThe synthesis of a hydrophilic polymer with acrylamide involves free-radical polymerization, which can be performed as **solution polymerization** (typically in water) for hydrophilic systems. Below are the detailed steps:\n\n#### **A. Materials Required**\n1. **Acrylamide (AAm):** Monomer (to be purified; see purification steps below).\n2. **Initiator:** Ammonium persulfate (APS) as the thermal initiator.\n3. **Cross-linker (optional):** N,N'-Methylenebisacrylamide (MBAA), if cross-linked polyacrylamide is desired.\n4. **Catalyst (optional):** N,N,N',N'-Tetramethylethylenediamine (TEMED) to accelerate the reaction.\n5. **Solvent:** Deionized water (ensures hydrophilicity).\n6. **Inert atmosphere tools:** Nitrogen gas (to remove oxygen).\n\n#### **B. Polymerization Procedure**\n1. **Preparation of Reaction Mixture:**\n   - **Monomer Solution:** Dissolve purified acrylamide in deionized water at a concentration of 10–30 wt%, depending on the desired polymer properties (higher concentrations increase viscosity and molecular weight).\n   - (Optional) **Cross-linker addition:** Add a small amount (0.1–1 mol% relative to AAm) of MBAA if creating a cross-linked structure is desired. For linear polyacrylamide, omit this step.\n   - Add sodium hydroxide (NaOH) to adjust the pH to around 7–8, as this can enhance polymerization.\n\n2. **Deoxygenate the Reaction System:**\n   - Bubble nitrogen gas into the solution for 15–30 minutes to remove dissolved oxygen, which would otherwise inhibit free-radical polymerization.\n\n3. **Initiate the Free-Radical Polymerization:**\n   - Dissolve ammonium persulfate (APS) in a small quantity of water and add it to the reaction mixture to initiate polymerization. APS is typically used at 0.2–1 mol% relative to the acrylamide concentration.\n   - (Optional but recommended) Add TEMED (0.05–0.1 mol%) to catalyze the decomposition of APS, ensuring a faster reaction and consistent molecular weight.\n\n4. **Maintain Controlled Reaction Conditions:**\n   - Carry out the reaction at 50–70 °C with gentle stirring to uniformly mix the solution.\n   - Allow polymerization to occur for 4–6 hours, depending on the desired degree of polymerization.\n\n5. **Termination and Purification:**\n   - After polymerization is complete, cool the mixture to room temperature.\n   - Dialyze the polymer solution against deionized water (using dialysis tubing with an appropriate molecular weight cutoff) for 24–48 hours to remove unreacted monomers, initiators, and byproducts.\n\n6. **Drying of Hydrogel (if necessary):**\n   - For hydrophilic polymer films or powders, precipitate the polymer in ethanol, dry it under vacuum at 40–50 °C, and store it in a desiccator.\n\n---\n\n### **Step 3: Purification of Acrylamide (AAm)**\n\nPurification of acrylamide is critical because commercial acrylamide often contains impurities such as storage inhibitors, byproducts of synthesis, or degradation products. Here's the purification process:\n\n#### **A. Materials Required**\n1. Crude acrylamide.\n2. Solvent: Deionized water and acetone.\n3. Activated carbon (to remove colored impurities).\n4. Refrigeration equipment (to allow recrystallization).\n5. Vacuum filtration apparatus.\n\n#### **B. Purification Procedure**\n1. **Dissolve Acrylamide:**\n   - Dissolve the acrylamide in deionized water at room temperature. Use a minimum quantity of water to create a saturated solution.\n\n2. **Remove Colored Impurities:**\n   - Add a small amount of activated carbon (0.1–0.5 wt% of AAm) to the solution.\n   - Heat the solution gently (to 40–50 °C) with stirring for 15–30 minutes.\n   - Filter the solution through a Buchner funnel or vacuum filtration apparatus to remove the activated carbon along with adsorbed impurities.\n\n3. **Recrystallize Acrylamide:**\n   - Cool the filtered solution slowly in a refrigerator (4–8 °C) to initiate crystallization of acrylamide.\n   - Once crystals have formed, collect them by vacuum filtration.\n\n4. **Wash Crystals:**\n   - Wash the crystals with cold acetone to remove any residual impurities.\n\n5. **Dry and Store:**\n   - Dry the purified acrylamide under vacuum at room temperature or in a desiccator for 24 hours.\n   - Store the acrylamide in an airtight container to prevent moisture absorption.\n\n---\n\n### **Step 4: Quality Control and Characterization**\n1. **Purified AAm Quality Check:**\n   - Use melting point analysis to confirm the purity of acrylamide.\n   - High-performance liquid chromatography (HPLC) can be used for further confirmation of AAm purity.\n\n2. **Hydrophilic Polymer Characterization:**\n   - Measure water absorption capacity to confirm hydrophilicity (e.g., equilibrium swelling tests).\n   - Confirm polymer composition and structure using spectroscopy (e.g., FTIR to verify the presence of amide groups and NMR for molecular details).\n   - Assess molecular weight and distribution using gel permeation chromatography (GPC).\n\n---\n\nThis step-by-step experimental scheme ensures the creation of a hydrophilic polymer with high purity and reproducibility, utilizing acrylamide effectively. Always ensure to follow laboratory safety protocols when handling acrylamide, as it is toxic in its monomeric form. I encourage you to discuss any uncertainties with a supervisor before beginning the experiment."
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+{
+  "design_question": "Describe the steps you would take to incorporate a functional group from the provided molecule into the polymer structure to enhance its hydrophilicity. Be specific in identifying reaction conditions and mechanisms.",
+  "design_answer": "Certainly, let us take a systematic and detailed approach to analyze and derive an experimental preparation scheme for synthesizing a hydrophilic polymer by incorporating the functional group from the provided molecule.\n\n---\n\n### Step 1: Analyze the Provided Molecule and Polymer Properties\nThe first step is to carefully analyze the structure of the **provided molecule** and **existing polymer**. Key points to consider:\n- **Functional Group Identification**: Identify hydrophilic functional groups (e.g., hydroxyl (-OH), carboxylic acid (-COOH), amine (-NH2), or sulfonic acid (-SO3H)) present in the provided molecule, which may enhance water compatibility of the polymer.\n- **Reactivity**: Assess whether the functional group can react with sites on the polymer or whether suitable modification is required (e.g., activation, coupling agent).\n- **Polymer Chemistry**: Understand the chemistry of the polymer, whether it is addition polymerizable (e.g., vinyl-based) or condensation polymerizable (e.g., ester, amide-based).\n\nKey question: Does the provided molecule contain a functional group that can be covalently bonded to the polymer, and what reaction pathway will best incorporate it?\n\n---\n\n### Step 2: Select Reaction Pathway for Functionalization\nTo systematically enhance the hydrophilicity:\n- If the provided molecule contains **reactive functional groups** such as hydroxyl (-OH), carboxylic acid (-COOH), or an amine group (-NH2), they can act as nucleophiles to react with electrophilic groups already present in the polymer chain, cross-linker, or monomer precursor.\n- Alternatively, grafting of the hydrophilic molecule onto the polymer chain might involve a coupling reaction or free-radical grafting using appropriate initiators.\n\nTo proceed, we need to select the most effective strategy from the following:\n1. **Pre-polymerization Functionalization:** Modify the monomers before polymerization to include hydrophilic functional groups.\n2. **Post-polymerization Grafting:** Modify the polymer after synthesis by introducing hydrophilic side chains.\n3. **Co-polymerization Approach:** Introduce the provided hydrophilic molecule as a co-monomer during the polymerization stage.\n\nOnce the strategy is clear, choose solvents, conditions (e.g., temperature, pH), and a mechanism suitable for the polymer modification.\n\n---\n\n### Step 3: Develop a Detailed Experimental Scheme\nAssume the provided molecule contains a **-COOH functional group** and is to be incorporated into the polymer's structure. Let us adopt a **grafting approach**. Here is a stepwise outline:\n\n#### Step 3.1: Activate the Provided Hydrophilic Molecule\n- Convert the **carboxylic acid (-COOH)** group into a more reactive derivative, such as an **acid chloride (-COCl)**, to enhance reactivity toward the polymer. This is typically achieved using a chlorinating agent like **thionyl chloride (SOCl2)**.\n  **Reaction**: R-COOH + SOCl2 → R-COCl\n  **Conditions**: \n    - Solvent: Dry dichloromethane (DCM) or chloroform to avoid unwanted hydrolysis.\n    - Temperature: 40–50°C for 1–2 hours under reflux.\n    - Note: Perform under a fume hood, as HCl gas evolves.\n\n#### Step 3.2: Select and Prepare the Polymer Substrate for Reaction\n- Choose a starting polymer that has functional groups capable of reacting with the acid chloride derivative. For example:\n  - Hydroxyl-functionalized polymers (e.g., poly(vinyl alcohol), PVA).\n  - Amine-functionalized polymers (e.g., chitosan).\n\n#### Step 3.3: Graft the Hydrophilic Molecule Onto the Polymer Backbone\n- React the polymer with the acid chloride derivative.\n  **Reaction**: R'-OH (polymer) + R-COCl → R'-OCO-R (ester linkage on polymer).\n  **Conditions**:\n    - Solvent: Use an aprotic solvent like tetrahydrofuran (THF).\n    - Catalyst: Use a mild base (e.g., pyridine or triethylamine) to neutralize the HCl formed during the reaction.\n    - Temperature: Room temperature to 40°C.\n    - Reaction Time: Typically 12–24 hours to ensure adequate grafting.\n\n---\n\n### Step 4: Purification of the Modified Polymer\n- After reaction completion, precipitate the hydrophilic polymer in a suitable non-solvent (e.g., methanol or cold water) to remove unreacted reagents and byproducts.\n- Redissolve the polymer in a good solvent and precipitate again if further purification is needed.\n\n---\n\n### Step 5: Characterization of the Hydrophilic Polymer\nTo confirm successful functionalization:\n1. **Fourier-Transform Infrared Spectroscopy (FTIR)**: Identify characteristic peaks corresponding to newly formed functional groups, such as ester carbonyl (C=O) at ~1730 cm⁻¹.\n2. **1H-NMR/13C-NMR Spectroscopy**: Verify the presence of the grafted hydrophilic groups in the polymer matrix.\n3. **Contact Angle Measurement**: Assess hydrophilicity by measuring the water contact angle — a decrease indicates enhanced hydrophilicity.\n4. **Thermal Stability (TGA/DSC)**: Evaluate whether the modification affects thermal properties.\n\n---\n\n### Additional Notes and Adjustments\nDepending on the molecule you have provided, steps and functionalization methods can be adjusted:\n- If the provided molecule has a primary amino group (-NH2), use an electrophile such as epoxide-modified polymer for coupling.\n- Solvents, pH, and reaction conditions must always be compatible with the polymer and reagent stability.\n\n---\n\nBy following this comprehensive experimental scheme, you should be able to successfully incorporate the hydrophilic functional group into the polymer backbone, significantly improving its hydrophilicity. Let me know if you'd like to further refine the specifics! 😊"
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+{
+  "design_question": "Describe the procedure for incorporating [Fe(CN)6]^{3-/4-} into the polymer matrix and discuss how this step ensures consistent interaction between the molecule and polymer network to improve hydrophilicity.",
+  "design_answer": "Certainly! Let us systematically approach your question about incorporating \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) into a polymer matrix while ensuring consistent interaction between the molecule and the polymer network to improve hydrophilicity. The molecule \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) has unique properties due to its charged nature and ability to form complex interactions, making it a viable candidate for enhancing hydrophilicity through electrostatic and chemical interactions with a polymeric network.\n\n### Step 1: Analysis of the Question\nKey points of your question:\n1. The goal is to incorporate \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) into a polymer matrix.\n2. The polymer should maintain consistent interactions with \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) to improve hydrophilicity.\n3. The procedure must include a step-by-step detailed experimental protocol backed with reaction conditions, reagent ratios, and practical considerations.\n\nBy analyzing this, it is evident that we need to:\n- Choose a polymer with functional groups that enable interaction with \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\).\n- Ensure uniform dispersion of the molecule throughout the polymer matrix.\n- Optimize conditions to retain hydrophilic properties and molecular stability.\n\n### Step 2: Step-by-Step Experimental Procedure\n\n#### 2.1. Selection of Polymer Substrate\n- Choose a hydrophilic polymer that has functional groups capable of interacting with \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\). Suitable candidates include:\n  - Poly(vinyl alcohol) (PVA) — due to its hydroxyl (-OH) groups.\n  - Polyacrylamide (PAM) — due to its amide (-CONH2) groups.\n  - Poly(N-vinylpyrrolidone) (PVP) — due to its lactam (-C=O and -N-) functional groups.\n\nFor this example, I will use **PVA**, given its versatility, hydrophilicity, and ease of post-functionalization.\n\n---\n\n#### 2.2. Preparation of the Polymer Solution\n1. **Dissolution of PVA**:\n   - Take **10 g of PVA (Mw 85,000–124,000, fully hydrolyzed)** and dissolve it in **100 mL of deionized water** by heating to **80 °C** with continuous stirring until a clear, viscous solution forms.\n   - This ensures that all hydroxyl groups are accessible for subsequent interactions.\n\n2. **Cool the solution** to room temperature while stirring to avoid gelation.\n\n---\n\n#### 2.3. Preparation of \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) Solution\n1. Dissolve **1 g of potassium ferricyanide (\\( K_{3}\\text{Fe(CN)}_{6} \\))** or potassium ferrocyanide (\\( K_{4}\\text{Fe(CN)}_{6} \\))** in 50 mL of deionized water**.\n   - This concentration ensures a sufficient amount of the molecule for even dispersion in the polymer matrix.\n\n2. If needed, adjust the pH of the solution to between **6 and 7** to maintain stability of the ferricyanide and ferrocyanide ions.\n\n---\n\n#### 2.4. Incorporation of \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) into the Polymer Matrix\nThere are two main methods of incorporation: **direct physical blending** or **chemical crosslinking**. Here, we will discuss both.\n\n##### (A) **Physical Blending Method**:\n   1. Mix the PVA solution and the \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) solution in a **1:1 volume ratio** under continuous stirring.\n   2. Continue stirring at room temperature for **2 hours** to ensure homogeneity.\n   3. Cast the mixture onto a clean glass or silicone mold to form a film.\n   4. Allow the film to dry at **50 °C overnight** in an oven.\n      - This method ensures that \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) ions are well-integrated into the polymer matrix through hydrogen bonding and electrostatic interactions with PVA's hydroxyl groups.\n\n##### (B) **Chemical Crosslinking Method**:\n   1. Add a crosslinker, such as **glutaraldehyde (GA)**, to improve the mechanical stability of the polymer network.\n      - Add **0.5 mL of GA solution (50% aqueous solution)** and **2 drops of HCl (1 M)** to the PVA- \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) mixture.\n      - Stir for an additional **30 minutes**.\n      - The crosslinker reacts with PVA’s hydroxyl groups, creating a chemically bound network in which \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) is immobilized.\n   2. Cast the crosslinked solution onto a mold and cure at **50 °C for 12 hours**.\n      - This approach enhances the stability of \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) within the polymer by forming a semi-permanent matrix.\n\n---\n\n#### 2.5. Post-Treatment and Washing\n- After drying or curing, wash the polymer film thoroughly with deionized water to remove any unbound \\( K_{x}\\text{Fe(CN)}_{6} \\) ions or residual crosslinkers.\n- Dry the film again at **50 °C for 6 hours**.\n\n---\n\n### Step 3: Mechanism of Interaction and Hydrophilicity Enhancement\n1. **Hydrophilicity Mechanism**:\n   - The incorporated \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) ions, being charged, interact with water molecules through electrostatic attraction, enhancing the hydrophilicity of the polymer.\n   - PVA’s hydroxyl groups also form hydrogen bonds with \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\), further stabilizing the interactions and facilitating water adsorption.\n\n2. **Consistent Interaction**:\n   - Physical blending ensures uniform dispersion of \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) throughout the polymer network.\n   - Chemical crosslinking immobilizes the ions, preventing migration or aggregation over time, which ensures consistent hydrophilic behavior.\n\n---\n\n### Step 4: Reaction Conditions and Practical Notes\n1. Keep the reaction environment free from contaminants or reducing agents, as they might reduce \\( [\\text{Fe(CN)}_{6}]^{3-} \\) to \\( [\\text{Fe(CN)}_{6}]^{4-} \\) or interfere with the polymer properties.\n2. Maintain a pH-neutral reaction medium to avoid decomposition of ferricyanides.\n\n---\n\n### Step 5: Summary\nTo incorporate \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) into a PVA polymer:\n- Dissolve PVA and ferricyanide preparations separately.\n- Physically blend the solutions or chemically crosslink them for improved stability.\n- Cast, dry, and post-treat the films to remove unreacted species.\n- This results in a hydrophilic polymer with a consistent distribution of \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\), enhancing its hydrophilicity through electrostatic and hydrogen-bonding interactions.\n\nBy following this step-by-step protocol, you can successfully prepare a hydrophilic polymer matrix containing \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\). Let me know if you have further questions!"
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+{
+  "design_question": "Explain how you would use the molecule POSS-Br to initiate an Atom Transfer Radical Polymerization (ATRP) process for enhancing the hydrophilicity of a polymer material. Include any critical preparatory steps you would employ in this synthesis.",
+  "design_answer": "Certainly! Your question involves designing an experimental scheme to use POSS-Br (Polyhedral Oligomeric Silsesquioxane functionalized with bromine) as an initiating agent in Atom Transfer Radical Polymerization (ATRP) for synthesizing a hydrophilic polymer. As per your request, I will address this systematically, covering the necessary steps, reaction conditions, reagents, and considerations for laboratory execution.\n\n---\n\n### **Analysis and Key Points**\n1. POSS-Br is a molecule with bromine functionalities that can act as an ATRP initiator. The goal is to use it to prepare a hydrophilic polymer that improves water affinity, potentially for applications such as coatings, biomedical devices, or membranes.\n2. ATRP is a controlled radical polymerization technique that allows precise molecular architecture control and functionalization.\n3. The hydrophilic character of the polymer can be enhanced by selecting monomers with hydrophilic groups, such as ethylene glycol, acrylamide, or methacrylic acids.\n4. Critical aspects include reagent stoichiometry and purity, solvent selection, catalyst preparation, and reaction control to ensure the desired hydrophilic properties.\n\n---\n\n### **Experimental Scheme for POSS-Br-Initiated ATRP**\n\n#### **Step 1: Materials Preparation**\n1. **Initiator**: POSS-Br (ensure it is dry and pure).\n2. **Monomer**: Select hydrophilic monomers, such as poly(ethylene glycol) methyl ether methacrylate (PEGMA), acrylamide, or hydroxyethyl methacrylate (HEMA). These monomers contain polar/hydrophilic groups favorable for water interaction.\n3. **Catalytic System**:\n    - Copper (I) halide (e.g., CuBr or CuCl) as the catalyst.\n    - Ligand such as N,N,N',N''-pentamethyldiethylenetriamine (PMDETA) or 2,2'-bipyridine (Bpy) to stabilize Cu(I) species in solution.\n4. **Solvent**: Toluene, dimethyl sulfoxide (DMSO), or anisole for polymerization (choose depending on monomer solubility and desired reaction rate).\n5. **Deoxygenate System**: A nitrogen or argon purge setup to ensure the reaction remains oxygen-free to prevent radical quenching.\n\n#### **Step 2: Experimental Setup**\n1. **Prepare POSS-Br Initiator Solution**:\n    - Dissolve weighed POSS-Br (calculated based on target molecular weight) into the reaction solvent under stirring.\n    - Select the initiator-to-monomer ratio based on the degree of polymerization (e.g., 1:50 to 1:100 for controlled polymer growth).\n\n2. **Catalyst and Ligand Assembly**:\n    - In a separate container, mix Cu(I) halide and the ligand in the appropriate ratio (typically 1:2 or 1:3 molar ratio).\n    - Add the solvent and stir vigorously to ensure complete dissolution.\n    - Note: The Cu(I) halide may darken the solution, indicating complex formation.\n\n3. **Monomer Addition**:\n    - Add the selected hydrophilic monomer to the POSS-Br solution. The monomer should be added in excess relative to the initiator to achieve desired polymer chain lengths (e.g., initiator:monomer = 1:100 for controlled polymerization).\n\n#### **Step 3: Reaction Conditions**\n1. **Deoxygenation**:\n    - Deoxygenate solutions (initiator solution, monomer, catalyst solution) by bubbling nitrogen gas through for at least 15–30 minutes. ATRP is highly sensitive to oxygen, as it inhibits the radical propagation mechanism.\n2. **Combine Components**:\n    - Under an inert atmosphere (nitrogen or argon), add the catalyst/ligand complex solution to the initiator and monomer mixture.\n    - Seal the vessel tightly to maintain the inert atmosphere and prevent oxygen contamination.\n3. **Reaction Temperature**:\n    - Control the reaction temperature between 50–90°C, depending on the monomer and solvent compatibility. PEGMA-based systems typically polymerize well at around 70°C.\n    - Use an oil bath or block heater to ensure uniform temperature control.\n\n4. **Polymerization Time**:\n    - Allow the polymerization to proceed for 6–12 hours, monitoring periodically for viscosity changes or sample aliquots (if needed). Longer times may lead to higher molecular weights but observe for potential side reactions.\n\n#### **Step 4: Termination and Workup**\n1. **Quench the Reaction**:\n    - Introduce oxygen or add a suitable radical scavenger (e.g., methanol) to terminate the reactive radicals.\n    - Cool the reaction mixture to room temperature.\n\n2. **Purification**:\n    - Precipitate the polymer by dripping the reaction mixture into a non-solvent (e.g., hexane or diethyl ether for PEGMA).\n    - Centrifuge or filter to collect the solid polymer.\n    - Wash repeatedly with fresh non-solvent to remove unreacted monomers, catalyst residuals, and ligands.\n\n3. **Drying**:\n    - Dry the purified polymer under vacuum or in a desiccator for 24–48 hours to ensure complete solvent removal.\n\n#### **Step 5: Characterization**\n1. **Confirm Polymer Structure**:\n    - Use proton NMR (1H-NMR) to verify monomer incorporation into the polymer and ensure the presence of hydrophilic moieties.\n    - Gel Permeation Chromatography (GPC) can be employed to measure molecular weight distribution and degree of polymerization.\n2. **Hydrophilicity Testing**:\n    - Measure water contact angle to quantify the hydrophilicity enhancement.\n    - Fourier Transform Infrared spectroscopy (FTIR) can confirm the presence of hydrophilic functional groups.\n\n---\n\n### **Critical Considerations**\n1. **Reagent Purity**: Ensure all reagents, especially POSS-Br, are dry and free of impurities. Any water or oxygen can interfere with ATRP chemistry.\n2. **Reaction Compatibility**: Consider the solubility of the monomer and initiator in the solvent used. For highly hydrophilic monomers, DMSO is a good solvent; for others, anisole or toluene may suffice.\n3. **Molar Ratios and Control**: Calculate precise molar ratios for initiator, monomer, catalyst, and ligand to achieve the desired molecular weight and controlled polymerization.\n4. **Avoid Oxygen Contamination**: Invest time to fully deoxygenate and maintain inert conditions throughout the setup and polymerization process.\n\nBy following this systematic synthesis scheme, POSS-Br can efficiently initiate ATRP, leading to hydrophilic polymers with well-controlled properties and architecture.\n\nLet me know if you need clarification or additional guidance on any step!"
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+{
+  "design_question": "Outline the steps required to incorporate POSS as an initiator in the synthesis of the polymer. How does the inclusion of POSS contribute to the hydrophilicity of the final polymer material?",
+  "design_answer": "To address your question systematically, we will first analyze the key aspects and then provide a detailed experimental preparation scheme for incorporating Polyhedral Oligomeric Silsesquioxane (POSS) as an initiator in polymer synthesis while enhancing the hydrophilicity of the final polymer material.\n\n---\n\n### **Analysis of the Question**\n1. **Objective**: To incorporate POSS as an initiator in the synthesis of a hydrophilic polymer. The primary goal is to introduce POSS into the polymer backbone to enhance material properties, including hydrophilicity.\n2. **Key Functional Role of POSS**: POSS is a nanoscale cage-like molecule with a silicon-oxygen framework. Its hydrophilic variants, which often contain hydroxyl (-OH) or other hydrophilic functional groups, can significantly improve the hydrophilicity of the resulting polymer due to its interaction with water and its ability to modify the surface energy of the polymer.\n3. **Experimental Challenges**:\n   - Proper functionalization of POSS to act as an effective initiator.\n   - Optimization of polymerization conditions (e.g., selection of monomers, solvent system, and initiator concentration).\n   - Control of POSS distribution within the polymer matrix to achieve uniform hydrophilicity.\n\n---\n\n### **Experimental Preparation Scheme for Incorporating POSS as an Initiator**\n\n#### Step 1: Selection of POSS Derivative\n- Choose a hydroxyl-functionalized POSS molecule (e.g., POSS-triol or POSS containing multiple -OH groups) as the base material. These hydroxyl groups make it easy to chemically modify POSS and act as initiation sites for polymerization.\n- If a more reactive variant is required, POSS molecules bearing amino (-NH2), carboxylic acid (-COOH), or methacryloyl (-C=C-) groups can also be used, depending on the type of polymerization to be conducted.\n\n---\n\n#### Step 2: Functionalization of POSS to Enable Initiation\nTo prepare POSS as an initiator, we need to attach initiator functional groups to the POSS framework, depending on the polymerization mechanism:\n\n- **For Free Radical Polymerization**:\n  1. React hydroxyl-functionalized POSS with acryloyl chloride or methacryloyl chloride under mild conditions to form acrylate-functionalized POSS.\n     - **Reaction Conditions**:\n       - Dissolve POSS (1 mole) in dry dichloromethane (DCM) or tetrahydrofuran (THF) under an inert nitrogen atmosphere.\n       - Add triethylamine (TEA) as a base (1.2 moles to neutralize HCl released).\n       - Dropwise add acryloyl chloride or methacryloyl chloride (1.1 moles) while stirring at 0°C (using an ice bath).\n       - After completion of addition, warm the reaction mixture to room temperature and stir for 4–6 hours.\n       - Filter off the TEA-HCl precipitate and purify POSS-acrylate by washing with brine and drying under reduced pressure.\n  2. This functionalized POSS can now participate as an active center in radical polymerization with hydrophilic monomers (e.g., acrylamide, methacrylic acid).\n\n- **For Ring-Opening Polymerization (ROP)**:\n  1. React hydroxyl-functionalized POSS with ε-caprolactone or lactide monomers using stannous octoate (Sn(Oct)2) as a catalyst.\n     - **Reaction Conditions**:\n       - Dissolve POSS in anhydrous toluene and add ε-caprolactone (10:1 molar ratio of monomer to POSS initiator).\n       - Add stannous octoate at 0.1 wt% of total monomer.\n       - Heat reaction mixture to 100°C under an inert nitrogen atmosphere and stir for 12–24 hours.\n       - Isolate POSS-initiated prepolymer via precipitation in cold methanol.\n\n- **For Controlled Living Polymerizations (e.g., Atom Transfer Radical Polymerization (ATRP))**:\n  1. React POSS-triol with α-bromoacetyl bromide to introduce bromo initiator groups.\n     - Dissolve POSS and add excess α-bromoacetyl bromide in dry dichloromethane with TEA as a base.\n     - Purify the POSS-functionalized initiator and use this in ATRP with a copper-based catalyst and ligand.\n\n---\n\n#### Step 3: Polymerization with Hydrophilic Monomers\n- Select hydrophilic monomers such as acrylamide, hydroxyethyl methacrylate (HEMA), or methacrylic acid for copolymerization.\n- Polymerization can proceed in solution, suspension, or bulk phases, using POSS-functionalized initiator prepared in Step 2.\n\n**Example: Free Radical Polymerization**\n1. Dissolve hydrophilic monomers (e.g., acrylamide, 10 g) and POSS initiator (1 g) in a solvent like deionized water or ethanol.\n2. Add an initiator (e.g., ammonium persulfate (APS)) to thermally trigger polymerization, or use photo-initiation with UV light if a photoinitiator group was attached to the POSS.\n3. Control reaction temperature (e.g., ~60–70°C for APS) and stir the mixture for 6–12 hours.\n4. Purify the POSS-modified hydrophilic polymer by dialysis or precipitation depending on solubility.\n\n---\n\n#### Step 4: Post-Polymerization Modifications (Optional)\nTo further enhance hydrophilicity:\n- Incorporate sulfonic acid groups or polyethylene glycol (PEG) chains into the polymer backbone or side chains.\n- Verify hydrophilicity improvement via water contact angle measurements and swelling ratio analysis in water.\n\n---\n\n### **How POSS Enhances Hydrophilicity**\n1. **Nanoscale Structure**: POSS molecules have a highly polar and hydrophilic silicon-oxygen core, which inherently increases water interaction.\n2. **Surface Energy Alteration**: The inclusion of POSS at regular intervals in the polymer matrix reduces the contact angle of water droplets, increasing hydrophilicity.\n3. **Increased Surface Roughness**: POSS enhances hydrophilic behavior by providing a nanostructured surface.\n4. **Functional Modifications**: POSS allows the introduction of additional hydrophilic groups (e.g., hydroxyl, carboxyl) that interact with water.\n\n---\n\n### **Conclusion**\nIncorporating POSS as an initiator in polymer synthesis offers a robust strategy to enhance hydrophilicity of the resulting material. The outlined preparation scheme systematically adjusts reaction conditions to prepare a POSS-functionalized polymer efficiently. Control over reaction conditions and functional groups ensures reproducibility and success in the lab. Would you like additional clarification on any of the steps?"
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+{
+  "design_question": "Propylene glycol is mentioned as a component in the preparation of hydrophilic polymers. Design an experimental protocol incorporating propylene glycol to enhance the hydrophilicity of a polymer surface. Include details such as concentration, mixing methods, and reaction conditions.",
+  "design_answer": "Excellent question! Let's work step by step to design an experimental protocol incorporating **propylene glycol (PG)** to enhance the hydrophilicity of a polymer surface. Before diving into the specifics, I'll analyze the question and highlight key points.\n\n---\n\n### **1. Key Points to Consider**\n- **Objective**: Incorporate propylene glycol into a protocol to increase the hydrophilicity of a polymer surface.\n- **Challenges**: A polymer’s surface must be modified in a controlled manner to achieve hydrophilicity without compromising its structural integrity.\n- **Propylene Glycol Properties**: PG has strong hydrophilic characteristics due to its hydroxyl (-OH) groups but requires a functionalization method to graft it or blend it effectively into a polymer.\n- **Methodology**: Since PG is not inherently polymerizable on its own, we must either (a) physically blend it into the polymer matrix or (b) chemically graft it onto the surface.\n\n---\n\n### **2. Protocol Design: Enhancing Hydrophilicity of a Polymer Surface**\n\nWe will use chemical surface functionalization of the polymer with grafted propylene glycol for long-lasting hydrophilicity. A two-step method is recommended: **(i) pre-activation of the polymer surface** followed by **(ii) grafting propylene glycol via coupling chemistry**.\n\n---\n\n#### **Step 1: Pre-Activation of Polymer Surface**\n1. **Objective**: To introduce reactive groups onto the polymer surface for PG grafting.\n2. **Method**: Plasma treatment or chemical activation with an oxidizing agent (e.g., potassium permanganate or chromic acid).\n\n   **Example: Chemical Activation with Potassium Permanganate**\n   - **Materials Required**: Polymer target, potassium permanganate (KMnO₄), sulfuric acid (H₂SO₄).\n   - **Procedure**:\n     1. Clean the polymer surface using ethanol and de-ionized water.\n     2. Submerge the polymer in an oxidizing solution (0.1 M KMnO₄ with 1 M H₂SO₄) at 70°C for 30 minutes.\n     3. Wash thoroughly with DI water and dry under nitrogen.\n   - **Expected Outcome**: Hydroxyl (-OH), carboxylic acid (-COOH), or carbonyl (-C=O) groups will form on the polymer surface, providing reactive sites for PG attachment.\n\n---\n\n#### **Step 2: Grafting Propylene Glycol to the Polymer Surface**\n1. **Objective**: Chemically bind propylene glycol to the activated polymer surface using coupling chemistry.\n2. **Materials Required**:\n   - Propylene glycol (99% pure).\n   - Carbodiimide coupling reagent (e.g., 1-ethyl-3-[3-dimethylaminopropyl]carbodiimide (EDC)).\n   - Hydroxybenzotriazole (HOBt) to enhance coupling efficiency.\n   - Phosphate buffer (pH = 7.2).\n\n3. **Procedure**:\n   - **Preparation of Coupling Solution**:\n     1. Dissolve 0.1 M EDC and 0.05 M HOBt in phosphate buffer.\n     2. Add 0.1 M propylene glycol to the solution, stirring at room temperature for 10 minutes.\n   - **Application**:\n     1. Immerse the activated polymer specimen in the coupling solution.\n     2. Maintain stirring at room temperature (25–30°C) for 16–18 hours.\n     3. Rinse the polymer thoroughly with DI water to remove unreacted PG.\n   - **Expected Outcome**: Propylene glycol molecules covalently bond to the surface through the hydroxyl and carboxylic acid groups introduced during activation.\n\n---\n\n#### **Step 3: Post-Treatment and Confirmation**\n1. **Drying**:\n   - Allow the polymer to dry under vacuum at 40°C for 24 hours.\n2. **Confirmation of Hydrophilicity**:\n   - Use **water contact angle measurement** to confirm increased hydrophilicity. Hydrophilic surfaces exhibit a contact angle <45°.\n   - Perform **FTIR spectroscopy** to verify successful grafting. Look for characteristic hydroxyl (-OH) peaks associated with propylene glycol in the 3200–3500 cm⁻¹ range.\n\n---\n\n### **3. Summary of Protocol**\n- Pre-treat the polymer surface for activation via oxidation (e.g., KMnO₄ or plasma treatment).\n- Conduct chemical coupling of propylene glycol using a carbodiimide reaction (EDC/HOBt system).\n- Ensure all reaction conditions (temperature, pH, timescale) are optimized for effective grafting.\n- Post-treat the polymer and confirm hydrophilicity enhancement via analytical tools like water contact angle or FTIR.\n\n---\n\nBy following this step-by-step experimental plan, you should be able to effectively incorporate propylene glycol into a functionalized hydrophilic polymer surface. Let me know if you'd like further explanations or adjustments to this protocol!"
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+{
+  "design_question": "Design an experimental scheme to deposit multiple nanometer-scale layers of charged molecular materials onto a polymer substrate, ensuring each layer enhances the overall hydrophilic properties of the polymer. Outline the control parameters you would use to achieve the desired thickness and hydrophilicity.",
+  "design_answer": "Certainly! Let’s break down the question systematically into steps for an experimental procedure to deposit nanometer-scale layers of charged molecular materials onto a polymer substrate, enhancing its hydrophilicity. This involves utilizing a well-established technique called **Layer-by-Layer (LbL) Assembly**. The key is to control the deposition of oppositely charged materials to form ultra-thin, uniform layers with tailored thickness and hydrophilic properties.\n\n---\n\n### Step-by-Step Design of the Experimental Scheme\n\n---\n\n#### **Step 1: Analyze the Question and Key Points**\nThe provided question centers on two interconnected objectives:\n1. **Nanometer-scale layering:** Controlled deposition of molecular materials with specific layer thicknesses (in the nanometer regime).\n2. **Enhanced hydrophilicity:** The added layers must introduce functional groups or properties that increase the hydrophilicity of the polymer substrate.\n\nThe solution lies in systematically assembling charged molecules (polyelectrolytes or other charged materials) and tuning their properties at the molecular scale using an *LbL Assembly* method.\n\n#### **Step 2: Materials and Reagents Required**\nBelow is a list of materials and reagents well-suited for this approach:\n1. **Polymer Substrate:** A hydrophobic polymer substrate (e.g., polyethylene terephthalate [PET], polyvinyl chloride [PVC], polystyrene, or a similar polymer).\n2. **Positively Charged Polyelectrolyte:** For example, poly(diallyldimethylammonium chloride) (PDDA) or poly-L-lysine.\n3. **Negatively Charged Polyelectrolyte:** For example, poly(sodium 4-styrenesulfonate) (PSS) or hyaluronic acid (HA).\n4. **Buffer Solution:** An aqueous buffer (e.g., phosphate-buffered saline [PBS] or NaCl solution) to maintain the ionic strength during deposition.\n5. **Deionized Water (DI Water):** To prepare the buffer and rinse between each deposition step.\n6. **Optional Hydrophilic Additives:** Small molecules or surfactants to improve wettability during or after deposition, e.g., poly(ethylene glycol) (PEG) or zwitterionic molecules.\n\n---\n\n#### **Step 3: Experimental Parameters**\nControl parameters to ensure nanometer-scale layering and hydrophilicity:\n1. **Layer Thickness:** Thickness of each layer (5-10 nm) controlled primarily by the concentration and adsorption time of the polyelectrolytes.\n2. **pH and Ionic Strength:** Buffer pH and salt concentration affect the charge density of polyelectrolytes and their binding efficiency.\n3. **Washing Steps:** Thorough rinsing between layers to remove loosely bound material and prevent uneven deposition.\n4. **Number of Layers:** Adjust the number of assembled bilayers (typically up to 10-20) to achieve the desired hydrophilic surface properties.\n\n---\n\n#### **Step 4: Procedure**\nBelow is a systematic procedure for the layer-by-layer deposition:\n\n---\n\n**Step 4.1: Substrate Preparation**\n- **Clean the Polymer Substrate:**\n  - Wash the polymer substrate (e.g., PET or PVC film) with ethanol and deionized water to remove contaminants.\n  - Dry with nitrogen or in a desiccated environment.\n  - Optionally, perform mild oxygen plasma treatment (if accessible) to activate the surface and introduce polar groups, further improving hydrophilicity and adhesion.\n\n---\n\n**Step 4.2: Prepare Polyelectrolyte Solutions**\n- Dissolve **PDDA** (positively charged polyelectrolyte) in the buffer solution (e.g., 0.5 M NaCl, pH 6.5-7) to a concentration of ~1 mg/mL.\n- Similarly, prepare a ~1 mg/mL solution of the **PSS** (negatively charged polyelectrolyte) in the buffer solution.\n- Filter both solutions through a 0.22 µm membrane to remove particulates.\n\n---\n\n**Step 4.3: Deposition of Layer-by-Layer Films**\nRepeat the following cycle for the desired number of bilayers:\n1. **Deposit the Positively Charged Layer:**\n   - Immerse the polymer substrate into the PDDA solution for 10 minutes at room temperature. Electrostatic interactions will adsorb the positively charged polymer onto the substrate surface.\n   - Gently rinse the substrate with DI water for 1-2 minutes to remove unbound PDDA.\n2. **Deposit the Negatively Charged Layer:**\n   - Immerse the polymer substrate into the PSS solution, again for 10 minutes at room temperature. Electrostatic interactions will cause the negatively charged PSS to bind to the positively charged PDDA layer.\n   - Rinse the substrate with DI water for 1-2 minutes to remove unbound PSS.\n3. **Repeat Steps 1 and 2** to build up the desired number of bilayers (e.g., 10 total repetitions = 10 PDDA/PSS layers).\n\n---\n\n**Step 4.4: Post-Treatment to Enhance Hydrophilicity**\n- After achieving the desired number of layers, rinse the final coated substrate with DI water and dry it under nitrogen flow or ambient conditions.\n- Optionally introduce functional groups, such as PEGylation, on the outermost layer by immersing the substrate in a PEG derivative solution (e.g., methoxy-PEG-silane at 1 wt% in DI water) for 1-2 hours followed by rinsing.\n\n---\n\n#### **Step 5: Characterization of the Hydrophilic Coatings**\nRun the following analyses to confirm coating integrity and hydrophilicity:\n1. **Water Contact Angle Measurement:** A lower contact angle (<30°) indicates higher hydrophilicity.\n2. **Ellipsometry or AFM (Atomic Force Microscopy):** To measure the thickness of each nanolayer and verify uniformity.\n3. **Zeta Potential Measurement:** Verify surface charge of the deposited layers at each stage.\n4. **ATR-FTIR or XPS Analysis:** Confirm the presence of functional groups that contribute to hydrophilicity (e.g., sulfonate or amine groups).\n\n---\n\n#### **Step 6: Troubleshooting and Optimization**\n- If thickness per layer exceeds 10 nm, reduce the polyelectrolyte concentration or adsorption time.\n- If hydrophilicity is insufficient, increase the number of bilayers or modify the final layer chemistry (e.g., adding a PEGylated or zwitterionic layer).\n- Adjust pH or ionic strength for better electrostatic interaction if deposition is uneven.\n\n---\n\n### Summary\nThis experimental procedure uses **Layer-by-Layer (LbL) Assembly** to deposit nanometer-scale layers of oppositely charged polyelectrolytes on a polymer substrate, enhancing hydrophilicity. Careful control of solution concentration, deposition time, and rinsing steps ensures uniform layer formation. The hydrophilicity of the final product can be fine-tuned by adjusting the number of layers or functionalizing the outermost layer with hydrophilic compounds such as PEG."
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+{
+  "design_question": "Explain how you would use a host-guest interaction between a suprastructure and a polymer in a layer-by-layer assembly to improve the hydrophilicity of the polymer. Include details about substrate preparation and the number of desired layers.",
+  "design_answer": "To answer your question systematically and thoroughly, I will analyze the problem, provide an experimental preparation scheme for using a host-guest interaction in a suprastructure/polymer layer-by-layer (LbL) assembly to improve hydrophilicity, and include specific details regarding substrate preparation, reaction conditions, and the desired number of layers.\n\n---\n\n### **1. Key considerations in the question:**\n- **Primary focus:** Use of host-guest chemistry in an LbL assembly to modify and enhance the hydrophilicity of a polymer.\n- **Materials involved:** A suprastructure with host-guest capabilities and a polymer that interacts with it. \n- **Goal:** Systematic preparation of a hydrophilic polymer by assembling layers with controlled chemistry.\n- **Details required:** Substrate preparation, reaction conditions, reagent quantities, and the target number of layers.\n\n---\n\n### **2. Host-guest interaction in polymer assembly:**\nHost-guest interactions rely on non-covalent binding between a \"host\" molecule (e.g., cyclodextrins) and a \"guest\" molecule (e.g., hydrophilic moieties or small aromatic compounds) to build supramolecular structures. This principle can be applied in an LbL assembly to create alternating layers of a hydrophilic polymer and a supramolecular host molecule, ultimately enhancing surface hydrophilicity.\n\n**Host example:** β-cyclodextrin (CD), which has a hydrophobic inner cavity and hydrophilic exterior.\n**Guest example:** A hydrophilic polymer functionalized with aromatic moieties, such as polyethylene glycol modified with ferrocene or adamantane groups.\n\n---\n\n### **3. Experimental Procedure: Layer-By-Layer Assembly**\n\n#### **Step 1: Substrate preparation**\n1. **Substrate selection:** Use a flat, stable substrate such as a glass slide, silicon wafer, or a nickel grid. The substrate must have a clean, smooth surface to promote uniform adhesion. \n2. **Cleaning:** \n   - Immerse the substrate in piranha solution (3:1 mixture of concentrated sulfuric acid and hydrogen peroxide) for 30 minutes. *(Caution: Piranha solution is highly reactive—handle with extreme care!)*\n   - Rinse thoroughly with deionized (DI) water and dry under a nitrogen stream.\n3. **Surface functionalization (if required):**\n   - To improve interaction between the substrate and the first polymer layer, functionalize the substrate surface with a positively charged monolayer, e.g., expose to a 1 mM solution of poly(allylamine hydrochloride) (PAH) in DI water for 5 minutes. Rinse with DI water and dry.\n\n---\n\n#### **Step 2: Preparation of aqueous solutions**\n1. Prepare a 5 mg/mL solution of β-cyclodextrin (host) in DI water.\n2. Prepare a 1 mg/mL solution of the hydrophilic polymer-functionalized with a guest molecule (e.g., adamantyl-polyethylene glycol), also in DI water.\n\n---\n\n#### **Step 3: Layer-by-layer (LbL) assembly**\n1. **Immersion cycle for layer formation:**\n   - **Host layer deposition:** Submerge the prepared substrate in the β-cyclodextrin solution for 10 minutes to allow adsorption via electrostatic or host-guest interactions. Ensure calm agitation during this process for uniform adsorption.\n   - **Rinse and dry:** Remove the substrate, rinse with DI water to remove excess β-cyclodextrin, and dry gently with nitrogen.\n   - **Guest/polymer layer deposition:** Submerge the β-cyclodextrin-coated substrate in the guest-functionalized hydrophilic polymer solution for 15 minutes. This will allow the guest groups to enter the host's hydrophobic cavity, forming host-guest complexes.\n   - **Rinse and dry:** Clean the substrate as in the previous step (DI water rinse + nitrogen drying).\n2. Repeat the immersion cycle (steps 3.1 through 3.4) to create additional layers. Each cycle adds one bilayer of host (cyclodextrin) and guest (functionalized hydrophilic polymer).\n\n---\n\n#### **Step 4: Number of desired layers**\n- **Determining optimal layers for hydrophilicity:** Perform contact angle measurements after depositing each bilayer. Hydrophilicity is indicated by a decrease in the water contact angle.\n- For most applications, 10–15 bilayers (~20–30 nm thick, depending on the size of the host and guest) are sufficient to ensure significant surface hydrophilicity.\n\n---\n\n#### **Step 5: Verification of assembly**\n1. Use spectroscopic and microscopic techniques to verify successful LbL assembly:\n   - **UV-vis absorbance:** Confirm increased optical density after each layer deposition if the polymer-host complex is UV-active.\n   - **Atomic force microscopy (AFM):** Visualize uniformity and thickness of the layers.\n   - **Contact angle measurement:** Ensure progressive improvement in hydrophilicity as layers are added.\n\n---\n\n### **4. Reaction Conditions & Notes:**\n- Maintain room temperature (20–25 °C) throughout the procedure to prevent degradation of the host or guest molecules.\n- All solutions should be prepared fresh and filtered (using a 0.22 μm membrane) before use to remove particulates.\n- Use ultrapure DI water for all rinsing steps to prevent contamination.\n- If working with charged variants of host or guest molecules, the ionic strength of the solution can be adjusted by adding NaCl (e.g., 0.1 M) to facilitate electrostatic interactions.\n\n---\n\n### **5. Summary**\nThis procedure uses a host-guest LbL assembly to enhance the hydrophilicity of a polymer-coated substrate. Starting with a clean, functionalized substrate, the process alternates between adsorption of a host molecule (e.g., β-cyclodextrin) and a guest-functionalized hydrophilic polymer. By repeating the alternating adsorption process for a defined number of bilayers (e.g., 10–15), surface modification is achieved, with improved hydrophilicity verified by techniques such as contact angle measurements and AFM imaging.\n\nThis systematic approach ensures the successful preparation of a hydrophilic polymer via controlled supramolecular assembly. Should you encounter any practical challenges in the lab, feel free to reach out for clarification!"
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+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe how you would ensure that N,N-dimethylacrylamide (DMAA) is effectively polymerized onto a polymer surface to enhance hydrophilicity. Include any necessary steps to prepare the surface before polymerization."}, {"role": "assistant", "content": "To ensure that N,N-dimethylacrylamide (DMAA) is effectively polymerized onto a polymer surface to enhance hydrophilicity, it is essential to consider both the surface preparation and the polymerization process itself. Below, I will systematically and comprehensively outline the procedure, incorporating detailed reaction conditions, reagent ratios, and practical laboratory considerations.\n\n---\n\n### **Step-by-Step Experimental Preparation Scheme**\n\n---\n\n#### **Step 1: Analyze the Question and Define the Key Points**\n\nThe main objective is to graft a hydrophilic polymer, specifically poly(N,N-dimethylacrylamide) (PDMAA), onto the surface of a base polymer to enhance the hydrophilicity of the material. Two critical aspects need to be addressed:\n1. **Surface preparation**: Modify the polymer surface to introduce reactive functional groups for subsequent DMAA polymerization.\n2. **Polymerization process**: Ensure that DMAA polymerizes effectively onto the functionalized surface in a controlled manner to create a uniform hydrophilic coating.\n\n---\n\n#### **Step 2: Surface Preparation**\n\nBefore DMAA can be polymerized onto the polymer surface, the surface must be treated to introduce functional groups (e.g., hydroxyl, carboxyl, or amine groups) that can act as initiation points for the polymerization process.\n\n1. **Cleaning the Base Polymer Surface:**\n    - Wash the polymer substrate thoroughly with a series of solvents to remove surface contaminants (e.g., organic residues, oils, or dust).\n    - Suggested protocol: rinse in deionized water, followed by immersion in ethanol or isopropanol, and then air-dry.\n\n2. **Activation via Oxidation (if applicable):**\n    - For non-reactive polymer surfaces (e.g., polyethylene or polypropylene), plasma treatment or oxidative treatment (e.g., using ozone or chromic acid) can introduce carboxyl or hydroxyl groups.\n    - Example: Plasma treatment with oxygen gas for 5\u201310 minutes at low pressure (~200 mTorr). Alternatively, immerse the polymer in 0.1 M chromic acid for 15\u201320 minutes, followed by rinsing thoroughly with deionized water.\n\n3. **Coupling Agent Application (Optional for Improved Attachment):**\n    - Apply a silane coupling agent if the polymer surface is inherently poor in chemical reactivity.\n    - Example: Treat the polymer surface with 0.1% (v/v) solution of 3-aminopropyltriethoxysilane (APTES) in ethanol for 30 minutes at room temperature, followed by rinsing and curing at 100 \u00b0C for 1 hour.\n\nThe resulting surface should contain active functional groups (e.g., hydroxyl, carboxyl, or amine moieties) to enable subsequent reaction with DMAA and initiators.\n\n---\n\n#### **Step 3: Polymerization of DMAA**\n\nDMAA will be grafted onto the prepared surface by free radical polymerization. This process involves the use of an initiator (e.g., a peroxide-based compound) and reaction conditions conducive to DMAA polymerization.\n\n1. **Preparation of Reaction Mixture:**\n    - Dissolve N,N-dimethylacrylamide (DMAA) in deionized water or an aqueous ethanol solution at a concentration of ~10\u201320% (w/v).\n    - Add an initiator, such as ammonium persulfate (APS), at 0.5\u20131.0% (w/v) relative to the DMAA monomer concentration.\n    - Include a catalyst or co-initiator for enhanced polymerization rates. For APS, N,N,N',N'-tetramethylethylenediamine (TEMED) can be used at 0.1% (w/v).\n    - Adjust the pH of the solution to ~7\u20138 using NaOH to ensure a stable reaction environment.\n\n2. **Immobilization of Initiator onto the Surface:**\n    - Coat the surface with a thin layer of APS solution (~0.1 M) and allow it to dry. This step ensures localized polymerization at the surface rather than in bulk solution.\n\n3. **Grafting of DMAA via Radical Polymerization:**\n    - Submerge the treated polymer surface into the DMAA reaction mixture.\n    - Maintain the reaction at ~40\u201360 \u00b0C for 4\u20138 hours (depending on monomer concentration and desired graft density). Ensure consistent stirring or gentle agitation of the solution to maintain uniform contact with the substrate.\n    - Optional: For UV-mediated polymerization, incorporate a photoinitiator (e.g., benzophenone) at ~1% (w/v) and expose the system to UV light (wavelength: 365 nm) for 1\u20132 hours.\n\n4. **Post-Polymerization Washing:**\n    - Thoroughly rinse the polymer substrate with deionized water to remove unreacted monomer and initiator residues.\n    - Use mild sonication (~40 kHz) in water for 10\u201315 minutes to ensure the removal of loosely bound polymer chains.\n\n---\n\n#### **Step 4: Characterization and Validation**\n\nTo confirm successful polymerization, employ the following characterization techniques:\n1. **Contact Angle Measurement:**\n    - Evaluate the hydrophilicity of the polymer surface by measuring the water contact angle. A significant reduction (e.g., <40\u00b0) compared to the untreated polymer indicates successful grafting of PDMAA.\n\n2. **Fourier Transform Infrared Spectroscopy (FTIR):**\n    - Look for characteristic amide peaks in the IR spectrum (e.g., C=O stretching at ~1650 cm\u207b\u00b9 and N-H bending at ~1540 cm\u207b\u00b9) as confirmation of DMAA polymerization.\n\n3. **Scanning Electron Microscopy (SEM):**\n    - Observe the surface morphology of the treated polymer. Uniform coating with polymerized PDMAA should appear smooth and continuous.\n\n4. **X-ray Photoelectron Spectroscopy (XPS):**\n    - Analyze surface elemental composition to confirm the presence of nitrogen from the DMAA structure.\n\n---\n\n#### **Step 5: Optimization of Grafting Density**\n\nThe grafting density of PDMAA can be optimized by altering the DMAA concentration, initiator ratio, or reaction time. Higher DMAA concentration or longer reaction times typically yield thicker hydrophilic coatings but may pose risks of delamination or brittleness. Iterative testing with the above characterization techniques will help refine the experimental parameters.\n\n---\n\n### **Conclusion**\n\nBy carefully preparing the polymer surface and conducting controlled radical polymerization of DMAA, you can achieve a robust hydrophilic coating that enhances surface wettability. This experimental scheme can be modified based on the specific polymer substrate or application requirements."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe how you would use the Ugi four-component reaction to synthesize a molecule capable of enhancing the hydrophilicity of a polymer. Include the specific roles of each component in the reaction."}, {"role": "assistant", "content": "### Question Analysis and Key Points\n\nThe student is asking how to use the **Ugi four-component reaction (Ugi-4CR)** to synthesize a molecule that can enhance the hydrophilicity of a polymer. To address this question systematically, we need to:\n\n1. **Understand the Ugi reaction:** The Ugi-4CR is a versatile reaction where an aldehyde (or ketone), an amine, a carboxylic acid, and an isocyanide combine to form a single product\u2014the output contains an amide functional group and typically multiple functional groups that can be leveraged for further modifications.\n\n2. **Design a molecule that enhances hydrophilicity:** Hydrophilic polymers often rely on functional groups such as hydroxyl (-OH), amide (-CONH-), carboxyl (-COOH), or sulfated groups to interact favorably with water. Incorporating such groups during or after the Ugi reaction is key.\n\n3. **Identify roles of the components:** Each of the four components in the Ugi reaction serves a specific purpose (structural building block or functional group provider).\n\n4. **Provide detailed experimental steps:** The synthesis process must include reagent ratios, reaction times, purification methods, and options to attach the synthesized product to the target polymer for enhanced hydrophilicity.\n\n---\n\n### Detailed Experimental Scheme for Hydrophilic Polymer Enhancement Using Ugi-4CR\n\n#### Objective:\nTo design and synthesize a hydrophilic molecule via the Ugi four-component reaction (Ugi-4CR) that can be incorporated into a polymer to enhance hydrophilicity.\n\n---\n\n#### Components to Use:\n1. **Aldehyde/Ketone:** Choose an aldehyde or ketone that offers no hydrophobic steric hindrance. For instance:\n    - **Formaldehyde (HCHO)**: A small molecule capable of adding functional flexibility and simplicity.\n    - Alternatively: Use **glyoxal** (HOCHCHO) to add more hydrophilic moieties directly.\n\n2. **Amine:** Select an amine containing hydrophilic groups such as hydroxyl (-OH), sulfonic acid (-SO3H), or amino (-NH2). For example:\n    - **Ethanolamine (HOCH2CH2NH2)**: Provides a hydroxyl group for hydrophilicity and potentially polymer compatibility.\n\n3. **Carboxylic Acid:** Use a carboxylic acid with water-soluble characteristics. For instance:\n    - **Glycine (H2NCH2COOH)**: Contains both amine and carboxylic acid functionalities to increase hydrophilicity. Glycine is simple and widely available.\n    - Alternatively: **Acryloyl acid derivatives** to introduce polymerizable double bonds.\n\n4. **Isocyanide:** Select an isocyanide that retains compatibility with water and does not introduce hydrophobic groups.\n    - Example: **Tert-butyl isocyanide (t-BuNC)**: Facilitates efficient reaction kinetics without hindering hydrophilicity.\n\n---\n\n#### Reaction Scheme:\nThe synthesis proceeds as follows:\n\n1. **Reaction Setup:**\n   - **Molar ratio:** Aldehyde:Amine:Carboxylic acid:Isocyanide should be **1:1:1:1**. This ensures maximum yield of the Ugi adduct.\n   - **Solvent:** Conduct the reaction in methanol or ethanol, as they are polar solvents that facilitate mixing and solvation for hydrophilic components.\n   - **Reaction temperature:** Typically at room temperature (20\u201325\u00b0C).\n   - **Reaction time:** Stir for 12\u201324 hours for complete conversion.\n\n2. **Procedure:**\n   - Dissolve the aldehyde (formaldehyde/glyoxal) in the solvent.\n   - Add the amine dropwise while stirring.\n   - Introduce the carboxylic acid while maintaining gentle stirring.\n   - Add the isocyanide last, observing a slight exothermic reaction (if the mixture warms up, cool it back to room temperature).\n   - Continue stirring until no starting materials remain (monitor progress via TLC or NMR spectroscopy).\n\n3. **Purification:**\n   - Isolate the Ugi adduct using vacuum filtration or rotary evaporation if the solvent cannot be recovered.\n   - Further purify by recrystallization from ethanol or methanol.\n\n---\n\n#### Example Hydrophilic Product Design:\nUsing **glyoxal, ethanolamine, glycine**, and **tert-butyl isocyanide**, the Ugi reaction yields a highly functionalized molecule with the following characteristics:\n   - **Hydroxyl groups** (from glyoxal and ethanolamine).\n   - **Amide linkage** (formed during the Ugi reaction).\n   - **Carboxylic acid group** (retained from glycine).\n\nThis product will be inherently hydrophilic due to the presence of hydroxyl and carboxylic groups.\n\n---\n\n#### Reaction Details (Example):\nReagent Quantities (for 1 mmol scale):\n- **Glyoxal (40% aqueous solution)**: 67 \u00b5L (provides 1 mmol of active CHO groups).\n- **Ethanolamine:** 61 \u00b5L (1 mmol).\n- **Glycine:** 75 mg (1 mmol).\n- **Tert-butyl isocyanide:** 107 \u00b5L (1 mmol).\n- Solvent: Use 5 mL methanol.\n\n---\n\n#### Incorporation into Polymer:\nOnce the Ugi adduct is synthesized, you can:\n1. Attach it to a polymer via covalent bonding if the polymer backbone contains active sites (e.g., -OH or -COOH groups).\n2. Directly polymerize the Ugi adduct if it contains functional groups (e.g., unsaturated bonds) that allow radical or addition polymerization.\n\n---\n\n### Summary:\nUsing the Ugi four-component reaction allows you to synthesize a hydrophilic functional molecule with precise control over functional groups. Each component serves a clear role:\n1. **Aldehyde/Ketone**: Facilitates condensation to yield the central scaffold.\n2. **Amine**: Adds nitrogen-containing hydrophilic groups for function and reactivity.\n3. **Carboxylic Acid**: Enhances hydrophilicity directly and stabilizes the product.\n4. **Isocyanide**: Finalizes the reaction by forming the amide backbone.\n\nThis methodology provides an efficient pathway to produce hydrophilic additives for materials applications and can be tuned further for specific polymer systems."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "How would you determine the degree of functionalization (DoF) after functionalizing a polymer with methacrylic anhydride (MA)? Describe this process and the calculations involved."}, {"role": "assistant", "content": "To determine the **degree of functionalization (DoF)** after functionalizing a polymer with methacrylic anhydride (MA), we need to consider a systematic approach that analyzes the chemical structure of the polymer before and after modification to quantify the extent of functionalization. Below, I\u2019ll walk you through the process, covering experimental techniques, calculation methods, and supporting details to help you successfully evaluate the DoF.\n\n---\n\n### **Key Points to Analyze**\n1. **What does Degree of Functionalization (DoF) mean?**\n   - DoF refers to the fraction (or percentage) of reactive functional groups on the polymer backbone that are successfully modified with the desired functional group\u2014in this case, the methacrylic group from MA.\n\n2. **Main experimental objective:**\n   - Quantitatively determine how many functional sites on the polymer (e.g., hydroxyl, amine, or other reactive groups) have reacted with methacrylic anhydride.\n\n---\n\n### **Step-by-Step Process with Detailed Procedures**\n\n#### **Step 1: Characterization Techniques to Measure DoF**\nThere are several analytical techniques that can be used to quantify DoF, depending on the composition and molecular structure of the polymer. Below are the most common methods:\n\n##### **A. Nuclear Magnetic Resonance (NMR) Spectroscopy**\n   - **Objective:** Use NMR (typically 1H-NMR or 13C-NMR) to compare the chemical shifts and integration values representing the modified groups and the unmodified functional groups.\n   - **Experimental Process:**\n     1. Prepare polymer samples before and after functionalization.\n     2. Dissolve the samples in an appropriate solvent (e.g., deuterated chloroform, DMSO-d6, or water, depending on polymer solubility).\n     3. Run an NMR spectrum and identify peaks corresponding to the methacrylic group's protons (e.g., vinyl protons or ester protons) and those of the unmodified polymer.\n     4. Integrate the peak areas associated with the functionalized groups (such as methacrylic vinyl (-CH=CH2) or ester groups (-COO-)).\n   - **Calculation:**\n     - Degree of functionalization (DoF) is calculated as:\n       \\[\n       \\text{DoF} = \\frac{\\text{Integration of functionalized groups}}{\\text{Total polymer group integration (before/after modification)}} \\times 100\n       \\]\n       For example, if the hydroxyl or amine group on the polymer backbone was targeted, a reduction in hydroxyl/amine signals and an increase in methacrylate signals can be correlated.\n\n##### **B. Fourier Transform Infrared (FTIR) Spectroscopy**\n   - **Objective:** Identify functional groups that appear (e.g., ester groups from MA) or disappear (e.g., hydroxyl groups modified during the reaction) by comparing IR spectra of the unmodified and modified polymer.\n   - **Experimental Process:**\n     1. Prepare polymer samples before and after functionalization.\n     2. Record FTIR spectra in the appropriate range (e.g., 4000\u2013400 cm\u207b\u00b9).\n     3. Identify new bands corresponding to methacrylic functional groups (characteristic C=O stretching around 1720 cm\u207b\u00b9, C=C stretching around 1650 cm\u207b\u00b9) and track the depletion of unmodified groups like hydroxyl stretching (O-H at \u223c3300 cm\u207b\u00b9).\n   - **Calculation:**\n     - Use peak intensities to semi-quantitatively estimate the degree of functionalization. FTIR is less accurate for detailed DoF calculations but can serve as a good complementary tool.\n\n##### **C. Mass Spectrometry (if necessary)**\n   - Measure the molecular weight change before and after functionalization using tools such as MALDI-TOF or ESI-MS.\n   - This is most useful for low molecular weight polymers or oligomers.\n\n---\n\n#### **Step 2: Direct Titration Method**\nIf the polymer contains reactive functional groups such as hydroxyl or amine groups, titration can provide direct quantitative data on DoF.\n\n##### **Experimental Procedure:**\n1. **Unmodified Polymer Titration**:\n   - Dissolve the unmodified polymer in a solvent (e.g., water or ethanol, depending on solubility).\n   - React the polymer with a titrant that reacts with the functional group (e.g., strong acid for hydroxyl or amine groups) and measure the consumption of titrant.\n\n2. **Modified Polymer Titration**:\n   - Repeat the titration with the modified polymer to measure how many residual functional groups remain unreacted.\n\n##### **Calculation:**\n   - Assuming methacrylic anhydride reacts in a 1:1 molar ratio with the functional group, the DoF is determined as:\n     \\[\n     \\text{DoF} = \\frac{\\text{Moles of modified functional groups}}{\\text{Moles of total functional groups (initially present)}} \\times 100\n     \\]\n     Here, \"moles of modified functional groups\" can be calculated by the difference in titration results before and after functionalization.\n\n---\n\n#### **Step 3: Experimental Controls**\n1. **Run blank experiments with unmodified polymer** to validate baseline characterization data.\n2. Ensure reaction completion by optimizing reaction parameters such as time, temperature, solvent, and catalyst (e.g., pyridine for MA-functionalization of hydroxyl-containing polymers).\n\n---\n\n### **Detailed Example Calculation**\nAssume the polymer starts with 1.00 mmol hydroxyl groups and after reaction with methacrylic anhydride, NMR analysis shows integration values corresponding to 0.80 mmol modified methacrylic groups.\n\n- **DoF Calculation:**\n  \\[\n  \\text{DoF} = \\frac{\\text{0.80 mmol}}{\\text{1.00 mmol}} \\times 100 = 80\\%\n  \\]\n\n---\n\n### **Practical Notes and Additional Tips**\n1. **Optimize reaction conditions**: Methacrylic anhydride functionalization might require mild conditions to avoid polymer degradation (e.g., reaction temperatures of 25\u201350\u00b0C, mild catalysts like pyridine, and solvents like DMSO or dichloromethane).\n2. **Monitor the reaction progress**: Use real-time NMR or FTIR spectroscopy data to confirm when the reaction reaches completion.\n3. **Repeat trials** for reproducibility and statistically evaluate surface or bulk functionalization (if applicable).\n\nBy following these steps, the student should be able to determine the DoF with adequate precision and understand the various dynamics involved in polymer functionalization."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the process of modifying a polymer using methacryloyl gelatin (GelMA). Specifically, outline how you would ensure the successful grafting of GelMA onto the polymer surface while maintaining its hydrophilic properties."}, {"role": "assistant", "content": "Certainly! Let's tackle this step by step to design a systematic preparation scheme for the modification of a polymer using methacryloyl gelatin (GelMA) while ensuring its hydrophilic properties are maintained. We'll analyze the question first and then delve into the detailed experimental steps, following the guidelines provided.\n\n---\n\n### **1. Analysis of the Question and Key Points**\nThe question revolves around the incorporation of methacryloyl gelatin (GelMA) onto a polymer surface. GelMA has hydrophilic properties due to the presence of gelatin and methacryloyl functional groups, and its grafting onto the polymer can enhance surface hydrophilicity. To ensure successful modification:\n- We need to confirm grafting occurs efficiently and preserves functionality.\n- We should optimize reaction conditions to ensure hydrophilic properties are enhanced.\n- A systematic experimental scheme must be developed with attention to reagent ratios, reaction conditions, and characterization.\n\n---\n\n### **2. Detailed Experimental Preparation Scheme**\n\nBelow is a step-by-step preparation method for grafting GelMA onto the polymer surface while maintaining its hydrophilic properties.\n\n---\n\n#### **Step 1: Preparation of Methacryloyl Gelatin (GelMA)**\nBefore we proceed to grafting, GelMA itself must be synthesized if not already available. Follow these steps:\n1. **Materials**: Gelatin, methacrylic anhydride (MA), phosphate-buffered saline (PBS), and reagents for purification (e.g., dialysis tubing).\n2. **Procedure**:\n   - Dissolve **gelatin** (e.g., Type A gelatin) in PBS at pH 7.4 under stirring at 50\u00b0C until fully dissolved (1\u201310 wt.% solution recommended).\n   - Slowly add **methacrylic anhydride** drop-wise (e.g., 10% volume/volume of methacrylic anhydride relative to the gelatin solution) under continuous stirring. Maintain the pH at 8.0 with NaOH (to avoid acidification of the gelatin solution).\n   - Stir at 50\u00b0C for 2 hours; the methacrylic anhydride reacts with amine groups on gelatin to form GelMA.\n   - Purify GelMA by dialysis against distilled water for 5\u20137 days to remove unreacted methacrylic anhydride and other impurities. Freeze-dry the solution to obtain GelMA powder.\n3. **Characterization**:\n   - Confirm the synthesis of GelMA using **proton nuclear magnetic resonance (\u00b9H NMR)** or **Fourier-transform infrared spectroscopy (FTIR)** to verify the presence of methacryloyl groups.\n\n---\n\n#### **Step 2: Activation of Polymer Surface**\nTo ensure GelMA can graft onto the polymer, the polymer surface must contain reactive groups (e.g., amine, carboxylic, or hydroxyl groups). Depending on the polymer type:\n1. **Materials**: Surface-activating agent (e.g., plasma treatment, UV activation, or chemical activation using carbodiimide chemistry).\n2. **Procedure**:\n   - If using a plasma treatment setup, expose the polymer surface to **oxygen plasma** for 1\u20135 minutes to introduce hydrophilic functional groups such as hydroxyl (-OH) or carboxylic (-COOH) groups.\n   - Alternatively, if using carbodiimide activation:\n     - Treat the surface with **1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC)** and **N-hydroxysuccinimide (NHS)** in aqueous conditions (pH 5.5\u20137.5). EDC will activate carboxylic groups on the polymer to create reactive esters for GelMA attachment.\n\n---\n\n#### **Step 3: Grafting GelMA Onto Polymer Surface**\nOnce the polymer surface is activated, GelMA can be grafted efficiently.\n1. **Materials**: GelMA solution, activated polymer, photoinitiator (e.g., Irgacure 2959 for UV curing or ammonium persulfate for redox curing).\n2. **Procedure**:\n   - Dissolve GelMA in deionized water or PBS to create a 10\u201320 wt.% solution at 37\u00b0C.\n   - Combine the polymer with the GelMA solution, immerse it in the GelMA solution, ensuring uniform coverage of the polymer surface.\n   - Add the appropriate **photoinitiator** (e.g., 0.1\u20130.5 wt.%) to the GelMA solution; this is necessary for photo-crosslinking at the methacryloyl groups.\n   - Subject the mixture to UV light (around 365 nm wavelength, 5\u201310 mW/cm\u00b2 intensity) or a thermal curing method (e.g., 60\u00b0C for 30 minutes) to initiate polymerization. This forms covalent bonds between GelMA and the surface.\n\n---\n\n#### **Step 4: Washing and Post-Treatment**\nRemove unbound GelMA and ensure quality grafting.\n1. **Procedure**:\n   - Wash the modified polymer thoroughly with distilled water or PBS to remove loosely bound GelMA or impurities that may affect hydrophilicity.\n   - Optionally, use gentle ultrasonic cleaning to enhance the washing process and prevent physical damage to the surface.\n\n---\n\n#### **Step 5: Characterization of Modified Polymer**\nAfter grafting, confirm GelMA attachment and evaluate hydrophilicity.\n1. **Surface Analysis**:\n   - Use **FTIR spectroscopy** to identify functional groups of GelMA on the polymer.\n   - Use **X-ray photoelectron spectroscopy (XPS)** or **atomic force microscopy (AFM)** for a detailed surface chemical analysis.\n2. **Hydrophilicity Assessment**:\n   - Measure the water contact angle of the polymer surface before and after modification. A lower water contact angle indicates improved hydrophilicity.\n   - Perform **swelling tests** in water or PBS to evaluate the hydrophilic nature.\n\n---\n\n### **3. Notes and Optimization Suggestions**\n1. Reaction **pH**, temperature, and initiator concentration must be optimized for successful GelMA grafting and polymerization.\n2. Ensure **sterility** if the modified polymer will be used for biological applications.\n3. Consider environmental factors like oxygen inhibition during photopolymerization and mitigate it by working in inert atmospheres (e.g., argon or nitrogen).\n\n---\n\n### **4. Summary**\nTo modify a polymer using GelMA:\n- Synthesize or procure GelMA with methacryloyl groups.\n- Activate the polymer surface to introduce reactive groups.\n- Utilize a crosslinking method (UV or chemical) to covalently bond GelMA to the polymer.\n- Characterize the grafted polymer, confirming functionality and hydrophilicity enhancements.\n\nThis systematic approach ensures successful grafting while retaining or enhancing the hydrophilic properties of the polymer.\n\n--- \n\nFeel free to discuss any points in detail!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Using ethylene glycol, propose a step-growth polymerization reaction that would allow the formation of a polymer with enhanced hydrophilicity. Ensure the monomer selection complies with the prerequisites for polymerizable functional groups."}, {"role": "assistant", "content": "Certainly! Let\u2019s systematically break down your question regarding the formation of a hydrophilic polymer using ethylene glycol and propose a comprehensive experimental preparation scheme based on step-growth polymerization principles. To meet your objectives, we will aim to enhance the polymer's hydrophilicity and provide detailed instructions for the synthesis.\n\n---\n\n### 1. **Analyze the question and summarize the key points:**\n   - **Objective:** Design a step-growth polymerization reaction using ethylene glycol to produce a hydrophilic polymer.\n   - **Key considerations:**\n     - Ethylene glycol is a diol (contains two hydroxyl groups, \u2013OH), making it suitable for step-growth polymerization.\n     - For step-growth polymerization, we need complementary monomers with functional groups that react with hydroxyl groups, such as diacids, diacyl chlorides, or their derivatives.\n     - The final polymer should exhibit enhanced hydrophilicity. Hydrophilicity can be improved by increasing the density of hydrophilic groups (-OH, -COOH, -C=O, amides, etc.) in the polymer backbone.\n   - **Chemistry involved:** Typical step-growth polymerization routes involve esterification or amidation reactions between diols and diacids (or diacid derivatives), or urethane reactions between diols and isocyanates.\n   - **Approach:** We will use ethylene glycol as the diol and pair it with a diacid containing hydrophilic groups.\n\n---\n\n### 2. **Propose the detailed synthesis process:**\n   We will design a copolymer of poly(ethylene glycol-co-succinate) using **ethylene glycol** and **succinic acid** as the monomers. Succinic acid (HOOC-(CH2)2-COOH) is chosen for its hydrophilic carboxylic acid groups and straightforward reactivity.\n\n---\n\n#### Step 1: Materials and reagent preparation\n   - **Monomer 1 (Diol):** Ethylene glycol (HOCH2CH2OH).\n   - **Monomer 2 (Diacid):** Succinic acid (HOOC-(CH2)2-COOH).\n   - **Catalyst:** Typically, a strong acid catalyst such as **p-toluenesulfonic acid (p-TSA)** or **sulfuric acid** is used for esterification.\n   - **Solvent (optional):** Xylene or toluene can be added to aid in azeotropic removal of water during the reaction.\n   - **Other equipment:** Dean-Stark apparatus (if using azeotropic water removal), reflux setup.\n\n---\n\n#### Step 2: Reaction schematic\nThe reaction involves the **esterification** of ethylene glycol and succinic acid to form an aliphatic polyester with hydrophilic ester linkages:\n\\[\nHOCH_2CH_2OH + HOOC-(CH_2)_2-COOH \\rightarrow [-CH_2CH_2-O-C(O)-(CH_2)_2-C(O)-]_n + nH_2O\n\\]\n\n---\n\n#### Step 3: Experimental setup and procedure\n1. **Reaction setup:**\n   - Assemble a round-bottom flask with a reflux condenser and a Dean-Stark trap (if using azeotropic water removal) to eliminate the water formed during the reaction.\n   - Add a magnetic stir bar to the flask for mixing.\n   - Preheat the flask in an oil bath to maintain a temperature of 140\u2013180 \u00b0C throughout the reaction.\n\n2. **Molar ratios of reactants:**\n   - Take ethylene glycol and succinic acid in a 1.1:1 molar ratio. For example:\n     - Ethylene glycol: 110 mmol (6.8 g, MW = 62.07 g/mol).\n     - Succinic acid: 100 mmol (11.8 g, MW = 118.09 g/mol).\n   - The slight excess of ethylene glycol ensures the complete reaction of the diacid, minimizing unreacted acid groups.\n\n3. **Catalyst addition:**\n   - Add 0.5\u20131 wt% (relative to the total mass of reactants) of p-toluenesulfonic acid (p-TSA) as the catalyst. Alternatively, a few drops of concentrated sulfuric acid can be used.\n\n4. **Heating and monitoring:**\n   - Heat the reaction mixture to 140\u2013180 \u00b0C under reflux with vigorous stirring.\n   - As the reaction proceeds, water is produced as a byproduct. Using a Dean-Stark apparatus, collect and remove water from the system to shift the equilibrium toward polyester formation.\n\n5. **Reaction duration:**\n   - Continue heating for 4\u20136 hours or until water formation ceases, indicating the completion of esterification.\n\n6. **Optional purification:**\n   - Cool the reaction mixture to room temperature. Dissolve the crude polymer in a minimal amount of dichloromethane (CH2Cl2) and precipitate it into cold methanol to purify the polymer. Collect the polymer by filtration and allow it to dry under vacuum.\n\n---\n\n#### Step 4: Expected results and hydrophilicity enhancement\n- **Polymer formed:** Poly(ethylene glycol-co-succinate), an aliphatic polyester containing hydrophilic ester groups (-C=O and -O).\n- **Hydrophilic character:** The incorporation of multiple ester linkages significantly enhances the hydrophilicity of the polymer compared to a purely aliphatic hydrocarbon chain polymer.\n\n---\n\n#### Step 5: Safety considerations\n1. Ensure proper ventilation when heating (e.g., using a fume hood) to prevent exposure to toxic vapors.\n2. Handle acids and organic solvents with care to avoid burns or inhalation hazards\u2014use nitrile gloves and safety goggles.\n\n---\n\n### Final Summary of the Experimental Scheme\n- **Reactants:** Ethylene glycol and succinic acid in a 1.1:1 molar ratio.\n- **Catalyst:** p-TSA (0.5\u20131 wt%) or sulfuric acid.\n- **Temperature:** 140\u2013180 \u00b0C under reflux.\n- **Reaction time:** 4\u20136 hours with water removal.\n- **Purification:** Precipitation into methanol.\n- **Product:** A hydrophilic polyester with ester linkages.\n\nThis systematic approach ensures that you achieve a polymer with enhanced hydrophilicity while providing a reliable experimental scheme for laboratory practice. Let me know if you have further questions or need a refinement of this scheme!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain how the molecule I-819 can be used to facilitate the synthesis of a hydrophilic polymer and what its specific function is during the experimental process."}, {"role": "assistant", "content": "To answer your question step-by-step, let us carefully analyze your question, identify the key points, and systematically explore how the molecule I-819 can be utilized to synthesize a hydrophilic polymer while discussing its specific function in the experimental process. Since we aim for a methodical explanation that you can practically apply in the laboratory, let me follow the rigorous scientific approach required as per your request.\n\n---\n\n### **Step 1: Analyzing the Question**\n- **Key Points to Understand:**\n  1. **Molecule I-819** and its functional role in facilitating the synthesis of a hydrophilic polymer.\n  2. The focus on **enhancing hydrophilicity** of the synthesized polymer.\n  3. Understanding the **reaction mechanism** or pathway by which I-819 contributes to the polymerization process.\n\n- **Important Contextual Considerations:**\n  - Once I-819's chemical nature is clear (likely a photoinitiator or crosslinking agent based on its molecular designation), we can determine how it participates in the experimental preparation. \n  - Hydrophilic polymers often involve incorporation of hydrophilic functional groups either into the monomer(s) or through modification of the polymer backbone.\n\n---\n\n### **Step 2: Understanding Molecule I-819**\n- Molecule I-819 is known as a **highly efficient photoinitiator**. This means it can absorb light and produce reactive species (e.g., free radicals) to initiate polymerization.\n- In the context of hydrophilic polymer synthesis, I-819 likely serves to initiate **free radical polymerization** of hydrophilic monomers (like acrylamide, acrylic acid, or polyethylene glycol derivatives). These monomers polymerize to form chains with hydrophilic properties.\n\n---\n\n### **Step 3: Designing the Experimental Preparation Sequence**\n\nLet us construct a detailed experimental protocol for synthesizing a hydrophilic polymer using I-819 to initiate polymerization. For clarity, I will break this down into steps.\n\n---\n\n#### **Step 3.1: Selection of Hydrophilic Monomers**\n- Choose appropriate monomers that contain **hydrophilic pendant groups**. Common choices include:\n  1. **Acrylamide (AM):** Offers -CONH2 groups for strong hydrophilicity.\n  2. **Acrylic Acid (AA):** Provides -COOH groups, enhancing water solubility.\n  3. **Polyethylene glycol methacrylate (PEG-MA):** Introduces hydroxyl (-OH) functionality, excellent for biocompatibility.\n- The choice of monomers can be tailored depending on whether you aim for nonionic, anionic, or neutral hydrophilicity.\n\n---\n\n#### **Step 3.2: Preparing the Reaction Mixture**\n1. **Weighing the Monomers:**\n   - Decide on specific molar ratios of monomers to achieve the desired hydrophilic balance. For example, blend **Acrylamide (5 g, 70 mol%)** with **Acrylic Acid (2.2 g, 30 mol%)** for copolymer synthesis.\n   \n2. **Dissolving Monomers:**\n   - Dissolve the monomers in **deoxygenated water** or a suitable solvent (e.g., DMSO if water solubility of some components is an issue). Ensure thorough mixing.\n\n3. **Adding Crosslinker (if required):**\n   - Add a crosslinking agent, e.g., **N,N'-methylenebisacrylamide (MBA)**, if you aim for a 3D network structure (e.g., hydrogels). Use ~0.5\u20131 wt% relative to the total monomer weight. \n\n4. **Incorporating the Initiator:**\n   - Add **I-819** into the reaction mixture. Optimal concentration is ~0.1\u20131 wt% relative to the monomer content.\n   - Ensure uniform mixing, as I-819 must be homogeneously distributed to ensure consistent radical generation during polymerization.\n\n---\n\n#### **Step 3.3: Polymerization Process**\n1. **Photopolymerization Setup:**\n   - Transfer the reaction mixture to a clean polymerization vessel (quartz or UV-transparent glass is ideal). Nitrogen purging is essential to remove residual oxygen during free-radical polymerization.\n\n2. **Light Source Selection:**\n   - Choose a UV lamp or LED source emitting at a wavelength compatible with the absorption range of I-819 (~365 nm for typical use). Adjust the light intensity to ~5\u201310 mW/cm\u00b2.\n\n3. **Reaction Conditions:**\n   - Expose the mixture to UV light for **10\u201330 minutes**. Maintain constant temperature (~25\u201340\u00b0C, depending on the monomers) to avoid thermal side reactions.\n\n4. **Polymer Formation:**\n   - I-819 absorbs UV light, generating radicals that attack the double bonds of the monomers, initiating chain propagation. The reaction continues until most monomers are consumed, yielding the desired hydrophilic polymer.\n\n---\n\n#### **Step 3.4: Post-Processing**\n1. **Purification:**\n   - Wash the polymer with water or ethanol to remove unreacted monomers and photoinitiator residues.\n   \n2. **Drying:**\n   - Dry the purified polymer under vacuum at ~40\u201350\u00b0C to avoid degradation of hydrophilic segments.\n\n3. **Characterization:**\n   - Characterize the polymer\u2019s hydrophilicity using tests such as:\n     - **Water absorption capacity** or swelling ratio (for hydrogels).\n     - **Contact angle measurement** to quantify surface hydrophilicity.\n     - **FTIR analysis** to confirm the presence of hydrophilic functional groups.\n\n---\n\n### **Step 4: Specific Role of I-819 in the Experimental Process**\n- As a **photoinitiator**, I-819 facilitates:\n  1. **Radical Generation Under UV Light:** Absorbs UV radiation and decomposes to produce radicals that initiate polymerization.\n  2. **Control of Polymerization Rate:** Allows precise control by adjusting UV exposure time and intensity.\n  3. **Minimized Thermal Side Effects:** Being a photoinitiator, it avoids harsh thermal conditions that could degrade hydrophilic groups.\n\nI-819 is particularly advantageous due to its **low light absorption threshold, excellent radical efficiency**, and ability to function well in aqueous/largely hydrophilic systems.\n\n---\n\n### **Step 5: Final Remarks and Suggestions**\n- I-819 is a versatile and efficient tool for synthesizing hydrophilic polymers under mild conditions. However, consistent handling of UV exposure and maintaining a deoxygenated atmosphere are critical to ensure efficiency.\n- When scaling this to the lab, ensure meticulous adherence to reagent ratios and reaction conditions. This will result in polymers with reproducible and robust hydrophilic properties.\n\n--- \n\nIf you have further questions regarding this approach, alternative monomers, or post-functionalization to enhance hydrophilicity, feel free to ask!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain how you would evaluate the effectiveness of a molecule in reducing condensation and fogging on the surface of the polymer after modifying it. What tests or measurements would you implement to confirm the hydrophilicity enhancement?"}, {"role": "assistant", "content": "Certainly, let's approach this question step by step, analyzing it thoroughly to ensure clarity and completeness. To evaluate the effectiveness of a molecule in reducing condensation and fogging on the surface of a polymer after modification, and subsequently confirm hydrophilicity enhancement, several systematic tests and measurements can be implemented. I'll provide a detailed procedure below.\n\n---\n\n### Step 1: **Key Considerations and Context Analysis**\nBefore designing the experimental evaluation scheme, the following aspects must be clarified and emphasized:\n1. **Objective**: Assess whether the modification enhances the hydrophilicity of the polymer and effectively reduces condensation and fogging.\n2. **Target Property**: Hydrophilicity should be quantified through measurable parameters, such as water contact angle, surface energy, or anti-fogging performance.\n3. **Practical Applicability**: The polymer's performance must be tested under realistic conditions (e.g., environments that mimic condensation or fogging scenarios).\n4. **Test Methods**: A combination of qualitative (visual) and quantitative (scientific) methods should be used.\n\n---\n\n### Step 2: **Experimental Design for Evaluation**\nTo systematically evaluate the effectiveness of the modified polymer, follow these experimental steps:\n\n#### A. **Surface Hydrophilicity Measurement**\nThe hydrophilicity of the polymer surface can be quantitatively assessed using the water contact angle test.\n\n1. **Apparatus**: Use a **goniometer** to measure the water contact angle on the polymer surface.\n2. **Procedure**:\n    - Place a water droplet (typically ~3\u20135 \u03bcL) on the polymer surface.\n    - Measure the contact angle formed between the baseline of the droplet and the tangent at the droplet contour using the goniometer.\n3. **Expected Results**:\n    - A reduction in the water contact angle indicates improved hydrophilicity. For hydrophilic polymers, the contact angle should ideally be <50\u00b0, with values closer to ~10\u00b0 denoting excellent hydrophilicity.\n4. **Repetition**:\n    - Perform measurements at multiple points on the polymer surface to confirm uniform hydrophilicity after modification.\n    - Average the gathered contact angle data to reduce variability.\n\n#### B. **Anti-Fogging Performance Test**\nEvaluate the polymer\u2019s effectiveness in reducing fogging under controlled environmental conditions.\n\n1. **Apparatus**:\n    - **Fog chamber** or a controlled humidity chamber that simulates condensation conditions.\n    - Heating and cooling equipment to alternate between temperature gradients.\n2. **Procedure**:\n    - Place the polymer sample inside the fog chamber.\n    - Introduce humid air or water vapor to stimulate fog formation.\n    - Cycle the temperature to create a condensation scenario (e.g., cooling the surface rapidly under high humidity).\n    - Observe fog formation visually.\n3. **Qualitative Criteria**:\n    - Observe if the modified polymer remains clear or becomes foggy during condensation. Hydrophilic surfaces spread water droplets into thin films, preventing fogging.\n4. **Quantitative Measurement**:\n    - Use **transmittance spectroscopy** to compare light transmission before and after condensation. A highly hydrophilic surface should maintain high transmittance (close to ~90%) even under fogging conditions.\n\n#### C. **Surface Energy Analysis**\nQuantify the surface energy to corroborate hydrophilicity enhancement.\n\n1. **Methods**:\n    - Employ **contact angle measurements** of multiple liquids with varying polarities (e.g., water, ethylene glycol, diiodomethane).\n    - Use the equations from the **sessile drop method** or the **Owens-Wendt model** to calculate the surface energy.\n2. **Expected Results**:\n    - Hydrophilic surfaces exhibit higher polar surface energy (dominated by high polarity components), which indicates improved interaction with water molecules.\n\n#### D. **Durability Testing of Hydrophilicity**\nEvaluate the longevity of the hydrophilic properties to ensure stable performance.\n\n1. **Tests**:\n    - Subject the polymer to repeated fog formation and wiping cycles (mechanical durability).\n    - Expose the polymer to UV light or temperature fluctuations to test chemical stability.\n2. **Criteria**:\n    - Consistent performance in condensation/fogging tests and unchanged water contact angle post-testing indicates durable hydrophilicity.\n\n#### E. **Chemical Characterization**\nIf surface modifications involve molecular or structural changes, confirm the presence of functional groups responsible for hydrophilicity enhancement.\n\n1. **Methods**:\n    - **FTIR spectroscopy**: Confirm characteristic functional groups such as hydroxyl (-OH) or amine (-NH2) groups added during modification.\n    - **XPS (X-ray photoelectron spectroscopy)**: Analyze surface elemental composition and confirm incorporation of hydrophilic components.\n2. **Criteria**:\n    - The appearance of hydrophilic functional groups (e.g., -OH peaks at ~3300 cm\u207b\u00b9 in FTIR) demonstrates successful modification.\n\n---\n\n### Step 3: **Systematic Data Analysis**\nAfter conducting the outlined experiments, analyze the gathered data for clear insights:\n1. **Compare Pre- and Post-Modification Results**: Determine the reduction in contact angle, improvement in anti-fogging performance, and increase in surface energy.\n2. **Correlate Observations**: Relate visual results (e.g., fog formation) with quantitative metrics (contact angle, transmittance percentage).\n3. **Confirm Consistency**: Ensure all metrics point toward improved hydrophilicity. Any discrepancies should be investigated (e.g., uneven modification distribution).\n\n---\n\n### Step 4: **Conclusion and Practical Recommendations**\nIf the polymer successfully meets the criteria above:\n- **Hydrophilicity Confirmation**: Reduced contact angle, higher surface energy, and effective anti-fogging behavior validate the molecule\u2019s effectiveness.\n- **Application Advice**: Recommend optimized synthesis and surface modification techniques for scaling production in future applications.\n\nIf the results show insufficient enhancement:\n- Suggest further optimization of the surface modification process, such as increasing the functional group density, altering reaction conditions, or trying additional hydrophilic compounds.\n\n---\n\nBy following this systematic experimental plan, both qualitative and quantitative evaluations will provide robust proof of hydrophilicity enhancement and anti-fogging effectiveness. This ensures a scientific, logical, and precise approach for assessing the polymer\u2019s performance."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "If plasma surface cleaning is required before applying the molecule VCN L1-B, explain the role and importance of the plasma cleaning process in ensuring effective hydrophilic modification of the polymer material."}, {"role": "assistant", "content": "Let's think through your question step by step to provide a thorough and detailed explanation of the role and importance of plasma surface cleaning before applying the molecule VCN L1-B as part of a hydrophilic polymer synthesis process. Throughout this process, I'll also explain its relevance to ensuring effective hydrophilic modification of the polymer material.\n\n---\n\n### Step 1: Analyze the Question and Summarize Key Points\nFrom your question, we need to focus on the following:\n1. **The role of plasma surface cleaning:** Why it is used as a preparatory step before applying VCN L1-B.\n2. **The importance of plasma surface cleaning in hydrophilic modification:** How it enhances the polymer surface's ability to undergo hydrophilic modification effectively.\n\nThese points suggest that the key issue is the preparation of the polymer surface to ensure optimal interaction or bonding with the hydrophilic molecule VCN L1-B for effective modification.\n\n---\n\n### Step 2: Answer the Question in Detail and Systematically\n\n#### **2.1. Overview of Plasma Cleaning in Surface Preparation**\nPlasma surface cleaning is a physical and chemical technique that uses a low-pressure gas plasma to modify the surface properties of materials. It is particularly effective for polymers because it:\n- Removes surface contaminants, such as oils, dust, organic residues, and weakly bound materials.\n- Physically activates the surface by introducing functional groups (e.g., hydroxyl -OH, carboxyl -COOH, or amine -NH2 groups) that improve surface reactivity.\n- Enhances the wettability and adhesion properties of the surface. This is critical for hydrophilic modifications.\n\nTypically, plasma cleaning is performed under vacuum conditions using a selected inert, oxygen, or argon gas. The plasma is generated by applying a high-frequency electric field, which ionizes the gas and creates a high-energy plasma environment.\n\n#### **2.2. Role of Plasma Surface Cleaning for VCN L1-B Application**\nBefore applying VCN L1-B to modify a polymer material for hydrophilicity, the plasma cleaning process plays several critical roles:\n\n1. **Surface Contaminant Removal:**\n   - Organic pollutants (e.g., oils or residual monomers) and atmospheric contaminants can block the binding sites on the polymer surface.\n   - Plasma cleaning removes these contaminants effectively, exposing a clean polymer surface for subsequent reactions with VCN L1-B.\n\n2. **Surface Activation:**\n   - Plasma treatment chemically activates the polymer surface by embedding hydrophilic functional groups (e.g., -OH or COOH), boosting reactivity with the functional groups on VCN L1-B.\n   - For example, certain polymers such as polypropylene or polyethylene that are inherently hydrophobic can be functionalized with oxygen-bearing groups during plasma treatment using oxygen plasma.\n\n3. **Improved Adhesion and Bonding:**\n   - The cleaning process improves molecular-level adhesion by creating an ideal interfacing environment. Hydrophilic molecules like VCN L1-B often require clean, active surfaces to anchor effectively through covalent or non-covalent interactions.\n   - A poorly prepared surface may result in weak or uneven attachment of VCN L1-B, drastically affecting the hydrophilic properties of the final product.\n\n4. **Even Distribution and Wettability Enhancement:**\n   - Plasma treatment increases surface energy, ensuring that VCN L1-B can spread and form a uniform coating on the polymer. This uniformity translates to consistent hydrophilic properties across the material surface.\n\n#### **2.3. Experimental Protocol for Plasma Cleaning**\nTo assist in successfully performing this step in the laboratory, let me outline a detailed experimental protocol for plasma surface cleaning before applying VCN L1-B:\n\n1. **Equipment Required:**\n   - Plasma cleaner (depending on lab availability, you might use low-pressure plasma or atmospheric-pressure plasma systems).\n   - Inert or reactive gas supply (e.g., Ar for inert cleaning, O\u2082 for oxidative cleaning).\n\n2. **Procedure:**\n   - **Step 1: Polymer Sample Placement:**\n     - Cut the polymer sample to the desired dimensions and ensure it is free from any visible macroscopic contaminants (e.g., dust or large particles). Place it in the plasma chamber.\n   - **Step 2: Chamber Evacuation:**\n     - Evacuate the chamber to a base pressure of 0.1\u20131 Torr to ensure minimal contamination during treatment.\n   - **Step 3: Gas Introduction:**\n     - Introduce the chosen plasma gas (e.g., oxygen gas for oxidative cleaning) at a steady flow rate. Maintain pressure in the range of ~0.2\u20130.5 Torr.\n   - **Step 4: Plasma Generation:**\n     - Activate the plasma by applying RF power (e.g., 13.56 MHz) at an appropriate power level (~50\u2013200 W, depending on sample size and desired cleaning intensity).\n     - Treat the polymer surface for approximately 5\u201315 minutes. The exact time depends on the polymer type and the level of contamination.\n\n3. **Post-Treatment Verification:**\n   - After plasma cleaning, verify the surface modification using techniques such as:\n     - **Contact Angle Measurement:** Ensure the treated surface has improved wettability (lower contact angle indicates greater hydrophilicity).\n     - **Fourier Transform Infrared Spectroscopy (FTIR):** Detect newly formed oxygen-containing groups on the polymer.\n     - **Surface Energy Analysis:** Quantify the increase in surface energy due to plasma treatment.\n\n4. **Storage Before Application of VCN L1-B:**\n   - If VCN L1-B application is not immediate, store the cleaned polymer material in a vacuum or inert atmosphere. Exposure to air can result in contamination or aging of the activated surface.\n\n#### **2.4. Importance of Plasma Cleaning in Hydrophilic Modification**\nWithout plasma surface cleaning, the effectiveness of hydrophilic modification using VCN L1-B may be significantly compromised. Problems that could arise include:\n- Inconsistent or poor bonding of VCN L1-B to the polymer substrate.\n- Non-uniform distribution of hydrophilic properties across the polymer surface.\n- Reduced durability and stability of the hydrophilic coating in aqueous environments.\n\nIn contrast, by using plasma cleaning to prepare the polymer surface, the reaction kinetics between VCN L1-B and the surface are greatly enhanced. This step leads to a more robust hydrophilic layer with improved functionality and longevity, ensuring the desired performance of the hydrophilic polymer.\n\n---\n\n### Final Thoughts:\nPlasma surface cleaning is an indispensable preparatory step when producing hydrophilic polymers with VCN L1-B. Its role in removing contaminants, activating the polymer surface, and preparing the substrate for seamless interaction with the hydrophilic molecule is pivotal. By following the detailed procedure and understanding the science behind this process, you will ensure a successful outcome in hydrophilic polymer synthesis experiments in the lab."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain the reasoning behind setting specific temperature and UV curing energy parameters during the molecule application process, and how these factors contribute to achieving enhanced hydrophilicity in the modified polymer."}, {"role": "assistant", "content": "Certainly! Let us approach your question step-by-step to fully explore the reasoning behind setting specific *temperature* and *UV curing energy* parameters during the modification of the polymer to enhance its hydrophilicity. Please follow along sequentially as we analyze the key factors at play, establish the practical rationale for these parameters, and relate them to the molecular mechanisms driving hydrophilicity.\n\n---\n\n### **1. Analysis of the Question and Key Points**\nThe question focuses on two critical process factors during the polymer modification for enhanced hydrophilicity:\n- **Temperature:** Why is a specific temperature range chosen during the synthesis or application of the polymer?\n- **UV Curing Energy:** How does the intensity and duration of UV exposure improve hydrophilicity?\n\nTo properly answer this, we need to:\n- Examine the molecular interactions between the functional species (e.g., hydrophilic monomers, oligomers, or additives) and the parent polymer.\n- Consider how temperature affects reaction kinetics, polymer cross-linking, and functional group mobility.\n- Understand the role of UV curing in initiating chemical reactions, stabilizing hydrophilic functionalities, polymerizing or cross-linking species, and minimizing undesired side reactions.\n\n---\n\n### **2. Step-by-Step Explanation**\n\n#### **Step 1: Setting the Specific Temperature Range**\n**Why is temperature important?**  \nIn the preparation of hydrophilic polymers, temperature directly impacts:\n1. **Reaction Kinetics:** Higher temperatures accelerate the polymerization or grafting reaction of hydrophilic monomers onto the polymer backbone by:\n   - Increasing the energy of molecular collisions.\n   - Reducing the activation energy needed for bond formation.\n2. **Diffusion and Incorporation:** Many hydrophilic functional groups (e.g., -OH, -NH2, -COOH) are relatively polar. At elevated temperatures, monomers or reagents have improved diffusion into the polymer matrix, promoting better surface wetting and incorporation.\n3. **Avoiding Degradation:** The temperature must not be so high as to cause the degradation or thermal decomposition of either the polymer backbone or functional groups.\n\n**Typical temperature considerations:**\n- Common hydrophilic monomers such as acrylic acid (AA), hydroxyethyl methacrylate (HEMA), or polyethylene glycol (PEG) derivatives polymerize effectively in the range of **60\u201380\u00b0C** in the presence of free-radical initiators (e.g., azobisisobutyronitrile, AIBN) or **40\u201360\u00b0C** with redox initiator systems.\n- For polymers susceptible to temperature degradation (e.g., hydrogels, proteins, or naturally derived polymers like gelatin), lower temperatures (even as low as 30\u201340\u00b0C) may be used.\n- Temperatures in the curing stage ensure effective volatilization of water or solvents, promoting strong adherence and uniform functionalization.\n\n**Optimal temperature settings:**\n- Determine experimentally by thermal analysis (e.g., thermogravimetric analysis, TGA) to pinpoint the range where the polymer remains stable and hydrophilic functionalization proceeds efficiently.\n\n---\n\n#### **Step 2: Setting the UV Curing Energy Parameters**\n**How does UV curing promote hydrophilicity?**  \nUV curing introduces functionality into the polymer matrix by initiating specific photochemical reactions. This process depends on UV wavelength, intensity, and exposure duration. Key mechanisms are:\n\n1. **Photoinitiation of Polymerization:**\n   - UV light triggers the decomposition of photoinitiators (e.g., benzophenone, Irgacure species) into reactive radicals.\n   - These radicals initiate chain reactions, leading to polymerization of hydrophilic precursor monomers or grafting of functional species onto the polymer backbone.\n   - For optimal curing, wavelengths of **300\u2013365 nm (near UV-A region)** are typical for activating most photoinitiators.\n\n2. **Formation of Hydrophilic Structures:**\n   - UV-generated radicals can directly form hydrophilic moieties such as -COOH (carboxyl) or -OH (hydroxyl) groups on the polymer surface by photooxidation reactions.\n   - This enhances surface energy, boosting the affinity for water molecules.\n\n3. **Cross-linking of Hydrophilic Components:**\n   - UV curing can stabilize hydrophilic functionality by forming a 3D network of cross-linked polymer chains, locking the hydrophilic groups into place and ensuring chemical stability in aqueous environments.\n\n4. **Optimizing UV Energy Parameters:**\n   - **Low UV energy (insufficient):** May lead to incomplete curing, leaving residual unreacted species or unbound hydrophilic groups.\n   - **Excess UV energy/intensity:** Can cause chain scission and degrade either the hydrophilic components or the polymer backbone, reducing performance.\n   - **Controlled Parameters:**\n     - Wavelength: ~300\u2013365 nm (activation of most typical photoinitiators).\n     - Intensity: ~100\u2013150 mW/cm\u00b2 (commonly sufficient for monomer cross-linking without degradation).\n     - Exposure time: Often optimized by experimentation, e.g., **30\u2013120 seconds**.\n\n---\n\n#### **Step 3: How These Factors Work Together to Enhance Hydrophilicity**\nThe interplay of temperature and UV curing determines the final hydrophilic properties of the polymer. Their mechanisms and contributions are summarized below:\n\n1. **Enhanced Incorporation of Hydrophilic Groups:**\n   - Temperature improves the diffusion and reaction kinetics of the hydrophilic monomers and functional groups, increasing the density of hydrophilic moieties on the polymer surface.\n   - UV curing ensures stable chemical bonding of these groups within the polymer matrix by initiating polymerization or photo-cross-linking.\n\n2. **Optimal Surface Modification:**\n   - Temperature promotes uniform interaction between the hydrophilic reagents and the polymer substrate.\n   - UV energy drives surface-specific reactions, ensuring the hydrophilic modification is localized near the polymer-water interface, enhancing water wettability and compatibility.\n\n3. **Long-Term Stability of Hydrophilic Surface:**\n   - Cross-linking at appropriate UV curing energy prevents leaching of hydrophilic agents in aqueous media, maintaining the hydrophilicity over time.\n\n---\n\n### **3. Summary**\nTo enhance hydrophilicity in a modified polymer:\n1. Set a specific **temperature range** suitable for hydrophilic monomer reactions, balancing reaction kinetics and polymer stability (e.g., **60\u201380\u00b0C** for free-radical polymerization or lower for sensitive systems).\n2. Optimize **UV curing energy parameters** to polymerize and/or cross-link hydrophilic functionalities without causing degradation (e.g., **300\u2013365 nm wavelength**, **100\u2013150 mW/cm\u00b2 intensity**, **30\u2013120 s exposure time**).\n3. Ensure these conditions promote uniform diffusion, bonding, and stabilization of hydrophilic groups, enabling both enhanced hydrophilicity and long-term stability.\n\nBy properly tuning both factors, you can control the functionality and performance of the final hydrophilic polymer in real-world applications.\n\nWould you like me to draft a specific experimental procedure for applying these principles?"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the process of using a polymerization reaction template to incorporate the molecule into a polymer structure in order to improve its hydrophilicity. Highlight any considerations specific to this molecule."}, {"role": "assistant", "content": "To systematically address your question regarding incorporating the molecule into a polymer structure via a polymerization reaction template to enhance hydrophilicity, allow me first to analyze the key aspects of your question and then design an experimental preparation scheme accordingly.\n\n---\n\n### **Analysis of Your Question**\n1. **Goal:**  \n   The objective is to integrate the provided molecule into a polymer structure to improve hydrophilicity. This involves leveraging functional groups in the molecule that contribute to hydrophilicity, such as hydroxyl (-OH), amine (-NH2), carboxyl (-COOH), or other polar groups.\n\n2. **Polymerization Reaction Template:**  \n   We need to select an appropriate polymerization method (e.g., free radical polymerization, condensation polymerization, or controlled/living polymerization) suited to the molecule and its functional groups.\n\n3. **Key Considerations:**  \n   Specific strategies will depend on the chemical structure of the molecule you provided, including:\n   - Whether the molecule serves as a monomer or requires functionalization.\n   - The compatibility of its functional groups with the polymer backbone.\n   - Reaction conditions to preserve the integrity of hydrophilic groups.\n\n4. **Output:**  \n   The synthesized polymer must exhibit enhanced hydrophilicity, which may be tested by water absorption, contact angle measurements, or dissolution behavior in aqueous environments.\n\n---\n\n### **Experimental Synthesis Scheme**\n\nBelow, I'll outline a detailed and systematic synthesis protocol for preparing a hydrophilic polymer while incorporating your molecule into the polymer structure. This procedure can be tailored depending on the exact chemical structure of the molecule you provided.\n\n#### **Step 1: Selection of Polymerization Method**\nBased on the functional groups in the molecule:\n- **Free Radical Polymerization** is suitable if the molecule contains unsaturation like a vinyl group (-CH=CH2).\n- **Condensation Polymerization** works well for molecules with carboxylic acids (-COOH), hydroxyl groups (-OH), or amines (-NH2).\n- **Ring-Opening Polymerization** may be chosen for cyclic molecules capable of hydrolysis.\n\nGiven the emphasis on hydrophilicity, monomers like acrylic acid, acrylamide, or their derivatives might be used.\n\n---\n\n#### **Step 2: Molecular Incorporation**\nIf the provided molecule does not possess reactive polymerizable groups, we may need to functionalize it, preparing it as a co-monomer. For instance:\n- **Functionalization Strategy:** Add polymerizable groups like methacrylate or acrylate by esterification or amidation reactions.\nExample:\n   - To functionalize a molecule with a hydroxyl (-OH) group:\n     - React it with methacrylic acid via esterification using a catalyst like dicyclohexylcarbodiimide (DCC) or 4-dimethylaminopyridine (DMAP).\n\n---\n\n#### **Step 3: Polymerization Reaction**\n**Reaction Type:**  \nLet\u2019s proceed step-by-step for free radical polymerization:\n\n1. **Reagents:**\n   - Monomer: Acrylic acid (hydrophilic base polymer).\n   - Co-monomer: Functionalized molecule.\n   - Initiator: Azobisisobutyronitrile (AIBN) or potassium persulfate (KPS).\n   - Solvent: Water or ethanol (to favor hydrophilicity).\n\n2. **Preparation:**\n   - **Molar Ratios:**  \n     A typical ratio for a copolymer is 1 mole of acrylic acid to 0.1\u20130.3 mole of functionalized co-monomer. Adjust based on desired hydrophilicity and molecular weight.\n\n3. **Reaction Conditions:**\n   - Temperature: 60\u201370 \u00b0C (optimal for AIBN decomposition).\n   - Atmosphere: Nitrogen to prevent oxidative deterioration.\n   - Time: 4\u20136 hours (ensures high conversion).\n\n4. **Procedure:**\n   - Dissolve the monomer and co-monomer in the solvent.\n   - Add the initiator under stirring.\n   - Heat the reaction mixture while maintaining nitrogen flow.\n   - Monitor viscosity changes as polymerization progresses.\n\n---\n\n#### **Step 4: Post-Polymerization Processing**\n1. **Purification:**\n   - Precipitate the polymer in a non-solvent like methanol or acetone.\n   - Filter and wash thoroughly to remove unreacted monomers.\n\n2. **Drying:**\n   - Dry the polymer under vacuum at 40\u201350 \u00b0C to avoid thermal degradation.\n\n---\n\n#### **Step 5: Characterization of Hydrophilicity**\n1. **Water Absorption:**\n   - Soak the polymer in water and measure the percentage increase in mass.\n2. **Contact Angle Measurement:**\n   - Analyze the angle formed between water droplets and the polymer surface.\n3. **Fourier Transform Infrared (FTIR) Spectroscopy:**\n   - Verify incorporation of hydrophilic functional groups.\n\n---\n\n### **Specific Considerations for the Provided Molecule**\nDepending on your molecule:\n1. **Functional Groups:** Pay attention to primary functional groups (e.g., hydroxyl, amine, carboxyl) for reactivity and hydrophilicity enhancement.\n2. **Steric Hindrance:** If bulky groups are present, ensure they do not impede polymerization or reduce hydrophilicity.\n3. **Hydrophilic Enhancement:** Incorporating additional hydrophilic monomers (e.g., ethylene glycol derivatives) alongside your molecule may improve water affinity.\n\n---\n\n### **Concluding Remarks**\nBy following this protocol, you can:\n1. Systematically integrate your molecule into a hydrophilic polymer structure.\n2. Achieve a material with enhanced water affinity suited for biomedical, coating, or other applications.\n\nLet me know if you can share the exact chemical structure of the molecule you provided for further tailoring!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Ethanolamine is one of the starting materials used in polymer modification. Propose how ethanolamine's structure and reactivity play a vital role in introducing hydrophilic functional groups into the polymer material."}, {"role": "assistant", "content": "To answer your question and explain how ethanolamine can be utilized in introducing hydrophilic functional groups into polymer materials, let us carefully approach this step by step, analyzing its structure and reactivity. We will then outline an experimental strategy for modifying a polymer, ensuring we cover all relevant details methodically, as per your request.\n\n---\n\n### Step 1: Key Points in the Question\n1. **Ethanolamine\u2019s Structure and Reactivity:**\n   - Ethanolamine (HOCH\u2082CH\u2082NH\u2082) has both hydroxyl (-OH) and amine (-NH\u2082) functional groups.\n   - These groups make ethanolamine reactive towards various chemical transformations, allowing it to graft hydrophilic groups onto polymers.\n   - Importantly, the hydroxyl group introduces hydrogen-bonding capacity, while the amine group can participate in nucleophilic reactions or protonation under acidic conditions.\n\n2. **Objective:**\n   - To design an experimental approach to modify a polymer using ethanolamine as a reagent to enhance its hydrophilicity.\n\n---\n\n### Step 2: Role of Ethanolamine in Enhancing Hydrophilicity\n- The **hydroxyl (-OH)** and **amine (-NH\u2082)** moieties of ethanolamine are highly hydrophilic. When these groups are covalently incorporated into a polymer backbone or grafted onto the surface, they:\n  1. Improve the polymer's *wetting properties* by interacting with water molecules via hydrogen bonding.\n  2. Increase solubility or water absorption (depending on the degree of functionalization).\n  \nAs an amphiphilic molecule, ethanolamine is particularly useful because it is small and reactive, enabling selective functionalization without drastically altering the polymer\u2019s mechanical properties.\n\n---\n\n### Step 3: Experimental Preparation Scheme for Polymer Modification with Ethanolamine\nHere, I propose a synthetic strategy where ethanolamine is chemically attached to an existing polymer backbone to enhance its hydrophilicity. The polymer system will depend on the functional groups present, but common strategies involve reacting ethanolamine with polymers bearing **reactive electrophilic groups** (e.g., anhydride, epoxide, or halide).\n\nLet us consider using **poly(maleic anhydride)** as the starting polymer, as it is a common material for functional modification.\n\n---\n\n#### **Reaction Schematic**\nPoly(maleic anhydride) (PMA) + Ethanolamine \u2192 Poly(maleic acid ethanolamine) (Modified PMA with hydrophilic groups)\n\n---\n\n### Experimental Steps for Synthesizing Hydrophilic Polymer\n\n#### **Materials:**\n1. **Poly(maleic anhydride)** (PMA) - Source of reactive anhydride groups.\n2. **Ethanolamine** - Hydrophilic reagent.\n3. **Solvent:** Dimethylformamide (DMF) or tetrahydrofuran (THF) - Polar, aprotic solvent for dissolution.\n4. **Catalyst (optional):** Triethylamine (TEA) or a few drops of pyridine to neutralize excess acidity.\n\n---\n\n#### **Step-by-Step Procedure:**\n\n##### 1. **Polymer Dissolution:**\n   - Dissolve **1 g of poly(maleic anhydride)** in **20 mL of dry DMF** under an inert atmosphere (e.g., nitrogen or argon) at room temperature. \n   - Stir continuously until the polymer is fully dissolved (1\u20132 hours).\n\n   *Note:* Ensure complete solubilization for a uniform reaction.\n\n##### 2. **Preparation of Ethanolamine Solution:**\n   - In a separate container, dissolve **0.1 mL of ethanolamine (1.5 mmol)** in **5 mL DMF.**\n   - This ensures accurate dispersion and avoids localized overreaction in the polymer solution.\n\n##### 3. **Controlled Addition:**\n   - Add the ethanolamine solution dropwise to the polymer solution with constant stirring at **room temperature.**\n   - Allow the reaction to proceed for **4\u20136 hours.**\n\n   *Key Reaction:* Ethanolamine reacts with the anhydride group of PMA, opening the cyclic anhydride and forming an amide bond (via the amine group) and a carboxylic acid group (from the hydroxyl group).\n\n##### 4. **Monitoring the Reaction:**\n   - Monitor the reaction progression using **FTIR spectroscopy.**\n     - Absorption peaks at ~1850 cm\u207b\u00b9 and ~1780 cm\u207b\u00b9 (characteristic of maleic anhydride) will diminish.\n     - New peaks around ~3300 cm\u207b\u00b9 (O-H stretch) and ~1650 cm\u207b\u00b9 (C=O stretch for amide) will appear.\n\n##### 5. **Precipitation and Purification:**\n   - Precipitate the modified polymer by adding the reaction mixture dropwise into **100 mL of cold diethyl ether** while stirring.\n   - Filter the precipitate using a vacuum filtration setup and wash with ether to remove residual ethanolamine and unreacted starting materials.\n\n##### 6. **Drying:**\n   - Dry the polymer under vacuum at **40\u201350\u00b0C** overnight.\n\n---\n\n### Reaction Stoichiometry and Yield Estimation:\n- For a 1 g sample of poly(maleic anhydride) (approx. 10 mmol of anhydride groups) and 1.5 mmol ethanolamine, this is a sub-stoichiometric reaction. Hence, only partial modification is expected (10\u201315% functionalization) to retain the polymer chain\u2019s physical integrity.\n\n---\n\n### Step 4: Post-Reaction Characterization\n\n1. **FTIR Analysis:**\n   - Confirm the disappearance of anhydride peaks and the appearance of O-H and N-H stretches.\n\n2. **Contact Angle Measurement:**\n   - Measure the water contact angle of the modified polymer film to assess the improvement in hydrophilicity. A decreased contact angle indicates better hydrophilicity.\n\n3. **Thermal Stability:**\n   - Perform thermogravimetric analysis (TGA) to ensure the modification does not compromise the polymer\u2019s thermal properties.\n\n---\n\n### Step 5: Conclusion\nEthanolamine\u2019s bifunctional nature (hydroxyl and amine) plays a pivotal role in enhancing polymer hydrophilicity by introducing hydrogen-bonding-capable groups. When properly reacted with polymers such as poly(maleic anhydride), ethanolamine introduces carboxylic acids and amides, enhancing hydrophilicity while maintaining the polymer matrix\u2019s structural integrity.\n\nBy following the outlined experimental scheme, you should be able to successfully utilize ethanolamine for producing hydrophilic polymers with applications in water-based coatings, biomedical materials, or membrane technologies.\n\nIf you have further questions or need clarification, feel free to ask!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "How can gamma-methacryloxypropyltrimethoxysilane (MPS) be utilized to introduce functional double bonds onto a substrate, and why is this step critical for preparing hydrophilic polymer coatings?"}, {"role": "assistant", "content": "To thoroughly answer your question, we will systematically analyze the problem and design a detailed experimental preparation scheme based on the requirements and context provided. Here's how gamma-methacryloxypropyltrimethoxysilane (MPS) can be utilized to introduce functional double bonds onto a substrate, and why this step is critical for preparing hydrophilic polymer coatings.\n\n---\n\n### **Step 1: Analyze the Question**\n- **Key molecule**: Gamma-methacryloxypropyltrimethoxysilane (MPS).\n- **Goal**: Introduce functional double bonds onto a substrate surface using MPS.\n- **Purpose**: The double bonds serve as reactive sites for preparing hydrophilic polymer coatings.\n- **Importance of double bonds**: These double bonds enable subsequent polymerization or surface grafting to form hydrophilic polymer networks, improving the substrate's wettability and compatibility with aqueous environments.\n\n---\n\n### **Step 2: Systematic Explanation and Experimental Design**\nHere is the detailed preparation scheme step-by-step:\n\n#### 2.1 **Substrate Pretreatment**\nBefore functionalizing the substrate with MPS, it is important to ensure the surface is clean and reactive:\n- **Importance**: Any contamination (organic or inorganic debris) will hinder adhesion of MPS and reduce the availability of silanol groups required for silane bond formation.\n- **Procedure**:\n  1. **Cleaning**: Immerse the substrate (e.g., glass, metal oxide, polymer film, etc.) in a solution of ethanol and deionized water (1:1 v/v) containing 1% (v/v) acetic acid. Sonicate the substrate for 20\u201330 minutes to remove debris.\n  2. **Activation**: If the substrate is non-reactive like glass or silicon wafer, use a plasma treatment or immerse the substrate in 1 M NaOH or piranha solution (a mixture of sulfuric acid and hydrogen peroxide) for 10 minutes to generate hydroxyl groups (-OH) for silane coupling.\n\n#### 2.2 **Preparation of MPS Solution**\n- **Reagents**:\n  - Gamma-methacryloxypropyltrimethoxysilane (MPS).\n  - Ethanol (solvent).\n  - Deionized water.\n  - Acetic acid or hydrochloric acid (catalyst for hydrolysis).\n- **Procedure**:\n  1. Prepare a solution with 5% (v/v) MPS in ethanol and deionized water mixture (90:10 ethanol/water by volume).\n  2. Add 0.1\u20130.5% (v/v) acetic acid or hydrochloric acid to the mixture to catalyze hydrolysis of the trimethoxysilane groups.\n  3. Stir the solution at room temperature for 30\u201360 minutes to form silanol (-Si-OH) groups through hydrolysis.\n\n---\n\n#### 2.3 **Functionalization of Substrate**\n- **Procedure**:\n  1. Immerse the cleaned and activated substrate in the prepared MPS solution. Ensure complete immersion for uniform functionalization.\n  2. Allow the substrate to react with MPS for 1\u20132 hours at room temperature or slightly elevated temperatures (~50 \u00b0C) to promote condensation reactions between silanol groups on the substrate and MPS molecules.\n  3. After functionalization, remove the substrate and rinse thoroughly with ethanol to remove non-reacted MPS molecules.\n  4. Dry the substrate under vacuum or by gentle heating (~70\u201380 \u00b0C) to ensure complete crosslinking and condensation.\n\n---\n\n#### 2.4 **Characterization of Double Bonds**\n- **Purpose**: Verify the successful modification of the substrate surface with double bonds from the MPS molecule.\n- **Techniques**:\n  - **FTIR Analysis**: Look for characteristic C=C stretching vibrations (~1635 cm\u207b\u00b9) and Si-O-Si vibrations (~1100 cm\u207b\u00b9) confirming the presence of double bonds and silane coupling.\n  - **Contact Angle Measurements**: A reduction in the contact angle after functionalization indicates the introduction of reactive groups.\n  - **XPS Analysis**: Detect the chemical changes confirming the incorporation of MPS onto the surface.\n\n---\n\n#### 2.5 **Polymerization of Hydrophilic Polymer**\nWith the substrate now bearing double bonds, hydrophilic polymers can be grafted or polymerized onto the surface:\n- **Importance of Double Bonds**: The methacrylate double bonds (-CH=CH\u2082) present on the surface serve as reactive sites for free-radical polymerization or covalent bonding of hydrophilic monomers, such as acrylamide, acrylic acid, or polyethylene glycol methacrylate (PEGMA).\n- **Procedure**:\n  1. Prepare an aqueous solution containing the hydrophilic monomer (e.g., 10\u201320% by mass acrylamide) and a radical initiator like ammonium persulfate (APS) or photoinitiator.\n  2. Place the MPS-functionalized substrate into the solution and initiate polymerization through heat (~60 \u00b0C) or UV irradiation, depending on the initiator.\n  3. After the polymerization is complete, rinse and dry the coated substrate.\n\n---\n\n### **Step 3: Why Is This Step Critical for Hydrophilic Polymer Coatings?**\n1. **Anchoring Sites**: The MPS introduces double bonds, which act as anchoring sites for grafting hydrophilic polymers. Without these bonds, polymerization would not occur uniformly or strongly on the surface.\n2. **Strong Adhesion**: The silanol groups formed during MPS coupling create robust covalent bonds with hydroxyl groups on the substrate, preventing delamination or weak adhesion.\n3. **Uniform Polymerization**: The presence of double bonds ensures a consistent reaction interface for hydrophilic polymers to grow, yielding homogeneous coatings.\n4. **Enhanced Hydrophilicity**: The resulting hydrophilic polymer layer lowers the surface energy of the substrate, increasing wettability by water.\n\n---\n\n### Final Notes:\nThe inclusion of MPS in the process is foundational for hydrophilic polymer coating preparation. As you practice this in the lab, ensure precision in contamination removal, reagent concentrations, and reaction conditions to achieve reliable and reproducible results. Don't forget to thoroughly characterize the intermediate and final products to validate each step."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe how you would use mercaptopropionic acid as a reactant to modify a polymer in an experiment designed to enhance its hydrophilicity. Specify the necessary reaction conditions based on your understanding of hydrophilic polymer synthesis."}, {"role": "assistant", "content": "### Step 1: Analyze the Question and Summarize the Key Points\n\nThe question involves **modifying a polymer using mercaptopropionic acid (MPA)** to enhance its hydrophilicity. Mercaptopropionic acid possesses two functional groups: a **thiol (-SH)** group and a **carboxylic acid (-COOH)** group. The **thiol group** can participate in reactions such as thiol-ene reactions or thiol-disulfide exchange, while the **carboxylic acid group** contributes hydrophilic properties, which aligns with the goal to increase the polymer\u2019s hydrophilicity.\n\nWe aim to:\n1. Identify a suitable method to attach mercaptopropionic acid to the polymer.\n2. Specify the reaction conditions (e.g., catalyst, temperature, solvent) and reagent ratios.\n3. Systematically detail the entire experimental process to ensure this functionalization can be achieved practically in the lab.\n\n---\n\n### Step 2: Detailed and Systematic Reaction Design\n\n#### **Approach: Grafting Mercaptopropionic Acid onto the Polymer Backbone**\nTo attach mercaptopropionic acid to a polymer, two commonly used reactions can be utilized, depending on the polymer's structure and available functional groups:\n- **Thiol-ene Reaction** if the polymer contains unsaturated bonds (C=C).\n- **Thiol-disulfide Exchange Reaction** if the polymer already has disulfide linkages.\n\nFor this analysis, I will assume we are modifying a polymer featuring **vinyl groups (C=C bonds)** through a **thiol-ene click chemistry approach**. This choice is widely applicable and allows controlled, efficient grafting with good functional group tolerance.\n\n---\n\n#### **Experimental Procedure**\n\n**Step 1: Materials and Equipment**\nYou will need:\n- Mercaptopropionic acid (MPA): The key reactant.\n- Polymer with vinyl functionality (e.g., poly(butyl acrylate-co-glycidyl methacrylate) or similar).\n- Photoinitiator: 2,2-Dimethoxy-2-phenylacetophenone (DMPA) or Irgacure 651, commonly used in thiol-ene reactions.\n- Solvent: Ethanol or a similar polar, hydrophilic solvent.\n- UV light source (e.g., a UV lamp emitting at 365 nm).\n- Nitrogen gas for inert atmosphere.\n- Glassware: Reaction flask, stirrer, and UV-transparent quartz cell.\n\n---\n\n**Step 2: Reaction Setup and Conditions**\n1. **Prepare the Reaction Mixture:**\n   - In a reaction flask, dissolve the polymer with vinyl groups (amount depends on desired functionalization, typically 1\u20132 g) in ethanol (20\u201330 mL).\n   - Add mercaptopropionic acid in molar excess (2:1 molar ratio of MPA to vinyl groups). This ensures all available vinyl groups react with MPA for maximum hydrophilicity.\n   - Introduce the photoinitiator, e.g., DMPA, at around 1 wt% of the total reaction mixture.\n\n2. **Degas the Reaction Mixture:**\n   - Bubble nitrogen gas through the reaction mixture for 15\u201320 minutes to remove dissolved oxygen. Oxygen can interfere with the photochemical reaction.\n\n3. **Expose to UV Light:**\n   - Place the reaction vessel under UV light (365 nm) at room temperature.\n   - Stir the reaction continuously to ensure uniform exposure and prevent localized overheating.\n   - Allow the reaction to proceed for 30\u201360 minutes. Monitor the reaction's progress using FTIR spectroscopy by observing the reduction in the vinyl group peak (1600\u20131660 cm\u207b\u00b9) and the appearance of thiol-modified peaks near 1700 cm\u207b\u00b9 (C=O stretching from the incorporated MPA).\n\n---\n\n**Step 3: Purification**\n1. After completing the reaction, remove the solvent using a rotary evaporator.\n2. Dissolve the polymer in a suitable solvent (e.g., ethanol or water) and precipitate it into an antisolvent (commonly diethyl ether or hexane).\n3. Wash the precipitated polymer thoroughly to remove unreacted mercaptopropionic acid and photoinitiator residues.\n4. Dry the purified polymer under vacuum at 40\u201350\u00b0C until constant weight is achieved.\n\n---\n\n**Step 4: Characterization**\n1. **FTIR Spectroscopy:** Verify successful grafting by checking the reduction of vinyl peaks (1600\u20131660 cm\u207b\u00b9) and appearance of carboxylic acid peaks (1700 cm\u207b\u00b9).\n2. **Contact Angle Measurement:** Test the hydrophilicity of the modified polymer by performing a water contact angle test. A lower water contact angle compared to the unmodified polymer indicates enhanced hydrophilicity.\n3. **Thermal Analysis (TGA/DSC):** Confirm thermal stability after modification.\n4. **NMR Spectroscopy:** Use \u00b9H NMR to confirm the successful attachment of mercaptopropionic acid onto the polymer backbone (look for thiol and vinyl proton disappearance).\n\n---\n\n### Final Notes on Optimization and Scaling Up\n\n- **Reaction Time Optimization:** If time allows, conduct small-scale trials varying UV exposure time to maximize grafting efficiency without degradation.\n- **Stoichiometry Adjustments:** Optimize the MPA/polymer ratio for functionalization balance and material performance.\n- **Scaling Up:** For larger-scale synthesis, ensure that UV light exposure is uniform by using a controlled photoreactor. Monitor the reaction temperature more closely to avoid local heating.\n\nThis systematic approach ensures successful modification of the polymer, enhancing its hydrophilicity via the attachment of mercaptopropionic acid. If you have additional details about the polymer involved, we can refine this scheme further."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "You are tasked with synthesizing poly(ethylene glycol) diacrylate (PEGDA). Based on the molecule provided, describe the procedure to functionalize polyethylene glycol (PEG) with acrylate groups and identify the key reaction steps involved in the acrylation process."}, {"role": "assistant", "content": "To synthesize poly(ethylene glycol) diacrylate (PEGDA), we need to functionalize a polyethylene glycol (PEG) molecule with acrylate groups. Before diving into the experimental details of the procedure, let\u2019s first analyze the question, summarize the critical points, and plan the process step-by-step.\n\n---\n\n### **1. Analyze the Question and Summarize Key Points**\n- **Objective**: To synthesize poly(ethylene glycol) diacrylate (PEGDA) by introducing acrylate functional groups to both hydroxyl (-OH) groups at the ends of a polyethylene glycol chain.\n- **Key Requirements**: \n  - A polyethylene glycol (PEG) molecule as the starting material.\n  - Acrylation reagents to react with the hydroxyl groups.\n  - Specific reaction conditions to ensure proper functionalization, avoiding side reactions or incomplete conversion.\n  - Reaction byproducts (e.g., water or acid byproducts) must be removed carefully to purify PEGDA.\n\n**Critical steps to achieve this**:\n1. Activation of acrylate functionality.\n2. Controlled reaction between PEG and acrylate precursor to obtain PEGDA.\n3. Purification of the final product to isolate pure PEGDA.\n\n---\n\n### **2. Step-by-Step Detailed Synthesis of PEGDA**\nBelow is a systematic synthesis procedure with details on reagents, conditions, and practical laboratory considerations for preparing PEGDA.\n\n---\n\n#### **Step 1: Select the Starting Materials and Reagents**\n1. **Polyethylene Glycol (PEG):**\n   - Use a dihydroxyl-terminated polyethylene glycol (HO-PEG-OH). The molecular weight of PEG can vary (e.g., PEG of Mw = 400 or 1000 g/mol) depending on the intended application of the PEGDA product.\n\n2. **Acryloyl Chloride**: \n   - Acryloyl chloride is used as the acrylate precursor. It reacts readily with hydroxyl groups to introduce acrylate moieties.\n\n3. **Base:**\n   - A base (e.g., triethylamine, TEA) is used to neutralize the HCl byproduct formed during the reaction and prevent side reactions involving the acid.\n\n4. **Solvent:**\n   - Use a dry, inert organic solvent such as dichloromethane (DCM) or tetrahydrofuran (THF).\n\n5. **Inhibitors:**\n   - Add a polymerization inhibitor (e.g., hydroquinone or 4-methoxyphenol, MEHQ) to prevent premature polymerization of the acrylate groups.\n\n---\n\n#### **Step 2: Reaction Setup**\n1. **Apparatus**: \n   - A reaction flask equipped with a magnetic stirrer, a dropping funnel (for controlled addition of reagents), and a reflux condenser.\n   - Maintain an inert atmosphere using nitrogen or argon gas if necessary to avoid moisture or oxygen contamination.\n   - A thermometer to monitor the reaction temperature.\n\n2. **Preparation of PEG Solution**:\n   - Dissolve the PEG in dry dichloromethane (DCM) or THF in the reaction flask. Use approximately 1 equivalent of PEG (dihydroxyl groups).\n\n3. **Addition of Base**:\n   - Add triethylamine (TEA) at a molar ratio of 2 equivalents per hydroxyl group of PEG to the reaction mixture. TEA will neutralize HCl generated during the acrylation reaction.\n\n---\n\n#### **Step 3: Acrylation Reaction**\n1. **Prepare Acryloyl Chloride Solution**:\n   - In a separate container, dilute acryloyl chloride in dry DCM or THF. The molar ratio of acryloyl chloride to PEG hydroxyl groups should be slightly higher (>1:1, typically 1.1\u20131.2 equivalents per hydroxyl group) to ensure full functionalization.\n\n2. **Controlled Addition**:\n   - Using the dropping funnel, add the acryloyl chloride solution slowly to the stirred PEG solution over ~30 minutes. This helps maintain a stable reaction and minimizes side reactions.\n\n3. **Reaction Conditions**:\n   - Maintain the reaction mixture at 0\u20135\u00b0C during the addition of acryloyl chloride to reduce the exothermic nature of the reaction.\n   - After the addition is complete, allow the reaction to stir at room temperature (~25\u00b0C) for 4\u20136 hours to ensure complete conversion to PEGDA.\n\n4. **Inhibitor Addition** (if not already added):\n   - Add a small amount of hydroquinone or MEHQ (e.g., ~100 ppm) to prevent premature polymerization of the acrylate-functionalized product.\n\n---\n\n#### **Step 4: Workup and Purification**\n1. **Neutralize Byproducts**:\n   - Filter the reaction mixture to remove the triethylamine hydrochloride salt precipitate.\n\n2. **Washing**:\n   - Wash the organic phase with deionized water or dilute sodium bicarbonate solution to neutralize and remove any unreacted acid (e.g., HCl).\n\n3. **Drying**:\n   - Dry the organic phase over anhydrous sodium sulfate to remove residual moisture.\n\n4. **Evaporation**:\n   - Use a rotary evaporator to remove the solvent under reduced pressure, isolating the crude PEGDA product.\n\n5. **Purification**:\n   - If needed, the product can be purified further by precipitation in cold diethyl ether or through column chromatography.\n\n---\n\n#### **Step 5: Product Characterization**\n1. **Nuclear Magnetic Resonance (NMR)**:\n   - Use 1H NMR spectroscopy to confirm successful acrylation. The vinyl protons of the acrylate group (-CH=CH2) should appear as distinctive peaks (~5.8\u20136.5 ppm).\n\n2. **Fourier Transform Infrared Spectroscopy (FTIR)**:\n   - Verify the presence of acrylate groups by observing the stretching vibration of the carbonyl groups (C=O) near 1720 cm\u207b\u00b9.\n\n3. **Gel Permeation Chromatography (GPC)**:\n   - Confirm the molecular weight of the PEGDA product and assess the polydispersity index (PDI).\n\n---\n\n### **Summary of Reaction**\nThe reaction can be summarized as:\n\\[ HO-PEG-OH + 2 \\, \\text{CH}_2=CH-\\text{COCl} \\xrightarrow[\\text{TEA}]{\\text{DCM or THF}} \\text{CH}_2=CH-\\text{COO}-PEG-\\text{OCO}-CH=CH_2 + 2 \\, \\text{HCl} \\]\n\nIn this synthetic scheme, PEG is di-functionalized with acrylate groups to yield PEGDA, which is widely used in hydrogel synthesis, bioconjugation, and tissue engineering.\n\n---\n\nBy following this carefully designed protocol, you will obtain high-purity PEGDA ready for further applications. Good luck, and remember to take necessary laboratory precautions, especially when handling acryloyl chloride and organic solvents! \ud83d\ude0a"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Design an experiment to incorporate the sodium salt of 5-sulfoisophthalic acid into a copolyester structure. What would be the role of this molecule in enhancing the hydrophilicity of the polymer material, and how would you ensure it is properly integrated during the condensation reaction?"}, {"role": "assistant", "content": "This is an excellent question, and I appreciate your interest in understanding how to enhance the hydrophilicity of polymer materials through structural modification. Let me guide you through the design and analysis step by step.\n\n---\n\n### ANALYSIS OF THE QUESTION AND KEY POINTS:\n1. **Goal**: To incorporate the sodium salt of 5-sulfoisophthalic acid (5-SSIPA) into a copolyester structure via a condensation reaction.\n2. **Purpose**: To enhance the hydrophilicity of the polymer material.\n3. **Key considerations**:\n   - The sodium salt of 5-SSIPA introduces sulfonic acid (-SO\u2083\u207bNa\u207a) groups into the polymer, which increases hydrophilicity due to the ionic, polar nature of the sulfonate group.\n   - The integration of 5-SSIPA into the copolyester backbone must be carefully controlled to ensure proper condensation without undesired side reactions (e.g., hydrolysis, incomplete incorporation).\n   - Proper stoichiometric balance and reaction conditions are crucial for copolymerization.\n\n---\n\n### SYSTEMATIC EXPERIMENTAL PREPARATION SCHEME:\n\n#### **Step 1: Selection of Monomers**\nTo prepare a copolyester containing 5-SSIPA, we need the following monomers:\n1. **Diacid component**: A combination of terephthalic acid (or its dimethyl ester, dimethyl terephthalate - DMT) with the sodium salt of 5-sulfoisophthalic acid (5-SSIPA).\n   - 5-SSIPA provides ionic hydrophilicity, while terephthalic acid forms the bulk of the aromatic backbone, ensuring mechanical integrity.\n2. **Diol component**: Ethylene glycol (EG) is most commonly used due to its reactivity and compatibility with aromatic polyesters.\n\nThese components will form the copolyester backbone, with 5-SSIPA serving as a hydrophilic modifier.\n\n---\n\n#### **Step 2: Experimental Design**\n\n**Reaction Mechanism**: The synthesis involves a polycondensation reaction. If using terephthalic acid, an esterification reaction precedes the condensation step. If using DMT, it will directly transesterify with ethylene glycol to produce the oligomers before polycondensation.\n\n---\n\n**Step 2.1: Reaction Setup**\n1. **Reactor Preparation**:\n   - Use a 3-neck round-bottom flask equipped with a mechanical stirrer, nitrogen inlet (to prevent oxidation), and a condenser (to collect by-products like methanol or water).\n   - A thermometer and heating mantle will provide accurate temperature control.\n\n2. **Reagents**:\n   - 5-Sulfoisophthalic acid sodium salt (5-SSIPA): 5\u201315 mol% of the total acid content (for sufficient hydrophilicity without drastically reducing crystallinity).\n   - Terephthalic acid (or dimethyl terephthalate - DMT): Remaining mol% of the aromatic diacid content.\n   - Ethylene glycol (EG): A stoichiometric excess is typically used (2\u20133 moles of EG per mole of total diacid) to drive the esterification/condensation equilibrium forward.\n\n---\n\n**Step 2.2: Reaction Sequence**\nThe reaction proceeds in two stages: (1) Formation of oligomers, and (2) Polycondensation.\n\n---\n\n### **Stage 1: Oligomer Formation**\n1. **Reagent Addition**:\n   - Charge the reactor with terephthalic acid (or DMT), 5-SSIPA, and ethylene glycol.\n   - Ensure thorough mixing of 5-SSIPA and terephthalic acid/DMT to achieve uniform distribution.\n\n2. **Catalyst**:\n   - Add 0.01\u20130.05 mol% of a transesterification catalyst, such as titanium(IV) isopropoxide (Ti(O-iPr)\u2084) or antimony trioxide (Sb\u2082O\u2083), for DMT. \n   - Alternatively, if terephthalic acid is used, a carboxyl-esterification catalyst like p-toluenesulfonic acid (p-TSA) may be used.\n\n3. **Temperature Control**:\n   - For DMT: Heat to 180\u2013200\u00b0C to drive the transesterification reaction. Methanol will be collected as a condensate (by-product).\n   - For terephthalic acid: Heat to 220\u2013240\u00b0C to facilitate esterification, with water as a by-product.\n\n4. **Monitoring**:\n   - Stir constantly and monitor the release of methanol or water to ensure the reaction progresses toward oligomer formation.\n   - Reaction time: Typically 2\u20134 hours to ensure full conversion.\n\n---\n\n### **Stage 2: Polycondensation**\n1. **Vacuum Application**:\n   - Once oligomers are formed, decrease the pressure gradually to <1 mmHg (high vacuum). This prevents side reactions and removes volatile by-products efficiently.\n\n2. **Temperature Control**:\n   - Increase the temperature to 250\u2013280\u00b0C in this step to achieve the required viscosity. Maintain stirring to ensure uniform mixing.\n\n3. **Duration**:\n   - The polycondensation reaction typically takes 2\u20136 hours, depending on the viscosity target (related to molecular weight).\n\n4. **Integration of 5-SSIPA**:\n   - The sulfonate groups of 5-SSIPA are already incorporated into the polyester backbone during Stage 1. To ensure proper integration, avoid using excessive 5-SSIPA levels that could lead to phase separation or poor polymerization.\n\n---\n\n#### **Step 3: Polymer Recovery and Analysis**\n1. Cool the reaction mixture and collect solidified polyester.\n   - The final product should be a copolyester with an ionic hydrophilic functionality due to the sulfonate groups from 5-SSIPA.\n\n2. **Purification**:\n   - Wash thoroughly with distilled water to remove unreacted monomers or residual sodium salts.\n\n3. **Characterization**:\n   - Conduct **Fourier-transform infrared spectroscopy (FTIR)** to confirm the incorporation of sulfonate groups (-SO\u2083\u207b).\n   - Use **Nuclear Magnetic Resonance (NMR)** spectroscopy to verify the molecular structure.\n   - Measure intrinsic viscosity and molecular weight using gel-permeation chromatography (GPC).\n   - Perform water contact angle measurements to confirm enhanced hydrophilicity.\n\n---\n\n### ROLE OF 5-SSIPA IN HYDROPHILICITY:\n1. The sulfonate (-SO\u2083\u207bNa\u207a) groups on 5-SSIPA are highly hydrophilic and enhance the water absorption capacity of the polymer, making it more suitable for applications such as water filtration membranes or hydrophilic coatings.\n2. The ionic nature of the sulfonate groups enables stronger interactions with water molecules, ensuring better wetting properties and potential ion-exchange functionality.\n\n---\n\n### TROUBLESHOOTING AND TIPS:\n1. Excessive use of 5-SSIPA (>15 mol%) may lead to phase separation, brittle polymers, or poor processability due to the disruption of crystallinity.\n2. Avoid hydrolysis of ester bonds by maintaining an anhydrous environment (once water by-products have been removed) and controlling vacuum application rates.\n3. Use high-purity reagents and prevent contamination to avoid side reactions.\n\n---\n\nBy following these steps meticulously, you can successfully incorporate 5-SSIPA into a copolyester and achieve a hydrophilic material tailored for your target application. Let me know if you have any further questions!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe a detailed experimental scheme for incorporating TMP(EO)3TA into a polymer matrix to enhance hydrophilicity. Outline the mixing, curing, and thickness measurement steps clearly."}, {"role": "assistant", "content": "To design a detailed experimental scheme for incorporating TMP(EO)\u2083TA (Trimethylolpropane triethoxylated triacrylate) into a polymer matrix to enhance hydrophilicity, we must carefully analyze the question, break it down into its essential components, and address each step of the synthetic process systematically. The preparation scheme will include mixing, curing, and thickness measurement. Let\u2019s proceed step by step:\n\n---\n\n### **Step 1: Analyzing the Task**\n**Key Points of the Question**:\n1. **Incorporating TMP(EO)\u2083TA** into a polymer matrix to enhance hydrophilicity.\n2. Systematic detailing of **mixing**, **curing**, and **thickness measurement** steps.\n3. Emphasis on reaction conditions, reagent ratios, molar quantities, and clear experimental instructions.\n\nTMP(EO)\u2083TA is a hydrophilic acrylate monomer with ethylene oxide groups that improve water affinity. Introducing it into a polymer matrix typically involves free radical polymerization, where it serves as a crosslinker or co-monomer. By appropriately tailoring the formulation, curing, and processing conditions, this compound can significantly enhance the polymer's hydrophilicity.\n\n---\n\n### **Step 2: Materials Required**\n1. **TMP(EO)\u2083TA** (hydrophilic monomer).\n2. **Base polymer matrix** (e.g., polyethylene glycol dimethacrylate (PEGDMA) or other acrylate-based matrix).\n3. Initiator: **2,2\u2019-Azobis(2-methylpropionitrile) (AIBN)** or **Irgacure-2959** for UV-initiated curing.\n4. Solvent: **Ethanol** or **DI water** (to enhance mixing and dissolve reactants).\n5. Substrate: Glass or silicon wafer for thin film deposition.\n6. Lab equipment: Spin coater (optional), UV curing station, precision micrometer or profilometer.\n\n---\n\n### **Step 3: Experimental Scheme**\n#### **A. Mixing Step**\nThe goal is to prepare a homogeneous solution containing TMP(EO)\u2083TA and the polymer matrix.\n\n1. **Reaction Mixture Preparation**:\n   - **Base Polymer Solution**: Dissolve 10 g of PEGDMA or another target polymer matrix in 50 mL of ethanol to create a 20% (w/v) solution. Stir at room temperature until complete dissolution (approximately 30 minutes).\n   - **TMP(EO)\u2083TA Addition**: Add TMP(EO)\u2083TA to the polymer solution. Typically, use TMP(EO)\u2083TA at **10-30 wt%** relative to the base polymer to ensure enhanced hydrophilicity. For example:\n     - For 10 g of PEGDMA, add 3 g of TMP(EO)\u2083TA.\n   - **Initiator Addition**: Add the polymerization initiator (e.g., 0.05 g of AIBN per 10 g of the polymer matrix).\n   - Mix the solution thoroughly under mechanical stirring at 300\u2013500 rpm for 1 hour to ensure homogeneity.\n\n2. **Degassing**:\n   - Place the reaction mixture in a vacuum desiccator for ~15 minutes to remove oxygen and avoid inhibition of free radical polymerization.\n\n---\n\n#### **B. Curing Step**\nCuring will involve polymerization of the TMP(EO)\u2083TA into the polymer matrix to create a crosslinked hydrophilic network.\n\n1. **Film Preparation**:\n   - Use a spin coater to spread the reaction mixture onto the substrate (e.g., a glass slide or silicon wafer). Spin at **2500 RPM** for 60 seconds to ensure uniform coating. Alternatively, apply the mixture using a drop-casting method for thicker films.\n   - Target initial thickness: **200\u2013500 \u03bcm**, depending on application.\n\n2. **Polymerization/Curing**:\n   - **Thermal Curing**:\n     - Place the coated substrate in an oven preheated to 70\u201380\u00b0C for 2 hours. Ensure constant temperature and uniform heat distribution in the oven.\n   - **UV Curing (Preferred for TMP(EO)\u2083TA)**:\n     - Use a UV curing station with a wavelength range of 365\u2013405 nm.\n     - Irradiate for 5 minutes at **10 mW/cm\u00b2** intensity. Extend curing time to 10 minutes if a higher crosslink density is desired.\n\n3. **Post-Curing Treatment**:\n   - After curing, rinse the film gently with DI water to remove unreacted monomers or initiator residues.\n   - Dry the cured polymer samples in an oven at 40\u00b0C for 30 minutes.\n\n---\n\n#### **C. Thickness Measurement Step**\n1. **Tools**:\n   - Use a precision micrometer or a profilometer to measure the final thickness of the cured polymer films.\n\n2. **Procedure**:\n   - Select three different regions of the cured film across the substrate to ensure uniformity.\n   - Measure thickness using the profilometer in **nanometer (nm)** or **micrometer (\u03bcm)** scales.\n   - Record and average the readings to determine the final thickness. Ensure it aligns with the desired range (e.g., 200\u2013500 \u03bcm).\n\n---\n\n### **Step 4: Enhancing Hydrophilicity**\nTo confirm enhanced hydrophilicity:\n1. Perform **contact angle measurements**. A reduced contact angle (<40\u00b0) on the cured film indicates hydrophilic behavior.\n2. Conduct **swelling studies**:\n   - Immerse the polymer in DI water and measure weight changes over time to assess water uptake and hydrophilicity.\n\n---\n\n### **Step 5: Notes on Experimental Conditions**\n1. **Safety Considerations**:\n   - Handle TMP(EO)\u2083TA and initiators with care in a fume hood.\n   - Wear gloves and safety goggles.\n\n2. **Optimization**:\n   - Adjust TMP(EO)\u2083TA concentration based on desired hydrophilicity. Higher wt% increases hydrophilicity but might reduce mechanical strength.\n\n3. **Storage**:\n   - Store the polymer films in sealed containers to prevent contamination and degradation.\n\n---\n\nThis detailed experimental scheme should enable successful incorporation of TMP(EO)\u2083TA into the polymer matrix for enhanced hydrophilicity. Let me know if you have further questions or need clarification on specific steps!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the steps you would take to calculate the value of \u03bb0 when modifying the polymer with '\u03bc_ref'. How does solving this boundary value problem contribute to determining the hydrophilic properties of the modified polymer?"}, {"role": "assistant", "content": "To address your question systematically, let's break it down and develop a logical and detailed approach. I'll provide a comprehensive explanation within the framework you've outlined, including analysis, experimental details, and how solving the boundary value problem contributes to determining the hydrophilic properties of the modified polymer.\n\n---\n\n### Part 1: **Analysis of the Question**\n\n#### Key Points:\n1. **Polymer Modification**: The question revolves around the modification of a polymer to enhance hydrophilicity, specifically using a parameter denoted as '\u03bc_ref'.\n2. **Value of \u03bb\u2080**: The goal is to calculate the value of a parameter \u03bb\u2080 while considering its dependence on '\u03bc_ref'.\n3. **Boundary Value Problem**: This suggests we are solving a mathematical or physical equation that governs the system's behavior, such as a differential equation with specific boundary conditions.\n4. **Relevance to Hydrophilicity**: Solving this problem has implications for understanding and predicting the hydrophilic properties of the modified polymer, which we must connect in our final explanation.\n\nWith these points clarified, we\u2019ll now devise a step-by-step methodology to calculate \u03bb\u2080 and explain its impact on the polymer\u2019s hydrophilicity.\n\n---\n\n### Part 2: **Detailed and Systematic Answer**\n\n#### **Step 1: Background on \u03bb\u2080 and \u03bc_ref**\nFor many hydrophilic polymers, \u03bb\u2080 represents a key parameter related to the system's equilibrium or characteristic property, such as water affinity, hydration dynamics, or solvation. \u03bc_ref presumably refers to a reference chemical potential associated with a specific solvent (e.g., water). By modifying the polymer with \u03bc_ref, we are altering its interaction with polar molecules like water.\n\nThe determination of \u03bb\u2080 therefore involves describing this interaction mathematically, which may be based on thermodynamic, kinetic, or transport properties of the system.\n\n#### **Step 2: Mathematical Framework**\nAssume the hydrophilic modification introduces a functional relationship involving \u03bb\u2080. Often, the relationship is governed by a differential equation involving mass transport, chemical potential, or free energy. For example:\n\n\\[\n\\frac{d^2\\lambda}{dx^2} - f(\\lambda, x, \\mu_{\\text{ref}}) = 0\n\\]\n\nHere:\n- \\(x\\): Spatial coordinate (e.g., polymer depth or solvent concentration gradient).\n- \\(f(\\lambda, x, \\mu_{\\text{ref}})\\): A function coupling \u03bb with the polymer-solution environment.\n- Boundary conditions: To solve this, we must specify boundary conditions such as:\n  - \\(\u03bb(x=0) = \u03bb_{\\text{surface}}\\) (surface hydrophilicity).\n  - \\(\u03bb(x=L) = \u03bb_{\\text{bulk}}\\) (bulk hydrophilicity at distance \\(L\\)).\n\nBoundary values ensure the problem reflects the physical system's constraints.\n\n#### **Step 3: Setting up the Experiment**\n1. **Polymer Pre-Treatment**:\n   - Select a base polymer and ensure it is ready for hydrophilic modification through surface activation techniques (e.g., plasma treatment, oxidation, or grafting).\n   - Ensure uniformity in the initial polymer properties to minimize experimental variability.\n\n2. **Modification with \u03bc_ref**:\n   - Introduce hydrophilic functional groups (e.g., \u2013OH, \u2013COOH, or poly(ethylene glycol) chains) through a coupling reaction influenced by \u03bc_ref.\n   - This may involve:\n     - A grafting agent (e.g., hydroxyethyl methacrylate (HEMA) or polyethylene glycol methacrylate).\n     - A controlled reaction environment (solvent, catalysts, etc.).\n\n3. **Parameter Setup for \u03bb\u2080 Determination**:\n   - Vary the applied \u03bc_ref during polymer modification using a range of controlled conditions.\n   - Each modification corresponds to a unique \u03bc_ref-induced structure.\n\n4. **Boundary Data Collection**:\n   - Measure relevant properties such as surface energy, water contact angles, or hydration levels across polymer depth.\n   - These measurements define our boundary conditions.\n\n#### **Step 4: Solving the Boundary Value Problem**\n1. Substitute experimental parameters and boundary conditions into the chosen governing equation (specific to your context, e.g., diffusion equation or chemical potential gradient).\n2. Use numerical methods (e.g., finite element analysis) for solutions if the equation is non-analytic. Software like MATLAB or COMSOL can perform this computation.\n3. Determine \u03bb\u2080 as a parameter that satisfies the equation under the given constraints.\n\n#### **Step 5: Validation and Interpretation**\n1. Correlate \u03bb\u2080 with experimentally observed hydrophilic properties:\n   - For example, as \u03bb\u2080 increases, water contact angle decreases, indicating greater hydrophilicity.\n2. If necessary, run additional experiments for polymers modified with different \u03bc_ref values to validate trends.\n\n---\n\n### Part 3: **How Solving the Boundary Value Problem Relates to Hydrophilicity**\n1. **Quantitative Understanding**: By calculating \u03bb\u2080, we can quantitatively describe the polymer's modified hydrophilicity. For instance, \u03bb\u2080 might define free energy at the water-polymer interface or solvent diffusion rate into the polymer network.\n2. **Optimization**: Solving the problem allows optimization of \u03bc_ref to achieve the desired hydrophilicity, assisting in fine-tuning the polymer properties for specific applications (e.g., biomedical hydrogels or membranes).\n3. **Predictability**: Theoretical solutions provide predictive power for how future modifications (via changes in \u03bc_ref) affect hydrophilic behavior, saving materials and time during experimental trials.\n\n---\n\n### Final Notes:\nUnderstanding and calculating \u03bb\u2080 involves careful synthesis, accurate experimental data, and robust mathematical solutions. Treat each step as iterative, where experimental observations refine model parameters. If you have additional context or polymer-specific data (e.g., chemical structure), I can help tailor the experimental and mathematical framework more precisely."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe how you would use multifactorial aziridines, such as CX-100, as crosslinking agents during the preparation of a hydrophilic polymer. What role do these crosslinking agents play in improving the hydrophilicity of the polymer material?"}, {"role": "assistant", "content": "To answer your question systematically and with thorough scientific rigor, let us carefully analyze the problem and break it down into its essential aspects, followed by providing a comprehensive experimental preparation approach for using multifactorial aziridines such as CX-100 as a crosslinking agent in hydrophilic polymer synthesis.\n\n---\n\n### Analysis of Key Points in the Question:\n1. **Focus on Hydrophilic Polymer Preparation**: You are asking about how to incorporate CX-100 (a multifactorial aziridine compound) as a crosslinking agent to prepare a hydrophilic polymer.\n2. **Role of Crosslinking Agents in Hydrophilicity**:\n   - Crosslinking agents help form a stable three-dimensional network within the polymer, which can contribute to enhanced water compatibility and mechanical properties.\n   - In the case of aziridines, their reactive aziridine functional groups can react with other polar or hydrophilic groups, improving water wettability and hydrophilicity.\n\nNow, let's delve into the detailed experimental preparation scheme, ensuring clarity for laboratory practice.\n\n---\n\n### Experimental Preparation Scheme for Using CX-100 as a Crosslinking Agent:\n\n#### Materials:\n1. **CX-100 (Multifunctional Aziridine)**: A commonly used trifunctional aziridine compound with excellent reactivity.\n2. **Hydrophilic Polymer Precursor**: Examples could include poly(acrylic acid), poly(vinyl alcohol), or other systems containing carboxyl (-COOH), hydroxyl (-OH), or amine (-NH2) functional groups.\n3. **Solvent**: Deionized water or aqueous alcohol mixtures (e.g., ethanol-water) for solubilizing the polymer precursor.\n4. **Catalyst (if needed)**: Acidic or basic catalysts to facilitate ring-opening reactions of aziridine groups.\n5. **Additives (optional)**: pH buffers, stabilizers, or surfactants if required for uniform dispersion.\n\n#### Step-by-Step Procedure:\n---\n\n**Step 1: Preparation of the Hydrophilic Polymer Precursor Solution**\n- Weigh out the required amount of the hydrophilic polymer precursor (e.g., poly(acrylic acid)).\n- Dissolve the polymer in deionized water or a compatible aqueous solvent system at room temperature (~25\u00b0C) under stirring. Use a magnetic stir bar to ensure complete dissolution.\n    - For example:\n      - Use 5 wt% poly(acrylic acid) in water for optimal solubility.\n- Add pH buffers if necessary to maintain neutrality (pH 7), to avoid undesired secondary reactions during crosslinking.\n\n---\n\n**Step 2: Addition of CX-100 Crosslinker**\n- Slowly add CX-100 (trifunctional aziridine) to the polymer solution under constant stirring. \n    - **Key Stoichiometry**: Maintain a functional group molar ratio of approximately 1:1 between aziridine groups (CX-100) and reactive groups (e.g., carboxyl groups of poly(acrylic acid)).\n    - For instance:\n      - Calculate the moles of \u2013COOH groups in the polymer precursor.\n      - Add an equimolar amount of CX-100 based on its molecular weight and assay.\n\n- Example: For a 5 wt% poly(acrylic acid) solution, using an average molecular weight of ~76 g/mol per \u2013COOH group, add the crosslinker proportionately.\n\n---\n\n**Step 3: Initiate Crosslinking Reaction**\n- Heat the solution gently to around 40\u201360\u00b0C while stirring to allow the aziridine functional groups to undergo ring-opening reactions with the polymer (e.g., carboxylic acid groups form amide linkages).\n    - **Note**: Aziridine groups react in a pH range of 6\u20139. If the pH is too low (<5), protonation could hinder the reactivity of the aziridine groups.\n    - In the presence of amines or hydroxyl groups, aziridine groups may form secondary amines or ether linkages. Adjust reaction conditions (e.g., temperature or catalyst) to selectively promote desired linkages.\n\n- Reaction Time: Allow the reaction to proceed for 4\u20136 hours to ensure complete crosslinking.\n\n---\n\n**Step 4: Stabilization and Washing of the Crosslinked Hydrophilic Polymer**\n- After the reaction is complete, cool the polymer solution to room temperature and precipitate the polymer network (if needed) by adding a nonsolvent, such as ethanol.\n- Wash the crosslinked polymer thoroughly with deionized water to remove unreacted CX-100 or other byproducts.\n\n---\n\n**Step 5: Drying the Crosslinked Polymer**\n- Dry the crosslinked hydrophilic polymer under vacuum at 50\u201360\u00b0C until a constant weight is achieved.\n\n---\n\n#### Role of CX-100 in Enhancing Hydrophilicity:\n1. **Crosslinking Effect**: CX-100 creates covalent bonds between polymer chains, resulting in a three-dimensional network that improves water retention and stability in aqueous environments.\n2. **Maintaining Polarity**: The hydrophilic domains of the polymer (e.g., -COOH, -OH, or -NH2 groups) remain accessible, ensuring good compatibility with water.\n3. **Hydrophilization via Aziridine Groups**: The aziridine groups promote reactions that introduce polar amide or hydroxyl groups, further enhancing hydrophilicity.\n\n---\n\n### Key Notes and Precautions for Success:\n1. **Reactivity Control**: The aziridine ring-opening mechanism is highly reactive. Control the pH and temperature to avoid premature side reactions.\n2. **Environmental Considerations**: Aziridines can sometimes exhibit toxicity. Work in a fume hood and use appropriate personal protective equipment (PPE).\n3. **Optimization**: The functional group molar ratio (e.g., aziridine to \u2013COOH groups) and reaction conditions should be fine-tuned based on the specific polymer system used.\n\n---\n\nBy systematically following this approach, you will achieve a hydrophilic polymer network with enhanced water affinity. Let me know if you need additional guidance during your experimental practice."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the steps you would take to incorporate a functional group from the provided molecule into the polymer structure to enhance its hydrophilicity. Be specific in identifying reaction conditions and mechanisms."}, {"role": "assistant", "content": "Certainly, let us take a systematic and detailed approach to analyze and derive an experimental preparation scheme for synthesizing a hydrophilic polymer by incorporating the functional group from the provided molecule.\n\n---\n\n### Step 1: Analyze the Provided Molecule and Polymer Properties\nThe first step is to carefully analyze the structure of the **provided molecule** and **existing polymer**. Key points to consider:\n- **Functional Group Identification**: Identify hydrophilic functional groups (e.g., hydroxyl (-OH), carboxylic acid (-COOH), amine (-NH2), or sulfonic acid (-SO3H)) present in the provided molecule, which may enhance water compatibility of the polymer.\n- **Reactivity**: Assess whether the functional group can react with sites on the polymer or whether suitable modification is required (e.g., activation, coupling agent).\n- **Polymer Chemistry**: Understand the chemistry of the polymer, whether it is addition polymerizable (e.g., vinyl-based) or condensation polymerizable (e.g., ester, amide-based).\n\nKey question: Does the provided molecule contain a functional group that can be covalently bonded to the polymer, and what reaction pathway will best incorporate it?\n\n---\n\n### Step 2: Select Reaction Pathway for Functionalization\nTo systematically enhance the hydrophilicity:\n- If the provided molecule contains **reactive functional groups** such as hydroxyl (-OH), carboxylic acid (-COOH), or an amine group (-NH2), they can act as nucleophiles to react with electrophilic groups already present in the polymer chain, cross-linker, or monomer precursor.\n- Alternatively, grafting of the hydrophilic molecule onto the polymer chain might involve a coupling reaction or free-radical grafting using appropriate initiators.\n\nTo proceed, we need to select the most effective strategy from the following:\n1. **Pre-polymerization Functionalization:** Modify the monomers before polymerization to include hydrophilic functional groups.\n2. **Post-polymerization Grafting:** Modify the polymer after synthesis by introducing hydrophilic side chains.\n3. **Co-polymerization Approach:** Introduce the provided hydrophilic molecule as a co-monomer during the polymerization stage.\n\nOnce the strategy is clear, choose solvents, conditions (e.g., temperature, pH), and a mechanism suitable for the polymer modification.\n\n---\n\n### Step 3: Develop a Detailed Experimental Scheme\nAssume the provided molecule contains a **-COOH functional group** and is to be incorporated into the polymer's structure. Let us adopt a **grafting approach**. Here is a stepwise outline:\n\n#### Step 3.1: Activate the Provided Hydrophilic Molecule\n- Convert the **carboxylic acid (-COOH)** group into a more reactive derivative, such as an **acid chloride (-COCl)**, to enhance reactivity toward the polymer. This is typically achieved using a chlorinating agent like **thionyl chloride (SOCl2)**.\n  **Reaction**: R-COOH + SOCl2 \u2192 R-COCl\n  **Conditions**: \n    - Solvent: Dry dichloromethane (DCM) or chloroform to avoid unwanted hydrolysis.\n    - Temperature: 40\u201350\u00b0C for 1\u20132 hours under reflux.\n    - Note: Perform under a fume hood, as HCl gas evolves.\n\n#### Step 3.2: Select and Prepare the Polymer Substrate for Reaction\n- Choose a starting polymer that has functional groups capable of reacting with the acid chloride derivative. For example:\n  - Hydroxyl-functionalized polymers (e.g., poly(vinyl alcohol), PVA).\n  - Amine-functionalized polymers (e.g., chitosan).\n\n#### Step 3.3: Graft the Hydrophilic Molecule Onto the Polymer Backbone\n- React the polymer with the acid chloride derivative.\n  **Reaction**: R'-OH (polymer) + R-COCl \u2192 R'-OCO-R (ester linkage on polymer).\n  **Conditions**:\n    - Solvent: Use an aprotic solvent like tetrahydrofuran (THF).\n    - Catalyst: Use a mild base (e.g., pyridine or triethylamine) to neutralize the HCl formed during the reaction.\n    - Temperature: Room temperature to 40\u00b0C.\n    - Reaction Time: Typically 12\u201324 hours to ensure adequate grafting.\n\n---\n\n### Step 4: Purification of the Modified Polymer\n- After reaction completion, precipitate the hydrophilic polymer in a suitable non-solvent (e.g., methanol or cold water) to remove unreacted reagents and byproducts.\n- Redissolve the polymer in a good solvent and precipitate again if further purification is needed.\n\n---\n\n### Step 5: Characterization of the Hydrophilic Polymer\nTo confirm successful functionalization:\n1. **Fourier-Transform Infrared Spectroscopy (FTIR)**: Identify characteristic peaks corresponding to newly formed functional groups, such as ester carbonyl (C=O) at ~1730 cm\u207b\u00b9.\n2. **1H-NMR/13C-NMR Spectroscopy**: Verify the presence of the grafted hydrophilic groups in the polymer matrix.\n3. **Contact Angle Measurement**: Assess hydrophilicity by measuring the water contact angle \u2014 a decrease indicates enhanced hydrophilicity.\n4. **Thermal Stability (TGA/DSC)**: Evaluate whether the modification affects thermal properties.\n\n---\n\n### Additional Notes and Adjustments\nDepending on the molecule you have provided, steps and functionalization methods can be adjusted:\n- If the provided molecule has a primary amino group (-NH2), use an electrophile such as epoxide-modified polymer for coupling.\n- Solvents, pH, and reaction conditions must always be compatible with the polymer and reagent stability.\n\n---\n\nBy following this comprehensive experimental scheme, you should be able to successfully incorporate the hydrophilic functional group into the polymer backbone, significantly improving its hydrophilicity. Let me know if you'd like to further refine the specifics! \ud83d\ude0a"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Design an experimental procedure to incorporate \u03b3-glycidoxypropyltrimethoxysilane into a polymer modification process. Explain its role in enhancing the hydrophilicity of the resulting material."}, {"role": "assistant", "content": "### Analysis of the Question:\nThe student is asking for an experimental procedure to incorporate **\u03b3-glycidoxypropyltrimethoxysilane (GPTMS)** into the polymer modification process, along with an explanation of how it contributes to enhancing the hydrophilicity of the resulting material. \n\n#### Key Points:\n1. **GPTMS Structure**: GPTMS is an organosilane compound with both epoxy functional groups and silane groups. The epoxy group can undergo ring-opening reactions, and the silane group can participate in hydrolysis and condensation reactions.\n2. **Role in Hydrophilicity**: GPTMS can enhance hydrophilicity because the hydrolyzed silane groups form silanol groups (-Si-OH) during polymer modification. These silanol groups can interact strongly with water, increasing hydrophilic properties.\n3. **Objective**: Develop a systematic, detailed synthesis procedure integrating GPTMS into a polymer to ensure controlled hydrophilicity enhancement.\n\n---\n\n### Experimental Procedure for Incorporating GPTMS:\n#### Materials and Reagents:\n- \u03b3-Glycidoxypropyltrimethoxysilane (GPTMS)\n- Base polymer (e.g., polyethylene glycol diacrylate \u2013 PEGDA or polyurethane elastomer)\n- Water (preferably deionized for silane hydrolysis)\n- Catalyst (e.g., hydrochloric acid or acetic acid for acid-catalyzed hydrolysis of silane)\n- Solvent (e.g., ethanol or isopropanol for silane dissolution)\n- Stirring apparatus, glass reactor equipped with temperature control\n- Optional crosslinker or secondary monomers with hydrophilic properties\n\n---\n\n#### Stepwise Experimental Procedure:\n**Step 1: Preparation of the GPTMS Solution**  \n1. Dissolve GPTMS in ethanol to form a homogeneous solution.  \n    - Typical concentration: Use 5\u201310 wt% GPTMS relative to the polymer matrix for moderate hydrophilicity.\n    - Example: For 50 g polymer, dissolve 2.5 g GPTMS in 20 mL ethanol.\n2. Gradually add deionized water (~5\u201310% volume of the GPTMS solution) to initiate hydrolysis of the methoxy groups to silanol groups (-Si-OH).  \n    - Reaction: GPTMS + H2O \u2192 Hydrolyzed silanol-containing intermediate.\n3. Add a small amount of acid catalyst (e.g., 0.1\u20130.5% of solution volume) to accelerate the hydrolysis reaction.  \n    - Maintain a mild temperature (~25\u201340\u00b0C) for 30\u201360 minutes while stirring.\n\n---\n\n**Step 2: Polymer Base Preparation**  \n1. Select a suitable polymer base for modification. If the polymer has hydroxyl (-OH), carboxyl (-COOH), or amine (-NH2) groups, they can react with the epoxy group in GPTMS.\n2. For a polymer like PEGDA, dissolve it in ethanol or other compatible solvents depending on the polymer solubility.  \n\n---\n\n**Step 3: Grafting of GPTMS onto the Polymer**  \n1. Slowly add the hydrolyzed GPTMS solution prepared in Step 1 to the polymer solution under constant stirring.  \n    - Use a polymer-to-GPTMS ratio tailored for desired hydrophilicity, e.g., 1:1 molar ratio of epoxy groups to hydroxyl groups in the polymer. Adjust based on experimental trials.\n2. Allow the epoxy group of GPTMS to undergo a ring-opening reaction with functional groups on the polymer backbone (e.g., -OH from PEG or polyurethane).  \n    - Reaction Conditions: Stir at 60\u201380\u00b0C for 2\u20138 hours, depending on the reactivity and viscosity of the mixture.\n    - Ensure the reaction proceeds in an inert atmosphere (e.g., nitrogen purging) to prevent oxygen-induced degradation.\n\n---\n\n**Step 4: Crosslinking/Condensation of Silane Groups**  \n1. After grafting GPTMS, allow the hydrolyzed silanol groups to undergo condensation reactions to form a crosslinked network within the polymer matrix.  \n    - Reaction: 2 Si-OH \u2192 Si-O-Si + H2O (polycondensation reaction).\n    - Maintain mild heating (40\u201360\u00b0C) with gentle stirring for an additional 4\u20136 hours to facilitate crosslinking.\n2. Add additional water (5\u201310 wt% of total materials) if condensation slows down.\n\n---\n\n**Step 5: Post-treatment and Curing**  \n1. After the reaction, remove excess ethanol and water by vacuum drying or solvent evaporation at a controlled temperature (~50\u00b0C).\n2. If needed, cure the polymer at elevated temperatures (e.g., 80\u2013120\u00b0C) to finalize crosslinking and stabilize the network.\n\n---\n\n**Step 6: Analysis of Modified Polymer**  \n1. Confirm success using characterization techniques:\n   - **FTIR**: Look for characteristic epoxy ring-opened signals (~900\u20131000 cm\u207b\u00b9) and Si-O-Si stretching (~1000\u20131100 cm\u207b\u00b9).\n   - **Contact Angle Measurement**: Assess enhanced hydrophilicity \u2013 smaller contact angles indicate improved hydrophilicity.\n   - **Thermal Analysis (TGA/DSC)**: Verify thermal stability and crosslinking density.\n   - **SEM/TEM**: Observe morphology changes post-modification.\n\n---\n\n### GPTMS Role in Enhancing Hydrophilicity:\n1. **Silanol Groups**: The hydrolyzed silane groups (-Si-OH) can form hydrogen bonds with water molecules, significantly increasing the material's ability to interact with water.\n2. **Epoxy Reactivity**: The epoxy group ensures covalent bonding of GPTMS to the polymer matrix, improving durability and compatibility of the hydrophilic segments.\n3. **Crosslinked Structure**: GPTMS can create a crosslinked network with silanol condensation, further increasing the polymer's water absorption capacity and improving hydrophilicity.\n\nBy following these detailed steps and understanding GPTMS's dual functionality, you can successfully integrate the material into a hydrophilic polymer system."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Design an experimental scheme to deposit multiple nanometer-scale layers of charged molecular materials onto a polymer substrate, ensuring each layer enhances the overall hydrophilic properties of the polymer. Outline the control parameters you would use to achieve the desired thickness and hydrophilicity."}, {"role": "assistant", "content": "Certainly! Let\u2019s break down the question systematically into steps for an experimental procedure to deposit nanometer-scale layers of charged molecular materials onto a polymer substrate, enhancing its hydrophilicity. This involves utilizing a well-established technique called **Layer-by-Layer (LbL) Assembly**. The key is to control the deposition of oppositely charged materials to form ultra-thin, uniform layers with tailored thickness and hydrophilic properties.\n\n---\n\n### Step-by-Step Design of the Experimental Scheme\n\n---\n\n#### **Step 1: Analyze the Question and Key Points**\nThe provided question centers on two interconnected objectives:\n1. **Nanometer-scale layering:** Controlled deposition of molecular materials with specific layer thicknesses (in the nanometer regime).\n2. **Enhanced hydrophilicity:** The added layers must introduce functional groups or properties that increase the hydrophilicity of the polymer substrate.\n\nThe solution lies in systematically assembling charged molecules (polyelectrolytes or other charged materials) and tuning their properties at the molecular scale using an *LbL Assembly* method.\n\n#### **Step 2: Materials and Reagents Required**\nBelow is a list of materials and reagents well-suited for this approach:\n1. **Polymer Substrate:** A hydrophobic polymer substrate (e.g., polyethylene terephthalate [PET], polyvinyl chloride [PVC], polystyrene, or a similar polymer).\n2. **Positively Charged Polyelectrolyte:** For example, poly(diallyldimethylammonium chloride) (PDDA) or poly-L-lysine.\n3. **Negatively Charged Polyelectrolyte:** For example, poly(sodium 4-styrenesulfonate) (PSS) or hyaluronic acid (HA).\n4. **Buffer Solution:** An aqueous buffer (e.g., phosphate-buffered saline [PBS] or NaCl solution) to maintain the ionic strength during deposition.\n5. **Deionized Water (DI Water):** To prepare the buffer and rinse between each deposition step.\n6. **Optional Hydrophilic Additives:** Small molecules or surfactants to improve wettability during or after deposition, e.g., poly(ethylene glycol) (PEG) or zwitterionic molecules.\n\n---\n\n#### **Step 3: Experimental Parameters**\nControl parameters to ensure nanometer-scale layering and hydrophilicity:\n1. **Layer Thickness:** Thickness of each layer (5-10 nm) controlled primarily by the concentration and adsorption time of the polyelectrolytes.\n2. **pH and Ionic Strength:** Buffer pH and salt concentration affect the charge density of polyelectrolytes and their binding efficiency.\n3. **Washing Steps:** Thorough rinsing between layers to remove loosely bound material and prevent uneven deposition.\n4. **Number of Layers:** Adjust the number of assembled bilayers (typically up to 10-20) to achieve the desired hydrophilic surface properties.\n\n---\n\n#### **Step 4: Procedure**\nBelow is a systematic procedure for the layer-by-layer deposition:\n\n---\n\n**Step 4.1: Substrate Preparation**\n- **Clean the Polymer Substrate:**\n  - Wash the polymer substrate (e.g., PET or PVC film) with ethanol and deionized water to remove contaminants.\n  - Dry with nitrogen or in a desiccated environment.\n  - Optionally, perform mild oxygen plasma treatment (if accessible) to activate the surface and introduce polar groups, further improving hydrophilicity and adhesion.\n\n---\n\n**Step 4.2: Prepare Polyelectrolyte Solutions**\n- Dissolve **PDDA** (positively charged polyelectrolyte) in the buffer solution (e.g., 0.5 M NaCl, pH 6.5-7) to a concentration of ~1 mg/mL.\n- Similarly, prepare a ~1 mg/mL solution of the **PSS** (negatively charged polyelectrolyte) in the buffer solution.\n- Filter both solutions through a 0.22 \u00b5m membrane to remove particulates.\n\n---\n\n**Step 4.3: Deposition of Layer-by-Layer Films**\nRepeat the following cycle for the desired number of bilayers:\n1. **Deposit the Positively Charged Layer:**\n   - Immerse the polymer substrate into the PDDA solution for 10 minutes at room temperature. Electrostatic interactions will adsorb the positively charged polymer onto the substrate surface.\n   - Gently rinse the substrate with DI water for 1-2 minutes to remove unbound PDDA.\n2. **Deposit the Negatively Charged Layer:**\n   - Immerse the polymer substrate into the PSS solution, again for 10 minutes at room temperature. Electrostatic interactions will cause the negatively charged PSS to bind to the positively charged PDDA layer.\n   - Rinse the substrate with DI water for 1-2 minutes to remove unbound PSS.\n3. **Repeat Steps 1 and 2** to build up the desired number of bilayers (e.g., 10 total repetitions = 10 PDDA/PSS layers).\n\n---\n\n**Step 4.4: Post-Treatment to Enhance Hydrophilicity**\n- After achieving the desired number of layers, rinse the final coated substrate with DI water and dry it under nitrogen flow or ambient conditions.\n- Optionally introduce functional groups, such as PEGylation, on the outermost layer by immersing the substrate in a PEG derivative solution (e.g., methoxy-PEG-silane at 1 wt% in DI water) for 1-2 hours followed by rinsing.\n\n---\n\n#### **Step 5: Characterization of the Hydrophilic Coatings**\nRun the following analyses to confirm coating integrity and hydrophilicity:\n1. **Water Contact Angle Measurement:** A lower contact angle (<30\u00b0) indicates higher hydrophilicity.\n2. **Ellipsometry or AFM (Atomic Force Microscopy):** To measure the thickness of each nanolayer and verify uniformity.\n3. **Zeta Potential Measurement:** Verify surface charge of the deposited layers at each stage.\n4. **ATR-FTIR or XPS Analysis:** Confirm the presence of functional groups that contribute to hydrophilicity (e.g., sulfonate or amine groups).\n\n---\n\n#### **Step 6: Troubleshooting and Optimization**\n- If thickness per layer exceeds 10 nm, reduce the polyelectrolyte concentration or adsorption time.\n- If hydrophilicity is insufficient, increase the number of bilayers or modify the final layer chemistry (e.g., adding a PEGylated or zwitterionic layer).\n- Adjust pH or ionic strength for better electrostatic interaction if deposition is uneven.\n\n---\n\n### Summary\nThis experimental procedure uses **Layer-by-Layer (LbL) Assembly** to deposit nanometer-scale layers of oppositely charged polyelectrolytes on a polymer substrate, enhancing hydrophilicity. Careful control of solution concentration, deposition time, and rinsing steps ensures uniform layer formation. The hydrophilicity of the final product can be fine-tuned by adjusting the number of layers or functionalizing the outermost layer with hydrophilic compounds such as PEG."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Design an experimental scheme where N,N-dimethylacrylamide (DMAA) is included to form a hydrophilic coating on a medical-grade polymer surface. Be specific about the steps and conditions required."}, {"role": "assistant", "content": "To design an experimental scheme incorporating **N,N-dimethylacrylamide (DMAA)** to create a **hydrophilic coating** on a medical-grade polymer surface, we will step through the process meticulously. The hydrophilic polymer coating must be stable, biocompatible, and offer sustained hydrophilicity, all of which are critical for medical applications.\n\n---\n\n### **Step 1: Key Question Analysis**\n\n**Primary Goal:**\n1. To utilize DMAA to form a hydrophilic coating on a medical-grade polymer surface.\n\n**Considerations:**\n1. The polymer surface must be modified to ensure the coating strongly adheres, as untreated polymer surfaces typically lack reactive groups for polymerization. \n2. The polymerization of DMAA will likely proceed via free-radical polymerization, a well-established method for hydrophilic polymer synthesis.\n3. Surface-induced polymerization or grafting may be used for coating stability.\n4. The hydrophilicity will stem from the DMAA side-chain's ability to form hydrogen bonds with water molecules.\n\nKey steps will include:\n1. Surface preparation of the medical-grade polymer.\n2. Initiating or facilitating graft polymerization of DMAA.\n3. Optimization of reaction conditions to achieve a uniform and functional hydrophilic coating.\n\n---\n\n### **Step 2: Experimental Scheme**\n\n#### **Step 2.1: Materials and Reagents**\n- **Substrate:** Medical-grade polymer (e.g., Polyurethane, Silicone, or Polyethylene).\n- **Monomer:** N,N-Dimethylacrylamide (DMAA).\n- **Photoinitiator:** Benzophenone (surface-attached or dissolved for UV-initiated polymerization), or similar radical initiators (e.g., Irgacure 2959 for aqueous photopolymerization).\n- **Solvent:** Ethanol or isopropanol, if needed, to clean the surface.\n- **Oxidizing agent:** Hydrogen peroxide (H\u2082O\u2082), for pretreating the polymer surface in cases where no reactive groups are present.\n- **Crosslinker (optional):** N,N\u2032-methylenebisacrylamide, if some degree of crosslinking is needed for coating durability.\n- **Buffers and additives** (if needed): To ensure biocompatibility and stability.\n\n---\n\n### **Step 2.2: Procedure**\n\n#### **A. Surface Preparation of the Medical-Grade Polymer**\n1. **Cleaning:** Rinse the medical-grade polymer in ethanol or isopropanol and ultrasonicate for 5\u201310 minutes to remove surface contaminants.\n2. **Oxidation/Activation:** \n   - Immerse the substrate in a solution of **30% hydrogen peroxide** at room temperature for 1\u20132 hours to create hydroxyl or peroxide groups on the surface. \n   - Alternately, plasma treatment (e.g., oxygen plasma for 5 minutes) can be used to increase surface wettability and introduce surface functionalities.\n3. **Functionalization with a Photoinitiator (if applicable):**\n   - Immerse the substrate in a solution of **Benzophenone (2% w/v)** dissolved in ethanol or acetone for 30 minutes at room temperature. This step enables photoinitiated radical grafting of DMAA onto the surface.\n\n#### **B. Preparation of the DMAA Polymerization Mixture**\n1. **Prepare the Monomer Solution:**\n   - Dissolve **N,N-dimethylacrylamide (DMAA)** monomer in distilled water or an alcohol-water mixture to create a 5\u201310% (v/v) solution.\n   - If durability is critical, add **0.01\u20130.05% N,N\u2032-methylenebisacrylamide** as a mild crosslinker.\n   - Adjust the solution to neutral pH using a buffer (e.g., phosphate-buffered saline) to ensure compatibility with medical surfaces.\n\n2. **Photoinitiator Activation (if not surface-tethered):**\n   - Add **Irgacure 2959 (0.2\u20130.5% w/v)** or a water-soluble photoinitiator to the solution for radical initiation under UV light.\n   - If thermal polymerization is preferred, **ammonium persulfate (0.5% w/v)** with **N,N,N\u2032,N\u2032-tetramethylethylenediamine (TEMED)** can substitute the photoinitiator.\n\n#### **C. Polymerization Process**\n1. Place the pre-treated medical-grade polymer substrate into the monomer solution, ensuring complete surface contact.\n2. Initiate polymerization:\n   - For **UV-initiated polymerization**, irradiate the substrate with a UV lamp (e.g., 365 nm wavelength) at an intensity of ~5 mW/cm\u00b2 for 15\u201330 minutes.\n   - For **thermal polymerization**, incubate at 40\u201360 \u00b0C for 2\u20134 hours.\n\n#### **D. Post-Polymerization Washing and Drying**\n1. Remove the substrate from the solution and rinse thoroughly with **water or weak ethanol solution** to remove unreacted monomers.\n2. Immerse the substrate in distilled water overnight at room temperature to leach out any remaining initiators or non-bonded polymer byproducts.\n3. Dry the coated substrate under vacuum or air-dry it in a dust-free environment.\n\n---\n\n### **Step 3: Reaction Parameters & Optimization**\n\n- **Monomer Concentration:** 5\u201310% w/v is optimal for forming a uniform, hydrophilic coating without excessive swelling.\n- **UV Curing Time:** Monitor for uniform polymerization, optimizing exposure time depending on lamp intensity and polymer surface geometry.\n- **Hydrophilic Test:** Assess surface hydrophilicity via **water contact angle measurement (target: <30\u00b0)** and confirm via XPS (for nitrogen incorporation from DMAA).\n\n---\n\n### **Step 4: Quality Control and Validation**\n1. Perform **water retention and stability tests** (e.g., immersion in saline solution at 37 \u00b0C for 24 hours) to verify coating durability.\n2. Conduct **biocompatibility tests** to confirm that the coated surface meets medical standards.\n\n---\n\n### **Concluding Remarks**\n\nThis process ensures a stable, covalently grafted hydrophilic coating incorporating N,N-Dimethylacrylamide. The use of photoinitiators and surface pretreatment maximizes adhesion, while the detailed reaction conditions ensure reproducibility for medical applications. Feel free to discuss specific materials or reaction constraints if adaption is needed to different substrates!\n\n"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the role of polysorbate in modifying a polymer to enhance its hydrophilicity and propose a method for incorporating it into a polyurethane-based prepolymer system."}, {"role": "assistant", "content": "Certainly! Let us break down your question systematically and address it in detail so that you can understand the role of polysorbate in enhancing polymer hydrophilicity and learn how to successfully incorporate it into a polyurethane-based prepolymer system.\n\n---\n\n### **Question Analysis and Key Points**\nYour question focuses on:\n1. **The role of polysorbate** in modifying a polymer to enhance hydrophilicity. Polysorbates are widely used non-ionic surfactants with amphiphilic properties, which can improve the hydrophilicity of a polymer system.\n2. **A method for incorporating polysorbate into a polyurethane (PU)-based prepolymer system**, which means an experimental approach to physically or chemically integrate polysorbate into the polymer during synthesis.\n\n---\n\n### **Step 1: Role of Polysorbate in Enhancing Hydrophilicity**\n**Polysorbate (e.g., Polysorbate-20, Polysorbate-80)** is a surfactant containing hydrophilic polyoxyethylene groups and hydrophobic fatty acid ester groups. These characteristics allow polysorbates to interact with both hydrophilic and hydrophobic components in polymer matrices. Here is its specific role in enhancing polymer hydrophilicity:\n\n1. **Introduction of Hydrophilic Groups:** The polyoxyethylene moieties (-CH\u2082CH\u2082O-) in polysorbate are highly hydrophilic and can interact with water or other polar environments. Incorporating polysorbate into a polymer matrix adds functional groups capable of forming hydrogen bonds with water, thereby increasing the polymer's affinity for water (hydrophilicity).\n   \n2. **Improved Surface Properties:** Polysorbate tends to migrate toward the polymer surface, where its hydrophilic groups can improve wettability and create a water-compatible outer layer. This effect is particularly desirable in biomedical applications (hydrogels, coatings) where contact with aqueous media is required.\n\n3. **Compatibility with Polyurethane Systems:** Polysorbates are miscible with polyurethane prepolymers and can be covalently or physically incorporated during synthesis without significantly disturbing the polymer's mechanical properties.\n\n---\n\n### **Step 2: Proposed Method for Incorporating Polysorbate into a Polyurethane-Based Prepolymer System**\n\nTo systematically incorporate polysorbate into a polyurethane-based system, here is a detailed preparative scheme:\n\n#### Overview of the Process:\nIn polyurethane synthesis, polymers are typically prepared by the reaction between a diisocyanate and a polyol in the presence of catalysts. Polysorbate can be incorporated **either as a hydrophilic polyol** or as an additive blended into the polymer matrix.\n\n---\n\n### **Experimental Scheme \u2013 Incorporation of Polysorbate**\n\n#### **Materials Required:**\n1. **Polyisocyanate:** e.g., methylene diphenyl diisocyanate (MDI) or toluene diisocyanate (TDI).\n2. **Polyols:** A conventional polyether or polyester polyol (base polyol for polyurethane synthesis).\n3. **Polysorbate (e.g., Polysorbate-20 or Polysorbate-80):** To introduce hydrophilicity into the polymer.\n4. **Catalyst:** Dibutyltin dilaurate (DBTL) or other organotin catalysts to accelerate the reaction.\n5. **Solvent (if required):** Tetrahydrofuran (THF) or dimethylformamide (DMF) as the reaction medium.\n6. **Chain Extender or Crosslinker (Optional):** Such as ethylene glycol or 1,4-butanediol, to enhance polymer properties.\n\n---\n\n#### **Step 1: Preparation of the Polyurethane Prepolymer**\n1. **Set-Up:**\n   - Use a round-bottom flask equipped with a mechanical stirrer, thermometer, and nitrogen inlet to prevent moisture contamination.\n   - Add the required polyisocyanate (e.g., MDI) and polyol in a molar ratio (usually 2:1 for diisocyanate to polyol).\n\n2. **Reaction Conditions:**\n   - Carry out the reaction at 70\u201380 \u00b0C under a nitrogen atmosphere.\n   - Stir the mixture until the reaction is complete (typically 1\u20132 hours), as indicated by the disappearance of the NCO absorption peak in IR spectroscopy (~2270 cm\u207b\u00b9).\n\n---\n\n#### **Step 2: Incorporation of Polysorbate**\n1. **Determine the Amount of Polysorbate:**\n   - To enhance hydrophilicity without sacrificing mechanical integrity, polysorbate can replace 5\u201320 wt% of the primary polyol used in the synthesis.\n   - Example: For 50 g of a polyol, incorporate 5\u201310 g of polysorbate.\n\n2. **Blend Polysorbate:**\n   - Add the pre-determined quantity of polysorbate slowly into the prepolymer mixture prepared in Step 1 while stirring at 70\u201375 \u00b0C.\n   - Ensure homogeneous mixing for approximately 30 minutes. The hydrophilic polyoxyethylene groups in the polysorbate will interact with the polyurethane network.\n\n---\n\n#### **Step 3: Chain Extension and Crosslinking**\n1. **Introduce a Chain Extender:**\n   - Add a small-molecule chain extender (e.g., ethylene glycol or 1,4-butanediol) to react with any remaining NCO groups in the prepolymer. This step increases molecular weight and forms a crosslinked polymer network.\n\n2. **Reaction Conditions:**\n   - Maintain the temperature at 70\u201380 \u00b0C for an additional 1\u20132 hours under stirring.\n   - Monitor the reaction by tracking the disappearance of the NCO group in IR spectroscopy.\n\n---\n\n#### **Step 4: Cure the Polymer**\n1. Allow the polymer to cool and set in a mold or solution-cast it, depending on the application.\n2. If a solvent was used (e.g., THF), remove the solvent by evaporation or precipitation in non-solvent (e.g., methanol).\n\n---\n\n### **Key Reaction Notes:**\n1. **Polysorbate Stability:** Ensure polysorbate is compatible at reaction temperatures. Overheating may degrade the polyoxyethylene chain, reducing effectiveness.\n2. **Optimize Ratios:** Excess polysorbate can weaken the mechanical properties of the polymer network (e.g., tensile strength).\n3. **Hydrophilic Balance:** The amount of polysorbate directly affects water uptake/swelling of the polymer. Optimize based on desired application (e.g., biomedical hydrogels or coatings).\n\n---\n\n### **Expected Results and Benefits**\n1. **Enhanced Hydrophilicity:** The incorporation of polysorbate introduces polyoxyethylene chains that significantly increase the water affinity of the polyurethane.\n2. **Improved Wettability:** The polymer surface becomes more hydrophilic, which can be confirmed using contact angle measurements (decreased water contact angle).\n3. **Versatility:** The modified polymer is suitable for use in water-compatible applications, such as drug delivery systems, tissue engineering scaffolds, or anti-fouling coatings.\n\n---\n\n### **Conclusion**\nThrough the experimental strategy outlined above, polysorbate can be successfully incorporated into a polyurethane-based prepolymer system, enhancing its hydrophilicity while maintaining structural and mechanical integrity. By optimizing polysorbate content during prepolymer synthesis, you can fine-tune the properties of your hydrophilic polymer for specific applications."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the steps you would take to prepare a dual-cross-linked hydrophilic polymer coating using quaternary ammonium groups. Why do you think these groups are important in modifying the surface properties of the polymer?"}, {"role": "assistant", "content": "To answer your question regarding the preparation of a dual-cross-linked hydrophilic polymer coating using quaternary ammonium groups, I will analyze the key aspects of the question, systematically provide the preparation steps, and delve into the details necessary for experimental implementation. Additionally, I will explain why quaternary ammonium groups are important for modifying the surface properties of the polymer.\n\n---\n\n**Analysis of the Question:**\n\n1. **Key Objectives:**\n   - To design a dual-cross-linked hydrophilic polymer coating.\n   - Incorporate quaternary ammonium groups into the polymer structure.\n   - Enhance surface hydrophilicity and functionality.\n\n2. **Quaternary Ammonium Groups:**\n   These positively charged groups can impart antibacterial properties, improve ionic conductivity, enhance hydrophilicity, and contribute to electrostatic interactions.\n\n3. **Dual-cross-linked Polymer:**\n   Dual cross-linking typically involves two distinct cross-linking strategies, such as covalent bonds and ionic interactions, to improve mechanical stability, durability, and functionality.\n\n---\n\n**Step-by-Step Preparation of Dual-Cross-Linked Hydrophilic Polymer Coating:**\n\n### Step 1: **Selection of Base Polymer**\nChoose a base polymer capable of functionalization with quaternary ammonium groups and suitable for cross-linking. For this experiment, polyvinyl alcohol (PVA) is an excellent candidate due to its hydrophilicity, ease of functionalization, and compatibility with cross-linking strategies.\n\n- **Materials Needed:** PVA (with molecular weight ~85,000\u2013124,000 g/mol), deionized water, stirring apparatus.\n- **Procedure:**\n  - Dissolve PVA in deionized water at 80\u00b0C under constant stirring to prepare a 10 wt.% aqueous solution. Ensure complete dissolution to form a homogeneous polymer solution.\n\n---\n\n### Step 2: **Functionalization with Quaternary Ammonium Groups**\nIntroduce quaternary ammonium groups into the polymer structure via chemical reactions or grafting.\n\n- **Reagents:**\n  - Epichlorohydrin (cross-linking agent).\n  - Trimethylamine or a similar tertiary amine (to form quaternary ammonium groups).\n- **Procedure:**\n  1. Add epichlorohydrin dropwise (molar ratio: PVA:epichlorohydrin = 1:1) to the cooled PVA solution (~30\u00b0C) while maintaining stirring.\n  2. After homogenization, introduce trimethylamine (molar ratio trimethylamine:epichlorohydrin = 1:1) to the solution.\n  3. Allow the reaction to proceed for 4\u20136 hours at 50\u00b0C under mild stirring.\n  4. Monitor the reaction using FTIR or ^1H NMR to verify the formation of quaternary ammonium groups.\n  5. Dilute the solution to adjust viscosity, if required.\n\n---\n\n### Step 3: **Covalent Cross-Linking**\nEstablish the first cross-linking network through covalent bonding.\n\n- **Reagents:**\n  - Glutaraldehyde (as a secondary cross-linker).\n- **Procedure:**\n  1. Add glutaraldehyde to the final quaternized polymer solution (molar ratio glutaraldehyde:PVA = 1:2).\n  2. Maintain stirring at room temperature (~25\u00b0C) for 4\u20138 hours.\n  3. Ensure covalent cross-linking occurs through aldehyde groups reacting with hydroxyl groups on PVA.\n  4. Confirm the cross-linking using gel formation tests or swelling ratio analysis.\n\n---\n\n### Step 4: **Ionic Cross-Linking**\nIntroduce a secondary ionic cross-linking network using divalent or trivalent cations to create additional stability.\n\n- **Reagents:**\n  - Metal ions such as calcium chloride (CaCl\u2082) or magnesium sulfate (MgSO\u2084) (ionic cross-linkers).\n- **Procedure:**\n  1. Add an aqueous solution of CaCl\u2082 (molar ratio CaCl\u2082:PVA = 1:5) to the polymer coating mixture.\n  2. Allow ionic cross-linking interactions to occur for 1\u20132 hours with gentle stirring.\n  3. Evaluate ionic cross-linking stability using mechanical tests.\n\n---\n\n### Step 5: **Polymer Coating Application**\nApply the prepared polymer to the target substrate (e.g., glass, metal, or polymer surface).\n\n- **Procedure:**\n  1. Clean the substrate thoroughly (e.g., with ethanol or acetone).\n  2. Dip-coat or spray-coat the polymer solution onto the substrate.\n  3. Dry the coated substrate at 50\u201370\u00b0C for several hours to ensure film formation.\n  4. Characterize the coating's uniformity and adhesion using SEM or AFM.\n\n---\n\n### Step 6: **Characterization**\nAssess the hydrophilic polymer coating for desired properties.\n\n- **Characterization Techniques:**\n  - **Hydrophilicity Test:** Water contact angle measurement to confirm enhanced hydrophilicity.\n  - **Antibacterial Activity:** Zone of inhibition tests to verify the efficacy of quaternary ammonium groups.\n  - **Mechanical Properties:** Tensile testing for polymer strength.\n  - **Chemical Analysis:** FTIR or XPS to confirm the presence of quaternary ammonium groups.\n\n---\n\n**Why Quaternary Ammonium Groups are Important:**\n\n1. **Hydrophilicity:** Quaternary ammonium groups improve water affinity due to their ionic nature, leading to enhanced wetting on the surface.\n2. **Antibacterial Properties:** The positively charged ammonium groups can disrupt bacterial membranes, reducing microbial contamination on the surface.\n3. **Electrostatic Interactions:** These groups enable ionic interaction, which can be exploited for secondary cross-linking or surface functionalization.\n4. **Functional Versatility:** Apart from hydrophilicity, they can also enhance chemical resistance and introduce ionic conductivity, making the coating suitable for diverse applications like biomedical devices or filtration membranes.\n\n---\n\nBy following these steps systematically and precisely, you can successfully prepare a dual-cross-linked hydrophilic polymer coating integrated with quaternary ammonium groups. This process not only optimizes surface hydrophilicity and functionality but also ensures durability and applicability in advanced material systems."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain how you would use triethoxyvinylsilane (A151) in the synthesis of a hydrophilic polymer. Specify the conditions and steps required for this molecule to effectively contribute to the polymerization process."}, {"role": "assistant", "content": "Thank you for your question. I appreciate your curiosity in the synthesis of hydrophilic polymers and your interest in triethoxyvinylsilane (A151) as a precursor. Let\u2019s examine this systematically, step-by-step, in detail.\n\n---\n\n### **Analysis and Key Points**\n\nTriethoxyvinylsilane (A151) is a silane coupling agent containing a vinyl group that facilitates participation in polymerization reactions, while its triethoxy functional group enables hydrolysis and condensation to generate silanol groups. Its versatility makes it an ideal component for enhancing the hydrophilicity of polymer systems.\n\nTo use A151 effectively in the synthesis of a hydrophilic polymer, the strategy typically involves:\n1. **Incorporating the vinyl group into the polymer backbone** via radical polymerization.\n2. **Introducing hydrophilic functional groups** through strategies like co-polymerization or post-modification.\n3. **Exploiting the triethoxy functionalities** for hydrolysis and cross-linking to introduce silanol (-SiOH) functionalities that enhance hydrophilicity.\n\nWe will design a practical synthesis scheme involving A151 based on these properties.\n\n---\n\n### **Experimental Preparation Scheme for the Synthesis of a Hydrophilic Polymer Using Triethoxyvinylsilane (A151)**\n\n#### **Step 1: Selection of Co-Monomer or Hydrophilic Modifier**\nSince A151 does not inherently contribute significant hydrophilicity, it is essential to co-polymerize A151 with a hydrophilic monomer such as:\n- **Acrylic acid (AA)**: A monomer with carboxylic acid groups that ensure hydrophilicity.\n- **Hydroxyethyl methacrylate (HEMA)**: Provides hydroxyl groups for enhanced hydrophilicity.\n\nFor this example, we will co-polymerize A151 with acrylic acid (AA).\n\n---\n\n#### **Step 2: Preparation of the Reaction Mixture**\n- **Reagents:**\n  - Triethoxyvinylsilane (A151): 0.2\u20130.5 mol\n  - Acrylic acid (AA): 1 mol\n  - Solvent: Ethanol or water (ethanol aids in solubilizing A151; water facilitates hydrolysis of the triethoxy groups later).\n  - Initiator: Azobisisobutyronitrile (AIBN), commonly used for radical polymerization; ~0.01 mol% relative to monomer concentrations.\n  - Catalyst (optional): Acidic catalysts such as HCl or H2SO4 for hydrolysis of the triethoxy group.\n\n---\n\n#### **Step 3: Radical Co-Polymerization**\nRadical polymerization introduces vinyl groups (from A151 and AA) into the polymer backbone.\n\n1. **Reaction Setup:**\n   - Use a three-neck flask equipped with a stirrer, condenser, and nitrogen inlet.\n   - Charge the flask with A151, acrylic acid, the solvent (ethanol or ethanol-water mixture), and AIBN.\n   - Purge the reaction mixture with nitrogen for ~30 minutes to eliminate oxygen, which can inhibit polymerization.\n\n2. **Reaction Conditions:**\n   - Maintain a temperature of **65\u201375\u00b0C** for 4\u20136 hours (this is the optimal range for AIBN decomposition and radical initiation).\n   - Stir continuously to ensure homogeneity of the reaction mixture.\n\n3. **Polymer Formation:**\n   - Co-polymerization proceeds, where vinyl groups polymerize to form the hydrophilic polymer backbone, incorporating silane groups.\n\n---\n\n#### **Step 4: Hydrolysis of Triethoxy Groups**\nPost-polymerization, the triethoxy groups on A151 are hydrolyzed to generate hydrophilic silanol groups. This step significantly enhances the hydrophilicity of the polymer.\n\n1. **Hydrolysis Conditions:**\n   - Add a small amount of acidic catalyst (e.g., dilute HCl, pH ~3\u20134) to the reaction mixture.\n   - Use water or a water-ethanol mixture as a solvent medium.\n   - Stir at room temperature (~20\u201325\u00b0C) for 6\u201312 hours to allow hydrolysis of the ethoxy groups (-OEt) into hydroxyl (-OH) groups, forming silanol (-SiOH).\n\n2. **Condensation (Optional):**\n   - Catalyze condensation between silanol groups to form cross-linked domains in the polymer structure. This creates a gel-like or network structure, further enhancing hydrophilicity and mechanical stability.\n\n---\n\n#### **Step 5: Purification**\nAfter the polymerization and hydrolysis reactions, purification ensures the removal of unreacted monomers, initiators, and by-products.\n1. **Precipitation:**\n   - Precipitate the polymer by adding the reaction solution to a non-solvent such as acetone or diethyl ether.\n2. **Washing:**\n   - Wash the polymer with water to remove soluble impurities.\n3. **Drying:**\n   - Dry the purified polymer in a vacuum oven at ~40\u201360\u00b0C.\n\n---\n\n#### **Step 6: Characterization**\nThe synthesized polymer may be characterized to confirm structure and hydrophilicity enhancement.\n1. **Structural Analysis:**\n   - Use Fourier-transform infrared (FTIR) spectroscopy to identify hydroxyl (-OH), carboxyl (-COOH), and silanol (-SiOH) groups in the polymer.\n2. **Thermal Properties:**\n   - Perform thermogravimetric analysis (TGA) or differential scanning calorimetry (DSC) to evaluate the polymer's thermal stability.\n3. **Hydrophilicity Test:**\n   - Measure water contact angle to confirm improved hydrophilicity.\n\n---\n\n### **Conclusion**\nThrough this experimental scheme, triethoxyvinylsilane (A151) plays a dual role:\n1. **Polymer Backbone Incorporation:** The vinyl group participates in radical co-polymerization, forming part of the backbone.\n2. **Hydrophilicity Enhancement:** The hydrolysis of triethoxy groups introduces silanol (-SiOH) functionalities, amplifying the hydrophilic character of the polymer.\n\nBy carefully following reaction conditions\u2014such as correct temperature, reagent ratios, hydrolysis conditions, and purification steps\u2014you should be able to synthesize a hydrophilic polymer that leverages the unique properties of A151 effectively.\n\nIf you have additional questions or need further clarification, don\u2019t hesitate to ask\u2014synthesizing high-performance hydrophilic polymers is a fascinating and rewarding process!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "When preparing a hydrophilic polymer using tannic acid (TA) and polyvinyl alcohol (PVA), what solvent system would you recommend to achieve good processability and stability of the mixture? Justify your choice."}, {"role": "assistant", "content": "Certainly! This is an excellent question regarding the synthesis of hydrophilic polymers, especially using tannic acid (TA) and polyvinyl alcohol (PVA). Let's systematically analyze your question and provide a detailed and scientifically rigorous response.\n\n---\n\n### **Step 1: Analysis of the Question**\nThe question centers on selecting a solvent system for the preparation of a hydrophilic polymer using tannic acid (TA) and polyvinyl alcohol (PVA). The key considerations here are:\n\n1. **Solubility Compatibility**:\n   Both tannic acid and polyvinyl alcohol must be dissolved or dispersed effectively in the solvent to ensure homogeneous blending.\n\n2. **Processability**:\n   The solvent system should facilitate smooth preparation, avoid aggregation or precipitation of components, and allow consistent polymer formation.\n\n3. **Stability**:\n   The solvent medium should maintain the stability of the components (chemically and thermodynamically) during reaction and polymer processing.\n\n4. **Hydrophilicity Enhancement**:\n   The solvent choice must align with the goal of maximizing hydrophilicity in the resulting polymer, as TA and PVA are both hydrophilic in nature.\n\n---\n\n### **Step 2: Recommended Solvent System**\nAn ideal solvent system for the synthesis of a hydrophilic polymer using tannic acid (TA) and polyvinyl alcohol (PVA) would be **water-based**, specifically:\n\n1. **Distilled Water**:\n   - Tannic acid is highly soluble in water due to its polyphenolic structure with hydroxyl groups, which readily form hydrogen bonds with water.\n   - Polyvinyl alcohol is also soluble in water, particularly at elevated temperatures, as its hydroxyl groups interact strongly with water molecules.\n\n2. **Addition of Ethanol (Optional)**:\n   - If necessary to enhance processability (such as to reduce viscosity or facilitate mixing), a small percentage (5\u201320%) of ethanol can be added to the system. Ethanol improves miscibility and can slightly reduce the polarity of the solvent, aiding in uniform blending of the components.\n\n---\n\n### **Step 3: Justification of the Solvent Choice**\nThe selection of distilled water (with optional ethanol) is justified as follows:\n\n1. **Compatibility**:\n   - Tannic acid (TA) is inherently highly hydrophilic due to its phenol groups, and polyvinyl alcohol (PVA) has hydroxyl-rich chains. Water effectively solubilizes both components while supporting hydrogen bonding interactions.\n   - Ethanol can help stabilize the mixture by reducing viscosity and enhancing mixing, without compromising the hydrophilic characteristics.\n\n2. **Processability**:\n   - Water is a green solvent, easy to handle, and readily evaporates during the drying or curing process of polymer preparation. Ethanol evaporates even more quickly, ensuring clean processing.\n\n3. **Stability**:\n   - At room temperature and mild reaction conditions, both tannic acid and polyvinyl alcohol remain chemically stable in water. Upon heating (e.g., 70\u201390\u00b0C), PVA dissolves completely, and TA remains intact, forming a homogeneous mixture ideal for polymer crosslinking.\n\n4. **Promotion of Hydrophilicity**:\n   - The use of water ensures the hydrophilic functionality of TA and PVA is retained and further emphasized in the polymer network, as no nonpolar solvents are introduced that could interfere with hydrophilicity.\n\n---\n\n### **Step 4: Detailed Experimental Preparation Scheme**\nHere is a step-by-step synthesis procedure for preparing the hydrophilic polymer using tannic acid (TA) and polyvinyl alcohol (PVA), utilizing the selected solvent system:\n\n1. **Materials Required**:\n   - Tannic acid (TA)\n   - Polyvinyl alcohol (PVA) (molecular weight 85,000\u2013124,000, 99+% hydrolyzed preferred)\n   - Distilled water\n   - Ethanol (optional, for processability)\n   - Magnetic stirrer and heating plate\n   - Beaker, thermometer, and other standard laboratory equipment\n\n2. **Step 1: Preparation of PVA Solution**:\n   - Add **5\u201310 g of PVA** to **100 mL of distilled water** in a beaker.\n   - Heat the mixture to **70\u201390\u00b0C** with stirring to dissolve the PVA completely. Monitor the temperature carefully to avoid overheating, which may degrade the polymer.\n\n3. **Step 2: Preparation of TA Solution**:\n   - Dissolve **1\u20133 g of tannic acid** into **20\u201350 mL of distilled water** in a separate container. Stir the solution to ensure complete dissolution. If ethanol is being used, add it to this solution in a **10\u201315 vol% ratio**.\n\n4. **Step 3: Mixing**:\n   - Slowly add the TA solution to the PVA solution while stirring continuously to ensure homogeneous blending.\n   - If necessary, maintain a mild heating condition (around **50\u201360\u00b0C**) to facilitate uniform mixing.\n\n5. **Step 4: Crosslinking (Optional)**:\n   - To form a crosslinked hydrophilic polymer network, introduce a crosslinking agent (e.g., boric acid or glutaraldehyde) in controlled quantities. Typically, use **1\u20133 wt% of the crosslinker** based on the total weight of PVA present.\n   - Continue stirring for an additional 30\u201360 minutes.\n\n6. **Step 5: Casting and Drying**:\n   - Pour the mixture onto a flat substrate (glass or Teflon mold) and allow it to cure or evaporate at room temperature or mild heating (~40\u201360\u00b0C) overnight.\n   - Peel off the resulting polymer film, and confirm hydrophilicity via contact angle measurement or water absorption studies.\n\n---\n\n### **Step 5: Concluding Remarks**\nThe solvent system consisting of distilled water (with optional ethanol) provides the optimal balance of compatibility, processability, and stability for synthesizing hydrophilic polymers based on tannic acid and polyvinyl alcohol. Additionally, it promotes the desired hydrophilicity due to the absence of nonpolar solvents.\n\nThis comprehensive approach ensures that you can successfully synthesize a high-quality hydrophilic polymer in the laboratory while maintaining environmental considerations and scientific rigor.\n\nIf you have further questions or need clarification on experimental details, feel free to ask!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the procedure for purifying the polymer product obtained after using methyl methacrylate (MMA) to modify the polymer. What would be the rationale for choosing specific solvents during the precipitation process?"}, {"role": "assistant", "content": "### Question Analysis and Key Points\nYour question focuses on the **purification of a polymer modified by methyl methacrylate (MMA)** and the choice of solvents during the **precipitation process**. Both aspects are essential for isolating the polymer product in a pure, high-quality form. To answer this question in a systematic manner, let us:\n1. Break down the steps of polymer purification after MMA modification.\n2. Discuss the rationale for solvent selection during precipitation in detail.\n\nThe underlying principles guiding the purification process are:\n- Separation of unreacted monomers or initiators, residual MMA, by-products, and solvents from the polymer.\n- Ensuring the polymer's integrity, hydrophilicity, and molecular structure remain unaltered.\n\n### Systematic Answer: Purification Procedure\n\n#### **Step 1: Dissolution of the Crude Polymer**\nAfter the MMA modification reaction is complete, the reaction mixture typically contains the following components:\n- The synthesized polymer (a blend of original polymer and MMA-based copolymer).\n- Unreacted monomers (MMA).\n- Initiators, additives, or catalysts (optional, depending on the conditions of the MMA modification reaction).\n- Reaction solvents.\n\n1. **Selection of a Solvent for Dissolution**:\n   - Choose a solvent in which the polymer is highly soluble.\n   - Common choices include **tetrahydrofuran (THF)**, **acetone**, or a similar organic solvent compatible with MMA-modified hydrophilic polymers.\n   - Ensure the solvent can dissolve not just the polymer but also smaller molecular impurities and residuals, which will facilitate separation in later steps.\n\n2. **Procedure**:\n   - Transfer the reaction mixture to a flask.\n   - Add the selected solvent gradually (approximately 10\u201315 mL per gram of crude polymer) while stirring gently.\n   - Heat the mixture slightly (e.g., to 30\u201350\u00b0C) to assist dissolution if required. Avoid temperatures that can degrade the polymer.\n\n#### **Step 2: Precipitation of the Purified Polymer**\nPrecipitation is a key isolation method in polymer purification. The goal is to selectively precipitate the polymer while leaving soluble by-products and impurities in the liquid phase.\n\n1. **Selection of a Precipitation Solvent**:\n   - Choose a nonsolvent, i.e., a solvent in which the polymer is **insoluble**, but one that can dissolve impurities and residual reactants effectively.\n   - The nonsolvent must also enable the precipitation of the polymer into a collectable solid without deforming its structure or molecular conformation.\n\n   **Common solvent pairings**:\n   - **Polymer-solvent (e.g., THF) and nonsolvent (e.g., methanol)**.\n   - **Acetone-chilled diethyl ether**.\n   - Other common nonsolvents: ethanol, isopropanol, water (depends on polymer solubility and hydrophilicity).\n\n2. **Precipitation Procedure**:\n   - Gradually add the reaction solution (dissolved polymer in solvent) dropwise into a large volume of cold nonsolvent (ratio of 1:5 or 1:10, polymer solution to nonsolvent, is typical). E.g., 10 mL of dissolved polymer solution is added to 100 mL of cold methanol.\n   - Stir continuously during the addition to ensure uniform mixing and efficient precipitation.\n   - Maintain the precipitation system at low temperatures (0\u20135\u00b0C using an ice bath) to increase polymer yield and enhance purity.\n\n3. **Observations**:\n   - The polymer will precipitate as a solid or gel-like phase, while the impurities remain dissolved in the nonsolvent.\n\n#### **Step 3: Collection of the Precipitated Polymer**\n1. Use vacuum filtration to separate the polymer precipitate from the liquid phase (mother liquor).\n   - Filter using a Buchner funnel lined with qualitative filter paper.\n   - Wash the precipitate with additional cold nonsolvent (e.g., cold methanol) to remove any residual impurities on the polymer surface.\n\n2. Dry the polymer under vacuum at a moderate temperature (e.g., 40\u201350\u00b0C) until constant weight is achieved.\n   - Avoid overheating, as this may degrade or modify the polymer.\n\n#### **Step 4: Verification of Purity**\n1. Check the polymer for purity using analytical techniques such as:\n   - **Fourier-transform infrared spectroscopy (FTIR)**: Ensure functional groups characteristic of MMA-modified hydrophilic polymers are present and impurities (e.g., unreacted MMA) are absent.\n   - **Nuclear magnetic resonance (NMR)**: Quantify how much MMA has been incorporated and confirm that no monomer residue remains.\n   - **Gel permeation chromatography (GPC)**: Analyze molecular weight distribution to confirm polymer integrity.\n\n---\n\n### Rationale for Solvent Selection in Precipitation\nChoosing the appropriate nonsolvent is critical for the success of the precipitation process.\n\n1. **Solubility Difference**:\n   - The polymer must be insoluble in the nonsolvent to allow efficient precipitation. This depends on the polymer's chemical structure and the solubility parameters (e.g., Hansen solubility parameters).\n   - The nonsolvent must be miscible with the initial solvent to promote even mixing.\n\n2. **Enhancing Hydrophilicity**:\n   - Since the polymer is hydrophilic (MMA-modified), water or polar organic solvents (e.g., ethanol, methanol) are often used as nonsolvents.\n\n3. **Temperature Effects**:\n   - Using a cold nonsolvent reduces polymer aggregation and enhances particle separation, ensuring uniform precipitation.\n\n4. **Impurity Removal**:\n   - The nonsolvent should be able to dissolve small-molecule impurities (unreacted MMA, catalyst residues, etc.) while leaving the high-molecular-weight polymer to precipitate cleanly.\n\n---\n\n### Final Notes\nBy following the outlined purification steps and carefully selecting the combination of solvent and nonsolvent, you will be able to obtain a high-purity MMA-modified hydrophilic polymer. The methodology is robust, scalable, and adaptable to various polymer systems. If you have specific constraints or additional details on the polymer system, such as its molecular weight or functional groups, I can further refine the approach. Always ensure safety protocols are in place when handling volatile and hazardous solvents."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "When using '\u4e19\u4e8c\u9187\u5355\u7532\u919a' (propylene glycol monomethyl ether) in the modification of a polymer, what considerations should be taken regarding its solubility and compatibility with other components? Outline how this might affect the overall hydrophilicity."}, {"role": "assistant", "content": "Certainly! As a seasoned professor with expertise in polymer science, let us approach your question systematically, step by step.\n\n---\n\n### **1. Analyzing the Question and Summarizing Key Points**\nThe question pertains to the use of propylene glycol monomethyl ether (PGME, \u4e19\u4e8c\u9187\u5355\u7532\u919a) as a modifying agent in the synthesis of hydrophilic polymers. Specifically, we need to delve into:\n- The solubility and compatibility of PGME with other components in the polymerization system.\n- How these factors affect the hydrophilicity enhancement of the polymer.\n- The experimental preparation scheme that incorporates PGME into the polymer while ensuring hydrophilicity improvement.\n\n### **2. Detailed Answer: Polymer Modification Scheme with PGME**\nTo address this question thoroughly, I will provide a systematic process to synthesize and functionalize a hydrophilic polymer with PGME while considering solubility, compatibility, and hydrophilicity enhancement.\n\n---\n\n#### **Step 1: Understanding PGME's Fundamental Properties**\nPropylene glycol monomethyl ether (PGME) has characteristics critical to its role as a modifier:\n- **Chemical structure**: PGME contains both a hydrophilic hydroxyl (-OH) group and a hydrophobic methyl ether functionality (-CH3).\n- **Solubility**: It is partially hydrophilic due to the hydroxyl group, capable of dissolving in aqueous and organic systems depending on the solvent polarity.\n- **Compatibility**: PGME can interact with hydrophilic or moderately hydrophobic components via hydrogen bonding or van der Waals interactions.\n\nKey considerations:\n1. PGME tends to form hydrogen bonds with water or hydrophilic polymers, enhancing compatibility in aqueous or polar environments.\n2. For hydrophobic systems, care must be taken to ensure miscibility or compatibility through proper adjustments in solvent or formulation.\n\n---\n\n#### **Step 2: Selecting the Polymer Substrate**\nTo incorporate PGME, choose a polymer substrate that:\n- Has functional groups (such as carboxyl, hydroxyl, or amine) for chemical coupling or physical blending with PGME.\n- Requires enhanced hydrophilicity for improved performance in aqueous environments.\nCommon candidates include:\n- Polyacrylic acid (PAA) or polyvinyl alcohol (PVA) for their hydrophilic backbone.\n- Copolymers of styrene derivatives modified to include polar groups.\n- Polyurethane with hydroxyl or amine functional groups.\n\n---\n\n#### **Step 3: Reaction Pathways and Mechanisms**\nPGME can be introduced into the polymer matrix via two main pathways:\n\n**A. Chemical Grafting or Crosslinking:**\nPGME can be chemically grafted to the polymer backbone through reactions involving hydroxyl or ether groups. Below is a typical experimental scheme:\n\n1. **Choose a coupling agent**:\n   - Select a coupling agent that reacts with the -OH group of PGME and the polymer's functional groups (e.g., carboxylic acid or amine).\n   - Commonly used coupling agents: diisocyanates (for urethanes), carbodiimides (for carboxylic acids), or epoxides.\n\n2. **Reaction setup**:\n   - Dissolve PGME in a polar solvent (such as acetone or methanol) to ensure uniform dispersion. For aqueous polymers, water can be used as a co-solvent.\n   - Add the polymer substrate in the same solvent system to ensure compatibility.\n   - Introduce the coupling agent at a stoichiometric ratio. For example:\n     - PGME:polymer:functional agent in a molar ratio of **1:1:0.8\u20131** ensures sufficient reaction while minimizing excess reagents.\n\n3. **Reaction conditions**:\n   - Maintain the temperature at ~60\u201380\u00b0C to activate functional groups without decomposing PGME.\n   - pH control (near neutral to slightly basic, pH ~7\u20138) may be necessary for hydroxyl group reactivity.\n\n4. **Post-reaction purification**:\n   - Precipitate the product if needed by adding a non-solvent (e.g., hexane or ethanol).\n   - Wash and dry the polymer to remove unreacted PGME or coupling agent.\n\n---\n\n**B. Physical Blending:**\nAlternatively, PGME can be blended physically into the polymer matrix if chemical bonding is unnecessary, provided that solubility and phase compatibility are sufficient.\n\n1. **Polymer preparation**:\n   - Dissolve the polymer in an appropriate solvent for blending (e.g., water or DMSO for hydrophilic polymers).\n   - Introduce PGME gradually under stirring, ensuring homogeneous mixing.\n\n2. **Compatibility considerations**:\n   - Ensure no phase separation occurs during mixing. The solvent should promote miscibility to avoid PGME aggregation.\n   - Optionally, introduce a surfactant or co-solvent to improve solubility.\n\n3. **Final product formation**:\n   - Evaporate/precipitate the solvent after blending, yielding a modified polymer matrix with enhanced hydrophilicity.\n\n---\n\n#### **Step 4: How PGME Enhances Hydrophilicity**\nBy integrating PGME into the polymer structure:\n1. The hydroxyl group interacts with water molecules, enhancing water affinity (hydrophilicity).\n2. The methyl ether group balances hydrophilic absorption and prevents excessive swelling for improved mechanical stability.\n3. Functional grafting further introduces hydrophilic domains, uniformly dispersing PGME as part of the polymer matrix.\n\n---\n\n### **Conclusion**\nIncorporating PGME to modify a polymer requires careful consideration of its solubility and compatibility:\n- Match PGME\u2019s reactivity and miscibility with the polymer and other reaction components.\n- Adjust molar ratios, solvent systems, and reaction conditions methodically to optimize hydrophilicity improvement.\n\nThis systematic approach ensures your experimental scheme succeeds in synthesizing a hydrophilic polymer effectively, ready for laboratory application. Should you pose a specific polymer system, I can tailor the preparation scheme further."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the role of allyl polyether in improving the hydrophilicity of a polymer. How would you ensure that its functional groups are effectively incorporated into the polymer structure?"}, {"role": "assistant", "content": "Certainly, let\u2019s carefully analyze, think logically, and address your question step by step. To begin with:\n\n---\n\n### **Step 1: Analyze the Question and Summarize the Key Points**\nYour question consists of two distinct but interrelated aspects:\n1. **Understanding the Role of Allyl Polyether.**\n   - How allyl polyether contributes to the improvement of hydrophilicity in the polymer structure.\n2. **Ensuring Functional Group Incorporation.**\n   - How to ensure that the functional groups of allyl polyether are effectively integrated during polymer synthesis.\n\nThese two parts form the foundation for designing a comprehensive and practical experimental scheme for synthesizing a hydrophilic polymer. Let us now discuss them systematically.\n\n---\n\n### **Step 2: Allyl Polyether and Its Role in Enhancing Hydrophilicity**\n1. **Chemical Nature of Allyl Polyethers:**\n   - Allyl polyethers are macromolecules containing **alkoxide chains** (e.g., ethylene oxide units -CH2CH2O-) with a terminal allyl group (-CH2=CH-CH2-).\n   - The alkoxide (-CH2CH2O-) chains are hydrophilic due to their polar nature, capable of forming hydrogen bonds with water molecules, thereby imparting significant hydrophilicity.\n\n2. **Incorporating Hydrophilicity into a Polymer:**\n   - When allyl polyether is incorporated into a polymer backbone or as a side chain, the hydrophilic alkoxide functionalities increase the polymer's ability to interact with water.\n   - This can improve properties such as water solubility, wettability, or biocompatibility, depending on the application.\n   - Ideal applications include hydrogels, coatings, or drug delivery systems where hydrophilicity is critical.\n\n---\n\n### **Step 3: Ensuring Functional Group Incorporation**\nThe allyl group (-CH2=CH-) attached to the polyether chain plays a key role in the polymerization process. It can participate in **radical polymerization** or **copolymerization**, ensuring that the polyether structure is effectively grafted onto or integrated into the polymer chain.\n\n---\n\n### **Step 4: Experimental Preparation Scheme for Incorporation of Allyl Polyether**\nThe specific approach to synthesizing a hydrophilic polymer with allyl polyether depends on the polymerization technique used. Below, I lay out a detailed example using **free-radical copolymerization**, which is a commonly adopted method.\n\n#### **Materials Required:**\n- **Monomer:** Allyl polyether (functional hydrophilic component).\n- **Co-monomer:** A hydrophobic/hydrophilic base monomer (e.g., acrylamide, methyl methacrylate, or styrene) to form the polymer backbone.\n- **Initiator:** Azobisisobutyronitrile (AIBN) for radical initiation.\n- **Solvent:** A suitable solvent such as ethanol, dimethylformamide (DMF), or water, depending on the solubility of the reactants.\n- **Crosslinking Agent (if needed):** Ethylene glycol dimethacrylate (EGDMA) to introduce structural stability.\n\n---\n\n#### **Step-by-Step Procedure:**\n1. **Preparation of Reaction Mixture:**\n   1. Accurately weigh out the allyl polyether and base monomer in the desired molar ratio (e.g., 10\u201330 mol% allyl polyether, depending on the desired hydrophilicity).\n   2. Add the reactants to a solvent (e.g., ethanol) to ensure proper solubility of both reactants.\n   3. Optionally, add a crosslinking agent if a three-dimensional network polymer is needed (e.g., for hydrogel formation).\n\n2. **Addition of Radical Initiator:**\n   - Dissolve 1\u20132 mol% of AIBN (based on total monomers) in the reaction mixture. AIBN decomposes under heat to generate free radicals which initiate polymerization.\n\n3. **Polymerization Reaction:**\n   1. Transfer the reaction mixture into a nitrogen-purged, sealed glass reactor to exclude oxygen, which can quench free radicals.\n   2. Heat the mixture to 60\u201370\u00b0C (the decomposition temperature of AIBN) and stir it continuously for 4\u20138 hours to allow polymerization. Monitor the viscosity increase, as this indicates polymer chain growth.\n\n4. **Post-Reaction Processing:**\n   - After polymerization, the reaction product is precipitated into a non-solvent (e.g., diethyl ether or cold water) to separate the polymer. The hydrophilic polymer is then washed and dried under vacuum at room temperature.\n\n---\n\n### **Step 5: Ensuring Effective Incorporation**\n1. **Reaction Conditions:**\n   - Carefully control molar ratios: The percentage of allyl polyether relative to the co-monomer must be optimized to balance hydrophilicity and mechanical properties.\n   - Maintain rigorously controlled temperatures to prevent side reactions.\n   - Use appropriate solvent systems to ensure both monomers are soluble.\n\n2. **Analysis of Grafting Efficiency:**\n   - **Fourier Transform Infrared Spectroscopy (FTIR):** To confirm the presence of characteristic allyl polyether peaks (e.g., -CH2CH2O- bands).\n   - **Nuclear Magnetic Resonance (NMR):** To quantify the composition and confirm integration of allyl polyether into the polymer backbone.\n   - **Thermal Gravimetric Analysis (TGA):** To measure thermal stability consistent with the grafted polymer.\n\n3. **Optimization Through Repetition:**\n   - Iterative experiments may be necessary to optimize the hydrophilicity of the resulting polymer by varying monomer ratios and crosslinking concentrations.\n\n---\n\n### **Conclusion:**\nIn summary, allyl polyethers contribute to the hydrophilicity of a polymer by introducing polar alkoxide chains capable of hydrogen bonding. Their allyl group enables radical or copolymerization processes for effective integration into a polymer structure. By employing free-radical polymerization with controlled reaction conditions, you can synthesize a hydrophilic polymer with well-incorporated allyl polyether functionalities. Analytical techniques are essential to confirm successful incorporation and adjust the synthesis parameters as needed. \n\nWith proper lab technique, you should be able to prepare hydrophilic polymers efficiently and tailor their properties to the desired application. Happy experimenting!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain the role of hydroxyethyl acrylate (HEA) as a monomer in the preparation of hydrophilic polymers and how it can be integrated into the experimental process."}, {"role": "assistant", "content": "Certainly, let\u2019s analyze your question and break it down systematically to ensure we cover the role of hydroxyethyl acrylate (HEA) comprehensively and provide a detailed step-by-step experimental preparation scheme.\n\n---\n\n### **Analysis of the Question:**\n\n1. You are interested in understanding the role of **hydroxyethyl acrylate (HEA)** as a monomer in imparting hydrophilic properties to polymers.\n2. You also want guidance on how HEA can be incorporated into an experimental process for synthesizing hydrophilic polymers.\n\nKey aspects that we need to address:\n- Chemical properties of HEA that make it hydrophilic.\n- How HEA can be polymerized or co-polymerized.\n- Detailed experimental steps, including reaction conditions, molar ratios, reagents needed, and other critical factors.\n\n---\n\n### **Understanding the Role of Hydroxyethyl Acrylate (HEA):**\n\nHydroxyethyl acrylate (HEA) is an acrylic monomer with a hydroxyl (-OH) group on the ethyl substituent. Its key properties that contribute to hydrophilicity are:\n1. **Hydrophilic Hydroxyl Group**: The \u2013OH group is polar and can form hydrogen bonds with water molecules, increasing the polymer\u2019s affinity for water.\n2. **Acrylate Functional Group**: The acrylate group allows HEA to undergo free radical polymerization, enabling it to form linear or crosslinked polymer networks.\n\nAs a monomer, HEA is often used in formulations to enhance hydrophilicity in biomedical applications (e.g., hydrogels), coatings, adhesives, and membranes.\n\n---\n\n### **Experimental Process for Synthesizing Hydrophilic Polymer Using HEA:**\n\nBelow is a systematic preparation scheme for synthesizing a hydrophilic polymer incorporating HEA, through **free radical polymerization**:\n\n#### **Step 1: Preparation of Materials and Equipment**\n**Materials Needed:**\n- Hydroxyethyl acrylate (HEA).\n- Co-monomers (optional, such as acrylamide or methacrylic acid for tailored properties).\n- Initiator (e.g., azobisisobutyronitrile, AIBN, or potassium persulfate).\n- Solvent (e.g., water, ethanol, or dimethylformamide (DMF) depending on solubility and desired polymer properties).\n- Crosslinker (optional, e.g., ethylene glycol dimethacrylate (EGDMA) for hydrogels).\n- pH-adjusting agent (if acidic or basic conditions are required).\n\n**Equipment Needed:**\n- Reaction flask (glass vessel with stirring mechanism).\n- Nitrogen gas source (to avoid oxygen interference during polymerization).\n- Thermostat or oil bath for temperature control.\n- Stirrer (magnetic or mechanical).\n\n---\n\n#### **Step 2: Reaction Setup**\n1. **Solution Preparation**:\n   - Dissolve the HEA monomer in a suitable solvent (e.g., ethanol for moderate polarity or water for full hydrophilic polymer synthesis).\n   - For co-polymerization, add additional monomers like acrylamide or methacrylic acid (adjust the ratio depending on desired hydrophilic and mechanical properties).\n   - If crosslinking is needed, incorporate the crosslinker (e.g., EGDMA) at a concentration of 1\u20135 mol% relative to the total monomer content.\n\n2. **Initiator Addition**:\n   - Add the initiator (e.g., AIBN at 0.5\u20132.0 wt% relative to monomer weight) to the solution.\n   - Dissolve the initiator completely to ensure uniform catalysis during polymerization.\n\n---\n\n#### **Step 3: Polymerization Reaction Conditions**\n1. **Degassing**:\n   - Purge the reaction flask with nitrogen for 15\u201330 minutes to remove dissolved oxygen, which can inhibit free radical polymerization.\n   \n2. **Temperature Control**:\n   - Heat the solution to the optimal temperature for the chosen initiator:\n     - For AIBN, ~70\u201380\u00b0C is ideal.\n     - For potassium persulfate, ~50\u201360\u00b0C may be used.\n\n3. **Reaction Duration**:\n   - Maintain the reaction at the set temperature for 4\u20136 hours, depending on the system. Monitor the viscosity of the solution as the polymer forms.\n\n4. **Neutralization (if pH-sensitive monomers are used)**:\n   - If acidic co-monomers like methacrylic acid were used, adjust the pH with a neutralizing agent post-reaction to ensure stability.\n\n---\n\n#### **Step 4: Post-Polymerization Processing**\n1. **Precipitation** (if in non-aqueous solution):\n   - Precipitate the polymer by pouring the reaction mixture into a non-solvent (e.g., ethyl acetate or acetone).\n   - Filter and wash the precipitate to remove unreacted monomers.\n\n2. **Drying**:\n   - Dry the polymer at 40\u201360\u00b0C in a vacuum oven to remove residual solvent.\n\n---\n\n#### **Step 5: Characterization**\nTo confirm the hydrophilic properties of the synthesized polymer, perform the following tests:\n1. **Water Contact Angle Measurement**:\n   - Assess the hydrophilicity by measuring the contact angle on a flat polymer surface.\n2. **Swelling Ratio Test** (for hydrogels):\n   - Immerse the polymer in water and measure its swelling capacity.\n3. **Fourier Transform Infrared Spectroscopy (FTIR)**:\n   - Analyze the presence of hydroxyl (-OH) groups and confirm polymer structure.\n4. **Solubility Test**:\n   - Evaluate the polymer\u2019s solubility in water or polar solvents.\n\n---\n\n### **Notes and Adjustments for HEA Incorporation**\n1. Carefully adjust the HEA content in the monomer feed to tune the hydrophilicity:\n   - Higher HEA ratios will generally yield higher hydrophilicity, but may reduce mechanical strength.\n   - Typical feed composition ranges may be HEA: 50%\u2013100%, with 0\u201350% co-monomers.\n2. If crosslinking is involved, ensure the crosslinker concentration is optimized to prevent over-crosslinking, which may cause reduced swelling or altered hydrophilicity.\n\n---\n\n### **Conclusion:**\n\nHydroxyethyl acrylate (HEA) serves as an excellent monomer to enhance hydrophilicity in polymers due to its hydroxyl group. Its integration into the polymerization process requires careful selection of reaction conditions, initiators, and solvent systems to achieve desired properties. By systematically following the outlined experimental scheme, the student should be able to successfully synthesize hydrophilic polymers and characterize their hydrophilic behaviors.\n\nDo not hesitate to bring up any nuances or ask further questions if clarification is needed\u2014science thrives on rigorous pursuit!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Outline the steps required to incorporate POSS as an initiator in the synthesis of the polymer. How does the inclusion of POSS contribute to the hydrophilicity of the final polymer material?"}, {"role": "assistant", "content": "To address your question systematically, we will first analyze the key aspects and then provide a detailed experimental preparation scheme for incorporating Polyhedral Oligomeric Silsesquioxane (POSS) as an initiator in polymer synthesis while enhancing the hydrophilicity of the final polymer material.\n\n---\n\n### **Analysis of the Question**\n1. **Objective**: To incorporate POSS as an initiator in the synthesis of a hydrophilic polymer. The primary goal is to introduce POSS into the polymer backbone to enhance material properties, including hydrophilicity.\n2. **Key Functional Role of POSS**: POSS is a nanoscale cage-like molecule with a silicon-oxygen framework. Its hydrophilic variants, which often contain hydroxyl (-OH) or other hydrophilic functional groups, can significantly improve the hydrophilicity of the resulting polymer due to its interaction with water and its ability to modify the surface energy of the polymer.\n3. **Experimental Challenges**:\n   - Proper functionalization of POSS to act as an effective initiator.\n   - Optimization of polymerization conditions (e.g., selection of monomers, solvent system, and initiator concentration).\n   - Control of POSS distribution within the polymer matrix to achieve uniform hydrophilicity.\n\n---\n\n### **Experimental Preparation Scheme for Incorporating POSS as an Initiator**\n\n#### Step 1: Selection of POSS Derivative\n- Choose a hydroxyl-functionalized POSS molecule (e.g., POSS-triol or POSS containing multiple -OH groups) as the base material. These hydroxyl groups make it easy to chemically modify POSS and act as initiation sites for polymerization.\n- If a more reactive variant is required, POSS molecules bearing amino (-NH2), carboxylic acid (-COOH), or methacryloyl (-C=C-) groups can also be used, depending on the type of polymerization to be conducted.\n\n---\n\n#### Step 2: Functionalization of POSS to Enable Initiation\nTo prepare POSS as an initiator, we need to attach initiator functional groups to the POSS framework, depending on the polymerization mechanism:\n\n- **For Free Radical Polymerization**:\n  1. React hydroxyl-functionalized POSS with acryloyl chloride or methacryloyl chloride under mild conditions to form acrylate-functionalized POSS.\n     - **Reaction Conditions**:\n       - Dissolve POSS (1 mole) in dry dichloromethane (DCM) or tetrahydrofuran (THF) under an inert nitrogen atmosphere.\n       - Add triethylamine (TEA) as a base (1.2 moles to neutralize HCl released).\n       - Dropwise add acryloyl chloride or methacryloyl chloride (1.1 moles) while stirring at 0\u00b0C (using an ice bath).\n       - After completion of addition, warm the reaction mixture to room temperature and stir for 4\u20136 hours.\n       - Filter off the TEA-HCl precipitate and purify POSS-acrylate by washing with brine and drying under reduced pressure.\n  2. This functionalized POSS can now participate as an active center in radical polymerization with hydrophilic monomers (e.g., acrylamide, methacrylic acid).\n\n- **For Ring-Opening Polymerization (ROP)**:\n  1. React hydroxyl-functionalized POSS with \u03b5-caprolactone or lactide monomers using stannous octoate (Sn(Oct)2) as a catalyst.\n     - **Reaction Conditions**:\n       - Dissolve POSS in anhydrous toluene and add \u03b5-caprolactone (10:1 molar ratio of monomer to POSS initiator).\n       - Add stannous octoate at 0.1 wt% of total monomer.\n       - Heat reaction mixture to 100\u00b0C under an inert nitrogen atmosphere and stir for 12\u201324 hours.\n       - Isolate POSS-initiated prepolymer via precipitation in cold methanol.\n\n- **For Controlled Living Polymerizations (e.g., Atom Transfer Radical Polymerization (ATRP))**:\n  1. React POSS-triol with \u03b1-bromoacetyl bromide to introduce bromo initiator groups.\n     - Dissolve POSS and add excess \u03b1-bromoacetyl bromide in dry dichloromethane with TEA as a base.\n     - Purify the POSS-functionalized initiator and use this in ATRP with a copper-based catalyst and ligand.\n\n---\n\n#### Step 3: Polymerization with Hydrophilic Monomers\n- Select hydrophilic monomers such as acrylamide, hydroxyethyl methacrylate (HEMA), or methacrylic acid for copolymerization.\n- Polymerization can proceed in solution, suspension, or bulk phases, using POSS-functionalized initiator prepared in Step 2.\n\n**Example: Free Radical Polymerization**\n1. Dissolve hydrophilic monomers (e.g., acrylamide, 10 g) and POSS initiator (1 g) in a solvent like deionized water or ethanol.\n2. Add an initiator (e.g., ammonium persulfate (APS)) to thermally trigger polymerization, or use photo-initiation with UV light if a photoinitiator group was attached to the POSS.\n3. Control reaction temperature (e.g., ~60\u201370\u00b0C for APS) and stir the mixture for 6\u201312 hours.\n4. Purify the POSS-modified hydrophilic polymer by dialysis or precipitation depending on solubility.\n\n---\n\n#### Step 4: Post-Polymerization Modifications (Optional)\nTo further enhance hydrophilicity:\n- Incorporate sulfonic acid groups or polyethylene glycol (PEG) chains into the polymer backbone or side chains.\n- Verify hydrophilicity improvement via water contact angle measurements and swelling ratio analysis in water.\n\n---\n\n### **How POSS Enhances Hydrophilicity**\n1. **Nanoscale Structure**: POSS molecules have a highly polar and hydrophilic silicon-oxygen core, which inherently increases water interaction.\n2. **Surface Energy Alteration**: The inclusion of POSS at regular intervals in the polymer matrix reduces the contact angle of water droplets, increasing hydrophilicity.\n3. **Increased Surface Roughness**: POSS enhances hydrophilic behavior by providing a nanostructured surface.\n4. **Functional Modifications**: POSS allows the introduction of additional hydrophilic groups (e.g., hydroxyl, carboxyl) that interact with water.\n\n---\n\n### **Conclusion**\nIncorporating POSS as an initiator in polymer synthesis offers a robust strategy to enhance hydrophilicity of the resulting material. The outlined preparation scheme systematically adjusts reaction conditions to prepare a POSS-functionalized polymer efficiently. Control over reaction conditions and functional groups ensures reproducibility and success in the lab. Would you like additional clarification on any of the steps?"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "During the synthesis of a hydrophilic polymer, poly(vinyl acetate) (PVAc) is often used in the preparation process. How would you prepare a substrate layer using PVAc, and why is this step important for enhancing hydrophilicity?"}, {"role": "assistant", "content": "To address your question systematically, we will examine the requirements for preparing a substrate layer using poly(vinyl acetate) (PVAc) and its importance in enhancing hydrophilicity during hydrophilic polymer synthesis. Let us proceed step-by-step, keeping in mind the logical rigor and detail you require.\n\n---\n\n### 1. **Key Points Analysis of the Question:**\n   - **Goal of the experiment:** To synthesize a hydrophilic polymer.\n   - **Role of PVAc:** PVAc is used in the preparation of a substrate layer during the synthesis process.\n   - **Task:** Devise an experimental procedure to prepare a substrate layer of PVAc.\n   - **Objective:** Explain the importance of this step in enhancing the hydrophilicity of the polymer.\n\n   The preparation and role of the PVAc substrate layer must be clearly explained, ensuring that it contributes to the hydrophilicity of the overall polymer system.\n\n---\n\n### 2. **Systematic Procedure for PVAc Substrate Preparation:**\n\nTo prepare a PVAc substrate layer, the following experimental steps can be followed. These steps involve the synthesis, deposition, and modification of PVAc for use as a base layer for the final hydrophilic polymer.\n\n#### **Step 1: Sourcing Poly(vinyl acetate) (PVAc)**\n   You can either use commercially available PVAc (available in pellet or powder form with known molecular weights) or synthesize PVAc in the laboratory via the free-radical polymerization of vinyl acetate (VAc) monomers.\n   \n   **Synthesis of PVAc (if needed):**\n   - Use vinyl acetate monomers with an appropriate free-radical initiator such as benzoyl peroxide (BPO) or azobisisobutyronitrile (AIBN).\n   - Dissolve the initiator (0.5\u20131% by weight of VAc) in a suitable solvent (ethanol or toluene).\n   - Polymerize under inert conditions (nitrogen atmosphere) at 60\u201370\u00b0C for several hours until polymerization is complete.\n\n   Ensure that the synthesized PVAc is purified by precipitation in methanol or ethanol, followed by drying in vacuum.\n\n#### **Step 2: Preparation of PVAc Solution for Substrate Layer**\n   - Dissolve PVAc powder (or use pre-synthesized PVAc) in a solvent such as ethanol, acetone, or tetrahydrofuran (THF). The choice of solvent depends on the molecular weight of PVAc and the desired viscosity of the solution.\n   - Typical concentration: Prepare a solution with **5\u201320 wt% PVAc** depending on substrate thickness requirements.\n   - Stir the solution thoroughly (at room temperature or slightly elevated temperatures) until the PVAc is fully dissolved.\n\n#### **Step 3: Substrate Layer Deposition**\n   - Use a substrate material such as a glass slide, silicon wafer, or polymer film as the base layer.\n   - Clean the substrate thoroughly using sequential sonication in solvents (e.g., acetone, isopropanol, and deionized water) and dry it with nitrogen gas to remove residual contaminants.\n\n   **Deposition techniques for PVAc:**\n   - **Spin Coating (recommended for uniform thickness):**\n     - Deposit the PVAc solution onto the substrate surface.\n     - Spin the substrate at 2000\u20134000 rpm for 30\u201360 seconds until a thin and uniform PVAc layer forms.\n     - Dry thoroughly (allow the solvent to evaporate) at room temperature or in an oven at 40\u201350\u00b0C.\n   - **Dip Coating:**\n     - Dip the substrate into the PVAc solution and slowly withdraw it at a controlled speed (~1\u20135 mm/s).\n     - Air dry the coated substrate and cure it in an oven at 50\u00b0C for several hours.\n   - **Drop Casting:**\n     - Deposit a controlled volume of the PVAc solution onto the substrate and allow it to spread evenly.\n     - Let the solvent evaporate slowly in ambient conditions or in an oven.\n\n   The final PVAc substrate layer thickness can be controlled by adjusting the solution concentration, coating speed, and deposition technique. Typical layer thickness ranges from **100 nm to a few microns**.\n\n#### **Step 4: Modification of PVAc Layer \u2013 Hydrolysis**\n   After forming the substrate layer, PVAc can be converted into poly(vinyl alcohol) (PVA) through hydrolytic treatment to introduce hydrophilic hydroxyl (-OH) groups. This step enhances the hydrophilicity of the PVAc layer.\n\n   - **Hydrolysis Reaction:**\n     - Immerse the PVAc-coated substrate in a solution of **sodium hydroxide (NaOH)** or potassium hydroxide (KOH) in ethanol or water. A typical concentration is **0.1\u20130.5 M NaOH in ethanol/water (80:20)**.\n     - Allow the hydrolysis reaction to proceed at **room temperature for 30\u201360 minutes**.\n   - Monitor the degree of hydrolysis carefully. Partial hydrolysis results in a balance of hydrophilicity and structural stability, while complete hydrolysis maximizes hydrophilicity.\n\n   - **Washing and Drying:**\n     - Wash the substrate gently with deionized water to remove residual NaOH/KOH and byproducts (e.g., sodium acetate or potassium acetate).\n     - Dry the modified PVAc (PVA) layer under nitrogen gas or in a low-temperature oven (50\u00b0C).\n\n---\n\n### 3. **Why is the PVAc Substrate Important?**\n\nThe PVAc substrate layer plays a critical role in enhancing hydrophilicity for subsequent polymer synthesis:\n1. **Adhesion and Compatibility:**\n   - PVAc acts as a uniform, adhesive base for the growth or deposition of a secondary hydrophilic polymer layer. This ensures strong interfacial bonding and prevents delamination.\n2. **Hydrophilic Transformation via Hydrolysis:**\n   - Hydrolyzing PVAc into PVA introduces a high density of hydrophilic hydroxyl (-OH) groups, which increases the overall water affinity of the system.\n3. **Template for Advanced Functionalization:**\n   - The presence of hydroxyl groups on PVA serves as reactive sites for further chemical modifications, such as graft polymerization using hydrophilic monomers (e.g., acrylic acid, acrylamide, or polyethylene glycol methacrylate).\n4. **Enhanced Wettability:**\n   - A partially or fully hydrolyzed PVAc layer improves the wettability of the substrate, crucial for applications such as coatings, membranes, and biomaterials.\n\n---\n\n### 4. **Experimental Considerations**\n   - *Safety Precautions:* Handle solvents and alkali solutions in a fume hood with proper PPE (gloves, goggles, lab coat).\n   - *Reaction Control:* Monitor the hydrolysis reaction to optimize the degree of hydrophilicity without over-degradation of the polymer.\n   - *Characterization:* Analyze the surface properties of the PVAc substrate through techniques such as water contact angle measurement, Fourier-transform infrared spectroscopy (FTIR, to confirm hydrolysis), and atomic force microscopy (AFM, for surface topography).\n\n---\n\n### Final Conclusion:\nTo prepare a PVAc substrate layer for enhancing hydrophilicity, dissolve and deposit PVAc using appropriate coating techniques. Modify the PVAc layer via hydrolysis to introduce hydrophilic hydroxyl groups, creating a PVA base that promotes adhesion, wettability, and further functionalization. This procedural framework allows a successful experiment and serves as a stepping stone for synthesizing advanced hydrophilic polymers."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Propose an approach to assess the influence of the topological polar surface area (TPSA) of the chosen molecule on the hydrophilicity of the modified polymer after the experiment."}, {"role": "assistant", "content": "To assess the influence of the topological polar surface area (TPSA) of the chosen molecule on the hydrophilicity of the modified polymer after the experiment, we need to systematically outline a detailed experimental protocol that incorporates measurement tools and analytical methods. Here's my detailed answer, broken down step by step:\n\n---\n\n### **Step 1: Analyze the Question**\nThe question requires us to evaluate the relationship between TPSA, a molecular descriptor that correlates strongly with hydrophilicity, and the hydrophilicity of the final polymer. The experiment involves:\n1. Modifying a polymer with a chosen molecule (with its TPSA as a key feature).\n2. Measuring the hydrophilicity of the resulting polymer.\n3. Linking the observed hydrophilicity to the molecule\u2019s TPSA.\n\nTPSA can serve as a helpful theoretical parameter when selecting or designing molecules for hydrophilic modification. A larger TPSA indicates greater polar functional group content, which is often associated with higher hydrophilicity.\n\n---\n\n### **Step 2: Design an Experimental Plan**\nTo assess the influence of TPSA on polymer hydrophilicity, the experiment can be broken down into four main phases: **polymer modification**, **hydrophilicity characterization**, **TPSA calculation**, and **correlation analysis**.\n\n---\n\n### **Phase 1: Polymer Modification**\nIn this phase, you will use the molecule provided to modify the base polymer, preparing a series of modified polymers.\n\n#### **Step 1.1: Base Polymer Selection**\n- Choose a polymer with tunable modification sites, such as **polyvinyl alcohol (PVA)** or **polyacrylamide (PAAM)**, which are hydrophilic but can be further modified.\n- Ensure hydroxyl, amine, or carboxylic groups are available for functionalization.\n\n#### **Step 1.2: Reaction Conditions**\n1. **Reagents**: Use the chosen molecule containing polar functional groups (TPSA known or calculable). Ensure it has reactive groups (e.g., hydroxyl, carboxyl, or amine).\n2. **Reaction Type**:\n   - If the molecule has carboxyl groups, employ **amide formation** or **esterification** (e.g., use N,N'-dicyclohexylcarbodiimide (DCC) or EDC in aqueous or organic solvents).\n   - If hydroxyl groups are present, use **etherification** or similar reactions with sodium hydroxide as a base.\n3. **Solvent**: Choose a solvent suitable for both the polymer and the chosen molecule. For hydrophilic polymers, water or dimethyl sulfoxide (DMSO) is often suitable.\n4. **Reaction Conditions**:\n   - Maintain temperature between **60\u201380\u00b0C** for esterification or amide formation.\n   - Adjust the reaction time to **4\u20136 hours** based on the reactivity of the molecule.\n   - Use a molar ratio of molecule to polymer functional groups as **2:1** to achieve sufficient modification.\n\n#### **Step 1.3: Purification**\n- Dialyze the solution against water for 48 hours to remove unreacted molecules and byproducts.\n- Freeze-dry the polymer to obtain a modified polymer sample.\n\n---\n\n### **Phase 2: Hydrophilicity Characterization**\nTo determine the hydrophilicity of the modified polymer, perform the following experiments:\n\n#### **Step 2.1: Contact Angle Measurement**\n- Prepare thin films of the modified polymer on a glass substrate.\n- Measure the water contact angle using a goniometer. Lower contact angles indicate higher hydrophilicity.\n- Ensure consistent experimental conditions (e.g., drop volume of 5 \u03bcL, temperature 25\u00b0C).\n\n#### **Step 2.2: Swelling Behavior**\n- Immerse the polymer sample in water at room temperature and measure the swelling ratio over time (e.g., equilibrium swelling after 48 hours). Hydrophilic polymers will absorb more water, leading to higher swelling ratios.\n  \n#### **Step 2.3: Surface Energy Analysis**\n- Perform surface energy characterization using an advanced tensiometer or surface analysis tool. Hydrophilic surfaces have higher polar component contributions.\n\n### **Phase 3: TPSA Calculation**\nThe TPSA values of the chosen molecule influence the hydrophilicity. To accurately measure TPSA:\n1. Use computational software like **ChemBioDraw, MarvinSketch**, or **SwissADME**.\n2. Input the structure of the chosen molecule and calculate its TPSA.\n3. For molecules already tested, TPSA values are readily available in the literature.\n\n### **Phase 4: Correlation Analysis**\nOnce hydrophilicity data and TPSA values are available:\n1. Plot the TPSA of the different molecules used for modification against the hydrophilicity metrics (e.g., contact angle, swelling ratio).\n2. Use statistical tools such as **linear regression analysis** to establish the relationship between TPSA and hydrophilicity. A positive trend (e.g., higher TPSA correlates to increased hydrophilicity) supports the hypothesis.\n\n---\n\n### **Additional Considerations**\n1. **Reproducibility**: Perform each step of synthesis and characterization in triplicate to minimize experimental error.\n2. **Controls**: Include unmodified polymer as a control sample.\n3. **Functional Group Characterization**:\n   - Use Fourier-transform infrared (FTIR) spectroscopy to confirm successful attachment of the molecule to the polymer.\n   - Use nuclear magnetic resonance (NMR) spectroscopy to quantify the degree of functionalization.\n\n---\n\n### **Summary**\nThis experimental scheme systematically explores the influence of TPSA on polymer hydrophilicity. By linking TPSA values to hydrophilicity measurements (contact angle, swelling, surface energy), you can evaluate the extent to which polar functional groups and TPSA contribute to hydrophilic behavior in the final polymer. This approach is both rigorous and comprehensive, providing the ability to scientifically validate the relationship between TPSA and hydrophilicity.\n\n---\nThis scheme should allow you to successfully complete the experiment and provide insight into the molecular design principles for enhanced hydrophilicity in polymers!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "How would you incorporate poly(ethoxylate-b-caprolactone) monomethacrylate oligomer as a functionalizing agent to create a hydrophilic polymer? Describe the step-by-step process and the expected structural changes to the polymer backbone."}, {"role": "assistant", "content": "Certainly! Let us break down your question systematically and design a detailed experimental preparation scheme for incorporating **poly(ethoxylate-b-caprolactone) monomethacrylate oligomer** as a functionalizing agent to synthesize a hydrophilic polymer. This step-by-step process also includes the expected structural changes to the polymer backbone.\n\n---\n\n### **Key Points of the Question:**\n\n1. **Objective:** Functionalize a polymer to enhance its hydrophilicity.\n2. **Given Functionalizing Agent:** The provided molecule is **poly(ethoxylate-b-caprolactone) monomethacrylate oligomer**. This is a block oligomer with hydrophilic ethoxylate (EO) segments, hydrophobic caprolactone (CL) moieties, and a reactive methacrylate group at one terminus.\n3. **Strategy:** Use the methacrylate group for **radical copolymerization** to integrate the oligomer into the polymer backbone.\n4. **Functionalization Target:** Generate a hydrophilic polymer backbone containing poly(ethoxylate-b-caprolactone) side chains to improve hydrophilicity and potentially tune amphiphilicity.\n\n---\n\n### **Step-by-Step Experimental Synthesis:**\n\n#### **Step 1: Selection of the Polymer Backbone**\nTo incorporate **poly(ethoxylate-b-caprolactone) monomethacrylate (PEG-b-PCL)** into a hydrophilic polymer, we need to copolymerize it with a compatible monomer through radical polymerization. Suitable hydrophilic monomers include:\n   - Acrylic acid (AA)\n   - Hydroxyethyl methacrylate (HEMA)\n   - N-vinylpyrrolidone (NVP)\n\nFor this synthesis, let's use **acrylic acid (AA)** as the primary monomer due to its strong hydrophilic nature and ability to form carboxylic functionalities in the resulting polymer.\n\n---\n\n#### **Step 2: Reaction Scheme Overview**\nThe process involves **free-radical copolymerization** of:\n   - Acrylic acid **(AA)** (hydrophilic base monomer).\n   - **Poly(ethoxylate-b-caprolactone) monomethacrylate (PEG-b-PCL)** oligomer (the functionalizing monomer).\n\nThe polarized methacrylate group in PEG-b-PCL enables its copolymerization with acrylic acid, while the ethoxylate and caprolactone blocks become part of the hydrophilic side chains.\n\n---\n\n#### **Step 3: Materials Required**\n1. **Monomers**:\n   - Acrylic acid (AA) - Base hydrophilic monomer.\n   - Poly(ethoxylate-b-caprolactone) monomethacrylate (PEG-b-PCL) - Functionalizing agent.\n2. **Initiator**:\n   - Azobisisobutyronitrile (**AIBN**), a commonly used radical initiator.\n3. **Solvent**:\n   - Anhydrous dioxane or dimethylformamide (DMF), which can dissolve both AA and PEG-b-PCL.\n4. **Chain Transfer Agent (Optional)**:\n   - Mercaptoethanol or dodecanethiol to control molecular weight.\n\n---\n\n#### **Step 4: Reaction Procedure**\n##### **Step 4.1: Preparation of the Reaction Mixture**\n1. **Calculate reagent quantities:**\n   - **Acrylic acid (AA)**: Determine the required molar amount (e.g., target MW: ~50,000 g/mol). Commonly, ratios of AA:PEG-b-PCL around **90:10 (molar)** provide good hydrophilicity.\n   - **PEG-b-PCL oligomer**: Measure a known mass based on its molecular weight (typically 2\u20135 kDa) and desired feed ratio.\n   - **Initiator (AIBN)**: Use ~1\u20132% molar of the total monomer concentration.\n   - **Solvent**: Add solvent (dioxane/DMF) to achieve 20\u201330 wt% monomer concentration for proper polymerization control.\n\n2. Add AA and PEG-b-PCL together in a clean, dry round-bottom flask containing the solvent. Ensure homogeneous dissolution (stirring, mild heating if needed).\n\n3. Add the AIBN initiator last to the monomer mixture under inert gas (nitrogen or argon flow) to prevent premature radical formation.\n\n##### **Step 4.2: Purge the System with Inert Gas**\n4. Degas the mixture by bubbling nitrogen/argon gas for ~30 minutes to eliminate dissolved oxygen, as free radicals are susceptible to oxygen quenching.\n\n##### **Step 4.3: Radical Polymerization**\n5. Place the reaction flask in an oil bath or a heating block and maintain the temperature at **60\u201370\u00b0C** for ~4\u20136 hours under constant stirring. The elevated temperature triggers the dissociation of AIBN, generating radicals for polymerization.\n\n6. During the copolymerization, the methacrylate group on PEG-b-PCL reacts with the double bond in AA, incorporating the PEG-b-PCL units into the polymer backbone with ethoxylate and caprolactone blocks forming the **hydrophilic pendant groups**.\n\n---\n\n#### **Step 5: Purification of the Polymer**\n1. After the reaction is complete, cool the mixture to room temperature and precipitate the polymer by adding the reaction mixture dropwise into a large volume of non-solvent (e.g., diethyl ether or ethanol).\n\n2. Filter and wash the precipitate with the non-solvent to remove unreacted monomers or oligomers.\n\n3. Dry the purified polymer under vacuum at 40\u201350\u00b0C until constant weight is achieved.\n\n---\n\n#### **Step 6: Characterization**\n1. **Fourier-transform infrared spectroscopy (FTIR):**\n   - To confirm the incorporation of PEG-b-PCL. Look for characteristic peaks of ethoxylate (-C-O-C-) and caprolactone groups.\n2. **Gel permeation chromatography (GPC):**\n   - To analyze molecular weight and distribution.\n3. **Contact angle measurement:**\n   - To evaluate the hydrophilicity of the resulting polymer.\n4. **Nuclear magnetic resonance (NMR):**\n   - To determine the composition and quantify the molar ratio of AA to PEG-b-PCL in the copolymer.\n\n---\n\n### **Expected Structural Changes**\n1. The methacrylate group of **PEG-b-PCL** copolymerizes with acrylic acid, integrating **PEG-b-PCL as hydrophilic pendant side chains** onto the polymer backbone.\n2. The resulting polymer has repeating units of acrylic acid and **side-chain blocks** of ethoxylate-caprolactone, which increase hydrophilicity due to:\n   - **Poly(ethoxylate) moieties** (highly hydrophilic and water-soluble).\n   - Moderate amphiphilicity from **poly(caprolactone)** units, which provide tunable hydrophobicity.\n\n---\n\n### **Conclusion**\nThe described free-radical copolymerization process effectively integrates **poly(ethoxylate-b-caprolactone) monomethacrylate oligomer** into a hydrophilic polymer backbone. By controlling the feed ratio and reaction conditions, the resulting polymer will exhibit enhanced hydrophilicity due to the ethoxylate groups, with potential amphiphilic behavior from the caprolactone moieties.\n\nThis step-by-step process should enable you to perform the experiment successfully in the lab! Let me know if you need further clarification."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain how hydroxyethyl acrylate (HEA) can be used to introduce unsaturated bonds into the molecular structure of a polymer and discuss how these bonds can enhance the hydrophilicity of the final material."}, {"role": "assistant", "content": "Certainly! Thank you for your thoughtful question. Let us carefully address this topic step by step, ensuring clarity and precise understanding, particularly focusing on how hydroxyethyl acrylate (HEA) can be harnessed within a hydrophilic polymer synthesis process. We will cover its role in introducing unsaturated bonds and how these bonds contribute to hydrophilicity enhancement.\n\n---\n\n### **Key Points of the Question**\n1. **Significance of Hydroxyethyl Acrylate (HEA):** We are tasked with exploring how HEA can introduce unsaturated bonds into the molecular structure of a polymer.\n2. **Hydrophilicity Enhancement:** Understand how incorporating HEA contributes to the hydrophilicity of the resulting polymer.\n3. **Experimental Process Design:** Develop detailed, step-by-step synthetic procedures using HEA within a polymerization context.\n\n---\n\n### **Step-by-Step Explanation and Experimental Design**\nWe will now undertake the design of an experiment using HEA to synthesize a hydrophilic polymer, integrate it into the polymer chain, and explain how this improves hydrophilicity.\n\n---\n\n#### **1. Overview of Hydroxyethyl Acrylate (HEA)**\nHEA is a monomer containing two key functional groups:\n   - **The acrylate group (-CH=CHCOO-):** Contains an unsaturated double bond, which enables its participation in polymerization reactions, such as free radical polymerization, to form the backbone of a polymer.\n   - **The hydroxyl group (-OH):** Hydrophilic in nature, which increases water affinity in the resulting polymer.\n\nThis bifunctionality allows HEA to be copolymerized with other monomers while simultaneously introducing hydrophilic and reactive sites into the polymer structure.\n\n---\n\n#### **2. Reaction Strategy: Introducing HEA into a Polymer**\nTo incorporate HEA into a polymer, we will employ **free radical polymerization**, which is a robust and versatile technique for acrylate-based monomers. The steps are as follows:\n\n---\n\n#### **Step 1: Selection of Copolymerizable Monomers**\n- Identify the desired copolymer structure and its intended hydrophilicity. Copolymerization with HEA ensures two outcomes:\n  1. Introduction of hydrophilic hydroxyl groups.\n  2. Incorporation of the unsaturated acrylate group.\n\nCommon comonomers for HEA in hydrophilic polymer synthesis include:\n   - **Methyl methacrylate (MMA):** For thermomechanical stability.\n   - **Acrylic acid (AA):** To further enhance hydrophilicity through its carboxylic acid functionality.\n   - **N-vinylpyrrolidone (NVP):** Provides additional hydrophilic sites.\n\n---\n\n#### **Step 2: Experimental Conditions for Polymerization**\nWe propose a free radical solution polymerization using the following:\n- **Monomers:** HEA (hydroxyethyl acrylate) and a comonomer (e.g., acrylic acid).\n- **Initiator:** Azo-based initiators such as azobisisobutyronitrile (AIBN) are ideal. Use at 1.0 mol% relative to total monomers for efficient initiation.\n- **Solvent:** A polar aprotic solvent like dimethylformamide (DMF), as it can dissolve both the monomers and the resulting hydrophilic polymer.\n- **Reaction Temperature:** 60-75 \u00b0C, as AIBN decomposes into free radicals at these temperatures.\n- **Reagent Ratios:** HEA to comonomer molar ratio should be tailored to achieve the desired level of hydrophilicity. Typically:\n  - HEA: 70 mol% (higher proportion for greater hydrophilicity).\n  - Comonomer (e.g., acrylic acid): 30 mol%.\n\n---\n\n#### **Step 3: Experimental Procedure**\n1. **Prepare the Reaction Mixture:**\n   - Dissolve HEA (e.g., 7 g, ~60 mmol) and comonomer acrylic acid (e.g., 2.5 g, ~35 mmol) in DMF (50 mL) in a 100 mL round-bottom flask equipped with a magnetic stir bar.\n   - Add AIBN (0.05 g, ~0.3 mmol) as the initiator.\n\n2. **Degas the Mixture:**\n   - Purge the solution with nitrogen or argon gas for 20-30 minutes to remove oxygen, which inhibits radical polymerization.\n\n3. **Polymerization Reaction:**\n   - Heat the reaction mixture at 65 \u00b0C under nitrogen atmosphere with constant stirring.\n   - Allow the reaction to proceed for 6-8 hours to achieve complete polymerization.\n\n4. **Precipitation and Recovery:**\n   - After cooling the reaction to room temperature, precipitate the polymer by adding the reaction mixture dropwise into diethyl ether, a nonsolvent for the polymer.\n   - Collect the polymer by filtration and dry under vacuum at 40 \u00b0C to obtain a hydrophilic polymer.\n\n---\n\n#### **3. Hydrophilicity Enhancement in the Final Material**\nIncorporating HEA into the polymer structure contributes to hydrophilicity in two ways:\n1. **Hydroxyl Groups (-OH):**\n   The hydroxyl groups on HEA provide strong hydrogen bonding with water molecules, enhancing the polymer's affinity for water.\n\n2. **Controlled Hydrophilic-Hydrophobic Balance:**\n   By adjusting the molar ratio of HEA to the comonomer during polymerization, one can finely tune the hydrophilic/hydrophobic balance of the polymer surface.\n\n---\n\n### **4. Crosslinking with HEA**\nIf desired, the unsaturated acrylate group in HEA retains its reactivity post-polymerization and can be further used for crosslinking reactions with additional monomers or oligomers:\n- **Example:** UV curing with photoinitiators to form crosslinked hydrophilic networks.\n- Crosslinking enhances mechanical strength while maintaining hydrophilicity.\n\n---\n\n#### **Final Remarks**\nYou now have a comprehensive, step-by-step synthetic strategy to use HEA for the preparation of hydrophilic polymers. By leveraging HEA's dual functionality (acrylate and hydroxyl groups), you can achieve tailored levels of hydrophilicity in the polymer. Adjusting monomer ratios, reaction conditions, and crosslinking will allow additional fine-tuning for diverse applications such as hydrogels, coatings, and biomedical materials. \n\nLet me know if you have further questions!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Design an experimental scheme for polymerization using N-Hydroxyethylacrylamide, specifying the type of initiator you would use, the solvent, and the conditions required to ensure optimal reaction."}, {"role": "assistant", "content": "Certainly! Let us tackle this problem step by step to design a well-thought-out experimental scheme for the polymerization of **N-Hydroxyethylacrylamide (NHEA)**, a molecule commonly used to prepare hydrophilic polymers. Here's how we will proceed:\n\n---\n\n### **Step 1: Analyze the question and summarize the key points**\nTo polymerize **N-Hydroxyethylacrylamide (NHEA)**, the following parameters need to be considered:\n1. **Polymerization Type:** The method of polymerization best suited for NHEA.\n2. **Initiator System:** Selection of an efficient initiator that ensures controlled polymerization.\n3. **Solvent Selection:** Determining an appropriate solvent to dissolve NHEA and promote hydrophilicity in the reaction medium.\n4. **Reaction Conditions:** Optimizing key variables such as temperature, time, concentration of reagents, and atmosphere (e.g., inert gas to prevent oxygen inhibition).\n5. **Polymer Characterization:** How to verify the success of the polymerization.\n\n---\n\n### **Step 2: Experimental Scheme for Polymerization**\n\nThe polymerization of **N-Hydroxyethylacrylamide (NHEA)** can be efficiently carried out using **free-radical polymerization**. Below is a detailed and systematic scheme to achieve this:\n\n#### **Reagents and Materials:**\n- **Monomer:** N-Hydroxyethylacrylamide (NHEA)\n- **Initiator:** Azobisisobutyronitrile (AIBN) \u2013 a thermal initiator commonly used for free-radical polymerizations\n- **Solvent:** Deionized water or a water/ethanol mixture for hydrophilic polymerization\n- **Inert Gas:** Nitrogen or argon for purging to remove oxygen\n- **Reaction Flask:** A round-bottom flask equipped with a magnetic stirrer, reflux condenser, and thermometer\n\n#### **Reaction Conditions:**\n1. **Monomer Concentration:** 10\u201320% (w/v) NHEA in the selected solvent.\n2. **Initiator Concentration:** AIBN at 0.5\u20131.0 weight percent relative to the weight of the monomer.\n3. **Temperature:** 60\u201375 \u00b0C (based on the thermal decomposition range of AIBN).\n4. **Time:** 4\u20138 hours for complete polymerization.\n\n---\n\n### **Step 3: Step-by-Step Procedure**\n\n#### **(1) Preparation of the Reaction Mixture**\n1. **Dissolving the Monomer:**\n   - Accurately weigh the required amount of **NHEA** (e.g., 10 g).\n   - Dissolve it in 90 mL of deionized water or a water/ethanol mixture (e.g., 80/20 v/v) under gentle magnetic stirring.\n   - Ensure the monomer is completely dissolved, as this is key for homogeneous polymerization.\n\n2. **Adding the Initiator:**\n   - Weigh and add **AIBN** (e.g., 0.1 g) to the monomer solution.\n   - Stir until the initiator is dissolved. AIBN is only slightly soluble in water, so a water/ethanol mixture may improve its solubility.\n\n#### **(2) Degassing the Reaction Mixture**\n- Transfer the reaction mixture to a round-bottom flask equipped with a reflux condenser.\n- Bubble **nitrogen gas** (or argon) through the reaction mixture for **30 minutes** to eliminate dissolved oxygen, which can inhibit the free-radical polymerization process.\n\n#### **(3) Thermal Polymerization**\n1. **Heating and Reaction:**\n   - Place the flask in an oil bath or water bath controlled at **65 \u00b0C**.\n   - Stir constantly using a magnetic stir bar to ensure even heating and mixing.\n   - Maintain the temperature for **4\u20138 hours**. You may observe an increase in viscosity as the reaction progresses, indicating polymer formation.\n\n2. **Monitoring the Reaction:**\n   - If needed, withdraw small aliquots of the reaction mixture at regular intervals to monitor the conversion of monomer to polymer using **NMR spectroscopy**, **FTIR**, or **GPC** (Gel Permeation Chromatography).\n\n#### **(4) Post-Polymerization Workup**\n1. **Precipitation (if desired):**\n   - After the reaction is complete, cool the mixture to room temperature.\n   - Precipitate the polymer by adding the reaction mixture into an excess of cold ethanol under vigorous stirring.\n   - Collect the polymer by filtration and wash with ethanol several times to remove unreacted monomer and impurities.\n\n2. **Drying the Polymer:**\n   - Dry the resulting polymer under vacuum at 40\u201350 \u00b0C until a constant weight is achieved.\n\n---\n\n### **Step 4: Polymer Characterization**\n\nThe synthesized polymer can be characterized using the following techniques:\n- **FTIR Spectroscopy:** To confirm the polymer structure, look for characteristic amide absorption bands (~1650 cm\u207b\u00b9) and hydroxyl groups (~3400 cm\u207b\u00b9).\n- **NMR Spectroscopy:** To verify monomer conversion and polymer integration.\n- **Gel Permeation Chromatography (GPC):** To determine the molecular weight (Mn, Mw) and polydispersity index (PDI).\n- **Contact Angle Measurements:** To evaluate the hydrophilicity of the polymer surface.\n\n---\n\n### **Step 5: Notes and Recommendations**\n- **Safety Precautions:**\n  - Handle AIBN carefully, as it is a thermal explosive. Store it in a cool and dry place and weigh it in a fume hood.\n  - Always work with proper personal protective equipment (PPE) and ensure good ventilation in the laboratory.\n- **Optimization Tips:**\n  - The reaction conditions (e.g., initiator concentration, temperature) can be adjusted depending on the molecular weight and PDI required for the polymer.\n  - For improved control over the polymer structure (e.g., block or graft copolymers), consider using another polymerization approach like RAFT (Reversible Addition-Fragmentation chain Transfer) polymerization.\n  \n---\n\n### Final Words\nThis experimental scheme provides a reliable and systematic approach to synthesizing hydrophilic polymers using **N-Hydroxyethylacrylamide**. By following these steps and maintaining rigorous control over the reaction conditions, the desired polymer with excellent hydrophilicity can be achieved. Let me know if you have any additional questions or need assistance with advanced polymerization techniques!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Considering dimethyl allylphosphonate, explain how you would optimize the PECVD process parameters, such as plasma power and pulsed versus continuous plasma configuration, to achieve uniform surface modification of the polymer."}, {"role": "assistant", "content": "To answer your question systematically and comprehensively, I will first analyze the query and derive key points, followed by detailing the process of optimizing the Plasma Enhanced Chemical Vapor Deposition (PECVD) process parameters for uniform surface modification of polymers using dimethyl allylphosphonate. By taking a logical and scientific approach, I will aim to provide specific experimental parameters to help you achieve your objective in the laboratory.\n\n---\n\n### **Key Points Analysis**\nThe key aspects of your question are:\n1. **Material of Interest**: Dimethyl allylphosphonate (DMAP), a molecule with polar functional groups, which suggests potential for imparting hydrophilic properties upon the polymer surface.\n2. **Goal**: Achieving uniform surface functionalization with the help of the PECVD process to enhance hydrophilicity.\n3. **Optimization Factors in PECVD**:\n   - **Plasma Power**: Balancing fragmentation and deposition to achieve the desired surface modification.\n   - **Pulsed vs. Continuous Plasma Configurations**: Examining the impact of each mode on deposition uniformity, crosslinking density, and preservation of the desired functional groups.\n4. **Outcome**: Uniform, controlled incorporation of dimethyl allylphosphonate onto the polymer surface to increase hydrophilicity while preserving the chemical integrity of functional groups.\n\nWith these points in mind, let us proceed step by step with the PECVD optimization process.\n\n---\n\n### **Systematic Explanation of PECVD Optimization Using Dimethyl Allylphosphonate**\n\n#### **Step 1: Understanding the Molecular Properties of Dimethyl Allylphosphonate**\nDimethyl allylphosphonate contains:\n- A polar phosphonate group (-PO3R2), which enhances surface wettability through hydrogen bonding or dipole interactions with water molecules.\n- An allyl group (-CH2CH=CH2), which allows potential crosslinking or copolymerization in the PECVD plasma environment.\n- Moderate thermal and chemical stability, which influences the choice of process conditions (e.g., plasma energy and substrate temperature).\n\nThis combination makes DMAP a suitable precursor for hydrophilic modification via PECVD.\n\n---\n\n#### **Step 2: Selection of Precursor Delivery System**\n1. Utilize a **vapor delivery system** to introduce dimethyl allylphosphonate (DMAP) into the PECVD chamber as a vapor-phase precursor. \n   - DMAP can be vaporized by heating mildly above room temperature (35\u201350\u00b0C) depending on its vapor pressure while avoiding decomposition.\n   - A carrier gas such as argon (Ar) or nitrogen (N2) can help transport the precursor into the chamber.\n\n#### **Step 3: Plasma Power Optimization**\nThe plasma power (or RF power) parameter controls the energy imparted to the precursor, influencing its fragmentation and reactivity:\n1. **Low Plasma Power (20\u201350 W)**:\n   - Promotes gentle fragmentation, preserving polar phosphonate groups.\n   - Results in longer deposition times but maintains functional group integrity and hydrophilicity.\n   - Suitable if minimal chemical alteration of DMAP is desired.\n   \n2. **Moderate Plasma Power (50\u2013150 W)**:\n   - Achieves a balance between precursor fragmentation and recombination.\n   - Increases deposition rate and enhances crosslinking, while still retaining polar functionalities under optimal conditions.\n   - Likely an ideal range for your experiment to ensure uniform surface coverage and effective functionalization.\n\n3. **High Plasma Power (>150 W)**:\n   - Causes excessive precursor fragmentation, leading to loss of functional groups and formation of non-hydrophilic crosslinked films (graphitic or carbon-rich layers).\n   - Avoid at high power if preservation of hydrophilic properties is critical.\n\n---\n\n#### **Step 4: Pulsed vs. Continuous Plasma Configuration**\nThe choice between pulsed and continuous plasma significantly affects surface uniformity and functional group preservation:\n\n1. **Pulsed Plasma**:\n   - Involves alternating \"on\" and \"off\" cycles of plasma generation.\n   - Benefits:\n     - Reduces excessive fragmentation by allowing functional group-containing fragments to deposit during the \"off\" periods.\n     - Better control over crosslinking density, reducing polymer damage or over-deposition.\n   - Parameters to consider:\n     - Duty Cycle (on/off ratio): Start with around 50% duty cycle (e.g., 500 ms \"on\", 500 ms \"off\").\n     - Frequency: Use typical ranges such as 1\u201310 kHz for controlled energy delivery.\n\n2. **Continuous Plasma**:\n   - Plasma remains \"on\" through the entire process.\n   - Benefits:\n     - Higher deposition rates and simpler process control.\n   - Drawbacks:\n     - Potential for over-fragmentation of DMAP, reducing hydrophilic group density.\n   - Suitable only if optimization of other parameters (low plasma power, short deposition time) prevents overreaction.\n\n**Recommendation**: Start with pulsed plasma to achieve higher uniformity and better functional group retention. Optimize duty cycle and frequency for your specific setup.\n\n---\n\n#### **Step 5: Deposition Temperature**\nThe substrate temperature during PECVD also affects deposition quality:\n- Maintain moderate substrate temperatures (40\u201380\u00b0C) to avoid premature polymer degradation or over-fragmentation of DMAP.\n- Higher temperatures may enhance crosslinking but can also result in the loss of polar functional groups.\n\n---\n\n#### **Step 6: Reaction Chamber Pressure**\nThe chamber pressure directly influences the mean free path of ions and radicals in the plasma:\n- Start with standard PECVD pressures (50\u2013200 mTorr) and ensure uniform precursor distribution.\n- Lower pressures favor higher energy collisions, whereas higher pressures reduce ion energy but enhance layer uniformity.\n\nExperiment with 100 mTorr as a baseline pressure for your trials.\n\n---\n\n#### **Step 7: Experimental Trials and Optimization**\nConduct a systematic evaluation of the combinations of key parameters:\n1. Plasma Power: Start with 50 W and incrementally increase up to 150 W.\n2. Pulsed Plasma Duty Cycle: Experiment with 30\u201370% duty cycles.\n3. Chamber Pressure: Test 100 mTorr \u00b1 50 mTorr.\n4. Temperature: Keep 60\u00b0C constant initially, then adjust if necessary.\n\n---\n\n#### **Step 8: Characterization and Evaluation**\nAfter surface modification, evaluate the polymer surface to confirm successful deposition of hydrophilic DMAP:\n1. **Contact Angle Measurement**:\n   - Quantify hydrophilicity by measuring water contact angles. Lower angles indicate increased hydrophilic modification.\n2. **Fourier Transform Infrared Spectroscopy (FTIR)**:\n   - Confirm the presence of phosphonate functional groups on the surface.\n3. **X-ray Photoelectron Spectroscopy (XPS)**:\n   - Detect elemental composition and confirm the incorporation of phosphorus (from DMAP) on the surface.\n4. **Surface Morphology**:\n   - Use Scanning Electron Microscopy (SEM) or Atomic Force Microscopy (AFM) to check for uniformity.\n5. **Adhesion Testing**:\n   - Verify the durability of the modified surface layer.\n\n---\n\n### **Conclusion**\nTo achieve uniform surface functionalization while preserving hydrophilicity, I recommend the following optimized process:\n1. **Plasma Configuration**: Pulsed plasma with a duty cycle around 50%.\n2. **Plasma Power**: Moderate power of ~100 W (adjust as necessary).\n3. **Temperature**: Substrate temperature of 60\u00b0C.\n4. **Pressure**: Chamber pressure of 100 mTorr.\n5. **Precursor Introduction**: Vaporized DMAP with N2 or Ar as carrier gas.\n\nConduct systematic variations in these parameters while evaluating the results through appropriate characterization techniques. By carefully balancing plasma power and deposition conditions, you should achieve a uniform, hydrophilic polymer surface.\n\nI hope this detailed explanation provides clarity. If you have further questions, don\u2019t hesitate to ask!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "A water dispersible polyurethane compound is to be modified using a silicone compound containing \u2014OH groups. How would you determine the appropriate ratio of the silicone compound to the polyurethane compound to ensure uniform dispersion while maintaining film integrity?"}, {"role": "assistant", "content": "### Analyzing the Question and Summarizing Key Points\n\nYour question pertains to the modification of a **water-dispersible polyurethane** with a **silicone compound containing \u2014OH groups.** Specifically, you are looking to determine the appropriate **ratio** of the silicone compound to the polyurethane to achieve:\n1. **Uniform dispersion** of the modified polymer in water.\n2. **Good film-forming properties** (film integrity) while maintaining hydrophilicity.\n\nThis problem requires understanding both chemistry fundamentals (polyurethane modification and silicone reactivity) and considerations of physical properties (film-forming, dispersibility).\n\nKey points of the question:\n- Polyurethane is the base polymer, and it is water-dispersible. This implies it likely contains hydrophilic ionic or non-ionic groups (e.g., sulfonates, carboxylates, or ethylene oxide/PEG chains) that facilitate dispersion in water.\n- Silicone compound has \u2014OH groups, suggesting it may participate in chemical bonding (via reaction with isocyanates in polyurethane) or physical interaction, potentially introducing hydrophobicity or altering the polymer's surface activity.\n- The challenge is optimizing the **silicone-to-polyurethane ratio** to balance uniform dispersion and good film integrity without compromising hydrophilicity. Incorrect ratios might lead to phase separation, poor dispersibility, or brittle/incompatible films.\n\nTo address this systematically, we need a detailed experimental scheme for synthesizing and evaluating the modified polymer.\n\n---\n\n### Detailed and Systematic Preparation Scheme\n\n#### Step 1: Define the Reaction Mechanism\nThe modification typically occurs through **grafting or blending**:\n1. If isocyanate groups (\u2014NCO) are still available in your prepolymer, the silicone compound (containing \u2014OH) can react with them to form urethane linkages (R\u2014N\u2014CO\u2014O\u2014Si). This creates a covalent bond, incorporating silicone into the polyurethane backbone.\n2. If no \u2014NCO is available, the silicone compound may mix physically with the polyurethane, assisted by hydrogen bonding or secondary interactions. In this case, phase compatibility becomes critical to prevent separation.\n\n---\n\n#### Step 2: Experimental Strategy to Determine Silicone-to-Polyurethane Ratio\n\n1. **Start with a theoretical calculation** based on molecular weights:\n   - Determine the molecular weight of the silicone compound (M_s) and the polyurethane (M_p).\n   - Calculate the number of \u2014OH groups in the silicone compound and the number of reactive sites (e.g., \u2014NCO or ionic sites) in the polyurethane.\n\n2. **Establish an initial range of silicone-to-polyurethane ratios:**\n   - Start with **silicone-to-polyurethane weight ratios** (0.5:100, 1:100, 2:100, 5:100, etc.).\n   - Too much silicone can compromise dispersion or overplasticize the film, while too little may not produce significant modification.\n\n3. **Reaction Stoichiometry (if grafting is used):**\n   - For a covalent reaction with \u2014NCO, ensure a moderate stoichiometric excess of \u2014NCO groups (e.g., [NCO]/[OH] \u2265 1.2) for complete reaction.\n   - Example: If your prepolymer contains 2 mmol of \u2014NCO groups per gram, and your silicone compound has 1 mmol of \u2014OH groups per gram, start with a 1:3 or 1:2 molar ratio of \u2014OH to \u2014NCO.\n\n4. **Solvent and Catalyst Selection:**\n   - Use a polar aprotic solvent (like DMF or acetone) for uniform mixing and control of viscosity.\n   - Incorporate a catalyst like dibutyltin dilaurate (DBTDL) if curing or grafting the silicone compound via reaction with \u2014NCO.\n\n---\n\n#### Step 3: Reaction Process\n1. **Stepwise Addition of Silicone:**\n   - Dissolve the water-dispersible polyurethane in a suitable solvent.\n   - Slowly add the silicone compound under stirring to prevent localized oversaturation, which can lead to phase separation. A mechanical stirrer or homogenizer is recommended for uniform dispersion.\n\n2. **Temperature and Reaction Time:**\n   - If a chemical reaction is expected (bonding silicone to polyurethane through \u2014NCO groups), maintain the temperature at 50\u201380\u00b0C for 2\u20136 hours, avoiding premature gelation.\n   - For physical blending, ensure thorough emulsification for 30\u201360 minutes at room temperature.\n\n3. **Water Dispersion Testing:**\n   - Gradually add water (pH ~7) to the reaction mixture under high-speed stirring to produce an aqueous dispersion. Test the stability of dispersion (check for sedimentation or agglomeration over time).\n\n---\n\n#### Step 4: Evaluate Film Integrity and Hydrophilicity\n1. **Prepare Thin Films:**\n   - Cast films of the modified polymer on a glass substrate and dry at 50\u201380\u00b0C for 24 hours.\n\n2. **Characterize the Films:**\n   - **Film integrity:** Test mechanical properties (tensile strength, elongation at break) using a universal testing machine. Optimize the silicone content to achieve films that are flexible and continuous.\n   - **Hydrophilicity:** Measure the water contact angle. Lower angles indicate higher hydrophilicity (~30\u201350\u00b0 is optimal).\n\n---\n\n#### Step 5: Optimize Ratio Based on Results\n1. Compare results for different silicone-to-polyurethane ratios.\n2. Select the lowest silicone ratio that maintains good film integrity and hydrophilicity, ensuring uniform dispersion in water.\n\n---\n\n### Final Notes\n- Typical starting ratios are in the range of **1\u20135% (w/w) silicone compound relative to polyurethane.** Increase gradually if needed.\n- Excess silicone might reduce hydrophilicity and cause phase separation, so balance is critical.\n\nBy following this systematic experimental protocol, you will be able to determine the optimal silicone-to-polyurethane ratio while ensuring uniform dispersion and maintaining film integrity."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe an experimental procedure to synthesize a hydrophilic polymer using trimethylolpropane (tri-hydroxy methyl propane), including details on how to enhance the hydrophilicity of the final polymer product."}, {"role": "assistant", "content": "### Thought Process:\nTo synthesize a hydrophilic polymer based on the provided molecule, trimethylolpropane (TMP), we need to leverage its tri-functional hydroxyl groups (-OH) as reactive sites. These hydroxyl groups make TMP an excellent precursor for forming a range of polymers, especially those designed for hydrophilicity due to the ability to introduce polar and hydrogen-bonding functional groups. To enhance the hydrophilicity of the final polymer product, we can introduce additional hydrophilic groups such as carboxyl (-COOH), hydroxyl (-OH), or ionic groups, such as sulfonic acid (-SO3H).\n\nTaking these aspects into consideration, I will provide a step-by-step systematic experimental procedure below for the synthesis of a hydrophilic polymer based on TMP, which includes techniques to increase hydrophilicity.\n\n---\n\n### Key Points for Planning the Synthesis:\n1. **Reactant Selection**: Trimethylolpropane (tri-hydroxy methyl propane) is the core monomer. Other monomers/reagents should be chosen to introduce hydrophilic functional groups.\n2. **Polymerization Route**: Select either a step-growth polymerization (e.g., esterification) or other functionalization using hydrophilic reactants.\n3. **Enhancing Hydrophilicity**: Use reagents containing groups like -COOH, -OH, or -SO3H. These groups increase hydrophilicity and water solubility.\n4. **Reaction Parameters**: Determine the ideal reaction conditions (temperature, catalysts, and solvent) to optimize polymerization and hydrophilicity.\n\n---\n\n### Detailed Experimental Procedure:\n#### **Synthesis of Hydrophilic Polymer from Trimethylolpropane**:\nWe will prepare a hydrophilic polyester by reacting trimethylolpropane (TMP) with a dicarboxylic acid (e.g., citric acid) followed by end-functionalization to enhance hydrophilicity.\n\n---\n\n#### **Step 1. Esterification Polymerization (Base Polymer Synthesis):**\n**Objective**: Cross-link TMP with citric acid to form a three-dimensional hydrophilic polyester network.\n\n- **Materials Needed**:\n  - Trimethylolpropane (TMP): 10 g (0.075 mol)\n  - Citric acid (CA): 14.02 g (0.073 mol, slight stoichiometric excess to favor ester bond formation and ensure residual unreacted carboxylic acid groups contribute to hydrophilicity)\n  - Catalyst: p-Toluenesulfonic acid (PTSA), 0.2 g (approx. 2 wt% of total reactants)\n  - Solvent: None (reaction performed in bulk to avoid solvent contamination for hydrophilic performance enhancement).\n  - Reaction vessel: 250-mL round-bottom flask with a reflux condenser.\n\n**Procedure**:\n1. Place TMP and citric acid in a round-bottom flask equipped with a magnetic stirrer, and add PTSA as a catalyst.\n2. Gradually heat the mixture to **140\u2013160\u00b0C** under inert nitrogen gas to prevent oxidation.\n3. Stir and maintain temperature for **4\u20135 hours**. Initially, the system will appear molten as ester bonds begin forming.\n4. Monitor the reaction progress by observing water evolution (a by-product of esterification) using a Dean-Stark trap if necessary.\n5. Monitor polymer formation using FT-IR spectroscopy. Look for diminishing O-H stretching (~3300 cm\u207b\u00b9) and increasing ester carbonyl band (~1730 cm\u207b\u00b9).\n6. Once complete, allow the reaction mixture to cool to room temperature.\n\n**Expected Product**:\nA hydrophilic polyester with terminal -COOH groups (from excess citric acid), as well as some unreacted -OH groups (from TMP).\n\n---\n\n#### **Step 2. Enhancing Hydrophilicity via Post-Functionalization**:\n**Objective**: Introduce additional hydrophilic ionic groups (e.g., sulfonic acid) to the polymer.\n\n- **Materials Needed**:\n  - Chlorosulfonic acid (HSO3Cl): 5 mL (be cautious with its high reactivity)\n  - Pyridine: 10 mL (acts as a scavenger for HCl formed by the reaction)\n  - Solvent: Dry dichloromethane (DCM), 50 mL.\n  - Product from Step 1: 5 g.\n\n**Procedure**:\n1. Dissolve the polyester from Step 1 in 50 mL of dry DCM in a 250-mL round-bottom flask under nitrogen atmosphere.\n2. Slowly add chlorosulfonic acid dropwise (over 30 minutes) to prevent localized overheating, stirring continuously at **0\u00b0C** (ice bath).\n3. After the addition, allow the mixture to gradually warm to room temperature and stir for another **4 hours**.\n4. Quench the reaction by carefully adding ice-cold water while stirring (beware of vigorous HCl release).\n5. Separate the aqueous phase containing the sulfonated polymer and dialyze it against water for 48 hours to remove residual salts and impurities.\n6. Lyophilize (freeze dry) the polymer solution to obtain the sulfonated hydrophilic polymer as a powder.\n\n**Expected Product**:\nThe final polymer now contains sulfonic acid (-SO3H) groups and residual -OH or -COOH groups, rendering it highly water-absorbent and hydrophilic.\n\n---\n\n#### **Step 3. Characterization and Confirmation**:\nPerform the following tests to verify the structure and hydrophilicity of the synthesized polymer:\n1. **FT-IR Spectroscopy**: Look for:\n   - Ester carbonyl (C=O) peaks around 1730 cm\u207b\u00b9.\n   - Sulfonic acid (S=O) doublet peaks around 1190\u20131260 cm\u207b\u00b9.\n2. **Contact Angle Measurement**: Drop water on the polymer film to observe its hydrophobicity; a lower contact angle indicates higher hydrophilicity.\n3. **Water Absorption Test**: Measure the water uptake (swelling ratio) by immersing the polymer in water.\n4. **Thermogravimetric Analysis (TGA)**: Check for thermal stability of the hydrophilic polymer.\n5. **NMR Spectroscopy**: Analyze the backbone structure and quantify functional group incorporation.\n\n---\n\n### Notes and Safety Considerations:\n1. **Stoichiometry Control**: Ensure a slight excess of citric acid in Step 1 to promote hydrophilicity through residual functional groups.\n2. **Reaction Environment**: Keep the system moisture-free during the sulfonation reaction to prevent side reactions.\n3. **Safety**:\n   - Handle chlorosulfonic acid in a fume hood due to its corrosive nature and potential HCl release.\n   - Ensure proper personal protective equipment (PPE), including gloves, goggles, and a lab coat.\n\n---\n\n### Conclusion:\nThis experimental protocol details the synthesis of a hydrophilic polymer using trimethylolpropane via esterification with citric acid followed by sulfonation. The resulting polymer is rich in hydrophilic functional groups (-OH, -COOH, and -SO3H), making it suitable for applications such as hydrophilic coatings, biomedical devices, or absorbent materials."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the key experimental steps you would follow to ensure the reaction involving POSS-Br proceeds efficiently under oxygen-free conditions."}, {"role": "assistant", "content": "To address your question scientifically and systematically, we will first analyze the problem, identify the key points, and then provide a detailed step-by-step experimental protocol to ensure an efficient reaction of POSS-Br under oxygen-free conditions.\n\n---\n\n### Step 1: **Analyze the Problem**\nThe key points you\u2019ve raised are:\n1. **Substrate**: POSS-Br is the compound in focus here.\n2. **Efficiency**: The goal is to maximize the reaction efficiency.\n3. **Reaction Conditions**: The reaction must be carried out under oxygen-free (inert) conditions, which often signifies safeguarding the reaction against oxygen interference, typically for sensitive reagents or catalysts.\n\n### Step 2: **Rationale for Oxygen-Free Conditions**\nOxygen, even in trace amounts, can inhibit reactions\u2014particularly those involving radicals, moisture-sensitive catalysts, or materials prone to oxidative damage (such as POSS derivatives). Therefore, specific strategies, such as inert gas purging or using a glovebox, are critical to maintaining an oxygen-free environment.\n\n---\n\n### Step 3: **Detailed Experimental Protocol**\nBelow is a systematic procedure to ensure the reaction proceeds efficiently under oxygen-free conditions:\n\n---\n\n#### **Step 3.1: Preparing the Setup**\n1. **Glassware Preparation**:\n   - Use Schlenk tubes, flasks, or a sealed reactor compatible with inert gas handling.\n   - Dry the glassware thoroughly in a vacuum oven (110 \u00b0C for at least 2 hours) before the experiment to ensure no residual moisture exists.\n\n2. **Assembly Under Inert Atmosphere**:\n   - Move the glassware into a glovebox (preferred) or connect it to a Schlenk line capable of argon or nitrogen purging.\n   - Ensure all joints are airtight by lubricating them with vacuum grease and securing them with clamps.\n\n3. **Selection of Solvent**:\n   - Use an anhydrous, oxygen-free solvent suitable for the reaction. Possible solvents are tetrahydrofuran (THF), dimethylformamide (DMF), or toluene.\n   - Before use, distill the solvent under inert gas if necessary, or use commercially available anhydrous solvents from sealed bottles.\n\n---\n\n#### **Step 3.2: Reaction Setup and Execution**\n1. **Introducing POSS-Br and Reagents**:\n   - Weigh POSS-Br under ambient conditions (if stable in air), or inside a glovebox if it is air sensitive.\n   - Introduce a stoichiometric or slightly excess amount of POSS-Br into the reactor based on the reaction requirement (e.g., 1 mmol for preliminary scale testing).\n   - Add any required co-reagents (e.g., a nucleophile, catalyst, or other reactive species), ensuring accurate molar ratios as dictated by your specific reaction.\n\n2. **Purging Oxygen**:\n   - If using a Schlenk line, perform **three cycles of evacuation and refilling** with argon or nitrogen to displace air completely.\n   - If using a glovebox, transfer all materials and seal the glassware tightly before removing it from the box.\n\n3. **Addition of Solvent**:\n   - Add the anhydrous solvent inside the inert atmosphere (e.g., through a septum using a syringe) to ensure no atmospheric exposure.\n   - Use approximately 10\u201315 mL of solvent for every mmol of POSS-Br, depending on the reaction scale and solubility of the compounds.\n\n4. **Stirring and Reaction Conditions**:\n   - Seal the reaction vessel and heat or cool it to the desired conditions (e.g., 60\u201380 \u00b0C for nucleophilic substitutions reactions if no incompatibilities arise).\n   - Ensure vigorous stirring to maintain homogeneity.\n   - If air-sensitive catalysts (e.g., transition metal complexes) or thermal initiators are involved, ensure their storage and handling under inert conditions before use.\n\n---\n\n#### **Step 3.3: Monitoring Reaction Progress**\n1. **Sampling**:\n   - Periodically withdraw small aliquots of the reaction mixture using a gas-tight syringe and analyze using gas chromatography (GC), high-performance liquid chromatography (HPLC), or nuclear magnetic resonance (NMR) spectroscopy to ensure reaction progression.\n   - Continue purging the reactor during sampling (if applicable).\n\n2. **Duration**:\n   - Allow the reaction to run for a pre-determined time (e.g., 8\u201324 hours), depending on the kinetic studies for POSS-Br reactions.\n\n---\n\n#### **Step 3.4: Workup**\n1. **Quenching the Reaction**:\n   - If applicable, the reaction may require quenching by adding a non-reactive diluent (e.g., ethanol) under inert conditions.\n   - Follow the quenching protocol as dictated by reagent incompatibilities or reaction type.\n\n2. **Removing Solvent**:\n   - Remove the solvent under reduced pressure (using a rotary evaporator) after purging the system once more with inert gas.\n\n3. **Purification**:\n   - Purify the product, if necessary, via recrystallization, column chromatography, or precipitation techniques.\n   - Store purified products in sealed containers under inert conditions.\n\n---\n\n### Step 4: **Reaction-Specific Optimizations**\nConsider the following for higher reaction specificity:\n- Catalyst concentration: If a catalyst (e.g., palladium or copper) is used, optimize its concentration (start with 5 mol% relative to POSS-Br).\n- Additives: In certain cases, a reductant (e.g., sodium ascorbate) or ligand might be required to accelerate the reaction.\n- Temperature or Pressure: Adjust based on initial yields; for example, radical reactions sometimes benefit from UV or controlled heating under pressure.\n\n---\n\n### Closing Remarks\nBy carefully following this process, you can ensure the reaction involving POSS-Br proceeds efficiently under oxygen-free conditions. The critical aspects include the proper establishment and maintenance of the inert atmosphere, precise measurements of reagents, and consistent monitoring of reaction progress. If there are any ambiguities specific to your experiment, feel free to share more details or consult particular reaction protocols for POSS-based compounds."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the role of 2,2'-azobis(2-methylpropionitrile) (AIBN) in the polymerization process and how the amount of AIBN influences the formation of hydrophilic polymers."}, {"role": "assistant", "content": "Certainly! Let's break the question into key components and systematically address it:\n\n---\n\n### **Question Analysis and Key Points:**\n1. **Role of 2,2'-azobis(2-methylpropionitrile) (AIBN):**\n   - AIBN is a commonly used free radical initiator in polymerization.\n   - The specific role of AIBN during polymerization needs to be clarified in terms of initiating the reaction and its impact on the resulting polymer properties.\n\n2. **Influence of AIBN Amount on Polymer Formation:**\n   - Investigate how the concentration of AIBN affects the polymerization rate, molecular weight, and hydrophilic nature of the final polymer.\n   - Explore the balance between initiator concentration and reaction control in achieving the desired hydrophilicity.\n\n---\n\n### **Systematic Answer to the Question:**\n\n#### **Step 1: Role of 2,2'-Azobis(2-methylpropionitrile) (AIBN) in Polymerization**\n   1. **Initiation of Polymerization:**\n      - AIBN is a thermal initiator that decomposes upon heating to release free radicals, which are essential for initiating chain polymerization reactions. Upon heating (generally between 60\u201390\u00b0C), AIBN undergoes homolytic cleavage to form two 2-cyanoprop-2-yl radicals:\n        \\[\n        \\text{R-N=N-R} \\xrightarrow{\\Delta} 2R^\\bullet\n        \\]\n        Here, \\(R^\\bullet\\) represents the free radical species.\n\n      - These radicals react with monomer molecules, forming reactive centers that propagate polymer chains.\n\n   2. **Control of Polymerization Kinetics:**\n      - The rate of polymerization depends on the concentration of free radicals generated by AIBN. A higher concentration of radicals accelerates the chain-initiation step but also increases the rate of chain-termination reactions, ultimately influencing the polymer's molecular weight.\n\n   3. **Impact on Hydrophilicity:**\n      - For hydrophilic polymer synthesis, AIBN facilitates polymerization of hydrophilic monomers (e.g., acrylamide, hydroxyethyl methacrylate) or ensures copolymerization with hydrophilic segments.\n      - The uniformity of radical formation by AIBN is critical to achieving a controlled polymer architecture, minimizing defects, and reliably incorporating hydrophilic functional groups.\n\n---\n\n#### **Step 2: Influence of AIBN Amount on Polymer Formation**\n   1. **Optimal AIBN Concentration:**\n      - **Low Concentration of AIBN:** \n        - Generates fewer radicals, leading to slower polymerization and longer polymer chains. This results in higher molecular-weight polymers with reduced termination events.\n        - For hydrophilic polymers, fewer radicals may allow better incorporation of hydrophilic monomers, enhancing solubility and water affinity.\n        - However, excessively low concentration can result in incomplete polymerization or uneven hydrophilic segment distribution.\n\n      - **High Concentration of AIBN:**\n        - Produces a higher number of free radicals, which accelerates initiation and polymerization.\n        - Leads to shorter polymer chains due to the increased likelihood of chain termination (e.g., radical recombination).\n        - At very high concentrations, hydrophilicity may be reduced, as the polymerization may favor formation of shorter hydrophobic blocks or inefficient incorporation of hydrophilic monomers.\n\n   2. **Determining the Right Balance:**\n      - The amount of AIBN should be optimized to achieve the desired hydrophilic properties without comprising chain uniformity or molecular weight distribution. This typically involves experimental trials with varying concentrations.\n      - A guideline for AIBN is to use 0.5\u20132.0 mol% relative to monomer concentration, though specific optimization depends on the nature of the monomers and reaction medium.\n\n---\n\n#### **Step 3: Experimental Scheme for Optimizing AIBN in Hydrophilic Polymer Synthesis**\n   We\u2019ll outline a general experiment where the influence of AIBN is studied systematically to find the optimal conditions:\n\n   1. **Materials:**\n      - Monomer: A hydrophilic monomer such as acrylamide or hydroxyethyl methacrylate (HEMA).\n      - Solvent: Deionized water or a suitable solvent compatible with the monomer (e.g., ethanol for HEMA).\n      - Initiator: AIBN (start with 1.0 mol% relative to total monomer).\n      - Additional reagents: Crosslinker (if needed) or a chain transfer agent (to modulate chain length).\n\n   2. **Procedure:**\n      - **Step 1: Preparation of Reaction Mixture**\n        - Dissolve the hydrophilic monomer in the chosen solvent at the desired concentration (e.g., 10\u201320% w/v).\n        - Add AIBN at an initial amount (e.g., 1.0 mol% of monomer) and mix thoroughly.\n      - **Step 2: Degassing**\n        - Purge the reaction mixture with nitrogen or argon gas for 15\u201330 minutes to remove dissolved oxygen, which can inhibit radical polymerization.\n      - **Step 3: Polymerization**\n        - Heat the mixture to 70\u00b0C (or the recommended temperature for AIBN) and maintain under constant stirring. Monitor the reaction for 1\u20136 hours, depending on the desired conversion and polymerization rate.\n      - **Step 4: Quenching and Isolation**\n        - Stop the reaction by cooling to room temperature and diluting with water (if needed). Precipitate the polymer using an anti-solvent (e.g., acetone for HEMA) or dialyze to remove unreacted species.\n\n   3. **Analysis of Results:**\n      - Measure molecular weight and distribution (e.g., using GPC or SEC).\n      - Evaluate hydrophilicity via water contact angle measurements, swelling tests, or solubility in water.\n      - Compare the results for multiple AIBN concentrations (e.g., 0.5, 1.0, and 2.0 mol%) to identify trends and optimize conditions.\n\n---\n\n### **Conclusion:**\n2,2\u2032-Azobis(2-methylpropionitrile) (AIBN) plays a critical role as a thermal initiator by generating free radicals that drive polymerization. The amount of AIBN significantly impacts the polymerization kinetics, molecular weight, chain architecture, and ultimately the hydrophilic properties of the polymer. A balance must be struck in choosing the appropriate AIBN concentration to achieve high polymerization efficiency while maximizing hydrophilicity. Systematic experimental trials are essential to determine optimal conditions, tailored to the specific monomers used and their reactivity.\n\n"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Design a procedure to uniformly dissolve benzophenone in a solvent mixture prior to its use in preparing a hydrophilic polymer coating. Specify the type of solvents you might choose and their potential effects on the final coating."}, {"role": "assistant", "content": "Certainly! The process of dissolving benzophenone uniformly in a solvent mixture to be used in preparing a hydrophilic polymer coating involves a number of considerations. Allow me to break this down step by step to provide a detailed and systematic experimental protocol, while discussing the choice of solvents and their impact on the final polymer coating.\n\n---\n\n### **1. Analyze the question and summarize the key points:**\n- **Objective:** Dissolve benzophenone uniformly in a solvent mixture as part of the preparation step for a hydrophilic polymer coating.\n- **Key considerations:**\n   - Benzophenone's solubility depends on the solvent polarity.\n   - The solvent must be compatible with the monomers and/or polymers used in the hydrophilic coating preparation.\n   - The solvent system should not interfere with hydrophilicity or polymerization reactions.\n   - Uniform dissolution is critical to ensure consistent coating performance.\n\n---\n\n### **2. Detailed procedure for dissolving benzophenone in a solvent mixture:**\n\n#### **Step 1: Solvent selection**\nTo dissolve benzophenone efficiently, a combination of polar and nonpolar solvents may be required. Benzophenone has moderate polarity due to the carbonyl functional group, so solvents of intermediate polarity are ideal. For a hydrophilic polymer formulation, the following solvent options are commonly used:\n\n1. **Ethanol (polar solvent):**\n   - It has good solubility for benzophenone.\n   - Enhances the hydrophilicity of the system.\n   - Evaporates relatively quickly, minimizing interference in subsequent polymerization.\n\n2. **Acetone (polar aprotic solvent):**\n   - Solubilizes benzophenone effectively.\n   - Compatible with many hydrophilic polymers' synthesis processes.\n\n3. **Tetrahydrofuran (THF, moderately polar):**\n   - Excellent solvent for benzophenone.\n   - Miscible with water, which may be useful for hydrophilic polymer coatings.\n\n4. **Isopropanol (IPA, polar):**\n   - Acts as a good miscible solvent and complements benzophenone's dissolution.\n\nAlternatively, for a two-solvent system:\n- Ethanol (polar) and THF (intermediate polarity) can be combined to tune solvent polarity.\n- Water can also be introduced in small amounts in specific cases to promote greater hydrophilicity.\n\n#### **Step 2: Determine reagent quantities**\n- Decide on the quantity of benzophenone to dissolve based on your hydrophilic polymer formulation. For example, if the coating mixture requires 10 g of benzophenone:\n  - Use a 1:10 (w/v) ratio initially as a starting point, i.e., 100 mL of solvent mixture per 10 g of benzophenone.\n  - Adjust solvent quantities based on solubility tests to ensure complete dissolution.\n\n#### **Step 3: Prepare the solvent mixture**\n1. Choose the primary solvent (e.g., THF) and secondary solvent (e.g., ethanol), ensuring they are miscible.\n2. Mix the solvents in appropriate proportions (common mixtures are 70:30, 50:50, or 30:70 by volume) to achieve the desired polarity for benzophenone dissolution.\n3. Stir the solvent mixture thoroughly for 5 minutes to ensure homogeneity.\n\n#### **Step 4: Dissolve benzophenone**\n1. Gradually add benzophenone to the solvent mixture under continuous stirring.\n   - Use a magnetic stirrer set at moderate speed (e.g., 300\u2013500 rpm).\n   - Maintain room temperature (20\u201325\u00b0C) initially, as benzophenone dissolves readily at this temperature.\n2. Monitor dissolution visually. If complete dissolution is not achieved:\n   - Slightly warm the solvent mixture to about 40\u201350\u00b0C using a water bath. Avoid overheating, which may degrade benzophenone.\n\n#### **Step 5: Filtration (if necessary)**\n- If undissolved particles remain, filter the solution through a fine-pore membrane (e.g., 0.45 \u00b5m) to obtain a clear, uniform solution.\n\n#### **Step 6: Storage of the solution**\n- Store the benzophenone solution in an amber glass container to protect it from light (benzophenone is light-sensitive).\n- Keep the solution at room temperature if used within 24 hours; otherwise, refrigerate to prevent solvent evaporation.\n\n---\n\n### **3. Potential effects of selected solvents on the final coating:**\n\n1. **Hydrophilicity impact:**\n   - Using polar solvents like ethanol or water can enhance the hydrophilicity of the final polymer coating.\n   - Nonpolar solvents should be minimized to avoid compromising hydrophilicity.\n\n2. **Polymerization compatibility:**\n   - Ensure the solvent system does not interfere with the polymerization reaction (e.g., radical initiators may react with some solvents).\n   - For hydrophilic polymer coatings, ethanol and THF are preferred due to their inert behavior in common polymerization systems (like free-radical or photoinitiated reactions).\n\n3. **Uniformity of coating:**\n   - The choice of solvent affects coating uniformity and surface morphology.\n   - High volatility of solvents like acetone and ethanol aids in quick evaporation but requires controlled drying conditions to prevent uneven coating.\n\n---\n\n### **Final Notes for Lab Execution:**\n- Perform a small-scale solubility test before preparing the full solution.\n- Document all quantities and observations for reproducibility.\n- Use proper safety measures when handling volatile solvents (work in a fume hood, avoid open flames, use PPE).\n\nBy following these steps and considerations, you should obtain a uniform benzophenone solution compatible with hydrophilic polymer synthesis, ensuring high-quality coating preparation. Let me know if you have further questions!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the steps you would take to integrate imidazole into a formulation containing a nucleophilic addition product and an epoxy resin. How would you adjust the formulation to ensure proper functionality and hydrophilicity enhancement?"}, {"role": "assistant", "content": "Certainly! Thank you for your thoughtful question. To proceed systematically and logically, let's work step by step through the integration of **imidazole** into your formulation to achieve functionality enhancement, hydrophilicity, and performance optimization. I will provide a detailed experimental preparation scheme as you requested.\n\n---\n\n### **Step 1: Analyze the Question and Key Points**\n1. **Components**: You are working with a **nucleophilic addition product, an epoxy resin, and imidazole**. These components suggest a formulation likely involving epoxy curing or modification.\n2. **Objective**: The goal is twofold:\n    - **To integrate imidazole into the epoxy resin system**, possibly as a curing agent or modifier.\n    - **To enhance hydrophilicity** of the polymer product, which may involve hydrophilic functional groups or further chemical grafting/modification.\n3. **Challenges**:\n    - Controlling reaction conditions to prevent over-curing or undesirable crosslinking.\n    - Balancing hydrophilicity addition with maintaining the physical and mechanical properties of the polymer.\n\n---\n\n### **Step 2: Experimental Preparation Scheme**\n\nHere is the detailed scheme for preparing a hydrophilic polymer based on epoxy resin, nucleophilic addition products, and imidazole integration:\n\n---\n\n#### **Step 2.1: Materials and Reagents**\n- **Epoxy Resin**: Typically, a diglycidyl ether of bisphenol A (DGEBA) or another suitable epoxy compound.\n- **Imidazole**: Used as a curing agent or nucleophilic catalyst.\n- **Hydrophilic Nucleophilic Addition Product**: Depending on the specific substrate, this could include polyols, amino alcohols, or carboxyl-functionalized compounds that react with epoxy groups.\n- **Solvent (if needed)**: Water-miscible solvents such as dimethylformamide (DMF) or ethanol to improve homogeneity.\n- **Optional Hydrophilic Modifiers**: Molecules like polyethylene glycol (PEG) or hydroxyl-/amine-functionalized compounds to boost hydrophilicity.\n\n---\n\n#### **Step 2.2: Reaction Scheme**\nWe will perform the synthesis in two stages: (a) Pre-functionalization of the epoxy resin with hydrophilic groups via nucleophilic addition, and (b) Imidazole integration.\n\n---\n\n### **Stage I: Pre-functionalization of Epoxy Resin**\nThe first step is to react the epoxy resin with the nucleophilic addition product to introduce hydrophilic functional groups. This process increases the water compatibility and polar character of the final polymer.\n\n1. **Reaction Setup**:\n   - Place the epoxy resin into a clean, dry reaction flask equipped with a mechanical stirrer, nitrogen inlet, and a temperature control system.\n   - Add a small amount of solvent (if the resin viscosity is high) to improve stirring.\n\n2. **Addition of Nucleophilic Addition Product**:\n   - Slowly add the hydrophilic nucleophilic addition product to the flask. \n   - Ratio: Maintain an **equimolar ratio of epoxide groups to nucleophilic functional groups** of your addition product. Adjust depending on whether you desire partial or full reaction (e.g., a 1:1 molar ratio for complete functionalization).\n\n3. **Reaction Conditions**:\n   - **Temperature**: Maintain between **50\u201380\u00b0C** to activate the epoxy rings without thermal degradation.\n   - **Time**: Reaction proceeds for **3\u20136 hours** under stirring, depending on reactivity.\n   - Monitor progress using Fourier-transform infrared spectroscopy (FTIR), looking for the disappearance of the epoxide band (~915 cm\u207b\u00b9).\n\n4. **Optional Purification**:\n   - If necessary, remove excess nucleophilic addition product via solvent washing or vacuum distillation.\n\n---\n\n### **Stage II: Integration of Imidazole**\nNext, we incorporate imidazole into the pre-functionalized epoxy system. Imidazole is a strong nucleophile and base, and in this context, it can act as both:\n- A curing agent to generate a crosslinked network.\n- A hydrophilicity enhancer due to its heterocyclic nature.\n\n1. **Reaction Setup**:\n   - Transfer the pre-functionalized epoxy resin (from Stage I) into a reaction flask.\n   - Add imidazole gradually under continuous stirring to ensure homogeneous mixing.\n\n2. **Molar Ratio**:\n   - The imidazole-to-epoxide ratio depends on its role in the formulation:\n     - If imidazole serves as the **sole curing agent**, a ratio of **0.1\u20130.2 moles of imidazole per mole of residual epoxide groups** is typically sufficient.\n     - If imidazole is used in synergy with other curing agents, the ratio might be lowered (~0.05 moles of imidazole per mole of epoxide groups).\n\n3. **Reaction Conditions**:\n   - **Temperature**: Heat the mixture to **100\u2013150\u00b0C** to promote the reaction between imidazole and remaining epoxide groups.\n   - **Time**: Allow the reaction to proceed for **1\u20132 hours** under a nitrogen blanket to avoid moisture interference and epoxy degradation.\n   - Monitor progress by FTIR and Differential Scanning Calorimetry (DSC) to ensure curing is near completion.\n\n4. **Crosslinking and Hydrophilicity Enhancement**:\n   - Imidazole may initiate curing and simultaneously introduce hydrophilic amine groups into the polymer, due to its high polar functionality.\n   - Additional small hydrophilic compounds (e.g., low-molecular-weight PEG or amine-functionalized molecules) can be added at this stage if further hydrophilicity is desired.\n\n---\n\n### **Post-Reaction Processing**\n1. **Cool and Collect**:\n   - After curing or modification is complete, cool the system to room temperature.\n   - The product may precipitate as a solid or form a gel, depending on the degree of crosslinking.\n\n2. **Characterization**:\n   - Conduct characterization to confirm enhanced hydrophilicity:\n     - **Water Contact Angle Measurement**: Lower contact angles indicate improved hydrophilicity.\n     - **FTIR Analysis**: Verify the reduction of epoxide peaks and the appearance of imidazole-related peaks.\n     - **Solubility Test**: Evaluate water compatibility of the modified polymer.\n     - **Thermal Analysis (DSC/TGA)**: Ensure the thermal stability of the final polymer.\n\n3. **Final Adjustments**:\n   - If additional hydrophilicity is needed, post-polymerization grafting with hydrophilic groups (e.g., carboxylic acids, sulfonates) can be performed.\n\n---\n\n### **Experimental Notes and Tips**:\n- Ensure precise temperature and reactant control to avoid over-curing or epoxide ring scission.\n- Keep all solvents and reagents anhydrous to prevent side reactions with water.\n- The hydrophilicity of the final product should always be assessed relative to the application (e.g., biomedical coatings, hydrogels, etc.).\n\n---\n\n### Conclusion\nBy following this step-by-step methodology, you can successfully integrate imidazole into the epoxy-basded formulation and achieve hydrophilicity enhancement. This approach allows for systematic tuning of both the curing process and the hydrophilic properties of the final polymer.\n\nIf you have additional details about your nucleophilic addition product or desired applications, I\u2019d be happy to refine these protocols even further. Good luck with your experiment, and let me know how it progresses!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Given a molecule like propylene glycol (PG), explain how varying its concentration could impact both the spontaneity of pattern formation on the polymer surface and the resulting hydrophilicity of the material."}, {"role": "assistant", "content": "Certainly! This is an excellent question that delves into the interplay between molecular design, reaction conditions, and the resulting polymer surface properties such as hydrophilicity and pattern formation. Let us analyze and systematically address your inquiry step by step.\n\n---\n\n### **Step 1: Analyzing the Question and Identifying Key Points**\n1. **Molecule of Interest:** The molecule provided is **propylene glycol (PG)**, which is a small bifunctional molecule containing two hydroxyl (-OH) groups. These hydroxyl groups are hydrophilic in nature and will play a significant role in both surface hydrophilicity and polymerization.\n  \n2. **Factors Under Study:**\n   - **Varying Concentration of PG:** The concentration of PG during the polymerization process is a variable to be examined.\n   - **Spontaneity of Pattern Formation:** PG concentration may impact the self-assembly process or microphase/macrophase separation during polymerization, which could lead to surface pattern formation.\n   - **Hydrophilicity of the Material:** Surface hydrophilicity depends on the distribution and availability of hydrophilic functional groups (e.g., hydroxyl groups) exposed on the polymer surface.\n\n3. **Goal:** To explain the relationship between **PG concentration** and its effect on **pattern formation** as well as on the **hydrophilicity** of the resulting polymer.\n\n---\n\n### **Step 2: Systematic Explanation**\n#### **Background Concepts**\nBefore diving into the synthesis scheme, it is essential to understand how PG contributes to polymerization and surface hydrophilicity:\n- PG is often used as a co-monomer or chain extender in polymer systems. Its primary action is to introduce hydroxyl groups into the polymer matrix.\n- Higher concentrations of PG can lead to an increase in hydrophilic functional groups, which improves the surface hydrophilicity.\n- Surface pattern formation can arise spontaneously due to phase separation (hydrophilic vs. hydrophobic domains) during polymerization or post-polymerization annealing.\n\n---\n\n### **Step 3: Experimental Preparation Scheme**\nTo study the effect of PG concentration, we will outline a typical polymerization reaction using a base polymer (such as polyethylene glycol diacrylate (PEGDA)) with PG incorporated. The experimental steps are as follows:\n\n---\n\n#### **Step 3.1: Materials and Reagents**\n1. **Base Polymer Precursor:** Polyethylene glycol diacrylate (PEGDA).\n2. **Hydrophilic Modifier:** Propylene glycol (PG).\n3. **Crosslinker (if needed):** Ethylene glycol diacrylate (EGDA) or similar.\n4. **Photoinitiator (if UV-polymerizable):** 2-hydroxy-2-methylpropiophenone.\n5. **Solvent (if applicable):** Dimethyl sulfoxide (DMSO) or deionized water.\n6. **Other Required Equipment:** UV light source (if photopolymerization), mold/template, mixers, etc.\n\n---\n\n#### **Step 3.2: Reaction Scheme and Process**\nThis scheme assumes a UV-curable system using PEGDA as the base polymer.\n\n1. **Solution Preparation:**\n   - Weigh out PEGDA (e.g., 1 mmol, based on your target polymer chain length and density).\n   - Dissolve PEGDA in a suitable solvent (e.g., DMSO or water) to a fixed total volume (e.g., 10 mL).\n   - Gradually add **propylene glycol** (PG) to the solution. Vary its concentration across different batches for comparison. Suggested PG concentrations: 0.1 mmol (low), 0.5 mmol (medium), and 1 mmol (high).\n\n2. **Crosslinking and Initiation:**\n   - Add a crosslinking agent (e.g., EGDA, 0.1 mmol if used) to control polymer network density.\n   - Add a photoinitiator (e.g., 0.05 mmol) into the mixture.\n   - Ensure the solution is homogeneously mixed before polymerization.\n\n3. **Polymerization (Reaction):**\n   - Pour the solution into a mold or onto a flat surface for thin-film preparation.\n   - Expose the mixture to UV light (wavelength: 365 nm) for 5\u201315 minutes, depending on the thickness of the sample and intensity of the UV source. Crosslinking will be triggered by the initiator.\n\n4. **Post-Processing:**\n   - Rinse the resulting polymer in deionized water to remove unreacted monomers or initiators.\n   - Dry the polymer under vacuum or room temperature, depending on the volatility of the solvent.\n\n---\n\n#### **Step 3.3: Characterization of Results**\n1. **Surface Pattern Formation:**\n   - Use AFM (Atomic Force Microscopy) or SEM (Scanning Electron Microscopy) to observe the formation of micro/nano-patterns on the polymer surface. Monitor how the PG concentration affects phase separation and the resulting patterns.\n\n2. **Hydrophilicity Measurements:**\n   - Measure the **contact angle** of water droplets on the polymer surface. Lower contact angles indicate higher hydrophilicity.\n   - Perform water absorption or swelling studies, which are strongly influenced by the concentration of hydroxyl-rich PG.\n\n---\n\n### **Step 4: Expected Results and Analysis**\n#### **Effect of PG on Pattern Formation:**\n- **Low PG Concentration:** At lower concentrations, PG may not significantly contribute to hydrophilic phase domains. Hence, pattern formation on the surface may be absent or negligible.\n- **Medium PG Concentration:** With moderate PG levels, phase separation may occur, leading to microstructured patterns due to competing hydrophilic and hydrophobic interactions.\n- **High PG Concentration:** Excess PG promotes more hydrophilic interactions, which could result in finer patterns or even homogeneous hydrophilic surfaces.\n\n#### **Effect of PG on Hydrophilicity:**\n- Higher concentrations of PG should lead to an increase in surface hydrophilicity due to the availability of hydroxyl groups. \n- However, excessive PG may sometimes lead to poorer crosslinking or reduce mechanical properties, so careful optimization is required.\n\n---\n\n### **Step 5: Conclusion**\nBy systematically varying the concentration of propylene glycol in the reaction mixture, you can study its influence on surface micro/nano-pattern formation and hydrophilicity. Ensure that the polymerization reaction is well-controlled and that post-synthesis characterization is thorough to understand the trends in detail.\n\nDetailed execution of the steps outlined will allow you to successfully complete the experiment and gain insight into the interplay between PG concentration, surface morphology, and hydrophilicity."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe how you would incorporate a radiation-curable acrylate containing hydrophilic alkylene oxide moieties (characterized by the formula \u03a9(CH2)\u03a9n(0-)\u03a3m-, where n is between 1 and 3, and m is between 1 and 10) into a polymer system to enhance its hydrophilicity. Include any relevant steps for curing and network formation in your explanation."}, {"role": "assistant", "content": "### Question Analysis:\nTo address your question, let us break it into its critical components:\n1. **Understanding the molecule**: The target molecule is a radiation-curable acrylate containing hydrophilic alkylene oxide moieties, which takes the general form of \\( \\Omega(\\text{CH}_2)\\Omega_n(\\text{O}-)\\Sigma_m- \\) where \\( n \\) (number of alkylene oxides) ranges from 1\u20133 and \\( m \\) (number of hydrophilic EO/PO units) from 1\u201310. Such hydrophilic functional groups enhance water compatibility through hydrogen-bonding interactions.\n2. **Objective**: To effectively incorporate this species into a polymer to make the overall material hydrophilic while developing a cross-linked network through radiation curing.\n3. **Steps**: This involves systematically integrating the reagents, selecting appropriate curing methodologies (likely UV or electron beam radiation), optimizing reaction conditions, and achieving final properties in the polymer system.\n\nWe must focus on specific details, including polymer system preparation, radiation-curing methods, and the formation of cross-linked hydrophilic networks. Now, let us systematically design your experimental preparation scheme.\n\n---\n\n### Experimental Preparation Scheme\n\n#### Step 1: Selection of base polymer system\nFirst, choose the polymer or prepolymer system to which you will add the hydrophilic acrylate. Depending on the final application's requirements:\n- For **soft, flexible materials**, use oligomers or prepolymers such as a urethane acrylate or polyester acrylate.\n- For **rigid materials**, select epoxy acrylates or highly cross-linked methacrylate formulations.\n\nThis choice should ensure compatibility with the targeted acrylate co-monomer and the desired mechanical and water-absorbing properties.\n\n#### Step 2: Monomer preparation\nThe hydrophilic acrylate monomer structure provides the basis for the addition of hydrophilic functional groups into the polymer network. Examples include acrylates functionalized with ethylene oxide (EO) or propylene oxide (PO) groups. Typical examples include:\n- Poly(ethylene glycol) diacrylate (PEGDA) or poly(propylene glycol) acrylate.\n- Structures where EO/PO chains are linear or branched.\n\nBefore proceeding, calculate the molar quantities based on the ratio of hydrophilic monomer to hydrophobic components. Typical formulas:\n- Incorporate **10-30 wt% of hydrophilic acrylate** relative to the total monomer weight for moderate hydrophilicity.\n- For higher hydrophilicity, increase to **40-60 wt% hydrophilic monomer**.\n\n#### Step 3: Preparation of the polymer mixture\nThoroughly mix **hydrophilic acrylate** with the base polymer (or oligomer). Use stimulating agents if viscosity issues arise:\n1. Add **hydrophilic acrylate** gradually to prevent phase separation.\n2. Include a photoinitiator (around **1\u20133 wt%** of total monomers), such as:\n   - Irgacure 2959 (water-compatible UV initiator).\n   - Darocur 1173 or benzophenone-based initiators, depending on acrylate compatibility.\n\nStir under nitrogen or vacuum to avoid oxygen inhibition (which can inhibit polymerization of acrylates).\n\n#### Step 4: Substrate preparation and coating\nIf forming films, evenly spread the polymer mixture over a clean substrate (e.g., glass, polyethylene, or a mold). Control the thickness of the desired film using a blade applicator or spin-coating.\n\n- Typical film thickness: 50\u2013300 \u03bcm.\n\n#### Step 5: Radiation curing\nRadiation curing is critical for polymer network formation:\n1. **UV curing**:\n   - Use a UV lamp emitting wavelengths between 280\u2013400 nm.\n   - Apply fluence of **2\u20134 J/cm\u00b2**. The intensity and exposure time depend on film thickness and photoinitiator used.\n   - Cure under a **nitrogen atmosphere** to prevent oxygen inhibition.\n   - Result: Formation of a cross-linked hydrophilic network.\n\n2. **Electron beam curing (optional)**:\n   - Use electron beam irradiation for solvent-free processing or highly cross-linked systems.\n   - Typical parameters: \\( 50-300 \\, \\text{keV} \\) energy and \\( 2-10 \\, \\text{kGy} \\) dose.\n   - Benefit: Does not require photoinitiators and eliminates concerns with oxygen inhibition.\n\n#### Step 6: Post-treatment and characterization\n1. **Swelling behavior**:\n   - Immerse cured polymer in deionized water to assess water uptake.\n   - Measure the equilibrium swelling ratio \\( Q \\) to quantify hydrophilicity:  \n     \\[\n     Q = \\frac{\\text{Weight of swollen polymer} - \\text{Weight of dry polymer}}{\\text{Weight of dry polymer}}\n     \\]\n   \n2. **Mechanical testing**:\n   - Use tensile testing to analyze elasticity and strength if flexibility is critical.\n   \n3. **Surface hydrophilicity**:\n   - Measure water contact angle to confirm hydrophilicity enhancement. Typical hydrophilic surfaces show contact angles \\( < 45^\\circ \\).\n\n4. **Network structure**:\n   - Use FTIR spectroscopy to confirm acrylate polymerization (C=C peak disappearance) and presence of hydrophilic groups.\n\n---\n\n### Summary of Key Reaction Conditions\n| **Step**                 | **Parameter**                  | **Typical Value/Range**   |\n|--------------------------|---------------------------------|---------------------------|\n| Hydrophilic monomer ratio| % Hydrophilic acrylate         | 10\u201360 wt%                |\n| Photoinitiator           | wt% of total                   | 1\u20133 %                    |\n| UV radiation dose         | Energy density                 | 2\u20134 J/cm\u00b2                |\n| Film thickness           | \u03bcm                              | 50\u2013300 \u03bcm                |\n| Swelling test condition  | Temperature                    | 25\u201337\u00b0C                  |\n| Water contact angle       | For hydrophilic surface        | \\( < 45^\\circ \\)         |\n\nBy following this carefully designed experimental procedure, you should achieve a hydrophilic polymer system with water-absorbing properties and a stable, cross-linked network! Always confirm through testing after each stage of synthesis."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "When integrating polyethylene glycol-based amines (such as ED2003) into a polymer network, what functional group interactions are critical for ensuring the resulting polymer exhibits increased hydrophilicity? Propose experimental conditions to optimize this reaction."}, {"role": "assistant", "content": "Certainly! Let's break this question into key components to ensure a thorough analysis and a systematic answer.\n\n---\n\n### **Key Analysis of the Question**\n1. **Polyethylene glycol-based amines (e.g., ED2003)**:\n   - ED2003 is a polyethylene glycol (PEG)-based amine, known for its hydrophilic nature due to its repeating ethylene glycol (EG) units. The amine termini add potential reactivity for covalent incorporation into polymer networks.\n   - The challenge lies in properly grafting or crosslinking ED2003 into the polymer to enhance hydrophilicity without compromising structural integrity.\n\n2. **Functional group interactions**:\n   - The specific chemical interactions (e.g., reactions of the terminal amine groups, interactions with other network moieties, or incorporation via crosslinking) dictate the success of the functionalization.\n\n3. **Experimental conditions**:\n   - Providing detailed experimental parameters (reagents, molar ratios, reaction conditions) is critical to ensuring successful synthesis and optimization in a laboratory setting.\n\n---\n\n### **Critical Functional Group Interactions for Hydrophilicity**\nTo ensure increased hydrophilicity of the resulting polymer, the following functional group interactions should be considered:\n- **Amine Functionality of ED2003**: The primary or secondary amines (-NH2/-NH) in ED2003 can react with functional groups such as carboxylic acids (-COOH), epoxy groups, or isocyanates (-NCO) via condensation, addition, or crosslinking reactions.\n- **PEG Backbone in ED2003**: The poly(ethylene glycol) chain itself provides inherent hydrophilic properties due to its high affinity to water (via hydrogen bonding). Its presence in the polymer enhances water-solubility, wettability, and overall hydrophilicity.\n\n---\n\n### **Proposed Experimental Scheme**\nBelow I outline a systematic experimental procedure for integrating ED2003 into a polymer matrix. I'll include a specific reaction, reaction conditions, and optimization steps.\n\n#### **Reaction Mechanism**: Crosslinking ED2003 with a multi-functional Epoxy Resin\nThis process leverages the reactivity between the terminal amine groups (-NH2) of ED2003 and the epoxy groups (-CH(O)CH2).\n\n---\n\n### **Step 1: Selection of Starting Materials and Reagents**\n- **Base Polymer**: Select a multi-functional epoxy resin with high epoxy equivalent weight (e.g., polyethylene glycol diglycidyl ether for biocompatibility or a diglycidyl ether of bisphenol A (DGEBA) for rigidity).\n- **Hydrophilic Modifier**: ED2003 (a PEG-based diamine with molecular weight ~2000 g/mol).\n- **Curing Agent**: To ensure effective network formation, include a co-monomer (e.g., triethylenetetramine (TETA)).\n\n#### **Preparation Conditions**\n1. **Reagent Ratios**:\n   - Epoxy Resin: Hydrophilic diamine (ED2003): Curing Agent = 1:0.5:0.25 (molar ratio).\n   - Example Calculations for 10 g of polymer network:\n     - Epoxy resin: ~5.0 g.\n     - ED2003: ~3.5 g.\n     - TETA: ~1.5 g.\n2. **Solvent**:\n   - Optional: Use a small amount of polar aprotic solvent (e.g., dimethylformamide, DMF) to improve miscibility if the reagents are not soluble in a common medium.\n\n#### **Procedure**:\n1. Dissolve the epoxy resin in DMF at room temperature under continuous stirring until a homogeneous solution forms.\n2. Gradually add ED2003 to the resin, ensuring complete mixing. Stir the mixture at 50\u201360\u00b0C (to reduce viscosity) for 1\u20132 hours.\n3. Add the curing agent (TETA) dropwise at ~50\u00b0C under stirring. Continue stirring for an additional 30 minutes to ensure uniform mixing.\n   - **Note**: Excess ED2003 can lead to a more hydrophilic product but may compromise the mechanical properties.\n4. Pour the formulation into a mold or flat casting surface. Allow the mixture to thermally cure at 80\u00b0C for 4 hours, then post-cure at 120\u00b0C for an additional 6 hours.\n\n#### **Optimization**:\n- Screen different molar ratios (e.g., ED2003:Epoxy ratios of 1:1, 1:0.75, and 1:0.5) to determine the optimal balance between hydrophilicity and mechanical properties.\n- Assess the effect of curing time and temperature ramp rate\u2014gradual heating often produces better crosslinked networks.\n\n---\n\n### **Step 2: Characterization of Hydrophilicity**\n- Perform water contact angle measurements for surface hydrophilicity. Expect angles < 30\u00b0 with a high ED2003 content.\n- Conduct swelling ratio tests in water to assess the polymer's ability to absorb water.\n- FTIR spectroscopy:\n   - Look for characteristic absorption peaks for ether groups (PEG, ~1100\u20131200 cm\u207b\u00b9) and secondary amine groups (NH bending, ~1600 cm\u207b\u00b9).\n   - Confirm the reduction of hydroxyl peaks (~3400 cm\u207b\u00b9), indicating successful amine-epoxy reactions.\n\n---\n\n### **Final Notes for Laboratory Practice**\n1. Ensure precise weighing of reagents with an analytical balance.\n2. Work in a well-ventilated fume hood when handling solvents and curing agents.\n3. Conduct small-scale trials to identify optimal reaction parameters before scaling up.\n\nThis detailed experimental pathway should allow for the successful integration of ED2003 into a hydrophilic polymer network, balancing both hydrophilicity and material properties."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Design an experimental protocol to incorporate N-carboxyethyl chitosan (CEC) into a polymer hydrogel system, ensuring the final material has improved hydrophilic properties. Describe the role of CEC in the resulting hydrogel's hydrophilicity."}, {"role": "assistant", "content": "Certainly. Let us carefully think through the question and break it down for clarity.\n\n### **Step 1: Analysis of the Question and Key Points**\nYour question centers on incorporating **N-carboxyethyl chitosan (CEC)**, a functionalized derivative of chitosan, into a polymer hydrogel system to enhance its **hydrophilic properties**. My task is to design a complete, step-by-step experimental protocol while justifying the choice of reagents and conditions, and explaining how CEC contributes to increased hydrophilicity in the resulting hydrogel.\n\n#### Key Points:\n1. The functional CEC (a derivative of chitosan) needs to be integrated into a polymer hydrogel matrix.\n2. The goal is to achieve greater hydrophilicity in the hydrogel, likely owing to CEC\u2019s inherent hydrophilic groups (e.g., carboxyl (-COOH) and amine (-NH2)).\n3. The experimental protocol must detail each step of the synthesis process, including reaction conditions, reagents, and their roles.\n\n---  \n\n### **Step 2: Systematic Experimental Protocol**\nBelow, I outline a suggested experimental protocol for incorporating CEC into a polymer hydrogel system. For simplicity, we assume the base hydrogel system is poly(vinyl alcohol) (PVA), known for its biocompatibility and film-forming properties. We will crosslink the CEC with PVA to form a composite hydrogel.\n\n#### **Materials Required:**\n- **N-carboxyethyl chitosan (CEC)**: The hydrophilic functional component.\n- **Poly(vinyl alcohol) (PVA)**: A base polymer for hydrogel synthesis.\n- **Glutaraldehyde** (50 wt% aqueous solution): A crosslinking agent.\n- **Distilled water**: Solvent.\n- **Hydrochloric acid (HCl)**: pH adjustment for crosslinking activation.\n- **Phosphate buffer solution (PBS)** (pH 7.4): Used to wash and neutralize the hydrogel.\n- **Glycerol** (optional): A plasticizer to enhance flexibility of the final hydrogel.\n\n---\n\n#### **Step-by-Step Protocol**\n\n1. **Preparation of PVA Solution (10 wt%):**\n   - Dissolve **10 g PVA** in **90 mL distilled water**.\n   - Heat at **90\u00b0C** with constant stirring to ensure complete dissolution.\n   - Cool the solution to room temperature before proceeding to the next step.\n\n2. **Preparation of CEC Solution (2.5 wt%):**\n   - Dissolve **2.5 g CEC** in **97.5 mL distilled water** under gentle stirring.\n   - The pH of the solution may need to be adjusted if CEC does not dissolve easily due to electrostatic interactions. Adjust the pH to **4-6 using 0.1 N HCl**, ensuring solubility.\n\n3. **Mixing PVA and CEC:**\n   - Gradually mix the CEC solution with the prepared PVA solution.\n   - For example, use a PVA-to-CEC ratio of **80:20 by mass** (e.g., 8 g PVA solution and 2 g CEC solution). \n   - Stir the combined solution thoroughly to ensure uniform dispersion of CEC in the PVA matrix. Monitor the mixture visually for homogeneity.\n\n4. **Addition of Crosslinking Agent:**\n   - Add **glutaraldehyde (GA)** dropwise to the PVA-CEC mixture. Typical GA concentrations range from **0.5-1 wt% based on the total polymer weight**.\n   - Stir the mixture continuously at **room temperature**. The crosslinking reaction between the primary amine groups of CEC and aldehyde groups of GA helps create a covalent network structure between PVA and CEC.\n\n5. **pH Adjustment for Crosslinking Reaction:**\n   - Using **0.1 M HCl**, adjust the pH of the mixture to **4-5** to optimize the reactivity of glutaraldehyde, which is most effective at slightly acidic conditions.\n\n6. **Casting the Hydrogel:**\n   - Pour the resulting viscous solution into a clean glass mold or Petri dish to ensure even distribution.\n   - Allow the hydrogel to cure at **room temperature for 12-24 hours**, ensuring proper crosslinking and network formation.\n\n7. **Post-Treatment and Washing:**\n   - After curing, immerse the hydrogel in **phosphate buffer solution (PBS, pH 7.4)** for 24 hours to remove residual glutaraldehyde and any unreacted components. This step ensures biocompatibility and neutrality of the hydrogel.\n   - Optionally, introduce **glycerol (e.g., 1 wt% of total polymer weight)** into the washing process to enhance flexibility.\n\n8. **Drying or Storage (Optional):**\n   - (If a dry hydrogel is needed) Dry the hydrogel in a vacuum oven at **40-50\u00b0C** until a constant weight is achieved.\n   - If maintaining hydrated conditions, store in PBS solution at **4\u00b0C** until use.\n\n---\n\n#### **Step 3: Role of CEC in the Hydrogel\u2019s Hydrophilicity**\nN-carboxyethyl chitosan (CEC) contributes significantly to the hydrophilicity of the resulting hydrogel:\n1. **Presence of Carboxyl Groups (-COOH):** The carboxyl groups of CEC are highly hydrophilic and can hydrogen bond with water, increasing the overall water-retention capacity of the hydrogel.\n2. **Amino Groups (-NH2):** The functional amine groups add additional sites for hydrogen bonding with water, further enhancing hydrophilicity.\n3. **Ionic Interactions:** The carboxyl groups (in their ionized form) can also increase ionic interactions, improving water adsorption and swelling behavior.\n4. **Homogeneous Dispersion:** When well-dispersed in the PVA matrix, CEC forms a network that promotes both physical and covalent bonding, increasing the integrity of the hydrogel while enhancing hydrophilicity.\n\n---\n\n### **Final Notes**\nThis protocol can be adjusted to the specific needs of your hydrogel application (e.g., biomedical, environmental, etc.) by tweaking the polymer blend ratios, crosslinker concentration, or reaction conditions. Additionally, to further analyze the hydrogel\u2019s hydrophilicity after preparation, characterization techniques such as **contact angle measurement**, **swelling ratio tests**, or **Fourier-transform infrared spectroscopy (FTIR)** can be utilized.\n\nIf you have further questions or need assistance during your experiment, feel free to ask. It is important to plan, prepare reagents carefully, and prioritize safety in the laboratory.\n\n"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "In the preparation of Prepolymer 2, hydroxyethyl acrylate is added during synthesis. Explain the purpose of using this molecule, including its functional groups, and how it aids in modifying the polymer to enhance hydrophilicity."}, {"role": "assistant", "content": "Alright, let's break the question into its components and systematically address each aspect to ensure clarity.\n\n### 1. **Analysis of the Question and Key Points**\nThe question pertains to the use of **hydroxyethyl acrylate (HEA)** in the synthesis of a polymer (specifically a prepolymer labeled \"Prepolymer 2\"). You want to understand:\n- The **purpose of HEA** in the reaction.\n- The **functional groups** in HEA and their roles.\n- How HEA contributes to the **enhancement of hydrophilicity** in the synthesized polymer.\n\nTo address these key points, we need to explore:\n- The molecular structure and properties of hydroxyethyl acrylate.\n- The chemistry underlying its role in polymer synthesis.\n- The specific enhancement of polymer hydrophilicity using HEA.\n\n---\n\n### 2. **Understanding Hydroxyethyl Acrylate: Functional Groups and Properties**\n\n#### (a) **Molecular Structure of HEA**:\n   - Hydroxyethyl acrylate (HEA) is a bifunctional molecule with the following structure:\n     ```\n     CH2=CH-COO-CH2-CH2-OH\n     ```\n     It contains two key functional groups:\n     1. **Acrylic group (-CH=CH2)**: This vinyl group can undergo **radical polymerization** or other chain-growth polymerization mechanisms when forming the polymer backbone. It serves as the **reactive site** for incorporation into the polymer chain.\n     2. **Hydroxyl group (-OH)**: This group is hydrophilic in nature, meaning it can form hydrogen bonds with water. It also allows for secondary chemical modifications, such as crosslinking or additional functionalization. \n\n#### (b) **Reactivity of HEA**:\nThe dual functionality of HEA (acrylic group for polymerization and hydroxyl group for hydrophilicity or further reactions) makes it a versatile monomer in polymer synthesis. Its structure allows it to:\n   - Participate in **copolymerization** with other monomers.\n   - Enhance the polymer's compatibility with water (owing to its hydrophilic nature).\n   - Provide functional groups for tailoring the polymer's mechanical or chemical properties.\n\n---\n\n### 3. **Purpose of Using Hydroxyethyl Acrylate in Prepolymer 2**\n\nDuring the synthesis of **Prepolymer 2**, HEA is introduced to achieve the following objectives:\n\n#### (a) **Incorporation of Hydrophilic Functional Groups**:\n- By including HEA in the monomer mixture during polymerization, the hydroxyl (-OH) groups from HEA are chemically bound to the polymer backbone. This incorporation leads to an increase in the overall **hydrophilicity** of the polymer.\n- The hydroxyl groups can form **hydrogen bonds** with water molecules, improving the polymer's ability to absorb water, swell, or dissolve in polar solvents. This is highly desirable for applications where water interaction is critical, such as in hydrogels, coatings, or biomaterials.\n\n#### (b) **Improving Polymer Versatility**:\n- The presence of hydroxyl groups from HEA introduces sites for **post-polymerization modification**. For example, hydroxyl groups can react with isocyanates to form urethane linkages or can be crosslinked to improve mechanical properties while retaining hydrophilicity.\n- This functionality provides flexibility in polymer design, allowing downstream tailoring of material properties.\n\n#### (c) **Modifying Surface Properties**:\n- When incorporated, HEA can facilitate **surface hydrophilization** of the polymer. If the polymer is used in coatings or membranes, the hydroxyl groups exposed at the surface reduce interfacial tension with water, thereby improving wettability and biocompatibility.\n\n#### (d) **Introducing Stability Against Phase Separation**:\n- The hydrophilic nature of HEA contributes to improved **compatibility** between hydrophilic and hydrophobic domains in copolymers. This reduces phase separation and ensures better dispersion of hydrophilic segments throughout the material.\n\n---\n\n### 4. **Experimental Preparation Scheme for Prepolymer 2**\n\nBelow is a generalized experimental scheme for incorporating HEA into a polymer while discussing the key details. While this is a guided outline, specific parameters (like temperatures or time) should align with the larger context provided for Prepolymer 2.\n\n#### **Step 1: Selection of Monomers**\n- HEA is added as part of the monomer mixture during polymerization.\n- Typical molar ratios would be determined based on the desired level of hydrophilicity. For instance, if the target hydrophilic content is moderate, HEA might comprise 10\u201330% of the total monomers by molar ratio.\n- Additional monomers with complementary properties (e.g., hydrophobic acrylates, crosslinkers, etc.) are selected to balance the polymer\u2019s hydrophilicity and structural integrity.\n\n#### **Step 2: Polymerization Mechanism**\n- HEA is often used in **free-radical polymerization**, though other mechanisms like controlled radical polymerization (e.g., RAFT or ATRP) may also be used.\n- A typical reaction mixture would contain:\n  - HEA: 10\u201330% molar fraction.\n  - Other acrylate monomers (e.g., methyl methacrylate, butyl acrylate): 70\u201390% molar fraction.\n  - Initiator (e.g., azobisisobutyronitrile, AIBN): 1\u20132 wt% relative to total monomers.\n  - Solvent: An inert solvent like ethanol or dimethylformamide (DMF) may be used to dissolve the monomers and improve miscibility.\n  - Optional additives: A chain-transfer agent (e.g., mercaptans) may be added to control molecular weight.\n\n#### **Step 3: Reaction Conditions**\n- The polymerization is initiated at elevated temperatures (e.g., 60\u201380\u00b0C for AIBN) in a nitrogen-purged environment to prevent inhibition by oxygen.\n- The reaction is allowed to proceed for several hours (e.g., 4\u201312 hours) with stirring to ensure uniform polymerization.\n\n#### **Step 4: Post-Polymerization Processing**\n- The resulting prepolymer is purified via:\n  - Precipitation into a non-solvent (e.g., diethyl ether).\n  - Filtration or dialysis to remove unreacted monomers and byproducts.\n\n#### **Step 5: Characterization**\n- The functional incorporation of HEA can be confirmed through techniques such as:\n  - **FTIR spectroscopy**: Identification of hydroxyl (-OH) groups and acrylic backbone.\n  - **NMR spectroscopy**: Verification of HEA\u2019s incorporation ratio.\n  - **Contact angle measurement**: Determination of surface hydrophilicity.\n\n---\n\n### 5. **How HEA Enhances Hydrophilicity**\n\n- The hydroxyl groups from HEA act as points of interaction with water, enabling the polymer to form **hydrogen bonds**. This greatly improves water compatibility and wettability.\n- Incorporation of HEA increases the polymer\u2019s **polar content**, reducing surface energy and enhancing **water absorption capacity**.\n- For biomedical or environmentally sensitive applications, this hydrophilicity can improve biocompatibility, reduce biofouling, or improve degradability.\n\n---\n\n### Final Summary\n\nHydroxyethyl acrylate is a bifunctional molecule with an acrylic group for chain polymerization and a hydroxyl group for enhancing polymer hydrophilicity. Its incorporation into Prepolymer 2 provides hydrophilic functionality, facilitates water interaction, and introduces sites for functional modification. By systematically controlling its concentration and reaction conditions, HEA enables precise tuning of polymer properties for a wide range of applications. If you need specific numeric calculations for this synthesis, feel free to ask!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "When using poly(ethylene glycol) (PEG) as a functionalizing molecule to enhance the hydrophilicity of a polymer, what steps would you take to ensure proper attachment onto the polymer matrix? Outline and justify each step in the process."}, {"role": "assistant", "content": "Certainly. Let us approach this question systematically to ensure your understanding, while providing a detailed, step-by-step outline of the synthesis process for functionalizing a polymer with a hydrophilic poly(ethylene glycol) (PEG) molecule.\n\n---\n\n### Key Points in the Problem\n\n1. **Objective**: Enhance the hydrophilicity of a polymer by attaching poly(ethylene glycol) (PEG) onto its matrix.\n2. **Challenges**: \n   - Ensuring proper chemical attachment of PEG to the polymer.\n   - Maintaining control over reaction conditions to achieve efficient grafting.\n   - Preserving the hydrophilic properties of PEG during the functionalization process.\n\n---\n\n### Step-by-Step Synthesis Process Using Poly(ethylene glycol) (PEG)\n\nBelow is a detailed plan of action to attach PEG molecules onto a polymer matrix, including comments on each step to ensure scientific rigor.\n\n---\n\n#### **Step 1: Analyze the Polymer Matrix**\n   - **Purpose**: Understanding the functional groups present on the polymer's surface determines the appropriate strategy for PEG attachment.\n   - **Actions**:\n     - Assess the chemistry of the polymer matrix (e.g., backbone functionality, surface reactivity). For instance:\n       - If the polymer contains hydroxyl (-OH), carboxylic acid (-COOH), or amine (-NH2) groups, these can serve as reactive handles for PEG attachment.\n       - If the polymer lacks such functional groups, surface modification (e.g., plasma treatment or chemical activation) may be required to introduce reactive sites.\n     - Determine whether you are grafting PEG along the polymer backbone (grafting-to method) or onto a pre-activated polymer chain end (grafting-from method).\n\n---\n\n#### **Step 2: Choose the Appropriate PEG Derivative**\n   - **Purpose**: Unmodified PEG is inert in most reactions, so a functionalized PEG derivative is required for efficient covalent bonding onto the polymer.\n   - **Actions**:\n     - Select a PEG derivative based on the polymer surface functionality:\n       - For coupling with -COOH (e.g., in poly(acrylic acid)): Use a PEG containing an amine (-NH2) or hydroxyl (-OH) group.\n       - For coupling with -OH, consider PEG terminated with a carboxylic acid or isocyanate (-N=C=O) functional group.\n       - For a more versatile approach, methoxy-PEG-succinimidyl carbonate (mPEG-SC) or PEG-diisocyanate can facilitate covalent attachment through reactive activated ends.\n     - Choose an appropriate molecular weight (common PEG molecular weights range from 200 to 20,000 Da) to balance hydrophilicity and polymer flexibility. Lower molecular weight provides better penetration into the matrix but less bulk hydrophilicity, while higher molecular weight PEG enhances hydration but reduces polymer mobility.\n\n---\n\n#### **Step 3: Surface Activation of the Polymer Matrix**\n   - **Purpose**: Enhance the polymer reactivity toward PEG.\n   - **Actions**:\n     - If the polymer lacks reactive functional groups, activate its surface by:\n       1. **Plasma Treatment**: Employ oxygen or ammonia plasma to introduce reactive oxygen-containing groups (e.g., -OH, -COOH) or amines (-NH2).\n       2. **Chemical Activation**: Use mild oxidation (e.g., sodium periodate for polysaccharides) or graft reactive monomers onto the polymer backbone.\n     - If reactive groups already exist on the polymer (e.g., -COOH on poly(acrylic acid)), proceed directly to coupling chemistry.\n\n---\n\n#### **Step 4: Reaction Setup for PEG Grafting**\n   - **Purpose**: Covalently attach PEG to the polymer matrix.\n   - **Reaction Pathways**:\n     1. **Amide Bond Formation** (if polymer possesses -COOH groups):\n        - **Chemistry**: React carboxylic acid groups on the polymer with amine-terminated PEG.\n        - **Activation**: Activate the -COOH groups with a coupling reagent like carbodiimides (e.g., EDC, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide) along with NHS (N-hydroxysuccinimide) to form a stable ester intermediate.\n        - **Conditions**:\n          - Solvent: Use a water-miscible solvent (e.g., DMF, DMSO, or PBS buffer, pH ~7).\n          - Molar ratio: Maintain a 1:1.1 molar ratio of polymer -COOH groups to PEG amine groups.\n          - Temperature: Perform reaction at room temperature (~25\u00b0C) or slightly elevated (e.g., 37\u00b0C) for 4\u201312 hours.\n        - **Expected Outcome**: Amide bonds form, covalently attaching the PEG molecule to the polymer matrix.\n     2. **Urethane Bond Formation** (if polymer possesses -OH groups):\n        - **Chemistry**: Isocyanate-terminated PEG reacts with hydroxyl groups on the polymer.\n        - **Conditions**:\n          - Solvent: Use an anhydrous solvent (e.g., tetrahydrofuran or DMF) to prevent isocyanate hydrolysis.\n          - Catalyst: Include dibutyltin dilaurate (DBTDL) as a catalyst to accelerate reaction kinetics.\n          - Temperature: Reaction should occur at 50\u201370\u00b0C under inert atmosphere (e.g., nitrogen) for 6\u20138 hours.\n        - **Expected Outcome**: Urethane linkages form, binding PEG to the polymer.\n\n---\n\n#### **Step 5: Purification of the Functionalized Polymer**\n   - **Purpose**: Remove unreacted reagents and excess PEG.\n   - **Actions**:\n     - Perform extensive washing of the polymer using water, ethanol, or suitable solvents to remove unreacted PEG and byproducts.\n     - Dialysis (if in solution) or Soxhlet extraction (if solid polymer) may also be employed for purification.\n     - Dry under vacuum to remove residual solvents and stabilize the polymer.\n\n---\n\n#### **Step 6: Characterization of the Modified Polymer**\n   - **Purpose**: Confirm the success of PEG grafting and measure the degree of hydrophilicity.\n   - **Analytical Techniques**:\n     1. **Fourier Transform Infrared Spectroscopy (FTIR)**:\n        - Observe characteristic peaks for PEG (C\u2013O\u2013C stretching near 1100 cm\u207b\u00b9) and newly formed functional groups (amide or urethane).\n     2. **Nuclear Magnetic Resonance (NMR)**:\n        - Use 1H NMR to detect PEG protons (chemical shifts around 3.4\u20133.7 ppm correspond to the ethylene oxide units in PEG).\n     3. **Contact Angle Measurements**:\n        - Measure the water contact angle to evaluate the improved hydrophilicity.\n     4. **Gravimetric Analysis**:\n        - Determine the degree of PEG grafting by comparing the polymer mass before and after functionalization.\n\n---\n\n### Justification of the Process\n\n1. **Surface Modification**: Ensures availability of reactive sites for PEG attachment, even for inert polymers.\n2. **Choice of Chemistry**: Selecting specific reagents and reaction conditions ensures high grafting efficiency with minimal PEG degradation.\n3. **Control of Reaction Parameters**: Optimizing molar ratios and temperature helps achieve reproducible results.\n4. **Characterization**: Essential to verify successful functionalization and quantify hydrophilicity improvements.\n\n---\n\nBy following the above systematic approach, you should be able to successfully graft PEG onto your polymer matrix and significantly enhance its hydrophilicity. Let me know if you need further clarification or assistance!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Using diethylene glycol diacrylate (DEGDA) as the chosen molecule, outline the steps for synthesizing a crosslinked polymer network. How would this structure contribute to improved hydrophilicity, and what methods would you use to assess the polymer's water-absorption capacity?"}, {"role": "assistant", "content": "To synthesize a crosslinked polymer network using diethylene glycol diacrylate (DEGDA) and assess its hydrophilicity and water absorption capacity, we will break this process into a detailed, systematic experimental preparation scheme. By following exact steps and describing relevant conditions, reagent ratios, and methods, you will be adequately prepared to complete the experiment successfully in the laboratory.\n\n---\n\n### **Step 1: Analyze the Question and Summarize Key Points**\n\n1. **Objective:** Synthesize a crosslinked polymer network from diethylene glycol diacrylate (DEGDA).\n2. **Challenges to Address:** Enhance hydrophilicity of the polymer and examine its water-absorption capacity.\n3. **Approach:**\n   - Leverage the diacrylate structure of DEGDA to form a crosslinked polymer network.\n   - Highlight how the ether linkages in DEGDA contribute to water affinity.\n   - Specify methods to assess water absorption, such as gravimetric analysis or swelling studies.\n\n### **Step 2: Experimental Plan for Synthesizing the Crosslinked Polymer**\n\n#### **Step 2.1: Materials and Reagents**\n- **Diethylene Glycol Diacrylate (DEGDA):** Monomer with two acrylic functional groups for crosslinking.\n- **Initiator:** Use a radical initiator such as azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO), depending on experimental setup (thermal or photoinitiated polymerization).\n- **Crosslinking Agent (Optional):** Although DEGDA already contains diacrylate groups that promote crosslinking, small amounts of a third monomer like acrylic acid (AA) may be introduced to further improve hydrophilicity.\n- **Solvent (if needed):** Ethanol or deionized water to dissolve monomers and ensure homogeneity.\n- **Deionized Water:** For later washing and testing.\n- **Nitrogen or Argon:** To create an inert atmosphere for polymerization and prevent oxygen inhibition.\n\n---\n\n#### **Step 2.2: Polymerization Method**\n\n##### **Option 1: Thermal Radical Polymerization**\n1. **Preparation of Reaction Mixture:**\n   - Dissolve DEGDA in a solvent (e.g., ethanol) at a desired concentration (e.g., 10\u201320 wt% relative to solvent).\n   - Add AIBN at a concentration of ~1\u20132 mol% relative to DEGDA monomer.\n   - Optional: If a comonomer such as acrylic acid is used, mix at a molar ratio of 90:10 (DEGDA:AA) to further boost hydrophilicity.\n\n2. **Degassing the Solution:**\n   - Place the reaction mixture in a reaction flask.\n   - Bubble nitrogen gas (or argon) through the solution for 10\u201315 minutes to remove dissolved oxygen that may inhibit free-radical polymerization.\n\n3. **Thermal Polymerization:**\n   - Heat the degassed reaction mixture to **60\u201370\u00b0C** under a nitrogen atmosphere.\n   - Polymerization will proceed via the initiation, propagation, and termination steps of free-radical mechanisms, forming a crosslinked network as DEGDA's two acrylate groups react with one another.\n   - Allow the reaction to proceed for **4\u20138 hours** to ensure full polymerization.\n\n---\n\n##### **Option 2: Photopolymerization (UV-Curing)**\n1. **Preparation of Reaction Mixture:**\n   - Dissolve DEGDA in ethanol at the desired concentration.\n   - Add a photoinitiator, such as Irgacure-2959, at ~1 wt% relative to the DEGDA.\n   - Optional: Add a comonomer such as a polyethylene glycol (PEG)-acrylate derivative for enhanced hydrophilicity.\n\n2. **Degassing Step:**\n   - Degas the reaction mixture with nitrogen/argon prior to UV exposure to avoid oxygen inhibition.\n\n3. **UV Irradiation:**\n   - Place the reaction mixture in a UV-curing chamber.\n   - Irradiate with UV light (wavelength ~365 nm) for **10\u201330 minutes**. The UV energy will activate the photoinitiator, initiating radical polymerization and creating the crosslinked network.\n\n---\n\n#### **Step 2.3: Purification of the Polymer**\n- After the polymerization reaction is complete:\n  - Wash the polymer thoroughly with ethanol and deionized water to remove unreacted monomers and other impurities.\n  - Dry the polymer in a vacuum oven or desiccator at 40\u201350\u00b0C until a constant weight is achieved.\n\n---\n\n### **Step 3: Assess How the Structure Improves Hydrophilicity**\n\nThe structure of the synthesized polymer network contributes to improved hydrophilicity in the following ways:\n1. **Ether Linkages in DEGDA Backbone:** The ether (-CH2-O-CH2-) groups in the diethylene glycol segment of DEGDA are inherently polar and capable of hydrogen bonding with water molecules, enhancing water affinity.\n2. **Crosslinked Network:** The polymer network's crosslinking density determines water uptake, as lower-density crosslinks create larger pores that enhance swelling and water absorption.\n3. **Optional Acrylic Acid (AA) Comonomer:** If incorporated, carboxylic acid groups (-COOH) in AA add ionizable groups that increase hydrophilicity by promoting osmotic swelling in water.\n\n---\n\n### **Step 4: Methods to Assess Water-Absorption Capacity**\n\nEvaluate the hydrophilicity and water-absorption properties of the synthesized polymer using the following methods:\n\n#### **4.1: Water-Swelling Capacity (Gravimetric Analysis)**\n1. **Procedure:**\n   - Dry the polymer to a constant weight (**W_d**) in a vacuum oven.\n   - Immerse the dried polymer sample in deionized water at room temperature and allow it to swell for 24 hours.\n   - Remove the swollen polymer, blot the surface with filter paper, and weigh it immediately (**W_s**).\n2. **Calculate Water Absorption:**\n   - Use the formula:\n     \\[\n     \\text{Water Absorption (%) = } \\frac{W_s - W_d}{W_d} \\times 100\n     \\]\n   - This gives the mass percentage of water absorbed by the polymer.\n\n---\n\n#### **4.2: Contact Angle Measurement**\n1. **Procedure:**\n   - Place the synthesized polymer as a thin film or disk in a contact angle goniometer.\n   - Drop a small droplet of water on the polymer surface and measure the contact angle.\n2. **Analysis:**\n   - A smaller contact angle (<90\u00b0) indicates higher hydrophilicity, while a larger angle (>90\u00b0) suggests hydrophobicity.\n\n---\n\n#### **4.3: Swelling Kinetics**\n1. **Procedure:**\n   - Measure polymer weight at different time intervals (e.g., every 10, 20, 30 minutes) during water immersion.\n   - Observe how rapidly the polymer absorbs water, indicating the speed of swelling.\n2. **Analysis:**\n   - Plot swelling ratio vs. time to determine the equilibrium swelling time and saturation behavior.\n\n---\n\n### **Conclusion**\n\nBy following the described experimental procedure, you can successfully prepare a hydrophilic, crosslinked polymer network using diethylene glycol diacrylate (DEGDA). The structural features of DEGDA, including hydrophilic ether linkages, and the potential use of hydrophilic comonomers, enhance water affinity. Use the outlined evaluation techniques, such as water-swelling capacity and contact angle measurement, to confirm the polymer's hydrophilicity and quantify its water absorption. This hands-on approach ensures a complete understanding of hydrophilic polymer preparation and testing methods."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe how you would use polyethylene glycol monomethyl ether (PEGME600) in a preparation scheme to modify a polymer to enhance its hydrophilicity. Specify the key reaction steps and conditions."}, {"role": "assistant", "content": "Certainly! To systematically describe how polyethylene glycol monomethyl ether (PEGME600) can be used to modify a polymer and enhance its hydrophilicity, let us proceed step-by-step:\n\n---\n\n### **Step 1: Analyze the Problem and Summarize Key Points**\n- **Objective**: Improve the hydrophilicity of a polymer by attaching polyethylene glycol monomethyl ether (PEGME600) chains to its structure. PEGME600 is hydrophilic due to its polyethylene glycol backbone, which is rich in ether groups (-CH\u2082-O-) capable of forming hydrogen bonds with water.\n- **Key Considerations**:\n  1. Choose a modification strategy based on the functional groups of the polymer backbone.\n  2. Ensure chemical compatibility between PEGME600 and the polymer.\n  3. Optimize reaction conditions to achieve an effective attachment of PEGME600.\n- **Approach**: Functionalize the polymer so it can react with PEGME600, using a coupling reaction (e.g., esterification, amidation, or click chemistry, depending on the polymer structure).\n\n---\n\n### **Step 2: Detailed Experimental Preparation Scheme**\nWe will assume the base polymer is a carboxylic acid-functionalized polymer (e.g., polymethacrylic acid or a polymer with pendent -COOH groups). If your polymer does not have carboxylic acid groups but has other reactive groups like hydroxyl (-OH), an amine (-NH\u2082), or others, minor adjustments can be provided.\n\n#### **2.1. Materials and Reagents**\n1. **Polymer with carboxylic acid (-COOH) groups**: For example, polymethacrylic acid (PMAA) as a model polymer.\n2. **Polyethylene glycol monomethyl ether (PEGME600)**: Molecular weight ~600 g/mol, provided as a liquid at room temperature.\n3. **Coupling Agent**: N,N'-Dicyclohexylcarbodiimide (DCC) or 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC\u00b7HCl) as a coupling agent to activate the -COOH group of the polymer.\n4. **Catalyst**: 4-Dimethylaminopyridine (DMAP) as a co-catalyst to facilitate esterification.\n5. **Solvent**: Anhydrous dichloromethane (DCM) or dimethylformamide (DMF) as an aprotic solvent.\n6. **Purification materials**: Methanol, diethyl ether, and deionized water.\n\n---\n\n### **2.2. Reaction Steps**\n\n#### **Step 2.2.1: Preparation of the Reaction Mixture**\n1. **Activation of Carboxylic Acid Groups**:\n   - Dissolve the carboxylic acid-functionalized polymer (PMAA) in DCM or DMF. Concentration: ~10-20 mg/mL.\n   - Add a molar equivalent (1:1 molar ratio to carboxylic acid groups) of DCC or EDC\u00b7HCl to the polymer solution. DCC/EDC activates the carboxylic acid groups to form reactive O-acylisourea intermediates.\n   - Optionally, add 0.1 molar equivalents of DMAP as a catalyst to improve reaction kinetics.\n   - Stir the mixture under inert gas (argon or nitrogen) for 30-60 minutes at room temperature.\n\n2. **Addition of PEGME600**:\n   - Slowly add PEGME600 to the activated polymer solution. Use a slight molar excess of PEGME600 (e.g., 1.1-1.2 molar equivalents relative to -COOH groups) to ensure complete reaction.\n   - Maintain stirring and allow the reaction to proceed at room temperature or slightly elevated temperatures (e.g., 35-40\u00b0C) under inert conditions for 12-24 hours.\n\n---\n\n#### **Step 2.2.2: Filtration and Work-Up**\n1. **Removal of By-Products**:\n   - Precipitate the reaction product by adding the reaction mixture into a large volume of cold methanol. Unreacted PEGME600 and small-molecule by-products (e.g., dicyclohexylurea from DCC) will remain soluble in methanol, while the polymer will precipitate.\n   - Filter the precipitated polymer using a vacuum filtration setup. Wash the polymer thoroughly with cold methanol to remove unreacted reagents.\n\n2. **Drying**:\n   - Dry the polymer precipitate under vacuum at room temperature for 24-48 hours or until a constant weight is achieved.\n\n---\n\n#### **Step 2.2.3: Characterization**\n1. **Fourier Transform Infrared Spectroscopy (FTIR)**:\n   - Check for the disappearance of the -COOH group peak (typically ~1700 cm\u207b\u00b9 for carbonyl) and the presence of -C-O-C- ether peaks (~1100 cm\u207b\u00b9) characteristic of PEG chains.\n2. **Nuclear Magnetic Resonance (NMR) Spectroscopy**:\n   - Use 1H NMR to confirm the presence of PEGME600 in the polymer. Characteristic PEG peaks include a singlet around \u03b4 ~3.5 ppm (for -OCH\u2082CH\u2082O- protons).\n3. **Contact Angle Measurements**:\n   - Measure the water contact angle on a film of the modified polymer to confirm improved hydrophilicity. A lower contact angle indicates greater hydrophilicity.\n4. **Gel Permeation Chromatography (GPC)**:\n   - Determine the molecular weight distribution of the modified polymer.\n\n---\n\n### **Step 3: Expected Outcomes**\n- By covalently attaching PEGME600 to the polymer backbone, the hydrophilicity of the polymer is significantly enhanced. This is due to the presence of hydrated ethylene oxide groups in PEG, which interact strongly with water molecules.\n- The resulting material is expected to exhibit better water dispersion or solubility and reduced fouling, making it suitable for applications such as hydrophilic coatings, biomedical devices, and drug delivery systems.\n\n---\n\n### **Alternative Strategies**\nIf the polymer lacks carboxylic acid groups:\n- For polymers with hydroxyl (-OH) groups: Convert -OH to tosylate groups using tosyl chloride, which can then react with PEGME600 under basic conditions (e.g., NaH).\n- For polymers with amine (-NH\u2082) groups: Directly react with PEGME600 activated with a carbonate group (e.g., PEGME600 carbonate derivative).\n\nLet me know if you need further guidance or adjustments for your specific polymer!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the steps required to synthesize an anti-fog modifier using octavinyl polyhedral oligomeric silsesquioxane and a polyether containing epoxy propylene and epoxy ethylene chains. Highlight the key reaction conditions you would implement to ensure a successful addition reaction."}, {"role": "assistant", "content": "### Question Analysis and Key Points\nThe student's question concerns the synthesis of an anti-fog modifier using two distinct components: **octavinyl polyhedral oligomeric silsesquioxane (OV-POSS)** and **a polyether containing epoxy propylene and epoxy ethylene chains**. The goal is to carry out a chemical addition reaction that ensures the functionalization of OV-POSS with hydrophilic polyether chains, ultimately enhancing its hydrophilicity for anti-fogging applications.\n\nThe key reaction involves:\n1. **Addition of the epoxy groups in the polyether chain to the vinyl groups on OV-POSS** (likely through a thiol-ene click reaction, radical addition reaction, or Michael addition).\n2. Optimization of the reaction conditions to maximize yield and minimize side reactions.\n\nHere\u2019s the detailed, step-by-step protocol for synthesizing the anti-fog modifier.\n\n---\n\n### Experimental Preparation Scheme\n\n#### Step 1: Materials and Reagents\n- **Octavinyl polyhedral oligomeric silsesquioxane (OV-POSS)**: The starting material containing vinyl groups.\n- **Polyether (with epoxy propylene and epoxy ethylene chains)**: Provides hydrophilic epoxy groups.\n- **Catalyst**: A platinum catalyst (e.g., Karstedt\u2019s catalyst) is highly effective for facilitating the selective addition reaction between the vinyl and epoxy groups.\n- **Solvent**: Toluene or tetrahydrofuran (THF) as the reaction medium. Choose based on reagent compatibility.\n- **Inert gas (e.g., nitrogen)**: To create a non-oxidizing atmosphere and avoid side reactions.\n\n---\n\n#### Step 2: Experimental Setup and Safety Precautions\n1. **Equipment Setup**:\n   - Use a three-neck round-bottom flask equipped with:\n     - A magnetic stirrer.\n     - A reflux condenser (to avoid evaporation of volatile reactants).\n     - A septum for sampling.\n     - A thermometer to monitor reaction temperature.\n\n2. **Safety Precautions**:\n   - Ensure the reaction is conducted under an inert atmosphere (nitrogen or argon) to prevent polymer degradation or unwanted oxidation.\n   - Use protective gloves and lab goggles, as both OV-POSS and the polyether can irritate skin and mucous membranes.\n\n---\n\n#### Step 3: Reaction Mechanism\nThe vinyl groups on OV-POSS react with the epoxy groups in the polyether via a **hydrosilylation reaction** (if using silane derivatives) or alternatively a **radical addition reaction** under catalytic or thermal conditions. We\u2019ll assume a platinum-catalyzed hydrosilylation pathway since it is highly specific for functionalizing vinyl groups.\n\n---\n\n#### Step 4: Detailed Procedure for Synthesis\n\n##### A. Catalyst Preparation\n1. Prepare an ultra-dilute solution of **Karstedt\u2019s catalyst** (Pt catalyst) in dry toluene or THF. Typical concentration: **10\u201320 ppm of platinum** relative to the total reactants. \n2. Store the catalyst solution in an amber vial away from light.\n\n---\n\n##### B. Reactant Mixture\n1. **Weigh OV-POSS**: Scale approximately **2.5 g (around 3.4 mmol)** of OV-POSS into the reaction flask.\n2. **Prepare polyether solution**:\n   - Dissolve **polyether epoxy chains** in dry toluene (e.g., 10 mL, concentration ~20 wt%) for easy mixing.\n   - Add a slight excess of the polyether epoxy chains (e.g., **1.2:1 molar ratio relative to OV-POSS**) to ensure complete vinyl group conversion.\n3. Add the catalyst solution: Typically, add **0.1 mL of the Karstedt catalyst solution**.\n\n---\n\n##### C. Reaction Conditions\n1. **Inert Atmosphere**:\n   - Purge the flask with nitrogen gas for 10 minutes before heating the reaction mixture.\n   - Maintain a slight nitrogen flow throughout the reaction.\n\n2. **Heating**:\n   - Heat to **90\u2013110\u00b0C** for **8\u201312 hours**. This temperature range is optimal for the platinum-catalyzed hydrosilylation of vinyl groups.\n   - Stir the solution continuously to ensure homogeneous mixing and avoid local over-heating.\n\n3. **Monitoring**:\n   - Monitor the reaction progress using **FTIR spectroscopy**. Disappearance of the vinyl C=C stretching band (~1600 cm\u207b\u00b9) and emergence of C-O-C bonds (~1100 cm\u207b\u00b9 for epoxide reaction products) confirm the successful addition.\n\n---\n\n#### Step 5: Purification\n1. Cool the reaction mixture to room temperature and dilute further with an inert solvent like THF.\n2. Precipitate the polymerized product by slowly dripping the reaction mixture into cold diethyl ether or methanol under stirring. This step removes unreacted polyether or low-molecular weight byproducts.\n3. Collect the precipitate via vacuum filtration and wash thoroughly with methanol.\n\n---\n\n#### Step 6: Characterization\n1. **Confirm the structure**:\n   - Use **NMR spectroscopy** (\u00b9H and \u00b9\u00b3C):\n     - Verify the absence of vinyl peaks (~5\u20136 ppm for C=C in OV-POSS).\n     - Appearance of peaks corresponding to epoxy-derived functionalities (~3\u20134 ppm for CH-O).\n   - Perform **FTIR** spectroscopy to ensure conversion.\n2. **Molecular weight**:\n   - Measure the molecular weight using **Gel Permeation Chromatography (GPC)** to confirm successful grafting of polyether chains onto OV-POSS.\n3. **Hydrophilicity testing**:\n   - Conduct contact angle measurements on a thin coating of the synthesized polymer to confirm its anti-fogging properties.\n\n---\n\n### Notes on Optimizing Hydrophilicity\n1. **Polyether Selection**:\n   - Choose a polyether with a higher proportion of **ethylene oxide** vs. propylene oxide units to maximize hydrophilicity.\n2. **Epoxy-to-Vinyl Ratio**:\n   - An excess of polyether is recommended to ensure complete functionalization.\n3. **Reaction Time**:\n   - Extend reaction time if FTIR shows incomplete vinyl group conversion after 12 hours.\n\n---\n\n### Final Remarks\nBy following this systematic protocol, students should be able to prepare a hydrophilic anti-fog modifier successfully in the lab. The controlled functionalization of OV-POSS with hydrophilic polyether chains enhances its anti-fogging capabilities, making it a suitable candidate for optical, automotive, or coating applications. Always prioritize precise molar ratios, reaction temperature control, and inert conditions for optimal results!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "How would you utilize pentaerythritol tetrathioglycolate (PTMP) in a polymer modification experiment to enhance hydrophilicity? Elaborate on the steps to ensure a consistent product and high reaction yield."}, {"role": "assistant", "content": "Certainly! Let us analyze your question and systematically construct a detailed response to ensure clarity and rigor for your experiment. The goal is to utilize pentaerythritol tetrathioglycolate (PTMP) in a polymer modification experiment to enhance hydrophilicity. With a hydrophilic end goal in mind, we can approach this by leveraging PTMP's thiol functional groups to graft hydrophilic functional groups onto the polymer matrix. I will break this down step by step, covering each step in detail.\n\n---\n\n### 1. Analysis of the Question\n\n- **Key molecule**: Pentaerythritol tetrathioglycolate (PTMP). This molecule possesses 4 thiol (-SH) groups, making it a highly reactive branching agent in polymer chemistry.\n- **Objective**: Enhance hydrophilicity of a polymer.\n- **Approach**: Modify the polymer using PTMP through chemical grafting.\n- **Desired outcome**: A hydrophilic polymer with consistent product quality and a high reaction yield.\n\n---\n\n### 2. Experimental Preparation Scheme for Hydrophilic Polymer Modification Using PTMP\n\n#### Step 1: Selection of the Polymer Substrate\nChoose a polymer substrate that readily undergoes functional group modification. Polymers such as polyethylene glycol (PEG), polyacrylamides, or polyvinyl alcohol (PVA) are good candidates. If the polymer lacks reactive sites, it may require pre-treatment, such as introducing double bonds or reactive pendant groups into its structure.\n\n#### Step 2: Solvent System\nUse an appropriate solvent that ensures efficient solubility of PTMP and the polymer. Possible solvents include polar organic solvents such as dimethyl sulfoxide (DMSO) or tetrahydrofuran (THF). DMSO is preferred for reactions targeting hydrophilic polymers due to its polar nature and compatibility with thiol chemistry.\n\n#### Step 3: Functionalization Reaction\nTo graft PTMP onto the polymer backbone, utilize a thiol-ene or thiol-Michael addition chemistry approach\u2014both are ideal to exploit PTMP\u2019s thiol groups in a controlled environment.\n\n- **Reaction conditions:**\n  - **Mechanism 1 - Thiol-Ene Click Reaction**:\n    - Requires unsaturated (C=C double bond) groups on the polymer.\n    - These can be naturally present or introduced via pre-modification. A free-radical initiator (e.g., azobisisobutyronitrile, AIBN) or photoinitiator (e.g., Irgacure) can be used under UV light or thermal conditions.\n    - Reaction temperature: 60-80\u00b0C (mild heating ensures reactivity and avoids side reactions).\n    - Reaction time: 4-6 hours under inert conditions (e.g., nitrogen or argon blanket to prevent thiol oxidation).\n\n  - **Mechanism 2 - Thiol-Michael Addition**:\n    - Requires electron-deficient alkene groups on the polymer (e.g., acrylates or maleimides).\n    - Reaction catalyst: Tertiary amines like triethylamine (TEA) or sodium hydroxide (NaOH) at 0.1 to 0.5 M concentration.\n    - Reaction temperature: 30-50\u00b0C (near ambient temperature avoids degradation).\n    - Reaction time: 3-4 hours with stirring.\n\n- **Reagent Ratios:**\n  - PTMP:Polymer = 1:2 molar ratio (excess polymer ensures complete utilization of PTMP\u2019s reactive sites while avoiding crosslinking-induced gelation).\n\n#### Step 4: Introduction of Hydrophilic Groups\nThe hydrophilicity of the modified polymer will be increased by appending polar functional groups. Some strategies include:\n- **Hydrolysis**: Post-reaction hydrolysis of ester groups on PTMP (if applicable) can generate hydroxyl (-OH) groups.\n- **Use of Polar Monomers or Crosslinkers**: You may alternatively consider coupling PTMP with hydrophilic crosslinkers such as acrylic acid, methacrylic acid, or sulfonic acid derivatives.\n\n#### Step 5: Purification\nTo ensure a consistent product, remove unreacted PTMP and polymer impurities using the following methods:\n- Dilute the reaction medium with excess water or alcohol, inducing precipitation of excess reagent.\n- Perform dialysis using a membrane with an appropriate molecular weight cutoff (MWCO). For instance, polyethylene glycol dialysis tubing works well for hydrophilic polymers.\n- Dry the purified polymer under vacuum or lyophilize to avoid thermal degradation.\n\n#### Step 6: Characterization of the Final Hydrophilic Polymer\nOnce the modified polymer is prepared, confirm the success of hydrophilic functionalization using the following techniques:\n- **Fourier-transform infrared spectroscopy (FTIR)**: Look for characteristic thiol peaks (2550 cm\u207b\u00b9) interactions and emergence of polar group peaks (-OH stretch ~3400 cm\u207b\u00b9 or sulfate peaks ~1200 cm\u207b\u00b9).\n- **Contact angle measurements**: Measure water contact angle to quantify surface hydrophilicity enhancement; a lower angle indicates higher hydrophilicity.\n- **NMR spectroscopy**: Proton-NMR can identify changes in the polymer backbone and confirm successful grafting of PTMP moieties.\n- **Thermal analysis**: Use Differential Scanning Calorimetry (DSC) or Thermogravimetric Analysis (TGA) to confirm thermal stability after modification.\n\n---\n\n### 3. Notes for Optimization and Troubleshooting\n1. **Prevent Oxidation of Thiols**: Work under inert conditions (N\u2082 or Argon) throughout the reaction to prevent thiol oxidation to disulfides, which would reduce yield.\n2. **Minimize Cross-Linking**:\n   - Adjust molar ratios of PTMP and polymer carefully. Excess PTMP may lead to undesired cross-linking and gelation, complicating purification.\n   - Graft hydrophilic side chains uniformly rather than allowing random polymer branching.\n3. **Yield Improvement**:\n   - Use high-purity reagents and solvents to avoid side reactions.\n   - Optimize reaction temperature and time to maximize utilization of PTMP.\n\n---\n\nBy systematically following this preparation scheme, you should achieve a high yield of a consistently hydrophilic polymer modified with PTMP, suitable for applications such as biomedical coatings, water purification membranes, or hydrophilic adhesives. Make sure to test the material under relevant application conditions to verify its enhanced hydrophilicity."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "How would you utilize the molecule polydopamine in your experimental design to create an initiation layer that facilitates the synthesis of hydrophilic polymers?"}, {"role": "assistant", "content": "To address your question using polydopamine as an initiation layer for the synthesis of hydrophilic polymers, let us proceed systematically and thoughtfully. Here are the critical steps to follow:\n\n---\n\n### **Step 1: Analyze the Question and Summarize Key Points**\nYou intend to use polydopamine (PDA) as the basis for creating an initiation layer to facilitate the synthesis of hydrophilic polymers. Polydopamine is a versatile material that exhibits strong adhesion to virtually any surface due to its catechol and amine groups. These functional groups can serve as reactive sites to anchor hydrophilic polymer chains either through grafting or polymerization strategies. The key goal is to build a surface-functionalized polymer layer with enhanced hydrophilicity by leveraging PDA's unique properties.\n\nConsequently, the experimental scheme must:\n1. Deposit PDA onto a substrate as the initiation layer.\n2. Identify mechanisms (grafting or polymerization) and hydrophilic monomers to create the polymer layer.\n3. Ensure the hydrophilic polymer is synthesized systematically, with precise reaction conditions, reagent ratios, and techniques.\n\n---\n\n### **Step 2: Systematic Answer**\nHere is the detailed experimental preparation scheme for synthesizing a hydrophilic polymer layer using PDA.\n\n---\n\n#### **Step A: Polydopamine Deposition on the Substrate**\n1. **Substrate Preparation**: Choose an appropriate substrate, such as glass, metals (e.g., titanium, stainless steel), or polymers (e.g., polyethylene, polystyrene). Clean the substrate to remove contaminants (if applicable):\n   - Wash substrate thoroughly with deionized (DI) water.\n   - Sonicate in ethanol followed by DI water for 15 minutes each.\n   - Dry substrate with nitrogen.\n\n2. **Polydopamine Coating**:\n   - Prepare a dopamine solution (2 mg/mL) in Tris buffer (10 mM, pH 8.5).\n   - Place the clean substrate into the dopamine solution and allow it to polymerize at room temperature for 12\u201324 hours under gentle stirring. Dopamine self-polymerizes into polydopamine under mildly alkaline conditions.\n   - After deposition, rinse the substrate thoroughly with DI water to remove any unreacted dopamine or loosely bound PDA particles.\n   - Dry the polydopamine-coated substrate under nitrogen or air.\n\n   **Mechanism and Role**: During polymerization, dopamine forms a PDA layer through covalent and \u03c0\u2212\u03c0 interactions. The catechol and amino groups on PDA provide a reactive initiation layer for further functionalization.\n\n---\n\n#### **Step B: Selection of Hydrophilic Monomers and Polymerization Method**\nChoose a hydrophilic monomer capable of forming the desired polymer layer. Common hydrophilic monomers include:\n   - Acrylamide (AM) for polyacrylamide.\n   - Polyethylene glycol methacrylate (PEGMA) for PEG-based hydrophilic polymers.\n   - N-vinylpyrrolidone (NVP) for polyvinylpyrrolidone.\n\nA suitable polymerization method must also be selected:\n   - **Grafting-to**: Attach preformed hydrophilic polymer chains to PDA.\n   - **Grafting-from**: Initiate polymerization directly from PDA.\n   - **Surface-initiated polymerization (SIP)**: Use PDA\u2019s reactive groups to create polymer chains directly.\n\n---\n\n#### **Step C: Experimental Design for Hydrophilic Polymerization**\nWe will use surface-initiated atom transfer radical polymerization (SI-ATRP) as an example due to its controllability. Let\u2019s synthesize polyacrylamide (PAAm) for enhanced hydrophilicity.\n\n1. **Step 1: Activate PDA Layer for ATRP initiation**\n   - Prepare a bromoisobutyryl bromide (BIBB) solution in dry dichloromethane (DCM).\n   - Immerse the PDA-coated substrate into the solution for 4\u20136 hours, ensuring covalent binding of ATRP initiator (BIBB) to PDA's amine groups.\n   - Wash substrate with DCM and ethanol to remove excess BIBB.\n   - Dry the substrate under inert gas.\n\n2. **Step 2: Prepare the Polymerization Solution**\n   - Dissolve acrylamide monomer (1 M concentration) in DI water.\n   - Add a catalyst system (CuBr/CuBr2 complex) and ligand (e.g., N,N,N\u2032,N\u2032\u2032-tetramethylethylenediamine, TMEDA) to the solution, ensuring a monomer:catalyst ratio of **100:1**.\n   - Degas the solution using nitrogen bubbling for 10 minutes to remove oxygen (oxygen inhibits ATRP).\n\n3. **Step 3: Initiate Polymerization on PDA Layer**\n   - Immerse the PDA-bound substrate into the polymerization solution.\n   - Maintain the reaction at room temperature or slightly elevated temperature (e.g., 25\u201335\u00b0C) for 2\u20134 hours, depending on the desired polymer thickness.\n   - After polymerization, remove the substrate and rinse thoroughly with DI water and ethanol to eliminate unreacted monomers and residual reagents.\n\n4. **Step 4: Post-Treatment (Optional)**\n   - Purify the polymer layer further if needed, such as soaking the substrate in ethanol or acetone.\n   - Dry the final polymer-coated substrate under nitrogen.\n\n---\n\n#### **Step D: Confirmation of Hydrophilic Polymer Coating**\nTo confirm successful polymer synthesis and hydrophilicity enhancement:\n1. **Surface Characterization**:\n   - Use Fourier-transform infrared spectroscopy (FTIR) to identify functional groups indicative of the hydrophilic polymer.\n   - Use scanning electron microscopy (SEM) or atomic force microscopy (AFM) to visualize the coating's morphology.\n\n2. **Hydrophilicity Tests**:\n   - Measure the water contact angle using a goniometer: A significantly reduced angle (e.g., <30\u00b0) indicates hydrophilic enhancements.\n   - Conduct dynamic water absorption tests.\n\n---\n\n### **Step 3: Wrap-Up**\nUsing polydopamine as an initiation layer not only provides a robust base for polymerization but also ensures excellent adhesion of hydrophilic polymer chains to the substrate. By selecting ATRP as the polymerization method and acrylamide as the hydrophilic monomer, we achieved a controllable synthesis of polyacrylamide on a PDA-coated substrate. Every reaction step, from polydopamine deposition to polymer layer confirmation, is critical for successful experimental implementation in the lab.\n\nLet me know if further clarification or customization is needed!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain how you would use a host-guest interaction between a suprastructure and a polymer in a layer-by-layer assembly to improve the hydrophilicity of the polymer. Include details about substrate preparation and the number of desired layers."}, {"role": "assistant", "content": "To answer your question systematically and thoroughly, I will analyze the problem, provide an experimental preparation scheme for using a host-guest interaction in a suprastructure/polymer layer-by-layer (LbL) assembly to improve hydrophilicity, and include specific details regarding substrate preparation, reaction conditions, and the desired number of layers.\n\n---\n\n### **1. Key considerations in the question:**\n- **Primary focus:** Use of host-guest chemistry in an LbL assembly to modify and enhance the hydrophilicity of a polymer.\n- **Materials involved:** A suprastructure with host-guest capabilities and a polymer that interacts with it. \n- **Goal:** Systematic preparation of a hydrophilic polymer by assembling layers with controlled chemistry.\n- **Details required:** Substrate preparation, reaction conditions, reagent quantities, and the target number of layers.\n\n---\n\n### **2. Host-guest interaction in polymer assembly:**\nHost-guest interactions rely on non-covalent binding between a \"host\" molecule (e.g., cyclodextrins) and a \"guest\" molecule (e.g., hydrophilic moieties or small aromatic compounds) to build supramolecular structures. This principle can be applied in an LbL assembly to create alternating layers of a hydrophilic polymer and a supramolecular host molecule, ultimately enhancing surface hydrophilicity.\n\n**Host example:** \u03b2-cyclodextrin (CD), which has a hydrophobic inner cavity and hydrophilic exterior.\n**Guest example:** A hydrophilic polymer functionalized with aromatic moieties, such as polyethylene glycol modified with ferrocene or adamantane groups.\n\n---\n\n### **3. Experimental Procedure: Layer-By-Layer Assembly**\n\n#### **Step 1: Substrate preparation**\n1. **Substrate selection:** Use a flat, stable substrate such as a glass slide, silicon wafer, or a nickel grid. The substrate must have a clean, smooth surface to promote uniform adhesion. \n2. **Cleaning:** \n   - Immerse the substrate in piranha solution (3:1 mixture of concentrated sulfuric acid and hydrogen peroxide) for 30 minutes. *(Caution: Piranha solution is highly reactive\u2014handle with extreme care!)*\n   - Rinse thoroughly with deionized (DI) water and dry under a nitrogen stream.\n3. **Surface functionalization (if required):**\n   - To improve interaction between the substrate and the first polymer layer, functionalize the substrate surface with a positively charged monolayer, e.g., expose to a 1 mM solution of poly(allylamine hydrochloride) (PAH) in DI water for 5 minutes. Rinse with DI water and dry.\n\n---\n\n#### **Step 2: Preparation of aqueous solutions**\n1. Prepare a 5 mg/mL solution of \u03b2-cyclodextrin (host) in DI water.\n2. Prepare a 1 mg/mL solution of the hydrophilic polymer-functionalized with a guest molecule (e.g., adamantyl-polyethylene glycol), also in DI water.\n\n---\n\n#### **Step 3: Layer-by-layer (LbL) assembly**\n1. **Immersion cycle for layer formation:**\n   - **Host layer deposition:** Submerge the prepared substrate in the \u03b2-cyclodextrin solution for 10 minutes to allow adsorption via electrostatic or host-guest interactions. Ensure calm agitation during this process for uniform adsorption.\n   - **Rinse and dry:** Remove the substrate, rinse with DI water to remove excess \u03b2-cyclodextrin, and dry gently with nitrogen.\n   - **Guest/polymer layer deposition:** Submerge the \u03b2-cyclodextrin-coated substrate in the guest-functionalized hydrophilic polymer solution for 15 minutes. This will allow the guest groups to enter the host's hydrophobic cavity, forming host-guest complexes.\n   - **Rinse and dry:** Clean the substrate as in the previous step (DI water rinse + nitrogen drying).\n2. Repeat the immersion cycle (steps 3.1 through 3.4) to create additional layers. Each cycle adds one bilayer of host (cyclodextrin) and guest (functionalized hydrophilic polymer).\n\n---\n\n#### **Step 4: Number of desired layers**\n- **Determining optimal layers for hydrophilicity:** Perform contact angle measurements after depositing each bilayer. Hydrophilicity is indicated by a decrease in the water contact angle.\n- For most applications, 10\u201315 bilayers (~20\u201330 nm thick, depending on the size of the host and guest) are sufficient to ensure significant surface hydrophilicity.\n\n---\n\n#### **Step 5: Verification of assembly**\n1. Use spectroscopic and microscopic techniques to verify successful LbL assembly:\n   - **UV-vis absorbance:** Confirm increased optical density after each layer deposition if the polymer-host complex is UV-active.\n   - **Atomic force microscopy (AFM):** Visualize uniformity and thickness of the layers.\n   - **Contact angle measurement:** Ensure progressive improvement in hydrophilicity as layers are added.\n\n---\n\n### **4. Reaction Conditions & Notes:**\n- Maintain room temperature (20\u201325 \u00b0C) throughout the procedure to prevent degradation of the host or guest molecules.\n- All solutions should be prepared fresh and filtered (using a 0.22 \u03bcm membrane) before use to remove particulates.\n- Use ultrapure DI water for all rinsing steps to prevent contamination.\n- If working with charged variants of host or guest molecules, the ionic strength of the solution can be adjusted by adding NaCl (e.g., 0.1 M) to facilitate electrostatic interactions.\n\n---\n\n### **5. Summary**\nThis procedure uses a host-guest LbL assembly to enhance the hydrophilicity of a polymer-coated substrate. Starting with a clean, functionalized substrate, the process alternates between adsorption of a host molecule (e.g., \u03b2-cyclodextrin) and a guest-functionalized hydrophilic polymer. By repeating the alternating adsorption process for a defined number of bilayers (e.g., 10\u201315), surface modification is achieved, with improved hydrophilicity verified by techniques such as contact angle measurements and AFM imaging.\n\nThis systematic approach ensures the successful preparation of a hydrophilic polymer via controlled supramolecular assembly. Should you encounter any practical challenges in the lab, feel free to reach out for clarification!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "How would you utilize glycerol as a key reactant to synthesize a hydrophilic polymer through an esterification reaction? Provide a detailed experimental scheme, including necessary reaction conditions and any precautions you would take during the process."}, {"role": "assistant", "content": "Certainly! To synthesize a hydrophilic polymer using glycerol as a key reactant through an esterification reaction, one can leverage glycerol\u2019s trifunctional nature (it has three hydroxyl groups) to create a polymer with hydrophilic pendant groups or a hydrophilic backbone. Let us carefully analyze and design an experimental scheme to carry out this process, adhering to the systematic approach you requested.\n\n---\n\n### **1. Analysis of the question and key points**\nThe question requires a detailed and systematic synthesis of a hydrophilic polymer using glycerol in an esterification reaction. Key points to address include:\n- Leveraging glycerol's multiple reactive hydroxyl groups as sites for polymer formation.\n- Achieving esterification while introducing hydrophilicity into the polymer chain.\n- Providing precise reaction conditions, reagent quantities, molar proportions, and necessary precautions for a successful experiment.\n\nGiven the question, it is ideal to combine glycerol with a diacid (or anhydride) and potentially copolymerize it with other hydrophilic monomers to tailor the polymer's properties. A widely-used hydrophilic polymer synthesis strategy involves polycondensation or step-growth polymerization.\n\n---\n\n### **2. Experimental preparation scheme**\nBelow, I provide a step-by-step experimental scheme for synthesizing a hydrophilic polymer using glycerol via an esterification reaction.\n\n---\n\n#### **Materials and equipment**\n- **Reagents:**\n  1. Glycerol (C\u2083H\u2088O\u2083) \u2013 the core reactant.\n  2. Adipic acid (C\u2086H\u2081\u2080O\u2084) \u2013 the diacid for esterification (you may substitute this with other diacids/anhydrides, such as maleic anhydride, for enhanced hydrophilicity).\n  3. Catalysts: Sulfuric acid (H\u2082SO\u2084) or p-toluenesulfonic acid (PTSA) \u2013 commonly used acid catalysts.\n  4. Solvent (optional): Toluene or xylene \u2013 sometimes used to form a water azeotrope for removing byproduct water.\n  5. Additional hydrophilic monomers (optional): Hydroxyethyl methacrylate (HEMA) or polyethylene glycol (PEG) if desired for further hydrophilic modification.\n\n- **Equipment:**\n  1. Three-neck round-bottom flask.\n  2. Condenser for reflux and water collection.\n  3. Magnetic stirrer and heating mantle.\n  4. Nitrogen gas for inert atmosphere (if required).\n  5. Thermocouple or thermometer.\n\n---\n\n#### **Step-by-step reaction procedure**\n\n##### **Step 1: Reaction setup**\n1. Prepare a **three-neck round-bottom flask** equipped with a magnetic stirrer.\n2. Connect a **condenser** to the flask to perform the reaction under reflux and collect the water generated during esterification.\n3. Optionally, run the reaction under an **inert nitrogen atmosphere** to prevent oxidative degradation.\n\n---\n\n##### **Step 2: Initial reactant loading**\n1. Add **glycerol** (1.00 mol) into the round-bottom flask. For instance, 92 g of glycerol (molecular weight = 92.09 g/mol) will be sufficient for 1.00 mol.\n2. Add **adipic acid** (1.00 mol) into the same flask. For instance, 146.14 g of adipic acid (molecular weight = 146.14 g/mol) will be sufficient for 1.00 mol.\n3. Add a catalytic amount of **sulfuric acid**: approximately 1\u20132 wt% of the reaction mass. For example, if the total mass of glycerol and adipic acid is ~238 g, add ~2 g (0.01 mol) of sulfuric acid.\n\n---\n\n##### **Step 3: Reaction conditions**\n1. Heat the system to 160\u2013200 \u00b0C using a heating mantle. Ensure vigorous stirring to maintain homogeneity.\n2. Maintain the reflux temperature so that the esterification proceeds effectively. You will visibly observe water collecting in the condenser receiver due to the condensation reaction.\n3. Monitor the reaction progress by observing the reduction in the hydroxyl group intensity via FTIR spectroscopy.\n\n---\n\n##### **Step 4: Removal of byproduct water**\n1. Collect the water byproduct during the reaction to shift equilibrium toward polymer formation.\n   - If water generation slows, you may use an azeotropic solvent (e.g., toluene or xylene) to assist in water removal.\n\n---\n\n##### **Step 5: Reaction time**\n1. Allow the reaction to proceed for **6\u201312 hours**, depending on the reactivity of the monomers and desired molecular weight. \n   - Longer reaction times tend to yield higher molecular weights but could risk side reactions.\n\n---\n\n##### **Step 6: Post-polymerization**\n1. Once the desired viscosity and hydrophilicity are achieved:\n   - Cool the reaction mixture to room temperature.\n   - Precipitate the polymer by adding the reaction mixture to excess cold alcohol (e.g., methanol or ethanol).\n2. Wash the polymer thoroughly with alcohol to remove unreacted monomers and catalyst residues.\n3. Dry the polymer under vacuum at 60\u201380 \u00b0C.\n\n---\n\n#### **Precautions during the experiment**\n1. Ensure the catalyst concentration is controlled to prevent excessive side reactions such as crosslinking.\n2. Prevent overheating above 200 \u00b0C, as glycerol may decompose or lead to unwanted oligomer formation.\n3. Use an inert atmosphere to minimize oxidative degradation of the polymer backbone if running long reaction times.\n4. Regularly monitor the reaction by FTIR or NMR spectroscopy to confirm ester bond formation and molecular structure.\n\n---\n\n#### **Optional hydrophilic enhancement**\nIf further hydrophilicity is required:\n1. Copolymerize **glycerol** and **adipic acid** with hydrophilic monomers such as **polyethylene glycol (PEG)** or **hydroxyethyl methacrylate (HEMA)**. For example:\n   - Use PEG with molecular weights of 400 or 1000 (adjust mole ratios accordingly).\n   - Maintain similar reaction conditions with controlled molar ratios (~30% hydrophilic monomer by weight).\n\n---\n\n#### **Conclusion**\nThe described polycondensation reaction between glycerol and adipic acid creates a hydrophilic polyester backbone. The ester groups contribute hydrophilicity while retaining mechanical stability. Additional copolymerization with PEG or HEMA can further enhance hydrophilicity, making this polymer ideal for applications such as hydrogels, biocompatible coatings, or water treatment membranes.\n\nBy following this carefully designed experimental scheme, students should successfully achieve the synthesis of a hydrophilic polymer using glycerol in the laboratory."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "In a Michael addition reaction, polyethylene glycol diacrylate (PEG400DA) reacts with a diamine to form an intermediate hydrophilic polymer. Outline a detailed experimental procedure for preparing this intermediate, focusing on how the molar ratio of the two reactants influences the hydrophilicity of the intermediate."}, {"role": "assistant", "content": "Certainly! I'll guide you systematically through the process of answering your question, focusing on analysis, experimental procedure, and key aspects such as the molar ratio's influence on hydrophilicity.\n\n---\n\n### **Step 1: Analyze the Question**\nThe reaction described involves a **Michael addition** reaction between **polyethylene glycol diacrylate (PEG400DA)** and a **diamine** to synthesize an intermediate hydrophilic polymer. The goal is not only to understand the preparation procedure but also to examine how the molar ratio of PEG400DA and diamine influences the hydrophilicity of the intermediate.\n\nKey Points:\n1. **Reactants**:\n   - PEG400DA: A difunctional acrylate-based reagent with hydrophilic properties due to the PEG chain (average molar mass ~400 g/mol per PEG chain).\n   - Diamine: A molecule containing primary amine groups (-NH2), capable of undergoing nucleophilic addition during the Michael addition reaction.\n2. **Reaction Conditions**: The Michael addition is a base-catalyzed nucleophilic reaction generally conducted in the presence of mild base and/or solvent.\n3. **Molar Ratio Effect**: The degree of functionality achieved in the product (extent of crosslinking and chain formation) depends on the molar ratio of the two reactants. This balance regulates:\n   - The density of amino and acrylate groups available for the reaction.\n   - The hydrophilicity of the product: A higher PEG content will enhance hydrophilicity, while excessive crosslinking via diamine could reduce it.\n\n---\n\n### **Step 2: Experimental Design for Polymer Preparation**\n\nHere is a detailed experimental scheme for synthesizing the intermediate hydrophilic polymer.\n\n---\n\n#### **Materials Required**\n1. **Polyethylene glycol diacrylate (PEG400DA)**: Commercially available; ensure purity >98%.\n2. **Diamine**: Choose a suitable hydrophilic diamine (e.g., ethylenediamine or 1,6-hexanediamine).\n3. **Solvent**: Deionized water or a polar aprotic solvent like dimethyl sulfoxide (DMSO). Avoid nonpolar solvents to maintain hydrophilicity.\n4. **Base Catalyst**: Triethylamine (TEA) or sodium bicarbonate (~0.1 equivalent to diamine) for mildly basic conditions.\n5. **pH Adjuster (Optional)**: Small amounts of dilute solutions of HCl or NaOH for fine-tuning.\n6. **Stirrer Setup**: Magnetic stirrer and sealed flask to prevent contamination.\n\n---\n\n#### **Step 1: Define Molar Ratios**\n\nThe molar ratio of PEG400DA to diamine is critical. The interaction of ratios with hydrophilicity is as follows:\n- **Molar Ratio**: PEG400DA:Diamine.\n   1. **Low Diamine (2:1 or higher)**: Excess PEG400DA results in incomplete crosslinking and introduces free hydrophilic PEG acrylate groups, enhancing hydrophilicity.\n   2. **Equimolar Ratio (1:1)**: A balanced reaction results in full reaction of all functional acrylate and amine groups, yielding a network with moderate hydrophilicity.\n   3. **High Diamine (1:2 or higher)**: Excess diamine introduces additional amino groups, which could slightly reduce the polymer's hydrophilicity due to reduced free PEG content.\n\nDecide on the desired hydrophilicity for your product and adjust the molar ratio accordingly. For example, if high hydrophilicity is desired, a PEG-rich environment (e.g., 2:1 molar ratio) is preferred.\n\n---\n\n#### **Step 2: Reaction Setup**\n\n1. **Prepare Reaction Mixture**:\n   - Dissolve PEG400DA (e.g., **2 mmol, 0.8 g for PEG400**) in 10 mL of the chosen solvent (water or DMSO) under mild stirring to form a homogenous solution.\n   - Add the diamine (e.g., **1 mmol, 0.06 g for ethylenediamine**) slowly, ensuring the desired molar ratio. Stir continuously.\n   - Add the base catalyst (e.g., **0.1 mmol of triethylamine**, ~0.01 mL).\n\n2. **Control Reaction Parameters**:\n   - **Temperature**: Maintain mild conditions (~25\u201340\u00b0C) to prevent side reactions or premature polymerization.\n   - **Stirring**: Stir gently (~500 RPM) but uniformly for effective mixing.\n   - **pH Monitoring**: Ensure the pH stays between 8\u201310 to facilitate the Michael addition reaction without degrading reactants.\n   - **Reaction Time**: Allow 2\u20134 hours for the reaction to complete. Monitor the reaction progress using infrared spectroscopy (IR peaks for acrylate at ~810 cm\u207b\u00b9 will disappear as the acrylate groups react).\n\n---\n\n#### **Step 3: Post-Reaction Steps**\n\n1. **Isolation**:\n   - After the reaction completes, remove the solvent using mild vacuum evaporation or dialysis (in case of water-based reactions) to purify the intermediate polymer.\n   - Adjust pH if necessary and wash the polymer with deionized water to remove unreacted diamine or PEG.\n\n2. **Characterization**:\n   - Use **Fourier-transform infrared spectroscopy (FTIR)** to confirm the disappearance of acrylate groups and appearance of new bonds (e.g., C-N stretching at ~1250 cm\u207b\u00b9).\n   - Check molecular weight distribution using **gel permeation chromatography (GPC)**.\n   - Confirm hydrophilicity by checking the water contact angle or swelling behavior in an aqueous environment.\n\n---\n\n### **Step 3: Discuss Influence of Molar Ratio on Hydrophilicity**\n\n- **PEG400DA-Rich Polymers**: High hydrophilicity due to excess free PEG chains. These materials swell significantly in water and are ideal for applications like hydrogels or bio-compatible materials.\n- **Balanced Ratios**: Moderate hydrophilicity with well-balanced crosslinked networks.\n- **Diamine-Rich Polymers**: Reduced hydrophilicity due to higher amine content, which could affect the degree of swelling or solubility in water.\n\nTailor the molar ratio based on the application. For hydrogels, PEG-rich conditions (e.g., 2:1) would be ideal. For structural purposes, a balanced (1:1) ratio provides mechanical stability without compromising water compatibility.\n\n---\n\n### **Conclusion**\n\nTo prepare a hydrophilic polymer via the Michael addition of PEG400DA and diamine:\n1. Choose a molar ratio suitable for your hydrophilicity requirements.\n2. Control reaction conditions (e.g., mild temperature, stirring, pH).\n3. Characterize the product to ensure hydrophilicity and chemical structure meet expectations.\n4. Adjust experimental parameters iteratively as needed for refinement.\n\nGood luck in the lab\u2014let me know if you want any additional clarifications!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "How would you use the molecule dimethylol propionic acid (DMPA) to prepare a hydrophilic polymer with enhanced water dispersibility and anionic stabilization properties? Describe the steps and the role of this molecule in the synthesis process."}, {"role": "assistant", "content": "Certainly! Enhancing the hydrophilicity and water dispersibility of polymers is a critical area in materials science, particularly in applications such as coatings, adhesives, and biomedical materials. Dimethylol propionic acid (DMPA) is a versatile monomer for introducing hydrophilic groups into polymer structures due to its unique structure\u2014it contains hydroxyl groups for polymerization and a carboxylic acid group that can impart anionic stabilization properties. Let\u2019s analyze your question step by step and provide a systematic experimental preparation scheme.\n\n---\n\n### Key Points from Your Question:\n1. **Target Polymer Properties**:\n   - Enhanced water dispersibility.\n   - Anionic stabilization properties.\n\n2. **Role of DMPA**:\n   - Hydrophilic hydroxyl groups for improved water affinity.\n   - Carboxylic acid groups for introducing ionic stabilization.\n\n3. **Preparation Method**:\n   - Choosing appropriate co-monomers or pre-polymers.\n   - Incorporating DMPA into the polymer backbone or as a pendant group.\n\nNow let\u2019s proceed with the detailed experimental design.\n\n---\n\n### Experimental Preparation Scheme for Hydrophilic Polymer Using DMPA:\n\n#### Step 1: Polymer Design and Selection of Co-monomers\nStart by selecting monomers or pre-polymers that can polymerize with DMPA to form a polymer matrix. Examples include diols (e.g., neopentyl glycol or ethylene glycol), diisocyanates (e.g., hexamethylene diisocyanate, HDI), or pre-polymers such as polyesters or polyethers. Given the goal of hydrophilicity, you should prioritize aliphatic diols or other flexible molecules with minimal steric hindrance.\n\n#### Step 2: Reaction Type\nIncorporate DMPA using a step-growth polymerization process, such as polyurethane or polyester synthesis, where its hydroxyl groups participate in esterification or urethane formation, and its carboxylic acid group is retained for ionic stabilization. An alternative approach is using free radical polymerization where DMPA is a co-monomer with vinyl-functionalized molecules.\n\n#### Step 3: Experimental Details\nLet us focus on the preparation of a polyurethane polymer with enhanced hydrophilic properties using DMPA.\n\n---\n\n### Experimental Procedure: Synthesis of Hydrophilic Polyurethane Using DMPA\n\n#### **Materials**:\n- **Dimethylol propionic acid (DMPA)**: Key hydrophilic monomer.\n- **Diisocyanate**: Hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI) for urethane linkage.\n- **Diols**: Ethylene glycol (EG) or neopentyl glycol (NPG) for additional polymer backbone properties.\n- **Neutralizing agent**: Triethylamine (TEA) or sodium hydroxide for ionic stabilization.\n- **Catalyst**: Dibutyltin dilaurate (DBTDL).\n- **Solvent**: N,N-dimethylformamide (DMF) or acetone (optional, for reaction medium).\n\n---\n\n#### **Steps in Synthesis**:\n\n##### **1. Pre-Polymer Formation (Isocyanate Reaction Stage)**:\n- Weigh the diisocyanate according to a stoichiometric ratio (NCO/OH ratio slightly above 1.05 to produce an NCO-terminated pre-polymer).\n- Add DMPA to the reaction vessel in stoichiometric proportions with OH functionality accounted for.\n- Introduce the diol (e.g., ethylene glycol) as the co-reagent.\n- Heat the reaction vessel to 60\u201380\u00b0C under nitrogen atmosphere while stirring.\n- Add the catalyst (DBTDL, typically 0.05\u20130.1% w/w) to enhance urethane linkage formation.\n\nReaction Pathway:\n\\[ \\text{R}{-}\\text{NCO} + \\text{HO}{-}\\text{R} \\rightarrow \\text{R}{-}\\text{NHCOO\u2212R} \\]\n\nRole of DMPA: The hydroxyl groups react to form urethane linkages, while the carboxylic acid groups remain unreacted.\n\n---\n\n##### **2. Neutralization (Carboxylate Formation via Ionization)**:\n- After forming the pre-polymer, introduce triethylamine (TEA) or sodium hydroxide to neutralize the carboxylic acid groups of DMPA.\n- Stir at room temperature for 30 minutes to ensure full neutralization.\n\nReaction Pathway:\n\\[ \\text{COOH} + \\text{NaOH (or TEA)} \\rightarrow \\text{COO}^- \\text{(anionic stabilization group)} \\]\n\nEffect of Neutralization: Enhances ionic stabilizing properties and increases water dispersibility due to the formation of carboxylate groups.\n\n---\n\n##### **3. Final Polymerization and Chain Extension**:\n- Introduce excess diol (optional for chain extension) or crosslinking agent to react with any remaining NCO groups.\n- Heat the mixture to 80\u201390\u00b0C for the completion of polymerization while monitoring viscosity changes.\n- Ensure complete conversion of NCO groups using an FTIR analysis (absence of peak at ~2270 cm\u207b\u00b9).\n- The resulting product will be a water-dispersible polyurethane with hydrophilic properties imparted by DMPA.\n\n---\n\n##### **4. Post-Treatment and Characterization**:\n- Dissolve the polymer in an aqueous medium to test for water dispersibility.\n- Characterize the polymer using techniques like FTIR (functional group confirmation), DSC/TGA (thermal stability), and DLS (particle size in dispersion).\n- Adjust pH and ionic strength as needed to optimize water dispersibility.\n\n---\n\n### Role of DMPA in the Polymer:\n1. **Hydrophilicity**: The hydroxyl groups of DMPA integrate into the polymer backbone, promoting water affinity.\n2. **Anionic Stabilization**: The carboxylic acid groups (after neutralization) form charged carboxylate groups that stabilize the polymer in aqueous systems and prevent aggregation.\n3. **Dispersion Enhancement**: The resulting polymer exhibits excellent water dispersibility, making it suitable for applications like coatings or adhesives.\n\n---\n\n### Final Notes:\nBy carefully controlling the reagent ratios, reaction conditions, and neutralization process, you can successfully synthesize a hydrophilic polymer with enhanced water dispersibility and stabilization properties using DMPA. Its unique structure is essential for achieving these properties.\n\nIf you have additional questions or wish to tweak the formulation for specific applications, feel free to ask!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "If polyethylene glycol (PEG) is chosen as the polyol component, outline the steps needed to introduce this molecule into the polymer chain. How does the structure of PEG contribute to the hydrophilicity of the final polymer material?"}, {"role": "assistant", "content": "Certainly! Let\u2019s break this question into two parts: first, outlining the step-by-step experimental preparation scheme for incorporating polyethylene glycol (PEG) into the polymer chain, and second, discussing how the structure of PEG enhances the hydrophilicity of the resulting polymer.\n\n---\n\n### Part 1: Experimental Preparation Scheme for Incorporating PEG into a Polymer Chain\n**Key Points of the Question:**\n- PEG is the chosen polyol component.\n- The goal is to integrate PEG into the polymer chain to enhance hydrophilicity.\n- A detailed preparation scheme is required, covering each step, including reaction conditions and reagent amounts.\n\nHere is the step-by-step synthesis process:\n\n#### Step 1: Select the Polymerization Type\nPolyethylene glycol (PEG), with its hydroxyl (-OH) end groups, is ideal for reactions that rely on hydroxyl functionality. Common polymerization methods to incorporate PEG into the chain include:\n1. **Condensation Polymerization** (e.g., with diacid chlorides or isocyanates to form polyesters or polyurethanes).\n2. **Free Radical Polymerization** (if PEG is first functionalized with acrylate or methacrylate groups).\n\nFor this example, we\u2019ll design a scheme based on **condensation polymerization**, creating a polyester by reacting PEG with a diacid or diacid chloride.\n\n---\n\n#### Step 2: Prepare Reagents\n**Key Materials:**\n- Polyethylene glycol (PEG): Select the desired molecular weight (e.g., PEG-400, PEG-600, etc.) depending on the desired flexibility and hydrophilicity in the final polymer.\n- Diacid or Diacid Chloride: Terephthaloyl chloride, succinic acid, or adipoyl chloride are commonly used.\n- Catalyst: Use a catalyst such as p-toluenesulfonic acid (PTSA) or dibutyltin dilaurate (DBTDL) to enhance the reaction rate.\n- Solvent: An inert solvent like toluene (optional for azeotropic removal of byproduct water in esterifications).\n\n---\n\n#### Step 3: Reaction Conditions and Experimental Procedures\nHere is the experimental procedure for incorporating PEG into a polyester polymer chain:\n\n1. **Pre-reaction Preparation:**\n   - Dry PEG under vacuum at 50-60\u00b0C to remove any residual moisture, as water interferes with condensation reactions.\n   - Prepare the diacid or diacid chloride in the desired molar ratio to PEG, typically a 1:1 molar ratio for linear polymers.\n\n2. **Reaction Setup:**\n   - In a three-neck round-bottom flask fitted with a stirrer, nitrogen inlet, and reflux condenser, combine PEG and the diacid/diacid chloride in the specified ratio.\n   - Add the catalyst (typically 0.5-1 wt% relative to the total monomer weight).\n\n3. **Reaction Conditions:**\n   - If using a diacid:\n     - Heat the reaction mixture gradually to 150-180\u00b0C under nitrogen to initiate esterification. Use azeotropic distillation (if a solvent like toluene is used) to continuously remove water byproduct.\n     - Maintain stirring until the reaction reaches completion, as indicated by cessation of water evolution or FTIR analysis (absence of -OH stretching).\n   - If using a diacid chloride:\n     - Keep the reaction temperature lower (50-80\u00b0C) to prevent side reactions. The reaction proceeds more rapidly, and instead of water, HCl gas is the byproduct.\n     - Provide adequate scavenging for HCl gas (e.g., add an HCl trap or conduct the reaction in a basic medium like pyridine).\n\n4. **Completion and Material Isolation:**\n   - After the reaction, cool the mixture to room temperature.\n   - Precipitate the polymer by pouring the reaction mixture into a nonsolvent (e.g., cold methanol or ethanol).\n   - Filter the precipitated polymer and wash with fresh methanol to remove any residual catalyst or unreacted monomers.\n   - Dry the polymer under vacuum at 40-50\u00b0C.\n\n5. **Structural Analysis of the Polymer:**\n   - Confirm the successful incorporation of PEG into the polymer chain using:\n     - Nuclear Magnetic Resonance (NMR) spectroscopy (look for characteristic PEG peaks at \u03b4 ~3.5 ppm).\n     - Fourier Transform Infrared (FTIR) spectroscopy (identify ester carbonyl peaks at ~1720 cm\u207b\u00b9 and absence of unreacted -OH stretches).\n\n---\n\n### Part 2: The Role of PEG in Enhancing Hydrophilicity\nPolyethylene glycol (PEG) has a unique structure that directly contributes to exceptional hydrophilicity. Here is how:\n\n1. **Molecular Structure of PEG:**\n   - PEG consists of a repeating unit: -(CH\u2082-CH\u2082-O)-. This hydrophilic backbone contains both hydrophobic (CH\u2082 groups) and hydrophilic (ether oxygen) components.\n   - The ether oxygens engage in water hydrogen bonding, while the flexible, linear chains allow for solvation and extensive interaction with water molecules.\n\n2. **Hydrophilicity Enhancement:**\n   - When incorporated into a polymer matrix, PEG acts as a hydrophilic domain. It forms pathways within the polymer that enable water absorption, resulting in increased wettability and hydrophilicity.\n   - Greater PEG content typically yields higher water uptake or water solubility, improving the polymer's performance in aqueous environments.\n   - The molecular weight of PEG also affects its hydrophilic character; shorter chains enhance hydrophilicity, while longer chains contribute more to flexibility and mechanical properties.\n\n3. **Applications:**\n   - PEG-based hydrophilic polymers are widely used in biomedical applications (e.g., hydrogels, drug delivery systems) because they resist protein adsorption and have high water retention capacity.\n   - They are also useful in coatings, membranes, and adhesives for environments requiring superior wettability.\n\n---\n\n### Summary\nTo incorporate PEG into the polymer chain, the experimental preparation involves condensation polymerization with a diacid or diacid chloride, carefully controlling the stoichiometry and reaction conditions. PEG\u2019s ether-rich structure enhances hydrophilicity by forming hydrogen bonds with water, making it crucial for biomedical, coating, and water-compatible polymer applications. Understanding PEG's chemistry and processing is essential in designing hydrophilic materials."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Using N-hydroxymethylacrylamide as a monomer, design a step-by-step polymerization process to create a hydrophilic polymer. Include details on the role of this molecule in the crosslinking structure."}, {"role": "assistant", "content": "Certainly! Let's carefully break the question down and provide a systematic, detailed explanation for the synthesis of a hydrophilic polymer utilizing **N-hydroxymethylacrylamide (NHMA)** as the monomer. We will also incorporate details on how NHMA contributes to the crosslinking structure.\n\n---\n\n### **Key Points**\n1. **N-hydroxymethylacrylamide (NHMA)** is a functional monomer that is hydrophilic due to its hydroxyl (-OH) and amide (-CONH2) groups. These enhance water solubility and hydrophilicity.\n2. NHMA possesses reactive hydroxymethyl (-CH2OH) groups that can participate in crosslinking through condensation reactions or covalent linkage.\n3. The goal is to polymerize NHMA into a hydrophilic polymer while exploiting the crosslinking ability of NHMA to enhance structural rigidity and hydrophilic properties.\n\nOur approach involves **radical polymerization**, a widely used method for synthesizing hydrophilic polymers, coupled with post-polymerization crosslinking to strengthen the structure.\n\n---\n\n### **Step-by-Step Polymerization Process Using NHMA**\n\n#### **Step 1: Preparation of Monomer Solution**\n1. **Reagents**: \n    - N-hydroxymethylacrylamide (NHMA) (monomer)\n    - Distilled deionized water (solvent, hydrophilic medium)\n    - Potassium persulfate (KPS) (initiator)\n    - N,N'-methylenebisacrylamide (MBA) (optional crosslinker, if enhanced structural rigidity is desired)\n2. **Steps**:\n    - Dissolve **NHMA** monomer (e.g., 10 g) in distilled deionized water (e.g., 50 mL) to form a clear solution. Stir gently to ensure uniform dissolution.\n    - If desired, add **N,N'-methylenebisacrylamide** (~0.2 g) as an external crosslinking agent. For this experiment, NHMA\u2019s hydroxymethyl (-CH2OH) group will also act as an intrinsic crosslinker.\n    - Prepare a separate solution of **potassium persulfate** (1 g in 10 mL water).\n\n#### **Step 2: Creation of Reaction Medium**\n1. **Reaction Vessel**: A clean glass reactor or flask equipped with magnetic stirring, a nitrogen inlet, a thermometer, and a heating mantle.\n2. **Nitrogen Purging**:\n    - Purge the monomer solution with nitrogen gas (10-15 min) to eliminate dissolved oxygen, as oxygen inhibits radical polymerization.\n\n#### **Step 3: Initiation of Radical Polymerization**\n1. **Reaction Conditions**:\n    - **Temperature**: Heat the reactor to ~70\u00b0C (optimal for potassium persulfate decomposition).\n    - **pH**: NHMA is stable in slightly acidic to neutral conditions (pH ~6-7), allowing ideal polymerization.\n2. **Procedure**:\n    - Gradually add the potassium persulfate solution to the monomer solution under constant stirring.\n    - Maintain stirring to ensure uniform mixing of initiator with monomer.\n    - Monitor the viscosity of the solution; the viscosity will increase as polymerization progresses (indicative of polymer formation).\n\n#### **Step 4: Polymerization Monitoring**\n1. **Reaction Duration**: Allow the polymerization reaction to proceed for 3-4 hours at 70\u00b0C.\n2. **Observations**:\n    - Gel formation or solution thickening indicates increasing molecular weight.\n    - Hydrophilic properties can be tested by sampling the polymer and dissolving it in water.\n\n---\n\n### **Step 5: Crosslinking**\nThe hydroxymethyl (-CH2OH) group of NHMA provides intrinsic crosslinking functionality. During polymerization, NHMA monomers can react via condensation reactions (elimination of water) or covalent bonding between hydroxymethyl groups, forming crosslinked structures.\n\n1. **Heating Step**:\n    - Post-polymerization, heat the polymer solution gently (~90\u00b0C) to encourage crosslinking via the hydroxymethyl (-CH2OH) groups. This forms a stronger network.\n    - Optionally, increase pH slightly (~8-9 using sodium carbonate) to enhance hydroxymethyl reactivity.\n\n2. **Optional Crosslinker Addition**:\n    - If additional crosslinking agents like **MBA** were added earlier, ensure controlled heating and stirring to promote uniform crosslink formation.\n\n---\n\n### **Step 6: Polymer Purification**\n1. **Dilution and Washing**:\n    - Dilute the polymerized solution with excess water to enhance hydration and dissolve any unreacted NHMA monomers.\n    - Wash the polymer thoroughly with water or ethanol (if soluble contaminants exist) to remove residual chemicals (e.g., initiator, unreacted monomers).\n2. **Precipitation**:\n    - Precipitate the polymer by adding it to a non-solvent (e.g., acetone or ethanol) if the polymer is insoluble in these solvents.\n3. **Drying**:\n    - Wash the polymer further and air dry it at room temperature or under mild vacuum at a slightly elevated temperature (~40-50\u00b0C).\n\n---\n\n### **Step 7: Characterization**\nTo confirm successful polymerization and crosslinking:\n1. **Solubility Test**: Evaluate the hydrophilicity of the polymer by testing its solubility in water.\n2. **FTIR Analysis**:\n    - Validate the presence of hydroxyl (-OH) and amide (-CONH2) functional groups, as well as evidence of crosslinking.\n3. **Thermal Analysis**: \n    - Differential Scanning Calorimetry (DSC) or Thermogravimetric Analysis (TGA) can confirm structural stability and crosslinking density.\n\n---\n\n### **Role of NHMA in Crosslinking**\n1. The hydroxymethyl (-CH2OH) group in NHMA acts as an intrinsic crosslinking site. During polymerization, adjacent NHMA units can form covalent or hydrogen bonds between their hydroxymethyl groups.\n2. Such crosslinking enhances the polymer's structural integrity, reduces solubility (in excessive crosslinking cases), and contributes to a three-dimensional network that retains high hydrophilicity due to remaining hydroxyl and amide groups.\n\n---\n\n### **Conclusion**\nBy this step-by-step approach, students can synthesize a hydrophilic polymer using NHMA while understanding its dual role as a monomer and a crosslinking agent. Following systematic laboratory practices\u2014careful control over reaction conditions, monomer ratios, and crosslinking\u2014ensures reproducibility and successful polymer generation.\n\nIf any step requires clarification, feel free to ask!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Design a complete experimental setup using phenolic epoxy as the starting polymer and describe how you would incorporate a functional group using triethanolamine to make the polymer hydrophilic. Include the necessary reactants, solvents, and environmental conditions (e.g., temperature, pH) for the synthesis."}, {"role": "assistant", "content": "Certainly! Let us carefully dissect your question and systematically create an experimental plan to synthesize a hydrophilic polymer using phenolic epoxy as the starting material and incorporating triethanolamine to enhance hydrophilicity. I shall break this process into a thoughtful, step-by-step experimental preparation scheme and ensure the details are intuitive and practical, focusing on the mechanistic considerations, experimental conditions, and rationale behind each step.\n\n---\n\n### **I. Key Analysis of the Question:**\n\n1. **Starting Polymer:** Phenolic epoxy polymer. It has reactive epoxide groups and phenolic moieties, which are amendable to reaction.\n   \n2. **Goal:** To introduce hydrophilic functional groups into the polymer structure to enhance its hydrophilicity.\n\n3. **Key Reactant:** Triethanolamine is a small molecule bearing three hydroxyl groups (-OH) and an amine (-NH) group. These groups can react with the epoxide in phenolic epoxy and provide hydrophilic functionality.\n\n4. **Chemical Strategy:** A **nucleophilic ring-opening reaction** where triethanolamine reacts with the epoxide rings in the phenolic epoxy backbone is the most appropriate pathway. This forms covalent bonds between triethanolamine and the polymer, while also increasing hydroxyl content.\n\n5. **Experimental Setup:** The scheme must include:\n   - Controlled reaction conditions for selective epoxide ring opening.\n   - A suitable solvent for uniform mixing of phenolic epoxy and triethanolamine.\n   - Post-reaction workup for purification and characterization.\n\n---\n\n### **II. Complete Experimental Preparation Scheme:**\n\nThe preparation scheme involves the following distinct steps:\n\n---\n\n#### **Step 1: Materials and Reagents**\n1. **Materials Needed:**\n   - Phenolic epoxy polymer (commercially available or synthesized as oligomers with controllable molecular weight).\n   - Triethanolamine (TEA, reagent grade, >99% purity).\n   - Solvent: Dimethylformamide (DMF, anhydrous, polar aprotic solvent).\n   - Catalyst (optional): Tertiary amine (e.g., N,N-dimethylbenzylamine (BDMA)) or heat.\n   - Deionized water (for post-reaction clean-up).\n   - Ethanol (for polymer washing and precipitation).\n\n2. **Apparatus:**\n   - A three-neck round-bottom flask (for temperature control and stirring).\n   - Magnetic stirrer with heating capabilities.\n   - Thermometer.\n   - Inert nitrogen gas setup.\n   - Condenser (if performing longer reactions).\n\n---\n\n#### **Step 2: Reaction Conditions and Functionalization Protocol**\n\n1. **Dissolution of Polymer:**\n   - Weigh 5 g of phenolic epoxy polymer and dissolve it in 50 mL of DMF in the three-neck flask under constant stirring at room temperature.\n   - Ensure complete dissolution of the polymer in DMF, as this provides a homogenous medium for reaction.\n   - Remove residual oxygen by purging with nitrogen gas for 10\u201315 minutes, as oxygen could interfere (e.g., through unwanted side reactions with radicals).\n\n2. **Addition of Triethanolamine:**\n   - Measure the molar equivalent amount of triethanolamine based on the number of epoxy groups in the starting polymer. Assume theoretical calculations: one mole of triethanolamine per mole of epoxide functionalities.\n   - Typically, use **1.05 mol** of TEA per mol of the epoxy groups to ensure complete reaction.\n   - Add the triethanolamine dropwise into the reaction solution to avoid exothermic overheating from the nucleophilic reaction.\n\n3. **Reaction Conditions:**\n   - Heat the reaction mixture to **80\u201390\u00b0C**, the optimal range for the epoxide ring-opening reaction.\n   - Stir constantly to maintain homogeneity.\n   - Maintain the heat and stirring for approximately **6\u20138 hours**, ensuring complete conversion of the epoxide groups.\n   - Monitor the reaction periodically using an appropriate method, such as FTIR spectroscopy (look for disappearance of the epoxy peak near 915 cm\u207b\u00b9 and appearance of hydroxyl groups at ~3200\u20133500 cm\u207b\u00b9).\n\n4. **Optional Catalyst:** To accelerate the process, you may add 0.5 wt% BDMA to the reaction mixture as a catalyst for epoxide ring opening.\n\n---\n\n#### **Step 3: Post-Reaction Workup**\n\n1. **Precipitation of Functionalized Polymer:**\n   - After completion of the reaction, cool the mixture to room temperature.\n   - Slowly add the reaction solution into a large excess (500 mL) of ethanol under stirring. This step precipitates the functionalized polymer.\n\n2. **Washing and Purification:**\n   - Wash the precipitated polymer with ethanol and deionized water to remove any unreacted triethanolamine and DMF residues.\n   - Dry the purified polymer in a vacuum oven at **40\u201350\u00b0C** until constant weight is achieved.\n\n---\n\n#### **Step 4: Characterization of the Hydrophilic Polymer**\n\n1. **Hydrophilicity Measurement:**\n   - Evaluate the hydrophilicity of the functionalized polymer using water contact angle measurements. A decrease in the contact angle compared to the starting material confirms improved hydrophilicity.\n   \n2. **Structural Characterization:**\n   - Use FTIR spectroscopy to confirm the successful ring-opening reaction (e.g., disappearance of epoxy group signal and appearance of O-H stretching from hydroxyl groups).\n   - Use NMR spectroscopy to confirm the covalent bonding between triethanolamine and the polymer backbone.\n   \n3. **Thermal and Mechanical Property Analysis:**\n   - Test properties such as thermal stability (TGA analysis) or mechanical integrity of the hydrophilic polymer using DMA.\n\n---\n\n### **III. Summary of the Experimental Setup**\n\n- **Reaction Type:** Nucleophilic epoxide ring-opening with triethanolamine.\n- **Polymer Functionalization:** Formation of hydroxyl-rich functionalized phenolic epoxy polymer.\n- **Solvent:** DMF (polar aprotic) for efficient reaction.\n- **Reaction Conditions:** 80\u201390\u00b0C for 6\u20138 hours under stirring, in the presence of inert nitrogen gas.\n- **Post-Reaction Workup:** Precipitate in ethanol, wash, and dry.\n- **Characterization Tools:** FTIR, NMR, contact angle measurement.\n\n---\n\nBy reacting phenolic epoxy with triethanolamine under the above conditions, hydrophilic hydroxyl and secondary amine functionalities will be incorporated into your polymer backbone, making it significantly more hydrophilic.\n\nGood luck with your experiments, and feel free to return with any further questions about synthesis or characterization!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe how glycidyl methacrylate (GMA) can be used to modify a polymer to introduce hydrophilic properties. Include the reaction mechanism and the functional groups formed during the process."}, {"role": "assistant", "content": "Certainly! Let us proceed step by step in tackling this question systematically, based on your request.\n\n---\n\n### **Step 1: Analyze the Question and Summarize Key Points**\n1. **What is being modified?**\n   A polymer (generic or existing polymer) is the starting substrate.\n   \n2. **What is introduced?**\n   Hydrophilic properties need to be incorporated into the polymer.\n\n3. **What reagent is used?**\n   Glycidyl methacrylate (GMA) is the modifying reagent of interest.\n\n4. **Mechanism and functional groups?**\n   A detailed explanation of how modification occurs, including the reaction mechanism and the hydrophilic functional groups formed, is required.\n\nKey takeaways: We need a comprehensive synthesis scheme where Glycidyl Methacrylate (GMA) modifies a polymer to improve hydrophilicity, detailing reaction pathways, functional groups formed, and experimental conditions.\n\n---\n\n### **Step 2: Explanation of the Synthesis Process**\n\nGlycidyl methacrylate (GMA) is a versatile monomer commonly used to functionalize polymers. Its molecular structure includes a methacrylate group and an epoxide group. By leveraging the chemical reactivity of these groups, GMA introduces hydrophilic functional groups, such as hydroxyl (-OH) or additional polar functionalities, into the polymer backbone. Here's a detailed step-by-step experimental design:\n\n---\n\n#### **Step 2.1: Select the Base Polymer**\nThe choice of the base polymer depends on the intended application. Common examples include:\n   - **Polyethylene (PE)** or **Polypropylene (PP)** (non-functionalized polymers).\n   - **Poly(methyl methacrylate) (PMMA)**, which already has functionalized methacrylate groups.\n   - **Poly(vinyl alcohol) (PVA)** or similar hydrophilic polymers that might benefit from further functionalization.\n\nFor simplicity, I'll assume the polymer contains reactive groups such as hydroxyl (-OH), amine (-NH\\(_2\\)), or carboxyl (-COOH) groups. \n\n---\n\n#### **Step 2.2: Proposed Reaction**\nWhen modifying a polymer using GMA, the two main functionalities of GMA (the **epoxide group** and **methacrylate group**) play distinct roles based on the polymer involved.\n\n1. **Epoxide Ring Opening Reaction**\n   - The epoxide group of GMA can react with nucleophilic groups on the surface of the polymer.\n   - Common nucleophilic groups include hydroxyl (-OH), amine (-NH\\(_2\\)), and carboxyl (-COO\\(^-\\)).\n   - Upon reaction, the epoxide ring opens to form **hydroxyether** linkages, resulting in new hydroxyl (-OH) groups that enhance the polymer's hydrophilicity.\n\n2. **Methacrylate Polymerization**\n   - If free-radical polymerization or copolymerization is desired, the methacrylate group of GMA can undergo polymerization to link with other monomers, creating a network that includes GMA units.\n\n---\n\n#### **Step 2.3: Reaction Mechanism**\n\nHere we focus on the **epoxide ring-opening reaction**, the most common scenario for hydrophilicity enhancement:\n\n1. **Activation of Nucleophile and Ring Opening:**\n   - A nucleophile (e.g., -OH, -NH\\(_2\\), or COO\\(^-\\)) attacks the less sterically hindered carbon in the epoxide ring of GMA.\n   - This results in ring opening and the formation of one hydroxyl group and one ether group. (For amine nucleophiles, the product is a \u03b2-amino alcohol.)\n\n2. **Example Reaction with a Hydroxyl Group (-OH):**\n   \\[\n   R-OH + \\text{[CH}_2\\text{-O-CH-CH}_2\\text{]} \\rightarrow R-O-CH_2CH(OH)CH_2 \\, \n   \\]\n\n---\n\n#### **Step 2.4: Experimental Procedure**\n\nBelow is a systematic approach for modifying a polymer using GMA.\n\n**Materials Needed:**\n   - Glycidyl methacrylate (GMA).\n   - A polymer substrate (e.g., polyvinyl alcohol, polyethylene glycol, etc.).\n   - Solvent: Use an inert, non-reactive solvent such as dimethylformamide (DMF) or toluene, depending on polymer solubility.\n   - Catalyst: Typically, a base such as triethylamine (TEA) or potassium hydroxide (KOH) facilitates epoxide ring opening.\n   - Optional radical initiator (for methacrylate polymerization): Azobisisobutyronitrile (AIBN).\n\n**Reaction Steps:**\n1. **Dissolution of Polymer:**\n   - Dissolve the polymer in a suitable solvent (e.g., PVA in water, PMMA in DMF).\n   - Polymer concentration: 1\u20135 wt.%.\n   \n2. **Addition of GMA:**\n   - Add glycidyl methacrylate to the reaction system. The GMA concentration is typically 5\u201310 mol-% with respect to the polymer repeat unit.\n\n3. **Catalyst Addition:**\n   - Add TEA or KOH (catalyst) to facilitate the epoxide ring opening.\n   - The typical molar ratio of catalyst to GMA is ~1:10.\n\n4. **Reaction Conditions:**\n   - Stir the mixture at 50\u201370 \u00b0C to promote reaction.\n   - Maintain the reaction for 6\u201312 hours to ensure complete functionalization.\n\n5. **Neutralization (Optional):**\n   - If a base catalyst is used (e.g., KOH), neutralize the solution using dilute acid (e.g., acetic acid) after reaction.\n\n6. **Purification:**\n   - Precipitate and isolate the modified polymer by adding the reaction mixture to a non-solvent (e.g., ethanol for PVA) to remove unreacted GMA.\n   - Dry the polymer under vacuum at 50\u201360 \u00b0C to constant weight.\n\n---\n\n### **Step 3: Hydrophilic Functional Groups Introduced**\n\nAfter the modification, the polymer surface gains hydroxyl (-OH) groups or secondary hydrophilic linkages arising from the opened epoxide. These groups:\n1. Improve wettability due to hydrogen-bond donating and accepting capacity.\n2. Allow for further functionalization or compatibility with aqueous systems.\n\n---\n\n### **Step 4: Additional Insights**\n1. **Copolymerization Option:**\n   - If using the methacrylate functionality of GMA, copolymerization with monomers like acrylamide or acrylic acid can result in a polymer with both hydrophilic and cross-linked properties.\n   - Radical initiators (e.g., AIBN) and thermal curing (65\u201380 \u00b0C) are typically required for this approach.\n\n2. **Applications:**\n   - Biomedical polymers (e.g., hydrogels, drug delivery systems).\n   - Coatings with anti-fouling or water-compatible properties.\n   - Adhesion promoters or surface-active agents.\n\n---\n\n### **Conclusion**\nTo modify a polymer and enhance its hydrophilicity, glycidyl methacrylate (GMA) can be used effectively due to its epoxide ring, which reacts with nucleophiles in the polymer, introducing hydroxyl groups. This process requires a suitable solvent, a catalytic base (KOH or TEA), and optimized reaction conditions (50\u201370 \u00b0C, 6\u201312 hours). The resulting hydrophilic polymer shows improved interaction with aqueous environments, expanding its application scope.\n\nIf you have further questions about implementing this method in the lab, do not hesitate to ask!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Propose a purification method to isolate the final product after modifying a polymer with dopamine hydrochloride. How would you ensure the product\u2019s hydrophilicity is preserved during purification?"}, {"role": "assistant", "content": "To design an effective purification method to isolate a polymer modified with dopamine hydrochloride, while ensuring the polymer\u2019s hydrophilicity is preserved, we need to approach this systematically. Below is the step-by-step analysis and detailed experimental procedure.\n\n---\n\n### **1. Key Points Analysis**\n- **Objective:** Isolate the dopamine-modified polymer after synthesis and ensure the hydrophilicity imparted by dopamine hydrochloride is retained during purification.\n- **Challenges:** Dopamine hydrochloride is hydrophilic and prone to oxidation during purification. Preservation of the polymer's hydrophilic features and avoidance of degradation or loss during purification must be considered.\n- **Focus:** Selection of purification techniques suited to hydrophilic polymers, avoiding exposure to conditions (e.g., high temperature, oxidative atmospheres) that might affect the dopamine structure.\n\n---\n\n### **2. Proposed Purification Method**\nThe purification process involves the removal of unreacted reagents, by-products, and residual solvents while retaining the hydrophilic properties of the modified polymer. Here's a systematic approach:\n\n#### Step 1: **Dilution and Solubilization**\n- **Objective:** Prevent aggregation or loss of hydrophilicity during purification.\n- **Procedure:**\n  - Dissolve the polymer solution in a hydrophilic solvent or solvent mixture that enhances solubility. For dopamine-modified polymers, aqueous media is ideal. Use water, ethanol, or a buffer solution with a neutral pH (e.g., phosphate-buffered saline at pH 7.4) to maintain dopamine's stability.\n  - Confirm solubility using gentle stirring or sonication (avoid high agitation to prevent heat buildup).\n\n#### Step 2: **Dialysis**\n- **Objective:** Remove low molecular weight impurities, unreacted dopamine hydrochloride, and small by-products.\n- **Procedure:**\n  - Select a dialysis membrane with a molecular weight cut-off (MWCO) appropriate for the polymer size (e.g., MWCO of 10,000 Da for smaller polymers or 50,000 Da for larger ones).\n  - Immerse the dialysis bag in deionized water or buffer solution maintained at neutral pH to avoid oxidation of dopamine functional groups.\n  - Exchange the dialysis water or buffer every 3\u20134 hours for the first 12 hours, then every 6\u20138 hours thereafter. Perform dialysis for 24\u201348 hours, depending on purity requirements.\n  - Ensure the dialysis system remains in a low-temperature environment (typically at ~4\u00b0C) to prevent polymer degradation or dopamine oxidation.\n\n#### Step 3: **Precipitation (if needed)**\n- **Objective:** Isolate the polymer by precipitation without compromising its hydrophilic character.\n- **Procedure:**\n  - Gradually add a non-solvent (e.g., acetone or ethanol) into the polymer solution with stirring to precipitate the polymer selectively.\n  - Avoid excessive non-solvent addition since it may cause collapse of hydrophilic chains or loss of dopamine functional groups.\n  - Collect the precipitate via centrifugation or filtration.\n\n#### Step 4: **Ultrafiltration or Size-Exclusion Chromatography**\n- **Objective:** Further purify the polymer by removing higher and lower molecular weight contaminants.\n- **Procedure:**\n  - Use ultrafiltration techniques employing hydrophilic membranes to selectively retain the polymer while removing impurities.\n  - Alternatively, pass the solution through size-exclusion chromatography (SEC) using a hydrophilic column (e.g., Sephadex or Superdex columns) to ensure separation while retaining the polymer\u2019s hydrophilicity.\n\n#### Step 5: **Final Drying**\n- **Objective:** Obtain the purified polymer in solid form without compromising its structure or hydrophilicity.\n- **Procedure:**\n  - Lyophilize (freeze-dry) the purified solution rather than subjecting it to oven drying. Lyophilization avoids exposure to heat and preserves hydrophilic features.\n  - Confirm the drying chamber is flushed with inert gas (e.g., nitrogen) to reduce oxidative stress on dopamine groups.\n\n---\n\n### **3. Ensuring Product Hydrophilicity During Purification**\nTo preserve the hydrophilic properties:\n1. **Control pH:** Keep the pH neutral throughout dialysis and filtration steps (e.g., ~pH 7\u20137.5). Dopamine hydrochloride can degrade or oxidize in acidic or basic conditions.\n2. **Protect from Oxidation:** Perform all handling in low-temperature environments and, where possible, under an inert atmosphere (e.g., nitrogen or argon). Dopamine is prone to oxidative degradation.\n3. **Maintain Solubility:** Use hydrophilic solvents or buffers to ensure polymer chains remain hydrated and functional groups (e.g., amine and hydroxyl groups) do not collapse or aggregate.\n4. **Avoid Heat:** Prefer cold methods such as lyophilization, dialysis, or ultrafiltration to eliminate heat exposure, which could damage functional groups.\n\n---\n\n### **4. Verification of Purification**\nAfter purification, verify the polymer\u2019s hydrophilicity through:\n- **Water Contact Angle Measurement:** A decrease in the contact angle compared to the unmodified polymer indicates enhanced hydrophilicity.\n- **Fourier-Transform Infrared (FTIR) Spectroscopy:** Check for characteristic peaks (e.g., O-H and N-H stretching) to confirm the presence of hydrophilic groups.\n- **Nuclear Magnetic Resonance (NMR):** Verify that dopamine groups remain intact post-purification.\n- **Thermogravimetric Analysis (TGA):** Confirm no degradation occurred during purification steps.\n\n---\n\nWith this detailed purification approach, your polymer modified with dopamine hydrochloride can be isolated while retaining its hydrophilic properties. Let me know if you require further clarification or guidance!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Given that 1,3,5-triformylbenzene (TFB) can react with both amino and hydroxyl groups, detail an experimental approach to incorporate TFB into a polymer coating for hydrophilic surface modification."}, {"role": "assistant", "content": "Certainly! Let us analyze your question systematically and design an experimental preparation scheme for incorporating 1,3,5-triformylbenzene (TFB) into a polymer coating for hydrophilic surface modification.\n\n### **Step 1: Analyze the key points in the question**\n1. **Target molecule properties**: TFB has reactive formyl (\u2013CHO) groups capable of undergoing condensation reactions with amino (\u2013NH\u2082) or hydroxyl (\u2013OH) groups.\n2. **Objective**: Incorporate TFB into a polymer coating to enhance hydrophilicity.\n3. **Reaction pathways**: Given TFB\u2019s chemical properties, the primary reactions likely involve Schiff base formation (reaction with amines) or acetal formation (reaction with hydroxyl groups).\n4. **Experimental goal**: Develop a hydrophilic polymer coating with surface modification that leverages TFB's functionality to improve hydrophilicity and performance.\n\n### **Step 2: Design the experimental scheme**\nWe will develop a step-by-step synthesis methodology, including reagent choices, reaction conditions, molar ratios, and equipment requirements.\n\n---\n\n#### **Step 2.1: Selection of polymer backbone**\nTo design a hydrophilic polymer coating, we select a polymer featuring either amino groups (e.g., polyethyleneimine) or hydroxyl groups (e.g., polyvinyl alcohol, PVA). Both polymers are inherently hydrophilic and thus provide a foundation for improving surface hydrophilicity.\n\nFor this synthesis, we will use **polyethyleneimine (PEI)** due to its abundant amino groups available for Schiff base condensation with TFB.\n\n#### **Step 2.2: Preparation of the polymer solution**\nPrepare an aqueous solution of PEI for the reaction:\n- **Reagents**:\n  - Branched polyethyleneimine (PEI) with a molecular weight of ~25,000.\n  - Deionized water.\n- **Procedure**:\n  - Dissolve PEI in deionized water at a concentration of 10 wt% (e.g., 10 g PEI in 100 mL water).\n  - Stir the solution at room temperature for 30 minutes until fully dissolved.\n- **Notes**: The resulting PEI solution serves as the base polymer for surface modification.\n\n---\n\n#### **Step 2.3: Adding TFB to the reaction**\nIntroduce TFB into the PEI solution to begin the Schiff base formation reaction:\n- **Reagents**:\n  - 1,3,5-Triformylbenzene (TFB; molecular weight = 192.14 g/mol).\n- **Procedure**:\n  - For every 10 g of PEI, add TFB in a molar ratio of **1:3** (TFB-to-primary amines).\n  - Approximate calculation:\n    - PEI has ~7 mmol primary amines per gram. For 10 g PEI, the total amines = 70 mmol.\n    - Add 23.33 mmol TFB (equivalent to ~4.48 g TFB).\n  - Dissolve TFB in ethanol or dimethyl sulfoxide (DMSO) to achieve complete solubility, then add this solution dropwise into the stirring PEI solution.\n\n---\n\n#### **Step 2.4: Reaction conditions**\nPerform the Schiff base condensation reaction under optimized conditions:\n- **Reaction environment**:\n  - Maintain the reaction at **50\u201360 \u00b0C** to promote condensation between formyl groups (TFB) and amino groups (PEI).\n  - Adjust the pH to ~8 using triethylamine or dilute NaOH to facilitate the reaction but avoid hydrolysis of the Schiff base.\n- **Time**:\n  - Stir the reaction mixture for 6\u201312 hours under nitrogen atmosphere to prevent oxidation.\n- **Mixing apparatus**:\n  - Use a magnetic stirrer for homogeneous mixing and a sealed reaction vessel for reducing contamination.\n\n---\n\n#### **Step 2.5: Purification of the polymer**\nIsolate and purify the modified polymer to remove unreacted TFB:\n- **Procedure**:\n  - Dialyze the reaction product against deionized water (using dialysis tubing, molecular weight cutoff ~12\u201314 kDa).\n  - Perform dialysis for up to 48 hours with frequent water changes to remove small molecule impurities.\n\n---\n\n#### **Step 2.6: Formation of hydrophilic polymer coating**\nApply the purified polymer onto the desired substrate to create a hydrophilic coating:\n- **Coating procedure**:\n  - Dissolve 1\u20135 wt% of the purified polymer in water or ethanol.\n  - Clean the substrate (e.g., glass, silicon wafer, or metal) with ethanol and deionized water, then dry thoroughly.\n  - Use spin coating, dip coating, or spray coating to apply the polymer solution evenly on the surface.\n  - Dry the coated substrate at **60\u201380 \u00b0C** in a vacuum oven for 2\u20133 hours to remove residual solvents and enhance adhesion.\n\n---\n\n### **Reaction scheme:**\nThe reaction between TFB and PEI follows this simplified chemical pathway:\n#### TFB + Amino groups (PEI) \u2192 Schiff base-modified PEI\nThe Schiff base structure (\u2013C=N\u2013) enhances surface hydrophilicity by introducing polar functional groups while maintaining polymer stability.\n\n---\n\n### **Step 3: Summary of the experiment**\n1. Dissolve PEI in deionized water to prepare the polymer base.\n2. Add TFB to the PEI solution in a controlled molar ratio of 1:3 (TFB-to-primary amine groups).\n3. Perform the reaction under mild temperature (50\u201360 \u00b0C) and optimized pH (~8) for 6\u201312 hours.\n4. Purify the modified polymer by dialysis to remove unreacted TFB.\n5. Coat the substrate with the polymer and cure at elevated temperatures to finalize the hydrophilic coating.\n\n### **Scientific rationale and expected outcome:**\nThe incorporation of TFB via Schiff base formation introduces polar groups into the polymer matrix, enhancing water affinity and hydrophilicity. This functionalized polymer coating should provide improved wettability and adhesion properties for surface modification applications.\n\nIf you have further questions, feel free to ask, and I\u2019ll gladly assist in refining any step or explaining the underlying chemistry!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Based on the molecule ethyl hydroxyethyl cellulose, explain how you would utilize it in the preparation of a hydrophilic polymer coating to enhance the polymer's wettability. Include the rationale behind its inclusion in the composition."}, {"role": "assistant", "content": "Certainly! Let\u2019s break down your question systematically to ensure thorough understanding and practical application for the preparation of a hydrophilic polymer coating using ethyl hydroxyethyl cellulose (EHEC). \n\n---\n\n### **Step 1: Analyze the Question \u2013 Key Points**\nThe molecule mentioned, **ethyl hydroxyethyl cellulose (EHEC)**, is a cellulose derivative. It contains both hydrophobic ethyl groups and hydrophilic hydroxyethyl groups, making it a surface-active agent. Its structure makes it highly valuable in improving hydrophilicity due to its excellent water retention and film-forming properties. Your question is to design a synthesis scheme for a **hydrophilic polymer coating**, aimed at enhancing the polymer's wettability.\n\nThus, the focus is:\n- Incorporating EHEC into the coating composition.\n- Optimizing the reaction to maximize hydrophilic properties.\n- Ensuring clear steps, conditions, and rationale for achieving a successful hydrophilic polymer film.\n\n---\n\n### **Step 2: Detailed Experimental Preparation Scheme**\nHere is a systematic approach for preparing a hydrophilic polymer coating using ethyl hydroxyethyl cellulose:\n\n---\n\n#### **Step 2.1: Gather Materials and Reagents**\nBefore starting, gather the following:\n1. **Ethyl Hydroxyethyl Cellulose (EHEC)** \u2013 hydrophilic component.\n2. **Acrylic Monomer** \u2013 such as acrylic acid (AA), acrylamide (AM), or hydroxyethyl methacrylate (HEMA) for polymer backbone formation.\n3. **Crosslinker** \u2013 such as N,N'-methylenebisacrylamide (MBA) to provide structural stability to the polymer network.\n4. **Initiator** \u2013 such as ammonium persulfate (APS) or potassium persulfate (KPS) for radical polymerization.\n5. **Deionized Water** \u2013 used as the reaction medium to aid hydrophilic interaction.\n6. **Neutralization Agent** \u2013 e.g., sodium hydroxide (NaOH), to adjust the pH of acrylic acid to improve solubility.\n\n---\n\n#### **Step 2.2: Design the Reaction Procedure**\nNow, let us synthesize the hydrophilic polymer coating step by step.\n\n---\n\n##### **Step 2.2.1: Prepare the EHEC Solution**\n- **Purpose**: Dissolve EHEC to distribute it homogeneously in the reaction matrix.\n- **Procedure**:\n   1. Measure **2-5 wt% of EHEC** relative to the final polymer solution\u2019s weight. The exact percentage can vary based on the hydrophilicity required.\n   2. Add EHEC slowly to **deionized water** under continuous stirring (around 300 rpm).\n   3. Heat the solution to **50-60\u00b0C** to promote complete dissolution, as EHEC dissolves more readily at elevated temperatures.\n   4. Stir until a clear viscous solution is obtained.\n- **Rationale**: EHEC acts as a film-former and hydrophilicity enhancer; a homogeneous solution ensures uniform properties throughout the film.\n\n---\n\n##### **Step 2.2.2: Prepare the Monomer Solution**\n- **Purpose**: Mix acrylic monomers and adjust the pH for solubility and polymerization readiness.\n- **Procedure**:\n   1. Add **acrylic acid (10 wt%)** to a separate container of water under stirring. Acrylic acid imparts hydrophilic carboxylic groups to the polymer.\n   2. **Neutralize the acrylic acid** by slowly adding 2 M NaOH until the solution pH reaches around **6.5\u20137.5**. This avoids excess acidity that might disrupt polymerization.\n   3. Add **1\u20132 wt% hydroxyethyl methacrylate (HEMA)** or acrylamide (AM), which contribute additional hydrophilic functional groups. Adjust the ratio if you wish to vary hydrophilic and mechanical properties.\n   4. Mix thoroughly to ensure all monomers are well-dispersed.\n\n---\n\n##### **Step 2.2.3: Combine Solutions**\n- **Purpose**: Blend EHEC into the monomer solution for copolymerization.\n- **Procedure**:\n   1. Slowly pour the prepared **EHEC solution** into the monomer solution while stirring continuously at 300-400 rpm.\n   2. Ensure no clumping occurs, and the mixture forms a uniform, viscous solution.\n- **Rationale**: EHEC integrates into the polymer matrix during polymerization, contributing hydroxyl groups and hydrophilic features.\n\n---\n\n##### **Step 2.2.4: Initiate Polymerization**\n- **Purpose**: Start radical polymerization to form the hydrophilic polymer.\n- **Procedure**:\n   1. Cool the solution to **25-30\u00b0C**, then add the initiator (e.g., 0.5 wt% APS) under gentle stirring.\n   2. Optionally, add **crosslinker** (e.g., 1 wt% MBA) to create a 3D network for more robustness.\n   3. Degas the solution by bubbling nitrogen gas through it for 30 minutes to prevent oxygen inhibition.\n   4. Heat the reaction vessel to **60-70\u00b0C** and maintain it for 2\u20133 hours to allow polymerization to proceed.\n- **Rationale**: Radical polymerization promotes the copolymerization of acrylic monomers with EHEC, forming a hydrophilic copolymer.\n\n---\n\n##### **Step 2.2.5: Coat the Substrate**\n- **Purpose**: Apply the polymer solution as a coating for testing hydrophilicity.\n- **Procedure**:\n   1. Once the polymerization is complete, cool the viscous polymer solution to room temperature.\n   2. Spin-coat or dip-coat the solution onto the desired substrate (e.g., glass, plastic) to form a thin film.\n   3. Dry the coated substrate at **40-50\u00b0C** in a vacuum oven for 24 hours to remove residual moisture and stabilize the film.\n- **Rationale**: Coating the substrate allows for testing of the hydrophilic properties imparted by the EHEC-polymer matrix.\n\n---\n\n#### **Step 2.3: Evaluate the Hydrophilic Polymer Coating**\n- **Contact Angle Measurement**: Measure the water contact angle of the coated surface to assess wettability. A smaller contact angle (<30\u00b0) indicates good hydrophilicity.\n- **Film Uniformity**: Inspect the film for transparency and defects to ensure quality.\n- **Water Retention**: Perform a water absorption or retention test to quantify hydrophilicity.\n\n---\n\n### **Step 3: Rationale for Using EHEC**\n- **Enhances Hydrophilicity**: EHEC contains abundant hydroxyl (-OH) groups that attract water molecules, reducing the water contact angle.\n- **Improves Film-Forming Ability**: Its cellulose backbone contributes to the uniformity and stability of the coating.\n- **Prevents Aggregation**: EHEC provides steric stabilization, ensuring even distribution of hydrophilic properties in the final polymer matrix.\n- **Environment-Friendly**: As a cellulose derivative, EHEC is biodegradable and non-toxic, making the process sustainable.\n\n---\n\n### **Conclusion**\nIn this process, EHEC serves as a vital component for enhancing the hydrophilicity of the polymer coating by introducing hydroxyl groups and water-compatible structures. By following the detailed protocol above, you should be able to successfully prepare a hydrophilic polymer coating with improved wettability."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the procedure for incorporating [Fe(CN)6]^{3-/4-} into the polymer matrix and discuss how this step ensures consistent interaction between the molecule and polymer network to improve hydrophilicity."}, {"role": "assistant", "content": "Certainly! Let us systematically approach your question about incorporating \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) into a polymer matrix while ensuring consistent interaction between the molecule and the polymer network to improve hydrophilicity. The molecule \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) has unique properties due to its charged nature and ability to form complex interactions, making it a viable candidate for enhancing hydrophilicity through electrostatic and chemical interactions with a polymeric network.\n\n### Step 1: Analysis of the Question\nKey points of your question:\n1. The goal is to incorporate \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) into a polymer matrix.\n2. The polymer should maintain consistent interactions with \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) to improve hydrophilicity.\n3. The procedure must include a step-by-step detailed experimental protocol backed with reaction conditions, reagent ratios, and practical considerations.\n\nBy analyzing this, it is evident that we need to:\n- Choose a polymer with functional groups that enable interaction with \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\).\n- Ensure uniform dispersion of the molecule throughout the polymer matrix.\n- Optimize conditions to retain hydrophilic properties and molecular stability.\n\n### Step 2: Step-by-Step Experimental Procedure\n\n#### 2.1. Selection of Polymer Substrate\n- Choose a hydrophilic polymer that has functional groups capable of interacting with \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\). Suitable candidates include:\n  - Poly(vinyl alcohol) (PVA) \u2014 due to its hydroxyl (-OH) groups.\n  - Polyacrylamide (PAM) \u2014 due to its amide (-CONH2) groups.\n  - Poly(N-vinylpyrrolidone) (PVP) \u2014 due to its lactam (-C=O and -N-) functional groups.\n\nFor this example, I will use **PVA**, given its versatility, hydrophilicity, and ease of post-functionalization.\n\n---\n\n#### 2.2. Preparation of the Polymer Solution\n1. **Dissolution of PVA**:\n   - Take **10 g of PVA (Mw 85,000\u2013124,000, fully hydrolyzed)** and dissolve it in **100 mL of deionized water** by heating to **80 \u00b0C** with continuous stirring until a clear, viscous solution forms.\n   - This ensures that all hydroxyl groups are accessible for subsequent interactions.\n\n2. **Cool the solution** to room temperature while stirring to avoid gelation.\n\n---\n\n#### 2.3. Preparation of \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) Solution\n1. Dissolve **1 g of potassium ferricyanide (\\( K_{3}\\text{Fe(CN)}_{6} \\))** or potassium ferrocyanide (\\( K_{4}\\text{Fe(CN)}_{6} \\))** in 50 mL of deionized water**.\n   - This concentration ensures a sufficient amount of the molecule for even dispersion in the polymer matrix.\n\n2. If needed, adjust the pH of the solution to between **6 and 7** to maintain stability of the ferricyanide and ferrocyanide ions.\n\n---\n\n#### 2.4. Incorporation of \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) into the Polymer Matrix\nThere are two main methods of incorporation: **direct physical blending** or **chemical crosslinking**. Here, we will discuss both.\n\n##### (A) **Physical Blending Method**:\n   1. Mix the PVA solution and the \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) solution in a **1:1 volume ratio** under continuous stirring.\n   2. Continue stirring at room temperature for **2 hours** to ensure homogeneity.\n   3. Cast the mixture onto a clean glass or silicone mold to form a film.\n   4. Allow the film to dry at **50 \u00b0C overnight** in an oven.\n      - This method ensures that \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) ions are well-integrated into the polymer matrix through hydrogen bonding and electrostatic interactions with PVA's hydroxyl groups.\n\n##### (B) **Chemical Crosslinking Method**:\n   1. Add a crosslinker, such as **glutaraldehyde (GA)**, to improve the mechanical stability of the polymer network.\n      - Add **0.5 mL of GA solution (50% aqueous solution)** and **2 drops of HCl (1 M)** to the PVA- \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) mixture.\n      - Stir for an additional **30 minutes**.\n      - The crosslinker reacts with PVA\u2019s hydroxyl groups, creating a chemically bound network in which \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) is immobilized.\n   2. Cast the crosslinked solution onto a mold and cure at **50 \u00b0C for 12 hours**.\n      - This approach enhances the stability of \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) within the polymer by forming a semi-permanent matrix.\n\n---\n\n#### 2.5. Post-Treatment and Washing\n- After drying or curing, wash the polymer film thoroughly with deionized water to remove any unbound \\( K_{x}\\text{Fe(CN)}_{6} \\) ions or residual crosslinkers.\n- Dry the film again at **50 \u00b0C for 6 hours**.\n\n---\n\n### Step 3: Mechanism of Interaction and Hydrophilicity Enhancement\n1. **Hydrophilicity Mechanism**:\n   - The incorporated \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) ions, being charged, interact with water molecules through electrostatic attraction, enhancing the hydrophilicity of the polymer.\n   - PVA\u2019s hydroxyl groups also form hydrogen bonds with \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\), further stabilizing the interactions and facilitating water adsorption.\n\n2. **Consistent Interaction**:\n   - Physical blending ensures uniform dispersion of \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) throughout the polymer network.\n   - Chemical crosslinking immobilizes the ions, preventing migration or aggregation over time, which ensures consistent hydrophilic behavior.\n\n---\n\n### Step 4: Reaction Conditions and Practical Notes\n1. Keep the reaction environment free from contaminants or reducing agents, as they might reduce \\( [\\text{Fe(CN)}_{6}]^{3-} \\) to \\( [\\text{Fe(CN)}_{6}]^{4-} \\) or interfere with the polymer properties.\n2. Maintain a pH-neutral reaction medium to avoid decomposition of ferricyanides.\n\n---\n\n### Step 5: Summary\nTo incorporate \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\) into a PVA polymer:\n- Dissolve PVA and ferricyanide preparations separately.\n- Physically blend the solutions or chemically crosslink them for improved stability.\n- Cast, dry, and post-treat the films to remove unreacted species.\n- This results in a hydrophilic polymer with a consistent distribution of \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\), enhancing its hydrophilicity through electrostatic and hydrogen-bonding interactions.\n\nBy following this step-by-step protocol, you can successfully prepare a hydrophilic polymer matrix containing \\( [\\text{Fe(CN)}_{6}]^{3-/4-} \\). Let me know if you have further questions!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Design a procedure for incorporating GMA into a polymer matrix to form a hydrophilic coating. Specify the steps required, including any necessary pre-treatment, reaction parameters, and curing conditions."}, {"role": "assistant", "content": "Certainly! Incorporating glycidyl methacrylate (GMA) into a polymer matrix to form a hydrophilic coating is a common strategy to enhance the polymer's hydrophilicity due to GMA\u2019s reactive epoxy group and methacrylate functionality. Let us proceed step by step while analyzing your question and systematically addressing all details.\n\n---\n\n### Step 1: **Analyze the Key Points**\n1. **Objective**: To modify a polymer matrix with GMA to create a hydrophilic coating.\n2. **Significance of GMA**: \n   - It serves as the key building block, offering:\n     - A methacrylate group for polymerization.\n     - An epoxy group for subsequent hydrophilic functionalization.\n3. **Requirements**:\n   - Pre-treatment of the polymer matrix to enable functionalization.\n   - Incorporation of GMA into the polymer structure.\n   - Curing and further reaction of the epoxy groups to introduce hydrophilic functionalities.\n\n---\n\n### Step 2: **Experimental Scheme**\nHere is the detailed procedure for incorporating GMA into a polymer matrix and forming a hydrophilic coating.\n\n---\n\n#### **A. Pre-treatment of the Polymer Matrix**\nBefore functionalizing any polymer surface with GMA, ensure that the surface is ready for effective adhesion and reaction.\n\n1. **Surface Cleaning**:\n   - Clean the polymer surface (if solid or film-based) to remove dirt, grease, or any contaminants.\n   - Use solvents such as ethanol or isopropyl alcohol (IPA) for thorough cleaning.\n   - Dry the surface using nitrogen gas or in a vacuum oven at 40\u201350\u00b0C to remove residual moisture.\n   \n2. **Surface Activation (if needed)**:\n   - If the polymer matrix is inert or hydrophobic, activate the surface to introduce functional groups (e.g., hydroxyl or carboxyl groups) for better reactivity:\n     - **Plasma Treatment**: Expose the polymer to oxygen plasma at low pressure (~0.3\u20130.8 Torr) for 1\u20133 minutes.\n     - **Chemical Etching**: Treat with a solution like chromic acid or potassium permanganate (5\u201310% w/v) for 10\u201330 minutes, followed by thorough rinsing and drying.\n\n---\n\n#### **B. Incorporation of GMA**\nThe incorporation of GMA into the polymer matrix can be achieved using free-radical polymerization or grafting techniques.\n\n1. **Preparation of the Reaction Mixture**:\n   - Dissolve **GMA** in a suitable solvent (e.g., acetone, ethanol) to ensure compatibility with the polymer matrix.\n   - Add a free-radical initiator such as **benzoyl peroxide (BPO)** or **azobisisobutyronitrile (AIBN)** at 1\u20132% molar equivalent of the GMA monomer. This will initiate polymer grafting.\n   - Optionally, include a co-monomer (e.g., acrylic acid or methacrylic acid at a 50:50 molar ratio with GMA) to introduce additional hydrophilic groups.\n\n   Example ratio of reagents:\n   - GMA: 0.2\u20130.5 M final concentration in solvent.\n   - Initiator (AIBN): 0.005 M (ensure 1\u20132% of GMA molar equivalent).\n   - Co-monomer (if used): Same molar concentration as GMA.\n\n2. **Polymer Grafting**:\n   - Immerse the polymer matrix (or substrate) into the reaction mixture.\n   - Degas the reaction system by purging with nitrogen or argon for 15\u201320 minutes to eliminate oxygen (oxygen can inhibit free-radical polymerization).\n   - Heat the reaction system to 50\u201370\u00b0C for 2\u20134 hours with constant stirring.\n\n3. **Post-reaction Washing**:\n   - After the reaction, rinse the modified polymer thoroughly with ethanol or acetone to remove any unreacted GMA or by-products.\n   - Dry the polymer matrix under a mild vacuum at ~50\u00b0C.\n\n---\n\n#### **C. Curing and Introduction of Hydrophilic Groups**\nThe next step is to utilize the epoxy groups of GMA for hydrophilization.\n\n1. **Epoxy Ring-Opening Reaction**:\n   - React the epoxy groups of GMA with a hydrophilic reagent, such as amines (e.g., ethanolamine, diethanolamine) or acids (e.g., citric acid).\n   - Prepare an aqueous or alcohol-based solution (10\u201320% w/v) of the hydrophilic reagent.\n   - Immerse the GMA-modified polymer surface in the solution and adjust pH to 7\u20139 (for amines) or mildly acidic (pH 5\u20136, for acids).\n   - Heat the system to ~40\u00b0C and allow the reaction to proceed for 1\u20132 hours, depending on the reagent used.\n\n2. **Curing**:\n   - After the reaction, rinse the polymer matrix with deionized water to remove unreacted reagents.\n   - Cure the polymer at 50\u201370\u00b0C for 1\u20132 hours to stabilize the hydrophilic layer.\n\n---\n\n### Step 3: **Reaction Conditions and Parameters Summary**\nHere is a concise summary for the parameter setup:\n\n1. **GMA Incorporation**:\n   - Initiation: Free-radical polymerization using AIBN or BPO.\n   - Solvent: Acetone or ethanol.\n   - Temperature: 50\u201370\u00b0C.\n   - Time: 2\u20134 hours.\n   - Molar Ratio: 2\u20135% initiator to GMA.\n\n2. **Epoxy Ring-Opening**:\n   - Reagent: Ethanolamine (or similar).\n   - pH: Basic (7\u20139) for amines; slightly acidic for acids.\n   - Time: 1\u20132 hours.\n   - Temperature: 40\u00b0C.\n   \n3. **Curing**:\n   - Time: 1\u20132 hours.\n   - Temperature: 50\u201370\u00b0C.\n\n---\n\n### Step 4: Additional Considerations\n- **Characterization**:\n  - Confirm hydrophilicity using contact angle measurements (smaller angles indicate higher hydrophilicity).\n  - Analyze the chemical structure using techniques like Fourier-transform infrared spectroscopy (FTIR) to verify the incorporation of GMA and subsequent modifications.\n- **Safety**:\n  - Work in a well-ventilated fume hood when handling volatile solvents like acetone or ethanol.\n  - Use gloves, safety goggles, and other appropriate protective equipment.\n\n---\n\nBy following the outlined procedure, you should be able to successfully incorporate GMA into the polymer matrix and create a hydrophilic coating. Let me know if additional clarifications or adjustments are needed!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Imagine you are provided with carboxy-functionalized rod-like polySQ and asked to utilize it as a precursor in sol-gel chemistry to create hydrophilic polymer coatings. What experimental conditions (e.g., temperature, solvents) would you optimize and why?"}, {"role": "assistant", "content": "To address your question regarding the utilization of carboxy-functionalized rod-like polySQ as a precursor in sol-gel chemistry to create hydrophilic polymer coatings, let's proceed systematically, as guided by the outlined requirements:\n\n---\n\n### **Step 1: Identifying the Key Aspects of the Problem**\n1. **Precursor Material**: Carboxy-functionalized rod-like polySQ.\n   - Understanding its critical functional groups (carboxylic acid groups) and its structural implications (rod-like polySQ backbone) is essential.\n   - The carboxylic acid groups provide reactive sites for chemical modification or processing in sol-gel chemistry to form hydrophilic coatings.\n\n2. **Target Objective**: Prepare a hydrophilic polymer coating.\n   - Hydrophilicity implies enhancing the polymer's affinity for water by incorporating functional groups (e.g., hydroxyl, amine, or other hydrophilic moieties) or optimizing the reaction morphology to expose hydrophilic sites.\n   - Sol-gel chemistry should be tailored to achieve a uniform, stable, hydrophilic coating on the substrate.\n\n3. **Experimental Parameters to Optimize**:\n   - Reaction conditions, including temperature, solvent selection, pH, catalyst concentration, and reaction duration, should be analyzed and justified.\n   - Control of hydrolysis and condensation steps typical of sol-gel chemistry is critical for uniform and defect-free coatings.\n\n---\n\n### **Step 2: Detailed Experimental Process for Synthesizing Hydrophilic Polymer Coating**\n\n#### **Step 2.1: Precursor and Solvent Preparation**\n- **Precursor (carboxy-functionalized polySQ)**:\n  - We assume that the precursor contains a carboxylic acid (-COOH) functionality along the polySQ rod-like backbone. This can act as a reactive site for sol-gel branching or a self-assembly moiety.\n  - Use 0.1\u20130.2 g of carboxy-functionalized polySQ (varied depending on the coating area required).\n\n- **Selection of Solvent**:\n  - Sol-gel reactions involve hydrolysis and condensation steps that are solvent-sensitive.\n  - Suggested solvents: Polar protic solvents like ethanol or isopropanol (88\u201399% pure) are recommended due to their ability to facilitate hydrolysis of precursors while maintaining uniform mixing.\n  - Ratio of solvent to precursor by mass: ~5:1 to ensure complete dissolution of polySQ.\n\n#### **Step 2.2: Optimizing Sol-Gel Reaction Conditions**\n1. **Hydrolysis**:\n   - Add **deionized water** (DI water) to the polySQ solution to induce hydrolysis of carboxylic sites and promote sol-gel reactions. The molar ratio of water to precursor is critical:\n     - Use approximately 10:1 molar ratio of water to precursor to ensure sufficient hydrolysis, as the carboxy-functionalized sites are hydrophilic and can accommodate excess water.\n   - Maintain pH around 3.5\u20135.0 using **acetic acid** as a weak acid catalyst.\n     - Acetic acid facilitates the hydrolysis step without over-accelerating condensation, which can lead to gelation inconsistencies.\n\n2. **Temperature**:\n   - Perform the hydrolysis at **40\u201345 \u00b0C** with constant stirring (500\u2013700 rpm) for 2\u20133 hours.\n   - This moderate temperature range ensures sufficient reaction rates while preserving the structural integrity of the polySQ backbone.\n\n3. **Condensation**:\n   - After hydrolysis is complete, increase the reaction temperature to **60\u201370 \u00b0C** to initiate the condensation step.\n   - Stirring should be maintained to avoid localized gelation, which could lead to non-uniform coatings.\n   - Add a small amount of **tetraethoxysilane (TEOS)** or another alkoxysilane (if added crosslinking is required) in a 1:1 molar ratio with carboxy-functionalized sites to promote silica-based network formation. The silanol intermediates will attach to the carboxy-functionalized polySQ, enhancing hydrophilicity and introducing structural robustness.\n\n#### **Step 2.3: Application as Coating**\n- Once the sol-gel material achieves the desired viscosity and homogeneity, it can be coated onto the desired substrate (e.g., glass, ceramics, or metals).\n  - Coating method: Use **dip-coating** or **spin-coating** depending on the substrate and desired layer thickness.\n  - Dip-coating protocol: Immerse the substrate, hold it for 1 minute to allow uniform polymer adhesion, then withdraw it at a rate of 1\u20132 mm/s.\n\n- Post-deposition curing:\n  - Cure the coated substrate in an oven at **80\u2013100 \u00b0C** for 12\u201324 hours to remove residual solvents and stabilize the polymer network.\n  - This step crosslinks the polymeric sol-gel and ensures a stable, hydrophilic coating.\n\n---\n\n### **Step 3: Theoretical Justification for Conditions**\n1. **Hydrolysis and Condensation Control**:\n   - Controlled pH (mildly acidic, 3.5\u20135) allows a balance between hydrolysis and condensation, avoiding premature gelation.\n   - Moderate temperature aids in molecular mobility, ensuring uniform reactions.\n\n2. **Solvent Choice**:\n   - Polar protic solvents like ethanol dissolve polySQ effectively and aid in hydrolysis of any added alkoxysilanes.\n   - A high solvent-to-precursor ratio facilitates homogeneity.\n\n3. **Enhancing Hydrophilicity**:\n   - Incorporating silanol [Si\u2013OH] groups from TEOS or functionalizing the carboxylic groups with hydrophilic moieties (e.g., hydroxyl or amine groups) enhances water affinity.\n\n4. **Coating Methodology**:\n   - Dip-coating provides reproducible thickness and defect-free surfaces in sol-gel processing.\n   - Post-deposition curing eliminates trapped solvents and solidifies the polymer networks.\n\n---\n\n### **Step 4: Notes for Experimental Practice**\n- **Safety Considerations**:\n  - Use a fume hood for handling solvents like ethanol.\n  - Wear gloves and goggles for handling acids and TEOS, which can be corrosive.\n\n- **Reproducibility**:\n  - Maintain consistent stirring speed and deposition conditions for reproducible results.\n\n- **Characterization**:\n  - Assess hydrophilicity through techniques like water contact angle measurement (<15\u00b0 is ideal for hydrophilic coatings).\n  - Use spectroscopic methods (e.g., FTIR) to confirm the presence of silanol and carboxylic acid groups after deposition.\n\n---\n\nBy following this methodology, you will obtain a well-controlled, hydrophilic polymer coating derived from carboxy-functionalized rod-like polySQ using sol-gel chemistry. Let me know if further clarification is needed!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Design an experimental scheme for synthesizing a hydrophilic polymer using photocrosslinkable methacrylic pullulan, ensuring the polymer is suitable for applications requiring high water retention. Include the methods for crosslinking and any functional group modifications."}, {"role": "assistant", "content": "Certainly! Let's approach this question step by step to systematically develop an experimental scheme for synthesizing a hydrophilic polymer using photocrosslinkable methacrylic pullulan. The goal is to create a hydrogel-like material with high water retention properties, ensuring it is ideal for applications requiring superior hydrophilicity (e.g., bioengineering scaffolds or wound dressings). I'll break down the process as follows:\n\n---\n\n### **Step 1: Analyze the Question and Summarize Key Points**\n\nThe key aspects of the question include:\n1. **Polymer Base Material:** Photocrosslinkable methacrylic pullulan (a polysaccharide derivative that can be functionalized to include methacrylate groups for crosslinking).\n2. **Desired Property:** High hydrophilicity with excellent water retention.\n3. **Experimental Requirements:**\n   - Synthesis of the hydrophilic polymer using methacrylic pullulan.\n   - Introduction of any necessary functional group modifications to enhance hydrophilicity.\n   - Use of photocrosslinking (via UV irradiation and photoinitiator) to form a well-structured polymer network.\n\nThe objective is thus to functionalize pullulan, photocrosslink it into a hydrogel, and optimize its water retention properties by controlling the degree of crosslinking and incorporating hydrophilic functional groups where necessary.\n\n---\n\n### **Step 2: Develop the Experimental Scheme**\n\n#### **(A) Materials Required**\n1. **Methacrylic Pullulan:**\n   - Prepared by modifying pullulan with methacrylate groups. If unavailable, this functionalization can be done in-house (see details in Step 2B).\n2. **Photoinitiator:** Irgacure 2959 (2-hydroxy-4\u2032-(2-hydroxyethoxy)-2-methylpropiophenone) is commonly used due to water solubility and suitability for UV curing.\n3. **Solvent for Dissolution:** Deionized water or a water/ethanol mixture.\n4. **Optional Co-monomer for Hydrophilicity Enhancement** (if needed):\n   - Acrylic acid, N-vinylpyrrolidone, or polyethylene glycol diacrylate (PEGDA) can be included to increase hydrophilic properties.\n\n#### **(B) Preparation of Methacrylic Pullulan (if pre-synthesized methacrylic pullulan is not available)**\n\n1. **Reagents Needed:**\n   - Pullulan (a polysaccharide polymer).\n   - Methacrylic anhydride (functionalizing agent with methacrylate groups).\n   - Base catalyst (e.g., triethylamine).\n   - Solvent: Deionized water or phosphate-buffered saline.\n\n2. **Synthesis Procedure:**\n   - Dissolve pullulan in deionized water (5\u201310 wt% concentration) under agitation at 25\u201350 \u00b0C.\n   - Slowly add methacrylic anhydride to the pullulan solution while maintaining the pH between 8 and 9 using a base (triethylamine or NaOH). Ensure dropwise addition to avoid rapid hydrolysis.\n   - Allow the reaction to proceed for 3\u20136 hours at room temperature, constantly monitoring the pH and stirring.\n   - The methacrylation of hydroxyl groups in pullulan results in methacrylic pullulan.\n   - Purify the product by dialyzing against deionized water for 48\u201372 hours to remove unreacted methacrylic anhydride and byproducts.\n   - Lyophilize the purified product to obtain methacrylic pullulan as a dry powder.\n\n---\n\n#### **(C) Photo-Crosslinking and Hydrogel Formation**\n\n1. **Reagents Needed:**\n   - Methacrylic pullulan (prepared or pre-synthesized).\n   - Photoinitiator: Irgacure 2959 (recommended concentration: 0.5 wt% relative to polymer).\n   - Water or an aqueous solvent.\n\n2. **Procedure:**\n   - Dissolve methacrylic pullulan (10\u201315 wt%) in deionized water at room temperature to form a clear solution.\n   - Add the photoinitiator (Irgacure 2959) to the solution and stir until completely dissolved. Ensure uniform mixing.\n   - Pour the solution into molds (e.g., Teflon molds or glass molds) to achieve the desired hydrogel shape/geometry.\n   - Expose the solution to UV light (typically 365 nm wavelength) for crosslinking. Use a UV lamp with an intensity of ~5\u201310 mW/cm\u00b2.\n   - UV irradiation time may vary (5\u201315 minutes), depending on the desired crosslinking density and mechanical strength of the final hydrogel.\n\n   **Notes on UV Crosslinking Conditions:**\n   - A longer exposure time generally increases crosslinking density but reduces swelling capacity. Optimize based on water retention requirements.\n   - Avoid overheating during UV curing to preserve polymer properties.\n\n---\n\n#### **(D) Enhancing Hydrophilicity**\nIf additional hydrophilicity is required, incorporate hydrophilic co-monomers into the formulation prior to crosslinking. For example:\n- Add acrylic acid to the polymer solution to introduce carboxylic groups.\n- Include PEGDA if increased elasticity and water absorption are desired.\nOptimize the ratio of methacrylic pullulan to hydrophilic co-monomer (e.g., 90:10 or 80:20) to improve final properties.\n\n---\n\n#### **(E) Characterization of the Hydrophilic Polymer**\n1. **Swelling Ratio:**\n   - Immerse the hydrogel in deionized water and measure its swelling behavior over time.\n   - Calculate the swelling capacity using the formula:\n     \\[\n     \\text{Swelling Ratio} = \\frac{\\text{Weight of swollen hydrogel} - \\text{Weight of dry hydrogel}}{\\text{Weight of dry hydrogel}}\n     \\]\n2. **Water Retention Test:**\n   - Monitor the water content retained by the hydrogel after exposure to different environmental conditions.\n3. **Mechanical Testing:**\n   - Assess the hydrogel\u2019s mechanical properties (e.g., elasticity, compressive strength) if required for load-bearing applications.\n4. **Fourier Transform Infrared Spectroscopy (FTIR):**\n   - Confirm the presence of methacrylate groups and successful crosslinking.\n\n---\n\n### **Step 3: Summary**\nThis experimental scheme provides a detailed methodology for synthesizing a hydrophilic polymer with excellent water retention properties, using methacrylic pullulan as a base. The process includes:\n1. Functionalization of pullulan with methacrylate groups.\n2. Photocrosslinking methacrylic pullulan under UV irradiation to form a hydrogel.\n3. Optional incorporation of hydrophilic co-monomers to enhance hydrophilicity.\n4. Evaluation of the polymer's water absorption and retention properties.\n\nBy carefully adjusting the degree of crosslinking and evaluating the role of hydrophilic additives, this approach allows tuning of the polymer\u2019s properties to meet the desired application. Let me know if you need help with protocol adjustments or further discussion!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "When synthesizing a hydrophilic polymer system, how would you incorporate 1,3,5-triformylbenzene (TFB) to enhance the stability of the crosslinked network? Outline the specific functional groups this molecule reacts with during the process."}, {"role": "assistant", "content": "Certainly, let us systematically address your question on how to incorporate **1,3,5-triformylbenzene (TFB)** into the synthesis of a hydrophilic polymer system to enhance the stability of the crosslinked network. First, we will analyze the question, identify the key points, and provide a comprehensive experimental preparation scheme. Let us proceed step by step:\n\n---\n\n### Key Considerations in the Question:\n1. **The role of TFB:** You wish to employ TFB as a crosslinking agent to enhance the stability of the polymer network. To do so, we must focus on its functional groups (**formyl groups, -CHO**) and identify functional groups in the polymer network that can react with these.\n2. **Hydrophilicity requirements:** Maintaining or enhancing the hydrophilic nature of the polymer system during the process is essential.\n3. **Reaction mechanism:** The interaction of TFB\u2019s formyl groups with complementary reactive groups is necessary to form the chemical bonds responsible for network crosslinking.\n\n--- \n\n### **Step-by-Step Synthesis Process:**\nBelow, I outline the experimental preparation scheme:\n\n#### Step 1: Selection of Polymer Precursor\n- Choose a hydrophilic monomer or polymer precursor that contains reactive functional groups capable of reacting with TFB\u2019s formyl groups. Examples of useful reactive groups include:\n  - **Amine groups (-NH2):** For Schiff base condensation to form imine bonds (-C=N).\n  - **Hydroxyl groups (-OH):** For acetal or hemiacetal formation in acidic conditions.\n- A suitable candidate could be a hydrophilic polymer such as poly(ethyleneimine) (PEI) or a functionalized poly(vinyl alcohol) (PVA) that has ample hydroxyl or amino groups.\n\n---\n\n#### Step 2: Preparation of Reaction Solution\n**Materials Required:**\n1. **1,3,5-Triformylbenzene (TFB):** Acts as a trifunctional aldehyde-based crosslinker.\n2. **Polymer precursor (e.g., PEI or PVA):** Provides the backbone with reactive groups (-NH2 or -OH).\n3. **Solvent:** Ensure a hydrophilic solvent to support solubility of reactants. Frequently used solvents include water, ethanol, or DMSO.\n4. **Catalyst (if applicable):**\n   - For Schiff base reactions: Acidic catalysts (e.g., acetic acid) to promote condensation.\n   - For hydroxyl-based crosslinking: Mild acids like p-toluenesulfonic acid.\n\n**Experimental Setup:**\n1. Dissolve the hydrophilic polymer precursor in the solvent. For instance:\n   - Dissolve PEI in water (e.g., at 10 wt% concentration).\n2. Separately dissolve TFB in the same solvent. Since TFB is sparingly soluble in water, use moderate stirring, heating (~40\u201350 \u00b0C), or employ DMSO if solubility challenges arise.\n\n---\n\n#### Step 3: Stoichiometric Ratios\n- The ratio of **TFB to reactive groups** on the polymer backbone is crucial for uniform crosslinking.\n- Calculate the stoichiometric ratio based on the molar amount of functional groups. For example:\n  - If PEI has ~5 mmol of amino groups, use ~1.6 mmol of TFB (1:3 ratio of amine groups to TFB\u2019s formyl groups ensures all sites are engaged).\n\n---\n\n#### Step 4: Reaction Conditions\n- Gradually combine the TFB solution with the polymer solution under constant stirring.\n- Maintain the reaction temperature between 40\u201350 \u00b0C to foster crosslinking. Avoid overheating as it can degrade sensitive groups and reduce hydrophilicity.\n- Allow the reaction to proceed for **6\u201312 hours** to ensure complete network formation.\n- Monitor progress using techniques such as:\n  - FTIR spectroscopy to verify the formation of imine bonds (-C=N) or acetal/ether linkages.\n\n---\n\n#### Step 5: Post-Processing\n1. **Purification:** If necessary, remove unreacted TFB or polymer by precipitation (e.g., using acetone) and dialysis in water to enhance purity.\n2. **Drying and Curing:** Dry the crosslinked polymer at ambient temperature or under vacuum at 40\u201350 \u00b0C to avoid disrupting the hydrophilic structure.\n\n---\n\n#### Step 6: Characterization of the Hydrophilic Polymer\n- Confirm the formation of the crosslinked network:\n  1. **FTIR Spectroscopy:** Look for characteristic peaks corresponding to imine (C=N, ~1640 cm\u207b\u00b9) or acetal bonds.\n  2. **Swelling Test:** Assess the hydrophilicity by studying the swelling behavior of the new polymer network in water or buffer solutions.\n  3. **Thermal Stability Tests (TGA/DSC):** Confirm that the crosslinking imparts the desired stability.\n  4. **Mechanical Tests:** Evaluate the strength of the crosslinked network using tensile/compression tests if applicable.\n\n---\n\n### **Functional Groups Involved:**\n**1,3,5-Triformylbenzene (TFB)** reacts with:\n1. **Amino groups (-NH2):** Via Schiff base condensation to form **imine bonds** (-C=N), which provide robust and stable crosslinks.\n2. **Hydroxyl groups (-OH):** Under acidic conditions, TFB can form acetals (R-CH(OR\u2019)\u2082) or hemiacetals (R-CH(OH)(OR')) with alcohol groups, leading to hydrophilic and chemically stable crosslinked structures.\n\n---\n\n### **Summary**\nIncorporating TFB into a hydrophilic polymer system enhances the stability of the crosslinked network through Schiff base condensation (imine bond formation) or acetal linkages, depending on the reactive groups of the polymer precursor. By systematically controlling the reaction stoichiometry, temperature, and catalysts, you can successfully synthesize a hydrophilic polymer with improved network stability, suitable for applications such as hydrogel formation, water-resistant coatings, and biomedical devices.\n\nBy following this protocol step by step, you should have no trouble incorporating TFB into your hydrophilic polymer system. Let me know if there are any additional questions!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Polysaccharides are often used to prepare hydrophilic polymer coatings. How would you modify a polymer surface with polysaccharides, and what factors would you evaluate to confirm the improvement in hydrophilicity?"}, {"role": "assistant", "content": "### Analysis of the Question:\n\nPolysaccharides are a class of hydrophilic macromolecules commonly used in biomedical and material applications due to their inherent hydrophilicity, biocompatibility, and versatility in chemical modification. Your question pertains to modifying a polymer surface with polysaccharides to enhance hydrophilicity and determining the successful improvement of hydrophilicity via evaluation methods.\n\nThe process requires:\n1. **Surface modification strategy:** Covalent or non-covalent attachment of polysaccharides to the polymer surface.\n2. **Factors to confirm hydrophilicity improvement:** Experimental evaluation using techniques such as water contact angle measurement and surface characterization tools.\n\n### Step-by-Step Experimental Preparation Scheme:\n\n#### Step 1: Selection of Polysaccharide\nChoose a hydrophilic polysaccharide that can adhere or bond to the polymer surface. Examples include:\n- **Chitosan** (due to its amine groups for chemical reactivity)\n- **Alginate** (carboxyl groups can form ionic or covalent bonds)\n- **Dextran** (hydroxyl groups for functionalization)\n- **Hyaluronic acid** (useful in biomedical applications due to biocompatibility)\n\n#### Step 2: Surface Functionalization of Polymer\nTo facilitate polysaccharide attachment, the polymer must be functionalized via various methods:\n1. **Plasma or UV/Ozone Treatment**:\n   - Use plasma treatment or UV/ozone oxidation to introduce reactive hydroxyl (-OH), carboxyl (-COOH), or carbonyl (-C=O) groups on the surface if the polymer is chemically inert (e.g., polyethylene or polystyrene).\n   - Example protocol: Treat polymer surfaces with oxygen plasma at 20\u201350 W for 3\u20135 minutes.\n2. **Activation with Chemical Coupling Agents**:\n   - Use coupling agents (such as EDC/NHS for carboxyl groups or silanes for hydroxyl groups) for surface activation.\n\n#### Step 3: Covalent Attachment of Polysaccharide\nAfter activation, polysaccharides can be covalently bonded to the polymer surface using established chemistry:\n1. **Carbodiimide Chemistry for Carboxyl Groups**:\n   - Use a solution of EDC (1-ethyl-3-(3-dimethylaminopropyl) carbodiimide) and NHS (N-hydroxysuccinimide) in water or buffer (e.g., MES buffer) to activate carboxyl groups on the surface.\n   - Dissolve polysaccharide in water or buffer at 1\u201310 mg/mL.\n   - React the functionalized surface with the polysaccharide solution at room temperature for 4\u20138 hours.\n2. **Epoxy Crosslinking**:\n   - If epoxy groups are introduced on the polymer surface during functionalization, polysaccharides with hydroxyl or amine groups can directly react under mild conditions (in buffers at pH 7\u20139).\n3. **Ionic Bonding or Adsorption**:\n   - For polymers with ionic charges after functionalization (e.g., quaternized surfaces), use oppositely charged polysaccharides (such as alginate or chitosan).\n\n#### Step 4: Washing and Post-Curing\n- Wash the modified polymer surface thoroughly with distilled water or buffer to remove unbound reagents and polysaccharide residues.\n- Perform mild drying under vacuum or ambient conditions, ensuring no thermal damage occurs to the polysaccharide layer.\n\n#### Step 5: Confirmation of Hydrophilicity Improvement\nEvaluate hydrophilicity enhancement using the following methods:\n1. **Water Contact Angle Measurement**:\n   - Measure the contact angles before and after modification using a contact angle goniometer.\n   - A reduction in water contact angle (e.g., from over 90\u00b0 to below 30\u00b0) indicates increased hydrophilicity.\n2. **Surface Characterization**:\n   - Perform **Fourier-Transform Infrared (FTIR) Spectroscopy** to confirm the presence of polysaccharide-specific functional groups (e.g., hydroxyl, amine, and carboxyl groups).\n   - Conduct **X-ray Photoelectron Spectroscopy (XPS)** to confirm the chemical composition changes.\n3. **Atomic Force Microscopy (AFM)**:\n   - Evaluate surface roughness after modification, as smoother surfaces often correlate with improved hydrophilicity due to uniform coatings.\n4. **Protein and Water Adsorption Tests** (if applicable):\n   - Measure protein adsorption or the water retention capacity of the surface to confirm hydrophilic behavior (typically, hydrophilic surfaces exhibit lower protein adsorption and higher water affinity).\n\n#### Step 6: Optimization for Application-Specific Properties\nEvaluate additional parameters based on application requirements:\n- **Durability and Stability:** Test the polysaccharide coating under various pH or temperature conditions to ensure adherence and stability.\n- **Biocompatibility:** If using the modified surface in biomedical applications, perform cell adhesion and proliferation studies to confirm application suitability.\n\n---\n\n### Recap of Factors to Evaluate Hydrophilicity Improvement:\n- Reduction in water contact angle.\n- Changes in surface chemistry indicative of polysaccharide attachment (FTIR, XPS, etc.).\n- Improved water adsorption/capacity or lower protein adhesion.\n- Enhanced biocompatibility or specific functional properties (application-dependent).\n\nBy employing these systematic steps, you can successfully modify a polymer surface with polysaccharides to enhance hydrophilicity and evaluate its improvement rigorously."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the steps you would take to synthesize 3-(bis(hydroxymethyl)amino)-2-hydroxypropyl methacrylate (D-GMA) and explain why this molecule is significant for enhancing the hydrophilicity of the polymer material."}, {"role": "assistant", "content": "Let us carefully approach your question step by step and systematically design a synthesis scheme for the molecule **3-(bis(hydroxymethyl)amino)-2-hydroxypropyl methacrylate (D-GMA)** while also explaining its significance. First, I will analyze the problem, summarize the key chemistry involved, and then provide a stepwise protocol for performing the synthesis in the laboratory.\n\n---\n\n### **Step 1: Analyze the Question and Summarize Key Points**\n\n**Aims of the Question:**\n1. To design a synthetic route for preparing **3-(bis(hydroxymethyl)amino)-2-hydroxypropyl methacrylate (D-GMA)**.\n2. To explain why incorporating D-GMA into a polymer structure improves the hydrophilicity of the material.\n\n**Important Observations:**\n- D-GMA contains a **methacrylate (vinyl ester)** moiety for polymerization, combined with functional groups that enhance hydrophilicity, such as:\n  - A central hydroxy group (-OH).\n  - Bis(hydroxymethyl)amino functionality (-CH2OH groups attached to an amine nitrogen).\n- These highly polar hydroxyl (-OH) groups and the amine's interaction with water contribute to its hydrophilic nature.\n- We will need to pay close attention to reaction conditions, as D-GMA contains highly reactive functional groups that require careful handling to avoid side reactions.\n\n---\n\n### **Step 2: Experimental Synthesis of D-GMA**\n\nI will now detail the synthesis process with a complete explanation of each step, the reagents required, conditions, and molar quantities to aid your understanding and performance in a laboratory setting.\n\n---\n\n#### **Step A: Synthesis of Hydroxymethylamines**\n\nThe first objective is to introduce bis(hydroxymethyl) functionality into an amine group. The precursor is **ammonia (NH3)** or a primary amine, reacted with **formaldehyde (CH2O)**.\n\n1. **Reactant Preparation:**\n   - React formaldehyde with ammonia solution (or methylamine) in an aqueous medium.\n   - Employ a molar ratio of **3:1 (formaldehyde:ammonia/methylamine)** to maximize the formation of bis(hydroxymethyl)amine.\n\n2. **Reaction Conditions:**\n   - Conduct the reaction in water as the solvent at a controlled **temperature of 50\u201360\u00b0C** for 4\u20136 hours with gentle stirring to ensure uniform mixing.\n   - The reaction scheme:\n     \\[\n     NH_3 + 2CH_2O \\rightarrow NH(CH_2OH)_2\n     \\]\n\n3. **Product Outcome:**\n   - The resulting intermediate is **bis(hydroxymethyl)amine (NH-CH2OH)2)** in aqueous solution.\n\n4. **Workup:**\n   - Cool the reaction mixture to room temperature.\n   - Extract and purify the product by crystallization or evaporation of water to concentrate it.\n\n---\n\n#### **Step B: Addition of Epichlorohydrin**\n\nNext, we introduce a secondary hydroxy group (-OH) using **epichlorohydrin**, an epoxide-containing compound, which reacts with the amine derivative from Step A.\n\n1. **Reactant Preparation:**\n   - Use **1 mol equivalent of bis(hydroxymethyl)amine** and **1.2 mol equivalents of epichlorohydrin** in an aqueous or organic solvent, such as methanol.\n\n2. **Reaction Conditions:**\n   - React the mixture at **35\u201350\u00b0C** for approximately 12\u201316 hours with stirring.\n\n3. **Reaction Mechanism:**\n   - Epichlorohydrin undergoes nucleophilic ring-opening by the amine, forming a hydroxypropyl-amine intermediate:\n     \\[\n     NH(CH_2OH)_2 + \\text{Epichlorohydrin} \\rightarrow \\text{3-(bis(hydroxymethyl)amino)-2-hydroxypropyl derivative.}\n     \\]\n\n4. **Workup:**\n   - Purify the product by extracting the reaction mixture with an organic solvent (e.g., ethyl acetate).\n   - Wash with brine to remove impurities, dry over anhydrous sodium sulfate, and evaporate the solvent under reduced pressure.\n\n---\n\n#### **Step C: Esterification with Methacrylic Acid**\n\nFinally, the **methacrylate moiety** is introduced by esterification of the hydroxypropyl-amine derivative.\n\n1. **Reactant Preparation:**\n   - Combine **1 mol equivalent of the hydroxypropyl-amine product** from Step B with **1.1 mol equivalents of methacrylic acid**.\n   - Include a **catalyst** such as **p-toluenesulfonic acid (PTSA)** or dicyclohexyl carbodiimide (DCC) if required.\n\n2. **Reaction Conditions:**\n   - Conduct the reaction in a dry organic solvent such as **toluene** at **60\u201370\u00b0C** under nitrogen atmosphere for 6\u20138 hours.\n   - Continuously remove the water (a by-product of esterification) using a Dean-Stark trap to drive the reaction forward.\n\n3. **Reaction Scheme:**\n   \\[\n   3-(\\text{bis(hydroxymethyl)amino)}-2-hydroxypropyl) + \\text{Methacrylic acid} \\rightarrow \\text{D-GMA}\n   \\]\n\n4. **Workup:**\n   - Allow the reaction mixture to cool to room temperature.\n   - Extract the crude product with an organic solvent (e.g., dichloromethane), wash with water, dry over anhydrous sodium sulfate, and evaporate the solvent under reduced pressure.\n\n5. **Purification:**\n   - Purify the product using column chromatography or recrystallization.\n\n---\n\n### **Step 3: Why D-GMA Enhances Hydrophilicity**\n\nThe hydrophilic nature of D-GMA arises due to its structural features:\n- The presence of three highly polar groups: a central **hydroxy (OH)** group and two **hydroxymethyl (-CH2OH)** groups attached to the amino group. These groups form hydrogen bonds with water, improving the polymer\u2019s wettability and water retention.\n- When copolymerized with other monomers, D-GMA structures remain exposed on the polymer surface, ensuring hydrophilic properties in applications like biomaterials, coatings, and hydrogels.\n\n---\n\n### **Step 4: Summarized Notes for Lab Execution**\n\n1. Strictly control the molar ratios of reactants to minimize by-products.\n2. Optimize temperatures to avoid degradation of reactive groups.\n3. Use inert atmospheres during esterifications to prevent side reactions (e.g., oxygen inhibiting methacrylate polymerization).\n4. Purify intermediates to ensure high product quality.\n\nBy carefully following these steps, you will obtain pure D-GMA suitable for use as a polymerizable hydrophilic monomer."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Suggest a suitable polymerization strategy to cure a hydrophilic bisphenol A-based (meth)acrylate modification of a polymer, ensuring that its hydrophilic properties are preserved. Why would you choose this particular polymerization method?"}, {"role": "assistant", "content": "Certainly! Let us carefully analyze the problem and provide a step-by-step explanation to help you understand the process and ensure successful implementation in the laboratory.\n\n---\n\n### Question Analysis:\n\nYou are seeking a suitable polymerization strategy to cure a *hydrophilic bisphenol A-based (meth)acrylate* while preserving its hydrophilic properties. The key aspects here are:\n\n1. **The monomer structure:** The bisphenol A-based (meth)acrylate likely includes both hydrophilic functional groups and acrylate/methacrylate moieties for polymerization.\n2. **Hydrophilicity preservation:** The polymerization method must avoid processes that could compromise the hydrophilic functional groups.\n3. **Polymerization approach:** The most appropriate strategy must ensure uniform curing with high efficiency to achieve the desired hydrophilic polymer.\n\nLet us now develop a detailed experimental scheme to address your request.\n\n---\n\n### Proposed Polymerization Strategy:\nThe most suitable approach for curing hydrophilic bisphenol A-based (meth)acrylates is **photopolymerization** via free radical initiation, specifically using UV light in the presence of a hydrophilic photoinitiator. This method ensures efficient curing under mild conditions, avoiding thermal degradation or reaction with hydrophilic functional groups.\n\n---\n\n### Step-by-Step Experimental Preparation Scheme:\n\n#### **Step 1: Materials and Reagents Selection**\n- **Monomer:** Hydrophilic bisphenol A-based (meth)acrylate.\n  - Verify the presence of hydrophilic functional groups such as hydroxyl (-OH) or ether (-C-O-C-) groups.\n  - Ensure the acrylate/methacrylate groups are available for free radical polymerization.\n- **Photoinitiator (PI):** A water-compatible, hydrophilic photoinitiator such as *Irgacure 2959* (2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone).\n  - This initiator is widely used in aqueous systems and is non-toxic.\n- **Diluent Solvent (if necessary):**\n  - If the bisphenol A derivative is highly viscous, use a hydrophilic solvent (e.g., ethanol, water, or a water-methanol mixture) to control viscosity.\n- **Other Additives:** Consider adding crosslinkers (e.g., ethylene glycol dimethacrylate) if a crosslinked polymer is required.\n\n---\n\n#### **Step 2: Preparing the Reaction Mixture**\n1. **Monomer Dissolution:**\n   - Dissolve the hydrophilic bisphenol A-based (meth)acrylate monomer in the chosen solvent if it is solid or viscous.\n   - Use a concentration of 10\u201350% monomer (w/v) depending on the desired polymer density.\n\n2. **Photoinitiator Incorporation:**\n   - Add the hydrophilic photoinitiator (e.g., Irgacure 2959) to the monomer solution.\n   - Typical photoinitiator concentrations range from 0.5% to 1.5% (w/w) relative to the total monomer weight.\n   - Ensure thorough mixing by stirring under moderate conditions.\n\n3. **Optional Additives:**\n   - If crosslinking is desired, add a small quantity of a bifunctional crosslinker (e.g., ethylene glycol dimethacrylate) at 1\u20135% molar concentration relative to the monomer.\n\n---\n\n#### **Step 3: Photopolymerization Process**\n1. **Sample Preparation:**\n   - Transfer the reaction mixture to a mold or substrate (e.g., a glass slide or petri dish).\n   - Ensure a uniform layer to enable consistent curing.\n\n2. **UV Light Exposure:**\n   - Use a UV lamp with a wavelength of 365 nm (appropriate for photoinitiator activation) and an intensity between 5\u201320 mW/cm\u00b2.\n   - Cure the monomer mixture by exposing it to UV light for 10\u201320 minutes. The curing time varies based on layer thickness and photoinitiator concentration.\n\n3. **Environmental Control:**\n   - Maintain ambient temperature (20\u201325 \u00b0C) during polymerization to prevent thermal effects that could degrade hydrophilic functionalities.\n   - Exclude oxygen during polymerization (e.g., by purging with nitrogen gas) to avoid inhibition of free radical polymerization.\n\n---\n\n#### **Step 4: Post-Polymerization Handling**\n1. **Polymer Washing:**\n   - Wash the cured polymer with distilled water or ethanol to remove unreacted monomer or photoinitiator residues.\n   - This step ensures the final polymer is free of impurities and safe for application.\n\n2. **Drying:**\n   - Dry the polymer under vacuum or at room temperature to preserve its hydrophilic properties.\n\n---\n\n### Why Choose Photopolymerization?\n\n1. **Preservation of Hydrophilicity:**\n   - Photopolymerization occurs under mild conditions that minimize the risk of side reactions, preserving the hydrophilic functional groups.\n   - Hydrophilic photoinitiators like Irgacure 2959 are compatible with aqueous systems and do not interfere with the hydrophilic nature of the polymer.\n\n2. **Efficient Curing:**\n   - UV-induced polymerization is fast and highly efficient, ensuring uniform curing of the bisphenol A-based (meth)acrylate.\n\n3. **Temperature Control:**\n   - Unlike thermal polymerization, UV curing is carried out at room temperature, avoiding the degradation of temperature-sensitive groups.\n\n4. **Process Simplicity:**\n   - Photopolymerization does not require complex equipment, making it a practical and economical choice for hydrophilic polymer preparation.\n\n---\n\n### Final Remarks:\nThe above procedure provides a systematic approach to cure hydrophilic bisphenol A-based (meth)acrylates while ensuring that the hydrophilic properties are preserved. UV photopolymerization with hydrophilic photoinitiators is a robust and versatile method, suitable for creating hydrophilic polymers tailored to a wide range of applications such as coatings, hydrogels, and biomedical materials.\n\nFeel free to follow up if you have any further questions!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe a detailed procedure for synthesizing a hydrophilic polymer using 2-(dimethylamino)ethyl methacrylate (DMAEMA) as a primary monomer through free radical polymerization. Include steps for purification and any post-modification, if applicable."}, {"role": "assistant", "content": "Certainly! To synthesize a hydrophilic polymer using **2-(dimethylamino)ethyl methacrylate (DMAEMA)** as the primary monomer via free radical polymerization, I'll provide a detailed and systematic experimental procedure. Let's analyze the question and move step by step for clarity.\n\n---\n\n### **Key Points of the Question**\n1. **Monomer information**: The main monomer is DMAEMA. This is an amphiphilic monomer and under appropriate conditions, it can be used to synthesize hydrophilic polymers.\n2. **Polymerization technique**: The synthesis should use free radical polymerization, a widely used and versatile method for polymerization.\n3. **Final product**: A hydrophilic polymer, with possible post-modification to increase or enhance hydrophilicity, if required.\n4. **Key steps required**: Detailed description of the **synthesis process**, **purification**, and **post-modification** with reaction specifics.\n\n---\n\n### **Detailed Procedure**\n\n#### **I. Materials and Reagents**\n- **2-(Dimethylamino)ethyl methacrylate (DMAEMA)** (monomer) - ensure it is inhibitor-free.\n- **Azoisobutyronitrile (AIBN)** - a thermal free radical initiator.\n- Solvent: Ethanol or a water-ethanol mixture (acts as the reaction medium and enhances hydrophilicity).\n- Deionized (DI) water.\n- Methanol (for purification by precipitation).\n- Optional post-modification reagents:\n  - **Hydrochloric acid (HCl)** (to quaternize amines and increase charge/hydrophilicity).\n\n---\n\n#### **II. Instrumentation**\n- Round-bottom flask with **magnetic stirrer** and reflux condenser.\n- Oil bath or water bath for controlled heating.\n- Nitrogen gas source for creating an inert atmosphere.\n- Rotary evaporator.\n- Ultrafiltration or dialysis membrane (for purification).\n\n---\n\n#### **III. Experimental Scheme**\n\n---\n\n### **Step 1: Monomer Preparation**\n1. **Remove inhibitors**: Commercial DMAEMA monomers usually contain inhibitors like hydroquinone or MEHQ (to prevent premature polymerization). You must remove them before polymerization. \n   - Pass the monomer through a **basic alumina column** to adsorb the inhibitors.\n   - Alternatively, you can perform a **distillation under reduced pressure** to purify the monomer.\n\n2. Store the purified monomer in a dry, nitrogen-filled sealed container to prevent degradation.\n\n---\n\n### **Step 2: Polymerization Reaction**\n\n**1. Preparation of Reaction Solution:**\n- Add monomer (DMAEMA) and solvent (ethanol or ethanol-water mixture) into a clean, dry 250 mL round-bottom flask.\n  - **Example composition**: For a 1:100 (initiator:monomer) ratio:\n    - DMAEMA: ~10 mL (~66 mmol; density = 0.942 g/mL, molecular weight = 157.2 g/mol).\n    - AIBN: ~0.108 g (0.66 mmol; molecular weight = 164.21 g/mol, as 1% molar ratio to monomer).\n    - Solvent: Add ~40 mL of ethanol or ethanol-water mixture (60:40) to dilute the mixture.\n\n- Ensure the mixture has good stirring to completely dissolve all reagents.\n\n**2. Degassing:**\n- Purge the reaction mixture with nitrogen gas to remove oxygen for ~30 minutes. Oxygen inhibits free radical polymerization by scavenging radicals.\n\n**3. Polymerization:**\n- Attach a reflux condenser to the flask and place the setup in an oil bath preheated to ~65\u00b0C.\n- Heat and stir the reaction mixture at this temperature for 8\u201312 hours.\n  - The specific temperature should be close to the decomposition temperature of AIBN (~65\u201370\u00b0C). Avoid overheating to prevent premature termination.\n  - Monitor the viscosity of the solution over time \u2014 increased viscosity indicates polymerization.\n\n---\n\n### **Step 3: Precipitation and Purification**\n1. **Precipitation**:\n   - After completing the reaction, cool the solution to room temperature.\n   - Slowly pour the reaction mixture into a large volume (~300 mL) of cold methanol or diethyl ether with vigorous stirring. This will precipitate the polymer product.\n   - Collect the precipitated polymer by filtration or centrifugation.\n\n2. **Reprecipitation**:\n   - Dissolve the polymer in a minimum amount of ethanol or DI water (depending on polymer solubility), then reprecipitate in cold methanol or diethyl ether. Repeat this process twice to remove unreacted monomers, initiator, and byproducts.\n\n3. **Drying**:\n   - Transfer the purified polymer to a vacuum oven or desiccator and dry at ~40\u201350\u00b0C (or ambient temperature) under reduced pressure for 24 hours to obtain the final polymer.\n\n---\n\n### **Step 4: Post-Modification (Optional)**\nTo enhance hydrophilicity, DMAEMA polymers can be chemically modified:\n\n- **Quaternization**:\n  - Dissolve the polymer in an ethanol-water mixture and add a few drops of concentrated HCl (or other acids like CH3I for methylation).\n  - Stir the mixture at room temperature for ~12 hours. The tertiary amines in DMAEMA will quaternize to form positively charged ammonium salts, significantly enhancing hydrophilicity.\n  - Purify the quaternized polymer by dialysis (using DI water) or precipitation, as described earlier.\n\n---\n\n### **Step 5: Characterization**\nOnce the final polymer is prepared, conduct the following characterization techniques:\n1. **Gel Permeation Chromatography (GPC)**: To determine molecular weight distribution (e.g., weight-average and number-average molecular weights, \\( Mw \\) and \\( Mn \\)).\n2. **Fourier Transform Infrared (FTIR) spectroscopy**: Confirm the chemical structure and identify functional groups (e.g., quaternized ammonium groups, C=O stretching from methacrylate backbone).\n3. **Dynamic Light Scattering (DLS)**: If using in aqueous solution, measure solubility, hydrodynamic diameter, or zeta potential.\n4. **Contact angle measurements**: Assess surface hydrophilicity.\n5. **Nuclear Magnetic Resonance (NMR)**: Verify polymerization efficiency and quantify chemical modification.\n\n---\n\n### **Summary**\nBy following this detailed free radical polymerization procedure, you will synthesize a hydrophilic polymer from DMAEMA. Optional quaternization further enhances hydrophilicity by introducing charged groups. Ensure proper purification and characterization for high-quality polymer products.\n\nFeel free to clarify any step or request further specific details!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe how you would use a multi-functional isocyanate compound such as hexamethylene diisocyanate to crosslink the polymer and explain its significance in achieving the desired hydrophilic properties."}, {"role": "assistant", "content": "Certainly, let's break down your inquiry regarding using hexamethylene diisocyanate (HDI), a multifunctional isocyanate, to crosslink polymers for improving hydrophilic properties. I will analyze your question first, summarize the key points, and provide a systematic and detailed experimental preparation scheme.\n\n---\n\n### **1. Analysis of the Question and Key Points**\nTo approach your question logically:\n- You inquire about crosslinking polymers using HDI and the significance of its role in achieving hydrophilic properties.\n- The primary focus is on utilizing HDI, an aliphatic diisocyanate compound, as a crosslinking agent.\n- HDI must react with functional groups in the polymer to form crosslinks that enhance hydrophilicity.\n\nKey considerations:\n1. HDI's bifunctionality allows it to react with nucleophilic functional groups (e.g., hydroxyl, amine) on the polymer backbone or side chains.\n2. Crosslinking needs to be controlled to minimize insolubility or brittleness while promoting hydrophilic features.\n3. Hydrophilic properties can be engineered with suitable functional additives and modification during the polymer crosslinking process.\n\n---\n\n### **2. Systematic Preparation Scheme for Crosslinking Using HDI**\n\nHere is the detailed step-by-step synthesis protocol to crosslink polymers with HDI. I will include reaction conditions, reagent quantities, and how they contribute to hydrophilicity.\n\n#### **Step 1: Preparation of Polymer Base**\nThe starting polymer should contain reactive functional groups capable of engaging in a reaction with the isocyanate groups (-NCO) of HDI. Common functional groups include:\n- Hydroxyl groups (-OH) in poly(vinyl alcohol) or polyethylene glycol (PEG).\n- Amine groups (-NH2) in poly(amidoamine) or other polymers with primary/secondary amines.\n\nIn this example, we will assume the base polymer is polyethylene glycol (PEG), chosen for its inherent hydrophilicity due to the ether (-O-) linkages along its backbone.\n\n1. **Materials Needed**:\n   - Polyethylene glycol (PEG, molecular weight ~2000 g/mol).\n   - Hexamethylene diisocyanate (HDI).\n   - Catalyst: Stannous octoate or dibutyltin dilaurate (to accelerate urethane bond formation).\n\n2. **Reagent Ratios**:\n   - Mole ratio of HDI to functional groups in the polymer: Adjust to maintain slight molar excess of HDI (1.1:1).\n   - For 10 g of PEG (approx. 5 mmol hydroxyl groups): Use **5.5 mmol of HDI**.\n\n3. **Significance of Polymer Choice**:\n   PEG itself is hydrophilic due to its ether functionalities, but crosslinking will stabilize this structure and reduce solubility without compromising hydrophilic behavior. This ensures water compatibility and an extended hydrophilic network.\n\n---\n\n#### **Step 2: Dissolution and Mixing**\n1. **Procedure**:\n   - Dissolve PEG in anhydrous toluene or dimethylformamide (DMF). Use solvent volume sufficient for complete homogeneity (e.g., 50 mL for 10 g PEG).\n   - Add HDI into the solution dropwise to prevent localized excess, which could lead to uneven crosslinking.\n   - Stir the solution at room temperature (or slightly elevated to ~40 \u00b0C) under nitrogen gas to prevent moisture interference with the isocyanate groups (moisture may lead to urea formation).\n\n2. **Reaction Conditions**:\n   - Maintain stirring for 1-2 hours.\n   - Introduce a catalyst such as stannous octoate (~0.1% w/v relative to polymer) after initial mixing to accelerate crosslinking.\n\n---\n\n#### **Step 3: Crosslinking Reaction**\n1. **Mechanism**:\n   - The HDI molecule reacts via its isocyanate (-NCO) groups with hydroxyl (-OH) groups from PEG to form urethane linkages (-NH-CO-O-).\n   - HDI's bifunctionality allows it to form a stable network of crosslinks between multiple polymer chains.\n\n2. **Control Parameters**:\n   - Temperature: Ideally 40\u201360 \u00b0C. Excess heat must be avoided to prevent polymer degradation or rapid gelation.\n   - Reaction time: 6\u201312 hours, depending on the concentration of reagents and desired degree of crosslinking.\n\n---\n\n#### **Step 4: Post-Reaction Processing**\n1. **Purification**:\n   - The resulting crosslinked polymer will be insoluble in the reaction solvent but may swell in water or other polar solvents.\n   - Wash the product with anhydrous acetone or ethanol to remove unreacted HDI and residual catalyst.\n   - Dry under vacuum at 40 \u00b0C for 24 hours.\n\n2. **Characterization**:\n   - Verify successful crosslinking and hydrophilic enhancement using:\n     - FTIR spectroscopy: Check for urethane peaks (characteristic C=O stretch at ~1690 cm\u207b\u00b9 and N-H stretch at ~3300 cm\u207b\u00b9).\n     - Swelling tests in water: Assess hydrophilic behavior by measuring water uptake or swelling percentage.\n     - Contact angle measurements: Demonstrate reduced hydrophobicity of the crosslinked polymer.\n\n---\n\n### **3. The Significance of HDI Crosslinking in Enhancing Hydrophilicity**\n1. **Formation of Crosslinked Networks**:\n   - HDI forms stable urethane bonds, creating a robust three-dimensional network. This structure improves the polymer's mechanical strength without compromising its ability to interact with water through hydrogen bonding.\n\n2. **Hydrophilic Nature**:\n   - Hydrophilic polymers like PEG retain their ability to swell or absorb water, thanks to the polar nature of urethane linkages and PEG's ether-based structure.\n\n3. **Applications**:\n   - Used in hydrogel formation, coatings, or biomedical devices requiring water compatibility.\n   - Crosslinking limits polymer dissolution in water while maximizing hydrophilic interaction, making it suitable for moist environments.\n\n---\n\n### **Conclusion**\nBy using HDI to crosslink a polymer such as PEG, you can create a hydrophilic network that balances structural stability with water compatibility. The detailed preparation protocol provided should guide you through the synthesis process systematically, enabling successful implementation in the laboratory."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe how you would utilize 3-glycidoxypropyltrimethoxysilane in a procedure to functionalize glass slides before coating a hydrophilic polymer. Specify the purpose of this treatment and how it contributes to enhancing the hydrophilicity of the final polymer material."}, {"role": "assistant", "content": "Certainly! As a materials science professor with expertise in hydrophilic polymers, I\u2019ll guide you step-by-step through the process of functionalizing glass slides with 3-glycidoxypropyltrimethoxysilane (GPTMS) as part of a preparation scheme for enhancing the hydrophilicity of the final polymer material. I will also explain the purpose of each step to enrich your understanding.\n\n---\n\n### **Step 1: Analyze the Question and Summarize Key Points**\n\n**Key Question Goals:**\n1. Design a procedure to functionalize glass slides using GPTMS.\n2. Specify the purpose of this surface treatment.\n3. Explain how the treatment enhances hydrophilicity of the final polymer material.\n\n---\n\n### **Step 2: Systematic Experimental Procedure**\n\nBelow is a detailed, systematic procedure for functionalizing glass slides with GPTMS and subsequently coating them with a hydrophilic polymer:\n\n---\n\n#### **Materials Required**\n1. Glass slides (cleaned thoroughly, as described in Step 3).\n2. 3-Glycidoxypropyltrimethoxysilane (GPTMS).\n3. Absolute ethanol or isopropanol (as the solvent).\n4. Deionized (DI) water.\n5. Glacial acetic acid (or another acid catalyst, e.g., HCl, if needed).\n6. Nitrogen (N\\(_2\\)) or argon gas (for inert environment, if used).\n7. Hydrophilic polymer precursor (specific to your experiment, such as poly(ethylene glycol)-based polymer, polyacrylamide, etc.).\n8. Oven or hot plate (for curing).\n9. Desired buffer/reagents for hydrophilic polymer synthesis and application.\n\n---\n\n#### **Step 3: Cleaning and Preparing Glass Slides**\nThe first step ensures the glass surface is free of contaminants like grease, dust, or residual organics that can inhibit silanization.\n\n1. **Initial Cleaning:** Immerse the glass slides in a piranha solution (3:1 concentrated sulfuric acid: 30% hydrogen peroxide) to remove organic residues. *(Caution: Handle piranha solution with extreme care! Always add H\\(_2\\)O\\(_2\\) to acid, not vice versa.)*\n   \n2. **Rinse:** After cleaning, rinse the slides thoroughly with copious amounts of deionized water.\n   \n3. **Ethanol/Isopropanol Wash:** Submerge the slides in ethanol or isopropanol to remove water from the surface. Allow them to air dry or gently dry them in a nitrogen/argon stream.\n   \n4. **Plasma Cleaning (Optional):** For further activation, expose the slides to oxygen plasma or UV-ozone treatment. This step increases surface hydroxyl groups, creating reactive sites for bonding with the silane.\n\n---\n\n#### **Step 4: Preparation of GPTMS Silanization Solution**\n1. Mix the silane solution by combining the following:\n   - 1% to 2% (v/v) GPTMS in absolute ethanol or isopropanol.\n   - Introduce a small amount (e.g., 0.1\u20130.2% v/v) of glacial acetic acid or any other acid catalyst to promote hydrolysis of the methoxy groups in GPTMS.\n   - Add DI water to the mixture in a molar ratio of approximately 1:3 molar equivalents of water to silane to initiate partial hydrolysis.\n   \n2. Allow the mixture to hydrolyze at room temperature for 15\u201330 minutes under constant stirring. The hydrolysis transforms the silane methoxy groups into reactive silanol groups (\\(-SiOH\\)), which will later condense with hydroxyl groups on the glass slide surface.\n\n---\n\n#### **Step 5: Functionalizing the Glass Slides**\n1. Immerse the cleaned glass slides in the silane solution completely, ensuring full coverage. Allow them to remain in the solution for 1\u20134 hours at room temperature or slightly elevated temperatures (e.g., 40\u201360\u00b0C).\n   \n2. After incubation, remove the slides from the solution and rinse gently with ethanol to remove loosely bound or excess silane.\n\n3. Cure the silane layer:\n   - Bake the coated slides in an oven at 100\u2013120\u00b0C for 1\u20132 hours. This step induces condensation reactions between the silanol groups of GPTMS and hydroxyl groups on the glass slide surface, forming covalent \\(-Si-O-Si-\\) linkages.\n   - This curing step stabilizes the silane layer and ensures strong attachment to the glass substrate.\n\n4. After curing, allow the slides to cool to room temperature in a clean and dust-free environment. At this stage, the glass slide is successfully functionalized with GPTMS.\n\n---\n\n#### **Step 6: Coating or Grafting the Hydrophilic Polymer**\n1. **Activation of Epoxide Groups:** The functionalized surface now contains terminal glycidoxy (epoxide) groups that can react chemically with hydrophilic polymer precursors or crosslinkers. These epoxide groups are highly reactive toward nucleophiles such as amines, hydroxyls, or thiols.\n\n2. Prepare the hydrophilic polymer:\n   - For example, if using a poly(ethylene glycol) (PEG)-based polymer, mix the PEG polymer or precursor with a coupling agent and initiator to react with the epoxide group.\n   - Another example is coating polyacrylamide or acrylate-based hydrogels by initiating free-radical polymerization on the reactive surface.\n\n3. Apply the polymer or precursor to the silanized slide:\n   - Spread or dip-coat the functionalized slides in the polymer solution.\n   - Allow the reaction between the epoxide groups on the GPTMS and the functional groups of the polymer to proceed for the required time, typically under ambient or slightly elevated temperatures (e.g., 40\u201360\u00b0C).\n   - Ensure proper curing/grafting steps, based on the polymer used.\n\n4. Rinse off any unreacted polymer with a compatible solvent, such as water or ethanol.\n\n---\n\n#### **Step 7: Evaluation of Surface Hydrophilicity**\n1. To confirm enhancement of hydrophilicity, conduct surface characterization:\n   - Perform water contact angle measurements before and after polymer coating. A significant decrease in the contact angle confirms higher hydrophilicity.\n   - Use techniques like FTIR or XPS to confirm successful silanization and polymer attachment.\n\n---\n\n### **Purpose of GPTMS Functionalization**\n\nFunctionalization with GPTMS serves the following purposes:\n1. **Enhanced Surface Adhesion:** The covalent \\(-Si-O-Si-\\) bonds between the GPTMS and the glass surface ensure strong adhesion of the polymer to the substrate.\n2. **Chemical Reactivity:** The epoxide group in GPTMS serves as a versatile anchor that forms covalent bonds with nucleophilic groups in hydrophilic polymers. This tailored reactivity facilitates uniform and strong polymer attachment.\n3. **Improved Hydrophilicity:** GPTMS-treated surfaces provide a functional interface that allows robust binding of hydrophilic polymers, which significantly increases the overall hydrophilicity of the material.\n\n---\n\n### **How This Treatment Enhances Hydrophilicity**\n\n1. **Stable Polymer Attachment:** By functionalizing glass with a reactive silane like GPTMS, the hydrophilic polymer can be stably grafted or attached to the surface. This prevents polymer delamination or degradation over time.\n2. **Uniform Hydrophilic Coating:** A robust interface promotes uniform polymer dispersion, minimizing hydrophobic regions and maximizing water attraction.\n3. **Water-Wicking Behavior:** Hydrophilic polymers, when attached to such functionalized surfaces, promote hydrogen bonding and capillary action, further enhancing hydrophilicity.\n\n---\n\n### **Conclusion**\n\nThe functionalization of glass slides with GPTMS is an essential preparatory step for grafting hydrophilic polymers. Through precise silanization and polymer coating, the hydrophilicity of the final material is greatly improved, allowing for applications in biomedical devices, antifouling surfaces, and hydrophilic coatings."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Considering 2-(dimethylamino)ethyl methacrylate (DMAEMA) as one of the monomers, how would you vary its flow rate during initiated chemical vapor deposition to influence the chemical composition of the copolymer for improved hydrophilicity? Justify your reasoning."}, {"role": "assistant", "content": "To answer your question about how to vary the flow rate of 2-(dimethylamino)ethyl methacrylate (DMAEMA) during initiated chemical vapor deposition (iCVD) to influence the chemical composition of the copolymer and enhance hydrophilicity, let's analyze the question step by step and design an experimental approach systematically. I will also provide justification for each decision and detailed experimental parameters.\n\n---\n\n### 1. **Analyze the Question and Summarize Key Points**\nAt the core of your question is DMAEMA, a monomer with an amine-containing side group, which introduces certain hydrophilic characteristics via hydrogen bonding or ionic interactions when protonated. However, the degree to which it contributes to the hydrophilicity of the resultant copolymer depends on its incorporation in the final polymer structure. Your query specifically asks:\n   - How varying the flow rate of DMAEMA during iCVD can influence the copolymer\u2019s chemical composition.\n   - How this can be used strategically to enhance the hydrophilicity of the polymer.\n\nKey considerations here include:\n   - The relationship between flow rate of DMAEMA, its partial pressure in the reactor, and its incorporation into the copolymer.\n   - The choice of a co-monomer (if any) and how the relative amount of DMAEMA in the polymer backbone affects the hydrophilicity.\n   - Optimizing the copolymer's overall composition to ensure maximum hydrophilicity while maintaining process control.\n\n---\n\n### 2. **Understanding the Principles Behind iCVD**\nBefore proceeding to the synthesis, understanding the mechanics of iCVD is crucial:\n   - iCVD relies on the adsorption of monomer vapors onto a substrate in the presence of an initiator species (e.g., a thermal initiator like tert-butyl peroxide or TBPO).\n   - The relative rates of adsorption and subsequent polymerization of each monomer correlate with the monomer's vapor pressure and flow rate, affecting the final copolymer composition.\n   - Controlling individual monomer flow rates allows us to tune the composition of the copolymer in situ.\n\nIn the context of DMAEMA, its relatively hydrophilic nature can be contrasted with a more hydrophobic co-monomer (e.g., methyl methacrylate or ethyl methacrylate). By modulating its flow rate, we can increase or decrease its incorporation into the copolymer to favor hydrophilicity.\n\n---\n\n### 3. **Experimental Preparation Scheme**\n\n#### **Step 1: Selection of Monomers**\n- **Monomer A:** DMAEMA (hydrophilic). Its flow rate will be varied to control the hydrophilic content.\n- **Monomer B (co-monomer):** Choose a complementary hydrophobic monomer (e.g., methyl methacrylate, MMA, or butyl acrylate, BA) to form a balanced copolymer structure. The purpose of the co-monomer is to help polymer chain propagation while introducing structural stability to the copolymer.\n\n---\n\n#### **Step 2: Reactor Setup for iCVD**\n1. Use a stainless steel iCVD reactor with precise flow controllers for each gas input.\n2. Equip the system with:\n   - A vaporizer for DMAEMA monomer.\n   - A separate vaporizer for the co-monomer.\n   - A thermal initiator vaporizer (e.g., tert-butyl peroxide).\n3. Maintain substrate temperature at ~30\u201340\u00b0C to promote physical adsorption of the monomers without initiating unwanted side reactions.\n\n---\n\n#### **Step 3: Optimization of Process Parameters**\nTo evaluate the effect of DMAEMA's flow rate, start with a baseline condition and systematically vary DMAEMA flow while keeping other parameters constant.\n\n**Baseline Conditions:**\n- **Monomer A (DMAEMA):** Flow rate = 2 sccm (standard cubic centimeters per minute).\n- **Monomer B (co-monomer):** Flow rate = 2 sccm.\n- **Initiator (TBPO):** Flow rate = 1 sccm.\n- **Reaction Pressure:** Maintain at ~0.5\u20131 Torr. Optimize pressure to ensure uniform adsorption of monomer vapors.\n- **Substrate Temperature:** 30\u00b0C.\n- **Filament Temperature:** 250\u2013280\u00b0C to thermally decompose the initiator into free radicals for polymerization.\n- **Reaction Time:** 30 minutes.\n\n---\n\n#### **Step 4: Systematic Variation of DMAEMA Flow Rate**\nTo study its effect on copolymer composition:\n1. Vary DMAEMA flow rate between 1\u20135 sccm in increments of 1 sccm while keeping other flow rates stable.\n2. For each increment:\n   - Record the total monomer incorporation using Fourier-transform infrared spectroscopy (FTIR) or X-ray photoelectron spectroscopy (XPS).\n   - Measure the resultant surface hydrophilicity using contact angle measurements: lower contact angle correlates to higher hydrophilicity.\n   - Analyze the final copolymer composition using nuclear magnetic resonance spectroscopy (NMR) or gel permeation chromatography (GPC).\n\n---\n\n#### **Step 5: Parameter Justification for Enhanced Hydrophilicity**\n- **Low DMAEMA Flow Rate (1\u20132 sccm):** Produces a copolymer with a lower DMAEMA content, favoring hydrophobic character.\n- **Moderate DMAEMA Flow Rate (3 sccm):** Balances hydrophilic and hydrophobic content, leading to moderate hydrophilicity.\n- **High DMAEMA Flow Rate (4\u20135 sccm):** Maximizes DMAEMA incorporation, increasing hydrophilicity but may compromise film uniformity if the monomer over-adsorbs.\n  - Consider protonating DMAEMA post-polymerization (e.g., with dilute HCl) to form positively charged ammonium groups, further enhancing hydrophilicity through ionic effects.\n\n---\n\n#### **Step 6: Post-Synthesis Characterization**\n1. Analyze copolymer structure via FTIR and XPS to confirm incorporation.\n   - Peaks at ~1730 cm\u207b\u00b9 (carbonyl stretch) indicate successful polymerization.\n   - Peaks related to amine groups (~2800\u20132900 cm\u207b\u00b9) confirm DMAEMA presence.\n2. Perform water contact angle measurements to quantify hydrophilicity:\n   - Ideal hydrophilic polymers exhibit contact angles <30\u00b0.\n3. Evaluate thermal stability (TGA) and molecular weight distribution (GPC).\n\n---\n\n### 4. **Justification for Approach**\n1. **Why flow rate matters:** In iCVD, the monomer\u2019s partial pressure directly affects its incorporation into the polymer. Increasing DMAEMA flow boosts its adsorption rate on the substrate, modifying the copolymer composition.\n2. **Optimizing hydrophilicity:** Higher DMAEMA fractions enhance polar moieties but must be balanced with co-monomers to maintain structural and process stability.\n3. **Post-polymerization treatment:** Protonation or further functionalization ensures maximal hydrophilicity and application-specific functionality.\n\n---\n\n### 5. **Summary**\nBy systematically varying the DMAEMA flow rate during iCVD and monitoring the copolymer's composition and hydrophilicity, a tailor-made polymer can be fabricated with enhanced hydrophilic properties. This approach provides precise control over chemical composition and surface characteristics, offering a robust design strategy for hydrophilic polymer synthesis."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain how you would monitor the progress of the polymerization reaction involving MDI using Raman spectroscopy. Identify which spectral feature of MDI you would focus on and how you would use this information to determine the conversion of the reaction."}, {"role": "assistant", "content": "Certainly! Let\u2019s systematically approach your question about monitoring the progress of a polymerization reaction involving MDI (methylene diphenyl diisocyanate) using Raman spectroscopy. I\u2019ll break down the process step by step to ensure clarity.\n\n---\n\n### **Step 1: Analyze the Question and Summarize Key Points**\nYour question pertains to monitoring a polymerization reaction involving MDI. Specifically, you are asking:\n- How Raman spectroscopy can be used for this purpose.\n- Which spectral feature of MDI should be monitored.\n- How to determine the reaction's progress (conversion) using the information from Raman spectroscopy.\n\nTo answer comprehensively, I will:\n1. Briefly explain the chemistry of MDI and its relevance to the reaction.\n2. Identify the key Raman-active functional group in MDI to monitor.\n3. Provide step-by-step guidance on using Raman spectroscopy to track conversion during polymerization.\n\n---\n\n### **Step 2: Overview of MDI Chemistry**\nMDI is a diisocyanate widely used in polymerization reactions, particularly in forming polyurethanes. A typical polymerization reaction involving MDI occurs between the \u2013N=C=O (isocyanate groups) of MDI and hydroxyl-containing compounds (such as polyols). During this process:\n- The isocyanate groups react with hydroxyl groups to form urethane linkages (-NH-CO-O-).\n- The consumption of the isocyanate group is a direct indicator of reaction progress.\n\nBecause MDI contains two isocyanate groups per molecule, monitoring the disappearance of the \u2013N=C=O functional group during the reaction is critical for determining the reaction's progress.\n\n---\n\n### **Step 3: Key Raman Spectral Feature of MDI**\nRaman spectroscopy is ideally suited for monitoring isocyanate functionality due to its sensitivity to certain vibrational modes. The key feature for MDI is:\n- The **Raman-active symmetric stretching vibration of the isocyanate group (\u2013N=C=O)**, which typically appears as a strong band in the Raman spectrum around **2230\u20132270 cm\u207b\u00b9**.\n\nThis distinct band is well-separated from other vibrational features, making it ideal for monitoring the consumption of \u2013N=C=O during the reaction.\n\n---\n\n### **Step 4: Experimental Monitoring Procedure with Raman Spectroscopy**\n\n#### **4.1. Initial Setup**\n1. **Instrumentation**: Use a Raman spectrometer equipped with a laser source (commonly 532 nm, 785 nm, or 1064 nm) suitable for your sample. Choose a laser wavelength to minimize fluorescence, especially for aromatic compounds like MDI.\n2. **Sample Preparation**: \n   - Prepare the polymerization reaction mixture by combining MDI with the co-monomer/polyol under controlled stoichiometry.\n   - Ensure the reaction is run in a sealed vessel (if necessary) to prevent moisture from interfering, as isocyanate groups are highly reactive with water.\n3. **Baseline Spectrum of MDI**:\n   - Before starting the reaction, record the Raman spectrum of pure MDI as a reference.\n   - Note the intensity of the isocyanate peak (~2230\u20132270 cm\u207b\u00b9).\n\n#### **4.2. Real-Time Reaction Monitoring**\n1. **Time-Resolved Spectroscopy**:\n   - Collect Raman spectra of the reaction mixture at regular intervals (e.g., every 5\u201310 minutes) during the polymerization reaction.\n   - Focus on the spectral region around 2100\u20132300 cm\u207b\u00b9 for tracking the isocyanate peak.\n\n2. **Monitoring the Intensity**:\n   - Observe the gradual decrease in the intensity of the isocyanate peak (~2230\u20132270 cm\u207b\u00b9) over time. The decrease indicates the consumption of isocyanate groups as the reaction progresses.\n\n#### **4.3. Quantifying Conversion of MDI**\n1. **Peak Intensity Ratio Method**:\n   - Use the intensity of the isocyanate peak at a specific time, \\( I_t \\), relative to its initial intensity, \\( I_0 \\).\n   - The conversion, \\( X \\), of MDI can be calculated as:\n     \\[\n     X = \\frac{I_0 - I_t}{I_0} \\times 100\\%\n     \\]\n     where \\( I_t \\) is the peak intensity of \u2013N=C=O at time \\( t \\) and \\( I_0 \\) is the initial peak intensity before the reaction starts.\n\n2. **Internal Standard (Optional)**:\n   - To improve accuracy, you can compare the isocyanate peak intensity to an internal standard (a non-reactive spectral feature in the same sample) rather than relying solely on the absolute intensity.\n\n#### **4.4. End-Point Determination**\n- The reaction is considered complete when the isocyanate peak at 2230\u20132270 cm\u207b\u00b9 is no longer detectable, indicating complete consumption of \u2013N=C=O groups.\n- If the intensity plateaus but does not reach zero, it may indicate incomplete reaction due to stoichiometric mismatch, side reactions, or reagent impurities.\n\n---\n\n### **Step 5: Important Considerations**\n1. **Controlling Reaction Conditions**:\n   - Perform the reaction under controlled temperature (typically 50\u201380\u00b0C for urethane formation) and exclude moisture to prevent side reactions.\n2. **Calibration**:\n   - Validate the Raman-based conversion determination by performing parallel experiments with a quantitative chemical analysis method (e.g., FTIR or NMR spectroscopy).\n3. **Interference**:\n   - Ensure no other components in the reaction mixture (e.g., solvents or additives) produce Raman bands overlapping with the \u2013N=C=O region.\n\n---\n\n### **Step 6: Summary**\nTo monitor the polymerization reaction of MDI using Raman spectroscopy, you focus on the isocyanate group\u2019s symmetric stretching band (~2230\u20132270 cm\u207b\u00b9). By tracking the intensity decrease of this band over time, you can determine the reaction conversion. This method is straightforward, non-destructive, and highly sensitive to changes in isocyanate concentration, allowing real-time reaction monitoring in the lab.\n\nWith careful execution of the outlined procedure and attention to details such as calibration and temperature control, you should be able to successfully track your polymerization reaction and evaluate its progress quantitatively.\n\nLet me know if you have further questions or need assistance with experimental design specifics!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Outline an experimental approach for utilizing acrylic acid (AA) in the synthesis of a hydrophilic polymer. What reactions need to occur to ensure the incorporation of this molecule into the polymer structure?"}, {"role": "assistant", "content": "Certainly. Let us now address your question methodically, considering the use of acrylic acid (AA) for synthesizing a hydrophilic polymer.\n\n---\n\n### 1. **Analysis of the Question and Key Points**:\n- The primary goal is to prepare a hydrophilic polymer using acrylic acid (AA) as one of the main building blocks.\n- Acrylic acid is a versatile molecule often used in the synthesis of hydrophilic polymers because of its carboxylic acid group (-COOH), which imparts hydrophilicity.\n- To achieve this, we need to strategically polymerize acrylic acid into a more hydrophilic macromolecular structure, ensuring the -COOH groups are preserved or functionalized to enhance hydrophilicity.\n- The two most common approaches include **homopolymerization** (polyacrylic acid) or **copolymerization** with other monomers to introduce additional functionality.\n\nNow, I will outline a step-by-step experimental scheme to create a hydrophilic polymer from acrylic acid, including all relevant reaction conditions and process details.\n\n---\n\n### 2. *Experimental Scheme for Synthesizing a Hydrophilic Polymer Using Acrylic Acid*\n\n#### **Step 1: Selection of Polymerization Method**\nAcrylic acid can be polymerized via free radical polymerization, which is widely used for producing hydrophilic polymers efficiently and reproducibly.\n\n- **Polymerization Strategy**:\n  - **Homopolymerization:** If the goal is to produce poly(acrylic acid) (PAA), acrylic acid is polymerized as the sole monomer.\n  - **Copolymerization:** To further enhance hydrophilicity or introduce specialized properties, AA can be copolymerized with other hydrophilic monomers (e.g., acrylamide, hydroxyethyl methacrylate).\n\nFor simplicity, I will describe both approaches.\n\n---\n\n#### **Step 2: Materials and Reagents**\n- **Monomers**:\n  - Acrylic acid (AA): Ensure it is of high purity (>99% to minimize impurities).\n  - Co-monomers (if needed): Acrylamide (AM) or other vinyl monomers.\n- **Initiator**:\n  - A water-soluble, free radical initiator such as ammonium persulfate (APS).\n- **Crosslinking Agent (if desired)**:\n  - N,N'-methylenebisacrylamide (MBA) can be added to form a crosslinked hydrogel structure.\n- **Solvent**:\n  - Deionized water or a water-organic mixture.\n- **pH Adjuster**:\n  - Sodium hydroxide (NaOH) or other bases if neutralization of acrylic acid is desired for specific properties.\n\n---\n\n#### **Step 3: Reaction Procedure (Homopolymerization of AA)**\n\n1. **Preparation of Reaction Mixture**:\n   - Dissolve acrylic acid monomer in deionized water to prepare a 10\u201330% (w/v) aqueous solution (depending on desired polymerization density).\n   - Optionally adjust the pH to ~7 by neutralizing a portion of the AA with NaOH, converting -COOH groups into sodium acrylate (-COONa); this will lead to a slightly hydrophilic, charged polymer.\n\n2. **Initiator Solution**:\n   - Dissolve 0.1\u20130.5% (w/v) ammonium persulfate (APS) in water and add the solution to the AA mixture under gentle stirring.\n\n3. **Polymerization Setup**:\n   - Transfer the solution to a nitrogen-purged reaction vessel (to eliminate oxygen, which inhibits radical polymerization).\n   - Heat the mixture to ~60\u201370\u00b0C while stirring gently; this will activate the persulfate initiator and initiate polymerization through the formation of free radicals on the double bonds of acrylic acid.\n\n4. **Completion**:\n   - Allow the polymerization to continue for 4\u20136 hours, maintaining a constant temperature.\n   - A viscous solution of poly(acrylic acid) (PAA) will result, with hydrophilic carboxylic acid groups (-COOH) distributed throughout the polymer backbone.\n\n---\n\n#### **Step 4: Reaction Procedure (Copolymerization Example)**\n\nIf copolymerization is desired (e.g., with acrylamide):\n\n1. **Preparation of Monomer Mixture**:\n   - Use a molar ratio of acrylic acid:acrylamide (AA:AM) = 70:30 or adjust based on the desired balance between carboxyl and amide functional groups.\n   - Dissolve the monomers in water similarly as described above, ensuring a total monomer concentration of ~10\u201320% (w/v).\n\n2. **Initiator and Polymerization Conditions**:\n   - Add ammonium persulfate (0.1\u20130.5% w/v) along with a crosslinker like MBA (0.1\u20130.3 mol% of total monomers for hydrogel formation).\n   - Carry out free radical polymerization as outlined in Step 3 under nitrogen atmosphere, heating at 60\u201370\u00b0C.\n\n3. **Resultant Polymer**:\n   - A copolymer of AA and AM (e.g., poly(AA-co-AM)) will be formed, containing both carboxylic acid (-COOH) and amide (-CONH2) groups. This structure is more hydrophilic and can form highly swellable hydrogels.\n\n---\n\n#### **Step 5: Purification of the Polymer**\n- Dialyze the resulting polymer solution against deionized water for 2\u20133 days to remove unreacted monomers and initiator residues.\n- Alternatively, precipitate the polymer by adding the reaction mixture to a non-solvent (e.g., acetone or ethanol), then filter and dry the polymer under vacuum.\n\n---\n\n### 3. *Ensuring Incorporation of Acrylic Acid into the Polymer Structure*\n\nThe incorporation of acrylic acid into the polymer backbone relies on free radical polymerization, wherein the vinyl double bond (-C=C-) of AA participates in chain growth. Key considerations are:\n- **Initiator Efficiency**: APS ensures rapid formation of free radicals to activate the acrylic acid monomers.\n- **Reaction Control**: Proper temperature and oxygen removal prevent side reactions.\n- **Crosslinking (Optional)**: Incorporating crosslinkers like MBA during synthesis enhances structural stability, especially for hydrogels, by attaching AA units through covalent bonding.\n\n---\n\n### 4. Notes for Experiment\n- **Hydrophilicity Enhancement**:\n  - Ensuring high molar content of AA in the polymer or copolymer will promote good water solubility or swellability, as the -COOH groups significantly interact with water.\n- **Alternative Functionalization**:\n  - The carboxylic groups (-COOH) can be further modified post-polymerization by converting them to carboxylate (-COO\u207b) via neutralization.\n\nWith this detailed plan, you should be able to synthesize a hydrophilic polymer efficiently while ensuring controlled reaction conditions and reproducible results.\n\nIf additional clarification or an alternative route is needed, feel free to ask!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Design an experimental sequence to synthesize a hydrophilic polymer using Dye-NHS ester as an initiator. Justify how this molecule contributes to the hydrophilicity of the resulting polymer without referencing proprietary information."}, {"role": "assistant", "content": "### Analysis of the Question\n\nYour question revolves around designing an experimental scheme for synthesizing a hydrophilic polymer using Dye-NHS ester as an initiator, while explaining the role of this molecule in improving hydrophilicity. Based on the given question, the following key points need to be addressed systematically:\n\n1. **Experimental framework:** Provide a detailed, step-by-step preparation sequence for polymer synthesis using Dye-NHS ester as the initiator. Specification of reaction conditions, quantities, and key synthetic procedures is required.\n2. **Hydrophilicity enhancement:** Scientifically justify why the Dye-NHS ester contributes to hydrophilicity and how its molecular structure influences the properties of the polymer.\n\nLet us proceed step by step, ensuring all scientific aspects are covered.\n\n---\n\n### Part 1: Experimental Sequence for Synthesizing a Hydrophilic Polymer\n\n**Objective:** To prepare a hydrophilic polymer initiated by Dye-NHS ester to ensure optimal hydrophilicity, while considering the functional reactivity of NHS esters and their incorporation into the polymer backbone.\n\n#### Step 1: Materials and Reagents Collection\n\n- **Dye-NHS ester:** Initiator molecule. NHS esters react efficiently with nucleophilic amines or hydroxyl-containing monomers.\n- **Hydrophilic monomer(s):** Choose monomers such as acrylamide (AM), polyethylene glycol (PEG) acrylate, N-vinylpyrrolidone (NVP), or hydroxyethyl methacrylate (HEMA), which form hydrophilic polymer chains.\n- **Solvent:** Prefer aqueous or mixed organic-aqueous solvents like DMSO-water or ethanol-water to promote solubility and maintain hydrophilicity during polymerization.\n- **Catalyst (optional):** Depending on the monomer, include catalysts such as ammonium persulfate (APS) for radical polymerization or use a thermal or photoinitiation pathway.\n- **Crosslinker (if needed):** For films or networks, optional hydrophilic crosslinkers like N,N\u2032-methylenebisacrylamide (MBA) may be added.\n\n---\n\n#### Step 2: Synthetic Procedure\n\n1. **Activation of Dye-NHS Ester:**\n   - Molecular dye components containing NHS esters act as coupling agents that facilitate polymer initiation. Dissolve Dye-NHS ester in an appropriate solvent (e.g., DMSO or ethanol) to activate the ester functionality.\n   - Place Dye-NHS ester (e.g., 0.01 mole) in a reaction vessel and stir at room temperature to ensure dissolution.\n\n2. **Preparation of Monomer Solution:**\n   - Prepare the hydrophilic monomer solution. Dissolve acrylamide (AM) or PEG acrylate in the solvent to create a mixture. Use a molar ratio of monomer to Dye-NHS ester in the range of **20:1\u201350:1**, depending on the desired molecular weight of the polymer.\n   - For example:\n     - Acrylamide (AM): Weigh ~2 g (0.03 mole).\n     - DMSO mixed with water (50:50 v/v) to maintain miscibility and control hydrophilicity.\n\n3. **Reaction Initiation (Coupling or Radical):**\n   - Slowly add Dye-NHS ester to the monomer solution under stirring. Allow the NHS ester to react with hydroxyl or amine groups of the monomers.\n   - If no natural nucleophiles are available, trigger radical polymerization using APS (0.01 mole) and heat (~60\u00b0C) in oxygen-free conditions (purge with nitrogen). Alternatively, UV irradiation could initiate polymerization using photoinitiators.\n\n4. **Polymer Chain Propagation:**\n   - Maintain the reaction temperature at 60\u00b0C for approximately 3\u20134 hours. If radical conditions are used, ensure uniform stirring under N2 atmosphere to prevent chain termination.\n\n5. **Polymer Purification:**\n   - Precipitate the polymer by pouring the reaction mixture into cold ethanol or acetone. Collect the precipitate by centrifugation or filtration.\n   - Wash the polymer thoroughly with ethanol and water to remove unreacted Dye-NHS ester or unreacted monomer traces.\n\n6. **Drying:**\n   - Dry the purified polymer in a vacuum oven at ~40\u00b0C to obtain the final hydrophilic polymer.\n\n---\n\n### Part 2: Justification of Hydrophilicity Improvement\n\n**Role of Dye-NHS Ester:**\n- **Reactive functionality:** The NHS ester group in Dye-NHS ester readily reacts with hydroxyl or amine-containing monomers, ensuring that the dye is covalently incorporated into the polymer backbone. This incorporation enhances the polarity and hydrophilicity of the polymer as NHS esters are compatible with hydrophilic monomers.\n  \n- **Dye contribution:** The molecular dye incorporated into the polymer backbone could contain hydrophilic substituents like sulfonic groups (-SO3H), carboxylic groups (-COOH), or hydroxyl groups (-OH). These substituents significantly increase the water solubility and wettability of the polymer surface.\n\n- **Hydrophilic scaffold:** As polymer chains grow, the NHS ester ensures functional grafting and compatibility with hydrophilic monomers, leading to an evenly distributed hydrophilic profile and preventing aggregation.\n\n---\n\n### Final Notes\n\nThe experiment outlined provides a clear, reproducible pathway for the synthesis of Dye-NHS ester-based hydrophilic polymers. The use of hydrophilic monomers in aqueous or mixed solvents complements the inherent polar properties introduced by Dye-NHS ester. By carefully controlling reagent ratios, reaction conditions, and purification steps, the student will achieve a hydrophilic polymer suitable for biomedical coatings, water purification, or other applications."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Methacrylic acid is used in the preparation of hydrophilic polymers. How would the carboxylic acid groups in methacrylic acid contribute to the hydrophilic nature of the final polymer, and what strategies can you use to ensure proper polymerization and uniform incorporation of this monomer into the polymer structure?"}, {"role": "assistant", "content": "Certainly. Let\u2019s analyze your question systematically and develop a detailed experimental preparation scheme for hydrophilic polymers based on methacrylic acid as a monomer.\n\n### **Analysis and Summarization**\nYour question involves:\n1. Understanding how the carboxylic acid groups in methacrylic acid contribute to the hydrophilicity of the final polymer.\n2. Strategies to ensure the proper polymerization and uniform incorporation of methacrylic acid into the polymer structure.\n\nThis requires a detailed explanation of the polymerization mechanism involving methacrylic acid and the optimization of experimental conditions to achieve an evenly distributed hydrophilic polymer.\n\n---\n\n### **Detailed Answer**\n\n#### **Step 1: Contribution of Carboxylic Acid Groups to Hydrophilicity**\nMethacrylic acid (MAA) contains a functional carboxylic acid group (-COOH), which plays a pivotal role in enhancing the hydrophilic nature of the polymer. The -COOH group:\n- **Hydrogen Bonding:** Can form strong hydrogen bonds with water molecules, increasing affinity for water.\n- **Ionization in Aqueous Media:** In slightly alkaline or neutral conditions, carboxylic acid groups can ionize to carboxylate anions (-COO\u207b), further improving water solubility and hydrophilicity.\n- **Functional Site for Further Modification:** Carboxylic acid groups can serve as anchor points for additional functionalization (e.g., grafting hydrophilic chains or biomolecules).\n\nIn a polymer structure, the presence of the -COOH group ensures that the resulting polymer has strong hydrophilic domains suitable for applications like biomaterials, water purification, or responsive hydrogels.\n\n---\n\n#### **Step 2: Strategies for Polymerization and Incorporation**\nTo ensure proper polymerization and uniform incorporation of MAA into the polymer structure, an optimized approach is required. Below is a step-by-step experimental preparation scheme:\n\n---\n\n### **Experimental Preparation Scheme**\n\n#### **Materials and Reagents**\n1. **Monomers:**\n   - Methacrylic acid (MAA): Primary hydrophilic monomer.\n   - Hydrophobic or neutral co-monomer (e.g., methyl methacrylate or acrylamide) for tuning hydrophilicity, if desired.\n2. **Initiator:**\n   - Azobisisobutyronitrile (AIBN) (for free radical polymerization) or potassium persulfate (KPS), depending on the polymerization method.\n3. **Solvent:**\n   - Water or polar solvent (e.g., ethanol-water mixture) to ensure the dissolution of methacrylic acid and enable hydrophilic interaction during polymerization.\n4. **Crosslinker (optional):**\n   - Bisacrylamide, if a crosslinked polymer/hydrogel is desired.\n5. **pH Modifiers:**\n   - Sodium hydroxide or ammonium hydroxide to adjust the pH and ionize carboxyl groups for increased hydrophilicity.\n\n---\n\n#### **Step 1: Monomer Selection and Composition**\n1. Decide the ratio of methacrylic acid to the co-monomer (if present) based on the desired hydrophilicity. A typical ratio could be:\n   - Pure MAA polymer (100% monomer).\n   - Copolymer with 70% MAA and 30% methyl methacrylate (MMM) or acrylamide.\n\n#### **Step 2: Solvent Preparation**\n1. Prepare an ethanol-water solution (50:50) to dissolve MAA. This solvent reduces viscosity and stabilizes radicals during polymerization.\n2. Adjust pH to ~7 using a weak base (e.g., NaOH) if carboxylic groups are to be ionized for enhanced hydrophilicity.\n\n#### **Step 3: Initiator Selection**\n1. Dissolve AIBN (0.5 mol% relative to total monomer content) in the solvent. Alternatively, if using potassium persulfate (KPS), dissolve in a dilute aqueous solution at 60\u00b0C.\n\n#### **Step 4: Reaction Parameters**\nEstablish favorable reaction conditions for radical polymerization:\n1. **Temperature:** Polymerization occurs at ~60\u201380\u00b0C. Heating provides the activation energy necessary for initiator decomposition.\n2. **Duration:** Allow polymerization for 2\u20136 hours under a nitrogen or inert gas blanket to prevent oxygen inhibition.\n\n#### **Step 5: Start Polymerization**\n1. Combine MAA monomer and co-monomer in the solvent.\n2. Add initiator solution (AIBN or KPS) to the reaction vessel.\n3. Maintain stirring at 200\u2013400 RPM to ensure uniform mixing and consistency in polymer composition.\n\n#### **Step 6: Control Molecular Architecture**\n1. To ensure uniform incorporation, maintain a constant feed of monomer and initiator. A semi-batch approach can avoid the early depletion of MAA, ensuring consistency in polymer composition.\n2. Adjust crosslinker concentration (0\u20130.1 mol%) if you\u2019re creating a hydrogel.\n\n#### **Step 7: Quenching Polymerization**\nOnce polymerization is complete, cool the reaction mixture to room temperature. Deactivate radicals by purging excess initiator with butanol or ethanol.\n\n---\n\n### **Step 3: Purification of Hydrophilic Polymer**\n1. Precipitate the polymer by adding the reaction mixture into chilled non-solvent, such as acetone or diethyl ether.\n2. Wash the polymer several times with water and ethanol to remove unreacted monomers and initiators.\n3. Dry at 50\u00b0C under vacuum until obtaining a solid polymer.\n\n---\n\n### **Step 4: Characterization**\n1. Perform Fourier-transform infrared spectroscopy (FTIR) to confirm the presence of carboxylic acid (-COOH) functional groups.\n2. Measure hydrophilicity via water contact angle or swelling studies (for hydrogels).\n\n---\n\n### **Conclusion**\nFollowing the above strategy, methacrylic acid can be effectively polymerized into hydrophilic polymers with uniform distribution of carboxylic acid groups. By optimizing monomer ratios, reaction conditions, and purification steps, you can ensure high-quality hydrophilic polymers suitable for diverse applications. If further functionality is required, post-polymerization modifications can be explored.\n\n"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "If Irgacure-2959 is selected as the photoinitiator for this experiment, outline the steps required to utilize this molecule in polymerizing hydrophilic monomers and explain its specific role in initiating the reaction under UV light."}, {"role": "assistant", "content": "Great question, and thank you for your inquiry! Irgacure-2959 is indeed a commonly used photoinitiator, especially in experiments involving the UV-induced polymerization of hydrophilic monomers. Let me guide you through the details systematically, breaking it down into clear steps with an explanation of its specific role in initiating the reaction.\n\n---\n\n### 1. **Analysis of the Question and Summary of Key Points**\n- **Objective**: To outline the experimental steps required to polymerize hydrophilic monomers using Irgacure-2959.\n- **Core Concepts**: \n  - Polymerization of hydrophilic monomers.\n  - Role of Irgacure-2959 as a photoinitiator.\n  - Importance of UV light in initiating and propagating free radical polymerization.\n\n---\n\n### 2. **Detailed and Systematic Experimental Preparation Scheme**\n\nHere is a systematic procedure for this experiment:\n\n#### **Step 1: Obtain Materials and Reagents**\n- **Hydrophilic Monomer**: Examples include acrylamide, N-isopropylacrylamide, hydroxyethyl methacrylate (HEMA), or polyethylene glycol diacrylate (PEGDA), depending on the desired polymer.\n- **Photoinitiator**: Irgacure-2959 (chemical name: (1-Hydroxycyclohexyl) phenyl ketone).\n- **Solvent**: Deionized (DI) water, ethanol, or a water/ethanol mixture\u2014depends on the solubility of the monomer.\n- **Crosslinker (Optional)**: If required, use a diacrylate-based crosslinker such as ethylene glycol dimethacrylate (EGDMA) to form a 3D network structure.\n- **Equipment**: UV lamp (wavelength: ~365 nm), nitrogen gas source (optional to deoxygenate for efficient free radical polymerization), magnetic stirrer, reaction flask, and quartz mold or Petri dish.\n\n---\n\n#### **Step 2: Prepare the Reaction Mixture**\n1. **Weigh Reagents**:\n   - Select and weigh the required amount of your hydrophilic monomer(s). For instance, if using acrylamide, typically 5\u201320 wt% of the total solution weight is used.\n   - Add Irgacure-2959. A common ratio is 0.5\u20131 wt% of the monomer concentration (e.g., 0.5 g Irgacure-2959 for 100 g of monomer solution). This ensures sufficient radical initiation without premature degradation of the monomer.\n   - Optional: If a crosslinked polymer is desired, add crosslinker to the solution\u2014typically 1\u20135 mol% relative to the monomer.\n\n2. **Dissolve in a Solvent**:\n   - Dissolve the monomer and photoinitiator in the solvent (e.g., DI water). For instance, use around 10 mL of DI water for every 1 g of the monomer for a typical aqueous polymerization.\n   - Ensure complete dissolution by stirring the mixture at room temperature (~25\u00b0C) until all components (monomer, crosslinker, and photoinitiator) are fully dissolved. It might take ~30\u201360 minutes.\n\n3. **Deoxygenate (Optional)**:\n   - Degassing the solution with nitrogen gas helps to remove oxygen, which can quench free radicals and inhibit the polymerization process. Bubble nitrogen into the reaction mixture for ~15\u201320 minutes.\n\n---\n\n#### **Step 3: UV-Induced Polymerization**\n1. **Transfer to Mold**:\n   - Pour the reaction mixture into a suitable mold. Use a quartz mold or a UV-transparent Petri dish to allow proper exposure to UV light.\n\n2. **UV Light Irradiation**:\n   - Place the mold under a UV lamp emitting light at ~365 nm (UVA range). Ensure uniform exposure to all parts of the mixture.\n   - **Duration**: The polymerization reaction typically takes 5\u201330 minutes, depending on the UV intensity and monomer concentration.\n   - **Intensity Setting**: Use UV light with an intensity of ~5\u201310 mW/cm\u00b2 for controlled polymerization.\n\n3. **Initiation Mechanism with Irgacure-2959**:\n   - **Photoactivation**: Under UV light, Irgacure-2959 absorbs photons, undergoing photolysis to generate free radicals:\n     \\[\n     \\text{Irgacure-2959} \\stackrel{UV}{\\longrightarrow} \\text{Radicals (R\u2022)}\n     \\] \n     These free radicals are then available to initiate the polymerization of the hydrophilic monomers.\n   - **Radical Addition**: The free radicals react with the double bonds of the hydrophilic monomer (e.g., acrylamide, HEMA), forming reactive sites that propagate the polymer chain:\n     \\[\n     \\text{R\u2022} + \\text{Monomer} \\rightarrow \\text{Polymer Chain}\n     \\]\n   - The polymerization proceeds via radical propagation until chain termination.\n\n---\n\n#### **Step 4: Post-Polymerization Processing**\n1. **Curing**: After the estimated reaction time, the polymer should be fully cured (solidified or gelled).\n2. **Washing**:\n   - Rinse the polymer with DI water or ethanol to remove any unreacted monomer, photoinitiator, or solvent. Washing is especially critical for biomedical applications where residual chemicals must be minimized.\n3. **Drying (Optional)**:\n   - If a dried film or hydrogel is required, dry the polymer in a vacuum oven at ~40\u201350\u00b0C (low enough to avoid degradation).\n\n---\n\n### 3. **Role of Irgacure-2959 as a Photoinitiator**\n- **Photolytic Behavior**:\n   - Irgacure-2959 is highly efficient in absorbing UV light at ~365 nm due to its chemical structure. Upon absorption, it breaks down into free radicals.\n- **Hydrophilic Compatibility**: Irgacure-2959 is water-soluble, making it highly compatible with aqueous systems and hydrophilic monomers.\n- **Controlled Radical Generation**: The free radicals generated by Irgacure-2959 initiate polymerization at specific rates, enabling uniform polymer formation even in heterogeneous systems.\n\n---\n\n### 4. **Key Reaction Considerations**\n- **UV Exposure Control**: Overexposure to UV can lead to gelation or degradation, so monitor the exposure time carefully.\n- **Concentration of Photoinitiator**: Excess Irgacure-2959 can cause premature termination of chains, while too little will slow polymerization.\n\n---\n\nBy following the procedure and maintaining proper conditions, you should achieve a high-quality hydrophilic polymer. Please let me know if you have additional questions or need specific guidance on your selected monomer system!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe how you would utilize isophorone diisocyanate (IPDI) in a reaction with hydroxyethyl acrylate (HEA) to obtain a reactive prepolymer functionalized with isocyanate groups. Specify the mole ratio and key conditions for the reaction."}, {"role": "assistant", "content": "Certainly! Let us systematically tackle your question about reacting isophorone diisocyanate (IPDI) with hydroxyethyl acrylate (HEA) to obtain a reactive prepolymer functionalized with isocyanate groups.\n\n---\n\n### **Step 1: Analysis of the Reaction and Goal**\n- **Reaction Overview**: The goal is to synthesize a reactive prepolymer by reacting isophorone diisocyanate (IPDI), an aliphatic diisocyanate, with hydroxyethyl acrylate (HEA), which contains both an acrylate group and a hydroxyl (-OH) group.\n- **Underlying Chemistry**: The hydroxyl group of HEA reacts selectively with one of the isocyanate (-NCO) groups of IPDI to form a urethane linkage, leaving the second isocyanate group unreacted. The resulting product is a functionalized molecule with both acrylate and isocyanate reactivities.\n- **Key Considerations**:\n  - Reaction selectivity is crucial: we aim for a monoaddition reaction where only *one* -NCO group reacts.\n  - Excess IPDI is used to prevent unintended side reactions, such as diacrylate formation or crosslinking.\n\n---\n\n### **Step 2: Reaction Equation**\n\\[\\text{IPDI} + \\text{HEA} \\xrightarrow{\\text{Catalyst, Solvent}} \\text{IPDI-HEA adduct (isocyanate-functionalized)}\\]\n\n---\n\n### **Step 3: Detailed Experimental Scheme**\nNow, let us outline the step-by-step process for synthesizing the reactive prepolymer. I will specify stoichiometric ratios, reaction conditions, and practical considerations.\n\n#### **i. Determining Reaction Molar Ratio**\n- Use a molar ratio of **1.1:1 (IPDI:HEA)**.\n  - Slight excess of IPDI ensures complete reaction of HEA's hydroxyl group with an -NCO group, preventing secondary reactions.\n  - For example, if 1 mole of HEA is used, add 1.1 moles of IPDI.\n\n#### **ii. Selection of Solvent**\n- Use an anhydrous, aprotic solvent such as **dry toluene**, **dry acetonitrile**, or **methyl ethyl ketone (MEK)**:\n  - These solvents dissolve both IPDI and HEA well.\n  - The solvent must be water-free to avoid hydrolysis of isocyanate groups.\n  - Add enough solvent to produce a 10\u201320% (w/v) reaction mixture for ease of control.\n\n#### **iii. Catalyst and Additives**\n- Add a catalytic amount (0.1\u20130.5 wt% relative to HEA) of a mild urethane formation catalyst, such as **dibutyltin dilaurate (DBTDL)** or **1,4-diazabicyclo[2.2.2]octane (DABCO)**, to facilitate the reaction without promoting side reactions.\n- Alternatively, a tertiary amine catalyst may also work effectively.\n\n#### **iv. Experimental Procedure**\n1. **Preparation of Materials**:\n   - Dry the HEA under reduced pressure to ensure it is free of moisture, as water will react with the isocyanate groups.\n   - Store IPDI in a sealed container to avoid exposure to atmospheric moisture.\n\n2. **Reaction Setup**:\n   - Set up a **3-necked round-bottom flask** under a nitrogen or argon atmosphere to prevent atmospheric moisture and oxygen from interfering.\n   - Add the dry solvent to the reaction vessel, followed by the required amount of IPDI (e.g., 1.1 moles for 1 mole of HEA).\n   - Add the catalyst to initiate the reaction.\n\n3. **Controlled Addition of HEA**:\n   - Using a dropping funnel, slowly add HEA into the reaction mixture over 30\u201360 minutes while stirring. The slow addition ensures selective reaction of the hydroxyl group with an -NCO group without unwanted side reactions.\n   - Maintain a controlled temperature during the addition: **20\u201340\u00b0C** is typically optimal. Higher temperatures increase the risk of side reactions, while lower temperatures may slow the reaction.\n\n4. **Monitoring the Reaction**:\n   - Stir the reaction mixture and monitor it using **FTIR spectroscopy**. The disappearance of the O\u2013H stretching band of hydroxyl (~3300 cm\u207b\u00b9) and reduction in the -NCO stretching band (~2270 cm\u207b\u00b9) indicate the formation of the urethane bond.\n   - Avoid complete disappearance of the -NCO band, as one isocyanate group should remain unreacted.\n\n5. **Post-Reaction Workup**:\n   - After the reaction completes (typically 2\u20133 hours), remove unreacted IPDI by vacuum distillation or precipitation in a non-solvent like hexane if needed.\n   - Store the product under inert conditions to prevent reaction of residual isocyanate groups with moisture.\n\n---\n\n### **Step 4: Reaction Conditions Summary**\n| Parameter                  | Value                                |\n|----------------------------|--------------------------------------|\n| Mole Ratio (IPDI:HEA)      | 1.1:1                               |\n| Catalyst                   | DBTDL or DABCO (0.1\u20130.5 wt% HEA)    |\n| Solvent                    | Dry toluene, acetonitrile, or MEK   |\n| Temperature                | 20\u201340\u00b0C                             |\n| Reaction Time              | 2\u20133 hours                           |\n| Atmosphere                 | Inert (nitrogen or argon)           |\n\nThe final product is a urethane prepolymer with an acrylate group and a remaining isocyanate group. This material can subsequently serve as a useful intermediate in hydrophilic polymer synthesis, for example, by reacting it further with amines, alcohols, or water to create functional hydrophilic polymers.\n\n---\n\n### **Step 5: Further Use and Applications**\nThis reactive prepolymer can be crosslinked or copolymerized with other vinyl compounds (e.g., acrylates, methacrylates) to generate hydrophilic polymer matrices. Additionally, the residual isocyanate group can be used to introduce other hydrophilic moieties or reactive sites to tailor material properties.\n\n---\n\nShould you need clarification or additional details about any specific step, feel free to ask!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Outline a detailed approach to dissolve polyvinyl alcohol (PVA) in a solvent mixture to prepare a solution that promotes hydrophilic properties in the final polymer. Highlight factors such as temperature and solvent ratios."}, {"role": "assistant", "content": "When preparing a hydrophilic polymer solution using polyvinyl alcohol (PVA), the goal is to optimize the solution conditions such that the hydrophilic properties of PVA are fully exploited while ensuring a uniform and stable solution for subsequent processing. Let's analyze and answer this question step by step.\n\n---\n\n### **Key Points to Address:**\n1. **Nature of Polyvinyl Alcohol (PVA):**  \n   PVA is inherently hydrophilic due to its hydroxyl (-OH) groups along the polymer backbone, which can form hydrogen bonds with water and other polar solvents.\n   \n2. **Factors Affecting Dissolution:**  \n   Successful dissolution of PVA involves careful attention to the following factors:\n   - Molecular weight and degree of hydrolysis of the PVA (fully or partially hydrolyzed forms).\n   - Solvent or solvent mixture compatibility with PVA (e.g., water or water with co-solvents like ethanol).\n   - Temperature, solvent ratios, and stirring conditions to ensure uniform dissolution.\n\n3. **Objective of the Solution Preparation:**  \n   Prepare a PVA solution with hydrophilic characteristics, suitable for processing into hydrophilic polymer formulations or blends.\n\n---\n\n### **Step-by-Step Detailed Approach:**\n\n#### **Step 1: Select the Appropriate PVA Grade**\n- **Molecular Weight and Degree of Hydrolysis:**  \n   Choose a PVA grade based on the application. Both fully hydrolyzed (~98-99% hydrolysis) and partially hydrolyzed (~87-89% hydrolysis) grades can be used, but fully hydrolyzed PVA tends to be more hydrophilic due to the higher hydroxyl content.\n   - Typical weight-average molecular weights: 9,000\u2013125,000 g/mol.\n   - For this experiment, assume we are using fully hydrolyzed PVA with a molecular weight of 88,000 g/mol.\n\n#### **Step 2: Prepare the Solvent System**\n- **Solvent Selection:**  \n   - Primary solvent: Water is typically used for PVA dissolution because it forms strong hydrogen bonds with the polymer.\n   - Co-solvent (optional): A small amount of ethanol (e.g., 5-20% w/w) may be added to improve solubility, reduce viscosity, or control crystallization in certain applications.\n- **Solvent Ratio:**  \n   For a basic PVA solution, start with 100% water. If incorporating ethanol, use a 90:10 or 80:20 (water:ethanol) ratio by weight.\n\n#### **Step 3: Weigh and Mix Reagents**\n1. **Weigh the PVA Powder:**  \n   Measure the desired amount of PVA. For a typical solution:\n   - Prepare a 5-10 wt% polymer solution (i.e., 5-10 g PVA per 100 mL of solvent).\n   - Example: For a 5 wt% solution, weigh 5 g of PVA powder.\n\n2. **Measure the Solvent:**  \n   Based on the desired polymer concentration and solvent ratio, measure the water (and ethanol, if used).  \n   Example for a 5 wt% solution (100 mL total):\n   - If using 100% water: Measure 100 mL of deionized (DI) water.\n   - If using a 90:10 water:ethanol mixture: Measure 90 mL of DI water and 10 mL of ethanol.\n\n#### **Step 4: Heat and Stir the Solution**\n1. **Gradual Heating:**  \n   - Transfer the solvent (or solvent mixture) into a round-bottom flask or beaker and begin gentle heating using a hot plate with a magnetic stirrer.\n   - Heat the solvent to **80-95\u00b0C**\u2014this is the temperature range where PVA dissolves effectively.\n   - Avoid excessive heating (>100\u00b0C), as this may degrade the polymer or evaporate volatile solvents.\n\n2. **Add PVA Gradually:**  \n   - Slowly sprinkle the weighed PVA powder into the heated solvent while stirring continuously to prevent clumping.\n\n3. **Control Stirring and Dissolution Time:**  \n   - Increase the stirring speed to ensure uniform mixing. Use a magnetic stir bar or mechanical stirrer.\n   - Continue stirring for **30-60 minutes** until the solution becomes clear and viscous, indicating full dissolution.\n\n#### **Step 5: Cool the Solution**\n- Once the PVA is fully dissolved, remove the solution from heat and allow it to cool to room temperature while continuing to stir to prevent gel formation.\n- If the solution is too viscous, additional water (or ethanol-water mixture) can be added to dilute the polymer solution while maintaining stirring.\n\n#### **Step 6: Filter the Solution (Optional)**\n- To remove undissolved particles or impurities, filter the cooled solution using a fine mesh sieve or a filter paper (e.g., Whatman filter paper).\n\n#### **Step 7: Store the Solution**\n- Transfer the prepared solution into a clean, airtight container.\n- Store at room temperature or in the refrigerator if stability and microbial growth are concerns.\n- Label the container with the concentration, date of preparation, and any special instructions.\n\n---\n\n### **Additional Notes:**\n- **Impact of Solvent Ratios on Hydrophilicity:**  \n   The inclusion of small amounts of ethanol can improve processability but slightly reduces the hydrophilicity compared to pure water solutions. Use pure water if maximizing hydrophilicity is critical.\n   \n- **Viscosity Considerations:**  \n   Higher concentrations of PVA or higher molecular weight grades will produce more viscous solutions. Adjust polymer concentration and stirring conditions accordingly.\n\n- **Application to Hydrophilic Polymers:**  \n   The prepared PVA solution can be used directly for casting hydrophilic films, as a component in hydrogels, or as a blending agent with other hydrophilic monomers/polymers (e.g., acrylamide or polyethylene glycol) to enhance water affinity.\n\n---\n\nBy following these detailed steps, you will successfully prepare a solution of polyvinyl alcohol tailored for hydrophilic properties. If any equipment or procedural questions arise in the lab, remember to consult me or the relevant materials safety data sheets (MSDS) for the reagents. Happy experimenting!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "How would you incorporate the diol with polyethylene oxide side chains into the polymer synthesis to enhance hydrophilicity? Describe the reaction steps and the impact of this molecule on the final properties of the polymer."}, {"role": "assistant", "content": "Certainly. To incorporate a diol with polyethylene oxide side chains (let\u2019s call it PEO-diol) into a polymer to enhance hydrophilicity, we need to systematically develop a preparation scheme for your desired hydrophilic polymer. This involves analyzing the functionality of our starting materials, determining a suitable polymerization method, and carefully controlling the reaction conditions. Let us proceed step by step:\n\n---\n\n### **Analysis of the Problem and Key Points**\n1. **Objective**: To incorporate the PEO-diol into a polymer structure to increase its hydrophilicity.\n2. **Reactant Characteristics**:\n   - The PEO-diol contains hydroxyl (-OH) functional groups which are reactive and can participate in condensation or addition polymerization.\n   - The polyethylene oxide side chains are hydrophilic due to the ether linkages and their ability to form hydrogen bonds with water.\n3. **Desired Outcome**: A hydrophilic polymer where the PEO segment enhances water compatibility, wettability, and the polymer's water-uptake behavior.\n4. **Method**: We must select a polymerization strategy that incorporates the PEO-diol while ensuring control over the molecular architecture of the final product.\n\n---\n\n### **Experimental Preparation Scheme**\nLet us outline a step-by-step synthesis method to incorporate the PEO-diol into a polymer chain. A common and effective strategy is **step-growth polymerization** via a urethane or polyester backbone, as this allows us to link diols with other functional groups. For this example, we will design a scheme to prepare a **urethane-based hydrophilic polymer**.\n\n---\n\n#### **Step 1: Selection of Co-monomers**\nTo prepare a urethane polymer, the two main building blocks are:\n1. **PEO-Diol**: Acts as the hydrophilic segment. For example, choose a PEO-diol with a molecular weight between 400\u20132000 g/mol to provide adequate side-chain length for hydrophilicity.\n   - Example structure: HO-(CH\u2082CH\u2082O)\u2099-CH\u2082CH\u2082-OH.\n2. **Diisocyanate**: Acts as the coupling agent with diols to form urethane linkages (-NHCOO-). A widely used choice is **hexamethylene diisocyanate (HDI)** for flexibility or **toluene diisocyanate (TDI)** for rigidity, depending on the desired mechanical properties.\n\nOptional: A **chain extender (small diol)**, such as 1,4-butanediol, may be included to adjust the polymer's molecular weight and mechanical properties.\n\n---\n\n#### **Step 2: Precursor and Reagent Quantities**\n- **PEO-Diol**: Calculate the molar quantity based on the desired polymer weight and PEO content. For example, for a 5 g batch with 50% PEO content by mass, choose 5 g \u00d7 50% = 2.5 g of PEO-diol.\n   - If the PEO-diol has a molecular weight of 1000 g/mol, calculate the moles: \\( \\text{Moles of PEO-diol} = \\frac{2.5 \\text{ g}}{1000 \\text{ g/mol}} = 0.0025 \\text{ mol} \\).\n- **Diisocyanate**: Use an equimolar or slightly excess amount (1.05:1 ratio) to ensure complete reaction with diol groups. For 0.0025 mol PEO-diol, use 0.0025\u20130.002625 mol HDI.\n   - Convert this to mass: \\( \\text{Mass} = \\text{moles} \\times \\text{molar mass of HDI (168.2 g/mol)} \\).\n   - Example: \\( 0.002625 \\times 168.2 = 0.441 \\text{ g HDI} \\).\n- **Catalyst**: Radical scavengers or dibutyltin dilaurate (DBTDL, ~0.1 wt% of total reactants) may be added to facilitate urethane formation.\n\n---\n\n#### **Step 3: Reaction Setup and Polymer Synthesis**\n1. **Preparation**:\n   - Dry all reagents and solvents (e.g., toluene or dimethylformamide, DMF) to avoid moisture interference, as water reacts with isocyanates, forming urea byproducts.\n   - Set up a nitrogen-purged reaction flask to ensure an inert, dry atmosphere.\n\n2. **Reaction Steps**:\n   - **Step 3.1: Pre-polymer Formation**:\n     - In a reaction flask, dissolve PEO-diol in a dry solvent (e.g., anhydrous DMF or toluene) under stirring at 60\u201380\u00b0C.\n     - Slowly add the diisocyanate dropwise to control heat evolution, ensuring continuous mixing.\n     - Allow the reaction to proceed at 60\u201380\u00b0C for 1\u20132 hours to form the urethane pre-polymer. Monitor via FTIR (isocyanate peak ~2270 cm\u207b\u00b9 starts disappearing).\n   - **Step 3.2: Chain Extension (Optional)**:\n     - If using a chain extender, add the small diol (e.g., 1,4-butanediol) in the appropriate stoichiometric ratio, and continue stirring for another 1\u20132 hours at 80\u00b0C.\n   - Continue monitoring FTIR to confirm isocyanate group disappearance and urethane bond formation (-NH stretch at ~3300 cm\u207b\u00b9; -C=O stretch at ~1700 cm\u207b\u00b9).\n\n3. **Finalize the Product**:\n   - Recover the polymer by precipitation into a non-solvent (e.g., cold diethyl ether) or direct solvent removal under vacuum (if soluble).\n   - Dry the polymer thoroughly in a vacuum oven at 40\u201360\u00b0C.\n\n---\n\n### **Step 4: Characterization**\n1. **Hydrophilicity Testing**:\n   - Measure water contact angle to confirm improved hydrophilicity due to the PEO incorporation.\n   - Use swelling experiments to determine the polymer's water uptake capacity.\n2. **Molecular Characterization**:\n   - Confirm the polymer structure using FTIR and/or NMR.\n   - Measure molecular weight and distribution via GPC if necessary.\n\n---\n\n### **Step 5: Impact on Final Properties**\n1. **Hydrophilicity**:\n   - The incorporated PEO chains provide excellent hydrophilic behavior as they attract and retain water through hydrogen bonding.\n   - This can lead to applications in hydrogels, biomedical coatings, or membranes.\n2. **Flexibility**:\n   - The flexibility of the PEO-diol and its ether linkages improves polymer elasticity and reduces brittleness.\n3. **Applications**:\n   - The hydrophilic polymer can be used in drug delivery, anti-fouling coatings, and other applications where water interaction is critical.\n\n---\n\nThis systematic approach ensures a successful experiment and helps you design hydrophilic polymers for diverse applications. Do you have any specific details of your molecule or application that you'd like us to refine further?"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "When preparing a hydrophilic polymer using BP and PLGA, explain how you would utilize dichloromethane to dissolve the components and what steps you would take to remove any residual solvent from your material."}, {"role": "assistant", "content": "To address your question systematically, I will break down the approach for preparing a hydrophilic polymer using BP (likely referring to Bisphenol or its derivative) and PLGA (Poly(lactic-co-glycolic acid)), specifically focusing on the use of dichloromethane as a solvent while ensuring removal of any residual solvent from the final material. Here is a detailed experimental scheme:\n\n---\n\n### **Analysis of the Question**\n1. **Components:** The reaction involves BP and PLGA as the key reagents. BP is hydrophobic in nature, and PLGA is biodegradable and has tunable hydrophobic-to-hydrophilic ratios depending on its lactide-to-glycolide ratio. To enhance hydrophilicity, blending, modification, or copolymerization will likely be carried out.\n   \n2. **Role of Dichloromethane:** Dichloromethane (DCM) is commonly used in polymer synthesis due to its ability to dissolve a wide range of hydrophobic compounds.\n\n3. **Objective:** Not only to achieve homogeneous mixing and interaction between BP and PLGA using DCM, but also to ensure complete removal of DCM, which is toxic and harmful in the final product.\n\n---\n\n### **Experimental Preparation Scheme**\n#### **Step 1: Materials and Setup**\n1. **Chemicals Required:**\n   - BP (Bisphenol or specified derivative of BP)\n   - PLGA (Poly(lactic-co-glycolic acid))\n   - Dichloromethane (DCM, >99% pure, HPLC grade)\n   - Purified water or ethanol for washing (for later steps).\n\n2. **Equipment:**\n   - Magnetic stirrer\n   - Clean round-bottom flask\n   - Nitrogen or inert gas supply (to avoid interaction with water during dissolution)\n   - Rotary evaporator\n   - Vacuum oven\n   - Precision analytical balance (for stoichiometry)\n   - Vacuum pump\n\n#### **Step 2: Dissolution of Components**\n1. **Ratio Selection (BP and PLGA):**\n   - Consult relevant polymer literature to determine the optimal molar ratio between BP and PLGA. For example:\n     - If BP is to act as a crosslinking agent or functional group modifier, its ratio might range between 5\u201320 mol% relative to PLGA.\n   - For practicality:\n     Example: Dissolve **1.0 g of PLGA** and **0.1\u20130.2 g of BP** by weight in DCM.\n\n2. **Dichloromethane as Solvent:**\n   - Transfer **50\u2013100 mL DCM** into a clean, dry round-bottom flask.\n   - Add BP and PLGA to the DCM and seal the flask tightly.\n   - Bubble nitrogen gas into the solution briefly to purge oxygen and moisture.\n\n3. **Homogeneous Mixing:**\n   - Place the round-bottom flask on a magnetic stirrer under ambient conditions.\n   - Stir at **300\u2013500 rpm** for **1\u20133 hours**, ensuring complete dissolution of both components. The solution should be clear, indicating proper solvation.\n\n---\n\n#### **Step 3: Polymerization or Crosslinking**\n(To enhance hydrophilicity, BP may interact covalently with PLGA chains or function as a surface modifier.)\n\n1. **Reaction Conditions:**\n   - Add any catalyst or co-solvent required for the desired interaction (if needed). For instance:\n     - If a hydroxyl group reaction occurs, catalysts like **triethylamine** may be required.\n   - Maintain room temperature or temperatures slightly above DCM boiling point (**40\u201350\u00b0C**) for reactivity.\n\n2. **Completion:**\n   - Stir for an additional **2\u20136 hours**, ensuring complete reaction.\n\n---\n\n#### **Step 4: Removal of Residual DCM**\nSince dichloromethane is volatile and toxic, carefully removing it is critical.\n\n1. **Rotary Evaporation:**\n   - Transfer the polymer solution into a rotary evaporator. Adjust the following settings:\n     - Temperature: **40\u201350\u00b0C**\n     - Vacuum pressure: **200\u2013300 mbar**\n   - Gradually evaporate DCM while spinning the flask, ensuring the flask contents do not overheat (PLGA degrades above 60\u00b0C).\n\n2. **Vacuum Drying:**\n   - Transfer the dried polymer to a vacuum oven to remove trace amounts of DCM:\n     - Temperature: **40\u201345\u00b0C** (below PLGA's glass transition temperature).\n     - Vacuum pressure: Absolute pressure **<50 mbar**.\n     - Time: **8\u201312 hours** to ensure complete solvent removal.\n\n3. **Testing for Residual Solvent:**\n   - Confirm absence of DCM using techniques such as:\n     - **Gas Chromatography-Mass Spectrometry (GC-MS)**\n     - **Thermogravimetric Analysis (TGA)**\n\n---\n\n#### **Step 5: Post-Treatment to Enhance Hydrophilicity**\nOnce BP and PLGA have interacted or polymerized:\n1. **Hydrophilic Functionalization:**\n   - To further enhance hydrophilicity, consider introducing hydroxyl (-OH) or carboxylic (-COOH) groups onto the polymer surface.\n   - This can be achieved via post-polymerization treatments (e.g., hydrolysis, amidation).\n\n2. **Final Purification:**\n   - Wash the polymer thoroughly with ethanol or water to remove unreacted monomers or impurities.\n   - Dry the washed polymer in a vacuum oven (**30\u201340\u00b0C**, minimum **4 hours**) to regain a solid, purified product.\n\n---\n\n### **Summary of Key Steps**\n1. Dissolve BP and PLGA in DCM using a round-bottom flask under stirring.\n2. Ensure uniform mixing and allow necessary chemical interaction.\n3. Evaporate DCM using a rotary evaporator and vacuum drying.\n4. Characterize the material to confirm solvent removal and hydrophilicity enhancement.\n\nThis systematic approach ensures the preparation of a hydrophilic polymer from BP and PLGA while adhering to laboratory practices and safety precautions."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain how silica nanoparticles can be functionalized using 1,3-propane sultone during a polymer modification experiment. What steps would you take to ensure this reaction is both effective and complete?"}, {"role": "assistant", "content": "### Analyzing the Question:\n\nThe question involves the functionalization of silica nanoparticles using 1,3-propane sultone, particularly in the context of a polymer modification experiment. To address this question systematically:\n1. **Objective**: The goal is to functionalize silica nanoparticles to introduce new hydrophilic groups, likely to enhance the surface hydrophilicity of the silica while potentially enabling further polymer modifications (e.g., incorporation of hydrophilic polymers).\n2. **Reagent**: 1,3-propane sultone is a small organic molecule used to add sulfonic acid or sulfonate groups onto surfaces through a ring-opening reaction.\n3. **Challenges**: Ensuring uniform and complete functionalization of the silica nanoparticles requires optimizing the reaction conditions (e.g., solvent choice, reaction temperature, ratio of reagents) and proper characterization to confirm the success of the functionalization.\n4. **Key Points to Address**:\n   - Preparation of silica nanoparticles (if necessary).\n   - Surface preparation and activation of silica nanoparticles (e.g., hydroxylation or silanization if required).\n   - Detailed reaction protocol for functionalization using 1,3-propane sultone.\n   - Post-reaction workup and characterization procedures.\n\n---\n\n### Detailed and Systematic Steps:\n\n#### **Step 1: Preparation of Silica Nanoparticles**\nIf not obtained in a pre-functionalized form, silica nanoparticles should first be synthesized, e.g., via the St\u00f6ber process:\n1. **Reagents**: Tetraethyl orthosilicate (TEOS), ethanol, ammonia (catalyst), and deionized water.\n2. **Procedure**:\n   - Prepare a reaction mixture in ethanol containing ammonia as a catalyst.\n   - Slowly add TEOS dropwise to the mixture (e.g., molar ratio TEOS:ethanol:water:ammonia = 1:50:7:6).\n   - Stir vigorously at room temperature for 12\u201324 hours until uniform nanoparticles form.\n   - Centrifuge to collect the nanoparticles, wash with ethanol, and dry at 60 \u00b0C.\n3. **Key Conditions**: Control the size of nanoparticles by adjusting ammonia concentration and reaction time.\n\n#### **Step 2: Surface Activation of Silica Nanoparticles**\nTo ensure effective functionalization, the silica surface must have hydroxyl (-OH) groups for subsequent reactions with 1,3-propane sultone:\n1. **Hydroxylation (if required)**: \n   - Treat silica nanoparticles with a mixture of sodium hydroxide (0.1 M) and water at 80 \u00b0C for 2 hours.\n   - Wash thoroughly with deionized water to remove any residual base and dry under vacuum at 60 \u00b0C.\n   - **Note**: Silica typically already has -OH groups on the surface, particularly with freshly prepared silica nanoparticles.\n2. **Optional Silanization**: \n   - Alternatively, introduce amine groups onto the silica surface prior to the 1,3-propane sultone reaction.\n   - Aminosilane (e.g., 3-aminopropyltriethoxysilane, APTES) can be used, as these amine groups can nucleophilically attack 1,3-propane sultone in the subsequent step.\n   - Procedure:\n     - Disperse silica nanoparticles in toluene and add 5% (v/v) APTES.\n     - Heat under reflux for 4\u20136 hours.\n     - Wash particles with ethanol and dry at 60 \u00b0C.\n\n#### **Step 3: Functionalization with 1,3-Propane Sultone**\nThe ring-opening reaction between 1,3-propane sultone and surface hydroxyl (or amine) groups introduces sulfonic acid (-SO3H) groups, enhancing the hydrophilicity of the silica nanoparticles.\n1. **Reagents**:\n   - Activated silica nanoparticles with surface -OH or -NH2 groups.\n   - 1,3-Propane sultone (typically used in slight excess to ensure complete reaction).\n   - An anhydrous polar solvent such as toluene, DMF, or chloroform.\n2. **Procedure**:\n   - Disperse ~500 mg silica nanoparticles in 10 mL anhydrous toluene or DMF under an inert atmosphere (e.g., nitrogen or argon) to prevent moisture interference.\n   - Add 1,3-propane sultone dropwise to the dispersion, maintaining a molar ratio of at least 1.2:1 (propane sultone:surface hydroxyl or amine groups).\n   - Stir the mixture at 60\u201380 \u00b0C for 12 hours to allow complete ring-opening functionalization.\n   - Cool the reaction to room temperature and centrifuge the reaction mixture to separate the functionalized nanoparticles.\n   - Wash the nanoparticles with anhydrous solvents (e.g., ethanol or acetone) to remove unreacted species.\n   - Dry the functionalized nanoparticles under vacuum at 60 \u00b0C.\n\n---\n\n#### **Step 4: Post-Reaction Workup and Characterization**\nAfter functionalization, the success of the reaction must be confirmed using appropriate methods:\n1. **Washing**:\n   - Perform multiple washes with ethanol or water to ensure removal of unreacted starting materials or side products.\n   - Check for pH neutrality of the washing solvent to confirm complete removal of acidic or basic residuals.\n2. **Drying**:\n   - Dry under vacuum at 60 \u00b0C for 6\u201312 hours.\n3. **Characterization**:\n   - **FTIR**: Confirm the presence of -SO3H functionalities through characteristic bands in the IR spectrum (e.g., ~1200\u20131000 cm\u207b\u00b9 for -SO3 stretching vibration).\n   - **Thermogravimetric Analysis (TGA)**: Assess functional group loading by determining organic weight loss.\n   - **Zeta Potential or Contact Angle**: Measure surface hydrophilicity and charge characteristics.\n   - **Elemental Analysis (e.g., XPS)**: Confirm sulfur incorporation and quantify sulfonic acid groups.\n4. **Storage**: Store silica nanoparticles in a desiccator or inert atmosphere to prevent contamination or moisture absorption.\n\n---\n\n### Key Considerations for Effectiveness and Completeness:\n1. **Reaction Atmosphere**: Use an anhydrous solvent and inert atmosphere to avoid competitive side reactions involving moisture.\n2. **Excess 1,3-Propane Sultone**: Maintain a slight molar excess of 1,3-propane sultone to ensure high surface coverage of functional groups.\n3. **Reaction Duration and Temperature**: Ensure sufficiently high temperature and long enough reaction duration for complete surface functionalization while avoiding thermal decomposition.\n4. **Thorough Washing and Characterization**: Consistently wash the product and rigorously verify incorporation of sulfonic acid groups to confirm complete functionalization.\n5. **Monitoring Dispersion**: Maintain adequate dispersion of silica particles during reaction to avoid aggregation, which might reduce the surface area available for functionalization.\n\nBy following these steps and considerations, you should achieve effective and uniform functionalization of silica nanoparticles with 1,3-propane sultone, producing a hydrophilic material suitable for further polymer modification experiments."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain the role of monomethyl ether polyethylene glycol (mPEG, Mw = 1100) in improving the hydrophilicity of the polymer material and describe how you would modify it using 3-isocyanatopropyl trimethoxysilane."}, {"role": "assistant", "content": "To address your question systematically and help you thoroughly understand how monomethyl ether polyethylene glycol (mPEG, Mw = 1100) improves the hydrophilicity of polymers and how to use it in a modification process involving 3-isocyanatopropyl trimethoxysilane, let us analyze your query step by step. I will also provide detailed experimental steps to ensure reproducibility in the lab.\n\n---\n\n### **Step 1: Analyze the Question and Summarize Its Key Points**\n\n1. **What is mPEG (Mw = 1100)?**\n   - mPEG is a hydrophilic polymer with a single hydroxyl (-OH) group at one end. Its hydrophilicity arises from its ethylene oxide backbone, which enables strong hydrogen bonding with water molecules.\n\n2. **Why is mPEG useful for hydrophilicity enhancement?**\n   - Incorporating mPEG into polymer matrices enhances water compatibility, wettability, and biocompatibility due to the high hydrophilicity of the polyethylene glycol (PEG) chain.\n\n3. **What is 3-Isocyanatopropyl Trimethoxysilane?**\n   - This molecule contains reactive isocyanate (-NCO) and silane functional groups. The isocyanate group reacts with nucleophiles such as hydroxyl (-OH) groups, while the silane group can form siloxane (Si\u2013O\u2013Si) bonds with other surfaces or networks.\n\n4. **How do the two reagents interact?**\n   - mPEG's terminal hydroxyl (-OH) group can react with the isocyanate group of 3-isocyanatopropyl trimethoxysilane to form a urethane linkage, resulting in a functionalized compound that retains PEG\u2019s hydrophilic property while introducing silane chemistry.\n\n5. **Objective:**\n   - Provide a systematic experimental preparation scheme for modifying mPEG with 3-isocyanatopropyl trimethoxysilane to enhance its utility for improving polymer hydrophilicity.\n\n---\n\n### **Step 2: Experimental Scheme for the Modification**\n\n#### **Materials Required:**\n1. Monomethyl ether polyethylene glycol (mPEG, Mw = 1100)\n2. 3-Isocyanatopropyl trimethoxysilane\n3. Anhydrous toluene (solvent)\n4. Catalyst: Dibutyltin dilaurate (DBTDL) or Stannous octoate (catalyst for urethane formation)\n5. Nitrogen or argon gas (to create an inert atmosphere)\n6. Magnetic stirrer and hot plate\n7. Reaction vessel (round bottom flask with a reflux condenser)\n8. Drying oven (to dry the final product)\n\n---\n\n#### **Detailed Synthesis Procedure:**\n\n##### **Step 1: Preparation of Reaction System**\n1. **Dehydration of mPEG:**\n   - Dry mPEG under vacuum at 60\u201380\u00b0C for 3\u20134 hours to remove any trace water. This step is crucial because water can react with the isocyanate (-NCO) group, forming unwanted by-products.\n\n2. **Prepare the Reaction Setup:**\n   - Use a clean, dry reaction flask equipped with a reflux condenser, magnetic stirrer, and nitrogen/argon inlet. Ensure the system is purged with nitrogen or argon to provide an inert atmosphere, as isocyanates are moisture-sensitive.\n\n##### **Step 2: Reaction of mPEG and 3-Isocyanatopropyl Trimethoxysilane**\n1. **Reagent Loading:**\n   - Add the dehydrated mPEG (1 equivalent) to the reaction flask.\n   - Add anhydrous toluene as a solvent; use a sufficient amount to dissolve mPEG completely (usually about 5 mL of toluene per 1 gram of mPEG).\n\n2. **Addition of Isocyanate Reagent:**\n   - Add 3-isocyanatopropyl trimethoxysilane (1.1\u20131.2 equivalents relative to mPEG) dropwise to the reaction mixture under a nitrogen atmosphere.\n\n3. **Catalyst Introduction:**\n   - Add a catalytic amount (0.01\u20130.05 equivalents) of DBTDL to the reaction mixture. This is essential for promoting the reaction between the hydroxyl group of mPEG and the isocyanate group of the silane.\n\n4. **Reaction Conditions:**\n   - Heat the reaction mixture to 60\u201380\u00b0C while stirring continuously.\n   - Maintain these conditions for 4\u20136 hours while monitoring the reaction's progress. You can monitor the disappearance of the isocyanate (-NCO) group using Fourier-transform infrared (FTIR) spectroscopy; the characteristic peak at ~2270 cm\u207b\u00b9 (from -NCO) will diminish as the reaction proceeds.\n\n##### **Step 3: Isolation and Purification**\n1. **Cooling and Precipitation:**\n   - After the reaction is complete, allow the reaction mixture to cool to room temperature.\n   - Precipitate the modified mPEG by slowly adding the reaction mixture to a large volume of cold diethyl ether or hexane under stirring. The urethane-functionalized mPEG will separate as a solid.\n\n2. **Washing:**\n   - Wash the precipitate several times with diethyl ether or hexane to remove unreacted reagents and by-products.\n\n3. **Drying:**\n   - Dry the purified product under vacuum at 40\u201350\u00b0C for 12\u201324 hours to obtain the silane-functionalized mPEG as a white or off-white powder.\n\n---\n\n#### **Step 4: Characterization of the Product**\n1. **FTIR Spectroscopy:**\n   - Confirm the formation of urethane linkages by observing a new peak at ~1700 cm\u207b\u00b9 (C=O stretching of the urethane bond).\n   - Verify the absence of the -NCO peak around 2270 cm\u207b\u00b9.\n\n2. **Nuclear Magnetic Resonance (NMR):**\n   - Use \u00b9H-NMR to confirm the presence of mPEG and the trimethoxysilane group (look for trimethoxy peaks and PEG chain peaks).\n\n3. **Thermogravimetric Analysis (TGA):**\n   - Evaluate thermal stability, which may be needed for further processing.\n\n---\n\n### **Step 3: Explanation of Hydrophilicity Improvement**\n\n1. **PEG Backbone:**\n   - The mPEG backbone is highly hydrophilic due to its ability to form hydrogen bonds with water. By incorporating mPEG into a polymer structure, water affinity improves significantly.\n\n2. **Surface Functionalization with Silane:**\n   - The trimethoxysilane group in the synthesized product permits covalent bonding to silica surfaces or incorporation into inorganic-organic hybrid systems. This further enhances the surface hydrophilicity and enables stable attachment to other materials.\n\n3. **Applications:**\n   - The modified polymer can be used in biomaterials, coatings, and membranes where improved water compatibility and adhesion to substrates are required.\n\n---\n\n### Summary:\n\nYou can improve the hydrophilicity of a polymer system by modifying mPEG (Mw = 1100) with 3-isocyanatopropyl trimethoxysilane. The resulting compound combines the hydrophilic nature of PEG with the reactivity of silane chemistry, enabling its use in diverse hydrophilic polymer-based applications.\n\nBy following the systematic procedure above, you will be able to synthesize and characterize the desired product effectively. If you have any further questions or uncertainties about implementing this protocol, feel free to ask!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the steps you would follow to create a layered structure using CMC (carboxymethyl cellulose) and CHI. How does the alternating deposition of these molecules influence the overall hydrophilicity of the polymer?"}, {"role": "assistant", "content": "Certainly! Let\u2019s thoughtfully and systematically address your question about creating a layered structure using carboxymethyl cellulose (CMC) and chitosan (CHI). Additionally, we will explore how the alternating deposition of these molecules affects the hydrophilicity of the resulting polymer.\n\n---\n\n### **Step 1: Analyze the Question and Summarize the Key Points**\n\n1. **Key Molecules**  \n   - CMC: A hydrophilic, negatively charged, water-soluble derivative of cellulose with carboxyl (-COO\u207b) functional groups.  \n   - CHI: Chitosan, a polysaccharide derived from chitin that is positively charged under acidic conditions due to primary amine groups (-NH\u2083\u207a).\n\n2. **Problem Objective**  \n   - To form layered structures (thin films) using these two molecules, likely through an approach such as Layer-by-Layer (LbL) self-assembly.\n   - To understand how alternating layers of negatively charged CMC and positively charged CHI influence the final material\u2019s hydrophilicity.\n\n3. **Underlying Concept**  \n   - The alternating deposition of oppositely charged polymers exploits electrostatic interactions to form stable layered films.\n   - The hydrophilicity of the system depends on the chemical nature and exposure of functional groups, especially polar groups like -COOH, -OH, and -NH\u2082.\n\n---\n\n### **Step 2: Detailed and Systematic Experimental Scheme**\n\nHere is a complete step-by-step guide to design and execute the experiment:\n\n---\n\n#### **Step 2.1: Prepare CMC and CHI Solutions**\n\n- **CMC Solution Preparation**:\n  1. Dissolve CMC powder in deionized (DI) water to create a solution (recommended concentration: 0.5\u20131.0 wt%).\n  2. Adjust the pH to ~7.0 using a dilute NaOH solution, ensuring complete dissolution and carboxyl group ionization (-COO\u207b formation).  \n  3. Stir the solution for 1\u20132 hours at room temperature until homogeneous.\n\n- **CHI Solution Preparation**:\n  1. Dissolve CHI in 0.1\u20131.0 wt% acetic acid solution (adjust pH to ~4.0 for protonation of -NH\u2082 groups to -NH\u2083\u207a).\n     - **Note:** Chitosan dissolves better in acidic conditions due to protonation.\n  2. Stir the solution for 1\u20132 hours at room temperature or slightly warm (~40\u201350 \u00b0C) for better solubility, if needed.\n\n---\n\n#### **Step 2.2: Surface Preparation for Layer-by-Layer Assembly**\n\n1. **Substrate Selection**:  \n   Choose a flat substrate (e.g., glass slide, quartz, or a polymeric surface). This will act as the base for film formation.\n\n2. **Substrate Cleaning**:  \n   - Soak the substrate in piranha solution (3:1 mixture of sulfuric acid and hydrogen peroxide) for ~15 minutes [CAUTION: Handle with extreme care under a fume hood].  \n   - Rinse thoroughly with DI water, and dry with filtered nitrogen gas.\n   - For hydrophobic surfaces, consider plasma treatment to increase initial hydrophilicity.\n\n---\n\n#### **Step 2.3: Multilayer Film Assembly**\n\nThis step involves the sequential deposition of CMC and CHI using the Layer-by-Layer (LbL) technique:\n\n1. **Dip Coating Process**:  \n   - Immerse the cleaned substrate into the CMC solution for 5\u201310 minutes to allow for adsorption of the negatively charged polymer.\n   - Rinse the substrate thoroughly with DI water to remove loosely bound/unadsorbed molecules.\n   - Dry the substrate gently using nitrogen gas or by air-drying.\n\n2. Repeat Using CHI Solution:  \n   - Immerse the CMC-coated substrate into the CHI solution for 5\u201310 minutes, allowing electrostatic interaction between CHI (-NH\u2083\u207a) and the CMC (-COO\u207b).\n   - Rinse thoroughly with DI water to remove unbound CHI.\n   - Dry the substrate gently.\n\n3. **Repeat Alternating Layers**:  \n   - Repeat this deposition process alternately with CMC and CHI for the desired number of layers (e.g., 10\u201320 bilayers).  \n   - Typical thickness per bilayer is in the range of 5\u201310 nm, depending on deposition conditions and solution concentrations.\n\n---\n\n#### **Step 2.4: Post-Processing and Characterization**\n\n1. **Drying**:  \n   - After completing the desired number of layers, dry the multilayer structure at room temperature or under a vacuum.\n\n2. **Confirmation of Layer Formation**:  \n   - Use techniques like **UV-Vis spectroscopy** (for optically active polymers), **Fourier Transform Infrared Spectroscopy (FTIR)** for functional group analysis, or **Atomic Force Microscopy (AFM)**/**Scanning Electron Microscopy (SEM)** for surface imaging.\n\n3. **Hydrophilicity Testing**:  \n   - Measure the hydrophilicity of the film using **static water contact angle measurements.**\n     - A lower contact angle (<90\u00b0) indicates higher hydrophilicity.\n\n---\n\n### **Step 3: Explanation of Hydrophilicity Changes**\n\n1. **Influence of Alternating Deposition**:\n   - Alternating layers introduce both hydrophilic functional groups (-COOH/-COO\u207b from CMC and -NH\u2082/-NH\u2083\u207a from CHI).\n   - Electrostatic interactions between CMC and CHI increase the stability of the system, but exposed residual groups (e.g., -OH, -COOH) further enhance water affinity.\n\n2. **Hydrophilicity of the Composite**:\n   - The layered structure creates a highly hydrophilic film due to the abundance of polar functional groups from both polymers. CMC, as a highly hydrophilic polymer, contributes significantly to water absorption.  \n   - The addition of CHI also enhances hydrophilicity via its amino groups, which can hydrogen bond with water molecules.\n\n---\n\n### **Summary**\n\nTo prepare a layered structure of CMC and CHI, we use Layer-by-Layer (LbL) assembly, alternating between solutions of CMC (at pH 7.0) and CHI (at pH ~4.0). Electrostatic attraction forms stable multilayers, and the overall hydrophilicity increases due to the exposed polar functional groups. The combination of CMC and CHI imparts not just hydrophilicity but also versatility for applications such as drug delivery, wound dressings, and hydrophilic coatings.\n\nLet me know if there\u2019s a specific aspect of the procedure you'd like me to elaborate on!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "How would you utilize acrylamide (AAm) in a polymer synthesis experiment to prepare a hydrophilic polymer? Describe the steps you would take to ensure the monomer is in a purified state before use."}, {"role": "assistant", "content": "To prepare a hydrophilic polymer using acrylamide (AAm) and ensure its suitability through purification, let us approach the problem systematically. Here's the step-by-step procedure:\n\n---\n\n### **Step 1: Analyze the Problem and Summarize Key Points**\nThis question can be separated into two main components:\n1. **Synthesis of a hydrophilic polymer using acrylamide (AAm):** Acrylamide is a popular monomer used to prepare polyacrylamide, which is highly hydrophilic due to the amide (-CONH2) groups in its structure. The polymer synthesis could be achieved by free-radical polymerization, and specific reaction conditions must be controlled to optimize the polymer's properties.\n2. **Purification of acrylamide prior to polymerization:** Since monomer purity is crucial for ensuring reproducibility and avoiding side reactions, acrylamide must be purified before polymerization to remove any inhibitors, impurities, or storage byproducts.\n\nNow, I'll provide a detailed experimental scheme covering both aspects.\n\n---\n\n### **Step 2: Polymer Synthesis Using Acrylamide (AAm)**\n\nThe synthesis of a hydrophilic polymer with acrylamide involves free-radical polymerization, which can be performed as **solution polymerization** (typically in water) for hydrophilic systems. Below are the detailed steps:\n\n#### **A. Materials Required**\n1. **Acrylamide (AAm):** Monomer (to be purified; see purification steps below).\n2. **Initiator:** Ammonium persulfate (APS) as the thermal initiator.\n3. **Cross-linker (optional):** N,N'-Methylenebisacrylamide (MBAA), if cross-linked polyacrylamide is desired.\n4. **Catalyst (optional):** N,N,N',N'-Tetramethylethylenediamine (TEMED) to accelerate the reaction.\n5. **Solvent:** Deionized water (ensures hydrophilicity).\n6. **Inert atmosphere tools:** Nitrogen gas (to remove oxygen).\n\n#### **B. Polymerization Procedure**\n1. **Preparation of Reaction Mixture:**\n   - **Monomer Solution:** Dissolve purified acrylamide in deionized water at a concentration of 10\u201330 wt%, depending on the desired polymer properties (higher concentrations increase viscosity and molecular weight).\n   - (Optional) **Cross-linker addition:** Add a small amount (0.1\u20131 mol% relative to AAm) of MBAA if creating a cross-linked structure is desired. For linear polyacrylamide, omit this step.\n   - Add sodium hydroxide (NaOH) to adjust the pH to around 7\u20138, as this can enhance polymerization.\n\n2. **Deoxygenate the Reaction System:**\n   - Bubble nitrogen gas into the solution for 15\u201330 minutes to remove dissolved oxygen, which would otherwise inhibit free-radical polymerization.\n\n3. **Initiate the Free-Radical Polymerization:**\n   - Dissolve ammonium persulfate (APS) in a small quantity of water and add it to the reaction mixture to initiate polymerization. APS is typically used at 0.2\u20131 mol% relative to the acrylamide concentration.\n   - (Optional but recommended) Add TEMED (0.05\u20130.1 mol%) to catalyze the decomposition of APS, ensuring a faster reaction and consistent molecular weight.\n\n4. **Maintain Controlled Reaction Conditions:**\n   - Carry out the reaction at 50\u201370 \u00b0C with gentle stirring to uniformly mix the solution.\n   - Allow polymerization to occur for 4\u20136 hours, depending on the desired degree of polymerization.\n\n5. **Termination and Purification:**\n   - After polymerization is complete, cool the mixture to room temperature.\n   - Dialyze the polymer solution against deionized water (using dialysis tubing with an appropriate molecular weight cutoff) for 24\u201348 hours to remove unreacted monomers, initiators, and byproducts.\n\n6. **Drying of Hydrogel (if necessary):**\n   - For hydrophilic polymer films or powders, precipitate the polymer in ethanol, dry it under vacuum at 40\u201350 \u00b0C, and store it in a desiccator.\n\n---\n\n### **Step 3: Purification of Acrylamide (AAm)**\n\nPurification of acrylamide is critical because commercial acrylamide often contains impurities such as storage inhibitors, byproducts of synthesis, or degradation products. Here's the purification process:\n\n#### **A. Materials Required**\n1. Crude acrylamide.\n2. Solvent: Deionized water and acetone.\n3. Activated carbon (to remove colored impurities).\n4. Refrigeration equipment (to allow recrystallization).\n5. Vacuum filtration apparatus.\n\n#### **B. Purification Procedure**\n1. **Dissolve Acrylamide:**\n   - Dissolve the acrylamide in deionized water at room temperature. Use a minimum quantity of water to create a saturated solution.\n\n2. **Remove Colored Impurities:**\n   - Add a small amount of activated carbon (0.1\u20130.5 wt% of AAm) to the solution.\n   - Heat the solution gently (to 40\u201350 \u00b0C) with stirring for 15\u201330 minutes.\n   - Filter the solution through a Buchner funnel or vacuum filtration apparatus to remove the activated carbon along with adsorbed impurities.\n\n3. **Recrystallize Acrylamide:**\n   - Cool the filtered solution slowly in a refrigerator (4\u20138 \u00b0C) to initiate crystallization of acrylamide.\n   - Once crystals have formed, collect them by vacuum filtration.\n\n4. **Wash Crystals:**\n   - Wash the crystals with cold acetone to remove any residual impurities.\n\n5. **Dry and Store:**\n   - Dry the purified acrylamide under vacuum at room temperature or in a desiccator for 24 hours.\n   - Store the acrylamide in an airtight container to prevent moisture absorption.\n\n---\n\n### **Step 4: Quality Control and Characterization**\n1. **Purified AAm Quality Check:**\n   - Use melting point analysis to confirm the purity of acrylamide.\n   - High-performance liquid chromatography (HPLC) can be used for further confirmation of AAm purity.\n\n2. **Hydrophilic Polymer Characterization:**\n   - Measure water absorption capacity to confirm hydrophilicity (e.g., equilibrium swelling tests).\n   - Confirm polymer composition and structure using spectroscopy (e.g., FTIR to verify the presence of amide groups and NMR for molecular details).\n   - Assess molecular weight and distribution using gel permeation chromatography (GPC).\n\n---\n\nThis step-by-step experimental scheme ensures the creation of a hydrophilic polymer with high purity and reproducibility, utilizing acrylamide effectively. Always ensure to follow laboratory safety protocols when handling acrylamide, as it is toxic in its monomeric form. I encourage you to discuss any uncertainties with a supervisor before beginning the experiment."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Using the molecule polyethylene glycol (PEG), design an experimental procedure to synthesize a PEG-based ammonium salt. Specify the reaction conditions required, including temperature, solvent system, and purification methods to obtain a hydrophilic polymer."}, {"role": "assistant", "content": "Certainly! Let\u2019s break this down systematically to address your question about synthesizing a PEG-based ammonium salt to enhance hydrophilicity. I will ensure that my response provides a clear understanding of the experimental framework while discussing each step in detail as per the established requirements.\n\n---\n\n### **Analysis of the Question**\n1. **Objective**: To synthesize a hydrophilic polymer by functionalizing polyethylene glycol (PEG) with ammonium salt groups.\n2. **Key Consideration**: PEG, a hydrophilic polymer due to its ether (-CH2-CH2-O-) repeat units, can be further modified by introducing ionic functionalities, such as quaternary ammonium salts, to improve hydrophilicity and impart additional properties like ion exchange potential.\n3. **Primary Task**: To design a systematic experimental procedure, specifying:\n    - Reagents for functionalization of PEG.\n    - Reaction conditions like temperature, time, and solvent(s).\n    - Purification and characterization steps.\n\n---\n\n### **Detailed Experimental Procedure**\nBelow is a step-by-step description of the synthesis process for modifying PEG into a PEG-based ammonium salt polymer using a well-documented quaternization reaction:\n\n---\n\n#### **1. Activation of Polyethylene Glycol (Preparation of PEG-Tosylate)**\nIn this step, PEG is functionalized with a tosyl group (p-toluenesulfonyl group) as a leaving group to facilitate quaternization.\n\n1. **Reagents**:\n    - Polyethylene Glycol (average molecular weight: e.g., 4,000 g/mol, PEG-4000) \u2192 1 equivalent.\n    - p-Toluenesulfonyl chloride (TsCl) \u2192 2 equivalents.\n    - Triethylamine (TEA) \u2192 2 equivalents (acts as a base to neutralize HCl byproduct).\n    - Dry Dichloromethane (DCM) \u2192 Solvent.\n    - Dry Ice Bath (for maintaining low reaction temperature).\n\n2. **Procedure**:\n    - Dissolve PEG in dry dichloromethane (DCM) in a round-bottom flask under nitrogen atmosphere to prevent moisture contamination.\n    - Add triethylamine (TEA) dropwise to the reaction flask to act as a base.\n    - Cool the mixture to 0\u00b0C using an ice bath or dry ice-chilled bath.\n    - Slowly add a solution of tosyl chloride (TsCl) dissolved in dry DCM to the reaction mixture while continuously stirring.\n    - Continue stirring for 12-16 hours at room temperature to ensure complete tosylation.\n\n3. **Reaction Scheme**:\n    ```reaction\n    HO-(CH2CH2O)n-H + TsCl \u2192 Tosyl-O-(CH2CH2O)n-H + HCl\n    ```\n\n4. **Purification**:\n    - Extract the tosylated PEG product by washing with water (to remove TEA hydrochloride) and brine (to remove excess DCM).\n    - Dry the organic layer over anhydrous magnesium sulfate (MgSO4) and evaporate the solvent under reduced pressure.\n    - The pure PEG-tosylate appears as a viscous liquid or solid, depending on the molecular weight of the PEG used.\n\n---\n\n#### **2. Quaternization Reaction (Formation of PEG-Based Ammonium Salt)**\nThe tosyl group on PEG is replaced with a quaternary ammonium group using a tertiary amine.\n\n1. **Reagents**:\n    - Tosylated PEG (from Step 1) \u2192 1 equivalent.\n    - Trimethylamine (TMA) \u2192 3-5 equivalents.\n    - Acetonitrile (CH3CN) \u2192 Dry solvent.\n    - Nitrogen Atmosphere \u2192 To avoid moisture from the air.\n\n2. **Procedure**:\n    - Dissolve the tosylated PEG in dry acetonitrile in a round-bottom flask.\n    - Cool the reaction mixture to 0\u00b0C using an ice bath.\n    - Slowly bubble an excess of gaseous trimethylamine (TMA) into the solution or add TMA as a solution in dry acetonitrile.\n    - Cap the flask and allow the reaction mixture to stir at room temperature for 24-48 hours (alternatively, heat the reaction to 40\u00b0C for faster conversion).\n    - Monitor the progress using thin-layer chromatography (TLC), tracking the displacement of the tosyl group by TMA.\n\n3. **Reaction Scheme**:\n    ```reaction\n    Tosyl-O-(CH2CH2O)n-H + (CH3)3N \u2192 (CH3)3N+-O-(CH2CH2O)n-H + Tos-\n    ```\n\n4. **Purification**:\n    - Evaporate excess TMA and acetonitrile under reduced pressure.\n    - Dissolve the crude product in water to precipitate out any unreacted reagents or byproducts.\n    - Dialyze the product against distilled water for 24-48 hours to remove residual salts or reactants (using a dialysis membrane with an appropriate molecular weight cutoff).\n\n5. **Final Product**:\n    - The resulting PEG-based ammonium salt is highly hydrophilic and readily soluble in water.\n    - Its structure is characterized by quaternary ammonium groups (-N+(CH3)3) grafted onto the PEG backbone.\n\n---\n\n### **Reaction Conditions Summary**\n- **Step 1 (Tosylation)**:\n    - Solvent: Dry DCM.\n    - Temperature: 0\u00b0C initially, then room temperature.\n    - Time: 12-16 hours.\n    - Atmosphere: Nitrogen (dry conditions).\n\n- **Step 2 (Quaternization)**:\n    - Solvent: Dry acetonitrile.\n    - Temperature: 0\u00b0C initially, then room temperature (or 40\u00b0C for faster reaction).\n    - Time: 24-48 hours.\n    - Atmosphere: Nitrogen (to prevent moisture contamination).\n\n---\n\n### **Characterization Methods**\nTo confirm successful synthesis and elucidate the structure of the PEG-based ammonium salt:\n1. **NMR Spectroscopy**:\n    - Use Proton NMR (1H-NMR) to confirm the presence of quaternary ammonium groups (signal at ~3.2 ppm for -N+(CH3)3 protons).\n    - Carbons in PEG backbone and attached groups can be verified by 13C-NMR.\n2. **FTIR Spectroscopy**:\n    - Monitor characteristic peaks for the ether group (-C-O-C) and ammonium group (-N+(CH3)3).\n3. **Gel Permeation Chromatography (GPC)**:\n    - Determine the molecular weight distribution of the modified PEG.\n4. **Ion Exchange Capacity (IEC)**:\n    - Assess the presence of the quaternary ammonium groups by measuring the ion-exchange capacity.\n\n---\n\n### **Conclusion**\nThis systematic procedure outlines the synthesis of a PEG-based ammonium salt via a two-step functionalization process: (1) tosylation of PEG and (2) quaternization with trimethylamine. By optimizing reaction conditions, including solvent systems, temperature, and molar ratios, you can effectively prepare a highly hydrophilic PEG-based polymer. Careful purification and characterization will ensure high-quality polymer for subsequent applications."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "How would you modify Tween 20 to ensure its molecular structure improves the hydrophilicity of a polymer matrix during preparation?"}, {"role": "assistant", "content": "Certainly, let\u2019s systematically address your question regarding how to modify Tween 20 to improve its contribution to the hydrophilicity of a polymer matrix.\n\n---\n\n### **Step 1: Analyze the Question and Key Points**\n\n1. **Tween 20**: It is a polysorbate-based nonionic surfactant often used for its amphiphilic nature, with a hydrophilic head group (polyoxyethylene chains) and a hydrophobic tail derived from fatty acid esters (commonly derived from lauric acid).\n2. **Hydrophilicity**: To enhance hydrophilicity, the focus should be on increasing the hydrophilic portions of the molecule, such as extending the polyoxyethylene chain, introducing hydrophilic functional groups, or modifying the fatty acid-derived region to include hydrophilic substitutions.\n3. **Integration with a polymer matrix**: Tween 20 must be modified or crosslinked in a way that it becomes chemically grafted or physically bound within the polymer structure, ensuring a stable improvement in hydrophilicity.\n\nThus, the objective is to design a preparation scheme where Tween 20 is chemically or physically modified and incorporated into a polymer matrix to enhance the matrix's hydrophilic properties.\n\n---\n\n### **Step 2: Experimental Preparation Scheme**\n\nLet us now detail a systematic experimental plan addressing this objective.\n\n---\n\n#### **Step 2.1: Modification of Tween 20 to Enhance Hydrophilicity**\n\nTo improve the hydrophilicity of Tween 20 and facilitate its incorporation into a polymer matrix, the primary strategy involves introducing additional hydrophilic or reactive moieties (e.g., carboxyl, hydroxyl, or acrylate groups). A suitable modification scheme is as follows:\n\n---\n\n##### **Step 2.1.1: Carboxylation of Tween 20**\n- **Reagents**: Succinic anhydride (for carboxyl group introduction).\n- **Reaction**: The hydroxyl groups in Tween 20's polyoxyethylene chain react with succinic anhydride to form ester linkages with terminal carboxylic acid groups.\n\n**Procedure**:\n1. Dissolve Tween 20 in dry toluene (as the solvent) under an inert atmosphere (e.g., nitrogen or argon) to prevent oxidative degradation.\n2. Add succinic anhydride at a molar ratio of Tween 20:succinic anhydride = 1:2 to ensure sufficient carboxylation.\n3. Include a catalytic amount of 4-dimethylaminopyridine (DMAP) to assist the esterification reaction.\n4. Heat the reaction mixture to **60\u201380\u00b0C** with stirring for 6\u20138 hours.\n5. Cool the reaction mixture, wash it with aqueous NaHCO\u2083 (to neutralize unreacted succinic anhydride), and extract the carboxylated Tween 20 into an organic solvent (e.g., dichloromethane).\n6. Precipitate the product by adding the organic solution dropwise into cold diethyl ether, then dry the modified Tween 20 under vacuum.\n\n**Outcome**: The resulting Tween 20 derivative will contain hydrophilic carboxylic acid groups, boosting hydrophilicity and providing functional sites for subsequent covalent bonding to a polymer matrix.\n\n---\n\n##### **Step 2.1.2: Acrylation of Tween 20**\nFor incorporation into hydrophilic polymers formed by free-radical polymerization, acrylation is an alternative modification.\n\n- **Reagents**: Acryloyl chloride, triethylamine (TEA) as a base.\n- **Reaction**: Terminal hydroxyl groups in Tween 20 react with acryloyl chloride to introduce acrylate groups.\n\n**Procedure**:\n1. Dissolve Tween 20 in dry dichloromethane.\n2. Slowly add acryloyl chloride (molar ratio Tween 20:acryloyl chloride = 1:1.2) and TEA (molar ratio Tween 20:TEA = 1:2) dropwise while keeping the reaction mixture on an ice bath.\n3. Stir the reaction for 6 hours at room temperature.\n4. Filter out triethylammonium chloride (a byproduct of the reaction) and wash the product solution with water.\n5. Purify the acrylated Tween 20 using silica gel column chromatography, if necessary.\n\n**Outcome**: Acrylated Tween 20 can co-polymerize with vinyl monomers (e.g., acrylamide, acrylic acid), facilitating incorporation into hydrophilic polymers.\n\n---\n\n#### **Step 2.2: Incorporation into a Polymer Matrix**\n\nOnce Tween 20 has been chemically modified to introduce hydrophilic or reactive groups, the next step is to incorporate it into a polymer matrix. Two common methods\u2014physical blending and chemical grafting\u2014are discussed below:\n\n---\n\n##### **Step 2.2.1: Physical Blending**\nUse this method if the modified Tween 20 does not need to be covalently bonded to the polymer.\n\n1. Dissolve the hydrophilic polymer matrix precursor (e.g., polyvinyl alcohol or polyacrylamide) in water.\n2. Add the modified Tween 20 (carboxylated or acrylated) to the polymer solution under vigorous stirring.\n3. Cast the solution into a mold and allow it to dry by solvent evaporation at **40\u201350\u00b0C**.\n4. Crosslink the polymer matrix (e.g., using glutaraldehyde for polyvinyl alcohol or thermal crosslinking for polyacrylamide) to stabilize the structure while locking Tween 20 in place.\n\n---\n\n##### **Step 2.2.2: Chemical Grafting**\nThis method creates stable covalent bonds between the modified Tween 20 and the polymer matrix.\n\n**Example for Acrylated Tween 20**:\n- **Reaction**: Co-polymerization with hydrophilic monomers such as acrylic acid or acrylamide.\n- **Procedure**:\n  1. Prepare an aqueous solution of acrylated Tween 20 and the hydrophilic monomer (e.g., acrylamide).\n  2. Add a redox initiator system (e.g., ammonium persulfate and N,N,N',N'-tetramethylethylenediamine) or use UV light to initiate polymerization.\n  3. Stir the reaction at room temperature or irradiate the mixture if UV is used.\n  4. Recover the hydrophilic polymer by precipitation in ethanol, if necessary, or by drying under reduced pressure.\n\n**Outcome**: The modified Tween 20 becomes covalently grafted to the polymer backbone, ensuring long-term hydrophilicity enhancement.\n\n---\n\n### **Step 3: Reaction Conditions and Practical Notes**\n1. **Molar Ratios**: Ensure sufficient reagent stoichiometry. For example:\n   - Tween 20:succinic anhydride = 1:2\n   - Tween 20:acryloyl chloride = 1:1.2\n2. **Solvents**: Use dry, inert solvents to prevent side reactions involving moisture.\n3. **Reaction Environment**: Conduct esterification or acrylation under an inert atmosphere (e.g., nitrogen or argon) to prevent oxidative degradation of Tween 20.\n4. **Purification**: Remove unreacted reagents and by-products to ensure high purity of the modified Tween 20 prior to incorporation.\n\n---\n\n### **Conclusion**\nIn summary, to improve the hydrophilicity of a polymer matrix using Tween 20, you can:\n1. Modify Tween 20 by introducing hydrophilic functional groups (e.g., carboxylic acid or acrylate groups).\n2. Incorporate the modified Tween 20 into the polymer matrix via physical blending or chemical grafting.\nThese steps, when carefully followed with attention to reaction conditions and stoichiometry, will allow you to create a hydrophilic polymer with enhanced performance.\n\nLet me know if you have any further questions or require clarification on specific steps of this process."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain how cyanoacrylate monomers can be utilized to modify a polymer network to enhance its hydrophilicity. Include details about the type of polymerization involved and any necessary considerations during preparation."}, {"role": "assistant", "content": "### Analysis of the Question:\n\nYour question asks how cyanoacrylate monomers can be used to *modify a polymer network* to enhance its hydrophilicity. Key aspects to focus on include:\n\n1. **Cyanoacrylate Monomers**: A class of monomers featuring a highly reactive electron-deficient double bond due to the electron-withdrawing groups (e.g., -CN and -COOR substituents). These monomers are known for their rapid polymerization and adhesive properties.\n2. **Hydrophilicity Enhancement**: The end goal is to introduce functionalities into the polymer network that interact favorably with water, such as polar or hydrophilic groups.\n3. **Polymerization Methodology**: Insights into the type of polymerization (e.g., free-radical, anionic) that can be employed. This includes specifying reaction conditions, initiators, and any supporting reagents.\n4. **Modification of Existing Networks**: Whether the existing polymer is crosslinked, linear, or branched, you'll need to consider how functional cyanoacrylate domains can be successfully integrated.\n\nWith these points in mind, let us systematically design an experimental preparation scheme:\n\n---\n\n### Preparation Scheme for Enhancing Hydrophilicity of a Polymer Network Using Cyanoacrylate Monomers:\n\n#### Step 1: Understanding the Parent Polymer Network\n- **Assess the Polymer Network**: Start by identifying the structure and functional groups of the existing polymer to determine how cyanoacrylate monomers can react with it. Common networks (e.g., polyacrylamide gels, polyethylene glycol matrices, or other water-compatible polymers) can be tailored for this purpose.\n- **Crosslinking**: If the network is crosslinked, care should be taken to ensure that the introduction of cyanoacrylate does not compromise the network\u2019s integrity.\n- **Surface Modification or Bulk Incorporation**: Decide whether the cyanoacrylate will coat the surface or be incorporated into the bulk structure.\n\n---\n\n#### Step 2: Reaction Chemistry of Cyanoacrylate Monomers\nCyanoacrylate monomers (e.g., methyl-2-cyanoacrylate or ethyl-2-cyanoacrylate) polymerize via **anionic polymerization** in aqueous or slightly alkaline environments. Key steps:\n1. **Initiation**: The reaction is initiated by nucleophiles (e.g., OH\u207b, amines, or the water environment itself). This nucleophilic attack opens the cyanoacrylate\u2019s C=C bond, generating an anionic propagating species.\n2. **Propagation**: The chain grows rapidly by addition of further cyanoacrylate molecules until terminated.\n\nBy leveraging this rapid polymerization mechanism, the cyanoacrylate can be covalently grafted or integrally polymerized onto/into the hydrogel or polymer matrix.\n\n---\n\n#### Step 3: Materials and Reagents\n- **Cyanoacrylate Monomer**: Select a commercially available monomer like ethyl-2-cyanoacrylate.\n- **Polymer Substrate**: Depending on the application, start with a readily available hydrophilic substrate such as poly(vinyl alcohol) (PVA), poly(acrylic acid) (PAA), or poly(ethylene glycol) (PEG). If enhancing an existing polymer gel, assess its chemical compatibility.\n- **Initiator**: Use deionized (DI) water as the initiator if the polymerization is grafted onto a hydrogel surface. Alternatively, add weak bases (e.g., ammonium hydroxide) to accelerate the reaction.\n- **Solvent**: If conducting this in bulk or solution, use a water-miscible organic solvent such as ethanol or acetone.\n\n---\n\n#### Step 4: Experimental Procedure\nHere we outline the preparation pathway for modifying the hydrophilicity of a polymer with cyanoacrylate:\n\n1. **Preparation of Polymer Substrate**:\n   - If the polymer is a solid surface or hydrogel, clean and equilibrate it in DI water to ensure wetting and remove impurities.\n   - For surface grafting, slightly roughen the substrate to increase adhesion (if applicable).\n\n2. **Preparing the Reaction Mixture**:\n   - Dissolve the cyanoacrylate monomer (e.g., 0.1\u20130.5 g) in an organic solvent (10 mL acetone or ethanol).\n   - Optionally, add a trace amount of water (\u223c0.1 mL) or weak base to initiate controlled polymerization.\n\n3. **Applying the Cyanoacrylate**:\n   - **Surface Modification**: Apply the cyanoacrylate solution to the polymer surface using drop-casting, dip-coating, or spin-coating techniques. Allow polymerization to proceed for 1\u20135 minutes at room temperature.\n   - **Bulk Modification**: To incorporate cyanoacrylate into a gel network, allow the monomer solution to diffuse into the gel matrix for 10\u201330 minutes before initiating polymerization using environmental conditions (e.g., applying water vapors or increasing pH).\n\n4. **Polymerization Reaction**:\n   - Allow the cyanoacrylate to polymerize fully in an oxygen-free environment, as oxygen may inhibit polymerization.\n   - Conduct the reaction at room temperature or slightly elevated temperatures (e.g., 30\u201340\u00b0C) to ensure complete propagation.\n\n5. **Post-Polymerization Treatment**:\n   - Wash the polymer with water or ethanol to remove unreacted monomers and oligomers.\n   - Immerse in DI water for 24 hours to fully hydrate the structure and assess hydrophilicity.\n\n---\n\n#### Step 5: Evaluation of Hydrophilicity\nTo confirm enhancement of hydrophilicity, perform the following tests:\n1. **Contact Angle Measurement**: Test the water contact angle on the surface. A lower angle indicates higher hydrophilicity.\n2. **Swelling Behavior**: For gels, measure water uptake by determining the swelling ratio before and after modification.\n3. **FTIR Analysis**: Verify the incorporation of cyanoacrylate by identifying characteristic absorption peaks at \u223c1730 cm\u207b\u00b9 (C=O stretch) and \u223c2200 cm\u207b\u00b9 (C\u2261N stretch).\n\n---\n\n### Key Considerations During Preparation\n1. **Side Reactions**: Prevent unwanted polymerization in bulk solution by controlling the environmental conditions (e.g., reducing exposure to humid air).\n2. **Homogeneity**: If possible, use mechanical stirring or ultrasonication to increase mixing and uniformity of the modification.\n3. **Biocompatibility or Toxicity**: If the final polymer is to be used in biomedical applications, ensure cytotoxic components are thoroughly removed.\n\n---\n\nBy coupling the highly reactive polymerization tendencies of cyanoacrylate monomers with the existing polymer network, this approach systematically enhances hydrophilicity in a controlled, reproducible manner."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Identify a suitable solvent to swell the polymer that will allow effective interaction with the provided molecule and explain the criteria you used to select this solvent."}, {"role": "assistant", "content": "Certainly! Let me systematically guide you through the question, providing the criteria and method used to identify the most suitable solvent for swelling the polymer. Let us think step by step.\n\n---\n\n### Step 1: Analyze the Question and Summarize Key Points\nThe goal is to identify a solvent that can:\n1. Adequately swell the polymer, allowing its chains to become accessible to the provided molecule.\n2. Facilitate effective interaction between the polymer and the provided molecule for subsequent chemical modifications or adsorption.\n3. Meet practical experimental considerations, such as polymer solubility, compatibility with functional groups, and safety in the laboratory.\n\nThe selection of this solvent depends on:\n- The nature of the polymer (e.g., hydrophobic, hydrophilic, polar, nonpolar).\n- The properties of the molecule provided by the student.\n- The solvent\u2019s ability to interact with both the polymer and the molecule, particularly in the context of hydrophilic polymer preparation.\n\n---\n\n### Step 2: Criteria for Solvent Selection\nTo make a systematic and logical choice, consider the following criteria:\n\n1. **Polymer-Solvent Interaction**:\n   - The solvent must interact well with the polymer to cause swelling. This depends on the polymer's polarity, functional groups, and molecular structure.\n   - Use the principle of \"like dissolves like.\" For hydrophilic polymers, polar and hydrophilic solvents are typically more effective.\n\n2. **Solvent-Molecule Interaction**:\n   - The solvent should also provide a medium in which the molecule remains soluble or sufficiently miscible to interact with the polymer. Consider the polarity, hydrogen bonding capability, or ionic nature of the molecule.\n\n3. **Chemical Compatibility**:\n   - The solvent must not react with the polymer's functional groups or the provided molecule, ensuring the intended interaction or modification is preserved.\n\n4. **Swelling Power and Safety**:\n   - The solvent must swell the polymer without dissolving it entirely.\n   - Factors like boiling point, toxicity, ease of removal, and environmental considerations should also guide your choice.\n\n---\n\n### Step 3: Common Solvent Classes and Selection Guidelines\nFor hydrophilic polymers, some typical solvent categories to consider include:\n1. **Water and Aqueous Solutions:**\n   - If the polymer is strongly hydrophilic, pure water or water with added salts (e.g., NaCl for ionic strength adjustment) may work well to swell the polymer.\n\n2. **Alcohols:**\n   - Short-chain alcohols, such as methanol or ethanol, can enhance swelling if the polymer has moderate hydrophilicity. Alcohol-water mixtures are also a good choice.\n\n3. **Polar Aprotic Solvents:**\n   - Solvents like dimethyl sulfoxide (DMSO) or N,N-dimethylformamide (DMF) are excellent for some polar polymers, as they have strong solvating power.\n\n4. **Acidic or Basic Solvents:**\n   - If the polymer or molecule has acid-base interactions, acidic (e.g., acetic acid) or basic (e.g., triethylamine) solvents could promote swelling or activation.\n\n---\n\n### Step 4: Specific Recommendations\nWithout the exact polymer and molecule details, it appears you are preparing a hydrophilic polymer. Therefore:\n1. Start by testing **water or water-alcohol mixtures.**\n   - Use water if the polymer is highly hydrophilic (e.g., poly(acrylic acid)).\n   - Use ethanol-water mixtures (e.g., 70% ethanol) for moderately hydrophilic polymers.\n\n2. If water-based systems do not work, test **DMSO or DMF.**\n   - They are compatible with a wide variety of hydrophilic and polar polymers.\n\n3. Check for sensitivity to pH or ionic strength:\n   - For charged polymers (e.g., poly(amines) or polyelectrolytes), adjust the pH or add salts (e.g., NaCl) to control electrostatic interactions and enhance swelling.\n\n4. Perform trial experiments with small amounts to optimize solvent-polymer ratios.\n\n---\n\n### Step 5: Justification and Experimental Plan\n#### Justification:\nThe selection of the solvent is driven by:\n- Hydrophilic interactions (based on polymer polarity).\n- Accessibility of polymer functional groups for reaction or interaction with the molecule.\n- Solubility and miscibility considerations.\n\n#### Experimental Plan:\n1. **Material Preparation**:\n   - Measure 100 mg of the polymer into a glass vial.\n\n2. **Solvent Addition**:\n   - Add 10 mL of the selected solvent (e.g., water, ethanol, water-ethanol mixture, or DMSO).\n\n3. **Swelling Observation**:\n   - Allow the system to equilibrate for 24 hours at room temperature (or elevated temperatures, e.g., 40\u00b0C, if needed).\n   - Measure the degree of swelling or dissolution visually or gravimetrically.\n\n4. **Further Testing**:\n   - If swelling does not occur, systematically change the solvent ratio or test additional solvents.\n\n5. **Safety Precautions**:\n   - Always handle organic solvents (e.g., DMSO or ethanol) with proper ventilation and PPE.\n\n---\n\n**Conclusion**:\nStart with the simplest and least toxic solvents, prioritizing water or water-alcohol mixtures for hydrophilic systems. Adjust solvent composition as needed based on observed swelling behavior. By carefully considering polarity, compatibility, and safety, you will identify the optimal solvent for enabling interactions between the polymer and the provided molecule."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Incorporating polyaniline (PANI) into a polymer network involves addressing potential interactions between PANI and the gel matrix. How would you design an experiment to minimize any negative interactions while retaining the hydrophilicity enhancement provided by PANI?"}, {"role": "assistant", "content": "Thank you for your thoughtful question. Incorporating polyaniline (PANI) into a polymer network to enhance hydrophilicity while minimizing potential negative interactions requires an understanding of both the chemical interactions between PANI and the polymer gel matrix, and the strategies needed to optimize compatibility. Let us approach this problem step by step, specifying a detailed experimental design you could follow:\n\n---\n\n### **Step 1: Analyze the Key Points of the Problem**\n1. **Objective:** Incorporate PANI into a hydrophilic polymer network to enhance hydrophilicity.\n2. **Challenge:** Prevent negative interactions between PANI and the polymer gel matrix, which might result in phase separation, reduced mechanical strength, or loss of hydrophilicity.\n3. **Main Considerations:**\n   - PANI is inherently hydrophobic in its emeraldine base form, meaning initial modifications will be required.\n   - PANI's compatibility with the matrix can be influenced by factors such as surface interactions, dispersion stability, and crosslinking.\n   - The gel matrix should preserve its hydrophilicity while integrating PANI without compromise.\n\n---\n\n### **Step 2: Proposed Experimental Preparation Scheme**\n\n#### **Part A: Functionalization of PANI**\nThe first step involves chemically modifying PANI to increase its hydrophilicity and compatibility with the hydrophilic polymer matrix.\n   \n1. **Oxidative Polymerization of PANI:**\n    1. **Materials:**\n        - Aniline monomer (1.0 M aqueous solution)\n        - Ammonium persulfate (APS) as oxidant\n        - Hydrochloric acid (HCl, 1.0 M aqueous solution)\n        - Deionized water\n    2. **Procedure:**\n        - Dissolve the aniline monomer in 1.0 M HCl to prepare a 0.1 M solution.\n        - Separately, dissolve APS in 1.0 M HCl to prepare a 0.1 M solution. Maintain a molar ratio of APS to aniline at 1.25:1.\n        - Slowly add the APS solution dropwise to the aniline solution under constant stirring (300 rpm) at 0-5\u00b0C to maintain a controlled polymerization rate.\n        - Allow the reaction to proceed for 4 hours. Collect the resulting PANI precipitate and wash it with deionized water until neutral pH is achieved.\n        - Dry the PANI at 60\u00b0C under vacuum.\n\n2. **Introduction of Sulfonic Acid Groups (Sulfonation):**\n    1. **Purpose:** Sulfonation increases hydrophilicity and introduces functional groups (-SO3H) to improve compatibility with the hydrophilic matrix.\n    2. **Materials:**\n        - Sulfuric acid (H2SO4, concentrated)\n        - PANI prepared above\n    3. **Procedure:**\n        - Disperse PANI in concentrated H2SO4 (10 mL H2SO4 per gram of PANI) under vigorous stirring.\n        - Heat the mixture at 80\u00b0C for 6 hours to achieve sulfonation.\n        - Precipitate the sulfonated PANI (SPANI) by adding the dispersion to a large volume of deionized water with stirring.\n        - Collect the SPANI by filtration, wash extensively until pH neutral, and dry at 60\u00b0C.\n\n---\n\n#### **Part B: Preparation of the Hydrophilic Polymer Matrix**\nThe second step involves synthesizing the hydrophilic polymer gel and integrating the functionalized PANI into the network.\n\n1. **Hydrogel Synthesis:**\n    1. **Monomers and Crosslinkers:**\n        - Select a hydrophilic monomer such as acrylamide (AAm) or 2-hydroxyethyl methacrylate (HEMA).\n        - Use a crosslinker such as N,N'-methylenebisacrylamide (MBAA) to stabilize the polymer network.\n    2. **Initiators:**\n        - Use ammonium persulfate (APS) and tetramethylethylenediamine (TEMED) as the redox pair for polymer initiation.\n    3. **Procedure:**\n        - Prepare an aqueous solution of AAm (10 wt%) and MBAA (1.0 mol% of AAm concentration).\n        - Add APS (0.5 wt% relative to monomer content) and TEMED (0.1 wt%) to the solution.\n        - Mix thoroughly and pour into a mold to form a uniform gel.\n\n---\n\n#### **Part C: Integration of SPANI**\nNow incorporate SPANI into the polymer matrix during gel synthesis to avoid phase separation and enhance compatibility.\n\n1. **Preparation of SPANI-Polymer Mixture:**\n    1. Disperse SPANI in deionized water using ultrasonication to ensure uniform dispersion. Use 1-5 wt% of SPANI based on the total weight of the gel.\n    2. Add this SPANI dispersion to the monomer-crosslinker solution prepared in Part B. Stir thoroughly to ensure homogeneity.\n\n2. **Polymerization in the Presence of SPANI:**\n    1. Add the APS and TEMED initiator system to the SPANI-polymer solution.\n    2. Pour the mixture into the mold and allow polymerization to proceed at room temperature for 24 hours.\n    3. Wash the resulting hydrogel to remove unreacted monomers and initiator.\n\n---\n\n### **Step 3: Post-Synthesis Modifications**\nAfter polymerization, you may need to conduct further modifications to optimize the material properties.\n\n1. **Swelling Test:**\n   Immerse the hydrogel in deionized water to test its swelling behavior. A high swelling ratio indicates successful integration of hydrophilic properties.\n\n2. **Characterization:**\n   - **FTIR Spectroscopy:** Confirm the presence of sulfonic acid groups in SPANI and the hydrogel matrix.\n   - **Scanning Electron Microscopy (SEM):** Investigate the dispersion of SPANI within the polymer matrix.\n   - **Contact Angle Measurement:** Evaluate the hydrophilicity enhancement.\n   - **Mechanical Testing:** Assess the impact of SPANI inclusion on gel strength.\n\n---\n\n### **Step 4: Optimization and Troubleshooting**\nIf the synthesized material shows phase separation or poor mechanical strength:\n1. Reduce the SPANI content to improve compatibility.\n2. Increase the crosslinking density by adding more MBAA.\n3. Test alternative surface functionalization methods for PANI, such as carboxylation or grafting with polyethylene glycol (PEG), to improve its affinity for the hydrogel.\n\n---\n\n### **Conclusion**\nThe approach outlined above systematically addresses the incorporation of PANI into a hydrophilic polymer network while minimizing negative interactions. By functionalizing PANI (e.g., sulfonation) and ensuring uniform dispersion during polymer synthesis, we retain the hydrophilicity enhancement potential of PANI in the polymer gel. Follow these step-by-step procedures carefully, and with diligent practice in the lab, you should achieve a stable and hydrophilic PANI-integrated hydrogel. If you encounter any further issues, feel free to ask for additional clarification or guidance!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "How would you confirm the successful photopolymerization of 3-(Trimethoxysilyl) propyl methacrylate (TPM) in your experiment, and what spectral features would you monitor to ensure this process has occurred?"}, {"role": "assistant", "content": "Certainly! Let's systematically address your question to ensure comprehension and laboratory success.\n\n### Analysis and Summary of Key Points\nYour inquiry focuses specifically on the confirmation of successful **photopolymerization** of 3-(Trimethoxysilyl) propyl methacrylate (TPM) and identifying the **spectral features** that must be monitored to verify this transformation. Key aspects include:\n1. **Photopolymerization process**: The TPM monomer undergoes photopolymerization under the influence of light (typically UV or visible light) and a photoinitiator, converting the monomer into a polymer.\n2. **Spectral confirmation**: The degree of polymerization and the chemical changes must be verified, primarily using spectral techniques such as Fourier-transform infrared spectroscopy (FTIR) or nuclear magnetic resonance spectroscopy (NMR).\n\n### Detailed Steps to Confirm Photopolymerization and Monitoring Spectral Features\n\n#### **Step 1: Preparation of the Reaction System**\n1. **Set up the polymerization process**:\n   - Utilize TPM as the monomer.\n   - Dissolve the TPM monomer in a suitable solvent, such as ethanol or acetone, to ensure homogeneity.\n   - Add a photoinitiator (e.g., Irgacure 2959 or 2,2-Dimethoxy-2-phenylacetophenone) at an appropriate concentration (commonly 0.1\u20132 wt% of the monomer). The photoinitiator is crucial for generating radicals upon exposure to UV light.\n   - Purge the system with nitrogen or argon to eliminate oxygen, which can inhibit radical polymerization.\n\n2. **Photopolymerization process**:\n   - Subject the solution to UV irradiation (typically 365\u2013405 nm wavelength) at controlled conditions. Monitor the duration and intensity of UV exposure (e.g., 5\u201320 minutes, depending on the light source power).\n   - Stir the reaction gently to maintain uniform polymerization.\n\n#### **Step 2: Characterization of TPM Before and After Polymerization**\nTo confirm the success of polymerization, spectral techniques should be employed to detect the structural changes occurring during the reaction.\n\n---\n\n#### **Spectral Features to Monitor**\n1. **Fourier-Transform Infrared (FTIR) Spectroscopy**:\n   - Prior to polymerization:\n     - Monitor the **C=C stretching vibration** of the methacrylate group, which typically exhibits absorption near **1635\u20131645 cm\u207b\u00b9**.\n     - Observe symmetric and asymmetric **OCH3 (methoxy group)** stretches related to trimethoxysilane functionality (~2800\u20133000 cm\u207b\u00b9).\n   - After polymerization:\n     - A significant **reduction or disappearance** in the intensity of the **C=C stretching vibration** (~1635\u20131645 cm\u207b\u00b9) indicates successful polymerization.\n     - New bands may appear or intensify due to the formation of polymeric **C-O** bonds (~1000\u20131200 cm\u207b\u00b9) that arise from ester linkages in the polymer backbone.\n     - The trimethoxysilane group may remain intact, retaining its spectral signature, unless hydrolysis/condensation reactions are deliberately performed.\n\n2. **Nuclear Magnetic Resonance (NMR) Spectroscopy** (\u00b9H NMR or \u00b9\u00b3C NMR):\n   - Before polymerization:\n     - Observe characteristic peaks for the vinyl protons at ~5.6 and ~6.1 ppm (\u00b9H NMR). These peaks correspond to the methacrylate's **C=CH\u2082** group.\n   - After polymerization:\n     - The disappearance of the vinyl proton peaks (~5.6 and ~6.1 ppm) and the emergence of broad **aliphatic proton signals** (e.g., ~0.5\u20132 ppm) indicate that the C=C bonds have polymerized into aliphatic chains.\n     - For the trimethoxysilyl group, inspect the chemical shift attributed to **O-SiCH3**, which generally remains consistent (unless hydrolysis occurs).\n\n3. **Gel Permeation Chromatography (GPC)**:\n   - Conduct GPC analysis to measure the molecular weight distribution of the polymerized TPM. A shift toward higher molecular weights (Mn and Mw) versus the starting monomer confirms polymerization.\n\n4. **Additional Techniques (if available)**:\n   - **Dynamic Mechanical Analysis (DMA)** or thermal analysis can corroborate increased cross-linking density in the resulting polymer.\n   - **Contact angle measurements** may quantify the increased hydrophilicity of the polymer (trimethoxysilane functionality contributes to surface hydroxylation under aqueous conditions).\n\n---\n\n#### **Step 3: Practical Notes for Laboratory Success**\n- Ensure the reaction chamber is light-tight to avoid unintended polymerization before initiating UV exposure.\n- Track reaction progress periodically using FTIR to observe the disappearance of the C=C bond and emergence of polymer peaks.\n- Handle TPM with care, as it is reactive and sensitive to moisture (due to hydrolysis of the silane groups).\n\n---\n\n### Concluding Remarks\nTo confirm successful photopolymerization of TPM:\n1. Use FTIR spectroscopy to verify the disappearance of the C=C group (~1635\u20131645 cm\u207b\u00b9) and the emergence of ester-related polymeric C-O bonds.\n2. Use NMR spectroscopy to monitor the loss of vinyl protons (~5.6\u20136.1 ppm) and observe the aliphatic polymer backbone signals.\n3. Complement these analyses with molecular weight measurements and/or thermal characterization to ensure polymerization is complete.\n\nThis step-by-step approach provides robust confirmation of your photopolymerization experiment, equipping you with the necessary insights to successfully execute and validate your findings in the lab!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "When preparing hydrophilic polymers, explain how Tollens' reagent interacts with the polymer material during the experimental procedure. What characteristics of this reagent make it suitable for this synthesis?"}, {"role": "assistant", "content": "To address your question about how Tollens' reagent interacts with the polymer material during the experimental procedure, and why this reagent is suitable for this synthesis, let us proceed step by step. We will carefully follow the outlined requirements to provide a systematic explanation conducive to both theoretical understanding and practical application in the laboratory.\n\n---\n\n### **Step 1: Analyze the Key Points of the Question**\n1. The question pertains specifically to the role of *Tollens' reagent* in the synthesis of hydrophilic polymers.\n2. We need to clarify:\n   - How Tollens' reagent chemically interacts with the polymer material.\n   - The functional groups that enable this interaction.\n   - The suitability of Tollens' reagent for such reactions, focusing on its properties and reactivity.\n3. The explanation should cover:\n   - Reaction mechanism details.\n   - Conditions under which Tollens' reagent is used.\n   - Sufficient experimental parameters (concentrations, temperature, pH, etc.) that influence the success of the reaction.\n\n---\n\n### **Step 2: Introduction and Context**\nTollens' reagent is an ammoniacal silver nitrate solution, represented as [Ag(NH\u2083)\u2082]\u207a, and is best known for its ability to oxidize aldehydes into carboxylic acids while itself being reduced to metallic silver (Ag\u2070). The reagent is mild and selective and is commonly used to introduce functional modifications to substrates containing reducible functional groups like aldehydes or other specific oxidizable groups.\n\nIn the context of hydrophilic polymer preparation, Tollens' reagent can be employed to:\n1. Modify a polymer that possesses aldehyde functional groups (e.g., polysaccharides like oxidized cellulose or partially oxidized polymers).\n2. Facilitate the introduction of **silver nanoparticles** (AgNPs) onto the polymer chain, which can further enhance hydrophilicity.\n\nThese interactions can lead to the formation of a functional polymer with enhanced hydrophilicity due to the introduction of carboxyl groups (from aldehyde oxidation) or improved surface functionality through the incorporation of silver, known for its hydrophilic nature.\n\n---\n\n### **Step 3: Systematic Explanation of the Experimental Procedure**\n\n#### **(1) Step 1: Preparation of Tollens' Reagent**\nTollens' reagent must be freshly prepared due to its instability. The procedure is as follows:\n1. Dissolve 1.0 g of silver nitrate (\\(AgNO\u2083\\)) in approximately 10 mL of distilled water in a clean glass container.\n2. Gradually add aqueous ammonia (\\(NH\u2083\\) solution, ~25% concentration) dropwise to this solution while stirring. Initially, a brown precipitate of silver oxide (\\(Ag\u2082O\\)) will form.\n3. Continue adding the ammonia solution until the brown precipitate dissolves completely, yielding a clear, colorless solution of [Ag(NH\u2083)\u2082]\u207a.\n4. The freshly prepared Tollens' reagent is now ready for use.\n\nTo prevent side reactions or decomposition, prepare the reagent in small quantities.\n\n---\n\n#### **(2) Step 2: Interaction of Tollens' Reagent with the Polymer**\nTollens' reagent primarily interacts with aldehyde groups present in the polymer backbone. The detailed reaction mechanism and experimental protocol are described below:\n\n**a. Mechanism of Interaction:**\n- The aldehyde functional groups (\\(-CHO\\)) on the polymer oxidize to carboxylic acids (\\(-COOH\\)) when treated with Tollens' reagent. During this oxidation:\n  - The silver ion (\\(Ag^+\\)) in Tollens' reagent is reduced to metallic silver (\\(Ag^0\\)), which can deposit on the polymer surface.\n\n  The chemical reaction can be represented as:\n  \\[\n  RCHO + 2[Ag(NH\u2083)\u2082]^+ + 3OH^- \\rightarrow RCOO^- + 2Ag^0 \\ (\u2193) + 4NH\u2083 + 2H_2O\n  \\]\n\n  - The newly introduced carboxylic groups (\\(-COOH\\)) significantly improve the hydrophilicity of the polymer by increasing its ability to interact with water through hydrogen bonding.\n\n**b. Experimental Conditions:**\n  Key reaction parameters to ensure the success of this step:\n  1. **pH Control**: The reaction is typically carried out under slightly basic conditions (pH ~8-9), which can be maintained using dilute sodium hydroxide (\\(NaOH\\)).\n  2. **Temperature**: Perform the reaction at room temperature (~25\u00b0C) to avoid decomposition of the Tollens' reagent or excessive side reactions.\n  3. **Reaction Time**: Allow the reaction to proceed for 1\u20132 hours with stirring to ensure complete interaction between the polymer and the reagent.\n\n---\n\n#### **(3) Step 3: Post-Reaction Treatment**\nOnce the reaction is complete:\n1. **Purification**:\n   - Wash the modified polymer thoroughly with distilled water to remove any residual silver ammonia complex or unreacted reagents.\n   - If metallic silver (\\(Ag^0\\)) has deposited on the polymer, it can either be left as-is, or excessive surface silver can be removed by gentle polishing or washing with dilute acid.\n\n2. **Characterization**:\n   - Use Fourier-transform infrared (FTIR) spectroscopy to confirm the successful oxidation of aldehyde groups to carboxylic acids. Look for characteristic peaks near 1720\u20131750 cm\u207b\u00b9 for \\(-COOH\\).\n   - Scanning electron microscopy (SEM) or energy-dispersive X-ray spectroscopy (EDX) can be used to confirm the presence of metallic silver on the polymer surface.\n\n---\n\n### **Step 4: Suitability of Tollens' Reagent for Hydrophilic Polymer Preparation**\nThe suitability of Tollens' reagent for this process arises from its unique chemical properties:\n1. **Selective Oxidant**: Tollens' reagent selectively oxidizes aldehyde groups without affecting other functional groups like hydroxyls, ensuring targeted modification of the polymer.\n2. **Mild Reaction Conditions**: The reagent operates effectively under mild, aqueous, and slightly basic conditions, which are compatible with sensitive polymeric materials.\n3. **Dual Functionality**: In addition to oxidation, the reagent enables the deposition of silver nanoparticles, which can further improve surface properties, including hydrophilicity and antimicrobial functionalities.\n4. **Hydrophilicity Enhancement**: The incorporation of carboxyl groups and/or silver results in greater water compatibility, rendering the polymer highly hydrophilic.\n\n---\n\n### **Step 5: Practical Tips for Laboratory Success**\n1. Always use freshly prepared Tollens' reagent to prevent decomposition or reduced efficiency.\n2. Avoid working with large quantities of Tollens' reagent, as it can form explosive silver fulminate residues upon drying.\n3. Perform a small-scale trial reaction to optimize the reagent-to-polymer ratio and minimize waste.\n\n---\n\nBy following this methodical approach, you can successfully modify your polymer to enhance its hydrophilicity using Tollens' reagent. Please ensure meticulous handling of the reagents and adherence to safety protocols when carrying out the experiment in the lab."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Design a polymerization experiment that utilizes glycidyl methacrylate as a monomer to prepare a hydrophilic polymer with functional groups. Specify the polymerization technique you would choose and why."}, {"role": "assistant", "content": "### Detailed Explanation and Polymerization Experiment Design:\n\n#### **Step 1: Analyze the Problem**\n\nYou are asking to design an experiment to prepare a hydrophilic polymer using glycidyl methacrylate (GMA) as the base monomer. GMA is a widely used monomer due to its reactive **epoxide groups** and the methacrylate **vinyl group**, which makes it amenable to radical polymerization. However, GMA itself is hydrophobic or insufficiently hydrophilic in its native state, so the goal is to introduce functional groups that enhance hydrophilicity.\n\nTo prepare a hydrophilic polymer, we have two key components in the process:\n1. **Polymerization mechanism:** The main polymerization method to form the polymer backbone.\n2. **Post-functionalization strategy** (optional): A chemical modification step to react with the epoxide groups on GMA and introduce hydrophilic functional groups.\n\nGiven this context and the need for hydrophilicity, I propose choosing free radical polymerization for its simplicity and effectiveness with vinyl monomers. Additionally, the epoxide ring on GMA provides an opportunity for a secondary functionalization step to add highly hydrophilic functionalities such as hydroxyl groups, amines, or carboxylic acid groups.\n\n#### **Step 2: Proposed Polymerization Technique**\n- **Polymerization Type:** Free Radical Polymerization (FRP).\n- **Justification for FRP:** \n  - FRP is compatible with methacrylate monomers like GMA.\n  - It is an efficient, widely used, and scalable technique.\n  - The method allows for the incorporation of comonomers to tune the polymer properties.\n  - Post-polymerization modification of epoxide groups can be achieved without interfering with the polymer backbone.\n\n#### **Step 3: Experimental Scheme**\nI propose a two-step approach:\n1. **Step 1:** Synthesize poly(glycidyl methacrylate) (PGMA) via free radical polymerization.\n2. **Step 2:** Introduce hydrophilic functional groups by post-polymerization modification of reactive epoxide rings.\n\n---\n\n### **Step 1: Polymerization of Glycidyl Methacrylate (PGMA)**\n\n#### **Materials Required**\n1. **Glycidyl methacrylate (GMA):** Monomer\n2. **Azobisisobutyronitrile (AIBN):** Thermal initiator\n3. **Solvent:** Toluene or dimethylformamide (DMF) (soluble GMA monomers); alternatively, polymerize in bulk.\n4. **Reaction apparatus:** Round-bottom flask with thermal stirrer, thermometer, reflux condenser, inert gas (nitrogen/argon).\n\n#### **Procedure**\n1. **Cleaning & Setup:**\n   - Clean and dry the round-bottom flask.\n   - Assemble stirring apparatus and attach a reflux condenser (to prevent solvent evaporation).\n   - Purge the system with an inert gas (e.g., argon or nitrogen) for about 30 minutes to remove oxygen, which inhibits radical polymerization.\n\n2. **Reagent Preparation:**\n   - Dissolve a predetermined amount of GMA in toluene or DMF. Typical concentrations are **10-30% by weight** in the solvent.\n   - Add AIBN as an initiator. Common usage is 1-2 mol% of the monomer. For instance, if 10 mmol (~1.42 g) of GMA is used, add 0.1-0.2 mmol (~0.016-0.032 g) of AIBN.\n   - Ensure all reagents are thoroughly mixed.\n\n3. **Reaction Conditions:**\n   - Degas the solution by gentle bubbling/purging with an inert gas.\n   - Heat the mixture under constant stirring at 65-70\u00b0C for 4-6 hours. This is the typical decomposition range for AIBN.\n   - Monitor the solution viscosity as polymerization progresses. The reaction is complete when there is no further change in viscosity or when the desired conversion is achieved.\n\n4. **Precipitation & Purification:**\n   - Cool the reaction to room temperature.\n   - Precipitate the polymer by dripping the reaction mixture into a non-solvent such as hexane or methanol, depending on solvent compatibility.\n   - Filter and wash the polymer. Dry in a vacuum oven at around 50\u00b0C to remove residual solvent.\n\n#### **Key Parameters**\n- Monomer-to-initiator ratio affects polymer chain length and molecular weight.\n- Free radical polymerization may result in some branching or slight cross-linking, especially under high monomer concentrations.\n\n---\n\n### **Step 2: Functionalization of PGMA to Enhance Hydrophilicity**\n\nThe synthesized PGMA contains reactive epoxide rings on its side chains. These rings can undergo nucleophilic substitution or ring-opening reactions to introduce hydrophilic functional groups, such as hydroxyl groups, amine groups, or zwitterionic moieties.\n\n#### **Materials Required**\n1. **Hydrophilic reagents:**\n   - Ethanolamine (to introduce hydroxyl and amine groups).\n   - Water (*if simple hydrolysis is preferred for hydroxylation*).\n   - Amines, e.g., 2-(dimethylamino)ethanol, for zwitterionic properties.\n2. **Catalyst:**\n   - Sulfuric acid or triethylamine (depending on the reaction type).\n3. **Solvent:** Methanol, ethanol, or water.\n4. **pH Adjuster:** Sodium hydroxide if a base-catalyzed reaction is chosen.\n\n#### **Procedure**\n1. **Epoxide Ring Opening:**\n   - Dissolve the PGMA polymer in a suitable solvent such as methanol or ethanol at a concentration of 5-10% w/v.\n   - Slowly add the hydrophilic reagent (e.g., ethanolamine) to the reaction mixture. Maintain a molar ratio of **1:1 or 1:2** (reagent to epoxide groups).\n   - Add a small quantity of a catalyst like sulfuric acid or triethylamine to initiate ring-opening.\n\n2. **Reaction Conditions:**\n   - Heat the solution gently at 50-60\u00b0C with stirring for 4-8 hours. Ensure complete solubilization.\n   - Monitor progress using techniques like FTIR (appearance of \u2013OH or amine-related bands) or NMR spectroscopy (disappearance of epoxide signals).\n\n3. **Neutralization and Precipitation:**\n   - Cool the reaction and neutralize the medium (if acidic) with sodium hydroxide or another neutralizing agent.\n   - Precipitate the modified polymer from a non-solvent (as described in Step 1), then clean and dry the product.\n\n---\n\n### **Final Product:**\nThe resulting polymer, functionalized PGMA, possesses hydrophilic groups such as hydroxyl or amine groups, making it significantly more hydrophilic than unmodified PGMA. The hydrophilicity can be tuned by varying the extent of functionalization or selecting reagents with high water affinity.\n\n#### **Characterization:**\n- **Fourier-transform infrared spectroscopy (FTIR):** To confirm the presence of hydrophilic groups (e.g., OH, NH).\n- **NMR spectroscopy:** To monitor epoxide conversion.\n- **Contact Angle Measurement:** To quantify hydrophilicity.\n\n---\n\n### **Conclusion:**\nThis two-step strategy (polymerization followed by functionalization) offers a robust and versatile method for producing functionalized hydrophilic polymers using glycidyl methacrylate. The approach allows for significant control over polymer properties and is compatible with various functionalization agents to meet diverse application needs (biomedical coatings, hydrogels, etc.)."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe how you would utilize diethanolamine in the synthesis of a hydrophilic polymer, considering its structural properties and potential reactivity. How does this molecule contribute to enhancing hydrophilicity?"}, {"role": "assistant", "content": "### Analysis of the Question and Key Points:\n\nThe focus of the question is on using **diethanolamine** (DEA, a molecule with two hydroxyl groups and one secondary amine group) in the synthesis of a **hydrophilic polymer**. To answer, we must:\n1. Analyze the structural properties and reactivity of diethanolamine.\n2. Propose an experimental scheme where diethanolamine is utilized as a monomer or co-monomer.\n3. Highlight how diethanolamine contributes to hydrophilicity.\n4. Provide systematic details of the synthesis steps, including reaction conditions, reagents, and quantitative aspects.\n\n### Detailed and Systematic Experimental Preparation Scheme:\n\n#### Step 1: Understanding the Role of Diethanolamine (DEA)\n**Structural Properties of Diethanolamine (DEA):**\n- Diethanolamine contains:\n  - Two hydroxyl groups (\u2013OH) that are hydrophilic and reactive.\n  - One secondary amine group (\u2013NH) that can participate in nucleophilic reactions, such as amidation or ring-opening polymerizations.\n- DEA's structure makes it a versatile molecule for introducing both **hydrophilic functional groups** (hydroxyls) and potential crosslinking points (secondary amine).\n\n**Contribution to Hydrophilicity:**\n- The hydroxyl groups increase **hydrophilicity** by forming hydrogen bonds with water.\n- The secondary amine can add sites for further chemical modifications, which can also influence water affinity, depending on the derivative.\n\n#### Step 2: Experimental Scheme for Synthesizing a Hydrophilic Polymer Using DEA\n\nDiethanolamine can be incorporated into a hydrophilic polymer in various ways. Here, I will provide a stepwise synthesis of a **polyurethane hydrogel**, a common class of hydrophilic polymers where DEA can play a key role.\n\n---\n\n### ***Synthesis of a Polyurethane-Based Hydrophilic Polymer Using Diethanolamine***\n\n#### **Overview of the Synthetic Pathway:**\nThe polymer will be prepared by the reaction of:\n1. Diethanolamine (a tri-functional monomer).\n2. A diisocyanate (e.g., hexamethylene diisocyanate, HDI) as the coupling/chain-extending agent.\n3. Polyethylene glycol (PEG, molecular weight 400\u20132000 Da) as a soft, hydrophilic segment to improve water interaction.\n4. A crosslinker or optional additives (if forming a 3D network).\n\n---\n\n#### **Step 1: Preparation of the Reaction Mixture**\n- **Reagents Required**:\n  - Diethanolamine (DEA): 0.01 moles.\n  - Polyethylene glycol (PEG, MW 1000): 0.005 moles.\n  - Hexamethylene diisocyanate (HDI): 0.015 moles (stoichiometric excess to ensure complete reaction with hydroxyl and amine groups).\n  - Catalyst: Dibutyltin dilaurate (0.1 wt% of the reaction mixture).\n  - Solvent: Anhydrous dimethylformamide (DMF, 15\u201320 mL).\n\n#### **Step 2: Reaction Setup**\n1. **Pre-mixing DEA and PEG**:\n   - Dissolve DEA and PEG in anhydrous DMF (10 mL).\n   - Stir at room temperature under an inert nitrogen atmosphere to prevent moisture contamination (isocyanates react with water to form ureas).\n   - DEA and PEG provide the hydroxyl functionality to react with HDI.\n\n2. **Addition of Hexamethylene Diisocyanate (HDI)**:\n   - Slowly add HDI to the reaction mixture at 60\u201370\u00b0C while stirring continuously.\n   - Maintain a **stoichiometric ratio** where the molar sum of hydroxyl groups (from DEA and PEG) and amine groups (from DEA) equals the number of isocyanate groups in HDI.\n   - The reaction involves the formation of urethane linkages (-NH-CO-O-) between hydroxyls and isocyanates and urea linkages (-NH-CO-NH-) between amines and isocyanates.\n\n3. **Catalysis**:\n   - Add dibutyltin dilaurate (0.1 wt%) as a catalyst to increase the reaction rate and enhance polymerization.\n\n4. **Reaction Monitoring**:\n   - Monitor the progress of the reaction using Fourier Transform Infrared Spectroscopy (FTIR). The disappearance of the \u2013NCO peak (~2270 cm\u207b\u00b9) indicates complete reaction with the hydroxyl and amine groups.\n\n---\n\n#### **Step 3: Formation of the Hydrogel (Optional Cross-Linking)**\n- To form a 3D hydrophilic network (a hydrogel), you can use an additional di- or tri-functional crosslinker (e.g., glycerol or trimethylolpropane). \n- Add the crosslinker in small amounts (0.001\u20130.002 moles) before introducing HDI to ensure homogeneous network formation.\n\n---\n\n#### **Step 4: Purification of the Polymer**\n1. Precipitate the polymer by pouring the reaction mixture into excess cold diethyl ether.\n2. Wash the precipitate with diethyl ether to remove unreacted monomers and catalyst residues.\n3. Dry the purified polymer in a vacuum oven at 50\u00b0C overnight.\n\n---\n\n#### **Step 5: Characterization of the Polymer**\n1. Confirm the structure using **FTIR**:\n   - Look for characteristic urethane (-NH-CO-O-) peaks (~1700 cm\u207b\u00b9).\n   - Absence of \u2013NCO peaks (~2270 cm\u207b\u00b9) indicates complete reaction.\n2. Investigate hydrophilicity:\n   - Measure the **water absorption/swelling ratio** to assess hydrophilicity.\n   - Conduct **contact angle measurements** to quantify surface hydrophilicity.\n3. Test the thermal properties (optional):\n   - Use **Thermogravimetric Analysis (TGA)** or **Differential Scanning Calorimetry (DSC)** to investigate thermal stability.\n\n---\n\n### Key Features of This Polymer:\n1. **Hydrophilicity**: The hydroxyl groups from DEA and PEG provide sites for hydrogen bonding, improving water affinity.\n2. **Biocompatibility** (optional): The polymer can be tailored for biomedical applications by selecting medical-grade PEG and diisocyanates.\n3. **Customizability**: Varying the PEG molecular weight or DEA-HD ratio tailors the polymer's hydrophilicity and mechanical properties.\n\n---\n\n### Conclusion\nIn this synthesis, **diethanolamine** plays a dual role:\n- Its hydroxyl groups enhance **hydrophilicity** by facilitating hydrogen bonding with water.\n- Its secondary amine group participates in reactions to form urea linkages, which contribute to the structural integrity of the polymer.\n\nBy following the steps above, a hydrophilic polyurethane polymer can be systematically prepared, ensuring precise control over the polymer's chemical and physical properties."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "How would you incorporate glycerol dimethacrylate into a thermoplastic polymer matrix to enhance its hydrophilicity? Detail the steps for blending it with other components and describe the curing process."}, {"role": "assistant", "content": "### Analysis of the Question:\n\nThe central idea of your question concerns the incorporation of **glycerol dimethacrylate (GDMA)** into a thermoplastic polymer matrix to enhance its hydrophilicity. GDMA has multiple hydroxyl (-OH) groups that contribute to hydrophilicity, and its methacrylate groups allow it to chemically bond or polymerize within a matrix.\n\nKey considerations:\n1. **Chemical Characteristics**: GDMA is a hydrophilic monomer with two methacrylate groups, which makes it ideal for copolymerization to enhance the hydrophilicity of thermoplastic polymers.\n2. **Polymer Compatibility**: Choosing a compatible thermoplastic polymer with free functional groups or open chains for blending and crosslinking.\n3. **Preparation Method**: Achieving homogeneous mixing, polymerization, and curing within the thermoplastic matrix.\n4. **Reaction Conditions**: Ensuring the methacrylate groups polymerize effectively without damaging the polymer matrix.\n\n### Experimental Preparation Scheme:\n\nHere\u2019s the step-by-step, systematic procedure to incorporate GDMA into a thermoplastic polymer matrix and enhance the hydrophilicity:\n\n---\n\n#### **Step 1: Selection of Thermoplastic Polymer Matrix**\nChoose a thermoplastic polymer that can physically or chemically blend with GDMA. Suitable candidates include:\n- Polyvinyl chloride (PVC)\n- Poly(methyl methacrylate) (PMMA)\n- Polystyrene (PS)\n- Polyethylene glycol (PEG) blends\n\nEnsure the polymer has sufficient thermal stability to withstand the curing process and can interact with methacrylate groups and hydroxyl functionalities.\n\n---\n\n#### **Step 2: Preparation of Materials**\n**Materials Needed:**\n- **GDMA**: Monomer to enhance hydrophilicity.\n- **Thermoplastic polymer**: Base matrix (e.g., PMMA).\n- **Crosslinking agent**: Ethylene glycol dimethacrylate (EGDMA) or other crosslinkers (optional).\n- **Thermal initiator**: Benzoyl peroxide (BPO) or azobisisobutyronitrile (AIBN) to initiate free radical polymerization.\n- **Solvent**: Tetrahydrofuran (THF), to facilitate mixing if the polymer matrix is not molten.\n- **Heat Source**: Oven or water bath to control curing temperature.\n\n---\n\n#### **Step 3: Formulate the Polymer Blend**\n1. **Weigh the Components**:\n   - GDMA (10\u201350 wt% relative to the polymer matrix, depending on desired hydrophilicity).\n   - Thermoplastic polymer (remaining weight percentage).\n   - Crosslinking agent (if used): 1\u20135 wt% based on GDMA content.\n   - Thermal initiator: 0.5\u20131 wt%.\n\n2. **Dissolve in a Solvent** (if necessary):\n   - Dissolve the thermoplastic polymer in THF. Ensure the solvent fully solubilizes the polymer to create a homogeneous solution.\n   - Separately, dissolve GDMA and the initiator in the same solvent, then mix this solution with the above polymer solution.\n\n---\n\n#### **Step 4: Mixing and Homogenization**\n- Use a mechanical mixer or ultrasonic stirring apparatus to create a homogeneous blend of GDMA and the thermoplastic polymer matrix. Maintain stirring for 30\u201360 minutes at room temperature for a uniform mixture.\n\n---\n\n#### **Step 5: Polymerization and Curing**\n1. **Transfer the Blend**:\n   - Pour the homogenized mixture into molds or onto a flat surface lined with a non-stick layer (e.g., Teflon-coated sheets).\n\n2. **Set the Reaction Temperature**:\n   - Gradually heat the material to the polymerization temperature (e.g., 60\u201380\u00b0C for BPO or AIBN systems).\n   - Ensure even heating throughout the polymer layer. This activates the thermal polymerization of the methacrylate groups.\n\n3. **Control Curing Time**:\n   - Allow curing to proceed for 2\u20136 hours, depending on the matrix\u2019s thickness and crosslink density. Longer curing ensures complete polymerization and bonding.\n\n---\n\n#### **Step 6: Post-Curing Treatment**\n1. **Remove Residual Solvent**:\n   - Dry the cured polymer at 50\u201370\u00b0C for 3\u20136 hours in a vacuum oven to eliminate any leftover solvent.\n\n2. **Enhanced Network Formation** (if required):\n   - Use UV curing or additional thermal treatment to strengthen bonding further.\n\n---\n\n#### **Step 7: Characterization**\nOnce the polymers are formed:\n1. **Hydrophilicity Testing**:\n   - Test the water contact angle (WCA) on the cured polymer surface.\n   - A decrease in the WCA indicates improved hydrophilicity.\n\n2. **Mechanical Testing**:\n   - Confirm that the addition of GDMA did not compromise the structural integrity of the polymer matrix.\n3. **Fourier Transform Infrared Spectroscopy (FTIR)**:\n   - Verify the successful incorporation of GDMA by identifying the characteristic hydroxyl and methacrylate functional group signals.\n\n---\n\n### Additional Notes:\n1. **Safety Precautions**:\n   - Handle GDMA and initiators (like BPO or AIBN) with care as they can be reactive and harmful.\n2. **Optimization**:\n   - The wt% ratio of GDMA and polymer matrix can be adjusted through preliminary trials to balance hydrophilicity and mechanical properties.\n\n---\n\nThis approach provides clear guidelines for incorporating glycerol dimethacrylate into a thermoplastic polymer matrix for enhanced hydrophilicity."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "In your synthesis of hydrophilic polymers, if isophorone diisocyanate (IPDI) is used to form a prepolymer, how would you ensure that the functional groups required for increased hydrophilicity are introduced into the polymer structure?"}, {"role": "assistant", "content": "To address your question systematically, let's analyze the problem and summarize key points:\n\n### Key Points:\n1. **Objective**: The synthesis involves using isophorone diisocyanate (IPDI) as a key reagent to form a prepolymer, and the goal is to introduce functional groups into the polymer structure that enhance hydrophilicity.\n2. **Challenge**: Isophorone diisocyanate contains isocyanate (-NCO) groups which offer reactivity for further modification. To achieve hydrophilicity, we need hydrophilic functional groups like hydroxyl (-OH), carboxylic (-COOH), sulfonic (-SO3H), or amine (-NH2).\n3. **Approach**: The experimental scheme should include:\n   - Reaction conditions to form the initial prepolymer with IPDI.\n   - Introduction of hydrophilic functional groups through precise chemical reactions.\n   - Control of reagent ratios, reaction conditions, and steps for purification.\n\nHere\u2019s the detailed experimental preparation scheme:\n\n---\n\n### Step-by-Step Synthesis Scheme:\n\n#### **Step 1: Formation of the Prepolymer**\n- **Objective**: React IPDI with a polyol to form the prepolymer containing pendant functional groups.\n- **Reagents**:\n  - IPDI: Acts as the diisocyanate source.\n  - Polyol: Choose a hydrophilic polyol such as polyethylene glycol (PEG) or glycerol to introduce intrinsic hydrophilicity. PEG with molecular weight 400-1000 g/mol is recommended for moderate chain length.\n- **Procedure**:\n  1. Dissolve PEG (or the polyol of choice) in anhydrous dimethylformamide (DMF) or tetrahydrofuran (THF).\n  2. Add a catalytic amount (0.2\u20130.5% w/w) of dibutyltin dilaurate (DBTDL) as the catalyst.\n  3. Gradually add IPDI to the stirred solution under nitrogen atmosphere or inert conditions to prevent moisture interference.\n  4. Maintain reaction at 70\u201380\u00b0C for 3\u20134 hours while stirring continuously to allow efficient reaction of -NCO groups with hydroxyl (-OH) groups of PEG.\n  5. Monitor the reaction using FTIR spectroscopy to ensure disappearance of the excess -NCO peak (~2260 cm\u207b\u00b9) corresponding to unreacted isocyanate.\n\n---\n\n#### **Step 2: Introduction of Hydrophilic Functional Groups**\n- **Objective**: Incorporate specific terminal hydrophilic groups that enhance water affinity beyond the hydrophilicity from PEG.\n- **Reagents**:\n  - Amino acids (e.g., lysine for -NH2 groups or glutamic acid for -COOH groups).\n  - Chain extenders with hydrophilic groups, such as diethanolamine (provides hydroxyl and amine groups).\n- **Procedure**:\n  1. After forming the IPDI-polyol prepolymer, cool the reaction mixture to room temperature.\n  2. Prepare an aqueous or alcoholic solution of the chosen hydrophilic reagent (e.g., lysine or glutamic acid).\n  3. Slowly add the solution to the prepolymer mixture under stirring. Monitor stoichiometric ratios carefully:\n     - For lysine: Use 1 mol equivalent of lysine per unreacted -NCO group.\n     - For diethanolamine: Use 1.2\u20131.3 mol equivalents per -NCO group to ensure full reaction.\n  4. Resume stirring at 50\u201370\u00b0C for 6\u20138 hours, ensuring complete grafting of functional groups.\n  5. Verify the incorporation by FTIR or NMR spectroscopy:\n     - FTIR: Appearance of peaks ~3300 cm\u207b\u00b9 (NH2 stretching) or ~1720 cm\u207b\u00b9 (-COOH stretching).\n     - NMR: Chemical shifts corresponding to the hydrophilic groups.\n\n---\n\n#### **Step 3: Finalization of the Polymer**\n- **Objective**: Purify the hydrophilic polymer and process it into usable form.\n- **Procedure**: \n  1. Precipitate the polymer by slowly adding the reaction mixture into excess cold water or ethanol, depending on solvent solubility.\n  2. Filter the precipitate and wash thoroughly to remove unreacted reagents or by-products.\n  3. Dry under vacuum at 50\u201360\u00b0C for 12\u201324 hours until moisture content is eliminated.\n  4. Characterize the final polymer for hydrophilicity:\n     - Test water contact angle (expected to be < 60\u00b0 for highly hydrophilic polymers).\n     - Measure swelling behavior in water or other polar solvents.\n\n---\n\n### Notes for Reaction Optimization:\n1. **Molar Ratios**: Ensure tight control of the molar ratios of IPDI, polyol, and hydrophilic chain extenders to avoid issues of cross-linking or incomplete functionalization.\n2. **Catalyst Use**: Avoid excessive catalyst concentrations as this may lead to side reactions and degrade product quality.\n3. **Reaction Atmosphere**: Isocyanates are moisture-sensitive; use a dry nitrogen atmosphere throughout the experiment.\n4. **Solvent Choice**: DMF is highly effective for dissolving reagents but toxic. Ensure proper ventilation or consider THF for safer handling.\n\n---\n\n### Conclusion:\nThe synthesis involves forming an IPDI-based hydrophilic prepolymer using PEG or glycerol, followed by functionalization with amino acids or hydrophilic extenders like diethanolamine. Reaction conditions (temperature, molar ratios, and atmosphere) should be finely tuned, and purification processes optimized for high-yield, hydrophilic polymer production.\n\nFeel free to discuss any further modifications or inquire if you're unclear about any steps!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "During free radical polymerization, you need to add IRGACURE 1173 as an initiator. Explain how you would incorporate this molecule in the reaction mixture and why it is critical to the curing process of the polymer network."}, {"role": "assistant", "content": "To address your question systematically, we will analyze the molecular context and discuss the role and integration of IRGACURE 1173 as an initiator during free-radical polymerization. This explanation will help you understand its importance and guide you toward performing the synthesis accurately in the laboratory.\n\n---\n\n**Analysis of the Questions' Key Points:**\n\n1. **IRGACURE 1173**: IRGACURE 1173 (1-Hydroxycyclohexyl phenyl ketone) is a photoinitiator commonly used in free-radical polymerization processes. It absorbs UV light and creates free radicals necessary to initiate polymerization.\n2. **Critical Role in Curing**: The photoinitiator is essential in triggering the polymerization reaction and ensuring the curing process forms a polymer network efficiently and uniformly.\n3. **Incorporation into the Reaction Mixture**: Understanding how to safely and precisely introduce IRGACURE 1173 into the system is vital for the stability of the reaction mixture and achieving the desired polymer properties.\n\n---\n\n**Detailed Experimental Procedure: Incorporating IRGACURE 1173 in the Polymerization Reaction**\n\nBelow is a step-by-step guide for incorporating IRGACURE 1173 in free-radical polymerization experiments. Follow this methodology carefully for laboratory success:\n\n---\n\n### **Step 1: Selection of Reactants and Materials**\nPrepare the following materials based on the designed polymer network:\n- **Monomer mixture**: Decide on the hydrophilic monomers to be polymerized. For example, hydroxyethyl methacrylate (HEMA), N-vinylpyrrolidone (NVP), or polyethylene glycol methacrylate (PEGMA) are commonly used for hydrophilic polymers.\n- **Cross-linker** (optional): If a network structure is desired, include a bifunctional or multifunctional monomer such as ethylene glycol dimethacrylate (EGDMA).\n- **Solvent** (optional): Select a solvent if dilution is needed for controlling viscosity (e.g., ethanol or water for hydrophilic systems).\n- **IRGACURE 1173**: The photoinitiator (1-Hydroxycyclohexyl phenyl ketone).\n- **Other additives**: Consider stabilizers or co-initiators (if applicable).\n\n---\n\n### **Step 2: Weighing and Ratio Calculation**\nAccurate weighing and molar ratios are critical for reproducibility. Example reaction ratios may be:\n- Monomers: Typically 95\u201398 wt% of the total composition.\n- Cross-linker: 2\u20135 wt%, depending on the desired network structure.\n- IRGACURE 1173: Added at 1\u20135 wt% of the total monomer weight. A typical starting point is around 2 wt%.\n  \n**Example Calculation**:\nIf preparing a 100 g reaction mixture:\n- Monomer: 95 g (e.g., HEMA).\n- Cross-linker (if used): 4 g (e.g., EGDMA for cross-linked hydrophilic polymers).\n- IRGACURE 1173: 1 g (2 wt%).\n\n---\n\n### **Step 3: Preparation of the Mixture**\n1. **Dissolve the Components**:\n   - Use a clean, glass reaction vessel. Start by dissolving the monomers and cross-linkers into the chosen solvent (if applicable). Stir gently to avoid introducing air bubbles.\n   - Add the IRGACURE 1173 after the monomers and cross-linkers are fully solubilized. Ensure uniform mixing for homogeneity. IRGACURE 1173 is soluble in many organic solvents but may precipitate in water. Select solvents accordingly if water is used.\n   \n2. **Reaction Mixture Observations**:\n   - Check for any cloudiness or precipitation in the solution. Adjust solvent or ratios as needed for complete solubility.\n\n---\n\n### **Step 4: UV Irradiation Setup**\n1. **UV Lamp Selection**:\n   - IRGACURE 1173 absorbs UV light within the wavelength range of 300\u2013400 nm. Ensure your UV lamp operates in this range. A typical choice is a medium-pressure mercury vapor lamp or LEDs emitting ~365 nm.\n2. **Intensity Calibration**:\n   - Calibrate the energy density of the UV light source. A standard protocol involves applying 2\u20135 mW/cm\u00b2 intensity, depending on the formulation's photoreactivity. Too low intensity may delay curing, while too high intensity may overheat the mixture or induce unwanted side reactions.\n\n---\n\n### **Step 5: Polymerization and Curing**\n1. **Initiation**:\n   - Illuminate the reaction mixture with the UV source. IRGACURE 1173 absorbs UV light and undergoes photochemical cleavage to generate free radicals. These radicals initiate chain polymerization and cross-linking (if applicable) of the monomers.\n   \n2. **Curing Duration**:\n   - Typical curing times range between 5\u201315 minutes, depending on the mixture's thickness and UV intensity. Monitor the reaction to avoid under- or over-curing.\n\n3. **Temperature Maintenance**:\n   - Keep the reaction vessel temperature constant during curing. Excessively high temperatures can accelerate degradation. A temperature range of 20\u201340\u00b0C is generally sufficient for hydrophilic polymer synthesis.\n\n---\n\n### **Step 6: Post-Curing and Analysis**\n1. **Post-Curing**:\n   - Expose the cured polymer to UV light for an additional 2\u20135 minutes, if necessary, to ensure complete polymerization and elimination of residual monomers.\n   \n2. **Characterization**:\n   - Perform tests to confirm success:\n     - FTIR spectroscopy to verify functional groups.\n     - Swelling tests for hydrophilicity (in water or similar solvents).\n     - Mechanical testing (if relevant).\n\n---\n\n**Importance of IRGACURE 1173 in the Curing Process:**\n\n- **Initiator Efficiency**: IRGACURE 1173 achieves high radical generation efficiency under UV light, ensuring rapid and uniform initiation of polymerization across the mixture.\n- **Control of the Network**: By controlling the quantity of IRGACURE 1173, you can regulate the kinetics and degree of curing to achieve desired polymer properties (e.g., mechanical strength, degree of swelling, or water affinity).\n- **Reduced Side Reactions**: IRGACURE 1173 typically decomposes cleanly under UV light, minimizing the generation of undesired byproducts.\n\n---\n\nBy following this step-by-step scheme, you will be able to incorporate IRGACURE 1173 into the reaction mixture effectively and ensure its critical role in forming the hydrophilic polymer network. Feel free to ask any follow-up questions or discuss potential optimizations for your specific polymer system!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe how you would utilize N-butylimidazole to introduce a cationic functional group into a polymer. Include the reaction conditions you would implement to achieve a homogenous product."}, {"role": "assistant", "content": "Certainly! Introducing a cationic functional group into a polymer using N-butylimidazole is an excellent way to increase hydrophilicity, as the resulting cationic charges will promote water attraction and solubility. Let\u2019s systematically address your question by analyzing and providing a detailed experimental scheme.\n\n---\n\n### **1. Problem Analysis and Key Points Identification**\nThe goal is to introduce a cationic functional group into a polymer using N-butylimidazole. Here's what we need to focus on:\n- Selection of a polymer backbone that can react with N-butylimidazole to form covalent bonds.\n- Functionalization via a reaction that grafts or incorporates N-butylimidazole-derived cationic groups onto the polymer.\n- Reaction conditions that avoid side reactions and ensure a homogenous product.\n- Specific details on reaction time, temperature, solvents, and mole ratios of reagents.\n\n---\n\n### **2. Experimental Design**\n\n#### **Step 1: Choosing a Suitable Polymer Backbone**\nTo react with N-butylimidazole, the polymer must contain electrophilic groups (e.g., alkyl halides, epoxides, or unsaturated groups). A common example is **poly(ethylene glycol)-bromoalkane** (PEG-Br), where the terminal bromine acts as an electrophile enabling a nucleophilic substitution reaction with the imidazole molecule.\n\nWhy PEG-Br?\n- It's water-compatible, providing inherent hydrophilicity.\n- The bromine on the polymer chain allows for efficient substitution by N-butylimidazole to introduce cationic imidazolium groups.\n\n#### **Step 2: Chemical Reaction Overview**\nThe targeted reaction is **nucleophilic substitution (SN2)** between the alkyl bromide group of the polymer (PEG-Br) and N-butylimidazole:\n\n\\[\nPEG-Br + N\\text{-}butylimidazole \\xrightarrow{\\text{SN2 Conditions}} PEG\\text{-}imidazolium-Bu^+Br^-\n\\]\n\nThe product is a cationic polymer functionalized with butylimidazolium groups, with the bromide acting as the counterion.\n\n#### **Step 3: Detailing the Experimental Procedure**\n\n---\n\n**a) Materials Required:**\n- Poly(ethylene glycol)-bromoalkane (PEG-Br) (molecular weight tailored to your needs, e.g., PEG Mw ~2000 or 4000, functionalized with terminal bromide).\n- N-butylimidazole.\n- Solvent: Acetonitrile (anhydrous, polar aprotic solvent to facilitate the SN2 mechanism).\n- Reaction flask (round-bottom flask with magnetic stirrer or overhead stirrer).\n- Nitrogen or argon gas for an inert atmosphere.\n- Reagents for post-synthesis purification: e.g., diethyl ether for polymer precipitation.\n- Analytical tools: FTIR or NMR for structural confirmation, TGA or DSC for thermal property verification.\n\n---\n\n**b) Reaction Setup:**\n1. **Polymer Dissolution**:\n   - Weigh out a known amount of PEG-Br (e.g., **2 g, ~1 mmol of terminal Br groups**).\n   - Dissolve PEG-Br in 20 mL of anhydrous acetonitrile under inert gas (e.g., nitrogen) with continuous stirring.\n\n2. **Addition of N-butylimidazole**:\n   - Use an equimolar or slight molar excess of N-butylimidazole (1.5 mmol, ~175 mg) to ensure all bromide groups are functionalized. The slight excess minimizes unreacted bromine sites on the polymer.\n   - Add the N-butylimidazole dropwise to the stirred PEG-Br solution under inert conditions.\n\n3. **Reaction Conditions**:\n   - Conduct the reaction at an elevated temperature (~70\u201380 \u00b0C) for optimal SN2 kinetics. Use an oil bath to control the temperature accurately.\n   - Stir the reaction mixture for 12\u201324 hours to ensure complete substitution. Monitor the reaction progress using thin-layer chromatography (TLC) or by taking aliquots for NMR analysis.\n\n4. **Work-Up**:\n   - Cool the reaction mixture to room temperature.\n   - Precipitate the polymer by slowly adding it to a large volume of cold hydrophobic solvent (e.g., diethyl ether). The cationic polymer will separate as a solid.\n   - Wash the resulting polymer precipitate with diethyl ether multiple times to remove unreacted N-butylimidazole and solvent.\n\n5. **Drying and Storage**:\n   - Dry the purified polymer in a vacuum oven at 40 \u00b0C for ~12 hours to remove residual solvent.\n   - Store the dried polymer in a desiccator to preserve its purity.\n\n---\n\n#### **Step 4: Characterization of the Product**\n1. **Structural Confirmation**:\n   - Use **NMR spectroscopy (1H-NMR)** to confirm the presence of cationic imidazolium groups. Peaks corresponding to the imidazole ring and attached butyl group should appear. The integration of these peaks against the PEG backbone provides quantitative confirmation of substitution.\n   - **FTIR analysis**: Look for characteristic peaks around 3100\u20133300 cm\u207b\u00b9 for the imidazole C\u2013H stretch and confirm the absence of any residual C\u2013Br bonds (should disappear at ~500\u2013600 cm\u207b\u00b9 in PEG-Br).\n\n2. **Molecular Weight Analysis**:\n   - Determine molecular weight shifts (e.g., using gel permeation chromatography\u2014GPC) as imidazole substitution will slightly increase the polymer's molar mass.\n\n3. **Thermal Properties**:\n   - Perform **DSC (Differential Scanning Calorimetry)** to study any changes in thermal transitions (e.g., glass transition or melting point shifts).\n   - **TGA (Thermogravimetric Analysis)** to examine stability and decomposition temperatures, ensuring polymer integrity.\n\n4. **Evaluation of Hydrophilicity**:\n   - **Contact Angle Measurements**:\n     Harvest the functionalized polymer as a coating or film and measure its water contact angle to confirm enhanced hydrophilicity due to the introduction of cationic groups.\n   - **Water Solubility Test**: Assess the degree of solubility in water or aqueous buffers.\n\n---\n\n### **3. Key Reaction Parameters and Suggestions for Homogeneity**\n- **Stoichiometry**: Use slightly excess N-butylimidazole (1.5 equiv.) to ensure complete substitution.\n- **Solvent Choice**: Polar aprotic solvent (acetonitrile) ensures good solvation for the polymer and promotes the SN2 mechanism.\n- **Temperature Control**: Elevated temperature (70\u201380 \u00b0C) speeds up the reaction, but don\u2019t exceed 90 \u00b0C to avoid polymer degradation.\n- **Inert Atmosphere**: Oxygen-free conditions (nitrogen or argon) prevent side reactions that may degrade imidazole or oxidize the polymer backbone.\n\n---\n\n### **4. Conclusion**\nBy reacting PEG-Br with N-butylimidazole under SN2 reaction conditions, we successfully introduce cationic butylimidazolium groups into the polymer. Careful control of reaction conditions ensures a homogenous polymer product, which can significantly enhance hydrophilicity. With this detailed experimental scheme, you should be able to execute the synthesis in a laboratory and validate your results through appropriate characterization techniques.\n\nIf you need clarifications during the synthesis or characterization process, don\u2019t hesitate to ask! Good luck!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain the role of polyvinylpyrrolidone (PVP), specifically when used in combination with other compounds, in creating graft polymerized coatings to enhance hydrophilicity. How would you ensure that PVP becomes effectively entrapped within the polymer matrix?"}, {"role": "assistant", "content": "To address your question, we will systematically approach the role of polyvinylpyrrolidone (PVP) in enhancing hydrophilicity when combined with other compounds, particularly in graft polymerizations to produce hydrophilic coatings. I will also provide an experimental preparation scheme that ensures PVP becomes effectively entrapped within the polymer matrix.\n\n---\n\n### **Key Points to Consider**\n1. **Polyvinylpyrrolidone's Properties**:\n   - PVP is a hydrophilic polymer due to its amide functional groups that can form hydrogen bonds with water molecules. It is non-toxic, biocompatible, and highly soluble in water, making it ideal for creating hydrophilic materials.\n   - When used in polymer coatings, PVP improves water absorption, antifouling properties, and biocompatibility of the substrate.\n\n2. **Graft Polymerization Technique**:\n   - Graft polymerization creates a covalent bond between the polymer backbone and side chains (like PVP), ensuring the coating is durable and strongly adhered to the substrate.\n\n3. **Challenges in Entrapping PVP**:\n   - PVP must become covalently linked or physically entrapped in the polymer matrix to prevent it from washing away or leaching out during use.\n   - Designing reaction conditions that promote grafting of PVP onto the polymer backbone is critical.\n\n---\n\n### Step-by-Step Experimental Preparation Scheme\n\n#### **Step 1: Surface Preparation**\n- Before initiating graft polymerization, prepare the substrate (e.g., glass, polymeric film, ceramic surface) to ensure proper adhesion.\n- **Procedure**:\n  - Clean the surface using ethanol or acetone, followed by water to remove impurities.\n  - Apply an oxygen plasma or UV treatment to introduce reactive functional groups (e.g., hydroxyl or carboxyl groups) onto the surface, increasing its reactivity for subsequent polymerization.\n\n---\n\n#### **Step 2: Selection of Base Polymer**\n- Select a hydrophobic or semi-hydrophilic base polymer (e.g., poly(acrylic acid), polyethylene glycol, or polystyrene) for grafting.\n- Choose a polymer that can interact with PVP chemically or physically by forming covalent bonds.\n\n- **Key Reaction Principle**: \n  Incorporation of PVP occurs through radical or ionic mechanisms, depending on the desired polymerization method.\n\n---\n\n#### **Step 3: Reaction System Design**\nChoose **graft polymerization conditions** that enhance the covalent grafting of PVP onto the polymer backbone. Here, we use *radical graft polymerization* as a general method.\n\n##### **Reaction Details**:\n1. **Initiator System**:\n   - Use an appropriate radical initiator (commonly, **potassium persulfate (KPS)** or **benzoyl peroxide**) to generate free radicals on the base polymer backbone, promoting the addition of PVP.\n\n2. **Solvent**:\n   - Use a polar, aprotic solvent (e.g., DMF or water) to dissolve PVP and the base polymer and allow proper interactions between the reactants.\n\n3. **Molar Ratios and Concentrations**:\n   - Base polymer: Adjust base polymer concentration between 5\u201315 wt%.\n   - PVP: Use PVP at 20\u201340 wt% to ensure an excess of the hydrophilic component.\n   - Initiator: Typically use 0.5\u20131 wt% based on the total weight of the solution.\n\n---\n\n#### **Step 4: Grafting Reaction Procedure**\n- **Experimental Setup**:\n   - Dissolve base polymer, PVP, and the radical initiator in the solvent under stirring at constant temperature.\n   - Maintain the reaction temperature between 60\u201380\u00b0C (optimal for radical reactions) under a nitrogen or argon atmosphere to prevent oxygen quenching.\n\n- **Reaction Mechanism**:\n   - The initiator generates free radicals on the backbone, which promote the grafting of PVP molecules. This forms covalent bonds between PVP and the polymer network, ensuring PVP is entrapped and permanently integrated.\n\n- **Reaction Time**:\n   - Allow the reaction to proceed for 4\u20136 hours to ensure complete grafting.\n\n---\n\n#### **Step 5: Post-Reaction Processing**\n- After the reaction:\n   - Cool the reaction mixture to room temperature.\n   - Wash the resulting polymer coating thoroughly with ethanol or water to remove unreacted PVP and initiators.\n   - Dry the coating under vacuum to eliminate residual solvents.\n\n---\n\n#### **Step 6: Characterization**\nTo confirm successful grafting and entrapment of PVP:\n1. **Contact Angle Measurement**:\n   - Measure the water contact angle of the coated surface. A lower contact angle (<30\u00b0) confirms enhanced hydrophilicity.\n\n2. **Fourier Transform Infrared Spectroscopy (FTIR)**:\n   - Identify the characteristic amide peak at ~1650 cm\u207b\u00b9, indicative of PVP grafting.\n\n3. **Scanning Electron Microscopy (SEM)**:\n   - Observe the coating morphology to ensure uniform distribution of PVP.\n\n4. **Leaching Test**:\n   - Test for stability by immersing the coated substrate in water and verifying that PVP does not leach out significantly.\n\n---\n\n### Additional Considerations\n1. **Crosslinkers**:\n   - To further secure PVP within the polymer matrix, add a crosslinker (e.g., glutaraldehyde or ethylene glycol dimethacrylate), which bridges PVP and the base polymer.\n   - Introduce ~5 wt% crosslinker during polymerization to form a denser network.\n\n2. **Scaling Up**:\n   - Optimize the reagent ratios during small-scale experiments to ensure consistent results before scaling up to larger batches.\n\n---\n\n### Summary\nPolyvinylpyrrolidone (PVP) enhances hydrophilicity when covalently grafted onto a polymer matrix. Using radical graft polymerization with the correct initiator, solvent system, and reaction conditions, PVP can be effectively entrapped within the polymer matrix. This ensures the hydrophilic properties are stable and durable under operational conditions. By systematically following the described experimental steps, your lab experiment should yield success in synthesizing hydrophilic coatings with entrapped PVP.\n\nLet me know if you need clarification on any step or further details on experimental variations!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the importance of tetraethylorthosilicate (TEOS) in achieving a hydrophilic polymer film. What specific reaction does TEOS participate in, and how does this contribute to the surface properties of the material?"}, {"role": "assistant", "content": "To answer your question systematically, let's break it down into clear and logical steps: \n\n---\n\n### **1. Analyzing the Question and Key Points**\n\nThe focus of your question lies on understanding:\n- The **importance of tetraethylorthosilicate (TEOS)** in hydrophilic polymer film preparation.\n- The **specific reaction TEOS undergoes** and its role in modifying surface properties.\n- How these reactions ultimately contribute to the **hydrophilicity of the polymer material's surface**.\n\nUnderstanding the chemistry of TEOS and its ability to interact with polymers to introduce hydrophilicity requires delving into its molecular structure as well as the process of hydrolysis and condensation, core steps in sol-gel chemistry.\n\n---\n\n### **2. Systematic and Detailed Answer**\n\n#### **2.1 The Role and Importance of TEOS**\n\nTetraethylorthosilicate (TEOS, Si(OC\u2082H\u2085)\u2084) is an organosilicate compound widely used in sol-gel processes to introduce silica-based functionalities to materials. Its role in the preparation of hydrophilic polymer films is essential for the following reasons:\n\n1. **Hydrophilic Functional Group Introduction**:\n   TEOS reacts to produce silanol groups (-SiOH) on hydrolysis, which are inherently hydrophilic. These silanol groups can interact with water molecules through hydrogen bonding, enhancing surface hydrophilicity.\n\n2. **Improving Uniformity and Cross-Linking**:\n   TEOS undergoes condensation reactions, leading to silica network formation. This silica layer provides a stable, interconnected architecture on the polymer surface, thereby enhancing its physical properties and distributing hydrophilicity uniformly.\n\n3. **Customizable Surface Functionalization**:\n   By controlling TEOS reaction parameters (e.g., pH, temperature, time, solvent), the density of silanol groups and their spatial distribution can be fine-tuned to achieve desired hydrophilicity.\n\n#### **2.2 The Specific Reaction TEOS Participates In**\n\nTEOS participates in a **two-step reaction process** characteristic of sol-gel chemistry:\n\n1. **Hydrolysis**:\n   TEOS reacts with water in the presence of an acid or base catalyst to generate silanol groups (-SiOH). This step typically occurs as follows:\n   \\[\n   Si(OC\u2082H\u2085)\u2084 + 4H\u2082O \u2192 Si(OH)\u2084 + 4C\u2082H\u2085OH\n   \\]\n   Here, hydrolysis replaces ethoxy groups (-OC\u2082H\u2085) on the TEOS molecule with hydroxyl groups (-OH), resulting in the formation of silicic acid (Si(OH)\u2084) and ethanol (C\u2082H\u2085OH) as a by-product.\n\n2. **Condensation**:\n   The silanol groups formed in the hydrolysis step undergo condensation reactions, resulting in the formation of siloxane bonds (-Si-O-Si-), which create a solid silica network:\n   \\[\n   Si(OH)\u2084 + Si(OH)\u2084 \u2192 Si-O-Si + H\u2082O\n   \\]\n   Alternatively:\n   \\[\n   Si(OH)\u2084 + Si(OC\u2082H\u2085)\u2084 \u2192 Si-O-Si + C\u2082H\u2085OH\n   \\]\n   These reactions lead to the development of a three-dimensional silica matrix.\n\n#### **2.3 Contribution to Hydrophilic Surface Properties**\n\nOnce the silica layer forms, the material surface gains desirable hydrophilic properties due to:\n- The presence of **free silanol groups (-SiOH)** on the exposed surface. These groups engage in hydrogen bonding with water, significantly increasing surface wettability.\n- The intrinsic **porosity** of the silica network, which supports water absorption and adhesion at the interface.\n  \nIn polymer films, this process facilitates enhanced interaction with aqueous environments, making them suitable for applications in fields like separation membranes, biomedical devices, and coatings that require hydrophilic properties.\n\n---\n\n### **3. Experimental Preparation Scheme for a TEOS-Based Hydrophilic Polymer Film**\n\nHere is a step-by-step guide to synthesizing a hydrophilic polymer film using TEOS via sol-gel chemistry:\n\n#### **Step 1: Materials Required**\n- Tetraethylorthosilicate (TEOS): 98% purity or higher.\n- Polymer substrate: A suitable hydrophobic polymer (e.g., poly(dimethylsiloxane) (PDMS), polystyrene, etc.).\n- Solvents: Ethanol (C\u2082H\u2085OH) as a co-solvent to ensure miscibility.\n- Deionized water (H\u2082O): For hydrolysis.\n- Acidic Catalyst: Hydrochloric acid (HCl) or acetic acid as a catalyst (preferred pH: 2\u20133).\n- Optional: Organosilanes such as 3-aminopropyltrimethoxysilane (APTMS) for further functionalization.\n\n#### **Step 2: Preparation of Sol Solution**\n1. Dissolve TEOS in ethanol at a TEOS-to-ethanol molar ratio of approximately **1:4**.\n2. Add deionized water to achieve a water-to-TEOS molar ratio of **4:1**, sufficient for full hydrolysis.\n3. Introduce a small amount of acid (HCl) to the solution. Begin with 0.01 M and adjust as necessary to maintain pH at 2\u20133. This acidic environment catalyzes the hydrolysis reaction.\n4. Stir the solution continuously at room temperature for 1\u20132 hours to allow hydrolysis to occur.\n\n#### **Step 3: Coating Polymer Substrate**\n1. Clean the surface of the hydrophobic polymer substrate (e.g., PDMS) thoroughly to remove dust, grease, or oils.\n   - Use isopropanol and deionized water for cleaning.\n2. Apply the sol solution to the polymer substrate using one of the following techniques:\n   - **Dip Coating**: Immerse the substrate into the sol solution and withdraw it at a controlled speed to create a uniform film.\n   - **Spin Coating**: Deposit a small amount of sol solution onto the substrate and spin it at ~2000\u20133000 rpm to achieve a uniform coat.\n\n#### **Step 4: Gelation and Aging**\n1. Allow the coated substrate to rest at room temperature or slightly elevated temperature (e.g., 40\u00b0C) for several hours to facilitate gelation.\n2. During this step, condensation reactions will densify the silica layer and establish siloxane bonds.\n\n#### **Step 5: Curing**\n1. Cure the sample by heating it at a temperature range of **60\u2013120\u00b0C** for 4\u20138 hours. This step removes any remaining solvent and consolidates the silica network.\n2. Optionally, higher curing temperatures (~200\u00b0C) may be used if the polymer substrate can tolerate it for better condensation of siloxane bonds.\n\n#### **Step 6: Characterization of Surface Hydrophilicity**\n- **Contact Angle Measurement**: Evaluate the success of the process by measuring the water contact angle on the polymer film. A reduction in the angle (e.g., <30\u00b0) confirms hydrophilicity.\n- **Fourier Transform Infrared Spectroscopy (FTIR)**: To verify the presence of silanol (-SiOH) and siloxane (-Si-O-Si-) groups, highlighting successful hydrolysis and condensation.\n\n---\n\n### **4. Summary**\n\nTEOS plays a pivotal role in creating hydrophilic polymer films through its hydrolysis and condensation reactions in sol-gel chemistry. The introduction of silanol groups and a silica network significantly enhances the surface's hydrophilicity. By customizing processing parameters (e.g., pH, water content, curing time), you can optimize the coating process to achieve desired properties. The outlined experimental scheme provides a reliable approach to achieving this goal in the laboratory.\n\nThis comprehensive understanding and experimental outline should equip you with the knowledge and confidence to conduct the experiment successfully."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Propose a polymerization setup using ethylene glycol dimethacrylate as a crosslinking agent, and discuss how the choice of this molecule affects the mechanical and hydrophilic properties of the polymer."}, {"role": "assistant", "content": "Absolutely, let's approach this step by step.\n\n---\n\n### **Step 1: Analyze the question and summarize the key points.**\n\n#### Key Points:\n1. **Monomer system and crosslinking agent**: The question specifies the use of **ethylene glycol dimethacrylate (EGDMA)** as a crosslinking agent.\n2. **Objective**: You need to design a polymerization setup, detailing the synthesis process and reaction conditions.\n3. **Properties to discuss**: \n   - Influence of **EGDMA** on the **mechanical properties**, such as rigidity and toughness, of the resulting polymer.\n   - Influence of **EGDMA** on the **hydrophilic properties** of the polymer.\n\n---\n\n### **Step 2: Answer the question in detail and systematically.**\n\n#### **Experimental Preparation Scheme for a Hydrophilic Polymer Crosslinked with EGDMA**\n\n---\n\n#### **1. Monomer Selection**\nTo design a hydrophilic polymer, we'll start by selecting a hydrophilic monomer \u2014 for example, **2-hydroxyethyl methacrylate (HEMA)**. HEMA is widely used in biomaterial applications (like hydrogels) due to its hydrophilic hydroxyl (-OH) group, which interacts with water.\n\n- **EGDMA** will serve as the crosslinking agent. Its two methacrylate groups can form covalent crosslinks between polymer chains, enhancing the mechanical strength while retaining hydrophilicity because of the ethylene glycol backbone of EGDMA.\n\n---\n\n#### **2. Reaction Setup**\nPolymerization of HEMA in the presence of EGDMA involves a free-radical polymerization process. Below are the experimental details:\n\n---\n\n**a) Apparatus and materials:**\n- **Monomers**: HEMA as the base monomer and EGDMA as the crosslinking agent.\n- **Solvent**: Use **water** or **ethanol** as solvents to ensure a homogeneous reaction phase.\n- **Initiator**: Azobisisobutyronitrile (**AIBN**) or potassium persulfate (**KPS**) can be used as free-radical initiators.\n- **Inert atmosphere**: Nitrogen (N\u2082) will be used to purge the system to remove oxygen, which inhibits radical polymerization.\n\n---\n\n**b) Reaction steps:**\n\n1. **Preparation of Reaction Mixture**:\n   - Weigh the monomer **HEMA** and the crosslinking agent **EGDMA**. \n     - Example molar ratio: **HEMA:EGDMA** = 95:5 (to maintain a hydrophilic network while providing sufficient crosslinking for mechanical strength).\n     - For 10 g total monomer mixture:\n       - HEMA = 9.5 g (approx. 80 mmol)\n       - EGDMA = 0.5 g (approx. 2.5 mmol)\n   - Dissolve the monomer and crosslinker in 20 mL ethanol or water to form a homogeneous solution.\n\n2. **Initiation**:\n   - Dissolve **AIBN** (approx. 1 wt% of total monomer weight, e.g., 0.1 g) in the monomer solution.\n   - Sonicate the solution for a few minutes to ensure proper dispersion.\n\n3. **Deoxygenation**:\n   - Transfer the solution to a round-bottom flask or reaction vessel.\n   - Purge the reaction mixture with nitrogen gas for 20\u201330 minutes to remove dissolved oxygen, which can quench free-radical polymerization.\n\n4. **Polymerization**:\n   - Heat the reaction mixture to **65\u201370\u00b0C** while stirring (AIBN decomposes to generate radicals at this temperature).\n   - Allow the reaction to proceed for **4\u20136 hours** to ensure complete polymerization. The time will depend on the desired crosslink density and molecular weight.\n\n5. **Post-Polymerization and Purification**:\n   - After polymerization, the resulting hydrogel or polymer matrix will form.\n   - Wash the polymer thoroughly with ethanol and deionized water to remove unreacted monomer and impurities.\n   - Dry the polymer in a vacuum oven at 40\u201350\u00b0C.\n\n---\n\n**c) Optimization Notes**:\n- **Crosslinker concentration**: Increasing EGDMA concentration above 5 wt% will result in higher crosslink density, which enhances mechanical properties but may reduce swelling (and hence hydrophilicity). A careful balance between these parameters is essential.\n- **Solvent polarity**: Water as a solvent can enhance hydrophilicity, but ethanol can sometimes improve chain mobility during polymerization.\n\n---\n\n#### **3. Effects of EGDMA on Polymer Properties**\n\n**a) Hydrophilicity**:\n- The hydrophilic nature of the polymer primarily arises from the HEMA monomer\u2019s hydroxyl (-OH) group, which forms hydrogen bonds with water. \n- **Impact of EGDMA**: EGDMA contributes a polyethylene glycol-based hydrophilic segment, which further enhances hydrophilicity. However, an excessive amount of EGDMA may reduce overall water-absorbing capacity due to increased crosslinked density, limiting the polymer chain\u2019s ability to stretch and absorb water.\n\n**b) Mechanical Strength**:\n- EGDMA introduces crosslinks between polymer chains, forming a 3D network structure.\n - **Low EGDMA concentration (<5 wt%)**: Polymer will form a flexible hydrogel with high water swelling.\n - **Higher EGDMA concentration (5\u201310 wt%)**: Crosslink density increases, leading to a stiffer, stronger polymer with reduced swelling. This is useful where mechanical robustness is critical (e.g., biomaterial scaffolds or coatings).\n - **Excessive EGDMA (>10 wt%)**: Can lead to brittleness due to overly rigid crosslinking.\n\n**c) Tunability**:\n- The ratio of HEMA to EGDMA can be adjusted to tailor the hydrogel or polymer\u2019s water absorption capacity, toughness, and elasticity, making this system versatile for various applications.\n\n---\n\n### **Step 3: Final Notes and Recommendations**\n\n- **Safety Precautions**: Always handle methacrylate monomers with gloves and work in a fume hood due to their volatility and potential skin sensitizing properties. EGDMA is also a potential irritant.\n- **Characterization**: After synthesis, confirm the polymer's properties:\n  - Use **Fourier-transform infrared spectroscopy (FTIR)** to check for functional group incorporation (e.g., hydroxyl and ester groups).\n  - Measure swelling degree in water to evaluate hydrophilicity.\n  - Conduct tensile tests to assess mechanical properties.\n\nBy following this preparation scheme and systematically varying the HEMA:EGDMA ratio, you can produce hydrophilic polymers with tunable mechanical properties, suitable for diverse applications such as biomedical devices, hydrogels, and coatings.\n\n--- \n\nWould you like further guidance on specific characterization techniques or potential modifications to this procedure?"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe a procedure for functionalizing an inert polymer surface using tannic acid in combination with metal ions. How would this approach improve the hydrophilicity of the polymer?"}, {"role": "assistant", "content": "Ah, this is an excellent and timely question, touching upon the functionalization of an inert polymer surface to improve hydrophilicity! Let's break it down step by step, analyze the key points, and systematically provide an experimental preparation scheme for the functionalization process.\n\n---\n\n### **Key Points in the Question:**\n1. **Objective:** Functionalization of an inert polymer surface to improve hydrophilicity.\n2. **Methodology:** Utilization of tannic acid (TA) in combination with metal ions.\n3. **Desired Outcome:** Enhanced hydrophilicity of the polymer surface, likely by modifying its physical or chemical surface properties, including introducing hydrophilic functional groups or hydrophilic coordination structures.\n\nNow, I will design a precise preparation procedure employing tannic acid and metal ions to achieve this goal.\n\n---\n\n### **Experimental Procedure for Functionalization Using Tannic Acid and Metal Ions**\nFunctionalizing a polymer surface with tannic acid (TA) and metal ions involves creating a hydrophilic coating that strongly adheres to the polymer while imparting hydrophilic functional groups like hydroxyl (-OH). The tannic acid works as a polyphenolic molecule, forming coordination complexes with metal ions, which enhance crosslinking and stability.\n\n#### **Materials Needed:**\n1. **Polymer Substrate:** An inert polymer (e.g., polyethylene, polypropylene, or polystyrene). Ensure the sample has a smooth, clean surface.\n2. **Tannic Acid (TA):** Pharmaceutical-grade or analytical-grade powder.\n3. **Metal Ions Solution:** Transition metal ions (e.g., Fe\u00b3\u207a or Cu\u00b2\u207a). Ferric chloride (FeCl\u2083\u00b76H\u2082O) is an excellent starting choice.\n4. **Solvent for TA Solution:** Deionized water or ethanol-water mixture (preferred: deionized water to avoid interference).\n5. **Cleaning Agents:** Ethanol, acetone, and deionized water.\n6. **Buffer Solution (Optional):** pH-sensitive polymers may benefit from a phosphate buffer to control pH for tannic acid deposition.\n7. **Glassware and Reaction Vessels:** Clean, hydrophilic containers (glass Petri dishes or beakers).\n\n#### **Step 1: Pre-Treatment of the Polymer Surface**\n1. **Purpose:** Clean and activate the polymer surface, improving adhesion of the hydrophilic coating.\n2. Procedure:\n   - Rinse the polymer substrate thoroughly in ethanol or acetone to remove grease or contaminants.\n   - Subject the substrate to oxygen plasma treatment or a UV-ozone treatment for 10\u201315 minutes to increase surface energy and create active sites (e.g., carboxyl or hydroxyl groups). This step is crucial for inert, low-surface-energy polymers.\n\n#### **Step 2: Preparation of Tannic Acid Solution**\n1. **Purpose:** Create a tannic acid solution for polymer deposition.\n2. Procedure:\n   - Dissolve tannic acid (e.g., 2 g) in 100 mL deionized water to achieve a 2% (w/v) solution.\n   - Stir the solution at room temperature until fully dissolved. The solution may appear slightly brown.\n\n#### **Step 3: Preparation of Metal Ion Solution**\n1. **Purpose:** Provide a source of metal ions for complexation with tannic acid.\n2. Procedure:\n   - Prepare a 0.1 M ferric chloride solution by dissolving 1.35 g of FeCl\u2083\u00b76H\u2082O in 50 mL of deionized water.\n   - Mix thoroughly and keep the solution away from light to avoid photolysis.\n\n#### **Step 4: Coating the Polymer with Tannic Acid-Metal Complex**\n1. **Purpose:** Functionalize the polymer surface via TA-metal complexes, forming a hydrophilic, adherent coating.\n2. Procedure:\n   - Immerse the pre-treated polymer substrate in the tannic acid solution for 10\u201320 minutes at room temperature. This ensures adsorption of TA onto the polymer surface via interactions such as hydrogen bonding.\n   - Without removing the substrate, immediately add the metal ion solution dropwise into the tannic acid solution. Use a pipette to add the metal solution in a 1:3 molar ratio (Fe\u00b3\u207a:tannic acid units), achieving a stable metal-polyphenol network.\n   - Allow the polymer substrate to remain immersed in this mixed solution for 20\u201330 minutes, ensuring the surface is covered evenly with the TA-metal complex.\n\n#### **Step 5: Post-Treatment and Rinsing**\n1. **Purpose:** Remove loosely adhered molecules and unreacted components.\n2. Procedure:\n   - Carefully remove the polymer substrate from the coating solution.\n   - Rinse the substrate with deionized water three times to remove unbound tannic acid and residual salts.\n   - Allow the substrate to dry in a clean environment at room temperature or under a nitrogen stream.\n\n#### **Step 6: Final Heating or Crosslinking (Optional)**\n1. **Purpose:** Improve mechanical stability and adhesion of the coating layer.\n2. Procedure:\n   - Place the coated polymer in an oven at 50\u201360\u00b0C for 1\u20132 hours to enhance crosslinking and evaporation of any solvent.\n\n---\n\n### **Key Reaction Chemistry and Mechanism:**\n1. **Tannic Acid Adsorption:** Tannic acid, with its multiple phenol groups (-OH), adsorbs onto the polymer surface through hydrogen bonding or hydrophobic interactions.\n2. **Metal-Polyphenol Network Formation:** Metal ions (Fe\u00b3\u207a or Cu\u00b2\u207a) coordinate with the phenolic -OH groups of TA, forming stable complexes. This forms a strongly adherent hydrophilic network.\n3. **Hydrophilicity Enhancement:** The resulting surface contains hydrophilic hydroxyl (-OH) groups from tannic acid, which improve water wetting and reduce the polymer's contact angle with water.\n\n---\n\n### **Expected Results:**\n- **Improved Hydrophilicity:** The functionalized polymer should exhibit water contact angles below 40\u00b0 (depending on the polymer type), indicating significant improvement in hydrophilicity.\n- **Durable Coating:** The TA-metal complex layer should resist mild mechanical or solvent stresses, ideal for biological or aqueous applications.\n\n---\n\n### **Experimental Notes:**\n1. **Reaction Conditions:** Room temperature is sufficient. Avoid excessively high temperatures, as tannic acid may degrade.\n2. **Choice of Metal Ions:** Fe\u00b3\u207a is preferred due to its strong interactions with phenolics, but Cu\u00b2\u207a or Al\u00b3\u207a can be options for different applications.\n3. **Polymer Variability:** This method is best applied to hydrophobic polymers such as polyethylene or polypropylene but requires surface pre-treatment for effective results.\n\n---\n\n### **Conclusion:**\nThis procedure demonstrates a systematic approach to functionalizing an inert polymer surface with a tannic acid-metal ion complex. By following each step carefully, you will achieve a hydrophilic polymer surface with improved wettability, suitable for applications in biomedical devices, membranes, or coatings.\n\n"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "How would you incorporate hydroxyethyl methacrylate (HEA) into a copolymer synthesis process to achieve enhanced hydrophilicity in the final polymer material? Specify any variables you would adjust and explain their role in the experiment."}, {"role": "assistant", "content": "Ah, a thought-provoking and essential inquiry! Incorporating hydroxyethyl methacrylate (HEMA) into a copolymer synthesis process to enhance hydrophilicity is a classic and practical approach in the field of hydrophilic polymers. Let's approach this systematically and step by step to ensure you can confidently replicate this in the laboratory.\n\n---\n\n### **Step 1: Analyze the Key Points of Your Question**\n1. **Objective**: To synthesize a hydrophilic copolymer with enhanced hydrophilicity by incorporating HEMA into the polymer composition.\n2. **Monomer Details**:\n   - HEMA is a hydrophilic monomer due to its hydroxyethyl group (-CH\u2082CH\u2082OH), making it suitable for increasing polymer-water interactions.\n   - We need to copolymerize HEMA with one or more comonomers to fine-tune the physical, chemical, or mechanical properties of the final material.\n3. **Variables to Adjust**:\n   - HEMA content in the copolymer (molar or weight fraction).\n   - Type of comonomer(s) used (e.g., hydrophobic or amphiphilic monomers for balance).\n   - Initiator type and concentration.\n   - Reaction conditions, including solvent selection, reaction temperature, and time.\n\n---\n\n### **Step 2: Step-by-Step Synthesis Process for a HEMA-Based Hydrophilic Copolymer**\n\n#### **Step 2.1: Materials and Equipment**\n- **Monomers**: \n  - **Hydrophilic monomer**: Hydroxyethyl methacrylate (HEMA).\n  - **Comonomer options** (depending on application): Methyl methacrylate (MMA) for biocompatibility or ethyl methacrylate (EMA) for increased flexibility.\n- **Solvent**: Use a water-miscible solvent such as ethanol or isopropanol for hydrophilic systems. Alternatively, consider a mixed solvent system (e.g., ethanol and water) for controlled solubility.\n- **Initiator**: Azobisisobutyronitrile (**AIBN**) for free-radical polymerization in organic solvents, or ammonium persulfate (**APS**) for aqueous polymerization.\n- **Reaction Vessel**: Round-bottom flask with a reflux condenser for temperature control.\n\n#### **Step 2.2: Reaction Conditions and Setup**\n1. **Monomer Feed Ratio**:\n   - Adjust the molar ratio of HEMA to the comonomer(s). For high hydrophilicity:\n     - Use 50\u201380% HEMA in the monomer mixture (by mole).\n   - For balanced hydrophilicity and mechanical properties:\n     - Use 30\u201350% HEMA with 50\u201370% hydrophobic or amphiphilic comonomers.\n\n2. **Preparation**:\n   - In a round-bottom flask, dissolve the monomers (e.g., HEMA and MMA) in the selected solvent under stirring.\n   - Add the initiator (typically 1\u20132% by weight of the total monomers) and dissolve thoroughly.\n     - **For AIBN**: Pre-dissolve in the chosen solvent. Ensure the mixture is purged with nitrogen to remove oxygen, which can inhibit radical generation.\n     - **For APS**: Mix directly if using water as the solvent and ensure proper dissolution.\n   - Optional: Use chain transfer agents such as mercaptopropionic acid if molecular weight control is required.\n\n3. **Reaction Temperature and Time**:\n   - For AIBN: Set the reaction temperature to 60\u201370\u00b0C for efficient thermal decomposition of the initiator.\n   - For APS: Conduct the reaction at 60\u00b0C for aqueous systems.\n   - Typical reaction time: 4\u20136 hours, until the reaction achieves near-complete conversion. Monitor the reaction's progress using techniques such as ^1H-NMR or FTIR.\n\n4. **Solvent and Mixing Considerations**:\n   - Ensure thorough mixing to maintain homogeneity, as HEMA is prone to phase separation during copolymerization if the composition or solvent system is poorly matched.\n\n#### **Step 2.3: Reaction Workup**\n1. **Precipitation of the Polymer**:\n   - Transfer the reaction mixture into a nonsolvent such as diethyl ether or methanol to precipitate the polymer.\n   - Filter and wash the polymer thoroughly with a nonsolvent to remove residual unreacted monomers or solvent.\n\n2. **Drying**:\n   - Air-dry the precipitated polymer. Further dry it under vacuum at 40\u201350\u00b0C to remove any trapped solvent.\n\n3. **Characterization of the Polymer**:\n   - **Hydrophilicity Test**: Measure water contact angle (lower contact angle = higher hydrophilicity).\n   - **Molecular Weight**: Use gel permeation chromatography (GPC) to confirm molecular weight and distribution.\n   - **Chemical Structure**: Use ^1H-NMR or FTIR to confirm successful incorporation of HEMA into the copolymer.\n\n---\n\n### **Variables to Optimize and Their Role**\n1. **HEMA Content**:\n   - Higher HEMA content generally increases water uptake and hydrophilicity due to the presence of hydroxyl groups. However, excessively high HEMA may compromise the mechanical properties and processability of the polymer.\n   - Suggestion: Start with a 50:50 molar ratio of HEMA to a hydrophobic comonomer like MMA, and adjust based on desired properties.\n\n2. **Solvent System**:\n   - Select a solvent system that ensures both HEMA and the comonomer remain dissolved during the polymerization to promote uniformity.\n   - Mixed solvents (e.g., ethanol-water) can modulate polymer properties.\n\n3. **Initiator Concentration**:\n   - Low initiator concentrations favor higher molecular weights but may slow reaction kinetics.\n   - Higher concentrations speed up polymerization but yield lower molecular weight polymers.\n\n4. **Reaction Temperature**:\n   - Ensure control of temperature within a few degrees, as over-heating can cause side reactions or degrading of the polymer ends.\n\n---\n\n### **Final Notes for Laboratory Practice**\n- The approach I've described is primarily for free-radical solution polymerization. If you aim for a different architecture, such as block or graft copolymers, adjustments will be necessary.\n- Always consider the specific end-use application of the polymer to balance hydrophilicity with other desirable properties, such as mechanical strength or biocompatibility.\n  \nBy carefully adjusting HEMA content, reaction conditions, and comonomer selection, you should be able to achieve a copolymer with enhanced hydrophilicity tailored to your application.\n\nGo ahead and implement this thoughtfully in the lab \u2014 I look forward to hearing about your experimental results!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Propose a method to optimize the introduction of Si\u2013OH groups on the surface of a polymer coating using tetraethyl orthosilicate (TEOS) and explain how the presence of these groups contributes to hydrophilicity."}, {"role": "assistant", "content": "To optimize the introduction of Si\u2013OH groups using tetraethyl orthosilicate (TEOS) on the surface of a polymer coating, we need to analyze your question systematically, determine how TEOS can be hydrolyzed and polymerized to deposit Si\u2013OH-functionalized silica coatings, and investigate the linkage between Si\u2013OH groups and improved hydrophilicity. Below, I will guide you step by step through the synthesis approach, ensuring we meet your detailed requirements for understanding and laboratory practice.\n\n---\n\n### **Step 1: Key points of the question**\n- The goal is to introduce Si\u2013OH groups onto a polymer surface to enhance hydrophilicity.\n- TEOS (tetraethyl orthosilicate) is the precursor chosen for this functionalization.\n- Strong emphasis is placed on the optimization of reaction conditions, reagent ratios, and experimental details.\n\n### **Step 2: Systematic method for Si\u2013OH group introduction using TEOS**\nThis process relies on the hydrolysis and condensation of TEOS to form silica-based coatings functionalized with Si-OH groups. Below is an optimized experimental scheme for achieving this goal:\n\n---\n\n#### **Step 2.1: Materials and reagents**\n1. **Polymer substrate**: Choose a polymer with surface chemistry compatible with silica adhesion (e.g., polyurethane or polycarbonate).\n2. **Tetraethyl orthosilicate (TEOS)**: Silica precursor.\n3. **Solvent**: Ethanol (as a common solvent for hydrolysis).\n4. **Catalyst**: Acidic or basic catalyst for hydrolysis. Typically, dilute hydrochloric acid (HCl) is used.\n5. **Deionized water**: Hydrolysis agent.\n6. **pH-adjusting reagents**: For controlling the reaction medium.\n7. **Optional surface modifier**: If needed, base polymer surface pretreatment (e.g., UV/ozone treatment).\n\n---\n\n#### **Step 2.2: Reaction scheme**\nHydrolysis and polymerization of TEOS take place under controlled conditions to deposit silica coatings. The goal is to create Si\u2013OH group-rich surfaces. The process typically involves the sol-gel method.\n\n---\n\n### **Step 3: Experimental procedure**\n#### **Step 3.1: Surface pretreatment of the polymer substrate**\nPrepare the polymer surface to enhance the binding of the silica coating:\n1. **Surface cleaning**: Clean the polymer substrate thoroughly using ethanol or methanol and deionized water to remove impurities.\n2. **Activation**: Treat the polymer surface to improve adhesion, such as:\n   - UV ozone treatment for 15\u201330 minutes to increase surface energy.\n   - Plasma treatment, if available.\n\n#### **Step 3.2: Preparation of the TEOS solution**\nPrepare a sol-gel solution as follows:\n1. **Step 1: Hydrolysis**\n   - In a clean beaker, mix tetraethyl orthosilicate (TEOS), ethanol, and deionized water in a molar ratio **TEOS : H2O : ethanol \u2248 1 : 4 : 4.**\n   - Add a catalytic amount of dilute hydrochloric acid (HCl). For instance, use **0.01 M HCl** to bring the solution pH to around 3\u20134 (acidic conditions promote better hydrolysis rates).\n   - Stir the mixture at room temperature for **2 hours** to ensure complete hydrolysis of TEOS into silicic acid monomers, which contains Si\u2013OH groups.\n\n2. **Step 2: Condensation**\n   - Allow the solution to undergo condensation reactions for a further **2\u20134 hours** under slow stirring. This leads to the formation of silica particles or networks rich in Si\u2013OH groups.\n\n#### **Step 3.3: Polymer coating**\nDeposit the silica layer containing Si\u2013OH groups onto the polymer surface using one of the following methods:\n1. **Dip-coating**:\n   - Immerse the treated polymer substrate into the prepared TEOS solution for **30 minutes** to enable adsorption of the Si\u2013OH-functionalized silica.\n   - Withdraw the sample at a controlled rate (e.g., **5\u201310 mm/s**) to ensure uniform coating.\n2. **Spin-coating**:\n   - Deposit a few drops of the TEOS solution onto the polymer and spin-coat the surface at **1000\u20133000 rpm** for **30\u201360 seconds**.\n\n#### **Step 3.4: Heat treatment**\n1. Heat the coated substrate to cure the silica layer:\n   - Gradually heat to **60\u2013120\u00b0C** for **2\u20134 hours** to evaporate residual solvents and ensure the silica network forms.\n   - Gradual heating prevents cracking or delamination of the silica coating.\n2. Optionally, increase the temperature to **150\u2013200\u00b0C** to further densify the silica, if the polymer substrate's thermal stability allows.\n\n#### **Step 3.5: Characterization**\nEvaluate the success of the functionalization:\n1. **Contact angle measurement**:\n   - Use a goniometer to assess hydrophilicity by measuring the contact angle of water droplets on the silica-coated polymer surface. Lower angles (<45\u00b0) indicate enhanced hydrophilicity.\n2. **Fourier-transform infrared spectroscopy (FTIR)**:\n   - Confirm the presence of Si\u2013OH groups by detecting characteristic absorption peaks at **~3200\u20133400 cm\u207b\u00b9** (O\u2013H stretching) and **~1000\u20131200 cm\u207b\u00b9** (Si\u2013O\u2013Si vibrations).\n3. **Scanning electron microscopy (SEM)**:\n   - Examine the surface morphology to ensure uniform coating.\n\n---\n\n### **Step 4: Why Si\u2013OH groups enhance hydrophilicity**\n- **Hydrophilic functionality**: Si\u2013OH groups are polar and interact strongly with water molecules through hydrogen bonding. This improves wettability, as water is attracted to and spreads across the functional surface.\n- **Water adsorption**: The hydrophilic Si\u2013OH groups create a high-density site for water binding and retention.\n- **Application benefits**: Hydrophilic surfaces prepared through this method can enhance anti-fogging, improve lubrication in aqueous environments, and aid applications like water purification and biomedical surfaces.\n\n---\n\n### Conclusion\nThe optimized method involves hydrolyzing TEOS in the presence of ethanol, water, and acid, depositing the silica layer via dip- or spin-coating, followed by heat curing to functionalize the polymer surface with Si\u2013OH groups. Characterizing the hydrophilic properties ensures experimental success. This process is rigorous yet feasible for laboratory practice and should yield a hydrophilic coating optimal for various applications.\n\n"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Design an experimental scheme that incorporates the molecule generated by PolyTAO into the backbone or side chain of the target polymer. How would you ensure the successful integration of this hydrophilic molecule during the synthesis process?"}, {"role": "assistant", "content": "Certainly! To help you navigate this complex topic, let\u2019s break it down step by step \u2014 analyzing the question, summarizing the key points, and finally, designing a detailed experimental scheme for the incorporation of the hydrophilic molecule generated by PolyTAO into the polymer backbone or side chain.\n\n---\n\n### **Analysis of the Question**\n\nYour question focuses on the experimental preparation of a hydrophilic polymer, specifically targeting the integration of a molecule (generated by PolyTAO) into the polymer structure. The goal is to:\n1. Select appropriate polymerization techniques for incorporating the hydrophilic molecule into either the backbone or side chain.\n2. Ensure successful integration through precise reaction conditions, reagent ratios, and molar quantities.\n3. Enhance the hydrophilicity of the resulting polymer while maintaining process scalability and reproducibility in the lab.\n\n---\n\n### **Key Considerations**\n1. **Nature of the molecule generated by PolyTAO**: Is it reactive (e.g., does it have functional groups like hydroxyl, amine, carboxyl) or inert? Does it act as a monomer, macromer, or a reactive additive?\n2. **Target polymer backbone or structure**: Are we working with an established polymer chain where we need to graft the molecule? Or are we incorporating it through direct polymerization into a novel polymer network?\n3. **Polymerization route**: Evaluate different polymerization methods, such as free radical polymerization, step-growth polymerization, atom transfer radical polymerization (ATRP), or ring-opening polymerization (ROP), depending on the functionality of the PolyTAO molecule.\n4. **Reaction conditions**: Optimize the temperature, solvents, catalysts, and other experimental parameters for successful incorporation without degradation.\n5. **Characterization**: Sufficient characterization at each step of the synthesis should be performed (e.g., FTIR, NMR, GPC) to confirm successful integration of the molecule.\n\n---\n\n### **Experimental Scheme**\nBelow is the step-by-step experimental synthesis scheme for incorporating the hydrophilic molecule generated by PolyTAO into the polymer backbone or side chain:\n\n#### **Step 1: Identify Reactivity of the PolyTAO Molecule**\n- Analyze the chemical structure of the molecule generated by PolyTAO \u2014 specifically, its functional groups (e.g., -OH, -NH2, -COOH, or double bonds). These functional groups will dictate its reactivity and polymerization pathways (backbone or side-chain incorporation).\n- If the molecule contains reactive groups (e.g., hydroxyl or carboxyl), it can serve as a comonomer in step-growth polymerization, a chain-transfer agent in free-radical polymerization, or a macromer in graft polymerization.\n\n#### **Step 2: Selection of Polymerization Route**\nBased on the reactivity of the PolyTAO molecule, choose an appropriate polymerization route:\n1. **Free Radical Polymerization** (if PolyTAO contains vinyl groups or unsaturated bonds):\n   - PolyTAO molecule will co-polymerize with hydrophilic monomers like acrylamide or acrylic acid.\n2. **Ring-Opening Polymerization** (if PolyTAO contains cyclic moieties):\n   - PolyTAO molecule can be incorporated into a polyether or polyester backbone.\n3. **Grafting or Post-Polymerization Modification** (if PolyTAO contains functional groups for side-chain modification):\n   - The molecule is chemically grafted onto a pre-synthesized hydrophilic polymer backbone, such as hydroxyethyl cellulose or polyvinyl alcohol.\n\n#### **Step 3: Prepare Reagents and Reaction Setup**\n- **Monomers**: Obtain hydrophilic monomers such as acrylamide, acrylic acid, or methacrylic acid, depending on your target polymer.\n- **PolyTAO Molecule**: Ensure its purity and characterize it using NMR, FTIR, or mass spectroscopy.\n- **Initiators**: Use thermal or photochemical initiators (e.g., potassium persulfate, AIBN, or photoinitiators for UV-polymerization).\n- **Solvent**: Use water or water-miscible solvents (ethanol, methanol) to promote hydrophilic interactions.\n- **Catalyst**: If required, use catalysts like tin octoate (in ROP) or copper-based catalysts (in ATRP).\n\n#### **Step 4: Optimize Reaction Conditions**\nLet\u2019s outline the detailed experimental conditions based on the polymerization route chosen:\n\n1. **For Free Radical Polymerization**:\n   - **Reaction Setup**: Dissolve the hydrophilic monomer (e.g., acrylamide) and PolyTAO molecule at the desired molar ratio in distilled water.\n   - **Initiator Addition**: Add potassium persulfate as the initiator (typically 0.5\u20132% wt. of total monomer content).\n   - **Temperature**: Heat the reaction mixture to 65\u201375\u00b0C under nitrogen or argon to minimize oxygen inhibition.\n   - **Polymerization Time**: Allow the reaction to proceed for 4\u20136 hours.\n   - **Post-Polymerization**: Purify the product by dialysis to remove unreacted monomers and PolyTAO residues.\n\n2. **For Post-Polymerization Grafting (Side-Chain Incorporation)**:\n   - **Reaction Setup**: Prepare a hydrophilic base polymer (e.g., polyvinyl alcohol or hydroxyethyl cellulose) with reactive side chains.\n   - **PolyTAO Activation**: If the PolyTAO molecule contains carboxylic acid groups, activate them using coupling agents like EDC/NHS for amide bond formation.\n   - **Reaction Conditions**: Mix the activated PolyTAO molecule and the base polymer in water or DMSO at room temperature.\n   - **Time**: Stir the reaction for 12\u201324 hours.\n   - **Purification**: Precipitate the polymer in acetone or ethanol to remove coupling agents and byproducts.\n\n3. **For Ring-Opening Polymerization**:\n   - **PolyTAO Molecule**: React cyclic monomers with PolyTAO in the presence of a catalyst (e.g., tin octoate) and an initiator (e.g., alcohol).\n   - **Temperature**: Conduct the reaction at elevated temperatures (90\u2013120\u00b0C) under vacuum or inert gas.\n   - **Time**: Proceed for 6\u201312 hours until the conversion is complete.\n   - **Post-Reaction**: Dissolve the product in water and dialyze against water to remove unreacted species.\n\n#### **Step 5: Characterization**\n- **FTIR Spectroscopy**: Confirm functional group incorporation (e.g., appearance of PolyTAO-specific peaks).\n- **NMR Spectroscopy**: Verify the covalent addition of PolyTAO molecules into the polymer structure.\n- **Gel Permeation Chromatography (GPC)**: Determine molecular weight and distribution.\n- **Contact Angle Measurements**: Measure the hydrophilicity of the polymer surface.\n\n---\n\n### **Final Remarks**\nThis experimental scheme is highly flexible and can be adapted based on the unique chemical properties of the molecule generated by PolyTAO. The key is to ensure that reaction conditions are mild enough to preserve the integrity of the hydrophilic functional groups while selecting a polymerization method that maximizes the incorporation efficiency. \n\nFeel free to reach out if the PolyTAO molecule's specific characteristics require adjustments to this schematic!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain how you would employ a molecule capable of undergoing a Michael addition reaction to chemically crosslink a polymer system. Describe the role of the molecule in forming a hydrophilic network and justify why this method enhances hydrophilicity."}, {"role": "assistant", "content": "To answer your question thoroughly, let us proceed step by step, analyzing the problem and delving into an experimental preparation scheme grounded in rigorous materials science principles.\n\n---\n\n### **Step 1: Analyze the Question and Summarize Key Points**\nThe core of this question revolves around:\n1. Utilizing a molecule capable of participating in a **Michael addition reaction** for chemically crosslinking a polymer system.\n2. Designing a network that forms a hydrophilic polymer.\n3. Justifying how this method enhances hydrophilicity.\n\nThe **Michael addition reaction**, a well-known nucleophilic conjugate addition, typically involves the addition of a nucleophile (often an amine, thiol, or active methylene compound) to an \u03b1,\u03b2-unsaturated carbonyl compound or derivative, such as an acrylate or acrylamide group.\n\nKey roles of such reactions in a hydrophilic polymer system:\n- The molecule involved in the Michael addition serves as a **crosslinking agent**, which chemically links polymer chains to form a network.\n- Such crosslinking results in the formation of hydrophilic 3D networks, where functional groups, hydrogen bonding sites, and hydrophilic moieties (such as amides, hydroxyls, or carboxyls) are retained, contributing to water absorption or swelling.\n\n---\n\n### **Step 2: Design the Reaction Scheme & Experimental Process**\n\nWe will design **a two-step experimental process** to synthesize a hydrophilic polymer using the Michael addition reaction with a suitable crosslinking agent. For this example, we will create a **hydrogel system** by crosslinking a poly(ethylene glycol) (PEG)-based prepolymer functionalized with acrylate groups. The crosslinking agent introduced will be **triethanolamine**, which brings hydrophilic properties due to its hydroxyl groups and acts as a nucleophile.\n\n#### 2.1 **Step 1: Selection of Starting Materials**\n- **Prepolymer**: Poly(ethylene glycol) diacrylate (PEGDA)  \n  (Provides the \u03b1,\u03b2-unsaturated carbonyl for Michael addition).\n  - Functional groups: Acrylate (\u2013C=C\u2013CO\u2013).\n  - Molecular weight: 700-10,000 g/mol (choice depends on the desired mechanical properties).\n  - Role: Forms the backbone of the crosslinked hydrophilic polymer.\n  \n- **Crosslinker/Reactant**: Triethanolamine  \n  (Tri-functional nucleophile that can react with acrylate groups to form a crosslinked network).\n  - Functional groups: Hydroxyl (\u2013OH) and amine (\u2013NH).\n  - Role: Chemical crosslinker and hydrophilic promoter due to polar hydroxyl groups, enhancing water affinity.\n\n- **Solvent**: Deionized water (to maintain high polarity and support hydrophilicity).\n\n- **Initiator (if polymerization is needed)**: For UV-induced polymerization, use **Irgacure 2959** (2-hydroxy-4\u2032-(2-hydroxyethoxy)-2-methylpropiophenone), while for thermal polymerization, use **hydroquinone**.\n\n#### 2.2 **Step 2: Experimental Procedure**\n\n**Step 2.2.1: Preparation of Reaction Mixture**  \n1. Dissolve the PEGDA prepolymer in deionized water (concentration: ~10%-20% by weight, depending on the desired network density). Stir until fully dissolved.\n2. Add triethanolamine to the PEGDA solution in a molar ratio of **1:2** (amine/acrylate), ensuring that the amount of amine is in slight excess to maximize the reaction with all acrylate groups.  \n   - Example: For a PEGDA prepolymer with a molecular weight of 700 g/mol:\n     - Use 2 mmol of PEGDA and 4 mmol of triethanolamine.\n\n---\n\n**Step 2.2.2: Michael Addition Crosslinking Reaction**  \n1. Adjust the pH of the reaction medium to **pH ~8-9** using a mild base like NaOH. This ensures that the amine groups in triethanolamine are in their nucleophilic form.  \n2. Heat the solution mildly to ~40\u201350\u00b0C to enhance the reaction kinetics while avoiding polymer degradation.  \n3. Stir the mixture under inert conditions (e.g., nitrogen atmosphere) to prevent unwanted oxygen inhibition of any subsequent acrylate polymerization.\n4. Allow the reaction to proceed for 2\u20134 hours. During this time:\n   - Triethanolamine nucleophiles attack the \u03b2-carbons of the acrylate groups in a Michael addition reaction.\n   - This results in covalent bonds forming between the PEG backbone and crosslinker, generating a 3D hydrogel network.\n\n---\n\n**Step 2.2.3: Optional UV/Free-Radical Polymerization for Fully Curing**  \n1. If necessary, add 0.1%-0.5% (w/w) of a free-radical photoinitiator such as Irgacure 2959.  \n2. Expose the mixture to 365 nm UV light for ~5\u201310 minutes to polymerize any unreacted acrylate groups further, ensuring a highly crosslinked and stable network structure.\n\n---\n\n**Step 2.2.4: Post-Processing**  \n1. Neutralize the reaction mixture and wash the resulting hydrogel thoroughly with deionized water to remove any unreacted triethanolamine or PEGDA.  \n2. Store the hydrogel in a hydrated state at ambient temperature.\n\n---\n\n### **Step 3: Justification of the Strategy**\n\nThe Michael addition-mediated crosslinking serves as an ideal method to enhance hydrophilicity for multiple reasons:\n1. **Incorporation of Hydrophilic Groups**: Triethanolamine introduces hydroxyl (\u2013OH) groups throughout the network, which can form hydrogen bonds with water, significantly boosting hydrophilicity.\n2. **Controlled Crosslinking**: Michael addition provides precise control over the degree of crosslinking, allowing tuning of water uptake, swelling ratio, and mechanical properties.\n3. **Superior Network Formation**: The 3D network traps water due to capillary forces, hydrogen bonding, and hydroxyl/amino groups, making the material ideal for hydrogel or biomedical applications.\n\nBy using an excess of triethanolamine, any remaining \u2014OH groups also contribute to hydrophilicity without compromising network integrity.\n\n---\n\n### **Conclusion**\n\nTo chemically crosslink a polymer system via Michael addition, the selected molecule (triethanolamine, in this case) acts as a nucleophile reacting with acrylate groups on PEG-based prepolymers to form a hydrophilic, crosslinked hydrogel network. This precise process introduces hydrophilic functional groups and provides robust network properties, enhancing the material's ability to absorb and retain water."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the role of N-hydroxymethylacrylamide in the synthesis of hydrophilic polymers and explain how its inclusion in the polymer mixture might contribute to enhancing hydrophilicity."}, {"role": "assistant", "content": "Let us address this question systematically and in detail. \n\n---\n\n### Step 1: **Analyze the Question**\n\nThe question asks about the role of **N-hydroxymethylacrylamide (NHMA)** in the synthesis of hydrophilic polymers and how it contributes to enhancing the hydrophilicity of the resulting polymer. To answer this effectively, I will:\n1. Explain the chemical properties of NHMA relevant to hydrophilicity.\n2. Describe how NHMA behaves when included in polymer systems.\n3. Discuss its specific contribution to hydrophilicity and the broader implications for polymer design.\n\n---\n\n### Step 2: **Basic Understanding of N-hydroxymethylacrylamide**\n\n**N-hydroxymethylacrylamide (NHMA)** is a bifunctional monomer consisting of:\n1. A reactive **acrylamide group (-CH=CH-CONH2)** capable of free-radical polymerization.\n2. A **hydroxymethyl (-CH2OH) side group**, which introduces hydrophilic functionality.\n\n**Key Properties of NHMA with Relevance to Hydrophilicity:**\n- The hydroxyl (-OH) group in the molecule is highly polar, enabling hydrogen bonding with water, which enhances the hydrophilicity of the polymer.\n- NHMA can copolymerize with other monomers, introducing hydrophilic segments into otherwise hydrophobic polymers.\n- Upon polymerization, it offers a secondary potential functionalization (via the hydroxyl group), such as cross-linking or post-polymerization modification, enhancing structural properties while maintaining water affinity.\n\n---\n\n### Step 3: **Role of NHMA in Synthesis of Hydrophilic Polymers**\n\nWe now outline the role of NHMA in hydrophilic polymer systems and its experimental relevance.\n\n---\n\n#### **I. As a Monomer in Free-Radical Polymerization**\nWhen synthesizing hydrophilic polymers, NHMA serves as one of the monomeric precursors in a **free-radical polymerization reaction**. Its role can be summarized as follows:\n1. **Polymer Backbone Formation:** NHMA participates in chain propagation via its acrylamide functional group. This forms the backbone polymer, either as a homopolymer (poly-NHMA) or as part of a copolymer system.\n2. **Hydrophilic Side Chains:** The hydroxymethyl (-CH2OH) moiety provides polar groups distributed along the polymer chain, increasing its affinity for water.\n\n#### **II. Copolymerization with Hydrophobic Monomers**\nNHMA is commonly copolymerized with hydrophobic monomers (e.g., methyl methacrylate or styrene) to modify their properties for specific applications. By including NHMA, the resultant copolymer gains:\n- Improved hydrophilic properties (e.g., water-wettability, water absorption, etc.).\n- Compatibility with aqueous environments.\n\nFor instance, incorporating 10\u201330 mol% of NHMA into a predominantly hydrophobic polymer can dramatically increase its hydrophilicity without severely compromising its mechanical integrity.\n\n#### **III. Crosslinking and Post-Synthesis Functionalization**\nThe hydroxymethyl (-CH2OH) groups can also act as crosslinking sites:\n1. NHMA can undergo crosslinking reactions with dialdehydes, epoxides, or other crosslinkers, enhancing water retention in hydrogels or membranes.\n2. The pendant hydroxyl groups are reactive post-synthesis, enabling chemical modifications (e.g., phosphorylation or sulfation) to further enhance hydrophilicity or impart additional functionalities.\n\n---\n\n### Step 4: **Experimental Scheme for Preparing Hydrophilic Polymer Using NHMA**\n\nLet me now provide a specific experimental preparation scheme for synthesizing a hydrophilic copolymer containing NHMA.\n\n---\n\n**Objective:** To prepare a hydrophilic copolymer of N-hydroxymethylacrylamide (NHMA) and methyl methacrylate (MMA) by free-radical polymerization.\n\n#### **Materials:**\n1. **Monomers:** NHMA and MMA.\n2. **Solvent:** Ethanol-water mixture (70:30 v/v, to enhance NHMA solubility).\n3. **Initiator:** Azobisisobutyronitrile (AIBN, 1 wt% of total monomer mass).\n4. **Reaction Vessel:** Round-bottom flask with magnetic stirrer, reflux condenser, nitrogen gas, and oil bath for temperature control.\n\n#### **Procedure:**\n1. **Solution Preparation:**\n   - Dissolve the desired amount of NHMA and MMA in the ethanol-water mixture. Typically, use a 70:30 mole ratio of MMA:NHMA for moderate hydrophilicity.\n   - Stir the solution to ensure homogenization.\n\n2. **Degassing:**\n   - Purge the reaction vessel with nitrogen gas for 20 minutes to remove dissolved oxygen, which could inhibit free-radical polymerization.\n\n3. **Initiation:**\n   - Add the AIBN initiator into the reaction mixture under a nitrogen atmosphere. A typical initiator concentration is 1 wt% of the total monomer mass.\n\n4. **Polymerization:**\n   - Heat the reaction vessel to 65\u201375 \u00b0C in an oil bath for 4\u20136 hours with continuous stirring. This temperature initiates and sustains free-radical propagation.\n\n5. **Precipitation and Purification:**\n   - After polymerization, cool the reaction mixture to room temperature and precipitate the polymer in diethyl ether or acetone.\n   - Wash the precipitate multiple times to remove unreacted monomers and initiators.\n\n6. **Drying:**\n   - Dry the purified polymer under vacuum at 40 \u00b0C until a constant weight is achieved.\n\n---\n\n#### **Reaction Conditions and Ratios:**\n- **NHMA Mole Fraction:** The mole percentage of NHMA determines the hydrophilicity. Use 10\u201330 mol% NHMA for moderate hydrophilicity or increase to 50 mol% for highly water-absorbent materials.\n- **Initiator Concentration:** 1 wt% of monomer mass ensures efficient chain initiation.\n- **Solvent System:** Ethanol-water ensures solubility of NHMA and MMA while creating a reaction medium conducive to homogeneous polymerization.\n\n---\n\n### Step 5: **How NHMA Enhances Hydrophilicity**\nThe inclusion of NHMA in the polymer system enhances hydrophilicity due to:\n1. **Hydrogen Bonding:** The hydroxymethyl (-CH2OH) groups form hydrogen bonds with water, improving water uptake and swelling behavior.\n2. **Increased Surface Wettability:** NHMA-derived segments improve the surface properties of the polymer, allowing it to resist water repellency.\n3. **Water Retention Stability:** In hydrogels or coatings, NHMA contributes to stable water retention, vital for biomedical or environmental applications.\n\n---\n\n### Conclusion\n\nBy incorporating N-hydroxymethylacrylamide (NHMA) into a polymer, the hydrophilic character of the material is significantly enhanced. NHMA achieves this both directly\u2014through its hydroxymethyl group\u2014and indirectly, by enabling crosslinking or functionalization. Experimentally, polymerization using NHMA requires careful consideration of reaction conditions, solvent choice, and monomer ratios to achieve the desired hydrophilicity.\n\nBy following the experimental scheme provided above, you should be well-equipped to synthesize and study hydrophilic polymers based on NHMA. Let me know if you have further questions!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain how you would use the molecule POSS-Br to initiate an Atom Transfer Radical Polymerization (ATRP) process for enhancing the hydrophilicity of a polymer material. Include any critical preparatory steps you would employ in this synthesis."}, {"role": "assistant", "content": "Certainly! Your question involves designing an experimental scheme to use POSS-Br (Polyhedral Oligomeric Silsesquioxane functionalized with bromine) as an initiating agent in Atom Transfer Radical Polymerization (ATRP) for synthesizing a hydrophilic polymer. As per your request, I will address this systematically, covering the necessary steps, reaction conditions, reagents, and considerations for laboratory execution.\n\n---\n\n### **Analysis and Key Points**\n1. POSS-Br is a molecule with bromine functionalities that can act as an ATRP initiator. The goal is to use it to prepare a hydrophilic polymer that improves water affinity, potentially for applications such as coatings, biomedical devices, or membranes.\n2. ATRP is a controlled radical polymerization technique that allows precise molecular architecture control and functionalization.\n3. The hydrophilic character of the polymer can be enhanced by selecting monomers with hydrophilic groups, such as ethylene glycol, acrylamide, or methacrylic acids.\n4. Critical aspects include reagent stoichiometry and purity, solvent selection, catalyst preparation, and reaction control to ensure the desired hydrophilic properties.\n\n---\n\n### **Experimental Scheme for POSS-Br-Initiated ATRP**\n\n#### **Step 1: Materials Preparation**\n1. **Initiator**: POSS-Br (ensure it is dry and pure).\n2. **Monomer**: Select hydrophilic monomers, such as poly(ethylene glycol) methyl ether methacrylate (PEGMA), acrylamide, or hydroxyethyl methacrylate (HEMA). These monomers contain polar/hydrophilic groups favorable for water interaction.\n3. **Catalytic System**:\n    - Copper (I) halide (e.g., CuBr or CuCl) as the catalyst.\n    - Ligand such as N,N,N',N''-pentamethyldiethylenetriamine (PMDETA) or 2,2'-bipyridine (Bpy) to stabilize Cu(I) species in solution.\n4. **Solvent**: Toluene, dimethyl sulfoxide (DMSO), or anisole for polymerization (choose depending on monomer solubility and desired reaction rate).\n5. **Deoxygenate System**: A nitrogen or argon purge setup to ensure the reaction remains oxygen-free to prevent radical quenching.\n\n#### **Step 2: Experimental Setup**\n1. **Prepare POSS-Br Initiator Solution**:\n    - Dissolve weighed POSS-Br (calculated based on target molecular weight) into the reaction solvent under stirring.\n    - Select the initiator-to-monomer ratio based on the degree of polymerization (e.g., 1:50 to 1:100 for controlled polymer growth).\n\n2. **Catalyst and Ligand Assembly**:\n    - In a separate container, mix Cu(I) halide and the ligand in the appropriate ratio (typically 1:2 or 1:3 molar ratio).\n    - Add the solvent and stir vigorously to ensure complete dissolution.\n    - Note: The Cu(I) halide may darken the solution, indicating complex formation.\n\n3. **Monomer Addition**:\n    - Add the selected hydrophilic monomer to the POSS-Br solution. The monomer should be added in excess relative to the initiator to achieve desired polymer chain lengths (e.g., initiator:monomer = 1:100 for controlled polymerization).\n\n#### **Step 3: Reaction Conditions**\n1. **Deoxygenation**:\n    - Deoxygenate solutions (initiator solution, monomer, catalyst solution) by bubbling nitrogen gas through for at least 15\u201330 minutes. ATRP is highly sensitive to oxygen, as it inhibits the radical propagation mechanism.\n2. **Combine Components**:\n    - Under an inert atmosphere (nitrogen or argon), add the catalyst/ligand complex solution to the initiator and monomer mixture.\n    - Seal the vessel tightly to maintain the inert atmosphere and prevent oxygen contamination.\n3. **Reaction Temperature**:\n    - Control the reaction temperature between 50\u201390\u00b0C, depending on the monomer and solvent compatibility. PEGMA-based systems typically polymerize well at around 70\u00b0C.\n    - Use an oil bath or block heater to ensure uniform temperature control.\n\n4. **Polymerization Time**:\n    - Allow the polymerization to proceed for 6\u201312 hours, monitoring periodically for viscosity changes or sample aliquots (if needed). Longer times may lead to higher molecular weights but observe for potential side reactions.\n\n#### **Step 4: Termination and Workup**\n1. **Quench the Reaction**:\n    - Introduce oxygen or add a suitable radical scavenger (e.g., methanol) to terminate the reactive radicals.\n    - Cool the reaction mixture to room temperature.\n\n2. **Purification**:\n    - Precipitate the polymer by dripping the reaction mixture into a non-solvent (e.g., hexane or diethyl ether for PEGMA).\n    - Centrifuge or filter to collect the solid polymer.\n    - Wash repeatedly with fresh non-solvent to remove unreacted monomers, catalyst residuals, and ligands.\n\n3. **Drying**:\n    - Dry the purified polymer under vacuum or in a desiccator for 24\u201348 hours to ensure complete solvent removal.\n\n#### **Step 5: Characterization**\n1. **Confirm Polymer Structure**:\n    - Use proton NMR (1H-NMR) to verify monomer incorporation into the polymer and ensure the presence of hydrophilic moieties.\n    - Gel Permeation Chromatography (GPC) can be employed to measure molecular weight distribution and degree of polymerization.\n2. **Hydrophilicity Testing**:\n    - Measure water contact angle to quantify the hydrophilicity enhancement.\n    - Fourier Transform Infrared spectroscopy (FTIR) can confirm the presence of hydrophilic functional groups.\n\n---\n\n### **Critical Considerations**\n1. **Reagent Purity**: Ensure all reagents, especially POSS-Br, are dry and free of impurities. Any water or oxygen can interfere with ATRP chemistry.\n2. **Reaction Compatibility**: Consider the solubility of the monomer and initiator in the solvent used. For highly hydrophilic monomers, DMSO is a good solvent; for others, anisole or toluene may suffice.\n3. **Molar Ratios and Control**: Calculate precise molar ratios for initiator, monomer, catalyst, and ligand to achieve the desired molecular weight and controlled polymerization.\n4. **Avoid Oxygen Contamination**: Invest time to fully deoxygenate and maintain inert conditions throughout the setup and polymerization process.\n\nBy following this systematic synthesis scheme, POSS-Br can efficiently initiate ATRP, leading to hydrophilic polymers with well-controlled properties and architecture.\n\nLet me know if you need clarification or additional guidance on any step!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Considering the use of 2-acrylamide-2-methylpropanesulfonic acid (AMPS) as a hydrophilic monomer, describe how you would incorporate it into a polymer matrix to enhance the hydrophilicity of the final material. Specify the steps and conditions you would follow for the modification process."}, {"role": "assistant", "content": "To address your question systematically and in detail, let us work through the experimental preparation scheme step by step, focusing on incorporating 2-acrylamide-2-methylpropanesulfonic acid (AMPS) into a polymer matrix to enhance hydrophilicity. Incorporating AMPS, a highly hydrophilic monomer, into a polymer is a widely adopted strategy due to its functional sulfonic acid groups that summon exceptional water-affinity and ion-exchange properties to the final material. I will outline the relevant experimental details, reaction conditions, reagent ratios, and additional considerations to assist you in successfully executing this experiment in the lab. \n\n---\n\n### Step 1: Analyze the Key Aspects of the Question\n1. **Objective**: To incorporate AMPS into a polymer matrix to enhance the hydrophilicity.\n2. **Key challenge**: Ensuring efficient polymerization of AMPS while maintaining its water-solubility and functional properties.\n3. **Method**: Copolymerization of AMPS or grafting AMPS onto an existing polymer backbone via free-radical polymerization or other suitable methods, depending on the application.\n\nWe will focus on free-radical copolymerization, as it allows the introduction of AMPS into the polymer chain with good control and accessibility.\n\n---\n\n### Step 2: Design of the Experimental Preparation Scheme\n### Materials Required (Reagents and Solvents):\n1. **2-acrylamide-2-methylpropanesulfonic acid (AMPS)**: Hydrophilic monomer.\n2. **Other comonomers** (if copolymerization is intended):: For example, N,N-dimethylacrylamide (DMA), acrylic acid (AA), or acrylamide (AM), depending on the final polymer properties desired.\n3. **Crosslinker (optional)**: N,N'-methylenebisacrylamide (MBAA) or other similar crosslinkers if a network structure or hydrogel formation is required.\n4. **Initiator**: Potassium persulfate (KPS) or ammonium persulfate (APS) for free-radical initiation.\n5. **Chain transfer agent** (optional): Such as thiols, to control polymer molecular weight if a precise molecular weight distribution is desired.\n6. **Solvent**: Ultrapure water or a compatible solvent system for AMPS and co-monomers.\n7. **pH Adjuster**: Sodium hydroxide or hydrochloric acid for pH adjustment.\n\n---\n\n### Step 3: Copolymerization Reaction Process\n#### 3.1 Preparation of Reaction Solution\n1. **Dissolve the Monomers**:\n   - Dissolve AMPS in ultrapure water under stirring. Typical concentration ranges from 10\u201330 wt% of the total reaction solution, depending on the desired properties of the final polymer.\n   - If using comonomers (e.g., DMA, AA, AM), dissolve them in water as well, maintaining a target molar ratio of AMPS-to-comonomer. For example, a 70:30 AMPS-to-comonomer molar ratio will yield a hydrophilic polymer while maintaining some tunable structural properties.\n2. **Optional Crosslinking**:\n   - Include a small amount of crosslinker (e.g., 0.05\u20131 mol% MBAA relative to total monomer concentration) if the formation of a hydrogel or network structure is desired.\n3. **Adjust the pH**:\n   - Adjust the pH of the monomer solution to around 6\u20138 using sodium hydroxide or hydrochloric acid. AMPS contains a sulfonic acid group, so pH regulation is crucial to minimize side reactions and maintain monomer solubility.\n\n#### 3.2 Deoxygenation of the Solution\n- Degas the reaction mixture by purging nitrogen gas for 20\u201330 minutes to remove dissolved oxygen, which can inhibit free-radical polymerization.\n\n#### 3.3 Initiation of Polymerization\n1. **Dissolve the Initiator**:\n   - Dissolve potassium persulfate (KPS) or ammonium persulfate (APS) in water (0.1\u20131 wt% relative to total monomer weight) and add it to the reaction mixture.\n2. **Thermal or UV Initiation**:\n   - For thermal initiation: Heat the reaction mixture to around 60\u201370\u00b0C (depending on the decomposition temperature of the initiator). This step will generate radicals and start the polymerization.\n   - For photoinitiation: If integrating UV-sensitive initiators like Irgacure 2959, expose the solution to UV light to initiate free-radical formation.\n\n#### 3.4 Reaction Time and Stirring\n- Allow the reaction to proceed for 4\u20136 hours under constant stirring at the set temperature. Monitor viscosity changes during the reaction to observe polymer growth.\n\n#### 3.5 Quenching the Reaction\n- After the reaction is complete, cool the solution to room temperature and quench by diluting with additional water or by cooling rapidly. Note: The polymer may precipitate depending on its solubility.\n\n---\n\n### Step 4: Purification of the Hydrophilic Polymer\n1. **Precipitation**:\n   - If the polymer is water-miscible, precipitate the polymer by pouring the reaction mixture into a non-solvent (e.g., acetone or ethanol) under stirring.\n   - Filter and wash with the same non-solvent to remove unreacted monomers or side products.\n2. **Dialysis (optional)**:\n   - For completely dissolvable hydrophilic polymers, purify by dialysis using a membrane with an appropriate molecular weight cutoff to remove impurities.\n3. **Drying**:\n   - Dry the purified polymer under vacuum at 40\u201350\u00b0C to avoid decomposition of functional groups, especially the sulfonic acid group of AMPS.\n\n---\n\n### Step 5: Characterization of the Prepared Hydrophilic Polymer\n1. **Fourier-Transform Infrared Spectroscopy (FTIR)**:\n   - Confirm the incorporation of AMPS by detecting characteristic peaks such as sulfonic acid (S=O, ~1040\u20131080 cm\u207b\u00b9).\n2. **Nuclear Magnetic Resonance (NMR)**:\n   - Use \u00b9H-NMR and \u00b9\u00b3C-NMR to verify the presence of AMPS in the polymer matrix.\n3. **Gel Permeation Chromatography (GPC)**:\n   - Assess molecular weight distribution and verify chain transfer control (if applicable).\n4. **Hydrophilicity Testing**:\n   - Conduct water absorption studies or contact angle measurements to quantify the improvement in hydrophilicity.\n\n---\n\n### Key Notes and Precautions:\n1. **Storage of AMPS**: Ensure AMPS is stored in a cool, dry place, as it may clump or degrade when exposed to high humidity.\n2. **Side Reactions**: Minimize side reactions by maintaining proper pH and avoiding prolonged exposure to high temperatures during polymerization.\n3. **Safety**: Wear appropriate PPE, as persulfate initiators and AMPS can cause irritation upon contact.\n\nBy following the above preparation scheme, you will successfully synthesize a hydrophilic polymer with AMPS incorporated into the matrix, ensuring enhanced water affinity and desired physical properties. Let me know if you have any further questions!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe a method to deposit a graphene oxide (GO)-modified polymer coating on a substrate, ensuring both high hydrophilicity and good mechanical stability of the coating."}, {"role": "assistant", "content": "To design a method for depositing a **graphene oxide (GO)-modified polymer coating** on a substrate with high hydrophilicity and good mechanical stability, let us proceed step by step while adhering to the scientific and detail-oriented guidelines.\n\n---\n\n### Step 1: **Analyze the Question and Summarize the Key Points**\nThe critical requirements of the question are as follows:\n1. The desired coating must exhibit **high hydrophilicity**, which implies the need for hydrophilic functional groups and compatibility between GO and the polymer.\n2. The coating must have **good mechanical stability**, ensuring it adheres well to the substrate and exhibits robust physical properties.\n3. A graphene oxide (GO)-modified polymer needs to be incorporated into the coating.\n\nKey approach: GO is a functional nanomaterial with numerous hydrophilic groups such as carboxyl (\u2013COOH), hydroxyl (\u2013OH), and epoxy (\u2013C\u2013O\u2013C), making it inherently hydrophilic. Its incorporation into a hydrophilic polymer matrix will enhance both the hydrophilicity and mechanical resilience of the coating. The preparation must involve systematic steps of substrate preparation, polymer-GO functionalization, and coating deposition.\n\n---\n\n### Step 2: **Design the Preparation Scheme**\nBelow is a systematic preparation scheme that addresses the requirements of high hydrophilicity and mechanical stability in detail.\n\n#### **A. Materials and Reagents**\n1. **Graphene Oxide (GO):** Commercially available or synthesized via the Hummers\u2019 method.\n2. **Hydrophilic Polymer Precursor:** Candidates could include:\n   - Poly(vinyl alcohol) (PVA)\n   - Polyethylene glycol diacrylate (PEG-DA)\n   - Polyacrylamide (PAM)\n3. **Crosslinker:** For mechanical stability, use crosslinking agents like glutaraldehyde (for PVA), N,N'-methylenebisacrylamide (for PAM), or UV light (for PEG-DA).\n4. **Solvent:** Water or aqueous ethanol for dissolving the polymer precursor.\n5. **Substrate:** Glass, metal, silicon wafer, or polymer.\n\n---\n\n#### **B. Experimental Procedure**\n\n##### **Step 1: Substrate Preparation**\n1. Choose a smooth, clean substrate (e.g., glass or silicon wafer).\n2. Wash the substrate thoroughly with:\n   - Distilled water and ethanol to remove organic contaminants.\n   - Optional: Perform plasma treatment to enhance surface activation, increasing adhesion of the polymer coating.\n3. Air-dry the substrate or dry in an oven at 70 \u00b0C.\n\n---\n\n##### **Step 2: Preparation of the GO-Modified Polymer Solution**\n1. **Disperse Graphene Oxide:**\n   - Disperse GO in deionized water (concentration ~2-5 mg/mL) using ultrasonication for 1 hour to create a stable colloidal suspension.\n   - Integrating GO: Higher GO loading enhances hydrophilicity, but excessive GO can reduce the flexibility of the polymer matrix. Typical GO mass fraction: ~0.5-5% relative to the polymer precursor.\n   \n2. **Prepare the Polymer Precursor Solution:**\n   - For **PVA:** Dissolve 10 g of PVA in 90 mL deionized water while gently heating (~80\u201390 \u00b0C) and stirring until completely dissolved.\n   - For **PEG-DA:** Use 10 wt% PEG-DA dissolved in water as the precursor solution.\n   - For **PAM:** Prepare a solution of acrylamide monomer (10\u201315 wt%) in water.\n   \n3. **Combine GO with the Polymer Precursor:**\n   - Gradually add the GO suspension into the polymer precursor under continuous stirring to form a homogeneous GO-polymer mixture.\n   - Optional chemical grafting: If stronger interactions between GO and the polymer are desired, modify GO with coupling agents (e.g., silanes or carbodiimides) to attach to the polymer chains.\n\n---\n\n##### **Step 3: Deposition of the Coating**\n1. **Spin Coating:** This is suitable for uniform coatings.\n   - Drop ~100 \u00b5L of the GO-polymer mixture onto the substrate.\n   - Spin the substrate at ~1000\u20133000 rpm for 30\u201360 seconds to spread the coating evenly.\n2. **Dip Coating:** Submerge the substrate into the GO-polymer solution, then withdraw it at a controlled rate (e.g., 10 mm/min) to form a uniform film.\n3. **Spray Coating (Optional):** Use for irregular or large-scale surfaces.\n   - Use a fine mist sprayer to evenly deposit the GO-polymer solution onto the substrate.\n\n---\n\n##### **Step 4: Crosslinking (Enhancing Mechanical Stability)**\n1. Select a crosslinking strategy based on the chosen polymer:\n   - **For PVA:** Immerse the coated substrate in a 1 wt% glutaraldehyde aqueous solution for 1 hour, followed by washing thoroughly with water.\n   - **For PEG-DA:** Cure the coating under UV light (365 nm) for 5\u201310 minutes.\n   - **For PAM:** Add N,N'-methylenebisacrylamide as a crosslinker during polymer precursor preparation and initiate crosslinking with a radical initiator like ammonium persulfate (APS) and TEMED.\n2. After crosslinking, wash the coating with water to remove unreacted reagents.\n\n---\n\n##### **Step 5: Drying and Post-Treatment**\n1. Dry the substrate under ambient conditions or in an oven at ~60 \u00b0C for 1\u20132 hours.\n2. (Optional) Conduct additional plasma treatment or annealing (~120 \u00b0C) to improve coating stability and adhesion, if needed.\n\n---\n\n#### **C. Characterization of the Coating**\n1. **Hydrophilicity Test:** Measure water contact angle. A contact angle <30\u00b0 indicates excellent hydrophilicity.\n2. **Mechanical Stability Test:** Perform adhesion tests (tape test or nano-scratch test) and monitor wear resistance under mechanical stress.\n3. **Morphology and Uniformity:** Use scanning electron microscopy (SEM) or atomic force microscopy (AFM) to analyze surface structure.\n4. **Chemical Composition:** Confirm successful incorporation of GO using Fourier-transform infrared spectroscopy (FTIR) or Raman spectroscopy.\n\n---\n\n### Final Notes:\nThis procedure ensures a hydrophilic polymer coating modified with GO, fulfilling the requirements for both enhanced hydrophilic properties and mechanical stability. The key to success lies in proper dispersion of GO without aggregation, appropriate polymer-GO compatibility, and effective crosslinking for stability."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Propylene glycol is mentioned as a component in the preparation of hydrophilic polymers. Design an experimental protocol incorporating propylene glycol to enhance the hydrophilicity of a polymer surface. Include details such as concentration, mixing methods, and reaction conditions."}, {"role": "assistant", "content": "Excellent question! Let's work step by step to design an experimental protocol incorporating **propylene glycol (PG)** to enhance the hydrophilicity of a polymer surface. Before diving into the specifics, I'll analyze the question and highlight key points.\n\n---\n\n### **1. Key Points to Consider**\n- **Objective**: Incorporate propylene glycol into a protocol to increase the hydrophilicity of a polymer surface.\n- **Challenges**: A polymer\u2019s surface must be modified in a controlled manner to achieve hydrophilicity without compromising its structural integrity.\n- **Propylene Glycol Properties**: PG has strong hydrophilic characteristics due to its hydroxyl (-OH) groups but requires a functionalization method to graft it or blend it effectively into a polymer.\n- **Methodology**: Since PG is not inherently polymerizable on its own, we must either (a) physically blend it into the polymer matrix or (b) chemically graft it onto the surface.\n\n---\n\n### **2. Protocol Design: Enhancing Hydrophilicity of a Polymer Surface**\n\nWe will use chemical surface functionalization of the polymer with grafted propylene glycol for long-lasting hydrophilicity. A two-step method is recommended: **(i) pre-activation of the polymer surface** followed by **(ii) grafting propylene glycol via coupling chemistry**.\n\n---\n\n#### **Step 1: Pre-Activation of Polymer Surface**\n1. **Objective**: To introduce reactive groups onto the polymer surface for PG grafting.\n2. **Method**: Plasma treatment or chemical activation with an oxidizing agent (e.g., potassium permanganate or chromic acid).\n\n   **Example: Chemical Activation with Potassium Permanganate**\n   - **Materials Required**: Polymer target, potassium permanganate (KMnO\u2084), sulfuric acid (H\u2082SO\u2084).\n   - **Procedure**:\n     1. Clean the polymer surface using ethanol and de-ionized water.\n     2. Submerge the polymer in an oxidizing solution (0.1 M KMnO\u2084 with 1 M H\u2082SO\u2084) at 70\u00b0C for 30 minutes.\n     3. Wash thoroughly with DI water and dry under nitrogen.\n   - **Expected Outcome**: Hydroxyl (-OH), carboxylic acid (-COOH), or carbonyl (-C=O) groups will form on the polymer surface, providing reactive sites for PG attachment.\n\n---\n\n#### **Step 2: Grafting Propylene Glycol to the Polymer Surface**\n1. **Objective**: Chemically bind propylene glycol to the activated polymer surface using coupling chemistry.\n2. **Materials Required**:\n   - Propylene glycol (99% pure).\n   - Carbodiimide coupling reagent (e.g., 1-ethyl-3-[3-dimethylaminopropyl]carbodiimide (EDC)).\n   - Hydroxybenzotriazole (HOBt) to enhance coupling efficiency.\n   - Phosphate buffer (pH = 7.2).\n\n3. **Procedure**:\n   - **Preparation of Coupling Solution**:\n     1. Dissolve 0.1 M EDC and 0.05 M HOBt in phosphate buffer.\n     2. Add 0.1 M propylene glycol to the solution, stirring at room temperature for 10 minutes.\n   - **Application**:\n     1. Immerse the activated polymer specimen in the coupling solution.\n     2. Maintain stirring at room temperature (25\u201330\u00b0C) for 16\u201318 hours.\n     3. Rinse the polymer thoroughly with DI water to remove unreacted PG.\n   - **Expected Outcome**: Propylene glycol molecules covalently bond to the surface through the hydroxyl and carboxylic acid groups introduced during activation.\n\n---\n\n#### **Step 3: Post-Treatment and Confirmation**\n1. **Drying**:\n   - Allow the polymer to dry under vacuum at 40\u00b0C for 24 hours.\n2. **Confirmation of Hydrophilicity**:\n   - Use **water contact angle measurement** to confirm increased hydrophilicity. Hydrophilic surfaces exhibit a contact angle <45\u00b0.\n   - Perform **FTIR spectroscopy** to verify successful grafting. Look for characteristic hydroxyl (-OH) peaks associated with propylene glycol in the 3200\u20133500 cm\u207b\u00b9 range.\n\n---\n\n### **3. Summary of Protocol**\n- Pre-treat the polymer surface for activation via oxidation (e.g., KMnO\u2084 or plasma treatment).\n- Conduct chemical coupling of propylene glycol using a carbodiimide reaction (EDC/HOBt system).\n- Ensure all reaction conditions (temperature, pH, timescale) are optimized for effective grafting.\n- Post-treat the polymer and confirm hydrophilicity enhancement via analytical tools like water contact angle or FTIR.\n\n---\n\nBy following this step-by-step experimental plan, you should be able to effectively incorporate propylene glycol into a functionalized hydrophilic polymer surface. Let me know if you'd like further explanations or adjustments to this protocol!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain how you would utilize 3-Trimethoxysilylpropyl methacrylate (TMSMA) in the experiment to improve adhesion of the polymer to a glass substrate. What specific steps would you take to activate the substrate prior to applying the polymer coating?"}, {"role": "assistant", "content": "To answer your question regarding the use of **3-Trimethoxysilylpropyl methacrylate (TMSMA)** to improve the adhesion of a polymer to a glass substrate, I will first analyze the key points of the question and then systematically present an experimental procedure with all the necessary details.\n\n---\n\n### **Key Points of the Question:**\n1. **Role of TMSMA**: TMSMA is a silane coupling agent containing both silane functionality (trimethoxysilyl) and a polymerizable methacrylate group. The dual functionality can form strong covalent bonds with the silanol groups on the glass surface and participate in polymerization reactions, thereby improving adhesion.\n2. **Activation of the Glass Substrate**: Glass substrates need to be cleaned and activated (typically through chemical or plasma methods) to ensure that the hydroxyl groups on the surface are accessible for reaction with the silane coupling agent.\n3. **Synthesis and Application Process**: Applying the polymer coating involves substrate pretreatment, TMSMA surface functionalization, and subsequent polymer deposition using appropriate conditions.\n\n---\n\n### **Detailed Experimental Scheme:**\n\n#### **Step 1: Glass Substrate Cleaning and Activation**\nThe first step is to prepare the glass surface to ensure high surface energy, cleanliness, and the presence of reactive hydroxyl (-OH) groups.\n1. **Materials Required**:\n   - Glass slides or substrates.\n   - Cleaning agents: Deionized (DI) water, ethanol (or isopropanol), and piranha solution (or equivalent cleaning method).\n   - Sodium hydroxide (NaOH) or hydrochloric acid (HCl) for surface activation.\n2. **Procedure**:\n   a. **Physical Cleaning**:\n      - Rinse the glass thoroughly with a 50:50 mixture of ethanol and DI water to remove dust and grease.\n      - Sonicate the glass slides in ethanol for 15 minutes for better cleaning.\n   b. **Chemical Cleaning** (if higher cleanliness is required):\n      - Prepare a piranha solution (3:1 mixture of H\u2082SO\u2084 and H\u2082O\u2082). Warning: Handle with extreme caution in a fume hood, as this reaction is highly exothermic.\n      - Immerse the glass slides in the piranha solution for 10-15 minutes to remove organic contaminants.\n      - Rinse thoroughly with DI water multiple times to remove all residual acid.\n   c. **Surface Hydroxylation**:\n      - Prepare an alkaline solution (0.1 M NaOH) or acidic solution (0.1 M HCl).\n      - Immerse the clean glass substrate in the NaOH (or HCl) solution for 30 minutes at room temperature.\n      - Rinse the glass substrate with DI water and dry with nitrogen gas.\n   d. **Final Drying**:\n      - Dry the glass substrates in a clean oven at 110\u2013120 \u00b0C for 30 minutes to completely remove moisture but ensure reactive -OH groups remain intact.\n      - Cool the substrates to room temperature in a desiccator before proceeding.\n\n---\n\n#### **Step 2: Functionalization with TMSMA**\nThe next step is to treat the activated glass substrate with TMSMA to create a silanized surface that enhances polymer adhesion.\n1. **Materials Required**:\n   - TMSMA.\n   - Ethanol or an ethanol-water mixture (95:5 ratio).\n   - Acetic acid (as a catalyst for hydrolysis).\n   - Glass substrates from Step 1.\n   - Glovebox or clean environment to minimize contamination.\n2. **Procedure**:\n   a. **Prepare the Silane Solution**:\n      - In a clean glass vial, mix ethanol and DI water in a 95:5 ratio (v/v).\n      - Add acetic acid dropwise to adjust the pH to ~4.5 (slightly acidic).\n      - Slowly add TMSMA to achieve a concentration of 2\u20135% (v/v) in the solution.\n      - Stir the solution at room temperature for 10\u201315 minutes to promote hydrolysis of the methoxysilyl groups to silanols (Si\u2013OH).\n   b. **Coating Process**:\n      - Immerse the cleaned and activated glass substrates in the TMSMA solution.\n      - Allow the substrates to sit in the solution for 15\u201330 minutes to enable sufficient binding of the silane to the glass surface through condensation reactions between TMSMA\u2019s Si\u2013OH groups and the glass\u2019s surface hydroxyl groups.\n   c. **Post-Treatment**:\n      - Remove the substrates from the solution and rinse them gently with ethanol to remove excess unreacted silane.\n      - Allow the substrates to dry at room temperature in a nitrogen atmosphere for 10\u201315 minutes.\n      - Cure the silanized substrates in a vacuum oven at 110\u2013120 \u00b0C for 1\u20132 hours to drive the condensation reaction to completion, forming a covalent Si\u2013O\u2013Si network.\n\n---\n\n#### **Step 3: Polymer Coating Application**\nWith the TMSMA-functionalized glass substrate prepared, the polymer (containing hydrophilic components) can now be coated. In this step, the methacrylate group in TMSMA can covalently bond with the polymer, ensuring strong adhesion.\n1. **Materials Required**:\n   - Polymer solution or monomer(s) for polymerization (compatible with the targeted application).\n   - Additional solvent (if needed) to adjust coating viscosity.\n   - Initiator for polymerization (e.g., thermal, UV, or redox initiators, depending on monomer choice).\n   - Spin coater (optional) or dip-coating setup.\n2. **Procedure**:\n   a. **Preparation of Polymer or Monomer Solution**:\n      - Dissolve the polymer in a suitable solvent if applying an existing polymer. Alternatively, prepare a monomer solution with the desired molar ratios for copolymerization.\n      - Add the initiator in the required proportion (commonly 1\u20135% w/w of the monomers).\n   b. **Coating onto the Substrate**:\n      - Place the TMSMA-functionalized glass substrate in a spin-coater or dip-coating setup.\n      - Deposit the polymer or monomer solution onto the substrate.\n      - Spread the solution evenly over the surface (e.g., spin-coating can use 1500\u20133000 rpm for 30\u201360 seconds, depending on viscosity).\n   c. **Polymerization** (if monomers are used):\n      - Expose the coated substrate to appropriate conditions (e.g., heat to 60\u201380 \u00b0C for thermal polymerization or UV lamp for photopolymerization, depending on initiator).\n   d. **Curing and Finalization**:\n      - Allow the polymer-coated substrate to cure and cool to room temperature.\n      - Rinse and dry the substrate if necessary to remove unreacted monomers or solvents.\n\n---\n\n### **Reaction Details and Mechanism:**\n1. **Glass Functionalization (Step 2)**:\n   - Hydrolyzed TMSMA silanol groups react with the surface hydroxyl groups on the glass, forming strong Si\u2013O\u2013Si covalent bonds while the methacrylate group remains exposed for further polymerization.\n   - Reaction mechanism:\n     \\[\n     \\text{Si-OCH}_3 + \\text{H}_2\\text{O} \\rightarrow \\text{Si-OH} + \\text{CH}_3\\text{OH}\n     \\]\n     \\[\n     \\text{Si-OH (TMSMA)} + \\text{Si-OH (glass)} \\rightarrow \\text{Si-O-Si (covalent bond)} + \\text{H}_2\\text{O}\n     \\]\n2. **Polymer-Coating Step**:\n   - The methacrylate groups on TMSMA copolymerize with monomers or cross-link with polymers, forming a durable interfacial bond.\n\n---\n\nBy following the steps outlined above, the adhesion of hydrophilic polymers to glass substrates will be greatly enhanced due to the dual functionality of TMSMA. Be sure to carefully monitor reaction conditions and maintain a clean working environment to ensure reproducibility of results."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the steps you would take to incorporate the given molecule into the polymer structure to enhance its hydrophilicity, ensuring you include any required reaction conditions or solvents."}, {"role": "assistant", "content": "Certainly! Let\u2019s carefully analyze your question and systematically outline an experimental preparation scheme for incorporating your given molecule into a polymer structure to enhance its hydrophilicity.\n\n---\n\n#### **Step 1: Analyze the Problem and Identify the Goals**\nYour goal is to enhance the hydrophilicity of a polymer by integrating a molecule you\u2019ve provided. To achieve this, we need to do two things:\n1. Identify the functional groups on your molecule that can be used to either directly participate in polymerization or attach as side groups to a polymer backbone.\n2. Choose an appropriate polymerization or grafting method (e.g., free radical polymerization, condensation polymerization, or post-polymerization modification) that facilitates efficient incorporation while maintaining or improving hydrophilic properties.\n\nLet\u2019s proceed by designing the experimental protocol step-by-step, ensuring each step contains precise reaction conditions and details for laboratory execution.\n\n---\n\n#### **Step 2: Experimental Design for Hydrophilic Polymer Synthesis**\n\n##### **(Step 2.1) Analyze the Given Molecule**\n- Examine the chemical structure of the molecule. Look for:\n  - **Hydrophilic functional groups** such as hydroxyl (-OH), amino (-NH2), carboxyl (-COOH), sulfonic acid (-SO3H), or polyhydric alcohols (e.g., poly(ethylene glycol), PEG) that will impart hydrophilicity.\n  - **Polymerizable groups** like vinyl (-C=C-) or epoxide rings, which can be used directly in polymerization.\n  - **Reactive groups** that can engage in post-polymerization modifications, such as -OH, -NH2, or acid anhydrides.\n\nLet me assume your molecule contains a vinyl group and a strongly hydrophilic group like a hydroxyl or sulfonic acid. We can then employ free radical polymerization for direct incorporation during polymer synthesis.\n\n---\n\n##### **(Step 2.2) Select the Polymerization Method**\nTo directly polymerize the hydrophilic molecule, the **free radical polymerization** method is well-suited because it:\n- Works with most vinyl monomers.\n- Is robust, straightforward, and widely adaptable.\n\nHere, we can use the provided molecule as a comonomer, alongside another hydrophilic monomer (e.g., acrylic acid or N-vinylpyrrolidone), to prepare a copolymer with enhanced hydrophilicity.\n\n---\n\n##### **(Step 2.3) Materials and Reagents**\n1. **Monomers**:\n   - The given molecule, which we shall call the \"functional monomer.\"\n   - Another hydrophilic comonomer (e.g., acrylic acid, acrylamide, or hydroxyethyl methacrylate, HEMA) to boost hydrophilicity further.\n2. **Initiator**:\n   - A radical initiator, typically **azobisisobutyronitrile (AIBN)** or **ammonium persulfate (APS)**.\n3. **Solvent**:\n   - A compatible polar solvent, such as water, ethanol, or a water-ethanol mixture.\n4. **Crosslinker** (optional):\n   - If a networked hydrogel structure is required, consider adding a bifunctional crosslinker like **ethylene glycol dimethacrylate (EGDMA)**.\n5. **pH Adjuster**:\n   - Sodium hydroxide (NaOH) or hydrochloric acid (HCl) to tune the pH of the reaction medium if required for specific monomers.\n\n---\n\n##### **(Step 2.4) Reaction Protocol**\n1. **Preparation of the Reaction Mixture**:\n   - Dissolve the hydrophilic monomer (e.g., acrylic acid) and the given functional monomer in the chosen solvent. These can be mixed at a molar ratio such as **1:1** or adjusted depending on the desired hydrophilicity and monomer reactivities.\n   - Add the radical initiator (e.g., AIBN) at a concentration of **0.5\u20131.0 wt% relative to the total monomer content**.\n   - If a crosslinking agent is required, add it at a low molar fraction (e.g., **1\u20132 mol% of the total monomers**).\n   - Ensure the solution is well-mixed and degas the reaction mixture by bubbling nitrogen or argon gas to remove oxygen, which can inhibit radical polymerization.\n\n2. **Polymerization Reaction**:\n   - Transfer the reaction mixture into a three-necked round-bottom flask equipped with a magnetic stirrer, reflux condenser, and thermometer.\n   - Initiate the reaction by heating the mixture to **60\u201380\u00b0C** under an inert nitrogen atmosphere. Maintain stirring throughout the reaction.\n   - Allow the polymerization to proceed for **4\u20136 hours**, depending on the reactivity of the monomers chosen.\n\n3. **Post-Reaction Processing**:\n   - After completion, cool the reaction mixture to room temperature.\n   - Precipitate the polymer by adding the reaction mixture dropwise into a nonsolvent (e.g., diethyl ether or acetone for aqueous polymerizations).\n   - Filter and wash the polymer thoroughly to remove unreacted monomers and impurities.\n\n4. **Drying and Storage**:\n   - Dry the purified polymer under vacuum at **40\u201350\u00b0C** until a constant weight is achieved.\n   - Store the polymer in a desiccator to prevent moisture absorption.\n\n---\n\n#### **Step 3: Characterization of the Synthesized Polymer**\nTo confirm the successful incorporation of your molecule and assess hydrophilicity:\n1. **FTIR Spectroscopy**: To identify characteristic functional group peaks in the polymer structure.\n2. **Contact Angle Measurement**: To measure the water contact angle and evaluate surface hydrophilicity.\n3. **NMR Spectroscopy**: To verify the incorporation of the hydrophilic groups and the functional monomer into the polymer backbone.\n4. **Swelling Studies (for hydrogels)**: Immerse the polymer in water and measure its swelling ratio as an indicator of hydrophilicity.\n\n---\n\n#### **Conclusion**\nBy following the outlined procedure, you\u2019ll successfully synthesize a hydrophilic polymer incorporating your molecule. The chosen method, free radical polymerization, is versatile for handling a wide range of vinyl-functionalized hydrophilic molecules. Always monitor the reaction conditions (temperature, pH, solvent system) for optimal results and ensure proper purification to obtain high-quality polymers.\n\nLet me know if you'd like a further refinement of this protocol or assistance with an alternative reaction pathway!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe a step-by-step procedure to include calcium chloride (CaCl2) in the polymerization process to enhance the hydrophilicity of the resulting material. What is the significance of adding this molecule, and how might it interact with other components during synthesis?"}, {"role": "assistant", "content": "Certainly! To address your question regarding the inclusion of calcium chloride (CaCl\u2082) in the polymerization process for improving the hydrophilicity of the resulting material, let us analyze the problem first, then proceed to systematically describe the step-by-step procedure, and finally discuss the significance and potential interaction of CaCl\u2082 with other components.\n\n---\n\n### **Step 1: Analyzing the Question**\n\nThe goal is to:\n1. Incorporate calcium chloride (CaCl\u2082) into the polymerization process.\n2. Enhance the hydrophilicity of the resulting polymer material.\n \nCaCl\u2082 is a hygroscopic salt known for its excellent water-attracting and dissolving properties. Adding CaCl\u2082 may increase the affinity of the polymer for water (hydrophilicity) either directly through ionic interactions with charged groups on the polymer or indirectly by influencing the polymerization process itself, such as affecting crosslinking or chain interactions.\n\nTo systematically prepare a polymer with improved hydrophilicity enhanced by CaCl\u2082, we need to carefully control all reaction parameters and understand the role that CaCl\u2082 plays during the polymerization process.\n\n---\n\n### **Step 2: Experimental Preparation Scheme**\n\nBelow is the detailed, step-by-step approach to designing an experimental polymerization process incorporating CaCl\u2082:\n\n---\n\n#### **Step 2.1: Selection of Monomers**\n- Choose monomers or comonomers that allow polymerization and have functional groups capable of interacting with CaCl\u2082. For instance:\n    - Acrylamide (AM) is a common monomer for hydrophilic polymer synthesis.\n    - Acrylic acid (AA) or methacrylic acid (MAA) can be used for introducing carboxylic acid groups, which interact with Ca\u00b2\u207a ions.\n- Optionally, copolymerization with hydrophilic monomers like hydroxyethyl methacrylate (HEMA) or polyethylene glycol methacrylate (PEGMA) might further augment the polymer's water-attracting properties.\n\n---\n\n#### **Step 2.2: Preparation of Reaction Solution**\n- **Solvent:** Prepare an aqueous medium as water facilitates the solubilization of CaCl\u2082 and is ideal for hydrophilic polymer synthesis.\n- **Calcium Chloride Pre-Dissolution:** Dissolve CaCl\u2082 in water before introducing it to the polymer reaction solution. The concentration of CaCl\u2082 typically ranges from 0.05 M to 0.5 M, depending on the desired enhancement in hydrophilicity.\n    - Example: For 0.2 M CaCl\u2082 concentration in 100 mL water, dissolve 2.2 g of CaCl\u2082 in water.\n\n---\n\n#### **Step 2.3: Polymerization Setup**\n- **Reaction Vessel:** Use a glass reactor equipped with a magnetic stirrer, nitrogen inlet (for inert atmosphere), and a temperature-controlled heating mantle.\n- **Initiator System:** Choose a suitable radical initiator (e.g., ammonium persulfate (APS), potassium persulfate (KPS), or azobisisobutyronitrile (AIBN) depending on solvent and conditions).\n\n---\n\n#### **Step 2.4: Reaction Conditions**\n1. **Initiator Activation:**\n   - Dissolve the initiator in the CaCl\u2082-containing aqueous solution. A typical initiator amount is 0.1\u20130.5 wt% of the total monomer content.\n   - For APS, dissolve 0.2 g APS in 50 mL water containing CaCl\u2082.\n   - Degas the solution by bubbling nitrogen through for 30 minutes to create an inert atmosphere.\n   - Heat the solution to ~70 \u00b0C to activate APS under controlled stirring conditions.\n\n2. **Addition of Monomers:**\n   - Add monomers (e.g., 10 g AM, 5 g AA, and optionally 1 g PEGMA) into the reactor slowly while stirring to ensure homogeneous mixing.\n   - Monitor the pH of the solution and adjust with NaOH or HCl if required. The optimal range is slightly acidic to neutral (pH ~6\u20137).\n\n3. **Crosslinking Agent:**\n   - If a crosslinked hydrogel is desired, add a crosslinker such as N,N\u2032-methylenebisacrylamide (MBA). Typical quantities are 0.1\u20130.5 wt% of monomer content.\n   - Example: Add 0.1 g MBA to the monomer mixture.\n\n4. **Role of CaCl\u2082:**\n   - During polymerization, CaCl\u2082 enhances ionic interactions with the polymer chains, potentially influencing chain orientation as well as hydration properties. Ca\u00b2\u207a ions can interact electrostatically with carboxyl groups on acrylic acid or hydroxyl groups in PEGMA or AM, creating ionic clusters that increase polymer hydrophilicity.\n\n5. **Polymerization Reaction:**\n   - Allow the polymerization to proceed for 2\u20134 hours under constant stirring and controlled temperature (~70\u201375 \u00b0C).\n   - Monitor the reaction's viscosity and appearance (gelation may occur if crosslinked).\n\n---\n\n#### **Step 2.5: Polymer Washing and Purification**\n- **Washing:**\n   - After polymerization, remove unreacted CaCl\u2082 and other impurities by washing the polymer thoroughly with distilled water.\n   - For hydrogels, immerse them in large volumes of water and replace the water daily for 2\u20133 days.\n\n- **Drying:**\n   - Dry the polymer for further characterization, e.g., in a vacuum drying oven at 50 \u00b0C. Alternatively, leave hydrogels hydrated for direct use.\n\n---\n\n### **Step 3: Significance of Adding CaCl\u2082**\n\n#### 3.1: **Enhancement of Hydrophilicity**\n- Calcium chloride is hygroscopic and readily attracts water, which translates to a polymer system with increased water-binding capacity.\n- The interaction between Ca\u00b2\u207a ions and functional groups on the polymer chains introduces ionic exchanges that promote enhanced water diffusion and retention, thus increasing hydrophilicity.\n\n#### 3.2: **Impact on Polymer Structure**\n- CaCl\u2082 may influence the polymer network by ionic crosslinking or modifying polymer chain conformations. These effects might result in a softer, more porous structure, which is ideal for applications like hydrogels, tissue scaffolds, and superabsorbent polymers.\n\n#### 3.3: **Applications**\n- CaCl\u2082-modified hydrophilic polymers may find applications in biomedical fields (e.g., drug delivery), agriculture (e.g., soil conditioners), water purification, and personal care (e.g., hydrating gels).\n\n---\n\n### **Step 4: Interaction with Other Components**\n- **Monomers and Ca\u00b2\u207a:** Ionic interactions between Ca\u00b2\u207a ions and acidic functional groups strengthen polymer-water bonding.\n- **Crosslinker and CaCl\u2082:** Ca\u00b2\u207a ions may compete with covalent crosslinking, leading to altered mechanical properties in crosslinked hydrogels.\n\n---\n\nBy following these detailed steps and understanding the significance and interactions during synthesis, your experiment should yield a successful hydrophilic polymer with enhanced properties attributed to the addition of calcium chloride. Let me know if you need further clarification or assistance!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Using a molecule with a primary amine and a carboxylic acid group, propose how you would identify the head and tail atoms and classify the polymerization mechanism to create a hydrophilic polymer. Explain the rationale behind your choices."}, {"role": "assistant", "content": "To address your question step by step, let us carefully analyze the given scenario and my approach to designing an experimental preparation scheme for a hydrophilic polymer based on your given molecule with a primary amine (-NH2) and a carboxylic acid (-COOH) group.\n\n---\n\n### **Step 1: Analyze the Question**\n\nThe key points from your question are:\n1. **Molecule provided**: The molecule contains a primary amine (-NH2) group and a carboxylic acid (-COOH) group.\n2. **Goal**: Identify the \"head\" and \"tail\" atoms in the molecule to enable polymerization and subsequently classify the polymerization mechanism.\n3. **Objective**: Synthesize a hydrophilic polymer, enhancing its hydrophilicity based on the structure and functionality of the given molecule.\n\nThe hydrophilic nature of the polymer likely stems from the presence of hydrophilic groups (e.g., -NH2, -COOH, or derivatives such as amides, if introduced through polymerization). This requires careful consideration of chemical reactivity and how these groups will be preserved or modified during polymerization.\n\n---\n\n### **Step 2: Understanding the Head, Tail, and Polymerization Mechanism**\n\nIn polymer chemistry:\n- The **head** refers to the reactive site in the monomer that initiates or propagates chain growth through covalent bonding.\n- The **tail** refers to another complementary site in the monomer that connects to the head of the next monomer molecule.\n- **Polymerization mechanism** depends on the functional groups available in the monomer; in this case, we will consider a condensation polymerization mechanism due to the presence of -NH2 and -COOH groups.\n\nFor your molecule:\n- The **primary amine (-NH2)** can act as the nucleophile, donating electrons to form bonds.\n- The **carboxylic acid (-COOH)** can act as the electrophile, accepting nucleophilic attack and enabling condensation.\n\nBased on this, the primary amine can be designated as the \"head\" of the monomer (responsible for initiating bonding), while the carboxyl group serves as its \"tail\" (allowing chain propagation with subsequent monomer molecules).\n\n---\n\n### **Step 3: Classify the Polymerization Mechanism**\n\nThe polymerization mechanism that naturally fits for such a setup is **step-growth polymerization via condensation reactions**, where the removal of a small molecule (e.g., water) accompanies the formation of covalent bonds between the monomer units.\n\n- In this case, the polymerization occurs between the -NH2 and -COOH groups of the molecule through **amide bond formation** (-CONH-).\n- As a result, the polymer will consist of repeating units containing amide linkages, which are polar and contribute significantly to the hydrophilicity of the final polymer.\n\n---\n\n### **Step 4: Detailed Experimental Design of the Polymerization Scheme**\n\nHere, I provide a step-by-step protocol to synthesize a hydrophilic polymer based on the monomer you described.\n\n---\n\n#### **Materials Required**\n1. Monomer with primary amine (-NH2) and carboxylic acid (-COOH) group\n2. Catalyst: Condensation catalysts like dicyclohexylcarbodiimide (DCC) or a carbodiimide derivative can be used to facilitate amide bond formation.\n3. Solvent: Dimethylformamide (DMF) or tetrahydrofuran (THF) to dissolve the monomer and enable proper mixing.\n4. Dehydrating agent: To promote the condensation reaction by scavenging water (e.g., molecular sieves or an agent like thionyl chloride, if necessary).\n\n---\n\n#### **Step 1: Pre-Treatment of Monomer Solution**\n- Dissolve the monomer in a suitable aprotic polar solvent like DMF or THF. The concentration of the solution can typically be in the range of 0.5\u20131.0 M to ensure sufficient reactivity without excessive viscosity.\n- Add a small amount of base (e.g., triethylamine, ~5 mol% relative to the monomer) to neutralize any acidic impurities, maintaining the amine functionality.\n\n---\n\n#### **Step 2: Addition of Catalyst**\n- Introduce the catalyst (e.g., DCC) to the reaction mixture in equimolar proportion to the monomer or slightly in excess (~1.1 equivalents).\n- If high dehydration efficiency is needed, include a drying agent to remove water produced during the condensation process.\n\n---\n\n#### **Step 3: Reaction Conditions**\n- Heat the reaction mixture gently (e.g., 50\u201380\u00b0C) for 12\u201324 hours under an inert atmosphere (e.g., nitrogen or argon) to prevent unwanted side reactions.\n- Monitor the reaction progression using spectroscopic techniques such as FTIR (to track the disappearance of -NH2 and -COOH bands) or NMR.\n\n---\n\n#### **Step 4: Purification of the Polymer**\n- After polymerization, cool the solution and precipitate the polymer by pouring the reaction mixture into a large volume of a non-solvent (e.g., cold methanol or diethyl ether).\n- Filter or centrifuge the precipitated polymer, then wash thoroughly with the non-solvent to remove excess reagent and by-products.\n- Dry the purified polymer under vacuum at room temperature or slightly elevated temperature (~40\u201350\u00b0C) until constant weight is achieved.\n\n---\n\n### **Outcome and Observations**\n- The resulting polymer will contain repeating amide linkages (-CONH-) in its backbone. The polar nature of these bonds ensures that the polymer has significant hydrophilicity.\n- The degree of polymerization and molecular weight can be adjusted by controlling the reaction conditions, reagent ratios, or introduction of chain stoppers (e.g., monofunctional amines or carboxylic acids).\n\n---\n\n### **Step 5: Enhancing Hydrophilicity**\nDepending on the application, additional functionalization can enhance hydrophilicity, such as:\n1. Grafting onto the polymer with hydrophilic side chains (e.g., PEGylation).\n2. Increasing the density of hydrophilic groups by copolymerization with monomers containing hydroxyl (-OH) groups or sulfonic acid (-SO3H) groups.\n\n---\n\n### **Summary**\n\n1. **Head-Tail Assignment**: The -NH2 group acts as the nucleophilic \"head,\" while the -COOH group is the electrophilic \"tail.\"\n2. **Polymerization Mechanism**: Step-growth condensation polymerization forms amide bonds (-CONH-) between monomers.\n3. **Protocol**: The synthesis involves dissolving the monomer, activating polymerization with a carbodiimide catalyst, and purifying the product post-reaction.\n4. **Enhancing Hydrophilicity**: Functional groups in the polymer backbone, such as amide bonds, inherently contribute hydrophilicity, while grafting or copolymerization offers additional pathways.\n\nBy following this systematic method, you can successfully prepare hydrophilic polymers from the given bifunctional monomer."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain how the combination of 1-propanol with water during the solution preparation phase might affect the interactions between the polymer and the added molecule. How is this relevant to increasing the hydrophilicity of the final polymer product?"}, {"role": "assistant", "content": "Certainly, let\u2019s systematically analyze your question and break it down step by step.\n\n---\n\n### **1. Key Points Analysis**\nYour question revolves around:\n- How the combination of **1-propanol with water** in the solution preparation phase influences the interactions between the polymer and the added molecule.\n- How this combination is relevant to enhancing the hydrophilicity of the final polymer product.\n\nThe essence of the question ties chemical solvent choices to polymer hydration and reactions that ultimately alter hydrophilicity.\n\n### **2. Detailed and Systematic Answer**\nTo answer this question fully, we need to address the following:\n1. **Role of solvents (1-propanol and water) in controlling polymer-molecule interactions**.\n2. How solvent polarity and hydrogen bonding mechanisms enable hydrophilicity modulation during synthesis.\n3. A proposed experimental preparation scheme that includes 1-propanol and water for hydrophilic polymer synthesis.\n\n---\n\n#### **Step-by-Step Explanation**\n\n### **2.1 The Interaction Between 1-Propanol, Water, and the Polymer**\nWhen preparing a solution of 1-propanol combined with water, the solvent mixture functions as a medium for modulating hydrogen bonding and hydrophobic interactions. Here\u2019s why:\n\n- **Solvent Polarity**:\n  - Water is a **highly polar** solvent, capable of forming extensive hydrogen bonds. It promotes the hydration and hydrophilicity of chemical groups like \u2013OH, \u2013COOH, or \u2013NH2 on the polymer molecule.\n  - 1-Propanol is moderately polar and includes both a hydrophilic hydroxyl (-OH group) and a hydrophobic alkane section. By combining these complementary solvents, you can tailor the solvent environment to balance polar and nonpolar interactions.\n\n- **Hydrogen Bonding**:\n  - 1-propanol can form weaker hydrogen bonds compared to water because the \u2013OH is attached to an alkyl group. However, its hydrophilic properties ensure compatibility with water.\n  - The presence of both water and 1-propanol allows optimization of hydrogen bond donation and acceptance in the system, facilitating interactions between the polymer backbone and any hydrophilic functional groups introduced.\n\n### **2.2 Relevance to Hydrophilicity**\nThe addition of 1-propanol to water significantly impacts polymer hydrophilicity for multiple reasons:\n\n1. **Improved Solvent Dynamics**:\n   The presence of 1-propanol ensures that hydrophilic functional groups (e.g., hydroxyl or amine groups) in the polymer precursor or the added molecule have access to water molecules, enhancing hydration.\n\n2. **Control Over Functional Group Orientation**:\n   The combined solvent mixture creates a favorable environment for the polymer structure to adopt a conformation that maximizes exposure of hydrophilic groups to water. 1-propanol can help solubilize and evenly distribute added molecules that might otherwise resist water solvation.\n\n3. **Enhanced Reaction Efficiency**:\n   During synthesis, intermediates or monomers containing hydrophilic groups may dissolve more uniformly in the water-1-propanol solution, improving reactivity and ensuring uniform incorporation of hydrophilic groups into the final polymer matrix.\n\n---\n\n### **Proposed Experimental Preparation Scheme**\n\n#### **Step 1: Prepare Solvent Mixture**\n- Combine **1-propanol and water** in a ratio of **30:70 vol/vol** (adjustable based on solubility requirements and polymer chemistry).\n  - This ratio balances moderate solvation power from 1-propanol with strong hydrogen bonding from water.\n\n#### **Step 2: Dissolve Polymer Precursor**\n- Add the polymer precursor (e.g., a hydrophilic monomer such as acrylamide or a combination of monomers like polyethylene glycol (PEG), acrylonitrile, etc.) to the solvent mixture at a concentration of **0.5\u20132 mol/L**.\n  - Stir the solution vigorously to ensure homogeneity.\n\n#### **Step 3: Introduce Hydrophilic Additives**\n- Introduce hydrophilic molecules or functionalization agents (e.g., hydroxyl-rich molecules, carboxylic acids, ammonium salts) to the solvent mixture. These can include molecules like glycerol, acrylic acid, or other modifiers.\n  - Maintain a **molar ratio** of additive to polymer precursor between **1:1\u20131:2** to ensure sufficient hydrophilic functional group incorporation.\n\n#### **Step 4: Polymerization Reaction**\nDepending on the type of polymer, perform one of the following polymerization techniques:\n- **Free Radical Polymerization**:\n  - Initiator: Use a radical initiator like ammonium persulfate (APS) or azobisisobutyronitrile (AIBN).\n  - Reaction Conditions: Conduct the polymerization at **60\u201370 \u00b0C** for 6\u201312 hours with continuous stirring.\n- **Condensation Reaction**:\n  - Catalyst: Use a condensation catalyst such as sulfuric acid or phosphoric acid.\n  - Reaction Conditions: Heat the reaction vessel under reflux at **80\u2013100 \u00b0C** for a suitable time (~12 hours).\n\n#### **Step 5: Purification**\n- Precipitate the polymer by adding a non-solvent (e.g., methanol or acetone) to isolate the hydrophilic polymer.\n- Wash the polymer thoroughly with water to remove unreacted monomers and residual solvent.\n\n#### **Step 6: Characterization**\n- Use techniques like **FTIR spectroscopy** to confirm the incorporation of hydrophilic groups into the polymer matrix.\n- Perform water contact angle measurements to evaluate hydrophilicity.\n\n---\n\n### **Conclusion**\nThe combination of 1-propanol with water during the solution preparation phase enhances polymer hydrophilicity by optimizing solvent dynamics, hydrogen bonding capabilities, and functional group orientations. This enables the added hydrophilic molecules or groups to interact effectively with the polymer precursor. Following the outlined preparation scheme, you can ensure successful synthesis of a hydrophilic polymer while maintaining rigorous experimental standards.\n\n"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the procedure for reacting 2-(cyclohexylamino)-ethanesulfonic acid with polyisocyanate under controlled temperature conditions to enhance the hydrophilicity of the polymer. What key parameters require monitoring during the reaction?"}, {"role": "assistant", "content": "Certainly! I appreciate your question, as it highlights a significant approach to tuning the hydrophilicity of a polymer through chemical modification. Let\u2019s methodically break this task down and develop a detailed experimental preparation scheme.\n\n---\n\n### Step 1: **Question Review and Key Points Summarized**\nThe problem involves reacting 2-(cyclohexylamino)-ethanesulfonic acid (commonly referred to as CHES) with a polyisocyanate to create a polymer with enhanced hydrophilicity. CHES is hydrophilic due to both its sulfonic acid group and secondary amine, and introducing it into a polyisocyanate structure would impart hydrophilicity to the resulting polymer. Key parameters to consider during this process include:\n1. Maintaining controlled temperature conditions (to avoid side reactions or premature crosslinking).\n2. Ensuring proper molar ratios of CHES to isocyanate groups for an optimized reaction.\n3. Proper solvent selection to ensure complete dissolution and adequate mixing of reactants.\n4. Monitoring reaction variables, such as the reaction time, temperature, and degree of polymerization.\n\n---\n\n### Step 2: **Reagent and Material Preparation**\n#### Required materials:\n1. **2-(Cyclohexylamino)-ethanesulfonic acid (CHES)**: Hydrophilic reactant.\n2. **Polyisocyanate** (e.g., hexamethylene diisocyanate [HDI], or a polyisocyanate oligomer): Base polymer reagent.\n3. **Solvent**: N,N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) is recommended for dissolving CHES and the polyisocyanate.\n4. **Catalyst (optional)**: Dibutyltin dilaurate (DBTDL) or triethylamine to promote urethane bond formation.\n5. **Desiccant or drying agent**: To remove water, since water reacts with isocyanates.\n6. **Nitrogen or argon gas**: To create an inert atmosphere and prevent reaction of the isocyanates with ambient moisture.\n\n#### Reaction overview:\nThe key reaction mechanism involves:\n- Reaction of the isocyanate (-N=C=O) groups from the polyisocyanate with the secondary amine (-NH-) group of CHES to form a urea linkage (-NH-CO-NH-).\n- The resultant polymer will have hydrophilic sulfonic acid (-SO\u2083H) side groups, enhancing the overall hydrophilicity.\n\n---\n\n### Step 3: **Experimental Procedure**\n#### (1) **Preparation of CHES Solution**:\n   - **Weigh CHES**: Based on the desired molar ratio (e.g., 1:1 ratio between CHES and isocyanate groups on the polyisocyanate), determine the number of moles of CHES required relative to the isocyanate functionality. For example, if 1 g of a polyisocyanate contains 4 mmol of -NCO groups, weigh 4 mmol (approximately 1.03 g) of CHES.\n   - **Dissolve CHES**: Dissolve CHES in DMF or DMSO in a dry reaction flask. Use enough solvent to create a homogenous solution (10-20 mL per gram of CHES). If necessary, gentle heating (~40\u201350\u00b0C) can assist dissolution.\n   - **Neutralize pH (optional)**: If the sulfonic acid group interferes with reactivity, consider neutralizing it with a base like triethylamine to its sulfonate (R-SO\u2083\u207b) form before reaction.\n\n#### (2) **Preparation of Polyisocyanate Solution**:\n   - **Dry the polyisocyanate**: Remove any moisture from the polyisocyanate by vacuum drying or storing it over desiccant in a dry container.\n   - **Weigh the polyisocyanate**: Quantify the amount needed based on the molar ratio desired.\n   - **Dissolve in solvent**: Add the polyisocyanate to DMF or DMSO to form a solution. Stir gently under an inert nitrogen atmosphere to prevent moisture absorption.\n\n#### (3) **Reaction Setup**:\n   - Combine the CHES and polyisocyanate solutions in a round-bottom flask equipped with a magnetic stir bar. Ensure the reaction is performed under an inert atmosphere (e.g., nitrogen or argon) to avoid isocyanate degradation.\n   - Add a catalytic amount of DBTDL or triethylamine (0.1\u20130.5% molar relative to isocyanate groups) if necessary to enhance reaction rates.\n   - Stir the mixture continuously.\n\n#### (4) **Reaction Conditions**:\n   - **Temperature Control**: Slowly raise the temperature to 50\u201370\u00b0C (optimal range). Ensure the reaction temperature does not exceed 80\u00b0C to prevent side reactions (e.g., isocyanate dimerization or trimerization, or thermal breakdown of CHES).\n   - **Reaction Time**: Allow the reaction to proceed for 8\u201312 hours. Continuously monitor the progress using Fourier-transform infrared spectroscopy (FTIR) to track the disappearance of the -N=C=O stretching band at ~2270 cm\u207b\u00b9 and the appearance of urea carbonyl (-C=O) stretching near 1640\u20131660 cm\u207b\u00b9.\n\n#### (5) **Post-Reaction Workup**:\n   - Cool the reaction mixture to room temperature.\n   - Precipitate the polymer by adding the reaction mixture into a large excess of a nonsolvent like diethyl ether or methanol.\n   - Wash the precipitated polymer thoroughly to remove residual solvent and unreacted CHES.\n   - Dry the polymer under vacuum at 40\u201350\u00b0C to remove any remaining solvent.\n\n---\n\n### Step 4: **Monitoring and Optimization**\n#### Key parameters to monitor:\n1. **Molar Ratios**: Ensure stoichiometry between CHES and polyisocyanate is balanced. Under-stoichiometric CHES leads to incomplete hydrophilicity; excess CHES can impede crosslinking.\n2. **Temperature**: Keep the reaction temperature stable to avoid side reactions or isocyanate degradation.\n3. **Moisture Control**: Isocyanates are highly reactive with water, leading to undesirable urea formation or foaming.\n4. **Reaction Progress**: Track the disappearance of isocyanate groups using FTIR.\n5. **Polymer Properties**: Analyze the final polymer (e.g., hydrophilicity via contact angle measurement, molecular weight via gel permeation chromatography [GPC], and chemical structure via NMR or FTIR).\n\n---\n\n### Step 5: **Final Remarks**\nThis experimental procedure ensures that the hydrophilic CHES is covalently attached to the polyisocyanate backbone to enhance the polymer's water affinity. By carefully controlling the reaction conditions and monitoring key parameters, you should be able to prepare a functionalized polymer with excellent hydrophilicity tailored to your application.\n\nWould you like me to explain the underlying reaction mechanisms (e.g., urea formation) or assist with troubleshooting potential challenges during this synthesis?"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe how you would verify that adipic acid dihydrazide has been successfully incorporated into a polymer to enhance its hydrophilicity. What specific analytical techniques would you use, and what results would you expect?"}, {"role": "assistant", "content": "Certainly, let\u2019s carefully analyze and systematically address your question.\n\n---\n\n### **Key Points to Analyze:**\n1. **Objective**: Verify the incorporation of adipic acid dihydrazide (AADH) into a polymer.\n2. **Rationale**: AADH is a hydrophilic functional group, and its successful incorporation into the polymer backbone or side chain is expected to enhance the hydrophilicity of the polymer.\n3. **Focus**: Use appropriate analytical techniques to confirm the successful incorporation of AADH into the polymer matrix.\n4. **Expected Outcome**: Identify key signatures (structural confirmation, compositional data, and hydrophilicity measurements) that verify AADH's presence and its impact on polymer properties.\n\n---\n\n### **Systematic Approach to Verification Using Analytical Techniques**\n\n#### **Step 1: Structural Confirmation (Chemical Bond Analysis)**\n**Objective**: Identify characteristic chemical groups of AADH (e.g., hydrazide groups, amide-like bonds) in the polymer structure.\n\n1. **FTIR (Fourier Transform Infrared Spectroscopy)**:\n   - **Purpose**: Confirm the presence of functional groups characteristic of AADH in the polymer.\n   - **Key Features to Look For**:\n     - **N\u2013H stretching vibrations**: A broad peak around 3200\u20133500 cm\u207b\u00b9 (characteristic of amine groups).\n     - **C=O stretching vibrations**: Carbonyl peaks near 1640\u20131700 cm\u207b\u00b9 in the amide region, indicative of the hydrazide group.\n     - **N\u2013N stretching**: Hydrazide-specific peaks in the range of 1000\u20131150 cm\u207b\u00b9.\n   - **Comparison**: Compare the FTIR spectrum of the modified polymer with the spectra of the base polymer and pure AADH. The emergence of new absorption bands corresponding to AADH groups indicates successful incorporation.\n\n2. **NMR (Nuclear Magnetic Resonance Spectroscopy)**:\n   - **Purpose**: Identify chemical shifts corresponding to the hydrogen and carbon atoms in the AADH structure.\n   - **Key Regions in \u00b9H NMR**:\n     - Proton peaks of the N\u2013H group (broad signal around 7\u20138 ppm, depending on hydrogen bonding).\n     - Incorporation of aliphatic protons from the AADH chain can give rise to peaks around 1.2\u20132.4 ppm.\n   - **Key Regions in \u00b9\u00b3C NMR**:\n     - Carbonyl carbons of AADH would appear in the range of 160\u2013180 ppm.\n   - **Expected Outcome**: Clear signals in both spectra corresponding to AADH indicate its presence in the polymer matrix.\n\n3. **XPS (X-ray Photoelectron Spectroscopy)**:\n   - **Purpose**: Provide elemental and bonding information on the polymer surface.\n   - **Analysis**: Look for nitrogen content (N 1s peak) from the hydrazide group. Deconvolution of N 1s and C 1s peaks can reveal the presence of specific bonding environments (e.g., C\u2013N, N\u2013N).\n\n---\n\n#### **Step 2: Quantification of Incorporation**\n**Objective**: Estimate the extent of AADH incorporation into the polymer.\n\n1. **Elemental Analysis (EA)**:\n   - **Purpose**: Quantify nitrogen and other elemental contents in the polymer (indicating AADH incorporation).\n   - **Comparison**: Compare nitrogen content before and after AADH modification. A significant increase in nitrogen indicates AADH incorporation.\n\n2. **Titration Method** (if applicable):\n   - If reactive hydrazide end-groups remain in the polymer, these can be quantified through titrimetric analysis using aldehydes (e.g., formaldehyde).\n\n3. **GPC (Gel Permeation Chromatography)**:\n   - **Purpose**: Assess changes in molecular weight distribution after polymer functionalization.\n   - **Expected Outcome**: An increase in molecular weight or polydispersity index (PDI) indicates successful modification. However, ensure that the reaction conditions do not lead to polymer degradation or crosslinking.\n\n---\n\n#### **Step 3: Verification of Enhanced Hydrophilicity**\n**Objective**: Confirm that AADH\u2019s incorporation improves the polymer's hydrophilic nature.\n\n1. **Water Contact Angle (WCA)**:\n   - **Purpose**: Measure the surface wettability of the polymer.\n   - **Expected Outcome**: A lower water contact angle after modification indicates improved hydrophilicity due to the incorporation of polar AADH groups.\n\n2. **Swelling Behavior**:\n   - **Experiment**: Immerse the polymer in water or a hydrophilic solvent and measure the swelling ratio.\n   - **Expected Outcome**: Increased swelling capacity of the polymer due to improved water absorption.\n\n3. **Zeta Potential (if relevant)**:\n   - **Purpose**: Measure the polymer surface charge in aqueous solution.\n   - **Expected Outcome**: A more negative surface potential may indicate the presence of polar groups (from AADH) enhancing hydrophilicity.\n\n4. **DSC (Differential Scanning Calorimetry)**:\n   - **Purpose**: Assess changes in thermal properties due to AADH incorporation.\n   - **Expected Outcome**: An increase in the glass transition temperature (Tg) may result from the introduction of hydrogen-bonding groups, which restrict polymer chain mobility.\n\n---\n\n### **Integration of Results**\n\nBy combining the results from the above techniques, systematic confirmation of AADH incorporation can be achieved:\n- **Structural Evidence**: FTIR, NMR, and XPS provide direct evidence of AADH linkage in the polymer.\n- **Compositional Evidence**: Elemental analysis and GPC quantify the extent of functionalization.\n- **Property Enhancement**: Hydrophilicity tests (e.g., WCA, swelling) validate functional improvement.\n\n---\n\n### **Expected Results and Discussion**\n1. **FTIR/NMR/XPS Analysis**: New peaks corresponding to AADH functional groups.\n2. **EA/GPC/Quantification**: Increased nitrogen content and possibly higher molecular weight after modification.\n3. **Hydrophilicity Tests**: Lower contact angle, increased swelling ratio, confirming improved hydrophilicity.\n\nBy systematically leveraging these methods, we can conclusively verify AADH incorporation and its effects on polymer hydrophilicity.\n\n"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "When using Carboxy-Functionalized Polyhedral Oligomeric Silsesquioxane (POSS-C), explain how changing the number of ethylene glycol (e.g., n=1 to n=6) repeating units could affect the hydrophilicity of the modified polymer."}, {"role": "assistant", "content": "Let us carefully analyze and systematically address your question.\n\n### **1. Analysis of the Question and Key Points**\nYour query seeks to explore the relationship between **ethylene glycol (EG) chain length** (i.e., number of repeating EG units, denoted as \\( n \\)) and the **hydrophilicity of a modified polymer** synthesized using Carboxy-Functionalized Polyhedral Oligomeric Silsesquioxane (POSS-C). Specifically, you are asking how varying \\( n \\) (from 1 to 6) influences the hydrophilic properties of the resulting polymer.\n\nTo fully address this question, we need to:\n- Provide a systematic explanation for why ethylene glycol contributes to hydrophilicity.\n- Examine trends in hydrophilicity as \\( n \\) increases (from \\( n=1 \\) to \\( n=6 \\)).\n- Tie these effects specifically to the POSS-C-based polymer.\n\n---\n\n### **2. Answer: Detailed and Systematic Explanation**\n\n#### **Step-by-step Synthesis Process of the Hydrophilic Polymer**\nTo study the effect of ethylene glycol chain length on the hydrophilicity of POSS-C-derived polymers, we propose a synthetic approach that incorporates ethylene glycol of varying lengths (e.g., \\( HO-(CH_2CH_2O)_n-H \\)) into the POSS-C framework. Here is a step-by-step experimental scheme:\n\n---\n\n#### **Step 1: Preparation of Methacrylate-Terminated POSS (Intermediate)**\n**Rationale:** To enhance compatibility and reactivity with ethylene glycol derivatives, POSS-C is often functionalized with polymerizable methacrylate groups. This step involves esterification of the carboxylic acid groups in POSS-C.\n\n**Reaction:**\n\\[ \\text{POSS-C} + \\text{Methacrylic Anhydride} \\xrightarrow{\\text{Catalyst (DMAP)}} \\text{Methacrylate-POSS (POSS-MA)} \\]\n\n- **Reagents:**\n  - Starting material: POSS-C (1.0 equivalent, typically in dry THF for solubility).\n  - Methacrylic anhydride (around 1.2 equivalents to ensure complete esterification).\n  - Catalyst: 4-Dimethylaminopyridine (DMAP, ~0.1 equivalent) to promote esterification.\n  - Solvent: Tetrahydrofuran (THF, anhydrous).\n\n- **Conditions:**\n  - Reaction temperature: 50\u201360\u00b0C.\n  - Reaction time: ~12\u201316 hours under stirring.\n  - Nitrogen atmosphere: To prevent polymerization of methacrylate under oxygen.\n\n- **Workup:**\n  - Purify the product via solvent evaporation and precipitation in methanol.\n  - Characterize the POSS-MA using FTIR or NMR (ensure disappearance of carboxylic acid signal and appearance of ester bonds).\n\n---\n\n#### **Step 2: Grafting Ethylene Glycol Chains of Varying Length**\n**Rationale:** Incorporation of ethylene glycol derivatives into the polymer enhances hydrophilicity due to the excellent water affinity of the EG moieties (via hydrogen bonding). The oligomers \\( HO-(CH_2CH_2O)_n-H \\) are reacted with POSS-MA to form polymerizable macromonomers.\n\n**Reaction:**\n\\[ \\text{POSS-MA} + HO-(CH_2CH_2O)_n-H \\xrightarrow{\\text{Catalyst (e.g., acid or base)}} \\text{POSS-grafted-EG} \\]\n\n- **Reagents:**\n  - POSS-MA (1.0 equivalent).\n  - Ethylene glycol oligomer (\\( HO-(CH_2CH_2O)_n-H \\), n varies from 1 to 6, 1.2 equivalents depending on desired grafting density).\n  - Catalyst: Acid (e.g., p-toluenesulfonic acid) if using esterification, or base (e.g., TBD or DBU) if using transesterification.\n\n- **Conditions:**\n  - Solvent: Typically use toluene or THF (ensure anhydrous conditions).\n  - Reaction temperature: 40\u201360\u00b0C.\n  - Reaction time: ~6 hours.\n\n- **Workup:**\n  - Remove unreacted ethylene glycol oligomer by dialysis or precipitation in hexane.\n  - Confirm grafting by characterizing via FTIR (EG signature peaks) and GPC (verify molecular weight increase).\n\n---\n\n#### **Step 3: Polymerization to Form Hydrophilic Polymer**\n**Rationale:** The POSS-grafted macromonomer obtained in Step 2 (with \\( n=1 \\) to \\( n=6 \\)) is polymerized to produce the final hydrophilic polymer.\n\n**Reaction:**\n\\[ n[\\text{POSS-grafted-EG}] \\xrightarrow{\\text{Free Radical Polymerization (Initiator)}} \\text{Hydrophilic POSS-Polymer.} \\]\n\n- **Reagents:**\n  - POSS-grafted macromonomer (variable molecular weight depending on \\( n \\)).\n  - Initiator: Azobisisobutyronitrile (AIBN, ~1 wt.%).\n  - Solvent: Anhydrous DMSO (for solubility of both hydrophobic and hydrophilic components).\n\n- **Conditions:**\n  - Polymerization temperature: ~70\u00b0C under nitrogen.\n  - Reaction time: ~24 hours.\n\n- **Workup:**\n  - Precipitate the polymer in cold diethyl ether.\n  - Dry under vacuum.\n\n---\n\n### **3. Relationship Between Ethylene Glycol Chain Length and Hydrophilicity**\nOnce the polymer is synthesized, the chain length of ethylene glycol (\\( n \\)) significantly influences the hydrophilicity of the resulting material. Here's how:\n\n1. **Hydrogen Bonding Capacity:**\n   - As \\( n \\) increases, the number of ether oxygen atoms (-O-) and hydroxyl terminals contributing to hydrogen bonding with water molecules also increases.\n   - This enhances the hydration layer around the polymer in aqueous systems, improving hydrophilicity.\n\n2. **Water Solubility:**\n   - Short EG chains (\\( n=1 \\) or 2) may not provide sufficient hydrophilicity for full water solubility. As \\( n \\) increases, the polymer becomes increasingly water-soluble due to a greater density of hydrophilic groups.\n\n3. **Hydrophilic-Hydrophobic Balance:**\n   - At smaller \\( n \\), the POSS structure (which is relatively hydrophobic) dominates in terms of physical behavior.\n   - Larger \\( n \\) ensures that the ethylene glycol units counterbalance POSS\u2019s hydrophobicity, yielding a more hydrophilic material.\n\n4. **Applications Tuning:**\n   - **Short EG Chains (\\( n=1\u20132 \\)):** Better for applications requiring amphiphilic behavior (e.g., emulsion stabilization or coatings).\n   - **Long EG Chains (\\( n=4\u20136 \\)):** Better for highly hydrophilic applications (e.g., hydrogels, water purification membranes, drug delivery vehicles).\n\n---\n\n### **4. Experimental Validation**\nTo experimentally confirm the hydrophilicity as a function of \\( n \\):\n- **Contact Angle Measurement:** Lower values indicate higher hydrophilicity.\n- **Water Absorption Test:** Measure the water uptake percentage for films or crosslinked samples.\n- **Swelling Behavior:** Monitor equilibrium swelling ratio in water for crosslinked materials.\n- **Thermogravimetric Analysis (TGA):** Thermal stability may slightly decrease with increasing \\( n \\) due to the higher organic content (EG chains).\n\n---\n\n### **5. Conclusion**\nBy increasing the number of EG repeating units (\\( n \\)), the hydrophilicity of the POSS-C-based polymer is systematically enhanced due to increased hydrogen bonding and water affinity. This tunable hydrophilicity is key for designing materials tailored for specific applications like hydrogels, coatings, or biomaterials."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe how you would utilize 3-(trimethoxysilyl)propyl methacrylate (TMSPMA) to create a polymer solution suitable for application onto a substrate, while maintaining its ability to crosslink during curing."}, {"role": "assistant", "content": "To address your question and to construct a well-prepared experimental preparation scheme for using 3-(trimethoxysilyl)propyl methacrylate (TMSPMA) to create a polymer solution suitable for application onto a substrate, while maintaining its ability to crosslink during curing, let us systematically break it down step by step. TMSPMA is an organosilane monomer with both methacrylate functionality (capable of free radical polymerization) and silane groups (capable of hydrolysis and subsequent condensation reactions). By leveraging these functionalities, we can prepare a hydrophilic, crosslinkable polymer solution.\n\n---\n\n### Key Points to Address:\n1. **Use of TMSPMA**: It contains a methacrylate group for free-radical polymerization and hydrolyzable trimethoxysilane groups that allow crosslinking.\n2. **Preparation of Solution**: The solution should be prepared to optimize its hydrophilic properties for application onto a substrate.\n3. **Crosslinking Capability**: Ensure the silane groups retain their reactivity for hydrolysis and condensation, which will enable crosslinking post-application and curing.\n\n---\n\n### Experimental Preparation Scheme:\n\n#### **Step 1: Selection of Solvent (Preparation of the Polymer Solution)**\nA suitable solvent must be selected to dissolve TMSPMA and maintain reaction stability. Commonly used solvents are ethanol, methanol, or a mixture of ethanol/water. Ethanol is a preferred choice since it improves solubility of TMSPMA and is compatible with hydrolysis of the silane groups.\n\n- **Reagents**:\n  - TMSPMA: 10 g (example weight, can be adjusted depending on intended polymer concentration).\n  - Ethanol: Enough to prepare a 10-20% (w/v) solution of TMSPMA in ethanol.\n  - DI Water: 3-5% by volume relative to the ethanol to enable controlled hydrolysis of the silane groups.\n\n- **Procedure**:\n  1. Add ethanol to a clean reaction vessel.\n  2. Gradually add TMSPMA to ethanol with gentle stirring to dissolve completely.\n  3. Add DI water dropwise to initiate partial hydrolysis of the trimethoxysilane groups.\n\n---\n\n#### **Step 2: Catalyst Addition for Controlled Hydrolysis**\nSince the trimethoxysilane groups of TMSPMA undergo hydrolysis (producing silanol groups) before condensation, a small amount of acid catalyst is necessary to promote this step.\n\n- **Reagents**:\n  - Glacial acetic acid (or dilute HCl): ~0.1-0.5 wt% relative to TMSPMA.\n\n- **Procedure**:\n  1. Add glacial acetic acid dropwise to the prepared TMSPMA-ethanol-water solution under mild stirring.\n  2. Continue stirring the mixture at room temperature for 30\u201360 minutes. The resulting solution contains hydrolyzed silanol groups, ensuring the TMSPMA remains in a crosslinkable state.\n\n**Notes**: Avoid prolonged hydrolysis or high water content, which might prematurely polymerize or gel the system.\n\n---\n\n#### **Step 3: Polymerization (Optional Step, if Pre-polymer Desired)**\nIf a partially polymerized (oligomeric) structure is desired before applying to the substrate, radical polymerization can be initiated.\n\n- **Reagents**:\n  - TMSPMA solution (prepared in Step 2).\n  - Azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO): ~0.5\u20131.0 wt% relative to TMSPMA.\n  - Appropriate solvent (ethanol works well).\n\n- **Procedure**:\n  1. Transfer the TMSPMA solution to a sealed glass reactor.\n  2. Add the initiator (AIBN or BPO) to the solution and stir gently.\n  3. Heat the solution to 60\u201370\u00b0C under an inert nitrogen atmosphere to initiate polymerization.\n  4. Monitor viscosity to stop the reaction at a desired oligomerization stage (to avoid fully polymerized gel formation).\n\n---\n\n#### **Step 4: Application onto a Substrate**\nAfter preparing the polymer solution or oligomer, it is applied onto the desired substrate.\n\n- **Procedure**: \n  1. Clean the substrate thoroughly using solvents (e.g., ethanol) to remove contaminants.\n  2. Coat the substrate with the TMSPMA solution using spin coating, dip coating, or spray coating, depending on the application.\n  3. Allow the solvent to evaporate at room temperature, forming a thin film.\n\n---\n\n#### **Step 5: Curing (Crosslinking Step)**\nThe final curing step ensures crosslinking between hydrolyzed silanol groups, forming a robust siloxane network.\n\n- **Conditions**:\n  - Humidity: Maintain a relative humidity of 50\u201370% during curing to promote condensation.\n  - Temperature: Cure at ~100\u2013120\u00b0C for 2\u20133 hours to facilitate complete siloxane bonding.\n\n---\n\n#### **Step 6: Characterization and Hydrophilicity Testing**\nOnce cured, the hydrophilicity of the film can be determined using contact angle measurements (lower contact angles indicate higher hydrophilicity). Additional characterization using FTIR can confirm crosslinking (siloxane bonds).\n\n---\n\n### Important Notes:\n1. The level of hydrolysis must be controlled to avoid premature gelling of the solution.\n2. Proper storage of the polymer solution (if not used immediately) is critical, ideally under an inert atmosphere to prevent unwanted reactions.\n3. Adjust solvent ratios or reaction conditions as per specific requirements for hydrophilicity and substrate compatibility.\n\nBy following these steps, you will have a TMSPMA-derived polymer solution that is hydrophilic, suitable for substrate application, and capable of crosslinking during curing."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe how the addition of hydrogen peroxide (H2O2) might interact with the electrodeposition process of chitosan and influence the structural parameters such as pore size, porosity, and overall hydrophilicity of the resulting polymer."}, {"role": "assistant", "content": "To adequately address your question on how the addition of hydrogen peroxide (H\u2082O\u2082) might interact with the electrodeposition process of chitosan and influence the structural parameters, including pore size, porosity, and overall hydrophilicity of the resulting polymer, let us proceed step by step, adhering to the outlined requirements for a systematic, detailed, and rigorous explanation. \n\n---\n\n### **Step 1: Analyze the Question and Key Points**\n1. **Understanding the Role of Hydrogen Peroxide (H\u2082O\u2082):**\n   Hydrogen peroxide is a mild oxidative agent. Its addition can introduce hydroxyl radicals (\u2022OH) and alter the ionic environment during electrodeposition processes. Therefore, it can impact the cross-linking density, pore formation, and surface chemistry of polymers like chitosan.\n   \n2. **Electrodeposition of Chitosan:**\n   Chitosan is a pH-responsive polysaccharide that can be electrodeposited on a substrate by taking advantage of its solubility at low pH. Under an applied electric field, chitosan undergoes deprotonation, gelation, and deposition on the electrode.\n\n3. **Structural Parameters of Interest:**\n   - **Pore Size:** Controlled by reaction kinetics and the interplay between coagulants and solvents.\n   - **Porosity:** Dictated by the deposition dynamics and potential cross-linking interactions between hydrogen peroxide and chitosan.\n   - **Hydrophilicity:** Dependent on the surface chemistry, oxidation states, and introduction of functional groups (e.g., hydroxyl groups).\n\n### **Step 2: Systematic Answer with Detailed Experimental Preparation Scheme**\n\nTo better understand the effects of adding H\u2082O\u2082, I will outline a step-by-step experimental preparation scheme for the electrodeposition of chitosan with hydrogen peroxide. Each step includes relevant conditions and expected outcomes.\n\n---\n\n### **Experimental Scheme: Electrodeposition of Chitosan in the Presence of Hydrogen Peroxide**\n\n#### Step 1: **Preparation of Chitosan Solution**\n1. **Reagents:**\n   - Chitosan: High molecular weight (>70% deacetylation) is preferred.\n   - Acetic acid (glacial): 1% (v/v) solution used as a solvent to dissolve chitosan.\n   - Hydrogen peroxide (H\u2082O\u2082): 30% stock solution.\n\n2. **Procedure:**\n   - Dissolve chitosan in a 1% acetic acid solution to obtain a 1-2% (w/v) solution. Stir the solution for 12 hours to ensure complete dissolution.\n   - After complete dissolution, adjust the pH to ~5.0 using sodium hydroxide (NaOH), as chitosan is soluble at acidic pH but precipitates at higher pH values.\n   - Add 1-10 mM hydrogen peroxide to the chitosan solution and mix gently for another 30 minutes. The exact concentration of H\u2082O\u2082 can be varied to study its effects on the polymer structure (discussed below).\n\n---\n\n#### Step 2: **Electrodeposition of Chitosan**\n1. **Setup:**\n   - Use a two-electrode configuration:\n     - Cathode: Conducting substrate (e.g., stainless steel or indium tin oxide, ITO glass).\n     - Anode: Platinum or graphite electrode.\n   - Power Supply: Constant voltage or current source, capable of applying voltages in the range of 1-3 V.\n\n2. **Procedure:**\n   - Submerge the electrodes in the chitosan solution (prepared above) with hydrogen peroxide.\n   - Apply a constant voltage (e.g., 2 V) for 5-10 minutes to precipitate chitosan on the cathode. During electrodeposition, chitosan is locally deprotonated near the electrode surface, forming a hydrogel-based film.\n\n   **Expected Role of Hydrogen Peroxide:**\n   - The presence of H\u2082O\u2082 introduces mild oxidative stress, which can:\n     - Generate hydroxyl radicals (\u2022OH) that react with the amino and hydroxyl groups of chitosan.\n     - Modify the gelation process, potentially resulting in looser cross-linking and enhanced porosity.\n     - Promote interactions between chitosan chains, introducing new hydroxyl-rich groups that enhance hydrophilicity.\n\n---\n\n#### Step 3: **Post-Treatment and Cross-Linking**\n1. **Reagents:**\n   - Sodium tripolyphosphate (TPP) as a cross-linking agent (optional), used to further stabilize the chitosan film.\n   - PBS (phosphate-buffered saline) to wash the deposited polymer.\n\n2. **Procedure:** \n   - After electrodeposition, carefully rinse the substrate with PBS to remove unbound chitosan and residual acetic acid.\n   - Optionally, immerse the substrate in a 1-2% (w/v) TPP solution for 10 minutes to cross-link the deposited chitosan. This step can enhance mechanical stability but could reduce porosity slightly.\n\n   **Expected Role of Hydrogen Peroxide:**\n   - Hydrogen peroxide can oxidize certain functional groups, which may lead to the introduction of carbonyl and carboxyl groups, further increasing hydrophilicity.\n\n---\n\n#### Step 4: **Characterization of the Polymer Film**\nConduct a detailed examination of the structural and hydrophilic properties of the resulting film.\n\n1. **Pore Size and Porosity:**\n   - Use scanning electron microscopy (SEM) or atomic force microscopy (AFM) to analyze the surface morphology and determine the pore size and porosity.\n   - Hydrogen peroxide's oxidative interactions with chitosan and its influence on hydrodynamic deposition rates are expected to increase pore size and porosity.\n\n2. **Hydrophilicity:**\n   - Measure the water contact angle (WCA). A lower WCA indicates higher hydrophilicity.\n   - Hydrogen peroxide is anticipated to introduce hydroxyl-rich oxidized functional groups, reducing the WCA and increasing compatibility with aqueous environments.\n\n3. **Chemical Composition:**\n   - Conduct Fourier-transform infrared spectroscopy (FTIR) to identify new functional groups formed due to H\u2082O\u2082 interaction.\n   - Peaks corresponding to hydroxyl (-OH) and carbonyl (-C=O) groups should become more prominent in the presence of H\u2082O\u2082.\n\n4. **Mechanical Stability and Swelling Behavior:**\n   - Perform swelling studies in aqueous media to assess the hydrophilicity and porosity.\n   - Films prepared with higher H\u2082O\u2082 concentrations may show increased swelling due to reduced cross-linking density.\n\n---\n\n### **Step 3: Analysis of Effects**\n\n1. **Pore Size:** In the presence of H\u2082O\u2082, pore size is expected to increase due to altered gelation dynamics and reduced ion-driven cohesion between chitosan chains.\n\n2. **Porosity:** Porosity will also increase because H\u2082O\u2082 generates hydroxyl radicals that disrupt the compactness of the deposited polymer network.\n\n3. **Hydrophilicity:** Hydrophilicity is enhanced due to the oxidative modification of chitosan chains, with the formation of hydroxyl and carboxyl groups contributing to water affinity.\n\n### **Step 4: Variations and Optimization**\n\nYou can vary the concentration of H\u2082O\u2082 (1\u201310 mM) to observe its impact systematically. At lower concentrations (e.g., 2 mM), structural changes may be less pronounced, while higher concentrations (e.g., 10 mM) may result in excessive oxidation and weaker mechanical integrity.\n\n---\n\n### **Conclusion**\nThe addition of hydrogen peroxide to the electrodeposition process of chitosan plays a crucial role in tuning the pore structure, porosity, and hydrophilicity of the resulting polymer. By optimizing the experimental parameters (e.g., H\u2082O\u2082 concentration, voltage, and deposition time), you can create a highly hydrophilic, porous polymer film tailored for applications such as drug delivery, biosensors, or tissue engineering scaffolds."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Design an experimental procedure to use '\u4e19\u70ef\u9170\u80fa\u57fa-\u53d4\u4e01\u57fa\u78fa\u9178\u94be\u76d0' in the preparation of a hydrophilic polymer. Include details on how this molecule contributes to the overall hydrophilicity enhancement."}, {"role": "assistant", "content": "Certainly! Thank you for bringing up this intriguing question regarding the use of '\u4e19\u70ef\u9170\u80fa\u57fa-\u53d4\u4e01\u57fa\u78fa\u9178\u94be\u76d0' (potassium acrylamide-based tert-butyl sulfonate) in the synthesis of a hydrophilic polymer. This molecule, with its distinctive structural design, has great potential for enhancing hydrophilicity due to the strong ionic character of the sulfonate group and the amide functionalities. Let us approach this systematically.\n\n---\n\n### Key Points Analysis\n1. **Objective**: Develop an experimental procedure to synthesize a hydrophilic polymer using '\u4e19\u70ef\u9170\u80fa\u57fa-\u53d4\u4e01\u57fa\u78fa\u9178\u94be\u76d0.'\n2. **Hydrophilicity Contributions from the Monomer**:\n   - **Amide Functional Groups**: Promote hydrogen bonding with water molecules.\n   - **Sulfonate Group (-SO\u2083\u207b)**: Strongly ionic and contributes significantly to water solubility and electrostatic interactions with water.\n3. **Synthetic Approach**: Design a polymerization scheme using this monomer, likely via free radical polymerization due to the presence of the acrylamide functional group. Consider supplemental monomers for copolymer formation if further structural or functional tuning is desired.\n\n---\n\n### Detailed and Systematic Experimental Procedure: Free Radical Polymerization\n\n#### 1. **Materials and Equipment**\n   - **Key Monomer**: \u4e19\u70ef\u9170\u80fa\u57fa-\u53d4\u4e01\u57fa\u78fa\u9178\u94be\u76d0 (provided by student).\n   - **Initiator**: Potassium persulfate (K\u2082S\u2082O\u2088) for aqueous polymerization or azobisisobutyronitrile (AIBN) for organic solvent-based polymerization.\n   - **Crosslinker**: N,N'-methylenebisacrylamide (to create hydrophilic gels, optional).\n   - **Solvent**: Deionized water (preferred for hydrophilic polymerization, unless the monomer requires organic solvents like dimethyl sulfoxide (DMSO)).\n   - **pH Adjusting Agent**: Dilute sodium hydroxide or sulfuric acid.\n   - **Nitrogen Gas**: For purge to remove oxygen during the reaction.\n   - Additional support equipment: Magnetic stirrer, reaction vessel with lid, UV/IR lamp (if photopolymerization is chosen), thermo-regulated water bath (for controlled temperature).\n\n---\n\n#### 2. **Experimental Design**\n\n##### **Step 1: Reaction Setup**\n   - Prepare a reaction vessel and ensure it is clean and oxygen-free.\n   - Add deionized water (50\u2013100 mL per gram of monomer) to the flask as the solvent. Adjust parameters depending on required polymer concentration.\n\n##### **Step 2: Monomer Preparation**\n   - Accurately weigh the monomer: typically, 0.5\u20132 g of \u4e19\u70ef\u9170\u80fa\u57fa-\u53d4\u4e01\u57fa\u78fa\u9178\u94be\u76d0 depending on desired polymer yield.\n   - Dissolve the monomer in the solvent under constant stirring to ensure complete dissolution. The strong ionic nature will typically allow for easy solubility in water.\n\n##### **Step 3: Initiator Addition**\n   - Prepare the initiator solution: Dissolve an appropriate amount of potassium persulfate (~0.01\u20130.1 g per gram of monomer) in deionized water.\n   - Add the initiator solution dropwise to the reaction solution under stirring to ensure uniform distribution.\n\n##### **Step 4: pH Adjustment (Optional based on monomer chemistry)**\n   - If necessary, adjust the pH of the reaction to optimize polymerization kinetics. The optimal pH for acrylamide-based systems is typically neutral to slightly acidic (pH 6\u20137). Use dilute NaOH or HCl to achieve this.\n\n##### **Step 5: Oxygen Purge**\n   - Purge the system with nitrogen gas for 10\u201315 minutes. Oxygen can inhibit free radical polymerization reactions.\n\n---\n\n##### **Step 6: Reaction Conditions**\n   - **Temperatures**: 60\u201375\u00b0C for potassium persulfate, or ~65\u00b0C for AIBN if using organic solvents.\n   - Stirring Rate: Approximately 300\u2013500 rpm for homogeneous mixing.\n   - Reaction Duration: 4\u20136 hours, or until polymerization is complete (monitor viscosity or turbidity increases).\n\n##### **Step 7: Crosslinking (Optional)**\n   - If forming crosslinked hydrogels, add N,N'-methylenebisacrylamide (~0.1\u20130.5% of total monomer mass) during the reaction. Ensure thorough mixing.\n\n---\n\n##### **Step 8: Polymer Purification**\n   - After completion of polymerization, remove non-reacted monomers and impurities via dialysis or repeated washing with deionized water.\n   - To precipitate and isolate the polymer, perform solvent exchange (e.g., precipitate in ethanol or acetone if needed).\n\n---\n\n#### 3. **Characterization of the Synthesized Polymer**\n   - **Hydrophilicity Testing**: Measure water contact angle of polymer films to confirm enhanced hydrophilicity.\n   - **Molecular Weight Analysis**: Conduct gel permeation chromatography (GPC).\n   - **Functional Group Verification**: FTIR spectroscopy to confirm retention of sulfonate and amide groups.\n   - **Thermal Stability**: Perform thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC).\n\n---\n\n### Hydrophilicity Enhancement via \u4e19\u70ef\u9170\u80fa\u57fa-\u53d4\u4e01\u57fa\u78fa\u9178\u94be\u76d0\nThe molecule provides hydrophilicity primarily through:\n1. **Amide Groups**: Contribute to hydrogen bonding, increasing water affinity.\n2. **Sulfonate Ionic Groups**: Strong electrostatic interactions with water molecules, making the polymer highly water-absorptive and hydrophilic.\n\nDepending on the application, this polymer can be ideal for water-retentive membranes, superabsorbent hydrogels, or coatings for biomedical devices.\n\n---\n\n### Conclusion\nBy following the above systematic procedure, students can successfully synthesize the hydrophilic polymer using \u4e19\u70ef\u9170\u80fa\u57fa-\u53d4\u4e01\u57fa\u78fa\u9178\u94be\u76d0. The detailed stepwise account ensures the experiment's reproducibility and facilitates the understanding of key mechanisms involved in hydrophilicity enhancement. Let me know if you need any additional clarification or adjustments for specific applications!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain how you would control the addition of alcohol over time during the synthesis process when IPDI is used as a reactant, and detail how this step contributes to enhancing the hydrophilicity of the polymer material."}, {"role": "assistant", "content": "To address your question comprehensively and systematically, let's break the problem into its core components: the role of IPDI (isophorone diisocyanate) in the polymer synthesis, the controlled addition of alcohol as a reactant, the contribution of alcohol addition to enhancing polymer hydrophilicity, and the key parameters necessary for experimental success.\n\n---\n\n### **Step 1: Analyzing the Problem**\n- **Key Reactant:** IPDI is a diisocyanate compound commonly used in the synthesis of urethane polymers. It has two reactive isocyanate functional groups (-NCO), which allow it to react with hydroxyl (-OH) groups in alcohols or other molecules to form urethane linkages.\n- **Main Objective:** The controlled addition of alcohol during the reaction with IPDI, with the intention of modifying the polymer structure to enhance hydrophilicity.\n- **Enhancing Hydrophilicity:** To make the polymer hydrophilic, hydroxyl-functional alcohols or polyols can be used that introduce hydrophilic groups such as hydroxyl (-OH), ether (-O-), or carboxylic acid (-COOH) groups into the polymer backbone or side chains.\n\nThe success of this step depends on controlling reagent addition and reaction kinetics, ensuring an adequate ratio of reactants and achieving a uniform distribution of hydrophilic groups in the polymer matrix.\n\n---\n\n### **Step 2: Detailed Experimental Preparation Scheme**\n\n#### **Materials Required**\n1. **IPDI (Isophorone Diisocyanate):** The diisocyanate reactant.\n2. **Hydrophilic Alcohol or Polyol:** Choose an alcohol with hydrophilic groups (e.g., polyethylene glycol (PEG), glycerol, or 2-hydroxyethyl methacrylate (HEMA)) to enhance hydrophilicity.\n3. **Solvent:** Dimethylformamide (DMF) or acetone may be used as an inert solvent to facilitate mixing and control viscosity.\n4. **Catalyst:** Dibutyltin dilaurate (DBTDL) or another suitable catalyst to accelerate urethane formation.\n5. **Deionized Water:** For post-synthesis purification.\n6. **Nitrogen Gas:** To provide an inert atmosphere and minimize moisture interference, as -NCO groups are reactive toward water.\n\n---\n\n#### **Step 3: Experimental Procedure**\n\n##### **Part A: Pre-Reaction Setup**\n1. **Prepare the Reaction Vessel:** Use a clean, dry, three-necked flask equipped with a mechanical stirrer, thermometer, and addition funnel. Ensure the setup is moisture-free because IPDI reacts with water.\n2. **Inert Atmosphere:** Purge the reaction vessel with nitrogen gas to create an inert environment, preventing unwanted side reactions (e.g., formation of urea due to moisture).\n3. **Prepare Solutions:**\n   - Dissolve IPDI in DMF (or desired solvent) to create a 10\u201320% (w/v) solution.\n   - Prepare the alcohol or polyol solution separately, ensuring accurate concentration (e.g., 20\u201325% w/v), depending on the target molar ratio relative to IPDI.\n\n---\n\n##### **Part B: Controlled Addition of Alcohol**\n1. **Set Reaction Temperature:** Heat the reaction vessel to 60\u201370\u00b0C, maintaining constant stirring (600\u2013800 rpm). This temperature range is optimal for urethane bond formation without spontaneous side reactions.\n2. **Initiate Reaction:** Introduce the catalyst (DBTDL at 0.1\u20130.5 wt%) into the IPDI solution. This step activates the isocyanate groups for reaction with hydroxyl groups.\n3. **Alcohol Addition (Key Step):**\n   - Use an addition funnel to add the alcohol solution dropwise over **3\u20135 hours**. This slow addition is critical to controlling reaction kinetics, preventing local saturation of alcohol, and ensuring uniform polymer chain formation.\n   - Monitor the molar ratio: Target an IPDI-to-alcohol ratio between **1:1 and 1:1.2**, depending on the final hydrophilic polymer design. A slight excess of alcohol guarantees complete reaction of all isocyanate groups and incorporation of hydrophilic functionality.\n   - Maintain stirring during addition to prevent localized concentration spikes and ensure homogeneous polymer formation.\n\n---\n\n##### **Part C: Post-Reaction and Purification**\n1. **Reaction Completion:** After alcohol addition, continue stirring at 60\u201370\u00b0C for an additional 1\u20132 hours to ensure all -NCO groups are fully reacted.\n2. **Neutralization Step:** Carefully add deionized water dropwise if necessary to quench any unreacted -NCO groups without introducing defects.\n3. **Purification:** Precipitate the polymer by pouring the reaction mixture into a nonsolvent (e.g., diethyl ether or hexane). Filter and wash the precipitate with deionized water to remove impurities and unreacted reagents.\n4. **Drying:** Dry the purified polymer under vacuum at 40\u201350\u00b0C to remove residual solvent.\n\n---\n\n### **Step 4: Role of Controlled Addition of Alcohol**\n- **Uniform Distribution:** Slow addition prevents uncontrolled crosslinking or excessive chain termination, resulting in a well-defined polymer structure with hydrophilic segments distributed uniformly.\n- **Hydrophilicity Enhancement:** Alcohol contributes hydrophilic groups (-OH, -O-) that improve water absorption, wetting properties, and overall hydrophilicity of the polymer.\n- **Improved Mechanical Properties:** Controlled addition enhances polymer chain regularity, improving mechanical strength and minimizing defects.\n\n---\n\n### **Step 5: Notes on Reaction Controls**\n1. **Monitoring:** Use FTIR spectroscopy during the reaction to monitor the disappearance of the -NCO peak (around 2270 cm\u207b\u00b9) and the appearance of a urethane peak (around 1680 cm\u207b\u00b9), confirming reaction progress.\n2. **Safety:** Handle IPDI with care in a fume hood and wear appropriate PPE, as it is toxic and moisture-sensitive.\n3. **Optimization:** Lab trials can fine-tune alcohol addition rates to balance hydrophilicity, reaction kinetics, and product yield.\n\n---\n\n### **Conclusion**\nThe controlled addition of alcohol during polymer synthesis with IPDI ensures successful reaction progress and the incorporation of hydrophilic groups, enhancing the hydrophilicity of the final polymer material. By adhering to the outlined methodology \u2014 including reagent preparation, reaction conditions, and purification steps \u2014 students can carry out the synthesis confidently and achieve high-quality materials."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain how you can design an experiment using a molecule capable of forming dynamic cross-links to prepare a hydrophilic polymer with controllable degradability. What factors would you consider to ensure the stability and functionality of the final material?"}, {"role": "assistant", "content": "To answer your question, we will develop a systematic experimental preparation scheme based on the principles of hydrophilic polymer synthesis and the design of materials with dynamic cross-links. This approach will allow us to engineer a hydrophilic polymer with controllable degradability, suitable for various applications such as drug delivery, tissue engineering, or bio-inspired materials.\n\n---\n\n### **Step-by-Step Approach**\n\n#### **Step 1: Key Points of the Question**\n- **Objective:** Design an experiment to synthesize a hydrophilic polymer that incorporates dynamic cross-links for controllable degradability.\n- **Key Considerations:**\n  1. Selection of hydrophilic monomers/polymers to enhance water affinity.\n  2. Incorporation of reversible or dynamic cross-links to introduce degradability.\n  3. Optimization of reaction conditions (solvent, temperature, pH, catalyst, etc.).\n  4. Factors to ensure stability and functionality, such as avoiding premature degradation and maintaining hydrophilic properties.\n\n#### **Step 2: Experimental Scheme Overview**\nTo prepare a hydrophilic polymer with controllable degradability, the experiment will involve:\n1. Selection of base polymer or monomers (hydrophilic).\n2. Functionalization or grafting with dynamic cross-linking groups.\n3. Polymerization process or cross-linking step, followed by purification.\n4. Characterization and testing of hydrophilicity, degradability, and stability.\n\n---\n\n### **Detailed Experimental Preparation Scheme**\n\n#### **Step 3: Selection of Materials**\n1. **Hydrophilic Monomers/Polymers:**\n   - Choose well-known hydrophilic monomers such as acrylamide, polyethylene glycol (PEG), or poly(ethylene oxide) (PEO).\n   - Alternatively, select functionalized hydrophilic molecules like hydroxyl or carboxyl-containing acrylates (e.g., acrylic acid or hydroxyethyl methacrylate).\n\n2. **Dynamic Cross-linking Groups:**\n   - Use molecules capable of forming reversible bonds:\n     - Schiff base chemistry (aldehyde + primary amine).\n     - Disulfide bonds.\n     - Boronic ester bonds (diol + boronic acid).\n     - Hydrogen bonding or ionic interactions (e.g., calcium alginate).\n   - Consider the application conditions: For physiological environments, dynamic bonds that respond to pH or reducing agents are ideal.\n\n---\n\n#### **Step 4: Experimental Procedure**\n##### **A. Preparation of Hydrophilic Polymer Solution**\n1. **Step:** Dissolve the hydrophilic monomer or polymer in a suitable solvent.\n   - Common solvents: Water, ethanol, or an aqueous buffer (pH ~7).\n   - Example ratio: For PEG, prepare a 20 wt% solution.\n2. **Consideration:** Adjust pH to maintain stable cross-linking functionality (e.g., ~pH 7\u20138 for Schiff base reactions).\n\n##### **B. Functionalization of Polymer with Dynamic Cross-linking Groups**\n3. **Step:** Add functional group precursors into the hydrophilic polymer solution to graft dynamic cross-linking moieties. \n   - Example: For aldehyde-amine Schiff base formation, PEG-dialdehyde can be prepared by oxidizing PEG with periodate. Dialdehyde groups can then react with primary amines during cross-linking.\n   - Ratios: Ensure the molar ratio of reactive groups matches the desired cross-linking density (e.g., aldehyde-to-amine molar ratio ~1.2:1 to ensure complete cross-linking).\n\n##### **C. Polymerization or Cross-link Formation**\n4. **Step:** Initiate polymerization or cross-linking under controlled conditions.\n   - Example: For Schiff base cross-linking:\n     - Mix the dialdehyde-grafted hydrophilic polymer with an amine-containing crosslinker (e.g., lysine or polyethyleneimine).\n     - Adjust the molar ratio to control the resulting polymer network density.\n     - Allow the reaction to proceed at room temperature (~20\u201325\u00b0C) for several hours.\n5. **Consideration:** For dynamic bonds, ensure reversibility under target degradation conditions (e.g., Schiff base stability depends on pH; rapid degradation occurs in acidic environments <pH 6).\n\n##### **D. Purification**\n6. **Step:** Remove unreacted reagents via techniques like dialysis or precipitation.\n   - Example: Dialyze the polymer gel in water or buffer for 24\u201348 hours to remove small molecule impurities.\n7. **Consideration:** Verify that dynamic cross-links remain intact after purification.\n\n---\n\n#### **Step 5: Characterization**\nAfter synthesizing the hydrophilic polymer, conduct the following tests:\n1. **Hydrophilicity:**\n   - Evaluate water absorption or swelling properties (e.g., swelling ratio in water).\n   - Measure contact angle (lower values indicate higher hydrophilicity).\n\n2. **Dynamic Cross-linking and Degradability:**\n   - Test the polymer under degradable conditions (e.g., acidic pH for Schiff bases, reducing environments for disulfide bonds).\n   - Measure mass loss over time to quantify degradability.\n\n3. **Stability:**\n   - Confirm that the polymer remains functional under storage conditions (e.g., stability in water at room temperature over weeks).\n   - Use FTIR or NMR spectroscopy to confirm retention of dynamic cross-linking groups.\n\n---\n\n#### **Step 6: Factors to Ensure Stability and Functionality**\nFinally, consider the following factors:\n1. **Reaction Environment:** Maintain favorable solvent, pH, and temperature to ensure proper cross-link formation without premature degradation.\n2. **Control of Cross-link Density:** Optimize the molar ratios to balance hydrophilicity, mechanical properties, and degradability (e.g., excessive cross-linking can hinder degradation).\n3. **Postprocessing:** Store the polymer in a hydrated environment to retain hydrophilic features.\n4. **Application-Specific Design:** Tune degradability based on intended use (e.g., rapid degradation for drug delivery vs. slow degradation for scaffolds).\n\n---\n\n#### **Summary**\nBy combining hydrophilic monomers/polymers with dynamic cross-linking groups, you can design a hydrophilic polymer with controlled degradability. Careful adjustment of reaction conditions (pH, molar ratios, solvent selection) and characterization techniques will help ensure the stability and functionality of the final material. This systematic approach will allow you to successfully prepare the material in a laboratory setting.\n\n"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe how the molecule '3-methacryloxypropyltrimethoxysilane (MAPTMS)' can be utilized in a sol-gel process to modify a polymer for enhanced hydrophilicity. Specifically, outline the steps needed to hydrolyze and condense this molecule to create a suitable intermediate for further polymerization."}, {"role": "assistant", "content": "Certainly, let us thoughtfully analyze and systematically address your question regarding the use of 3-methacryloxypropyltrimethoxysilane (MAPTMS) in a sol-gel process to modify a polymer for enhanced hydrophilicity. Following this, I will provide a detailed, step-by-step experimental scheme to accomplish this synthetic goal in the laboratory.\n\n---\n\n### **Step 1: Key Points of the Question**\nTo accurately address your question:\n1. **Objective:** Enhance the hydrophilicity of a polymer by modifying it with MAPTMS through a sol-gel process.\n2. **Main Reactant:** MAPTMS, which is an organosilane compound featuring both methacryloyl functionality (for later polymerization) and silane groups (for hydrolysis and condensation).\n3. **Preparation Strategy:** Use the sol-gel process to hydrolyze and condense MAPTMS into a suitable intermediate (organosilica network or oligomers) that can subsequently graft to or be incorporated into the target polymer.\n4. **Experimental Details:** Design a systematic approach that considers the precise reaction conditions (e.g., catalyst, pH, solvent, temperature, reagent ratios) for controlling hydrolysis and condensation.\n\n---\n\n### **Step 2: Detailed Experimental Procedure**\n\nHere is a systematic experimental preparation scheme for the hydrolysis and condensation of MAPTMS in the sol-gel process:\n\n#### **2.1 Materials Required**\n- **Reagent:** 3-methacryloxypropyltrimethoxysilane (MAPTMS, \u226598% purity).\n- **Hydrolysis Catalyst:** Acidic catalyst (e.g., hydrochloric acid, acetic acid) at a dilute concentration (typically pH ~3-5).\n- **Solvent:** Aqueous-alcohol mixture (e.g., ethanol/water system).\n- **Deionized Water:** For facilitating hydrolysis.\n- **Optional Additives:** Small amounts of surfactants or stabilizers (e.g., Triton X-100) to enhance dispersion, if required.\n\n#### **2.2 Outline of the Reaction Steps**\n\n1. **Preparation of Reaction Mixture:**\n   - **Volume Ratios:** Prepare an ethanol-water solution with an **ethanol:water molar ratio of 4:1**. Write down the desired volume based on your required scale. Ethanol acts as a co-solvent to dissolve hydrophobic MAPTMS, while water provides the source for hydrolysis.\n   - **pH Adjustment:** Use dilute HCl solution to adjust the pH of the ethanol-water mixture to approximately 3-4. This mildly acidic pH is optimal for silane hydrolysis without promoting excessive condensation at this stage.\n\n2. **Hydrolysis of MAPTMS:**\n   - Dissolve MAPTMS into the acidic ethanol-water solution with stirring at room temperature (~25\u00b0C).\n   - Recommended **MAPTMS:water molar ratio:** 1:3. This ensures each methoxy group (-OCH3) on the silane is sufficiently hydrolyzed into a silanol (-Si-OH). For instance, if you use 10 mmol MAPTMS, you should add 30 mmol water.\n   - **Stirring and Time:** Stir the reaction mixture continuously for **1-2 hours** to allow hydrolysis to proceed. During this time, you may observe the formation of a clearer solution, indicating the conversion of MAPTMS to silanol groups.\n\n3. **Condensation of Silanols:**\n   - Adjust the hydrolysis step to transition to silanol condensation by slightly raising the temperature to ~50\u00b0C under **gentle stirring**. This promotes the formation of Si-O-Si bonds between hydrolyzed silanol groups, leading to the formation of a partially condensed organosilica network (oligomeric siloxane intermediates).\n   - Monitor viscosity changes in the reaction mixture, which indicate that partial condensation is occurring. Do not allow full gelation, as the product should remain in a soluble or colloidal state.\n\n4. **Optional Stabilization/Homogenization:**\n   - If your intermediate forms aggregates or larger particles during condensation, use a sonicator or mild surfactant to redisperse and stabilize the solution.\n\n5. **Storage:** Store the condensed MAPTMS intermediate at low temperature (~4\u00b0C) if it is not used immediately, as further crosslinking may proceed over time.\n\n#### **2.3 Key Observations:**\n- During hydrolysis, methanol (by-product) can be detected as the methoxy (-OCH3) groups are replaced with hydroxyl (-OH).\n- During condensation, the formation of Si-O-Si linkages can be confirmed using FTIR spectroscopy by observing characteristic peaks at ~1000 cm\u207b\u00b9 (Si-O-Si stretching).\n\n---\n\n### **Step 3: Subsequent Polymerization Step**\nAfter preparing the MAPTMS-derived organosilica network:\n1. It can be incorporated into or grafted onto your target polymer matrix through the methacryloyl (-C=C-) functionality on MAPTMS, which enables polymerization with other vinyl monomers.\n2. Use free radical polymerization (e.g., with an initiator like AIBN or potassium persulfate) to covalently anchor MAPTMS-derived hydrophilic moieties into the polymer.\n\n---\n\n### **Step 4: Consideration for Enhancing Hydrophilicity**\nThe resulting polymer will be made hydrophilic due to the following:\n1. **Si-OH Surface Groups:** The hydrolysis and partial condensation of MAPTMS leave residual silanol (-Si-OH) groups, which enhance hydrophilicity via hydrogen bonding with water.\n2. **Post-Polymerization Functionalization:** If desired, additional functional hydrophilic groups (e.g., by reacting amino or carboxylic acids) can be introduced through post-grafting techniques to further increase water affinity.\n\n---\n\n### **Step 5: Notes on Laboratory Practice**\n- Perform the sol-gel process in a moisture-controlled environment to avoid uncontrolled gelation or crosslinking.\n- Always ensure the stoichiometry of MAPTMS, water, and catalysts is properly calculated to guide the progression of hydrolysis and condensation.\n\n---\n\nThis step-by-step protocol should now enable you to successfully use MAPTMS in a sol-gel process to create intermediates suitable for modifying polymers with enhanced hydrophilicity."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe how you would incorporate a sulfonic acid type amphoteric surface active agent, derived from alpha-hydroxyalkyldialkylamine reacted with benzyl chloride, into a polymer system to enhance its hydrophilicity. Be specific about the reaction steps and the resulting molecular interactions."}, {"role": "assistant", "content": "Certainly! Let us approach your question step by step, breaking it into its parts while focusing on the desired goal: incorporating a sulfonic acid-type amphoteric surfactant, derived from the reaction of alpha-hydroxyalkyldialkylamine with benzyl chloride, into a polymer system to enhance its hydrophilicity.\n\n### **Key Points**\n1. **Objective:** Enhance the hydrophilicity of a polymer system using a specifically derived sulfonic acid-type amphoteric surfactant.\n   - This surfactant is synthesized by reacting alpha-hydroxyalkyldialkylamine with benzyl chloride.\n\n2. **Requirements:**\n    - Detailed synthesis process for the sulfonic acid-type surfactant.\n    - Method for incorporating the surfactant into the polymer system.\n    - Clear instructions on experimental conditions, reagent proportions, reaction mechanisms, and molecular interactions.\n\n---\n\n### **Detailed Experimental Preparation Scheme**\n\n#### **Part I: Synthesis of Sulfonic Acid-Type Amphoteric Surfactant**\nWe first need to synthesize the surfactant, which involves the reaction of alpha-hydroxyalkyldialkylamine with benzyl chloride.\n\n##### **Step 1: Preparation of Alpha-Hydroxyalkyldialkylamine**\n1. **Reagents Required:**\n   - Dialkylamine (e.g., dimethylamine or diethylamine).\n   - Alpha-hydroxyalkyl halide (e.g., 2-chloroethanol).\n   - Solvent: Tetrahydrofuran (THF) or ethanol.\n\n2. **Reaction Conditions:**\n   - Perform the reaction in a round-bottom flask under an inert nitrogen atmosphere to prevent oxidation.\n   - Combine dialkylamine and alpha-hydroxyalkyl halide in a 1:1 molar ratio.\n   - Add THF as a solvent to maintain homogeneity.\n   - Stir the mixture at **room temperature** for 8\u201312 hours.\n   - Monitor the reaction progress using thin-layer chromatography (TLC).\n\n3. **Reaction Mechanism:**\n   A nucleophilic substitution occurs, where the alpha-hydroxyalkyl halide reacts with the amine to produce alpha-hydroxyalkyldialkylamine and a byproduct (e.g., HCl or NaCl).\n\n4. **Purification:**\n   - Neutralize the reaction solution with a base (if acidic byproducts form).\n   - Use distillation or recrystallization to obtain the alpha-hydroxyalkyldialkylamine.\n\n---\n\n##### **Step 2: Reaction with Benzyl Chloride**\n1. **Reagents Required:**\n   - Alpha-hydroxyalkyldialkylamine (from **Step 1**).\n   - Benzyl chloride (functionalization agent).\n   - Solvent: Dimethylformamide (DMF).\n\n2. **Reaction Conditions:**\n   - Add benzyl chloride to the alpha-hydroxyalkyldialkylamine in a **2:1 molar ratio**.\n   - Use DMF as a solvent and perform the reaction at **40\u201360\u00b0C** for 8\u201310 hours under stirring.\n   - Include a catalytic amount of potassium carbonate (K2CO3) or another weak base to facilitate the reaction and neutralize liberated HCl.\n\n3. **Reaction Mechanism:**\n   - Benzyl chloride reacts with the hydroxy and amine groups of alpha-hydroxyalkyldialkylamine, forming a structure with benzyl substitution.\n   - This molecule serves as the precursor **(intermediate)** for the sulfonic acid-containing surfactant.\n\n4. **Purification:**\n   - Wash the crude product with ethyl acetate to remove unreacted benzyl chloride.\n   - Purify using column chromatography, employing a methanol/water solvent mixture.\n\n---\n\n##### **Step 3: Functionalization to Incorporate Sulfonic Acid**\n1. **Reagents Required:**\n   - Intermediary product (benzyl-functionalized alpha-hydroxyalkyldialkylamine).\n   - Sulfonating agent: Chlorosulfonic acid or sodium bisulfite.\n\n2. **Reaction Conditions:**\n   - Use a well-ventilated fume hood, as sulfonating agents release acidic vapors.\n   - Add the sulfonating agent dropwise to the benzyl-functionalized compound at **0\u20135\u00b0C**.\n   - Let the reaction proceed at room temperature for **6\u201312 hours** under stirring.\n\n3. **Reaction Mechanism:**\n   - The sulfonating agent introduces sulfonic acid (-SO3H) groups onto the benzyl-functionalized molecule, forming a sulfonic acid-type amphoteric surfactant.\n\n4. **Purification:**\n   - Neutralize excess sulfonating agent with dilute NaOH.\n   - Dialyze the product to remove impurities, followed by lyophilization.\n\n---\n\n#### **Part II: Incorporation into Polymer System**\nWith the surfactant ready, the next step involves introducing it into the polymer system to enhance hydrophilicity.\n\n##### **Step 4: Polymer System Selection**\n1. The polymer must be compatible with the surfactant. Examples include:\n   - Polyvinyl alcohol (PVA).\n   - Polyacrylamide (PAM).\n   - Polyethylene glycol (PEG).\n\n2. Polymer characteristics to modify:\n   - Hydrophilicity, wettability, or biocompatibility.\n\n---\n\n##### **Step 5: Blending Method**\nThe surfactant can be introduced into the polymer system using either **grafting** or **physical blending**.\n\n1. **Grafting Approach:**\n   - Use radical polymerization to covalently bind the surfactant to the polymer backbone.\n   - Initiators: Potassium persulfate or benzoyl peroxide.\n   - Reaction Conditions:\n     - Dissolve the polymer in an aqueous solution.\n     - Add the surfactant (in 10\u201320% w/w ratio).\n     - Initiate the reaction at **70\u201380\u00b0C** under nitrogen for 6 hours.\n\n2. **Physical Blending Approach:**\n   - Dissolve the polymer and surfactant in a common solvent (e.g., water, ethanol).\n   - Use sonication or mechanical stirring to homogeneously mix the two.\n   - Cast the solution onto a substrate (glass or Teflon) and dry at **room temperature** to remove the solvent.\n\n---\n\n##### **Step 6: Characterization**\nTo confirm enhanced hydrophilicity:\n1. **Contact Angle Measurement:** Verify reduced water contact angle on surfaces.\n2. **FTIR Analysis:** Confirm sulfonic acid functional groups (-SO3H) in the polymer structure.\n3. **Tensile Strength Tests:** Ensure mechanical integrity of the polymer post-modification.\n\n---\n\n### **Molecular Interactions**\n1. **Hydrophilic Effect:**\n   - Sulfonic acid (-SO3H) groups form hydrogen bonds with water, increasing surface hydrophilicity.\n   - Benzyl groups help improve polymer-surfactant compatibility by introducing aromatic interactions.\n\n2. **Amphoteric Behavior:**\n   - The structure allows interactions with both acidic and basic solvents, further enhancing wettability.\n\n---\n\n### **Conclusion**\nBy systematically synthesizing the sulfonic acid-type amphoteric surfactant and effectively incorporating it into a polymer matrix, the hydrophilicity of the polymer can be enhanced through increased water affinity, amphoteric character, and hydrogen-bonding capabilities. This approach ensures optimal polymer performance in applications requiring high wettability or biocompatibility.\n\n"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "When incorporating silane derivatives containing an epoxy group and polyethylene glycol chains into a polymeric network, what factors would you consider to ensure optimal hydrophilicity? Include how 3-isocyanatopropyltrimethoxysilane can influence these factors."}, {"role": "assistant", "content": "To address your question regarding incorporating silane derivatives containing an epoxy group and polyethylene glycol (PEG) chains into a polymeric network to enhance hydrophilicity, let us systematically break it down step-by-step while considering all relevant factors, including the role of 3-isocyanatopropyltrimethoxysilane. Here's a detailed analysis and an experimental framework:\n\n---\n\n### **Step 1: Analyze the Question**\n- **Goal:** To enhance the hydrophilicity of a polymeric network using silane derivatives with epoxy and PEG chains.\n- **Key Consideration:** Silane chemistry, PEG hydrophilicity, crosslinking mechanisms, and surface characteristics of the polymer networks.\n- **Role of 3-Isocyanatopropyltrimethoxysilane:** A trifunctional silane compound with an isocyanate (-NCO) group for covalent bonding and trimethoxysilane (-Si(OCH3)3) groups for hydrolysis/condensation to form a siloxane network.\n\n---\n\n### **Step 2: Factors Influencing Hydrophilicity**\n1. **Incorporation of PEG Chains:**\n   - PEG is inherently hydrophilic due to its repeating ether oxygen atoms that interact with water molecules via hydrogen bonding.\n   - The molecular weight and chain length of PEG influence hydrophilicity. Higher molecular weight PEG derivatives yield better water affinity but can reduce crosslinking density.\n\n2. **Functionalization via Silane Derivatives:**\n   - Silane derivatives (such as those containing epoxy and PEG chains) can act as crosslinkers, imparting hydrophilicity while also ensuring compatibility with the polymer matrix.\n   - Hydrolysis and condensation reactions of silane moieties allow network formation, anchoring hydrophilic domains effectively into the polymer.\n\n3. **Role of Epoxy Groups:**\n   - Epoxy groups facilitate nucleophilic addition reactions with primary amines, alcohols, or thiols (present in the polymer matrix) to establish covalent bonds within the material.\n\n4. **Role of 3-Isocyanatopropyltrimethoxysilane:**\n   - The isocyanate group reacts with nucleophilic groups in the polymer (e.g., hydroxyl or amines) to form strong urethane bonds, ensuring anchoring.\n   - After attachment, the trimethoxysilane group undergoes hydrolysis (in the presence of water or moisture) into silanol groups (-SiOH), followed by condensation into polysiloxane bonds, leading to network integrity.\n\n5. **Hydrophobic/Hydrophilic Balance:**\n   - Proper balancing is required to ensure that the PEG hydrophilicity is not overshadowed by residual hydrophobic siloxane domains or other non-polar groups in the polymer.\n\n---\n\n### **Step 3: Experimental Preparation Scheme**\nThe following step-by-step synthesis procedure incorporates silane derivatives with epoxy and PEG chains for a hydrophilic polymeric network: \n\n#### **Materials:**\n- Silane derivative with an epoxy group and PEG chain (e.g., epoxy-PEG-silane).\n- 3-Isocyanatopropyltrimethoxysilane.\n- Polymer matrix with reactive groups (e.g., hydroxyl-terminated or amino-terminated polymer).\n- Solvent: Anhydrous toluene or ethanol, depending on the solubility of components.\n- Catalyst for silane hydrolysis/condensation, such as acetic acid or ammonium hydroxide (for pH control).\n- Water (controlled for hydrolysis of silane functionalities).\n\n---\n\n#### **Step 1: Functionalization with 3-Isocyanatopropyltrimethoxysilane**\n1. **Reaction Design**:\n   - React 3-isocyanatopropyltrimethoxysilane with the polymer's reactive groups (e.g., \u2013OH or \u2013NH2).\n   - Allow urethane bond formation (amine or hydroxyl group attacking the \u2013NCO group).\n\n2. **Procedure**:\n   - Dissolve the polymer (5 mmol hydroxyl or amino groups) in 50 mL of anhydrous toluene under inert conditions (e.g., nitrogen).\n   - Add 3-isocyanatopropyltrimethoxysilane (5.5 mmol, slightly excess to ensure complete reaction) dropwise.\n   - Heat the solution to 50\u201360\u00b0C for 4\u20136 hours with continuous stirring to allow the nucleophilic reaction to occur.\n   - Confirm reaction completion using FTIR (disappearance of the isocyanate peak at ~2270 cm\u207b\u00b9 and appearance of urethane peaks ~1680 cm\u207b\u00b9).\n\n---\n\n#### **Step 2: Incorporation of Epoxy-PEG-Silane**\n1. **Reaction Design**:\n   - Incorporate the silane derivative with an epoxy-PEG group into the functionalized polymer network to introduce hydrophilic PEG domains.\n   - Utilize the trimethoxysilane groups for hydrolysis and condensation to form siloxane linkages.\n\n2. **Procedure**:\n   - Dissolve the functionalized polymer (from Step 1) in 50 mL of ethanol or a similar polar solvent.\n   - Add the epoxy-PEG-silane (molar ratio of PEG-silane to polymer hydroxyl/amine groups = 1:1).\n   - Add catalytic amounts of acetic acid (~0.1 mL) to the mixture to initiate silane hydrolysis at ambient temperature.\n   - Stir the solution at room temperature for 12\u201324 hours to allow for silane hydrolysis into silanol groups (-SiOH) and subsequent condensation into a stable network.\n   - Monitor the reaction via FTIR (appearance of Si\u2013O\u2013Si bonds at ~1100 cm\u207b\u00b9 and disappearance of Si\u2013OCH3 peaks).\n\n---\n\n#### **Step 3: Network Formation and Curing**\n1. **Crosslinking Reaction**:\n   - To enhance network stability, cure the polymer in a humid environment, facilitating further condensation of silanol groups into polysiloxanes.\n   - Optional heat treatment (e.g., 70\u2013100\u00b0C) may help accelerate curing without degrading the PEG components.\n\n2. **Post-treatment:**\n   - Wash the polymer network with ethanol and distilled water to remove residual unreacted components.\n   - Dry the polymer network under vacuum at 40\u201350\u00b0C to constant weight.\n\n---\n\n### **Step 4: Characterization**\n- Confirm the incorporation of PEG and silane derivatives using:\n  - **FTIR:** Characteristic peaks for PEG (C\u2013O at ~1100 cm\u207b\u00b9), siloxanes (Si\u2013O\u2013Si at ~1100 cm\u207b\u00b9), and urethane groups (~1680 cm\u207b\u00b9).\n  - **NMR (\u00b9H or \u00b2\u2079Si):** To detect polymer backbone modifications and silane species.\n  - **Contact Angle Measurements:** Assess surface hydrophilicity (values near or below 30\u00b0 indicate high hydrophilicity).\n  - **Water Swelling Test:** Quantify the hydrophilic character by absorption/swelling behavior.\n\n---\n\n### **Conclusion**\nIncorporating silane derivatives containing epoxy and PEG chains into a polymeric network enhances hydrophilicity via PEG's water affinity and silane's functional versatility. 3-Isocyanatopropyltrimethoxysilane contributes by forming stable covalent linkages and integrating siloxane domains into the polymer. Precise control over reaction conditions (e.g., molar ratios, hydrolysis pH, and curing process) ensures optimal hydrophilicity and structural stability."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "You are tasked with utilizing N-(isobutoxy)methylacrylamide in the preparation of a hydrophilic polymer. Describe the chemical reaction mechanism this molecule participates in and its contribution to the overall hydrophilicity of the final polymer."}, {"role": "assistant", "content": "### Step 1: Analyze the Question and Summarize Key Points\nTo answer the question comprehensively, it is important to understand the functional characteristics of **N-(isobutoxy)methylacrylamide**, its reactivity, and how it can be incorporated into a polymer structure to enhance hydrophilicity. Key considerations include:\n1. **Chemical Reactivity**:\n   - The acrylamide group allows the molecule to participate in addition polymerization reactions via the double bond.\n   - The N-(isobutoxy)methyl group can be hydrolyzed under suitable conditions to yield functional groups that improve hydrophilicity.\n2. **Mechanism**:\n   - The molecule participates in radical polymerization or other chain-growth polymerization mechanisms involving the acrylamide moiety.\n   - Post-reaction hydrolysis can introduce hydrophilic groups to enhance water affinity.\n3. **Overall Contribution**:\n   - The hydrophilicity arises from functional groups (such as hydroxyl groups) introduced by hydrolysis after polymerization.\n\nThe experimental plan must outline a polymerization scheme and post-synthesis modification to maximize hydrophilicity.\n\n---\n\n### Step 2: Detailed and Systematic Description of the Preparation Scheme\nBelow is the detailed preparation scheme for synthesizing the hydrophilic polymer using **N-(isobutoxy)methylacrylamide**.\n\n#### **Step 2.1: Materials and Reagents**\n- **Monomer**: N-(isobutoxy)methylacrylamide\n- **Initiator**: Common radical polymerization initiators, such as azobisisobutyronitrile (AIBN) or potassium persulfate (KPS).\n- **Solvent**: Water or an organic solvent (acetone, ethanol, or dimethylformamide [DMF]) for controlling the reaction environment.\n- **Crosslinker (optional)**: N,N\u2019-methylenebisacrylamide (MBA) to improve mechanical properties of the polymer.\n- **Acid catalyst**: Hydrochloric acid (HCl) or sulfuric acid (H2SO4) for hydrolysis in post-polymerization stages.\n\n---\n\n#### **Step 2.2: Experimental Preparation Scheme**\nThe synthesis will be divided into two phases:\n1. **Polymerization Reaction Phase**: Formation of the polymer backbone.\n2. **Post-Polymerization Hydrolysis Phase**: Enhancing hydrophilicity by converting hydrophobic groups to hydrophilic ones.\n\n---\n\n### **Phase 1: Radical Polymerization**\n#### **Step 1: Preparation of the Reaction Mixture**\n1. **Reagent Quantities**:\n   - Monomer (N-(isobutoxy)methylacrylamide): Depending on the desired degree of polymerization, use approximately **10 mmol** for smaller scale reactions.\n   - Solvent: Ensure a solvent volume sufficient to fully dissolve the monomer. For aqueous polymerizations, use 50 mL deionized water.\n   - Initiator (e.g., AIBN): Add 1 mol% relative to the monomer concentration (e.g., 0.1 mmol).\n   - Crosslinker (optional): Add N,N\u2019-methylenebisacrylamide in amounts ranging from 0.5\u20132 mol% of the monomer concentration for gel-like polymers.\n\n2. **Mixing**:\n   Dissolve the monomer, initiator, and optional crosslinker in the solvent under nitrogen or argon to prevent oxygen inhibition of radical initiated polymerization.\n\n#### **Step 2: Polymerization Reaction**\n1. The reaction mixture is placed in a reaction vessel equipped with a stirrer and thermometer.\n2. **Reaction Conditions**:\n   - Temperature: Heat to 60\u201370\u00b0C (specific to the initiator decomposition temperature; for AIBN, 65\u00b0C is suitable).\n   - Duration: Allow polymerization to proceed for 4\u20136 hours to ensure high monomer conversion.\n3. **Monitoring**:\n   - Monitor viscosity changes in the reaction mixture, indicative of polymer formation.\n   - Optionally, take aliquots for spectroscopic analysis (e.g., FTIR) to confirm double bond consumption.\n\n4. **Isolation**:\n   - Precipitation Method: Precipitate the polymer by adding the reaction mixture to a non-solvent (e.g., cold methanol or acetone).\n   - Filtration and Washing: Wash with methanol to remove impurities and unreacted monomer.\n\n---\n\n### **Phase 2: Hydrolysis**\n#### **Step 1: Hydrolysis Setup**\nTo enhance hydrophilicity, the N-(isobutoxy)methyl group can be hydrolyzed to introduce hydrophilic functionalities (e.g., hydroxyl or amide groups).\n\n1. **Reagent Quantities**:\n   - Acid catalyst (e.g., HCl): Prepare a 0.1\u20130.5 M solution. Use 20\u201350 mL per 10 mmol of polymer.\n2. **Reaction Medium**:\n   - Dissolve the isolated polymer in water or a polar solvent capable of facilitating hydrolysis.\n\n#### **Step 2: Hydrolysis Reaction**\n1. Heat the solution to 80\u201395\u00b0C under acidic conditions.\n2. Reaction Time: Maintain for 12\u201324 hours for complete hydrolysis.\n3. Monitor Progress:\n   - Use FTIR spectroscopy (monitor disappearance of isobutoxy absorption bands and appearance of hydroxyl or amide bands).\n   - pH titration may be used to confirm acid consumption.\n\n#### **Step 3: Neutralization and Purification**\n1. Neutralize the solution using a mild base (e.g., sodium bicarbonate) if the polymer is acid-sensitive.\n2. Dialysis: Purify the hydrophilic polymer by dialysis against deionized water for 2\u20133 days to remove salts and residual acid.\n3. Drying: Lyophilize or air-dry the purified polymer.\n\n---\n\n### **Step 3: Mechanistic Insights**\n#### **Polymerization Mechanism**\nThe acrylamide moiety undergoes free radical polymerization initiated by AIBN. Radicals generated by initiators attack the double bond, forming a propagating chain that incorporates the monomer into the polymer backbone.\n\n#### **Hydrolysis Mechanism**\nUnder acidic conditions, the isobutoxy group undergoes hydrolysis:\n1. Cleavage of the N-(isobutoxy)methyl group.\n2. Formation of primary amide and/or hydroxyl groups, which can form hydrogen bonds with water.\n\n---\n\n### Summary\nThe overall hydrophilicity of the polymer arises from the conversion of hydrophobic isobutoxy functional groups into hydrophilic ones during the post-polymerization hydrolysis phase. This design leverages the reactivity of acrylamide and the functional group's transformability, resulting in a highly water-friendly polymer ideal for hydrophilic applications. Ensure careful monitoring and purification to obtain optimal results."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the synthetic procedure you would use to prepare a quaternary ammonium salt (14QAS) starting from a tertiary amine and a bromoalkane. Include the reaction conditions and steps required to ensure high product yield."}, {"role": "assistant", "content": "Certainly! I will provide you with a systematic and detailed experimental scheme for the preparation of a quaternary ammonium salt (14QAS) starting from a tertiary amine and a bromoalkane. Quaternary ammonium salts are widely used in hydrophilic polymer systems to enhance ionic and hydrophilic characteristics.\n\n---\n\n### Key Points in the Question:\n1. **Substrates**:\n   - The starting materials are a **tertiary amine** (R\u2083N) and a **bromoalkane** (R\u2032-Br).\n   - The tertiary amine provides the basic nitrogen atom, while the bromoalkane introduces the alkyl group to generate the quaternary ammonium structure.\n\n2. **Reaction Goal**:\n   - The reaction is a **nucleophilic substitution reaction (SN2)**, where the nucleophilic nitrogen in the tertiary amine attacks the electrophilic carbon in the bromoalkane to form the quaternary ammonium salt, R\u2083N\u207aR\u2032-Br\u207b.\n\n3. **Optimizing Product Yield**:\n   - The presence of unwanted side reactions or incomplete conversions should be minimized.\n   - Reaction parameters, such as solvent, stoichiometry, temperature, and reaction duration, must be optimized for high yield.\n\n---\n\n### Synthetic Procedure for Preparing 14QAS:\n\n#### **Step 1: Preparation and Reagent Ratio Setup**\n1. **Reagents Required**:\n   - Tertiary amine: Choose an appropriate tertiary amine (e.g., trimethylamine, triethylamine, or other trialkylamines depending on the desired final structure).\n   - Bromoalkane: Select the desired bromoalkane (e.g., 1-bromotetradecane if preparing a tetradecyl quaternary salt).\n   - Solvent: Use a polar aprotic solvent such as **acetonitrile (CH\u2083CN)** or a nonpolar solvent like **toluene**. Acetonitrile is often preferred because it promotes the SN2 reaction mechanism.\n\n2. **Molar Ratio**:\n   - Use a slight **excess of bromoalkane** (1.1\u20131.2 equivalents with respect to the tertiary amine) to drive the reaction to completion.\n\n3. **Reaction Vessel**:\n   - Utilize a **round-bottom flask** equipped with a reflux condenser to maintain a constant temperature.\n\n---\n\n#### **Step 2: Reaction Procedure**\n1. **Dissolution**:\n   - Dissolve the tertiary amine in acetonitrile in the round-bottom flask. For example, if using 10 mmol of the tertiary amine, dissolve it in approximately 20\u201330 mL of acetonitrile.\n\n2. **Addition of Bromoalkane**:\n   - Slowly add the bromoalkane to the solution of tertiary amine while stirring at room temperature. Add it dropwise if needed to ensure controlled mixing.\n   - Example: For 10 mmol of tertiary amine, add approximately 11\u201312 mmol (1.1\u20131.2 equivalents) of bromoalkane.\n\n3. **Heating**:\n   - Heat the reaction mixture under reflux (70\u201390 \u00b0C, depending on the solvent used). The exact temperature may vary depending on the reactivity of the specific tertiary amine and bromoalkane, typically optimized within this range.\n   - Allow the reaction to proceed for 12\u201324 hours to ensure complete conversion.\n\n4. **Monitoring Progress**:\n   - Use **thin-layer chromatography (TLC)** or **NMR spectroscopy** to monitor the reaction\u2019s progression. \n\n---\n\n#### **Step 3: Workup and Purification**\n1. **Precipitation of the Product**:\n   - After completion, cool the reaction mixture to room temperature. The quaternary ammonium salt may precipitate in the reaction solvent (depending on the solubility).\n   - If precipitation occurs, filter the solid product using a B\u00fcchner funnel and wash it with a small amount of cold solvent (e.g., diethyl ether) to remove unreacted bromoalkane or impurities.\n\n2. **Recrystallization (if necessary)**:\n   - If the quaternary ammonium salt is not pure, recrystallize it from a suitable solvent mixture. A common choice is a mixture of **ethanol and diethyl ether** or **methanol and ether**, depending on the salt\u2019s solubility.\n\n3. **Drying**:\n   - Dry the purified quaternary ammonium salt under vacuum at 40\u201350 \u00b0C to remove any residual solvent.\n\n---\n\n### Additional Notes:\n- **Yield Considerations**:\n   - Using a polar aprotic solvent like acetonitrile is critical to enhance the nucleophilicity of the nitrogen and to promote the SN2 mechanism, which improves yield.\n   - Employing an excess of bromoalkane helps to drive the reaction forward.\n   - Prolonged heating under reflux ensures complete conversion of reactants.\n  \n- **Safety Precautions**:\n   - Handle bromoalkanes with care, as they are irritants and potentially toxic.\n   - Work in a well-ventilated fume hood and wear proper personal protective equipment.\n\n- **Example Calculation**:\n   - If using 10 mmol of trimethylamine (MW = 59.11 g/mol) and 12 mmol of 1-bromotetradecane (C14H29Br, MW = 273.3 g/mol), the required masses of the reagents are:\n     - Trimethylamine: \\( 0.01 \\, \\text{mol} \\times 59.11 \\, \\text{g/mol} = 0.591 \\, \\text{g} \\)\n     - 1-Bromotetradecane: \\( 0.012 \\, \\text{mol} \\times 273.3 \\, \\text{g/mol} = 3.28 \\, \\text{g} \\)\n\n---\n\nBy following this systematic procedure, you should be able to successfully prepare a quaternary ammonium salt with a high yield. Feel free to ask if you have further questions or require modifications for specific tertiary amines or bromoalkanes!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain the mechanism by which NaBH4 (sodium borohydride) interacts with HAuCl4 during the preparation process. How does this reaction contribute to the hydrophilicity of the final polymer?"}, {"role": "assistant", "content": "Excellent question! Let's carefully analyze the problem and systematically unpack every detail to ensure clarity and comprehensiveness.\n\n---\n\n### **Key Question Analysis:**\n1. **Reagents Involved:**\n   - **NaBH\u2084 (Sodium Borohydride):** A powerful reducing agent commonly used in both organic and inorganic synthesis.\n   - **HAuCl\u2084 (Gold Chloride or Chloroauric Acid):** A gold-containing precursor that can reduce into nanoparticles or different gold states depending on the reducing agent and reaction conditions.\n\n2. **Synthesis Context:**\n   - The interaction between NaBH\u2084 and HAuCl\u2084 likely pertains to some reduction mechanism where NaBH\u2084 reduces HAuCl\u2084 to metallic gold nanoparticles (AuNPs) or other metallic gold forms.\n   - The gold nanoparticles or species formed may play a role in modifying the hydrophilicity of the final polymer.\n\n3. **Hydrophilicity Enhancement:**\n   - The formation of AuNPs or some intermediates could contribute to improving the hydrophilicity of the polymer when surface-functionalized with hydrophilic moieties.\n   - Understanding the mechanism will reveal how this reaction fits into the broader context of hydrophilic polymer synthesis.\n\n---\n\n### **Step-by-Step Answer:**\n\n#### **Step 1: The Mechanism of NaBH\u2084 and HAuCl\u2084 Interaction**\nWhen NaBH\u2084 interacts with HAuCl\u2084, it reduces the Au\u00b3\u207a ions (from the HAuCl\u2084) to metallic gold (Au\u2070), typically producing gold nanoparticles (AuNPs) in the process. Let us break this mechanism down:\n\n- **Reduction Reaction:**\n  - HAuCl\u2084 in water dissociates into Au\u00b3\u207a ions and Cl\u207b ions:\n    \\[\n    HAuCl_4 \\longrightarrow Au^{3+} + 4Cl^{-} + H^{+}.\n    \\]\n\n  - Sodium borohydride (NaBH\u2084) donates electrons to the gold cation (Au\u00b3\u207a), reducing it to metallic gold (Au\u2070), which often nucleates to form nanoparticles. The reaction follows:\n    \\[\n    NaBH_4 + 3H_2O + 4Au^{3+} \\longrightarrow 4Au^{0} + NaB(OH)_4 + 3H^{+}.\n    \\]\n\n- **Formation of Nanoparticles:**\n  - Au\u2070 atoms aggregate to form colloidal gold nanoparticles (AuNPs) in the aqueous solution. The size and distribution of these nanoparticles depend on factors such as the NaBH\u2084 concentration, temperature, reaction time, and stabilizers (if present).\n\n- **Reaction Conditions:**\n  - The reduction is fast and occurs at ambient temperature. Stirring is usually required to ensure uniform mixing of the reducing agent and the gold precursor.\n  - A freshly prepared sodium borohydride solution is typically used since it decomposes rapidly in water, releasing hydrogen gas.\n\n#### **Step 2: Linking This to the Hydrophilicity of the Final Polymer**\nHow exactly does this reaction contribute to the hydrophilicity of the polymer? The answer lies in the **role of the gold nanoparticles and subsequent surface functionalization**.\n\n1. **Surface Interaction with the Polymer:**\n   - Gold nanoparticles have a high surface energy, which allows them to interact with various functional groups on the polymer. This creates an **attachment point for hydrophilic groups**.\n\n2. **Surface Functionalization:**\n   - Often, AuNPs are surface-functionalized with hydrophilic ligands or molecules, such as thiols, carboxylic acids, or polyethylene glycols (PEG). These hydrophilic moieties, once integrated with the polymer, dramatically enhance the hydrophilicity of the overall material.\n\n3. **Uniform Dispersion & Compatibility:**\n   - Due to their colloidal nature, AuNPs can uniformly disperse throughout the polymer matrix. This ensures an even distribution of hydrophilic groups, leading to a highly hydrophilic material.\n\n4. **Crosslinking or Anchoring with the Polymer:**\n   - If the polymer is designed with reactive sites (e.g., amine, thiol, hydroxyl, or carboxylic groups), gold nanoparticles can act as a cross-linker or anchor by forming stable chemical interactions (e.g., Au-S bonds, Au-NR\u2082 complexes). These cross-linked or anchored regions may also expose hydrophilic functional groups, further improving the material's water affinity.\n\n#### **Step 3: Overall Role in Polymer Hydrophilicity**\nThe reduction of HAuCl\u2084 by NaBH\u2084 to form AuNPs plays a critical role in the hydrophilicity of the polymer for the following reasons:\n- AuNPs provide a high-surface-area platform for the attachment of hydrophilic functional groups.\n- Surface-functionalized AuNPs can be embedded within the polymer matrix, ensuring that hydrophilic regions are uniformly present throughout the material.\n- If the polymer structure itself incorporates hydrophilic groups, the presence of AuNPs can enhance the exposure and accessibility of these groups, thereby increasing overall hydrophilicity.\n\n---\n\n### **Comprehensive Summary:**\nIn summary:\n1. NaBH\u2084 reduces HAuCl\u2084 to form metallic gold nanoparticles (AuNPs) via a redox reaction. During this process, Au\u00b3\u207a ions from HAuCl\u2084 are reduced to Au\u2070, with NaBH\u2084 being oxidized.\n2. AuNPs can then act as scaffolding or anchoring sites for hydrophilic functional groups, either through direct functionalization of the nanoparticle surface or by interacting with the polymer matrix.\n3. The incorporation of hydrophilic AuNPs into the polymer enhances its hydrophilicity by providing water-attracting moieties and creating a more hydrophilic polymer structure.\n\nThis reaction demonstrates the versatility of AuNPs in improving material properties via strategic chemical modifications. Be sure to maintain precise control over reaction parameters\u2014such as reagent concentrations and mixing conditions\u2014to achieve highly uniform and functional nanoparticles for the targeted hydrophilic polymer synthesis."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "What steps would you take to ensure effective mixing of UPy-D400 into a polymer formulation, and how would you verify its successful incorporation into the final polymer structure?"}, {"role": "assistant", "content": "To address your question and help you understand the experimental process thoroughly, let us first break it down into key components, so we can approach the task systematically. Based on your question, we aim to figure out:\n\n1. **Key Points to Analyze:**\n   - What is UPy-D400, and why is it being incorporated into the polymer formulation?\n   - How can effective mixing of UPy-D400 (a hydrophilic or functional additive) into the polymer matrix be ensured?\n   - What experimental steps and parameters are critical during the incorporation process to maintain homogeneity and preserve the integrity of the UPy-D400 structure and functionality?\n   - How do we verify or confirm that UPy-D400 has been successfully incorporated into the polymer structure?\n\n2. **Step-by-Step Experimental Strategy:**\n   I will now provide a detailed and systematic approach, specifying each step in the preparation process, along with important reaction conditions, equipment, and analytical techniques for successful execution in the lab.\n\n---\n\n### **Step 1: Understanding UPy-D400 and Its Significance**\n- **UPy-D400 description**: UPy (ureido-pyrimidinone) is a functional group known for its hydrogen-bonding interactions, making it valuable for improving a polymer\u2019s hydrophilicity, self-healing, or supramolecular properties. D400 is typically a hydrophilic chain attached to the UPy group, likely based on polyethylene glycol (PEG) or another water-compatible structure.\n- **Incorporation Goal**: The goal is to mix UPy-D400 effectively into the polymer formulation in a uniform manner to retain its hydrophilicity or supramolecular assembly properties.\n\n---\n\n### **Step 2: Pre-treatment and Preparation of UPy-D400**\n1. **Purity Verification**: Before use, ensure that UPy-D400 is free of moisture and impurities since these can impact its reactivity and dispersion. Dry the material under vacuum at ~40\u201350 \u00b0C for 3\u20134 hours.\n    - **Equipment**: Vacuum oven or desiccator.\n    - **Control Parameter**: Ensure no thermal degradation occurs by limiting temperature.\n\n2. **Optional Solubilization**: If UPy-D400 has limited dispersibility in the polymer matrix at high viscosities, prepare a stock solution:\n    - Solubilize UPy-D400 in a hydrophilic solvent such as ethanol, methanol, or dimethyl sulfoxide (DMSO) if the polymer formulation can tolerate the solvent.\n    - Typical concentration: 10\u201330 wt%, depending on the target ratio in the formulation.\n    - Stir the solution at room temperature (25\u201330 \u00b0C) to ensure complete dissolution.\n\n---\n\n### **Step 3: Preparation of the Polymer and Mixing with UPy-D400**\n3. **Selection of Base Polymer**:\n   - Choose the polymer type that aligns with the hydrophilic design goal. For example, polyacrylamides, hydroxyl-functionalized polymers, or PEG-based networks work well.\n   - If the polymer is being synthesized in situ (e.g., via polymerization of monomers), UPy-D400 can be incorporated directly into the reaction system.\n\n4. **Mixing Parameters**:\n    - **Method**: Use a mechanical stirrer, twin-screw extruder (for molten polymers), or magnetic stirrer (for liquid/slurry systems).\n    - **Process**: Gradually add UPy-D400 (solid or solution form) to the polymer formulation under consistent stirring. \n        - Stirring Speed: Generally between 300\u20131000 rpm for liquid systems.\n        - Mixing Time: 30\u201360 minutes depending on the viscosity of the polymer solution.\n\n5. **Reaction/Polymerization with UPy-D400** (If the polymer is synthesized in situ):\n    - **Chemical Considerations**:\n      - If UPy-D400 contains reactive functional groups (e.g., hydroxyl, amine, or urethane), ensure it participates in the polymerization or crosslinking reaction. Adjust monomer and crosslinker ratios accordingly.\n    - **Reaction Conditions**:\n      - Typical temperatures for hydrophilic polymer synthesis are ~40\u201370 \u00b0C to maintain UPy functional integrity.\n      - Maintain the reaction in inert conditions (e.g., nitrogen or argon atmosphere) to avoid unwanted side reactions.\n      - Example: If using acrylamide-based monomers, UPy-D400 can be incorporated as a co-monomer, with molar ratios tailored to achieve ~2\u201310 mol% UPy-D400 in the final structure.\n\n---\n\n### **Step 4: Post-Processing and Verification**\n6. **Post-Mixing Homogenization**: After incorporating UPy-D400 into the polymer blend, ensure proper homogenization:\n    - Utilize shear mixing or sonication for liquid-state formulations or melt-blending for molten polymers.\n\n7. **Formulation Stabilization**: If the polymer is crosslinked, cure the formulation under suitable conditions (e.g., UV light for photocurable systems or mild heating for thermally activated cure).\n\n---\n\n### **Step 5: Verification of Successful Incorporation**\n8. **Visual/Physical Inspection**:\n    - Inspect for macroscopic uniformity (e.g., absence of phase separation, visible aggregates).\n    - Measure viscosity changes in the formulation (increased viscosity often indicates successful hydrogen-bonding interactions).\n\n9. **Chemical and Structural Analysis**:\n    - **FTIR Spectroscopy**:\n        - Look for characteristic peaks of UPy groups (e.g., N\u2013H at ~3200\u20133500 cm\u207b\u00b9, C=O at ~1700 cm\u207b\u00b9) in the final polymer. Compare it with the pristine spectra of UPy-D400.\n    - **NMR Spectroscopy**:\n        - Confirm the presence of UPy-D400 by detecting signature chemical shifts (e.g. pyrimidinone protons) in the final polymer.\n    - **X-ray Diffraction (XRD)** (if crystalline domains are present):\n        - Check for new crystalline peaks from UPy interactions, which indicate successful interaction and self-assembly in the polymer matrix.\n\n10. **Water Absorption/Contact Angle Testing**:\n    - Validate the enhanced hydrophilicity by measuring water contact angle (should decrease after UPy-D400 incorporation).\n    - Alternatively, perform swelling experiments to test water uptake in hydrophilic environments.\n\n---\n\n### **Conclusion**\nBy following these steps, you can ensure the successful incorporation of UPy-D400 into the polymer formulation. The detailed checks and balances ensure uniform mixing during preparation and adequate verification for successful integration into the polymer structure. This approach provides a systematic synthesis pathway while ensuring reproducibility for experimental success. \u2727"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Design an experimental scheme using rape oil as a key reagent to modify a polymer for increased hydrophilicity, and outline all necessary steps and conditions."}, {"role": "assistant", "content": "Thank you for posing the question regarding the use of rape oil to modify a polymeric system for enhanced hydrophilicity. As your professor, I will analyze the problem, summarize the critical points, and carefully design a methodical and detailed experimental preparation scheme. This response aligns with your needs and laboratory practice requirements.\n\n---\n\n### **Key Points of the Question:**\n1. **Objective:** Increase the hydrophilicity of a polymer system using rape oil as a key reagent.\n2. **Primary Considerations:** Design the experimental procedure systematically, focusing on the functionalization chemistry that employs rape oil.\n3. **Essential Details:** Include necessary steps such as reaction conditions, reagent ratios, molar quantities, temperatures, catalysts, and purification.\n\n---\n\n### **Scientific Approach and Analysis:**\nRape oil (commonly known as rapeseed oil) is composed mainly of triglycerides, where long-chain fatty acids are esterified with glycerol. To enhance hydrophilicity, it will be necessary to modify its hydrophobic aliphatic chains with hydrophilic functional groups. The polymer itself must be selected or synthesized to permit such functionalization. The key mechanism here involves exploiting the reactivity of rape oil (such as its unsaturated bonds or ester group) to improve the hydrophilicity of the resulting polymer.\n\n---\n\n### **Experimental Preparation Scheme:**\nBelow is a systematic formulation of the experimental procedure:\n\n---\n\n#### **Step 1: Polymer Selection and Pretreatment**\n1. **Polymer Choice:** Select a polymer capable of functionalization, such as polyethylene, polypropylene, or polyacrylate. For enhanced hydrophilicity, a base polymer containing reactive groups (e.g., hydroxyl or carboxyl) or capable of grafting is ideal.\n   - Example: Poly(acrylic acid) or poly(vinyl alcohol) can serve as an excellent starting point.\n2. **Pre-treatment (if necessary):**\n   - If starting with a hydrophobic polymer (e.g., polyethylene), perform surface activation via plasma treatment or chemical oxidation to introduce functional groups such as hydroxyl groups.\n   - **Reagents and Conditions:**\n     - Plasma treatment: Treat polymer with oxygen plasma for 2\u20135 minutes at low pressure (~10\u201320 Pa).\n     - Chemical oxidation: Soak polymer in an aqueous solution of a strong oxidant (e.g., KMnO\u2084 in acidic medium) at room temperature for 1\u20132 hours.\n\n---\n\n#### **Step 2: Modification of Rapeseed Oil**\n1. **Objective:** Introduce hydrophilic functionality into rapeseed oil by functionalizing its fatty acid chains with polar groups (e.g., hydroxyl, carboxyl).\n   \n2. **Reaction Pathway: Epoxidation, followed by hydrolysis**\n   - **Epoxidation of Unsaturated Bonds:** Use rapeseed oil's unsaturated fatty acids (e.g., oleic acid) to introduce epoxy groups, which can then be hydrolyzed to form hydroxyl groups.\n   - **Reaction Setup and Conditions:**\n     - In a 3-neck flask, add 100 g of rapeseed oil.\n     - Add 0.05 mol of hydrogen peroxide (H\u2082O\u2082, 30%) and catalytic acetic acid (0.01 mol).\n     - Stir at 60\u00b0C for 4\u20136 hours under mild reflux.\n   - Post-epoxidation, perform hydrolysis:\n     - Add dilute sulfuric acid (0.1 mol H\u2082SO\u2084) to the reaction mixture.\n     - Heat to 80\u201385\u00b0C for 3 hours until hydroxyl groups are introduced on the fatty acid chains.\n   - Purify the hydroxylated rape oil product via solvent extraction, e.g., diethyl ether, followed by drying.\n\n---\n\n#### **Step 3: Polymer Functionalization via Grafting**\n1. **Objective:** Use hydroxylated rapeseed oil as a hydrophilic modifier to graft onto the polymer backbone.\n   \n2. **Reaction Pathway: Esterification or amidation**\n   - If the polymer contains carboxyl or hydroxyl groups (e.g., poly(acrylic acid)), esterification or amidation can bond the hydrophilic segments.\n   - **Reaction Procedure:**\n     - Dissolve 10 g of the base polymer in 100 mL of dimethylformamide (DMF) or another suitable solvent.\n     - Add 0.5 mol hydroxylated rape oil and 0.1 mol of coupling agent (e.g., dicyclohexylcarbodiimide, DCC) along with 0.01 mol of catalyst (e.g., 4-dimethylaminopyridine, DMAP).\n     - Stir at 80\u201390\u00b0C for 6\u20138 hours.\n   - Ensure reflux and proper stirring throughout the reaction.\n   - Monitor functionalization progress using FTIR spectroscopy (look for emergence of ester carbonyl peaks).\n\n---\n\n#### **Step 4: Purification of Hydrophilic Polymer**\n1. Precipitate the modified polymer by adding the reaction mixture dropwise into an excess of non-solvent (e.g., water or ethanol).\n2. Wash the precipitated polymer repeatedly with fresh solvent to remove uncoupled rape oil and reaction byproducts.\n3. Dry the washed polymer under vacuum at 60\u201370\u00b0C overnight.\n\n---\n\n#### **Step 5: Characterization**\n1. **Hydrophilicity Testing:**\n   - Perform water contact angle measurements to compare the hydrophilicity of the original polymer and the modified polymer.\n   - Expect a significant decrease in the water contact angle if functionalization is successful.\n2. **Structural Characterization:**\n   - Use FTIR to confirm the introduction of hydrophilic groups.\n   - Run NMR to verify the structural modification of rape oil and its grafting onto the polymer.\n3. **Thermal Analysis:**\n   - Use DSC/TGA to ensure the thermal stability of the modified polymer.\n\n---\n\n### **Final Notes:**\n- Carefully note all molar ratios and quantities during the experiment.\n- Perform reactions involving peroxide or acids in a well-ventilated fume hood with appropriate protective equipment.\n\nThis experimental scheme outlines the modification of a polymer using rape oil through logical steps, ensuring enhanced hydrophilicity. Let me know if further clarification or adjustments are required, and good luck with your laboratory work!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain the role of the molecule REASOAP SR-10 in the synthesis of a hydrophilic polymer. Specifically, discuss how its reactive group contributes to the formation of a hydrophilic network during the curing process."}, {"role": "assistant", "content": "To systematically answer your question about the role of the molecule REASOAP SR-10 in the synthesis of a hydrophilic polymer and its contributions through its reactive groups, let us proceed step by step. This breakdown will help you fully understand the relevance of the molecule and guide you on how to use it effectively during the polymer synthesis.\n\n---\n\n### Step 1: **Analyze the Question and Summarize Key Points**\n\nKey aspects of your question:\n1. Identify the role of **REASOAP SR-10** within the synthesis of a hydrophilic polymer.\n2. Understand how its **reactive group** contributes to the curing process.\n3. Explain how the reactive group plays a role in developing the **hydrophilic network** within the polymer matrix.\n\nThus, we need to investigate:\n- The structure of REASOAP SR-10 and its functional groups.\n- The chemistry of its reactive group and how it participates in curing.\n- The contribution of its molecular structure to overall hydrophilicity.\n\n---\n\n### Step 2: **Detailed, Systematic Explanation**\n\n#### (i) **Chemical Nature of REASOAP SR-10**\n\nWhile the precise molecular structure and exact reactive groups of REASOAP SR-10 must be verified from its datasheet or literature, let us assume for this explanation that it includes key reactive functional groups such as **epoxy, hydroxyl, or acrylic** moieties. These functional groups are typically involved in covalent crosslinking reactions during curing processes, which are common in polymer synthesis.\n\nAdditionally, REASOAP SR-10 likely incorporates **hydrophilic side groups** such as -OH, -COOH, or ether (-C-O-C-) linkages, which enhance water affinity and contribute to the polymer's hydrophilicity.\n\n#### (ii) **Role of REASOAP SR-10 in Polymer Synthesis**\n\nREASOAP SR-10 serves as a **functional crosslinker or comonomer** in the synthesis of the hydrophilic polymer. It contributes in the following ways:\n\n1. **Introduction of Reactive Sites:**\n   Its reactive groups (e.g., epoxy, hydroxyl, or acrylic) can enable:\n   - Covalent bonding with other monomers.\n   - Formation of a crosslinked polymeric network during curing.\n\n2. **Enhancement of Hydrophilicity:**\n   The presence of polar or hydrophilic groups in REASOAP SR-10 (e.g., hydroxyl or ether units) increases the water-attracting ability of the final polymer. These groups can form hydrogen bonds with water and improve polymer wettability.\n\n3. **Formation of a Crosslinked Hydrophilic Network:**\n   During curing, the reactive groups in REASOAP SR-10 chemically link chains into a 3D network. This crosslinked structure improves water uptake without dissolving, a key feature for certain hydrophilic polymers like hydrogels.\n\n#### (iii) **Curing Process and Reactive Group Chemistry**\n\n- The reactive group in REASOAP SR-10 determines the specific curing reaction.\n  - For **epoxy groups**, crosslinking typically involves an amine-based curing agent that reacts with the epoxy ring.\n  - For **acrylic groups**, curing involves free-radical polymerization initiated by a thermal or photochemical initiator (e.g., benzoyl peroxide or UV light).\n  - For **hydroxyl groups**, curing may occur via esterification with diacids or urethane formation with isocyanates.\n\n- Optimal curing conditions (e.g., temperature, catalysts, and molar ratios) should be chosen based on the reactive group.\n\n---\n\n### Step 3: **Experimental Preparation Scheme for the Synthesis**\n\nHere is a generalized preparation scheme for a hydrophilic polymer incorporating REASOAP SR-10:\n\n1. **Materials Required:**\n   - Monomers (e.g., acrylic acid, N-vinylpyrrolidone, or other hydrophilic monomers).\n   - REASOAP SR-10 as the reactive hydrophilic crosslinker.\n   - Curing agent or initiator (depending on reactive group: e.g., a free-radical initiator for acrylic groups or an amine-based curing agent for epoxies).\n   - Solvent (if required for homogeneity, e.g., water or ethanol).\n\n2. **Step-by-Step Procedure:**\n   - **Step 1: Monomer Mixing:**\n     In a clean reaction flask, mix a selected hydrophilic monomer (e.g., acrylic acid) with the desired amount of REASOAP SR-10. Maintain a molar ratio such that REASOAP SR-10 contributes ~10-20 mol% to promote crosslinking without excessive rigidity.\n\n   - **Step 2: Addition of Initiator/Curing Agent:**\n     Add the curing agent or initiator based on the reactive group in REASOAP SR-10. For example:\n       - If REASOAP SR-10 has acrylic groups, dissolve a free-radical initiator like benzoyl peroxide (0.5 wt%) in the monomer mixture.\n       - If REASOAP SR-10 has epoxy groups, introduce a stoichiometric quantity of an amine curing agent such as triethylenetetramine.\n\n   - **Step 3: Polymerization/Curing:**\n     Heat the reaction mixture to the required temperature (e.g., 60\u201380\u00b0C for free-radical polymerization or room temperature for epoxy curing). For UV-curable systems, expose the mixture to a UV lamp under nitrogen to avoid oxygen inhibition.\n\n   - **Step 4: Post-Curing (If Necessary):**\n     Cure the polymer for additional time (e.g., 2\u20134 hours) at a slightly elevated temperature (e.g., 100\u00b0C) to ensure complete crosslinking.\n\n   - **Step 5: Washing and Drying:**\n     Wash the resultant polymer product to remove any unreacted monomers or byproducts. Use distilled water or a suitable solvent. Dry the polymer in a vacuum oven at 50\u201360\u00b0C.\n\n3. **Precautions:**\n   - Ensure the REASOAP SR-10 and other monomers are fully dissolved/mixed to avoid phase separation.\n   - Control temperature accurately, as overheating can lead to side reactions or degradation.\n\n4. **Characterization:**\n   - Confirm the hydrophilicity of the polymer using contact angle measurements or swelling tests in water.\n   - Verify the crosslinked structure via FTIR spectroscopy (to detect functional groups) or thermal analysis (DSC/TGA).\n\n---\n\n### Step 4: **Specific Contribution of REASOAP SR-10\u2019s Reactive Group**\n\nThe reactive group of REASOAP SR-10 plays a dual role:\n1. It directly participates in the covalent crosslinking reaction to form a stable 3D polymer network.\n2. It introduces hydrophilic functionality to the network, allowing the polymer to exhibit water-swelling or water-retention behavior, crucial for hydrophilic applications like coatings, membranes, or hydrogels.\n\n---\n\n### Conclusion\n\nIn summary, REASOAP SR-10 is a valuable component in hydrophilic polymer synthesis due to its dual functionality: crosslinking via reactive groups and enhancing hydrophilicity through polar side groups. By carefully optimizing reaction conditions and polymerization parameters, you can exploit its properties to produce a robust and hydrophilic polymer network capable of absorbing water or interacting with aqueous environments. Following the above experimental scheme should allow you to successfully synthesize and characterize the desired hydrophilic polymer product."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Design a step-by-step procedure to immobilize DNA onto the polymer surface, ensuring that the modification increases the hydrophilic characteristics of the polymer."}, {"role": "assistant", "content": "Certainly, immobilizing DNA onto a polymer surface is an excellent method to enhance the polymer's hydrophilicity due to DNA's inherent hydrophilic properties arising from its sugar-phosphate backbone. Let\u2019s tackle this systematically and design a robust experimental procedure for this modification.\n\n### Step 1: Analyze the Question\nThe goal is to immobilize DNA onto a polymer surface to enhance the polymer's hydrophilicity. To achieve this:\n- The polymer surface must be activated or functionalized to offer reactive sites for DNA immobilization.\n- DNA immobilization should be done under conditions that preserve its structural and functional integrity.\n- Select a coupling chemistry suitable for covalent attachment to ensure stable immobilization of DNA on the polymer.\n\n### Step 2: Experimental Preparation Scheme\nBelow is a detailed step-by-step procedure to modify the polymer and immobilize DNA:\n\n---\n\n#### **Step 1: Surface Activation (Introduce Reactive Functional Groups)**\nTo immobilize DNA, the polymer surface (e.g., a hydrophobic polymer like polyethylene or a partially hydrophilic polymer like polyacrylamide) needs to be activated. One common method is oxidation or functionalization with specific groups like -COOH, -NH2, or -OH that can react with DNA.\n\n1. **Clean the Polymer Surface:**\n   - Wash the polymer surface with ethanol and distilled water thoroughly to remove any impurities or residues.\n   - Dry the polymer with nitrogen gas.\n\n2. **Introduce Carboxyl Groups (if not already present):**\n   If the polymer is inert or hydrophobic (e.g., polyethylene, polystyrene), oxidative methods like plasma treatment or chemical oxidation can be used:\n   - **Plasma Treatment:** Expose the polymer to oxygen plasma to introduce surface carboxyl and hydroxyl groups.\n     - Conditions: Oxygen plasma, 200 W, 10 minutes, room temperature.\n   - Alternatively, use potassium permanganate or a chromic acid solution to oxidize the polymer surface:\n     - **Chromic Acid:** Immerse the polymer in an aqueous solution containing 10% w/v sodium dichromate and 1M sulfuric acid. Incubate at 60 \u00b0C for 1 hour.\n     - After oxidation, rinse with copious amounts of deionized water to remove residual chemicals.\n\n---\n\n#### **Step 2: Crosslinker Coupling for DNA Immobilization**\nFunctionalizing the surface with a crosslinker ensures effective binding between the polymer and DNA. One effective choice for DNA immobilization is the use of carbodiimide chemistry (e.g., EDC/NHS coupling) to attach the DNA via its amine or phosphate groups.\n\n1. **Activation of Carboxyl Groups:**\n   - Prepare a fresh solution of EDC (1-ethyl-3-(3-dimethylaminopropyl) carbodiimide) and NHS (N-hydroxysuccinimide).\n     - Dissolve 0.1 M EDC and 0.05 M NHS in a buffer solution at a pH of 5.5 (e.g., MES buffer).\n   - Immerse the polymer surface in the EDC-NHS solution and incubate for 2 hours at room temperature under mild agitation.\n   - This step activates the carboxyl groups on the polymer, creating reactive esters that can covalently bind amino groups in DNA.\n\n2. **DNA Solution Preparation:**\n   - Dissolve the DNA (single-stranded or double-stranded, depending on your application) in phosphate-buffered saline (PBS) at a concentration of 50\u2013100 \u00b5M.\n   - Ensure the DNA is free from contaminants like salts or organic solvents; purify if necessary.\n\n3. **Covalent Coupling of DNA:**\n   - Add the DNA solution onto the EDC/NHS-activated polymer surface.\n   - Incubate at room temperature for 4\u20136 hours or at 4 \u00b0C overnight to allow efficient binding.\n   - During this step, the amino group in DNA (e.g., from nucleobases or chemically modified DNA with terminal -NH2 groups) reacts with the ester group on the polymer surface, forming a stable amide bond.\n\n---\n\n#### **Step 3: Post-Immobilization Washing and Confirmation**\nAfter coupling, unbound DNA and reagents must be removed, and the degree of DNA modification needs to be verified.\n\n1. **Washing:**\n   - Wash the polymer surface thoroughly with PBS buffer to remove unreacted DNA and any residual EDC/NHS.\n   - Perform additional washing with deionized water to ensure the removal of salts.\n\n2. **Blocking Remaining Active Sites:**\n   - To avoid nonspecific interactions, block any unreacted carboxyl groups on the polymer surface by treating with 1M ethanolamine (pH 8.0) for 30 minutes.\n   - Wash again with PBS buffer.\n\n3. **Characterization:**\n   - Confirm DNA immobilization using techniques like:\n     - UV-Vis spectroscopy to measure DNA absorbance at 260 nm on the surface.\n     - X-ray photoelectron spectroscopy (XPS) or Fourier-transform infrared spectroscopy (FTIR) to detect characteristic phosphate or amide bond peaks.\n     - Contact angle measurements to confirm increased hydrophilicity (a decrease in water contact angle indicates successful surface modification and enhanced hydrophilicity).\n\n---\n\n### Summary of Key Reaction Conditions and Reagent Ratios:\n- **Surface Oxidation (if needed):** Chromic acid treatment or oxygen plasma.\n- **Carbodiimide Coupling:** 0.1 M EDC, 0.05 M NHS in MES buffer (pH 5.5).\n- **DNA Concentration:** 50\u2013100 \u00b5M in PBS buffer.\n- **Reaction Time:** 4\u20136 hours at room temperature or overnight at 4 \u00b0C.\n- **Blocking Agent:** 1M ethanolamine (pH 8.0).\n\nThis detailed and systematic scheme should enable the successful immobilization of DNA onto your polymer surface, significantly enhancing its hydrophilicity. Feel free to consult me for further clarifications or scaling adjustments for your specific setup."}]}
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+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "When preparing a hydrogel using agarose as the polymer matrix, describe how black phosphorus (BP) sheets can be added to the system to enhance the hydrophilicity of the final material. Include the conditions needed for successful dispersion and integration."}, {"role": "assistant", "content": "Certainly! When preparing a hydrogel using agarose as the polymer matrix and incorporating black phosphorus (BP) sheets to enhance the hydrophilicity of the final material, we must carefully consider the dispersion of BP sheets in the polymer matrix and the interactions needed to create a stable, hydrophilic system. Let's proceed step by step:\n\n---\n\n### **Step 1: Key Points and Analysis**\n1. **Objective:** To enhance the hydrophilicity of an agarose-based hydrogel by integrating black phosphorus (BP) sheets.\n2. **Challenges:**\n   - Black phosphorus sheets are hydrophobic in their native form and can aggregate in aqueous environments, so dispersing them uniformly is critical.\n   - BP sheets are sensitive to oxidation in aqueous solutions, so careful handling and stabilization are needed to preserve their properties.\n   - Compatibility between BP sheets and the agarose matrix requires establishing physical or chemical interactions.\n3. **Strategies:**\n   - Functionalizing BP sheets to improve their solubility and dispersion in aqueous solutions.\n   - Processing the agarose in conditions that allow uniform integration of BP sheets without degrading either component.\n\n---\n\n### **Step 2: Experimental Preparation Scheme**\n\n#### **Step 2.1: Materials Required**\n1. **Agarose:** High-purity agarose as the polymer matrix.\n2. **Black Phosphorus (BP) Sheets:** Exfoliated BP sheets with controlled thickness (e.g., nanoscale sheets).\n3. **Dispersing Agent:** A suitable surfactant or stabilizer such as polyvinylpyrrolidone (PVP) or sodium cholate to improve BP dispersion.\n4. **Deionized (DI) Water:** As a solvent for agarose preparation.\n5. **Optional Functionalizing Agents:** For example, dopamine or polyethylene glycol (PEG) to modify BP sheets chemically for enhanced hydrophilicity and compatibility.\n6. **Crosslinkers (if required):** If agarose requires additional crosslinking for mechanical stability.\n\n---\n\n#### **Step 2.2: Preparation of Black Phosphorus (BP) Dispersion**\n1. **Exfoliation of BP Sheets:**\n   - Weigh a specific amount of black phosphorus crystals (e.g., 100 mg).\n   - Prepare a solution of surfactant or stabilizer in deionized water (e.g., use 0.1\u20130.5 wt% PVP or 1% sodium cholate).\n   - Add the BP crystals to the solution and sonicate using a probe-tip ultrasonicator for 2\u20133 hours at 4 \u00b0C (to prevent overheating and oxidation). Set the sonicator to a pulsed mode (e.g., 10 s on, 10 s off) to avoid degradation of BP sheets.\n   - After sonication, centrifuge the solution at 5000 rpm for 15 minutes to remove larger aggregates, leaving a stable dispersion of BP sheets in the supernatant.\n\n2. **Optional Functionalization:**\n   - If additional hydrophilicity or stability is needed:\n     - Functionalize BP sheets with molecular modifiers such as dopamine or PEG by adding them to the BP dispersion. \n     - For example, add dopamine (10 mg/mL) under mildly basic conditions (e.g., pH ~8 using tris buffer) to graft it onto the BP surface.\n   - Stir the mixture for 12 hours at room temperature under an inert atmosphere (e.g., nitrogen or argon).\n\n---\n\n#### **Step 2.3: Preparation of Agarose Hydrogel Matrix**\n1. **Agarose Solution Preparation:**\n   - Weigh the desired amount of agarose (e.g., 1\u20133 wt% depending on the desired stiffness of the hydrogel).\n   - Dissolve the agarose in deionized water by heating the solution to 90\u201395 \u00b0C with constant stirring. Ensure the agarose completely dissolves to form a clear solution.\n\n2. **Integration of BP Sheets:**\n   - Cool the agarose solution to approximately 50\u201360 \u00b0C (still in the liquid state but not too hot to degrade BP sheets).\n   - Slowly add the prepared BP dispersion dropwise under constant stirring to the agarose solution. Maintain the BP-to-agarose weight ratio as desired (e.g., 0.2\u20130.5 wt% BP relative to the agarose).\n   - Stir the mixture for 10\u201315 minutes to ensure uniform distribution of BP sheets within the agarose matrix.\n\n---\n\n#### **Step 2.4: Gelation and Crosslinking**\n1. **Gelation:**\n   - Pour the BP-agarose solution into a mold or container of desired shape.\n   - Allow the solution to cool to room temperature, promoting the physical gelation of agarose.\n\n2. **Optional Crosslinking (If Required):**\n   - If mechanical strength or stability enhancement is needed, introduce a chemical crosslinker (e.g., genipin or glutaraldehyde) at this stage. Ensure that the crosslinking reaction conditions (e.g., pH, reaction time) are mild enough to preserve BP integrity.\n\n---\n\n### **Step 3: Final Steps and Considerations**\n1. **Oxidation Mitigation:**\n   - Store the prepared hydrogel under an inert environment (e.g., nitrogen or argon) during experiments to minimize BP oxidation. \n   - Alternatively, incorporate antioxidants such as ascorbic acid or sodium ascorbate into the system to prolong BP stability.\n\n2. **Characterization:**\n   - Verify the uniform dispersion of BP sheets and their interaction with the agarose matrix using techniques such as optical microscopy, scanning electron microscopy (SEM), or transmission electron microscopy (TEM).\n   - Assess the hydrophilicity of the prepared hydrogel using water contact angle measurements.\n\n3. **Applications Testing:**\n   - Test the performance of the hydrogel in its intended application (e.g., biomedical, environmental, or sensing applications). \n\n---\n\n### **Summary**\nIncorporating BP sheets into an agarose-based hydrogel requires optimizing both the exfoliation and dispersion of BP sheets and their integration into the agarose matrix. Key steps include the preparation of a stable BP dispersion, functionalization (if needed), and careful mixing with the agarose solution under controlled conditions to prevent aggregation or degradation. The resulting hydrogel benefits from the enhanced hydrophilicity and potential functional properties imparted by the BP sheets.\n\nBy following this preparation scheme, you can reliably produce a high-quality BP-agarose hydrogel for further experimentation. Let me know if you have any additional questions or require clarification!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain the role of 2-acrylamido-2-methyl propane sulfonic acid (AMPS) in enhancing the hydrophilicity of the polymer during its copolymerization process."}, {"role": "assistant", "content": "Certainly! Let's address your question systematically while following the outlined requirements for clarity and depth. The focus here is understanding the role of 2-acrylamido-2-methyl propane sulfonic acid (AMPS) in enhancing the hydrophilicity of a polymer during its copolymerization process.\n\n---\n\n### **Key Points from the Question**\n1. **Analyzing the molecule**: AMPS is a highly functional monomer with both amide and sulfonic acid groups. These groups contribute significantly to the hydrophilicity of the polymer.\n2. **Core topic**: We aim to determine and explain how AMPS enhances hydrophilicity during copolymerization and the mechanisms that underlie its behavior.\n\nNow, I will answer systematically step by step:\n\n---\n\n### **Detailed Explanation and Experimental Preparation for Copolymerization Involving AMPS**\n\n#### **I. Properties of AMPS Relevant to Hydrophilicity**\nAMPS is a hydrophilic monomer for several reasons:\n1. **Sulfonic Acid Group (-SO\u2083H)**:\n   - The sulfonic acid functional group is highly polar and ionizable. This polarity enables AMPS-containing polymers to interact strongly with water molecules through hydrogen bonding and ionic interactions, thereby enhancing hydrophilicity.\n   - The sulfonic group also provides excellent water solubility and anti-fouling properties, making AMPS ideal for polymers in aqueous environments.\n   \n2. **Amide Group (-CONH\u2082)**:\n   - The amide group can form hydrogen bonds, further contributing to hydrophilicity.\n   - It assists in stabilizing the polymer structure with dual hydrophilic capabilities from both the amide and sulfonic acid functionalities.\n\nTogether, these groups make AMPS a building block for hydrophilic polymers, enabling applications such as water-absorbent materials, medical hydrogels, and ion-exchange membranes.\n\n---\n\n#### **II. Copolymerization Process Using AMPS**\n\n**Objective**: To introduce AMPS as a co-monomer during the synthesis of a hydrophilic polymer, enhancing the polymer's interaction with water.\n\n##### **1. Selection of Co-Monomers**\nWhen designing the copolymerization scheme:\n- Select co-monomers that are compatible with AMPS. Examples include non-ionic hydrophilic monomers (e.g., acrylamide, N-vinyl pyrrolidone) or ionic monomers (e.g., acrylic acid).\n  \n- The choice of co-monomers depends on the targeted polymer properties. For hydrophilic polymers, acrylamide (AM) or acrylic acid (AA) are common partners in copolymerization with AMPS.\n\n##### **2. Reaction Conditions**\n- **Reaction Type**: Free-radical copolymerization is the preferred method for incorporating AMPS due to its efficiency.\n- **Initiator**: Use a water-soluble initiator such as potassium persulfate (KPS) or ammonium persulfate (APS), as AMPS is highly hydrophilic.\n- **Solvent**: An aqueous system is suitable since AMPS and most co-monomers dissolve well in water.\n- **Temperature**: Set the reaction temperature within 60\u201380\u00b0C, which is typical for persulfate initiators.\n- **pH Control**: Important to maintain pH between 5\u20137 to ensure the sulfonic acid group remains ionized, maximizing hydrophilic properties.\n\n##### **3. Proportions and Molar Ratios**\n- The molar ratio of AMPS to co-monomer (e.g., acrylamide) depends on the desired hydrophilicity. Typical ratios are 1:1 or 1:2 (AMPS:co-monomer).\n- Example: For 10 g total monomer weight:\n  - AMPS: 5 g\n  - Acrylamide (AM): 5 g\n\n##### **4. Reaction Monitoring**\n- Stir the solution continuously to ensure homogeneous mixing of AMPS during polymerization.\n- Monitor viscosity as the reaction progresses, indicating polymer formation.\n\n---\n\n#### **III. Role of AMPS in Enhancing Hydrophilicity**\nDuring copolymerization, AMPS contributes to hydrophilicity in several ways:\n1. **Ionic Nature**:\n   - The sulfonic acid group dissociates in water, creating negative charges on the polymer chain. These charges attract water molecules and repel contaminants, maximizing hydrophilic behavior.\n   \n2. **Hydrogen Bonding**:\n   - Both the sulfonic group and amide group enable the polymer to form strong hydrogen bonds with water molecules, further enhancing water retention.\n\n3. **Copolymer Formation**:\n   - AMPS forms covalent bonds with co-monomers (e.g., acrylamide) during free-radical polymerization. The resulting polymer chain integrates AMPS units uniformly, ensuring hydrophilicity throughout the polymer.\n\n4. **Structural Impact**:\n   - The bulkiness of the AMPS molecule contributes to chain separation within the polymer, preventing aggregation. This structural feature increases surface area exposure to water, boosting hydrophilicity.\n\n---\n\n#### **IV. Example Protocol for Copolymerization of AMPS and Acrylamide**\n1. **Materials**:\n   - AMPS: 5 g\n   - Acrylamide: 5 g\n   - Distilled water: 100 mL\n   - Potassium persulfate (KPS): 0.1 g (initiator)\n\n2. **Procedure**:\n   1. Dissolve acrylamide and AMPS in distilled water to form a homogeneous solution.\n   2. Add KPS to the solution while stirring under nitrogen purge to eliminate oxygen (oxygen inhibits free-radical polymerization).\n   3. Heat the solution to 70\u00b0C and maintain constant stirring for 2 hours.\n   4. After polymerization, cool the mixture and precipitate the polymer by adding it dropwise into acetone (non-solvent).\n\n3. **Characterization**:\n   - Test hydrophilicity using water absorption studies, contact angle measurements, or swelling ratio analysis.\n\n---\n\n#### **Key Takeaways**\n- AMPS plays a critical role in enhancing hydrophilicity through its sulfonic acid and amide groups, providing ionic and hydrogen-bonding capabilities.\n- During copolymerization, careful control of molar ratios, reaction conditions, and solvent systems ensures successful incorporation of AMPS into the polymer chain.\n- AMPS-based hydrophilic polymers can be tailored for diverse applications, including water treatment, superabsorbent materials, and biomedical devices.\n\nBy following this systematic approach, you can fully leverage AMPS's properties to synthesize a polymer with enhanced hydrophilicity.\n\n--- \n\nLet me know if you'd like further clarification on any step or additional insights!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain how you would incorporate alkylene oxides into the backbone of a polyurethane polymer to enhance its hydrophilicity. Include specific steps in the synthesis process."}, {"role": "assistant", "content": "Incorporating alkylene oxides into the backbone of a polyurethane polymer is an effective strategy to enhance its hydrophilicity. I will systematically address your question by analyzing the key points and providing a detailed experimental preparation scheme, including reaction conditions, reagent ratios, molar quantities, and other relevant details to ensure a clear understanding and practical implementation.\n\n---\n\n### **Key Points to Consider**\n1. **Objective**: To enhance the hydrophilicity of a polyurethane polymer by introducing alkylene oxides, such as polyethylene glycol (PEG) or polypropylene glycol (PPG), as soft segments into the polymer backbone.\n2. **Polyurethane Basics**: Polyurethane synthesis involves the reaction between polyols and di- or multi-functional isocyanates. Alkylene oxides serve as hydrophilic polyols due to their ether linkages.\n3. **Primary Requirements**: \n   - Selection of hydrophilic alkylene oxides as polyol precursors.\n   - Control of molar ratios to achieve the desired hydrophilicity and mechanical properties.\n   - Prevention of phase separation during polymerization.\n\n---\n\n### **Experimental Preparation Scheme**\n\n#### **Step 1: Selection of Raw Materials**\n1. **Polyols (Hydrophilic Component)**:  \n   Use polyethylene glycol (PEG) with controlled molecular weights, e.g., PEG-400 or PEG-1000, depending on the desired degree of hydrophilicity. PEG is a copolymer of ethylene oxide, making it particularly suitable for introducing hydrophilic properties.\n   - For lower hydrophilicity: You might consider polypropylene glycol (PPG), a copolymer of propylene oxide, as its hydrophilic nature is less pronounced than PEG.\n2. **Isocyanates**:  \n   Select aromatic or aliphatic di-isocyanates, such as:\n   - Aromatic: Methylene diphenyl diisocyanate (MDI).\n   - Aliphatic: Hexamethylene diisocyanate (HDI).  \n   Aliphatic di-isocyanates are less likely to yellow with time and exposure, suitable for applications in coatings and biomedical devices.\n3. **Chain Extender (Optional)**:  \n   Use a small diol such as 1,4-butanediol (BDO) or ethylene glycol to tune mechanical properties.\n\n---\n\n#### **Step 2: Pre-experiment Setup**\n1. **Equipment**:\n   - A glass reactor equipped with stirring, temperature control, and nitrogen purging.\n2. **Safety Precautions**:\n   - Isocyanates are highly reactive and toxic. Work in a fume hood with gloves and proper protective equipment.\n3. **Solvents** (if required for miscibility): Use dry solvents such as dimethylformamide (DMF) or tetrahydrofuran (THF). Ensure solvents are anhydrous to prevent side reactions with water.\n\n---\n\n#### **Step 3: Synthesis Process**\n1. **Molar Ratios**:  \n   - Maintain a 1:1 isocyanate-to-hydroxyl ratio for a stoichiometric reaction.\n   - If PEG is the soft segment, select molecular weights and adjust ratios based on desired hydrophilicity. For example:\n     - For enhanced hydrophilicity: Use PEG-1000 and target 50% by weight in the final polymer.\n     - For reduced hydrophilicity: Use PEG-400 and target 30% by weight in the final polymer.\n\n2. **Reaction Conditions**:\n   - Dry all materials before use to avoid water interfering with the isocyanate reaction.\n   - Degas PEG and solvents by purging with dry nitrogen for 30 minutes.\n   - Tropsch the isocyanates under inert gas (e.g., nitrogen).\n\n3. **Step-by-Step Polymerization**:\n   **Step 3.1: Formation of Prepolymer**  \n   - Add the calculated amount of PEG to a reactor with anhydrous solvent (if required).\n   - Heat the reactor to 60\u201380\u00b0C under gentle stirring.\n   - Introduce the di-isocyanate slowly in the stoichiometric ratio (NCO:OH = 1:1). Monitor the progress with FTIR spectroscopy\u2014hydroxyl depletion and NCO peaks should be tracked.\n   - Allow the reaction between PEG and di-isocyanate to form the prepolymer. This typically takes **2\u20134 hours**.\n\n   **Step 3.2: Polymer Formation**  \n   - Cool the reaction mixture to 40\u201360\u00b0C.\n   - If a chain extender is used (e.g., BDO), add it slowly in the calculated stoichiometric ratio (NCO:OH = 1:1). Chain extenders help tune mechanical properties.\n   - Continue stirring at 40\u201360\u00b0C for an additional **3\u20136 hours**.\n\n4. **Post-reaction Monitoring**:\n   - Analyze the polymer structure using **FTIR**: Ensure complete reaction of isocyanate and hydroxyl groups.\n   - Gel permeation chromatography (GPC) can be used to analyze molecular weight distribution.\n\n---\n\n#### **Step 4: Purification and Post-processing**\n- Allow the polymer to cure if necessary (e.g., for coatings).\n- Optionally wash with ethanol or other solvents to remove unreacted reactants or side products.\n- Dry the polymer in a vacuum oven at 40\u201360\u00b0C to remove residual solvents.\n\n---\n\n#### **Step 5: Testing Hydrophilicity**\n- Perform water contact angle measurements. Hydrophilic polymers typically exhibit a low contact angle (<90\u00b0).\n- Optional: Measure swelling properties in water, as PEG-incorporated polyurethane will absorb water due to its hydrophilic nature.\n\n---\n\n### **Notes on Optimization**\n1. **Balancing Hydrophilicity**: Excess PEG can reduce mechanical properties like tensile strength and elasticity. Carefully optimize its weight fraction in the polymer backbone.\n2. **Curing Agents** (if necessary): Select curing agents depending on the application, such as water for polyurethane foams or UV-activated agents for coatings.\n3. **Environmental Considerations**: Use greener alternatives if possible, such as bio-based isocyanates.\n\n---\n\nBy following these steps, you should be able to successfully synthesize a polyurethane polymer with enhanced hydrophilicity, customized to your experimental requirements. Let me know if you'd like further assistance with detailed calculations or any specific adjustments!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the steps you would take to use sulfonic acid group-containing surfactants to prepare a modified hydrophilic polymer. Include the reaction conditions and catalysts required for the process."}, {"role": "assistant", "content": "Alright, let\u2019s systematically develop an experimental preparation scheme for synthesizing a sulfonic acid group-modified hydrophilic polymer using a sulfonic acid group-containing surfactant. I'll analyze the problem first and then outline each step clearly.\n\n---\n\n### **Step 1: Problem Analysis**\nThe challenge is to prepare a hydrophilic polymer modified with sulfonic acid groups. Sulfonic acid groups (-SO\u2083H) are strongly hydrophilic due to their high polarity and ability to attract water. Incorporating these groups into a polymer will greatly enhance its hydrophilicity.\n\nWe will achieve this by:\n1. Choosing an appropriate polymer backbone that can react with the sulfonic acid group-containing surfactant.\n2. Ensuring the sulfonic acid groups can chemically attach (often through grafting or copolymerization methods) or become stably incorporated into the polymer matrix.\n3. Optimizing reaction conditions (temperature, pH, catalysts) for efficient grafting/modification.\n\n---\n\n### **Step 2: Experimental Design**\nHere is a systematic synthesis process. The approach will use free radical copolymerization to attach a sulfonic acid group-containing surfactant onto a vinyl monomer or polymer backbone.\n\n#### **Materials Required:**\n1. **Base Polymer**: A suitable vinyl monomer such as acrylamide, methacrylic acid, or vinyl acetate.\n2. **Sulfonic Acid Group-Containing Surfactant**: Sodium dodecylbenzenesulfonate (SDBS), known for its strong sulfonic acid group (-SO\u2083Na).\n3. **Initiator (Radical Source)**: Potassium persulfate (KPS) or ammonium persulfate (APS).\n4. **Solvent/Medium**: Deionized water or an aqueous ethanol solution (depending on polymer solubility).\n5. **Crosslinking Agent (if needed)**: N,N'-methylenebis(acrylamide) for structural integrity.\n6. **Catalyst**: Sodium metabisulfite, which facilitates decomposition of the persulfate initiator for rapid radical formation.\n\n---\n\n### **Step 3: Reaction Mechanism and Steps**\n\n#### **1. Pre-Treatment and Solution Preparation**\n1. **Preparation of Reaction Medium**:\n   - Dissolve the base monomer (e.g., acrylamide) in deionized water, keeping the concentration around 15-25 wt%. \n   - Add a small amount of crosslinker (if mechanical strength is desired), e.g., N,N'-methylenebis(acrylamide), at 0.1-0.5 wt%.\n\n2. **Preparation of Sulfonic Acid Surfactant Solution**:\n   - Dissolve the sulfonic acid surfactant (e.g., SDBS) in water. Maintain a surfactant concentration of ~1-5 wt%, optimizing based on the desired degree of sulfonation. \n   - Adjust the pH to ~6-7 if needed, ensuring all reactants stay in a suitable ionic state.\n\n3. **Initiator Solution**:\n   - Dissolve potassium persulfate (KPS) in deionized water (at ~0.5-1 wt%). Optionally, prepare sodium metabisulfite (0.5 wt%) in a separate container to accelerate initiation.\n\n---\n\n#### **2. Polymerization Reaction: Radical Copolymerization**\n1. **Reaction Setup**:\n   - Use a three-neck round-bottom flask with a reflux condenser, magnetic stirrer, thermometer, and nitrogen inlet (to maintain an inert nitrogen atmosphere).\n   - Add the prepared monomer solution and sulfonic acid group-containing surfactant solution to the flask.\n\n2. **Degassing**:\n   - Purge the flask with nitrogen gas for 20-30 minutes to remove dissolved oxygen, which can inhibit radical polymerization.\n\n3. **Initiation**:\n   - Heat the reaction mixture to 60-70\u00b0C under a nitrogen atmosphere.\n   - Slowly add the persulfate initiator solution dropwise into the reaction flask. If using sodium metabisulfite, add it simultaneously.\n   - Stir the mixture constantly to ensure uniform distribution of radicals.\n\n4. **Polymerization**:\n   - Maintain the reaction temperature at 65-70\u00b0C for 4-6 hours. Monitor the viscosity of the reaction mixture as polymerization progresses.\n\n---\n\n#### **3. Post-Polymerization and Purification**\n1. **Precipitation**:\n   - Once polymerization is complete, cool the reaction mixture to room temperature. Precipitate the polymer by adding the mixture dropwise into a large volume of a non-solvent (e.g., ethanol or acetone) with stirring.\n\n2. **Washing**:\n   - Wash the precipitated polymer thoroughly to remove unreacted monomers, surfactant residues, and salts. Use ethanol and deionized water alternately.\n\n3. **Drying**:\n   - Dry the purified polymer in a vacuum oven at 40-50\u00b0C until constant weight is achieved.\n\n---\n\n### **Step 4: Characterization**\n1. **FTIR Analysis**:\n   - Confirm the presence of sulfonic acid groups on the polymer backbone by identifying the characteristic -SO\u2083 stretching vibration peak (~1035\u20131080 cm\u207b\u00b9) in the FTIR spectrum.\n\n2. **Contact Angle Measurement**:\n   - Evaluate the hydrophilicity of the modified polymer surface using contact angle goniometry. A lower contact angle indicates enhanced hydrophilicity.\n\n3. **Thermogravimetric Analysis (TGA)**:\n   - Assess the thermal stability of the modified polymer.\n\n4. **Water Absorption Test**:\n   - Quantify the increase in water absorption (swelling ratio) after sulfonation as a measure of hydrophilicity.\n\n---\n\n### **Key Reaction Equation**\nIf acrylamide (CH\u2082=CHCONH\u2082) is used as the base monomer, the reaction involves free radical copolymerization with SDBS:\n\n\\[ \\text{CH}_{2}=\\text{CHCONH}_{2} + \\text{C}_{12}\\text{H}_{25}\\text{C}_{6}\\text{H}_{4}\\text{SO}_{3}^{-} \\longrightarrow \\text{[Polymer-SO}_{3}\\text{H]} \\]\n\n---\n\n### **Important Notes**\n1. **Temperature Control**: Ensure the temperature does not exceed 70\u00b0C to avoid decomposition of reactants.\n2. **Molar Ratios**:\n   - Monomer (vinyl monomer): 1 mmol.\n   - Sulfonic acid surfactant: 0.1-0.3 mmol.\n   - Initiator (KPS): 0.01-0.05 mmol.\n3. **Safety**: Work with sulfonic acid surfactants in a well-ventilated fume hood, as they can release fumes during dissolution.\n\nBy following this method step by step, you should successfully prepare a sulfonic acid-modified hydrophilic polymer and understand its chemistry thoroughly.\n\n---\n\nWould you like further clarification on any part of the process?"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Given a specific molecule of your choice that enhances hydrophilicity, propose a mechanism for incorporating it into a polymer material to increase water affinity. What type of functional groups on the polymer backbone would facilitate this modification?"}, {"role": "assistant", "content": "Certainly! Let's break this down step by step and propose a detailed experimental strategy for synthesizing a hydrophilic polymer by incorporating a specific functionality into a polymer backbone to increase its water affinity.\n\n---\n\n### **Step 1: Analyze the Question**\n#### Key Points:\n1. **Objective**: To enhance polymer hydrophilicity by chemically modifying the polymer backbone with a hydrophilic molecule.\n2. **Key Deliverable**: A detailed experimental preparation scheme, including:\n   - The choice of a specific hydrophilic molecule.\n   - A method or mechanism to chemically incorporate the molecule into the polymer material.\n   - Consideration of functional groups on the polymer backbone that facilitate this modification.\n\n---\n\n### **Step 2: Selection of Hydrophilic Molecule**\nTo increase hydrophilicity, we need a molecule or functionality that exhibits strong interactions with water, such as:\n- Hydroxyl (-OH) groups\n- Amine (-NH\u2082) groups\n- Carboxylic acid (-COOH) groups\n- Sulfonic acid (-SO\u2083H) groups\n- Polyethylene glycol (PEG)-based chains (ethylene oxide units).\n\nFor this scheme, I will choose **polyethylene glycol (PEG)** as the hydrophilic molecule. PEG provides excellent hydrophilicity due to its rich ether oxygen atoms capable of hydrogen bonding with water molecules.\n\n---\n\n### **Step 3: Selection of Polymer Backbone and Functional Groups**\nPotential polymer backbones for modification include those that contain reactive functional groups or can be suitably functionalized to include:\n- Hydroxyl (-OH)\n- Amino (-NH\u2082)\n- Epoxy groups\n- Double bonds for radical reactions\n\nFor this scheme, let\u2019s use **poly(methyl methacrylate) (PMMA)** as the polymer backbone because:\n1. It has good compatibility with modification chemistry.\n2. Its ester groups can be hydrolyzed to introduce carboxylic acids (-COOH) or reacted with suitable hydrophilic molecules such as PEG.\n\n---\n\n### **Step 4: Experimental Preparation Scheme**\nNow, I will outline a systematic scheme for the modification of PMMA with PEG to create a hydrophilic polymer.\n\n---\n\n#### **Step 4.1: Materials and Reagents**\n1. **Poly(methyl methacrylate) (PMMA)** \u2013 backbone polymer.\n2. **Hydrophilic molecule**: Polyethylene glycol monomethacrylate (PEG-MA) (or PEG with appropriate terminal functionality).\n3. **Solvent**: Dimethylformamide (DMF) or tetrahydrofuran (THF).\n4. **Initiator**: Azobisisobutyronitrile (AIBN) for free radical polymerization.\n5. **Catalysts/Additional Reagents**: Depending on the specific modification route (e.g., DCC/NHS for ester bond formation, or NaOH for hydrolysis).\n\n---\n\n#### **Step 4.2: Reaction Mechanisms and Steps**\n##### **Option 1: Grafting PEG on the PMMA Backbone via Free Radical Polymerization**\n1. **Dissolve PMMA and PEG Monomer**: \n   - Dissolve PMMA and PEG-monomethacrylate in DMF at a concentration of approximately 0.5\u20131.0 M (molecular weight ratios can be chosen to control the degree of modification).\n   \n2. **Introduce Initiator**:\n   - Add AIBN at 1\u20133 wt% of the total monomer weight and purge the reaction flask with nitrogen to remove oxygen that inhibits free radical polymerization.\n\n3. **Polymerization**:\n   - Heat the mixture to 60\u201370\u00b0C under constant stirring for 6\u20138 hours.\n   - Monitor the reaction progress using ^1H NMR to observe the consumption of C=C double bonds in the monomers.\n\n4. **Purification**:\n   - Precipitate the modified polymer (PMMA-g-PEG) in an anti-solvent such as cold methanol or acetone.\n   - Filter and dry under vacuum.\n\n##### **Option 2: Hydrolysis of PMMA and Coupling with PEG**\n1. **Hydrolyze PMMA**:\n   - Dissolve PMMA in a mixture of methanol and NaOH at reflux conditions (approximately 60\u00b0C) for 6 hours. This converts a portion of the ester groups into carboxylic acid groups (-COOH).\n\n2. **Activate the Carboxylic Acid Groups**:\n   - Add dicyclohexylcarbodiimide (DCC) and N-hydroxysuccinimide (NHS) in stoichiometric amounts relative to the carboxylic acid groups, stirring the solution at 0\u00b0C for 30 minutes.\n   - This forms active ester intermediates.\n\n3. **Couple PEG Chains**:\n   - Add PEG with terminal amine (-NH\u2082) or hydroxyl (-OH) groups.\n   - Allow the reaction to proceed for 12\u201324 hours at room temperature to couple PEG onto the PMMA backbone via amide or ester linkages.\n\n4. **Purification**:\n   - Remove unreacted PEG and byproducts by dialysis or precipitation in an anti-solvent (e.g., ether).\n   - Dry the modified polymer under vacuum.\n\n---\n\n### **Step 5: Characterization and Confirmation**\n1. **Fourier Transform Infrared Spectroscopy (FTIR)**:\n   - Confirm the introduction of PEG by detecting characteristic C-O-C (ether) and O-H stretches.\n   \n2. **Nuclear Magnetic Resonance (NMR)**:\n   - ^1H NMR to identify PEG-specific resonances and quantify the degree of modification.\n\n3. **Contact Angle Measurements**:\n   - Measure the water contact angle to verify enhanced hydrophilicity (lower angles indicate higher hydrophilicity).\n\n4. **Thermogravimetric Analysis (TGA)**:\n   - Assess thermal stability of the modified polymer.\n\n---\n\n### **Step 6: Conclusion**\nUsing the above approach, PEG can be systematically and chemically incorporated into the PMMA backbone to enhance its hydrophilicity. The proposed grafting or coupling methodology ensures site-specific modification, maintains the structural integrity of the polymer, and significantly increases its water affinity. Both methods outlined are widely used and can be tailored depending on the specific application or properties desired in the final material.\n\nWould you like me to further elaborate on any step or consider a different hydrophilic molecule/polymer system?"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "How would you utilize chitosan variants as polycations within the experimental setup to modify a polymer for enhanced hydrophilicity? Specify the buffer conditions required."}, {"role": "assistant", "content": "Certainly, thank you for your question. Let us carefully analyze the problem, step by step, to systematically propose a sound experimental preparation scheme. \n\n### **Analysis of Your Question**\n\nThe main goal of your question is to use *chitosan variants as polycations* to modify a polymer in order to enhance its hydrophilicity. Breaking this down into key points:\n\n1. **Chitosan Variants**: Chitosan is a naturally derived polysaccharide composed of \u03b2-(1\u21924)-linked D-glucosamine and some N-acetyl-D-glucosamine units. Since chitosan has primary amine groups (-NH2), it can act as a polycation in appropriate pH conditions. Variants may include different degrees of deacetylation (DD) and molecular weights, which will affect their solubility and reactivity.\n\n2. **Hydrophilicity Modulation**: The hydrophilic character of polymers can be enhanced either by introducing charged functional groups, polar groups, or chemically/physically grafting hydrophilic moieties. Using a polycationic chitosan structure is a promising approach as it increases polar functionality.\n\n3. **Experimental Setup & Buffer Conditions**: Since chitosan is only soluble under acidic or mildly acidic pH due to protonation of the amine groups, precise buffer conditions are critical for its preparation and subsequent functionalization steps.\n\nWith this understanding, let me now provide a step-by-step experimental preparation scheme in detail.\n\n---\n\n### **Detailed Experimental Preparation Scheme**\n\n#### **1. Materials Required**\n1. **Chitosan Variant**:\n   - Select a chitosan variant with a degree of deacetylation (DD) \u2265 80% for higher amino group content.\n   - Use a medium molecular weight (~100\u2013300 kDa) chitosan for a balance of solubility and mechanical properties.\n   \n2. **Target Polymer**: Choose a polymer with reactive functional groups that can interact with chitosan (e.g., carboxylic groups, epoxides, or halides).\n\n3. **Reagents**:\n   - Acetic acid (weak acid for chitosan dissolution)\n   - Reaction coupling agents (carbodiimides like EDC/NHS for amine-carboxyl reactions, or glutaraldehyde for Schiff base crosslinking)\n   - Buffer systems (phosphate buffer or acetate buffer depending on target polymer chemistry)\n\n4. **Solvents**:\n   - Deionized (DI) water for dissolving hydrophilic components.\n   - Ethanol or other organic solvents for polymer processing, if required.\n\nNow, let us move on to the experimental design.\n\n---\n\n#### **2. Preparation of the Chitosan Solution**\n1. **Dissolution of Chitosan**:\n   - Weigh out the required amount of chitosan (typically 1% w/v solution).\n   - Dissolve chitosan in 1% (v/v) acetic acid solution at room temperature (~25\u00b0C) under constant stirring for 2\u20134 hours until a clear, homogenous solution forms.\n   - Adjust the pH to 5\u20136 using dilute NaOH to ensure protonation of amino groups, making chitosan positively charged. This is critical for hydrophilic modification reactions.\n\n2. **Buffer Preparation** (Optional for Downstream Steps):\n   - Prepare a weak phosphate buffer (pH 6\u20137) or acetate buffer (pH 5\u20136) as required for subsequent coupling or grafting.\n\n#### **3. Activation of the Target Polymer**\n   (Specific to the functional groups present on the polymer)\n1. **If the Polymer Contains Carboxylic Groups**:\n   - Treat the polymer with 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) (10\u201350 mM) and N-hydroxysuccinimide (NHS) (10\u201320 mM) in a buffer (e.g., MES buffer, pH 6.0) to activate the carboxylic groups.\n   - Incubate the polymer solution at room temperature for 15\u201330 minutes with gentle stirring.\n\n2. **If the Polymer Contains Epoxide or Chloride Groups**:\n   - Directly react these groups with chitosan at slightly elevated temperatures (e.g., 40\u201350\u00b0C) to enable a substitution or crosslinking reaction.\n\n#### **4. Coupling Chitosan to the Polymer**\n1. Add the chitosan solution dropwise to the activated polymer solution (in EDC/NHS-activated carboxylic polymers) while stirring.\n2. Maintain reaction conditions for coupling:\n   - pH: Adjust to a mildly acidic range (5\u20136) to retain amino group protonation.\n   - Temperature: ~25\u201330\u00b0C.\n   - Reaction Time: Stir for 4\u20136 hours to ensure efficient coupling.\n\n3. **Control Reaction Stoichiometry**:\n   - Molar ratio of polymer carboxylic groups to chitosan NH2 groups: 1:2 to maximize hydrophilic functionalization.\n\n#### **5. Post-Modification Purification**\n1. Dialyze the reaction mixture (if water-soluble) using a membrane (MWCO ~10\u201330 kDa) to remove unreacted reagents, coupling catalysts, and by-products.\n2. If the polymer is insoluble, wash thoroughly with DI water followed by ethanol to remove impurities.\n\n#### **6. Characterization of Modified Polymer**\n1. Perform Fourier-transform infrared spectroscopy (FTIR) to confirm new bonding (e.g., amide bonds at ~1650 cm\u207b\u00b9, Schiff base formation at ~1630\u20131640 cm\u207b\u00b9).\n2. Use contact angle measurements to evaluate hydrophilicity improvements (contact angle should decrease after modification).\n3. Thermogravimetric analysis (TGA) or scanning electron microscopy (SEM) can also be used to evaluate bulk properties or structural changes.\n\n---\n\n### **Buffer Conditions**\n1. **During Chitosan Dissolution**: Use 1% acetic acid (v/v) to protonate chitosan's amino groups, ensuring solubility.\n2. **During Coupling Reactions**:\n   - Use a pH ~5.5 acetate buffer or a mild phosphate buffer (pH ~6.0) to maintain charge balance and enhance crosslinking stability.\n\n---\n\n### **Key Points for Laboratory Success**\n1. Always confirm the compatibility of your chosen buffer with the target polymer and chitosan.\n2. Avoid excessively high or low pH values to prevent chitosan precipitation (optimum: pH 5\u20136).\n3. Carefully control the molar ratios of functional groups to ensure efficient coupling.\n\nBy following this systematic approach, you should obtain a hydrophilic polymer modified with chitosan variants, significantly enhancing its hydrophilicity. If you encounter any challenges during the experiment, feel free to reach out.\n\nGood luck with your laboratory work!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain the role of surfactants, such as sodium dodecyl benzene sulfonate (SDBS), in improving the distribution and stability of TiO2 particles during polymer modification for hydrophilicity enhancement."}, {"role": "assistant", "content": "Certainly, let's dive into your question thoughtfully and step by step, integrating both theoretical insights and practical considerations to strengthen your understanding of the role surfactants, like sodium dodecyl benzene sulfonate (SDBS), play in the context of improving the dispersion and stability of TiO\u2082 particles during polymer modification for enhanced hydrophilicity.\n\n---\n\n### 1. **Analyzing the Question and Summarizing Key Points**\n\n- **Question Focus:** Understanding the mechanism by which surfactants like SDBS assist in improving TiO\u2082 particle distribution and stability in the polymer matrix to enhance hydrophilicity.\n- **Context:** TiO\u2082 is often employed as a functional additive in hydrophilic polymer preparation due to its photocatalytic activity, surface properties, and ability to enhance hydrophilicity. However, proper dispersion and stability of TiO\u2082 within the polymer are critical for achieving desired properties.\n- **Key Role of Surfactant (SDBS):** To enhance distribution and stability by addressing challenges such as particle aggregation and poor interfacial interaction between TiO\u2082 and the polymer matrix.\n\n---\n\n### 2. **Systematic and Detailed Explanation**\n\nLet me now break this down systematically, focusing on surfactant function, interaction mechanisms, and experimental considerations.\n\n---\n\n#### **(A) Challenges with TiO\u2082 in Polymer Modification**:\n1. **Agglomeration of TiO\u2082 Nanoparticles**:\n   - TiO\u2082 nanoparticles possess high surface energy, which drives their tendency to aggregate.\n   - Aggregation reduces the effective surface area of TiO\u2082 available for interaction and diminishes its beneficial properties (e.g., hydrophilicity enhancement and photocatalytic activity).\n\n2. **Hydrophobic Incompatibility**:\n   - TiO\u2082 particles often have a surface chemistry that may not distribute well in polymeric matrices with differing hydrophilic/hydrophobic balance.\n\n---\n\n#### **(B) Role of SDBS as a Surfactant**:\nSodium dodecyl benzene sulfonate (SDBS) is an anionic surfactant, and its amphiphilic structure makes it an excellent dispersing agent. Its role can be detailed as follows:\n\n1. **Adsorption onto TiO\u2082 Nanoparticle Surfaces**:\n   - The sulfonate head group (-SO\u2083\u207b) in SDBS has strong electrostatic affinity for the TiO\u2082 surface.\n   - The adsorption of SDBS introduces a negative charge layer around each TiO\u2082 nanoparticle, imparting electrostatic repulsion.\n   - This prevents aggregation by overcoming the attractive Van der Waals forces between particles.\n\n2. **Enhanced Hydrophilicity via Amphiphilicity**:\n   - The hydrophilic sulfonate head ensures compatibility with hydrophilic components in the polymer or aqueous reaction medium.\n   - The hydrophobic tail of SDBS can interact with nonpolar domains, facilitating better dispersion within the hydrophilic polymer matrix.\n\n3. **Stabilization in Suspension**:\n   - SDBS forms a stable colloidal suspension of TiO\u2082 particles in aqueous media, which is crucial for uniform incorporation into the polymerization process.\n\n4. **Improved Interfacial Interaction**:\n   - Even after incorporation into the polymer matrix, SDBS helps maintain the spatial separation of TiO\u2082 particles.\n   - Additionally, the hydrophilic sulfonate groups on the surface of TiO\u2082 create active sites for hydrophilic polymer chains to interact, thereby enhancing overall polymer hydrophilicity.\n\n---\n\n#### **(C) Step-by-Step Experimental Scheme**\n\n1. **Preparation of TiO\u2082 Suspension Using SDBS**:\n   - **Materials**: TiO\u2082 nanoparticles, SDBS, deionized water.\n   - **Process**:\n     1. Dissolve an appropriate amount of SDBS in deionized water (e.g., 1\u20132% w/v surfactant solution).\n     2. Add TiO\u2082 nanoparticles gradually to the SDBS solution under stirring.\n     3. Sonicate the solution for 30\u201360 minutes to break up agglomerates and achieve fine dispersion.\n   - **Key Considerations**:\n     - The concentration of SDBS should be sufficient to cover the entire surface of TiO\u2082 particles without leading to micelle formation.\n     - Ultrasonication helps disintegrate existing agglomerates, and vigorous stirring ensures homogeneous dispersion.\n\n2. **Incorporation into Polymerization or Polymer Matrix**:\n   - **For in situ polymerization**:\n     1. After preparing the stable TiO\u2082\u2013SDBS suspension, introduce it into the polymerization reaction medium.\n     2. Ensure compatibility between the polymerization conditions and TiO\u2082 dispersion (e.g., pH, ionic strength).\n   - **For blending with pre-synthesized polymer**:\n     1. Mix the TiO\u2082\u2013SDBS suspension with the polymer solution or melt under strong shear forces to achieve uniform distribution.\n\n3. **Polymer Crosslinking and Hydrophilicity Enhancement**:\n   - The incorporated TiO\u2082 particles, stabilized by SDBS, enhance hydrophilicity because:\n     - They increase the water-attracting properties of the polymer due to their surface hydrophilic functionality.\n     - The sulfonate groups of SDBS on the surface of TiO\u2082 participate in further hydrogen bonding or electrostatic interactions with water.\n\n4. **Post-treatment**:\n   - Remove excess unbound SDBS by washing the polymer (if non-covalently bound SDBS could impact final properties).\n   - Conduct curing or thermal treatments as required for polymerization completion.\n\n---\n\n#### **(D) Reaction Conditions and Ratios**\n\n1. **SDBS to TiO\u2082 Ratio**:\n   - An SDBS-to-TiO\u2082 weight ratio of approximately 1:10 to 1:5 often works optimally, depending on the TiO\u2082 particle size and specific surface area.\n\n2. **Dispersion Medium**:\n   - Use deionized water or a compatible aqueous media to prepare the TiO\u2082 suspension.\n\n3. **Sonication Conditions**:\n   - Ultrasonic frequency: ~20\u201340 kHz.\n   - Duration depends on the degree of dispersion observed visually (typically 30\u201360 min).\n\n4. **Polymerization Compatibility**:\n   - Adjust pH to prevent destabilization of TiO\u2082 suspension during polymerization (neutral to slightly acidic pH works well for SDBS-stabilized TiO\u2082).\n\n---\n\n### 3. **Summary**\n\nThe use of sodium dodecyl benzene sulfonate (SDBS) plays a pivotal role in achieving effective dispersion and stabilization of TiO\u2082 nanoparticles during polymer modification. By adsorbing onto the TiO\u2082 surface, SDBS prevents aggregation and promotes compatibility with the polymer matrix, ensuring that the hydrophilic properties of both the TiO\u2082 and the surfactant synergistically enhance the hydrophilicity of the final polymer.\n\nThrough proper experimental design, including optimized SDBS-to-TiO\u2082 ratios, dispersion techniques, and integration into the polymer system, one can successfully prepare hydrophilic polymers with uniformly distributed TiO\u2082 particles that exhibit improved performance and stability."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Design a step-by-step experimental scheme for synthesizing a hydrophilic polymer by reacting isophorone diisocyanate (IPDI) with appropriate reagents. Specify reaction conditions, solvents, and the role of IPDI in enhancing hydrophilicity."}, {"role": "assistant", "content": "### Question Analysis and Key Points\n\nThe objective is to design an experimental scheme for synthesizing a hydrophilic polymer using **isophorone diisocyanate (IPDI)**. The core challenges here include:\n1. Understanding the chemistry of IPDI, a commonly used diisocyanate with two reactive isocyanate (-NCO) groups that can form urethane or urea linkages.\n2. Selecting appropriate reagents that can react with IPDI to yield a hydrophilic polymer. Typically, incorporation of hydrophilic functionality (e.g., polyethers, amines, or hydroxyl-containing groups) is required to enhance water affinity.\n3. Providing systematic experimental details, including reaction conditions, solvent choices, molar ratios, and any catalysts if needed, for each step of the proposed synthesis.\n\nNow, let\u2019s proceed step-by-step to design a detailed experimental preparation scheme.\n\n---\n\n### Step-by-Step Experimental Scheme for Synthesizing a Hydrophilic Polymer Using IPDI\n\n#### Step 1: Selection of Reagents and Reaction Strategy\nTo enhance hydrophilicity, we aim to introduce hydrophilic functional groups into the polymer backbone. For this, we will:\n1. **Use a diol or polyether polyol** with hydrophilic characteristics, such as **polyethylene glycol (PEG)**, which has ether linkages (-CH2-CH2-O-) that significantly improve water compatibility.\n2. Optionally, introduce ionic or zwitterionic groups that further enhance water solubility. For example, adding a tertiary amine group (later quaternized) or carboxylic acid can be effective.\n\nIPDI will act as the key diisocyanate component to react with these reagents, forming urethane linkages that hold the polymer structure together. Its unique asymmetric structure provides an additional advantage in controlling the polymer\u2019s physical properties.\n\n---\n\n#### Step 2: Reaction 1 \u2013 Preparation of Prepolymer\nWe will synthesize a prepolymer by reacting IPDI with polyethylene glycol (PEG).\n\n**Materials:**\n- Isophorone diisocyanate (IPDI)\n- Polyethylene glycol (PEG, molecular weight 400\u20131000, depending on desired polymer properties)\n- Organic solvent: **anhydrous dimethylformamide (DMF)** or **toluene**\n- Catalyst: Dibutyltin dilaurate (DBTDL)\n\n**Procedure:**\n1. Dry all glassware and reagents (anhydrous conditions are critical to avoid unwanted water reactions with isocyanate groups).\n2. Dissolve a calculated amount of PEG in 50 mL of anhydrous DMF or toluene. The PEG should be used in slight stoichiometric excess relative to one isocyanate group of IPDI. For example, for 1 mole of IPDI, use ~1.05 moles of PEG.\n3. Add a catalytic amount of DBTDL (e.g., 0.05\u20130.1 wt% of the reaction mixture) to accelerate the reaction.\n4. Add IPDI slowly to the PEG solution under a nitrogen blanket with continuous stirring to ensure proper mixing. The reaction temperature should be maintained at 50\u201360\u00b0C for 3\u20134 hours (optimize this based on monitoring).\n5. Monitor the reaction progress by tracking the disappearance of the NCO stretch (~2275 cm\u207b\u00b9) in FTIR spectroscopy.\n\n**Outcome:** A urethane-linked prepolymer with terminal isocyanate groups (-NCO) is formed.\n\n---\n\n#### Step 3: Reaction 2 \u2013 End-Capping with a Hydrophilic Chain Extender\nTo further enhance hydrophilicity, react the prepolymer\u2019s terminal -NCO groups with a **hydrophilic chain extender**, such as a diol containing ionic or polar groups. \n\n**Materials:**\n- Chain extender: Amino alcohol like **2-aminoethanol** or a diol like **dimethylolpropionic acid (DMPA)**\n- Organic solvent: Water-miscible solvents like acetone\n- Neutralizing agent (if DMPA is used): **Triethylamine (TEA)** or NaOH\n\n**Procedure:**\n1. Dissolve the prepolymer obtained from Step 2 in a suitable solvent like acetone, ensuring complete solubility.\n2. Dissolve the chain extender (e.g., 0.9\u20131.0 moles of DMPA or amino alcohol per mole of IPDI used in Step 1) separately in a small volume of solvent.\n   - If DMPA is used: Neutralize DMPA with TEA to form a carboxylate salt, which enhances solubility in the reaction medium.\n3. Add the chain extender solution dropwise into the prepolymer solution under nitrogen at room temperature. Allow the reaction to proceed for 4\u20136 hours, monitoring the -NCO stretch in FTIR.\n4. Terminate the reaction when no free -NCO groups are observed in FTIR.\n\n**Outcome:** The final product is a hydrophilic polymer containing urethane linkages and polar/ionic side groups from the chain extender.\n\n---\n\n#### Step 4: Purification and Characterization\n1. **Purification:**\n   - Precipitate the polymer into a non-solvent like hexane (if acetone is used as the reaction medium) to remove impurities.\n   - Alternatively, dialyze the polymer solution (if water-soluble) against distilled water to eliminate unreacted species.\n2. **Characterization:**\n   - Use **FTIR spectroscopy** to confirm the absence of -NCO groups and the presence of urethane (-NH-CO-) linkages.\n   - Determine the molecular weight using **GPC (gel permeation chromatography)**.\n   - Check hydrophilicity and water interaction using contact angle measurements or solubility tests.\n\n---\n\n#### Reaction Conditions Summary\n| Step               | Reagents/Materials                              | Solvent   | Catalyst | Temperature | Time    |\n|--------------------|------------------------------------------------|-----------|----------|-------------|---------|\n| Prepolymerization  | IPDI + PEG (1:1.05 mol)                        | DMF/Toluene | DBTDL    | 50\u201360\u00b0C     | 3\u20134 hrs |\n| Chain Extension    | Prepolymer + DMPA/2-Aminoethanol               | Acetone   | None     | RT          | 4\u20136 hrs |\n\n---\n\n### Role of IPDI in Enhancing Hydrophilicity\nAlthough IPDI itself is hydrophobic, its role is pivotal in this synthesis:\n1. It provides the reactive isocyanate groups needed to form urethane linkages with hydrophilic reagents.\n2. Its bulky, asymmetric structure contributes to the polymer\u2019s solubility and physical flexibility, improving hydrophilic group accessibility.\n\n---\n\nBy following these steps, a hydrophilic polymer with urethane linkages and excellent water compatibility can be successfully synthesized. Let me know if you need help tailoring this approach further for specific experimental requirements!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe how d-glucose 6-phosphate monobarium salt (GPS-Ba) can be utilized as a template in the synthesis of a hydrophilic polymer. What is the significance of its interaction with the polymer precursor during the preparation process?"}, {"role": "assistant", "content": "Great question! Let's break down the problem methodically and tackle it step by step.\n\n---\n\n### **Step 1: Analyzing the question**\n**Key points:**\n- The molecule in question is **D-glucose 6-phosphate monobarium salt (GPS-Ba)**.\n- It needs to be used as a **template** in the synthesis of a **hydrophilic polymer**.\n- You are asking for details about both the synthesis process (experimental preparation scheme) and the significance of its interaction with the polymer precursor during the preparation.\n\n**Hydrophilic polymers** are materials that attract water due to their high affinity for polar molecules such as water. In this case, GPS-Ba offers unique advantages because:\n1. **Hydrophilicity of D-glucose 6-phosphate**: The molecule has highly hydrophilic functional groups (-OH, -COOH, and -PO4), which can significantly enhance the hydrophilicity of the polymer matrix.\n2. **Template role**: Because GPS-Ba has coordination sites through its phosphate group, it can interact with precursors (monomers or crosslinking agents) to create a structured or functionalized polymer with controlled architecture.\n3. **Significance of Ba2+ ion**: The presence of barium adds ionic strength and may influence the polymerization environment (e.g., by stabilizing certain intermediates or by controlling precursor interactions).\n\n---\n\n### **Step 2: Detailed experimental preparation scheme**\nI'll describe a systematic experiment in which GPS-Ba acts as a template. Additionally, I'll delve into each step of the polymer synthesis, discussing reaction conditions, reagents, and their molar ratios.\n\n---\n\n#### **Materials and reagents**\n1. **D-glucose 6-phosphate monobarium salt (GPS-Ba)**\n2. **Monomer** (e.g., acrylamide, acrylic acid, or hydroxyethyl methacrylate)\n3. **Crosslinking agent** (e.g., N,N\u2019-methylenebisacrylamide or ethylene glycol dimethacrylate)\n4. **Initiator** for free-radical polymerization (e.g., ammonium persulfate (APS) or azobisisobutyronitrile (AIBN))\n5. **Solvent**: Water or a water-miscible organic solvent (e.g., ethanol)\n6. **Additional catalyst or stabilizer** (if necessary)\n7. **Neutralizing agent** (e.g., NaOH or HCl solution to adjust pH)\n\n---\n\n#### **Synthetic strategy**\nPreparation of hydrophilic polymer with GPS-Ba involvement proceeds in these systematic stages:\n\n---\n\n#### **Step 2.1: Preparation of the reaction system**\n1. Dissolve **GPS-Ba** in deionized water to create a homogeneous solution. The phosphate groups of GPS-Ba will ionize, providing a hydrophilic environment and ionic strength to enhance precursor interactions.\n   - Concentration: Aim for 0.1\u20130.2 M GPS-Ba solution.\n   - pH: Adjust pH to 7\u20138 using a dilute NaOH/HCl solution since phosphate groups perform optimally in near-neutral conditions.\n2. To this solution, add the chosen **monomer** (e.g., acrylamide) at a molar ratio suited for polymerization:\n   - Suggested monomer-to-template ratio: 10:1 to ensure sufficient interaction while maintaining a polymerizable volume.\n3. Add the **crosslinking agent** at a small fraction (typically 1\u20135 mol% of the monomer) to control the polymer's physical structure while retaining hydrophilicity.\n\n---\n\n#### **Step 2.2: Free radical polymerization with GPS-Ba as the template**\n1. Introduce the **initiator** (e.g., APS or AIBN) to the reaction system to generate radicals for polymerization:\n   - Initiator concentration: 0.5\u20132 wt% relative to the monomer. Ensure complete dissolution for an optimal reaction.\n   - Temperature: 50\u201370\u00b0C for thermal initiators like AIBN or APS. Maintain gentle stirring to ensure uniform heat distribution and thorough mixing.\n2. Allow polymerization to proceed for 4\u201312 hours. During this time, GPS-Ba templates the polymer by facilitating localized monomer interactions via its phosphate groups.\n\n**Mechanism of interaction:**\n- The phosphate groups in GPS-Ba act as functional sites, interacting with the amide or carboxylic acid groups in the monomer through hydrogen bonding and ionic coordination.\n- The barium ions (Ba2+) stabilize polar intermediates and potentially catalyze some chain-transfer reactions. This improves the polymerization rate and yields a hydrophilic polymer with tailored architecture.\n\n---\n\n#### **Step 2.3: Finalization and purification**\n1. After polymerization, quench the reaction by adding ice-cold deionized water or ethanol.\n2. Purify the synthesized polymer by dialysis to remove unreacted GPS-Ba. Alternatively, extraction via ultrafiltration may be used.\n3. Dry the polymer under a vacuum at ~40\u00b0C to avoid thermal degradation.\n\n---\n\n#### **Step 2.4: Characterization**\nTo confirm the presence of hydrophilic functional groups and polymer structure:\n1. Perform **Fourier-transform infrared spectroscopy (FTIR)** to verify interaction between GPS-Ba phosphate groups and polymer backbone.\n2. Conduct **contact angle measurements** to evaluate hydrophilicity.\n3. Use **gel permeation chromatography (GPC)** to analyze molecular weight distribution.\n\n---\n\n### **Step 3: Significance of GPS-Ba in the process**\nThe role of GPS-Ba is pivotal and multidimensional:\n1. **Template structuring**: GPS-Ba organizes monomers via its hydrophilic and ionic phosphate groups, leading to localized polymer growth and enhanced functional group dispersion.\n2. **Hydrophilicity enhancement**: Incorporating GPS-Ba ensures integration of polar regions (phosphate and hydroxyl groups) into the polymer matrix, increasing water affinity.\n3. **Controlled polymerization**: Ba2+ ions stabilize polar intermediates, minimizing undesirable side reactions and ensuring predictable polymer architecture.\n4. **Functionalization**: GPS-Ba leaves behind structural imprints on the polymer, enhancing specific functionalities (e.g., ion-exchange capacity or reactivity), depending on the intended application.\n\n---\n\n### **Step 4: Practical tips for success**\n1. Ensure thorough dissolution of GPS-Ba before adding any monomer.\n2. Maintain precise temperature control during polymerization to avoid runaway reactions.\n3. Use appropriate purification techniques to remove excess GPS-Ba, as residual salt may influence the physical properties of the polymer.\n\n---\n\n### **Conclusion**\nUsing **D-glucose 6-phosphate monobarium salt (GPS-Ba)** as a template provides both structural and functional advantages in synthesizing hydrophilic polymers. Its hydrophilic nature enhances water affinity, while its ionic phosphate groups facilitate organized polymerization. This method is scientifically robust and practically feasible for designing hydrophilic polymers tailored to various applications, such as biomedical materials, water purification membranes, or functional coatings.\n\nLet me know if you have further questions\u2014I'd be happy to elaborate!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "In the preparation of hydrophilic polymers, what factors should be considered when applying ZnCl2 to a substrate? Suggest specific parameters such as concentration, application method, and environmental conditions to achieve optimal results."}, {"role": "assistant", "content": "Certainly! Let\u2019s analyze your question step by step to provide a systematic and detailed answer.\n\n---\n\n### **Analysis of the Question**\nYour question focuses on the application of ZnCl\u2082 to a substrate in the context of hydrophilic polymer preparation. ZnCl\u2082 (zinc chloride) is a versatile reagent, often used in polymer science due to its hygroscopic properties, catalytic activity, and ability to enhance hydrophilicity by modifying surface chemistry. To achieve optimal performance, the following key considerations need to be addressed:\n\n1. **ZnCl\u2082 concentration**: The concentration of ZnCl\u2082 affects its ability to activate the substrate surface or participate in the polymerization process.\n2. **Application method**: How ZnCl\u2082 is applied to the substrate (e.g., solution immersion, spin coating, dip-coating, spray coating, etc.) can determine uniformity and reaction efficiency.\n3. **Environmental conditions**: Parameters such as temperature, pH, humidity, and reaction time have a significant influence on the functionalization of the substrate and the successful incorporation into a hydrophilic polymer system.\n\n---\n\n### **Step-by-Step Detailed Answer**\n\nBelow, I outline an experimental preparation scheme for applying ZnCl\u2082 to a substrate with optimal parameters for hydrophilic polymer synthesis.\n\n#### **Step 1: Preparation of ZnCl\u2082 Solution**\n1. **Concentration**: Prepare a ZnCl\u2082 aqueous solution with a typical concentration range of **0.1 M to 0.5 M**, depending on the substrate's surface area, compatibility, and the desired surface modification.\n   - For highly porous or absorptive substrates, use a lower concentration (e.g., 0.1 M) to prevent excessive deposition, which might limit polymer interaction.\n   - For non-porous substrates or when stronger surface modification is desired, 0.3\u20130.5 M is appropriate.\n2. **Solvent Selection**: Use distilled water as the solvent for ZnCl\u2082, unless the substrate is water-sensitive. In such cases, ethanol, methanol, or a water-ethanol blend may be used to dissolve ZnCl\u2082.\n\n#### **Step 2: Surface Preparation of the Substrate**\nBefore applying the ZnCl\u2082 solution, ensure the substrate is clean and prepared:\n1. **Cleaning**: Remove any surface impurities by washing the substrate with ethanol or isopropanol, followed by deionized water. Dry the substrate in air or in an oven at **80\u2013100\u00b0C**.\n2. **Activation (if applicable)**: For stronger ZnCl\u2082 adherence, activate the substrate surface using plasma treatment, UV-ozone treatment, or mild etching with a dilute acid (e.g., 1 M HCl) to remove oxides and impurities.\n\n#### **Step 3: Application of ZnCl\u2082 to the Substrate**\nChoose an application method tailored to the substrate and experimental goals:\n1. **Dip Coating**:\n   - Immerse the substrate in the ZnCl\u2082 solution for **5\u201330 minutes** to allow sufficient interaction and coverage.\n   - Use gentle stirring of the ZnCl\u2082 solution to ensure even contact.\n   - After immersion, remove the substrate and drain excess solution to achieve a uniform layer. Optionally, rinse briefly with the solvent to remove excess ZnCl\u2082 crystals.\n2. **Spin Coating** (for smooth, uniform layers):\n   - Place the substrate on a spin-coater and deposit a controlled amount of ZnCl\u2082 solution (e.g., 100\u2013500 \u00b5L, depending on substrate size).\n   - Use a two-step spin program: typically, **500 rpm for 10 seconds** followed by **2000 rpm for 30 seconds** to spread the solution and achieve uniform coverage.\n3. **Spray Coating** (for large or uneven surfaces):\n   - Use a fine mist spray to apply the ZnCl\u2082 solution evenly over the substrate. Optimize the nozzle distance (10\u201320 cm) and application pressure to avoid droplet formation.\n4. **Drying**:\n   - After application, dry the substrate under controlled conditions (see Step 5) to solidify the ZnCl\u2082 layer.\n\n#### **Step 4: Environmental Conditions**\nDuring and after ZnCl\u2082 application, control the environmental factors to enhance reaction performance:\n1. **Temperature**: Perform the application process at **room temperature (20\u201325\u00b0C)** to prevent thermal decomposition of ZnCl\u2082. Higher temperatures may lead to ZnCl\u2082 crystallization instead of forming a uniform surface layer.\n2. **Humidity**: Avoid high humidity during the application process (keep it below **50% RH**) to prevent premature hydrolysis of ZnCl\u2082 and delamination.\n3. **pH Control (if applicable)**: ZnCl\u2082 is highly hygroscopic and can hydrolyze in aqueous media. Keep the solution mildly acidic (pH ~5\u20136) by adding a buffer (e.g., acetic acid) if necessary.\n\n#### **Step 5: Post-Application Treatment**\n1. **Thermal Treatment** (optional but beneficial):\n   - After ZnCl\u2082 application, cure the substrate at **80\u2013120\u00b0C** for **30\u201360 minutes** in an oven or a vacuum chamber. This step ensures better bonding to the substrate and removes residual solvent.\n2. **Rinsing (if needed)**:\n   - For applications requiring a clean but hydrophilically modified surface (e.g., before polymer grafting), briefly rinse the substrate with a dilute ethanol/water solution and air-dry to remove loosely bound ZnCl\u2082.\n\n#### **Step 6: Integration with Hydrophilic Polymer Preparation**\n1. If ZnCl\u2082 is used as a catalytic or functional layer for subsequent polymerization (e.g., free radical or graft polymerization of hydrophilic monomers like acrylamide, hydroxyethyl methacrylate, or polyethylene glycol):\n   - Introduce the monomer solution directly over the ZnCl\u2082-coated substrate.\n   - Adjust the reaction conditions (e.g., temperature, initiator concentration) to ensure uniform polymer growth.\n\n2. For applications where ZnCl\u2082 enhances surface wettability prior to functionalization:\n   - Assess surface wettability by measuring the water contact angle. A reduction in the angle compared to the untreated substrate indicates successful hydrophilicity enhancement.\n\n---\n\n### **Key Experimental Parameters Summary**\n| **Parameter**            | **Recommended Range/Value**                  |\n|---------------------------|----------------------------------------------|\n| ZnCl\u2082 Concentration       | 0.1\u20130.5 M                                   |\n| Application Method        | Dip coating, spin coating, or spray coating |\n| Drying Temperature        | 80\u2013120\u00b0C                                    |\n| Application Temperature   | 20\u201325\u00b0C (room temperature)                  |\n| Relative Humidity         | <50% RH                                     |\n| Reaction pH (if aqueous)  | Mildly acidic (pH ~5\u20136)                     |\n| Drying/Curing Time        | 30\u201360 minutes                               |\n\n---\n\nThis systematic approach should allow you to successfully apply ZnCl\u2082 to a substrate and progress toward hydrophilic polymer synthesis. Let me know if you\u2019d like to discuss specific polymer systems or reaction mechanisms!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "If you were to use POSS-Br in an ATRP-based reaction, how would you control the polymerization to achieve the desired balance between hydrophilic and hydrophobic properties in the resulting polymer? Include any factors you would consider in your design."}, {"role": "assistant", "content": "To design an ATRP (Atom Transfer Radical Polymerization) reaction using POSS-Br (Polyhedral Oligomeric Silsesquioxane functionalized with bromine) as an initiator, the goal is to control the polymerization such that the resulting polymer achieves an optimized balance between hydrophilic and hydrophobic properties. Below, I will analyze your question systematically and provide a comprehensive experimental preparation scheme.\n\n---\n\n### **Step 1: Analyze the Question**\nThe key points to consider in this synthesis are:\n1. **Use of POSS-Br as the initiating site**: POSS is inherently hydrophobic due to its silicon-oxygen cage structure, but the functionalization with bromine allows POSS to act as an ATRP initiator. This combination of hydrophobic POSS with compatible hydrophilic polymer chains can lead to a balanced amphiphilic polymer matrix.\n2. **Control of the polymerization conditions**: ATRP provides excellent control over molecular weight and chain architecture, which is critical for achieving the desired balance of hydrophobic and hydrophilic properties.\n3. **Selection of monomers**: By incorporating specific hydrophilic and hydrophobic monomers, the hydrophilicity/hydrophobicity of the resulting polymer can be tuned.\n4. **Reaction conditions**: Factors such as the catalyst, solvent, temperature, monomer ratios, and reaction time need optimization for balanced polymer characteristics.\n\n---\n\n### **Step 2: Systematic Preparation Scheme Using POSS-Br**\nThe following outlines all steps of the experimental design:\n\n---\n\n#### **Step 2.1: Materials Required**\n**Reagents:**\n1. POSS-Br as ATRP initiator.\n2. Hydrophilic monomers (e.g., poly(ethylene glycol) methyl ether methacrylate (PEGMA), 2-hydroxyethyl methacrylate (HEMA)).\n3. Optionally, hydrophobic monomers (e.g., styrene or methyl methacrylate (MMA)).\n4. Catalyst system (e.g., Cu(I) halide and ligand such as N,N,N',N\",N\"-pentamethyldiethylenetriamine (PMDETA) or bipyridine).\n5. Solvent (e.g., anisole, DMF, or toluene).\n6. Reducing agent (e.g., Cu(0) powder if an activator regeneration process is used).\n7. Purification agents (e.g., methanol or water for precipitation; activated carbon for copper removal).\n\n**Equipment:**\n- Schlenk flask or inert-atmosphere glovebox for oxygen-free conditions.\n- Magnetic stirrer, oil bath/heating mantle.\n- NMR spectrometer for monomer conversion tracking.\n- Gel permeation chromatography (GPC) for molecular weight analysis.\n\n---\n\n#### **Step 2.2: Reaction Design**\n1. **Initiator Setup**:\n   - POSS-Br serves as the bromine-functional initiator for ATRP, which actively supports controlled polymer growth. The hydrophobic POSS structure will remain central and will anchor grafted polymer chains.\n\n2. **Monomer Selection**:\n   - Hydrophilic monomers such as PEGMA or HEMA are incorporated to enhance hydrophilicity.\n   - Adding a hydrophobic monomer like MMA or styrene in varying ratios enables fine control over the polymer's amphiphilicity.\n   - The ratio between hydrophilic and hydrophobic monomers should be adjusted depending on the desired property. A typical range could be 70:30 (hydrophilic to hydrophobic).\n\n3. **Catalyst and Ligand**:\n   - Use Cu(I) halide (e.g., CuCl or CuBr) as the catalyst.\n   - Typically, a ligand like PMDETA or bipyridine is chosen to stabilize the Cu(I) species.\n   - Maintain a typical catalyst-to-initiator molar ratio of 1:1.\n\n4. **Solvent**:\n   - Solvent polarity affects polymerization. Use anisole or DMF for hydrophilic monomers.\n   - For better control, solvent must dissolve POSS-Br, and facilitate the solubility of Cu catalyst and ligand.\n\n5. **Reaction Temperature**:\n   - Control the reaction temperature between 50\u201390 \u00b0C, as higher temperatures generally speed up the polymerization but may reduce control over molecular weight and dispersity.\n\n---\n\n#### **Step 2.3: Experimental Procedure**\n1. **Prepare Reaction Mixture**:\n   - In a Schlenk flask under nitrogen atmosphere or vacuum, add POSS-Br (initiator), Cu(I) halide (catalyst), ligand, and selected monomers (hydrophilic and hydrophobic).\n   - Dilute the mixture with pre-cooled solvent (e.g., anisole or DMF).\n   - Add reducing agent (if necessary) to ensure activation of the catalyst.\n\n2. **Polymerization**:\n   - Begin polymerization at the controlled temperature (e.g., 70 \u00b0C).\n   - Monitor reaction progress by withdrawing aliquots periodically for NMR or GPC analysis.\n   - Depending on the degree of polymerization, the reaction typically runs for 6\u201324 hours.\n\n3. **End the Reaction**:\n   - To terminate the polymerization, expose the reaction mixture to air to deactivate the Cu species.\n   - Add an antioxidant (e.g., hydroquinone) if necessary to prevent side reactions.\n\n4. **Purification of Polymer**:\n   - Precipitate the polymer by adding the reaction mixture to a non-solvent (e.g., methanol or water).\n   - Recover polymer by filtration and dry under vacuum.\n   - If copper residuals are present, treat the polymer with activated carbon or use dialysis in aqueous solution.\n\n---\n\n#### **Step 2.4: Characterization**\n1. **Molecular Weight and Dispersity**:\n   - Use GPC analysis to confirm the molecular weight and dispersity (target dispersity = 1.1\u20131.3 for controlled AT).\n   - Ensure that the molecular weight falls within the range necessary for your intended application.\n\n2. **Hydrophilicity Assessment**:\n   - Measure the hydrophilicity/hydrophobicity via contact angle measurement or water absorption tests.\n\n3. **Structural Analysis**:\n   - Confirm the successful incorporation of hydrophilic/hydrophobic monomers by FTIR spectroscopy.\n\n---\n\n#### **Step 2.5: Factors to Optimize Balance Between Hydrophilic and Hydrophobic Properties**\n1. **Monomer Ratio**:\n   - Adjust hydrophilic-to-hydrophobic monomer ratio carefully. A higher percentage of PEGMA or HEMA will enhance hydrophilicity, while increasing MMA will boost hydrophobicity.\n\n2. **Chain Architecture**:\n   - Consider synthesizing block copolymers or graft polymers, as the arrangement of hydrophilic and hydrophobic segments affects overall properties.\n\n3. **Molecular Weight**:\n   - Higher molecular weights generally reduce the mobility of chains, which can affect surface properties.\n\n4. **End Group Functionalization**:\n   - Post-polymerization modification can be done to introduce ionic or polar groups at chain ends to further tune hydrophilicity.\n\n---\n\n### **Conclusion**\nUsing POSS-Br in an ATRP reaction provides excellent control over polymer architecture. By carefully selecting hydrophilic and hydrophobic monomers, optimizing reaction conditions, and tailoring molecular weight and structure, you can precisely control the amphiphilic balance in the resulting polymer. Follow these steps systematically, and ensure each parameter is adjusted based on experimental data for successful synthesis.\n\nIf you have more information (e.g., intended application or specific surface property requirements), I can further refine this scheme to optimize your outcome."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe the role of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) in the synthesis process and explain how its incorporation enhances the hydrophilicity of the resulting polymer."}, {"role": "assistant", "content": "Certainly! Let\u2019s analyze your question and address it step-by-step, thoroughly discussing the role of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) in the synthesis of hydrophilic polymers.\n\n---\n\n### **Step 1: Analyze the Question and Key Points**\nThe question targets two aspects:\n1. The role of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) in the synthesis process.\n2. How AMPS improves the hydrophilicity of the resulting polymer.\n\nTo answer this, we need to:\n- Understand the chemical structure and properties of AMPS.\n- Explain its function during polymerization.\n- Illustrate how its structural features contribute to hydrophilicity.\n\n---\n\n### **Step 2: Describe AMPS and Its Role in Synthesis**\n\n#### **1. Chemical Properties of AMPS**\nAMPS is a monomer with the structural formula CH\u2082=CH-CONH-C(CH\u2083)\u2082-CH\u2082-SO\u2083H. The key functional groups are:\n- A **vinyl group (-CH=CH\u2082)**: Enables chain propagation in polymerization by undergoing free radical addition polymerization.\n- A **sulfonic acid group (-SO\u2083H)**: Highly hydrophilic due to its ionic nature and ability to hydrogen bond with water molecules.\n- An **amide group (-CONH-)**: Enhances hydrogen bonding interactions and affects polymer stability.\n\nThese functional groups collectively make AMPS a versatile and highly polar monomer.\n\n#### **2. Role of AMPS in the Polymerization Process**\nAMPS typically participates in **free radical polymerization** or **copolymerization** with other monomers such as acrylamide, acrylic acid, or other methacrylate derivatives. Here's how AMPS operates in the reaction:\n\n- **Initiation**: In the presence of an initiator (such as potassium persulfate, APS, or azobisisobutyronitrile, AIBN), AMPS\u2019s vinyl group forms a reactive radical.\n- **Propagation**: The radical reacts with other monomeric units (either AMPS itself or a comonomer), forming extended polymer chains.\n- **Termination**: Radical termination occurs when two growing chains terminate with combined radicals or other deactivators, completing polymer growth.\n\n#### **Experimental Parameters to Consider**:\n- **Solvent Medium**: Due to its ionic nature, water or mixed solvent systems (water-methanol) are ideal for dissolving AMPS.\n- **pH Regulation**: The -SO\u2083H groups in AMPS are pH-sensitive; near-neutral pH (6-7) prevents excessive protonation or deprotonation that may destabilize the reaction.\n- **Reaction Temperature**: Generally, 40\u201370\u00b0C for free radical polymerization is used to decompose the initiator and maintain efficient chain growth.\n- **Molar Ratios**: The proportion of AMPS in the comonomer feed controls the degree of hydrophilicity. For highly water-soluble polymers, higher AMPS content, ~30\u201350 mol%, is often used.\n\n---\n\n### **Step 3: Enhancement of Hydrophilicity by AMPS**\n\nThe incorporation of AMPS significantly enhances the hydrophilicity of the resulting polymer. Here\u2019s how:\n\n#### **1. Sulfonic Acid Groups (-SO\u2083H)**\n- The **sulfonic acid group** is extremely hydrophilic due to its strong ionic character. When incorporated into a polymer, these groups are highly effective at attracting and binding water molecules through ion-dipole interactions and hydrogen bonding.\n- Even under harsh conditions like saline or high-temperature environments (e.g., oil field applications), the -SO\u2083H groups retain their hydrophilic properties, making AMPS-based polymers highly water-compatible and stable.\n\n#### **2. Hydrogen Bonding Contributions**\nThe amide group (-CONH-) in AMPS can establish hydrogen bonds with water molecules, increasing the water retention ability of the polymer.\n\n#### **3. Increased Solubility**\nPolymers containing AMPS dissolve better in aqueous systems because their ionic groups lower the surface energy and reduce hydrophobic interactions. This makes these polymers suitable for hydrogel formation, coatings, or drug delivery systems.\n\n#### **4. Ionic Charge Density**\nCopolymerizing AMPS with neutral or slightly hydrophobic monomers introduces charged groups that enhance water compatibility. This is especially useful in tailoring water-absorbing polymers or superabsorbents.\n\n---\n\n### **Step 4: A Synthesis Plan for an AMPS-Based Hydrophilic Polymer**\nBelow is a stepwise protocol for the preparation of a hydrophilic polymer containing AMPS:\n\n#### **Materials:**\n- AMPS monomer\n- Comonomer (e.g., acrylamide or acrylic acid)\n- Initiator (e.g., APS for aqueous initiation or AIBN for organic solvent systems)\n- Solvent (deionized water or water-methanol)\n- pH buffer (e.g., phosphate buffer for neutral pH control)\n- Nitrogen gas (to create an inert atmosphere)\n\n#### **Procedure:**\n1. **Preparation of Monomer Solution:**\n   - Dissolve AMPS in deionized water (e.g., 10\u201320 wt% concentration).\n   - Add desired comonomer (e.g., acrylamide) in a specific molar ratio (e.g., AMPS:acrylamide = 30:70 for moderate hydrophilicity, or 50:50 for more hydrophilic polymers). Stir thoroughly.\n\n2. **Adjust pH:**\n   - Use a pH meter to adjust the pH of the solution to ~6.5-7.0 using NaOH or HCl as needed.\n\n3. **Deoxygenation:**\n   - Bubble nitrogen gas through the reaction mixture for 30 minutes to remove dissolved oxygen, which can inhibit radical polymerization.\n\n4. **Initiation:**\n   - Dissolve the initiator (e.g., potassium persulfate) in a small amount of water and add it to the monomer solution. Typical initiator concentration is 0.1\u20131 wt% based on the total monomer weight.\n   - Raise the reaction temperature to ~60\u00b0C to activate the initiator.\n\n5. **Polymerization:**\n   - Allow the reaction to proceed under constant stirring (300\u2013500 rpm) for 4\u20136 hours. Maintain an inert nitrogen atmosphere throughout.\n\n6. **Termination and Purification:**\n   - Cool the reaction mixture to room temperature to terminate the polymerization.\n   - Precipitate the polymer in ethanol or acetone to remove unreacted monomers.\n   - Wash the precipitate and dry under vacuum at 50\u00b0C.\n\n#### **Expected Results**:\nThe resulting polymer will exhibit enhanced hydrophilicity, as evidenced by its high water absorption capacity, swelling behavior in aqueous media, or solubility in water. Characterization using methods such as FTIR (to confirm sulfonic group incorporation), TGA (to assess thermal stability), and contact angle measurement (to evaluate hydrophilicity) can verify the polymer's properties.\n\n---\n\n### **Conclusion**\nAMPS plays a dual role in polymer synthesis:\n1. It acts as a hydrophilic monomer that incorporates ionic and hydrogen-bonding groups into the polymer backbone.\n2. It enhances polymer hydrophilicity due to its sulfonic acid and amide groups.\n\nThrough careful control of reaction parameters, AMPS-containing polymers can be tailored for applications ranging from hydrogels to water treatment and biomedical systems."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Design an experimental procedure using HMDS to evaluate how its exposure time affects the contact angle of water on a polymer surface. Include steps for surface cleaning, treatment, and analysis."}, {"role": "assistant", "content": "This is an interesting and insightful question, as analyzing the effect of hexamethyldisilazane (HMDS) exposure time on the wettability of a polymer surface can provide valuable insights into surface modification chemistry and its influence on hydrophilicity. To answer this systematically and in detail, let's break it down step by step while emphasizing surface cleaning, treatment, experimental design, and analysis.\n\n---\n\n### Key Points from the Question:\n1. **Objective**: Evaluate how the exposure time of HMDS affects the contact angle of water on a polymer surface. \n2. **Key Steps**: Surface cleaning (to remove contaminants), surface HMDS treatment (to modify surface properties), and analysis (to measure water contact angle and assess changes in hydrophilicity).\n3. **Critical Parameters**: Exposure time to HMDS, contact angle measurement, and reproducibility.\n\n---\n\n### Detailed Experimental Procedure:\n\n#### Step 1: **Material Preparation and Surface Cleaning**\n1. **Materials Required**:\n   - Polymer samples (e.g., polymethyl methacrylate (PMMA), polyethylene (PE), or polydimethylsiloxane (PDMS)).\n   - Hexamethyldisilazane (HMDS) \u2013 analytical grade.\n   - Solvents for cleaning: ethanol, acetone, deionized (DI) water.\n   - Clean glassware and a desiccator.\n   - Nitrogen (N\u2082) gas or compressed dry air for drying.\n\n2. **Surface Cleaning Protocol**:\n   - Clean the polymer surfaces thoroughly to remove dust, oils, and any organic contaminants. Follow this procedure:\n     - Sonicate the polymer samples in ethanol for 10 minutes.\n     - Rinse them with acetone to remove residual organic contaminants.\n     - Wash the surfaces with DI water to eliminate any residual impurities.\n     - Dry the samples with nitrogen gas or place them in a vacuum desiccator for 30 minutes to ensure a dry, clean surface.\n   - **Note**: Surface cleaning is crucial to ensure that observed changes in wettability are solely due to HMDS treatment and not residual contamination.\n\n---\n\n#### Step 2: **HMDS Treatment**\n1. **Reaction Vessel Setup**:\n   - Use a vacuum desiccator or a sealed reaction chamber that can be evacuated and refilled with HMDS vapor. Ensure cleanliness of the chamber prior to introducing the polymer samples.\n   - Place the polymer samples evenly spaced on a clean glass tray or holder, ensuring uniform exposure to HMDS vapor.\n\n2. **Introducing HMDS**:\n   - Add approximately 1\u20132 mL of HMDS to a small Petri dish or watch glass and place it at the bottom of the desiccator/chamber.\n   - Seal the chamber and evacuate the air within to reduce ambient humidity and create a low-pressure environment (optional but recommended).\n\n3. **Exposure Process**:\n   - Allow HMDS to vaporize and interact with the polymer surfaces for specific exposure times. Design the experiment to test different exposure times to study their effect on the contact angle. Suggested time intervals: 5 minutes, 15 minutes, 30 minutes, 1 hour, and 2 hours.\n   - After each exposure time, remove the polymer sample carefully from the chamber and proceed to characterization (detailed in Step 4 below).\n\n4. **Post-Treatment Drying (Optional)**:\n   - After exposure, polymer samples can be baked at 60\u201380 \u00b0C for 15 minutes in a hot-air oven or placed in a vacuum desiccator for 30 minutes to ensure evaporation of unreacted HMDS.\n\n5. **Reaction Mechanism**:\n   - HMDS reacts with surface hydroxyl (-OH) groups, replacing them with methyl (-CH\u2083) groups. This results in changes to surface wettability and potentially increases hydrophobicity (reduces hydrophilicity). By varying exposure time, the extent of surface modification can be controlled.\n\n---\n\n#### Step 3: **Characterization and Analysis**\n1. **Contact Angle Measurement**:\n   - Use a contact angle goniometer to measure the static water contact angle on the HMDS-treated polymer surfaces. Follow these steps:\n     - Place a polymer sample on the goniometer stage.\n     - Deposit a ~2 \u00b5L droplet of DI water on the polymer surface using a microsyringe.\n     - Measure the contact angle between the baseline of the droplet and the tangent at the contact point with the surface.\n   - Record the contact angle for each exposure time.\n   - Perform 3\u20135 measurements on different locations of each sample to ensure reproducibility and report the average contact angle.\n\n2. **Surface Chemistry Analysis (Optional)**:\n   - Use Fourier-transform infrared spectroscopy (FTIR) to confirm the surface chemical modification (e.g., disappearance of -OH groups and appearance of -CH\u2083 functional groups).\n   - Conduct X-ray photoelectron spectroscopy (XPS) to quantify the elemental composition and extent of HMDS interaction.\n\n3. **Control Experiment**:\n   - Measure the contact angle of untreated polymer surfaces as a control for comparison with HMDS-treated samples.\n   - Also consider treating the polymer with shorter (1\u20132 minute) and longer exposure times (e.g., 4\u20136 hours) for better understanding of saturation behavior.\n\n---\n\n#### Step 4: **Data Analysis**\n1. **Plot the Results**:\n   - Plot contact angle versus HMDS exposure time. This will help visualize trends (e.g., a potential increase in the contact angle due to surface modification).\n   - Analyze whether the contact angle plateaus after a certain exposure time, indicating saturation of surface modification.\n\n2. **Interpretation**:\n   - Compare the treated samples to the untreated control to evaluate the effect of HMDS treatment.\n   - Discuss surface wettability changes in terms of surface energy and the extent of surface modification.\n\n---\n\n### Safety Considerations:\n1. HMDS is volatile and flammable, so work in a fume hood and avoid open flames.\n2. Wear proper personal protective equipment (PPE), including gloves, goggles, and a lab coat.\n3. Dispose of HMDS and other chemical waste according to institutional safety guidelines.\n\n---\n\n### Conclusion:\nThis experimental procedure addresses your question in a structured manner. By cleaning the surface, treating it with HMDS vapor under controlled conditions, and analyzing the water contact angle, you can systematically evaluate how HMDS exposure time affects the hydrophilicity of the polymer. This approach ensures reproducibility, reliability, and scientific rigor, providing meaningful results for your study."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "When using tetraethylorthosilicate (TEOS) in the experimental process, explain how its role affects the structure and hydrophilicity of the polymer material, and outline a step-by-step approach for incorporating it effectively."}, {"role": "assistant", "content": "Of course. Let\u2019s analyze your question step by step and design a detailed experimental preparation scheme for incorporating tetraethylorthosilicate (TEOS) into a hydrophilic polymer to achieve enhanced hydrophilicity.\n\n---\n\n### **Analysis of the Question**\nThe key points in your question are:\n1. **Role of TEOS**: Understanding the chemical function of tetraethylorthosilicate (TEOS) in the polymer synthesis and how it influences the structure and hydrophilicity of the polymer.\n2. **Experimental Process for Incorporation**: A systematic approach to integrating TEOS into the polymer synthesis, with a focus on achieving improved hydrophilicity.\n3. **Reaction Details**: Consideration of reaction conditions, reagent ratios, and molar quantities to optimize the process.\n\nTo address these, we\u2019ll first discuss the underlying principles and role of TEOS in enhancing polymer hydrophilicity, followed by a detailed, step-by-step synthesis procedure.\n\n---\n\n### **Role of TEOS in Polymer Materials**\nTEOS, a silicon-based alkoxide, is a precursor commonly used in sol-gel chemistry and hybrid organic-inorganic material synthesis. Its hydrolysis and condensation reactions produce polysiloxane or silica networks. TEOS contributes to hydrophilicity in two ways:\n1. **Silica Network Formation**: Hydrolysis of TEOS in the presence of water generates silanol (\u2013Si\u2013OH) groups. These hydroxyl groups are intrinsically hydrophilic and can form hydrogen bonds with water. As a result, incorporating TEOS into a polymer matrix increases the density of hydrophilic sites.\n2. **Crosslinking and Hybrid Structures**: TEOS can form covalent or physical interactions with organic polymer chains, creating a hybrid material with enhanced mechanical properties while retaining high hydrophilicity due to the silica\u2019s surface chemistry.\n\nThus, TEOS essentially serves as a hydrophilic crosslinking agent and a structural modifier for the polymer material.\n\n---\n\n### **Step-by-Step Experimental Process**\n\nBelow is a comprehensive experimental preparation scheme for synthesizing a TEOS-modified hydrophilic polymer:\n\n---\n\n#### **Step 1: Materials Preparation**\n**Chemicals Required:**\n1. Tetraethylorthosilicate (TEOS) \u2013 the precursor for silica formation.\n2. Precursor polymer \u2013 select a hydrophilic monomer such as poly(ethylene glycol) (PEG), poly(vinyl alcohol) (PVA), or poly(acrylamide) (PAM).\n3. Deionized water \u2013 for hydrolysis of TEOS.\n4. Ethanol \u2013 as a solvent for TEOS to improve miscibility.\n5. Catalysts:\n   - Acidic catalyst (e.g., HCl) for hydrolysis.\n   - Basic catalyst (e.g., NH\u2084OH) for condensation.\n6. Crosslinker (optional) \u2013 such as glutaraldehyde if additional network formation is required.\n\n---\n\n#### **Step 2: Hydrolysis of TEOS**\n1. **Reaction Setup**:\n   - Mix TEOS and ethanol in a molar ratio of 1:5 (TEOS:Ethanol) in a stirred beaker or reaction flask.\n   - Gradually add the catalyst (acidic, typically dilute HCl) dropwise into the solution. \n   - Use deionized water at a molar ratio of 1:4 (TEOS:H\u2082O) to ensure effective hydrolysis.\n\n2. **Conditions**:\n   - Maintain constant stirring at room temperature (20\u201325\u00b0C) for 2\u20134 hours to fully hydrolyze TEOS into silanol intermediates (Si\u2013(OH)\u2084).\n\n3. **Mechanism**:\n   - Hydrolysis reaction (acidic conditions):\n     \\[\n     Si(OC\u2082H\u2085)\u2084 + 4H\u2082O \\xrightarrow{\\text{HCl}} Si(OH)\u2084 + 4C\u2082H\u2085OH\n     \\]\n   - This step replaces ethoxy groups with hydroxyl groups, making the system hydrophilic.\n\n---\n\n#### **Step 3: Condensation and Polymer Matrix Incorporation**\n1. **Mixing with Polymer Precursor**:\n   - In a separate vessel, prepare the polymer precursor solution (e.g., dissolve PEG, PVA, or PAM in deionized water or ethanol). The polymer-to-TEOS ratio should be approximately 1:1\u20131:2 (w/w).\n   - Combine the hydrolyzed TEOS solution with the polymer precursor under stirring to ensure homogeneous mixing.\n\n2. **Condensation Reaction**:\n   - Add a basic catalyst (e.g., NH\u2084OH) dropwise to initiate the condensation of silanol groups.\n   - Reaction conditions: temperature 40\u201360\u00b0C, constant stirring for 4\u20136 hours.\n   - Condensation reaction:\n     \\[\n     Si(OH)\u2084 + Si(OH)\u2084 \\xrightarrow{\\text{NH\u2084OH}} Si\u2013O\u2013Si + 2H\u2082O\n     \\]\n\n3. **Hybrid Formation**:\n   - Silica particles or crosslinked silica structures form in situ within the polymer matrix, physically or chemically linking to polymer chains.\n   - These silica regions provide enhanced hydrophilicity due to their surface hydroxyl groups.\n\n---\n\n#### **Step 4: Gelation and Curing**\n1. Transfer the mixture into molds or appropriate substrates if forming a specific polymer shape is required.\n2. Cure the sample by heating at 60\u201380\u00b0C for 6\u201312 hours to solidify the polymer network and promote complete condensation.\n\n---\n\n#### **Step 5: Post-Treatment and Washing**\n1. Wash the cured material with deionized water and ethanol to remove unreacted precursors, ethanol byproducts, and weakly bonded silica particles.\n2. Dry the sample in a vacuum oven at 50\u201360\u00b0C until a constant weight is achieved.\n\n---\n\n### **Key Notes on Reaction Ratios and Optimization**\n1. **TEOS-to-polymer ratio**: A higher TEOS ratio increases hydrophilicity but could compromise flexibility. Experiment with ratios like 1:1 or 1:2 for optimization.\n2. **Catalyst Concentration**: Acidic or basic catalyst concentration should be optimized to ensure controlled hydrolysis and condensation without excessive gelation.\n3. **Hydrolysis Time**: Ensure TEOS is fully hydrolyzed before proceeding to prevent poor silica distribution within the polymer matrix.\n\n---\n\n### **Additional Remarks**\n- To further enhance hydrophilicity, you may consider incorporating other co-monomers, such as acrylic acid or hydrophilic functional groups, into the polymer matrix during synthesis.\n- TEOS-modified hydrophilic polymers are ideal for applications like hydrogels, membranes, and biomedical coatings.\n\n---\n\nBy following this systematic synthesis approach, you should be able to successfully incorporate TEOS into your polymer to increase hydrophilicity while maintaining a robust material structure. Let me know if you have further questions!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Evaluate the effect of varying photoinitiator concentration on achieving hydrophilicity in the polymer. How would you optimize this parameter to ensure successful hydrophilic modification?"}, {"role": "assistant", "content": "To systematically approach your question, let's break it into manageable components and address them step by step to ensure a robust understanding of the relationship between photoinitiator concentration and hydrophilicity in polymer synthesis. The photoinitiator concentration is critical in photopolymerization reactions because it impacts both the polymer structure and its hydrophilicity. \n\n---\n\n### **Step 1: Analyze the Question and Key Points**\n1. **Key Points**:\n   - The effect of photoinitiator concentration on hydrophilicity in the resulting polymer.\n   - The optimization of photoinitiator concentration for successful hydrophilic modification.\n\n2. **Understanding the Problem**:\n   - Photoinitiators generate free radicals under light exposure to initiate polymerization.\n   - Varying the photoinitiator concentration influences the polymer's crosslink density, molecular weight, chain structure, and ultimately the distribution of hydrophilic functional groups within the polymer.\n\n---\n\n### **Step 2: Systematic Answer and Experimental Guidelines**\nTo evaluate and optimize photoinitiator concentration for enhancing hydrophilicity, one must design and implement a photopolymerization experiment. Below, I will outline the approach in detail:\n\n---\n\n#### **Step 2.1: Define the Experimental System**\n- **Polymer Composition**: Identify the monomer(s) used for hydrophilic polymer synthesis. Examples include:\n  - Monomers such as acrylamide, hydroxyethyl methacrylate (HEMA), or acrylic acid, which naturally impart hydrophilicity. \n  - Comonomers for additional functionality, e.g., N-vinyl pyrrolidone (NVP).\n\n- **Photoinitiator**: A commonly used photoinitiator, such as Irgacure 2959 or 2,2-dimethoxy-2-phenylacetophenone (DMPA), will be analyzed for its effect.\n\n- **Reaction Conditions**:\n  - Light wavelength: Match the spectrum to the absorption range of the photoinitiator, typically UV light around 365 nm.\n  - Reaction medium: Aqueous or hydroorganic systems to support hydrophilic polymerization.\n\n#### **Step 2.2: Experimental Procedure**\n1. **Preparation of Monomer Solution**:\n   - Dissolve hydrophilic monomer(s), such as HEMA (1 M), in deionized water or an appropriate solvent, depending on solubility.\n   - (Optional) Add comonomers in desired mole ratios if copolymerization is required.\n\n2. **Photoinitiator Addition**:\n   - Prepare a series of monomer solutions with varying photoinitiator concentrations. For example:\n     - Concentrations at 0.1%, 0.25%, 0.5%, 1.0%, and 2.0% (w/v) relative to the monomer weight.\n   - Ensure complete dissolution of the photoinitiator by stirring thoroughly in a dark environment to avoid premature initiation.\n\n3. **Polymerization Setup**:\n   - Transfer the solutions into mold chambers (e.g., glass Petri dishes or vials) for uniform light exposure.\n   - Degas the monomer solution under nitrogen or argon to remove dissolved oxygen, which inhibits free radical polymerization.\n\n4. **Photopolymerization**:\n   - Illuminate the samples uniformly with UV light (365 nm) at a controlled intensity.\n   - Polymerization time can range from 10 minutes to 1 hour, depending on the system and photoinitiator efficiency. Monitor the reaction.\n\n---\n\n#### **Step 2.3: Characterization and Evaluation of Hydrophilicity**\nPost-polymerization, evaluate the hydrophilicity of the resulting polymers. The hydrophilicity depends on factors such as surface functional groups, swelling behavior, and water absorption, which are influenced by photoinitiator concentration.\n\n1. **Key Characterization Techniques**:\n   - **Contact Angle Measurement**:\n     - Hydrophilicity is inversely related to the water contact angle. Lower contact angles indicate higher hydrophilicity.\n   - **Swelling Ratio**:\n     - Immerse the polymer in water and measure the mass change over time. Higher swelling ratios reflect better hydrophilic behavior.\n   - **Fourier Transform Infrared Spectroscopy (FTIR)**:\n     - Confirm the incorporation of hydrophilic functional groups (e.g., hydroxyl or carboxyl peaks).\n\n2. **Expected Trends**:\n   - At low photoinitiator concentrations: Polymerization may be incomplete, resulting in reduced crosslink density and poor hydrophilicity due to insufficient chain propagation.\n   - At high photoinitiator concentrations: Excessive free radicals can lead to rapid termination reactions, forming a dense, highly crosslinked network that may restrict the hydration capacity or functional group accessibility.\n\n---\n\n#### **Step 2.4: Optimization of the Photoinitiator Concentration**\nBased on the experimental results, optimize the photoinitiator concentration:\n1. **Determine the Optimal Range**:\n   - Identify the concentration that achieves a balance between adequate polymerization and sufficient hydrophilic functional group exposure.\n   - Typically, this might fall within a moderate concentration range (e.g., 0.5%\u20131.0% w/v), depending on the specific system.\n\n2. **Reiterate Synthesis**:\n   - Fine-tune the photoinitiator concentration within the identified range to confirm reproducibility and enhance polymer hydrophilicity further.\n\n3. **Consider Additives or Secondary Modifications**:\n   - If optimal photoinitiator concentration alone does not yield desired hydrophilicity, consider post-polymerization modification or blending of hydrophilic monomers.\n\n---\n\n### **Summary**\nTo study the effect of photoinitiator concentration on hydrophilicity, conduct a systematic photopolymerization experiment by preparing polymer formulations with varying photoinitiator levels and characterizing hydrophilicity using contact angles, swelling behavior, and chemical analysis. The optimal concentration balances efficient polymerization with accessibility to hydrophilic functional groups, likely in the moderate range of photoinitiator. Through careful optimization, you can ensure successful hydrophilic modification of the polymer while maintaining reproducibility and efficiency.\n\n"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain how you would incorporate 'acryloyloxyethyltrimethylammonium chloride' into a polymer backbone to introduce hydrophilic properties, and describe the subsequent steps required to prepare the final polymer material."}, {"role": "assistant", "content": "Absolutely, let us systematically analyze and address your question. To incorporate the hydrophilic monomer **acryloyloxyethyltrimethylammonium chloride** (AETMAC) into a polymer backbone and achieve a hydrophilic polymer while meeting your needs for clarity and practicality in the laboratory, we will need to design a controlled polymerization experiment. Here's how we proceed:\n\n---\n\n### Step 1: Analyze the Problem\n1. **Key Objective:** Incorporating the hydrophilic monomer **AETMAC** into the polymer backbone to impart hydrophilic properties.\n2. **Suitable Polymerization Method:** Since AETMAC contains a polymerizable acrylate group (-C=C-), it can undergo radical polymerization with other monomers. **Solution polymerization** or **emulsion polymerization** are commonly used methods for water-soluble hydrophilic polymers.\n3. **Polymer Design:** We can create a homopolymer (all AETMAC polymerized together) or a copolymer (AETMAC polymerized with other monomers like acrylamide or acrylic acid).\n\n---\n\n### Step 2: Experimental Preparation Scheme\nBelow is the detailed synthesis protocol with reagents, reaction conditions, and procedural steps to guide you through laboratory implementation.\n\n---\n\n#### **Preparation Method: Radical Copolymerization**\n\n##### **Materials and Chemicals Required:**\n1. **Monomers:**\n   - **Acryloyloxyethyltrimethylammonium chloride (AETMAC):** Hydrophilic monomer.\n   - **Optional co-monomer (e.g., acrylamide or acrylic acid):** Enhances other physical properties such as viscosity and mechanical strength.\n2. **Solvent:**\n   - **Deionized water (or a water/ethanol mixture):** Ideal solvent for water-soluble hydrophilic polymers.\n3. **Initiator:**\n   - **Ammonium persulfate (APS):** A radical initiator for water-based reactions.\n4. **Crosslinker (optional):**\n   - For a lightly crosslinked polymer, add **N,N'-methylene bisacrylamide** in small quantities.\n\n##### **Procedure:**\n\n**Step 1: Preparation of the Reaction Solution**\n1. **Dissolve Monomers:** In an Erlenmeyer flask or a reaction vessel, dissolve the desired amount of **AETMAC** (typically 0.5\u20131.0 mol equivalent relative to total monomers) in **deionized water**.\n2. **Add Optional Co-monomer:** For a copolymer, weigh and add the co-monomer to the solution (e.g., acrylamide in 1:1 molar ratio with AETMAC or differing ratios to tune properties).\n3. **Maintain Neutral pH:** Adjust the pH of the solution to 6\u20137 using NaOH or HCl as needed to optimize the solubility and polymerization kinetics.\n4. **Introduce Crosslinker:** If desired, dissolve **N,N'-methylene bisacrylamide** (typically \u22641 mol% of total monomers) for partial crosslinking.\n\n**Step 2: Dissolve Polymerization Initiator**\n1. **Prepare Initiator Solution Separately:** Dissolve **ammonium persulfate (APS)** in deionized water (e.g., 0.5\u20131.0 wt% relative to total monomers).\n2. **Keep Initiator Fresh:** Only add APS to the reaction mixture immediately before polymerization to avoid premature initiation.\n\n**Step 3: Polymerization Reaction**\n1. **Degas the Solution:** Oxygen inhibits radical polymerization, so sparge the monomer solution with nitrogen gas for 20\u201330 minutes to remove dissolved oxygen.\n2. **Mix Polymerization Components:** Gradually add the APS solution to the monomer under stirring.\n3. **Control Temperature:** Increase the reaction temperature to 50\u201370\u00b0C to initiate radical polymerization. Maintain the solution at this temperature for 4\u20136 hours with continuous stirring.\n4. **Monitor Viscosity Change:** As the polymerization occurs, the viscosity of the solution will increase. Ensure the reaction remains homogeneous by adjusting stirring speed if necessary.\n\n---\n\n**Step 4: Purification of the Polymer**\n1. **Precipitation (Optional):** If the final polymer is soluble but needs further purification, precipitate the polymer by dripping the mixture into a nonsolvent like cold methanol while stirring.\n2. **Dialysis:** For water-soluble polymers, dialyze the reaction mixture against deionized water to remove unreacted monomers, impurities, and low molecular weight byproducts.\n3. **Drying:** Freeze-dry or dry the purified product in a vacuum oven at \u226440\u00b0C to preserve its hydrophilic qualities.\n\n**Step 5: Characterization**\n1. **Molecular Weight:** Use gel permeation chromatography (GPC) or viscometry to analyze the molecular weight distribution of the final polymer.\n2. **Hydrophilicity Testing:** Test surface hydrophilicity by measuring the water contact angle or conducting swelling studies in aqueous media.\n3. **FTIR:** Confirm the presence of characteristic functional groups (such as quaternary ammonium peaks) to ensure AETMAC integration into the polymer.\n\n---\n\n### Step 3: Notes and Reaction Tips\n1. **Reagent Ratios:** Adjust the ratio of **AETMAC** to co-monomers depending on the desired hydrophilicity and polymer properties. Higher AETMAC content results in greater hydrophilicity.\n2. **Safety Considerations:** AETMAC is generally stable but handle radical initiators like APS with care due to their oxidative nature.\n3. **Reaction Optimization:** Perform small-scale preliminary reactions to optimize reagent concentrations and polymerization conditions before scaling up.\n\n---\n\nThis systematic protocol incorporates **AETMAC** into the polymer backbone and enhances hydrophilicity. By following these steps, you should be able to successfully synthesize hydrophilic polymers suitable for various applications, such as water treatment, biomedical materials, or surface modification.\n\nLet me know if you have specific concerns about polymer design or application!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Describe how the molecule Tween 20 can be chemically modified and incorporated into a polymer matrix to enhance its hydrophilicity. Include details of any reactions or catalysts that might be required."}, {"role": "assistant", "content": "Certainly! Thank you for your question. Let\u2019s systematically approach the task of chemically modifying Tween 20 and incorporating it into a polymer matrix to enhance hydrophilicity. Here's how we proceed, step by step.\n\n---\n\n### **1. Analysis of the Question and Key Points**\n#### Key Points:\n- **Tween 20**: Tween 20 is a surfactant with a polyoxyethylene chain, which gives it inherent hydrophilicity. It contains hydroxyl groups in its polyether structure.\n- **Enhancing Hydrophilicity**: The goal is to chemically modify Tween 20 so that it becomes more hydrophilic when integrated into a polymer matrix.\n- **Incorporation into a Polymer Matrix**: Chemical modification and integration into a polymer network must occur under controlled conditions to ensure compatibility with the matrix and stability of the final material.\n\n#### Summary of the Approach:\nTo enhance hydrophilicity using Tween 20, we will:\n1. Modify its structure by functionalizing the hydroxyl groups to create reactive sites for polymerization.\n2. Couple it to a polymer backbone through covalent linkage, utilizing appropriate catalysts and reaction conditions.\n3. Optimize the polymerization reaction and validate the hydrophilicity of the resulting material.\n\nNow, let\u2019s delve into the experimental preparation scheme step by step.\n\n---\n\n### **2. Detailed Experimental Preparation Scheme**\n\n#### **Step 1: Functionalizing Tween 20**\nTo integrate Tween 20 into a polymer matrix, the hydroxyl groups in its structure must be activated to allow polymer attachment. A common strategy is using acryloyl chloride or glycidyl methacrylate to introduce polymerizable functional groups.\n\n**Reaction:**\nHydroxyl groups on Tween 20 react with acryloyl chloride to form acrylate-functionalized Tween 20.\n\n- **Reagents**: Tween 20, Acryloyl chloride, Triethylamine (TEA).\n- **Solvent**: Dichloromethane (DCM) or anhydrous toluene.\n- **Reaction Conditions**:\n  - Dissolve Tween 20 in DCM or toluene under inert conditions (argon or nitrogen atmosphere).\n  - Slowly add acryloyl chloride dropwise in the presence of TEA to neutralize HCl produced during the reaction.\n  - Maintain the temperature at 0\u20135\u00b0C during addition, then stir at room temperature for 6\u201312 hours.\n\n**Key Parameters**:\n- Molar ratio of Tween 20:acryloyl chloride:TEA = 1:2:2 to ensure complete activation of hydroxyl groups.\n- Monitor reaction progress using thin-layer chromatography (TLC) or FTIR spectroscopy (look for the formation of ester bonds by observing C=O stretching at ~1720 cm\u207b\u00b9).\n\n---\n\n#### **Step 2: Copolymerization of Tween 20**\nOnce Tween 20 is functionalized, it can be grafted onto a hydrophilic polymer matrix, such as poly(acrylamide) or poly(acrylic acid), by free radical polymerization.\n\n**Reaction:**\nCopolymerization of acrylate-functionalized Tween 20 with acrylamide or acrylic acid.\n\n- **Reagents**: Acrylate-functionalized Tween 20, acrylamide or acrylic acid, initiator (e.g., potassium persulfate (KPS)), crosslinker (N,N'-methylenebisacrylamide).\n- **Solvent**: Water or a water/ethanol mixture.\n- **Reaction Conditions**:\n  - Prepare an aqueous solution of acrylamide, functionalized Tween 20, and the crosslinker.\n  - Add KPS as a radical initiator and gently heat the solution to 40\u201360\u00b0C.\n  - Stir under nitrogen atmosphere or vacuum to remove oxygen, which inhibits polymerization.\n  - Allow the reaction to proceed for 4\u20136 hours.\n\n**Key Parameters**:\n- Ratios:\n  - Functionalized Tween 20: acrylamide = 1:10\u20131:50 (optimize hydrophilicity without compromising the integrity of the polymer).\n  - Crosslinker ~1\u20132 mol% relative to monomer units.\n- Polymerization temperature: 40\u201360\u00b0C.\n\n**Outcome**:\nThe resulting polymer matrix incorporates Tween 20 as a hydrophilic segment, providing amphiphilic characteristics and enhanced water absorption.\n\n---\n\n#### **Step 3: Validation of the Hydrophilic Polymer**\nAfter polymer synthesis, the material\u2019s hydrophilicity can be characterized through water contact angle measurements and swelling tests.\n\n- **Contact Angle**: Measure the contact angle of a water droplet on the polymer surface to determine hydrophilicity. Lower contact angles indicate higher hydrophilicity.\n- **Swelling Ratio**: Immerse polymer samples in water and calculate the swelling degree to evaluate water uptake.\n- **Spectroscopic Analysis**: Use FTIR to confirm the presence of Tween 20 in the matrix (polyoxyethylene stretching bands at ~1100 cm\u207b\u00b9) and ensure successful covalent bonding.\n\n---\n\n### **3. Summarizing Benefits of This Approach**\nBy functionalizing Tween 20 and incorporating it into a polymer matrix, the hydrophilicity is enhanced due to the increased density of hydrophilic groups (polyoxyethylene chains and hydroxyl groups) within the network. Additionally, covalent bonding ensures it remains stably integrated, unlike physical blending methods.\n\nIn the lab, following this scheme will allow precise control over the polymer composition, enabling better optimization for hydrophilic properties tailored to specific applications.\n\nIf you have further questions or need clarification on any step, feel free to ask!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "How would you incorporate nano-SiO2 into a polymer solution to ensure uniform dispersion and effective integration into the polymer matrix? Detail the steps you would follow."}, {"role": "assistant", "content": "To address your question systematically, we need to carefully analyze the problem and provide a detailed experimental preparation scheme that enables the incorporation of nano-SiO\u2082 into a polymer solution, ensuring uniform dispersion and effective integration into the polymer matrix. Here is a step-by-step method to achieve this, along with the reasoning and conditions for each step.\n\n---\n\n### **1. Key Analysis and Summary of the Problem**\n#### Key Concepts:\n- **Nano-SiO\u2082** is a hydrophilic nanoparticle that often aggregates due to its high surface energy and hydrogen bonding among hydroxyl groups on the surface.\n- **Effective incorporation**: It is critical to ensure the uniform dispersion of nano-SiO\u2082 into the polymer matrix to avoid agglomerated nanoparticles and to maintain the desired properties (e.g., hydrophilicity, transparency, and mechanical properties) of the final polymer composite.\n- **Polymer compatibility**: Depending on the polymer system, the dispersion can be either via covalent bonding, physical entrapment, or surface modification.\n\n#### Approach:  \nWe will use a combination of surface modification of nano-SiO\u2082 and sonication-assisted dispersion methods, followed by uniform mixing into the polymer solution.\n\n---\n\n### **2. Detailed, Step-by-Step Experimental Preparation Scheme**\n\n#### **Step 1: Surface Modification of Nano-SiO\u2082 (Optional but Recommended)**\nPurpose: Nano-SiO\u2082 particles are prone to aggregation; therefore, surface modification (via silanization) with hydrophilic or polymer-compatible groups improves dispersion and compatibility with the polymer matrix.\n\n1. **Reagents:**\n   - Nano-SiO\u2082\n   - Silane coupling agent (e.g., 3-aminopropyltriethoxysilane (APTES) or methacryloxypropyltrimethoxysilane (MPTMS), depending on the polymer system)\n   - Ethanol or toluene (as solvent)\n   - Water (deionized)\n   - Acetic acid (to adjust pH for silanization)\n\n2. **Procedure:**\n   a. In a glass beaker, prepare a solution of ethanol and deionized water in a 95:5 volume ratio.\n   b. Adjust the pH of this solution to ~4.5 using acetic acid (acidity promotes hydrolysis of the silane agent).\n   c. Add the silane coupling agent to the ethanol-water mixture under magnetic stirring (e.g., 2 wt% of silane based on the weight of nano-SiO\u2082).\n   d. Gradually add nano-SiO\u2082 to the solution and sonicate for 1 hour to break any agglomerates.\n   e. Stir the reaction at 60\u201380\u00b0C for 4 hours to complete the silanization reaction.\n   f. After the reaction, collect the modified nano-SiO\u2082 by centrifugation and wash thoroughly with ethanol to remove unreacted silane.\n   g. Dry the modified nano-SiO\u2082 in a vacuum oven at 60\u00b0C for 12 hours.\n\n#### **Step 2: Preparation of the Polymer Solution**\nPurpose: Dissolve the polymer in an appropriate solvent to ensure a homogeneous medium for introducing nano-SiO\u2082.\n\n1. **Reagents:**\n   - Desired polymer (e.g., PVA, PVP, or a hydrophilic polymer of your interest)\n   - Solvent (depending on polymer solubility; common solvents include water, ethanol, or DMF)\n\n2. **Procedure:**\n   a. Weigh the required amount of polymer (e.g., 5 g for a 10 wt% polymer solution).\n   b. Dissolve the polymer in the solvent under constant stirring at the appropriate temperature (e.g., 80\u00b0C for PVA in water) to ensure complete dissolution.\n   c. Allow the polymer solution to cool to room temperature, ensuring it is homogeneous and free from undissolved particles.\n\n#### **Step 3: Dispersion of Nano-SiO\u2082**\nPurpose: Achieve a uniform distribution of nano-SiO\u2082 in the polymer solution using sonication and stirring.\n\n1. **Reagents:**\n   - Modified nano-SiO\u2082 (prepared in Step 1 or unmodified nano-SiO\u2082 if skipping Step 1)\n   - Polymer solution (prepared in Step 2)\n\n2. **Procedure:**\n   a. Calculate the desired amount of nano-SiO\u2082 to incorporate into the polymer solution (e.g., 1\u20135 wt% relative to the weight of the polymer).\n   b. Pre-disperse nano-SiO\u2082 in a small volume of the same solvent used for the polymer solution using a probe sonicator. Use short bursts (10\u201330 seconds) to avoid overheating the solvent.\n   c. Gradually add the pre-dispersed nano-SiO\u2082 into the polymer solution under continuous stirring.\n   d. Use a probe sonicator to ensure uniform dispersion. Sonicate for 5\u201310 minutes in pulse mode (e.g., 5 seconds on, 5 seconds off) while maintaining the solution temperature below 40\u00b0C.\n\n#### **Step 4: Integration and Final Mixing**\nPurpose: Ensure stable and uniform integration of nano-SiO\u2082 into the polymer matrix.\n\n1. Continue stirring the polymer-nano-SiO\u2082 mixture for 1\u20132 hours at room temperature.\n2. Check the dispersion visually or using analytical techniques such as dynamic light scattering (DLS) or scanning electron microscopy (SEM).\n3. If visible aggregates are still present, apply additional sonication or filtration through a mesh to remove large agglomerates.\n\n#### **Step 5: Polymer Processing or Film Casting**\nPurpose: Process the polymer-nano-SiO\u2082 mixture into the desired form (e.g., film, gel, or coating).\n\n1. Pour the homogeneous solution onto a substrate (e.g., glass or PTFE molds) for film casting.\n2. Dry the film slowly at room temperature to avoid defects, followed by thermal treatment (e.g., 60\u00b0C for several hours) to remove residual solvent.\n\n---\n\n### **3. Notes on Reaction Conditions and Considerations**\n- **Safety:** Nano-SiO\u2082 is an inhalation hazard; always handle it in a fume hood while wearing appropriate PPE.\n- **Sonication:** Prolonged sonication can degrade some polymers. Use optimized parameters to avoid this.\n- **Surface Modification:** If your polymer has specific functional groups (e.g., hydroxyls or amines), consider using silanes with complementary groups to enhance bonding between nano-SiO\u2082 and the polymer matrix.\n- **Verification:** Use analytical techniques (e.g., SEM for morphology, FTIR for chemical interaction, TGA for thermal stability) to confirm successful integration of nano-SiO\u2082.\n\n---\n\nBy following this systematic approach, you should achieve uniform dispersion and effective integration of nano-SiO\u2082 into the polymer matrix, resulting in a high-performance composite material with enhanced hydrophilicity."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "What precautions would you take to ensure successful free-radical polymerization when using N,N-\u4e8c\u7532\u57fa\u4e19\u70ef\u9178\u80fa as a monomer in a hydrophilic polymer synthesis? Include considerations for reaction temperature and initiators in your explanation."}, {"role": "assistant", "content": "To answer your question systematically and comprehensively, we will identify the key points regarding the use of **N,N-dimethylacrylamide (DMAA, N,N-\u4e8c\u7532\u57fa\u4e19\u70ef\u9178\u80fa)** as a monomer in the context of free-radical polymerization for synthesizing a hydrophilic polymer. I will walk you through the details of the synthesis process, including critical precautions to ensure the success of the reaction.\n\n---\n\n### **Key Points for Analysis**\n1. **Monomer background**: DMAA is hydrophilic due to its amide group, which can engage in hydrogen bonding. It is an excellent choice when designing hydrophilic polymers.\n2. **Polymerization method**: Free-radical polymerization is widely used for DMAA because it allows easy control over reaction conditions and is compatible with various initiators.\n3. **Critical considerations**:\n   - Temperature regulation (a crucial factor in the rate of reaction, polymer quality, and prevention of undesirable side reactions).\n   - Choice of initiators (specific initiators and concentrations significantly influence the polymerization process).\n   - Oxygen inhibition (oxygen scavenges free-radicals and can inhibit polymerization efficiency).\n   - Reaction solvent/medium (for consistent monomer solubility and controllable mixing).\n   \nHaving identified these, let us proceed step by step in developing a detailed experimental approach that covers all the necessary precautions.\n\n---\n\n### **Detailed Steps and Precautions for Free-Radical Polymerization**\n\n#### **1. Selection of the Initiator**\nFree-radical polymerization requires an initiator to generate free radicals that start the polymerization chain reaction. Common initiators for polymerizing DMAA include:\n   \n- **Thermal initiators**:\n  - **Azobisisobutyronitrile (AIBN)**: A widely used free-radical initiator that decomposes thermally to generate radicals. It requires temperatures in the range of **60\u201380\u00b0C** (initiator half-life depends on temperature).\n  - **Potassium persulfate (KPS)**: Also effective for water-based polymerization, especially if the solvent is aqueous.\n\n- **Redox initiator systems**:\n  - In cases where low temperatures (e.g., room temperature) are desired, a redox system such as **ammonium persulfate (APS)** combined with a reducing agent like **N,N,N',N'-tetramethylethylenediamine (TEMED)** can be used to initiate polymerization.\n\n##### **Precaution 1**: Initiator concentration must be optimized:\nUse initiator concentrations in the range of **0.1\u20131.0 wt% of the total monomer weight**, depending on the desired molecular weight of the polymer (lower initiator concentrations generally yield higher molecular weights).\n\n##### **Precaution 2**: Avoid premature decomposition of the initiator:\nAdd the initiator to the reaction mixture **after all other components (monomer, solvent, chain transfer agents, etc.) are fully dissolved and mixed**. For thermal initiators like AIBN, ensure the reaction vessel has reached the desired polymerization temperature before introducing the initiator.\n\n---\n\n#### **2. Reaction Temperature Control**\nTemperature is a critical factor in free-radical polymerization for DMAA:\n- **AIBN**: Requires **60\u201380\u00b0C**, typically 70\u00b0C is optimal for generating radicals at a sustainable rate.\n- **KPS**: Functions effectively in the range of **60\u201380\u00b0C**, with decomposition accelerated by higher temperature.\n- **Redox initiators (e.g., APS/TEMED)**: Operate at **room temperature to around 40\u00b0C**, advantageous for thermally sensitive applications.\n\n##### **Precaution 3**: Use a controlled heating mechanism:\nEmploy a thermostated water bath or oil bath with precise temperature control to keep the reaction mixture at the target temperature. Temperature fluctuations can affect the polymerization rate and molecular weight distribution.\n\n##### **Precaution 4**: Avoid excessive heat:\nOverheating can lead to radical termination reactions, undesirable crosslinking, or side reactions, leading to polymer degradation or gelation.\n\n---\n\n#### **3. Purging with Inert Gas (Removing Oxygen)**\nOxygen in the reaction environment interferes with free-radical polymerization by scavenging radicals and forming peroxides, resulting in reduced polymerization efficiency or premature termination.\n\n##### **Precaution 5**: Degas the reaction mixture:\n- Purge the reaction system (flask, solvent, monomer, etc.) with **inert gas (e.g., nitrogen or argon)** for at least **15\u201330 minutes** before initiating polymerization. Use a gas inlet system connected to the reaction vessel.\n- Perform the reaction under a nitrogen or argon blanket to maintain an oxygen-free atmosphere throughout the reaction.\n\n---\n\n#### **4. Choice of Solvent**\nDMAA is water-soluble, making it well-suited for **aqueous or mixed solvent polymerizations**. However, other polar solvents such as **methanol, ethanol, or dimethyl sulfoxide (DMSO)** can also be used depending on the specific application.\n\n##### **Precaution 6**: Choose a solvent that:\n- Ensures complete solubility of the monomer and initiator.\n- Does not interfere with the reaction or generate side reactions.\n- Can stabilize the resulting polymer (e.g., aqueous solutions often aid in maintaining hydrophilic polymer properties).\n\n##### **Precaution 7**: Maintain solvent proportions:\nExcess solvent may dilute the reaction mixture and reduce polymerization kinetics. Typically, **30\u201350 wt% monomer concentration** is used for polymerization in solution. Adjust based on the target polymer and reactor type.\n\n---\n\n#### **5. Reaction Time and Monitoring**\nPolymerization time should be optimized to allow complete monomer conversion while minimizing degradation or chain termination from prolonged reaction.\n\n##### **Precaution 8**: Monitor the reaction:\n- Check the mixture's viscosity and perform monomer conversion analysis using tools such as **NMR spectroscopy** or **gas chromatography**.\n- Terminate the reaction promptly when desired conversion (usually >95%) is achieved by rapid cooling or addition of a radical inhibitor (e.g., hydroquinone).\n\n---\n\n#### **6. Post-Polymerization Purification**\nAfter polymerization, the polymer must be purified to remove unreacted monomer, initiator residues, or side products.\n\n##### **Precaution 9**: Choose a suitable purification process:\n- **Precipitation method**: Precipitate the polymer into a nonsolvent (e.g., precipitate DMAA polymer using diethyl ether or acetone). Collect the polymer via filtration and dry under vacuum.\n- **Dialysis**: For water-soluble polymers (e.g., where a hydrophilic polymer is intended), use dialysis to remove low molecular weight impurities.\n\n---\n\n### **Summary**\nTo ensure a successful free-radical polymerization of N,N-dimethylacrylamide for a hydrophilic polymer:\n1. Choose an appropriate initiator (e.g., AIBN for thermal, APS/TEMED for redox).\n2. Carefully control reaction temperature within the optimal ranges and avoid overheating.\n3. Purge the system with nitrogen or argon to exclude oxygen.\n4. Use a proper solvent to ensure solubility and avoid side reactions.\n5. Monitor reaction progress and terminate at the desired conversion.\n6. Purify the polymer thoroughly to remove traces of impurities.\n\nBy following these steps and precautions, you will enhance the hydrophilicity of the resulting polymer while achieving a high-purity product with controlled molecular weight characteristics. Let me know if you need clarification or further discussion!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "In an experiment aimed at enhancing polymer hydrophilicity, how would you utilize methylacryloyloxyethyl-N,N-dimethylpropanesulfonate (DMAPS) as a monomer during the synthesis process? Please outline the preparation steps and reaction conditions."}, {"role": "assistant", "content": "Certainly! Let's analyze your question and systematically outline a detailed experimental synthesis process using methylacryloyloxyethyl-N,N-dimethylpropanesulfonate (DMAPS) as a monomer to enhance polymer hydrophilicity.\n\n---\n\n### 1. **Key Points in the Question**\n- **Objective**: To use DMAPS as a functional hydrophilic monomer in the experimental synthesis of a polymer with enhanced hydrophilicity. This will leverage the zwitterionic nature of DMAPS, which has sulfonate (-SO\u2083\u207b) and quaternary ammonium groups (-N\u207a(CH\u2083)\u2082).\n- **Approach**: Incorporate DMAPS into a polymer backbone via free-radical polymerization to ensure its hydrophilic moieties are part of the resulting polymer chain.\n- **Deliverables**: The preparation steps, detailed reaction conditions, and reagent requirements.\n\nBased on this information, the target synthesis likely involves copolymerization or homopolymerization of DMAPS to prepare a water-soluble or hydrophilic polymer. Let me now outline the necessary steps.\n\n---\n\n### 2. **Experimental Preparation Scheme for Hydrophilic Polymer Using DMAPS**\n\n#### (A) **Materials and Reagents**\n1. **Monomer**: Methylacryloyloxyethyl-N,N-dimethylpropanesulfonate (DMAPS).\n2. **Co-monomers** (optional): Depending on the desired polymer composition, hydrophobic monomers such as methyl methacrylate (MMA) or hydrophilic co-monomers like acrylic acid (AA) or acrylamide (AM) can be used.\n3. **Solvent**: Deionized water (for aqueous polymerization) or a mixture of water and ethanol.\n4. **Initiator**: A water-soluble free-radical initiator (e.g., ammonium persulfate (APS), or potassium persulfate (KPS)).\n5. **Cross-linker** (optional): For gel formation, cross-linkers like N,N'-methylenebisacrylamide (MBAA) can be used.\n6. **pH Adjusting Agents**: Sodium hydroxide (NaOH) or hydrochloric acid (HCl), if needed.\n\n---\n\n#### (B) **Experimental Steps**\n\n**Step 1: Reaction Setup**\n- Use a clean, dry round-bottom flask or a reaction vessel equipped with a magnetic stirrer and nitrogen purging system.\n- Add the required amount of DMAPS and other desired monomers (if performing copolymerization) to the reaction flask.\n- Depending on the solubility of DMAPS and co-monomers, dissolve them in deionized water or a water-ethanol solvent mixture. The concentration of the monomers should usually be around **10\u201320% (w/v)**.\n\n**Step 2: Degassing**\n- **Why?** Oxygen inhibits free radical polymerization, so purging the reaction mixture with nitrogen (or argon) is essential.\n- Bubble nitrogen through the reaction solution for **15\u201330 minutes** while stirring.\n\n**Step 3: Initiator Preparation**\n- Prepare a fresh solution of the free-radical initiator, such as **ammonium persulfate (APS)** or **potassium persulfate (KPS)**, in a small amount of deionized water.\n- The typical initiator-to-monomer molar ratio is **1:100 to 1:200**, depending on the desired polymer molecular weight. For example:\n  - If using 1 g of DMAPS (MW = 295.34 g/mol), this is approximately **3.38 mmol**. The initiator amount would be **0.0169\u20130.0338 mmol** (e.g., 4\u20138 mg of APS or KPS).\n\n**Step 4: Polymerization Reaction**\n- Heat the reaction mixture to **60\u201370\u00b0C** while maintaining stirring and continuous nitrogen flow.\n- Slowly add the initiator solution dropwise to the reaction mixture to initiate polymerization.\n- Allow the polymerization to proceed for **4\u20136 hours** under constant temperature and stirring. Over time, the mixture will become more viscous, indicating polymer formation.\n\n**Step 5: Termination**\n- After completing the polymerization, cool the reaction mixture to room temperature and expose it to air to terminate the reaction. Antioxidants (e.g., hydroquinone) can also be added to quench free radicals if necessary.\n\n**Step 6: Purification**\n- Precipitate the polymer by adding the reaction mixture into a non-solvent like acetone or ethanol for hydrophilic polymers.\n- Collect the precipitated polymer via filtration or centrifugation, and wash it several times with the non-solvent to remove unreacted monomers and by-products.\n- Dry the purified polymer under vacuum at **40\u201350\u00b0C** until constant weight is achieved.\n\n---\n\n#### (C) **Optimization Tips**\n1. **Solvent Selection**: DMAPS is hydrophilic, so aqueous systems are generally preferred. However, for copolymerization with hydrophobic monomers, incorporate a water-miscible organic solvent like ethanol.\n2. **Cross-Linking (Optional)**: If you want a hydrogel, add a small amount (<1 mol%) of MBAA as the cross-linker.\n3. **Polymer Composition**: Vary the ratio of DMAPS to co-monomers to tune the hydrophilicity of the final polymer.\n4. **Reaction pH**: Keep the pH neutral (around 6\u20137) to prevent premature decomposition of the persulfate initiator or hydrolysis of the sulfonate groups.\n\n---\n\n#### (D) **Characterization**\nAfter synthesis, you must confirm the successful incorporation of DMAPS and verify the polymer's hydrophilicity. Suggested methods:\n1. **FTIR Spectroscopy**: Confirm functional groups, especially sulfonate (-SO\u2083\u207b) at ~1040\u20131080 cm\u207b\u00b9.\n2. **NMR Spectroscopy**: Identify the chemical structure and verify the presence of DMAPS' zwitterionic moieties.\n3. **Water Contact Angle Measurements**: Evaluate surface hydrophilicity.\n4. **Swelling Tests** (for hydrogels): Quantify water absorption to assess hydrophilic performance.\n\n---\n\n### 3. **Summary**\nBy effectively utilizing DMAPS as a monomer in polymerization, we introduce zwitterionic moieties that significantly enhance the hydrophilicity of the resulting polymer. The outlined procedure includes crucial steps, reaction conditions, and optimization tips to ensure reproducibility and success in the lab. This synthesis can be easily tailored for homopolymerization or copolymerization, depending on the specific application.\n\nFeel free to discuss any step in further detail if you have questions!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Given the molecule 'methoxy polyethylene glycol acrylate', outline a detailed experimental procedure for its use in forming an amine-terminated intermediate that can be further modified to enhance the hydrophilicity of a polymer material."}, {"role": "assistant", "content": "To address your question regarding the preparation of an amine-terminated intermediate from the molecule **methoxy polyethylene glycol acrylate (MPEG-A)**, I will design a detailed experimental procedure. By following these steps systematically, we can achieve the formation of the amine-functionalized intermediate, which can further be used for enhancing the hydrophilicity of a polymer material. Let us first analyze and break down the problem:\n\n---\n\n### **1. Question Analysis and Key Points**\n- **Molecule of focus:** Methoxy polyethylene glycol acrylate (MPEG-A). This molecule contains:\n  - A polyethylene glycol (PEG) segment, which imparts inherent hydrophilicity.\n  - A methoxy group (-OCH3) at one terminal, providing end termination and stability.\n  - An acrylate functional group (-CH=CHCO-) at the other end, which is reactive and can be used for polymer synthesis or further functionalization.\n\n- **Objective:** Synthesize an **amine-terminated intermediate** starting from MPEG-A, as a precursor to modify and enhance the hydrophilicity of polymer materials.\n  \n- **General Approach:** This involves modifying the acrylate group of MPEG-A into an amine-functionalized group. Acrylate groups are highly reactive and can undergo nucleophilic addition reactions with an appropriate amine-containing reagent, forming an amine-functionalized product.\n\n---\n\n### **2. Detailed Experimental Procedure**\n\nBelow, I outline a step-by-step preparation of the amine-terminated intermediate **methoxy polyethylene glycol amine (MPEG-NH2):**\n\n---\n\n#### **Step 1: Materials and Reagents**\n- **Methoxy polyethylene glycol acrylate (MPEG-A)** (molecular weight tuned\u2014commonly ~500 to 4000 Da, depending on the desired flexibility/hydrophilicity).\n- **Ethanolamine** or **diethanolamine** (nucleophilic amine to react with the acrylate group).\n- **Solvent:** Tetrahydrofuran (THF), anhydrous (if required, dimethylformamide (DMF) can also be used as an alternative polar aprotic solvent).\n- **Catalyst:** Triethylamine (TEA) to optimize the reaction by neutralizing side-products (optional, depending on the conditions).\n- **Purification materials:** Silica gel, rotary evaporator.\n- **Nitrogen or Argon:** For inert atmosphere if necessary.\n\n---\n\n#### **Step 2: Reaction Setup**\n\n- Prepare a **dry round-bottom flask** equipped with a magnetic stir bar.\n- If needed, ensure the reaction is conducted under an **inert atmosphere** (e.g., by purging with nitrogen) to avoid contamination or oxidation.\n\n---\n\n#### **Step 3: Reaction Mechanism**\n\nThe functionalization occurs via **Michael addition**, where the nucleophilic nitrogen in ethanolamine or diethanolamine attacks the electrophilic \u03b2-carbon of the acrylate group in MPEG-A, resulting in the formation of an amine-functionalized product.\n\n1. **Reagent Ratios**: \n   - For each mole of MPEG-A acrylate, use 1.2\u20131.5 moles of ethanolamine to ensure complete reaction (the slight excess helps drive the reaction to completion).\n   - TEA as a catalyst can be added in catalytic quantities (e.g., ~5 mol% relative to MPEG-A).\n\n---\n\n#### **Step 4: Reaction Conditions**\n1. Dissolve **methoxy polyethylene glycol acrylate (MPEG-A)** in an anhydrous solvent, such as THF or DMF, at a concentration of ~10 wt%.\n2. Gradually add ethanolamine (1.2\u20131.5 eq.) dropwise to the solution under constant stirring.\n3. Maintain the reaction temperature at **50\u201360\u00b0C** for 6\u201312 hours. The temperature facilitates the nucleophilic attack while avoiding product degradation.\n4. Monitor the reaction progress via **thin-layer chromatography (TLC)** or nuclear magnetic resonance (NMR) by observing the disappearance of the acrylate proton signals (typically ~6 ppm in NMR).\n\n---\n\n#### **Step 5: Quenching and Work-Up**\n\n1. After the reaction is complete, cool the mixture to room temperature.\n2. If necessary, neutralize excess ethanolamine by adding a small amount of dilute HCl, followed by washing with water.\n3. Evaporate the solvent (e.g., THF) under reduced pressure using a rotary evaporator.\n4. Purify the product via **column chromatography** if needed (silica gel with a polar eluent such as ethyl acetate:hexane or methanol:chloroform).\n5. Characterize the final product (**MPEG-NH2**) using techniques such as:\n   - **1H NMR spectroscopy:** Confirm the disappearance of acrylate peaks and the appearance of amine-associated peaks.\n   - **Mass spectrometry (MS):** Verify the product mass matches the expected structure.\n\n---\n\n#### **Step 6: Storage**\n- Store the purified MPEG-NH2 in a desiccator or under inert conditions (argon environment) at low temperatures (e.g., 4\u00b0C) to avoid degradation.\n\n---\n\n### **3. Final Notes and Reaction Scheme**\n\n---\n\n1. **Reaction Scheme:**\n   Methoxy polyethylene glycol acrylate (MPEG-A) + Ethanolamine \u2192 Methoxy polyethylene glycol amine (MPEG-NH2)\n\n2. **Key Considerations:**\n   - Carefully control reaction conditions to prevent side reactions such as acrylate polymerization.\n   - Optimize ethanolamine quantity to achieve efficient Michael addition while minimizing unreacted starting material.\n\n3. **Potential Applications:**\n   Once the amine-terminated MPEG-NH2 is prepared, it can be further functionalized (e.g., via reaction with carboxylic acids, isocyanates, or other hydrophilic groups) to prepare advanced hydrophilic polymers with tailored properties.\n\n---\n\nThis method provides a clear and reliable route to prepare the required amine-functionalized intermediate for further use in hydrophilic polymer modification. If you have further questions, feel free to ask!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "When applying the silicon dioxide (SiO2) coating to a polymer substrate, why is it necessary to repeat the spray coating and heating processes multiple times? Discuss the potential impact on the surface properties."}, {"role": "assistant", "content": "Ah, this is an excellent question regarding the functionalization of a polymer substrate with a silicon dioxide (SiO\u2082) coating. Let us carefully analyze the question and address it systematically by thinking step by step, delving into the underlying principles of material science and surface engineering.\n\n---\n\n### 1. **Question Analysis and Key Points**\n\nIn this problem:\n- We are concerned with the process of applying a SiO\u2082 coating to a polymer substrate via successive steps of **spray coating** followed by **heating.**\n- You are asking specifically why it is necessary to **repeat these steps multiple times**.\n- Additionally, we should examine how repeating these steps influences the **surface properties** of the coated polymer.\n\nThe key points to explore are:\n1. The physical and chemical rationale for repeating the cycles of coating and heating,\n2. The role of each step (spray coating and heating),\n3. The influence on surface properties, with a focus on aspects like thickness, uniformity, adhesion, hydrophilicity, and surface durability.\n\n---\n\n### 2. **Systematic Answer and Step-by-Step Explanation**\n\n#### **Step 1: Spray Coating Process**\nSpray coating is used to deposit a thin film of SiO\u2082 precursor solution (e.g., a silica sol or tetraethyl orthosilicate, TEOS solution) onto the polymer substrate. When a single layer of any coating is applied, some challenges commonly arise:\n- A single layer is often insufficient for achieving **complete surface coverage,** especially on substrates with imperfections, porous structures, or irregular geometries.\n- Uneven spraying or surface tension effects can result in a thin coating layer that is non-uniform.\n- A single layer may exhibit poor film thickness, which limits its desired functional properties (e.g., hydrophilicity, robustness, or thermal stability).\n\n#### **Step 2: Heating Process**\n- Heating is required primarily to **condense and densify the SiO\u2082 coating.**\n- Sol-gel precursors like TEOS undergo hydrolysis and condensation reactions to form a silica network, but these reactions need thermal activation to proceed fully.\n- Heating also promotes adhesion of the SiO\u2082 layer to the polymer substrate by improving intermolecular interactions and potentially enhancing chemical bonding at the interface.\n- However, a single heating step may not achieve full densification of the material or optimal cross-linking, leaving voids or defects in the silica film.\n\n---\n\n#### **Why Is Repetition Necessary?**\nRepeating the spray coating and heating processes builds successive layers of the SiO\u2082 coating. Each iteration addresses the limitations of the previous layer by adding **thickness, uniformity, and durability**. Specifically:\n\n1. **Improved Surface Coverage:**\n   - A single spray may leave some areas of the polymer substrate exposed due to surface irregularities or spray inconsistencies.\n   - By repeating the process, subsequent layers cover these imperfections, ensuring a uniform and complete SiO\u2082 film.\n\n2. **Increased Coating Thickness:**\n   - A thicker SiO\u2082 layer is required to achieve functional surface properties such as high hydrophilicity, mechanical strength, and better thermal or UV resistance.\n   - The thickness of SiO\u2082 coatings follows an additive principle: each spray-and-heat cycle results in additional material deposition.\n\n3. **Enhanced Uniformity:**\n   - Repeated cycles smooth out inconsistencies in the film that may arise after a single spray-and-heat step, leading to a more homogeneous coating.\n\n4. **Improved Adhesion:**\n   - Successive heating steps enhance the interactions between SiO\u2082 and the polymer surface, promoting stronger adhesion. This is particularly critical for polymers, which are generally hydrophobic and may initially exhibit poor bonding affinity to hydrophilic SiO\u2082 layers.\n\n5. **Optimization of Surface Properties:**\n   - Each layer contributes to the evolution of desirable surface characteristics. For instance:\n     - Surface **hydrophilicity** increases as the SiO\u2082 layer becomes thicker and more uniform, exposing many hydroxyl (-OH) groups on the surface.\n     - Surface durability improves as the silica network becomes more cross-linked and compact with each heating step.\n     - Optical or mechanical properties may stabilize with the formation of a defect-free, continuous film.\n\n---\n\n### **Step 3: Potential Impact on Surface Properties**\nAfter several cycles of coating and heating, the surface properties of the polymer substrate are profoundly enhanced. Let us explore these enhancements in detail:\n\n1. **Hydrophilicity:**\n   - SiO\u2082 is inherently hydrophilic due to surface silanol groups (-Si-OH), which attract water molecules through hydrogen bonding.\n   - Repeated applications ensure that these groups are exposed over the entire surface, imparting strong hydrophilic properties.\n\n2. **Coating Uniformity and Smoothness:**\n   - Repetition addresses thickness variations or gaps in the initial layers, yielding a smoother, more uniform film. Surface uniformity is essential for applications such as optical coatings or wettability control.\n\n3. **Mechanical and Chemical Durability:**\n   - Multi-layer coatings are more resistant to abrasion, peeling, or chemical attack because they are thicker, more cross-linked, and better adhered to the substrate.\n   - The heating step in each cycle ensures that each new layer adds strength without compromising the integrity of the previous layers.\n\n4. **Barrier Properties:**\n   - SiO\u2082 is an effective barrier against oxygen, moisture, and other environmental contaminants. A thicker, denser film achieved via multiple cycles enhances these barrier properties.\n\n---\n\n### **Experimental Recommendations**\n- Based on the above explanation, I recommend the following general experimental scheme to optimize the SiO\u2082 application:\n  1. **Prepare a Sol-Gel Solution:** If using TEOS as the SiO\u2082 precursor, prepare a solution with a catalyst (e.g., acidic or basic) to initiate hydrolysis. You may also use pre-synthesized silica nanoparticles in a suitable dispersion medium.\n  2. **Spray Coating Step:** Apply a fine mist of the SiO\u2082 solution onto the polymer substrate, ensuring even coverage.\n  3. **Heating Step:** Heat the coated substrate to 60\u2013120 \u00b0C (or higher, depending on the polymer\u2019s thermal stability) to promote condensation and adhesion of SiO\u2082.\n  4. **Repeat Cycles:** Perform at least 3\u20135 cycles for complete coverage, uniformity, and durability.\n  5. **Post-Treatment:** For specific applications, you may consider curing the coating further at higher temperatures or under specific environmental conditions.\n\n---\n\nIn conclusion, repeating the spray coating and heating processes is essential for achieving uniform, thick, and durable SiO\u2082 layers on a polymer substrate. Each cycle improves the surface coverage, adhesion, and surface properties such as hydrophilicity, ultimately resulting in a functionalized surface suitable for a wide variety of applications.\n\n"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Design an experiment using allyl ether sulfate to modify a polymer. Outline the quantities and conditions you would use, specifying the stages where allyl ether sulfate is added."}, {"role": "assistant", "content": "### Step-by-Step Answer:\n\nTo design an experimental procedure for modifying a polymer with **allyl ether sulfate (AES)**, we aim to introduce hydrophilic characteristics into the polymer structure. This modification typically exploits the reactive **allyl group (-CH2-CH=CH2)** and the **sulfate groups (-OSO3H)** present in AES. The following outlines the steps for a systematic approach.\n\n---\n\n### **Step 1: Analyze the Objective and Key Reaction Points**\n\n1. **Objective:** \n   Enhance a given polymer's hydrophilicity by chemically modifying it using allyl ether sulfate (AES). The hydrophilic sulfate groups can impart polar or ionic characteristics to otherwise relatively hydrophobic polymers, improving their performance in applications like water absorption, adhesion, or emulsification.\n   \n2. **Key Reaction Considerations:**\n   - Allyl ether sulfate is amphiphilic, with an electrophilic nature around its sulfate group and a reactive allyl functionality. It can undergo copolymerization or surface grafting via free-radical or other coupling mechanisms.\n   - Suitable initiation methods include **free-radical polymerization** (if the polymer has unsaturated bonds) or **grafting reactions** (if the polymer has active hydroxyl, amine, or carboxylic acid groups).\n   - Reaction conditions must preserve the integrity of the sulfate group while ensuring high efficiency in the allyl group\u2019s reactivity.\n\n3. **Polymer Type:**\n   Let\u2019s assume the polymer contains hydroxyl (-OH) or carboxyl (-COOH) functional groups. (This procedure can be adapted to other functionalized polymers as discussed below.)\n\n---\n\n### **Step 2: Design the Experimental Scheme**\n\n#### **Materials Required:**\n1. **Polymer substrate:** Assume we use Polyvinyl Alcohol (PVA) or a hydroxyl-functional acrylic polymer.\n2. **Allyl ether sulfate (AES):** Commercially available as a sodium salt (e.g., sodium allyl ether sulfate).\n3. **Initiator:** Water-soluble radical initiator (e.g., potassium persulfate (KPS) or ammonium persulfate (APS)) for graft polymerization.\n4. **Solvent:** Deionized water or a compatible aqueous medium.\n5. **Reaction aids:** Acid/base for pH adjustment (if needed).\n6. **Other reagents:** Sodium chloride (optional, to adjust ionic properties).\n\n#### **Step-by-Step Instructions:**\n\n---\n\n#### **Step 2.1: Polymer Dissolution (Pre-treatment)**\n1. **Weigh polymer substrate:**\n   - For example, PVA: 5 g. (This is scalable depending on intended application.)\n2. **Dissolve polymer:**\n   - Dissolve the weighed PVA in **deionized water** (~100 mL) under stirring and heating (80\u201390\u00b0C) until fully dissolved.\n\n---\n\n#### **Step 2.2: Preparation of the Allyl Ether Sulfate Solution**\n1. **Weigh allyl ether sulfate (AES):**\n   - Use a specific ratio with respect to the polymer (example: molar ratio of AES functional groups: polymer OH groups is 1.5:1). Calculate AES needed from its molecular weight and concentration:\n     - If using AES sodium salt, weigh approximately **6 g AES powder** (assuming polymer molecular weight of ~100 kDa for 5 g).\n2. **Dissolve AES in water or reaction medium:**\n   - Dissolve AES in **15 mL deionized water.**\n\n---\n\n#### **Step 2.3: Graft Polymerization Reaction**\n\n1. **Combine polymer solution and AES solution:**\n   - Lower the temperature of the dissolved PVA to 70\u00b0C.\n   - Add the prepared AES solution dropwise with continuous stirring at 70\u00b0C to ensure uniform interaction.\n\n2. **Add initiator (free-radical generation):**\n   - Dissolve **0.1 g potassium persulfate (KPS)** or ammonium persulfate (APS) in ~5 mL deionized water.\n   - Add the initiator to the reaction mixture in a dropwise fashion.\n   - Maintain stirring and heating at 70\u00b0C\u201375\u00b0C for 2\u20134 hours to allow sufficient time for graft polymerization.\n\n---\n\n#### **Step 2.4: pH Adjustment and Purification**\n1. **Adjust pH:** \n   - Check pH of the reaction mixture. If it becomes too acidic (due to sulfate group interactions), carefully neutralize to pH ~7 using a dilute sodium hydroxide (NaOH) solution.\n2. **Cool the mixture:** \n   - Allow the polymerized product to cool to room temperature.\n3. **Precipitate the product (if needed):**\n   - Add the mixture dropwise into excess 95% ethanol to precipitate the modified polymer. Filter and wash with ethanol to remove unreacted AES and other impurities.\n4. **Dry the polymer:**\n   - Dry the precipitated polymer in a vacuum oven at **50\u00b0C** for ~24 hours.\n\n---\n\n#### **Step 2.5: Characterization**\n1. Verify the successful modification of the polymer using:\n   - **Fourier Transform Infrared Spectroscopy (FTIR):** Look for characteristic sulfate peaks (~1220\u20131270 cm\u207b\u00b9).\n   - **Thermogravimetric Analysis (TGA):** Evaluate thermal stability changes.\n   - **Contact Angle Measurement/Aqueous Swelling Studies:** Assess hydrophilicity.\n   - **Elemental analysis or ion chromatography:** Confirm sulfate ion incorporation.\n\n---\n\n### **Quantities Chart for a 5 g Polymer Batch**\n\n| Component            | Quantity          |\n|----------------------|-------------------|\n| Polymer (PVA)        | 5 g              |\n| Deionized Water      | 100 mL (for polymer) + 15 mL (AES solution) |\n| Sodium Allyl Ether Sulfate (AES) | ~6 g |\n| Potassium Persulfate | 0.1 g            |\n| NaOH (for pH adjustment) | As required |\n| Ethanol (for precipitation)| ~200 mL     |\n\n---\n\n### **Step 3: Summarize Key Learnings**\n1. Allyl ether sulfate introduces hydrophilic sulfate groups into the polymer, enhancing water-solubility or swelling properties.\n2. Graft polymerization requires careful stoichiometric calculations, controlled heating, and correctly chosen initiators to balance efficiency and sulfate group integrity.\n3. Purification by ethanol precipitation and characterization methods validate the hydrophilic nature and structural integration of AES.\n\nThis detailed, stepwise procedure ensures a systematic approach to modifying polymers with hydrophilic allyl ether sulfate. Would you like me to clarify any specific step or reaction condition?"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "The molecule MPEG is mentioned as a component in the experiment involving hydrophilic polymer preparation. Describe a detailed procedure for incorporating MPEG into a polymer synthesis process to enhance its hydrophilicity, ensuring you address monomer proportions and polymerization conditions."}, {"role": "assistant", "content": "Alright, let us carefully address your question and design an experimental preparation scheme for incorporating MPEG (Methoxy-polyethylene glycol) into a hydrophilic polymer synthesis process. Our goal is to enhance the hydrophilicity of the final polymer. I will approach this step by step as per your requirements.\n\n---\n\n### **Step 1: Analyze the Problem**\nThe target is to incorporate MPEG into a polymer to improve its hydrophilicity. MPEG is known for its excellent hydrophilic properties due to the presence of polyethylene glycol segments, which introduce polar ether groups capable of hydrogen bonding with water molecules. Incorporation of MPEG into a polymer backbone or polymer matrix can significantly increase water affinity.\n\nKey considerations for this experiment:\n- MPEG typically has a terminal methoxy group on one end and a hydroxyl (-OH) functional group on the other, making it suited for reactions such as esterification, urethane formation, or radical polymerization.\n- The chosen polymerization scheme must ensure uniform incorporation of MPEG without compromising the hydrophilicity of the polymer.\n- Reaction conditions, monomer ratios, and reagents must be carefully controlled for reproducibility.\n\n---\n\n### **Step 2: Selection of Polymerization Strategy**\nFor incorporating MPEG, two main strategies are commonly employed:\n1. **Grafting MPEG onto an existing polymer backbone.**\n2. **Copolymerizing MPEG with other monomers to form a hydrophilic polymer.**\n\nHere, we will focus on designing a **copolymerization experiment**, as MPEG can be effectively utilized as a macromonomer due to the presence of its hydroxyl group. Specifically, we will utilize free-radical polymerization and functionalize MPEG with a reactive group, such as acrylate or methacrylate, to incorporate it into a growing polymer chain.\n\n---\n\n### **Step 3: Experimental Synthesis of Hydrophilic Polymer**\nBelow, I describe a detailed procedure for synthesizing a hydrophilic polymer using MPEG.\n\n---\n\n#### **3.1 Functionalization of MPEG with Methacrylate**\nBefore MPEG can take part in radical polymerization, it must be functionalized with a methacrylate group. This allows MPEG to act as a macromonomer in the free-radical polymerization process.\n\n1. **Reagents:**\n   - MPEG (Molecular weight: 1000\u20135000 g/mol, commercially available as a waxy solid or viscous liquid).\n   - Methacrylic anhydride (MAA) or methacryloyl chloride (used to introduce the methacrylate group).\n   - Triethylamine (TEA) as a base.\n   - Solvent: Dry tetrahydrofuran (THF) or dimethylformamide (DMF).\n   - 4-dimethylaminopyridine (DMAP) as a catalyst.\n\n2. **Procedure:**\n   - In a dry reaction vessel under an inert nitrogen atmosphere, dissolve MPEG (1 mol equivalent) in dry THF or DMF.\n   - Add TEA (1.2 mol equivalents) slowly to neutralize the acid generated during the reaction.\n   - Slowly add methacryloyl chloride (1.1 mol equivalents) dropwise to the stirred solution at 0\u00b0C to prevent side reactions.\n   - Introduce a catalytic amount of DMAP to accelerate the esterification reaction.\n   - Allow the reaction mixture to warm to room temperature and stir continuously for 8\u201312 hours to ensure complete conversion of the hydroxyl group to a methacrylate ester.\n   - Purify the methacrylated MPEG by precipitating the product in cold diethyl ether and drying under vacuum.\n\n3. **Confirmation:**\n   - Use nuclear magnetic resonance (NMR) spectroscopy to confirm the successful methacrylation of MPEG:\n     - Look for characteristic peaks corresponding to the methacrylate vinyl protons (~5.6 and ~6.2 ppm) and the MPEG methylene protons (~3.5 ppm).\n\n---\n\n#### **3.2 Free-Radical Copolymerization**\nWith methacrylated MPEG (MPEG-MA) prepared, we perform free-radical polymerization with a comonomer to synthesize the hydrophilic polymer.\n\n1. **Reagents:**\n   - Methacrylated MPEG (MPEG-MA) as the hydrophilic macromonomer (1 mol equivalent).\n   - A hydrophobic or hydrophilic comonomer (e.g., methyl methacrylate (MMA) or hydroxyethyl methacrylate (HEMA)). Select HEMA for enhanced hydrophilicity.\n   - Azobisisobutyronitrile (AIBN) as a radical initiator (1 wt% relative to total monomers).\n   - Solvent: Ethanol, methanol, or a water-alcohol mixture (depending on the solubility of the reaction components).\n\n2. **Procedure:**\n   - In a round-bottom flask, dissolve MPEG-MA and the comonomer (MMA or HEMA) in the chosen solvent. Maintain a total monomer concentration of 20\u201340 wt% for controlled polymerization.\n   - Add AIBN as the radical initiator to the solution.\n   - Purge the reaction mixture with nitrogen gas for 30 minutes to remove dissolved oxygen, which can inhibit the radical polymerization.\n   - Heat the reaction mixture to 65\u201370\u00b0C and stir for 6\u20138 hours. Monitor the reaction progress using gel permeation chromatography (GPC) or viscosity measurements.\n   - Once the polymerization is complete, precipitate the polymer by pouring the reaction mixture into excess cold diethyl ether or acetone.\n   - Wash the precipitate several times with the nonsolvent to remove unreacted monomers and oligomers. Dry the polymer under vacuum.\n\n3. **Molar Ratios:**\n   - For a hydrophilic polymer with balanced hydrophilicity, use an MPEG-MA:comonomer ratio of 1:2 to 1:5, depending on the molecular weight of MPEG.\n   - Example: For MPEG-MA (MPEG MW = 2000 g/mol) and HEMA, use 5 mmol MPEG-MA and 10\u201320 mmol HEMA.\n\n---\n\n#### **3.3 Characterization of the Final Polymer**\n1. **Solubility Test:**\n   - Assess the solubility of the polymer in water to confirm improved hydrophilicity.\n\n2. **Thermal Characterization:**\n   - Use differential scanning calorimetry (DSC) or thermogravimetric analysis (TGA) to evaluate the thermal properties of the polymer.\n\n3. **Structural Analysis:**\n   - Use Fourier-transform infrared spectroscopy (FTIR) or NMR to confirm the incorporation of MPEG in the polymer. Look for characteristic ether peaks from MPEG (~1100 cm\u207b\u00b9 in FTIR) and vinyl proton disappearance in NMR.\n\n---\n\n### **Step 4: Summarized Recommendations for Laboratory Practice**\n1. Maintain strict inert conditions during MPEG functionalization to avoid hydrolysis of methacryloyl chloride.\n2. Use freshly distilled solvents and purified reagents to minimize side reactions.\n3. Control the polymerization temperature and reaction time precisely for consistent molecular weight distribution.\n\nBy following this procedure, the synthesized polymer should exhibit significantly enhanced hydrophilicity due to the presence of MPEG segments, making it suitable for biomedical, coating, or water-compatible applications.\n\nI hope this systematically addresses your question. Please let me know if you\u2019d like further clarification on any step!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "What experimental parameters, such as temperature and chamber pressure, would you consider critical when utilizing functionalized phosphate carbon to modify the surface properties of a polymer?"}, {"role": "assistant", "content": "Certainly, let us analyze your question and address it in a systematic and detailed manner to ensure clarity and practical understanding of the experimental procedure.\n\n---\n\n**Step 1: Analyze the Question and Identify Key Points**\n\nThe central topic of your question is: *What experimental parameters are critical (e.g., temperature, pressure) when using functionalized phosphate carbon (FPC) to modify the surface properties of a polymer?*\n\nKey points:\n1. The goal is surface modification of a polymer to enhance its properties (e.g., hydrophilicity).\n2. The functionalizing agent is *functionalized phosphate carbon (FPC)*, a material known for its reactive phosphate groups that can engage with polymer surfaces.\n3. The critical conditions (such as temperature and pressure) for this modification process must be optimized to ensure successful grafting or interaction of the FPC with the polymer.\n\n---\n\n**Step 2: Systematic Answer\u2014Explanation of Parameters and Suggested Experimental Scheme**\n\nTo modify a polymer\u2019s surface using FPC, the process often relies on a chemical interaction between the phosphate groups and functional groups on the polymer surface (such as hydroxyl, carboxyl, or amine groups). Here is a step-by-step experimental preparation scheme, detailing critical parameters for successful modification.\n\n### **1. Polymer Surface Pre-treatment**\n\nBefore any surface modification, the polymer surface must typically be pre-treated to activate it. This might involve:\n- **Cleaning**: Use solvents (e.g., ethanol or acetone) to remove grease or contaminants.\n- **Plasma treatment**: Expose the polymer to oxygen or argon plasma to increase surface energy and introduce reactive groups.\n\n#### Critical Parameters:\n- Plasma chamber pressure: 10\u2013100 Pa (low pressure ensures ionized gas flow).\n- Treatment time: 5\u201310 minutes.\n- Temperature: Room temperature (to prevent thermal degradation of the polymer).\n\n---\n\n### **2. Preparation of Functionalized Phosphate Carbon (FPC)**\n\nThe FPC, often synthesized by grafting phosphate groups onto carbon (e.g., graphene oxide or activated carbon), should be dispersed in a solvent to facilitate interaction with the polymer. \n\n- Prepare an aqueous or alcohol-based dispersion of FPC.\n- Typical concentration: 0.1\u20130.5% w/v (sufficient for uniform coating without aggregation).\n\n#### Critical Parameters:\n- **Temperature of dispersion preparation**: 25\u201340 \u00b0C (to maintain stability of FPC).\n- **Sonication time**: 30\u201360 minutes (to achieve a uniform dispersion of FPC).\n- **pH adjustment**: Adjust pH using dilute NaOH or HCl if needed, ideally between 6 and 8, as phosphate groups are stable under neutral/near-neutral conditions.\n\n---\n\n### **3. Surface Functionalization Reaction**\n\nNow comes the critical step: modification of the polymer using FPC. Typically, this is achieved by immersing the polymer in the FPC dispersion or applying FPC via a coating method. Depending on the nature of your polymer, the reaction may involve physical adsorption, chemical bonding, or both.\n\n#### Reaction Procedure:\n- Immerse or coat the polymer with the FPC dispersion.\n- Use mild agitation (e.g., magnetic stirring) to ensure uniform coverage.\n\n#### Critical Parameters:\n1. **Temperature**: 50\u201380 \u00b0C. This range prevents degradation of the polymer while providing sufficient energy for interaction between the polymer surface and FPC. For thermally sensitive polymers, work at lower temperatures (30\u201350 \u00b0C).\n2. **Duration**: 1\u20134 hours. Longer times allow stronger interactions but must be optimized to prevent undesirable surface reactions.\n3. **Pressure (if using a sealed chamber)**: Atmospheric pressure is typically sufficient. However, if working in a controlled atmosphere (e.g., nitrogen or vacuum), maintain chamber pressure at 0.9\u20131 atm.\n\n---\n\n### **4. Post-treatment: Removal of Excess FPC**\n\nAfter surface modification, any unreacted or excess FPC must be removed to avoid affecting the polymer's functionality.\n\n#### Procedure:\n- Wash the polymer thoroughly with deionized water or a mild phosphate-buffered solution (PBS) to remove unattached FPC.\n- Dry the polymer at low temperature (30\u201350 \u00b0C) in an oven or under a vacuum for 12\u201324 hours.\n\n#### Critical Parameters:\n1. Washing solvent: Deionized water or PBS, pH 6\u20137.5.\n2. Drying temperature: 30\u201350 \u00b0C to prevent thermal damage to the polymer or decomposition of chemically bonded phosphate groups.\n\n---\n\n### **5. Characterization of Modified Polymer Surface**\n\nTo confirm successful modification, various characterization techniques should be employed:\n- **Contact Angle Measurement**: Determine the hydrophilicity of the modified surface (expect a decrease in water contact angle if hydrophilic phosphate groups are successfully attached).\n- **FTIR or XPS Analysis**: Analyze the chemical composition of the surface and confirm the presence of phosphate functional groups.\n- **SEM or AFM**: Examine the surface morphology to check for uniform coverage of FPC.\n\n---\n\n**Final Notes on Critical Parameters**\n- Maintain precise control of temperature during all steps to preserve the integrity of the polymer and phosphate groups.\n- Work under clean and controlled conditions to prevent contamination, which can interfere with surface interactions.\n- Optimize the time, temperature, and concentration of FPC experimentally, focusing on your specific polymer type.\n\nBy following this scheme and carefully tailoring the parameters to your specific materials, you should achieve excellent surface modification, enhancing the hydrophilicity of the polymer. Let me know if you'd like further assistance with this or any related topic!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Explain how you would utilize 2-acrylamido-2-methylpropanesulfonic acid (AMPS) to synthesize an intermediate product for a hydrophilic polymer. Include details of any neutralization steps and justify their role in the reaction."}, {"role": "assistant", "content": "Sure! Let us proceed step by step to analyze your question, summarize the key points, and design a detailed experimental preparation scheme for the synthesis of an intermediate product using 2-acrylamido-2-methylpropanesulfonic acid (AMPS). \n\n---\n\n### **Step 1: Analyze the Question and Summarize Key Points**\nThe goal of this question is to utilize AMPS, a hydrophilic and highly charged monomer due to its sulfonic acid functional group, to synthesize an intermediate product for a hydrophilic polymer. Key points to be addressed include:\n1. Reaction steps involving AMPS.\n2. Consideration of the sulfonic acid group, including its acidic nature, and whether it needs to be neutralized in the reaction process.\n3. Reaction conditions (solvent, temperature, pH, etc.), reagent quantities, and specific outcomes.\n\n---\n\n### **Step 2: Systematic Answer \u2013 Experimental Preparation Scheme**\n\n#### **Introduction to AMPS Chemistry**\nAMPS (2-acrylamido-2-methylpropanesulfonic acid) is a popular hydrophilic monomer because of its sulfonic acid group, which imparts strong ionic interactions and water affinity. In its unneutralized form, the sulfonic acid group (\u2013SO\u2083H) is an acidic proton donor. Depending on the reaction requirements, we can leave this group protonated or neutralize it to a sulfonate anion (\u2013SO\u2083\u207b). For most polymerization processes or intermediate synthesis, the neutralization step is critical to control pH, improve reactivity, and avoid potential acid-catalyzed side reactions like hydrolysis.\n\n#### **Proposed Scheme: Neutralization and Preparation of a Hydrophilic Intermediate**\n\nHere\u2019s a stepwise scheme to synthesize an intermediate using AMPS:\n\n---\n\n### **Step 1: Neutralization of AMPS**\n1. **Objective**:\n   Neutralize the sulfonic acid group (\u2013SO\u2083H) of AMPS to form its sodium salt (sodium AMPS, Na-AMPS). This ensures:\n    - Adjusted pH for subsequent reactions (around neutral or slightly basic).\n    - Improved solubility and reactivity of AMPS in aqueous systems.\n\n2. **Reagents**:\n   - 2-Acrylamido-2-methylpropanesulfonic acid (AMPS).\n   - Sodium hydroxide (NaOH) solution or another suitable base (like KOH).\n\n3. **Experimental Procedure**:\n   - Dissolve the required amount of AMPS (e.g., **10 g, 0.048 mol**) in distilled water (100 mL with stirring). AMPS is highly water-soluble.\n   - Prepare an equimolar aqueous solution of NaOH. For **0.048 mol** AMPS, use **0.048 mol of NaOH, which corresponds to about 1.92 g NaOH**.\n   - Add the NaOH solution dropwise to the AMPS solution under vigorous stirring while monitoring the pH using a pH meter.\n   - Stop addition when a pH of **6.8\u20137.5** is reached (indicating complete conversion of \u2013SO\u2083H to \u2013SO\u2083\u207b, without over-neutralizing to alkalinity).\n   - The reaction is as follows:\n     \\[\n     \\text{AMPS} + \\text{NaOH} \\rightarrow \\text{Sodium-AMPS (Na-AMPS)}\n     \\]\n\n4. **Important Notes**:\n   - Do not exceed pH 7.5; strong alkalinity could affect the acrylamide group, causing unwanted side reactions (e.g., hydrolysis to acrylic acid derivatives).\n   - The solution should remain transparent and homogeneous.\n\n---\n\n### **Step 2: Creation of the Intermediate Product**\n1. **Objective**:\n   Use sodium AMPS (Na-AMPS) in a polymerization or conjugation reaction to synthesize the desired hydrophilic intermediate.\n\n2. **Choice of Polymerization Technique**:\n   - For this step, we can opt for a **free-radical polymerization**, as it\u2019s a common and efficient route for hydrophilic polymer synthesis.\n   - The intermediate could be a homopolymer of AMPS or a copolymer with other hydrophilic/acrylic monomers (depending on the target properties).\n\n3. **Reagents**:\n   - Sodium-AMPS (prepared above).\n   - Water-soluble radical initiator (e.g., **ammonium persulfate (APS)**, potassium persulfate, or azobisisobutyronitrile (AIBN) in certain solvents).\n   - Optional comonomers if copolymerization is desired (e.g., acrylamide, acrylic acid, etc.).\n   - Deionized water as a solvent.\n\n4. **Experimental Procedure**:\n   - Prepare an aqueous solution with the desired concentration of Na-AMPS. For a typical reaction:\n     - Use **10 g (0.048 mol)** of Na-AMPS in 100 mL of deionized water.\n   - If using a comonomer, add it at the desired feed ratio. For example:\n     - Add **4.26 g (0.06 mol)** of acrylamide for a 50:50 molar copolymerization.\n   - Purge the solution with nitrogen gas for **30 minutes** to remove dissolved oxygen, which could inhibit polymerization.\n   - Add 0.1\u20131 wt% APS (relative to the total monomer mass) as the radical initiator. For example:\n     - Use approximately **0.01 g APS**.\n   - Maintain the reaction temperature at **60\u201370\u00b0C** for 2\u20134 hours with constant stirring.\n   - After the reaction, precipitate the intermediate polymer product by adding the solution dropwise into a nonsolvent (e.g., ethanol).\n   - Collect the intermediate by filtration, washing with ethanol, and drying under vacuum at 60\u00b0C.\n\n---\n\n### **Step 3: Justification of Neutralization**\nNeutralization of AMPS is critical for the following reasons:\n1. Prevents unwanted side reactions due to the acidic \u2013SO\u2083H group (e.g., hydrolysis of the acrylamide group or acid catalysis).\n2. Facilitates better control of reaction conditions (pH, ionic strength), essential for achieving high polymerization efficiency.\n3. Improves water solubility of the monomer and its compatibility with comonomers or initiators, enabling a more homogenous reaction mixture.\n\n---\n\nBy following the above process, you can successfully synthesize an intermediate product based on AMPS. Let me know if you'd like assistance with specific variations in comonomers or reaction techniques!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "When incorporating the molecule 2,4,7,9-tetramethyl-5-decyne-4,7-diol tetraethoxy ether into a reaction to synthesize a hydrophilic polymer, what parameters would you optimize (e.g., molar ratios, reaction time, or catalyst concentration) to achieve a controllable and uniform modification?"}, {"role": "assistant", "content": "Certainly! Let us analyze and systematically address your question regarding the incorporation of **2,4,7,9-tetramethyl-5-decyne-4,7-diol tetraethoxy ether** into a reaction to synthesize a hydrophilic polymer. We will also explore the optimization of reaction parameters to ensure a controllable and uniform modification. This step-by-step response will cover the key aspects of the process, including molar ratios, reaction time, catalyst concentration, and other relevant factors important for successful synthesis.\n\n---\n\n### **Step 1: Analyze the structure and function of 2,4,7,9-tetramethyl-5-decyne-4,7-diol tetraethoxy ether**\nFirst, examine the role and features of the molecule you have provided:\n- **Structure**: The compound contains both **hydrophobic aliphatic chains** (methyl and decyne functionality) and **hydrophilic ethoxy ether groups** (-CH2-O-CH2). This makes it an amphiphilic molecule that can act as a surface-active agent or stabilizing moiety in polymer systems.\n- **Role in modification**: Its ethoxy ether groups provide a potential route for enhancing hydrophilicity when incorporated into a polymer chain. Adding this molecule could impart desirable water affinity and surface-wetting properties to the resulting polymer.\n- **Challenges**: The hydrophilic modification process must balance the distribution of hydrophilic and hydrophobic elements to ensure uniform and controlled integration.\n\n---\n\n### **Step 2: Key parameters to optimize the synthesis**\nTo achieve a controllable and uniform hydrophilic modification of the polymer while incorporating **2,4,7,9-tetramethyl-5-decyne-4,7-diol tetraethoxy ether**, the following reaction parameters require careful optimization:\n\n1. **Molar ratio of monomers/reagents**:\n   - The ratio between the polymerizable base monomer(s) (e.g., acrylic acid, acrylamide, or polyethylene glycol methacrylate) and the modifying agent (your provided molecule) must be carefully controlled.\n   - Excess modifying agent leads to phase separation or irregular incorporation, while insufficient amounts will not achieve the desired hydrophilicity.\n   - A typical starting molar ratio for functional monomer: modifying agent is **10:1 to 20:1**. Depending on solubility and reactivity, you may need to adjust the ratio slightly for optimal results.\n\n2. **Catalyst concentration**:\n   - If the synthesis involves radical polymerization, catalysts such as **azobisisobutyronitrile (AIBN)** or **persulfates** (e.g., potassium persulfate) are commonly used.\n   - Catalyst concentration typically ranges from **0.5-1 wt%** of the total monomer weight. Lower concentrations may result in incomplete reaction, while higher concentrations can lead to uncontrolled polymerization or the formation of side products.\n\n3. **Reaction solvent**:\n   - A polar solvent (e.g., water, dimethyl sulfoxide (DMSO), or ethanol) that solubilizes both the base monomers/oligomers and the hydrophilic ether moiety on the modifying agent is preferred.\n   - Water-ethanol mixtures are often an excellent choice for balancing hydrophilicity and hydrophobicity.\n\n4. **Reaction temperature**:\n   - Polymerization temperature significantly impacts the reaction rate and uniformity of incorporation.\n   - For free radical polymerization with AIBN, reaction temperatures of **60\u201380\u00b0C** are typical. For certain water-soluble initiators (e.g., ammonium persulfate), operating between **50\u201370\u00b0C** often yields better control.\n\n5. **Reaction time**:\n   - The polymerization time influences the degree of incorporation and completeness of hydrophilic modification.\n   - Start with a **2\u20134-hour reaction window**, monitoring the conversion and molar mass evolution (via gel permeation chromatography or FTIR if feasible). Extension beyond this point may result in undesirable crosslinking.\n\n6. **pH conditions**:\n   - If the polymerization involves ionizable groups, such as acrylic acid, pH control is necessary to ensure proper reaction. For example:\n     - A pH of **7\u20139** works well with neutral or mildly alkaline conditions to avoid premature ester or ether hydrolysis.\n\n---\n\n### **Step 3: Detailed synthesis scheme**\nUsing the above parameters, the following is a proposed experimental synthesis scheme:\n\n1. **Preparation of Reaction Mixture**:\n   - Dissolve the base monomer (e.g., acrylamide or acrylic acid) in a solvent mixture (e.g., water/ethanol).\n   - Add a measured amount of **2,4,7,9-tetramethyl-5-decyne-4,7-diol tetraethoxy ether** to the reaction flask, ensuring the molar ratio to the monomer lies between **10:1 to 20:1**.\n   - Stir the solution until fully homogenized.\n\n2. **Catalyst Addition**:\n   - Prepare a separate stock solution of the initiator (e.g., AIBN in ethanol or ammonium persulfate in water).\n   - Add this solution dropwise to the reaction flask under constant stirring, maintaining the final concentration of the catalyst at **0.8 wt%** of the total monomer weight.\n\n3. **Purging and Polymerization**:\n   - Purge the reaction flask with nitrogen or argon for **30 minutes** to eliminate oxygen, which can inhibit radical polymerization.\n   - Heat the reaction mixture to **70\u00b0C** while stirring continuously for **3 hours**.\n\n4. **Post-reaction Workup**:\n   - After the reaction, cool the mixture to room temperature.\n   - Precipitate the polymer by adding the reaction mixture into a large excess of a non-solvent (e.g., acetone or diethyl ether).\n   - Filter and wash the polymer thoroughly to remove unreacted components.\n   - Dry the resulting polymer in a vacuum oven at **40\u00b0C** overnight.\n\n---\n\n### **Step 4: Characterization and Evaluation**\nAfter synthesis, evaluate the polymer's hydrophilicity and modification uniformity:\n- **Contact angle measurements**: To determine surface hydrophilicity.\n- **FTIR spectroscopy**: To verify the incorporation of the ethoxy ether groups by identifying specific C-O-C stretch signals.\n- **Gel permeation chromatography (GPC)**: To assess the molecular weight distribution and uniformity.\n- **Water absorption/swelling studies**: To confirm hydrophilic property improvements.\n\n---\n\n### **Conclusion**\n- By carefully optimizing the molar ratios, catalyst concentration, reaction time, and temperature, you can achieve a controllable and uniform modification of the polymer with **2,4,7,9-tetramethyl-5-decyne-4,7-diol tetraethoxy ether**.\n- Employing rigorous characterization methods allows you to ensure the hydrophilic properties of the resulting polymer align with the intended application.\n\nIf you have further questions about adjustments to these parameters or additional characterization techniques, don't hesitate to ask!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "In an experimental setup, how would you systematically vary the concentration of TMS-PEG to study its effect on the hydrophilicity of the modified polymer? Suggest a methodology to evaluate and quantify the change in hydrophilicity across different samples."}, {"role": "assistant", "content": "Certainly! Thank you for asking such a thoughtful question. Let's approach this systematically to design your experimental setup and methodology for varying the concentration of TMS-PEG (trimethylsilane-polyethylene glycol) to study its effect on enhancing the hydrophilicity of the modified polymer.\n\n---\n\n### **Step 1: Analyzing the Question**\n\n- **Key Objective**: The goal is to systematically vary the TMS-PEG concentration and evaluate its effect on the hydrophilicity of the polymer.\n- **Specific Tasks**:\n  1. Prepare a series of modified polymer samples with varying concentrations of TMS-PEG.\n  2. Characterize and quantify the hydrophilicity of these polymers.\n- **Evaluation Criteria**: Quantify changes in hydrophilicity using appropriate analytical techniques, such as contact angle measurements or water absorption capacity testing.\n- **Critical Variables**:\n  - Concentration of TMS-PEG used in synthesis.\n  - Consistency in other synthetic parameters to isolate the effect of TMS-PEG.\n\n---\n\n### **Step 2: Experimental Design**\n\n---\n\n#### **A. Synthesis of Modified Polymer**\n\n1. **Polymer Platform**: Start with the base polymer that is to be modified with TMS-PEG. For example, let's assume the base polymer contains reactive hydroxyl or carboxyl groups suitable for chemical grafting or modification.\n\n2. **Reagents and Chemicals**:\n   - Base polymer (e.g., poly(vinyl alcohol), poly(acrylic acid), etc.).\n   - TMS-PEG (functionalized polyethylene glycol with reactive end groups, such as methoxysilyl groups).\n   - An appropriate coupling agent (if necessary) to link TMS-PEG to the base polymer.\n   - Solvent (e.g., ethanol, water, or an appropriate buffer, depending on the solubility of reactants).\n   - Catalyst (e.g., acids, bases, or silanization activators if using methoxysilyl groups).\n\n3. **Procedure**:\n   - Prepare a series of reaction solutions with varying concentrations of TMS-PEG (e.g., 0.1%, 0.5%, 1%, 2%, 5% by weight relative to the base polymer).\n   - Dissolve the base polymer in the solvent at a suitable concentration (e.g., 5\u201310 wt%).\n   - Gradually add TMS-PEG to the polymer solution while stirring to promote homogeneous mixing.\n   - Adjust the pH or add a coupling agent/catalyst as required to initiate the reaction (e.g., in the case of silanization, acidic or basic conditions may be required).\n   - Allow the reaction to proceed at a controlled temperature (e.g., 50\u201370\u00b0C) while stirring for the recommended reaction time (e.g., 24\u201348 hours for silanization reactions).\n\n4. **Post-Reaction Curing and Purification**:\n   - After the reaction is complete, remove unreacted TMS-PEG by dialyzing the solution against pure solvent or precipitating the polymer from the solution, followed by thorough washing.\n   - Dry the polymer under vacuum at a low temperature to avoid degradation of grafted TMS-PEG.\n\n---\n\n#### **B. Systematic Variation**\n\n- To study the effect of TMS-PEG concentration:\n  - Prepare a **set of samples** where the TMS-PEG concentration differs (e.g., 0.1%, 0.5%, 1%, 2%, 5% by weight relative to the base polymer).\n  - Ensure all other reaction parameters\u2014such as temperature, time, base polymer concentration, and solvent\u2014remain **constant** to isolate the effect of TMS-PEG concentration.\n  - Label the samples clearly and store them under consistent conditions.\n\n---\n\n### **Step 3: Hydrophilicity Evaluation**\n\nHydrophilicity can be evaluated using the following techniques. Systematic characterization is essential to extract reliable and quantitative data.\n\n#### **A. Contact Angle Measurements**\n1. **Principle**: Contact angle measures the wettability of a solid surface. Lower contact angles indicate higher hydrophilicity.\n2. **Equipment**: Contact angle goniometer.\n3. **Procedure**:\n   - Prepare thin polymer films or coatings on a flat substrate.\n   - Measure the static contact angle of a water droplet (2\u20135 \u00b5L) placed on the surface of each sample.\n   - Take multiple measurements on different areas of each sample to ensure reproducibility.\n4. **Analysis**: Compare the contact angles across different samples. Plot TMS-PEG concentration vs. contact angle to understand the correlation.\n\n#### **B. Water Absorption Studies**\n1. **Principle**: Hydrophilic polymers absorb more water than hydrophobic ones.\n2. **Procedure**:\n   - Immerse dry polymer samples (of known weight) in deionized water for a fixed duration (e.g., 24 hours).\n   - Remove excess water gently and weigh the swollen samples to calculate water uptake.\n   - Water absorption (%) = [(Wet Weight \u2212 Dry Weight) / Dry Weight] \u00d7 100.\n3. **Analysis**: Compare water absorption as a function of TMS-PEG concentration.\n\n#### **C. FTIR Spectroscopy**\n1. **Principle**: Confirm the extent of TMS-PEG incorporation by identifying characteristic PEG peaks (e.g., C\u2013O\u2013C stretching at ~1100 cm\u207b\u00b9).\n2. **Procedure**:\n   - Record FTIR spectra of all samples and the base polymer.\n   - Use the relative intensity of PEG characteristic peaks to assess modification levels.\n\n#### **D. Swelling Behavior**\n- Hydrophilicity can also be inferred from the swelling ratio in an aqueous environment. This involves immersing the polymer in water, measuring its dimensions or weight over time, and comparing swelling behavior across samples.\n\n---\n\n### **Step 4: Data Analysis and Interpretation**\n\n1. Plot the concentration of TMS-PEG (x-axis) against:\n   - Contact angle (y-axis, inversely proportional to hydrophilicity).\n   - Water absorption (%) or swelling ratio (y-axis, directly proportional to hydrophilicity).\n\n2. Analyze trends:\n   - Increased TMS-PEG concentration is expected to enhance hydrophilicity (lower contact angle, higher water absorption) up to a saturation point. Beyond this, additional TMS-PEG may have diminishing returns due to steric hindrance or aggregation.\n\n3. Statistical Analysis:\n   - Use statistical tools (e.g., ANOVA) to confirm the significance of observed trends.\n\n---\n\n### **Conclusion**\n\nBy systematically varying TMS-PEG concentration and employing the outlined evaluation methods, you can reliably quantify its effect on polymer hydrophilicity. This approach not only provides valuable insights but also establishes a robust framework for optimizing the synthesis process.\n\n---\n\nFeel free to ask additional questions or seek clarification on any step of the procedure!"}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Design an experimental scheme to prepare a hydrophilic polymer coating using acrylamide (AM) as the primary monomer. Ensure you include key steps such as polymerization initiation, cross-linking, and any necessary post-treatment processes."}, {"role": "assistant", "content": "Certainly, thank you for the detailed context and specific question. Let us now design a systematic experimental scheme for synthesizing a hydrophilic polymer coating using acrylamide (AM) as the primary monomer. I will adhere to the outlined requirements, breaking down the synthesis into essential steps and providing detailed information on reaction conditions, reagent ratios, and other critical parameters to facilitate the experiment's successful execution in the laboratory.\n\n---\n\n### **Step 1: Analysis of Key Points**\nYour objective is to synthesize a hydrophilic polymer coating using acrylamide (AM) as the primary monomer. The polymer must exhibit high hydrophilicity, making it suitable for applications such as biocompatible coatings or anti-fouling surfaces. \n\nFor this, we'll focus on:\n1. **Polymerization initiation** \u2013 Efficiently initiating polymerization using a free-radical approach.\n2. **Cross-linking** \u2013 Introducing a cross-linking agent to ensure that the coating exhibits the desired mechanical properties and stability.\n3. **Post-treatment** \u2013 If applicable, further processing to enhance the hydrophilic performance or functional properties of the polymer.\n\nThe process will rely on aqueous polymerization to align with the hydrophilic property requirements. Let us proceed step by step.\n\n---\n\n### **Step 2: Detailed Experimental Scheme**\n\n#### **2.1 Materials Required**\n1. **Monomer**: Acrylamide (AM) \u2013 A hydrophilic monomer with water-soluble properties.\n2. **Cross-linker**: N,N\u2032-methylenebisacrylamide (MBAA) \u2013 A commonly used cross-linker for acrylamide-based systems to introduce network structures.\n3. **Initiator**: Ammonium persulfate (APS) \u2013 A water-soluble initiator to generate radicals.\n4. **Accelerator**: N,N,N\u2032,N\u2032-Tetramethylethylenediamine (TEMED) \u2013 To speed up the radical formation process initiated by APS.\n5. **Solvent**: Deionized water.\n6. **Substrate for Coating**: Glass slides, polymer films, or other support surfaces requiring hydrophilic coatings.\n\n---\n\n#### **2.2 Synthesis Steps**\n\n**Step 1: Surface Preparation (Substrate Pre-treatment)**\n1. **Purpose**: Ensure strong adhesion of the hydrophilic polymer coating to the substrate.\n2. **Procedure**:\n   - Clean the substrate (e.g., glass slides) thoroughly with a detergent solution.\n   - Immerse in a mixture of ethanol and water (1:1 ratio) to remove organic contaminants.\n   - Rinse with deionized water and dry under a stream of nitrogen.\n   - For glass substrates, further activate the surface by treating with an oxygen plasma or 1 M NaOH for 10 minutes to improve adhesion.\n\n---\n\n**Step 2: Preparation of the Monomer Solution**\n1. **Purpose**: Synthesize an aqueous precursor solution containing all necessary reagents.\n2. **Procedure**:\n   - Weigh **5.0 g of acrylamide (AM)** and dissolve it in **40 mL of deionized water** in a glass beaker. Stir at room temperature until fully dissolved.\n   - Add **0.05 g of N,N\u2032-methylenebisacrylamide (MBAA)** as the cross-linking agent while continuing to stir.\n   - Prepare a solution of **0.02 g of ammonium persulfate (APS)** in **1 mL of deionized water**, and add it to the reaction mixture. This acts as the radical initiator.\n   - Add **5 \u03bcL of TEMED** to the reaction mixture while stirring. TEMED acts as an accelerator, facilitating the decomposition of APS and generating free radicals for polymerization.\n   - Degas the solution under a flow of nitrogen or argon for 5\u201310 minutes to remove dissolved oxygen, which can inhibit free-radical polymerization.\n\n---\n\n**Step 3: Coating Application**\n1. **Purpose**: Uniformly apply the monomer solution to the substrate.\n2. **Procedure**:\n   - Place the pretreated substrate on a clean, leveled surface.\n   - Apply a thin layer of the monomer solution (ca. 50\u2013100 \u03bcm thickness) using a spin-coating technique or dip-coating method for uniform coating. Control the speed and withdrawal rate for optimal thickness.\n   - If spin-coating, spin at **1000 rpm for 30 seconds**.\n\n---\n\n**Step 4: Polymerization**\n1. **Purpose**: Induce free-radical polymerization to form the hydrophilic polymer network.\n2. **Procedure**:\n   - Transfer the coated substrate to a covered humidified chamber maintained at **50\u201360\u00b0C**.\n   - Allow polymerization to proceed for **2 hours**.\n   - The heat will decompose APS, initiating polymerization, while TEMED accelerates the process. MBAA will introduce cross-links into the polymer, stabilizing it as a coating.\n\n---\n\n**Step 5: Post-treatment**\n1. **Purpose**: Remove unreacted monomers and enhance hydrophilicity.\n2. **Procedure**:\n   - Immerse the coated substrate in deionized water and gently agitate it for **24 hours** to remove any unreacted monomer or unbound polymer.\n   - Replace the water every 6 hours for effective purging.\n   - Optionally, treat the coating with dilute ethanol (10% v/v) for surface restructuring to improve uniformity.\n\n---\n\n**Step 6: Characterization and Analysis**\n1. **Surface Hydrophilicity**:\n   - Measure the **water contact angle** on the coated substrate to confirm hydrophilicity. Values below 30\u00b0 indicate high hydrophilicity.\n2. **Chemical Structure**:\n   - Use **FTIR spectroscopy** to verify the successful incorporation of acrylamide and cross-links.\n3. **Adhesion Test**:\n   - Conduct an adhesion test (e.g., tape peeling) to confirm the robustness of the coating on the substrate.\n\n---\n\n### **Step 3: Notes and Additional Tips**\n1. The concentration of cross-linker (MBAA) should be carefully tuned. If too high, the polymer may become overly rigid and lose its hydrophilicity. If too low, the polymer may lack mechanical stability.\n2. TEMED must be handled carefully in small amounts, as excessive TEMED can cause uncontrolled polymerization.\n3. Ensure the polymerization chamber has consistent temperature control to obtain uniform cross-linking and polymer growth.\n\n---\n\nThis systematic procedure should enable the successful preparation of a thin, uniform, and mechanically stable hydrophilic polymer coating. Feel free to ask additional clarifying questions if needed, and I encourage you to carefully plan and document the steps during the experiment."}]}
+{"messages": [{"role": "system", "content": "You are a seasoned professor in the field of materials science, with primary research focusing on the monomer synthesis of hydrophilic polymers."}, {"role": "user", "content": "Formulate an aqueous coating preparation using an oligomer synthesized from glycidol and polyfunctional isocyanate resin. Specify how you would disperse the polymer in water and incorporate a curing agent, taking into account a solvent-free system."}, {"role": "assistant", "content": "Thank you for the detailed description of your question! Let us carefully think through your problem step by step to design a systematic experimental preparation scheme for an aqueous coating based on a hydrophilic polymer derived from glycidol and a polyfunctional isocyanate resin. To meet the requirements of a solvent-free system and to achieve excellent dispersion in water, we must break this problem into logical stages. \n\n### Key Points of the Question:\n1. **Polymer Synthesis**:\n   - Use glycidol as one reactive monomer (highly hydrophilic).\n   - Combine it with a polyfunctional isocyanate resin to form a hydrophilic oligomer or prepolymer with tunable molecular architecture.\n2. **Aqueous Dispersion of Polymer**:\n   - Post-synthesis, the polymer must be made water-dispersible.\n   - Design must involve methods to introduce hydrophilic segments, allowing effective water compatibility.\n3. **Incorporation of a Curing Agent**:\n   - Developing a crosslinked network during cure, taking care to adjust reactivity.\n   - Use of solvent-free strategies compatible with the prepolymer/coating formulation.\n\n### Detailed Experimental Preparation Scheme:\nLet us now work through the experiment systematically.\n\n---\n\n#### Step 1: **Synthesis of Hydrophilic Oligomer**\n##### Reaction:\nThe reaction involves **glycidol** (a highly reactive epoxide) and the **polyfunctional isocyanate resin**. Glycidol's hydroxyl and epoxide groups are reactive and will readily react with the isocyanate groups (-N=C=O), forming urethane and secondary hydroxyl functional groups. The secondary hydroxyl groups enhance water dispersibility while maintaining hydrophilicity.\n\n##### Reagents and Molar Ratios:\n- **Polyfunctional isocyanate resin** (e.g., hexamethylene diisocyanate (HDI) trimer or toluene diisocyanate (TDI) trimer): 1 mole (starting material).\n- **Glycidol**: Use a slight molar excess (1.1\u20131.2 moles) relative to -NCO groups in the resin to ensure all isocyanates are fully reacted and optimize hydrophilicity.\n- **Catalyst**: Dibutyltin dilaurate (DBTDL) or triethylamine (concentration: ~0.1% w/w of total reaction mixture) to promote reaction.\n\n##### Procedure:\n1. Set up a three-neck round-bottom flask equipped with a thermometer, stirrer, and reflux condenser under nitrogen atmosphere to prevent moisture interference.\n2. Add the polyfunctional isocyanate resin (e.g., HDI trimer) to the flask. Heat to 50\u201360 \u00b0C under stirring.\n3. Slowly add glycidol dropwise over 1\u20132 hours using an addition funnel, maintaining the temperature at 50\u201360 \u00b0C to avoid excessive exothermicity.\n4. Add a trace amount of DBTDL catalyst to accelerate the reaction.\n5. Allow the reaction to proceed for 4\u20136 hours at 50\u201360 \u00b0C until FTIR spectroscopy confirms the disappearance of the isocyanate peak (~2270 cm\u207b\u00b9).\n6. The resulting product will be a hydrophilic oligomer containing secondary hydroxyl and urethane linkages.\n\n##### Key Notes:\n- Ensure a nitrogen blanket to prevent interaction with atmospheric moisture during the reaction.\n- Avoid overheating, as this may lead to side reactions such as oligomer gelation or crosslinking.\n\n---\n\n#### Step 2: **Dispersing the Hydrophilic Oligomer in Water**\nTo create a solvent-free aqueous coating, we will modify the synthesized oligomer to make it dispersible in water. The free hydroxyl groups on the oligomer allow neutralization and ionic stabilization in water.\n\n##### Procedure:\n1. **Neutralization with Acid**:\n   - Add a small amount of neutralizing acid (e.g., dilute acetic acid or lactic acid) to the oligomer, converting some hydroxyl groups into carboxylate salts for improved dispersibility.\n   - Acid addition should be done at room temperature with continuous stirring.\n   - Recommended neutralization ratio: ~10\u201315% of hydroxyl groups.\n2. **Water Addition**:\n   - Slowly add deionized water to the neutralized oligomer under vigorous stirring at room temperature to form a stable aqueous dispersion.\n   - Continue stirring for 30 minutes to ensure uniform dispersion.\n\n---\n\n#### Step 3: **Incorporating the Curing Agent**\nNow that we have a stable water-dispersible polymer system, a curing agent is added to allow crosslinking during coating formation. An ideal curing agent will crosslink the hydroxyl groups of the oligomer while being compatible with the solvent-free, aqueous system.\n\n##### Choice of Curing Agent:\n- **Polycarbodiimide** or **blocked isocyanate** derivatives are excellent curing agents for hydroxyl-functional systems, as they promote urethane crosslinking upon curing at elevated temperatures (e.g., 120\u2013150 \u00b0C).\n- Molar ratio: Use curing agent at ~0.8\u20131.0 equivalents per hydroxyl group.\n\n##### Procedure:\n1. Add the chosen curing agent directly to the aqueous dispersion of the oligomer under stirring.\n2. Mix thoroughly for 15\u201320 minutes at room temperature to ensure homogeneity.\n3. The final coating formulation is now ready for application.\n\n---\n\n#### Step 4: **Thermal Curing of the Coating**\nAfter coating application, curing is essential to achieve full crosslinking and develop robust film properties.\n\n##### Procedure:\n1. Apply the prepared aqueous coating onto the substrate (e.g., steel, plastic, or glass) using standard methods like dip coating or spraying.\n2. Bake the coated substrate in an oven at 120\u2013150 \u00b0C for 30\u201360 minutes, depending on the curing agent and substrate tolerance.\n3. Allow the coating to cool to room temperature.\n\n---\n\n### Final Notes:\n1. The hydrophilicity of the final coating can be tuned by adjusting the glycidol-to-isocyanate ratio during synthesis.\n2. The choice of curing agent and baking conditions depend on the substrate and desired coating properties.\n3. Test the coating for adhesion, water resistance, and appearance to validate application goals.\n\nBy following this experimental scheme, you will successfully prepare a hydrophilic aqueous coating system that meets the requirements of solvent-free processing. Let me know if there are additional aspects to clarify!"}]}